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WO2010113570A1 - Procédé de production de résine à base de vinyle - Google Patents

Procédé de production de résine à base de vinyle Download PDF

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Publication number
WO2010113570A1
WO2010113570A1 PCT/JP2010/052789 JP2010052789W WO2010113570A1 WO 2010113570 A1 WO2010113570 A1 WO 2010113570A1 JP 2010052789 W JP2010052789 W JP 2010052789W WO 2010113570 A1 WO2010113570 A1 WO 2010113570A1
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Prior art keywords
polymerization
vinyl
poa
group
weight
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Japanese (ja)
Inventor
悠太 田岡
真輔 新居
仲前　昌人
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2011507060A priority Critical patent/JP5548678B2/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
    • 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
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences

Definitions

  • the present invention relates to a method for producing a vinyl resin by suspension polymerization of a vinyl compound using a polymerization tank with a reflux condenser having excellent productivity. More specifically, the present invention relates to a method for producing a vinyl resin in which the obtained vinyl chloride polymer particles are uniform and have excellent antifoaming properties against dry foam generated in the middle to late stage of polymerization in a polymerization tank.
  • the wet foam is a foam mainly composed of water mainly derived from polyvinyl alcohol.
  • dry foam is foaming mainly composed of polyvinyl chloride (PVC) or vinyl chloride monomer (VCM), and occurs mainly in the middle to late stage of polymerization.
  • PVC polyvinyl chloride
  • VCM vinyl chloride monomer
  • Patent Document 1 Japanese Patent Laid-Open No. 2-180908 discloses that when the removal amount of the polymerization reaction heat in the reflux condenser is 10% or less of the total polymerization reaction amount, silicone such as dimethylpolysiloxane, A method of adding low saponification degree polyvinyl alcohol or the like is disclosed.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 3-212409 discloses a degree of saponification with respect to 100 parts by weight of vinyl chloride monomer when the amount of polymerization reaction heat removed by the reflux condenser does not exceed 10% of the total polymerization reaction heat.
  • Patent Document 3 Japanese Patent Laid-Open No. 55-137105 discloses that ion-modified polyvinyl alcohol having a saponification degree of 60 to 80% is added before the start of polymerization.
  • Patent Document 4 Japanese Patent Laid-Open No. 7-179507
  • water-soluble polyvinyl alcohol having a saponification degree of 70 to 85 mol% and a polymerization degree of 700 to 3000 is added at the time of polymerization conversion of 5 to 50%, and polymerization is performed. Is disclosed in a temperature range of 58-70 ° C.
  • Patent Document 5 Japanese Patent Application Laid-Open No. 7-53607 discloses that water-soluble polyvinyl alcohol having a saponification degree of 70 to 85 mol% and a polymerization degree of 700 to 3000 is continuously or A method of sequential addition is disclosed.
  • Patent Document 6 Japanese Patent Application Laid-Open No. 7-18007 discloses a method of adding water-soluble polyvinyl alcohol having a saponification degree of 75 to 85 mol% and a polymerization degree of 1500 to 2700 at a polymerization conversion rate of 30 to 60%. Has been.
  • Patent Document 7 Japanese Patent Laid-Open No. 8-73512 discloses a method of adding partially saponified polyvinyl alcohol having a saponification degree of 20 to 55 mol% and an average polymerization degree of 150 to 600 between a polymerization rate conversion of 20 to 60%. Is disclosed.
  • Patent Document 8 Japanese Patent Laid-Open No. 10-1503 discloses a method of adding a vinyl alcohol polymer having a saponification degree of 85 mol% or less at a polymerization conversion rate of 30 to 90%.
  • Patent Document 9 Japanese Patent Application Laid-Open No. 11-116630
  • a vinyl alcohol polymer having a saponification degree of 85 mol% or less is added continuously or divided into two or more times at a polymerization conversion rate of 30 to 90%.
  • a method is disclosed.
  • Patent Document 11 Japanese Patent Laid-Open No. 2001-233904 discloses that the dielectric constant is 32 c. g. s. e. s. u.
  • a method of adding a polyvinyl alcohol polymer having an ionic group at the terminal and further containing an oxyalkylene group is disclosed. (Y: degree of saponification, ⁇ : block character)
  • Patent Document 12 Japanese Patent Laid-Open No. 59-155408 discloses a method for producing a modified PVA characterized by saponifying a copolymer of an unsaturated monomer containing an oxyalkylene group and vinyl acetate. It is disclosed.
  • the oxyalkylene group in the unsaturated monomer used for the production of the modified PVA include polyoxyethylene groups, polyoxypropylene groups, polyoxybutylene groups having about 1 to 50 repeating units.
  • Patent Documents 1 and 2 have a problem in that dry foam generation is severe and the bulk specific gravity of the vinyl chloride resin tends to decrease. Further, the methods described in Patent Documents 3, 4, 5, 6, and 7 have a problem that the polymerization time is long and productivity is low because no reflux condenser is used. Furthermore, in the methods described in Patent Documents 8, 9, 10, and 11, a polymerization tank with a reflux condenser is used, and the productivity is high. It is not satisfactory, and problems such as adhesion of scale remain, and further improvement is desired.
  • Patent Document 12 discloses a method for producing a modified PVA containing an oxyalkylene group, but there is no description or suggestion about suppression of dry foam.
  • the resulting vinyl polymer particles are uniform and have a defoaming property against dry foam generated from the middle to the later stage of the polymerization. It aims at providing the manufacturing method of the outstanding vinyl resin.
  • the present inventors perform suspension polymerization of vinyl compounds in the presence of a dispersion stabilizer for suspension polymerization using a polymerization tank equipped with a reflux condenser.
  • a vinyl alcohol polymer containing a polyoxyalkylene group represented by the following general formula (I) in the side chain with respect to 100 parts by weight of the vinyl compound It has been found that the above problem can be solved by adding 0.001 to 5 parts by weight of a polyoxyalkylene-modified vinyl alcohol polymer (A) having a polyoxyalkylene group modification amount of 0.01 to 10 mol%.
  • the present invention has been 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 productivity of vinyl resin can be increased.
  • vinyl polymer particles having a uniform particle diameter can be obtained, a high-quality vinyl resin can be provided.
  • the reflux condenser is used for efficiently removing the heat of polymerization reaction generated by suspension polymerization of a vinyl compound.
  • the gas of the unreacted vinyl compound (monomer) generated from the suspension in the polymerization tank is liquefied by the reflux condenser and returned to the polymerization tank, whereby the polymerization heat is removed.
  • the temperature of the cooling water in the reflux condenser is usually about 10 to 50 ° C.
  • the temperature control of the polymerization tank is performed in combination with the temperature control by the jacket or coil of the polymerization tank in addition to the heat removal by the reflux condenser.
  • the removal amount of the polymerization reaction heat in the reflux condenser is not particularly limited, but is preferably 10 to 80%, more preferably 20 to 60% of the total polymerization reaction heat amount.
  • the suspension polymerization of the vinyl compound is performed in the presence of a dispersion stabilizer for suspension polymerization.
  • the dispersion stabilizer for suspension polymerization is not particularly limited, and examples thereof include cellulose derivatives such as methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, water-soluble polymers such as gelatin, polyvinyl alcohol, and polyvinylpyrrolidone.
  • polyvinyl alcohol having a saponification degree of 60 to 95 mol%, preferably 68 to 93 mol%, and a polymerization degree of 200 to 3,500, preferably 500 to 2500 is suitably used.
  • the amount of the dispersion stabilizer for suspension polymerization is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 2 parts by weight, more preferably 0.02 to 2 parts by weight based on 100 parts by weight of the vinyl compound. 1 part by weight is more preferred.
  • the amount is less than 0.01 part by weight, the polymerization stability may decrease when suspension polymerization of the vinyl compound.
  • the amount exceeds 5 parts by weight the waste liquid after suspension polymerization becomes cloudy. Chemical oxygen demand (COD) may be high.
  • the above general A vinyl alcohol polymer containing a polyoxyalkylene group represented by the formula (I) in the side chain (hereinafter, the vinyl alcohol polymer may be abbreviated as PVA), and the polyoxyalkylene group modification amount is 0.
  • a polyoxyalkylene-modified vinyl alcohol polymer (A) (hereinafter, the polyoxyalkylene-modified vinyl alcohol polymer may be abbreviated as POA-modified PVA) in an amount of 0.01 to 10 mol% is added.
  • POA-modified PVA (A) needs to have a polyoxyalkylene (POA) group modification amount of 0.01 to 10 mol%.
  • POA group modification amount exceeds 10 mol%, the proportion of hydrophobic groups contained in one molecule of POA-modified PVA (A) increases, and the water solubility of the PVA may decrease.
  • POA group modification amount is less than 0.01 mol%, the water solubility of the POA modified PVA (A) 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 obtained from, for example, the proton NMR of the POA modified polyvinyl ester which is the precursor of the PVA, for example, POA modified polyvinyl acetate (POA modified PVAc). Can do. Specifically, after re-precipitation purification of POA-modified PVAc with n-hexane / acetone three or more times, it is dried under reduced pressure at 50 ° C. for 2 days to prepare POA-modified PVAc for analysis.
  • the PVAc is dissolved in CDCl 3 and measured at room temperature using 500 MHz proton NMR (JEOL GX-500). From the peak ⁇ (4.7 to 5.2 ppm) derived from the main chain methine of the vinyl ester and the peak ⁇ (0.8 to 1.0 ppm) derived from the terminal methyl group of the oxybutylene unit (unit 2) of the POA group
  • the POA group modification amount is calculated using the following formula.
  • POA group modification amount (mol%) ⁇ (number of protons of ⁇ / 3n) / (number of protons of ⁇ + (number of protons of ⁇ / 3n)) ⁇ ⁇ 100 n is the number of oxybutylene units (unit 2)
  • the degree of polymerization of POA-modified PVA (A) is preferably 200 or more, more preferably 200 to 3000, and still more preferably 300 to 2500. If the degree of polymerization is less than 200, the effect of suppressing dry foam is insufficient, and on the contrary, the wet foam may become intense. If it exceeds 3000, the plasticizer absorbability of the resulting vinyl resin may be reduced.
  • POA-modified PVA (A) may be used alone, or two or more kinds having different characteristics may be mixed and used.
  • the degree of saponification of POA-modified PVA (A) is preferably 50 to 99 mol%, more preferably 60 to 98 mol%, still more preferably 65 to 95 mol%. If the degree of saponification is less than 50 mol%, the effect of suppressing dry foam may not be obtained, and foaming may occur. If it exceeds 99%, the plasticizer absorbability of the resulting vinyl resin may be reduced.
  • the number of repeating units m of the unit 1 of the POA group represented by the general formula (I) must be 1 ⁇ m ⁇ 10, preferably 1 ⁇ m ⁇ 5, more preferably 1 ⁇ m ⁇ 3, and 1 ⁇ m. ⁇ 2 is particularly preferred.
  • the number of repeating units n of unit 2 (polyoxybutylene) must be 3 ⁇ n ⁇ 20, preferably 5 ⁇ n ⁇ 18, and particularly preferably 8 ⁇ n ⁇ 15.
  • n is less than 3
  • the interaction between POA groups does not appear, and the viscosity of the POA-modified PVA aqueous solution may be low.
  • n is more than 20, the hydrophobicity of the POA group becomes high, and POA-modified PVA ( The water solubility of A) may decrease.
  • copolymerization of an unsaturated monomer having a POA group represented by the general formula (I) and a vinyl ester monomer is carried out 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.
  • polymerizes is higher than 200 degreeC, since it becomes difficult to obtain POA modified PVA (A) which has the target POA group modification amount, it is unpreferable.
  • the temperature employed in the copolymerization for example, by controlling the polymerization rate, the heat generated by the polymerization is balanced with the heat released from the surface of the reactor. Examples thereof include a method and a method of controlling by an external jacket using an appropriate heating medium, but the latter method is preferable from the viewpoint of safety.
  • 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) for the purpose of preventing coloring.
  • 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 POA-modified PVA (A) 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 POA-modified PVA (A) is preferably water-dispersible.
  • a method for introducing an ionic functional group into the terminal part of the POA-modified PVA (A) vinyl acetate is used in the presence of a thiol compound such as thiolacetic acid, mercaptopropionic acid, 3-mercapto-1-propanesulfonic acid sodium salt.
  • a method of polymerizing a vinyl ester monomer such as 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 —, wherein R 5 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
  • R2 An example in which is a hydrogen atom and R3 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 POA-modified PVA (A) is added at a time when the polymerization conversion of the vinyl compound is 10% or more, preferably 15% to 90%, and more preferably 18% to 87%. More preferably, 20% to 85% is particularly preferable.
  • foaming due to dry foam occurs immediately before the internal pressure of the polymerization tank starts to decrease or immediately after the internal pressure of the polymerization tank starts to decrease, it is also preferable to add at this point.
  • forms such as aqueous solution, aqueous dispersion, organic solvent solutions, such as methanol, and a methanol-water mixed solution, is mentioned.
  • the concentration of the POA-modified PVA (A) solution is usually 0.01 to 30% by weight.
  • the temperature of the solution of the POA-modified PVA (A) is not particularly limited, and may be one raised to room temperature or the polymerization temperature.
  • the addition amount of the POA-modified PVA (A) is 0.001 to 5 parts by weight, preferably 0.001 to 0.5 parts by weight, based on 100 parts by weight of the vinyl compound to be subjected to suspension polymerization. More preferred is 0.01 to 0.1 parts by weight.
  • vinyl compounds used for suspension polymerization 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, and the like. Esters and anhydrides; styrene, acrylonitrile, vinylidene chloride, vinyl ether and the like. Of these, vinyl chloride is particularly preferred.
  • the suspension polymerization of vinyl chloride may be homopolymerization or copolymerization.
  • 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
  • any oil-soluble catalyst or water-soluble catalyst conventionally used for polymerization of vinyl chloride monomers and the like can be used.
  • the oil-soluble catalyst include percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, t-butyl percarbonate.
  • Perester compounds such as oxypivalate, t-hexylperoxypivalate, ⁇ -cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, 3, Examples thereof include peroxides such as 5,5-trimethylhexanoyl peroxide and lauroyl peroxide; azo compounds such as azobis-2,4-dimethylvaleronitrile and azobis (4-2,4-dimethylvaleronitrile).
  • water-soluble catalyst include potassium persulfate, ammonium persulfate, hydrogen peroxide, cumene hydroperoxide, and the like. These oil-soluble catalysts or water-soluble catalysts can be used alone or in combination of two or more.
  • 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. Further, it is optional to add a pH adjusting agent, a crosslinking agent, etc., and a plurality of the above additives may be used in combination.
  • a partially saponified vinyl alcohol polymer having a saponification degree of 60 mol% or less may be used as a dispersion stabilizing aid.
  • the addition amount is preferably 0.1 to 120 parts by weight, more preferably 0.5 to 110 parts by weight, and particularly preferably 1 to 100 parts by weight with respect to 100 parts by weight of the dispersion stabilizer for suspension polymerization.
  • the partially saponified vinyl alcohol polymer used as a dispersion stabilizing aid in addition to the unmodified partially saponified vinyl alcohol polymer, 10 mol% of an ionic group such as a carboxyl group or an oxyalkylene group is added to the side chain or terminal. Examples thereof include partially saponified vinyl alcohol polymers.
  • oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan trioleate, glycerin tristearate, ethylene oxide propylene oxide block copolymer, polyoxyethylene sorbitan monolaurate, polyoxy Water-soluble emulsifiers such as ethylene glycerol oleate and sodium laurate may be used.
  • 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.
  • Evaluation of vinyl chloride polymer particles and dry foam generation state was performed as follows. (Evaluation of vinyl chloride polymer particles) For the vinyl chloride polymer particles, the particle size distribution and the amount of scale adhesion were measured according to the following methods. (1) Particle size distribution The content of JIS standard sieve 42 mesh on and 200 mesh pass was expressed in weight%. It shows that the smaller the content, the smaller the coarse particles or fine powder, and the more uniform particles are obtained. A: Less than 0.5% B: 0.5% or more and less than 1% C: 1% or more (2) Bulk specific gravity Measured according to JIS K6721.
  • Example 1 (Production of POA-modified PVA (A)) Into a 3 L reactor equipped with a stirrer, reflux condenser, nitrogen inlet tube, comonomer dropping port and initiator addition port, 400 g of vinyl acetate, 600 g of methanol, and 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 75 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
  • POA-modified PVA (A) had a polymerization degree of 520, a saponification degree of 70 mol%, and a POA modification amount of 0.4 mol%.
  • the pressure in the polymerization tank at the start of the polymerization was 1.02 MPa. Subsequently, the polymerization was continued, and when the polymerization conversion rate reached 70%, 10 L of the aqueous solution of POA-modified PVA (A) synthesized above (0.02 parts as PVA (A)) was added. When the pressure in the polymerization tank reached 0.5 MPa, the polymerization was stopped, the unreacted monomer was recovered, the polymer slurry was taken out, and dried at 65 ° C. overnight to obtain vinyl chloride polymer particles. . Table 1 shows the evaluation results of the resulting vinyl chloride polymer particles and the state of occurrence of dry foam.
  • Examples 2-14 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 Vinyl chloride was prepared in the same manner as in Example 1 except that POA-modified PVA (A) synthesized in the same manner as in Example 1 was used and POA-modified PVA (A) was added at the time of polymerization conversion shown in Table 1. Was subjected to suspension polymerization 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 (A) and vinyl chloride polymer particles.
  • 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
  • Comparative Example 2 instead of POA-modified PVA (A), suspension polymerization of vinyl chloride was carried out in the same manner as in Example 1 except that a POA-modified amount of 0.005 mol% was synthesized and used. Combined particles were obtained. The evaluation results are shown in Table 1. There were coarse particles, uniform polymer particles could not be obtained, foaming after polymerization occurred, and scale adhered to the inner wall of the polymerization tank.
  • Comparative Example 3 instead of POA-modified PVA (A), suspension polymerization of vinyl chloride was carried out in the same manner as in Example 1 except that a POA-modified amount of 11 mol% was synthesized and used. Vinyl chloride polymer particles could not be obtained because the block could not be polymerized.
  • Comparative Example 4 The vinyl chloride polymer was subjected to suspension polymerization of vinyl chloride in the same manner as in Example 1 except that POA-modified PVA (A) synthesized in the same manner as in Example 1 was added when the polymerization conversion was 5%. Particles were obtained. The evaluation results are shown in Table 1. Uniform polymer particles were not obtained due to the presence of coarse particles, and there were many bubbles after the polymerization, and the scale adhered to the inner wall surface of the polymerization tank.
  • Comparative Examples 5 and 6 As the POA-modified PVA (A), 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. There were coarse particles, uniform polymer particles could not be obtained, foaming after polymerization occurred, and scale adhered to the inner wall of the polymerization tank.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Une résine à base de vinyle présentant une excellente propriété antimousse sur la mousse sèche générée pendant la polymérisation et causant un faible dépôt de tartre peut être obtenue par addition d'un polymère à base d'alcool de vinyle à modification polyoxyalkylène (A) qui est un polymère à base d'alcool de vinyle contenant un groupe polyoxyalkylène représenté par la formule (I) dans une chaîne latérale et qui présente une quantité de modification par le groupe polyoxyalkylène de 0.01 à 10 en pourcentage molaire dans une quantité de 0.001 à 5 parts en poids relativement à 100 parts en poids d'un composé à base de vinyle en fin de conversion de polymérisation de 10% ou plus, lors de la polymérisation d'une suspension du composé à base de vinyle en présence d'un stabilisant de dispersion destiné à la polymérisation de suspension au moyen d'un bain de polymérisation avec un condenseur de reflux. Dans la formule (I), R1 représente un atome hydrogène ou un groupe méthyle; R2 représente un atome hydrogène ou un groupe alkyle comportant 1 à 8 atomes de carbone; m et n représentent respectivement le nombre d'unités de répétition d'oxyalkylène et correspondent aux rapports suivants: 1 ≤ m ≤ 10 et 3 ≤ n ≤ 20.
PCT/JP2010/052789 2009-04-01 2010-02-23 Procédé de production de résine à base de vinyle Ceased WO2010113570A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2013115239A1 (ja) * 2012-01-30 2015-05-11 株式会社クラレ 懸濁重合用分散安定剤

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6058402A (ja) * 1983-09-07 1985-04-04 Nippon Synthetic Chem Ind Co Ltd:The 分散安定剤
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6058402A (ja) * 1983-09-07 1985-04-04 Nippon Synthetic Chem Ind Co Ltd:The 分散安定剤
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2013115239A1 (ja) * 2012-01-30 2015-05-11 株式会社クラレ 懸濁重合用分散安定剤

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