WO2022230828A1 - ビニルアルコール系重合体、これを含む粉末、これらの製造方法、紙加工剤及び乳化重合用分散剤 - Google Patents

ビニルアルコール系重合体、これを含む粉末、これらの製造方法、紙加工剤及び乳化重合用分散剤 Download PDF

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WO2022230828A1
WO2022230828A1 PCT/JP2022/018783 JP2022018783W WO2022230828A1 WO 2022230828 A1 WO2022230828 A1 WO 2022230828A1 JP 2022018783 W JP2022018783 W JP 2022018783W WO 2022230828 A1 WO2022230828 A1 WO 2022230828A1
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pva
powder
mass
group
degree
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French (fr)
Japanese (ja)
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美鈴 藤森
悠太 田岡
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to US18/557,186 priority Critical patent/US20240218097A1/en
Priority to CN202280031233.0A priority patent/CN117203247A/zh
Priority to EP22795741.2A priority patent/EP4332127A4/en
Priority to JP2023517521A priority patent/JP7846680B2/ja
Publication of WO2022230828A1 publication Critical patent/WO2022230828A1/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
    • 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
    • C08F16/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/02—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F16/04—Acyclic compounds
    • C08F16/06—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
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on 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; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on 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; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling 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
    • C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to vinyl alcohol polymers, powders containing the same, methods for producing these, paper processing agents, and dispersants for emulsion polymerization.
  • Vinyl alcohol polymer (hereinafter sometimes referred to as "PVA") is known as a water-soluble synthetic polymer, and is a stable polymer for paper processing, fiber processing, adhesives, emulsion polymerization and suspension polymerization. It is widely used for applications such as agents, inorganic binders, and films.
  • PVA containing structural units derived from carboxylic acid or derivatives thereof is known (see Patent Document 1).
  • Such PVA is used as a sizing agent for acidic paper containing aluminum sulfate, as a water-resistant coating film in combination with a cross-linking agent, as an adhesive, etc., by utilizing the reactivity of carboxylic acid.
  • a cross-linking agent for acidic paper containing aluminum sulfate
  • a cross-linking agent as an adhesive, etc.
  • it because of its good water solubility, it is useful and widely used as a water-soluble packaging film for agricultural chemicals, laundry detergents, industrial chemicals, and the like.
  • aqueous solution of PVA For industrial PVA film production, it is common to use an aqueous solution of PVA with water as the solvent as the film-forming solution, taking into consideration the environment and economy. Also, when PVA is used as a component of a coating agent or an adhesive, water is often used as a solvent. When using an aqueous solution of PVA as a film-forming solution, coating agent, adhesive, paper processing agent, etc., the PVA should be prepared at a high concentration in order to shorten the drying time and reduce the energy required for drying. is preferred. Also, when PVA is used as a dispersant for emulsion polymerization, PVA may be prepared to a high concentration and used. However, conventional aqueous solutions of PVA have the disadvantage that when the concentration is increased, the viscosity rises markedly and the coatability and the like deteriorate.
  • the present invention has been made to solve the above problems, and includes PVA in which an increase in viscosity when made into a high-concentration aqueous solution is suppressed, a powder containing such PVA, a method for producing these, and such
  • An object of the present invention is to provide a paper processing agent containing PVA and a dispersant for emulsion polymerization.
  • the PVA of [1] which is; [3] At least one selected from the group consisting of the above monomers having a carboxy group and derivatives thereof is maleic acid, maleic acid monoalkyl ester, maleic acid dialkyl ester, maleic anhydride, fumaric acid, monoalkyl fumarate PVA of [1], which is at least one selected from the group consisting of esters and dialkyl fumarate; [4] The PVA of any one of [1] to [3], which satisfies the following formula (I); S ⁇ P>250 (I) In formula (I), S is the content (mol %) of structural units derived from at least one selected from the group consisting of the above-mentioned carboxy group-containing monomers and derivatives thereof, relative to all structural units.
  • P is the viscosity average degree of polymerization.
  • g A is the degree of branching at an absolute molecular weight of 200,000.
  • g B is the degree of branching at an absolute molecular weight of 800,000.
  • a method for producing PVA [11] The method for producing powder according to any one of [7] to [9], wherein a copolymer of at least one selected from the group consisting of monomers having a carboxy group and derivatives thereof and a vinyl ester is prepared. obtaining step (1), obtaining a saponified product of the copolymer (2), and heat-treating the saponified product (3).
  • a method for producing a powder wherein the content of the powder passing through the sieve is 12% by mass or less; [12] A paper processing agent containing the PVA of any one of [1] to [6]; [13] A dispersant for emulsion polymerization containing the PVA of any one of [1] to [6]; This is achieved by providing either
  • a PVA in which an increase in viscosity when made into a highly concentrated aqueous solution is suppressed a powder containing such a PVA, a method for producing the same, a paper processing agent containing such a PVA, and an emulsion polymerization agent. Dispersants can be provided.
  • FIG. 1 is a graph showing the relationship between the absolute molecular weights and the intrinsic viscosities ([ ⁇ ] branch and [ ⁇ ] linear ) of PVA-1 and PVA-1′ in Examples.
  • FIG. 2 is a graph showing the relationship between the absolute molecular weight of PVA-1 and the degree of branching (g m ) in Examples.
  • the PVA (vinyl alcohol polymer) of the present invention is PVA containing a structural unit derived from at least one selected from the group consisting of monomers having a carboxy group and derivatives thereof, and having an absolute molecular weight of 200,000 or more. In the range of 800,000 or less, the minimum degree of branching is 0.93 or less, the viscosity average degree of polymerization is 750 or less, and the degree of saponification is 65 mol% or more.
  • “at least one selected from the group consisting of monomers having a carboxy group and derivatives thereof” may be referred to as "monomer (a)".
  • the PVA of the present invention contains structural units derived from vinyl alcohol units and monomer (a).
  • the PVA is usually obtained by saponifying a vinyl ester polymer (copolymer of monomer (a) and vinyl ester) containing a structural unit derived from monomer (a).
  • Derivatives of a monomer having a carboxy group include esters and anhydrides of a monomer having a carboxy group.
  • a carboxy group (--COOH) may exist in the form of a salt (--COONa, etc.).
  • a structural unit derived from the monomer (a) may form a crosslinked structure and bond with other structural units.
  • Monomer (a) includes ethylenically unsaturated monocarboxylic acids, ethylenically unsaturated dicarboxylic acids and derivatives thereof.
  • ethylenically unsaturated monocarboxylic acids and derivatives thereof include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
  • ethylenically unsaturated dicarboxylic acids and their derivatives include ethylenically unsaturated dicarboxylic acids, their monoesters, their diesters, their anhydrides, and the like.
  • Ethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.
  • Monoesters of ethylenically unsaturated dicarboxylic acids include monomethyl maleate, monoethyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl citraconate, monoethyl citraconate, monomethyl mesaconate, monoethyl mesaconate, monomethyl itaconate, itaconic acid.
  • Examples include monoalkyl unsaturated dicarboxylic acid esters such as monoethyl.
  • Diesters of ethylenically unsaturated dicarboxylic acids include dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl citraconate, diethyl citraconate, dimethyl mesaconate, diethyl mesaconate, dimethyl itaconate, diethyl itaconate.
  • dialkyl unsaturated dicarboxylic acid esters such as Examples of anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride and citraconic anhydride.
  • the monomer (a) is preferably an ethylenically unsaturated dicarboxylic acid, and its monoester, diester and anhydride, and maleic acid and monoalkyl maleate.
  • Esters, dialkyl maleates, maleic anhydride, fumaric acid, monoalkyl fumarate and dialkyl fumarate are more preferred, with monomethyl maleate, dimethyl maleate, maleic anhydride, monomethyl fumarate and dimethyl fumarate being particularly preferred.
  • 1 type(s) or 2 or more types can be used for a monomer (a).
  • the lower limit of the content (S) of the structural unit derived from the monomer (a) with respect to the total structural units of the PVA of the present invention is preferably 0.1 mol%, more preferably 0.5 mol%. 0 mol % is more preferred, and 1.5 mol % is particularly preferred.
  • the upper limit of the content (S) is preferably 15 mol%, more preferably 10 mol%, still more preferably 5 mol%, and even more preferably 3 mol% in some cases.
  • the above content (S) can be determined by 1 H-NMR analysis of the vinyl ester polymer before saponification of the PVA of the present invention.
  • the minimum degree of branching is 0.93 or less in the absolute molecular weight range of 200,000 or more and 800,000 or less.
  • the degree of branching is an index representing the degree of branched structure of a polymer, and the degree of branching of a linear polymer, ie, a polymer having no branched structure, is set to 1, and the closer to 0, the more the branched structure.
  • the degree of branching is obtained for each absolute molecular weight in the range of 200,000 to 800,000. Then, the smallest degree of branching in the above range is set as the minimum degree of branching.
  • the absolute molecular weight of PVA when the absolute molecular weight of PVA is not distributed over the entire range of 200,000 or more and 800,000 or less, for example, when only PVA with an absolute molecular weight of 600,000 or less is included, the absolute molecular weight is 200,000 or more and 60,000.
  • the smallest degree of branching in the range of 10,000 or less is the minimum degree of branching. That is, the PVA of the present invention consisting of a plurality of molecules includes molecules having an absolute molecular weight within the range of 200,000 or more and 800,000 or less, and the absolute molecular weight is distributed over the entire range of 200,000 or more and 800,000 or less. It doesn't have to be.
  • the degree of branching gm at each absolute molecular weight of the PVA of the present invention is obtained from the following formulas (1) and (2).
  • g m ′ [ ⁇ ] branch /[ ⁇ ] linear (1)
  • gm gm ' (1/ ⁇ ) (2)
  • [ ⁇ ] branch is the intrinsic viscosity at the absolute molecular weight x (x is 200,000 or more and 800,000 or less) of the PVA (branched PVA) of the present invention having a branched structure. , values calculated from the light scattering detector and the viscosity detector.
  • [ ⁇ ] linear is the intrinsic viscosity of linear PVA at the above absolute molecular weight x, and is similarly a value calculated from a differential refractive index detector, a light scattering detector and a viscosity detector.
  • the linear PVA the viscosity of the 4% by mass aqueous solution is within ⁇ 20% of the PVA of the present invention to be measured, and the degree of saponification is within ⁇ 3 mol% of unmodified PVA (vinyl acetate homopolymer saponified product) is used.
  • the intrinsic viscosity at each absolute molecular weight of the PVA and linear PVA of the present invention can be measured by the method described in Examples.
  • the relationship between the intrinsic viscosity ratio g m ′ and the degree of branching g m represented by the above formula (1) is given by the above formula (2).
  • the minimum degree of branching is 0.93 or less, and a sufficient branched structure (crosslinking) is formed. Therefore, according to the PVA of the present invention, an increase in viscosity is suppressed when an aqueous solution of high concentration is formed.
  • the upper limit of the minimum degree of branching is preferably 0.8, more preferably 0.6, and even more preferably 0.4, 0.25 or 0.18 in some cases.
  • the lower limit of the minimum degree of branching may be, for example, 0.01 or 0.05, preferably 0.11, and more preferably 0.20.
  • the branches in the PVA are formed by heat treatment, such as ester bonding between the carboxy group and the hydroxy group of the PVA. Therefore, the minimum degree of branching can be adjusted by heat treatment conditions such as heat treatment temperature and heat treatment time, content of structural units derived from the monomer (a), degree of saponification, and the like.
  • the PVA of the present invention includes PVA having an absolute molecular weight within the range of 200,000 or more and 800,000 or less.
  • the PVA of the present invention preferably contains PVA with an absolute molecular weight of 200,000 and PVA with an absolute molecular weight of 800,000, and the absolute molecular weight is distributed over the entire range of at least 200,000 to 800,000. is more preferable.
  • the upper limit of the viscosity-average degree of polymerization (P) of the PVA of the present invention is 750, preferably 700, more preferably 600, and even more preferably 500.
  • the lower limit of the viscosity-average degree of polymerization (P) may be, for example, 100, or 150 or 200.
  • the viscosity average degree of polymerization (P) is a value measured according to JIS K6726:1994. Specifically, it can be determined by the method described in the Examples.
  • the lower limit of the content of vinyl alcohol units to all structural units in the PVA of the present invention is preferably 65 mol%, more preferably 70 mol%, and even more preferably 80 mol% or 85 mol%.
  • the upper limit of the vinyl alcohol unit content is preferably 99.9 mol %, more preferably 99 mol %.
  • the lower limit of the saponification degree of the PVA of the present invention is 65 mol%, preferably 80 mol%, more preferably 85 mol%.
  • the degree of saponification is equal to or higher than the above lower limit, the water solubility is enhanced and the insoluble content is reduced, making it easier to prepare a uniform PVA aqueous solution of high concentration.
  • the upper limit of the degree of saponification may be 100 mol%, preferably 99.9 mol%, more preferably 99 mol%, and even more preferably 92 mol% in some cases.
  • the degree of saponification is a value measured by the method described in JIS K6726:1994.
  • the PVA of the present invention preferably satisfies the following formula (I). S ⁇ P>250 (I)
  • S is the content (mol%) of structural units derived from the monomer (a) with respect to all structural units.
  • P is the viscosity average degree of polymerization.
  • the extent of the effects of carboxylic acid modification (formation of a branched structure, etc.) and the extent of effects due to the degree of polymerization are balanced, and coatability and the like are further improved.
  • coating unevenness during coating tends to be more suppressed, and the strength of the resulting film tends to increase.
  • the lower limit of S ⁇ P is more preferably 300, and may be even more preferably 400, 500, 600 or 700.
  • the upper limit of S ⁇ P is preferably 4,000, more preferably 3,000, and even more preferably 2,000.
  • the PVA of the present invention preferably satisfies the following formula (II). 1.0 ⁇ g A /g B ⁇ 9.0 (II)
  • g A is the degree of branching at an absolute molecular weight of 200,000 (the degree of branching of PVA with an absolute molecular weight of 200,000 among the PVA of the present invention).
  • g B is the branching degree at an absolute molecular weight of 800,000 (the branching degree of PVA having an absolute molecular weight of 800,000 among the PVA of the present invention).
  • the ratio g A /g B in formula (II) increases. From such a viewpoint, the ratio g A /g B is more preferably less than 7.0, more preferably less than 6.0, less than 5.0, less than 4.0, less than 3.5 or less than 3.0 is even more preferable.
  • the insoluble content is preferably 0.1 ppm or more and less than 2000 ppm.
  • the insoluble content may be more preferably less than 1,500 ppm, and even more preferably less than 1,000 ppm. Since the amount of the insoluble matter is small in this way, it is possible to improve the coatability of the PVA aqueous solution.
  • the insoluble content may be 1 ppm or more, 10 ppm or more, or 100 ppm or more.
  • ppm is a mass standard, and the said insoluble content (ppm) shows the content rate of the insoluble content in PVA.
  • the insoluble matter can be obtained by the method described in the Examples.
  • the value of the ratio g A /g B and the content of the insoluble matter tend to increase as the proportion of PVA that is excessively heated and excessively crosslinked increases. Therefore, as will be described later, when heat-treating a saponified product of a vinyl ester polymer (copolymer), fine powder that is likely to be heated excessively is removed in advance, the heat treatment is performed while removing the fine powder, or the fine powder is removed after the heat treatment. can reduce the ratio g A /g B and the content of the insoluble matter.
  • the PVA of the present invention may contain structural units other than vinyl alcohol units, vinyl ester units, and structural units derived from the monomer (a).
  • monomers that give the other structural units include ⁇ -olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene; N-methylacrylamide, N-ethylacrylamide, 2-acrylamido-2-methylpropane acrylamide derivatives such as sulfonic acid; methacrylamide derivatives such as N-methyl methacrylamide and N-ethyl methacrylamide; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether and n-butyl vinyl ether; ethylene glycol vinyl ether, Hydroxy group-containing vinyl ethers such as 1,3-propanediol vinyl ether and 1,4-butanediol vinyl ether; allyl acetate; 3,4-
  • the content of the other structural units with respect to the total structural units of the PVA of the present invention may be preferably 20 mol% or less, more preferably 10 mol% or less, 3 mol% or less, 1 mol% or less, or 0.1 mol % or less may be even more preferable.
  • the content of the other structural unit may be, for example, 0.1 mol % or more, or 1 mol % or more.
  • the PVA of the present invention may not have an aliphatic hydrocarbon group having 12 carbon atoms at its terminal, and may not have an aliphatic hydrocarbon group having 6 to 18 carbon atoms at its terminal. good too.
  • a terminal aliphatic hydrocarbon group can be introduced, for example, by a chain transfer agent having an aliphatic hydrocarbon group having from 6 to 18 carbon atoms.
  • the chain transfer agent include alkylthiols having 6 to 18 carbon atoms such as n-dodecanethiol.
  • the powder of the present invention is powder containing the PVA of the present invention. Since the powder contains the PVA of the present invention, even when the PVA is dissolved in water so as to have a high concentration, the increase in the viscosity of the aqueous solution can be suppressed.
  • the PVA of the present invention is usually the main ingredient.
  • a main component means a component with the largest content on a mass basis.
  • the lower limit of the content of the PVA of the present invention with respect to the non-volatile content of the powder of the present invention is preferably 50% by mass, more preferably 70% by mass, still more preferably 90% by mass, and even more preferably 99% by mass.
  • the upper limit of the content of the PVA of the present invention with respect to the non-volatile content of the powder of the present invention may be 100% by mass.
  • Non-volatile matter other than the PVA of the present invention that may be contained in the powder of the present invention includes PVA other than the PVA of the present invention, resins other than PVA, surfactants, additives such as plasticizers, and additives used during production Each compound etc. are mentioned.
  • the content of volatile matter in the powder of the present invention is usually 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less.
  • Volatile matter that can be contained in the powder of the present invention includes alcohol, water, and the like.
  • the powder of the invention may be the PVA powder of the invention.
  • the upper limit of the content of powder (fine powder) that passes through a 180 ⁇ m sieve is preferably 12% by mass, and may be more preferably 10% by mass, 8% by mass or 5% by mass.
  • the fine powder tends to be excessively heated by the heat treatment, and the cross-linking proceeds too much to become an insoluble matter. Therefore, by setting the content of the powder that passes through a sieve with a mesh size of 180 ⁇ m to the above upper limit or less, the insoluble matter is reduced, and the coatability and the like when used as an aqueous solution are improved.
  • the lower limit of the content of powder that passes through a sieve with an opening of 180 ⁇ m may be 0.1% by mass or 1% by mass.
  • the mesh size of the sieve conforms to the nominal mesh size W of JIS Z 8801-1-2006 (hereinafter the same).
  • the content of powder that passes through a sieve with an opening of 1.00 mm is 97% by mass or more, and the content of powder that passes through a sieve with an opening of 500 ⁇ m is 40% by mass or more. preferable.
  • the lower limit of the content of powder that passes through a sieve with an opening of 1.00 mm is more preferably 98% by mass, and even more preferably 99% by mass.
  • the upper limit of the content of powder that passes through a sieve with an opening of 1.00 mm may be 100% by mass or 99.9% by mass.
  • the upper limit of the content of powder that passes through a sieve with an opening of 500 ⁇ m may be 70% by mass or 60% by mass.
  • the particle size distribution of the powder of the present invention can be adjusted by sieving during the manufacturing process or after manufacturing.
  • the insoluble content is preferably 0.1 ppm or more and less than 2000 ppm.
  • the insoluble content may be more preferably less than 1,500 ppm, and even more preferably less than 1,000 ppm. Since the insoluble matter is small in this way, the coatability of the aqueous solution obtained from the powder of the present invention can be improved.
  • the insoluble content may be 1 ppm or more, 10 ppm or more, or 100 ppm or more.
  • the measurement of the insoluble content of the powder can be performed in the same manner as the measurement of the insoluble content of PVA.
  • PVA and powders of the present invention can be used in a variety of applications similar to conventional PVA and powders thereof. Examples are given below, but are not limited thereto.
  • Vinyl chloride dispersant Applications dispersion stabilizers and dispersing aids for suspension polymerization of vinyl chloride and vinylidene chloride Metal corrosion inhibitor, brightener for zinc plating, antistatic agent (3)
  • Adhesives, binders Uses Adhesives, adhesives, rewetting adhesives, various binders, additives for cement and mortar (4)
  • Flocculant Application Suspended and dissolved in water flocculant, metal flocculant (8)
  • Film application Water-soluble film, polarizing Films, barrier films, textile product
  • the PVA and powder of the present invention are suppressed from increasing in viscosity when made into a high-concentration aqueous solution. Therefore, it is particularly suitable for applications in which it is used in the form of an aqueous solution.
  • Such uses include adhesives, films (film forming solutions), paper processing agents, dispersants for emulsion polymerization, and the like.
  • an aqueous solution containing the PVA of the present invention, an adhesive containing the PVA of the present invention, a film containing the PVA of the present invention, a paper processing agent containing the PVA of the present invention, and a dispersant for emulsion polymerization containing the PVA of the present invention. etc. are also preferred embodiments of the present invention.
  • the content of the PVA of the present invention in the aqueous solution, adhesive, film forming solution, etc. is, for example, 1% by mass or more and 30% by mass or less, may be 5% by mass or more and 20% by mass or less, or 10% by mass. or more.
  • the above aqueous solution, adhesive, film-forming solution, etc. may further contain components other than the PVA and water of the present invention. Examples of such other components include components contained in conventionally known adhesives, film-forming solutions, and the like.
  • the paper processing agent of the present invention contains the PVA of the present invention.
  • the paper processing agent of the present invention may be in the form of powder or may be in the form of liquid such as an aqueous solution.
  • the paper coating agent of the present invention may be a coating agent for paper.
  • the paper processing agent can be the same as conventionally known paper processing agents except that the PVA of the present invention is used.
  • the paper processing agent may further contain components other than the PVA of the present invention. Other components include, for example, pigments, dispersants, plasticizers, pH adjusters, antifoaming agents, surfactants, and resins other than the PVA of the present invention.
  • the dispersant for emulsion polymerization of the present invention contains the PVA of the present invention.
  • the dispersant for emulsion polymerization of the present invention may be in the form of a powder or in the form of a liquid such as an aqueous solution.
  • the dispersant for emulsion polymerization can be the same as conventionally known dispersants for emulsion polymerization except that the PVA of the present invention is used.
  • the dispersant for emulsion polymerization may further contain components other than the PVA of the present invention. Other components include, for example, surfactants, buffers, polymerization degree modifiers, PVA other than the PVA of the present invention, and the like.
  • the dispersant for emulsion polymerization is particularly preferably used as a dispersant for emulsion polymerization of ethylenically unsaturated monomers.
  • the method for producing the PVA or powder of the present invention is not particularly limited, the following method is preferred. That is, the method for producing PVA or powder of the present invention is step (1) of obtaining a copolymer of the monomer (a) and a vinyl ester; Step (2) of obtaining a saponified product of the copolymer, and Step (3) of heat-treating the saponified product Prepare.
  • step (1) a copolymer of monomer (a) and vinyl ester is obtained.
  • monomer (a) examples and suitable examples of the monomer (a) are as described above.
  • vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, and vinyl versatate. Among them, vinyl acetate is preferred.
  • Examples of polymerization methods include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among these methods, a bulk polymerization method performed without a solvent and a solution polymerization method performed using a solvent such as alcohol are preferable, and a solution polymerization method performed in the presence of a lower alcohol is more preferable. As the lower alcohol, alcohols having 3 or less carbon atoms are preferable, methanol, ethanol, n-propanol and isopropanol are more preferable, and methanol is even more preferable. In performing a polymerization reaction by a bulk polymerization method or a solution polymerization method, either a batch system or a continuous system can be employed as the reaction system.
  • initiators used in the polymerization reaction examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy -2,4-dimethylvaleronitrile); and known initiators such as organic peroxide initiators such as benzoyl peroxide and n-propylperoxycarbonate.
  • organic peroxide initiators such as benzoyl peroxide and n-propylperoxycarbonate.
  • a copolymerizable monomer can be further copolymerized within a range that does not impair the gist of the present invention.
  • Specific examples of such other monomers are as described above as monomers that provide other structural units.
  • a chain transfer agent may coexist during copolymerization for the purpose of adjusting the degree of polymerization of the obtained PVA.
  • 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 3-mercaptopropionic acid; thiocarboxylic acids such as thioacetic acid.
  • the amount of the chain transfer agent to be added is determined according to the chain transfer constant of the chain transfer agent to be added and the desired degree of polymerization of PVA, but is generally 0.1 to 10% by mass based on the vinyl ester used. is preferred.
  • step (2) the copolymer (vinyl ester polymer) obtained in step (1) above is saponified in a solution using an alkali catalyst or an acid catalyst to obtain a saponified product.
  • an alcoholysis or hydrolysis reaction using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as p-toluenesulfonic acid can be applied.
  • Solvents used in the saponification reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; and aromatic hydrocarbons such as benzene and toluene. These can be used alone or in combination of two or more. Among these, it is convenient and preferable to use methanol or a mixed solution of methanol and methyl acetate as a solvent and perform the saponification reaction in the presence of sodium hydroxide as a basic catalyst.
  • the saponification reaction can be carried out using a belt-type reactor, a kneader-type reactor, a tower-type reactor, or the like.
  • the temperature for saponification is not particularly limited, it is preferably 20° C. or higher and 60° C. or lower.
  • a gel-like product precipitates as the saponification progresses, it is preferable to pulverize the product and further proceed with the saponification. Thereafter, the resulting solution is neutralized to complete saponification and washed to obtain a saponified product.
  • the saponification method is not limited to the methods described above, and known methods can be employed.
  • step (3) the saponified product obtained through step (2) is heat-treated.
  • the heat treatment is preferably performed under an air atmosphere or a nitrogen atmosphere.
  • the heat treatment is preferably performed on a solid, more preferably powdery (particulate) saponified product.
  • the saponified product may be pre-dried, and the saponified product from which volatile matter has been removed to some extent may be subjected to heat treatment.
  • the heat treatment may be performed while stirring the saponified product.
  • the heat treatment can be performed using, for example, a cylindrical agitation dryer or the like.
  • heat treatment is performed at a heat treatment temperature of 110°C or higher and a heat treatment time of 1 hour or longer.
  • the lower limit of the heat treatment temperature may be 115°C or 120°C.
  • the upper limit of the heat treatment temperature may be 150°C, 140°C, 130°C, or 125°C.
  • the lower limit of the heat treatment time is preferably 2 hours, more preferably 3 hours, even more preferably 4 hours, and even more preferably 5 hours.
  • the upper limit of the heat treatment time may be 24 hours, 12 hours, or 8 hours.
  • the content of powder that passes through a 180 ⁇ m sieve in the saponified product at the end of step (3) is 12% by mass or less.
  • the upper limit of the content of powder that passes through this 180 ⁇ m sieve may preferably be 10% by mass, 8% by mass or 5% by mass.
  • the heat treatment may be divided into a plurality of times, and fines may be removed by sieving between each heat treatment. Further, fine powder may be removed after the heat treatment.
  • step (2) a step of pulverizing the saponified product into particles, a step of sieving the particulate saponified product, and the like may be provided.
  • the modification rate of PVA (the content of structural units derived from the monomer (a) in PVA) was obtained by a method using 1 H-NMR using a vinyl ester polymer that is a precursor of PVA.
  • the modification rate is obtained by the following procedure. That is, the vinyl ester polymer, which is the precursor of PVA, was sufficiently purified by reprecipitation three times or more using n-hexane/acetone as a solvent, and then the resulting purified product was dried at 70°C for one day. to prepare a sample for analysis. This sample is dissolved in CDCl 3 and measured at room temperature using 1 H-NMR.
  • the modification rate (content S of structural units derived from monomer (a)) can be calculated using the following formula.
  • S (mol%) ⁇ (number of protons in ⁇ /3)/(number of protons in ⁇ + (number of protons in ⁇ /3)) ⁇ ⁇ 100
  • hexafluoroisopropanol is used as a mobile phase, and gel permeation chromatography (GPC) is measured using a differential refractive index detector, a light scattering detector, and a viscosity detector.
  • the intrinsic viscosity for each absolute molecular weight of 200,000 or more and 800,000 or less of the linear PVA was obtained.
  • the straight-chain PVA used was unmodified PVA having a 4% by mass aqueous solution viscosity within ⁇ 20% of the PVA to be measured and a degree of saponification within ⁇ 3 mol%. Specific measurement conditions for GPC are shown below.
  • Solvent Hexafluoroisopropanol (containing sodium trifluoroacetate at a concentration of 20 mmol/L)
  • Flow rate 1.0 mL/min
  • Sample concentration 0.1 mass/vol%
  • Injection volume 100 ⁇ L
  • Intrinsic viscosity [ ⁇ ] of PVA to be measured for each measured absolute molecular weight The degree of branching gm for each absolute molecular weight was determined by the formulas (1) and (2).
  • the lowest branching degree gm in the absolute molecular weight range of 200,000 or more and 800,000 or less was defined as the minimum branching degree. Also, the ratio g A /g B between the degree of branching g A at an absolute molecular weight of 200,000 and the degree of branching g B at an absolute molecular weight of 800,000 was determined. As an example of the measurement results, the results of PVA-1 are shown in FIGS.
  • FIG. 1 is a graph (Mark-Houwink plot) plotting the absolute molecular weights and intrinsic viscosities ([ ⁇ ] branch or [ ⁇ ] linear ) of the PVA-1 to be measured and the corresponding linear PVA PVA-1′. is.
  • PVA-1′ is an unmodified PVA with a 4% aqueous solution viscosity of 9.2 mPa ⁇ s and a degree of saponification of 88 mol %.
  • FIG. 2 is a graph plotting the degree of branching gm for each absolute molecular weight of PVA-1 obtained by the above formulas (1) and (2) based on the results shown in FIG.
  • the particle size distribution of the PVA powder was measured by the dry sieving method described in JIS Z8815:1994. Using sieves with openings of 1.00 mm, 500 ⁇ m, and 180 ⁇ m, the ratio of the mass of the powder passing through the sieve with an opening of 1.00 mm to the mass of the PVA powder before sieving (content: mass%), The mass ratio (content: mass %) of powder that passed through a sieve with an opening of 500 ⁇ m and the mass ratio (content: mass %) of powder that passed through a sieve with an opening of 180 ⁇ m were determined. Incidentally, the above-mentioned opening complies with the nominal opening W of JIS Z8801-1-2006.
  • the filter was thoroughly washed with hot water at 30°C to remove the solution adhering to the filter, leaving only undissolved particles on the filter, and then the filter was dried in a heat dryer at 120°C for 1 hour.
  • the mass of the undissolved particles was calculated by comparing the mass of the filter after drying with the mass of the filter before being used for filtration.
  • the mass of the insoluble particles with respect to the PVA powder (12 g) used was defined as the insoluble content (ppm).
  • a PVA aqueous solution was prepared, and the viscosity (mPa ⁇ s) was measured using a Brookfield viscometer (rotor speed: 12 rpm, temperature: 20°C).
  • the method for preparing the PVA aqueous solution was as follows. 90 parts by mass of water was added to 10 parts by mass of PVA, and the mixture was heated to 90°C with stirring and cooled after 1 hour.
  • the same non-denatured PVA used in the GPC measurement for determining the degree of branching was selected as a reference non-denatured PVA. Viscosity measurements were similarly performed for unmodified PVA.
  • the viscosity ratio between them (viscosity of standard unmodified PVA/PVA of Example or Comparative Example) was calculated. When the viscosity ratio was greater than 1.0, it was determined that the increase in viscosity was suppressed, and when the viscosity ratio was greater than 1.2, it was determined that the increase in viscosity was particularly sufficiently suppressed.
  • Example 1 (Production of PVA-1) 700 parts by mass of vinyl acetate and 1,050 parts by mass of methanol were charged into a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a comonomer dropping port, and a polymerization initiator addition port, and the system was stirred for 30 minutes while nitrogen bubbling was performed. was replaced with nitrogen. Monomethyl maleate was used as the monomer (a), and a methanol solution of monomethyl maleate (concentration 10%) was replaced with nitrogen by bubbling nitrogen gas.
  • Examples 2 to 7 and Comparative Examples 1 to 5 (Production of PVA-2 to PVA-12) Polymerization conditions such as the amount of vinyl acetate and methanol used, the type and amount of monomer (a) used; saponification conditions such as the concentration of the vinyl ester polymer in saponification and the molar ratio of sodium hydroxide to vinyl acetate units; Each PVA (PVA-2 to PVA-12) of Examples 2 to 7 and Comparative Examples 1 to 5 was prepared in the same manner as in Example 1, except that the heat treatment conditions were changed as shown in Table 1. powder was obtained. Table 2 shows the physical properties and evaluation results of these PVA.
  • an unmodified PVA (straight-chain PVA) that serves as a reference for measuring the degree of branching and evaluating the viscosity of an aqueous solution corresponding to each of the produced PVA (PVA-1 to 13) was prepared according to the production method of Comparative Example 6 above. manufactured by However, the unmodified PVA was not subjected to heat treatment after predrying.
  • each PVA of Examples 1 to 7 suppresses an increase in viscosity when made into a high-concentration aqueous solution.
  • each PVA of Examples 1 and 7 is excellent in that it has a small amount of insoluble matter in addition to a sufficient effect of suppressing thickening. It is considered that this is influenced by the fact that the minimum degree of branching is in an appropriate range and the ratio g A /g B of the degree of branching is small.
  • each PVA of Comparative Examples 1 to 3 had a high degree of polymerization, and the introduction of a branched structure resulted in a further increase in viscosity. Since the PVA of Comparative Example 4 had a low degree of saponification and was easily crosslinked by heat, the number of thermally crosslinked sites increased, and a uniform aqueous solution could not be obtained. As for PVA of Comparative Example 4, a 10% by mass high-concentration aqueous solution could not be obtained, so it was determined that the problem of suppressing an increase in viscosity when forming a high-concentration aqueous solution could not be solved. Since the PVA of Comparative Example 5 has few branches, the effect of suppressing thickening was not exhibited. The PVA of Comparative Example 6 did not contain a structural unit derived from the monomer (a), and did not form branches even when heat-treated, and thus did not show an effect of suppressing thickening.
  • the PVA of the present invention can be used for various purposes such as coating agents, adhesives, film raw materials, paper processing agents, and dispersants for emulsion polymerization.

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US18/557,186 US20240218097A1 (en) 2021-04-27 2022-04-25 Vinyl alcohol polymer, powder containing same, methods for producing these, paper processing agent, and dispersant for emulsion polymerization
CN202280031233.0A CN117203247A (zh) 2021-04-27 2022-04-25 乙烯醇系聚合物、包含其的粉末、它们的制造方法、纸加工剂和乳液聚合用分散剂
EP22795741.2A EP4332127A4 (en) 2021-04-27 2022-04-25 VINYL ALCOHOL POLYMER, POWDER COMPRISING IT, PROCESSES FOR PRODUCING IT, PAPER TREATMENT AGENT AND DISPERSANT FOR EMULSION POLYMERIZATION
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