WO2018038112A1 - 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 - Google Patents
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 Download PDFInfo
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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
- 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
- C08F218/06—Vinyl formate
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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
- 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
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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
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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
- 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
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
Definitions
- the present invention relates to a modified vinyl alcohol polymer having a polyoxyalkylene group.
- the present invention also relates to a dispersion stabilizer for suspension polymerization, particularly a dispersion stabilizer suitable for suspension polymerization of vinyl compounds, particularly vinyl chloride.
- dispersion stabilizers such as polyvinyl alcohol and methylol.
- Dispersion stabilizers such as cellulose, vinyl acetate / maleic anhydride copolymer, and gelatin are used.
- PVA polyvinyl alcohol
- the dispersion stabilizers described in Patent Documents 1 to 8 have the required performance, specifically, (1) resin particles having few coarse particles, and (2) resin particles having a uniform particle size as much as possible. (3) A resin having a high porosity can be obtained even in a small amount of use, and as a result, the removal of the monomer component is facilitated and the resin has a high plasticizer absorbency, (4) It is hard to say that satisfactory performance is obtained with respect to the suppression of foaming during polymerization.
- an object of the present invention is to provide a dispersion stabilizer for suspension polymerization that satisfies the required performances of (1) to (4) above when suspension-polymerizing a vinyl compound such as vinyl chloride. .
- the present inventors have a predetermined polyoxyalkylene group having an oxybutylene unit and an oxyethylene unit (hereinafter referred to as “modified group”) in the side chain.
- modified group a modified vinyl alcohol polymer having a modification rate of 0.01 mol% to 10 mol% as a dispersion stabilizer for suspension polymerization of vinyl compounds.
- the present invention is a modified vinyl alcohol polymer having a monomer unit represented by the following general formula (I) and having a modification rate of 0.01 mol% to 10 mol%.
- Formula (I): (In the formula, BO represents an oxybutylene unit, EO represents an oxyethylene unit, m and n represent the number of repeating units of each oxyalkylene unit, and 1 ⁇ m ⁇ 10 and 1 ⁇ n ⁇ 60.)
- the modified vinyl alcohol polymer according to the present invention has a viscosity average polymerization degree of 300 to 5,000.
- the modified vinyl alcohol polymer according to the present invention has a saponification degree of 60 mol% to 99.9 mol%.
- the modified vinyl alcohol polymer according to the present invention has a viscosity average polymerization degree of 1000 or less.
- the modified vinyl alcohol polymer according to the present invention has a saponification degree of 65 mol% to 80 mol%.
- the present invention is a dispersion stabilizer for suspension polymerization containing the modified vinyl alcohol polymer according to the present invention.
- a vinyl compound monomer or a vinyl compound monomer and a monomer copolymerizable therewith
- This is a method for producing a vinyl-based resin which comprises carrying out suspension polymerization by dispersing a mixture in water.
- the dispersion stabilizer for suspension polymerization according to the present invention When suspension polymerization of a vinyl compound is performed using the dispersion stabilizer for suspension polymerization according to the present invention, resin particles with little formation of coarse particles and high particle size uniformity can be obtained. Furthermore, since the formation of coarse particles is small, blocking during polymerization is suppressed, and particles with high uniformity in particle diameter can be obtained, thereby reducing scale adhesion. And since the polymer particle
- the dispersion stabilizer for suspension polymerization of the present invention contains a modified vinyl alcohol polymer (modified PVA) having a monomer unit represented by the following general formula (I).
- n is preferably 3 or more, and more preferably 5 or more. Further, m is preferably 9 or less, and more preferably 8 or less. n is preferably 20 or more, more preferably 30 or more, and more preferably 40 or more. N is preferably 55 or less, and more preferably 50 or less.
- the modified PVA has a modification rate of 0.01 mol% or more and 10 mol% or less. If the modification rate exceeds 10 mol%, the proportion of hydrophobic groups contained in one molecule of the modified PVA is increased, and the water solubility of the modified PVA is reduced, and therefore it is difficult to use as a dispersion stabilizer for suspension polymerization. Become. Therefore, the modification rate is important to be 10 mol% or less, preferably 5 mol% or less, more preferably 2 mol% or less, and even more preferably 1 mol% or less.
- the modification rate is important to be 0.01 mol% or more, preferably 0.05 mol% or more, and more preferably 0.1 mol% or more.
- the modification rate is the ratio (mol%) of the number of moles of the monomer unit represented by the general formula (I) to the number of moles of all the monomer units constituting the modified PVA.
- the modification rate can be determined by proton NMR.
- the modified PVA is saponified to a saponification degree of 99.95 mol% or more, and then thoroughly washed with methanol to prepare a modified PVA for analysis.
- the prepared modified PVA for analysis is dissolved in heavy water, and a few drops of a heavy NaOH aqueous solution is added to adjust the pH to 14, followed by measurement at 80 ° C. using proton NMR.
- the viscosity average degree of polymerization of the modified PVA is preferably 300 or more, more preferably 400 or more, and more preferably 500 or more in order to increase the dispersion stability when the vinyl compound is subjected to suspension polymerization. Even more preferred.
- the viscosity average degree of polymerization of the modified PVA is preferably 5000 or less, more preferably 4000 or less, and more preferably 3000 or less in order to prevent the aqueous solution viscosity from becoming high and difficult to handle. Even more preferably, it is still more preferably 1500 or less, and still more preferably 1000 or less.
- the viscosity average polymerization degree is measured in accordance with JIS K6726: 1994. That is, it is obtained from the intrinsic viscosity [ ⁇ ] measured in water at 30 ° C. after completely saponifying and purifying the modified PVA.
- the degree of saponification of the modified PVA is preferably 60 mol% or more, more preferably 65 mol% or more, and even more preferably 70 mol% or more in order to increase water solubility and facilitate handling. preferable. Further, the degree of saponification of the modified PVA is preferably 99.9 mol% or less in order to increase the porosity of the particles obtained when the vinyl compound is subjected to suspension polymerization and to increase the plasticizer absorbability. % Or less is more preferable, and 80 mol% or less is even more preferable.
- the degree of saponification of the modified PVA is measured according to JIS K6726: 1994. That is, it can be determined by quantifying the residual acetic acid group (mol%) in the sample with sodium hydroxide and subtracting it from 100.
- a method of copolymerizing a vinyl ester monomer typified by vinyl acetate and saponifying the resulting modified vinyl ester polymer is simple and preferable.
- vinyl ester monomers include vinyl formate, vinyl formate, vinyl propionate, vinyl valelate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, and vinyl versatate. Is mentioned.
- Formula (II) (Wherein BO is an oxybutylene unit (—CH 2 CH (CH 2 CH 3 ) O—), EO is an oxyethylene unit (—CH 2 CH 2 O—), and m and n are repetitions of the respective oxyalkylene units. Represents the number of units, 1 ⁇ m ⁇ 10, 1 ⁇ n ⁇ 60.)
- the polymerization method is not particularly limited, and a known polymerization method such as solution, emulsification, suspension, and bulk polymerization is arbitrarily used. In consideration of a saponification reaction described later, an alcohol such as methanol, ethanol, or isopropyl alcohol is used as a solvent. Solution polymerization is preferred.
- the preparation method of each monomer component is a divided preparation or a batch preparation such as a method of continuously adding a vinyl ester monomer and / or a comonomer. Any means may be used.
- the polymerization initiator used in the solution polymerization is not particularly limited, but azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), Azo compounds such as azobisdimethylvaleronitrile and azobismethoxyvaleronitrile, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, etc.
- the polymerization reaction temperature is not particularly limited, but can usually be set in a range of about 30 to 90 ° C. From the viewpoint of ease of operation and polymerization control, it is recommended that the polymerization be performed near the boiling point of the solvent used.
- monomers copolymerizable with vinyl ester monomers such as unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, or alkyl esters of these unsaturated monocarboxylic acids, maleic acid, fumaric acid Acids, unsaturated dicarboxylic acids such as itaconic acid or alkyl esters of these unsaturated dicarboxylic acids, nitriles or amides such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, etc.
- unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid
- alkyl esters of these unsaturated monocarboxylic acids maleic acid, fumaric acid Acids
- unsaturated dicarboxylic acids such as itaconic acid or alkyl esters of these unsaturated
- Olefin sulfonic acid or a salt thereof, vinyl ether, vinyl ketone, ⁇ -olefin, vinyl halide, vinylidene halide and the like can be copolymerized singly or in combination.
- the mixing ratio of such monomers is suitably 10 mol% or less, preferably 5 mol% or less in total with respect to the total number of moles of the vinyl ester monomer and the unsaturated monomer represented by formula (I). It is.
- the present invention is also intended to adjust the degree of polymerization of the resulting modified vinyl ester polymer upon copolymerization of the unsaturated monomer represented by the general formula (II) and the vinyl ester monomer.
- Copolymerization may be carried out in the presence of a chain transfer agent as long as the gist of the present 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.
- the addition amount of the chain transfer agent may be determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target modified vinyl ester polymer. In general, the addition amount of the chain transfer agent is preferably 0.1% by mass or more and 10% by mass or less based on the vinyl ester monomer.
- the saponification method for producing the modified PVA is not particularly limited, and it is preferable to use the polymer obtained by the above-described method in combination with an alcohol as a solvent according to a conventional method.
- the alcohol include methanol, ethanol, butanol and the like.
- the concentration of the polymer in the alcohol can be selected from the range of 20 to 50% by mass.
- Alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate and other alkali metal hydroxides and alcoholates can be used as the alkali catalyst, and as the acid catalyst, hydrochloric acid, An inorganic acid aqueous solution such as sulfuric acid and an organic acid such as p-toluenesulfonic acid can be used. These catalysts must be used in an amount of 1 to 100 mmol equivalents relative to the vinyl ester monomer. In such a case, the saponification temperature is not particularly limited, but is usually in the range of 10 to 70 ° C., and preferably in the range of 30 to 50 ° C. The reaction is usually carried out over 1 to 3 hours.
- the dispersion stabilizer for suspension polymerization of the present invention may contain PVA other than the above modified PVA and 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 preferably contains 10% by mass or more of modified PVA, more preferably contains 30% by mass or more, and 70% by mass. It is still more preferable to contain more than%.
- the dispersion stabilizer for suspension polymerization of the present invention can be suitably used particularly 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 when vinyl chloride is used alone or together with a monomer capable of copolymerizing vinyl chloride with 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
- the dispersion stabilizer for suspension polymerization of the present invention is suitable for producing a vinyl chloride resin for softness in terms of producing vinyl chloride resin particles having excellent plasticizer absorbability, but is excellent in demonomerization, particle size distribution, etc. Therefore, it can be applied to the production of rigid vinyl chloride resin.
- the dispersion stabilizer for suspension polymerization of the present invention can be used alone or in combination with other stabilizers such as cellulose derivatives and surfactants.
- the dispersion stabilizer for suspension polymerization of the present invention By using the dispersion stabilizer for suspension polymerization of the present invention, it is always possible to obtain a vinyl chloride resin having excellent physical properties such as the resin particles are porous, the particle size distribution is uniform, and the fisheye is small.
- examples of the polymerization method of the vinyl compound will be described in detail, but the method is not limited thereto.
- the polymerization initiator may be one conventionally used for the polymerization of vinyl compounds, such as diisopropylpropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, diethoxyethylperoxydicarbonate, etc.
- Perester compounds such as percarbonate compounds, t-butylperoxyneodecanoate, ⁇ -cumylperoxyneodecanoate, t-butylperoxyneodecanoate, acetylcyclohexylsulfonyl peroxide, 2,4,4 -Peroxides such as trimethylpentyl-2-peroxyphenoxyacetate, azo compounds such as azobis-2,4-dimethylpareronitrile, azobis (4-methoxy-2,4-dimethylpareronitrile), and further Potassium sulfate, ammonium persulfate, hydrogen peroxide, etc. alone or It can be used in conjunction look.
- a polymerization regulator e.g., a chain transfer agent, a gelation improver, an antistatic agent, a PH regulator and the like that are used as appropriate for the polymerization of the vinyl compound.
- the charging ratio of each component and the polymerization temperature for carrying out the polymerization of the vinyl compound may be determined in accordance with the conditions conventionally employed in the suspension polymerization of the vinyl compound, and there is no particular limitation.
- Azobisisobutyronitrile (2.5 g) was charged into a polymerization vessel, a comonomer solution was added dropwise thereto, polymerized at 60 ° C. for 9 hours, and then cooled to stop the polymerization.
- the total amount of vinyl acetate added until the polymerization was stopped was 1500 g, the total amount of methanol was 1440 g, and the total amount of monomer A was 141 g.
- the autoclave was degassed under vacuum, 5 kg of vinyl chloride monomer was added, and polymerization was carried out at 57 ° C. for 4 hours.
- the average particle size, particle size distribution, plasticizer absorption and bulk specific gravity of the obtained vinyl chloride resin were evaluated.
- the average particle size is measured according to JIS Z8815: 1994, 60 mesh (aperture 250 ⁇ m), 80 mesh (aperture 180 ⁇ m), 100 mesh (aperture 150 ⁇ m), 150 mesh (aperture 106 ⁇ m), 200 mesh ( Using a sieve having a mesh opening of 75 ⁇ m, the average particle size is 50% of the particle size (D50), and the difference between the particle size (D80) of 80% and 20% (D20). Distribution.
- the bulk specific gravity was measured in accordance with JIS K6720-2: 1999.
- the plasticizer absorption was measured by the following procedure. Glass fiber was packed in the bottom of an aluminum alloy container having an inner diameter of 25 mm and a depth of 85 mm, and 10 g of vinyl chloride resin was charged. To this was added 15 ml of a plasticizer (dioctyl phthalate, hereinafter referred to as DOP), and the mixture was allowed to stand for 30 minutes to fully penetrate the DOP into the vinyl chloride resin. Thereafter, excess DOP was centrifuged at an acceleration of 1500 G, and the mass of DOP absorbed in 10 g of vinyl chloride resin was measured and converted to DOP mass parts (phr) per 100 mass parts of vinyl chloride resin.
- DOP plasticizer
- the polymer slurry was taken out from the reactor, and the state of scale adhesion in the reactor was visually observed and evaluated according to the following criteria.
- the total amount of vinyl acetate added until the polymerization was stopped was 1500 g, and the total amount of methanol was 1290 g.
- unreacted vinyl acetate was removed by a conventional method, and the resulting polymer was saponified with sodium hydroxide by a conventional method to prepare a dispersion stabilizer.
- the viscosity average degree of polymerization, degree of saponification, and modification rate of the obtained dispersion stabilizer were measured by the above-described analysis method. As a result, the viscosity average degree of polymerization was 520, the degree of saponification was 74.2 mol%, and the degree of modification was 0.25 mol. %Met.
- the suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used for evaluation.
- Example 3 As a modified species, 1700 g of vinyl acetate, 1133 g of methanol, and 159.9 g of the same monomer A as in Example 1 were charged into a polymerization vessel, and the system was purged with nitrogen for 30 minutes. 2.5 g of azobisisobutyronitrile was charged into a polymerization vessel, polymerized at 60 ° C. for 9 hours, and then cooled to stop the polymerization. Thereafter, a dispersion stabilizer was prepared in the same manner as in Example 1. Evaluation was performed by carrying out suspension polymerization of vinyl chloride under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used.
- Example 4 When the polymer after removing unreacted vinyl acetate obtained in the same manner as in Example 3 was saponified with sodium hydroxide by a conventional method, the amount of sodium hydroxide was increased by 0.4 mmol, and a dispersion stabilizer was added. Produced. The saponification degree of the obtained dispersion stabilizer was 79.0 mol%. Thereafter, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used, and evaluation was performed.
- Example 6 A dispersion stabilizer was prepared in the same manner as in Example 3 except that the amount of the modified species was changed. Evaluation was performed by carrying out suspension polymerization of vinyl chloride under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used.
- Example 7 A dispersion stabilizer was prepared in the same manner as in Example 2 except that the amount of methanol charged was changed to 200 g. Evaluation was performed by carrying out suspension polymerization of vinyl chloride under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used.
- a dispersion stabilizer was prepared in the same manner as in Example 1. Evaluation was performed by carrying out suspension polymerization of vinyl chloride under the same conditions as in Example 1 except that the obtained disper
- Example 9 A dispersion stabilizer was prepared in the same manner as in Example 8 except that the amount of the modified species was changed. Evaluation was performed by carrying out suspension polymerization of vinyl chloride under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used.
- Example 1 Evaluation was performed by carrying out suspension polymerization of vinyl chloride under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used. In addition, when NMR of the obtained dispersion stabilizer was measured, a peak derived from a modified species observed with polyvinyl acetate was not observed with polyvinyl alcohol.
- the dispersion stabilizer according to the present invention is extremely advantageous industrially.
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Abstract
Description
一般式(I):
nは20以上が好ましく、30以上がより好ましく、40以上がより好ましい。また、nは55以下が好ましく、50以下がより好ましい。
〈分散安定剤の製造〉酢酸ビニル825g、メタノール923g、変性種として一般式(II)で示され、m=5~9、n=45~55であるポリオキシアルキレンアルケニルエーテル(花王社提供ラテムルPD-450、以下「単量体A」という。)35.3gを重合缶に仕込み、30分間系内を窒素置換した。単量体Aについてm=5~9、n=45~55であることは製造元に確認し、また、NMRにより確認した。また、単量体Aをメタノールと酢酸ビニルの混合溶液(メタノール:酢酸ビニル=42:58(質量比))に溶解して濃度13質量%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。アゾビスイソブチロニトリル2.5gを重合缶に仕込み、コモノマー溶液を滴下して60℃で9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酢酸ビニルの総量は1500g、メタノールの総量は1440g、単量体Aの総量は141gであった。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体を常法により水酸化ナトリウムでけん化して分散安定剤を作製した。得られた分散安定剤の粘度平均重合度、けん化度及び変性率を先述した分析法によって測定したところ、粘度平均重合度は520、けん化度は74.2モル%および変性率は0.16モル%であった。
A:泡立ちはただちに1mm以下となった。
B:1mm以上の泡が攪拌後10分以上残った。
C:1mm以上の泡が攪拌後60分以上残った。
A:反応器内にスケールの付着はほとんどない。
B:反応器内のバッフルや内壁に容易に除去できるスケールの付着が見られる。
C:反応器内のバッフルや内壁に除去しにくいスケールの付着が多く見られる。
酢酸ビニル825g、メタノール800g、変性種として実施例1と同様の単量体A141gを重合缶に仕込み、30分間系内を窒素置換した。また、メタノールと酢酸ビニルの混合溶液(メタノール:酢酸ビニル=42:58(質量比))を調製し、窒素ガスのバブリングにより窒素置換した。アゾビスイソブチロニトリル2.5gを重合缶に仕込み、60℃に昇温した。還流が始まってから混合溶液を8時間滴下しながら60℃で重合し、滴下終了から1時間後に冷却して重合を停止した。重合を停止するまで加えた酢酸ビニルの総量は1500g、メタノールの総量は1290gであった。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体を常法により水酸化ナトリウムでけん化して分散安定剤を作製した。得られた分散安定剤の粘度平均重合度、けん化度及び変性率を先述した分析法によって測定したところ、粘度平均重合度は520、けん化度は74.2モル%および変性率は0.25モル%であった。また、得られた分散安定剤を使用した以外は実施例1と同様の条件で塩化ビニルの懸濁重合を実施し、評価を行なった。
酢酸ビニル1700g、メタノール1133g、変性種として実施例1と同様の単量体A159.9gを重合缶に仕込み、30分間系内を窒素置換した。アゾビスイソブチロニトリル2.5gを重合缶に仕込み、60℃で9時間重合した後冷却して重合を停止した。その後、実施例1と同様にして分散安定剤を作製した。得られた分散安定剤を使用した以外は実施例1と同様の条件で塩化ビニルの懸濁重合を実施し、評価を行なった。
実施例3と同様にして得られた、未反応の酢酸ビニルを除去後の重合体を、常法により水酸化ナトリウムでけん化する際に水酸化ナトリウム量を0.4mmol増やして、分散安定剤を作製した。得られた分散安定剤のけん化度は79.0モル%だった。その後は、得られた分散安定剤を使用した以外は実施例1と同様の条件で塩化ビニルの懸濁重合を実施し、評価を行なった。
変性種量を変えた以外は実施例3と同様にして分散安定剤を作製した。得られた分散安定剤を使用した以外は実施例1と同様の条件で塩化ビニルの懸濁重合を実施し、評価を行なった。
仕込みのメタノール量を200gに変更した以外は実施例2と同様にして分散安定剤を作製した。得られた分散安定剤を使用した以外は実施例1と同様の条件で塩化ビニルの懸濁重合を実施し、評価を行なった。
酢酸ビニル1700g、メタノール1133g、変性種として一般式(II)で示され、m=5~9、n=15~25であるポリオキシアルキレンアルケニルエーテル(花王社提供ラテムルPD-420、以下「単量体B」という。)82.9gを重合缶に仕込み、30分間系内を窒素置換した。次いで、アゾビスイソブチロニトリル2.5gを重合缶に仕込み、60℃で9時間重合した後冷却して重合を停止した。その後は、実施例1と同様にして分散安定剤を作製した。得られた分散安定剤を使用した以外は実施例1と同様の条件で塩化ビニルの懸濁重合を実施し、評価を行なった。
変性種量を変えた以外は実施例8と同様にして分散安定剤を作製した。得られた分散安定剤を使用した以外は実施例1と同様の条件で塩化ビニルの懸濁重合を実施し、評価を行なった。
酢酸ビニル1700g、メタノール1133g、変性種として一般式(II)で示され、m=5~9、n=25~35であるポリオキシアルキレンアルケニルエーテル(花王社提供ラテムルPD-430、以下「単量体C」という。)109.6gを重合缶に仕込み、30分間系内を窒素置換した。アゾビスイソブチロニトリル2.5gを重合缶に仕込み、60℃で9時間重合した後冷却して重合を停止した。その後は、実施例1と同様にして分散安定剤を作製した。得られた分散安定剤を使用した以外は実施例1と同様の条件で塩化ビニルの懸濁重合を実施し、評価を行なった。
けん化度、変性種および重合度を変えた以外は実施例1と同様にして分散安定剤を作製した。得られた分散安定剤を使用した以外は実施例1と同様の条件で塩化ビニルの懸濁重合を実施し、評価を行なった。
酢酸ビニル1600g、メタノール605g、変性種としてポリオシキプロピレンアクリレート(日油株式会社提供ブレンマー PP800、以下「単量体D」という。)0.7gを重合缶に仕込み、30分間系内を窒素置換した。また、単量体Dをメタノールに溶解して濃度10質量%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。アゾビスイソブチロニトリル2.5gを重合缶に仕込み、コモノマー溶液を滴下して60℃で9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、メタノールの総量は1066g、単量体Dの総量は44.6gであった。その後は、実施例1と同様にして分散安定剤を作製した。得られた分散安定剤を使用した以外は実施例1と同様の条件で塩化ビニルの懸濁重合を実施し、評価を行なった。なお、得られた分散安定剤のNMRを測定したが、ポリ酢酸ビニルで観測された変性種由来のピークはポリビニルアルコールでは観測されなかった。
Claims (7)
- 粘度平均重合度が300~5000である請求項1記載の変性ビニルアルコール系重合体。
- けん化度が60モル%~99.9モル%である請求項1又は2に記載の変性ビニルアルコール系重合体。
- 粘度平均重合度が1000以下である請求項1~3のいずれか一項に記載の変性ビニルアルコール系重合体。
- けん化度が65モル%~80モル%である請求項1~4のいずれか一項に記載の変性ビニルアルコール系重合体。
- 請求項1~5のいずれか一項に記載の変性ビニルアルコール系重合体を含有する懸濁重合用分散安定剤。
- 請求項6に記載された懸濁重合用分散安定剤を用いて、ビニル系化合物単量体、又はビニル系化合物単量体とそれに共重合し得る単量体との混合物を水中に分散させて懸濁重合を行うことを含むビニル系樹脂の製造方法。
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