WO2022075300A1 - Produit réticulé - Google Patents

Produit réticulé Download PDF

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Publication number
WO2022075300A1
WO2022075300A1 PCT/JP2021/036758 JP2021036758W WO2022075300A1 WO 2022075300 A1 WO2022075300 A1 WO 2022075300A1 JP 2021036758 W JP2021036758 W JP 2021036758W WO 2022075300 A1 WO2022075300 A1 WO 2022075300A1
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mass
crosslinked product
examples
tert
polyether polymer
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PCT/JP2021/036758
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English (en)
Japanese (ja)
Inventor
俊幸 船山
和樹 宇野
友訓 原田
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株式会社大阪ソーダ
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Priority to JP2022555493A priority Critical patent/JPWO2022075300A1/ja
Publication of WO2022075300A1 publication Critical patent/WO2022075300A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to a crosslinked product using a polyether polymer and a polymethyl methacrylate resin.
  • Rubber materials using polyether polymers are widely used as fuel hoses, air hoses, and tube materials in automobile applications, taking advantage of their heat resistance, oil resistance, ozone resistance, etc.
  • heat resistance Is getting tougher year by year.
  • organic nickel compounds particularly nickel dibutyldithiocarbamate, have been widely used as an effective antiaging agent capable of improving heat resistance and ozone resistance even in a polyether polymer such as epihalohydrin-based rubber.
  • the present inventors have made the polymethylmethacrylate in the composition containing the polyether polymer for the crosslinked product and the polymethylmethacrylate resin. It has been found that when the relationship between the resin content ratio and the extraction ratio when the crosslinked product is soxley-extracted using acetone as a solvent has a certain relationship, it has excellent heat resistance and oil resistance.
  • Item 1 A crosslinked product prepared from a rubber composition containing (a) a polyether-based polymer, (b) a polymethyl methacrylate resin, and (c) a cross-linking agent.
  • B the mass of the rubber composition
  • B / A and the crosslinked product (mass X) are used as a solvent for soxley extraction at 78 ° C.
  • 6 A crosslinked product in which Y / X satisfies the following formula (1) when the extraction amount (mass Y) after the time is changed.
  • Item 2 The crosslinked product according to Item 1, wherein the (a) polyether-based polymer contains at least one unit selected from ethylene oxide, propylene oxide, epichlorohydrin, and allyl glycidyl ether as a constituent unit.
  • the crosslinked product of the present invention has excellent heat resistance and oil resistance, it can be widely applied to fields in which heat-resistant and oil-resistant synthetic rubber is used.
  • it is useful as a rubber material for various fuel-based laminated hoses for automobiles, air-based laminated hoses, tubes, belts, diaphragms, seals, etc., and rubber materials for general industrial equipment / devices.
  • the crosslinked product of the present invention is a crosslinked product prepared from a rubber composition containing (a) a polyether polymer, (b) a polymethyl methacrylate resin, and (c) a cross-linking agent.
  • a polyether polymer containing (a) a polyether polymer, (b) a polymethyl methacrylate resin, and (c) a cross-linking agent.
  • B / A and the crosslinked product (mass X) are used as a solvent for soxley extraction at 78 ° C. 6
  • excellent heat resistance and oil resistance can be obtained. 0.10 ⁇ (Y / X) / (B / A) ⁇ 0.90 (1)
  • the reason why such an action effect is obtained is not always clear, but it is presumed as follows.
  • the acetone extraction content of the rubber crosslinked product is reduced by using (a) a polyether polymer and (b) a polymethyl methacrylate resin in combination and applying shearing at a high temperature. This suggests the formation of a chemical bond between the domains of (a) the polyether polymer and (b) the polymethyl methacrylate resin.
  • the larger the B / A the larger the mass ratio of the (b) polymethylmethacrylate resin in the rubber composition.
  • Y / X when the crosslinked product (mass X) is the extraction amount (mass Y) after soxley extraction is performed at 78 ° C. for 6 hours using acetone as a solvent indicates the mass ratio of the acetone extract in the crosslinked product. ..
  • the acetone extract is a relatively low molecular weight component that is not involved in cross-linking in the cross-linked product. Therefore, the smaller the Y / X, the higher the crosslink density.
  • (Y / X) / (B / A) indicates the amount of the uncrosslinked component in the crosslinked product with respect to the amount of the (b) polymethylmethacrylate resin component in the rubber composition, and (a) the polyether-based polymer.
  • -(B) Means the amount of chemical bond between the domains of the polymethyl methacrylate resin.
  • the crosslinked product of the present invention is produced from a rubber composition containing (a) a polyether polymer, (b) a polymethyl methacrylate resin, and (c) a crosslinking agent.
  • the (a) polyether-based polymer in the rubber composition of the present invention includes alkylene oxides such as ethylene oxide, propylene oxide and n-butylene oxide, methyl glycidyl ether, ethyl glycidyl ether, n-glycidyl ether and allyl glycidyl ether. It is preferably a polymer obtained by polymerizing a compound selected from glycidyls such as phenylglycidyl ether, epihalohydrins such as epichlorohydrin and epibromhydrin, and styrene oxide, and is preferably a polymer obtained by polymerizing ethylene oxide, propylene oxide, etc.
  • alkylene oxides such as ethylene oxide, propylene oxide and n-butylene oxide
  • methyl glycidyl ether ethyl glycidyl ether
  • n-glycidyl ether n-glycidyl
  • the polyether-based polymer may be used alone or in combination of two or more.
  • the polyether polymer preferably has 20 mol% or more of epichlorohydrin-based structural units, more preferably 30 mol% or more, particularly preferably 40 mol% or more, and may have 100 mol% or less, 90 mol. % Or less, 80 mol% or less, and 75 mol% or less.
  • the polyether polymer preferably has 10 mol% or more of the structural unit based on ethylene oxide, more preferably 20 mol% or more, particularly preferably 25 mol% or more, preferably 80 mol% or less, and 70 mol% or less. It is more preferable to have it, and it is particularly preferable to have it in an amount of 60 mol% or less.
  • the total of the building blocks based on ethylene oxide and the building blocks based on epichlorohydrin is preferably 90 mol% or more, more preferably 93 mol% or more, and particularly preferably 97 mol% or more. ..
  • the polyether polymer may have 1 mol% or more of structural units based on allyl glycidyl ether, 2 mol% or more, 3 mol% or more, and 15 mol% or less. It may have 10 mol% or less, and may have 7 mol% or less.
  • the polymerization composition is determined by the chlorine content and iodine value.
  • Chlorine content is measured by potentiometric titration according to the method described in JIS K7229. From the obtained chlorine content, the mole fraction of the constituent unit based on epichlorohydrin is calculated. The iodine value is measured by a method according to JIS K6235. From the obtained iodine value, the mole fraction of the constituent unit based on allyl glycidyl ether is calculated.
  • the mole fraction of the constituent unit derived from alkylene oxide is calculated from the mole fraction of the constituent unit based on epichlorohydrin and the molar fraction of the constituent unit based on allylglycidyl ether.
  • the weight average molecular weight of the polymer used is not particularly limited, but the lower limit of the weight average molecular weight is preferably 200,000 or more, more preferably 300,000 or more, and the weight.
  • the upper limit of the average molecular weight is preferably 3 million or less, more preferably 2 million or less.
  • a material capable of ring-opening polymerization of an oxylan compound is used as a catalyst, and the monomer can be polymerized.
  • the polymerization temperature is, for example, in the range of ⁇ 20 to 100 ° C.
  • This polymerization may be either solution polymerization or slurry polymerization.
  • the catalysts include, for example, a catalyst system mainly composed of organic aluminum in which an oxo acid compound of water or phosphorus or acetylacetone is reacted, a catalyst system mainly composed of organic zinc in which water is reacted, and organic tin-phosphorus. Examples thereof include an acid ester condensate catalyst system.
  • the polymethylmethacrylate resin (b) of the present invention is a homopolymer of a methyl methacrylate monomer (methyl methacrylate monomer) or a copolymer of a methyl methacrylate monomer and an acrylic acid ester monomer. However, other monomers may be copolymerized. In the case of the copolymer, it is preferable to contain a structural unit based on methyl methacrylate in an amount of 80% by mass or more.
  • the polymethyl methacrylate resin may be used alone or in combination of two or more.
  • acrylic acid ester monomer examples include methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and (meth) acrylic acid.
  • Benzyl, cyclohexyl (meth) acrylate and the like can be exemplified.
  • Examples of other monomers include nitrile-based monomers such as acrylonitrile and methacrylonitrile, and maleimide-based monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. ..
  • the method for producing the polymethyl methacrylate resin is not particularly limited, and known emulsification polymerization methods, suspension polymerization methods, bulk polymerization methods, solution polymerization methods and the like can be exemplified.
  • polymethylmethacrylate resin of the present invention commercially available ones can be used, for example, the product name: Parapet series (manufactured by Kuraray Co., Ltd.) and the product name: Acrypet series (manufactured by Mitsubishi Rayon Co., Ltd.) are used. can do.
  • the bicut softening temperature of the polymethyl methacrylate resin is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 95 ° C. or higher, preferably 130 ° C. or lower, more preferably 120 ° C. or lower, and further. It is preferably 115 ° C. or lower.
  • the Vicat softening temperature is measured according to JIS K7206.
  • the mass ratio of the (a) polyether-based polymer and (b) polymethylmethacrylate resin in the rubber composition of the present invention is 85: between (a) the polyether-based polymer and (b) the polymethylmethacrylate resin. It is preferably 15 to 30:70, more preferably 80:20 to 40:60, and particularly preferably 75:25 to 50:50.
  • the total content of (a) the polyether polymer and (b) the polymethyl methacrylate resin in 100% by mass of the rubber composition of the present invention is preferably 45% by mass or more, more preferably 50% by mass or more, and further. It is preferably 60% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.
  • Examples of the (c) cross-linking agent of the present invention include known cross-linking agents that utilize the reactivity of chlorine atoms and known cross-linking agents that utilize the reactivity of side chain double bonds.
  • Known cross-linking agents that utilize the reactivity of chlorine atoms include polyamine-based cross-linking agents, thiourea-based cross-linking agents, thiadiazol-based cross-linking agents, mercaptotriazine-based cross-linking agents, pyrazine-based cross-linking agents, quinoxalin-based cross-linking agents, and bisphenol-based cross-linking agents.
  • cross-linking agent utilizing the reactivity of the side chain double bond
  • a sulfur-based cross-linking agent and an organic peroxide-based cross-linking agent can be exemplified.
  • the cross-linking agent may be used alone or in combination of two or more. Of these, a quinoxaline-based cross-linking agent is preferable.
  • polyamine-based cross-linking agent examples include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, p-phenylenediamine, cumendiamine, N, N,'-dicinnamilyden-1,6-hexanediamine, ethylenediamine carbamate, and hexane.
  • examples include methylenediamine carbamate.
  • thiourea-based cross-linking agent examples include ethylene thiourea, 1,3-diethyl thiourea, 1,3-dibutyl thiourea, and trimethyl thiourea.
  • thiadiazole-based cross-linking agent examples include 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-thiadiazole-5-thiobenzoate and the like.
  • Examples of the mercaptotriazine-based cross-linking agent include 2,4,6-trimercapto-1,3,5-triazine, 2-hexylamino4,6-dimercaptotriazine, 2-diethylamino-4,6-dimercaptotriazine, 2 -Cyclohexylamino-4,6 dimercaptotriazine, 2-dibutylamino-4,6-dimercaptotriazine, 2-anilino-4,6-dimercaptotriazine, 2-phenylamino-4,6-dimercaptotriazine, etc. can give.
  • Examples of the pyrazine-based cross-linking agent include 2,3-dimercaptopyrazine derivatives, and examples of 2,3-dimercaptopyrazine derivatives include pyrazine-2,3-dithiocarbonate and 5-methyl-2,3-di. Examples thereof include mercaptopyrazine, 5-ethylpyrazine-2,3-dithiocarbonate, 5,6-dimethyl-2,3-dimercaptopyrazine, 5,6-dimethylpyrazine-2,3-dithiocarbonate and the like.
  • Examples of the quinoxaline-based cross-linking agent include 2,3-dimercaptoquinoxaline derivatives, and examples of 2,3-dimercaptoquinoxaline derivatives include quinoxaline-2,3-dithiocarbonate and 6-methylquinoxaline-2,3-. Examples thereof include dithiocarbonate (quinomethionate), 6-ethyl-2,3-dimercaptoquinoxaline, 6-iopropylquinoxaline-2,3-dithiocarbonate, 5,8-dimethylquinoxaline-2,3-dithiocarbonate and the like.
  • bisphenol-based cross-linking agent examples include 4,4-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone (bisphenol S), 1,1-cyclohexylidene-bis (4-hydroxybenzene), 2-chloro-1, 4-Cyclohexylene-bis (4-hydroxybenzene), 2,2-isopropyridene-bis (4-hydroxybenzene) (bisphenol A), hexafluoroisopropyrine-bis (4-hydroxybenzene) (bisphenol AF), and Examples thereof include 2-fluoro-1,4-phenylene-bis (4-hydroxybenzene).
  • Sulfur-based cross-linking agents include sulfur, morpholine disulfide, tetramethylthium disulfide, tetraethylthium disulfide, tetrabutyltiuram disulfide, N, N'-dimethyl-N, N'-diphenylthiuram disulfide, dipentanemethylenetiuram tetrasulfide, and disulfide. Examples thereof include pentamethylene thiuram tetrasulfide and dipentamethylene thiuram hexasulfide.
  • organic peroxide-based cross-linking agent examples include tert-butyl hydroperoxide, 1,1,3,3, -tetramethylbutylhydroperoxide, cumenehydroperoxide, diisopropylbenzenehydroperoxide, di-tert-butyl peroxide, and dicumyl peroxide.
  • Tert-butylcumyl peroxide 1,1-tert-butylperoxycyclohexane, 2,5-dimethyl-2,5-ditert-butylperoxyhexane, 2,5-dimethyl-2,5-ditertdibutylperoxyhe Xin-3,1,3-bisstart-butylperoxyisopropylbenzene, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, 1,1-bisstart-butylperoxy-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis tert-butylperoxyvalerate, benzoyl peroxide, tert-butyl peroxide isobutyrate, tert-butylperoxy2-ethylhexanoate, tert-butylperoxybenzoate, tert-butylperoxyisopropylcarbo Examples include nat,
  • the blending amount of the cross-linking agent is preferably 0.1 to 20 parts by mass, preferably 0 to 20 parts by mass when the total of (a) the polyether polymer and (b) the polymethyl methacrylate resin is 100 parts by mass. .2 to 10 parts by mass is more preferable, and 0.3 to 5 parts by mass is particularly preferable.
  • a known accelerator that is, a crosslinking accelerator used together with a crosslinking agent can be used as it is in the rubber composition of the present invention.
  • cross-linking accelerator examples include thiuram-based cross-linking accelerator, thiazole-based cross-linking accelerator, morpholine sulfide-based cross-linking accelerator, sulfenamide-based cross-linking accelerator, guanidine-based cross-linking accelerator, thiourea-based cross-linking accelerator, and aldehyde-.
  • the cross-linking accelerator may be used alone or in combination of two or more.
  • thiuram-based cross-linking accelerator examples include tetramethylthium disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, dipentamethylene thiuram hexasulfide, and tetramethyl thiuram monosulfide.
  • thiazole-based cross-linking accelerator examples include mercaptobenzothiazole, dibenzothiadyl-disulfide, various metal salts of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, and 2- (N, N-diethylthiocarbamoylthio).
  • Benzothiazole, 2- (4'-monohorino-dithio) benzothiazole, di-2-benzothiazolyl disulfide and the like can be mentioned.
  • Examples of the morpholine sulfide-based cross-linking accelerator include morpholine disulfide.
  • sulfenamide-based cross-linking accelerator examples include N-cyclohexyl-2-benzothiadyl-sulfenamide, N, N-dicyclohexyl-2-benzothiadyl-sulfenamide, N-oxydiethylene-2-benzothiadyl-sulfenamide, and N.
  • N-cyclohexyl-2-benzothiadyl-sulfenamide N, N-dicyclohexyl-2-benzothiadyl-sulfenamide, N-oxydiethylene-2-benzothiadyl-sulfenamide, and N.
  • the third butyl-2-benzothiadyl-sulfenamide, N-third butyl-di (2-benzothiazole) sulfenamide and the like can be mentioned.
  • guanidine-based cross-linking accelerator examples include diphenylguanidine and ditrilguanidine.
  • thiourea-based cross-linking accelerator examples include ethylene thiourea, diethylene thiourea, dibutyl thiourea, dilauryl thiourea, trimethyl thiourea, and diphenyl thiourea.
  • aldehyde-ammonia-based cross-linking accelerator examples include hexamethylenetetramine.
  • dithiocarbamate-based cross-linking accelerator examples include zinc dimethyldithiocarbamate, zinc diethylcarbamate, zinc N-pentamethylenedithiocarbamate and the like.
  • Examples of the xanthogenate-based cross-linking accelerator include zinc isopropylxanthogenate and zinc butylxanthogenate.
  • fatty acid alkali metal salt-based cross-linking accelerator examples include sodium stearate and potassium stearate.
  • DBU salt-based cross-linking accelerator examples include DBU-carbonate, DBU-stearate, DBU-2-ethylhexylate, DBU-benzoate, DBU-salicylate, and DBU-3-hydroxy-2-naphthoate.
  • DBU-phenol resin salt DBU-2
  • DBN salt-based cross-linking accelerator examples include DBN-carbonate, DBN-stearate, DBN-2-ethylhexylate, DBN-benzoate, DBN-salicylate, and DBN-3-hydroxy-2-naphthoate.
  • DBN-phenol resin salt examples include DBN-2-mercaptobenzothiazole salt, DBN-2-mercaptobenzimidazole salt and the like.
  • the blending amount of the cross-linking accelerator shall be 0.1 to 15 parts by weight when the total of (a) the polyether polymer and (b) the polymethyl methacrylate resin of the present invention is 100 parts by weight. Is preferable, 0.1 to 10 parts by weight is more preferable, and 0.1 to 5 parts by weight is particularly preferable.
  • the acid receiving agent used in the present invention known acid receiving agents can be used, but metal compounds and / or inorganic microporous crystals are preferable.
  • the metal compound include oxides of Group II (Groups 2 and 12) metals in the periodic table, hydroxides, carbonates, carboxylates, silicates, borates, phosphites, and Group III of the periodic table.
  • Metal oxides hydroxides, carboxylates, silicates, sulfates, nitrates, phosphates, periodic table Group IV (Groups 4 and 14) metal oxides, Examples thereof include metal compounds such as basic carbonates, basic carboxylates, basic subphosphates, basic sulfites, and tribasic sulfates.
  • the metal compound include magnesia, magnesium hydroxide, aluminum hydroxide, barium hydroxide, sodium carbonate, magnesium carbonate, barium carbonate, fresh lime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, and the like.
  • the inorganic microporous crystal means a crystalline porous body, and can be clearly distinguished from an atypical porous body such as silica gel and alumina.
  • examples of such inorganic microporous crystals include zeolites, aluminophosphate-type molecular sieves, layered silicates, synthetic hydrotalcites, alkali metal titanates and the like.
  • Particularly preferred acid receiving agents include synthetic hydrotalcite.
  • the zeolites are, in addition to natural zeolites, various zeolites such as A-type, X-type, and Y-type synthetic zeolites, sodalites, natural or synthetic mordenites, and ZSM-5, and metal substituents thereof. It may be used in combination of two or more kinds.
  • the metal of the metal substituent is often sodium.
  • As the zeolites those having a large acid receptivity are preferable, and type A zeolites are preferable.
  • the synthetic hydrotalcite is represented by the following general formula (1).
  • Z is a real number of 1 to 5
  • w is a real number of 0 to 10, respectively.
  • the blending amount of the acid receiving agent shall be 0.1 to 15 parts by mass when the total of (a) the polyether polymer of the present invention and (b) the polymethyl methacrylate resin is 100 parts by mass. It is preferably 0.5 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass.
  • anti-aging agents include benzimidazole-based anti-aging agents, dithiocarbamate-based anti-aging agents, amine-based anti-aging agents, phenol-based anti-aging agents, thiourea-based anti-aging agents, organic thioic acids, and subphosphorus. Acids are mentioned, and at least one selected from these is preferable, benzimidazole-based anti-aging agents and dithiocarbamate-based anti-aging agents are more preferable, and dithiocarbamate-based anti-aging agents are more preferable.
  • Examples of the benzimidazole-based antiaging agent include zinc salts of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and 2-mercaptobenzimidazole.
  • dithiocarbamate-based antiaging agent examples include nickel diethyldithiocarbamate, nickel dimethyldithiocarbamate, nickel dibutyldithiocarbamate, nickel diisobutyldithiocarbamate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, N.
  • examples thereof include copper ethyl-N-phenyldithiocarbamate, copper N-pentamethylene dithiocarbamate, and copper dibenzyldithiocarbamate.
  • amine-based antiaging agent examples include phenyl- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, p- (p-toluenesulfonylamide) -diphenylamine, 4,4'-( ⁇ , ⁇ '-dimethylbenzyl) diphenylamine, 4 , 4'-Dioctyl diphenylamine, high temperature reaction product of diphenylamine and acetone, low temperature reaction product of diphenylamine and acetone and low temperature reaction product, low temperature reaction product of diphenylamine, aniline, acetone, reaction product of diphenylamine and diisobutylene, octylated diphenylamine, Dioctylated diphenylamine, p, p'-dioctyl-diphenylamine, octylated diphenylamine mixture, substituted diphenylamine, alkylated
  • Examples thereof include quinoline, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 4,4'-bis (a, a-dimethylbenzyl) diphenylamine, N, N'-di-2-naphthyl-. It is preferably at least one selected from p-phenylenediamine.
  • phenolic antiaging agent examples include 2,5-di- (t-amyl) -hydroquinone, 2,5-di-t-butylhydroquinone, and hydroquinone monomethyl ether, and the monophenolic agent is 1-oxy-3-.
  • Methyl-4-isopropylbenzene 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6 -Di-t-butyl-4-sec-butylphenol, butyl hydroxyanisole, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-t-butyl- ⁇ -dimethylamino-p -Cresol, alkylated phenol, aralkyl substituted phenol, phenol derivative, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2 , 2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2-methylenebis (6
  • 2,2'-Methylenebis (4-ethyl-6-tert-butylphenol), 2'2-Methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert- Butylphenol), preferably at least one selected from 4,4'-thiobis (3-methyl-6-tert-butylphenol).
  • thiourea-based antiaging agent examples include 1,3-bis (dimethyl-aminopropyl) -2-thiourea and tributylthiourea. It was
  • Dilauryl thiodipropionate disstearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, pentaerythritol-tetrakis- ( ⁇ ) as organic thioacids -Lauryl-thiopropionate), dilauryl-thiodipropionate and the like are exemplified.
  • phosphites examples include tris (nonyl-phenyl) phosphite, tris (mixed mono- and di-nonylphenyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monotridecyl phosphite, and diphenyl isodecyl.
  • the lower limit of the amount of the antiaging agent added is 0.01 part by mass or more when the total of (a) the polyether polymer and (b) the polymethylmethacrylate resin of the present invention is 100 parts by mass. It is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and the upper limit is preferably 3.5 parts by mass or less, and 3.0 parts by mass. The following is particularly preferable.
  • a known reinforcing agent can be used, specifically, calcium carbonate, talc, silica, clay, carbon fiber, glass fiber, carbon black, titanium oxide, magnesium oxide, hydrotalcite, and hydroxylation.
  • examples thereof include magnesium, antimony oxide, zinc oxide and the like, and carbon black and silica are preferable.
  • carbon black examples include furnace black, acetylene black, thermal black, channel black, graphite and the like, and specifically, SAF, ISAF, HAF, EPC, XCF, FEF, GPF, HMF, SRF, FT and MT. It can be exemplified. These carbon blacks may be used alone or in combination of two or more.
  • the type of silica is not particularly limited, and is, for example, wet method silica (hydrous silicic acid), dry method silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like.
  • wet method silica is preferable.
  • Wet method silica is a fine particle of hydrous silicic acid produced by acid decomposition of an aqueous sodium silicate solution or an alkaline earth metal silicate, and is a filler for rubber mainly composed of silicon dioxide.
  • the blending amount of the reinforcing agent is preferably 10 to 100 parts by mass, preferably 20 parts by mass when the total of (a) the polyether polymer and (b) the polymethyl methacrylate resin of the present invention is 100 parts by mass. It is more preferably to 80 parts by mass.
  • processing aid examples include paraffin waxes such as paraffin waxes and hydrocarbon waxes and hydrocarbon resins; fatty acids such as stearic acid and palmitic acid; fatty acid amides such as stearoamide and oleylamide; n-.
  • Fatty acid esters such as butyl stearate; sorbitan fatty acid esters such as sorbitan stearate; fatty alcohols; etc. may be mentioned, and these may be used alone or in combination of two or more.
  • the blending amount of the processing aid shall be 0.1 to 20 parts by mass when the total of (a) the polyether polymer of the present invention and (b) the polymethyl methacrylate resin is 100 parts by mass. Is preferable, and 0.3 to 10 parts by mass is more preferable.
  • plasticizer examples include phthalic acid derivatives such as dioctyl phthalate (bis phthalate (2-ethylhexyl)) and diallyl ester phthalate, adipic acid derivatives such as dibutyl diglycol-adipate and di (butoxyethoxy) ethyl adipate, and sebacic acid.
  • phthalic acid derivatives such as dioctyl phthalate (bis phthalate (2-ethylhexyl)) and diallyl ester phthalate
  • adipic acid derivatives such as dibutyl diglycol-adipate and di (butoxyethoxy) ethyl adipate
  • sebacic acid examples include sebacic acid derivatives such as dioctyl and trimellitic acid derivatives such as trioctyl remeritate, and these may be used alone or in combination of two or more.
  • the blending amount of the plasticizer may be 0.1 to 50 parts by mass when the total of (a) the polyether polymer and (b) the polymethyl methacrylate resin of the present invention is 100 parts by mass. It is preferably 3 to 35 parts by mass, and more preferably 3 to 35 parts by mass.
  • any means conventionally used in the field of polymer processing for example, a mixing roll, a Banbury mixer, various kneaders and the like can be used.
  • knead at a high temperature such as 180 ° C. to 250 ° C. It is also possible to knead (a) a polyether polymer and (b) a polymethyl methacrylate resin at a high temperature of 180 ° C to 250 ° C in advance, and then add a cross-linking agent or the like to knead. be.
  • the high temperature is preferably a temperature about 60 ° C. to 150 ° C. higher than the Vicat softening temperature of the polymethyl methacrylate resin used.
  • Crosslinked product of the present invention is produced from the rubber composition of the present invention and obtained by cross-linking. It is usually obtained by heating to 100 to 200 ° C., and the crosslinking time varies depending on the temperature, but it is usually carried out between 0.5 and 300 minutes.
  • any method such as compression molding by a mold, injection molding, air bath, heating by infrared rays or microwaves can be used.
  • the crosslinked product of the present invention is a crosslinked product prepared from a rubber composition containing (a) a polyether polymer, (b) a polymethyl methacrylate resin, and (c) a cross-linking agent.
  • a polyether polymer containing (a) a polyether polymer, (b) a polymethyl methacrylate resin, and (c) a cross-linking agent.
  • B / A and the crosslinked product (mass X) are used as a solvent for soxley extraction at 78 ° C. 6
  • the lower limit of (Y / X) / (B / A) is 0.10 or more, may be 0.15 or more, may be 0.20 or more, and may be 0.25 or more. It may be 0.30 or more, 0.35 or more, and the upper limit is 0.90 or less, preferably 0.80 or less, and preferably 0.75 or less. More preferably, it is more preferably 0.70 or less, particularly preferably 0.65 or less, most preferably 0.60 or less, even more preferably 0.55 or less, and 0. More preferably, it is 50 or less.
  • the B / A is preferably 0.10 or more, more preferably 0.12 or more, still more preferably 0.15 or more, preferably 0.70 or less, more preferably 0.60 or less, still more preferably 0. It is 50 or less, particularly preferably 0.40 or less.
  • Soxhlet extraction is performed according to JIS-K6229. Specifically, the crosslinked product is cut into 1 cm pieces, weighed 5 g, placed in a cylindrical filter paper, and set in a cylinder. Further, 100 ml of acetone is placed in an Erlenmeyer flask and set at the bottom. The heater is set to 78 ° C., the cooling is set to 20 ° C., and Soxhlet extraction is performed for 6 hours. Take out the cylindrical filter paper, volatilize acetone, measure the mass, and use the reduced amount of the sample as the extraction amount.
  • a crosslinked product satisfying the above formula (1) can be produced, for example, as follows.
  • the mass ratio of (a) the polyether polymer and (b) the polymethyl methacrylate resin in the rubber composition of the present invention may be adjusted to the above-mentioned preferable range. Further, as described above, in the rubber composition of the present invention, it is preferable to knead at a high temperature such as 180 ° C. to 250 ° C., and in advance, at a high temperature such as 180 ° C. to 250 ° C., (a) a polyether system. It is also preferable to knead the polymer and (b) the polymethyl methacrylate resin, and then add a cross-linking agent or the like to knead the mixture.
  • each compounding agent shown in Table 1 was kneaded with a pressure kneader to prepare an A kneading compound.
  • This A kneading compound was kneaded with an open roll to prepare a B kneading compound.
  • A is a raw material of the A kneading compound
  • B is a raw material to be blended in the A kneading compound when the B kneading compound is produced.
  • the unit in the formulation is parts by mass.
  • Example 1 the polyether polymer and the polymethyl methacrylate resin were pre-kneaded at a pressure kneader at 190 ° C., and the polyether polymer and the polymethyl methacrylate resin were pre-kneaded.
  • other raw materials for the A kneading compound were added and further kneaded at 150 ° C. to prepare the A kneading compound.
  • To the obtained A kneaded sheet 1.7 parts by mass of quinomethionate was added to a total of 100 parts by mass of the polyether polymer and the polymethyl methacrylate resin, and the sheet was formed by an open roll.
  • Comparative Example 1 the compounding agents shown in Table 1 were kneaded at 150 ° C. with a pressure kneader to prepare an A kneading compound, which was molded into a sheet using an open roll to obtain an A kneading sheet. To 100 parts by mass of the polyether polymer, 1.7 parts by mass of quinomethionate was added to the obtained A kneaded sheet, and the sheet was formed into a sheet by an open roll. In Example 3, the compounding agents shown in Table 1 were kneaded at 190 ° C.
  • a tensile test was carried out according to JIS K6251 and a hardness test was carried out according to JIS K6253.
  • Heat resistance test according to JIS K6257 accelerated aging test A-2 method, tensile test according to JIS K6251 after heat resistance test (150 ° C x 168 hours, 150 ° C x 288 hours), hardness according to K6253 The test was carried out.
  • An oil resistance test was carried out according to JIS K6258, a tensile test was carried out according to JIS K6251 after an engine oil resistance test (grade: 5W-40, 150 ° C. x 70 hours), and a hardness test was carried out according to K6253. ..
  • Soxhlet extraction is performed according to JIS-K6229. Specifically, the crosslinked sheet is cut into 1 cm pieces, weighed in 5 g (X), placed in a cylindrical filter paper, and set in a cylinder. Further, 100 ml of acetone is placed in an Erlenmeyer flask and set at the bottom. The heater is set to 78 ° C., the cooling is set to 20 ° C., and Soxhlet extraction is performed for 6 hours. Take out the cylindrical filter paper, volatilize acetone, measure the mass, and use the weight loss (Y) of the sample as the extraction amount.
  • Y weight loss
  • Table 2 shows the test results obtained from each test method.
  • Tb means the tensile strength specified in the tensile test
  • Eb means the elongation specified in the tensile test
  • Hs means the hardness.
  • the crosslinked product obtained by cross-linking the rubber composition of the present invention has excellent heat resistance and oil resistance, and is therefore useful as a tube material for fuel hoses, air hoses, etc., and rubber packing, especially in automobile applications.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Pour un produit réticulé utilisant un polymère polyéther, il est difficile d'améliorer la résistance à la chaleur, la résistance à l'huile, etc. au-delà de l'état courant ; et la présente invention s'attaque au problème d'améliorer encore la résistance à la chaleur, la résistance à l'huile, etc. d'un produit réticulé utilisant un polymère polyéther. Il a été découvert qu'un produit réticulé utilisant un polymère polyéther et une résine de poly(méthacrylate de méthyle) a une remarquable résistance à la chaleur et une remarquable résistance à l'huile lorsqu'il y a une relation spécifique entre la teneur de la résine de poly(méthacrylate de méthyle) dans une composition contenant la résine de poly(méthacrylate de méthyle) et le polymère polyéther pour le produit réticulé et le taux d'extraction lorsque le produit réticulé est soumis à une extraction au Soxhlet à l'aide d'acétone en tant que solvant.
PCT/JP2021/036758 2020-10-06 2021-10-05 Produit réticulé WO2022075300A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4288570A (en) * 1980-05-12 1981-09-08 Monsanto Company Thermoplastic compositions of epichlorohydrin rubber and poly(alkyl methacrylate) resin
JPS58111843A (ja) * 1981-12-25 1983-07-04 Osaka Soda Co Ltd ブレンドゴム加硫組成物
JPS591565A (ja) * 1982-06-28 1984-01-06 Osaka Soda Co Ltd ブレンドゴム加硫組成物
JPS5980566A (ja) * 1982-10-27 1984-05-10 Nok Corp キヤブレ−タ−スロツトルオ−プナ−用ダイアフラム
JPS6474253A (en) * 1987-09-16 1989-03-20 Nippon Zeon Co Rubber blend
JPH0457846A (ja) * 1990-06-26 1992-02-25 Sumitomo Chem Co Ltd メタクリル樹脂組成物
JPH0959507A (ja) * 1995-08-18 1997-03-04 Tokai Rubber Ind Ltd 高分子組成物の製法および架橋体の製法ならびにそれにより得られた架橋体
JPH11302493A (ja) * 1998-04-23 1999-11-02 Tokai Rubber Ind Ltd 形状記憶用樹脂組成物およびそれを用いた形状記憶製品
JP2004182786A (ja) * 2002-11-29 2004-07-02 Nippon Zeon Co Ltd 半導電性ゴムロール用ゴム組成物及び半導電性ゴムロール

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4288570A (en) * 1980-05-12 1981-09-08 Monsanto Company Thermoplastic compositions of epichlorohydrin rubber and poly(alkyl methacrylate) resin
JPS58111843A (ja) * 1981-12-25 1983-07-04 Osaka Soda Co Ltd ブレンドゴム加硫組成物
JPS591565A (ja) * 1982-06-28 1984-01-06 Osaka Soda Co Ltd ブレンドゴム加硫組成物
JPS5980566A (ja) * 1982-10-27 1984-05-10 Nok Corp キヤブレ−タ−スロツトルオ−プナ−用ダイアフラム
JPS6474253A (en) * 1987-09-16 1989-03-20 Nippon Zeon Co Rubber blend
JPH0457846A (ja) * 1990-06-26 1992-02-25 Sumitomo Chem Co Ltd メタクリル樹脂組成物
JPH0959507A (ja) * 1995-08-18 1997-03-04 Tokai Rubber Ind Ltd 高分子組成物の製法および架橋体の製法ならびにそれにより得られた架橋体
JPH11302493A (ja) * 1998-04-23 1999-11-02 Tokai Rubber Ind Ltd 形状記憶用樹脂組成物およびそれを用いた形状記憶製品
JP2004182786A (ja) * 2002-11-29 2004-07-02 Nippon Zeon Co Ltd 半導電性ゴムロール用ゴム組成物及び半導電性ゴムロール

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