Classifications

• • 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
  • 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
  • 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
  • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
  • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08L27/06—Homopolymers or copolymers of 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
  • 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
  • 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
  • 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
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

• the present invention relates to a composition, a dispersant for suspension polymerization, and a method for producing a vinyl polymer.
• PVA Vinyl alcohol polymers
• PVA Water-soluble synthetic polymers.
• PVA is used in a variety of applications, including as a raw material for films and fibers, an additive for paper and fiber processing, an adhesive, a dispersant (also called a dispersion stabilizer, etc.) and a dispersion aid for emulsion polymerization and suspension polymerization, and a binder for inorganic materials.
• Patent Document 1 describes a vinyl alcohol polymer characterized by having a carbonyl group, a formyl group, and an alkenyl group in the same or different molecules, and describes that the vinyl alcohol polymer can be used as a dispersant for suspension polymerization.
• Patent Document 1 does not disclose a dispersant that can obtain polymer particles with a small average particle size, few coarse particles, and good plasticizer absorption, even when suspension polymerization is performed under high temperature conditions.
• the present invention aims to provide a composition containing a vinyl alcohol polymer and an amphiphilic substance, a dispersant for suspension polymerization containing the same, and a method for producing a vinyl polymer, which can produce polymer particles with a small average particle size, few coarse particles, and good plasticizer absorption even when suspension polymerization is performed at high temperatures.
• a composition comprising a vinyl alcohol-based polymer (A) and an amphiphilic substance (B), wherein the vinyl alcohol-based polymer (A) is a vinyl alcohol-based polymer having a carbonyl group and a saponification degree of 60 mol% or more, and the amphiphilic substance (B) comprises at least one selected from the group consisting of a surfactant and a vinyl alcohol-based polymer having a saponification degree of less than 60 mol%; [2] The composition according to [1], wherein the vinyl alcohol polymer (A) further has a formyl group and an alkenyl group; [3] The composition according to [1] or [2], wherein the vinyl alcohol polymer (A) has a structure represented by the following formula (1) containing the carbonyl group: In formula (1), m is an integer from 1 to 11.
• the present invention provides a composition containing a vinyl alcohol polymer and an amphiphilic substance, which can produce polymer particles with a small average particle size, few coarse particles, and good plasticizer absorption even when suspension polymerization is performed at high temperatures, a dispersant for suspension polymerization containing the composition, and a method for producing a vinyl polymer.
• composition of the present invention comprises a vinyl alcohol-based polymer (A) and an amphiphilic substance (B), wherein the vinyl alcohol-based polymer (A) is a vinyl alcohol-based polymer having a carbonyl group and a saponification degree of 60 mol% or more, and the amphiphilic substance (B) comprises at least one selected from the group consisting of surfactants and vinyl alcohol-based polymers having a saponification degree of less than 60 mol%.
• the vinyl alcohol polymer (A) (hereinafter also referred to as "PVA (A)") is a vinyl alcohol polymer having a carbonyl group and a saponification degree of 60 mol% or more.
• the PVA (A) may contain PVA molecules that do not have a carbonyl group.
• the PVA (A) is a PVA (aggregate of PVA molecules) having a saponification degree of 60 mol% or more measured by the method described below, and at least some of the PVA molecules therein have a carbonyl group.
• the PVA (A) preferably further has a formyl group and an alkenyl group.
• the PVA (A) may contain PVA molecules that do not have at least one of a carbonyl group, a formyl group, and an alkenyl group.
• the PVA (A) may have a carbonyl group, a formyl group, and an alkenyl group in the same or different molecules.
• PVA (A) has a carbonyl group, a formyl group, and an alkenyl group in the same or different molecules, it is not necessary that all of the carbonyl group, the formyl group, and the alkenyl group are contained in one molecule of PVA (A).
• PVA (A) may be, for example, a mixture of PVA (a) having two groups among carbonyl group, formyl group, and alkenyl group, and PVA (b) having the remaining group.
• both PVA (a) and PVA (b) may have one or more groups among carbonyl group, formyl group, and alkenyl group.
• PVA (A) may be a mixture of three or more kinds of PVA.
• a PVA having all of a carbonyl group, a formyl group, and an alkenyl group in one molecule and a mixture of multiple types of PVA having a carbonyl group, a formyl group, and an alkenyl group in one molecule have substantially similar properties, and it is generally very difficult to distinguish between these two forms by analysis or the like.
• PVA(A) is a polymer having a vinyl alcohol unit as a structural unit.
• PVA(A) may be obtained, for example, by polymerizing a vinyl ester in the presence of an aliphatic unsaturated aldehyde and saponifying the resulting vinyl ester polymer.
• the lower limit of the saponification degree of PVA(A) is 60 mol%, preferably 65 mol%, and more preferably 70 mol%.
• the upper limit of the saponification degree may be 100 mol%, but is preferably 95 mol%, more preferably 90 mol%, even more preferably 85 mol%, and even more preferably 80 mol%.
• the surfactant performance is optimized, and various performances when used, for example, as a dispersant for suspension polymerization (polymer particles with a small average particle size, few coarse particles, and good plasticizer absorption properties can be obtained) are improved.
• the saponification degree is a value measured by the method described in JIS K6726:1994.
• PVA(A) preferably has a structure represented by the following formula (1) that contains a carbonyl group.
• m is an integer from 1 to 11. It is preferable that m is an integer from 2 to 9, and in some cases it is preferable that m is an integer from 3 to 7.
• the carbonyl group content relative to the total content of vinyl alcohol units and vinyl ester units in PVA (A) is preferably 0.01 mol% to 5 mol%, more preferably 0.03 mol% to 3 mol%, even more preferably 0.05 mol% to 2 mol%, even more preferably 0.1 mol% to 1 mol%, and particularly preferably 0.15 mol% to 0.3 mol%.
• the carbonyl group content in PVA (A) is within the above range, various performances are improved when used, for example, as a dispersant for suspension polymerization.
• the carbonyl group content is a value determined by the method described in the examples below.
• the formyl group content relative to the total content of vinyl alcohol units and vinyl ester units in PVA (A) is preferably 0.01 mol% or more and 5 mol% or less, more preferably 0.03 mol% or more and 3 mol% or less, even more preferably 0.05 mol% or more and 2 mol% or less, and even more preferably 0.1 mol% or more and 1 mol% or less.
• the upper limit of the formyl group content may be 0.5 mol% or 0.3 mol%.
• the alkenyl group is a monovalent group obtained by removing any one hydrogen atom from an alkene.
• the number of carbon atoms in the alkenyl group is preferably 2 to 13, more preferably 3 to 12, even more preferably 4 to 11, and in some cases even more preferably 5 to 9.
• the alkenyl group may be linear or may have a branched structure, but is preferably linear.
• the alkenyl group is preferably located at the end of the polymer chain.
• PVA(A) has an alkenyl group
• the alkenyl group has a carbon-carbon double bond at the end (tip).
• PVA(A) has a vinyl group at the end (tip).
• the alkenyl group in PVA(A) is a group represented by the following formula (5).
• n is an integer from 1 to 11. It is preferable that n is an integer from 2 to 9, and in some cases it is more preferable that n is an integer from 3 to 7.
• the content of alkenyl groups relative to the total content of vinyl alcohol units and vinyl ester units in PVA (A) is preferably 0.01 mol% to 5 mol%, more preferably 0.03 mol% to 3 mol%, even more preferably 0.05 mol% to 1 mol%, and even more preferably 0.1 mol% to 0.5 mol%.
• the upper limit of the content of the alkenyl groups may be 0.3 mol%.
• the content of the alkenyl groups in PVA (A) is within the above range, various performances are improved when used, for example, as a dispersant for suspension polymerization.
• the content of the alkenyl groups is a value obtained by the method described in the examples below.
• the suitable range of the content of vinyl groups relative to the total content of vinyl alcohol units and vinyl ester units in PVA (A) is the same as the suitable range of the content of alkenyl groups.
• the PVA (A) preferably has a group represented by the following formula (2) at the end of the polymer chain.
• R 1 is an alkenyl group or an alkyl group.
• R 1 in formula (2) is an alkenyl group
• the number of carbon atoms of the alkenyl group represented is preferably 2 to 13, more preferably 3 to 12, even more preferably 4 to 11, and even more preferably 5 to 9 in some cases.
• the alkenyl group may be linear or may have a branched structure, but is preferably linear.
• a group having a methylene group at the terminal on the carbonyl group side (a group represented by R-CH 2 - (R is an alkenyl group)) is preferable, a group having a carbon-carbon double bond at the terminal (tip) is more preferable, and a group represented by the above formula (5) is even more preferable.
• a group in which R 1 is an alkenyl group is usually formed when an aliphatic unsaturated aldehyde acts as a chain transfer agent.
• a structure is introduced, for example, by polymerizing and saponifying a vinyl ester in the presence of an aliphatic unsaturated aldehyde, and then heat-treating the PVA.
• R 1 in formula (2) is an alkyl group
• the alkyl group is a monovalent group represented by —C s H (2s+1) , where s is preferably an integer of 1 to 12.
• PVA (A) contains a group in which R 1 is an alkyl group in formula (2)
• the content of the group in which R 1 is an alkyl group in formula (2) relative to the total content of vinyl alcohol units and vinyl ester units in PVA (A) is preferably 0.01 mol% to 5 mol%, more preferably 0.03 mol% to 3 mol%, even more preferably 0.05 mol% to 2 mol%, and even more preferably 0.1 mol% to 1 mol%.
• the content of the group in which R 1 is an alkyl group in formula (2) in PVA (A) is within the above range, various performances are improved when used, for example, as a dispersant for suspension polymerization.
• the content of the group in which R 1 is an alkyl group in formula (2) is a value obtained by the method described in the examples below.
• the group in which R1 is an alkyl group is introduced to the end of the polymer chain when, for example, a vinyl ester is polymerized in the presence of an aliphatic saturated aldehyde, and the aliphatic saturated aldehyde acts as a chain transfer agent.
• the aliphatic saturated aldehyde acetaldehyde is preferred.
• the PVA (A) may contain both a group in which R 1 in formula (2) is an alkenyl group and a group in which R 1 in formula (2) is an alkyl group.
• the PVA (A) preferably has a terminal group derived from an aliphatic unsaturated aldehyde or a structural unit derived from an aliphatic unsaturated aldehyde.
• the number of carbon atoms of the aliphatic unsaturated aldehyde is preferably 3 to 14, more preferably 4 to 12, and in some cases even more preferably 6 to 10.
• the aliphatic unsaturated aldehyde preferably has a carbon-carbon double bond, more preferably has a carbon-carbon double bond at the end (tip). That is, the aliphatic unsaturated aldehyde preferably contains a vinyl group.
• the aliphatic unsaturated aldehyde having a carbon-carbon double bond is preferably an aliphatic unsaturated aldehyde having an alkenyl group having a methylene group at the end of the carbonyl group side, that is, a group represented by R-CH 2 - (R is an alkenyl group).
• the aliphatic unsaturated aldehyde is preferably an aliphatic unsaturated aldehyde other than an ⁇ , ⁇ -unsaturated aldehyde.
• the aliphatic unsaturated aldehyde is a compound represented by the following formula (6).
• p is an integer from 1 to 11. It is preferable that p is an integer from 2 to 9, and in some cases it is more preferable that p is an integer from 3 to 7.
• Examples of the aliphatic unsaturated aldehydes include 2-propenal, 3-butenal, 4-pentenal, 5-hexenal, 3-methyl-5-hexenal, 6-heptenal, 6-octenal, 7-octenal, 7-methyl-7-octenal, 3,7-dimethyl-7-octenal, 8-nonenal, 9-decenal, 10-undecenal, and 11-dodecenal.
• the terminal group derived from an aliphatic unsaturated aldehyde that the PVA (A) preferably has is, among the groups represented by the following formula (2) above, a group in which R 1 is an alkenyl group.
• the specific form and preferred form of the group (terminal group) represented by the above formula (2) are as described above.
• the group in which R1 is an alkenyl group is introduced to the end of the polymer chain when the vinyl ester is polymerized in the presence of an aliphatic unsaturated aldehyde and the aliphatic unsaturated aldehyde acts as a chain transfer agent, as described above.
• the structural unit derived from an aliphatic unsaturated aldehyde that PVA (A) preferably has is represented by the following formula (3) or (4).
• R 2 to R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
• q represents an integer of 1 to 11.
• r represents an integer of 1 to 11.
• R 2 to R 4 are preferably hydrogen atoms.
• q is preferably an integer of 2 to 9, and in some cases is more preferably an integer of 3 to 7.
• the structural unit represented by formula (3) is usually formed when an aliphatic unsaturated aldehyde acts as a monomer, and is introduced into a polymer chain.
• R 5 to R 7 are preferably hydrogen atoms.
• r is preferably an integer of 2 to 9, and in some cases is more preferably an integer of 3 to 7.
• the structural unit represented by formula (4) is usually formed when the formyl group in the structural unit represented by formula (3) above further acts as a chain transfer agent.
• PVA (A) has a tertiary carbon atom (a carbon atom directly bonded to three carbon atoms). It is also preferable that PVA (A) has a structural unit containing a tertiary carbon atom. In such a case, that is, when PVA (A) has a branched structure, various performances are improved when used, for example, as a dispersant for suspension polymerization.
• PVA (A) has a structural unit represented by the above formula (3) or (4), and R 2 to R 7 are hydrogen atoms
• PVA (A) has a tertiary carbon atom.
• PVA (A) may have structural units other than the structural units derived from vinyl esters (vinyl alcohol units and vinyl ester units) and the structural units derived from aliphatic unsaturated aldehydes.
• monomers which give the other structural units include ⁇ -olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene; acrylic acid, methacrylic acid; acrylic acid esters such as methyl acrylate and ethyl acrylate; methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; acrylamide derivatives such as N-methylacrylamide, N-ethylacrylamide, and 2-acrylamido-2-methylpropanesulfonic acid; methacrylamide derivatives such as N-methylmethacrylamide and N-ethylmethacrylamide; maleic acid; maleic acid esters such as monomethyl maleate and dimethyl maleate; fumaric acid; fumaric acid esters such as
• the proportion of the other structural units in the total structural units in PVA (A) may preferably be 20 mol% or less, more preferably 10 mol% or less, and even more preferably 5 mol% or 1 mol%. On the other hand, the proportion of the other structural units may be, for example, 0.1 mol% or more, or 1 mol% or more.
• the lower limit of the viscosity average polymerization degree of PVA (A) may be, for example, 100, but may be preferably 200, more preferably 300, even more preferably 400, and even more preferably 500.
• the viscosity average polymerization degree is equal to or higher than the lower limit, the protective colloid property is enhanced, and various performances are improved when used, for example, as a dispersant for suspension polymerization.
• the upper limit of this viscosity average polymerization degree is preferably 2,000, more preferably 1,500, even more preferably 1,000, and even more preferably 800.
• PVA (A) can be produced, for example, by a process including a step (step A) of polymerizing a vinyl ester in the presence of an aliphatic unsaturated aldehyde and/or an aliphatic saturated aldehyde, and a step (step B) of saponifying the obtained vinyl ester polymer.
• step A vinyl ester is polymerized in the presence of an aliphatic unsaturated aldehyde and/or an aliphatic saturated aldehyde to obtain a vinyl ester polymer.
• Methods for polymerizing vinyl ester include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among these methods, bulk polymerization without a solvent and solution polymerization using a solvent such as alcohol are preferred. As the alcohol, alcohols having 3 or less carbon atoms are preferred, methanol, ethanol, n-propanol, and isopropanol are more preferred, and methanol is even more preferred.
• a batch or continuous reaction method can be used. There is no particular restriction on the polymerization temperature when carrying out the polymerization reaction, but a range of 5°C to 200°C is appropriate.
• vinyl esters examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, and vinyl versatate. Of these, vinyl acetate is preferred.
• the polymerization initiator used in the polymerization reaction may be any of the known polymerization initiators, such as azo initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); and organic peroxide initiators such as benzoyl peroxide, n-propyl peroxycarbonate, and diisopropyl peroxydicarbonate.
• the amount of polymerization initiator used is preferably 0.01 to 5% by mass, based on the vinyl ester used.
• aliphatic unsaturated aldehyde examples include acetaldehyde, propionaldehyde, butylaldehyde, 1-pentanal, 1-hexanal, 1-octanal, 1-nonanal, 1-decanal, etc., with acetaldehyde being preferred.
• the aliphatic unsaturated aldehyde and the aliphatic saturated aldehyde may be used alone or in combination of two or more.
• the amount of the aliphatic unsaturated aldehyde and the aliphatic saturated aldehyde used is preferably, for example, 0.1 to 10 mass% relative to the vinyl ester.
• chain transfer agent other than the aliphatic unsaturated aldehyde and the aliphatic saturated aldehyde may be allowed to coexist.
• chain transfer agents include ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol and 3-mercaptopropionic acid; thiocarboxylic acids such as thioacetic acid; and halogenated hydrocarbons such as trichloroethylene and perchloroethylene.
• copolymerizable monomers include those mentioned above as monomers that provide other structural units.
• step B the vinyl ester polymer obtained in step A is saponified, for example, in an alcohol solution using an alkali catalyst or an acid catalyst to obtain PVA.
• a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide, or sodium methoxide
• an acid catalyst such as p-toluenesulfonic acid
• the solvent 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.
• methanol or a mixed solution of methanol and methyl acetate as the solvent and perform the saponification reaction in the presence of sodium hydroxide, which is a basic catalyst, because it is simple.
• Saponification can be performed using a belt reactor, a kneader reactor, a tower reactor, or the like.
• the manufacturing method may further include, after step B, a step of washing the resin solid containing PVA, a step of drying the resin solid containing PVA, a step of heat treating the resin solid containing PVA, etc.
• amphiphilic Substance (B) The amphiphilic substance (B) contained in the composition of the present invention includes at least one selected from the group consisting of surfactants and vinyl alcohol-based polymers having a degree of saponification of less than 60 mol%.
• the amphiphilic substance means a substance (polymer, compound, etc.) having a hydrophilic group and a hydrophobic group in the same molecule.
• the amphiphilic substance (B) is preferably at least one selected from the group consisting of surfactants and vinyl alcohol-based polymers having a degree of saponification of less than 60 mol%.
• an operation called hot charging may be performed in which an aqueous solution of PVA is added to a polymerization solution heated to a temperature of 60°C or higher.
• hot charging is performed using an aqueous solution containing a conventional dispersant for suspension polymerization, PVA may aggregate, resulting in coarse polymerized particles.
• the mechanism by which PVA aggregates is unclear, but it is speculated that when an aqueous solution containing PVA that has affinity with water molecules due to electrostatic interactions or hydrogen bonds is instantly mixed with a high-temperature solution with a different polarity from the PVA aqueous solution, the balance of affinity is lost and PVA aggregates.
• the function of PVA as a dispersant tends to decrease at high temperatures of 60°C or higher, and a dispersant that is stable even at high temperatures of 60°C or higher is required.
• the inventors have found that by combining PVA (A) with an amphiphilic substance (B), it is possible to suppress the aggregation of PVA (A) when hot charging an aqueous solution of PVA (A), and that even when suspension polymerization is performed at a high temperature of 60°C or higher, it is possible to obtain polymer particles with a small average particle size, few coarse particles, and good plasticizer absorption.
• amphiphilic substance (B) suppresses the sudden loss of the balance of affinity between the substances and further stabilizes the colloidal particles, thereby suppressing the aggregation of PVA (A).
• the content of the amphiphilic substance (B) in the composition of the present invention is preferably 0.001% by mass or more and 30% by mass or less, more preferably 0.01% by mass or more and 20% by mass or less, even more preferably 0.1% by mass or more and 10% by mass or less, and even more preferably 1.0% by mass or more and 5.0% by mass or less, relative to PVA (A) (100% by mass).
• the amphiphilic substance (B) contains multiple compounds, the total content of the compounds is preferably within the above range. By having the content of the amphiphilic substance (B) within the above range, the aggregation inhibition effect of the PVA (A) molecules themselves is improved, and the stability of suspension polymerization is superior.
• anionic surfactants and nonionic surfactants are preferred, and anionic surfactants are more preferred. Only one type of surfactant may be used, or two or more types may be used in combination.
• anionic surfactants include alkyl sulfates, alkyl sulfonates, alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfates (alkyl ether sulfates), polyoxyalkylene alkyl ether carboxylates (alkyl ether acetates), ⁇ -olefin sulfonates, phosphate salts, acyl amino acid salts, acyltaurate salts, acyl lactates, soaps (higher fatty acids), alkyl sulfosuccinates, acyl hydrolyzed collagen salts, and acyl isethionates, among which acyl amino acid salts and acyltaurate salts are preferred, and acyl amino acid salts are more preferred.
• Anionic surfactants are preferably metal salts, more preferably alkali metal salts, and even more preferably sodium salts.
• acyl amino acid salts include sodium lauroyl sarcosine, sodium lauroyl methylalanine, sodium cocoyl glutamate, potassium cocoyl glycine, and the like, and sodium lauroyl sarcosine is preferred.
• acyltaurate salts include sodium lauroyl taurate. Only one type of anionic surfactant may be used, or two or more types may be used in combination.
• nonionic surfactants include polyoxyethylene lauryl ether, oleyl ether, octylphenyl ether, nonylphenyl ether, polyoxyethylene monostearate, palmitate, and oleate. Only one type of nonionic surfactant may be used, or two or more types may be used in combination.
• the vinyl alcohol polymer having a degree of saponification of less than 60 mol% is preferably a vinyl alcohol polymer having a degree of saponification of 40 mol% or less.
• the lower limit of the degree of saponification of a vinyl alcohol polymer having a degree of saponification of less than 60 mol% is preferably 10 mol%, more preferably 20 mol%, and even more preferably 30 mol%.
• the vinyl alcohol polymer having a degree of saponification of less than 60 mol% is preferably an anion-modified vinyl alcohol polymer.
• anion-modified vinyl alcohol polymers include carboxylic acid-modified vinyl alcohol polymers and phosphonic acid-modified vinyl alcohol polymers, and carboxylic acid-modified vinyl alcohol polymers are more preferred.
• the carboxyl group of the carboxylic acid-modified vinyl alcohol polymer may be in the form of a salt.
• the viscosity average degree of polymerization of the vinyl alcohol polymer having a degree of saponification of less than 60 mol% is, for example, preferably 50 to 500, more preferably 100 to 300.
• the various performances are improved when the composition of the present invention is used as a dispersant for suspension polymerization.
• the mass ratio of the hydrophobic group to the hydrophilic group is 4:1 or more and 1:4 or less.
• the composition of the present invention may further contain other components other than PVA (A) and amphiphilic substance (B).
• the other components include solvents such as water and alcohol, resins other than PVA (A) and amphiphilic substance (B), additives such as surfactants and plasticizers, and various compounds used during production.
• the composition of the present invention may be in the form of a solution such as an aqueous solution, or in the form of a powder.
• the lower limit of the total amount of PVA (A) and amphiphilic substance (B) in the non-volatile content of the composition of the present invention is preferably 30% by mass, more preferably 50% by mass, and in some cases even more preferably 70% by mass, 90% by mass, or 99% by mass.
• the upper limit of the total amount of PVA (A) and amphiphilic substance (B) in the non-volatile content of the composition of the present invention may be 100% by mass.
• the non-volatile content refers to components other than the solvent.
• composition of the present invention can be used in a variety of applications similar to those of conventionally known PVA, such as raw materials for films and fibers, additives for paper and fiber processing, adhesives, dispersants for emulsion polymerization and suspension polymerization, and inorganic binders.
• the composition of the present invention can be particularly suitably used as a dispersant for suspension polymerization of vinyl compounds and the like, as described in detail below.
• the dispersant for suspension polymerization of the present invention includes the composition of the present invention described above.
• a dispersant is an additive used to enhance the dispersibility of a monomer during suspension polymerization and control the particle size of the resulting polymer particles.
• the lower limit of the total amount of PVA (A) and amphiphilic substance (B) in the non-volatile content of the dispersant of the present invention is preferably 30% by mass, more preferably 50% by mass, and even more preferably 70% by mass, 90% by mass, or 99% by mass.
• the upper limit of the total amount of PVA (A) and amphiphilic substance (B) in the non-volatile content of the dispersant of the present invention may be 100% by mass.
• Non-volatile components other than PVA (A) and amphiphilic substance (B) that may be contained in the dispersant of the present invention include resins other than PVA (A) and amphiphilic substance (B), additives such as surfactants and plasticizers, and each compound used during production.
• the content of the volatile content in the dispersant may be 20% by mass or less, 15% by mass or less, or 10% by mass or less.
• Examples of volatile matters that may be contained in the dispersant of the present invention include alcohol, water, and the like.
• the dispersant of the present invention may be substantially composed of PVA (A) and amphiphilic substance (B).
• the shape of the dispersant of the present invention is not particularly limited, but may be a powder.
• the dispersant of the present invention may be a solution such as an aqueous solution.
• the content of volatile matters in the dispersant may be, for example, 50% by mass or more and 99.9% by mass.
• One embodiment of the dispersant of the present invention may be a dispersant for suspension polymerization that uses PVA (A) and amphiphilic substance (B) in combination.
• a method for producing a dispersant that includes a step of mixing PVA (A) and amphiphilic substance (B), and a dispersant obtained by mixing PVA (A) and amphiphilic substance (B) are also embodiments of the present invention.
• the dispersants of these embodiments may also further contain components other than PVA (A) and amphiphilic substance (B).
• the dispersant of the present invention is suitable as a dispersant for suspension polymerization of vinyl compounds.
• the dispersant of the present invention polymerization stability under high temperature conditions is improved, and polymer particles with a small average particle size and few coarse particles can be efficiently obtained.
• the polymer particles obtained by suspension polymerization using the dispersant of the present invention also have good plasticizer absorption.
• the method for producing a vinyl polymer of the present invention comprises a step of polymerizing a vinyl compound in the presence of PVA (A) and an amphipathic substance (B).
• the production method is similar to known methods for producing vinyl polymers, except that PVA (A) and an amphipathic substance (B) are used as dispersants.
• the method for producing a vinyl polymer of the present invention generally involves suspension polymerization of a vinyl compound in an aqueous medium.
• aqueous medium in addition to pure water, aqueous solutions containing various additive components or aqueous media containing other organic solvents can be used.
• the method for producing a vinyl polymer of the present invention may also include a step of adding PVA (A) and an amphiphilic substance (B) to the aqueous medium.
• the amount of PVA (A) added is not particularly limited, but is preferably 100 ppm or more and 50,000 ppm or less, more preferably 200 ppm or more and 20,000 ppm or less, and in some cases 10,000 ppm or less, 5,000 ppm or less, or 2,000 ppm or less, based on the mass of the vinyl compound.
• the amount of amphiphilic substance (B) added is preferably 0.001% by mass or more and 30% by mass or less relative to PVA (A), more preferably 0.01% by mass or more and 20% by mass or less, even more preferably 0.1% by mass or more and 10% by mass or less, and even more preferably 1.0% by mass or more and 5.0% by mass or less.
• the content of amphiphilic substance (B) within the above range, the aggregation suppression effect of the PVA (A) molecules themselves is improved, and the stability of suspension polymerization is more excellent.
• the PVA (A) and the amphiphilic substance (B) may be premixed and fed to the suspension polymerization system of the vinyl compound, or the PVA (A) and the amphiphilic substance (B) may be fed separately.
• the PVA (A) and the amphipathic substance (B) may be handled, for example, as a powder, or may be mixed with a medium such as water and handled as a solution. That is, when PVA (A) and the amphipathic substance (B) are mixed, for example, a powder of PVA (A) and a powder of the amphipathic substance (B) may be mixed, or a solution of PVA (A) and a solution of the amphipathic substance (B) may be mixed, or a solution of PVA (A) into which powder of the amphipathic substance (B) is added may be used. These powders or solutions may be charged into a polymerization tank or the like. The powder or solution of PVA (A) and the powder or solution of the amphipathic substance (B) may be charged separately into a polymerization tank or the like.
• the PVA (A) and the amphiphilic substance (B) may be the dispersant of the present invention.
• the dispersant of the present invention may be used alone or in combination with other dispersants, etc.
• the polymerization initiator used in the method for producing a vinyl polymer of the present invention can be one that has been conventionally used in the polymerization of vinyl compounds. Specifically, the same polymerization initiators as those exemplified in the polymerization of the vinyl ester monomers described above can be used.
• additives include polymerization regulators such as aldehydes, halogenated hydrocarbons, and mercaptans, and polymerization inhibitors such as phenol compounds, sulfur compounds, and N-oxide compounds.
• polymerization regulators such as aldehydes, halogenated hydrocarbons, and mercaptans
• polymerization inhibitors such as phenol compounds, sulfur compounds, and N-oxide compounds.
• pH adjusters, scale inhibitors, crosslinking agents, etc. can also be added. Multiple additives described above may be used in combination.
• Vinyl compounds that can be suspension polymerized in the vinyl polymer manufacturing method 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 ethers, etc.
• vinyl chloride is preferred.
• the vinyl polymer manufacturing method of the present invention is particularly suitable for use when vinyl chloride is suspended in a single polymer or in a combination of 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 acid esters such as methyl (meth)acrylate and ethyl (meth)acrylate; ⁇ -olefins such as ethylene and propylene; unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid; acrylonitrile; styrene; vinylidene chloride; vinyl ethers, etc.
• vinyl esters such as vinyl acetate and vinyl propionate
• (meth)acrylic acid esters such as methyl (meth)acrylate and ethyl (meth)acrylate
• ⁇ -olefins such as ethylene and propylene
• unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid
• acrylonitrile acrylonitrile
• styrene vinylidene chloride
• vinyl ethers etc.
• the charging ratio of each component, polymerization temperature, polymerization time, etc. can be the same as the conditions conventionally used in the suspension polymerization of vinyl compounds such as vinyl chloride.
• the method for producing a vinyl polymer of the present invention can be suitably applied to suspension polymerization at a high temperature of 60°C or higher (e.g., 60°C or higher and 80°C or lower), but the polymerization temperature may be lower than 60°C.
• the polymerization temperature may be, for example, 30°C or higher and 80°C or lower, 40°C or higher and 75°C or lower, or 50°C or higher and 70°C or lower.
• the method for producing a vinyl polymer of the present invention can efficiently produce vinyl polymer particles that are highly stable during polymerization, have a small average particle size, and contain few coarse particles, even when the polymerization temperature is high. Furthermore, the vinyl polymer particles obtained by the production method of the present invention also have good plasticizer absorption.
• CH linked to OH groups has a peak at 3.8 to 4.0 ppm (integral value [M])
• CH linked to OAc groups has a peak at 4.2 to 4.6 ppm (integral value [N]).
• the methyl group adjacent to the carbonyl group is assigned to 2.08 to 2.22 ppm (integral value [O])
• the methylene group that is not adjacent to the methine group linked to an OH group or an OAc group and is adjacent to a formyl group or a carbonyl group is assigned to 2.3 to 2.5 ppm (integral value [P]).
• the peak of the proton constituting the formyl group appears at 9.5 to 10.0 ppm (integral value [Q]).
• CH linked to OH groups has a peak at 3.8 to 4.0 ppm (integral value [M])
• CH linked to OAc groups has a peak at 4.2 to 4.6 ppm (integral value [N]).
• the peak of protons derived from alkenyl groups is assigned to 5.7 to 6.0 ppm (integral value [R]).
• the CH linked to the OH group has a peak at 3.8 to 4.0 ppm (integral value [M]), and the CH linked to the OAc group has a peak at 4.2 to 4.6 ppm (integral value [N]).
• the peak of the proton derived from the formyl group is assigned to 9.5 to 10.0 ppm (integral value [Q]).
• the formyl group content of PVA was calculated as a value relative to the structural units derived from vinyl alcohol monomers (vinyl alcohol units and vinyl ester units) from the following formula.
• Formyl group content (mol%) ⁇ [Q]/([M]+[N]) ⁇ 100
• CH linked to OH groups has a peak at 3.8 to 4.0 ppm (integral value [M])
• CH linked to OAc groups has a peak at 4.2 to 4.6 ppm (integral value [N]).
• the peak of the proton of the methyl group derived from the alkyl group of formula (2) is assigned to 2.08 to 2.22 ppm (integral value [T]) or 0.7 to 1.0 ppm (integral value [S]).
• the content of the alkyl group was calculated from the following formula as a value relative to the structural units derived from the vinyl alcohol monomer (vinyl alcohol units and vinyl ester units).
• the content of the alkyl group corresponds to the content of the group in formula (2) where R 1 is an alkyl group in the PVA.
• Alkyl group content (mol%) ⁇ ([T]/3+[S]/3)/([M]+[N]) ⁇ 100
• the solid content concentration at the time of stopping the polymerization was 43.6% by mass and the polymerization rate was 45%. Subsequently, the unreacted monomer was removed by occasionally adding methanol at 30°C under reduced pressure, and a methanol solution of a vinyl ester polymer (concentration 38.2% by mass) was obtained.
• a methanol solution of a vinyl ester polymer 34 parts by mass of the polymer in the solution
• methanol solution 58.0 parts by mass of a methanol solution of a vinyl ester polymer (34 parts by mass of the polymer in the solution) was prepared by further adding methanol to the methanol solution, and 1.78 parts by mass of a 10% by mass methanol solution of sodium hydroxide, 0.88 parts by mass of ion-exchanged water, and 10 parts by mass of methyl acetate were added to the methanol solution, and saponification was carried out at 40° C. (the polymer concentration in the saponification solution was 30% by mass, the water content of the saponification solution was 1% by mass, and the molar ratio of sodium hydroxide to vinyl acetate units in the polymer was 0.0128).
• a gel-like substance was generated about 15 minutes after the addition of the methanol solution of sodium hydroxide, and the gel was crushed in a crusher and left at 40° C. for 1 hour to allow saponification to proceed. Thereafter, 160 parts by mass of methyl acetate and 40 parts by mass of methanol were added, and the solution was left to wash at 40° C. for 30 minutes. This washing operation was repeated twice, and the white solid obtained by dehydration was vacuum-dried at 40° C. for 16 hours to obtain PVA-1 as PVA (A).
• the physical properties of PVA-1 are shown in Table 3.
• PVA-2 to PVA-4 were produced as PVA (A) in the same manner as in Production Example 1, except that the type and amount of aldehyde used in polymerization, the amount of AIBN used, and the molar ratio of sodium hydroxide to vinyl acetate units (NaOH molar ratio) in saponification were changed as shown in Table 1.
• the physical properties of PVA-2 to PVA-4 are shown in Table 3.
• the temperature inside the reaction vessel was adjusted to 60°C, 0.5 parts by mass of 3-MPA was added, and then 1.2 parts by mass of 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added to start polymerization.
• the polymerization temperature was maintained at 60°C, and a 50% methanol solution of 3-MPA was continuously added at 4mL/hr so that 3-MPA was 5 parts by mass in the entire system.
• the polymerization rate reached 40%, the polymerization was stopped by cooling.
• unreacted vinyl acetate was removed under reduced pressure to obtain a methanol solution of modified polyvinyl acetate (modified PVAc).
• a NaOH methanol solution (10% concentration) was added to the modified PVAc solution adjusted to a concentration of 27% by mass so that the alkali molar ratio (moles of NaOH/moles of vinyl ester units in modified PVAc) was 0.0042 to perform saponification.
• the water content of the saponified solution was adjusted to 1% by mass.
• a polyvinyl alcohol polymer PVA-5 was obtained as an amphiphilic substance (B), which has a viscosity average degree of polymerization of 140, a degree of saponification of 40 mol%, and contains a carboxyl group as an ionic group at the end.
• the degree of polymerization of PVA-5 and the presence or absence of a carboxyl group at the end were confirmed as follows.
• the methanol solution of the modified PVAc obtained before the saponification reaction from which unreacted vinyl acetate had been removed was poured into n-hexane to precipitate the modified PVAc, and the recovered modified PVAc was dissolved in acetone for reprecipitation purification three times, followed by drying under reduced pressure at 60°C to obtain a purified modified PVAc.
• the methanol solution of the modified PVAc purified product was saponified with an alkali molar ratio of 0.2, followed by Soxhlet extraction with methanol for three days, and then drying to obtain a purified modified PVA.
• the viscosity average degree of polymerization of the modified PVA was measured according to the conventional method of JIS K6726:1994 and found to be 140.
• the modified PVA was dissolved in heavy water and subjected to nuclear magnetic resonance analysis, confirming the presence of a carboxyl group (COONa group) at one end of the molecule.
• Example 1 A 4% by mass aqueous solution of PVA-1 and a 30% by mass aqueous solution of sodium lauroyl sarcosine (manufactured by Kawaken Fine Chemicals Co., Ltd., "SOYPON (registered trademark) SLP") as an amphiphilic substance (B) were mixed in a mass ratio of 750:1 under a condition of 25°C to obtain an aqueous solution which is a composition in which the content of sodium lauroyl sarcosine relative to PVA-1 (100% by mass) is 1% by mass.
• SOYPON registered trademark
• Examples 2 to 10 Comparative Examples 1 to 3
• the compositions (aqueous solutions) of Examples 2 to 10 and Comparative Examples 1 to 3 were obtained in the same manner as in Example 1, except that the type of PVA (A) and the type and amount of amphiphilic substance (B) used were changed as shown in Table 3.
• the autoclave was degassed until the pressure inside the autoclave was 0.0067 MPa to remove oxygen. Then, 800 parts by mass of vinyl chloride was charged, and the contents inside the autoclave were heated to 65 ° C., and polymerization was started under stirring. The pressure inside the autoclave at the start of polymerization was 1.02 MPa. 2.5 hours after the start of polymerization, the polymerization was stopped when the pressure inside the autoclave reached 0.70 MPa, and unreacted vinyl chloride was removed. Thereafter, the polymerized slurry was taken out and dried at 65° C. for 17 hours to obtain vinyl chloride polymer particles.
• Amount of coarse particles in vinyl chloride polymer particles The amount of the vinyl chloride polymer particles that did not pass through a sieve with a mesh size of 250 ⁇ m (60 mesh in terms of the mesh size of the JIS standard sieve) was calculated in mass %. The smaller the value, the fewer the coarse particles, indicating that the dispersant used has excellent polymerization stability.
• Plasticizer Absorption (%) 100 ⁇ [(Z ⁇ X)/(Y ⁇ X) ⁇ 1]
• compositions of Examples 1 to 10 were used as dispersants for suspension polymerization, vinyl chloride polymer particles with a small average particle size, few coarse particles, and good plasticizer absorption were obtained even when suspension polymerization was performed under high temperature conditions such as 65°C.
• Each of the compositions of Examples 1 to 10 was confirmed to be useful as a dispersant for suspension polymerization.
• Comparative Examples 1 to 3 the average particle size of the vinyl chloride polymer particles obtained by suspension polymerization under high temperature conditions was large, and there were many coarse particles. The plasticizer absorption was also low.
• composition of the present invention can be used as a dispersant during suspension polymerization of vinyl compounds.

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