JPH0368608A - Acrylonitrile compolymer and preparation thereof - Google Patents
Acrylonitrile compolymer and preparation thereofInfo
- Publication number
- JPH0368608A JPH0368608A JP20386589A JP20386589A JPH0368608A JP H0368608 A JPH0368608 A JP H0368608A JP 20386589 A JP20386589 A JP 20386589A JP 20386589 A JP20386589 A JP 20386589A JP H0368608 A JPH0368608 A JP H0368608A
- Authority
- JP
- Japan
- Prior art keywords
- acrylonitrile copolymer
- polymerization
- acrylonitrile
- compd
- formula
- 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 15
- 150000002902 organometallic compounds Chemical class 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052790 beryllium Inorganic materials 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 150000003623 transition metal compounds Chemical class 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001573 beryllium compounds Chemical class 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229940043430 calcium compound Drugs 0.000 claims description 2
- 150000001674 calcium compounds Chemical class 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 150000002681 magnesium compounds Chemical class 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 22
- 239000002904 solvent Substances 0.000 abstract description 7
- 230000000737 periodic effect Effects 0.000 abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 125000002524 organometallic group Chemical group 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 9
- 229920002239 polyacrylonitrile Polymers 0.000 description 9
- -1 propyl beryllium Chemical compound 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002901 organomagnesium compounds Chemical class 0.000 description 4
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZKSADANYBSWZAB-UHFFFAOYSA-N CCCCCC[Mg]CCCCCC Chemical group CCCCCC[Mg]CCCCCC ZKSADANYBSWZAB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WGZPYSVPKIZOMF-UHFFFAOYSA-N C(C)[Mg]N(CC)CC Chemical compound C(C)[Mg]N(CC)CC WGZPYSVPKIZOMF-UHFFFAOYSA-N 0.000 description 1
- HQQXFHCBRUIMSD-UHFFFAOYSA-N C1(=CC=CC=C1)CC[Ca] Chemical compound C1(=CC=CC=C1)CC[Ca] HQQXFHCBRUIMSD-UHFFFAOYSA-N 0.000 description 1
- YMTKZUROOGUACT-UHFFFAOYSA-N CC(C)CC[Mg]CCC(C)C Chemical group CC(C)CC[Mg]CCC(C)C YMTKZUROOGUACT-UHFFFAOYSA-N 0.000 description 1
- ODHFJIDDBSDWNU-UHFFFAOYSA-N CCCC[Mg]CCCC Chemical group CCCC[Mg]CCCC ODHFJIDDBSDWNU-UHFFFAOYSA-N 0.000 description 1
- RCZPHVPIOWNERS-UHFFFAOYSA-N CCCO[Ti] Chemical compound CCCO[Ti] RCZPHVPIOWNERS-UHFFFAOYSA-N 0.000 description 1
- WXJHKVKWWWQZER-UHFFFAOYSA-N CCC[Ba]CCC Chemical compound CCC[Ba]CCC WXJHKVKWWWQZER-UHFFFAOYSA-N 0.000 description 1
- ABXKXVWOKXSBNR-UHFFFAOYSA-N CCC[Mg]CCC Chemical group CCC[Mg]CCC ABXKXVWOKXSBNR-UHFFFAOYSA-N 0.000 description 1
- VLPNUWNKSJVFJY-UHFFFAOYSA-N CC[Mg]C Chemical compound CC[Mg]C VLPNUWNKSJVFJY-UHFFFAOYSA-N 0.000 description 1
- BYKOWANXVGYJCA-UHFFFAOYSA-N CC[Sr]CC Chemical compound CC[Sr]CC BYKOWANXVGYJCA-UHFFFAOYSA-N 0.000 description 1
- OBBRHJBMQXGEEK-UHFFFAOYSA-N COCC[Mg] Chemical compound COCC[Mg] OBBRHJBMQXGEEK-UHFFFAOYSA-N 0.000 description 1
- ZASAJMJGPSLNJZ-UHFFFAOYSA-N C[Si](C)(C)CC[Mg] Chemical compound C[Si](C)(C)CC[Mg] ZASAJMJGPSLNJZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-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
- QQWBXRUCDIOFDM-UHFFFAOYSA-M F[Mg]Cc1ccccc1 Chemical compound F[Mg]Cc1ccccc1 QQWBXRUCDIOFDM-UHFFFAOYSA-M 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- ZXRRHFSTAFVGOC-UHFFFAOYSA-N [AlH3].[K] Chemical compound [AlH3].[K] ZXRRHFSTAFVGOC-UHFFFAOYSA-N 0.000 description 1
- HXEMAHFTVFVYMX-UHFFFAOYSA-M [Br-].CC[Ca+] Chemical compound [Br-].CC[Ca+] HXEMAHFTVFVYMX-UHFFFAOYSA-M 0.000 description 1
- XATBLMRJQUUXPN-UHFFFAOYSA-N [Li].[Li].C(CCC)C(C)([Zn]CC)CCCC Chemical compound [Li].[Li].C(CCC)C(C)([Zn]CC)CCCC XATBLMRJQUUXPN-UHFFFAOYSA-N 0.000 description 1
- BRRORWOTKMALRA-UHFFFAOYSA-N [Mg+2].C[Si](C)(C)[NH-].C[Si](C)(C)[NH-] Chemical compound [Mg+2].C[Si](C)(C)[NH-].C[Si](C)(C)[NH-] BRRORWOTKMALRA-UHFFFAOYSA-N 0.000 description 1
- AOAJSDIIVLNNBM-UHFFFAOYSA-N [Mg]CCC1=CC=CC=C1 Chemical compound [Mg]CCC1=CC=CC=C1 AOAJSDIIVLNNBM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- VRWRYXRXVZEJKF-UHFFFAOYSA-N beryllium;ethane Chemical compound [Be+2].[CH2-]C.[CH2-]C VRWRYXRXVZEJKF-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- VZDMFNJJUXFAIU-UHFFFAOYSA-N calcium;benzene Chemical compound [Ca+2].C1=CC=[C-]C=C1.C1=CC=[C-]C=C1 VZDMFNJJUXFAIU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- NKKMVIVFRUYPLQ-NSCUHMNNSA-N crotononitrile Chemical compound C\C=C\C#N NKKMVIVFRUYPLQ-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- KZLUHGRPVSRSHI-UHFFFAOYSA-N dimethylmagnesium Chemical group C[Mg]C KZLUHGRPVSRSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- NEMFQSKAPLGFIP-UHFFFAOYSA-N magnesiosodium Chemical compound [Na].[Mg] NEMFQSKAPLGFIP-UHFFFAOYSA-N 0.000 description 1
- WRYKIHMRDIOPSI-UHFFFAOYSA-N magnesium;benzene Chemical compound [Mg+2].C1=CC=[C-]C=C1.C1=CC=[C-]C=C1 WRYKIHMRDIOPSI-UHFFFAOYSA-N 0.000 description 1
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical class [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 1
- TUPQEGQHLZFSAP-UHFFFAOYSA-N magnesium;diethylazanide Chemical compound [Mg+2].CC[N-]CC.CC[N-]CC TUPQEGQHLZFSAP-UHFFFAOYSA-N 0.000 description 1
- TXZBQHZEKIROSD-UHFFFAOYSA-N magnesium;diphenylazanide Chemical compound [Mg+2].C=1C=CC=CC=1[N-]C1=CC=CC=C1.C=1C=CC=CC=1[N-]C1=CC=CC=C1 TXZBQHZEKIROSD-UHFFFAOYSA-N 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical group [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- BFRJXURCBYWDDT-UHFFFAOYSA-N magnesium;trimethylsilanide Chemical compound [Mg+2].C[Si-](C)C.C[Si-](C)C BFRJXURCBYWDDT-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- MJKYCJBIICJHRD-UHFFFAOYSA-N pentane-2,4-dione;vanadium Chemical compound [V].CC(=O)CC(C)=O MJKYCJBIICJHRD-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000005309 thioalkoxy group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アクリロニトリル（以下、ｒＡＮＪと略記す
る）系共重合体およびその製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an acrylonitrile (hereinafter abbreviated as rANJ) copolymer and a method for producing the same.
さらに詳しくは、機械的強度および湿潤状態における耐
熱性などに優れた繊維素材や金属の選択吸着用素材、あ
るいは導電性ポリマー用などとして有用なＡＮ系共重合
体、ならびにそれを工業的有利に製造する方法に関する
。More specifically, we will focus on AN-based copolymers useful as fiber materials with excellent mechanical strength and heat resistance in wet conditions, materials for selective adsorption of metals, conductive polymers, etc., and their industrially advantageous production. Regarding how to.
従来、ＡＮ系共重合体は、繊維に成形した際のかさ高さ
や、風合い、保温性などに優れるうえに、共重合成分の
種類によっては鮮やかな色調に染色することができ、か
つ染色耐候性にも優れるなどの物性を有することから、
衣料用として広く用いられている。Conventionally, AN-based copolymers have excellent bulk, texture, and heat retention properties when molded into fibers, and depending on the type of copolymer component, they can be dyed in vivid colors, and they have excellent dyeing and weather resistance. Because it has physical properties such as excellent
Widely used for clothing.
このＡＮ系共重合体は通常ラジカル重合開始剤を用いて
、ＡＮとコモノマーとを共重合させることにより製造さ
れている。しかしながら、このような方法によって得ら
れるＡＮ系共重合体においては、核磁気共鳴の方法（以
下、ｒＮＭＲＪと略記する）による測定によれば少なく
ともＡＮモノマーユニットのみからなる重合体連鎖部分
に分子構造の規則性は存在しない。この共重合体を溶媒
１こ溶解して繊維やフィルム等に成形した場合、成形品
は結晶性が低くて、機械的特性に関しては十分に満足し
うるものではなく、また、耐熱性、中でも湿潤状態にお
ける耐熱性に劣る。特に繊維は、寸法安定性、引張強度
、弾性率などが不足しているため、高品位織物などの高
級衣料分野への展開が制限されているのみならず、産業
資材・宇宙工学分野等への用途展開も制約されているの
が現状である。This AN-based copolymer is usually produced by copolymerizing AN and a comonomer using a radical polymerization initiator. However, in the AN-based copolymer obtained by such a method, measurements by nuclear magnetic resonance method (hereinafter abbreviated as rNMRJ) show that at least the molecular structure of the polymer chain consisting only of AN monomer units is There are no regularities. When this copolymer is dissolved in one solvent and molded into fibers, films, etc., the molded product has low crystallinity and is not fully satisfactory in terms of mechanical properties. Poor heat resistance under certain conditions. In particular, fibers lack dimensional stability, tensile strength, and modulus of elasticity, which not only limits their use in the field of high-end clothing such as high-grade textiles, but also in the fields of industrial materials and space engineering. The current situation is that the development of applications is also restricted.
一方、ＡＮのホモポリマーの分野では尿素−ＡＮの包接
化合物にγ線などの活性線を照射すると、立体規則性を
有するポリアクリロニトリル（以下、ｒＰＡＮ Ｊと略
称する）、いわゆる高立体規則性ＰＡＮが得られること
が知られている。この方法によれば、これまで得られて
いなかった良好なＰＡＮの単結晶が得られることが報告
されている〔「ポリマー・ジャーナル」第１９巻、９９
７ページ（１９８７年）〕。また、この方法によって得
らイック・トリアット分￥＝２５％のＰＡＮの水存在下
の融点は１８３℃であるのに対し同トリアット分率６２
％のＰＡＮのそれは１９０℃にもなる。また、その繊維
は熱水中のヤング率が従来のＰＡＮ繊維に比して著しく
向上し、かつ湿潤状態における耐熱性が改善されるとい
う特徴を有している。また、このＰＡＮの溶液に硫酸銅
などの金属塩を添加すると、金属イオンがＡＮ系共重合
体分子のシアノ基に対してメソ位に選択的に配位するた
め〔「ポリマー・ジャーナル」第１８巻、２７７ページ
（１９８６年）〕、金属の選択的吸着素材や導電性ポリ
マーの材料としても好適である。On the other hand, in the field of AN homopolymers, when urea-AN clathrate compounds are irradiated with actinic rays such as gamma rays, stereoregular polyacrylonitrile (hereinafter abbreviated as rPAN J), so-called highly stereoregular PAN, is produced. is known to be obtained. It has been reported that according to this method, a good single crystal of PAN, which has not been obtained so far, can be obtained ["Polymer Journal" Vol. 19, 99]
7 pages (1987)]. Furthermore, the melting point of PAN with a triat content of 25% obtained by this method in the presence of water is 183°C, whereas the same triat content is 62°C.
% of PAN is as high as 190°C. Further, the fiber has characteristics that the Young's modulus in hot water is significantly improved compared to conventional PAN fibers, and the heat resistance in a wet state is improved. In addition, when a metal salt such as copper sulfate is added to this PAN solution, the metal ion selectively coordinates to the meso position with respect to the cyano group of the AN-based copolymer molecule ["Polymer Journal" No. 18] Vol., p. 277 (1986)], it is also suitable as a material for selectively adsorbing metals and as a material for conductive polymers.
しかしながら、前記のＡＮ−尿素包接化合物にγ線を照
射して、高立体規則性ＰＡＮを得る方法は、ＡＮと尿素
との特殊な化合物を利用するものであるため他のモノマ
ーを共に包接させて重合することが一般には不可能であ
る。すなわち、この方法によりＡＮ系共重合体を製造す
ることができない。However, the method of obtaining highly stereoregular PAN by irradiating the AN-urea clathrate compound with gamma rays uses a special compound of AN and urea, so other monomers are also included. In general, it is impossible to polymerize in such a manner. That is, an AN-based copolymer cannot be produced by this method.
本発明は、このように従来のＡＮ系共重合体が有する低
結晶性、低機械的特性、特に湿潤状態における低耐熱性
等の種々の欠点を克服するために、ＡＮモノマーユニッ
トのみからなる連鎖部分の立体規則性の高いＡＮ系共重
合体を得ることを目的としてなされたものである。In order to overcome the various drawbacks of conventional AN-based copolymers such as low crystallinity, low mechanical properties, and especially low heat resistance in a wet state, the present invention provides a chain consisting only of AN monomer units. This was done with the aim of obtaining an AN-based copolymer with high stereoregularity of its parts.
本発明者らはＡＮの共重合に関する研究を鋭意重ね、特
殊なアニオン重合触媒を用いてＡＮの共重合実験を行う
と、ＡＮ系共重合体のＡＮモノマーユニットのみからな
る二連子の立体規則性を飛躍的に高めた共重合体が得ら
れることを見いだした。The present inventors have diligently conducted research on the copolymerization of AN, and when conducting copolymerization experiments of AN using a special anionic polymerization catalyst, it was found that the stereoregularity of the diadlet consisting only of AN monomer units in the AN-based copolymer We have discovered that a copolymer with dramatically improved properties can be obtained.
即ち、ＡＮを共重合するにあたり以下に述べるような有
機金属化合物を開始剤として重合を行うと、これによっ
て得られるＰＡＮＡＮ系共重合体Ｎモノマーユニットの
みからなる二連子の立体規則性は従来の技術によって得
られるＰＡＮＡＮ系共重合体れに比して大幅に向上し、
アイソタクティック・トリアッド分率で０．３５から高
いものでは約０．６にもなることが分かった。That is, when AN is copolymerized using an organometallic compound as described below as an initiator, the stereoregularity of the resulting PANAN-based copolymer diad consisting only of N monomer units is different from that of the conventional one. Significantly improved compared to PANAN copolymer obtained by technology,
It was found that the isotactic triad fraction ranges from 0.35 to about 0.6 in higher cases.
すなわち、開始剤として、アルカリ土類金属を含有する
有機金属化合物、あるいは周期律表第１゜■および■族
の金属を二種以上組み合わせたいわゆるアート・コンプ
レックスと呼ばれる有機金属化合物を用いると、顕著に
立体規則性を向上させることができる。また、アルカリ
土類金属を含有する有機金属化合物と遷移金属化合物と
を組合せて用いるいわゆるチーグラー・ナツタ型の開始
剤系を用いても、同様の効果を発現できることが分かっ
た。In other words, if an organometallic compound containing an alkaline earth metal or an organometallic compound called an art complex, which is a combination of two or more metals from groups 1 and 2 of the periodic table, is used as an initiator, stereoregularity can be improved. It has also been found that the same effect can be achieved by using a so-called Ziegler-Natsuta type initiator system that uses a combination of an organic metal compound containing an alkaline earth metal and a transition metal compound.
以下に、本発明で使用する開始剤の例を挙げるが、これ
らの例は本発明の特許請求の範囲をなんら制限するもの
ではない。Examples of initiators used in the present invention are listed below, but these examples are not intended to limit the scope of the claims of the present invention.
まず、アルカリ土類金属を含む有機金属化合物としては
ベリリウム、マグネシウム、カルシウム、ストロンチウ
ム、バリウムを含有する有機金属化合物が用いられる。First, as the organometallic compound containing an alkaline earth metal, an organometallic compound containing beryllium, magnesium, calcium, strontium, and barium is used.
このうち、有機ベリリウム化合物としては、式Ｒ２Ｂｅ
で表される形のものとしてジエチルベリリウム、ノルマ
ルプロピルベリリウム、ノルマルブチルエチルベリリウ
ム等があり、式ＲＢｅＸの形で表されるグリニヤール・
タイプのものにフェニルベリリウムクロライド、アリル
ベリリウムブロマイド等がある。また、有機カルシウム
化合物にはジフェニルカルシウム、フェニルエチルカル
シウムなどの式Ｒ，Ｃａで表されるものとエチルカルシ
ウムブロマイド、ノルマルブチルカルシウムヨーダイト
などの式ＲＣａＸで表されるものがある。勿論、ジエチ
ルストロンチウムおよびジノルマルプロピルバリウムな
ども有効である。Among these, the organic beryllium compound has the formula R2Be
Diethyl beryllium, normal propyl beryllium, normal butylethyl beryllium, etc. are represented by the formula RBeX.
Types include phenylberyllium chloride and allylberyllium bromide. Further, organic calcium compounds include those represented by the formula R,Ca such as diphenylcalcium and phenylethylcalcium, and those represented by the formula RCaX such as ethylcalcium bromide and n-butylcalcium iodite. Of course, diethylstrontium and di-normal propylbarium are also effective.
更に、有機マグネシウム化合物も多くの有効な化合物を
有し、例えば、式Ｒ２Ｍｇ （Ｒは脂肪族もしくは芳香
族炭化水素またはそれらの組合せからなる炭化水素基）
で表される、ジメチルマグネシウム、ジエチルマグネシ
ウム、ジノルマルプロピルマグネシウム、ジノルマルブ
チルマグネシウム、ジイソアミルマグネシウム、ジノル
マルヘキシルマグネシウム、ジアリルマグネシウム、ジ
フェニルマグネシウムなどの同一炭化水素基を二個有す
る有機マグネシウム化合物、ならびに、メチルエチルマ
グネシウム、ノルマルブチルエチルベリリウム、フェニ
ルエチルマグネシウムなどの二つの異なる炭化水素基を
有する有機マグネシウム化合物が挙げられる。更にいわ
ゆるグリニヤール試薬ＲＭｇＸ （Ｒは前記と同じ、Ｘ
はハロゲンである）といわれるものも開始剤として本発
明の効果を発現するのに有効である。これにはエチルマ
グネシウムクロライド、ノルマルブチルマグネシウムブ
ロマイド、フェニルマグネシウムヨーダイト、ベンジル
マグネシウムフルオライドなどが含まれる。Additionally, organomagnesium compounds also have many useful compounds, such as those with the formula R2Mg (R is a hydrocarbon group consisting of an aliphatic or aromatic hydrocarbon or a combination thereof).
Organomagnesium compounds having two identical hydrocarbon groups such as dimethylmagnesium, diethylmagnesium, di-normal propylmagnesium, di-normal butylmagnesium, diisoamylmagnesium, di-normalhexylmagnesium, diallylmagnesium, diphenylmagnesium, etc., represented by Examples include organomagnesium compounds having two different hydrocarbon groups, such as methyl ethyl magnesium, n-butylethyl beryllium, and phenylethyl magnesium. Furthermore, the so-called Grignard reagent RMgX (R is the same as above,
is a halogen) are also effective as initiators to exhibit the effects of the present invention. These include ethylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium iodite, benzylmagnesium fluoride, etc.
更には、これらのアルキル基をアミン基、アルコキシ基
、アルキルシリル基、チオアルコキシ基′およびそれら
の複合された置換基にて置き換えた有機マグネシウム化
合物もより高い効果を発揮する。例えば、エチルジエチ
ルアミノマグネシウムのような式Ｒ，ＮＭｇＲで表され
る化合物、およびビス（ジエチルアミノ）マグネシウム
、ビス（ジフェニルアミノ）マグネシウムのような式Ｒ
ＪＭｇＮＲ２で表される化合物である（これら２つの式
中のＲは前記と同様であるが、Ｒ２として表される２つ
のＲは互いに結合しそれらが結合している窒素原子とと
もに複素環を形成していてもよい）；メトキシエチルマ
グネシウムのような式ＲＯＭｇＲ（Ｒは前記と同様）で
表される化合物；ジメトキシマグネシウム、ジェトキシ
マグネシウム、ジノルマルブトキシマグネシウムのよう
な式ＲＯＭｇＯＲ（Ｒは前記と同様）で表される化合物
；ビス（トリメチルシリル）マグネシウムのような式Ｒ
３ＳｔＭｇＳｔＲ３（Ｒは前記と同様）で表される化合
物；トリメチルシリルエチルマグネシウムのような式Ｌ
ＳｔＭｇＲ（Ｒは前記と同様）で表される化合物；チオ
メトキシエチルマグネシウムのような式Ｒ３ＭｇＲ（Ｒ
は前記と同様）で表される化合物；ビス（チオメトキシ
〉マグネシウムのような式Ｒ３Ｍｇ５Ｒ（Ｒは前記と同
様）で表される化合物；ならびに壮キ寸ビス（トリメチ
ルシリルアミノ）マグネシウムのような式（Ｒ３Ｓｉ）
２ＮＭｇＮ（ＳｉＬ） ２で表される化合物および式（
Ｒ３Ｓｉ）２ＮＭｇＲ（両式中のＲは前記と同様）で表
される化合物などである。Furthermore, organomagnesium compounds in which these alkyl groups are replaced with amine groups, alkoxy groups, alkylsilyl groups, thioalkoxy groups, and composite substituents thereof also exhibit higher effects. For example, compounds represented by formula R such as ethyldiethylaminomagnesium, NMgR, and compounds represented by formula R such as bis(diethylamino)magnesium and bis(diphenylamino)magnesium.
It is a compound represented by JMgNR2 (R in these two formulas is the same as above, but the two Rs represented as R2 are bonded to each other to form a heterocycle with the nitrogen atom to which they are bonded. Compounds represented by the formula ROMgR (R is the same as above) such as methoxyethylmagnesium; ROMgOR (R is the same as above) such as dimethoxymagnesium, jetoxymagnesium, di-normal butoxymagnesium Compounds represented by formula R such as bis(trimethylsilyl)magnesium
Compound represented by 3StMgStR3 (R is the same as above); Formula L such as trimethylsilylethylmagnesium
A compound represented by StMgR (R is the same as above); a compound represented by formula R3MgR (R
compounds represented by the formula R3Mg5R (where R is the same as above) such as bis(thiomethoxy)magnesium; and compounds represented by the formula (R3Si) such as bis(trimethylsilylamino)magnesium )
2NMgN(SiL) Compound represented by 2 and formula (
R3Si)2NMgR (R in both formulas is the same as above), and the like.
また、これらの有機金属化合物に対して遷移金属化合物
を組み合わせて用いることも可能である。It is also possible to use a transition metal compound in combination with these organometallic compounds.
即ちその遷移金属化合物とは通常チーグラー・ナツタ触
媒と言われている重合開始剤の原料の一部であり、主な
ものとしてはジクロロチタニウム、トリクロロチタニウ
ム、テトラクロロチタニウム、テトラノルマルプロポキ
シチタニウム、テトラヒドロキシチタニウム、ジシクロ
ペンタジェニルジクロロチタニウムなどで代表されるチ
タン化合物やトリクロロバナジウム、テトラクロロバナ
ジウム、オキシトリクロライドバナジウム、アセチルア
セトンバナジウムなどのバナジウム化合物やさらにはト
リクロロチタニウムなど数多くの化合物がある。That is, the transition metal compound is a part of the raw material of a polymerization initiator that is usually called a Ziegler-Natsuta catalyst, and the main ones are dichlorotitanium, trichlorotitanium, tetrachlorotitanium, tetranormal propoxytitanium, and tetrahydroxy. There are many compounds such as titanium compounds such as titanium and dicyclopentagenyl dichlorotitanium, vanadium compounds such as trichlorovanadium, tetrachlorovanadium, oxytrichloride vanadium, acetylacetone vanadium, and even trichlorotitanium.
更に、周期律表第１．■および■族の金属を二種以上組
み合わせたいわゆるアート・コンプレックスの例として
は、次の一般式で表されるものを挙げることができる。Furthermore, periodic table 1. An example of a so-called art complex, which is a combination of two or more metals of group (1) and group (2), is represented by the following general formula.
即ち、Ｍ’Ｍ’Ｒ，ｌ、Ｈｌ、。That is, M'M'R,l, Hl.
Ｍ’ＡｌＲ４−、Ｈｎ、 Ｍ’＾ＩＲ，−、Ｘ、、、
Ｍ”（ＡＩＲ，−、、Ｈ，）２゜Ｍ’ＡＩＲ，−Ｒ（Ｎ
Ｒ２）！、、 ＬｉＺｎＲｓ−ｎ（ＮＲ２）−１および
い２２ｎＲ＊−０（ＮＲ，）、である。M'AlR4-, Hn, M'^IR,-, X,...
M'(AIR,-,,H,)2゜M'AIR,-R(N
R2)! ,, LiZnRs-n(NR2)-1 and 22nR*-0(NR,).
ここで、式中のＲはたがいに同一でも異なっていてもよ
く、それぞれ脂肪族または芳香族炭化水素もしくはそれ
らの組合せによってなる炭化水素である。Ｍｌはリチウ
ム、ナトリウム、カリウムのうちから選ばれた一種の金
属、Ｍ２はマグネシウム、ベリリウム、カルシウム、亜
鉛、カドミウムのうちから選ばれた一種の金属、Ｘは弗
素、塩素、臭素、沃素のうちから選ばれた一種の元素で
あり、ｎは零または正の整数で同一分子内における５−
ｎ、４−ｎあるいは３−ｎの添え字が負にならない範囲
の値をとるものとする。Here, R in the formula may be the same or different, and each represents a hydrocarbon consisting of an aliphatic or aromatic hydrocarbon or a combination thereof. Ml is a metal selected from lithium, sodium, and potassium; M2 is a metal selected from magnesium, beryllium, calcium, zinc, and cadmium; X is a metal selected from fluorine, chlorine, bromine, and iodine. It is a selected type of element, where n is zero or a positive integer and 5-
It is assumed that the subscript of n, 4-n, or 3-n takes a value within a range that does not become negative.
具体的に上記一般式で表される有機金属化合物の例を示
すと、弐〇’Ｍ”Ｒ，、Ｈ，の例としては、トリエチル
ナトリウムマグネシウム、メチルジエチルリチウムマグ
ネシウム、ジイソブチルヒドロナトリウムマグネシウム
、ノルマルブチルジヒドロリチウムマグネシウムをあげ
ることができる。Specifically, examples of organometallic compounds represented by the above general formula include triethyl sodium magnesium, methyl diethyl lithium magnesium, diisobutylhydrosodium magnesium, n-butyl Dihydrolithium magnesium can be given.
式Ｍ’ＡＩＲ，，，）１．、の例としては、テトラエチ
ルリチウムアルミニウム、トリエチルノルマルフチルリ
チウムアルミニウム、テトラエチルカリウムアルミニウ
ム、テトラエチルナトリウムアルミニウム、トリエチル
ヒドロリチウムアルミニウム、ジフェニルジヒドロリチ
ウムアルミニウム、ベンジルトリヒドロリチウムアルミ
ニウムなどを挙げることができる。Formula M'AIR,,,)1. Examples include tetraethyl lithium aluminum, triethyl normal phthyl lithium aluminum, tetraethyl potassium aluminum, tetraethyl sodium aluminum, triethylhydrolithium aluminum, diphenyldihydrolithium aluminum, benzyltrihydrolithium aluminum and the like.
弐Ｍ”ＡＩＲ，、Ｘ、の例としては、ペンタエチルマグ
ネシウムアルミニウム、ペンタノルマルブチルマグネシ
ウムアルミニウム、テトラエチルメチルマグネシウムア
ルミニウム、テトラエチルクロロマグネシウムアルミニ
ウム、ベンジルジエチルジクロロマクネシウムアルミニ
ウム、ジフェニルトリクロロマグネシウムアルミニウム
、ペンタエチル亜鉛アルミニウム、ペンタエチルベリリ
ウムアルミニラム、ペンタエチルカルシウムアルミニウ
ム、ペンタエチルカドミウムアルミニウム、エチルテト
ラクロロマグネシウムアルミニウム、ジエチルトリヒド
ロマグネシウムアルミニウムなどがある。Examples of 2M"AIR,, Examples include pentaethyl beryllium aluminum, pentaethyl calcium aluminum, pentaethyl cadmium aluminum, ethyltetrachloromagnesium aluminum, and diethyltrihydromagnesium aluminum.
式Ｍ２（ＡｌＨ３−、、Ｈ−） ２の例としては、ビス
（テトラエチルアルミニウム）マグネシウム、ビス（フ
ェニルトリヒドロアルミニウム）マグネシウム、ビス（
テトラヒドロアルミニウム）マグネシウム、ビス（テト
ラエチルアルミニウム）亜鉛、ビス（テトラエチルアル
ミニウム）ベリリウム、ビス（フェニルトリヒドロアル
ミニウム）カルシウム、ビス（テトラエチルアルミニウ
ム〉カドミウムなどが挙げられる。Examples of formula M2(AlH3-,,H-)2 include bis(tetraethylaluminum)magnesium, bis(phenyltrihydroaluminum)magnesium, bis(
Examples include magnesium (tetrahydroaluminium), zinc bis(tetraethylaluminum), beryllium (bis(tetraethylaluminum)), calcium bis(phenyltrihydroaluminium), and cadmium (bis(tetraethylaluminum)).
式Ｍ’ＡｌＲ５−１，（ＮＲ２）−の例には、ジフェニ
ルアミノテトラエチルマグネシウムアルミニウム、ビス
（ジフェニルアミノ〉トリエチルマグネシウムアルミニ
ウム、ジエチルアミノトリエチルマグネシウムアルミニ
ウム、ジフェニルアミノテトラエチル亜鉛アルミニウム
、ビス（ジフェニルアミノ）トリエチルベリリウムアル
ミニウム、ジエチルアミノトリエチルカルシウムアルミ
ニウム、ジエチルアミノトリエチルカドミウムアルミニ
ウム等々がある。Examples of formula M'AlR5-1, (NR2)- include diphenylaminotetraethylmagnesiumaluminum, bis(diphenylamino>triethylmagnesiumaluminum, diethylaminotriethylmagnesiumaluminum, diphenylaminotetraethylzincaluminum, bis(diphenylamino)triethylberylliumaluminum , diethylaminotriethylcalcium aluminum, diethylaminotriethylcadmium aluminum, and the like.
式Ｌ１２ｎＲ３−Ｒ（ＮＲ２） ｎの例としては、ジフ
ェニルアミノジエチル亜鉛リチウム、ビス（ジフェニル
アミノ）ノルマルブチル亜鉛リチウムなどが挙げられ、
また式Ｌ１２ＺｎＲ４−ｎ（ＮＲ２）。の例には、ジノ
ルマルブチルジエチル亜鉛ジリチウム、ジフェニルアミ
ノジノルマルブチルエチル亜鉛ジリチウムなどが挙げら
れる。Examples of the formula L12nR3-R(NR2)n include diphenylaminodiethylzinclithium, bis(diphenylamino)n-butylzinclithium, etc.
and formula L12ZnR4-n(NR2). Examples include di-n-butyl diethyl zinc dilithium, diphenylamino di-n-butylethyl zinc dilithium, and the like.
次に、重合条件について述べると、重合圧力は大気圧よ
り高い圧力が好ましい。重合温度は室温でも構わないが
望ましくは５０℃以上、更に望ましくは１００℃以上で
ある。ＰＡＮあるいはＡＮ系共重合体は一般的に２００
℃よりやや低い温度にて分解着色することが知られてお
り、分解着色が起らない温度条件下に重合する。Next, regarding the polymerization conditions, the polymerization pressure is preferably higher than atmospheric pressure. The polymerization temperature may be room temperature, but is preferably 50°C or higher, more preferably 100°C or higher. PAN or AN copolymers are generally 200
It is known that decomposition and coloration occur at temperatures slightly lower than °C, and polymerization occurs under temperature conditions that do not cause decomposition and coloration.
重合溶媒としては前述の開始剤の重合能を阻害しないも
のであれば各種の有機溶媒を用いることができるが、芳
香族炭化水素基を分子内に含有する有機溶媒を使用する
と、立体規則性がより向上したＡＮ系共重合体が得られ
るので好ましい。本発明の重合機構は未だ十分には明ら
かではないものの、溶媒分子内の芳香族系のπ電子がＡ
Ｎ系共重合体の立体規則性懲戒に対して何等かの重要な
役割を果たしているものと考えられる。本発明の範囲を
限定するものではないが、これらの芳香族炭化水素基含
有有機溶媒としては、例えば、ベンゼン、トルエン、オ
ルトキシレン、メタキシレン、パラキシレン、ナフタレ
ン、ジフェニルエーテル、ビフェニールなどを挙げるこ
とができる。As the polymerization solvent, various organic solvents can be used as long as they do not inhibit the polymerization ability of the above-mentioned initiator, but if an organic solvent containing an aromatic hydrocarbon group in the molecule is used, the stereoregularity will be reduced. This is preferred because a more improved AN-based copolymer can be obtained. Although the polymerization mechanism of the present invention is not yet fully clear, the aromatic π electrons in the solvent molecules are
It is thought that it plays some important role in controlling the stereoregularity of the N-based copolymer. Although not limiting the scope of the present invention, examples of these aromatic hydrocarbon group-containing organic solvents include benzene, toluene, ortho-xylene, meta-xylene, para-xylene, naphthalene, diphenyl ether, and biphenyl. can.
本発明でいう、ＡＮのみからなる三連子のアイソタクテ
ィック・トリアッド分率は次のように測定される。即ち
、重水素化ジメチルスルフオキシド（以下、ｒＯＭｓＯ
Ｊと略記する〉中に溶解した溶液の１３Ｃ−ＮＭＩＩ（
質量数１３の炭素同位体を利用した核磁気共鳴測定装置
）によって観測される２７．９〜２９、 ｌｐｐｍの範
囲に現れる三本のメチン基（−ＣＨ＜）の炭素のピーク
強度から算定される。さらに具体的にはポリマー・ジャ
ーナル１７巻１２３３頁（１９８５）に記載されている
上山らの方法で帰属したトリアット・タフティシティ−
に基づくピーク同定によって求められる。即ち、１３Ｃ
−ＮＭＲの核磁気共鳴吸収ピーク・チャートにおいてこ
の全メチン・ピーク強度に対するｍｍのピーク強度の割
合がアイソタクティック・トリアッド分率である。In the present invention, the isotactic triad fraction of a triad consisting only of AN is measured as follows. That is, deuterated dimethyl sulfoxide (rOMsO
13C-NMII (abbreviated as J)
It is calculated from the peak intensity of the three methine groups (-CH<) carbons that appear in the range of 27.9 to 29 lppm observed by a nuclear magnetic resonance measurement device that uses a carbon isotope with a mass number of 13. . More specifically, the triatto tufticity assigned by the method of Ueyama et al. described in Polymer Journal Vol. 17, p. 1233 (1985)
It is determined by peak identification based on That is, 13C
- In the NMR nuclear magnetic resonance absorption peak chart, the ratio of the mm peak intensity to the total methine peak intensity is the isotactic triad fraction.
この測定に際して、装置として、例えば日本電気製フー
リエ交換ＮＭＲ（ＦＸ−２００）を使用し、溶媒として
重水素化ＤＭＳＯを用い、試料濃度を３〜２０重量％に
調整する。測定条件としては、温度８０℃、観測周波数
幅１０００Ｈｚ、データ・ポイン） １６ ｋ 、照射
時間６．５μ５（４５°パルス）、パルス遅延時間２．
５８１サンプリング時間８．１ｓ、積算回数６４Ｘ１０
〜６４ Ｘ１００に設定する。In this measurement, for example, a Fourier exchange NMR (FX-200) manufactured by NEC Corporation is used as an apparatus, deuterated DMSO is used as a solvent, and the sample concentration is adjusted to 3 to 20% by weight. The measurement conditions were: temperature 80°C, observation frequency width 1000Hz, data point) 16k, irradiation time 6.5μ5 (45° pulse), pulse delay time 2.
581 sampling time 8.1s, integration number 64X10
~64 Set to 100.
本発明のＡＮ系共重合体中のＡＮ含有率は、この共重合
体の立体規則性の効果を十分に発現するためには５０重
量％以上であることが必要である。The AN content in the AN-based copolymer of the present invention needs to be 50% by weight or more in order to fully exhibit the effect of stereoregularity of this copolymer.
この含有率が５０％より低下すると、ΔＮ部分の立体規
則性が如何に向上しても共重合体全体としての物性（例
えば、水共存下の融点など）は立体規則性のない場合の
共重合体並に低下する。If this content decreases below 50%, no matter how much the stereoregularity of the ΔN portion improves, the physical properties of the copolymer as a whole (for example, melting point in the presence of water) will be the same as that of a copolymer without stereoregularity. It decreases to the same level as merging.
本発明のＡＮ系共重合体の製造において、ＡＮと共重合
すべきコモノマーとしては、一般にはＡＮと共重合可能
なるエチレン系不飽和モノマーであればよいが、ＡＮ部
分の立体規則性の効果をより大きく発現させるためには
コモノマー分子内にハロゲン原子を含有しないものが望
ましい。コモノマーとしては、例えばメタクリロニトリ
ル（以下、ｒＭＡＮ Ｊと略記する）、クロトンニトリ
ル、アリルニトリルなどのニトリル基含有モノエチレン
系不飽和モノマーや、アクリル酸メチル（以下、ｒＭＡ
Ｊと略記する）、メタクリル酸メチルなどのアクリ、ル
酸系モノエチレン系不飽和モノマーエチレン、アセチレ
ン、プロピレン、ブタジェン、スチレンなどの炭化水素
系エチレン系不飽和モノマー、酢酸ビニル、イソ酪酸ビ
ニルなどのビニルエステル類等が挙げられる。In the production of the AN-based copolymer of the present invention, the comonomer to be copolymerized with AN may generally be an ethylenically unsaturated monomer that is copolymerizable with AN. In order to achieve greater expression, it is desirable that the comonomer molecule does not contain a halogen atom. Examples of comonomers include nitrile group-containing monoethylenically unsaturated monomers such as methacrylonitrile (hereinafter abbreviated as rMAN J), crotonitrile, and allylnitrile, and methyl acrylate (hereinafter rMAN J).
(abbreviated as J), acrylic acid-based monoethylenically unsaturated monomers such as methyl methacrylate, hydrocarbon-based ethylenically unsaturated monomers such as ethylene, acetylene, propylene, butadiene, and styrene, vinyl acetate, vinyl isobutyrate, etc. Examples include vinyl esters.
本発明のＡＮ系共重合体は１０．０００以上、好ましく
は１０．０００〜約５００．０００の粘度平均分子量を
有する。分子量が１０．０００未満であると、繊維や膜
などへの成形が困難であるか、または成形できても実用
上十分な強度をもつものが得られない。The AN-based copolymer of the present invention has a viscosity average molecular weight of 10.000 or more, preferably 10.000 to about 500.000. If the molecular weight is less than 10,000, it will be difficult to mold into fibers or membranes, or even if it can be molded, it will not have sufficient strength for practical use.
粘度平均分子量は、２５℃ジメチルスルフオキシドに測
定すべき共重合体を溶解し、常法により固有粘度〔η〕
を求めた後、次に示す立体規則性の高いホモポリアクリ
ロニトリルの粘度式を近似的に用いて算出する。The viscosity average molecular weight is determined by dissolving the copolymer to be measured in dimethyl sulfoxide at 25°C and measuring the intrinsic viscosity [η] using a conventional method.
After determining, the following viscosity formula for homopolyacrylonitrile with high stereoregularity is used to approximately calculate the viscosity.
Ｃη）＝ ０．２０４ｘＭ’−”
本発明のＡＮ系共重合体の顕著な特性は水共存下の高い
融点などにみられるが、この融点の測定は示差走査熱量
計（以下、ＤＳＣと略記する）を用いて行われる。標準
的には乾燥試料約３ｍｇおよびそれと同重量の純水とを
試料として用い、これを例えばセイコー電子社製５ＳＣ
５０００熱分析システムＤＳＣ−２００により、昇温速
度５℃／分で加熱して測定する。その際の融点は第１図
のように吸熱ピークとして現われ、この吸熱ピークの発
現する温度を水共存下の融点と定義する。ＤＳＣによる
測定法の詳細は、例えば、繊維学会編「繊維・高分子測
定法の技術」 （朝食書店、１９８５）の２２９ページ
に記載されている。Cη) = 0.204xM'-" The remarkable characteristics of the AN-based copolymer of the present invention are seen in its high melting point in the coexistence of water, but this melting point can be measured using a differential scanning calorimeter (hereinafter abbreviated as DSC). ).Standardally, approximately 3 mg of a dry sample and the same weight of pure water are used as samples, and this is carried out using, for example, a 5SC manufactured by Seiko Electronics Co., Ltd.
Measurement is performed using a 5000 thermal analysis system DSC-200 while heating at a temperature increase rate of 5° C./min. The melting point at that time appears as an endothermic peak as shown in FIG. 1, and the temperature at which this endothermic peak appears is defined as the melting point in the presence of water. Details of the DSC measurement method are described, for example, on page 229 of ``Techniques for Fiber/Polymer Measurement Methods'' (edited by the Japan Institute of Textile Science and Technology) (Shokusho Shoten, 1985).
本発明の、ＡＮのみからなる三連子のアイソタクティッ
ク・トリアッド分率が０．３５以上のＡＮ系共重合体は
、水存在下での融点が上昇するなど結晶性が高い。この
共重合体から得られる繊維は機械的強度および湿潤状態
での耐熱性に優れ、例えば、一般の衣料分野はもちろん
、高級衣料分野、産業資材分野、宇宙工学分野などにお
いて有用である。The AN-based copolymer of the present invention having an isotactic triad fraction of 0.35 or more in the triad consisting only of AN has high crystallinity, such as an increased melting point in the presence of water. Fibers obtained from this copolymer have excellent mechanical strength and heat resistance in a wet state, and are useful, for example, in the field of general clothing, high-end clothing, industrial materials, space engineering, and the like.
さらに、本発明の共重合体は、金属イオンを選択的に配
位する性質を有しているので、金属の選択的吸着素材と
して有用であり、また金属を配位した重合体は、導電性
ポリマーとしても効果が期待される。Furthermore, since the copolymer of the present invention has the property of selectively coordinating metal ions, it is useful as a material for selectively adsorbing metals, and the copolymer coordinating metals has the property of selectively coordinating metal ions. It is also expected to be effective as a polymer.
以下、実施例に従って、本発明をさらに詳細に説明する
が、本発明はこれらの例によって対等限定されるもので
はない。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１
蒸発成分を凝縮しそれを還流できるように組まれた第２
図のような装置において、まず３００ｃｃの三つロフラ
スコ５を窒素置換し、これにキシレン（三種の異性体混
合物）を５０ｃｃ入れて温度を１２０℃に調節した。重
合開始剤としてジノルマルヘキシルマグネシウムの１．
０モル濃度へブタン溶液１、０ ｃｃを添加してｌ０分
間放置した。次に、へＮＯ３５ｃｃおよびＭＡＮを９．
５ ｃｃ滴下して３０分重合させた。Example 1 A second system designed to condense the evaporated components and reflux them
In the apparatus shown in the figure, first, a 300 cc three-necked flask 5 was purged with nitrogen, 50 cc of xylene (a mixture of three isomers) was added thereto, and the temperature was adjusted to 120°C. 1. di-n-hexylmagnesium as a polymerization initiator.
1.0 cc of butane solution was added to 0 molar concentration and left for 10 minutes. Next, add 35cc of NO and MAN to 9.
5 cc was added dropwise and polymerized for 30 minutes.
これに、適当量の塩酸メタノール混合溶液を加えて重合
反応を終了させ、以下、濾過と水洗を繰り返して後、乾
燥標量した結果収量は０．８ｇであった。To this, an appropriate amount of a mixed solution of hydrochloric acid and methanol was added to terminate the polymerization reaction, and after repeated filtration and washing with water, the yield was 0.8 g as a result of dry weighing.
共重合体の粘度平均分子量は１０５．０００であった。The viscosity average molecular weight of the copolymer was 105.000.
この共重合体を重水素化ＤＭＳＯに５重量％溶解して、
”Ｃ−ＮＭＲ測定を行ったところ、ＡＮのみからなる三
連子のアイソタクティック・トリアッド分率は０．５２
であった。また共重合体中のモノマーユニット含有率は
、やはり”Ｃ−ＮＭＲのシアノ基のビ−ク面積比から算
出するとＡＮが５５％、ＭＡＮが４５％であった。This copolymer was dissolved in 5% by weight in deuterated DMSO,
``C-NMR measurements showed that the isotactic triad fraction of the triad consisting only of AN was 0.52.
Met. Furthermore, the monomer unit content in the copolymer was 55% for AN and 45% for MAN, as calculated from the peak area ratio of cyano groups in C-NMR.
これをセイコー電子社ｇｉＳＳＣ５０００熱分析システ
ムＤＳＣ−２００を用いて、本文中に記述した方法によ
って測定したこの試料の水共存下の融点は１７１℃であ
った。The melting point of this sample in the presence of water was 171° C. when measured using Seiko Electronics' giSSC5000 thermal analysis system DSC-200 according to the method described in the text.
比較例１ 実施例■と同様の図２のような装置を用いた。Comparative example 1 An apparatus as shown in FIG. 2 similar to that in Example (2) was used.
キシレン３００ｃｃに開始剤のアゾビスイソブチロニト
リル０．１ｇを溶解して供給し温度を５０℃に調製した
後、ＡＮ５．ＯｃｃおよびＭＡＮ ５．Ｑｃｃを滴下し
て２時間の重合を行った。After dissolving 0.1 g of initiator azobisisobutyronitrile in 300 cc of xylene and adjusting the temperature to 50°C, AN5. Occ and MAN 5. Qcc was added dropwise to carry out polymerization for 2 hours.
ここで得られた共重合体を濾過と水洗とを繰り返して後
、乾燥様量した結果収量は３．４ｇであった。The copolymer obtained here was repeatedly filtered and washed with water, and then dried and weighed, and the yield was 3.4 g.
共重合体の粘度平均分子量は８６．０００であった。The viscosity average molecular weight of the copolymer was 86.000.
この共重合体を実施例１と同様に１３Ｃ−ＮＭＲ測定を
行ったところ、ＡＮのみからなる二連子のアイソタクテ
ィック・トリアッド分率は０．２６であった。When this copolymer was subjected to 13C-NMR measurement in the same manner as in Example 1, the isotactic triad fraction of the diad consisting only of AN was 0.26.
また共重合体中のモノマーユニット含有率は、ＡＮが５
７％、ＭＡＮが４３％であった。Furthermore, the monomer unit content in the copolymer is AN=5.
7% and MAN was 43%.
ＤＳＣを用いて測定したこの試料の水共存下の融点は１
６８℃であった。The melting point of this sample in the presence of water measured using DSC is 1
The temperature was 68°C.
実施例２
実施例１と同様の装置で、仕込モノマーをＡＮ２、０
ｃｃ、 ＭＡ ８． Ｏｃｃとした以外は実施例１とま
ったく同様の操作によって重合を行った。これに、適当
量の塩酸メタノール混合溶液を加えて重合反応を終了さ
せ、以下濾過と水洗を繰り返して後、乾燥様量した結果
収量は１．４ｇであった。Example 2 Using the same equipment as in Example 1, the charged monomer was AN2,0.
cc, MA 8. Polymerization was carried out in exactly the same manner as in Example 1 except that Occ was used. To this, an appropriate amount of a mixed solution of hydrochloric acid and methanol was added to terminate the polymerization reaction, and after repeated filtration and washing with water, the resulting product was dried and weighed, and the yield was 1.4 g.
共重合体の粘度平均分子量は７９．０００であった。The viscosity average molecular weight of the copolymer was 79.000.
この共重合体を重水素化ＤＭＳＯに５重量％溶解して、
” Ｃ−ＮＭＲ測定を行ったところ、ＡＮのみからなる
二連子のアイソタクティック・トリアッド分率は０．５
２であった。また共重合体中のモノマーユニット含有率
は、ＡＮが８５％、ＭＡが１５％であった。This copolymer was dissolved in 5% by weight in deuterated DMSO,
” When C-NMR measurements were performed, the isotactic triad fraction of the diad consisting only of AN was 0.5.
It was 2. Furthermore, the monomer unit content in the copolymer was 85% for AN and 15% for MA.
この試料の水共存下の融点は１５９℃であった。The melting point of this sample in the presence of water was 159°C.
比較例２
仕込モノマーをＡＮ ７．０ｃｃ、 ＭＡ ３、Ｑｃｃ
とした以外は比較例１とまったく同様の操作によって重
合を行った。収量は３．５ｇであった。Comparative Example 2 Charged monomers were AN 7.0cc, MA 3, Qcc
Polymerization was carried out in exactly the same manner as in Comparative Example 1 except for the following. Yield was 3.5g.
共重合体の粘度平均分子量は６７、０００であり、ＡＮ
のみからなる二連子のアイソタクティック・トリアッド
分率は０゜２７、共重合体中のモノマーユニット含有率
は、ＡＮが８２％、ＭＡが１８％であった。The viscosity average molecular weight of the copolymer is 67,000, and AN
The isotactic triad fraction of the diad consisting of only 0°27 was 0°27, and the monomer unit content in the copolymer was 82% for AN and 18% for MA.
この試料の水共存下の融点は１５３℃であった。The melting point of this sample in the presence of water was 153°C.
比較例３
仕込モノマーをＡＮ ３． ＯｃｃＳＭＡ ７． Ｏｃ
ｃとした以外は比較例１とまったく同様の操作によって
重合を行った。収量は３，１ｇであった。Comparative Example 3 Charged monomer was AN 3. OccSMA7. Oc
Polymerization was carried out in exactly the same manner as in Comparative Example 1, except that the procedure was as follows. Yield was 3.1 g.
共重合体の粘度平均分子量は１０８．０００であり、Ａ
Ｎのみからなる二連子のアイソタクティック・トリアッ
ド分率は０．２６であり、共重合体中のモノマーユニッ
ト含有率は、ＡＮが４２％、ＭＡが５８％であった。The viscosity average molecular weight of the copolymer is 108.000, and A
The isotactic triad fraction of the diad consisting only of N was 0.26, and the monomer unit content in the copolymer was 42% for AN and 58% for MA.
また、この試料の水共存下の融点は１５０℃であった。Further, the melting point of this sample in the presence of water was 150°C.
実施例３〜１１
重合開始剤を変化させ、その他の操作は実施例１とまっ
たく同様にして行った結果を表１に示す。Examples 3 to 11 Table 1 shows the results obtained by changing the polymerization initiator and performing the other operations in exactly the same manner as in Example 1.
実施例１２および１３
有機金属化合物としてジノルマルヘキシルマグネシウム
を固定してこれを実施例１と同量用い、これに対して等
モルの遷移金属化合物を使用して重合を行った結果を表
２に示す。Examples 12 and 13 Table 2 shows the results of polymerization using di-normal hexylmagnesium fixed as an organometallic compound and using the same amount as in Example 1, and using an equimolar amount of a transition metal compound. show.
ｌａ”Ｆ余日
５６一
実施例１４
重合溶媒をキシレンのかわりにノルマルトリデカンを用
いた以外はすべて実施例工に準じて行った結果、共重合
体の収量は０．７ｇ、粘度平均分子量は７３．０００で
あり、ＡＮのみからなる二連子のアイソタクティック・
トリアッド分率は０．４３であり、共重合体中のモノマ
ーユニット含有率は、ＡＮが５８％、ＭＡＮが４２％で
あった。la"F Atoday 56-Example 14 The procedure was carried out in accordance with the example except that n-tridecane was used instead of xylene as the polymerization solvent. The yield of the copolymer was 0.7 g, and the viscosity average molecular weight was 73.000, and the isotactic doublet consisting only of AN.
The triad fraction was 0.43, and the monomer unit content in the copolymer was 58% for AN and 42% for MAN.
また、この試料の水共存下の融点は１６９℃であった。Further, the melting point of this sample in the presence of water was 169°C.
実施例１５
重合溶媒をキシレンのかわりにノルマルトリデカンを用
いた以外はすべて実施例２に準じて行った結果、共重合
体の収量は０．７ｇ、粘度平均分子量は１６９．０００
であり、ＡＮのみからなる二連子のアイソタクティック
・トリアッド分率は０．４４であり、共重合体中のモノ
マーユニット含有率は、ＡＮが８３％、ＭＡが１７％で
あった。Example 15 Everything was carried out according to Example 2 except that n-tridecane was used instead of xylene as the polymerization solvent. As a result, the yield of the copolymer was 0.7 g, and the viscosity average molecular weight was 169.000.
The isotactic triad fraction of the dyad consisting only of AN was 0.44, and the monomer unit content in the copolymer was 83% for AN and 17% for MA.
また、この試料の水共存下の融点は１５７℃であった。Further, the melting point of this sample in the presence of water was 157°C.
実施例１６
重合圧力を４気圧とし、重合温度を１５０℃とした以外
はすべて実施例２に準じて行った結果、共重合体の収量
は１．６ｇ、粘度平均分子量は１４７．０００であり、
ＡＮのみからなる二連子のアイソタクティック・トリア
ッド分率は０．５５であり、共重合体中のモノマーユニ
ット含有率は、ＡＮが５６％、ＭＡが４４％であった。Example 16 Everything was carried out according to Example 2 except that the polymerization pressure was 4 atm and the polymerization temperature was 150°C. As a result, the yield of the copolymer was 1.6 g, the viscosity average molecular weight was 147.000,
The isotactic triad fraction of the diad consisting only of AN was 0.55, and the monomer unit content in the copolymer was 56% for AN and 44% for MA.
さらに、この試料の水共存下の融点は１５５℃であった
。Furthermore, the melting point of this sample in the presence of water was 155°C.
実施例１７
重合温度を５５℃とした以外はすべて実施例２に従って
重合を行った結果、共重合体の収量は０．８ｇ１粘度平
均分子量は９５．０００であり、ＡＮのみからなる二連
子のアイソタクティック・トリアッド分率は０．５７で
あり、共重合体中のモノマーユニット含有率は、ＡＮが
５７％、ＭＡが４３％であった。Example 17 The polymerization was carried out in accordance with Example 2 except that the polymerization temperature was 55°C. The yield of the copolymer was 0.8 g and the viscosity average molecular weight was 95.000. The isotactic triad fraction was 0.57, and the monomer unit content in the copolymer was 57% for AN and 43% for MA.
さらに、この試料の水共存下の融点は１５５℃であった
。Furthermore, the melting point of this sample in the presence of water was 155°C.
実施例１８
重合温度を３８℃とした以外はすべて実施例２に従って
重合を行った結果、共重合体の収量は０．５ｇ、粘度平
均分子量は７０．０００であり、ＡＮのみからなる二連
子のアイソタクティック・トリアッド分率は０．３９で
あり、共重合体中の七ノマーユニット含有率は、ＡＮが
５６％、ＭＡが４４％であった。Example 18 The polymerization was carried out in accordance with Example 2 except that the polymerization temperature was 38°C. The yield of the copolymer was 0.5 g, the viscosity average molecular weight was 70.000, and the copolymer was a bistrand consisting only of AN. The isotactic triad fraction of was 0.39, and the content of heptanomer units in the copolymer was 56% for AN and 44% for MA.
さらに、この試料の水共存下の融点は１５３℃であった
。Furthermore, the melting point of this sample in the presence of water was 153°C.
第１図は、水共存下の融点の測定に用いる示差走査熱量
計・吸発熱曲線を示し、横軸は対象とする系の温度、縦
軸は上方が発熱、下方が吸熱を示す。
第２図は重合装置の概要を示す図である。
１・・・磁気回転器、 ２・・・断熱材、３・・・磁
気回転子、 ４・・・温度調節可能な油浴、５・・・
三つロフラスコ、
６・・・滴下ロート、 ７・・・冷却管、８・・・窒
素供給用ゴムホース、
９・・・排気用ゴムホース、
ＩＯ・・・流動パラフィン浴。FIG. 1 shows a differential scanning calorimeter/endotherm/endotherm curve used to measure the melting point in the presence of water, where the horizontal axis shows the temperature of the target system, and the vertical axis shows heat generation at the top and endotherm at the bottom. FIG. 2 is a diagram showing an outline of the polymerization apparatus. 1...Magnetic rotator, 2...Insulating material, 3...Magnetic rotor, 4...Temperature adjustable oil bath, 5...
Three-bottle flask, 6...Dripping funnel, 7...Cooling pipe, 8...Rubber hose for nitrogen supply, 9...Rubber hose for exhaust, IO...Liquid paraffin bath.
Claims (7)
合体において、アクリロニトリル・モノマーユニットの
みからなる三連子のアイソタクティック・トリアッド分
率が０．３５以上であって、粘度平均分子量が１０，０
００以上であるアクリロニトリル系共重合体。(1) In a copolymer containing 50% by weight or more of acrylonitrile, the isotactic triad fraction of the triad consisting only of acrylonitrile monomer units is 0.35 or more, and the viscosity average molecular weight is 10.0
An acrylonitrile copolymer having a molecular weight of 00 or more.
体を得るに際し、アルカリ土類金属を含有する有機金属
化合物を単独で用いるかまたはこれと遷移金属化合物と
の組合せ、または、周期律表第 I 、IIおよびIII族の金
属を二種以上含む有機金属化合物を開始剤系として用い
重合することを特徴とする請求項１記載のアクリロニト
リル系共重合体の製法。(2) When obtaining an acrylonitrile copolymer by polymerizing in an organic solvent, an organometallic compound containing an alkaline earth metal is used alone or in combination with a transition metal compound, or 2. The method for producing an acrylonitrile copolymer according to claim 1, characterized in that the polymerization is carried out using an organometallic compound containing two or more metals of groups I, II and III as an initiator system.
て、Ｒ＿２Ｍｇ、ＲＭｇＸ、Ｒ＿２ＮＭｇＲ、Ｒ＿２Ｎ
ＭｇＮＲ＿２、（Ｒ＿３Ｓｉ）＿２ＮＭｇＲ、（Ｒ＿３
Ｓｉ）＿２ＮＭｇＮ（ＳｉＲ＿３）＿２、Ｒ＿３ＳｉＭ
ｇＲ、Ｒ＿３ＳｉＭｇＳｉＲ＿３、ＲＯＭｇＲ、ＲＯＭ
ｇＯＲ、ＲＳＭｇＲおよびＲＳＭｇＳＲで表されるマグ
ネシウム化合物；式Ｒ＿２ＢｅおよびＲＢｅＸで表され
るベリリウム化合物；ならびに式Ｒ＿２ＣａおよびＲＣ
ａＸで表されるカルシウム化合物の中から選ばれた少な
くとも一種を用いる請求項２記載のアクリロニトリル系
共重合体の製法。 ここで、式中のＲはたがいに同一でも異なっていてもよ
く、それぞれ脂肪族または芳香族炭化水素もしくはそれ
らの組合せによってなる炭化水素であり、また式Ｒ＿２
ＮＭｇＲおよびＲ＿２ＮＭｇＮＲ＿２で表される化合物
においてはＲ＿２として表される二個のＲはたがいに結
合しそれらが結合している窒素原子とともに複素環を形
成していてもよい。(3) As organometallic compounds containing alkaline earth metals, R_2Mg, RMgX, R_2NMgR, R_2N
MgNR_2, (R_3Si)_2NMgR, (R_3
Si)_2NMgN(SiR_3)_2, R_3SiM
gR, R_3SiMgSiR_3, ROMgR, ROM
Magnesium compounds represented by gOR, RSMgR and RSMgSR; beryllium compounds represented by formulas R_2Be and RBeX; and formulas R_2Ca and RC
3. The method for producing an acrylonitrile copolymer according to claim 2, wherein at least one selected from calcium compounds represented by aX is used. Here, R in the formula may be the same or different and each is a hydrocarbon consisting of an aliphatic or aromatic hydrocarbon or a combination thereof, and the formula R_2
In the compounds represented by NMgR and R_2NMgNR_2, the two Rs represented as R_2 may be bonded to each other to form a heterocycle with the nitrogen atom to which they are bonded.
体を得るに際し、式Ｍ＾１Ｍ＾２Ｒ＿３＿−＿ｎＨ＿ｎ
、Ｍ＾１ＡｌＲ＿４＿−＿ｎＨ＿ｎ、Ｍ＾２ＡｌＲ＿５
＿−＿ｎＸ＿ｎ、Ｍ＾２（ＡｌＲ＿４＿−＿ｎＨ＿ｎ）
＿２、Ｍ＾２ＡｌＲ＿５＿−＿ｎ（ＮＲ＿２）＿ｎ、Ｌ
ｉＺｎＲ＿３＿−＿ｎ（ＮＲ＿２）＿ｎ、およびＬｉ＿
２ＺｎＲ＿４＿−＿ｎ（ＮＲ＿２）＿ｎで表される有機
金属化合物の中から選ばれた少なくとも一種を用いる請
求項２記載のアクリロニトリル系共重合体の製法。 ここで、式中のＲはたがいに同一でも異なっていてもよ
く、それぞれ脂肪族または芳香族炭化水素もしくはそれ
らの組合せによってなる炭化水素である。また、Ｍ＾１
はリチウム、ナトリウム、カリウムのうちから選ばれた
一種の金属、Ｍ＾２はマグネシウム、ベリリウム、カル
シウム、亜鉛、カドミウムのうちから選ばれた一種の金
属、Ｘは弗素、塩素、臭素、沃素のうちから選ばれた一
種の元素であり、更に、ｎは零または正の整数で同一分
子内における５−ｎ、４−ｎあるいは３−ｎの添え字が
負にならない範囲の値をとるものとする。(4) When obtaining an acrylonitrile copolymer by polymerization in an organic solvent, the formula M^1M^2R_3_-_nH_n
, M^1AlR_4_-_nH_n, M^2AlR_5
＿−＿nX_n, M^2(AlR_4_−_nH_n)
_2, M^2AlR_5_-_n(NR_2)_n, L
iZnR_3_-_n(NR_2)_n, and Li_
3. The method for producing an acrylonitrile copolymer according to claim 2, wherein at least one selected from organometallic compounds represented by 2ZnR_4_-_n(NR_2)_n is used. Here, R in the formula may be the same or different, and each represents a hydrocarbon consisting of an aliphatic or aromatic hydrocarbon or a combination thereof. Also, M^1
is a metal selected from lithium, sodium, and potassium, M^2 is a metal selected from magnesium, beryllium, calcium, zinc, and cadmium, and X is a metal selected from fluorine, chlorine, bromine, and iodine. A type of element selected from .
する有機化合物を用いる請求項２記載のアクリロニトリ
ル系共重合体の製法。(5) The method for producing an acrylonitrile copolymer according to claim 2, wherein an organic compound having an aromatic hydrocarbon group in the molecule is used as the organic solvent.
アクリロニトリル系共重合体の製法。(6) The method for producing an acrylonitrile copolymer according to claim 2, wherein the polymerization is carried out under pressure higher than atmospheric pressure.
クリロニトリル系共重合体の製法。(7) The method for producing an acrylonitrile copolymer according to claim 2, wherein the polymerization is carried out at a temperature higher than 50°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20386589A JPH0368608A (en) | 1989-08-08 | 1989-08-08 | Acrylonitrile compolymer and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20386589A JPH0368608A (en) | 1989-08-08 | 1989-08-08 | Acrylonitrile compolymer and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0368608A true JPH0368608A (en) | 1991-03-25 |
Family
ID=16480985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20386589A Pending JPH0368608A (en) | 1989-08-08 | 1989-08-08 | Acrylonitrile compolymer and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0368608A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004065434A1 (en) * | 2003-01-23 | 2004-08-05 | Teijin Limited | Polymer for carbon fiber precursor |
| US6826508B2 (en) | 2002-10-31 | 2004-11-30 | Kabushiki Kaisha Piyo | Tire pressure gauge |
| JP2007197554A (en) * | 2006-01-26 | 2007-08-09 | Teijin Ltd | Stereoregular polyacrylonitrile-based resin composition and method for producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4842230A (en) * | 1971-10-04 | 1973-06-20 | ||
| JPS6479206A (en) * | 1987-09-22 | 1989-03-24 | Asahi Chemical Ind | Preparation of acrylonitrile polymer |
| JPH02115252A (en) * | 1988-09-15 | 1990-04-27 | Arco Chem Technol Inc | Blow moldable styrene.maleic anhydride/ polybutylene terephthalate composition |
-
1989
- 1989-08-08 JP JP20386589A patent/JPH0368608A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4842230A (en) * | 1971-10-04 | 1973-06-20 | ||
| JPS6479206A (en) * | 1987-09-22 | 1989-03-24 | Asahi Chemical Ind | Preparation of acrylonitrile polymer |
| JPH02115252A (en) * | 1988-09-15 | 1990-04-27 | Arco Chem Technol Inc | Blow moldable styrene.maleic anhydride/ polybutylene terephthalate composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6826508B2 (en) | 2002-10-31 | 2004-11-30 | Kabushiki Kaisha Piyo | Tire pressure gauge |
| WO2004065434A1 (en) * | 2003-01-23 | 2004-08-05 | Teijin Limited | Polymer for carbon fiber precursor |
| US7338997B2 (en) | 2003-01-23 | 2008-03-04 | Teijin Limited | Polymer for carbon fiber precursor |
| JP2007197554A (en) * | 2006-01-26 | 2007-08-09 | Teijin Ltd | Stereoregular polyacrylonitrile-based resin composition and method for producing the same |
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