Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/42—Nitriles
  • C08F220/44—Acrylonitrile
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/56—Acrylamide; Methacrylamide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/12—Esters of phenols or saturated alcohols
  • C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/12—Esters of phenols or saturated alcohols
  • C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking

Definitions

• crosslinking copolymer rubber typically acrylic rubber
• the method of crosslinking copolymer rubber usually involves heating at approximately 150°C to 190°C for several minutes to several tens of minutes as the primary crosslinking, and then heating in a heated air environment at 140°C to 200°C for several hours as the secondary crosslinking (Patent Document 1).
• the present invention was made in consideration of these circumstances, and aims to provide a copolymer rubber that has good scorch stability and can give a cross-linked rubber product with sufficient mechanical properties without secondary cross-linking.
• R 1 is an alkyl group having 1 to 4 carbon atoms
• R 2 is a group represented by R 7 or OR 8
• R 7 is an alkyl group having 1 to 8 carbon atoms which may have a substituent
• R 8 is an alkyl group having 1 to 8 carbon atoms which may have a substituent or a polyalkylene glycol group which may have a substituent
• R 3 , R 4 and R 6 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• R 5 is a hydrogen atom, R 7 or a group represented by OR 8
• R 3 is a hydrogen atom, R 2 is a group represented by OR 8
• the present invention provides a copolymer rubber that has good scorch stability and can give a cross-linked rubber product with sufficient mechanical properties without secondary cross-linking.
• the copolymer rubber of the present invention is obtained by copolymerizing a butenedioic acid diester structure-containing monomer represented by the general formula (1) described below with a radical polymerizable monomer.
• R 1 is an alkyl group having 1 to 4 carbon atoms
• R 2 is a group represented by R 7 or OR 8
• R 7 is an alkyl group having 1 to 8 carbon atoms which may have a substituent
• R 8 is an alkyl group having 1 to 8 carbon atoms which may have a substituent or a polyalkylene glycol group which may have a substituent
• R 3 , R 4 and R 6 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• R 5 is a hydrogen atom, R 7 or a group represented by OR 8
• R 1 and R 2 may be bonded to each other to form a ring
• R 4 and R 5 may be bonded to each other to form
• the units derived from the butenedioic acid diester structure-containing monomer represented by general formula (1) act as crosslinkable monomer units in the copolymer rubber of the present invention. Although the mechanism by which they act as crosslinkable monomer units is not entirely clear, it is presumed that carboxyl groups are generated in the units derived from the butenedioic acid diester structure-containing monomer represented by general formula (1) during crosslinking, and these act as crosslinking points.
• the copolymer rubber of the present invention contains units derived from the butenedioic acid diester structure-containing monomer represented by general formula (1) as crosslinkable monomer units, and can provide a crosslinked rubber product having sufficient mechanical properties without secondary crosslinking while having good scorch stability.
• the bond form of the group represented by -COO-C(-R 1 )(-R 2 )(-R 3 ) to the carbon atom may be a cis bond or a trans bond, but is preferably a trans bond. That is, the butenedioic acid diester structure-containing monomer represented by general formula (1) has a fumaric acid diester structure (trans bond type) or a maleic acid diester structure (cis bond type), and preferably has a fumaric acid diester structure (trans bond type).
• R 1 to R 6 may be linear, branched, or have a cyclic structure.
• R 1 is not particularly limited as long as it is an alkyl group having 1 to 4 carbon atoms, but from the viewpoint of achieving both scorch stability and crosslinking rate at a higher level, it is preferably a methyl group or an ethyl group, and more preferably a methyl group.
• R 1 and R 2 are bonded to each other to form a ring, R 1 is preferably a methylene group.
• R2 is a group represented by R7 or OR8 .
• R7 is an alkyl group having 1 to 8 carbon atoms which may have a substituent
• R8 is an alkyl group having 1 to 8 carbon atoms which may have a substituent or a polyalkylene glycol group which may have a substituent.
• polyalkylene glycol group examples include a polyethylene glycol group, a polypropylene glycol group, a group consisting of a copolymer chain of ethylene glycol and propylene glycol, etc.
• the number of repeating alkylene glycol units is preferably 1 to 3.
• Substituents include halogen atoms such as fluorine, chlorine, and bromine atoms; alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, and isopropoxy; nitro groups; cyano groups; phenyl groups, 4-methylphenyl groups, 2-chlorophenyl groups, 1-naphthyl groups, 2-naphthyl groups, and aryl groups having 6 to 10 carbon atoms.
• R 2 is preferably a group represented by OR 8.
• R 8 is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a linear polyalkylene glycol group having 2 to 8 carbon atoms, more preferably a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms, even more preferably a linear alkyl group having 2 to 6 carbon atoms or a branched alkyl group having 4 to 8 carbon atoms, and particularly preferably an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a 2-ethylhexyl group.
• the ring (a ring formed by bonding together both ends of a chain represented by -R 1 -C * -R 2 -, where C * is a carbon atom bonded to R 1 , R 2 , R 3 and an oxygen atom) is preferably a 5- or 6-membered ring which may have an oxygen atom, and is preferably a 5- or 6-membered ring which has an oxygen atom.
• 5-membered rings include 5-membered rings formed by bonding together both ends of a chain represented by -(CH 2 ) 2 -C * -O-CH 2 - or -(CH 2 ) 2 -C * -(CH 2 ) 2 -, and 5-membered rings in which one or more hydrogen atoms in these chains are substituted with a substituent such as an alkyl group.
• the six-membered ring include a six-membered ring formed by bonding together both ends of a chain represented by -(CH 2 ) 3 -C * -O-CH 2 - or -(CH 2 ) 3 -C * -(CH 2 ) 2 -, and a six-membered ring formed by replacing one or more hydrogen atoms in such a chain with a substituent such as an alkyl group.
• a ring formed by bonding together both ends of a chain represented by -(CH 2 ) 2 -C * -O-CH 2 - or -(CH 2 ) 3 -C * -O-CH 2 - is preferred.
• R3 is not particularly limited as long as it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but from the viewpoint of achieving both scorch stability and crosslinking rate at a higher level, it is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Note that, in general formula (1), when R3 is a hydrogen atom, R2 is a group represented by OR8 .
• R 4 is not particularly limited as long as it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but from the viewpoint of achieving both scorch stability and crosslinking rate at a higher level, it is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
• R 4 and R 5 are bonded to each other to form a ring, R 4 is preferably a methylene group.
• R5 is a hydrogen atom, a group represented by R7 or OR8 , where R7 and OR8 are the same as R7 and OR8 as R2 .
• R5 is preferably a group represented by R7 , more preferably a linear alkyl group having 1 to 8 carbon atoms, even more preferably a linear alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an n-propyl group.
• the ring (a ring formed by bonding both ends of a chain represented by -R 4 -C * -R 5 -, where C * is a carbon atom bonded to R 4 , R 5 , R 6 and an oxygen atom) is preferably a 5- or 6-membered ring which may have an oxygen atom, and is preferably a 5- or 6-membered ring which does not have an oxygen atom.
• the ring include those mentioned above as the ring formed by bonding R 1 and R 2 to each other, and among them, a ring formed by bonding both ends of a chain represented by -(CH 2 ) 2 -C * -(CH 2 ) 2 - or -(CH 2 ) 3 -C * -(CH 2 ) 2 - is preferred.
• R 6 is not particularly limited as long as it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but from the viewpoint of achieving both scorch stability and crosslinking rate at a higher level, it is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
• the butenedioic acid diester structure-containing monomer represented by general formula (1) is preferably a butenedioic acid diester structure-containing monomer represented by the following general formula (2) or general formula (3), from the viewpoint of achieving both scorch stability and crosslinking rate at a higher level.
• R 1 , R 3 , R 4 , R 6 , and R 8 are each independently the same as the groups in general formula (1);
• R 9 is an alkyl group having 1 to 17 carbon atoms which may have a substituent;
• R 10 is an alkyl group having 1 to 8 carbon atoms which may have a substituent or a polyalkylene glycol group which may have a substituent;
• R 1 and R 8 may be bonded to each other to form a ring;
• R 4 and R 10 may be bonded to each other to form a ring.
• the bond form of the group represented by -COO-C(-R 1 )(-OR 8 )(-R 3 ) to the carbon atom may be a cis bond or a trans bond, but is preferably a trans bond.
• the butenedioic acid diester structure-containing monomer represented by general formula (1) has a fumaric acid diester structure (trans bond type) or a maleic acid diester structure (cis bond type), and preferably has a fumaric acid diester structure (trans bond type).
• R 1 , R 3 , R 4 , R 6 , and R 8 to R 10 may be linear, branched, or have a cyclic structure.
• R 1 , R 3 , R 4 , R 6 and R 8 are each independently the same as the groups in formula (1), and the preferred groups are also the same.
• R 9 is an alkyl group having 1 to 17 carbon atoms which may have a substituent, and preferably an alkyl group having 1 to 16 carbon atoms which may have a substituent. Examples of the substituent include those mentioned above.
• R 9 in general formula (2) corresponds to the group represented by -C(-R 4 )(-R 5 )(-R 6 ) in general formula (1).
• R 9 is preferably a linear alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, more preferably a linear alkyl group having 2 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms, even more preferably a linear alkyl group having 2 to 4 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, and particularly preferably an ethyl group, an n-butyl group or a cyclohexyl group.
• R 10 is an alkyl group having 1 to 8 carbon atoms which may have a substituent, or a polyalkylene glycol group which may have a substituent. Examples of the substituent include those described above.
• R 10 in general formula (3) is the same as R 8 in general formula (3).
• R 10 is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a linear polyalkylene glycol group having 2 to 8 carbon atoms, more preferably a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms, even more preferably a linear alkyl group having 2 to 6 carbon atoms or a branched alkyl group having 4 to 8 carbon atoms, and particularly preferably an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a 2-ethylhexyl group.
• the ring (a ring formed by bonding both ends of a chain represented by -R 4 -C * -OR 10 -, where C * is a carbon atom bonded to R 4 , OR 10 , R 6 , and an oxygen atom) is preferably a 5-membered or 6-membered ring which may have an oxygen atom, and is preferably a 5-membered or 6-membered ring which has an oxygen atom.
• the ring include those mentioned above as the ring formed by R1 and R2 bonding to each other, and among these, a ring formed by bonding to each other at both ends of a chain represented by -(CH 2 ) 2 -C * -O-CH 2 - or -(CH 2 ) 3 -C * -O-CH 2 - is preferred.
• the method for producing the butenedioic acid diester structure-containing monomer represented by the general formula (1) is not particularly limited, and a suitable combination of conventionally known methods can be used.
• the content ratio of the butenedioic acid diester structure-containing monomer unit represented by general formula (1) is preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, and even more preferably 1 to 5% by weight.
• the radical polymerizable monomer is not particularly limited as long as it has radical polymerizability and is copolymerizable with the butenedioic acid diester structure-containing monomer represented by the above general formula (1), and examples thereof include (meth)acrylic acid ester monomers (meaning acrylic acid ester monomers and/or methacrylic acid ester monomers.
• (meth)acrylate, etc.) (meth)acrylonitrile monomers, aromatic vinyl monomers, conjugated diene monomers, (meth)acrylamide monomers, vinyl acetate monomers, ethylene monomers, and the like.
• the radical polymerizable monomer preferably includes at least one selected from a (meth)acrylic acid ester monomer, a (meth)acrylonitrile monomer, an aromatic vinyl monomer, a conjugated diene monomer, a (meth)acrylamide monomer, a vinyl acetate monomer, and an ethylene monomer, and more preferably includes a (meth)acrylic acid ester monomer.
• the copolymer rubber of the present invention may be, for example, an acrylic rubber containing (meth)acrylic acid ester monomer units; a nitrile rubber containing (meth)acrylonitrile monomer units; a styrene-butadiene rubber containing styrene units as aromatic vinyl monomer units and butadiene units as a conjugated diene monomer; a conjugated diene rubber containing conjugated diene monomer units; etc.
• the copolymer rubber of the present invention is an acrylic rubber containing (meth)acrylic acid ester monomer units.
• the copolymer rubber of the present invention is an acrylic rubber containing (meth)acrylic acid ester monomer units
• the (meth)acrylic acid ester monomers forming the (meth)acrylic acid ester monomer units are not particularly limited, but examples thereof include (meth)acrylic acid alkyl ester monomers and (meth)acrylic acid alkoxyalkyl ester monomers.
• the (meth)acrylic acid alkyl ester monomer is not particularly limited, but is preferably an ester of an alkanol having 1 to 8 carbon atoms with (meth)acrylic acid, and specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate.
• methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, with ethyl acrylate and n-butyl acrylate being particularly preferred. These can be used alone or in combination of two or more.
• the (meth)acrylic acid alkoxyalkyl ester monomer is not particularly limited, but is preferably an ester of an alkoxyalkyl alcohol having 2 to 12 carbon atoms and (meth)acrylic acid, and more preferably an ester of an alkoxyalkyl alcohol having 2 to 8 carbon atoms and (meth)acrylic acid.
• Examples of the other copolymerizable monomers include ester monomers other than the butenedioic acid diester structure-containing monomer represented by general formula (1), conjugated diene monomers, non-conjugated diene monomers, aromatic vinyl monomers, ⁇ , ⁇ -ethylenically unsaturated nitrile monomers such as (meth)acrylonitrile monomers, acrylamide monomers such as (meth)acrylamide monomers, and other olefin monomers.
• Ester monomers other than the butenedioic acid diester structure-containing monomer represented by general formula (1) include ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid esters and ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid diesters other than the butenedioic acid diester structure-containing monomer represented by general formula (1). Note that ester monomers other than the butenedioic acid diester structure-containing monomer represented by general formula (1) are usually non-crosslinkable monomers.
• copolymerizable monomers include carboxyl group-containing monomers.
• carboxyl group-containing monomers include ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomers, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids, and ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acids.
• the glass transition temperature of the copolymer rubber of the present invention is preferably 0°C or lower, more preferably -70 to -5°C, and even more preferably -50 to -15°C.
• the emulsifier is not particularly limited, and examples include nonionic emulsifiers, anionic emulsifiers, and cationic emulsifiers.
• Cationic emulsifiers include, for example, alkyltrimethylammonium chloride, dialkylammonium chloride, and benzylammonium chloride.
• peroxide either inorganic or organic peroxides may be used.
• peroxides and azo compounds can be used alone or in combination of two or more.
• the amount of peroxide and azo compound used in the initial polymerization step is preferably 0.001 to 0.5 parts by weight, more preferably 0.002 to 0.4 parts by weight, and even more preferably 0.003 to 0.3 parts by weight, per 100 parts by weight of the monomer components used in the polymerization.
• the reducing agent other than the metal ion compound in a reduced state can be used alone or in combination of two or more.
• the amount of the reducing agent other than the metal ion compound in a reduced state used in the initial polymerization step is preferably 0.005 to 0.080 parts by weight, more preferably 0.010 to 0.060 parts by weight, and even more preferably 0.020 to 0.040 parts by weight, per 100 parts by weight of the monomer component used in the polymerization.
• polymerization auxiliary materials such as molecular weight regulators, particle size regulators, chelating agents, and oxygen scavengers can be used as necessary.
• a method of adding the emulsion polymerization liquid to an aqueous solution containing the coagulant while stirring the aqueous solution containing the coagulant is preferred.
• the particle size of the water-containing crumbs generated by coagulation can be controlled to a relatively uniform range, and the washing efficiency of the generated water-containing crumbs can be improved.
• the solids concentration of the emulsion polymerization liquid used for coagulation is not particularly limited, and may be used as obtained by emulsion polymerization, but from the viewpoint of more appropriately controlling the particle size of the water-containing crumbs produced by coagulation, it is preferable to adjust the solids concentration to the range of 5 to 50% by weight, more preferably to the range of 10 to 45% by weight, and particularly preferably to the range of 20 to 40% by weight.
• the washing method is not particularly limited, but for example, a method of washing the hydrous crumbs obtained by the coagulation operation with water is included, and preferably a method of mixing the hydrous crumbs obtained by the coagulation operation with water is included.
• the temperature during washing is not particularly limited, but is preferably 5 to 60°C, more preferably 10 to 50°C, and the mixing time is 1 to 60 minutes, more preferably 2 to 30 minutes.
• the amount of water mixed with the hydrous crumbs during water washing is not particularly limited, but from the viewpoint of increasing the efficiency of water washing, it is preferable to use an amount of water that is 50 parts by weight or more per 100 parts by weight of the monomer components used in the polymerization, more preferably 50 to 15,000 parts by weight, even more preferably 100 to 10,000 parts by weight, and particularly preferably 500 to 5,000 parts by weight.
• the washing time is not particularly limited, but is preferably 1 to 120 minutes, more preferably 2 to 60 minutes, and even more preferably 3 to 30 minutes.
• the number of times of water washing is not particularly limited, and is preferably 1 to 10 times, more preferably 1 to 5 times, and even more preferably 1 to 3 times.
• the number of times of water washing refers to the number of times when the operation of adding water to the wet crumbs, mixing for a predetermined time, and separating the wet crumbs from the water used for water washing is defined as one water washing.
• the washed wet crumbs may be dried.
• a dryer such as a hot air dryer, a reduced pressure dryer, an expander dryer, a kneader type dryer, or a screw type extruder.
• the drying temperature for the hydrous crumbs is not particularly limited, but is preferably 80 to 250°C, more preferably 100 to 200°C, and even more preferably 110 to 180°C.
• the rubber composition of the present invention contains the copolymer rubber of the present invention and a crosslinking agent.
• the crosslinking agent is not particularly limited, but may be any of the conventionally known crosslinking agents, such as polyamine compounds, such as diamine compounds, and carbonates thereof; sulfur; sulfur donors; triazine thiol compounds; polyepoxy compounds; organic ammonium carboxylates; organic peroxides; metal dithiocarbamate salts; polycarboxylic acids; quaternary onium salts; imidazole compounds; and isocyanuric acid compounds. These crosslinking agents may be used alone or in combination of two or more.
• polyamine compounds and carbonates thereof are not particularly limited, but polyamine compounds having 4 to 30 carbon atoms and carbonates thereof are preferred. Examples of such polyamine compounds and carbonates thereof include aliphatic polyamine compounds and carbonates thereof, and aromatic polyamine compounds.
• Aliphatic polyamine compounds and their carbonates are not particularly limited, but examples include hexamethylenediamine, hexamethylenediamine carbamate, and N,N'-dicinnamylidene-1,6-hexanediamine.
• Aromatic polyamine compounds are not particularly limited, but examples include 4,4'-methylenedianiline, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-(m-phenylenediisopropylidene)dianiline, 4,4'-(p-phenylenediisopropylidene)dianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminobenzanilide, 4,4'-bis(4-aminophenoxy)biphenyl, m-xylylenediamine, p-xylylenediamine, and 1,3,5-benzenetriamine. Among these, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane is preferred.
• the crosslinking agent is preferably a polyamine compound and its carbonate, more preferably an aliphatic polyamine compound and its carbonate, and even more preferably hexamethylenediamine carbamate, from the viewpoint of achieving both scorch stability and crosslinking speed at a higher level and further improving the mechanical properties of the resulting crosslinked rubber product.
• the content of the crosslinking agent in the rubber composition of the present invention is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the copolymer rubber of the present invention.
• the rubber composition of the present invention may contain a rubber other than the copolymer rubber of the present invention described above.
• rubber other than the copolymer rubber of the present invention include, but are not limited to, rubber that does not contain units of the butenedioic acid diester structure-containing monomer represented by general formula (1) (acrylic rubber, natural rubber, polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, silicone rubber, fluororubber, olefin-based elastomer, styrene-based elastomer, vinyl chloride-based elastomer, polyester-based elastomer, polyamide-based elastomer, polyurethane-based elastomer, polysiloxane-based elastomer, etc.). These may be used alone or in combination of two or more.
• the content of the copolymer rubber of the present invention in the rubber composition of the present invention may be appropriately selected depending on the intended use, but is preferably 70 parts by weight or more, more preferably 90 parts by weight or more, even more preferably 95 parts by weight or more, and particularly preferably 100 parts by weight, per 100 parts by weight of the rubber component in the rubber composition of the present invention (i.e., an embodiment in which the rubber component of the rubber composition of the present invention is substantially composed of only the copolymer rubber of the present invention).
• guanidine compound a diazabicycloalkene compound, and an aliphatic monovalent secondary amine compound are preferred, and a guanidine compound and a diazabicycloalkene compound are particularly preferred.
• These crosslinking accelerators can be used alone or in combination of two or more.
• the content of the crosslinking accelerator in the rubber composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 7.5 parts by weight, and particularly preferably 1 to 5 parts by weight, based on 100 parts by weight of the copolymer rubber of the present invention.
• the rubber composition of the present invention may contain an antioxidant as necessary.
• the antioxidant include, but are not limited to, phenolic antioxidants such as doubly hindered phenolic antioxidants, semi-hindered phenolic antioxidants, less hindered phenolic antioxidants, and phenolic antioxidants that do not have a hindered group; phosphite ester antioxidants; sulfur ester antioxidants; secondary amine antioxidants such as phenyl- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, p-(p-toluenesulfonylamido)-diphenylamine, 4,4'-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine, N,N-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, and butyraldehyde-aniline condensates; imidazole antioxidants;
• ⁇ Crosslinking test> A crosslinking test was carried out on the rubber composition using a rubber vulcanization tester (trade name "Moving Die Rheometer MDR", manufactured by Alpha Technologies) at 170°C for 20 minutes in accordance with JIS K6300-2. From the results of the crosslinking test, the minimum torque (ML) (unit: dN ⁇ m), the maximum torque (MH) (unit: dN ⁇ m), and T90 (unit: min) were determined. Note that T90 refers to the time required for the torque to increase by 90% from the minimum torque ML when "maximum torque MH-minimum torque ML" is taken as 100%, and it can be determined that the smaller the T90 value, the faster the crosslinking speed.
• butenedioic acid diester structure-containing monomer represented by the following formulas (a) to (e) were used.
• the butenedioic acid diester structure-containing monomers (a) to (e) were produced according to the following Production Examples.
• Example 1 (Production of copolymer rubber (A-1)) A mixing vessel equipped with a homomixer was charged with 46.294 parts of ion-exchanged water, 60.0 parts of ethyl acrylate as monomers, 38.1 parts of n-butyl acrylate, and 1.9 parts of the butenedioic acid diester group-containing monomer (a) represented by the above formula (a), and 1.8 parts of tridecyloxyhexa(oxyethylene) phosphate sodium salt as an anionic emulsifier, and the mixture was stirred to obtain a monomer emulsion.
• a mixing vessel equipped with a homomixer was charged with 46.294 parts of ion-exchanged water, 60.0 parts of ethyl acrylate as monomers, 38.1 parts of n-butyl acrylate, and 1.9 parts of the butenedioic acid diester group-containing monomer (a) represented by the above formula (a), and 1.8 parts of tridecyloxyhe
• the copolymer rubber obtained by copolymerizing the butenedioic acid diester structure-containing monomer represented by general formula (1) with a radically polymerizable monomer had a long scorch time (t5) and good scorch stability, and was capable of giving a cross-linked rubber product with sufficient mechanical properties without secondary cross-linking (Examples 1 to 7).
• the copolymer rubber that does not contain units derived from the butenedioic acid diester structure-containing monomer represented by general formula (1) had a short scorch time (t5) and was poor in scorch stability (Comparative Examples 1-2).

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=91717950

Family Applications (1)

Country Status (5)

Citations (11)

• 2023
  • 2023-12-25 WO PCT/JP2023/046463 patent/WO2024143285A1/ja not_active Ceased
  • 2023-12-25 KR KR1020257020548A patent/KR20250129649A/ko active Pending
  • 2023-12-25 JP JP2024567810A patent/JPWO2024143285A1/ja active Pending
  • 2023-12-25 CN CN202380085192.8A patent/CN120344573A/zh active Pending
  • 2023-12-27 TW TW112150943A patent/TW202444775A/zh unknown

Patent Citations (11)

Also Published As

Similar Documents

Legal Events