JPH02242822A - Production of polyoxyalkylene derivative - Google Patents
Production of polyoxyalkylene derivativeInfo
- Publication number
- JPH02242822A JPH02242822A JP6207289A JP6207289A JPH02242822A JP H02242822 A JPH02242822 A JP H02242822A JP 6207289 A JP6207289 A JP 6207289A JP 6207289 A JP6207289 A JP 6207289A JP H02242822 A JPH02242822 A JP H02242822A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- alkyl
- parts
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 5
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- 239000002879 Lewis base Substances 0.000 claims abstract description 4
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 229920002396 Polyurea Polymers 0.000 abstract description 4
- 239000012434 nucleophilic reagent Substances 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 4
- 229920006122 polyamide resin Polymers 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 30
- 229920000642 polymer Polymers 0.000 description 29
- -1 oxytetramethylene Chemical group 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000001450 anions Chemical class 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012038 nucleophile Substances 0.000 description 8
- AYKYOOPFBCOXSL-UHFFFAOYSA-N p-hydroxyphenylacetonitrile Natural products OC1=CC=C(CC#N)C=C1 AYKYOOPFBCOXSL-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Chemical class 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000269 nucleophilic effect Effects 0.000 description 4
- 239000012053 oil suspension Substances 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- TZCFWOHAWRIQGF-UHFFFAOYSA-N 3-chloropropane-1-thiol Chemical compound SCCCCl TZCFWOHAWRIQGF-UHFFFAOYSA-N 0.000 description 2
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- WICQXESQFGXSKV-UHFFFAOYSA-N disulfuryl fluoride Chemical compound FS(=O)(=O)OS(F)(=O)=O WICQXESQFGXSKV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- AXKGIPZJYUNAIW-UHFFFAOYSA-N (4-aminophenyl)methanol Chemical compound NC1=CC=C(CO)C=C1 AXKGIPZJYUNAIW-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-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
- KODLUXHSIZOKTG-UHFFFAOYSA-N 1-aminobutan-2-ol Chemical compound CCC(O)CN KODLUXHSIZOKTG-UHFFFAOYSA-N 0.000 description 1
- VDTHWBLOSZIMMN-UHFFFAOYSA-N 1-chloro-3-(3-chloropropylsulfanyl)propane Chemical group ClCCCSCCCCl VDTHWBLOSZIMMN-UHFFFAOYSA-N 0.000 description 1
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- MVGJRISPEUZYAQ-UHFFFAOYSA-N 2-methyl-2-nitropropan-1-ol Chemical compound OCC(C)(C)[N+]([O-])=O MVGJRISPEUZYAQ-UHFFFAOYSA-N 0.000 description 1
- CXURGFRDGROIKG-UHFFFAOYSA-N 3,3-bis(chloromethyl)oxetane Chemical compound ClCC1(CCl)COC1 CXURGFRDGROIKG-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- FAYGEALAEQKPDI-UHFFFAOYSA-N 4-(2-methoxyethyl)phenol Chemical compound COCCC1=CC=C(O)C=C1 FAYGEALAEQKPDI-UHFFFAOYSA-N 0.000 description 1
- BKCUGMAGOAPJRG-UHFFFAOYSA-N 4-(nitromethyl)phenol Chemical compound OC1=CC=C(C[N+]([O-])=O)C=C1 BKCUGMAGOAPJRG-UHFFFAOYSA-N 0.000 description 1
- NZKAHCXIOQIGCS-UHFFFAOYSA-N 4-(sulfanylmethyl)benzonitrile Chemical compound SCC1=CC=C(C#N)C=C1 NZKAHCXIOQIGCS-UHFFFAOYSA-N 0.000 description 1
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 description 1
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910017049 AsF5 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910005143 FSO2 Inorganic materials 0.000 description 1
- 229910005185 FSO3H Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- KQWYQZYVKPPMBX-UHFFFAOYSA-N chembl1972400 Chemical compound CCCCCCCCCCCCOP(=O)OCCCCCCCCCCCC KQWYQZYVKPPMBX-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- MJUJXFBTEFXVKU-UHFFFAOYSA-N diethyl phosphonate Chemical group CCOP(=O)OCC MJUJXFBTEFXVKU-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- NNTJKSMVNWGFTB-UHFFFAOYSA-N disulfuryl chloride Chemical compound ClS(=O)(=O)OS(Cl)(=O)=O NNTJKSMVNWGFTB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002919 oxepanes Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- WEYVCQFUGFRXOM-UHFFFAOYSA-N perazine Chemical class C1CN(C)CCN1CCCN1C2=CC=CC=C2SC2=CC=CC=C21 WEYVCQFUGFRXOM-UHFFFAOYSA-N 0.000 description 1
- 229960002195 perazine Drugs 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ポリアミド樹脂、ポリウレア樹脂、塗料、接
着剤及び界面活性剤等の原料として有用な両末端を変性
したポリオキシアルキレンの製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing polyoxyalkylene modified at both ends, which is useful as a raw material for polyamide resins, polyurea resins, paints, adhesives, surfactants, and the like.
ポリオキシアルキレンの両末端変性法としては、例えば
、ポリオキシアルキレングリコールをシアノエチル化し
、さらに水素還元して両末端をアミン変性したポリオキ
シアルキレンを得る方法（ヨーロッパ特許明細書７，５
９４号）、テトラヒドロフラン（以下ＴＨＦと略す）の
リビング生長末端をケテンシリルアセクールで停止する
ことにより両末端をカルボキシ変性したポリオキシテト
ラメレングリール酸を得る方法（ＰｏｌｙｍｅｒＰｒｅ
ｐｒｉｎｔｓ、 Ｊａｐａｎ ３５ （２）、２５
３． （１９８６））等が知られている。しかしこれら
の方法では末端は比較的定量的に変換されるが、副生じ
た不純物の除去が困難であったり、高価なケテンシリル
アセクールを過剰に使用したりなど工業的観点から満足
できるものではない。As a method for modifying both ends of polyoxyalkylene, for example, polyoxyalkylene glycol is cyanoethylated and further reduced with hydrogen to obtain a polyoxyalkylene in which both ends are modified with amine (European Patent Specification 7, 5).
No. 94), a method for obtaining polyoxytetramene glycol acid in which both ends are modified with carboxy by terminating the living growing end of tetrahydrofuran (hereinafter abbreviated as THF) with ketenesilylacecool (PolymerPre
prints, Japan 35 (2), 25
3. (1986)) are known. However, although these methods convert the terminals relatively quantitatively, they are not satisfactory from an industrial perspective, as it is difficult to remove by-product impurities and an excessive amount of expensive ketene silyl acecool is used. do not have.
本発明は上記した両末端変性ポリオキシアルキレンの従
来技術の問題点を解決し、ポリアミド樹脂、ポリウレア
樹脂、塗料の改質剤及び界面活性剤等として有用な変性
ポリオキシアルキレン誘導体の製造法を提供するもので
ある。The present invention solves the above-mentioned problems of the conventional technology of polyoxyalkylene modified at both ends, and provides a method for producing modified polyoxyalkylene derivatives useful as polyamide resins, polyurea resins, paint modifiers, surfactants, etc. It is something to do.
本発明者らは、上記実情に鑑み、鋭意検討した結果、Ｔ
ＨＦ又はＴＨＦと３．４及び７員環状エーテル類の混合
物をジカチオン活性ポリエーテルを生成しうる触媒を用
いて重合させ、リビング生長末端を有機求核試薬で処理
することにより両末端を変性したポリオキシテトラメチ
レン又はポリオキシテトラメチレン鎖ペースコーポリエ
ーテルが得られることを見い出し、本発明を完成した。In view of the above-mentioned circumstances, the inventors have made extensive studies and found that T.
A mixture of HF or THF and 3,4- and 7-membered cyclic ethers is polymerized using a catalyst capable of producing dicationically active polyethers, and the living growing ends are treated with an organic nucleophile to produce a polyester modified at both ends. It was discovered that an oxytetramethylene or polyoxytetramethylene chain paceco polyether can be obtained, and the present invention was completed.
即ち本発明は、テトラヒドロフラン、又はテトラヒドロ
フランと３．４及び７員環状エーテル類とをジカチオン
活性ポリエーテルの生成に有効な触媒を用いて重合又は
共重合し、その活性種を次の一般式（１）〜（４）、
（式中、Ａは酸素または硫黄、Ｘは水素原子、アルキル
基、アルコキシ基、アミノ基、水酸基、ニトロ基、シア
ノ基、ホスホン酸基、リン酸基、スルホン酸基、硫酸基
またはハロゲン原子を示し、ｍはＯ〜５の整数である。That is, the present invention involves polymerizing or copolymerizing tetrahydrofuran or tetrahydrofuran and 3.4- and 7-membered cyclic ethers using a catalyst effective for producing dicationically active polyethers, and converting the active species into the following general formula (1). ) to (4), (wherein A is oxygen or sulfur, X is hydrogen atom, alkyl group, alkoxy group, amino group, hydroxyl group, nitro group, cyano group, phosphonic acid group, phosphoric acid group, sulfonic acid group, It represents a sulfuric acid group or a halogen atom, and m is an integer of O to 5.
）、
Ａ−Ｒ−Ｙ（２）
（式中、Ａは上記−数式（１）で定義した通りであり、
Ｒは炭素数２〜８のアルキル基またはアラルキル基、Ｙ
はアミノ基、ニトロ基、シアノ基、アルコキシ基、ホス
ホン酸基、リン酸基、スルホン酸基、硫酸基またはハロ
ゲン原子を示す。）Ｈｇ ＮＲＩ Ｓ ｉ
（ＯＲ＋ ）ｎ （３）（Ｒ１） ｐ
（式中、Ｒ１は炭素数１〜８のアルキル基、Ｒ２は炭素
数１〜８のアルキル基又はアリール基を示し、ｎは２又
は３、ｐは０又は１であり、ｎ＋ｐは３である。）、
ＯＰ ＯＲ３（４）
ＯＲ。), A-R-Y(2) (wherein A is as defined in formula (1) above,
R is an alkyl group or aralkyl group having 2 to 8 carbon atoms, Y
represents an amino group, a nitro group, a cyano group, an alkoxy group, a phosphonic acid group, a phosphoric acid group, a sulfonic acid group, a sulfuric acid group, or a halogen atom. ) Hg NRI Si
(OR+)n (3)(R1) p (wherein, R1 is an alkyl group having 1 to 8 carbon atoms, R2 is an alkyl group or aryl group having 1 to 8 carbon atoms, n is 2 or 3, and p is 0 or 1 and n+p is 3), OP OR3 (4) OR.
（式中、Ｒ１及びＲ４は同一でも異なっていてもよ（、
炭素数２〜８のアルキル基又は了り−ル基を示す。）で
表わされる。有機求核試薬またはルイス塩基で処理する
ことを特徴とする末端変性したポリオキシアルキレン誘
導体の製法である。(In the formula, R1 and R4 may be the same or different (,
It represents an alkyl group or an alkyl group having 2 to 8 carbon atoms. ). This is a method for producing a terminal-modified polyoxyalkylene derivative, which is characterized by treatment with an organic nucleophile or a Lewis base.
本発明でいうＴＨＦとはＣ，−Ｃ，アルキル置換ＴＨＦ
も含まれる。たとえば２−１及び３−メチルＴＨＦなど
である。３，４及び７員環状エーテルとは、エチレンオ
キシド、プロピレンオキシドなどのエポキシド類、オキ
セタン、３．３−ビス（クロロメチル）−オキセタンな
どのオキセタン類及びオキセパン類である。THF in the present invention is C, -C, alkyl substituted THF.
Also included. For example, 2-1 and 3-methylTHF. The 3-, 4-, and 7-membered cyclic ethers include epoxides such as ethylene oxide and propylene oxide, oxetanes such as oxetane, 3,3-bis(chloromethyl)-oxetane, and oxepanes.
本発明においてジカチオン活性ポリエーテルを与える触
媒とはフロロスルホン酸（ＦＳＯ３Ｈ）、ポリフロロ脂
肪族スルホン酸（ＲｆＳＯ，Ｈ；ここにＲｆは１個以上
の炭素原子を含有し且つα炭素原子に少なくとも１個の
フッ素置換基を有するポリフロロ脂肪族（ポリフロロ環
式脂肪族）基である）、過塩素酸（Ｈ（４０，）から得
られる強酸の無水物、及び混合無水物であり、たとえば
、（ＦＳＯ２）２０、（ＣＦ３ ＳＯ２）２０、ＦＳＯ
！ ＯＯｚ ５ＣＦ３ 、Ｃ１ｚ Ｏｖなどである。In the present invention, the catalysts that give dicationically active polyethers are fluorosulfonic acid (FSO3H), polyfluoroaliphatic sulfonic acid (RfSO,H; where Rf contains one or more carbon atoms and at least one α carbon atom). are polyfluoroaliphatic (polyfluorocycloaliphatic) groups with fluorine substituents), anhydrides of strong acids obtained from perchloric acid (H(40,), and mixed anhydrides, such as (FSO2) 20, (CF3 SO2)20, FSO
! These include OOz 5CF3 and C1z Ov.
また上記強酸の相当するハロゲン化酸とルイス酸との反
応で得られる塩、たとえばＦＳＯｚ Ｆ−３ｂＦｓ
（ＦＳＯｚ ” ５ｂＦｂ −）、ＣＦｓ ＳＯｘ Ｆ
−３ｂＦｓ （ＣＦ３ ＳＯ□Ｓ ｂＦｈ −） 、
ＣＦｓ Ｓｏｗ Ｃ１−３ｂｃＩｌｓ（ＣＦ、ＳＯ，“
５ｂＣｊ！、−）、Ｃｆ０．Ｆ・ＢＦ３ （Ｃ／！Ｏ
，” ＢＦ４− ）などである。さらに上記強酸とジ第
−級グリコールとの成るジエステルである１、４−ブタ
ンビス（フロロスルホネート）、１．４−７”タンビス
（トリフロロスルホネート）、及びポリオキシテトラメ
チレングリコールの相当するジエステルなども含まれる
。これらジカチオン活性ポリエーテルを与える触媒は公
知の方法によって調製できる。さらに有機ジカルボン酸
シバライドと強酸との塩、ルイス酸との塩であり、たと
えばテレフタル酸クロリドと過塩素酸銀から得られる
・ＳｂＣ／！ａなどである。ここでいう強酸は前記のも
のを示し、ルイス酸はカチオン重合において非停止性の
対アニオンを与えるルイス酸で、たとえば５ｂＣ１ｓ
、５ｂＦｓ 、ＡｓＦ５ 、ＰＦｓ、ＢＦ、などである
。In addition, salts obtained by reaction of the above-mentioned strong acids with corresponding halogenated acids and Lewis acids, such as FSOz F-3bFs
(FSOz ” 5bFb −), CFs SOx F
-3bFs (CF3 SO□S bFh -),
CFs Sow C1-3bcIls (CF, SO, “
5bCj! , -), Cf0. F・BF3 (C/!O
,"BF4-), etc.Furthermore, 1,4-butanebis(fluorosulfonate), 1.4-7"butanebis(trifluorosulfonate), which is a diester consisting of the above-mentioned strong acid and di-primary glycol, and polyoxy Also included are corresponding diesters of tetramethylene glycol. Catalysts that provide these dicationically active polyethers can be prepared by known methods. Furthermore, it is a salt of an organic dicarboxylic acid cybaride with a strong acid or a salt with a Lewis acid, such as .SbC/! obtained from terephthalic acid chloride and silver perchlorate. a, etc. The strong acid mentioned here refers to the one mentioned above, and the Lewis acid is a Lewis acid that provides a non-terminating counter anion in cationic polymerization, for example, 5bC1s.
, 5bFs, AsF5, PFs, BF, etc.
本発明において一般式（１）で表わされる有機求核試薬
は、例えば、フェノール、チオフェノーノ堕４−アミノ
フェノール、２−アミノチオフェノール、４−アミノチ
オフェノール、４−ニトロフェノール、４−（ニトロメ
チル）フェノール、４−メチルフェノール、４−メトキ
シフェノール、４−（２−メトキシエチル）フェノール
、４−シアノフェノール、４−シアノメチルフェノール
、４−クロロチオフェノール、３．４−ジクロロフェノ
ール、４−（ジエチルホスホノ）−フェノール、４−（
エチルオキシスルホニル）−フェノールなどのフェノキ
シアニオンあるいはフェニルチオアニオンがあげられる
。In the present invention, the organic nucleophile represented by the general formula (1) is, for example, phenol, thiophenol-4-aminophenol, 2-aminothiophenol, 4-aminothiophenol, 4-nitrophenol, 4-(nitromethyl) Phenol, 4-methylphenol, 4-methoxyphenol, 4-(2-methoxyethyl)phenol, 4-cyanophenol, 4-cyanomethylphenol, 4-chlorothiophenol, 3.4-dichlorophenol, 4-(diethyl) Phosphono)-phenol, 4-(
Examples include phenoxy anions and phenylthio anions such as (ethyloxysulfonyl)-phenol.
これらのアニオンは、有機不活性溶媒、例えばトルエン
、キシレン及びＴＨＦなどに、上記相当する化合物を溶
解し、アルカリ金属、アルカリ金属水素化物、アルカリ
金属アルコラード及びアルカリ金属アルキル等で処理す
ることによって容易に得られる。また本発明において一
般式（２）で表わされる有機求核試薬は、例えば２−ア
ミノエタノール、２−アミノエタンチオール、３−クロ
ロ−１−プロパンチオール、１−アミノ−２−ブタノー
ル、４−アミノ−１−ブタノール、２−メチル−２−ニ
トロ−１−プロパツール、エチレンシアノヒドリン、４
−クロロ−１−ブタノール、２−メトキシ−１−エチル
アルコール、４−メトキシ−１−ブチルアルコール、４
−アミノベンジルアルコール、４−シアノフェニルメタ
ンチオールなどがあげられる。本発明において一般式（
３）で表わされる有機求核試薬は、例えば、３−アミノ
プロピルトリメトキシシラン、３−アミノプロピルトリ
エトキシシラン、３−アミノプロピルジェトキシメチル
シランなどがあげられる。These anions can be easily obtained by dissolving the above-mentioned corresponding compounds in an organic inert solvent such as toluene, xylene, THF, etc. and treating with an alkali metal, alkali metal hydride, alkali metal alcoholade, alkali metal alkyl, etc. can get. Further, in the present invention, the organic nucleophile represented by the general formula (2) is, for example, 2-aminoethanol, 2-aminoethanethiol, 3-chloro-1-propanethiol, 1-amino-2-butanol, 4-amino -1-butanol, 2-methyl-2-nitro-1-propanol, ethylene cyanohydrin, 4
-chloro-1-butanol, 2-methoxy-1-ethyl alcohol, 4-methoxy-1-butyl alcohol, 4
-aminobenzyl alcohol, 4-cyanophenylmethanethiol, and the like. In the present invention, the general formula (
Examples of the organic nucleophile represented by 3) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyljethoxymethylsilane.
また本発明において一般式（４）で表わされる有機求核
試薬は、例えば、ホスホン酸ジエチルエステル、ホスホ
ン酸ジプチルエステル、ホスホン酸ジラウリルエステル
、ホスホン酸ジフェニルエステルなどがあげられる。Further, in the present invention, examples of the organic nucleophilic reagent represented by the general formula (4) include diethyl phosphonate, diptyl phosphonate, dilauryl phosphonate, and diphenyl phosphonate.
また本発明において使用するルイス塩基とは、例えば−
数式（５）
％式％（５）
（式中、Ｒ□、Ｒ１、Ｒ４は同一でも異っていてもよく
、（３）および（４）式で定義した通りであり、Ｚは窒
素原子またはリン原子を表わす。）、ピリジン類、キノ
リン類、Ｎ Ｃ＋＝ｓアルキル置換モルホリンまたは
とペラジンである。Further, the Lewis base used in the present invention is, for example, -
Formula (5) % Formula % (5) (In the formula, R□, R1, and R4 may be the same or different and are as defined in formulas (3) and (4), and Z is a nitrogen atom or represents a phosphorus atom), pyridines, quinolines, N C+=s alkyl-substituted morpholine or perazine.
本発明においてジカチオン活性ポリエーテルを得る重合
または共重合反応温度は特に限定はないが、通常−２０
°Ｃないし２０℃が適当である。In the present invention, the temperature of the polymerization or copolymerization reaction to obtain the dicationically active polyether is not particularly limited, but is usually -20
°C to 20°C is suitable.
２０℃以下の低温では速度が低下するし、一方高温では
生成した末端ジカチオンが不安定となり、死活する恐れ
がある。用いる触媒量は重合の速度、目的とするポリエ
ーテルの分子量等によって変わってくるが、一般にはモ
ノマー１モルに対し０゜００１ないし０．１モル程度、
好ましくは０．０１モル前後がよい。一方、重合時間は
温度、触媒量によって変るが、本重合系ではモノマー反
応率と得られるポリエーテルの分子量はかなり相関があ
り、目的とする分子量によって決められる。一般に成る
樹脂のソフトセグメントとして用いられるポリエーテル
は分子量は５００ないし５０００のオリゴマー領域であ
り、これを得るには重合時間は５ないし６０分程度であ
る。勿論ポリエーテルの分子量は限定されず、敵方ない
し数十万の分子量を得るには６０分以上の重合時間を必
要とする。At a low temperature of 20° C. or lower, the rate decreases, while at a high temperature, the generated terminal dication becomes unstable and may become lifeless. The amount of catalyst used varies depending on the rate of polymerization, the molecular weight of the target polyether, etc., but is generally about 0.001 to 0.1 mole per mole of monomer.
Preferably it is around 0.01 mol. On the other hand, although the polymerization time varies depending on the temperature and the amount of catalyst, in the present polymerization system, there is a considerable correlation between the monomer reaction rate and the molecular weight of the polyether obtained, and it is determined by the desired molecular weight. The polyether used as the soft segment of general resins has a molecular weight in the oligomer range of 500 to 5,000, and the polymerization time to obtain this is about 5 to 60 minutes. Of course, the molecular weight of the polyether is not limited, and a polymerization time of 60 minutes or more is required to obtain a molecular weight of several hundred thousand.
以上の重合反応はバルク重合でも溶液重合でもよく、溶
液重合ではトルエン、キシレン、塩化メチレン、塩化エ
チレンなどカチオン重合に対し不活性な有機溶媒が用い
られる。但し、重合系への水分の混入は、生成ジカチオ
ンの死活の原因になるので乾燥雰囲気、乾燥溶媒下に行
うのが好ましい。The above polymerization reaction may be either bulk polymerization or solution polymerization, and in solution polymerization, an organic solvent inert to cationic polymerization, such as toluene, xylene, methylene chloride, or ethylene chloride, is used. However, since the introduction of water into the polymerization system causes the death of the dication produced, it is preferable to carry out the reaction in a dry atmosphere and under a dry solvent.
かくして得られたジカチオン活性ポリエーテルは、予め
準備された有機求核アニオンまたは有機求核試薬によっ
て処理される。添加される求核アニオンの量は重合に用
いた触媒１モル当り２ないし１０モル、好ましくは２な
いし５モルである。The dicationically active polyether thus obtained is treated with a previously prepared organic nucleophilic anion or organic nucleophile. The amount of nucleophilic anion added is from 2 to 10 mol, preferably from 2 to 5 mol, per mol of catalyst used for polymerization.
求核アニオンまたは求核試薬で処理された反応混合物は
、両末端が、添加された求核試薬に相当した変性ポリオ
キシアルキレン誘導体となる。The reaction mixture treated with a nucleophilic anion or a nucleophile becomes a modified polyoxyalkylene derivative with both ends corresponding to the added nucleophile.
この反応混合物の後処理方法は、添加した求核アニオン
または求核試薬の種類によって異なるが、一般にはアル
カリ水を加え、水洗し、溶媒を除去することによって高
純度、高収率で目的物が得られる。The post-treatment method for this reaction mixture varies depending on the type of nucleophilic anion or nucleophilic reagent added, but generally the target product is obtained with high purity and high yield by adding alkaline water, washing with water, and removing the solvent. can get.
このようにして得られたポリオキシアルキレン誘導体は
、両末端に例えばアミノ基のような活性水素を持つ重合
体では、トリレンジイソシアナートまたは４．４′−ジ
フェニルメタンジイソシアナートのようなポリイソシア
ナート化合物と反応させるとポリウレア樹脂ができる。The polyoxyalkylene derivative obtained in this way is a polyisocyanate such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate in the case of a polymer having active hydrogen such as an amino group at both ends. When reacted with other compounds, polyurea resin is produced.
また、テレフタル酸のようなジカルボン酸化合物と反応
させるとポリアミド樹脂ができ、弾性特性、低温柔軟性
が改善される。また活性水素を持たない重合体では耐衝
撃性、低温柔軟性などの改善のため塗料、接着剤等の添
加剤として有用である。Additionally, when reacted with a dicarboxylic acid compound such as terephthalic acid, a polyamide resin is produced, which improves elastic properties and low-temperature flexibility. In addition, polymers without active hydrogen are useful as additives for paints, adhesives, etc. to improve impact resistance, low-temperature flexibility, etc.
次に本発明を実施例によってさらに詳しく説明する。実
施例においてポリエーテルの分子量はＶＰ Ｏ（Ｖａｐ
ｏｒ Ｐｒｅｓｓｕｒｅ Ｏｓｍｏｍｅｔｅｒ ；日立
０Ｐｅｒｋｉｎ−Ｅ１ｍｅｒ製１１５型）により求めた
。また末端基は酸−アルカリ滴定による中和当量、’
ＨＳ１３Ｃ−ＮＭＲ（日本電子製ＪＮＭ ＦＸ−６０
Ｑ）スペクトル（闘条件； ＣＤ Ｃｌ ３内部標準−
ＴＭＳ）及び１．Ｒ（赤外分光分析、日本分光Ａ−１０
２）によって確認した。Next, the present invention will be explained in more detail by way of examples. In the examples, the molecular weight of the polyether is VPO (Vap
or Pressure Osmometer (Model 115, manufactured by Hitachi Perkin-Elmer). In addition, the terminal group is the neutralization equivalent determined by acid-alkali titration, '
HS13C-NMR (JNM FX-60 manufactured by JEOL
Q) Spectrum (fighting conditions; CD Cl 3 internal standard -
TMS) and 1. R (infrared spectroscopy, JASCO A-10
2) was confirmed.
なお、実施例中の部は、特にことわりのない限り重量部
を表わす。In addition, parts in the examples represent parts by weight unless otherwise specified.
実施例１
１００ｃｃのフラスコに水素化ナトリウム（Ｎａ８１６
０％オイルサスペンション） ０．４８８部をとり、フ
ラスコ内を窒素置換した。これに脱水、精製したＴＨＦ
、３５部を添加、水冷下、４−アミノフェノール１．４
６部を添加して４−アミノフェノールのフェノキシアニ
オン溶液を得た。Example 1 Sodium hydride (Na816
0% oil suspension) was taken, and the inside of the flask was purged with nitrogen. This is dehydrated and purified THF
, added 35 parts, cooled with water, 4-aminophenol 1.4
6 parts were added to obtain a phenoxy anion solution of 4-aminophenol.
次に攪拌装置、温度計、シリカゲル管を備え、窒素置換
した５００ｃｃ四ツロフラスコに脱水、精製したＴ Ｈ
Ｆ ７２．１部をとり、氷−食塩浴で０°Ｃに保冷した
。攪拌下に無水トリフロロメタンスルホン酸（ＣＦｉ
ＳＯ２）ｚ Ｏｌｌ、７２部を添加、重合を開始した。Next, the dehydrated and purified T
72.1 parts of F was taken and kept cool at 0°C in an ice-salt bath. Trifluoromethanesulfonic anhydride (CFi
72 parts of SO2)zOll was added to start polymerization.
以後Ｏ″Ｃで３０分間重合反応を行った後予め調製した
上記４−アミノフェノールのフェノキシアニオン溶液を
添加して、１０分間攪拌することによって反応を停止し
た。反応混合物をトルエン１８０部で希釈し、水１００
部を加えて洗浄した。静置分液後有機層からトルエンを
減圧留去し、油状ポリマー２１．８ｇ（収率３０．２％
）を得た。Thereafter, the polymerization reaction was carried out at O''C for 30 minutes, and then the above-prepared phenoxy anion solution of 4-aminophenol was added, and the reaction was stopped by stirring for 10 minutes.The reaction mixture was diluted with 180 parts of toluene. , water 100
was added and washed. After static separation, toluene was distilled off from the organic layer under reduced pressure to obtain 21.8 g of oily polymer (yield 30.2%).
) was obtained.
このポリマーは、”Ｃ−ＮＭＲ分析の結果、７０、０
、２６．０ ｐｐｍに主鎖のテトラメチレンエーテルに
由来するピークが認められ、末端ヒドロキシル基に隣接
するメチレン基のピーク（６１，５，２９、４ｐｐｍ）
はなく、末端フェニルエーテルに隣接するメチレン基の
ピークが６８．０ ｐｐｍに認められた。As a result of C-NMR analysis, this polymer was found to be 70,0
, a peak derived from the main chain tetramethylene ether was observed at 26.0 ppm, and a peak of the methylene group adjacent to the terminal hydroxyl group (61, 5, 29, 4 ppm)
A peak of methylene group adjacent to the terminal phenyl ether was observed at 68.0 ppm.
一方ＶＰＯより求めた分子量は４３００、滴定により求
めたアミノ基当量は４．７１Ｘ１０−’ｍｏｌ／ｇであ
った。これらの値より両末端にアミノ基を持ったポリオ
キシテトラメチレンであることが認められた。On the other hand, the molecular weight determined by VPO was 4300, and the amino group equivalent determined by titration was 4.71×10-'mol/g. From these values, it was confirmed that it was polyoxytetramethylene having amino groups at both ends.
実施例２
１００ｃｃのフラスコに無水のエタノール５０部、金属
ナトリウム０．５部をとり、これに４−クロロチオフェ
ノール３．８０部を添加、４−クロロチオフェノールの
チオフェノキシアニオン溶液を得た。Example 2 50 parts of anhydrous ethanol and 0.5 parts of metallic sodium were placed in a 100 cc flask, and 3.80 parts of 4-chlorothiophenol was added thereto to obtain a thiophenoxy anion solution of 4-chlorothiophenol.
攪拌装置、温度針、シリカゲル管を備え、窒素置換した
５００ｃｃフラスコに脱水、精製したＴＨＦ ７２．１
部、アジポイルクロリド２．２部をとり、氷−食塩浴に
て０℃に保冷した。これに過塩素酸銀５．２部とＴ Ｈ
Ｆ ７２．１部の混合物を添加し、重合を開始、以後Ｏ
″Ｃで１５分間重合反応を行った。Dehydrated and purified THF 72.1 was placed in a 500 cc flask equipped with a stirrer, temperature needle, and silica gel tube and purged with nitrogen.
1 part and 2.2 parts of adipoyl chloride were taken and kept cool at 0°C in an ice-salt bath. To this, 5.2 parts of silver perchlorate and T H
Add 72.1 parts of F mixture to start polymerization, then O
The polymerization reaction was carried out for 15 minutes at "C".
この反応液に予め調整した上記４−クロロチオフェノー
ルのチオフェノキシアニオン溶液を添加して反応を停止
した。以下実施例１と同様に処理し、油状のポリマー３
４．９部（収率２４．２％）を得た。The reaction was stopped by adding the previously prepared thiophenoxy anion solution of 4-chlorothiophenol to this reaction solution. The following treatment was carried out in the same manner as in Example 1, and the oily polymer 3
4.9 parts (yield 24.2%) were obtained.
このポリマーはＩ３Ｃ−ＮＭＲ，１，Ｒの結果、芳香環
に由来するスペクトルが得られた。また、ＶＰＯより求
めたこのポリマーの分子量は、１８１０であった。これ
らの値より両末端にＰ−クロロフェル基を持ったポリオ
キシテトラメチレンであることが認められた。As a result of I3C-NMR, 1,R of this polymer, a spectrum derived from aromatic rings was obtained. The molecular weight of this polymer determined by VPO was 1,810. From these values, it was confirmed that it was polyoxytetramethylene having P-chlorofer groups at both ends.
実施例３
１００ｃｃのフラスコに水素化ナトリウム（ＮａＨ１６
０％オイルサスペンション） ０．４８８部をとり、フ
ラスコ内を窒素置換した。これに脱水・精製したＴＨＦ
４０部を添加、水冷下、エチレンシアンヒドリン０．９
５を少量ずつ添加してエチレンシアンヒドリンアニオン
を得た。Example 3 Sodium hydride (NaH16
0% oil suspension) was taken, and the inside of the flask was purged with nitrogen. This is dehydrated and purified THF
Added 40 parts, cooled with water, 0.9 ethylene cyanohydrin
5 was added little by little to obtain ethylene cyanohydrin anion.
攪拌装置、温度計、シリカゲル管を備え、窒素置換した
５００ｃｃのフラスコに脱水・精製したＴＨＦ ７２．
１部をとり、氷−食塩浴で０°Ｃに保冷した。攪拌下に
無水フロロスルホン酸（ＦＳＯｚ）ｇ。72. Dehydrated and purified THF was placed in a 500 cc flask equipped with a stirrer, thermometer, and silica gel tube and purged with nitrogen.
One portion was taken and kept at 0°C in an ice-salt bath. g of fluorosulfonic anhydride (FSOz) under stirring.
、１．２部を添加し重合を開始した。以後０℃で３００
分間重合反応行い、予め調整した上記エチレンジ、アン
ヒドリンアニオンに添加して、１０分間撹拌することに
より反応を停止した。以下実施例１と同様に処理し油状
ポリマー１９．２部（収率２６．６％）を得た。, 1.2 parts were added to initiate polymerization. After that, 300 at 0℃
The polymerization reaction was carried out for a minute, and the reaction was stopped by adding the above-mentioned ethylene dianhydrin anion prepared in advance and stirring for 10 minutes. Thereafter, the same treatment as in Example 1 was carried out to obtain 19.2 parts of an oily polymer (yield: 26.6%).
このポリマーは、”Ｃ−ＮＭＲの結果、実施例１と同様
に主鎖のテトラメチレンエーテルに由来するピークが認
められ、末端ヒドロキシル基に隣接するメチレン基のピ
ークは認められなかった。As a result of C-NMR of this polymer, as in Example 1, a peak derived from tetramethylene ether in the main chain was observed, and no peak from the methylene group adjacent to the terminal hydroxyl group was observed.
また、末端シアノエチル基の２つのメチレン基に由来す
るピークが６６．５ ｐｐｍと１８．５ ｐｐｍに認め
られた。１．Ｒの結果、２２５０ｃｍ−’にニトリル基
の吸収が認められた。ｖＰＯから求めたこのポリマーの
分子量は３９４０であった。Furthermore, peaks derived from the two methylene groups of the terminal cyanoethyl group were observed at 66.5 ppm and 18.5 ppm. 1. As a result of R, absorption of nitrile group was observed at 2250 cm-'. The molecular weight of this polymer determined from vPO was 3940.
実施例４
１００ｃｃのフラスコに水素化ナトリウム（ＮａＨ，６
０％オイルサスペンション）０．４８８部をとり、フラ
スコ内を窒素置換した。これに脱水・精製したＴＨＦ４
０部を添加し、水冷下３−クロロートプロパン千オール
３．２３部を少量ずつ添加して３−クロロ−１−プロパ
ンチオールのチオラートアニオンを得た。Example 4 Sodium hydride (NaH, 6
0% oil suspension) was taken, and the inside of the flask was purged with nitrogen. This is dehydrated and purified THF4
0 part was added thereto, and 3.23 parts of 3-chloropropane 1,000ol was added little by little under water cooling to obtain a thiolate anion of 3-chloro-1-propanethyl.
次に攪拌装置、温度計、シリカゲル管を備え、窒素置換
した５００ｃｃ四ツロフラスコに脱水・精製したＴ Ｈ
Ｆ ７２．１部をとり、氷−水浴で５℃に保冷した。攪
拌した、別途無水トリフルオロメタンスルホン酸とＴＨ
Ｆより合成したｌ、 ４−ブタンビス（トリフルオロ
スルホネート）４．７０部を添加し、重合を開始した。Next, the dehydrated and purified T
72.1 parts of F was taken and kept cool at 5°C in an ice-water bath. Separately stirred trifluoromethanesulfonic anhydride and TH
4.70 parts of 1,4-butane bis(trifluorosulfonate) synthesized from F was added to initiate polymerization.
以後５°Ｃで３００分間重合反応行った後、予め調整し
た上記３−クロロ−１−プロパンチオールのチオラート
アニオンを添加して、１０分間攪拌することにより重合
反応を停止した。以下、実施側１と同様に処理した油状
ポリマー８．７部（収率１２．１％）を得た。Thereafter, the polymerization reaction was carried out at 5°C for 300 minutes, and then the above-prepared thiolate anion of 3-chloro-1-propanethiol was added, and the polymerization reaction was stopped by stirring for 10 minutes. Hereinafter, 8.7 parts (yield: 12.1%) of an oily polymer was obtained which was treated in the same manner as in Example 1.
このポリマーは、”Ｃ−ＮＭＲの結果、末端の３−クロ
ロプロピルスルフィド基の３つのメチレン基に由来する
ピークが３２．０．３４．１，４４．１ｐｐ−に認めら
れた。ＶＰＯより求めたこのポリマーの分子量は２６０
０であった。As a result of C-NMR, peaks derived from the three methylene groups of the terminal 3-chloropropylsulfide group were observed at 32.0, 34.1, and 44.1 pp-. Obtained from VPO. The molecular weight of this polymer is 260
It was 0.
実施例５
攪拌装置、温度計、シリカゲル管を備え、窒素置換した
５００ｃｃフラスコに脱水・精製したＴＨＦ ７２．１
部をとり、氷−食塩浴で０°Ｃに保冷した。Example 5 Dehydrated and purified THF 72.1 was placed in a 500 cc flask equipped with a stirrer, thermometer, and silica gel tube and purged with nitrogen.
An aliquot was taken and kept at 0°C in an ice-salt bath.
攪拌下に無水トリフロロメクンスルホン酸１．７部を添
加、０°Ｃで１５分間重合反応を行った。これに３−ア
ミノプロピルトリメトキシシラン２．４０部を添加し重
合反応を停止した。窒素雰囲気下、弱塩基型のイオン交
換樹脂を通すことにより触媒残渣を除き、Ｔｌ（Ｆを減
圧留去し油状ポリマー１１．５部（収率１６．０％）を
得た。1.7 parts of trifluoromecnesulfonic anhydride was added while stirring, and a polymerization reaction was carried out at 0°C for 15 minutes. 2.40 parts of 3-aminopropyltrimethoxysilane was added to this to stop the polymerization reaction. The catalyst residue was removed by passing through a weakly basic ion exchange resin in a nitrogen atmosphere, and Tl (F) was distilled off under reduced pressure to obtain 11.5 parts of an oily polymer (yield: 16.0%).
このポリマーは、” Ｈ−ＮＭＲの結果３．４ ｐｐｍ
と１．６ ｐｐｍに主鎖のテトラメチレンエーテルに由
来するピークが、３．６ ｐｐｍに末端のメトキシシリ
ル基に由来するピークが認められた。ＶＰＯから求めた
このポリマーの分子量は２２５０であった。This polymer has a H-NMR result of 3.4 ppm.
A peak derived from the main chain tetramethylene ether was observed at 1.6 ppm, and a peak derived from the terminal methoxysilyl group was observed at 3.6 ppm. The molecular weight of this polymer determined from VPO was 2250.
実施例６
１００ｃｃのフラスコを窒素置換し、脱水・精製したＴ
ＨＦ４０部、金属ナトリウム０．３部をとり、これにホ
スホン酸ジエチルエステル２．０部を添加し停止剤を得
た。Example 6 A 100cc flask was replaced with nitrogen, and T was dehydrated and purified.
40 parts of HF and 0.3 parts of sodium metal were taken, and 2.0 parts of diethyl phosphonate was added thereto to obtain a terminator.
攪拌装置、温度計、シリカゲル管を備え、窒素置換した
５００ｃｃのフラスコに脱水・精製したＴＨＦ ７２．
１部をとり、氷−食塩浴でＯ″Ｃに保冷した。攪拌下に
無水クロロスルホン酸１．２部を添加し重合を開始した
。以後０℃で１０分間重合反応を行い、予め調整した上
記ホスホン酸ジエチルエステルアニオンに添加して、１
０分間攪拌することにより反応を停止した。以下実施例
１と同様に処理し油状ポリマー６．６部（収率９．２％
）を得た。72. Dehydrated and purified THF was placed in a 500 cc flask equipped with a stirrer, thermometer, and silica gel tube and purged with nitrogen.
1 part was taken and kept cool at O''C in an ice-salt bath. 1.2 parts of chlorosulfonic anhydride was added under stirring to start polymerization. Thereafter, the polymerization reaction was carried out at 0 °C for 10 minutes, and the pre-adjusted Added to the above phosphonic acid diethyl ester anion, 1
The reaction was stopped by stirring for 0 minutes. Thereafter, the same procedure as in Example 1 was carried out to obtain 6.6 parts of oily polymer (yield: 9.2%).
) was obtained.
このポリマーは、” Ｈ−ＮＭＲの結果３．４ ＰＰｌ
１１と１．６ ｐｐｍに主鎖のテトラメチレンエーテル
に由来するピークが、１．４ ｐｐｍと４．２ ｐｐｍ
に末端のホスホン酸ジエチルエステル基のエチル基に由
来するピークが認められた。ＶＰＯから求めたこのポリ
マーの分子量は１３４０であった。This polymer has a H-NMR result of 3.4 PPI
There are peaks at 11 and 1.6 ppm derived from main chain tetramethylene ether, and peaks at 1.4 ppm and 4.2 ppm.
A peak derived from the ethyl group of the terminal phosphonic acid diethyl ester group was observed. The molecular weight of this polymer determined from VPO was 1340.
実施例７
１００ｃｃのフラスコに無水のエタノール５０部、金属
ナトリウム０．５部をとり、これに４−シアノメチルフ
ェノール１．９３部を添加、４−シアノメチルフェノー
ルのフェノキシアニオン溶液を得た。Example 7 50 parts of anhydrous ethanol and 0.5 parts of metallic sodium were placed in a 100 cc flask, and 1.93 parts of 4-cyanomethylphenol was added thereto to obtain a phenoxy anion solution of 4-cyanomethylphenol.
次に攪拌装置、温度計、シリカゲル管を備え、窒素置換
した５００ｃｃフラスコに脱水・精製したＴ ＨＦ ５
６．９部、３−メチルＴＨＦ１９゜０部をとり、氷−食
塩浴で０°Ｃに保冷した。攪拌下に無水フロロスルホン
酸１．２部を添加、重合を開始した。Next, the dehydrated and purified THF 5 was placed in a 500cc flask equipped with a stirrer, thermometer, and silica gel tube and purged with nitrogen.
6.9 parts of 3-methyl THF and 19.0 parts of 3-methyl THF were taken and kept cooled at 0°C in an ice-salt bath. While stirring, 1.2 parts of fluorosulfonic anhydride was added to initiate polymerization.
以後Ｏ″Ｃで２０分間重合反応を行った後、予め調整し
た上記４−シアノメチルフェノールのフェノキシアニオ
ン溶液に添加して、１０分間攪拌することによって重合
反応を停止した。以下実施例１と同様に処理し油状ポリ
マー１３．４部（収率１７゜７％）を得た。Thereafter, the polymerization reaction was carried out at O''C for 20 minutes, and then added to the above-prepared phenoxy anion solution of 4-cyanomethylphenol, and the polymerization reaction was stopped by stirring for 10 minutes.The following is the same as in Example 1. 13.4 parts of oily polymer (yield: 17.7%) was obtained.
この水リマーは”Ｃ−ＮＭＲの結果、ＴＨＦに由来する
ピークが２６．３ ｐｐｍと７０．４ ｐｐｍに、３−
メチルＴＨＦのメチル基とメチン基に由来するピークが
１７．０ ｐｐｍと３３．４ ｐｐｍに認められた。As a result of C-NMR, this water remer has peaks derived from THF at 26.3 ppm and 70.4 ppm, and 3-
Peaks derived from the methyl group and methine group of methylTHF were observed at 17.0 ppm and 33.4 ppm.
ポリマー組成はＴＨＦ：３−メチルＴＨＦ＝８７：１３
であった。Ｉ、Ｒ分析の結果シアノ基の吸収が２２５０
ｃｍ−’に認められた。ＶＰＯから求めたこのポリマー
の分子量は２７９０であった。Polymer composition is THF:3-methylTHF=87:13
Met. As a result of I, R analysis, the absorption of cyano group is 2250
cm-'. The molecular weight of this polymer determined from VPO was 2,790.
実施例８
１００ｃｃのフラスコに水素化ナトリウム（ＮａＨ１６
０％オイルサスペンション）０．４９部をとり、フラス
コ内を窒素置換した。これに脱水・精製したＴＨＦ４０
部を添加し、水冷下２−メトキシ−１−エチルアルコー
ルを少量ずつ添加して２−メトキシ−１−エチルアルコ
ールアニオンを得た。Example 8 Sodium hydride (NaH16
0% oil suspension) was taken, and the inside of the flask was purged with nitrogen. Dehydrated and purified THF40
2-methoxy-1-ethyl alcohol was added little by little under water cooling to obtain 2-methoxy-1-ethyl alcohol anion.
攪拌装置、温度針、シリカゲル管を備え、窒素置換した
５００ｃｃのフラスコに脱水・精製したＴＨＦ ５６．
９部、３−メチルＴＨＦ１９．Ｏ部をとり、氷−食塩浴
にてＯ′Ｃに保冷した。攪拌下に無水トリフロロメタン
スルホン酸１，７２部を添加し重合を開始した。以後０
°Ｃで１０分間重合反応を行い、予め調整した上記２−
メトキシ−１−エチルアルコールアニオンに添加し、１
０分間攪拌することにより重合反応を停止した。以下実
施例１と同様に処理し油状ポリマー７．６部（収率１０
．０％）を得た。Dehydrated and purified THF in a 500 cc flask equipped with a stirrer, temperature needle, and silica gel tube and purged with nitrogen 56.
9 parts, 3-methylTHF19. Part O was taken and kept cool at O'C in an ice-salt bath. While stirring, 1.72 parts of trifluoromethanesulfonic anhydride was added to initiate polymerization. From now on 0
A polymerization reaction was carried out at °C for 10 minutes, and the above 2-
Added to methoxy-1-ethyl alcohol anion, 1
The polymerization reaction was stopped by stirring for 0 minutes. Thereafter, the treatment was carried out in the same manner as in Example 1, and 7.6 parts of oily polymer (yield: 10
．． 0%) was obtained.
このポリマーは１３ｃｍＮＭＲの結果、ＴＨＦと３−メ
チルＴＨＦＯ共重合体であり、組成比はＴＨＦ８６％、
３−メチルＴＨＦ１４％であった。As a result of 13 cm NMR, this polymer is a copolymer of THF and 3-methyl THFO, with a composition ratio of 86% THF,
3-MethylTHF was 14%.
１３Ｃ−ＮＭＲの結果、骨格のテトラメチレンエーテル
に由来するピークが７１．０ｐｐｍと２７．０ ｐｐｍ
に、末端のメトキシ基に由来するピークが５７．８ｐｐ
ｍに認められた。ＶＰＯから求めたこのポリマーの分子
量は１４９０であった。As a result of 13C-NMR, the peaks derived from the tetramethylene ether of the skeleton were 71.0 ppm and 27.0 ppm.
The peak derived from the terminal methoxy group was 57.8pp.
It was recognized by m. The molecular weight of this polymer determined from VPO was 1490.
実施例９
攪拌装置、温度計、シリカ゛ゲル管を備え、窒素置換し
た５０．Ｏｃｃフラスコに脱水・精製したＴＨＦ ７２
．１部をとり、氷−食塩浴で０°Ｃに保冷した。Example 9 A 50.5-liter cell was equipped with a stirring device, a thermometer, and a silica gel tube, and the atmosphere was replaced with nitrogen. Dehydrated and purified THF 72 in Occ flask
．． One portion was taken and kept at 0°C in an ice-salt bath.
攪拌下に無水トリフロロメタンスルホン酸１．７部を添
加、０°Ｃで５分間重合反応を行った。これにトリメチ
ルアミン０．７９部を添加し重合反応を停止した。得ら
れたポリマー溶液を大量の臭化ナトリウムの飽和水溶液
に投入し、アンモニウム塩の対アニオンを臭素イオンに
変換した後ポリマーを塩化メチレンを用いて抽出し、塩
化メチレンを減圧除去し油状ポリマー４．１部（収率５
．７％）を得た。1.7 parts of trifluoromethanesulfonic anhydride was added while stirring, and a polymerization reaction was carried out at 0°C for 5 minutes. 0.79 parts of trimethylamine was added to this to stop the polymerization reaction. The obtained polymer solution was poured into a large amount of saturated aqueous solution of sodium bromide to convert the counter anion of the ammonium salt into bromide ion, and then the polymer was extracted using methylene chloride, and the methylene chloride was removed under reduced pressure to obtain an oily polymer 4. 1 part (yield 5
．． 7%).
このポリマーは、’ Ｈ−ＮＭＲ分析の結果３．４ｐｐ
ＩＩ＋と１．６ ｐｐｍに主鎖のテトラメチレンエーテ
ルに由来するピークが、３．２ ｐｐｍに末端のトリメ
チルアンモニウム塩基のメチル基に由来するピークが認
められた。ＶＰＯから求めたこのポリマーの分子量は７
７０であった。As a result of 'H-NMR analysis, this polymer has a ppm of 3.4pp.
A peak derived from the main chain tetramethylene ether at 1.6 ppm and II+ was observed, and a peak derived from the methyl group of the terminal trimethylammonium base was observed at 3.2 ppm. The molecular weight of this polymer determined from VPO is 7
It was 70.
保土谷化学工業株式会社 小 林 四 部Hodogaya Chemical Industry Co., Ltd. Elementary Hayashi 4th Department
Claims (1)
４および７員環状エーテル類とをジカチオン活性ポリエ
ーテルの生成に有効な触媒を用いて重合または共重合し
、その活性種を次の一般式（１）〜（４）、 ▲数式、化学式、表等があります▼（１） （式中、Ａは酸素または硫黄、Ｘは水素原子、アルキル
基、アルコキシ基、アミノ基、水酸基、ニトロ基、シア
ノ基、ホスホン酸基、リン酸基、スルホン酸基、硫酸基
またはハロゲン原子を示し、ｍは０〜５の整数である。 ）、 ▲数式、化学式、表等があります▼（２） （式中、Ａは上記一般式（１）で定義した通りであり、
Ｒは炭素数２〜８のアルキル基またはアラルキル基、Ｙ
はアミノ基、ニトロ基、シアノ基、アルコキシ基、ホス
ホン酸基、リン酸基、スルホン酸基、硫酸基またはハロ
ゲン原子を示す。）▲数式、化学式、表等があります▼
（３） （式中、Ｒ＿１は炭素数１〜８のアルキル基、Ｒ＿２は
炭素数１〜８のアルキル基またはアリール基を示し、ｎ
は２または３、ｐは０または１であり、ｎ＋ｐは３であ
る。） ▲数式、化学式、表等があります▼（４） （式中、Ｒ＿３及びＲ＿４は同一でも異なっていてもよ
く、炭素数１〜８のアルキル基またはアリール基を示す
。）で表わされる有機求核試薬またはルイス塩基で処理
することを特徴とする末端変性したポリオキシアルキレ
ン誘導体の製法。[Claims] Tetrahydrofuran, or tetrahydrofuran and 3,
4- and 7-membered cyclic ethers are polymerized or copolymerized using a catalyst effective for producing dicationically active polyethers, and the active species thereof are formed by the following general formulas (1) to (4), ▲mathematical formula, chemical formula, and table. etc.▼(1) (In the formula, A is oxygen or sulfur, , represents a sulfuric acid group or a halogen atom, and m is an integer from 0 to 5.), ▲Mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, A is as defined in the above general formula (1) and
R is an alkyl group or aralkyl group having 2 to 8 carbon atoms, Y
represents an amino group, a nitro group, a cyano group, an alkoxy group, a phosphonic acid group, a phosphoric acid group, a sulfonic acid group, a sulfuric acid group, or a halogen atom. ) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼
(3) (In the formula, R_1 is an alkyl group having 1 to 8 carbon atoms, R_2 is an alkyl group or aryl group having 1 to 8 carbon atoms, and n
is 2 or 3, p is 0 or 1, and n+p is 3. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(4) (In the formula, R_3 and R_4 may be the same or different and represent an alkyl group or an aryl group having 1 to 8 carbon atoms.) A method for producing a terminal-modified polyoxyalkylene derivative, which comprises treatment with a nuclear reagent or a Lewis base.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6207289A JPH02242822A (en) | 1989-03-16 | 1989-03-16 | Production of polyoxyalkylene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6207289A JPH02242822A (en) | 1989-03-16 | 1989-03-16 | Production of polyoxyalkylene derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02242822A true JPH02242822A (en) | 1990-09-27 |
Family
ID=13189513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6207289A Pending JPH02242822A (en) | 1989-03-16 | 1989-03-16 | Production of polyoxyalkylene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02242822A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997006202A1 (en) * | 1995-08-10 | 1997-02-20 | Kazunori Kataoka | Block polymer having functional groups at both ends |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6422921A (en) * | 1987-06-26 | 1989-01-25 | Minnesota Mining & Mfg | Production of first class diamines |
-
1989
- 1989-03-16 JP JP6207289A patent/JPH02242822A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6422921A (en) * | 1987-06-26 | 1989-01-25 | Minnesota Mining & Mfg | Production of first class diamines |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997006202A1 (en) * | 1995-08-10 | 1997-02-20 | Kazunori Kataoka | Block polymer having functional groups at both ends |
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