JPH0718011A - Emulsifier for emulsion polymerization - Google Patents
Emulsifier for emulsion polymerizationInfo
- Publication number
- JPH0718011A JPH0718011A JP18924193A JP18924193A JPH0718011A JP H0718011 A JPH0718011 A JP H0718011A JP 18924193 A JP18924193 A JP 18924193A JP 18924193 A JP18924193 A JP 18924193A JP H0718011 A JPH0718011 A JP H0718011A
- Authority
- JP
- Japan
- Prior art keywords
- group
- emulsion
- polymer
- emulsifier
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 42
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 125000002252 acyl group Chemical group 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229920001519 homopolymer Polymers 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229920001400 block copolymer Polymers 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 229920005604 random copolymer Polymers 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 17
- -1 polyoxyethylene nonylphenyl ether Polymers 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 229920006254 polymer film Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical group CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000007278 cyanoethylation reaction Methods 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002818 heptacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical group CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- VRYGRLBNIVQXMY-UHFFFAOYSA-M sodium;acetic acid;chloride Chemical compound [Na+].[Cl-].CC(O)=O VRYGRLBNIVQXMY-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、乳化重合用乳化剤に関
する。FIELD OF THE INVENTION The present invention relates to an emulsifier for emulsion polymerization.
【０００２】[0002]
【従来の技術】乳化重合用乳化剤としては、従来よりド
デシルベンゼンスルホン酸ナトリウム、ポリオキシエチ
レンノニルフェニルエーテル等のアニオン系界面活性剤
やノニオン系界面活性剤が利用されている。しかし、こ
れら乳化剤を用いたポリマーエマルションから得られた
ポリマーフィルムにあっては、使用した乳化剤が、遊離
の状態で前記ポリマーフィルム中に残留する。このた
め、該フィルムの耐水性、接着性が劣る等の問題点があ
った。As an emulsifying agent for emulsion polymerization, anionic surfactants such as sodium dodecylbenzene sulfonate and polyoxyethylene nonylphenyl ether and nonionic surfactants have been conventionally used. However, in the polymer film obtained from the polymer emulsion using these emulsifiers, the emulsifier used remains in the polymer film in a free state. Therefore, there have been problems such as poor water resistance and adhesiveness of the film.
【０００３】そこで、上記の問題点の改善策として、共
重合性の不飽和基を有する反応性乳化剤が数多く提案さ
れた。例えば、特公昭４６−１２４７２号、特開昭５４
−１４４３１号、特公昭４６−３４８９４号、特公昭５
６−２９６５７号、特開昭５１−３０２８５号、特公昭
４９−４６２９１号及び特開昭５６−１２７６９７号等
にはアニオン性の反応性界面活性剤が記載され、また、
特開昭５６−２８２０８号及び特開昭５０−９８４８４
号等には非イオン性の反応性界面活性剤につきそれぞれ
記載されていて、各種モノマーについて乳化重合が試み
られている。Therefore, many reactive emulsifiers having a copolymerizable unsaturated group have been proposed as measures for solving the above problems. For example, JP-B-46-12472 and JP-A-54
-14431, JP-B-46-34894, JP-B-5
6-29657, JP-A-51-30285, JP-B-49-46291 and JP-A-56-127697 describe anionic reactive surfactants.
JP-A-56-28208 and JP-A-50-98484
JP-A No. 2004-135242 describes nonionic reactive surfactants, and emulsion polymerization of various monomers has been attempted.
【０００４】しかし、非イオン性の反応性乳化剤は、乳
化重合時の安定性に問題があり、重合中の凝集物が多か
ったり、生成粒子が粗く、経時安定性が劣る等の問題点
を有していた。また硫酸エステル塩，スルホン酸塩型の
アニオン性の反応性乳化剤は、乳化重合時の安定性は割
合良好であるが、ポリマーエマルションから得られたポ
リマー又はポリマーフィルムは耐水性，耐熱性，接着性
において充分満足するものが得られていないのが実情で
ある。However, nonionic reactive emulsifiers have problems in stability during emulsion polymerization, and have problems such as a large number of aggregates during polymerization and coarse particles produced, resulting in poor stability over time. Was. Sulfate ester and sulfonate type anionic reactive emulsifiers have a good stability in emulsion polymerization, but polymers or polymer films obtained from polymer emulsions have water resistance, heat resistance and adhesiveness. The reality is that we have not been able to obtain satisfactory results in.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記の実情
に鑑みてなされたものであって、その目的は、乳化重合
時の安定性を良好なものにし得、しかも、ポリマーエマ
ルションから得られたポリマー及びポリマーフィルムの
耐水性，耐熱性および接着性が著しく改善できる改良さ
れた反応性乳化重合用乳化剤を提供するところにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to improve the stability during emulsion polymerization and to obtain the polymer emulsion. Another object of the present invention is to provide an improved emulsifier for reactive emulsion polymerization, which can remarkably improve the water resistance, heat resistance and adhesiveness of polymers and polymer films.
【０００６】[0006]
（１）発明の経過 本発明者らは鋭意研究を重ねた結果、アニオン性の親水
基としてエーテルカルボン酸又はその塩を有し、また不
飽和基の結合位置が乳化剤の疎水基部分であることが乳
化重合用乳化剤として適していることを見出し、本発明
に到達したものである。(1) Progress of the invention As a result of intensive studies, the inventors of the present invention have an ether carboxylic acid or a salt thereof as an anionic hydrophilic group, and the bonding position of the unsaturated group is a hydrophobic group portion of the emulsifier. Has been found to be suitable as an emulsifying agent for emulsion polymerization, and has arrived at the present invention.
【０００７】（２）発明の概要 以上の知見に基づき、本発明は、下記一般式（Ｉ）で表
わされる乳化重合用乳化剤（以下、「本発明乳化剤」と
もいう。）を要旨とするものである。(2) Outline of the Invention Based on the above findings, the present invention is based on an emulsifier for emulsion polymerization represented by the following general formula (I) (hereinafter, also referred to as "the emulsifier of the present invention"). is there.
【０００８】[0008]
【化４】 [Chemical 4]
【０００９】［式中、Ｒ1 は炭素数６〜３０の炭化水素
基もしくはアシル基である。Ｒ2 は水素原子またはメチ
ル基である。Ａは炭素数２〜４のアルキレン基または置
換アルキレン基である。ｎは０〜５０の整数、ｍは１〜
２００の整数であり、ｎ又はｍが２以上の場合、（Ａ
Ｏ）n 又は（ＡＯ）m は、下式（ｉ）で示される、１種
の繰返し単位からなるホモポリマー[In the formula, R 1 is a hydrocarbon group having 6 to 30 carbon atoms or an acyl group. R 2 is a hydrogen atom or a methyl group. A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group. n is an integer of 0 to 50, m is 1
Is an integer of 200, and when n or m is 2 or more, (A
O) n or (AO) m is a homopolymer consisting of one type of repeating unit represented by the following formula (i)
【００１０】[0010]
【化５】 [Chemical 5]
【００１１】であってもよいし、下式（ii）で示され
る、異なるＡ（Ａ1 ，Ａ2 …）を有する２種以上の繰返
し単位からなるブロックポリマーまたはランダムポリマ
ーOr a block polymer or a random polymer represented by the following formula (ii) consisting of two or more kinds of repeating units having different A (A 1 , A 2 ...)
【００１２】[0012]
【化６】 [Chemical 6]
【００１３】であってもよい。ｐは１または２であり、
Ｍは水素原子，アルカリ金属，アンモニウムイオンまた
はアルカノールアミン残基である。］以下、発明の構成
に関する主要な事項につき項分けして説明する。It may be p is 1 or 2,
M is a hydrogen atom, an alkali metal, an ammonium ion or an alkanolamine residue. The main items relating to the structure of the invention will be described below item by item.
【００１４】（３）置換基 上記一般式（Ｉ）の化合物において、置換基Ｒ1 は、炭
素数６〜３０の炭化水素基もしくはアシル基である。炭
化水素基としてはアルキル基、アルケニル基、アルキル
フェニル基、アラルキルフェニル基が挙げられ、アルキ
ル基としては、例えばヘキシル基，ヘプチル基，オクチ
ル基，ノニル基，デシル基，ウンデシル基，ドデシル
基，トリデシル基，テトラデシル基，ペンタデシル基，
ヘキサデシル基，ヘプタデシル基，オクタデシル基，ノ
ナデシル基，トリコシル基，ペンタコシル基，ヘプタコ
シル基等のアルキル基が挙げられる。(3) Substituent In the compound of the general formula (I), the substituent R 1 is a hydrocarbon group having 6 to 30 carbon atoms or an acyl group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkylphenyl group, and an aralkylphenyl group. Examples of the alkyl group include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecyl group. Group, tetradecyl group, pentadecyl group,
Examples thereof include alkyl groups such as hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, tricosyl group, pentacosyl group, and heptacosyl group.
【００１５】アルケニル基としては、例えば、ヘキセニ
ル基，ヘプテニル基，オクテニル基，ノネニル基，デセ
ニル基，ウンデセニル基，ドデセニル基，トリデセニル
基，テトラデセニル基，ペンタデセニル基，ヘキサデセ
ニル基，ヘプタデセニル基，オクタデセニル基等が例示
される。Examples of the alkenyl group include hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group and the like. It is illustrated.
【００１６】アルキルフェニル基としては、ブチルフェ
ニル，オクチルフェニル，ノニルフェニル，ドデシルフ
ェニル，ジノニルフェニル等が挙げられ、更にアラルキ
ルフェニル基としては、モノ（又はジ、トリ）スチレン
化フェニル基，モノ（又はジ、トリ）ベンジルフェニル
基，クミルフェニル基等が挙げられる。Examples of the alkylphenyl group include butylphenyl, octylphenyl, nonylphenyl, dodecylphenyl, dinonylphenyl and the like, and further examples of the aralkylphenyl group include mono (or di, tri) styrenated phenyl group and mono ( Alternatively, di, tri) benzylphenyl group, cumylphenyl group and the like can be mentioned.
【００１７】アシル基としてオクタノイル，ドデカノイ
ル，オクタデシノイル，オクタデセニノイル等が挙げら
れる。Ｒ2 は水素原子またはメチル基である。Examples of the acyl group include octanoyl, dodecanoyl, octadecinoyl, octadeceninoyl and the like. R 2 is a hydrogen atom or a methyl group.
【００１８】また、Ａは、炭素数２〜４のアルキレン基
または置換アルキレン基である。具体的には、アルキレ
ン基としてエチレン基，プロピレン基，ブチレン基，イ
ソブチレン基等であり、置換アルキレン基としては１，
２−ブチレンオキシド基，プロピレンオキシド基等であ
る。ｎは０〜５０の整数、ｍは１〜２００の整数であ
り、より好ましくはｎは０もしくは１〜２０、ｍは２〜
１００の範囲である。A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group. Specifically, the alkylene group is ethylene group, propylene group, butylene group, isobutylene group or the like, and the substituted alkylene group is 1,
2-butylene oxide group, propylene oxide group and the like. n is an integer of 0 to 50, m is an integer of 1 to 200, more preferably n is 0 or 1 to 20, and m is 2
The range is 100.
【００１９】前記ｎ又はｍが２以上の場合、式（Ｉ）に
おける（ＡＯ）n 又は（ＡＯ）m は、１種類の繰返し単
位からなるホモポリマー（前式（ｉ）参照）であっても
よいし、異なる置換基Ａ（Ａ１，Ａ２，Ａ３……）を有
する２種以上の繰返し単位からなるブロックポリマーま
たはランダムポリマー（前式（ii）参照）であってもよ
い。あるいは、ｎ又はｍが１である場合の化合物と、ｎ
又はｍが２以上の場合における（ＡＯ）n 又は（ＡＯ）
m がホモポリマー，ブロックポリマーあるいはランダム
ポリマーである化合物の中から２種以上を混合した混合
物であってもよい。When n or m is 2 or more, (AO) n or (AO) m in the formula (I) may be a homopolymer consisting of one kind of repeating unit (see the above formula (i)). Alternatively, it may be a block polymer or a random polymer (see the previous formula (ii)) composed of two or more kinds of repeating units having different substituents A (A1, A2, A3 ...). Alternatively, a compound where n or m is 1, and n
Or (AO) n or (AO) when m is 2 or more
It may be a mixture of two or more compounds selected from the compounds in which m is a homopolymer, a block polymer or a random polymer.
【００２０】又、Ｍは水素原子，アルカリ金属，アンモ
ニウムイオン又はアルカノールアミン残基である。アル
カリ金属は例えばナトリウム、カリウム、リチウム等
が、アルカノールアミン残基は例えばモノエタノールア
ミン、トリエタノールアミン、ジイソプロパノール残基
等が挙げられる。M is a hydrogen atom, alkali metal, ammonium ion or alkanolamine residue. Examples of the alkali metal include sodium, potassium and lithium, and examples of the alkanolamine residue include monoethanolamine, triethanolamine and diisopropanol residues.
【００２１】（４）合成 本発明の乳化重合用乳化剤を得るための反応条件は特に
限定されるものではなく、例えば、ノニルフェノールに
グリシジルメタクリレートを１モル反応させた後に、常
法に従ってアルキレンオキシドを付加した後、ヒドロキ
シル基を酸化するか、もしくは、モノハロゲン化酢酸を
反応させてカルボキシル化を行なうか、または、アクリ
ロニトリル，アクリル酸エステルを反応させ、アルカリ
でケン化を行ない、必要に応じてアルカリ性物質で中和
することにより製造できる。(4) Synthesis The reaction conditions for obtaining the emulsifier for emulsion polymerization of the present invention are not particularly limited. For example, after reacting 1 mol of nonylphenol with glycidyl methacrylate, alkylene oxide is added according to a conventional method. After that, oxidize the hydroxyl group, or react with monohalogenated acetic acid to carry out carboxylation, or react with acrylonitrile and acrylic acid ester and perform saponification with alkali. It can be produced by neutralizing with.
【００２２】（５）乳化重合用モノマー 本発明乳化剤を用いた乳化重合に適用されうるモノマー
としては各種のものを挙げることができ、例えば、アク
リル酸，アクリル酸メチル，アクリル酸ブチル，アクリ
ル酸２−エチルヘキシル，メタクリル酸メチル，アクリ
ロニトリル，アクリルアミド，アクリル酸ヒドロキシエ
チルエステル等のアクリル系モノマー，例えば、スチレ
ン，ジビニルベンゼン等の芳香族系モノマー，酢酸ビニ
ル等のビニルエステル系モノマー，塩化ビニル，塩化ビ
ニリデン等のハロゲン化オレフィン系モノマー，ブタジ
エン，イソプレン，クロロプレン等の共役ジオレフィン
系モノマー等の他、エチレン，無水マレイン酸，マレイ
ン酸メチル等がある。本発明の乳化剤は、上記モノマー
の１種または２種以上の乳化重合または懸濁重合に利用
できる。(5) Emulsion Polymerization Monomer Various monomers can be used as the monomer applicable to the emulsion polymerization using the emulsifier of the present invention. For example, acrylic acid, methyl acrylate, butyl acrylate, acrylic acid 2 -Acrylic monomers such as ethylhexyl, methyl methacrylate, acrylonitrile, acrylamide, hydroxyethyl acrylate, for example, aromatic monomers such as styrene and divinylbenzene, vinyl ester monomers such as vinyl acetate, vinyl chloride, vinylidene chloride, etc. In addition to halogenated olefinic monomers, conjugated diolefinic monomers such as butadiene, isoprene, chloroprene, etc., there are ethylene, maleic anhydride, methyl maleate and the like. The emulsifier of the present invention can be used for emulsion polymerization or suspension polymerization of one or more of the above monomers.
【００２３】（６）重合条件 本発明乳化剤を使用した乳化重合反応に使用される重合
開始剤は従来公知のものでよく、例えば、過酸化水素，
過硫酸カリウム，アゾビスイソブチロニトリル，ベンゾ
イルパーオキサイド等が利用される。また、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
ウム等が使用される。(6) Polymerization conditions The polymerization initiator used in the emulsion polymerization reaction using the emulsifier of the present invention may be a conventionally known one, for example, hydrogen peroxide,
Potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, etc. are used. As the polymerization accelerator, sodium hydrogen sulfite, ferrous ammonium sulfate, etc. are used.
【００２４】本発明乳化剤の使用量は、通常、全モノマ
ーに対して０．１〜２０重量％、より好ましくは、０．
２〜５．０重量％が適当である。なお、所望により、他
種乳化剤または保護コロイド剤を併用してもよい。The amount of the emulsifier of the present invention to be used is usually 0.1 to 20% by weight, more preferably 0.
2 to 5.0% by weight is suitable. If desired, other emulsifiers or protective colloid agents may be used in combination.
【００２５】本発明の乳化剤を添加して得られるポリマ
ーエマルションは、例えば接着剤，被覆剤，含浸補強剤
等として、木材，金属，紙，布，その他コンクリート等
に適用することができる。またエマルションあるいはラ
テックスから取り出したポリマーは樹脂，ゴム，ポリマ
ー改質剤等に使用することができる。The polymer emulsion obtained by adding the emulsifier of the present invention can be applied to wood, metal, paper, cloth, concrete and the like as an adhesive, a coating agent, an impregnating reinforcing agent and the like. The polymer taken out from the emulsion or latex can be used as a resin, a rubber, a polymer modifier and the like.
【００２６】[0026]
【作用】本発明の乳化重合用乳化剤は共重合性の二重結
合である（メタ）アクリル基を有しアニオン性の親水基
としてカルボン酸又はその塩であることが特徴である。
従来のスルホン酸塩又は硫酸エステル塩型の反応性乳化
剤と比べ、乳化重合により得られたエマルションから作
製したポリマー及びポリマーフィルムの耐熱着色性が優
れている。また、乳化重合後、無機塩もしくは酸を添加
し、ポリマーを取り出す場合、本発明乳化重合用乳化剤
はカルボン酸塩であるため、酸によりカルボン酸にな
り、ポリマーの凝集が非常に容易である。更にポリマー
凝集後の廃液には遊離の乳化剤がほとんど存在しないた
め廃水負荷が軽減出来る。The emulsifier for emulsion polymerization of the present invention is characterized in that it has a (meth) acrylic group which is a copolymerizable double bond and is a carboxylic acid or a salt thereof as an anionic hydrophilic group.
Compared with the conventional sulfonate or sulfate ester type reactive emulsifiers, the polymers and polymer films produced from emulsions obtained by emulsion polymerization have excellent heat resistance. When an inorganic salt or an acid is added after the emulsion polymerization and the polymer is taken out, the emulsifier for emulsion polymerization of the present invention is a carboxylic acid salt, so that the acid turns into a carboxylic acid, and the aggregation of the polymer is very easy. Furthermore, since the free liquid emulsifier hardly exists in the waste liquid after polymer coagulation, the waste water load can be reduced.
【００２７】[0027]
【実施例】以下、実施例および比較例により本発明の実
施態様および効果につき述べるが、例示は単に説明用の
ものであって、発明思想の限定または制限を意図したも
のではない。なお、文中「％」および「部」とあるのは
それぞれ重量基準を意味する。The embodiments and effects of the present invention will be described below with reference to Examples and Comparative Examples, but the examples are merely for the purpose of illustration and are not intended to limit or limit the inventive idea. In the text, "%" and "parts" mean weight basis.
【００２８】製造例１ オートクレーブにノニルフェノール２２０ｇ（１．０モ
ル）、触媒としてトリエチルアミン１．５ｇを仕込み、
次にグリシジルメタクリレート１４２ｇ（１．０モル）
を加え、１００℃にて５時間撹拌し、反応させた後、オ
ートクレーブ内を減圧し、トリエチルアミンを除去し
た。アルカリ触媒のもとで圧力１．５ｋｇ／ｃｍ2 、温
度８０℃の条件にて、エチレンオキシド４４０ｇ（１０
モル）を付加させて、ノニルフェノールグリシジルメタ
クリレート１モル、エチレンオキシド１０モル付加体を
得た（以下、「グリシジルメタクリレート」を単に［Ｇ
ＭＡ］、「エチレンオキシド」を単に［ＥＯ］ともい
う）。 Production Example 1 An autoclave was charged with 220 g (1.0 mol) of nonylphenol and 1.5 g of triethylamine as a catalyst.
Next, 142 g (1.0 mol) of glycidyl methacrylate
Was added, and the mixture was stirred at 100 ° C. for 5 hours to cause a reaction, and then the pressure inside the autoclave was reduced to remove triethylamine. At a pressure of 1.5 kg / cm 2 and a temperature of 80 ° C. under an alkaline catalyst, 440 g of ethylene oxide (10 g
1 mole of nonylphenol glycidyl methacrylate and 10 moles of ethylene oxide were added (hereinafter, "glycidyl methacrylate" is simply referred to as [G
MA], "ethylene oxide" is also simply referred to as [EO]).
【００２９】次に、撹拌機および温度計を備えた反応容
器に上記の反応組成物であるノニルフェノールＧＭＡ１
モルＥＯ１０モル付加体４０１ｇ（０．５モル）仕込
む。次に撹拌しながらモノクロール酢酸ナトリウム６
４．１ｇ（０．５５モル）を室温にて、３０分をかけて
仕込む。続いて水酸化ナトリウム２２ｇ（０．５５モ
ル）を４０℃にした反応容器内に３時間をかけて添加す
る。その後、４０℃にて１７時間反応させる。Next, the above reaction composition of nonylphenol GMA1 was placed in a reaction vessel equipped with a stirrer and a thermometer.
Mol EO 10 mol 401g (0.5 mol) of addition product is charged. Then, with stirring, monochloro sodium acetate 6
Charge 4.1 g (0.55 mol) at room temperature over 30 minutes. Then, 22 g (0.55 mol) of sodium hydroxide is added to the reaction vessel heated to 40 ° C. over 3 hours. Then, it is made to react at 40 degreeC for 17 hours.
【００３０】次に、１０％硫酸を５００ｍｌ加え、７５
℃に昇温し、撹拌後静置して水層を除去する。次に、油
層に塩化メチレン４００ｍｌ、水２００ｍｌを加え水洗
する。水洗を３回行なった後、油層の塩化メチレンを蒸
留により除去した。油層の残った反応組成物を４８％水
酸化ナトリウムでｐＨ８．０まで中和し、下記化７の本
発明乳化剤［Ａ］を得た。Next, add 500 ml of 10% sulfuric acid, and add 75
The temperature is raised to ℃, after stirring, the mixture is allowed to stand and the aqueous layer is removed. Next, 400 ml of methylene chloride and 200 ml of water are added to the oil layer and washed with water. After washing with water three times, methylene chloride in the oil layer was removed by distillation. The reaction composition remaining in the oil layer was neutralized to pH 8.0 with 48% sodium hydroxide to obtain the emulsifier [A] of the present invention represented by the following chemical formula 7.
【００３１】製造例２ また、ノニルフェノールＧＭＡ１モルＥＯ３０モル付加
体を同様の操作にて、末端水酸基のカルボキシル基化を
行ない、下記化８の本発明乳化剤［Ｂ］を得た。 Production Example 2 Further, the terminal hydroxyl group was converted to a carboxyl group by the same operation using a nonylphenol GMA 1 mol EO 30 mol adduct to obtain the emulsifier [B] of the present invention represented by the following chemical formula 8.
【００３２】[0032]
【化７】 [Chemical 7]
【００３３】[0033]
【化８】 [Chemical 8]
【００３４】製造例３ オートクレーブにジスチリルフェノール３００ｇ（１モ
ル）、触媒としてトリエチルアミン１．５ｇを仕込み、
次にグリシジルメタクリレート１４２ｇ（１．０モル）
を加え、１００℃にて５時間撹拌し、反応させた後、オ
ートクレーブ内を減圧し、トリエチルアミンを除去し
た。次にアルカリ触媒のもとで圧力１．５ｋｇ／ｃｍ
2 、温度１３０℃の条件にて、プロピレンオキシド５８
０ｇ（１０モル）を、次いでエチレンオキシド１３２０
ｇ（３０モル）をそれぞれ付加し、ジスチリルフェノー
ルグリシジルメタクリレート１モル、プロピレンオキシ
ド１０モル、エチレンオキシド３０モル付加体を得た。
この付加体２３４．２ｇ（０．１モル）を、撹拌機及び
温度計を備えた反応容器に仕込む。次に、撹拌を行ない
ながら、５０℃にてアクリロニトリル５．３（０．１モ
ル）を１時間で添加し、続いて温度を８０℃に昇温し、
１時間シアノエチル化反応を行なった。 Production Example 3 An autoclave was charged with 300 g (1 mol) of distyrylphenol and 1.5 g of triethylamine as a catalyst.
Next, 142 g (1.0 mol) of glycidyl methacrylate
Was added, and the mixture was stirred at 100 ° C. for 5 hours to cause a reaction, and then the pressure inside the autoclave was reduced to remove triethylamine. Next, pressure 1.5kg / cm under alkaline catalyst.
2 , propylene oxide 58 under conditions of temperature 130 ℃
0 g (10 mol) then ethylene oxide 1320
g (30 mol) was added to each to obtain an adduct of distyrylphenol glycidyl methacrylate (1 mol), propylene oxide (10 mol) and ethylene oxide (30 mol).
234.2 g (0.1 mol) of this adduct is charged into a reaction vessel equipped with a stirrer and a thermometer. Next, with stirring, acrylonitrile 5.3 (0.1 mol) was added at 50 ° C. over 1 hour, and then the temperature was raised to 80 ° C.,
The cyanoethylation reaction was carried out for 1 hour.
【００３５】次に、１０％塩酸２００ｍｌ、水２００ｍ
ｌを加え、９０℃に昇温し、３時間撹拌を行ないシアノ
基のケン化を行なった。その後、減圧脱水した後アセト
ン２００ｍｌを加え、濾過した後、濾液中のアセトンを
蒸留して除き、下記化９の本発明乳化剤［Ｃ］を得た。Next, 200 ml of 10% hydrochloric acid and 200 m of water
1 was added, the temperature was raised to 90 ° C., and the mixture was stirred for 3 hours to saponify the cyano group. Then, the mixture was dehydrated under reduced pressure, 200 ml of acetone was added, the mixture was filtered, and the acetone in the filtrate was distilled off to obtain an emulsifier [C] of the present invention represented by the following chemical formula 9.
【００３６】[0036]
【化９】 [Chemical 9]
【００３７】製造例４ 製造例１〜製造例３に準じ各乳化剤を製造し、本発明乳
化剤［Ｄ］〜［Ｉ］を得た（下記［化１０］参照）。 Production Example 4 Each emulsifier was produced according to Production Example 1 to Production Example 3 to obtain the emulsifiers [D] to [I] of the present invention (see [Chemical Formula 10] below).
【００３８】[0038]
【化１０】 [Chemical 10]
【００３９】使用例１ 撹拌機，還流冷却器，温度計および滴下漏斗を備えた反
応器に、イオン交換水２９４ｇと表１に示す本発明乳化
剤６ｇを仕込み、８０℃まで昇温させた。窒素ガスにて
水中の溶存酸素を除去した後、アクリル酸エチル２０ｇ
と過硫酸アンモニウム０．５ｇを加えて先行重合させ、
重合開始１０分後より、３時間をかけてアクリル酸エチ
ル１８０ｇを滴下、重合させてエマルションを得た。こ
のときの乳化重合の安定性、エマルションの機械安定
性，起泡性およびこのエマルションより製造したポリマ
ーフィルムの耐水性のテスト結果を表１に示した。ま
た、比較として表１に示す従来の乳化剤についても、同
様のテストを実施した。 Use Example 1 A reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel was charged with 294 g of ion-exchanged water and 6 g of the emulsifier of the present invention shown in Table 1 and heated to 80 ° C. After removing dissolved oxygen in water with nitrogen gas, ethyl acrylate 20 g
And 0.5 g of ammonium persulfate are added for pre-polymerization,
After 10 minutes from the start of the polymerization, 180 g of ethyl acrylate was added dropwise over 3 hours for polymerization to obtain an emulsion. Table 1 shows the results of the emulsion polymerization stability, the mechanical stability of the emulsion, the foamability, and the water resistance of the polymer film produced from this emulsion. In addition, the same test was performed for the conventional emulsifiers shown in Table 1 for comparison.
【００４０】[0040]
【表１】 [Table 1]
【００４１】使用例２ アクリル酸ブチル１００ｇ、スチレン１００ｇ、イオン
交換水２９０ｇ、過硫酸カリウム０．５ｇおよび表２に
示す本発明乳化剤１０ｇを混合して混合モノマー乳濁液
を調製し、窒素ガスにて溶存酸素を除去した。次に、撹
拌機，還流冷却器，温度計および滴下漏斗を備えた反応
器に上記混合モノマーの乳濁液を１００ｇ仕込み、８０
℃に昇温させて重合させた。続いて残りの混合モノマー
の乳濁液４００．５ｇを３時間かけて滴下し、重合を行
なわせ、エマルションを得た。USE EXAMPLE 2 100 g of butyl acrylate, 100 g of styrene, 290 g of ion-exchanged water, 0.5 g of potassium persulfate and 10 g of the emulsifier of the present invention shown in Table 2 were mixed to prepare a mixed monomer emulsion, which was mixed with nitrogen gas. Dissolved oxygen was removed. Next, 100 g of the above emulsion of mixed monomers was charged into a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, and
Polymerization was carried out by raising the temperature to ° C. Subsequently, 400.5 g of the remaining mixed monomer emulsion was added dropwise over 3 hours to carry out polymerization to obtain an emulsion.
【００４２】このときの乳化重合安定性、エマルション
の機械安定性，起泡性，エマルションより製造したポリ
マーフィルムの耐水性および接触角のテスト結果を表２
に示した。また、比較として表２に示す従来の乳化剤に
ついても同様のテストを実施した。The results of the emulsion polymerization stability, the mechanical stability of the emulsion, the foamability, and the water resistance and contact angle of the polymer film produced from the emulsion are shown in Table 2 below.
It was shown to. Also, for comparison, the same test was performed for the conventional emulsifiers shown in Table 2.
【００４３】[0043]
【表２】 [Table 2]
【００４４】使用例３ 撹拌機，還流冷却器，温度計および滴下漏斗を備えた反
応器に、イオン交換水２５０ｇおよび表３に示す本発明
乳化剤５ｇを仕込み、８０℃まで昇温させた。窒素ガス
にて水中の溶存酸素を除去した後、アクリル酸ブチル１
２５ｇとメタクリル酸メチル１２５ｇとを混ぜて得た混
合モノマー２５０ｇ中の２０ｇと、過硫酸アンモニウム
０．５ｇとを加えて先行重合させ、次に重合開始１０分
後より、３時間をかけて残りの混合モノマー２３０ｇを
滴下して重合させ、エマルションを得た。また、比較と
して表３に示した他の反応性乳化剤についても同様の操
作にてエマルションを調製した。 Use Example 3 To a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel were charged 250 g of ion-exchanged water and 5 g of the emulsifier of the present invention shown in Table 3, and the temperature was raised to 80 ° C. After removing dissolved oxygen in water with nitrogen gas, butyl acrylate 1
20 g of 250 g of a mixed monomer obtained by mixing 25 g and 125 g of methyl methacrylate and 0.5 g of ammonium persulfate were added to carry out a prepolymerization, and 10 minutes after the initiation of the polymerization, the remaining mixing was carried out for 3 hours. 230 g of the monomer was added dropwise and polymerized to obtain an emulsion. Further, for comparison, emulsions were prepared in the same manner for the other reactive emulsifiers shown in Table 3.
【００４５】このときの乳化重合安定性および得られた
エマルションについて、未重合の乳化剤の定量およびそ
のエマルションより作成したポリマーフィルムの接触
角，接着力及び耐水性を測定した結果を表３に示した。Regarding the emulsion polymerization stability at this time and the obtained emulsion, the amount of unpolymerized emulsifier was quantified, and the contact angle, adhesive strength and water resistance of the polymer film prepared from the emulsion were measured. .
【００４６】[0046]
【表３】 [Table 3]
【００４７】使用例４ 撹拌機，還流冷却器，温度計および滴下ロートを備えた
反応器に、イオン交換水２５０ｇおよび表４に示す本発
明乳化剤５ｇを仕込み、８０℃まで昇温させた。窒素ガ
スにて水中の溶存酸素を除去した後、メタクリル酸メチ
ル２００ｇとアクリル酸メチル５０ｇとを混ぜて得た混
合モノマー２５０ｇ中の２０ｇと過硫酸カリウム０．５
ｇとを加えて先行重合させ、次に重合開始１０分後よ
り、３時間をかけて残りの混合モノマー２３０ｇを滴下
して重合させ、滴下終了後８０℃にて１時間熟成を行な
いエマルションを得た。次に硫酸１％、塩化カルシウム
２％を含む水溶液５００ｍｌの中に、上記エマルション
１００ｇを加え、撹拌しポリマーを凝集沈殿させる。 Use Example 4 In a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 250 g of ion-exchanged water and 5 g of the emulsifier of the present invention shown in Table 4 were charged and the temperature was raised to 80 ° C. After removing dissolved oxygen in water with nitrogen gas, 20 g in 250 g of a mixed monomer obtained by mixing 200 g of methyl methacrylate and 50 g of methyl acrylate and 0.5 g of potassium persulfate.
Then, after 10 minutes from the start of the polymerization, 230 g of the remaining mixed monomer is added dropwise to polymerize, and after the completion of the addition, aging is carried out at 80 ° C. for 1 hour to obtain an emulsion. It was Next, 100 g of the above emulsion is added to 500 ml of an aqueous solution containing 1% of sulfuric acid and 2% of calcium chloride and stirred to cause the polymer to coagulate and precipitate.
【００４８】この沈殿物を濾別回収し、乾燥して、ポリ
マー粉末を得た。このポリマーの耐熱着色性を調べるた
め、２３０℃に調整した熱風恒温器に１時間入れ、取り
出し冷却後、ポリマーの着色を調べた。その結果を表４
に示した。また比較として表４に示す従来の乳化剤につ
いても、同様のテストを実施した。The precipitate was collected by filtration and dried to obtain a polymer powder. In order to examine the heat-resistant coloring property of this polymer, it was put in a hot air thermostat adjusted to 230 ° C. for 1 hour, taken out and cooled, and then the coloring of the polymer was examined. The results are shown in Table 4.
It was shown to. For comparison, the same test was performed for the conventional emulsifiers shown in Table 4.
【００４９】[0049]
【表４】 [Table 4]
【００５０】[0050]
【発明の効果】以上説明したとおり、本発明により、乳
化重合時における安定性を良好にし得、しかも、ポリマ
ーエマルションから得られたポリマー及びポリマーフィ
ルムの耐水性，耐熱性および接着性を著しく改善できる
改良された反応性乳化重合用乳化剤を提供でき、関連産
業界の発展および需要者の利益に寄与する。As described above, according to the present invention, the stability during emulsion polymerization can be improved, and the water resistance, heat resistance and adhesiveness of the polymer and the polymer film obtained from the polymer emulsion can be remarkably improved. It is possible to provide an improved emulsifier for reactive emulsion polymerization, which contributes to the development of related industries and the interests of consumers.
Claims (1)
用乳化剤。 【化１】 ［式中、Ｒ1 は炭素数６〜３０の炭化水素基もしくはア
シル基である。Ｒ2 は水素原子またはメチル基である。
Ａは炭素数２〜４のアルキレン基または置換アルキレン
基。ｎは０〜５０の整数、ｍは１〜２００の整数であ
り、ｎ又はｍが２以上の場合、（ＡＯ）n 又は（ＡＯ）
m は、下式（ｉ）で示される、１種の繰返し単位からな
るホモポリマー 【化２】 であってもよいし、下式（ii）で示される、異なるＡ
（Ａ1 ，Ａ2 …）を有する２種以上の繰返し単位からな
るブロックポリマーまたはランダムポリマー 【化３】 であってもよい。ｐは１または２であり、Ｍは水素原
子，アルカリ金属，アンモニウムイオンまたはアルカノ
ールアミン残基である。］1. An emulsifying agent for emulsion polymerization represented by the following general formula (I). [Chemical 1] [In the formula, R 1 is a hydrocarbon group having 6 to 30 carbon atoms or an acyl group. R 2 is a hydrogen atom or a methyl group.
A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group. n is an integer of 0 to 50, m is an integer of 1 to 200, and when n or m is 2 or more, (AO) n or (AO)
m is a homopolymer represented by the following formula (i) and consisting of one kind of repeating unit: Or a different A represented by the following formula (ii)
Block polymer or random polymer composed of two or more kinds of repeating units having (A 1 , A 2 ...) May be p is 1 or 2, and M is a hydrogen atom, an alkali metal, an ammonium ion or an alkanolamine residue. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18924193A JPH0718011A (en) | 1993-06-30 | 1993-06-30 | Emulsifier for emulsion polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18924193A JPH0718011A (en) | 1993-06-30 | 1993-06-30 | Emulsifier for emulsion polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0718011A true JPH0718011A (en) | 1995-01-20 |
Family
ID=16237983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18924193A Pending JPH0718011A (en) | 1993-06-30 | 1993-06-30 | Emulsifier for emulsion polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0718011A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005220325A (en) * | 2004-02-09 | 2005-08-18 | Nippon Shokubai Co Ltd | Method for suspension-polymerizing (meth)acrylate monomer |
-
1993
- 1993-06-30 JP JP18924193A patent/JPH0718011A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005220325A (en) * | 2004-02-09 | 2005-08-18 | Nippon Shokubai Co Ltd | Method for suspension-polymerizing (meth)acrylate monomer |
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