CN1188494A - Halogenated elastomer compositions - Google Patents
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- CN1188494A CN1188494A CN96194897A CN96194897A CN1188494A CN 1188494 A CN1188494 A CN 1188494A CN 96194897 A CN96194897 A CN 96194897A CN 96194897 A CN96194897 A CN 96194897A CN 1188494 A CN1188494 A CN 1188494A
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Abstract
Rubber compositions in which the rubber is a halogenated butyl elastomer are crosslinkable by virtue of containing a crosslinking agent such as zinc oxide and an accelerator which is a salt of an organic thiosulfate.
Description
Field of the present invention
The present invention relates to comprise the composition of halogenated elastomer, particularly contain the elasticity interpolymer of vinylbenzene, linking agent and the thiosulfates promotor of the replacement of iso-butylene and contraposition haloalkyl.
Background of the present invention
The halogenated copolymers of iso-butylene and be well-known polymer materials up to the isoprene (isoprene-isobutylene rubber) of about 4mol%, their vulcanizate provides some many other outstanding character that elastomerics did not have based on diolefine.Goods by many sulfurized halogenated elastomer preparations provide the oil resistant of raising and character and the oxytolerant and the ozone decomposability of lipid.The isoprene-isobutylene rubber vulcanizate has shown good wear resistance, to the good pressuretightness of air, water vapour and many organic solvents, and ageing-resistant and Exposure to Sunlight.This class character makes these materials become the desirable candidate of one or more application such as water pipe, organic fluid pipe, tire construction integral part, pad, binder composition and various moldingss.
More recently, have been found that new halogenated elastomer multipolymer presents and the many identical character of halogenated butyl rubber, but more anti-ozone and solvent, and easier sulfuration.These materials are C
4-C
7Isoolefine such as iso-butylene and to the halogenation product of the random copolymers of ring-alkylated styrenes comonomer, wherein at least some alkyl substituents comprise halogen in the styrene monomer unit.
In U.S. Pat 5,162, these multipolymers and manufacture method thereof are more specifically disclosed in 445, its whole disclosures are incorporated herein for reference.Aromatics monochloromethyl in this analog copolymer allows to finish in every way easy crosslinked, comprises by being usually used in vulcanizing the zinc oxide or the promoted zinc oxide vulcanization system of halogenated butyl rubber.
Yet some in these promoted zinc oxide cross-linking systems can be brought serious scorching problem.
U.S. Pat 5,373,062 discloses and has been characterized as the halogenated elastomer compositions that has used promoted zinc oxide linking agent and bismuth carboxylate scorching inhibitor.
The purpose of this invention is to provide halogenated elastomer compositions, but the said composition high-speed vulcanization, but do not have serious scorching problem, and can reach high-caliber crosslinked.
Summary of the present invention
According to the present invention, have been found that a kind of improved promotion vulcanization system that is used for halogenated elastomer, comprise linking agent in the vulcanization system and contained one or more promotor that are connected the following formula group on alkyl, organic abutment or the polymkeric substance
-S-SO
2-OM
The monovalent ion that wherein M is monovalence metal, normal polyvalent metal, proton of addition obtains in nitrogenous base or normal in nitrogenous base the resulting polyvalent ion of the two or more protons of addition.
The halogenated elastomer compositions that comprises these linking agents and promoter material can high-speed vulcanization to a high sulphided state, and avoids the scorching problem.
Detailed description of the present invention
Halogenated elastomer in the present composition comprises chlorination or brominated butyl rubber, C
4-C
7Isoolefine and to the chlorination or the brominated copolymer of ring-alkylated styrenes, their mixture, or one or both these elastomericss and vulcanizable diene elastomer such as natural or synthesizing cis polyisoprene, polyhutadiene, butadiene-styrene copolymer or ethene, propylene and the mixture of the elastocopolymer of the non-conjugated diene of 10mol% (being known as EPDM rubber) at the most.
Halobutyl rubber can be based on iso-butylene and the chlorination or the brominated copolymer of about 4mol% isoprene at the most.General these elastomeric number-average molecular weight scopes are between about 50,000 and about at the most 500,000, and can be by well known in the art as be disclosed in U.S. Pat 2,940,960 and US3,099,644 polymerization and halogenation method preparation, it is for reference that the disclosure of these files is introduced into this paper.
Based on C
4-C
7Isoolefine such as iso-butylene and be known in the art now to the halogenated copolymers of ring-alkylated styrenes such as p-methylstyrene, this can be confirmed from above-mentioned U.S. Pat 5,162,445.
Preferred material is C
4-C
7Isoolefine such as iso-butylene and to the halogenated products of the random copolymers of ring-alkylated styrenes comonomer, wherein at least some alkyl substituents comprise halogen in the styrene monomer unit.Preferred material be characterized as the isobutylene copolymers that comprises monomeric unit below the random interval of polymer chain:
The structure that wherein has formula 2 in the polymer chain at least about the comonomer unit of 5mol%, R and R ' are hydrogen or C independently
1-C
4Alkyl, R " be hydrogen, C independently
1-C
4Alkyl or X and X are bromine or chlorine, and multipolymer does not conform to any halogen in addition basically in main polymer chain.
About the iso-butylene as the isoolefine comonomer, these multipolymers also comprise:
A) multipolymer of forming by iso-butylene and monomer, wherein R with formula 2 structures " be hydrogen or C
1-C
4Alkyl, for example iso-butylene and single halogen replace to alkylstyrene copolymers;
B) comprise iso-butylene and the terpolymer with monomer mixture of formula 1 and 2 structures, wherein R " be hydrogen or C
1-C
4Alkyl, for example terpolymer of iso-butylene, p-methylstyrene that ring-alkylated styrenes and single halogen are replaced;
C) comprise iso-butylene and have the terpolymer of the monomeric mixture of formula 2 structures, wherein with regard to formula 2 monomers of vast scale, R " be hydrogen or C
1-C
4Alkyl is for described formula 2 monomers of small proportion, R " be bromine or chlorine, iso-butylene, single halogenated for example to ring-alkylated styrenes and dihalogenated terpolymer to ring-alkylated styrenes; With
D) comprise iso-butylene and have the tetrapolymer of the monomeric mixture of formula 1 and 2 structures, wherein with regard to formula 2 monomers of vast scale, R " be hydrogen or C
1-C
4Alkyl is for described formula 2 monomers of small proportion, R " be bromine or chlorine, for example iso-butylene, to ring-alkylated styrenes, single halogenated to ring-alkylated styrenes and dihalogenated tetrapolymer to ring-alkylated styrenes.
As mentioned above, use C
4-C
7Isoolefine and conduct are by these halogenated copolymers of copolymer to ring-alkylated styrenes of halogenation object.Preparation has mentioned component (a) and (b), (c) or multipolymer (d) degree function as halogenating reaction.For example Ruo halogenation will produce the multipolymer of (b) feature, and strong halogenation will produce (a) or (d) multipolymer of feature, and the strongest halogenation has generation the terpolymer of (c) feature.
The most preferably elastomerics that is used for the present composition is a random elastomeric bromination terpolymer, comprise iso-butylene and p-methylstyrene (PMS), contain the about 20mol%PMS of the 0.5-that has an appointment, the about 15mol%PMS of 2-more preferably from about, wherein the PMS monomeric unit of about 60mol% comprises a single brooethyl group at the most.The scope of the number-average molecular weight of general these elastocopolymers is about 50,000 to about 250,000, more preferably from about 80,000 to about 180,000.The 5mol% that has an appointment in total PMS monomer content of terpolymer extremely about 60mol% comprises a single brooethyl group that bromination does not take place substantially at main polymer chain or in aromatic ring.The bromine content scope of these terpolymers generally is about 0.1 to about 5mol%.
An advantage that comprises the elastic composition of halogenated butyl rubber or especially halogenated isobutylene-PMS multipolymer is, they can be with other general objects elastomerics such as polyhutadiene, natural rubber etc. and EPDM elastomerics covulcanization more easily.These characteristics are mainly owing to the following fact: by with sulphur that is used to vulcanize more the height unsaturated elastic body and the irrelevant mechanism of promoted sulfur system, can be with these halogenated materials and height unsaturated rubber covulcanization more.
Can be separately or be used from the known vulcanizing agent of sulfuration halogenated elastomer with zinc oxide one or the example of promotor is, bromination alkyl phenol resin, N, N '-diethyl thiourea, two catechol boric acid two (neighbour-tolyl) guanidinesalts, dipentamethylene thiuram tetrasulfide, ethylidene trithio carbamate, 2-mercaptobenzothiazole, curing alkyl or aryl benzothiazole, tetramethyl-thiuram disulfide, zinc diethyldithiocarbamate, zinc dibutyl dithiocarbamate and ziram.Known vulcanization system comprises zinc oxide and dipentamethylene thiuram tetrasulfide.Preferably independent zinc oxide in the present composition, preferred amount is used 0.05-10 part, more preferably 0.1-5 part, most preferably 2-3 part for per 100 weight part halogenated elastomers.
Preferred promoter material is a compound that primary carbon atom links to each other of each thiosulfuric acid ester group and alkyl or abutment wherein, the polymkeric substance that links to each other with primary carbon atom in the side chain that is connected in the host polymer chain with thiosulfuric acid ester group wherein.Therefore the thiosulfuric acid ester group is often with-CH
2-S-SO
2-OM form exists.
(it is wherein single-S-SO to promotor
2-OM group is connected in the compound of alkyl) comprise the alkyl or aryl thiosulfates, be sometimes referred to as " Bunte salt ".The example of these compounds has ethylmercapto group vitriol, benzylthio-vitriol etc.Alkyl can be the alkyl that 1-20 carbon atom arranged, and the aryl of 6-20 carbon atom is arranged or the aralkyl or the alkaryl of 7-21 carbon atom are arranged.In the alkyl nullvalent substituting group can be arranged in addition.
(it is to contain the connection mode-S-SO that connects by organic abutment to promotor
2The compound of-OM group) contains two, three or four-S-SO usually
2-OM group.The example of this compounds is to have those of following formula
X[-(CH
2)
n’CH
2-S-SO
2-OM]
n”
Wherein n ' is at least 1 integer, n " be 2,3 or 4, X represents the remainder of abutment.
Two-S-SO is being arranged
2In the compound of-OM group, abutment is a divalence, and this compounds can be expressed from the next
MO-O
2S-S-X’-S-SO
2-OM
X ' for example can be straight or branched alkylidene group or alkylene group group in this formula, preferably contains 2-40 carbon atom, more preferably contains 5-16 carbon atom.The example of this class group is ethylidene, pentamethylene, hexamethylene, octamethylene, nonamethylene, 1, the inferior decyl, 1 of 10-, the inferior dodecyl of 12-, 3-methyl isophthalic acid, 5-pentylene and inferior 1,6-oneself-the 2-thiazolinyl.As a kind of version, divalent abutment can be to have substituent alkylidene group of one or more aryl (as phenyl) or alkylene group.The example of such group is 2-phenyl-tetramethylene.
In other cases, X ' has the structure that comprises two or more alkylidene units, and paired this type of unit passes through oxygen or sulphur atom, passes through-SO
2-,-NH
2+-,-N (C
1-6Alkyl)-or-COO-group or connect by arylidene or cycloalkylidene.The representative of this class formation is to have those of following formula
-(CH
2)
a-O-(CH
2)
a-
-(CH
2)
a-O-CH
2-O-(CH
2)
a-
-(CH
2)
b-cyclohexylidene-(CH
2)
b-
-(CH
2)
c-COO-(CH
2)
a-
-(CH
2)
c-COO-Y-OOC-(CH
2)
c-，
Each a and c represent the integer of 2-20 independently, and each b represents the integer of 1-10 independently, and Y represents-(CH
2)
c-or-(CH
2CH
2O)
dCH
2CH
2-group, wherein d represents the integer of 1-5.Preferred a value is 3-8, and preferred b value is 1-4, and preferred c value is 3-18, more preferably 3-12.
Other example of abutment X ' is to have those of following formula
-(CH
2)
c-SO
2-(CH
2)
c-
-(CH
2)
c-NH-(CH
2)
c-
With
-(CH
2)
c-NH
2+-(CH
2)
c-
Wherein each c represents the value of 2-20 independently, preferred 3-18, more preferably 3-12.
When the value of a, b or c in the formula greater than 2 the time, the polymethylene group can be a straight or branched, but preferred and-SO
2The terminal carbon that-OM group links to each other is a primary carbon atom.
Promoter compound with three or four thiosulfuric acid ester groups comprises wherein three or four-C
mH
2m-S-SO
2-OM group (m generally is 3-6) is a substituting group in the aromatic ring (as benzene or naphthalene nucleus), (also can comprise other substituting group), or as the substituent compound in one or more ring of two or three cyclophane compounds of group (as biphenyl, phenyl ether, sulfobenzide or benzophenone).
Other example of trivalent abutment is to have those of following formula
-A
1-OCH
2CH(OA
1-)CH
2OA
1-
With
A-C(AOOCA
1-)
3
Each A in the formula
1Be alkylidene group, for example C independently
2-18, preferred C
3-12Alkylidene group and A are C
1-6Alkyl;
With those of following formula
N[(CH
2)-
c]
3And HN+[(CH)-
c]
3
Each c is the value of 2-20 independently in the formula, preferred 3-18, more preferably 3-12.
Other example of tetravalence abutment is to have those of following formula
C (A
1)
4(A
1)
3Si-O-Si (A
1)
3
A in the formula
1Has meaning same as described above; And have those of following formula
C[CH
2OCO(CH
2)-
c]
4
Each c is the value of 2-20 independently in the formula, preferred 3-18, more preferably 3-12.
The example of polymkeric substance is to have those of following formula
With esterification and polyvinyl alcohol partial esterification, wherein polymer chain forms by being selected from following unit
R ' expression C in the formula
1-12Alkyl, c is the round values of 2-20, and in the polymkeric substance at least 10%, preferably at least 20%, for example the unit of 25%-75% is for containing-S-SO
2Those unit of-OM group.
When the M in the following formula in promoter material represented monovalent metal, it for example was a basic metal, as sodium, lithium or potassium.Sodium is preferred basic metal.M is expression 1 normal polyvalent metal in addition, as magnesium, calcium, barium, zinc, nickel, cobalt or aluminium.
M represents that the univalent ion that formed by proton of addition in nitrogenous base, nitrogenous base can be ammonia or simple primary, second month in a season or tertiary amine in the formula
R
2NH
2, R
2R
3NH or R
2R
3R
4N
R in the formula
2, R
3And R
4Represent alkyl group independently of one another, as C
1-20Alkyl, C
5-9Cycloalkyl or alkyl-cycloalkyl are as cyclohexyl or methylcyclohexyl, benzyl, phenyl or substituted-phenyl, as tolyl or chloro-phenyl-, as long as R
2, R
3And R
4In no more than one be phenyl or substituted-phenyl.
Preferred amine be weakly alkaline relatively those.These comprise the weakly alkaline amine that causes steric hindrance around nitrogen-atoms, and the sterically hindered reason is that for example, the existence of tertiary alkyl is if any the tertiary alkyl of 4-12 carbon atom, as the tertiary butyl, tert-pentyl or 1,1,3,3-tetramethyl butyl.The example of this type of amine is secondary amine R
2R
3NH, R in the formula
2And R
3In one of be tertiary alkyl, another is benzyl or cyclohexyl or alkyl-cyclohexyl.In addition, R
2And R
3It can be tertiary alkyl.Other example is a tertiary amine, R in the formula
2Be tertiary alkyl and R
3And R
4It is benzyl.
Other weakly alkaline amine that is fit to is primary amine R
2NH
2, R in the formula
2Be phenyl or substituted-phenyl and secondary amine R
2R
3NH, R in the formula
2Be phenyl or substituted-phenyl,, R
3Be C
1-12Alkyl.The example of this type of amine is aniline, Tolylamine, methylphenylamine, N-butylaniline and N-isohexyl aniline.A special category of this secondary amine comprises R in the formula
2Represent secondary alkyl, preferred C
3-12Secondary alkyl or cyclohexyl and R
3Those of expression 4-phenyl amino phenylene.These amine comprise such as N-sec.-propyl-N '-phenyl-Ursol D, N-sec-butyl-N '-phenyl-Ursol D, N-1,3-dimethylbutyl-N '-phenyl-Ursol D, N-1, the compound of 4-dimethyl amyl group-N '-phenyl-Ursol D and N-cyclohexyl-N '-phenyl-Ursol D.Although the existence of second nitrogen-atoms in the 4-phenyl amino phenylene group, this type of amine plays monobas effect, because in fact this second nitrogen-atoms do not have alkalescence.
Other example that forms the nitrogenous base of thiosulfates salt of the present invention is guanidine and replaces guanidine, as shown in the formula those
With the isothiourea that replaces, as shown in the formula those
Each R in the formula
2Represent hydrogen, alkyl such as C independently
1-20Alkyl, C
5-9Cycloalkyl or alkyl-cycloalkyl, benzyl, phenyl or substituted-phenyl, as tolyl, and R
5Expression C
1-20Group, C
5-9Cycloalkyl or alkyl-cycloalkyl or benzyl.The specific examples that replaces guanidine is diphenylguanidine and two-o-tolyl guanidine; The specific examples that replaces isothiourea is S-ethyl isothiourea and S-benzylisothiourea.
M represents the 1 normal polyvalent cation that the two or more protons of addition form in nitrogenous base in the formula, and the alkali that is obtained by this class ion comprises Alkylenediamine, the N of following formula, N '-two substituted alkylene diamines, phenylenediamine and N, N '-disubstituted benzenes diamines
R
2NH-A-NHR
2
A represents alkylidene group-(CH in the formula
2)
c-, c is the value of 2-20, preferred 2-12, it can be a straight or branched, or phenylene, as or to phenylene, each R
2Independently represent alkyl, as C
1-20Alkyl, C
5-9Cycloalkyl or alkyl-cycloalkyl, benzyl, phenyl or substituted-phenyl need only R when A is phenylene
2Neither phenyl neither substituted-phenyl.
In preferred amine, A represents inferior a heatable brick bed base, R
2Be tertiary alkyl, as the tertiary butyl, tert-pentyl or 1,1,3,3-tetramethyl butyl, or phenyl.The example of this type of amine is N, N '-diphenyl ethylene diamine, N, N '-di-t-butyl-1,4-tetramethylene-diamine and N, N '-two (1,1,3, the 3-tetramethyl butyl)-hexamethylene diamines.
In preferred amine, A represents phenylene, R
2Be secondary alkyl, preferred C
3-12Secondary alkyl or cyclohexyl.The example of this type of amine is N, N '-two-sec-butyl-Ursol D, N, N '-two (1, the 3-dimethylbutyl)-Ursol D, N, N '-two (1,4-dimethyl amyl group)-Ursol D, N, N '-two (1-ethyl-3-methyl amyl)-p-phenylenediamine, N, N '-two (1-methylheptyl)-Ursol D and N, N '-dicyclohexyl-Ursol D.
Possible alkali also comprises the polyalkylenepolyamines of following formula
R
2NH-(A’-NH)
n-A’NHR
2
A ' expression has the alkylidene group of 2-8 carbon atom in the formula, and n is the numerical value of 1-5, each R
2Represent C independently
1-20Alkyl, C
5-9Cycloalkyl or alkyl-cycloalkyl, benzyl, phenyl or substituted-phenyl.
In other cases, the nitrogen in the nitrogenous base is a heterocyclic part.Alkali can be monocyclic, is fused to compound in another ring as pyridine or nitrogen heterocyclic ring, as quinoline.And heterocycle can be saturated, as morpholine or piperidines, maybe can comprise one or more pairs of keys, as pyrroline or 1, and the 2-dihyaroquinoline.
M represents in the middle of the compound of this type of alkali therein, and those compounds that are preferably used as promotor are that wherein M represents 1,2-dihyaroquinoline ionic compound, and it can randomly have ring substituents.This type of ionic example is 2,2,4-trimethylammonium-1,2-dihyaroquinoline, 2,2,4-trimethylammonium-6-(C
1-12Alkoxyl group)-1, the 2-dihyaroquinoline, as 2,2,4-trimethylammonium-6-oxyethyl group-1,2-dihydroquinoline, 2,2,4-trimethylammonium-6-(C
1-18Alkyl)-1, the 2-dihyaroquinoline, as 2,2,4-trimethylammonium-6-dodecyl-1,2-dihyaroquinoline and 2,4-diethyl-2-methyl isophthalic acid, 2-dihyaroquinoline.Other class alkali that forms divalent cation by two protons of addition is represented by following general formula:
A in the formula
2Expression-(CH
2)
c-, wherein c is the integer of 2-20, preferred 3-12 ,-(CH
2)
c-can be straight or branched or C
2-20Alkylene group or inferior alkadienyl are as butenylidene or Ya Xin-2,6-dialkylene.These alkali correspondingly form two (isothiourea) and two (guanidine) ion.
Promotor of the present invention is in U.S. Pat 4,417, and is open and required as claim in 012,4,520,154 and 4,587,296.The purposes of the material of describing in these patents is as being used to vulcanize the stablizer of dience rubber, is provided at the anaerobism of the prolongation anti-overcure-reversion on aging.
Composition of the present invention also can contain halogenated elastomer and vulcanizable diene elastomer, the blend of for example natural or synthesizing cis-polyisoprene, polyhutadiene, divinyl and elastomeric multipolymer of vinylbenzene EPDM and analogous material.This type of blend also contains every type of elastomerics of about 90% (weight) of the 10%-that has an appointment.
Vulcanisable compound of the present invention also can comprise other habitual additive known in the art, comprises weighting agent such as carbon black or silicon-dioxide, stablizer, oxidation inhibitor, softening agent, processing oils and similar additive known in the art.
Also available any suitable mixing device preparation of vulcanisable compound and mixing are as double roll mill, Banbury mixer (Brabender Plasticorder), Ban Buli mixing roll, kneader or similar mixing device.Blending temperature and time range are respectively about 15 °-180 ℃ and about 4-10 minute.Behind the uniform mixture that forms weighting agent that halogenated elastomer and arbitrariness select for use, processing aid etc., by on kneading device or independent kneading device such as double roll mill, further introducing early stage vulcanization retarder and vulcanization system of the present invention, preparation is made sheet with mixture afterwards as known in the art for the mixture of sulfuration usefulness.
Can realize the present invention is more fully understood by the following examples, except as otherwise noted, wherein all umbers all by weight, all temperature all refer to degree centigrade.
Embodiment 1
The masterbatch that at first prepares preferred elastomer of the present invention with following ratio:
Material weight part
Exxpro?89-4 100.0
N-660 carbon black 60.0
Stearic acid 1.0
Exxpro 89-4 is the brominated copolymer of the p-methylstyrene of 95% iso-butylene and 5%, and mooney viscosity is about 40 (ML1+8@125 ℃), is made by Exxon chemical company.
Masterbatch is made on the Ban Buli mixing roll of test usefulness, and mixing of rubber is 1.0 minutes separately, adds 2/3rds stearic acid and carbon black and mixing to 110 ℃.Added remaining carbon black and stearic acid then also mixing 1.0 minutes.At 121 ℃ masterbatch row is unloaded.
Then the part masterbatch is further mixed in opening rubber mixing machine, add zinc oxide and promotor.Provided ratio in the Table I, and according to the test result of ASTM standard method of test for compound.
MBTS is a vulcanization accelerator, benzothiazyl disulfide.DURALINK
HTS is the registered trademark of the two thiosulfates two hydration sodium salts of hexamethylene of Monsanto company sale.
Test result in the Table I shows, uses DURALINK
HTS can obtain crosslinked more rapid rate, and this can be by shorter t
90The peak lift velocity of time and Geng Gao obtains proof.DURALINK in addition
HTS has provided higher degree of crosslinking, and this can be shown by higher limit tension and modulus numeral.
Embodiment 2
This is a comparing embodiment, and some known vulcanization accelerators of display application come crosslinked preferred halogenated rubber.MBT is a 2-mercaptobenzothiazole; MBTS as described in example 1 above, TBBS is tertiary butyl benzo thiazole-sulfinyl amine, TBSI is tertiary butyl benzo thiazole-sulfenimide.What show among masterbatch and the embodiment 1 is identical.
The test result that has provided used ratio in the Table II and obtained.Clearly show by test result, the known accelerators that none is tested provide can with DURALINK
The result that HTS compares.And in many cases, the raising of promotor volume production given birth to lower modulus and lower maximum rheometer moment of torsion.
Table I material 12345 masterbatch 161.0 161.0 161.0 161.0 161.0 zinc oxide 3.22 3.22 3.22 3.22 3.22MBTS-0.55 1.10--DURALINK
HTS---0.55 1.10 vulcanizing ingredient results: MDR 2000@180 ℃ Rmax, dNm 20.8 18.1 15.0 20.9 20.2t
10, divide 3.6 4.1 2.8 1.1 1.1t
25, divide 11.2 6.0 4.3 2.2 2.1t
90Divide 38.5 32.3 35.9 19.3 7.6 peak lift velocity, dNm/min. 1.0 1.7 2.3 3.5 9.3 tension character: limit tension, Mpa 9.6 15.7 14.6 16.6 17.0 ultimate elongations, % 421 326 488 222 220100% modulus, Mpa 2.2 3.5 2.7 6.1 6.6
Table II material 6789 10 11 12 13 14 masterbatch 161.0 161.0 161.0 161.0 161.0 161.0 161.0 161.0 161.0 zinc oxide 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0MBT-0.23 0.46------MBTS---0.46 0.91----TBBS-----180 ℃ of Rmax of 0.33 0.66--TBSI-------0.56 1.11 curameter result: MDR 2000@, dNm 16.0 14.5 13.2 15.0 13.8 13.9 12.1 14.7 12.9t10, divide 4.2 3.7 2.9 4.7 3.9 3.2 2.2 4.8 3.9t
25, divide 14.8 7.8 5.0 8.2 5.5 6.3 4.1 8.8 6.3t
90Divide 37.4 32 4 34.4 32.3 34.3 26.9 17.5 30.2 25.4 peak lift velocity, dNm/min 0.8 1.1 1.1 1.2 1.7 0.7 1.0 0.9 1.1 tension character: limit tension, Mpa 125 1.30 12.1 14.1 14.3 12.5 13.3 12.7 12.9 ultimate elongations, % 131 148 158 156 185 159 216 159 190100% modulus, Mpa 8.5 7.3 6.3 7.8 6.3 6.3 4.4 6.5 5.1
Embodiment 3
In mode similar to Example 1, preparation and test contain the rubber combination of list-Bunte salt promotor.
Except that without the Exxpro 90-10, identical component, identical ratio are used in the masterbatch, as described in the following examples 4.Use a spot of zinc oxide, compare with embodiment 1, and more do not contain promotor and contain DURALINK
The control sample of HTS.Ratio and test result have been provided in the Table III.
Presentation of results in the present composition list-Bunte salt as the effect of promotor.
Embodiment 4.
For the purposes of blend in the present composition that discloses alkadiene rubber and halogenated elastomer, prepare in a similar manner and test another series of samples.
The masterbatch that is used for blend has following ratio:
Material weight part
Exxpro?90-10 40.0
Polyhutadiene 50.0
Natural rubber 10.0
N-660 carbon black 50.0
Naphthenic oil 12.0
Tackifying resin 5.0
Mixing aid 4.0
Summation 171.0
Exxpro 90-10 is the brominated copolymer of 92.5% iso-butylene and 7.5% p-methylstyrene, and mooney viscosity is about 45 (ML1+8@125 ℃).Polyhutadiene is 98% cis 1 that is obtained by 1,3-butadiene, the 4-homopolymer.Mixing aid is Struktol
40MS, tackifying resin are Escorez
1102, make by Exxon chemical company.
The ratio and the test result of compound component have been provided in the Table IV.Zinc ethyl hexanoate, fatty acid zinc salt also are used as vulcanization leveller and participate in relatively.
The result shows by t
10And t
25Time representation contain DURALINK
The composition of HTS, faster in the sulfurating stage in early days; Although the last character of all samples is similar, DURALINK
The HTS sample can be realized these character quickly.
Table III material 15 16 17 18 19 masterbatch 161.0 161.0 161.0 161.0 161.0 zinc oxide 1.0 0.5 1.0 0.5 1.0DURALINK
HTS-0.5 0.5--thiosulfuric acid benzyl ester sodium salt---0.63 0.63 vulcanizing ingredient result: MDR 2000@180 ℃ Rmax, dNm 30.8 25.7 30.7 24.9 28.6t
10, divide 2.6 2.8 2.1 2.1 1.5t
25, divide 3.8 4.2 2.7 3.0 2.2t
90Divide 15.4 32.1 14.6 33.5 15.5 peak lift velocity, dNm/min.4.0 4.8 9.7 4.8 7.8 tension character: limit tension, Mpa 15.1 16.3 16.6 16.0 15.2 ultimate elongations, % 142 185 129 174 133100% modulus, Mpa 10.2 9.1 11.9 9.3 10.6
Table IV material 20 21 22 masterbatch 171.0 171.0 171.0 zinc oxide 2.0 2.0 2.0TBBS 2.0 2.0 2.0DURALINK
HTS--3.2 sulphur 0.8 0.8 0.8 caproic acid ethyl ester zinc salt-2.9-vulcanizing ingredient results: ODR 2000@160 ℃ Rmax, dNm 34.1 37.0 30.4t
10, divide 12.0 11.9 5.6t
25, divide 17.2 16.8 6.7t
90Divide 25.9 24.2 17.3 peak lift velocity, dNm/min.3.6 4.6 4.6 tension character: limit tension, Mpa 13.9 12.7 14.1 ultimate elongations, % 622 611 684100% modulus, Mpa 1.68 1.4 1.4
Claims (25)
1. a compositions crosslinkable comprises being selected from chlorination or brominated butyl rubber and C
4-C
7Isoolefine and to the chlorination of ring-alkylated styrenes comonomer or the halogenated elastomer mixture of brominated copolymer, the promoter material of linking agent and per 100 weight part halogenated elastomer 0.1-10.0 weight parts, wherein promoter material contains one or more and is connected following formula group on alkyl, organic abutment or the polymkeric substance
-S-SO
2-OM
Monovalent ion or the normal polyvalent ion that the two or more protons of addition obtain in nitrogenous base that wherein M is monovalence metal, normal polyvalent metal, proton of addition obtains in nitrogenous base.
2. the composition according to claim 1 is wherein in promoter compound, two or more-S-SO
2-OM group is connected on the generation positively charged ion of abutment, or in the promotor polymkeric substance, is connected in the side chain of host polymer chain on the primary carbon atom.
3. composition according to claim 2, wherein promoter material is the compound with following formula
X[-CH
2)n’CH
2-S-SO
2-OM]n”
N ' is at least 1 round values in the formula, n " be 2,3 or 4, X represents the remainder of abutment.
4. composition according to claim 2, wherein promoter material is the compound with following formula
MO-O
2S-S-X’-S-SO
2-OM
X ' expression alkylidene group or comprise the group of two or more alkyl unit in the formula, paired this type of unit is by an oxygen or sulphur atom, by-SO
2-,-NH-,-NH
2+-,-N (C
1-6Alkyl)-or-COO-group or connect by arylidene or cycloalkylidene group.
5. composition according to claim 4, wherein X represents C
2-16Alkylidene group or have the group of following formula
-(CH
2)
a-O-(CH
2)
a-
-(CH
2)
a-O-CH
2-O-(CH
2)
a-
-(CH
2)
b-cyclohexylidene-(CH
2)
b-
-(CH
2)
c-COO-(CH
2)
a-
-(CH
2)
c-COO-Y-OOC-(CH
2)
c-，
-(CH
2)
c-SO
2-(CH
2)
c-or
-(CH
2)
c-NH
2+-(CH
2)
c-
Each a represents the integer of 3-8 independently, and b represents the integer of 1-4, and c represents the integer of 3-12, and Y represents-(CH
2)
c-or-(CH
2CH
2O)
dCH
2CH
2-group and d represent the integer of 1-5.
6. composition according to claim 5, wherein each M represents basic metal or normal magnesium, calcium, barium, zinc, cobalt or nickel, promoter material also can comprise crystal water.
7. composition according to claim 6, wherein each M represents sodium.
8. composition according to claim 5, wherein each M represents ammonium ion or following ion
R
2NH
3+, R
2R
3NH
2+ or R
2R
3R
4NH+
R in the formula
2, R
3And R
4Represent C independently of one another
1-20Alkyl, C
5-9Cycloalkyl or alkyl-cycloalkyl, benzyl, phenyl or substituted-phenyl, condition is R
2, R
3And R
4In no more than one be phenyl or substituted-phenyl.
9. composition according to Claim 8, wherein M represents ion R
2R
3NH+, R in the formula
2And R
3In one of be C
4-12Tertiary alkyl, another is a benzyl; Or R in the formula
2One of be C
3-12Secondary alkyl or cyclohexyl, another is a 4-phenyl amino phenyl.
10. composition according to claim 5, wherein M represent guanidine or as shown in the formula the replacement guanidinium ion
Or the isothiourea ion of the replacement of following formula
R in the formula
2Represent hydrogen, C independently of one another
1-20Alkyl, C
5-9Cycloalkyl or alkyl-cycloalkyl, benzyl, phenyl or substituted-phenyl, R
5Expression C
1-20Alkyl, C
5-9Cycloalkyl or alkyl-cycloalkyl or benzyl.
11. the composition according to claim 5, wherein M represent randomly cyclosubstituted 1,2-dihyaroquinoline ion.
12. the composition according to claim 5, wherein M represents the divalent ion of normal following formula
R
2N+H
2-A-N+H
2R
2
A represents-(CH in the formula
2)
c-, c is value or the phenylene group of 2-20, each R
2Represent C independently
1-20Alkyl, C
5-9Cycloalkyl or alkyl-cycloalkyl, phenylbenzyl or substituted-phenyl, condition is R when A is phenylene
2Neither phenyl neither substituted-phenyl.
13. the composition according to claim 12, wherein A represents phenylene group, each R
2Expression C
3-12Secondary alkyl group.
14. the composition according to claim 5, wherein M represents the divalent ion of normal following formula
C is the integer of 2-20 in the formula.
15. the composition according to claim 1, wherein single-S-SO
2-OM group be selected from C
1-20Alkyl, C
6-20Aryl and C
7-21The univalence hydrocarbyl group of aralkyl or alkaryl links to each other.
16. the composition of claim 1, wherein linking agent is a zinc oxide, measures to be per 100 weight part halogenated elastomer 0.05-10 weight parts.
17. the composition of claim 16, wherein the amount of linking agent and promoter material is respectively 0.1-5 weight part and 0.5-5 weight part/per 100 weight part halogenated elastomers.
18. the composition of claim 17, wherein halogenated elastomer is a bromination.
19. the composition of claim 1, wherein halogenated elastomer is C
4-C
7The halogenated copolymers of isoolefine and right-ring-alkylated styrenes copolymerization, described multipolymer comprise the monomeric unit of the random distribution following formula structure therein of the about 20mol% of about 0.5-:
Wherein R and R ' are independently selected from hydrogen and low alkyl group, R " be independently selected from hydrogen, low alkyl group and X, X is bromine or chlorine, wherein multipolymer is gone up substantially and is not contained the halogen in ring element and be substantially free of halogen in main polymer chain.
20. the composition of claim 19, wherein linking agent is a zinc oxide, and content is the 2-3 weight part, and promoter material is the hydration sodium salt of two-hexamethylene thiosulfates, and content is the 1-3 weight part, based on 100 weight part halogenated elastomers.
21. the composition of claim 20, wherein said halogenated copolymers are the terpolymers of iso-butylene, p-methylstyrene and single brominated p-methylstyrene.
22. the composition of claim 21, the p-methylstyrene monomeric unit of the about 60mol% of wherein about 5-comprises single brooethyl group.
23. the composition of claim 22, the bromine content scope of wherein said terpolymer are the about 5mol% of about 0.1-.
24. the composition of claim 1, wherein one or more vulcanizable diene elastomers with their vulcanization system with 90: 10～10: 90 weight ratio blend.
25. the composition of claim 24, wherein diene elastomer is selected from natural or synthesizing cis-polyisoprene, polyhutadiene, butadiene-styrene copolymer and EPDM rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96194897A CN1188494A (en) | 1995-04-26 | 1996-04-12 | Halogenated elastomer compositions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/428,994 | 1995-04-26 | ||
| CN96194897A CN1188494A (en) | 1995-04-26 | 1996-04-12 | Halogenated elastomer compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1188494A true CN1188494A (en) | 1998-07-22 |
Family
ID=5128884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96194897A Pending CN1188494A (en) | 1995-04-26 | 1996-04-12 | Halogenated elastomer compositions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1188494A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303144C (en) * | 2004-06-24 | 2007-03-07 | 华东理工大学 | High performance butyl-rubber damping material |
-
1996
- 1996-04-12 CN CN96194897A patent/CN1188494A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303144C (en) * | 2004-06-24 | 2007-03-07 | 华东理工大学 | High performance butyl-rubber damping material |
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