KR20090077769A - Particle-matrix composition coated with mixture comprising polysulfide polymer - Google Patents

Abstract

The invention pertains to a composition comprising a particle and a matrix, wherein the particle is at least partially coated with a compound or a mixture of compounds comprising at least one of a) a polysulfide polymer and a curing system; and b) a cured polysulfide polymer obtained from a polysulfide polymer having at least two epoxy end groups. Most preferred polysulfide polymers are: formula (I), (II), (III) and formula (IV) wherein n is independently 1-200 and R' is formula (V) wherein m is 0 to 10, R3 is independently H or CH3, and the end indicated with the double asterisk is bonded to the epoxide group. The invention further relates to particle-elastomers comprising said composition, and skim products, tires, tire treads, and belts comprising these particle-elastomers.

Description

Particle-matrix composition coated with mixture comprising polysulfide polymer

The present invention relates to a composition comprising particles and a matrix, wherein the particles are at least partially coated with a mixture of compounds; The invention also relates to a particle-elastomer composition. The invention further relates to a skimmed product, a tire, a tire tread and a belt comprising said particle-elastomeric composition.

In the tire and belt industry, among other things, better mechanical, heat build-up and hysteresis properties are required. It has long been known that the mechanical properties of rubber can be improved by using a large amount of sulfur as a crosslinking agent to increase the crosslink density of the vulcanized rubber. However, the use of large amounts of sulfur faces the disadvantage of high heat generation, which leads to a significant reduction in resistance to flex cracking and heat resistance, among other properties in the final product. To eliminate this drawback, treated chopped fibers, pellets prepared therefrom or treated pellets, in particular pellets treated with polysulfide, burnt salts, and sulfur to sulfur-vulcanizing systems Has been proposed. These pellets also contain wax to improve processability.

JP 66008866 describes the use of benzothiazole sulfide as an adhesion promoter for polyamide fibers. However, the method does not provide tires and belts with low crack growth, low loss modulus and low tan delta. In JP 56129280, JP 60072928, JP 60072929, and JP 60072972, polysulfide polymers are applied as part of an adhesive system to bond fibers such as polyester and aramid fibers to rubber. None of these methods provide tires and belts with low crack growth, low loss modulus and low tan delta.

In WO 2006/087161 the fibers are treated with polysulfide, sulfur and burnt salts and blended into rubber. This reference describes the use of polysulfide monomers in combination with sulfur to allow the composition to act as a curing system for the burnt salt.

U.S. Patent No. 3,673,150 is impregnated with glass fibers with Thiokol A, a polymer of the formula (CH ₂ CH ₂ S ₄ ) _n obtained from sodium tetrasulfide and ethylene dichloride and containing no epoxide groups. If Thiokol A is considered a polysulfide polymer according to the present invention, the composition of US Pat. No. 3,673,150 lacks a curing system. If Thiokol A is considered a curing agent, it is a curing agent for the crosslinked chain of polyolefins having two or more sulfur atoms, but it cannot cure Thiokol A itself. Thus, Thiokol A is not a curing system for polysulfide polymers and depends on the definition of Thiokol A, which is a polysulfide polymer or curing system but not both at the same time.

Waxed pellets are also known in the art. For example, EP 0 889 072 describes the coating of aramid pellets with polymeric components such as waxes. However, these pellets do not include waxes containing peroxides or azo.

US Pat. No. 6,068,922 describes pellets comprising aramid fibers and extrudable polymers such as polyethylene, polypropylene, or polyamides. The fibers can be coated with conventional sizing agents (RF, epoxy, silicone). Coatings containing radical initiators are not described.

The present invention provides a solution to this problem by using a new class of treated particles (eg chopped fibers, staple fibers, pulp or powder) in the sulfur-vulcanization of rubber; It provides particles and pellets thereof that solve the old problem of reduced hysteresis and heat generation in rubber compositions.

To this end, the present invention relates to a composition comprising particles and a matrix, wherein the particles are cured polysulfide polymers obtained from polysulfide polymers and curing systems (a) and polysulfide polymers having two or more epoxy end groups. at least partially coated with a compound or mixture of compounds comprising at least one of (b).

More specifically, the composition comprises a linear or branched polysulfide polymer compound of formula (V).

A-B-C

In Formula V above,

B is a residue comprising independently 1 to 200 repeating units of the formula-[XR ₂ -XR ₁ -S _x ]-wherein X is independently CH ₂ , S or O; x is 2, 3 or 4; R ₁ and R ₂ are substituted or unsubstituted alkylene having 1 to 10 carbon atoms, substituted or unsubstituted arylene having 6 to 10 carbon atoms, alkyleneoxy having 1 to 5 carbon atoms, and alkyleneoxy having 2 to 10 carbon atoms. Independently selected from alkylene; Wherein the substituent is a residue comprising independently 1 to 200 repeating units of the formula D- [XR ₂ -XR ₁ -S _x ] -E, wherein X, R ₁ , R ₂ and x are provided above Or X, R ₁ and R ₂ are independently a bond and the residues XR ₂ -XR ₁ contain two or more atoms; one of D and E is a bond and the other has the same meaning as A) Is};

A and C are independently selected from hydrogen and a group containing at least one of halogen, epoxy, hydroxy, isocyanate, silyl and vinyl.

The compound may essentially have a linear molecular structure, but may also have a partially branched linear structure. In the above Formula V, when R ₁ and / or R ₂ means substituted alkylene having 1 to 10 carbon atoms or substituted arylene having 6 to 10 carbon atoms, the substituent is represented by the formula D- [XR ₂ -XR _1- S _x ] -E is a residue containing independently 1 to 200 repeating units, in which the groups R ₁ and R ₂ are independently alkylene having 1 to 10 carbon atoms, arylene having 6 to 10 carbon atoms, and carbon atoms Alkyleneoxy having 1 to 5 and alkyleneoxyalkylene having 2 to 10 carbon atoms.

X is preferably selected from S and O. Alkylene groups can be exemplified by methylene, ethylene, propylene, isopropylene, butylene, isobutylene, neopentylene, hexylene and the like. The arylene group may be exemplified by phenylene, benzylene or methylbenzylene and the like, and the residues XR ₂ -XR ₁ -are alkyleneoxyalkylene groups, for example, methyleneoxymethylene, ethyleneoxyethylene, methyleneoxyethylene Oxy, ethyleneoxyethyleneoxy, propenyloxypropylene, and the like, wherein the oxy group can be replaced with sulfide. Specific examples include, for example, the formulas -CH ₂ OCH ₂ OCH _2- , -C ₂ H ₄ OCH ₂ OC ₂ H _4- , -C ₂ H ₄ OC ₂ H ₄ OC ₂ H _4- , -C ₃ H ₆ OCH ₂ OC ₃ H _6- , -C ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H _4- , -CH ₂ SCH ₂ SCH _2- , -C ₂ H ₄ SCH ₂ SC ₂ H _4- , -C ₂ H ₄ SCH ₂ SC ₂ H _4- , -C ₂ H ₄ OC ₂ H ₄ SC ₂ H ₄ OC ₂ H ₄ -It can be represented by. Most preferred divalent organic groups XR ₂ -XR ₁ -are those represented by the formula -C ₂ H ₄ OCH ₂ OC ₂ H _4- . The above-mentioned divalent organic group comprises 1 to 200 repeating units of the formula D- [XR ₂ -XR ₁ -S _x ] -E, wherein X, R ₁ , R ₂ and x have the meanings provided above. It may be branched by a substituent including independently.

Examples of reactive terminal groups A and C (and / or D and E) include epiclohydrin, glycidyl ether of bisphenol A, vinyl triethoxysilane and (3-glycidyloxypropyl) trimethoxysilane Including but not limited to. Most preferred groups groups A and C are the reaction products of H, glycidyl, and polysulfide polymers, where A or C is a reactive compound glycidylether or F of H and bisphenol A. Some branched and unbranched polysulfide polymers having 5 to 38 repeat units are commercially available under the trade names Thioplast ™ G, Thiokol® LP, Thioplast ™ EPS and Thiokol® ELP.

Among the most preferred polysulfide polymers are commercially available polymers of formulas (I), (II), (III) and (IV).

In the above formulas (I), (II), (III) and (IV),

n is independently 1 to 200,

(여기서, m은 0 내지 10이고, R₃은 독립적으로 H 또는 CH₃이고, 2개의 별표로 표시된 말단은 에폭사이드 그룹에 결합된다)이다. R 'is

Wherein m is 0 to 10, R ₃ is independently H or CH ₃ , and the two asterisk terminated groups are bonded to the epoxide group.

(여기서, n은 2 내지 6이고, R은 수소, 할로겐, 니트로, 하이드록시, C1-C12알킬, C1-C12알콕시 및 C7-C12아르알킬로부터 독립적으로 선택된다)의 폴리설파이드의 배합물(C)이다.Many different curing systems for similar compounds are described, for example, in Journal of Applied Polymer Science, 1959, vol. 2, issue 4, pages 39-45; and Topics in Sulfur Chemistry, volume 3, page 26. Curing systems include lead oxide (IV), Mn (IV) oxide, low molecular weight phenolic resins, diisocyanates, polyisocyanates, diepoxides, polyepoxides, dicumyl peroxide, cumene hydroperoxide, calcium peroxide, peroxide Zinc, sodium perborate, sodium periodate, iodine, tetrabutylammonium peroxydisulfate, p-quinonedioxime, and combinations of sulfur and polysulfide. Preferred curing systems are sulfur and

(C) A combination of polysulfides, wherein n is 2 to 6 and R is independently selected from hydrogen, halogen, nitro, hydroxy, C 1 -C 12 alkyl, C 1 -C 12 alkoxy and C 7 -C 12 aralkyl to be.

Polysulfide polymers with glycidyl functionality can be selected from any epoxy curing system known in the art. Examples of curing agents include, but are not limited to, polyols such as polyvinylalcohols and polyetherpolyols, polyacid anhydrides, polycarboxylic acids, polyisocyanates and primary amines. In some cases, additional catalyst is required for curing to occur. In addition, polysulfide polymers having two or more glycidyl groups can be cured on their own without addition to the curing system. The term "cured" polysulfide polymer having two or more epoxy end groups is a polysulfide polymer molecule having two or more epoxy end groups wherein the polysulfide polymer molecule has two or more epoxy end groups through its glycidyl group. It is meant to be at least partially coupled to a sulfide polymer molecule.

In a preferred embodiment, the present invention relates to a composition comprising particles and matrix having enhanced rubber properties in an elastomer. The matrix can be a wax or a polymer. Based on the weight of the composition, the composition contains up to 85% by weight matrix, preferably wax. Examples of suitable waxes are microcrystalline waxes of higher alkyl chains such as C22-C38 alkyl chains, paraffin waxes or alkyl long chain fatty acid waxes such as C12-C40 alkanecarboxylic acids. Instead of the wax, the matrix can also be selected from extrudable polymers. For example, polyethylene, polypropylene or polyamide, or mixtures of such extrudable polymers and waxes are particularly useful. Extrudeable polymers can be modified or unmodified polymers and copolymers.

The composition comprising the coated particles may be in the form of such particles or may be compressed into pellets by conventional means. Alternatively, the particles can be contained in a matrix and shaped into pellets, for example, by cutting the particle-matrix composition into pellets.

The pellet may consist of any person in accordance with the present invention. Preferred particles are selected from aramid, polyester, polyamide, cellulose, glass and carbon. The particles can be in any form, for example chopped fibers, staple fibers, pulp, fibrils, fibrids, beads, powders, and the like. Aramid fibers (including cut fibers, staple fibers and pulp) and powders are preferred, and more particularly poly (p-phenylene-tetraphthalamide) or co-poly- (paraphenylene / 3,4'-oxydi Particular preference is given to particles of phenylene terephthalamide). Most preferred are chopped fibers, staple fibers and powders. Powders and beads have the further advantage that they are obtained directly from the polymer without the need for a spinning step.

"Pellets" includes synonymous or closely related terms such as tablets, briquettes, pastilles, granules, etc., in addition to pellets. Pellets are prepared from any particles, including shot fibers, chopped fibers, staple fibers, pulp, fibrils, fibrids, beads and powders, by mixing these particles with a matrix of wax and / or extrudable polymers and coating chemicals Can be.

For example, pellets can be prepared according to the method described in WO 00/58064. Alternatively, pellets may be prepared directly using waxes, polysulfide polymers, and, optionally, polysulfide curing systems, such as chopped fibers or powders. The particles and the wax and / or extrudable polymer matrix, and optionally the curing agent, and other chemicals are mixed vigorously and optionally heated to a temperature above the boiling point of the wax or extruded polymer. The mixture is then shaped into pellets or tablets at temperatures below the boiling point of the wax or extruded polymer. Waxes (and / or extrudable polymers) may be used in amounts up to 85% by weight, based on the weight of the composition. Alternatively, the pellet can also be prepared from a mixture of particles and matrix, and then polysulfide polymer and curing system and / or cured polysulfide polymer are added to at least partially coat the particles contained in the pellet.

Treatment of the composition thereof is based on the polysulfide polymer and polysulfide curing chemicals, preferably Thiokol® LP, 2-mercapto-benzothiazyl disulfide, which chemicals further contain sulfur or sulfur donors . The composition of the present invention may also contain wax as a carrier medium to improve the process. Examples of suitable waxes are microcrystalline waxes of higher alkyl chains such as C22-C38 alkyl chains, paraffin waxes or alkyl long chain fatty acid waxes such as C12-C40 alkanecarboxylic acids. After the treatment, the composition can be used as is or subdivided into an appropriate size for use in a rubber compound. After the treatment, the fibers can be cut to the appropriate length for use in the rubber compound, the cut fibers can be treated with the chemicals, or the cut fibers and the chemicals including the wax can be mixed, optionally heated and administered. It is molded in an easy form.

Alternatively, the treatment of particles, including fibers and powders, or pellets made therefrom, may be based on glycidyl functional polysulfide polymers, with no additional curing agent required.

Suitable amounts of coatings are 0.5 to 50% by weight, preferably 1 to 30% by weight, more preferably 2 to 15% by weight, based on the weight of the composition.

Treatment of the composition is carried out using a solution of polysulfide polymer, 2-mercaptobenzothiazyl disulfide (MBTS) and sulfur in a suitable solvent (e.g. toluene) or a dispersion of said chemical in e.g. toluene / water. Can be done. 2-mercaptobenzothiazyl disulfide can be replaced with other benzothiazole derivatives.

Pellets prepared according to the process described in WO 00/58064 are solutions of polysulfide polymer, 2-mercaptobenzothiazyl disulfide (MBTS) and sulfur in a suitable solvent (eg toluene) or toluene, for example And / or a mixture of the chemicals in a suitable matrix (e.g. stearic acid). The matrix can be used in amounts up to 85% by weight, based on the weight of the composition.

Pellets can be prepared directly using powder or chopped fibers, wax and polysulfide polymer (A), 2-mercaptobenzothiazyl disulfide (MBTS), and sulfur as described above. Preferably, the wax is stearic acid. The wax may be used in an amount of 85% by weight or less based on the weight of the composition.

Preferred coatings are 10 to 98% by weight, more preferably 50 to 95% by weight, 0.1 to 20% by weight curing system, more preferably 0.5 to 10% by weight, based on the weight of the coating, and Sulfur optionally 0.01 to 10% by weight, more preferably 0.2 to 2.5% by weight. The amount of sulfur is either the amount of sulfur used by itself or the amount of sulfur that occurs when a sulfur donor is used. In the composition, stearic acid may preferably be present in an amount of up to 85% by weight, preferably 45 to 67% by weight.

The meaning of "cover" is well known to the skilled person and can be found in any relevant textbook. Thus, the coated particle is a particle containing a layer of coating material (coating) around its surface. If the particles are partially covered, only part of the particles are covered with the layer. In principle, there is no difference between coating the particles and making them into pellets and manufacturing the particles into pellets and then coating them. The coating composition will completely penetrate the pellets and coat the individual particles therein. It is also possible for the coating material or part of the coating material to penetrate between the filaments and the microfilaments by penetrating between the fibers of the particles or even penetrating the particles.

Compositions comprising polysulfide polymers having glycidyl end groups can be heat treated. Preferably, the composition is heated at 80 to 200 ° C. for 1 to 60 minutes. More preferably, the composition is heated at 120-170 ° C. for 5-25 minutes.

In another aspect, the invention relates to rubber compositions which are vulcanization reaction products of rubber, sulfur and optionally sulfur donors, and compositions according to the invention. The compositions of the present invention not only act as modulus enhancers, strength improvers but also reduce hysteresis. Furthermore, the vulcanization process carried out in the presence of the compositions and the use of these compositions in the sulfur-vulcanization of rubber are known.

The invention also relates to the vulcanization process carried out in the presence of the composition and the use of these compositions in the vulcanization of rubber. In addition, the present invention also encompasses rubber products comprising at least partly rubbers vulcanized in the presence of the composition, preferably vulcanized with sulfur. The present invention not only provides good hysteresis behavior, but also provides improvements to some rubber properties, with no noticeable side effects on the remaining properties, as compared to similar sulfur-vulcanized systems without any composition.

The present invention is applicable to all natural and synthetic rubbers. Examples of such rubbers are natural rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, isoprene isobutylene rubber, brominated isoprene-isobutylene rubber, chlorinated isoprene-isobutyl Ethylene rubbers, ethylene-propylene-diene ter-polymers as well as blends of two or more of these rubbers and one or more of these rubbers with other rubbers and / or thermoplastics.

Sulfur, together with the sulfur donor, provides the required amount of sulfur during the vulcanization process. Examples of sulfur that can be used in the vulcanization process include various types of sulfur, such as sulfur powder, precipitated sulfur and insoluble sulfur. Examples of sulfur donors include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylene thiuram hexasulfide, dipentamethylene thiuram tetrasulfide, dithiodimorpholine and mixtures thereof It is not limited to this.

Sulfur donors can be used in place of or in combination with sulfur. "Sul" herein may further include a mixture of sulfur and sulfur donor (s). In addition, when applied to sulfur donors, reference to the amount of sulfur used in the vulcanization process means the amount of sulfur donor needed to provide the same amount of sulfur specified.

More particularly, the present invention provides 100 parts by weight of one or more natural or synthetic rubbers (a); 0.1 to 25 parts by weight of sulfur and / or sulfur donor (b) to provide sulfur corresponding to 0.1 to 25 parts by weight of sulfur; And preferably from 0.1 to 20 parts by weight of a vulcanization reaction product of the composition (c) of the present invention comprising powder, chopped fibers, staple fibers or pellets made therefrom.

The particles of the present invention are based on natural and synthetic polymers. Examples of such polymers include, but are not limited to, aramids such as para-aramids, polyamides, polyesters, celluloses such as rayon, glass and carbon as well as combinations of two or more of these yarns. Most preferably the particles are poly (para-phenylene-terephthalamide) fibers available under the tradename Twaron® or co-poly- (para-phenylene / 3,4'-jade, available under the trade name Technora®. Diphenylene terephthalamide).

The amount of sulfur synthesized with the rubber is generally 0.1 to 25 parts by weight, more preferably 0.2 to 8 parts by weight based on 100 parts of the rubber. The amount of sulfur donor that is synthesized with rubber is the amount that provides the same amount of sulfur, that is, the amount that provides the same amount of sulfur when using sulfur by itself. The amount of the composition synthesized with the rubber is 0.1 to 25 parts by weight, more preferably 0.2 to 10.0 parts by weight, most preferably 0.5 to 5 parts by weight based on 100 parts of the rubber. These components can be used as pre-mixes or can be added simultaneously or separately or together with other rubber synthetic components. In most situations it is also desirable to have a vulcanization accelerator in the rubber compound. Conventional known vulcanization accelerators can be used. Preferred vulcanization accelerators include mercaptobenzothiazole, 2,2'-mercapto-benzothiazole disulfide; N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide, N, N-dicyclohexyl-2-benzothiazole sulfenamide and 2- (morpholino Sulfenamide promoters including thio) benzothiazole; Thiophosphoric acid derivative promoters, thiuram, dithiocarbamate, diphenyl quanidine, diorthotolyl guanidine, dithiocarbamylsulfenamide, xanthate, triazine promoters and mixtures thereof.

When a vulcanization accelerator is used, an amount of 0.1 to 8 parts by weight based on 100 parts by weight of the rubber composition is used. More preferably, the vulcanization accelerator comprises 0.3 to 4.0 parts by weight based on 100 parts by weight of rubber. Other conventional rubber additives may also be used in their usual amounts. For example, reinforcing agents such as carbon black, silica, clay, chalk and other inorganic fillers as well as mixtures of fillers may be included in the rubber composition. Other additives such as process oils, tackifiers, waxes, antioxidants, anti-ozone agents, pigments, resins, plasticizers, processing aids, facts, compounding and activating agents such as stearic acid and oxidation Zinc may be included in conventional known amounts. For a more complete list of rubber additives that may be used in the formulations of the present invention, see W. Hofmann, "Rubber Technology Handbook, Chapter 4, Rubber Chemicals and Additives, pp. 217-353, Hanser Publishers, Munich 1989). See.

In addition, scorch retardants such as phthalic anhydride, pyromellitic anhydride, benzene hexacarboxylic acid trianhydride, 4-methylphthalic anhydride, trimellitic anhydride, 4-chlorophthalic anhydride, N-cyclohexyl-thioptal Imides, salicylic acid, benzoic acid, maleic anhydride and N-nitrosodiphenylamine may also be included in the rubber composition in conventional known amounts. Finally, in certain applications, it may be desirable to include steel-cord adhesion increasing agents, such as cobalt salts and dithiosulfate, in conventional known amounts.

The process is carried out for a period of up to 24 hours at a temperature of 110-220 ° C. More preferably, the process is carried out in the presence of 0.1 to 20 parts by weight of the composition for a period of up to 8 hours at a temperature of 120 to 190 ° C., more particularly the composition comprises chopped fibers, staple fibers or pellets. Very even more preferred is the use of 0.2 to 5 parts by weight of coated chopped fibers, coated staple fibers or fiber pellets made therefrom. All additives mentioned above with respect to the rubber composition may also be present during the vulcanization process of the present invention.

In a more preferred embodiment of the vulcanization process, vulcanization is carried out in the presence of 0.1 to 8 parts by weight of one or more vulcanization accelerators, based on 100 parts by weight of rubber, for a period of up to 8 hours at a temperature of 120 to 190 ° C.

The present invention also includes articles of manufacture comprising sulfur-vulcanized rubber vulcanized in the presence of the compositions of the present invention, such as scheme products, tires, tire treads, tire undertreats or belts.

The invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.

Experiment method

In the examples which follow, rubber compounding, vulcanization and testing are in accordance with standard methods unless otherwise indicated. The base compound was mixed in a Farrel Bridge ™ BR 1.6 L Banbury type internal mixer (preheat at 50 ° C., rotation speed 77 rpm, mixing time 6 min under full cooling).

The vulcanized materials were added to the compound in a Schwabenthan Polymix ™ 150 L two roll mill (friction 1: 1.22, temperature 70 ° C., 3 minutes).

Curing properties are measured using Monsanto ™ rheometer MDR 2000E (arc 0.5 °) according to ISO 6502/1999. Delta S is defined as the degree of crosslinking and is derived by subtracting the lowest torque (ML) from the highest torque (MH).

Sheets and test samples were vulcanized by compression molding in a Fomtyne ™ TP-400 press.

Tensile measurements were performed using a Zwick ™ 1445 tensile tester (ISO-2 dumbbell, tensile properties in accordance with ASTM D 412-87, tear strength in accordance with ASTM D 624-86).

Abrasion was measured using a Zwick abrasion tester (DIN 53516) as the volume loss per 40 m path being moved.

Heat accumulation and compressive cure after dynamic loading were measured using Goodrich ™ Flexometer (load 1 MPa, 0.445 cm stroke, frequency 30 Hz, onset temperature 100 ° C., run time 120 minutes or blow out; ASTM D 623-78 ) Was measured.

Dynamic mechanical analyzes such as loss modulus and tan delta (Table 5) were performed using an Eplexor ™ dynamic mechanical analyzer (initial strain 10%, frequency 15 Hz, ASTM D 2231).

Example 1

Aramid short pellets are prepared according to WO 00/58064, which contains 80% by weight Twaron and 20% by weight polyamide resin. Treatment of these pellets was carried out in the following manner. Thioplast ™ EPS 25 and Thioplast ™ EPS 70 can be purchased from Akzo Nobel Thioplast. Thioplast ™ EPS 25 is a mixture of polysulfide polymers of formulas (I) and (IV) in which R 'is -CH _2- , n is less than 7, and the viscosity and branching viscosity of 2 to 3 Pa.s are also 2 mol%. Thioplast ™ EPS 70 has a diglycidyl ether of bisphenol A or F with R'-epoxide replaced with H and n of less than 7, a viscosity of 5 to 10 Pa.s and a powder of 0.57 at 20 ° C. A slightly branched polysulfide polymer of the above formula, which is a group obtained by reacting a polysulfide polymer precursor with a map. Thioplast ™ EPS is dissolved in toluene in the presence of a small amount of isohexadecane to prepare a solution of 66% by weight of Thioplast ™ EPS and isohexadecane in toluene. A 2.3 wt% solution of the surfactant Elfapur ™ LM 75 S in water was prepared. Thioplast ™ solution was added to the aqueous solution under vigorous stirring, followed by ultraturrax to obtain a stable dispersion comprising about 8% by weight of Thioplast ™ EPS. About 25 g of para-aramid pellets were soaked in 110 ml of the dispersion for about 5 minutes, then the treated pellets were filtered and dried. After drying, the pellets were treated at 150 ° C. for 15 minutes. The p-aramid fiber pellet compositions are summarized in the aramid fiber compositions and treatments in Table 1.

Aramid Fiber Compositions and Treatments Particles: Matrix: Polysulfide polymer (wt%: wt%: wt%) process caution Entry Twaron: PA: EPS 25 = 71.4: 17.9: 10.7 none compare T1 Twaron: PA: EPS 70 = 69.0: 17.2: 13.8 none compare T2 Twaron: PA: EPS 25 = 73.1: 18.3: 8.6 15 minutes, 150 ℃ The present invention T3 Twaron: PA: EPS 70 = 75.5: 18.9: 5.6 15 minutes, 150 ℃ The present invention T4

PA = polyamide resin; EPS 25 = Thioplast ™ EPS 25; EPS 70 = Thioplast ™ EPS 70.

The promoter used was N-cyclohexyl-2-benzothiazole sulfenamide (CBS).

Detailed formulations are listed in Table 2.

Rubber formulation incorporating aramid fiber composition Experiment → A B C D One 2 Ingredient ↓ NR SMR 10 80 80 80 80 80 80 BR Buna CB 24 20 20 20 20 20 20 Black N-339 55 57 55 55 55 55 Zinc oxide 5 5 5 5 5 5 Stearic acid 2 2 2 1.5 2 1.5 Aromatic oils 8 8 8 8 8 8 Degradation Agent 6PPD 2 2 2 2 2 2 Antioxidant TMQ One One One One One One Accelerator CBS 1.5 1.5 1.5 1.5 1.5 1.5 sulfur 1.5 1.5 1.5 1.5 1.5 1.5 T1 0 0 One 0 0 0 T2 0 0 0 One 0 0 T3 0 0 0 0 One 0 T4 0 0 0 0 0 One

NR = natural rubber; BR = polybutadiene; 6PPD = N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine; TMQ = polymerized 2,2,4-trimethyl-1,2-dihydroquinoline antioxidant; CBS = N-cyclohexyl benzothiazyl sulfenami

The vulcanized rubbers listed in Table 2 were tested according to ASTM / ISO standards. A and B are control experiments (rubber alone), C and D are comparative experiments (not cured), and 1 and 2 are experiments according to the invention. The results are provided in Tables 3-6.

Influence of the Mixture on Processing Properties (Money Viscosity) at 100 ° C Experiment → A B C D One 2 ML (1 + 4), MU 54 55 57 55 59 59

The data in Table 3 shows that the fiber composition according to the invention has a low viscosity which is demonstrated by the ML (1 + 4) value.

Effect of the Mixture on Delta Torque at 150 ° C Experiment → A B C D One 2 Delta S (Nm) 1.75 1.79 1.83 1.78 1.82 1.80

The data in Table 4 shows that the compositions according to the invention (mixtures 1 and 2) do not affect the expansion of the crosslinks demonstrated by the delta S values.

Evaluation of Fiber Compositions for Improvements in Mechanical Properties Experiment → A B C D One 2 Modulus, 300% (MPa) 13.1 14.8 14.8 14.5 15.6 15.4 Tear strength (kNm) 135 120 130 130 145 145

It is evident from the data in Table 5 that the compositions of the present invention (mixtures 1 and 2) containing polysulfide polymers have good elastic modulus and tear strength.

Evaluation of Improvements to Dynamic Mechanical Properties Experiment → A B C D One 2 Temperature rise (℃) 32 37 28 28 26 26 Stop time (min) 25 18 29 35 42 45 Loss modulus (MPa) 1.2 1.33 1.21 1.25 1.05 1.09 Tangent Delta 0.158 0.167 0.159 0.156 0.136 0.138

Note that compositions containing polysulfide polymers (mixtures 1 and 2) exhibit improved dynamic mechanical properties.

Example 2

Aramid short pellets are prepared according to WO 00/58064, which contains 80% by weight Twaron and 20% by weight polyethylene resin. Treatment of these pellets was carried out in the following manner.

Thiokol® LP 32 can be purchased from Toray Fine Chemicals Co., Ltd. Thiokol® LP 32 is a slightly branched polysulfide polymer mixture of polysulfides of formulas (I) and (III) with n average 24 and a viscosity of 45 Pa.s and a branching degree of 0.5 mol%. Thiokol® LP 32 was dissolved in toluene to prepare a 66 wt% Thiokol® LP 32 solution. A 1.7 wt% solution of the surfactant Elfapur ™ LM 75 S in water was prepared. Thiokol® LP 32 solution was added to the aqueous solution under vigorous stirring, followed by ultraturrax to obtain a stable dispersion comprising about 10% by weight of Thiokol® LP 32. About 25 g of para-aramid pellets comprising 80% Twaron and 20% polyethylene by weight were soaked in 150 ml of the dispersion for about 5 minutes, then the treated pellets were filtered and dried. Sulfur and 2-mercaptobenzothiazyl disulfide were dissolved in toluene to give a solution containing 0.4 wt% sulfur and 0.8 wt% 2-mercaptobenzothiazyl disulfide. Thiokol® LP 32 was dissolved in toluene and toluene solution containing sulfur and 2-mercaptobenzothiazyl disulfide was added to 8% by weight of Thiokol® LP 32, 0.4% by weight of 2-mercaptobenzothiazyl disulfide and 0.2% by weight of sulfur. A solution containing% was obtained.

A second batch of about 25 g of para-aramid pellets comprising 80% Twaron and 20% polyethylene by weight was soaked in 100 ml of the dispersion for about 5 minutes, then the treated pellets were filtered and dried.

The third and fourth batches of about 25 g of para-aramid pellets comprising 80 wt% Twaron and 20 wt% polyethylene were subjected to melted stearic acid and Thiokol ® LP 32, 2-mercaptobenzothiazyl containing Thiokol ® LP 32. Mix with melted stearic acid containing disulfide and sulfur respectively. The pellet was then cooled and the solidified small amount of stearic acid possibly containing a small amount of Thiokol® LP 32, 2-mercaptobenzothiazyl disulfide and sulfur was sieved off.

The p-aramid fiber composition is summarized in Table 7.

Fiber pellet composition ingredient Composition (wt%: wt%: wt%) caution Entry Twaron: PE: LP 32: Elfa 67.8: 17.0: 13.6: 1.6 compare T5 Twaron: PE: SA: LP 32 30.2: 7.6: 57.8: 4.4 compare T6 Twaron: PE: LP 32: MBTS: S 71.5: 17.9: 9.9: 0.5: 0.2 The present invention T7 Twaron: PE: SA: LP 32: MBTS: S 30.6: 7.7: 56.9: 4.5: 0.2: 0.1 The present invention T8

PE = polyethylene; LP 32 = Thiokol® LP 32; Elfa = Elfapur ™ LM 75 S; MBTS = 2-mercaptobenzothiazyl disulfide; SA = stearic acid

The accelerator used is N-cyclohexyl-2-benzothiazole sulfenamide (CBS). Detailed formulations are listed in Table 8.

Rubber formulation with aramid pellets Experiment → E F G H 3 4 Ingredient ↓ NR SMR 10 80 80 80 80 80 80 BR Buna CB 24 20 20 20 20 20 20 Black N-339 55 57 55 55 55 55 Zinc oxide 5 5 5 5 5 5 Stearic acid 2 2 2 0 2 0 Aromatic oils 8 8 8 8 8 8 Degradation Agent 6PPD 2 2 2 2 2 2 Antioxidant TMQ One One One One One One Accelerator CBS 1.5 1.5 1.5 1.5 1.5 1.5 sulfur 1.5 1.5 1.5 1.5 1.5 1.5 T5 0 0 1.5 0 0 0 T6 0 0 0 3 0 0 T7 0 0 0 0 1.5 0 T8 0 0 0 0 0 3

NR = natural rubber; BR = polybutadiene; 6PPD = N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine; TMQ = polymerized 2,2,4-trimethyl-1,2-dihydroquinoline antioxidant

The vulcanized rubbers listed in Table 8 were tested according to ASTM / ISO standards. E and F are control experiments (rubber alone), G and H are comparative experiments (without curing system), and 3 and 4 are experiments according to the invention. The results are provided in Tables 9-12.

Influence of the Mixture on Processing Properties (Money Viscosity) at 100 ° C Experiment → E F G H 3 4 ML (1 + 4), MU 53 55 53 53 54 51

The data in Table 9 shows that the fiber composition according to the present invention has a low viscosity, which is evidenced by the ML (1 + 4) value.

Effect of the Mixture on Delta Torque at 150 ° C Experiment → E F G H 3 4 Delta S (Nm) 1.72 1.75 1.76 1.79 1.97 1.92

The data in Table 10 shows the highest reinforcement demonstrated by the delta torque value for the fiber compositions according to the invention (both polysulfide polymer and curing system are present, mixtures 3 and 4).

Evaluation of Fiber Compositions for Improvements in Mechanical Properties Experiment → E F G H 3 4 Modulus of elasticity, 300% (MPa) 13.2 14.8 13.9 14.7 15.5 15.5 Intensity (IRHD) 71 71 73 72 75 75

It is evident from the data in Table 11 that the compositions of the present invention (mixtures 1 and 2) containing polysulfide polymers have good elastic modulus and tear strength.

Evaluation of Improvements to Dynamic Mechanical Properties Experiment → E F G H 3 4 Temperature rise (℃) 24 26 24 24 19 20 Loss modulus (MPa) 1.12 1.07 1.11 0.96 0.89 0.87 Tangent Delta 0.157 0.148 0.146 0.136 0.120 0.122

Note that compositions containing polysulfide polymers (mixtures 3 and 4) exhibit improved dynamic mechanical properties.

Claims (21)

A composition comprising particles and a matrix, At least partially with a compound or mixture of compounds wherein said particles comprise at least one of a polysulfide polymer and a curing system (a) and a cured polysulfide polymer (b) obtained from a polysulfide polymer having at least two epoxy end groups Coated, composition. The composition of claim 1 wherein the particles are fibers, fibrids, fibrils, powders or beads. 3. The composition of claim 1, wherein the polysulfide polymer is a linear or branched compound of formula V. 4. Formula V A-B-C In Formula V above, B is a residue comprising independently 1 to 200 repeating units of the formula-[XR ₂ -XR ₁ -S _x ]-wherein X is independently CH ₂ , S or O; x is 2, 3 or 4; R ₁ and R ₂ are substituted or unsubstituted alkylene having 1 to 10 carbon atoms, substituted or unsubstituted arylene having 6 to 10 carbon atoms, alkyleneoxy having 1 to 5 carbon atoms, and alkyleneoxy having 2 to 10 carbon atoms. Independently selected from alkylene; Wherein the substituent is a residue comprising independently 1 to 200 repeating units of the formula D- [XR ₂ -XR ₁ -S _x ] -E, wherein X, R ₁ , R ₂ and x are provided above Or X, R ₁ and R ₂ are independently a bond and the residues XR ₂ -XR ₁ contain two or more atoms; one of D and E is a bond and the other has the same meaning as A) Is}; A and C are independently selected from hydrogen and a group containing at least one of halogen, epoxy, hydroxy, isocyanate, silyl and vinyl. 4. A compound according to claim 3, wherein R ₁ and / or R ₂ means substituted alkylene having 1 to 10 carbon atoms or substituted arylene having 6 to 10 carbon atoms, wherein the substituent is represented by the formula D- [XR ₂ -XR ₁ -S _x ] -E is a residue containing independently 1 to 200 repeating units, in which the groups R ₁ and R ₂ are alkylene having 1 to 10 carbon atoms, arylene having 6 to 10 carbon atoms, and 1 carbon atom. Independently selected from alkyleneoxy of from 5 to 5, and alkyleneoxyalkylene of from 2 to 10 carbon atoms. The method according to claim 3 or 4, wherein the groups A, C, D and / or E of the polysulfide polymer ABC are glycidyl or a diglycidyl ether of bisphenol A or a diglycidyl ether of bisphenol F. A group obtained by the reaction or a resin thereof; Provided that one of D and E is a bond and the other is H, and A and C are both H. 6. The composition of claim 1, wherein the polysulfide polymer is at least one of formulas I, II, III, and IV. 7. Formula I

Formula II

Formula III

Formula IV

In the above formulas (I), (II), (III) and (IV), n is independently 1 to 200, R 'is

Wherein m is 0 to 10, R ₃ is independently H or CH ₃ , and the two asterisk terminated groups are bonded to the epoxide group. The coating according to claim 1, wherein the coating comprises a polysulfide polymer and a curing system, wherein the curing system comprises lead oxide (IV), Mn (IV), low molecular weight phenolic resins, Diisocyanate, polyisocyanate, diepoxide, polyepoxide, cumene hydroperoxide, dicumyl peroxide, calcium peroxide, zinc peroxide, sodium periodate, sodium perborate, tetrabutylammonium peroxydisulfate, p-qui The composition is selected from nondioxime, iodine, and a mixture of sulfur and polysulfide. 8. The method of claim 7, wherein the curing system is sulfur and chemical formula

Wherein n is 2 to 6 and R is a mixture of polysulfides of hydrogen, halogen, nitro, hydroxy, C 1 -C 12 alkyl, C 1 -C 12 alkoxy and C 7 -C 12 aralkyl independently . The composition of claim 1, wherein the coating comprises 10 to 98 weight percent polysulfide polymer and 0.1 to 20 weight percent curing system, based on the weight of the coating. The composition of claim 1, wherein the matrix is a wax. The composition of claim 10, wherein the wax is a saturated alkanecarboxylic acid having 12 to 40 carbon atoms. The composition of claim 11 comprising up to 85% by weight of aliphatic fatty acid wax, or synthetic microcrystalline wax having a C22-C38 alkyl chain, based on the weight of the composition. The composition of claim 1, wherein the particles are selected from aramid, polyester, polyamide, cellulose, glass and carbon. The composition of claim 1, wherein the particles are selected from chopped fibers, staple fibers, pulp and powder. The fiber according to claim 1, wherein the particles are poly (p-phenylene-terephthalamide) or co-poly- (paraphenylene / 3,4′-oxydiphenylene terephthalamide) fibers. Phosphorus composition. The composition of claim 1, wherein the particles are pretreated fibers by sizing. The method according to any one of claims 1 to 16, wherein the amount of the coating is 0.5 to 50% by weight, preferably 1 to 30% by weight, more preferably 2 to 15, based on the weight of the composition. Composition by weight. 100 parts by weight of one or more natural or synthetic rubbers (a), 0.1 to 25 parts by weight of sulfur and / or sulfur donor (b) to provide sulfur corresponding to 0.1 to 25 parts by weight and A particle-elastomer composition comprising 0.1 to 20 parts by weight of the composition (c) according to any one of claims 1 to 17. A scheme product comprising the particle-elastomer composition of claim 18 and a skim additive. A tire comprising the composition according to claim 18 and / or the scheme product according to claim 19. A tire tread, undertread or belt comprising the particle-elastomer composition according to claim 18 and / or the scheme product according to claim 19.