WO2015156312A1 - 懸濁重合用分散安定剤及びビニル樹脂の製造方法 - Google Patents
懸濁重合用分散安定剤及びビニル樹脂の製造方法 Download PDFInfo
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- WO2015156312A1 WO2015156312A1 PCT/JP2015/060959 JP2015060959W WO2015156312A1 WO 2015156312 A1 WO2015156312 A1 WO 2015156312A1 JP 2015060959 W JP2015060959 W JP 2015060959W WO 2015156312 A1 WO2015156312 A1 WO 2015156312A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
-
- 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
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
- C08F18/08—Vinyl acetate
-
- 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
- C08F2/18—Suspension polymerisation
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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
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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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
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Definitions
- the present invention relates to a dispersion stabilizer for suspension polymerization comprising a dispersant, a dispersoid containing a polymer having an ethylenically unsaturated monomer unit, and an aqueous emulsion containing a graft polymer as an optional component.
- the present invention also relates to a method for producing a vinyl resin in which a vinyl compound is subjected to suspension polymerization in the presence of a dispersion stabilizer for suspension polymerization.
- PVA partially saponified polyvinyl alcohol
- 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, it is difficult to increase the solid content concentration, and handleability is insufficient. For this reason, attempts have been made to use an aqueous emulsion as a dispersion stabilizer for suspension polymerization in order to improve handling.
- Patent Documents 1 and 2 describe a method of using an aqueous emulsion as a dispersion stabilizer for suspension polymerization of a vinyl compound.
- dispersion stabilizers (1) even when the amount used is small, the plasticizer has a high absorbability and can be easily processed, and (2) even when the amount used is small. Little fish eye during vinyl polymer sheet molding, (3) Even when the amount used is small, the hue deterioration of vinyl polymer due to heat is small or suppressed during molding (4) Handling of dispersion stabilizer Performance such as excellent properties is required.
- Patent Document 1 describes a dispersion stabilizer for suspension polymerization of a vinyl compound comprising an aqueous emulsion having a high ratio of graft polymer.
- the dispersion stabilizer was able to increase the solid content concentration to about 15%, and the handling property was slightly improved. However, it is difficult to further increase the solid content concentration, and handling properties and economical efficiency are insufficient. Other performances were also insufficient.
- Patent Document 2 describes a dispersion stabilizer for suspension polymerization comprising an aqueous emulsion having a high ratio of graft polymer. In the dispersion stabilizer for suspension polymerization, the viscosity was lowered by reducing the amount of polyvinyl alcohol, and the solid content concentration could be increased to about 30%. As a result, handling was improved over the dispersion stabilizer described in Patent Document 1, but it was still insufficient.
- An object of the present invention is to provide a dispersion stabilizer for suspension polymerization that satisfies the required performances (1) to (4).
- the above problem is a dispersion stabilizer for suspension polymerization comprising an aqueous emulsion containing a dispersant (A), a dispersoid (B), a graft polymer (C), and an aqueous medium, and the dispersant (A) is a surface active agent. Containing a dispersant, the dispersoid (B) contains a polymer having an ethylenically unsaturated monomer unit, and the graft polymer (C) graft-polymerizes the ethylenically unsaturated monomer to the dispersant (A).
- the mass ratio [A / (A + B + C)] of the dispersant (A) to the total amount of (A), (B) and (C) is 0.001 or more and less than 0.18, (A ), (B) and (C) to the total amount of the graft polymer (C) [C / (A + B + C)] is 0 or more and less than 0.04, and (A), (B) and (C) Dispersion stabilizer for suspension polymerization having a total content of 35 to 70% by mass Solved by.
- the dispersoid (B) in the dispersion stabilizer contains a polyvinyl ester, and it is more preferable that the polyvinyl ester is polyvinyl acetate. It is also preferred that the weight average molecular weight of the aqueous emulsion solid content measured using gel permeation chromatography is 1,000,000 or less. It is also preferred that the dispersant (A) contains a nonionic surfactant or a cationic surfactant.
- the object is to produce the dispersion stabilizer by obtaining 100 parts by weight of an ethylenically unsaturated monomer in an aqueous medium in the presence of 1 to 20 parts by weight of the dispersant (A). It is also solved by providing. At this time, it is preferable to obtain the aqueous emulsion by polymerizing the ethylenically unsaturated monomer in the presence of the chain transfer agent and the dispersant (A).
- a method for producing a vinyl resin in which a vinyl compound is suspension-polymerized in an aqueous medium in the presence of the dispersion stabilizer is a preferred embodiment of the present invention.
- the mass ratio of the vinyl compound to the aqueous medium is preferably 0.57 to 1.25.
- the vinyl compound When the vinyl compound is subjected to suspension polymerization using the dispersion stabilizer of the present invention, vinyl polymer particles having high plasticizer absorbability and easy processing can be obtained. Moreover, the generation of fish eyes when the obtained vinyl polymer is formed into a sheet is small, and the hue deterioration of the vinyl polymer due to heat is suppressed during the forming. In particular, these effects are exhibited even when the amount of the dispersion stabilizer used is small. Furthermore, a dispersion stabilizer having a high solid content concentration can be produced, and a dispersion stabilizer excellent in productivity and handling properties is provided.
- the dispersion stabilizer for suspension polymerization of the present invention is a dispersion stabilizer for suspension polymerization comprising an aqueous emulsion containing a dispersant (A), a dispersoid (B), a graft polymer (C) and an aqueous medium,
- Dispersant (A) contains a surfactant
- dispersoid (B) contains a polymer having an ethylenically unsaturated monomer unit
- graft polymer (C) contains ethylenically unsaturated polymer in dispersant (A).
- a saturated monomer is graft-polymerized, and the mass ratio [A / (A + B + C)] of the dispersant (A) to the total amount of (A), (B) and (C) is 0.001 or more and 0. Less than .18, and the mass ratio [C / (A + B + C)] of the graft polymer (C) to the total amount of (A), (B) and (C) is 0 or more and less than 0.04, and (A) , (B) and (C) in a total content of 35% to 70% by mass.
- the aqueous emulsion may be simply abbreviated as an emulsion.
- each component will be described in detail.
- the dispersion stabilizer for suspension polymerization of the present invention comprises an aqueous emulsion containing a dispersant (A), a dispersoid (B), a graft polymer (C) and an aqueous medium.
- the dispersant (A) used in the present invention contains a surfactant.
- the surfactant include nonionic surfactants and ionic surfactants. These may be used alone or in combination of two or more.
- Nonionic surfactants, cationic surfactants and zwitterionic surfactants are preferred as the surfactants from the viewpoints of economy, stabilization of emulsions, and performance improvement as a dispersant for suspension polymerization.
- nonionic surfactants and cationic surfactants are more preferable from the viewpoint of improving the performance of the dispersion stabilizer for suspension polymerization by adjusting the ratio of the graft polymer (C).
- the nonionic surfactant contained in the dispersant (A) is a polyoxyethylene polyoxyalkylene glycol such as polyoxyethylene polyoxypropylene glycol, a polyethylene glycol ester such as polyethylene glycol stearate, or a polyoxyethylene lauryl ether.
- Surfactants containing polyoxyethylene groups and aromatic rings such as polyoxyethylene alkyl ethers such as polyoxyethylene distyrenated phenyl ether, polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan monolaurate, glycerol monostearate
- reactive surfactants such as glycerin ester and polyoxyethylene allyl glycidyl nonyl phenyl ether.
- Polyoxyethylene alkyl ethers, polyoxyethylene sorbitan esters, and glycerin esters are preferably used from the viewpoints of economy, improved performance of the dispersant for suspension polymerization, and stabilization of the emulsion.
- the ionic surfactant contained in the dispersant (A) includes alkylamine acetates such as stearylamine acetate, alkylammonium salts such as stearyltrimethylammonium chloride, and cationic interfaces such as alkylbetaines such as laurylbetaine.
- An activator is preferred. These may be used alone or in combination of two or more. Alkyl ammonium salts and alkyl betaines are more preferred from the viewpoints of economy, improved performance of the dispersant for suspension polymerization, and stabilization of the emulsion.
- the content of the surfactant in the dispersant (A) is usually 50% by mass or more, preferably 80% by mass or more, and more preferably 95% by mass or more.
- the dispersant (A) may further contain polyvinyl alcohol.
- the saponification degree of the polyvinyl alcohol is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and further preferably 73 mol%. More preferably, it is 78 mol% or more. About an upper limit, Preferably it is 99.5 mol%, More preferably, it is 95 mol%, More preferably, it is 90 mol%.
- the viscosity average degree of polymerization of polyvinyl alcohol is usually 100 to 8000, preferably 100 to 4000, more preferably 150 to 3000.
- the saponification degree of polyvinyl alcohol is a value obtained by measurement according to JIS-K6726.
- the polyvinyl alcohol can be obtained by polymerizing a vinyl ester and saponifying the obtained polymer by a conventional method according to a conventionally known method.
- a method for polymerizing the vinyl ester conventionally known methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method can be applied.
- the polymerization catalyst an azo catalyst, a peroxide catalyst, a redox catalyst, or the like is appropriately selected depending on the polymerization method.
- the saponification reaction it is possible to apply a known alcoholysis or hydrolysis using an alkali catalyst or an acid catalyst. Among them, a saponification reaction using methanol as a solvent and a caustic soda (NaOH) catalyst is simple and most preferable. .
- the vinyl ester units constituting the polyvinyl alcohol include units derived from various vinyl ester compounds, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, Examples include vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, and vinyl benzoate. Of these, vinyl acetate is most preferred.
- the polyvinyl alcohol contained in the dispersant (A) may be a copolymer of vinyl ester and another monomer as long as the effect of the present invention is not impaired.
- Other monomers that can be used include, for example, ⁇ -olefins such as ethylene, propylene, n-butene and isobutylene; acrylic acid and its salts; acrylamide; N-methylacrylamide, N-ethylacrylamide, N, N-dimethyl.
- Acrylamide derivatives such as acrylamide, diacetone acrylamide, acrylamide propane sulfonic acid and salts thereof, acrylamide propyldimethylamine and salts thereof or quaternary salts thereof, N-methylol acrylamide and derivatives thereof; methacrylamide; N-methyl methacrylamide, N- Ethyl methacrylamide, methacrylamide propane sulfonic acid and salts thereof, methacrylamide propyl dimethylamine and salts thereof or quaternary salts thereof, N-methylol methacrylamide and derivatives thereof Methacrylamide derivatives such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, 2,3-diacetoxy Vinyl ethers such as 1-vinyloxy
- polyvinyl alcohol having a high content of 1,2 glycol obtained by saponifying a polymer obtained by polymerizing vinyl ester at a temperature higher than normal polymerization conditions can also be preferably used.
- the 1,2-glycol bond content in this case is not particularly limited, but 1.9 mol% or more, preferably 2.0 mol% or more, more preferably 2.1 mol% or more is used.
- the 1,2-glycol bond is in the above range, it is possible to obtain a dispersion stabilizer in which the particle size of the particles contained in the emulsion is smaller.
- polyvinyl alcohol may be synthesized using a chain transfer agent for the purpose of adjusting the polymerization degree of polyvinyl alcohol contained in the dispersant (A) or introducing a modified species at the terminal.
- Chain transfer agents include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; thiols such as 2-hydroxyethanethiol, 3-mercaptopropionic acid, dodecanethiol and thioacetic acid; carbon tetrachloride, trichloroethylene And halogenated hydrocarbons such as perchlorethylene; and phosphinic acid salts such as sodium phosphinate monohydrate.
- thiols, aldehydes and ketones are preferably used. What is necessary is just to determine the addition amount of a chain transfer agent according to the chain transfer constant of the chain transfer agent to add, and the polymerization degree of the target polyvinyl ester. In general, the content is preferably 0.1% by mass to 10% by mass with respect to the vinyl ester.
- the value of the weight average molecular weight / number average molecular weight (Mw / Mn) of the polyvinyl alcohol contained in the dispersant (A) is not particularly limited. From the viewpoint of
- the block character of the residual vinyl ester group of the polyvinyl alcohol contained in the dispersant (A) is not particularly limited, but it is usually 1.0 or less, and the viewpoint of controlling the particle diameter of the emulsion and ensuring the stability of the emulsion. Is preferably 0.8 or less, more preferably 0.6 or less.
- the content of polyvinyl alcohol in the dispersing agent (A) is usually 50% by mass or less, preferably 20% by mass or less, and more preferably 5% by mass or less.
- the dispersant (A) may further contain water-soluble cellulose.
- water-soluble cellulose various cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like are used, and there is no particular limitation on the viscosity.
- % Aqueous solution is 0.5 mPa ⁇ s or more and 5000 mPa ⁇ s or less.
- Examples of the ethylenically unsaturated monomer used as a raw material for the polymer having an ethylenically unsaturated monomer unit contained in the dispersoid (B) include olefins such as ethylene, propylene and isobutylene, vinyl chloride, fluorine.
- Halogenated olefins such as vinyl fluoride, vinylidene chloride, vinylidene fluoride, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valelate, vinyl laurate, vinyl stearate, vinyl pivalate, isopropenyl acetate, palmitic acid
- Vinyl esters such as vinyl and vinyl benzoate, acrylic esters such as acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, 2-hydroxyethyl acrylate, Metacri Methacrylic acid esters such as methyl acrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylamin
- acrylamide monomers such as acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acrylamide-2-methylpropanesulfonic acid and its sodium salt, styrene, ⁇ -methylstyrene, p-styrenesulfone Examples thereof include styrene monomers such as acids and sodium salts and potassium salts thereof, and other N-vinylpyrrolidone.
- unsaturated monomers can be used alone or in admixture of two or more. This constitutes the ethylenically unsaturated monomer unit of the polymer from which these unsaturated monomers are obtained.
- the polymer having an ethylenically unsaturated monomer unit contained in the dispersoid (B) is preferably a polyvinyl ester from the economical aspect and the performance of the dispersion stabilizer for suspension polymerization. More preferably.
- Examples of the vinyl ester monomer used as a raw material for the polyvinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl pivalate, isopropenyl acetate, Examples include vinyl palmitate and vinyl benzoate. These are used by homopolymerization or copolymerization within a range not inhibiting the effects of the present invention. Among these, it is preferable from the viewpoints of productivity, economy, and handling properties to use vinyl acetate alone or a copolymerized ethylenically unsaturated monomer as mentioned above with vinyl acetate as a main component.
- the content of the polymer having an ethylenically unsaturated monomer unit in the dispersoid (B) is usually 50% by mass or more, preferably 80% by mass or more, more preferably 95% by mass or more, and the dispersoid ( More preferably, B) consists essentially of a polymer having ethylenically unsaturated monomer units.
- Examples of the aqueous medium contained in the emulsion include water or water containing water and an organic solvent.
- the amount of water in the aqueous medium is preferably 90% by mass or more.
- the average particle size of the particles contained in the emulsion is not particularly limited, but the average particle size measured by a dynamic light scattering method is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and further preferably 2.5 ⁇ m or less. preferable. On the other hand, it is preferable that an average particle diameter is 0.05 micrometer or more. When the average particle diameter exceeds 5 ⁇ m, the stability of the emulsion may be lowered. On the other hand, when the average particle size is less than 0.05 ⁇ m, the fish eyes of the sheet may increase during processing of the vinyl resin obtained using the dispersant for suspension polymerization.
- the measurement by the dynamic light scattering method can be performed using, for example, a laser zeta electrometer ELS-8000 manufactured by Otsuka Electronics Co., Ltd.
- the particle size of the particles is the mass ratio of the dispersant (A) and the dispersoid (B) at the time of synthesis, and further the emulsion production conditions (polymerization temperature, polymerization time, type of monomer, type of polymerization initiator, dispersion) It is adjusted by appropriately selecting the addition time of the agent (A), the amount of chain transfer agent used, etc.).
- the stability of the emulsion can also be controlled by adjusting the solid content concentration of the emulsion.
- the method for producing the emulsion is not particularly limited, but a method of polymerizing the above-described ethylenically unsaturated monomer in an aqueous medium in the presence of the dispersant (A) is preferable. At this time, a polymer having an ethylenically unsaturated monomer unit contained in the dispersoid (B) is formed. Specifically, the above-mentioned ethylenically unsaturated monomer is temporarily or continuously added to the aqueous solution of the dispersant (A), and peroxides such as hydrogen peroxide, ammonium persulfate and potassium persulfate are added.
- peroxides such as hydrogen peroxide, ammonium persulfate and potassium persulfate are added.
- a method of adding a polymerization initiator such as a polymerization initiator and performing emulsion polymerization is preferable.
- a method of synthesizing the dispersoid (B) in advance, mixing with the dispersant (A) in water, and post-emulsifying can also be mentioned, but this is not preferable because the standing stability of the emulsion is lowered and precipitation tends to occur.
- the polymerization initiator may be used in combination with a reducing agent and used in a redox system. In that case, hydrogen peroxide is usually used together with tartaric acid, sodium tartrate, L-ascorbic acid, Rongalite and the like. Ammonium persulfate and potassium persulfate are used together with sodium hydrogen sulfite, sodium hydrogen carbonate and the like.
- the amount of the dispersant (A) used is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 1 to 12 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer.
- the amount of the dispersant (A) used is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 1 to 12 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer.
- the amount of the dispersant (A) used is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 1 to 12 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer.
- aqueous emulsion by polymerizing an ethylenically unsaturated monomer in an aqueous medium in the presence of a chain transfer agent and a dispersant (A).
- a chain transfer agent By using a chain transfer agent, the emulsion becomes more stable. Further, the ratio of the graft polymer (C) in the emulsion can be easily adjusted, and the weight average molecular weight of the emulsion can be lowered. Furthermore, the performance as a dispersion stabilizer for suspension polymerization is further improved.
- a thiol compound and an aldehyde compound are preferable as the chain transfer agent. These may be used alone or in combination of two or more.
- a thiol compound is more preferable from a viewpoint with high reactivity.
- the chain transfer agent may be added either temporarily or continuously. Further, the amount of the chain transfer agent to be used is not particularly limited, but is usually 0.01 to 50 parts by weight, preferably 0.05 to 40 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer. More preferably 0.1 to 30 parts by mass.
- the thiol compound described above is not particularly limited, and both alkyl thiol and functional thiol can be used.
- alkyl thiol is a straight chain having 4 to 18 carbon atoms from the viewpoint of handleability and odor. Or a branched alkylthiol is preferable.
- Examples include n-butanethiol, n-pentanethiol, n-hexanethiol, cyclohexanethiol, adamantylthiol, n-heptanethiol, n-octanethiol, n-nonanethiol, n-decanethiol, n-undecanethiol, n -Dodecanethiol, t-dodecanethiol, n-hexadecanethiol, n-octadecanethiol and the like.
- thiol having a functional group examples include thioacetic acid, mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptopropanesulfonic acid, 2-mercaptoethanol and the like. However, it is not limited only to these.
- the emulsion of the present invention needs to contain a dispersant (A) and a dispersoid (B). And the emulsion of this invention may contain the graft polymer (C) formed by graft-polymerizing an ethylenically unsaturated monomer to a dispersing agent (A) as an arbitrary component.
- a dispersant A
- a dispersoid B
- the emulsion of this invention may contain the graft polymer (C) formed by graft-polymerizing an ethylenically unsaturated monomer to a dispersing agent (A) as an arbitrary component.
- the dispersant (A) is present at the interface of the vinyl compound and serves as a surfactant, or a role of efficiently dissolving the dispersoid (B) into the vinyl compound, or the dispersoid (B) and the graft polymer (C). It plays a role in stabilizing the dispersion, reducing the number of fish eyes when processing vinyl resin sheets, and improving hue.
- the dispersoid (B) dissolves in the vinyl compound during suspension polymerization and participates in a change in morphology inside the resulting vinyl polymer particles, and plays a role in reducing the number of fish eyes and improving plasticizer absorbability.
- the graft polymer (C) is present at the interface of the vinyl compound because it has both a portion that dissolves in the vinyl compound and a hydrophilic group.
- the graft polymer (C) has both the performance of the dispersant (A) and the dispersoid (B).
- the dispersant (A) the effect of reducing the hue and the number of fish eyes when the vinyl resin is processed into a sheet is the dispersant (A).
- dispersant (B) low compared with dispersoid (B). Therefore, when the ratio of the graft polymer (C) is as low as possible, the performance as a dispersant for suspension polymerization is improved.
- the graft polymer (C) since the graft polymer (C) has both a hydrophilic group and a hydrophobic group, it has an effect of improving the stability of the aqueous emulsion, particularly in a low concentration aqueous emulsion.
- the graft polymer (C) is usually produced when an ethylenically unsaturated monomer is polymerized in the presence of the dispersant (A).
- These three types of components interact with each other, and as a dispersion stabilizer for suspension polymerization, the polymerization stability of the vinyl compound, the improvement of the plasticizer absorbability of the resulting vinyl polymer particles, and the sheet processing of the vinyl resin Contributes to the number of fish eyes and hue. That is, these ratios are important for improving the performance of the dispersion stabilizer for suspension polymerization.
- the mass ratio [A / (A + B + C)] of the dispersant (A) to the total amount of the dispersant (A), the dispersoid (B), and the graft polymer (C) is 0.001 or more and less than 0.18. Is preferably 0.005 or more and 0.15 or less, and more preferably 0.01 or more and 0.12 or less.
- the mass ratio [A / (A + B + C)] is less than 0.001, it is difficult to stabilize the dispersion of the dispersoid (B) and the graft polymer (C) contained in the emulsion, and the solution stability of the emulsion is lowered.
- the mass ratio [A / (A + B + C)] is determined by adjusting the degree of saponification or the degree of polymerization when the one containing polyvinyl alcohol is used as the dispersant (A) at the time of emulsion synthesis. It can be adjusted by changing the probability of the grafting reaction by using the dispersant (A) in the presence of, adjusting the amount of the dispersant (A) used, using a chain transfer agent, an additive or the like.
- the total amount of the dispersant (A), the dispersoid (B) and the graft polymer (C) can be determined by measuring the amount of solid content obtained by drying the emulsion.
- the amount of the dispersant (A) in the emulsion can be determined by the following method.
- the supernatant After centrifuging the emulsion, the supernatant is recovered. Only the dispersant (A) is contained in the supernatant.
- the amount of the dispersant (A) in the emulsion can be determined by measuring the amount of solid content obtained by drying the supernatant. From these values, the mass ratio [A / (A + B + C)] is determined.
- the emulsion may contain the graft polymer (C), but the mass ratio of the graft polymer (C) to the total amount of the dispersant (A), the dispersoid (B) and the graft polymer (C) [C / (A + B + C)] needs to be 0 or more and less than 0.04.
- the effect of the graft polymer (C) include improvement in plasticizer absorbability of the obtained vinyl polymer particles, improvement in hue when a vinyl resin is processed into a sheet, and the like. However, the effect is small compared to the dispersant (A) and the dispersoid (B), and may cause problems such as an increase in fish eyes when the vinyl resin is processed into a sheet.
- the mass ratio [C / (A + B + C)] is 0.04 or more, the ratio of the dispersant (A) and the dispersoid (B) is decreased, and thus obtained when used as a dispersion stabilizer for suspension polymerization.
- the plasticizer absorbability of the resulting vinyl polymer particles is reduced, the hue deteriorates when the vinyl resin is processed into a sheet, and fish eyes increase.
- the ratio of graft polymer (C) increases, the weight average molecular weight of the emulsion solid content mentioned later may increase according to the manufacturing conditions of an emulsion, and a viscosity may become high.
- the stability of the emulsion itself may be improved particularly in a low concentration region, but it may be difficult to obtain an emulsion having a high solid content concentration, and the economy may be lowered.
- the mass ratio [C / (A + B + C)] is adjusted by the following method or the like.
- the saponification degree or polymerization degree is adjusted, and as other methods, a dispersant (A) such as a surfactant that is difficult to graft is used.
- the emulsion solid content is determined from a method of washing the emulsion with acetone and water (see Patent Documents 1 and 2) and the ratio of toluene insoluble matter (see Japanese Patent Laid-Open No. 10-081865) to the total amount of emulsion solid content.
- requiring by subtracting the ratio of the dispersing agent (A) with respect to the whole quantity is mentioned.
- the former is a method of removing the dispersoid (B) with acetone and then removing the dispersant (A) with water.
- the latter uses the fact that the components insoluble in toluene are the graft polymer (C) and the dispersant (A), so that the graft polymer (C) and the dispersant (A) with respect to the total solid content (A + B + C) in the emulsion.
- the mass ratio [(A + C) / (A + B + C)] of the total amount is obtained.
- the mass ratio [C / (A + B + C)] can be obtained by subtracting the mass ratio [A / (A + B + C)] from the mass ratio [(A + C) / (A + B + C)]. Since both are synonymous methods, the value of the ratio of the graft polymer is almost the same regardless of which method is used.
- the ratio of the graft polymer remaining without being dissolved in water and acetone becomes 0 or more.
- the graft polymer ratio may be negative depending on the measurement error. Therefore, when the toluene-insoluble matter is measured for the precipitate from which the dispersant has been removed by centrifuging the emulsion solution, the proportion of the graft polymer can be determined more accurately, specifically, described in the examples. It can be measured by the method.
- the weight average molecular weight of the solid content of the emulsion measured using gel permeation chromatography is preferably 1,000,000 or less, more preferably 700,000 or less, and even more preferably 500,000 or less.
- the weight average molecular weight is adjusted by adjusting the degree of saponification or polymerization, adjusting the type and amount of the dispersant (A), and polymerization. It can be adjusted by changing the length of the trunk or branch of the graft polymer by selecting an initiator or using a chain transfer agent.
- the plasticizer absorbability of vinyl polymer particles obtained using the dispersion stabilizer for suspension polymerization decreases, the fish eye increases when the vinyl resin is processed into a sheet, the hue deteriorates, There is a possibility that the viscosity of the resulting emulsion is increased and the stability of standing is deteriorated.
- the total content of the dispersant (A), the dispersoid (B) and the graft polymer (C) in the emulsion is 35% by mass to 70% by mass, preferably 40% by mass to 70% by mass, and preferably 50% by mass. % To 65% by mass is more preferable. When this content is less than 35%, it is not preferable in terms of productivity and economy. Moreover, the viscosity of an emulsion falls too much and the problem of the solution stability of an emulsion falling arises. When it exceeds 70 mass%, the viscosity of an emulsion will increase and handling property will fall.
- 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.
- polymerization regulators such as aldehydes, halogenated hydrocarbons and mercaptans
- polymerization inhibitors such as phenol compounds, sulfur compounds and N-oxide compounds
- pH adjusters such as sodium bicarbonate
- cross-linking agents such as phenol compounds, sulfur compounds and N-oxide compounds
- antiseptics such as An antifoaming agent etc.
- the dispersion stabilizer for suspension polymerization of the present invention is suitably used for suspension polymerization of a vinyl compound in an aqueous medium.
- a preferred embodiment of the present invention is a method for producing a vinyl resin in which a vinyl compound is suspension-polymerized in an aqueous medium in the presence of the dispersion stabilizer of the present invention.
- vinyl compounds include vinyl halides such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid, methacrylic acid, their esters and salts; maleic acid, fumaric acid, their esters and anhydrides; 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.
- 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.
- 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-hexylperoxypivalate, ⁇ -cumylperoxyneodecanate; 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 can 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.
- the ratio of the vinyl compound to be charged and the aqueous medium is not particularly limited. In general, the lower the ratio of the vinyl compound to the aqueous medium, the more stable the polymerization but the lower the productivity. The higher the ratio of the vinyl compound to the aqueous medium, the higher the productivity but the unstable the polymerization.
- the mass ratio of the vinyl compound to the aqueous medium (vinyl compound / aqueous medium) is preferably 0.57 to 1.25, more preferably 0.57 to 1.11. is there. When the mass ratio (vinyl compound / aqueous medium) is less than 0.57, the productivity of the resulting vinyl resin may be lowered.
- the mass ratio of the vinyl compound (vinyl compound / aqueous medium) in the vinyl resin production method of the present invention is preferably 0.75 to 1.25.
- the ratio of such vinyl compounds is high, and the fish eyes of the molded vinyl resin products are reduced with the dispersion stabilizer for suspension polymerization of the present invention under conditions where the polymerization tends to be unstable. The effect to do is demonstrated more.
- the dispersion stabilizer for suspension polymerization of the present invention may be used alone, but the dispersion stabilizer and the viscosity average polymerization degree are 650 or more, and the degree of saponification It is preferable that the vinyl compound is subjected to suspension polymerization in the presence of PVA in which is 65 mol% or more. By using such PVA in combination, the polymerization stability of the vinyl compound is further improved, and the generation of coarse resin particles is further suppressed.
- the saponification degree of the polyvinyl alcohol suitably used in the present invention is preferably 65 mol% or more, more preferably 65 mol% or more and 95 mol% or less, and 70 mol% or more and 90 mol% or less. Is more preferable.
- the saponification degree of polyvinyl alcohol is less than 65 mol%, the water solubility of polyvinyl alcohol is lowered, and the handleability may be deteriorated.
- the viscosity average polymerization degree of polyvinyl alcohol suitably used in the present invention is preferably 650 or more, more preferably 650 or more and 8000 or less, and further preferably 650 or more and 3500 or less.
- the viscosity average degree of polymerization of polyvinyl alcohol is determined by measuring the intrinsic viscosity in an acetone solution (Akio Nakajima: High) after saponifying the polyvinyl alcohol substantially completely and then acetylating it into a polyvinyl ester. Molecular chemistry 6 (1949)).
- the amount of the polyvinyl alcohol used in combination with the dispersion stabilizer for suspension polymerization of the present invention is not particularly limited, but is 40 to 900 parts by mass with respect to 100 parts by mass of the dispersion stabilizer for suspension polymerization of the present invention.
- the amount is preferably 100 to 900 parts by mass.
- the addition amount of the polyvinyl alcohol is less than 40 parts by mass, the polymerization stability may be adversely affected.
- the addition amount exceeds 900 parts by mass, the effect of adding the dispersant for suspension polymerization of the present invention may be insufficient.
- the above-mentioned polyvinyl alcohol may be used alone, or two or more types having different characteristics may be used in combination.
- the saponification degree of the polyvinyl alcohol is a value obtained by measurement according to JIS-K6726.
- Said PVA can be manufactured by the method mentioned above as a manufacturing method of the polyvinyl alcohol contained in a dispersing agent (A).
- water-soluble cellulose ethers such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, etc., which are usually used for suspension polymerization of vinyl compounds in an aqueous medium; gelatin Water-soluble polymers such as sorbitan monolaurate, sorbitan trioleate, glycerin tristearate, ethylene oxide propylene oxide block copolymer and other oil-soluble emulsifiers; polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate, sodium laurate, etc.
- a water-soluble emulsifier may be used in combination.
- part and % represent parts by mass and mass%, respectively.
- Dispersant (A) ratio c / [(a / 100) ⁇ b] a: Solid content (%) of diluted emulsion b: Mass of diluted emulsion (g) c: solid content mass in the supernatant (g)
- the ratio of the graft polymer (C) insoluble in toluene and the ratio of the dispersoid (B) dissolved in toluene to the total amount of emulsion solids were determined.
- Toluene insoluble component ratio in the precipitate Dry mass (g) of toluene insoluble matter / dry mass (g) of precipitate
- Ratio of graft polymer (C) Ratio of toluene insoluble component in precipitate x [1- (Ratio of dispersant A)]
- Dispersoid (B) ratio 1-[(Dispersant A ratio) + (Graft polymer C ratio)]
- Emulgen 1150S-60 manufactured by Kao Corporation
- a nonionic surfactant as a dispersing agent (A) in a 2 L glass polymerization vessel provided with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet 9 parts and 0.1 part of sodium acetate were charged and completely dissolved at 80 ° C.
- Examples 2 to 10, Comparative Example 1 Production of (Em-2 to 10, 12)] Emulsions shown in Table 1 in the same manner as in Example 1 except that the polymerization conditions such as the type of ethylenically unsaturated monomer, the type of dispersant (A), the amount used, and the amount of ion-exchanged water charged were changed. (Em-2 to 10, 12) were produced.
- Table 1 shows the production conditions and physical properties of the synthesized emulsion
- Table 2 shows the type of the dispersant (A) used.
- Example 11 Production of (Em-11)]
- Example 1 except that polymerization conditions such as the amount of ion-exchanged water charged and dodecanethiol as a chain transfer agent were mixed with vinyl acetate monomer in the ratio shown in Table 1 and added continuously for polymerization.
- polymerization conditions such as the amount of ion-exchanged water charged and dodecanethiol as a chain transfer agent were mixed with vinyl acetate monomer in the ratio shown in Table 1 and added continuously for polymerization.
- emulsions (Em-11) shown in Table 1 were produced. The production conditions and the physical properties of the synthesized emulsion are shown in Table 1.
- the polymerization was completed by adding 18 parts of an ammonium persulfate aqueous solution in four portions.
- the solid content of the obtained emulsion is 30%, the weight average molecular weight (Mw) is 620,000, the ratio of the dispersant (A) to the total emulsion solid content is 0.06, the ratio of the dispersoid (B) is 0.88, An emulsion having a graft polymer (C) ratio of 0.06 and a standing stability of less than 30 days was obtained.
- Emulsions (Em-14) shown in Table 1 were produced in the same manner as in Comparative Example 2 except that the amount of ion-exchanged water charged was changed in accordance with the change in the target solid content.
- the production conditions and the physical properties of the synthesized emulsion are shown in Table 1.
- Example 2-1 A 5 L autoclave was charged with 100 parts of deionized aqueous solution of polyvinyl alcohol having a degree of polymerization of 2000 and a saponification degree of 80 mol% with respect to the vinyl chloride monomer, and the above Em-1 was chlorinated in terms of solid content. It charged so that it might be set to 200 ppm with respect to a vinyl monomer, and deionized water was added and charged so that the total of the deionized water charged might be 1200 parts.
- Plasticizer absorbability Weigh the mass of a syringe with a capacity of 5 mL packed with 0.02 g of absorbent cotton (assuming Ag), put 0.5 g of vinyl chloride resin particles into it, weigh the mass (assum it as Bg), and then there 1 g of dioctyl phthalate (DOP) was added and allowed to stand for 15 minutes, and then centrifuged at 3000 rpm for 40 minutes to measure the mass (referred to as Cg). And plasticizer absorptivity (%) was calculated
- required from the following formula. Plasticizer absorbency (%) 100 ⁇ [ ⁇ (CA) / (BA) ⁇ -1]
- SM-T-H1 color meter
- Example 2-2 to 2-11 A vinyl chloride resin particle was obtained by suspension polymerization of vinyl chloride in the same manner as in Example 2-1, except that Em-2 to 11 were used instead of Em-1. Table 3 shows the evaluation results of the vinyl chloride resin particles.
- Example 2-12 A vinyl chloride resin particle was obtained by suspension polymerization of vinyl chloride in the same manner as in Example 2-1, except that the total amount of deionized water used was 1390 parts. Table 4 shows the evaluation results of the vinyl chloride resin particles.
- Example 2-1 A suspension polymerization of vinyl chloride was carried out in the same manner as in Example 2-1, except that Em-1 was not used.
- Table 3 shows the evaluation results of the vinyl chloride resin particles. In this case, the plasticizer absorbability of the obtained vinyl chloride resin particles was insufficient, the fish eyes were very large, and the hue was not satisfactory.
- Example 2-2 Suspension polymerization of vinyl chloride was carried out in the same manner as in Example 2-1, except that Em-12 was used instead of Em-1.
- Table 3 shows the evaluation results of the vinyl chloride resin particles. In this case, the obtained vinyl chloride resin particles had a large number of fish eyes, and the hue was not satisfactory.
- Example 2-3 Suspension polymerization of vinyl chloride was carried out in the same manner as in Example 2-1, except that Em-13 was used instead of Em-1.
- Table 3 shows the evaluation results of the vinyl chloride resin particles. In this case, the plasticizer absorbability of the obtained vinyl chloride resin particles was insufficient, the fish eyes were very large, and the hue was not satisfactory.
- Example 2-4 Suspension polymerization of vinyl chloride was carried out in the same manner as in Example 2-1, except that Em-14 was used instead of Em-1.
- Table 3 shows the evaluation results of the vinyl chloride resin particles. In this case, the plasticizer absorbability of the obtained vinyl chloride resin particles was insufficient, the fish eyes were very large, and the hue was not satisfactory.
- a vinyl chloride resin particle was obtained by suspension polymerization of vinyl chloride in the same manner as in Comparative Example 2-2, except that the total amount of deionized water used was 1390 parts.
- Table 4 shows the evaluation results of the vinyl chloride resin particles. In this case, the plasticizer absorbability of the obtained vinyl chloride resin particles was insufficient, the fish eyes were very large, and the hue was not satisfactory.
- the emulsion of the present invention absorbs the plasticizer even under polymerization conditions with a higher proportion of vinyl chloride used. It is possible to exert an excellent effect on improvement of properties, reduction of fish eyes, and improvement of hue.
- the dispersion stabilizer of the present invention when used for suspension polymerization of a vinyl compound, polymer particles having high plasticizer absorbability and easy processing even when the amount used is small. This makes it possible to reduce fish eyes and improve hue when molding a vinyl resin sheet. Furthermore, it can be produced as a high-concentration liquid exceeding 35%, and can be directly charged into a polymerization tank in which a vinyl compound is subjected to suspension polymerization, so that it is extremely excellent in handling property and economical efficiency. Therefore, the industrial usefulness of the dispersion stabilizer for suspension polymerization of the present invention is extremely high.
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Abstract
Description
本発明の懸濁重合用分散安定剤は、分散剤(A)、分散質(B)、グラフトポリマー(C)及び水性媒体を含有する水性エマルションからなる懸濁重合用分散安定剤であって、分散剤(A)が界面活性剤を含有し、分散質(B)がエチレン性不飽和単量体単位を有する重合体を含有し、グラフトポリマー(C)が分散剤(A)にエチレン性不飽和単量体をグラフト重合させてなるものであり、(A)、(B)及び(C)の合計量に対する分散剤(A)の質量比[A/(A+B+C)]が0.001以上0.18未満であり、(A)、(B)及び(C)の合計量に対するグラフトポリマー(C)の質量比[C/(A+B+C)]が0以上0.04未満であり、かつ(A)、(B)および(C)の合計含有量が35%~70質量%であるものである。以下、前記水性エマルションのことを単にエマルションと略記することがある。以下、各成分について詳述する。
本発明の懸濁重合用分散安定剤は、分散剤(A)、分散質(B)、グラフトポリマー(C)及び水性媒体を含有する水性エマルションからなる。本発明で用いられる分散剤(A)は、界面活性剤を含有する。当該界面活性剤としてはノニオン性界面活性剤及びイオン性界面活性剤が挙げられる。これらは単独で用いても、2種類以上を併用しても構わない。経済性、エマルションの安定化、懸濁重合用分散剤としての性能向上の観点から前記界面活性剤として、ノニオン性界面活性剤、カチオン性界面活性剤及び両性イオン系界面活性剤が好ましい。なかでも、グラフトポリマー(C)の割合の調整による懸濁重合用分散安定剤の性能向上の面からノニオン性界面活性剤及びカチオン性界面活性剤がよりに好ましい。
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。例えば、アルデヒド、ハロゲン化炭化水素、メルカプタンなどの重合調節剤;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、特にビニル化合物の水性媒体中での懸濁重合に好適に用いられる。本発明の分散安定剤の存在下、水性媒体中で、ビニル化合物を懸濁重合するビニル樹脂の製造方法が本発明の好適な実施態様である。ビニル化合物としては、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。
本発明のビニル樹脂の製造方法において、本発明の懸濁重合用分散安定剤を単独で使用してもよいが、当該分散安定剤、及び、粘度平均重合度が650以上であり、かつけん化度が65モル%以上であるPVAの存在下、ビニル化合物を懸濁重合することが好ましい。このようなPVAを併用することで、ビニル化合物の重合安定性がより向上し、粗大樹脂粒子の発生がさらに抑制される。
エマルションを温度20℃、湿度65%で乾固させ厚み約500μmのエマルションフィルムを作成した。当該フィルムを移動相と同じ溶媒に溶解して、エマルション中の固形分が溶解した溶液を得た後、当該溶液をゲルパーミエーションクロマトグラフィー(GPC)を用い測定した。[装置:東ソー株式会社製HLC-8220GPC、カラム:GMHHR-H(S)×2、移動相:HFIP+20mM CF3COONa、測定温度:40℃、標品:ポリメチルメタクレート(PMMA)]
エマルションを濃度約5%に希釈した。希釈したエマルション約2gをアルミ容器にとり105℃で3h乾燥させて、得られた固形分の質量を測定した。前記希釈液の正確な固形分含有量a(%)を下記式により求めた。
固形分含有量a(%)=[固形分(g)/乾燥前の希釈エマルション(g)]×100
分散剤(A)の割合=c/[(a/100)×b]
a:希釈エマルションの固形分含有量(%)
b:希釈エマルションの質量(g)
c:上澄み中の固形分質量(g)
前述の遠心分離によって得られた沈殿物を粉砕し、乾燥機にて105℃で3時間絶乾させた後、約1gを精秤し、約50mLのトルエンに浸漬し、室温中で24時間静置した。これらが入った容器を手で軽く振り、直ちに不溶分を200メッシュのステンレス金網で回収した。不溶分を金網ごと105℃で24h乾燥させた後、質量を測定した。下記式により、エマルション固形分全量に対する、トルエンに不溶解性であるグラフトポリマー(C)の割合およびトルエンに溶解する分散質(B)の割合を求めた。
沈殿物中のトルエン不溶解成分比=
トルエン不溶解分の乾燥質量(g)/沈殿物の乾燥質量(g)
グラフトポリマー(C)の割合=
沈殿物中のトルエン不溶解成分比×[1-(分散剤Aの割合)]
分散質(B)の割合=
1-[(分散剤Aの割合)+(グラフトポリマーCの割合)]
エマルションの放置安定性は合成したエマルションを25℃にて放置し、沈殿物が生じるまでの日数を確認し評価した。
A:30日以上沈殿が生じなかった
B:30日以内に沈殿が生じた
還流冷却器、滴下ロート、温度計、窒素吹込口を供えた2Lガラス製重合容器にイオン交換水108部、分散剤(A)としてノニオン性界面活性剤であるエマルゲン1150S-60(花王社製)9部、酢酸ナトリウム0.1部を仕込み80℃で完全に溶解した。次に窒素置換した後、還元剤として1%炭酸水素ナトリウム水溶液を3.1部、開始剤として1%過硫酸アンモニウム水溶液を11部仕込み、200rpmで撹拌しながら、1%過硫酸アンモニウム水溶液11部および、エチレン性不飽和単量体として酢酸ビニルモノマー100部を3時間かけて連続的に添加し重合を完結させた。得られたエマルション中の固形分量は45%、エマルションの重量平均分子量(Mw)が28万、エマルション固形分全体に対する分散剤(A)の割合が0.08、分散質(B)の割合が0.92、グラフトポリマー(C)の割合が0、放置安定性が30日以上のエマルションを得た。
エチレン性不飽和単量体の種類、分散剤(A)の種類、使用量、イオン交換水の仕込み量の重合条件等を変更したこと以外は、実施例1と同様にして表1に示すエマルション(Em-2~10、12)を製造した。製造条件および合成したエマルションの物性値を表1に、用いた分散剤(A)の種類を表2に示す。
イオン交換水の仕込量等の重合条件および、連鎖移動剤としてドデカンチオールを酢酸ビニルモノマーに対し表1に示す割合で混合させて連続的に添加し重合を行ったこと以外は、実施例1と同様にして表1に示すエマルション(Em-11)を製造した。製造条件および合成したエマルションの物性値を表1に示す。
還流冷却器、滴下ロート、温度計、窒素吹込口を供えた2Lガラス製重合容器にイオン交換水232部、分散剤(A)としてノニオン性界面活性剤であるポリオキシエチレンノニルフェニルエーテル9部、酢酸ナトリウム0.1部を仕込み80℃で完全に溶解した。次に窒素置換した後、開始剤として1%過硫酸アンモニウム水溶液を4部、酢酸ビニルモノマー11部を仕込み、200rpmで撹拌しながら、酢酸ビニルモノマー89部を3時間かけて連続的に添加、1%過硫酸アンモニウム水溶液を18部を4分割添加し重合を完結させた。得られたエマルションの固形分は30%、重量平均分子量(Mw)が62万、エマルション固形分全体に対する分散剤(A)の割合が0.06、分散質(B)の割合が0.88、グラフトポリマー(C)の割合が0.06、放置安定性が30日未満のエマルションを得た。
目標固形分の変更に伴い仕込むイオン交換水の量を変更したこと以外は、比較例2と同様にして表1に示すエマルション(Em-14)を製造した。製造条件および合成したエマルションの物性値を表1に示す。
分散質(B)としてあらかじめ合成しておいた粘度平均重合度250のポリ酢酸ビニル粉末100部に水133部、分散剤(A)としてエマルゲン1150S-60を9部加え攪拌し水性エマルションを得ようと試みたが分散質(B)が分散せず、沈殿を生じたままであった。
容量5Lのオートクレーブに重合度2000、けん化度80モル%のポリビニルアルコールを塩化ビニル単量体に対して800ppmとなるように100部の脱イオン水溶液として仕込み、上記Em-1を固形分換算で塩化ビニル単量体に対して200ppmとなるように仕込み、仕込む脱イオン水の合計が1200部となるように脱イオン水を追加して仕込んだ。次いで、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部をオートクレーブに仕込み、オートクレーブ内に圧力0.2MPaとなるように窒素を導入、導入した窒素のパージ、という作業を計5回行い、オートクレーブ内を十分に窒素置換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約3.5時間経過後、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、塩化ビニル樹脂粒子を得た。
実施例2-1で得られた塩化ビニル樹脂粒子について、可塑剤吸収性、シート加工した際のフィッシュアイ数および厚膜を作成し、色相(YI)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。
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)、そこに塩化ビニル樹脂粒子0.5gを入れ質量を量り(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(%)=100×[{(C-A)/(B-A)}-1]
得られた塩化ビニル樹脂粒子100部、DOP(ジオクチルフタレート)50部、三塩基性硫酸鉛5部及びステアリン酸亜鉛1部を150℃で7分間ロール練りして0.1mm厚のシートを作製し100mm×100mm当たりのフィッシュアイの数を測定した。
得られた塩化ビニル樹脂粒子100部、錫系安定剤であるTVS♯N-2000E(日東化成製)3部、ウルトラマリンブルー0.01部を170℃で10分間0.4mmの厚さでロール練りしたのち、得られたシートを185℃、120kg/cm2の圧力で5分間加熱しながらプレスし、その後、20℃、150kg/cm2の圧力で5分間冷却しながらプレスし、42×25×5mmの厚膜を作成した。
作成した厚膜の色相(YI)をカラーメーター(スガ試験機製SM-T-H1)を用いてJIS-K7105に準じて測定した。値が大きいほど、塩化ビニル樹脂が熱により分解し、黄色く着色していることを示している。
Em-1に代えてEm-2~11をそれぞれ使用したこと以外は実施例2-1と同様にして塩化ビニルの懸濁重合を行い、塩化ビニル樹脂粒子を得た。塩化ビニル樹脂粒子の評価結果を表3に示す。
用いる脱イオン水の量を計1390部としたこと以外は実施例2-1と同様にして塩化ビニルの懸濁重合を行い、塩化ビニル樹脂粒子を得た。塩化ビニル樹脂粒子の評価結果を表4に示す。
Em-1を使用しなかったこと以外は実施例2-1と同様にして、塩化ビニルの懸濁重合を行った。塩化ビニル樹脂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樹脂粒子の可塑剤吸収性が不十分であり、フィッシュアイが非常に多く、色相も満足できるものではなかった。
Em-1に代えて、Em-12を使用したこと以外は実施例2-1と同様にして塩化ビニルの懸濁重合を行った。塩化ビニル樹脂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樹脂粒子のフィッシュアイが非常に多く、色相も満足できるものではなかった。
Em-1に代えて、Em-13を使用したこと以外は実施例2-1と同様にして塩化ビニルの懸濁重合を行った。塩化ビニル樹脂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樹脂粒子の可塑剤吸収性が不十分であり、フィッシュアイが非常に多く、色相も満足できるものではなかった。
Em-1に代えて、Em-14を使用したこと以外は実施例2-1と同様にして塩化ビニルの懸濁重合を行った。塩化ビニル樹脂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樹脂粒子の可塑剤吸収性が不十分であり、フィッシュアイが非常に多く、色相も満足できるものではなかった。
Em-1に代えて、粘度平均重合度250、けん化度60モル%の部分けん化ポリビニルアルコール(PVA-1)30wt%水溶液を使用したこと以外は実施例2-1と同様にして塩化ビニルの懸濁重合を行った。塩化ビニル樹脂粒子の評価結果を表5に示す。この場合、得られた塩化ビニル樹脂粒子の可塑剤吸収性が不十分であり、フィッシュアイが非常に多く、色相も満足できるものではなかった。また、PVA-1はこれ以上の高濃度溶液として合成すると粘度が非常に高くなる恐れがあり、ハンドリング性が悪化する。また、PVAの水溶液を調製する場合、水に溶解させる手間がかかる。したがった、合成した際にすでに液体の状態である本発明のエマルションと比較して経済性、生産性に劣る。
用いる脱イオン水の量を計1390部としたこと以外は比較例2-2と同様にして塩化ビニルの懸濁重合を行い、塩化ビニル樹脂粒子を得た。塩化ビニル樹脂粒子の評価結果を表4に示す。この場合、得られた塩化ビニル樹脂粒子の可塑剤吸収性が不十分であり、フィッシュアイが非常に多く、色相も満足できるものではなかった。また、表4の実施例2-1、2-12、比較例2-2、2-6をそれぞれ比較すると本発明のエマルションは、より使用する塩化ビニルの割合が多い重合条件下でも可塑剤吸収性向上、フィッシュアイ削減、色相改善に対して優れた効果を発揮することができる。
Claims (9)
- 分散剤(A)、分散質(B)、グラフトポリマー(C)及び水性媒体を含有する水性エマルションからなる懸濁重合用分散安定剤であって、
分散剤(A)が界面活性剤を含有し、
分散質(B)がエチレン性不飽和単量体単位を有する重合体を含有し、
グラフトポリマー(C)が分散剤(A)にエチレン性不飽和単量体をグラフト重合させてなるものであり、
(A)、(B)及び(C)の合計量に対する分散剤(A)の質量比[A/(A+B+C)]が0.001以上0.18未満であり、
(A)、(B)及び(C)の合計量に対するグラフトポリマー(C)の質量比[C/(A+B+C)]が0以上0.04未満であり、かつ
(A)、(B)および(C)の合計含有量が35~70質量%である懸濁重合用分散安定剤。 - 分散質(B)がポリビニルエステルを含有する請求項1に記載の分散安定剤。
- 前記ポリビニルエステルがポリ酢酸ビニルである請求項2に記載の分散安定剤。
- ゲルパーミエーションクロマトグラフィーを用いて測定した前記水性エマルション固形分の重量平均分子量が100万以下である請求項1~3のいずれかに記載の分散安定剤。
- 分散剤(A)がノニオン性界面活性剤またはカチオン性界面活性剤を含有する請求項1~4のいずれかに記載の分散安定剤。
- 分散剤(A)1~20質量部の存在下、水性媒体中で、エチレン性不飽和単量体100質量部を重合させることにより前記水性エマルションを得る請求項1~5のいずれかに記載の分散安定剤の製造方法。
- 連鎖移動剤及び分散剤(A)の存在下、エチレン性不飽和単量体を重合させることにより前記水性エマルションを得る請求項6に記載の分散安定剤の製造方法。
- 請求項1~5のいずれかに記載の分散安定剤の存在下、水性媒体中で、ビニル化合物を懸濁重合するビニル樹脂の製造方法。
- 前記水性媒体に対する前記ビニル化合物の質量比(ビニル化合物/水性媒体)が0.57~1.25である請求項8に記載のビニル樹脂の製造方法。
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