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WO2007069422A1 - Adjuvant stabilisant de dispersion pour la polymérisation en suspension d'un composé vinylique - Google Patents

Adjuvant stabilisant de dispersion pour la polymérisation en suspension d'un composé vinylique Download PDF

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Publication number
WO2007069422A1
WO2007069422A1 PCT/JP2006/322725 JP2006322725W WO2007069422A1 WO 2007069422 A1 WO2007069422 A1 WO 2007069422A1 JP 2006322725 W JP2006322725 W JP 2006322725W WO 2007069422 A1 WO2007069422 A1 WO 2007069422A1
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Prior art keywords
compound
carbon atoms
suspension polymerization
hydrogen atom
vinyl
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Japanese (ja)
Inventor
Masaki Kato
Masato Nakamae
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2007550104A priority Critical patent/JP5001174B2/ja
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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

Definitions

  • the present invention relates to a dispersion stabilizing aid for suspension polymerization of vinyl compounds.
  • the partially saponified polybulal alcohol polymer is dissolved in water or a mixed solution of water and another organic solvent. Used. From this, the dispersion stabilizing aid for suspension polymerization of Bulle compounds can be [1] high concentration of the solution, [2] low foaming when preparing the solution, [ 3) The solution has a low viscosity, and [4] the solution has excellent long-term storage stability.
  • dispersion stabilizers for suspension polymerization of vinyl compounds include: [5] Suspension polymerization of vinyl compounds, which has a large plasticizer absorption rate and is easy to process. In order to prevent the formation of fisheye and other monomer components, it is required as a required performance to obtain porous vinyl polymer particles with a particle diameter as uniform as possible. ing.
  • the partially saponified polyvinyl alcohol polymer has low solubility in water, and when preparing a high-concentration solution, the viscosity of the solution is high, so that the handleability is high. Poor and prepared solutions have a low cloud point and thus cannot be stored for a long time.
  • the partially saponified polyvinyl alcohol polymer has low solubility in water. Therefore, when preparing a solution of the dispersion stabilizing aid for suspension polymerization, the partially saponified polyvinyl alcohol polymer force is partially saponified.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 7-286003 discloses a method for suspension polymerization of butyl chloride using an oil-soluble partially saponified polybutyl alcohol and an acetylene glycol derivative having a saponification degree of 20 to 60%. It is disclosed.
  • Patent Document 2 Japanese Patent Laid-Open No. 10-101737 uses a partially saponified polybulal alcohol having an average polymerization degree of 200 to 600 and a saponification degree of 20 to 55 mol% and a nonionic surfactant of HLB 10 to 18. A method for suspension polymerization of salt mulberry is disclosed.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 4-154810 discloses an aqueous dispersion having a vinyl ester polymer having an amino group, an ammonium group, a force propyl group, a sulfone group, etc. in the side chain as a dispersoid. The use is described.
  • Patent Document 4 Japanese Patent Laid-Open No. 10-259213 uses a partially saponified vinyl ester-based aqueous resin solution containing an oxyalkylene group, a carboxyl group, a sulfonic acid group, an amino group, and an ammonium group. Is described.
  • a method for suspension polymerization of vinyl chloride using partially saponified polyvinyl acetate having a viscosity of 15 mPas (corresponding to an average degree of polymerization of 74 to 80) and a nonionic emulsifier is disclosed.
  • Patent Document 6 Japanese Patent Laid-Open Publication No.
  • Sho 56-167745 discloses that polybulal alcohol having a saponification degree of 65 mol% or more and an average polymerization degree of 100 to 3000 is used as a dispersion stabilizer, a saponification degree of 25 to 65 mol%, and an average polymerization degree
  • An aqueous dispersion having a dispersoid of 1000 or less polyvinyl ester is disclosed, and it is described that the aqueous dispersion can be used as a dispersion stabilizing aid for suspension polymerization of vinyl chloride.
  • Patent Document 7 discloses an aqueous dispersion containing a terminal ion-modified polybulle ester polymer having a saponification degree of 60 mol% or less and an average polymerization degree of 50 to 3000 as a dispersoid, such as vinyl chloride. It is disclosed that it is used as a dispersion stabilizing aid for suspension polymerization of monomers.
  • Patent Document 8 Japanese Patent Application Laid-Open No. 52-110797 discloses a dispersion stabilizing aid for suspension polymerization of chlorinated bulle comprising partially saponified polybulal alcohol having a saponification degree of 30 to 65 mol% and a polymerization degree of 60 to 6000. It is disclosed.
  • Patent Document 9 discloses an aqueous solution having a saponification degree of 60 mol% or less, an average polymerization degree of 4000 or more, and a polybule ester polymer having an average particle size of 100 ⁇ m or less as a dispersoid. Dispersion stabilizing aids for vinyl compounds that have a dispersion power are disclosed.
  • Patent Document 10 Japanese Patent Laid-Open No. 7-62006
  • partially saponified polybulal alcohol having a saponification degree of 70 to 85 mol% and an average polymerization degree of 1500 to 3000 is used as a dispersion stabilizer, and the saponification degree is 20 to 55.
  • a partially saponified polybutyl alcohol dispersion stability aid with a mol% and an average degree of polymerization of 100 to 600 the reaction is started after the dispersion stability aid is dissolved in a mixed solution of water and an organic solvent or an organic solvent.
  • Patent Document 1 Japanese Patent Laid-Open No. 7-286003
  • Patent Document 2 JP-A-10-101737
  • Patent Document 3 Japanese Patent Laid-Open No. 4-154810
  • Patent Document 4 Japanese Patent Laid-Open No. 10-259213
  • Patent Document 5 Japanese Patent Laid-Open No. 53-6392
  • Patent Document 6 Japanese Unexamined Patent Publication No. 56-167745
  • Patent Document 7 W091Z15518
  • Patent Document 8 Japanese Patent Laid-Open No. 52-110797
  • Patent Document 9 Japanese Patent No. 3340492
  • Patent Document 10 Japanese Patent Laid-Open No. 7-62006
  • the present invention relates to a dispersion stabilization aid for suspension polymerization from a partially saponified polyvinyl alcohol polymer.
  • the purpose of the present invention is to provide a dispersion stabilizing aid for suspension polymerization of vinyl compounds, which is excellent in storage stability without precipitating a partially saponified polyvinyl alcohol polymer even when stored for a long period of time.
  • a dispersion stabilizing aid for suspension polymerization of an aqueous solution-based vinyl compound containing a compound (B) represented by the following general formula (I) or a nonionic hydrophilic surfactant (C) is:
  • R ⁇ R 2 and R 5 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.
  • a hydroxyalkyl group, R 4 represents a hydrogen atom, a hydroxyl group or an alkoxyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6)
  • the dispersion stabilizer for suspension polymerization of vinyl compounds of the present invention has a partially saponified polyvinyl alcohol polymer (hereinafter referred to as a partially saponified PVA system) having an average saponification degree of less than 70 mol% and an average polymerization degree of 650 or less.
  • a partially saponified PVA system having an average saponification degree of less than 70 mol% and an average polymerization degree of 650 or less.
  • the plasticizer has a high absorption rate and is easy to process. Further, it is possible to easily remove monomer components such as the remaining vinyl compound, and to obtain the effect of obtaining porous polymer particles having a uniform particle diameter.
  • the partially saponified PVA polymer (A) used in the present invention has a saponification degree of less than 70 mol%, preferably 65 mol% or less, particularly preferably 60 mol% or less.
  • the lower limit of the saponification degree is not particularly limited, but from the viewpoint of production of the partially saponified PVA polymer, the saponification degree is preferably 10 mol% or more, more preferably 20 mol% or more.
  • the degree of polymerization of the partially saponified PVA polymer (A) is 650 or less, preferably 600 or less, particularly preferably 550 or less.
  • the lower limit of the average degree of polymerization is not particularly limited, but from the viewpoint of producing a partially saponified PVA polymer, the average degree of polymerization is preferably 50 or more, more preferably 80 or more.
  • the content of the partially saponified PVA polymer (A) contained in the aqueous solution is preferably 5% by weight or more, more preferably 10% by weight or more, and still more preferably. It is 15% by weight or more, and particularly preferably 20% by weight or more. If the content of the partially saponified PVA polymer (A) is less than 5% by weight, the number of times the aqueous solution is prepared tends to be disadvantageous in terms of cost. Moreover, although there is no restriction
  • the vinyl ester polymer used as a raw material for producing the partially saponified PVA polymer (A) is a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion of a vinyl ester.
  • a conventionally known method such as a polymerization method or a dispersion polymerization method. It can be manufactured more.
  • preferred polymerization methods are the solution polymerization method, emulsion polymerization method and dispersion polymerization method. In the polymerization operation, any one of a batch method, a semi-batch method and a continuous method can be adopted.
  • butyl ester examples include butyl acetate, vinyl formate, propionate, vinyl caprylate, and versatic butyl. I like Bull! /.
  • an ethylenically unsaturated monomer that can be copolymerized with burster can be allowed to coexist within a range that does not impair the effects of the present invention.
  • ethylenically unsaturated monomers include, for example, ethylene, propylene, acrylic acid, methacrylic acid, fumaric acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, acrylonitrile, metathalyl-tolyl, acrylamide, Methacrylamide, trimethyl- (3-acrylamide-3-dimethylpropyl) ammonium chloride, acrylamide-2-methylpropanesulfonic acid and its sodium salt, ethyl vinyl ether, butyl vinyl ether, chloride butyl, vinyl bromide, fluoride Examples thereof include butyl, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, sodium vinyl sulfonate, sodium ally
  • the partially saponified PVA polymer (A) used in the present invention may preferably have a modified product of such a partially saponified PVA polymer that may have an ionic functional group at the terminal.
  • ionic functional groups include a carboxyl group and a sulfonic acid group, among which a carboxyl group is preferable.
  • These ionic groups include salts thereof, and alkali metal salts are preferred from the viewpoint that the partially saponified PVA polymer (A) is preferably water-dispersible.
  • Partially saponified PVA polymer (A) The production method of (A) is capable of adopting various methods that are not particularly limited.
  • Partially saponified Chain transfer agent having carboxyl group as a method to obtain PVA polymer (A) more economically and efficiently
  • a method is preferred in which butyl esters such as butyl acetate are polymerized in the presence of a thiol having a carboxyl group and then saponified (Japanese Patent Application Laid-Open Nos. 57-028121 and 57-105410). See the official gazette).
  • 3 3 2 2 to 6 are alkenyloxy groups are OCH, -OCH CH, -OCH CH CH, one OCH CH CH
  • n 1
  • the compound (B) is represented by the general formula (I), wherein R 1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 3 is a hydrogen atom or a hydroxyalkyl group having 1 to 6 carbon atoms, R 4 is a hydrogen atom, a hydroxyl group or an alkoxyl group having 1 to 6 carbon atoms, and R 5 is an alkyl group having 1 to 6 carbon atoms.
  • Glycol ether can be a Louis compound.
  • glycol ether compounds include, for example, ethylene dalcol monomethyl etherenole, ethylene glyconoresin methinore ethenore, ethylene glycol
  • Ethereol Ethylene glycolenoresipropinoreatenore, Ethyleneglycololemonobutinoreatenore, Ethyleneglycol dibutinoreether, Propyleneglycololemonomethylenether, Propyleneglycoldimethylether, Propyleneglycolmonoethylether, Propyleneglycol Nore chinino ethenore, propylene glycol monopropinore ethenore, propylene glycol dipropyl ether, propylene glycol -Monomonobutino ether, propylene glycol dibutyl ether and the like.
  • ethylene glycol monomethyl ether and diethylene glycol diethylene glycol which are condensates of ethylene glycol.
  • dipropylene glycol monomethyl ether dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, hexapropylene glycol dimethyl ether and the like, which are condensates of propylene glycol, can be mentioned.
  • Examples include 3-methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol. Among these, 3-methoxy-3-methyl-1-butanol is particularly preferred from the viewpoint of long-term storage stability of an aqueous solution.
  • the compound (B) is a compound in which R 1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It is an alkyl group, R 3 is a hydrogen atom or a hydroxyalkyl group having 1 to 6 carbon atoms, R 4 is a hydrogen atom or a hydroxyl group, and R 5 is a hydrogen atom. .
  • glycol compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylenedaricol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,3 propanediol, 1,4 butanediol, 1,6 Hexanediol, 3-Methyl-1,3 Butanediol, 3-Methyl-1,5 Pentanediol, etc. Among these, 3-Methyl-1, 5 Pentanediol is particularly preferred.
  • the compound (B) represented by the general formula (I) may be used alone or in combination of two or more.
  • the content of the compound (B) represented by the general formula (I) contained in the aqueous solution is preferably 0.01% by weight or more, more preferably 0.05. % By weight or more, particularly preferably 0.1% by weight or more.
  • the upper limit of the content is not particularly limited, but from the viewpoint of the environmental load on the wastewater discharged by suspension polymerization of bur compounds, 40 20% by weight or less is more preferable.
  • nonionic hydrophilic surfactant (C) used in the present invention examples include polyoxyethylene (hereinafter abbreviated as POE) sorbitan monooleate, POE sorbitan monostearate, POE sorbitan tetraoleate and the like.
  • POE polyoxyethylene
  • POE alkylphenols POE ⁇ polyoxypropylene (hereinafter abbreviated as POP) cetyl ether, ⁇ ⁇ POP-decyl tetradecyl ether, ⁇ ⁇ POP monobutyl ether, P OE ⁇ POP hydrogenated lanolin, POE ⁇ POP glycerin ether POE ⁇ POP alkyl ethers such as Tetronic POE 'tetra POP ethylene diamine condensates; POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate, POE hydrogenated castor oil triiso Stearate, POE hydrogenated castor oil monopyroglutamate monoisostearate POE hydrogenated castor oil derivatives such as acid diesters, POE hydrogenated castor oil maleic acid; POE beeswax 'lanolin derivatives such as POE sorbbit beeswax; Alcohol noramides such as coconut oil fatty acid
  • acetylene glycols with an oxide of ethylene oxide in which the addition weight of the ethylene oxide adduct is 50% by weight or more, is particularly preferred.
  • 2, 4, 7, 9-tetramethyl-5-decyne 4 , 7-diol ethylene oxide oxide is preferred.
  • These nonionic hydrophilic surfactants can be used alone or in combination of two or more.
  • the content of the nonionic hydrophilic surfactant (C) contained in the aqueous solution is preferably from 0.1 to 20% by weight, more preferably from 0.3 to 18% by weight, particularly preferably 0.5 to 15% by weight. If the content of the nonionic hydrophilic surfactant (C) is less than 0.1% by weight, it is difficult to obtain the effect of enhancing the long-term storage stability of the aqueous solution. If the content exceeds 20% by weight, the aqueous solution There is a tendency for foaming to become intense during preparation
  • the dispersion stabilizing aid for suspension polymerization of vinyl compounds of the present invention includes, as necessary, preservatives, antifungal agents, antiblocking agents, antifoaming agents usually used for suspension polymerization of vinyl compounds. Additives such as foaming agents can be blended.
  • Examples of vinyl compounds that can be used for suspension polymerization include halogenated burs such as vinyl chloride; bur esters such as butyl acetate and propionate burs; acrylic acid, methatalic acid, their esters and salts Maleic acid, fumaric acid, esters thereof and water-free substances; styrene, acrylonitrile, salt vinylidene, butyl ether and the like.
  • the dispersion stabilizer for suspension polymerization of a vinyl compound of the present invention is a monomer capable of copolymerizing vinyl chloride alone or with salt-vinyl and salt-vinyl. Can be suitably used in suspension polymerization in an aqueous medium.
  • Monomers that are copolymerized with vinyl chloride include: butyl esters such as butyl acetate and butyl propionate; (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate; ethylene, propylene, etc. ⁇ -olefins; unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid; acrylo-tolyl, styrene, vinylidene chloride, butyl ether and the like.
  • any oil-soluble catalyst or water-soluble catalyst can be used.
  • the oil-soluble catalyst include percarbonate compounds such as diisopropyl baroxy dicarbonate, di-2-ethenorehexenoreperoxydicarbonate, and jetoxetinoreperoxydicarbonate; t-butylperoxyneodecane, t Perester compounds such as butyl peroxypivalate, t-hexoxyloxypivalate, a Tamil peroxyneodecanate; acetyl cyclohexyl sulfo-lperoxide, 2, 4, 4 trimethylpentyl-2-per Peroxides such as oxyphenoxyacetate, 3, 5, 5-trimethylhexanoyl peroxide, lauroyl peroxide; azobis-2,4 dimethylvale-tolyl, azobis (4-2,4 dimethyl
  • water-soluble catalyst examples include potassium persulfate, ammonium persulfate, hydrogen peroxide, and tamennoide mouth peroxide. These oil-soluble catalysts or water-soluble catalysts can be used alone or in combination of two or more.
  • additives Upon suspension polymerization of the vinyl compound, other various 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, phenol compounds and N-oxide compounds.
  • polymerization regulators such as aldehydes, halogenated hydrocarbons and mercaptans
  • polymerization inhibitors such as phenol compounds, phenol compounds and N-oxide compounds.
  • a dispersion stabilizer In suspension polymerization of a vinyl compound, a dispersion stabilizer is usually used to stabilize the polymerization reaction, and the dispersion stabilizer aids the adjustment of the particle size of the resulting bull polymer particles, Used to increase the absorption of the agent.
  • the dispersion stabilizer In suspension polymerization of a vinyl compound using the dispersion stabilizing aid for suspension polymerization of the present invention, the dispersion stabilizer is generally used as a suspension stabilizer for a bull compound in an aqueous medium.
  • Water-soluble cellulose ethers such as methyl cellulose, hydrangea chinose resinose, hydroxypropino resinose, hydroxypropino methenocellulose, water soluble polymers such as polybutyl alcohol, gelatin; sorbitan monolaurate, Oil-soluble emulsifiers such as sorbitan trioleate, glycerin tristearate, and ethylene oxide propylene oxide block copolymer; polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerol glycol DOO, water-soluble emulsifiers and the like are used, such as sodium laurate, among them, saponification degree 65 to 99 mol 0 I preferably 68-96 mole 0/0, the degree of polymerization 500 to 4000, preferably from 550 to 3 500 Polybulal alcohol is preferably used.
  • the weight ratio of the added amount of the dispersion stabilizer and the dispersion stabilizer varies depending on the type of dispersion stabilizer used, etc., so it cannot be defined uniformly. However, the range of 95 / 5-20 / 80 is preferred, and 90Z10-30Z70 is particularly preferred.
  • the dispersion stabilizer and the dispersion stabilizing aid may be charged all at the beginning of the polymerization, or may be charged separately during the polymerization.
  • the partially saponified PVA polymer (VA) and the compound ( ⁇ ) represented by the general formula (I) or the nonionic hydrophilic surfactant (C) are water or It is dissolved or dispersed in a mixed solution of water and another organic solvent to form an aqueous solution.
  • the temperature of the aqueous solution is not particularly limited. It can be suitably used not only at a low temperature of about 20 ° C but also at a high temperature exceeding 90 ° C.
  • parts and% indicate parts by weight and% by weight, respectively.
  • a 10-liter reactor equipped with a stirrer, nitrogen inlet, additive inlet, and initiator inlet was charged with 4410 g of vinyl acetate and 1890 g of methanol, heated to 60 ° C, and then nitrogen was bubbled through the system for 30 minutes. Replaced.
  • a 50% concentration solution in which 3-mercaptopropionic acid (hereinafter referred to as 3-MPA) was dissolved in methanol as a chain transfer agent was prepared, and nitrogen substitution was performed by publishing with nitrogen gas. Adjust the temperature inside the reactor to 60 ° C, add 3-M PA2.Og, then add 1.2 g of 2,2,1azobis (4-methoxy-1,2,4-dimethylvaleronitol). The polymerization was started.
  • the polymerization temperature is maintained at 60 ° C and 3—MP A 50% methanol solution of A was continuously added at 26 mLZhr. After 4 hours, when the polymerization rate reached 58%, the polymerization was stopped by cooling. Next, unreacted vinyl acetate was removed under reduced pressure to obtain a methanol solution of modified polyvinyl acetate (modified PVAc). Add the NaOH methanol solution (10% concentration) to the modified PVAc solution adjusted to 30% so that the alkali molar ratio (number of moles of NaOH Z, number of moles of bullester units in the modified PVAc) is 0.002. Saponified.
  • a polyvinyl alcohol polymer (partially saponified PVA polymer) having a polymerization degree of 140 and a saponification degree of 40 mol% and containing a carboxyl group as an ionic group at the terminal was obtained.
  • the measurement of the degree of polymerization of the partially saponified PVA polymer and the presence or absence of a carboxyl group at the terminal were confirmed as follows.
  • the methanol solution of denatured PVAc obtained before the saponification reaction from which unreacted vinyl acetate has been removed is put into n-xane to precipitate denatured PVAc, and the recovered denatured PVAc is dissolved in acetone. Purification was carried out three times, and then dried under reduced pressure at 60 ° C. to obtain a purified modified PVAc.
  • This methanol solution of the modified PVAc purified product was saponified at an alkali molar ratio of 0.2, and then subjected to Sotshlet extraction with methanol for 3 days and then dried to obtain a purified modified PVA product.
  • the average degree of polymerization of the modified PVA was 140 when measured according to a conventional method of JIS K6726.
  • this modified PVA was dissolved in heavy water and subjected to nuclear magnetic resonance analysis, it was confirmed that a carboxyl group (COONa group) was present at one end of the molecule! /.
  • Poly Bulle alcohol manufactured by Kuraray Co., Ltd. PVA-420H: polymerization degree 2000, saponification degree 8 0 mole 0/0
  • a dispersion stabilizer Partially saponified PVA polymer (polymerization degree 140, saponification degree 40 mol%, modified with terminal force SCOONa group) and glycol ether compound were dissolved in deionized water at the ratio shown in Table 1 to prepare an aqueous solution. This was used as a dispersion stabilizing aid.
  • the partially saponified PVA polymer was used in an amount corresponding to 4 OO ppm with respect to the salt monomer.
  • the dispersion stabilizer and dispersion stabilizer obtained in this way were applied to a glass-lined autoclave in which the scale adhesion inhibitor NOXOL WSW (CIRS) was applied to a solid content of 0.3 gZ m 2.
  • the average particle size and plasticizer absorption (CPA) of the salty-bull polymer particles obtained by polymerizing the salty-bull were measured according to the following methods.
  • the particle size distribution was measured by dry sieve analysis using a Tyler mesh standard wire mesh, and the average particle size was determined.
  • MMB 3 Toxyl-3 unit til- ⁇ 'tanol
  • EGBE Ethylene liqueol mono thiol
  • the dispersion stabilizing aid for suspension polymerization of the present invention is a partially saponified PVA polymer (A) and the compound (B) represented by the general formula (I) or nonionic
  • the vinyl chloride polymer particles obtained by polymerization of vinyl compounds are used to absorb plasticizers. It can be seen that is large.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un adjuvant stabilisant de dispersion pour la polymérisation en suspension d'un composé vinylique. L'adjuvant stabilisant de dispersion est composé : d'une solution aqueuse contenant un polymère de type alcool polyvinylique partiellement saponifié ayant un degré moyen de saponification inférieur à 70 mol% et un degré moyen de polymérisation inférieur ou égal à 650 ; et d'un composé représenté par la formule générale (I) ci-dessous ou d'un tensioactif hydrophile non ionique. Lorsqu'on prépare une solution aqueuse de l'adjuvant stabilisant de dispersion pour la polymérisation en suspension, la formation de mousse due au polymère de type alcool polyvinylique partiellement saponifié est supprimée, ce qui empêche ainsi la précipitation du polymère de type alcool polyvinylique partiellement saponifié. En conséquence, l'adjuvant stabilisant de dispersion pour la polymérisation en suspension est excellent en termes de stabilité au stockage à long terme. (I) (Dans la formule, R1, R2 et R5 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle ayant 1-6 atomes de carbone ; R3 représente un atome d'hydrogène, un groupe alkyle ayant 1-6 atomes de carbone ou un groupe hydroxyalkyle ayant 1-6 atomes de carbone ; R4 représente un atome d'hydrogène, un groupe hydroxyle ou un groupe alcoxy ayant 1-6 atomes de carbone ; et n représente un nombre entier de 1-6).
PCT/JP2006/322725 2005-12-16 2006-11-15 Adjuvant stabilisant de dispersion pour la polymérisation en suspension d'un composé vinylique Ceased WO2007069422A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150032750A (ko) * 2012-07-19 2015-03-27 가부시키가이샤 구라레 현탁 중합용 분산 안정제 및 비닐계 수지의 제조 방법
WO2015156312A1 (fr) * 2014-04-09 2015-10-15 株式会社クラレ Agent de stabilisation de dispersion pour polymérisation en suspension, et procédé de fabrication de résine vinylique
WO2018116885A1 (fr) * 2016-12-19 2018-06-28 株式会社クラレ Solution aqueuse de dispersant pour polymérisation en suspension
WO2025206110A1 (fr) * 2024-03-29 2025-10-02 日本酢ビ・ポバール株式会社 Polymère d'alcool polyvinylique et son procédé de production

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JPH04154810A (ja) * 1990-10-19 1992-05-27 Kuraray Co Ltd ビニル系化合物の懸濁重合用の分散助剤
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