WO2017170577A1 - カルボキシル基含有重合体組成物の製造方法 - Google Patents
カルボキシル基含有重合体組成物の製造方法 Download PDFInfo
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- WO2017170577A1 WO2017170577A1 PCT/JP2017/012700 JP2017012700W WO2017170577A1 WO 2017170577 A1 WO2017170577 A1 WO 2017170577A1 JP 2017012700 W JP2017012700 W JP 2017012700W WO 2017170577 A1 WO2017170577 A1 WO 2017170577A1
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
- C08F2/08—Organic solvent with the aid of dispersing agents for the polymer
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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
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Definitions
- the present invention relates to a method for producing a carboxyl group-containing polymer composition.
- carboxyl group-containing polymers have been used as gelling bases for cosmetic thickeners, moisturizers for poultices, emulsifiers, suspension stabilizers, batteries, and the like.
- the carboxyl group-containing polymer is added to water or the like to prepare a uniform dispersion, and then neutralized with an alkali and used.
- the carboxyl group-containing polymer is a fine powder, when dispersed in water or the like, a lump (mamako (seed powder)) tends to occur.
- Mamako is formed, a gel-like layer is formed on the surface of Mamako, so that the speed at which water penetrates into Mamako is slow, and it is difficult to obtain a uniform dispersion.
- a carboxyl group-containing polymer is produced by polymerizing ⁇ , ⁇ -unsaturated carboxylic acid or the like, a polyhydric alcohol fatty acid ester alkylene oxide adduct and a polyhydric alcohol fatty acid are used. It is known that a carboxyl group-containing polymer composition having excellent dispersibility in water can be obtained by adding a specific amount of at least one compound of the ester and polymerizing the polymer (see Patent Document 1). .
- the carboxyl group-containing polymer composition disclosed in Patent Document 1 is excellent in dispersibility in water immediately after production and the transparency of the neutralized viscous liquid, it is stored at room temperature for about one month, for example. Then, there exists a problem that the dispersibility to water etc. deteriorates. That is, the carboxyl group-containing polymer composition disclosed in Patent Document 1 has room for improvement in terms of storage stability.
- storage stability means “excellent dispersibility is maintained over a long period of time”.
- the main object of the present invention is to provide a method for producing a carboxyl group-containing polymer composition having excellent dispersibility in water immediately after production, storage stability, and transparency of a neutralized viscous liquid. There is.
- a carboxyl group containing a copolymer of a monomer containing ⁇ , ⁇ -unsaturated carboxylic acid (a-1) and compound (a-2) having at least two ethylenically unsaturated groups in the molecule A method for producing a carboxyl group-containing polymer composition comprising a polymer (A) and a nonionic surfactant (B), wherein in the step of copolymerizing monomers, ⁇ , ⁇ -unsaturation
- the polymerization rate of the carboxylic acid (a-1) became 70 to 100% (that is, 70% of the total ⁇ , ⁇ -unsaturated carboxylic acid (a-1) used in the step of copolymerizing the monomers).
- the resulting carboxyl group-containing polymer composition has improved storage stability. I found it excellent. Furthermore, the carboxyl group-containing polymer composition obtained by such a production method can also be dispersed without damaging the transparency of the neutralized viscous liquid even when dispersed in water or the like immediately after production. I found it to be improved.
- the present invention is an invention that has been completed based on such findings and further earnest studies.
- a carboxyl group-containing polymer that is a copolymer of a monomer comprising an ⁇ , ⁇ -unsaturated carboxylic acid (a-1) and a compound (a-2) having at least two ethylenically unsaturated groups in the molecule
- a method for producing a carboxyl group-containing polymer composition comprising A) and a nonionic surfactant (B), Comprising the step of copolymerizing the monomers, In this step, when the polymerization rate of the ⁇ , ⁇ -unsaturated carboxylic acid (a-1) reaches 70 to 100%, the nonionic surfactant (B) is added to the system.
- a method for producing a polymer composition Item 2.
- Item 2. The carboxyl group according to Item 1, wherein the addition amount of the nonionic surfactant (B) is 0.5 to 9 parts by mass with respect to 100 parts by mass of the ⁇ , ⁇ -unsaturated carboxylic acid (a-1).
- a method for producing a polymer composition Item 2.
- Item 2. The carboxyl group according to Item 1, wherein the addition amount of the nonionic surfactant (B) is 0.5 to 9 parts by mass with respect to 100 parts by mass of the ⁇ , ⁇ -unsaturated carboxylic acid (a-1).
- the production method of the present invention is a copolymer of a monomer containing an ⁇ , ⁇ -unsaturated carboxylic acid (a-1) and a compound (a-2) having at least two ethylenically unsaturated groups in the molecule.
- a method for producing a carboxyl group-containing polymer composition comprising a certain carboxyl group-containing polymer (A) and a nonionic surfactant (B), comprising a step of copolymerizing the monomers. Yes.
- the nonionic surfactant ( B) is added.
- the nonionic surfactant (B) may be added at least when the polymerization rate is 70 to 100%, and further added when the polymerization rate is 0% or more and less than 70%. The same effect can be expected.
- the addition amount is 100 parts by mass of the component (B) addition when the polymerization rate is 70 to 100%. On the other hand, it exceeds 0 mass part and about 50 mass parts or less is mentioned.
- a neutralizing agent such as an alkaline compound
- a monomer comprising an ⁇ , ⁇ -unsaturated carboxylic acid (a-1) and a compound (a-2) having at least two ethylenically unsaturated groups in the molecule is copolymerized.
- a carboxyl group-containing polymer (A) is produced by this step. That is, at least an ⁇ , ⁇ -unsaturated carboxylic acid (a-1) and a compound (a-2) having at least two ethylenically unsaturated groups are used as monomers, and the monomer containing these is used as a monomer.
- the manufacturing method of this invention may include processes other than the said process.
- the ⁇ , ⁇ -unsaturated carboxylic acid (a-1) (sometimes referred to as monomer (a-1)) is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, maleic acid, Examples thereof include olefinic unsaturated carboxylic acids having 3 to 5 carbon atoms such as itaconic acid and fumaric acid.
- these ⁇ , ⁇ -unsaturated carboxylic acids (a-1) they are inexpensive and easily available, and the neutralized viscous liquid using the resulting carboxyl group-containing polymer composition has high transparency.
- Acrylic acid, methacrylic acid and the like are preferably used.
- These ⁇ , ⁇ -unsaturated carboxylic acids may be used alone or in combination of two or more.
- the compound (a-2) having at least two ethylenically unsaturated groups is not particularly limited, and examples thereof include two or more substitutions of polyol.
- Acrylic acid esters Methacrylic acid esters with two or more polyols; Allyl ethers with two or more polyols; Diallyl phthalate, triallyl phosphate, allyl methacrylate, tetraallyloxyethane, triallyl cyanurate, adipic acid
- examples include divinyl, vinyl crotonate, 1,5-hexadiene, divinylbenzene and the like.
- the polyol include ethylene glycol, propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, polyglycerin, trimethylolpropane, pentaerythritol, saccharose, sorbitol and the like.
- pentaerythritol triallyl ether is used from the viewpoint of easy viscosity adjustment of the neutralized viscous liquid using the obtained carboxyl group-containing polymer composition.
- Erythritol tetraallyl ether, tetraallyloxyethane, triallyl phosphate, and polyallyl saccharose are preferably used.
- These compounds (a-2) having at least two ethylenically unsaturated groups may be used alone or in combination of two or more.
- the ratio of the compound (a-2) having at least two ethylenically unsaturated groups is preferably 0.01 to 10 parts by mass, more preferably 100 parts by mass of ⁇ , ⁇ -unsaturated carboxylic acid.
- the amount is 0.05 to 10 parts by mass, and more preferably 0.05 to 3 parts by mass.
- the resulting carboxyl group-containing polymer composition can be suitably used as a neutralized viscous liquid.
- “100 parts by mass of ⁇ , ⁇ -unsaturated carboxylic acid” means the total amount of ⁇ , ⁇ -unsaturated carboxylic acid (a-1) used in the production method of the present invention. .
- an ⁇ , ⁇ -unsaturated compound (from the viewpoint of adjusting the viscosity of the neutralized viscous liquid using the resulting carboxyl group-containing polymer composition ( a-3) or the like may be used.
- the ⁇ , ⁇ -unsaturated compound (a-3) is not particularly limited as long as it is different from the ⁇ , ⁇ -unsaturated carboxylic acid (a-1).
- Acrylates such as octyl acrylate, 2-ethyl acrylate, decyl acrylate, lauroyl acrylate, stearyl acrylate, glycidyl acrylate; methacrylic acid esters corresponding to the above acrylate esters; vinyl glycidyl ether, isopropenyl glycidyl Glycidyl ethers such as ether, allyl glycidyl ether and butenyl glycidyl ether; acrylic amides such as acrylamide, N-methyl acrylamide, N-ethyl acrylamide and Nt-butyl acrylamide S; me
- acrylic acid esters and methacrylic acid esters are preferably used, and in particular, straight chain having 12 to 40 (particularly 15 to 30) carbon atoms or Acrylic acid esters and methacrylic acid esters having a branched alkyl group are preferred, and stearyl methacrylate, eicosanyl methacrylate, behenyl methacrylate, and tetracosanyl methacrylate are more preferably used.
- These ⁇ , ⁇ -unsaturated compounds (a-3) may be used alone or in combination of two or more.
- a trade name Blemmer VMA70 manufactured by NOF Corporation may be used as the acrylic acid esters and methacrylic acid esters.
- the amount of ⁇ , ⁇ -unsaturated compound (a-3) used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of ⁇ , ⁇ -unsaturated carboxylic acid (a-1).
- the amount is preferably 1 to 10 parts by mass. If the amount of ⁇ , ⁇ -unsaturated compound (a-3) used is 0.1 parts by mass or more, the effect of adjusting the viscosity of the neutralized viscous liquid using the resulting carboxyl group-containing polymer composition is suitably obtained. It can be expressed.
- the amount of ⁇ , ⁇ -unsaturated compound (a-3) used is 20 parts by mass or less, the viscosity of the neutralized viscous liquid using the resulting carboxyl group-containing polymer composition is too low. Can be suppressed.
- ⁇ , ⁇ -unsaturated carboxylic acid (a-1) compound having at least two ethylenically unsaturated groups (a-2)
- the total proportion of the ⁇ , ⁇ -unsaturated compound (a-3) is not particularly limited, but is preferably 50% by mass or more, more preferably about 80% by mass to 100% by mass, and still more preferably 90% by mass.
- the total ratio may be substantially 100% by mass.
- the ratio of the ⁇ , ⁇ -unsaturated carboxylic acid (a-1) in the monomer constituting the carboxyl group-containing polymer (A) is not particularly limited, but is preferably 95% by mass or more, more preferably Is about 96% to 99% by weight, more preferably about 97% to 98% by weight.
- the method for copolymerizing these monomers is not particularly limited, and known or conventional methods can be applied. Specifically, for example, it can be carried out by any of the following methods (1) to (3).
- Method (1) ⁇ , ⁇ -unsaturated carboxylic acid (a-1) and compound (a-2) having at least two ethylenically unsaturated groups (if necessary, ⁇ , ⁇ -unsaturated compound ( a-3) and a) are co-polymerized from the beginning of polymerization (for example, all are co-existing).
- Method (2) The ⁇ , ⁇ -unsaturated carboxylic acid (a-1) is mixed with an ethylenically unsaturated group.
- the method of attaching is not particularly limited, and for example, it may be previously allowed to coexist with ⁇ , ⁇ -unsaturated carboxylic acid (a-1), or compound (a-2) having at least two ethylenically unsaturated groups It may be added continuously in the same manner as described above.
- Method (3) Method of polymerizing ⁇ , ⁇ -unsaturated carboxylic acid (a-1) and compound (a-2) having at least two ethylenically unsaturated groups while continuously adding
- the method for subjecting it to the polymerization is not particularly limited. For example, it may be charged into the polymerization system in advance, or ⁇ , ⁇ -It may be added continuously in the same manner as the unsaturated carboxylic acid (a-1) and the compound (a-2) having at least two ethylenically unsaturated groups.
- the method (1) will be specifically described.
- ⁇ , ⁇ -unsaturated carboxylic acid (a-1) previously weighed in a desired amount in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas blowing tube, and a cooling tube.
- a compound (a-2) having at least two ethylenically unsaturated groups, a radical polymerization initiator, and an inert solvent for example, ⁇ , ⁇ -unsaturated carboxylic acid (a-1) previously weighed in a desired amount in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas blowing tube, and a cooling tube.
- a compound (a-2) having at least two ethylenically unsaturated groups, a radical polymerization initiator, and an inert solvent.
- the polymerization reaction can be performed by heating to 20 to 120 ° C., preferably 30 to 90 ° C. in a warm bath or the like. The polymerization reaction is usually completed in 2 to 10 hours.
- the unsaturated compound (a-3) is used, the ⁇ , ⁇ -unsaturated carboxylic acid (a-1), the compound (a-2) having at least two ethylenically unsaturated groups, and ⁇ ,
- the total charged amount of ⁇ -unsaturated compound (a-3) is desirably 1% by mass or more, preferably 5% by mass or more from the viewpoint of increasing volumetric efficiency and improving productivity.
- the reaction from the viewpoint of smooth progress of 30 wt% or less, preferably not more than 25 wt%.
- a preferable total charge is 1 to 30% by mass, and more preferably 5 to 25% by mass.
- the inert solvent examples include ⁇ , ⁇ -unsaturated carboxylic acid (a-1), compound (a-2) having at least two ethylenically unsaturated groups, and ⁇ , ⁇ -unsaturated compound (a-3).
- the obtained carboxyl group-containing polymer composition is not particularly limited as long as it is a solvent that does not dissolve.
- the inert solvent include aliphatic hydrocarbons having 2 to 8 carbon atoms which may be substituted with halogen such as ethylene dichloride, normal pentane, normal hexane, isohexane, normal heptane, normal octane, isooctane, etc .; cyclopentane C 5-7 alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, etc .; aromatic hydrocarbons optionally substituted with halogen such as benzene, toluene, xylene, chlorobenzene; ethyl acetate, isopropyl acetate, etc.
- halogen such as ethylene dichloride, normal pentane, normal hexane, isohexane, normal heptane, normal octane, isooctane, etc .
- acetic acid alkyl esters such as methyl ethyl ketone and methyl isobutyl ketone.
- ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone.
- these inert solvents ethylene dichloride, normal hexane, cyclohexane, normal heptane, and ethyl acetate are preferable from the viewpoint of stable quality and easy availability.
- radical polymerization initiator is not particularly limited. Specific examples thereof include ⁇ , ⁇ ′-azoisobutyronitronyl, 2,2′-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2′-azobisisobutyrate, benzoyl peroxide, lauroyl. Peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide and the like can be mentioned.
- a radical polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.
- the amount of radical polymerization initiator varies depending on the type and reaction temperature, and cannot be determined unconditionally. However, from the viewpoint of increasing the polymerization reaction rate, the monomer of the carboxyl group-containing polymer (A) is usually used.
- the amount of the radical polymerization initiator is preferably 0.1 to 10% by mass, more preferably 0.3 to 3% by mass.
- the atmosphere during the reaction is preferably an inert gas atmosphere such as nitrogen gas or argon gas from the viewpoint of avoiding the influence of oxygen.
- the nonionic surface activity in the system is increased.
- Add agent (B) That is, the nonionic surfactant (B) is in a state where the copolymerization of the ⁇ , ⁇ -unsaturated carboxylic acid (a-1) is incomplete (the polymerization rate is 70% or more and less than 100%) Is completed (the polymerization rate is 100%), it is added to the system.
- the nonionic surfactant (B) in the production method of the present invention, by adding the nonionic surfactant (B) at a specific timing, dispersibility in water immediately after production, storage stability, and transparency of the neutralized viscous liquid can be improved. It becomes possible to produce a carboxyl group-containing polymer composition excellent in all.
- the said nonionic surfactant (B) is added at the time of the said polymerization rate being 70% or more at least, even if it adds separately at the time of less than 70%, the same effect will be expressed.
- the polymerization rate in the copolymerization step can be confirmed by the method described in Examples.
- the nonionic surfactant (B) is composed of a hydrophilic part and a hydrophobic part.
- hydrophobic portion include polyhydric alcohol fatty acid esters and hydroxy fatty acid addition polymers.
- polyhydric alcohol part of the polyhydric alcohol fatty acid ester examples include glycerin, polyglycerin, trimethylpropanol, sorbit, sorbitan and the like.
- polyhydric alcohol residue of the nonionic surfactant (B) those derived from these polyhydric alcohols are preferred.
- One type of polyhydric alcohol part may be sufficient, and two or more types may be sufficient as it.
- Suitable examples of the fatty acid portion of the polyhydric alcohol fatty acid ester include stearic acid, isostearic acid, palmitic acid and the like. That is, as the fatty acid residue of the nonionic surfactant (B), those derived from these fatty acids are preferable.
- the fatty acid moiety may be one type or two or more types.
- examples of the polyhydric alcohol fatty acid ester in the hydrophobic portion of the nonionic surfactant (B) include stearic acid ester, isostearic acid ester, palmitic acid ester, and hardened castor oil derivative.
- Suitable examples of the addition polymer of hydroxy fatty acid in the hydrophobic part of the nonionic surfactant (B) include addition polymers of 2-hydroxy palmitic acid, 16-hydroxy palmitic acid, and 12-hydroxy stearic acid. Is mentioned.
- hydrophilic part of the nonionic surfactant (B) examples include a carboxy group, a hydroxy group, an amino group, a sulfonyl group, and an ether group.
- the ether group in the hydrophilic part of the nonionic surfactant (B) may be an oxyalkylene chain such as polyoxyalkylene.
- Preferable examples of the oxyalkylene chain in the nonionic surfactant (B) include an oxyalkylene group represented by the following formula.
- R 1 represents a hydrogen atom, a methyl group or an ethyl group, and n represents an integer of 1 to 100. If n is an integer of 2 or more, plural R 1 may each be the same or may be different.
- a polyhydric alcohol fatty acid ester alkylene oxide adduct is preferably exemplified.
- the polyhydric alcohol fatty acid ester alkylene oxide adduct is a compound in which an alkylene oxide is added to a fatty acid ester of a polyhydric alcohol.
- the polyhydric alcohol fatty acid ester alkylene oxide adduct functions as an emulsifier.
- Suitable examples of the polyhydric alcohol moiety in the polyhydric alcohol fatty acid ester alkylene oxide adduct include glycerin, polyglycerin, trimethylpropanol, sorbit, sorbitan and the like as described above. That is, the polyhydric alcohol residue of the polyhydric alcohol fatty acid ester alkylene oxide adduct is preferably derived from these polyhydric alcohols.
- One type of polyhydric alcohol part may be sufficient, and two or more types may be sufficient as it.
- suitable examples of the fatty acid moiety in the polyhydric alcohol fatty acid ester alkylene oxide adduct include stearic acid, isostearic acid, palmitic acid and the like as described above. That is, as the fatty acid residue of the polyhydric alcohol fatty acid ester alkylene oxide adduct, those derived from these fatty acids are preferred.
- the fatty acid moiety may be one type or two or more types.
- examples of the polyhydric alcohol fatty acid ester in the polyhydric alcohol fatty acid ester alkylene oxide adduct include stearic acid ester, isostearic acid ester and palmitic acid ester, and hardened castor oil derivatives.
- Suitable examples of the oxyalkylene chain in the polyhydric alcohol fatty acid ester alkylene oxide adduct include an oxyalkylene group represented by the above general formula (I).
- the HLB in the nonionic surfactant (B) is preferably 5 to 8.
- nonionic surfactant (B) examples include polyoxyethylene glyceryl triisostearate, polyoxyethylene (30) triisostearate hydrogenated castor oil, polyoxyethylene hydrogenated castor oil derivative, polyoxyethylene glycerin fatty acid ester And polyoxyethylene tristearate trimethylol.
- polyoxyethylene glycerin fatty acid ester examples include polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl distearate, polyoxyethylene glyceryl tristearate, polyoxyethylene glyceryl isostearate, polyoxyethylene glyceryl diisostearate, tris Polyoxyethylene glyceryl isostearate, block copolymer of 2-hydroxypalmitic acid and alkylene glycol, block copolymer of 16-hydroxypalmitic acid and alkylene glycol, and block copolymer of 12-hydroxystearic acid and alkylene glycol Is mentioned.
- Preferred examples of polyhydric alcohol fatty acid ester alkylene oxide adducts when the hardened castor oil derivative is a polyhydric alcohol fatty acid ester include polyoxyethylene hardened castor oil, polyoxyethylene hardened castor oil laurate, isostearin Acid polyoxyethylene hydrogenated castor oil, triisostearic acid polyoxyethylene hydrogenated castor oil, and the like.
- polyhydric alcohol fatty acid ester alkylene oxide adducts a carboxyl group-containing polymer composition having excellent dispersibility can be obtained with a small amount of use, and the thickening effect is maintained while maintaining the high transparency of the neutralized viscous liquid. Therefore, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil isostearate, polyoxyethylene hydrogenated castor oil triisostearate and polyoxyethylene sorbite tetraoleate are preferred.
- the addition amount of the nonionic surfactant (B) (that is, nonionic properties at the time when the polymerization rate is 70% or more and 100% or less)
- the addition amount of the surfactant (B) is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the carboxyl group-containing polymer (A).
- the addition amount of the nonionic surfactant (B) is preferably about 0.5 to 9 parts by mass, more preferably 3 to 7 parts by mass.
- the method for producing the carboxyl group-containing polymer composition of the present invention can be carried out, for example, in the following methods (1A) and (2A).
- the ⁇ , ⁇ -unsaturated compound (a-3) the method for subjecting it to polymerization is not particularly limited. For example, it may be charged in a reaction vessel in advance, or the ⁇ , ⁇ -unsaturated carboxylic acid (a-1) and the ethylenically unsaturated group may be used. May be continuously added to the reaction vessel in the same manner as the compound (a-2) having at least two.
- ⁇ , ⁇ -unsaturated carboxylic acid (a-1), which is previously weighed in a desired amount in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas blowing tube and a cooling tube, A compound (a-2) having at least two ethylenically unsaturated groups, an ⁇ , ⁇ -unsaturated compound (a-3), a radical polymerization initiator, and an inert solvent are charged if necessary.
- Nitrogen gas is blown into the contents.
- the polymerization reaction can be carried out by heating to 20 to 120 ° C., preferably 30 to 90 ° C. in a warm bath or the like.
- the polymerization reaction is usually completed in 2 to 10 hours.
- the nonionic surfactant (B) is diluted with an inert solvent, added to the slurry in the system, and stirred until uniform.
- the inert solvent is distilled off from the reaction solution by heating under reduced pressure or normal pressure, and the carboxyl group-containing polymer composition can be obtained as a white fine powder.
- an alkaline component such as sodium hydroxide or triethanolamine
- alcohol gel means “gel obtained by dissolving a carboxy group-containing polymer composition in an aqueous solution containing a total of 54 to 94% by weight of a single component or a plurality of component alcohols”.
- the polymerization rate of ⁇ , ⁇ -unsaturated carboxylic acid (a-1) is, for example, 70.
- the non-ionic surfactant (B) was added to the system at the time when it reached -80% to produce a carboxyl group-containing polymer composition, the resulting carboxyl group-containing polymer composition was A neutralized viscous liquid or alcohol gel having excellent dispersibility in water and the like and excellent in viscosity and transparency can be obtained.
- Dispersibility 100 g of ion-exchanged water is put into a 200 mL (milliliter) beaker, and the temperature of the ion-exchanged water is adjusted to 25 ° C.
- 3.0 g of the carboxyl group-containing polymer composition was charged all at once without stirring, and the swelling state of the carboxyl group-containing polymer composition was visually observed, and the carboxyl group-containing polymer composition was observed.
- Measure the time (minutes) required to completely get wet without any dry parts referred to as “dispersion time”. If the time required for swelling is 30 minutes or less, it can be judged that the dispersibility is excellent.
- Dispersibility stability (storage stability)
- the carboxyl group-containing polymer composition was measured by the method (1) 30 days after the production with respect to the dispersion time (referred to as “dispersion time 1”) measured by the method (1) within 24 hours after the production.
- the polymerization rate was calculated by the following formula.
- the amount of the unreacted monomer (a-1) is the amount of the monomer (a-1) not added to the system at that time out of the total amount of the monomer (a-1) used in the polymerization reaction. ) And the total amount of monomer (a-1) present in an unreacted state in the system.
- each amount of monomer (a-1) is based on weight.
- the amount of the unreacted monomer (a-1) was measured using liquid chromatography such as high performance liquid chromatography.
- Viscosity and transparency of alcohol gel 51.7 g of ion-exchanged water and 96.0 g of ethanol are placed in a 200 mL (milliliter) beaker, and 0.75 g of a carboxy group-containing polymer composition is added with stirring. . After uniformly dispersing, stirring is stopped, an ethanol solution of triethanolamine (50% by weight) is added so that the pH is 6 to 8, and stirring is performed with a hand mixer or the like until the gel is uniform. After soaking in a constant temperature bath at 25 ° C., the viscosity and transparency are measured. As for the viscosity, a Brookfield viscometer (model number: DV1MRVTJ0) was used. 5 is measured at 20 rpm.
- the transmittance of light having a wavelength of 425 nm is measured using a spectrophotometer (model number: UV-3150) manufactured by Shimadzu Corporation. If it is 95% or more, it can be said that the transparency is high.
- Example 1 In a 500 mL (milliliter) four-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube and a cooling tube, 40 g of acrylic acid and an alkyl group having 18 to 24 carbon atoms in the alkyl group as a (meth) acrylic acid alkyl ester VMA 70 (manufactured by NOF Corporation, 10-20 parts by mass of stearyl methacrylate, 10-20 parts by mass of eicosanyl methacrylate, 59-80 parts by mass of behenyl methacrylate, and tetracosanyl methacrylate content of 1% by mass or less 0.88 g of a mixture), 0.20 g of pentaerythritol tetraallyl ether as a compound (a-2) having at least two ethylenically unsaturated groups, and 0.22 g of 2,2′-azobis (methyl isobutyrate) as a radical polymerization initi
- the flask was charged and the contents of the flask were kept stirring for another hour. Thereafter, the set temperature of the oil bath was set to 100 ° C. and heated, and normal hexane was removed from the flask. Thereafter, the contents of the flask were transferred to a vacuum dryer (Yamatho, Vacuum Dry Oven DP33), the oven set temperature was set to 115 ° C., the set pressure was set to 10 mmHg, and dried for 8 hours. 38 g of a carboxyl group-containing polymer composition was obtained. As shown in Table 1, the polymerization rate when polyoxyethylene (3) castor oil was added was 98%.
- Example 2 is the same as Example 1 except that the timing of adding polyoxyethylene (3) castor oil is changed to the time when the polymerization rate is 70% (the time when the polymerization rate is maintained at 60 to 65 ° C. for about 2 hours) As a result, 38 g of a white fine powder carboxyl group-containing polymer composition was obtained.
- Example 3 Same as Example 1 except that polyoxyethylene (3) castor oil was changed to polyisoethylene stearate polyoxyethylene (30) hydrogenated castor oil (Emulex RWIS-330, manufactured by Nippon Emulsion Co., Ltd.) in Example 1. As a result, 38 g of a white fine powder carboxyl group-containing polymer composition was obtained.
- Example 4 In Example 1, 38 g of a white fine powder carboxyl group-containing polymer composition was obtained in the same manner as in Example 1 except that Bremer VMA-70 was not used.
- Example 5 In Example 1, not only when the polymerization rate was 98% (after completion of heating) but also when the polymerization rate was 50% (when kept at 60 to 65 ° C. for about 1 hour) 0.4 g of normal hexane. Example 1 except that 0.4 g of polyoxyethylene (3) castor oil (Nikko Chemical Co., Ltd., NIKKOL CO3) was added as a nonionic surfactant (B) (emulsifier). Similarly, 38 g of a carboxyl group-containing polymer composition as a white fine powder was obtained.
- polyoxyethylene (3) castor oil Nikko Chemical Co., Ltd., NIKKOL CO3
- B nonionic surfactant
- Example 1 is the same as Example 1 except that the timing of adding polyoxyethylene (3) castor oil is changed to the time when the polymerization rate is 50% (the time when the polymerization is held at 60 to 65 ° C. for about 1 hour). As a result, 38 g of a white fine powder carboxyl group-containing polymer composition was obtained.
- Example 2 In Example 1, the carboxyl group of the white fine powder was changed in the same manner as in Example 1 except that the timing of adding the polyoxyethylene (3) castor oil was changed to before the polymerization (when the polymerization rate was 0%). 38 g of a containing polymer composition was obtained.
- Example 6 In a 500 mL (milliliter) four-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube and a cooling tube, 40 g of acrylic acid and an alkyl group having 18 to 24 carbon atoms in the alkyl group as a (meth) acrylic acid alkyl ester VMA 70 (manufactured by NOF Corporation, 10-20 parts by mass of stearyl methacrylate, 10-20 parts by mass of eicosanyl methacrylate, 59-80 parts by mass of behenyl methacrylate, and tetracosanyl methacrylate content of 1% by mass or less 0.88 g of a mixture), 0.20 g of pentaerythritol tetraallyl ether as a compound (a-2) having at least two ethylenically unsaturated groups, and 0.22 g of 2,2′-azobis (methyl isobutyrate) as a radical poly
- Example 6 (Comparative Example 3) In Example 6, the timing of adding the nonionic surfactant (B) was changed to the time when the polymerization rate was 0% (the time when the monomer or the like was charged) in the same manner as in Example 6, 38 g of powdery carboxyl group-containing polymer composition was obtained.
- Example 6 obtained by adding the nonionic surfactant when the polymerization rate of the ⁇ , ⁇ -unsaturated carboxylic acid (a-1) was 75% was obtained. It can be seen that the product has a high viscosity when used as an alcohol gel, and the alcohol gel is also highly transparent.
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Abstract
Description
項1. α,β-不飽和カルボン酸(a-1)及び分子内にエチレン性不飽和基を少なくとも2個有する化合物(a-2)を含む単量体の共重合体であるカルボキシル基含有重合体(A)と、ノニオン性界面活性剤(B)とを含む、カルボキシル基含有重合体組成物を製造する方法であって、
前記単量体を共重合させる工程を備えており、
当該工程において、前記α,β-不飽和カルボン酸(a-1)の重合率が70~100%となった時点で、系中に前記ノニオン性界面活性剤(B)を添加する、カルボキシル基含有重合体組成物の製造方法。
項2. ノニオン性界面活性剤(B)の添加量が、α,β-不飽和カルボン酸(a-1)100質量部に対して、0.5~9質量部である、項1に記載のカルボキシル基含有重合体組成物の製造方法。
α,β-不飽和カルボン酸(a-1)(単量体(a-1)と称する場合がある)としては、特に限定されず、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、フマル酸等の炭素数3~5のオレフィン系不飽和カルボン酸等が挙げられる。これらのα,β-不飽和カルボン酸(a-1)の中でも、安価で入手が容易であり、得られるカルボキシル基含有重合体組成物を用いた中和粘稠液の透明性が高いことから、アクリル酸、メタクリル酸などが好適に用いられる。なお、これらのα,β-不飽和カルボン酸は、それぞれ単独で使用してもよいし、2種以上を組み合わせて用いてもよい。
エチレン性不飽和基を少なくとも2個有する化合物(a-2)(エチレン性不飽和基を2個以上有する化合物(a-2))としては、特に限定されず、例えば、ポリオールの2置換以上のアクリル酸エステル類;ポリオールの2置換以上のメタクリル酸エステル類;ポリオールの2置換以上のアリルエーテル類;フタル酸ジアリル、リン酸トリアリル、メタクリル酸アリル、テトラアリルオキシエタン、トリアリルシアヌレート、アジピン酸ジビニル、クロトン酸ビニル、1,5-ヘキサジエン、ジビニルベンゼン等が挙げられる。なお、前記ポリオールとは、エチレングリコール、プロピレングリコール、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、グリセリン、ポリグリセリン、トリメチロールプロパン、ペンタエリスリトール、サッカロース、ソルビトール等が挙げられる。これらのエチレン性不飽和基を少なくとも2個有する化合物の中でも、得られるカルボキシル基含有重合体組成物を用いた中和粘稠液の粘度調整が容易である観点から、ペンタエリスリトールトリアリルエーテル、ペンタエリスリトールテトラアリルエーテル、テトラアリルオキシエタン、リン酸トリアリル、ポリアリルサッカロースが好適に用いられる。なお、これらのエチレン性不飽和基を少なくとも2個有する化合物(a-2)は、それぞれ単独で使用してもよいし、2種以上を組み合わせて用いてもよい。
カルボキシル基含有重合体(A)を構成する単量体としては、得られるカルボキシル基含有重合体組成物を用いた中和粘稠液の粘度を調整する観点から、α,β-不飽和化合物(a-3)等を用いてもよい。
方法(1):α,β-不飽和カルボン酸(a-1)とエチレン性不飽和基を少なくとも2個有する化合物(a-2)と(さらに必要であればα,β-不飽和化合物(a-3)と)を重合初期から共存させて(例えば、それぞれを全量共存させて)共重合する方法
方法(2):α,β-不飽和カルボン酸(a-1)に、エチレン性不飽和基を少なくとも2個有する化合物(a-2)を連続的に添加しながら重合させる方法
当該方法(2)においてα,β-不飽和化合物(a-3)を使用する場合、これを重合に付す方法は特に限定されず、例えば、あらかじめα,β-不飽和カルボン酸(a-1)と共存させておいてもよいし、エチレン性不飽和基を少なくとも2個有する化合物(a-2)と同様に連続的に添加してもよい。
方法(3):α,β-不飽和カルボン酸(a-1)と、エチレン性不飽和基を少なくとも2個有する化合物(a-2)とを、連続的に添加しながら重合させる方法
当該方法(3)においてα,β-不飽和化合物(a-3)を使用する場合、これを重合に付す方法は特に限定されず、例えば、あらかじめ重合系に仕込んでおいてもよいし、α,β-不飽和カルボン酸(a-1)及びエチレン性不飽和基を少なくとも2個有する化合物(a-2)と同様に連続的に添加してもよい。
ノニオン性界面活性剤(B)は、親水部と疎水部とから構成される。疎水部の例としては、例えば、多価アルコール脂肪酸エステルやヒドロキシ脂肪酸の付加重合物などが挙げられる。
式:-(CH2-CHR1-O)n -
[式中、R1は水素原子、メチル基またはエチル基を示し、nは1~100の整数を示す。nが2以上の整数である場合、複数のR1は、それぞれ同一であってもよいし、異なっていてもよい。]
当該方法(2A)においてα,β-不飽和化合物(a-3)を使用する場合、これを重合に付す方法は特に限定されず、例えば、あらかじめ反応容器に仕込んでおいてもよいし、α,β-不飽和カルボン酸(a-1)及びエチレン性不飽和基を少なくとも2個有する化合物(a-2)と同様に反応容器に連続的に添加してもよい。
実施例及び比較例により得られたカルボキシル基含有重合体組成物を、以下の方法により測定、評価した。
200mL(ミリリットル)容のビーカーに、イオン交換水100gを入れ、イオン交換水の温度を25℃に調整する。このビーカーに、カルボキシル基含有重合体組成物3.0gを無攪拌条件下で一気に投入し、該カルボキシル基含有重合体組成物の膨潤状態を目視で観察して、該カルボキシル基含有重合体組成物が乾いた部分無く、すべて濡れきるのに要する時間(分)(「分散時間」と称する)を測定する。膨潤するのに要する時間が30分間以下であれば、分散性に優れていると判断できる。
カルボキシル基含有重合体組成物を製造後24時間以内に上記(1)の方法で測定した分散時間(「分散時間1」と称する)に対する、製造後30日後に上記(1)の方法で測定した分散時間(「分散時間2」と称する)の比[=分散時間2/分散時間1]を保存安定性(分散性の安定性:時間が経っても良好な分散性が維持される特性)の指標とした。上記比が1に近いほど保存安定性がよく、0.8~1.2であれば良好と判断できる。
重合率は、下記の式により算出した。未反応の単量体(a-1)の量は、重合反応に用いた単量体(a-1)の総量のうち、その時点で系中に添加していない単量体(a-1)と、系中で未反応の状態で存在している単量体(a-1)の合計量を意味する。また、式において、単量体(a-1)の各量は、重量を基準としたものである。未反応の単量体(a-1)の量は、高速液体クロマトグラフィー等の液体クロマトグラフィーを用いて測定した。
200mL(ミリリットル)容のビーカーに、イオン交換水51.7g、エタノール96.0gを入れ、撹拌しながら、カルボキシ基含有重合体組成物0.75gを添加する。均一に分散させた後、撹拌を止め、トリエタノールアミンのエタノール溶液(50重量%)をpHが6~8になるよう添加し、ハンドミキサー等でゲルが均一になるまで撹拌する。25℃の恒温槽に浸した後、粘度及び透明性を測定する。粘度については、BrookField社製の粘度計(型番:DV1MRVTJ0)を用い、スピンドルNo.5を使用して20rpmで測定する。5000mPa・s以上であれば高粘度といえる。透明性については、島津製作所社製の分光光度計(型番:UV-3150)を用いて、波長425nmの光の透過率を測定する。95%以上であれば透明性が高いといえる。
攪拌機、温度計、窒素吹き込み管及び冷却管を備えた500mL(ミリリットル)容の四つ口フラスコに、アクリル酸40g、アルキル基の炭素数が18~24である(メタ)アクリル酸アルキルエステルとしてブレンマーVMA70(日油株式会社製、メタクリル酸ステアリルが10~20質量部、メタクリル酸エイコサニルが10~20質量部、メタクリル酸ベヘニルが59~80質量部及びメタクリル酸テトラコサニルの含有率が1質量%以下の混合物)0.88g、エチレン性不飽和基を少なくとも2個有する化合物(a-2)としてペンタエリスリトールテトラアリルエーテル0.20g、ラジカル重合開始剤として2,2’-アゾビス(イソ酪酸メチル)0.116g、及び反応溶媒としてノルマルヘキサン230.9gを仕込んだ。その後、内容物を攪拌しながらフラスコ内の酸素を除去するために、溶液中に窒素ガスを吹き込んだ。その後、撹拌と窒素ガスの吹き込みを続けた状態で、オイルバスの設定を60~65℃に設定し、フラスコの内容物を3時間加熱した。その後、3時間60~65℃に保持した。加熱終了直後、ノルマルヘキサン2.0gにノニオン性界面活性剤(B)(乳化剤)としてポリオキシエチレン(3)ヒマシ油(日光ケミカル株式会社製、NIKKOL CO3)2.0gを溶解させたものを、フラスコに投入し、フラスコの内容物を更に1時間撹拌を続けた。その後、オイルバスの設定温度を100℃に設定して加熱し、フラスコ内からノルマルヘキサンを除去した。その後、フラスコの内容物を減圧乾燥機(Yamatho社製、バキュームドライオーブンDP33)に移し、オーブンの設定温度を115℃に設定し、設定圧力を10mmHgに設定して8時間乾燥し、白色微粉末のカルボキシル基含有重合体組成物38gを得た。表1に示すように、ポリオキシエチレン(3)ヒマシ油を投入した時点の前記重合率は、98%であった。
実施例1において、ポリオキシエチレン(3)ヒマシ油を添加するタイミングを前記重合率が70%の時点(60~65℃で2時間程度保持した時点)に変更したこと以外は実施例1と同様にして、白色微粉末のカルボキシル基含有重合体組成物38gを得た。
実施例1において、ポリオキシエチレン(3)ヒマシ油をトリイソステアリン酸ポリオキシエチレン(30)硬化ヒマシ油(日本エマルジョン株式会社製、エマレックスRWIS-330)に変更したこと以外は実施例1と同様にして、白色微粉末のカルボキシル基含有重合体組成物38gを得た。
実施例1において、ブレンマーVMA-70を使用しなかったこと以外は実施例1と同様にして、白色微粉末のカルボキシル基含有重合体組成物38gを得た。
実施例1において、前記重合率が98%(加熱終了後)の時点だけでなく、前記重合率が50%の時点(60~65℃で1時間程度保持した時点)においてもノルマルヘキサン0.4gにノニオン性界面活性剤(B)(乳化剤)としてポリオキシエチレン(3)ヒマシ油(日光ケミカル株式会社製、NIKKOL CO3)0.4gを溶解させたものを添加したこと以外は、実施例1と同様にして、白色微粉末のカルボキシル基含有重合体組成物38gを得た。
実施例1において、ポリオキシエチレン(3)ヒマシ油を添加するタイミングを前記重合率が50%の時点(60~65℃で1時間程度保持した時点)に変更したこと以外は実施例1と同様にして、白色微粉末のカルボキシル基含有重合体組成物38gを得た。
実施例1において、ポリオキシエチレン(3)ヒマシ油を添加するタイミングを重合前(前記重合率が0%の時点)に変更したこと以外は実施例1と同様にして、白色微粉末のカルボキシル基含有重合体組成物38gを得た。
攪拌機、温度計、窒素吹き込み管及び冷却管を備えた500mL(ミリリットル)容の四つ口フラスコに、アクリル酸40g、アルキル基の炭素数が18~24である(メタ)アクリル酸アルキルエステルとしてブレンマーVMA70(日油株式会社製、メタクリル酸ステアリルが10~20質量部、メタクリル酸エイコサニルが10~20質量部、メタクリル酸ベヘニルが59~80質量部及びメタクリル酸テトラコサニルの含有率が1質量%以下の混合物)0.88g、エチレン性不飽和基を少なくとも2個有する化合物(a-2)としてペンタエリスリトールテトラアリルエーテル0.20g、ラジカル重合開始剤として2,2’-アゾビス(イソ酪酸メチル)0.116g、及び反応溶媒としてノルマルヘキサン230.9gを仕込んだ。その後、内容物を攪拌しながらフラスコ内の酸素を除去するために、溶液中に窒素ガスを吹き込んだ。その後、撹拌と窒素ガスの吹き込みを続けた状態で、オイルバスの設定を60~65℃に設定し、フラスコの内容物を3時間加熱した。その後、1時間60~65℃に保持し(重合率75%)、ノルマルヘキサン2.0gに、ノニオン性界面活性剤(B)(乳化剤)として12-ヒドロキシステアリン酸とポリオキシエチレンのブロック共重合体(クローダ製、Hypermer B246)2.0gを溶解させたものを、フラスコに投入した。さらに、2時間、60~65℃に保持し、反応を完結させた。その後、オイルバスの設定温度を100℃に設定して加熱し、フラスコ内からノルマルヘキサンを除去した。その後、フラスコの内容物を減圧乾燥機(Yamatho社製、バキュームドライオーブンDP33)に移し、オーブンの設定温度を115℃に設定し、設定圧力を10mmHgに設定して8時間乾燥し、白色微粉末のカルボキシル基含有重合体組成物38gを得た。
実施例6において、ノニオン性界面活性剤(B)を添加するタイミングを、前記重合率が0%の時点(モノマー等を仕込む時点)に変更したこと以外は実施例6と同様にして、白色微粉末のカルボキシル基含有重合体組成物38gを得た。
Claims (2)
- α,β-不飽和カルボン酸(a-1)及び分子内にエチレン性不飽和基を少なくとも2個有する化合物(a-2)を含む単量体の共重合体であるカルボキシル基含有重合体(A)と、ノニオン性界面活性剤(B)とを含む、カルボキシル基含有重合体組成物を製造する方法であって、
前記単量体を共重合させる工程を備えており、
当該工程において、前記α,β-不飽和カルボン酸(a-1)の重合率が70~100%となった時点で、系中に前記ノニオン性界面活性剤(B)を添加する、カルボキシル基含有重合体組成物の製造方法。 - ノニオン性界面活性剤(B)の添加量が、α,β-不飽和カルボン酸(a-1)100質量部に対して、0.5~9質量部である、請求項1に記載のカルボキシル基含有重合体組成物の製造方法。
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US16/088,779 US10988560B2 (en) | 2016-03-30 | 2017-03-28 | Method for producing carboxyl-group-containing polymer composition |
EP17775114.6A EP3438194A4 (en) | 2016-03-30 | 2017-03-28 | PROCESS FOR PRODUCING POLYMER COMPOSITION CONTAINING CARBOXYL GROUPS |
CN201780020268.3A CN108884290B (zh) | 2016-03-30 | 2017-03-28 | 含羧基聚合物组合物的制造方法 |
JP2018508090A JP6871913B2 (ja) | 2016-03-30 | 2017-03-28 | カルボキシル基含有重合体組成物の製造方法 |
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WO2019244951A1 (ja) * | 2018-06-20 | 2019-12-26 | 住友精化株式会社 | 漂白剤成分を含む組成物及びその製造方法 |
WO2019244952A1 (ja) * | 2018-06-20 | 2019-12-26 | 住友精化株式会社 | 漂白剤成分を含む組成物及びその製造方法 |
WO2020179602A1 (ja) * | 2019-03-01 | 2020-09-10 | 住友精化株式会社 | ポリマー水分散組成物 |
WO2023127737A1 (ja) * | 2021-12-27 | 2023-07-06 | 住友精化株式会社 | カルボキシル基含有水溶性共重合体及びその用途 |
WO2023127738A1 (ja) * | 2021-12-27 | 2023-07-06 | 住友精化株式会社 | カルボキシル基含有水溶性共重合体及びその用途 |
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CN111777707B (zh) * | 2020-07-02 | 2022-12-16 | 南京紫鸿生物科技有限公司 | 一种高浓度酒精凝胶及用于高浓度酒精凝胶的卡波姆 |
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CN108884290B (zh) | 2021-01-08 |
JP6871913B2 (ja) | 2021-05-19 |
US10988560B2 (en) | 2021-04-27 |
EP3438194A1 (en) | 2019-02-06 |
US20190077896A1 (en) | 2019-03-14 |
KR20180132068A (ko) | 2018-12-11 |
CN108884290A (zh) | 2018-11-23 |
JPWO2017170577A1 (ja) | 2019-02-07 |
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