The combined mixture of olefinic polymers and monomineralic aromatic polymers

 

(57) Abstract:

Describes a polymer composition containing (a) from 0.5 to 99 wt.%, calculated on the total weight of (a), (b) and (C) aliphatic homopolymer-olefin, or a copolymer, or a copolymer of aliphatic-olefin and non-aromatic monomer capable of copolymerization; (b) from 0.5 to 99 wt.%, calculated on the total weight of (a), (b) and (C), homopolymer or copolymer monomineralic aromatic monomers, or copolymers nonoverridable aromatic monomer and a monomer capable of copolymerization and are not aliphatic-olefin % and (C) from 0.5 to 99 wt.%, calculated on the total weight of (a), (b) and (C) a polymeric agent compatibility, characterized in that the polymer as designated agent compatibility mostly use statistical copolymer of aliphatic-olefin and vinylidene aromatic monomer. The technical result is an improvement of the properties of the mixture. 5 C. and 12 C.p. f-crystals, 13 tables.

The invention relates to polymer mixtures containing olefinic polymer, monotinicity aromatic polymer and the agent compatibility. In addition, the present invention relates to a composition capable of expanding and containing the specified polymer is level; industrial product obtained by molding from polymeric mixture; and a method of packaging a substance or article by using the polymer composition.

Monolinoleate aromatic polymers such as polystyrene and polystyrene modified with rubber, can be very easily subjected to thermoforming and have impact strength and resistance to low temperatures during thermoforming. Thermoforming (thermoforming) is a method in which a resin sheet or workpiece softened by heating to a temperature below the temperature at which the resin is completely melted or plastification, is subjected to molding under pressure or in vacuo to give it the desired shape. However, monolinoleate aromatic polymers with a high degree of crystallinity are brittle and can be subjected to thermoforming only at high temperatures. Monolinoleate aromatic polymers are known to have low resistance to cracking under the action of the environment. Cracking under the action of the environment occurs when the molded resin parts are subjected to conditions under which they are under naprezenia materials such as fat - or oil-containing food products are packaged in a molded container. The presence of grease or fat in the food product, as well as the voltage supplied to the container when it is filling, sealing, and transportation, lead to the fact that these containers lose their strength and are easily destroyed.

Olefin polymers such as polyethylene, polypropylene, have relatively good resistance to oils and fats, and therefore, they are especially preferred polymers for the manufacture of containers for food products and similar materials. However, in industrial production or forming methods, olefinic polymers are used much less frequently than monolinoleate aromatic polymers. It is connected with considerable difficulties in the manufacture of olefin polymers due to their low glass transition temperature and relatively clear point of melting at an elevated temperature.

It would be desirable to combine the strength and resistance to solvents of olefin polymers with high modulus and ability to thermoforming monomineralic aromatic polymers by mixing the two resins. However, mixing monovinyl and these two resins. Attempts to solve the incompatibility issue have focused on the use of assigned amounts of the two resins and the use of so-called agent that improves compatibility.

Such agents that improves the compatibility and used for mixing the olefin polymers and monomineralic aromatic polymers, which are described in the literature are: graft copolymers of polystyrene and polyethylene, see Polymer 18, 69 (1977), J. Appl. Polymer. Sci. 17, 2597 (1973), 21 Polymer 1469 (1980), U.S. patent 4690976 and 4716197;

graft copolymers of polystyrene and ternary ethylene-propylene rubber (EPDM rubber), see J. Appl. Polymer. Sci. 17, 2597 (1973), ANTEC 92 Conference Proceedings, Society of Plastic Engineers, May 3-7, Detroit 2635 (1992);

di-block copolymers of styrene and diene, see the Japan Patent JP-A-48-43031 and JP-A-49-28637, U.S. Patent 4031166, European Patents EP-A-0060524 and EP-A-0060525;

hydrogenated diplomaprimary styrene and diene see Polymers Blends, E. Martuscelli, Ed. 201 (1981). J. Polym. Sci.; Polym. Letters. Ed. 19,79 (1981). J. Polym. Sci.; Polym. Phys. Ed. 19, 1269 (1981), J. Polym. Sci.; Polym. Phys. Ed. 20, 2209 (1982). The UK patent GB-A-1,363,466, Patent DD-A-241375, U.S. Patent 4020025 and the Japan Patent JP-A-81-38338;

the copolymers of ethylene and styrene, see U.S. Patent 3980736 and 3851015;

triblocaltara styrene-diene-styrene, see Eur. Polym. J. 19, 81 (1983), and Abramasi Patent EP-A-0060525, U.S. patent 4188432, Polym. Eng. & Sci. 21(5), 985 (1981). J. Appl. Polym. Sci. 26, 1 (1981), and Polymer Blands and Alloys Technology, Vol.3 Technomic Publiching Co., 117 (1992); and

the elastomer containing the main polymer chain monomers of styrene and a diene hydrocarbon, which the monomers are distributed heterogeneous on a microscopic level, but homogeneous at the macroscopic level. This elastomer can be obtained by polymerization of styrene and a diene in the presence of a lithium catalyst, resulting in a gain copolymer, which can be then added to the mixture of monomers for subsequent copolymerization, see Japan Patent JP 56-36534.

There is a hypothesis that compatibility between two immiscible or incompatible polymers can be influenced by adding an agent that improves adhesion between the boundary surfaces of polymers. In addition, it has been suggested that for good adhesion agent to improve compatibility should have a molecular segments that are not mixed with the corresponding polymer domains. This requires that the time had certain structural units, compatible with the corresponding polymer domains. For this reason, the proposed agents to improve the compatibility is zi in the frame of the polymer chain, not resistant to thermooxidation and ultraviolet radiation, resulting in their processing and use of products made from them, are certain difficulties. Adding large quantities of antioxidant eliminates some of the difficulties in processing, but leads to migration of the antioxidant to the surface of the manufactured products, reducing thus, the external appearance of the product. Saturated copolymers having a hydrogenated rubber blocks, such as triblocaltara styrene-ethylene/butylene - styrene (SEBS) were more stable, but generally not as effective agents for compatibility, as unsaturated agents for compatibility. In addition, the copolymers and especially hydrogenated block copolymers are expensive because of the high cost of their production. In line with this, the problem of other less expensive agents for compatibility, which would have at least the same or even better features than existing agents compatibility, it is still relevant. In addition, it would be highly desirable to obtain such agents compatibility, which would be resistant to oxidation and ultraviolet radiation when used is also to receive such expandable materials or materials capable of expansion, which would combine the properties of olefin polymers and monomineralic polymers in applications requiring expansion or foaming.

The present invention relates to a polymer mixture containing:

(a) from 0.5 to 99 wt.% (based on total weight of (a), (b) and (c) aliphatic homopolymer or interpolymer - olefin, or aliphatic - olefin and non-aromatic monomer capable of copolymerization with him;

(b) from 0.5 to 99 wt.% (based on the total weight of (a), (b) and (c)) homopolymer or interpolymer monomineralic aromatic monomers, or interpolymer nonoverridable aromatic monomer and copolymerizable with him monomer, non-aliphatic - olefin:

(c) from 0.5 to 99 wt.% (based on the total weight of (a), (b) and (c)), mainly statistical interpolymer containing aliphatic - olefin and vinylidene aromatic monomer.

In another aspect, the present invention relates to a composition capable of extension and containing the specified polymer mixture and foaming additive.

In another aspect, the present invention relates to expanded onto a composition obtained by foaming of the molding of the polymer mixture of the present invention.

In another aspect, the present invention relates to a method of packaging a substance or article, ensuring uniform mixing of components (a), (b) and (c) of this mixed polymer composition and providing the mixture in the form of attachments around or appropriate to obtain the substance or article that you want and packaging.

All references to the Periodic Table of Elements relate to the Periodic Table of the Elements, published and copyrighted CRC Press. Inc., 1989. Also, any reference to a Group or Group refers to a Group or Groups of the Periodic Table of Elements, where the numbering of the Groups used the system upac.

The term "polymer" used in the present description, refers to a polymer compound obtained by polymerization of one or more monomers. Thus, the General term "polymer" encompasses the term " homopolymer, usually used in relation to polymers obtained from only one monomer, and the term interpolymer defined below.

The term "interpolymer" as used in this description refers to polymers obtained by polymerization of at least two different monomers. Thus, the General term is slichnih monomers, and to the polymer derived from more than two different monomers.

In the present invention, in the description of polymer or interpolymer comprising or containing certain monomers, it is assumed that such polymers or interpolymer include or contain polymerized therein units derived from such a monomer. For example, if the monomer was ethylene CH2=CH2derived this link is included in the polymer, a is-CH2-CH2-.

In the following detailed description of the invention, the component of the mixture (a) may be cited as the olefinic resin or polymer; component of the mixture (b) monotinicity aromatic resin or polymer, component a mixture of (s) - agent compatibility.

Used the term "mainly statistical" statistical interpolymers, including - olefin and vinylidene aromatic monomer, indicates that the distribution of monomers in the specified interpolymer can be described by statistical Bernoulli model or statistical model Marcovina first or second order, as described by J. C. Rondall in POLYMER SEQUENCE DETERMINATION, Carbon -13 NMR Method, Academic Press New York, 1977, pp. 71-78. Preferably, essentially statistical intbag number vinylidene aromatic monomer in blocks vinylidene aromatic monomer, consisting of more than 3 links. More preferably, interpolymer was not characterized by a high degree or isotacticity or syndiotactic. This means that in13C-NMR spectrum, mainly statistical interpolymer the peak areas corresponding to the main methylene chain methine bond breaking and carbon, or representing the sequence of meso dyads or racemic sequence of dyads, shall not exceed 75 percent of the total area of the peaks of the underlying methylene chain and marinovich carbon.

Used in the present description, the term "linear" means that the polymer does not have the long branched chains. That is, the main chain of the polymer or interpolymer is unbranched or has only branching that occur from substituent (s) attached to the vinyl parts of the monomers constituting the main chain of the polymer.

The term "generally linear" means that the main chain of the polymer or interpolymer substituted with three or less long-chain branches /1000 carbon atoms, more preferably from 0.01 long chain branches /1000 carbons to 1 long chain branching /1000 carbons, and especially from 0.05 length of the main linear chain further elaborated in U.S. Patent N 527223 and 5278272, introduced in the present description by reference. Linear or generally linear polymer different from the polymer obtained by free radical polymerization under high pressure, which, as is well known to specialists in this area has numerous long-chain branching.

Olefin polymers suitable for use as component (a) in the mixtures of this invention are aliphatic homopolymers or interpolymers - olefin, or interpolymers aliphatic - olefin and non-aromatic monomer capable of forming with him interpolymer. Preferred olefin polymers for use in the present invention are homopolymers or aliphatic interpolymer (including cycloaliphatic interpolymer) - olefin having from 2 to 18 carbon atoms. Suitable examples are homopolymers of ethylene or propylene and interpolymer two or more monomers. Other preferred olefin polymers are interpolymer ethylene and one or more other olefins having from 3 to 8 carbon atoms. Examples of monomers that can cure them are 1-butene, 4-IU is n or more non-aromatic monomers, capable of copolymerization. Such additional monomers that can form interpolymer, are for example, diolefine, carboxylic acid containing unsaturated ethylene communication (both mono-and bifunctional), and derivatives of these acids, such as esters and anhydrides. Examples of such monomers are acrylic acid, methacrylic acid, vinyl acetate and maleic anhydride. Olefinic polymers can be, in addition, are characterized by their degree of long or short chain branching chain and distribution of such branches.

One class of olefin polymers receive mainly by polymerization at high pressure using free radical initiator of polymerization, resulting in a traditional dlinnozerny branched low-density polyethylene (LDPE). LDPE used in the present composition generally has a density of less than 0,94 g/cm3(ASTM D 792) and the index melting point of from 0.01 to 100, and preferably from 0.1 to 50 grams/10 minutes (as determined by test method ASTM D 1238, condition I).

Another class are linear olefin polymers in which there are no long-chain branching and which are known as traditional high-density (HDPE), obtained by polymerization Ziegler (for example, U.S. Patent N 4076698 (Anderson and others), and sometimes called heterogeneous polymers.

HDPE is mainly composed of long linear polyethylene chains, HDPE used in the present composition generally has a density of at least of 0.94 grams per cubic centimeter (g/cm3) as determined by test method ASTM D 1505, and the index of fusion (ASTM-1238, condition I) in the range from 0.01 to 100, and preferably from 0.1 to 50 grams/10 minutes.

Heterogeneous LLDPE used in the present composition has a density, mainly from 0.85 to 0.94 g/cm3(ASTM D 792), and the index of fusion (ASTM-1238, condition I) in the range from 0.01 to 100, and preferably from 0.1 to 50 grams/10 minutes. The preferred LLDPE is interpolymer ethylene and one or more other olefins having 3 to 18 carbon atoms, and more preferably 3-8 carbon atoms. The preferred comonomers are 1-butene, 4-methyl-1-penten, 1-hexene and 1-octene.

Another class is the class of uniformly branched or homogeneous polymers (homogeneous LLDPE). Homogeneous polymers do not contain any long-chain branching and have only branching originating from monomers (when cash is anti USA N 3645992 (Elston), and a polymer obtained using the so-called catalysts is the only site in the periodic reactor having a relatively high concentration of olefin as described in U.S. Patent N 502679 and 5055438 (Canich). Homogeneously branched/homogeneous polymers are polymers in which a statistical distribution of comonomers within a given molecule interpolymer and in which molecules of interpolymer have a similar ratio of ethylene/comonomer within this interpolymer.

Homogeneous LLDPE used in the present composition has a density mainly from 0.85 to 0.94 g/cm3(ASTM D 792), and the index of fusion (ASTM-1238, condition I) in the range from 0.01 to 100 and preferably from 0.1 to 50 grams/10 minutes. The preferred LLDPE is interpolymer ethylene and one or more other olefins having 3 to 18 carbon atoms, and more preferably from 3-8 carbon atoms. The preferred comonomers are 1-butene, 4-methyl-1-penten, 1-hexene and 1-octene.

In addition, there is a class with mostly linear olefin polymers (SLOP), which can mainly be used in the component (a) mixtures of the present invention. These polymers have good technogene polymers, mainly linear interpolymer ethylene/ - olefin have only one melting peak, as opposed to the traditional heterogeneous linear interpolymers ethylene/ - olefin obtained by polymerization Ziegler, and having two or more melting peaks (determined using differential scanning calorimetry). Essentially linear olefin polymers have been disclosed in U.S. Patent N 527223 and 5278 272, which have been incorporated herein by reference.

The density of SLOP, measured in accordance with ASTM D-792, basically, is from 0.85 g/cm3to 0.97 g/cm3preferably from 0.85 g/cm3to 0,955 g/cm3and especially from 0.85 g/cm3to 0.92 g/cm3.

Index melting SLOP, according to ASTM D - 1238, condition 190oC/2,16 kg (also known as 12) is generally from 0.01 g/10 min to 1000 g/10 minutes, preferably from 0.01 g/10 minutes to 100 g/10 minutes, and especially from 0.01 g/10 min to 10 g/10 minutes.

SLOP can be homopolymers C2-C20olefins such as ethylene, propylene, 4-methyl-1-penten etc. or it can be interpolymers ethylene, at least one C3-C20- olefin and/or C2-C20unsaturated by acetylene communication monomer and/or C3-C20- olefins, diolefins and/or unsaturated by acetylene communication monomers in combination with other unsaturated monomers.

Particularly preferred olefin polymer components (a) are LDPE, HDPE, heterogeneous and homogeneous LLDPE, SLOP, polypropylene (PP), especially isotactic polypropylene and rubber hard polypropylene or interpolymer of ethylene and propylene (EP) or mixtures thereof.

Basically, the mixture of the present invention contain at least 0.5 to 99 wt.%, preferably at least 20-80 wt.%, most preferably at least 35-70 wt.% olefin polymer (a), based on the total weight (a), (b) and (c).

Monovinylacetylene aromatic polymers suitable for use in component (b) of these compounds are homopolymers or interpolymer nonoverridable aromatic monomer or interpolymer nonoverridable aromatic monomer and a monomer capable of copolymerization with him, and non-aliphatic - olefin. Suitable monolinoleate aromatic monomers represented by the following formula:

< / BR>
in which R1was selected from the group of radicals consisting of hydrogen and alkyl of RA is Noah 1-5 substituents, selected from the group consisting of halogen, C1-4-alkyl and C1-4-halogenoalkane. Typical monovinylacetylene aromatic monomers are styrene, paramilitary - methylsterol, tert-butalbiral, chloresterol, including all isomers of these compounds, etc. are Particularly preferred monolinolein aromatic monomer to obtain monomineralic aromatic polymers used in the practice of the present invention is styrene.

In addition MobileDevice aromatic monomer, other examples of suitable comonomers capable of copolymerization, are N-familymed maleic acid, acrylamide, unsaturated ethylene communication nitrile monomers such as Acrylonitrile and Methacrylonitrile containing unsaturated ethylene connection of mono - and bifunctional carboxylic acids and their derivatives such as esters and, in the case of bifunctional acids, anhydrides, such as acrylic acid, C1-4-alkylacrylate or methacrylates, such as n-butyl acrylate and methyl methacrylate, maleic anhydride, etc., In some cases it is also desirable to copolymerizate a crosslinking monomer, such as divinylbenzene in monomineralic aromatic mi to form interpolymer, preferably contain, polymerized at least 50 wt.% and preferably at least 90 wt.% one or more monomineralic aromatic monomers.

To improve droproot properties monomineralic aromatic polymers, these polymers can be appropriately modified rubber. Examples of suitable rubbers are homopolymers of C4-6-dienes with conjugated double bonds, especially butadiene or isoprene; copolymers of one or more monomineralic aromatic monomers and one of several C4-6-dienes with conjugated double bonds, especially butadiene or isoprene; copolymers of ethylene and propylene or ethylene, propylene and diene with non-conjugate double bonds, especially 1,6-hexadiene or ethylidenenorbornene (norbornene); homopolymers of C4-5alkylacrylate; copolymers C4-6alkylacrylate and co monomer capable of forming a copolymer, especially nonoverridable aromatic monomer or C1-4alkylmethacrylamide. As an example, can also be grafted polymers of the above rubber-modified polymers, where the grafted polymer is monotinicity aromaticheski the data modified rubber polymer is styrene. The preferred rubber-modified polymer is polybutadiene or a copolymer of styrene/butadiene. The above-mentioned rubbers can be obtained by anionic polymerization in solution or free radical polymerization in solution, bulk, emulsion or suspension. Kucukodabasi elastomers obtained by the polymerization in the emulsion can be agglomerative with the formation of larger particles having a bi-modal or tri-modal, and so on, the size distribution, if necessary.

Monolinoleate aromatic polymers with modified uteroplacental properties are well known to specialists in this field and are commercially available. Suitable polymers with modified uteroplacental properties can be obtained by mixing kauchukopodobnoe polymer with a pre-prepared matrix polymer having the desired chemical composition, by graft-polymerization of the matrix in the presence of pre-dissolved rubber, or a combination of such methods.

Preferred monolinoleate aromatic polymers with modified uteroplacental properties are obtained by RAS the polymerization of the obtained solution, preferably while stirring the solution so that in the formed dispersed grafted polymer with modified uteroplacental properties with rubber domains, which contain inclusions of matrix polymer dispersed in the resulting polymer matrix. Such modified rubber polymers, known as polymerized in bulk or in solution, polymers, high impact strength is well known to specialists in this field and are commercially available. Additional quantities kauchukopodobnoe polymer, especially emulsion grafted kucukodabasi polymers can be mixed, if necessary, in monomineralic aromatic polymer with modified uteroplacental properties.

Highly preferred monolinolein aromatic monomer is styrene, as specified by the modified polymer is high impact polystyrene. The most preferred vysokozharoprochnyh polystyrene can be obtained by polymerization in solution or mixture contains from 5 to 15 (more preferably from 6 to 9 wt.% polybutadiene rubber. Especially preferred vysokozharoprochnyh policy is respectfully from 100,000 to 225,000, and more preferably from 150,000 to 225,000). When measuring such molecular mass method was used gel chromatography using polystyrene standard.

Suitable polymers that can be used as component (b) are also monolinoleate aromatic polymers having a high degree syndiotactic configuration. Under a high degree syndiotactic configuration involves stereochemical structure with mainly syndiotactic configuration, stereostructure, in which phenyl groups or substituted phenyl groups as side chains are located alternately at opposite directions relative to the main chain consisting of carbon-carbon bonds. The regularity of the molecular structure quantitatively determined by the method of nuclear magnetic resonance in nuclei13C, well known to specialists in this field. Preferably, the degree of syndiotactic, as measured by the method13C-NMR spectroscopy, was more than 75% r dyads, preferably more than 90% r dyads. Suitable examples syndiotactic polymers are polystyrene, poly(and upomyanutye polymers as main components. Examples of poly(alkylthiol) is poly(methylsterol), poly(atistical) poly(isopropyl-styrene), poly(tert-butalbiral), etc. , poly(galottery) includes poly(chloresterol), poly(brostrom) and poly(forstera) and so on Poly(alkoxystyrene) includes poly(mitoxantron), poly(atoxicity), etc.

Syndiotactic the polymer used as component (b) typically has srednevekovoy molecular weight of from 10,000 to 10,000,000, preferably from 100,000 to 5,500,000, and srednekamennogo molecular weight of from 5,000 to 5,500,000, preferably from 50,000 to 2,500,000. Syndiotactic polymer has a melting point of from 160 to 310oC.

Preferred monovinylacetylene aromatic polymers for use as component (b) of the present invention are polystyrene, syndiotactic polystyrene modified with rubber vysokozharoprochnyh polystyrene, poly(vinyltoluene) and poly - methylsterol).

The mixture according to the present invention mainly contains at least 0.5 wt.%, preferably at least 10 wt.%, more preferably at least 15 wt.% to 99 weight percent, preferably to 80 weight percent, more preferably to 60 weight percent of monumenti (c) mixture for the polymer composition of the present invention are, essentially, statistical copolymers containing aliphatic - olefin and vinylidene aromatic monomer.

Aliphatic - olefin monomers contained in the component agent that improves compatibility (c) are aliphatic and cycloaliphatic - olefins having from 2 to 18 carbon atoms, and preferably olefins having from 2 to 8 carbon atoms. The most preferred aliphatic - olefin component agent compatibility (c) is ethylene or propylene, preferably ethylene, optionally together with one or more other olefins having from 3 to 8 carbon atoms, such as ethylene and propylene, or ethylene and octene or ethylene, propylene and octene.

Suitable vinylidene aromatic monomers included in the component (c) are monolinoleate aromatic monomers represented by the following formula:

< / BR>
in which R1and Ar were defined above. Suitable examples are styrene and (lower alkyl) or halogen-substituted derivatives. Preferred examples are styrene - methylsterol, (lower alkyl)- or phenylsilane the ring derivatives of styrene, such as ortho-, meta-, and para - IU eticheskim monomer is styrene.

Agent component compatibility (c) used in the present invention, is preferably pseudotachylites linear or generally linear, and more preferably a linear interpolymers aliphatic - olefin and nonoverridable aromatic monomer. These pseudotachylites linear interpolymer have been described in the patent application U.S. per. N 545403, filed July 3, 1990 (corresponding to European Patent EP-A-0416815), which was included in the present description by reference.

Specific distinctive feature pseudotachylites interpolymer is that everything is phenyl or substituted phenyl group, substituted at the main polymer chain, were separated by two or more methylene units. In other words, pseudotachylites interpolymer, including - olefin and vinylidene aromatic monomer, can be described by the following General formula (using styrene as the spatial hindered monomer and ethylene as the olefin to illustrate):

< / BR>
where j, k and l 1.

Obviously, during the polymerization reaction of ethylene and styrene using a catalyst, as described later, if satr shall be ethylene or hindered monomer, which was inserted in reverse order. Ethylene, on the other hand, can be inserted at any time. After the inverted insertion difficult monomer as the monomer must be ethylene, because the insertion of another difficult monomer at this stage would hamper the Deputy too close to the previously inserted complicated monometr.

Most preferably, component (c) agent compatibility was pseudotachylites linear interpolymers containing ethylene and styrene.

The content of units derived from vinylidene aromatic monomer contained in the component (c) agent compatibility, and preferably in pseudotachylites linear interpolymer, is preferably at least 1.0% mol, more preferably from 1.5 to less than 55 mole%, very preferably from 3.0 to 50 mole% and most preferably from 15.0 to 35 mole%.

It is preferable to use more high molecular weight components (c), having a MW greater than 13,000. Also preferably, such polymers possessed the index of fusion (12), ASTM D -1238 Procedure A, condition E, less than 125, more preferably from 0.01 to 100, dies), basically, statistical interpolymer, as will be described later, a certain amount of atactic vinylidene aromatic homopolymer may be formed as a result of homopolymerization vinylidene aromatic monomer at elevated temperatures. Generally speaking, the higher the polymerization temperature, the higher the number of the formed homopolymer. The presence vinylidene aromatic homopolymer, mainly prevents the purposes of the present invention and is valid. Vinylidene aromatic homopolymer may be separated from the component (c), if necessary, for example by extraction using a suitable extracting agent, such as acetone or chloroform. For the purpose of the present invention it is preferable that the component (c) vinylidene aromatic homopolymer is present in an amount of not more than 20 wt.% by weight of the component (c), and more preferably less than 15 wt.%.

Basically, the statistical interpolymer can be modified by graft copolymerization, hydrogenation, introduction of functional groups, or by other reactions well known to specialists in this field, progout easily be sulfatirovanne or chlorinated to obtain functionalized derivatives of established methods.

Pseudotachylites interpolymer can be obtained as described in patent application U.S. reg. room 545403, filed July 3, 1990 (according to European Patent EP-A-0416815). In the preferred operating conditions for such polymerization, the pressure was from atmospheric up to 3000 atmospheres and temperatures from the 30oC to 200oC. the Polymerization at temperatures above the temperature of autopolymerizing of the respective monomers may result in formation of some amounts of polymerization products of homopolymer resulting from free radical polymerization.

Examples of suitable catalysts and methods for obtaining pseudotachylites of interpolymers been disclosed in the patent application U.S. reg. N 545403, filed July 3, 1990 (EP-A-416815), the patent application U.S. reg. N 547718, filed July 3, 1990 (EP-A-468651); the patent application U.S. reg. room 702475, filed may 20, 1991 (EP-A - 514828); the patent application U.S. reg. room 876268, filed may 1, 1992, (EP-A-520732), the patent application U.S. reg. room 884966, filed may 15, 1992 (corresponding to WO 93/23412), the patent application U.S. reg. room 8003, filed January 21, 1993, the patent application U.S. reg. room 884966 filed March 19, 1993, the patent application U.S. reg. room 82197, filed June 24, 1993, as well as in Paestum links.

The mixture of the present invention contain an effective amount of the component (c) to achieve the best dispersive ability of the pigment of component (a) in the component (b) mixture or component (b) in the component (a) of the mixture compared with the mixtures (a) and (b) not containing the component (c). Thus, the component (c) may be used in amounts of at least 0.5 to 99, preferably at least 1-50 wt.%, and more preferably at least 2-20 wt.% on the total weight of (a), (b) and (c). If the number of (c) is too low, it will produce bad compatibility (a) and (b) in the mixture. If the number of (c) is too high, the mixture loses the desired rigidity given to her by the component (b).

Preferably, if the mixture of the present invention contain from 35 to 75 wt. % (a), from 15 to 60 wt.% (b) and from 2 to 20 wt.% pseudotachylites interpolymer (c).

In accordance with another preferred embodiment of the present invention, these mixtures of component (a) selected from the group consisting of low density polyethylene, high density polyethylene, mostly linear polyethylene, linear low density polyethylene and polypropylene, and the component (b) is selected from the group consisting of homopolymer St="ptx2">

In another preferred embodiment of the present invention the mixture contains from 40 to 87 wt.% component (a), from 11 to 40 wt.% syndiotactic polystyrene as component (b) and from 2 to 20 wt.% percent pseudotachylites linear interpolymer, including-olefin and monotinicity aromatic monomer (c). According to another preferred variant, the component (a) in these mixtures is polypropylene.

The polymer mixture of the present invention can be prepared by any standard method of mixing, for example, using a single screw extruder and twin screw extruder, mixer of Brabender (Brabender), continuous mixer Farrel (Farrel) and two mixers. The order of mixing and the shape of the blend components do not play a decisive importance. Mixing temperature is preferably such that allow you to obtain a homogeneous mixture of components. Typical temperatures are temperatures above the softening point or melting at least one of the components, and more preferably above the softening point or melting of all components.

The polymer mixture of the present invention may also contain additives such is more of elastomeric modifiers to improve impact strength, etc.

The polymer mixture of the present invention can be molded into films, sheets, press articles, foams and articles from foam using standard methods. Suitable methods are injection molding, press-moulding, extrusion and thermoforming. The product can be made one way or the two-stage methods. In one method, the stage of mixing and stirring United and are continuously on the instrument with adequate mixing capacity. In the two-stage process, a mixture is first prepared in pellet form by appropriately mixing and granulating, and then subjected to a conventional method of molding. By using these components (c) agents compatibility with their good dispersing properties can be applied more economical one-step method.

Sheet products are usually ekstragiruyut in one stage, and in most cases subjected to thermoforming as described in U.S. Patent 4386187, which is at present a description here by reference. Film products can also be manufactured by extrusion and thermoforming, as well as by casting or paredpochteniya made on a separate stage. Foam sheet products can be prepared as described in U.S. Patent 4020025, which is introduced into the present description by reference, and which describes the first stage of mixing polymer granules with subsequent extrusion foam sheet. Products made of foam can be manufactured by extrusion of the foam. Press articles in the form of castings are usually produced by two-stage method, including a first stage mixing, followed by a stage of injection molding. In the Japan Patent JP 48-43031 was described method of molding articles of foam by dry mixing is able to decompose a pore-forming agent, with subsequent injection molding.

The polymer mixture of the present invention can be used to produce films, such as label film, foam, especially packaging foam and rigid insulating foam, elastic can stretch the polymer granules, refrigeration lines, capable of thermoforming sheets and other products that are molded by injection molding or similar methods. The mixture of the present invention have been particularly useful in that they can be made from waste olefin and nonoverridable aromatics is an effective method of recycling waste polymeric materials.

In a preferred aspect, the present invention relates to the expanding composition, including a polymer mixture of the present invention and expanding agent. The term "expanding agent" means the agent or compound that expansion, for example, heat, pressure changes, or mechanical changes its physical or chemical state, contributing to an increase in its volume. The preferred extension agents are conventional foaming agents commonly used for the manufacture of pins.

In a preferred embodiment, the expanding composition is made in the form of beads.

In an advantageous embodiment, the foam composition is obtained by foaming an expandable composition. Preferably the foaming composition is made in the form of a sheet or Board.

In another aspect the present invention relates to an article molded from the polymer blend of the present invention. Preferably, an industrial product produced by thermoforming, extrusion, injection molding or molding by blowing. This industrial product is preferably made in the form of a sheet or film.

In more detail, the invention is illustrated in the following examples, which, however, should not be construed as limiting its scope. Comparative examples were marked with the letter "C".

Value index melting, as given in the examples were measured according to ASTM D -1238 at 190oC with a load of 2.16 kg

The magnitude limit of the coloring strength is ANO in the examples were measured according to ASTM D 882-91, Method A, except that the length of the Etalon was 25.4 mm (1 inch) and the speed of the RAM was 5 mm per minute.

The amount of hardness, as given in the examples were the energies of the tensile strength, measured according to ASTM D 882-91, Method A, except that the length of the Etalon was 25.4 mm (1 inch) and the speed of the RAM was 5 mm per minute.

The magnitude of the module, as given in the examples, was equal to 2 percent secant module, measured according to ASTM D 882-91, Method A, except that the length of the Etalon was 25.4 mm (1 inch) and the speed of the RAM was 5 mm per minute.

The percentage of vinylidene aromatic monomer present in the agents compatibility pseudotachylites of interpolymers used in the polymer mixtures according to the present invention were identified by13C-NMR spectroscopy. All percentages expressed by weight, unless otherwise indicated.

EXAMPLES

Agents to improve the compatibility, used as component (c) in the polymer mixtures of the present invention, were prepared by the following methods. Copolymers of ethylene/styrene were obtained using (tert-butylamide)dimethyl (those the catalyst in a ratio of one to one according to the following procedure. A two-liter reactor with a stirrer was loaded with the desired amount of mixed alkangovolo solvent (Isopar-E, available from Exxon Chemicals Inc.) and the desired amount of co monomer styrene. Hydrogen is fed into the reactor by means of a differential boost pressure (the pressure difference indicated by Delta) from tank 75 ml. Reactor was heated to the desired temperature and saturated with ethylene to the desired pressure. The catalyst and socialization were mixed in a dry box by precapitalism pipette the desired number 0005 M solution of acetalization Isopar-E or toluene in the solution catalysts Isopar-E or toluene. The resulting solution was transferred into the tank for loading catalyst and introduced into the reactor.

Polymerization was carried out with ethylene on demand. Additional loading of the catalyst and socializaton, if they were used, was carried out in the same manner and periodically added to the reactor. After completing the cycle, the polymer solution was removed from the reactor and the reaction was suppressed isopropyl alcohol. Hindered phenolic antioxidant (Irganox 1010, available from Coba Geigy Corp.) was added to the polymer, except in the case of obtaining ES-4, using tert-butylcatechol. Volatile products is S="ptx2">

Conditions of formation and properties pseudotachylites of interpolymers were given in tables 1 and 2 (table. 1 - 13 see the end of the description), respectively. It was found that pseudotachylites interpolymer agents compatibility contain a small amount of amorphous polystyrene.

In the comparative examples used the following agents combine (if used).

KRATON G-1657, supplied by Shell Chemical Company, which was a mixture of diblock and triblock copolymers containing 13 wt.% styrene and having an index melting 2,23;

KRATON G-1652, supplied by Shell Chemical Company, which is blockcopolymers styrene/ethylene-butylene/styrene containing 29 wt.% styrene;

VECTOR 6241-D supplied by Dexco Polymers, which is a triblock copolymer of styrene/butadiene/styrene (SBS) containing 43 wt.% styrene and having an index melting 5,2; and

STEREON 840A supplied Fierstone Synthetic Rubber and Latex Co. who was the diblock copolymer of styrene/butadiene (SB) containing 43 wt.% styrene and having an index melting 2,32.

Olefinic polymer components (a) used in examples are shown in table 3.

Monolinoleate aromatic polymer components (b) used in Prince Rheocord Model 90, pressed on the press for hot forming and tested in tension. Except mixtures containing syndiotactic polystyrene (SPS), mixtures were prepared at approximately the same conditions. The granulated mixture of resins in a total amount of 40 g was mixed in the melt in the mixer of khaak (Haake) for 15 minutes at 180oC and a rotor speed of 30 revolutions per minute in nitrogen atmosphere. A mixture of SPS/HDPE were mixed with 270oC and pressed into sheets at 290oC. Thickness ranged from 0.7 mm to 1.1 mm, which varied from sheet to sheet. The sheet was cut into strips of a width of 1.27 cm (1/2 inch) using a cutter Thwing-Albert Model LDC-50. The cutter is adapted to cut the sheet samples for stretching without cracking at the edges, sending cracks from the strips. Properties of samples for tensile strength were determined using tester strain Instron 1123 when the speed of the slide 5 mm/min and the width of the clip 2.54 cm (1 inch). Five samples were tested for each mixture and the average value was considered as a typical value for this mixture.

The amount of hardness were determined by the area under the curves stretching.

Example 1

Polymer blends were prepared from polystyrene obseg(comparative). The compositions of the mixtures as well as their properties are given in table 5.

The data in table 5 show that the polymer mixture, combine using the ES-1 according to the present invention, provide a more rigid and dense mixture than mixtures containing an equivalent amount of KRATON G-1657 SEBS as a part-time. The stiffness of the mixtures, the shared according to the invention, was significantly increased at 2.5 wt.% (part-time and continued to increase as the level was increased to 20 percent. SEBS block copolymers was only two times less effective at the level of 2.5 percent and its properties were not improved by increasing this level. On the contrary, when the level of SEBS 5 percent and above, the stiffness of the mixture was decreased, as evidenced by the reduction module, which was undesirable. Reducing the stiffness of the mixtures of the present invention was significantly less when the same quantities of the agent compatibility.

Example 2

Polymer blends were prepared from General purpose polystyrene STYRON 612 and LDPE 3 in various respects mixing for a set number of agent compatibility ES-2 (invention) and without this agent (comparative). The compositions of mixtures, as well as their properties Pref is Acento polystyrene LDPE leads to a sharp deterioration in the toughness of LDPE, leaving almost no mechanical strength at 30% introduction of polystyrene. With the introduction of agent compatibility and the mixture was zakusalas to high levels of polystyrene. At levels higher than 30 percent polystyrene mixture was significantly more rigid than the main LDPE, as evidenced by the module.

Example 3

Polymer blends were prepared from General purpose polystyrene STYRON 612 and different types of olefinic polymers with different ways of mixing the agent compatibility selected from the ES-2 (invention), a mixture of ES-2 and KRATON G-1657 (invention), and KRATON G-1657 (comparative) as well as without this agent (comparative). The compositions of mixtures, as well as their properties are shown in table 7.

The data in table 7 show that when the agent compatibility ES in a mixture of 10%, were obtained mixture having excellent rigidity. SLOP with lower density, gives a mixture that is more plastic, but lower module. A mixture of intermediate density SLOP 2 were sufficiently strong and rigid. Addition of 5% of the agent compatibility ES to PS - enriched (80% PS) blends relatively little effect on impact strength. At such a high level PS PS resin obviously OOI interest, as the mixture combines rigidity and resistance to high temperatures. Adding 10 percent agent compatibility ES lengthens the mixture of HDPE/PS greater than 10 percent. For PS - rich blends (65% PS) 5 percent of the agent compatibility ES, apparently, is not enough to extend less than 10 percent. A threefold increase in toughness was achieved by introduction of a 10 percent agent compatibility ES in the mixture DPE/PS with 50 percent of PS.

Example 4

Polymer blends were prepared from different types monomineralic aromatic polymers and various types of olefin polymers in various relations with the agent compatibility ES-2 or ES-3 (invention) and without agent compatibility (comparative). The compositions of mixtures, as well as their properties were given in table 8.

In table 8 the influence of the chemical composition of styrene polymers on the properties of the mixtures. On the properties of the mixtures was not significantly influenced by the presence of groups of co monomer of the acrylate (SBA) or p-methylstyrene (PVT) in the molecular structure. As a mixture of LDPE/SBA, and a mixture of LDPE/PVT combined with ES have satisfactory impact strength and rigidity. A mixture of LDPE/SAN was not well compatible, as these mixtures. Sommese kernie mixtures were made of General purpose polystyrene STYRON 612 and polymers LDPE and HDPE at various mixing relations with several different agents compatibility according to the invention. The compositions of mixtures, as well as their properties were given in tables 9 and 10.

The data in tables 9 and 10 show that for mixtures LDPF or HDPE with agents compatibility GPPS, styrene content in ES preferably constituted 15-35 M%. The optimal number of agent compatibility slightly differed for different mixtures. To a mixture of LDPE/PS resin ES with 20 M% styrene, was the most effective. Resin ES with 25 M% styrene (ES-9), more effective for mixtures of HDPE/PS enriched HDPE. The mixture of HDPE 2/STYRON 612/ES-9: 60/30/10 is distinguished by its exceptionally high elongation and toughness. Like HDPE resin, the mixture was formed into a neck (i.e., narrowing) during the tensile tests.

Example 6

Polymer mixtures, especially suitable for making industrial gaskets, for example, refrigerators and film for labels, were prepared from several vysokozharoprochnyh polystyrene and polymers LDPE and HDPE at various mixing relations with several different pseudostatic interpolymer agents compatibility (invention). Were comparisons made with several copolymers used as agents to improve the compatibility. The compositions of mixtures, as well as their properties, etc the effective agent compatibility for all mixtures PE/HIPS. In a mixture of HDPE 3/STYRON 404 HIPS: 35/55 this agent compatibility is the same or more effective than the vector 6241-D SBS as the steepness and the module, and exceeds the SEBS copolymer. In a mixture of LDPE/HIPS 60/30 several copolymers ES 18-27 M% styrene are more effective than SB block copolymers. As block copolymers of butadiene-styrene has poor thermal stability and stability to ultraviolet radiation, these copolymers ES are preferred for these applications. Replacement resin HDPE resin having a high molecular weight tends to improve properties.

Example 7

Weatherproof polymer mixtures were prepared from General purpose polystyrene STYRON 612 and polymers LDPE and HDPE in various respects mixing with several different pseudotachylites interpolymer agents compatibility (invention) and with several copolymers (comparative). The compositions of mixtures, as well as their properties were given in table 12.

Weatherproof polymer mixture can be obtained from the GPPS resin and polyethylene resin using the ES copolymer as an agent to improve compatibility. In a mixture containing 50 percent or less polistirolio-copolymer SBS.

All of these compounds, based on PPS, effectively combined with copolymers ES with 18-25 M% styrene. Polymer blends were prepared from syndiotactic polystyrene SPS 2 and high molecular weight of the modified rubber polypropylene PROFAXTMSD 613 at various mixing relations with several pseudotachylites interpolymer agents compatibility ES (invention) and copolymers (comparative). The composition of the mixtures, as well as their properties were given in table 13. Components, and 0.25 percent of an antioxidant Irganox 1010 and 0.25 percent of antioxidant Irgafos 168 were mixed for 10 minutes in batches of 40 g in the mixer of Brabender (Brabender) periodic type, operating at 60 rpm and 260oC.

The mixture was cooled and grinded into powder in the mill Wiley (Wiley), and then was molded by pressing in a small microbrush for tensile tests, with the size of 0.33 cm (0,130 inches) x 0,46 cm (0,183 inches) x 1.8 cm (0.75 inches) (length pattern). The cycle of direct pressing 2 min/10 min/2 minutes for pre-heating/pressure/cooling was used at the temperature of molding 300oC. Elongation at break and modulus of elongation were determined at 23oC / min net and the (10 mil) radius cut) by testing the impact of the 23oC.

The data in table 13 show that the mixtures according to the invention have better stiffness (modulus) than mixtures containing an equivalent amount of Kraton G1652, and thus have an increased elasticity and impact strength (Izod).

1. The polymer composition containing (a) from 0.5 to 99 wt.%, calculated on the total weight of (a), (b) and (C) aliphatic homopolymer-olefin, or a copolymer, or a copolymer of aliphatic-olefin and non-aromatic monomer capable of copolymerization; (b) from 0.5 to 99 wt.%, calculated on the total weight of (a), (b) and (C), homopolymer or copolymer monomineralic aromatic monomers or copolymer nonoverridable aromatic monomer and a monomer capable of copolymerization and are not aliphatic-olefin, and (C) from 0.5 to 99 wt.%, calculated on the total weight of (a), (b) and (C) a polymeric agent compatibility, characterized in that the polymer as designated agent compatibility mostly use statistical copolymer of aliphatic-olefin and vinylidene aromatic monomer.

2. Composition under item 1, characterized in that (a) contains a homopolymer or copolymer of olefin having from 2 to 18 carbon atoms.

3. The composition according to p. bolee-olefins, having 3 to 8 carbon atoms.

4. Composition under item 1, characterized in that monotinicity aromatic monomer (b) represented by formula

< / BR>
in which R1choose from the group of radicals consisting of hydrogen and alkyl radicals containing three or less carbon atoms, and Ar is a phenyl group or a phenyl group having from 1 to 5 substituents selected from the group consisting of C1-4-alkyl and C1-4-halogenoalkane.

5. Composition under item 1, characterized in that the monomer (b) capable of forming a copolymer, selected from the group consisting of N-phenylmaleimide, acrylamide, Acrylonitrile, Methacrylonitrile, maleic anhydride, acrylic acid, C1-4-alkylacrylate or C1-4-alkyl methacrylates.

6. The composition according to p. 4, wherein (b) includes polystyrene, vysokozharoprochnyh polystyrene modified with rubber, poly(vinyltoluene) or poly(-methylsterol).

7. Composition under item 1, characterized in that, in the main statistical copolymer component (C) contains aliphatic-olefin and monotinicity aromatic monomer.

8. The composition according to p. 7, characterized in that the olefin has from 2 to 8 carbon atoms, and monolinolein the Alov, consisting of hydrogen and alkyl radicals containing three or less carbon atoms, and Ar is a phenyl group or a phenyl group substituted by 1 to 5 substituents selected from the group consisting of C1-4-alkyl and C1-4-haloalkyl.

9. The composition according to p. 8, characterized in that the olefin is ethylene, and monomineralic aromatic monomer is styrene.

10. The composition according to p. 7, characterized in that, in the main statistical copolymer contains from 1 to less than 55 mol.% nonoverridable aromatic monomer.

11. Composition under item 1, characterized in that, in the main statistical copolymer has an index melting point of from 0.01 to 100.

12. Composition under item 1, characterized in that (a) are selected from the group consisting of low density polyethylene, high density polyethylene, mostly linear polyethylene, linear low density polyethylene and polypropylene, and (b) is selected from the group consisting of homopolymer styrene-modified rubber vysokomarochnogo polystyrene, poly(vinyltoluene) and poly(-methylstyrene).

13. The composition according to p. 7, characterized in that it comprises from 40 to 87 wt.% (a) from 11 to 40 wt.% syndiotactic polystyrene in quality what it contains polymer composition under item 1 and the extending agent is in the form of granules.

15. Expanded onto the composition, characterized in that it is obtained by foaming an expandable composition for p. 14 is in the form of a sheet or plate.

16. Industrial product, characterized in that formed from the polymer composition by p. 1 by thermoforming, extrusion, injection molding or blow molding and has the form of a sheet or film.

17. The method of packaging of substances or articles, characterized in that a homogeneous mixture of components (a), (b) and (C) polymer composition under item 1 are in the form of a shell for covering or container suitable for introducing the substances or articles that need to be Packed, and the shell is in the form of a sheet or film, and the substance or product are food and the container is designed for packing liquid.

 

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