[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2012101886A1 - Procédé de production d'un polymère carboxylé - Google Patents

Procédé de production d'un polymère carboxylé Download PDF

Info

Publication number
WO2012101886A1
WO2012101886A1 PCT/JP2011/074785 JP2011074785W WO2012101886A1 WO 2012101886 A1 WO2012101886 A1 WO 2012101886A1 JP 2011074785 W JP2011074785 W JP 2011074785W WO 2012101886 A1 WO2012101886 A1 WO 2012101886A1
Authority
WO
WIPO (PCT)
Prior art keywords
carboxyl group
meth
vinyl
producing
acrylate
Prior art date
Application number
PCT/JP2011/074785
Other languages
English (en)
Japanese (ja)
Inventor
剛史 長谷川
洋慈 堀江
佐々木　裕
Original Assignee
東亞合成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東亞合成株式会社 filed Critical 東亞合成株式会社
Priority to JP2012554622A priority Critical patent/JP5890324B2/ja
Publication of WO2012101886A1 publication Critical patent/WO2012101886A1/fr

Links

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
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP

Definitions

  • the present invention relates to a method for producing a carboxyl group-containing polymer, and more particularly to a method for producing a vinyl monomer having a carboxyl group by living radical polymerization using an atom transfer radical polymerization method.
  • Vinyl polymers produced by general radical polymerization usually have a relatively wide molecular weight distribution. Moreover, the structure of each terminal of the vinyl polymer is not uniform.
  • various living radical polymerization methods have been proposed in which vinyl polymers having a narrow molecular weight distribution are obtained and specific functional groups can be introduced at almost arbitrary positions in the polymer.
  • atom transfer radical polymerization is preferably used as a method for producing a vinyl polymer because it has a high degree of freedom in designing a polymerization initiator and a catalyst. .
  • Non-Patent Document 1 describes that the atom transfer radical polymerization method cannot be applied to polymerization of a vinyl monomer having a carboxyl group such as (meth) acrylic acid. The reason is that the transition metal atom reacts with the carboxyl group and radical polymerization does not proceed in a living manner.
  • Non-Patent Document 2 describes that a carboxyl group-containing polymer having a narrow molecular weight distribution and a controlled terminal structure can be obtained by protecting a carboxyl group and deprotecting it after polymerization.
  • Non-Patent Document 3 describes that a carboxyl group is neutralized with sodium hydroxide and polymerization is performed in water, and a polymer having a narrow molecular weight distribution is obtained.
  • Patent Document 2 discloses that a polymer having a narrow molecular weight distribution is obtained by using a transition metal (iron, cobalt, rhodium, ruthenium, etc.) other than copper.
  • Non-Patent Document 2 requires a deprotection reaction after the polymerization, and there is a problem that the polymerization process becomes complicated.
  • the method disclosed in Non-Patent Document 3 has a problem that the terminal structure that can be produced is limited because the polymerization is performed in water.
  • the method disclosed in Patent Document 2 has a problem that the transition metal used is expensive.
  • the present invention has been made in view of the above problems, and its purpose is to apply an atom transfer radical polymerization method to the polymerization of a vinyl monomer having a carboxyl group such as (meth) acrylic acid to obtain a molecular weight.
  • An object of the present invention is to provide a method for easily and inexpensively obtaining a polymer having a narrow distribution and an arbitrary terminal.
  • the present inventors have found that in a method for producing a vinyl monomer having a carboxyl group by living radical polymerization by an atom transfer radical polymerization method, a vinyl monomer having a carboxyl group is produced. It was found that a polymer having a narrow molecular weight distribution can be obtained inexpensively and easily by neutralizing the polymer with a basic substance and then polymerizing, thereby completing the present invention.
  • the present invention is as follows. 1.
  • a method for producing a vinyl monomer having a carboxyl group by living radical polymerization by an atom transfer radical polymerization method the vinyl monomer having a carboxyl group is neutralized with a basic substance and then polymerized in an organic solvent.
  • a process for producing a carboxyl group-containing polymer 2.
  • the method for producing a carboxyl group-containing polymer according to 1 above, wherein the equivalent ratio of the carboxyl group in the vinyl monomer to the basic substance to be neutralized is 1: 0.3-3. . 3.
  • 3. The method for producing a carboxyl group-containing polymer as described in 1 or 2 above, wherein the basic substance is an organic amine. 4). 4.
  • 10. 10 The vinyl polymer as described in 9 above, wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is less than 1.8. .
  • the method for producing a carboxyl group-containing polymer according to the present invention comprises neutralizing a vinyl monomer having a carboxyl group with a basic substance, and then living radical polymerization by an atom transfer radical polymerization method in an organic solvent. I do. Therefore, since the living radical polymerization proceeds without the transition metal complex as a catalyst reacting with the carboxyl group, a vinyl polymer having a narrow molecular weight distribution can be obtained. Moreover, according to the production method of the present invention, a polymer having an arbitrary terminal can be produced inexpensively and easily. Furthermore, a basic substance can be easily removed by including the process of processing a polymerization liquid using a cation exchange resin.
  • the method for producing a carboxyl group-containing polymer according to the present invention is based on an atom transfer radical polymerization method in an organic solvent after neutralizing a vinyl monomer having a carboxyl group with a basic substance. Living radical polymerization is performed.
  • This atom transfer radical polymerization method is living radical polymerization using an organic halide or a sulfonyl halide compound as a polymerization initiator and a transition metal complex as a catalyst.
  • the polymerization initiator used in the atom transfer radical polymerization method is an organic halide or a sulfonyl halide compound.
  • organic halide various organic compounds having one or more carbon-halogen bonds in the molecule (where halogen is other than fluorine) can be used, including aliphatic hydrocarbon-based halogen compounds and alicyclic hydrocarbon-based compounds. Examples include halogen compounds, aromatic hydrocarbon halogen compounds, and heterocyclic halogen compounds.
  • aliphatic hydrocarbon halogen compound examples include methyl 2-bromopropionate, ethyl 2-bromopropionate, butyl 2-bromopropionate, methyl 2-bromoisobutyrate, ethyl 2-bromoisobutyrate, and 2-bromoisobutyric acid.
  • butyl methyl 2-bromoisobutyrate, ethyl 2-bromoisobutyrate, butyl 2-bromoisobutyrate, dimethyl 2,3-dibromosuccinate, diethyl 2,3-dibromosuccinate, dibutyl 2,3-dibromosuccinate, Dimethyl 2,4-dibromoglutarate, diethyl 2,4-dibromoglutarate, dibutyl 2,4-dibromoglutarate, dimethyl 2,5-dibromoadipate, diethyl 2,5-dibromoadipate, 2,5-dibromo Dibutyl adipate, dimethyl 2,6-dibromopimelate, 2, - Jiburomopimerin diethyl, 2,6 Jiburomopimerin dibutyl, 2,7-dibromo-slip phosphate dimethyl, 2,7-dibromo-slip phosphate diethyl, such as 2,7-dibromo-
  • aromatic hydrocarbon halogen compound examples include bis (bromomethyl) benzene, bis (1-bromoethyl) benzene, bis (1-bromoisopropyl) benzene, tris (bromomethyl) benzene, tris (1-bromoethyl) benzene, And tris (1-bromoisopropyl) benzene.
  • halogenated sulfonyl compound examples include: R 1 —C 6 H 4 —SO 2 X X—SO 2 —C 6 H 4 —SO 2 —X C 6 H 3 — (SO 2 —X) 3 And the like.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • X represents chlorine, bromine or iodine.
  • the amount of the polymerization initiator used with respect to the monomer is selected according to the molecular weight of the target polymer as in the case of living anion polymerization.
  • the following calculation formula can be used. That is, the number average molecular weight in the polymerization process is represented by the following formula.
  • the transition metal complex used as a catalyst for the atom transfer radical polymerization method is a complex of a metal element selected from Groups 8 to 11 of the periodic table.
  • the transition metal complex consists of a transition metal and a ligand.
  • Specific examples of the transition metal are copper, nickel, ruthenium or iron.
  • a copper complex is preferable from the viewpoint of reaction control and cost.
  • Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, and cuprous perchlorate. Of these, cuprous chloride and cuprous bromide are preferred from the viewpoint of polymerization control.
  • the ligand that forms a complex with the transition metal is preferably a bidentate or more nitrogen ligand.
  • the amount of the polymerization initiator and the catalyst may be determined from the type of monomer used and the relationship between the amount of solvent and the required reaction rate. In general, the amount is 0.1 to 1.5 moles of catalyst per mole of polymerization initiator, and more preferably 0.5 to 1.0 mole of catalyst per mole of polymerization initiator.
  • vinyl monomer having a carboxyl group in the molecule used in the present invention examples include unsaturated monobases such as acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, and acryloxypropionic acid.
  • unsaturated monobases such as acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, and acryloxypropionic acid.
  • Unsaturated dibasic acids such as acid, maleic acid, itaconic acid, fumaric acid, mesaconic acid, citraconic acid, and cyclohexanedicarboxylic acid
  • unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride Thing etc. are mentioned. These may be used alone or in combination of two or more.
  • (meth) acrylic acid is preferable because it is inexpensive and easily causes a copolymerization reaction with other various monomers.
  • other copolymer monomers may be used in combination.
  • the combined proportion is not particularly limited, but in the present invention, the proportion of the carboxyl group-containing vinyl monomer in the charged monomer is preferably 70% by mass or more. It has been difficult in the prior art to obtain a polymer containing 70% by mass or more of a carboxyl group-containing vinyl monomer unit by living radical polymerization with a narrow molecular weight distribution.
  • the carboxyl group-containing vinyl monomer according to the present invention and the other copolymerizable monomer are not particularly limited as long as they are unsaturated compounds having radical polymerizability.
  • This unsaturated compound includes alkyl (meth) acrylate, vinyl monomer having cyano group, vinyl monomer having hydroxyl group, aromatic vinyl monomer, vinyl monomer having amino group, amide group Vinyl monomers having an alkoxyl group, vinyl monomers having an alkoxyl group, conjugated diene monomers, maleimide monomers, vinyl ester monomers, vinyl ether monomers, vinyl monomers having a glycidyl group, Examples thereof include monoalkyl esters of saturated dicarboxylic acids, dialkyl esters of unsaturated dicarboxylic acids, and monomers having silicon-containing groups. These can be used alone or in combination of two or more.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, (meth ) 2-methylpentyl acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth)
  • vinyl monomer having a cyano group examples include acrylonitrile, methacrylonitrile, ⁇ -ethylacrylonitrile, ⁇ -isopropylacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -fluoroacrylonitrile and the like. These may be used alone or in combination of two or more.
  • Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, Mono (meth) acrylic acid ester of polyalkylene glycol such as polyethylene glycol and polypropylene glycol, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropyl Bae alkenyl phenol, and the like. These can be used alone or in combination of two or more.
  • Aromatic vinyl monomers include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butyl Styrene, tert-butoxystyrene, vinyltoluene, divinyltoluene, benzyl (meth) acrylate, vinylnaphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, styrenesulfonic acid and salts thereof, ⁇ -Methyl styrene sulfonic acid and its salts. These can be used alone or in combination of two or more.
  • vinyl monomers having an amino group examples include aminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, (meth) 2-diethylaminoethyl acrylate, 2- (di-n-propylamino) ethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, (meth) acrylic acid 2- (di-n-propylamino) propyl, (meth) acrylic acid 3-dimethylaminopropyl, (meth) acrylic acid 3-diethylaminopropyl, (meth) acrylic acid 3- (di-n-propylamino) propyl, etc. Is mentioned. These can be used alone or in combination of two or more.
  • vinyl monomers having an amide group examples include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N- Examples include butoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, and N-alkoxymethyl (meth) acrylamide. These can be used alone or in combination of two or more.
  • vinyl monomers having an alkoxyl group examples include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate, and (meth) acrylic acid.
  • Conjugated diene monomers include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, chloroprene (2-chloro-1,3-butadiene) ) And the like. These can be used alone or in combination of two or more.
  • maleimide monomer examples include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4 -Methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4- Hydroxyphenyl) maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. These can be used alone or in combination of two or more.
  • vinyl ester monomer examples include methylene aliphatic monocarboxylic acid ester, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl butyrate, vinyl benzoate, vinyl formate, vinyl cinnamate, vinyl versatate, and the like. These can be used alone or in combination of two or more.
  • vinyl ether monomer examples include vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl phenyl ether, vinyl cyclohexyl ether and the like. These can be used alone or in combination of two or more.
  • vinyl monomers having a glycidyl group examples include glycidyl (meth) acrylate, (meth) allyl glycidyl tethel, ⁇ -methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl, 3,4- Examples thereof include epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.
  • Examples of monoalkyl esters of unsaturated dicarboxylic acids include monoalkyl esters such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. . These can be used alone or in combination of two or more.
  • Examples of the dialkyl ester of unsaturated dicarboxylic acid include dialkyl esters such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. These can be used alone or in combination of two or more.
  • Monomers having silicon-containing groups include vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane.
  • Vinyltris (2-hydroxymethoxyethoxy) silane vinyltriacetoxysilane, vinyldiethoxysilanol, vinylethoxysiladiol, vinylmethyldiethoxysilane, vinyldimethoxyethoxysilane, vinylmethyldiacetoxysilane, allyltrimethoxysilane, allyl Triethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltris (2-methoxyethoxy) silane Down, 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl dimethyl ethoxysilane, 3-acryloxy propyl dimethoxysilane, and 2-acrylamide-ethyl triethoxysilane and the like. These can be used alone or in combination of two or more.
  • alkyl (meth) acrylate a monomer having a hydroxyl group and an aromatic vinyl monomer are preferable, and an acrylate ester is more preferable.
  • a carboxyl group-containing polymer can be produced at a low cost.
  • the above-mentioned unsaturated compound having radical polymerizability is added and the polymerization is continued to synthesize a block copolymer. it can. At that time, it is also possible to polymerize an unsaturated compound having radical polymerizability first, add a vinyl monomer having a carboxyl group, and perform block polymerization.
  • Basic substance examples of basic substances that neutralize the carboxyl groups of vinyl monomers include amine compounds such as ammonia, ammonium hydroxide, hydrazine, hydrazine hydrate, and various organic amines; Metal oxides such as sodium oxide, potassium oxide, potassium peroxide, calcium oxide, strontium oxide and barium oxide; metal hydroxides such as barium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and strontium hydroxide; Metal hydrides such as sodium hydride, potassium hydride, calcium hydride; carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate; acetic acid such as sodium acetate, potassium acetate, calcium acetate Examples include salt. Among these, an organic amine is preferable from the viewpoint of easy removal after living radical polymerization.
  • organic amines examples include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, 2-ethylhexylamine, 3- (2-ethylhexyloxy) propylamine, 3-methoxypropylamine, and 3-ethoxypropylamine.
  • Aliphatic secondary amines such as aliphatic primary amines, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-2-ethylhexylamine, di-n-octylamine, trimethylamine
  • Aliphatic amines such as aliphatic tertiary amines such as triethylamine, tripropylamine, triisopropylamine, tributylamine, tetramethylethylenediamine, tri-n-octylamine
  • N, N, N ′, N′-tetra Aliphatic polyamines such as tilethylenediamine, N, N, N ′, N ′′, N ′′ -pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine; aniline, toluidine, Aromatic primary amines such as m-to
  • the equivalent ratio (a: b) of the carboxyl group (a) in the vinyl monomer to the basic substance (b) to be neutralized is preferably 1: 0.3-3, and 1: 0. More preferably, it is 5 to 2, and further preferably 1: 0.7 to 1.5.
  • the equivalent ratio of the basic substance (b) is less than 0.3, the polymerization may not proceed.
  • the equivalent ratio of the basic substance (b) exceeds 3, the molecular weight distribution may not be sufficiently controlled.
  • the basic substance used for neutralization may cause the polymer to be colored and deteriorated after a long time, it is preferably removed after the living radical polymerization is completed.
  • the removal method is not particularly limited, it is preferable to remove using a cation exchange resin because the process is simple.
  • the exchange group of the cation exchange resin include a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, and a phenol group.
  • Such cation exchange resins are commercially available, for example, trade name “Diaion” manufactured by Mitsubishi Chemical Corporation, trade name “Amberlite” manufactured by Dow Chemical Company, and the like.
  • the amount of ion exchange resin is preferably 20 g or more per 1 g of polymer soot in the batch method.
  • the living radical polymerization in the present invention is performed in an organic solvent.
  • organic solvents include dioxane, dimethylformamide, dimethyl sulfoxide, methanol, ethanol or 2-propanol. Among these, from the viewpoint of solubility, dioxane, dimethylformamide and dimethylsulfoxide are preferable, and dimethylformamide is more preferable.
  • the mixing ratio of dimethylformamide is preferably 50% by mass or more.
  • the polymerization temperature is preferably 50 to 130 ° C, more preferably 80 to 100 ° C.
  • the polymerization temperature is less than 50 ° C.
  • the polymerization rate becomes very slow, and the polymerization may hardly proceed.
  • the polymerization temperature exceeds 130 ° C., the growth radicals may stop with each other as the radical concentration increases, making it difficult to control the polymerization.
  • the number average molecular weight of the vinyl polymer obtained by the production method according to the present invention is 500 to 100,000 in terms of polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”). Is preferred. If the number average molecular weight is less than 500, the original performance of the vinyl polymer may not be expressed. On the other hand, when the number average molecular weight exceeds 100,000, polymerization control may be difficult.
  • GPC gel permeation chromatography
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC is preferably less than 1.8, and more preferably less than 1.6.
  • the polymerization rate and average molecular weight were evaluated as follows. Evaluation method (1) Polymerization rate The polymerization solution was sampled, 1 H NMR measurement was performed, and the integral ratio of the monomer and the polymer was obtained. Measurement solvent: heavy dimethyl sulfoxide (2) weight average molecular weight (Mw) and number average molecular weight (Mn) Using a gel permeation chromatograph (model name “waters2695”, manufactured by Waters), Mw and Mn were measured under the following conditions and converted to standard polystyrene. ⁇ Measurement conditions> Column: TSKgel Super HZM-N 2 (Tosoh Corporation) Column temperature: 40 ° C Eluent: Tetrahydrofuran Flow rate: 0.5 ml / min Detector: RI
  • Example 1 A 100 ml glass reaction vessel was charged with 46 mg of copper chloride (divalent), 400 mg of tris (2- (dimethylamino) ethyl) amine, and 3.5 g of dimethylformamide. After stirring at room temperature for 10 minutes, 5 g of acrylic acid and 7 g of triethylamine (equivalent ratio 1: 1) was added, and deoxygenation was performed by bubbling with nitrogen for 30 minutes. Next, 77 mg of butyl 2-bromoisobutyrate and 1.4 g of tin 2-ethylhexanoate were added as polymerization initiators, and polymerization was carried out at 90 ° C.
  • the polymerization solution was sampled and evaluated. After the start of polymerization, 17.5 g of the polymerization solution 5 hours later was stirred with 150 g of a cation exchange resin (trade name “Amberlite IR120B” manufactured by Organo Corporation) to remove the amine. Next, this polymerization solution was filtered and dissolved, to obtain 2.3 g of a carboxyl group-containing polymer. The polymerization results are shown in Table 1.
  • Example 11 A 100 ml glass reaction vessel was charged with 46 mg of copper chloride (divalent), 400 mg of tris (2- (dimethylamino) ethyl) amine, and 3.5 g of dimethylformamide. After stirring at room temperature for 10 minutes, 6 g of methacrylic acid and 7 g of triethylamine was added, and deoxygenation was performed by bubbling with nitrogen for 30 minutes. Next, 77 mg of butyl 2-bromoisobutyrate and 1.4 g of tin 2-ethylhexanoate were added as polymerization initiators, and polymerization was carried out at 90 ° C. The polymerization results are shown in Table 3.
  • Example 12 A 100 ml glass reaction vessel was charged with 46 mg of copper chloride (divalent), 400 mg of tris (2- (dimethylamino) ethyl) amine, and 3.5 g of dimethylformamide. After stirring at room temperature for 10 minutes, 5 g of acrylic acid and 7 g of triethylamine was added, and deoxygenation was performed by bubbling with nitrogen for 30 minutes. Next, 77 mg of butyl 2-bromoisobutyrate and 1.4 g of tin 2-ethylhexanoate were added as polymerization initiators, and polymerization was carried out at 90 ° C.
  • the production method according to the present invention can produce a carboxyl group-containing polymer directly without deprotection after polymerization.
  • the obtained polymer has a narrow molecular weight distribution and is useful as a water-soluble polymer or amphiphilic copolymer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)

Abstract

Cette invention concerne un procédé de production de polymères carboxylés qui comprend l'application d'un procédé de polymérisation radicalaire par transfert d'atomes à la polymérisation d'un monomère de vinyle contenant un groupe carboxy, par ex., acide (méth)acrylique, pour obtenir à bon marché et facilement un polymère ayant une distribution étroite des poids moléculaires et qui présente toute terminaison souhaitée. Le procédé de production selon l'invention qui consiste à polymériser un monomère de vinyle contenant un groupe carboxy par polymérisation radicalaire vivante par un procédé de polymérisation radicalaire par transfert d'atomes, est caractérisé par la neutralisation dudit monomère de vinyle contenant un groupe carboxy avec une substance basique, puis la polymérisation du monomère obtenu dans un solvant organique.
PCT/JP2011/074785 2011-01-27 2011-10-27 Procédé de production d'un polymère carboxylé WO2012101886A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012554622A JP5890324B2 (ja) 2011-01-27 2011-10-27 カルボキシル基含有重合体の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011015040 2011-01-27
JP2011-015040 2011-01-27

Publications (1)

Publication Number Publication Date
WO2012101886A1 true WO2012101886A1 (fr) 2012-08-02

Family

ID=46580472

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/074785 WO2012101886A1 (fr) 2011-01-27 2011-10-27 Procédé de production d'un polymère carboxylé

Country Status (2)

Country Link
JP (1) JP5890324B2 (fr)
WO (1) WO2012101886A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014136950A1 (fr) * 2013-03-08 2014-09-12 横浜ゴム株式会社 Procédé de fabrication d'un polymère d'éther vinylique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001131221A (ja) * 1999-11-09 2001-05-15 Kao Corp イオン性高分子化合物の製法
JP2002509948A (ja) * 1998-03-30 2002-04-02 カーネギー・メロン・ユニヴァーシティー 水を媒体とする重合系への原子転移ラジカル重合の応用
JP2002540234A (ja) * 1999-03-23 2002-11-26 カーネギー−メロン ユニバーシティ フリーラジカル的に（共）重合可能なモノマーの制御された重合のための触媒法、およびそれによって製造される官能性高分子系
JP2007112932A (ja) * 2005-10-21 2007-05-10 Toyo Ink Mfg Co Ltd ブロック樹脂
JP2009529601A (ja) * 2006-03-10 2009-08-20 ワーウィック イフェクト ポリマーズ リミテッド ポリマー

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4850988B2 (ja) * 1998-06-01 2012-01-11 株式会社カネカ 重合方法
JP3100589B1 (ja) * 1999-05-20 2000-10-16 伯東株式会社 紙パルプ製造工程におけるシュウ酸カルシウムスケール抑制剤およびその抑制方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002509948A (ja) * 1998-03-30 2002-04-02 カーネギー・メロン・ユニヴァーシティー 水を媒体とする重合系への原子転移ラジカル重合の応用
JP2002540234A (ja) * 1999-03-23 2002-11-26 カーネギー−メロン ユニバーシティ フリーラジカル的に（共）重合可能なモノマーの制御された重合のための触媒法、およびそれによって製造される官能性高分子系
JP2001131221A (ja) * 1999-11-09 2001-05-15 Kao Corp イオン性高分子化合物の製法
JP2007112932A (ja) * 2005-10-21 2007-05-10 Toyo Ink Mfg Co Ltd ブロック樹脂
JP2009529601A (ja) * 2006-03-10 2009-08-20 ワーウィック イフェクト ポリマーズ リミテッド ポリマー

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DANG JING ET AL.: "Atom Transfer Radical polymerization of acrylic acid", ADHESION IN CHINA, January 2008 (2008-01-01), pages 29 - 31 *
E. J. ASHFORD ET AL.: "First example of the atom transfer radical polymerisation of an acidic monomer: direct synthesis of methacrylic acid copolymers in aqueous media", CHEMICAL COMMUNICATIONS, no. 14, 21 July 1999 (1999-07-21), pages 1285 - 1286 *
X.-S. WANG ET AL.: "Facile synthesis of acidic copolymers via atom transfer radical polymerization in aqueous media at ambient temperature", MACROMOLECULES, vol. 33, no. 2, 25 January 2000 (2000-01-25), pages 255 - 257 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014136950A1 (fr) * 2013-03-08 2014-09-12 横浜ゴム株式会社 Procédé de fabrication d'un polymère d'éther vinylique
US9376515B2 (en) 2013-03-08 2016-06-28 The Yokohama Rubber Co., Ltd. Production method for vinyl ether polymer

Also Published As

Publication number Publication date
JP5890324B2 (ja) 2016-03-22
JPWO2012101886A1 (ja) 2014-06-30

Similar Documents

Publication Publication Date Title
TWI291472B (en) Catalytic processes for the controlled polymerization of free radically (co)polymerizable monomers and functional polymeric systems prepared thereby
US5728747A (en) Stable free radical polymerization processes and compositions thereof
JPH10508885A (ja) ポリマー合成
JP5252492B2 (ja) ブロック共重合体の製造法
JP7131007B2 (ja) 重合体組成物
JP5890324B2 (ja) カルボキシル基含有重合体の製造方法
WO2017166914A1 (fr) Initiateur d'atrp à trois bras présentant une structure conjuguée plate et procédé pour sa préparation
JPWO2010109928A1 (ja) ビニルエーテル系星型ポリマーおよびその製造方法
JP5189746B2 (ja) スチレン系重合体の製造方法
JP5090792B2 (ja) 重合体の製造方法
JP2005194487A (ja) 顔料分散用樹脂及びそれを含有する塗料組成物
JP2009067840A (ja) ポリマーの製造方法
WO2018199268A1 (fr) Composition adhésive à base de 2-cyanoacrylate
JP2011208047A (ja) 重合体の製造方法
JP2019189731A (ja) 顔料分散樹脂、顔料分散体および塗料組成物
WO2021095739A1 (fr) Procédé de fabrication de microparticules de polymère, et agent stabilisant de dispersion
JP2009256290A (ja) 単量体及びその重合体、制御ラジカル用触媒及びそれを用いた制御ラジカル重合方法
JP5495736B2 (ja) 改良された重合方法
JP2010254850A (ja) （メタ）アクリル系ブロック共重合体の製造方法
JP2009221447A (ja) アクリル系重合体の製造方法
JP2005281688A (ja) アニオン重合体の製造方法
JP7395262B2 (ja) 硬化性組成物および（メタ）アクリル系重合体
JP5564047B2 (ja) 高分子量共重合体
JP7484116B2 (ja) 重合体の製造方法
JP2006176587A (ja) 連鎖移動剤およびそれを用いた重合方法

Legal Events

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

Ref document number: 11857269

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2012554622

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11857269

Country of ref document: EP

Kind code of ref document: A1