CN100339434C - Flame-retardant rubber composition, rubber articles and wire covering materials - Google Patents

Flame-retardant rubber composition, rubber articles and wire covering materials Download PDF

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CN100339434C
CN100339434C CNB2004800036031A CN200480003603A CN100339434C CN 100339434 C CN100339434 C CN 100339434C CN B2004800036031 A CNB2004800036031 A CN B2004800036031A CN 200480003603 A CN200480003603 A CN 200480003603A CN 100339434 C CN100339434 C CN 100339434C
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mass parts
rubber
composition
acid
flame
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CN1747999A (en
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森冈诚次
小林伸敏
后藤秀且
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Yinnenshi Materials Co ltd
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JSR Corp
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Abstract

A flame-retardant rubber composition obtained by compounding a combination of (A) an ethylene/alpha-olefin random copolymer and (B) an unsaturated nitrile/conjugated diene rubber or a combination of (A) an ethylene/alpha-olefin random copolymer, (B) an unsaturated nitrile/conjugated diene rubber, and (C) a hydrogenated diene polymer with surface-treated natural magnesium hydroxide; and rubber articles made from the composition. The rubber composition and the rubber articles exhibit excellent flame retardance, weather resistance, and oil resistance as well as excellent mechanical characteristics, thus being useful in various fields including roll of copying machine, belt, sealant, wire covering material, and hoses.

Description

Flame-retardant rubber composition, rubber item and wire covering materials
Technical field
The present invention relates to the flame-retardant rubber composition of weathering resistance, oil-proofness, flame retardant resistance, mechanical characteristics and excellent in workability.In more detail, relate to excellent in flame retardance, even when burning, do not produce toxic gases such as halogen gas simultaneously yet, in addition, do not contain environmental pollutants such as phosphorus and lead, and all rerum natura balance excellences such as weathering resistance, mechanical characteristics, useful especially flame-retardant rubber composition and rubber item thereof in purposes such as the roller of duplicating machine, band, sealing material, wire covering materials.
Background technology
With the propylene diene copolymer rubber is the ethylene-alpha-olefin class random copolymers (following abbreviate as sometimes " EP (D) M ") of representative, because therefore excellences such as mechanical characteristics, thermotolerance, weathering resistance extensively are used in the purposes such as trolley part, technically classified rubber parts, electronic unit, building building materials article.Recently, because the high performance of automobile, electronic product etc., be that the environment for use condition of the rubber item of example becomes more and more severeer with roller, band, wire covering materials etc.In the environment for use of these rubber items, the rising of envrionment temperature is remarkable, further improves flame retardant resistance when requiring hot environment to use.
In the past, as the most general method of giving the rubber combination flame retardant resistance, will consider the method for using the halogen fire retardant.But, though mixing, these fire retardants can bring into play flame retardant effect on a small quantity, have the problem of corrodibility and generation toxic gas when having burning.
As the flame-retardant rubber composition that does not use the halogen fire retardant, have use phosphorus type flame retardant composition (for example, open flat 2-263851 communique referring to the spy), but phosphorus type flame retardant need prevent based on its hygroscopic oozing out, think certain improvement is arranged though prevent to ooze out by mixed olefins class synthetic rubber and silane coupling agent, but from rerum natura and viewpoints nuisanceless and that environment is in harmonious proportion such as flexible and flexibilities, may not be fully satisfied.
Recently, as nuisanceless and environment mediation type fire retardant, the hydrate of mineral-type metallic compounds such as aluminium hydroxide, magnesium hydroxide receives publicity, and the olefines synthetic rubber has also been carried out studying (for example, opening flat 6-107870 communique referring to the spy).But, hydrate for this mineral-type metallic compound, for the flame retardant resistance that obtains to satisfy, the loading level that needs the hydrate of raising mineral-type metallic compound, if raising loading level, then have mechanical characteristics, particularly tensile strength reduces, and also has flexibility, processibility to reduce such problem.And the purposes according to using requires oil-proofness.
On the other hand, for the character of the excellence of utilizing EP (D) M, and then keep further feature, always to studying with the mixture of various rubber.In this mixing system, with unsaturated nitrile-conjugated diene copolymer (following abbreviate as sometimes " NBR ".) mixture be known as heat-resistant aging, oil-proofness, the rubber combination that has excellent weather resistance.But these 2 kinds of rubber solubility coefficient separately differs greatly, and when therefore mixing them, is difficult to obtain uniform composition.In addition, the vulcanization rate of these 2 kinds of rubber phases has difference, so there is boundary in the rerum natura of gained sulfide.Therefore, mechanical properties for the mixture that improves EP (D) M and NBR, for example open the combination of the nitrile rubber and halogenation EP (D) M that have proposed to have functional group in the clear 59-226038 communique the spy, in addition, open in the flat 8-127682 communique the spy, proposed the rubber combination that constitutes by acrylate-unsaturated nitrile-conjugated diene copolymer, ethylene-propylene analog copolymer and hydrogenating conjugate diene analog copolymer.But, if in these rubber combinations, use the water and the thing of mineral-type metallic compounds such as aluminium hydroxide that the non-halogen fire retardant as nuisanceless and environment mediation type receives publicity recently, magnesium hydroxide, flame retardant resistance then in order to obtain to satisfy, need to improve the water of mineral-type metallic compound and the loading level of thing, if raising loading level, then have mechanical characteristics, particularly tensile strength reduces, and also has flexibility, processibility to reduce such problem.
The present invention proposes in view of the above problems, excellent in flame retardance is provided, while weathering resistance, mechanical characteristics, excellent in workability, and has an oil-proofness, useful especially flame-retardant rubber composition and rubber item thereof in the wire covering materials of distribution and automobile electrical gas distribution etc., the insulating tape purposes in duplicating machine, instruments such as the roller of duplicating machine, band, sealing material.
Summary of the invention
The inventor constantly further studies in order to address the above problem, and found that, by using surface-treated brucite, can further improve mechanical characteristics, has so far finished the present invention.
Promptly, the invention provides a kind of flame-retardant rubber composition, its with respect to (A) ethylene ' alpha '-olefin class random copolymers 95～15 mass parts, (condition is (B) unsaturated nitrile-conjugated diene rubber 5～85 mass parts, (A)+(B) mass parts=100), contain (D) surface-treated brucite 50～400 mass parts.
In addition, the present invention also provides a kind of flame-retardant rubber composition, its with respect to (A) ethylene ' alpha '-olefin class random copolymers 3～62 mass parts, (B) unsaturated nitrile-conjugated diene rubber 35～94 mass parts, (condition is (C) hydrogenated diene base polymer 3～62 mass parts, (A)+(B) mass parts+(C)=100), contain (D) surface-treated brucite 50～400 mass parts.
In the present invention, it is the natural mineral of main component that above-mentioned (D) magnesium hydroxide is preferably pulverized with the magnesium hydroxide, carry out the magnesium hydroxide that surface treatment obtains with at least a kind that is selected from fatty acid ester, wax, lipid acid, fatty acid metal salt, winterized stearin, silane coupling agent and the titanic acid ester coupler, wherein, more preferably pulverizing with the magnesium hydroxide is the natural mineral of main component, carries out the magnesium hydroxide that surface treatment obtains with fatty acid ester or wax.
In rubber combination of the present invention, the Mooney viscosity [ML of preferably above-mentioned (A) ethylene ' alpha '-olefin class random copolymers 1+4(100 ℃)] be 20～300.In addition, the preferred unsaturated nitrile of above-mentioned (B) unsaturated nitrile-conjugated diene rubber unit content is unsaturated nitrile-conjugated diene rubber of 33～70 quality %, and more preferably unsaturated nitrile unit content is 40～60 quality %.
In addition, in rubber combination of the present invention, above-mentioned (C) hydrogenated diene analog copolymer polymkeric substance preferably has vinyl bonds content, and to be lower than 25% polybutadiene block and vinyl bonds content be the hydride of the segmented copolymer of the conjugated diolefine polymer block more than 25%, below 90%.
Rubber combination of the present invention preferably further contains metal-salt 1～10 mass parts of (E) vinyl unsaturated carboxylic acid.
Rubber combination preferred oxygen index of the present invention (LOI) is more than 28%.
Rubber combination of the present invention can become rubber item useful in purposes such as wire covering materials by cross-linking.
The best mode that carries out an invention
Below, specifically describe the embodiment of flame-retardant rubber composition of the present invention.
Flame-retardant rubber composition of the present invention roughly is divided into following 3 kinds of forms, first, contain (A) ethylene ' alpha '-olefin class random copolymers, (B) unsaturated nitrile-conjugated diene rubber and (D) these 3 kinds of compositions of brucite as the rubber combination (first kind of mode) of main component, second, contain (A) ethylene ' alpha '-olefin class random copolymers, (B) unsaturated nitrile-conjugated diene rubber, (C) the hydrogenated diene base polymer and (D) these 4 kinds of compositions of brucite as the rubber combination (second way) of main component, the 3rd, in the rubber combination of the above-mentioned first kind of mode or the second way, further contain the rubber combination (the third mode) of the metal-salt of (E) vinyl unsaturated carboxylic acid.
Specify each integrant below.
(A) ethylene ' alpha '-olefin class random copolymers:
As (A) ethylene ' alpha '-olefin class random copolymers used among the present invention (below be also referred to as " (A) composition "), can enumerate ethylene, propylene copolymer rubber, ethylene, propylene non-conjugated diene terpolymer rubber, ethene 1-butylene copolymer rubber, ethene 1-butylene non-conjugated diene terpolymer rubber etc. is the random copolymers of main component with the alpha-olefin of ethene and carbonatoms 3～10.
As the alpha-olefin of above-mentioned carbonatoms 3～10, can enumerate propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene etc., preferred especially propylene, 1-butylene.
As above-mentioned non-conjugated diene, can enumerate 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 5-methyl isophthalic acid, 8-nonadiene, Dicyclopentadiene (DCPD), 5-ethylidene norbornene, 5-vinyl-2-norbornylene, 2,5-norbornadiene etc., preferred especially 1,4-hexadiene, Dicyclopentadiene (DCPD), 5-ethylidene-2-norbornene.
In these ethylene ' alpha '-olefin class random copolymerss, preferably with 10 moles of ratio copolymerization alpha-olefins more than the %.In addition, as non-conjugated diene, preferred ethylidene norbornene, Dicyclopentadiene (DCPD), 1, the 4-hexadiene, when being 100 moles of % with the summation of ethene and alpha-olefin, its content is preferably 3～10 moles of % (more preferably 3～8 moles of %).In addition, representing with iodine number, is below 40, preferred 5～30, more preferably 7～20.In ethylene ' alpha '-olefin class random copolymers, ethylene content is more than 90 moles of %, and when alpha-olefin content was lower than 10 moles of %, the flexibility of this copolymer rubber was not enough, is not preferred.In addition, the Mooney viscosity [ML of ethylene ' alpha '-olefin class random copolymers 1+4(100 ℃)] be 20～300, preferred 40～200, more preferably 60～200.The crystallization degree that X-ray diffraction is measured is below 20%, more preferably below 15%.The crystallization degree surpasses at 20% o'clock, has the tendency of the flexibility reduction of copolymer rubber, is not preferred.
There is no particular limitation to the polymerization process of (A) composition, can polymerization in the presence of known catalyzer such as vanadium class catalyzer, titanium class catalyzer, class of metallocenes catalyzer.For example in the occasion of vanadium class catalyzer, can make with the following method, promptly in the presence of catalyzer that at least a kind of solvent soluble vanadium compound and at least a kind of organo-aluminium compound constitute, as required, on one side supply with hydrogen as molecular weight regulator, on one side the method for polymerising ethylene, alpha-olefin and non-conjugated diene.The polymerization of this moment can use vapor phase process (thermopnore or agitated bed) also can use liquid phase method (slurry method or solution method) to implement.The preferred VOCl of above-mentioned solvent soluble vanadium compound 3, VCl 4, VOCl 3Perhaps VCl 4At least a kind with alcohol resultant of reaction.At this moment,, can enumerate methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, n-hexyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, nonylcarbinol, n-dodecane alcohol etc. as above-mentioned alcohol, wherein, the alcohol of preferred carbonatoms 3～8.In addition, as above-mentioned organo-aluminium compound, can enumerate triethyl aluminum, triisobutyl aluminium, three-n-hexyl aluminium, monochlor(in)ate diethyl aluminum, monochlor(in)ate diisobutyl aluminum, sesquialter ethylaluminium chloride, sesquialter chlorinated butyl aluminium, ethylaluminium dichloride, dichloride butyl aluminium, as the methylaluminoxane of the resultant of reaction of trimethyl aluminium and water etc., the mixture of mixture, triisobutyl aluminium and the sesquialter chlorinated butyl aluminium of preferred especially sesquialter ethylaluminium chloride, sesquialter chlorinated butyl aluminium, sesquialter ethylaluminium chloride and triisobutyl aluminium.In addition, as above-mentioned solvent, use varsol usually.Preferred varsol is Skellysolve A, normal hexane, normal heptane, octane, octane-iso, hexanaphthene etc.These varsols can separately or merge use more than 2 kinds.
For ethylene ' alpha '-olefin class random copolymers of the present invention, also can be when polymerization, to add the extending oil polymkeric substance that the described tenderizer in back obtains.
(B) unsaturated nitrile-conjugated diene rubber:
As (B) unsaturated nitrile-conjugated diene rubber used among the present invention (below be also referred to as " (B) composition "), can enumerate copolymer rubber, conjugated diolefine and the unsaturated nitrile of conjugated diolefine and unsaturated nitrile and the copolymer rubber of the co-polymerized monomer that contains polar group beyond the unsaturated nitrile, also have their partial cross-linked copolymer rubber.
As the conjugated diolefine that constitutes (B) composition (below be also referred to as " (b-1) "), can enumerate 1,3-divinyl, isoprene, 1,3-hexadiene, 2-methyl isophthalic acid, 3-divinyl, 2,3-dimethylbutadiene, 2-trimethoxysilyl-1,3-divinyl, 1,3-pentadiene, 2,4-dimethyl-1,3-divinyl etc., these can a kind of separately or merging use more than 2 kinds.Wherein, preferred especially 1,3-butadiene and isoprene.
As the unsaturated nitrile that constitutes (B) composition (below be also referred to as " (b-2) "), can enumerate vinyl cyanide, methacrylonitrile, α-ethyl acrylonitrile, α-sec.-propyl vinyl cyanide, α-Lv Bingxijing, α-fluorine vinyl cyanide, ethacrylonitrile etc., preferred especially vinyl cyanide.
Specific examples as the co-polymerized monomer that contains polar group beyond the unsaturated nitrile that constitutes (B) composition (below be also referred to as " (b-3) "), can enumerate methyl acrylate, ethyl propenoate, the vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, sec-butyl acrylate, vinylformic acid 2-methyl butyl ester, vinylformic acid 3-methyl butyl ester, the just own ester of vinylformic acid, the positive heptyl ester of vinylformic acid, the vinylformic acid n-octyl, 2-EHA, acrylamide, N-methylol (methyl) acrylamide, N-(2-hydroxyethyl) (methyl) acrylamide, N, two (2-hydroxyethyl) (methyl) acrylamides of N-, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, Ba Dousuan 2-hydroxyl ethyl ester, Ba Dousuan 2-hydroxypropyl acrylate, styracin 2-hydroxyl ethyl ester, styracin 2-hydroxypropyl acrylate, vinyl carbinol, neighbour-hydroxy styrenes, between-hydroxy styrenes, right-hydroxy styrenes, glycol monomethyl (methyl) acrylate, propylene glycol list (methyl) acrylate, vinyl-amine, allylamine, neighbour-amino-benzene ethene, between-amino-benzene ethene, right-amino-benzene ethene, (methyl) vinylformic acid 2-amino ethyl ester, the amino propyl ester of (methyl) vinylformic acid 2-, (methyl) glycidyl acrylate, allyl glycidyl ether, propenal, ethenyl methyl ketone, phthalic acid divinyl ester, diallyl phthalate, N, N-methylene-bis (methyl) acrylamide, N, N-ethylenebis (methyl) acrylamide, N, two (methyl) acrylamides of N-hexa-methylene, (methyl) vinylformic acid, Ba Dousuan, styracin, methylene-succinic acid, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid, methacrylic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, ω-carboxyl-polycaprolactone list (methyl) acrylate, tetrahydrofurfuryl acrylate, two (methyl) acrylate of the poly-alkane glycol of polyoxyethylene glycol (alkane diol units numerical example as be 2～23), two (methyl) acrylate of the poly-alkane glycol of polypropylene glycol (alkane diol units numerical example as be 2～23) etc.These monomers can a kind of independent or merging use more than 2 kinds.Wherein preferred especially vinylformic acid, ethyl propenoate, n-butyl acrylate, tert-butyl acrylate, sec-butyl acrylate.
(B) content of the conjugated diene unit in the composition is 15～65 quality % when the quality % of (b-1)+(b-2)+(b-3)=100, more preferably 20～50 quality %.When the content of monomer (b-1) was lower than 15 quality %, there was the tendency that reduces in caoutchouc elasticity.On the other hand, if surpass 65 quality %, with the intermiscibility deterioration of magnesium hydroxide, the physical strength of gained rubber combination descends.
The content of unsaturated nitrile unit (b-2) is preferably 33～70 quality %, more preferably 40～60 quality %.When the content of monomer (b-2) was lower than 33 quality %, with the intermiscibility deterioration of magnesium hydroxide, the physical strength of gained rubber combination descended.In addition, also there is the tendency of reduction in oil-proofness.On the other hand, monomer (b-2) if content surpass 70 quality %, caoutchouc elasticity may descend.
The content of the co-polymerized monomer unit (b-3) of the polar functionalities beyond the unsaturated nitrile is 0～50 quality %, more preferably 0～40 quality %.Monomer (b-3) if content surpass 50 quality %, then there is the tendency that descends in caoutchouc elasticity.
The partial cross-linked copolymer rubber that is comprised in (B) of the present invention composition can by make multi-functional unsaturated monomer and above-mentioned (b-1) and (b-2) or (b-1) and (b-2) and (b-3) copolymerization obtain.
Multi-functional unsaturated monomer (below be also referred to as " (X) ") in 1 molecule, contain more than 2 can radical polymerization vinyl, can carry out polymerization by common emulsion polymerization.For example, multivalence allylic cpd, (methyl) acrylic compound, divinyl compound, bismaleimide compound, oxime compound etc.Can enumerate the cyanuric acid triallyl ester particularly; the tricarbimide triallyl ester; three (methyl) vinylformic acid trihydroxymethylpropanyl ester; N; N '--the phenylene dimaleimide; ethylene glycol bisthioglycolate (methyl) acrylate; 1; 3-butyleneglycol two (methyl) acrylate; 1; 4-butyleneglycol two (methyl) acrylate; 1; 6-hexylene glycol two (methyl) acrylate; polyoxyethylene glycol two (methyl) acrylate; 2; 2 '-two (4-methacryloyl diethoxy phenyl) propane; tetramethylolmethane three (methyl) acrylate; Vinylstyrene; bismaleimides; N; N '-methylene-bisacrylamide; the para-quinone dioxime; right, to '-the dibenzoyl quininie dioxime; triazine thiol etc.These also can a kind of independent or merging use more than 2 kinds.
There is no particular limitation to the polymerization process of (B) unsaturated nitrile-conjugated diene rubber, can enumerate radical polymerization method, anionic polymerization etc.As the radical polymerization method, comprise mass polymerization, suspension polymerization, emulsion polymerization method etc., in the present invention, owing to use the vinyl cyanide rubber latex, therefore special preferred polymeric can obtain the emulsion polymerization method of stable emulsified dispersed liquid when finishing.This emulsion polymerization gets final product with common polymerization process, for example in the presence of emulsifying agent, in water-medium, make given monomer emulsification, free radical polymerization starter initiated polymerization, reach given polymerisation conversion after, stop polymeric method etc. with short-stopper.
As emulsifying agent, can enumerate anionic species tensio-active agent, nonionic class tensio-active agent, cationic tensio-active agent and amphoterics etc.In addition, also can use fluorine class tensio-active agent.These emulsifying agents can only use a kind, also can merge use more than 2 kinds.Usually mostly use the anionic species tensio-active agent, for example use the hard soap of carbonatoms more than 10, sylvate etc.Can enumerate capric acid, lauric acid, tetradecanoic acid, palmitinic acid, oleic acid, stearic sylvite and sodium salt etc. particularly.
As free radical polymerization initiator, can use organo-peroxides such as benzoyl peroxide, lauroyl peroxide, tertbutyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, ditertiary butyl peroxide and dicumyl peroxide.In addition, also can use with Diisopropyl azodicarboxylate and be the inorganic peroxide of representative and the redox class catalyzer that is combined as representative of these superoxide and ferrous sulfate etc. as diazonium compound, the Potassium Persulphate of representative.These free radical polymerization initiators can only use a kind, also can merge use more than 2 kinds.
In order to regulate the molecular weight of (B) unsaturated nitrile-conjugated diene rubber, also can use chain-transfer agent.As this chain-transfer agent, can use alkyl sulfhydryls such as uncle-lauryl mercaptan, n-dodecyl mercaptan, tetracol phenixin, sulphur glycols (thioglycols), diterpene, terpinolene and γ-terpinene class etc.
In the polymerization of (B) unsaturated nitrile-conjugated diene rubber, both can begin polymerization to whole disposable putting into such as various monomers, emulsifying agent, free radical polymerization initiator and chain-transfer agent in the reaction vessel, and also can when reaction be carried out, append, add continuously or intermittently.This polymerization can be used the reactor of having removed oxygen, carries out under 0～100 ℃, preferably carries out under 0～80 ℃ polymerization temperature.In the reaction also can the appropriate change temperature or operational condition such as stirring etc.Polymerization methods both can be a continous way, also can be step.
Polymeric stops and can reach the time point of given polymerisation conversion, is undertaken by adding short-stopper.As short-stopper, can use naphtoquinone compounds such as amine compound such as azanol, diethyl hydroxylamine, quinhydrones etc.After polymerization stops, as required, remove unreacted monomer from reaction system, make latex coagulation, the unsaturated nitrile-conjugated diene rubber that obtains using among the present invention with methods such as steam distillations.
There is no particular limitation to the molecular weight of (B) unsaturated nitrile-conjugated diene rubber, preferred Mooney viscosity [ML 1+4(100 ℃)] be 20～200.
(A) components in proportions in the rubber combination of first kind of mode of the present invention, with respect to (A) ethylene ' alpha '-olefin class random copolymers and (B) total amount 100 mass parts of unsaturated nitrile-conjugated diene rubber, be 95～15 mass parts, preferred 80～20 mass parts.On the other hand, (B) components in proportions in the rubber combination of first kind of mode of the present invention is 5～85 mass parts, preferred 20～80 mass parts.
By containing more than (B) unsaturated nitrile-conjugated diene rubber 15 mass parts, can further improve flame retardant resistance and oil-proofness, if but surpass 90 mass parts, then there is the tendency that worsens in weathering resistance.
(C) hydrogenated diene base polymer:
(C) hydrogenated diene base polymer that uses among the present invention (below be also referred to as " (C) composition ") is to contain at least a kind following (i) and/or (ii) and the hydride of at least a kind of (iii) following and/or segmented copolymer (iv) (below be also referred to as " multipolymer before the hydrogenation ").
(i) aromatic ethenyl compound is the above polymerization of aromatic vinyl thing blocks of 80 quality %,
(ii) vinyl bonds content is lower than 25% polybutadiene polymers block,
(iii) vinyl bonds content is at the conjugated diolefin polymer block more than 25%, below 90%,
The (iv) block of random copolymer of aromatic ethenyl compound and conjugated diolefine.
Multipolymer can followingly easily obtain before this hydrogenation, promptly in inert organic solvents such as aromatic hydrocarbon solvents such as clicyclic hydrocarbon solvent, benzene, dimethylbenzene, toluene, ethylbenzene such as aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane for example, with organic alkali metal compound as polymerization starter, make conjugated diolefine, perhaps vinyl aromatic compounds and conjugated diolefine are carried out active anionic polymerization, after obtaining segmented copolymer, this multipolymer of hydrogenation.
As vinyl aromatic compounds, can enumerate vinylbenzene, t-butyl styrene, alpha-methyl styrene, p-methylstyrene, to ethyl styrene, Vinylstyrene, 1,1-diphenyl benzene ethene, vinyl naphthalene, vinyl anthracene, N, the N-diethyl-to amino-ethyl vinylbenzene, vinyl pyridine etc.Wherein, optimization styrene.
In addition, as conjugated diolefine, can enumerate 1,3-divinyl, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-octadiene, 1,3-hexadiene, 1,4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene, chloroprene etc.Wherein, preferred 1,3-butadiene, isoprene.
There is no particular limitation to the ratio of components of conjugated diolefine in the multipolymer before the above-mentioned hydrogenation and vinyl aromatic compounds, can make it the scope at conjugated diolefine 5～100 quality % and aromatic ethenyl compound 0～95 quality % usually.
In addition, in above-mentioned block of random copolymer (iv), also comprise the so-called alternation type (taper type) that aromatic ethenyl compound content changes continuously in a part.In addition, example as the segmented copolymer that contains above-mentioned polymer blocks before the hydrogenation, can enumerate (i)-(iii), (i)-(iv), (ii)-(iii), [(i)-(iii)] x-Y, [(i)-(iv)] x-Y, [(ii)-(iii)] x-Y, (i)-(iii)-(ii), (i)-(iii)-(iv), (i)-(iii)-(i), (i)-(iv)-(i), (i)-(iv)-(iii), (ii)-(iii)-(ii), [(i)-(iii)-(ii)] x-Y, [(i)-(iii)-(i)] x-Y, [(i)-(iv)-(i)] x-Y, [(i)-(iv)-(iii)] x-Y, (i)-(iii)-(i)-(iii), (iii)-(i)-(iii)-(i), [(i)-(iii)-(i)-(iii)] x-Y, [(iii)-(i)] x-Y, [(iv)-(i)] x-Y, (ii)-(i)-(iii)-(i), (iii)-(i)-(iv)-(i), (iii)-(i)-(iv)-(iii), [(iii)-(i)-(ii)-(iii)] x-Y, [(iv)-(i)-(ii)-(i)] x-Y, [(iv)-(i)-(iii)-(i)] x-Y, [(iv)-(i)-(iv)-(i)] x-Y, [(iv)-(i)-(iv)-(iii)] x-Y, (iv)-(i)-(ii)-(i)-(ii), (iv)-(ii)-(i)-(ii)-(i), (iv)-(i)-(iii)-(i)-(iii), (iv)-(iii)-(i)-(iii)-(i), [(iv)-(i)-(ii)-(i)-(ii)] x-Y, (iv)-(i)-(ii)-(i)-(ii)-(i), (condition is [(iv)-(i)-(ii)-(i)-(ii)-(i)] x-Y etc., x 2, and Y is the residue of coupler.)。Wherein, especially preferably contain more than at least 1 above-mentioned (ii) with the hydride of the segmented copolymer of above-mentioned polymer blocks (iii).
As above-mentioned coupler, halogen compounds, epoxy compounds, carbonyl compound, polyvinyl compound etc. can be enumerated, dimethyl dichlorosilane (DMCS), METHYL TRICHLORO SILANE, butyl trichlorosilane, tetrachloro silicane, ethylene dibromide, epoxidised soybean oil, Vinylstyrene, tin tetrachloride, butyl tin trichloride, germanium tetrachloride, two (Trichloromonosilane base) ethane, diethylene adipate, dimethyl adipate, dimethyl terephthalate (DMT), diethyl terephthalate, polymeric polyisocyanate etc. can be enumerated particularly.
For hydrogenated diene base polymer of the present invention, the segmented copolymer by hydrogenation obtains as mentioned above carries out selective hydration.For hydrogenation ratio, be more than 80%, to be preferably more than 95% as two keys of the conjugated diolefine origin of unsaturated part.
There is no particular limitation for the molecular weight of hydrogenated diene base polymer of the present invention, and weight-average molecular weight is 30,000～2,000,000, preferred 40,000～1,000,000, and more preferably 50,000～500,000.
In addition, above-mentioned hydrogenated diene base polymer also can import to functional groups such as amino, alkoxysilyl, hydroxyl, acid anhydrides, epoxy group(ing) in this diolefinic polymer, as the hydrogenated diene base polymer use of modification.The hydrogenated diene base polymer of this modification can be enumerated following multipolymer.
(I) in the presence of organic alkali metal compound, polymerized conjugated diene monomer or vinyl aromatic monomers and conjugate diene monomer are at the active site of resulting polymers, make it and epoxy compounds or ketone compound reaction, become polymkeric substance, afterwards, the polymkeric substance that this polymkeric substance of hydrogenation obtains.
(II) in the presence of organic alkali metal compound; polymerized conjugated diene monomer or vinyl aromatic monomers and conjugate diene monomer; this polymkeric substance of hydrogenation makes at least a kind of polymkeric substance that obtains with the polymer reaction that obtains that is selected from the compound that contains (methyl) acryl, the compound that contains epoxy group(ing) or the maleic anhydride in solution or in the mixing roll such as forcing machine.And,
(III) in the presence of organic alkali metal compound, polymerized conjugated diene monomer or vinyl aromatic monomers and conjugate diene monomer, use epoxidation 1,2-polyhutadiene, epoxidised soybean oil, epoxy linseed oil, benzene-1,2,4-triisocyanate, oxalic acid diethyl ester, diethyl malonate, diethylene adipate, Octyl adipate, dimethyl phthalate, diethyl phthalate, diethyl terephthalate, pyromellitic acid dianhydride etc. are as coupler, thus the molecular chain importing-OH of central authorities base ,-the NH-CO base ,-NH 2Functional groups such as base and the polymkeric substance that obtains.
(A) components in proportions in the rubber combination of the second way of the present invention with respect to (A) composition and (B) composition and (C) total amount 100 mass parts of composition, is 3～62 mass parts, preferred 5～55 mass parts, more preferably 10～40 mass parts.When (A) components in proportions was lower than 3 mass parts, weathering resistance worsened, if surpass 62 mass parts, then oil-proofness worsens.
In addition, (B) components in proportions in the rubber combination of the second way of the present invention is 35～94 mass parts, preferred 40～80 mass parts, more preferably 50～80 mass parts.When (B) composition was lower than 35 mass parts, oil-proofness worsened, and on the other hand, if surpass 94 mass parts, then weathering resistance worsens.
And (C) components in proportions in the rubber combination of the second way of the present invention is 3～62 mass parts, preferred 5～55 mass parts, more preferably 10～40 mass parts.When (C) components in proportions was lower than 3 mass parts, mechanical characteristics worsened, if surpass 62 mass parts, then oil-proofness worsens.
(D) magnesium hydroxide:
The hydrogenation magnesium that uses among the present invention (below be also referred to as " (D) composition ") is to pulverize natural mineral such as natural brucite ore, surface-treated magnesium hydroxide.
Usually the magnesium hydroxide that uses in the fire retardant purposes roughly is divided into synthesis method and natural mineral pulverizing manufactured, but make with synthesis method, for example in the slurries of caustic alkali or slaked lime, add contained magnesium in seawater or the bittern, make it to react the magnesium hydroxide that obtains; The magnesium hydroxide that adds sodium hydroxide and hot-water cure in the magnesium hydroxide slurry and obtain; The magnesium hydroxide that hot-water cure alkalescence magnesium salts slurries obtain; Even the magnesium hydroxides that magnesium salt solution and ammonia react obtain etc. can not obtain effect of the present invention through surface treatment.
It will be the natural mineral pulverizing of main component with the magnesium hydroxide that surface-treated brucite of the present invention is to use the medium pulverizer that can heat, carry out surface treatment with at least a kind the surface treatment agent that is selected from for example fatty acid ester, wax, lipid acid, fatty acid metal salt, winterized stearin, silane coupling agent and the titanic acid ester coupler, perhaps pulverize and surface treatment is carried out simultaneously, below the volume average particle size 5 μ m and have a particle of the coating layer of this surface treatment agent.
Preferred 1～5 μ m of volume average particle size, more preferably 3～5 μ m, the preferred 7～20cm of specific surface area 2/ g.The addition of surface treatment agent is with respect to the total amount of magnesium hydroxide and surface treatment agent, preferred about 0.5～5 quality %.Temperature during heating is generally about 50～200 ℃, preferred about 80～150 ℃.It is serious that surface treatment agent of no use carries out the aggegation of surface-treated magnesium hydroxide particles, and rerum natura reduces, and can not obtain effect of the present invention.
The fatty acid ester that uses as surface treatment agent among the present invention can be enumerated Laurate methyl, Myristicin acid methylester, Uniphat A60, methyl stearate, Witconol 2301, methyl erucate, mountain Yu acid methyl esters, butyl laurate, butyl stearate, Isopropyl myristate, Wickenol 111, Wickenol 155, the coconut fatty acid monooctyl ester, octyl stearate, special tallow fatty acids monooctyl ester, the lauric acid Lauryl Ester, the stearic acid stearyl, the longer chain fatty acid high alcohol ester, mountain Yu acid mountain Yu Ji ester, monoesters such as tetradecanoic acid hexadecyl ester can also be enumerated the amyl-based polyol long chain fatty acid ester, the partial esterification thing of amyl-based polyol long chain fatty acid ester, the amyl-based polyol fatty acid ester, the amyl-based polyol medium chain fatty acid ester, amyl-based polyol C9 chain fatty acid ester, the dipentaerythritol long chain fatty acid ester, special fatty acid esters such as compound medium chain fatty acid ester.
The lipid acid that uses as surface treatment agent among the present invention can be enumerated stearic acid, oleic acid, palmitinic acid, linolic acid, lauric acid, sad, mountain Yu's acid, montanic acid etc.
The fatty acid metal salt that uses as surface treatment agent among the present invention is the metal-salt of stearic acid, oleic acid, palmitinic acid, linolic acid, lauric acid, sad, mountain Yu's acid, montanic acid etc. for example, as metal, can enumerate Na, K, Al, Ca, Mg, Zn, Ba, Co, Sn, Ti, Fe etc.
The winterized stearin that uses as surface treatment agent can be enumerated tallow winterized stearin, castor-oil plant sclerosis wet goods in the present invention.
The silane coupling agent that uses as surface treatment agent can be enumerated vinyltrimethoxy silane in the present invention, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyl trichloro silane, vinyl nitrilotriacetic base silane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl three ('beta '-methoxy oxyethyl group) silane, γ-Qiu Jibingjisanjiayangjiguiwan, methyltrimethoxy silane, Union carbide A-162, hexamethyldisilazane, γ-phenylamino propyl trimethoxy silicane, N-[β-(N-vinyl benzylidene amino) ethyl]-gamma-amino propyl trimethoxy silicane hydrochloride etc.
The titanic acid ester coupler that uses as surface treatment agent can be enumerated isopropyl triisostearoyl titanate, three (N-aminoethylamino ethyl) isopropyl titanate, two (dioctylphosphoric acid ester) metatitanic acid diisopropyl ester, two (dioctyl phosphite) titanium isopropylate, two (two (tridecyl) esters of phosphorous acid) metatitanic acid four monooctyl esters, four (2,2-two allyloxy methyl isophthalic acid-butyl) two (two (tridecyl)) phosphorous acid ester titanic acid ester, two (dioctyl pyrophosphate) oxyacetate titanate, two (dioctyl pyrophosphate) ethylene titanate etc. in the present invention.
The special preferred fat acid esters of surface treatment agent or the wax that use.
In addition, in the present invention,, as required, also can use phosphorus type flame retardants such as ammonium polyphosphate based flame retardant, phosphoric acid ester in order to improve flame retardant effect; Silicone compounds; Silica glass etc., moreover, can use water glass etc. as flame retardant, in order further to prevent drippage, also can use silicon nitride staple fibre etc.
For the content of (D) composition in composition, in first and second kinds of modes, with respect to (A) composition and (B) total amount 100 mass parts or (A) composition and (B) composition and (C) total amount 100 mass parts of composition of composition, be more than 50 mass parts, more than preferred 65 mass parts.If be lower than 50 mass parts, then can not obtain to have the composition of sufficient flame retardant resistance.On be limited to below 400 mass parts, below preferred 200 mass parts.When the amount of oxyhydroxide was very few, flame retardant resistance was not enough, on the other hand, when the amount of oxyhydroxide is too much, was difficult to mixingly, and simultaneously rubber significantly reduces as elastomeric characteristic and mechanical characteristics.
According to the present invention, be flame-retardant rubber composition more than 28% by reducing the content of (D) composition, can obtaining oxygen index (LOI).
(E) metal-salt of ethene unsaturated carboxylic acid:
The metal-salt of (E) ethene unsaturated carboxylic acid that uses in the third mode of the present invention (below be also referred to as " (E) composition ") is unsaturated monocarboxylic acids such as vinylformic acid, methacrylic acid, Ba Dousuan, 3-butenoic acid; Unsaturated dicarboxylic acids such as toxilic acid, fumaric acid, methylene-succinic acid; The monoesters of unsaturated dicarboxylic acids such as monomethyl maleate, ethyl maleate, methylene-succinic acid mono ethyl ester; Unsaturated polycarboxylic acid outside above-mentioned; At least a kind metal-salt with ester of the residual unsaturated polycarboxylic acid of monobasic free carboxy at least etc.As metal, so long as with salifiable the getting final product of above-mentioned ethene unsaturated carboxylic acid shape, there is no particular limitation to this, preferred especially zinc, magnesium, calcium and aluminium.In the metal-salt of these ethene unsaturated carboxylic acids, by rerum natura and easy acquired setting out, the special acrylic acid zinc salt of preferable methyl.When using the zinc salt of methacrylic acid,, make zn cpdss such as zinc oxide, zinc carbonate, preferred 0.5～2.5 mole scope internal reaction and obtaining at 0.5～3.2 mole with respect to 1 mole of methacrylic acid.
When adding the metal-salt (E) of ethene unsaturated carboxylic acid,, add (E) composition 1～10 mass parts with respect to (A) composition and (B) total amount 100 mass parts or (A) composition and (B) composition and (C) total amount 100 mass parts of composition of composition.When this ratio is lower than 1 mass parts, can not obtain better mechanical characteristics, if surpass 10 mass parts, the then mixing difficulty that becomes.
Other mixing element:
In addition, actual when using rubber combination of the present invention, remove the composition of above-mentioned (A) composition～(E), as required, all right mixed cross-linker, weighting agent, softening agent etc.In addition, all right suitably mixed carbon black toughener, metal oxide, tenderizer, antiaging agent and processing aid etc.And this moment, as rubber constituent, also can mix other rubber.There is no particular limitation for this other rubber constituent, can use styrene butadiene copolymer rubber, divinyl rubber, synthetic polyisoprene, butadiene isoprene copolymer rubber, butadiene-styrene-isoprene copolymer rubber, acrylic rubber, isoprene-isobutylene rubber, natural rubber, neoprene etc.
As linking agent, be representative with sulphur, in addition can also use sulfocompound, superoxide etc.When this linking agent was 100 mass parts with rubber constituent, mixed usually 0.5～10 mass parts was especially preferably mixed 1～6 mass parts.
As sulphur, can enumerate powder sulphur, sedimentation sulphur, colloid sulphur, surface-treated sulphur, insoluble sulphur etc. particularly.As sulfocompound, can enumerate sulfur subchloride, sulfur dichloride, polymer polysulfide etc. particularly.In addition, under crosslinking temperature, discharge active sulphur and crosslinked sulphur compound can be enumerated morpholine disulfide, curing alkylphenol, tetramethyl-thiuram disulfide, dipentamethylene thiuram tetrasulfide, Selenium dimethyl dithiocarbamate etc.
As organo-peroxide; can enumerate dicumyl peroxide, di-t-butyl peroxide, two-t-butylperoxy (peroxy)-3; 3; 5-trimethyl-cyclohexane, tertbutyl peroxide, tert-butyl peroxide cumyl, benzoyl peroxide, 2; 5-dimethyl-2; 5-two (t-butylperoxy) hexin-3,2; 5-dimethyl-2; 5-two (benzoyl peroxy) hexane, 2; 5-dimethyl-2; single (the t-butylperoxy)-hexane, 1 of 5-, two (t-butylperoxy sec.-propyl) benzene of 3-etc.Wherein, preferably use dicumyl peroxide, di-t-butyl peroxide, two-t-butylperoxy-3,3, the 5-trimethyl-cyclohexane.These organo-peroxides can be used in combination more than a kind or 2 kinds.
In addition, as crosslinking accelerator, can enumerate N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine, N-oxygen diethylidene-2-[4-morpholinodithio base sulfinyl amine, N particularly, N-di-isopropyl-sulfinyl amine compounds such as 2-[4-morpholinodithio base sulfinyl amine; Thiazole compounds such as 2-mercaptobenzothiazole, 2-(2 ', 4 '-dinitrophenyl) mercaptobenzothiazole, 2-(4 '-morpholinodithio) benzothiazole, dibenzothiazyl-disulfide; Guanidine compounds such as diphenylguanidine, di-o-tolyl guanidine, two adjacent nitrile guanidines, adjacent nitrile biguanides, phthalic acid diphenylguanidine; Aldehyde amine or aldehyde-ammoniac compounds such as acetaldehyde-aniline reaction thing, butyl aldehyde aniline condensation product, vulkacit H, aceto-aldehyde ammonia; Imidazolines such as 2-mercaptoimidazoline; Thioureas such as diphenyl thiourea, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, di-o-tolyl thiocarbamide; Thiuram compounds such as tetramethylthiuram monosulfide, tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, four sulfuration pentylidene thiurams; Dithio Barbiturates compounds such as ziram, zinc diethyldithiocarbamate, zinc dibutyl dithiocaarbamate, zinc-ethylphenyl dithiocarbamate, butyl phenyl zinc dithiocarbamate, Sodium dimethyldithiocarbamate 40min, Selenium dimethyl dithiocarbamate, tellurium dimethyldithiocarbamate; Xanthogenate compounds such as dibutyl xanthogenic acid zinc; Zinc acrylate resin compounds such as zinc acrylate resin, hydroxide zinc acrylate resin, zinc methacrylate; Compounds such as zinc oxide.
Further, as crosslinking coagent, can enumerate sulphur particularly; Quininie dioxime compounds such as para-quinone dioxime; Multi-functional methyl acrylic ester compound such as trihydroxy methyl propane trimethyl acrylate, polyethylene glycol dimethacrylate; Allylic compounds such as diallyl phthalate, cyanuric acid triallyl ester; Also has the maleimide compound in addition; Vinylstyrene etc.
As softening agent, can enumerate phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate (DOP), phthalic acid butyl octyl ester, phthalic acid two-(2-ethylhexyl) ester, dimixo-octyl phthalate, Di Iso Decyl Phthalate; Fatty acid esters such as dimethyl adipate, diisobutyl adipate, hexanodioic acid two-(2-ethylhexyl) ester, di-isooctyladinpate, diisodecyl adipate, hexanodioic acid octyl-decyl ester, nonane diacid two-(2-ethylhexyl) ester, diisooctyl azelate, diisobutyl azelate, Uniflex DBS, sebacic acid two-(2-ethylhexyl) ester, diisooctyl sebacate; 1,2,4-benzenetricarboxylic acid isodecyl ester, 1,2,4-benzenetricarboxylic acid monooctyl ester, 1,2,4-benzenetricarboxylic acid n-octyl, 1,2,4-benzenetricarboxylic acid ester in the different ninth of the ten Heavenly Stems etc. 1,2,4-benzenetricarboxylic acid ester class, and softening agent such as fumaric acid two-(2-ethylhexyl) ester, diglycol monotertiary oleic acid ester, glycero-monoricinoleate, tricresyl phosphate Lauryl Ester, tricresyl phosphate stearyl, tricresyl phosphate-(2-ethylhexyl) ester, epoxidised soybean oil, polyether ester.Softening agent can separately or merge use more than 2 kinds.In addition, softening agent also can be dispersed in unsaturated nitrile-conjugated diene rubber in advance and use.
As the carbon black toughener, can enumerate SAF carbon black, ISAF carbon black, HAF carbon black, FEF carbon black, GPF carbon black, SRF carbon black, FT carbon black, MT carbon black, Shawinigan black, Ketjen Black etc.These can separately or merge use more than 2 kinds.
As weighting agent, can enumerate silicon-dioxide, water-ground limestone, chalk, light calcium carbonate, atomic thin sensitization lime carbonate, special lime carbonate, alkaline magnesium carbonate, the potter's clay clay, sintered clay, the agalmatolite clay, the clay of silane treatment, synthetic calcium silicate, synthetic magnesium silicate, synthetic aluminium silicate, magnesiumcarbonate, aluminium hydroxide, magnesium hydroxide outside (D) of the present invention composition, magnesium oxide, potter's clay, sericite, talcum, the micro mist talcum, wollastonite, zeolite, xonotonite, asbestos, PMF (Porcessed Mineral Fiber), sepiolite, potassium titanate, ellestadite, gypsum fiber, glass sphere, silica spheres, hydrotalcite, the flyash ball, the shirasu ball, carbon class ball, aluminum oxide, barium sulfate, Tai-Ace S 150, calcium sulfate, molybdenumdisulphide etc.These can separately or merge use more than 2 kinds.
As metal oxide, can enumerate zinc oxide, active zinc flower, surface-treated zinc oxide, zinc carbonate, combined oxidation zinc, composite reactive zinc oxide, surface-treated magnesium oxide, magnesium oxide, calcium hydroxide, atomic thin calcium hydroxide, yellow lead oxide, red lead, white lead etc.These can separately or mix more than 2 kinds and use.
As tenderizer, can enumerate petroleum-type tenderizer, plant oil tenderizer, ointment.The petroleum-type tenderizer can be enumerated aromatic hydrocarbons, naphthenic, paraffin class tenderizer etc.Plant class tenderizer can be enumerated Viscotrol C, Oleum Gossypii semen, Toenol 1140, rapeseed oil, soybean oil, plam oil, Oleum Cocois, peanut oil, Japan tallow (Japan tallow) etc.Ointment can be enumerated dark substitute, white factice, sugar and oil cream etc.
As protective agent, can enumerate naphthylamines class, diphenylamine, Ursol D class, quinoline, hydroquinone derivatives class, single, double, three, Polyphenols, thiobis phenols, Hinered phenols, phosphorous acid esters, imidazoles, dithiocarbamic acid nickel salt class, phosphoric acid class protective agent etc.These can separately or mix more than 2 kinds and use.
As processing aid, can enumerate stearic acid, oleic acid, lauric acid, Zinic stearas, calcium stearate, potassium stearate, sodium stearate, stearylamide etc.These can separately or mix more than 2 kinds and use.
Rubber item:
Use the rubber item of rubber combination of the present invention followingly to make.
At first, use mixing rolls such as Banbury mixer, mixing rubber combination of the present invention and/or other rubber constituent under 70～180 ℃ temperature, for example weighting agent, carbon black toughener, tenderizer, other mixture etc.Afterwards, cool off mixing thing, use Banbury mixer or mixing roll,, make it to be shaped to given shape toward wherein further linking agent such as mix sulphur and crosslinking accelerator etc.Then, crosslinked under 130～200 ℃ temperature, obtain required cross-linked rubber, i.e. rubber item.
(embodiment)
Further describe the present invention particularly below by embodiment, but the present invention is not subjected to any restriction of these embodiment.
In addition, part in embodiment, the comparative example and % are quality criteria unless stated otherwise.
The hydrogenated diene base polymer that uses in embodiment and the comparative example is in order to the below manufactured.
The Production Example of hydrogenated diene base polymer (1)
In the reaction vessel of 10 liters of the internal volumes of nitrogen replacement, add hexanaphthene 5000g, 1,3-divinyl 300g, tetrahydrofuran (THF) 0.25g and n-Butyl Lithium 0.9g, under 70 ℃ of polymerization initiation temperatures, carry out the 1st step polymerization, after reaction finishes, make temperature be 20 ℃ and add tetrahydrofuran (THF) 5.5g after, add 1,3-butadiene 700g and carry out adiabatic polymerisation.After reaction finishes, add dimethyl dichlorosilane (DMCS) 0.6g, carry out 15 minutes coupled reaction.Reaction makes catalyzer (n-Butyl Lithium) inactivation after finishing, and obtains the preceding multipolymer of hydrogenation.
Making the temperature of the reaction soln that contains the preceding multipolymer of gained hydrogenation is 90 ℃, adds the hydrogenation catalyst based on two luxuriant titanium (titanocene) compounds, under hydrogen pressure 0.8MPa, carries out 2 hours hydrogenation.
After the reaction, be back to normal temperature, normal pressure, and take out from reaction vessel, stir and put in the water, steam distillation removes and desolvates, and obtains polymkeric substance (C-1).Gained hydrogenated diene base polymer (C-1) is (ii)-(iii)-(ii) type, hydrogenation ratio is 98%, and the vinyl bonds content in the block polyhutadiene (ii) is 12%, and the vinyl bonds content in the block polyhutadiene (iii) is 30%, weight-average molecular weight is 250,000.
The Production Example of hydrogenated diene base polymer (2)
In the autoclave of 5 liters of the internal volumes of nitrogen replacement, add hexanaphthene 2.5kg, tetrahydrofuran (THF) 15g, vinylbenzene (block (i)) 165g and n-Butyl Lithium 0.55g, carrying out polymerization at 50 ℃ is more than 98% until polymerisation conversion, then, add 1,3-divinyl (block is (iii)) 220g, carrying out polymerization is more than 98% until polymerisation conversion, further, add vinylbenzene (block (i)) 165g, carrying out polymerization is 100% until polymerisation conversion.
After polymerization finished, making reaction solution was 70 ℃, used titanocene dichloride to carry out hydrogenation as hydrogenation catalyst.Gained hydrogenated diene base polymer (C-2) is (i)-(iii)-(i) type, and the styrene content of bonding is 45 quality %, hydrogenation ratio 98%, and the vinyl bonds content in the polyhutadiene of block C is 80%, weight-average molecular weight is 100,000.
In addition, measure the characteristic of polymkeric substance in order to following method.
Vinyl bonds content: use infrared analysis, calculate with the Hampton method.
Hydrogenation ratio: solvent uses zellon, by 100MHz, 1The H-NMR spectrum is calculated.
Weight-average molecular weight: solvent uses trichlorobenzene, and the gel permeation chromatography (GPC) under using 135 ℃ is obtained by polystyrene conversion.
The styrene content of bonding: use carbon tetrachloride solution, by 270MHz, 1The H-NMR spectrum is calculated.
In addition, each composition that uses in embodiment, comparative example is as described below.
(A) ethylene ' alpha '-olefin class random copolymers;
(A-1) EPDM-1:JSR society system EP57C[ML 1+4(100 ℃)=90]
(A-2) EPDM-2:JSR society system EP21[ML 1+4(100 ℃)=38]
(B) unsaturated nitrile-conjugated diene rubber;
(B-1) NBR-1:JSR society system N217SH[AN content=47]
(B-2) NBR-2:JSR society system N220SH[AN content=41]
(B-3) NBR-3:JSR society system N237H[AN content=34]
(B-4) NBR-4:JSR society system N250S[AN content=20]
(C) hydrogenated diene base polymer;
The polymkeric substance (C-1, C-2) that obtains with above-mentioned manufacturing process
(D) magnesium hydroxide;
(D-1) brucite (fatty acid treatment): the refreshing island system MagseedsW-H3 of chemical industry society volume average particle size 2.5 μ m, specific surface area 8.9cm 2/ g
(D-2) brucite (wax processing): the refreshing island system MagseedsW-W3 of chemical industry society volume average particle size 2.5 μ m, specific surface area 8.9cm 2/ g
(D-3) brucite (silane coupling agent processing): the refreshing island system S-1 of chemical industry society volume average particle size 4.0 μ m, specific surface area 5.0cm 2/ g
(R-1) synthetic magnesium hydroxide (fatty acid treatment): the chemical system Kisuma5A of the society volume average particle size 0.8 μ m that coordinates, specific surface area 5.5cm 2/ g
(E) metal-salt of vinyl unsaturated carboxylic acid
(E-1) zinc methacrylate, the system Actor ZMA of chemical industry society of Kawaguchi
Other:
Carbon black: the system Seast SO of East Sea Carbon society
Stearic acid: Hua Wangshe system LUNAC S-30
Zinc oxide: just with chemical industrial society oxygenerating zinc
Organo-peroxide: dicumyl peroxide, the Japanese grease system Percumyl D-40 (purity 40%) of society
Crosslinking coagent: trihydroxy methyl propane trimethyl acrylate, the system Highcross M of Seiko chemistry society
In addition, AN represents acrylonitrile unit.
(embodiment 1)
Brucite (D-1) 80 mass parts, FEF carbon black 10 mass parts, zinc oxide 5 mass parts and stearic acid 1 mass parts crossed with the fatty acid treatment of NBR-1 (B-1) 50 mass parts of EPDM-1 (A-1) 50 mass parts of Banbury mixer (society of Kobe Steel system) mixing conduct (A) composition, conduct (B) composition, conduct (D) composition.Afterwards, cooling mixture, further use 10 inches open roll that organo-peroxide 4 mass parts and crosslinking coagent 2 mass parts are mixed with this mixture, use sheet material metal die 15cm * 15cm * 0.2cm moulding, use then 170 ℃ press-forming machine carry out 20 minutes crosslinked, make the rubber sheet of thickness 2mm, for various evaluations.
Estimate mechanical characteristics (tensile strength, tensile elongation), hardness, flame retardant resistance, oil-proofness and the weathering resistance of gained crosslinked rubber composition respectively with following method, it the results are shown in the table 1.
(1) tensile strength and tensile elongation: measure according to JIS-K6251.
(2) hardness:, measure according to JIS-K6253 as the index of flexibility.
(3) flame retardant resistance: measure oxygen index (LOI) according to JIS-K6269.Oxygen index is in the test film of wide 14mm, thick 2mm, the numerical value of the minimum oxygen concn of representing with the capacity % of mixed gas that keeps required oxygen of material combustion and nitrogen, and this value is big more, and flame retardant resistance is good more.
(4) weathering resistance: according to JIS-K6259, at ozone concn 500pphm, estimated under the static 20% tensile condition in 40 ℃, 200 hours, research has or not be full of cracks.
(5) oil-proofness: according to JIS-K6258, use IRM903 test oil (No. 3 oil), by obtaining volume change (Δ V) in 70 hours test of 100 ℃ of dippings.
(comparative example 1)
Brucite (D-1) with the synthetic magnesium hydroxide (R-1) of fatty acid treatment replaces the fatty acid treatment of (D) composition to cross with embodiment 1 the same carrying out, obtains crosslinked rubber composition.Its evaluation result is shown in Table 1.
Table 1
Embodiment Comparative example
1 2 3 4 5 6 7 8 9 1 2 3 4
EPDM-1(A-1) 50 50 50 50 50 75 40 50 50 50 10
EPDM-2(A-2) 50 100
NBR-1(B-1) 50 50 50 40 50 25 60 50 50 90
NBR-2(B-2) 50
NBR-3(B-3) 50
NBR-4(B-4) 10
Magnesium hydroxide (D-1) 80 150 80 80 80 80 80 40
Magnesium hydroxide (D-2) 80 150 150
Magnesium hydroxide (D-3) 80
Magnesium hydroxide (R-1) 80
Magnesium hydroxide (R-2)
Zinc oxide 5 5 5 5 5 5 5 5 5 5 5 5 5
Stearic acid 1 1 1 1 1 1 1 1 1 1 1 1 1
Carbon black 10 10 10 10 10 10 10 10 10 10 10 10 10
Organo-peroxide 4 4 4 4 4 4 4 4 4 4 4 4 4
Crosslinking coagent 2 2 2 2 2 2 2 2 2 2 2 2 2
Add up to 202.0 272.0 202.0 202.0 202.0 202.0 202.0 202.0 202.0 202.0 162.0 272.0 272.0
Normality rerum natura tensile strength (MPa) tensile elongation (%) hardness (Duro/A) 14.6 400 82 9.3 388 88 13.8 369 82 13.6 370 82 13.5 356 80 14.0 370 81 17.8 572 79 14.6 473 81 10.8 308 82 12.4 390 80 13.9 636 64 9.1 291 92 13.9 708 82
Oil-proofness IRM903: Δ V 44.3 41.9 47.2 35.7 46.6 34.4 67.4 34.8 50.5 45.0 47.2 5.5 77.6
Weathering resistance NC NC NC NC NC NC NC NC NC NC NC C-4 NC
Flame retardant resistance oxygen index (%) 29 35 29 29 29 29 28 29 29 29 21 35 31.5
(embodiment 2～9, comparative example 2～4)
With the blending ratio shown in the table 1,, obtain crosslinked rubber composition with embodiment 1 the same carrying out.Its evaluation result is shown in Table 1.
From the result shown in the table 1 as can be seen, use the embodiment 1 of surface-treated brucite to compare with the comparative example 1 that uses the synthetic magnesium hydroxide of surface-treated, mechanical characteristics has improved about 18%.
Equally as can be seen, use embodiment 4, the embodiment 6 of surface-treated brucite to compare with the comparative example 1 that uses the synthetic magnesium hydroxide of surface-treated, mechanical characteristics has improved about 10～13%.
As can be seen, content at magnesium hydroxide of the present invention is lower than in the comparative example 2 of 50 mass parts, can not expect the effect of flame retardant resistance, also have, in the few comparative example 3 of ethylene ' alpha '-olefin class random copolymers ratio, weathering resistance is poor, has only in the comparative example 4 of ethylene ' alpha '-olefin class random copolymers as rubber constituent the oil-proofness variation.
(embodiment 10)
In Banbury mixer (society of Kobe Steel system), hydrogenated diene base polymer (C-1) 15 mass parts of EPDM (A-1) 15 mass parts of mixing conduct (A) composition, NBR (B-1) 70 mass parts of conduct (B) composition, conduct (C) composition, magnesium hydroxide (D-2) 80 mass parts, carbon black 10 mass parts, zinc oxide 5 mass parts and stearic acid 1 mass parts of conduct (D) composition.Afterwards, cooling mixture further uses 10 inches open roll that organo-peroxide 4 mass parts and crosslinking coagent 2 mass parts are mixed with this mixture, uses following method, estimates press workability, Mooney viscosity.Then, use sheet material metal die 15cm * 15cm * 0.2cm with remaining mixture forming, use 170 ℃ press-forming machine carry out 20 minutes crosslinked, make the rubber sheet of thickness 2mm, estimate physical strength, hardness, flame retardant resistance, oil-proofness, weathering resistance.
Estimate mechanical characteristics (tensile strength, tensile elongation), hardness, flame retardant resistance, oil-proofness and the weathering resistance of gained crosslinked rubber composition respectively with following method and with embodiment 1 the same method, it the results are shown in the table 2.
(1) press workability: with the 50mm φ forcing machine (L/D=12) of mechanical industry society system in the present, 100 ℃ of temperature, extrusion moulding under the revolution 30rpm, the outward appearance of evaluation sample.
Zero: good
*: poor
(2) Mooney viscosity: measure according to JIS-K6300-1.
In addition, condition determination is ML 1+4(125 ℃)
Table 2
Embodiment Comparative example
10 11 12 13 14 15 16 17 5 6 7 8
EPDM-1(A-1) 15 15 15 15 15 30 65 30 55 15
NBR-1(B-1) 70 70 70 70 70 70 35 70 70 30 70 100
Hydrogenated diene base polymer (C-1) 15 15 7.5 15 30 15 15
Hydrogenated diene base polymer (C-2) 15 7.5
Magnesium hydroxide (D-2) 80 80 80 80 150 80 80 150 80 80 40 80
Zinc methacrylate (E-1) 2 2 2 2 2 2 2
Zinc oxide 5 5 5 5 5 5 5 5 5 5 5 5
Stearic acid 1 1 1 1 1 1 1 1 1 1 1 1
Carbon black 10 10 10 10 10 10 10 10 10 10 10 10
Crosslinking coagent 2 2 2 2 2
Organo-peroxide 4 4 4 4 4 4 4 4 4 4 4 4
Add up to 202 202 202 202 272 202 202 272 202 202 162 202
Extrude processibility ○ ○ ○ ○ ○ ○ △ ○ ○ △ ○ ○
Mooney viscosity ML 1+4(125℃) 43 44 46 45 48 44 44 48 37 44 41 47
Normality rerum natura tensile strength (MPa) tensile elongation (%) hardness (Duro A) 16.0 400 85 17.4 480 86 16.3 470 89 17.0 470 88 15.0 450 95 14.4 400 81 13.3 410 80 13.4 450 92 16.9 470 86 16.0 500 85 17.0 420 80 16.7 460 82
Oil-proofness IRM903: Δ V 44 41 41 41 40 42 70 40 45 110 47 5
Flame retardant resistance oxygen index (%) 30 30 30 30 38 30 30 38 30 30 23 30
Weathering resistance NC NC NC NC NC NC NC NC A-3 NC NC C-4
(embodiment 11～17, comparative example 5～8)
With the blending ratio shown in the table 2,, obtain rubber combination and crosslinked rubber composition with embodiment 10 the same carrying out.Its evaluation result is shown in Table 2.
From the following practical work of the result shown in the table 2 is conspicuous.
The pressurization processibility of the rubber combination of embodiment 10～17 is good, the balance excellence of mechanical characteristics, oil-proofness, weathering resistance, flame retardant resistance.
On the other hand, comparative example 5 is the examples that do not have to use (A) composition, the weathering resistance deterioration.
Comparative example 6 be (B) components in proportions at extraneous example of the present invention, the oil-proofness deterioration,
Comparative example 7 is that (D) components in proportions is in extraneous example of the present invention, flame retardant resistance deterioration.
Comparative example 8 is not have to use (A) and (C) example of composition, weathering resistance deterioration.
Industrial applicibility
Rubber composition of the present invention possesses anti-flammability, weatherability and oil resistivity, and mechanical property is excellent, therefore can be used for wire covering materials, the insulating tape purposes of distribution and automobile electrical gas distribution etc. in the roller, band, encapsulant, instrument of the manifolders such as duplicator, printer, further can be for the sebific duct class, the covering class of these sebific ducts and the multiple uses such as sealing of building materials field that need anti-flammability and oil resistivity etc.

Claims (10)

1. a flame-retardant rubber composition contains
(A) ethylene/alpha-olefin hydro carbons random copolymers 15～95 mass parts,
(B) unsaturated nitrile/conjugated diene rubber 5～85 mass parts, condition are, (A)+(B)=100 mass parts and
(D) pulverizing with the magnesium hydroxide is the natural mineral of main component, and with at least a kind of magnesium hydroxide 50～400 mass parts of carrying out surface treatment and preparing that is selected from fatty acid ester, wax, lipid acid, fatty acid metal salt, winterized stearin, silane coupling agent and the titanate coupling agent.
2. a flame-retardant rubber composition contains
(A) ethylene/alpha-olefin hydro carbons random copolymers 3～62 mass parts,
(B) unsaturated nitrile/conjugated diene rubber 35～94 mass parts,
(C) hydrogenated diene base polymer 3～62 mass parts, condition are, (A)+(B)+(C)=100 mass parts and
(D) pulverizing with the magnesium hydroxide is the natural mineral of main component, and with at least a kind of magnesium hydroxide 50～400 mass parts of carrying out surface treatment and preparing that is selected from fatty acid ester, wax, lipid acid, fatty acid metal salt, winterized stearin, silane coupling agent and the titanate coupling agent.
3. claim 1 or 2 described flame-retardant rubber compositions, the mooney viscosity [ML of therein ethylene/alpha-olefines random copolymers (A) 1+4(100 ℃)] be 20～300.
4. claim 1 or 2 described flame-retardant rubber compositions, wherein the unsaturated nitrile unit content of unsaturated nitrile/conjugated diene rubber (B) is 33～70 quality %.
5. the described flame-retardant rubber composition of claim 2, wherein the hydrogenated diene base polymer (C) in the rubber combination is to have vinyl bonds content to be lower than 25% polybutadiene block and vinyl bonds content be the hydride of the segmented copolymer of the conjugated diolefine polymer block more than 25%, below 90%.
6. the described flame-retardant rubber composition of claim 1 with respect to total amount 100 mass parts of composition (A) and composition (B), further contains metal-salt 1～10 mass parts of (E) vinyl unsaturated carboxylic acid.
7. the described flame-retardant rubber composition of claim 2 with respect to total amount 100 mass parts of composition (A), composition (B) and composition (C), further contains metal-salt 1～10 mass parts of (E) vinyl unsaturated carboxylic acid.
8. claim 1 or 2 described flame-retardant rubber compositions, oxygen index is more than 28%.
9. rubber item, it is with claim 1 or the crosslinked manufacturing of 2 described flame-retardant rubber compositions.
10. wire covering materials, it is with claim 1 or the crosslinked manufacturing of 2 described flame-retardant rubber compositions.
CNB2004800036031A 2003-02-05 2004-02-04 Flame-retardant rubber composition, rubber articles and wire covering materials Expired - Lifetime CN100339434C (en)

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