WO2010113568A1 - Stabilisateur de dispersion pour polymérisation en suspension - Google Patents

Stabilisateur de dispersion pour polymérisation en suspension Download PDF

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WO2010113568A1
WO2010113568A1 PCT/JP2010/052787 JP2010052787W WO2010113568A1 WO 2010113568 A1 WO2010113568 A1 WO 2010113568A1 JP 2010052787 W JP2010052787 W JP 2010052787W WO 2010113568 A1 WO2010113568 A1 WO 2010113568A1
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polymerization
vinyl
poa
mol
group
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PCT/JP2010/052787
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Japanese (ja)
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悠太 田岡
真輔 新居
昌人 仲前
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株式会社クラレ
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Priority to JP2011507058A priority Critical patent/JP5632830B2/ja
Publication of WO2010113568A1 publication Critical patent/WO2010113568A1/fr

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    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the present invention relates to a dispersion stabilizer for suspension polymerization.
  • it relates to a dispersion stabilizer for suspension polymerization of vinyl compounds.
  • Dispersion stabilizers for suspension polymerization of vinyl compounds include [1] high plasticizer absorbability even when used in small amounts, and easy processing, [2] removal of monomer components such as residual vinyl compounds. There are demands for performance that are easy, [3] few coarse particles, and [4] particles that are as uniform in particle size as possible and that can prevent scale adhesion.
  • Patent Documents 1 to 7 a method of using a dispersion stabilizing aid in combination has been proposed.
  • a method has been proposed in which a vinyl alcohol resin having a low polymerization degree, a low saponification degree, and an oxyalkylene group is used as a dispersion stabilizing aid in a dispersion stabilizer for suspension polymerization of vinyl compounds.
  • the present invention provides a dispersion stabilizer for suspension polymerization that satisfies the above-mentioned required performances [1] to [4] and is excellent in polymerization stability when suspension polymerization of vinyl compounds such as vinyl chloride is carried out.
  • the purpose is to do.
  • a dispersion stabilizer for suspension polymerization containing 0.1 to 10 mol% of a polyoxyalkylene-modified vinyl alcohol polymer (B) solves the above-mentioned problems. It came to be completed.
  • R1 represents a hydrogen atom or a methyl group
  • R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • m and n represent the number of repeating units of each oxyalkylene unit, and 1 ⁇ m ⁇ 10 and 3 ⁇ n ⁇ 20.
  • unit 1 a unit represented by the number m of repeating units
  • unit 2 a unit represented by the number of repeating units n is referred to as unit 2.
  • the arrangement of the unit 1 and the unit 2 may be random or block.
  • the weight ratio (A) / (B) of the vinyl alcohol polymer (A) to the polyoxyalkylene-modified vinyl alcohol polymer (B) is 99/1 to 5/95.
  • the saponification degree of the vinyl alcohol polymer (A) (hereinafter, the vinyl alcohol polymer may be abbreviated as PVA) used in the present invention is 60 mol% or more, preferably 65 to 95 mol%. More preferably, it is 70 to 90 mol%.
  • the degree of saponification is less than 60 mol%, the water solubility of PVA is lowered and the handleability is deteriorated.
  • the saponification degree of PVA is a value that can be measured according to JIS-K6726.
  • the viscosity average polymerization degree of PVA (A) is 200 or more, preferably 500 or more, more preferably 550 to 8000, and further preferably 600 to 3500.
  • the viscosity average polymerization degree of the PVA polymer is less than 200, the polymerization stability when the vinyl compound is subjected to suspension polymerization is lowered.
  • the viscosity average degree of polymerization may be simply referred to as the degree of polymerization.
  • PVA (A) may be used alone, or two or more types having different characteristics may be used in combination.
  • polyoxyalkylene-modified vinyl alcohol copolymer (B) used in the present invention (hereinafter, the polyoxyalkylene-modified vinyl alcohol copolymer may be abbreviated as POA-modified PVA) is represented by the above general formula (I). Is contained in the side chain.
  • POA-modified PVA (B) needs to have a polyoxyalkylene (POA) group modification amount of 0.1 to 10 mol%.
  • POA group modification amount exceeds 10 mol%, the proportion of hydrophobic groups contained in one molecule of POA modified PVA (B) increases, and the water solubility of the PVA may decrease.
  • the POA group modification amount is preferably 5 mol% or less, and particularly preferably 2 mol% or less.
  • the POA group modification amount is less than 0.1 mol%, the water solubility of the POA modified PVA (B) is excellent, but the number of POA groups contained in the PVA is small, and the physical properties based on the POA modification are low. It may not develop.
  • the POA group modification amount is represented by the mole fraction of the POA group with respect to the main chain methylene group of PVA.
  • the POA group modification amount of the POA-modified PVA (A) is, for example, a POA-modified polyvinyl ester that is a precursor of the PVA.
  • a POA-modified polyvinyl acetate hereinafter, polyvinyl acetate is abbreviated as PVAc). In some cases).
  • PVAc polyvinyl acetate
  • POA group modification amount (mol%) ⁇ (number of protons of ⁇ / 3n) / (number of protons of ⁇ + (number of protons of ⁇ / 3n)) ⁇ ⁇ 100 n represents the number of repeating units of unit 2.
  • POA-modified PVA (B) has a polymerization degree of 200 to 1,000. When the degree of polymerization exceeds 1000, it is difficult to remove the monomer component from the vinyl polymer particles obtained by suspension polymerization of the vinyl compound, or the plasticizer absorbability is lowered, which is not preferable. When the degree of polymerization is less than 200, the physical properties of PVA as a polymer are not expressed, which is not preferable.
  • the degree of polymerization of POA-modified PVA (B) is measured by the same method as the method for measuring the degree of polymerization of PVA (A) described above.
  • the saponification degree of the POA-modified PVA (B) is less than 60 mol% from the viewpoint of water solubility and water dispersibility, preferably 58 mol% or less, more preferably 55 mol% or less, and even more preferably 52 mol% or less. is there. Although there is no restriction
  • the saponification degree of POA-modified PVA (B) is a value that can be measured according to JIS-K6726.
  • the number m of repeating units of the unit 1 of the POA group represented by the general formula (I) needs to satisfy 1 ⁇ m ⁇ 10.
  • m is preferably 1.5 or more.
  • m is preferably 5 or less, and more preferably 3 or less.
  • the number of repeating units n of unit 2 (polyoxybutylene) needs to satisfy 3 ⁇ n ⁇ 20.
  • n is preferably 5 or more, and particularly preferably 8 or more.
  • n exceeds 20, the hydrophobicity of the POA group increases, and the water solubility of the POA-modified PVA (B) may decrease.
  • n is preferably 18 or less, and more preferably 15 or less.
  • POA-modified PVA (B) can be produced by copolymerizing an unsaturated monomer having a POA group represented by the general formula (I) and a vinyl ester monomer in an alcohol solvent or without.
  • a method of saponifying the obtained POA-modified vinyl ester copolymer with a solvent is preferred.
  • the temperature employed when copolymerizing the unsaturated monomer having a POA group and the vinyl ester monomer is preferably 0 to 200 ° C, more preferably 30 to 140 ° C.
  • a copolymerization temperature lower than 0 ° C. is not preferable because a sufficient polymerization rate cannot be obtained.
  • the polymerization method used for copolymerizing an unsaturated monomer having a POA group and a vinyl ester monomer may be any of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization.
  • the polymerization method any known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method can be used.
  • a bulk polymerization method or a solution polymerization method in which polymerization is performed without a solvent or an alcohol solvent is suitably employed, and an emulsion polymerization method is employed for the purpose of producing a copolymer having a high degree of polymerization.
  • the alcohol solvent methyl alcohol, ethyl alcohol, propyl alcohol, and the like can be used, but are not limited thereto. These solvents can be used in combination of two or more.
  • azo initiators As the initiator used for copolymerization, conventionally known azo initiators, peroxide initiators, redox initiators and the like are appropriately selected according to the polymerization method.
  • the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethyl valeronitrile), etc.
  • peroxide initiators include perisopropyl compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl Perester compounds such as peroxyneodecanate, ⁇ -cumylperoxyneodecanate, t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpent
  • the initiator can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator.
  • the redox initiator include a combination of the above-described peroxide and a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.
  • an antioxidant such as tartaric acid may be added to the polymerization system in an amount of 1 to 100 ppm (based on the vinyl ester monomer).
  • vinyl ester monomers vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, Examples include vinyl stearate, vinyl oleate, and vinyl benzoate. Among them, vinyl acetate is most preferable.
  • the unsaturated monomer having a POA group and the vinyl ester monomer are copolymerized
  • other monomers may be copolymerized within a range not impairing the gist of the present invention.
  • monomers that can be used include ⁇ -olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, and I-propyl acrylate.
  • Acrylates such as n-butyl acrylate, I-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and its salts; methyl methacrylate, methacryl Methacrylic acid such as ethyl acetate, n-propyl methacrylate, I-propyl methacrylate, n-butyl methacrylate, I-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate Beauty treatment Acrylamide; N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and its salt, acrylamidopropyl
  • the PVA (A) and POA-modified PVA (B) used in the present invention may have an ionic functional group at the terminal.
  • these ionic functional groups include a carboxyl group and a sulfonic acid group, and among them, a carboxyl group is preferable.
  • These ionic groups include salts thereof, and alkali metal salts are preferred from the viewpoint that PVA (A) and POA-modified PVA (B) are preferably water-dispersible.
  • a thiol compound such as thiol acetic acid, mercaptopropionic acid, 3-mercapto-1-propanesulfonic acid sodium salt
  • a method of polymerizing a vinyl ester monomer such as vinyl acetate and saponifying the resulting polymer can be used.
  • Copolymerization may be carried out in the presence of a chain transfer agent.
  • chain transfer agents include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; and halogenated hydrocarbons such as trichloroethylene and perchloroethylene. Of these, aldehydes and ketones are preferably used.
  • the addition amount of the chain transfer agent is determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target vinyl ester polymer, but is generally 0.1% relative to the vinyl ester monomer. ⁇ 10% by weight is desirable.
  • Examples of the solvent that can be used in this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene; These can be used alone or in combination of two or more. Among them, it is convenient and preferable to perform the saponification reaction using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst.
  • Examples of the unsaturated monomer having a POA group represented by the general formula (I) include unsaturated monomers represented by the following general formula (II).
  • R1 is a hydrogen atom or a methyl group
  • R2 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R3 is a hydrogen atom or —COOM.
  • M represents a hydrogen atom, an alkali metal or an ammonium group.
  • R4 is a hydrogen atom, a methyl group or —CH 2 —COOM, where M is as defined above.
  • X is —O—, —CH 2 —O—, —CO—, —CO—O— or —CO—NR 5 —.
  • R5 represents a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms.
  • m and n represent the number of repeating units of each oxyalkylene unit, and 1 ⁇ m ⁇ 10 and 3 ⁇ n ⁇ 20.
  • R2 of the unsaturated monomer represented by the general formula (II) a hydrogen atom, a methyl group or a butyl group is preferable, and a hydrogen atom or a methyl group is more preferable. Furthermore, it is particularly preferable that R1 of the unsaturated monomer represented by the general formula (II) is hydrogen, R2 is a hydrogen atom or a methyl group, and R3 is a hydrogen atom.
  • the unsaturated monomer represented by the general formula (II) is specifically polyoxyethylene polyoxybutylene.
  • polyoxyethylene polyoxybutylene monoacrylic acid amide, polyoxyethylene polyoxybutylene monomethacrylic acid amide, polyoxyethylene polyoxybutylene monovinyl ether are preferably used, polyoxyethylene polyoxybutylene monomethacrylic acid amide, Polyoxyethylene polyoxybutylene monovinyl ether is particularly preferably used.
  • R1 in the general formula (II) is a hydrogen atom
  • R3 in which is a hydrogen atom is one in which the terminal OH group of the unsaturated monomer exemplified above is substituted with an alkoxy group having 1 to 8 carbon atoms.
  • unsaturated monomers in which the OH group at the terminal of polyoxyethylene polyoxybutylene monomethacrylamide or polyoxyethylene polyoxybutylene monovinyl ether is substituted with a methoxy group are preferably used.
  • An unsaturated monomer in which the OH group at the terminal of butylene monomethacrylamide is substituted with a methoxy group is particularly preferably used.
  • the weight ratio (A) / (B) of PVA (A) to POA-modified PVA (B) in the dispersion stabilizer for suspension polymerization of the present invention is not particularly limited, but may be 99/1 to 5/95. preferable. When the weight ratio (A) / (B) is larger than 99/1, the plasticizer absorbability of the vinyl polymer obtained by suspension polymerization of the vinyl compound may be deteriorated or the particle size distribution may be widened. There is.
  • the weight ratio (A) / (B) is preferably 97/3 or less, and more preferably 95/5 or less. When the weight ratio (A) / (B) is smaller than 5/95, the polymerization stability may be lowered when the vinyl compound is subjected to suspension polymerization.
  • the weight ratio (A) / (B) is preferably 10/90 or more, and more preferably 15/85 or more.
  • the dispersion stabilizer for suspension polymerization of the present invention is particularly suitably used for suspension polymerization of vinyl compounds.
  • vinyl compounds include vinyl halides such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid, methacrylic acid, esters and salts thereof; maleic acid, fumaric acid, esters and anhydrides thereof; Examples include styrene, acrylonitrile, vinylidene chloride, vinyl ether and the like.
  • the dispersion stabilizer for suspension polymerization of the present invention is particularly preferably used in suspension polymerization of vinyl chloride alone or together with a monomer capable of copolymerizing with vinyl chloride and vinyl chloride. Used.
  • Monomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylic esters such as methyl (meth) acrylate and ethyl (meth) acrylate; ethylene, ⁇ -olefins such as propylene; unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid; acrylonitrile, styrene, vinylidene chloride, vinyl ether and the like.
  • vinyl esters such as vinyl acetate and vinyl propionate
  • (meth) acrylic esters such as methyl (meth) acrylate and ethyl (meth) acrylate
  • ethylene, ⁇ -olefins such as propylene
  • unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid
  • acrylonitrile, styrene, vinylidene chloride, vinyl ether and the like
  • oil-soluble or water-soluble polymerization initiators conventionally used for polymerization of vinyl chloride monomers and the like can be used.
  • oil-soluble polymerization initiator include percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, t -Perester compounds such as butyl peroxypivalate, t-hexyl peroxypivalate, ⁇ -cumyl peroxyneodecanate; acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate Peroxides such as 3,5,5-trimethylhexanoyl peroxide and lauroyl peroxide; azo compounds such as azobis-2,4-dimethylvaleronitrile
  • additives can be added to the polymerization reaction system as necessary.
  • the additive include polymerization regulators such as aldehydes, halogenated hydrocarbons and mercaptans, and polymerization inhibitors such as phenol compounds, sulfur compounds and N-oxide compounds.
  • a pH adjuster, a crosslinking agent, etc. can also be added arbitrarily.
  • the polymerization temperature is not particularly limited, and can be adjusted to a high temperature exceeding 90 ° C. as well as a low temperature of about 20 ° C.
  • the dispersion stabilizer for suspension polymerization of the present invention is blended with additives such as preservatives, antifungal agents, antiblocking agents, antifoaming agents and the like that are usually used in suspension polymerization and emulsion polymerization, if necessary. be able to.
  • dispersion stabilizer for suspension polymerization of the present invention may be used alone, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose which are usually used for suspension polymerization of vinyl compounds in an aqueous medium are used.
  • Water-soluble cellulose ethers such as; water-soluble polymers such as gelatin; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan trioleate, glycerin tristearate, ethylene oxide propylene oxide block copolymers; polyoxyethylene sorbitan monolaurate, poly
  • a water-soluble emulsifier such as oxyethylene glycerol oleate or sodium laurate may be used in combination.
  • the amount added is not particularly limited, but is preferably 0.01 to 1.0 part by weight per 100 parts by weight of the vinyl compound.
  • Example 1 (Production of POA-modified PVA (B)) Into a 3 L reactor equipped with a stirrer, reflux condenser, nitrogen inlet tube, comonomer dropping port and initiator addition port, 550 g of vinyl acetate, 450 g of methanol, 3.3 g of POA group-containing monomer (monomer A) were added. The system was purged with nitrogen for 30 minutes while charging and nitrogen bubbling. Also, a comonomer solution having a concentration of 20% was prepared by dissolving POA group-containing monomer (monomer A) in methanol as a delay solution, and nitrogen substitution was performed by bubbling nitrogen gas.
  • the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. While the delay solution was added dropwise so that the monomer composition (ratio of vinyl acetate and monomer A) in the polymerization solution was constant, polymerization was performed at 60 ° C. for 3 hours and then cooled to stop the polymerization. The total amount of comonomer solution added until the polymerization was stopped was 40 ml. The solid content concentration when the polymerization was stopped was 24.4%. Subsequently, unreacted vinyl acetate monomer was removed while adding methanol occasionally at 30 ° C.
  • AIBN 2,2′-azobisisobutyronitrile
  • the dispersion stabilizer thus obtained was charged into a glass-lined autoclave in which the scale adhesion inhibitor NOXOL WSW (CIRS) was applied to a solid content of 0.3 g / m 2 .
  • CIRS scale adhesion inhibitor
  • Examples 2 to 16 Except for changes in saponification conditions such as the amount of vinyl acetate and methanol charged, polymerization conditions such as the type and amount of POA comonomer used during polymerization, the concentration of PVAc during saponification, and the molar ratio of sodium hydroxide to vinyl acetate units Using POA-modified PVA (B) synthesized in the same manner as in Example 1, suspension polymerization of vinyl chloride was performed in the same manner as in Example 1 to obtain vinyl chloride polymer particles.
  • Table 2 shows the structure of the comonomer used, and Table 1 shows the evaluation results of the obtained POA-modified PVA (B) and vinyl chloride polymer particles.
  • Comparative Example 1 The suspension polymerization of vinyl chloride was carried out in the same manner as in Example 1 except that the POA-modified PVA (B) was not used and the PVA (A) powder was used as it was as a dispersion stabilizer. In this case, vinyl chloride polymer particles could not be obtained because vinyl chloride was blocked and could not be polymerized.
  • Comparative Example 2 The vinyl chloride polymer was subjected to suspension polymerization of vinyl chloride in the same manner as in Example 1 except that the POA-modified PVA (B) was synthesized and used with a POA group modification amount of 0.005 mol%. Particles were obtained. The evaluation results are shown in Table 1. Uniform polymer particles could not be obtained due to the presence of coarse particles, and the amount of scale adhered was large and stable polymerization could not be performed.
  • Comparative Example 3 A vinyl chloride polymer particle was obtained by carrying out suspension polymerization of vinyl chloride in the same manner as in Example 1, except that a POA-modified PVA (B) having a polymerization degree of 150 was synthesized and used. The evaluation results are shown in Table 1. Uniform polymer particles could not be obtained due to the presence of coarse particles, and the amount of scale adhered was large and stable polymerization could not be performed.
  • Comparative Example 4 Except that a POA-modified PVA (B) having a polymerization degree of 1500 was synthesized and used, suspension polymerization of vinyl chloride was performed in the same manner as in Example 1 to obtain vinyl chloride polymer particles. The evaluation results are shown in Table 1. Uniform polymer particles could not be obtained due to the presence of coarse particles, and the amount of scale adhered was large and stable polymerization could not be performed.
  • Comparative Examples 6 and 7 As the POA-modified PVA (B), suspension polymerization of vinyl chloride was carried out in the same manner as in Example 1 except that the types of POA comonomer shown in Table 2 were used to obtain vinyl chloride polymer particles. The evaluation results are shown in Table 1. Uniform polymer particles could not be obtained due to the presence of coarse particles, and the amount of scale adhered was large and stable polymerization could not be performed.
  • the dispersion stabilizer for suspension polymerization of the vinyl compound of the present invention since the polymerization stability is high, the formation of coarse particles is small, and particles having a uniform particle size are obtained. can get. Further, blocking and scale adhesion due to unstable polymerization are reduced. Thus, the industrial evaluation of the dispersion stabilizer for suspension polymerization of the present invention is extremely high.

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Abstract

L'invention concerne un stabilisateur de dispersion pour la polymérisation en suspension, qui comprend: un polymère d'alcool vinylique (A) qui présente un degré de saponification supérieur ou égal à 60% par mole et un degré de polymérisation moyen (viscosité) supérieur ou égal à 200; et un polymère d'alcool vinylique modifié par du polyoxyalkylène (B) qui contient un groupe polyoxyalkylène représenté par la formule générale (I) dans une chaîne latérale et présente un degré de polymérisation moyen (viscosité) compris entre 200 et 1000, un degré de saponification inférieur à 60% par mole, et une quantité de groupes polyoxyalkylène modifiés comprise entre 0,1 et 10% par mole. Lorsque la polymérisation en suspension est mise en oeuvre à l'aide du stabilisateur de dispersion pour la polymérisation en suspension, il est possible de produire des particules polymères contenant peu de grosses particules formées à l'intérieur et présentant des diamètres de particules uniformes. Il est également possible de réduire le blocage par le tartre ou son adhésion. Dans la formule (I), R1 représente un atome d'hydrogène ou un groupe méthyle; R2 représente un atome d'hydrogène ou un groupe alkyle présentant 1 à 8 atomes de carbone; et m et n représentent chacun le nombre d'unités oxyalkylène répétées, m et n satisfaisant une exigence représentée par les formule suivantes : 1 ≤ m ≤ 10 et 3 ≤ n ≤ 20.
PCT/JP2010/052787 2009-04-01 2010-02-23 Stabilisateur de dispersion pour polymérisation en suspension WO2010113568A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
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JP2011126931A (ja) * 2009-12-15 2011-06-30 Kuraray Co Ltd 分散液および感熱記録材料
WO2013115239A1 (fr) * 2012-01-30 2013-08-08 株式会社クラレ Stabilisateur de dispersion pour polymérisation en suspension
WO2019156006A1 (fr) 2018-02-08 2019-08-15 デンカ株式会社 Polymère à base d'alcool vinylique modifié, et agent de stabilisation de dispersion pour polymérisation en suspension

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Publication number Priority date Publication date Assignee Title
CN111868103B (zh) * 2018-03-20 2022-11-01 株式会社可乐丽 悬浮聚合用分散稳定剂

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JP2004075870A (ja) * 2002-08-20 2004-03-11 Nippon Synthetic Chem Ind Co Ltd:The 分散安定剤

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JPH111505A (ja) * 1997-06-11 1999-01-06 Nippon Synthetic Chem Ind Co Ltd:The 分散安定剤
JP2004075870A (ja) * 2002-08-20 2004-03-11 Nippon Synthetic Chem Ind Co Ltd:The 分散安定剤

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JP2011126931A (ja) * 2009-12-15 2011-06-30 Kuraray Co Ltd 分散液および感熱記録材料
WO2013115239A1 (fr) * 2012-01-30 2013-08-08 株式会社クラレ Stabilisateur de dispersion pour polymérisation en suspension
WO2019156006A1 (fr) 2018-02-08 2019-08-15 デンカ株式会社 Polymère à base d'alcool vinylique modifié, et agent de stabilisation de dispersion pour polymérisation en suspension
US11345768B2 (en) 2018-02-08 2022-05-31 Denka Company Limited Modified vinyl alcohol-based polymer and dispersion stabilizer for suspension polymerization

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