Rubber mixture composition and method for its preparing (variants)

FIELD: rubber compositions, chemical technology.

SUBSTANCE: invention relates to rubber mixture compositions and methods for their preparing. Preparing a rubber mixture composition involves mixing from 5 to 90 wt.-% of rubber component chosen from butyl rubber, halogenated butyl rubber, stellate butyl rubber, halogenated stellate butyl rubber, isobutylene homopolymer, chloroprene, butadiene-nitrile rubbers, ethylene-propylene-diene triple copolymers, ethylene-propylene copolymers, butadiene styrene rubbers, polybutadiene, polyisoprene, isoolefin-alkylstyrene copolymer, halogenated isoolefin-alkylstyrene copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicon rubber, propylene oxide polymer and their mixtures, from 0.01 to 5 wt.-% of amine compound represented by the formula: (R1R2R3)N wherein R1 means either hydrogen atom or hydrocarbyl group comprising from C4 to C30 carbon atoms; R2 means either hydrogen atom or hydrocarbyl group comprising from C1 to C30 carbon atoms, and R3 means either hydrogen atom or hydrocarbyl group comprising from C1 to C30 carbon atoms under condition that at least one radical among R1, R2 and R3 doesn't mean hydrogen atom, from 5 to 90 wt.-% of isoolefin copolymer comprising a link derivatized from halogenmethylstyrene, isoolefin link comprising from 4 to 7 carbon atoms, and copolymer comprises from 0.5 to 20 wt.-% of halogenmethylstyrene links and usual additives. Invention provides preparing the rubber mixture composition possessing the enhanced strength before treatment and enhanced stability against heat aging after vulcanization.

EFFECT: improved preparing method, improved and valuable properties of composition.

51 cl, 4 tbl, 3 ex

 

The technical field to which the invention relates.

The present invention in General relates to elastomeric compositions with improved resistance against heat aging and resistance to treatment. Such elastomeric compositions include compositions of halogenated elastomer, such as isorevenue copolymer containing derivateservlet from kilometerstirana link and Amin. This composition may also include additional rubber or halogenated rubber component.

Background of invention

For the manufacture of durable molded the most common elastomers need to be structured, i.e. to be cured or vulcanized. However, as a result of structuring between the polymer molecules of rubber formed of a relatively permanent relationship. After the formation of these relationships, these latter inhibiting adequate fluidity required for further processing or molding. Thus, the processing and molding of elastomeric articles often necessary to vulcanization.

However, to structuring these elastomers often do not have sufficient strength, also known as strength before treatment, allows to simplify the implementation of the manipulation and processing. Strength up processing refers to the cohesion of str is oblasti and dimensional stability of the rubber under the action of a relatively small voltage before vulcanization or curing. Strength before treatment is important in such industries as the manufacture of tires, where the inner shell and the other layers of the tire can be molded in a single phase, whereas the vulcanization is carried out at a later stage. Strength before treatment is important, enabling the manufacturer to shape and stretch unvulcanized elastomer while maintaining other valuable properties, such as low air permeability.

Vehicle modifications strength before treatment without chemical structure (i.e. the formation of covalent bonds) as a result of the vulcanization process is isomerizate (i.e. getting ionomer). Isomerizate amines are also known in the art as "quaternization" due to the formation of Quaternary amine (ammonium ion). Since this process is reversible, isomerizate provides strength to the processing at lower temperatures, and good processability at higher temperatures. A typical method of isomerization is added to the elastomeric composition of the tertiary amines, the amine functional group interacts with acidic functional group of the polymer with the achievement of stable interactions that increase the resistance to treatment. In the US 389853 and 42568576 in General described the use of tertiary amines for direct modification globaleconomic compositions to improve their strength before treatment. However, halobutilic, such as bromobutyl rubber, does not show very high reactivity in relation to these amines. Therefore, to achieve sufficient strength to handle the mixture must be heated for a significant period of time.

Summary of the invention

When creating the present invention, it was found that the strength of elastomers to processing and/or resistance against heat aging of elastomers, particularly halogenated elastomers, greatly enhance the mixing of rubber with the amine or phosphine and isoretinoin copolymer that includes a link derivateservlet from kilometerstirana. Considering the purpose of the present description, the composite elastomer and the amine may be in the form of "ionomer or ionomer composition. Ion meter can be obtained in situ and with a little heat or without.

The object of the present invention is a composition and method of preparation of the composition, and this composition includes at least two components. In the composition of the invention may contain further rubber component. In one embodiment, the first component is isorevenue copolymer that includes a link derivateservlet from kilometerstirana. The content of this copolymer in the composition is 5 cm to 90 wt.% of the composition. The halogen atom may be any halogen atom, it is chlorine atom or bromine.

In one embodiment, souletin contains from 4 to 7 carbon atoms and the copolymer includes from 0.5 to 20 wt.% links p-alkylthiol where from 0.01 to 60 mole percent of methyl groups on the benzene ring of the p-alkylthiol contain a halogen atom. In a preferred embodiment, isorevenue copolymer is an elastomer EXXPRO™ (ExxonMobil Chemical Company, Houston, Texas).

Amine or phosphine compound corresponding to the formula (R1R2R3)Q in which Q denotes an element of group 15, preferably a nitrogen atom or phosphorus, and in which R1denotes either a hydrogen atom or hydrocarbonous group with C4With30, R2denotes either a hydrogen atom or hydrocarbonous group with C1With30and R3denotes either a hydrogen atom or hydrocarbonous group with C1With30provided that at least one of R1, R2and R3does not denote a hydrogen atom. Amine is contained in an amount of from 0.1 to 5 wt.% of the composition. In another embodiment, the composition contains an amine in an amount of from 0.1 to 60 mol % relative to the amount in mol % of a halogen atom, in composition.

If additional elastomeric component (in the present description on the " "rubber" or "rubber component") may be included in the composition in an amount from 5 to 90 wt.% of the composition. This additional rubber selected from butyl rubber, halogenated butyl rubber, star-shaped butyl rubber, halogenated star-shaped butyl rubber, isobutilene of homopolymer, butadiene rubber, chloroprene, on BNR rubbers, ethylene-propylene-diene ternary copolymers, ethylene-propylene copolymers, Starovoitova rubbers, polybutadiene, polyisoprene, italianatestyle copolymer, halogenated italianatestyle copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicone rubber, propyleneoxide polymer and mixtures thereof.

Detailed description of the invention

The composition according to the present invention includes at least two components: isorevenue copolymer that includes a link derivateservlet from kilometerstirana, and amine or phosphine component. In another embodiment, may include additional rubber. Scope of the invention also includes the method of preparation of the composition with aminoven and other components. In the process of combining the original composition is uncured (or unvulcanized), but can also be vulcanized with the formation of vulcanized composition.

Regarding the reference to "groups" of the Periodic table, then use the Naya new numbering scheme groups of the Periodic table are identical to those what is presented in Hawley's Condensed Chemical Dictionary 852 (edition 13th, 1997).

Occurring in the present description the term "elastomer" refers to any polymer or composition of polymers corresponding to the definition in ASTM D1566. The terms "elastomer" and "rubber"used in the present description, can be used interchangeably.

Isorevenue copolymer that includes a link derivateservlet from kilometerstirana

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-gallmeister 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, to the which at least some alkyl replacement group, available 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, MIRCEN, 6,6-dimethylfuran, hexadiene, cyclopentadiene and piperylene, as well as other monomers, such as described in EP 0279456, 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 their combined what I am.

In another embodiment, the copolymer is a statistical elastomeric copolymer 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, a lower alkyl, preferably alkyl with C1With7or 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-CRR1 N-CRR1X can be a styrene substituents on the ring or in the ortho-or meta-or para-position, preferably in the para-position. Up to 60 mole percent n-substituted styrene units, members of 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 vulcanization more specifically described in US 5162445.

The most widespread use of such functionalized materials are elastomeric random copolymers of isobutylene and p-methylstyrene, comprising from 0.5 to 20 mol% of units of p-methylstyrene in which up to 60 mole percent metal Sames the participating groups, located on the benzyl ring contain a bromine atom or chlorine, preferably a bromine atom (p-brometalia), as well as their options, functionalized with residues of 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-alkylthiophene links in at least 95 wt.% polymer is in the range of 10% 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), sostavlyayuscyeye 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 and is almost free from the ring atoms of halogen or of halogen atoms in the main polymer chain. In one embodiment, the Soberania copolymer is a copolymer of units, derivatizing from samanaleya with4With7, 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 D1646, modified method) is from 30 to 60 units.

Amine/phosphine component

Amines or phosphines, which enter into the composition of the invention represented by the formula (R1R2R3)Q in which Q denotes an element of group 15, preferably a nitrogen atom or phosphorus, and in which R1denotes either a hydrogen atom or hydrocarbonous group4With30, R2denotes either a hydrogen atom or hydrocarbonous group with C1With30and R3denotes either a hydrogen atom or hydrocarbonous group with C1With30preferably with C1C8provided that at least one of R1, R2and R3does not denote a hydrogen atom. In a preferred embodiment, R3denotes a methyl or ethyl group, one of R1or R2means hydrocarbonous group6With20and the other of the seat is t a methyl or ethyl group. These gidrolabilna groups may be independently saturated, unsaturated, cyclic or aromatic.

You can use any Amin, if only it was sufficiently compatible with the rubber component and isoretinoin copolymer and in the absence of a permanent structure. When you need superior strength before treatment, in the preferred embodiment, as the amine component, use one that is able to isomerizate copolymer component. In a single target version of such amines can be more difficult and can be represented by the formula (R1R2R3)N, in which each of R1and R2independently denotes hydrocarbonous group4With30and R3denotes either a hydrogen atom or hydrocarbonous group1With30.

Examples of acceptable amine components include, though not limited to, N,N-dimethylhexylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylethanolamine, N,N-diethylcarbamyl, N,N-dimethylbenzylamine, N,N-methylpropionitrile.

Isorevenue copolymer, amine and in the presence of the rubber components are combined in amounts effective to achieve the target of improving the strength to processing and/or stability. Thus, the specific con is entrale each component generally depend on the specific components used. The relative amount of rubber and Amin usually determine the degree of influence on the properties of the composition. When, for example, use halogenated rubber component, the preferred amine content ranges from 0.05 to 2 molar equivalents. Amin in terms of atoms of halogen rubber or souleimanova copolymer, more preferably from 0.1 to 1 molar EQ. Amin in terms of atoms of halogen rubber or copolymer.

The present invention is particularly effective when used composition souleimanova copolymer and another rubber. The relative amount souleimanova copolymer, amine or phosphine, in the presence and rubber component usually depend on the specific rubber component. In a preferred embodiment, the amine or phosphine and the copolymer is used only in such quantities as necessary for improvement to the desired degree of strength to processing and/or stability. For example, the mass percentage of the rubber component can be varied from just 5 to 95 wt.% the composition, more preferably from 10 to 90 wt.% composition, and even more preferably from 20 to 80 wt.% song.

The method used for combining at least two components, the critical value has not provided adequate dispersion of amine and the other to the of mponents in the mass of rubber. Thus, you can apply any of the mixing device. In one embodiment, the components are combined and mixed at a temperature of from 20 to 200°C. the Mixture can be simplified by heating the mixture in a closed rubber mixer or plasticators for rubber to a temperature of from 50 to 200°and from 50 to 150°in another embodiment. It should be noted that after the mixture reached, in order to ensure adequate monomerization there is no need for heating of the mixture and/or smesimosti for long periods of time. After the components are mixed, the need for additional time of mixing or heat for the reaction is absent.

The order of mixing is not decisive. For convenience, you can mix the at least two components. Alternatively you can first combine the rubber component and the amine (and other components if present) followed by the addition souleimanova copolymer. For some purposes, it may be necessary preliminary preparation of the amine composition and rubber and then adding souleimanova copolymer or a preliminary preparation of the composition souleimanova of the copolymer rubber with the subsequent addition of an amine.

In reasonable quantities it is possible to use various additives. So, for example, anywhere on the stage during preparation of the composition it is possible to combine different amplifiers or fillers, such as carbon black, clay, silica, talc, etc. you Can add various pigments, such as titanium dioxide, carbon black, etc. Other additives include antioxidants, stabilizers, softeners, lubricants, antistatic agents, waxes, flame retardants and plasticizers.

After combining souleimanova copolymer, amine and in the presence and rubber composition having improved durability to handle, can be used directly in molded, extruded or molded products. In order to achieve desired for molding viscosity, it may be necessary to heat the composition.

Additional rubber component

In the composition of the invention may be supplemented with additional elastomer or rubber component. The term "rubber" or "rubber component" in the sense in which it is used in the present description, may include, although their list in any case is not limited to, the following polymers: butyl rubber, halogenated butyl rubber, star-shaped butyl rubber, halogenated star-shaped butyl rubber, isobutilene Homo-polymer, chloroprene, on BNR rubbers, ethylenepropylene ternary copolymers, ethylene-propylene copolymers, Starovoitova rubbers, polybutadiene, polyisoprene, otolaryngology sprinklers the measures halogenated otolaryngology copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicone rubber, propyleneoxide polymer and mixtures thereof. Other acceptable rubbers are described, for example, in Rubber Technology (Maurice Morton, ed., Chapman & Hall, 1995) and in the art is well known.

The term "butyl rubber" in the sense in which it is used in the present description, is defined as denoting a polymer mainly consisting of repeating units of isobutylene, but including a small number of repeating units of multilatina. In a preferred embodiment, from 85 to 99.5 wt.% butyl rubber accounted for duplicate links, derivatizing in the polymerization of isobutylene, whereas from 0.1 to 15 wt.% duplicate links derivateservlet from multilatina containing from 4 to 8 carbon atoms, such as butadiene, isoprene, hexadiene etc., preferably isoprene.

The term "halogenated butyl rubber" is defined as denoting butyl rubber, which contains at least the 0.05 wt.% atoms, halogen, such as chlorine or bromine, preferably bromine. Preferred halogenated butylketone are those that contain from 0.1 to 15 wt.% of halogen atoms, more preferably from 0.5 to 10.0 wt.% atoms is alogena, in terms of the total weight of halogenated polymer. Halogenated butyl rubber containing various amounts of chemically bound halogen, described in numerous patents (see, for example, US 2631984, 2732354, 3099644, 2944578, 3943664, 2964489 and 4130534).

The concept of "on BNR rubbers" in the sense in which it is used in the present description, refers to copolymers of Acrylonitrile with conjugate diene containing from 4 to 8 carbon atoms, preferably butadiene.

The term "ethylene-propylene copolymers," in the sense in which it is used in the present description, is defined as denoting the elastomeric or thermoplastic curable copolymers, which include units of ethylene and propylene. Preferred ethylene-propylene copolymer is a one in which the content of the ethylene component is in the range from 20 to 90 wt.% copolymer.

The concept of "ethylenepropylene ternary copolymers" in the sense in which it is used in the present description, is defined as denoting an elastomeric or thermoplastic curable ternary copolymers, including ethylene, propylene and diene units. The preferred diene units are 5-ethylidenenorbornene, 5-methyladenosine, Dicyclopentadiene, 1,4-hexadiene and 5-vinylnorbornene the new,

The concept of "italianatestyle copolymers and halogenated italianatestyle copolymers" in the sense in which they used in the present description, refer to copolymers comprising units of isoolefine and alkylthiol, preferably methylstyrene.

Vulcanizing agents and accelerators

Such compositions can also be vulcanizate using conventional hardeners or curing agents. Their examples include sulfur and sulfur vulcanizing agents; various organic peroxides such as benzoyl peroxide, documentparser, 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexane and 2,2'-bis(tert-BUTYLPEROXY)diisopropylbenzene; hydrocellulose vulcanizing agents; metal oxides such as zinc oxide and magnesium oxide, and organic zinc salts such as zinc stearate; diamines; devulcanized substances, such as various maleimide; etc. as they are all presented in US 5073597. Moreover, there can be used various phenolic resins known in the art and in 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 Van Duin u Aniko Souphanthong, 68 Rubber Chemistry and Technology 717-727 (1995).

The amount of vulcanizing substances usually vary depending on the type used in the constituent substances 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 all quantities are in terms of 100 miscast. song.

Whenever using halogenated butyl rubber or any halogenated rubber, for every 100 frequent. halogenated rubber use a small amount of oxide compounds of alkali-earth element, such as magnesium oxide, the content of which is equal to 3 frequent. one hundred grams of rubber (part./100) or less, it is advisable 2 frequent./100 or less. The oxide of alkaline-earth element is added as an agent, a cleansing from the halides of hydrogen.

You can also use conventional catalysts (accelerators), such as those known in the art and in literature. For example, you can use the acceptable number of different catalysts for Friedel-such as the chloride of divalent tin, salicylic acid, p-toluensulfonate acid, zinc chloride, etc.

Vulcanizing the group and uskoritel is used in such quantities, so when attainable degree of vulcanization at 23°acceptable for this specific rubber solvent, at least 90%, expediently at least 95, or 96%, preferably at least 97 or 98% vulcanizing rubber remained extrahieren. Acceptable solvents include xylene, cyclohexane, acetone, hexane, toluene, etc.

It was found that when the composition of the present invention vulcanized, after vulcanization compositions show improved thermal stability and resistance to thermal aging. Thus not only improves the durability to handle, but improve the characteristics of the vulcanized rubber product as a whole.

The compositions of the present invention are used for a variety of end purposes. So, for example, rubber or rubber chemicals-copolymer compositions used in the manufacture of pipes, hoses, gaskets, diaphragms, tires, inner shells for tires, films, bumpers, membranes, adhesives, cameras for tires and other products.

To illustrate the above discussion presents the following examples. Although these examples can be attributed to some variants of execution of the present invention, they should not be construed as limiting in any particular way, the scope of invention.

Example 1

In accordance with the tvii with the following details were preparing a number of mixtures, presented in table 1. Used two elastomer company ExxonMobil Chemical: Bromobutyl 2222, according to the specification contained 2 wt.% bromine and having a Mooney viscosity of 32 at 125° (1+8) (ASTM D1646, modified method), and the elastomer EXXPRO™ 89-1 (company ExxonMobil Chemical Company, Houston, Texas), commercially available brominated isobutylene/p-methylstyrene copolymer containing a 0.75 mol% of bromine atoms or 1.2 wt.% atoms of bromine in 5 wt.% parts of p-methylstyrene (PMS), including polymer possessing a Mooney viscosity of 35 at 125° (1+8) (ASTM D1646, modified method).

Three masterbatches (MS) were mixed in a closed laboratory rubber mixer (rubber mixer BR Banbury firm Farrel Co.) with the introduction of all of the components shown in table 1, except for the amine component. MS (mix 1A through 1G) were prepared on the basis of bromatologia elastomer. MC2 (mix 2A and 2B) and the machine (mix 3A and 3B) was prepared from a mixture of bromatologia elastomer and elastomer EXXPRO™. As the amine used tertiary amine, N,N-dimethylhexylamine, product Armeen DM16D (firm Akzo Nobel Co.). This amine was added in dvuhseriynyy elasticator for rubber in amounts shown in table 1.

In accordance with the compositions shown in table 1 (except Amin), the mass of each of the MS in General was 1500, the rubber mixer worked with a speed of 100 rpm when the fact is the water temperature value, which is circulated through the walls of the rubber mixer, 60°C. First in a rubber mixer was loaded elastomers, and all other components were added after 30 s after the introduction of the rubber mixer elastomers. The mixed compounds were removed from the rubber mixer when the temperature of this compound was achieved 150°C.

Components of MS, are presented in table 1, except as described above, were: liquid paraffin, mineral oil Drakeol™ 35 (firm PenRe Co.); carbon black, identified as carbon black N 660; stearic acid (company Witco Co.); magnesium oxide, Maglite™ For (firm S.R. Hall Co.).

The above amine was added to a 350-gram portions of the three compounds on the basis of MS in laboratory plasticators for rubber with shaft sizes 6×13-inch (or 15.2×33 cm) (firm KBS Corp.). Elasticator was equipped with a circulation system through the shafts of cooling water with a temperature of 27°C. the Process of mixing in plasticators started with mixing the compounds on the basis of MS in plasticators with subsequent gradual addition of liquid amine and continued with repeated cutting and plasticities until then, until he dispergirovanija evenly.

Further, the compounds of table 1 were Kalandarishvili low speed between two calender rolls, the temperature of which was maintained at a level of 85°C. the calendering Process WA is whether by heating compounds on the calender to the temperature when the compound remained on one of the rolls in the form of a uniform layer. Following this, to achieve a uniform temperature of the compound was left on a rotating roll for 2 min, after which the compound was removed in the form of a homogeneous sheet of a thickness of 3 mm.

Such leaves between pieces of polyester film Mylar in the form at 100°vypressovyvaniem square elements with dimensions of 0.2×15×15 see test cut samples with dimensions of 0.5×3 inches (1,25×7.6 cm).

Strength tests before treatment was performed using two different Instron testing machines, one of which was equipped with an artificial climate chamber, heated to 40°C. the Samples were pressed at a distance of 1 inch (2.54 cm) between the clamps of the testing machine. The test was performed by moving the clamps in opposite directions with a speed of 5 inches/minute (12.7 cm/min), 100%elongation, i.e. the total length of the extrusion 1 inch (2.54 cm). "Conditional stress (force divided by the original cross-sectional area) at 100%elongation was defined as "the strength to handle", which is shown in table 1 for 2 temperature test room (25° (C) and 40°C.

In the above laboratory plasticators another portion of 250 grams of each of the calendered samples of table 1 were additionally mixed with typical vulcanis is the MT group for the inner lining of the tire. Shafts of plasticators kept cold using circulating through them water with a temperature of 24°C. vulcanizing Components group included 3 part./100 zinc oxide (Kadox™ 930C company Zinc Corporation of America), 0,5 frequent./100 sulfur (firm R.E.Carroll, Inc.) and 1.5 ppm 100 MBTS (2-mercaptobenzothiazole) (AltaxTMcompany R.T. Vanderbilt Company, Inc.). The concept of "frequent./100" (parts per hundred rubber) denote the proportion reflecting the content of the component per 100 g of the total quantity of elastomer or elastomeric compositions of table 1. Further, the compounds were vulcanizable in a hot press at 160°C for 18 to 27 min, over time, equal to 90% of the length of cure (t90) plus 2 min, as determined in coremetrics.com test device ODR 2000E (Alpha Instruments), who worked at 160°With arc 3° and standard velocity of 100 cycles/min for 60 minutes

All test results are presented in table 1. Samples 1A through 1G showed a gradual increase in strength before treatment with increasing amine content from zero to 1.5 ppm 100. This increase in strength before treatment indicates the Association of ions between the polymer molecules when adding a tertiary amine.

In the cases of compounds 2B and 3B strength before treatment with the amine content of 0.5 ppm 100 was similar strength to sample processing 1G when maintained and amine 1,5 frequent./100, moreover, the sample CG had a slightly higher strength to handle than the sample 2B. This indicates that in the presence of the elastomer EXXPRO™ 89-1 Association of ions was much stronger. When the content of the amine 1.0 and 1.5 ppm 100 compounds 2 and 3 on the basis of MS showed very high values of viscosity, resulting in the manufacture of homogeneous sheets by calendering was impossible.

The results of testing vulcanized rubber mixtures are presented in units of shore hardness A. we know from experience that usually as heat aging halobutyl compounds hardness increases, as happened in the cases of compounds 1A, 2A and 3A. However, adding a tertiary amine reduced the hardening due to aging under the influence of heat. From the data presented in table 1, it is obvious that from 0.5 to 1.0 part./100 tertiary amine enough to the actual cessation of thermal aging after 48 h of aging at 125°C.

This example demonstrates improved strength before processing by adding a tertiary amine in bromoethylene compounds, in particular when this compound contains commercially available brominated isobutylene/p-methylstyrene copolymer (elastomer EXXPRO™). The example also demonstrates improved stability to thermal aging is the result of adding the tertiary amine in bromobutyl the th component in the mixture bromatologia component and elastomer EXXPRO™ .

Example 2

A series of compounds shown in table 2A, were mixed in a closed laboratory rubber mixer in accordance with the method described in example 1. This series used three of the elastomer, two of which are described in example 1 (Bromobutyl 2222 and elastomer EXXPRO™ 89-1), and the third commercially available brominated isobutylene/p-methylstyrene copolymer elastomer, the elastomer EXXPRO™ 3035 (company ExxonMobil Chemical Company, Houston, pc. Texas). This third polymer had a main chain containing 5 wt.% PMS to the synthesized and of 0.48 mole% of bromine, and a Mooney viscosity of 45 at 125° (1+8) (ASTM D1646, modified method). In this series of tertiary amine was injected into a closed rubber mixer close to the end of the mixing cycle. In this example, also used vulcanizing the group described in example 1, introduction to 2-roll elasticator for rubber, as set forth in example 1.

In this series of experiments comparing pairs of rubber mixtures with the addition of tertiary amine and without it. In cases of rubber compounds 4A and 4B compare the rubber on bambuterol basis, in the cases 5A and 5B compare the composition of bromobutyl with 2.0 frequent./100 elastomer EXXPRO™ 89-1, and in cases 6A and 6B compare bromoethylene composition with 2.0 frequent./100 elastomer EXXPRO™ 3035. In the case of directly bromobutyl in rubber compound 4B was added 1 part./100 amine, and SL is tea mixed elastomeric compounds in rubber compounds 5B and 6B was added to the reduced amount of the same amine, 0,5 frequent./100.

Strength to handle each rubber compound of example 2 was determined in the same test as in example 1, but the samples were stretched to rupture at 40°and rate of stretching 10 inches/min (25.4 cm/min). This example demonstrates the increase in voltage when the elongation of 100% (a measure of strength before treatment) by adding amine. Pair 6A and 6B, where the used elastomer EXXPRO™ 3035, showed the greatest increase in voltage when the elongation of 100%, and relative elongation at break. In this example, as in example 1, the addition of amine weakened the effects of thermal aging. In table 2B shows that all rubber compounds containing tertiary amine, showed reduced changes as thermal aging after vulcanization in regard to the voltage when the elongation, elongation at break and hardness.

This example also shows that the addition of amine does not affect the physical properties of rubber compounds to aging. Moreover, in cases bromobutyl compounds containing or not containing elastomeric polymers EXXPRO™ in composition, was demonstrated increased stability to thermal aging due to the addition of the tertiary amine.

Example 3

A series of model compounds for the inner lining of the tire shown in table 3, were mixed in secretoneurin rubber mixer in accordance with the method of example 2, where all the components were loaded into a closed rubber mixer. Materials in this series were prepared on the basis of the following composition: octabromodiphenyl star butyl rubber (BrSBB 6222, company ExxonMobil Chemical Company, Houston, pc. Texas) and commercially available brominated isobutylene/p-methylstyrene copolymer (elastomer EXXPRO™ 90-3, company ExxonMobil Chemical) in a ratio of 70/30. Product BrSBB 6222 contained the specified amount of 2.4 wt.%, bromine and had a Mooney viscosity of 32 at 125° (1+8) (ASTM D1646, modified method). Elastomer EXXPRO 90-3 had a main chain containing 5 wt.% PMS links to the synthesized comprised of 0.52 mole% of bromine and had a Mooney viscosity at 125 55°C. In rubber compounds of this series were also used homogenizing additive Struktol™ 40 MS (firm Struktol Company and increase the stickiness of phenolic resin SP-1068 (firm Schenectady International Inc.). As a tertiary amine for materials in this series used trioxadecyl from the same source, and that Amin examples 1 and 2.

Rubber compound in this series included increasing the number of amine from scratch in rubber compound 7 to 1.08 ppm 100 in the rubber mixture 10. Tensile strength at break before processing the rubber composition of table 3 was determined by testing at 40°in accordance with the method, which was used in example 2. Stress at elongation at 100% elongation at break of all rubber is s mixtures in table 3 are different from each other slightly. This example shows that the tertiary amine, which is vysokopatogennym, such as trioxadecyl with 3 side chains C16attached to the nitrogen atom, in the creation of a strong Association between the polymer chains is not as effective as Amin examples 1 and 2.

In all these examples demonstrate the usefulness of the present invention. The addition of tertiary amines in the rubber and copolymer components increase the strength before treatment, at the same time increasing the resistance of the vulcanized product against thermal aging. Shown in tables 1 and 2 data show that the presence of the amine increases resistance against heat aging and in the case of independent use of the product Bromobutyl 2222. When together with the product Bromobutyl 2222 contains halogenated otoolefan-alkylthiophenes copolymer, such as an elastomer EXXPRO™and add Amin, increase strength before treatment and resistance to thermal aging. To meet the different technological requirements can vary the number of different components, as well as the choice of the amine.

Although the present invention is described and illustrated with reference to specific ways of its implementation, for the usual specialists in the art it is obvious that the very things the ity of the invention leads to many different options, 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 jurisdictions in which such incorporation 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
Compositions 1A-3B
The rubber mixture (part./100)1A1B1B1G2A2B3A3B
Bromobutyl 222210010010010070705050
Elastomer EXXPRO™ 89-1000030305050
Vaseline oil1010101010 101010
Carbon black N 6605050505050505050
Stearic acid22222222
MgO0,150,150,150,150,150,150,150,15
N,N-dimethylhexylamine0,00,51,01,50,00,50,00,5
The strength to handle the stress at elongation 100%
25°C, MPa0,241MX 0.3170,3580,3880,2360,3350,2410,381
40°C, MPaof 0.1820,2200,2550,3050,1760,2430,1780,270
Shore a hardness after vulcanization
To aging55,352,552,753,154,152,353,5
After aging for 48 hours at 125°59,553,753,151,360,153,158,351,9

Table 2A
Compositions 4A-6B
The rubber mixture (part./100)4A4B5A5B6A6B
Bromobutyl 222210010080808080
Elastomer EXXPRO™ 89-100202000
Elastomer EXXPRO™ 303500002020
Vaseline oil101010101010
Carbon black N 660505050505050
Stearic acid222222
MgO0,150,150,150,15/td> 0,150,15
N,N-dimethylhexylamine0100,500,5

Table 2B
Properties of compositions 4A-6B
4A4B5A5B6A6B
The limit of the tensile strength before treatment at 40°
Stress at elongation of 100%, MPa0,1880,2120,2080,2830,2110,292
Elongation, %317341351575326643
The ultimate tensile strength of the vulcanizate to aging at the test temperature of 25°
Stress at elongation of 100%, MPa1,201,211,241,381,271,23
Deformation at break, %68868562 699723748
Stress at elongation of 100%, MPa1,941,511,761,681,831,49
Deformation at break, %564644518640596698
The ultimate tensile strength of the vulcanizate after aging for 48 hours at 140°s, test temperature: 25°
Stress at elongation of 100%, MPa1,791,481,991,521,881,48
Deformation at break, %562640512634586697
Hardness (vulcanizate) shore a
To aging47,151,154,753,754,351,9
After aging (48 h at 120°)to 58.153,1to 58.155,558,254,1
After aging for 48 hours at 140°) 60,754,559,755,357,154,1

Table 3
Compositions 7-10
The rubber mixture (part./100)78910
BrSBB 622270707070
Elastomer EXXPRO™ 90-330303030
Vaseline oil10101010
Struktol 40 MS5555
Carbon black N 66060606060
Resin SP-10684444
Stearic acid2222
MgO0,150,150,150.15
Trioxadecyl00,360,721,08
The limit of the tensile strength before treatment, 40°
Stress at elongation at 100% MPa 0,2390,2370,2350,256
Elongation, %376374426365

1. The composition of the rubber, including

at least one isorevenue copolymer that includes a link derivateservlet from kilometerstirana, isorevenue link containing in the range from 4 to 7 carbon atoms, and the copolymer includes from 0.5 to 20 wt.% kilometerstirana links; and amine compound corresponding to the formula (R1R2R3)N, in which R1denotes either a hydrogen atom or hydrocarbonous group4With30, R2denotes either a hydrogen atom or hydrocarbonous group with C1With30and R3denotes either a hydrogen atom or hydrocarbonous group with C1With30provided that at least one of R1, R2and R3does not denote a hydrogen atom,

the rubber component selected from butyl rubber, halogenated butyl rubber, star-shaped butyl rubber, halogenated star-shaped butyl rubber, isobutilene of homopolymer, chloroprene, butadiene-nitrile rubbers, ethylene-propylene-diene ternary copolymers, ethylene-propylene copolymers, the best choice of rubber chemicals is, polybutadiene, polyisoprene, souletin-alkylthiophenes copolymer, halogenated otoolefan-alkylthiophenes copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicone rubber, propyleneoxide polymer and mixtures thereof, and conventional additives.

2. The composition according to claim 1, wherein the rubber component is contained in an amount of 5 to 90 wt.% song.

3. The composition according to claim 2, characterized in that the rubber component is a halogenated butyl rubber.

4. The composition according to claim 1, characterized in that isorevenue copolymer is a halogenated isobutylene/p-methylstyrene copolymer.

5. The composition according to claim 4, characterized in that from 0.01 to 60 mol.% methyl groups contained in styrene are geometrinae group.

6. The composition according to claim 3, characterized in that the halogenated butyl rubber contains from 85 to 99.5 wt.% duplicate links, derivatizing from isobutylene, from 0.1 to 15 wt.% duplicate links, derivatizing of a conjugated diene, and from 0.1 to 15 wt.% of halogen atoms.

7. The composition according to claim 3, characterized in that the halogenated butyl rubber contains from 85 to 99.5 wt.% duplicate links, derivatizing from isobutylene, from 0.1 to 15 wt.% duplicate links, derivative is different from isoprene, and from 0.1% to 15 wt.% bromine atoms.

8. The composition according to claim 4, characterized in that the copolymer contains isobutilene links in an amount of from 88 to 98 wt.% copolymer.

9. The composition according to claim 1, characterized in that the composition comprises from 0.05 to 2 molar equivalents. amine compound relative to the number of moles of halogen contained in the composition.

10. The composition according to claim 1, wherein R3means hydrocarbonous group with C1C8.

11. The composition according to claim 1, wherein both R1and R2represent a hydrogen atom.

12. The composition according to claim 1, wherein both R1and R2denote hydrocarbonous group4With30.

13. The composition according to claim 1, wherein R1means hydrocarbonous group with C4With30and R2means hydrocarbonous group with C1With4.

14. The composition according to claim 1, wherein R1means hydrocarbonous group4With30, R2means hydrocarbonous group with C1With4and R3means hydrocarbonous group with C1C8.

15. The composition according to claim 1, characterized in that the amine compound chosen from N,N-dimethylhexylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylethanolamine, N,N-diethylacrylamide, N-dimethylbenzylamine, N,N-methylpropylamine.

16. The composition according to claim 1, wherein the amine compound is contained in an amount of from 0.01 to 5 wt.% song.

17. The composition according to claim 1, characterized in that it vulcanized.

18. The composition according to claim 1, wherein the rubber component is a halogenated otoolefan-alkylthiophenes copolymer.

19. The composition according to claim 1, wherein the amine compound is an N,N-dimethylhexylamine.

20. The method of preparation of the composition of the rubber mixture comprising a combination of at least one souleimanova copolymer that includes a link derivateservlet from kilometerstirana, isorevenue link containing in the range from 4 to 7 carbon atoms, and the copolymer includes from 0.5 to 20 wt.% kilometerstirana links; and

amine compound corresponding to the formula (R1R2R3)N, in which R1denotes either a hydrogen atom or hydrocarbonous group4With30, R2denotes either a hydrogen atom or hydrocarbonous group with C1With30and R3denotes either a hydrogen atom or hydrocarbonous group with C1With30provided that at least one of R1, R2and R3does not denote a hydrogen atom,

from 5 to 90 wt.% rubber components is the selected from butyl rubber, halogenated butyl rubber, star-shaped butyl rubber, halogenated star-shaped butyl rubber, isobutilene of homopolymer, chloroprene, butadiene-nitrile rubbers, ethylene-propylene-diene ternary copolymers, ethylene-propylene copolymers, the best choice rubbers, polybutadiene, polyisoprene, souletin-alkylthiophenes copolymer, halogenated otoolefan-alkylthiophenes copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicone rubber, propyleneoxide polymer and mixtures thereof, and conventional additives.

21. The method according to claim 20, characterized in that the rubber component is a halogenated butyl rubber.

22. The method according to item 21, wherein the halogenated butyl rubber contains from 85 to 99.5 wt.% duplicate links, derivatizing from isobutylene, from 0.1 to 15 wt.% duplicate links, derivatizing of a conjugated diene, and from 0.1% to 15 wt.% of halogen atoms.

23. The method according to item 22, wherein the halogenated butyl rubber contains from 85 to 99.5 wt.% duplicate links, derivatizing from isobutylene, from 0.1 to 15 wt.% duplicate links, derivatizing from isoprene, and from 0.1 to 15 wt.% bromine atoms.

24. The method according to claim 20, characterized in that is that the copolymer contains isobutilene links in an amount of from 88 to 98 wt.% copolymer.

25. The method according to claim 20, characterized in that the copolymer is a halogenated isobutylene/p-methylstyrene copolymer.

26. The method according A.25, wherein from 0.01 to 60 mol.% methyl groups are geometrinae group.

27. The method according to claim 20, characterized in that the composition comprises from 0.05 to 2 molar equivalents. amine compound relative to the number of moles of halogen, in composition.

28. The method according to claim 20, wherein R3means hydrocarbonous group with C1C8.

29. The method according to claim 20, wherein both R1and R2represent a hydrogen atom.

30. The method according to claim 20, wherein both R1and R2denote hydrocarbonous group4With30.

31. The method according to claim 20, wherein R1means hydrocarbonous group with C4With30and R2means hydrocarbonous group with C1With4.

32. The method according to claim 20, wherein R1means hydrocarbonous group with C4With30, R2means hydrocarbonous group with C1With4and R3means hydrocarbonous group with C1C8.

33. The method according to claim 20, characterized in that the amine compound chosen from N,N-dimethylhexylamine, N,N-dimethylhexylamine, N,N-dimethylmaleic lamina, N,N-dimethylethanolamine, N,N-diethylacrylamide, N,N-dimethylbenzylamine, N,N-methylpropylamine.

34. The method according to claim 20, wherein the amine compound is contained in an amount of from 0.01 to 5 wt.% song.

35. The method according to claim 20, characterized in that this composition vulcanized.

36. The method of preparation of the composition of the rubber mixture comprising a combination of from 5 to 90 wt.% the rubber component selected from butyl rubber, halogenated butyl rubber, star-shaped butyl rubber, halogenated star-shaped butyl rubber, isobutilene of homopolymer, chloroprene, butadiene-nitrile rubbers, ethylene-propylene-diene ternary copolymers, ethylene-propylene copolymers, the best choice rubbers, polybutadiene, polyisoprene, souletin-alkylthiophenes copolymer, halogenated otoolefan-alkylthiophenes copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicone rubber, propyleneoxide polymer and mixtures thereof;

0.01 to 5 wt.% amine compounds represented by the formula (R1R2R3)N, in which R1denotes either a hydrogen atom or hydrocarbonous group with C4With30, R2denotes either a hydrogen atom or hydrocarbonous group with C1With30and R denotes either a hydrogen atom or hydrocarbonous group with C1With30provided that at least one of R1, R2and R3does not denote a hydrogen atom; from 5 to 90 wt.% souleimanova copolymer that includes a link derivateservlet from kilometerstirana, isorevenue link containing in the range from 4 to 7 carbon atoms, and the copolymer includes from 0.5 to 20 wt.% kilometerstirana links and conventional additives.

37. The method according to p, wherein the rubber component is a halogenated butyl rubber.

38. The method according to clause 37, wherein the halogenated butyl rubber contains from 85 to 99.5 wt.% duplicate links, derivatizing from isobutylene, from 0.1 to 15 wt.% duplicate links, derivatizing of a conjugated diene, and from 0.1% to 15 wt.% of halogen atoms.

39. The method according to § 38, wherein the halogenated butyl rubber contains from 85 to 99.5 wt.% duplicate links, derivatizing from isobutylene, from 0.1 to 15 wt.% duplicate links, derivatizing from isoprene, and from 0.1% to 15 wt.% bromine atoms.

40. The method according to p, characterized in that the copolymer contains isobutilene links in an amount of from 88 to 98 wt.% copolymer.

41. The method according to p, characterized in that the copolymer is a halogenated isobutyl is n/a-methylstyrene copolymer.

42. The method according to paragraph 41, wherein from 0.01 to 60 mol.% methyl groups present in the benzene ring of alkylthiol contain a halogen atom.

43. The method according to p, characterized in that the composition comprises from 0.05 to 2 molar equivalents. amine relative to the number of moles of halogen, in composition.

44. The method according to p, wherein R3means hydrocarbonous group with C1C8.

45. The method according to p, wherein both R1and R2represent a hydrogen atom.

46. The method according to p, wherein both R1and R2denote hydrocarbonous group with C4With30.

47. The method according to p, wherein R1means hydrocarbonous group with C4With30and R2means hydrocarbonous group with C1With4.

48. The method according to p, wherein R1means hydrocarbonous group with C4With30, R2means hydrocarbonous group with C1With4and R3means hydrocarbonous group with C1C8.

49. The method according to p, characterized in that the amine compound chosen from N,N-dimethylhexylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylethanolamine, N,N-diethylacrylamide, N,N-dimethylbenzylamine, N,N-methylpropylamine.

50. JV the property on p, wherein the amine compound is an N,N-dimethylhexylamine.

51. The method according to p, characterized in that this composition vulcanized.



 

Same patents:

FIELD: polymer materials.

SUBSTANCE: invention relates to thermoplastic elastomer composition for manufacturing products such as films, which composition contains dynamically curable mixture of (A) halogenated isobutylene/p-methylstyrene copolymer, (B) polyamide, and (C) antioxidant having melting point above 70°C and below 200°C, granulated elastomer (A) obtained by granulation in presence of antioxidant (C) as granulator being dispersed as a domain in the continuous phase of polyamide (B) and composition containing (A) and (B) components being dynamically cured. Thus obtained film is characterized by better stretching than film made from composition containing curing agent as granulator and by excellent durability and stability at low temperature as compared to film made from talc-containing composition.

EFFECT: increased durability, heat resistance, elasticity and air impermeability.

7 cl, 3 tbl, 5 ex

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

FIELD: polymer materials.

SUBSTANCE: invention relates to air bladders such as inner tire cover or pneumatic tire tube including composition based on halogenated terpolymer constituted by units derived from C4-C8-isoolefins, units derived from C4-C14-multiolefins, and units derived from p-alkylstyrene. Compositions based on halogenated terpolymer are characterized by low air permeability, good adhesion to tire body, and acceptable longevity, which all allows their use in manufacture of air bladder.

EFFECT: improved performance characteristics of air bladders.

11 cl, 1 dwg, 8 tbl

FIELD: polymer mixtures and rubber industry.

SUBSTANCE: low-permeable elastomer composition useful in manufacturing pneumatic diaphragm such as inside shell of tire comprises elastomer, filler, stratified clay, polybutene softener having molecular mass 400 to 10000, and curing agent. Elastomer can be random copolymer including unit derived from C4-C7-isomonoolefin and can be selected from halogenated isobutylene/p-methylstyrene copolymer, star-shaped butyl rubber, halogenated butyl rubber, and their combinations. Composition as a whole forms nanocomposite. Prior to be mixed with copolymer, clay may optionally be subjected to additional stratification treatment.

EFFECT: improved pneumatic diaphragm properties of composition and improved processability thereof.

13 cl, 19 tbl, 44 ex

FIELD: rubber industry; automotive industry; production of the sealing layer at manufacture of the tubeless tires and the pneumatic constructions.

SUBSTANCE: the invention is pertaining to rubber industry and the automotive industry and is dealt with production of the sealing layer at manufacture of the tubeless tires and the pneumatic constructions. The rubber mixture contains the isoprene rubber, the filled chlorbutyl rubber produced by interaction at comixing of the butyl rubber and the hlorinated hydrocarbon of the common formulaСnН(2n+2)С1х, where n = 10-30, х = 7-24, at the temperature of 80-150°С at the presence of the colloid silicon dioxide introduced into the mixture in the process of their comixing, brimstone, the sulfonamide accelerant, the stearic acid, zinc oxide, the high-pressure polyethylene, the engineering carbon, the alkylphenolamide resin. The technical result of the invention consists in the increased protection of the rubber mixture from the possible premature vulcanization in the processes of its preparation and reprocessing.

EFFECT: the invention ensures the increased protection of the rubber mixture from the possible premature vulcanization in the processes of its preparation and reprocessing.

2 tbl, 1 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to elevated-viscosity thermoplastic halogenated elastomer compositions and to a process for preparing the same. Composition according to invention contains thermoplastic polymer, at least one isoolefin copolymer comprising unit derived from halomethylstyrene, and at least one hindered amine or phosphine compound having the respective structure R1R2 R3N or R1R2R3P wherein R1 is H or C-1-C6-alkyl, R2 is C1-C30-alkyl and R3 is C4-C30-alkyl and further wherein R3 represents alkyl higher than R-1. A process for preparing elevated-viscosity thermoplastic composition consists in mixing thermoplastic polymer, at least one isoolefin copolymer comprising unit derived from halomethylstyrene, and at least one hindered amine or phosphine compound to obtain thermoplastic elastomer compositions, including dynamically cured ones, containing more finely dispersed elastomer.

EFFECT: improved mechanical properties.

4 cl, 10 tbl

Rubber composition // 2254348

FIELD: rubber industry.

SUBSTANCE: invention concerns a method for grafting polymers based on conjugated diene monomers to brominated butyl rubbers and using thus obtained grafted copolymers in rubber compositions, which, after vulcanization, acquire improved physical characteristics. Grafting procedure comprises mixing solid brominated butyl rubber with solid polymers based on conjugated diene monomer including some quantity of bonds C-S-(S)n-C with n being an integer equal from 1 to 7. Mixing is conducted at temperature above 50 over a period of time long enough to complete the grafting. Rubber composition containing above grafted polymer optionally includes one or more curing agents. Cured rubber composition is intended for manufacturing tracks.

EFFECT: increased shock-absorbing capacity of products.

14 cl, 5 dwg, 5 tbl, 3 ex

FIELD: plastic, rubber, chemical, petrochemical, paint-vehicle, air and other industrials.

SUBSTANCE: halogenated or halosulfonated 4-methylpentene-1 (co)polymer is obtained in tetrachloroethane or chlorobenzene solution and contains chemically coupled chlorine and/or bromine, or chlorine and sulfur, or bromine and sulfur, or simultaneously chlorine, bromine and sulfur in form of groups -SO2Cl and -SO2Br, wherein content of chlorine and/or bromine and sulfur is 1-73 mass % and 0,2-4,0 mass %, respectively. Also disclosed are polymer, elastomer composition, binding agent and articles based on halogenated and halosulfonated 4-methylpentene-1 (co)polymer.

EFFECT: butene-1 (co)polymer, article and composition therefrom with increased controlling strength, elasticity, fire-retarding, as well as controlling flow point, percent elongation, etc.

FIELD: plastic, rubber, chemical, petrochemical, paint-vehicle, air and other industrials.

SUBSTANCE: halogenated or halosulfonated butene-1 (co)polymer is obtained in tetrachloroethane or chlorobenzene solution and contains chemically coupled chlorine and/or bromine, or chlorine and sulfur, or bromine and sulfur, or simultaneously chlorine, bromine and sulfur in form of groups -SO2Cl and -SO2Br, wherein content of chlorine and/or bromine and sulfur is 1-73 mass % and 0,2-4,0 mass %, respectively. Also disclosed are polymer, elastomer composition, binding agent and articles based on halogenated and halosulfonated butene-1 (co)polymer.

EFFECT: butene-1 (co)polymer, article and composition therefrom with increased controlling strength, elasticity, fire-retarding, as well as controlling flow point, percent elongation, etc.

9 cl, 19 tbl, 6 dwg

FIELD: polymer materials.

SUBSTANCE: invention, in particular, relates to isobutylene-based halogenated polymers showing elevated pre-treatment strength and elevated impermeability as well as to and a method for preparation thereof. Non-cured thin barrier layer for rubber products comprises 3-95% isobutylene-based polymer and 95-3% semicrystalline polymer having melting temperature from about 25 to about 105°C and melting heat from about 9 to about 50 J/g as measured by differential scanning calorimetry. This barrier layer is used for inside tire envelope and as inner tube. Rubber compound contains semi-crystalline propylene polymer with about 75 wt % propylene units and is prepared on common rubber manufacture equipment.

EFFECT: improved pre-treatment strength, pre-treatment elongation, and pre-treatment relaxation properties at elevated temperature and improved aging resistance and barrier properties.

35 cl, 8 tbl

Rubber mix // 2309962

FIELD: rubber industry; production of rubber mixes used for manufacture of collar seals for oil equipment.

SUBSTANCE: proposed rubber mix contains the following constituents, mass-% (per 100 parts by mass of rubber): butadiene-nitrile rubber Grade БНКС-40AM and БНКС-40AMH, 80.0; hydrogenated butadiene-nitrile rubber Grade БНКВ, 40-30; Terban, 20.0; sulfur, 3.5; sulfenamide M, 0.50; altax, 0.50; stearic acid, 1.00; colophony, 2.0; dibutoxyethyl adipate, 11.0; white carbon, 5.0; zinc white, 4.0; diafen, 2.0; commercial carbon П-803, 20.0; commercial carbon П-245; modifying agent РУ-Д, 2.0; aramide or polyamide fibers, 10.00.

EFFECT: enhanced tear resistance of vulcanizing agents; increased service life of collar seal; possibility of using collar seals at low temperatures.

3 tbl

FIELD: composite materials.

SUBSTANCE: invention relates to nanocomposite comprising (i) clay; (ii) copolymer constituted by units derived from C4-C7-isomonoolefin, units derived from p-methylstyrene, and units derived from p-halomethylstyrene; or butylrubber constituted by units derived from C4-C7-isoolefin, units derived from multiolefin, and units derived from halogenated multiolefin; and (iii) one or several stratifying additives including amine, said stratifying additive being present in nanocomposite in amount between 0.1 and 20%. Nanocomposite is applicable for manufacturing internal shells for tires and inner tubes for automotives, including trucks and other vehicles for transportation loads and/or passengers.

EFFECT: reduced air permeability of nanocomposite products.

18 cl, 5 tbl

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

FIELD: rubber industry; chemical industry; production of the vulcanized rubber mixture made on the basis of an acrylate rubber and partially on the hydrogenated butadiene-nitril caoutchoucks.

SUBSTANCE: the invention is pertaining to production of the vulcanized rubber mixture made on the basis of the acrylate rubber and partially on the basis of the hydrogenated butadiene-nitril caoutchoucks, which is used for manufacture of the hardware products operable at the temperatures up to 150°С and having the heightened wear resistance and which may be used in production of the industrial rubber products - the rings, the sleeves gaskets, the drive belts operating in the friction pairs at the heightened temperatures. The vulcanized rubber mixture made on the basis of the acrylate rubber of the heightened wear resistance includes the mineral filler, the engineering carbon, the antioxidant, the plasticizer, the partially hydrogenated butadiene-nitril caoutchouck, the quaternary ammonium base, the metallic stearate, the brimstone, the vulcanization accelerators, zinc oxide, the anti-adhesive agent, the anti-scorching agent. The rubber mixture made on the basis of the acrylate rubber of the heightened wear resistance allows to increase the level of the values of the indexes: the wear resistance, the tensile strength, the frost hardiness, the resistance to the action of the aggressive mediums of the aromatic series.

EFFECT: the invention ensures the increased level of the values of the indexes of the rubber mixture made on the basis of the acrylate rubber of the heightened wear resistance: the wear resistance, the tensile strength, the frost hardiness, the resistance to the action of the aggressive mediums of the aromatic series.

3 cl, 2 tbl

FIELD: rocket fuels.

SUBSTANCE: invention relates to rocket engineering and deals with epoxide molding composition for armoring channeled and channel-free inserted charges of mixed solid propellant with diameter 300-700 mm prepared by filling technique and operated within a large temperature range. Composition comprises 39-42% epoxide dian resin as modifier and plasticizer, 6.48-10.80% m-phenylenediamine as aromatic diamine, and 1.44-3.00% polyethylenepolyamine as aliphatic amine. Aromatic and aliphatic amines are taken at weight ratio 4.5:1.

EFFECT: improved technological, mechanical, and adhesion properties.

2 tbl, 7 ex

FIELD: sealing composition and materials.

SUBSTANCE: invention relates to a method for preparing a composition designated for electric sealing and contacting wave guide tracts used in electronic engineering industry and instrument making. The composition comprises the following ratio of components, mas. p. p.: epoxy diane resin ED-20, 30-40; silver powder of the grade pure, 90-110; polyethylene polyamine of the grade A, 3.5-5.5, and cyclohexanone as a solvent, 40-70. Invention provides enhancing moisture resistance under condition of 98% of moisture at temperature +40°C for 12 days, increasing adhesion and providing impact resistance to temperature effect in the range from -60°C to +85°C.

EFFECT: improved and enhanced properties of composition.

2 tbl, 3 ex

FIELD: polymers, in particular water-resistant epoxy composition for production of coats, filling floors, compounds.

SUBSTANCE: claimed composition contains (mass pts): law molecular epoxydianic oligomer with molecular mass of 400-700 and epoxy number of 11-21 - 100; fluorine-containing epoxy oligomer based on 2,2-bis-(p-oxyphenyl)-hexafluoropropane diepohypropyl ester with molecular mass of 650 and epoxy number of 15 - 5-10; triethylenetetramine as amine curing agent - 13.6. Law molecular epoxydianic oligomer is used in form of 50 mass % solution in mixture of ethylcellosolve with xylene taken in ratio of 1:7. Fluorine-containing epoxy oligomer is used in form of 50 mass % solution in mixture of ethylcellosolve with xylene taken in ratio of 1:7.

EFFECT: coating with increased water resistance.

1 tbl, 7 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to elevated-viscosity thermoplastic halogenated elastomer compositions and to a process for preparing the same. Composition according to invention contains thermoplastic polymer, at least one isoolefin copolymer comprising unit derived from halomethylstyrene, and at least one hindered amine or phosphine compound having the respective structure R1R2 R3N or R1R2R3P wherein R1 is H or C-1-C6-alkyl, R2 is C1-C30-alkyl and R3 is C4-C30-alkyl and further wherein R3 represents alkyl higher than R-1. A process for preparing elevated-viscosity thermoplastic composition consists in mixing thermoplastic polymer, at least one isoolefin copolymer comprising unit derived from halomethylstyrene, and at least one hindered amine or phosphine compound to obtain thermoplastic elastomer compositions, including dynamically cured ones, containing more finely dispersed elastomer.

EFFECT: improved mechanical properties.

4 cl, 10 tbl

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to leucine-containing stabilizing composition improving color used in treatment of thermoplastic polymers based on polyolefins. The stabilizing composition comprises: (a) at least one sterically hindered phenol; (b) at least one phosphorus-containing secondary antioxidant, and (c) at least leucine or its isomer wherein the mass ratio of components (a):(b):(c) is in the range from 1:5:3 to 2:0.5:0.1, respectively. Also, invention describes a method for improving stability of thermoplastic polymers color based on polyolefins that involves addition to their composition before or after processing the stabilizing composition conferring the stability property in the amount from 0.001 to 5 wt.-% as measured for thermoplastic polymer. Invention describes a method for preparing the stabilizing composition improving color involving mixing components (a), (b) and (c) wherein (a) represents at least one sterically hindered phenol, (b) represents at least one phosphorus-containing secondary antioxidant, and (c) represents at least leucine or its isomer wherein the mass ratio of components (a):(b):(c) is in the range from 1:5:3 to 2:0.5:0.1, respectively. Invention provides conferring the stability property to polyolefin-base thermoplastic polymers resulting to improvement of the color stability of final products.

EFFECT: improved and valuable properties of compositions.

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

Dispersion // 2320680

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention elates to dispersions. Invention describes a method for preparing an aqueous dispersion. Method involves the first step for mixing, the first material not mixing with this phase, the first polymeric material and the second polymeric material wherein: (a) the first polymeric material comprises a repeating monomer of the formula (I) given in the invention description wherein A and B are similar or different and chosen from aromatic and heteroaromatic groups that can be substituted, and at least of them comprises a relatively polar atom or group; R1 and R2 comprise independently relatively nonpolar atoms or groups; or the first polymeric material is prepared or can be prepared by formation of compound wherein A, B, R1 and R2 mean groups described above in an aqueous solvent, and carrying out reaction of groups C=C of indicated compound each with other to yield the first polymeric material; (b) the second polymeric material comprises a functional group able to react with the first polymeric material to form covalent bonds between the first and the second polymeric materials; (c) the mass ratio of the first polymeric material to mass of the first phase is 0.0025 or less; (d) the mass ratio of the second polymeric material to mass of the first phase is 0.035 or less; (e) the indicated first phase comprises water. Also, invention describes methods for preparing dispersions (variants) and dispersions (variants). Invention provides preparing stable dispersion of materials.

EFFECT: improved preparing method of dispersions.

37 cl, 15 ex

Up!