WO2021161838A1 - Composé de diarylamine, agent de charge traité en surface et composition de polymère - Google Patents

Composé de diarylamine, agent de charge traité en surface et composition de polymère Download PDF

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WO2021161838A1
WO2021161838A1 PCT/JP2021/003554 JP2021003554W WO2021161838A1 WO 2021161838 A1 WO2021161838 A1 WO 2021161838A1 JP 2021003554 W JP2021003554 W JP 2021003554W WO 2021161838 A1 WO2021161838 A1 WO 2021161838A1
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carbon atoms
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meth
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晶洋 尾上
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日本ゼオン株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/20—[b, e]-condensed with two six-membered rings with hydrogen atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds

Definitions

  • the present invention provides a novel diarylamine-based compound capable of providing a surface-treating filler exhibiting an excellent anti-aging effect on a polymer material, a surface-treating filler obtained by using such a diarylamine-based compound, and a surface-treating filler.
  • the present invention relates to a polymer composition containing such a surface treatment filler.
  • polymers composed of organic compounds have contributed to the development of humankind in various forms such as plastics, rubbers, fibers, and films. Since these are used in various environments depending on the application, improvements have been made so that they can be used for a long period of time by imparting durability under the assumed environment. For example, products have been developed that impart ultraviolet resistance to plastics used outdoors and cold resistance to rubber that functions even in extremely cold regions.
  • Patent Document 1 discloses an antiaging agent that improves heat resistance.
  • an anti-aging agent alone cannot suppress the reduction in molecular weight of the polymer due to heat and the unintended cross-linking reaction, and therefore, it is insufficient to meet the heat resistance requirement in a higher temperature region such as 190 ° C. or higher. ..
  • the present invention has been made in view of the above circumstances, and is obtained by using a novel diarylamine-based compound, such a diarylamine-based compound, which can provide a surface-treating filler showing an excellent anti-aging effect on a polymer material. It is an object of the present invention to provide a surface treatment filler to be used, and a polymer composition containing such a surface treatment filler.
  • the present inventor has found that the above object can be achieved by a specific diarylamine compound having a group capable of binding to a hydroxyl group, and completes the present invention. It came to.
  • a diarylamine-based compound represented by the following general formula (1) is provided.
  • a 1 is a group capable of binding to a hydroxyl group
  • a 2 is a (m + n) -valent organic group having 1 to 30 carbon atoms which may have a substituent.
  • a 3 is a chemical single bond or a divalent group containing a group selected from an ether group, a keto group, an ester group, and an amide group
  • a 4 is the following formula (2).
  • a 4 is preferably a group represented by the following formula (9).
  • "*" indicates the bonding position to the group represented by A 3, hydrogen atoms bonded in the formula (9), with the carbon atoms forming the aromatic ring, the number of carbon atoms It may be substituted with 1 to 30 monovalent organic groups.
  • a 1 is preferably a silyl group having at least one alkoxy group.
  • a 3 is preferably an amide group.
  • a surface treatment filler obtained by immobilizing the above diarylamine compound on the surface of the filler.
  • the surface treatment filler of the present invention is preferably obtained by immobilizing a diarylamine compound on the surface of silica.
  • a polymer composition containing a polymer and the above-mentioned surface treatment filler.
  • the polymer is preferably rubber.
  • the rubber is preferably acrylic rubber.
  • a novel diarylamine-based compound capable of providing a surface-treating filler exhibiting an excellent anti-aging effect on a polymer material, a surface-treating filler obtained by using such a diarylamine-based compound, And, a polymer composition containing such a surface treatment filler can be provided.
  • the diarylamine compound of the present invention is a compound represented by the following general formula (1).
  • the diarylamine compound of the present invention is immobilized on the surface of the filler, and the compound represented by the following general formula (1) is used as a surface-treated filler immobilized on the surface, whereby excellent aging of the polymer material is achieved.
  • the surface-treating filler obtained by using such a diarylamine-based compound of the present invention, which can exhibit an inhibitory action, is preferably used as an antiaging agent.
  • a 1 is a group capable of binding to a hydroxyl group
  • a 2 is a (m + n) -valent organic group having 1 to 30 carbon atoms which may have a substituent.
  • a 3 is a chemical single bond or a divalent group containing a group selected from an ether group, a keto group, an ester group, and an amide group
  • a 4 is the following formula (2). It is a monovalent group having a structure excluding one hydrogen atom forming a carbon-hydrogen bond in the compound selected from (8), where m is an integer of 1 to 5 and n is an integer of 1 to 5. Is.) (In the above formulas (2) to (8), the hydrogen atom bonded to the carbon atom forming the aromatic ring is substituted with a monovalent organic group having 1 to 30 carbon atoms which may have a substituent. May be.)
  • a 1 is a group capable of binding to a hydroxyl group, and is not particularly limited as long as it is a group capable of reacting with a hydroxyl group to form a chemical bond. Examples thereof include an isocyanato group, an isothiocyanate group, an epoxy group and a carboxyl group.
  • a 1 contributes to the immobilization of the diarylamine compound of the present invention on the filler surface by reacting with the hydroxyl group contained in the filler.
  • the A 1 an alkoxysilyl group, i.e., preferably a silyl group having at least one alkoxy group, more preferably an alkoxysilyl group represented by the following general formula (10).
  • R 1 is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and further preferably 2 carbon atoms.
  • R 2 is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and further preferably an alkyl group having 2 carbon atoms.
  • x is an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
  • Examples of the alkoxysilyl group constituting A 1 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, an ethyldimethoxysilyl group, a diethylmethoxysilyl group, and a methyl.
  • Examples thereof include a diethoxysilyl group, a dimethylethoxysilyl group, an ethyldiethoxysilyl group and a diethylethoxysilyl group.
  • trimethoxysilyl group, a triethoxysilyl group, and a triisopropoxysilyl group are preferable, and a triethoxysilyl group is particularly preferable, from the viewpoint that the filler can be more preferably immobilized on the surface.
  • Examples thereof include an aromatic hydrocarbon ring group having 6 to 30 carbon atoms which may have a substituent.
  • the position of the substituent can be any position.
  • the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy group having 1 to 10 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro group; cyano group; methyl group and ethyl group.
  • An alkyl group having 1 to 10 carbon atoms such as a t-butyl group; and the like can be mentioned.
  • Specific examples of the aliphatic hydrocarbon group constituting A 2 include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group and a decamethylene group. Examples thereof include an alkylene group having 1 to 20 carbon atoms.
  • Specific examples of the aromatic hydrocarbon ring group constituting A 2 include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group and 1,5-naphthylene.
  • Examples include a group, a 2,6-naphthylene group, a 4,4'-biphenylene group and the like. Among these, an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 2 to 5 carbon atoms is more preferable.
  • a 3 is a chemical single bond, or an ether group, a keto group, an ester group, and a divalent group containing a group selected from an amide group.
  • R 3 and R 4 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • n is an integer of 1 to 5, preferably 1 or 2, and more preferably 1.
  • a 4 is carbon in the compound is selected from the following formulas (2) to (8) - a monovalent radical having one except the structure of the hydrogen atoms to form hydrogen bonds be.
  • the hydrogen atom bonded to the carbon atom forming the aromatic ring is substituted with a monovalent organic group having 1 to 30 carbon atoms which may have a substituent. May be good.
  • "*" in the above general formula (1) shows a carbon atom position which binds to A 3. That is, the compounds represented by the above formulas (2) to (8) are monovalent substituents having a structure excluding one hydrogen atom at the carbon atom positions marked with "*", and are "*". (for "*" are assigned multiple compounds, "*" is out of the plurality of carbon atoms positions are assigned to any one of the carbon atoms located) carbon atom positions accompanied by a suffix in a a 3 Can form chemical bonds.
  • the hydrogen atom bonded to the carbon atom forming the aromatic ring may be substituted with a monovalent organic group having 1 to 30 carbon atoms, and such a 1-valent carbon atom may be substituted.
  • the organic groups of to 30 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group and n-hexyl group.
  • Alkyl group having 1 to 30 carbon atoms such as n-heptyl group, n-octyl group, n-nonyl group and n-decyl group; carbon such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group.
  • the organic group having 1 to 30 carbon atoms may have a substituent, and the position of the substituent can be any position.
  • the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy group having 1 to 10 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro group; cyano group; methyl group and ethyl group.
  • An alkyl group having 1 to 10 carbon atoms such as a t-butyl group; and the like can be mentioned.
  • the compound represented by the above formula (2) is represented by the above formula (3) from the viewpoint of being able to further enhance the anti-aging effect.
  • the compound, the compound represented by the above formula (5) and the above formula (6) is preferable, and the compound represented by the above formula (2) is particularly preferable.
  • R 5 represents an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, more preferably 2 carbon atoms
  • R 6 is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and further preferably an alkyl group having 2 carbon atoms.
  • p is an integer of 1 to 30, preferably an integer of 1 to 20, more preferably an integer of 2 to 5, still more preferably 3
  • q is an integer of 0 to 2, preferably 0 or 1. , More preferably 0.
  • the method for producing the diarylamine compound represented by the general formula (1) is not particularly limited, but for example, the diarylamine compound represented by the general formula (1) is represented by the general formula (11). Examples of the represented compound include the following methods.
  • trimellitic anhydride and 4-aminodiphenylamine are reacted in a solvent, and the compound represented by the following formula (12) and / or the following formula (13) is used.
  • a reaction solution containing the represented compound is obtained.
  • the imidization reaction is usually carried out in the presence of an acid catalyst or a base catalyst.
  • the acid used as the acid catalyst include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; and organic acids such as p-toluene sulfonic acid, 10-campar sulfonic acid and acetic acid.
  • Bases used as base catalysts include tertiary amines such as triethylamine, diisopropylethylamine, N-methylmorpholine; pyridines such as pyridine, picoline, lutidine, 4- (dimethylamino) pyridine; sodium hydroxide, potassium hydroxide, carbonic acid. Examples include, but are not limited to, inorganic bases such as potassium.
  • the reaction of trimellitic anhydride, 4-aminodiphenylamine, and the imidization reaction may proceed at the same time.
  • the diarylamine compound represented by the general formula (1) is a compound represented by the following general formula (16)
  • the following method can be mentioned.
  • R 5 , R 6 , p, and q are the same as those in the general formula (11).
  • the compound represented by the following formula (17) is formed by reacting trimellitic anhydride and 4,4'-diaminodiphenylamine in a solvent and advancing imidization by heating. To get.
  • the reaction and imidization of trimellitic anhydride with 4,4'-diaminodiphenylamine in the following reaction formula can be the same as in the case of the compound represented by the above general formula (11).
  • the compound represented by the above formula (17) obtained by the above reaction is reacted with phthalic anhydride in a solvent, and imidization is promoted by heating to carry out the following formula ( The compound shown in 18) is obtained.
  • the reaction and imidization of phthalic anhydride with the compound represented by the above formula (17) in the following reaction formula can be the same as that of the compound represented by the above general formula (11).
  • the amino group-containing silane compound represented by the following general formula (15) in addition to the compound represented by the above formula (18) obtained by the above reaction, the amino group-containing silane compound represented by the following general formula (15) (in the following general formula (15), R 5 , R 6 , p and q are added. , The same as the above general formula (16)), the compound represented by the above general formula (16) can be obtained.
  • the diarylamine compound represented by the general formula (1) is a compound represented by the general formula (11) and a compound represented by the general formula (16) (that is,).
  • a 4 is is a group derived from a compound represented by the formula (2), and the formula in case of a group derived from the compound represented by (3)), it is exemplified a method for manufacturing
  • a 4 is, in the above formulas (4) - is a group derived from a compound represented by (8) or the like, for example, the method described in WO 2018/159459, WO 2011/058918 It can be produced by combining the method described in No. 1 and the method described in International Publication No. 2011/093443 with the above method and a known synthetic method.
  • the surface treatment filler of the present invention is a diarylamine compound represented by the general formula (1) obtained by immobilizing the diarylamine compound represented by the general formula (1) on the surface of the filler. It is a surface-treated filler.
  • the surface-treating filler of the present invention can be blended with a polymer material to exhibit an excellent anti-aging effect on the polymer material, and is suitable as an anti-aging agent.
  • the filler used in the present invention is not particularly limited, but silica is preferable from the viewpoint that the diarylamine compound represented by the above general formula (1) can be suitably fixed on the surface thereof.
  • silica examples include dry white carbon, wet white carbon, colloidal silica, and precipitated silica. Among these, wet white carbon containing hydrous silicic acid as a main component is preferable. Further, a carbon-silica dual phase filler in which silica is supported on the surface of carbon black may be used. These silicas can be used alone or in combination of two or more.
  • the nitrogen adsorption specific surface area of silica (measured by the BET method according to ASTM D3037-81) is preferably 50 to 300 m 2 / g, more preferably 80 to 220 m 2 / g, and particularly preferably 100 to 170 m 2 / g. Is.
  • the pH of silica is preferably pH 5-10.
  • the diarylamine compound represented by the general formula (1) as a method for immobilizing on the filler surface is not particularly limited, the A 1 diaryl amine compound represented by the general formula (1)
  • a method capable of reacting the constituent groups capable of bonding with the hydroxyl group with the hydroxyl groups present on the surface of the filler may be adopted.
  • the Examples thereof include a method of mixing the diarylamine compound represented by the general formula (1) with the filler.
  • the amount of the diarylamine compound represented by the above general formula (1) fixed to the filler is not particularly limited, but is preferably 0.1 to 10% by weight with respect to 100 parts by weight of the filler. Parts, more preferably 0.5 to 7 parts by weight, still more preferably 1 to 5 parts by weight, and particularly preferably 1.2 to 3 parts by weight.
  • the fixed amount of the diarylamine compound represented by the general formula (1) in the above range, the antiaging effect on the polymer material can be further enhanced.
  • the above general state of being fixed to the filler with respect to 100 parts by weight of the filler (when the molecule is eliminated due to the immobilization reaction, the state after the molecule is eliminated).
  • the amount of the diarylamine compound represented by the formula (1) is preferably in the above range.
  • the polymer composition of the present invention is obtained by blending the above-mentioned surface treatment filler with the polymer.
  • the surface treatment filler usually acts as an anti-aging agent for the polymer in the polymer composition of the present invention.
  • Examples of the polymer used in the present invention include synthetic resin and rubber.
  • the synthetic resin can be used without particular limitation as long as it is a synthetic resin used for applications requiring heat resistance, and examples thereof include polyolefins, polystyrene-based resins, polyesters, polycarbonates, and polyamides. These synthetic resins may be used alone or in combination of two or more.
  • the rubber can be used without particular limitation as long as it is used for applications requiring heat resistance.
  • natural rubber isoprene rubber, butadiene rubber, butyl rubber, chloroprene rubber, and styrene-butadiene copolymer are used.
  • Rubber containing conjugated diene units such as rubber, acrylonitrile-butadiene copolymer rubber (nitrile rubber), styrene-butadiene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber; acrylic rubber; Hydrin rubber; ethylene propylene rubber; and the like can be mentioned.
  • These rubbers may have a hydroxyl group, a carboxyl group, an alkoxysilyl group, an amino group, an epoxy group and the like. Further, these rubbers may be hydrogenated, and examples thereof include an acrylonitrile-butadiene copolymer rubber hydrogenated additive (hydrogenated nitrile rubber). These rubbers may be used alone, in combination of two or more, or in combination of the synthetic resins described above. Among these, acrylic rubber is particularly preferable because it has a high effect of improving the heat resistance when applied to acrylic rubber or hydrogenated nitrile rubber, which is required to have high heat resistance.
  • the method of blending the surface treatment filler into the polymer is not particularly limited, and in addition to the method of blending in the polymer latex or the polymer solution, any method after the polymer is precipitated by coagulating the polymer latex or the polymer solution.
  • examples thereof include a method of blending in the process of. For example, it may be blended at the stage of producing polymer pellets, at the stage of blending and kneading various compounding agents, or at the stage of molding using a molding machine.
  • the compounding time that can be sufficiently uniformly dispersed in the polymer may be appropriately selected.
  • the blending amount of the surface treatment filler is preferably 20 to 90 parts by weight, more preferably 30 to 80 parts by weight, and further preferably 40 to 70 parts by weight with respect to 100 parts by weight of the polymer.
  • Acrylic rubber as an example of the polymer constituting the polymer composition of the present invention comprises 50 to 100% by weight of a (meth) acrylic acid ester monomer unit, 10 to 0% by weight of a crosslinkable monomer unit, and if necessary. It is a rubber having a unit of 50 to 0% by weight of other monomers copolymerizable with the monomer forming these monomer units, and the ratio of each monomer unit constituting the acrylic rubber is adjusted. Thereby, the physical properties of the rubber can be adjusted.
  • (meth) acrylic refers to acrylic and / or methacrylic.
  • Acrylic rubber is known as rubber that has excellent oil resistance, especially oil resistance at high temperatures, and also has good heat resistance, and is in demand as hoses for automobiles, oil seals, O-rings, conveyor belts built into devices and machines, etc. It is increasing.
  • the (meth) acrylic acid ester monomer forming the (meth) acrylic acid ester monomer unit which is the main component of the acrylic rubber is not particularly limited, but for example, a (meth) acrylic acid alkyl ester is preferable.
  • Monomers, (meth) acrylic acid alkoxyalkyl ester monomers and the like can be mentioned.
  • the (meth) acrylic acid alkyl ester monomer is not particularly limited, but an ester of alkanol having 1 to 8 carbon atoms and (meth) acrylic acid is preferable, and specifically, methyl (meth) acrylic acid, ( Ethyl acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) Examples thereof include 2-ethylhexyl acrylate and cyclohexyl (meth) acrylate.
  • ethyl (meth) acrylate and n-butyl (meth) acrylate are preferable, and ethyl acrylate and n-butyl acrylate are more preferable. These can be used alone or in combination of two or more.
  • the (meth) acrylic acid alkoxyalkyl ester monomer is not particularly limited, but an ester of an alkoxyalkyl alcohol having 2 to 8 carbon atoms and (meth) acrylic acid is preferable, and specifically, (meth) acrylic acid.
  • 2-ethoxyethyl (meth) acrylate and 2-methoxyethyl (meth) acrylate are preferable, and 2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are particularly preferable. These can be used alone or in combination of two or more.
  • the content of the (meth) acrylic acid ester monomer unit in the acrylic rubber is 50 to 100% by weight, preferably 60 to 99.5% by weight, and more preferably 70 to 99.5% by weight. If the content of the (meth) acrylic acid ester monomer unit is too small, the weather resistance, heat resistance and oil resistance of the obtained rubber crosslinked product may decrease.
  • the breakdown of the (meth) acrylic acid ester monomer unit is 30 to 100% by weight of the (meth) acrylic acid alkyl ester monomer unit and 70 to 0% by weight of the (meth) acrylic acid alkoxyalkyl ester monomer unit. Is preferable.
  • the crosslinkable monomer forming the crosslinkable monomer unit is not particularly limited, but is an ⁇ , ⁇ -ethylene unsaturated carboxylic acid monomer; a monomer having a halogen atom or an epoxy group; a diene unit amount. Body; etc.
  • the ⁇ , ⁇ -ethylenic unsaturated carboxylic acid monomer is not particularly limited, and for example, ⁇ , ⁇ -ethylene unsaturated monocarboxylic acid having 3 to 12 carbon atoms and ⁇ , ⁇ - having 4 to 12 carbon atoms are used. Examples thereof include an ethylenically unsaturated dicarboxylic acid and a monoester of ⁇ , ⁇ -ethylene unsaturated dicarboxylic acid having 4 to 12 carbon atoms and an alkanol having 1 to 8 carbon atoms.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms include acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, crotonic acid, and cinnamic acid.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms include butenedioic acid such as fumaric acid or maleic acid, itaconic acid, citraconic acid, and chloromaleic acid.
  • Monoesters of ⁇ , ⁇ -ethylenic unsaturated dicarboxylic acid having 4 to 12 carbon atoms and alkanol having 1 to 8 carbon atoms include monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monomethyl maleate, and monoethyl maleate.
  • Itaconic acid monochain alkyl ester such as monobutyl maleate; monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexenyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate, monocyclohexenyl maleate and other alicyclic structures
  • Butendionic acid monoesters monomethyl itaconic acid, monoethyl itaconic acid, monobutyl itaconic acid, monocyclohexyl itaconic acid and the like; and the like.
  • a monochain alkyl ester of butenioic acid or a monoester of butendioate having an alicyclic structure is preferable, and monobutyl fumarate, monobutyl maleate, monocyclohexyl fumarate and monocyclohexyl maleate are more preferable.
  • These ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more.
  • the dicarboxylic acid may be copolymerized as an anhydride, and may be hydrolyzed to generate a carboxyl group at the time of crosslinking.
  • the monomer having a halogen atom is not particularly limited, and for example, an unsaturated alcohol ester of a halogen-containing saturated carboxylic acid, a (meth) acrylic acid haloalkyl ester, a (meth) acrylic acid haloacyloxyalkyl ester, or (meth) acrylic.
  • an unsaturated alcohol ester of a halogen-containing saturated carboxylic acid a (meth) acrylic acid haloalkyl ester, a (meth) acrylic acid haloacyloxyalkyl ester, or (meth) acrylic.
  • acrylic include acid (haloacetylcarbamoyloxy) alkyl esters, halogen-containing unsaturated ethers, halogen-containing unsaturated ketones, halomethyl group-containing aromatic vinyl compounds, halogen-containing unsaturated amides, and haloacetyl group-containing unsaturated monomers.
  • Examples of the unsaturated alcohol ester of the halogen-containing saturated carboxylic acid include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetate.
  • Examples of the (meth) acrylic acid haloalkyl ester include (meth) acrylic acid chloromethyl, (meth) acrylic acid 1-chloroethyl, (meth) acrylic acid 2-chloroethyl, (meth) acrylic acid 1,2-dichloroethyl, and (meth) acrylic acid. ) 2-Chloropropyl acrylate, 3-chloropropyl (meth) acrylate, 2,3-dichloropropyl (meth) acrylate and the like.
  • Examples of the (meth) acrylic acid haloacyloxyalkyl ester include (meth) acrylic acid 2- (chloroacetoxy) ethyl, (meth) acrylic acid 2- (chloroacetoxy) propyl, and (meth) acrylic acid 3- (chloroacetoxy) propyl. , (Meta) acrylate 3- (hydroxychloroacetoxy) propyl and the like.
  • Examples of the (meth) acrylic acid (haloacetylcarbamoyloxy) alkyl ester examples include 2- (chloroacetylcarbamoyloxy) ethyl (meth) acrylic acid and 3- (chloroacetylcarbamoyloxy) propyl (meth) acrylic acid.
  • Examples of the halogen-containing unsaturated ether include chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 3-chloropropyl vinyl ether, 2-chloroethyl allyl ether, 3-chloropropyl allyl ether and the like.
  • halogen-containing unsaturated ketone examples include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, and 2-chloroethyl allyl ketone.
  • halomethyl group-containing aromatic vinyl compound examples include p-chloromethylstyrene and p-chloromethyl- ⁇ -methylstyrene.
  • halogen-containing unsaturated amide examples include N-chloromethyl (meth) acrylamide.
  • haloacetyl group-containing unsaturated monomer examples include 3- (hydroxychloroacetoxy) propyl allyl ether and p-vinylbenzyl chloroacetic acid ester.
  • the monomer having an epoxy group is not particularly limited, and examples thereof include an epoxy group-containing (meth) acrylic acid ester and an epoxy group-containing ether.
  • examples of the epoxy group-containing (meth) acrylic acid ester include glycidyl (meth) acrylate, and examples of the epoxy group-containing ether include allyl glycidyl ether.
  • Examples of the diene monomer include a conjugated diene monomer and a non-conjugated diene monomer.
  • Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, and piperylene.
  • Examples of the non-conjugated diene monomer include ethylidene norbornene, dicyclopentadiene, dicyclopentadienyl (meth) acrylate, and 2-dicyclopentadienyl ethyl (meth) acrylate.
  • crosslinkable monomers can be used alone or in combination of two or more.
  • the content of the crosslinkable monomer unit in the acrylic rubber is 0 to 10% by weight, preferably 0.5 to 7% by weight, and more preferably 0.5 to 5% by weight. If the content of the crosslinkable monomer unit is too large, the elongation of the obtained rubber crosslinked product may decrease or the compression set may increase.
  • the other monomer copolymerizable with each of the above-mentioned monomers is not particularly limited, and for example, an aromatic vinyl monomer, an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer, and an acryloyloxy group are used. Examples thereof include monomers having more than one, olefin-based monomers, and vinyl ether compounds.
  • Examples of the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, and divinylbenzene.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile.
  • Examples of the polyfunctional (meth) acrylic monomer include ethylene glycol (meth) acrylic acid diester and propylene glycol (meth) acrylic acid diester.
  • Examples of the olefin-based monomer include ethylene, propylene, 1-butene, 1-octene and the like.
  • Examples of the vinyl ether compound include vinyl acetate, ethyl vinyl ether, butyl vinyl ether and the like. Among these, styrene, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile and metaacrylonitrile are more preferable.
  • the content of other monomer units in the acrylic rubber is 0 to 50% by weight, preferably 0 to 39.5% by weight, and more preferably 0 to 29.5% by weight.
  • the acrylic rubber used in the present invention can be obtained by polymerizing the above-mentioned monomer.
  • any of an emulsion polymerization method, a suspension polymerization method, a massive polymerization method and a solution polymerization method can be used, but a conventionally known method for producing acrylic rubber is considered from the viewpoint of ease of control of the polymerization reaction and the like. It is preferable to use the emulsification polymerization method under normal pressure, which is generally used as the above.
  • the emulsion polymerization may be a batch type, a semi-batch type, or a continuous type.
  • the polymerization is usually carried out in a temperature range of 0 to 70 ° C, preferably 5 to 50 ° C.
  • the Mooney viscosity [ML1 + 4, 100 ° C.] (polymer Mooney) of the acrylic rubber produced in this manner used in the present invention is preferably 10 to 80, more preferably 20 to 70, and particularly preferably 25 to 60. ..
  • the polymer composition of the present invention may contain other antioxidants other than the surface treatment filler in addition to the polymer and the surface treatment filler as an antioxidant.
  • the other anti-aging agent is not particularly limited, but a compound represented by the following general formula (19) is preferably used.
  • Ra and R b each independently represent an organic group having 1 to 30 carbon atoms which may have a substituent.
  • Z a and Z b independently represent a chemical single bond or -SO 2-.
  • r and s are independently 0 or 1, and at least one of r and s is 1.
  • Ra and R b each independently represent an organic group having 1 to 30 carbon atoms which may have a substituent.
  • the organic group having 1 to 30 carbon atoms constituting Ra and R b is not particularly limited, but for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec- Alkyl group having 1 to 30 carbon atoms such as butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group; cyclopropyl Cycloalkyl group having 3 to 30 carbon atoms such as group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; ary
  • the organic groups constituting Ra and R b described above may have a substituent, and the position of the substituent may be any position.
  • a substituent when the organic group is an alkyl group, a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkoxy having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group or an isopropoxy group.
  • the substituents include halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; and 1 to 1 to carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group. Examples thereof include 10 alkoxy groups; nitro groups; cyano groups; alkyl groups having 1 to 10 carbon atoms such as methyl groups, ethyl groups, and t-butyl groups; and the like.
  • examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; nitro group; cyano group; and the like.
  • the organic groups constituting Ra and R b have a substituent, the carbon number of the organic group does not include the carbon number of the substituent.
  • R a and R b are each independently an alkyl group having 2 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent. It preferably has a linear or branched alkyl group having 2 to 20 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, or a substituent. It is more preferably a naphthyl group which may have a substituent, and may be a linear or branched alkyl group having 2 to 8 carbon atoms which may have a substituent, or a phenyl group which may have a substituent.
  • a linear or branched alkyl group having 2 to 8 carbon atoms, which may have a substituent is particularly preferable.
  • substituents include an alkyl group having 1 to 30 carbon atoms in which the organic group may have a substituent and an aryl group having 6 to 30 carbon atoms which may have a substituent. The same ones as illustrated can be mentioned.
  • Preferred specific examples of the organic groups constituting R a and R b include ⁇ -methylbenzyl group, ⁇ , ⁇ -dimethylbenzyl group, t-butyl group, phenyl group, 4-methylphenyl group and the like. Among these, ⁇ , ⁇ -dimethylbenzyl group or 4-methylphenyl group is more preferable, and ⁇ , ⁇ -dimethylbenzyl group is further preferable. It should be noted that these can be independent of each other.
  • Z a and Z b are each independently a chemical single bond or ⁇ SO 2- , and it is preferable that they are chemically single bonds.
  • r and s are independently 0 or 1, and at least one of r and s is 1. It is preferable that r and s are both 1.
  • the compound represented by the general formula (19) is preferably any of the compounds represented by the following general formulas (20) to (22).
  • R a, R b, Z a and Z b is as defined in the above general formula (19).
  • the compounds represented by the general formulas (20) to (22) are preferable, and the compounds represented by the general formula (22) are more preferable.
  • -Z a- R a and -Z b- R b are independent of each other, and are ⁇ -methylbenzyl group, ⁇ , ⁇ -dimethylbenzyl group, and t-butyl. It is preferably a group, a phenylsulfonyl group, or a 4-methylphenylsulfonyl group, more preferably an ⁇ , ⁇ -dimethylbenzyl group, or a 4-methylphenylsulfonyl group, and is an ⁇ , ⁇ -dimethylbenzyl group. Is even more preferable.
  • Ra and R b are linear or branched alkyls having 2 to 8 carbon atoms which may independently have substituents.
  • the groups, as well as Z a and Z b, are chemical single bonds, preferably r and s of 1.
  • the compound represented by the above general formula (19) is obtained by applying a known method for producing a phenothiazine-based compound to obtain a precursor phenothiazine-based compound, and then oxidizing the obtained compound. Can be manufactured.
  • the compound represented by the general formula (19) is prepared by the reaction method described in International Publication No. 2011/093443, using the compound represented by the following general formula (23) (phenothiazine) as a starting material. , Introducing substituents (-Z a- R a , -Z b- R b ) at the 1, 3, 6, and / or 8-positions of the phenothiazine ring in general formula (23), and phenothiazine. It can be obtained by oxidizing the S of the ring to -SO 2-.
  • Ra and R b each independently represent an organic group having 1 to 30 carbon atoms which may have a substituent, and may have a substituent. 1-30 aromatic or cyclic aliphatic groups are preferred.
  • the aromatic group having 1 to 30 carbon atoms is not particularly limited, and for example, an aromatic hydrocarbon group such as a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, or an anthranyl group, a frill group, a pyrrolyl group, or a thienyl group.
  • Aromatic heterocyclic groups such as pyridyl group and thiazolyl group.
  • the cyclic aliphatic group having 1 to 30 carbon atoms is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • a cyclopropyl group a cyclobutyl group
  • a cyclopentyl group a cyclohexyl group.
  • Ra and R b a phenyl group and a 4-methylphenyl group are preferable independently of each other.
  • the organic groups constituting Ra and R b described above may have a substituent, and the position of the substituent may be any position.
  • Examples of such a substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group; a nitro group; a cyano group; a methyl group.
  • a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom
  • an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group
  • a nitro group such as a cyano group
  • An alkyl group having 1 to 10 carbon atoms such as an ethyl group and a t-butyl group; and the like can be mentioned.
  • the blending amount of the compound represented by the general formula (19) in the polymer composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the polymer. It is 5 parts by weight, more preferably 0.5 to 3 parts by weight.
  • an antioxidant other than the compound represented by the above general formula (19) may be blended, and examples of such an antioxidant include 2,6-di-t-butyl-p-cresol, 2. 6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-sec butylphenol, 2- (1-methylcyclohexyl) ) -4,6-Dimethylphenol, 2,6-di-t-butyl- ⁇ -dimethylamino-p-cresol, 2,4-bis [(octylthio) methyl] -o-cresol, styrenated phenol, alkylated Monophenolic anti-aging agents such as phenol; 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4' -Methylenebis (2,6-di-t-butyl
  • antioxidant additives methods for preparing polymer compositions, etc.> Further, in addition to other antioxidants such as a polymer, a surface treatment filler, and a compound represented by the above general formula (19) used as necessary, the polymer composition of the present invention is further added.
  • the agent may be contained.
  • additives include those commonly used in the field of using synthetic polymeric materials.
  • reinforcing fillers such as carbon black
  • non-reinforcing fillers such as calcium carbonate and clay
  • light stabilizers such as aluminum carbonate and clay
  • anti-scorch agents plasticizers
  • processing aids such as lubricants; adhesives; lubricants; flame retardants; Molds; antistatic agents; colorants; silane coupling agents; cross-linking agents; cross-linking accelerators; cross-linking retarders; etc.
  • the blending amount of these additives is not particularly limited as long as it does not impair the purpose and effect of the present invention, and an amount suitable for the blending purpose can be appropriately blended.
  • the polymer composition of the present invention can be prepared, for example, by mixing and kneading each component with a Banbury mixer, a kneader, or the like, and then further kneading with a kneading roll.
  • the blending order of each component is not particularly limited, but after sufficiently mixing the components that are difficult to react or decompose with heat, the cross-linking agent, which is a component that easily reacts or decomposes with heat, is short at a temperature at which reaction or decomposition does not occur. It is preferable to mix in time.
  • a rubber cross-linked product can be obtained by cross-linking the rubber.
  • the rubber crosslinked product can be obtained by molding with a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, etc., and fixing the shape as a rubber crosslinked product by a cross-linking reaction. Can be done. In that case, cross-linking may be performed after molding in advance, or cross-linking may be performed at the same time as molding.
  • the molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C.
  • the cross-linking temperature is usually 130 to 220 ° C., preferably 150 to 190 ° C.
  • the cross-linking time is usually 2 minutes to 10 hours, preferably 3 minutes to 6 hours.
  • a method used for cross-linking rubber such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.
  • the secondary crosslinking time varies depending on the heating method, cross-linking temperature, shape, etc., but is preferably 1 to 48 hours.
  • the heating method and heating temperature may be appropriately selected.
  • the rubber crosslinked product obtained in this way has excellent heat resistance. Therefore, the rubber cross-linked product obtained by using the above rubber composition makes use of its characteristics, O-ring, packing, diaphragm, oil seal, shaft seal, bearing seal, mechanical seal, well head seal, electrical / electronic equipment.
  • Various seals such as seals for pneumatic equipment, cylinder head gaskets attached to the joints between the cylinder block and the cylinder head, rocker cover gaskets attached to the joints between the rocker cover and the cylinder head, oil pans and cylinders.
  • Oil pan gasket installed at the connection with the block or transmission case, fuel cell separator gasket installed between a pair of housings that sandwich a unit cell with a positive electrode, electrolyte plate, and negative electrode, gasket for the top cover of a hard disk drive.
  • gaskets such as; various belts; fuel hose, turbo air hose, oil hose, radiator hose, heater hose, water hose, vacuum brake hose, control hose, air conditioner hose, brake hose, power steering hose, air hose, marine hose, etc.
  • hoses such as risers and flow lines; various boots such as CVJ boots, propeller shaft boots, constant velocity joint boots, rack and pinion boots; damping materials such as cushioning materials, dynamic dampers, rubber couplings, air springs, and anti-vibration materials. It is preferably used as a rubber component; and is particularly applicable to applications used under harsh high temperatures.
  • Rate of change in elongation at break (%) [(Elongation at break after heating (%))-(Elongation before heating (%))] / (Elongation at break before heating (%))] ⁇ 100
  • a surface-treated silica prepared by fixing the represented compound was prepared.
  • the surface-treated silica is obtained by reacting 100 parts of silica with a compound represented by the above formula (24) at a ratio of 2.4 parts (considering the desorbed ethanol molecule, the above formula (24)).
  • the compound represented by (reacted at a ratio of 1.8 parts).
  • Example 1 100 parts of acrylic rubber (trade name “Hytemp AR212HR”, manufactured by Nippon Zeon Co., Ltd.), surface-treated silica obtained in Synthesis Example 3 (surface treatment in which the compound represented by the above formula (24) is fixed on the silica surface).
  • Silica 50.9 parts, silane coupling agent (trade name "KBM-403", manufactured by Shinetsu Silicone Co., Ltd.), 1 part, stearic acid 2 parts, ester wax (trade name "Greg G8205”, manufactured by Dainippon Ink Co., Ltd.) After kneading 1 part and 1 part of the compound represented by the above formula (25) obtained in Synthesis Example 4 at 50 ° C.
  • a rubber crosslinked product obtained by using acrylic rubber containing surface-treated silica in which a compound represented by the above formula (24) is fixed on a silica surface has a elongation at break after heating. It was high, and the rate of change in elongation at break before and after heating was small, and deterioration due to heating was effectively suppressed (Example 1).
  • the obtained rubber crosslinked product has a small elongation at break after heating and is heated. The rate of change in breaking elongation before and after was also large, and the deterioration due to heating was large (Comparative Examples 1 and 2).

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Abstract

L'invention concerne un composé de diarylamine représenté par la formule générale (1) ci-dessous.　(A1)m – A2 – (A3 – A4)n (dans la formule générale (1) : A1 est un groupe qui est capable de se lier avec un groupe hydroxyle ; A2 est un groupe organique en C1–30 facultativement substitué ayant une valence de (m + n) ; A3 est une simple liaison chimique ou un groupe divalent contenant un groupe choisi parmi des groupes éther, des groupes céto, des groupes ester et des groupes amide ; A4 est un groupe monovalent dérivé d'un composé diarylamine spécifique ; m est un nombre entier de 1 à 5 ; et n est un nombre entier de 1 à 5.)
PCT/JP2021/003554 2020-02-10 2021-02-01 Composé de diarylamine, agent de charge traité en surface et composition de polymère WO2021161838A1 (fr)

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Publication number Priority date Publication date Assignee Title
US4156677A (en) * 1977-06-28 1979-05-29 Union Carbide Corporation Polymer composite articles containing amino substituted mercapto organo silicon coupling agents
WO2011002038A1 (fr) * 2009-06-30 2011-01-06 日本ゼオン株式会社 Nouveau composé diarylamine, et agent antivieillissement, composition de polymère, produit de caoutchouc réticulé et article moulé de celui-ci, et procédé de production d'un composé diarylamine
WO2011093443A1 (fr) * 2010-01-29 2011-08-04 日本ゼオン株式会社 Composé hétérocyclique réuni par fusion et composition
CN102584886A (zh) * 2012-01-17 2012-07-18 华南理工大学 一种硅烷偶联剂及其制备方法
WO2018159459A1 (fr) * 2017-03-03 2018-09-07 日本ゼオン株式会社 Composé à base de diarylamine, agent antivieillissement et composition de polymère

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Publication number Priority date Publication date Assignee Title
US4156677A (en) * 1977-06-28 1979-05-29 Union Carbide Corporation Polymer composite articles containing amino substituted mercapto organo silicon coupling agents
WO2011002038A1 (fr) * 2009-06-30 2011-01-06 日本ゼオン株式会社 Nouveau composé diarylamine, et agent antivieillissement, composition de polymère, produit de caoutchouc réticulé et article moulé de celui-ci, et procédé de production d'un composé diarylamine
WO2011093443A1 (fr) * 2010-01-29 2011-08-04 日本ゼオン株式会社 Composé hétérocyclique réuni par fusion et composition
CN102584886A (zh) * 2012-01-17 2012-07-18 华南理工大学 一种硅烷偶联剂及其制备方法
WO2018159459A1 (fr) * 2017-03-03 2018-09-07 日本ゼオン株式会社 Composé à base de diarylamine, agent antivieillissement et composition de polymère

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LUO, K. ET AL.: "Effects of antioxidant functionalized silica on reinforcement and anti-aging for solution-polymerized styrene butadiene rubber: Experimental and molecular simulation study", MATERIALS AND DESIGN, vol. 154, 2018, pages 312 - 325, XP055848535 *

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