WO2018096937A1 - Alcool polyvinylique modifié et procédé de production associé - Google Patents

Alcool polyvinylique modifié et procédé de production associé Download PDF

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Publication number
WO2018096937A1
WO2018096937A1 PCT/JP2017/040464 JP2017040464W WO2018096937A1 WO 2018096937 A1 WO2018096937 A1 WO 2018096937A1 JP 2017040464 W JP2017040464 W JP 2017040464W WO 2018096937 A1 WO2018096937 A1 WO 2018096937A1
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terminal
mol
general formula
vinyl
polymerization
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PCT/JP2017/040464
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Japanese (ja)
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渡辺　亘
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デンカ株式会社
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Priority to JP2018543257A priority Critical patent/JP6505328B2/ja
Publication of WO2018096937A1 publication Critical patent/WO2018096937A1/fr

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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
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F16/04—Acyclic compounds
    • C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis

Definitions

  • the present invention relates to a modified vinyl alcohol polymer and a method for producing the same.
  • the present invention also relates to a dispersion stabilizer for suspension polymerization, particularly a dispersion stabilizer suitable for polymerization of vinyl compounds represented by vinyl chloride.
  • vinyl compounds such as vinyl chloride are dispersed in an aqueous medium in the presence of a dispersion stabilizer, and polymerization is performed using an oil-soluble catalyst.
  • Suspension polymerization is widely practiced.
  • factors governing the quality of vinyl resins include polymerization rate, water-monomer ratio, polymerization temperature, type and amount of catalyst, type of polymerization tank, stirring speed, and type of dispersion stabilizer.
  • the influence of the type of dispersion stabilizer is very large.
  • each resin particle has a function of making it porous. For example, it has a function of forming resin particles having a large specific gravity.
  • cellulose derivatives such as methyl cellulose and carboxymethyl cellulose, partially saponified polyvinyl alcohol, and the like have been used alone or in combination.
  • polyvinyl alcohol (PVA) has excellent properties and is most commonly used.
  • PVA polyvinyl alcohol
  • An aldehyde-derived carbonyl group is introduced into the mixture, and an unsaturated double bond is introduced by undergoing a dehydration reaction or a deacetic acid reaction at the time of saponification (see, for example, Patent Document 1), and heat treatment is performed in a specific oxygen concentration atmosphere
  • Various modified vinyl alcohol polymers have been proposed, such as introducing a carboxyl group (see, for example, Patent Document 2).
  • the present invention is suitable for obtaining resin particles having a fine, high uniformity of particle size, high plasticizer absorbability, and proper bulk specific gravity when suspension polymerization of vinyl compounds such as vinyl chloride.
  • An object is to provide a dispersion stabilizer.
  • a modified vinyl alcohol polymer having a predetermined carbonyl terminal and a predetermined formyl terminal, each terminal (terminal glycol group, terminal methylol).
  • the content of carbonyl terminal represented by general formula (I) is 10 mol.
  • a modified vinyl alcohol polymer having a formyl terminal content of 1 to 25 mol% and a total content of 15 to 45 mol% in the general formula (II) Has been found to be effective as a dispersion stabilizer for suspension polymerization of vinyl compounds.
  • the present invention is a modified vinyl alcohol polymer having a carbonyl terminal represented by the general formula (I) and a formyl terminal represented by the general formula (II), which comprises a terminal glycol group, a terminal methylol group, a terminal carboxyl group.
  • the content of the carbonyl terminal represented by the general formula (I) is from 10 mol% to 40 mol% based on the total content of the acid base, the carbonyl terminal represented by the general formula (I) and the formyl terminal represented by the general formula (II).
  • a modified vinyl alcohol polymer having a formyl terminal content of 1 mol% to 25 mol% and a total content of 15 mol% to 45 mol% shown in the general formula (II).
  • R represents an alkyl group having 2 to 9 carbon atoms.
  • the modified vinyl alcohol polymer according to the present invention has a viscosity average polymerization degree of 500 to 1000, and an absorbance at a wavelength of 320 nm of a 0.2 mass% aqueous solution of 0.2 or more.
  • the modified vinyl alcohol polymer according to the present invention has a saponification degree of 60 mol% to 80 mol%.
  • the modified vinyl alcohol polymer according to the present invention has a terminal glycol group, a terminal methylol group, a terminal carboxylate group, a carbonyl terminal represented by the general formula (I), and a general formula (II).
  • the content of the terminal carboxylate group is 2 mol% to 8 mol% with respect to the total content of the formyl terminals.
  • 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.
  • This is a method for producing a modified vinyl alcohol polymer.
  • R represents an alkyl group having 2 to 9 carbon atoms.
  • a vinyl ester monomer is subjected to suspension polymerization in an aqueous medium while introducing a gas containing oxygen and in the presence of an aldehyde represented by the general formula (III). It is a manufacturing method of the modified vinyl alcohol polymer including the process of obtaining a polymer.
  • R represents an alkyl group having 2 to 9 carbon atoms.
  • the dispersion stabilizer for suspension polymerization of the present invention When the dispersion stabilizer for suspension polymerization of the present invention is used for suspension polymerization of vinyl compounds, it is possible to obtain resin particles that are fine and have high uniformity in particle size, high plasticizer absorbability, and appropriate bulk specific gravity. It becomes possible. As described above, the dispersion stabilizer for suspension polymerization of the present invention can have the required performance which is difficult to achieve with the prior art. Moreover, when the particle size uniformity of the resin particles is high and the plasticizer absorbability is high, it is possible to expect a reduction in fish eye and further excellent demonomerization. Therefore, the dispersion stabilizer for suspension polymerization according to the present invention is extremely advantageous industrially.
  • the dispersion stabilizer for suspension polymerization of the present invention contains a modified vinyl alcohol polymer (modified PVA) having a carbonyl terminal represented by the following general formula (I) and a formyl terminal represented by the general formula (II).
  • modified PVA modified vinyl alcohol polymer having a carbonyl terminal represented by the following general formula (I) and a formyl terminal represented by the general formula (II).
  • R represents an alkyl group having 2 to 9 carbon atoms.
  • the content of the carbonyl terminal shown in the general formula (I) in the modified PVA is as follows: each terminal (terminal glycol group, terminal methylol group, terminal carboxylate group, carbonyl terminal shown in the general formula (I) and general formula (II). It should be 10 mol% to 40 mol% with respect to the total content of the formyl end shown).
  • the content of the carbonyl terminal represented by the general formula (I) is less than 10 mol%, the unsaturated double bond starting point due to the carbonyl terminal is decreased or the protective colloid property is decreased. A vinyl resin having a diameter cannot be obtained.
  • the content of the carbonyl terminal represented by the general formula (I) needs to be 10 mol% or more, preferably 15 mol% or more, and preferably 20 mol% with respect to the total content of each terminal. % Or more is more preferable.
  • a terminal glycol group or vinyl acetate which is a heterogeneous bond terminal is used.
  • the terminal methylol group derived from the monomer must be controlled by precision polymerization or the like, which is disadvantageous for industrial production.
  • the content of the carbonyl terminal represented by the general formula (I) is required to be 40 mol% or less, preferably 38 mol% or less, and preferably 35 mol% based on the total content of each terminal. % Or less is more preferable.
  • the terminal glycol group means 1,2 glycol terminal (—CH 2 —CH (OH) —CH (OH) —CH 3 ), and the terminal methylol group means —CH 2 CH 2 OH.
  • the terminal carboxylate group refers to —CH 2 COOX (X is a metal atom such as an alkali metal such as Na).
  • R at the carbonyl terminal shown in the general formula (I) in the modified PVA is an alkyl group having 2 to 9 carbon atoms.
  • acetaldehyde having 1 carbon atom at the carbonyl terminal represented by formula (I) since the boiling point is low, it is difficult to control the polymerization, and in the suspension polymerization method, acetic acid is used because of high water solubility.
  • the affinity with vinyl monomer droplets is low, and there are drawbacks of poor polymerization stability, which is not industrially suitable. Therefore, the carbon number of R is preferably 2 or more, and more preferably 3 or more.
  • the carbon number of R is preferably 9 or less, more preferably 8 or less, even more preferably 6 or less, and even more preferably 5 or less.
  • R may be linear or branched.
  • R examples include ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t- Examples thereof include a pentyl group, hexyl group, isohexyl group, heptyl group, octyl group and the like.
  • the content of the formyl terminal shown in the general formula (II) in the modified PVA is as follows in each terminal (terminal glycol group, terminal methylol group, terminal carboxylate group, carbonyl terminal shown in the general formula (I) and general formula (II). It should be 1 mol% to 25 mol% with respect to the total content of the formyl end shown). When the content is less than 1 mol%, the unsaturated double bond starting point due to the formyl end is reduced or the protective colloid property is lowered, and as a result, a vinyl resin having an appropriate particle size cannot be obtained. .
  • the content of the formyl terminal represented by the general formula (II) is required to be 1 mol% or more, preferably 2 mol% or more with respect to the total content of each terminal. % Or more is more preferable.
  • the modified PVA is a modified PVA having a content of the formyl terminal represented by the general formula (II) exceeding 25 mol% with respect to the total content of the respective terminals
  • the vinyl system is used when used as a dispersant. Affects resin coloration. Moreover, it may become chemically unstable, and the viscosity of the aqueous solution may increase or gelate. Therefore, the content of the formyl terminal represented by the general formula (II) needs to be 25 mol% or less, preferably 23 mol% or less, and preferably 20 mol with respect to the total content of each terminal. % Or less is more preferable.
  • terminal glycol group, terminal methylol group, and terminal carboxylate group of the vinyl alcohol polymer are described in Shigetoshi Aiya, “PVA Fine Structure”, Polymer Processing, 38 (8), P388-396, 1989. As shown, it can be identified and quantified from the peak position of proton NMR and its integrated value.
  • the carbonyl terminal shown in the general formula (I) and the formyl terminal shown in the general formula (II) can also be obtained from the peak position of proton NMR and its integrated value.
  • a procedure for measuring the content of the terminal glycol group, terminal methylol group, terminal carboxylate group, carbonyl terminal represented by general formula (I), and formyl terminal represented by general formula (II) will be described.
  • the vinyl alcohol polymer is completely saponified to a saponification degree of 99.95 mol% or more, and then thoroughly washed with methanol to prepare a vinyl alcohol polymer for analysis.
  • saponification is unnecessary, and the analysis is performed as it is.
  • a 1 H-NMR spectrum with the number of integrations shown in Table 1 at the measured temperature was obtained.
  • the content of any terminal is calculated from the integrated value of the peak indicating each terminal described in Table 1, with the integrated value of the peak of the methylene group (1.2 to 2.0 ppm) of the main chain of PVA as a reference.
  • the terminal carboxylate group is in chemical equilibrium with the terminal ⁇ -lactone structure. Since proton NMR measurement is performed at pH 14 as described above, even when a terminal ⁇ -lactone structure is present in the modified PVA, all of them are changed to terminal carboxylate groups. Therefore, in the present invention, the content of the terminal carboxylate group means the total content of the terminal carboxylate group and the terminal ⁇ -lactone structure.
  • the total content of each terminal (terminal glycol group, terminal methylol group, terminal carboxylate group, carbonyl terminal represented by general formula (I) and formyl terminal represented by general formula (II))
  • the content of the terminal carboxylate group is preferably from 2 mol% to 8 mol%.
  • the affinity of the modified PVA for the vinyl compound is improved, the voids are increased, and the plasticizer absorption amount is increased. This is because improvement in physical properties can be seen.
  • the content of the terminal carboxylate group is 8 mol% or less, desirably 6 mol% or less, the protective colloid properties are enhanced and the dispersibility is improved.
  • the viscosity average degree of polymerization of the modified PVA according to the present invention can be 200 to 3500, which is generally used, but the viscosity average degree of polymerization is preferably 500 to 1000.
  • the viscosity average degree of polymerization is 500 or more, there is an advantage that the protective colloid property is enhanced and the secondary particles are easily refined.
  • generated by setting a viscosity average polymerization degree to 1000 or less can increase, and plasticizer absorptivity can be improved.
  • 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 saponification degree of the modified PVA according to the present invention is preferably 60 mol% or more from the viewpoint of water solubility and water dispersibility, more preferably 65 mol% or more, and even more preferably 70 mol% or more. preferable.
  • the degree of saponification of the modified PVA according to the present invention is preferably 80 mol% or less, and more preferably 75 mol% or less, from the viewpoint of increasing the porosity of the vinyl resin particles to be produced.
  • 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.
  • the modified PVA according to the present invention is proportional to the double bond amount of the polymer (modified PVA) from the viewpoint of promoting the refinement of the generated vinyl particles and easily increasing the porosity of the generated vinyl particles.
  • the absorbance at a wavelength of 320 nm of the 0.2% by mass aqueous solution is preferably 0.2 or more, more preferably 0.3 or more, and still more preferably 0.4 or more.
  • the modified PVA according to the present invention preferably has an absorbance at a wavelength of 320 nm of a 0.2 mass% aqueous solution of 2.0 or less from the viewpoint of increasing the amount of double bonds and decreasing the stability of the polymer (modified PVA). More preferably, it is 1.5 or less.
  • the absorbance at a wavelength of 320 nm of a 0.2 mass% aqueous solution of modified PVA is measured as follows.
  • a modified PVA to be measured is dissolved in water to prepare a 0.2 mass% aqueous solution at 25 ° C.
  • the said aqueous solution is put into a cell (optical path length 10mm), and the light absorbency in wavelength 320nm is measured.
  • the absorbance was measured using an absorptiometer “UV-1800” manufactured by Shimadzu Corporation.
  • the method for producing the modified PVA according to the present invention is not particularly limited, but is represented by the following formula (III) while introducing (typically blowing) a gas containing oxygen when radically polymerizing the vinyl ester monomer.
  • the resulting polymer is dissolved in alcohols and treated with an alkali such as sodium hydroxide or ammonia, or with an acid such as hydrochloric acid or paratoluenesulfonic acid to obtain a vinyl ester polymer.
  • the saponification method is simple and efficient.
  • the concept of “introducing a gas containing oxygen” refers to additionally sending oxygen from outside the reaction system into the reaction system, and oxygen due to air or the like initially exists in the reaction system. However, the oxygen is not treated as introduced oxygen.
  • R represents an alkyl group having 2 to 9 carbon atoms.
  • R are as described in formula (I).
  • Specific examples of the aldehyde represented by the formula (III) include propionaldehyde, butyraldehyde, pentylaldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, and decanaldehyde.
  • the aldehyde represented by the formula (III) may be used alone or in combination.
  • Vinyl ester monomers include vinyl acetate, vinyl formate, vinyl propionate, vinyl valelate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, saturated branched fatty acid vinyl, and versa Examples thereof include vinyl tick acid.
  • the polymerization method of the modified PVA according to the present invention is not particularly limited, and a known polymerization method such as solution, emulsification, suspension, and bulk polymerization can be arbitrarily used.
  • a method of producing by a polymerization method having a high concentration of vinyl ester monomer and a high concentration of aldehyde as a modified species is preferable because a carbonyl group is easily introduced at the terminal, and a suspension polymerization method is preferred.
  • the method of introducing oxygen can be arbitrarily selected, but it is preferable to introduce a gas diluted with an inert gas such as nitrogen, argon or helium so that the oxygen concentration becomes 1 to 9% by mass.
  • an inert gas such as nitrogen, argon or helium
  • the oxygen concentration is less than 1% by mass, a sufficient amount of oxygen is not introduced into the reaction field, and it becomes difficult to obtain a target PVA having a formyl end. If it exceeds 9% by mass, the explosion limit oxygen concentration of vinyl acetate (9 to 10% by mass) is exceeded, which raises a safety concern.
  • introduction of oxygen into the reaction system can be arbitrarily selected, the method of performing polymerization while bubbling directly into the polymerization solution can increase the contact area between the reaction system and oxygen, so that introduction efficiency is good.
  • the amount of oxygen to be introduced can be arbitrarily selected, but the amount of oxygen based on the monomer amount is preferably in the range of 0.02 mol% to 20 mol%. If it exceeds 20 mol% or more, it reacts with radicals during polymerization and polymerization does not proceed, which is not preferable in production. On the other hand, when it is 0.02 mol% or less, it becomes difficult to obtain a modified PVA having a sufficient formyl end.
  • the polymerization initiator for radical polymerization of the vinyl ester monomer is not particularly limited, but azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis (4-methoxy-2,4 -Dimethylvaleronitrile), azo compounds such as azobisdimethylvaleronitrile, azobismethoxyvaleronitrile, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2 Peroxides such as peroxyphenoxy acetate, percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, t-butyl Over oxy neodecanate, alpha-cumylperoxy neode
  • the polymerization rate refers to a value measured by a polymer concentration measurement method.
  • the polymerization solution is sampled during the polymerization, the weight is measured, the polymer concentration of the polymerization solution is calculated based on the weight of the polymer obtained by distilling off the monomer and the solvent, and the amount of polymer relative to the monomer is determined for polymerization. Calculate the rate.
  • the dispersion stabilizer for suspension polymerization of the present invention is a monomer that can be copolymerized with a vinyl ester monomer, for example, an unsaturated monoester such as acrylic acid, methacrylic acid, crotonic acid, etc., within the range that does not impair the spirit of the present invention.
  • Carboxylic acids or alkyl esters of these unsaturated monocarboxylic acids unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid or alkyl esters of these unsaturated dicarboxylic acids, nitriles such as acrylonitrile, methacrylonitrile, acrylamide and methacrylamide
  • olefin sulfonic acid such as amide, ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid or salts thereof, vinyl ether, vinyl ketone, ⁇ -olefin, vinyl halide, vinylidene halide, etc. can be copolymerized. .
  • the mixing ratio of such monomers is 10 mol% or less, preferably 5 mol% or less, based on the total number of moles of the vinyl ester monomer.
  • Saponification can be performed by dissolving the vinyl ester polymer obtained above in an alcohol and in the presence of an alkali catalyst or an acid catalyst.
  • the alcohol include methanol, ethanol, butanol and the like.
  • the concentration of the polymer in the alcohol is selected from the range of 20 to 70% by weight.
  • 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.
  • the amount of such a catalyst used must be 1 to 100 mmol equivalents relative to the vinyl ester monomer.
  • the saponification temperature is not particularly limited, but is usually in the range of 10 to 70 ° C., preferably 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 a pH adjuster, a crosslinking agent, an antiseptic, 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 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, and esters thereof 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 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 the production of soft vinyl chloride in terms of producing vinyl chloride particles having excellent plasticizer absorbability, but from the point of excellent particle size distribution, etc. It can also be applied to vinyl production.
  • the fact that vinyl chloride particles having excellent plasticizer absorbability can be produced means that there are many voids in the resulting vinyl chloride particles, so that the dispersion stabilizer for suspension polymerization of the present invention also has demonomerization properties. It can be expected that it is excellent and that the resulting vinyl chloride particles have less fish eyes.
  • 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.
  • a vinyl chloride resin having a porous resin particle and a uniform particle size distribution can be obtained even when suspension polymerization is carried out by a high temperature water charging polymerization method.
  • examples of the polymerization method of the vinyl compound will be described in detail, but the method is not limited thereto.
  • the above-mentioned dispersion stabilizer for suspension polymerization is 0.01% by mass to 0.3% by mass with respect to the vinyl compound monomer, preferably 0.8%. 04 mass% to 0.15 mass% is added.
  • 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.
  • dispersion stabilizer for suspension polymerization of the present invention it is possible to obtain resin particles that are fine and have high uniformity in particle size, high plasticizer absorbability, and appropriate bulk specific gravity.
  • the resin particles obtained using the dispersion stabilizer for suspension polymerization of the present invention can have an average particle size of 140 ⁇ m or less, preferably 130 ⁇ m or less, typically 110 ⁇ m to 140 ⁇ m.
  • the average particle size is 60 mesh (aperture 250 ⁇ m), 80 mesh (aperture 180 ⁇ m), 100 mesh (aperture 150 ⁇ m), 150 mesh (aperture 106 ⁇ m), 200 mesh (aperture)
  • D50 particle diameter having a cumulative frequency of 50% (mass basis) when the particle size distribution is determined using a sieve having an opening of 75 ⁇ m.
  • the resin particles obtained using the dispersion stabilizer for suspension polymerization according to the present invention have a particle size (D80) having a cumulative frequency of 80% (mass basis) when the particle size distribution is determined by the above method.
  • the difference in particle diameter (D20) with a cumulative frequency of 20% (mass basis) can be 60 ⁇ m or less, preferably 55 ⁇ m or less, and typically 40 ⁇ m to 60 ⁇ m.
  • the resin particles obtained using the dispersion stabilizer for suspension polymerization of the present invention can have a plasticizer absorption of 23 phr or more, and preferably have a plasticizer absorption of 30 phr or more. Typically having a plasticizer uptake of 23 phr to 35 phr.
  • the plasticizer absorption amount of the resin is measured by the following procedure. Glass fiber is 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 resin is charged.
  • DOP dioctyl phthalate
  • the resin particles obtained using the dispersion stabilizer for suspension polymerization of the present invention are 0.40 g / mL or more, preferably 0.42 g / mL or more, and typically 0.40 g / mL to It can have a bulk specific gravity of 0.45 g / mL.
  • the bulk specific gravity is measured according to JIS K6720-2: 1999.
  • Example 1 Provide of dispersion stabilizer> A polymerization can was charged with 100 parts of vinyl acetate (monomer), 120 parts of water, 0.087 part of polyvinyl alcohol as a dispersant, 1.5 parts of modified normal butyraldehyde, and 0.026 part of azobisisobutyronitrile. Then, an oxygen-nitrogen mixed gas (oxygen concentration 4%, total oxygen amount 0.11 mol% with respect to vinyl acetate) was heated while being blown into the gas phase immediately above the polymerization solution to polymerize at 60 ° C, and the polymerization rate reached 90%. At that time, the polymerization was stopped.
  • an oxygen-nitrogen mixed gas oxygen concentration 4%, total oxygen amount 0.11 mol% with respect to vinyl acetate
  • unpolymerized vinyl acetate is removed by a conventional method, and the resulting polymer is dissolved in methanol, saponified with sodium hydroxide by a conventional method, and methanol is separated by filtration, and then in a gear oven at 90 ° C. for 80 minutes. By drying, a powdery modified vinyl alcohol polymer (dispersion stabilizer) was obtained.
  • the viscosity average polymerization degree was 600, the saponification degree was 71 mol%, the absorbance was 0.29, the terminal carboxylate group content was 3.7 mol%, and the general formula was measured.
  • the carbonyl terminal shown in (I) was 26.3 mol%
  • the formyl terminal shown in general formula (II) was 3.7 mol%.
  • 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 with a mesh opening of 75 ⁇ m, the particle diameter (D50) with a cumulative frequency of 50% (mass basis) is the average particle diameter, the particle diameter (D80) with a cumulative frequency of 80% (mass basis) and a cumulative frequency of 20% (mass) The difference in the particle size (D20) of the “standard” was defined as the particle size distribution.
  • 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, 15 mL of a plasticizer (dioctyl phthalate, hereinafter referred to as DOP) was added and allowed to stand for 30 minutes to allow the DOP to sufficiently penetrate 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 dioctyl phthalate
  • Table 2 shows the modified species and the amount charged, the total amount of oxygen supplied by the oxygen-nitrogen mixed gas, the oxygen concentration of the oxygen-nitrogen mixed gas, the location where the oxygen-nitrogen mixed gas was blown, the polymerization rate, the degree of polymerization, and the degree of saponification.
  • a modified vinyl alcohol polymer (dispersion stabilizer) was obtained in the same manner as in Example 1 except that the conditions were changed.
  • “gas phase” is a method in which the oxygen-nitrogen mixed gas discharge port is placed in the gas phase directly above the polymerization liquid and blown in the same manner as in Example 1.
  • “Liquid phase” refers to a method (bubbling) in which an oxygen-nitrogen mixed gas discharge port is inserted into a polymerization solution. Subsequently, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used. Table 2 shows the results of evaluating the properties of the modified vinyl alcohol polymer (dispersion stabilizer) and the vinyl chloride resin in the same manner as in Example 1.
  • Example 5 The modified vinyl acetate polymer obtained in Example 2 was saponified by adjusting the amount of sodium hydroxide to obtain a modified vinyl alcohol polymer having a saponification degree of 80%.
  • a suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used.
  • Table 2 shows the results of evaluating the properties of the dispersion stabilizer and the vinyl chloride resin in the same manner as in Example 1.
  • Example 7 The modified vinyl alcohol polymer obtained in Example 6 was heat treated at 120 ° C. for 4 hours to obtain a resin with increased absorbance. A suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used. Table 2 shows the results of evaluating the properties of the dispersion stabilizer and the vinyl chloride resin in the same manner as in Example 1.
  • Example 10 100 parts of vinyl acetate, 1.3 parts of modified normal butyraldehyde and 0.083 parts of azobisisobutyronitrile were charged into a polymerization vessel, and an oxygen-nitrogen mixed gas (oxygen concentration of 3%, total amount of oxygen with respect to vinyl acetate was 0). .05 mol%) was heated to 65 ° C. while blowing into the gas phase directly above the polymerization solution, and the polymerization was stopped when the polymerization rate reached 70%. Thereafter, saponification was performed in the same procedure as in Example 1, and a powdery modified vinyl alcohol polymer (dispersion stabilizer) was obtained after separation operation. A suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used. Table 2 shows the results of evaluating the properties of the dispersion stabilizer and the vinyl chloride resin in the same manner as in Example 1.
  • Example 1 The modified vinyl alcohol polymer was changed in the same manner as in Example 1 except that the charged amount of the modified species was changed to the conditions shown in Table 2, and the reaction system was changed to nitrogen atmosphere by nitrogen substitution and polymerization was performed while introducing nitrogen from the gas phase. (Dispersion stabilizer) was obtained. Subsequently, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used. Table 2 shows the results of evaluating the properties of the dispersion stabilizer and the vinyl chloride resin in the same manner as in Example 1. In this case, since the average particle diameter of the obtained vinyl chloride resin particles is large and the particle size distribution is wide, the dispersion stabilizer has insufficient dispersibility.
  • Comparative Example 2 The polymerization rate and the degree of saponification were changed to the conditions shown in Table 2, and the reaction system was liquid-sealed without replacing with nitrogen, and air introduction from the outside was shut off. Other conditions were modified in the same manner as in Example 1. A vinyl alcohol polymer (dispersion stabilizer) was obtained. Subsequently, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that the obtained dispersion stabilizer was used. Table 2 shows the results of evaluating the properties of the dispersion stabilizer and the vinyl chloride resin in the same manner as in Example 1. In this case, since the average particle diameter of the obtained vinyl chloride resin particles is large and the particle size distribution is wide, the dispersion stabilizer has insufficient dispersibility. In Comparative Example 2, some formyl ends are formed, which is considered to be caused by air originally present in the reaction system.
  • Table 2 shows the results of evaluating the properties of the dispersion stabilizer and the vinyl chloride resin in the same manner as in Example 1. In this case, since the average particle diameter of the obtained vinyl chloride resin particles is large and the particle size distribution is wide, the dispersion stabilizer has insufficient dispersibility.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un stabilisateur de dispersion qui convient à une utilisation dans la polymérisation en suspension d'un composé vinylique pour obtenir des particules de résine qui sont fines et ont une uniformité élevée de taille de particule, des propriétés d'absorption de plastifiant élevées, et un poids spécifique apparent approprié. Le stabilisateur de dispersion comprend un polymère d'alcool vinylique modifié comprenant des extrémités terminales carbonyle représentées par la formule générale (I) et des extrémités terminales formyle représentés par la formule générale (II), la teneur en extrémités carbonyle représentée par la formule générale (I), la teneur en extrémités formyle représentées par la formule générale (II), et la teneur totale en ces deux types d'extrémités étant comprise entre 10 et 40 % en moles, 1 et 25 % en moles, et 15 et 45 % en moles, respectivement, par rapport à la teneur totale en groupes glycol terminaux, en groupes méthylol terminaux, en groupes sels d'acide carboxylique terminaux, en extrémités terminales carbonyle représentées par la formule générale (I) et en extrémités terminales formyle représentées par la formule générale (II). (Dans la formule (I), R représente un groupe alkyle en C2-9).
PCT/JP2017/040464 2016-11-24 2017-11-09 Alcool polyvinylique modifié et procédé de production associé WO2018096937A1 (fr)

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WO2021145393A1 (fr) * 2020-01-16 2021-07-22 三菱ケミカル株式会社 Résine d'alcool polyvinylique, procédé de production de résine d'alcool polyvinylique, dispersant et dispersant de polymérisation en suspension
JPWO2022097572A1 (fr) * 2020-11-04 2022-05-12
WO2024075829A1 (fr) * 2022-10-06 2024-04-11 株式会社クラレ Composition, agent dispersant pour la polymérisation en suspension et procédé de production de polymère à base de vinyle

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JP2020200460A (ja) * 2019-06-10 2020-12-17 株式会社クラレ ポリビニルアルコール、その製造方法及びその用途
EP3878285A1 (fr) * 2020-03-12 2021-09-15 Kuraray Co., Ltd. Boîtiers alimentaires synthétiques comprenant de l'alcool polyvinylique et procédé pour leur fabrication

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JPH07228624A (ja) * 1994-02-17 1995-08-29 Kuraray Co Ltd ポリビニルアルコ−ル粒状成形ゲル及びその製造法
WO2008096727A1 (fr) * 2007-02-07 2008-08-14 Kuraray Co., Ltd. Stabilisant de dispersion pour polymérisation en suspension d'un composé vinylique et procédé de fabrication d'un polymère de composé vinylique
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WO2015019614A1 (fr) * 2013-08-07 2015-02-12 株式会社クラレ Agent de stabilisation de dispersion pour la polymérisation en suspension, et procédé de fabrication de résine de vinyle
WO2015119144A1 (fr) * 2014-02-05 2015-08-13 株式会社クラレ Agent dispersant pour la polymérisation en suspension d'un composé de vinyle

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JPH07228624A (ja) * 1994-02-17 1995-08-29 Kuraray Co Ltd ポリビニルアルコ−ル粒状成形ゲル及びその製造法
WO2008096727A1 (fr) * 2007-02-07 2008-08-14 Kuraray Co., Ltd. Stabilisant de dispersion pour polymérisation en suspension d'un composé vinylique et procédé de fabrication d'un polymère de composé vinylique
WO2012043280A1 (fr) * 2010-09-27 2012-04-05 積水化学工業株式会社 Alcool polyvinylique modifié, acétal polyvinylique modifié et composition de bouillie céramique
WO2015019614A1 (fr) * 2013-08-07 2015-02-12 株式会社クラレ Agent de stabilisation de dispersion pour la polymérisation en suspension, et procédé de fabrication de résine de vinyle
WO2015119144A1 (fr) * 2014-02-05 2015-08-13 株式会社クラレ Agent dispersant pour la polymérisation en suspension d'un composé de vinyle

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Publication number Priority date Publication date Assignee Title
WO2021145393A1 (fr) * 2020-01-16 2021-07-22 三菱ケミカル株式会社 Résine d'alcool polyvinylique, procédé de production de résine d'alcool polyvinylique, dispersant et dispersant de polymérisation en suspension
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JPWO2022097572A1 (fr) * 2020-11-04 2022-05-12
WO2022097572A1 (fr) * 2020-11-04 2022-05-12 株式会社クラレ Dispersant pour polymérisation en suspension et procédé de production de polymère à base de vinyle
JP7321394B2 (ja) 2020-11-04 2023-08-04 株式会社クラレ 懸濁重合用分散剤及びビニル系重合体の製造方法
WO2024075829A1 (fr) * 2022-10-06 2024-04-11 株式会社クラレ Composition, agent dispersant pour la polymérisation en suspension et procédé de production de polymère à base de vinyle

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