MXPA97009109A

MXPA97009109A - Compositions of elastomero halogen

Info

Publication number: MXPA97009109A
Application number: MXPA/A/1997/009109A
Authority: MX
Inventors: Ignatzhoover Frederick
Original assignee: Monsanto Company
Priority date: 1995-04-26
Filing date: 1997-11-25
Publication date: 1998-02-01

Abstract

Rubber compositions in which the rubber is a halogenated butyl elastomer, are crosslinkable in that they contain an entanglement agent such as zinc oxide and an accelerator which is a salt of an organic thiosulfate.

Description

COMPOSITIONS OF HALOGENATED ELASTOMER FIELD OF L INVENTION The present invention relates to compositions containing elastorne ha i o ge na two, part i cularrnen + e in erpoli m ros ol. rich ore containing sun > ut full and it is irt.no par-a haloal qu? 1 -subst? t uido, agents of relacin and accelerators of thiosul fato.

BACKGROUND OF THE INVENTION Halogenated copolymers of isobutylene and up to about K mole of isoprene (butyl rubber) are known Luen polymeric materials whose vulcanizates offer some pneumatic properties not possessed by many elastomer-based elastomers. Ready-made articles Many cured halogenated astorians offer improved resistance to oils and fats as well as oxygen resistance and ozone degradation. Butyl rubber vulcanizates exhibit good resistance to abrasion, excellent water repellency, water vapor, and many Organic solvents, as well as resistance to aging and sunlight. These properties make these materials ideal candidates for one or more applications such as water hoses, organic fluid hoses, components under tire construction, packaging, crushes, «.ornposi ior.es, and various molded articles, and I have also discovered new types of new halted elastomers that offer many of the same properties with halogenated butyl rubber, but they are even more resistant to ozone and solvent and are more readily curable. These materials are the product of halogenac on random flakes of a solid form of C4 to O7, such as isobutylene, and a comonomer of para-al uil est LI? O where at least some from the groups to the tit the substit yents present in the monornero units of os < 1 re not co nt ne ne 1 o ge no. These copolymers and their method of preparation are described in particular in the U.S. Patent. No. 5,162,445, the entire description of which is incorporated herein by reference. The aromatic groups present in such copolymers allow easy entanglement to be achieved in a variety of ways, including by means of rust zinc or z nc promoted oxide curing systems normally used to cure halogenated butyl rubber. However, some systems of oxidation of z nc promoted promote serious problems of healing. The Patent of E.U.A. 5,373,062 discloses halogenated elastomer compositions showing a promoted zinc oxide crosslinking agent and an inhibitor scorched from. ai b? * Li or bismuth. An object of this invention is to provide halogenated olastomer compositions that cure rapidly, but without serious pi'vival problems, and achieve a high level of interlacing.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention, an improved promoted cured system for waves has been discovered. These are locos where the curing system contains an entanglement agent and an accelerator material containing one or more groups of the formula - S 2 O-0M attached to a hydrocarbon radon, an organic bridging group or a polymer, and M is a monovalent metal, the equivalent of a metal mu Iti to the entity, a monovalent on derivative by the addition of a proton to a nt rogenous liase, or the equivalent of a derived muíivalent ion by the addition of two or more protons to a base nor rogenoosa. Halogenated elastomer composites containing these entanglement agents and accelerating materials quickly heal to a high state of healing, and avoid problems of prior healing.

DETAILED DESCRIPTION OF THE INVENTION The one or more inventor has observed the compositions of this invention include chlorinated or brominated butyl rubber, chlorinated or brominated intermediates of a C-to-C isoolefin. and a para-al qui lest enomixtures thereof or mixtures of one or both of these elastomers with vulcanizable diene elastomers such as copolymers or natural or synthetic of LS- or 11-O, polybutadiene, butadiene-this reindeer or copolymers elasto-elasto-elasto , propylene and up to 10 mol% of a non-conjugated diene (known as EPDM rubber). The halobutne rubbers can be based on chlorinated or brominated isobutyl binders with up to about 4 mol% isoprene. These elastomers generally have an average molecular weight within the range of about 50,000 to about 500,000 and can be prepared by polymerization and halogenated method well known in the art as described in U.S. Pat. Nos. 2,940,960 and 3,099,644, the descriptions of which are incorporated herein by reference. Halogenated interpolymers based on Ci, C a soolefma, such as isobutylene, and a para-alkylstyrene, such as para-rnethyltin, are also now known in the art as tested in the U.S. Patent. aforementioned No. 5,162,445.

The most preferred materials are the product of the haeganization of a random copolymer of an isoolefin from C to C? , l as 1 sobut 1 log, and a group of para-alkylstyrene where at least some of the groups'. alkyl subst 1 listeners present in the sterndrive units contain halogen. The preferred materials can be characterized as full-sized interpolymers containing the following oneroero units randomly separated on the polymer chains: S and wherein at least about 5 mole% of the comonomer units present in the polymer chain are of the structure of formula 2, R and R 'are independently hydrogen or Ci to C alkyl, R "is independently hydrogen, alkyl of Ci to C4 or X, and X is bromine or chlorine, and where the interpola is otherwise substantially sub- stantially free from < What is it? hal in 1 n 'adona of polymer base structure. With reference to the so-and-so or the "monomer of i soole" (these latter are inclusive of) copol Moor consisting of lsobutylene and a monoinerO having the structure of the f la 2 where "it is Hydrogen or alkyl from Ci to O4, for example, copolymers of filled isobuf and a parabolic acid reagent, which are comprised of isobutylene and a mixture of hormones having the structure of the fibers. formulas 1 and 2 wherein R "is hydrogen or Ci a ^ alkyl. for example, terpolymers of isobutylwood, a para-alkylstyrene and a para-alkynesterone have not been used; c) polymers that comprise i sobut 1 log and a mixture of rnonorneros that have the structure of formula 2 where, with respect to a higher proportion "monomial Jel of the formula", R "is hydrogen or Ci alkyl to C4 and, with respect to a smaller proportion- of said monomer of formula 2, R "is bromine or chlorine, for example, a lime filler of full isobuf, a substituted mono-halo substituted parathion and a para-alkylate. substituted di-halo-styrene; and d) terpol irneros that comprise isobutylene and a mixture of atoms that have the structure of lines 1 and where, with respect to a larger proportion of the monoinero of the formula?, R "is hydrogen or alkyl from Ci to C-, and, with r-spec a smaller proportion of said inonornero of formula 2, R "is bromine or chlorine, for example, a full isobutyl radical, a para-alkylstyrene, a non-halogenated para-alkylate, and a parabolic acid or substi tute. As noted above, these halogenated nitrites are prepared using a co-polarizer of a C 1 to C isoolefin and a para-alquatene as the halogenation substrate. (a), (b), (c) or (d) above will be produced as a function of the severity of the halogenation reaction, for example, the mild halogenation would be prone to produce polyterms of the characteristics of (b) ), the strongest heylogenation will result in the characteristics of (a) or (cl) and the very strong halogenation producing terpo lime that have the characteristics of (c) .The most preferred elastomers used in the compositions The present invention is randomized elastomepic brominated polyols comprising isob? ti log and para-methylstyrene (PMS) containing from about 0.5 to about 20 mol% of PMS, preferably from about 2 to about 15 mol% of PMS, wherein up to approximately 00% molar- of the PMS inonornero units contain a monoclonal group L- These elastomeric lunar flakes usually exhibit an average molecular weight on the scale of about 50,000 to about 250,000, more I preferred about 80,000 to approve 180,000. From about 5 to about a one-half molar rite of the total PMS onerous content of the terpol contains a non-briquetting graph with essentially no broth occurring in the polymer base or in the the attic ring ring. The bromine content of these polymeric substances generally ranges from about 0.1 to about b mol%. An advantage of the compositions containing halogenated butyl rubberor, par icularly, the isobutyl ether-filled polymers - PMS halogenated is that they can be more covulcanised with other elastomers of general purpose such as polybutadiene, natural rubber, and sirnil-as well as the omeros. of FPDM. This characteristic is mainly due to the fact that these halogenated materials can be made to co-cure with more highly unsaturated rubber by mechanisms that are independent of the sulfur and promoted sulfur systems used to cure the highly unsaturated rubbery elastomers. Illustrative of known curing agents or accelerators that can be used alone or in conjunction with zinc oxide for halogenated cure elastomers are brominated alkyl phenol resin.; N, N'-d? Et? Lt? Ourea; salt of di-or + o- (tol i 1) dicatecol borate mdma; dipentamethyl tetrasulfide len urarn; f-ethylhexylcarbamate ethyl; ? - m < .r aptobenzot Lazol; d) Alkyl or ap L benzothiazole, disul furo of et rarnet i Ltiu rain, diethyldi t loear'bamat o of zinc, dibutyl dit bicarbonate of zinc, and dirnetildithiocarbamate of zinc.

A known curing system comprises zinc oxide and tetra phenyl sulfide di pent arnet ilen iuram. In the compositions of the invention, zinc oxide alone is preferred, in a preferred amount of 0.05 to 10 parts, preferably less than 0.1 to 5. 1 (1 parts and most preferred 2 to 3 parts by weight per 100 parts halogenated by weight) The preferred accellar materials are compounds wherein the thiosulfate groups are attached to a primary carbon atom of the hydrocarbon radical or group of bypass, and Ib polymers where the thiosulfate groups are linked to primary car bonuses in side chains attached to the main polymer chain. Therefore, the phosulfate groups usually occur in the -CH2-S-SO2-OM form. Accelerators that are compounds where a single The group -S-SO2-OM is attached to a hydrocarbon radical include alkyl or aryl thiosulfates - sometimes referred to as "Bunte salts". Illustrative of these compounds are salts of etii t. losulfate, benzylsulfate salts and the like. The hydrocarbon radical can be alkyl of 1-20 atoms of carbon, aryl of 6-20 carbon or aralkyl or alkapol atoms of 7-21 carbon atoms. Other substudents, not reactive, They may be present in the high-tech orb bond. The aeelc- > r-ares that are compounds that contain groups of the -formula -S O2 -OM li a o'-, by? n an organic bridging group usually contain two, three or four groups - -SO2-OM. Illustrative of said compounds are those Jß < read the formula XI "-CH2) n 'OH2" S-S02 -OM "ln •• where n' has an integral value of at least 1, n" has the value 2, 3 or 4 and X represents the rest of the bridging group. In the compounds having two S-SO2-OM groups, the bridging group is divalent, and said compounds can be represented by the formula MO-O2 SSX '~' - ~ S02 -OM In this formula X 'can be, for example, a straight or branched chain alkylene or alkene group, preferably one containing from 2 to 40 carbon atoms, and more preferably one containing from 5 to 16 carbon atoms. Examples of such groups are ethylene, full pent arnet, hexarnetylene, oct arnet to log, nonamet-, log, decarnet 1 log, dodecameti le or, 3-rnet? Ii, 5-? Ent full and 1, 6-hex-2 -emleno. As a variant, a bivalent bridging group can be an alkylene or alkenyl group having one or more substituents, eg, phenyl. An example of such a radical is 2-phenyl-1, 4-bu 1 -wood. In other cases, X 'has a structure comprising i 1 two or more units of alqua lorio, stoppages of said units being linked to rails of an oxygen or sulfur, or through a group O2 - NH2 + -, -M (to the quilo of Oi-ß) - or -COO -, or through an arylene lime or qui cloal qui leño. Representative of said structures are those of the formula - (CH2) a-0- (CH2) a "- (CH2) a -0-CH2-0- (CH2) a - - (0.12) b - clo clohexa leño- ( CH2) b - - (CH2) c -000-ÍCH2) a • (CH2) c -C00-Y-00C-CCH2) c "- every a and each c independently represents an integer from 2 to 20, each b represents independently an integer from 1 to 10, and Y represents a group - (CH2) c ~ or a group - (CH2 CI-I2) d CH2 CH2 - where d represents an integer from 1 to 5. The preferred values for a are from 3 to 0, preferred values pair-a b are L a 4, and preferred values for c are 3 to 18, more especially 3 to 12. Other examples of the jumper crane X 'are those that have the formula - ( CH2) -S02- (CH2) c - ~ (CH2) c-NH- (CH2) c ~ y - (CH2) C-NH2 + - (CH2) e- wherein each c independently has a value of 2 to 20, preferably from 3 to 18, and much preferred from 3 to -L2.

I,.

Where the values of a, b or c exceed 2, the polyrnetic groups can be straight or branched chain, f > However, the terminal carbon atom, which is the group - O2-OM, is a primary carbon source. The accelerator compounds having three or four thiosulfate groups include those in which three or four groups -0ml-12m ~ SS 2-OM, in having typically a value of 3 to 6, are subsfinguents in a formal nucleus, - example a nucleus of benzene on phthalene, (which may also contain other substituents), or as substituents in one or more nuclei of a di- or tpnuclear aromatic compound, eg, bifemlo, ether - difenilico, diffele sulfone or Canvas fenona Other examples of trivalent groups of puen eo are those of the formula -Ai -OCH2 CH (O i -) OH2 OAi - • and AC (A00 (.Al-) 3 where each A 'is independently an alkylene group, for example, an alkylene group of C2-I8, preferably C3-12, and A is alkyl of Ci-e, and also those of the formula N [(0H2-c 33 and HN "I" (CH2-C3 where each c independently has a value- from 2 to 20, preferably from 3 to 18, more especially from 3 to 12. Other examples of groups of tetravalent bridges are those with the formula C (f.) 4 and (A1) 3S? -0-S? (Ai) 3 where Al has the same meaning as before; and that'-, they have the formula where each c independently has a value of? to 20, from 3 to 10 and very low from 3 to 12. Examples of polymers are those of the formula 01.20 002 ~ 0M (0 ~ CI-1-CH) n and polyvinyl alcohols matched and partially mattes where the polymer chain is formed from units selected from -C CHH - CCHhfe2-- ,, --CCHH - OOHH22-- ,,, and -CH-CH2- wherein R 'represents a C1-12 alkyl group and c has an integer value of 2 to 20, and at least 10%, preferably At least 20%, for example 25% to 75%, of the units in the polymer are those that contain the -S-SO2-OM group. When M in the above formula - of the accelerator material represents a monovalent metal, this may be for example an alkali metal, for example sodium, lithium or potassium.

Sodium is the preferred alkali metal. M can represent alternatively the lens of a multivalent metal, for example magnesium, calcium, barium, z nc, nickel, cobalt or Lumi ni o. Fn where M represents a monovalent ion formed by the addition of a proon to a nitrogenous base, the nitrogenous base can be either a primary or a primary, secondary or tertiary amine, R2NH2. R2R3NH or R2 R3 R «N on where each R2, R3 and R4 r * epresentatively represents an alkyl group, for example a C1-20 alkyl group. a cycloalkyl group or a cycloalkyl group of C5-9, for example cyclohexyl or methy1-cyclohexyl, a benzyl group, a phenyl group or a substituted feriio group, for example a tolyl or chlorophenoyl group, always and when not more than one of R2, R3 and R4 is a substituted phenyl or femlo group. The amines re fe rula are those that are relatively basic weakly. Lists include animas where the weak basic characteristic is a result of osteopc impediment around the mitogenic atom due, for example, to the presence of a ter-alkyl group, for example a ter-to-quilo group having 4 to L2 carbon atoms, such as tert-butyl, ter-aryl or 1,1,3,3-tet rabbet lbut 1I0. Examples of said amines are the secondary amines R2R3NH wherein one of R2 and R3 is a ter-alkyl group and the other is a benzyl group or a cyclohexyl or alky1cyclohexyl group. Alternatively, R2 and R3 can be groups ter- \ lquiLo. Other examples are tertiary amines wherein R2 e < -, a ter-alkyl group and R3 and R * are benzyl groups. Other weakly suitable basic amines are the primary amines, R2NI-12, wherein R 2 is a substituted phenyl or phenyl, and the secondary animas, R 2 NH 3, wherein R2 is a substituted group or substituted phenyl and R3 is an alkyl group of C? -i2. Examples of such amines are anilin, toluidines, N-rneti Lamia na, N-but Tna 1 ma and N-isohexylaninyl ma. A special class of said secondary amines comprises those wherein R 2 represents a secondary alkyl group, preferably, a secondary alkyl group of C 3-12, or a cyclohexyl group, and R 3 represents a 4-phenylamino ferulene group. These amines include compounds such as Na sopropa 1-N '-phenyl-p-pheni lendiami na, N-sec-but 11-N'-phenyl-p-phenyl nadiarni, Nl, 3-dirnethylbutyl-N'-phenyl- p-fe i lendiarnina, N-l, -dim tlppent LI-N '-f ru l-p-faith ni l n ia ina and N-cyclohexyl-N' - phe ny 1 -p-phen? Lend? Arn? na These amines function as rnono-acid bases despite the presence of the second nitrogen atom in group 4-phenylaininofemlene, because this second nitrogenous atom has in fact no basic hydrogenation. Other examples of nitrogenous bases forming thiosulfate salts of the invention are guanidine and substituted guamdines, for example those of the formula NH R2NH-C-NHR2 ^ or sub-surface areas, [> Or, for example, that of the fo rmu SR5 / MH-- C -NH2 where each R2 independently represents hLdr qono, an alkyl group, for example a C1-20 aliquote group /? 1 I read chloro Lqui 1 or from O5-9, a benzyl group, a feminine group or a fem group, the substituted one; for example a tolyl group, and R5 represents a group of C1-20. a cycloalkyl group or the cycloalkyl group < | ULlo of C5-9 or? N group bencalo. Specific examples of substituted guides are diphenoligine and di-tololigine; Specific examples of substituted isothioureas are S-eta 1 isotaourea and S-bencLli sotio? r-ea. Where M represents an equivalent of a multivalent cation formed by the addition of two or more protons to a nitrogenous base, the bases from which said ions can be derived include alkylene di amines, N, N'-disubstituted alkylene di amines, femlendia and N, N'-disubstituted N-N-N-alkyl radicals of the formula R2NH-A-NHR2 wherein A represents an alkylene radical - (CH2) C- wherein c has a value of 2 to 10, preferably 2 to 12, and which may be straight or branched chain, or a femlene, for example a meta- or para-a-phenylene radical, and each R2 independently represents an alkyl group, for example a C1-20 alkyl group. A cycloalkyl or alkoylcycloalkyl group of Cs-9. a beneyl group, a femlo group or substituted phenyl group, provided that no R2 is a phenyl or substituted phenyl group when A is a phenylene radical. In preferred weeks wherein A represents an alkylene radical, R 2 is a ter-alkyl group, for example + er butyl, t-arnyl or 1, 1, 3, 3-tetramet Llbutyl, or a phenolyl group. Examples of said amines are N, N'-di-fistlet and diamine, N, N'-d? -tert-butii-i, 4-tet card Lien d La na and N, N'-b? s (1, l, 3, J-tetrameti Ibutil) - 1.6-hexame? i gave amine. In preferred amines wherein A represents a non-ferrous radical, R 2 is a secondary alkyl group, preferably a C 3-12 secondary alkyl group or a cyclohexyl group. Examples of said amines are N, N'-di-ec-buta 1-p-fe lendiarnin, N, N '~ b? S (1,3-d? Met? Ibut? I) -p-femlendiarní na, N , N'-bis (1,4-d? Rnet? Lpent? L) ~? -fen? Lend? Am? Na, N, N "-b? S (L-et 11- 3 -metí lpentii) -p -feru lendiarnine, N, N '-bs (l -methylheptyl) -p-femlendiarnine and N, N'-di-cyclohexy 1-y ~ fem lendiaini na Possible bases also include poly-alkylene poly-amines of the formula R2 H - (A'-NH) n-A'NHR2 wherein A 'represents an alkylene radical of 2 to 8 carbon atoms, n has a value of 5, and each R2 independently represents a C1-20 alkyl group, a cycloalkyl or C5-9 alkylcycloalkyl group, a benzyl group, a femlo group or a substituted femlo group, in other cases, the nitrogen of the mitogenic base It is part of a ring hot eror.i cl i co. The base may be non-ionic, for example, pin dina, or a compound where the nitrogen-containing anion which contains nitrogen is fused to another ring, as by virtue of its axis. i no 11 n. deine s, a n to 11 or heterocyclic may be saturated, as for example in orfol ina or p pen di na. or it may contain one or more direct bonds, for example, in pyrroline or L, 2-da hi droquinol ina. Of the compounds wherein M represents said base, those preferred to be used as an accelerator are the compounds wherein M represents an on of 1,2-dihydroquinol, which may optionally have substudents of ring. Examples of said aones are 2, 2, 4-t ramet il-l, 2-diha droq? Inol io, 2, 2, 4-t rinetil-b- (C? -i2 alkoxy) -1.2-dihydroquinolone, for example?, 2, 4-tprnet? l-6-ethoxy-1,2-dihydroquinolinio, 2, 2, 4-tprnet? l -h- (Ci-iß) -l. 2-dihydroquinolinio alkyl, for example 2, 2, 4-tprnet? l-6-dodec? 1-L, 2-dihi dr-oqui no Linio, and 2, 4-diet i L-2-? Net i 1 -1, 2-d? H? Droq? Nol? Mo. Other kinds of Liases that form divalent cations by the addition of two protons are represented by the general formula wherein A2 i represents a radical ((.112) c -, at oe? e it is an integer from 2 to 20, preferably from 1 12, and the radical - (OH2) c - can be straight or branched chain or a radical to the quemleno or to cadieni leño of C2-20, for example a radical bu -2-emleno or octa-2, 6-d? em leño.Tstas bases form ions of your s (isot Louronio) and bi s (- guanidinium), respectively The accelerators of the invention are described and claimed in US Patent Nos. 4,417,012, 4,520, L54 and 4,587,296 The use described in these patents for the materials is as "stabilizers" for vulcanized diene rubber The compositions of this invention may also contain a mixture of halogenated elastomers with vulcanizable diene elastomers such as eis-pol LI soprene, polybutylene adiene, butadiene copolymers with elastomers of It is natural or synthetic EPDM reindeer and imitation materials. Mixtures may contain from about 10 to about 90% by weight of each type of elastoinero. The vulcanizable composition may also contain other conventional additives known in the teemee, including fillers such as black or silicon, stabilizers, antioxidants, plastics, processing oils and similar additives such as those known in the art. The vulcanizable composition can also be prepared and Mixing using any suitable mixing device such as a two-roll mill, a blender (Brabender Plast i corcler), a Banbury mixer, a mixer or a similar mixing device, emperatures and mixing times may vary from approximately 15 ° to li) 0 ° C and approximately 4 to 10 minutes, respectively. After forming a homogeneous mixture of the halogenated elastomer and the optical fillers, processing aids and the like, the mixture is then prepared for vulcanization by further incorporation of the singe retardant and the curing system of this invention into the mixing device. or in a separate mixing device such as a two-roll mill, after which the mixture is laminated as is well known in the art. A more complete understanding of the invention can be obtained by reference to the following examples, in which all parts are by weight and all temperatures in degrees centigrade, unless otherwise specified. A preferred filler of the preferred elastomer of the invention was prepared first using the following proportions: Weight-bearing material Exxpro 09-4 100.0 Black smoke N-660 60.0 Stearic acid 10 Ex xpro 89 -4 is a brightened copolymer of 95% of i sobut ilono and > "i% of p-met i Lest i reno, with an ooney viscosity of approximately 40 (ML I« -8 (•) 125"C) manufactured by Txxon Chemical Compa y. The master batch was produced in a Banbur-y Laboratory mixer, mixing the rubber only for 1.0 minute, adding two thirds of the black and steapeous acid, and mixing at 110 ° C. Later the rest of the black and the acid was mixed and mixed during LO minute. The master load was discharged at 1 1 ° C. Portions of the master batch were then further mixed in a mixing mill, adding zinc oxide and accelerator. The proportions are set forth in Table I, together with the test results of the compounds prepared according to all test methods of the ASTM standard. MBTS is a vulcanization accelerator, benzot lazyl dlsulfide. DURALINKR HTS is a registered trademark for bis-thiosulfate of hexarnetiieno, salt of sodao dihi dratada, sold by Monsanto Company ,. The results of the test in Table I show that a much faster interlacing velocity was obtained with DURALTNKR HTS, as it becomes evident during the shorter times and the much higher peak vercidity. In addition, the DURALTNKR HTS gives a much higher degree of entanglement as shown by the much higher final module and tensile figures.

EXAMPLE 2 This is a comparative example showing the bonding of the preferred halogenated rubber using known vulcanization accelerator vanes. MBT is 2-mereaptobenzothiazole; MBTS is as described in Example 1, TBBS sulfenainide of t-butylbenzothiol and TBSI is sulferumide of t-but lbenzothiazol. The master load is The nnsma shown in Example 1. The proportions used and the test results obtained are shown in Table II. It is clear from the preliminary results that none of the known and tested accelerators gave comparable results with DURAL1NKR HTS. Moreover, in many cases, increased throttle levels produced lower modulus and torque for maximum torque.

TABLE I Materi l 1 2 3 4 5 Master Load 161.0 161.0 161.0 61.0 161.0 Zinc oxide 3.22 3.22 3.22 3.22 3.22 MBTS - 0.55 1.10 DURALINKR HTS - - - 0.55 1.10 Curing meter results: MDR 2000 g 180 ° C Rmax, dNm 20.0 18.1 15.0 20. q 20.2 uncle, mi '3..6 4. L 2.B 1 .1 1.1 5. min. LL.2 6..0 4.3 2.2 2.1 t9o, min. 30.5 32.3 35.9 19. 7.6 Peak Speed, dNin / man. L.O 1.7 2.3 3.5 9.3 Tension properties: MPa of final tension 9.6 15. 14.6 16. b 17.0 Final lengthening,% 421 326 488 222 220 Module 100%, MPa 2.2 3.5 2.7 B.l 6.6 TABLE II Material 6 7 8 9 10 Master Load 161.0 161.0 161.0 161.0 161.0 Zinc Oxide 2.0 2.0 2.0 2.0 2.0 MBT 0.23 0.46 - - MBTS - - 0.4 0.91 GBDS - - - - TBSI - - - _ Results of the curing meter: MDR 2000 180 ° C Rrnax, dNrn 16.0 14.5 13.2 15.0 13.8 fio. rnin 4.2 3.7 2.9 4.7 3.9 t-25 - min. 14.8 7.8 5.0 8.2 5.5 tg o, rn i n. 37.4 32.4 34.4 32.3 34.3 Peak Speed, dNrn / rnin. 0.8 1.1 1.1 1.2 1.7 Tension properties: MPa of tension f-inal 1 .5 1. 1 .1 14. L 14. Final lengthening,% 131 1 8 L5G? R.6 185 Module 1110%, MPa 8.5 7.3 6.3 7.8 6.3 TABLE II (continued) Material U 1? 13 1_4 C rga rnaest a 161.0 L61.0 161.0 161.0 Zinc Oxide 2.0 2. (1 2.0 2.0 MBT - - - _ MBTS - TBBS 0.33 0.66 TBST - - 0.56 L.ll Results of the curing meter: MDR 2000 (? 180 '3C Rrnax, dNrn 13.9 12.1 14.7 12.9 uncle, min. 3.2 2.2 4.0 3.0 t25. inm. 6.3 4.1 8.8 5.3 tgo, inm. 26.9 17.5 30.2 25.4 Peak Speed, dNin / min. 0.7 1.0 0.9 1.1 Tension properties: Final voltage MPa 12.5 13.3 12.7 L2.9 Final elongation,% 159 216 159 190 Module 100%, MPa 6.3 4.4 6.5 5.1 EXAMPLE 3 In a manner similar to that of Example 1, rubber compositions containing Lan? N mono-B? Nte salt accelerator were prepared and tested. The same ingredients and in the same proportions, were present in the master load, except that Exxpro 90-10 was used or described in example 4 below. Lower levels of zinc oxide were used, compared to Example 1, and control samples that did not contain accelerator and that contained DURALINKR HTS were compared. Proportions and test results are set in the rTT table. The results demonstrate the effectiveness of the ono-Bunte salts as accelerators in the composition of the invention.

EXAMPLE 4 To show the use of the diene hydrocarbon rubber mixtures with the halogenated elastomers in the composition of the invention, another series of samples in a similar manner was carried out and tested. The master load for the mixture has the following proportions: Material Parts by weight Exxpro 90-10 40.0 2 b Pol i butadieno 00.0 Natural rubber 10.0 Black smoke N-660 50.0 Ace 1 e na f teni eo 12.0 Adhesive resin 5.0 Ad Mixing aid 4.0 Total 171.0 Erxxpro 90-10 is a brominated copolymer of 92.5% full and 7.5 isobut % of p -met i lest i re no, with a viscosity of Mooney of about 45 (ML lt-H 0125 ° C) "Pole and butadiene was a 1, -some 98% Limero of 1, 3-but adiono. The mixing aid and Struktol 40MS, and the tackifying resin was Escorez 1102, manufactured by Exxon Chemical Company. The proportions of the mixture ingredients and the test results are shown in L quad-or IV. The zinc halide, a zinc salt of fatty acid, is also available as a curing agent. The results show that the composition containing DURAL1NKR HTS was much faster in the initial stages of curing, as indicated by the times t o and t25; Although the final properties of all the samples were comparable, the DURALINKR HTS sample reached these properties much more quickly. 07 TABLE III Matter 15 16 1 10 19 Ca ga rna e t L 61.0 161.0! (• "¡1.0 1 1. 161.0 Oxide of inc l.O 0.5 1.0 0.5 1.0 DURALINKR HRS - 0.5 0.5 - - Thiosul fato of Nabencilo 0.6 0.63 Results of the meter «cured him: MDR 2000 1Ü0 '' C Rrnax, dNm 30.8 25.7 30.7 24.9 28.6 uncle, inin. 2.6 2.8 2.1 2.1 1.5 t25. mui 3.8 4.2 2.7 3.0 2.2 tgo, inin. 15.4 32.1 14.6 33.5 15.5 Paco speed, dNrn / rnin. 4.0 4. 9.7 4.0 Sealing properties: Final tension MPa 15.1 16.3 L6.6 16.0 15.2 Long elongation,% 142 185 129 174 133 Module 100%, MPa 10.2 9.1 11.9 9.3 10.6 TABLE IV Material 20 21 22 Load Rating 171.0 171.0 171.0 Zinc Oxide 2.0 2.0 2.0 TBBS 2.0 2.0 2.0 DURALINKR HTS 3.2 twenty Azu fre o.p 0.0 0.8 t i Zinc Lhexanoate 2..9 Cure meter results: MDR 2000 0 1B0 ° C Rrn x, dNm 34.1 37.0 30.4 uncle, rn i n. 12, .0 11.9 5.6 t25 - min. 17.2 16"0 6.7 19 o, in i n. 25.9 24.2 17.3 Peak speed, dNrn / min. 3.6 4.6 4.6 Properties of tension: MPa of fmal voltage 13.9 12.7 14.1 Elongation fmaL,% 622 611 684 Module 100%, MPa 1.68 1.4 1.4

Claims

NOVELTY OF THE INVENTION CLAIMS

1. - An interlayer composition comprising a mixture of a halogenated elastomer selected from chlorinated or bleached methyl ether of an isoolefin of Ci, a C7 and a polyurethane of para-alkyl quot, an entanglement agent and je 0.1 to LO. f) parts by weight, per 100% parts of the halogenated elastomer by weight, of an accelerating compound which contains one or more groups of the formula -S-SO2-OM attached to a hydrocarbon radical or a bridging group organic where M is a monovalent metal, the equivalent of a multivalent metal, a monovalent ion derived by the addition of a proton to a mitogenic base, or the equivalent of a multivalent ion derived by the addition of two or more protons to a base Mtrogeneous

2. A composition according to claim 1, wherein in the accelerating compound, two or more -S-SO2-OM groups are attached to a primary cation of a bridging group.

3. A composition according to claim 2, wherein the accelerator material is a compound having the formula MO-O2 -SX '-S-SO2 -OM, wherein X' represents an alkylene radical or a radical comprising two or more alkyl units, pairs of such units being linked to an oxygen or sulfur atom, through a group - SO2 -, -NH-, -NH2 + -, -M (alkyl of Oi-ß) - or -COO-, oat through a radical apleno or ci cloalqui Log,.

4. A composition according to claim 3, wherein X represents an alkylene radical of C2-16 or a radical having the formula - (CH2) a ~ 0 ~ (CH2) a ~, - (CH2) a-0-CH2-0- (CH2) a -, - (CH2) b - ac 1 ohex full- (CH2) b -. -CH2) c -C00- (CH2)? -, - (CH2) c -C00-Y-00C- (CH2) c ", - C CH2) c -SO2" (CH2) c - O - (CH2) c -NH2 * - (OH2) c ~, where e a represents independently an integer from 3 to 8, b represents an integer from 1 to 4, c represents an integer from 3 to 12, Y represents a group ~ (CH2 ) C or a group - (CH2 CH20) d CH2 C-H2 - yd r-e represents an integer from L to

5. 5. A composition according to claim 4, wherein each M represents an alkali metal or a equivalent of magnesium, calcium, barium, zinc, cobalt or nickel, and the accelerator material may also contain water of crystallization.

6. A composition according to claim 5, wherein each M represents sodLO.

7. A composition according to claim 4, wherein each M represents an ammonium ion or an R2NH3 + ion. R2 R3NH2 + or R2R3RANH +, wherein each of R2, R3 R "independently represent an alkyl group of Ci-20? N cycloalkyl group or a C5-9 heavenly alkyl, a benzyl group, a femlo group or a phenyl group replaced, As long as no more than one of R2, R3 and R4 is an item or faith, it is substi tuted. 0.- A composition (Je conformi ad with the rei indication 7, in which M represents an ion R R3NH +, where one of R2 and R3 is a ter-aLquilo group of C4-12 and the other is a benc or where one of R2 is a sec-to-quilo group of C3-12 or? n cyclohexyl group and the other is a group 4- feni 1 -amino feni lo. 9. A composition according to claim 4, in which M represents a guarudimo ion or g ua n 1 din 1 or its bst L tu 1 do of the fo rrn u 1 a: NH2 + R2NH-C -NHR2 or an isothiouromo ion of the formula: SRS I + -NI-.2 -C-NH2, wherein each R2 independently represents hydrogen, a C1-20 alkyl group, a cycloalkyl group or alkylcycloalkyl Lo of C5-9 . a benzyl group, a phen group, or a phen 1 group subsumed, and R 5 represents a C1-20 alkyl group. a cycloalkyl group or a C5-9alkylalkyl or a benzyl group. 10. A co-position according to claim 4, in which M represents an optionally substituted 1,2-dihydro-qumolinium ion ring. 11. A composition according to the rei indication 4, in which M represents the equivalent of a divalent ion of the formula R2N + H2 -A-N + H2 R2. where A represents a radical - (CH2 -te -, where c has a value of 2 !? a? 0 or a femlene radical, and each R2 independently represents an alkyl group of O1-20. a cycloalkyl group or a cycloalkyl group of C5-9, a beneyl group of a substituted phenyl or phenyl group, provided that neither R2 nor phenyl is substituted or substituted when A represents phenylene. 12. A composition according to claim 1, in which A represents a para-femlene radical and each R2 represents a sec-to-chyl group of C3-12- 13. A confounding composition with claim 4 , in which M represents the equivalent of? n divalent ion of the formula wherein c is an integer from 2 to 20. 14. A composition according to claim 1, wherein only a -S-SO2-OM group is attached to a molent hydrocarbon radical selected from alkyl of 1-20. carbons, radicals aplo of 6-20 carbons and Radicals araLquilo or al canlo de? -21 car-bonds. 15. The composition according to claim 1, wherein the entanglement agent is zinc oxide, present in an amount of from 0.5 to 10 parts by weight per 100 parts of the halogenated elastomer by weight. 16. The composition according to the embodiment 15, in which the entanglement agent and the accelerator material are present in an amount of from 0.1 to 5 and 0.5 to 5 parts by weight, respectively, per 100. parts of the halogenated elastoinero by weight. 17. The composition according to claim 16, wherein the halogenated elastoinerole is b romura. 1

8. The composition according to claim 1, wherein the halogen elastomer is a halogenated interpol of a Ci isoolefin, a C7 copolymerized with para-alkyl styrene, said e-polymer contains from about 0.5 to about 20% molar units of rnonoinero of the following structure distributed randomly in it: wherein R and R 'are independently selected from the group consisting of hydrogen and lower alkyl, R "is independently selected from the group consisting of hydrogen, lower alkyl and X, and X is bromine or chlorine, and wherein the e-polymer is substantially Ring-free halogen-free and halogen-free present in the chain of the base structure of pol-ene 19.- The composition according to claim 18, wherein the entanglement agent is zinc oxide, present in a quantity of from 2 to 3 parts by weight, and the accelerator material - is a sodium hydrated salt of bis-L, 6-hexarnet thio sulphate, present in an amount of from 1 to 3 parts by weight, in base to 100 parts by weight of the halogenated elastomer 20. The composition according to claim 19, wherein said halogenated metal ester is a terpolymer of Lsobutiieno, para-methyl-urethane and rnonobro-or-para-methyl-urethane. .- The composition of in accordance with claim 20, wherein from about 5 to 30 Approximately 100% molar units of the para-inet resin contain a non-bromomethyl group. The composition is in accordance with claim 21, wherein said terpoliner has a bromine content. .n the scale from approximately 0.1 to apr-ox and 5% molar. 23. The composition according to claim 1, in the one or more vulcanizable diene agents, together with their curing systems, are mixed with it in a weight ratio of 90: LO at 10:90. 24. The composition according to claim 23, wherein the diene elastomer is selected from cis-pol usoprene, poly ibadotiene, natural or synthetic butadiene-esterfirn copolymers and EPDM rubber.