WO2013115239A1 - 懸濁重合用分散安定剤 - Google Patents
懸濁重合用分散安定剤 Download PDFInfo
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- WO2013115239A1 WO2013115239A1 PCT/JP2013/052025 JP2013052025W WO2013115239A1 WO 2013115239 A1 WO2013115239 A1 WO 2013115239A1 JP 2013052025 W JP2013052025 W JP 2013052025W WO 2013115239 A1 WO2013115239 A1 WO 2013115239A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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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
Definitions
- the present invention relates to a dispersion stabilizer for suspension polymerization of a vinyl compound containing a polyoxyalkylene-modified vinyl alcohol polymer.
- a partially saponified vinyl alcohol polymer (hereinafter, the vinyl alcohol polymer may be abbreviated as PVA) is used as a dispersion stabilizer for suspension polymerization of vinyl compounds (for example, vinyl chloride).
- vinyl compounds for example, vinyl chloride
- partially saponified PVA has low solubility in water and handling properties are insufficient, so that a hydrophilic polyoxyethylene group is introduced into the side chain of PVA in order to improve the handling property. Attempts have been made to improve water solubility.
- Patent Document 7 discloses a method using PVA having a saponification degree of 65 to 85 mol%, an average polymerization degree of 500 to 1000, and having an oxyalkylene group in the side chain as a dispersion stabilizer for suspension polymerization of vinyl compounds. Proposed.
- the dispersion stabilizers described in Patent Documents 1 to 7 have the required performance, specifically: (1) The plasticizer has high absorbency even when used in a small amount, and (2) For removal of monomer components such as the remaining vinyl compound, (3) that there are few coarse particles, (4) particles that have as uniform a particle size as possible, and scale adhesion can be prevented. It is hard to say that satisfactory performance has been obtained.
- the present invention provides a dispersion stabilizer for suspension polymerization that satisfies the required performances of the above (1) to (4) and is excellent in polymerization stability in suspension polymerization of vinyl compounds such as vinyl chloride. For the purpose.
- the present inventors have a specific polyoxyalkylene group in the side chain, a viscosity average polymerization degree of less than 500, a saponification degree of more than 70 mol%, and a polyoxyalkylene group modification rate of 0.1 mol. It has been found that a dispersion stabilizer for suspension polymerization containing a polyoxyalkylene-modified vinyl alcohol polymer (A) in an amount of not less than 10% and not more than 10 mol% achieves the above object. Furthermore, the present inventors have made extensive studies and have completed the present invention.
- the present invention [1] A suspension containing a polyoxyalkylene-modified vinyl alcohol polymer (A) having a polyoxyalkylene group having 2 to 4 carbon atoms in the alkylene group and 2 to 100 repeating units in the side chain A dispersion stabilizer for polymerization,
- the polyoxyalkylene-modified vinyl alcohol polymer (A) has a viscosity average degree of polymerization of less than 500, a saponification degree of greater than 70 mol%, and a polyoxyalkylene group modification rate of 0.1 mol% or more and 10 mol. % Of the dispersion stabilizer for suspension polymerization.
- the dispersion stabilizer for suspension polymerization of the present invention is a specific polyoxyalkylene-modified vinyl alcohol polymer (A) described below (hereinafter, polyoxyalkylene-modified vinyl alcohol polymer may be abbreviated as POA-modified PVA). ).
- the dispersion stabilizer for suspension polymerization may contain PVA (B) other than the POA-modified PVA (A) and other components as long as the gist of the present invention is not impaired.
- PVA polyoxyalkylene-modified vinyl alcohol polymer
- the POA-modified PVA (A) used in the present invention is a polyoxyalkylene group having 2 to 4 carbon atoms in the alkylene group and 2 to 100 repeating units (hereinafter, the polyoxyalkylene group is abbreviated as POA group).
- the viscosity average polymerization degree is less than 500
- the saponification degree is greater than 70 mol%
- the POA group modification rate is 0.1 mol% or more and 10 mol% or less.
- the POA-modified PVA (A) has the specific POA group in the side chain, has a viscosity average polymerization degree of less than 500, and a caking degree of more than 70 mol%. Further, by using the POA group represented by the above general formula (I) as the POA group, the plasticizer absorbability and the demonomerization property of the vinyl polymer particles obtained are further improved.
- R 1 and R 2 are both hydrogen atoms, or one of them is a methyl group, the other is a hydrogen atom, and R 3 and R 4 are Any one is a methyl group or an ethyl group, and the other is a hydrogen atom.
- R 1 and R 2 are hydrogen atoms, and from the viewpoint of the production method, it is more preferable that R 3 is a hydrogen atom and R 4 is a methyl group or an ethyl group.
- R 5 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- the alkyl group having 1 to 8 carbon atoms include a methyl group, a butyl group, a hexyl group, and an octyl group.
- R 5 is preferably a hydrogen atom, a methyl group or a butyl group, and more preferably a hydrogen atom or a methyl group.
- m and n each represent the average number of repeating units of oxyalkylene, and 1 ⁇ m ⁇ 50 and 1 ⁇ n ⁇ 50.
- a unit having the number of repeating units m is referred to as unit 1
- a unit having the number of repeating units n is referred to as unit 2.
- the arrangement of unit 1 and unit 2 may be in the form of either a random copolymer or a block copolymer. From the standpoint that the physical properties based on the oxyalkylene group are more easily expressed, Preferably there is.
- the number m of repeating units 1 in the POA group unit 1 represented by the general formula (I) is preferably 1 ⁇ m ⁇ 30, more preferably 1 ⁇ m ⁇ 20, further preferably 1 ⁇ m ⁇ 10, and 1 ⁇ m ⁇ 10. 5 is particularly preferred.
- the number of repeating units n of the POA group unit 2 represented by the general formula (I) is preferably 2 ⁇ n ⁇ 40, more preferably 4 ⁇ n ⁇ 35, and further preferably 6 ⁇ n ⁇ 30.
- the method for producing the POA-modified PVA (A) is not particularly limited, but the unsaturated monomer having a POA group represented by the general formula (I) and a vinyl ester monomer are copolymerized.
- a method of saponifying the obtained POA-modified vinyl ester polymer is preferable.
- the unsaturated monomer having a POA group represented by the general formula (I) is preferably an unsaturated monomer represented by the following general formula (II). Therefore, a method of copolymerizing an unsaturated monomer represented by the following general formula (II) and a vinyl ester monomer and saponifying the obtained POA-modified vinyl ester polymer is more preferable.
- R 1 , R 2 , R 3 , R 4 , R 5 , m, and n are the same as those in the general formula (I).
- R 6 represents a hydrogen atom or —COOM, where M represents a hydrogen atom, an alkali metal or an ammonium group.
- R 7 represents a hydrogen atom, a methyl group or —CH 2 —COOM, where M is as defined above.
- X is -O -, - CH 2 -O - , - CO -, - (CH 2) k -, - CO-O -, - CO-NR 8 - or -CO-NR 8 -CH 2 - represents a.
- R 8 represents a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms, and 1 ⁇ k ⁇ 15.
- R 7 is preferably a hydrogen atom or a methyl group.
- R 1 and R 2 are both hydrogen atoms, one of R 3 and R 4 is a methyl group or an ethyl group, and the other is hydrogen. More preferably, it is an atom, R 5 is a hydrogen atom or a methyl group, and R 6 is a hydrogen atom.
- R 1 and R 2 in the general formula (II) are both hydrogen atoms
- R 3 and R 4 are either ethyl groups
- the other is a hydrogen atom
- R 5 is a hydrogen atom
- R 6 is hydrogen.
- unsaturated monomers represented by the general formula (II) include polyoxyalkylene mono (meth) acrylamide, polyoxyalkylene mono (meth) allyl ether, polyoxyalkylene monovinyl ether, polyoxyalkylene mono Specific examples include (meth) acrylates.
- polyoxyethylene polyoxybutylene monoacrylamide N-methylene polyoxyethylene polyoxybutylene monoacrylamide, polyoxyethylene polyoxybutylene monomethacrylamide, N-methylene polyoxyethylene.
- Polyoxybutylene monomethacrylamide poly Reoxyethylene polyoxybutylene monoallyl ether, polyoxyethylene polyoxybutylene monomethallyl ether, polyoxyethylene polyoxybutylene monovinyl ether, polyoxyethylene polyoxybutylene monoacrylate, polyoxyethylene polyoxybutylene monomethacrylate, etc. Can be mentioned.
- polyoxyethylene polyoxybutylene monoacrylamide, N-methylene polyoxyethylene polyoxybutylene monoacrylamide, polyoxyethylene polyoxybutylene monomethacrylamide, N-methylene polyoxyethylene polyoxybutylene monomethacrylamide, polyoxyethylene Polyoxybutylene monoallyl ether is preferably used, and polyoxyethylene polyoxybutylene monomethacrylamide, N-methylene polyoxyethylene polyoxybutylene monomethacrylamide, polyoxyethylene polyoxybutylene monoallyl ether is particularly preferably used.
- R 1 and R 2 are both hydrogen atoms
- R 3 and R 4 are either methyl groups
- the other are hydrogen atoms
- R 5 is a hydrogen atom
- R 6 is a hydrogen atom.
- unsaturated monomers in which polyoxybutylene of the unsaturated monomer represented by the general formula (II) exemplified above is replaced with polyoxypropylene.
- polyoxyethylene polyoxypropylene monomethacrylamide, N-methylene polyoxyethylene polyoxypropylene monomethacrylamide, and polyoxyethylene polyoxypropylene monoallyl ether are preferably used.
- N-methylene polyoxyethylene polyoxypropylene monomethacrylamide is particularly preferably used.
- R 5 in the general formula (II) is an alkyl group having 1 to 8 carbon atoms
- the unsaturated monomer represented by the general formula (II) is specifically R 1 in the general formula (II) is a hydrogen atom.
- R 2 is a hydrogen atom
- any one of R 3 and R 4 is a methyl group or an ethyl group, the other is a hydrogen atom
- R 5 is a hydrogen atom
- R 6 is a hydrogen atom. Examples thereof include those in which the terminal hydroxyl group of the unsaturated monomer represented by the general formula (II) is substituted with an alkoxy group having 1 to 8 carbon atoms.
- polyoxyethylene polyoxybutylene monomethacrylamide, N-methylene polyoxyethylene polyoxybutylene monomethacrylamide, polyoxyethylene polyoxybutylene monoallyl ether, polyoxyethylene polyoxypropylene monomethacrylamide, N-methylene Polyoxyethylene polyoxypropylene monomethacrylamide and polyoxyethylene polyoxybutylene monomethacrylamide are preferably used as unsaturated monomers in which the hydroxyl group at the terminal of polyoxyethylene polyoxypropylene monoallyl ether is substituted with a methoxy group.
- N-methylene polyoxyethylene polyoxybutylene monomethacrylamide, polyoxyethylene polyoxypropylene monomethacrylamide, N-methylene polyoxy Hydroxyl end Ji Ren polyoxypropylenemonool methacrylamide unsaturated monomer substituted with a methoxy group are particularly preferably used.
- the temperature when copolymerizing the unsaturated monomer represented by the general formula (II) and the vinyl ester monomer is not particularly limited, but is preferably 0 ° C. or higher and 200 ° C. or lower, and 30 ° C. or higher and 140 ° C. The following is more preferable.
- a copolymerization temperature lower than 0 ° C. is not preferable because a sufficient polymerization rate cannot be obtained.
- polymerization is higher than 200 degreeC, it is difficult to obtain POA modified PVA (A) which has the target POA group modification rate.
- the polymerization method employed for copolymerizing the unsaturated monomer represented by the general formula (II) and the vinyl ester monomer includes batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization. Either is acceptable.
- As the polymerization method an arbitrary method can be adopted from known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among these, a bulk polymerization method or a solution polymerization method in which polymerization is performed in the absence of a solvent or in the presence of an alcohol solvent is preferably employed.
- an emulsion polymerization method is employed.
- the alcohol solvent used in the bulk polymerization method or the solution polymerization method methanol, ethanol, n-propanol or the like can be used, but is not limited thereto. These solvents may be used alone or in combination of two or more.
- azo initiators As the initiator used for copolymerization, conventionally known azo initiators, peroxide initiators, redox initiators and the like are appropriately selected according to the polymerization method.
- the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethyl valeronitrile), etc.
- peroxide initiators include perisopropyl compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl Perester compounds such as peroxyneodecanate, ⁇ -cumylperoxyneodecanate, t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpent
- the initiator can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator.
- the redox initiator include a combination of the above-described peroxide and a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.
- Vinyl ester monomers used for copolymerization include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, and lauric acid. Examples thereof include vinyl, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate and the like. Of these, vinyl acetate is most preferred.
- Copolymerization may be carried out in the presence of a chain transfer agent as long as the gist of the invention is not impaired.
- Chain transfer agents include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; halogenated hydrocarbons such as trichloroethylene and perchloroethylene; sodium phosphinate 1 And phosphinic acid salts such as hydrates. Of these, aldehydes and ketones are preferably used.
- the addition amount of the chain transfer agent may be determined according to the chain transfer constant of the added chain transfer agent and the degree of polymerization of the target vinyl ester polymer. In general, the content is preferably 0.1% by mass or more and 10% by mass or less based on the vinyl ester monomer.
- the saponification reaction of the POA-modified vinyl ester polymer may be an alcoholysis 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. Hydrolysis reactions can be applied.
- the solvent that can be used in this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene. These can be used alone or in combination of two or more. Among them, it is convenient and preferable to perform the saponification reaction using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst.
- the POA-modified PVA (A) has a POA group modification rate of 0.1 mol% to 10 mol%, preferably 0.2 mol% to 5 mol%. More preferably, it is 3 mol% or more and 2 mol% or less.
- the POA group modification rate is represented by the mole fraction of POA groups with respect to the total of monomer units constituting the POA-modified PVA (A).
- the POA group modification rate of the POA-modified PVA (A) exceeds 10 mol%, the proportion of hydrophobic groups contained in one molecule of the POA-modified PVA (A) increases, and the water solubility of the POA-modified PVA (A) increases.
- the POA group modification rate is a unit of an unsaturated monomer having a POA group represented by the above general formula (I) in the side chain in the number of moles of all monomer units constituting the POA-modified PVA. The ratio of the number of moles (mol%).
- the POA group modification rate of the POA-modified PVA may be obtained from the POA-modified PVA or from the precursor POA-modified vinyl ester polymer, and both can be obtained by proton NMR.
- the POA group modification is performed by the following method.
- the rate can be calculated. That is, for example, when obtaining from a POA-modified vinyl ester polymer, specifically, first, the reprecipitation purification of the POA-modified vinyl ester polymer is sufficiently performed three or more times using an n-hexane / acetone mixed solvent. After that, drying is performed under reduced pressure at 50 ° C. for 2 days to prepare a sample of POA-modified vinyl ester polymer for analysis.
- the sample is then dissolved in CDCl 3 and measured at room temperature using proton NMR.
- the peak ⁇ 4.7 to 4.7
- the POA group modification rate can be calculated from the area of 5.2 ppm) and the area of the peak ⁇ (0.8 to 1.0 ppm) derived from the proton of the terminal methyl group of unit 2 using the following formula.
- n represents a repeating unit of unit 2.
- POA group modification rate (mol%) ⁇ (Area of peak ⁇ / 3n) / (Area of peak ⁇ + (Area of peak ⁇ / 3n) ⁇ ⁇ 100
- the viscosity average polymerization degree of the POA-modified PVA (A) is less than 500, preferably 50 or more and 450 or less, more preferably 100 or more and 400 or less, and more preferably 150 or more and 350 or less. Is more preferable.
- the viscosity average polymerization degree of the POA-modified PVA (A) is 500 or more, it is difficult to remove the residual monomer component from the vinyl polymer particles obtained by suspension polymerization of the vinyl compound, or the POA-modified PVA (A) is obtained.
- the plasticizer absorbability of the vinyl polymer particles decreases.
- the saponification degree of the POA-modified PVA (A) is important to be greater than 70 mol% from the viewpoint of water solubility and water dispersibility, and is preferably from 71 mol% to 90 mol%, preferably 71.5 mol%. More preferably, it is 80 mol% or less, and more preferably 72 mol% or more and 77 mol% or less.
- the saponification degree of POA-modified PVA (A) is a value obtained by measurement according to JIS K6726.
- the dispersion stabilizer for suspension polymerization of the present invention preferably contains PVA (B) having a viscosity average polymerization degree of 500 or more and a saponification degree of 60 mol% or more in addition to the POA-modified PVA (A). .
- PVA (B) having a viscosity average polymerization degree of 500 or more and a saponification degree of 60 mol% or more in addition to the POA-modified PVA (A).
- the saponification degree of PVA (B) used in the present invention is preferably 60 mol% or more, more preferably 65 mol% or more and 95 mol% or less, and 70 mol% or more and 90 mol% or less. Further preferred. When the degree of saponification of PVA (B) is less than 60 mol%, the water solubility of PVA (B) may be reduced and the handleability may deteriorate.
- the degree of saponification of PVA (B) is a value that can be measured according to JIS K6726.
- the viscosity average polymerization degree of PVA (B) is preferably 500 or more, more preferably 550 or more and 5000 or less, and further preferably 600 or more and 3500 or less.
- the viscosity average polymerization degree of PVA (B) is less than 500, the polymerization stability when the vinyl compound is subjected to suspension polymerization is lowered.
- the viscosity average polymerization degree of PVA (B) can be calculated by the same method as the above-mentioned POA modified PVA (A).
- PVA (B) may be used alone, or two or more types having different characteristics may be used in combination.
- the dispersion stabilizer for suspension polymerization of the present invention may contain other various additives as long as the gist of the present invention is not impaired.
- the additive include polymerization regulators such as aldehydes, halogenated hydrocarbons and mercaptans; polymerization inhibitors such as phenol compounds, sulfur compounds and N-oxide compounds; pH regulators; cross-linking agents; An antifungal agent, an antiblocking agent, and an antifoaming agent.
- the dispersion stabilizer for suspension polymerization of the present invention is particularly suitably used for suspension polymerization of vinyl compounds.
- vinyl compounds 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; Examples include styrene, acrylonitrile, vinylidene chloride, vinyl ether and the like.
- the dispersion stabilizer for suspension polymerization of the present invention is particularly preferably used in suspension polymerization of vinyl chloride alone or together with a monomer capable of copolymerizing with vinyl chloride and vinyl chloride. Used.
- Monomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylic esters such as methyl (meth) acrylate and ethyl (meth) acrylate; ethylene, ⁇ -olefins such as propylene; unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid; acrylonitrile, styrene, vinylidene chloride, vinyl ether and the like.
- vinyl esters such as vinyl acetate and vinyl propionate
- (meth) acrylic esters such as methyl (meth) acrylate and ethyl (meth) acrylate
- ethylene, ⁇ -olefins such as propylene
- unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid
- acrylonitrile, styrene, vinylidene chloride, vinyl ether and the like
- oil-soluble or water-soluble polymerization initiators conventionally used for polymerization of vinyl chloride monomers and the like can be used.
- oil-soluble polymerization initiator include percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, t -Perester compounds such as butyl peroxypivalate, t-hexyl peroxypivalate, ⁇ -cumyl peroxyneodecanate; acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate Peroxides such as 3,5,5-trimethylhexanoyl peroxide and lauroyl peroxide; azo compounds such as azobis-2,4-dimethylvaleronitrile
- water-soluble polymerization initiator examples include potassium persulfate, ammonium persulfate, hydrogen peroxide, cumene hydroperoxide, and the like. These oil-soluble or water-soluble polymerization initiators may be used alone or in combination of two or more.
- the polymerization temperature is not particularly limited, and can be adjusted to a high temperature exceeding 90 ° C. as well as a low temperature of about 20 ° C.
- dispersion stabilizer for suspension polymerization of the present invention may be used alone, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose which are usually used for suspension polymerization of vinyl compounds in an aqueous medium are used.
- Water-soluble cellulose ethers such as gelatin; water-soluble polymers such as gelatin; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan trioleate, glycerin tristearate, ethylene oxide propylene oxide block copolymer; polyoxyethylene sorbitan monolaurate, polyoxyethylene
- part and % represent parts by mass and mass%, respectively.
- the POA-modified PVA (A) obtained by the following production examples was evaluated according to the following method.
- Viscosity average polymerization degree and saponification degree of PVA The viscosity average polymerization degree and saponification degree of PVA were determined by the method described in JIS K6726.
- the POA group modification rate of PVA was determined according to the method using proton NMR described above. For proton NMR, 500 MHz JEOL GX-500 was used.
- the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 1.6 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. While the delay solution was dropped to make the monomer composition (ratio of vinyl acetate and monomer A) in the polymerization solution constant, polymerization was performed at 60 ° C. for 6 hours and then cooled to stop the polymerization. The total amount of comonomer added until the polymerization was stopped was 32 g. The solid content concentration when the polymerization was stopped was 7.6%. Subsequently, unreacted vinyl acetate monomer was removed while sometimes adding methanol under reduced pressure at 30 ° C.
- AIBN 2,2′-azobisisobutyronitrile
- POA-modified PVA (A1) had a viscosity-average polymerization degree of 300, a saponification degree of 74 mol%, and a POA group modification rate of 0.7 mol%.
- Example 1 The PVA (B) having a viscosity average polymerization degree of 2000 and a saponification degree of 80 mol% was 800 ppm with respect to the vinyl chloride monomer, and the POA-modified PVA (A1) was 200 ppm with respect to the vinyl chloride monomer.
- Dispersion stabilizer was prepared by dissolving in deionized water. The dispersion stabilizer thus obtained was charged into a 5 L autoclave.
- the polymerization was stopped when the pressure in the autoclave after the elapse of 3.5 hours from the start of the polymerization became 0.70 MPa, and after removing the unreacted vinyl chloride monomer, the polymerization reaction product was taken out, Drying was performed at 65 ° C. for 16 hours to obtain vinyl chloride polymer particles.
- Amount of scale adhesion 100 parts of the vinyl chloride polymer particles obtained in Example 1, 50 parts of dioctyl phthalate (DOP), 5 parts of tribasic lead sulfate and 1 part of lead stearate are roll-kneaded at 150 ° C. for 7 minutes. Then, five sheets having a thickness of 0.1 mm and 140 mm ⁇ 140 mm were prepared, the number of fish eyes of each sheet was measured, and the total number of fish eyes was used as an index of the amount of scale adhesion, and evaluated according to the following criteria. .
- Plasticizer absorbability [ ⁇ (CA) / (BA) ⁇ -1] ⁇ 100
- Residual monomer amount As an indicator of demonomerization, the polymerization reaction product in the suspension polymerization of vinyl chloride was taken out, dried at 65 ° C for 5 hours, and the residual monomer amount at that time was determined by headspace gas chromatography. Measured by chromatography.
- Examples 2 to 12 A vinyl chloride polymer particle was obtained by suspension polymerization of vinyl chloride in the same manner as in Example 1 except that POA-modified PVA (A2 to 12) was used instead of POA-modified PVA (A1).
- Table 3 shows the physical properties of the POA-modified PVA (A2 to 12) used and the evaluation results of the obtained vinyl chloride polymer particles.
- Example 1 Suspension polymerization of vinyl chloride was performed in the same manner as in Example 1 except that POA-modified PVA (A1) was not used.
- Table 3 shows the physical properties of the POA-modified PVA (A) used and the evaluation results of the obtained vinyl chloride polymer particles. In this case, the plasticizer absorbability of the obtained vinyl chloride polymer particles was insufficient, and the amount of residual monomer was large.
- Example 3 In Example 1, POA-modified PVA (A14) having a saponification degree of 60 mol% was used in place of POA-modified PVA (A1). However, the POA-modified PVA (A14) was not dissolved in water, and vinyl chloride heavy Suspension polymerization of the coalesced particles could not be performed.
- the dispersion stabilizer for suspension polymerization of the present invention when used, since the polymerization stability is high, the formation of coarse particles is small, and particles having a uniform particle diameter are obtained. Blocking and scale adhesion due to instability are reduced. Furthermore, it is possible to obtain polymer particles that are extremely excellent in plasticizer absorbability and demonomerization. Therefore, the industrial usefulness of the dispersion stabilizer for suspension polymerization of the present invention is extremely high.
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Abstract
Description
[1]アルキレン基の炭素数が2~4であり、繰り返し単位数が2以上100以下のポリオキシアルキレン基を側鎖に有するポリオキシアルキレン変性ビニルアルコール系重合体(A)を含有する懸濁重合用分散安定剤であって、
該ポリオキシアルキレン変性ビニルアルコール系重合体(A)は、粘度平均重合度が500未満であり、けん化度が70モル%より大きく、かつポリオキシアルキレン基変性率が0.1モル%以上10モル%以下である、懸濁重合用分散安定剤。
[2]前記ポリオキシアルキレン基が、下記一般式(I)で示されるポリオキシアルキレン基である上記[1]の懸濁重合用分散安定剤;
[3]さらに、粘度平均重合度が500以上、けん化度が60モル%以上のビニルアルコール系重合体(B)を含有する上記[1]または[2]の懸濁重合用分散安定剤;
[4]前記R1および前記R2がともに水素原子である上記[1]~[3]のいずれかの懸濁重合用分散安定剤;
本発明の懸濁重合用分散安定剤は、後述する特定のポリオキシアルキレン変性ビニルアルコール系重合体(A)(以下、ポリオキシアルキレン変性ビニルアルコール系重合体をPOA変性PVAと略記することがある)を含有する。また、当該懸濁重合用分散安定剤は、本発明の趣旨を損なわない範囲で、上記POA変性PVA(A)以外のPVA(B)や、他の成分を含有してもよい。以下、各成分について詳述する。
本発明で用いられるPOA変性PVA(A)は、アルキレン基の炭素数が2~4であり、繰り返し単位数が2以上100以下のポリオキシアルキレン基(以下、ポリオキシアルキレン基をPOA基と略記することがある)を側鎖に有し、粘度平均重合度が500未満であり、けん化度が70モル%より大きく、かつPOA基変性率が0.1モル%以上10モル%以下である。
POA基変性率(モル%)={(ピークβの面積/3n)/(ピークαの面積+(ピークβの面積/3n)}×100
粘度平均重合度=([η]×103/8.29)(1/0.62)
本発明の懸濁重合用分散安定剤は、上記POA変性PVA(A)に加えて、さらに粘度平均重合度が500以上、けん化度が60モル%以上のPVA(B)を含有することが好ましい。このように、粘度平均重合度がPOA変性PVA(A)よりも高いPVA(B)を併用する組成物からなる分散安定剤とすることで、懸濁重合時の重合安定性が向上し粗粒化をより一層抑制できるため好ましい。
本発明の懸濁重合用分散安定剤は、本発明の趣旨を損なわない範囲で、その他の各種添加剤を含有してもよい。該添加剤としては、例えば、アルデヒド類、ハロゲン化炭化水素類、メルカプタン類などの重合調節剤;フェノール化合物、イオウ化合物、N-オキサイド化合物などの重合禁止剤;pH調整剤;架橋剤;防腐剤;防黴剤、ブロッキング防止剤;消泡剤等が挙げられる。
本発明の懸濁重合用分散安定剤は、特にビニル系化合物の懸濁重合に好適に用いられる。ビニル系化合物としては、塩化ビニル等のハロゲン化ビニル;酢酸ビニル、プロピオン酸ビニル等のビニルエステル;アクリル酸、メタクリル酸、これらのエステルおよび塩;マレイン酸、フマル酸、これらのエステルおよび無水物;スチレン、アクリロニトリル、塩化ビニリデン、ビニルエーテル等が挙げられる。これらの中でも、本発明の懸濁重合用分散安定剤は、特に好適には塩化ビニルを単独で、または塩化ビニルおよび塩化ビニルと共重合することが可能な単量体と共に懸濁重合する際に用いられる。塩化ビニルと共重合することができる単量体としては、酢酸ビニル、プロピオン酸ビニルなどのビニルエステル;(メタ)アクリル酸メチル、(メタ)アクリル酸エチルなどの(メタ)アクリル酸エステル;エチレン、プロピレンなどのα-オレフィン;無水マレイン酸、イタコン酸などの不飽和ジカルボン酸類;アクリロニトリル、スチレン、塩化ビニリデン、ビニルエーテル等が挙げられる。
PVAの粘度平均重合度およびけん化度は、JIS K6726に記載の方法により求めた。
PVAのPOA基変性率は、上述したプロトンNMRを用いた方法に準じて求めた。なお、プロトンNMRは、500MHzのJEOL GX-500を用いた。
撹拌機、還流冷却管、窒素導入管、コモノマー滴下口および開始剤の添加口を備えた3Lの反応器に、酢酸ビニル690g、メタノール2310g、表2に示す構造のブロック共重合POA基含有モノマー(単量体A)7.1gを仕込み、窒素バブリングをしながら30分間系内を窒素置換した。また、ディレー溶液としてPOA基含有モノマー(単量体A)をメタノールに溶解して濃度20%としたコモノマー溶液を調製し、窒素ガスのバブリングにより窒素置換した。反応器の昇温を開始し、内温が60℃となったところで、2,2’-アゾビスイソブチロニトリル(AIBN)1.6gを添加し重合を開始した。ディレー溶液を滴下して重合溶液中のモノマー組成(酢酸ビニルと単量体Aの比率)が一定となるようにしながら、60℃で6時間重合した後冷却して重合を停止した。重合を停止するまで加えたコモノマーの総量は32gであった。また重合停止時の固形分濃度は7.6%であった。続いて30℃、減圧下でメタノールを時々添加しながら未反応の酢酸ビニルモノマーの除去を行い、POA変性PVAcのメタノール溶液(濃度63%)を得た。さらに、これにメタノールを加えて調製したPOA変性PVAcのメタノール溶液78.8g(溶液中のPOA変性PVAc50.0g)に、1.01gのアルカリ溶液(水酸化ナトリウムの12%水溶液)を添加してけん化を行った(けん化溶液のPOA変性PVAc濃度30%、POA変性PVAc中の酢酸ビニルユニットに対する水酸化ナトリウムのモル比0.0052)。40℃で1時間放置してけん化を進行させた後、酢酸メチル150gを加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノール200gを加えて室温で3時間放置洗浄した。上記の洗浄操作を3回繰り返した後、遠心脱液して得られた白色固体を真空乾燥機中50℃で1日間放置してPOA変性PVA(A1)を得た。POA変性PVA(A1)の粘度平均重合度は300、けん化度は74モル%およびPOA基変性率は0.7モル%であった。
酢酸ビニルおよびメタノールの仕込み量、重合時に使用するPOA基を有する不飽和単量体の種類およびその使用量、並びに重合率等の重合条件、けん化時におけるPOA変性PVAcの濃度、酢酸ビニルユニットに対する水酸化ナトリウムのモル比等のけん化条件を変更したこと以外は、実施例1と同様にしてPOA変性PVA(A2~16)を製造した。製造条件を表1に、用いたPOA基を有する不飽和単量体の構造を表2に示す。
粘度平均重合度2000、けん化度80モル%のPVA(B)が塩化ビニル単量体に対して800ppm、上記POA変性PVA(A1)が塩化ビニル単量体に対して200ppmとなるように、それぞれ脱イオン水に溶解させ、分散安定剤を調製した。このようにして得られた分散安定剤を、容量5Lのオートクレーブに仕込んだ。次いで、オートクレーブにクミルパーオキシネオデカノエートの70%トルエン溶液0.65部およびt-ブチルパーオキシネオドデカネートの70%トルエン溶液1.05部を仕込み、オートクレーブ内の圧力が0.0067MPaとなるまで脱気して酸素を除いた後、塩化ビニル940部を仕込み、オートクレーブ内の内容物を57℃に昇温して撹拌下で塩化ビニル単量体の重合を開始した。重合開始時におけるオートクレーブ内の圧力は0.80MPaであった。重合を開始してから3.5時間経過後のオートクレーブ内の圧力が0.70MPaとなった時点で重合を停止し、未反応の塩化ビニル単量体を除去した後、重合反応物を取り出し、65℃にて16時間乾燥を行い、塩化ビニル重合体粒子を得た。
実施例1で得られた塩化ビニル重合体粒子について、平均粒子径、粒度分布、スケール付着量、可塑剤吸収性および残留モノマー量を以下の方法にしたがって評価した。評価結果を表3に示す。
タイラーメッシュ基準の金網を使用して、乾式篩分析により粒度分布を測定し、塩化ビニル重合体粒子の平均粒子径を求めた。
JIS標準篩い42メッシュオンの含有量を質量%で表示した。
A:0.5%未満
B:0.5%以上1%未満
C:1%以上
JIS標準篩い60メッシュオンの含有量を質量%で表示した。
A:5%未満
B:5%以上10%未満
C:10%以上
なお、42メッシュオンの含有量および60メッシュオンの含有量はともに、値が小さいほど粗大粒子が少なくて粒度分布がシャープであり、重合安定性に優れていることを示している。
実施例1で得られた塩化ビニル重合体粒子100部、ジオクチルフタレート(DOP)50部、三塩基性硫酸鉛5部およびステアリン酸鉛1部を7分間150℃でロール練りして、厚み0.1mm、140mm×140mmのシートを5枚作製し、各シートのフィッシュアイの数を測定し、合計したフィッシュアイの数をスケール付着量の指標とし、以下の基準で評価した。
A:4個未満
B:4個以上11個未満
C:11個以上
脱脂綿を0.02g詰めた容量5mLのシリンジの質量を量り(Agとする)、そこに塩化ビニル重合体粒子0.5gを入れ質量を秤量し(Bgとする)、そこにジオクチルフタレート(DOP)1gを入れ15分静置後、3000rpm、40分遠心分離して質量を量った(Cgとする)。そして、下記の計算式より可塑剤吸収性(%)を求めた。
可塑剤吸収性(%)=[{(C-A)/(B-A)}-1]×100
脱モノマー性の指標として、塩化ビニルの懸濁重合における重合反応物を取り出したのち、65℃にて5時間乾燥を行い、その時点での残留モノマー量をヘッドスペースガスクロマトグラフィーにて測定した。
POA変性PVA(A1)に代えて、POA変性PVA(A2~12)をそれぞれ使用したこと以外は実施例1と同様にして塩化ビニルの懸濁重合を行い、塩化ビニル重合体粒子を得た。使用したPOA変性PVA(A2~12)の物性および得られた塩化ビニル重合体粒子の評価結果を表3に示す。
POA変性PVA(A1)を使用しなかったこと以外は実施例1と同様にして、塩化ビニルの懸濁重合を行った。使用したPOA変性PVA(A)の物性および得られた塩化ビニル重合体粒子の評価結果を表3に示す。この場合、得られた塩化ビニル重合体粒子の可塑剤吸収性が不十分であり、残存モノマー量が多かった。
POA変性PVA(A1)に代えて、粘度平均重合度が630であるPOA変性PVA(A13)を使用したこと以外は実施例1と同様にして塩化ビニルの懸濁重合を行った。使用したPOA変性PVA(A)の物性および得られた塩化ビニル重合体粒子の評価結果を表3に示す。この場合、得られた塩化ビニル重合体粒子の可塑剤吸収性が不十分であり、残存モノマー量が多かった。
実施例1においてPOA変性PVA(A1)に代えて、けん化度が60モル%であるPOA変性PVA(A14)を使用したが、該POA変性PVA(A14)は水に溶解せず、塩化ビニル重合体粒子の懸濁重合を行なうことができなかった。
POA変性PVA(A1)に代えて、POA基変性率が0.05モル%であるPOA変性PVA(A15)を使用したこと以外は実施例1と同様にして、塩化ビニルの懸濁重合を行った。使用したPOA変性PVA(A15)の物性および得られた塩化ビニル重合体粒子の評価結果を表3に示す。この場合、得られた塩化ビニル重合体粒子の可塑剤吸収性が不十分であり、残存モノマー量が多かった。
POA変性PVA(A1)に代えて、POA基変性率が11モル%であるPOA変性PVA(A16)を使用したが、該POA変性PVA(A16)は水に溶解せず、塩化ビニル重合体粒子の懸濁重合を行うことができなかった。
Claims (4)
- アルキレン基の炭素数が2~4であり、繰り返し単位数が2以上100以下のポリオキシアルキレン基を側鎖に有するポリオキシアルキレン変性ビニルアルコール系重合体(A)を含有する懸濁重合用分散安定剤であって、
該ポリオキシアルキレン変性ビニルアルコール系重合体(A)は、粘度平均重合度が500未満であり、けん化度が70モル%より大きく、かつポリオキシアルキレン基変性率が0.1モル%以上10モル%以下である、懸濁重合用分散安定剤。 - さらに、粘度平均重合度が500以上、けん化度が60モル%以上のビニルアルコール系重合体(B)を含有する請求項1または2に記載の懸濁重合用分散安定剤。
- 前記R1および前記R2がともに水素原子である請求項1~3のいずれかに記載の懸濁重合用分散安定剤。
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JP7488818B2 (ja) | 2019-07-09 | 2024-05-22 | デンカ株式会社 | 変性ビニルアルコール系重合体及び懸濁重合用分散安定剤 |
WO2021125020A1 (ja) | 2019-12-17 | 2021-06-24 | デンカ株式会社 | ポリビニルアルコール系樹脂組成物、懸濁重合用分散安定剤及びビニル系樹脂の製造方法 |
CN114555696A (zh) * | 2019-12-17 | 2022-05-27 | 电化株式会社 | 聚乙烯醇系树脂组合物、悬浮聚合用分散稳定剂以及乙烯基系树脂的制造方法 |
CN114555696B (zh) * | 2019-12-17 | 2024-03-05 | 电化株式会社 | 聚乙烯醇系树脂组合物、悬浮聚合用分散稳定剂以及乙烯基系树脂的制造方法 |
JP7483754B2 (ja) | 2019-12-17 | 2024-05-15 | デンカ株式会社 | ポリビニルアルコール系樹脂組成物、懸濁重合用分散安定剤及びビニル系樹脂の製造方法 |
WO2021206128A1 (ja) | 2020-04-07 | 2021-10-14 | デンカ株式会社 | 変性ビニルアルコール系重合体、懸濁重合用分散安定剤及びビニル系化合物の重合方法 |
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JPWO2013115239A1 (ja) | 2015-05-11 |
CN104066753A (zh) | 2014-09-24 |
CN104066753B (zh) | 2016-05-04 |
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