JPH048727A - Production of terminal stabilized epihalohydrin polymer - Google Patents
Production of terminal stabilized epihalohydrin polymerInfo
- Publication number
- JPH048727A JPH048727A JP11059290A JP11059290A JPH048727A JP H048727 A JPH048727 A JP H048727A JP 11059290 A JP11059290 A JP 11059290A JP 11059290 A JP11059290 A JP 11059290A JP H048727 A JPH048727 A JP H048727A
- Authority
- JP
- Japan
- Prior art keywords
- containing compound
- epihalohydrin
- epoxy group
- anhydride
- initiator
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 26
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 cyanide compound Chemical class 0.000 claims abstract description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 229940014800 succinic anhydride Drugs 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- FUQLWKAHHXZNOT-UHFFFAOYSA-N C(OC)COC.[Zn].C(#N)[Co](C#N)(C#N)(C#N)(C#N)C#N Chemical compound C(OC)COC.[Zn].C(#N)[Co](C#N)(C#N)(C#N)(C#N)C#N FUQLWKAHHXZNOT-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 241000238557 Decapoda Species 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000003944 halohydrins Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- KKNQBVYRSZDQNR-UHFFFAOYSA-N CC(=O)C.[Zn].C(#N)[Co](C#N)(C#N)(C#N)(C#N)C#N Chemical compound CC(=O)C.[Zn].C(#N)[Co](C#N)(C#N)(C#N)(C#N)C#N KKNQBVYRSZDQNR-UHFFFAOYSA-N 0.000 description 1
- SAGSSAKRCDYMFM-UHFFFAOYSA-N COCCOCCOC.[Zn].C(#N)[Co](C#N)(C#N)(C#N)(C#N)C#N Chemical compound COCCOCCOC.[Zn].C(#N)[Co](C#N)(C#N)(C#N)(C#N)C#N SAGSSAKRCDYMFM-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- RCTFHBWTYQOVGJ-UHFFFAOYSA-N chloroform;dichloromethane Chemical compound ClCCl.ClC(Cl)Cl RCTFHBWTYQOVGJ-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JKXONPYJVWEAEL-UHFFFAOYSA-N oxiran-2-ylmethyl acetate Chemical compound CC(=O)OCC1CO1 JKXONPYJVWEAEL-UHFFFAOYSA-N 0.000 description 1
- YLNSNVGRSIOCEU-UHFFFAOYSA-N oxiran-2-ylmethyl butanoate Chemical compound CCCC(=O)OCC1CO1 YLNSNVGRSIOCEU-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- UMVAHUBFIVIZAX-UHFFFAOYSA-N zinc cobalt(2+) 1,2-dimethoxyethane tetracyanide Chemical compound C(OC)COC.[C-]#N.[Zn+2].[Co+2].[C-]#N.[C-]#N.[C-]#N UMVAHUBFIVIZAX-UHFFFAOYSA-N 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］
本発明は末端安定化エピハロヒドリン重合体の製造方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a terminally stabilized epihalohydrin polymer.
［従来の技術〕
ハロゲン化アルキル基を含むポリエーテルボリオールは
その分子構造により、耐油性、難燃性等の性能を有する
ポリウレタンの原料としての有用性が期待される。その
ようなポリエーテルポリオールの製造方法としては、従
来アルキレンオキサイドの重合に使用されてきたアルカ
リ金属水酸化物を重合触媒として用いる方法や、三フッ
化ホウ素等を使用するカチオン重合等によるエピハロヒ
ドリンの開環重合による方法が考えられるがエピハロヒ
ドリン及びその間環生成物であるハロヒドリンがアルカ
リ条件下で不安定であることや、副生成物が多く分子量
を太き（することが困難である等の理由で実用的なポリ
エーテルポリオールの製造方法は知られていなかった。[Prior Art] Due to its molecular structure, polyether polyol containing a halogenated alkyl group is expected to be useful as a raw material for polyurethane having properties such as oil resistance and flame retardancy. Methods for producing such polyether polyols include methods using alkali metal hydroxides as polymerization catalysts, which have conventionally been used in the polymerization of alkylene oxides, and cationic polymerization using boron trifluoride, etc. to open epihalohydrins. A method using ring polymerization is considered, but it is not practical because epihalohydrin and its ring product halohydrin are unstable under alkaline conditions, and there are many by-products and the molecular weight is large (difficult to do so). There was no known method for producing a conventional polyether polyol.
そこで検討の結果複金属シアン化物錯体を触媒として使
用することにより、エピハロヒドリンをエポキシ基含有
化合物の一部又は全部の成分として使用したエポキシ基
含有化合物の重合によるポリエーテルポリオールの製造
方法を既に提案した。As a result of our studies, we have already proposed a method for producing polyether polyols by polymerizing epoxy group-containing compounds using epihalohydrin as part or all of the components of the epoxy group-containing compounds by using double metal cyanide complexes as catalysts. .
しかしながら、そのような製造方法によっても、特にエ
ピハロヒドリンが開環したへロヒドノンの構造を分子末
端の一部又は全部に有するため、末端水酸基の安定性と
いう点に問題があった〇
［発明の解決しようとする課題］
そこで我々は、エピハロヒドリンの開環重合により製造
されるポリエーテルポリオールのへロヒドリン末端構造
の不安定さを解消することを目的とし、検討を行なった
結果、複金属シアン化合物錯体を触媒としてエピハロヒ
ドリンをエポキシ基含有化合物の一部又は全部使用して
開始剤存在下関環重合し、続いて、末端基に対し、十分
な量の酸無水物を反応させることにより末端をカルボキ
シル基として安定化し、さらに必要に応じてエピハロヒ
ドリンを含まないエポキシ基含有化合物を重合させるこ
とで末端の安定化されたポリエーテル重合物を製造でき
ることを見出した。However, even with such a production method, there was a problem in terms of the stability of the terminal hydroxyl group, especially since epihalohydrin has a ring-opened helohydron structure at part or all of the molecular terminal. Therefore, with the aim of solving the instability of the helohydrin terminal structure of polyether polyols produced by ring-opening polymerization of epihalohydrin, we conducted studies and found that double metal cyanide complexes can be used as catalysts. As a method, epihalohydrin is polymerized in the presence of an initiator using part or all of an epoxy group-containing compound, and then the terminal group is stabilized as a carboxyl group by reacting with a sufficient amount of acid anhydride. They have also discovered that it is possible to produce a polyether polymer with stabilized terminals by polymerizing an epoxy group-containing compound that does not contain epihalohydrin, if necessary.
［課題を解決する為の手段］
本発明は開始剤存在下において複金属シアン化合物錯体
を触媒として使用し、エポキシ基含有化合物の一部又は
全部がエピハロヒドリンであるエポキシ基含有化合物の
重合反応において、エポキシ基含有化合物を重合後、酸
無水物を反応させる末端が安定化されたエピハロヒドリ
ン重合体の製造方法を提供するものである。[Means for Solving the Problems] The present invention uses a double metal cyanide complex as a catalyst in the presence of an initiator, and in a polymerization reaction of an epoxy group-containing compound in which part or all of the epoxy group-containing compound is epihalohydrin, The present invention provides a method for producing an epihalohydrin polymer whose terminals are stabilized by polymerizing an epoxy group-containing compound and then reacting with an acid anhydride.
本発明における複金属シアン化物錯体触媒とは、例えば
特公昭５９− １５３３６号公報記載のシアン化コバル
ト亜鉛−グライム等、米国特許第３２７８４５７号、第
３２７８４５８号、第３２７８４５９号公報に記載され
ている２種以上の金属を含むシアンイオンを一部又は全
部の配位子にもつ錯体のことであり、エポキシ基の開環
重合反応を触媒する能力のあるものをいう。本発明で使
用できる複金属シアン化物錯体として具体的にはへキサ
シアノコバルト亜鉛−グライム、ヘキサシアノコバルト
亜鉛−ジグライム、ヘキサシアノコバルト亜鉛−アセト
ン錯体等があげられる。The double metal cyanide complex catalyst in the present invention includes, for example, cobalt zinc cyanide-glyme described in Japanese Patent Publication No. 59-15336, and catalysts such as those described in U.S. Pat. It refers to a complex that has some or all of its ligands containing cyanide ions containing more than one species of metal, and has the ability to catalyze the ring-opening polymerization reaction of epoxy groups. Specific examples of the double metal cyanide complex that can be used in the present invention include zinc hexacyanocobalt-glyme, zinc hexacyanocobalt-diglyme, zinc hexacyanocobalt-acetone complex, and the like.
本発明で使用できるエピハロヒドリンとしてはエビフル
オロヒドリン、エピクロルヒドリン、エビブロモヒドリ
ンがあげられるが、経済的にはエピクロルヒドリンが最
も好ましい。Epihalohydrin that can be used in the present invention includes shrimp fluorohydrin, epichlorohydrin, and shrimp bromohydrin, and economically, epichlorohydrin is the most preferred.
本発明ではエピハロヒドリンとその他のエポキシ基含有
化合物を共重合させることも可能である。その場合、エ
ピハロヒドリンと他のエポキシ基含有化合物を添加する
時期を選択することにより、ランダム共重合体、ブロッ
ク共重合体いずれも製造することが可能である。エピク
ロルヒドリンとの共重合に使用できるエポキシ基含有化
合物としては、アリール又はアリルグノシジルエーテル
、有機カルボン酸グリシジルエステル、アルキレンオキ
サイドがあげられ、炭素数２〜１０の化合物が好ましい
。具体的には、フェニルグリシジルエーテル、トルイル
グリシジルエーテル、アリルグＩ／シジルエーテル、グ
リシジルアセテート、グリシジルプロビオネート、グリ
シジルブチレート、エチレンオキサイド、プロピレンオ
キサイド、１−ブテンオキサイドなどがあげられる。In the present invention, it is also possible to copolymerize epihalohydrin and other epoxy group-containing compounds. In that case, by selecting the timing of adding epihalohydrin and other epoxy group-containing compounds, it is possible to produce both random copolymers and block copolymers. Examples of epoxy group-containing compounds that can be used for copolymerization with epichlorohydrin include aryl or allyl gnosidyl ethers, organic carboxylic acid glycidyl esters, and alkylene oxides, with compounds having 2 to 10 carbon atoms being preferred. Specific examples include phenyl glycidyl ether, tolyl glycidyl ether, allylg I/cidyl ether, glycidyl acetate, glycidyl probionate, glycidyl butyrate, ethylene oxide, propylene oxide, and 1-butene oxide.
本発明では水やアルコール化合物等の任意の官能基数の
水酸基又はカルボキシル基末端の開始剤が使用できるが
、特にフェノール性水酸基を有する１価又は多価フェノ
ール化合物及び／又は１価又は多価有機カルボン酸化合
物を開始剤として使用することが好ましい。該フェノー
ル化合物としてはフェノール、クロルフェノール、ブロ
モフェノール、クレゾール、ヒドロキノン、メチルヒト
キノン、ビフェノール、ビスフェノールＡ、ビスフェノ
ールＢ、ビスフェノールＦ、テトラブロモビスフェノー
ルＡ、フェノール樹脂等があげられる。該有機カルボン
酸化合物としては、フタル酸、イソフタル酸、テレフタ
ル酸、コハク酸、フマル酸、マレイン酸、アジピン酸、
酢酸、プロピオン酸などがあげられる。In the present invention, initiators having arbitrary functional numbers of hydroxyl or carboxyl groups such as water or alcohol compounds can be used, but in particular monovalent or polyvalent phenol compounds having phenolic hydroxyl groups and/or monovalent or polyvalent organic carboxyl groups can be used. Preference is given to using acid compounds as initiators. Examples of the phenol compound include phenol, chlorophenol, bromophenol, cresol, hydroquinone, methylhumanquinone, biphenol, bisphenol A, bisphenol B, bisphenol F, tetrabromobisphenol A, and phenol resin. Examples of the organic carboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, succinic acid, fumaric acid, maleic acid, adipic acid,
Examples include acetic acid and propionic acid.
本発明においては、開始剤と複金属シアン化物錯体触媒
との混合物に、必要ならば溶媒存在下でエピハロヒドリ
ン及び／又は共重合させるエポキシ化合物を反応させる
温度条件下に少量ずつ添加しながら重合を行なうことが
できる。In the present invention, polymerization is carried out by adding epihalohydrin and/or an epoxy compound to be copolymerized little by little to a mixture of an initiator and a double metal cyanide complex catalyst in the presence of a solvent, if necessary, under reaction temperature conditions. be able to.
又、この重合はあらかじめ全ての原料を反応容器に仕込
み、反応温度に昇温することでも行なうことができる。This polymerization can also be carried out by charging all the raw materials in a reaction vessel in advance and raising the temperature to the reaction temperature.
本発明で使用する複金属シアン化物錯体の量は、反応さ
せるエピハロヒドリン等のモノマーに対し、重量で００
０１％から１％、好ましくは０．０５％から０．５％で
ある。この範囲以下では反応速度が遅くなるため実際的
ではなく、この範囲以上では経済的理由から好ましくな
い。本発明では必要に応じて溶媒が使用できるが、使用
できる溶媒としては、炭化水素系、ハロゲン化炭化水素
系、エーテル系、ケトン系などが一般に使用できる。具
体的にはトルエン、キシレン、テトラヒドロフラン、グ
ライム、ジエチルエーテル、ジオキサン、塩化メチレン
クロロホルム、四塩化炭素、テトラクロルエタン、トリ
クロルエタン、メチルエチルケトン、アセトンなどがあ
げられる。反応温度は４０℃から １５０℃、より好ま
しくは６０℃から１３０℃の範囲である。４０℃以下で
は反応が遅（実際的ではなくなり、 １５０℃を越える
と副反応が増加してくる。The amount of the double metal cyanide complex used in the present invention is 0.00% by weight based on the monomer such as epihalohydrin to be reacted.
0.01% to 1%, preferably 0.05% to 0.5%. If it is less than this range, the reaction rate will be slow and it is not practical, and if it is more than this range, it is not preferable for economic reasons. In the present invention, a solvent can be used if necessary, and generally usable solvents include hydrocarbons, halogenated hydrocarbons, ethers, ketones, and the like. Specific examples include toluene, xylene, tetrahydrofuran, glyme, diethyl ether, dioxane, methylene chloride chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, methyl ethyl ketone, and acetone. The reaction temperature ranges from 40°C to 150°C, more preferably from 60°C to 130°C. Below 40°C, the reaction is slow (not practical), and above 150°C, side reactions increase.
本発明ではさらに開始剤とエピハロヒドリンを一部又は
全部含むエポキシ基含有化合物の重合が終了した時点で
、反応混合物に酸無水物を添加し末端カルボキシ基とし
て安定化させる。In the present invention, when the polymerization of the epoxy group-containing compound containing part or all of the initiator and epihalohydrin is completed, an acid anhydride is added to the reaction mixture to stabilize it as a terminal carboxy group.
又、末端カルボキシル基として安定化させた重合体に更
にエピクロルヒドリンを含まないエポキシ基含有化合物
を反応させることにより、末端安定化されたポリオール
化合物が製造できる。Furthermore, a terminal-stabilized polyol compound can be produced by reacting a polymer stabilized as a terminal carboxyl group with an epoxy group-containing compound that does not contain epichlorohydrin.
本発明で使用する酸無水物として好ましいものは、無水
フタル酸、無水コハク酸、無水マレイン酸、無水テトラ
ヒドロフタル酸、無水へキサヒドロフタル酸があげられ
る。Preferred acid anhydrides used in the present invention include phthalic anhydride, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
酸無水物は、溶媒に溶解して加えても良いし、そのまま
加えても良い。反応温度は４０〜１５０℃より好ましく
は６０〜１３０℃の範囲である。酸無水物の反応が終了
した時点で、次に付加重合させるエピハロヒドリンを含
まないアルキレンオキサイドは炭素数２から１０のグリ
シジルエーテル、グリシジルエステル及び又はアルキレ
ンオキサイドでもよいが、より好ましくはエチレンオキ
サイド、プロピレンオキサイド、１−ブテンオキサイド
、インブテンオキサイド、１−ヘキセンオキサイド、シ
クロヘキセンオキサイド、スチレンオキサイド、アリル
グリシジルエーテルから選ばれる。エピハロヒドリンを
含まないエポキシ基含有化合物の付加重合は、反応温度
条件下に反応混合物にエポキシ基含有化合物を少量づつ
添加しながら行なっても良いし、始めに一括してエポキ
シ基含有化合物を加えても良い。反応温度は４０〜１５
０℃より好ましくは６０〜１３０℃の範囲である。触媒
は先のエピハロヒドリンを含むエポキシ基含有化合物の
重合時に使用した触媒がそのまま活性を有しているが、
必要に応じて追加しても良い。The acid anhydride may be added after being dissolved in a solvent, or may be added as is. The reaction temperature is in the range of 40 to 150°C, more preferably 60 to 130°C. Once the acid anhydride reaction is completed, the epihalohydrin-free alkylene oxide to be added and polymerized next may be a glycidyl ether, glycidyl ester, and/or alkylene oxide having 2 to 10 carbon atoms, but more preferably ethylene oxide or propylene oxide. , 1-butene oxide, inbutene oxide, 1-hexene oxide, cyclohexene oxide, styrene oxide, and allyl glycidyl ether. Addition polymerization of an epoxy group-containing compound that does not contain epihalohydrin can be carried out by adding the epoxy group-containing compound little by little to the reaction mixture under reaction temperature conditions, or by adding the epoxy group-containing compound all at once at the beginning. good. The reaction temperature is 40-15
The temperature is preferably in the range of 60 to 130°C. The catalyst used in the polymerization of the epoxy group-containing compound containing epihalohydrin is still active, but
You may add more if necessary.
［作用］
本発明で得られる末端が安定化されたエピハロヒドリン
を含むポリエーテル重合体は、従来のへロヒドリンを末
端の一部又は全部に有する構造のポリエーテル重合体に
対し、本質的に末端ハロヒドリン構造を有しないため、
脱ハロゲン化水素反応が起こりにくく、安定性が著しく
向上し、長期の保存安定性にもより優れている。[Function] The polyether polymer containing epihalohydrin whose terminals are stabilized obtained by the present invention essentially contains terminal halohydrin, as opposed to the conventional polyether polymer having a structure having helohydrin at a part or all of its terminals. Because it has no structure,
Dehydrohalogenation reaction is difficult to occur, stability is significantly improved, and long-term storage stability is also excellent.
［実施例］
実施例１
ビスフェノールＡ２７．８ｇとエピクロルヒドリン１８
．５ｇとへキサシアノコバルト亜鉛−グライム錯体０．
０５ｇの混合物をオートクレーブ中で８０℃に加熱した
。発熱反応が終了した後、無水コハク酸２４． Ｏｇを
加え、更に８０℃で３０分加熱した。その後プロピレン
オキサイド２３．２ｇを加えて８０℃に１時間加熱して
反応させた。未反応のエポキシドを脱気して、油状物２
６０ｇを得た。生成物はＧＰＣ分析で単一ピークを示し
、酸価０．７５、水酸基価は４６．０ｍｇＫＯＨ／ｇで
あった。[Example] Example 1 27.8 g of bisphenol A and 18 g of epichlorohydrin
．． 5g and hexacyanocobalt zinc-glyme complex 0.
05 g of the mixture was heated to 80° C. in an autoclave. After the exothermic reaction is completed, succinic anhydride 24. Og was added, and the mixture was further heated at 80°C for 30 minutes. Thereafter, 23.2 g of propylene oxide was added, and the mixture was heated to 80° C. for 1 hour to react. Degas the unreacted epoxide to form oil 2.
60g was obtained. The product showed a single peak in GPC analysis, and had an acid value of 0.75 and a hydroxyl value of 46.0 mgKOH/g.
実施例２
安息香酸１２．２ｇフェニルグリシジルエーテル３０ｇ
とエピクロルヒドリン９２．５ｇとへキサシアノコバル
ト亜鉛−グライム錯体０．０５ｇの混合物をオートクレ
ーブ中で１００℃に加熱した。発熱反応が終了した後、
無水コハク酸１６．３ｇを加えて１００℃に３０分間加
熱した。その後エチレンオキサイド１０ｇを加えて８０
℃に１時間加熱して反応させた。未反応のエポキシドを
脱気して、油状物１５８ｇを得た。生成物はＧＰＣ分析
で単一ピークを示し、酸価０．６０、水酸基価は３８．
０ｍｇＫＯＨ／ｇであった。Example 2 Benzoic acid 12.2g Phenyl glycidyl ether 30g
A mixture of 92.5 g of epichlorohydrin and 0.05 g of hexacyanocobalt zinc-glyme complex was heated to 100° C. in an autoclave. After the exothermic reaction has finished,
16.3 g of succinic anhydride was added and heated to 100° C. for 30 minutes. Then add 10g of ethylene oxide and
The mixture was heated to 1 hour to react. Unreacted epoxide was degassed to obtain 158 g of an oil. The product showed a single peak in GPC analysis, with an acid value of 0.60 and a hydroxyl value of 38.
It was 0 mgKOH/g.
実施例３
テレフタル酸１６．６ｇとエピクロルヒドリン１４０ｇ
とへキサシアノコバルト亜鉛−グライム錯体ｏ、 ０５
ｇの混合物をオートクレーブ中で８０℃に加熱した。発
熱反応が終了した後、無水マレイン酸２０．６ｇを加え
、３０分間加熱した。その後ブチレンオキサイド１７．
３ｇを加えて８０℃に１時間加熱して反応させた。未反
応のエポキシドを脱気して、油状物１９４ｇを得た。生
成物はＧＰＣ分析で単一ピークを示し、酸価０．５０、
水酸基価は５９、０ｍｇＫＯＨ／ｇであった。Example 3 16.6 g of terephthalic acid and 140 g of epichlorohydrin
Hexacyanocobalt zinc-glyme complex o, 05
The mixture of g was heated to 80° C. in an autoclave. After the exothermic reaction was completed, 20.6 g of maleic anhydride was added and heated for 30 minutes. Then butylene oxide 17.
3 g was added and heated to 80° C. for 1 hour to react. Unreacted epoxide was degassed to obtain 194 g of an oil. The product showed a single peak in GPC analysis, with an acid value of 0.50,
The hydroxyl value was 59.0 mgKOH/g.
実施例４
イソフタル酸３３．２ｇとエピクロルヒドリン７４、０
ｇとテトラヒドロフラン３３．２ｇとへキサシアノコバ
ルト亜鉛−グライム錯体０． （１５ｇの混合物をオー
トクレーブ中で８０℃に加熱した。発熱反応が終了した
後、無水コハク酸４１ｇを加え、８０℃で３０分間加熱
した。その後プロピレンオキサイド１１６ｇを内温か１
００℃を越えないように少量ずつ添加して反応させた。Example 4 33.2 g of isophthalic acid and 74.0 g of epichlorohydrin
g, 33.2 g of tetrahydrofuran, and 0.g of hexacyanocobalt zinc-glyme complex. (15 g of the mixture was heated to 80 °C in an autoclave. After the exothermic reaction had finished, 41 g of succinic anhydride was added and heated at 80 °C for 30 minutes. Then 116 g of propylene oxide was added to the internal temperature of
The mixture was added little by little and reacted so as not to exceed 00°C.
未反応のエポキシドを脱気して、油状物２６０ｇを得た
。生成物はＧＰＣ分析で単一ピークを示し、酸価は０．
７５、水酸基価は８９．０ｍｇＫＯＨ／ｇであった。Unreacted epoxide was degassed to obtain 260 g of an oil. The product showed a single peak in GPC analysis, and the acid value was 0.
75, and the hydroxyl value was 89.0 mgKOH/g.
比較例１
ビスフェノールＡ ２７．８ｇとエピクロルヒドリン１
８５．０ｇとへキサシアノコバルト亜鉛−グライム錯体
０．０５ｇの混合物をオートクレーブ中で８０℃減圧下
で未反応モノマーを脱気して、油状物２１０ｇを得た。Comparative example 1 Bisphenol A 27.8g and epichlorohydrin 1
A mixture of 85.0 g and 0.05 g of hexacyanocobalt zinc-glyme complex was placed in an autoclave at 80° C. and unreacted monomers were degassed under reduced pressure to obtain 210 g of an oily substance.
生成物はＧＰＣ分析で単一ピークを示し、酸価０．５０
、水酸基価は６０．０ｍｇＫＯＨ／ｇであった。The product showed a single peak in GPC analysis and had an acid value of 0.50.
, and the hydroxyl value was 60.0 mgKOH/g.
以上の実施例、比較例の生成物の安定性を表１に示す。Table 1 shows the stability of the products of the above Examples and Comparative Examples.
［発明の効果〕
本発明による末端安定化されたエビへロヒドリン重合体
は、過酷な条件下においても分解等による酸化の増大が
ほとんどないものである。[Effects of the Invention] The end-stabilized shrimp herohydrin polymer according to the present invention exhibits almost no increase in oxidation due to decomposition or the like even under severe conditions.
しかも、エビへロヒドリン重合体の合成に引き続き同一
触媒で末端安定化の処理を行なうことができるという効
果も有する。Moreover, it has the effect that terminal stabilization treatment can be performed using the same catalyst subsequent to the synthesis of the shrimp herrohydrin polymer.
Claims (1)
媒として使用し、エポキシ基含有化合物の一部又は全部
がエピハロヒドリンであるエポキシ基含有化合物の重合
反応において、エポキシ基含有化合物を重合後、酸無水
物を反応させる末端が安定化されたエピハロヒドリン重
合体の製造方法。 ２、開始剤存在下において複金属シアン化合物錯体を触
媒として使用し、エポキシ基含有化合物の一部又は全部
がエピハロヒドリンであるエポキシ基含有化合物の重合
反応において、エポキシ基含有化合物を重合後、酸無水
物を反応させ、その後さらにエピハロヒドリンを含まな
いエポキシ基含有化合物を反応させる特許請求の範囲第
１項記載の製造方法。３、エピハロヒドリンがエピクロ
ルヒドリンである特許請求の範囲第２項記載の製造方法
。 ４、酸無水物が無水フタル酸、無水コハク酸、無水マレ
イン酸、無水テトラヒドロフタル酸、無水ヘキサヒロド
フタル酸である特許請求の範囲第２項記載の方法。 ５、エピクロルヒドリンを含まないエポキシ基含有化合
物が、炭素数２から１０のアルキレンオキサイド又はグ
リシジルエーテル化合物である特許請求の範囲第２項記
載の製造方法。 ６、該開始剤がフェノール性水酸基含有化合物又はカル
ボキシル基含有化合物である特許請求の範囲第２項記載
の製造方法。[Scope of Claims] 1. In the polymerization reaction of an epoxy group-containing compound in which part or all of the epoxy group-containing compound is epihalohydrin using a double metal cyanide complex as a catalyst in the presence of an initiator, an epoxy group-containing compound A method for producing an epihalohydrin polymer with stabilized terminals, which involves polymerizing and then reacting with an acid anhydride. 2. In the polymerization reaction of an epoxy group-containing compound in which a part or all of the epoxy group-containing compound is epihalohydrin using a double metal cyanide complex as a catalyst in the presence of an initiator, after polymerizing the epoxy group-containing compound, acid anhydride is added. 2. The manufacturing method according to claim 1, wherein the epoxy group-containing compound that does not contain epihalohydrin is reacted. 3. The manufacturing method according to claim 2, wherein the epihalohydrin is epichlorohydrin. 4. The method according to claim 2, wherein the acid anhydride is phthalic anhydride, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride. 5. The manufacturing method according to claim 2, wherein the epoxy group-containing compound that does not contain epichlorohydrin is an alkylene oxide or glycidyl ether compound having 2 to 10 carbon atoms. 6. The manufacturing method according to claim 2, wherein the initiator is a phenolic hydroxyl group-containing compound or a carboxyl group-containing compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11059290A JP2960477B2 (en) | 1990-04-27 | 1990-04-27 | Method for producing terminal-stabilized epihalohydrin polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11059290A JP2960477B2 (en) | 1990-04-27 | 1990-04-27 | Method for producing terminal-stabilized epihalohydrin polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH048727A true JPH048727A (en) | 1992-01-13 |
| JP2960477B2 JP2960477B2 (en) | 1999-10-06 |
Family
ID=14539766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11059290A Expired - Fee Related JP2960477B2 (en) | 1990-04-27 | 1990-04-27 | Method for producing terminal-stabilized epihalohydrin polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2960477B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0743093A1 (en) * | 1995-05-15 | 1996-11-20 | ARCO Chemical Technology, L.P. | Highly active double metal cyanide complex catalysts |
| CN113457564A (en) * | 2021-07-07 | 2021-10-01 | 贵州省材料产业技术研究院 | Esterified SMA (styrene maleic anhydride) modified quaternary ammonium phosphonium salt high-molecular antibacterial surfactant and application thereof |
-
1990
- 1990-04-27 JP JP11059290A patent/JP2960477B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0743093A1 (en) * | 1995-05-15 | 1996-11-20 | ARCO Chemical Technology, L.P. | Highly active double metal cyanide complex catalysts |
| CN113457564A (en) * | 2021-07-07 | 2021-10-01 | 贵州省材料产业技术研究院 | Esterified SMA (styrene maleic anhydride) modified quaternary ammonium phosphonium salt high-molecular antibacterial surfactant and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2960477B2 (en) | 1999-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5032671A (en) | Preparation of lactone polymers using double metal cyanide catalysts | |
| EP0749999B1 (en) | Method for polymerizing macrocyclic polyester oligomers | |
| US3483169A (en) | Polyester-polyethers and process of preparing the same | |
| CN110317332B (en) | Catalyst system for preparing block polymer and method for catalytically synthesizing block polymer | |
| CN114269806A (en) | Degradable polyether | |
| JPH0730171B2 (en) | Unsaturated poly (α-hydroxy acid) copolymer | |
| US5391700A (en) | Process for producing polyester by ring-opening copolymerization | |
| CN111925508B (en) | Preparation method of polycaprolactone and product thereof | |
| JPH048727A (en) | Production of terminal stabilized epihalohydrin polymer | |
| EP0408719A4 (en) | Hydroxyethers of epoxidized polybutenes | |
| Steinmann | Investigations on the curing of epoxides with phthalic anhydride | |
| CN104812799A (en) | Polyalkylene carbonate resin and method for producing same | |
| US3767618A (en) | Process for the preparation of epoxy resins by interfacial condensation and the resultant resins | |
| US3464958A (en) | Production of polyether ester copolymers of tetrahydrofuran and cyclic acid anhydride | |
| KR20230036995A (en) | Double metal cyanide catalyst, preparation method of the catalyst, and preparation method of polyalkylene carbonate using the catalyst | |
| JPH048726A (en) | Production of terminal polyfunctionalized epihalohydrin polymer | |
| JP2001011170A (en) | Production of polycarbonate | |
| CN100430136C (en) | Double metal cyanide catalysts | |
| JP2966889B2 (en) | Method for producing polyetherester polyol | |
| US3624012A (en) | Process for preparing halogenated copolymers of olefinically unsaturated cycloaliphatic monoanhydrides with cyclic monoethers | |
| JPH03265626A (en) | Production of epihalohydrin polymer | |
| JP3013918B2 (en) | Method for producing aliphatic polyester | |
| CN114437330B (en) | Catalyst system for copolymerization of cyclic monomer sequences and method for preparing block polyester | |
| US3480567A (en) | Polymerization of a vicinal alkylene oxide using a novel organometallic compound-polyol cocatalyst | |
| JPH04227925A (en) | Production of polyoxyalkylene compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080730 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080730 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090730 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |