WO2020137781A1 - Composition de caoutchouc d'épihalogénohydrine - Google Patents

Composition de caoutchouc d'épihalogénohydrine Download PDF

Info

Publication number
WO2020137781A1
WO2020137781A1 PCT/JP2019/049768 JP2019049768W WO2020137781A1 WO 2020137781 A1 WO2020137781 A1 WO 2020137781A1 JP 2019049768 W JP2019049768 W JP 2019049768W WO 2020137781 A1 WO2020137781 A1 WO 2020137781A1
Authority
WO
WIPO (PCT)
Prior art keywords
epihalohydrin
rubber composition
parts
epihalohydrin rubber
weight
Prior art date
Application number
PCT/JP2019/049768
Other languages
English (en)
Japanese (ja)
Inventor
榊田　宏
Original Assignee
日本ゼオン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to JP2020563152A priority Critical patent/JP7375774B2/ja
Publication of WO2020137781A1 publication Critical patent/WO2020137781A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • 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
    • C08L71/03—Polyepihalohydrins

Definitions

  • the present invention relates to an epihalohydrin rubber composition, and more specifically, to an epihalohydrin rubber composition having particularly excellent storage stability, which provides a crosslinked product having low metal corrosiveness, tensile strength, and heat aging resistance.
  • the present invention relates to an epihalohydrin rubber composition that can be produced and a crosslinked product obtained by crosslinking the same.
  • Crosslinked molded products of epihalohydrin rubber such as binary copolymers of epichlorohydrin and ethylene oxide and ternary copolymers of epichlorohydrin, ethylene oxide and allyl glycidyl ether, have heat resistance and heat aging resistance. It is widely used in various rubber products such as hoses, tubes, diaphragms, gaskets, O-rings, tire inner liners, and electric wire coating materials.
  • crosslinking agents such as triazine thiol compounds, thiadiazole compounds, diazine thiol compounds, sulfur and sulfur donors have been used for crosslinking epihalohydrin rubber.
  • a cross-linking agent for example, when a triazine thiol compound is used, a cross-linking reaction occurs via a halogen atom in the epihalohydrin monomer unit in the epihalohydrin rubber, and as a result, hydrogen halide is generated and hydrogen halide It is said that the crosslinked molded product of halohydrin rubber has a problem in metal corrosivity and the like because it harms metals and the like.
  • Patent Document 1 discloses a binary copolymer of epichlorohydrin and allyl glycidyl ether, and three copolymers of epichlorohydrin, ethylene oxide and allyl glycidyl ether.
  • a rubber composition containing an epihalohydrin rubber such as a copolymer, a peroxide crosslinking agent and a piperidinyloxy radical compound is crosslinked with peroxide, and the resulting crosslinked product is converted from a reaction product of the piperidinyloxy radical compound. It is described that the following piperidine compound is contained. And it is described that the crosslinked product obtained by such a method is excellent in fatigue resistance and heat aging resistance. However, this method does not particularly take into consideration storage stability of the rubber composition and improvement of metal corrosiveness of a crosslinked product obtained from the rubber composition.
  • the problem to be solved by the present invention is an epihalohydrin rubber composition which is particularly excellent in storage stability, has low metal corrosiveness, and can provide a crosslinked product excellent in tensile strength, heat aging resistance and the like.
  • An object is to provide an epihalohydrin rubber composition and a crosslinked product obtained by crosslinking it.
  • the present inventor as a result of intensive research to solve the above problems, as an epihalohydrin rubber, containing a specific range amount of monomer units of a compound having a glycidyl ether group, containing an epihalohydrin unit and a compound unit having a glycidyl ether group
  • An epihalohydrin rubber composition obtained by blending a specific range amount of an organic peroxide cross-linking agent, a specific range amount of a cross-linking retarder and a specific range amount of an anti-aging agent into the copolymer is particularly preferable. It was found that a crosslinked product having excellent storage stability, low metal corrosiveness, and excellent tensile strength and heat aging resistance can be provided, and the present invention has been completed based on this finding.
  • an epihalohydrin rubber composition comprising an epihalohydrin rubber, an organic peroxide crosslinking agent, a crosslinking retarder and an antioxidant
  • the epihalohydrin rubber is a copolymer containing an epihalohydrin unit and a compound unit having a glycidyl ether group,
  • the content of the monomer unit of the compound having a glycidyl ether group in the copolymer is 5 to 15% by weight
  • the organic peroxide crosslinking agent is contained in an amount of 0.24 to 2 parts by weight per 100 parts by weight of the epihalohydrin rubber.
  • the epihalohydrin rubber composition is provided.
  • the content of the monomer unit of the compound having a glycidyl ether group in the copolymer is preferably 6 to 13% by weight, more preferably 7 to 12% by weight.
  • the epihalohydrin rubber is preferably at least one selected from a binary copolymer of epihalohydrin and a compound having a glycidyl ether group, and a terpolymer of epihalohydrin, an alkylene oxide and a compound having a glycidyl ether group. It consists of a copolymer.
  • the epihalohydrin is preferably epichlorohydrin.
  • the alkylene oxide is preferably ethylene oxide.
  • the compound having a glycidyl ether group is preferably allyl glycidyl ether.
  • the epihalohydrin rubber composition preferably contains 0.32 to 1.2 parts by weight, more preferably 0.4 to 0.8 parts by weight, of the organic peroxide crosslinking agent per 100 parts by weight of the epihalohydrin rubber.
  • the organic peroxide cross-linking agent is preferably dialkyl peroxide, peroxyketal or peroxyester, more preferably dicumyl peroxide.
  • the epihalohydrin rubber composition preferably contains 0.012 to 0.12 parts by weight, more preferably 0.0192 to 0.072 parts by weight, of the crosslinking retarder per 100 parts by weight of the epihalohydrin rubber.
  • the cross-linking retarder is preferably a nitroso compound, more preferably 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl.
  • the epihalohydrin rubber composition preferably contains 1 to 3.5 parts by weight, more preferably 1.5 to 3 parts by weight, per 100 parts by weight of the epihalohydrin rubber.
  • the antiaging agent is preferably at least one selected from aromatic secondary amine compounds, dithiocarbamate compounds, benzimidazole compounds and amine-ketone compounds, and more preferably 4,4′- It is at least one selected from bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine, nickel dibutyldithiocarbamate and 2-mercaptobenzimidazole.
  • an epihalohydrin rubber crosslinked product obtained by crosslinking the above epihalohydrin rubber composition.
  • an epihalohydrin rubber composition having particularly excellent storage stability, having low metal corrosion resistance, tensile strength, heat aging resistance, fuel oil resistance, cold resistance (that is, resistance to embrittlement at low temperatures), resistance to Provided are an epihalohydrin rubber composition capable of giving a crosslinked product excellent in compression set and the like, and a crosslinked product obtained by crosslinking the same.
  • the epihalohydrin rubber composition of the present invention and the crosslinked product obtained by crosslinking the same are specifically described below.
  • the epihalohydrin rubber used as a rubber component in the epihalohydrin rubber composition of the present invention is a copolymer containing an epihalohydrin unit and a compound unit having a glycidyl ether group, and the compound having a glycidyl ether group in the copolymer.
  • This copolymer is a binary copolymer composed of epihalohydrin, a compound having a glycidyl ether group and a compound having a glycidyl ether group. It may be a combination or a terpolymer composed of epihalohydrin, an alkylene oxide and a compound having a glycidyl ether group. Also, a mixture of these may be used.
  • epihalohydrin examples include epichlorohydrin, epibromohydrin, 2-methylepichlorohydrin, and the like, of which epichlorohydrin is preferable.
  • Examples of the compound having a glycidyl ether group include compounds having a carbon-carbon unsaturated bond and a glycidyl ether group such as vinyl glycidyl ether, allyl glycidyl ether and o-allyl phenyl glycidyl ether, and among them, allyl glycidyl ether is preferable.
  • alkylene oxide examples include ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxy-4-chloropentane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1 ,2-epoxydecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosan, 1,2-epoxyisobutane, 2,3-epoxyisobutane, etc.
  • a copolymer containing epihalohydrin and a compound having a glycidyl ether group as a copolymerization component such as the binary copolymer and the ternary copolymer, each copolymer
  • the content of the monomer unit of the compound having a glycidyl ether group in the combined product is 5 to 15% by weight.
  • the crosslinked product obtained from the epihalohydrin rubber composition has tensile strength, heat resistance, fuel oil resistance, cold resistance (that is, embrittlement resistance at low temperature), compression set resistance. It is not preferable from the viewpoint of sex.
  • the content is preferably 6 to 13% by weight, and particularly preferably 7 to 12% by weight from the viewpoint of storage stability of the epihalohydrin rubber composition and metal corrosiveness of the crosslinked product obtained from the epihalohydrin rubber composition.
  • the content of the epihalohydrin monomer unit in the binary copolymer of epihalohydrin and a compound having a glycidyl ether group used as the epihalohydrin rubber in the present invention is 85 to 95% by weight, preferably 87 to 94%. %, and more preferably 88 to 93% by weight.
  • the total content of the monomer unit of epihalohydrin and the monomer composition of alkylene oxide is 85 to 95% by weight, preferably Is 87 to 94% by weight, and more preferably 88 to 93% by weight.
  • the content of the epihalohydrin monomer unit is preferably 48 to 78% by weight, and the content of the alkylene oxide monomer is preferably 10 to 45% by weight.
  • the 13 C-NMR was measured, it can be calculated from 13 C-NMR chart obtained.
  • the peak derived from the carbon bonded to chlorine in the epichlorohydrin unit is observed at a chemical shift of 40 to 50 ppm, and the peak of allyl glycidyl ether unit is observed.
  • a peak derived from unsaturated carbon is observed at a chemical shift of 110 to 140 ppm.
  • the epihalohydrin rubber used in the present invention includes a binary copolymer of the above epihalohydrin and a compound having a glycidyl ether group, and a terpolymer of the above epihalohydrin, an alkylene oxide and a compound having a glycidyl ether group. And may be used alone or as a mixture of these copolymers.
  • the Mooney viscosity ML 1+4 (100° C.) of the epihalohydrin rubber used in the present invention is usually 30 to 160, preferably 40 to 120. If the Mooney viscosity is too low or too high, the kneading processability with the compounding agent will deteriorate, which is not preferable.
  • the method for producing the epihalohydrin rubber used in the present invention is not particularly limited, and it may be produced by copolymerizing a predetermined amount of each predetermined monomer according to a known polymerization method. For example, it can be produced by the methods of Production Examples 1 to 5 described in this specification.
  • the Mooney viscosity can be set to a desired value by appropriately adjusting the composition of the monomers.
  • the organic peroxide crosslinking agent used in the epihalohydrin rubber composition of the present invention is preferably a dialkyl peroxide, a peroxyketal or a peroxyester.
  • dialkyl peroxide examples include dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl- 2,5-di(tert-butylperoxy)hexyne-3 and the like can be mentioned.
  • Peroxyketals include 1,1-di(tert-hexylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, n-butyl 4,4-di(tert-butylperoxy)valerate And so on.
  • peroxyesters examples include tert-butylperoxybenzoate, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxy-2-ethylhexyl monocarbonate, Examples thereof include tert-butylperoxylaurate, tert-butylperoxy-3,5,5-trimethylhexanoate and tert-hexylperoxyisopropyl monocarbonate.
  • dicumyl peroxide and di(2-tert-butylperoxyisopropyl) are preferred because unreacted components after crosslinking are less likely to remain and the boiling point of the decomposed product is relatively low and the decomposed product is easily removed.
  • Benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,1-di(tert-butylperoxy)cyclohexane and the like are preferable, and dicumyl peroxide is particularly preferable.
  • the organic peroxide cross-linking agent contained in the epihalohydrin rubber composition of the present invention is an epihalohydrin rubber via a double bond in a monomer unit of a compound having a glycidyl ether group in the above copolymer constituting the epihalohydrin rubber. Can be crosslinked. Therefore, the amount of the organic peroxide crosslinking agent used in the present invention is appropriately determined based on the content of the monomer unit of the compound having a glycidyl ether group in the copolymer. From this point of view, the epihalohydrin rubber composition of the present invention contains the organic peroxide crosslinking agent in an amount of 0.24 to 2 parts by weight per 100 parts by weight of the above epihalohydrin rubber.
  • the crosslinked product obtained from the epihalohydrin rubber composition has tensile strength, compression set resistance, heat aging resistance, fuel oil resistance, cold resistance (that is, embrittlement resistance at low temperature). It is not preferable from the viewpoint of, for example, even when it exceeds 2 parts by weight, the crosslinked product obtained from the epihalohydrin rubber composition has tensile strength, compression set resistance, heat aging resistance, heat resistance (that is, embrittlement resistance at low temperature). ) Etc. are not preferable.
  • the epihalohydrin rubber composition of the present invention contains 100 parts by weight of the above-mentioned epihalohydrin rubber.
  • the content is preferably 0.32 to 1.2 parts by weight, more preferably 0.4 to 0.8 parts by weight.
  • the theoretical active oxygen amount of the organic peroxide cross-linking agent with respect to 1 part by weight of the carbon-carbon unsaturated bond in the epihalohydrin rubber is preferably 0.001 to 0.05 part by weight, more preferably 0.004 part by weight. To 0.04 parts by weight, more preferably 0.008 to 0.03 parts by weight.
  • the crosslinking retarder contained in the epihalohydrin rubber composition of the present invention is preferably a nitroso compound.
  • the nitroso compound include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6 ,6-Tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,5,5-tetramethylpiperidine-1-oxyl, bis(2 ,2,6,6-Tetramethyl-1-piperidinyloxy-4-yl)sebacate, 4,4′-[(1,10-dioxo-1,10-decanediyl)bis(oxy)]bis[2 ,2,6,6-Tetramethyl]-1-piperidinidinyloxy, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl monophosphate, 3-carboxy
  • the cross-linking start time can be appropriately delayed, the time from the cross-linking start to the cross-linking completion can be appropriately adjusted, and the cross-linking density of the resulting cross-linked product can be adjusted.
  • a crosslinked product having desired properties can be advantageously obtained.
  • the epihalohydrin rubber composition of the present invention contains the crosslinking retarder in an amount of 0.0072 to 0.24 part by weight per 100 parts by weight of the above epihalohydrin rubber.
  • it is not preferable from the viewpoint of the storage stability of the epihalohydrin rubber composition and the heat aging resistance of the crosslinked product obtained from the epihalohydrin rubber composition, and when it exceeds 0.24 parts by weight.
  • it is not preferable from the viewpoint of heat aging resistance, fuel oil resistance, tensile strength, etc. of the crosslinked product obtained from the epihalohydrin rubber composition.
  • the crosslinking retarder is preferably 0.012 to 0.12 parts by weight, more preferably 0.0192 to 0 per 100 parts by weight of the above epihalohydrin rubber. Contains 0.072 parts by weight.
  • the amount of the crosslinking retarder with respect to 1 part by weight of the carbon-carbon unsaturated bond in the epihalohydrin rubber is preferably 0.003 to 0.1 part by weight, more preferably 0.005 to 0.07 part by weight. And more preferably 0.007 to 0.05 parts by weight.
  • the antioxidant contained in the epihalohydrin rubber composition of the present invention is preferably an aromatic secondary amine compound, a dithiocarbamate compound, a benzimidazole compound or an amine-ketone compound.
  • aromatic secondary amine compound include N,N′-di-2-naphthyl-p-phenylenediamine, N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4′-bis( ⁇ , ⁇ -Dimethylbenzyl)diphenylamine, p-(p-toluenesulfonylamide)diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N- Phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'
  • Examples of the dithiocarbamate-based compound include nickel dibutyldithiocarbamate.
  • Examples of the benzimidazole compound include zinc salt of 2-mercaptobenzimidazole and 2-mercaptobenzimidazole.
  • As the amine-ketone compound 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, a reaction product of diphenylamine and acetone And so on.
  • 4,4′-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine, nickel dibutyldithiocarbamate or 2-mercaptobenzimidazole is preferable.
  • As the antiaging agent one of these may be used alone or two or more of them may be used in combination, but it is preferable to use two or more of them in combination.
  • the epihalohydrin rubber composition of the present invention contains the antioxidant in an amount of 0.5 to 4 parts by weight per 100 parts by weight of the above epihalohydrin rubber.
  • the amount is less than 0.5 parts by weight, it is not preferable from the viewpoint of heat aging resistance, fuel oil resistance, compression set resistance, etc. of the crosslinked product obtained from the epihalohydrin rubber composition, and even when it exceeds 4 parts by weight.
  • the epihalohydrin rubber composition of the present invention preferably contains 1 to 3.5 parts by weight, more preferably 1.5 to 3 parts by weight of an antioxidant per 100 parts by weight of the above epihalohydrin rubber. contains.
  • the epihalohydrin rubber composition of the present invention is a rubber other than the above epihalohydrin rubber, for example, isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, etc., within a range that does not impair the desired effect of the present invention.
  • Unsaturated rubber; butyl rubber, ethylene-propylene rubber, ethylene-acrylic rubber, acrylic rubber, chlorosulfonated polyethylene, chlorinated polyethylene, nitrile rubber, hydrogenated nitrile rubber, silicon rubber, fluorine rubber, etc. Highly saturated rubber and the like may be included.
  • the content of these rubbers can be appropriately adjusted, but is preferably 40 parts by weight or less, more preferably 20 parts by weight or less, and further preferably 10 parts by weight or less with respect to 100 parts by weight of the epihalohydrin rubber.
  • the epihalohydrin rubber composition of the present invention in addition to the above-mentioned organic peroxide cross-linking agent, cross-linking retarder and anti-aging agent, compounding agents usually used in rubber compositions, for example, reinforcing properties of carbon black and silica.
  • Fillers; non-reinforcing fillers such as calcium carbonate and clay; processing aids such as fatty acid esters; plasticizers such as polyether ester compounds; acid acceptors such as hydrotalcite; co-use such as trimethylolpropane trimethacrylate You may contain a crosslinking agent etc.
  • the epihalohydrin rubber composition of the present invention may contain a light stabilizer, a lubricant, an adhesive, a lubricant, a flame retardant, a mildew proofing agent, a colorant, an antistatic agent and the like which are usually used in the rubber industry.
  • a light stabilizer e.g., a lubricant, an adhesive, a lubricant, a flame retardant, a mildew proofing agent, a colorant, an antistatic agent and the like which are usually used in the rubber industry.
  • the content of these compounding agents in the epihalohydrin rubber composition of the present invention may be appropriately selected so as to satisfy processing conditions and various performances normally required for a rubber cross-linked product.
  • the method for preparing the epihalohydrin rubber composition of the present invention is not particularly limited, and a commonly used method can be used. For example, by using a mixer such as an open roll, a Banbury mixer, and a screw mixer, the epihalohydrin rubber, the organic peroxide cross-linking agent, the cross-linking retarder and the anti-aging agent, and optionally other compounding agents are mixed. A method can be adopted. The order of compounding the epihalohydrin rubber, the organic peroxide cross-linking agent, the cross-linking retarder and the antioxidant, and other compounding agents is not particularly limited.
  • the epihalohydrin rubber composition of the present invention can be formed into a crosslinked product by molding with a molding machine and heating during molding or by heating subsequent to molding. It is preferable that such heating is usually performed at 100° C. or higher for 1 minute to 5 hours.
  • crosslinking at 100° C. or higher for 1 minute to 5 hours is used as a primary crosslinking step, and if necessary, the primary crosslinked product obtained in the primary crosslinking step may be used at 100 to 220° C.
  • a step of secondary cross-linking by heating for 5 to 48 hours may be further added.
  • the conditions of the secondary cross-linking as needed for the primary cross-linked product are usually a heating temperature of 100 to 220° C., preferably 130 to 210° C., more preferably 150 to 180° C., and a heating time of 0. It is 5 to 48 hours, preferably 0.7 to 24 hours, more preferably 1 to 12 hours.
  • the epihalohydrin rubber composition of the present invention is particularly excellent in storage stability, has low metal corrosion resistance, tensile strength, heat aging resistance, fuel oil resistance, cold resistance (that is, embrittlement resistance at low temperatures), and compression resistance. It is possible to give a crosslinked product which is excellent in permanent set property and the like.
  • the crosslinked product of the epihalohydrin rubber composition of the present invention can be suitably used for automobile hoses, air duct hoses, OA equipment rolls, electrophotographic equipment conductive rolls, and the like.
  • Mooney scorch time (T5) was used as JIS Scorch stability test of the epichlorohydrin rubber composition. It was measured at 125° C. using an L rotor according to K6300:2013.
  • the Mooney scorch time (T5) is the time until the Mooney viscosity increases from the minimum value (Vm) by 5 points. The larger the Mooney scorch time (T5), the better the scorch stability.
  • the scorch stability was judged according to the following criteria, and each sample was graded to 1 to 4.
  • Mooney scorch time (T5) is 30 minutes or more 2: Mooney scorch time (T5) is 20 minutes or more and less than 30 minutes 3: Mooney scorch time (T5) is 10 minutes or more, less than 20 minutes If 4: Mooney scorch time (T5) is less than 10 minutes
  • volume change rate is less than 50% 2: When the volume change rate is 50% or more and less than 60% 3: When the volume change rate is 60% or more and less than 70% 4: Volume change rate is 70% If more than
  • Production example 1 Production of Polymerization Catalyst
  • the closed pressure-resistant glass container was replaced with nitrogen, and 200 parts of toluene and 60 parts of triisobutylaluminum were supplied. After dipping this glass container in ice water and cooling, 230 parts of diethyl ether was added and stirred. Next, while cooling with ice water, 13.6 parts of phosphoric acid was added and further stirred. At this time, the internal pressure of the container increased due to the reaction between triisobutylaluminum and phosphoric acid, so depressurization was carried out at appropriate times. Then, the obtained reaction mixture was aged in a warm water bath at 60° C. for 1 hour to obtain a catalyst solution.
  • the monomer composition ratio of the epichlorohydrin rubber (a-3) was measured by 13 C-NMR and found to be 75.5 wt% of epichlorohydrin monomer unit and 13.4 wt% of ethylene oxide monomer unit.
  • the allyl glycidyl ether monomer unit was 11.1 wt %.
  • the Mooney viscosity of the obtained epichlorohydrin rubber (a-1) was 71.
  • Production Example 3 Production of epichlorohydrin rubber (a-2) Put 323.05 parts of epichlorohydrin, 26.95 parts of allyl glycidyl ether, and 3500 parts of toluene in an autoclave, and raise the temperature of the inner solution to 60°C with stirring under a nitrogen atmosphere. After warming, 10 parts of the catalyst solution obtained in Production Example 1 above was added to start the reaction. Every 30 minutes after the start of the reaction, 7 parts of the catalyst solution was added over 5 hours. Then, 15 parts of water was added and stirred to terminate the reaction.
  • Example 1 To 100 parts of the epichlorohydrin rubber (a-1) obtained in Production Example 2 above, 40 parts of a filler (carbon black) "SEAST SO (registered trademark) (FEF)" (manufactured by Tokai Carbon Co., Ltd.) and a filler ( Wet silica) "Nipsil (registered trademark) VN-3" (manufactured by Tosoh Silica Co., Ltd.) 50 parts, plasticizer (polyether ester compound) "Adeka Sizer (registered trademark) RS735" (manufactured by ADEKA), 35 parts, processed Auxiliary agent (fatty acid ester) "Splender R300V” (manufactured by Kao) 3.0 parts, Acid acceptor (hydrotalcite) "DHT-4A” (manufactured by Kyowa Chemical Industry Co., Ltd.) 3.0 parts, calcium carbonate "Shiragika CC” 3.0 parts (manufactured by Shiraishi Calcium Co
  • Example 2 An epichlorohydrin rubber composition was prepared in the same manner as in Example 1 except that the epichlorohydrin rubber (a-2) obtained in Production Example 3 was changed.
  • Example 3 0.56 parts of peroxide (dicumyl peroxide) "Parkmill (registered trademark)-D” (manufactured by NOF Corporation), and nitroso compound (TEMPOL) were added to the epichlorohydrin rubber (a-3) obtained in Production Example 4 above. : 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl) "Polystop 7300P” (manufactured by Hakutosha Co., Ltd.) A chlorohydrin rubber composition was prepared.
  • Example 4 Anti-aging agent (4,4'-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine) "Nocrac (registered trademark) CD” (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) 0.50 parts, anti-aging agent (dibutylthiocarbamic acid) Nickel) 0.50 parts of "Nocrac (registered trademark) NBC” (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), peroxide (dicumyl peroxide) "Park Mill (registered trademark)-D” (manufactured by NOF Corporation) 0.32 Part, and nitroso compound (TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl) "Polystop 7300P” (manufactured by Hakutosha Co., Ltd.), 0.02 part.
  • An epichlorohydrin rubber composition was prepared in the same manner as in.
  • Table 1 shows the test results of the epichlorohydrin rubber compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 7. Table 1 also shows the composition of each epichlorohydrin rubber composition. Further, Table 1 also shows the amount of theoretical active oxygen amount of organic peroxide per 1 g of double bond for Percumyl D (organic peroxide), and TEMPOL (crosslinking retarder) for TEMPOL (crosslinking retarder). The amount of the crosslinking retarder) added is also shown.
  • a binary copolymer of epichlorohydrin and allyl glycidyl ether wherein the content of allyl glycidyl ether monomer units (AGE) is 7.7% by weight.
  • a copolymer terpolymer of epichlorohydrin rubber (a-2) or a terpolymer of epichlorohydrin, ethylene oxide and allyl glycidyl ether, which comprises a monomer unit (AGE) of allyl glycidyl ether A terpolymer having a content of 11.1 or 6.9% by weight, epichlorohydrin rubber (a-1) or epichlorohydrin rubber (a-3), was used.
  • Comparative Example 2 and Comparative Example 3 blended in an amount of less than 2 parts by weight or more than 2 parts by weight, and an amount of crosslinking retarder (TEMPOL) exceeding 0.24 parts by weight per 100 parts by weight of epichlorohydrin rubber (a-1) or 0.
  • Comparative Examples 4 and 5 blended in an amount of less than 0.0072 parts by weight, and less than 0.5 parts by weight or 4 parts by weight of an antioxidant per 100 parts by weight of epichlorohydrin rubber (a-1).
  • the epichlorohydrin rubber compositions of Comparative Example 6 and Comparative Example 7 blended in an amount exceeding the above range show storage stability of the epichlorohydrin rubber composition, tensile strength of a crosslinked product of the epichlorohydrin rubber composition, heat aging resistance, The fuel oil resistance, cold resistance (brittle resistance at low temperature), metal corrosion resistance, and compression set resistance were inferior in one or more.
  • the epihalohydrin rubber composition of the present invention is particularly excellent in storage stability, has low metal corrosion resistance, tensile strength, heat aging resistance, fuel oil resistance, cold resistance (brittle resistance at low temperature), compression permanent resistance. It is possible to give a crosslinked product which is excellent in terms of strainability and the like.
  • the crosslinked product of the epihalohydrin rubber composition of the present invention can be suitably used for automobile hoses, air duct hoses, OA equipment rolls, electrophotographic equipment conductive rolls, and the like.

Landscapes

  • 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)

Abstract

L'invention concerne une composition de caoutchouc d'épihalogénohydrine qui présente une stabilité au stockage particulièrement excellente et qui est en mesure de donner un produit réticulé présentant une faible corrosivité du métal et une excellente résistance à la traction, une excellente résistance au vieillissement thermique, au carburant, etc. La présente invention concerne une composition de caoutchouc d'épihalogénohydrine obtenue par mélange d'une quantité d'un agent de réticulation de type peroxyde organique qui se situe dans une plage spécifique, d'une quantité d'un retardateur de réticulation qui se situe dans une plage spécifique et d'une quantité d'un inhibiteur de vieillissement qui se situe dans une plage spécifique, avec un copolymère qui contient des motifs d'épihalogénohydrine et des motifs d'un composé présentant des groupes de type glycidyléther, le copolymère comprenant une quantité, dans une plage spécifique, de motifs monomères du composé présentant des groupes glycidyléther.
PCT/JP2019/049768 2018-12-26 2019-12-19 Composition de caoutchouc d'épihalogénohydrine WO2020137781A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020563152A JP7375774B2 (ja) 2018-12-26 2019-12-19 エピハロヒドリンゴム組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018242275 2018-12-26
JP2018-242275 2018-12-26

Publications (1)

Publication Number Publication Date
WO2020137781A1 true WO2020137781A1 (fr) 2020-07-02

Family

ID=71126024

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/049768 WO2020137781A1 (fr) 2018-12-26 2019-12-19 Composition de caoutchouc d'épihalogénohydrine

Country Status (2)

Country Link
JP (1) JP7375774B2 (fr)
WO (1) WO2020137781A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023190181A1 (fr) * 2022-03-31 2023-10-05 株式会社大阪ソーダ Composition de réticulation et matériau de caoutchouc obtenu par réticulation de celle-ci
EP4209540A4 (fr) * 2020-09-02 2024-10-16 Nok Corp Composition de caoutchouc copolymère éthylène/propylène

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0680827A (ja) * 1992-09-01 1994-03-22 Sumitomo Chem Co Ltd ゴム組成物
JPH07157566A (ja) * 1993-12-09 1995-06-20 Daiso Co Ltd エピクロルヒドリン系ポリマー加硫用組成物
JP2004107540A (ja) * 2002-09-19 2004-04-08 Nippon Zeon Co Ltd エピハロヒドリンゴム組成物及びエピハロヒドリンゴム架橋成形体の製造方法
JP2005187710A (ja) * 2003-12-26 2005-07-14 Nippon Zeon Co Ltd エピハロヒドリンゴム組成物
JP2013147582A (ja) * 2012-01-20 2013-08-01 Daiso Co Ltd 加硫用ゴム組成物及びその加硫物
CN104861631A (zh) * 2015-04-28 2015-08-26 安徽同丰橡塑工业有限公司 一种耐磨橡胶
JP2016501974A (ja) * 2012-12-31 2016-01-21 ダウ グローバル テクノロジーズ エルエルシー 架橋オレフィンブロックコポリマーを有する熱可塑性加硫物
JP2018506598A (ja) * 2014-12-09 2018-03-08 アーケマ・インコーポレイテッド スコーチ防止性のペルオキシドの液体状および溶融性固体状グレード

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0680827A (ja) * 1992-09-01 1994-03-22 Sumitomo Chem Co Ltd ゴム組成物
JPH07157566A (ja) * 1993-12-09 1995-06-20 Daiso Co Ltd エピクロルヒドリン系ポリマー加硫用組成物
JP2004107540A (ja) * 2002-09-19 2004-04-08 Nippon Zeon Co Ltd エピハロヒドリンゴム組成物及びエピハロヒドリンゴム架橋成形体の製造方法
JP2005187710A (ja) * 2003-12-26 2005-07-14 Nippon Zeon Co Ltd エピハロヒドリンゴム組成物
JP2013147582A (ja) * 2012-01-20 2013-08-01 Daiso Co Ltd 加硫用ゴム組成物及びその加硫物
JP2016501974A (ja) * 2012-12-31 2016-01-21 ダウ グローバル テクノロジーズ エルエルシー 架橋オレフィンブロックコポリマーを有する熱可塑性加硫物
JP2018506598A (ja) * 2014-12-09 2018-03-08 アーケマ・インコーポレイテッド スコーチ防止性のペルオキシドの液体状および溶融性固体状グレード
CN104861631A (zh) * 2015-04-28 2015-08-26 安徽同丰橡塑工业有限公司 一种耐磨橡胶

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4209540A4 (fr) * 2020-09-02 2024-10-16 Nok Corp Composition de caoutchouc copolymère éthylène/propylène
WO2023190181A1 (fr) * 2022-03-31 2023-10-05 株式会社大阪ソーダ Composition de réticulation et matériau de caoutchouc obtenu par réticulation de celle-ci

Also Published As

Publication number Publication date
JP7375774B2 (ja) 2023-11-08
JPWO2020137781A1 (ja) 2021-11-18

Similar Documents

Publication Publication Date Title
US5912288A (en) Vulcanized rubber composition
EP0042278A2 (fr) Addition d'asphalte à des mélanges de caoutchoucs halobutyles
JP7375774B2 (ja) エピハロヒドリンゴム組成物
US10894878B2 (en) Halogen free and fire-resistant rubber composition and hose
EP0796897A1 (fr) Composition de caoutchouc a faible deformation permanente a la compression
EP0317346A1 (fr) Procédé de fabrication d'une composition de caoutchouc dérivée de fluoroélastomère et de copolymère caoutchouteux éthylène-alpha-oléfine et procédé de fabrication d'un article en caoutchouc moulé avec cette composition
KR101017114B1 (ko) 에틸렌-알킬아크릴레이트 공중합 고무 조성물
EP0485906B1 (fr) Composition de caoutchouc vulcanizable
JPH093246A (ja) 水素化ｎｂｒ組成物
US5523353A (en) Rubber composition
US20230027517A1 (en) Rubber composition and vulcanized molded article
JP3633322B2 (ja) エチレン−アクリレート共重合ゴム組成物
KR100396015B1 (ko) 가황고무조성물
JPH05287150A (ja) 含フツ素エラストマー組成物
KR101821482B1 (ko) 난연성 탄성 소재를 포함하는 조성물 및 이의 제조방법
JP3804413B2 (ja) エチレン・プロピレン系共重合ゴム組成物
JP2006213743A (ja) 水素化ニトリルゴム組成物
JP3344187B2 (ja) 耐フロン冷媒用水素化ｎｂｒ組成物
CN110536923B (zh) 氢化nbr组合物
JP2005344037A (ja) 水素化ｎｂｒゴム組成物
Oliveira et al. The effect of the vulcanizing system on cure and mechanical properties of NBR/EPDM blends
JP2853305B2 (ja) 耐熱性ゴム組成物
JPH02245046A (ja) ゴム組成物
EP0595551A2 (fr) Tuyau pour radiateur de véhicule
JPH08283482A (ja) ゴム組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19901447

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020563152

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19901447

Country of ref document: EP

Kind code of ref document: A1