TW201617305A - 可羥矽基化之丁香酚聚醚及丁香酚聚醚矽氧烷的製造及其用途 - Google Patents
可羥矽基化之丁香酚聚醚及丁香酚聚醚矽氧烷的製造及其用途 Download PDFInfo
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- TW201617305A TW201617305A TW104129146A TW104129146A TW201617305A TW 201617305 A TW201617305 A TW 201617305A TW 104129146 A TW104129146 A TW 104129146A TW 104129146 A TW104129146 A TW 104129146A TW 201617305 A TW201617305 A TW 201617305A
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- Prior art keywords
- glycidyl ether
- group
- eugenol
- polyether
- ether
- Prior art date
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- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 title claims abstract description 264
- 229920000570 polyether Polymers 0.000 title claims abstract description 156
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 131
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000005770 Eugenol Substances 0.000 title claims abstract description 128
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229960002217 eugenol Drugs 0.000 title claims abstract description 128
- -1 siloxanes Chemical class 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 238000000034 method Methods 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 230000008569 process Effects 0.000 claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 54
- 239000003054 catalyst Substances 0.000 claims description 51
- 125000002947 alkylene group Chemical group 0.000 claims description 30
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000012634 fragment Substances 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 14
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 13
- 150000002118 epoxides Chemical class 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 150000002596 lactones Chemical class 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- ANLABNUUYWRCRP-UHFFFAOYSA-N 1-(4-nitrophenyl)cyclopentane-1-carbonitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1(C#N)CCCC1 ANLABNUUYWRCRP-UHFFFAOYSA-N 0.000 claims description 4
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- XPQPWPZFBULGKT-UHFFFAOYSA-N undecanoic acid methyl ester Natural products CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 claims description 4
- JHEPBQHNVNUAFL-AATRIKPKSA-N (e)-hex-1-en-1-ol Chemical compound CCCC\C=C\O JHEPBQHNVNUAFL-AATRIKPKSA-N 0.000 claims description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- VASBMTKQLWDLDL-UHFFFAOYSA-N but-3-enoxybenzene Chemical compound C=CCCOC1=CC=CC=C1 VASBMTKQLWDLDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 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 claims description 3
- GJEZBVHHZQAEDB-SYDPRGILSA-N (1s,5r)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC[C@H]2O[C@H]21 GJEZBVHHZQAEDB-SYDPRGILSA-N 0.000 claims description 2
- ZNCCGGMWVUBVBO-UHFFFAOYSA-N 1-(oxiran-2-ylmethyl)pyrrolidin-2-one Chemical compound O=C1CCCN1CC1OC1 ZNCCGGMWVUBVBO-UHFFFAOYSA-N 0.000 claims description 2
- SYQIWVMFOAHDMK-UHFFFAOYSA-N 2,2,3,3-tetramethyloxirane Chemical compound CC1(C)OC1(C)C SYQIWVMFOAHDMK-UHFFFAOYSA-N 0.000 claims description 2
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 claims description 2
- RSONLRWFEVQLQC-UHFFFAOYSA-N 2-(2,2,3,3,3-pentafluoropropyl)oxirane Chemical compound FC(F)(F)C(F)(F)CC1CO1 RSONLRWFEVQLQC-UHFFFAOYSA-N 0.000 claims description 2
- WUKHWLIEBSRTRH-UHFFFAOYSA-N 2-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)oxirane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)CC1CO1 WUKHWLIEBSRTRH-UHFFFAOYSA-N 0.000 claims description 2
- KGYUZRBIQCDOCN-UHFFFAOYSA-N 2-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)oxirane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC1CO1 KGYUZRBIQCDOCN-UHFFFAOYSA-N 0.000 claims description 2
- ZGHZSTWONPNWHV-UHFFFAOYSA-N 2-(oxiran-2-yl)ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCC1CO1 ZGHZSTWONPNWHV-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 claims description 2
- JFDMLXYWGLECEY-UHFFFAOYSA-N 2-benzyloxirane Chemical compound C=1C=CC=CC=1CC1CO1 JFDMLXYWGLECEY-UHFFFAOYSA-N 0.000 claims description 2
- OVFUAYYHQWUHCD-UHFFFAOYSA-N 2-butan-2-yloxirane Chemical compound CCC(C)C1CO1 OVFUAYYHQWUHCD-UHFFFAOYSA-N 0.000 claims description 2
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 claims description 2
- MPGABYXKKCLIRW-UHFFFAOYSA-N 2-decyloxirane Chemical compound CCCCCCCCCCC1CO1 MPGABYXKKCLIRW-UHFFFAOYSA-N 0.000 claims description 2
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 claims description 2
- UHXMPWNOJMTYCV-UHFFFAOYSA-N 2-methyloxirane;2-methylprop-2-enoic acid Chemical compound CC1CO1.CC(=C)C(O)=O UHXMPWNOJMTYCV-UHFFFAOYSA-N 0.000 claims description 2
- BBILJUBMQKCJMS-UHFFFAOYSA-N 2-methyloxirane;prop-2-enoic acid Chemical compound CC1CO1.OC(=O)C=C BBILJUBMQKCJMS-UHFFFAOYSA-N 0.000 claims description 2
- LXVAZSIZYQIZCR-UHFFFAOYSA-N 2-nonyloxirane Chemical compound CCCCCCCCCC1CO1 LXVAZSIZYQIZCR-UHFFFAOYSA-N 0.000 claims description 2
- NMOFYYYCFRVWBK-UHFFFAOYSA-N 2-pentyloxirane Chemical compound CCCCCC1CO1 NMOFYYYCFRVWBK-UHFFFAOYSA-N 0.000 claims description 2
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 claims description 2
- AVTRXHPXQNZVFK-UHFFFAOYSA-N 3-(oxiran-2-yl)propyl acetate Chemical compound CC(=O)OCCCC1CO1 AVTRXHPXQNZVFK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 claims description 2
- KKWQCCPQBCHJBZ-UHFFFAOYSA-N 4-(oxiran-2-ylmethyl)morpholine Chemical compound C1COCCN1CC1CO1 KKWQCCPQBCHJBZ-UHFFFAOYSA-N 0.000 claims description 2
- IXUYURKVFANPPC-UHFFFAOYSA-N C(C1CO1)OCCCC(C(OC(C)C)(OC(C)C)OC(C)C)CCCCCCCC Chemical compound C(C1CO1)OCCCC(C(OC(C)C)(OC(C)C)OC(C)C)CCCCCCCC IXUYURKVFANPPC-UHFFFAOYSA-N 0.000 claims description 2
- GKLXZYMUWOOVDQ-UHFFFAOYSA-N C(C1CO1)OCCCC(C(OC)(OC)C)CCCCCCCC Chemical compound C(C1CO1)OCCCC(C(OC)(OC)C)CCCCCCCC GKLXZYMUWOOVDQ-UHFFFAOYSA-N 0.000 claims description 2
- FYSWWDHYUCBHPR-UHFFFAOYSA-N C(C1CO1)OCCCC(C(OC)(OC)CCCOCC1CO1)CCCCCCCC Chemical compound C(C1CO1)OCCCC(C(OC)(OC)CCCOCC1CO1)CCCCCCCC FYSWWDHYUCBHPR-UHFFFAOYSA-N 0.000 claims description 2
- MTDLVDBRMBSPBJ-UHFFFAOYSA-N C(C1CO1)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound C(C1CO1)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC MTDLVDBRMBSPBJ-UHFFFAOYSA-N 0.000 claims description 2
- YMNPHIPHSDTGEP-UHFFFAOYSA-N C(C1CO1)OCCCC(C(OCCC)(OCCC)OCCC)CCCCCCCC Chemical compound C(C1CO1)OCCCC(C(OCCC)(OCCC)OCCC)CCCCCCCC YMNPHIPHSDTGEP-UHFFFAOYSA-N 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 claims description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 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 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- YLNSNVGRSIOCEU-UHFFFAOYSA-N oxiran-2-ylmethyl butanoate Chemical compound CCCC(=O)OCC1CO1 YLNSNVGRSIOCEU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical group CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 claims 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 claims 1
- OIPZQYANGIDALK-UHFFFAOYSA-N 2-(11-methyldodecoxymethyl)oxirane Chemical compound CC(C)CCCCCCCCCCOCC1CO1 OIPZQYANGIDALK-UHFFFAOYSA-N 0.000 claims 1
- BFMNHBIWNXFWJI-UHFFFAOYSA-N 2-(16-methylheptadecoxymethyl)oxirane Chemical compound CC(C)CCCCCCCCCCCCCCCOCC1CO1 BFMNHBIWNXFWJI-UHFFFAOYSA-N 0.000 claims 1
- LUKZQXIIABXJOH-UHFFFAOYSA-N 2-(2,2-dimethylpropoxymethyl)oxirane Chemical compound CC(C)(C)COCC1CO1 LUKZQXIIABXJOH-UHFFFAOYSA-N 0.000 claims 1
- IXORNPPEKYKHCI-UHFFFAOYSA-N 2-(2-butyloctoxymethyl)oxirane Chemical compound CCCCCCC(CCCC)COCC1CO1 IXORNPPEKYKHCI-UHFFFAOYSA-N 0.000 claims 1
- DMMVFDWCKYSBMW-UHFFFAOYSA-N 2-(2-dodecylhexadecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCC(CCCCCCCCCCCC)COCC1CO1 DMMVFDWCKYSBMW-UHFFFAOYSA-N 0.000 claims 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 claims 1
- ROTXOCNLESZVTD-UHFFFAOYSA-N 2-(2-hexyldecoxymethyl)oxirane Chemical compound CCCCCCCCC(CCCCCC)COCC1CO1 ROTXOCNLESZVTD-UHFFFAOYSA-N 0.000 claims 1
- MFASXWKINCTMCP-UHFFFAOYSA-N 2-(2-methylbutan-2-yloxymethyl)oxirane Chemical group CCC(C)(C)OCC1CO1 MFASXWKINCTMCP-UHFFFAOYSA-N 0.000 claims 1
- XPDNYCQECCKURY-UHFFFAOYSA-N 2-(2-methylbutoxymethyl)oxirane Chemical group CCC(C)COCC1CO1 XPDNYCQECCKURY-UHFFFAOYSA-N 0.000 claims 1
- AQKDMKKMCVJJTC-UHFFFAOYSA-N 2-(2-methylpropoxymethyl)oxirane Chemical group CC(C)COCC1CO1 AQKDMKKMCVJJTC-UHFFFAOYSA-N 0.000 claims 1
- RCBZNUVPIKHRRL-UHFFFAOYSA-N 2-(2-propylheptoxymethyl)oxirane Chemical compound CCCCCC(CCC)COCC1CO1 RCBZNUVPIKHRRL-UHFFFAOYSA-N 0.000 claims 1
- PIRNLVINTMLQLX-UHFFFAOYSA-N 2-(3,5,5-trimethylhexoxymethyl)oxirane Chemical compound CC(C)(C)CC(C)CCOCC1CO1 PIRNLVINTMLQLX-UHFFFAOYSA-N 0.000 claims 1
- YGOZVDCPBOZJMK-UHFFFAOYSA-N 2-(3-methylbutoxymethyl)oxirane Chemical group CC(C)CCOCC1CO1 YGOZVDCPBOZJMK-UHFFFAOYSA-N 0.000 claims 1
- CFHNJMSXJNUUTN-UHFFFAOYSA-N 2-(8-methylnonoxymethyl)oxirane Chemical compound CC(C)CCCCCCCOCC1CO1 CFHNJMSXJNUUTN-UHFFFAOYSA-N 0.000 claims 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical group CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims 1
- INSCMIFABOJDRE-UHFFFAOYSA-N 2-(heptoxymethyl)oxirane Chemical compound CCCCCCCOCC1CO1 INSCMIFABOJDRE-UHFFFAOYSA-N 0.000 claims 1
- JPEGUDKOYOIOOP-UHFFFAOYSA-N 2-(hexoxymethyl)oxirane Chemical compound CCCCCCOCC1CO1 JPEGUDKOYOIOOP-UHFFFAOYSA-N 0.000 claims 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical group COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims 1
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 claims 1
- QGJIHMFIXIWYAY-UHFFFAOYSA-N 2-(pentan-2-yloxymethyl)oxirane Chemical group CCCC(C)OCC1CO1 QGJIHMFIXIWYAY-UHFFFAOYSA-N 0.000 claims 1
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- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical group CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 claims 1
- SFJRUJUEMVAZLM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxirane Chemical group CC(C)(C)OCC1CO1 SFJRUJUEMVAZLM-UHFFFAOYSA-N 0.000 claims 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 claims 1
- FNAIUDVEQSQIDK-UHFFFAOYSA-N C(C)C(COCC1CO1)CCCCCCCC Chemical compound C(C)C(COCC1CO1)CCCCCCCC FNAIUDVEQSQIDK-UHFFFAOYSA-N 0.000 claims 1
- MNWYBJTUAPRTGD-UHFFFAOYSA-N C(C1CO1)OCCCC(C(OCC)(OCC)CC)CCCCCCCC Chemical compound C(C1CO1)OCCCC(C(OCC)(OCC)CC)CCCCCCCC MNWYBJTUAPRTGD-UHFFFAOYSA-N 0.000 claims 1
- IDZYIMQZSBQWLE-UHFFFAOYSA-N C(CCC)C(COCC1CO1)CCCCCCCCCCCC Chemical compound C(CCC)C(COCC1CO1)CCCCCCCCCCCC IDZYIMQZSBQWLE-UHFFFAOYSA-N 0.000 claims 1
- UOYAXPHMCUEDSO-UHFFFAOYSA-N C(CCCC)C(COCC1CO1)CCCCC Chemical compound C(CCCC)C(COCC1CO1)CCCCC UOYAXPHMCUEDSO-UHFFFAOYSA-N 0.000 claims 1
- UGKCPEUSUNEZJR-UHFFFAOYSA-N CC(COCC1CO1)CCCCCCCCC Chemical compound CC(COCC1CO1)CCCCCCCCC UGKCPEUSUNEZJR-UHFFFAOYSA-N 0.000 claims 1
- RLTRRLFFYPIIHY-UHFFFAOYSA-N CCCCCCCCC(CCC(CCC)OCC1CO1)C(OC)(OC)OC Chemical compound CCCCCCCCC(CCC(CCC)OCC1CO1)C(OC)(OC)OC RLTRRLFFYPIIHY-UHFFFAOYSA-N 0.000 claims 1
- WFDIJRYMOXRFFG-XPULMUKRSA-N acetyl acetate Chemical group [14CH3]C(=O)OC([14CH3])=O WFDIJRYMOXRFFG-XPULMUKRSA-N 0.000 claims 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 claims 1
- VYXHEFOZRVPJRK-UHFFFAOYSA-N ethyl 3-methyloxirane-2-carboxylate Chemical compound CCOC(=O)C1OC1C VYXHEFOZRVPJRK-UHFFFAOYSA-N 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明係關於一種製造可羥矽基化之丁香酚類聚醚之方法;將其轉化成聚醚矽氧烷;以及可藉由此方法製造之產物;及該等產物用作界面活性劑之用途。
Description
本發明係關於一種製造可羥矽基化之丁香酚類聚醚之方法;將其轉化成聚醚矽氧烷;以及可藉由此方法製造之產物;及該等產物用作界面活性劑之用途。
聚醚及聚醚矽氧烷通常用作添加劑用於製造食物包裝或印刷於食物包裝上。特定言之,在此領域中,所採用之物質就其遷移至食物中之可能性而言遭受極嚴格要求。為避免將該等物質吸收至人體中,該等物質必須具有極小(若存在)遷移可能性。因此,甚至在基本聚醚組分之合成期間極大強調使用毒理學上不加批判之起始材料,尤其醇性起始物。特別重要的為起始材料在少量下無毒,且在該等起始材料不在反應中經歷完全轉化而得到聚醚且因此仍存在於產物中之情況下展現僅極少遷移至食物中。
因此,本發明之一目標為提供聚醚,其符合與食物接觸之添加劑之嚴格目標,且同時為含允許視情況存在之另一反應得到聚醚矽氧烷之反應性基團之穩定均質化合物。
然而,DMC催化之聚醚製造中典型地採用之多種醇性起始
物僅在有限程度(即使有的話)上符合食物一致性之標準及極少遷移。
現已出人意料地發現,在DMC催化之聚醚製造中使用丁香酚作為起始物提供尤其均質、具有小莫耳質量分佈且不尋常穩定之產物。穩定性之評估特定言之必須考慮如下事實:使用丁香酚作為起始物導致末端雙鍵幾乎完全保存,亦即不遭受重組形成異丁香酚之聚醚。此具有巨大優點,因為末端雙鍵之保存使得無數其他化學反應為可能,特定言之與Si-H官能性矽氧烷之羥矽基化。
基於芳族醇(亦即酚)為起始物之界面活性劑聚醚如例如US 5296627 A及US 6646091 B2中所描述為充分熟知的。
丁香酚之鹼催化之烷氧基化原則上亦為已知的。舉例而言,Moustapha等人在Egyptian J.Chem.2005,48(3),273-285中提及丁香酚之鈉金屬催化之乙氧基化。該產物未詳細表徵且僅在氣相層析分析中用作銀-烯烴錯合物之溶劑。
文獻EP 94386 B1及DE 3342509 A1描述包含丁香酚類聚醚之組成物。
丁香酚之鹼金屬催化之烷氧基化之首次詳細描述係描述於EP 1717259 A1中。在其中所敘述之實例中,丁香酚最初饋入作為起始物且隨後與鹼性催化劑(諸如甲醇鈉)摻合。自此催化步驟移除甲醇之後,在140-160℃之溫度下添加環氧乙烷、環氧丙烷及/或環氧丁烷。此程序明確提供純異丁香酚類聚醚,亦即丁香酚烯丙基在鹼性烷氧基化期間經歷定量重組形成2-丙烯基。所得結構單元作為異丁香酚為熟習此項技術者已知。
在Macromol.Symp.2010,293,15-19中,Luinstra等人亦描述
聚醚類結構,其中丁香酚烯丙基仍穩定以便使該等結構經受ADMET聚合。該等作者採用二乙二醇二甲苯磺酸酯與兩莫耳丁香酚之取代反應。然而,未描述含丁香酚聚合物。
含丁香酚基團之聚醚矽氧烷原則上亦揭示於科學文獻中且可藉由三種合成原理獲得。
專利申請案JP 11158266 A及授權專利EP 2134771 B1描述例如藉由用含氫環狀氫矽氧烷(諸如D4H)平衡丁香酚封端之聚矽氧烷將丁香酚併入聚醚矽氧烷主鏈中。
專利US 6313329 B1揭示一種將丁香酚單元引入聚醚矽氧烷結構中之尤其精緻方法。此包含習知末端不飽和聚醚連同十一碳烯酸甲酯在Pt催化下初始羥矽基化至含SiH之聚矽氧烷上,且隨後用酚氧進行聚矽氧烷鍵結之甲酯之轉酯化以消除甲醇。然而,在水性系統中所得酚酯之預期的不穩定性將可能嚴重限制該等產物之商業效用。
最常用之方法,由於其為工業上最有利於實施,包含藉由一般在由Pt化合物催化下之羥矽基化來連接丁香酚烯丙基與Si-H官能性聚矽氧烷。舉例而言,授權專利EP 818495 B1描述亦包含丁香酚單元之三官能性聚醚矽氧烷用於織物及皮革之永久加工。
在大多數情況下,不僅丁香酚且亦習知末端不飽和聚醚(例如烯丙基醇之烷氧基化物)羥矽基化至含SiH之烷基聚矽氧烷上,在個別情況下亦使用其他末端不飽和化合物,諸如烯烴。如EP 1010748 B1、EP 887367 A3及EP 845520 B1中所描述,該等包含丁香酚之聚醚矽氧烷用作柴油消泡劑。
化妝品調配物構成另一廣泛應用領域,其中該等聚醚矽氧烷用作佐劑,如描述於EP 1260552 B1、US 6346595 B1、EP 916689 B1及US 7287784 B2中。
2011亦可見至少在一定程度上包含聚合物鍵結之丁香酚單元之含聚甘油的聚醚矽氧烷之描述。申請案EP 2492301 A1及EP 2492333 A1描述由丁香酚-縮水甘油加合物產生之聚甘油烯丙醚羥矽基化至含SiH之聚醚矽氧烷上。該等親水性聚矽氧烷可用作增稠劑或乳化劑。
在製程工程方面,藉由羥矽基化製造含丁香酚基團及聚醚基團之聚醚矽氧烷之先前技術方法的缺點為兩種或多於兩種不飽和產物必須同時添加至含SiH之聚醚矽氧烷。就待添加之反應物(諸如丁香酚及聚醚)(且自然地亦含SiH之聚矽氧烷)之間的分子量與親水性/疏水性特徵而言之顯著差異阻礙製造均勻組成之聚醚矽氧烷,其中不同反應物均勻分佈於所有矽氧烷鏈上。不充分混合極快速導致非均質組成之產物,且當務之急為避免此發生於品質及成本方面。
使用溶劑使反應介質均質化當然為可想像的,但就成本及製程工程而言為不利的,因為在羥矽基化之後隨後需要在另一方法步驟中再次移除所添加之溶劑。
因此,其似乎適用於試圖在一個分子/聚合物中合併可羥矽基化之丁香酚之芳族特徵與聚醚之可調諧親水性/疏水性特徵,且隨後在不使用溶劑之情況下使該分子/聚合物經受與適合聚醚矽氧烷之羥矽基化反應。
由於丁香酚之鹼金屬催化之烷氧基化明確提供異丁香酚類
聚醚(見下文),該等聚醚無法羥矽基化至含SiH之聚矽氧烷上。眾所周知,2-丙烯基不能進行羥矽基化。
因此,本發明之一目標為基於丁香酚作為起始物來製造可羥矽基化之烷氧基化產物,其中烯丙基仍完整無損且因此可羥矽基化。
出人意料地發現,丁香酚聚醚類聚醚矽氧烷可藉由一種方法以簡單方式獲得,該方法包含步驟1,製造丁香酚類聚醚;及步驟2,SiH官能性矽氧烷與來自步驟1之至少一種丁香酚類聚醚反應形成至少一個SiC鍵。
根據本發明,術語「丁香酚類聚醚(eugenol-based polyether)」理解為意謂由至少三個烷氧基單元組成且使用丁香酚作為醇性起始物製造之聚醚。
本發明提供一種製造烷氧基化產物之方法,其中至少一種環氧化物與丁香酚在至少一種過渡金屬催化劑存在下反應。
過渡金屬催化劑較佳為雙金屬氰化物催化劑。
極為出人意料的為,在根據本發明之方法中,丁香酚可用作烷氧基化反應之起始物以獲得所定義之可羥矽基化產物,因為使用丁香酚之先前技術方法具有許多缺點(見下文)。尤其出人意料的為,多取代芳族與醇性(酚系)起始物丁香酚適用於製造僅在最小程度上(即使有的話)為雙峰之具有相對較窄分子量分佈之烷氧基化產物。
根據本發明之方法中使用其他芳族與醇性起始物,例如癒創木酚(CAS 90-05-1)及2-萘酚(CAS 135-19-3)替代丁香酚之廣泛測試展示
具有顯著更多雙峰分佈之GPC。在兩種情況下,根據OH數甚至未實現預期莫耳質量。根據MALDI-Tof分析,主要成分為比預期具有更少莫耳之環氧丙烷添加至其上之靶分子。另外,GPC展示指派至具有大約兩倍莫耳質量之產物之高分子量峰。
此觀測將誤導熟習此項技術者認為多取代酚基如在2-萘酚中,其中酚環在間位及對位攜有稠合第二苯基,或苯基上之第二取代基如在癒創木酚中存在於羥基之鄰位,限制該等起始物之可用性。隨後所有更出人意料的為,酚環之羥基的鄰位攜有甲氧基且酚環之羥基的對位攜有烯丙基之5-烯丙基癒創木酚(亦稱為丁香酚)可同樣易於在根據本發明之方法中用作起始物。OH數與預期一致,且GPC僅展示對應於相對較高莫耳質量之負擔的開始。其他細節描述於實驗部分中。
根據本發明之一尤其較佳方法包含第一步驟,其中至少一種環氧化物與丁香酚在至少一種過渡金屬催化劑及視情況其他組分存在下反應;及第二步驟,其中進行來自步驟1之產物與Si-H官能性矽氧烷之至少一個反應。尤其較佳為在第二步驟中來自步驟1之產物及包含末端不飽和基團之其他組分與Si-H官能性矽氧烷反應時。
尤其較佳為一種製造丁香酚聚醚類聚醚矽氧烷之方法,其中該方法包含步驟1,製造丁香酚類聚醚;及步驟2,SiH官能性矽氧烷與來自步驟1之至少一種丁香酚類聚醚反應形成至少一個SiC鍵。根據本發明如此製造之產物作為界面活性劑具有尤其突出的適用性且為極良好分散劑。
根據本發明,術語「丁香酚類聚醚」理解為意謂可藉由根據本發明之方法獲得之聚醚。在此方法中,丁香酚經烷氧基化使得在反應期間丁香酚不經歷重組形成異丁香酚,亦即,丁香酚烯丙基未重組形成2-丙烯基。
在本發明之上下文中,術語「烷氧基化產物(alkoxylation product)」或「聚醚(polyether)」不僅涵蓋聚醚、聚醚醇(polyetherol/polyether alcohol)及聚醚酯醇且亦涵蓋聚醚碳酸酯醇,其可彼此同義使用。術語「聚(poly)」不必定理解為意謂分子或聚合物中存在大量醚官能基或醇官能基。其實際上僅用於指示存在個別單體構建塊之至少重複單元或具有相對較高莫耳質量之其他組成物且進一步展現一定多分散性。
結合本發明之片語「聚」不僅專門涵蓋分子中具有一個或多個單體之至少3個重複單元之化合物,而特定言之亦涵蓋展現分子量分佈且擁有至少200g/mol平均分子量之化合物的組成物。此定義考慮到所討論之行業領域中習慣將此類化合物稱為聚合物,即使其似乎不符合按照OECD或REACH準則之聚合物定義。
術語「丁香酚類聚醚」因此不僅指烷氧基化物但亦涵蓋丁香酚之反應產物,其中除環氧烷之外,使可藉由開環(共)聚合之其他單體反應,如下文中更特定闡明。
本發明同樣主張藉由根據本發明之方法製成之符合本文所描述之式(I)的產物及另外該等產物用作界面活性劑之用途。
本發明同樣主張藉由根據本發明之方法製成之符合本文所
描述之式(II)的產物及另外該等產物用作界面活性劑之用途。
下文例示性地描述本發明提供之主題而無任何意圖使本發明限於此等說明性具體實例。在下文中參考化合物之範圍、通式或類別時,此等應不僅涵蓋明確提及的化合物之相應範圍或群,且亦涵蓋可藉由提取個別值(範圍)或化合物獲得的化合物之所有子範圍及子群。當在本說明書之上下文中引用文獻時,其形成已引用文獻之上下文之內容(尤其關於主題)被認為全文形成本發明之揭示內容之一部分。當本發明中使用化學(實驗)式時,指定指數可不僅為絕對數目且亦為平均值。與聚合化合物相關之指數較佳為平均值。除非另外說明,否則百分比為呈重量%形式之數字。若下文中報導量測值,除非另外說明,否則此等量測已在標準條件(25℃及1013毫巴)下進行。當下文中報導平均值時,除非另外說明,否則所討論之值為重量平均值。
根據本發明之製造丁香酚聚醚類聚矽氧烷之方法較佳包含以下步驟:1. 製造聚醚,其中至少一種環氧化物與丁香酚在至少一種過渡金屬催化劑存在下反應,2. SiH官能性矽氧烷與來自步驟1之丁香酚類聚醚反應形成至少一個SiC鍵。
已展示來自步驟1之根據本發明之聚醚允許步驟2中之反應使用較小過量聚醚以實現高於常用聚醚(例如烯丙基官能化聚醚)所需之SiH轉化率。此意謂較小量之游離聚醚仍在產物中。優於常用聚醚矽氧烷之另一重要優點為實現更高轉化率。
根據本發明之丁香酚類聚醚較佳具有式(I)中所展示之構造:
其中a=1至1000,較佳2至500,尤其較佳3至500,更佳大於3至100,特別較佳4至50,b=0至1000,較佳1至500,更佳大於1至200,特別較佳0至50,c=0至1000,較佳1至100,更佳大於1至80,特別較佳0至50,d=0至1000,較佳1至100,更佳大於1至80,特別較佳0至50,e=1至10,f=0至500,較佳1至300,尤其較佳2至200且特別較佳0至100,其限制條件為a+b+c+d+f之總和不小於3,且其限制條件為具有指數a、b、c、d及f之基團在分子鏈內可自由互換,且具有指數c與d之基團中無一者可跟隨自身或各別其他基團,且其限制條件為不同單體單元與具有指數a、b及f之片段可彼此呈嵌段結構,其中個別嵌段亦可出現多次且彼此之間可隨機分佈,或者具有隨機分佈且另外彼此可自由互換,意為其可以任何所需順序配置,具有如下限制:具有指數c與d之基團中無一者可跟隨自身或各別其他基團,且其中,R1=在每次出現時獨立地為氫基或C1-C8烷基,較佳為氫、甲基或乙基,
尤其較佳為氫,R2=在每次出現時獨立地為氫基、C1-C20烷基、芳基或烷芳基,較佳為氫、甲基、乙基、辛基、癸基、十二烷基、苯基、苄基,更佳為氫、甲基或乙基,或R1與基團R2中之一者可一起形成包括與R1及R2鍵結之原子之環,此環較佳包含5至8個碳原子,R3=在每次出現時獨立地為包含2至30個碳原子、特定言之高達24個碳原子之飽和或不飽和、脂族或芳族烴基,其視情況進一步經取代,例如R3亦可包含矽烷基、烷氧基矽烷基或羧酸酯基,例如二烷氧基烷基矽烷基或三烷氧基矽烷基,較佳三甲氧基矽烷基、三乙氧基矽烷基、二甲氧基甲基矽烷基或二乙氧基甲基矽烷基,R4、R7=在每次出現時獨立地為氫及/或有機基團,較佳為烷基、烯基、亞烷基、烷氧基、芳基及/或芳烷基,或者視情況R4及/或R7可不存在,其中,當R4及R7不存在時,存在C=C雙鍵替代基團R4及R7,橋接片段Z可存在或不存在;當橋接片段Z不存在時,則R5、R6=在每次出現時獨立地為氫及/或有機基團,較佳為烷基、烯基、亞烷基、烷氧基、芳基及/或芳烷基,其中,當基團R4或R7中之一者不存在時,各別偕基(亦即,在R4不存在時為R5及在R7不存在時為R6)為亞烷基、較佳亞甲基(=CH2);當橋接片段Z存在時,則R5、R6=經由片段Z以環脂族或芳族形式橋接之烴基,其中Z表示可
進一步經取代之二價伸烷基或伸烯基,R10=在每次出現時獨立地為氫基或C1-C8烷基或酯基-C(O)-R11或乙醯乙酸酯基-C(O)-CH2-C(O)-R12或矽烷醚基團-Si(R13)3或胺基甲酸酯基-C(O)-N-(R14)2,其中,R11、R12、R13=在每次出現時獨立地為直鏈或分支鏈、飽和或不飽和、視情況進一步經取代之C1-C30烷基、芳基或烷芳基,且R14=在每次出現時獨立地為氫及/或直鏈或分支鏈、飽和或不飽和、視情況進一步經取代之C1-C30烷基、芳基或烷芳基,R10較佳為氫、甲基、乙醯基或乙醯乙酸酯基,更佳為氫或乙醯基。
通式(I)之丁香酚類聚醚較佳包含指數a之至少一個片段,更佳指數a之至少兩個不同片段。
烷氧基化反應所採用之起始物為丁香酚,其在去質子化之後可導致展示於式(I)中片段a之左側的片段。
丁香酚(CAS號97-53-0)為藉由化學名稱已知之烯丙基取代之酚。丁香酚(CAS號97-53-0)為藉由化學名稱4-烯丙基-2-甲氧基苯酚、4-丙-2-烯基-2-甲氧基苯酚、4-烯丙基鄰苯二酚-2-甲醚及5-烯丙基癒創木酚已知之烯丙基取代之酚。丁香酚為天然原料且為丁香油及甘椒油之主要成分。丁香酚可藉由丁香油之鹼水溶液處理(提取)獲得。丁香酚原料之可持續來源及石化原料之隨之而來的避開為出於生態觀點之一實質性優點,尤其在進一步認為丁香酚不與任何作為食物之用途競爭時。
可使用之環氧烷一般包括熟習此項技術者已知之所有環氧烷及可以純形式或以任何所需混合物形式使用之此等環氧烷。可使用且導
致式(I)中指定之具有指數a的片段之環氧烷化合物之實例包括環氧乙烷、1,2-環氧丙烷(環氧丙烷)、1,2-環氧-2-甲基丙烷(環氧異丁烷)、表氯醇、2,3-環氧-1-丙醇、1,2-環氧丁烷(環氧丁烷)、2,3-環氧丁烷、2,3-二甲基-2,3-環氧丁烷、1,2-環氧戊烷、1,2-環氧-3-甲基戊烷、1,2-環氧己烷、1,2-環氧環己烷、1,2-環氧庚烷、1,2-環氧辛烷、1,2-環氧壬烷、1,2-環氧癸烷、1,2-環氧十一烷、1,2-環氧十二烷、氧化苯乙烯、1,2-環氧環戊烷、1,2-環氧環己烷、乙烯基環氧環己烷、(2,3-環氧丙基)苯、乙烯基環氧乙烷、3-苯氧基-1,2-環氧丙烷、2,3-環氧甲醚、2,3-環氧乙醚、2,3-環氧異丙醚、硬脂酸3,4-環氧丁酯、乙酸4,5-環氧戊酯、2,3-環氧丙烷甲基丙烯酸酯、2,3-環氧丙烷丙烯酸酯、丁酸縮水甘油酯、縮水甘油酸甲酯、2,3-環氧丁酸乙酯、4-(三甲基矽烷基)丁烷1,2-環氧化物、4-(三乙基矽烷基)丁烷1,2-環氧化物、3-(全氟甲基)-1,2-環氧丙烷、3-(全氟乙基)-1,2-環氧丙烷、3-(全氟丁基)-1,2-環氧丙烷、3-(全氟己基)-1,2-環氧丙烷、4-(2,3-環氧丙基)嗎啉、1-(環氧乙烷-2-基甲基)吡咯烷-2-酮。較佳為使用環氧乙烷、環氧丙烷、環氧丁烷及氧化苯乙烯。尤其較佳為使用環氧乙烷及環氧丙烷。在一極尤其較佳具體實例中,以1:3至3:1、較佳1:2至1:1之莫耳比採用環氧乙烷與環氧丙烷。
可使用且導致式(I)中指定之具有指數b的片段之縮水甘油醚一般包括熟習此項技術者已知之所有縮水甘油醚及可以純形式或以任何所需混合物形式採用之此等縮水甘油醚。
較佳為甲基、乙基、丙基、丁基、異丁基、第三丁基、2-戊基、3-戊基、2-甲基丁基、3-甲基丁基、2-甲基-2-丁基、3-甲基-2-丁基、2,2-二甲基丙基、己基、庚基、辛基、2-乙基己基、2-丙基庚基、2-丁基辛烷
基、2-甲基十一烷基、2-丙基壬基、2-乙基癸基、2-戊基庚基、2-己基癸基、2-丁基十四烷基、2-十二烷基十六烷基、2-十四烷基十八烷基、3,5,5-三甲基己基、異壬烷基、異十三烷基、異肉豆蔻基、異硬脂基、2-辛基十二烷基、三苯甲基、C(O)-(CH2)5-C-(CH3)3(新癸酸基)、C12/C14烷基、苯基、甲苯基、第三丁基苯基或苄基之縮水甘油醚以及3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三丙氧基矽烷、3-縮水甘油氧基丙基三異丙氧基矽烷、雙(3-縮水甘油氧基丙基)二甲氧基矽烷、雙(3-縮水甘油氧基丙基)二乙氧基矽烷、3-縮水甘油氧基己基三甲氧基矽烷、3-縮水甘油氧基己基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基乙基二乙氧基矽烷。尤其較佳為2-乙基己基、新癸酸基、C12/C14烷基、甲苯基、第三丁基苯基之縮水甘油醚,且極尤其較佳為第三丁基苯基或甲苯基之縮水甘油醚。
可使用之縮水甘油醚亦包括多官能縮水甘油醚,諸如1,4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、環己烷二甲醇二縮水甘油醚、新戊二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、聚甘油-3縮水甘油醚、甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚或季戊四醇四縮水甘油醚;及亦允許將分支鏈結構元素引入式(I)之最終烷氧基化產物中之此等縮水甘油醚。
式(I)中指定之具有指數c的片段可藉由執行與CO2之共聚合來引入聚醚中。
可使用且導致式(I)中指定之具有指數b的片段之環酐一般包括熟習此項技術者已知之所有環酐及可以純形式或以任何所需混合物
形式採用之此等環酐。較佳可使用之飽和、不飽和或芳族環狀二羧酸酐包括丁二酸酐、辛(烯)基丁二酸酐、癸(烯)基丁二酸酐、十二(烯)基丁二酸酐、順丁烯二酸酐、伊康酸酐、戊二酸酐、己二酸酐、檸康酸酐、偏苯三酸酐、鄰苯二甲酸酐、六氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、二氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐及甲基四氫鄰苯二甲酸酐;以及多官能酐,諸如苯均四酸二酐、二苯甲酮-3,3',4,4'-四甲酸二酐、1,2,3,4-丁烷四甲酸二酐及順丁烯二酸酐與乙烯、異丁烯、丙烯腈、乙酸乙烯酯或苯乙烯之自由基聚合的均聚物或共聚物。
尤其較佳為丁二酸酐、順丁烯二酸酐、鄰苯二甲酸酐及六氫鄰苯二甲酸酐,尤其順丁烯二酸酐及鄰苯二甲酸酐。
可使用且導致式(I)中指定之具有指數f的片段之內酯一般包括熟習此項技術者已知之所有內酯及可以純形式或以任何所需混合物形式採用之此等內酯。
較佳為戊內酯或己內酯及可未經取代或經烷基、較佳甲基取代之此等戊內酯或己內酯。較佳為ε-己內酯或δ-戊內酯,尤其ε-己內酯。
OH官能性起始物化合物之烷氧基化可在鹼、酸或過渡金屬催化下進行。如在開始時所提及,鹼性催化劑不可用於丁香酚之烷氧基化,因為此導致重組形成異丁香酚。
在根據本發明之製造丁香酚類聚醚的方法之步驟1中,丁香酚之烷氧基化可在過渡金屬催化劑存在下進行。烷氧基化較佳在雙金屬氰化物(DMC)催化劑存在下進行。
用於烷氧基化反應之DMC催化劑之製造及用途自20世紀
60年代已為已知且概述於例如US 3,427,256、US 3,427,334、US 3,427,335、US 3,278,457、US 3,278,458及US 3,278,459中。舉例而言,US 5,470,813、US 5,482,908及EP 1276563 B1中甚至已同時研發出更有效DMC催化劑,具體言之鋅-鈷六氰錯合物。
根據本發明之方法中所用之雙金屬氰化物催化劑(DMC催化劑)較佳為EP 1276563 B1中所描述之雙金屬氰化物催化劑,尤其其中描述為較佳或尤其較佳之DMC催化劑。
下文中更詳細描述根據本發明之方法之兩個步驟。
步驟1:
根據本發明之製造丁香酚類聚醚的方法之第一步驟包含執行起始物丁香酚與包含環氧化物基團(環氧烷及縮水甘油醚)的化合物之DMC催化之烷氧基化。所有方法步驟可在相同或不同溫度下進行。根據本發明之方法之烷氧基化反應藉由最初將由丁香酚與雙金屬氰化物催化劑組成之起始物混合物饋入反應器中來起始。
反應混合物中之催化劑濃度較佳為>0wppm(質量百萬分率)至1000wppm,較佳>0wppm至500wppm,更佳0.1wppm至400wppm且最佳10wppm至300wppm。此濃度係以所形成之烷氧基化產物之總質量計。
催化劑較佳僅一次計量至反應器中。催化劑量將設定為使得為該方法提供足夠的催化活性。催化劑可以固體形式或以催化劑懸浮液形式計量。所用懸浮液介質可為惰性溶劑或有利地丁香酚或者兩種組分之混合物。
最初饋入反應器中以起始反應之起始物(丁香酚)、DMC催化劑與任何懸浮液介質之起始物混合物可根據WO 98/52689之教示藉由汽提進行預處理,隨後開始單體之計量添加。此包含經由反應器饋料端摻合惰性氣體與反應混合物且藉由使用連接至反應器系統之真空設備施加負壓自反應混合物移除相對揮發性組分。以此簡單方式,可自反應混合物移除可能抑制催化劑之物質,諸如低級醇或水。添加惰性氣體且同時移除相對揮發性組分尤其在反應啟動時可為有利的,因為反應物之添加或次級反應亦可將抑制化合物引入反應混合物中。
將環氧丙烷或至少一種其他環氧化合物計量至最初饋入之起始物混合物中。為起始烷氧基化反應且使雙金屬氰化物催化劑活化,一般最初僅添加待計量之環氧化物之一定總量。在此起始階段中,環氧化物與丁香酚之莫耳比較佳為0.1:1至15:1,較佳0.2:1至10:1,特定言之0.4:1至5:1。
放熱反應之起始可藉由例如監測壓力及/或溫度來偵測。在氣態環氧烷之情況下,反應器中壓力突然下降指示正在併入環氧烷,反應已因此起始且已達到起始階段之末端。在非氣態環氧烷及縮水甘油醚/酯之情況下,反應之開始藉由其中設定之熱量的演變來指示。
起始階段之後,亦即反應初始化之後,可視莫耳質量訴求而定計量另外環氧烷。或者,亦有可能添加不同環氧烷化合物與縮水甘油醚/酯之任何所需混合物,且此等亦可以任何所需順序分別且連續添加。
反應可例如在惰性溶劑中進行以降低反應混合物之黏度。適合惰性溶劑為例如烴,尤其甲苯、二甲苯或環己烷。然而,此為比較不佳
的。
在根據本發明之產物中,計量的環氧化物(包括在起始階段中添加之環氧化物)之總和之莫耳比以所採用之起始物化合物計較佳為1至105:1,特定言之1至103:1。
環氧烷化合物之添加較佳在60℃至250℃之溫度下、更佳在90℃至160℃之溫度下、特定言之在120℃至150℃之溫度下執行。
執行烷氧基化之壓力較佳為0.02巴至100巴,更佳0.05巴至20巴且特定言之0.2巴至2巴絕對值。實質上在負壓下執行烷氧基化允許極安全地執行反應。烷氧基化可視情況在惰性氣體(例如氮氣)存在下執行,或對製造聚醚碳酸酯而言在二氧化碳存在下、在此情況下亦在較佳1巴至20巴絕對值之正壓下執行。
可用於製造酯改質之聚醚的內酯或環酐可在起始階段儘早添加至丁香酚與DMC催化劑之混合物中或在稍後時間點與環氧烷之計量添加同時引入。所提及之共聚單體亦可各自與環氧烷交替連續計量至反應器中。
此處,環氧烷單體與環酐之莫耳比可變化。以酐計,典型地採用至少等莫耳量之環氧烷單體。較佳為使用莫耳過量之環氧烷以便確保完全酐轉化。
可在烷氧基化期間以按環氧烷單體計化學計算量不足或過量來添加內酯。
在根據本發明之方法之步驟1之一個特定具體實例中,有利的可為在烷氧基化過程期間將其他起始物引入反應混合物中。
另外量之丁香酚之計量添加可例如在特定時間點或者在兩個或多於兩個時間點以逐份方式執行。此可包含在所需數目之部分內均勻分佈丁香酚總量但亦有可能以不同大小之部分劃分總量。
除上文所描述之丁香酚之不連續添加之外,亦可連續執行該添加。此可包含在烷氧基化反應期間執行一次連續添加或兩次或多於兩次。較佳連續執行丁香酚之添加。尤其較佳為一次且隨後以連續方式執行丁香酚之添加時。
在單體添加及任何後反應完成單體轉化之後,典型地藉由真空蒸餾、氣提或其他除臭方法移除未反應單體之任何殘餘物及任何其他揮發性成分。揮發性次要組分可不連續(分批)或連續移除。在根據本發明之基於DMC催化之方法中,通常可避開過濾。
丁香酚類聚醚之末端羥基可保持游離或可完全或在一定程度上改質以便可實現稍後應用基質中之最佳相容性。
可想像的改質不僅包括例如與異氰酸酯之進一步縮合或加成反應且亦包括轉酯化、酯化及醚化。
在一個較佳具體實例中,該反應可用矽烷醇形成物質或單異氰酸酯、較佳用單異氰酸酯執行,如描述於申請案EP 2415797(US 2012/029090)中。
可採用之適合單異氰酸酯在最簡單的情況下包括異氰酸烷基酯、異氰酸芳酯及異氰酸芳烷基酯。較佳可採用異氰酸甲酯、異氰酸乙酯、異氰酸丁酯、異氰酸己酯、異氰酸辛酯、異氰酸十二烷基酯、異氰酸甲苯甲醯酯及異氰酸硬脂基酯,異氰酸丁酯為尤其較佳的。亦可採用雙官
能異氰酸酯,諸如MDI、IPDI及TDI,但此為比較不佳的。
在另一較佳具體實例中,該反應可執行為與諸如乙醯乙酸乙酯或乙醯乙酸第三丁酯之乙醯乙酸酯進行轉酯化。此類轉酯化有利地在90-140℃之溫和反應條件下進行,一般導致甚至在無催化劑之情況下良好轉化率。視需要,亦可藉由使聚醚與雙烯酮反應來引入乙醯乙酸酯基。
較佳為末端羥基保持游離或經乙醯化或甲基化或經碳酸酯或乙醯乙酸酯封端時。尤其較佳為末端OH基團保持游離或經乙醯化時。
丁香酚類聚醚之游離羥基之化學改質可為在羥矽基化反應之前或之後經Si-H官能性聚矽氧烷化學改質。
較佳為式(I)之丁香酚類聚醚之多分散性(Mw/Mn)藉由GPC測定為<2.5、較佳<2.0且更佳>1.05至<1.5時。
根據本發明之式(I)之丁香酚類聚醚可用於多種應用中,包括特定言之用作界面活性劑且更特定言之用作分散劑。
該方法之步驟1原則上可獨立且在無隨後方法步驟2之情況下執行。本發明同樣提供步驟1之方法產物。然而,較佳為步驟1之方法產物在步驟2中進一步反應時。
步驟2:
根據本發明之方法之步驟2較佳以羥矽基化形式進行。此包含在貴金屬催化下在來自步驟1之末端不飽和丁香酚類聚醚與SiH官能性矽氧烷之間形成SiC鍵。
方法步驟2提供SiH官能性矽氧烷較佳由進行先前技術之平衡方法來實現,較佳對磺化樹脂。具有末端及/或側位SiH官能基之分支鏈
或直鏈、視情況羥矽基化聚(有機)矽氧烷之平衡描述於先前技術中,例如文獻EP 1 439 200 A1、DE 10 2007 055 485 A1及DE 10 2008 041 601中。此等文獻以引用的方式併入本文中且被認為形成本發明之揭示內容之一部分。
較佳採用之聚矽氧聚醚嵌段共聚物之製備可由先前技術方法實現,其中具有末端及/或側位SiH官能基之分支鏈或直鏈聚有機矽氧烷與不飽和聚醚或由至少兩個不飽和聚醚組成之聚醚混合物反應。該反應較佳以貴金屬催化之羥矽基化形式進行,如描述於例如EP 1 520 870中。文獻EP 1 520 870以引用的方式併入本文中且因此被認為形成關於根據本發明之方法之步驟2的揭示內容之一部分。所用貴金屬催化劑較佳為包含鉑之催化劑。
根據步驟2之反應可在飽和聚醚存在或不存在下進行。方法步驟2較佳在飽和聚醚存在下執行。有可能在不同於飽和聚醚之其他溶劑存在下執行方法步驟2。較佳為不使用不同於飽和聚醚之溶劑時。方法步驟2亦可在酸緩衝劑存在下執行。然而,該步驟較佳在酸緩衝劑不存在下執行。較佳為該方法步驟在酸緩衝劑及不同於飽和聚醚之溶劑不存在下執行時,且尤其較佳為步驟2僅包含使丁香酚類聚醚反應時。
步驟2不僅可採用來自步驟1之末端不飽和丁香酚類聚醚且亦可採用不同於其之其他直鏈及/或分支鏈不飽和聚醚化合物以及其他末端不飽和有機化合物。此可特別有利於使包含丁香酚聚醚之聚矽氧烷之相容性能夠調整以適應特定應用基質。
此類聚醚有利地為可藉由任何先前技術方法獲得之烯丙基聚醚。
此類末端不飽和有機化合物較佳為可攜有其他取代基之烯烴或炔烴化合物。可使用之化合物之實例包括烯丙基縮水甘油醚、甘油單烯丙醚、烯丙基苯甲醚、烯丙基苯酚、丁香酚、己烯醇、十六烯及十一烯酸甲酯,尤其較佳為十六烯、丁香酚及甘油單烯丙醚。
有可能僅使用丁香酚類聚醚或者此等丁香酚類聚醚與末端不飽和化合物之任何所需混合物。較佳為不飽和丁香酚類聚醚與不飽和化合物之所用莫耳比以丁香酚類聚醚與不飽和化合物之總和計為0.001mol%至100mol%,較佳10mol%至100mol%且更佳20mol%至80mol%時。
根據本發明之方法可用於製造例如下文中所描述之聚矽氧烷化合物。
根據本發明之式(II)聚矽氧烷化合物:MgM'hDiD'jD"mTkQl式(II)
為以下彼等者,其中,
M=[R15 3SiO1/2]
M'=[R16R15 2SiO1/2]
D=[R15 2SiO2/2]
D'=[R16R15SiO2/2]
D"=[R17R15SiO2/2]
T=[R15SiO3/2]
Q=[SiO4/2]
g=0-20,較佳0-10,更佳2,
h=0-20,較佳0-10,更佳0,i=0-1000,較佳0-500,更佳0-200,j=0-20,較佳1-15,更佳1-10,k=0-20,較佳0-10,更佳0,l=0-20,較佳0-10,更佳0,m=0-20,較佳1-15,更佳1-10,其限制條件為g+h+i+j+k+l+m之總和不小於3且總和h+j1,且,R15=在每次出現時獨立地為相同或不同C1-C16烴基,或H,較佳為甲基、乙基或苯基,更佳為甲基,R16=在每次出現時獨立地為相同或不同聚醚基團,其限制條件為至少10%基團為丁香酚類聚醚基團;丁香酚類聚醚基團較佳對應於通式(III):
且較佳非丁香酚類聚醚對應於通式(IV)之基團,
其中,指數a至f及基團R1至R10如上文所定義,R17=在每次出現時獨立地為相同或不同C1-C16烴基,其亦包含雜原子
且可進一步經取代,較佳有關由烯丙基縮水甘油醚、甘油單烯丙醚、烯丙基苯甲醚、丁香酚、己烯醇、十六烯及十一烯酸甲酯,更佳十六烯、丁香酚及甘油單烯丙醚產生之SiC鍵聯基團。
有利地在需要相容性調適之系統中採用不僅包含式(III)之丁香酚類聚醚且亦包含式(IV)之其他非丁香酚類聚醚之通式(II)化合物;當聚醚矽氧烷僅包含丁香酚類聚醚結構時,亦可經由丁香酚類聚醚之固有結構實現相容性之任何必要調適。
根據本發明之聚矽氧烷化合物較佳可藉由根據本發明之上文所描述之方法獲得。
根據本發明之式(II)聚矽氧烷化合物及根據本發明之組成物可用於多種應用中,其作為界面活性劑之用途為一特定實例。
本發明因此進一步提供式(I)產物用作界面活性劑之用途。本發明同樣提供式(I)產物用作分散添加劑之用途。
另外,本發明進一步提供式(II)產物用作界面活性劑之用途。本發明同樣提供式(II)產物用作分散添加劑之用途。
量測方法:
參數或量測值較佳藉由下文中所描述之方法測定。特定言之,此等方法用於本智慧財產權之實施例。
使用Shimadzu Biotech Axima(CFR 2.8.420081127)儀器以反射模式執行MALDI-Tof分析。使分子量為1000g/mol之脈衝提取最佳化。將樣本溶解於氯仿(4-5g/l)中且將2μL此溶液塗覆至石墨作為基質。
在本發明之上下文中,所製造的丁香酚類聚醚及包含丁香酚
聚醚之聚矽氧烷之重量平均分子量與數目平均分子量係藉由凝膠滲透層析法(GPC)測定,在該等聚醚之情況下相對於聚丙二醇標準且在該等聚矽氧烷之情況下相對於聚苯乙烯標準來校準測定,在30℃溫度及1mL/min流動速率下使用裝備有RI偵測器及由0.8×5cm前管柱與兩個0.8×30cm主管柱組成之SDV 1000/10000Å管柱組合之Agilent 1100儀器進行GPC(流動相:THF)。樣本濃度為10g/l且注射體積為20μL。
根據國際標準方法進行濕法化學分析:碘值(IN;DGF C-V 11a(53);酸值(AN;DGF C-V2);OH數(ASTM D 4274 C)。
多分散指數(PDI)為Mw除Mn之商(PDI=Mw/Mn)。
以下實施例中例示性描述本發明,而無任何意圖將本發明限於實施例中所提及之具體實例,本發明範疇藉由整個說明書及申請專利範圍確定。
實施例1:合成丁香酚類聚醚(本發明):
最初於5公升高壓釜饋入351g丁香酚,且使該丁香酚與100ppm(以總批料計)六氰鈷酸鋅雙金屬氰化物催化劑摻合。藉由饋入氮氣至3巴壓力且隨後減壓至大氣壓使反應器惰性化。此操作重複超過兩次。在攪拌時,將反應器內容物加熱至100℃且抽空至約20毫巴以移除揮發性組分。30分鐘後,將溫度升高至130℃且將100g環氧丙烷計量至抽空反應器中以使催化劑活化。內部壓力最初上升至約0.8巴。壓力開始緩慢下降且在約7分鐘之後已下降至-0.1巴。隨後計量另一50g PO,造成壓力再一次上升至0.8巴。12分鐘後,壓力已下降至-0.1巴,且計量另一50g PO。一旦壓力已下降至0巴,開始PO之緩慢連續計量添加。在已添加總計210g PO之後,
壓力突然下降至-0.9巴,用來指示反應之真正開始。隨後連續計量38g環氧丙烷歷經約10分鐘。此隨後進行一小時後反應。隨後連續計量1110g EO與1290g PO之混合物,使得溫度保持恆定。在另一半小時之後反應後,藉由施加壓力(P<20毫巴)使批料除臭以移除未經轉化之環氧烷之殘餘物。隨後攪拌500ppm之ANOX 20 AM歷經15分鐘。此得到OH數為40.2mg KOH/g且AN為0.1mg KOH/g之無色至淡黃色產物。根據OH數之分子量為1395g/mol。根據GPC,Mw=1394g/mol,Mn=1316g/mol且PDI為1.06。
實施例2:合成丁香酚類聚醚(本發明):
最初於5公升高壓釜饋入164.2g丁香酚,且使該丁香酚與100ppm(以總批料計)六氰鈷酸鋅雙金屬氰化物催化劑摻合。藉由饋入氮氣至3巴壓力且隨後減壓至大氣壓使反應器惰性化。此操作重複超過兩次。在攪拌時,將反應器內容物加熱至100℃且抽空至約20毫巴以移除揮發性組分。30分鐘後,將溫度升高至130℃且將70g環氧丙烷計量至抽空反應器中以使催化劑活化。內部壓力最初上升至約0.8巴。壓力開始緩慢下降且在約30分鐘之後已下降至-0.4巴。隨後開始環氧丙烷之緩慢連續添加。在添加另一56g PO之後壓力上升至0.7巴,且隨後在添加總計200g PO之後突然下降至-0.8巴,且此突然下降用來指示反應之真正開始。隨後連續計量1673g環氧丙烷,使得溫度保持恆定。在另一半小時之後反應後,藉由施加壓力(P<20毫巴)使批料除臭以移除未經轉化之環氧烷之殘餘物。隨後攪拌500ppm之ANOX 20 AM歷經15分鐘。此得到OH數為26.8mg KOH/g且AN為0.1mg KOH/g之無色至淡黃色產物。根據OH數之分子量為2093g/mol。根據GPC,Mw=1957g/mol,Mn=1830g/mol且PDI為1.07。
實施例3:合成丁香酚類聚醚(本發明):
最初於5公升高壓釜饋入544g丁香酚,且使該丁香酚與200ppm(以總批料計)六氰鈷酸鋅雙金屬氰化物催化劑摻合。藉由饋入氮氣至3巴壓力且隨後減壓至大氣壓使反應器惰性化。此操作重複超過兩次。在攪拌時,將反應器內容物加熱至80℃且抽空至約20毫巴以移除揮發性組分。30分鐘後,將溫度升高至140℃且將80g環氧丙烷計量至抽空反應器中以使催化劑活化。內部壓力最初上升至約0.6巴。壓力開始緩慢下降且在約10分鐘之後已下降至-0.2巴。隨後計量另一74g PO,造成壓力歷經60分鐘緩慢下降至-0.8巴。隨後開始612g環氧乙烷與691g環氧丙烷之混合物之計量添加。計量110g之EO/PO混合物歷經30分鐘,使反應器中之壓力上升至0.5巴。隨後歷經15分鐘添加另一54g混合物。壓力上升至1.5巴,隨後突然下降至-0.5巴,用來指示反應之真正開始。隨後連續計量剩餘環氧烷混合物(1139g)歷經40分鐘。在另一半小時之後反應後,藉由施加壓力(P<20毫巴)使批料除臭以移除未經轉化之環氧烷之殘餘物。隨後攪拌500ppm之ANOX 20 AM歷經15分鐘。此得到OH數為81.8mg KOH/g且AN為0.1mg KOH/g之無色至淡黃色產物。根據OH數之分子量為685g/mol。根據GPC,Mw=640g/mol,Mn=583g/mol且PDI為1.10。
實施例4:合成丁香酚類聚醚(本發明):
最初於5公升高壓釜饋入503g丁香酚,且使該丁香酚與100ppm(以總批料計)六氰鈷酸鋅雙金屬氰化物催化劑摻合。藉由饋入氮氣至3巴壓力且隨後減壓至大氣壓使反應器惰性化。此操作重複超過兩次。在攪拌時,將反應器內容物加熱至120℃且抽空至約20毫巴以移除揮發性組分。
30分鐘後,將溫度升高至130℃且將70g環氧丙烷計量至抽空反應器中以使催化劑活化。內部壓力最初上升至約0.5巴。壓力開始緩慢下降且在約20分鐘之後已下降至-0.9巴。隨後緩慢地計量196g PO歷經40分鐘時段,造成壓力上升至0.5巴。後反應30分鐘後,壓力下降至-0.4巴,且開始1078g EO與1154g PO之混合物之計量添加。計量60g之EO/PO混合物歷經30分鐘,造成反應器中之壓力最初上升至輕微正壓且隨後突然下降至-0.9巴,用來指示反應之真正開始。隨後連續計量剩餘環氧烷混合物(2172g)歷經75分鐘。在另一半小時之後反應後,藉由施加壓力(P<20毫巴)使批料除臭以移除未經轉化之環氧烷之殘餘物。隨後攪拌500ppm之ANOX 20 AM歷經15分鐘。此得到OH數為51.6mg KOH/g且AN為0.1mg KOH/g之無色至淡黃色產物。根據OH數之分子量為1087g/mol。根據GPC,Mw=1012g/mol,Mn=945g/mol且PDI為1.07。
實施例5:來自實施例1之丁香酚類聚醚(本發明)之乙醯化
在保護性氣體下,最初將裝備有滴液漏斗及回流冷卻器之2公升三頸燒瓶饋入來自實施例1之丁香酚類聚醚及催化量之濃鹽酸,且加熱所得混合物。隨後緩慢添加乙酸酐。完成添加之後將混合物攪拌另一4h。隨後蒸餾出任何殘餘酸,得到OH數為0.1mg KOH/g且AN為0.1mg KOH/g之無色至淡黃色產物。在兩個獨立量測之分析量測不準確範圍內,OH數表明已實現聚醚之末端OH基團之定量乙醯化。在量測不準確範圍內,與來自實施例1之聚醚相比GPC保持不變。根據GPC,Mw=1424g/mol,Mn=1316g/mol且PDI為1.08。
實施例6:合成2-萘酚類聚醚(比較實施例):
類似於實施例2進行反應。最初饋入144.1g 2-萘酚及200ppm(以總批料計)六氰鈷酸鋅雙金屬氰化物催化劑,且添加1856g PO。在反應開始之前有必要逐份添加215g PO。此造成壓力上升至最大2巴,隨後在添加最終PO部分之後其歷經12分鐘下降至-0.9巴。計量剩餘環氧丙烷歷經75分鐘。此得到OH數為31.8mg KOH/g且AN為0.2mg KOH/g之無色至淡黃色產物。根據OH數之分子量為1764g/mol。根據GPC,Mw=1945g/mol,Mn=1730g/mol且PDI為1.12。
實施例7:合成癒創木酚類聚醚(比較實施例):
類似於實施例2進行反應。最初饋入125g癒創木酚及100ppm(以總批料計)六氰鈷酸鋅雙金屬氰化物催化劑,且添加1894g PO。此得到OH數為31.7mg KOH/g且AN為0.1mg KOH/g之無色至淡黃色產物。根據OH數之分子量為1769g/mol。根據GPC,Mw=1936g/mol,Mn=1667g/mol且PDI為1.16。
實施例8:用丁香酚類聚醚製造聚醚矽氧烷(本發明)
在具有溫度計、回流冷卻器及KPG攪拌器之500mL三頸燒瓶中,將通式[Me2SiHO1/2]2[Me2SiO2/2]37[MeSiHO2/2]3之79.0g SiH官能性矽氧烷
與來自實施例4之171g丁香酚類聚醚摻合。攪拌混合物,且加熱至90℃。隨後將反應混合物與卡爾施泰特催化劑(Karstedt's catalyst)(CAS號:68478-92-2)於二甲苯(1.5% Pt)中之0.17g溶液摻合。觀測放熱反應。攪拌混合物兩小時。此得到淡黃色澄清單相液體。
實施例9:用丁香酚類聚醚製造聚醚矽氧烷(本發明)
在具有溫度計、回流冷卻器及KPG攪拌器之500mL三頸燒瓶中,將通式[Me3SiO1/2]2[Me2SiO2/2]13[MeSiHO2/2]5之44.3g SiH官能性矽氧烷與來自實施例4之205.7g丁香酚類聚醚摻合。攪拌混合物,且加熱至90℃。隨後將反應混合物與卡爾施泰特催化劑(CAS號:68478-92-2)於二甲苯(1.5% Pt)中之0.17g溶液摻合。觀測放熱反應。攪拌混合物兩小時。此得到淡黃色澄清單相液體。
實施例10:用丁香酚類聚醚及非丁香酚類聚醚製造聚醚矽氧烷(本發明)
在具有溫度計、回流冷卻器及KPG攪拌器之500mL三頸燒瓶中,將通式[Me3SiO1/2]2[Me2SiO2/2]13[MeSiHO2/2]5之40.0g SiH官能性矽氧烷與來自實施例4之94.8g丁香酚類聚醚及通式CH2=CHCH2O-(CH2CH2O)13(CH2CH(CH3)O)13Me之132.7g聚醚摻合。攪拌混合物,且加熱至90℃。隨後將反應混合物與卡爾施泰特催化劑(CAS號:68478-92-2)於二甲苯(1.5% Pt)中之0.18g溶液摻合。觀測放熱反應。攪拌混合物兩小時。此得到淡黃色澄清單相液體。
實施例11:用丁香酚類聚醚製造聚醚矽氧烷(本發明)
在具有溫度計、回流冷卻器及KPG攪拌器之500mL三頸燒
瓶中,將通式[Me2SiHO1/2]2[Me2SiO2/2]28之112.0g SiH官能性矽氧烷與來自實施例4之138.0g丁香酚類聚醚摻合。攪拌混合物,且加熱至90℃。隨後將反應混合物與卡爾施泰特催化劑(CAS號:68478-92-2)於二甲苯(1.5% Pt)中之0.17g溶液摻合。觀測放熱反應。攪拌混合物兩小時。此得到淡黃色澄清單相液體。
實施例12:用丁香酚類聚醚製造聚醚矽氧烷(本發明)
在具有溫度計、回流冷卻器及KPG攪拌器之500mL三頸燒瓶中,將通式[Me3SiO1/2]2[MeSiHO2/2]1之32.0g SiH官能性矽氧烷與來自實施例4之218.0g丁香酚類聚醚摻合。攪拌混合物,且加熱至90℃。隨後將反應混合物與卡爾施泰特催化劑(CAS號:68478-92-2)於二甲苯(1.5% Pt)中之0.2g溶液摻合。觀測放熱反應。攪拌混合物五小時。此得到淡黃色澄清單相液體。
實施例13:用丁香酚類聚醚及非丁香酚類聚醚製造聚醚矽氧烷(本發明)
在具有溫度計、回流冷卻器及KPG攪拌器之500mL三頸燒瓶中,將通式[Me3SiO1/2]2[Me2SiO2/2]113[MeSiHO2/2]5之150g SiH官能性矽氧烷與來自實施例4之45.9g丁香酚類聚醚及通式CH2=CHCH2O-(CH2CH2O)13(CH2CH(CH3)O)2H之55.1g聚醚摻合。攪拌混合物,且加熱至90℃。隨後將反應混合物與卡爾施泰特催化劑(CAS號:68478-92-2)於二甲苯(1.5% Pt)中之0.15g溶液摻合。觀測放熱反應。攪拌混合物兩小時。此得到淡黃色稍混濁液體。
實施例14:用丁香酚類聚醚及十二烯製造聚醚矽氧烷(本發明)
最初將通式Me3SiO[SiMe2O]70[SiHMeO]20SiMe3之164g SiH官能性矽氧烷饋入1L三頸燒瓶中。將該矽氧烷加熱至80℃且與呈卡爾施泰特催化劑形式之6mg Pt摻合。隨後,緩慢逐滴添加44g之1-十二烯。隨後緩慢計量來自實施例4之424g聚醚。在80℃下攪拌反應混合物另一2h。此得到澄清、均質的經烷基改質與經聚醚改質之矽氧烷。
實施例15a:用丁香酚類聚醚製造聚醚矽氧烷(本發明)
最初將具有KPG攪拌器及回流冷卻器之250mL三頸燒瓶饋入通式Me3SiO[SiMe2O]61.5[SiMeH]6.5SiMe3之80g矽氧烷及具有以下所展示之通式的112g聚醚:
超過SiH官能基之雙鍵超出量為12%。劇烈攪拌混合物,且加熱至80℃。以卡爾施泰特催化劑形式添加8ppm Pt。在80℃下攪拌反應混合物4小時。此得到澄清產物。SiH轉化率為97%。
實施例15b:用烯丙基類聚醚製造聚醚矽氧烷(非本發明)
最初將具有KPG攪拌器及回流冷卻器之250mL三頸燒瓶饋入通式Me3SiO[SiMe2O]61.5[SiMeH]6.5SiMe3之80g矽氧烷及具有以下所展示之通式的100g聚醚:
超過SiH官能基之雙鍵超出量為12%。劇烈攪拌混合物,且加熱至80℃。以卡爾施泰特催化劑形式添加8ppm Pt。在80℃下攪拌反應混合物4
小時。此得到澄清產物。SiH轉化率僅為89%。SiH轉化率即使在另一2小時反應時間之後並未提高。
實施例15a與實施例15b之比較展示根據本發明之聚醚使得有可能使用較小過量聚醚實現高SiH轉化率。此意謂較小量之游離聚醚仍在產物中。優於常用聚醚矽氧烷之另一重要優點為實現更高轉化率。
實施例16:效能評估
a.)用根據本發明之聚醚製造顏料製劑(顏料漿)之配方:
b.)製造與測試方法:
將原料連續稱重至250mL寬頸燒瓶中且均質化。隨後將直徑為2.5-2.8mm之200g玻璃珠稱重至混合物中。將混合物分散於DAS H[/A]200K分散器中2小時(排氣階段1)。仍溫熱樣本經由400μm快速篩過濾且隨後靜置24h。
製造基於Neocryl XK 90之儲備漆用於測定顏色特性。
將表2中之條目1至條目6稱重至250mL玻璃瓶中。將直徑為2.5-2.8mm之100g玻璃珍珠稱重至混合物中,且在排氣階段1將混合物分散於DAS H[/A]200K分散器中1小時。隨後添加條目7至條目10,且將混合物分散另一10分鐘。漆經由400μm快速篩過濾,且在使用之前在室溫下靜置24h。
白色漆之著色:
將10g漆且在每種情況下0.2g漿料稱重至體積為60ml之小的Dürrmann裝飾燒杯中。將混合物在DAC 150 FVZ快速混合機(Speedmixer)中在3000rpm下均質化1分鐘。隨後使用100μm線繞刮刀將著色漆塗覆至Leneta 2DX對比卡。三分鐘初始乾燥時間之後,執行擦去
測試。24小時澈底乾燥時間之後,使用利用「包括鏡面光澤(specular gloss included)」設置之X-Rite SP 62球形分光光度計量測L*a*b*值。計算非摩擦表面對比摩擦表面之△E值;及顏色強度。比色值再現為CIE L*a*b*顏色模型之成分(DIN 6174:「Farbmetrische Bestimmung von Farbmaßzahlen und Farbabständen im angenähert gleichförmigen CIELAB-Farbenraum」[根據大致均勻CIELAB顏色空間進行色座標及色差之比色評估])。
所尋求的為展示高顏色強度及低△E值之流動白色系顏料製劑,如藉由來自實施例1之本發明聚醚獲得。
c.)結果
Claims (15)
- 一種製造烷氧基化產物之方法,其中至少一種環氧化物與丁香酚在至少一種過渡金屬催化劑存在下反應。
- 如申請專利範圍第1項之方法,其特徵在於至少一種過渡金屬催化劑為雙金屬氰化物催化劑。
- 如申請專利範圍第1項與第2項中任一項之方法,其中至少一種環氧化物選自環氧乙烷、環氧丙烷、環氧異丁烷、表氯醇、2,3-環氧-1-丙醇、環氧丁烷、2,3-環氧丁烷、2,3-二甲基-2,3-環氧丁烷、1,2-環氧戊烷、1,2-環氧-3-甲基戊烷、1,2-環氧己烷、1,2-環氧環己烷、1,2-環氧庚烷、1,2-環氧辛烷、1,2-環氧壬烷、1,2-環氧癸烷、1,2-環氧十一烷、1,2-環氧十二烷、氧化苯乙烯、1,2-環氧環戊烷、1,2-環氧環己烷、乙烯基環氧環己烷、(2,3-環氧丙基)苯、乙烯基環氧乙烷、3-苯氧基-1,2-環氧丙烷、2,3-環氧甲醚、2,3-環氧乙醚、2,3-環氧異丙醚、硬脂酸3,4-環氧丁酯、乙酸4,5-環氧戊酯、2,3-環氧丙烷甲基丙烯酸酯、2,3-環氧丙烷丙烯酸酯、丁酸縮水甘油酯、縮水甘油酸甲酯、2,3-環氧丁酸乙酯、4-(三甲基矽烷基)丁烷1,2-環氧化物、4-(三乙基矽烷基)丁烷1,2-環氧化物、3-(全氟甲基)-1,2-環氧丙烷、3-(全氟乙基)-1,2-環氧丙烷、3-(全氟丁基)-1,2-環氧丙烷、3-(全氟己基)-1,2-環氧丙烷、4-(2,3-環氧丙基)嗎啉、1-(環氧乙烷-2-基甲基)吡咯烷-2-酮或其混合物。
- 如申請專利範圍第1項至第3項中任一項之方法,其特徵在於至少一種環氧化物選自環氧乙烷、環氧丙烷或其混合物。
- 如申請專利範圍第4項之方法,其特徵在於以3:1至1:3之莫耳比採用 環氧乙烷與環氧丙烷。
- 如申請專利範圍第1項至第5項中任一項之方法,其特徵在於其包含共反應選自環酐、CO2、縮水甘油醚、內酯或其混合物之至少一種其他組分。
- 如申請專利範圍第1項至第6項中任一項之方法,其特徵在於其包含第一步驟,其中至少一種環氧化物與丁香酚在至少一種過渡金屬催化劑及視情況其他組分存在下反應,及第二步驟,其中進行來自步驟1之產物與Si-H官能性矽氧烷之至少一個反應。
- 如申請專利範圍第7項之方法,其特徵在於在該第二步驟中,該來自步驟1之產物及至少一種包含末端不飽和基團之其他組分與Si-H官能性矽氧烷反應。
- 一種式(I)產物,
- 一種式(II)產物,MgM'hDiD'jD"mTkQl 式(II)其中,M=[R15 3SiO1/2] M'=[R16R15 2SiO1/2]D=[R15 2SiO2/2]D'=[R16R15SiO2/2]D"=[R17R15SiO2/2]T=[R15SiO3/2]Q=[SiO4/2]g=0-20,較佳0-10,更佳2,h=0-20,較佳0-10,更佳0,i=0-1000,較佳0-500,更佳0-200,j=0-20,較佳1-15,更佳1-10,k=0-20,較佳0-10,更佳0,l=0-20,較佳0-10,更佳0,m=0-20,較佳1-15,更佳1-10,其限制條件為g+h+i+j+k+l+m之總和不小於3且總和h+j1,且,R15=在每次出現時獨立地為相同或不同C1-C16烴基,或H,較佳為甲基、乙基或苯基,更佳為甲基,R16=在每次出現時獨立地為相同或不同聚醚基團,其限制條件為至少10%之該等基團為丁香酚類聚醚基團;該等丁香酚類聚醚基團較佳對應於通式(III):
- 如申請專利範圍第9項與第10項中任一項之產物,其特徵在於在式(I)、式(II)、式(III)及式(IV)中,具有該指數b之片段選自甲基縮水甘油醚、乙基縮水甘油醚、丙基縮水甘油醚、丁基縮水甘油醚、異丁基縮水甘油醚、第三丁基縮水甘油醚、2-戊基縮水甘油醚、3-戊基縮水甘油醚、2-甲基丁基縮水甘油醚、3-甲基丁基縮水甘油醚、2-甲基-2-丁基縮水甘油醚、3-甲基-2-丁基縮水甘油醚、2,2-二甲基丙基縮水甘油醚、己基縮水甘油醚、庚基縮水甘油醚、辛基縮水甘油醚、2-乙基己 基縮水甘油醚、2-丙基庚基縮水甘油醚、2-丁基辛烷基縮水甘油醚、2-甲基十一烷基縮水甘油醚、2-丙基壬基縮水甘油醚、2-乙基癸基縮水甘油醚、2-戊基庚基縮水甘油醚、2-己基癸基縮水甘油醚、2-丁基十四烷基縮水甘油醚、2-十二烷基十六烷基縮水甘油醚、2-十四烷基十八烷基縮水甘油醚、3,5,5-三甲基己基縮水甘油醚、異壬烷基縮水甘油醚、異十三烷基縮水甘油醚、異肉豆蔻基縮水甘油醚、異硬脂基縮水甘油醚、2-辛基十二烷基縮水甘油醚、三苯甲基縮水甘油醚、C(O)-(CH2)5-C-(CH3)3縮水甘油醚、C12/C14-烷基縮水甘油醚、苯基縮水甘油醚、甲苯基縮水甘油醚、第三丁基苯基縮水甘油醚、苄基縮水甘油醚、3-縮水甘油氧基丙基-三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三丙氧基矽烷、3-縮水甘油氧基丙基三異丙氧基矽烷、雙(3-縮水甘油氧基丙基)二甲氧基矽烷、雙(3-縮水甘油氧基丙基)二乙氧基矽烷、3-縮水甘油氧基己基三甲氧基矽烷、3-縮水甘油氧基己基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基乙基二乙氧基矽烷及其混合物。
- 一種如申請專利範圍第9項之產物用作界面活性劑之用途。
- 一種如申請專利範圍第9項之產物用作分散添加劑之用途。
- 一種如申請專利範圍第10項之產物用作界面活性劑之用途。
- 一種如申請專利範圍第10項之產物用作分散添加劑之用途。
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-
2014
- 2014-09-05 DE DE102014217790.1A patent/DE102014217790A1/de not_active Withdrawn
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2015
- 2015-08-11 EP EP15750041.4A patent/EP3189093B1/de active Active
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2018
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WO2016034375A1 (de) | 2016-03-10 |
US10160832B2 (en) | 2018-12-25 |
JP2017525828A (ja) | 2017-09-07 |
JP6792551B2 (ja) | 2020-11-25 |
CN106715528B (zh) | 2019-08-23 |
EP3189093B1 (de) | 2019-10-02 |
US20170283554A1 (en) | 2017-10-05 |
DE102014217790A1 (de) | 2016-03-10 |
EP3189093A1 (de) | 2017-07-12 |
US10407546B2 (en) | 2019-09-10 |
CN106715528A (zh) | 2017-05-24 |
US20190100620A1 (en) | 2019-04-04 |
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