JP2007126540A - Emulsifier for emulsion polymerization, method for producing polymer emulsion, and the resultant polymer emulsion - Google Patents
Emulsifier for emulsion polymerization, method for producing polymer emulsion, and the resultant polymer emulsion Download PDFInfo
- Publication number
- JP2007126540A JP2007126540A JP2005319854A JP2005319854A JP2007126540A JP 2007126540 A JP2007126540 A JP 2007126540A JP 2005319854 A JP2005319854 A JP 2005319854A JP 2005319854 A JP2005319854 A JP 2005319854A JP 2007126540 A JP2007126540 A JP 2007126540A
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- Prior art keywords
- emulsion
- emulsifier
- polymerization
- emulsion polymerization
- acid
- 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.)
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- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 59
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 56
- 239000000839 emulsion Substances 0.000 title claims description 55
- 229920000642 polymer Polymers 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 125000000129 anionic group Chemical group 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 5
- 238000006116 polymerization reaction Methods 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 2
- -1 sulfate ester Chemical class 0.000 description 52
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 150000005215 alkyl ethers Chemical class 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000021523 carboxylation Effects 0.000 description 4
- 238000006473 carboxylation reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical class CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 125000003118 aryl 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 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 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 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 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 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 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 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 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 239000000123 paper Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000223 polyglycerol Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002023 wood Substances 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-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
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 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
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 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
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Abstract
Description
本発明は乳化重合する際に用いられる乳化重合用乳化剤に関し、さらにそれを用いたポリマーエマルションの製造方法及びその製造方法により得られ得るポリマーエマルションに関する。 The present invention relates to an emulsifier for emulsion polymerization used in emulsion polymerization, and further relates to a method for producing a polymer emulsion using the same and a polymer emulsion obtainable by the production method.
従来、乳化重合用乳化剤としてはアルキルフェノールや脂肪族アルコールにアルキレンオキサイドを付加したエーテル型のポリオキシアルキレンアルキルフェノールエーテルやポリオキシアルキレンアルキルエーテルの非イオン型界面活性剤やこれを硫酸エステル化したアニオン型界面活性剤が単独あるいは併用で使用されてきた。 Conventionally, as an emulsifier for emulsion polymerization, an ether type polyoxyalkylene alkylphenol ether obtained by adding an alkylene oxide to an alkylphenol or an aliphatic alcohol, a nonionic surfactant of polyoxyalkylene alkyl ether, or an anionic type interface obtained by converting this to a sulfate ester. Activators have been used alone or in combination.
しかし、疎水基にアルキルフェノールを含む界面活性剤は、その生分解生成物の生態毒性が問題視されており、自然環境に排出された場合、生態系に悪影響を及ぼすことが問題となっている。よって、アルキルフェノールを疎水基に含まない脂肪族アルコール型の界面活性剤への代替が進められてきている。 However, the surfactant containing alkylphenol in the hydrophobic group is regarded as a problem of ecotoxicity of its biodegradation product, and when it is discharged into the natural environment, it has a problem of adversely affecting the ecosystem. Therefore, the substitution to the fatty alcohol type surfactant which does not contain alkylphenol in the hydrophobic group has been advanced.
また、ポリオキシアルキレンアルキルエーテルにおいては、乳化重合用乳化剤として性能不足である場合や水生生物毒性、皮膚刺激性などのため使用できる範囲が限られることがある。ポリオキシアルキレンアルキルエーテルの問題点として、未反応のエチレンオキサイドやプロピレンオキサイドが製品中に残存すること、副生成物として発がん性や刺激性の高い物質が発生することが挙げられる。例えば、合成時には有害なジオキサンが生成することや、アルキレンオキサイド鎖の酸化分解により有害性のアルデヒド類を生成することが知られており、シックハウス症候群やＶＯＣ問題が騒がれる近年、アルデヒド等を含む乳化剤をエマルションの製造に用いるのは好ましくない。 In addition, in the case of polyoxyalkylene alkyl ether, the usable range may be limited due to insufficient performance as an emulsifier for emulsion polymerization, aquatic toxicity, skin irritation and the like. Problems with polyoxyalkylene alkyl ethers include unreacted ethylene oxide and propylene oxide remaining in the product, and generation of highly carcinogenic and irritating substances as by-products. For example, it is known that harmful dioxane is generated at the time of synthesis, and that harmful aldehydes are generated by oxidative decomposition of alkylene oxide chains. Is not preferred for the production of emulsions.
これに対し、アルキレンオキサイドから誘導されないノニオン活性剤として、ポリグリセリン脂肪酸エステルを乳化重合用乳化剤として用いた技術が開示されている（特許文献１）。
上記ポリグリセリン脂肪酸エステルは、ポリオキシアルキレンアルキルエーテルのように有害なジオキサンやホルムアルデヒドが発生せず、またアルキレンオキサイドを出発原料としていないため高い安全性を持った乳化剤である。 The polyglycerin fatty acid ester is an emulsifier having high safety because it does not generate harmful dioxane or formaldehyde unlike polyoxyalkylene alkyl ether and does not use alkylene oxide as a starting material.
また、ポリグリセリン脂肪酸エステルはその性能を変化させる場合、脂肪酸の種類、グリセリンの重合度を変えることにより操作できる。またモノエステル体だけでなく、脂肪酸とポリグリセリンのモル比を任意に変えることによりポリエステル体を作ることが可能であるため、ポリオキシアルキレンアルキルエーテルに比べ幅広い性質を持たすことができる利点がある。 Moreover, when changing the performance, polyglycerol fatty acid ester can be operated by changing the kind of fatty acid and the polymerization degree of glycerol. Moreover, since it is possible to make a polyester body by arbitrarily changing not only the monoester body but also the molar ratio of fatty acid to polyglycerin, there is an advantage that it can have a wider range of properties than polyoxyalkylene alkyl ethers.
しかし、ポリグリセリン脂肪酸エステルはアルカリ溶液中では加水分解を起こしやすく、また乳化重合用乳化剤として用いた場合、重合時の安定性、ポリマーエマルションの化学安定性、ポリマーエマルションから得られたポリマーフィルムの性質は充分に満足し得るものではなく、多くの解決すべき問題点が残されている。 However, polyglycerol fatty acid esters are prone to hydrolysis in alkaline solutions, and when used as an emulsifier for emulsion polymerization, stability during polymerization, chemical stability of the polymer emulsion, and properties of the polymer film obtained from the polymer emulsion Is not fully satisfactory, and many problems to be solved remain.
そこで、本発明は、親水基としてポリオキシアルキレン鎖を含まず、重合時のエマルションの乳化安定性を良好なものとし、得られたポリマーエマルションの機械安定性や化学安定性が優れると共にポリマーエマルションから得られたポリマーフィルムの光沢性、接着性、耐熱性等の諸特性を優れたものとする乳化重合用乳化剤を提供することを目的とする。 Therefore, the present invention does not contain a polyoxyalkylene chain as a hydrophilic group, makes the emulsion stability during polymerization good, and provides excellent mechanical stability and chemical stability of the obtained polymer emulsion, as well as from the polymer emulsion. It is an object of the present invention to provide an emulsifier for emulsion polymerization that makes the obtained polymer film excellent in properties such as gloss, adhesion, and heat resistance.
本発明者らは、鋭意研究を重ねた結果、親水基部分としてポリグリセリン及びアニオン性親水基を持つ乳化重合用乳化剤が適していることを見出し、本発明に到達したものである。 As a result of extensive research, the present inventors have found that an emulsifier for emulsion polymerization having polyglycerin and an anionic hydrophilic group as the hydrophilic group portion is suitable, and has reached the present invention.
すなわち、本発明は、下記の一般式（１）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である。
（式中、Ｒは炭化水素基あり、ｎは１〜２００である。また、Ｘ１及びＸ２のうち少なくとも一つはアニオン性親水基であり、残りのＸ１及びＸ２は水素原子又は炭化水素基である。） (In the formula, R is a hydrocarbon group and n is 1 to 200. Further, at least one of X 1 and X 2 is an anionic hydrophilic group, and the remaining X 1 and X 2 are hydrogen atoms or It is a hydrocarbon group.)
本発明の乳化重合用乳化剤は、前記一般式（１）において、アニオン性親水基として、下記一般式（２）〜（６）のいずれかで表されるアニオン性親水基の１種以上を持つことができる。
（式中、Ｒ２は二塩基酸からカルボキシル基を除いた残基を表す。Ｍ及びＭ’は水素原子、金属原子、アンモニウムまたは炭化水素基を表し、ＭとＭ’は異なるものでも同一のものでも良い。）
また、本発明の乳化重合用乳化剤は、前記一般式（１）で表される化合物と、該化合物以外の他のノニオン界面活性剤及びアニオン界面活性剤の群から選ばれた少なくとも１種類の界面活性剤との混合物であっても良い。
(In the formula, R 2 represents a residue obtained by removing a carboxyl group from a dibasic acid. M and M ′ represent a hydrogen atom, a metal atom, an ammonium or a hydrocarbon group, and M and M ′ are the same even if they are different. Things can be used.)
Moreover, the emulsifier for emulsion polymerization of the present invention is at least one interface selected from the group consisting of the compound represented by the general formula (1) and other nonionic surfactants and anionic surfactants other than the compound. It may be a mixture with an activator.
本発明のポリマーエマルションの製造方法は、モノマーに対して、前記の乳化重合用乳化剤を０．１〜２０重量％の量で使用し、水性媒体中で前記に記載のモノマーを重合させる、または前記モノマー重合後のポリマーに添加することにある。 The method for producing a polymer emulsion of the present invention uses the above-mentioned emulsifier for emulsion polymerization in an amount of 0.1 to 20% by weight with respect to the monomer, and polymerizes the monomer described above in an aqueous medium, or It is to be added to the polymer after monomer polymerization.
そして、本発明のポリマーエマルションは、前記ポリマーの製造方法により得られるものである。 And the polymer emulsion of this invention is obtained by the manufacturing method of the said polymer.
本発明の乳化重合用乳化剤によれば、重合時の乳化安定性を良好なものとし、得られたポリマーエマルションの機械安定性や化学安定性が優れると共に、ポリマーエマルションを実際に使用した際のフィルム光沢性、接着性、耐熱性等の諸特性向上に優れた効果を発揮する。さらに、ジオキサンやアルデヒド類などの有害物質を大幅に低減したポリマーエマルションを得ることができる。 According to the emulsifier for emulsion polymerization of the present invention, the emulsion stability during polymerization is good, the mechanical stability and chemical stability of the obtained polymer emulsion are excellent, and the film when the polymer emulsion is actually used It exhibits excellent effects in improving various properties such as gloss, adhesion, and heat resistance. Furthermore, a polymer emulsion in which harmful substances such as dioxane and aldehydes are greatly reduced can be obtained.
以下、発明の実施の形態について項分けして説明する。 Hereinafter, the embodiments of the invention will be described separately.
上記一般式（１）の化合物において、式中Ｒは炭化水素基を表わす。炭化水素基としては例えば、アルキル基、アルケニル基、アリール基、シクロアルキル基、シクロアルケニル基等が挙げられる。 In the compound of the general formula (1), R represents a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and a cycloalkenyl group.
アルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、２級ブチル、ターシャリブチル、ペンチル、イソペンチル、２級ペンチル、ネオペンチル、ターシャリペンチル、ヘキシル、２級ヘキシル、ヘプチル、２級ヘプチル、オクチル、２−エチルヘキシル、２級オクチル、ノニル、２級ノニル、デシル、２級デシル、ウンデシル、２級ウンデシル、ドデシル、２級ドデシル、トリデシル、イソトリデシル、２級トリデシル、テトラデシル、２級テトラデシル、ヘキサデシル、２級ヘキサデシル、ステアリル、イコシル、ドコシル、テトラコシル、トリアコンチル、２−ブチルオクチル、２−ブチルデシル、２−ヘキシルオクチル、２−ヘキシルデシル、２−オクチルデシル、２−ヘキシルドデシル、２−オクチルドデシル、２−デシルテトラデシル、２−ドデシルヘキサデシル、２−ヘキサデシルオクタデシル、２−テトラデシルオクタデシル、モノメチル分枝−イソステアリル基等が挙げられる。 Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, secondary pentyl, neopentyl, tertiary pentyl, hexyl, secondary hexyl, heptyl, 2 Secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl , Hexadecyl, secondary hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, - octyldodecyl, 2-decyltetradecyl, 2-dodecyl-hexadecyl, 2-hexadecyl octadecyl, 2-tetradecyl-octadecyl, monomethyl branched - and the like isostearyl group.
アルケニル基としては、例えば、ビニル、アリル、プロペニル、ブテニル、イソブテニル、ペンテニル、イソペンテニル、ヘキセニル、ヘプテニル、オクテニル、ノネニル、デセニル、ウンデセニル、ドデセニル、テトラデセニル、オレイル等が挙げられる。 Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.
アリール基としては、例えば、フェニル、トルイル、キシリル、クメニル、メシチル、ベンジル、フェネチル、スチリル、シンナミル、ベンズヒドリル、トリチル、エチルフェニル、プロピルフェニル、ブチルフェニル、ペンチルフェニル、ヘキシルフェニル、ヘプチルフェニル、オクチルフェニル、ノニルフェニル、デシルフェニル、ウンデシルフェニル、ドデシルフェニル、フェニルフェニル、ベンジルフェニル、スチレン化フェニル、クミルフェニル、スチレン化クレシル、ベンジルキシリル、α−ナフチル、β−ナフチル基等が挙げられる。 As an aryl group, for example, phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, Nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, styrenated phenyl, cumylphenyl, styrenated cresyl, benzylxylyl, α-naphthyl, β-naphthyl groups and the like can be mentioned.
シクロアルキル基、シクロアルケニル基としては例えば、シクロペンチル、シクロヘキシル、シクロヘプチル、メチルシクロペンチル、メチルシクロヘキシル、メチルシクロヘプチル、シクロペンテニル、シクロヘキセニル、シクロヘプテニル、メチルシクロペンテニル、メチルシクロヘキセニル、メチルシクロヘプテニル基等が挙げられる。 Examples of the cycloalkyl group and cycloalkenyl group include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl group, and the like. Is mentioned.
また、Ｒは上記に記載の炭化水素基を２種類以上含んでいても良い。 R may contain two or more of the hydrocarbon groups described above.
一般式（１）において、Ｒは炭素数６から３０のアルキル基またはアルケニル基であることが好ましい。 In the general formula (1), R is preferably an alkyl group or alkenyl group having 6 to 30 carbon atoms.
通常、Ｒはアルコールから水酸基を除いた残基である。これらのアルコールは、天然由来のアルコール、または工業的に製造されるアルコールである。 Usually, R is a residue obtained by removing a hydroxyl group from alcohol. These alcohols are naturally occurring alcohols or industrially produced alcohols.
天然由来のアルコールとしては、オクチルアルコール、デシルアルコール、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、オレイルアルコールなどが挙げられる。 Naturally occurring alcohols include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and the like.
工業的に製造されるアルコールとしては、プロピレン或いはブテンまたはその混合物から誘導される高級オレフィンを経て、オキソ法により製造される分岐型飽和一級アルコールで、例えばイソノナノール、イソデカノール、イソウンデカノール、イソドデカノール、イソトリデカノールなどの他、市販品としてはエクソン・モービル社製のＥｘｘａｌシリーズがある。 Industrially produced alcohols are branched saturated primary alcohols produced by the oxo process via higher olefins derived from propylene or butene or mixtures thereof, such as isononanol, isodecanol, isoundecanol, isododecane. In addition to Knoll and Isotridecanol, there are Exxal series manufactured by Exxon Mobil as a commercial product.
ｎ−パラフィンやエチレンオリゴマーから誘導されるオレフィンを経て、オキソ法により製造される直鎖型と分岐型のアルコールの混合物として、Ｓｈｅｌｌl社製のネオドール（Ｎｅｏｄｏｌ）シリーズ、三菱化学社製のダイヤドール（Ｄｉａｄｏｌ）シリーズ、Ｓａｓｏｌ社製のサフォール（Ｓａｆｏｌ）シリーズやリアル（Ｌｉａｌ）シリーズが使用できる。 As a mixture of linear and branched alcohols produced by the oxo process via olefins derived from n-paraffins and ethylene oligomers, the Neodol series from Shelll, the diamond dolls from Mitsubishi Chemical ( Diadol series, Sasol series made by Sasol, and Real series can be used.
また、ゲルベ反応によるアルコールの２量化によって得られるゲルベアルコールには、２−エチル−1−ヘキサノール、２−ブチル−１−ヘキサノール、２−エチル−１−ヘプタノール、２−プロピル−１−オクタノール、２−プロピル−１−ヘプタノール、４−メチル−２−プロピル−１−ヘキサノール、２−プロピル−５−メチル−１−ヘキサノールなどがあり、またはパラフィンを空気酸化して製造され、水酸基が炭素鎖の末端以外へランダムに結合しているセカンダリーアルコールなどがある。 In addition, Gerve alcohol obtained by dimerization of alcohol by Gerbe reaction includes 2-ethyl-1-hexanol, 2-butyl-1-hexanol, 2-ethyl-1-heptanol, 2-propyl-1-octanol, 2 -Propyl-1-heptanol, 4-methyl-2-propyl-1-hexanol, 2-propyl-5-methyl-1-hexanol, etc., or produced by air oxidation of paraffin, and the hydroxyl group is the terminal of the carbon chain There are secondary alcohols that are randomly bound to the other.
また、これらのアルコールを２種類以上配合して使用することも可能である。 Moreover, it is also possible to mix and use two or more of these alcohols.
Ｘ１及びＸ２のうち少なくとも一つはアニオン性親水基であり、残りのＸ１及びＸ２は水素原子又は上記に記載の炭化水素基である。 At least one of X 1 and X 2 is an anionic hydrophilic group, and the remaining X 1 and X 2 are a hydrogen atom or the hydrocarbon group described above.
前記アニオン性親水基としては、下記の一般式（２）〜（６）で表される、サルフェート基（式２）、ホスフェート基（式３）、カルボキシレート基（式４又は５）、スルホサクシネート基（式６）が挙げられる。
式（２）〜（６）中、Ｒ２は二塩基酸からカルボキシル基を除いた残基を表す。Ｍ及びＭ’は水素原子、金属原子、アンモニウムまたは炭化水素基を表し、ＭとＭ’は異なるものでも同一のものでも良い。 In formulas (2) to (6), R 2 represents a residue obtained by removing a carboxyl group from a dibasic acid. M and M ′ represent a hydrogen atom, a metal atom, ammonium or a hydrocarbon group, and M and M ′ may be different or the same.
Ｒ２は、二塩基酸からカルボキシル基を除いた残基である。このような二塩基酸としては、例えばシュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸等の飽和脂肪族ジカルボン酸；シクロペンタンジカルボン酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸等の飽和脂環族ジカルボン酸；フタル酸、イソフタル酸、テレフタル酸、トリレンジカルボン酸、キシリレンジカルボン酸等の芳香族ジカルボン酸；マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸等の不飽和脂肪族ジカルボン酸；テトラヒドロフタル酸、メチルテトラヒドロフタル酸、ナジック酸（エンドメチレンテトラヒドロフタル酸）、メチルナジック酸、メチルブテニルテトラヒドロフタル酸、メチルペンテニルテトラヒドロフタル酸等の不飽和脂環族ジカルボン酸等が挙げられる。 R 2 is a residue obtained by removing a carboxyl group from a dibasic acid. Examples of such dibasic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecane Saturated aliphatic dicarboxylic acids such as diacids; saturated alicyclic dicarboxylic acids such as cyclopentanedicarboxylic acid, hexahydrophthalic acid and methylhexahydrophthalic acid; phthalic acid, isophthalic acid, terephthalic acid, tolylene dicarboxylic acid, xylylene diene Aromatic dicarboxylic acids such as carboxylic acids; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; tetrahydrophthalic acid, methyltetrahydrophthalic acid, nadic acid (endomethylenetetrahydrophthalic acid) , Methyl nadic acid, methylbutenyltetrahy Rofutaru acid, and unsaturated alicyclic dicarboxylic acids such as methyl pentenyl tetrahydrophthalic acid.
また、Ｍ及びＭ’は水素原子、金属原子、アンモニウム又は炭化水素基を表す。金属原子としては例えば、リチウム、ナトリウム、カリウム等のアルカリ金属原子、マグネシウム、カルシウム等のアルカリ土類金属原子（但し、アルカリ土類金属原子は通常２価であるから、１／２）等が挙げられる。アンモニウムとしては、例えば、アンモニア、メチルアミン、ジメチルアミン、エチルアミン、ジエチルアミン、（イソ）プロピルアミン、ジ（イソ）プロピルアミン、モノエタノールアミン、Ｎ−メチルモノエタノールアミン、Ｎ−エチルモノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノプロパノールアミン、ジプロパノールアミン、トリプロパノールアミン、２−アミノ−２−メチル−１，３−プロパンジオール、アミノエチルエタノールアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシプロピル）エチレンジアミン等のアンモニウムが挙げられる。炭化水素基としては上記に記載のものが挙げられる。また、Ｍ及びＭ’は異なるものでも同一のものでも良く、上記記載のものを２種類以上含んでいても良い。 M and M ′ each represents a hydrogen atom, a metal atom, ammonium or a hydrocarbon group. Examples of the metal atom include alkali metal atoms such as lithium, sodium and potassium, alkaline earth metal atoms such as magnesium and calcium (however, since alkaline earth metal atoms are usually divalent, 1/2), etc. It is done. Examples of ammonium include ammonia, methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine, di (iso) propylamine, monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, diethanolamine. , Triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol, aminoethylethanolamine, N, N, N ′, N′-tetrakis (2 -Ammonium such as hydroxypropyl) ethylenediamine. Examples of the hydrocarbon group include those described above. M and M ′ may be different or the same, and may contain two or more of the above-described ones.
一般式（１）において、Ｘ１及びＸ２は上記に記載のアニオン性親水基を２種類以上含んでいても良い。 In the general formula (1), X 1 and X 2 may contain two or more types of the anionic hydrophilic groups described above.
また、一般式（１）において、ｎは１〜２００で、好ましくは１〜６０である。 Moreover, in General formula (1), n is 1-200, Preferably it is 1-60.
また、一般式（１）のポリグリセリン部分が直鎖状に繋がっていても良く、図１に示すようにポリグリセリン部分が樹状に繋がっているものでも良い。 Moreover, the polyglycerin part of General formula (1) may be connected with linear form, and as shown in FIG. 1, the polyglycerin part may be connected with dendritic form.
本発明の乳化重合用乳化剤は、炭化水素基部分とポリグリセリン部分のモル比が１：１〜５：１、アニオン性親水基部分とポリグリセリン部分のモル比が１：１〜５：１、で含まれているのが有利である。 In the emulsifier for emulsion polymerization of the present invention, the molar ratio of the hydrocarbon group part to the polyglycerin part is 1: 1 to 5: 1, the molar ratio of the anionic hydrophilic group part to the polyglycerin part is 1: 1 to 5: 1, Is advantageously included.
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、高級アルコールとグリシドールを反応させ、得られた反応組成物のポリグリセリン部分に種々のアニオン性親水基を導入して本発明の乳化重合用乳化剤を得ることができる。また、必要に応じ公知の方法で精製を行っても良い。 The reaction conditions for obtaining the emulsifier for emulsion polymerization of the present invention are not particularly limited. For example, a higher alcohol and glycidol are reacted, and various anionic hydrophilic groups are added to the polyglycerin portion of the obtained reaction composition. It can introduce | transduce and can obtain the emulsifier for emulsion polymerization of this invention. Moreover, you may refine | purify by a well-known method as needed.
高級アルコールへのポリグリセリンの導入は、ポリグリセリンアルキルエーテルの公知の製造方法を適用することにより可能である。ポリグリセリンアルキルエーテルの製造方法は、例えば、特開２００１−１１４７２０号公報、特開２０００−３８３６５号公報、特開平９−１８８７５５号公報、特開平６−２９３６８８号公報において開示されている方法によることができる。 Introduction of polyglycerin into higher alcohol is possible by applying a known production method of polyglycerin alkyl ether. The production method of polyglycerin alkyl ether is, for example, according to the method disclosed in JP 2001-114720 A, JP 2000-38365 A, JP 9-188755 A, JP 6-293688 A. Can do.
また、ポリグリセリン部分へのアニオン性基の導入は公知の方法を用いて行うことができる。例えば、一般式（２）のアニオン性親水基を導入するには、スルファミン酸、クロロスルホン酸、無水硫酸、または硫酸を用い硫酸エステル化することにより得ることができる。一般式（３）のアニオン性親水基を導入するには、五酸化二リンまたはポリリン酸を用いリン酸エステル化することにより得ることができる。一般式（４）のアニオン性親水基を導入するには、モノハロゲン低級カルボン酸（モノクロル酢酸、モノブロムプロピオン酸等）を用いエーテルカルボキシル化することにより得ることができる。一般式（５）のアニオン性親水基を導入するには、二塩基酸（無水物である方が好ましい）を用いてエステルカルボキシル化することにより得ることができる。また、一般式（６）のアニオン性親水基を導入するには、無水マレイン酸でエステルカルボキシル化した後、亜硫酸ナトリウムでスルホン化することにより得ることができる。 The introduction of an anionic group into the polyglycerin moiety can be performed using a known method. For example, in order to introduce the anionic hydrophilic group of the general formula (2), it can be obtained by sulfate formation using sulfamic acid, chlorosulfonic acid, sulfuric anhydride, or sulfuric acid. In order to introduce the anionic hydrophilic group of the general formula (3), it can be obtained by phosphoric esterification using diphosphorus pentoxide or polyphosphoric acid. The anionic hydrophilic group of the general formula (4) can be introduced by ether carboxylation using a monohalogen lower carboxylic acid (monochloroacetic acid, monobromopropionic acid, etc.). In order to introduce the anionic hydrophilic group of the general formula (5), it can be obtained by ester carboxylation using a dibasic acid (preferably an anhydride). The anionic hydrophilic group of the general formula (6) can be introduced by ester carboxylation with maleic anhydride and then sulfonation with sodium sulfite.
［乳化重合用モノマー］
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モノマー、ブタジエン、イソプレン、クロロプレン等の共役系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。
[Emulsion polymerization monomer]
Examples of the monomer that can be applied to the emulsion polymerization using the emulsifier for emulsion polymerization of the present invention include various monomers such as acrylic acid, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. Acrylic monomers such as acrylonitrile, acrylamide, and acrylic acid hydroxy ester, aromatic monomers such as styrene and divinylbenzene, vinyl ester monomers such as vinyl acetate, halogenated olefin monomers such as vinyl chloride and vinylidene chloride, butadiene, In addition to conjugated diolefin monomers such as isoprene and chloroprene, 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.
［重合条件］
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。
[Polymerization conditions]
The polymerization initiator used in the emulsion polymerization reaction using the emulsifier for emulsion polymerization of the present invention may be a conventionally known one, such as hydrogen peroxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, etc. Available. As the polymerization accelerator, sodium bisulfite, ferrous ammonium sulfate, and the like can be used. Further, as a chain transfer agent, mercaptans such as α-methylstyrene dimer, n-butyl mercaptan, t-dodecyl mercaptan, halogenated hydrocarbons such as carbon tetrachloride and carbon tetrabromide may be used.
本発明の乳化重合用乳化剤の使用量は、通常、全モノマーに対して０．１〜２０．０％が適当である。なお、より好ましくは、０．２〜１０．０％が適当である。 The use amount of the emulsifier for emulsion polymerization of the present invention is usually suitably 0.1 to 20.0% with respect to all monomers. In addition, 0.2 to 10.0% is more preferable.
本発明の乳化重合用乳化剤は、それ単独でも乳化重合は良好に完結しうるが、さらに他のアニオン界面活性剤又は／及びノニオン界面活性剤を併用してもよく、これにより乳化重合時の重合安定性が向上し、また後工程における処理特性を向上させることができる。 かかるアニオン界面活性剤、及びノニオン界面活性剤としては特に限定されないが、例えば、アニオン界面活性剤としては、脂肪酸セッケン、ロジン酸セッケン、アルキルスルホン酸塩、アルキルアリールスルホン酸塩、アルキルスルホコハク酸塩、ポリオキシアルキレンアルキル硫酸塩、ポリオキシアルキレンアリール硫酸塩などが挙げられ、ノニオン界面活性剤としては、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシアルキレンアルキルエーテル、ポリグリセリンアルキルエーテル、アルキルポリグルコシド、ポリグリセリン脂肪酸エステル、ポリオキシアルキレン脂肪酸エステル、ソルビタン脂肪酸エステルなどが挙げられる。 The emulsifier for emulsion polymerization of the present invention alone can complete the emulsion polymerization satisfactorily. However, other anionic surfactants and / or nonionic surfactants may be used in combination, whereby polymerization during emulsion polymerization is performed. The stability can be improved and the processing characteristics in the subsequent process can be improved. The anionic surfactant and the nonionic surfactant are not particularly limited. Polyoxyalkylene alkyl sulfate, polyoxyalkylene aryl sulfate, and the like. Nonionic surfactants include polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyglycerin alkyl ether, alkyl polyglucoside, polyglycerin fatty acid. Examples include esters, polyoxyalkylene fatty acid esters, sorbitan fatty acid esters, and the like.
これら他の界面活性剤の使用量としては、本発明の乳化重合用乳化剤１００部に対して、０．５〜１００重量部含まれることが好ましく、より好ましくは５〜６０重量部である。さらに好ましくは１０〜３０重量部である。 The amount of these other surfactants to be used is preferably 0.5 to 100 parts by weight, more preferably 5 to 60 parts by weight with respect to 100 parts by weight of the emulsifier for emulsion polymerization of the present invention. More preferably, it is 10-30 weight part.
また、乳化重合時の重合安定性を向上させる目的で公知の保護コロイド剤を併用することができる。併用できる保護コロイド剤としては、完全けん化ポリビニルアルコール（ＰＶＡ）、部分けん化ＰＶＡ、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、ポリアクリル酸、アラビアゴムなどがある。 Moreover, a well-known protective colloid agent can be used together in order to improve the polymerization stability at the time of emulsion polymerization. Examples of protective colloid agents that can be used in combination include fully saponified polyvinyl alcohol (PVA), partially saponified PVA, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyacrylic acid, and gum arabic.
本発明の乳化重合用乳化剤の他の使用方法としては、ポリマーエマルションの安定性を改善するために、重合終了後のポリマーに添加することができる。 As another method of using the emulsifier for emulsion polymerization of the present invention, it can be added to the polymer after the completion of polymerization in order to improve the stability of the polymer emulsion.
［作用、その他］
本発明の乳化重合用乳化剤によれば、重合時の乳化安定性を良好なものとし、得られたポリマーエマルションの機械安定性や化学安定性が優れると共に、ポリマーエマルションを実際に使用した際のフィルム光沢性、接着性、耐熱性等の諸特性向上に優れた効果を発揮する。さらに、ジオキサンやアルデヒド類などの有害物質を大幅に低減したポリマーエマルションを得ることができる。
[Action, other]
According to the emulsifier for emulsion polymerization of the present invention, the emulsion stability during polymerization is good, the mechanical stability and chemical stability of the obtained polymer emulsion are excellent, and the film when the polymer emulsion is actually used It exhibits excellent effects in improving various properties such as gloss, adhesion, and heat resistance. Furthermore, a polymer emulsion in which harmful substances such as dioxane and aldehydes are greatly reduced can be obtained.
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など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, other concrete, etc. as an adhesive, a coating agent, an impregnation reinforcing agent, and the like. Further, the polymer taken out from the emulsion or latex can be used as a resin, rubber, polymer modifier and the like.
以下、実施例および比較例に基づき本発明をより詳細に説明するが、これらの例により本発明はなんら限定されることはない。なお、文中「部」は特に記載がない限り質量基準である。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited at all by these examples. In the text, “part” is based on mass unless otherwise specified.
〈製造例１〉
撹拌機、窒素導入管、及び温度計を備えた反応器にイソトリデシルアルコールを２００部と触媒として水酸化ナトリウムを仕込み、１２０℃まで昇温させ減圧脱水した。次に１２０℃を保持したままグリシドール２９６部を１時間かけて滴下し、さらに２時間撹拌した。生成物に水を加え陽イオン交換樹脂および陰イオン交換樹脂を通過させ脱塩した後、減圧脱水して中間体Ａを得た。中間体Ａにスルファミン酸１００部を仕込み１２０℃で３時間反応させて、硫酸エステル化を行った。未反応スルファミン酸を除去して、本発明品の乳化重合用乳化剤Ａを得た。
<Production Example 1>
Into a reactor equipped with a stirrer, a nitrogen introduction tube, and a thermometer, 200 parts of isotridecyl alcohol and sodium hydroxide as a catalyst were charged, heated to 120 ° C. and dehydrated under reduced pressure. Next, 296 parts of glycidol was dropped over 1 hour while maintaining 120 ° C., and the mixture was further stirred for 2 hours. Water was added to the product to pass through a cation exchange resin and an anion exchange resin for desalting, followed by dehydration under reduced pressure to obtain Intermediate A. The intermediate A was charged with 100 parts of sulfamic acid and reacted at 120 ° C. for 3 hours to carry out sulfate esterification. Unreacted sulfamic acid was removed to obtain an emulsifier A for emulsion polymerization of the present invention.
〈製造例２〉
製造例１の方法に準じて、グリシドールを１１１０部とした以外は同様の条件で反応、精製して、グリセリンの付加、硫酸エステル化を行った後、モノエタノールアミンで中和して本発明品の乳化重合用乳化剤Ｂを得た。
<Production Example 2>
According to the method of Production Example 1, except that glycidol was changed to 1110 parts, the reaction and purification were performed under the same conditions, glycerin was added and sulfate esterified, and then neutralized with monoethanolamine. Emulsifier B for emulsion polymerization was obtained.
〈製造例３〉
撹拌機、窒素導入管、及び温度計を備えた反応器にラウリルアルコール１８６部と触媒として水酸化ナトリウムを仕込み、１２０℃まで昇温させ減圧脱水した。次に１２０℃を保持したままグリシドール２２２部を１時間かけて滴下し、さらに２時間撹拌した。生成物に硫酸を加え中和後、脱水し、析出物を濾別して中間体Ｃを得た。中間体Ｃにスルファミン酸１００部を仕込み１２０℃で３時間反応させて、硫酸エステル化を行った。未反応スルファミン酸を除去した後、イソプロピルアルコールに溶解して中和等量の水酸化ナトリウムを加えた後、減圧トッピングして本発明品の乳化重合用乳化剤Ｃを得た。
<Production Example 3>
Into a reactor equipped with a stirrer, a nitrogen introducing tube, and a thermometer, 186 parts of lauryl alcohol and sodium hydroxide as a catalyst were charged, heated to 120 ° C. and dehydrated under reduced pressure. Next, 222 parts of glycidol was added dropwise over 1 hour while maintaining 120 ° C., and the mixture was further stirred for 2 hours. Sulfuric acid was added to the product for neutralization, followed by dehydration, and the precipitate was filtered off to obtain Intermediate C. The intermediate C was charged with 100 parts of sulfamic acid and reacted at 120 ° C. for 3 hours to carry out sulfate esterification. After removing unreacted sulfamic acid, it was dissolved in isopropyl alcohol, neutralized equivalent amount of sodium hydroxide was added, and then topped under reduced pressure to obtain an emulsifier C for emulsion polymerization of the present invention.
〈製造例４〉
撹拌機、窒素導入管、及び温度計を備えた反応器にネオドール２３を１９２部と触媒として水酸化ナトリウムを仕込み、１２０℃まで昇温させ減圧脱水した。次に１２０℃を保持したままグリシドール７４０部を１時間かけて滴下し、さらに２時間撹拌した。生成物に水を加え陽イオン交換樹脂および陰イオン交換樹脂を通過させ脱塩した後、減圧脱水して中間体Ｄを得た。中間体Ｄに無水リン酸４５部を仕込み８０℃で３時間反応させて、リン酸エステル化して本発明品の乳化重合用乳化剤Ｄを得た。
<Production Example 4>
A reactor equipped with a stirrer, a nitrogen introduction tube, and a thermometer was charged with 192 parts of neodol 23 and sodium hydroxide as a catalyst, heated to 120 ° C. and dehydrated under reduced pressure. Next, 740 parts of glycidol was dripped over 1 hour, maintaining 120 degreeC, and also it stirred for 2 hours. Water was added to the product to pass through a cation exchange resin and an anion exchange resin for desalting, followed by dehydration under reduced pressure to obtain Intermediate D. Intermediate D was charged with 45 parts of anhydrous phosphoric acid and reacted at 80 ° C. for 3 hours to form a phosphoric ester to obtain an emulsifier D for emulsion polymerization of the present invention.
〈製造例５〉
撹拌機、窒素導入管、及び温度計を備えた反応器にラウリルアルコール１８６部と触媒として水酸化カリウムを仕込み、１２０℃まで昇温させ減圧脱水した。次に１２０℃を保持したままグリシドール２２２０部を１時間かけて滴下し、さらに２時間撹拌した。生成物に硫酸を加え中和後、脱水し、析出物を濾別して中間体Ｅを得た。中間体Ｅに無水マレイン酸１００部を仕込み８０℃で２時間反応させた後、無水亜硫酸ナトリウムによりスルホン化して本発明品の乳化重合用乳化剤Ｅを得た。
<Production Example 5>
A reactor equipped with a stirrer, a nitrogen introduction tube, and a thermometer was charged with 186 parts of lauryl alcohol and potassium hydroxide as a catalyst, heated to 120 ° C. and dehydrated under reduced pressure. Next, 2220 parts of glycidol was dropped over 1 hour while maintaining 120 ° C., and the mixture was further stirred for 2 hours. Sulfuric acid was added to the product for neutralization, followed by dehydration, and the precipitate was filtered off to obtain Intermediate E. The intermediate E was charged with 100 parts of maleic anhydride, reacted at 80 ° C. for 2 hours, and then sulfonated with anhydrous sodium sulfite to obtain an emulsifier E for emulsion polymerization of the present invention.
〈製造例６〉
撹拌機、窒素導入管、及び温度計を備えた反応器にＥｘｘａｌ ｌｌを１７２部と触媒として水酸化カリウムを仕込み、１２０℃まで昇温させ減圧脱水した。次に１２０℃を保持したまま１２０℃まで昇温させグリシドール４４４０部を１時間かけて滴下し、さらに２時間撹拌した。生成物に水を加え陽イオン交換樹脂および陰イオン交換樹脂を通過させ脱塩した後、減圧脱水して中間体Ｆを得た。中間体Ｆにモノクロル酢酸ナトリウム１１６部と触媒として水酸化ナトリウムを仕込み８０℃で３時間反応させてエーテルカルボキシル化した後、中和、精製して本発明品の乳化重合用乳化剤Ｆを得た。
<Production Example 6>
Into a reactor equipped with a stirrer, a nitrogen introduction tube, and a thermometer, 172 parts of Exxall ll and potassium hydroxide as a catalyst were charged, heated to 120 ° C. and dehydrated under reduced pressure. Next, the temperature was raised to 120 ° C. while maintaining 120 ° C., 4440 parts of glycidol was added dropwise over 1 hour, and the mixture was further stirred for 2 hours. Water was added to the product to pass through a cation exchange resin and an anion exchange resin for desalting, followed by dehydration under reduced pressure to obtain Intermediate F. The intermediate F was charged with 116 parts of sodium monochloroacetate and sodium hydroxide as a catalyst, reacted at 80 ° C. for 3 hours for ether carboxylation, then neutralized and purified to obtain an emulsifier F for emulsion polymerization of the present invention.
〈製造例７〉
製造例３の方法に準じて、ラウリルアルコールの代わりに２−プロピル−１−ヘプタノールを１５８部、またグリシドールを１４８部とした以外は同様の条件で反応、中和して本発明品の乳化重合用乳化剤Ｇを得た。
<Production Example 7>
In accordance with the method of Production Example 3, the reaction product was subjected to reaction and neutralization under the same conditions except that 158 parts of 2-propyl-1-heptanol and 148 parts of glycidol were used instead of lauryl alcohol, and emulsion polymerization of the product of the present invention. Emulsifier G for use was obtained.
〈製造例８〉
製造例１の方法に準じて、イソトリデシルアルコールの代わりにデシルアルコールを１５８部、またグリシドールを７４０部とした以外は同様の条件で反応して本発明品の乳化重合用乳化剤Ｈを得た。
<Production Example 8>
According to the method of Production Example 1, an emulsifier H for emulsion polymerization of the present invention was obtained by reacting under the same conditions except that 158 parts of decyl alcohol and 740 parts of glycidol were used instead of isotridecyl alcohol. .
〈製造例９〉
製造例４の方法に準じて、ネオドール２３の代わりにスチレン化フェノール（モノ体、ジ体、トリ体混合物）を３０５部、またグリシドールを１１１０部とした以外は同様の条件で反応して本発明品の乳化重合用乳化剤Ｉを得た。
<Production Example 9>
According to the method of Production Example 4, the present invention was reacted under the same conditions except that 305 parts of styrenated phenol (mono, di, and tri mixture) and 1110 parts of glycidol were used instead of neodol 23. An emulsifier I for emulsion polymerization was obtained.
〈実施例及び比較例〉
実施例及び比較例に用いた乳化重合用乳化剤は表１の通りである。
<Examples and Comparative Examples>
Table 1 shows emulsifiers for emulsion polymerization used in Examples and Comparative Examples.
〈使用例１〉
アクリル酸ブチル１００部、スチレン１００部、イオン交換水２９０部および乳化重合用乳化剤１０部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。次に攪拌機、還流冷却器、温度計および滴下漏斗を備えた反応器に、上記混合モノマー乳濁液を１００部仕込み、８０℃に昇温し、過硫酸カリウム０．５部を加えて先行重合させた。次いで、重合開始１０分後より残りの混合モノマー乳濁液４００部を３時間かけて滴下して重合させた。さらに、続けて重合温度にて２時間熟成した後、冷却してポリマーエマルションを得た。使用した乳化重合用乳化剤は表２に示す通りである。
<Usage example 1>
A mixed monomer emulsion was prepared by mixing 100 parts of butyl acrylate, 100 parts of styrene, 290 parts of ion-exchanged water and 10 parts of an emulsifier for emulsion polymerization, and dissolved oxygen was removed with nitrogen gas. Next, a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel was charged with 100 parts of the above mixed monomer emulsion, heated to 80 ° C., and 0.5 parts of potassium persulfate was added for prepolymerization. I let you. Subsequently, after 10 minutes from the start of polymerization, the remaining 400 parts of the mixed monomer emulsion was added dropwise over 3 hours for polymerization. Further, after aging for 2 hours at the polymerization temperature, the mixture was cooled to obtain a polymer emulsion. The emulsifiers for emulsion polymerization used are as shown in Table 2.
使用した乳化重合用乳化剤のジオキサン及びホルムアルデヒドの含有量及び、得られたポリマーエマルションについて、重合安定性、機械安定性、粒子径、フィルムの光沢性をそれぞれ評価した。評価方法は以下の通りである。結果は表２に示す。 The contents of dioxane and formaldehyde of the emulsifier for emulsion polymerization used, and the obtained polymer emulsion were evaluated for polymerization stability, mechanical stability, particle diameter, and gloss of the film, respectively. The evaluation method is as follows. The results are shown in Table 2.
［ジオキサン及びホルムアルデヒドの含有量］
乳化重合用乳化剤に含まれるジオキサンをＧＣ、ホルムアルデヒドをアセチルアセトン法を用い吸光光度法で定量を行った。結果、ジオキサン量が１ｐｐｍ未満：○、１〜１０ｐｐｍ：△、１０ｐｐｍ以上：×、ホルムアルデヒド量が１ｐｐｍ未満：○、１〜１０ｐｐｍ：△、１０ｐｐｍ以上：×、として示した。
[Contents of dioxane and formaldehyde]
The dioxane contained in the emulsifier for emulsion polymerization was determined by spectrophotometry using GC and formaldehyde using the acetylacetone method. As a result, the amount of dioxane was less than 1 ppm: ◯, 1-10 ppm: Δ, 10 ppm or more: x, and the formaldehyde amount was less than 1 ppm: ◯, 1-10 ppm: Δ, 10 ppm or more: x.
［重合安定性］
重合後のポリマーエマルションを８０メッシュのろ布を用いてろ過し、ろ布上の残渣を水洗後、乾燥し、その重量をエマルションの固形分に対し％で表示した。
[Polymerization stability]
The polymer emulsion after polymerization was filtered using an 80-mesh filter cloth, and the residue on the filter cloth was washed with water and dried, and the weight was expressed in% relative to the solid content of the emulsion.
［機械安定性］
ポリマーエマルション５０ｇをマーロン型試験器にて荷重１０ｋｇ、回転数１０００ｒｐｍで５分間撹拌し、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、乾燥し、その重量をエマルションの固形分に対し％で表示した。
[Machine stability]
50 g of the polymer emulsion was stirred for 5 minutes at a load of 10 kg and a rotation speed of 1000 rpm with a Marlon type tester, the resulting aggregate was filtered through an 80 mesh wire mesh, the residue was washed with water and dried, and its weight was determined as the solid content of the emulsion. In%.
［粒子径］
動的光散乱式粒度分布測定装置（日機装製 ＭＩＣＲＯＴＲＡＣ ＵＰＡ ９３４０）にて測定しμｍで表示した。
[Particle size]
It measured with the dynamic light-scattering type particle size distribution analyzer (MICROTRAC UPA 9340 made by Nikkiso) and displayed in μm.
［フィルムの光沢性］
ガラスプレート上に０．５ｍｍ（ｗｅｔ）のエマルション膜を作り、室温で２４時間放置してフィルムを作成した。このフィルムの光沢性を目視にて、優れる：○、可：△、不可：×の３段階で評価し示した。
[Glossiness of film]
A 0.5 mm (wet) emulsion film was formed on a glass plate and allowed to stand at room temperature for 24 hours to prepare a film. The glossiness of the film was visually evaluated and evaluated in three stages: excellent: ○, acceptable: Δ, impossible: x.
〈使用例２〉
攪拌機、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１３５部、緩衝剤として炭酸水素ナトリウム０．５部を仕込み、８０℃まで昇温させ、窒素ガスにて水中の溶存酸素を除去した。これとは別にメタクリル酸メチル７５部、アクリル酸エチル１７１部、アクリル酸４部、乳化重合用乳化剤８部、イオン交換水１１０部とを混合して、モノマーエマルションを調製した。次に、上記で調製したモノマーエマルション４０部を一括して上記反応容器に添加し、１０分間撹拌後、重合開始剤である過硫酸アンモニウム０．５部を加え、１０分間撹拌した。次に残りのモノマーエマルションを３時間かけて滴下して重合反応を行い、４０℃まで冷却後、アンモニア水でｐＨ８〜９に調整してポリマーエマルションを得た。使用した乳化重合用乳化剤は表３に示す通りである。
<Usage example 2>
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 135 parts of ion-exchanged water and 0.5 part of sodium bicarbonate as a buffering agent, heated to 80 ° C. Dissolved oxygen was removed. Separately, 75 parts of methyl methacrylate, 171 parts of ethyl acrylate, 4 parts of acrylic acid, 8 parts of an emulsifier for emulsion polymerization, and 110 parts of ion-exchanged water were mixed to prepare a monomer emulsion. Next, 40 parts of the monomer emulsion prepared above were added all at once to the reaction vessel, and after stirring for 10 minutes, 0.5 part of ammonium persulfate as a polymerization initiator was added and stirred for 10 minutes. Next, the remaining monomer emulsion was added dropwise over 3 hours to conduct a polymerization reaction, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion. The emulsifiers used for emulsion polymerization are as shown in Table 3.
得られたポリマーエマルションについて、重合安定性、粒子径、ＶＯＣ量、化学安定性をそれぞれ評価した。重合安定性、粒子径の評価方法は上記と同様である。ＶＯＣ量、化学安定性の評価方法は以下の通りである。結果は表３に示す。 The obtained polymer emulsion was evaluated for polymerization stability, particle diameter, VOC amount, and chemical stability. The evaluation methods for polymerization stability and particle diameter are the same as described above. The methods for evaluating the VOC amount and chemical stability are as follows. The results are shown in Table 3.
［ＶＯＣ量］
ポリマーエマルションに含まれるＶＯＣ量をヘッドスペースＧＣにより測定を行った。
結果、１０ｐｐｍ未満：○、１０〜５０ｐｐｍ：△、５０ｐｐｍ以上：×、として示した。
[VOC amount]
The amount of VOC contained in the polymer emulsion was measured by headspace GC.
The results are shown as less than 10 ppm: ◯, 10-50 ppm: Δ, 50 ppm or more: x.
［化学安定性］
ポリマーエマルション１０ｇに各濃度の水酸化カルシウム水溶液１０ｍｌを撹拌しつつ加え、ポリマーが凝析する水酸化カルシウム濃度を（モル／Ｌ）：０．１、０．５、１．０、２．０、４．０、６．０、として示した。
[Chemical stability]
To 10 g of the polymer emulsion, 10 ml of a calcium hydroxide aqueous solution of each concentration is added with stirring, and the calcium hydroxide concentration at which the polymer coagulates (mol / L): 0.1, 0.5, 1.0, 2.0, 4.0, 6.0.
〈使用例３〉
攪拌機、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２５０部を仕込み、８０℃まで昇温させ、窒素ガスにて水中の溶存酸素を除去した。次にアクリル酸ブチル１２５部とアクリル酸２−エチルヘキシル１２５部に乳化重合用乳化剤５部を溶解させた混合モノマー液のうち５０部を反応器に仕込み、次いで過硫酸アンモニウム０．５部を加えて先行重合させ、重合開始１０分後より３時間かけて残りの混合モノマー液２０５部を滴下して重合させた。続けて重合温度にてさらに２時間熟成した後、４０℃まで冷却後、アンモニア水でｐＨ８〜９に調整してポリマーエマルションを得た。使用した乳化重合用乳化剤は表４に示す通りである。
<Usage example 3>
A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was charged with 250 parts of ion-exchanged water, heated to 80 ° C., and dissolved oxygen in water was removed with nitrogen gas. Next, 50 parts of a mixed monomer solution prepared by dissolving 5 parts of an emulsifier for emulsion polymerization in 125 parts of butyl acrylate and 125 parts of 2-ethylhexyl acrylate was charged into the reactor, and then 0.5 part of ammonium persulfate was added to the reactor. Polymerization was performed, and the remaining 205 parts of the mixed monomer solution was added dropwise over 3 hours from 10 minutes after the start of the polymerization. Subsequently, the mixture was further aged for 2 hours at the polymerization temperature, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion. The emulsifiers for emulsion polymerization used are as shown in Table 4.
得られたポリマーエマルションについて、重合安定性、機械安定性、耐熱着色性、接着性をそれぞれ評価した。重合安定性、機械安定性の評価方法は上記と同様である。耐熱着色性、接着性の評価方法は以下の通りである。結果は表４に示す。 About the obtained polymer emulsion, polymerization stability, mechanical stability, heat-resistant coloring property, and adhesiveness were evaluated, respectively. The evaluation methods for polymerization stability and mechanical stability are the same as described above. The evaluation methods for heat resistant colorability and adhesiveness are as follows. The results are shown in Table 4.
［耐熱着色性］
ガラス板上に０．５ｍｍ厚のポリマーフィルムを作製し、２００℃に調整した熱風乾燥器内で３０分間熱処理して、ポリマーフィルムの着色を目視で調べた。結果、全く着色が認められない：○、淡い黄色に着色している：△、濃い褐色に着色している：×、として示した。
[Heat resistant coloring]
A polymer film having a thickness of 0.5 mm was prepared on a glass plate, heat-treated for 30 minutes in a hot air dryer adjusted to 200 ° C., and the coloring of the polymer film was visually examined. As a result, no coloration was observed: ○, pale yellow coloration: Δ, dark brown coloration: x.
［接着性］
５ｃｍ幅に切ったＰＥＴフィルム上にエマルションを２５μｍ（ｄｒｙ）の厚さに塗工し、熱処理した後ＳＵＳ板に貼り付け、ローラ圧着する。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。
[Adhesiveness]
The emulsion is applied to a thickness of 25 μm (dry) on a PET film cut to a width of 5 cm, heat-treated, then attached to a SUS plate, and roller-pressed. The film was peeled off so that the adhesive surface was 5 cm × 5 cm, and a time (second) until the film was peeled off by hanging a weight of 200 g on the edge of the film was measured.
〈使用例４〉
攪拌機、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１３１部、緩衝剤として炭酸水素ナトリウム０．５部を仕込み、７０℃まで昇温させ、窒素ガスにて水中の溶存酸素を除去した。これとは別に酢酸ビニル２５０部、乳化重合用乳化剤８部、イオン交換水１１０部とを混合して、モノマーエマルションを調製した。次に、上記で調製したモノマーエマルション４０部を一括して上記反応容器に添加し、１０分間撹拌後、重合開始剤である過硫酸アンモニウム０．５部を加え、１０分間撹拌した。次に残りのモノマーエマルションを３時間かけて滴下して重合反応を行い、４０℃まで冷却後、アンモニア水でｐＨ８〜９に調整してポリマーエマルションを得た。使用した乳化重合用乳化剤は表５に示す通りである。
<Usage example 4>
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 131 parts of ion-exchanged water and 0.5 part of sodium bicarbonate as a buffering agent, heated to 70 ° C. Dissolved oxygen was removed. Separately, 250 parts of vinyl acetate, 8 parts of an emulsifier for emulsion polymerization, and 110 parts of ion-exchanged water were mixed to prepare a monomer emulsion. Next, 40 parts of the monomer emulsion prepared above were added all at once to the reaction vessel, and after stirring for 10 minutes, 0.5 part of ammonium persulfate as a polymerization initiator was added and stirred for 10 minutes. Next, the remaining monomer emulsion was added dropwise over 3 hours to conduct a polymerization reaction, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion. The emulsifiers for emulsion polymerization used are as shown in Table 5.
得られたポリマーエマルションについて、重合安定性、粒子径、接着性をそれぞれ評価した。重合安定性、粒子径の評価方法は上記の評価方法と同様である。接着性の評価方法は以下の通りである。結果を表５に示す。 The obtained polymer emulsion was evaluated for polymerization stability, particle diameter, and adhesiveness. The evaluation method of polymerization stability and particle diameter is the same as the above evaluation method. The evaluation method of adhesiveness is as follows. The results are shown in Table 5.
［接着性］
５ｃｍ幅に切った合板上にエマルションを２５μｍ（ｄｒｙ）の厚さに塗工し、熱処理した後５ｃｍ幅の綿製の布を貼り付け、ローラ圧着する。接着面が５ｃｍ×５ｃｍとなるように布を剥がし、はがした布の端に１Ｋｇの重りを吊り下げて剥がれるまでの時間（秒）を測定した。
[Adhesiveness]
The emulsion is coated on a plywood cut to a width of 5 cm to a thickness of 25 μm (dry), heat-treated, and then a 5 cm wide cotton cloth is affixed and roller-pressed. The cloth was peeled off so that the adhesive surface was 5 cm × 5 cm, and a time (second) until the piece was peeled off by hanging a 1 kg weight on the edge of the peeled cloth was measured.
表２〜表５の結果から、本発明にかかる乳化重合用乳化剤は、乳化剤に含まれるアルデヒドやジオキサン生成量が極めて少量であり、エマルションの重合安定性、機械安定性等が良好で、ＶＯＣなど有害な副生成物の発生を大幅に低減することができる。また、得られたポリマーエマルションのフィルム光沢性、接着性、耐熱性などの諸特性が従来の界面活性剤からなる比較品の乳化剤を用いたものより優れることが明らかである。 From the results of Tables 2 to 5, the emulsifier for emulsion polymerization according to the present invention has a very small amount of aldehyde and dioxane produced in the emulsifier, and has good polymerization stability and mechanical stability of the emulsion, such as VOC. Generation of harmful by-products can be greatly reduced. In addition, it is apparent that the obtained polymer emulsion is superior in properties such as film gloss, adhesion, and heat resistance to those using a comparative emulsifier made of a conventional surfactant.
本発明の乳化重合用乳化剤を用いて重合し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など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 polymerization using the emulsifier for emulsion polymerization of the present invention can be applied to wood, metal, paper, cloth, other concrete, etc., for example, as an adhesive, a coating agent, an impregnation reinforcing agent and the like. Further, the polymer taken out from the emulsion or latex can be used as a resin, rubber, polymer modifier and the like.
Claims (5)
A polymer emulsion obtained by the production method according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005319854A JP2007126540A (en) | 2005-11-02 | 2005-11-02 | Emulsifier for emulsion polymerization, method for producing polymer emulsion, and the resultant polymer emulsion |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011001277A (en) * | 2009-06-17 | 2011-01-06 | Daicel Chemical Industries Ltd | New polyglycerol derivative or salt thereof, and method for producing the same |
| JP2013224455A (en) * | 2008-04-17 | 2013-10-31 | Daicel Corp | Polyglycerol derivative |
| JP2013227526A (en) * | 2012-03-26 | 2013-11-07 | Nippon Synthetic Chem Ind Co Ltd:The | Synthetic resin emulsion, coating agent formed by using the same, and coating layer |
-
2005
- 2005-11-02 JP JP2005319854A patent/JP2007126540A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013224455A (en) * | 2008-04-17 | 2013-10-31 | Daicel Corp | Polyglycerol derivative |
| JP2011001277A (en) * | 2009-06-17 | 2011-01-06 | Daicel Chemical Industries Ltd | New polyglycerol derivative or salt thereof, and method for producing the same |
| JP2013227526A (en) * | 2012-03-26 | 2013-11-07 | Nippon Synthetic Chem Ind Co Ltd:The | Synthetic resin emulsion, coating agent formed by using the same, and coating layer |
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