WO2013108588A1 - 乳化重合用乳化剤 - Google Patents
乳化重合用乳化剤 Download PDFInfo
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- WO2013108588A1 WO2013108588A1 PCT/JP2013/000026 JP2013000026W WO2013108588A1 WO 2013108588 A1 WO2013108588 A1 WO 2013108588A1 JP 2013000026 W JP2013000026 W JP 2013000026W WO 2013108588 A1 WO2013108588 A1 WO 2013108588A1
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- 0 C*1CCCC1 Chemical compound C*1CCCC1 0.000 description 3
- XTVMZZBLCLWBPM-UHFFFAOYSA-N CC(C)(C)C1CCCCC1 Chemical compound CC(C)(C)C1CCCCC1 XTVMZZBLCLWBPM-UHFFFAOYSA-N 0.000 description 2
- GWESVXSMPKAFAS-UHFFFAOYSA-N CC(C)C1CCCCC1 Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N CC1CCCCC1 Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N CC1(C)CCCCC1 Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
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- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/24—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of a carbon skeleton containing six-membered aromatic rings
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- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/125—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups
- C07C59/13—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups containing rings
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/30—Sulfur
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
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- 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
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- 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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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2636—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing sulfur
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
Definitions
- the present invention relates to an emulsifier used in an emulsion polymerization step, and more particularly a reactive emulsifier, which can improve the stability of a polymer dispersion and thereby improve the physical properties of a polymer film obtained thereby. It relates to an emulsifier.
- Conventional emulsifiers for emulsion polymerization include soaps, sodium dodecylbenzenesulfonate, anionic surfactants such as polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene nonylphenyl, and the like.
- Nonionic surfactants such as ethers and polyoxyethylene alkyl ethers are used, but in polymer films obtained from polymer dispersions using these emulsifiers, the emulsifier used is free in the polymer film. Therefore, there are problems such as poor water resistance and adhesiveness of the film. Therefore, many reactive emulsifiers having a copolymerizable unsaturated group have been proposed as measures for improving the above problems (for example, Patent Documents 1 to 3).
- the reactive emulsifier having an acrylic group or a methacrylic group as a copolymerizable unsaturated group proposed in the prior art is excellent in copolymerization with a monomer, but deteriorates polymerization stability during emulsion polymerization.
- Reactive emulsifiers having an allyl group as a copolymerizable unsaturated group may be inferior in copolymerizability between the reactive emulsifier and the monomer depending on the monomer species and the polymerization conditions, and polymer films obtained from polymer dispersions are also available.
- the present invention has been made in view of the above circumstances, and its purpose is to improve the polymerization stability during emulsion polymerization, solve the problem of foaming, and obtain from the polymer dispersion after polymerization.
- Another object of the present invention is to provide a reactive emulsifier for emulsion polymerization that can remarkably improve various properties such as water resistance and adhesiveness of the polymer film obtained.
- the present invention provides a reactive emulsifier for emulsion polymerization that can significantly improve the properties of the resulting polymer dispersion even when styrene, which is a particular problem in commercial production, is contained as a monomer as described above. With the goal.
- the emulsifier for emulsion polymerization of the present invention contains a compound represented by the following general formula (I) in order to solve the above problems.
- R 0 represents an alkyl group having 1 to 4 carbon atoms
- R 1 represents one or two groups selected from the following groups.
- 2 represents hydrogen or a methyl group
- D represents a polymerizable unsaturated group represented by any of the following chemical formulas D-1 or D-2, wherein R 3 represents a hydrogen atom or a methyl group
- m1 represents a number of 1 to 2
- m2 represents a number of 1 to 3
- m3 represents a number of 0 or 1
- A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group
- n represents an alkylene Represents the average number of moles of oxide added, and represents a number in the range of 0 to 1,000
- X is a hydrogen atom, or — (CH 2 ) a —SO 3 M, — (CH 2 ) b —COOM, —PO 3 M 2
- the emulsifier for emulsion polymerization of the present invention is represented by the chemical formula D-1 and the chemical formula D-2 in the above general formula (I), where m1 is an average value in the range of 1 ⁇ m1 ⁇ 1.5.
- the value of (D-1) / (D-2), which is the molar ratio of groups, is preferably larger than 2.
- X represents a hydrogen atom or SO 3 M, where M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium residue, or an alkanolamine residue, A which represents an alkylene group having 2 carbon atoms can be suitably used.
- the stability during emulsion polymerization is improved, the problem of foaming is improved, and various properties such as water resistance and adhesiveness of the polymer film obtained from the polymer dispersion are remarkably improved.
- An emulsifier can be provided.
- the emulsifier for emulsion polymerization of the present invention contains a compound represented by the following general formula (I) as a main component as described above.
- R 0 represents an alkyl group having 1 to 4 carbon atoms
- R 1 represents one or two groups selected from the following groups
- R 2 in the formula represents hydrogen or Represents a methyl group
- D represents a polymerizable unsaturated group represented by either of the following chemical formulas D-1 or D-2, in which R 3 represents a hydrogen atom or a methyl group
- m1 represents 1 represents a number of 1 to 2
- m2 represents a number of 1 to 3
- m3 represents a number of 0 or 1
- the total number of m1, m2, and m3 is 2 to 5.
- D and R 1 s may be the same as or different from each other.
- A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group
- n represents the average number of added moles of alkylene oxide, and represents a number in the range of 0 to 1,000.
- X is a hydrogen atom, or — (CH 2 ) a —SO 3 M, — (CH 2 ) b —COOM, —PO 3 M 2 , —P (Z) O 2 M, and —CO—CH 2 —CH ( SO 3 M) represents an anionic hydrophilic group selected from COOM, in which a and b each represent a number of 0 to 4, Z represents a residue obtained by removing X from the general formula (I) And M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium residue, or an alkanolamine residue, respectively.
- D is specifically a 1-propenyl group or a 2-methyl-1-propenyl group or (meta ) Represents an allyl group.
- these 1-propenyl group, 2-methyl-1-propenyl group, or (meth) allyl group may be present alone or as a mixture. It is preferably a group.
- m1 representing the number of substituents of D is a number of 1 or more, preferably 1 or 2, and the substitution position of D is preferably the ortho position (2nd or 6th position).
- m1 is preferably in the range of 1 ⁇ m1 ⁇ 1.5 as an average value
- the groups represented by chemical formula D-1 and chemical formula D-2 are in a molar ratio of both (D-1).
- the value of / (D-2) is preferably larger than 2.
- the (AO) n chain portion in the general formula (I) is one or two kinds of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran (1,4-butylene oxide) as alkylene oxide having 2 to 4 carbon atoms.
- the above can be selected and obtained by addition polymerization.
- the polymerization form such as alkylene oxide to be added is not limited. One type of alkylene oxide homopolymer, two or more types of alkylene oxide random copolymers, block copolymers, or random adducts and block copolymers. It may be a combination.
- an oxyethylene group is particularly preferable.
- one type is preferably selected from ethylene oxide, and the (AO) n chain portion preferably contains 50 to 100 mol% of oxyethylene groups, more preferably 70 to It is a (poly) oxyalkylene chain containing 100 mol%.
- Polymerization degree n represents the average number of added moles of alkylene oxide, and is a number in the range of 0 to 1,000, preferably a number in the range of 0 to 100. More specifically, when X in the general formula (I) is a hydrogen atom, the degree of polymerization n is preferably a number in the range of 10-50. When X is an ionic hydrophilic group, the polymerization degree n is preferably a number in the range of 0 to 50, more preferably a number in the range of 3 to 30.
- the content of the oxyethylene group in the (AO) n chain and the degree of polymerization n are variable in the degree of hydrophilicity or hydrophobicity of the emulsifier. It is preferable to appropriately design the composition of the chain portion of (AO) n according to the characteristics of the polymer dispersion, the characteristics of the polymer film, or the monomers and applications to be used.
- X in the general formula (I) is a hydrogen atom, or (CH 2 ) a—SO 3 M, — (CH 2 ) b —COOM, —PO 3 M 2 , —P (Z) O 2 M, — CO—CH 2 —CH (SO 3 M) —COOM (wherein, a and b each represent a number of 0 to 4, and Z represents a residue obtained by removing X from the above general formula (I)).
- An anionic hydrophilic group represented by In the formula (I) representing the above anionic hydrophilic group M represents a hydrogen atom, an alkali metal atom such as lithium, sodium or potassium, an alkaline earth metal atom such as magnesium or calcium, or an ammonium or alkanolamine residue.
- ammonium include ammonium of ammonia or ammonium of alkylamine such as monomethylamine and dipropylamine.
- alkanolamine residues include monoethanolamine residue, diethanolamine residue, and triethanolamine. Examples include residues.
- a group represented by —SO 3 M, —PO 3 M 2 or P (Z) O 2 M is preferable.
- the —PO 3 M 2 represents a monoester form with the residue Z obtained by removing X from the above general formula (I), and —P (Z) O 2 M represents the above general formula (I) to X
- the diester form with the residue Z except for is represented. As described above, these can be used alone in the present invention, or can be used as a mixture in the present invention.
- the reaction is followed by Claisen rearrangement in the presence of alkali to obtain a phenol derivative having a polymerizable group on the aromatic ring, or (ii) the reaction of phenol and allyl halide by a known method, followed by the presence of alkali
- a method of obtaining a phenol derivative having a polymerizable group in an aromatic ring by carrying out Claisen rearrangement and then introducing a substituent into the aromatic ring under known conditions.
- an emulsifier for emulsion polymerization having the desired ionic hydrophilic group can be obtained by introducing an ionic hydrophilic group into the nonionic compound by a known method.
- the synthesis route in the present invention is not particularly limited, and methods other than those described above can also be used.
- the polymerizable unsaturated group represented by D is a 1-propenyl group, a 2-methyl-1-propenyl group or a (meth) allyl group as described above.
- (Meth) allyl group is introduced by (meth) allylation reaction of styrenated phenol.
- those having 1-propenyl group or 2-methyl-1-propenyl group are (meth) allylation reaction of styrenated phenol or styrenated alkylphenol (hereinafter sometimes abbreviated as styrenated (alkyl) phenol).
- an allyl styrenated (alkyl) phenol is obtained by reacting an allyl halide with a styrenated (alkyl) phenol together with a basic substance such as sodium hydroxide or potassium hydroxide and further heating to about 100 ° C.
- reaction compositions (i) to (iv) a reaction composition containing a diallyl body and the like in addition to the target (mono) allyl body can be obtained.
- the allyl group is rearranged to a 1-propenyl group, and the main target propenyl styrenated phenol is obtained.
- unrearranged allyl is obtained.
- a composition containing a certain amount of styrenated phenol can be obtained.
- allyl styrenated phenol obtained by the above reaction formula (ii) is 1-propenyl.
- D in the general formula (I) of the present invention which is one of the objects, is 1-propenyl.
- X in the general formula (I) is an ionic hydrophilic group
- the compound obtained by the above method is further introduced into the ionic hydrophilic group.
- the reaction conditions for introducing the anionic hydrophilic group in which a is 0 in — (CH 2 ) a —SO 3 M are not particularly limited.
- sulfamic acid, sulfuric acid It can be produced by reacting sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid and the like.
- reaction conditions for introducing an anionic hydrophilic group in which a is represented by a number of 1 to 4 in — (CH 2 ) a —SO 3 M are not particularly limited, and examples thereof include propane sultone, It can be produced by reacting butane sultone or the like.
- the reaction conditions for introducing the anionic hydrophilic group represented by — (CH 2 ) b —COOM are not particularly limited.
- the hydroxyl group is oxidized, or the monohalogen Carboxylation can be carried out by reacting with chloroacetic acid, or saponification can be carried out by reacting with acrylonitrile and acrylic acid ester and saponification with an alkali.
- reaction conditions for introducing the anionic hydrophilic group to be introduced are not particularly limited, and can be produced, for example, by reacting diphosphorus pentoxide, polyphosphoric acid, orthophosphoric acid, phosphorus oxychloride and the like.
- a monoester type compound and a diester type compound are obtained as a mixture, but these may be separated or used as they are as a mixture. Also good. Further, the reaction can be performed in the presence of water to increase the content ratio of the monoester compound.
- the reaction conditions for introducing the anionic group represented by —CO—CH 2 —CH (SO 3 M) —COOM are not particularly limited.
- maleic anhydride is reacted. It can be produced by monoesterification and sulfonation by reacting with anhydrous sodium sulfite.
- alkalis such as sodium hydroxide and potassium hydroxide
- alkanolamines such as ammonia, an alkylamine, monoethanolamine, and diethanolamine.
- the monomer applied to emulsion polymerization using the emulsifier for emulsion polymerization of the present invention is not particularly limited, and can be applied to various types.
- Examples of the monomer constituting the acrylate emulsion include (meth) acrylic acid esters), (meth) acrylic acid (ester) / styrene, (meth) acrylic acid ester) / vinyl acetate, (meth) acrylic acid ester) / Acrylonitrile, (meth) acrylic acid (ester) / butadiene, (meth) acrylic acid (ester) / vinylidene chloride, (meth) acrylic acid (ester) / allylamine, (meth) acrylic acid (ester) / vinyl pyridine, ( (Meth) acrylic acid (ester) / (meth) acrylic acid alkylolamide, (meth) acrylic acid (ester) / N, N-dimethylaminoethyl (meth) acrylate, (meth) acrylic acid (ester) / N, N -Diethylaminoethyl vinyl ether and the like.
- styrene emulsion in addition to styrene alone, for example, styrene / acrylonitrile, styrene / butadiene, styrene / fumaronitrile, styrene / maleinonitrile, styrene / cyanoacrylate, styrene / phenylvinyl acetate, styrene / chloromethylstyrene Styrene / dichlorostyrene, styrene / vinyl carbazole, styrene / N, N-diphenylacrylamide, styrene / methyl styrene, acrylonitrile / butadiene / styrene, styrene / acrylonitrile / methyl styrene, styrene / acrylonitrile / methyl st
- vinyl acetate emulsion in addition to vinyl acetate alone, for example, vinyl acetate / styrene, vinyl acetate / vinyl chloride, vinyl acetate / acrylonitrile, vinyl acetate / maleic acid (ester), vinyl acetate / fumaric acid (ester) Vinyl acetate / ethylene, vinyl acetate / propylene, vinyl acetate / isobutylene, vinyl acetate / vinylidene chloride, vinyl acetate / cyclopentadiene, vinyl acetate / crotonic acid, vinyl acetate / acrolein, vinyl acetate / alkyl vinyl ether, and the like.
- Monomers used for halogenated olefin polymerization include, for example, vinyl chloride, vinylidene chloride, vinyl chloride / maleic acid (ester), vinyl chloride / fumaric acid (ester), vinyl chloride / vinyl acetate, vinyl chloride / chloride. And vinylidene chloride, vinylidene chloride / vinyl acetate, vinylidene chloride / vinyl benzoate, and the like.
- the polymerization initiator used in the emulsion polymerization reaction using the emulsifier for emulsion polymerization of the present invention is not particularly limited.
- hydrogen peroxide, ammonium persulfate, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, etc. can be used.
- the polymerization accelerator sodium bisulfite, ferrous ammonium sulfate, and the like can be used.
- chain transfer agent mercaptans such as ⁇ -methylstyrene dimer, n-butyl mercaptan, t-dodecyl mercaptan, halogenated hydrocarbons such as carbon tetrachloride and carbon tetrabromide may be used.
- the amount of the emulsifier of the present invention varies depending on the type of monomer and the like, and is not limited thereto, but is usually preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight of the total amount of monomers. 0.2 to 10.0 parts by mass.
- anionic surfactants or cationic surfactants and / or other surfactants can be used as long as the effects of the present invention can be maintained.
- a nonionic surfactant may be used in combination, whereby the polymerization stability during emulsion polymerization can be improved, and the processing characteristics in the subsequent steps can be improved.
- the anionic surfactant, the cationic surfactant and the nonionic surfactant are not particularly limited.
- examples of the anionic surfactant include fatty acid soap, rosin acid soap, alkylsulfonate, alkylaryl Examples include sulfonates, alkylsulfosuccinates, polyoxyalkylene alkyl sulfates, polyoxyalkylene aryl sulfates, and examples of cationic surfactants include stearyl trimethyl ammonium, cetyl trimethyl ammonium, and lauryl trimethyl ammonium.
- Nonionic surfactants include polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, alkyl polyglucoside, polyglycerin alkyl ether, polyoxyalkylene. Fatty acid esters, polyglycerol fatty acid esters, and the like sorbitan fatty acid ester.
- the amount of the surfactant used in combination is preferably 0.5 to 95% by mass, more preferably 5 to 60% by mass, and still more preferably 10% by mass in the emulsifier for emulsion polymerization of the present invention. ⁇ 30% by mass.
- a known protective colloid agent can be used in combination for the purpose of improving the polymerization stability during emulsion polymerization.
- protective colloid agents that can be used in combination include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyacrylic acid, and gum arabic.
- the emulsifier for emulsion polymerization of the present invention can be added to the polymer after completion of polymerization in order to improve the stability of the polymer emulsion.
- the emulsifier for emulsion polymerization of the present invention can also be applied to suspension polymerization.
- the emulsifier for emulsion polymerization of the present invention has a copolymerizable unsaturated group in the hydrophobic group portion of the molecule, is excellent in copolymerizability with a polymerizable monomer, particularly a styrene monomer, and is incorporated into the polymer composition.
- Cheap Therefore, as a copolymerizable reactive emulsifier, the amount of the emulsifier present in a free state in the polymer film obtained from the polymer emulsion is remarkably reduced, and various properties such as water resistance, adhesiveness, heat resistance and weather resistance of the film are reduced. Exhibits extremely excellent effects in improving characteristics. In addition, foaming and mechanical stability of the polymer emulsion are remarkably improved.
- Synthesis example of compound represented by general formula (I) (Synthesis Example 1)
- NaOH 40 g (1.0 mol) and 210 g of acetone were charged, and the internal temperature was raised to 40 ° C. while stirring.
- 91 g (1.2 mol) of allyl chloride was added dropwise over 1 hour. After completion of dropping, the reaction was further continued at 40 ° C. for 2 hours.
- the reaction product was filtered to remove NaCl as a by-product, and then acetone was removed under reduced pressure to obtain 314 g of allylstyrenated phenyl ether.
- This allyl phenyl ether was charged into an autoclave, and stirred at 200 ° C. for 5 hours. At this stage, a rearrangement reaction occurred to give 2-allyl styrenated phenol. 290 g of this 2-allyl styrenated phenol was transferred to an autoclave, and 440 g (10 mol) of ethylene oxide was added under the conditions of a pressure of 1.5 kg / cm 3 and a temperature of 130 ° C. using potassium hydroxide as a catalyst. A crude product (mixture) containing 99% of the compound represented by the general formula (I) (Product 1 of the present invention) was obtained. During this reaction, the allyl group was quantitatively changed to a 1-propenyl group.
- the reaction product was filtered to remove by-produced NaCl, and then acetone was removed under reduced pressure to obtain 302 g of 2-allylstyrenated methylphenyl ether.
- This 2-allyl styrenated methyl phenyl ether was charged into an autoclave and kept stirred at 200 ° C. for 5 hours. At this stage, a rearrangement reaction occurred to give 2-allylstyrenated methylphenol.
- 302 g of this 2-allyl styrenated methylphenol was transferred to an autoclave, 440 g (10 mol) of ethylene oxide was added under the conditions of a pressure of 1.5 kg / cm 3 and a temperature of 130 ° C. using potassium hydroxide as a catalyst.
- a crude product (mixture) containing 99% of the compound represented by the formula (Product 11 of the present invention) was obtained. During this reaction, the allyl group was quantitatively changed to a 1-propenyl group.
- a part of the polymer dispersion was taken, and the particle size was measured with a dynamic light scattering particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., product name MICROTRAC UPA9340).
- the dropping funnel was charged with 36 g of the previously prepared mixed monomer emulsion, added to the reactor at once, and heated to 80 ° C. Then, after continuing stirring for 15 minutes, 0.5 g of ammonium persulfate as a polymerization initiator was dissolved in 20 g of ion-exchanged water and added to initiate polymerization. Next, 15 minutes after the addition of the polymerization initiator, the remaining 324 g of the mixed monomer emulsion was dropped and polymerized over 3 hours. Further, after aging for 2 hours in succession, the mixture was cooled and adjusted to pH 8 with aqueous ammonia to obtain a polymer dispersion for use in the evaluation experiment of the present invention.
- the obtained polymer dispersion was evaluated for polymerization stability, average particle size, mechanical stability, and foaming property, and the polymer film was also evaluated for water whitening resistance and water absorption.
- the evaluation results are shown in Table 1.
- the polymer dispersion obtained was evaluated for polymerization stability, average particle diameter, mechanical stability, and foaming property, and the polymer film was evaluated for water whitening resistance and adhesive retention.
- the evaluation results are shown in Table 2.
- the dropping funnel was charged with 36 g of the previously prepared mixed monomer emulsion, added to the reactor at once, and heated to 80 ° C. Then, after continuing stirring for 15 minutes, 0.5 g of ammonium persulfate as a polymerization initiator was dissolved in 20 g of ion-exchanged water and added to initiate polymerization. Next, 15 minutes after the addition of the polymerization initiator, the remaining 324 g of the mixed monomer emulsion was dropped and polymerized over 3 hours. Further, after aging for 2 hours in succession, the mixture was cooled and adjusted to pH 8 with aqueous ammonia to obtain a polymer dispersion for use in the evaluation experiment of the present invention.
- the obtained polymer dispersion was evaluated for polymerization stability, average particle diameter, mechanical stability, and foaming property, the polymer film was evaluated for water whitening resistance, and water absorption was measured.
- the evaluation results are shown in Table 3.
- the polymer dispersion obtained was evaluated for polymerization stability, average particle diameter, mechanical stability, and foaming property, and the polymer film was evaluated for water whitening resistance and adhesive retention.
- the evaluation results are shown in Table 4.
- the polymer dispersion obtained by adding the emulsifier for emulsion polymerization of the present invention can be applied, for example, to a resin, metal, paper, wood, cloth, concrete, etc. as an adhesive, an adhesive, a coating agent, an impregnation reinforcing agent, etc. Can be applied.
- the polymer dispersion or the solid polymer taken out from the polymer dispersion can be used as a resin, rubber, or polymer modifier.
Abstract
Description
本発明の乳化重合用乳化剤を用いた乳化重合に適用されるモノマーは特に限定されず、種々のものに適用可能である。例えばアクリレート系エマルション、スチレン系エマルション、酢酸ビニル系エマルション、SBR(スチレン/ブタジエン)エマルション、ABS(アクリロニトリル/ブタジエン/スチレン)エマルション、BR(ブタジエン)エマルション、IR(イソプレン)エマルション、NBR(アクリロニトリル/ブタジエン)エマルション等の製造に使用でき、2種以上のモノマーを混合して乳化重合することもできる。
本発明の乳化重合用乳化剤を使用した乳化重合反応に使用される重合開始剤は特に限定されず、例えば、過酸化水素、過硫酸アンモニウム、過硫酸カリウム、アゾビスイソブチロニトリル、ベンゾイルパーオキシド等を使用できる。重合促進剤としては、亜硫酸水素ナトリウム、硫酸第1鉄アンモニウム等が使用できる。また、連鎖移動剤として、α-メチルスチレンダイマー、n-ブチルメルカプタン、t-ドデシルメルカプタンなどのメルカプタン類、四塩化炭素、四臭化炭素などのハロゲン化炭化水素などを用いてもよい。
本発明の乳化重合用乳化剤は、その分子中の疎水基部分に共重合性の不飽和基を有し、重合性モノマー、殊にスチレン系モノマーとの共重合性に優れ、ポリマー組成に組み込まれやすい。そのため、共重合性の反応性乳化剤として、ポリマーエマルションから得られたポリマーフィルム中に遊離した状態で存在する乳化剤量が著しく減少し、フィルムの耐水性、接着性、耐熱性、耐候性等の諸特性の向上に極めて優れた効果を発揮する。かつポリマーエマルションの泡立ち、機械安定性等が著しく改善される。
(合成例1)
撹拌機、温度計、還流管を備えた反応容器に、スチレン化フェノール(モノスチレン化フェノール:ジスチレン化フェノール:トリスチレン化フェノール=72:27:1の混合物)230g(1.0モル)、NaOH40g(1.0モル)およびアセトン210gを仕込み、撹拌しながら内温を40℃に昇温した。次にアリルクロライド91g(1.2モル)を1時間かけて滴下した。滴下終了後、さらに40℃に2時間保ち、反応を行った。反応生成物を濾過し、副生したNaClを除去した後、減圧下にアセトンを除去し、アリルスチレン化フェニルエーテル314gを得た。このアリルフェニルエーテルをオートクレーブに仕込み、200℃で5時間撹拌保持した。この段階で転位反応が起こり、2-アリルスチレン化フェノールとした。この2-アリルスチレン化フェノール290gをオートクレーブに移し、水酸化カリウムを触媒とし、圧力1.5kg/cm3、温度130℃の条件にて、エチレンオキサイド440g(10モル)を付加させて、次の一般式(I)で表される化合物(本発明品1)が99%含まれる粗製物(混合物)が得られた。この反応時にアリル基は、1-プロペニル基に定量的に変化した。
撹拌器、温度計及び窒素導入管を備えた反応容器に、上記合成例1で得られた化合物(本発明品1)730g(1モル)を仕込み、反応装置内の雰囲気を窒素で置換後、温度120℃の条件にてスルファミン酸97g(1モル)を反応させた後、精製して次の一般式(I)で表される化合物(本発明品3)を得た。
撹拌機および温度計を備えた反応容器に合成例1で得られた化合物(本発明品1)730g(1モル)仕込んだ。モノクロル酢酸ナトリウム128g(1.1モル)及び水酸化ナトリウム44g(1.1モル)を40℃にした反応容器内に3時間をかけて添加した。その後、40℃にて撹拌しながら17時間反応させた後、精製して次の一般式(I)で表される化合物(本発明品4)を得た。
撹拌機および温度計を備えた反応容器に合成例1で得られた化合物(本発明品1)730g(1モル)仕込んだ。次に撹拌しながら無水リン酸94g(0.33モル)を仕込み、撹拌しながら80℃で5時間リン酸化を行った後、苛性ソーダで中和して、次の一般式(I)で表される化合物(本発明品5)を得た。本組成物をNMRにて確認したところ、モノエステル/ジエステルの比率は56/44であった。
撹拌機、温度計、還流管を備えた反応容器に、2-アリルスチレン化フェノール(上記一般式(I)において、m2が1.5で表される化合物)を300g(1.0モル)を仕込み、水酸化カリウムを触媒とし、圧力1.5kg/cm3、温度130℃の条件にて、プロピレンオキサイド175g(3モル)を、次いでエチレンオキサイド440g(10モル)を付加させた。この反応時にアリル基は、1-プロペニル基に定量的に変化した。さらにこのプロピレンオキサイド及びエチレンオキサイドブロック付加体905g(1モル)を撹拌器、温度計及び窒素導入管を備えた反応容器に仕込み、反応装置内の雰囲気を窒素で置換後、温度120℃の条件にてスルファミン酸97g(1モル)を反応させた後、精製して次の一般式(I)で表される化合物(本発明品6)を得た。
エチレンオキサイドの付加反応時の温度を130℃から115℃に変更した他は、合成例1及び合成例3に準じて次の一般式(I)で表される化合物(本発明品7)を得た。この反応時にアリル基は、80%の転化率で1-プロペニル基に変化した。
ジスチレン化フェノール及びモノスチレン化フェノールの混合物の代わりにモノスチレン化フェノールを用い、アリルクロライドの量を91g(1.2モル)から152g(2.0モル)に増やした他は、合成例1及び合成例3に準じて次の一般式(I)で表される化合物(本発明品9)を得た。
撹拌機、温度計、還流管を備えた反応容器に、スチレン化メチルフェノール(モノスチレン化メチルフェノール:ジスチレン化メチルフェノール:トリスチレン化メチルフェノール=70:20:10)253g(1.0モル)、NaOH40g(1.0モル)およびアセトン210gを仕込み、撹拌しながら内温を40℃に昇温した。次にアリルクロライド91g(1.2モル)を1時間かけて滴下した。滴下終了後、さらに40℃に2時間保ち、反応を行った。反応生成物を濾過し、副生したNaClを除去した後、減圧下にアセトンを除去し、2-アリルスチレン化メチルフェニルエーテル302gを得た。この2-アリルスチレン化メチルフェニルエーテルをオートクレーブに仕込み、200℃で5時間撹拌保持した。この段階で転位反応が起こり、2-アリルスチレン化メチルフェノールとした。この2-アリルスチレン化メチルフェノール302gをオートクレーブに移し、水酸化カリウムを触媒とし、圧力1.5kg/cm3、温度130℃の条件にて、エチレンオキサイド440g(10モル)を付加させて、次式で表される化合物(本発明品11)が99%含まれる粗製物(混合物)が得られた。この反応時にアリル基は、1-プロペニル基に定量的に変化した。
撹拌器、温度計及び窒素導入管を備えた反応容器に、上記合成例11で得られた化合物(本発明品11)742g(1モル)を仕込み、反応装置内の雰囲気を窒素で置換後、温度120℃の条件にてスルファミン酸97g(1モル)を反応させた後、精製して次式で表される化合物(本発明品13)を得た。
撹拌機および温度計を備えた反応容器に合成例11で得られた化合物(本発明品11)742g(1モル)仕込んだ。モノクロル酢酸ナトリウム128g(1.1モル)及び水酸化ナトリウム44g(1.1モル)を40℃にした反応容器内に3時間をかけて添加した。その後、40℃にて撹拌しながら17時間反応させた後、精製して次式で表される化合物(本発明品14)を得た。
撹拌機および温度計を備えた反応容器に合成例11で得られた化合物(本発明品11)742g(1モル)仕込んだ。次に撹拌しながら無水リン酸94g(0.33モル)を仕込み、撹拌しながら80℃で5時間リン酸化を行った後、苛性ソーダで中和して、次式で表される化合物(本発明品15)を得た。本組成物をNMRにて確認したところ、モノエステル/ジエステルの比率は56/44であった。
原料をスチレン化メチルフェノールからメチルスチレン化メチルフェノールに変更し、アリルクロライドの量を91g(1.2モル)から105g(1.4モル)、エチレンオキサイドの量を440g(10モル)から880g(20モル)に増やした他は、合成例11及び合成例13に準じて次式で表される化合物(本発明品16)を得た。
上記合成例により得られた乳化重合剤を使用して、下記使用例に記載した通り、乳化重合を行い、得られたポリマーディスパージョン及びポリマーフィルムについて測定及び評価を行った。用いた測定・評価方法は以下の通りである。
ポリマーディスパージョンを80メッシュの金網で乳化重合工程中に生成した凝集物をろ過して、ろ過残渣を水洗後、105℃で2時間乾燥し、その質量をディスパージョンの固形分に対する質量%で示した。なお、本測定において凝集物量が小さい程、乳化重合工程における重合安定性が高いことを意味する。
ポリマーディスパージョンの一部を取り、動的光散乱式粒度分布測定装置(日機装株式会社製、製品名MICROTRAC UPA9340)にて粒子径を測定した。
ポリマーディスパージョンの50gを秤取し、マーロン型試験機にて荷重10kg、回転数1,000rpmで5分間処理し、生成した凝集物を80メッシュの金網でろ過し、残渣を水洗後、105℃で2時間乾燥し、その質量をディスパージョンの固形分に対する質量%で示した。なお、本測定において凝集物量が小さいほど、高せん断条件下におけるポリマーディスパージョンの安定性が高いことを意味する。
ポリマーディスパージョンを水で2倍に希釈し、100mlネスラー管に30ml入れ、30回倒立させてから静置5分後における泡の量(ml)を測定した。
ポリマーディスパージョンを市販のガラス板に膜厚120μm(dry)になるように塗布し、20℃×65%RHの雰囲気下で24時間乾燥させたものを25℃のイオン交換水に浸漬し、16ポイントの印刷文字の上にガラス板を置き、ポリマーフィルムを通して文字を透かして見たときに、その文字が判別できなくなるまでの日数を測定した。その結果を、以下の基準に基づいて評価した。
◎:21日以上
○:11日~20日
△:1日~10日
×:1日未満
5cm幅に切ったPETフィルム上に使用例2において得られたポリマーディスパージョンを25μm(dry)の厚さに塗工し、熱処理した後SUS板に貼り付け、ローラ圧着した。接着面が5cm×5cmとなるようにフィルムを剥がし、フィルムの端に200gの重りを吊り下げて剥がれるまでの時間(秒)を測定した。その結果を、以下の基準に基づいて評価した。
○:900秒以上
△:300秒以上~900秒未満
×:300秒未満
得られたポリマーディスパージョンを市販のガラス板に膜厚120μm(dry)になるように塗布し、20℃×65%RHの雰囲気下で24時間乾燥させ、ポリマーフィルムをガラス板から注意深く剥がし、そのポリマーフィルムを5cm×5cmの大きさに切り出し、ポリマーフィルム質量(初期質量)を測定した。次いで、これを25℃のイオン交換水に浸漬し、24時間後、水からポリマーフィルム取り出し、表面の水分を清浄なろ紙で軽くふき取った後、ポリマーフィルム質量(浸漬後質量)を測定し、次の計算式にてフィルムの吸水率を求めた。
吸水率(質量%)={(浸漬後のポリマーフィルム質量-浸漬前のポリマーフィルム質量)/浸漬前のポリマーフィルム質量}×100
モノマーとしてスチレン123.75g、アクリル酸ブチル123.75g、アクリル酸2.5gを、表1に示した本発明品又は比較品の乳化剤5.0g及びイオン交換水105gをホモミキサーで混合して混合モノマー乳濁液を調製した。これとは別に、撹拌機、還流冷却器、温度計、窒素導入管及び滴下漏斗を備えた反応器に、イオン交換水122g、炭酸水素ナトリウム0.25gを仕込んだ。滴下漏斗に上記事前調製した混合モノマー乳濁液のうち36gを仕込み、反応器に一括添加し、80℃に昇温させた。その後、15分間撹拌を継続した後に、重合開始剤として過硫酸アンモニウム0.5gをイオン交換水20gに溶解して加えて重合を開始させた。次いで、重合開始剤の添加15分後より3時間かけて、混合モノマー乳濁液の残りの324gを滴下して重合させた。さらに、続けて2時間熟成した後、冷却してアンモニア水でpHを8に調整して本発明の評価実験に供するポリマーディスパージョンを得た。
上記使用例1において、モノマー成分のうち、スチレンをアクリル酸2-エチルヘキシルに変更した以外は使用例1と同様の操作で乳化重合を行い、本発明の評価実験に供試するポリマーディスパージョンを得た。
モノマーとしてスチレン123.75g、アクリル酸ブチル123.75g、アクリル酸2.5gを、表3に示した本発明品又は比較品の乳化剤5.0g及びイオン交換水105gをホモミキサーで混合して混合モノマー乳濁液を調製した。これとは別に、撹拌機、還流冷却器、温度計、窒素導入管及び滴下漏斗を備えた反応器に、イオン交換水122g、炭酸水素ナトリウム0.25gを仕込んだ。滴下漏斗に上記事前調製した混合モノマー乳濁液のうち36gを仕込み、反応器に一括添加し、80℃に昇温させた。その後、15分間撹拌を継続した後に、重合開始剤として過硫酸アンモニウム0.5gをイオン交換水20gに溶解して加えて重合を開始させた。次いで、重合開始剤の添加15分後より3時間かけて、混合モノマー乳濁液の残りの324gを滴下して重合させた。さらに、続けて2時間熟成した後、冷却してアンモニア水でpHを8に調整して本発明の評価実験に供するポリマーディスパージョンを得た。
上記使用例1において、モノマー成分のうち、スチレンをアクリル酸2-エチルヘキシルに変更した以外は使用例1と同様の操作で乳化重合を行い、本発明の評価実験に供試するポリマーディスパージョンを得た。
Claims (3)
- 下記の一般式(I)で表される化合物を含有することを特徴とする乳化重合用乳化剤。
R0は炭素数1~4のアルキル基を示し、R1は以下に示す基から選択された1種又は2種の基を示し、式中、R2は水素又はメチル基を示し、
Dは下記化学式D-1又はD-2のいずれかで表される重合性の不飽和基を表し、これらの式中、R3は水素原子又はメチル基を表し、
m1は1~2の数を表し、m2は1~3の数を表し、m3は0又は1の数を示し、
Aは炭素数2~4のアルキレン基又は置換アルキレン基を表し、nはアルキレンオキシドの平均付加モル数を表し、0~1,000の範囲にある数を表し、
Xは水素原子、又は-(CH2)a-SO3M、-(CH2)b-COOM、-PO3M2、-P(Z)O2M、及び-CO-CH2-CH(SO3M)-COOMから選択されたアニオン性親水基を表し、これらの式中、a及びbはそれぞれ0~4の数を表し、Zは前記一般式(I)からXを除いた残基を表し、Mはそれぞれ、水素原子、アルカリ金属原子、アルカリ土類金属原子、アンモニウム残基、又はアルカノールアミン残基を表す。
- 前記一般式(I)において、m1が平均値として1<m1<1.5の範囲の数を示し、かつ化学式D-1及び化学式D-2によりそれぞれ表される基のモル比である(D-1)/(D-2)の値が2より大きいことを特徴とする、請求項1に記載の乳化重合用乳化剤。
- 前記一般式(I)において、Xは水素原子又はSO3Mを表し、ここでMは水素原子、アルカリ金属原子、アルカリ土類金属原子、アンモニウム残基、又はアルカノールアミン残基を表し、Aは炭素数2のアルキレン基を表すことを特徴とする、請求項1又は2に記載の乳化重合用乳化剤。
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