CN1026986C - Heat-resistant rubber composition - Google Patents
Heat-resistant rubber composition Download PDFInfo
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- CN1026986C CN1026986C CN 88108524 CN88108524A CN1026986C CN 1026986 C CN1026986 C CN 1026986C CN 88108524 CN88108524 CN 88108524 CN 88108524 A CN88108524 A CN 88108524A CN 1026986 C CN1026986 C CN 1026986C
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Abstract
Disclosed is a heat-resistant rubber composition comprising (A) 100 parts by weight of an ethylene/ alpha -olefin copolymer or a modified ethylene/ alpha -olefin copolymer formed by graft-copolymerization with at least one compound selected from the group consisting of unsaturated carboxylic acids and anhydrides and esters thereof, and (B) (i) 10 to 100 parts by weight of a silica type filler which has been treated with a silane compound, or (ii) a combination of 10 to 100 parts by weight of said silane-treated silica type filler or an untreated silica type filler and 0.5 to 30 parts by weight of a polyorganosiloxane .
Description
The present invention relates to a kind of heat-resistant rubber comosition, especially the rubber combination that the present invention relates to contains modification or unmodified ethylene/alpha-olefin copolymer rubber and a kind of silica-type filler or a kind of mixed fillers through silane treatment or untreated silica type filler and special polysiloxane through special silane treatment, and this type of filler provides good mechanical property, resistant to thermal aging performance and electrical property for the rubber after solidifying.
The ethylene/alpha-olefin copolymer rubber has good mechanical property and electrical insulation capability, and it is widely used in auto parts, electric parts, and the general industry part, or the like.In recent years, usually require auto parts, electric parts etc. to have high ageing-resistant performance.
Therefore, in synthetic rubber processing technology book series " ethylene-propylene rubber(EPR) ", narrated and attempted oxidation inhibitor is joined in such rubber, but do not reached satisfied improvement effect.
The composition that contains ethylene/alpha-olefin copolymer and silica-type filler has been used for various conventional rubbers field.We have known if the silica-type filler is carried out surface treatment with trimethylchlorosilane or analogue, can give its hydrophobic property, and then this silica-type filler through silane treatment is joined in the ethylene/alpha-olefin copolymer.
Fair when the physical properties of this type of composition begins, but its ageing resistance still dislikes not enough.
We also know and can join in the ethylene/alpha-olefin copolymer strengthening silicon-dioxide and organopolysiloxane, as join in the ethylene propylene rubber.Japanese Patent Application Publication specification sheets 116739/81 and 120744/81 is introduced silicon-dioxide that organochlorosilane is handled and a kind of organopolysiloxane such as dimethyl polysiloxane and is joined in the ethylene propylene rubber, and Japanese Patent Application Publication specification sheets 195757/82 points out that silicon-dioxide and a kind of organopolysiloxane that will fully separate join in the ethylene propylene rubber.
If we find the silica-type filler with having an alkenyl, the trialkoxy silane of a chlorination alkenyl or a chlorination alkyl joins in the ethylene/alpha-olefin copolymer rubber after handling, or join in the ethylene/alpha-olefin copolymer rubber through silica-type filler that silane treatment is crossed or undressed silica-type filler and mixture with organopolysiloxane of a chlorination alkyl this, the heat aging property of so this rubber will be greatly improved.
Therefore, main purpose of the present invention is under the prerequisite of good mechanical property that does not reduce the ethylene/alpha-olefin copolymer rubber and electrical insulation capability, improves its heat aging property.
Another object of the present invention provides a kind of rubber combination, even said composition can generate a kind of high strength and high curing rubber that extends sustainment rate of still demonstrating under the thermal ageing condition.
Or rather, according to the present invention, a kind of heat-resistant rubber comosition is provided, it comprises the ethylene/alpha-olefin copolymer or the ethene improved/alpha-olefin copolymer of (A) 100 weight parts, wherein modified copolymer is to be generated by at least a compound graft copolymerization that is selected from unsaturated carboxylic acid, its acid anhydride and ester, (B) (ⅰ) the silica-type filler handled of the silane compound of 10 to 100 weight parts, the molecular formula of used silane compound is as follows:
R in the formula
1Represent alkenyl, chlorination alkenyl or chlorine alkyl, R
2Represent low-carbon alkyl, perhaps (ⅱ) 10 to 100 weight parts are by the silica-type filler of said silane treatment or the mixed fillers of undressed silica-type filler and 0.5 to 30 weight part polysiloxane, and the general formula of polysiloxane is as follows:
R in the formula
1Represent the saturated or unsaturated alkyl of univalent, R
2Represent chlorine alkyl or alkenyl, a is the number between 1 to 2.5, and b is the number between 0.01 to 1.2,
And a and b sum must be between 1.8 to 3,
In the present invention, be added in the ethylene/alpha-olefin copolymer rubber after the silica-type filler handled with the represented special silane coupling agent of molecule formula I, the heat aging property of this rubber will be improved significantly.
More precisely, example can clearly be seen that shown in hereinafter, composition of the present invention is after carrying out 96 hours test under 180 ℃, its intensity and elongation retention are at least 68%, generally are at least 70%, be preferably 87%, generally speaking, thermal test carries out under 140 ℃, if after this test, sustainment rate reaches 70% at least, can think that then this composition is heat-stable.From then on can understand the superiority of the present composition in the data at an easy rate.
How the present invention improves heat aging property significantly, and its reason can't get across fully.Yet it is believed that this effect may be to cause owing to the separation surface between filler and the ethylene/alpha-olefin copolymer rubber significantly improves.
When adding the mixture of silane-modified or unmodified silica-type filler and a kind of organopolysiloxane of representing by the molecule formula II, can reach above-mentioned effect of the present invention equally.(A) ethylene/alpha-olefin copolymer rubber
The ethylene/alpha-olefin copolymer rubber is as the basic polymkeric substance in the present composition, it is a kind of ethene and at least a multipolymer that is selected from the 'alpha '-olefin monomers that contains 3 to 10 carbon atoms, the example of this alpha-olefin is a propylene, 1-butylene, the 1-amylene, the 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene.The content of ethene is generally 50～95 moles of %, is preferably 60～92 moles of %.
The ethylene/alpha-olefin copolymer rubber also can contain at least one polyenoid component.
As the specific example of polyenoid component, that can mention has a linear non-conjugated diene, as 1, and 4-hexadiene, 1, the 6-octadiene, 2-methyl isophthalic acid, 5-hexadiene, 6-methyl isophthalic acid, 5-heptadiene and 7-methyl isophthalic acid, 6-octadiene; The ring-type non-conjugated diene, as cyclohexadiene, dicyclopentadiene, methyl tetrahydroindene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornylene and 6-chloromethyl-5-isopropenyl-2-nirbornene; And trienes as 2,3-diisopropylidene-5-norbornylene, 2-ethylidene-3-isopropylidene-5-norbornylene, 2-propenyl-2,2-norbornadiene, 1,3,7-sarohornene and 1,4,9-triolefin in the last of the ten Heavenly stems.Ring-type non-conjugated diene and 1,4-hexadiene are best, and dicyclopentadiene and 5-ethylidene-2-norbornene are especially good.The amount that the polyenoid component carries out copolymerization should make formed multipolymer iodine number be up to 30, preferably is up to 20.
Its limiting viscosity of used multipolymer (η) is preferably 0.5 to 4.0 deciliter/gram, especially 1.0 to 3.5 deciliter/gram (measuring in naphthalane under 135 ℃ of conditions).
If its limiting viscosity of the rubber combination that is obtained (η) is too little and be lower than above-mentioned scope, then its mechanical property deficiency; If its limiting viscosity (η) is higher than above-mentioned scope, then can reduce its processing characteristics.
The ethylene/alpha-olefin copolymer rubber can be a kind of multipolymer with unsaturated carboxylic acid or derivatives thereof (as a kind of acid anhydrides or ester) graft copolymerization.If use this ethylene/alpha-olefin copolymer rubber through modification, its tensile strength of rubber behind so final the curing just can further be improved, and surpasses the tensile strength that unmodified rubber reached.In addition, tensile strength under the thermal ageing condition and elongation retention can further be improved.
Can mention following compounds as with the example of unsaturated carboxylic acid, its acid anhydride and the ester of the graft copolymerization of ethylene/alpha-olefin copolymer rubber, be in no way limited to listed compound yet can be used for graft compound of the present invention.
Unsaturated carboxylic acid:
Vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, tetrahydrophthalic acid and two ring (2,2,1)-hept-2-ene"s-5,6-dicarboxylic acid.
Unsaturated carboxylic acid anhydrides:
Maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydronaphthalic anhydride and two ring (2,2,1)-hept-2-ene"s-5,6-dicarboxylic anhydride.
Maleic anhydride the best wherein.
Esters of unsaturated carboxylic acids:
Methyl acrylate, methyl methacrylate, dimethyl maleic acid ester, monomethyl maleic acid ester, the diethyl fumarate, dimethyl itaconic ester, diethyl citraconate, dimethyl tetrahydro phthalic ester and dimethyl two rings (2,2,2) hept-2-ene"-5, the 6-dicarboxylic ester.
Wherein methyl acrylate and ethyl propenoate the best.
As grafted monomer, these unsaturated carboxylic acids and derivative thereof can use separately, also can use with the form of two or more mixtures.In a word, the consumption of the unsaturated carboxylic acid or derivatives thereof of using as grafting is preferably 0.1 to 10 weight part, and especially 0.2 to 5 weight part is better, is as the criterion with per 100 parts by weight of ethylene/alpha-olefin copolymer rubber.
If the amount of grafted monomer very little and be lower than above-mentioned scope, then is difficult to reach the purpose of further improvement intensity and heat aging property.If the amount of grafted monomer is higher than above-mentioned scope, it is not enough that then resulting its processing characteristics of rubber combination or cold tolerance are tending towards again.
The graft copolymerization of ethylene/alpha-olefin copolymer rubber and unsaturated carboxylic acid or derivatives thereof carries out in the presence of free-radical initiator.
This reaction can be carried out in solution or under molten state.Carry out if this is reflected under the molten state, in forcing machine, carry out continuous reaction so and then can reach top efficiency.
Graft reaction uses preferably that to have decomposition temperature be 150 ℃ to 270 ℃, be 1 minute free-radical initiator in the decomposition temperature half-life.
As special case, the organo-peroxide that can mention and organic peracid ester such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2.5-dimethyl-2.5-two (peroxide benzoate) hexin-3,1,4-two (tert-butyl hydroperoxide different third) benzene, lauroyl peroxide, tertiary butyl peracetic acid ester, 2.5-dimethyl-2,5-two (t-butyl peroxy) hexin-3,2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, TBPB tertiary butyl perbenzoate, the tertiary butyl is crossed the phenylacetic acid ester, the tertiary butyl is crossed secondary octanoate, and the tertiary butyl is crossed pivalate, and cumyl crosses pivalate and the tertiary butyl is crossed the diethylacetic acid ester.
Consider mechanical property and processing characteristics, its mooney viscosity of ethylene/alpha-olefin copolymer rubber (ML modification or unmodified
1+4(100 ℃)) be preferably 5 to 180, especially 10 to 120 for well.
(B) the silica-type filler of silane treatment
The silane compound of representing with following molecular formula
R in the formula
1Represent alkenyl, chlorination alkenyl or chlorine alkyl, preferably allyl group, vinyl or chloropropyl, R
2Represent low-carbon alkyl,, use as the silane coupling agent that the silica-type filler is carried out silane treatment as methyl or ethyl.As special case, that can mention has allyltrimethoxysilanis, an allyltriethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, r-chloropropyl trimethoxyl silane and chloropropyl triethoxysilane, spendable silane coupling agent are not limited to the above-mentioned compound that exemplifies.
All known silica-type fillers all can be used as by the filler of silane treatment, for example, preferably use dry method silicon-dioxide, wet method silicon-dioxide, synthetic silicate type white carbon black, talcum and clay.In these silica-type fillers, specific surface area (surface area test method) is 50 to 400 meters
2/ gram, especially 100 to 300 meters
2The dry method silicon-dioxide of/gram is particularly suitable for reaching purpose of the present invention.In various silica-type fillers, the silanol group content of dry method silicon-dioxide is less relatively, if this silicon-dioxide is handled with above-mentioned silane, then this silanol group is closed, and can think that this silicon-dioxide combines with rubber effectively by the functional group of silane.
The silane coupling agent consumption of being represented by above-mentioned molecule formula I is 0.1～5%(weight), be preferably 0.5～4%(weight), most preferably be 1～3%(weight), be as the criterion with carbon content in the filler of handling.
If the amount of silane coupling agent is very little, just can not reach desirable heat aging property, if the amount of silane coupling agent is too many, then be again uneconomic.
If use silane treatment silica-type filler, then can improve heat aging property significantly, in addition, because the unit weight of filler increases, the ethylene/alpha-olefin copolymer rubber can successfully carry out with mixing of filler, and therefore, silane treatment has special industrial significance.
The processing of silane coupling agent is carried out with known method, for example, it is to infeed in the treatment chamber that is made of the vertical pipe type stove continuously silica-type filler and silane compound simultaneously and react that the method that can mention has a kind of method, and this disclose announcement in 17049/66 at Japanese Patent; Another kind method is that the silica-type filler contacts under relatively low temperature with silane compound, carries out pyroprocessing then, and then with the further drying treatment of rare gas element, this discloses in 6379/85 at Japanese Patent and has disclosed.
The content of carbon is measured according to follow procedure in the silica-type filler of silane treatment.
Or rather, the silica-type filler of silane treatment is a thorough drying in 150 ℃ nitrogen gas stream, measures the content of carbon then with elemental analyser.
Certainly, in concrete enforcement of the present invention, use the polysiloxane of chloride alkyl, also can use untreated silica-type filler.
(C) organopolysiloxane
In the present invention, the organopolysiloxane that uses as organopolysiloxane has the general formula as following molecular formula (II):
（R
1）
a（R
2）
bSiO
（4-a-b）/2（Ⅱ）
R in the formula
1Represent univalence hydrocarbyl, especially low-carbon alkyl or phenyl, R
2Represent chlorine alkyl or alkenyl, a is the number between 1 to 2.5, and b is between 0.01 to 1.2, the especially number between 0.05 to 1.0, and a and b sum must be in 1.8 to 3 scopes.
R in the preferred use molecule formula II
1Be the organopolysiloxane of methyl or phenyl, in addition, the R in the molecule formula II
2The chlorine alkyl that preferably has 3 to 8 carbon atoms as γ-chloropropyl or δ-chloropropyl, or has the alkenyl of 2 to 8 carbon atoms, as vinyl or allyl group.
The number-average molecular weight of organopolysiloxane (Mn) is 10
2To 10
6, be preferably 10
3To 10
5, most preferably be 5 * 10
3To 5 * 10
4
If the polymerization degree is higher than above-mentioned scope, then organopolysiloxane is not enough to compatiblely with the ethylene/alpha-olefin copolymer rubber, thereby causes that intensity reduces.If the polymerization degree is lower than above-mentioned scope, just be difficult to obtain desired heat aging property.
(D) prescription
According to a kind of particular embodiment of the present invention, in rubber combination, the silica-type filler (B) that has at least the above-mentioned special silane coupling agent of a kind of usefulness to handle, its consumption is 10 to 100 weight parts, be preferably 15 to 80 weight parts, be preferably 20 to 60 weight parts especially, it is added in the modification or unmodified ethylene/alpha-olefin copolymer rubber (A) of 100 weight parts.
If the add-on of the silica-type filler of silane treatment is lower than or is higher than above-mentioned scope, then its mechanical property of rubber after the sulfuration such as tensile strength and elongation will be not enough, and its heat aging property also is unsafty.
According to another kind of particular embodiment of the present invention, in rubber combination, with above-mentioned special organopolysiloxane (C) with 0.5 to 30 weight part, preferred 1 to 25 weight part, preferred especially 1.5 to 20 weight parts join in the modification or unmodified ethylene/alpha-olefin copolymer (A) of 100 weight parts, silica-type filler that will handle with above-mentioned silane coupling agent then or undressed (B) is with 10 to 100 weight parts, preferred 15 to 80 weight parts, and preferred especially 20 to 60 weight parts add.
If the amount of organopolysiloxane (C) very little and be lower than above-mentioned scope, just be difficult to obtain desired heat aging property, if the amount of organopolysiloxane (C) is too many and be higher than above-mentioned scope, then be difficult to obtain desired intensity, and said composition involves great expense.Therefore the consumption of organopolysiloxane (C) very little or all bad too much.In addition, silica-type filler (B) consumption of handling with silane coupling agent very little or too much can not obtain desired intensity, and silica-type filler (B) consumption of crossing with silane treatment very little or also bad too much.
The preferably combination of each relevant component will describe in detail in will giving an example below.
According to the intended purpose of solidifying product, can be with known various additives, as rubber stiffener, tenderizer, solidifying agent, auxiliary curing agent adds in the rubber combination of the present invention.
In the present invention, although according to predetermined purposes difference, the total amount of composition can change, and is as the criterion with whole composition, and total consumption of above-mentioned component (A) to (C) preferably is 60%(weight at least), be 80%(weight especially at least).
Carbon black as rubber stiffener can be semi-reinforcing carbon black (SRF), general purpose furnace black (GPF) pushes furnace black (FEF) fast, medium super abrasion furnace black (ISAF), super abrasion furnace black (SAF), fine particle thermal black (FT) and MT medium thermal black (MT).
The consumption of rubber stiffener is corresponding decision with intended purpose.But the amount of preferable rubber stiffener reaches as high as 50 weight parts, especially reaches as high as 30 weight parts, is as the criterion with the total amount of the component (A) to (C) of per 100 weight parts.
It is gratifying that the general tenderizer of General Purpose Rubber uses in the present invention.For example, that can mention has an oil type tenderizer, as treated oil, lubricating oil, and ucon oil, paraffin, whiteruss, petroleum pitch and Vaseline; The coal-tar type tenderizer, as coal tar, coal-tar pitch; Saturated oil type tenderizer, as Viscotrol C, Toenol 1140, rape seed oil and Oleum Cocois; Wax, as beeswax, carnauba wax and lanolin, Yatall MA, ointment; Lipid acid and soap such as ricinolic acid, palmitinic acid, barium stearate, calcium stearate and zinc laurate, synthesized polymer material such as petroleum resin, atactic polypropylene(APP), coumarone-indene resin and vibrin, ester type softening agent such as Octyl adipate and dioctyl phthalate (DOP), and Microcrystalline Wax and rubber substitute (ointment).
The add-on of tenderizer is corresponding decision with intended purpose.But preferably the consumption of tenderizer is up to 50 weight parts, especially is up to 30 weight parts for well, is as the criterion with the total amount of the above-mentioned component (A) to (C) of per 100 weight parts.
Composition of the present invention is made solidifying product with following method with the uncured rubber mixture, earlier rubber stock is made desired shape, then as the ordinary rubber curing, rubber stock is solidified.Can adopt the solidifying agent method or finish solidification treatment with the electron beam radiation method.
The compound of sulphur and organo-peroxide can be used as solidifying agent.When with the compound of sulphur, that can mention has sulphur, sulfur subchloride, sulfur dichloride, morpholine disulfide, curing alkylphenol, tetramethyl-thiuram disulfide and dimethyl thiocarbamate selenium.Preferably use sulphur.The compound amount of sulphur is 0.1 to 10 weight part, is preferably 0.5 to 5 weight part, is as the criterion with per 100 weight part modifications or unmodified ethylene/alpha-olefin copolymer rubber (A).When using organo-peroxide, that can mention has dicumyl peroxide, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, 2,5-dimethyl-2,5-two (benzoyl peroxide) hexane, 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3,5-two-tert-butyl peroxide, two-t-butylperoxy-3,3,5-trimethyl-cyclohexane and tertbutyl peroxide.Wherein, preferably use dicumyl peroxide, two-tert-butyl peroxide and two-t-butylperoxy-3,3,5-trimethyl-cyclohexane.The consumption of organo-peroxide is 3 * 10
-4To 5 * 10
-2Mole number is preferably 1 * 10
-3To 3 * 10
-2Mole number is as the criterion with per 100 weight parts hexene/alpha-olefin copolymer rubber (A).
When the compound that uses sulphur during as solidifying agent, the best incorporated curing catalyst uses.The curing catalyst that can mention has thiazole type such as N-cyclohexyl-2-[4-morpholinodithio-sulfinyl amine, N-oxydiethylene--2-[4-morpholinodithio-sulfinyl amine, N, N-di-isopropyl-2-[4-morpholinodithio-sulfinyl amine, 2-mercaptobenzothiazole, 2-(2,4-dinitrobenzene) mercaptobenzothiazole, 2-2,6-diethyl-4-morpholine sulfo-) benzothiazole and dibenzothiazyl-disulfide; Guanidine type promotor, as vulkacit D, triphenyl guanidine, two-ortho position-tolyl guanidine, neighbour-tolyl two guanidines, and vulkacit D phthalic ester; Aldehyde amine or aldehyde ammonia type promotor, as the reaction product of acetaldehyde/aniline, butyraldehyde/aniline condensation thing, vulkacit H and aldamine, imidazoline type promotor is as the 2-mercaptoimidazoline; Thiocarbamide type promotor, as thiocarbanilide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea and two-ortho position-tolylthiourea; Thiuram type promotor, as tetramethylthiuram monosulfide, tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide and four sulfuration pentamethyl-thiurams, dithionate's type promotor, as ziram, zinc diethyldithiocarbamate, two-just-zinc dibutyl dithiocarbamate, zinc-ethylphenyl dithiocarbamate, zinc dibutyl dithiocarbamate, Sodium dimethyldithiocarbamate 40min; Selenium dimethyl dithiocarbamate and tellurium diethyl dithiocarbamate, xanthogenate type promotor is as dibutyl xanthogenic acid zinc; And the promotor of other type, as the flowers of zinc.The consumption of vulcanization accelerator is 0.1 to 20 weight part in the ethylene/alpha-olefin copolymer rubber of per 100 weight parts, is preferably 0.2 to 10 weight part.
When using organo-peroxide, preferably be used in combination with auxiliary curing agent as solidifying agent.Auxiliary curing agent can be a sulphur, quininie dioxime type auxiliary agent, as paraquinonedioxime, iso-butylene acid type promotor is as poly-di glycol ester, allylic auxiliary agent, as diallyl phthalate and triallyl cyanurate, maleimide type auxiliary agent, and other analog assistant are as Vinylstyrene.The amount of every mole of organo-peroxide adding vulcanization aid is 0.5 to 2 mole, preferably about 1 mole.
When adopting electron beam to be cured without solidifying agent, the energy of electron beam is 0.1 to 10 million-electron-volt, is preferably 0.3 to 2.0 million-electron-volt.This electron beam is applied on the uncured rubber mixture of moulding by following method, so absorbed electron beam amount is 0.5 to 35 megarad, 0.5 to 10 megarad preferably.In this case, above-mentioned auxiliary curing agent can be used in combination with the organo-peroxide solidifying agent.The auxiliary curing agent amount that adds in per 100 parts by weight of ethylene/alpha-olefin copolymer rubber (A) is 1 * 10
-4To 1 * 10
-1Mole is preferably 1 * 10
-3To 3 * 10
-2Mole.In addition, also can in composition of the present invention, add tinting material as required, anti-aging agent, dispersion agent and fire retardant.
(E) preparation of rubber combination
The uncured rubber mixture of the present composition prepares according to following method.
Or rather, ethylene/alpha-olefin copolymer rubber (A), the silica-type filler of handling with silane coupling agent (can select organopolysiloxane (C) for use) (B), in case of necessity, rubber stiffener and tenderizer use mixing machine under 80 to 170 ℃ of conditions, kneaded 3 to 10 minutes as banbury mixer, use roller such as mill then, add vulcanizing agent in case of necessity, curing catalyst or auxiliary curing agent, mixture was kneaded in 40 to 80 ℃ roller 5 to 30 minutes, and kneaded mixture is recovered the back and forms band shape or sheet rubber stock.
The rubber stock extrusion die press of preparation like this, stack or press are molded as predetermined shape.In this forming operation or afterwards, with rubber stock be incorporated into solidify jar in and heating 1 to 30 minute under 150 ℃ to 270 ℃ conditions, perhaps with rubber stock according to the aforesaid method electron beam irradiation, thereby obtain solidifying product.This solidification treatment can be used model, also can be without model.Under the situation without model, moulding and curing operation normally carry out in a continuous manner.
If adopt the electron beam irradiation sulfuration, then do not contain solidifying agent in the rubber stock.
Heating in the vulcanizing boiler can be adopted warm air, glass sphere thermopnore, uhf electromagnetic wave, steam or the like.
Shown in following embodiment, so the rubber combination of the present invention of preparation has good mechanical property, and electrical insulation capability and heat aging property are specially adapted to produce the electric wire foreskin, pipe, belt, rubber rollers, packing ring, sealing member, rubber hose etc.
To describe the present invention in detail with following embodiment, these embodiment are the connotation of the scope of the invention without limits.
Example 1:
According to following prescription, with silica-type filler (B) the preparation rubber combination of ethylene/alpha-olefin copolymer rubber (A) and silane treatment.
The ethylene/alpha-olefin copolymer rubber
Ethylene content: 68 moles of %
Alpha-olefin: propylene
〔η〕：1.8
Iodine number: the 5(ethylidene norbornene)
The silicon-dioxide of silane treatment (B)
Silicon-dioxide: dry method silicon-dioxide, its specific surface area are 200 meters
2/ gram
Silane coupling agent: r-chloropropyl trimethoxyl silane
Treatment capacity (carbon content): 2.0%(weight)
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
The silicon-dioxide of silane treatment: 30.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide
1): 5.0 weight parts
Sulphur: 0.2 weight part
Antioxidant MB
2): 2.0 weight parts
Antioxidant 200
3): 1.0 weight parts
Annotate:
1) the Mitsui Dcp 40c that provides by Mitsui petroleum chemistry company
2) 2-mercaptobenzimidazole that provides by Ouchi Shinko.
3) by Ouchi Shinko provide 2,6-two-tertiary butyl-4-methylphenol.
Kneaded 20 minutes under 60 to 70 ℃ of conditions with 8 inch mills, then with this mixture cure under pressure 10 minutes under 170 ℃ of conditions, form the cured sheets of 2 mm thick, this sheet is used for measuring.
Measure following performance according to the method for JIS K-6301:
Physicals under the standard state
Tensile strength (TB) and elongation (EB)
Heat-resistant aging (thermal ageing condition: 180 ℃ * 96 hours)
Tensile strength retention rate AR(TB) and elongation AR(EB)
Gained the results are shown in the table I.
Example 2
With the step of same method repetition example 1, difference is with following ethylene/alpha-olefin copolymer rubber:
Ethylene content: 80 moles of %
Alpha-olefin: propylene
〔η〕：1.5
Example 3
With the step of same method repetition example 1, difference is to use following ethylene/alpha-olefin copolymer rubber:
Ethylene content: 80 moles of %
Alpha-olefin: propylene
〔η〕：1.5
Iodine number: the 3(vinyl norbornene)
Example 4
With the step of same method repetition example 1, difference is to use following ethylene/alpha-olefin copolymer rubber:
Ethylene content: 90 moles of %
Alpha-olefin: 1-butylene
〔η〕：1.3
Comparative Examples 1
With the step of same method repetition example 1, difference is to replace the silicon-dioxide of handling with untreated silica.
Example 5
With the step of same method repetition example 1, difference is to use the silicon-dioxide of following silane treatment:
Silicon-dioxide: dry method silicon-dioxide, its specific surface area are 200 meters
2/ gram
Silane coupling agent: vinyltrimethoxy silane
Treatment capacity (carbon content): 2.5%(weight)
Example 6
With the step of same method repetition example 1, difference is to use the silicon-dioxide of following silane treatment:
Silicon-dioxide: dry method silicon-dioxide, its specific surface area are 200 meters
2/ gram
Silane coupling agent: allyltrimethoxysilanis
Treatment capacity (carbon content): 3.0%(weight)
Example 7
With the step of same method repetition example 1, difference is the treatment capacity of silane treatment silicon-dioxide, and its carbon content becomes 0.5%(weight).
Example 8
With the step of same method repetition example 1, difference is the disposal amount of silane treatment silicon-dioxide, and its carbon content becomes 3.5%(weight).
Example 9
Repeat the step of example 2 with same method, difference is to use the ethylene/alpha-olefin copolymer rubber of modification, and this modified copolymer rubber is with maleic anhydride modified and formation with ethylene/alpha-olefin copolymer rubber used in the example 2.
Maleic anhydride content: per 100 gram copolymer rubbers 5 * 10
-3Mole
Example 10
With the step of same method repetition example 9, difference is to use the silicon-dioxide of following silane treatment.
Silicon-dioxide: dry method silicon-dioxide, its specific surface area are 200 meters
2/ gram
Silane coupling agent: vinyltrimethoxy silane
Treatment capacity (carbon content): 2.5%(weight)
Example 11
With the step of same method repetition example 9, difference is to use the silicon-dioxide of following silane treatment.
Silicon-dioxide: dry method silicon-dioxide, its specific surface area are 200 meters
2/ gram
Silane coupling agent: allyltrimethoxysilanis
Treatment capacity (carbon content): 3.0%(weight)
Example 12
With the step of same method repetition example 4, difference is to use the ethylene/alpha-olefin copolymer rubber of modification, and this modified copolymer rubber forms ethylene/alpha-olefin copolymer rubber used in the example 4 with the ethyl propenoate modification.
Ethyl propenoate content: per 100 gram copolymer rubbers 10
-2Mole
Example 13
With the step of same method repetition example 1, difference is that the ethylene/alpha-olefin copolymer rubber that uses is as follows, and prescription is also done following change:
The ethylene/alpha-olefin copolymer rubber
Ethylene content: 70 moles of %
Alpha-olefin: propylene
〔η〕：2.7
Iodine number: 10(vinylidene norbornylene)
Prescription:
Ethylene/alpha-olefin copolymer: 100.0 weight parts
The silicon-dioxide of silane treatment: 30.0 weight parts
Stearic acid 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Vulkacit D PTT
1): 0.5 weight part
Promotor ZnBDC
2): 1.5 weight parts
Accelerant MBT S
3): 3.0 weight parts
Sulphur: 1.5 weight parts
Oxidation inhibitor AANP
4): 1.0 weight parts
Annotate:
1) dipentamethylene thiuram tetrasulfide that provides by Ouchi Shinko
2) two-just-butyl dithiocarbamate that provides by Ouchi Shinko
3) dibenzothiazyl-disulfide that provides by Ouchi Shinko
4) the 3-acetaldol that provides by Ouchi Shinko and the powdery condenses of naphthalidine.
Example 14
With the step of same method repetition example 1, difference is to fill a prescription and does following change.
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
The silicon-dioxide of silane treatment: 15.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide
1): 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB
2): 2.0 weight parts
Oxidation inhibitor 200
3): 1.0 weight parts
Example 15
With the step of same method repetition example 1, difference is done following change at prescription.
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
The silicon-dioxide of silane treatment: 50.0 weight parts
Stearic acid: 2.0 weight parts
Ucon oil
1): 20.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:2.0 weight part
Oxidation inhibitor 200:1.0 weight part
Annotate:
1) the lucant HC-600 that provides by Mitsui petroleum chemistry company
Example 16
With the step of same method repetition example 1, difference is to use the silicon-dioxide of following silane treatment.
The silicon-dioxide of silane treatment
Silicon-dioxide: Nipsil VH
3
Silane coupling agent: r-chloropropyl trimethoxyl silane
Treatment capacity (carbon content): 2.5%(weight)
Comparative Examples 2
With the step of same method repetition example 16, difference is to fill a prescription and does following change.
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
The silicon-dioxide of silane treatment: 5.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:2.0 weight part
Oxidation inhibitor 200:1.0 weight part
Comparative Examples 3
With the step of same method repetition example 16, difference is to fill a prescription and does following change.
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
The silicon-dioxide of silane treatment: 110.0 weight parts
Stearic acid: 2.0 weight parts
Ucon oil
1): 60.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:2.0 weight part
Oxidation inhibitor 200:1.0 weight part
Annotate:
1) routine gained the results are shown in the table I more than the Lucant HC-600 that is provided by Mitsui petroleum chemistry company.
Example 17
According to following prescription, prepare a kind of rubber combination to (C) component with requisite (A).
Ethylene/alpha-olefin copolymer rubber (A)
Ethylene content: 68 moles of %
Alpha-olefin: propylene
〔η〕：1.8
Iodine number: the 5(ethylidene norbornene)
The silicon-dioxide of silane treatment (B)
Silicon-dioxide: dry method silicon-dioxide, its specific surface area are 200 meters
2/ gram
Silane coupling agent: chloropropyl trimethicone
Treatment capacity (carbon content): 2.0%(weight)
Organopolysiloxane (C)
Chemical structural formula: (CH
3)
1.6(CCH
2CH
2CH
2)
0.2SiO
Number-average molecular weight: 5.0 * 10
3
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
The silicon-dioxide of silane treatment: 30.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide
1): 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB
2): 2.0 weight parts
Oxidation inhibitor 200
3): 1.0 weight parts
Annotate:
1) the Mitsui DCP 40C that provides by Mitsui petroleum chemistry company,
2) 2-mercaptobenzimidazole that provides by Ouchi shinko,
3) the 2.6-di-tert-butyl-4-methy phenol that provides by Ouchi shinko
Kneaded 20 minutes under 60 to 70 ℃ with 8 English inch mills, then with this mixture 170 ℃ of following press vulcanizations 10 minutes, form the sulfuration sheet of 2 mm thick, this sheet is used for measuring.
Measure following performance according to the method for JIS K6301:
Physicals under the standard state
Tensile strength (TB) and elongation (EB)
Heat-resistant aging (thermal ageing condition: 180 ℃ * 96 hours)
Tensile strength retention rate AR(TB)
With elongation retention AR(EB)
Gained the results are shown in the table II.
Example 18
With the step of same method repetition example 17, difference is to use following ethylene/alpha-olefin copolymer rubber.
Ethylene content: 80 moles of %
Alpha-olefin: propylene
〔η〕：1.5
Example 19
With the step of same method repetition example 17, difference is to use following ethylene/alpha-olefin copolymer rubber.
Ethylene content: 80 moles of %
Alpha-olefin: propylene
〔η〕：3.0
Iodine number: the 3(vinyl norbornene)
Example 20
With the step of same method repetition example 17, difference is to use following ethylene/alpha-olefin copolymer rubber.
Ethylene content: 90 moles of %
Alpha-olefin: 1-butylene
〔η〕：1.3
Example 21
With the step of same method repetition example 17, difference is to use following poly organic silicon alkane,
Poly organic silicon alkane
Chemical structural formula: (CH
3)
1.8(CH
2=H)
0.2SiO
Number-average molecular weight: 5.1 * 10
3
Example 22
With the step of same method repetition example 17, difference is to have used the silicon-dioxide with following silane treatment,
Silicon-dioxide: have 200 meters
2The dry method silicon-dioxide of/gram specific surface area
Silane coupling agent: vinyltrimethoxy silane
Treatment capacity (carbon content): 2.5%(weight)
Example 23
With the step of same method repetition example 17, difference has been to use the silicon-dioxide of following silane treatment,
Silicon-dioxide: have 200 meters
2The dry method silicon-dioxide of/gram specific surface area
Silane coupling agent: vinyltrimethoxy silane
Treatment capacity (carbon content): 30%(weight)
Comparative example 4
With the step of same method repetition example 17, difference is not use poly organic silicon alkane, and uses untreated silica.
Comparative example 5
With the step of same method repetition example 17, difference is to use following organopolysiloxane and untreated silica,
Polydimethylsiloxane
Number-average molecular weight: 4.8 * 10
3
Example 24
With the step of same method repetition example 17, difference is the treatment capacity of silane treatment silicon-dioxide (carbon content) is become 0.5%(weight).
Example 25
With the step of same method repetition example 17, difference is the treatment capacity of silane treatment silicon-dioxide (carbon content) is become 3.5%(weight).
Example 26
With the step of same method repetition example 17, difference is the number-average molecular weight of poly organic silicon alkane is become 6 * 10
4
Example 27
With the step of same method repetition example 17, difference is to use following organopolysiloxane,
Organopolysiloxane
The average composition: (CH
3)
1.9(ClCH
2CH
2CH
2)
0.1SiO
Number-average molecular weight: 5.5 * 10
3
Example 28
With the step of same method repetition example 17, difference is to use following organopolysiloxane,
Organopolysiloxane
The average composition: (CH
3)
1.5(ClCH
2CH
2CH
2)
0.5SiO
Number-average molecular weight: 5.5 * 10
3
Example 29
With the step of same method repetition example 17, difference is that the ethene improved/alpha-olefin copolymer rubber that uses is obtained with maleic anhydride modified by the ethylene/alpha-olefin copolymer rubber that uses in the example 18,
Maleic anhydride content: per 100 gram copolymer rubbers 5 * 10
-3Mole
Example 30
With the step of same method repetition example 17, difference is to use following organopolysiloxane,
Organopolysiloxane
The average composition: (CH
3)
1.8(CH
2=CH)
0.2SiO
Number-average molecular weight: 4.8 * 10
3
Example 31
With the step of same method repetition example 29, difference is to use the silicon-dioxide of following silane treatment,
Silicon-dioxide: have 200 meters
2The dry method silicon-dioxide of/gram specific surface area
Silane coupling agent: vinyltrimethoxy silane
Treatment capacity (carbon content): 2.5%(weight)
Example 32
With the step of same method repetition example 20, difference is that the ethene improved/alpha-olefin copolymer rubber that uses is obtained with the ethyl propenoate modification by the ethylene/alpha-olefin copolymer rubber that uses in the example 20.
Ethyl propenoate content: per 100 gram copolymer rubbers 10
-2Mole
Example 33
Repeat the step of example 17 with same method, difference is to use following ethylene/alpha-olefin copolymer rubber, prescription is become as described below, and is cured 20 minutes at 160 ℃.
The ethylene/alpha-olefin copolymer rubber
Ethylene content: 70 moles of %
Alpha-olefin: propylene
〔η〕：2.7
Iodine number: the 10(ethylidene norbornene)
Prescription:
Ethylene/alpha-olefin copolymer: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
The silicon-dioxide that silane treatment is crossed: 30.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Vulkacit D PTT
1): 0.5 weight part
Promotor ZnBDC
2): 1.5 weight parts
Accelerant MBT S
3): 3.0 weight parts
Sulphur: 1.5 weight parts
Oxidation inhibitor: 1.0 weight parts
Annotate: the 1) dipentamethylene thiuram tetrasulfide that provides by Ouchi Shinko.
2) the di-n-butyl disulfide group carbaminate that provides by Ouchi Shinko.
3) dibenzothiazyl-disulfide that provides by Ouchi Shinko.
4) the 3-acetaldol that provides by Ouchi Shinko and the condensation powder of naphthalidine.
Example 34
With the step of same method repetition example 17, difference is prescription is become as described below,
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
The silicon-dioxide of silane treatment: 15.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:2.0 weight part
Oxidation inhibitor 200:1.0 weight part
Example 35
With the step of same method repetition example 17, difference is prescription is become as described below,
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
The silicon-dioxide of silane treatment: 50.0 weight parts
Stearic acid: 2.0 weight parts
Ucon oil
1): 20.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:2.0 weight part
Oxidation inhibitor 200:1.0 weight part
Annotate:
1) the Lucant HC-600 that provides by Mitsui petroleum chemistry company,
Example 36
With the step of same method repetition example 17, difference is that the quantitative change of organopolysiloxane is 20 weight parts.
Example 37
With the step of same method repetition example 17, difference is to use the silicon-dioxide of following silane treatment,
The silicon-dioxide of silane treatment
Silicon-dioxide: Nipsil VH
3
Silane coupling agent: r-chloropropyl trimethoxyl silane
Treatment capacity (carbon content): 2.5%(weight)
Comparative example 6
With the step of same method repetition example 17, difference is prescription is become as described below.
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100 weight parts
Organopolysiloxane: 3.0 weight parts
The silicon-dioxide of silane treatment: 5.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:2.0 weight part
Oxidation inhibitor 200:1.0 weight part
Comparative example 7
With the step of same method repetition example 37, difference is prescription is become as described below,
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100 weight parts
Organopolysiloxane: 3.0 weight parts
The silicon-dioxide of silane treatment: 110.0 weight parts
Stearic acid: 2.0 weight parts
Ucon oil: 60.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:2.0 weight part
Oxidation inhibitor: 1.0 weight parts
The foregoing description obtains the results are shown in table 2.
Example 38
With the ethylene/alpha-olefin copolymer rubber (A) of following modification, silica filler (B) and organopolysiloxane (C),, ethene improved/alpha-olefin copolymer rubber by following formulation rubber combination
Alpha-olefin: propylene
Ethylene/propene mol ratio: 80/20
Mooney viscosity ML
1+4(100 ℃): 20
Maleic anhydride content: 0.5%(weight)
Silica-type filler (B)
Have 200 meters
2The dry method silicon-dioxide of/gram specific surface area
Organopolysiloxane (C)
Chemical structural formula: (CH
2)
1.8(CH
2=CH)
1.2SiO
Number-average molecular weight Mn:5.1 * 10
3
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
Silica-type filler: 30.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide
1): 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB
2): 2.0 weight parts
Oxidation inhibitor 200
3): 1.0 weight parts
Annotate:
1) the Mitsui DCP 40C that provides by Mitsui petroleum chemistry company
2) 2-mercaptobenzimidazole that provides by Ouchi shinko
3) the 2.6-di-t-butyl-4-cresylol that provides by Ouchi shinko
With 8 inches mill, kneaded 20 minutes at 60 to 70 ℃, subsequently with mixture 170 ℃ of following cure under pressures 10 minutes, form the cured sheet of 2 mm thick, this sheet material is used for test.
Following performance is that the method according to JIS K-6301 records.
Physicals under the standard state
Tensile strength (TB) and elongation (EB)
Heat-resistant aging (thermal ageing condition: 180 ℃ * 96 hours)
Tensile strength retention rate AR(TB) and elongation retention AR(EB)
What obtain the results are shown in table 3.
Example 39
With the step of same method repetition example 38, difference is to use the ethylene/alpha-olefin copolymer rubber of following modification.
Alpha-olefin: propylene
Ethylene/alpha-olefin mol ratio: 70/30
Iodine number: the 2(vinyl norbornene)
Mooney viscosity ML
1+4(100 ℃): 60
Maleic anhydride: 0.5%(weight)
Example 40
With the step of same method repetition example 38, difference is to use the ethylene/alpha-olefin copolymer rubber of following modification.
Alpha-olefin: 1-butylene
Ethene/1-butylene mol ratio: 90/10
Mooney viscosity ML
1+4(100 ℃): 15
Maleic anhydride: 1.0%(weight)
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
Organopolysiloxane: 20.0 weight parts
Silicon-dioxide thin slice: 30.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide
1): 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB
2): 2.0 weight parts
Oxidation inhibitor 200
3): 1.0 weight parts
Example 42
With the step of same method repetition example 38, difference is to use following organopolysiloxane.
Organopolysiloxane
Chemical structural formula: (CH
3)
1.9(CH
2=CH)
0.1SiO
Number-average molecular weight: 4.5 * 10
3
Example 43
With the step of same method repetition example 38, difference is to use following organopolysiloxane.
Organopolysiloxane
The average composition: (CH
3)
1.5(CH
2=CH)
0.5SiO
Number-average molecular weight: 6.1 * 10
3
Example 44
With the step of same method repetition example 38, difference is that the number-average molecular weight of organopolysiloxane becomes 8.0 * 10
4
Example 45
With the step of same method repetition example 38, difference is to use following silica-type filler.
Silica filler
Silicon-dioxide: Nipsil VH
3(providing) by Nippon silica
Example 46
With the step of same method repetition example 38, difference is to use following silica-type filler, and prescription becomes as described below.
The silica-type filler
Calcined clay (SatentonN0.1 that provides by Englhard mining industry and chemical company)
Prescription:
The ethylene/alpha-olefin copolymer rubber of modification: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
Calcined clay: 60.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide
1)5.0 weight part
Sulphur: 0.2 weight part
Oxidation inhibitor MB
2)2.0 weight part
Oxidation inhibitor 200
3)1.0 weight part
Comparative example 8
With the step of same method repetition example 38, difference is not use organopolysiloxane.
Comparative example 9
With the step of same method repetition example 38, difference is to use following organopolysiloxane.
Polydimethylsiloxane
Number-average molecular weight: 4.8 * 10
3
Example 47
With the step of same method repetition example 38, difference is to use the ethylene/alpha-olefin copolymer rubber of following modification.
Alpha-olefin: 1-butylene
Ethene/1-butylene mol ratio: 90/10
Mooney viscosity ML
1+4(100 ℃): 30
Ethyl propenoate content: 2.0%(weight)
Comparative example 10
With the step of same method repetition example 46, it is as described below that difference is that prescription becomes.
Prescription:
The ethylene/alpha-olefin copolymer rubber of modification: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
Calcined clay: 5.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:2.0 weight part
Oxidation inhibitor 200:1.0 weight part
Comparative example 11
With the step of same method repetition example 46, it is as described below that difference is that prescription becomes.
Prescription:
The ethylene/alpha-olefin copolymer rubber of modification: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
Calcined clay: 110.0 weight parts
Stearic acid: 2.0 weight parts
Ucon oil
1): 60.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:2.0 weight part
Oxidation inhibitor 200:1.0 weight part
Annotate:
1) the Lucant HC-600 that provides by Mitsui petroleum chemistry company
Comparative example 12
With the step of same method repetition example 46, difference is to replace with unmodified ethylene/alpha-olefin copolymer rubber the ethylene/alpha-olefin copolymer rubber of modification.
The foregoing description obtains the results are shown in table 3.
Example 47
With following ethylene/alpha-olefin copolymer rubber (A), silica-type filler (B) and organopolysiloxane (C) are by following formulation rubber combination.
Ethylene/alpha-olefin copolymer rubber (A)
Ethylene content: 68 moles of %
Alpha-olefin: propylene
〔η〕：1.8
Iodine number: the 5(ethylidene norbornene)
Silica-type filler (B)
Silicon-dioxide: have 200 meters
2The dry method silicon-dioxide of/gram specific surface
Organopolysiloxane (C)
Chemical structural formula: (CH
2)
1.8(CH
2=CH)
0.2SiO
Number-average molecular weight Mn:5.0 * 10
3
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
Silica-type filler: 30.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide
1): 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB
2): 2.0 weight parts
Oxidation inhibitor 200
3): 1 weight part
Annotate:
1) the Mitsui DCP40C that provides by Mitsui petroleum chemistry company
2) 2-mercaptobenzothiazole that provides by Ouchi Shinko
3) 2,6 di tert butyl 4 methyl phenol that provides by Ouchi Shinko
Kneaded 20 minutes under 60 to 70 ℃ with 8 inches mills, subsequently 170 ℃ with mixture cure under pressure 10 minutes, form the cured sheet of 2 mm thick, this sheet material is used for test.
Method according to JIS K-6301 records following character.
Physical properties under the standard state
Tensile strength (TB) and elongation (EB)
Heat-resistant aging (thermal ageing condition: 180 ℃ * 96 hours)
Tensile strength retention rate AR(TB) and elongation retention AR(EB) obtain the results are shown in table 4.
Example 48
With the step of same method repetition example 47, difference is with following ethylene/alpha-olefin copolymer rubber.
Ethylene content: 80 moles of %
Alpha-olefin: propylene
〔η〕：1.5
Example 49
With the step of same method repetition example 47, difference is with following ethylene/alpha-olefin copolymer rubber.
Ethylene content: 80 moles of %
Alpha-olefin: propylene
〔η〕：3.0
Iodine number: the 3(vinyl norbornene)
Example 50
In kind repeat the step of example 47, difference is to use following ethylene/alpha-olefin copolymer rubber.
Ethylene content: 90 moles of %
Alpha-olefin: 1-butylene
〔η〕：1.3
Comparative example 13
With the step of same method repetition example 47, difference is not use organopolysiloxane.
Comparative example 14
With the step of same method repetition example 47, difference is to use following organopolysiloxane.
Polydimethylsiloxane
Number-average molecular weight: 4.8 * 10
3
Example 51
With the step of same method repetition example 47, difference is to use following organopolysiloxane.
Organopolysiloxane
The average composition: (CH
3)
1.9(CCH
2CH
2CH
2)
0.1SiO
Number-average molecular weight: 5.5 * 10
3
Example 52
With the step of same method repetition example 47, difference is to use following organo-siloxane.
Organopolysiloxane
The average composition: (CH
3)
1.5(CCH
2CH
2CH
2)
0.5SiO
Number-average molecular weight: 5.2 * 10
3
Example 53
With the step of same method repetition example 47, difference is that the number-average molecular weight of organopolysiloxane becomes 6.0 * 10
4
Example 54
With the step of same method repetition example 48, difference is that the ethene improved/alpha-olefin copolymer rubber that uses is obtained with maleic anhydride modified by the ethylene/alpha-olefin copolymer rubber that uses in the example 48.
Maleic anhydride content: per 100 gram copolymer rubbers 5 * 10
-3Mole
Example 55
With the step of same method repetition example 54, difference is to use following silica-type filler.
Silica filler
Wet method silicon-dioxide: Nipsil VH
3(Nippon Silica provides)
Example 56
With the step of same method repetition example 50, difference is that the ethene improved/alpha-olefin copolymer rubber that uses is obtained with the ethyl propenoate modification by the ethylene/alpha-olefin copolymer rubber that uses in the example 50.
Ethyl propenoate content: per 100 gram copolymer 1s 0
-2Mole
Example 57
Repeat the step of example 47 with same method, difference is to use following ethylene/alpha-olefin copolymer rubber, fill a prescription as follows and 160 ℃ of curing 20 minutes down.
The ethylene/alpha-olefin copolymer rubber
Ethylene content: 70 moles of %
Alpha-olefin: propylene
〔η〕：2.7
Iodine number: the 10(ethylidene norbornene)
Prescription:
Ethylene/alpha-olefin copolymer: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
Silica-type filler: 30.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Vulkacit D PTT
1): 0.5 weight part
Promotor ZnBDC
2): 1.5 weight parts
Accelerant MBT S
3): 3.0 weight parts
Sulphur: 1.5 weight parts
Oxidation inhibitor AANP
4): 1.0 weight parts
Annotate:
1) dipentamethylene thiuram tetrasulfide that provides by Ouchi Shinko
2) zinc dibutyl dithiocaarbamate that provides by Ouchi Shinko
3) the curing hexichol thiazolyl that provides by Ouchi Shinko
4) the 3-acetaldol that provides by Ouchi Shinko and the condensation meal of naphthalidine.
Example 58
With the step of same method repetition example 47, difference is prescription is become as described below.
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 weight parts
Organopolysiloxane: 20.0 weight parts
Silica-type filler: 30.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide
1): 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB
2): 2.0 weight parts
Oxidation inhibitor 200
3): 1.0 weight parts
Example 59
With the step of same method repetition example 54, difference is prescription is become as follows.
Prescription:
Ethene improved/alpha-olefin copolymer rubber: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
Silica-type filler: 15.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide
1): 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB
2): 2.0 weight parts
Oxidation inhibitor 200
3): 1.0 weight parts
Example 60
With the step of same method repetition example 54, difference is prescription is become as follows.
Prescription:
Ethene improved/alpha-olefin copolymer rubber: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
Silica-type filler: 50.0 weight parts
Stearic acid: 2.0 weight parts
Ucon oil
1): 20.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:2.0 weight part
Oxidation inhibitor 200:1.0 weight part
Annotate:
1) the Lucant HC-600 that provides by Mitsui petroleum chemistry company
Comparative example 15
With the step of same method repetition example 55, difference is prescription is become as follows.
Prescription:
Ethene improved/alpha-olefin copolymer rubber: 100.0 weight parts
Organopolysiloxane: 3.0 weight parts
Silica-type filler: 5.0 weight parts
Stearic acid: 2.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:2.0 weight part
Oxidation inhibitor 200:1.0 weight part
Comparative example 16
With the step of same method repetition example 55, difference is prescription is become as follows.
Prescription:
Ethylene/alpha-olefin copolymer rubber: 100.0 amount parts
Organopolysiloxane: 3.0 weight parts
Silica-type filler: 110.0 weight parts
Stearic acid: 2.0 weight parts
Ucon oil
1): 60.0 weight parts
The flowers of zinc: 5.0 weight parts
Organo-peroxide: 5.0 weight parts
Sulphur: 0.2 weight part
Oxidation inhibitor MB:3.0 weight part
Oxidation inhibitor 200:1.0 weight part
Annotate:
1) the Lucant HC-600 the foregoing description that is provided by Mitsui petroleum chemistry company obtains the results are shown in table 4.
Claims (11)
1, a kind of heat-resistant rubber comosition, it contains (A) 100 parts by weight of ethylene/alpha-olefin copolymer or ethene improved/alpha-olefin copolymer, this modified copolymer is to be selected from unsaturated carboxylic acid, their acid anhydride and ester graft copolymerization forms with at least a, (B) (i) the silica-type filler handled with silane compound of 10 to 100 weight parts, the structural formula of said silane compound is as follows:
R in the formula
1Represent alkenyl, chlorination alkenyl or chlorine alkyl,
R
2Represent low-carbon alkyl,
Or the mixture of (ii) forming by the organopolysiloxane of the silica-type filler of 10 to the 100 said silane treatment of weight part or untreated silica type filler and 0.5 to 30 weight part, said organopolysiloxane on average composed as follows:
(R
1)
a(R
2)bSiO
(4-a-b)/2
R in the formula
1Represent the saturated or unsaturated alkyl of monovalence, R
2Represent chlorine alkyl or alkenyl, a is the number between 1 to 2.5, and b is the number between 0.01 to 1.2, and a and b sum must be in 1.8 to 3 scopes.
2, rubber combination as claimed in claim 1, the limiting viscosity of therein ethylene/alpha-olefin copolymer are 0.5 to 4.0 deciliter/gram (recording in 135 ℃ naphthalane).
3, it is 50/50 to 95/5 that rubber combination as claimed in claim 1, therein ethylene/alpha-olefin copolymer have the ethylene/alpha-olefin mol ratio.
4, rubber compound as claimed in claim 1, ethylene/alpha-olefin copolymer rubber (A) wherein contains unconjugated polyenoid, in an amount equivalent to the iodine number that reaches as high as 30.
5, rubber combination as claimed in claim 1, ethene improved/alpha-olefin copolymer wherein is monomer-grafted to ethylene/alpha-olefin copolymer and obtain with one, and monomeric consumption is per 100 parts by weight of ethylene/alpha-olefin copolymer 0.1 to 10 weight part.
6, rubber combination as claimed in claim 5, wherein monomer is a maleic anhydride.
7, rubber combination as claimed in claim 1, wherein the silica-type filler crossed of silane treatment is that a kind of to have carbon content be 0.1-5(weight) %(is as the criterion with the filler of handling) the silica-type filler crossed of silane treatment.
8, rubber combination as claimed in claim 1, wherein silane compound is the chloropropyl trialkoxy silane, vinyl trialkyl oxysilane or allyl group trialkoxy silane.
9, rubber combination as claimed in claim 1, silica-type filler are to have 100 to 300 meters
2The dry method silicon-dioxide of/gram (surface area test method) specific surface area.
10, rubber combination as claimed in claim 1, wherein the number-average molecular weight of organopolysiloxane is 100 to 10
6
11, heat-resistant rubber comosition as claimed in claim 1 is characterized in that, described composition further comprises 0.1 to 20 weight part solidifying agent and 0.1 to 20 weight part auxiliary curing agent.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP262585/87 | 1987-10-20 | ||
| JP26258687A JPH07119348B2 (en) | 1987-10-20 | 1987-10-20 | Modified rubber composition |
| JP262586/87 | 1987-10-20 | ||
| JP262583/87 | 1987-10-20 | ||
| JP262584/87 | 1987-10-20 | ||
| JP26258387A JPH01108238A (en) | 1987-10-20 | 1987-10-20 | Heat-resistant rubber composition containing surface-treated silica |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034738A CN1034738A (en) | 1989-08-16 |
| CN1026986C true CN1026986C (en) | 1994-12-14 |
Family
ID=26545607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88108524 Expired - Lifetime CN1026986C (en) | 1987-10-20 | 1988-10-20 | Heat-resistant rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1026986C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386372C (en) * | 2002-03-01 | 2008-05-07 | 罗狄亚化学公司 | Use of pretreated silicon dioxide as stabilizer |
| DE102005006870A1 (en) * | 2005-02-14 | 2006-08-24 | Byk-Chemie Gmbh | Surface-modified nanoparticles, process for their preparation and their use |
| JP6463881B2 (en) * | 2012-09-27 | 2019-02-06 | 東洋アルミニウム株式会社 | Food container |
| CN116285125B (en) * | 2023-03-28 | 2024-01-19 | 常州窗友塑胶有限公司 | Sealing adhesive tape and preparation method thereof |
-
1988
- 1988-10-20 CN CN 88108524 patent/CN1026986C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1034738A (en) | 1989-08-16 |
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