Halogenated elastomeric compositions showing elevated viscosity

FIELD: polymer materials.

SUBSTANCE: invention relates to elevated-viscosity halogenated elastomers as constituents of thermoplastic composition,. The latter comprises thermoplastic material and at least one isoolefin copolymer including unit derived from halomethylstyrene, which are mixed with at least one hindered amine or phosphine of formula R1R2R3N or R1R2R3P. In a preferred embodiment, R1,R2, andR3 represent lower and higher alkyl groups. Thus obtained ionically bound amine- or phosphine-modified elastomers are suitable for preparing thermoplastic mixed elastomeric compositions.

EFFECT: improved mixing homogeneity due to elevated viscosity of copolymer and formation of finer dispersion of one polymer system in the matrix of another polymer system.

20 cl, 10 tbl, 5 ex

 

The technical field to which the invention relates.

The present invention relates to halogenated elastomers having high viscosity. These compositions with high viscosity are mixtures souleimanova copolymer comprising at least link derivateservlet from kilometerstirana, and at least one amine or phosphine.

Background of invention

Thermoplastic elastomer is generally defined as a polymer or mixture of polymers which can be processed and re-processed the same way as conventional thermoplastic materials, and which, nevertheless, has properties and performance characteristics similar to that operating temperature has vulcanized rubber. Mixtures or alloys of plastic and elastomeric rubber acquire increasing importance in obtaining high performance thermoplastic elastomers, especially as substitutes for thermoset rubbers in a variety of applications.

Polymer blends which have a combination of both thermoplastic and elastic properties, is usually prepared by combining a thermoplastic polymer with an elastomeric composition such that the elastomer is homogeneous and uniformly dispergirovanija as the basics of discrete particles in a continuous phase of thermoplastic material. Early work dedicated to the vulcanized compositions found in the patent US 3037954, which describes static vulcanization, as well as the technology of dynamic vulcanization, where can vulcanizate elastomer is dispersed in a resinous thermoplastic polymer and the elastomer vulcanized with simultaneous continuous stirring and shear effects on the polymer mixture. The resulting composition is microglial dispersion of vulcanized elastomer, such as butyl rubber, chlorinated butyl rubber, polybutadiene and polyisoprene, seamless matrix of thermoplastic polymer, such as polypropylene.

Depending on the end use of such a thermoplastic elastomer (TPE) compositions can include one or a mixture of thermoplastic materials, such as the propylene homopolymers and propylene copolymers and the like thermoplastic materials used in conjunction with one or a mixture of vulcanized or unvulcanized elastomers such as ethylene-propylene rubber, TAPD (ternary ethylene-propylene diene with links) rubber, diolefines rubber, butyl rubber or similar elastomers. TPE compositions can also be prepared, when used thermoplastic material is a structural resin, oblad the expansion of its good high-temperature properties, such as polyamide or polyester, used in combination with vulcanized or unvulcanized elastomer. Examples of such TPE compositions and methods of processing such compositions, including methods of dynamic vulcanization can be found in US 4130534, 4130535, 4594390, 5021500, 5177147 and 5290886, as well as in WO 92/02582.

Particularly preferred elastomeric polymers that can be used for the preparation of TPE compositions are halogenated statistical isorevenue copolymers comprising at least derivateservlet from kilometerstirana links. Halogenated elastomeric copolymers of this type (denoted as BEAM polymers, brominated isobutylene-p-methylstyrene copolymers) and the retrieval method described in US 5162445. Vulcanizate TPE compositions comprising these copolymers are described, in addition to other literature in the US 5013793 and 5051477.

TPE composition is usually prepared by mixing in the melt or processing in the melt of thermoplastic and elastomeric components at temperatures in excess of 150°and in terms of mixing with a high shear rate (shear rate above 100 1/C-1to prepare a fine dispersion of one polymer system in a matrix of another polymer system. The finer the dispersion, the better the mechanical properties of the TPE product.

Thanks AK is ivali expiration and characteristics of liquefaction under the influence of shear forces, inherent in such BEAMS polymers, values reduce the viscosity of these polymers at elevated temperatures and shear rates, which are natural while mixing, be much more pronounced than the decrease of the viscosity of thermoplastic component, which is mixed BEAMS polymer. However, the difference in minimizing the viscosity of the BEAM and thermoplastic components during mixing and/or processing is essential to achieve uniform mixing and fine morphology of the mixture, which is crucial for good mechanical properties of the mixture.

Summary of the invention

According to the invention features a composition, preferably a thermoplastic composition comprising halogenated elastomer and increases the viscosity of the additive, such as hindered amine or phosphine. In one embodiment, the halogenated elastomer is a copolymer of samanaleya with4With7including links, derivateservlet from kilometerstirana. This copolymer is blended with at least one difficult aminoven or phosphine compounds having the corresponding structure (R1R2R3)N or (R1R2R3)R, where R1denotes H or alkyl with C1With6, R2denotes alkyl with C With30and R3denotes alkyl with C4With30and, in addition, where R3represents a higher alkyl than R1and the said mixing is carried out at a temperature which exceeds the melting point of the specified difficulty amine or phosphine compounds. In a preferred embodiment, the mixing is carried out in such a way as to create a homogeneous mixture.

The invention further proposes a method of increasing the viscosity of the copolymer samanaleya with C4C7that includes a mixture of this copolymer with difficult aminoven or phosphine compound.

The invention proposes a new technique aimed at increasing the viscosity of BEAM copolymers so that their viscosity during wysokosciowe thermal mixing more closely approached viscosity thermoplastic materials with which they are mixed, or met her, thus facilitating more uniform mixing and the formation of more fine dispersion of one polymer system in a matrix of another polymer system.

Detailed description of the invention

In the sense in which it is used in the present description, the term "dynamic vulcanization" means a vulcanization process or curing of the rubber contained in thermoplastic elastomer of the composition is, in which the rubber vulcanized under conditions of high shear at a temperature which exceeds the melting point of thermoplastic component. Thus, the rubber is simultaneously structure and is dispersed in the form of fine particles in thermoplastic matrix, although, as noted above, it is also possible existence of other structures.

In the sense in which it is used in the present description, the term "vulcanized" means that the rubber component, which is to be vulcanized, cured to a state in which the elastomeric properties of the structured rubber similar to the properties of the rubber in its conventional vulcanized state, not to mention thermoplastic elastomer composition. The degree of vulcanization can be expressed by the values of the content of the gel or, on the contrary, the content of extractable components. Alternatively, the degree of vulcanization can be expressed by the density of cross-links. All of these characteristics in this area is well known in the art and shown, for example in US 5100947 and 5157081.

In the sense in which it is used in the present description, the term "composition" includes mixtures of product haloiding static copolymers samanaleya with4With7such as isobutylene, and alkylthiophenes somone who measure with the addition to the influence on the viscosity, such as amine or phosphine. The composition may also include other components.

In the example in the present description reference groups of the Periodic table of elements used in the new numbering scheme for groups of the Periodic table of elements, which is represented in Hawley's Condensed Chemical Dictionary 852 (13th ed. 1997).

Occurring in the present description the term "elastomer" refers to any polymer or composition of polymers corresponding to the definition according to the standard ASTM D 1566. The terms "elastomer" and "rubber"used in the present description, can be used interchangeably.

Isorevenue copolymer comprising derivateservlet from kilometerstirana link

The compositions of the present invention include at least one halogenated elastomer. In one embodiment, the halogenated elastomer is a statistical copolymer comprising at least links derivateservlet from isoolefine with4With7such as links, derivateservlet from isobutylene, and links derivateservlet from kilometerstirana. Kilometerstirana link can be ortho-, meta -, or para-alkyl substituted styrene unit. In one embodiment, derivateservlet from kilometerstirana element is a p-halomethyl the Tyrol, containing at least 80%, more preferably at least 90 wt.%, para-isomer. As halogroup" may be any atom of halogen, suitable atom of chlorine or bromine. Halogenated elastomer may also include functionalized copolymers in which at least some of the alkyl substitute groups present in the styrene monomer units contain benzyl halogen atom or any other functional group, optionally as described below. These copolymers in the present description are called "isoretinoin copolymers, including link, derivateservlet from kilometerstirana", or simply "isoretinoin copolymers".

Isorevenue copolymer can also include links, derivateservlet from other monomers. Otoolefan copolymer may be a connection With4C12, non-limiting examples of which are compounds such as isobutylene, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butene, 2-butene, metilidinovy ether, inden, vinyltrimethylsilane, hexene and 4-methyl-1-penten. Such a copolymer may also include links derivateservlet from multilatina. Multilevel is a polyunsaturated olefin with4C14such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, mi the price 6,6-dimethylfuran, hexadiene, cyclopentadiene and piperylene, as well as other monomers, such as described in EP 0279456 and US 5506316 and 5162425. Appropriate links derivateservlet of styrene monomers that may be contained in the copolymer include styrene, methylsterol, chloresterol, mitoxantron, inden, indene derivatives, and combinations thereof.

In another embodiment, the copolymers are statistical elastomeric copolymers link, derivatizing from ethylene, or link, derivatizing from α-olefin with3With6and link, derivatizing from kilometerstirana, preferably p-kilometerstirana containing at least 80%, more preferably at least 90 wt.%, para-isomer and also include functionalized copolymers in which at least some alkyl replacement group in the styrene monomer units contain benzyl halogen atom or any other functional group.

Preferred isorevenue copolymers can be characterized as a copolymer comprising the following monomer units, statistically distributed along the polymer chain:

in which each of R and R1independently denotes a hydrogen atom, lower alkyl, predpochtitel is on alkyl with C 1no C7or primary or secondary alkylhalogenide, and X denotes a functional group, such as halogen atom. Suitable halogen atoms are chlorine atoms, bromine or combinations thereof. In the preferred embodiment, each of R and R1denotes a hydrogen atom. Group-CRR1H-CRR1X can be substituents in the styrene ring in either the ortho-or meta-or para-position, preferably in the para-position. Up to 60 mole percent n-substituted styrene units included in the copolymer structure may have the above functionalized structure (2) in one embodiment, and from 0.1 to 5 mol % in another embodiment. And yet in another embodiment, the content of the functionalized structure (2) is from 0.4 to 1 mol %.

The functional group X may be a halogen atom or any other functional group that can enter the nucleophilic substitution of benzyl halogen atom other groups, such as residues of carboxylic acids, salts of carboxylic acids, esters of carboxylic acids, amides and imides, hydroxyl, alkoxide, venexiana, tialata, thioester, xanthogenate, cyanide, lanata, the amino and mixtures thereof. These functionalized somnolence copolymers, method for their preparation and methods of functionalization and Wu is kansasii more specifically described in US 5162445.

The most widespread use of such functionalized materials are elastomeric random copolymers of isobutylene and p-methyl styrene, comprising from 0.5 to 20 mol % of units of p-methylstyrene in which up to 60 mol % metal alternative groups present on the benzyl ring contain a bromine atom or chlorine, preferably a bromine atom (p-brometalia), as well as their options, functionalized residues, acids or esters, in which the halogen atom is substituted by a residue of maleic anhydride or acrylic or methacrylic acid. These copolymers are referred to as "halogenated isobutylene/p-methylstyrene copolymers" or "bronirovannymi isobutylene/p-methylstyrene copolymers", they are technically accessible as elastomers EXXPRO™ (company ExxonMobil Chemical Company, Houston, Texas). It is obvious that the use of the terms "halogenated" or "octabromodiphenyl" is not limited to the method of halogenation of the copolymer, they merely serve to describe copolymer, which includes links derivateservlet from isobutylene, links, derivateservlet of p-methylstyrene, and links derivateservlet of p-kilometerstirana.

In the preferred embodiment, these functionalized polymers have essentially homogeneous compositional distribution, resulting in the content of p-alkylthiols the x links in at least 95 wt.% polymer is in the 10%range relative to the average content of p-alkylthiophene links in the polymer. More preferred polymers are also characterized by a narrow molecular weight distribution (Mw/Mn), constituting less than 5, more preferably less than 2.5, preferably srednevozrastnoe molecular weight in the range of from 200,000 to 2000000 and preferred srednekamennogo molecular weight in the range of from 25,000 to 750,000 people, as it determines gel chromatography.

Such copolymers can be obtained by suspension polymerization of the monomer mixture using a Lewis acid as catalyst, followed by halogenoalkanes, preferably by bromirovanii, in solution in the presence of halogen and initiator of free-radical polymerization, such as heat and/or light and/or a chemical initiator, and optional subsequent electrophilic substitution of bromine atom other functional derivational link.

Preferred halogenated isobutylene/p-methylstyrene copolymers are brominated polymers which generally contain from 0.1 to 5 wt.% brometalia groups. And yet in another embodiment, the number brometalia groups is from 0.2 to 2.5 wt.%. To put it differently, the preferred copolymers contain from 0.05 to 2.5 mol % of bromine atoms in recalculation on weight of the polymer, more preferably from 0.1 to 1.25 mol % of bromine atoms, is almost free from the ring atoms of halogen or of halogen atoms in the main polymer chain. In one embodiment, the copolymer is a copolymer of units, derivatizing from samanaleya with4C7, links, derivatizing of p-methylstyrene, and links, derivatizing of p-kilometerstirana, and p-kilometerstirana links are in the copolymer in an amount of from 0.4 to 1 mol%, calculated on the copolymer. In another embodiment, this p-gallmeister is a p-brometalia. The Mooney viscosity (1+8, 125°With ASTM standard D 1646, modified method) is from 30 to 60 unit.

Amine/phosphine component

Increasing the viscosity of BEAM copolymers reach the mixing of BEAM copolymer with relevant dull aminovymi or phosphine compounds or additives to increase viscosity) under the influence of shear force and at temperatures that exceed the melting temperature of the amine or phosphine, over a period of time sufficient to allow the amine or phosphine to be uniformly dispersed in the BEAM material, usually from 1 to 10 min, and at preferred temperatures in the range from 100 to 180°C.

Suitable preferred additive for increasing the viscosity, which can be used include those which correspond to the formula (R1R2R3)Q in which Q is oznachaet element of group 15, preferably a nitrogen atom or phosphorus, and in which R3denotes alkyl with C10C20, a R1and R2that are the same or different, represent a lower alkali, more preferably alkali with C1With6. From obstructed amine/phosphine compounds that can be used, the preferred tertiary amines include those that meet the above-mentioned formula (R1R2R3)N. Particularly preferred amines are decollimation, hexadecyldimethylamine, alkyldiphenylamine hydrogenated tall oil, allylmethylamine digidrirovannoe tall oil, etc. connections.

Preferred hampered phosphine compounds of the formula (R1R2R3)P are also those in which R3denotes alkyl with C10With20, a R1and R2that are the same or different, represent a lower alkali, more preferably alkali with C1With6. These phosphines are analogues of the above amines.

The amount of amine or phosphine introduced into the BEAM copolymer, should be sufficient to increase the viscosity of the composition (increase given shear rate and temperature). The resulting composition can be called in different ways: as "amino - or phosphine/copolymer" composition or com is ositio "additive for increasing the viscosity/copolymer, or as the song "amine - or phosphine/BEAMS". In one embodiment, the viscosity of the composition of the additive for increasing the viscosity/BEAMS" at 220°and shear rate 100 1/s exceeds 1300, in another embodiment it is at 220°and shear rate 100 1/s ranges from 1300 to 6000 PA·and at 220°and shear rate 100 1/s - from 1400 to 5000 PA·in yet another variant. In another embodiment, the viscosity of the composition of the additive for increasing the viscosity/BEAM at 220°and a shear rate of 1000 1/s greater than 200, in another embodiment it is at 220°and a shear rate of 1000 1/s ranges from 200 to 600 PA·and at 220°and a shear rate of 1000 1/s - from 220 to 550 PA·in yet another variant. Usually enough from 0.05 to 2 molar EQ., more preferably from 0.1 to 1 molar EQ., amine or phosphine to the halogen BEAM.

The composition of the additive for increasing the viscosity/BEAM, amine/BEAM in one embodiment, the present invention is prepared essentially in the absence of solvent. More specifically, amine and BEAM components of mixed methods for professionals in this field known in the art, without addition of organic solvent. In the composition or during the mixing of the components, solvents, mainly organic solvents, essentially absent. The term "essentially no" imply that contains the I is less than 5 wt.% solvent from the weight of all available songs and less than 2 wt.% in another version.

Modified BEAM polymers of the present invention should be distinguished from ionomers described in US 5162445 or WO 94/10214. The receipt of such materials according to these references includes carried out in an organic solvent of the reaction of nucleophilic substitution, in which benzyl halogen atom contained in the BEAM-polymer replaces, thereby rendering the polymer ion meter with ionogenic amine or phosphine functional group. The materials obtained in accordance with the present invention, are believed to ion associated polymer chains without any substitution of the halogen atom in the polymer chains. Thanks to the Association of ions creates a modified polymer having high viscosity compared to the viscosity of the original BEAMS of the polymer.

Thermoplastic polymers

Isorevenue copolymer with high viscosity according to the invention can be used for blending with thermoplastics. Thermoplastic polymers suitable for use in performing the present invention include amorphous, partially crystalline or substantially completely crystalline polymers selected from polyolefins, polyamides, polyimides, polyesters, polycarbonates, polysulfones, polylactones, Polyacetals, Acrylonitrile-butadiene-styrene copolymer resins, poly is teleocidin, copolymers of ethylene/carbon monoxide, polyphenylensulfide, polystyrene, styrene-Acrylonitrile copolymer resins, resins of copolymers of styrene/maleic anhydride, aromatic polyketones and mixtures thereof. These and other thermoplastics are described, for example, in US 6013727.

The polyolefins suitable for use in compositions according to the invention are thermoplastic, at least partially crystalline polyolefin, the homopolymers and copolymers, including polymers obtained using catalysts of the type catalysts, Ziegler-Natta or catalysts for the sole areas, such as metallocene catalysts. They should be obtained from monoolefinic monomers, each of which contains from 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-penten, copolymers comprising units of these monomers, and the like, and the preferred monomer is propylene. Used in the description and the claims the term "polypropylene" includes the homopolymers of propylene, as well as reactor copolymers of polypropylene which can contain from 1 to 20 wt.% parts of ethylene or alpha-olefin co monomer containing from 4 to 16 carbon atoms, and mixtures thereof. Polypropylene can be highly crystalline isotactic or syndiotactic polypropylene, usually on edusim narrow range of glass transition temperature (TC). When performing the invention can be used technically available polyolefins.

The term "polypropylene" includes the homopolymers of propylene, as well as reactor copolymers of polypropylene which can contain from 1 to 20 wt.% derivatizing of ethylene units or parts, derivatizing from another α-olefin co monomer containing from 4 to 6 carbon atoms. Polypropylene can be highly crystalline isotactic or syndiotactic polypropylene. Reactor copolymer can be either statistical or block copolymer. Other acceptable thermoplastic polyolefin resins include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polyethylene, very low density (PEEP), ethylene copolymer resins, blastomere copolymers of ethylene and 1-alkene, polybutene and mixtures thereof.

To an acceptable thermoplastic polyamides (nayanam) include crystalline or resinous high molecular weight solid polymers including copolymers and ternary copolymers containing in the polymer chain recurring amide units. The polyamides can be obtained by polymerization of one or more Epsilon-lactams, such as caprolactam, pyrrolidine, laurinlactam and aminoundecanoic lactam, or amino acid, or p is secondarily dibasic acids and diamines. Suitable nylony as fibre-forming and moulding grades. Examples of such polyamides are polycaprolactam (nylon-6), polyarylate (nylon-12), polyhexamethylenediamine (nylon-6,6), polyhexamethylenediamine (nylon-6,9), polyhexamethylene (nylon-6,10), polyhexamethylenediamine (nylon-6,if) and the product of polycondensation of 11-aminoundecanoic acid (nylon-11). When performing the present invention can be also effectively used technically available thermoplastic polyamides, preferably linear crystalline polyamides, softening temperature or melting point which is in the range from 160 to 230°C.

Acceptable thermoplastic polyesters, which can be used include polymeric products of the interaction of one or a mixture of aliphatic or aromatic polycarboxylic acids, esters or anhydrides and one or a mixture of diols. Examples of suitable polyesters include poly(TRANS-1,4-cyclohexyl), poly(alkane(C2With6)bicarboxylic), such as poly(TRANS-1,4-cyclohexylglycine) and poly(TRANS-1,4-cyclohexanediol); poly(CIS - or TRANS-1,4-cyclohexanediamine)alkalicarbonate, such as poly(CIS-1,4-cyclohexanedimethanol)oxalate and poly(CIS-1,4-cyclohexanedimethanol)succinate; the floor is(alkylen(C 2With4)terephthalate), such as polyethylene terephthalate and polyethylenterephthalat; poly(alkylen(C2With4)isophthalate), such as polietilentireftalat and polytetramethylene, etc. materials. Preferred polyester derivateservlet from aromatic dicarboxylic acids such as naphthalene and oftalmica acid, and diols with2With4such as polyethylene terephthalate and polybutylene terephthalate. Preferred polyesters are usually characterized by a melting point in the range from 160 to 260°C.

Polyphenylenether (PFA) thermoplastic engineering resin that can be used in accordance with the present invention, are well known technically available materials derived oxidative dehydrocondensation polymerization of alkyl substituted phenols. Usually they are linear polymers, the glass transition temperature which is within the range from 190 to 235°C. Examples of preferred PFA polymers include poly (2,6-dialkyl-1,4-phenylenebis ethers, such as poly-2,6-dimethyl-1,4-phenylenebis ether, poly-2-methyl-6-ethyl-1,4-phenylenebis ether, poly-2,6-dipropyl-1,4-phenylenebis ether and poly-2-ethyl-6-propyl-1,4-phenylenebis ether. These polymers, method of production thereof and mixtures with polystyrene additionally described in US 3383435.

On the other thermoplastic resin, which can be used include polycarbonate similar to those described above polyesters, such as segmented copolymers of simple esters and phthalates; polycaprolactone polymers; styrene resins, such as copolymers of styrene with less than 50 mol % of Acrylonitrile (SAN), and resinous copolymers of styrene, Acrylonitrile and butadiene (ABS); sulfonic polymers, such as polyphenylsulfone etc. structural resins, which are known in the art.

Supplements

The composition of the invention may include plasticizers, vulcanizing group and may also include reinforcing and newsrevue fillers, antioxidants, stabilizers, oils to improve the processing properties of rubber, plasticizers, oil filling rubber phase latex, lubricants, antiadhesive, antistatic agents, waxes, foaming agents, pigments, flame retardants and other substances to improve the processing properties, known in the art for the preparation of rubber mixtures. Such additives can comprise up to 50 wt.% the whole composition. Fillers and diluents which can be used include conventional inorganic materials such as calcium carbonate, clay, silica, talc, titanium dioxide, carbon black, etc. Oils to improve the processing properties of the rubber are usually in zelenoye, naphthenic or aromatic oil, derivateservlet from petroleum fractions, but preferably vaseline. Use oils of this type, which is common in tandem with the specific rubber or rubber contained in the composition, and the amount, calculated on the total content of rubber may be in the range from zero to 1-200 miscast. one hundred parts of rubber (part./100). The composition may also contain plasticizers, such as trimellitate esters.

Moreover, you can use various phenolic resins known in the art, and literature, as well as various phenol-formaldehyde resins, as they are represented in "The Chemistry of Phenol-Formaldehyde Resin Vulcanization of EPDM: Part I. Evidence for Methylene Crosslinks," by Martin VanDuin and Aniko Souphanthong, 68 Rubber Chemistry and Technology 717-727 (1995).

Curing the substance of the present invention may include any number of components, such as complex metal-based or metal-containing ligand, accelerators, resins or other components known in the art as influence the vulcanization of the elastomer. In its broadest embodiment, curing the substance is at least a metal oxide or a complex with ligand-based metal of groups 2-14, where at least one ligand can undergo substitution reactions with inducing the connection is. In one embodiment, the at least one curing substance is a metal oxide, such as zinc oxide, slaked lime, magnesium oxide, carbonates and hydroxides of alkali metals. Thus, in particular, the usual vulcanizing group, which, as a rule, used when performing the present invention include the following curing of the substance on the basis of metals: ZnO, CaO, MgO, Al2About3, CrO3, FeO, Fe2About3and NiO, and/or carboxylates of these metals. These metal oxides can be used in combination with the corresponding complex based on a metal carboxylate or carboxylate ligand and either sulfur or alkylperoxide connection [see also Formulation Design and Curing Characteristics of NBR Mixes for Seals, Rubber World 25-30 (1993)].

The amount of vulcanizing substances usually vary depending on the type of substance used and in particular from the target degree of vulcanization, as is well known in the art. For example, the amount of sulfur is usually from 1 to 5, and preferably from 2 to 3, miscast. 100 miscast. of the composition. The amount of peroxide curing substance is usually from 0.1 to 2.0 miscast., the amount of phenolic curing resin is usually from 2 to 10 miscast., and the number of difficult amine is from 0.1 to 2 miscast., and the f number is specified in terms of 100 miscast. song.

These metal oxides can be used in combination with another compound, such as fatty acid, and the range of curing substances in the present description is not limited to a single metal oxide or a complex with a metal-containing ligand. Examples of organic or fatty acids that can be used during execution of the invention are stearic, oleic, lauric, palmitic, myristic acid and mixtures thereof, and hydrogenated oils from a number of palm, castor oils, fish oil and Flaxseed oil. The use of these curing substances discussed in Rubber Technology 20-58 (Maurice Mortin, ed.. Chapman & Hall, 1995) and in Rubber World Magazine's Blue Book 2001 109-137 (Don R. Smith, ed., Lippincott &Peto, Inc. 2001), as well as in the US 5332787.

In one embodiment, a curing group may be contained in an amount of from 0.5 to 20 ppm 100 composition and from 1 to 10 ppm 100 in another embodiment. In another embodiment, curing of the group in the composition is essentially absent. The phrase "essentially absent" means that the traditional curing groups, such as phenolic resins, sulfur, peroxides, metals and oxides of metals and metal-containing complexes with the ligands, compositions do not contain.

Processing

The BEAM component of thermoplastic elastomer is usually found in small, i.e. microme the historical size, particles in a continuous plastic phase, although depending on the amount of rubber relative to the plastic material and vulcanizing the group, or the degree of vulcanization of the rubber is also possible co-continuous morphology or a phase inversion. In the final vulcanized thermoplastic rubber composition suitable for at least partially structured, and in the preferred embodiment, its structure in whole or in part. Partial or complete structuring can be achieved by adding to the mixture of thermoplastic polymer with rubber corresponding vulcanizing group for rubber and vulcanized rubber to the target extent in conventional vulcanizing conditions. However, in the preferred embodiment, the rubber must be structured according to the method of dynamic vulcanization.

Dynamic vulcanization is carried out by mixing thermoplastic and elastomeric components at elevated temperature in conventional mixing equipment such as rolls, Banbury mixers™, Brabender mixers™, rubber continuous operation, the mixing syringe-machine and other Unique characteristics of dynamically cured compositions is that, despite the fact that full or partial vulcanization of the rubber component, such compositions can be processed and repeat is about to be processed by the conventional methods of processing plastic materials, such as extrusion, injection molding, blow molding and direct pressing. Waste or Burr can be utilized and recycled again.

For specialists in this field of technology is obvious the quantities, types, curing and vulcanization conditions that are necessary for carrying out the vulcanization of BEAM rubber. The rubber can be vulcanized using varying amounts of vulcanizing groups, with varying temperatures and varying time of vulcanization in order to achieve the desired optimal structuring. You can use any known vulcanizing group for rubber, if only it was acceptable in the conditions of vulcanization taking into account specifically used BEAMS of the rubber and thermoplastic component. These vulcanizing groups include sulfur, sulfur donors, metal oxides, resins, peroxide group on the basis hydrocellulose vulcanizing group, platypodinae or peroxide catalysts, etc. as with accelerators and joint vulcanizing agents, and without them. Such vulcanizing groups are well known in the art and in the literature on vulcanization of elastomers.

Depending on the target applications, the amount of rubber contained in the composition may be in the range from 10 to 90 wt.% of the total amount of polymer in the composition. For most applications, particularly when the rubber component vulcanized dynamically, the amount of the rubber component is usually less than 70 wt.%, more preferably less than 50 wt.%, and most preferably from 10 to 40 wt.%, of the total polymer in the composition.

Treatment temperature TPE compositions in the melt is usually in the range from a temperature higher than the melting point of the high-melting polymer contained in the TPE composition, up to 300°C. the Preferred temperature processing are typically in the range from 140 to 260°C, from 150 to 240°in another embodiment, however, from 170 to 220°in yet another variant.

Shortness of amine or phosphine compound can be combined with BEAM rubber component at any stage of the mixing, i.e. when initially mixed BEAM and a thermoplastic polymer, or at a time when mixed with vulcanizing group or other additives in the preparation of dynamically vulcanized compositions. However, in the preferred embodiment, hindered amine or phosphine material first compounding with BEAMS polymer at temperatures up to 300°obtaining a modified BEAM polymer with high viscosity, and then this modified polymer is mixed with a thermoplastic resin and in which the Yomi other additives, contained in the TPE composition.

Thermoplastic composition according to the invention is formed by mixing, in any order, amine or phosphine, souleimanova copolymer and a thermoplastic material. In one embodiment, the first copolymer is mixed with the amine or phosphine with obtaining compositions amine or phosphine/copolymer, followed by mixing with a thermoplastic material. In another embodiment, these three components are mixed simultaneously. Moreover, in one embodiment, the present invention such a thermoplastic composition is prepared almost in the absence of solvent. More specifically, amine and BEAM components are mixed according to the method that the experts in this field known in the art, without addition of organic solvent. Next, the thus prepared composition amine or phosphine/copolymer can be mixed in the absence of solvent with a thermoplastic material. Solvents, mainly organic solvents, such as hexane, methylene chloride and other solvents, which are known as solvent polyolefins, nylony and halogenated elastomers in the composition or during the mixing of components is essentially absent. The phrase "essentially absent" means that the solvent content is less than 5 wt.% in terms of the weight is at all available songs.

Thermoplastic compositions according to the invention may include from 10 to 90 wt.% a thermoplastic material and from 90 to 10 wt.% souleimanova copolymer. In another embodiment, a thermoplastic composition according to the invention can contain from 20 to 80 wt.% a thermoplastic material, and from 80 to 20 wt.% souleimanova copolymer. In yet another embodiment, a thermoplastic composition according to the invention comprise from 40 to 60 wt.% a thermoplastic material, and from 60 to 40 wt.% souleimanova copolymer. Vulcanized thermoplastic compositions have a tensile tensile strength greater than 1000 psi in one embodiment, and greater than 2000 psi in another embodiment (ASTM D1708, as presented below in the description text). Such vulcanized thermoplastic composition have a value of strain at break greater than 200% in one embodiment, and greater than 300% in another embodiment (ASTM D1708, as presented below in the description text).

EXAMPLES

The invention is illustrated by the following examples. Used in these examples, the materials are presented in table 1.

Example 1

This example illustrates the reduction of the viscosity of the brominated isobutylene/p-methylstyrene copolymer (table 1 designated as the BEAMS 1, 2 and 3). Samples of each rubber was subjected to a shear stress of shear rates from 50 to 5000-1the application of capillary plastometer at a temperature of 220° C. viscosity Data were further corrected for inlet pressure and profile of non-Newtonian expiration. Presented for comparison only viscosity at 100, 500, 1000 and 1500 C. table 2 shows the decrease in viscosity for each of these rubbers as a function of increasing shear rate.

Example 2

All tertiary amines, DM16D, DMHTD and MINT, mixed BEAM 2 by using a Brabender mixer™who worked at 150°and at 60 rpm amine was added in amounts that were molar equivalent content of bromine atoms in the BEAM. As shown by the data in table 3, adding DM16D was able to increase viscosity of BEAM at 220°s at all shear rates.

The presence of a tertiary amine DM16D in the BEAM did not lead to any thermal degradation of the BEAM, as evidenced by the data of table 4. Viscosity values of BEAM after adding DM16D at each temperature remained relatively constant during cyclic exposure to heat in the range from 100 to 250°C.

The increase in the viscosity values in the modification of BEAM tertiary amine depends on the structure of the amine. If we compare the figures in table 5 with the data of table 3, hexadecyldimethylamine DM16D provides a greater increase in viscosity in comparison with the increase with DMHTD, which is a dimethyl, but the advantage is but 18the group R3unlike C16group R3the DM16D. When used MNT, which is allylmethylamine digidrirovannoe tall oil and has as alkyl groups as R2and R3groups, mainly C18(see table 6), the increase in viscosity was less significant in comparison with that achieved by adding DM16D.

Example 3

A mixture consisting of 60 wt.% polypropylene with the RAF (spreading rate of the melt) 1,5 (firm ExxonMobil, PP4292) and 40 wt.% BEAMS 2, modified with 0.5 molar equiv. DM16D, were prepared by mixing the components using a Brabender mixer™ at 80 rpm and 220°With over a 5 minute period.

Preparing the control mixture, which was in all other respects identical, except that of BEAM 2 is not modified with the amine (control mixture). Structural characteristics of the resulting mixtures was investigated AFM (atomic force microscopy), followed by processing the image to determine the size of dispersed particles in units srednekamennogo equivalent diameter. To prevent relaxation of samples all samples were analyzed within 8 h after the cutting of the end face in a frozen state. During the cutting of the end face in a frozen state these samples were cooled to -150°and pruned and the maznyj knives in cryogenic Reichert microtome. Next to warm to room temperature without condensing it was kept in an oven in a stream of dry nitrogen gas. Finally, for AFM analysis of samples from the cut ends were placed in a small steel vise. Measuring AFM studies were carried out in air under the scanning probe microscope NanoScope Dimension 3000 (digital instrument) using a rectangular Si console. AFM phase images of all samples were converted into TIFF format and processed using the instrument PHOTOSHOP™ (Adobe Systems, Inc.). For measuring research images used a set of image processing (firm Reindeer Games, Inc.). The results of measuring research of images recorded in a text file for processing data using EXCEL™. The obtained data are presented in table 7. These results demonstrate almost 30%reduction in the size of particles dispersed BEAM of rubber in comparison with their size in the sample.

In the following examples were prepared additional thermoplastic compound or composition of the ion related alloys (ASCS), containing a variable number of tertiary amine, and their mechanical properties were evaluated in comparison with the properties of control samples that did not contain additives tertiary amine. The use is consistent in the composition of these mixtures of thermoplastic polymer was a polypropylene (PP) RR, polypropylene with the RAF 2,8, dostepny company ExxonMobil Chemical Co.

Example 4

Tertiary amine, when it was added to the mixture of thermoplastic material with the elastomer was mixed with vaseline and mineral oil. A mixture of PP/BEAM was prepared by mixing in a mixer of Brabender at a temperature of 190°and a rotor speed of 60 rpm PP granules are first melted in the presence of an acceptable stabilizer, such as product Irganox 1076. Further added to the elastomer, and then diluted oil product Armeen DM16D. In the end to perform the functions of acid binding agent to this mixture was added a metal oxide, such as MgO. Table 8 presents several compositions of ASCS with a ratio of thermoplastic/elastomer in a mixture of 40/60 (amounts expressed in mass units). In the case of proposed according to the invention the composition (b) was picked up exactly stoichiometric couple of on the content of bromine and amino groups, whereas in the proposed invention the compositions (a) and (b) were respectively more and less of the amino groups than the number of bromine.

Each composition ISS table 8 were subjected to molding by direct pressing at 190° within 15 minutes of obtaining the plates of a thickness of about 0.08 inch. Using these molded plates (up tests were stored in ambient conditions for 48 h) was carried out by spymania characterization of tensile stress/strain. With this purpose used the samples in the form micropetala (ASTM D1708) (test temperature: 25°s; speed of movement of the slider Instron machine: 2 inch/min). According to the data of table 8, the introduction of the Association of ions in a mixture of PP/BEAM/oil [examples of compositions according to the invention with (a) through (C), which contained 10 ppm 100 oil] significantly increased the strain at break, maximum voltage near the moment of break and ultimate tensile strength (determined by area under the curve of stress-strain) in comparison with the characteristics of the material of the control.

Example 5

Data for other compositions of ASCS with a ratio of thermoplastic/elastomer in a mixture of 30/70 presented in table 9 (amounts expressed in mass units). In cases proposed by the invention compositions (d) and (e) respectively with 10 and 20 ppm 100 oil picked up exact stoichiometric couple regarding the content of bromine and amino groups. Here again it can be noted that the introduction of associations of ions in the mixture of PP/BEAM/oil (10 or 20 ppm 100 oil) significantly increased the strain at break, maximum voltage near the moment of rupture and tensile strength at elongation in comparison with the control characteristics of the materials.

Table 10 presents the composition of ASCS with a ratio of thermoplastic is CNY material/elastomer in a mixture of 30/70, made using BEAMS with a higher Mooney viscosity. In this series also varied the oil content. In cases proposed by the invention compositions (f), (g) and (h) have picked up exact stoichiometric couple regarding the content of bromine and amino groups. The results show that the introduction of the Association of ions in the mixture of PP/BEAM/oil (10, 20 or 30/100 oil) increased the maximum stress near the moment of rupture and tensile strength at elongation in comparison with the same characteristics of materials in the control examples. At higher oil content strain at break in the mixture without associations ions was higher than that of the corresponding mixture with associations ions, possibly due to the higher molecular weight of BEAM 2.

Although the present invention is described and illustrated with reference to specific ways of its implementation, to the ordinary person skilled in the field of technology is apparent that the invention leads to many different variants, which in the present description is not illustrated. For these reasons, in order to determine the actual scope of the present invention should apply only to the attached claims.

All mentioned in the present description priority documents included in full in accordance with all Yu what indictee, that such inclusion permit. Moreover, in accordance with all jurisdictions in which such incorporation allow, in the present description in full includes all mentioned in the present description documents, and test methods.

Table 1
The materials used
DesignationDescriptionMaterial
BEAM 1BEAM rubber, the Mooney viscosity: 35%*, of 0.75 mol % Br, 5 wt.% links PMSEXXPRO™ 89-1, company ExxonMobil Chemical
BIMSBEAM rubber, the Mooney viscosity: 45%*, of 0.75 mol % Br, 5 wt.% links PMSEXXPRO™ 89-4, company ExxonMobil Chemical
BISSBEAM rubber, the Mooney viscosity: 65%*, 1,1 mol % Br, 5 wt.% links PMSEXXPRO™ 91-11, company ExxonMobil Chemical
DM16DTertiary amine, hexadecyldimethylamineproduct Armeen DM16D, the company Akzo Nobel Chemical
DMHDTTertiary amine, alkyldiphenylamine hydrogenated tall oilproduct Armeen DMHDT, the company Akzo Nobel Chemical
MNTTertiary amine, allylmethylamine digidrirovannoe tall oilproduct Armeen M2HT, the company Akzo Nobel Chmical
* the Mooney viscosity was determined at 125°With ASTM D1646.
** gidrirovannoe tall oil contains the following saturated products: 3.5% of C14-, 0,5% C15-, 31% C16and 1% With17-61% of C18and 3% unsaturated With18product (2/3 alkyl groups are C18)

Table 2
Viscosity values of BEAM with low and high viscosity Mooney
Shear rate (1/s)Viscosity* BEAM 2The viscosity of BEAM 3
10012741468
500378383
1000200197
1500136133
*Determined at 220°using capillary plastometer. Values expressed in PA·C.

Table 5
Viscosity values of BEAM 2, a modified DMHTD, 220°PA·
Shear rate (1/s)BEAM

2
The BEAM from 0.1 EQ. DMHTDThe BEAM from 0.25 EQ. DMHTDBEAMS with 0.5 EQ. DMHTDThe BEAM from 1.0 EQ. DMHTD
1001274189219163209*
500378517594861963
1000200317315472499
1500136*211312339
Table 6
Viscosity values of BEAM 2, a modified MNT, 220°PA·
Shear rate (1/s)BEAM

2
The BEAM from 0.1 EQ. MNTThe BEAM from 0.25 EQ. MNTBEAMS with 0.5 EQ. MNTThe BEAM from 1.0 EQ. MNT
1001274B/And a*199723722227
500378B/And496645679
1000200B/And263368388
1500 136B/And182276275
*B/And indicates no change relative to pure BEAM 2

0,09 1200
Table 7
The particle size dispersion of BEAM
MixtureThe particle size of the dispersion (in micrometers)
Control sample2,08
The modified BEAM1,42
Table 8
The mixture of the copolymer with polypropylene
Component/property (miscast.)Control sample(a)(b)(in)
PP 477218181818
BEAM 127272727
ArmeenDM16D- 1,51,00,5
Oil4,54,54,54,5
Irganox 10760,090,090,090,09
MgO (Maglite D)is 0.135is 0.135is 0.135is 0.135
Stress at elongation at 100%, psi570950830720
Stress at elongation of 200%, psi-11701100960
Deformation at break, %130500470410
The maximum stress near the moment of rupture, psi58018001400
Ultimate tensile strength, psi670624024401850
Table 9
The mixture of the copolymer with polypropylene
Component/property (miscast.)Control sampleControl sample(g)(d)
PP 477213,513,513,513,5
Component/property (miscast.)Control sampleControl sample(g)(d)
BEAM 131,531,531,531,5
Armeen DM16D--1,161,16
Oil 4,59,04,59,0
Irganox 10760,090,090,090,09
MgO (Maglite D)is 0.135is 0.135is 0.135is 0.135
Stress at elongation at 100%, psi10075440280
Stress at elongation of 200%, psi7024660460
Deformation at break, %570350640680
The maximum stress near the moment of rupture, psi8313801100
Ultimate tensile strength, psi 27012054704430
Table 10
The mixture of the copolymer with polypropylene
Component/property (miscast.)Control sampleControl sampleControl sample(e)(W)(d)
PP 477213,513,513,513,513,513,5
BEAM 231,531,531,531,531,531,5
ArmeenDM16D---1,161,161,16
Oil4,59,013,54,59,013,5
Irganox 10760,090,090,090,090,09
MgO (Maglite D)is 0.135is 0.135is 0.135is 0.135is 0.135is 0.135
Stress at elongation at 100%, psi18013036550320440
Component/property (miscast.)Control sampleControl sampleControl sample(e)(W)(d)
Stress at elongation of 200%, psi16010026830510630
Deformation at break, %6509201280710710600
The maximum stress near the moment of rupture, psi3530,219001230
Ultimate tensile strength,
psi730450110810052004500

1. Thermoplastic composition comprising a thermoplastic material, at least one isorevenue copolymer that includes a link derivateservlet from kilometerstirana, mixed with at least one difficult aminoven or phosphine compounds having the corresponding structure of R1R2R3N or R1R2R3P, where R1denotes H or alkyl with C1With6, R2denotes alkyl with C1With30and R3denotes alkyl with C4With30and, in addition, where R3represents a higher alkyl than R1and the mixing is carried out at a temperature which exceeds the melting point of the specified difficulty amine or phosphine compound, and the viscosity of this composition at 220°and shear rate 100 1/s greater than 1300 PA·with or higher than 200 PA·at 220°and a shear rate of 1000 1/gallop is determined according to ASTM D 1646, moreover, at least one difficulty amine or phosphine compound is used in a quantity sufficient to increase the viscosity of the composition at the specified temperature and shear rate.

2. The composition according to claim 1, where R3denotes alkyl with C10With30.

3. The composition according to claim 1, in which the shortness of the compound is a tertiary amine and where R3denotes alkyl with C10C20.

4. The composition according to claim 3, where each of R1and R2denotes methyl.

5. The composition according to claim 1, comprising from 0.05 to 2 moles of amine or phosphine to a halogen.

6. The composition according to claim 1, in which isorevenue copolymer is a halogenated isobutylene/p-methylstyrene copolymer.

7. The composition according to claim 1, in which in the process of mixing souleimanova copolymer and amine or phosphine solvent essentially absent.

8. The composition according to claim 7, in which the shortness of the compound is a hindered amine, in which R3denotes alkyl with C10With20and each of R1and R2denotes methyl.

9. The composition according to claim 1, in which the viscosity of the composition amine or phosphine/copolymer at 220°and a shear rate of 1000 1/s greater than 200 PA·C.

10. The composition according to claim 7, in which the copolymer contains from 0.05 to 2 moles of amine or phosphine to a halogen.

11. Method of increasing the viscosity of thermoplastic composition according to claims 1 to 10, in which thermoplastic material, at least one isorevenue copolymer that includes a link derivateservlet from kilometerstirana, mixed with at least one difficult aminoven or phosphine compounds having the corresponding structure of R1R2R3N or R1R2R3P, where R1denotes H or alkyl with C1With6, R1denotes alkyl with C1With30and R3denotes alkyl with C4With30and, in addition, where R3represents a higher alkyl than R1pick songs amine or phosphine/copolymer, and such mixing is carried out at a temperature which exceeds the melting point of the specified difficulty amine or phosphine compound, to obtain the composition having a viscosity at 220°and shear rate 100 1/s more than 1300 PA·or greater than 200 PA·at 220°and a shear rate of 1000 1/s as determined according to ASTM D 1646, and at least one difficulty amine or phosphine compound used in a quantity sufficient to increase the viscosity of the composition at the specified temperature and shear rate

12. The method according to claim 11, where R3denotes alkyl with C10With20.

13. the procedure according to claim 11, where shortness compound is a tertiary amine.

14. The method according to claim 11, where each of R1and R2denotes methyl.

15. The method according to claim 11, where the copolymer contains from 0.05 to 2 moles of amine or phosphine to a halogen.

16. The method according to claim 11, where the solvent is essentially absent.

17. The method according to claim 11, where isorevenue copolymer is a halogenated isobutylene/p-methylstyrene copolymer.

18. Thermoplastic composition according to claim 1, characterized in that it is prepared by mixing a thermoplastic material, at least one souleimanova copolymer that includes a link derivateservlet from kilometerstirana, with at least one difficult aminoven or phosphine compounds having the corresponding structure of R1R2R3N or R1R2R3R, where R1denotes H or alkyl with C1With6, R2denotes alkyl with C1With30and R3denotes alkyl with C4With30and, in addition, where R3represents a higher alkyl than R1obtaining compositions amine or phosphine/copolymer, and such mixing is carried out at a temperature which exceeds the melting point of the specified difficulty amine or phosphine connection with obtaining a composition having a viscosity at 22° C and a shear rate 100 1/s more than 1300 PA·or greater than 200 PA·at 220°and a shear rate of 1000 1/s as determined according to ASTM D 1646, and at least one difficulty amine or phosphine compound is used in a quantity sufficient to increase the viscosity of the composition at the specified temperature and shear rate.

19. The composition according to p, where the viscosity of the composition amine or phosphine/copolymer at 220°and shear rate 100 1/s ranges from 1300 to 6000 PA·as determined according to ASTM D 1646.

20. The composition according to p, where the viscosity of the composition amine or phosphine/copolymer at 220°and a shear rate of 1000 1/s greater than 200 PA·as determined according to ASTM D 1646.

Priority points and features:

Paragraph 1, except for the sign of at least one isorevenue copolymer that includes a link derivateservlet of salmeterol priority from 07.06.2001.

Paragraphs 2-4 shall have priority from 07.06.2001.

Paragraph 5 in part from 0.05 to 2 moles of amine takes priority from 11.10.2000, and a sign from 0.05 to 2 moles of phosphine takes priority from 07.06.2001.

Item 6 has priority from 11.10.2000.

Paragraph 7-9 have priority from 07.06.2001.

Paragraph 10 in part from 0.05 to 2 moles of amine takes priority from 11.10.2000.

Paragraph 11, except the sign of the Sabbath. - at least one isorevenue copolymer that includes a link derivateservlet from kilometerstirana priority from 07.06.2001.

Item 12-14 have priority from 07.06.2001.

Item 15 in part from 0.05 to 2 moles of amine takes priority from 11.10.2000, and a sign from 0.05 to 2 moles of phosphine takes priority from 07.06.2001.

Paragraph 16 priority from 07.06.2001.

Item 17 is the priority of 11.10.2000.

Paragraph 18, except for the sign of at least one isorevenue copolymer that includes a link derivateservlet from kilometerstirana priority from 07.06.2001.

Paragraph 19-20 have priority from 07.06.2001.



 

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8 cl, 7 tbl, 1 ex

FIELD: rubber industry.

SUBSTANCE: invention relates to the development of fluorine-containing rubber-base rubber mixture used in preparing rubber-technical articles with capacity to work at temperature up to 200°C in oils and fuels medium. Method involves preparing rubber mixture of the following composite, mas. p.p.: fluorine-containing rubber, 90-97; acrylate rubber, 3-10; blocked diamine of the formula: [H2N-R1-R-R2-NH2] MCl as a vulcanizing agent wherein R1 and R2 mean cyclic or aromatic hydrocarbon radicals; R means aliphatic hydrocarbon radical; M means alkaline metals, 2-10; technical carbon, 10-30; vulcanization activating agent, 3-5; acceptor of halogen-hydrocarbons, 3-6, and stearic acid, 1-2. Invention provides enhancing heat stability, resistance against corrosion, to reduce viscosity and to improve technological properties in processing.

EFFECT: improved and valuable properties of rubber mixture.

2 tbl

FIELD: chemistry, in particular organic polymeric compounds and compositions.

SUBSTANCE: claimed composition contains epoxy-dianic resin with molecular weight at most 390, aliphatic epoxy resin, and triethyleneamin as curing agent. Composition is obtained by addition of 5-10 mass pts of aliphatic epoxy resin to 100 mass pts of epoxy-dianic resin and mixture is blended to obtain homogeneous mass. Then 13-14 mass pts of triethyleneamin as reduced to 100 mass pts of resin is admixed and cured at room temperature for one day followed by auxiliary curing at 100-120°C for 3-5 h. Composition of present invention is useful in production of heat resistant polymeric constructional materials for aerospace and machine industry.

EFFECT: epoxy compositions with improved strength and heat resistance.

2 cl, 3 tbl, 3 ex

FIELD: phenoplast production, in particular casting composition for technical applications.

SUBSTANCE: claimed casting composition included (mass %): novolac phenol-formaldehyde resin 47-49.3; wood powder 28.4-29.5; urotropine 7.1-7.4; kaolin 3.2-3.4; burnt magnesia 0.7-0.9; nigrosine 1.4-1.5; talk 3.7-3.9; naphthalene 1.9-2; stearin 0.2-0.4; calcium stearate 0.4-0.6; polyethylene wax 0.5-0.7; phosphoric acid triphenyl ester 1-5. Composition of present invention has increased destructive torque stress and decreased viscosity coefficient at 120°C and shear velocity gradient of 15 l/s.

EFFECT: composition with increased destructive torque stress and decreased viscosity coefficient.

4 ex, 1 tbl

FIELD: rubber industry.

SUBSTANCE: curing agent contains, wt %: sulfur 45.0-90.0, 1,4-bis(trichloromethyl)benzene 5.0-40.0, hexamethylenetetramine 1.0-5.0, and wax 2.0-10.0. Agent is prepared by mixing sulfur melt with molten 1,4-bis(trichloromethyl)benzene at 115-120°C followed by adding hexamethylenetetramine and wax, raising temperature to 140-150°C, and stirring resulting melt at this temperature during 30-40 min, whereupon melt is cooled in thin layer to 15-20°C.

EFFECT: improved distribution of curing agent in rubber compound, increased resistance to reversion during prolonged vulcanization of rubber and to thermal-oxidative action.

3 cl, 5 tbl, 7 ex

FIELD: organic synthesis.

SUBSTANCE: alkenylsuccinylamides are prepared via (i) alkenylation of maleic anhydride with poly-α-olefin or polyisobutylene having 10 to 30 carbon atoms and molecular mass 800-1000 in presence of initiators at 60-100°C for 0.5-1 h and then at 165-175°C for 3.5-4.5 h, molar ration of polymeric reagent to maleic anhydride being 1:(1-1.1) followed by (ii) condensation of resulting alkenylsuccinic anhydride in presence of oil containing 5-methyl-1,4,7,10-teraaminodecane or 8 -methyl-1,4,7,10,13,16-hexaaminohexadecane first at 30-58°C for 0.5-1.0 h and then at 136-145°C for 3.5-4.0 h at alkenylsuccinic anhydride-to-amine molar ratio (1-1.5):1. In step (i), initiator is selected from t-butyl peroxide and methyl ethyl ketone peroxide in amounts 0.8-1.4% of the summary weight of initial reactants, whereas oil is industrial oil 20A or I-40A.

EFFECT: simplified technology, enabled use of accessible raw materials, and improved quality of product.

4 cl, 1 tbl

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