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WO2019198764A1 - Composition d'alcool polyvinylique ainsi qu'application de celle-ci, et procédé de fabrication de résine à base de vinyle - Google Patents

Composition d'alcool polyvinylique ainsi qu'application de celle-ci, et procédé de fabrication de résine à base de vinyle Download PDF

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Publication number
WO2019198764A1
WO2019198764A1 PCT/JP2019/015666 JP2019015666W WO2019198764A1 WO 2019198764 A1 WO2019198764 A1 WO 2019198764A1 JP 2019015666 W JP2019015666 W JP 2019015666W WO 2019198764 A1 WO2019198764 A1 WO 2019198764A1
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composition
vinyl
salt
mol
group
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English (en)
Japanese (ja)
Inventor
忠仁 福原
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2020513433A priority Critical patent/JP7333777B2/ja
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Anticipated expiration legal-status Critical
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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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • C08F8/14—Esterification
    • 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

Definitions

  • Polyvinyl alcohol (hereinafter sometimes abbreviated as “PVA”) has been used in various products such as dispersion stabilizers for suspension polymerization of vinyl compounds, coating agents, adhesives, polarizing films, water-soluble films, pharmaceuticals, and cosmetics. Used for applications. In addition, it is known that various performances are improved due to the presence of a reactive group such as a double bond in PVA, or a special effect is exhibited.
  • a dispersion stabilizer for suspension polymerization of a vinyl compound As an application that requires the storage stability of PVA, a dispersion stabilizer for suspension polymerization of a vinyl compound can be mentioned.
  • PVA having a double bond As a dispersion stabilizer for suspension polymerization of a vinyl compound, the polymerization reaction of the vinyl compound is stabilized (Patent Documents 1 and 2).
  • Patent Document 1 discloses a suspension polymerization containing a polyvinyl alcohol polymer having a double bond in a side chain obtained by acetalizing a polyvinyl alcohol polymer with a monoaldehyde having an olefinic unsaturated double bond. Dispersion stabilizers are described.
  • Patent Document 2 discloses a dispersion stabilizer comprising a polyvinyl alcohol polymer having a double bond in a side chain, obtained by esterifying a polyvinyl alcohol polymer with a carboxylic acid having an unsaturated double bond or a salt thereof. Are listed.
  • polymerization stability means that the dispersion of droplets made of a vinyl compound is good during suspension polymerization, and as a result, particles of vinyl resin having a uniform diameter and suppressing coarsening are obtained. It means that it is obtained.
  • composition (D) in which the modified polyvinyl alcohol (A) has a methacryloyl group in the side chain is also a preferred embodiment of the present invention.
  • a composition (D) in which the unsaturated monocarboxylic acid or a salt thereof (B) is methacrylic acid or sodium methacrylate is also a preferred embodiment of the present invention.
  • a composition (D) further comprising at least one compound (C) selected from the group consisting of xyl radical (C3) is also a preferred embodiment of the present invention.
  • a method for producing a vinyl resin including a step of suspension polymerization of a vinyl compound in the presence of the composition (D) is also a preferred embodiment of the present invention.
  • a method for producing a vinyl resin using a polyvinyl alcohol (F) having a viscosity average polymerization degree of 1500 or more and 3500 or less and a saponification degree of 78 mol% or more and less than 92 mol% is also a preferred embodiment of the present invention.
  • composition (D) in the present invention comprises a modified PVA (A) and at least one unsaturated monocarboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, sodium acrylate and sodium methacrylate or a salt thereof ( B).
  • the production method of the composition (D) is not particularly limited.
  • a method of reacting a derivative (ii) a method of adding an unsaturated monocarboxylic acid or a salt thereof (B) after reacting polyvinyl alcohol (E) with an unsaturated carboxylic acid or a derivative thereof as an esterifying agent.
  • B reacting polyvinyl alcohol
  • the heating temperature is preferably 80 to 180 ° C.
  • the heating time is appropriately set in relation to the heating temperature, but is usually 10 minutes to 24 hours.
  • polyvinyl alcohol (E) is PVA which does not have a double bond in a side chain (hereinafter, may be referred to as “PVA (E)”).
  • a mixed powder is obtained by mixing PVA (E) with an unsaturated carboxylic acid or derivative thereof as an esterifying agent.
  • a method of heating the obtained mixed powder is preferred.
  • an esterification reaction can be advanced, suppressing the progress of an undesirable crosslinking reaction.
  • the modified PVA (A) can be obtained, and a powder comprising the composition (D) can be obtained together with the unsaturated monocarboxylic acid or its salt (B).
  • Modified PVA (A) Modified PVA (A) is synthesized by reacting PVA (E) with an esterifying agent, but PVA (E) is a vinyl ester monomer that is bulk polymerization, solution polymerization, suspension polymerization, emulsion weight It can be produced by a conventionally known method such as a combination method or a dispersion polymerization method. Polymerization methods that are preferable from an industrial viewpoint are the solution polymerization method, the emulsion polymerization method, and the dispersion polymerization method. In the polymerization operation, any one of a batch method, a semi-batch method and a continuous method can be adopted.
  • vinyl ester monomer used for polymerization examples include vinyl acetate, vinyl formate, vinyl propionate, vinyl caprylate, and vinyl versatate. Among these, vinyl acetate is preferred from the industrial viewpoint.
  • the vinyl ester monomer When the vinyl ester monomer is polymerized, the vinyl ester monomer may be copolymerized with another monomer as long as the gist of the present invention is not impaired.
  • 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-acrylate.
  • Acrylic acid esters such as propyl, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and salts thereof; methyl methacrylate, Methacrylic acid such as ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate Acid ester Acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide, acrylamide propane sulfonic acid and
  • Chain transfer agents include aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, and benzaldehyde; ketones such as acetone, methyl ethyl ketone, hexanone, and cyclohexanone; mercaptans such as 2-hydroxyethanethiol and dodecyl mercaptan; trichloroethylene, perchloroethylene Halogenated hydrocarbons such as 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 polyvinyl ester, but is generally 0.1 to 10 mass relative to the vinyl ester monomer. % Is desirable.
  • the modified PVA (A) has 0.01 to 1.50 mol% of acryloyl group or methacryloyl group in the side chain.
  • the amount of modification by the acryloyl group or methacryloyl group (hereinafter sometimes abbreviated as “introduction modification group amount”) can be determined by the content of double bonds in the acryloyl group or methacryloyl group.
  • the double bond means a carbon-carbon double bond.
  • the amount of introduced modification group is preferably 0.03 mol% or more.
  • the amount of the introduced modifying group exceeds 1.50 mol%, the production is difficult and the gelation easily occurs, and the performance when left for a long time after the production is lowered.
  • the composition (D) is used as a dispersion stabilizer for suspension polymerization of a vinyl compound, the resulting vinyl-based resin has low plasticizer absorbability and increases fish eyes.
  • the amount of the introduced modifying group is preferably 1.3 mol% or less, and more preferably 1 mol% or less.
  • Examples of the unsaturated carboxylic acid or derivative thereof used for esterification of PVA (E) include acrylic acid or a salt thereof, methacrylic acid or a salt thereof, methacrylic anhydride, acrylic acid anhydride, alkyl acrylate ester, and alkyl methacrylate ester. Can be mentioned. Unsaturated carboxylic acid or its derivative (s) can be used alone or in combination of two or more.
  • the viscosity average degree of polymerization is a value obtained by measurement according to JIS-K6726 (1994). Specifically, when the saponification degree is less than 99.5 mol%, the intrinsic viscosity [ ⁇ ] (liter / liter) measured in water at 30 ° C. is used for the saponified PVA until the saponification degree is 99.5 mol% or more.
  • the lower limit of the saponification degree of the modified PVA (A) is preferably 35 mol% or more, and the upper limit is preferably 57 mol% or less, more preferably 54 mol% or less.
  • the saponification degree is a value obtained by measurement according to JIS-K6726 (1994).
  • composition (D) of the present invention comprises a compound having a conjugated double bond and having two or more hydroxyl groups bonded to carbon atoms constituting the conjugated double bond, or a salt thereof or an oxide thereof (C1). It is preferable that the compound further contains at least one compound (C) selected from the group consisting of: alkoxyphenol (C2); and cyclic nitroxyl radical (C3).
  • a compound having a conjugated double bond and having two or more hydroxyl groups bonded to carbon atoms constituting the conjugated double bond, or a salt or oxide (C1) thereof, is defined as conjugated double as defined herein.
  • the bond includes conjugation by a carbon-carbon double bond, conjugation by a carbon-heteroatom double bond, and conjugation by an aromatic compound.
  • Examples of a compound having a conjugated double bond and having two or more hydroxyl groups bonded to carbon atoms constituting the conjugated double bond, or a salt thereof or an oxide thereof (C1) include catechol, t-butyl Hydroquinone, 2,6-di-t-butylhydroquinone, pyrogallol, 1,3,5-trihydroxybenzene, hexahydroxybenzene; gallic acid or salts thereof; methyl gallate, ethyl gallate, propyl gallate, octyl gallate Catechins such as epicatechin, epigallocatechin and epigallocatechin-3-gallate; ascorbic acid or salts thereof; benzoquinone; dehydroascorbic acid and the like.
  • a compound having two or more hydroxyl groups bonded to carbon atoms constituting a conjugated double bond is preferable, and a compound having two or more phenolic hydroxyl groups is more preferable.
  • the alkoxyphenol (C2) in the present invention refers to a compound in which at least one hydrogen atom of the benzene ring is substituted with an alkoxy group and at least one is substituted with a hydroxyl group.
  • the other hydrogen atom may be substituted with an alkyl group such as a methyl group or an ethyl group or a halogen group, and the number or bonding position thereof is not limited.
  • the carbon number of the alkoxy group is usually 10 or less, preferably 8 or less, more preferably 6 or less, further preferably 4 or less, and particularly preferably 2 or less.
  • the carbon chain of the alkoxy group may be linear or branched, but is preferably linear from the viewpoint of availability. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and among them, a methoxy group is preferable.
  • the alkoxyphenol (C2) used in the present invention is preferably a compound in which one hydrogen atom of the benzene ring is substituted with an alkoxy group and one is substituted with a hydroxyl group.
  • the bonding position of the alkoxy group is not particularly limited, but from the viewpoint of availability, the ortho position or the para position is preferable, and the para position is more preferable.
  • alkoxyphenol (C2) examples include methoxyphenol, ethoxyphenol, propoxyphenol, and butoxyphenol. Among these, methoxyphenol is preferable from the viewpoint of availability.
  • the hetero atom constituting the ring include an oxygen atom, a phosphorus atom, and a sulfur atom in addition to the nitrogen atom.
  • the number of atoms forming the ring is usually 5 or 6.
  • Substituents such as an alkyl group, a hydroxyl group, a carboxyl group, a sulfo group, and a halogen group may be bonded to the atoms forming the ring.
  • the number of substituents and the bonding position of the substituents are not particularly limited, and a plurality of substituents may be bonded to the same or different atoms.
  • the cyclic nitroxyl radical is preferably 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) or a derivative thereof.
  • TEMPO derivative 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl is preferably used.
  • the compound (C) is a compound having a conjugated double bond and having two or more hydroxyl groups bonded to the carbon atoms constituting the conjugated double bond, or a salt thereof or an oxide thereof ( Or an alkoxyphenol (C2), a compound having a conjugated double bond and having two or more hydroxyl groups bonded to carbon atoms constituting the conjugated double bond, or a salt thereof or an oxide thereof ( C1) is more preferred.
  • composition (D) of the present invention is used for various applications. Examples thereof are given below, but the invention is not limited to them.
  • Dispersant use Dispersion stabilizers for organic and inorganic pigments such as paints and adhesives, and dispersion stabilizers for suspension polymerization of various vinyl compounds such as vinyl chloride, vinylidene chloride, styrene, (meth) acrylate, and vinyl acetate.
  • Coating agent Paper coating agent, sizing agent, textile processing agent, leather finish agent, paint, antifogging agent, metal corrosion inhibitor, galvanizing brightener, antistatic agent
  • Adhesive applications Adhesives, adhesives, rewet adhesives, various binders, additives for cement and mortar
  • Emulsifier applications Emulsifiers for emulsion polymerization, post-emulsifiers such as bitumen
  • Flocculant applications Suspension in water And coagulants of materials and dissolved materials, metal flocculants
  • Paper processing applications paper strength enhancers, oil and solvent resistance imparting agents, smoothness improvers, surface gloss improvement aids, sealants, barrier agents, light resistance Imparting agent, waterproofing agent, dye / developer dispersant, Adhesion improver, binder
  • Agricultural applications Agricultural binders, Agrochemical spreading agents, Agricultural coatings, Soil improvers, Erosion inhibitors, Agrochemical dispersants (8) Medical and cosmetic applications:
  • composition (D) of the present invention is a dispersion stabilizer for suspension polymerization of a vinyl compound containing the composition (D).
  • the composition (D) of the present invention has high performance even when stored for a long period of time, stabilizes the polymerization reaction, and reduces the formation of coarse particles. Further, a vinyl resin having high plasticizer absorbability and less fish eye can be obtained.
  • the dispersion stabilizer for suspension polymerization may contain various additives as long as the gist of the present invention is not impaired.
  • the additives include polymerization regulators such as aldehydes, halogenated hydrocarbons and mercaptans; polymerization inhibitors such as phenolic compounds, sulfur compounds and N-oxide compounds; pH adjusting agents; cross-linking agents; An antifungal agent, an antiblocking agent, an antifoaming agent, a compatibilizing agent, and the like. 10 mass% or less is preferable with respect to the total amount of a composition (D), and, as for content of the various additives in the dispersion stabilizer for suspension polymerization, 5 mass% or less is more preferable.
  • a preferred embodiment of the present invention is a method for producing a vinyl resin in which a vinyl compound is suspension-polymerized in the presence of the composition (D) of the present invention.
  • a preferred embodiment of the present invention is a polyvinyl alcohol having a viscosity average polymerization degree of 1500 or more and 3500 or less and a saponification degree of 78 mol% or more and less than 92 mol% in the presence of the composition (D) of the present invention.
  • This is a method for producing a vinyl resin in which (F) is used in combination and a vinyl compound is subjected to suspension polymerization.
  • Examples of the vinyl compound 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 chloride alone or a combination of monomers that can be copolymerized with vinyl chloride and vinyl chloride is preferable.
  • 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 and propylene ⁇ -olefin; unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid; acrylonitrile; styrene; vinylidene chloride; vinyl ether and the like.
  • the polymerization temperature is not particularly limited, and may be about 20 ° C. or over 90 ° C.
  • a polymerization vessel with a reflux condenser can also be used.
  • water solubility such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or the like usually used for suspension polymerization of the vinyl compound in an aqueous medium.
  • a water-soluble emulsifier such as sodium acid may be used in combination.
  • the viscosity average polymerization degree of PVA was measured according to JIS-K6726 (1994). Specifically, when the saponification degree is less than 99.5 mol%, the intrinsic viscosity [ ⁇ ] (liter / liter) measured in water at 30 ° C. is used for the saponified PVA until the saponification degree is 99.5 mol% or more.
  • the viscosity average degree of polymerization (P) was determined by the following formula using g).
  • the degree of saponification of the modified PVA (A) is a value measured for the modified PVA (A) isolated by reprecipitation purification of the powder comprising the obtained composition (D).
  • P ([ ⁇ ] ⁇ 10 4 /8.29) (1 / 0.62)
  • the degree of saponification of PVA was determined by the method described in JIS-K6726 (1994).
  • the degree of saponification of the modified PVA (A) is a value measured for the modified PVA (A) isolated by reprecipitation purification of the powder comprising the obtained composition (D).
  • composition 1 PVA (E) having 4.6 parts of methacrylic anhydride as an esterifying agent and 0.3 part of t-butylhydroquinone as compound (C) having a viscosity average polymerization degree of 250 and a saponification degree of 45 mol% Add to 100 parts to obtain a mixed powder. The resulting mixed powder was heat-treated at 120 ° C. for 6 hours, and then 1.5 parts of methacrylic acid as an unsaturated monocarboxylic acid or a salt thereof (B) was added to modify the methacryloyl group. A powdery composition 1 containing PVA (A), unsaturated monocarboxylic acid or a salt thereof (B), and compound (C) was obtained.
  • the usage-amount of the said unsaturated monocarboxylic acid or its salt (B) is the quantity with respect to 100 parts of modified PVA (A).
  • modified PVA (A) a peak of a double bond introduced in the vicinity of 6.0 to 6.5 ppm was confirmed, and the amount of introduced modified group was 0.23 mol% with respect to the total monomer units.
  • the modified PVA (A) had a viscosity average polymerization degree of 250 and a saponification degree of 45 mol%.
  • the mass ratio of the modified PVA (A) / unsaturated monocarboxylic acid or salt (B) in composition 1 was 98.5 / 1.5.
  • compositions 2 to 13 The types and amounts of PVA (E), esterifying agent, compound (C), unsaturated monocarboxylic acid or salt (B), and heat treatment conditions are as shown in Tables 1 and 2.
  • Compositions 2 to 13 were produced in the same manner as in Production of Composition 1, except that the changes were made. Conditions and results are shown in Tables 1 and 2.
  • Example 1 As a suspension polymerization test for vinyl compounds, composition 1 which was allowed to stand at 50 ° C. for 6 months after production was dissolved in methanol as a dispersion stabilizer for suspension polymerization, and 10 parts were charged into an autoclave. The concentration of Composition 1 in the methanol solution was 500 ppm with respect to the amount of vinyl chloride charged. Next, 100 parts of PVA having a viscosity average polymerization degree of 2000 and a saponification degree of 80 mol% was dissolved in deionized water as PVA to be used in combination. The concentration of the PVA used in combination was 800 ppm with respect to the charged amount of vinyl chloride.
  • the pressure in the autoclave at the start of polymerization was 0.80 MPa. After about 3.5 hours from the start of the polymerization, when the pressure in the autoclave reached 0.70 MPa, the polymerization was stopped, unreacted vinyl chloride was removed, the polymerization reaction product was taken out, and 65 ° C. Was dried for 16 hours to obtain vinyl chloride polymer particles.
  • the content of JIS standard sieve 60 mesh on was expressed in mass%. A: Less than 5% B: 5% or more and less than 10% C: 10% or more
  • Examples 2-5 Using the obtained compositions 2 to 5, a suspension polymerization test of a vinyl compound was performed. A suspension polymerization of vinyl chloride was carried out in the same manner as in Example 1 except that the composition (D) used as the dispersion stabilizer for suspension polymerization was changed as shown in Table 2. Table 2 shows the conditions and the evaluation results of the obtained vinyl chloride polymer particles.
  • Comparative Example 2 The obtained composition 7 was used for suspension polymerization of a vinyl compound in the same manner as in Example 1. Since the unsaturated monocarboxylic acid or salt (B) contained in the composition 7 is oleic acid, the particle size of the vinyl chloride polymer particles is large, the particle size distribution is wide, the plasticizer absorbability is low, and the fish eye There were many. The conditions and results are shown in Table 2.
  • Comparative Example 3 The obtained composition 8 was used for suspension polymerization of a vinyl compound in the same manner as in Example 1. Since the degree of saponification of the modified PVA (A) in the composition 8 was too high, the plasticizer absorbability was low and there were many fish eyes. The conditions and results are shown in Table 2.
  • Comparative Example 6 The obtained composition 11 was used for suspension polymerization of a vinyl compound in the same manner as in Example 1. Since the side chain of the modified PVA (A) contained in the composition 11 is a maleyl group, the vinyl chloride polymer particles have a large particle size, a wide particle size distribution, low plasticizer absorbability, and many fish eyes. The conditions and results are shown in Table 2.
  • Comparative Example 7 The obtained composition 12 was used for suspension polymerization of a vinyl compound in the same manner as in Example 1. Since there were too many unsaturated monocarboxylic acids or its salt (B) contained in the composition 12, the particle size distribution was wide, the plasticizer absorptivity was low, and there were many fish eyes. The conditions and results are shown in Table 2.

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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)
  • General Chemical & Material Sciences (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition (D) qui comprend un alcool polyvinylique modifié (A), et un acide monocarboxylique ou un sel de celui-ci (B), et qui est caractéristique en ce que l'alcool polyvinylique modifié (A) présente un degré de polymérisation moyen en viscosité supérieur ou égal à 100 et inférieur ou égal à 600, un degré de saponification supérieur ou égal à 33% en moles et inférieur ou égal à 60%, et possède sur une chaîne latérale ０,０１% en moles ou plus à １,５０% en moles ou moins d'un groupe acryloyle ou d'un groupe méthacryloyle, l'acide monocarboxylique ou le sel de celui-ci (B) consiste en au moins un élément choisi dans un groupe constitué d'un acide acrylique, d'un acide méthacrylique, d'un acrylate de sodium et d'un méthacrylate de sodium, et le rapport massique alcool polyvinylique modifié (A) / acide monocarboxylique ou sel de celui-ci (B) dans cette composition (D), est compris entre ８２／１８ et ９９,９／０,１. Ainsi, l'invention fournit une composition comprenant un alcool polyvinylique modifié, qui présente d'excellentes performances en tant qu'agent de dispersion pour polymérisation en suspension d'un composé vinyle y compris après écoulement d'une longue période après fabrication.
PCT/JP2019/015666 2018-04-11 2019-04-10 Composition d'alcool polyvinylique ainsi qu'application de celle-ci, et procédé de fabrication de résine à base de vinyle Ceased WO2019198764A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3819316A4 (fr) * 2018-07-05 2022-03-30 Kuraray Co., Ltd. Polymère d'alcool vinylique modifié, procédé de production associé, stabilisateur de dispersion pour polymérisation en suspension, et procédé de production de polymère vinylique
JPWO2022230828A1 (fr) * 2021-04-27 2022-11-03

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WO2007119735A1 (fr) * 2006-04-12 2007-10-25 Kuraray Co., Ltd. Stabilisateur de dispersion
JP2007321099A (ja) * 2006-06-02 2007-12-13 Tohcello Co Ltd 不飽和カルボン酸変性ビニルアルコール系重合体の製造方法及びこれを用いたガスバリア性膜若しくはガスバリア性積層体

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Publication number Priority date Publication date Assignee Title
JP2001288214A (ja) * 2000-04-04 2001-10-16 Diabond Industry Co Ltd 変性ポリビニルアルコール・酢酸ビニル共重合体の製造方法
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EP3819316A4 (fr) * 2018-07-05 2022-03-30 Kuraray Co., Ltd. Polymère d'alcool vinylique modifié, procédé de production associé, stabilisateur de dispersion pour polymérisation en suspension, et procédé de production de polymère vinylique
US11414507B2 (en) 2018-07-05 2022-08-16 Kuraray Co., Ltd. Modified vinyl alcohol polymer, method for producing same, dispersion stabilizer for suspension polymerization, and method for producing vinyl polymer
JPWO2022230828A1 (fr) * 2021-04-27 2022-11-03
WO2022230828A1 (fr) * 2021-04-27 2022-11-03 株式会社クラレ Polymère d'alcool vinylique, poudre le comprenant, ses procédés de production, agent de traitement de papier et dispersant pour la polymérisation en émulsion

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