JP2009280652A - Polyoxyalkylene-modified organopolysiloxane compound - Google Patents
Polyoxyalkylene-modified organopolysiloxane compound Download PDFInfo
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- JP2009280652A JP2009280652A JP2008131990A JP2008131990A JP2009280652A JP 2009280652 A JP2009280652 A JP 2009280652A JP 2008131990 A JP2008131990 A JP 2008131990A JP 2008131990 A JP2008131990 A JP 2008131990A JP 2009280652 A JP2009280652 A JP 2009280652A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 91
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 46
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 14
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 14
- 239000006185 dispersion Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004945 emulsification Methods 0.000 abstract description 5
- 230000007928 solubilization Effects 0.000 abstract description 5
- 238000005063 solubilization Methods 0.000 abstract description 5
- 239000006260 foam Substances 0.000 abstract description 4
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 74
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 60
- 238000000034 method Methods 0.000 description 44
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 41
- 229910052757 nitrogen Inorganic materials 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 34
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 31
- 239000003513 alkali Substances 0.000 description 27
- -1 polyoxyethylene Polymers 0.000 description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 21
- 239000002253 acid Substances 0.000 description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000005587 bubbling Effects 0.000 description 18
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 description 17
- OXQKEKGBFMQTML-UHFFFAOYSA-N alpha-Glucoheptitol Chemical compound OCC(O)C(O)C(O)C(O)C(O)CO OXQKEKGBFMQTML-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000003463 adsorbent Substances 0.000 description 11
- 238000005907 ketalization reaction Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000811 xylitol Substances 0.000 description 10
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 10
- 229960002675 xylitol Drugs 0.000 description 10
- 235000010447 xylitol Nutrition 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 238000007664 blowing Methods 0.000 description 9
- 238000006459 hydrosilylation reaction Methods 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005903 acid hydrolysis reaction Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 125000005037 alkyl phenyl group Chemical group 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 150000005846 sugar alcohols Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 2
- 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 2
- HEBKCHPVOIAQTA-IMJSIDKUSA-N L-arabinitol Chemical compound OC[C@H](O)C(O)[C@@H](O)CO HEBKCHPVOIAQTA-IMJSIDKUSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JVWLUVNSQYXYBE-UHFFFAOYSA-N Ribitol Natural products OCC(C)C(O)C(O)CO JVWLUVNSQYXYBE-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006567 deketalization reaction Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 2
- 229910000105 potassium hydride Inorganic materials 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- PDVFSPNIEOYOQL-UHFFFAOYSA-N (4-methylphenyl)sulfonyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OS(=O)(=O)C1=CC=C(C)C=C1 PDVFSPNIEOYOQL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- USEGQJLHQSTGHW-UHFFFAOYSA-N 3-bromo-2-methylprop-1-ene Chemical compound CC(=C)CBr USEGQJLHQSTGHW-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- HVSJHYFLAANPJS-UHFFFAOYSA-N 3-iodo-2-methylprop-1-ene Chemical compound CC(=C)CI HVSJHYFLAANPJS-UHFFFAOYSA-N 0.000 description 1
- 125000006032 3-methyl-3-butenyl group Chemical group 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- IZMWJUPSQXIVDN-UHFFFAOYSA-N 4-bromo-2-methylbut-1-ene Chemical compound CC(=C)CCBr IZMWJUPSQXIVDN-UHFFFAOYSA-N 0.000 description 1
- DMAYBPBPEUFIHJ-UHFFFAOYSA-N 4-bromobut-1-ene Chemical compound BrCCC=C DMAYBPBPEUFIHJ-UHFFFAOYSA-N 0.000 description 1
- WKEVRZCQFQDCIR-UHFFFAOYSA-N 4-chlorobut-1-ene Chemical compound ClCCC=C WKEVRZCQFQDCIR-UHFFFAOYSA-N 0.000 description 1
- WOMUECWVNKNZEP-UHFFFAOYSA-N 4-iodo-2-methylbut-1-ene Chemical compound CC(=C)CCI WOMUECWVNKNZEP-UHFFFAOYSA-N 0.000 description 1
- VUSYNHBKPCGGCI-UHFFFAOYSA-N 4-iodobut-1-ene Chemical compound ICCC=C VUSYNHBKPCGGCI-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-FOQJRBATSA-N 59096-14-9 Chemical compound CC(=O)OC1=CC=CC=C1[14C](O)=O BSYNRYMUTXBXSQ-FOQJRBATSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明はポリオキシアルキレン変性オルガノポリシロキサン化合物に関する。さらに詳しくは、界面活性能、耐塩性及びオルガノポリシロキサンとの相溶性に優れ、反応性官能基数が１分子中に１個のみ導入できるような制御が可能なポリオキシアルキレン変性オルガノポリシロキサン化合物、及びそれを得るためのポリオキシアルキレン化合物に関する。 The present invention relates to a polyoxyalkylene-modified organopolysiloxane compound. More specifically, a polyoxyalkylene-modified organopolysiloxane compound that is excellent in surface activity, salt resistance, and compatibility with organopolysiloxane and that can be controlled so that only one reactive functional group can be introduced per molecule, And a polyoxyalkylene compound for obtaining the same.
オルガノポリシロキサンは耐熱性、耐候性、離型性、撥水性、生理的不活性に優れるため、プラスチック、繊維、塗料、化粧品等の様々な分野で使用されている。しかし、オルガノポリシロキサンは疎水性であり水やアルコール等への相溶性に乏しい。このため、配合する基剤への可溶化、乳化、相溶化、分散等を行うために、従来よりポリオキシエチレンアルキル（又はアルキルフェニル）エーテル、ポリオキシエチレンアルキルエステル、ポリオキシエチレンポリオキシプロピレンブロックコポリマー（プルロニック型）、ポリグリセリンアルキル（又はアルキルフェニル）エーテル、ポリグリセリンアルキルエステル等の非イオン性界面活性剤が使用されている。 Organopolysiloxane is excellent in heat resistance, weather resistance, releasability, water repellency, and physiological inertness, and is therefore used in various fields such as plastics, fibers, paints and cosmetics. However, organopolysiloxane is hydrophobic and poor in compatibility with water and alcohol. For this reason, polyoxyethylene alkyl (or alkylphenyl) ether, polyoxyethylene alkyl ester, polyoxyethylene polyoxypropylene block has been conventionally used for solubilization, emulsification, compatibilization, dispersion, etc. in the base to be blended. Nonionic surfactants such as copolymers (pluronic type), polyglycerin alkyl (or alkylphenyl) ether, polyglycerin alkyl ester and the like are used.
しかし、ポリオキシエチレンアルキル（又はアルキルフェニル）エーテル、ポリオキシエチレンアルキルエステル、ポリオキシエチレンポリオキシプロピレンブロックコポリマー（プルロニック型）はオルガノポリシロキサンとの相溶性が乏しいため、添加量を多くしなければならない。これに加えて、非イオン性界面活性剤の親水性基がポリオキシエチレン鎖のみの場合、塩の存在下では界面活性能の維持が十分でない、例えば気泡が維持しにくくなる等の問題があるため配合可能な基剤に制限があった。 However, polyoxyethylene alkyl (or alkylphenyl) ether, polyoxyethylene alkyl ester, and polyoxyethylene polyoxypropylene block copolymer (pluronic type) are poorly compatible with organopolysiloxane, so the addition amount must be increased. Don't be. In addition to this, when the hydrophilic group of the nonionic surfactant is only a polyoxyethylene chain, there is a problem that the surface activity is not sufficiently maintained in the presence of a salt, for example, bubbles are difficult to maintain. Therefore, the base that can be blended is limited.
また、ポリグリセリンアルキル（又はアルキルフェニル）エーテルやポリグリセリンアルキルエステルを用いる場合、塩の存在下においても上記の非イオン性界面活性剤と比較して界面活性能の維持が可能だが、親水性基にポリグリセリンを使用しているため非常に高粘度であり、高温化または水溶液でしかハンドリングできず、加えてオルガノポリシロキサンとの相溶性にも乏しいという問題があった。さらに、ポリグリセリンは一般的にジグリセリン、トリグリセリン、テトラグリセリン、ペンタグリセリン、ヘキサグリセリン等の混合物であり、蒸留等の操作により単一成分のものを得なければ１分子中に複数個のエーテル基やエステル基を有する化合物が生成し、それが原因で気泡安定化、可溶化、乳化、相溶化、分散等ができないおそれがある。 In addition, when polyglycerin alkyl (or alkylphenyl) ether or polyglycerin alkyl ester is used, it is possible to maintain the surface active ability in the presence of a salt as compared with the nonionic surfactant described above. In addition, since polyglycerin is used, it has a very high viscosity, can be handled only at a high temperature or in an aqueous solution, and has a problem of poor compatibility with organopolysiloxane. Furthermore, polyglycerin is generally a mixture of diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, and the like. If a single component is not obtained by an operation such as distillation, a plurality of ethers are contained in one molecule. There is a possibility that a compound having a group or an ester group is produced, and that bubbles cannot be stabilized, solubilized, emulsified, compatibilized or dispersed.
この課題を解決するため、これまでにポリオキシアルキレン変性オルガノポリシロキサン化合物を界面活性剤として用いることも提案されている（例えば特許文献１）。
しかし、ポリオキシアルキレン変性オルガノポリシロキサン化合物は、オルガノポリシロキサンとの相溶性に優れるため添加量を少なくできるが、やはり塩の存在下では界面活性能の維持が十分でなく、気泡の破壊や、可溶化物、乳化物、相溶化物、分散物の分離等が起こる問題があった。 However, the polyoxyalkylene-modified organopolysiloxane compound is excellent in compatibility with the organopolysiloxane, so that the amount added can be reduced. However, in the presence of a salt, the maintenance of the surface activity is not sufficient, the destruction of bubbles, There was a problem that separation of a solubilized product, an emulsified product, a compatibilized product and a dispersion occurred.
したがって、オルガノポリシロキサンとの相溶性に優れることに加え、塩の存在下においても気泡安定化、可溶化、乳化、相溶化、分散等が十分に維持でき、且つ、製造時に扱い易く蒸留等の操作が不要なポリオキシアルキレン変性オルガノポリシロキサン化合物が求められていた。 Therefore, in addition to excellent compatibility with the organopolysiloxane, it is possible to sufficiently maintain bubble stabilization, solubilization, emulsification, compatibilization, dispersion, etc. even in the presence of salt, and it is easy to handle during production, such as distillation. There has been a demand for polyoxyalkylene-modified organopolysiloxane compounds that do not require manipulation.
本発明の課題は、オルガノポリシロキサンとの相溶性に優れることに加え、塩の存在下においても気泡安定化、可溶化、乳化、相溶化、分散等の界面活性能が十分に維持できるポリオキシアルキレン変性オルガノポリシロキサン化合物を提供することである。 In addition to being excellent in compatibility with organopolysiloxanes, the object of the present invention is a polyoxy compound that can sufficiently maintain surface activity such as bubble stabilization, solubilization, emulsification, compatibilization, and dispersion even in the presence of a salt. It is to provide an alkylene-modified organopolysiloxane compound.
すなわち、本発明は、式（１）で表されるポリオキシアルキレン変性オルガノポリシロキサン化合物である。 That is, the present invention is a polyoxyalkylene-modified organopolysiloxane compound represented by the formula (1).
また、式（１）のポリオキシアルキレン変性オルガノポリシロキサン化合物の合成原料である、式（３）で表されるポリオキシアルキレン化合物である。 Moreover, it is a polyoxyalkylene compound represented by Formula (3), which is a synthesis raw material of the polyoxyalkylene-modified organopolysiloxane compound of Formula (1).
更に、塩化白金酸を触媒として請求項２記載のポリオキシアルキレン化合物をヒドロシリル化反応させることによって、請求項１記載のポリオキシアルキレン変性オルガノポリシロキサン化合物を製造する。 Furthermore, the polyoxyalkylene-modified organopolysiloxane compound according to claim 1 is produced by subjecting the polyoxyalkylene compound according to claim 2 to a hydrosilylation reaction using chloroplatinic acid as a catalyst.
また、本発明は、下記のＡ工程、Ｂ工程、Ｃ工程およびＤ工程を実施することにより得られる、前記ポリオキシアルキレン化合物に係るものである。 Moreover, this invention concerns on the said polyoxyalkylene compound obtained by implementing the following A process, B process, C process, and D process.
（Ａ工程） ペンチトールまたはヘプチトールに式（４）で表される化合物を理論当量に対して１．２〜１．５倍量、酸触媒をペンチトールまたはヘプチトールに対して５×１０−６〜５×１０−４モル％用いてケタール化反応を行い、一つの水酸基を有するケタール化物を得る工程。
（Ｂ工程） 前記ケタール化物の前記水酸基にアルカリ触媒の存在下で炭素数２〜４のアルキレンオキシドを温度８０〜１４０℃で開環重合させる工程。
（Ｃ工程） 次いで炭素数３〜５のアルケニルハライドを用いてアルカリ触媒の存在下でアルケニルエーテル化反応を行う工程。
（Ｄ工程） 次いで酸を用いて酸加水分解を行う工程。
(Step A) The compound represented by the formula (4) in pentitol or heptitol is 1.2 to 1.5 times the theoretical equivalent, and the acid catalyst is 5 × 10 −6 to pentitol or heptitol. A step of performing a ketalization reaction using 5 × 10 −4 mol% to obtain a ketalized product having one hydroxyl group.
(Step B) A step of subjecting the hydroxyl group of the ketalized product to ring-opening polymerization of an alkylene oxide having 2 to 4 carbon atoms at a temperature of 80 to 140 ° C. in the presence of an alkali catalyst.
(Step C) Next, a step of performing an alkenyl etherification reaction in the presence of an alkali catalyst using an alkenyl halide having 3 to 5 carbon atoms.
(D process) Next, the process of performing acid hydrolysis using an acid.
あるいは、Ｂ工程を行なわず、Ｄ工程の後に下記Ｇ工程を行なうことができる。
（Ｇ工程） 前記酸加水分解後に生成した水酸基にアルカリ触媒の存在下で炭素数２〜４のアルキレンオキシドを温度８０〜１４０℃で開環重合させる工程。
この発明においては、（Ａ工程）、（Ｃ工程）、（Ｄ工程）、（Ｇ工程）の順で実施する。
Alternatively, the following G step can be performed after the D step without performing the B step.
(Step G) A step of ring-opening polymerization of an alkylene oxide having 2 to 4 carbon atoms at a temperature of 80 to 140 ° C. in the presence of an alkali catalyst on the hydroxyl group generated after the acid hydrolysis.
In this invention, it implements in order of (A process), (C process), (D process), and (G process).
あるいは、前記Ｂ工程を省略することなく、前記Ｄ工程の後に上記のＧ工程を行なうことができる。
この発明においては、（Ａ工程）、（Ｂ工程）、（Ｃ工程）、（Ｄ工程）、（Ｇ工程）の順で実施する。
Alternatively, the G process can be performed after the D process without omitting the B process.
In this invention, it implements in order of (A process), (B process), (C process), (D process), (G process).
本発明のポリオキシアルキレン変性オルガノポリシロキサン化合物は、糖アルコール残基を構成単位とする新規化合物であり、オルガノポリシロキサンとの相溶性に優れることに加え、塩の存在下においても気泡安定化、可溶化、乳化、相溶化、分散等の界面活性能が十分に維持できるものである。 The polyoxyalkylene-modified organopolysiloxane compound of the present invention is a novel compound having a sugar alcohol residue as a structural unit, and in addition to being excellent in compatibility with the organopolysiloxane, it also stabilizes bubbles in the presence of a salt, The surface active ability such as solubilization, emulsification, compatibilization and dispersion can be sufficiently maintained.
また、本発明のポリオキシアルキレン化合物は、ポリオキシアルキレン変性オルガノポリシロキサン化合物の合成原料として有用である。 The polyoxyalkylene compound of the present invention is useful as a raw material for synthesizing a polyoxyalkylene-modified organopolysiloxane compound.
さらに、本発明の製造方法は、前駆体の反応性官能基を１分子中に１個のみ導入できるような制御が可能であって、高純度で効率よく製造することができる。 Furthermore, the production method of the present invention can be controlled so that only one reactive functional group of the precursor can be introduced in one molecule, and can be produced efficiently with high purity.
本発明の新規ポリオキシアルキレン変性オルガノポリシロキサン化合物は、式（１）で表される構造を有する。ポリオキシアルキレン変性オルガノポリシロキサン化合物の原料であるポリオキシアルキレン化合物は、式（３）で表される構造を有する。 The novel polyoxyalkylene-modified organopolysiloxane compound of the present invention has a structure represented by the formula (1). The polyoxyalkylene compound that is a raw material of the polyoxyalkylene-modified organopolysiloxane compound has a structure represented by the formula (3).
式（１）において、Ｒ１は炭素数１〜８のアルキル基であり、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、イソペンチル基、ヘキシル基、イソヘプチル基、２−エチルヘキシル基、オクチル基等が挙げられ、好ましくはメチル基である。 In the formula (1), R 1 is an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group. Hexyl group, isoheptyl group, 2-ethylhexyl group, octyl group and the like, preferably methyl group.
式（１）において、Ｒ２はＲ１、Ｘのいずれかであり、Ｘは式（２）で表される基である。 In Formula (1), R 2 is either R 1 or X, and X is a group represented by Formula (2).
式（２）において、Ｒ３は炭素数３〜５のアルキレン基であり、例えば、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、ペンテン基、イソペンテン基等が挙げられ、好ましくはプロピレン基、イソブチレン基である。 In the formula (2), R 3 is an alkylene group having 3 to 5 carbon atoms, and examples thereof include a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentene group, and an isopentene group, preferably a propylene group, An isobutylene group.
また式（２）及び式（３）において、ｄ及びｅは、それぞれ独立に０〜５０を満たし、ｄ＝０の場合にはｅ＝１〜５０であり、ｅ＝０の場合にはｄ＝１〜５０である。 In the formulas (2) and (3), d and e each independently satisfy 0 to 50. When d = 0, e = 1 to 50, and when e = 0, d = 1-50.
ｄ及びｅは、好ましくは０〜４０、より好ましくは０〜３０である。ｄ＝０の場合、ｅは好ましくは１．５〜３０、より好ましくは２〜２０である、ｅ＝０の場合、ｄは好ましくは１．５〜３０、より好ましくは２〜２０である。 d and e are preferably 0 to 40, more preferably 0 to 30. When d = 0, e is preferably 1.5-30, more preferably 2-20. When e = 0, d is preferably 1.5-30, more preferably 2-20.
ｄまたはｅが５０を超えると化合物の粘度が高くなる、あるいは室温で凝固するため、ハンドリング性が悪くなるため好ましくない。 When d or e exceeds 50, the viscosity of the compound becomes high, or it solidifies at room temperature.
式（３）において、Ｒ５は炭素数３〜５のアルケニル基であり、例えば、アリル基、メタリル基、３−ブテニル基、３−メチル−３−ブテニル基等が挙げられ、好ましくはアリル基、メタリル基である。 In the formula (3), R 5 is an alkenyl group having 3 to 5 carbon atoms, and examples thereof include an allyl group, a methallyl group, a 3-butenyl group, a 3-methyl-3-butenyl group, and preferably an allyl group. , A methallyl group.
式（２）及び式（３）において、ＡＯは炭素数２〜４のオキシアルキレン基であり、具体的にはオキシエチレン基、オキシプロピレン基、オキシブチレン基、オキシトリメチレン基、オキシテトラメチレン基等が挙げられ、好ましくはオキシエチレン基、オキシプロピレン基である。また、炭素数２〜４のオキシアルキレン基は単一で付加したものでも、２種以上がブロック状に付加したものでもランダム状に付加したものでもよい。２種以上がブロック状に付加したものあるいはランダム状に付加したものの場合、５０ｍｏｌ％以上、より好ましくは７０ｍｏｌ％以上、さらに好ましくは８０ｍｏｌ％以上はオキシエチレン基である。オキシエチレン基の割合が５０ｍｏｌ％未満の場合、親水性が低下してしまうため好ましくない。 In the formulas (2) and (3), AO is an oxyalkylene group having 2 to 4 carbon atoms, specifically an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytrimethylene group, an oxytetramethylene group. Etc., and preferably an oxyethylene group or an oxypropylene group. The oxyalkylene group having 2 to 4 carbon atoms may be added singly, or two or more oxyalkylene groups may be added in a block form or randomly added. In the case where two or more kinds are added in a block form or randomly added, 50 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more is an oxyethylene group. When the ratio of the oxyethylene group is less than 50 mol%, the hydrophilicity is lowered, which is not preferable.
本発明のポリオキシアルキレン変性オルガノポリシロキサン化合物は、具体的には下記の工程を用いて製造することにより得られる。 The polyoxyalkylene-modified organopolysiloxane compound of the present invention is specifically obtained by producing using the following steps.
まず、本発明のポリオキシアルキレン化合物を後述のようにして製造する。次いで、ポリオキシアルキレン化合物を塩化白金酸を触媒として、後述のようにヒドロシリル化反応させることによって、本発明のポリオキシアルキレン変性オルガノポリシロキサン化合物を製造することができる。 First, the polyoxyalkylene compound of the present invention is produced as described below. Next, the polyoxyalkylene compound of the present invention can be produced by subjecting the polyoxyalkylene compound to a hydrosilylation reaction using chloroplatinic acid as a catalyst as described below.
（ヒドロシリル化反応）
式（３）で表される化合物と、式（５）で表されるハイドロジェンオルガノポリシロキサンとを触媒存在下ヒドロシリル化反応を行うことにより、式（１）で表されるポリオキシアルキレン変性オルガノポリシロキサン化合物を製造する。
(Hydrosilylation reaction)
A polyoxyalkylene-modified organo represented by the formula (1) is obtained by performing a hydrosilylation reaction between the compound represented by the formula (3) and the hydrogenorganopolysiloxane represented by the formula (5) in the presence of a catalyst. A polysiloxane compound is produced.
（式中、Ｒ１は炭素数１〜８のアルキル基、Ｒ２はＲ１、水素原子のいずれかであり、ａ＝０〜７００、ｂ＝０〜１００であり、ｂ＝０の場合にはＲ２の少なくとも一つは水素原子である。） (In the formula, R 1 is an alkyl group having 1 to 8 carbon atoms, R 2 is either R 1 or a hydrogen atom, a = 0 to 700, b = 0 to 100, and b = 0. In which at least one of R 2 is a hydrogen atom.)
式（３）で表される化合物と、式（５）のハイドロジェンオルガノポリシロキサンの反応に用いる触媒としては、ニッケル、ルテニウム、ロジウム、パラジウム、イリジウム、白金などの第ＶIII 族遷移金属又はそれらの化合物が挙げられるが、塩化白金酸が入手しやすく、また、そのアルコール溶液が均一系触媒であるため、取り扱いが容易であり好ましい。この反応には、必要に応じて溶媒を使用してもよい。 As a catalyst used for the reaction of the compound represented by the formula (3) and the hydrogen organopolysiloxane of the formula (5), a Group VIII transition metal such as nickel, ruthenium, rhodium, palladium, iridium, platinum or the like Although chloroplatinic acid is easily available and the alcohol solution is a homogeneous catalyst, it is easy to handle and preferable. In this reaction, a solvent may be used as necessary.
ヒドロシリル化飯能に用いる溶媒としては、例えば、四塩化炭素、トルエン、キシレン、ヘキサン、オクタン、ジブチルエーテル、ジオキサン、テトラヒドロフラン、酢酸エチル、酢酸ブチル、メチルエチルケトン、エタノール、イソプロパノール、１−ブタノール等を挙げることができる。また、仕込み方法は、式（３）の化合物及び式（５）のハイドロジェンオルガノポリシロキサンを一括で仕込む方法や、式（３）の化合物の一部と式（５）のハイドロジェンオルガノポリシロキサンを仕込み、次いで式（３）の化合物の残りを連続的に仕込む方法、及び式（５）のハイドロジェンオルガノポリシロキサンを仕込み、次いで式（３）の化合物を連続的に仕込む方法等がある。また、式（５）のＳｉ−Ｈの反応性基を完全に反応させるため、末端に二重結合を有する炭素数４〜８の炭化水素、具体的には１−ブテン、イソブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテンなどを追加して反応することもできる。 Examples of the solvent used for hydrosilylation Hanno include carbon tetrachloride, toluene, xylene, hexane, octane, dibutyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate, methyl ethyl ketone, ethanol, isopropanol, 1-butanol and the like. it can. The charging method is a method of charging the compound of formula (3) and the hydrogenorganopolysiloxane of formula (5) all together, or a part of the compound of formula (3) and the hydrogenoorganopolysiloxane of formula (5). And then continuously charging the remainder of the compound of the formula (3) and charging the hydrogen organopolysiloxane of the formula (5) and then continuously charging the compound of the formula (3). Further, in order to completely react the Si—H reactive group of the formula (5), a hydrocarbon having 4 to 8 carbon atoms having a double bond at the end, specifically 1-butene, isobutene, 1-pentene. , 1-hexene, 1-heptene, 1-octene and the like can also be reacted.
式（３）で表される化合物は、以下のＡ〜Ｄ工程を実施することによって製造できる。 The compound represented by Formula (3) can be manufactured by implementing the following AD process.
（Ａ工程：ケタール化反応）
炭素数５または７の糖アルコールとケタール化剤を酸触媒の存在下で反応させ、水酸基を１個有する糖アルコール誘導体を製造する。
(Step A: ketalization reaction)
A sugar alcohol derivative having one hydroxyl group is produced by reacting a sugar alcohol having 5 or 7 carbon atoms with a ketalizing agent in the presence of an acid catalyst.
ケタール化反応に用いる糖アルコールとしては炭素数５のペンチトールや炭素数７のヘプチトールが用いられ、ペンチトールとしては、Ｄ−アラビトール、Ｌ−アラビトール、キシリトール、リビトールが挙げられ、へプチトールとしては、α−Ｄ−グルコヘプチトール、β−Ｄ−グルコヘプチトール、β−Ｌ−グルコヘプチトール、α−Ｄ−マンノヘプチトール、α−Ｌ−マンノヘプチトール、β−Ｄ−マンノヘプチトール、β−Ｄ−アルトロヘプチトール、β−Ｌ−アルトロヘプチトール、β−Ｄ−ガラヘプチトール、β−Ｌ−ガラヘプチトール、β−イドヘプチトール、β−アロヘプチトール、α−Ｄ−アロヘプチトールが挙げられるが、好ましくはＤ−アラビトール、Ｌ−アラビトール、キシリトール、リビトールであり、より好ましくはキシリトールである。これらは、天然物、合成物のいずれでもよく、単独で用いても、２種以上の混合物で用いてもよい。 As the sugar alcohol used in the ketalization reaction, pentitol having 5 carbon atoms or heptitol having 7 carbon atoms is used. Examples of pentitol include D-arabitol, L-arabitol, xylitol, ribitol, and heptitol as α-D-glucoheptitol, β-D-glucoheptitol, β-L-glucoheptitol, α-D-mannoheptitol, α-L-mannoheptitol, β-D-man Noheptitol, β-D-altoheptitol, β-L-altoheptitol, β-D-galaheptitol, β-L-galaheptitol, β-idheptitol, β-alloheptitol, α-D-alloheptyl Tol, preferably D-arabitol, L-arabitol, xylitol, ribitol, more preferably ki Is Lithol. These may be either natural products or synthetic products, and may be used alone or in a mixture of two or more.
次に、本発明においては、ケタール化剤として、式（４）で表される化合物が用いられる。式（４）において、Ｒ６及びＲ７はそれぞれ水素原子または炭素数１〜４のアルキル基を示し、Ｒ８及びＲ９はそれぞれ炭素数１〜４のアルキル基を示す。但し、Ｒ６及びＲ７の少なくとも１つは炭素数１〜４のアルキル基である。ここで炭素数１〜４のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基が挙げられ、これらは単独でも２種以上が混合したものでもよく、好ましくはメチル基、エチル基であり、より好ましくはメチル基である。 Next, in the present invention, a compound represented by the formula (4) is used as a ketalizing agent. In Formula (4), R 6 and R 7 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 8 and R 9 each represent an alkyl group having 1 to 4 carbon atoms. However, at least one of R 6 and R 7 is an alkyl group having 1 to 4 carbon atoms. Here, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and these may be used alone or in combination of two or more, preferably a methyl group or an ethyl group. More preferably a methyl group.
ペンチトールまたはヘプチトールと、式（４）で表される化合物とを用いてケタール化反応を行う場合、用いられる式（４）で表される化合物の仕込み量は理論当量に対して１．２〜１．５倍量であり、より好ましくは１．３〜１．５倍量であり、さらに好ましくは１．３〜１．４倍量である。なお、理論当量とは、化学方程式上必要とされる当量をいい、ペンチトールに対して２当量、ヘプチトールに対して３当量を表す。具体的に説明すると、ペンチトールの場合、ペンチトール1 モルに対して式（４）で表される化合物の仕込み量は２．４〜３．０モルであり、より好ましくは２．６〜３．０モルであり、さらに好ましくは２．６〜２．８モルとなる。また、へプチトールの場合、ヘプチトール１モルに対して式（４）で表される化合物は３．６〜４．５モルであり、より好ましくは３．９〜４．５モルであり、さらに好ましくは３．９〜４．２モルとなる。 When the ketalization reaction is performed using pentitol or heptitol and the compound represented by the formula (4), the amount of the compound represented by the formula (4) used is 1.2 to The amount is 1.5 times, more preferably 1.3 to 1.5 times, and still more preferably 1.3 to 1.4 times. The theoretical equivalent refers to an equivalent required in the chemical equation, and represents 2 equivalents to pentitol and 3 equivalents to heptitol. Specifically, in the case of pentitol, the amount of the compound represented by the formula (4) is 2.4 to 3.0 mol, more preferably 2.6 to 3 with respect to 1 mol of pentitol. The amount is 0.0 mol, and more preferably 2.6 to 2.8 mol. In the case of heptitol, the compound represented by the formula (4) is 3.6 to 4.5 mol, more preferably 3.9 to 4.5 mol, even more preferably 1 mol of heptitol. Is 3.9 to 4.2 moles.
式（４）で表される化合物の仕込み量が理論当量に対して１．２倍量より少ない場合、完全にケタール基に置換できず、ペンチトールの場合モノケタール体や未反応ペンチトールが、ヘプチトールの場合モノケタール体、ジケタール体、未反応ヘプチトールが残存する割合が多くなる。したがって、ケタール化されていない水酸基が多くなり、また、次のアルケニル化工程において１分子中にアルケニル基が複数個含まれた化合物の含有量が多くなることから、共重合体原料や変性材料として用いる場合、架橋して固化するなど望ましくない性能が出てしまう恐れがある。一方、理論当量に対して１．５倍量を上回ると、過剰原料の回収に時間を要し効率的ではないことに加え、二量体が副生し反応物は増粘または固化してしまう恐れがある。 When the amount of the compound represented by the formula (4) is less than 1.2 times the theoretical equivalent, it cannot be completely substituted with a ketal group, and in the case of pentitol, a monoketal or unreacted pentitol is converted into heptitol. In this case, the proportion of remaining monoketal, diketal, and unreacted heptitol increases. Accordingly, the number of hydroxyl groups that are not ketalized increases, and the content of a compound containing a plurality of alkenyl groups in one molecule increases in the next alkenylation step. When used, there is a risk of undesirable performance such as cross-linking and solidification. On the other hand, when the amount exceeds 1.5 times the theoretical equivalent, it takes time to recover excess raw materials and is not efficient, and dimers are by-produced to thicken or solidify the reaction product. There is a fear.
このケタール化反応により、式（６）で表される水酸基を１個有するペンチトールジケタールまたはヘプチトールトリケタールが得られる。 By this ketalization reaction, pentitol diketal or heptitol triketal having one hydroxyl group represented by formula (6) is obtained.
なお、得られる水酸基を１個有するペンチトールジケタールまたはヘプチトールトリケタールは水酸基の位置が異なる構造異性体や立体異性体の混合物として得られるが、これらをそのまま使用しても、蒸留等を行い1 種の異性体にしてから使用してもよい。例えば、キシリトールを用いて上記のケタール化を行った場合、１，２，３，４−ジ−Ｏ−イソプロピリデン−ＤＬ−キシリトール及び１，２，４，５−ジ−Ｏ−イソプロピリデン−ＤＬ−キシリトールの生成比が約９０：１０の混合物として得られる。 The obtained pentitol diketal or heptitol triketal having one hydroxyl group can be obtained as a mixture of structural isomers and stereoisomers having different hydroxyl positions. It may be used after making one isomer. For example, when the above ketalization is performed using xylitol, 1,2,3,4-di-O-isopropylidene-DL-xylitol and 1,2,4,5-di-O-isopropylidene-DL -A mixture with a xylitol production ratio of about 90:10 is obtained.
ケタール化反応において使用する酸触媒としては、酢酸、塩酸、塩化亜鉛、塩化アンモニウム、燐酸、硝酸、硫酸、硫酸銅、パラトルエンスルホン酸、三フッ化ホウ素エーテラート、五酸化二リン等の酸触媒が挙げられ、パラトルエンスルホン酸が特に好ましい。パラトルエンスルホン酸は無水物でも一水和物でもよい。酸触媒の使用量は、ペンチトールまたはヘプチトールに対して、５×１０−６〜５×１０−４モル％、より好ましくは７×１０−６〜４×１０−４モル％、さらに好ましくは１×１０−５〜３×１０−４モル％である。酸触媒の使用量が５×１０−６モル％を下回るとケタール化反応が完全に進行しない。また、５×１０−４モル％を上回ると反応副生物と過剰分の式（４）で表される化合物を回収中にケタール基の分解が起こり、また着色して色相が増加する。なお、反応に用いる式（４）で表される化合物はいずれも中性であることが好ましい。 Acid catalysts used in the ketalization reaction include acid catalysts such as acetic acid, hydrochloric acid, zinc chloride, ammonium chloride, phosphoric acid, nitric acid, sulfuric acid, copper sulfate, paratoluenesulfonic acid, boron trifluoride etherate, and diphosphorus pentoxide. And paratoluenesulfonic acid is particularly preferred. Paratoluenesulfonic acid may be an anhydride or a monohydrate. The amount of the acid catalyst used is 5 × 10 −6 to 5 × 10 −4 mol%, more preferably 7 × 10 −6 to 4 × 10 −4 mol%, more preferably 1 with respect to pentitol or heptitol. It is * 10 < -5 > -3 * 10 <-4> mol%. When the amount of the acid catalyst used is less than 5 × 10 −6 mol%, the ketalization reaction does not proceed completely. On the other hand, if it exceeds 5 × 10 −4 mol%, the reaction by-product and excess compound represented by the formula (4) will be recovered during the recovery of the ketal group, and it will be colored to increase the hue. In addition, it is preferable that all the compounds represented by Formula (4) used for reaction are neutral.
本発明の方法では、ケタール化反応における条件は特に制限はないが、反応温度は３０〜９０℃が好ましく、６０〜８０℃がより好ましい。反応温度が３０℃未満になるとペンチトールジケタールまたはヘプチトールトリケタールが高粘度になり撹拌効率が低下する恐れがある。また、９０℃を超えると着色の原因となる場合がある。ケタール化反応後の副生物および過剰の式（４）の化合物の回収は、通常は常圧、不活性ガス気流下で行われるが、これらの化合物を完全に留去させるには、副生物および過剰の式（４）の化合物の留出が終了した時点で減圧状態にした後に留去を行うことが好ましい。留出が継続している段階で減圧状態にするとケタール基が分解して、目的生成物のケタール基置換率が低下してしまうことがあるため好ましくない。 In the method of the present invention, the conditions in the ketalization reaction are not particularly limited, but the reaction temperature is preferably 30 to 90 ° C, more preferably 60 to 80 ° C. When the reaction temperature is less than 30 ° C., the pentitol diketal or heptitol triketal has a high viscosity, which may reduce the stirring efficiency. Moreover, when it exceeds 90 degreeC, it may become a cause of coloring. Recovery of by-products after the ketalization reaction and excess compound of formula (4) is usually carried out at normal pressure and under an inert gas stream. To completely distill off these compounds, by-products and It is preferable to perform distillation after reducing the pressure when the distillation of the excess compound of formula (4) is completed. If the pressure is reduced while the distillation continues, the ketal group may be decomposed and the ketal group substitution rate of the target product may decrease, which is not preferable.
本発明において用いられる酸触媒の使用量は極めて微量であるため、得られた水酸基を１個有するペンチトールジケタールまたはヘプチトールトリケタールを、さらに別の反応用原料に用いる場合、中和処理や除去を行わなくてもよい。但し、用途によっては触媒の失活や除去が必要な場合があるが、その場合には水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、酢酸ナトリウムなど一般的に使用されるアルカリ中和剤や、酸吸着能を有する吸着剤を用いて処理を行うのが好ましい。酸吸着能を有する吸着剤の市販品としては、キョーワード１００（ＭｇＯ）、キョーワード３００（２．５ＭｇＯ・
Ａｌ２Ｏ３・ ｘＨ２Ｏ）、キョーワード５００（Ｍｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ）、キョーワード６００（２ＭｇＯ・
６ＳｉＯ２・ ｘＨ２Ｏ）、キョーワード１０００（Ｍｇ４．５Ａｌ２（ＯＨ）１３ＣＯ３・３．５Ｈ２Ｏ）（協和化学工業（株）製）、トミックスＡＤ−１００（ＭｇＯ：９７．８％）、トミックスＡＤ−５００（ＭｇＯ：３７．４％、Ａｌ２Ｏ３：１７．２％、ＣＯ２：８．１％）、トミックスＡＤ−８００（ＳｉＯ２: ４２．１％、ＣａＯ：３１．５％）（富田製薬（株）製）などを例示することができる。
Since the amount of the acid catalyst used in the present invention is extremely small, when the obtained pentitol diketal or heptitol triketal having one hydroxyl group is used as another reaction raw material, neutralization treatment is performed. Or removal. However, depending on the application, it may be necessary to deactivate or remove the catalyst. In that case, commonly used alkali neutralizers such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acetate, and acid The treatment is preferably performed using an adsorbent having an adsorbing ability. Commercially available adsorbents having acid adsorption ability include Kyoward 100 (MgO), Kyoward 300 (2.5 MgO ·
Al 2 O 3 · xH 2 O ), Kyowaad 500 (Mg 6 Al 2 (OH ) 16 CO 3 · 4H 2 O), Kyowaad 600 (2MgO ·
6SiO 2 · xH 2 O), Kyowaad 1000 (Mg 4.5 Al 2 (OH ) 13 CO 3 · 3.5H 2 O) (manufactured by Kyowa Chemical Industry Co., Ltd.), Tomix AD-100 (MgO: 97. 8%), Tomix AD-500 (MgO: 37.4% , Al 2 O 3: 17.2%, CO 2: 8.1%), Tomix AD-800 (SiO 2: 42.1 %, CaO: 31.5%) (manufactured by Tomita Pharmaceutical Co., Ltd.).
（Ｂ工程：アルキレンオキシド開環重合反応）
Ａ工程で得られた化合物は、ケタール化反応に関与しない残り１つの水酸基を有している。この水酸基を有する化合物とアルキレンオキシドとをアルカリ触媒の存在下で開環重合させて、ポリオキシアルキレン化合物を製造する。
(Step B: alkylene oxide ring-opening polymerization reaction)
The compound obtained in Step A has one remaining hydroxyl group that does not participate in the ketalization reaction. A polyoxyalkylene compound is produced by ring-opening polymerization of the hydroxyl group-containing compound and alkylene oxide in the presence of an alkali catalyst.
アルキレンオキシド開環重合において用いるアルカリ触媒は、金属ナトリウム、金属カリウム、水素化ナトリウム、水素化カリウム、水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシド、カリウムメトキシド等が挙げられ、これらの１種または２種以上の混合物でもよい。 Examples of the alkali catalyst used in the alkylene oxide ring-opening polymerization include metal sodium, metal potassium, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, and the like, A mixture of two or more kinds may be used.
アルキレンオキシド開環重合条件は、例えば、アルカリ触媒量は原料とアルキレンオキシドの合計量に対して０．０１〜２質量％が好ましく、反応温度は６０〜１６０℃が好ましく、８０〜１４０℃がより好ましい。 Regarding the alkylene oxide ring-opening polymerization conditions, for example, the alkali catalyst amount is preferably 0.01 to 2% by mass with respect to the total amount of the raw material and the alkylene oxide, the reaction temperature is preferably 60 to 160 ° C, and more preferably 80 to 140 ° C. preferable.
（Ｃ工程：アルケニルエーテル化反応）
水酸基を有する化合物と、アルケニルハライドとをアルカリ触媒の存在下で反応させてアルケニル基を有するポリオキシアルキレン化合物を製造する。
(Step C: alkenyl etherification reaction)
A polyoxyalkylene compound having an alkenyl group is produced by reacting a compound having a hydroxyl group with an alkenyl halide in the presence of an alkali catalyst.
本発明のアルケニルエーテル化反応は、公知の技術を用いて行うことができ、具体的には水酸基を有するケタール基含有ポリオキシアルキレン化合物に、アルカリ触媒の存在下アルケニルハライドを作用させる。アルケニル化反応において用いるアルカリ触媒としては、金属ナトリウム、金属カリウム、水素化ナトリウム、水素化カリウム、水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシド、カリウムメトキシド等が挙げられる。これらの１種または２種以上の混合物でもよく、好ましくは水酸化ナトリウム、水酸化カリウムである。 The alkenyl etherification reaction of the present invention can be performed using a known technique. Specifically, an alkenyl halide is allowed to act on a ketal group-containing polyoxyalkylene compound having a hydroxyl group in the presence of an alkali catalyst. Examples of the alkali catalyst used in the alkenylation reaction include metal sodium, metal potassium, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide and the like. These may be used alone or as a mixture of two or more thereof, preferably sodium hydroxide or potassium hydroxide.
アルケニル化反応において用いるアルケニル基含有ハロゲン化合物としては、直鎖または分岐の炭素数３〜５の末端アルケニル基を有するハロゲン化物を用いる。具体例としては、アリルクロライド、アリルブロマイド、アリルアイオダイド、メタリルクロライド、メタリルブロマイド、メタリルアイオダイド、３−ブテニルクロライド、３−ブテニルブロマイド、３−ブテニルアイオダイド、３−メチル−３−ブテニルクロライド、３−メチル−３−ブテニルブロマイド、３−メチル−３−ブテニルアイオダイド等が挙げられ、好ましくはアリルクロライド、メタリルクロライドである。 As the alkenyl group-containing halogen compound used in the alkenylation reaction, a halide having a linear or branched terminal alkenyl group having 3 to 5 carbon atoms is used. Specific examples include allyl chloride, allyl bromide, allyl iodide, methallyl chloride, methallyl bromide, methallyl iodide, 3-butenyl chloride, 3-butenyl bromide, 3-butenyl iodide, 3-methyl. Examples include -3-butenyl chloride, 3-methyl-3-butenyl bromide, and 3-methyl-3-butenyl iodide, and allyl chloride and methallyl chloride are preferable.
アルケニル化反応における反応温度は、６０〜１４０℃が好ましく、８０〜１３０℃がより好ましい。６０℃よりも低いと反応速度が低下し、反応時間の増加や未反応物増加の原因となり、１４０℃よりも高いと二重結合の内部転位が起こる原因となる。 The reaction temperature in the alkenylation reaction is preferably 60 to 140 ° C, more preferably 80 to 130 ° C. When the temperature is lower than 60 ° C., the reaction rate decreases, causing an increase in reaction time and an increase in unreacted substances.
アルケニル化反応終了後の精製は、公知の方法で行なうことができる。例えば過剰のアルケニルハライドを留去後、水を加え塩析により分層させて過剰のアルカリ触媒および無機塩を分離除去させる方法を用いる。塩析工程に用いる水の量は、アルケニル化反応において用いたアルカリ触媒１００質量部に対して、２００〜５００質量部が好ましい。条件としては、温度が６０〜１００℃、２０分〜４時間静置させるのが好ましく、水層と有機層が分層した後、水層の抜き操作を行う。 Purification after completion of the alkenylation reaction can be performed by a known method. For example, after distilling off excess alkenyl halide, water is added and the layers are separated by salting out to remove excess alkali catalyst and inorganic salt. The amount of water used in the salting-out step is preferably 200 to 500 parts by mass with respect to 100 parts by mass of the alkali catalyst used in the alkenylation reaction. As conditions, it is preferable to leave the temperature at 60 to 100 ° C. for 20 minutes to 4 hours. After the aqueous layer and the organic layer are separated, the water layer is removed.
水層の抜き操作後の有機層には若干のアルカリ分が残っているため、中和を行うことが好ましい。通常は酸による中和を行うが、ケタール基を有する化合物の場合、水などの存在下で強酸性領域ではケタール基がケタール基の分加水解が起こり得る。そのため、本発明においては、酸、またはアルカリ吸着能を有する吸着剤を用いて中和を行うが、中和時のｐＨを調整することでケタール基が分解されることなくアルカリ分の除去が可能となる。 Since a slight amount of alkali remains in the organic layer after the operation of removing the aqueous layer, neutralization is preferably performed. Usually, neutralization with an acid is performed, but in the case of a compound having a ketal group, the ketal group can be hydrolyzed in the presence of water or the like in a strongly acidic region. Therefore, in the present invention, neutralization is performed using an adsorbent having an acid or alkali adsorption capacity, but the alkali content can be removed without decomposing the ketal group by adjusting the pH during neutralization. It becomes.
本発明において用いる酸としては、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸等、ピバル酸、シュウ酸、塩酸、燐酸、硝酸、硫酸、パラトルエンスルホン酸無水物、パラトルエンスルホン酸一水和物、ベンゼンスルホン酸、シクロヘキサンカルボン酸、安息香酸、サリチル酸、アセチルサリチル酸等が挙げられ、塩酸、リン酸、酢酸が好ましい。また、アルカリ吸着能を有する吸着剤としては、アルカリ吸着能を有するものであれば各種のものが使用可能であり、例えば活性白土、合成ゼオライト、活性炭、活性アルミナ、シリカゲル、マグネシアなどが挙げられ、好適な吸着剤の市販品としては、キョーワード６００、キョーワード７００（Ａｌ２Ｏ３・９ＳｉＯ２・Ｈ２Ｏ）（協和化学工業（株）製）、トミックスＡＤ−３００（ＭｇＯ：１３．２％、Ａｌ２Ｏ３：３１．０％、ＳｉＯ２：３０．５％）、トミックスＡＤ−６００（ＭｇＯ：１４．２％、ＳｉＯ２：６３．２％）、トミックスＡＤ−７００（Ａｌ２Ｏ３：１１．２％、ＳｉＯ２：６８．０％）（富田製薬（株）製）等を例示することができる。これら用いる酸、またはアルカリ吸着能を有する吸着剤は、１種または２種以上の混合物でもよい。また、酸についてはそのまま用いても水等で希釈したものでもよい。 Examples of acids used in the present invention include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, etc., pivalic acid, oxalic acid, hydrochloric acid, phosphoric acid, nitric acid Sulfuric acid, p-toluenesulfonic acid anhydride, p-toluenesulfonic acid monohydrate, benzenesulfonic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, acetylsalicylic acid, and the like, and hydrochloric acid, phosphoric acid, and acetic acid are preferred. In addition, as the adsorbent having alkali adsorption ability, various ones can be used as long as they have alkali adsorption ability, and examples thereof include activated clay, synthetic zeolite, activated carbon, activated alumina, silica gel, magnesia, As commercially available products of suitable adsorbents, Kyoward 600, Kyoward 700 (Al 2 O 3 .9SiO 2 .H 2 O) (manufactured by Kyowa Chemical Industry Co., Ltd.), Tomix AD-300 (MgO: 13.2) %, Al 2 O 3 : 31.0%, SiO 2 : 30.5%), Tomix AD-600 (MgO: 14.2%, SiO 2 : 63.2%), Tomix AD-700 (Al 2 O 3 : 11.2%, SiO 2 : 68.0%) (manufactured by Tomita Pharmaceutical Co., Ltd.) and the like. These adsorbents having acid or alkali adsorption ability may be used singly or as a mixture of two or more. The acid may be used as it is or diluted with water or the like.
本発明において、中和後のｐＨは好ましくは５．０〜７．５、より好ましくは５．３〜７．２、さらに好ましくは５．５〜７．０の範囲に調整するのがよい。中和後のｐＨが５．０を下回るとケタール基を有する化合物の場合、ケタール基の分加水解が起こり得るので好ましくない。また、ｐＨが７．５を超えるとアルカリ金属化合物が残存し、共重合体原料や変性材料として利用する際に副反応を引き起こしたり、末端二重結合の内部転位を引き起こしたりする原因となるので好ましくない。酸またはアルカリ吸着能を有する吸着剤による処理温度は、一義的には定められないが、通常は５０〜１００℃が好ましく、６０〜９０℃がより好ましい。添加量については、残存するアルカリ触媒の量や種類により異なるが、原料仕込量に対し０．５〜５質量％の範囲を目安とすればよい。少なすぎるとアルカリ分を完全に中和することができず、一方多すぎるとケタール基が含有されている場合、ケタール基が分解されてしまう恐れがある。酸、またはアルカリ吸着能を有する吸着剤による中和後、析出した塩や処理後の吸着剤を濾過または遠心分離などにより除去できるが、必要に応じて前述のＡ工程やＣ工程で用いた酸、アルカリ吸着能を有する吸着剤活性白土、合成ゼオライト系吸着剤、イオン交換樹脂等を用いてさらに高度に精製することも可能である。 In the present invention, the pH after neutralization is preferably adjusted to 5.0 to 7.5, more preferably 5.3 to 7.2, and still more preferably 5.5 to 7.0. When the pH after neutralization is less than 5.0, a compound having a ketal group is not preferable because the hydrolysis of the ketal group can occur. In addition, when the pH exceeds 7.5, the alkali metal compound remains, causing side reactions when used as a copolymer raw material or a modified material, or causing internal rearrangement of terminal double bonds. It is not preferable. The treatment temperature with the adsorbent having acid or alkali adsorption ability is not uniquely determined, but is usually preferably 50 to 100 ° C, more preferably 60 to 90 ° C. The amount of addition varies depending on the amount and type of the remaining alkali catalyst, but a range of 0.5 to 5% by mass with respect to the raw material charge may be used as a guide. If the amount is too small, the alkali content cannot be completely neutralized. On the other hand, if the amount is too large, the ketal group may be decomposed if it contains a ketal group. After neutralization with an adsorbent having an acid or alkali adsorption ability, the deposited salt and the treated adsorbent can be removed by filtration or centrifugation, etc., but the acid used in the above-mentioned A and C steps as necessary. Further, it is possible to further refine it using an adsorbent activated clay having an alkali adsorption capacity, a synthetic zeolite adsorbent, an ion exchange resin or the like.
（Ｄ工程：脱ケタール化反応）
ケタール基を有する化合物を酸加水分解することにより水酸基を有する化合物を製造する。
(Step D: Deketalization reaction)
A compound having a hydroxyl group is produced by acid hydrolysis of a compound having a ketal group.
酸加水分解の方法としては、例えば、ケタール基を有する化合物１００質量部に対し、酸を０．２〜５質量部、水を５〜４０％添加し酸加水分解処理を行い、不活性ガスを吹き込みながら生成したカルボニル化合物及び水を留出させた後、アルカリで中和してｐＨを中性とし、脱水を行い生成した塩を濾別する方法がある。使用する酸としては、例えば、塩酸、燐酸、硫酸などの鉱酸や、酢酸、ｐ−トルエンスルホン酸などの有機酸を挙げることができる。これらの中で、後処理などの点から、塩酸及び燐酸を好適に使用することができる。必要に応じて、水との接触をよくするために、エタノール、イソプロピルアルコールなどのアルコールを同時に添加することができる。 As a method of acid hydrolysis, for example, with respect to 100 parts by mass of a compound having a ketal group, 0.2 to 5 parts by mass of acid and 5 to 40% of water are added to perform acid hydrolysis, and inert gas is added. There is a method in which the carbonyl compound and water generated while blowing are distilled, neutralized with an alkali to neutralize the pH, and dehydrated to filter the generated salt. Examples of the acid to be used include mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid, and organic acids such as acetic acid and p-toluenesulfonic acid. Among these, hydrochloric acid and phosphoric acid can be preferably used from the viewpoint of post-treatment. If necessary, an alcohol such as ethanol or isopropyl alcohol can be added at the same time to improve contact with water.
なお、式（３）でｅ＝０の場合、水酸基とヒドロシリル基が結合した副生成物の生成を抑制するために、前記ヒドロシリル化反応を行った後にＤ工程の脱ケタール化反応を行ってもよい。 In addition, when e = 0 in the formula (3), the deketalization reaction in step D may be performed after the hydrosilylation reaction in order to suppress the formation of a by-product in which a hydroxyl group and a hydrosilyl group are bonded. Good.
（Ｇ工程：アルキレンオキシド開環重合反応）
酸加水分解後に生成した水酸基を有する化合物と、アルキレンオキシドとをアルカリ触媒の存在下で開環重合させてポリオキシアルキレン化合物を製造する。この工程は、前述の（Ｂ工程：アルキレンオキシド開環重合反応）と同じ条件で実施できる。
(Step G: alkylene oxide ring-opening polymerization reaction)
A polyoxyalkylene compound is produced by ring-opening polymerization of a compound having a hydroxyl group formed after acid hydrolysis and an alkylene oxide in the presence of an alkali catalyst. This step can be carried out under the same conditions as described above (Step B: alkylene oxide ring-opening polymerization reaction).
以上のようにして、本発明のオルガノポリシロキサン化合物を製造できる。本発明のオルガノポリシロキサン化合物は、界面活性能に優れ、且つ、耐塩性とオルガノポリシロキサンとの相溶性にも優れたオルガノポリシロキサン化合物となり、化粧品材料、繊維油剤、塗料添加剤、整泡剤等の広範囲の用途で使用することができる。また、本発明のポリオキシアルキレン化合物は、製造時に扱い易く蒸留等の操作が不要であり、オルガノポリシロキサン化合物の合成原料として非常に有用である。さらに本発明のオルガノポリシロキサン化合物の製造方法は、反応性官能基数が１分子中に１個のみ導入できるような制御が可能で、オルガノポリシロキサン化合物を高純度で効率よく製造することができるため有用である。 As described above, the organopolysiloxane compound of the present invention can be produced. The organopolysiloxane compound of the present invention is an organopolysiloxane compound having excellent surface activity and excellent salt resistance and compatibility with organopolysiloxane, and is a cosmetic material, fiber oil agent, paint additive, foam stabilizer. It can be used in a wide range of applications. In addition, the polyoxyalkylene compound of the present invention is easy to handle during production and does not require operations such as distillation, and is very useful as a raw material for synthesizing organopolysiloxane compounds. Furthermore, the method for producing an organopolysiloxane compound of the present invention can be controlled so that only one reactive functional group can be introduced per molecule, and the organopolysiloxane compound can be produced with high purity and efficiency. Useful.
以下に、実施例を挙げて本発明をさらに詳細に説明する。なお、合成品の分析は下記に記す方法で行った。 Hereinafter, the present invention will be described in more detail with reference to examples. The analysis of the synthesized product was performed by the method described below.
（測定方法）
水酸基価：ＪＩＳ Ｋ １５５７−１
動粘度：ＪＩＳ Ｋ ２２８３
不飽和度：ＪＩＳ Ｋ １５５７−３
（ガスクロマトグラフィー−質量分析（以下、ＧＣ−ＭＳと省略する）による化合物の同定およびガスクロマトグラフィー測定による純度（以下、ＧＣ純度と省略する）測定方法）
サンプル：０．１質量％トルエン溶液
サンプル注入量：１μL
カラム：Ｊ＆Ｗ １２３−７０３３ ＤＢ−ＷＡＸ（３０ｍ×３２０μｍ×０．５μｍ）
キャリヤーガス：Ｈｅ ３ｍＬ／ｍｉｎ
カラム温度：１６０℃、３０分後、５℃／ｍｉｎで２４０℃まで昇温
検出器：ＦＩＤ
（ＩＲスペクトルの測定条件）
装置：ＪＡＳＣＯ ＦＴ／ＩＲ−４１０
測定方法：液膜法
測定範囲：４００〜４０００ｃｍ−１
分解：２ｃｍ−１
積算回数：１６回
(Measuring method)
Hydroxyl value: JIS K1557-1
Kinematic viscosity: JIS K 2283
Unsaturation degree: JIS K 1557-3
(Identification of compounds by gas chromatography-mass spectrometry (hereinafter abbreviated as GC-MS) and purity by gas chromatography measurement (hereinafter abbreviated as GC purity) measurement method)
Sample: 0.1% by weight toluene solution Sample injection volume: 1 μL
Column: J & W 123-3-7033 DB-WAX (30 m × 320 μm × 0.5 μm)
Carrier gas: He 3mL / min
Column temperature: 160 ° C., 30 minutes later, temperature increased to 240 ° C. at 5 ° C./min. Detector: FID
(IR spectrum measurement conditions)
Apparatus: JASCO FT / IR-410
Measuring method: liquid film method Measuring range: 400 to 4000 cm −1
Decomposition: 2 cm -1
Integration count: 16 times
［実施例１］
（Ａ工程）
撹拌羽根、窒素吹き込み管、熱電対、冷却管及び油水分離管を取り付けた３リットル容量の四ツ口フラスコにキシリトール７００ｇ、２，２−ジメトキシプロパン１２９１ｇ、パラトルエンスルホン酸一水和物２７ｍｇをとり、反応系内を窒素ガスで置換後６０〜９０℃に保持し、２時間反応させた。反応終了後副生したメタノールおよび過剰分２，２−ジメトキシプロパンを常圧窒素気流下で加熱留去させ、留出物は冷却管、油水分離管を経由して凝縮後回収した。留出物が止まったことを確認して、８０〜１００℃、１０ｍｍＨｇ（ゲージ圧力）で１時間微量の副生物および過剰原料の除去を行い、１０１４ｇのサンプルを得た。性状は１０℃で液体であり、水酸基価は２２３ＫＯＨｍｇ／ｇ、動粘度（２５℃）は５００ｍｍ２／ｓだった。また、ＧＣ−ＭＳの結果、式（７）及び式（８）
で表されるジイソプロピリデンキシリトールの混合物であり、ＧＣ純度はそれぞれ式（７）の化合物が８６％、式（８）の化合物が９％だった。また、キシリトール及びモノイソプロピリデンキシリトールは含有していなかった。（以下、代表構造として式（７）で表す。）
[Example 1]
(Process A)
700 g of xylitol, 1291 g of 2,2-dimethoxypropane, and 27 mg of paratoluenesulfonic acid monohydrate were placed in a three-liter four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, a cooling tube, and an oil / water separation tube. The inside of the reaction system was replaced with nitrogen gas, and kept at 60 to 90 ° C. for reaction for 2 hours. Byproduct methanol and excess 2,2-dimethoxypropane by-produced after completion of the reaction were distilled off by heating under a normal pressure nitrogen stream, and the distillate was recovered after condensation via a condenser and an oil / water separator. After confirming that the distillate had stopped, trace amounts of by-products and excess raw materials were removed at 80 to 100 ° C. and 10 mmHg (gauge pressure) for 1 hour to obtain 1014 g of sample. The properties were liquid at 10 ° C., the hydroxyl value was 223 KOH mg / g, and the kinematic viscosity (25 ° C.) was 500 mm 2 / s. Moreover, as a result of GC-MS, Formula (7) and Formula (8)
The GC purity was 86% for the compound of formula (7) and 9% for the compound of formula (8), respectively. Moreover, xylitol and monoisopropylidene xylitol were not contained. (Hereinafter, represented by the formula (7) as a representative structure)
（Ｂ工程）
次に、撹拌装置、窒素導入管及び熱電対を取り付けた５リットル容量のオートクレーブに上記の方法で得たジイソプロピリデンキシリトール４６４ｇ、水酸化カリウム３ｇを仕込み、系中を窒素で置換した後撹拌しながら８０℃まで昇温し、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で脱水を行った。次に系中を窒素で置換した後１００℃まで昇温し、エチレンオキシド８８１ｇを計量槽に計り取り、１２０℃、０．５ＭＰａ（ゲージ圧力）以下の条件でエチレンオキシドを５時間かけて圧入し、さらに１時間反応を続けた。次に８５℃まで降温し、未反応のエチレンオキシドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。反応物の一部を抜き取り、中和、脱水及び濾過により精製サンプルを得た。この分析を行ったところ反応中間生成物の水酸基価は８４ＫＯＨｍｇ／ｇ、動粘度（２５℃）は２１０ｍｍ２／ｓだった。
(Process B)
Next, 464 g of diisopropylidene xylitol obtained by the above method and 3 g of potassium hydroxide were charged into a 5 liter autoclave equipped with a stirrer, a nitrogen introducing tube and a thermocouple, and the system was replaced with nitrogen and stirred. The temperature was raised to 80 ° C., and dehydration was performed in nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Next, after the inside of the system was replaced with nitrogen, the temperature was raised to 100 ° C., 881 g of ethylene oxide was measured into a measuring tank, and ethylene oxide was injected over 5 hours under the conditions of 120 ° C. and 0.5 MPa (gauge pressure), The reaction was continued for 1 hour. Next, the temperature was lowered to 85 ° C., and unreacted ethylene oxide was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. A part of the reaction product was extracted, and a purified sample was obtained by neutralization, dehydration and filtration. When this analysis was performed, the hydroxyl value of the reaction intermediate product was 84 KOH mg / g, and the kinematic viscosity (25 ° C.) was 210 mm 2 / s.
（Ｃ工程）
続いて５０℃以下まで冷却後、水酸化カリウム３００ｇ、アリルクロライド１８８ｇを仕込み、系中を窒素で置換した後、撹拌しながら１１０℃まで昇温し３時間反応させた。水８２０ｇを添加し１０分攪拌後１時間静置させ分層した下層のアルカリを含む水を排出し、残りの有機層は１０質量％燐酸で中和し、１００℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで１時間脱水を行い濾過により式（９）で表されるケタール基含有ポリオキシアルキレン化合物１１１０ｇを得た。水酸基価は３ＫＯＨｍｇ／ｇ、動粘度（２５℃）は１６０ｍｍ２／ｓ、不飽和度は１．４ｍｅｑ／ｇだった。
(Process C)
Subsequently, after cooling to 50 ° C. or less, 300 g of potassium hydroxide and 188 g of allyl chloride were charged, and the system was replaced with nitrogen, and then the temperature was raised to 110 ° C. with stirring and reacted for 3 hours. 820 g of water was added, and the mixture was stirred for 10 minutes and allowed to stand for 1 hour. Then, the separated layer-containing alkali-containing water was discharged, and the remaining organic layer was neutralized with 10% by mass phosphoric acid. Pressure) Hereinafter, dehydration was performed for 1 hour by nitrogen bubbling, and 1110 g of a ketal group-containing polyoxyalkylene compound represented by the formula (9) was obtained by filtration. The hydroxyl value was 3 KOH mg / g, the kinematic viscosity (25 ° C.) was 160 mm 2 / s, and the degree of unsaturation was 1.4 meq / g.
（Ｄ工程）
続いて式（９）のケタール基含有ポリオキシアルキレン化合物６８３ｇを撹拌羽根、窒素吹き込み管、熱電対及び冷却管を取り付けた１リットル容量の四ツ口フラスコに仕込み、水６８ｇ、１０質量％燐酸４１ｇを添加した。密閉状態で２時間撹拌後、窒素バブリングで水及びアセトンを系外に留去した。次いで１０質量％水酸化ナトリウム水溶液２９ｇを用いて中和した後水を添加し、１１０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で水分の除去を行い、次いでキョーワード１０００及びキョーワード７００（協和化学工業（株）製）を各２ｇ添加し、９０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で２時間精製し、濾過により式（１０）で表されるポリオキシアルキレン化合物５６３ｇを得た。水酸基価は３６０ＫＯＨｍｇ／ｇ、動粘度（２５℃）は６００ｍｍ２／ｓ、不飽和度は１．５ｍｅｑ／ｇだった。
(D process)
Subsequently, 683 g of the ketal group-containing polyoxyalkylene compound of the formula (9) was charged into a 1 liter four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple and a cooling tube, and 68 g of water and 41 g of 10% by mass phosphoric acid. Was added. After stirring for 2 hours in a sealed state, water and acetone were distilled out of the system by nitrogen bubbling. Next, the mixture was neutralized with 29 g of 10% by weight aqueous sodium hydroxide, water was added, water was removed in nitrogen bubbling at 110 ° C. and below −0.097 MPa (gauge pressure), and then Kyoward 1000 and Kyowa. 2 g of each word 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, purified at 90 ° C., −0.097 MPa (gauge pressure) or less in nitrogen bubbling for 2 hours, and filtered to obtain the poly (10) 563 g of an oxyalkylene compound was obtained. The hydroxyl value was 360 KOH mg / g, the kinematic viscosity (25 ° C.) was 600 mm 2 / s, and the degree of unsaturation was 1.5 meq / g.
（ヒドロシリル化反応）
続いて撹拌羽根、窒素吹き込み管、熱電対及び冷却管を取り付けた５００ミリリットル容四ツ口フラスコに式（１０）で表されるハイドロジェンジメチルポリシロキサン（ＨＭＳ−３０１、アヅマックス（株）製）２７ｇと、得られた式（１１）で表されるポリオキシアルキレン化合物９０ｇ、イソプロピルアルコール５９ｇ、酢酸カリウム０．０４ｇ、触媒として塩化白金酸六水和物のイソプロピルアルコール溶液（１×１０−３モル／リットル）を白金換算で１２ｐｐｍとなるように仕込み、窒素雰囲気下昇温してイソプロピルアルコール還流下で反応を行った。途中サンプリングを行い、Ｎ／１０水酸化カリウムのイソプロピルアルコール溶液を加えて水素ガスが発生しなくなるまで反応を継続し、式（１２）で表される変性オルガノポリシロキサン化合物１０７ｇを得た。反応後のサンプルのＩＲを測定し、Ｓｉ−Ｈ結合に由来する約２１６０ｃｍ−１のピークの消失を確認した。
(Hydrosilylation reaction)
Subsequently, 27 g of hydrogen dimethylpolysiloxane represented by the formula (10) (HMS-301, manufactured by AMAX Co., Ltd.) is added to a 500 ml four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, and a cooling tube. And 90 g of the obtained polyoxyalkylene compound represented by the formula (11), 59 g of isopropyl alcohol, 0.04 g of potassium acetate, and an isopropyl alcohol solution of chloroplatinic acid hexahydrate as a catalyst (1 × 10 −3 mol / Liter) was added to 12 ppm in terms of platinum, and the reaction was carried out under reflux of isopropyl alcohol by raising the temperature in a nitrogen atmosphere. Sampling was performed during the reaction, and an isopropyl alcohol solution of N / 10 potassium hydroxide was added to continue the reaction until no hydrogen gas was generated, thereby obtaining 107 g of a modified organopolysiloxane compound represented by the formula (12). The IR of the sample after the reaction was measured, and the disappearance of the peak at about 2160 cm −1 derived from the Si—H bond was confirmed.
［実施例２］
（Ｃ工程）
実施例１のＡ工程でジイソプロピリデンキシリトールを得た後、Ｂ工程を実施せず、Ｃ工程を実施した。
すなわち、撹拌装置、窒素導入管及び熱電対を取り付けた５リットル容量のオートクレーブに、実施例１のＡ工程で得たジイソプロピリデンキシリトール７９５ｇ、水酸化カリウム３９８ｇ、アリルクロライド３０４ｇを仕込み、系中を窒素で置換した後、撹拌しながら徐々に１１０℃まで昇温し３時間反応させた。水１２００ｇを添加し１０分攪拌後１時間静置させ分層した下層のアルカリを含む水を排出し、残りの有機層は１０質量％燐酸で中和し、１００℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで１時間脱水を行い濾過により式（１３）で表されるケタール基含有アルケニル化合物８２１ｇを得た。水酸基価は９ＫＯＨｍｇ／ｇ、動粘度（２５℃）は２１ｍｍ２／ｓ、不飽和度は３．５ｍｅｑ／ｇだった。
[Example 2]
(Process C)
After obtaining diisopropylidene xylitol in the A process of Example 1, the C process was implemented without implementing the B process.
That is, in a 5 liter autoclave equipped with a stirrer, a nitrogen inlet tube and a thermocouple, 795 g of diisopropylidene xylitol obtained in Step A of Example 1, 398 g of potassium hydroxide and 304 g of allyl chloride were charged. After substituting with nitrogen, the temperature was gradually raised to 110 ° C. with stirring and reacted for 3 hours. After adding 1200 g of water and stirring for 10 minutes, the mixture was allowed to stand for 1 hour, and the layered alkali-containing water was discharged. The remaining organic layer was neutralized with 10% by mass phosphoric acid, and 100 ° C., −0.097 MPa (gauge Pressure) Hereinafter, 821 g of a ketal group-containing alkenyl compound represented by formula (13) was obtained by dehydration by nitrogen bubbling for 1 hour and filtration. The hydroxyl value was 9 KOH mg / g, the kinematic viscosity (25 ° C.) was 21 mm 2 / s, and the degree of unsaturation was 3.5 meq / g.
（Ｄ工程）
続いて式（１３）のケタール基含有アルケニル化合物７２９ｇを撹拌羽根、窒素吹き込み管、熱電対及び冷却管を取り付けた１リットル容量の四ツ口フラスコに仕込み、水７３ｇ、１０質量％燐酸４４ｇを添加した。密閉状態で２時間撹拌後、窒素バブリングで水及びアセトンを系外に留去した。次いで１０質量％水酸化ナトリウム水溶液３０ｇを用いて中和した後水を添加し１１０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で水分の除去を行い、次いでキョーワード１０００及びキョーワード７００（協和化学工業（株）製）を各１ｇ添加し、９０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で２時間精製し、濾過により式（１４）で表されるアルケニル化合物４８４ｇを得た。水酸基価は１１６９ＫＯＨｍｇ／ｇ、動粘度（２５℃）は１２０００ｍｍ２／ｓ、不飽和度は４．６ｍｅｑ／ｇだった。
(D process)
Subsequently, 729 g of the ketal group-containing alkenyl compound of formula (13) was charged into a 1 liter four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple and a cooling tube, and 73 g of water and 44 g of 10% by mass phosphoric acid were added. did. After stirring for 2 hours in a sealed state, water and acetone were distilled out of the system by nitrogen bubbling. Next, after neutralizing with 30 g of a 10% by mass aqueous sodium hydroxide solution, water was added to remove water in nitrogen bubbling at 110 ° C. or lower and −0.097 MPa (gauge pressure) or less, and then Kyoward 1000 and Kyoward 700 g (manufactured by Kyowa Chemical Industry Co., Ltd.) each was added, purified at 90 ° C., −0.097 MPa (gauge pressure) or less in nitrogen bubbling for 2 hours, and filtered to obtain an alkenyl compound represented by formula (14) 484 g was obtained. The hydroxyl value was 1169 KOH mg / g, the kinematic viscosity (25 ° C.) was 12000 mm 2 / s, and the degree of unsaturation was 4.6 meq / g.
（Ｇ工程）
次に、撹拌装置、窒素導入管及び熱電対を取り付けた５リットル容量のオートクレーブに上記の方法で得た式（１４）で表されるアルケニル化合物３１０ｇ、水酸化カリウム３ｇを仕込み、系中を窒素で置換した後撹拌しながら８０℃まで昇温し、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で脱水を行った。次に系中を窒素で置換した後１００℃まで昇温し、エチレンオキシド７１２ｇを計量槽に計り取り、１２０℃、０．５ＭＰａ（ゲージ圧力）以下の条件でエチレンオキシドを８時間かけて圧入し、さらに１時間反応を続けた。次に８５℃まで降温し、未反応のエチレンオキシドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。さらに、１１０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で水分の除去を行い、次いでキョーワード１０００及びキョーワード７００（協和化学工業（株）製）を各２ｇ添加し、９０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で２時間精製し、濾過により式（１５）で表されるポリオキシアルキレン化合物１０３４ｇを得た。水酸基価は３６６ＫＯＨｍｇ／ｇ、動粘度（２５℃）は６００ｍｍ２／ｓ、不飽和度は１．３ｍｅｑ／ｇだった。
(G process)
Next, 310 g of the alkenyl compound represented by the formula (14) obtained by the above method and 3 g of potassium hydroxide were charged into a 5 liter autoclave equipped with a stirrer, a nitrogen introduction tube and a thermocouple, and the system was filled with nitrogen. Then, the temperature was raised to 80 ° C. with stirring, and dehydration was performed in a nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Next, after the system was replaced with nitrogen, the temperature was raised to 100 ° C., 712 g of ethylene oxide was measured into a measuring tank, and ethylene oxide was injected over 8 hours under the conditions of 120 ° C. and 0.5 MPa (gauge pressure), The reaction was continued for 1 hour. Next, the temperature was lowered to 85 ° C., and unreacted ethylene oxide was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. Further, moisture was removed in nitrogen bubbling at 110 ° C. or less than −0.097 MPa (gauge pressure), and then 2 g of KYOWARD 1000 and KYOWARD 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and 90 ° C. -0.097 MPa (gauge pressure) or less, purified in nitrogen bubbling for 2 hours, and filtered to obtain 1034 g of a polyoxyalkylene compound represented by the formula (15). The hydroxyl value was 366 KOH mg / g, the kinematic viscosity (25 ° C.) was 600 mm 2 / s, and the degree of unsaturation was 1.3 meq / g.
（ヒドロシリル化反応）
続いて撹拌羽根、窒素吹き込み管、熱電対及び冷却管を取り付けた５００ミリリットル容四ツ口フラスコに式（１１）で表されるハイドロジェンジメチルポリシロキサン（ＨＭＳ−３０１、アヅマックス（株）製）２５ｇと、得られた式（１５）で表されるポリオキシアルキレン化合物９２ｇ、イソプロピルアルコール５９ｇ、酢酸カリウム０．０５ｇ、触媒として塩化白金酸六水和物のイソプロピルアルコール溶液（１×１０-3モル／リットル）を白金換算で１２ｐｐｍとなるように仕込み、窒素雰囲気下昇温してイソプロピルアルコール還流下で反応を行った。途中サンプリングを行いＮ／１０水酸化カリウムのイソプロピルアルコール溶液を加えて水素ガスが発生しなくなるまで反応を継続し、式（１６）で表される変性オルガノポリシロキサン化合物１０１ｇを得た。反応後のサンプルのＩＲを測定し、Ｓｉ−Ｈ結合に由来する約２１６０ｃｍ−１のピークの消失を確認した。
(Hydrosilylation reaction)
Subsequently, 25 g of hydrogen dimethylpolysiloxane (HMS-301, manufactured by AMAX Co., Ltd.) represented by the formula (11) in a 500 ml four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, and a cooling tube. And 92 g of the obtained polyoxyalkylene compound represented by the formula (15), 59 g of isopropyl alcohol, 0.05 g of potassium acetate, and isopropyl alcohol solution of chloroplatinic acid hexahydrate as a catalyst (1 × 10 −3 mol / Liter) was added to 12 ppm in terms of platinum, and the reaction was carried out under reflux of isopropyl alcohol by raising the temperature in a nitrogen atmosphere. The reaction was continued until isopropyl alcohol solution of N / 10 potassium hydroxide was added and hydrogen gas was not generated, and 101 g of a modified organopolysiloxane compound represented by formula (16) was obtained. The IR of the sample after the reaction was measured, and the disappearance of the peak at about 2160 cm −1 derived from the Si—H bond was confirmed.
［実施例３］
（Ｇ工程）
撹拌装置、窒素導入管及び熱電対を取り付けた５リットル容量のオートクレーブに実施例２の方法で得た式（１４）で表されるアルケニル化合物３１０ｇ、水酸化カリウム（東亞合成（株）製）３ｇを仕込み、系中を窒素で置換した後撹拌しながら８０℃まで昇温し、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で脱水を行った。次に系中を窒素で置換した後１００℃まで昇温し、エチレンオキシド１４２３ｇを計量槽に計り取り、１２０℃、０．５ＭＰａ（ゲージ圧力）以下の条件でエチレンオキシドを１６時間かけて圧入し、さらに１時間反応を続けた。次に８５℃まで降温し、未反応のエチレンオキシドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。さらに、１１０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で水分の除去を行い、次いでキョーワード１０００及びキョーワード７００（協和化学工業（株）製）を各２ｇ添加し、９０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で２時間精製し、濾過により式（１７）で表されるポリオキシアルキレン化合物１３８７ｇを得た。水酸基価は２１８ＫＯＨｍｇ／ｇ、動粘度（２５℃）は４３０ｍｍ２／ｓ、不飽和度は０．８ｍｅｑ／ｇだった。
[Example 3]
(G process)
310 g of alkenyl compound represented by formula (14) obtained by the method of Example 2 and 3 g of potassium hydroxide (manufactured by Toagosei Co., Ltd.) in a 5 liter autoclave equipped with a stirrer, a nitrogen introducing tube and a thermocouple. After replacing the system with nitrogen, the temperature was raised to 80 ° C. while stirring, and dehydration was performed in nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Next, after replacing the system with nitrogen, the temperature was raised to 100 ° C., 1423 g of ethylene oxide was weighed into a measuring tank, and ethylene oxide was injected under pressure of 120 ° C. and 0.5 MPa (gauge pressure) or less over 16 hours. The reaction was continued for 1 hour. Next, the temperature was lowered to 85 ° C., and unreacted ethylene oxide was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. Further, moisture was removed in nitrogen bubbling at 110 ° C. or less than −0.097 MPa (gauge pressure), and then 2 g of KYOWARD 1000 and KYOWARD 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and 90 ° C. -0.097 MPa (gauge pressure) or less, purified in nitrogen bubbling for 2 hours, and filtered to obtain 1387 g of a polyoxyalkylene compound represented by the formula (17). The hydroxyl value was 218 KOH mg / g, the kinematic viscosity (25 ° C.) was 430 mm 2 / s, and the degree of unsaturation was 0.8 meq / g.
（ヒドロシリル化反応）
続いて撹拌羽根、窒素吹き込み管、熱電対及び冷却管を取り付けた５００ミリリットル容四ツ口フラスコに式（１１）で表されるハイドロジェンジメチルポリシロキサン（ＨＭＳ−３０１、アヅマックス（株）製）１５ｇと、得られた式（１７）で表されるポリオキシアルキレン化合物９２ｇ、イソプロピルアルコール５４ｇ、酢酸カリウム０．０４ｇ、触媒として塩化白金酸六水和物のイソプロピルアルコール溶液（１×１０-3モル／リットル）を白金換算で１２ｐｐｍとなるように仕込み、窒素雰囲気下昇温してイソプロピルアルコール還流下で反応を行った。途中サンプリングを行いＮ／１０水酸化カリウムのイソプロピルアルコール溶液を加えて水素ガスが発生しなくなるまで反応を継続し、式（１８）で表される変性オルガノポリシロキサン化合物１９２ｇを得た。反応後のサンプルのＩＲを測定し、Ｓｉ−Ｈ結合に由来する約２１６０ｃｍ−１のピークの消失を確認した。
(Hydrosilylation reaction)
Subsequently, hydrogendimethylpolysiloxane represented by the formula (11) (HMS-301, manufactured by AMAX Co., Ltd.) 15 g in a 500 ml four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, and a cooling tube And 92 g of the obtained polyoxyalkylene compound represented by the formula (17), 54 g of isopropyl alcohol, 0.04 g of potassium acetate, and an isopropyl alcohol solution of chloroplatinic acid hexahydrate as a catalyst (1 × 10 −3 mol / Liter) was added to 12 ppm in terms of platinum, and the reaction was carried out under reflux of isopropyl alcohol by raising the temperature in a nitrogen atmosphere. Halfway sampling was performed and an isopropyl alcohol solution of N / 10 potassium hydroxide was added to continue the reaction until hydrogen gas was not generated. Thus, 192 g of a modified organopolysiloxane compound represented by the formula (18) was obtained. The IR of the sample after the reaction was measured, and the disappearance of the peak at about 2160 cm −1 derived from the Si—H bond was confirmed.
（実施例４）
実施例１、２及び３で得られた変性オルガノポリシロキサン化合物及び従来より公知の非イオン性界面活性剤を用いて、以下の試験を行い、気泡安定性を調べた。変性オルガノポリシロキサン化合物または界面活性剤２ｇと５質量％食塩水１９８ｇを１リットル容のトールメスシリンダーに採り、かき混ぜにより界面活性剤を完全に溶解した。トールメスシリンダーを４０℃の恒温槽に入れ、液温を４０±２℃に保持し、ディフーザーストーンを用いて窒素ガスを毎分５００ｍｌで吹き込み発泡させた。泡の高さが１リットル容を示す標線に達したとき、窒素ガスの吹き込みをやめた。窒素ガスの吹き込みをやめてから、５分間隔で２５分後まで、泡の容積の経時変化を調べた。結果を表２に示す。
Example 4
Using the modified organopolysiloxane compounds obtained in Examples 1, 2 and 3, and conventionally known nonionic surfactants, the following tests were conducted to examine the bubble stability. 2 g of the modified organopolysiloxane compound or surfactant and 198 g of 5% by mass saline were placed in a 1 liter tall graduated cylinder, and the surfactant was completely dissolved by stirring. The tall graduated cylinder was placed in a constant temperature bath of 40 ° C., the liquid temperature was kept at 40 ± 2 ° C., and nitrogen gas was blown at a rate of 500 ml per minute using a diffuser stone. When the height of the foam reached the mark indicating 1 liter volume, nitrogen gas blowing was stopped. The change in the foam volume over time was examined from the end of the blowing of nitrogen gas until 25 minutes after 5 minutes. The results are shown in Table 2.
（比較例１〜３）
表１に示す変性オルガノポリシロキサン化合物及び界面活性剤を用いて、実施例３と同様の方法で試験を行い、塩存在の有無における気泡安定性を調べた。結果を表２に示す。
(Comparative Examples 1-3)
Using the modified organopolysiloxane compounds and surfactants shown in Table 1, tests were conducted in the same manner as in Example 3 to examine the bubble stability in the presence or absence of salt. The results are shown in Table 2.
表２の結果より、実施例１、２及び３で得られた本発明の界面活性剤は、長時間の気泡安定性及び耐塩性に優れていることが分かる。一方、従来のポリエーテルを用いたポリオキシアルキレン変性オルガノポリシロキサン化合物や非イオン性界面活性剤を用いた比較例では、実施例と比較して長時間の気泡安定性及び耐塩性が劣っていることがわかる。
From the results in Table 2, it can be seen that the surfactants of the present invention obtained in Examples 1, 2 and 3 are excellent in long-term bubble stability and salt resistance. On the other hand, in the comparative example using the polyoxyalkylene-modified organopolysiloxane compound and the nonionic surfactant using the conventional polyether, the long-term bubble stability and salt resistance are inferior compared to the examples. I understand that.
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