TWI585195B - A fluorine-containing phosphate amide, a flame-retardant resin containing the same, a flame retardant liquid and a flame retardant solvent for organic synthesis - Google Patents
A fluorine-containing phosphate amide, a flame-retardant resin containing the same, a flame retardant liquid and a flame retardant solvent for organic synthesis Download PDFInfo
- Publication number
- TWI585195B TWI585195B TW102111557A TW102111557A TWI585195B TW I585195 B TWI585195 B TW I585195B TW 102111557 A TW102111557 A TW 102111557A TW 102111557 A TW102111557 A TW 102111557A TW I585195 B TWI585195 B TW I585195B
- Authority
- TW
- Taiwan
- Prior art keywords
- fluorine
- group
- bis
- trifluoroethyl
- phosphate
- Prior art date
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims description 92
- 239000011737 fluorine Substances 0.000 title claims description 83
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 82
- 239000003063 flame retardant Substances 0.000 title claims description 76
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 74
- 239000007788 liquid Substances 0.000 title claims description 67
- 229910019142 PO4 Inorganic materials 0.000 title claims description 63
- -1 phosphate amide Chemical class 0.000 title claims description 61
- 239000010452 phosphate Substances 0.000 title claims description 49
- 239000002904 solvent Substances 0.000 title claims description 34
- 229920005989 resin Polymers 0.000 title claims description 27
- 239000011347 resin Substances 0.000 title claims description 27
- OCBMNKXTDPSDKN-UHFFFAOYSA-N decan-1-amine;phosphoric acid Chemical compound OP(O)(O)=O.CCCCCCCCCCN OCBMNKXTDPSDKN-UHFFFAOYSA-N 0.000 claims description 40
- 238000003786 synthesis reaction Methods 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 125000001153 fluoro group Chemical group F* 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims description 10
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 4
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 description 61
- 238000006460 hydrolysis reaction Methods 0.000 description 46
- 230000007062 hydrolysis Effects 0.000 description 41
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 31
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 13
- 239000012044 organic layer Substances 0.000 description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006880 cross-coupling reaction Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 150000003014 phosphoric acid esters Chemical class 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229940080818 propionamide Drugs 0.000 description 5
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 5
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 5
- BRWBDEIUJSDQGV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-methoxyhexane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BRWBDEIUJSDQGV-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- AOSLLHRECOJPNJ-UHFFFAOYSA-N 2-[chloro(2,2,2-trifluoroethoxy)phosphoryl]oxy-1,1,1-trifluoroethane Chemical compound FC(F)(F)COP(Cl)(=O)OCC(F)(F)F AOSLLHRECOJPNJ-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 4
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 4
- 239000010720 hydraulic oil Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- JWHXMVCSSSOAHL-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropan-1-amine Chemical compound NC(F)(F)C(F)(F)C(F)(F)F JWHXMVCSSSOAHL-UHFFFAOYSA-N 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- ZIIRNMSLBKKJPJ-UHFFFAOYSA-N COC(CC(F)(F)F)(CC(F)(F)F)C(=O)NC(C)C Chemical compound COC(CC(F)(F)F)(CC(F)(F)F)C(=O)NC(C)C ZIIRNMSLBKKJPJ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-O isopropylaminium Chemical compound CC(C)[NH3+] JJWLVOIRVHMVIS-UHFFFAOYSA-O 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- RVSIYYNULVSROE-UHFFFAOYSA-N 2,2,6-trimethyl-3,4-bis(2,2,2-trifluoroethyl)-1H-pyridine Chemical compound FC(CC1=C(C(NC(=C1)C)(C)C)CC(F)(F)F)(F)F RVSIYYNULVSROE-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 2
- WNKLRZXHVZWCFB-UHFFFAOYSA-N CC(C)NC(C)(CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F Chemical compound CC(C)NC(C)(CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F WNKLRZXHVZWCFB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- WXJNIVWQUXQFCD-UHFFFAOYSA-N FC(CC1(CNCC(N1)(C)CC(F)(F)F)C)(F)F.P(O)(O)(O)=O Chemical compound FC(CC1(CNCC(N1)(C)CC(F)(F)F)C)(F)F.P(O)(O)(O)=O WXJNIVWQUXQFCD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CNJVMZPOYUPBRF-UHFFFAOYSA-N OP(O)(O)=O.CC(C)NC(C)(CCC(F)(F)F)CC(F)(F)F Chemical compound OP(O)(O)=O.CC(C)NC(C)(CCC(F)(F)F)CC(F)(F)F CNJVMZPOYUPBRF-UHFFFAOYSA-N 0.000 description 2
- WVKUSIAWZULCKO-UHFFFAOYSA-N OP(O)(O)=O.CNC(CC(F)(F)F)CC(F)(F)F Chemical compound OP(O)(O)=O.CNC(CC(F)(F)F)CC(F)(F)F WVKUSIAWZULCKO-UHFFFAOYSA-N 0.000 description 2
- KIDNKLCIMZQGQO-UHFFFAOYSA-N P(=O)(O)(O)O.FC(CC1(CCCC(CCC1)NC(C)C)CC(F)(F)F)(F)F Chemical compound P(=O)(O)(O)O.FC(CC1(CCCC(CCC1)NC(C)C)CC(F)(F)F)(F)F KIDNKLCIMZQGQO-UHFFFAOYSA-N 0.000 description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- XBUGKDHALPQOTH-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) hydrogen phosphate Chemical compound FC(F)(F)COP(=O)(O)OCC(F)(F)F XBUGKDHALPQOTH-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 235000008434 ginseng Nutrition 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000004713 phosphodiesters Chemical class 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- MPSMMJPLERAHAL-UHFFFAOYSA-N (4-propylphenoxy)boronic acid Chemical compound CCCC1=CC=C(OB(O)O)C=C1 MPSMMJPLERAHAL-UHFFFAOYSA-N 0.000 description 1
- WLCGYIWOKVWFLB-UHFFFAOYSA-N (4-propylphenyl)boronic acid Chemical compound CCCC1=CC=C(B(O)O)C=C1 WLCGYIWOKVWFLB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 1
- WQLARYCJNJRHPK-UHFFFAOYSA-N 1,3,3,5,5-pentamethyl-2,6-bis(2,2,2-trifluoroethyl)piperazine Chemical compound FC(CC1N(C(C(NC1(C)C)(C)C)CC(F)(F)F)C)(F)F WQLARYCJNJRHPK-UHFFFAOYSA-N 0.000 description 1
- JGZIGHCTUBYUGI-UHFFFAOYSA-N 1,3,5-trimethyl-3,5-bis(2,2,2-trifluoroethyl)piperazine Chemical compound FC(CC1(CN(CC(N1)(C)CC(F)(F)F)C)C)(F)F JGZIGHCTUBYUGI-UHFFFAOYSA-N 0.000 description 1
- OUEYPASPHBLRTO-UHFFFAOYSA-N 1-N-methyl-2-N-[3-propan-2-yl-4,5-bis(2,2,2-trifluoroethyl)-1H-indol-2-yl]propane-1,2-diamine Chemical compound FC(CC=1C(=C2C(=C(NC2=CC1)NC(CNC)C)C(C)C)CC(F)(F)F)(F)F OUEYPASPHBLRTO-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- NAYIXKXYHOLMRC-UHFFFAOYSA-N 1-phenyl-4-propylbenzene Chemical group C1=CC(CCC)=CC=C1C1=CC=CC=C1 NAYIXKXYHOLMRC-UHFFFAOYSA-N 0.000 description 1
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical compound C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 1
- DRVMZMGCPWFDBI-UHFFFAOYSA-N 2,2,2-trifluoroethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC(F)(F)F DRVMZMGCPWFDBI-UHFFFAOYSA-N 0.000 description 1
- ZYDUNXCLPOKBNQ-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1,3-dihydropyridine Chemical compound CC1(C)CC=CC(C)(C)N1 ZYDUNXCLPOKBNQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C07F9/59—Hydrogenated pyridine rings
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/24—Catalysts containing metal compounds of tin
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
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- C09K21/00—Fireproofing materials
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- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Description
本發明係關於含氟磷酸酯醯胺。更詳細而言,係關於在樹脂用難燃劑、可燃性液體用之難燃劑、有機合成用難燃性溶劑、蓄電池電解液用之難燃性溶劑、難燃性液壓油、難燃性潤滑劑、難燃性萃取溶劑及難燃性洗淨劑等用途為有用之水解耐性優異之含氟磷酸酯醯胺、含有其之難燃性樹脂、難燃性液體及有機合成用難燃性溶劑。
磷酸酯及磷酸酯醯胺等之磷酸酯類,因為具有來自磷原子之卓越難燃性、自熄性,被廣泛利用在作為各種樹脂之難燃劑(例如專利文獻1~3)。
關於難燃化之用途為多樣化中,即使對於磷酸酯類,亦追求更高度之性能。亦即,為了減少對被添加體之物性、機能之影響,追求以更少量添加量表現難燃效果、或即使在高溫條件亦難以變質之具有化學、熱穩定性等。
尤其是磷酸酯類,在化學性穩定性面有容易受到水解之課題。磷酸酯類受到水解時,難燃性降低或消失,有因為呈現磷酸般之酸性而影響被添加體之性能或耐久性的情況而成為問題。對於如此問題,提案各種構造之磷酸酯類(專利文獻4、5等),水解耐性已有所改善。然而,依然殘存以少量添加量用以表現難燃效果之難燃性提高之課題。
又,磷酸酯類當中於常溫呈現液體性狀之比較低分子量之化合物時,不僅樹脂難燃劑,亦被利用在鋰離子蓄電池電解液用之難燃劑(專利文獻6)、液壓油(專利文獻7)、萃取溶劑(專利文獻8)及有機合成用溶劑(專利文獻9)等各式各樣之用途。作為如此之磷酸酯類,雖使用磷酸三甲酯或磷酸三丁酯等,但此等對水解除了亦無充分耐性外,為具有引火點之可燃性物質故難燃效果亦不充分。
另一方面,於酯側鏈具有氟原子之磷酸酯類,已知藉由磷原子與氟原子的加乘效果而具有高度難燃性,以更少量之添加顯示難燃效果(非專利文獻1)。又,含氟磷酸酯類亦具有對氧化顯示優異耐性之特徵,正進行尤其是將追求高度安全性與抗氧化性之鋰離子蓄電池電解液用之難燃劑作為中心之研究(非專利文獻1、專利文獻10)。
然而,含氟磷酸酯類,作為由於電子吸引性之氟原子的影響之水解耐性相當微弱。又,為水解生成物之磷酸二酯因為顯示強酸性(非專利文獻2),此係成為觸
媒而容易加速水解。據此,作為樹脂之難燃劑之際,有難燃性持續之課題,作為萃取溶劑或有機合成用溶劑之際亦有限定使用條件之課題。又,即使在蓄電池電解液之用途亦不可忽視從各構件所帶來水分的影響,由於水解,磷酸二酯之生成造成對電池性能之不良影響。
於含氟磷酸酯類之中,即使連於分子中具有P-N鍵結之含氟磷酸酯醯胺亦已知(非專利文獻3、專利文獻11)。此含氟磷酸酯醯胺藉由水解切斷P-N鍵結時為了生成胺而中和磷酸二酯。據此,預料前述之酸觸媒作用的影響被減輕,而具有經改善之水解耐性。尚且,報告作為含氟磷酸酯醯胺之醯胺部位取代基,係無取代或直鏈烷基者。
又,未具有引火點,且實質上無因水解劣化的化合物,例如已知有全氟己烷、全氟烷基醚、全氟烷基胺等之全氟烷基化合物。此等係利用低蒸發潛熱,主要係作為工業零件洗淨製程之排水劑使用。惟此等全氟烷基化合物因為與各種有機化合物的相溶性不夠充分,故被用在樹脂用難燃劑、有機合成用溶劑、蓄電池電解液用難燃劑或萃取溶劑等廣泛用途實為困難。
[專利文獻1]日本特開昭54-19919號公報
[專利文獻2]日本特開平11-181428號公報
[專利文獻3]日本特開2001-139823號公報
[專利文獻4]日本特開昭57-207642號公報
[專利文獻5]WO01/4204號公報
[專利文獻6]日本特開2002-203597號公報
[專利文獻7]日本特表2008-519146號公報
[專利文獻8]日本特開2001-192746號公報
[專利文獻9]日本特開2009-102576號公報
[專利文獻10]日本特開平8-88023號公報
[專利文獻11]日本特開2011-141974號公報
[非專利文獻1]J. Electrochemical Society, 150, A161-169 (2003)
[非專利文獻2]Seriya Khimicheskaya, 1491-1497 (1982)
[非專利文獻3]J. Fluorine Chemistry, 113, 111-122 (2002)
如前述,磷酸酯類具有難燃性提高與水解耐性之課題,含氟磷酸酯醯胺具有可解決此等課題的可能性。然而,對於在前述先前文獻所示之含氟磷酸酯醯胺,本發明者們研究水解耐性之際,判斷仍尚未充分。
本發明係鑑於此等之課題而完成者。亦即,以提供一種具有以少量之添加即顯示難燃效果等之高度難燃性,且具有充分水解耐性之含氟磷酸酯醯胺為目的。
本發明者們,為了解決先前的課題經深入研究的結果,發現具有特定構造之含氟磷酸酯醯胺以少量添加而顯示難燃效果,且具有非常優異之水解耐性而完成本發明。亦即,本發明係關於下述之要旨者。
1.一種含氟磷酸酯醯胺,其特徵係以下述一般式(1)表示,
(式中,R1、R2表示可相同或相異且至少一方之氮原子鍵結碳為2級碳或3級碳之碳數1~20的分支或直鏈烷基;惟,R1及R2可具有選自由烷氧基、羥基、胺基、甲胺基、乙胺基、二甲胺基、二乙胺基及氟原子所構成之群之取代基;又,R1與R2可彼此鍵結形成5~8員環之環狀構
造;X、Y表示相同或相異之氫原子或氟原子;n、m表示1~6之整數)。
2.如項1之含氟磷酸酯醯胺,其係下述一般式(2)所示;
(式中,R1、R2表示相同或相異,皆為氮原子鍵結碳為2級碳或3級碳之碳數3~20的分支烷基;又,R1及R2可具有選自由烷氧基、羥基、胺基、甲胺基、乙胺基、二甲胺基、二乙胺基及氟原子所構成之群之取代基;又,R1與R2可彼此鍵結形成5~8員環之環狀構造;X、Y表示相同或相異之氫原子或氟原子;n、m表示1~6之整數)。
3.一種難燃性樹脂,其係含有前述一般式(1)及/或前述一般式(2)所示之含氟磷酸酯醯胺。
4.一種難燃性液體,其係含有前述一般式(1)及/或前述一般式(2)所示之含氟磷酸酯醯胺。
5.一種有機合成用難燃性溶劑,其係由含有前述一般式(1)及/或前述一般式(2)所示之含氟磷酸酯醯胺
或項4之難燃性液體所構成。
根據本發明,係提供一種具有以少量添加顯示難燃效果等優異難燃性,且具有非常優異之水解耐性之含氟磷酸酯醯胺。藉由將此含有於樹脂,得到以少量之添加且長期可持續維持難燃效果的樹脂。又,由本發明所提供特定構造之含氟磷酸酯醯胺,除了優異之難燃性與水解耐性之外,因為具有液體狀態之溫度幅度寬廣,具有比較高之介電常數,與有機化合物的相溶性良好等之特徵,提高單獨藉由含氟磷酸酯醯胺、或含氟磷酸酯醯胺配合於可燃性液體之難燃性液體,可利用於有機合成用難燃性溶劑或蓄電池用之難燃性電解液等多樣用途。
本發明之含氟磷酸酯醯胺,係前述一般式(1)所示。亦即,其特徵為在醯胺部位,具有氮原子與至少一個2級或3級碳鍵結之分支構造的烷基。原本含氟磷酸酯類係由於氟原子電子吸引性的影響,雖預料對於水解不具有充分之耐性,於本發明之醯胺部位具有分支構造之含氟磷酸酯醯胺,係對於水解具有顯著提高之耐性。該驚人的顯著效果之主要原因雖未明確,但推測恐怕是由於來自上述構造之電子效果與立體效果的加乘效果。
在一般式(1),作為R1、R2之例,可列舉甲
基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、t-丁基、n-戊基、t-戊基、n-己基、環己基、n-辛基、環辛基、2-乙基己基、n-癸基、n-十二基、n-十四基、n-十六基、n-十八基、n-二十基、2-甲氧乙基、2-乙氧乙基、2-羥乙基、2-胺乙基、2-(甲基胺基)乙基、2-(二甲基胺基)乙基、2-(乙基胺基)乙基、2-(二乙基胺基)乙基、2,2,2-三氟乙基、2-甲氧基-1-甲基乙基、2-乙氧基-1-甲基乙基、2-羥基-1-甲基乙基、2-胺基-1-甲基乙基、2-(甲基胺基)-1-甲基乙基、2-(二甲基胺基)-1-甲基乙基、2-(乙基胺基)-1-甲基乙基、2-(二乙基胺基)-1-甲基乙基、2-甲氧基-1,1-二甲基乙基、2-乙氧基-1,1-二甲基乙基、2-羥基-1,1-二甲基乙基、2-胺基-1,1-二甲基乙基、2-(甲基胺基)-1,1-二甲基乙基、2-(二甲基胺基)-1,1-二甲基乙基、2-(乙基胺基)-1,1-二甲基乙基、2-(二乙基胺基)-1,1-二甲基乙基等。
在一般式(1),X、Y表示相同或相異之氫原子或氟原子,n、m表示1~6之整數。作為一般式(1)所示之含氟磷酸酯醯胺之例,可列舉磷酸雙(2,2,2-三氟乙基)N-異丙基甲醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基乙醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基n-丙醯胺、磷酸雙(2,2,2-三氟乙基)二異丙醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基n-丁醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基n-戊醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基n-己醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基環己醯胺、磷酸雙(2,2,2-
三氟乙基)N-異丙基n-辛醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基環辛醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基n-癸基醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基n-十二烷醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基n-十四烷醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基n-十六烷醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基n-十八烷醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基n-二十烷醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基-2-甲氧基乙醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基-2-乙氧基乙醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基-2-羥基乙醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基-2-胺基乙醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基-2-(甲基胺基)乙醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基-2-(二甲基胺基)乙醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基-2-(乙基胺基)乙醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基-2-(二乙基胺基)乙醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基-2,2,2-三氟乙基醯胺、磷酸雙(2,2,2-三氟乙基)N-(2-甲氧基-1-甲基乙基)甲醯胺、磷酸雙(2,2,2-三氟乙基)N-(2-甲氧基-1-甲基乙基)異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-(2-羥基-1-甲基乙基)甲醯胺、磷酸雙(2,2,2-三氟乙基)N-(2-羥基-1-甲基乙基)異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-(2-胺基-1-甲基乙基)甲醯胺、磷酸雙(2,2,2-三氟乙基)N-(2-胺基-1-甲基乙基)異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-[2-(甲基胺基)-1-甲基乙基]甲醯胺、磷酸雙(2,2,2-三氟乙基)N-[2-(甲基胺基)-1-甲基乙基]異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-[2-(二
甲基胺基)-1-甲基乙基]甲醯胺、磷酸雙(2,2,2-三氟乙基)N-[2-(二甲基胺基)-1-甲基乙基]異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-sec-丁基甲醯胺、磷酸雙(2,2,2-三氟乙基)N-sec-丁基乙醯胺、磷酸雙(2,2,2-三氟乙基)N-sec-丁基n-丙醯胺、磷酸雙(2,2,2-三氟乙基)N-sec-丁基異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-sec-丁基n-丁醯胺、磷酸雙(2,2,2-三氟乙基)二sec-丁醯胺、磷酸雙(2,2,2-三氟乙基)N-sec-丁基t-丁醯胺、磷酸雙(2,2,2-三氟乙基)N-t-丁基甲醯胺、磷酸雙(2,2,2-三氟乙基)N-t-丁基乙醯胺、磷酸雙(2,2,2-三氟乙基)N-t-丁基n-丙醯胺、磷酸雙(2,2,2-三氟乙基)N-t-丁基異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-t-丁基n-丁醯胺、磷酸雙(2,2,2-三氟乙基)二t-丁醯胺、磷酸雙(2,2,2-三氟乙基)N-t-戊基甲醯胺、磷酸雙(2,2,2-三氟乙基)N-t-戊基異丙基醯胺、磷酸雙(2,2-二氟乙基)N-異丙基甲醯胺、磷酸雙(2,2-二氟乙基)二異丙醯胺、磷酸雙(2,2,3,3-四氟丙基)N-異丙基甲醯胺、磷酸雙(2,2,3,3-四氟丙基)二異丙醯胺、磷酸雙(2,2,3,3,3-五氟丙基)N-異丙基甲醯胺、磷酸雙(2,2,3,3,3-五氟丙基)二異丙醯胺、磷酸雙(2,2,3,3,4,4,5,5-八氟戊基)N-異丙基甲醯胺、磷酸雙(2,2,3,3,4,4,5,5-八氟戊基)二異丙醯胺、磷酸雙(2,2,3,3,4,4,5,5,6,6,7,7-十二氟庚基)N-異丙基甲醯胺、磷酸雙(2,2,3,3,4,4,5,5,6,6,7,7-十二氟庚基)二異丙醯胺、磷酸2,2,3,3-四氟丙基2,2,2-三氟乙基N-異丙基甲醯胺、磷酸2,2,3,3-四氟丙基2,2,2-三氟乙基二異丙醯胺等。
尚且,作為R1與R2彼此鍵結為4~8員環之環狀構造而成之含氟磷酸酯醯胺之例,可列舉磷酸雙(2,2,2-三氟乙基)2-甲基吡咯烷、磷酸雙(2,2,2-三氟乙基)2,5-二甲基吡咯烷、磷酸雙(2,2,2-三氟乙基)2-甲基吡啶、磷酸雙(2,2,2-三氟乙基)2-乙基吡啶、磷酸雙(2,2,2-三氟乙基)2,2-二甲基吡啶、磷酸雙(2,2,2-三氟乙基)2,6-二甲基吡啶、磷酸雙(2,2,2-三氟乙基)2,2,6-三甲基吡啶、磷酸雙(2,2,2-三氟乙基)2,2,6,6-四甲基吡啶、磷酸雙(2,2,2-三氟乙基)2-甲基嗎啉醯胺(morpholide)、磷酸雙(2,2,2-三氟乙基)2,6-二甲基嗎啉醯胺、磷酸雙(2,2,2-三氟乙基)2,2,6,6-四甲基嗎啉醯胺、磷酸雙(2,2,2-三氟乙基)2-甲基哌嗪、磷酸雙(2,2,2-三氟乙基)2,6-二甲基哌嗪、磷酸雙(2,2,2-三氟乙基)2,2,6,6-四甲基哌嗪、磷酸雙(2,2,2-三氟乙基)N’-甲基-2-甲基哌嗪、磷酸雙(2,2,2-三氟乙基)N’-甲基-2,6-二甲基哌嗪、磷酸雙(2,2,2-三氟乙基)N’-甲基-2,2,6,6-四甲基哌嗪、磷酸雙(2,2,3,3-四氟丙基)2-甲基吡啶、磷酸雙(2,2,3,3,3-五氟丙基)2-甲基吡啶、磷酸雙(2,2,3,3,4,4,5,5-八氟戊基)2-甲基吡啶、磷酸雙(2,2,3,3,4,4,5,5,6,6,7,7-十二氟庚基)2-甲基吡啶、磷酸雙(2,2,3,3,4,4,5,5,6,6,7,7-十二氟庚基)2,2,6,6-四甲基吡啶、磷酸2,2,3,3-四氟丙基2,2,2-三氟乙基2-甲基吡啶等。
又,本發明之含氟磷酸酯醯胺當中,如前述一般式(2)所示醯胺氮原子與2個2級或3級碳鍵結時,具有更提高之水解耐性。作為如此之一般式(2)所示之含
氟磷酸酯醯胺之例,可列舉磷酸雙(2,2,2-三氟乙基)二異丙醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基環己醯胺、磷酸雙(2,2,2-三氟乙基)N-異丙基環辛醯胺、磷酸雙(2,2,2-三氟乙基)N-(2-甲氧基-1-甲基乙基)異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-(2-羥基-1-甲基乙基)異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-(2-胺基-1-甲基乙基)異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-[2-(甲基胺基)-1-甲基乙基]異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-[2-(二甲基胺基)-1-甲基乙基]異丙基醯胺、磷酸雙(2,2,2-三氟乙基)N-sec-丁基異丙基醯胺、磷酸雙(2,2,2-三氟乙基)二sec-丁醯胺、磷酸雙(2,2,2-三氟乙基)N-sec-丁基t-丁醯胺、磷酸雙(2,2,2-三氟乙基)N-t-丁基異丙基醯胺、磷酸雙(2,2,2-三氟乙基)二t-丁醯胺、磷酸雙(2,2,2-三氟乙基)N-t-戊基異丙基醯胺、磷酸雙(2,2-二氟乙基)二異丙醯胺、磷酸雙(2,2,3,3-四氟丙基)二異丙醯胺、磷酸雙(2,2,3,3,3-五氟丙基)二異丙醯胺、磷酸雙(2,2,3,3,4,4,5,5-八氟戊基)二異丙醯胺、磷酸雙(2,2,3,3,4,4,5,5,6,6,7,7-十二氟庚基)二異丙醯胺、磷酸2,2,3,3-四氟丙基2,2,2-三氟乙基二異丙醯胺、磷酸雙(2,2,2-三氟乙基)2,6-二甲基吡咯烷、磷酸雙(2,2,2-三氟乙基)2,6-二甲基吡啶、磷酸雙(2,2,2-三氟乙基)2,2,6-三甲基吡啶、磷酸雙(2,2,2-三氟乙基)2,2,6,6-四甲基吡啶、磷酸雙(2,2,2-三氟乙基)2,6-二甲基嗎啉醯胺、磷酸雙(2,2,2-三氟乙基)2,2,6,6-四甲基嗎啉醯胺、磷酸雙(2,2,2-三氟乙基)2,6-二甲基哌嗪、磷酸雙(2,2,2-三氟乙基)2,2,6,6-四甲
基哌嗪、磷酸雙(2,2,2-三氟乙基)N’-甲基-2,6-二甲基哌嗪、磷酸雙(2,2,2-三氟乙基)N’-甲基-2,2,6,6-四甲基哌嗪、磷酸雙(2,2,3,3-四氟丙基)2,6-二甲基吡啶、磷酸雙(2,2,3,3,3-五氟丙基)2,6-二甲基吡啶、磷酸雙(2,2,3,3,4,4,5,5-八氟戊基)2,6-二甲基吡啶、磷酸雙(2,2,3,3,4,4,5,5,6,6,7,7-十二氟庚基)2,6-二甲基吡啶、磷酸2,2,3,3-四氟丙基2,2,2-三氟乙基2,6-二甲基吡啶等。
本發明之一般式(1)或(2)所示之含氟磷酸酯醯胺,可遵循非專利文獻3等所示之方法合成。亦即,如流程圖(3)所示,可藉由使由三氯化磷與含氟醇所衍生之含氟氯磷酸酯(5)與2級胺(6)反應而合成。
所得到之含氟磷酸酯醯胺,粗生成物雖可直接使用在難燃用途,可由公知之萃取法、蒸餾法或再結晶法等純化,可減低化、或實質上不含作為雜質存在之水
分、磷酸、磷酸縮合物、氯化物、原料胺、原料醇及中間體含氟氯磷酸酯等之含量。
其次對於本發明之含氟磷酸酯醯胺之利用法進行說明。本發明之含氟磷酸酯醯胺,具有不具引火點等優異難燃性,不僅中性條件,即使在酸性或鹼性條件亦具有穩定等非常優異之水解耐性。又,在物性面,因為合併具有以高沸點且低凝固點液體狀態之溫度幅度廣、具有比較高之介電常數等特徵,可利用在單獨或對材料之配合的各種用途。
藉由將本發明之含氟磷酸酯醯胺添加於樹脂,可賦予樹脂難燃機能。尤其是本發明之含氟磷酸酯醯胺,因為具有優異難燃性與水解耐性,以少量添加之樹脂的難燃化為可能,且經過長期依然可維持難燃性。
作為對樹脂之添加方法,可列舉於樹脂合成時混合原料單體使其聚合之方法、或於樹脂成型時藉由公知之混煉法等混合之方法等。作為應賦予難燃性之樹脂,例如可列舉聚乙烯樹脂及聚酯樹脂等之熱可塑性樹脂、聚胺基甲酸乙酯樹脂及酚樹脂等之熱硬化性樹脂等。對此等樹脂之含氟磷酸酯的添加量,相對於樹脂之重量比為2~20%。添加量未滿2%時難燃性不夠充分,超過20%時對樹脂特性之影響增大故為不佳。
本發明之含氟磷酸酯醯胺,可使用在配合可燃性液,使引火點消失或上昇,著火時賦予無法繼續燃燒之自熄性等可燃性液體的難燃化。本發明之含氟磷酸酯醯
胺因為相對於有機化合物具有非常優異之相溶性,可配合多樣之可燃性液體。作為應賦予難燃性之可燃性液體,可列舉作為有機合成用溶劑、蓄電池電解液、萃取溶劑及洗淨劑等使用之可燃性液體,例如可列舉庚烷、十二烷、甲苯、乙苯等之烴類、二氯乙烷、氯苯等之鹵素化烴類、乙醇、1-丁醇、1-辛醇、乙二醇、甘油等之醇類、二異丙基醚、二n-丁基醚、四氫呋喃等之醚類、甲基乙基酮、環己酮等之酮類、乙酸、2-乙基己烷酸等之羧酸類、乙酸丁酯、琥珀酸二乙酯、酞酸二乙酯等之酯類、γ-丁內酯等之內酯類、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸乙烯酯、碳酸丙烯酯等之碳酸酯類、三n-丁胺、N,N-二甲基苯胺等之胺類、N,N-二甲基甲醯胺、N-甲基吡咯啶酮、1,3-二甲基咪唑啉酮等之醯胺類、二n-丁基硫化物等之硫化物類、二甲基亞碸等之亞碸類、磷酸三乙酯、磷酸三n-丁酯等之磷酸酯類等。相對於上述可燃性液體含氟磷酸酯之添加量,雖因可燃性液體之種類、用途而有所不同,但通常以相對於可燃性液體之容量比為0.1~10倍。
藉由本發明之含氟磷酸酯醯胺之配合而難燃化之難燃性液體當中,引火點消失之非引火性液體時,從安全性更高、可減輕該液體操作設備之約束之利點為大。尚且,相對於可燃性液體所添加之含氟磷酸酯醯胺的沸點低時,以比較少量之添加量可使引火點消失特別有效。
可將本發明之含氟磷酸酯醯胺或包含其之難燃性液體作為有機合成用溶劑使用。作為有機合成反應,
例如可列舉酯化反應、醚化反應、醯胺化反應、胺基化反應、水解反應、交叉耦合反應、氧化反應、還原反應、鹵素化反應及聚合反應等。
本發明之含氟磷酸酯醯胺因為水解耐性優異,將使水共存之反應、反應中生成水之反應、或水解反應等作為用以安全實施之溶劑非常有效。又,本發明之含氟磷酸酯醯胺因為具有優異之難燃性、且相對於氧化亦具有優異之耐性,將氧化反應作為工業上用以安全實施之溶劑特別有效。反應條件雖因反應之種類而不同,但因為本發明之含氟磷酸酯為低溶點、熱穩定性高,可在-30~200℃之廣泛溫度範圍實施反應。
各反應後,如有必要使反應液與水接觸,可去除水溶性之未反應原料、生成物及觸媒等。此時,本發明之含氟磷酸酯因為即使為酸性、中性、鹼性之任一條件相對於水解為穩定,萃取條件並未限定。生成物藉由晶析法或蒸餾法等可從含有含氟磷酸酯醯胺之溶液分離。此時,本發明之含氟磷酸酯醯胺因為係比較高沸點,目的生成物為低沸點成分時,蒸餾法因為製程簡單故特別有效。
又,本發明之含氟磷酸酯醯胺不僅與可燃性液體的相溶性優異,亦可溶解電解質鹽等之鹽。據此,可將本發明之含氟磷酸酯醯胺或包含其之難燃性液體作為蓄電池電解液之溶劑使用。作為此時之蓄電池,可列舉鋰離子蓄電池、鋰空氣電池、鎂離子蓄電池、鈉離子蓄電池、鋁離子蓄電池等。尤其是將空氣作為正極之鋰空氣電池等
之金屬空氣電池的情況,藉由與外氣的接觸由吸濕容易招致電解液成分的水解。據此將水解耐性優異之本發明之含氟磷酸酯醯胺或包含其之難燃性液體作為溶劑使用係非常有效。
本發明之含氟磷酸酯醯胺或包含其之難燃性液體,利用含氟磷酸酯醯胺優異難燃性、水解耐性及作為液體之溫度範圍廣等之物性值特徵,除了上述用途之外,亦可使用在難燃性液壓油、難燃性潤滑劑、難燃性萃取溶劑、難燃性洗淨劑等之用途。
以下雖使用實施例詳細說明本發明,但本發明並非藉由此實施例而被限定者。
磷酸雙(2,2,2-三氟乙基)二異丙醯胺(BTFDIA)之合成
於附攪拌機之四口燒瓶,加入氯仿832g、雙
(2,2,2-三氟乙基)氯磷酸酯(純度90.3%)447g,於冰-食鹽浴冷卻至0℃。攪拌下,一邊將反應溫度控制在0~5℃一邊從滴下漏斗以3小時滴下二異丙基胺334g。滴下終了後,恢復至室溫,繼續攪拌12小時。反應終了後,加入5%碳酸氫鈉水溶液2500g並攪拌後,分餾有機層。從有機層餾除氯仿後,由蒸餾純化,分餾沸點80℃/0.8kPa之餾分,得到無色之液體432g。
由NMR、GC-MS之分析,確認所得到之液體為磷酸雙(2,2,2-三氟乙基)二異丙醯胺。
1H-NMR(CDCl3、TMS)
δ 4.20~4.35(m、4H)、3.41~3.56(m、2H)、1.25(d、J=4Hz、12H)
13C-NMR(CDCl3、TMS)
δ 122.88(dq、J=12Hz、278Hz)、62.50(dq、J=4Hz、38Hz)、46.70(d、J=5Hz)、22.30(d、J=1Hz)
19F-NMR(CDCl3、CFCl3)
δ -75.76(t、J=9Hz)
GC-MS(EI)
m/z 330[M-CH3]+、302、288、268、242、188、162、142、108、84、43
於附攪拌機之四口燒瓶,加入氯仿83g、雙(2,2,2-三氟乙基)氯磷酸酯(純度90.3%)45g,於冰-食鹽浴冷卻至0℃。攪拌下,一邊將反應溫度控制在0~5℃一邊從滴下漏斗以2小時滴下N-異丙基n-丙胺33g。滴下終了後,恢復至室溫,繼續攪拌12小時。反應終了後,加入5%碳酸氫鈉水溶液250g並攪拌後,分餾有機層。從有機層餾除氯仿後,由蒸餾純化,分餾沸點82℃/0.8kPa之餾分,得到無色之液體41g。
由NMR、GC-MS之分析,確認所得到之液體為磷酸雙(2,2,2-三氟乙基)N-異丙基n-丙醯胺。
1H-NMR(CDCl3、TMS)
δ 4.20~4.35(m、4H)、3.41~3.56(m、1H)、2.95~2.87(m、2H)、1.63~1.53(m、2H、J=8Hz)、1.25(d、J=4Hz、6H)0.88(t、3H、J=8Hz)
19F-NMR(CDCl3、CFCl3)
δ -75.74(t、J=9Hz)
GC-MS(EI)
m/z 330[M-CH3]+、315、302、288、274、246、225、204、163、135、108、84、56、43
於附攪拌機之四口燒瓶,加入氯仿119g、雙(2,2,2-三氟乙基)氯磷酸酯(純度90.3%)22.6g,於冰-食鹽浴冷卻至0℃。攪拌下,一邊將反應溫度控制在0~5℃一邊從滴下漏斗以3小時滴下2-甲基哌啶17.5g。滴下終了後,恢復至室溫,繼續攪拌12小時。反應終了後,加入2.5%碳酸氫鈉水溶液300g並攪拌後,分餾有機層。從有機層餾除氯仿後,由蒸餾純化,分餾沸點78℃/0.4kPa之餾分,得到無色之液體23g。
由NMR、GC-MS之分析,確認所得到之液體為磷酸雙(2,2,2-三氟乙基)2-甲基吡啶。
1H-NMR(CDCl3、TMS)
δ 4.23~4.33(m、4H)、3.81~3.87(m、1H)、3.28
~3.33(m、1H)、2.96~3.06(m、1H)、1.60~1.70(m、4H)、1.36~1.53(m、2H)、1.24(d、3H、J=8Hz)
13C-NMR(CDCl3、TMS)
δ 122.79(dd、J=11、278Hz)、62.91(dq、J=5Hz、37Hz)、62.75(dq、J=5Hz、38Hz)、47.45(d、J=3Hz)、39.35(d、J=3Hz)、30.52(d、J=4Hz)、25.90(d、J=4Hz)、18.63(s)、16.50(d、J=2Hz)
19F-NMR(CDCl3、CFCl3)
δ -75.76(t、8Hz)、-75.79(t、8Hz)
GC-MS(EI)
m/z 328[M-CH3]+、300、274、245、174、163、97、83、55、41
於附攪拌機之四口燒瓶,加入氯仿120g、雙(2,2,2-三氟乙基)氯磷酸酯(純度90.3%)48g及三乙胺
19g,於冰-食鹽浴冷卻至0℃。攪拌下,一邊將反應溫度控制在0~5℃一邊從滴下漏斗以2小時滴下N-t-丁基甲基胺14g。滴下終了後,恢復至室溫,繼續攪拌12小時。反應終了後,加入2.5%碳酸氫鈉水溶液250g並攪拌後,分餾有機層。從有機層餾除氯仿後,由蒸餾純化,分餾沸點59℃/0.1kPa之餾分,得到無色之液體36g。
由NMR、GC-MS之分析,確認所得到之液體為磷酸雙(2,2,2-三氟乙基)N-t-丁基甲醯胺。
1H-NMR(CDCl3、TMS)
δ 4.33~4.25(m、4H)、2.74(d、3H、J=10)、1.34(s、9H)
13C-NMR(CDCl3、TMS)
δ 123.12(dq、J=11Hz、277Hz)、62.81(dq、J=5Hz、38Hz)、55.69(d、J=3Hz)、31.20(d、J=4Hz)、28.91(d、J=4Hz)
19F-NMR(CDCl3、CFCl3)
δ -75.60(t、J=8Hz)
GC-MS(EI)
m/z 316[M-CH3]+、274、256、216、176、118、96、83、70、56、42、30
於附攪拌機之四口燒瓶,加入氯仿120g、雙(2,2,3,3-四氟丙基)氯磷酸酯(純度93.9%)54g,於冰-食鹽浴冷卻至0℃。攪拌下,一邊將反應溫度控制在0~5℃一邊從滴下漏斗以2小時滴下二異丙基胺33g。滴下終了後,恢復至室溫,繼續攪拌12小時。反應終了後,加入2.5%碳酸氫鈉水溶液250g並攪拌後,分餾有機層。從有機層餾除氯仿後,由蒸餾純化,分餾沸點105℃/0.2kPa之餾分,得到無色之液體44g。
由NMR、GC-MS之分析,確認所得到之液體為磷酸雙(2,2,3,3-四氟丙基)二異丙醯胺。
1H-NMR(CDCl3、TMS)
δ 5.92(tt、1H、J=3Hz、47Hz)、4.39~4.51(m、4H)、3.42~3.57(m、2H)、1.26(d、J=4Hz、12H)
19F-NMR(CDCl3、CFCl3)
δ -137.97(d、2F、J=47Hz)、-125.15(dt、2F、J=3Hz、13Hz)
GC-MS(EI)
m/z 394[M-CH3]+、379
於附攪拌機之四口燒瓶,加入氯仿150g、雙(2,2,2-三氟乙基)氯磷酸酯(純度90.3%)38g及三乙胺15g,於冰-食鹽浴冷卻至0℃。攪拌下,一邊將反應溫度控制在0~5℃一邊從滴下漏斗以2小時滴下N-異丙基-2-甲氧乙基胺14g。滴下終了後,恢復至室溫,繼續攪拌15小時。反應終了後,加入2.5%碳酸氫鈉水溶液200g並攪拌後,分餾有機層。從有機層餾除氯仿後,由蒸餾純化,分餾沸點75℃/0.1kPa之餾分,得到無色之液體32g。
由NMR、GC-MS之分析,確認所得到之液體為磷酸雙(2,2,2-三氟乙基)N-異丙基-2-甲氧基乙醯胺。
1H-NMR(CDCl3、TMS)
δ 4.38~4.28(m、4H)、3.70~3.60(m、1H)、
3.46(t、J=8Hz、2H)、3.35(s)、3.21(td、J=6Hz、14Hz、2H)、1.21(d、7Hz、6H)
13C-NMR(CDCl3、TMS)
δ 123.10(dq、J=11Hz、277Hz)、72.24(s)、62.92(dq、J=4Hz、38Hz)、58.74(s)、49.32(d、J=4Hz)、42.63(d、J=5Hz)、21.60(d、J=3Hz)
19F-NMR(CDCl3、CFCl3)
δ -75.71(t、J=8Hz)
GC-MS(EI)
m/z 346[M-CH3]+、316、300、288、274、220、163、70、59、55、44、43
將於實施例1~實施例6所得到之含氟磷酸酯醯胺由Seta式引火點測定裝置(吉田科學器械(股)製,RT-1型)測定引火點。又,使用錐板型黏度計(BrookField製DV-1PRIME型)測定於20℃之黏度。進而,遵循JIS K0065之方法,測定凝固點。將結果表示於表1。
從表1得知,本發明之含氟磷酸酯醯胺之BTFDIA、BTFINA、BTFMPI、BTFTBMA、BTPDIA及BTFIMEA皆未具有引火點,不燃性且具有高的安全性,又,具有高沸點且低凝固點,液體狀態之溫度範圍寬廣的特徵。
於耐壓玻璃容器加入磷酸酯類2.0g、γ-丁內酯8.0g、水0.5g,並栓緊,以油浴中、125℃下加熱250小時。加熱後,將試驗液以GC及1H-NMR分析,由下式算出水解率。
水解率/%=(水解體/莫耳)/[(磷酸酯類/莫耳)+(水解體/莫耳)]×100
於此作為磷酸酯類,於實施例13使用於實施例1所得到之BTFDIA,於實施例14使用於實施例2所得到之
BTFINA,於實施例15使用於實施例3所得到之BTFMPI,於實施例16使用於實施例4所得到之BTFTBMA,於實施例17使用於實施例5所得到之BTPDIA,於實施例18使用於實施例6所得到之BTFIMEA。於比較例1~比較例4,作為磷酸酯類,各自使用以往所知之磷酸雙(2,2,2-三氟乙基)二甲醯胺、磷酸雙(2,2,2-三氟乙基)二乙醯胺、磷酸參(2,2,2-三氟乙基)及磷酸三甲酯。將結果表示於表2。
從表2,為本發明之含氟磷酸酯醯胺之BTFDIA、BTFINA、BTFMPI、BTFBMA、及BTPDIA及BTFIMEA,相對於以往所知之磷酸酯類明顯具有突出之水解耐性。
於耐壓玻璃容器加入磷酸酯類2.0g、1mol/L氫氧化鉀水溶液2.0g,並栓緊,以油浴中、攪拌下、85℃下加熱50小時。加熱後,將試驗液以GC及1H-NMR分析,由下式算出水解率。
水解率/%=(水解體/莫耳)/[(磷酸酯類/莫耳)+(水解體/莫耳)]×100
其他方式,於耐壓玻璃容器加入磷酸酯類2.0g、1mol/L硫酸水溶液2.0g,並栓緊,以油浴中、攪拌下、85℃下加熱50小時。加熱後,將試驗液以GC及1H-NMR分析,由下式算出水解率。
水解率/%=(水解體/莫耳)/[(磷酸酯類/莫耳)+(水解體/莫耳)]×100
於此作為磷酸酯類,於實施例19使用於實施例1所得到之BTFDIA,於實施例20使用於實施例2所得到之BTFINA,於實施例21使用於實施例3所得到之BTFMPI,於實施例22使用於實施例4所得到之
BTFTBMA,於實施例23使用於實施例5所得到之BTPDIA,於實施例24使用於實施例6所得到之BTFIMEA。於比較例5~比較例8,作為磷酸酯類,各自使用以往所知之磷酸雙(2,2,2-三氟乙基)二甲醯胺、磷酸參(2,2,2-三氟乙基)、磷酸三甲酯及磷酸三乙酯。將結果表示於表3。
從表3,為本發明之含氟磷酸酯醯胺之BTFDIA、BTFINA、BTFMPI、BTFTBMA、及BTPDIA及BTFIMEA,判斷在鹼性及酸性條件之兩者皆具有非常優異之水解耐性。對於此,判斷為以往所知之含氟磷酸酯類之磷酸雙(2,2,2-三氟乙基)二甲醯胺、磷酸參(2,2,2-三氟乙基)、磷酸三甲酯及磷酸三乙酯,在鹼性條件、酸性條件
中之任一者或兩者並未具有充分之水解耐性。
於燒瓶置入多元醇(Polyol)(商品名:MN-3050ONE,三井化學(股)製)100g、矽油(商品名:L-520、日本Unica(股)製)1.2g、錫系觸媒(二月桂酸二丁基錫)0.25g、胺系觸媒(商品名:KaoraizaNo.1,花王(股)製)0.15g、水4.5g、二氯甲烷3.0g、難燃劑(表示於表4之量),以攪拌機攪拌1分鐘使其均勻混合。其次,加入二異氰酸酯(商品名:TDI80/20,三井化學(股)製)55g,攪拌5秒後,將內容物注入剖面為正方形的容器時,立即產生發泡。將此發泡體於30分鐘120℃之爐內使其硬化。從所得到之發泡體切取試料,由MVSS-302進行燃燒試驗。將結果表示於表4。
從表4,為本發明之含氟磷酸酯醯胺之
BTFDIA、BTFMPI及BTPDIA,判斷可用比係傳統難燃劑之磷酸三甲酯更少的添加量將樹脂難燃化。
切取以實施例25~27、比較例10所得到之胺基甲酸乙酯樹脂,於85℃、相對濕度85%之高溫高濕度試驗中保持2週後,由MVSS-302進行燃燒試驗。將結果表示於表5。
從表5得知,本發明之含氟磷酸酯醯胺之BTFDIA、BTFMPI及BTPDIA因為水解耐性優異,故含有此之樹脂經過長期難燃效果依然持續。對於此含有傳統難燃劑之磷酸三甲酯之樹脂,因為於高溫高濕度條件容易水解,長期間持續難燃效果實為困難。
含氟磷酸酯醯胺之介電常數及施主數(donor number)
將於實施例1~實施例6所得到之含氟磷酸酯醯胺各自由阻抗分析儀(東洋Technica(股)製,Versa STAT型)測定於25℃(1kHz)之介電常數。又,遵循J.Organomet.Chem.,108,153,(1976)所記載之方法,從Ph2Si(OH)2混合液之29SiNMR之Si化學位移值算出施主數。又,對於係既知之非水解性之含氟難燃性液體之參(全氟丙基)胺(比較例13)及甲基全氟己醚(比較例14)亦進行同樣之測定。尚且,對於比較例13及14,因為Ph2Si(OH)2皆無法溶解故無法算出施主數。將結果表示於表6。
從表6,為本發明之含氟磷酸酯醯胺之BTFDIA、BTFINA、BTFMPI、BTFTBMA、BTPDIA及BTFIMEA,判斷具有比其他含氟難燃性液體更高之介電常數,又,具有中程度之施主性。
於實施例1所得到之BTFDIA 2g加入表7所示之可燃性液體2g,激烈振動混合並以目視確認混合狀態。同樣使用係既知之含氟難燃性液體之參(全氟丙基)胺及甲基全氟己醚實施同樣之混合試驗。
其次,將混合液體0.1ml浸漬於直徑21mm之石英過濾器,從25mm下方以打火機火燄接近3秒,調查是以繼續燃燒。試驗實施3次,3次皆未滿3秒火燄即消失消炎時記為○,1次以上繼續燃燒3秒以上時記為×。尚且,於比較例21~23,係對於未配合難燃劑之可燃性液體實施上述燃燒試驗者。將結果表示於表7。
從表7,係現有之含氟難燃性液體之參(全氟
丙基)胺及甲基全氟己醚,與經檢討之可燃性液體未均勻混合並分離為二層。對於此,係本發明之含氟磷酸酯醯胺之BTFDIA,判斷與各可燃性液體皆均勻混合。又,判斷配合含氟磷酸酯醯胺之可燃性液體賦予自熄性。
將於實施例1及實施例2所得到之含氟磷酸酯醯胺5m1各自與1,3-二甲基咪唑啉酮(簡稱DMI、沸點226℃、引火點107℃)5ml混合。對於此混合液體,由Seta式引火點測定裝置(吉田科學器械(股)製,RT-1型)測定引火點。同樣將磷酸三乙酯5ml與1,3-二甲基咪唑啉酮5ml混合,測定引火點。將結果表示於表8。
如表8所示,本發明之含氟磷酸酯醯胺因為具有優異之難燃性,藉由對可燃性液體之DMI的配合,判斷可調製係未具有引火點之難燃性液體之非引火性液體。對於此,係比較之磷酸酯類之磷酸三乙酯,因為具有
引火點之可燃性,即使與DMI混合之際亦觀測到引火點,充分難燃化實為困難。
於100ml舒倫克管(Schlenk tube)加入實施例1所得到之BTFDIA 10ml(12.5g)、水10ml,並加入乙酸丁酯1.3g及NaOH0.6g,於70℃加熱並攪拌2小時。反應後,分離為二層,分析各層之際,確認以乙酸丁酯之轉化率100%進行水解反應。尚且,BTFDIA之水解完全未觀察到。
係本發明之含氟磷酸酯醯胺之BTFDIA為未具有引火點之不燃性,且因為對於水解具有非常優異之安定性,藉由使用其作為溶劑,可安全實施關於水解反應等之水的有機合成反應。
於100ml舒倫克管加入實施例1所得到之BTFDIA 20ml(25g),並加入4-n-丙基苯基硼酸1.1g使其溶解,氮氣取代後,於攪拌下添加三苯基膦0.040g、溴苯0.97g、二氯雙(三苯基膦)鈀(II)0.047g及碳酸銫4.0g,於80℃反應4小時。
反應後,將反應液以20ml之水清洗後,將有機層(下層)進行GC分析之際,溴苯之轉化率為74%,確認以選擇率99%生成係交叉耦合生成物之4-n-丙基聯苯。尚且,在GC分析無法觀察到BTFDIA之分解。
本發明之含氟磷酸酯醯胺之BTFDIA因為未具有引火點之不燃性,藉由使用其作為溶劑,可更安全實施交叉耦合反應等之有機合成反應。
於100ml舒倫克管加入實施例1所得到之BTFDIA 10ml(12.5g)及1,3-二甲基咪唑啉酮(DMI)10ml(10.6)g,並加入4-n-丙基苯基硼酸1.1g使其溶解。氮氣取代後,於攪拌下添加三苯基膦0.040g、溴苯0.97g、二氯雙(三苯基膦)鈀(II)0.047g及碳酸銫4.0g,於80℃反應4小時。
反應後,將反應液進行GC分析之際,溴苯之轉化率為79%,確認以選擇率99%生成係交叉耦合生成物之4-n-丙基聯苯。尚且,在GC分析無法觀察到BTFDIA之分解。
如實施例40所示,BTFDIA與DMI之混合液係未具有引火點之難燃性液體(非引火性液體)。據此,藉由使用其作為溶劑,可更安全實施交叉耦合反應等之有機合成反應。
於20ml舒倫克管加入實施例1所得到之BTFDIA 9ml(11g)、苄醇0.15g及氧化白金0.067g,其次,將填充氧氣之氣袋連接於舒倫克管,將系統內以氧氣取代後,於100℃下反應42小時。
反應後,將反應液進行GC分析之際,苄醇之轉化率為62%,確認苯甲醛以選擇性100%生成。尚且,在GC分析無法觀察到BTFDIA之分解。
本發明之含氟磷酸酯醯胺之BTFDIA因為具有優異之氧化耐性,且為不燃性,藉由使用其作為溶劑,可安全實施危險性高之氧化反應。
於50ml舒倫克管加入實施例1所得到之BTFDIA 10ml(12.5g),於25℃之恆溫槽中一邊攪拌,一邊以少量添加LiN(SO2CF3)2(LiTFSI)而求得溶解度。即使對於既知之非水解性之含氟難燃性液體之參(全氟丙基)胺(比較例25)及甲基全氟己醚(比較例26)亦藉由同樣方法調查溶解度。將結果表示於表9。
從表9,係本發明之含氟磷酸酯醯胺之BTFDIA,判斷將作為鋰離子蓄電池及鋰空氣電池等之電解質鹽使用之LiTFSI可以高濃度溶解。據此,本發明之含氟磷酸酯醯胺或包含其之難燃性液體,可作為鋰離子蓄電池及鋰空氣電池等之電解液溶劑使用。
本發明之含氟磷酸酯醯胺,係具有以少添加量使樹脂等之難燃化為可能之等高度難燃性、且因為具有優異水解耐性及良好物性值,在樹脂用難燃劑、可燃性液體用之難燃劑、有機合成用難燃性溶劑、蓄電池電解液用之難燃性溶劑、難燃性液壓油、難燃性潤滑劑、難燃性萃取溶劑及難燃性洗淨劑等之用途極為有用。
Claims (5)
- 一種含氟磷酸酯醯胺,其特徵係以下述一般式(1)表示;
- 如請求項1之含氟磷酸酯醯胺,其係下述一般式(2)所示;
- 一種難燃性樹脂,其係含有如請求項1或2之含氟磷酸酯醯胺。
- 一種難燃性液體,其係含有如請求項1或2之含氟磷酸酯醯胺。
- 一種有機合成用難燃性溶劑,其係由含有如請求項1或2之含氟磷酸酯醯胺或請求項4之難燃性液體所構成。
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