JPS6341537A - Production of phosphazene polymer - Google Patents
Production of phosphazene polymerInfo
- Publication number
- JPS6341537A JPS6341537A JP61186164A JP18616486A JPS6341537A JP S6341537 A JPS6341537 A JP S6341537A JP 61186164 A JP61186164 A JP 61186164A JP 18616486 A JP18616486 A JP 18616486A JP S6341537 A JPS6341537 A JP S6341537A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- elements
- polymerization
- sulfuric acid
- 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 61
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 62
- -1 cyclic phosphazene compound Chemical class 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 150000001768 cations Chemical class 0.000 claims abstract description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 6
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 7
- 150000001255 actinides Chemical group 0.000 claims description 6
- 150000002602 lanthanoids Chemical group 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052776 Thorium Inorganic materials 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 2
- 125000004122 cyclic group Chemical group 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 88
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract description 4
- 229910017920 NH3OH Inorganic materials 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 29
- 238000000034 method Methods 0.000 description 22
- 239000000499 gel Substances 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000011521 glass Substances 0.000 description 18
- 239000000956 alloy Substances 0.000 description 17
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000002023 wood Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 13
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 13
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 13
- 125000000552 p-cresyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1O*)C([H])([H])[H] 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 4
- 229940008406 diethyl sulfate Drugs 0.000 description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 3
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 3
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 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
- PEJQKHLWXHKKGS-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octachloro-1,3,5,7-tetraza-2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraphosphacycloocta-1,3,5,7-tetraene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 PEJQKHLWXHKKGS-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical compound C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect 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
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XJEVHMGJSYVQBQ-SECBINFHSA-N (1r)-2,3-dihydro-1h-inden-1-amine Chemical compound C1=CC=C2[C@H](N)CCC2=C1 XJEVHMGJSYVQBQ-SECBINFHSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KEIFWROAQVVDBN-UHFFFAOYSA-N 1,2-dihydronaphthalene Chemical compound C1=CC=C2C=CCCC2=C1 KEIFWROAQVVDBN-UHFFFAOYSA-N 0.000 description 1
- WELKBINNNXKQQS-UHFFFAOYSA-N 1,4-benzoquinone imine Chemical compound N=C1C=CC(=O)C=C1 WELKBINNNXKQQS-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 1
- QMEQBOSUJUOXMX-UHFFFAOYSA-N 2h-oxadiazine Chemical compound N1OC=CC=N1 QMEQBOSUJUOXMX-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical class [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Chemical group 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000003974 aralkylamines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000004428 fluoroalkoxy group Chemical group 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 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
- 239000010720 hydraulic oil Substances 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- OZIRORHUKSXTLG-UHFFFAOYSA-N naphtho[1,2-h]quinoline Chemical compound C1=CC2=CC=CN=C2C2=C1C1=CC=CC=C1C=C2 OZIRORHUKSXTLG-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はホスファゼン重合体の製造方法に関するもので
ある。更に詳しくはへキサクロロシクロトリホスファゼ
ンおよび/またはオクタクロロシクロテトラホスファゼ
ンを重合する際、原子団SO4を含む化合物を触媒とし
て用いる新規な触媒重合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 phosphazene polymer. More specifically, the present invention relates to a novel catalytic polymerization method in which a compound containing an atomic group SO4 is used as a catalyst when polymerizing hexachlorocyclotriphosphazene and/or octachlorocyclotetraphosphazene.
(従来の技#)
ポリホスファゼンに関する研究は古り、1897年IL
N−5tokesはヘキサクロロシクロトリホスファ
ゼン(以下3 PNCと略記する)を強熱することによ
りホスファゼン重合体を得たがCAtner、Chem
−J、 19.782(1897) ]、それは有機溶
媒に不溶なゴム状物で極めて加水分解され易い性質を有
しているため、そのまま最近まで見過ごされてきた。(Conventional Technique #) Research on polyphosphazenes is old; IL
N-5tokes obtained a phosphazene polymer by igniting hexachlorocyclotriphosphazene (hereinafter abbreviated as 3PNC), but CAtner and Chem.
-J, 19.782 (1897)], it is a rubbery substance that is insoluble in organic solvents and has the property of being extremely easily hydrolyzed, so it has been overlooked until recently.
1960年代になって)1. R−AI Icock等
により3PNCを無触媒、真空封管中で注意深く加熱す
ることにより有機溶媒に可溶なホスファゼン重合体が得
られることが見出され(米国特許第3,370,020
号)、更に該重合体の分子骨格を形成するリン原子と結
合している塩素原子を適当な置換基(例えば、フルオロ
アルコキシ基、パーフルオロアルコキシ基、アリルオキ
シ基、アリールオキシ基、アルコキシ基およびアミノ基
等)で置換することにより、水、酸、塩基等に対して極
めて安定な重合体が得られる様になった。In the 1960s) 1. It was discovered by R-AI Icock et al. that a phosphazene polymer soluble in organic solvents could be obtained by carefully heating 3PNC without a catalyst in a vacuum sealed tube (U.S. Pat. No. 3,370,020).
), and further substituents (for example, fluoroalkoxy groups, perfluoroalkoxy groups, allyloxy groups, aryloxy groups, alkoxy groups, and amino It has become possible to obtain polymers that are extremely stable against water, acids, bases, etc.
これらのホスファゼン重合体は、耐熱性、耐炎性、耐油
性等に優れた性質を有し、また燃焼ガスおよび熱分解ガ
スの毒性が少ないことがら、居住にかかわる発泡ゴム材
料やグラスチック用難燃剤として優れていると云われて
いる。また−80〜−90℃の低温に於ても可撓性を保
持するゴムにもなり得ると共に、耐油性、針作動油性等
の優れた性質を有するため、0−リング、ガスケット、
燃料ホース等として工業分野への利用研究が行なわれて
いる。These phosphazene polymers have excellent properties such as heat resistance, flame resistance, and oil resistance, and are low in toxicity from combustion gas and pyrolysis gas, so they are used as flame retardants for foam rubber materials and glass materials used in housing. It is said to be excellent. It can also be used as a rubber that maintains flexibility even at low temperatures of -80 to -90°C, and has excellent properties such as oil resistance and needle hydraulic oil resistance, so it can be used for O-rings, gaskets, etc.
Research is being conducted on its use in the industrial field as fuel hoses, etc.
最近は、このホスファゼン重合体は生体組織との相互作
用が極めて小さいことや、その代鮒物が無害であること
から縫合糸、血管代用物、人工臓器、医薬品担持体等と
して生体、医学分野への利用研究も活発に行なわれてい
る。Recently, this phosphazene polymer has been used in the biological and medical fields as sutures, blood vessel substitutes, artificial organs, pharmaceutical carriers, etc. because its interaction with living tissue is extremely small and its substitute is harmless. Research on the use of is also actively being conducted.
これらホスファゼン重合体の有用性が次第に高まりつつ
あるにも拘らず、出発物質である3PNCの重合体を旨
く製造する方法に問題が残されている。Despite the increasing utility of these phosphazene polymers, problems remain in how to successfully prepare the starting 3PNC polymers.
金時間とを必要とし、しかも、重合率を上げるとしばし
ば溶媒に不溶性のゲル化物の生成を伴ない、それが、上
記の様な有用な重合体生成物の製造を困難にしてきた。In addition, increasing the polymerization rate is often accompanied by the formation of gels that are insoluble in solvents, which has made it difficult to produce useful polymer products such as those described above.
また、重合体の分子量の制御も、これら初期の熱重合方
法を用いたのでは極めて困難であった。Furthermore, it was extremely difficult to control the molecular weight of the polymer using these early thermal polymerization methods.
これらの初期の方法の欠点を克服または最小限にするた
め触媒を用いた重合の研究が多くなされてきた。例えば
、三弗化硼素、アルキルアルミニウムおよびアルキルア
ルミニウムハライドの様なアルミニウム又は硼素のルイ
ス酸触媒を使用する方法(%開昭52−44900 )
、無機塩特にCrCA!2、N1(J2、MgCJ2等
の様な金属ハライドを触媒とする方法(%開昭53−1
29300)、式M(OR)xの金属アルコキシドを触
媒とする方法(特開昭53−47396 )、チーグラ
ー型触媒例えばTi、 Zr、 )If、 V等の化合
物と共触媒として硼素又はアルミニウム化合物を組合せ
た触媒糸を使用する方法(%開昭55−16076)、
トリフェニルアンチモン(特開昭55−120629
)またはトリフェニルアンチモンとハロゲンを組合せた
糸(特開昭55−123623 )を触媒とする方法、
イオウまたはチオカルバメート化合物を触媒とする方法
(特開昭54−152693、同58−1646璽9)
、ルイス酸と中性塩を組合せた糸を触媒と−する方法(
%開昭55−123624 )等がある。Much work has been done on catalytic polymerization to overcome or minimize the shortcomings of these earlier methods. For example, a method using aluminum or boron Lewis acid catalysts such as boron trifluoride, alkyl aluminum and alkyl aluminum halides (% open 52-44900)
, inorganic salts especially CrCA! 2. A method using a metal halide such as N1 (J2, MgCJ2, etc.) as a catalyst (%
29300), a method using a metal alkoxide of the formula M (OR) Method of using combined catalyst threads (% 1976-16076),
Triphenylantimony (JP-A-55-120629
) or a method using thread combining triphenylantimony and halogen (Japanese Unexamined Patent Publication No. 55-123623) as a catalyst,
A method using sulfur or a thiocarbamate compound as a catalyst (JP-A-54-152693, JP-A No. 58-1646, 9)
, a method using a thread made of a combination of a Lewis acid and a neutral salt as a catalyst (
% Kaisho 55-123624).
これらの触媒を用いる重合反応では、触媒は先す3PN
Cのリン原子に結合した塩素原子を塩素アニオンの形で
引き抜くことから重合が開始されるものと考えられてい
る。圓えば塩化アルミニウム(AJ(J、)触媒を例に
とると下式の様にして重合の開始反応が起る。In polymerization reactions using these catalysts, the catalyst is first 3PN
It is believed that polymerization is initiated by abstracting the chlorine atom bonded to the phosphorus atom of C in the form of a chlorine anion. Taking aluminum chloride (AJ) catalyst as an example, the polymerization initiation reaction occurs as shown in the following formula.
PNC
l
即ち、これらの触媒はいわゆるルイス酸としχ働いてい
る。PNC l That is, these catalysts act as so-called Lewis acids.
この機構によれば、上式でAlCl3の様なルイス酸の
代りにHCJやHNo3の様なプロトン酸を触媒として
使用した場合、開始反応の結果、同じプロトン酸である
HCA!が生成するので上式の平衡を著しく左側に偏ら
せ、その結果、開始反応が行き難いと説明されている(
%開昭53−71000)。According to this mechanism, when a protonic acid such as HCJ or HNo3 is used as a catalyst instead of a Lewis acid such as AlCl3 in the above equation, as a result of the initiation reaction, the same protonic acid HCA! is generated, which shifts the equilibrium in the above equation significantly to the left, and as a result, it is explained that the initiation reaction is difficult to proceed (
% Kaisho 53-71000).
事実、HCIやHBrの様なフ”ロトン酸存在丁では重
合が著しく阻害され、しかも分子蓋の非常に低いオリゴ
マーしか生成しないと報告され“Cいる〔特開昭51−
1600 、 Macrornolecules8、
36〜42(1975)、 Polymer l
l、31〜43(1970))。一方、この様な考え方
に反し、特定な構造のプロトン酸を触媒に使用し、高分
子蒼重合体を高い収率で得ている例も見られる。例えば
、メタンスルホン酸ヤポリリン酸の様な強酸もしくはこ
れら強酸の金属塩又は有機金属塩およびこれらの塩とハ
ロ塊状ホスファゼンとの反応生成物を触媒とする方法(
%開昭5l−1600)、有機スルホン酸を触媒とする
方法(%開昭58−45230 )等がそれで、これら
の場合プロトン酸を構成するアニオン部分が重合活性に
重要な役割を果しているものと解される。In fact, it has been reported that polymerization is significantly inhibited in the presence of fluorotonic acids such as HCI and HBr, and only oligomers with very low molecular caps are produced.
1600, Macronolecules8,
36-42 (1975), Polymer l
I, 31-43 (1970)). On the other hand, contrary to this idea, there are also examples of using protonic acids with specific structures as catalysts to obtain high-molecular blue polymers in high yields. For example, a method using as a catalyst a strong acid such as methanesulfonic acid and polyphosphoric acid, a metal salt or an organic metal salt of these strong acids, and a reaction product of these salts and a halo massive phosphazene (
%Kaisei 5l-1600), a method using an organic sulfonic acid as a catalyst (%Kaisei 58-45230), etc. In these cases, the anion moiety constituting the protonic acid plays an important role in polymerization activity. be understood.
この様にホスファゼンの重合反応について報告されてい
る結果は複雑で統一的に解釈出来1゛、その重合機構は
未だ充分には解明されていない。As described above, the results reported on the polymerization reaction of phosphazene are complex and cannot be interpreted in a unified manner1, and the polymerization mechanism has not yet been fully elucidated.
また、上記の触媒を用いた重合方法は初期の熱重合法に
比べ多くの利点はあるが、上記欠点を充分に克服したも
のとは云い難い。Moreover, although the polymerization method using the above-mentioned catalyst has many advantages over the initial thermal polymerization method, it cannot be said that the above-mentioned drawbacks have been fully overcome.
すなわち、これら触媒を使用することにより比較的低い
温度、短い反応時間で重合体を得ることが出来るが、重
合率を成る一定値より上げるとやはりゲルが生成したり
、重合率を上げてもゲルが生成t7ない様な場合は生成
重合体の分子量が極めて低かったり、また場合によって
は重合が促進されると同時にゲルの生成も促進される等
多くの欠点を有しているのが実情である。In other words, by using these catalysts, polymers can be obtained at relatively low temperatures and in a short reaction time, but if the polymerization rate is increased beyond a certain value, gels will still form, and even if the polymerization rate is increased, gels will still form. The reality is that in cases where no t7 is produced, the molecular weight of the polymer produced is extremely low, and in some cases, polymerization is accelerated and at the same time gel formation is also promoted. .
(解決しようとする問題点)
そこで本発明者等はこれらの欠点を克服または最小限に
抑えるため鋭意検討した結果、ホスファゼンを重合する
際、化学式SO4で表わされる原子団を含む化合物を触
媒として使用する新規重合方法を見出すに至った。(Problems to be Solved) As a result of intensive studies to overcome or minimize these drawbacks, the present inventors discovered that a compound containing an atomic group represented by the chemical formula SO4 is used as a catalyst when polymerizing phosphazene. We have discovered a new polymerization method.
本発明の目的は高分子量ホスファゼン重合体を容易に高
い転化率で製造しえて、しかもゲルの生成を実質的に伴
わないホスファゼン重合体の製造法を与えることにあり
、また重合体の分子量ならびに分子量分布を希望に応じ
て容易に調整しうるホスファゼン重合体の製造法を与え
ることにある。An object of the present invention is to provide a method for producing a phosphazene polymer that can easily produce a high molecular weight phosphazene polymer at a high conversion rate and that does not substantially involve the formation of gel. The object of the present invention is to provide a method for producing a phosphazene polymer whose distribution can be easily adjusted as desired.
(問題点を解決するための手段)
本発明の新規な触媒である原子団SO4を含む、すなわ
ち化学式SO4で表わされる原子団を含む化合物とは、
サルフェート陰イオン(SO4)まタハスルホニルジオ
キシM(−〇−80□−〇−)を含む化合物で、具体的
にはサルフェート陰イオンを含む化合物として硫酸、硫
酸と含窒素化合物との錯体、硫酸塩、硫酸水素塩、硫酸
塩または硫酸水素塩と硫酸との錯体、またスルホニルジ
オキシ基を含む化合物として硫酸ニススル等があげられ
るが、これらに限定されるものではない。なお、ここで
硫酸塩とはオキシ硫酸塩をも含む意味で用いている。(Means for Solving the Problems) The novel catalyst of the present invention, a compound containing an atomic group SO4, that is, a compound containing an atomic group represented by the chemical formula SO4, is:
Compounds containing sulfate anions (SO4) or tahasulfonyldioxy M (-〇-80□-〇-), specifically compounds containing sulfate anions include sulfuric acid, complexes of sulfuric acid and nitrogen-containing compounds, sulfuric acid Salts, hydrogen sulfates, sulfates or complexes of hydrogen sulfates and sulfuric acid, and compounds containing sulfonyldioxy groups include, but are not limited to, sulfuric acid. Note that the term sulfate is used herein to include oxysulfate as well.
本発明の新規な触媒である化学式SO4で表わされる原
子団を含む化合物は上述のHCI J+)HI3 rの
様なプロトン酸や、AlCl3の様なルイス酸と本質的
に異なることがわかった。即ちこれら触媒を使用するこ
とにより重合が容易に起り、ゲルの生成が殆んどないた
め、高い転化率でホスファゼン重合体を得ることが出来
るという特徴が見られ、更にその使用条件を変えること
によって、例えば当該触媒の種類、その使肚E重合時間
、重合温度等の条件を変えることによって、得られる重
合体の分子量および分子量分布も容易に制御できるとい
う利点も併せて有していることが明らかになった。It has been found that the novel catalyst of the present invention, a compound containing an atomic group represented by the chemical formula SO4, is essentially different from the above-mentioned protonic acids such as HCI J+)HI3 r and Lewis acids such as AlCl3. In other words, by using these catalysts, polymerization occurs easily and there is almost no gel formation, so it is possible to obtain phosphazene polymers at a high conversion rate. It is clear that this method also has the advantage that the molecular weight and molecular weight distribution of the resulting polymer can be easily controlled by changing conditions such as the type of catalyst, its polymerization time, and polymerization temperature. Became.
本発明の新規触媒の1例である硫酸と含窒素化合物との
錯体を構成する含窒素化合物としてはアミン、アミド、
イミド、ヒドロキシルアミン、オキシム、ヒドラジン、
ヒドラジド、ヒドラゾン、ニトロソアミン、ニトロアミ
ン、アミジン、アミドキシム、グアニジン、尿素、セミ
カルバジド、アミノカルボン酸、アミド酸、スルファミ
ド酸、含窒素チオカルボン酸、含窒素チオ尿素、アラル
キルアミン、ベンゾキノンイミン、アニル、アニリド、
イミド酸、ヒドロオ=13−
キサム酸等アンモニア誘導体、含窒素脂肪族および芳香
族化合物、およびビロール、ビロリン、ピロリジン、イ
ンドール、インドリン、イソインドール、カルバゾール
、インジゴ、ポルフィリン等窒素l原子含有5員環化合
物、ピリジン、ヒドロピリジン、ピペリジン、キノリン
、ヒドロキノリン、イソキノリン、アクリジン、ベンゾ
キノリン、ナフトキノリン、フェナントロリン等窒素1
i子含有6員環化合物、ピラゾール、イミダゾール、イ
ミダシリン、イミダゾリジン、ベンゾイミダゾール等窒
素2原子含有5員環化合物、ジアジン、ヒドロピリミジ
ン、ピペラジン、ベンゾジアジン、ジベンゾジアジン等
窒素2原子含有6員環化合物、トリアゾール、ベンゾト
リアゾール、トリアジン等窒素3原子含有5員環化合物
、オキサゾール、イソオキサゾール、オキサジン等窒素
l原子および酸累l原子含有複素環化合物、チアゾール
、ベンゾチアゾール、インチアゾール、チアジン等窒素
1原子および硫黄l原子含有複素環化合物、オキサジア
ゾール、オキサジアジン等窒素2原子および酸素1原子
含有複素環化合物、チアンジアゾール、チアンジアジン
等悩素2原子および硫黄l原子含有複素環化合物等の含
窒素環状化合物等があげられる。The nitrogen-containing compounds constituting the complex of sulfuric acid and nitrogen-containing compound, which is an example of the novel catalyst of the present invention, include amines, amides,
imide, hydroxylamine, oxime, hydrazine,
hydrazide, hydrazone, nitrosamine, nitroamine, amidine, amidoxime, guanidine, urea, semicarbazide, aminocarboxylic acid, amic acid, sulfamic acid, nitrogen-containing thiocarboxylic acid, nitrogen-containing thiourea, aralkylamine, benzoquinoneimine, anil, anilide,
Ammonia derivatives such as imidic acid and hydroxamic acid, nitrogen-containing aliphatic and aromatic compounds, and nitrogen-containing 5-membered ring compounds such as virol, viroline, pyrrolidine, indole, indoline, isoindole, carbazole, indigo, and porphyrin. , pyridine, hydropyridine, piperidine, quinoline, hydroquinoline, isoquinoline, acridine, benzoquinoline, naphthoquinoline, phenanthroline, etc. Nitrogen 1
5-membered ring compounds containing 2 nitrogen atoms, such as i-containing 6-membered ring compounds, pyrazole, imidazole, imidacilline, imidazolidine, benzimidazole, etc., 6-membered ring compounds containing 2 nitrogen atoms, such as diazine, hydropyrimidine, piperazine, benzodiazine, dibenzodiazine, etc. , 5-membered ring compounds containing 3 nitrogen atoms such as triazole, benzotriazole and triazine; heterocyclic compounds containing nitrogen and acid atoms such as oxazole, isoxazole and oxazine; 1 nitrogen atom such as thiazole, benzothiazole, inthiazole and thiazine and nitrogen-containing cyclic compounds such as sulfur l atom-containing heterocyclic compounds, oxadiazole, oxadiazine, etc., two nitrogen atoms and oxygen one atom containing heterocyclic compounds, thiandiazole, thiandiazine, etc. Examples include compounds.
本発明の新規触媒の他の例である硫酸塩を構成する陽イ
オンとしてはCu%Mg、 Zn、 Al、TI!、T
M、 Zr、 Th、 Sb、 Bi、 VSTa%C
r。The cations constituting the sulfate, which is another example of the novel catalyst of the present invention, include Cu%Mg, Zn, Al, TI! , T
M, Zr, Th, Sb, Bi, VSTa%C
r.
Mn、 Fe%Co、 Ni、 T、a、 Ce、 U
等元素周期律表のIa(アルカリ金属)を除(Ib〜■
族元素およびランタニド族、アクチニド族元素等の金属
陽イオンがあげられ、さらにはN2I]5、N2H6、
Nll、Ofl 等の陽イオンもあげられる。Mn, Fe%Co, Ni, T, a, Ce, U
Eliminate Ia (alkali metals) in the periodic table of equal elements (Ib~■
Examples include metal cations such as group elements, lanthanide group elements, actinide group elements, and furthermore, N2I]5, N2H6,
Cations such as Nll and Ofl can also be mentioned.
また硫酸水素塩、硫酸塩または硫酸水素塩と硫酸との錯
体等の触媒系の成分である硫酸塩および硫酸水素塩を構
成する陽イオンとしては上記金属イオンの他にIa族元
素、NH4、NR4、N01N2II5、N2H6、N
■I30■11C6115N三十
N およびP l−14等の陽イオンも含まれる。但し
、ここでRは置換または無置換芳香族基、または直鎖ま
たは分枝鎖アルキル、アルケニル基を表わし、それらの
炭素数は1〜8が適当である。In addition to the metal ions mentioned above, the cations constituting the sulfate and hydrogen sulfate, which are components of catalyst systems such as hydrogen sulfate, sulfate, or complexes of hydrogen sulfate and sulfuric acid, include group Ia elements, NH4, NR4 , N01N2II5, N2H6, N
Cations such as ■I30■11C6115N30N and Pl-14 are also included. Here, R represents a substituted or unsubstituted aromatic group, or a linear or branched alkyl or alkenyl group, and the number of carbon atoms thereof is preferably 1 to 8.
本発明の新規触媒の他の例である硫酸ニスデル等とは、
一般式R,−0−8O2−0−1’t2 で表わされ
る一連の化合物である。ここでR1ハアルカリ金属、水
素、置換または無置換芳香族基、または炭素数1−10
の直鎖または分枝鎖アルキル、アルケニル基あるいは脂
環式基を表わし、R2は置換または無置換芳香族基、ま
たは炭素数1−10の直鎖または分枝鎖アルキル、アル
ケニル基、脂環式基またはアミノ基(Nl12’)を表
わす。Other examples of the novel catalyst of the present invention, such as Nisdel sulfate, are:
These are a series of compounds represented by the general formula R, -0-8O2-0-1't2. where R1 is an alkali metal, hydrogen, a substituted or unsubstituted aromatic group, or has 1 to 10 carbon atoms;
represents a straight-chain or branched alkyl, alkenyl group, or alicyclic group, and R2 is a substituted or unsubstituted aromatic group, or a straight-chain or branched alkyl, alkenyl group, or alicyclic group having 1 to 10 carbon atoms. group or an amino group (Nl12').
本発明方法に於て、この様な化学式SO4で表わされる
原子団を含む化合物の使用量は特に限定されず広い範囲
内で適宜選択すれば良いが、反応系内の仕込みモノマー
に対して通常0.01ないし20モル%、好ましくは0
.05ないし10重量%共存させるのが良い。In the method of the present invention, the amount of the compound containing the atomic group represented by the chemical formula SO4 is not particularly limited and may be appropriately selected within a wide range. .01 to 20 mol%, preferably 0
.. 05 to 10% by weight is preferable.
重合触媒の使用量が少ないとホスファゼン重合体な高収
率で得ることが困難であり、また使用量が多いと重合体
収率が高くなるが、その分子量は低下する傾向がある。If the amount of polymerization catalyst used is small, it is difficult to obtain a phosphazene polymer in high yield, and if the amount used is large, the polymer yield increases, but the molecular weight tends to decrease.
重合反応は無溶媒または適当な溶媒の存在下で通常行な
われる。溶媒は原料モノマー、生成重合体および触媒と
反応しない様なものから適宜選択されるが、例えばベン
ゼン、トルエン、キシレン、クロルベンゼン、ジクロル
ベンゼン、トリクロルベンゼン、テトラクロルベンゼン
、ニトロベンゼン、ベンゼンスルホニルクロリド、ジヒ
ドロナフタレン、テトラヒドロナフタレン、ビフェニル
等芳香族系溶媒、および四塩化炭素、パークロルエチレ
ン、トリクロルエチレン、テトラクロルエタン、ジクロ
ルエタン、[素化パラフィン等脂肪族系溶媒があげられ
る。本発明では上記重合反応を密閉糸で行なっても良い
し、開放糸で行なっても良い。重合温度としては通常1
50ないし300℃、好ましくは150ないし260℃
、さらに好ましくは180ないし250℃が採用される
。重合温度が低過ぎると重合反応が起り難い傾向となり
、また逆に重合17一
温度が高過ぎると生成するホスファゼン重合体の解重合
及びゲル化が起る傾向となる。The polymerization reaction is usually carried out without a solvent or in the presence of a suitable solvent. The solvent is appropriately selected from those that do not react with the raw material monomer, the produced polymer, and the catalyst, such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, nitrobenzene, benzenesulfonyl chloride, Examples include aromatic solvents such as dihydronaphthalene, tetrahydronaphthalene, and biphenyl, and aliphatic solvents such as carbon tetrachloride, perchlorethylene, trichloroethylene, tetrachloroethane, dichloroethane, and [chlorinated paraffin]. In the present invention, the above polymerization reaction may be carried out using a closed thread or an open thread. The polymerization temperature is usually 1
50 to 300°C, preferably 150 to 260°C
, more preferably 180 to 250°C. If the polymerization temperature is too low, the polymerization reaction tends to be difficult to occur, and conversely, if the polymerization temperature is too high, the resulting phosphazene polymer tends to undergo depolymerization and gelation.
重合時間は一般に05ない1750時間程度である。The polymerization time is generally about 0.5 to 1750 hours.
この様にして生成したホスファゼン重合体は通常公知の
単離手段例えば再沈澱法等によって容易に単離、精製さ
れる。The phosphazene polymer thus produced can be easily isolated and purified by conventional isolation methods such as reprecipitation.
(発明の効果)
本発明方法によれば、重合反応が容易に起り、またゲル
の生成が殆んどないので、高い転化率で可溶性のホスフ
ァゼン重合体が容易に得らi+、また触媒の種類、使用
量、重合時間、重合温度等の重合条件を適宜選択するこ
とによって目的物のホスファゼン重合体の分子量および
分子綾分布を希望に応じ容易に変化させることができる
。(Effects of the Invention) According to the method of the present invention, the polymerization reaction occurs easily and there is almost no gel formation, so it is possible to easily obtain a soluble phosphazene polymer with a high conversion rate. By appropriately selecting polymerization conditions such as the amount used, polymerization time, and polymerization temperature, the molecular weight and molecular weight distribution of the target phosphazene polymer can be easily changed as desired.
(実施例)
以下に、本発明の実施例を示すが、本発明の範囲はこれ
らの実施例によって限定されるものではない。(Examples) Examples of the present invention are shown below, but the scope of the present invention is not limited by these Examples.
実施例1
窒素置換した内容積約20 mllのガラス製重合管に
31)NC3,59,3PNCに対し1.7モル%相当
の硫酸および1.2.4− ) +3クロルベンゼン3
.5mJを仕込んだ後、それを真空ポンプで引きながら
減圧封管した。次にそれを220℃のウッド合金浴につ
けて35時間靜装し、重合させた。Example 1 Sulfuric acid and 1.2.4- ) +3 chlorobenzene 3 equivalent to 1.7 mol % based on 31) NC3,59,3PNC were added to a glass polymerization tube with an internal volume of about 20 ml that was purged with nitrogen.
.. After charging 5 mJ, the tube was sealed under reduced pressure while being pulled with a vacuum pump. Next, it was immersed in a Wood alloy bath at 220°C for 35 hours to polymerize.
重合後、内容物をl Omlのトルエンに注いで不溶分
(ゲルおよび触媒残渣)と可溶分(未反応原料および可
溶性重合体等)にそれぞれ分別l〜だ。After polymerization, the contents were poured into 1 Oml of toluene and separated into insoluble components (gel and catalyst residue) and soluble components (unreacted raw materials, soluble polymer, etc.).
可溶分は更に30 mlのへブタンに注いで重合体を沈
澱として分離した。The soluble content was further poured into 30 ml of hebutane to separate the polymer as a precipitate.
得られた重合体を再び10rILlのトルエンに溶解シ
、p−クレゾールNa塩のジグライム溶液(1モル/
l ) 50 ml中に、50〜60℃で攪拌下、ゆっ
くり滴加した。The obtained polymer was dissolved again in 10ml of toluene, and a diglyme solution of p-cresol Na salt (1 mol/ml) was added.
l) It was slowly added dropwise into 50 ml under stirring at 50 to 60°C.
攪拌下、40時間還流を続けて反応させた後、内容物を
大波のメタノールに注ぎp−クレゾール置換重合体を分
離した。収量は2.19.9で、それは原料3PNCに
換算した収率で28%に相当する。After the reaction was continued under stirring for 40 hours under reflux, the contents were poured into a large amount of methanol to separate the p-cresol substituted polymer. The yield was 2.19.9, which corresponds to a yield of 28% in terms of raw material 3PNC.
尚、この置換重合体のGPC分析の結果、数平均分子量
は5.5万で、また重置平均分子社は54.6万であっ
た。3PNCの重合の際、ゲルの生成は認められなかっ
た。As a result of GPC analysis of this substituted polymer, the number average molecular weight was 55,000, and the weight average molecular weight was 546,000. No gel formation was observed during the polymerization of 3PNC.
実施1’!i2〜5
実施例1に於て、触媒に使用する硫酸の鎗を変える以外
は実施例1と同様の条件で重合させ、1部のものについ
ては更にp−クレゾール置換体を合成したところ表1の
様な結果が得られた。Implementation 1'! i2-5 In Example 1, polymerization was carried out under the same conditions as in Example 1 except that the sulfuric acid used as a catalyst was changed, and for some of the polymers, p-cresol substituted products were further synthesized. Table 1 The following results were obtained.
尚、何れの場合も、重合中にはゲルの生成は殆んど認め
られなかった。In any case, almost no gel formation was observed during the polymerization.
表 1
*) p−クレゾール置換重合体の分子針重合条件
3PNC3,4M、トリクロルベンゼン 3.5ml!
220℃で3.5時間重合
実施例6
窒素置換した内容積約20TrLlのガラス製重合管に
3PNC3,5,9,3PNCに対し、1.5モル%相
当の硫酸および1,2.4−)リクロルベンゼン3.5
mlを仕込んだ後、それを真空ポンプで引きながら減圧
封管した。次に、それを220℃のウッド合金浴につけ
て5時間静置し重合させたところ58.6%の収率で重
合体が得られた。Table 1 *) Molecular needle polymerization conditions of p-cresol substituted polymer
3PNC3.4M, trichlorobenzene 3.5ml!
Polymerization at 220°C for 3.5 hours Example 6 In a glass polymerization tube with an internal volume of about 20 TrLl, which was purged with nitrogen, sulfuric acid and 1,2.4-) equivalent to 1.5 mol% were added to 3PNC3,5,9,3PNC. Lichlorbenzene 3.5
After charging ml, the tube was sealed under reduced pressure while being pulled with a vacuum pump. Next, it was immersed in a Wood alloy bath at 220°C and allowed to stand for 5 hours to polymerize, resulting in a polymer with a yield of 58.6%.
尚、重合の際、ゲルの生成は殆んど認められなかった。Incidentally, during the polymerization, almost no gel formation was observed.
実施例7
窒素置換した内容積約20m7のガラス製重合管に3P
NC3,5&、3PNCに対し0.7モル%相当の硫酸
ヒドロキシルアミンおよび1,2.4−トリクロルベン
ゼン3.5mJを仕込んだ後、それを真空ポンプで引き
ながら減圧封管した。次にそれを220℃のウッド合金
浴につけて3.5時間静置重合させた。1合後、実施N
lと同様の後処理をしてp−クレゾール置換重合体を得
た。Example 7 3P in a glass polymerization tube with an internal volume of about 20 m7 that was purged with nitrogen.
After charging hydroxylamine sulfate and 3.5 mJ of 1,2,4-trichlorobenzene equivalent to 0.7 mol % based on NC3,5&,3PNC, the tube was sealed under reduced pressure while being pulled with a vacuum pump. Next, it was immersed in a Wood alloy bath at 220°C and allowed to stand and polymerize for 3.5 hours. After 1 go, implementation N
A p-cresol substituted polymer was obtained by post-treatment in the same manner as in 1.
収量は1.781で、それは原料3PNCに換算した収
率で22.8%に相当する。尚、この置換重合体のGP
C分析の結果、数平均分子量はI O,2万で、また重
量平均分子鼠は66.0万であった。The yield was 1.781, which corresponds to a yield of 22.8% in terms of raw material 3PNC. In addition, GP of this substituted polymer
As a result of C analysis, the number average molecular weight was IO, 20,000, and the weight average molecular weight was 660,000.
重合の際のゲルの生成は殆んどなかった。There was almost no gel formation during polymerization.
実施例8〜11
実施例7に於て、触媒に使用する硫酸ヒドロキシルアミ
ンの1を変化させ、重合時間を3.5時間の代りに3時
間にする以外は実施例7と同様の条件で重合させ、1部
のものについては更にp−クレゾール置換体を合成した
ところ表2の様な結果が得られた。Examples 8 to 11 Polymerization was carried out under the same conditions as in Example 7, except that 1 of the hydroxylamine sulfate used as the catalyst was changed and the polymerization time was changed to 3 hours instead of 3.5 hours. When p-cresol substituted products were further synthesized for some of the products, the results shown in Table 2 were obtained.
尚、何れの場合も、重合の際のゲルの生成は殆んど認め
られなかった。In any case, almost no gel formation was observed during polymerization.
表 2
養) p−クレゾール置換重合体の分子量重合条件 3
PNC3,5,9,)リクロルベンゼ:/ 3.5m
l。Table 2) Molecular weight polymerization conditions of p-cresol substituted polymer 3
PNC3,5,9,) Lichlorbenze: / 3.5m
l.
220℃で3時間重合
参考例1
実施例1Oに於て、0.72モル%の硫酸ヒドロキシル
アミンの代りに0.72モル%の塩酸ヒドロキシルアミ
ンを使用する以外は実施例10と同様の条件で重合を試
みたが重合体は生成しなかった。Polymerization at 220°C for 3 hours Reference Example 1 The same conditions as Example 10 were used except that in Example 1O, 0.72 mol% hydroxylamine hydrochloride was used instead of 0.72 mol% hydroxylamine sulfate. Polymerization was attempted, but no polymer was produced.
実施例12〜21
窒素置換した内容積綿20m1のガラス製重合管に3P
NC3,5,!i’、所定鼠の各種ぎ窒素化合物と硫酸
との錯体および1.2.4− ) IJジクロルンゼン
3.5−を仕込んだ後、それを真空ポンプで引きながら
減圧封むした。次にそれを220℃のウッド合金浴につ
けて所定時間静置重合した。重合後の内容物の後処理は
実施例1に準じて実施した。その結果、表3に示す結果
が得られた。Examples 12-21 3P in a glass polymer tube with an inner volume of 20 m1 of cotton that was purged with nitrogen
NC3,5,! i', a complex of various types of nitrogen compounds and sulfuric acid, and 1.2.4-) IJ dichlorunzene 3.5- were charged, and the mixture was sealed under reduced pressure while being pulled with a vacuum pump. Next, it was immersed in a Wood alloy bath at 220° C. and polymerized by standing for a predetermined period of time. Post-treatment of the contents after polymerization was carried out in accordance with Example 1. As a result, the results shown in Table 3 were obtained.
表 3
重合条件 3PNC3,5g、トリクロルベンゼン 3
.5−1220℃で重合
24一
実施例22
窒素置換した内容積綿20mJのガラス製1合管に3P
NC3,5,91ニトロシル硫酸の43%硫酸溶液20
.1m、9および1,2.4−)リクロルベンゼン3.
5mlを仕込んだ後、それを真空ポンプで引きながら減
圧封管した。次にそれを220℃のウッド合金浴につけ
て8時間静置重合し、た後、実施例1と同様の後処理を
したところ可溶性重合体が47%の収率で得られた。Table 3 Polymerization conditions 3PNC3.5g, trichlorobenzene 3
.. Polymerization at 5-1220°C 24-Example 22 3P in a glass tube with an internal volume of 20 mJ of nitrogen-substituted cotton
43% sulfuric acid solution of NC3,5,91 nitrosyl sulfuric acid 20
.. 1m,9 and 1,2.4-)lychlorobenzene3.
After charging 5 ml, the tube was sealed under reduced pressure while being pulled with a vacuum pump. Next, it was immersed in a Wood alloy bath at 220° C. and allowed to stand for 8 hours for polymerization. After that, it was subjected to the same post-treatment as in Example 1, and a soluble polymer was obtained in a yield of 47%.
実施例23〜28
窒素置換した内容積綿20 mlのガラス製重合管に3
PNC3,5g、所定量の各種含窒素化合物と硫酸との
錯体およびテトラリン3.5m/を(l込んだ後、それ
を真空ポンプで引きながら減圧封管した。Examples 23 to 28 Into a glass polymerization tube with an internal volume of 20 ml of cotton that was purged with nitrogen,
After adding 3.5 g of PNC, a predetermined amount of a complex of various nitrogen-containing compounds and sulfuric acid, and 3.5 m/l of tetralin, the tube was sealed under reduced pressure while being pulled with a vacuum pump.
次にそれを220℃のウッド合金浴につけて所定時間静
置重合した。重合後の内容物の後処理は実施例1に準じ
て実施したところ表4に示す様な結果が得られた。Next, it was immersed in a Wood alloy bath at 220° C. and polymerized by standing for a predetermined period of time. Post-treatment of the contents after polymerization was carried out according to Example 1, and the results shown in Table 4 were obtained.
表 4
重合条件 3PNC3,5,9,テトラリン 3.5
ml。Table 4 Polymerization conditions 3PNC3,5,9, Tetralin 3.5
ml.
220℃で重合
実施例29
窒A置換した内容棟線20m1のガラス製重合管に3P
NC3,5,9、無水硫酸銅80 mllおよび1.2
.4−)リクロルベンゼン3.5mA’を仕込んだ後、
それを貞9ポンプで引きながら減圧封管した。Polymerization at 220°C Example 29 3P in a 20m1 glass polymerization tube with nitrogen A replacement
NC3,5,9, anhydrous copper sulfate 80 ml and 1.2
.. 4-) After charging 3.5 mA' of lychlorobenzene,
The tube was sealed under reduced pressure while being pulled with a Tei 9 pump.
次にそれをウッド合金浴につけて220℃で2時間静置
重合した後、実施例1と同様の後処理をしたところ可溶
性重合体が27%の収率で得られ、そのp−クレゾール
置換体の数平均および重量平均分子量はそれぞれ21万
および159万であった。尚、重合の際ゲルの生成は殆
んど認められなかった。Next, it was immersed in a Wood's alloy bath and allowed to stand at 220°C for 2 hours of polymerization, followed by the same post-treatment as in Example 1. A soluble polymer was obtained in a yield of 27%, and its p-cresol substituted product The number average and weight average molecular weights were 210,000 and 1,590,000, respectively. Incidentally, almost no gel formation was observed during the polymerization.
実施例30
実施例29に於て無水硫酸銅80m9の代りに無水硫酸
アルミニウム171.4 mlを使用する以外は実施例
29と全く同様の重合および後処理を行なったところ、
可溶性重合体が19%の収率で得られ、そのp−クレゾ
ール置換体の数平均および重量平均分子量はそれぞれ2
5万および143万であった。尚、重合の際ゲルの生成
は殆んど認められなかった。Example 30 Polymerization and post-treatment were carried out in exactly the same manner as in Example 29, except that 171.4 ml of anhydrous aluminum sulfate was used instead of 80 m9 of anhydrous copper sulfate.
A soluble polymer was obtained with a yield of 19%, the number average and weight average molecular weight of the p-cresol substituted product being 2, respectively.
50,000 and 1.43 million. Incidentally, almost no gel formation was observed during the polymerization.
実施例31〜41
窒素WIL換した内容棟線20 mlのガラス製重合管
に3PNC3,59、所定量の各ね硫酸塩の無水物およ
び1,2.4−)リクロルベンゼン3.5m7Iを仕込
んだ後、それを真仝ポンプで引きながら減圧封管した。Examples 31 to 41 A 20 ml glass polymerization tube with nitrogen exchanged contents was charged with 3PNC3,59, a predetermined amount of anhydrous sulfate, and 3.5 m7I of 1,2,4-)lychlorobenzene. After that, the tube was sealed under reduced pressure while being pulled with a true pump.
次にそれを220℃のウッド合金浴につけ所定時間静置
重合した後、実施例1と同様の後処理を実施したところ
表5に示す結果が得られた。Next, it was placed in a Wood alloy bath at 220° C. and allowed to stand for polymerization for a predetermined period of time, and then subjected to the same post-treatment as in Example 1, and the results shown in Table 5 were obtained.
U)
駆
実施例42
窒素置換した内容棟線204のガラス製重合管に3PN
C3,5,9,無水硫酸銅115.1mJおよびテトラ
リン3.5mlを仕込んだ後、それを真空ポンプで引き
ながら減圧封管した。U) Practical Example 42 3PN was added to the glass polymer tube of the nitrogen-substituted content ridge line 204.
After charging C3,5,9, 115.1 mJ of anhydrous copper sulfate, and 3.5 ml of tetralin, the tube was sealed under reduced pressure while being pulled with a vacuum pump.
次にそれを220℃のウッド合金浴につけて24時間重
合した後、実施例1と同様の後処理を実施したところ可
溶性重合体が51%の収率で得られた。Next, it was immersed in a Wood alloy bath at 220° C. to polymerize for 24 hours, and then the same post-treatment as in Example 1 was carried out, and a soluble polymer was obtained in a yield of 51%.
尚、重合の際、ゲルの生成は認められなかった。Note that no gel formation was observed during the polymerization.
実施例43
窒素置換した内容棟線20−のガラス製重合管に3PN
03.5,9.硫酸ニッケルと硫酸との錯体35 ml
および1.2.4−トリクロルベンゼン3.5mlを仕
込んだ後、それを真空ポンプで引きながら減圧封管した
。Example 43 3PN in a glass polymerization tube with nitrogen-substituted content line 20-
03.5,9. Complex of nickel sulfate and sulfuric acid 35 ml
After charging 3.5 ml of 1,2,4-trichlorobenzene, the tube was sealed under reduced pressure while being pulled with a vacuum pump.
次にそれをウッド合金浴につけて220℃で3時間重合
した後、実施例1と同様の後処理をしたところ可溶性重
合体が31%の収率で得られ、そのp−クレゾール置換
体の数平均および重量平均分子閂はそれぞれ15万およ
び88万であった。重合の際のゲルの生成は3%であっ
た。Next, it was immersed in a Wood alloy bath and polymerized at 220°C for 3 hours, followed by the same post-treatment as in Example 1. A soluble polymer was obtained in a yield of 31%, and the number of p-cresol substituted products was The average and weight average molecular weights were 150,000 and 880,000, respectively. Gel formation during polymerization was 3%.
尚、硫酸ニッケルと硫酸との錯体は次の様にして合成し
た。The complex of nickel sulfate and sulfuric acid was synthesized as follows.
内容積100mjの三角フラスコに微粉砕した硫酸ニッ
ケル・六水和物(Ni 804・6 H2O) 2Iを
仕込み、これに攪拌しながら30 mlの濃硫酸をゆっ
くり加えた。80℃で3時間攪拌を続けた後16時間室
温に放置した。Finely ground nickel sulfate hexahydrate (Ni 804.6 H2O) 2I was placed in an Erlenmeyer flask with an internal volume of 100 mj, and 30 ml of concentrated sulfuric acid was slowly added to the flask while stirring. After continuing stirring at 80° C. for 3 hours, the mixture was left at room temperature for 16 hours.
次に、冷却・攪拌しながら乾燥したエーテル60mjを
ゆっくり加えた。更に30分間攪拌を続けた後装置し、
分離した沈澱の上澄液を除去した。沈澱に乾燥したエー
テルを加えて攪拌・分離する上記の操作を繰り返して余
剰の硫酸を除去した後、ガラスフィルターで沈澱なμ則
り、、真空下室温で30時間乾燥したところ淡黄色の粉
末が得られた。Next, 60 mj of dry ether was slowly added while cooling and stirring. After continuing stirring for an additional 30 minutes, the device was
The supernatant liquid of the separated precipitate was removed. After repeating the above procedure of adding dry ether to the precipitate, stirring and separating to remove excess sulfuric acid, the precipitate was filtered through a glass filter and dried under vacuum at room temperature for 30 hours to obtain a pale yellow powder. It was done.
との錯体は硫酸ニッケル・六水和物中の水分子が、硫酸
分子で置換された構造を写していると考えられている。It is thought that the complex with nickel sulfate hexahydrate has a structure in which the water molecules in nickel sulfate hexahydrate are replaced with sulfuric acid molecules.
実施例44〜51
実施例43に於て、硫酸ニッケルと硫酸との錯体の代り
に実施例43に記載したと同様の方法で合成した各種硫
酸塩と硫酸との錯体の所定普を使用し、220℃で3時
間・重合する代りに所定時間重合する以外は実施例43
と全く同様の重合および後処理を行なったところ、表6
に示す様な結果が得られた。Examples 44 to 51 In Example 43, instead of the complex of nickel sulfate and sulfuric acid, prescribed complexes of various sulfates and sulfuric acid synthesized in the same manner as described in Example 43 were used, Example 43 except that instead of polymerizing at 220°C for 3 hours, polymerization was performed for a predetermined period of time.
When polymerization and post-treatment were carried out in exactly the same manner as in Table 6,
The results shown are obtained.
実施例53
窒素置換した内容積的201rLlのガラス製重合管に
3PNC3,!Ml、硫酸第2鉄・硫酸錯体35 ml
およびテトラリン3.5mJを仕込んだ後、それを真空
ポンプで引きながら減圧封管した。Example 53 3PNC3,! in a glass polymerization tube with an internal volume of 201rLl that was purged with nitrogen! Ml, ferric sulfate/sulfuric acid complex 35 ml
After charging 3.5 mJ of tetralin, the tube was sealed under reduced pressure while being pulled with a vacuum pump.
次にそれをウッド合金浴につけて、220℃で24時間
重合した後、実施例1と同様の後処理をしたところ可溶
性重合体が43%の収率で得られた。尚、重合の際、ゲ
ルの生成は認められなかった。Next, it was immersed in a Wood alloy bath and polymerized at 220° C. for 24 hours, followed by the same post-treatment as in Example 1, and a soluble polymer was obtained in a yield of 43%. Note that no gel formation was observed during the polymerization.
実施例54
窒素置換した内容積的20−のガラス製重合管に3PN
C3,5g、硫酸銅・硫酸錯体16m9および1,2.
4−1リクロルベンゼン7mを仕込んだ後、それを真空
ポンプで引きながら減圧封管した。Example 54 3PN was placed in a 20-volume glass polymerization tube purged with nitrogen.
C3.5g, copper sulfate/sulfuric acid complex 16m9 and 1,2.
After charging 7 m of 4-1-lichlorobenzene, the tube was sealed under reduced pressure while being pulled with a vacuum pump.
次にそれをウッド合金浴につけて、220℃で24時間
重合した後、実施例1と同様の後処理をしたところ可溶
性重合体が30%の収率で得られた。Next, it was immersed in a Wood alloy bath and polymerized at 220° C. for 24 hours, followed by the same post-treatment as in Example 1, and a soluble polymer was obtained in a yield of 30%.
実施例55
窒素置換した内容積的20−のガラス製重合管に3PN
03.5g、硫酸水素アンモニウム11.5−および1
,2.4−)リクロルベンゼン3.54を仕込んだ後、
それを真空ポンプで引きながら減圧封管した。Example 55 3PN was placed in a 20-volume glass polymerization tube purged with nitrogen.
03.5 g, ammonium hydrogen sulfate 11.5- and 1
, 2.4-) After charging 3.54 chlorbenzene,
The tube was sealed under reduced pressure while being pulled with a vacuum pump.
次にそれをウッド合金浴につけて、220℃で4時間重
合した後、実施例1と同様の後処理をしたところ可溶性
重合体が24%の収率で得られ、そのp−クレゾール置
換体の数平均および重置平均分子量はそれぞれ21万お
よび220万であった。Next, it was immersed in a Wood alloy bath and polymerized at 220°C for 4 hours, followed by the same post-treatment as in Example 1. A soluble polymer was obtained in a yield of 24%, and the p-cresol substituted product was The number average and weight average molecular weights were 210,000 and 2.2 million, respectively.
実施例56〜58
実施例55に於て硫酸水素アンモニウムの代りに無水の
各種硫酸水素化合物の所定址を使用し、重合時間4時間
の代りに所定時間重合する以外は実施例55と全く同様
の操作を実施したところ表7に示す様な結果が得られた
。Examples 56 to 58 Completely the same as Example 55, except that in Example 55, a prescribed amount of anhydrous various hydrogen sulfate compounds was used instead of ammonium hydrogen sulfate, and the polymerization time was polymerized for a prescribed time instead of 4 hours. When the operation was carried out, the results shown in Table 7 were obtained.
表 7
重合条件 3PNC3,5,9,)リクロルベンゼン
3.5ml。Table 7 Polymerization conditions 3PNC3,5,9,) Lichlorobenzene 3.5ml.
220℃で1合
実施例59
窒素置換した内容積的20mのガラス製重合管に3PN
Ca、sy、硫酸水素テトラブチルアンモニウム34.
1mfIおよび1,2.4−)リクロルベンゼン3.5
mlを仕込んだ後、それを真空ポンプで引きながら減圧
封管した。1 cup at 220°C Example 59 3PN was placed in a glass polymerization tube with an internal volume of 20 m purged with nitrogen.
Ca, sy, tetrabutylammonium hydrogen sulfate 34.
1mfI and 1,2.4-)lychlorobenzene 3.5
After charging ml, the tube was sealed under reduced pressure while being pulled with a vacuum pump.
次にそれをウッド合金浴につけて250℃で5.5時間
重合した後、実施例1と同様の後処理をしたところ可溶
性重合体が50%の収率で得られた。尚、重合の際ゲル
の生成は2%であった。Next, it was immersed in a Wood alloy bath and polymerized at 250° C. for 5.5 hours, and then subjected to the same post-treatment as in Example 1, resulting in a soluble polymer with a yield of 50%. The amount of gel produced during polymerization was 2%.
実施例60
実施例59に於て硫酸水素テトラブチルアンモニウム3
4.1m、9の代りに硫酸水素アミノアセトニ) 1フ
ル15.5−を使用し、重合時間5.5時間の代りに7
時間重合する以外は実施例59と全く同様の操作を実施
したところ可溶性重合体が18%の収率で得られた。尚
、重合の際ゲルの生成は2%であった。Example 60 Tetrabutylammonium hydrogen sulfate 3 in Example 59
4.1 m, 1 full 15.5- was used instead of 9, and 7 was used instead of 5.5 hours for polymerization time.
The same procedure as in Example 59 was carried out except that the polymerization was carried out over a period of time, and a soluble polymer was obtained in a yield of 18%. The amount of gel produced during polymerization was 2%.
実施例61
窒素置換した内容積的20m1のガラス製重合管に3P
NC3,5#、3PNCに対して1.4モル%相当の硫
酸ジエチルおよび1,2.4−)リクロルベンゼン3.
5mlを仕込んだ後、それを真空ポンプで引きながら減
圧封管した。Example 61 3P in a glass polymerization tube with an internal volume of 20 m1 purged with nitrogen
3. Diethyl sulfate and 1,2.4-)lychlorobenzene equivalent to 1.4 mol% based on NC3,5#, 3PNC.
After charging 5 ml, the tube was sealed under reduced pressure while being pulled with a vacuum pump.
次にそれをウッド合金浴につけて220℃で6時間重合
した後、実施例1と同様の後処理をしたところ可溶性重
合体が38%の収率で得られ、そのp−クレゾール置換
体の数平均および重量平均分子量はそれぞれ5−2万お
よび107万であった。尚、重合の際ゲルの生成は1.
5%であった。Next, it was immersed in a Wood alloy bath and polymerized at 220°C for 6 hours, followed by the same post-treatment as in Example 1. A soluble polymer was obtained in a yield of 38%, and the number of p-cresol substituted polymers was 38%. The average and weight average molecular weights were 50,000-20,000 and 1,070,000, respectively. Note that gel formation during polymerization is as follows: 1.
It was 5%.
実施例62
実施例61に於て、3PNCに対して1.4モル%相当
の硫酸ジエチルを使用する代りに、0.6モル%相当の
硫酸ジエチルを使用し、重合時間6時間の代りに5時間
重合する以外は実施例61と全く同様の操作を実施した
ところ、可溶性重合体が42%の収率で得られた。Example 62 In Example 61, instead of using diethyl sulfate equivalent to 1.4 mol% based on 3PNC, diethyl sulfate equivalent to 0.6 mol% was used, and the polymerization time was 5 hours instead of 6 hours. When the same operation as in Example 61 was carried out except for the time polymerization, a soluble polymer was obtained in a yield of 42%.
実施例63〜67
実施例61に於て、3PNCに対して1.4モル%相当
の硫酸ジエチルを使用する代りに、スルホニルジオキシ
基を含む各種化合物の所装置を使用し、220℃で6時
間重合する代りに所定温度で所定時間重合する以外は実
施例61と全く同様の操作を実施したところ表8に示す
様な結果が得られた。Examples 63 to 67 In Example 61, instead of using diethyl sulfate equivalent to 1.4 mol% based on 3PNC, an apparatus containing various compounds containing a sulfonyldioxy group was used, and 6 When the same operation as in Example 61 was carried out, except that the polymerization was carried out at a predetermined temperature for a predetermined time instead of a time polymerization, the results shown in Table 8 were obtained.
実施例68
窒素置換した内容積的2 () 1nlのガラス製重合
管に3PNC3,5,9,31)NCに対し0,37モ
ル%相当の硫酸水素ヒドラジニウム硫酸錯体(N2H5
IISO4・ll2SO4)および1,2.47)リク
ロルベンゼン3.5TrLlを仕込んだ後、それを真空
ポンプで引きながら減圧封管した。Example 68 Hydrogen sulfate hydrazinium sulfate complex (N 2 H
After charging IISO4.ll2SO4) and 3.5TrLl of 1,2.47) lychlorobenzene, the tube was sealed under reduced pressure while being pulled with a vacuum pump.
次にそれを220℃のウッド合金浴につけて1時間20
分重合した後、実施例1と同様の後処理を行なったとこ
ろ可溶性重合体が29%の収率で得られた。Next, it was placed in a wood alloy bath at 220°C for 1 hour at 20°C.
After the partial polymerization, the same post-treatment as in Example 1 was performed, and a soluble polymer was obtained in a yield of 29%.
実施例69
窒素置換した内容積的20ydのガラス製重合管にオク
タクロロシクロテトラホスファゼン(4PNC) 3.
5.9.4 PNCに対し1,8モル%相当の硫酸およ
び1,2.4− ) IJジクロルンゼン3.5TrL
lを仕込んだ後、それを真空ポンプ゛C引きながら減圧
封管した。Example 69 Octachlorocyclotetraphosphazene (4PNC) was added to a 20 yd glass polymerization tube purged with nitrogen.3.
5.9.4 Sulfuric acid and 1,2.4-)IJ dichlorunzene 3.5TrL equivalent to 1.8 mol% based on PNC
1 was charged, and the tube was sealed under reduced pressure while pulling the vacuum pump C.
次にそれを220℃のウッド合金袷につけて4時間重合
した後、実施例1と同様の後処理をしたところ可溶性重
合体が13%の収率で得られた。Next, it was placed on a wood alloy liner at 220° C. and polymerized for 4 hours, and then subjected to the same post-treatment as in Example 1, and a soluble polymer was obtained in a yield of 13%.
蕗考例2
実施例55に於て硫酸水素アンモニウム11,5mlの
代りに硫酸アンモニウム13.2m、9を使用する以外
は実施例55と同様の条件で重合を試みたが重合体の生
成は認められなかった。Fushimi Example 2 Polymerization was attempted under the same conditions as in Example 55 except that 13.2ml of ammonium sulfate, 9 was used instead of 11.5ml of ammonium hydrogen sulfate, but no polymer formation was observed. There wasn't.
参考例3
実施例58に於て、硫酸水素す) IJウム12.1m
lの代りに硫酸ナトリウム14.3mlを使用し、重合
時間を2時間の代りに7時間にする以外は実施例58と
同様の条件で重合を試みたが重合体の生成は認められな
かった。Reference Example 3 In Example 58, hydrogen sulfate (IJum) 12.1 m
Polymerization was attempted under the same conditions as in Example 58, except that 14.3 ml of sodium sulfate was used instead of 1, and the polymerization time was changed to 7 hours instead of 2 hours, but no polymer formation was observed.
%許出願人 丸善石油化学株式会社
新日曹化工株式会社
手 続 補 正 書
昭和61年 9月90
昭和61年特許願 第186164号
2、発明の名称
ホスファゼン重合体の製造法
3、補正をする者
事件との関係 特許出願人
住所
氏 名 丸善石油化学株式会社 (ほか1名)(名 称
)
4、代理人
昭和 年 月 日 (自 発)
(1)明細書第16頁下から第4行のr20モル係」を
「20重量%」に訂正する。% Applicant: Maruzen Petrochemical Co., Ltd. Nippon Sokako Co., Ltd. Procedures Amendment September 90, 1988 Patent Application No. 186164 2, Name of Invention Process for Producing Phosphazene Polymer 3, Amended Relationship with the Patent Applicant’s Case Patent Applicant Address Name Maruzen Petrochemical Co., Ltd. (1 other person) (Name) 4. Agent Showa Month, Day (Voluntary) (1) Line 4 from the bottom of page 16 of the specification Correct "r20 molar ratio" to "20% by weight".
Claims (14)
は4)で表わされる環状ホスファゼン化合物を原子団S
O_4を含む化合物の存在下で加熱して重合することを
特徴とするホスファゼン重合体の製造法。(1) Add a cyclic phosphazene compound represented by (NPCl_2)_y (where y is 3 and/or 4) to the atomic group S
A method for producing a phosphazene polymer, which comprises polymerizing by heating in the presence of a compound containing O_4.
含窒素化合物との錯体である特許請求の範囲第1項に記
載の製造法。(2) The production method according to claim 1, wherein the compound containing the atomic group SO_4 is sulfuric acid or a complex of sulfuric acid and a nitrogen-containing compound.
またはオキシム化合物である特許請求の範囲第2項に記
載の製造法。(3) The production method according to claim 2, wherein the nitrogen-containing compound is hydroxylamine, hydrazine, or an oxime compound.
bないしVIII族の金属元素およびランタニド族、アクチ
ニド族元素の硫酸塩無水物である特許請求の範囲第1項
に記載の製造法。(4) Compounds containing the atomic group SO_4 are I of the Periodic Table of Elements
The manufacturing method according to claim 1, which is a sulfate anhydride of metal elements of groups B to VIII and elements of the lanthanide group and actinide group.
びランタニド族、アクチニド族元素がCu、Mg、Zn
、Al、Ti、Zr、Th、Bi、V、Mn、Fe、N
iおよびCeである特許請求の範囲第4項に記載の製造
法。(5) Metal elements of groups Ib to VIII of the Periodic Table of Elements and elements of the lanthanide group and actinide group include Cu, Mg, and Zn.
, Al, Ti, Zr, Th, Bi, V, Mn, Fe, N
The manufacturing method according to claim 4, wherein i and Ce.
aないしVIII族の金属元素およびランタニド族、アクチ
ニド族元素の硫酸水素塩無水物である特許請求の範囲第
1項に記載の製造法。(6) Compounds containing the atomic group SO_4 are I of the Periodic Table of Elements
The manufacturing method according to claim 1, which is an anhydrous hydrogen sulfate of metal elements of groups A to VIII and elements of the lanthanide group and actinide group.
R_4^+(Rは置換または無置換芳香族基、または直
鎖または分枝鎖アルキルもしくはアルケニル基を表わす
)、NO^+、N_2H^5^+、N_2H_6^2^
+、NH_3OH^+、C_6H_5N≡N^+および
PH_4^+の群から選ばれた陽イオンと硫酸水素陰イ
オンとからなる硫酸水素塩無水物である特許請求の範囲
第1項に記載の製造法。(7) Compounds containing the atomic group SO_4 are NH_4^+, N
R_4^+ (R represents a substituted or unsubstituted aromatic group, or a straight or branched chain alkyl or alkenyl group), NO^+, N_2H^5^+, N_2H_6^2^
+, NH_3OH^+, C_6H_5N≡N^+, and PH_4^+, which is a hydrogen sulfate anhydride consisting of a cation selected from the group of NH_3OH^+, C_6H_5N≡N^+, and PH_4^+ and a hydrogen sulfate anion. .
、N_2H_6^2^+およびNH_3OH^+の陽イ
オンと硫酸陰イオンとからなる硫酸塩無水物である特許
請求の範囲第1項に記載の製造法。(8) A compound containing the atomic group SO_4 is N_2H_5^+
, N_2H_6^2^+ and NH_3OH^+ cations and sulfate anhydrides, which are sulfate anhydrides, according to claim 1.
aないしVIII族の金属元素およびランタニド族、アクチ
ニド族元素の硫酸塩または硫酸水素塩と硫酸との錯体で
ある特許請求の範囲第1項に記載の製造法。(9) Compounds containing the atomic group SO_4 are I of the Periodic Table of Elements
The production method according to claim 1, which is a complex of sulfuric acid or hydrogen sulfate of a metal element of groups A to VIII, a lanthanide group, or an actinide group element, and sulfuric acid.
NR_4^+(Rは置換または無置換芳香族基、または
直鎖または分枝鎖アルキルもしくはアルケニル基を表わ
す)、NO^+、N_2H_5^+、N_2H_6^2
^+、NH_3OH^+、C_6H_5N≡N^+およ
びPH_4^+の群から選ばれた陽イオンの硫酸塩無水
物または硫酸水素塩無水物と硫酸との錯体である特許請
求の範囲第1項に記載の製造法。(10) The compound containing the atomic group SO_4 is NH_4^+,
NR_4^+ (R represents a substituted or unsubstituted aromatic group, or a straight or branched chain alkyl or alkenyl group), NO^+, N_2H_5^+, N_2H_6^2
^+, NH_3OH^+, C_6H_5N≡N^+ and PH_4^+ A complex of sulfate anhydride or hydrogen sulfate anhydride of a cation selected from the group of PH_4^+ and sulfuric acid. Manufacturing method described.
−−O−SO_2−O−R_2(ここでR_1はアルカ
リ金属、水素、C_1〜C_1_0の直鎖、分枝鎖また
は環状の脂肪族炭化水素基、または芳香族基を表わし、
R_2はC_1〜C_1_0の直鎖、分枝鎖または環状
の脂肪族炭化水素基、芳香族基、またはアミノ基を表わ
す)で表わされる化合物である特許請求の範囲第1項に
記載の製造法。(11) The compound containing the atomic group SO_4 has the general formula R_1
--O-SO_2-O-R_2 (where R_1 represents an alkali metal, hydrogen, a linear, branched or cyclic aliphatic hydrocarbon group of C_1 to C_1_0, or an aromatic group,
2. The manufacturing method according to claim 1, wherein R_2 is a compound represented by C_1 to C_1_0 (representing a linear, branched or cyclic aliphatic hydrocarbon group, aromatic group, or amino group).
よびランタニド族、アクチニド族元素がNa、Cu、M
g、Zn、Al、Ti、Zr、Th、Bi、V、Mn、
Fe、NiおよびCeである特許請求の範囲第6項また
は第9項記載の製造法。(12) Metal elements of groups I a to VIII of the periodic table of elements and elements of the lanthanide group and actinide group are Na, Cu, M
g, Zn, Al, Ti, Zr, Th, Bi, V, Mn,
The manufacturing method according to claim 6 or 9, wherein Fe, Ni and Ce are used.
トリホスファゼンである特許請求の範囲第1項ないし第
12項のいずれかに記載の製造法。(13) The production method according to any one of claims 1 to 12, wherein the cyclic phosphazene compound is hexachlorocyclotriphosphazene.
雰囲気下、150℃ないし300℃の温度で0.01な
いし20重量%の原子団SO_4を含む化合物と共に、
0.5ないし50時間反応させることからなる特許請求
の範囲第1ないし第12項のいずれかに記載の製造法。(14) Hexachlorocyclotriphosphazene under an inert atmosphere at a temperature of 150°C to 300°C with a compound containing 0.01 to 20% by weight of the atomic group SO_4,
The manufacturing method according to any one of claims 1 to 12, which comprises reacting for 0.5 to 50 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61186164A JPH0647448B2 (en) | 1986-08-08 | 1986-08-08 | Method for producing phosphazene polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61186164A JPH0647448B2 (en) | 1986-08-08 | 1986-08-08 | Method for producing phosphazene polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6341537A true JPS6341537A (en) | 1988-02-22 |
JPH0647448B2 JPH0647448B2 (en) | 1994-06-22 |
Family
ID=16183507
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61186164A Expired - Lifetime JPH0647448B2 (en) | 1986-08-08 | 1986-08-08 | Method for producing phosphazene polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0647448B2 (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55136107A (en) * | 1979-03-19 | 1980-10-23 | Akzo Nv | Preparation of phosphagen polymer |
-
1986
- 1986-08-08 JP JP61186164A patent/JPH0647448B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55136107A (en) * | 1979-03-19 | 1980-10-23 | Akzo Nv | Preparation of phosphagen polymer |
Also Published As
Publication number | Publication date |
---|---|
JPH0647448B2 (en) | 1994-06-22 |
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