Functionalised multi-branched polymers including functionalised polymers synthesised by anionic polymerisation and use thereof

FIELD: chemistry.

SUBSTANCE: invention relates to functionalised multi-branched polymers which include a reaction product of a cross-linking agent and a polymer synthesised by anionic polymerisation and subsequently hydrolysed, a synthesis process thereof and different versions of use thereof.

EFFECT: structure of polymers disclosed herein provides the polymers with improved processing properties and makes said polymers suitable for use in hot-melt adhesives.

16 cl, 8 tbl

 

The technical field

The invention relates to functionalized multiresolutional polymers, which include the reaction product of a crosslinking agent and a polymer synthesized by anionic polymerization, process for their synthesis and different versions of their application, in particular as a hot-melt glue. Thus, the present invention relates to the field of polymers.

The level of technology

Molecular architecture and, in particular, branching, i.e. the introduction of several chains are chemically linked with cross-linking agent, can have a big impact on the performance and properties of polymers. The most widely used method of obtaining multiresolution polymer is anionic polymerization. Although in the literature to obtain branched polymers described various cross-linking agents, the two most widely used cross-linking agents are multi-functional CHLOROSILANES and divinylbenzene. For example, in U.S. patent 3280084 disclosed the use of divinylbenzene as a crosslinking agent for chains polybutadiene lithium. The resulting polymer has a branched structure, the center of which forms polydivinylbenzene, which runs polybutadiene chain. Using the foregoing methods, it is also possible to synthesize multiresistant the polymer chain which is formed by copolymers of styrene and butadiene. In U.S. patent 3639517 also disclosed the use of divinylbenzene to get multirating copolymers of styrene and butadiene, in which the chains are of different molecular weight. The chain was obtained by repeated addition of styrene and initiator with the formation of blocks of polystyrene of different molecular weight, to which was then added butadiene, multiresolution copolymers received, associating the received circuit with divinylbenzene. These defunctionalization multiresolution polymers are used to increase the viscosity index of lubricating oils.

Roovers, Hadjichristidis and Fetters (Macromolecules, Vol 16, 214 (1983)), and Toporowski and Roovers (J. Polym. ScL, Part A, Polym. Chem., Vol 24, 3009 (1986)) describe a method of obtaining multiresolution polymers using multi-functional CHLOROSILANES. The technique consists of linking chains active polymers with polyarylene using it when using Si (CH2CH2SiCl3]4or [CH2Si-(CH2CH2SiCl3)]2received polyisoprenes, polybutadienes and polystyrenes with 12 or 18 circuits, respectively.

Oligomers of acrylic monomers functionalized with at least one ether, carboxyl, anhydrite or epoxy functional group), copolymerizing with styrene has also been successfully used as cross-linking agents to get Union the th polymerization of polymers to obtain multiresolution polymers (U.S. patent 7517934). In the first stage using n-utility as an initiator receive copolymers poly(styrene-butadiene) lithium. In the second stage to the copolymers, polystyrene-butadiene) lithium add a certain amount of acrylic oligomers in the ratio below 1, so that preferably is the binding chains. This method allows to obtain defunctionalization multiresolution polymers containing from 12 to 14 linked chains. These defunctionalization multiresolution polymers are used, for example, for the modification of plastics, bitumen modification, as well as to obtain bounding when pressed adhesives.

The invention

The invention relates to functionalized multiresolutional polymers obtained by the reaction between the polymer synthesized by anionic polymerization using functionalized and protected initiator of General formula Li-Qn-Z-T-(A-R1R2R3)mand the binding agent, which has from 1 to 30 functional groups. The present invention also relates to polymers obtained by removing the protective groups (A-R1R2R3)mand to functionalized gidrirovanny multiresolutional polymers. The present invention also discloses methods of obtaining these polymers, and their n the applicatio, especially in the compositions of hot-melt adhesives, for the modification of plastics and for bitumen modification. The polymers according to the invention have advantages compared with the known prior art polymers with respect to their mechanical properties, rheological properties of the mixture and the physical and chemical interaction with different substrates. These properties make them the preferred application including, for example, to obtain a hot-melt adhesives, bitumen modification and modification impact resistance of engineering plastics.

In the first aspect of the present document provides functionalized multicasualty the polymer that includes the reaction product of:

(a) a cross-linking agent to the number of functional groups of from 1 to 30, preferably from 5 to 20. In the prior art known binding agents that are useful for obtaining multiresolution polymers of the present invention, such as, for example, the oligomers formed acrylic monomers functionalized with at least one ether, carboxyl, anhydrite or epoxy functional group), copolymerizable with styrene (for example, as disclosed in U.S. patent 7517934), or, alternatively, divinylbenzene (as disclosed in U.S. patent 3280084 and 3949020), or, alternatively, the multifunction is the CHLOROSILANES Roovers, Hadjichristidis and Fetters (Macromolecules, Vol 16, 214 (1983)), and Toporowski and Roovers (J. Polym. Sci., Part A, Polym. Chem., Vol 24, 3009 (1986)). Preferred cross-linking agent is an oligomer obtained by radical polymerization of at least one monomer selected from the group consisting of aromatic vinyl monomers, and at least one monomer selected from the group consisting of functionalized epoxy group of acrylic monomers, functionalized anhydrite group of acrylic monomers, functionalized ester group of the acrylic monomers, functionalized with a carboxyl group of acrylic monomers, and any mixtures thereof where the binding agent has srednetsenovoj molecular weight (MP) of from about 1,000 to about 10,000 g/mol and srednevekovoi molecular weight (Mw) of from about 1500 up to about 20,000 g/mol, where present in the acrylic monomer functional groups provide reaction stitching;

(b) and the polymer synthesized by anionic polymerization reaction, characterized in that the polymer synthesized by anionic polymerization, also referred to herein as anionic polymerized polymer of formula (I): Li-Qn-Z-T-(A-R1R2R3)mwhere Q represents alkeneamine aromatic monomers, conjugated diene, or their mixtures, anionic polymerized under dei is a journey of Li-Z, Z is a branched or unbranched hydrocarbon linking group of from 3 to 25 carbon atoms; T is an element selected from oxygen, sulfur and nitrogen; And R1R2R3) is a protective group, where a is an element selected from C or Si, R1, R2, R3independently selected from hydrogen, alkyl groups, alkyl groups, substituted C1-C5alkyl, C1-C5thioalkyl and C1-C5dialkylamino group, aryl group or aryl group, substituted C1-C5alkyl, C1-C5thioalkyl and C-C5dialkylamino group, cycloalkyl groups containing from 5 to 12 carbon atoms, or cycloalkyl groups containing from 5 to 12 carbon atoms, substituted C1-C5-alkyl, C1-C5thioalkyl and C1-C5dialkylamino group, m represents 1 when T represents oxygen or sulphur and m represents 2, when T represents nitrogen, n represents the number of units of diene monomers, alkenyl aromatic monomers or other monomers in their anionic polymerized mixtures. In the present invention With1-C5alkyl represents an alkyl chain comprising from 1 to 5 carbon atoms, linear mud is branched, preferably linear, examples of these1-C5alkyl groups are methyl, ethyl, propyl, butyl and pentyl. As is known in the prior art and as described below, since the crosslinking reaction occurs between the crosslinking agent and the polymer synthesized by anionic polymerization, the polymer must be active, or live, in whole or in part. The resulting material is easier to handle than a linear polymer, it also demonstrates a lower viscosity than linear polymer of similar molecular weight. In addition, it can be noted improvement in rheology, compatibility and polarity multiresolution polymers that gives them such an advantage as compatibility with a large number of surfaces. In addition, their surface activity, which makes the application useful for improving adhesion, compatibility, solubility and dispersibility. Functional groups present in multiresolution polymers can be preferably used to modify the surface properties defunctionalizing polymers. When mixing multiresolution polymers of the present invention with defunctionalization polymers, functional groups that are distinct in nature from defunctionalizing polymer are separated and migrate to the surface of the mixture, thereby changing the properties of the surface is resti. In the second aspect of the present document provides functionalityand multiresolution polymers obtained from the polymers according to the first aspect of the present invention, such as polymers, which can be obtained by removing the protective groups (A-R1R2R3)mpresent on the functionalized multiresolution polymers, as well as functionalityand hydrogenated multiresolution polymers, characterized by the fact that they can be obtained by hydrogenation of any of the polymers according to the first aspect of the present invention, or polymers which can be obtained by removal of the protective groups as described in the second aspect of the present invention. In the third aspect of the present invention provides a method of obtaining any of the polymers described in the first and second aspects of the present invention, which includes the reaction of the polymers synthesized by anionic polymerization with cross-linking agent, and a method of obtaining a hydrogenated multiresolution polymers according to the first aspect, comprising the hydrogenation of functionalized multiresolution polymers at temperatures from 25°C to 150°C before removing the protective groups.

In the fourth aspect provides a method of obtaining a hydrogenated multiresolution polymers according to the second aspect,characterized in that it includes the hydrogenation of functionalized multiresolution polymers at temperatures from 25°C to 150°C after removal of the protective groups. In addition to the advantages according to the first and second aspects of the present invention, hydrogenated multiresolution polymers for the third and fourth aspects are materials that are resistant to heat, hydrolysis and ultraviolet radiation, which is necessary for applications requiring high thermal stability or exposure to a humid environment or atmosphere for the materials.

In the fifth aspect of the present invention provides a method of obtaining multiresolution polymers with removed the protective groups as described in the second aspect, characterized in that the protective group is removed by treatment with an acid, such as hydrochloric acid, acetic acid, p-toluensulfonate, ion-exchange resin Amberlyst® 15, as a rule, at the boiling temperature of the solvent for different multiresolution polymers, or by using other methods described by T.W. Greene and P.G.M. Wuts, Protective Groups in Organic Synthesis, Second edition, Wiley, New York, 1991.

In the sixth aspect of the present invention provides an adhesive composition that contains functionalized multicasualty polymer in the first and second aspects of the invention, characterized in that the reaction product with the holds from about 0.001 to about 5% by weight of a crosslinking agent to the total number of cross-linking agent and a polymer, synthesized by anionic polymerization, which are introduced into the reaction according to the first aspect.

In the seventh aspect of the present invention provides a reinforced material or a composite material, which includes a functionalized multicasualty polymer according to the first or second aspect of the invention, mixed with a reinforcing material or the material to be reinforced. Specified armorey material includes, but is not limited to, bitumen, adhesives, mixtures with other polymers and nanomaterials.

In the eighth aspect of the present invention provides modified bitumen, which contains bitumen, mixed with functionalized multiresolutional polymer according to the first or second aspects of the invention. Bitumen, which include the polymers according to the invention are characterized by good compatibility in the environment and good physical properties.

In the ninth aspect of the present invention provides a modified plastic, which includes plastic, mixed with functionalized multiresolutional polymer according to the first or second aspect of the invention, where the mixture contains from about 1 to about 40 percent by weight of functionalized multiresolutional polymer by total weight of functionalized multiresolutional polymer and plastics. P is liner according to the invention improves the physical properties of plastics, in particular the impact strength, compared with the original plastic.

Detailed description of the invention

The following describes preferred embodiments of the present invention. Typically, the number of reactive polymer chains synthesized by anionic polymerization, significantly higher moles than the number of cross-linking agent, which means that it is possible that not all chains are covalently linked with cross-linking agent, although preferably with cross-linking agent covalently bound from 1 to 30 polymer chains synthesized by anionic polymerization.

In a preferred embodiment, in functionalized multiresolution polymers of the formula Li-Qn-Z-T-(A-R1R2R3)mdescribed in the first aspect, T is an oxygen. In another preferred embodiment, in functionalized multiresolution polymers of the formula Li-Qn-Z-T-(A-R1R2R3)mdescribed in the first aspect, T is a nitrogen. These functional groups increase the surface activity, which makes the application useful, if it is preferable to improve adhesion, compatibility, solubility and dispersibility. In another embodiment, in functionalized multiresolution polymers of the formula Li-Qn-Z-T-(A-R1R2R3)mdescribed in the first aspect, T represents sulphur.

The number of required protective groups depends on the introduced functional groups. For example, if T represents oxygen or sulphur, m preferably represents 1, and if T is a nitrogen, m preferably represents 2.

As already mentioned in the first aspect, Z is a branched or unbranched hydrocarbon connecting group comprising from 3 to 25 carbon atoms. Useful for the synthesis of the polymers according to the invention the group Z is known in the prior art, preferably Z represents propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl pentadecyl, hexadecyl, heptadecyl or octadecyl.

R1, R2and R3group together And form a protective group. Protective groups for O, N or S is well known in the prior art. R1, R2and R3can be independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, penttila, isopentyl, neopentyl and tert-pentile. Generally, the preferred carbon protective groups, i.e., And preferably is a carbon (C), because such groups are, as a rule, are more dostupnymi cheap, but if Z represents oxygen (O), good results were obtained with protective groups on the basis of silicon (Si).

Useful for the present invention are synthesized by anionic polymerization of the polymers known in the prior art. Such synthesized by anionic polymerization of the polymers can undergo reactions limiting the growth of chains or binding assays with cross-linking agent. Anionic polymerization is a well-known method, in which polymerization of conjugated diolefins or other anionic polymerized monomers used initiators, such as organic initiators with alkaline metals. Anionic polymerization can be conducted as a continuous process, batch or semi-continuous. Obtained by anionic polymerization of the polymers is usually called "living polymers", as in each reaction stage of the interaction with the monomer forms a carbanion, which allows the polymer to continue to grow until complete absorption of the monomers. The polymers remain active even after absorbing monomers, and they continue to respond and grow when adding additional monomers. Detailed description of the methodology is given in "Anionic Polymerization: Principles and Practical Applications, Hsieh, H.L., Quirk, Roderic P., Marcel Dekker Inc, New York, 1996, descriptions of which are incorporated here by reference. The method of anionic polymerization CCA is i.i.d. attractive to obtain block copolymers with well-defined structures. Received this methodology polymers depending on the functional groups used to produce the initiator or cross-linking agents can be a radial, linear or branched polymers.

Anionic polymerization in order to avoid premature termination of the initiator or polymer chains usually carried out in a nonpolar hydrocarbon solvents at moderate temperatures, in a vacuum or in an atmosphere of inert gas with the use of reagents of high purity. The polymers can be homopolymers or copolymers, including random copolymers and block copolymers. Commercial polymers synthesized by anionic polymerization, or anionic polymerized commercial polymers include thermoplastic, elastomeric and thermoplastic elastomeric polymers. Synthesized by anionic polymerization of polymers for use in the present invention have an average molecular weight at the peak of the distribution from about 3,000 g/mol to about 400,000 g/mol. This includes synthesized by anionic polymerization of polymers with a molecular weight of from about 20,000 g/mol to about 200,000 g/mol, although the invention is not limited to polymers that fall within the specified ranges of molecular weight. In the present invention the molecular weight sinteziruet the x anion polymerization and polymer molecular weight functionalized multiresolution polymers belong to the molecular weight at the peak of the distribution, Mp.

Suitable for obtaining the above synthesized by anionic polymerization of conjugated polymers diolefine (or diene) known in the art and include, but are not limited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene and myrcenol.

Examples of anionic polymerized alkenyl aromatic monomers include, but are not limited to, styrene, alpha-methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha methylvinylketone, 2-alpha methylvinylketone, 1,2-diphenyl-4-methylhexane and mixtures thereof and their alkyl, cycloalkyl, aryl and alcylaryl derivatives, where the total number of carbon atoms in the substituted component, as a rule, does not exceed 18. Examples of the latter compounds include 3-methylsterol, 3,5-dietitian, 2-ethyl-4-benzylthio, 4-fenestral, 4-p-cholersterol, 4-(tert-butyl)-styrene, 2,4-dividercolor and 4,5-dimethyl-1-vinylnaphthalene.

Other anionic polymer clay is ishemia monomers include acrylamide, Acrylonitrile, nitrobutane, vinyl isocyanates, anhydrides, methacrylates, acrylates, carbodiimide, lactones, lactams, cyclic siloxanes, and ethylene.

Of anionic polymerized monomers can be obtained by a variety of polymers/copolymers that include, but are not limited to polystyrene, polybutadiene, polyisoprene, polyethers, polyacetylene and polyphenoloxidase. These polymers can also be a elastomers and thermoplastic elastomers derived from block copolymers, gradient or random copolymers of styrene (S), butadiene (b) and isoprene (I) of variable size and number of blocks. Examples of such elastomers and thermoplastic elastomers include block copolymers SB, SI, SBR, (SB)mS (where m is an integer), SBS, SIS, BSB, ISI, as well as their hydrogenated and partially hydrogenated analogs, including SEBS, SEB, SEP and others. As an illustration, examples synthesized by anionic polymerization of polymers suitable for use as a modifier of bitumen and adhesives include linear elastomers obtained by copolymerization of at least one alkenylphenol aromatic monomer, and at least one conjugated diene monomer.

In a preferred embodiment, functionalized multicasualty polymer characterized by the fact that sin is airway anionic polymerization of the polymer synthesized from conjugated diene monomers and alkenyl monomers, where the diene portion is characterized by an approximate molar content of 1,2-structures from 8 to 80%.

In some examples, the linear elastomers molar proportion alkenyl aromatic monomers relative to paired the diene monomers is preferably from about 0.1 to about 1.0, preferably from about 0.2 to about 0.5 and more preferably from about 0.3 to about 0.4. In the preferred method of polymerization of functionalized multicasualty polymer described in the first aspect, characterized by the fact that synthesized by anionic polymerization of the polymer obtained from alkenyl aromatic monomers, conjugated diene monomers, or a mixture thereof. For example, for the application of the polymers in the mixture with plastic, the authors of the present invention unexpectedly found that good results can be obtained if the polymers of polystyrene.

As an example, the specified preferred method of polymerization synthesized by anionic polymerization of the polymer obtained from alkenyl aromatic monomers and conjugated diene monomers in the molar proportion of an aromatic vinyl monomer relative to paired the diene monomers from about 0.05 to about 1.0.

Preferably, functionalityand multiresolution polymers contain at least one polymer clay is, selected from the group consisting of polystyrene, polybutadiene, polyisoprene and statistical copolymers, namely block copolymers or gradient copolymers derived from monomers selected from the group consisting of styrene, butadiene and isoprene. The molecular weight of the polymer chains according to the invention can be adjusted depending on the needs due to changes in the number of polymerized monomers (n), but usually the chain of the polymer have a molecular weight at the peak of the distribution of Mpfrom about 3,000 to about 300,000 g/mol. Preferably, Mpchains of the polymer ranges from 20000 g/mol to 200,000 g/mol.

The molecular weight synthesized by anionic polymerization of the polymers of the present invention is conveniently measured by gel permeation chromatography (GPC) calibration setup using a standard calibration curve. Calibration is performed by using polymers of known molecular weight, however, they must have the same molecular structure and the same composition as that of the investigated polymers. Synthesized by anionic polymerization of polymers significantly monodisperse (srednevekovaja molecular weight / Brednikova molecular weight is close to unity), so as the molecular weight of the polymer, it is advisable to specify the molecular weight at the peak p is opredeleniya M p. In addition, the molecular weight described multiresolution polymers correlates with the molecular weight at the peak of the distribution of cross-linked chains. Determination of the degree of crosslinking of branched polymers, i.e. the determination of the number of covalently linked chains in multiresolution polymers, defined relative molecular mass multiresolution polymers at the peak of the distribution to the molecular weight of the chain at the peak of the distribution.

Synthesized by anionic polymerization, the polymer may contain alkeneamine aromatic monomers, conjugated diene monomers or mixtures thereof, which are anionic polymerized. In one embodiment, the amount of conjugated diene monomers ranges from 8 to 80% by moles.

Examples of initiators for functionalized and protected synthesized by anionic polymerization of the polymers of formula (II) Li-Z-T-(A-R1R2R3)minclude, but are not limited to

tert-alkoxy-alkyllithium,

omega-(tert-alkoxy)-1-alkyllithium, for example, 3-(1,1-dimethylamine)-1-properities and 3-(tert-butyldimethylsilyloxy)-1-properities,

tert-alkylthio-alkyllithium,

omega-(tert-alkylthio)-1-alkyllithium, for example, 3 -(1,1-dimethylethyl)-1-properities,

omega-(tert-butoxydiglycol)-1-alkyllithiums,

omega-(tert-butoxydiglycol)-1-alkyllithiums,

p> (dialkylamino)-1-alkyllithium,

omega(dialkylamino)-1-alkyllithium, for example, 3-(dimethylamino)-1-properities, (bis-tert-alkylsilane)-1-alkyllithiums,

omega-(bis-tert-alkylsilane)-1-alkyllithium, for example, 3-(di-tert-butyldimethylsilyloxy)-1-properities.

Additional examples of substances that can be used in the present invention include, but are not limited to:

3-(1,1-dimethylamine)-1-properities,

3-(1,1-dimethylmethoxy)-2-methyl-1-properities,

3-(1,1-dimethylmethoxy)-2,2-dimethyl-1-properities,

4-(1,1-dimethylamine)-1-butyllithium,

5-(1,1-dimethylamine)-1-intelliteam,

6-(1,1-dimethylamine)-1-hexyllithium,

8-(1,1-dimethylamine)-1-ostilities,

3-(1,1-DIMETHYLPROPANE)-1-properities,

3-(1,1-DIMETHYLPROPANE)-2-methyl-1-properities,

3-(1,1-DIMETHYLPROPANE)-2,2-dimethyl-1-properities,

4-(1,1-DIMETHYLPROPANE)-1-butyllithium,

5-(1,1-DIMETHYLPROPANE)-1-intelliteam,

6-(1,1-DIMETHYLPROPANE)-1-hexyllithium,

8-(1,1-DIMETHYLPROPANE)-1-ostilities,

3-(t-butyldimethylsilyloxy)-1-properities,

3-(t-butyldimethylsilyloxy)-2-methyl-1-properities,

3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-properities,

4-(t-butyldimethylsilyloxy)-1-butyllithium,

5-(t-butyldimethylsilyloxy)-1-intelliteam,

6-(t-butyldimethylsilyloxy)-1-hexyllithium,

8-(t-butyldimethylsilyloxy)-1-OK what Illicium,

3-(trimethylsilyloxy)-2,2-dimethyl-1-properities,

3-(dimethylamino)-1-properities,

3-(dimethylamino)-2-methyl-1-properities,

3-(dimethylamino)-2,2-dimethyl-1-properities,

4-(dimethylamino)-1-butyllithium,

5-(dimethylamino)-1-intelliteam,

6-(dimethylamino)-1-hexyllithium,

8-(dimethylamino)-1-properities,

3-(hexamethyleneimino)-1-properities,

4-(hexamethyleneimino)-1-utility,

5-(hexamethyleneimino)-1-intelliteam,

6-(hexamethyleneimino)-1-hexyllithium,

8-(hexamethyleneimino)-1-ostilities,

3-(t-butyldimethylsilyl)-1-properities,

3-(t-butyldimethylsilyl)-2-methyl-1-properities,

3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-properities,

4-(t-butyldimethylsilyl)-1-butyllithium,

6-(t-butyldimethylsilyl)-1-hexyllithium,

3-(trimethylsilyl)-2,2-dimethyl-1-properities,

3-(1,1-dimethylethyl)-1-properities,

3-(1,1-dimethylethyl)-2-methyl-1-properities,

3-(1,1-dimethylethyl)-2,2-dimethyl-1-properities,

4-(1,1-dimethylethyl)-1-butyllithium,

5-(1,1-dimethylethyl)-1-intelliteam,

6 (1,1-dimethylethyl)-1-hexyllithium,

8-(1,1-dimethylethyl)-1-ostilities,

3-(1,1-dimethylpropyl)-1-properities,

3-(1,1-dimethylpropyl)-2-methyl-1-properities,

3-(1,1-dimethylpropyl)-2,2-dimethyl-1-properities,

4-(1,1-dimethylpropyl)-1-butyllithium,

5-(1,1-dimethylpropyl is)-1-intelliteam,

6-(1,1-dimethylpropyl)-1-hexyllithium,

8-(1,1-dimethylpropyl)-1-ostilities.

The compounds of formula (II) Li-Z-T-(A-R1R2R3)mcan be obtained, if this formula represents a compound of the formula Li-Z-O-C-R1R2R3Li-Z-O-Si-R1R2R3Li-Z-N(C-R1R2R3)2Li-Z-N(C-R1R2R3)2Li-Z-S-C-R1R2R3and Li-Z-S-Si-R1R2R3the reaction of the corresponding halogenoalkanes, for example, Cl-Z-T-(A-R1R2R3)mand Br-Z-T-(A-R1R2R3)mwith metallic lithium in an inert hydrocarbon solvent at a temperature of its boiling point.

Tertiary amines 1-halogenoalkane, useful for, for example, Li-Z-N-(A - R1R2R3)2compounds of the present invention, are compounds with the following structure:

X-Z-N-(A-R1R2R3)2

and

where z is an integer from 1 to 7

and X represents a halogen, preferably CL and Br.

Examples of tertiary amines 1 halogenoalkanes include, but are not limited to:

3-(N,N-dimethylamino)-1-propyl-halide,

3-(N,N-dimethylamino)-2-methyl-1-propyl-halide,

3-(N,N-dimethylamino)-2,2-dimethyl-1-propyl-halide,

4-(N,N-dimethylamine is)-1-butyl halide,

5-(N,N-dimethylamino)-1-pentyl a halide,

6-(N,N-dimethylamino)-1-hexyl-halide,

3 (N,N-diethylamino)-1-propyl-halide,

3-(N,N-diethylamino)-2-methyl-1-propyl-halide,

3-(N,N-diethylamino)-2,2-dimethyl-1-propyl-halide,

4-(N,N-diethylamino)-1-butyl halide,

5-(N,N-diethylamino)-1-pentyl a halide,

6-(N,N-diethylamino)-1-hexyl-halide,

3-(N-ethyl-N-methylamino)-1-propyl-halide,

3-(N-ethyl-N-methylamino)-2-methyl-1-propyl-halide,

3-(N-ethyl-N-methylamino)-2,2-dimethyl-1-propyl-halide,

4-(N-ethyl-N-methylamino)-1-butyl halide,

5-(N-ethyl-N-methylamino)-1-pentyl a halide,

6-(N-ethyl-N-methylamino)-1-hexyl-halide,

3-(piperidino)-1-propyl-halide,

3-(piperidino)-2-methyl-1-propyl-halide,

3-(piperidino)-2,2-dimethyl-1-propyl-halide,

4-(piperidino)-1-butyl halide,

5-(piperidino)-1-pentyl a halide,

6-(piperidino)-1-hexyl-halide,

3-(pyrrolidino)-1-propyl-halide,

3-(pyrrolidino)-2-methyl-1-propyl-halide,

3-(pyrrolidino)-2,2-dimethyl-1-propyl-halide,

4-(pyrrolidino)-1-butyl halide,

5-(pyrrolidino)-1-pentyl a halide,

6-(pyrrolidino)-1-hexyl-halide,

3-(hexamethyleneimino)-1-propyl-halide,

3-(hexamethyleneimino)-2-methyl-1-propyl-halide,

3-(hexamethyleneimino)-2,2-dimethyl-1-propyl g is logarithm,

4-(hexamethyleneimino)-1-butyl halide,

5-(hexamethyleneimino)-1-pentyl a halide,

6-(hexamethyleneimino)-1-hexyl-halide,

3-(N-isopropyl-N-methyl)-1-propyl-halide,

2-(N-isopropyl-N-methyl)-2-methyl-1-propyl-halide,

3-(N-isopropyl-N-methyl)-2,2-dimethyl-1-propyl-halide,

and 4-(N-isopropyl-N-methyl)-1-butyl halide.

Halogen selected from chlorine and bromine.

Omega-hydroxy-protected halogenoalkane to the present invention, but are not limited to:

3-(1,1-dimethylamine)-1-propyl-halide,

3-(1,1-dimethylmethoxy)-2-methyl-1-propyl-halide,

3-(1,1-dimethylmethoxy)-2,2-dimethyl-1-propyl-halide,

4-(1,1-dimethylamine)-1-butyl halide,

5-(1,1-dimethylamine)-1-pentyl a halide,

6-(1,1-dimethylamine)-1-hexyl-halide,

8-(1,1-dimethylamine)-1-octyl a halide,

3-(1,1-DIMETHYLPROPANE)-1-propyl-halide,

3-(1,1-DIMETHYLPROPANE)-2-methyl-1-propyl-halide,

3-(1,1-DIMETHYLPROPANE)-2,2-dimethyl-1-propyl-halide,

4-(1,1-DIMETHYLPROPANE)-1-butyl-halide,

5-(1,1-DIMETHYLPROPANE)-1-pentyl a halide,

6-(1,1-DIMETHYLPROPANE)-1-hexyl-halide,

8-(1,1-DIMETHYLPROPANE)-1-octyl a halide,

4-(methoxy)-1-butyl halide,

4-(ethoxy)-1-butyl halide,

4-(propyloxy)-1-butyl halide,

4-(1-methylethoxy)-1-butyl halide,

3-(Triveni is methoxy)-2,2-dimethyl-1-propyl-halide,

4-(triphenylmethane)-1-butyl halide,

3-[3-(dimethylamino)-1-propyloxy]-1-propyl-halide,

3-[2-(dimethylamino)-1-ethoxy]-1-propyl-halide,

3 -[2-(diethylamino)-1-ethoxy]-1-propyl-halide,

3-[2-(isopropyl) amino)-1-ethoxy]-1-propyl-halide,

3-[2-(1-piperidine)-1-ethoxy]-1-propyl-halide,

3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyl-halide,

4-[3-(dimethylamino)-1-propyloxy]-1-butyl halide,

6-[2-(1-piperidine)-1-ethoxy]-1-hexyl-halide,

3-[2-(methoxy)-1-ethoxy]-1-propyl-halide,

3-[2-(ethoxy)-1-ethoxy]-1-propyl-halide,

(methoxy)-1-ethoxy-1-butyl halide,

5-[2-(ethoxy)-1-ethoxy]-1-pentyl a halide,

3-[3-(methylthio)-1-propyloxy]-1-propyl-halide,

3-[4-(methylthio)-1-Butylochka]-1-propyl-halide,

3-(methylthiomethyl)-1-propyl-halide,

6-[3-(methylthio)-1-propyloxy]-1-hexyl-halide,

3-[4-(methoxy)-benzyloxy]-1-propyl-halide,

3-[4-(1,1-dimethylmethoxy)-benzyloxy]-1-propyl-halide,

3-[2,4-(dimethoxy)-benzyloxy]-1-propyl-halide,

8-[4-(methoxy)-benzyloxy]-1-octyl a halide,

4-[4-(methylthio)-benzyloxy]-1-butyl halide,

3-[4-dimethylamino)-benzyloxy]-1-propyl-halide,

6-[4-(dimethylamino)-benzyloxy]-1-hexyl-halide,

5-(triphenylmethane)-1-pentyl a halide,

6-(triphenylmethane)-1-hexyl-halide,

8-(what reptilelike)-1-octyl a halide,

3-(t-butyldimethylsilyloxy)-1-propyl-halide,

3-(t-butyldimethylsilyloxy)-2-methyl-1-propyl-halide,

3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyl-halide,

4-(t-butyldimethylsilyloxy)-1-butyl halide,

5-(t-butyldimethylsilyloxy)-1-pentyl a halide,

6-(t-butyldimethylsilyloxy)-1-hexyl-halide,

8-(t-butyldimethylsilyloxy)-1-octyl a halide,

3-(t-butyldiphenylsilyl)-1-propyl-halide,

3-(t-butyldiphenylsilyl)-2-methyl-1-propyl-halide,

3-(t-butyldiphenylsilyl)-2,2-dimethyl-1-propyl-halide,

6-(t-butyldimethylsilyloxy)-1-hexyl-halide,

and 3-(trimethylsilyloxy)-2,2-dimethyl-1-propyl-halide.

Halogen selected from chlorine and bromine.

These omega-hydroxy-protected halogenoalkane can be obtained by methods described A.Alexaquis, .Gardette, S.Colin, Tetrahedron Letters, 29, 1988, 2951. .Figadere, X.Franck, A.Cave, Tetrahedron Letters, 34, 1993, 5893, J.Almena, F.Foubelo, M.Yus, Tetrahedron, 51, 1995, 11883. T.Ferrari, P.Vogel, SYNLETT, 1991, 233.

Omega-thio-protected halogenoalkane useful for the present invention include, but are not limited to:

3-(methylthio)-1-propyl-halide,

3-(methylthio)-2-methyl-1-propyl-halide,

3-(methylthio)-2,2-dimethyl-1-propyl-halide,

4-(methylthio)-1-butyl halide,

5-(methylthio)-1-pentyl a halide,

6-(methylthio)-1-hexyl-halide,

8-(Matilde is)-1-octyl a halide,

3-(methoxymethyl)-1-propyl-halide,

3-(methoxymethyl)-2-methyl-1-propyl-halide,

3-(methoxymethyl)-2,2-dimethyl-1-propyl-halide,

4-(methoxymethyl)-1-butyl halide,

5-(methoxymethyl)-1-pentyl a halide,

6-(methoxymethyl)-1-hexyl-halide,

8-(methoxymethyl)-1-octyl a halide,

3-(1,1-dimethylethyl)-1-propyl-halide,

3-(1,1-dimethylethyl)-2-methyl-propyl halide,

3-(1,1-dimethylethyl)-2,2-dimethyl-1-propyl-halide,

4-(1,1-dimethylethyl)-1-butyl halide,

5-(1,1-dimethylethyl)-1-pentyl a halide,

6-(1,1-dimethylethyl)-1-hexyl-halide,

8-(1,1-dimethylethyl)-1-octyl a halide,

3-(11-dimethylpropyl)-1-propyl-halide,

3-(1,1-dimethylpropyl)-2-methyl-1-propyl-halide,

3-(1,1-dimethylpropyl)-2,2-dimethyl-1-propyl-halide,

4-(1,1-dimethylpropyl)-1-butyl halide,

5-(1,1-dimethylpropyl)-1-pentyl a halide,

6-(1,1-dimethylpropyl)-1-hexyl-halide,

8-(1,1-dimethylpropyl)-1-octyl a halide,

3-(cyclopentyl)-1-propyl-halide,

3-(cyclopentyl)-2-methyl-1-propyl-halide,

3-(cyclopentyl)-2,2-dimethyl-1-propyl-halide,

4-(cyclopentyl)-1-butyl halide,

5-(cyclopentyl)-1-pentyl a halide,

6-(cyclopentyl)-1-hexyl-halide,

8-(cyclopentyl the IO)-1-octyl a halide,

3-(cyclohexylthio)-1-propyl-halide,

3-(cyclohexylthio)-2-methyl-1-propyl-halide,

3-(cyclohexylthio)-2,2-dimethyl-1-propyl-halide,

4-(cyclohexylthio)-1-butyl halide,

5-(cyclohexylthio)-1-pentyl a halide,

6-(cyclohexylthio)-1-hexyl-halide,

8-(cyclohexylthio)-1-octyl a halide,

3-(t-butyldimethylsilyl)-1-propyl-halide,

3-(t-butyldimethylsilyl)-2-methyl-1-propyl-halide,

3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyl-halide,

3-(t-butyldimethylsilyl)-2-methyl-1-propyl-halide,

4-(t-butyldimethylsilyl)-1-butyl halide,

6-(t-butyldimethylsilyl)-1-hexyl-halide

and 3-(trimethylsilyl)-2,2-dimethyl-1-propyl-halide.

Halogen selected from chlorine and bromine.

These omega-thio-protected halogenoalkane can be obtained by methods described Franck, A.Cave, Tetrahedron Letters, 34, 1993, 5893, J.Almena, F.Foubelo, M.Yus, Tetrahedron, 51, 1995, 11883, D.F.Taberb Y.Wang, J.Org, Chem., 58, 1993, 6470, F.D.Tosteb I.W.J.Still, Synlett, 1995, 159 and in U.S. patent No. 5493044. As mentioned earlier, not all polymer chains synthesized by anionic polymerization, covalently linked with a crosslinking agent. Share-linked chains can vary from about 2 to about 98% by weight, preferably with cross-linking agent covalently bound from 1 to 30 circuits synthesized by anionic polymerization of the polymer. Predpochtite is) the amount of added cross-linking agent such that the molar ratio synthesized by anionic polymerization of polymer to crosslinking agent is from 1:1 to 30:1.

Synthesized by anionic polymerization, the polymer may have a molecular weight at the peak of the distribution from about 20,000 to about 500,000 g/mol. In another embodiment of the first aspect of the invention functionalized multicasualty polymer characterized by the fact that it has the molecular weight at the peak of the distribution from 5000 to 2000000 g/mol.

Typically, the crosslinking agent is present in low regard, for this reason, in the preferred embodiment, the weight of a crosslinking agent ranges from 0.001 to 5% on the total amount of cross-linking agent and synthesized by anionic polymerization of the polymer in the reaction.

Preferred crosslinking agent of the present invention is an oligomer obtained by radical polymerization of at least one monomer selected from the group consisting of alkenyl aromatic monomers, functionalized epoxy group of the acrylic monomers and mixtures thereof, and at least one monomer selected from the group consisting of alkenyl aromatic monomers, functionalized epoxy group of acrylic monomers, functionalized anhydrite group acrylic is s monomers, functionalized ester group of the acrylic monomers, functionalized with a carboxyl group of acrylic monomers and any mixtures thereof, where the crosslinking agent is srednecenovogo molecular weight of from about 500 to about 10,000 g/mol and srednevekovoy molecular weight of from about 1,000 to about 20,000 g/mol. Srednevekovoy molecular weight and srednecenovogo molecular weight determined using gel permeation chromatography, as described above, but in this case, use the standard polystyrene samples. There are commercially available cross-linking agents, for example, ADR-4318® from BASF. Preferred as cross-linking agents oligomers contain from about 1 to about 60% by moles functionalized epoxy group or functionalized with a carboxyl group of acrylic monomers.

Other preferred crosslinking agents include divinylbenzene or multi-functional CHLOROSILANES. In another example, can also be used mixtures of the preferred cross-linking agents.

All the preferred options of the first aspect of the invention is valid for the second aspect of the invention.

Methods of obtaining functionalized multiresolution polymers in the first and second aspects and preferred embodiments of the present invention known to specialists in this about the Asti, although the preferred variants of the methods of synthesis of these polymers is shown below.

The preferred option includes a reaction synthesized by anionic polymerization of polymers with cross-linking agent. The crosslinking reaction is preferably carried out in the same reaction mixture, where the synthesis synthesized by anionic polymerization of the polymer.

Preferably synthesized by anionic polymerization of the polymer synthesized in the first stage of the reaction, after which its interaction with cross-linking agent is performed on the second stage of the reaction.

In another embodiment, a method of polymerization involves the polymerization of monomers synthesized by anionic polymerization of the polymer, adding a sufficient amount of agent termination for inactivation of biological circuits synthesized by anionic polymerization of the polymer and the reaction of at least some part of the living chains with cross-linking agent.

In another preferred embodiment, the proportion of cross-linking agent against synthesized by anionic polymerization of the polymer may range from 0.001 to 5% by weight. Preferably, the average number of polymer chains synthesized by anionic polymerization, which react with cross-linking agent is from about 2 to about 30.

This method of polymerization according to the previous aspects, preferably x is specified, however, from 2 to 90% by moles synthesized by anionic polymerization of the polymer reacts stitching, preferably from 20 to 60% by moles.

Examples of methods of hydrogenation, useful for the present invention are disclosed in U.S. patent 4970254, U.S. patent 5166277, U.S. patent 5393843, U.S. patent 5496898 and U.S. patent 5583185. Hydrogenation of functionalized multiresolution polymers can be carried out in situ in the reaction medium, such as hexane, cyclohexane or heptane. For example, the solution is in contact with gaseous hydrogen in the presence of a catalyst, such as Nickel, titanium catalyst, etc. Hydrogenation generally takes place at temperatures from 25°C to 150°C at a hydrogen pressure of 0.5 ATM to 20 ATM. For the hydrogenation process can be monitored using infrared spectroscopy (IR) or nuclear magnetic resonance (NMR). The hydrogenation reaction is conducted to recover at least 85% of unsaturated bonds synthesized by anionic polymerization chains, preferably, prior to hydrogenation, at least 90% of unsaturated bonds, more preferably, the process continues to hydrogenation, at least 99% of unsaturated bonds. The stage of removing the protective group can be performed before or after the optional hydrogenation of unsaturated multiresolution polymers. For example, is to remove tert-alkyl groups, the protected polymer is mixed with ion exchange resins, such as Amberlyst® 15, and is heated to a high temperature, for example 150°C., or the boiling point of the solvent (cyclohexane) to complete the process of removing the protective groups. In addition, tert-alkyl protective group can also be removed by reaction of the polymer with triperoxonane acid or p-toluensulfonate. Additional ways to remove tert-alkyl protective groups can be found in T.W.Greene, P.G.M.Wuts, Protective groups in Organic Synthesis, Second Edition, Wiley, New York, 1991, c.41. Tert-butyldimethylsilyloxy group can be removed by treatment functionalized multi-branched polymer acids such as hydrochloric acid, acetic acid, p-toluensulfonate, Dowes 50W-X8, or sources of fluoride ions, for example, Tetra-N-butylammonium fluoride, potassium fluoride and 18-crown-6 or a complex of pyridine-hydrofluoric acid. Additional ways to remove tert-butyldimethylsilyloxy group can be found T.W.Greene, P.G.M.Wuts, Protective groups in Organic Synthesis, Second Edition, Wiley, New York, 1991, c.80-83. Functionalityand multiresolution polymers, unsaturated or hydrogenated, purified by conventional means, such as removal of the catalyst by washing with an aqueous solution of acid, with subsequent removal of the solvent or by precipitation of the polymer. Suddenly, improve properties of functionalized multiresolution polymers with removed protective groups t is the train in many cases are protected functionalized multiresolution polymers, especially for applications such as adhesives, bitumen modification of plastics. This allows, for example, be applied directly protected polymers in the compositions of hot-melt adhesives without the need for removing the protective groups, which entails the reduction of the duration of the process and reducing the cost of production. Not wishing to be bound by any theory, the inventors suggest that this behavior may be due to the fact that the polymers lose their protective group during the process of obtaining various types of compositions.

The present invention is not limited only to new polymers and methods of their synthesis, and includes its composition. For example, functionalityand multiresolution polymers in the first and second aspects of the invention may be incorporated in the adhesive composition. Preferably, the polymer that is contained in these adhesive compositions, characterized by the fact that the reaction mixture contains from about 0.001 to about 5% by weight of a crosslinking agent to the total number entering the reaction of a crosslinking agent and synthesized by anionic polymerization of the polymer. Adhesives, especially hot melt adhesives, obtained using the polymers of the present invention, exhibit improved properties of strength, tackiness and strength in shear is about than known in the prior art hot melt adhesives. The adhesive composition may contain at least one additive selected from the group consisting of enhancing the adhesiveness of the resin, stabilizers, plasticizers and antioxidants. In some of these applications, about 15-30, and more preferably 18 to 25 weight parts multiresolutional polymer of the present invention is mixed with other components conventional adhesive compositions, such as substances that enhance adhesion, stabilizers, plasticizers and antioxidants, to give the specified adhesive compositions of improved properties in comparison with adhesives obtained in the same song using the same type of polymer, but without the introduction of functional groups, protected or unprotected, in the limit positions and/or hydrogenation of unsaturated chains. Examples of suitable improves adhesion substances include resin with high and low softening temperature that is compatible with the polymer. These include hydrogenated resin, kanifolnye esters, polyterpene resins, terpene phenolic resins and coumarone-indene resin. In some illustrative embodiments, the amount of thickening resins in the compositions ranges from about 45 to about 65% by weight. Plasticizers commonly known as oil-fillers include mineral oils, paraffinic oils and naphthenic oils. In some Illustra the positive variation amount of the plasticizer in the composition is from about 15 to about 30% by weight. For inhibition of the oxidation processes taking place under the influence of heat and ultraviolet rays, can be used antioxidants are usually added to the adhesive composition in an amount of from about 0.05 to about 3% by weight. Examples of antioxidants include phenolic compounds and thiol compounds. In a preferred embodiment, the composition includes from 15 to 30% by weight increases the adhesiveness of the resin, from about 15 to about 30 percent by weight of a plasticizer and from about 0.05 to about 2 percent by weight of antioxidants. In a preferred embodiment, the adhesive composition can be used in various applications, for example, in adhesives for packaging, labels, masking tape, construction and as pressure-sensitive adhesives for use in the manufacture of disposable elastic products. In addition, the polymers of the present invention is useful for the reinforcement materials and the production of composite materials, which means that these polymers can be mixed with a reinforcing material or the material to be reinforced. The materials to be reinforced, can be selected from the group consisting of bitumen, plastic and the material of the tire. Good results were obtained when the reinforcement of plastics selected from polyamides, polyurethanes, polyesters, polysulfones, polyetherketones, poly is verificationof, polyetherimides, polycarbonates, polyesters, polystyrene, and their copolymers. Reinforced material or a compound useful for the manufacture of products, which can be an extruded product, a die cast product, molded under pressure, the product or bus. Another aspect is modified bitumen, which contains bitumen, mixed with functionalized multiresolutional polymer according to any one of the first and second aspects. Bitumen may contain from about 1 to about 25% by weight of functionalized multiresolutional polymer by total weight of the bitumen and functionalized multiresolutional polymer. Preferably, modified bitumen contains from about 5 to about 20% by weight of functionalized multiresolutional polymer. These betamovie mixture, modified functionalized multidisiciplinary polymers can be used in such applications as road construction, bitumen membrane, and the like. In addition, the polymers of the present invention are useful for the modification of plastics, preferably with the use of mixtures which contain from about 1 to about 40 percent by weight of functionalized multiresolutional polymer by total weight of functionalized multiresolutional polymer and PLA is MASSY. The plastic material preferably contains at least one polymer selected from the group consisting of polystyrene, polybutadiene, polyisoprene and statistical copolymers, block copolymers or gradient copolymers obtained from monomers selected from the group consisting of styrene, butadiene, isoprene, and which have an average molecular weight at the peak of the distribution from about 3,000 to about 300,000 g/mol. Functionalityand multiresolution polymers, mixed with plastics, preferably characterized by the fact that the reaction product contains from about 0.1 to about 8% by weight of a crosslinking agent to the total number of functionalized multiresolutional polymer. The polymers of the present invention for mixing with plastics preferably contain polystyrene. The polymers according to the invention and plastics can be mixed in a wide range of proportions, but preferred is a content of from 1 to 20% by weight of functionalized multiresolutional polymer by total weight of functionalized multiresolutional polymer and plastics. The polymers can be mixed with a wide variety of plastics, but preferably plastic selected from the group consisting of polyamides, polyurethanes, polyesters, polysulfones, polyetherketones, polyetheretherketones, polimi is s, polyetherimides, polycarbonates, polyesters, polystyrene, and their copolymers. Furthermore, this mixed with the polymer according to the invention, the plastic can be mixed with other plastics that you want to modify, the proportion of modified plastics with functionalized multiresolutional polymer in a mixture of plastics can vary from 1 to 40% by weight of the total weight of the functionalized plastics and multiresolutional polymer.

In the Description of the present invention and the claims the word "contains" and its variants is not intended to exclude other technical characteristics, additives, components or steps. For specialists in this area other objects, advantages and features of the invention should be combined partly from the description and partly from the practice of the invention. The following Examples are given for illustrative purposes and do not limit the present invention.

Examples

Synthesis of functionalized alcohol groups multiresolution polymers

Functionalityand BUT-groups (protected or removed from the protective groups) SB multiresolution copolymers synthesized in a 20 l Buchi reactor using 3-(t-butyldimethylsilyloxy)-1-propylite as an initiator, trade name PFI-103, available from FMC. In all cases the Ah used 6500 g of cyclohexane, 1130 g of a solution of styrene in cyclohexane (24% by weight), 50 ml of THF (except solutions of vinyl polymers, which was added 10 ml THF) and 46 ml PFI-103 in cyclohexane (15 mass%), the reaction was carried out at 65°C for 15 minutes, then added 610 g of 1,3-butadiene. After about 35 minutes the temperature was increased to 70°C and SB copolymer was made by adding 11 ml ADR-4318 in cyclohexane (20 mass%), the specified stage was carried out for 20 minutes. In the case of hydrogenated copolymers temperature was immediately increased to 90°C. and then was added 31 ml of a solution of metallocene titanium catalyst in THF/cyclohexane (0.2 M). Block copolymers, which should not be gidrirovanny, iactiveaware 23 ml BHT (10% by weight in cyclohexane). For comparison, were synthesized defunctionalization multiresolution SB copolymers. These defunctionalization copolymers were synthesized using the same procedure as functionalityand polymers, with the exception that instead of the PFI-103 into the reaction was added 48 ml of n-utility (2,6% by weight in cyclohexane).

After the stage of synthesis of some functionalized multiresolution SB copolymers with protected BUT groups were subjected to hydrolysis to obtain multiresolution polymers to remove the protective group and, functionalized BUT-groups. The above reaction was carried out in 10 l glass reactor, treating the polymer solutions of hydrochloric acid at a temperature of 80°C for 3 hours. The copolymer was treated with steam to remove the solvent and dried in a vacuum oven at a temperature of 80°C. For the determination of molecular weight, degree of branching and the percentage of crosslinking the copolymers was investigated by the method of gel permeation chromatography (THF as eluent, universal calibration curve)to determine the microstructure, composition and removing the protective groups of the copolymers were examined by the method1H-NMR.

Characteristics of branched copolymers are shown in Table 1.

Table 1
Characteristics multiresolution copolymer used in the adhesive compositions
SampleThe type of polymer1Mplinear
polymer2,
g/mol
Mpstitched
polymer3,
g/mol
Sewn product4, mass%The degree of crosslinking5All of styrene6, mass% The content of vinyl6, mass%Hydrogenation of6, mass%
S9618 C01 (standard)SBS-r medium
content
vinyl
47300426100369,032,213,3no data
N 18RO-SBS-r with the average content of vinyl4590044400050the 9.72725no data
N 18 dep7HO-SBS-r with the average content of vinyl4590044400050the 9.72725no data
N-17SBS-r with high
content
vinyl
43200397400509,236 36no data
N-10RO-SBS-r with high
the content of vinyl
445004659003710,530,438,4no data
N-09 dep7HO-SBS-r with a high content of vinyl4440047260040,110,631,939no data
H9618-11SEBS-r with high
content
vinyl
48500reset to 512,00051,510,630,13899
H9618-07RO-SEBS-r with a high content of vinyl5960058800044,99,930,238,499
H9618-15 RO-SEBS-r with a high content of vinyl431004397003710,232,438,698
H9618-06 dep7HO-SEBS-r
high
content
vinyl
53200520400to 43.19,832,447,897
1"r" refers to multiresolutional products.
2the molecular weight at the peak of the distribution copolymer SB, determined by the GPC method using the method of the universal calibration curve.
3the molecular weight at the peak of the distribution of the products of fusion, determined by the GPC method using the method of the universal calibration curve.
4the amount of product stapling (branched)obtained in percent by weight from GPC curves.
5the degree of crosslinking (degree of branching), obtained from the relation of Mpproduct stitching to Mplinear product.
6specified by1H-NMR, the content of vinyl groups, showing the content of the butadiene dep refers to the ACPs is the iMER to remove the protective groups.

Synthesis of functionalized tertiary amino group multiresolution polymers

Functionalityand tertiary amino group multiresolution SB copolymers synthesized in a 2 l Buchi reactor using 3-dimethylamino-1-propylite as an initiator, trade name AI-200. In all cases used a 723 g of cyclohexane, 180 ml of a solution of styrene in cyclohexane (24% by weight, the density 0,78), 3.7 g THF and 4.4 ml AI-200 in cyclohexane (11% by weight, a density of 0.8 g/ml, molar mass 229,3 g/mol), the reaction was carried out at 60°C for 15 minutes, then added 68 g of 1,3-butadiene. After about 40 minutes was added 0.8 ml, 1.3 ml or 1.8 ml of a crosslinking agent ADR-4318 (solution in cyclohexane, 20% by weight, a density of 0.79 g/ml) to obtain the molar ratio of crosslinking agent to initiator 0,04, of 0.07 and 0.1, respectively. Solutions of polymers iactiveaware of 4.7 ml BHT (10% by weight in cyclohexane).

For the determination of molecular weight, degree of branching and the percentage of crosslinking the copolymers was investigated by the method of gel permeation chromatography (THF as eluent, universal calibration curve)to determine the microstructure, composition and removing the protective groups of the copolymers were examined by the method1H-NMR.

Thus, there were obtained functionalityand multires ellenie copolymers with tertiary amino groups at the ends of the chain, their characteristics are shown in Table 2.

Table 2
Characteristics of functionalized tertiary amino group multiresolution copolymers
SampleADR-
4318/AI-
200,
mol/mol
Mp
linear
copolymer1,
g/mol
Mp
stitched
polymer2,
g/mol
Stitched
product3,
%
weight
Level
stitching4
Just
styrene5,
%
weight
Included
s
vinyl5,
%
weight
m-SB-0,045780048440014,58,433,238,0
Amin 1
m-SB-0,075850051690028,98,832,837,6
Amin 2
m-SB-0,15950050980037,58,632,839,1
Amin 3
1the molecular weight at the peak of the distribution copolymer SB, determined by the GPC method using the method of the universal calibration curve.
2the molecular weight at the peak of the distribution of the products of fusion, determined by the GPC method with POM is the method using a universal calibration curve.
3the amount of product stapling (branched)obtained in percent by weight from GPC curves.
4the degree of crosslinking (degree of branching), obtained from the relation of Mpproduct stitching to Mplinear product.
5specified by1H-NMR, the content of vinyl groups, showing the content of the butadiene

The results show that the number of products of crosslinking increases with increasing amount of added ADR-4318, while the degree of crosslinking remains almost constant. Thus, the degree of crosslinking depends on the initial size of the chain SB copolymer, while the percentage of cross-linked product depends on the amount of added cross-linking agent. Characteristics ADR-4318.

tr>
CompositionADR-4318
Styrene, mass%11,88
MMA, mass%1,01
JENA, mass%at 79.67
GMA, mass%7,44
Physical propertiesADR-4318
Mn (GPC)g/mol2,600
Mw (GPC)g/mol7,200
Mw/Mn2,7
The viscosity at 25°C (CP)28,500
Tg,°C-61,0
EEW (g/mol)2,017
Fn (Mn/EEW)1,31

The composition of the hot melt resin Escorez 5380

Samples multiresolution hydrogenated copolymers (SEBS-r with a high content of vinyl, RO-SEBS-r with a high content of vinyl and HO-SEBS-r with high vinyl content) was investigated using the adhesive compositions shown in Table 3. Oil Primol 352 refers to naphthenic oils, resin Escorez 5380 is hydrocarbonate cycloaliphatic resin, and the I-1010 is an antioxidant.

td align="center"> 120
Table 3
The composition used to produce hot-melted resin with the resin Escorez 5380
Phr1
The polymer sample100
Primol 352
Escorez 5380250
I-10103
1Phr refers to the "number of parts of polymer per hundred parts of rubber.

Bounding by pressing the hot melt adhesive was prepared in a metal container, heated and agitation system with adjustable speed. The temperature was maintained in the range of 177°C±2°C. the cooking Time was about 2 hours for each sample of the adhesive. The adhesives were applied to the Mylar (PET) with a thickness of 0.002 mm at 165°C and covered with silicone paper to avoid contamination. To study the adhesives were stored under controlled conditions at 50% humidity and 23°C. samples for the determination of the peel strength at 180°, the initial loop tack and tensile shear was a film impregnated with adhesives. Used to analyses the substrate consisted of a panel of stainless steel with a mirror finish. All analyses were carried out in controlled conditions (50% humidity and 23°C). The viscosity was measured using Brookfield viscometer, model RVII. Adhesive properties were determined using the following equipment: an instrument for determining the initial adhesion Loop Tack tester device to define which of the strength of adhesion/remove AR-100 Adhesion Release Tester and device for determining the tensile shear Shear Bank.

Table 4 shows thermal, mechanical and rheological properties of adhesive compositions. Despite the differences in the viscosity of the adhesives at a temperature of 177°C all they are applicable and the values of viscosity were typical of the hot melt. The values of the softening temperature followed the same trend as the viscosity, where the adhesive containing the sample RO-SEBS-r with a high content of vinyl, had a maximum value. The values of elongation for the three adhesives were very high, and for this reason it is not possible to interpret their impact on the performance of adhesives.

Table 4
The adhesive composition
Example123
The polymer sampleN-9618-11N-9618-07N-9618-06 dep
The type of polymerSEBS-rRO-SEBS-rHO-SEBS-r
highhighhigh
contentcontentcontent
vinylvinylvinyl
The viscosity300094501790
Brookfield
177°C, SP
Temperature108,0123,6110,8
softening,° C
Elongation, %1279,01548,11032,5

Table 5 presents the results of the analysis of the properties of the adhesives after aging in an oven at a temperature of 177°Poluchenie results indicate that the properties of the adhesives exceed commercial requirements for sustainability, as their viscosity has no tendency to increase in the tip is of the required 72 hours. Typically, SBS and SEBS products increased viscosity refers to the process of gelation of polymers. Further proof of thermal stability of the adhesive is no "skin" in the samples subjected to thermal aging at a temperature of 177°C in an oven for 72 hours.

Table 5
Analysis of thermal stability at 177°C (aging in the oven)
The adhesive composition
Example123
SampleN-9618-11N-9618-07N-9618-06
polymerdep
TypeSEBS-rRO-SEBS-rHO-SEBS-r
polymerhighhighhigh
contentcontentcontent
vinylvinylvinyl
time, h
Viscosity according to Brookfield,24261183171468
JV at 177°C
4824287300978
72252274671261
The separation of the phases24NoNoNo
48NoNoNo
72NoNoNo
Education "Corky"24NoNoNo
48NoNoNo
72NoNoNo

Table 6 shows the results of analyses that demonstrate the stickiness of the product. In the case of determining the tensile shear for the sample prepared with protected functional groups (RO-SEBS-r with a high content of vinyl), and for the sample prepared with functional groups with the removal of the second protection (HO-SEBS-r with a high content of vinyl), were obtained higher values of tensile shear compared with the sample prepared with defunctionalization product (SEBS-r with a high content of vinyl). For glue, prepared from the protected functionalized gidrirovanny polymer, the improvement in strength is more than 100% compared to defunctionalization gidrirovanny polymer, while for the glue obtained from functionalized gidrirovanny polymer, the improvement in strength is almost 200%.

The measurement of the initial stickiness of the loop is a measure of the attractive forces between the surface of the adhesive and the substrate, therefore, the density of the impregnation does not have much influence on this parameter. It is noticed that for the sample prepared from the protected functionalized gidrirovanny polymer (RO-SEBS-r with a high content of vinyl), stickiness decreases slightly, while for the adhesive prepared with functionalized gidrirovanny polymer with removed protective groups (HO-SEBS-r with a high content of vinyl), stickiness increases by approximately 50% compared with the control sample, which represents only the hydrogenated polymer (SEBS-r with a high content of vinyl).

In the case of determining the peel strength at 180° was observed the same trend when determining the initial sticky the t loop, where the adhesive containing the resin HO-SEBS-r with a high content of vinyl shows the maximum value.

Table 6
Properties of adhesives
The adhesive composition
Example123
The polymer sampleN-9618-11N-9618-07N-9618-06 dep
The type of polymerSEBS-r with a high content of vinylRO-SEBS-r with a high content of vinylHO-SEBS-r with a high content of vinyl
Static shear load of 1000 g, min2,4a 3.96,4
The initial stickiness of the loop, PLI0,4820,3280,639
Tensile strength at 180°, PLI0,9560,8532,215

The composition of the baths the adhesives resin Piccolyte HM-106

Adhesive compositions containing resin Piccolyte HM-106, were obtained by the composition shown in Table 7. Adhesives were prepared in a 1 l glass reactor at 160°C, adding first the oil and then the antioxidant, resin and polymer. The mixture was cooked for approximately 1 hour with constant stirring at a constant current of nitrogen. The adhesives were applied to the Mylar (PET) film at 165°C and covered with silicone paper to avoid contamination. To determine the stickiness of the sample and SAFT (time loss stickiness) samples were prepared from impregnated with adhesives film. The stickiness of the sample was determined at 2.5 cm samples using the Digital device Polyken Probe Tack Tester TMI 80-02-01 with probe stainless steel 0.5 cm in diameter according to the method of ASTM D 2979. Analysis SAFT was performed in an oven with forced air circulation (Cheminstruments) at 48°C and a weight of 0.25 kg Used for analyses of the substrate consisted of a panel of stainless steel with a mirror finish. The viscosity was measured using Brookfield viscometer, model RVII.

Table 7.
The composition to obtain a hot-melt adhesive resin Piccolyte HM-106.
Phr1
The polymer sampleResin Piccolyte HM-106200
Naphthenic acid NYNAS96
I-1330/I-1682/2
1Phr refers to the "number of parts of polymer per hundred parts of rubber.

The results of the hot-melt adhesives prepared from the resin Piccolyte HM-106, are shown in Table 8. For each family of adhesives trends observed for the Brookfield viscosity at 160°C and 180°C are similar, regardless of the temperature measurement. The viscosity of the adhesives containing polymer with an average grade vinyl and hydrogenated polymer was higher than the viscosity of the adhesives prepared with digidrirovanny polymer with a high content of vinyl. Thus, it is a consequence of the nature of the polymer and reflects that the adhesive is prepared from a polymer with a high content of vinyl, has a lower viscosity than the adhesive containing polymer with an average content of the vinyl of the same composition and molecular weight. On the other hand, the content of vinyl negidrirovannah the polymer does not affect the softening temperature of the adhesive, which was higher for the adhesive prepared with gidrirovanie polymers.

td align="left"> 12
Table 8
The results of the analysis of the hot-melt adhesive prepared from the resin Piccolyte HM-106
ExampleSampleType
polymer
The viscosity
Brookfield at 160°C, SP
The viscosity
Brookfiel d at 180°C, SP
Temperature
softening, °C
Stickiness
of the sample, g
SAFT,
4S9618 C01SBS-r-co. the average content of vinyl3625180094.21068122
5N 18RO-SBS-r with the average content of vinyl5730385081.3170260
6N 18 depHO-SBS-r with the average content of vinyl6530392088.71723426
7N-17SBS-r with a high content of vinyl2695153082.9681191
8N-10RO-SBS-r
high vinyl content
160090578.71290131
9N-09 depHO-SBS-r with a high content of vinyl139583786.61348227
10N-11SEBS-r
high
the content of vinyl
1660065001196021050
11N-15RO-SEBS-r with a high content of vinyl2270112097.7934--
N-06 depHO-SEBS-r with a high content of vinyl745028601209321995

Sticky glue samples prepared with digidrirovannye polymers, shows a similar tendency as compared with the samples of the adhesive prepared with gidrirovanie polymers. Adhesives containing protected functionalityand polymers or functionalityand polymers with removed protective groups show very similar values of stickiness, which is always higher than the adhesiveness of adhesives, prepared with defunctionalization polymers, namely 1.6 times higher in the case negidrirovannah polymers with an average content of vinyl, two times higher than in the case negidrirovannah resins with a high content of vinyl and 1.5 times higher in the case of adhesives prepared with gidrirovanie resins. It was also observed that the increase in the content of vinyl reduce the stickiness. In the case of SAFT, glues, prepared with gidrirovanie resins are more resistant to the time shift compared to adhesives prepared with digidrirovannye resins. The results of the analysis SAFT show that the adhesives containing functionalityand multiresolution polymer is, are more resistant to the shift in time than adhesives that contain defunctionalization multiresolution resin.

1. Functionalized multicasualty polymer which contains reaction product:
(A) a cross-linking agent to the number of functional groups of from 1 to 30, preferably from 5 to 20, which represents an oligomer, which can be obtained free-radical polymerization of at least one monomer selected from the group which consists of alkenyl aromatic monomers, functionalized epoxy group of the acrylic monomers and mixtures thereof; and at least one monomer selected from the group which consists of alkenyl aromatic monomers, functionalized epoxy group of acrylic monomers, functionalized anhydrite group of acrylic monomers, functionalized ester group of the acrylic monomers, functionalized with a carboxyl group of acrylic monomers and any mixtures thereof, where the crosslinking agent has srednetsenovoj molecular weight of from about 1,000 to about 10,000 g/mol and srednevekovoi molecular weight of from about 1,500 to about 20,000 g/mol;
(B) and synthesized by anionic polymerization and subsequently hydrolyzed polymer
characterized in that the synthesized anionic the polymerization of the polymer has the formula (I) Li-Q n-Z-T-Nmwhere Q represents alkeneamine aromatic monomers, conjugated diene, or their mixtures, anionic polymerized under the action of Li-Z, Z is a branched or unbranched hydrocarbon linking group of from 3 to 25 carbon atoms; T is an element selected from oxygen, sulfur and nitrogen; m is 1 when T represents oxygen or sulphur and m represents 2, when T represents nitrogen, n represents the number of units of diene monomers, alkenyl aromatic monomers or other monomers in their anionic polymerized mixtures.

2. Functionalized multicasualty polymer according to claim 1, characterized in that it contains from 1 to 30 circuits synthesized by anionic polymerization of the polymer, covalently linked with a crosslinking agent.

3. Functionalized multicasualty polymer according to claim 1 or 2, characterized in that the synthesized anionic polymerization of the polymer obtained from alkenyl aromatic monomers, conjugated diene monomers, or a mixture thereof, preferably in a molar proportion alkenyl aromatic monomers relative to paired the diene monomers from 0.05 to 1.04.

4. Functionalized multicasualty polymer according to claim 3, characterized in that sineserye the first anionic polymerization, the polymer includes, at least one polymer selected from the group consisting of polystyrene, polybutadiene, polyisoprene and statistical copolymers or statistical gradient polymers derived from monomers selected from the group consisting of styrene, butadiene and isoprene.

5. Functionalized multicasualty polymer according to claim 3, characterized in that the synthesized anionic polymerization of the polymer has an average molecular weight at the peak of the distribution from 3000 to 300000 g/mol, preferably from 20,000 to 300,000 g/mol.

6. Functionalized multicasualty polymer according to claim 3, characterized in that synthesized by anionic polymerization of a polymer derived from a conjugated diene monomers and has a content of 1,2-structures from 8 to 80% by moles.

7. Functionalized multicasualty polymer according to claim 3, characterized in that the synthesized anionic polymerization of the polymer is the percentage of cross-linked chains of from 2 to 90% by mass.

8. Functionalized multicasualty polymer according to claim 3, characterized in that the synthesized anionic polymerization of the polymer has an average molecular weight at the peak of the distribution from 20000 to 500000 g/mol.

9. Functionalized multicasualty polymer according to claim 3, characterized in that the functionalized multicasualty polymer has come rudnyy the molecular weight at the peak of the distribution from 5000 to 2000000 g/mol.

10. Functionalized hydrogenated multicasualty polymer, characterized by the fact that it can be obtained by hydrogenation of any of the polymers according to claim 3.

11. A method of obtaining a hydrogenated multiresolutional polymer of claim 10, characterized in that it comprises the hydrogenation of functionalized multiresolutional polymer at a temperature of from 25 to 150°C before removing the protective groups, characterized in that the hydrogenation is at least 85%.

12. Adhesive composition, which contains the functionalized multicasualty polymer according to claim 1, which contains at least one additive selected from the group consisting of enhancing the adhesiveness of the resin, stabilizers, plasticizers and antioxidants.

13. Reinforced material, which contains the functionalized multicasualty polymer according to claim 1, mixed with a reinforcing material or the material to be reinforced, characterized in that the material to be reinforced, selected from the group consisting of bitumen, plastic and material tire.

14. The product is made of reinforced material according to item 13.

15. Modified bitumen, which contains bitumen, mixed with functionalized multiresolutional polymer according to claim 1, which contains from 1 to 25% by weight of functionalityof the frame multiresolutional polymer.

16. Modified plastic, which includes plastic, mixed with functionalized multiresolutional polymer according to claim 1, characterized in that the mixture contains from 1 to 40% by weight of functionalized multiresolutional polymer by total weight of functionalized multiresolutional polymer and plastics.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention includes a method of conducting polymerisation to obtain a polymer containing styrene and 1,3-butadiene monomer units, where said method includes: (A) feeding less than 60 wt % of the total amount of butadiene used in polymerisation into a reactor containing all the amount of styrene used in polymerisation, and a solvent; (B) feeding at least one initiator into the reactor and providing conditions for the reaction to occur over a time t; (C) feeding the remaining amount of butadiene into the reactor in two or more separate feeds; and where for each subsequent feeding of butadiene, the amount of the fed butadiene is less than the amount of butadiene fed into the reactor immediately before said feeding, or is equal to the amount of butadiene fed into the reactor immediately before said feeding. For each butadiene feed, the butadiene is fed over a time tnc and after each feed, the reaction is carried out over a time tnr, where n is the number of butadiene feeds, and where the polymer contains polymer chains having higher styrene content in a direction towards the middle of the polymer chains, and lower styrene content at the ends of the chains. The invention includes a polymer, a composition for articles and an article.

EFFECT: obtaining a special rubber structure.

22 cl, 9 tbl, 2 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: method of obtaining in solvent mixture of nanoparticles and liquid polymer, synthesised in one reactor, is described, with method containing the following stages: (a) carrying out either polymerisation of first monomer until liquid polymer is obtained, or copolymerisation of first monomer and second monomer until liquid polymer is obtained, in reaction container, where first monomer is selected from group, consisting of C4-C8 -conjugated dienes and their mixtures, and second monomer is selected from group, consisting of styrene, α-methylstyrene, 1-vinylnaphthaline, 2-vinylnaphthaline, 1-α-methylvinylnaphthaline, 2-α-methylvinylnaphthaline, vinyltoluol, methoxystyrene, tert-butoxystyrene and their alkyl, cycloalkyl, aryl, alkaryl and aralkyl derivatives, in which total number of carbon atoms in derivative in not larger than 18, or any di- or tri-substituted aromatic hydrocarbons and their mixtures; (b) partial stop of polymerisation by application of agent for inhibition of active centres; and (c) addition of polyfunctional comonomer, monovinylaromatic monomer and optional loading of polymerisation initiator; where said nanoparticles have core, which includes monovinylaromatic monomer, and shell, including first monomer or first and second monomer, with nanoparticles being formed as a result of self-aggregation into micelles and cross-linking of micelles by polyfunctional comonomer. Also described is method of obtaining caoutchouc composition, with method including: obtaining described above mixture of nanoparticles and liquid polymer and adding mixture to caoutchouc composition. Method of tyre manufacturing with application of nanoparticles and liquid polymer is described, with method including: obtaining described above mixture of nanoparticles and liquid polymer, adding mixture to caoutchouc composition; formation of tyre tread from caoutchouc composition; and constructing tyre with application of said tread. Composition of substances for application on caoutchouc composition, obtained in accordance with method described above, is described. Said composition, in fact, consists of: micellar nanoparticles, belonging to "core-shell" type, where nanoparticles are formed as a result of self-aggregation into micelles and cross-linking of micelles by polyfunctional comonomer; and liquid polymer, which is characterised by Mw value in the range from approximately 10000 to approximately 120000; where nanoparticles are dispersed and mixed inside liquid polymer.

EFFECT: simplification of method of obtaining mixture of nanoparticles and liquid polymer and their further processing.

22 cl, 2 dwg, 4 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of synthetic rubbers, in particular diene (co)polymers, such as polybutadiene, polyisoprene and styrene-butadiene rubber (SBR), used in production of tyres and industrial rubber articles, in modifying bitumens, in electrical engineering and in other fields. Described is a method of producing (co)polymers which is carried out in two parallel reactors, in each of which dienes are polymerised or copolymerised with each other and/or with arylvinyl compounds. An organolithium initiator, an electron donor additive and a branching agent are fed into the first reactor, and an organolithium initiator, an electron donor additive and a functionalising agent are fed into the second reactor. The polymerised mixtures obtained in the first reactor and the second reactor are mixed with each other and a chain termination reaction is then carried out.

EFFECT: obtaining said branched compounds that are characterised by a statistical distribution of monomer units, high content of vinyl units, a narrow molecular mass distribution and a controlled content of branched and functionalised parts in the copolymer.

15 cl, 20 ex

FIELD: chemistry.

SUBSTANCE: flame-extinguishing polymer composition contains a combustible polymer mixed with a bromated flame-extinguishing additive selected from one or more compounds given below: (i) a copolymer containing styrene and 2,3-dibromopropylmaleimide repeating units; (ii) a bromated polyester containing bromine atoms bonded with aliphatic groups; (iii) an allyl ether which is bromated on a novolac resin ring; (iv) 3-bromo-2-hydroxypropyl ether of novolac resin; (v) 2,3-dibromopropyl ether cresol-novolac resin, and (vi) a bromated polymer or a copolymer obtained via ROMP.

EFFECT: stability of the flame-extinguishing additive at high temperatures, low toxicity and avoiding significant loss of physical properties of the polymer during use thereof.

7 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: composition contains at least one bitumen and at least one graft polymer, having a polymer backbone chain and at least one side graft component linked to the polymer backbone chain. Said graft component has a branched or straight saturated hydrocarbon chain having 18-110 carbon atoms. The graft polymer is obtained by reacting at least one double bond of the polymer and a thiol group of the graft component, where the polymer is obtained by copolymerisation of diene monomers. The invention also relates to a method of preparing such thermoreversibly crosslinked bitumen-polymer compositions, as well as use of such compositions in road construction, particularly for producing binding materials for roads, and in different industries.

EFFECT: bitumen-polymer compositions have, at operating temperatures, properties of bitumen-polymer compositions which are irreversibly cross-linked, particularly in terms of elasticity and stickiness, and have low viscosity at treatment temperatures.

17 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer composition which is used to make sterilisable containers, for example, sterilisable bags or medical packaging for intravenous solutions, for example. The composition contains a heterophase propylene copolymer and styrene-based elastomer(s), wherein the ratio of the flow rate MFR2 (230°C) of the heterophase propylene copolymer to the flow rate MFR2 (230°C) of the styrene-based elastomer (MFR2 (230°C) (A)/MFR2 (230°C)(B))≤1.0. The heterophase copolymer contains a polypropylene matrix and an elastomeric propylene copolymer which contains at least one comonomer selected from a group comprising ethylene and C4-C20 alpha-olefins. The weight content of styrene in each styrene-based elastomer is equal to less than 15%, and the total weight content of styrene-based elastomers (B) from the total amount of polymers in the polymer composition ranges from 16.0 to 46.0%. The polymer composition disclosed herein is particularly suitable for making heat-sealable films.

EFFECT: polymer composition provides high air-tightness of articles made therefrom after sterilisation while maintaining high strength and dullness.

22 cl, 3 tbl

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: invention relates to a method of producing a functional polymer. The polymer contains one or more types of polyene monomer moieties and at least one functionalising link which contains an aryl group, having at least one directly bonded OR group, where R is a hydrolysable protective group. The method involves: a) obtaining a solution containing an initiating compound and ethylenically unsaturated monomers which contain at least one type of polyene, at least one type of C8-C20 vinyl aromatic compound and an ethylenically unsaturated compound of formula CH2=CHR1, where R1 is an aryl group having at least one substitute, where R is a hydrolysable protective group; and b) facilitating anionic initiation with said initiating compound of polymerisation of said ethylenically unsaturated monomers to obtain a carbanionic polymer. At least one functionalising link is obtained from said monomer containing an R1 group.

EFFECT: obtaining functional polymers which improve interaction with filler.

16 cl, 19 tbl, 87 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of modifying the surface of a polyethylene terephthalate granulate in order to increase heat-, light-, wear- and hydrolytic resistance, as well as reduce gas permeability of polymer materials. The method involves treating the surface of a polyethylene terephthalate granulate with a modifier while heating. The modifier used is a mixture of fluorine-containing prepolymers in amount of 2 pts.wt per 100 pts.wt polyethylene terephthalate in weight ratio of 83(I):12(II+III):5(IV), represented by formulae (I)-(IV) in the claim. Said compounds are obtained in advance by reacting 4,4'-diphenylmethane diisocyante with 1,1,5-trihydroperfluoropentanol-1 in the presence of catalytic amounts of di-n-butyltin dilaurate in molar ratio of 1:1:0.005, respectively, in a medium of chlorobenzene and n-hexane in volume ratio of 8:1, at temperature of 80°C, ultrasound frequency 40 kHz for 2 hours. Modification is carried out in a medium of chlorobenzene at 150°C for 4 hours.

EFFECT: method widens the operating temperature range of articles made from polyethylene terephthalate.

3 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of modifying the surface of a polyethylene terephthalate granulate in order to increase heat-, light-, wear- and hydrolytic resistance, as well as reduce gas permeability of polymer materials. The method involves treating the surface of polyethylene terephthalate with a modifier while heating, wherein the modifier used is a fluorine-containing prepolymer with isocyanate groups in amount of 2 pts.wt per 100 pts.wt polyethylene terephthalate of general formula: , n=5-7, m=2-4. Said modifier is obtained by reacting polymethylene polyphenylene isocyanate with content of isocyanate groups of 29.5-31.0% with trifluoroacetic acid in the presence of catalytic amounts of di-n-butyl tin dilaurate with molar ratio of reactants of 1:0.3:0.003, respectively, in a medium of o-dichlorobenzene at temperature of 70°C, ultrasound frequency of 40 kHz for 6 hours. Modification is carried out in a medium of chlorobenzene at 150°C for 4 hours in the presence of catalytic amounts of di-n-butyl tin dilaurate.

EFFECT: modifying the surface of a polyethylene terephthalate granulate using said method enables to widen the operating temperature range of articles made from polyethylene terephthalate.

1 tbl, 1 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to a method for preparing laevomycetin ointment with glutaric aldehyde and ethonium on the basis of modified laevomycetin, consisting in the fact that laevomycetin 100 mg/ml detoxified and polymerised at first in glutaric aldehyde 0.1-0.2% at 38-40°C for 3-5 days, then in 0.2% ethonium at 38-40°C for 2-3 days, is used for preparing 1-3% Vaseline ointment.

EFFECT: preparing the ointment with low toxicity and high bactericidal activity.

3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing oxidation-resistant ultrahigh molecular weight polyethylene (UHMWPE) material. The method involves forming UHMWPE with an additive and treatment with gamma-rays or an electron beam. Exposure is carried out on air under normal atmospheric conditions with a dose of 2-40 Mrad. The exposed head has oxidation index after artificial ageing which is equal to or lower than that of standard UHMWPE material sterilised with gamma-rays.

EFFECT: UHMWPE material exhibits improved wear resistance and good resistance to oxidation.

48 cl, 5 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing a functionalised polymer. Described are versions of a method of producing a functionalised polymer comprising the following steps: (a) polymerisation of a conjugated diene monomer, optionally along with a monomer capable of copolymerisation with a conjugated diene monomer, in the presence of a coordination catalyst to form a polymer; (b) inhibiting said polymerisation step with a Lewis base; and (c) reaction of the polymer with a functionalising agent different from the Lewis base used at step (b). Described also is a functionalised polymer obtained using a method comprising the following steps: (a) polymerisation of a conjugated diene monomer, optionally along with a monomer capable of copolymerisation with a conjugated diene monomer, in the presence of a coordination catalyst to form a polymer; (b) inhibiting said polymerisation step with a Lewis base; and (c) reaction of the polymer with a functionalising agent different from the Lewis base used at step (b).

EFFECT: inhibiting polymerisation without destructive effect on the capacity of the reactive polymer to react with the functionalising agent, reduced risk of uncontrolled polymerisation, reduced contamination of equipment.

14 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: method involves reacting a polymer solution in an organic solvent with a chlorinating agent. The chlorinating agent used is aqueous sodium hypochlorite with concentration 0.05-0.2 mol/l. Reaction takes place in molar ratio 1,2-polybutadiene: sodium hypochlorite equal to 1:1-2.5 at temperature from minus 10 to 30°C for 1-5 hours at pH of the reaction mixture of 4-6, which is maintained using a buffer system consisting of a mixture of phosphoric acid and sodium hydrophosphate in form of a 0.3 M aqueous solution.

EFFECT: high safety of the chlorination process owing to use sodium hypochlorite.

2 cl, 1 tbl, 22 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a butyl-rubber based ionomer, a peroxide-vulcanised article made from a butyl rubber-based monomer, as well as an article having a substrate containing stainless steel material, glass material or mylar material, and a butyl rubber-based ionomer bonded to said substrate. The ionomer includes repeating structural units based on at least one isoolefin monomer, at least 0.5 mol % repeating structural units based on at least one olefin monomer with several unsaturated bonds, at least 0.5 mol % repeating structural units based on an allyl halide and at least 0.5 mo l% ionomeric part based on a product of reacting an ally halide with a nitrogen- or phosphorus-based nucleophile of formula , where A denotes a nitrogen or phosphorus atom and R1, R2 and R3 are selected from a group consisting of linear or branched alkyl substitutes with 1-4 carbon atoms, an aryl substitute which is monocyclic or is formed by condensed rings with 4-8 carbon atoms, and/or a heteroatom selected from a boron, nitrogen, oxygen, silicon, phosphorus or sulphur atom.

EFFECT: obtaining a butyl polymer with improved adhesion to surfaces for making articles and in composite materials obtained based thereon.

17 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer nanoparticle having a nucleus/shell configuration with an interphase region between the nucleus and the shell, which contains at least one polymerised monomer selected from a polymerised nucleus monomer and a polymerised shell monomer. The nucleus of the polymer nanoparticle is uniformly cross-linked by at least one cross-linking agent. The average diameter of the polymer nanoparticles can be less than 250 nm. Described also is a rubber composition containing polymer nanoparticles and use thereof to make tyres, as well as methods of producing polymer nanoparticles. To form a uniformly cross-linked nucleus, polymerisation of the nucleus is carried out through step-by-step addition in several loads or batching synchronised amounts of the nucleus monomer and the cross-linking agent. The size, composition and/or configuration of the interphase region is varied, thereby achieving desirable physical and/or chemical properties of the resultant polymer nanoparticles and compositions to which the nanoparticles are added.

EFFECT: improved physical and chemical properties.

45 cl, 6 tbl, 7 ex, 19 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to polyamines and methods of using said polyamines for scale treatment in different industrial process streams. Disclosed are hydrophobically modified silicon-containing polyamines, containing repeating structural links of two types, a composition based thereon and a method of reducing or eliminating scales in an industrial process, involving addition of the disclosed polymer or composition into a process stream.

EFFECT: disclosed hydrophobically modified silicon-containing polyamines are suitable for aluminosilicate scale treatment in hard-to-clean industrial process streams, such as process streams in a Bayer method of extracting alumina from bauxite, streams of radioactive wastes and effluent streams formed during production of kraft paper.

30 cl, 9 tbl, 156 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing a polymer, having at least one functional terminal group, and a liquid polymer dispersed therein. The invention also relates to a composition and a coating containing the obtained polymer product. The method involves: (a) producing a 'living' polymer, where production of said 'living' polymer is initiated based on an anionic mechanism, and said polymer contains a cation; (b) adding a functional initiator precursor of the formula FI-H, where H is hydrogen and FI is a functional group, said H terminates said 'living' polymer resulting in a liquid polymer, and FI and said cation form a functional initiator; (c) adding a monomer, where said functional initiator initiates anionic polymerisation of said monomer; and (d) terminating the polymerisation reaction initiated at step (c). Steps (a) through (c) may be conducted in a single reactor, allowing a liquid polymer to be dispersed in a functionalised polymer in a single polymerisation step.

EFFECT: liquid polymer does not have to be handled separately and processing efficiency is improved.

15 cl, 2 tbl, 7 ex

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