Reactive block-copolymer and method for production thereof (versions)

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing block-copolymers which contain a reactive functional group. Described is a method of producing a block-copolymer, involving: a) reaction of an acrylic monomer, having functional groups which are epoxy, acid, anhydride, amine, amide and hydroxy groups, and one or more vinyl monomers in the presence of a free-radical initiator a stable free radical at the first step to obtain a reaction product which contains a residual unreacted acrylic monomer; and b) reaction at the second step of one or more vinyl monomers with the reaction product from the first step to obtain a second block which contains a residual unreacted acrylic monomer. Also described are versions of said method of producing a block-copolymer. Described is a block-copolymer obtained using said methods, containing: a) a first block which contains monomer links of a functionalised acrylic monomer, having functional groups which are epoxy, acid, anhydride, amine, amide and hydroxy groups, and monomer links of a vinyl monomer; and b) a second block which contains monomer links of one or more vinyl monomers and monomer links of a functionalised acrylic monomer, having functional groups which are epoxy, acid, anhydride, amine, amide and hydroxy groups in the first block. Described is a thermoplastic polymer composition which is used to obtain materials with high impact resistance and mechanical strength, which contains: (a) 1-98 wt % of a first thermoplastic, having functional groups selected from a group consisting of amine, amide, imide, carboxyl groups, carbonyl, carbonate ester, anhydride, epoxy, sulpho, sulphonyl, thionyl, sulphydryl, cyano and hydroxy; (b) 0.01-25 wt % of said block-copolymer, which contains a functional group which is capable of reacting with the functional group in the thermoplastic; and (c) 1-98 wt % of a second thermoplastic polymer which is miscible or compatible with the second block of said block-copolymer.

EFFECT: obtaining block-copolymers which can be used as reactive compatibility agents of thermoplastic mixtures of polymers.

31 cl, 10 dwg, 14 tbl, 56 ex

 

The technical FIELD

The present invention relates to a method for producing block copolymers containing a reactive functional group, such as anhydrite, epoxy, amino, amido, hydroxyl or acid groups, in two or more blocks via free radical polymerization in the presence of a stable free radical, to compositions comprising block copolymers containing reactive monomer or monomers in two or more blocks via free radical polymerization, and to the use of a composition of matter as agent compatibility in the blending polymers.

The LEVEL of TECHNOLOGY

Blending of polymers provides a tremendous opportunity to obtain materials with improved characteristics property/value. Since most polymer pairs is immiscible, the strategy compatibility necessary to obtain maximum synergy properties. This strategy is usually cheaper and less time consuming than the development of new monomers and/or new methods of polymerization to create a completely new polymer materials. An additional advantage of the mixtures of polymers is that a wide range of material properties is achieved by simply changing the composition of the mixture. Compatibility of mixtures of polymers can be achieved by using as the clients compatibility which are macromolecular structures that demonstrate activity at the interface in heterogeneous mixtures of polymers. Usually chain agent compatibility have a modular structure with one main unit, miscible with one component of the mixture, and the second block, mixing with the other component of the mixture. Another selection option for compatibility is the addition of a reactive polymer, miscible with one component of the mixture and reactive toward the functional groups attached to a second component mixture, which leads to the formation "in situ" block - or graft copolymers. This technique has certain advantages over the addition of the previously received block or graft copolymers. Usually reactive polymers can be obtained by free-radical copolymerization or by grafting in the melt reactive groups in a chemically inert polymer chain. In addition, reactive polymers only form block or graft copolymers at the site where they are needed, i.e. at the interface of immiscible polymer blends.

Was carried out the successful development agents compatibility, which provide compositions of polyolefins, such as polypropylene, and minerals, glass and/or polar thermoplastics with excellent the physical properties. By the early 1970s agents compatibility, based on malarvannan polypropylene, are available for the production of composite materials based on polyolefin. Residues of maleic anhydride of these agents compatibility react with nucleophilic amines and hydroxyl functional groups in the polyamides, polyesters and polycarbonates, and aminosilane used for surface modification of glass and other mineral fillers.

Attempts to apply a similar solution to other major hydrocarbon polymer group, styrene were unsuccessful. The reaction with maleic anhydride polystyrene random chain of polystyrene and is not localized at the ends of the chain, as in the case of polypropylene. Similarly, the copolymerization of styrene monomer and maleic anhydride leads to alternating copolymer, the copolymerization of styrene with other nucleophilic reactive monomers random chain of polystyrene. Such candidate agents compatibility contain functional groups that are reactive towards nucleophiles present in the polar thermoplastics and aminodiphenylamine fillers, and therefore interact with the polar phase composites (for example, glass, minerals, and/or polar thermoplastic polymers), PR is leading in some cases to the formation of a more homogeneous dispersion of one material in another. However, since the architecture of these candidates as agents compatibility statistical, because there is no single domains, and therefore there is no domain that is compatible with the styrene phase of the composite and sufficient length of the chain, wrapped in polystyrene in the composite. As a result, even when the improved dispersion of one phase in another specified improvement in the physical material properties of polymer blends and copolymers is not achieved, and, in fact, sometimes even degradation of physical properties in comparison with the same material without the use of candidate agents compatibility (Dong, C. et. al. Polymer.1996, 37, 14, 3055-3063; Chang, F. et al. Polym. Eng. Sci, 1991, 31, 21, 1509-1519; Jannasch, P. et. al. J. Appl. Polym. Sci., 1995, 58, 753-770).

Successful development strategy of polyolefin composites and failure with polystyrene composites were studied and reported Fumio Ide (Ide, F. et. al. J. Appl. Polym. Sci., 1974, 18, 4, 963-74). As mentioned in the application US 2005/004310 A1, researchers have recognized that the presence of reactive functional groups such as maleic anhydride, was necessary agents compatibility, but not enough for good compatibility. In addition, the location of the nucleophilic reactive functional groups of the agent compatibility in the architecture of the polymer was statistical. Materials agents compatibility, which is predstavlyaet the structure of the block copolymer, in which each of the blocks is thermodynamically compatible with one of the two polymeric materials to be mixed are more effective as agents of compatibility than their interchangeable parts of a statistical copolymer (application no 2004/0077788 A1). Well-defined block copolymers of styrene containing reactive groups, were prepared and applied as reactive agents compatibility, but they usually have significant disadvantages, such as: i) a comprehensive synthesis technology, ii) the presence of volatile and corrosive fragments and (iii) adding extraneous polymer with other chemical and physical properties (Park, S. et. al. Polymer, 2001, 42, 7465-7475; U.S. Pat. No. 6417274 B1; Koulouri, E.G. et. al. Macromolecules, 1999, 32, 6242-6248).

To obtain well-defined block copolymers that are used as agents compatibility, there have been several approaches, one approach is the use of processes of a living polymerization. The processes of living polymerization in which the reaction of chain breakage suppressed or significantly reduced, allow to obtain block copolymers, because the lifetime of each individual chain is extended to a period that is comparable to the duration of the process (minutes or hours). It is possible to obtain block copolymers with function the functional groups of the anionic polymerization, but this method presents serious limitations for its wide practical application. On the one hand, it requires conditions of high purity monomers, because the traces of humidity destroy the catalyst for many of the monomers it is very difficult to manage, requiring extremely low temperatures. In addition, polymerization of monomers having functional groups, impractical, as the catalyst may be destroyed due to the presence of many functional groups. In the industrial application of the foregoing methods is reduced to two or more monomers and does not provide the opportunity to get technologically important functional monomers.

Because of limitations in the process of anionic polymerization more promising method for producing block copolymers with a greater variety of monomers is a technique based on living or kaijuusha free radical polymerization. This can be achieved by adding to a different standard methods of free radical polymerization reagent, which greatly reduces the frequency of irreversible chain termination or transfer reactions circuit, giving living or kasiisi the nature of the polymerization, which is also called "controlled polymerization" or "controlled free radical polymerization". There are several is like ways to get this mode (Sawamoto et. al. Chem. Rev. 2001, 101, 3689-3745), but most of them are limited to industrial technology because they require reagents that are not commercially readily available on the market. Among these techniques that is particularly advantageous for a specified reagents are available in the market, is kasirivu free radical polymerization regulated nitroxide (mediated by nitroxide radical polymerization NMRP) and their derivatives (such alkoxyamines, patent US 6455706 B2, which act as a stable free radicals, limiting growth of the polymer chain and not limiting its rapid and reversible manner, taking into account the short time the growth of the chain by using the stage of adding the monomer (patent US 5401804; EP 0869137 A1; US patent 6258911 B1; US patent 6262206 and patent US 6255448 B1).

Mediated nitroxide radical polymerization or NMRP was used to obtain diblock copolymers as additives for the preparation of compositions of lubricating oils, as reported Visger and others (patent US 6531547 B1), and recently this technique was used to obtain pure diblock copolymers, which are able to be active as agents compatibility in mixtures of polymers. Claim US 2005/0004310 filed Hong and others, reveals the compatibility of styrene polymer/polyamide or styro inogo polymer/glass using iblokov styrene and styrene reactive unit. The technique, reported includes cleaning first synthesized block (dilution THF, addition of methanol or water/methanol and drying) before addition of the second monomer to obtain the purified block-polystyrene. A variant of this approach, which was successfully applied in polyphenylenevinylene mixtures (patent US 6765062 B2) represents the synthesis of polymers with terminal functional groups using functional alkoxyamine (patent US 6566468 B1; application US 2004/0049043 A1). This approach requires special regulatory agent carrying an epoxy functional group, which is believed to be commercially available and more expensive than simple regulatory agents, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) or derivatives of TEMPO. Another approach to the synthesis of pure block copolymers takes advantage of the natural alternating polymerization of certain monomers, such maleic anhydride and styrene, in the presence of nitroxide to regulate the molecular weight and polydispersity, as described in published application US 2004/0077788 A1, named as block copolymers containing functional group.

Successful reactive agents compatibility, described in the preceding technologies, represent a non-statistical block polymers based n the copolymers, consisting of one reactive unit and one inert block or, in special cases, only one reactive monomer at the end of the polymer chain. However, to get the pure blocks, requires an intermediate stage of purification, such as evaporation of solvent, precipitation and evaporation, and cleaning stage increases the cost of the process. Only when the monomers naturally create alternating composition, such as in the case of styrene and maleic anhydride, which blocks formed by reactivity, cleaning stage is not required. Therefore, there is a need for improvements in the field of agents compatibility.

The INVENTION

The present invention provides a method of obtaining a block copolymer having a first block having functional groups backed acrylic monomer that does not use cleaning stage after polymerization of the first block so that the amount of unreacted residual monomer, which has a functional group, intentionally left in the reaction product of the first stage. The second block added to the first block to form a block copolymer. The second block is preferably polymerized from at least one vinyl monomer and residual neproreagirovavshimi the first monomer, which has a functional group. Functional groups, therefore, add to the second block as the first block, which, as found, provides a block copolymer having good characteristics as agent for compatibility.

In one embodiment of the present invention provides a method of obtaining a block copolymer, which comprises the reaction of an acrylic monomer, which has a functional group, and one or more vinyl monomers in the presence of a free radical initiator and a stable free radical to obtain the product of the reaction, where the reaction product includes residual unreacted acrylic monomer, and the reaction of one or more vinyl monomers with the reaction product to obtain a second block, where the second block includes residual unreacted acrylic monomer.

In one embodiment of the present invention provides a block copolymer which has a structure that includes a first block, which comprises Monomeric units functionalized acrylic monomer and Monomeric units of a vinyl monomer and a second block, which comprises Monomeric units of one or more vinyl monomers and Monomeric units functionalized acrylic monomer of the first block. Predpochtitelno embodiment the block copolymer adapted for use as an agent compatibility of mixtures of materials, especially for mixtures of thermoplastic polymers.

Unlike agents compatibility of the block copolymer described in the prior art, it was unexpectedly discovered that the crude block copolymers according to this application (where at least one type of reactive acrylic monomer is present in the first and in the second block, after the monomers remaining from the first synthesis unit, do not remove and thus included in the second block) can work effectively as reactive agents compatibility thermoplastic mixtures of polymers. In one embodiment of the present invention provides the following mixed composition, which is typical for mixed formulations, in which the copolymers according to the invention act as agents of compatibility.

Typical mixed composition according to the invention includes from about 1 to about 98% by weight of the first thermoplastic polymer that has a functional group selected from the group consisting of amino, amido, amido, carboxyl, carbonyl, carbonate of ester, anhydride, amoxilina, sulfo, sulfonyloxy, sulfanilic, sulfhydryl, cyano and hydroxyl, from approximately 0.01 to approximately 25% of the weight of the block copolymer that includes a first block, which has monomer units funktsionalizirovannogo monomer and Monomeric units of a vinyl monomer, and the second block, which has monomer units of one or more vinyl monomers and Monomeric units functionalized acrylic monomer in the first block, and from about 1 to about 98% by weight of the second thermoplastic polymer that is miscible or compatible with the second block of the block copolymer, where the acrylic monomer has a functional group that is reactive with functional groups in the first thermoplastic polymer.

BRIEF DESCRIPTION of DRAWINGS

A better understanding of the invention can be achieved when the detailed description of embodiments of the invention according to the examples set forth below, considered in conjunction with the attached drawings, which are described as follows.

Figure 1 is a schematic way of periodic process according to the present invention.

Figure 2 is a schematic way of a continuous process according to the present invention.

Figure 3 is photomicrography composition of the mixture according to the present invention.

Figa and 4b represents photomicrography composition of the mixture prior art.

Figure 5 is photomicrography composition of the mixture according to the present invention.

6 is photomicrography compo is icii mixture prior art.

Fig.7 is photomicrography composition of the mixture prior art.

Figa and 8b represent photomicrography composition of the mixture according to the present invention.

DETAILED description of the INVENTION

The present invention provides a method, a block copolymer obtained by the above method in which the composition, microstructure and molecular weight of the copolymer carefully regulate, and use of the block copolymer as an agent compatibility. The term microstructure refers to the detailed sequence or arrangement of links of each monomer in the average or normal chain of the copolymer. The term composition refers to the full average relative amount of monomers in the copolymer chains, which can be expressed in molar or weight ratio. In particular, one embodiment of the invention includes a block copolymer having a first block of a statistical copolymer with a total size of the circuit from 1 to 720 monomer unit and the second unit, which includes the residual monomers formed during polymerization of the first block and one or more additional monomers, where the second block has a size of from 100 to 2000 monomer units.

The block copolymer can be obtained according to the present invention using a two-stage method, including: (1) the reaction Smoot is a new monomer, having functional groups and one or more vinyl monomers in the presence of a free radical initiator and a stable free radical with obtaining the product of the reaction, where the reaction product includes residual unreacted acrylic monomer, and (2) the reaction of one or more vinyl monomers with the reaction product from the first stage to obtain a second block, where the second block includes residual unreacted acrylic monomer. The monomers are polymerized using a stable free radical and traditional svobodnoradikal initiator or alkoxyamine, in the second stage, add the monomers and optional more kolichestvo initiator. The solvents can be used optionally on one or both stages.

The reaction product from the first stage includes a first block, which is a copolymer of acrylic monomer and one or more vinyl monomers, and the amount of acrylic monomer, which was not subjected to polymerization. In the second stage, one or more vinyl monomers copolymerizing with acrylic monomer remaining after the first stage, to add to the first block and the formation of the second block of the block copolymer. The initial portion of the second unit may have a tendency to have the ü higher ratio of acrylic monomer, because acrylic monomer could be exhausted before the formation of the last portion of the second block in the polymerization of one or more vinyl monomers in the practical absence of the acrylic monomer.

The block copolymer of the present invention has many uses, one of which is as an agent compatibility for obtaining mixtures of different materials, such as two different thermoplastic or thermoplastic and glass or clay, which are in other cases a relatively immiscible. Such agents compatibility, used in the past for mixing, often consisted of a block copolymer having a first block that is compatible with the first material and the second block that is compatible with the second material, where the first and second blocks were each well-cleaned. It was unexpectedly found that a block copolymer having relatively polluted the second block, where the second block comprises a monomer used in the first block, works well.

CHEMICAL SYNTHESIS of BLOCK COPOLYMERS

In the first stage acrylic monomer, which has a functional group, copolymerizing in the reactor with at least one vinyl monomer using a free radical initiator and a stable free radical, which forms the first block in the reactor. The reaction is carried out so as to leave the number is the amount of the residual unreacted acrylic monomer after the completion of the first stage, to the first block was mixed with residual unreacted acrylic monomer. The solvent may be used in the first stage, when it is considered necessary. Or in the same reactor, or in a different reactor, at least one vinyl monomer reacts with the first block and the residual unreacted acrylic monomer to addition of the second block to the first block with the formation of a block copolymer having at least first and second blocks. The first block usually contains more functional groups of the acrylic monomer of the second block, but the second unit has some functional groups, because the residual unreacted acrylic monomer with the first stage was added into the polymer chain of the second block.

The reaction product from the first stage includes a copolymer of acrylic monomer and one or more vinyl monomers, which includes the first block of the functionalized block copolymer, and a variable number of unreacted monomers, including acrylic monomer, which is not polymerizable. The number of functional acrylic monomer in the first block and contained in residual monomers can be calculated using commercially available software, such as POLYRED (outdoor package software the m-aided analysis and design of the polymerized systems, developed by the University of Wisconsin Polymerization Reaction Engineering Laboratory). Typically, the composition of the copolymer comprising the first unit, will depend on the initial composition, the final conversion and constants copolymerization (for determining copolymerization constants and values for a variety of pairs of monomers, see J. Brandrup, E. Immergut, E.A. Grulke. Polymer Handbook, fourth edition, John Wiley and Sons, Inc. 11/181). The number of functional acrylic monomer in residual monomers can be experimentally determined by conventional analytical techniques such as gas chromatography, nuclear magnetic resonance (NMR) or any technique that provides a quantitative measure of the monomer in the mixture of monomers. If a solvent is used during the first stage, the amount of solvent should be taken into account to correct a certain percentage of the weight (wt.%) specific monomer remaining in the mixture of unreacted monomers. If the technique can determine the number of all species contained in the reaction product from the first stage (NMR, for example), then you can count the number of functional acrylic monomer in residual monomers (molecules functional acrylic monomer*100/(total number of monomer molecules) and the number of functional acrylic monomer included in the polymer (functional molecules is kilowog monomer in the polymer*100/(total number of monomer molecules in the polymer).

The residual monomers from the first block contains at least 1 wt%./weight. functionalized acrylic monomer, but more preferably in the range of 5-95 wt%./weight. and most preferably in the range of 5-85 wt%./weight. In the second stage, one or more vinyl monomers copolymerizing with acrylic monomer and other monomers, brought from the first stage, to add to the first block and the formation of the second block of the block copolymer. The number of functional acrylic monomer in the second block will depend on the concentration of residual functional acrylic monomer in residual monomers of the first block, from the first conversion unit and the number of monomers added in the second stage. The composition of the second unit at different conversions can also be calculated using commercially available software, such as POLYRED, including the calculation of three or more monomers, which are included in the polymerization of the second block. The preferred concentration of the functionalized acrylic monomer in the block copolymer is from about 0.5 to about 70 weight percent, but more preferably in the range of from 0.5 to about 50 wt%./weight. The total number of functional acrylic monomer included in the block copolymer, may be the quantified using techniques such as NMR.

To the synthesis of block copolymers in accordance with the method in which the first block is not clear or are not getting the conversion to 100%, was applied in 1994, Georges and others (US 5401804). Recently Visger and others (patent US 6531547 B1) and Ro etc. (WO 2004/005361 A1revealed the synthesis of block copolymers using a process which comprises the polymerization of at least one vinylaromatic monomer until you get a certain conversion (5-95 mol.% if Visger and 5-99% if Ro), and then add the monomer derived from methacrylic acid (Ro), or acrylic monomer and optionally an additional amount vinylaromatic monomers (Visger). Ro discusses the advantage of the absence of the stage of selection of the first block from the standpoint of removal of heavy precipitated phase and the selection phase of the first polymer block. Unlike the previous technology in the present invention, the functional acrylic monomer is polymerized in the first block (unlike vinylaromatic monomer)to include reactive groups (epoxy, acid, anhydrous, amino, amide and hydroxy-group), which are required in various applications described below (for example, when the reaction with the functional thermoplastic polymer in polymer mixtures). Unlike the previous technology in the present invention is onverse monomers in the first block and the number of initial functional acrylic monomer is calculated, to ensure the presence of residual functional acrylic monomer, which will be included in the following blocks, and not just as a way to facilitate the next stage of the polymerization, avoiding the stage of cleaning. In the present invention it was found that the presence of reactive groups in the second block is advantageous for the application of these block copolymers as agents of compatibility for different mixtures and composites. The presence of a functional acrylic monomer in the subsequent blocks has at least two advantages.

One advantage is that the acrylic monomer modifies the polarity of the subsequent blocks to match the polarity of one of the components of the polymer mixture. The advantage of using functional acrylic monomers is that, in General, they are more polar than the monomers, such as vinylaromatic monomers, and the presence of a controlled quantity of functional acrylic monomers in the second and/or subsequent blocks can raise polarity, improve their Miscibility with various materials such as thermoplastic polymers.

Another advantage is that in the case of applications, such as agents compatibility of mixtures, previous researchers have shown excellent feature is the Tiki treated diblock copolymers, statistical copolymers. Thus, the need cleansing stage for the first block is required to obtain good results (Stott, P. US 2005/004310 A1), if the monomers used in the synthesis of the first block, did not form patterns, such as alternating block, eliminating the need cleansing stage (Saldivar and other US 2004/0077788 A1). On the contrary, in the present invention it was unexpectedly found that the diblock copolymers that have not been cleaned after synthesis of the first block and which include a functional reactive group in the first and second or subsequent blocks have excellent characteristics as agents of compatibility. In the present invention believe that one possible explanation for this behavior is that the second block (mixed with non-functional thermoplastic polymer containing reactive functional groups (inclusive of unreacted monomers of the first stage), able to join reactive thermoplastic polymer at different points, as illustrated in Figure 1 below, improving edge contact between preaction-able and reactive thermoplastic polymer (see, for example, a comparison between the behavior of disloca against triblock and stable structure, which is formed by triblock in Chin-An et. al. Macromolecules, 197, 30, 549-560). In the case of statistical copolymers of this benefit is generally not achieved, since the functional groups are distributed randomly along the chain and the number of monomer units of vinyl monomers miscible with thermoplastic polymer, probably not large enough to form a weave of thermoplastic monomer, and although they are firmly attached to the functional thermoplastic polymer, their interaction with thermoplastic polymer is not strong enough.

Illustration 1.

In three cases, it is considered that the number of vinyl monomers that are compatible or miscible with thermoplastic polymer, enough to intertwine with thermoplastic polymer (the above polymerization rate weave).

Figure 1 is a schematic representation of the structure of purified dibelka, peeled and triblock block copolymer containing reactive functional acrylic monomer in both blocks according to the present invention.

Preferred stable free radical for use in the method according to the invention contains a group ·0-N< is selected from the group of compounds with nitroxyl radical. Typical examples of compounds with nitroxyl radical include, but are not limited to

Other connections include family according to the procedures mentioned in the patent US 4521429 filed Solomon and others WO 2004014926 (A3)filed Couturier, Jean Luc and others, patent US 2003125489 filed Nesvadba Peter and others, patent US 2001039315 filed Nesvadba Peter and others In cases where the polymerized large amounts of methacrylic monomer, nitroxide, such as tert-butyl-1-diethylphosphino-2,2-dimethylpropanamide, tert-butyl-1-phenyl-2-methylpropionitrile preferred.

Preferred free radical initiators for use in the method according to the invention include peroxy and azo compounds. Typical examples include, but are not limited to, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), peroxide Dibenzoyl (VRO), tert-AMYLPEROXY-2-ethylhexanoate, tert-BUTYLPEROXY-2-ethylhexanoate, 2,5-Bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane and tert-butylperoxybenzoate.

Although the method of radical polymerization mediated nitroxides specifically mentioned in this application to get the agents compatibility according to the present invention is skilled in this technology specialists recognize that any of the other widely-known so-called "living", "pseudo-living" or "controlled" the JV is how radical polymerization can be used in the present invention. Such stable methods of free radical polymerization include the presence of particles that are reversible cut chain due to: (i) reversible homolytic cleavage of covalent particles, (ii) reversible formation of stable hypervalent radicals and (iii) the transfer circuit with feedback (Moad, G.; Solomon, D. The Chemistry of Radical Polymerization. 2ndedition. Elsevier, UK, 2006, chapter 9; Controlled Radical Polymerization. Matyjaszewski, K., editor, American Chemical Society, Washington, D.C, 1997, Chapter 1; Sawamoto, et. al., Chem. Rev. 2001, 101, p.3691). These methods include, but are not limited to, infantery, organogeny infantery, reactions are reversible chain transfer on the principle of addition-fragmentation (RAFT)polymerization mediated sorientiruemsya radicals, radical polymerization atom transfer (ATRP), reversible radical polymerization atom transfer (reverse-ATRP) - mediated metalcomplexes radical polymerization centered oxygen radical polymerization mediated centered oxygen radical-mediated centered nitrogen radicals, the polymerization with the transfer of the iodine-mediated telluride polymerization mediated STIBINE polymerization. Any of these methods to ensure stable free radical polymerization can be used according to the present invention.

In the present invention one of the monomers n is ecstasy an acrylic monomer, having a functional group, which is added during the first stage. Acrylic monomers containing vinyl groups, that is, two carbon atoms connected to each other by a double bond directly attached to the carbonyl carbon (C=C-CO-). The functional group contained in the acrylic monomers include, but are not limited to, epoxy, acid, anhydrous, amino, amide and hydroxyl groups. Preferred acrylic monomers that have functional groups include: glycidylmethacrylate, acrylic acid, methacrylic acid, 2-hydroxyethylmethacrylate, 2-dimethylaminoethylmethacrylate and 2-diethylaminoethylmethacrylate.

In the present invention one or more vinyl monomers added in the first stage and the second stage of the polymerization process. The vinyl monomer is a compound which has a vinyl group= -. Examples of vinyl monomers are styrene, substituted styrene, ethylene, isoprene, isobutylene, butadiene, acrylates, methacrylates, substituted acrylates, substituted methacrylates, Acrylonitrile, N-phenylmaleimide, N-cyclohexylmaleimide. Preferred vinyl monomers in the first stage include styrene, substituted styrene, acrylates, methacrylates, substituted acrylates and substituted methacrylates. Preferred vinyl monomers in the WTO the stage include styrene, substituted styrene, Acrylonitrile, N-aromatic substituted maleimide, N-alkyl substituted maleimide, acrylic acid, methyl methacrylate, alkyl substituted acrylates, aryl-substituted acrylates, the alkyl substituted methacrylates, the aryl-substituted methacrylates and 2-hydroxyethylmethacrylate.

In one embodiment of the functional acrylic monomer selected from the group consisting of glycidylmethacrylate, 2-hydroxyethylmethacrylate, acrylic acid and 2-diethylaminoethylmethacrylate, and the vinyl monomer used in the first stage, is a styrene. In one embodiment of vinyl monomers in the second stage can be selected from the group of, but not limited to, consisting of styrene, N-phenylmaleimide, methyl methacrylate and butyl methacrylate.

In the preferred embodiment of the functional acrylic monomer is glycidylmethacrylate.

In the preferred embodiment, the styrene is used as the vinyl monomer in the second stage.

In a particular embodiment of the vinyl monomer in the second stage includes an N-aromatic substituted maleimide or N-alkyl substituted maleimide.

In a particular embodiment of the vinyl monomer in the second stage selected from the group consisting of styrene, substituted styrene, Acrylonitrile, N-aromatic substituted maleimide, N-alkyl substituted maleimides, acrylic key is lots of methyl methacrylate, alkyl substituted acrylates, aryl-substituted acrylates, alkyl substituted of methacrylates, aryl-substituted of methacrylates and 2-hydroxyethylmethacrylate.

In a specific embodiment of an acrylic monomer selected from the group consisting of glycidylmethacrylate, acrylic acid, methacrylic acid, 2-hydroxyethylmethacrylate, 2-dimethylaminoethylmethacrylate and 2-diethylaminoethylmethacrylate.

In a particular embodiment the vinyl monomers of the first stage is selected from the group consisting of styrene, substituted styrene, substituted acrylates and substituted methacrylates.

In a specific embodiment of an acrylic monomer selected from the group consisting of acrylic functional monomers bearing epoxy, acid, anhydrous, amino, amide and hydroxyl groups.

In a specific embodiment, one or more monomers in the second stage are styrene.

In a more specific embodiment of the acrylic monomer is glycidylmethacrylate and the vinyl monomer used in the first stage, is a styrene.

In a more specific embodiment of the acrylic monomer is acrylic acid, and vinyl monomer used in the first stage, is styrene.

In a more specific embodiment of the acrylic monomer is a 2-hydroxyethylmethacrylate and vinyls the first monomer, used in the first stage, the styrene.

In a more specific embodiment of the acrylic monomer is a 2-diethylaminoethylmethacrylate and the vinyl monomer used in the first stage, the styrene.

In a more specific embodiment of the acrylic monomer is glycidylmethacrylate, the vinyl monomer used in the first stage, styrene, and vinyl monomers used in the second stage, the styrene and N-phenylmaleimide.

In a more specific embodiment of the acrylic monomer is glycidylmethacrylate, the vinyl monomer used in the first stage, styrene, and vinyl monomers used in the second stage, styrene, N-phenylmaleimide and methyl methacrylate.

In another more specific embodiment of the acrylic monomer is glycidylmethacrylate, the vinyl monomer used in the first stage, styrene, and vinyl monomers used in the second stage, styrene, methyl methacrylate and butyl acrylate.

In the present invention the ratio of the functional acrylic monomer in the stage one is in the range from about 0.1 to about 98 percent by weight, more preferably in the range of from about 5 to about 95 percent by weight.

In the present invention the reaction product from stage 1 contains residual unreacted monomial is ry. The residual monomers of the first block contains at least 1 wt%./weight. functionalized acrylic monomer, but preferably contain in the range of 5-95 wt%./weight and most preferably in the range of 5-85 wt%./weight. The weight or mass percentage of component represents the weight or mass of the component divided by the weight or the weight of the mixture, which contains the component and denoted by the notation wt%./weight. or % weight or % weight.

In cases where the monomers do not react with acids, can be used acids as promoters to reduce the reaction time. Promoters include, but are not limited to, strong acids, inorganic acids, sulfonic acids, acidic clay, organic sulfonic acids, carboxylic acids, acidic salts of these acids and monetary sulphurous and sulphuric acids.

Process conditions

The synthesis conditions for the polymerization reaction for obtaining the copolymers of the present invention is described next. Can be used in the processes of swelling or dissolution. For the dissolution process can be used any solvent which forms a solution with the starting monomers, the initiator and the stable free radical or alkoxyamine. In cases where solvent is added during the second stage, can be used any solvent which forms a solution with the outcome of the first block, the remaining monomer and additional monomer. Typical solvents include aromatic or substituted aromatic hydrocarbons as well as aliphatic and substituted aliphatic hydrocarbons. If used, the preferred solvents are substituted aromatic hydrocarbon, more preferably toluene, xylene or ethylbenzene, or polar solvents, such as acetone, chloroform, ethyl acetate, or water. When used, the solvent is preferably present in amounts from about 5 to about 95% by weight based on the mixture of monomers and solvent.

In the case of low percentage of solvent dissolution process similar to the process of swelling, and the solvent is mainly used to control the reaction rate for better removal of heat of reaction, to reduce viscosity and to use larger compositions of monomers that are not miscible in all proportions (for example, styrene/N-phenylmaleimide or styrene/acrylamide), without separation of phases. The low percentage of solvent is preferably 10-30% by weight and more preferably 15-25% by weight relative to the mixture of monomers and solvent. The percentage of solvent from less than about 5% is almost useless, because no obvious advantages to use the project for a solvent. It may be better to go to the swelling, and not to use a very low percentage of solvent.

In the case of a high percentage of solvent dissolution process similar to the typical process of dissolution, which has a much lower viscosity, lower the reaction rate, as well as easier control of temperature and heat produced by the reaction of polymerization. A high percentage of the solvent is preferably between about 60 and about 95 percent by weight, more preferably between about 70 and about 90% by weight and most preferably between about 75 and about 88% by weight relative to the mixture of monomers and solvent. The percentage of solvent, greater than about 95%, allowing too little polymer, and the process becomes inefficient. Can be used in the percent of solvent is between approximately 30 and approximately 60%, but it is not recommended because it leads to excessive dilution to obtain high performance advantage of the process of swelling, and too intense to take advantage of low viscosity typical of the process of dissolution.

The preferred process temperatures are in the range of from about 70 to about 180°C, but more preferred is sustained fashion in the range from about 90 to about 170°C. and most preferably between about 110 and about 130°C. Temperature lower than about 70°C. do not allow radical nitroxide type to act as the regulatory fragment of the living polymer, as further explained below, because at these temperatures the radical nitroxide type prevents the living character of the polymerization. Temperature higher than about 200°C promotirovat too many side reactions, and also the living character of the polymerization under these conditions.

The initiator is usually used in a ratio of about 1 part of initiator to approximately 50 to approximately 12,000 parts in moles of monomer, more preferably about 1 mol of initiator to approximately 100 to approximately 3000 of moles of monomer and most preferably about 1 mol of initiator to about 100 to about 1500 moles of monomer. Molar ratio of approximately 1 part of initiator to less than about 50 parts of the monomer allows to obtain a polymer with a very low molecular weight, which is usually not very good for applications that include compatible mixtures of polymers.

The above-mentioned initiators have half-lives of the order of several minutes or less, usually less than 10 minutes at the preferred temperatures of the process. The amount of stable free radical (SFR) on both the ora is preferably in the range of from about 1 to about 1.9 moles per mole of initiator, more preferably between approximately 1 and approximately 1.6-moles per mole of initiator. The ratio of SFR to the initiator, less than about 1 mol SFR per mole of initiator, lead to the loss of the living character of the polymerization. However, ratios greater than about 1.9 moles SFR per mole of initiator, can slow down the reaction too much and make the process uneconomical. An additional amount of initiator may also be added in the second stage polymerization.

After downloading ingredients, monomers, initiator and stable free radical or alkoxyamine instead of the initiator and nitroxide in the reactor and rapid heating to the appropriate temperature the majority of the polymer chains sooner begins to grow during the reaction, because the initiator will quickly disintegrate at the same temperature. Almost simultaneous initiation of most circuits contributes to the reduction of polydispersity. In addition, shortly after the initiation, and adding only one or more Monomeric units, each living (growing or active) polymer chain will be hidden active centers (decontamination) being muted stable free radical, which will be present in slight excess relative to the number of growing or living chains. Chain with hidden and the active centers will remain in this state for some time, while the stable free radical is released again (activation), and the circuit becomes active living again and capable of adding one or more Monomeric units, until it becomes again a chain with hidden active centers. The cycle of living conditions - with hidden centers - living - with hidden centers repeats itself a certain amount of time until such time as more monomer is available in the reaction, or the temperature is lowered below the minimum temperature to activate the stable free radical, which is less than about 100°C for most of nitrotetrazolato.

Irreversible reactions of chain breakage such as those that occur through interactions between two live circuits are blocked because of the lower effective concentration of the living polymer. The final process is like a real living process (for example, anionic polymerization), and he, like so, I think, is quasigeoid (also called "regulated"). Since all chains grow approximately with the same speed and initiated at approximately the same time, molecular weight distribution tends to be narrow with a relatively low polydispersity. It is known from the prior art that the degree of such polymerization can the t to be measured by the degree of linearity of the growth srednekamennogo molecular weight of the polymer with the conversion and the change curves of the molecular mass distribution towards higher values of the outputs of polymerization.

After heating for a period of from 1 to 10 hours, more usually 1 to 6 hours, the conversion reaches about 10-95%, more typically about 40-85%. Up to this point formed the first block pseudourea statistical copolymer with or without some degree of alternation of simple and multiple bonds. At this point, add a mixture of one or more vinyl monomers. These monomers together with the residual monomers from the first stage will be the second block. As soon as the solution is heated again, the chain will continue to grow due to hidden active centers, re-living cycles, adding monomer units of residual (unreacted) monomer with the first stage and also from the monomers added in the second stage according to their reactivity until then, until all the monomer is not exhausted or the reaction is not complete otherwise.

In the process, just described, the temperature may be constant and can be set to one of the values mentioned in the preferred embodiments of the present invention, or may be modified in the direction of increasing, but still within the range specified in the preferred embodiments of the present invention to accelerate the depletion of the monomer after the initial stages of the conversion.

The STRUCTURE of BLOCK COPOLYMERS

The block copolymers according to the present invention is clucalc the first block, comprising Monomeric units functionalized acrylic monomer and Monomeric units of a vinyl monomer and a second block comprising Monomeric units of one or more vinyl monomers and Monomeric units functionalizing acrylic monomer in the first block.

This method of synthesis described above, and assuming that the reaction ratio determines the instantaneous composition of the copolymer chains, added to the growing chain, each main unit or part of the copolymer will produce a shift in the composition of definitely receiving each of the main portions of the gradient copolymer. In this case, these units or parts will have some statistical in nature, and some gradient in nature. What character dominates in each unit or part, will depend on how different are constants copolymerization and the sequence of addition of monomers, carried out during synthesis. Furthermore, the method of synthesis dictates the average composition of each of the main blocks or parts in the final chain of the copolymer. In the case of vinyl monomers added in the second stage, there is a tendency to alternation with residual monomers from the first stage, the polymerization will lead to the formation of triblock after only a monomer, which has a tendency to rotate, exhausted,other monomers will continue Homo - or copolymerizate.

The typical structure of the obtained copolymers:

R(I)-{(A)m(B)n}-{(A)0(B)p(C)q}z-I(R),

where R represents the balance of nitroxide used to regulate the polymerization agent to improve compatibility;

I represents the balance of the radical initiator used to initiate polymerization, or labile alkyl group, originally attached to the oxygen nitroxide group contained in alkoxyamine;

But is an acrylic monomer having a functional group,

B and C are vinyl monomers which are different or the same;

m is an integer from 5 to 500;

n is an integer from 1 to 400;

o is an integer from 1 to 450; less than m;

p is an integer from 0 to 350; p less than n; and

q is an integer from 1 to 900.

Given the structure of these main blocks or parts end formed as the result of a copolymer, one of the possible architectures will include: (i) the unit is mainly statistical copolymer of a and b (with the fluidity of the composition), (ii) the main part of the gradient copolymer or a block consisting of terpolymer a, b and C only a and C, if a monomer has been exhausted during the first stage) and iii) by the end of the second part of the block or the chain will consist of the unit and possibly a,which can be considered as a unit independently. In the case that a certain amount of monomer In the remains after the first stage, the second block or part will be a gradient copolymer, progressively more enriched With less enriched Century

More monomers can be incorporated into block copolymers. For example, if the fourth monomer D will be added during the first synthesis unit, the resulting structure will include a monomer D in the first and in the second block in a concentration that depends on its initial concentration and reactivity. Thus, the composition of this dibaca could be described as: R(I)-{(A)m(B)n(D)r}-{(A)0(B)p(D)t(C)q}-I(R), where r is an integer from 1 to 400 and t is an integer smaller than r. If the monomer D is added during the second synthesis unit, the resulting structure will include D only in the second block. Thus, the composition of this dibaca could be described as: R(I)-{(A)m(B)n}-{(A)0(B)p(C)q(D)t}-I(R), where t is an integer from 1 to 400. If the monomer D tends to alternate with the remaining monomers from the first stage, the polymerization will triblock, after only the monomer D is exhausted, other monomers will continue Homo - or copolymerizate.

The functional group contained in the acrylic monomers can be, but not limited to, epoxy, acid, Academy of Sciences of idreno, amino, amide and hydroxyl groups. Preferred acrylic monomers having a functional group include glycidylmethacrylate, acrylic acid, methacrylic acid, 2-hydroxyethylmethacrylate, 2-dimethylaminoethylmethacrylate and 2-diethylaminoethylmethacrylate.

Examples of vinyl monomers are styrene, substituted styrene, ethylene, isoprene, isobutylene, butadiene, acrylates, methacrylates, substituted acrylates, substituted methacrylates, Acrylonitrile, N-phenylmaleimide, N-cyclohexylmaleimide. Preferred vinyl monomers in the first block is styrene, substituted styrene, acrylates, methacrylates, substituted acrylates and substituted methacrylates.

Preferred vinyl monomers in the second block are styrene, substituted styrene, Acrylonitrile, N-aromatic substituted maleimide, N-alkyl substituted maleimide, acrylic acid, methyl methacrylate, alkyl substituted acrylates, aryl-substituted acrylates, the alkyl substituted methacrylates, the aryl-substituted methacrylates and 2-hydroxyethylmethacrylate.

In a particular embodiment the acrylic monomer is glycidylmethacrylate, and the vinyl monomer in the first and in the second block is a styrene.

In a particular embodiment the acrylic monomer is glycidylmethacrylate, the vinyl monomer in the first block is styrene, VI is silt monomers in the second block are styrene and N-phenylmaleimide.

In a particular embodiment the acrylic monomer is glycidylmethacrylate, the vinyl monomer used in the first block is a styrene, and vinyl monomers in the second block is styrene, N-phenylmaleimide and methyl methacrylate.

In a particular embodiment the acrylic monomer is glycidylmethacrylate, the vinyl monomer in the first block is a styrene, and vinyl monomers in the second block are styrene, methyl methacrylate and butyl acrylate.

The preferred concentration of the residual functional acrylic monomer in residual monomers of the first block is in the range of about 1-95% weight/weight, but more preferably in the range of from about 5 to about 85% weight/weight.

The preferred concentration of the functionalized acrylic monomer in the block copolymer is between about 0.5 and about 70 percent by weight, but more preferably in the range of from about 0.5 to about 50% weight/weight.

For the implementation of specific embodiment 1, shown below, in the system of the monomers And is glycidylmethacrylate, represents styrene and is a styrene. Glycidylmethacrylate tends to react in a statistical manner with styrene, forming the first block, with the present of poly(styrene-co-glycidylmethacrylate). In the second stage, the addition of styrene will lead to the formation of a gradient of the block that contains fewer molecules of glycidylmethacrylate, after remaining glycidylmethacrylate of the first block is diluted with a large amount of styrene added in the second step, carrying out the embodiment 1. Due to the number of monomer units in the first block, you can control the conversion of the first block, but due to the number of monomer units in the second block can be controlled or the amount of monomer added in the second stage, or the final conversion. The composition of each block can be controlled by the molar percent of monomer added during the first and second stage.

Embodiment 1.

Where:

I represents the balance of the radical initiator used to initiate polymerization or labile alkyl groups originally attached to the oxygen nitroxide group contained in alkoxyamine;

R represents the residue of nitroxide used to regulate the polymerization agent compatibility;

m is an integer from 5 to 500;

n is an integer from 1 to 400;

o is an integer from 1 to 450; o less than m; and

p is an integer from 0 to 350.

Taking into account these main blocks or parts formed by horse the aqueous copolymer of one of the possible architectures will include: (i) the unit is mainly statistical copolymer of a and b (with a shift of the composition), ii) alternating copolymer consisting of terpolymer a, b and C, or alternating copolymer a and C, or alternating copolymer, and depending on the reaction ability of each monomer, and (iii) as soon as the monomer To be exhausted, the remaining monomer or monomers will continue Homo - or copolymerization of forming the third block.

Another typical composition of the obtained copolymers:

R(I)-{(A)m(B)n}-{(A)o(B)p(C)q}z-{(A)r(B)s}z-I(R),

where R represents the balance of nitroxide used to regulate the polymerization agent compatibility;

I represents the balance of the radical initiator used to initiate polymerization or labile alkyl groups originally attached to the oxygen nitroxide group contained in alkoxyamine;

But is an acrylic monomer having functional groups;

B and C represent other vinyl monomers;

m is an integer from 5 to 500;

n is an integer from 1 to 400;

o is an integer from 1 to 450; o less than m;

p is an integer from 0 to 350; p less than n;

q is an integer from 1 to 900;

r is an integer from 0 to 450; r is equal to or less than o; and

s is an integer from 0 to 350; s is equal to or less than the R.

In a particular embodiment, the monomers are: A = glycidylmethacrylate, styrene, C = N-phenylmaleimide and D = styrene. Monomers a and b load to the first stage of obtaining a statistical copolymer. After conversion 66-70% was achieved, add the monomers C and D. In this second block styrene will alternate with N-phenylmaleimide, also including the remaining glycidylmethacrylate. Depending on the ratios of the monomers a, b, C and D and the conversion achieved in the second block, the second block may be: (i) mainly alternating block, or ii) main alternating block and after the exhaustion of the monomer and a monomer B/D can continue the education of the third block homopolymer, or (iii) mainly alternating block and after the exhaustion of the monomer, the monomers B/D and a can continuously form the third block copolymer. The structure obtained in each case (i, ii and iii), shown below as Embodiments 2A, 2b and 2C.

The embodiment 2A

Where in Embodiments 2A, 2b and 2C:

I represents the balance of the radical initiator used to initiate polymerization agent compatibility or labile alkyl groups originally attached to the oxygen nitroxide group contained in alkoxyamine;

R represents the residue of nitroxide used to regulate the polymerization agent compatibility;

m is an integer from 5 to 50;

n is an integer from 1 to 400;

o is an integer from 1 to 450; less than m;

p is an integer from 0 to 350; p less than n;

q is an integer from 1 to 900;

r is an integer equal to or less than about; and

s is an integer less than R.

Various structures shown in the Embodiments 2A, 2b and 2C, can be obtained by varying the ratio of monomers and the conversion of the first and second unit, which makes them very versatile technique to produce different structures.

The block copolymers of the present invention used acrylic monomers as "carriers" of functional groups, because you can find almost all of the important functional groups in commercially available and relatively cheap acrylic monomers. For example, epoxypropan can be entered when using glycidylmethacrylate, the acid group with the use of acrylic acid, the amine group using 2-(diethylamino)ethyl methacrylate, amide group using acrylamide or maleimide and a hydroxyl group at the 2-hydroxyethylmethacrylate. Another advantage is that the functional acrylic monomer, which is included in the second block, can increase its polarity, making it more miscible with certain thermoplastic polymers (this polarity can be adjusted by regulating the number is TBA residual functional acrylic monomer and the number of monomers, added in the second stage), as the acrylic monomers, in General, have a higher polarity compared with other monomers, such as vinylaromatic monomers. The presence of functional acrylic monomers in the first block and the remaining unreacted monomers of the first stage leads to a mixture with a relatively high polarity, to include other highly polar monomers in the second stage, such as N-phenylmaleimide and methyl methacrylate, without addition of a solvent. Commercial availability and variety of functional groups found in relatively inexpensive acrylic monomers, and higher polarity of these types of monomers advantageous than using vinylaromatic monomers with functional groups, such as described in patent US 6531547 B1 and in WO 2004005361 A1.

Depending on the nature of the functional acrylic monomer block copolymers can be soluble in water, they can carry positive or negative charge or charges on their functional groups, or they can be neutral. Also, depending on the nature of the functional acrylic monomer and vinyl monomer block copolymers can form affilie copolymers.

In the prior art for methods of obtaining the block copolymer is in using the live polymerizati necessary sequence of several chemical stages: the first stage monomer, forming the first block is subjected to homopolymerization until it runs out, if must be received cleared blocks. If the first monomer is not completely consumed, it must be removed before you add the second monomer. Further chemical stages of the second monomer type, and it is polymerized, increasing living chains, which are formed during the first stage, and it turns out the second block. The need for removal of residual monomer before loading the second monomer is an additional and difficult stage, which is avoided in the method according to the present invention.

Triblock-Copolymer

Triblock-copolymer can be obtained according to the present invention using a two-stage process, including: 1) the reaction of the acrylic monomer having functional groups and one or more vinyl monomers in the presence of a bifunctional regulatory agent (see, for example, patent US 6258911 B1) with the formation of the reaction product, where the reaction product includes residual unreacted acrylic monomer, and 2) the reaction of one or more vinyl monomers with the reaction product from stage one, where the blocks are formed with the inclusion of residual unreacted acrylic monomer. The solvents can be used optionally at the same or about what their stages. Radical initiators can be used optionally on one or both stages.

One possible structure of triblock copolymers:

R-{(A)0(B)p(C)q}z-{(A)m(B)n(I-I)}-{(A)0(B)p(C)q}z-R

where R is the residue of nitroxide, or regulating agent used to control the polymerization agent compatibility;

I-I is the remainder of the molecule that is used to initiate polymerization or labile alkyl groups originally attached to the oxygen contained in alkoxyamine nitroxide group;

And - acrylic monomer having a functional group;

In other or the same vinyl monomers;

m is an integer from 5 to 500;

n is an integer from 1 to 400;

o is an integer from 1 to 450; less than m;

p is an integer from 0 to 350; p less than n; and

q is an integer from 1 to 900.

Depending on other vinyl monomers added during the first and second stage, the quantity regulating agent and initiator and conversion at each stage can be obtained a wide range of structures.

Method that can be used to obtain a triblock copolymers containing functional acrylic monomers in two or three of these blocks contains the continuation of the polymerization after reaching a certain conversion of the second block is-polymerization. The third block does not need to be synthesized after diblock purified by dissolving it in one or more vinyl monomers. Not necessarily more initiator may be added and may not be used a solvent.

PERIODIC PROCESS

The present invention also provides a chemical periodic way for the implementation of the polymerization reaction, which is carried out in two stages as follows:

a) the First stage, including the addition of all reagents, including the first block of the block copolymer in a reactor with stirring and heating to achieve a conversion of from about 14 to about 95%, and

b) a Second stage comprising adding additional monomer to the product of the first reactor and continuing the reaction in another reaction vessel or vessels without mixing up conversion, down from about 90 to about 100%.

The reactor used in the first stage, is a reactor with a stirrer, equipped with a blade screw or anchor type. The reactor should also have some tools for heat exchange with the outer part, such as a shirt or a coil for heating and cooling. After goal conversions in the range 14-95%, more preferably 50-90%, increases Vya the bone of the reaction mixture and stirring becomes difficult, therefore, the reaction product is sent to the tank for mixing where add additional monomers prior to the final move in the reactor, which completes the reaction. The second reactor is preferably a vessel without mixing equipment for easier cleaning, such as lamellar or cylindrical reactor or reactors. This second reactor should be provided with some device for exchanging heat, such as the outer shirt, dip in thermal fluid, or any other similar device. After reaching a high conversion rate, which can be facilitated by increasing the temperature during the reaction, the polymer is removed from the second stage reactor or reactors and crushed into smaller pieces in a mechanical mill. The final conversion of less than about 90% is not suitable as a large amount of residual monomer would remain, affecting the properties and transport of the final product.

Figure 1

According to Figure 1 periodic process 10 according to the present invention is shown schematically. The solution of nitroxy radical, an acrylic monomer having functional groups and one or more vinyl monomers add to the tank 12, which is connected by a pipe 14 to a pump 16. With the ect in the tank 12 is pumped through the pipeline 18 into the reactor 20. The catalyst or initiator is placed in the reservoir 22, which is connected by a pipe 24 with the pump 26. The pump 26 pumps the catalyst or initiator through the pipeline 28 to the reactor 20. The reactor 20 is a reactor of a continuous action with a stirrer and connected by a pipe 30 with the pump 32. Formed after the first block of the block copolymer in the reactor 20, the copolymer and unreacted monomer is pumped by pump 32 through pipe 34 to the mixer 36. A solution of one or more vinyl monomers add to the tank 38. The contents of the tank 38 flows through the pipe 40 into the pump 42 pumps the contents of the pipe 44 to the mixer 36. These monomers will be part of the second block of the block copolymer. Mixer with agitator 36 is connected by a pipe 46 with the pump 48. After additional monomers are thoroughly mixed, the solution is pumped by pump 48 through the pipe 50 into a series of sheet molds 52. The conversion in the reactor 20 is typically in the range from approximately 14 to approximately 95%. Leaf mold 52 form a second reaction vessel, which has no mixing, this shows schematically how the heat is supplied and removed through the pipe 54 into thermal bath 56. Various methods can be used to remove heat, such as a reactor with a jacket or circulation of the reactants through the Yu of the heat exchanger. Solid polymer facing sheet molds, and then pulverized using a granulator 58, typically a pellet mill with a rotating knife or hammer mill. The crushed product is then prepared for packing or optional may be subjected to drying in an oven to remove any residual monomer, brought with end-stage polymerization.

Acrylic monomer having a functional group, one or more vinyl monomers, vitroceramica and the initiator can be loaded directly into the reactor 20. Selecting or manipulating the ratio of initiator to monomer and/or the ratio of nitroxyethyl to the initiator, it is possible to regulate the molecular weight of the copolymer. Examples that provide further capacity to the effects of these relationships on the molecular weight, are presented below. In the same way you can control the microstructure of the block copolymer, receiving a given structure. The reactor 20 is shown in the form of the reactor of continuous mixer, but can be used in other types of reactors, preferably providing any type of mixing. The reactor 52 is shown in the form of the reactor of sheet ingot molds, but other types of reactors such as tubular reactor can be used, preferably providing a stationary reaction zone.

CONTINUOUS PROCESS the

The present invention also provides a continuous process the reaction block polymerization or polymerization in solution, including two successive stages of the process as follows:

a) a First stage comprising heating the reaction mixture in the reactor continuous mixer with achievable conversions between 14 and 95% weight. and

b) a Second stage comprising heating in the mixing reactor, in which the achieved conversion is between about 60 and about 100%.

The reactor used in the first stage, similar to that described for periodic process; that is, the reactor with stirring, equipped with a mixer, screw-type or anchor type and provided some way of heat exchange with the external surface. The preferred conversion are approximately between 10-95%, more preferably 50-90%, at temperatures preferred in the present invention. Conversion of less than about 10%, make use of the first reactor inefficient, and conversion of greater than about 95%, making the process difficult to control due to the high viscosity of the reaction mixture and can too to broaden the molecular weight distribution of the polymer in the provision of dissimilar material. The second reactor is a CME is sustained fashion mixer, as shown, for example, in patent US 4824257; 5121992 and 7045581 and in the publication no WO 2006034875, which provides further conversion, not too broadening molecular weight distribution, and allows you to get more easy transporting polymer and heat dissipation. Mixing mixers demonstrate shorter periods of treatment than their counterparts - tanks with stirring, and is known from the prior art that for a living or quasigeoid of polymerization molecular weight distribution of the polymer is determined by the distribution of residence time in the reactor. In addition, since the conversion in the second reactor is higher than in the first, the viscosity will also be very high, and in these conditions the mixing mixers provide the perfect way to transport the polymer and removal of heat of reaction, as these reactors mainly have the best ratio of surface area to volume for heat exchange. Conversion of less than about 60% of output, lead to inefficient use of the second reactor and leave too much unreacted monomer. After the second reactor, the process should ensure that any way to remove unreacted monomer, such as equipment for volatilisation or extruder with venting. Unreacted monomer can regenerativ is sterile and can be recycled in the process.

Figure 2

According to Figure 2 continuous process 60 is shown schematically according to the present invention. The solution nitroxyethyl, an acrylic monomer having functional groups and one or more vinyl monomers add to the tank 62. The contents of the tank 62 is pumped by pipeline 64, pump 66, which downloads the contents of the pipe 68 into the reactor 70, as it may be a reactor of the continuous mixer. The catalyst or initiator is placed in the tank 72, and the contents of the tank 72 is pumped through the pipeline 74 to the pump 76, which ends the catalyst or initiator in the pipe 78 into the reactor 70. The first block of the block copolymer is formed in the reactor 70, where the conversion is preferably in the range of from about 14 to about 95%. The copolymer and unreacted monomer derived from reactor 70 through pipe 80 to the pump 82, which pumps the liquid through pipe 84 in the tubular reactor of the type 86, which may be mixing with a mixer. A solution of one or more vinyl monomers add to the tank 88. The contents of the tank 88 is pumped through the pipeline 90 in the pump 92 which pumps the contents of the pipe 94 into the reactor 86. Conversion in the range from about 60 to about 100% is achieved in the reactor 86, and the block copolymer and nepor agirbasli monomer derived from reactor 86 through pipe 96 in the equipment for volatilisation 98. The monomer is removed from the equipment for volatilisation 98 through the pipeline 100, which flows into the capacitor 102. The condensate is formed and flows through the pipe 104 into the condensate 106. The block copolymer is removed from the equipment for volatilisation 98 pipeline 108 in a pump 110 for transportation. Srednetsenovoj molecular weight (Mn) of block copolymer (b) is between approximately 5000 and approximately 300,000. Mn of the block copolymer is preferably between about 5,000 and about 200,000, more preferably between about 10,000 and about 150000, and most preferably between about 20,000 and about 120000.

COMPATIBILITY of MIXTURES

Another embodiment of the present invention is a reactive block copolymers as agents compatibility songs, including:

(a) 1-98% of the weight of a thermoplastic polypropylene polymer having a functional group selected from the group comprising: the amino, amide, kidney, carboxyl, carbonyl, carbonate, anhydrite, epoxy, sulfo, sulfonyloxy, sulfinyl, sulfhydryl, cyano, and hydroxy;

(b) 0.01-25 wt%. the block copolymer including:

i) a first block containing Monomeric units functionalized acrylic monomer and Monomeric units of a vinyl monomer; and

ii) a second block containing mo is Mernie links of one or more vinyl monomers and Monomeric units functionalized acrylic monomer in the first block, where the block copolymer contains functional groups capable of reaction with the chemical residues of plastics, including thermoplastics having a functional group in the component (a); and

(C) 1-98 wt%. thermoplastic polymer miscible or compatible with the second block of the block copolymer described in the component (b).

The invention thus provides many applications in which the block copolymer according to the invention is used as the agent compatibility, which provides a composition of matter to create a compatible mixture, and also the way to use the agent compatibility.

The polymer miscible or compatible with the first unit of the above-mentioned block copolymer include those that may be described as hydrogenated or partially hydrogenated homopolymers and statistical spindle-shaped or block-polymers (copolymers, including terpolymers, terpolymer etc.) dienes with conjugated double bonds and/or monovinyl aromatic compounds. Diene with conjugated double bonds include isoprene, butadiene, 2,3-dimethylbutadiene and/or mixtures thereof, such as isoprene and butadiene. Monovinyl aromatic compounds include any of the following and mixtures thereof: monovinyl monoaromatic compounds, such as styrene or alkylated styrene, substituted at the alpha-the low carbon atoms styrene, such as alpha methylsterol, or ring of carbon atoms, such as o-, m-, p-methylsterol, atillery, propellera, isopropylthio, butalbiral, isobutylester, tert-butalbiral (for example, p-tertbutylphenol). Also included vinylsilane, methylethylidene and ethylvanillin. Specific examples include statistical polymers of butadiene and/or isoprene and polymers of isoprene and/or butadiene and styrene, and also specific ester polymers, such as syndiotactic polystyrene. Typical block copolymers include polystyrene-polyisoprene, polystyrene-polybutadiene, polystyrene-polybutadiene-polystyrene, polystyrene-ethylene-butylene-polystyrene, polyvinyl cyclohexanecarbonyl polyisoprene and poly cyclohexanecarbonyl polybutadiene. Spindle-shaped polymers include polymers of the preceding monomers, obtained by the methods known in this technology. Other mesterolone the polymer miscible or compatible with the second block copolymer include, but are not limited to, Polyphenylene ether (RRE), polivinilbutilovy ether and tetramethylpentane, methyl methacrylate, alkyl substituted acrylates, the alkyl substituted methacrylates and their copolymers with styrene. They also include the polyolefins, where the term polyolefin is defined as a polymer of the majority of those monomers, which are the camping olefins and can be polyethylene, polypropylene or copolymers of ethylene and/or propylene or vinyl acetate. They also include structural thermoplastic, such as aliphatic and aromatic polycarbonates (a type of polycarbonate of bisphenol a), polyesters (such poly(utilityrelated) and poly(ethyleneterephthalate)), polyamides, Polyacetal, Polyphenylene ether or mixtures thereof. All these structural thermoplastics are prepared according to known commercial processes. Reference to such processes can be found in technical publications such as Encyclopedia of Polymer Science and Engineering, John Wiley and Sons. 1988, with appropriate introduction to the topic of structural thermoplastic.

Thermoplastic polymers which have functional groups

Preferred thermoplastic polymers having a functional group selected from the group consisting of: aliphatic and aromatic polycarbonates (a type of polycarbonate of bisphenol a), polyesters (such poly(utilityrelated) and poly(ethyleneterephthalate)), polyamides, acetal resin, polifenoljnogo ether, polyolefin, having apachegroup, anhydrite or acid functional group, polysulfones, polyurethanes and mixtures thereof. All of these thermoplastics receive according to well-known commercial processes. Reference to such processes can be found in technical publications such as Encyclopedia of Polymer Science and Engineeing, John Wiley and Sons. 1988, with appropriate introduction to the topic of thermoplastic. Specific details about thermoplastic resins obtained by polycondensation, followed by the next.

Polyphenylene ethers and polyamides of the present invention described in the patent US 5290863, which is incorporated into the present application by reference. Polyphenylene esters include a variety of structural units having the formula:

In each of these parts, each independent of Q1independently represents halogen, primary or secondary lower alkyl (i.e. alkyl containing up to 7 carbon atoms), phenyl, haloalkyl, aminoalkyl, hydrocarbonate or halohydrocarbons, where at least two carbon atoms separating the oxygen atoms and halogen; and each Q2independently is hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonate or halohydrocarbons as defined for Q1.

Examples of suitable primary or lower alkyl groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3 - or 4-methylpentyl and suitable heptylene group. Examples of secondary lower alkyl group is an isopropyl and sec-butyl.

Preferably, any alkyl radical is a normal C is ro, and not branched. In most cases, each Q1represents alkyl or phenyl, especially C1-4alkyl, and each Q2represents hydrogen. Suitable Polyphenylene esters are disclosed in many patents.

Polyphenylene esters are usually obtained oxidative interaction of at least one corresponding monohydroxylation connection. Particularly suitable and readily available monohydroxylation connection - 2,6-xylenes, where each Q1is methyl and each Q2is hydrogen and where the polymer is characterized as a poly(2,6-dimethyl-1,4-phenylenebis ether), and 2,3,6-trimethylphenol, where each Q1and one Q2- mately, and the other Q2- hydrogen.

Included are both a homopolymer and a copolymer Polyphenylene esters. Suitable homopolymers are those homopolymers which contain, for example, parts of 2,6-dimethyl-1,4-venereologia ether. Suitable copolymers include random copolymers containing such units in combination with links, for example, 2,3,6-trimethyl-1,4-venereologia ether. Many suitable statistical copolymers as well as homopolymers, as disclosed in the prior art.

Also included Polyphenylene esters containing groups, which modify properties such as molecular weight, melt viscosity and/or the impact strength. Such polymers are described in the prior art and can be obtained by carrying out graft copolymerization on Polyphenylene live by well-known methods such vinyl monomers as Acrylonitrile, and vinyl aromatic compounds (e.g. styrene), or such polymers as polystyrene or polyurethane elastomers. The product usually contains both vaccinated and unvaccinated groups. Other suitable polymers are United Polyphenylene esters, in which the binder reacts in a known manner with the hydroxy groups of two chains polivinilovogo ether, to obtain a polymer with a higher molecular weight containing the reaction product of hydroxyl groups and a binder. Illustrative binders are low molecular weight polycarbonates quinones, heterocycles and formal.

Polyphenylene ether generally has srednesemennyh molecular weight within a range of approximately 3000-40000 and srednevekovoi molecular weight within a range of approximately 20000-80000, as determined by gel chromatography. His own viscosity is most often in the range of about 0.15-0.6 DL/g as measured in chloroform at 25°C.

Polyphenylene esters that can be used for the purposes of the present invention include those that include the up molecules having at least one of the end groups of the formula

where Q1and Q2are as previously defined; each R1is independently hydrogen or alkyl provided that the total number of carbon atoms in both R1the radicals is 6 or less; and each of R2is independently hydrogen or a radical of the primary1-6the alkyl. Preferably, each R1represents hydrogen, and each R2represents alkyl, especially methyl or n-butyl.

Polymers containing aminoalkylsilane end groups of the formula (II)can be obtained by actuation of a corresponding primary or secondary monoamine as one of the components of the reaction mixture oxidative interaction, especially when using copper or mn containing catalyst. Such amines, especially dialkylamines and preferably di-n-butylamine and dimethylamine, frequently become chemically attached to polivinilovomu ether, most often replacing one of the a-hydrogen atoms in one or more radicals Q1. The main center of the reaction is a radical Q1adjacent to the hydroxyl group on the terminal group of the polymer chain. During further processing and/or blending am dealkylation end groups may undergo various reactions, probably with the inclusion of an intermediate link such as meiden-quinone type the formula

with the numerous favorable effects often including an increase in the impact resistance and compatibility with other components of the mixture, as indicated in the references cited in the patent US 5290863.

For a skilled in this technology specialist is evident from the prior art that Polyphenylene esters, considered for use in the present invention include all currently known Polyphenylene esters regardless of changes in the structural parts or additional chemical properties.

Polyamides, considered included in the invention are the polyamides obtained by the polymerization moneymoneymoney acid or its lactam having at least 2 carbon atoms between the amino and carboxylic acid, essentially equimolar proportions of a diamine which contains at least 2 carbon atoms between the amino groups and a dicarboxylic acid, or moneymoneymoney acid or its lactam, as defined above together with essentially in equimolar proportions of a diamine and dicarboxylic acid. The term "essentially equimolar" ratio includes strictly equimolar ratio, and small is lonene from them, found in traditional methods for stabilizing the viscosity of the obtained polyamides. Dicarboxylic acid can be used in the form of a functional derivative, for example a complex ester or carboxylic acid.

Examples of the above-mentioned monobasic moneymoneymoney acids or their lactams, which are suitable for the production of polyamides include those compounds which contain from 2 to 16 carbon atoms between the amino groups and carboxylic acid groups, these carbon atoms form a ring containing CO(NH) group in the case of a lactam. As specific examples aminocarbonyl acids and lactams can be mentioned aminocaproic acid, butyrolactam, bialoleka, caprolactam, caprolactam, alantolactone, undecalactone, dodecalactam and 3 - and 4-aminobenzene acid.

Diamines suitable for use in obtaining polyamides include alkyl normal chain and branched chain, aryl and ascaridiasis. Illustrative diamines are trimethylenediamine, tetramethylaniline, pentamethylenebis, octamethylene, hexamethylenediamine were (which is often preferred), trimethylhexamethylenediamine, m-phenylenediamine and m-xylylenediamine.

Dicarboxylic acids may be represented by the formula

Can be used both crystalline and amorphous polyamides with crystal particles, is often preferred because of their resistance to solvents. Typical examples of the polyamides or Nasonov, as they are often called, include, for example, polyamide-6 (polycaprolactam), 6,6-(polyhexamethylenediamine), 11, 12, 4,6, 6,10 6,12 and as the polyamides of terephthalic acid and/or isophthalic acid, and trimethylhexamethylenediamine; from adipic acid and m - xylylenediamine; from adipic acid, azelaic acid and 2,2-bis(p-AMINOPHENYL)propane or 2,2-bis(p-aminocyclohexane)propane and terephthalic acid and 4,4'-diaminodicyclohexylmethane. Mixtures and/or copolymers of two or more of the foregoing polyamides or their prepolymers, respectively, are also within the scope of the claims of the present invention. Preferred polyamides are polyamide 6, 4,6, 6,6, 6,9, 6,10, 6,12, 11 and 12, the preferred polyamide 6,6. Commercially available thermoplastic polyamides may advantageously be used in practice of this is bretania with linear crystalline polyamides, having a melting temperature between 165 and 230°C is preferable.

The polyesters that can be used as a component in the compositions of the invention, mainly, have a relatively high molecular weight and can be branched or linear polymers. They include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (RHT), politological-bis-melanterite (PCT) and thermoplastic elastomeric polyester or a combination of these thermoplastic elastomeric polyesters with other above-mentioned polyether type RHT. Polyesters suitable for compositions of the present invention, include, as a rule, linear saturated condensation products of diols and dicarboxylic acids or their reactive derivatives. Preferably, they are complex polymeric glycol esters of terephthalic acid and isophthalic acid. These polymers are commercially available or can be obtained by known methods, such as alcoholysis of esters of phthalic acid with a glycol and subsequent polymerization, by heating the glycols with the free acids or with halide their derivatives, and similar processes. Such polymers and methods for their production are described in the references cited in the patent US 5290863, and other references.

Predpochtite the global polyesters are the family, including high molecular weight polymeric glycol terephthalate or isophthalate having the repeating unit of the formula

where n is an integer from two to ten, and usually from two to four, and mixtures of such esters, including sobolifera terephthalic and isophthalic acids of up to 30 mole percent isophthalic units.

Especially preferred polyesters are poly(ethyleneterephthalate) and poly(1,4-butilstearat).

Especially preferred when high melt strength, are branched poly(1,4-butylanthraquinone) polymers with high melt viscosity, which include small amounts, for example up to 5 mol. percent, based on the terephthalate units, branching component containing at least three ester forming groups. Branched component may be such that provides branching in the acid portion of the polyester of the link or link glycol, or it may be a hybrid. Illustrative of such branching components are three - or tetracarbonyl acid, such as tremezzina acid, pyromellitate acid and their lower alkalemia esters and the like, or preferably, thetruly, such as pentaerythritol, triola, such as trimethylolpropane, or dihydroxycinnamate KIS is the notes and hydroxycarbonate acid and derivatives such as dimethylhydroxylamine etc. Adding polyepoxide, such as tripyridyltriazine, which is known to increase the viscosity of the polyester phase due to branching, can improve the physical properties of the mixtures of the present invention.

Branched poly(1,4-butylanthraquinone) resin and obtaining them are described in U.S. patent 3953404.

To illustrate, high molecular weight polyesters used in the practice of the present invention have intrinsic viscosity of at least about 0.2 deciliters per gram, and more often from about 0.4 to 1.5 deciliters per gram as measured in solution in ortho-chlorophenol or in a mixture of 60/40 phenol/tetrachlorethane at a temperature of from 25 to 30°C.

Linear polyesters include thermoplastic poly(alkylenedioxy) and their acyclic analogues. They usually consist of structural units of the formula:

where R8- saturated divalent aliphatic or epicycle hydrocarbon radical containing from about 2 to 10, and typically from about 2 to 8 carbon atoms, and a2is a divalent aromatic radical containing from about 6 to 20 carbon atoms. They are usually produced by reaction of at least one diol such as ethylene glycol, 1,4-butanediol or 1,4-cyclohex dimethanol, with at least one aromatic dicarboxylic acid such as isophthalic or terephthalic acid or its lower alkilany complex ether. Polyalkylacrylate, especially polyethylene terephthalate and polybutylene terephthalate, and especially the latter, are preferred. Such polyesters are known in the prior art, as illustrated in the references cited in the patent US 5290863.

Linear polyesters generally have srednekislye molecular weight in the range from about 20000 to 70000, as defined characteristic viscosity at 30°C in a mixture of 60% (by weight) phenol and 40% 1,1,2,2-tetrachlorethane. When the deformation resistance is an important factor, the molecular weight of the polyester should be relatively high, typically above approximately 40000.

Polycarbonates suitable for use in the present compositions include aliphatic and aromatic polycarbonates. The raw materials for aliphatic polycarbonates are diols and carbonates, such as diethyldithiocarbamate obtained by postironium of hydroxiapatite or 1,3-dioxolane-2-ones formed from CO2and oxiranes. Aliphatic polycarbonates can also be obtained from 1,3-dioxane-2-ones obtained by thermal depolymerization of the corresponding polycarbonates.

Currently im the s receipt of aliphatic polycarbonates include transesterification of diols with lower diallylmalonate, dioxolane or diphenylcarbonate in the presence of a catalyst, such as alkali metal compounds of tin and titanium. Polymerization disclosure cycle six-membered cyclic carbonate (1,3-dioxane-2-ones in the presence of bicyclic carbonates, which act as crosslinking agents, leads to solid hard thermosetting materials. Cross-linked polycarbonates with exceptional properties also received free radical polymerization of diethylene glycol bis(allylcarbamate). Based on the carbonate, ethylene glycol, other fossanova ways were found on the basis of CO2with urea or dialkylammonium as an intermediate connection or WITH. Other ways include cationic or free radical polymerization, polymerization by ring opening of cyclic orthoepical carbonic acid. These reactions lead to politicallycorrect.

Molecular weight linear aliphatic polycarbonates process-dependent and are in the range between 500 and 5000. The polycarbonates with molecular weights up to approximately 30,000 obtained by transesterification, while the polycarbonates with molecular weight more than 50,000 produced by polymerization of carbonates having the six-membered rings.

Among the preferred polycarbonates are the homopolymers of aromatic polycarbonate. Article is alternia links in such homopolymers mainly have the formula

where a3- aromatic radical. Suitable radicals And3include m-phenylene, p-phenylene, 4,4'-biphenylene, 2,2-bis(4-phenylene)propane, 2,2-bis(3,5-dimethyl-4-phenylene)propane and similar radicals such which correspond dihydroxyaluminum compounds disclosed by name or formula, in General or specifically, in patent US 4217438. Also included radicals containing non-hydrocarbonaceous group. They can be substituents such as chlorine, nitro, alkoxy and the like, and also binders radicals, such as tio, sulfoxy, sulfon, ester, amide, simple ether and carbonyl. Most often, however, all But3radicals are hydrocarbon radicals.

Radicals And3preferably have the formula

where each And4and a5represents the only ring divalent aromatic radical and Y is a bridging radical in which one or two atoms separate And4from a5. The free valence bonds in formula IX are usually in the meta - or para-positions And4and a5relative to Y. These values And3can be defined as derived from bisphenol formula BUT(A4(Y(A5(HE. The oft-repeated reference to bisphenola will be made hereinafter, but it should be clear, Thu the values And 3derived from the corresponding compounds, in addition to bisphenol, can be used as appropriate.

In formula IX values And4and a5may be unsubstituted phenylene or substituted derivatives, illustrated substituents are one or more alkyl, alkenyl (e.g., stitched-vaccinated groups, the type of vinyl and allyl), halo (especially chlorine and/or bromine), nitro, alkoxy and the like, an Unsubstituted phenylene radicals are preferred. And a4and And5are preferably p-phenylene, although both may be o - or m-phenylene, or one can be o-phenylene or m-phenylene and the other p-phenylene.

Bridging radical, Y, is one in which one or two atoms, preferably one, separate And4from a5. This is most often a hydrocarbon radical and particularly a saturated radical such as methylene, cyclohexylmethyl, 2-[2,2,1]-bicyclogermacrene, ethylene, 2,2-propylene, 1,1-(2,2-dimethylpropylene), 1,1-cyclohexyl, 1,1-cyclopentadecane, 1,1-cyclododecene or 2,2-Adamantine, especially cemalcilar-radical. However, also included are unsaturated radicals and radicals, fully or partly composed of atoms other than carbon and hydrogen. Examples of such radicals - 2,2-dichloroethylidene, carbonyl, thio, hydroxy and sulfon. For reasons of availability and particular Ave the date for the purposes of the present invention, the preferred radical of formula IX represents a 2,2-bis(4-phenylene)propane radical, obtained from bisphenol a and in which Y is isopropylidene and4and And5each represents a p-phenylene.

There are various ways to obtain polycarbonate homopolymers. They include interfacial and other ways in which the phosgene reacts with bisphenolate, methods of transesterification, in which bisphenol react with dellcorporate, and methods, including the conversion of cyclic polycarbonate oligomers to linear polycarbonates. The latter method is disclosed in US patent 4605731 and 4644053.

Preferred polyhydric phenol is a diatomic phenol, such as bisphenol A. Suitable polycarbonate resins for the practice of the present invention may be any commercial polycarbonate resin. Srednevekovaja molecular weight suitable polycarbonate resins (as determined by gel chromatography relative to polystyrene) may be from about 20,000 to about 500000, preferably from about 40,000 to about 400000. However, compositions in which the polycarbonates have molecular weight in the range of about 80000-200000 often have favorable properties.

It is also possible to use polymer mixture according to the invention a mixture of different polycarbonates, which as mentioned above aromatic polycarbonate.

the using block copolymer as an agent compatibility

Typically, a minimum of about 0.5% of the weight of the reactive block copolymer according to the invention, and preferably range from approximately 1 to approximately 7 will be sufficient to observe the effects of compatibility in mixed formulations of structural thermoplastic, using properties such as improvement of mechanical properties. The block copolymer can also be used in quantities above the minimum, but limited in range so that it had a positive effect on the characteristics of the mixture, as a rule, without sacrificing other desirable features. Thus, typical mixtures include the following: (a) a thermoplastic having a functional group, 98-1% by weight, (b) thermoplastic polymer miscible or compatible with the second block of the block copolymer, 1-98% by weight and (C) reactive block copolymer of 1-20% by weight. Preferred mixtures of the present invention include from about 40 to about 90% weight thermoplastics having a functional group, 10-60% by weight of thermoplastics, miscible or compatible with the second block of the block copolymer, and from about 2 to about 5% by weight of the reactive block copolymer. This range of compositions will usually lead to materials with the properties of high impact resistance and mechanical strength.

As a rule, mixed the compositions according to the invention can be prepared by mixing thermoplastic having the functional group of thermoplastic miscible/compatible with one of the blocks of the copolymer and the reactive block copolymer according to the invention, in any order and the effect on the mixture temperature sufficient to melt the mixture, for example 180°C and above. Such mixing and heating can be achieved using conventional equipment for polymer manufacturing processes, known in the prior art, such as mixers periodic operation, one or more screw extruders, continuous kneading machine, etc. also compatible compositions of the present invention may contain various additives, for example stabilizers, fire retardant products, antioxidants, fillers, substances to improve the processing properties and the pigments in the standard and traditional quantities that depend on the desired end use. As examples of fillers may be mentioned, for example, the metal oxide type oxide of iron and Nickel, nonmetals, such as carbon fiber, silicates (e.g. mica, aluminum silicate (clay), titanium dioxide, glass flakes, glass beads, glass fibers, polymer fibers, etc. If used, conventional additives and fillers mechanically mixed, and the composition of the invention is then formed by the known methods./p>

Additional applications for the block copolymer as an agent compatibility

In a specific embodiment thermoplastic polymer having functional groups is polycarbonate and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a polystyrene.

In a specific embodiment thermoplastic polymer having functional groups is a polycarbonate and thermoplastic polymer miscible or compatible with the second block of the block copolymer is high impact polystyrene.

In a specific embodiment thermoplastic polymer having functional groups is a polycarbonate and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a high-impact polystyrene, and to obtain the composition of the functionalized block copolymer melt is mixed first with a polycarbonate resin, which is pre-hydrolized to increase the number of available functional groups. Product stage extrusion dried and then treated in the melt a large number of polycarbonate and polystyrene with a high resistance to obtain the final composition.

In a specific embodiment thermoplastic polymer having functional groups is poly what arboretum, and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a copolymer of styrene, Acrylonitrile and butadiene (ABS).

In a specific embodiment thermoplastic polymer having functional groups is polycarbonate and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a copolymer of styrene, Acrylonitrile and n-butyl acrylate.

In a specific embodiment thermoplastic polymer having functional groups is polycarbonate and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a copolymer of styrene, Acrylonitrile, butadiene and n-butyl acrylate.

In a specific embodiment thermoplastic polymer having functional groups is polycarbonate and thermoplastic polymer miscible or compatible with the second block of the block copolymer is Polyphenylene ether.

In a specific embodiment thermoplastic polymer having functional groups is a polycarbonate and thermoplastic polymer miscible or compatible with the second block of the block copolymer, is a blend of polystyrene with a high resistance and polivinilovogo ether.

In a particular embodiment thermoplastics the second polymer, having a functional group is a polycarbonate and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a hydrogenated block copolymer of styrene and diene monomer.

In a specific embodiment thermoplastic polymer having functional groups is polycarbonate, and the reactive block copolymer includes glycidylmethacrylate as a functionalized acrylic monomer and styrene as a vinyl monomer in the first and second block.

In a specific embodiment thermoplastic polymer having functional groups is a polycarbonate, and the reactive block copolymer includes glycidylmethacrylate as a functionalized acrylic monomer and styrene as a vinyl monomer in the first block. Vinyl monomers in the second block is styrene and N-phenylmaleimide.

In a specific embodiment thermoplastic polymer having functional groups is a polycarbonate, and the reactive block copolymer includes glycidylmethacrylate as a functionalized acrylic monomer and styrene as a vinyl monomer in the first block. Vinyl monomers in the second block are styrene, N-phenylmaleimide and methyl methacrylate.

In a specific embodiment thermoplastic polymer clay is, having a functional group is polycarbonate, and the reactive block copolymer includes glycidylmethacrylate as a functionalized acrylic monomer and styrene as a vinyl monomer in the first block. Vinyl monomers in the second block are styrene, methyl methacrylate and butyl acrylate.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a block copolymer of styrene and diene monomer.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a hydrogenated block copolymer of styrene and diene monomer.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a styrene acryloylmorpholine.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a polystyrene.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a high impact polystyrene.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a copolymer of styrene, Acrylonitrile and butadiene.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a copolymer of styrene, Acrylonitrile and n-butyl acrylate.

In particular OPL is not the same thermoplastic polymer, having a functional group selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a copolymer of styrene, Acrylonitrile, butadiene and n-butyl acrylate.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and the reactive block copolymer includes glycidylmethacrylate as a functionalized acrylic monomer and styrene as a vinyl monomer in the first and second block.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and the reactive block copolymer includes glycidylmethacrylate as a functionalized acrylic monomer and styrene as a vinyl monomer in the first block. Vinyl monomers in the second block is styrene and N-phenylmaleimide.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and the reactive block copolymer includes glycidylmethacrylate as f is unctionalities acrylic monomer and styrene as a vinyl monomer in the first block. Vinyl monomers in the second block are styrene, N-phenylmaleimide and methyl methacrylate.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and mixtures thereof, and the reactive block copolymer includes glycidylmethacrylate as a functionalized acrylic monomer and styrene as a vinyl monomer in the first block. Vinyl monomers in the second block are styrene, methyl methacrylate and butyl acrylate.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polypentaerythritols, polyhexamethylenediamine and mixtures thereof and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a polystyrene.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polypentaerythritols, polyhexamethylenediamine and mixtures thereof and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a high impact polystyrene.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of prepenalty carboxamide, polyhexamethylenediamine and mixtures thereof and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a copolymer of styrene, Acrylonitrile and butadiene.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polypentaerythritols, polyhexamethylenediamine and mixtures thereof and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a copolymer of styrene, Acrylonitrile and n-butyl acrylate.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polypentaerythritols, polyhexamethylenediamine and mixtures thereof and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a copolymer of styrene, Acrylonitrile, butadiene and n-butyl acrylate.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polypentaerythritols, polyhexamethylenediamine and mixtures thereof and thermoplastic polymer miscible or compatible with the second block of the block copolymer is Polyphenylene ether.

In a specific embodiment thermoplastic polymer having functional group is chosen from the group consisting of polypentaerythritols, polyhexamethylenediamine and mixtures thereof and thermoplastic polymer miscible or compatible with the second block of the block copolymer, is a blend of polystyrene with a high resistance and polivinilovogo ether.

In a specific embodiment thermoplastic polymer having functional groups selected from the group consisting of polypentaerythritols, polyhexamethylenediamine and mixtures thereof and thermoplastic polymer miscible or compatible with the second block of the block copolymer is a hydrogenated block copolymer of styrene and diene monomer.

Mixed composition

Typically, a minimum of about 0.5% of the weight of the reactive block copolymer according to the invention and preferably range from approximately 1 to approximately 7% of the weight will be sufficient to observe the effects of compatibility in thermoplastic compositions of the mixture, which is used as the improvement of mechanical properties. The block copolymer can also be used in quantities above the minimum, but limited in range so that it positively influenced by the characteristics of the mixture, as a rule, without compromising other desirable characteristics. Thus, a typical mixture will include the following: (a) a thermoplastic polymer, available is a functional group, 98-1% by weight, (b) thermoplastic polymer miscible or compatible with the second block of the block copolymer, 1-98% by weight and (C) reactive block copolymer of 1-20% by weight. Preferred mixtures of the present invention include from about 40 to about 90% by weight of thermoplastic polymers having a functional group, 10-60% by weight of thermoplastic polymer miscible or compatible with polystyrene and from about 2 to about 5% by weight of the reactive block copolymer. This range of compositions will usually lead to materials with the properties of high impact resistance and mechanical strength.

Typically, the compositions of the mixtures according to the invention can be prepared by mixing thermoplastic polymer having functional groups of thermoplastic miscible/compatible with the second block of the block copolymer and the reactive block copolymer according to the invention in any order and the effect on the mixture temperature sufficient to melt the mixture, for example 180°C and above. Such mixing and heating can be carried out using conventional equipment for polymer manufacturing processes, known in the prior art, such as mixers periodic operation, one or more screw extruders, kneading machines of continuous action, etc. also compatible the compositions of the present invention may contain various additives, for example stabilizers, flame retardants, antioxidants, fillers, substances to improve the processing properties and the pigments in the standard and traditional quantities that depend on the desired end use. As examples of fillers may be mentioned, for example, the metal oxide type oxide of iron and Nickel, nonmetals, such as carbon fiber, silicates (e.g. mica, aluminum silicate (clay), titanium dioxide, glass flakes, glass beads, glass fibers, polymer fibers, etc. If used, conventional additives and fillers mechanically mixed, and the composition of the invention is then formed by the known methods.

The adhesive layer

Functional block copolymers can also be used as agents compatibility of thermoplastic polymers as a material for the bonding layer for the adhesive connection of the layers of plastic film with one another with formation of a laminar structure. The usual process for the use of glued layers includes extruding two layers of plastic and the adhesive layer where the adhesive layer is located between the two layers of plastic.

Use with clay

A mixture of functional block copolymers and clay can be used to enable and efficient dispersion of the clay in thermoplastics the x polymers. Thermoplastic polymers include those thermoplastic polymers that may be described as hydrogenated or partially hydrogenated products of homopolymers and statistical, spindle-shaped or block-polymers (copolymers, including terpolymers, terpolymer etc.) dienes with conjugated double bonds and/or monovinyl aromatic compounds. Diene with conjugated double bonds include isoprene, butadiene, 2,3-dimethylbutadiene and/or mixtures thereof, such as isoprene and butadiene. Monovinyl aromatic compounds include any of the following and mixtures thereof: monovinyl monoaromatic compounds, such as styrene or alkylated styrene, substituted at the alpha carbon atom of styrene, such as alpha methylsterol, or ring of carbon atoms, such as o-, m-, p-methylsterol, atillery, propellera, isopropylthio, butalbiral, isobutylester, tert-butalbiral (for example, p-tertbutylphenol). Also included vinylsilane, methylethylidene and ethylvanillin. Specific examples include statistical polymers of butadiene and/or isoprene and polymers of isoprene and/or butadiene and styrene, and also specific ester polymers, such as syndiotactic polystyrene. Typical block copolymers include polystyrene-polyisoprene, polystyrene-polybutadiene, polystyrene-polybutadiene is-polystyrene, polystyrene-ethylene-butylene-polystyrene, polyvinyl cyclohexane-hydrogenated polyisoprene and poly (vinyl cyclohexane-hydrogenated polybutadiene. Spindle-shaped polymers include polymers of the preceding monomers, obtained by the methods known in this technology. Other mesterolone the polymer miscible or compatible with the second block copolymer include, but are not limited to, ether Polyphenylene (RRE), polivinilbutilovy ether and tetramethylpentane, methyl methacrylate, alkyl substituted acrylates, the alkyl substituted methacrylates and their copolymers with styrene. They also include the polyolefins, where the term polyolefin is defined as a polymer of the majority of those monomers are olefins and can be polyethylene, polypropylene or copolymers of ethylene and/or propylene or vinyl acetate. They also include structural thermoplastic, such as aliphatic and aromatic polycarbonates (a type of polycarbonate of bisphenol a), polyesters (such poly(utilityrelated) and poly(ethyleneterephthalate)), polyamides, Polyacetal, Polyphenylene ether or mixtures thereof. All these structural thermoplastics are prepared according to known commercial processes. Reference to such processes can be found in technical publications such as Encyclopedia of Polymer Science and Engineering, John Wiley and Sons., 1988, when the corresponding is negreni in the topic of structural thermoplastic.

A mixture of functional block copolymers and clay can be used to enable and efficient dispersion of the clay in the functional polymers. Functional polymers include, but are not limited to, aliphatic and aromatic polycarbonates (such as the polycarbonate of bisphenol a), polyesters (such as poly(butilstearat) and poly(ethyleneterephthalate)), polyamides, Polyacetal, Polyphenylene ether, polyolefin, with epoxy, anhydrite or acid functional group, polysulfones, polyurethanes, and mixtures thereof.

A mixture of functional block copolymers, clay and functionalized polyolefin may be used to enable and efficient dispersion of clay containing no functional groups of the polyolefin and improve their mechanical properties.

Examples

The following examples serve to illustrate many aspects of the present invention. A wide variety of properties can be obtained in various mixtures by simple changing the molecular weight of the block agent compatibility, the number of reactive monomers and conversion of the first block. The following examples explain the invention in more detail, but they should not be considered as limiting the present invention specific examples presented. The scope of the invention is properly determined in accordance with formalisable, which is ultimately submitted.

Obtain diblock copolymers

Reagents: Glycidylmethacrylate from Dow Quimica Mexicana, S.A. de C.V.; VRO from Akzo Nobel; 4 hydroximino from CIBA; N-phenylmaleimide, methyl methacrylate, butylmethacrylate and butyl acrylate were purchased from Sigma-Aldrich. 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-hydroxy-TAMRA) from CIBA. These reagents were used as received. Styrene from Quimir or used in the form as was obtained (examples 1, 7-9, 14-17), or was washed with NaOH solution to remove the inhibitor, and dried with anhydrous sodium sulfate.

Examples 2-6, 8, 10-14. The General procedure (see table 1 with the number of agents in each example). Styrene (St), glycidylmethacrylate (GMA), nitroxide and initiator (benzoyl peroxide VRO) were placed in a glass reactor with a double jacket, and oxygen was removed by bubbling nitrogen for 3 minutes. Oil, heated to 131°C, tsirkulirovavshy on the outer jacket, and the mixture was stir at 145 rpm After the desired conversion has been reached, the heating was suspended and additional styrene and optional monomers (see table 2) were added to the reactor with stirring. After 3 min of stirring the reaction was or continued in a glass reactor before conversion was achieved more than 10-20% or directly transferred into the WTO the second reactor. Nitrogen was barotiwala, and the reactor was immersed in an oil bath which was pre-heated to 125-130°C for 18-24 hours to reach a given conversion.

Examples 1, 7, 9. Styrene (St), glycidylmethacrylate (GMA), nitroxide and initiator (benzoyl peroxide VRO) were added to a reactor of stainless steel with a double jacket for 20 liters, and the oxygen was removed, maintaining the pressure in the reactor with nitrogen (up to 6 kg/cm2), the pressure drop three times. The heated oil was tsirkulirovavshy on the outer jacket until the temperature has not been reached 127-129°C and started mixing (60-80 rpm). After you have achieved the desired conversion, the heating was suspended and additional styrene and optional monomers (see table 2) were added to the reactor with stirring. After 1-3 min of stirring, the reaction product is directly transferred into the reactor in the form of plates. Nitrogen was barotiwala through the reaction product, and the oil was tsirkulirovavshy double jacket reactor in the form of plates, in order to maintain the internal temperature of the 127-129°C. Heating was continued until, until he achieved the desired conversion. The product is unloaded from the reactor in the form of sheet ingot molds and grind to obtain a diblock copolymer in the form of granules.

Table 1
Diblock copolymers. The composition of the first stage
Number exampleThe FIRST STAGE
St (mmol)GMA (mmol)GMA (mol.%)andNitroxide (mmol)VRO (mmol)Conversion (%)
1179.8635.8816.60.560.4370.00
2179.8835.7216.50.560.4370.00
3214.328.914.00.620.4885.20
4293.7158.8616.34.313.3289.58
5 200.784.152.00.860.6680.76
6530.5847.288.12.481.9185.00
7265.9052.7816.50.830.6482.90
8266.2452.8616.50.830.6470.00
9163.9936.4318.10.720.5570.00
10190.20At 27.9412.70.700.5478.18
11211.2541.97 16.50.660.5176.07
12205.0340.7416.50.640.4976.07
13474.1994.1016.51.501.1566.40
14460.7691.4816.51.441.1170.00
aDiscusses the relation of the original GMA to St
NOTE: table 1 shows the number calculated for the synthesis of 100 g of disloca, while the actual amount was increased or decreased depending on the size of the reactor used for each case.

Table 2
Diblock copolymers. The composition of the second stage
Number example The SECOND STAGETOTAL
St (mmol)The butyl acrylate (mmol)Butylmethacrylate (mmol)N-phenylmaleimide (mmol)ConversionGMA (mol.%)b
1729.520.000.000.00993.8
2730.570.000.000.00993.8
3731.680.000.000.00990.9
4572.320.000.000.00996.3
5750.950.000.000.0099 0.4
6357.110.000.000.00995.0
7619.550.000.000.00995.6
8620.380.000.000.00995.6
9745.240.000.000.00973.8
10547.99148.430.000.00973.1
11421.99217.380.000.00984.7
12409.550.0 210.890.00974.7
13292.730.000.00At 36.099210.5
14284.620.000.0052.649210.3
bConsiders the ratio of the total GMA to the monomers (1-St and second stage)
NOTE: table 2 shows the number calculated for the synthesis of 100 g of disloca, while the actual number was higher or lower depending on the size of the reactor used for each case.

Molecular mass distribution relative to polystyrene determined by GPC (ASTM D3536-91) using a Waters 410, RI detector, eluent THF, 1.0 ml/min at 40°C; linear Styragel columns 4 HR and 3 HR. The results are shown in table 3.

Table 3
Properties of diblock copolymers
The number of the example of the diblock copolymerThe first stageTotal
MuMwPDIMnMwPDI
120212225461.12926181425271.54
224068298701.24647711098871.70
327682305851.10920601381321.50
4782688571.1316994203531.20
515269168371.105064876101 1.50
615965179941.1325329306241.21
727526326981.1949768745091.50
832331385281.1965338965071.48
924144275551.14676971052331.55
1023490305951.30705281534452.18
1120813257411.24610061253482.05
1220813 257411.2450622916061.81
1327569344471.2545396742891.64
1432331385281.1935273662881.88

Residual glycidylmethacrylate (GMA). To determine the amount of residual GMA reaction mixture of example 2 (the first stage after was reached 70%conversion) was analyzed using gas chromatography, and the amount of GMA was determined using a calibration curve GMA at a known concentration.

Table 4 shows the data of the calibration curve used to determine the content of GMA: Standards contain different amounts of GMA and a set amount of toluene as an internal standard, both dissolved in THF. The chromatogram was integrated, and the relative areas were calculated (peak area GMA/square toluene), linear regression is used to correlate the relative peak area to concentrate the radio GMA (relative area = 0.4192 *(concentration GMA) + 0.1138; R2=0.9972). A sample of 100 mg of the reaction mixture of example 2 (the first stage after 70%conversion) was dissolved in THF by the addition of the same amount of toluene as an internal standard, which was used in the standards.

Table 4
Data from the calibration curve of the gas chromatography used to determine % weight./weight. GMA
Concentration standards GMA (mg/ml)The peak area (relative to internal standard)
00
1.04240.602686
5.2122.59247
10.4244.40227
15.6366.273665
20.8489.029951
26.0611.10497

The mixture of example 2 in the first stage shows the chromatogram with a relative peak area 2.203, which corresponds (using the linear regression equation) concentration 4.984 mg/ml whereas the number is the number of sample this corresponds to 4.34% wt./weight. GMA. After reaching 70%conversion only 30% of the sample containing the monomers and the concentration of GMA in the monomers is then equal to 14.47% wt./weight. (4.34 g GMA*100 g of reaction mixture/30 g of a mixture of residual monomers).

Synthesis of standard materials. To compare the features iblokov obtained in examples 1-14 were obtained three statistical copolymer. The General procedure (see table 5 number of reagents in each example). Styrene (St), glycidylmethacrylate (GMA), nitroxide and initiator (benzoyl peroxide VRO) were placed in the reactor, the nitrogen was barotiwala through the mixture, and the reactor was immersed in an oil bath which was pre-heated to 125-130°C for 20-24 hours to reach a given conversion.

The number of monomer units in each block can be adjusted by the first conversion unit, the total conversion and the amount of initiator and regulatory agent. The composition of each block can be adjusted molar percentage of monomer added during the first and second stage. This can better be understood from examples 1-11, where different total glycidylmethacrylate (example 4 has a 6.3 mol.% GMA, while in example 5, there is a 0.4 mol.%), and different molecular weight in both blocks (in the example 4 has srednesemennyh molecular weight (Mn) first the th block 7826, then as in example 8 has a Mn 32331; in the example 1 has a common Mn 92618, whereas in example 4 has a common Mn 16994), depending on the initial composition of the monomers, nitroxide and initiator, the amount of styrene added in the second stage, the conversion of the first block and the total conversion. The total number of functional acrylic monomer (GMA in this case) can be adjusted initial amount added GMA, the conversion of the first block and the number of monomers added in the second stage. For example, in examples 2, 7 and 11 have the same percentage of GMA, added in the first stage (16.5 mol.%), but as the amount of styrene added in the second stage, is different, they have different total number of GMA. In the examples containing GMA and styrene in the first stage, because of the reactivity of the two monomers is similar, the initial molar percentage GMA added in the first stage, similar to (but below) the molar percentage included in the first block. For example 2, the amount of residual GMA in residual monomers were quantified using gas chromatography (see description below table 3) obtaining 14.47% wt./weight. compared to the original mass percentage, which is at 21.33% wt./weight.

Another system in which the reactive group is contained in both blocks, is a system consisting of spezialmaterie and styrene in the first stage and N-phenylmaleimide and styrene in the second stage (examples 13 and 14). In these examples, while N-phenylmaleimide tends to rotate the copolymer will consist of a triblock, where the second block contains N-phenylmaleimide, and the third block will consist mainly of polystyrene.

Polymer mixture

Compatibility polistirolbetona copolymer and mixtures PET.

Examples 18-24. Raw material: commercial statistical poly(styrene-co-butyl acrylate) (66 mol. percent styrene and PET bottle grade (LV. 0.75-0.9 DL/g, measured in the 60/40 phenol/dichlorobenzene at 25°C).

Examples 18-24. The methods of mixing

Mixtures were prepared in 90/10 weight ratio of the granules PET and acrylic copolymer according to table 6. For examples 51-56 agent that improves compatibility was added during the process. The samples were analyzed using 100X magnification optical microscope for large particles, and the particles were not observed at 100X magnification, the morphology of the blends was determined using transmission electron microscope Carl Zeiss EM 120 kV after microcomedone at room temperature. Sections were stained pairs RUO Li4.

Table 6
The composition of the polystyrene-acrylic copolymer/PET blends
But the EP sample mixture The diblock copolymer from table 1PET/poly(styrene-co-butyl acrylate/diblock copolymerPET (g)Poly(styrene-co-butyl acrylate) (g)The diblock copolymer (g)
1819010551.45.72.9
1979010551.45.72.9
2099010551.45.72.9
21109010551.45.72.9
22119010 551.45.72.9
23129010551.45.72.9
24no9010054.06.00.0

Table 7
Microscopic analysis of mixtures 18-24
The number of sample mixtureParticle size (µm)
MaxThe average size
183.551.01
191.360.44
202.320.33
213.701.21
2236.353.02
2323.753.15
2410.760.44

In experiments 18-24 characteristics of different block copolymers evaluated from the viewpoint of reducing the size of particles in mixtures of polymers. Table 7 shows that most of the block copolymers are effective in reducing the maximum particle size (with the exception of examples 22 and 23, in which low characteristics can be attributed to rheological disadvantages of mixing, due to the low Tg of the copolymers, which contain acrylate or methacrylate). Characteristics of the block copolymers depend on a variety of variables such as the number of functional groups in each block, the molecular weight of each block and composition (polarity). In the present invention, these variables can be easily adjusted to get the kind of agents compatibility with different composition and molecular weights, which can be tested to determine the correlation between the structure/composition and characteristics.

In relation to Figure 3, 4A and 4b pictures to THOSE of examples 20 and 24 showed as poly(styrene-co-butyl acrylate (dark particles) distributed in the PET matrix. In the learn example 24 photos presented at Figo and 4b show a mixture without an agent compatibility, composed of fine particles (less than 0.44 micrometers, μm) and the combination of very large particles (about 10 micrometers). In the case of example 20, shown in Figure 3, the addition of only 5% agent compatibility clearly improves the dispersion of poly(styrene-co-butyl acrylate), resulting in a more uniform distribution with an average particle size of 0.33 μm and a maximum particle size of 2.32 μm. Compatibility of mixtures of PET and poly(styrene-co-methylmethacrylate).

Examples 25-34. Raw material: Amorphous PET (Eastman plastic, EASTAR copolyester 6763 natural) and poly(styrene-co-methyl methacrylate) (SET 115 from Resirene). PET pre-dried under reduced pressure for 4 hours at 65°C.

Examples 25-34. Mixing, General procedure: All components are physically mixed dry mixture in the proportions indicated in the following table (table 8) to obtain 60 g of a mixture. The mixture was then mixed using a Haake mixer at 60 rpm at 150°C for 5 minutes after reaching the constant rotating torque. The samples were analyzed using 100X magnification in an optical microscope for large particles, and the particles were not observed at 100X magnification, the morphology of the blends was determined using transmission electron microscope Carl eiss EM 120 kV after microcomedone at 0°C. Sections were stained pairs RUO Li4.

80
Table 8
The composition of the blends PET/poly(styrene-co-methyl methacrylate)
The number of sample mixtureThe diblock copolymer from table 1PET/poly(styrene-co-methyl methacrylate)/diblock copolymerPET (g)Poly(styrene-co-methyl methacrylate) (g)The diblock copolymer (g)
2518020346.611.71.7
2638020346.611.71.7
2748020346.611.71.7
28520346.611.71.7
2968020346.611.71.7
30680200.547.811.90.3
3168020545.711.42.9
3278020346.611.71.7
3398020346.611.71.7
34 no8020048.012.00.0

Table 9
Microscopic analysis of mixtures 25-34
The number of sample mixtureParticle size (nm)
MinimumMaxThe average size
252241268530
26113800408
2760807354
2861118451010
29133706347
30951265462
31912133292
321111070464
333261277640
3473261681632

Examples 25-34 show the compatibility of PET and poly(styrene-co-methylmethacrylate). In these examples we present three statistical measurements of particle size (minimum, maximum and average size) effectively reduced by using different diblock copolymers (see table 9). As the mixture 34 without an agent compatibility contains large particles of poly(styrene-co-methyl methacrylate), this mixture could be observed using an optical microscope. As can be seen in Fig.6, photomicrography mixture 34 shows poly(styrene-co-methyl methacrylate), dispersed in PET, with average particle sizes 1632 nm. On the contrary, the picture of THE example 29, shown in Figure 5, demonstrates that the compatible mixture has a significantly smaller average particle size 347 nm, and that even the largest particle (706 nm) is smaller than the minimum particle size obtained without and the enta compatibility.

Compatibility of polyethylene terephthalate and blends of SEBS.

Examples 35-40. Raw material: retalitory PET bottle grade (I.V. 0.8 DL/g, measured in the 60/40 phenol/dichlorobenzene at 25°C.) was dried for 2 h at 130°C before use; SEBS CH-6170 and CH-6110 from Dynasol.

Examples 35-40. Mixing, General procedure: All components are physically mixed dry mixture in the proportions indicated in the following table (table 10) to obtain 2 kg of the mixture. The mixture was extruded using a twin screw extruder ZSK-30 from Coperion and temperature profile: 248-270°C. the Samples were cut into pellets and dried. The materials were injectively at a temperature of 260-275°C and a mold temperature of 65-70°C. the Injected materials were evaluated according to ASTM D638 and ASTM D256, as shown in table 11.

Table 10
The composition of the blends PET/SEBS.
The number of sample mixtureThe diblock copolymer from table 1 or table 5PET/SEBSa/DeblockRET (g)SEBS (g)Diblock (g)
351675 2051500.0400.0100.0
368752051500.0400.0100.0
3716801551600.0300.0100.0
388801551600.0300.0100.0
39no703001400.0600.00.0
40no703001400.0600.00.0
andIn all cases, was used SEBS SN with the sole exception of the rooms of example 40, using SEBS SN.

Table 11
Mechanical properties of examples 35-40
The number of sample mixtureYield strength (Kpsi) ASTM D638The limit of the relative deformation during elongation (%) ASTM D638The tensile strength (Kpsi) ASTM D638Relative deformation tensile Break (%) ASTM D638Impact strength Izod (0.125 inch)lb-ft/inch ASTM D256
354.584.78-0.0011.27
364.654.81-0.0013.71
375.174.792.57134.421.63
385.28 4.90-0.0011.35
39NDNDNDND1.34
40NDNDNDND0.89
ND: not defined

The compatibility of PET and SEBS shown in the examples 35-40, is achieved with the use of various reactive block copolymers. In these examples, a statistical copolymer with the same composition (examples 35 and 37 containing polymer 16) is also included for comparison purposes. The mechanical properties of these mixtures show that reactive diblock copolymer 8 has superior properties in comparison with a statistical copolymer in similar compositions (table 11, a mixture of 35 vs. 36 and a mixture of 37 vs. 38). When compared to the impact strength Izod these mixes, you get superior strength with the block copolymer 8 compared with the statistical copolymer 16 (a mixture of 35 vs. 36 and a mixture of 37 vs. 38). The mixture without the agent compatibility was evaluated using even more SEBS (30% SEBS), to emphasize that even with the high amounts of impact strength modifier mixture is too low, the properties of resistance to shock loads.

Examples 35-40 show how the block copolymers of the present invention can effectively modify the properties of resistance to shock loads recyclebank PET, making them analogous to the SEBS.

Compatible mixtures of polycarbonate and acrylonitrilebutadienestyrene (PC/ABS)

Examples 41-53. Raw material: polycarbonate Lexan 121 was acquired from General Electric and Terluran GP35 (ABS) from BASF. The materials were dried for 4 hours before using.

Examples 41-53. Mixing, the General procedure. All the components were physically mixed dry mixture in the proportions indicated in the following table (table 12) to obtain 2 kg of the mixture. The mixture would be extruded using a twin screw extruder ZSK-30 from Coperion temperature profile: 248-270°C. the Samples were cut into pellets. The materials were injected at a temperature 265-275°C. and a mold temperature of 45°C. the Injected materials were evaluated according to ASTM D638 and ASTM D256, shown in table 13.

Example 48 was analyzed using 100x magnification optical microscope. As can be seen in Fig.7, photomicrography mixture 48 shows a co-continuous morphology. On the contrary, for a compatible mixture of example 53, shown in Figa and 8b, the observed particles at 100x magnification were smaller and were then analyzed using transmission electron microscope (Jeol 200KV), after m is crotonylene at 0°C staining pairs RUO Li 4(ABS shown in the pictures in the dark. Photomicrography of example 53, Figa and 8b, shows a dramatic improvement in the particle size ABS dispersed in PET compared to a mixture without the agent compatibility. The average particle size is 0.867 micrometer.

Table 12
The composition of mixtures of PC/ABS
The number of sample mixtureThe diblock copolymer from table 1 or table 5PC/ABS/deblockRS (g)ABS (d)Diblock (g)
41no505001000.01000.00.0
421350505952.4952.495.2
431450505 952.4952.495.2
44no604001200.0800.00.0
4515604031165.0776.758.3
461450503970.9970.958.3
4714604031165.0776.758.3
48no703001400.0600.00.0
491470 3051333.3571.495.2
5013604051142.9761.995.2
5114604051142.9761.995.2
5213703051333.3571.495.2
5314703031359.2582.558.3

346.84
Table 13
Mechanical properties of examples 41-53
The number of sample mixtureLimit fluid is tee
(Kpsi) ASTM D638
The limit of the relative deformation during elongation (%) ASTM D638The tensile strength (Kpsi) ASTM D638Module uprugosti tensile (Kpsi) ASTM D638Impact strength Izod (0.125 inch) lb-ft/inch ASTM D256
416.752.992.82334.130.29
427.024.3118.05358.720.81
437.144.6216.38348.261.01
447.464.526.78343.351.13
457.464.7919.49333.001.53
467.064.3420.923.04
477.664.9521.68346.054.27
487.965.0312.88338.144.44
498.165.2317.78349.014.87
507.615.0021.00340.345.12
517.594.9119.09350.985.44
528.135.1716.77349.735.47
538.125.2822.25344.566.27

Table 13 demonstriruyuschie properties and impact strength Izod mixtures of PC/ABS using: i) different ratios of PC to ABS, ii) different agents compatibility iii) statistical copolymer with the same molecular weight and composition of the investigated block copolymer. The best characteristics of the block copolymer (table 13, example 47 using dibaca example 14) in comparison with the statistical copolymer (example 45 using statistical block copolymers of example 15) is shown in all mechanical properties of the mixture and more clearly observed in impact strength Izod. In fact shock, the statistical copolymer (1.53 lb-ft/in), example 45), similar to the shock load, the statistical copolymer prepared without an agent compatibility (1.13 lb-ft/inch, example 44), and is lower than the impact load, the diblock copolymer (4.27 lb-ft/inch, example 47). The best properties resistance to shock loads obtained for mixtures containing more polycarbonate treated 6.24 lb-ft/inch for a compatible mixture of 3 wt%. agent compatibility against 4.44 lb-ft/inch for mixtures without an agent compatibility.

Examples 41-53 show how the block copolymers of the present invention can improve the properties of resistance to shock loads of polycarbonate, making them more compatible with ABS.

Compatible mixtures of polycarbonate and high impact polystyrene

Examples 54-56. Raw material: polycarbonate Lexan 121 the 141 was acquired from General Electric; high impact polystyrene (HIPS)containing 40 rubber was obtained as a special mark from Resirene; additive that improves the fluidity, Joncryl ADP 1200 from Johnson Polymers and antioxidant U-626 from Crompton. The polymers were dried prior to use.

Examples 54-56. Mixing, the General procedure. All the components were physically mixed dry mixture in the proportions indicated in the following table (table 14). The mixture was extruded using a twin-screw extruder (ZSK-30 from Coperion) and temperature profile: 255-270°C. the Samples were cut into pellets and dried. The materials were injected at a temperature 265-275°C in the mold at a temperature of 45°C. Impact strength Izod injected material was evaluated according to ASTM D256, as shown in table 14.

Table 14
The composition of mixtures of PC/HIPS and the strength Izod
The number of sample mixtureThe diblock copolymer from table 1 or table 5Lexan 121/Lexan 141/HIPS 40/diblock copolymerLexan 121 (d)Lexan 141 (g)HIPS 40 (g)The diblock copolymer (g)Impact strength is about Izod (0.125 inch) lb-ft/inch ASTM D256
54no47.5020.532.00712.50307.50480.000.003.6
551647.5020.532.003712.50307.50480.0045.004.6
56247.5020.532.003712.50307.50480.0045.006.1

Properties resistance to shock loads Izod mixtures of PC/HIPS evaluated in the examples 54-56 using the block copolymer 2 (see table 1), statistical copolymer 16 (see table 5) and agentless compatibility. The results show that the block copolymer has better specifications than the achieved performance in use is assured a statistical copolymer as an agent compatibility and of course the best performance than using a mixture without an agent compatibility.

Examples 54-56 show how the block copolymers of the present invention can improve the properties of resistance to shock loads of polycarbonate, making them more compatible with high impact polystyrene.

With the description of the invention above, various modifications of the techniques, procedures, materials and equipment will be apparent skilled in this technology specialists. It is intended that all such variations within the scope of the claims and the invention is included in the scope of protection of the attached claims.

1. A method of obtaining a block copolymer that includes
a) the reaction of the acrylic monomer having a functional group, representing epoxy, acid, anhydrous, amino, amide and hydroxy-group, and one or more vinyl monomers in the presence of a free radical initiator and a stable free radical at the first stage, with the formation of the reaction product, which includes residual unreacted acrylic monomer; and
b) the reaction at the second stage, one or more vinyl monomers with the reaction product from the first stage, with the formation of the second block, which includes residual unreacted acrylic monomer.

2. The method according to the .1, characterized in that the acrylic monomer is selected from the group consisting of glycidylmethacrylate, acrylic acid, methacrylic acid, 2-hydroxyethylmethacrylate, 2-dimethylaminoethylmethacrylate and 2-diethylaminoethylmethacrylate.

3. The method according to claim 1, characterized in that the vinyl monomer in the first stage is a styrene.

4. The method according to claim 1, characterized in that the vinyl(s) monomer(s) in the second stage the selected(s) from the group consisting of styrene, N-phenylmaleimide, methyl methacrylate and butyl acrylate.

5. The method according to claim 1, characterized in that the reaction product of the first stage includes at least 0,03 mol.% unreacted residual acrylic monomer.

6. The method according to claim 1, wherein the stable free radical is a free nitroxyl radical.

7. The method according to claim 1, wherein the stable free radical is a 2,2,6,6-tetramethyl-1-piperidinyloxy.

8. The method according to claim 1, wherein the free radical initiator selected from the group consisting of 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), Dibenzoyl peroxide (VRO), traceminerals-2-ethylhexanoate, tertBUTYLPEROXY-2-ethylhexanoate 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane and tributylphosphorotrithioate.

9. The method according to claim 1, characterized in that the molar is the rate of the total number of monomer to initiator is in the range 50 ÷ 12000.

10. The method according to claim 1, further comprising adding additional initiator during the second stage.

11. The method according to claim 1, characterized in that the first stage is carried out in a reactor with stirring until then, it had not reached a conversion of from about 14 to about 90%.

12. The method according to claim 11, characterized in that the second stage is carried out in the second reactor without stirring until then, it had not reached a conversion of from about 90 to about 100%.

13. The method according to item 12, wherein the second reactor is a reactor in the form of leaf mold.

14. The method according to claim 11, characterized in that the second stage is carried out in the second reactor with stirring until the achieved conversion of from about 60 to about 100%.

15. The method according to 14, wherein the second reactor is a reactor-mixer.

16. A method of obtaining a block copolymer that includes
a) the reaction at the first stage of styrene and acrylic monomer having a functional group selected from the group consisting of glycidylmethacrylate, acrylic acid, 2-hydroxyethylmethacrylate and 2-diethylaminoethylmethacrylate, in the presence of a free radical initiator and a stable free radical based nitroxide at a temperature of between approximately 80°and approximately 135°C, with conversion in the range between approximately 14 and approximately 90%, with the formation of the reaction product comprising the first block and the residual monomer, where the reaction product comprises at least about 0.03 mol.% unreacted acrylic monomer; and
b) the reaction at the second stage, one or more monomers selected from the group consisting of styrene, N-phenylmaleimide, methyl methacrylate and butyl acrylate with the reaction product of the first stage, with the formation of the second block containing monomer units of acrylic monomer with the first stage.

17. A method of obtaining a block copolymer that includes
a) the reaction of the acrylic monomer having a functional group, representing epoxy, acid, anhydrous, amino, amide and hydroxy-group, and one or more vinyl monomers in the presence of a free radical initiator and a stable free radical, with the formation of the reaction product containing the first block and the residual unreacted acrylic monomer; and
b) reaction of one or more vinyl monomers with the reaction product of the first stage in the presence of a solvent, with the formation of a block copolymer comprising a second block that is attached to the first block, where the second block has a functional group, secured by the residual unpar eagerbeaver acrylic monomer.

18. The method according to 17, characterized in that the first stage is carried out in a reactor with stirring until then, it had not reached a conversion of from about 14 to about 90%, and the second stage is carried out in the second reactor with or without stirring until then, it had not reached a conversion of from about 90 to about 100%.

19. The block copolymer obtained by the method according to any one of claims 1 or 17, including
a) a first block comprising Monomeric units functionalized acrylic monomer having a functional group, representing epoxy, acid, anhydrous, amino, amide and hydroxy-group, and monomer units of vinyl monomer; and
b) a second block comprising Monomeric units of one or more vinyl monomers and Monomeric units functionalized acrylic monomer having a functional group, representing epoxy, acid, anhydrous, amino, amide and hydroxy-group in the first block.

20. The block copolymer according to claim 19, in which the functionalized acrylic monomer in the block copolymer is from about 0.5 to about 70% weight.

21. The block copolymer according to claim 19, in which the residual monomers from the first block contains at least 1 wt.%/weight. functionalized acrylic monomer.

22. The block copolymer according to claim 19, in to the m acrylic monomer selected from the group consisting of glycidylmethacrylate, acrylic acid, methacrylic acid, 2-hydroxyethylmethacrylate, 2-dimethylaminoethylmethacrylate and 2-diethylaminoethylmethacrylate.

23. The block copolymer according to claim 19, in which the vinyl monomer of the first block selected from the group consisting of styrene, substituted styrene, substituted acrylates and substituted methacrylates.

24. The block copolymer according to claim 19, in which the vinyl(s) monomer(s) in the second selected block(s) from the group consisting of styrene, substituted styrene, Acrylonitrile, N-aromatic substituted maleimide, N-alkyl substituted maleimide, acrylic acid, methyl methacrylate, alkyl substituted acrylates, aryl-substituted acrylates, alkyl substituted of methacrylates, aryl-substituted of methacrylates and 2-hydroxyethylmethacrylate.

25. Thermoplastic polymer composition applicable for materials with high resistance and mechanical strength, including
(a) 1-98 wt.% the first thermoplastic having a functional group selected from the group consisting of amino, amide, imido, carboxyl group, carbonyl, carbonate ester, anhydride, epoxy, sulfo, sulfonyl, sulfinil, sulfhydryl, cyano and hydroxy;
(b) 0.01-25 wt.% the block copolymer according to claim 19, which contains a functional group which is capable of reaction with the functional group of thermoplastic; br/> (c) 1-98 wt.% the second thermoplastic polymer that is miscible or compatible with the second block of the block copolymer according to claim 19.

26. The composition according A.25, in which the block copolymer obtained by the method according to claim 1.

27. The composition according A.25, in which the block copolymer obtained by the method according to 17.

28. The composition according A.25, in which thermoplastic polymer is srednesemennyh molecular weight that is between 5000 and 200,000.

29. The composition according A.25, in which the first thermoplastic polymer selected from the group consisting of aliphatic or aromatic polycarbonates, polyesters, polyamides, polivinilovogo ether, polyolefin, having apachegroup, anhydride or acid functional group, polysulfones, polyurethanes and mixtures thereof.

30. The composition according A.25, in which the second thermoplastic polymer selected from the group consisting of polystyrene, polyamidine styrene, butadiene random copolymers, styrene block copolymers, polystyrene, high impact, hydrogenated block copolymer of styrene and a diene monomer, polivinilovogo ether, polyacrylates, polymethacrylates, acrylic statistical copolymers, block copolymers of acrylate, methacrylate random copolymers, methacrylate block copolymers, polyolefins, polyurethanes, polyvinyl chloride, polyvinylidene the IDA, polyvinyl, polyvinylidenedifluoride copolymers, copolymers containing units of styrene and Acrylonitrile, copolymers containing parts of Acrylonitrile-styrene and butadiene, copolymers containing parts of Acrylonitrile-styrene and n-butyl acrylate, copolymers containing units of Acrylonitrile, butadiene and n-butyl acrylate and mixtures thereof.

31. The composition according to p. 25, additionally comprising one or more polymer additives selected from the group consisting of stabilizers, antioxidants, auxiliary additives to improve the fluidity, flame retardants, modifiers, increasing shock strength, nucleating, pigments and fillers.



 

Same patents:

FIELD: manufacturing process.

SUBSTANCE: invention relates to manufacture of flexible multilayer packaging materials for food products, particularly to multilayer material comprising layers of aluminuim foil and fat- and water-proof paper. The multilayer packaging material comprises as an adhesive for joining layers of aluminuim foil and fat- and water-proof paper an adhesive composition based on an aqueous dispersion of a copolymer of acrylic acid ester and styrene. The composition also includes a coalescent additive - isomeric mixture of 2,2,4-trimethyl-1,3-pentadiol-monoisobutyran, antiseptic - a composition of tri-n-butyltin naphthenate with nitrogen organic compound, antifoam based on mineral oil, a thickening agent - sodium salt of carboxymethyl cellulose and distilled water.

EFFECT: increased adhesive bond strength of multilayer packaging material, the material resistance to multiple excesses, produceability.

1 dwg

The invention relates to compositions for bonding, sealing and performance of coatings on the basis of a copolymer of styrene, which is suitable as a binder in obtaining adhesives, coatings and masses jointing

The invention relates to a water dispersion glue-based dispersion of a copolymer or terpolymer with fire-retardant agent-based compounds of boron or aluminum

The invention relates to the chemistry of macromolecular compounds, namely to a new product thermostabilization in weight styrene and derivatives divinylsulfide containing 20 wt.% styrene of the General formula:

< / BR>
where R - link (E)-4-thio-2,5-hexadien-1-ol m = 96-774, n = 113-190,

when R-link 3-(VINITI)-1,2-epoxypropane m = 72-600, n = 120-200, or stitched mesh of a copolymer of styrene with 3,7-dithio - 1,8-nonadien-5-I, containing 238-1594 parts of styrene, or mixtures thereof, and 80% of the polymerization mixture, which can be used as an adhesive for bonding rubber, glass, metals, semi-precious stones, porcelain, ceramics, leather, etc

FIELD: transport.

SUBSTANCE: treads and/or subtread for heavy vehicles consists, at least partially, of rubber composition including 80-100 wt % of natural rubber and 0-20 wt % of synthetic polyisoprene rubber. It includes also reinforcing filler containing a) 30-50 wt % of superfine silicon dioxide, and b) technical carbon in amount of 0.75-1.25 wt % defined by equation C=-0.8Si+44.3 where Si is the quantity of fine silicon dioxide. Besides, composition includes silane binder and sulfuric hardening system containing 1.5-3 wt % of free sulfur and 0.9-1.1A wt % of sulphenamide accelerator where A is defined as a function of quantity of sulfur and weight fraction of silicon dioxide of total amount of reinforcing filler.

EFFECT: increased strength of tire.

18 cl

FIELD: chemistry.

SUBSTANCE: invention relates to a rubber composition for use in a mixture with impact-resistant plastic, a method of preparing a mixture of polymer composition and impact-resistant plastic, as well as a composition of impact-resistant plastic. The rubber composition for use in a mixture with impact-resistant plastic contains a polymer obtained by polymerising at least one conjugated diene in the presence of an anionic initiator and a viscosity-reducing additive. Said polymer contains carboxylate terminal groups formed by adding carbon dioxide to break polymerisation chains and has Mooney viscosity ML1+4 greater than approximately 35 and solution viscosity X, where X is greater than approximately 75 cP. The viscosity-reducing additive has polymer solution viscosity from X to 0.4X-0.58X.

EFFECT: obtaining polymers with improved strength properties for use in impact-resistant plastic, as well as use of an additive which reduces polymer solution viscosity while maintaining high bulk viscosity.

28 cl, 5 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to polymer chemistry, particularly to novel block copolymer compositions and methods of preparing said compositions. The novel block copolymer compositions are particularly suitable for making articles by moulding or extrusion. The block copolymer composition contains 100 pts.wt solid block copolymer obtained via anionic polymerisation and 5-250 pts.wt plasticising modifier. The block copolymer contains at least two blocks A and at least one block B. Block A is a monoalkenylarene block, block B is selected from polymer blocks containing at least one conjugated diene and at least one monoalkenylarene and having random or controlled distribution. The plasticising modifier contains a conjugated diene and has a structure similar to the structure of block B of said block copolymer. The plasticising modifier is synthesised and/or treated together with the block copolymer in situ to obtain a homogeneous mixture of modifier and block copolymer.

EFFECT: jointly prepared mixtures of modifying plasticisers and block copolymers are characterised by higher breaking and tearing strength compared to similar mixtures containing oil, as well as higher plasticity without considerable deterioration of processability.

17 cl, 1 dwg, 7 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: composition contains (a) 100 pts.wt solid selectively hydrogenated block-copolymer, having general formula A-B-A, (A-B)nX, where n varies from 2 to 3, and (b) 5-250 pts.wt hydrogenated plastification modifier which contains at least one hydrogenated conjugated diene selected from isoprene, 1,3-butadiene and mixtures thereof. Before hydrogenating the block-copolymer, each block A is a monoalkenylarene polymer block and each block B is a conjugated diene block. Each block A has average molecular weight varying from 3000 to 60000, and each block B has average molecular weight varying from 30000 to 300000. The total amount of monoalkenylarene in the hydrogenated block-copolymer ranges from 20 to 80 wt %. The plastification modifier is characterised by content of vinly groups (V2) before hydrogenation such that the ratio V2/V1 lies between 0.8 and 1.2. The ratio (MW2)/(MW1) of the average molecular weight of said plastification modifier (MW2) to the average molecular weight of block B (MW1) ranges from 0.01 to 0.3, with minimum molecular weight (MW2) 2000 and maximum molecular weight (MW2) 13000. The plastification modifier is further characterised by a polydispersity index (PDI). If PDI of said plastification modifier lies between 1.0 and less than 1.5, then the average molecular weight of said plastification modifier lies between 2000 and 7000. If PDI lies between 1.57 and 1.7, then the average molecular weight lies between 6800 and 13000.

EFFECT: considerably high breaking stress and improved compressions set of block-copolymer compositions, which enables to obtain compositions with low volatility at given hardness, as well as improved organoleptic properties, improved fogging characteristics and low level of extraction.

24 cl, 14 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: moulded article is made from a polymer composition containing 99-30 pts.wt cyclic olefin polymer (A); and 1-70 pts.wt soft copolymer (B) obtained through polymerisation of at least two monomers selected from a group consisting of olefins, dienes and aromatic vinyl hydrocarbons and having glass transition temperature not higher than 0°C. Said polymer composition also contains 100 pts.wt of the total amount of cyclic olefin polymer (A) and soft copolymer (B), 0.001-1 pts.wt radical initiator (C), 0-1 pts.wt polyfunctional compound (D) containing two or more radically polymerisable functional groups in a molecule, and 0.5-10 pts.wt nonionic or anionic antistatic additive (E). The moulded article, particularly a container, is used for work in pure production facilities when producing articles such as cassettes for semiconductor wafers.

EFFECT: moulded articles having high wear and impact resistance can be made from the polymer composition.

16 cl, 3 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: glass-like blocks contain 25-50 mol % alpha-methylstyrene and have glass transition temperature ranging from 120 to 140°C. Polymerisation is carried out at temperature from 35 to 60°C, and relatively high content of solid substance while continuously adding styrene, which leads to high degree of conversion of alpha-methylstyrene. The invention also describes elastomeric compositions with high operating temperature, containing a block-copolymer and an olefin polymer or a copolymer, a selectively hydrogenated elastomeric block-copolymer and an article made therefrom, which is a film, fibre, nonwoven film or multilayer sheet.

EFFECT: improved characteristics.

25 cl, 1 dwg, 9 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel compositions containing (a) anionic block-copolymers of monoalkenylarenes and conjugated dienes, where one of the blocks is characterised by controlled distribution of monomer links of the copolymer of conjugated diene and monoalkenylarene and demonstrates specific assembly of monomers in the copolymer block, and (b) special-purpose softening modifiers having a specific structure. The invention also discloses methods of preparing said novel compositions and different versions of final use and field of using said compositions.

EFFECT: improved fluidity, reduced hardness, improved stress relaxation characteristics of the polymer compositions, which makes them especially attractive for use in personal hygiene purposes where nonwoven materials, elastic films and fibres are used.

36 cl, 11 ex, 12 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: composition contains from 30 wt % to less than 50 wt % propylene-alpha-olefin copolymer and from more than 50 wt % to 70 wt % styrene block-copolymer. The propylene-alpha-olefin copolymer has at least 70 wt % links formed from propylene, and from 10 to 25 wt % links formed from C2- or C4-C10-alpha-olefin and has heat of fusion less than 37 J/g and melt flow index from 0.1 to 100 g/10 min. The composition has modulus of elasticity in tension less than 20 MPa, ultimate tensile stress of at least 5 MPa and elongation at failure of at least 900% and low relative instantaneous shrinkage.

EFFECT: composition has good physical properties such as elasticity and flexibility, and can also be easily processed using traditional equipment for processing polyolefins.

21 cl, 8 dwg, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer composition which forms a "liquid in solid substance" polymer system at room temperature and having the prolonged release effect of a liquid organic compound, and articles made from said composition. The composition contains 0.1-50 pts. wt thermoplastic polymer (A) and 0.1-20 pts. wt block-copolymer (B). Block-copolymer (B) contains a block (b1) having high compatibility with a thermoplastic polymer (A), but low compatibility with a liquid compound (C), and a block (b2) having high compatibility with the liquid compound (C), but low compatibility with thermoplastic polymer (A). Block-copolymer (B) acts like a surfactant by forming a boundary surface between polymer (A) of the matrix and liquid compound (C).

EFFECT: composition enables to hold a liquid compound dispersed therein with high concentration.

28 cl, 5 dwg, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a composition of a hot melt pressure-sensitive adhesive (HMSPA), a laminated system and a pressure sensitive label containing said adhesive. The HMSPA composition contains: a) 30-50% mixture of styrene diblock- and triblock-copolymers, total content of the styrene monomer in the said mixture between 14 and 40%; b) 40-55% tackifying resin with melting point between 70 and 150°C, obtained through hydrogenation, polymerisation or copolymerisation of mixtures of aliphatic unsaturated hydrocarbons containing approximately 5, 9 or 10 carbon atoms; c) 4-20% hydrocarbon coil containing less than 15% aromatic compounds; d) 1-6% filler selected from calcium carbonate or a homopolymer or a copolymer polyethylene with low molecular weight. The laminated system includes an adhesive layer consisting of HMPSA and a paper front material. The pressure sensitive label is made from the laminated system.

EFFECT: HMPSA composition provides low susceptibility to decolouration during storage of articles.

15 cl, 11 ex

FIELD: chemistry.

SUBSTANCE: multimodal copolymer of ethylene and one or more alpha-olefins contains 4-10 carbon atoms and is characterised by density of 924-935 kg/m3, melt flow index PTR5 of 0.5-6.0 g/10 min, melt flow index PTR2 of 0.1-2.0 g/10 min, and shear thinning index UVS2.7/210 of 2-50. The multimodal ethylene copolymer is obtained in two steps by polymerisation in the presence of a catalyst with a single polymerisation centre of ethylene, hydrogen and one or more alpha-olefins having 4-10 carbon atoms. A low-molecular weight component (A) of the ethylene polymer is obtained in a first polymerisation zone and a high-molecular weight component of the ethylene copolymer (B) is obtained in a second polymerisation zone. The first and second polymerisation steps can be carried out in any order and the next step is carried out in the presence of a polymer obtained at the previous step. Components (A) and (B) are present in the multimodal ethylene copolymer in amount of 30-70 wt % and 70-30 wt %, respectively, of the total amount of components (A) and (B). Component (A) has weight-average molecular weight of 5000-100000 g/mol and density of 945-975 kg/m3, and component (B) has weight-average molecular weight of 100000-1000000 g/mol and density of 890-935 kg/m3.

EFFECT: tubes have good mechanical properties and are suitable for transporting liquids under pressure.

15 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: multimodal ethylene copolymer has density of 924-960 kg/m3, melt flow index STR5 of 0.5-6.0 g/10 min, melt flow index STR2 of 0.1-2.0 g/10 min and shear thinning index IUVS2.7/210 of 2-50. The multimodal ethylene copolymer contains at most 100 ppm by weight of volatile compounds. The multimodal ethylene copolymer is obtained in two steps by polymerisation in the presence of a catalyst with a single polymerisation centre of ethylene, hydrogen and one or more alpha-olefin having 4-10 carbon atoms. A low-molecular weight component (A) of the ethylene polymer is obtained in a first polymerisation zone and a high-molecular weight component of the ethylene copolymer (B) is obtained in a second polymerisation zone. The first and second polymerisation steps can be carried out in any order and the next step is carried out in the presence of a polymer obtained at the previous step. Components (A) and (B) are present in the multimodal ethylene copolymer in amount of 30-70 wt % and 70-30 wt %, respectively, of the total amount of components (A) and (B). Component (A) has weight-average molecular weight of 5000-100000 g/mol and density of 945-975 kg/m3, and component (B) has weight-average molecular weight of 100000-1000000 g/mol and density of 890-935 kg/m3.

EFFECT: improved properties of the compound.

15 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: composition contains (A) about 10-80 wt % soft rubber-like resin based on a vinyl aromatic copolymer, (B) about 4-60 wt % rubber-modified resin based on a vinyl aromatic copolymer and (C) about 5-80 wt % resin based on a vinyl aromatic-vinyl cyanide copolymer. Resin (A) contains as a dispersion phase rubber particles with content of graft polymer of about 40-90%, and average particle diameter of about 6-20 mcm. The moulded article is made by moulding from said thermoplastic resin composition and has a soft surface touch with average surface roughness of about 400-800 nm.

EFFECT: invention enables to obtain moulded articles with a pleasant low lustre and high impact viscosity.

16 cl, 5 dwg, 2 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: method for partial hydrogenation of random copolymers of vinyl aromatic compounds and conjugated dienes is realised in the presence of 2-methoxyethyl tetrahydrofuran as a randomising agent. Reaction of the random copolymer of a vinyl aromatic compound and a conjugated diene dissolved in a hydrocarbon solvent is carried out with hydrogen in the presence of a titanium complex and an alkylating agent until the required degree of hydrogenation is achieved. The alkylating agent is selected from compounds of general formula MgR1R2, where R1 and R2 are identical or different alkyl radicals with 1-12 carbon atoms. The weight-average molecular weight Mw of the starting random butadiene-styrene copolymer can reach 200000-1000000.

EFFECT: invention improves control of the degree of hydrogenation of the copolymer and enables to maintain or improve mechanical and dynamic properties.

11 cl, 4 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: method is carried out in at least two reactors connected in series, where 20-80 wt % of a first polymer is obtained in a suspension in a first reactor and 80-20 wt % second polymer is obtained in a suspension in a second reactor in the presence of the first polymer. One of the polymers is a low molecular weight polymer and the other is a high molecular weight polymer. A stream or suspension containing the obtained polymer is removed from the second reactor and transferred into a stripping reservoir operating under conditions such conditions as pressure and temperature through which at least 50 mol % of the liquid component of the suspension or the non-polymer component of the stream entering the stripping reservoir is removed from the stripping reservoir in vapour form. Stream or suspension concentration of components entering the stripping reservoir, having molecular weight lower than 50 g/mol, Clight products (mol %), satisfies the inequality Clight products<7+0.07(40-Tc)+4.4(Pc-0,8)-7(CH2/CEt), where Tc and Pc respectively denote temperature (°C) and manometric pressure (MPa) at the point where vapour from the stripping reservoir is condensed, and CH2 and CEt denote molar concentration of hydrogen and ethylene, respectively, in the stripping reservoir.

EFFECT: realising the process without need to recompress the liquid evaporated in the first stripping reservoir.

17 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: multimodal copolymer of ethylene and one or more alpha-olefins containing 4-10 carbon atoms is characterised by density of 937-950 kg/m3, flow melt index STR5 of 0.5-2.0 g/10 min, flow melt index STR2 of 0.2-1.0 g/10 min, and shear thinning index IUVS2.7/210 of 0.3-20. The multimodal copolymer contains 30-70 wt % low-molecular weight ethylene polymer, selected from an ethylene homopolymer and a copolymer of ethylene and one or more alpha-olefins containing 4-10 carbon atoms, and is characterised by weight-average molecular weight of 5000-100000 g/mol and density of 960-977 kg/m3, and 30-70 wt % copolymer of high-molecular weight ethylene and one or more alpha-olefins containing 4-10 carbon atoms, and is characterised by average molecular weight of 100000-1000000 g/mol and density of 890-929 kg/m3.

EFFECT: compositions are flexible; tubes made therefrom can be easily bent or coiled into a ring; the tubes are characterised by sufficient mechanical strength, which enables their use under pressure.

15 cl, 1 dwg, 3 tbl, 5 ex

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