WO2008015870A1 - Procédé de production de fines particules de polymère - Google Patents
Procédé de production de fines particules de polymère Download PDFInfo
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- WO2008015870A1 WO2008015870A1 PCT/JP2007/063498 JP2007063498W WO2008015870A1 WO 2008015870 A1 WO2008015870 A1 WO 2008015870A1 JP 2007063498 W JP2007063498 W JP 2007063498W WO 2008015870 A1 WO2008015870 A1 WO 2008015870A1
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- macromonomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- 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
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
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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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
Definitions
- the present invention relates to a method for producing polymer fine particles. More specifically, the present invention provides a high-quality polymer fine particle having a uniform particle size by suspension polymerization in a stable state without causing aggregation of the particles. It relates to a method of manufacturing with high productivity.
- Spherical polymer fine particles of micron size are used as cosmetic additives, supports for various chemical substances, spacers, column fillers for chromatography, light diffusing agents, porogens, light weight agents, It is used as an anti-blocking agent, a surface modifier for recording paper, and the like.
- hydrophilic crosslinked polymer fine particles can be used as hydrogel fine particles, and are useful as cosmetic additives, carriers, porogens, lightening agents, and surface modifiers for recording paper.
- Patent Document 1 Japanese Patent Laid-Open No. 1 213307
- Patent Document 2 JP-A-11-60616
- Patent Document 3 JP-A-9-143210
- Patent Document 4 Japanese Patent Laid-Open No. 2003-34725
- Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-149569
- Patent Document 6 International Publication WO 01Z04163 Pamphlet
- Patent Document 7 Japanese Unexamined Patent Publication No. 2000-35697
- An object of the present invention is to provide high-quality polymer fine particles having a particle size of several / zm to several tens;
- An object of the present invention is to provide a method for producing with good productivity while maintaining a good dispersion stabilizer that does not cause mutual aggregation.
- the present invention is a high-quality polymer having a uniform particle size while maintaining suspension stability with high polymerization stability even when producing hydrophilic crosslinked polymer fine particles having a high degree of crosslinking. It is an object of the present invention to provide a suspension polymerization method capable of producing fine particles smoothly according to productivity.
- a specific macromonomer is used as a dispersion stabilizer, that is, a polymer derived from a vinyl monomer, at least of which
- suspension polymerization is carried out using a macromonomer having a radically polymerizable unsaturated group at one end as a dispersion stabilizer, it has a particle size of the order of several zm to several tens of zm, Uniform, high-quality spherical polymer fine particles maintain good dispersion stability and polymerization stability without causing aggregation, agglomeration, and adhesion to the polymerization equipment during and after polymerization.
- the specific macromonomer is a dispersion stabilizer used in producing hydrophilic polymer fine particles, particularly hydrophilic crosslinked polymer fine particles by reverse phase suspension polymerization.
- the hydrophilic vinyl monomer is subjected to reverse phase suspension polymerization using the specific macromonomer as a dispersion stabilizer, the degree of crosslinking is increased using a large amount of polyfunctional vinyl monomer.
- a good dispersion stabilizer and polymerization without causing aggregation and agglomeration of the polymer particles and adhesion of the polymer particles to the polymer device. It was found that high-quality hydrophilic crosslinked polymer fine particles having a relatively uniform particle size can be obtained with high productivity while maintaining stability.
- the present inventors obtained radical polymerization of a bure monomer at 150 to 350 ° C as the macromonomer used as a dispersion stabilizer during suspension polymerization, particularly reverse phase suspension polymerization.
- HC C (X) (where X is monovalent)
- a polar monomer) and a macromonomer having a (meth) atallyloyl group at the end of a polymer derived from a Z- or beryl monomer, as a dispersion stabilizer is excellent in function and suitable, the weight average molecular weight of the macromonomer is preferably 1000 to 30000, the macromonomer is a structural unit derived from a hydrophilic bulur monomer and a hydrophobic vinyl-based monomer. It is preferable to have both structural units derived from a monomer, and the structural unit derived from a hydrophobic vinyl monomer at that time includes (meth) acrylic acid alkyl ester having 8 or more carbon atoms.
- the structural unit derived from is preferable, and the structural unit derived from the vinyl monomer having a carboxyl group is preferable as the structural unit derived from the hydrophilic vinyl monomer. Based on these findings, the present invention was completed 1st.
- the present invention provides:
- the present invention provides:
- the macromonomer used as the dispersion stabilizer is a macromonomer having a (meth) atallyloyl group at the end of a polymer derived from a vinyl monomer;
- At least a part of the structural unit derived from the hydrophilic vinyl monomer in the macromonomer is a structural unit derived from a vinyl monomer having a carboxyl group, and the macromonomer comprises all of the macromonomer.
- the average particle size of the polymer fine particles produced by suspension polymerization is 2 to: LOO ⁇ m, The production method according to any one of (1) to (8) above;
- Polymer fine particles produced by suspension polymerization have a water absorption ratio of 5 to 50 times, an average particle diameter in a saturated swelling state with water of 5 to 70 m, and a saturated swelling state with water.
- suspension polymerization is carried out using a macromonomer having a radically polymerizable unsaturated group at at least one terminal as a dispersion stabilizer.
- a macromonomer having a radically polymerizable unsaturated group at at least one terminal as a dispersion stabilizer.
- high-quality spherical polymer fine particles having an appropriate particle size of the order of several / zm to several tens / zm and having a relatively uniform particle size are polymerized during and after polymerization. Can be produced with good productivity while maintaining high dispersion stability and polymerization stability without causing aggregation, agglomeration, and adhesion to the polymerization apparatus.
- the method of the present invention is particularly suitable for reversed-phase suspension polymerization using a hydrophilic vinyl monomer, and is a radically polymerizable unsaturated group at least at one terminal of a polymer derived from a bull monomer.
- the polymer particles are aggregated, agglomerated, polymerized even in the case of producing highly crosslinked hydrophilic polymer particles having a high degree of crosslinking using a large amount of polyfunctional butyl monomer.
- High-quality hydrophilic crosslinked polymer fine particles having a uniform particle diameter without causing adhesion to the apparatus can be produced with high productivity.
- V is a structural unit derived from a hydrophilic vinyl monomer (particularly a structural unit derived from a hydrophilic vinyl monomer having a carboxyl group).
- a structural unit derived from a hydrophobic vinyl-based monomer especially a structural unit derived from an alkyl ester of (meth) acrylic acid having 8 or more carbon atoms]
- the above-described present invention is excellent. The effect is more obvious Written by the author.
- polymer fine particles having an average particle diameter in the range of 2 to LOO ⁇ m and having a uniform particle diameter and having no spherical aggregation can be produced smoothly.
- it has a water absorption ratio of 5 to 50 times, the average particle size in a saturated swelling state with water is 5 to 70 ⁇ m, and a particle size of 150 ⁇ m or more in a saturated swelling state with water. It is possible to smoothly produce hydrophilic polymer fine particles in which the content ratio of the particles shown is 0.3% by mass or less.
- the fine polymer particles obtained by the method of the present invention are cosmetic additives, carriers for various chemical substances, spacers, column fillers for chromatography, light diffusing agents, porogens, lightening agents, It can be used effectively for applications such as anti-blocking agents and surface modifiers for recording paper.
- FIG. 1 is a view showing an apparatus used for measuring the water absorption magnification of polymer fine particles.
- FIG. 2 is a photograph of a dispersion of polymer fine particles obtained in Example 1 taken with a digital microscope.
- FIG. 3 is a photograph taken with a digital microscope of a state in which the polymer fine particles obtained in Example 1 were saturated and swollen with water.
- FIG. 4 is a photograph taken with a digital microscope of a dispersion of polymer fine particles obtained in Example 10.
- FIG. 5 is a photograph taken with a digital microscope of a state in which the polymer fine particles obtained in Example 10 were saturated and swollen with water.
- FIG. 6 is a photograph taken with a digital microscope of a dispersion of polymer fine particles obtained in Example 11.
- FIG. 7 is a photograph taken with a digital microscope of a state in which the polymer fine particles obtained in Example 11 were saturated and swollen with water. Explanation of symbols
- “suspension polymerization of a vinyl monomer” refers to normal phase suspension polymerization in which an aqueous phase is a dispersion medium and an oil phase is a dispersoid, and a reverse phase in which an oil phase is a dispersion medium and an aqueous phase is a dispersoid. Includes both phase suspension polymerizations.
- an oil phase (an oil phase containing a hydrophobic vinyl monomer or a hydrophobic vinyl monomer) is oil in the aqueous phase.
- the aqueous phase hydrophilic vinyl
- the polymer fine particles are produced by wZo-type reverse phase suspension polymerization in which a monomer aqueous solution is suspended in the form of water droplets. In the present invention, either normal phase suspension polymerization or reverse phase suspension polymerization is used.
- the macromonomer (M) used as a dispersion stabilizer in the present invention may have a linear structure or a structure branched into three or more.
- the macromonomer (M) has a linear structure! /, It has a radically polymerizable unsaturated group only at one end of the macromonomer (M).
- each may have a radically polymerizable unsaturated group at both ends.
- the macromonomer (M) when the macromonomer (M) has a structure branched into three or more, it may have a radically polymerizable unsaturated group at one or two or more of the three or more terminals.
- a macromonomer (M) force having a linear structure and having a radical-polymerizable unsaturated group only at one end is easy to produce a macromonomer and is stable in suspension polymerization. It is preferably used as a dispersion stabilizer because of its excellent crystallization function.
- the radically polymerizable unsaturated group that the macromonomer (M) has at its end is formed by radical polymerization.
- the radically polymerizable unsaturated group at the terminal of the macromonomer (M) any of the unsaturated groups that can be used is, for example, the following general formula (I);
- the radically polymerizable unsaturated group at the end of the macromonomer (M) is a substituted vinyl group represented by the above general formula (I) [hereinafter referred to as “oc-substituted vinyl group (I)”].
- a (meth) attalyloyl group is excellent in copolymerization with a bull-type monomer during suspension polymerization of the bull-type monomer and provides good dispersion stability. I like it.
- the ⁇ -substituted bur group (I) has excellent copolymerizability with the vinyl monomer and low homopolymerization, so that it can be consumed by homopolymerization on the continuous phase side. Particularly preferred because of its small size.
- the "polar group X" in the a-substituted vinyl group (I) represented by the above general formula (I) refers to a group having an atom other than a carbon atom and a hydrogen atom, or an aryl group.
- Specific examples of the group X include COOR (where R is a hydrogen atom or a monovalent hydrocarbon group), -CONR (R
- R 2 is a hydrogen atom or monovalent hydrocarbon group
- OR R is a hydrogen atom or monovalent hydrocarbon group
- OCOR R is a hydrogen atom or monovalent hydrocarbon group
- OCOOR R is a hydrogen atom
- NCOOR R is a hydrogen atom or a monovalent hydrocarbon group
- halogen atom CN, a phenyl group, a substituted phenyl group, and the like.
- the polar group X may be COOR, or one CONR.
- the molecular weight of the macromonomer (M) is preferably 1000 to 30000 in terms of weight average molecular weight, more preferably 2000 to 20000, more preferably than force S. If the molecular weight of the macromonomer (M) is too low or too high, the function as a dispersion stabilizer tends to deteriorate.
- the weight average molecular weight of the macromonomer [macromonomer (M)] in the present specification is the weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC). As described in the Examples section below
- the main part of the macromonomer (M) (polymer part derived from vinyl monomer) has a structural unit force derived from one or more vinyl monomers, and is particularly hydrophobic. Structural units derived from vinyl monomers (hereinafter sometimes referred to as “hydrophobic vinyl monomer units”) and structural units derived from hydrophilic vinyl monomers (hereinafter referred to as “hydrophilic monomers”). It is preferred to have both a sex bul monomeric unit "and sometimes a).
- the macromonomer (M) is formed from both hydrophobic vinyl monomer units and hydrophilic vinyl monomer units, the macromonomer is separated from the continuous phase (oil phase or water phase) during suspension polymerization.
- the hydrophobic bull monomer unit is 20 ° C. It is preferable that it is formed from a hydrophobic vinyl monomer having a water solubility of 2% by mass or less, particularly 0.5% by mass or less. This can stabilize the dispersion and further improve the dispersion stability during suspension polymerization.
- Monomers having a solubility in water at 20 ° C of 0.5% by mass or less include propyl methacrylate, butyl acrylate, butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, acrylic 2-Ethylhexyl acid, 2-Ethyl methacrylate Hexyl, stearyl acrylate, stearyl methacrylate, lauryl acrylate, lauryl methacrylate, isoborn acrylate, isoborn methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, perfluoroalkyl acrylate, metatali Perfluoroalkyl oxalate, benzyl acrylate, benzyl methacrylate, styrene, a-methylstyrene, etc., and a single unit whose solubility in water at 20 ° C is 0.5 to 2.0% by mass Examples of
- the hydrophobic vinyl monomer unit in the macromonomer (M) can be formed from one or two of the aforementioned hydrophobic vinyl monomers.
- the macromonomer (M) When a dispersion stabilizer consisting of a macromonomer (M) is used in reversed-phase suspension polymerization, in order to increase the affinity for the organic solvent phase (usually a hydrophobic organic solvent phase) that forms the continuous phase, the macromonomer ( M) preferably has a structural unit derived from an alkyl ester of (meth) acrylic acid having 8 or more carbon atoms as a hydrophobic vinyl monomer unit.
- the structure of the alkyl group may be linear, branched or cyclic.
- the hydrophilic vinyl monomer unit in the macromonomer (M) having a hydrophobic vinyl monomer unit and a hydrophilic vinyl monomer unit is formed from a vinyl monomer having a hydrophilic group.
- the hydrophilic group includes a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphonic acid group and salts thereof, a hydroxyl group, an amino group (a quaternized product thereof or an acid neutralization thereof).
- hydrophilic bur monomer examples include unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, butylacetic acid, and allyloxypropionic acid, maleic acid, fumaric acid, mesaconic acid, and citraconic acid. It has a carboxyl group such as an unsaturated acid anhydride that generates a carboxyl group by hydrolysis of unsaturated dibasic acid such as itaconic acid or cyclohexanedicarboxylic acid, maleic anhydride, tetrahydrophthalic anhydride, etc.
- unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, butylacetic acid, and allyloxypropionic acid
- maleic acid, fumaric acid, mesaconic acid, and citraconic acid has a carboxyl group such as an unsaturated acid anhydride that generates a carboxyl group by hydrolysis of unsaturated dibasic acid such as it
- Vinyl monomers or bur monomers having a group that can become a carboxyl group acrylonitrile, acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate Carboxyl groups such as Vinyl monomers having other hydrophilic groups; allylic sulfonic acid, styrene sulfonic acid, butyl sulfonic acid, acrylamide-2-methylpropane sulfonic acid, methacrylamide-2-methylpropane sulfonic acid, allylphosphonic acid, buluphosphonic acid, etc.
- N N-dimethylaminoethyl (meth) acrylate, N, N-jetylaminoethyl (meth) acrylate, N, N-dimethyl aminopropyl
- examples include (meth) acrylate, vinyl monomers having amino groups such as N, N-dimethylaminopropyl (meth) acrylamide, or (part) acid neutralized products or (part) quaternized products. be able to.
- the hydrophilic vinyl monomer unit in the macromonomer (M) can be formed from one or two of the aforementioned hydrophilic vinyl monomers.
- the macromonomer (M) has a structural unit composed of acrylic acid, methacrylic acid, maleic acid, acrylamide, hydroxyethyl acrylate, and hydroxychetyl methacrylate as a hydrophilic bur monomer unit. I prefer that.
- the hydrophilic bur monomer constituting the hydrophilic vinyl monomer unit in the macromonomer (M) has an acidic group such as a carboxyl group as the hydrophilic group
- the acidic At least a part of the groups may be neutralized with an alkali (sodium hydroxide, potassium hydroxide, ammonia, amine compound, etc.).
- the macromonomer (M) is a bulle monomer unit having a carboxyl group and a hydrophilic bulle monomer. It is preferable to have as a unit.
- the vinyl monomer unit having a carboxyl group may be directly introduced into the macromonomer (M) by producing the macromonomer (M) using a bulle monomer having a carboxyl group.
- a macromonomer using a bur monomer having a group capable of reacting with a carboxyl group, a carboxylic anhydride group, or the like (for example, a hydroxyl group, an epoxy group, an amino group, or an oxazoline group).
- the macromonomer may be reacted with a compound that generates a carboxyl group (dicarboxylic acid, water-free dicarboxylic acid, etc.) to introduce a carboxyl group into the macromonomer.
- the ester bond is decomposed to form a macromonomer.
- a carboxyl group may be introduced into the monomer.
- the content of the hydrophobic bull monomer units and the hydrophilic bull monomer units in the macromonomer (M) depends on the type of suspension polymerization (normal phase suspension polymerization or reverse phase suspension).
- a dispersion stabilizer in the macromonomer (M) which can vary depending on the type and composition of the vinyl monomer to be subjected to suspension polymerization, the type and use of the polymer fine particles produced by suspension polymerization
- the content of the hydrophobic vinyl monomer unit is generally 1 to 99% by mass, especially 5 to 95%. It is preferred that the content by weight and the content of the hydrophilic vinyl monomer units is 1 to 99% by weight, especially 5 to 95% by weight! /.
- the macromonomer (M) when the macromonomer (M) is produced using a vinyl-based monomer, a polymer having a radically polymerizable unsaturated group at the terminal and a radical having no radically polymerizable unsaturated group at the terminal is used.
- a small amount of coal (non-macromonomer polymer) may be produced as a by-product, and it is difficult to separate the macromonomer from the non-macromonomer polymer.
- the content of the hydrophobic vinyl monomer unit relative to the macromonomer (M) and the hydrophilic bull monomer unit refers to the content ratio relative to the total mass of the macromonomer (M) including the non-macromonomer polymer.
- the macromonomer (M) when performing reverse phase suspension polymerization using the macromonomer (M) as a dispersion stabilizer, the macromonomer 30 to 99% by mass of a structural unit (hydrophobic bule monomer unit) derived from an alkyl ester of (meth) acrylic acid having 8 or more carbon atoms,
- the structural unit (hydrophilic vinyl monomer unit) derived from a vinyl monomer having a carboxyl group in a proportion of 60 to 90% by mass is 1 to 70% by mass, particularly 10 to 40% by mass.
- M macromonomer having a ratio as a dispersion stabilizer
- the method for producing the macromonomer (M) is not particularly limited, and can be produced by a conventionally known method (see, for example, Patent Documents 5, 6, and 7).
- a production method of a macromonomer having an a-substituted vinyl group (I) at the terminal and a macromonomer having a (meth) attalyloyl group at the terminal preferably used in the present invention is exemplified as follows. It is as follows.
- a vinyl monomer as a raw material for the macromonomer (M) (preferably the above-described hydrophobic bull monomer and hydrophilic bull monomer) is added at 150 to 350 ° C, preferably 180 ° C. ⁇ 320.
- a macromonomer having an a- substituted vinyl group (I) at the end of a polymer having a structural unit derived from a bull monomer is produced by radical polymerization at C, more preferably 190 to 270 ° C. Can do.
- radical source for the radical polymerization reaction a thermal initiation reaction of a vinyl monomer such as styrene or a radical polymerization catalyst can be used.
- a radical polymerization catalyst a conventionally known catalyst can be used.
- Specific examples thereof include benzoyl peroxide, lauroyl peroxide, orthochloroperoxybenzoic acid, orthomethoxyperoxybenzoic acid, 3, 5 , 5 Trimethylhexanoyl peroxide, t-butylperoxy 2-ethylhexanoate, di-t-butyl peroxide, di-t-hexylsilver oxide, di-t-amyl peroxide, t-butyl peroxybivalate, etc.
- Peroxides azo compounds such as azobisisobutyronitrile, azobiscyclohexacarbonyl nitrile, azobis (2,4 dimethylvale-tolyl); persulfate compounds such as potassium persulfate Can be mentioned.
- the amount of radical polymerization catalyst used is preferably 0 to 3 parts by mass, more preferably 0.0001 to 1 part by mass, with respect to 100 masses of the total amount of bulur monomers for producing macromonomers. Furthermore, 0.001 to 0.5 mass part is more preferable.
- radical polymerization methods can be employed for radical polymerization of the bulle monomer, and among them, radical polymerization by bulk polymerization or solution polymerization is preferably employed because it can efficiently produce a macromonomer.
- Polymerization may be performed in a lag, such as batch polymerization, continuous polymerization, semi-batch polymerization (polymerization method where raw materials are supplied continuously but continuous reaction liquid is not extracted). Preference is also given to the point at which the polymerization gives a macromonomer having a narrow composition distribution and molecular weight distribution and high homogeneity. In particular, continuous polymerization using a stirred tank reactor is preferred. Adopted.
- the content of the macromonomer having a radically polymerizable unsaturated group at the terminal is 50% by mass. More preferably (non-macromonomer polymer content is 50% by mass or less) 70% by mass or more (30% by mass or less) More preferably 80% by mass or more (20% by mass) 90% by mass or more (10% by mass or less) is particularly preferable.
- a polymerization system for producing the macromonomer is used in combination with a vinyl monomer.
- the total content of the polymer is Te total mass [Komotodzu ⁇ of the polymerization system, 50 to: L00 mass 0/0, further [this ⁇ or 60 to: L00 mass 0/0, especially [this 70 to: Polymerization is carried out so that L00% by mass, that is, to produce a macromonomer with a solvent content in the polymerization system of 50% by mass or less, further 40% by mass or less, particularly 30% by mass or less. It is preferable to carry out polymerization.
- a macromonomer-producing bull monomer is dissolved, and a macromonomer or other polymer to be produced is not preferably precipitated.
- solvents that can be used include aromatic alcohols such as benzyl alcohol, aliphatic alcohols such as isopropanol and butanol, ketones such as methyl ethyl ketone and isobutyl methyl ketone, esters such as butyl acetate, and methyl Ethylene glycol monoalkyl ethers such as sorb and butyl ceguchi sorb, diethylene glycol monoalkyl ethers such as carbitol, ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, diglycol methyl Examples thereof include diglycol alkyl ethers such as ethers.
- the macromonomer (M) is produced by the method (a), it is formed by copolymerization of the macromonomer (M) and the vinyl monomer present in the dispersed phase during suspension polymerization.
- the constituent monomer of the macromonomer (X position) It is more preferable that the proportion of the buyl monomer is 50 mol% or less, more preferably 30 mol% or less.
- the proportion of the copolymer produced by copolymerization with the vinyl monomer present in the dispersed phase that has a block polymer type structure with the vinyl monomer having a narrow molecular weight distribution is 30 moles. % Or more is preferable and 50 mol% or less is more preferable.
- the copolymer formed by the copolymerization of the macromonomer ( ⁇ ) and the vinyl monomer present in the dispersed phase is to be removed by suspension after the suspension polymerization, the latter is preferably selected.
- the macromonomer ( ⁇ ) when the macromonomer ( ⁇ ) is produced by the method of (a), as a hydrophobic monomer constituting the macromonomer, it does not have a hydrogen atom at the ⁇ -position of the vinyl group (for example, ⁇ Uses a vinyl monomer (which is a carboxy group), and uses a vinyl monomer having a hydrogen atom at the ⁇ -position of the vinyl group as a hydrophilic monomer. Suitable for reversed-phase suspension polymerization This is preferable because a dispersion stabilizer can be obtained.
- the polar group X bonded to the terminal unsaturated bond is derived from the hydrophilic monomer unit, and the terminal unsaturated bond is closer to the dispersed phase (hydrophilic) of reversed-phase suspension polymerization and is copolymerized immediately. It is because it becomes easy to do.
- a vinyl monomer for producing the macromonomer in order to produce a macromonomer having a (meth) atalyloyl group at the end and having a carboxyl group suspended in the molecular chain, a vinyl monomer for producing the macromonomer is used.
- radical polymerization is carried out according to a conventional method using a radical polymerization catalyst in the same manner as in the above (a), and a reactive group (for example, A polymer having a carboxyl group, etc.) and having a hydroxyl group suspended in the molecular chain, and then reacting the terminal reactive group with glycidyl (meth) acrylate, (meth) acrylic chloride, etc.
- a compound having a carboxyl group such as a dicarboxylic acid anhydride is reacted with a hydroxyl group suspended at a terminal to form a carboxyl group in the molecular chain. It is possible to produce a monomer.
- the vinyl monomer having a hydroxyl group used for the production of the macromonomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate.
- a vinyl monomer is radically polymerized in an organic solvent. Examples thereof include a method for producing a polymer having a force lpoxyl group at the terminal.
- mercaptane acts as a chain transfer agent to introduce a carboxyl group at one end of the polymer.
- the preferred amount of mercabtan used is equimolar to the polymer obtained by radical polymerization, and the amount of monomer used and the required weight average molecular weight can be easily calculated.
- the amount of mercaptan used is preferably about 0.1 to 5 g per lOOg of the bull monomer. Good.
- the polymerization temperature during radical polymerization is preferably 50 to 140 ° C.
- Ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, n xane, cyclohexane, n-heptane, octane, Decane and the like are preferably used.
- the polymerization initiator include azobis 2-methylbutyoxy-tolyl, azobisisobutychi-tolyl, azobisdimethylvaleronitrile, t-butyl peroxypivalate, and t-butyl peroxyoctanoate.
- the preferred amount used is 0.13 parts by mass per 100 parts by mass of the vinyl monomer.
- polymer microparticles are produced by suspension polymerization of a vinyl monomer using the macromonomer (M) described above as a dispersion stabilizer.
- any of radical polymerizable vinyl monomers can be used.
- the macromonomer (M) is used as a dispersion stabilizer and the oil phase (hydrophobic in the aqueous phase).
- Polymer fine particles are produced by oZw-type normal phase suspension polymerization in which an oil phase containing a vinyl monomer or a hydrophobic bull monomer is suspended in oil droplets.
- the vinyl monomer to be polymerized by suspension is a hydrophilic vinyl monomer
- the aqueous monomer hydrophilic vinyl monomer
- M macro monomer
- Polymer fine particles are produced by wZo-type reversed-phase suspension polymerization in which an aqueous solution in which the polymer is dissolved is suspended in the form of water droplets.
- the hydrophobic bull monomer used in the oZw type normal phase suspension polymerization is not particularly limited as long as it is a radical polymerizable hydrophobic vinyl monomer.
- Specific examples of hydrophobic vinyl monomers that can be used in normal-phase suspension polymerization include styrene, o-methylstyrene, m-methylenostyrene, p-methylstyrene, ex-methylenostyrene, and p-ethylenostyrene.
- the hydrophilic vinyl monomer used for the wZo-type reverse phase suspension polymerization is not particularly limited as long as it is a radical polymerizable hydrophilic vinyl monomer.
- hydrophilic vinyl monomers that can be used in reverse phase suspension polymerization include hydrophilic vinyl monomers having hydrophilic groups such as carboxyl group, sulfone group, phosphone group, amide group, amino group, and hydroxyl group. System monomers can be used.
- Specific examples of hydrophilic vinyl monomers that can be used include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconic acid, monobutyl maleate, and cyclohexanedicarboxylic acid.
- Vinyl monomers having a carboxy group or their (partially) neutralized products N, N dimethylaminoethyl (meth) acrylate, N, N jetylaminoethyl (meth) acrylate, N, N Butyl monomers having amino groups such as dimethylaminopropyl (meth) acrylate, N, N dimethylaminopropyl (meth) acrylamide, or their (partial) acid intermediates, or (partial) quaternary N-Buylpyrrolidone, Ataliloylmorpholine; Acid Phosphoxchichinoremetatalylate, Acid Phosphoxypropino Bullet monomers with phosphate groups such as metatalylate, 3-chloro 2-acid phosphoxypropyl metatalylate or their (partial) alkali neutralized products; 2-- (meth) acrylamide 2-methylpropane Sulfonic acid, 2-sulfoethyl (meth) acrylate, 2-
- one or two of the above-described monofunctional hydrophobic vinyl monomers and hydrophilic vinyl monomers are used as the bull monomers in suspension polymerization.
- a polyfunctional vinyl monomer having two or more radically polymerizable unsaturated groups can be used.
- a hydrophilic polymer fine particle is produced by reverse-phase suspension polymerization of a hydrophilic vinyl monomer using a macromonomer (M) as a dispersion stabilizer
- M macromonomer
- a polyfunctional compound is used together with a monofunctional compound. It is preferable to use a vinyl monomer, whereby hydrophilic cross-linked polymer fine particles having improved strength and shape retention can be obtained.
- the “vinyl monomer” referred to in the present invention is a general term for a monofunctional bull monomer and a polyfunctional vinyl monomer.
- the polyfunctional vinyl monomer is a vinyl monomer having two or more radically polymerizable groups with a hydrophilic vinyl monomer or a hydrophobic vinyl monomer as a base.
- Specific examples that can be used are polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, trimethylol propantry (meth) acrylate, trimethylol propane.
- Examples include di- or tri (meth) acrylate of polyols such as tri (meth) acrylate of modified ethylene oxide, bisamides such as methylene bis (meth) acrylamide, dibutene benzene, allyl (meth) acrylate. One or more of these can be used.
- the polyfunctional vinyl monomer used for reversed-phase suspension polymerization is excellent in solubility in a mixture of polyethylene glycol diatalylate, hydrophilic bur monomer based on methylenebisacrylamide, and water.
- it is advantageous when used in an increased amount and is preferably used.
- the polyfunctional vinyl monomer When a polyfunctional vinyl monomer is used during suspension polymerization, the polyfunctional vinyl monomer
- the proportion of the polymer used may vary depending on the type of vinyl monomer used and the use of the polymer fine particles obtained by suspension polymerization, but if the polymer fine particles require cross-linking properties, It is preferably 0.1 to 100 mol with respect to a total of 100 mol of monofunctional bull monomers (not including macromonomers) used for polymerization. More preferred is 0.5 to 10 mol.
- a (partially) alkali neutralized product of (meth) acrylic acid which is a hydrophilic vinyl monomer as a vinyl monomer (monofunctional vinyl monomer) and Z or 2-acrylamide-2-me A (partial) alkali neutralized product of tilpropane sulfonic acid is used alone or in combination, and at least one of the above-mentioned polyfunctional vinyl monomers (especially polyethylene glycol ditalylate, methylenebisacrylamide).
- At least one of them is a monofunctional bulle monomer total of 100 monolayers, compared to 0.1 to: L00 monole, and further, 0.2 to 50 monole, specially 0.5
- a dispersion stabilizer comprising a macromonomer ( ⁇ ) when used at a ratio of ⁇ 10 mol, it has a water absorption ratio of 5 to 50 times, and the average in a saturated swelling state with water Particle size is 5 to 70 ⁇ m and saturated swelling with water
- the cross-linked hydrophilic polymer fine particle fraction of particles showing a particle size of more than 0.99 mu m in state of 3 mass% or less 0.1 can it to smooth production.
- hydrophilic bur monomer other than the above-mentioned (meth) acrylic acid or 2-acrylamido-2-methylpropanesulfonic acid according to the required characteristics required for polymer fine particles.
- the amount used is preferably 80% by mass or less, more preferably 50% by mass or less, based on the total amount of the monofunctional vinyl monomer.
- hydrophilic bulle monomers used in combination polymerization stability is good, and polymer fine particles having the above-mentioned characteristics can be easily obtained. Therefore, (meth) acrylamide and hydroxyethyl (meth) acrylate are used. Especially preferred is (meth) acrylamide.
- Alkali compounds for obtaining (partial) alkali neutrals include alkali metal hydroxides (such as sodium hydroxide and potassium hydroxide), ammonia, and amine compounds. Can be used. In the case where the volatilization of alkali compounds such as polymer fine particles is suppressed, an alkali metal hydroxide is added. On the contrary, it is preferable to use ammonia or low-boiling amine compounds when it is desired to remove alkaline compounds by volatilization.
- the degree of neutralization of the vinyl monomer 1 to 100% is preferable, 10 to 95% is more preferable, and 40 to 90% is particularly preferable. If a monomer having a carboxyl group or carboxylate such as (partial) neutralized salt of (meth) acrylic acid is used as the bull monomer, two functional groups that react with the carboxyl group are used. The degree of crosslinking can be further increased by using the compound having the above. As such a compound, a polyfunctional epoxy compound is preferred, and ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether are particularly preferred. There are two methods for adding these compounds: a method in which the vinyl monomer is mixed with the monomer before the polymerization and a method in which the compound is added to the polymer fine particle dispersion after the polymerization. Good.
- Suspension polymerization of bulle monomers for producing polymer fine particles is conventionally known except that macromonomer (M) is used as a dispersion stabilizer. Can be done.
- the suspension polymerization may be carried out by any of a continuous method, a batch method, and a semibatch (half batch) method. In the case of a batch method, the bull monomers may be polymerized in a lump or may be divided and polymerized.
- the hydrophobic monofunctional vinyl monomer alone or a hydrophobic monofunctional vinyl monomer is used.
- the oil phase is dissolved in a suitable water-insoluble organic solvent, and if necessary, the polyfunctional butyl monomer is further added and dispersed in the water phase (aqueous dispersion medium) in the form of fine oil droplets.
- a dispersion stabilizer composed of the macromonomer (M) polymer fine particles are produced by polymerization at a temperature of 10 to LOO ° C. using a radical polymerization catalyst.
- examples of the water-insoluble organic solvent for dissolving the hydrophobic monofunctional vinyl monomer include aliphatic hydrocarbon solvents having 6 or more carbon atoms, benzene, and toluene.
- Aromatic hydrocarbon solvents such as ethylene and xylene, ketone solvents such as methylisoptyl ketone, esters such as isoamyl acetate, and the like can be used.
- the macromonomer (M) is highly hydrophilic (having a high ratio of hydrophilic monomer units), and is preferably dissolved in a polar solvent such as water or alcohol, or uniformly dispersed in a solvent. It is preferable to add to the system.
- a polar solvent such as water or alcohol
- the macromonomer (M) preferably does not form micelles in water. Those that form micelles are not preferred because emulsion polymerization reaction proceeds simultaneously with suspension polymerization and a large amount of fine particles of 1 ⁇ m or less are formed.
- the amount of macromonomer (M) used [the amount used when the macromonomer (M) contains a small amount of non-macromonomer polymer] has a uniform particle size while maintaining good dispersion stability. In order to obtain polymer fine particles, 0.1 to 50 parts by mass is preferable with respect to 100 parts by mass of the total amount of the bull monomers (not including the macromonomer) 0.2 to 20 parts by mass. More preferably, it is 0.5 to 10 parts by mass. If the amount of the macromonomer (M) used is too small, the dispersion stability of the vinyl monomer in the polymerization system and the generated polymer particles will be poor, and the generated polymer particles will aggregate, settle, Variation in diameter tends to occur. On the other hand, when the amount of the macromonomer (M) used is too large, the amount of fine particles produced by the emulsion polymerization reaction tends to increase.
- the mass ratio of the aqueous phase (dispersion medium) to the oil phase (dispersoid) in the polymerization system is 99: 1 to 40:60, and the special ratio 95: 5 to 60:
- the ability to carry out the polymerization in such a manner that it is about 40 ⁇ m is preferable from the viewpoint of achieving both productivity, dispersion stability during polymerization, and control of the particle size of the polymer fine particles.
- normal phase suspension polymerization is carried out with stirring, and oil droplets (oil phase) containing a hydrophobic bulle monomer are placed in an aqueous phase (dispersion medium) in an amount of 1 to 500 m, especially 2 to: LOO m It is preferable to carry out the polymerization in a state of being dispersed with a particle size of 5 to obtain polymer fine particles having an appropriate particle size with a uniform particle size.
- hydrophobic organic solvent forming the oil phase for example, an aliphatic hydrocarbon solvent having 6 or more carbon atoms, benzene, toluene, xylene, ethylbenzene.
- Aromatic hydrocarbon solvents such as silicone solvents such as otamethylcyclotetrasiloxane can be used, especially hexane, cyclohexane, and n-heptane strength. It is preferably used because it is easy to remove after the polymerization.
- the hydrophilic vinyl monomer (and its neutralized salt) is preferably dissolved in water and converted into an aqueous solution, which is then stored in the polymerization system.
- concentration of the hydrophilic bur monomer in the aqueous solution in which the hydrophilic vinyl monomer is dissolved added to the polymerization system is 5 to 80% by mass, particularly 20 to 60% by mass. It is preferable that turbid polymerization is performed smoothly and productivity is good.
- the hydrophilic vinyl monomer used for reverse phase suspension polymerization is a vinyl monomer having an acidic group such as a carboxyl group or a sulfonic acid group
- the hydrophilic vinyl monomer was added to water. After that, neutralizing the acidic group in the bull monomer with an aqueous solution such as aqueous ammonia, aqueous sodium hydroxide, or aqueous potassium hydroxide solution dissolved the hydrophilic bull monomer well.
- An aqueous solution can be prepared.
- a hydrophilic vinyl monomer to be dissolved in water and added to the polymerization system a monofunctional hydrophilic vinyl monomer and a polyfunctional vinyl monomer (particularly the above-mentioned specific polyfunctional bulle system) are used. Monomer) is highly preferred.
- the macromonomer (M) is preferably added to the polymerization system after being dissolved or uniformly dispersed in a hydrophobic organic solvent forming a dispersion medium (oil phase).
- the amount of macromonomer (M) used [the amount used when the macromonomer (M) contains a small amount of non-macromonomer polymer] has a uniform particle size while maintaining good dispersion stability.
- 0.1 to 50 parts by mass is preferable with respect to 100 parts by mass of the total amount of the bull monomers (not including the macromonomer). More preferred is 20 parts by mass, and even more preferred is 0.5 to 10 parts by mass.
- the amount of the macromonomer (M) used is too small, the dispersion stability of the vinyl monomer in the polymerization system and the generated polymer particles will be poor, and the generated polymer particles will aggregate, settle, and have a particle size. Variation easily occurs.
- macromonomer aggregates (micelles) are likely to be produced, and the amount of by-product fine particles ( ⁇ ⁇ or less) produced is reduced. May increase.
- the mass ratio of the oil phase (dispersion medium) to the aqueous phase (dispersoid) in the polymerization system is 99: 1 to 20:80, particularly 95: 5 to 30:70. It is preferable to carry out the polymerization in such a way that the productivity, the dispersion stability during the polymerization, and the control of the particle size of the polymer fine particles are compatible.
- suspension polymerization is carried out with stirring, and water droplets (aqueous phase) containing a hydrophilic vinyl monomer are dispersed in the oil phase (dispersion medium) from 1 to: LOOO / zm, especially 2 to 500 m. It is preferable to carry out the polymerization in a state of being dispersed in a diameter in order to obtain hydrophilic polymer fine particles having an appropriate particle diameter with a uniform particle diameter.
- Usable radical polymerization catalysts include, for example, cumene hydride mouth peroxide, t-butyl hydride mouth peroxide, benzoyl peroxide, lauroyl peroxide, orthochloroperoxybenzoyl, orthomethoxyperoxide benzoyl, 3, 5, 5 Organic peroxides such as trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxide, t-butylperoxybivalate, Examples thereof include azo compounds such as dimethyl barre mouth-tolyl), peroxodisulfates such as persulfuric acid lithium and ammonium persulfate, and one or more of these can be used. .
- suspension polymerization is normal phase suspension polymerization
- a radical polymerization catalyst having high solubility in the dispersed phase (oil phase) and further low solubility in water of radicals generated by decomposition is preferable.
- benzoyl peroxide and peroxylauroyl peroxide are preferred.
- suspension polymerization when the suspension polymerization is reverse phase suspension polymerization, those having high solubility in the dispersed phase (aqueous phase) and low solubility in the continuous phase (oil phase) of radicals generated by decomposition are preferred.
- peroxodisulfates such as potassium persulfate and ammonium persulfate
- hydride peroxide compounds such as t-butyl hydroperoxide and cumene hydride peroxide are preferred.
- Decomposition of the initiator generation of radicals
- a dox reaction can be used.
- reducing compound used to start redox any known reducing compound that has been used in the past can be used. Especially, water-soluble sodium sulfite, sodium bisulfite, hydrosulfite Sodium is preferred. These reducing compounds are preferably added as an aqueous solution after adding a dispersed phase (aqueous phase) to a continuous phase (oil phase) and dispersing the dispersed phase to a desired particle size.
- any of the above-mentioned peroxides and peroxodisulfate can be used, but those that are soluble in both the oil phase and the aqueous phase are good.
- Particularly preferred are hydride peroxide compounds such as t-butyl hydride peroxide and cumene hydride peroxide, which are preferred because of their high polymerization rates.
- the amount of radical polymerization initiator used can be adjusted according to the type of vinyl monomer to be used, the particle size and molecular weight of the polymer fine particles, etc.
- the content is preferably 0.001 to 5% by mass, particularly 0.01 to 1% by mass, based on the total mass of the body. If the amount of the radical polymerization catalyst used is too small, the yield of the polymer fine particles may decrease. On the other hand, if the amount is too large, the molecular weight of the polymer becomes small and the strength and water absorption performance of the polymer fine particles are insufficient. The polymerization rate may become too high, making it difficult to carry out suspension polymerization stably.
- poorly water-soluble inorganic calcium salts such as poorly water-soluble tricalcium and pyrophosphate
- polyvinyl alcohol Hydrophilic polymers such as carboxymethylcellulose and sodium polyacrylate
- key-on surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate
- non-ionic surfactants such as polyoxyethylene lauryl
- Nonionic surfactants such as ether can be mentioned.
- a non-ionic surfactant with a relatively high HLB of 2 to L0 such as sorbitan monooleate and sorbitan monopalmitate. Or two or more of them may be used in combination.
- the amount of the other dispersion stabilizer used is 0.01 to 20 parts by mass with respect to 100 parts by mass of the vinyl monomer.
- the content is preferably 0.1 to 10 parts by mass. If the amount of other dispersion stabilizer used is too large, the dispersion stability during suspension polymerization may decrease, or the amount of fine particles by-produced below L m may increase.
- a dispersion liquid in which polymer fine particles are dispersed in the liquid can be obtained.
- the method for separating the polymer fine particles with a dispersion force is not particularly limited, and can be carried out by a method known in the art.
- a method for separating polymer fine particles for example, (1) a dispersion containing polymer fine particles is heated and Z or decompressed as it is to remove volatile matters such as a liquid medium and dry polymer fine particles. (2) The polymer fine particle dispersion is treated by sedimentation, centrifugation, decantation, filtration, etc.
- Examples thereof include a method of obtaining polymer fine particles by drying after removing a vinyl monomer. Washing the polymer fine particles recovered from the dispersion before drying is desirable in terms of improving the purity of the polymer fine particles and improving the dispersibility.
- azeotropic dehydration is performed in advance before drying the polymer fine particles to remove the water in the polymer fine particles. It is preferable to dry after removing. By drying after removing water in advance, the polymer fine particles can be prevented from being fused at the time of drying, and polymer fine particles having excellent dispersibility can be obtained. In general, it is preferable to dry the polymer fine particles at a temperature of 40 to 100 ° C, particularly 50 to 90 ° C as the temperature of the dispersion or dry particle powder! /.
- Polymer fine particles obtained by the method of the present invention in which a vinyl monomer is suspension-polymerized using the macromonomer (M) as a dispersion stabilizer generally have an average particle size of 2 to: LOOm.
- the reverse-phase suspension polymerization method uses, in particular, a macromonomer having an ⁇ -substituted vinyl group or an allyloyl group, the macromonomer has a weight average molecular weight of 1,000 to 30,000, and the macromonomer
- the average particle size is 2 to: Spherical polymer fine particles in the range of LOO / zm and having a uniform particle diameter (very few coarse particles) can be obtained.
- the water absorption ratio is 5 to 50 times
- the average particle size in the saturated swelling state with water is 5 to 70 ⁇ m
- 150 ⁇ m in the saturated swelling state with water Polymer fine particles (hydrophilic polymer fine particles) in which the ratio of particles having the above particle diameter is 0.3% by mass or less can be produced smoothly.
- the (partial) alkali neutralized product of the acid is used in an amount of 50% by mass or more of the total amount of the monofunctional vinyl monomer, and at least one of the above-mentioned polyfunctional vinyl monomers (especially polyethylene glycol ditalylate, At least one of methylenebisacrylamide) is 0.1 to L00 mol, more preferably 0.2 to 50 mol, especially 0.5 mol, based on a total of 100 mol of monofunctional bull monomers.
- M macromonomer
- the water absorption magnification is 5 to 50 times, and the normal state in the water saturated swelling state is obtained.
- Average particle size It is possible to smoothly produce hydrophilic polymer fine particles in which the proportion of particles having a particle diameter of 5 to 70 ⁇ m and a particle size of 150 ⁇ m or more in a water-saturated swelling state is 0.3% by mass or less.
- the particle size of the polymer fine particles produced by suspension polymerization can be adjusted by adjusting the stirring conditions of the polymerization system during suspension polymerization.
- the average particle diameter of the polymer fine particles (dried polymer fine particles) in this specification the water absorption ratio of the polymer fine particles, the average particle diameter in the saturated swelling state with water, and 150 in the saturated swelling state with water.
- the ratio of particles having a particle size of m or more is a value measured or determined by the method described in the section of the following examples.
- the ratio was measured or evaluated as follows.
- Each weighing bottle is stored in an airless dryer and dried at 150 ° C for 1 hour, and the weight at that time is measured for each weighing bottle [W (g)], and the solid content concentration (NV) ( % By mass).
- Macromonomer Macromonomer Macromonomer by gel permeation chromatography (GPC) When a small amount of polymer is contained, the macromonomer containing non-macromonomer polymer remains The weight average molecular weight (Mw) and number average molecular weight (Mn) of the macromonomer were determined in terms of polystyrene.
- HLC-8120GPC manufactured by Tosoh Corporation is used as a GPC device, and TSKgel super MP-M (four) is used as a column to dissolve the macromonomer in the solvent tetrahydrofuran.
- the solution (concentration 5 mgZml) was used as a sample, and tetrahydrofuran was used as a developing solvent, and measurement was performed under the conditions of a flow rate of 0.6 mlZ and a column temperature of 40 ° C.
- the measurement results were analyzed using a calibration curve prepared with standard polystyrene, and the weight average molecular weight (Mw) and number average molecular weight (Mn) of the macromonomer (macromonomer yarn and composition) in terms of polystyrene were determined.
- Example 1 From the constituent monomer composition of the macromonomer determined by the described method and the Mn determined in (2) above, the methylene group bonded to the ester bond of the (meth) acrylate unit contained per macromonomer The number of protons of a is a (number).
- the area of the peak derived from the proton of the methylene group bonded to the ester bond of the (meth) acrylate unit is b.
- F (%) calculated by the following formula ( ⁇ ) was defined as the introduction rate of terminal ethylenically unsaturated groups.
- the dispersion of polymer fine particles obtained by suspension polymerization is filtered through a polyethylene filter cloth (200 mesh; mesh size: 114 m, “Nip Power Mesh 200 mesh” manufactured by NBC) and remains on the polyethylene filter cloth.
- the mass of the polymer and other residues was measured after drying at 40 ° C. for 24 hours, and was determined as a ratio (% by mass) to the mass of the dispersion of polymer fine particles used for filtration.
- the particle size distribution is measured using the laser diffraction scattering type particle size distribution meter (“MT-3000” manufactured by Nikkiso) using the n-heptane dispersion obtained in (i) above.
- N-Heptane is used as the circulating dispersion medium during measurement.
- the n-heptane dispersion is put into the circulating dispersion medium, and the measurement is performed after irradiating the ultrasonic wave with an output of 25 w for 1 minute with the ultrasonic homogenizer built in the device.
- the refractive indexes of the dispersion medium and the sample were 1.39 and 1.53, respectively.
- the median diameter m) calculated from the volume-based particle size distribution is the average particle diameter of the polymer particles.
- Fig. 1 is a burette with a branch pipe for introducing air
- 2a and 2b are pinch cocks
- 3a, 3b and 3c are silicon tubes
- 4 is polytetrafluoroethylene tubes
- 5 is polytetrafluoroethylene Sealing material for fixing the polyethylene tube 4 to the branch pipe
- 6 is a port
- 7 is a bottomed cylinder with many holes on the bottom (for support)
- 9a and 9b are filter papers for fixing the sample (polymer fine particles) (, ADVANTEC No.
- Buret 1 lower branch force is also filled with force ion exchange water up to 8 sheets of filter paper placed at the bottom of open bottomed cylinder 7 with holes placed in funnel 6 through silicon tube 3c. Close the lower cock and the pinch cock 2b. Next, the pinch cock 2 above the burette is removed, and ion-exchanged water 12 is supplied to the top of the burette 1 through the silicon tube 3a attached to the top of the burette 1. After supplying, close the pinch cock 2a, and then open the cock at the bottom of the burette and the pinch cock 2b.
- the filter paper 8 is filled with ion-exchanged water from the top of the burette 1, and the polytetrafluorocarbon in which the same volume of air as the ion-exchanged water supplied to the sample from the filter paper 8 is installed inside the branch pipe. It enters a state where it is introduced into the burette 1 through the polyethylene tube 4.
- the filter paper 9a is uniformly placed on the center, and another filter paper 9b is placed thereon, and the filter paper 9a and 9b are fastened with the adhesive tape 11, and the sample 12 is fixed.
- the aqueous dispersion was passed through a sieve (diameter 70 mm) having a mesh size of 150 m with a note V, and remained on the sieve. Wash the residue with a sufficient amount of ion-exchanged water, taking care not to spill the residue from the sieve!
- the residue-retained sieve is directly put in an air dryer and dried at 150 ° C, and then left to cool in a desiccator.
- the weight of the sieve after cooling (the total mass of the sieve and the residue) (W)
- the ratio of particles having a particle size of 150 m or more in a saturated swelling state with water (hereinafter referred to as “content of water-saturated swollen particles (150 ⁇ m or more)”] Ask].
- W is the mass when only the sieve is dried (g), W is the total mass after drying the sieve and the residue (g),
- W represents the mass (50 g) of the sample (dried polymer fine particles).
- the molecular weight of the macromonomer (M-1) recovered in (2) above was determined by the method described above.
- the weight average molecular weight (Mw) was 3800 and the number average molecular weight (Mn) was 1800.
- the macromonomer (M-1) obtained in Production Example 1 was dissolved in n-heptane at 40 ° C, and the concentration of solid content [macromonomer (M-1)] was 30.0 ⁇ 0. 5 mass 0/0 of the macromonomer (M 1) containing solution (dispersion stabilizer liquid) was prepared.
- the solid content is a value calculated from the mass of the residue when a solution containing a macromonomer is heated at 150 ° C. for 1 hour.
- Example 7 was used in the amounts shown in Table 4 below (Examples 7 and 8), and the same operations as in (1) to (5) of Example 1 were performed to obtain polymer fine particles (PA-2) to Each (PA-8) dispersion was produced.
- Type ⁇ 2 N- 3 B-2 6 N- 3 B-246 N- 3 B-246 Use a (parts by mass) 10.0 10.0 10.0 10.0 8.00 8.0].
- Comparative Examples 1 to 8 where a macromonomer having a polymerizable unsaturated group was used as a dispersion stabilizer, agglomeration occurred immediately after the start of polymerization, and reverse phase suspension polymerization was practically impossible (Comparative Example 1) to 4), or even if it is possible to produce polymer fine particles by reversed-phase suspension polymerization, a large number of large aggregated particles are generated, having a predetermined appropriate particle size, and without uniform aggregation. The primary particles could not be obtained (Comparative Examples 5 to 8).
- the macromonomer (M-1) obtained in Production Example 1 was dissolved in n-heptane at 40 ° C, and the concentration of solid content [macromonomer (M-1)] was 30.0 ⁇ 0. 5 mass 0/0 of the macromonomer (M 1) containing solution (dispersion stabilizer liquid) was prepared.
- solid content refers to a value calculated from the mass force of the residue when a solution containing a macromonomer is heated at 150 ° C. for 1 hour.
- the reducing agent aqueous solution ion-exchanged water in which ferrous sulfate was dissolved at a concentration of 800 ppm was added to 1.67 parts by (Liquid in which 0.074 parts by mass of sulfite sodium was dissolved) 1. With 74 parts by mass added, the first stage polymerization was started. After the addition of the reducing agent aqueous solution, the temperature inside the polymerization reactor immediately increased and it was confirmed that the polymerization started. The temperature in the polymerization reactor reached the peak temperature (39 ° C) in a few minutes.
- Example 9 From the results of Example 9, a macromonomer [specifically, macromonomer (M-1)] having a radical polymerizable unsaturated group at the end of the polymer derived from the vinyl monomer was dispersed and stabilized.
- hydrophilic (water-swellable) polymer fine particles are produced by reverse-phase suspension polymerization using as an agent, even when reverse-phase suspension polymerization is performed in two stages, the particle diameters are uniform and several; It has an appropriate particle size on the order of several tens of meters, has excellent strength and water absorption performance, maintains a spherical shape even during water absorption swelling, and does not produce secondary particles due to aggregation of particles in water. It can be seen that fine polymer particles can be obtained that can be well dispersed in form.
- n a polymerization solvent.
- the macromonomer (M-1) obtained in Production Example 1 was dissolved in n-heptane at 40 ° C, and the concentration of solid content [macromonomer (M-1)] was 30.0 ⁇ 0. 5 mass 0/0 of the macromonomer (M 1) containing solution (dispersion stabilizer liquid) was prepared.
- solid content refers to a value calculated from the mass force of the residue when a solution containing a macromonomer is heated at 150 ° C. for 1 hour.
- the polymerization reactor force was also determined by visually observing the presence or absence of polymer fine particles in the polymerization reactor when the dispersion of polymer fine particles (PA-10) was taken out. There was only a small amount of polymer particles adhering in the vicinity of the liquid level inside, and the adhesion to the wall of the polymerization reactor was weak.
- the water-saturated swollen particles of 0) maintained a spherical shape! /, And had a particle size distribution centered around 40 ⁇ m.
- Example 10 Except that the dispersion stabilizer was changed to the one shown in Table 6 below, the same operations as in (1) to (5) of Example 10 were performed to obtain polymer fine particles (PA-11) and polymer fine particles ( When a dispersion of PA-12) (in-oil dispersion) was produced, a dispersion of polymer fine particles could be produced stably as in Example 10.
- PA-11 polymer fine particles
- PA-12 in-oil dispersion
- Powdered polymer fine particles (PA-11) and polymer fine particles (PA-12) obtained in (3) above are poured into a large excess of ion-exchanged water and left at 25 ° C for 1 hour. The sample was swollen to saturation, and the state was observed with the same digital microscope as used in Example 10 at a magnification of 420 times.
- Water-saturated swollen particles have a particle size distribution centered around 45 ⁇ m
- polymer fine particles (PA-12) water-saturated swollen particles have a particle size distribution centered around 50 ⁇ m.
- Figure 6 shows a digital microscope photograph (420x magnification) of the dispersion (dispersion in oil) of the polymer fine particles (PA-11) obtained in (1) above.
- Fig. 7 shows a digital microscope photograph (magnification 420 times) of water-saturated swollen particles of polymer particles (PA-11) in ii).
- Dispersion stabilizer type and amount used polyethylene glycol diatalylate (“Aronix M-243” manufactured by Toagosei Co., Ltd., average molecular weight 425) was changed as shown in Table 6 below.
- the dispersion stabilizer for the polymer fine particles (PA-13), the dispersion stabilizer for the polymer fine particles (PA-14), and the polymer fine particles ( PA-15) dispersion stabilizers were produced for each (a dispersive dispersion is also a medium-in-oil dispersion).
- Examples 13-15 since sorbitan monopalmitate (SP-10) used in Examples 13-15 has low solubility in n-heptane at low temperatures, in Examples 13-15, three types of dispersion stabilizers and n -After charging heptane into the polymerization reactor, adjust the temperature in the polymerization reactor to 35 ° C and stir for 1 hour to dissolve the dispersion stabilizer uniformly (dispersion stabilizer solution; oil phase ) was prepared. In any of Examples 13 to 15, a dispersion of polymer fine particles could be stably produced as in Example 10.
- SP-10 sorbitan monopalmitate
- the polymer fine particle group power of V, misaligned polymer fine particles, even multiple polymerization Aggregated particles (secondary particles) in which the body fine particles were coalesced were not observed.
- high-quality spherical polymer fine particles having an appropriate particle diameter of several / zm to several tens / zm order, generally 2 to It can be produced with good productivity while maintaining high dispersion stability and polymerization stability without causing aggregation and agglomeration of polymer particles and adhesion to a polymerization apparatus after polymerization.
- Polymer fine particles obtained by the method of the present invention of which the hydrophilic polymer fine particles obtained by the method of the present invention are cosmetic additives, carriers for various chemical substances, spacers, and column packing for chromatography. It is useful as an agent, a light diffusing agent, a porosifying agent, a lightening agent, an antiblocking agent, a surface modifier for recording paper, and the like.
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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)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
Claims
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AT07768247T ATE524497T1 (de) | 2006-08-04 | 2007-07-05 | Verfahren zur herstellung von feinen polymerteilchen |
US12/375,606 US8415433B2 (en) | 2006-08-04 | 2007-07-05 | Process for producing polymer microparticles |
PL07768247T PL2048165T3 (pl) | 2006-08-04 | 2007-07-05 | Sposób wytwarzania drobnych cząstek polimerowych |
EP07768247A EP2048165B1 (en) | 2006-08-04 | 2007-07-05 | Process for producing fine polymer particle |
CN200780029006XA CN101501077B (zh) | 2006-08-04 | 2007-07-05 | 聚合物微粒的制造方法 |
MX2009001242A MX2009001242A (es) | 2006-08-04 | 2007-07-05 | Proceso para producir particulas finas de polimero. |
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JP2006212718A JP5256590B2 (ja) | 2006-08-04 | 2006-08-04 | 重合体微粒子の製造方法 |
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EP (1) | EP2048165B1 (ja) |
JP (1) | JP5256590B2 (ja) |
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CN (1) | CN101501077B (ja) |
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TWI454487B (zh) * | 2008-10-22 | 2014-10-01 | Toagosei Co Ltd | A method for producing polymer microparticles |
JP2016121140A (ja) * | 2014-12-24 | 2016-07-07 | 日光ケミカルズ株式会社 | ジェル状化粧料 |
WO2017204281A1 (ja) * | 2016-05-27 | 2017-11-30 | 日光ケミカルズ株式会社 | 凹凸補正化粧料 |
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Publication number | Publication date |
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EP2048165A1 (en) | 2009-04-15 |
ATE524497T1 (de) | 2011-09-15 |
CN101501077A (zh) | 2009-08-05 |
MX2009001242A (es) | 2009-03-16 |
US20100069592A1 (en) | 2010-03-18 |
JP2008037971A (ja) | 2008-02-21 |
KR20090045307A (ko) | 2009-05-07 |
EP2048165B1 (en) | 2011-09-14 |
CN101501077B (zh) | 2011-09-07 |
US8415433B2 (en) | 2013-04-09 |
PL2048165T3 (pl) | 2012-02-29 |
JP5256590B2 (ja) | 2013-08-07 |
EP2048165A4 (en) | 2009-11-11 |
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