WO2016076349A1 - 懸濁重合用分散安定剤及びビニル系樹脂の製造方法 - Google Patents
懸濁重合用分散安定剤及びビニル系樹脂の製造方法 Download PDFInfo
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- WO2016076349A1 WO2016076349A1 PCT/JP2015/081716 JP2015081716W WO2016076349A1 WO 2016076349 A1 WO2016076349 A1 WO 2016076349A1 JP 2015081716 W JP2015081716 W JP 2015081716W WO 2016076349 A1 WO2016076349 A1 WO 2016076349A1
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- Prior art keywords
- vinyl
- pva
- polymerization
- less
- dispersion stabilizer
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 64
- 229920005989 resin Polymers 0.000 title claims abstract description 47
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- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 44
- 239000006185 dispersion Substances 0.000 title claims abstract description 36
- 239000003381 stabilizer Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 25
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- 238000002835 absorbance Methods 0.000 claims abstract description 31
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 9
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- -1 ethylene, propylene, n-butene Chemical class 0.000 description 9
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- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
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- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical class CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- SIGUVTURIMRFDD-UHFFFAOYSA-M sodium dioxidophosphanium Chemical compound [Na+].[O-][PH2]=O SIGUVTURIMRFDD-UHFFFAOYSA-M 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical class [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F116/00—Homopolymers 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
- C08F116/02—Homopolymers 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 by an alcohol radical
- C08F116/04—Acyclic compounds
- C08F116/06—Polyvinyl alcohol ; Vinyl alcohol
-
- 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
- C08F114/00—Homopolymers 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
- C08F114/02—Monomers containing chlorine
- C08F114/04—Monomers containing two carbon atoms
- C08F114/06—Vinyl chloride
-
- 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
- C08F14/00—Homopolymers and 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
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—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 by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
-
- 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
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/38—Alcohols, e.g. oxidation products of paraffins
-
- 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
- C08F18/00—Homopolymers and 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
- C08F18/08—Vinyl acetate
-
- 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
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
- C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
Definitions
- the present invention relates to a dispersion stabilizer for suspension polymerization containing a vinyl alcohol polymer.
- the present invention also relates to a method for producing a vinyl resin in which a vinyl monomer is subjected to suspension polymerization using the dispersion stabilizer.
- the performance required for the dispersion stabilizer is as follows: (1) the number of coarse particles of the resulting polymer is small, (2) the particle size distribution of the obtained polymer is sharp, and (3) the resulting polymer.
- the bulk specific gravity is high and the mass per unit volume is large.
- Patent Document 1 describes a dispersion stabilizer in which acetaldehyde is introduced at the end of a vinyl alcohol polymer and further subjected to heat treatment. Although the performance of the dispersion stabilizer was improved by heat treatment as compared with the conventional product, it was difficult to say that the required performance was completely satisfied.
- the present invention provides a dispersion stabilizer for suspension polymerization that satisfies the above-mentioned performances (1) to (3), and is particularly capable of obtaining a vinyl resin having excellent polymerization stability, a small particle diameter, and a high bulk specific gravity. And it aims at providing the manufacturing method of vinyl resin.
- the present inventors have found that the PVA in which the absorbance, saponification degree, viscosity average polymerization degree, and YI value of the powder shape are within a specific range at a specific wavelength. It has been found that the above problem can be solved by a dispersion stabilizer for suspension polymerization containing (A).
- the absorbance (a1) at a wavelength of 280 nm of an aqueous solution having a concentration of 0.1% by mass is less than 0.25
- the absorbance (a2) at a wavelength of 320 nm of the aqueous solution is less than 0.030
- the saponification degree is 68 mol% or more and 98 A dispersion stabilizer for suspension polymerization containing a vinyl alcohol polymer (A) having a mol% or less, a viscosity average polymerization degree of more than 1500 and less than 4500, and a YI value in a powder form of 5 or more
- the absorbance (b1) at a wavelength of 280 nm of an aqueous solution having a concentration of 0.1% by mass is 0.25 or more
- the absorbance (b2) at a wavelength of 320 nm of the aqueous solution is 0.030 or more
- the saponification degree is 65 mol%.
- [4] A method for producing a vinyl resin, in which a vinyl monomer is subjected to suspension polymerization in an aqueous medium using the dispersion stabilizer for suspension polymerization according to any one of [1] to [3]; [5] The method for producing a vinyl resin according to [4], wherein the mass ratio (vinyl monomer / aqueous medium) of the vinyl monomer used in the suspension polymerization to the aqueous medium is 0.75 or more. ; [6] The method for producing a vinyl resin according to [4] or [5], wherein the vinyl monomer is vinyl chloride; About.
- the dispersion stabilizer for suspension polymerization of the present invention provides a vinyl resin having excellent polymerization stability, a small particle size, and an improved bulk specific gravity.
- the absorbance (a1) at a wavelength of 280 nm of an aqueous solution having a concentration of 0.1% by mass is less than 0.25
- the absorbance (a2) at a wavelength of 320 nm of the aqueous solution is less than 0.030.
- the absorption at the wavelength 280 nm is attributed to the structure of —CO— (CH ⁇ CH) 2 — in PVA.
- the absorption at a wavelength of 320 nm is attributed to the structure of —CO— (CH ⁇ CH) 3 — in PVA.
- the absorbance (a1) at a wavelength of 280 nm of an aqueous solution having a concentration of 0.1% by mass is less than 0.25
- the absorbance (a2) at a wavelength of 320 nm of the aqueous solution is 0.8. It is less than 030.
- the absorbance (a1) is preferably 0.20 or less, and more preferably 0.15 or less.
- the absorbance (a2) is preferably 0.020 or less, and more preferably 0.015 or less.
- the saponification degree of PVA (A) used in the present invention needs to be 68 mol% or more and 98 mol% or less. If the degree of saponification is less than 68 mol%, PVA (A) becomes insoluble in water and the handleability may deteriorate. Furthermore, suspension polymerization of vinyl monomers becomes unstable, and the resulting vinyl resin particles may be coarsened. On the other hand, if the degree of saponification exceeds 98 mol%, the solubility in cold water is lowered, and the handleability may be deteriorated. Furthermore, suspension polymerization of vinyl monomers becomes unstable, and the resulting vinyl polymer particles may be coarsened.
- the saponification degree of PVA (A) is preferably 70 mol% or more, and more preferably 72 mol% or more. On the other hand, the saponification degree is preferably 95 mol% or less, and more preferably 92 mol% or less.
- the degree of saponification of the above PVA (A) is measured according to JIS-K6726 (1994).
- the viscosity average polymerization degree of PVA (A) used in the present invention is more than 1500 and less than 4500.
- the viscosity average polymerization degree of PVA (A) is 1500 or less, the stability of the suspension polymerization of the vinyl monomer is lowered, and the resulting vinyl polymer particles tend to be coarse. Furthermore, there arises a problem that particles having high uniformity in particle diameter cannot be obtained.
- the viscosity average degree of polymerization is 4500 or more, the water-solubility of PVA is lowered and the handleability may be deteriorated.
- the viscosity average degree of polymerization is preferably more than 1700, more preferably more than 1800.
- the viscosity average degree of polymerization is preferably less than 4000, and more preferably less than 3500.
- the viscosity average degree of polymerization of PVA (A) is determined by measuring the intrinsic viscosity in an acetone solution from the formula of Nakajima after saponifying the PVA polymer substantially completely and then acetylating it to a vinyl ester polymer ( Akio Nakajima: Polymer Chemistry 6 (1949)).
- the YI (yellow index) value in the powder shape of PVA (A) used in the present invention is 5 or more. If the YI value is less than 5, the stability of the suspension polymerization of the vinyl monomer is lowered, and the resulting vinyl polymer particles are coarse. In addition, since particles with high uniformity in particle diameter cannot be obtained, problems such as reduction in bulk specific gravity also occur.
- the YI value is preferably 10 or more, and more preferably 15 or more.
- the upper limit of the YI value is not particularly limited, but when the dispersion stabilizer of the present invention is used for suspension polymerization of a vinyl monomer, 90 or less is preferable and 85 or less from the viewpoint of the hue of the resulting vinyl resin. Is more preferable.
- the value of YI can be arbitrarily adjusted by controlling saponification conditions such as the amount of saponification catalyst and heat treatment conditions such as temperature and time during the production of PVA (A).
- saponification conditions such as the amount of saponification catalyst
- heat treatment conditions such as temperature and time during the production of PVA (A).
- an inert gas such as nitrogen, oxygen, air, or the like can be used.
- the PVA (A) is produced by subjecting a PVA synthesized by polymerizing a vinyl ester monomer and saponifying the obtained polymer according to a conventional method to heat treatment.
- a method for polymerizing the vinyl ester monomer conventionally known methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method can be applied.
- the polymerization catalyst an azo catalyst, a peroxide catalyst, a redox catalyst, or the like is appropriately selected depending on the polymerization method.
- the saponification reaction can be applied by alcoholysis or hydrolysis using a conventionally known alkali catalyst or acid catalyst. Among them, saponification reaction using methanol as a solvent and caustic soda (NaOH) catalyst is most convenient. preferable.
- the PVA (A) can be produced by optimizing the heat treatment conditions. Although the mechanism of action when the PVA (A) of the present invention is used for suspension polymerization of vinyl chloride is not clear, it can be estimated as follows. By heat-treating PVA, a dehydration reaction of a hydroxyl group in the molecule occurs and an enone structure is generated. At this time, in PVA in which a carbonyl group is introduced at the end of the molecular chain, dehydration by heat treatment occurs preferentially from the molecular end starting from the carbonyl group, and the enone structure may not be uniformly introduced into the molecular chain. is there.
- the heat treatment conditions are strict for the purpose of randomly introducing an enone structure into the molecule, an unnecessarily enone structure is introduced into the molecule and the solubility in water is reduced.
- the PVA (A) of the present invention since the PVA (A) of the present invention has an enone structure randomly in a relatively long chain, it is stably bonded in the form of loop train tail by adsorption to vinyl chloride monomer and subsequent graft reaction. Since it is easy to achieve the state, improvement of protective colloid performance can be expected. In particular, at the stage of particle control at the end of the suspension polymerization reaction, performance is exhibited in reducing the particle diameter of the obtained vinyl resin or improving the bulk specific gravity.
- the vinyl ester unit constituting the PVA (A) includes units derived from various vinyl ester compounds.
- monomers When synthesizing the PVA (A) used in the present invention, 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 its salts; acrylamide; N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, Acrylamide derivatives such as diacetone acrylamide, acrylamide propane sulfonic acid and salts thereof, acrylamide propyl dimethylamine and salts or quaternary salts thereof, N-methylol acrylamide and derivatives thereof; methacrylamide; N-methyl methacrylamide, N-ethyl methacryl Amides, methacrylamide propanesulfonic acid and salts thereof, methacrylamide propyldimethylamine and salts thereof or quaternary salts thereof, N-methylol me
- a chain transfer agent may be used for the purpose of adjusting the degree of polymerization within the range not impairing the gist of the present invention or introducing a modified species at the terminal.
- chain transfer agents such as 2-hydroxyethanethiol, 3-mercaptopropionic acid, dodecanethiol, thioacetic acid; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, perchloroethylene; sodium phosphinate 1 water Examples thereof include phosphinic acid salts such as hydrates. Of these, thiols are preferably used.
- the content is preferably 0.1% by mass or more and 10% by mass or less based on the vinyl ester monomer.
- an aldehyde such as acetaldehyde or propionaldehyde
- the double bond tends to be chained from the end of PVA by heat treatment after saponification, and the absorbance (a2) at a wavelength of 320 nm of a 0.1 mass% aqueous solution. ) May be difficult to be less than 0.030.
- the value of the weight average molecular weight / number average molecular weight (Mw / Mn) of the PVA (A) is not particularly limited, but is usually 10 or less and preferably 6 or less.
- the block character of the residual vinyl ester group of the PVA (A) is not particularly limited, but is usually 1.0 or less, and preferably 0.8 or less from the viewpoint of the polymerization stability of the vinyl monomer.
- PVA (B) In the present invention, PVA (B) having an absorbance (b1) at a wavelength of 280 nm of an aqueous solution having a concentration of 0.1% by mass of 0.25 or more and an absorbance (b2) at a wavelength of 320 nm of the aqueous solution of 0.030 or more. , And preferably used in combination with PVA (A).
- the dispersion stabilizer of the present invention preferably further contains PVA (B).
- the absorbance (b1) is more preferably 0.30 or more, and further preferably 0.40 or more.
- the absorbance (b2) is more preferably 0.050 or more, and further preferably 0.15 or more.
- absorbance (b1) is less than 0.25 or (b2) is less than 0.030, it is caused by insufficient adsorption of PVA (B) to vinyl monomer at the initial stage of suspension polymerization. And since the vinyl-type resin particle obtained becomes coarse, there exists a possibility that bulk specific gravity may fall.
- the saponification degree of the PVA (B) is preferably 65 mol% or more and 82 mol% or less from the viewpoint of performance as a dispersion stabilizer.
- the saponification degree is more preferably 68 mol% or more.
- the saponification degree is more preferably 80 mol% or less, and further preferably 77 mol% or less.
- the degree of saponification of the above PVA (B) can be obtained by measuring according to JIS-K6726 (1994).
- the PVA (B) preferably has a viscosity average polymerization degree of 500 or more and 1500 or less.
- the viscosity average degree of polymerization is more preferably 600 or more.
- the viscosity average polymerization degree is more preferably 1200 or less, and further preferably 1000 or less.
- the viscosity average degree of polymerization of the PVA (B) was determined by measuring the intrinsic viscosity in an acetone solution (Akio Nakajima) after saponifying the PVA substantially completely and then acetylating it to a vinyl ester polymer. : Polymer chemistry 6 (1949)).
- PVA (A) and PVA (B) as a dispersion stabilizer, and the mass ratio (A / B) of PVA (A) and PVA (B) is 6 / It is preferably 94 or more and 60/40 or less, and more preferably 10/90 or more and 50/50 or less.
- PVA (A) and PVA (B) may be dissolved simultaneously and used separately or charged separately. Further, PVA (A) or PVA (B) may be dissolved using an organic solvent or the like.
- additives may be added as long as the gist of the present invention is not impaired.
- the additive include PVA usually used for suspension polymerization in an aqueous medium such as a low saponification degree PVA used for increasing the plasticizer absorbability of the obtained vinyl resin; methyl cellulose, hydroxyethyl cellulose Water-soluble cellulose ethers such as hydroxypropylcellulose and hydroxypropylmethylcellulose; water-soluble polymers such as gelatin; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan trioleate, glycerin tristearate, and ethylene oxide propylene oxide block copolymer; polyoxyethylene Water-soluble emulsifiers such as sorbitan monolaurate, polyoxyethylene glycerol oleate, sodium laurate; polymerization regulators such as aldehydes, halogenated hydrocarbons, mercaptans Ph
- a preferred embodiment of the present invention is a method for producing a vinyl resin in which a vinyl monomer is suspension-polymerized in an aqueous medium using the dispersion stabilizer.
- vinyl monomers used in the method for producing a vinyl resin of the present invention 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; styrene; acrylonitrile; vinylidene chloride; vinyl ether and the like.
- vinyl monomers vinyl chloride is particularly preferable.
- the production method of the present invention is particularly preferably used in the case of suspension polymerization of vinyl chloride alone or together with vinyl chloride and a monomer capable of copolymerizing with vinyl chloride.
- 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.
- 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-hexylperoxypivalate, ⁇ -cumylperoxyneodecanate; 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-dimethylvaleronit
- water-soluble polymerization initiator examples include potassium persulfate, ammonium persulfate, hydrogen peroxide, and cumene hydroperoxide. These oil-soluble or water-soluble polymerization initiators can be used alone or in combination of two or more.
- 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 aqueous medium used for the suspension polymerization of the vinyl monomer may contain a water-soluble organic solvent as long as the effect of the present invention is not impaired.
- the amount of water in the aqueous medium is preferably 90% by mass or more, and the aqueous solvent is more preferably water.
- the mass ratio of the vinyl monomer to be charged and the aqueous medium is not particularly limited. In general, the lower the ratio of the vinyl monomer to the aqueous medium, the more stable the polymerization, but the lower the productivity. The higher the ratio of the vinyl monomer to the aqueous medium, the higher the productivity. , Polymerization becomes unstable.
- the mass ratio of the vinyl monomer to the aqueous medium (vinyl monomer / aqueous medium) is preferably 0.57 to 1.25, more preferably 0. .57 to 1.11.
- the mass ratio (vinyl monomer / aqueous medium) is less than 0.57, the productivity of the resulting vinyl resin may be lowered.
- the mass ratio (vinyl monomer / aqueous medium) exceeds 1.25, the polymerization stability is lowered and coarse resin particles may be generated.
- the mass ratio of the vinyl monomer to the aqueous medium is preferably 0.75 or more.
- a method for producing a vinyl resin in which a vinyl monomer is suspension-polymerized in an aqueous medium using PVA (A) and PVA (B) is also a preferred embodiment of the present invention.
- the above-described dispersion stabilizer of the present invention is preferably used.
- part and % represent parts by mass and mass%, respectively.
- the PVA obtained by the following production examples was evaluated according to the following method.
- Viscosity average polymerization degree of PVA The viscosity average degree of polymerization of PVA is determined by the equation of Nakajima (Akio Nakajima: Polymer Chemistry) from the measurement of the intrinsic viscosity in acetone solution after acetylating the PVA substantially completely and then acetylating it to a vinyl ester polymer. 6 (1949)).
- the saponification reaction was started in a methanol solution having a PVAc concentration of 30% and a temperature of 40 ° C. using sodium hydroxide as a saponification catalyst at a molar ratio of 0.0047 to PVAc. Since gelation occurred after 23 minutes, the contents were once taken out, pulverized using a mixer, returned to 40 ° C., and reacted so that the reaction time at 40 ° C. was 1 hour in total. After completion of the reaction, drying under reduced pressure to remove methanol, followed by heat treatment at 80 ° C. for 1 hour, then 90 ° C. for 1 hour, and then 120 ° C. for 4 hours under normal pressure and air atmosphere, and PVA (A1) Obtained.
- the viscosity average polymerization degree of PVA (A1) is 1550, the saponification degree is 80 mol%, the absorbance (a1) at a wavelength of 280 nm and the absorbance (a2) at 320 nm of an aqueous solution having a concentration of 0.1% are 0.008, 0.004, respectively.
- the value of YI was 41.
- PVA Amount of vinyl acetate and methanol, amount of initiator used during polymerization, polymerization conditions such as target polymerization rate, saponification conditions such as amount of sodium hydroxide, time PVA (A2 to A7, A9, A12 to A14) shown in Table 1 was produced in the same manner as PVA (A1) except that the heat treatment conditions such as temperature and temperature were changed.
- PVA (A8, A10) In the same manner as described in JP-A-8-283313, acetaldehyde was used as a chain transfer agent at the time of polymerization, and the degree of polymerization was controlled by the amount used, and charged with vinyl acetate and methanol The same as PVA (A1) except that the amount, the amount of initiator used during polymerization, the polymerization conditions such as the target polymerization rate, the saponification conditions such as the amount of sodium hydroxide, and the heat treatment conditions such as time and temperature were changed. PVA (A8, A10) shown in Table 1 was produced.
- PVA (A11) In the manufacturing process of PVA (A1), what was obtained without performing heat treatment is PVA (A11). PVA (A11) was obtained in the same manner as PVA (A1) except that no heat treatment was performed.
- Example 1 Prepare 100 parts of deionized aqueous solution in which PVA (A1) in an amount of 880 ppm relative to vinyl chloride is charged in a 5 L autoclave, and add deionized water so that the total amount of deionized water is 1200 parts. Prepared. Next, 0.65 parts of 70% toluene solution of cumylperoxyneodecanoate and 1.05 parts of 70% toluene solution of t-butylperoxyneodecanoate were charged into the autoclave. Nitrogen was introduced into the autoclave so that the pressure became 0.2 MPa, and then purged with nitrogen was performed a total of 5 times.
- Example 2 Instead of using a deionized aqueous solution of PVA (A1), a deionized aqueous solution in which PVA (A1) (240 ppm with respect to vinyl chloride) and PVA (B1) (640 ppm with respect to vinyl chloride) were used was used. In the same manner as in Example 1, suspension polymerization of vinyl chloride was performed to obtain vinyl chloride resin particles. Table 2 shows the evaluation results of the vinyl chloride resin particles.
- Examples 3-14 Except having changed the kind and usage-amount of PVA (A) and PVA (B) as shown in Table 1, suspension polymerization of vinyl chloride was performed like Example 2, and the vinyl chloride resin particle was obtained.
- Table 2 shows the evaluation results of the vinyl chloride resin particles.
- Comparative Examples 1-6 Except that the types and amounts of PVA (A) and PVA (B) used were changed as shown in Table 1, suspension polymerization of vinyl chloride was carried out in the same manner as in Example 2 to obtain vinyl chloride resin particles. It was. Table 2 shows the evaluation results of the vinyl chloride resin particles.
- the agent When the agent is used, the polymerization is very stable even under conditions where the proportion of the vinyl monomer is high and the composition tends to be unstable, and vinyl chloride resin particles with high bulk specific gravity are obtained with little formation of coarse particles.
- the dispersion stabilizer composed of PVA (A) and PVA (B) was more excellent in the above properties (Examples 2 to 14). Therefore, the industrial usefulness of the production method of the present invention is extremely high.
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Abstract
Description
[1]濃度0.1質量%水溶液の波長280nmでの吸光度(a1)が0.25未満、前記水溶液の波長320nmでの吸光度(a2)が0.030未満、けん化度が68モル%以上98モル%以下、粘度平均重合度が1500超4500未満、かつ粉末形状でのYI値が5以上であるビニルアルコール系重合体(A)を含有する懸濁重合用分散安定剤;
[2]さらに、濃度0.1質量%水溶液の波長280nmでの吸光度(b1)が0.25以上、前記水溶液の波長320nmでの吸光度(b2)が0.030以上、けん化度が65モル%以上82モル%以下、かつ粘度平均重合度が500以上1500以下であるビニルアルコール系重合体(B)を含有する[1]に記載の懸濁重合用分散安定剤;
[3]ビニルアルコール系重合体(A)およびビニルアルコール系重合体(B)の質量比(A/B)が6/94以上60/40以下である[2]に記載の懸濁重合用分散安定剤;
[4][1]~[3]のいずれかに記載の懸濁重合用分散安定剤を用いて水性媒体中でビニル系単量体を懸濁重合するビニル系樹脂の製造方法;
[5]懸濁重合に使用するビニル系単量体と水性媒体との質量比(ビニル系単量体/水性媒体)が0.75以上である[4]に記載のビニル系樹脂の製造方法;
[6]ビニル系単量体が塩化ビニルである[4]または[5]に記載のビニル系樹脂の製造方法;
に関する。
本発明の懸濁重合用分散安定剤は、濃度0.1質量%水溶液の波長280nmでの吸光度(a1)が0.25未満、前記水溶液の波長320nmでの吸光度(a2)が0.030未満、けん化度が68モル%以上98モル%以下、粘度平均重合度が1500超4500未満、かつ粉末形状でのYI値が5以上であるビニルアルコール系重合体(A)を含有するものである。
本発明で用いられるPVA(A)は、濃度0.1質量%水溶液の波長280nmでの吸光度(a1)が0.25未満であり、かつ前記水溶液の波長320nmでの吸光度(a2)が0.030未満である。上記吸光度(a1)は0.20以下が好ましく、0.15以下がより好ましい。上記吸光度(a2)は0.020以下が好ましく、0.015以下がより好ましい。上記吸光度(a1)が0.25以上、または(a2)が0.030以上の場合、PVA自体が熱劣化していて、十分な性能が得られないおそれがある。
本発明では、濃度0.1質量%水溶液の波長280nmでの吸光度(b1)が0.25以上、かつ前記水溶液の波長320nmでの吸光度(b2)が0.030以上であるPVA(B)を、PVA(A)と併用して使用することが好ましい。本発明の分散安定剤は、さらに、PVA(B)を含有することが好ましい。上記吸光度(b1)は0.30以上がより好ましく、0.40以上がさらに好ましい。また、上記吸光度(b2)は0.050以上がより好ましく、0.15以上がさらに好ましい。吸光度(b1)が0.25未満、または(b2)が0.030未満である場合、懸濁重合の初期段階でPVA(B)のビニル系単量体への吸着力が足りないことに起因して、得られるビニル系樹脂粒子が粗粒化するため、かさ比重が低下するおそれがある。
PVA(A)、PVA(B)以外に、本発明の趣旨を損なわない範囲で、その他の各種添加剤を添加してもよい。上記添加剤としては、例えば、得られるビニル系樹脂の可塑剤吸収性を高めるために用いられる低けん化度PVA等の水性媒体中で懸濁重合する際に通常使用されるPVA;メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロースなどの水溶性セルロースエーテル;ゼラチンなどの水溶性ポリマー;ソルビタンモノラウレート、ソルビタントリオレート、グリセリントリステアレート、エチレンオキシドプロピレンオキシドブロックコポリマーなどの油溶性乳化剤;ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレングリセリンオレート、ラウリン酸ナトリウムなどの水溶性乳化剤;アルデヒド類、ハロゲン化炭化水素類、メルカプタン類などの重合調節剤;フェノール化合物、イオウ化合物、N-オキサイド化合物などの重合禁止剤;pH調整剤;架橋剤;防腐剤;防黴剤、;ブロッキング防止剤、;消泡剤が挙げられる。その添加量については特に制限は無いが、ビニル系単量体100質量部に対して1.0質量部以下が好ましい。
前記分散安定剤を用いて水性媒体中でビニル系単量体を懸濁重合するビニル系樹脂の製造方法が本発明の好適な実施態様である。本発明のビニル系樹脂の製造方法で用いられるビニル系単量体としては、塩化ビニル等のハロゲン化ビニル;酢酸ビニル、プロピオン酸ビニル等のビニルエステル;アクリル酸、メタクリル酸、これらのエステルおよび塩;マレイン酸、フマル酸、これらのエステルおよび無水物;スチレン;アクリロニトリル;塩化ビニリデン;ビニルエーテル等が挙げられる。これらのビニル系単量体の中でも、特に塩化ビニルが好ましい。本発明の製造方法は、塩化ビニルを単独で、または塩化ビニルおよび塩化ビニルと共重合することが可能な単量体を共に懸濁重合する際に特に好適に用いられる。塩化ビニルと共重合することができる単量体としては、酢酸ビニル、プロピオン酸ビニルなどのビニルエステル;(メタ)アクリル酸メチル、(メタ)アクリル酸エチルなどの(メタ)アクリル酸エステル;エチレン、プロピレンなどのα-オレフィン;無水マレイン酸、イタコン酸などの不飽和ジカルボン酸類;アクリロニトリル;スチレン;塩化ビニリデン;ビニルエーテル等が挙げられる。
PVAの粘度平均重合度は、PVAを実質的に完全にけん化した後、アセチル化してビニルエステル系重合体とした後、アセトン溶液中の極限粘度の測定から中島の式(中島章夫:高分子化学6(1949))を用いて算出した。
PVAのけん化度は、JIS K6726(1994)記載の方法で求めた。
0.1質量%のPVA水溶液を調整し島津製作所社製吸光光度計「UV2100」を用いて波長280nmおよび320nmの吸光度(光路長10mm)を測定した。
PVAの色相:スガ試験機製カラーメーター「SM-T-H1」にて粉体測定用セルを用いて測定した。
PVA(A1)の製造
酢酸ビニル(以下、VAcと略すことがある)1400部、メタノール600部を重合缶に仕込み、窒素置換後加熱して沸点まで昇温させた後、VAcに対して0.05%のアゾビスイソブチロニトリル、メタノール10部を加え重合を行った。重合率が40%となったところで重合を停止し、減圧下、メタノールを添加しながら残存するVAcをメタノールとともに系外に追い出し、ポリビニルアセテート(以下PVAcと略す)のメタノール溶液(濃度40%)を得た。次いで、PVAc濃度30%、温度40℃のメタノール溶液中で、PVAcに対してモル比0.0047の割合で水酸化ナトリウムをけん化触媒として用いてけん化反応を開始した。23分後ゲル化したため、一旦内容物を取り出した後、ミキサーを用いて粉砕し、再度40℃に戻し、40℃での反応時間が計1時間となるように反応させた。反応終了後、減圧下乾燥を行いメタノールを除去したのち、常圧、空気雰囲気下、80℃で1時間、次いで90℃で1時間、さらに120℃で4時間熱処理を行い、PVA(A1)を得た。PVA(A1)の粘度平均重合度は1550、けん化度は80モル%、濃度0.1%水溶液の波長280nmにおける吸光度(a1)及び320nmにおける吸光度(a2)はそれぞれ0.008、0.004、YIの値は41であった。
酢酸ビニルおよびメタノールの仕込み量、重合時に使用する開始剤使用量、目標重合率等の重合条件、水酸化ナトリウムの量等のけん化条件、時間や温度等の熱処理条件を変更したこと以外は、PVA(A1)と同様にして表1に示すPVA(A2~A7、A9、A12~A14)を製造した。
特開平8-283313号公報に記載方法と同様にして、重合時にアセトアルデヒドを連鎖移動剤として用い、その使用量によって重合度をコントロールしたこと、酢酸ビニルおよびメタノールの仕込み量、重合時に使用する開始剤使用量、目標重合率等の重合条件、水酸化ナトリウムの量等のけん化条件、時間や温度等の熱処理条件を変更したこと以外は、PVA(A1)と同様にして表1に示すPVA(A8、A10)を製造した。
PVA(A1)の製造工程において、熱処理を行わずに得たものがPVA(A11)である。熱処理を行わなかったこと以外はPVA(A1)と同様にしてPVA(A11)を得た。
特開平8-283313号公報に記載方法と同様にして、重合時に用いるアセトアルデヒドの使用量、酢酸ビニルおよびメタノールの仕込み量、重合時に使用する開始剤使用量、目標重合率等の重合条件、水酸化ナトリウムの量等のけん化条件、時間や温度等の熱処理条件を変更したこと以外は、PVA(A8)と同様にして表1に示すPVA(B1~B3)を製造した。
容量5Lのオートクレーブに塩化ビニルに対して880ppmとなる量のPVA(A1)が溶解した脱イオン水溶液を100部仕込み、さらに脱イオン水の合計が1200部となるように脱イオン水を追加して仕込んだ。次いで、クミルパーオキシネオデカノエートの70%トルエン溶液0.65部およびt-ブチルパーオキシネオドデカネートの70%トルエン溶液1.05部をオートクレーブに仕込んだ。オートクレーブ内に圧力0.2MPaとなるように窒素を導入し、その後窒素のパージを行う操作を計5回行い、オートクレーブ内を十分に窒素置換して酸素を除いた後、塩化ビニル940部を仕込んだ。オートクレーブ内の内容物を57℃に昇温して撹拌下で塩化ビニル単量体の重合を開始した。重合開始時におけるオートクレーブ内の圧力は0.80MPaであった。重合を開始してから約3.5時間経過後、オートクレーブ内の圧力が0.70MPaとなった時点で重合を停止し、未反応の塩化ビニル単量体を除去した後、重合反応物を取り出し、65℃にて16時間乾燥を行い、塩化ビニル樹脂粒子を得た。以下に示す方法で得られた粒子を評価した。
得られた塩化ビニル樹脂粒子について、(1)平均粒子径、(2)粒度分布、(3)かさ比重を以下の方法にしたがって評価した。評価結果を表2に示す。
タイラーメッシュ基準の金網を使用して、JIS Z8815に記載の乾式篩法により粒度分布を測定した。その結果からRosin-Rammlerプロットを用いて平均粒子径を算出した。評価結果を表2に示す。
得られた塩化ビニル樹脂粒子中の、JIS標準篩い42メッシュオンの樹脂粒子の含有量を質量%で表示した。評価結果を表2に示す。
A:0.5%未満
B:0.5%以上1%未満
C:1%以上
得られた塩化ビニル樹脂粒子中の、JIS標準篩い60メッシュオンの樹脂粒子の含有量を質量%で表示した。
A:5%未満
B:5%以上10%未満
C:10%以上
なお、42メッシュオンの樹脂粒子の含有量および60メッシュオンの樹脂粒子の含有量はともに、値が小さいほど粗大粒子が少なくて粒度分布がシャープであり、重合安定性に優れていることを示している。
JIS K6721に従って塩化ビニル樹脂のかさ比重を測定した。評価結果を表2に示す。
PVA(A1)の脱イオン水溶液の代わりに、PVA(A1)(塩化ビニルに対して240ppm)とPVA(B1)(塩化ビニルに対して640ppm)とが溶解した脱イオン水溶液を用いたこと以外は実施例1と同様にして塩化ビニルの懸濁重合を行い、塩化ビニル樹脂粒子を得た。塩化ビニル樹脂粒子の評価結果を表2に示す。
PVA(A)、PVA(B)の種類および使用量を表1に示すとおりに変更したこと以外は実施例2と同様にして塩化ビニルの懸濁重合を行い、塩化ビニル樹脂粒子を得た。塩化ビニル樹脂粒子の評価結果を表2に示す。
使用するPVA(A)、PVA(B)の種類および使用量を表1に示すとおりに変更したこと以外は実施例2と同様にして塩化ビニルの懸濁重合を行い、塩化ビニル樹脂粒子を得た。塩化ビニル樹脂粒子の評価結果を表2に示す。
Claims (6)
- 濃度0.1質量%水溶液の波長280nmでの吸光度(a1)が0.25未満、前記水溶液の波長320nmでの吸光度(a2)が0.030未満、けん化度が68モル%以上98モル%以下、粘度平均重合度が1500超4500未満、かつ粉末形状でのYI値が5以上であるビニルアルコール系重合体(A)を含有する懸濁重合用分散安定剤。
- さらに、濃度0.1質量%水溶液の波長280nmでの吸光度(b1)が0.25以上、前記水溶液の波長320nmでの吸光度(b2)が0.030以上、けん化度が65モル%以上82モル%以下、かつ粘度平均重合度が500以上1500以下であるビニルアルコール系重合体(B)を含有する請求項1に記載の懸濁重合用分散安定剤。
- ビニルアルコール系重合体(A)およびビニルアルコール系重合体(B)の質量比(A/B)が6/94以上60/40以下である請求項2に記載の懸濁重合用分散安定剤。
- 請求項1~3のいずれかに記載の懸濁重合用分散安定剤を用いて水性媒体中でビニル系単量体を懸濁重合するビニル系樹脂の製造方法。
- ビニル系単量体と水性媒体との質量比(ビニル系単量体/水性媒体)が0.75以上である請求項4に記載のビニル系樹脂の製造方法。
- ビニル系単量体が塩化ビニルである請求項4または5に記載のビニル系樹脂の製造方法。
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WO2018194122A1 (ja) * | 2017-04-21 | 2018-10-25 | 株式会社クラレ | ビニル化合物の懸濁重合用分散安定剤及びその製造方法、並びにビニル系重合体の製造方法 |
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JP7144421B2 (ja) | 2017-08-08 | 2022-09-29 | 株式会社クラレ | 懸濁重合用分散安定剤及びそれを用いたビニル系重合体の製造方法 |
US11434310B2 (en) | 2017-08-08 | 2022-09-06 | Kuraray Co., Ltd. | Dispersion stabilizer for suspension polymerization and method for producing vinyl polymer using same |
US11365268B2 (en) | 2018-07-27 | 2022-06-21 | Denka Company Limited | Method for producing polyvinyl alcohol |
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WO2023008438A1 (ja) * | 2021-07-30 | 2023-02-02 | 株式会社クラレ | ポリビニルアルコール系樹脂、懸濁重合用分散剤、ビニル系重合体粒子の製造方法、及びポリビニルアルコール系樹脂の製造方法 |
Also Published As
Publication number | Publication date |
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EP3219735A4 (en) | 2018-08-22 |
JPWO2016076349A1 (ja) | 2017-08-24 |
TW201623340A (zh) | 2016-07-01 |
EP3219735A1 (en) | 2017-09-20 |
JP6704350B2 (ja) | 2020-06-03 |
EP3219735B1 (en) | 2022-03-16 |
TWI669318B (zh) | 2019-08-21 |
US9834629B1 (en) | 2017-12-05 |
US20170335030A1 (en) | 2017-11-23 |
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