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
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
  • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
• • 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
  • C08F20/00—Homopolymers and 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
• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms

Definitions

• This disclosure relates to a vinyl polymer and a method for producing the same.
• the living radical polymerization method includes a reversible addition-cleaving chain transfer polymerization method (RAFT method), a nitroxy radical method (NMP method), an atom transfer radical polymerization method (ATRP method), and a polymerization method using an organic tellurium compound (TERP method). ), A polymerization method using an organic antimony compound (SBRP method), a polymerization method using an organic bismuth compound (BIRP method), an iodine transfer polymerization method and the like are known.
• SBRP method organic antimony compound
• BIRP method organic bismuth compound
• iodine transfer polymerization method and the like are known.
• the RAFT method, the NMP method and the ATRP method are industrially used from the viewpoint of controllability of polymerization and ease of implementation.
• the RAFT method is attracting attention as a metal-free polymerization method that can be applied to the widest range of vinyl monomers. Vinyl-based polymers obtained by the RAFT method are
• RAFT agent polymerization control agent having a thiocarbonylthio group, such as a dithioester compound, a xanthate compound, a trithiocarbonate compound, a dithiocarbamate compound, etc.
• RAFT agent polymerization control agent having a thiocarbonylthio group
• a polymerization control agent such as a dithioester compound, a xanthate compound, a trithiocarbonate compound, a dithiocarbamate compound, etc.
• Patent Document 1 describes a compound having two dithioester groups as a RAFT agent having two thiocarbonylthio groups (1,4-bis (phenylthio).
• a polyacrylic acid ester produced by living radical polymerization using carbonylsulfanylmethyl) benzene) is disclosed.
• Non-Patent Document 1 uses a compound having two trithiocarbonate groups (1,4-bis (n-butylsulfanylthiocarbonylsulfanylmethyl) benzene) as a RAFT agent having two thiocarbonylthio groups.
• the polyacrylic acid ester produced by living radical polymerization was disclosed.
• Patent Document 1 and Non-Patent Document 1 do not have sufficient heat resistance (particularly, heat resistance under conditions higher than 150 ° C.), and there is room for further improvement.
• the present disclosure has been made in view of the above circumstances, and an object thereof is to provide a vinyl-based polymer having excellent heat resistance.
• the vinyl-based polymer obtained by living radical polymerization using a RAFT agent contains a polymer having a specific structural formula. It was also found that the inclusion of a polymer having this specific structural formula in an amount exceeding a predetermined amount causes a decrease in heat resistance when the vinyl-based polymer is subjected to high temperature conditions. Based on this finding, the inventor has completed the present disclosure. Specifically, according to the present disclosure, the following means are provided.
• the polymer (P1) represented by the following formula (1) and the polymer (P2) represented by the following formula (2) are contained, and the polymer (P1) and the polymer (P2) are contained.
• R 1 and R 3 are independently hydrogen atom, chlorine atom, alkyl group, aryl group, aralkyl group, heterocyclyl group, alkoxy group, alkylthio group and dialkoxy.
• Phosphino group alkoxycarbonyl group, "-O-Ar 1 ", “-S-Ar 1 " or “-NR 4 R 5 " (where Ar 1 indicates an aryl group or an aralkyl group, R 4 and R 5 independently indicates a monovalent hydrocarbon group), and any hydrogen atom bonded to the carbon atom may be substituted.
• R 2 is a substituted or unsubstituted divalent aromatic hydrocarbon. Indicates a hydrogen group.
• A indicates a polymer chain having a structural unit derived from a vinyl monomer.
• the vinyl monomer is the vinyl polymer of [1] or [2], which contains a (meth) acrylic compound.
• a method for producing a vinyl-based polymer by a living radical polymerization method wherein a compound (R1) represented by the following formula (3) and a compound (R2) represented by the following formula (4) are used.
• the step of polymerizing a vinyl monomer using the contained RAFT agent is included, and the content of the compound (R2) in the RAFT agent is 10 mol with respect to the total amount of the compound (R1) and the compound (R2). % Or less, a method for producing a vinyl-based polymer.
• R 1 and R 3 are independently hydrogen atom, chlorine atom, alkyl group, aryl group, aralkyl group, heterocyclyl group, alkoxy group, alkylthio group and dialkoxy. It indicates a phosphino group, an alkoxycarbonyl group, "-O-Ar 1 ", “-S-Ar 1 " or "-NR 4 R 5 " (where Ar 1 is an aryl group or an aralkyl group, R 4 and R 5 is an independently monovalent hydrocarbon group), and any hydrogen atom bonded to the carbon atom may be substituted.
• R 2 is a substituted or unsubstituted divalent aromatic hydrocarbon. Indicates a hydrogen group.
• a vinyl-based polymer having excellent heat resistance can be obtained.
• (meth) acrylic means acrylic and / or methacrylic
• (meth) acrylate means acrylate and / or methacrylate
• (meth) acrylo means acrylo and / or methacrylo.
• the vinyl-based polymer of the present disclosure (hereinafter, also referred to as "vinyl-based polymer (P)") is a polymer (P1) which is a vinyl-based polymer represented by the following formula (1) and the following formula (2). Includes a polymer (P2) which is a vinyl-based polymer represented by.
• the content of the polymer (P2) is 10 mol% or less with respect to the total amount (100 mol%) of the polymer (P1) and the polymer (P2).
• R 1 and R 3 are independently hydrogen atom, chlorine atom, alkyl group, aryl group, aralkyl group, heterocyclyl group, alkoxy group, alkylthio group and dialkoxy. It indicates a phosphino group, an alkoxycarbonyl group, "-O-Ar 1 ", “-S-Ar 1 " or “-NR 4 R 5 " (where Ar 1 is an aryl group or an aralkyl group, R 4 and R 5 is an independently monovalent hydrocarbon group), and any hydrogen atom bonded to the carbon atom may be substituted.
• R 2 is a substituted or unsubstituted divalent aromatic hydrocarbon. Indicates a hydrogen group.
• A indicates a polymer chain having a structural unit derived from a vinyl monomer.
• R 1 and R 3 include, as an alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and the like.
• Examples thereof include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group and a nonadecil group. These may be linear or branched.
• Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a 1-naphthyl group, a 2-naphthyl group and the like.
• Examples of the aralkyl group include a benzyl group and a phenethyl group.
• Examples of the heterocyclyl group include 1-pyrrolyl group, 1-imidazolyl group, 2-oxo-1-pyrrolidinyl group, phthalimide group and the like.
• Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and the like.
• alkylthio group methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group, tetradecylthio group, hexadecylthio group, Examples thereof include an octadecylthio group and a nonadecylthio group.
• dialkoxyphosphino group examples include a dimethoxyphosphino group, a diethoxyphosphino group, a methoxyethoxyphosphino group and the like.
• alkoxycarbonyl group examples include a methoxycarbonyl group and an ethoxycarbonyl group.
• Examples of the group represented by "-O-Ar 1 " include a phenoxy group and a benzyloxy group.
• Examples of the group represented by “-S-Ar 1 " include a phenyl sulfide group and a benzyl sulfide group.
• Examples of the group represented by "-NR 4 R 5 " include N, N-dimethylamino group, N, N-diethylamino group, N-methyl-N-ethylamino group, N-phenyl-N-methylamino group, and the like. Examples thereof include an N-phenyl-N-ethylamino group.
• examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom and the like), a cyano group and the like.
• R 1 and R 3 are preferably monovalent groups having 1 to 20 carbon atoms. Among these, at least one of R 1 and R 3 is preferably a substituted or unsubstituted alkyl thio group, and R 1 and R 3 are preferable because they have a high transfer constant and are excellent in controllability of polymerization. Is more preferably a substituted or unsubstituted alkylthio group.
• R2 is preferably a divalent group having 6 to 20 carbon atoms.
• R 2 include a substituted or unsubstituted phenylene group and a group represented by "-R 6 -B 1 -R 7- " (however, R 6 and R 7 have independent carbon atoms. 1 to 5 alkylene groups, B 1 is a substituted or unsubstituted phenylene group).
• substituents include an alkyl group (for example, a methyl group, an ethyl group, etc.), a halogen atom, and the like.
• R2 is preferably "-CH 2 -phenylene group-CH 2- ", “-CH (CH 3) -phenylene group-CH (CH 3 ) -", or “-C (". CH 3 ) 2 -Phenylene group-C (CH 3 ) 2- ".
• a in the above formulas (1) and (2) is a polymerized chain having a structural unit derived from a vinyl monomer.
• the polymer chains of the vinyl-based polymer (P) (that is, the polymer chains of the polymer (P1) and the polymer (P2)) are formed by A in the above formulas (1) and (2).
• the vinyl monomer constituting the polymerized chain various vinyl monomers having radical polymerizable properties can be used.
• the vinyl monomer include (meth) acrylic acid ester compounds, aromatic vinyl compounds, unsaturated carboxylic acids, unsaturated acid anhydrides, hydroxy group-containing vinyl compounds, amino group-containing vinyl compounds, and amide group-containing vinyls. Examples thereof include compounds, alkoxy group-containing vinyl compounds, nitrile group-containing vinyl compounds, maleimide compounds and the like.
• the vinyl monomer one of these may be used alone, or two or more thereof may be used in combination.
• vinyl monomer examples include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and isopropyl (meth) acrylic acid as the (meth) acrylic acid ester compound.
• aromatic vinyl compounds examples include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, vinylxylene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethyl.
• Styrene pn-butyl styrene, p-isobutyl styrene, pt-butyl styrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-chloro styrene, m-chloro styrene, p-chloro styrene , P-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol, o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid Examples thereof include styrene-based compounds such as acid and divinylbenzene, and vinylnaphthalene.
• unsaturated carboxylic acids examples include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, cinnamon acid, and monoalkyl esters of unsaturated dicarboxylic acids (maleic acid, fumaric acid, itaconic acid, and citraconic acid). Monoalkyl esters such as acids) and the like.
• unsaturated acid anhydride examples include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.
• hydroxy group-containing vinyl compound examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and (meth).
• Hydroxyalkyl compounds of (meth) acrylate such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and polyethylene glycol-polypropylene glycol mono
• Polyalkylene glycol mono (meth) acrylate compound such as (meth) acrylate; unsaturated alcohol such as allyl alcohol; N-substituted maleimide compound such as N- (4-hydroxyphenyl) maleimide; o-hydroxystyrene, m-hydroxystyrene And hydroxyl group-containing styrene compounds such as p-hydroxystyrene.
• amino group-containing vinyl compound examples include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, and (meth) acrylic.
• 2- (Di-n-propylamino) ethyl acid 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, 2- (di-n-propylamino) propyl (meth) acrylate , (Meta) acrylate 3-dimethylaminopropyl, (meth) acrylate 3-diethylaminopropyl, (meth) acrylate 3- (di-n-propylamino) propyl and the like.
• Examples of the amide group-containing vinyl compound include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide and the like.
• Examples of the alkoxy group-containing vinyl compound include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate, and 2 (meth) acrylate.
• nitrile group-containing vinyl compound examples include cyanomethyl (meth) acrylate, 1-cyanoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 1-cyanopropyl (meth) acrylate, and 2-cyanopropyl (meth) acrylate.
• Examples thereof include acid 8-cyanooctyl, (meth) acrylonitrile, ⁇ -ethylacrylonitrile, ⁇ -isopropylacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -fluoroacrylonitrile and the like.
• maleimide compound examples include maleimide and N-substituted maleimide compounds.
• N-substituted maleimide compound include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, and N-tert-butylmaleimide.
• N-alkyl-substituted maleimide compounds such as N-pentylmaleimide, N-hexylmaleimide, N-heptylmaleimide, N-octylmaleimide, N-laurylmaleimide, and N-stearylmaleimide; N-cyclopentylmaleimide, N-cyclohexylmaleimide, etc.
• N-Cycloalkyl-substituted maleimide compounds N-aralkyl-substituted maleimide compounds such as N-benzylmaleimide; N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-acetylphenyl) maleimide, N- ( Examples thereof include N-aryl substituted maleimide compounds such as 4-methoxyphenyl) maleimide, N- (4-ethoxyphenyl) maleimide, N- (4-chlorophenyl) maleimide, and N- (4-bromophenyl) maleimide.
• unsaturated dicarboxylic acid dialkyl esters, vinyl ester compounds, vinyl ether compounds and the like can also be used in the production of the vinyl polymer (P).
• the monomer constituting the polymer chain of the vinyl-based polymer (P) can be relatively easily produced by the living radical polymerization method, and the degree of freedom in selecting the monomer is high.
• it is preferable to include a (meth) acrylic compound and it is particularly preferable to include a compound represented by the following formula (5).
• R 8 represents a hydrogen atom or a methyl group
• R 9 represents a linear or branched alkylene group having 2 to 6 carbon atoms
• R 10 represents a hydrogen atom or a carbon number of carbon atoms.
• N represents an integer of 0 to 100.
• the compound represented by the above formula (5) include the (meth) acrylic acid ester compound, the alkoxy group-containing vinyl compound, the (meth) acrylic acid hydroxyalkyl compound, and the polyalkylene glycol mono (meth) exemplified above. )
• An acrylate compound can be mentioned.
• the group “-(R 9 O) n-R 10 " in the above formula (5) preferably has 2 or more carbon atoms, and preferably 3 or more carbon atoms. Is more preferable.
• the upper limit of the carbon number of the group "-(R 9 O) n-R 10 " is preferably 10 or less, more preferably 8 or less, from the viewpoint of maintaining the polymerization controllability.
• the amount of the (meth) acrylic compound among the monomers constituting the polymerized chain of the vinyl-based polymer (P) is preferably 50 mol% or more with respect to the total amount of the monomers constituting the polymerized chain. Yes, more preferably 70 mol% or more, further preferably 80 mol% or more, still more preferably 90 mol% or more.
• the vinyl-based polymer (P) is a mixture of the polymer (P1) and the polymer (P2). More specifically, the vinyl-based polymer (P) contains the polymer (P1) as a main component and the polymer (P2) as an impurity.
• the content of the polymer (P2) is 10 mol% or less with respect to the total amount (100 mol%) of the polymer (P1) and the polymer (P2).
• a vinyl-based polymer having excellent heat resistance under more severe high temperature conditions can be obtained. From this point of view, the content of the polymer (P2) in the vinyl-based polymer (P) is preferably 9.5 mol% or less with respect to the total amount of the polymer (P1) and the polymer (P2).
• the lower limit of the content of the polymer (P2) is not particularly limited, but from the viewpoint of ease of production, it is, for example, 0.01 mol% or more with respect to the total amount of the polymer (P1) and the polymer (P2). , 0.05 mol% or more, more preferably 0.1 mol% or more.
• impurities contained in the vinyl-based polymer (P) can be identified by the methods shown below.
• the vinyl-based polymer (P) is subjected to gel permeation chromatography (GPC) fractionation under the conditions described in Examples described later, and the obtained high molecular weight fraction is concentrated to obtain a concentrate.
• GPC gel permeation chromatography
• 1 H-NMR measurement of this concentrate was carried out, and the proton peaks derived from R1 , R2 and R3 in the above formulas (1) and (2), and the polymerization next to the thiocarbonylthio group were carried out.
• the integral value of the proton peaks derived from R1 and R3 is 0.5 times that of the integral value of the proton peaks derived from R2 , respectively.
• the integral value of the proton peak on the carbon of the polymer chain next to the carbonylthio group is observed at the same magnification. Utilizing this, it can be confirmed that the structure of the compound in the fraction on the high molecular weight side obtained by GPC fractionation is the structure of the polymer (P2).
• the "structural unit derived from the vinyl monomer" of the vinyl-based polymer (P) can be analyzed by a pyrolysis gas chromatograph / mass spectrometry (pyrolysis GC / MS).
• the "RAFT agent” used for the synthesis of the vinyl polymer (P) can be analyzed by pyrolysis GC / MS) and a matrix-assisted laser desorption / ionization method (MALDI-TOF / MS).
• the content of the polymer (P2) in the vinyl-based polymer (P) can be calculated by the method shown below.
• GPC measurement of the vinyl-based polymer (P) is performed under the conditions described in Examples described later, and a GPC chart in which the peak intensity is plotted against LogM (M is the molecular weight) is obtained.
• the peak start point is A
• the end point is B
• the peak on the high molecular weight side and the peak on the low molecular weight side appearing on the GPC chart are vertically divided (each LogM when vertically divided is X), and the peak intensity for each LogM is taken.
• the content (mol%) of the polymer (P2) in the vinyl-based polymer (P) is calculated from the following formula (6).
• Y (n) / M (n) represents the number of molecules (mol).
• the vinyl-based polymer (P) can be obtained by polymerizing a vinyl monomer by a living radical polymerization method.
• the target vinyl-based polymer (P) is obtained by charging an organic solvent and a monomer into a reactor, adding a radical polymerization initiator, and preferably heating and copolymerizing.
• the method of charging each raw material may be a batch-type initial batch charging in which all the raw materials are collectively charged, or a semi-continuous charging in which at least a part of the raw materials is continuously supplied into the reactor, and all the raw materials are continuously supplied.
• a continuous polymerization method may be used in which the product is continuously extracted from the reactor.
• the polymerization method used to obtain the vinyl-based polymer (P) the reversible addition-fragment chain transfer polymerization method (RAFT method) is particularly preferable.
• RAFT agent polymerization control agent
• free radical polymerization initiator RAFT agent
• RAFT agent a polymerization control agent
• R1 , R 2 and R 3 are synonymous with R 1 , R 2 and R 3 in the above formulas (1) and (2).
• R 1 , R 2 , and R 3 in the above equations (3) and (4) the description of R 1 , R 2 , and R 3 of the above equations (1) and (2) will be described.
• the compound (R1) and the compound (R2) include compounds having a structural formula obtained by arbitrarily combining the above-mentioned examples of R 1 , R 2 , and R 3 .
• the compound (R1) and the compound (R2) are preferably trithiocarbonate compounds in that they have a high migration constant and are excellent in the controllability of polymerization.
• a RAFT agent containing the compound (R1) as a main component and the compound (R2) as an impurity can be used as the RAFT agent.
• the content of the compound (R2) in the RAFT agent is the same as that of the compound (R1) from the viewpoint of obtaining a vinyl-based polymer having excellent heat resistance. It is preferably 10 mol% or less with respect to the total amount (100 mol%) with the compound (R2).
• the content of the compound (R2) is more preferably 9.5 mol% or less, and more preferably 9.2 mol% or less, based on the total amount of the compound (R1) and the compound (R2). It is even more preferably 9.0 mol% or less, still more preferably 8.5 mol% or less, and particularly preferably 8.5 mol% or less.
• the lower limit of the content of the compound (R2) in the RAFT agent is not particularly limited, but from the viewpoint of the availability of the RAFT agent, for example, 0.01 mol with respect to the total amount of the compound (R1) and the compound (R2). % Or more, preferably 0.05 mol% or more, and more preferably 0.1 mol% or more.
• the content of the compound (R2) in the RAFT agent can be adjusted, for example, by subjecting a mixture of the compound (R1) and the compound (R2) to a purification treatment.
• the purification method is not particularly limited, and examples thereof include recrystallization, reprecipitation, extraction, sublimation, chromatography, and column adsorption.
• the content of the compound (R2) in the RAFT agent can be adjusted by appropriately selecting the number of purifications and the purification method. From the viewpoint of obtaining a vinyl-based polymer having excellent heat resistance under higher temperature conditions (for example, conditions higher than 150 ° C.), the number of purifications for purifying the mixture of the compound (R1) and the compound (R2) is multiple. It is preferable to set the number of times. When the purification is performed a plurality of times, the purification method for each purification method may be the same or different.
• the compound (R2) contained in the RAFT agent can be identified and the content can be calculated by 1 H-NMR measurement. That is, since 1 H-NMR measurement can observe only the proton peaks derived from R 1 , R 2 and R 3 in the above equations (3) and (4), these proton peaks can be used.
• the structure of the RAFT agent and compound (R2) can be determined.
• the content of the compound ( R2 ) in the RAFT agent is the proton peak ( b) derived from R1 and R3 when the integral value of the proton peak (a) derived from R2 is normalized to 1. It can be calculated from the integral value of. Specifically, when the RAFT agent contains the compound (R2) as an impurity , the protons derived from R1 and R3 with respect to the integrated value of the proton peak (a) derived from R2 in the above formula (4). The integral value of the peak (b) is observed at 0.5 times that of the compound (R1).
• radical polymerization initiator used for the polymerization by the RAFT method known radical polymerization initiators such as azo compounds, organic peroxides and persulfates can be used.
• azo compounds are preferable because they are easy to handle for safety and side reactions during radical polymerization are unlikely to occur.
• the azo compound examples include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (4-methoxy-2, 4-Dimethylvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1- Carbonitrile), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (N-butyl-2-methylpropionamide) and the like.
• the radical polymerization initiator only one type may be used, or two or more types may be used in combination.
• the amount of the radical polymerization initiator used is not particularly limited, but is preferably 0.5 mol or less, preferably 0.2 mol or less, with respect to 1 mol of the RAFT agent, from the viewpoint of obtaining a polymer having a smaller molecular weight distribution. Is more preferable. Further, from the viewpoint of stably performing the polymerization reaction, the lower limit of the amount of the radical polymerization initiator used is preferably 0.01 mol or more, more preferably 0.05 mol or more with respect to 1 mol of the RAFT agent. preferable. The amount of the radical polymerization initiator used with respect to 1 mol of the RAFT agent is preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.2 mol.
• the polymerization reaction is preferably carried out in a solvent using a polymerization solvent known in living radical polymerization.
• the polymerization solvent used is preferably an organic solvent capable of dissolving the monomer, and for example, aromatic compounds such as benzene, toluene, xylene and anisole; ester compounds such as methyl acetate, propyl acetate and butyl acetate; acetone, methyl ethyl ketone and Examples thereof include ketone compounds such as cyclohexanone.
• the polymerization solvent one type may be used alone, or two or more types may be used in combination. When a hydrophilic monomer is used, alcohol, water or the like can be used as the polymerization solvent.
• the amount of the polymerization solvent used is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, based on 100 parts by mass of the total amount of the monomers used in the reaction.
• the amount of the polymerization solvent used is 100 parts by mass or less, a high polymerization rate can be obtained in a short time, which is preferable.
• the reaction temperature is preferably 40 ° C. or higher and 100 ° C. or lower, more preferably 45 ° C. or higher and 90 ° C. or lower, and further preferably 50 ° C. or higher and 80 ° C. or lower.
• the reaction temperature is 40 ° C. or higher, it is preferable that the polymerization reaction can proceed smoothly, and when the reaction temperature is 100 ° C. or lower, side reactions can be suppressed and restrictions on the initiators and solvents that can be used are relaxed. It is preferable in that it is done.
• the reaction time can be appropriately set depending on the monomer to be used and the like, but is preferably 1 hour or more and 48 hours or less, and more preferably 2 hours or more and 24 hours or less. If necessary, the polymerization reaction may be carried out in the presence of a chain transfer agent such as an alkylthiol compound having 2 to 20 carbon atoms.
• a chain transfer agent such as an alkylthiol compound having 2 to 20 carbon atoms.
• the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is preferably in the range of 2,000 to 1,000,000. ..
• Mn is 2,000 or more, it is preferable in that the desired property can be expressed in the vinyl-based polymer (P). Further, when Mn is 1,000,000 or less, it is preferable in that processability such as coatability and handleability can be sufficiently ensured.
• the Mn of the vinyl polymer (P) is more preferably 5,000 or more, still more preferably 8,000 or more, and particularly preferably 10,000 or more.
• the upper limit of Mn of the vinyl polymer (P) is more preferably 800,000 or less, further preferably 700,000 or less, still more preferably 600,000 or less, and particularly preferably 500, It is 000 or less.
• the preferable range of Mn of the vinyl-based polymer (P) can be determined by appropriately combining the above-mentioned upper limit and lower limit.
• the Mn of the vinyl polymer (P) is more preferably 5,000 to 800,000, still more preferably 8,000 to 700,000, and even more preferably 10,000 to 600,000. ..
• the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC of the vinyl-based polymer (P) is preferably in the range of 2,000 to 1,000,000.
• the Mw of the vinyl-based polymer (P) is more preferably 5,000 or more, still more preferably 8,000 or more, and particularly preferably 10,000 or more.
• the upper limit of Mw of the vinyl-based polymer (P) is more preferably 800,000 or less, further preferably 700,000 or less, still more preferably 600,000 or less, and particularly preferably 500, It is 000 or less.
• the range of Mw of the vinyl-based polymer (P) is more preferably 5,000 to 800,000, still more preferably 8,000 to 700,000, and even more preferably 10,000 to 600,000. Is.
• the molecular weight distribution (Mw / Mn) of the vinyl-based polymer (P) is preferably 3.0 or less from the viewpoint of making the heat resistance more excellent.
• the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, still more preferably 2.0 or less.
• the lower limit of the molecular weight distribution (Mw / Mn) is not particularly limited, but is, for example, 1.01 or more from the viewpoint of ease of manufacture.
• the vinyl-based polymer (P) obtained by this production method can be used in a wide range of applications. Specifically, it can be applied to various uses such as dispersants, industrial rubbers, binders, adhesives, paints, coating agents, and surfactants. In addition, examples of applicable fields include automobile parts, home appliances / OA equipment parts, medical equipment parts, packaging materials, civil engineering and construction materials, electric wires, miscellaneous goods, and the like.
• the method for measuring the molecular weight of the polymer is as follows. ⁇ Molecular weight measurement> The obtained vinyl-based polymer was subjected to gel permeation chromatography (GPC) measurement under the following conditions to obtain a number average molecular weight (Mn) and a weight average molecular weight (Mw) in terms of polystyrene. Further, the molecular weight distribution (Mw / Mn) was calculated from the obtained Mn and Mw values.
• GPC gel permeation chromatography
• the vinyl polymer is obtained.
• the impurities contained were identified. That is, if the concentrate (impurity) of the fraction on the high molecular weight side has the structure of the following polymer (1), the ratio of the integrated values of (A) / (B) / (C) is 6/2/4. In the case of the structure of the polymer (2), the ratio of (A) / (B) / (C) is 6/4/8. (In the formula, n is an integer.)
• the above polymerization solution was reprecipitated and purified from methanol and vacuum dried to obtain a vinyl polymer I.
• the molecular weights of the obtained vinyl-based polymer I were Mn68,000, Mw76,000, and Mw / Mn1.12 as measured by GPC (in terms of polystyrene).
• the ratio of the integrated values of the concentrates (A) / (B) / (C) of the polymer fraction was 6/4/8. there were. From this result, it was found that the impurity has the structure of the polymer (2). Further, when the content of the polymer (2) in the vinyl-based polymer I was calculated, it was calculated to be 5.0 mol% with respect to the total amount of the polymer (1) and the polymer (2) of 100 mol%.
• the vinyl-based polymers I and II in which the content of the polymer (2) is 10 mol% or less with respect to the total amount of the polymer (1) and the polymer (2) is 100 mol%. , 170 ° C., excellent heat resistance under high temperature conditions of 500 hours.
• the vinyl-based polymers III and IV having a polymer (2) content of more than 10 mol% were inferior in heat resistance to the vinyl-based polymers I and II.

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• 2021
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