CN102939317B - 聚合物阻燃剂 - Google Patents
聚合物阻燃剂 Download PDFInfo
- Publication number
- CN102939317B CN102939317B CN201180030257.6A CN201180030257A CN102939317B CN 102939317 B CN102939317 B CN 102939317B CN 201180030257 A CN201180030257 A CN 201180030257A CN 102939317 B CN102939317 B CN 102939317B
- Authority
- CN
- China
- Prior art keywords
- polycarbonate
- group
- alcohol
- urethane
- alkyl
- 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.)
- Expired - Fee Related
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- 239000004417 polycarbonate Substances 0.000 claims abstract description 125
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 125
- 238000004519 manufacturing process Methods 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 82
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 47
- 239000003063 flame retardant Substances 0.000 claims description 43
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 43
- 229910052698 phosphorus Inorganic materials 0.000 claims description 41
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 39
- 239000011574 phosphorus Substances 0.000 claims description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 37
- 239000006260 foam Substances 0.000 claims description 37
- -1 methoxyl group Chemical group 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000011496 polyurethane foam Substances 0.000 claims description 30
- 150000002148 esters Chemical class 0.000 claims description 22
- 229920003023 plastic Polymers 0.000 claims description 21
- 239000004033 plastic Substances 0.000 claims description 21
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical group CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 abstract description 23
- 229920002635 polyurethane Polymers 0.000 abstract description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 18
- 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 description 17
- 125000001931 aliphatic group Chemical group 0.000 description 15
- 239000005056 polyisocyanate Substances 0.000 description 15
- 229920001228 polyisocyanate Polymers 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000004970 Chain extender Substances 0.000 description 8
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 7
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229960003742 phenol Drugs 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000005677 organic carbonates Chemical class 0.000 description 5
- 238000006366 phosphorylation reaction Methods 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 125000005587 carbonate group Chemical group 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000026731 phosphorylation Effects 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- OGIXFKHEVNCMPJ-UHFFFAOYSA-N 1-chloro-2-[chloro(phenyl)phosphoryl]benzene Chemical compound ClC1=CC=CC=C1P(Cl)(=O)C1=CC=CC=C1 OGIXFKHEVNCMPJ-UHFFFAOYSA-N 0.000 description 2
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229930182556 Polyacetal Natural products 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical group 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- UXXXZMDJQLPQPH-UHFFFAOYSA-N bis(2-methylpropyl) carbonate Chemical compound CC(C)COC(=O)OCC(C)C UXXXZMDJQLPQPH-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000002576 ketones Chemical group 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- 239000012312 sodium hydride Substances 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种包含至少一个含磷基团的聚碳酸酯,该聚碳酸酯作为阻燃剂的用途,一种在其中使用该包含至少一个含磷基团的聚碳酸酯生产聚氨酯的方法以及可以由该方法得到的聚氨酯。
Description
本发明涉及一种包含至少一个含磷基团的聚碳酸酯,该聚碳酸酯作为阻燃剂的用途,一种通过使用该包含至少一个含磷基团的聚碳酸酯生产聚氨酯的方法以及可以由该方法得到的聚氨酯。
对于为聚合物,尤其是聚氨酯,非常具体的是聚氨酯泡沫提供阻燃性存在许多不同方法。第一种方法是形成外壳以防止火焰到达易燃材料。热水解产物由聚合物基体除去氧并导致在聚合物表面形成碳层。该碳层防止火焰引起位于该层以下的塑料热分解或氧化分解。所用术语为膨胀。含磷化合物以及尤其是有机磷化合物广泛用于在火灾情况下形成碳化外壳。有机磷阻燃剂大多数基于磷酸酯、膦酸酯或亚磷酸酯。
卤代化合物也用作阻燃剂。与含磷阻燃剂相反,这些化合物在火焰的气相内起作用。低反应性卤素自由基在这里清除各种衍生于该聚合物的降解产物的高反应性自由基,由此抑制火焰通过自由基蔓延。含溴阻燃剂在这里特别有效。另一特别有效的阻燃剂是磷酸三氯异丙酯(TCPP),其不仅包含磷酸酯,而且包含卤素氯,因此通过上述两种机理起作用。
然而,卤代阻燃剂,尤其是含溴阻燃剂,由于毒理学、环境和法规原因是不希望的。含卤素的阻燃剂也在火灾情况下增加烟浓度。因此,试图全面避免含卤素的阻燃剂。
已知的无卤素阻燃剂实例是固体阻燃剂如蜜胺或多磷酸铵。这些固体颗粒对聚合物,尤其是对聚氨酯泡沫的性能具有不利影响。固体阻燃剂也尤其在聚氨酯的生产过程中引起问题。例如,聚氨酯的生产优选使用液体原料,包括呈溶液形式的那些。固体颗粒的使用在常用于聚氨酯生产的混合物中导致分离现象,并且批料的寿命因此仅为约1天。此外,固体阻燃剂颗粒磨损例如泡沫装置中的计量单元。所述阻燃剂也对发泡工艺过程中的化学方法具有不利影响且对泡沫性能具有不利影响。
许多液体阻燃剂如磷酸三乙酯(TEP)或乙烷膦酸二乙酯(DEEP)例如导致来自塑料的释放物,使得这些具有令人不爽的臭味。此外,液体阻燃剂对在聚氨酯泡沫生产过程中的发泡反应具有不利影响,并且也对泡沫的性能,例如机械性能具有不利影响。已知的液体阻燃剂也常常用作增塑剂。
为了对抗释放物问题,已经对聚氨酯开发了可结合(einbaubare)阻燃剂。可结合阻燃剂,如Clariant的OP560,通常就异氰酸酯而言具有≤2的官能度且通常降低聚氨酯泡沫的交联密度,由此损害泡沫,尤其是硬质聚氨酯泡沫的性能。
WO 2003104374A1、WO 2004076509A2和WO 2005052031A1描述了膦酸反应的超支化聚丙烯腈、聚丙烯酰胺、聚酰胺和多胺作为防锈剂、润滑剂、纺织品添加剂和阻燃剂的用途。所述化合物不适合用于聚氨酯以及尤其是聚氨酯泡沫,因为含氮结构严重影响泡沫形成方法的催化。
在EP 474076B1中,Bayer AG描述了高度支化的多磷酸酯作为聚碳酸酯的阻燃剂。这些由芳族二羟基化合物和膦酸酯或多磷化合物构成的材料的结构使得它们在用于聚氨酯生产的多元醇中具有不良溶解性,并且这使得难以在聚氨酯中加工这类化合物。
WO 2007066383描述了与磷化合物,如9,10-二氢-9-氧杂-10-磷杂菲10-氧化物反应的超支化聚酯以及这些作为树脂阻燃剂的用途。酯基的低热稳定性和水解稳定性是不利的。
因此,本发明的目的是提供一种也可以用于生产聚氨酯的无卤素阻燃剂。
本发明的另一目的是提供其使用不会在聚合物中,尤其是在聚氨酯中,具体是在聚氨酯泡沫中导致释放物且其在聚合物中,尤其是在聚氨酯中,具体是在聚氨酯泡沫中中的使用不会导致性能,尤其是机械性能受损的阻燃剂。
本发明的另一目的是提供一种不仅可以在热塑性材料的挤出过程中使用而且可以在交联塑料的生产过程中使用的阻燃剂。
本发明的这些目的经由一种包含至少一个含磷基团的聚碳酸酯、该聚碳酸酯作为阻燃剂的用途、一种通过使用该包含至少一个含磷基团的聚碳酸酯生产聚氨酯的方法以及可以由该方法得到的聚氨酯实现。
聚碳酸酯在这了是可以由醇或酚与光气反应或由醇或酚与碳酸二烷基或二芳基酯酯交换而得到的化合物。因此,聚碳酸酯形式上为碳酸的酯。对本发明而言,当该分子具有至少3个,优选至少5个,尤其是至少10个-O-(CO)-O-基团时,使用术语聚碳酸酯。当共聚物具有上述最小数目的-O-(CO)-O-基团时,它们也在下文称为聚碳酸酯。在本发明的一个实施方案中,本发明聚碳酸酯中至少50%,特别优选至少70%,尤其是至少90%的端基为OH基团。
聚碳酸酯的生产是众所周知的且例如广泛描述于Becker/Braun,Kunststoff-Handbuch[塑料手册],第3/1卷,Polycarbonate,Polyacetale,Polyester,Celluloseester[聚碳酸酯、聚缩醛、聚酯、纤维素酯],Carl-Hanser-Verlag,Munich 1992,第118-119页以及“Ullmann′sEncyclopedia of Industrial Chemistry”,第6版,2000年电子版,VerlagWiley-VCH中。
对本发明而言,除了线性聚碳酸酯外,优选使用支化或超支化聚碳酸酯。支化或超支化聚碳酸酯也是已知的且例如描述于WO 9850453和WO2005026234中。
对本发明而言,特别优选使用可以通过使至少一种通式RO[(CO)O]nR的有机碳酸酯(A)与至少一种具有至少3个OH基团的脂族、脂族/芳族或芳族醇(B)反应并消去醇ROH而生产的超支化聚碳酸酯,其中R各自相互独立地为具有1-20个碳原子的直链或支化脂族、芳族/脂族或芳族烃基并且其中基团R也可以相互键合形成环,以及n为1-5的整数,或者通过使光气、双光气或三光气与所述脂族或芳族醇(B)反应并消去氯化氢而生产的超支化聚碳酸酯。反应的进行在这里应使包含OH基团的化合物与光气或碳酸酯的比例给出过量存在的OH基团。此时有机碳酸酯(A)的使用优于光气、双光气或三光气的使用。所有在这里有机碳酸酯(A)与其反应的醇的平均OH官能度优选大于2。
对本发明而言,超支化聚碳酸酯是具有-O-(CO)-O-基团且同时具有结构和分子非均匀性的未交联大分子。一方面,它们可以类似于树枝状聚合物具有衍生于中心分子的结构,但具有非均匀支链链长。另一方面,它们也可以具有线性结构,具有官能侧基,或者呈这两种极端情况的组合形式,可以具有线性和支化部分的分子。对于树枝状聚合物和超支化聚合物的定义,也参见P.J.Flory,J.Am.Chem.Soc.1952,74,2718和H.Frey等,Chem.Eur.J.2000,6,第14期,2499。
在本发明上下文中,“超支化”是指支化度(DB)为10-99.9%,优选20-99%,特别优选20-95%。“树枝状”在本发明上下文中是指支化度为99.9-100%。对于“支化度”的定义,参见H.Frey等,Acta Polym.1997,48,30。
用作通式RO[(CO)O]nR的原料的有机碳酸酯(A)的基团R各自相互独立地为具有1-20个碳原子的直链或支化脂族、芳族/脂族或芳族或杂芳族烃基。两个基团R也可以相互键合形成环。该基团优选为脂族烃基,特别优选具有1-5个碳原子的直链或支化烷基,或取代或未取代的苯基。
碳酸酯A)可以优选为通式RO(CO)OR的简单碳酸酯,从而在此时n为1。
n通常为1-5,优选1-3的整数。
例如碳酸二烷基或二芳基酯可以由脂族、芳脂族或芳族醇,优选一元醇与光气的反应制备。它们也可以通过醇或酚借助CO在贵金属、氧气或NOx存在下的氧化羰基化制备。就碳酸二芳基或二烷基酯的制备方法而言,也参见“Ullmann’s Encyclopedia of Industrial Chemistry”,第6版,2000年电子版,Verlag Wiley-VCH。
合适碳酸酯A)的实例包括脂族、芳族/脂族或芳族碳酸酯,如碳酸亚乙酯、碳酸1,2-或1,3-亚丙酯、碳酸二苯基酯、碳酸二-甲苯基酯、碳酸二-二甲苯基酯、碳酸二萘基酯、碳酸乙基·苯基酯、碳酸二苄基酯、碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二丁酯、碳酸二异丁酯、碳酸二戊酯、碳酸二己酯、碳酸二环己基酯、碳酸二庚酯、碳酸二辛酯、碳酸二癸酯或碳酸二-十二烷基酯。
其中n大于1的碳酸酯A)的实例包括二碳酸二烷基酯,如二碳酸二(叔丁基)酯,或三碳酸二烷基酯,如三碳酸二(叔丁基)酯。
优选使用脂族碳酸酯,尤其是其中基团包含1-5个碳原子的那些,例如碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二丁酯或碳酸二异丁酯,或芳族碳酸酯碳酸二苯基酯。
使有机碳酸酯与至少一种具有至少3个OH基团的脂族或芳族醇(B)或与两种或更多种不同醇的混合物反应。该混合物的平均OH官能度此时大于2,优选大于2.5。
具有至少3个OH基团的化合物实例包括甘油,三羟甲基甲烷,三羟甲基乙烷,三羟甲基丙烷,1,2,4-丁三醇,三(羟基甲基)胺,三(羟基乙基)胺,三(羟基丙基)胺,季戊四醇,双甘油,三甘油,聚甘油,二(三羟甲基丙烷),异氰脲酸三(羟基甲基)酯,异氰脲酸三(羟基乙基)酯,间苯三酚,三羟基甲苯,三羟基二甲基苯,五羟基联苯(phloroglucide),六羟基苯,1,3,5-苯三甲醇,1,1,1-三(4'-羟基苯基)甲烷,1,1,1-三(4’-羟基苯基)乙烷,或糖类,例如葡萄糖,糖衍生物,基于三元或更高级多官能醇和氧化乙烯、氧化丙烯或氧化丁烯的三元或更高级多官能聚醚醇,或其混合物,或聚酯醇。这里特别优选甘油、三羟甲基乙烷、三羟甲基丙烷、1,2,4-丁三醇、季戊四醇,还有基于氧化乙烯或氧化丙烯的其聚醚醇。
这些多官能醇(B)还可以以与二元醇(B’)的混合物使用,条件是所有所用醇的平均总OH官能度大于2。具有2个OH基团的合适化合物的实例包括乙二醇,二甘醇,三甘醇,1,2-和1,3-丙二醇,二丙二醇,三丙二醇,新戊二醇,1,2-、1,3-和1,4-丁二醇,1,2-、1,3-和1,5-戊二醇,己二醇,环戊二醇,环己二醇,环己烷二甲醇,二(4-羟基环己基)甲烷,二(4-羟基环己基)乙烷,2,2-二(4-羟基环己基)丙烷,1,1'-二(4-羟基苯基)-3,3,5-三甲基环己烷,间苯二酚,氢醌,4,4’-二羟基联苯,二(4-羟基苯基)硫化物,二(4-羟基苯基)砜,二(羟基甲基)苯,二(羟基甲基)甲苯,二(对羟基苯基)甲烷,二(对羟基苯基)乙烷,2,2-二(对羟基苯基)丙烷,1,1-二(对羟基苯基)环己烷,二羟基二苯甲酮,基于氧化乙烯、氧化丙烯、氧化丁烯或其混合物的二元聚醚多元醇,聚四氢呋喃,聚己内酯,或基于二醇和二羧酸的聚酯醇。
二醇用于微调聚碳酸酯的性能。若使用二元醇,则二元醇(B’)与至少三元醇(B)的比例由本领域熟练技术人员设定且取决于聚碳酸酯的所需性能。醇(B’)的量基于所有醇(B)和(B’)一起的总量通常为0-39.9mol%。该量优选为0-35mol%,特别优选0-25mol%,非常特别优选0-10mol%。
光气、双光气或三光气与醇或醇混合物的反应通常在消去氯化氢下进行,而碳酸酯与醇或醇混合物得到本发明高官能度高度支化聚碳酸酯的反应在由该碳酸酯分子消去单官能醇或酚下进行。
作为多官能醇(B)和作为双官能醇(B’),优选基于所用醇的总摩尔量使用大于70mol%,特别是大于90mol%的脂族醇,尤其仅使用脂族醇。此外优选本发明的聚碳酸酯在碳酸酯骨架中不包含芳族成分。
由本发明方法形成的高度支化的高官能度聚碳酸酯在反应之后分别具有羟基和/或碳酸酯基团封端以及氨基甲酰氯基团封端,即没有进一步改性。它们在各种溶剂中,例如在水,醇,如甲醇、乙醇、丁醇,醇/水混合物,丙酮,2-丁酮,乙酸乙酯,乙酸丁酯,乙酸甲氧基丙酯,乙酸甲氧基乙酯,四氢呋喃,二甲基甲酰胺,二甲基乙酰胺,N-甲基吡咯烷酮,碳酸亚乙酯或碳酸亚丙酯中具有良好溶解性。
对本发明而言,高官能度聚碳酸酯为除了形成聚合物骨架的碳酸酯基团以外还具有至少3个,优选至少6个,更优选至少10个官能端基或官能侧基的产物。官能基团是碳酸酯基团或氨基甲酰氯基团和/或OH基团,其中OH基团的比例优选为至少50%,特别优选至少70%,尤其是至少90%,在每种情况下基于官能端基或官能侧基的量。原则上讲,官能端基或官能侧基的数目没有上限,但具有非常高官能基团数目的产物可能具有不希望的性能,例如高粘度或不良溶解性。本发明的高官能度聚碳酸酯大多数具有不超过500个官能端基或官能侧基,优选不超过100个官能端基或官能侧基。
在高官能度聚碳酸酯的生产中,包含OH基团的化合物与光气或碳酸酯的比例优选以使得最简单的所得缩合物平均包含一个碳酸酯或氨基甲酰氯基团和不止一个OH基团或一个OH基团和不止一个碳酸酯或氨基甲酰氯基团的方式调节。
得到超支化聚碳酸酯的反应通常在0-300°C,优选0-250°C,特别优选60-200°C,非常特别优选60-160°C的温度下在本体中或在溶液中进行。此时通常可以使用对相应原料呈惰性的任何溶剂。优选使用有机溶剂,如癸烷、十二烷、苯、甲苯、氯苯、二甲苯、二甲基甲酰胺、二甲基乙酰胺或溶剂石脑油。
在一个优选实施方案中,缩合反应在本体中进行。为了加速该反应,可以从反应平衡中除去在反应过程中释放的单官能醇或酚ROH,例如通过蒸馏任选在减压下除去。
若希望通过蒸馏除去,则通常可行的是使用在反应过程中释放在盛行的压力下沸点低于140°C的醇或酚ROH的碳酸酯。
还可以加入催化剂或催化剂混合物以加速该反应。合适的催化剂是催化酯化或酯交换反应的化合物,实例是碱金属氢氧化物、碱金属碳酸盐、碱金属碳酸氢盐,优选钠、钾或铯的氢氧化物、碳酸盐或碳酸氢盐,叔胺,胍类,铵化合物,化合物,有机铝、有机锡、有机锌、有机钛、有机锆或有机铋化合物,还有已知为双金属氰化物(DMC)催化剂的化合物,例如如DE 10138216或DE 10147712所述。
优选使用氢氧化钾,碳酸钾,碳酸氢钾,二氮杂双环辛烷(DABCO),二氮杂双环壬烯(DBN),二氮杂双环十一碳烯(DBU),咪唑类,如咪唑、1-甲基咪唑或1,2-二甲基咪唑,四丁醇钛,四异丙醇钛,氧化二丁基锡,二月桂酸二丁基锡,二辛酸锡,乙酰丙酮锆或其混合物。
催化剂的加入量基于醇或醇混合物的用量通常为50-10000重量ppm,优选100-5000重量ppm。
此外还可以通过加入合适的催化剂或通过选择合适的温度来控制分子间缩聚反应。此外可借助起始组分的组成和停留时间调节超支化聚碳酸酯的平均分子量。
存在多种终止分子间缩聚反应的方式。例如可以将温度降低到反应停止的范围。
此外,可以钝化催化剂,例如在碱性催化剂情况下加入酸性组分,实例是路易斯酸或有机或无机质子酸。
本发明的高官能度聚碳酸酯大多数在0.1毫巴至20巴,优选1毫巴至5巴的压力范围内在分批、半分批或连续操作的反应器或反应器级联中生产。
在一个进一步优选的实施方案中,本发明的聚碳酸酯除了由于反应而固有存在的官能基团外还可以包含其他官能基团。在这里官能化可以在提高分子量的反应过程中发生或者随后发生,即在实际缩聚反应结束之后发生。
若在提高分子量的反应之前或之中加入除了羟基或碳酸酯基团之外还具有其他官能基团或官能单元的组分,则该产物包含具有无规分布的不同于碳酸酯、氨基甲酰氯或羟基的官能团的聚碳酸酯聚合物。
随后的官能化可以通过额外的工艺步骤实现,在该步骤中使所得高官能度、高度支化或超支化聚碳酸酯与可以与该聚碳酸酯的OH和/或碳酸酯或氨基甲酰氯基团反应的合适官能化试剂反应。此外,还可以经由与氧化烯如氧化乙烯、氧化丙烯或氧化丁烯反应而将包含羟基的高官能度聚碳酸酯转化成高官能度聚碳酸酯聚醚多元醇。本发明特别优选的聚碳酸酯在这里不仅为未官能化聚碳酸酯,而且为聚碳酸酯聚醚醇。
本发明的聚碳酸酯包含至少一个含磷基团。该至少一个含磷基团优选为通式(I)的基团:
其中Y为O或S,t为0或1,R1和R2相互独立地为氢、C1-C16烷基、C2-C16链烯基、C2-C16炔基、C1-C16烷氧基、C2-C16链烯氧基、C2-C16炔氧基、C3-C10环烷基、C3-C10环烷氧基、芳基、芳氧基、C6-C10芳基-C1-C16烷基、C6-C10芳基-C1-C16烷氧基、C1-C16-(S-烷基)、C2-C16-(S-链烯基)、C2-C16-(S-炔基)、C3-C10-(S-环烷基)、S-芳基、NHC1-C16烷基、NH芳基、SR3、COR4、COOR5、CONR6R7,并且基团R3、R4、R5、R6和R7相互独立地为C1-C16烷基、C2-C16链烯基、C2-C16炔基、C3-C10环烷基、芳基、芳基-C1-C16烷基、C1-C16-(S-烷基)、C2-C16-(S-链烯基)、C2-C16-(S-炔基)或C3-C10-(S-环烷基),或基团R1和R2与磷原子一起形成环体系。
R1和R2相同或不同,优选为C1-C16烷基、C1-C16烷氧基、C3-C10环烷基、C3-C10环烷氧基、芳基或芳氧基。Y优选为O且t优选为1。
特别优选R1和R2相同,各自为苯基、甲氧基苯基、甲苯基、呋喃基、环己基、苯氧基、乙氧基或甲氧基。
为了生产包含至少一个含磷基团的聚碳酸酯,优选在碱存在下使含有OH基团的聚碳酸酯与通式(II)的化合物反应:
其中X为Cl、Br、I、烷氧基或H,优选Cl,且Y、R1和R2如上所定义。
式(II)化合物是已知的且可市购,或者可以通过使用由文献众所周知的合成途径制备。合成途径例如描述于Science of Synthesis 42(2008);HoubenWeyl E1-2(1982);Houben Weyl 12(1963-1964)]中。
对于通过使含有OH基团的化合物与通式(II)的化合物反应而生产本发明包含至少一个含磷基团的聚碳酸酯存在已知反应。由其中X为Cl、Br或I的式(II)的磷化合物开始的这些反应例如描述于WO 2003062251;Dhawan,Balram;Redmore,Derek,J.Org.Chem.(1986),51(2),179-183;WO 9617853;Kumar,K.Ananda;Kasthuraiah,M.;Reddy,C.Suresh;Nagaraju,C,Heterocyclic Communications(2003),9(3),313-318;Givelet,Cecile;Tinant,Bernard;Van Meervelt,Luc;Buffeteau,Thierry;Marchand-Geneste,Nathalie;Bibal,Brigitte.J.Org.Chem.(2009),74(2),652-659中。
其中X为烷氧基的反应—一个实例是使用甲基膦酸二苯基酯或亚磷酸三苯酯的酯交换—例如描述于RU 2101288和US 2005020800中。
其中X为H的反应—一个实例是使用二苯基氧化膦的反应—例如描述于Tashev,Emil;Tosheva,Tania;Shenkov,Stoycho;Chauvin,Anne-Sophie;Lachkova,Victoria;Petrova,Rosica;Scopelliti,Rosario;Varbanov,Sabi,Supramolecular Chemistry(2007),19(7),447-457中。
合适碱的实例是金属氢化物,如氢化钠,或非亲核胺碱,如三乙胺或Hunig碱,双环胺,如DBU,N-甲基咪唑,或N-甲基吗啉,N-甲基哌啶,吡啶,或取代吡啶,如卢剔啶。特别优选三乙胺和N-甲基咪唑。碱的用量在这里通常为等摩尔的。然而,碱也可以过量使用或者任选用作溶剂。
原料的反应量通常相对于所需官能化程度为化学计量的。可能有利的是相对于多元醇的羟基官能度使用过量磷组分。通过使用小于化学计算量的磷组分可以实现无规的部分磷酸化。所用原料的比例优选应使得本发明包含至少一个含磷基团的聚碳酸酯的磷含量至少为3重量%,特别优选至少5重量%,尤其是至少7重量%。除了式(II)化合物的量外,此时所述磷含量的另一前提是在聚碳酸酯中存在足够的OH基团。这些量可以经由在聚碳酸酯的生产过程中反应的适当进行而调节,尤其经由至少三官能多元醇的比例和反应时间而调节,由此控制转化率并因此控制所得聚碳酸酯的分子量。此时可以使聚碳酸酯中的所有或一部分OH基团与磷组分反应。
在这里生产本发明包含至少一个含磷基团的聚碳酸酯的反应优选在溶剂存在下进行。适合磷酸化反应的溶剂是惰性有机溶剂,如DMSO,卤代烃如二氯甲烷、氯仿、1,2-二氯乙烷或氯苯。进一步合适的溶剂是醚类,如乙醚、甲基叔丁基醚、二丁基醚、二烷或四氢呋喃。进一步合适的溶剂是烃类,如己烷、苯或甲苯。进一步合适的溶剂是腈类,如乙腈或丙腈。进一步合适的溶剂是酮类,如丙酮、丁酮或叔丁基甲基酮。还可以使用溶剂的混合物,并且也可以在无溶剂下操作。
该反应通常在0°C至反应混合物的沸点,优选0-110°C,特别优选室温至110°C的温度下进行。
反应混合物以常规方式后处理,例如经由过滤、与水混合、分离各相以及任选层析提纯粗产物。产物有时呈高粘度油的形式,在减压和轻微升高的温度下对其除去挥发性成分或提纯。所得产物为固体时,提纯方法也可以使用重结晶或浸煮。
另一磷官能化方法包括使本发明的聚碳酸酯与有机磷酰胺,例如亚新戊基N,N-二甲基亚磷酸酰胺(neopentylene N,N-dimethyl-phosphoramidite)反应[参见Nifant'ev,E.E.;Koroteev,M.P.;Kaziev,G.Z.;Koroteev,A.M.;Vasyanina,L.K.;Zakharova,I.S.Russian Journal of GeneralChemistry(Translation of Zhurnal Obshchei Khimii)(2003),73(11),1686-1690]或BINOL N,N-二甲基亚磷酸酰胺[参见Hu,Yuanchun;Liang,Xinmiao;Wang,Junwei;Zheng,Zhuo;Hu,Xinquan,Journal of OrganicChemistry(2003),68(11),4542-4545]。在化学中使用P-亚胺酸酯(P-amidite)作为磷酸化试剂是众所周知的[参见DE 4329533 A1 19950309]。
将本发明包含至少一个含磷基团的聚碳酸酯用作阻燃剂,优选在塑料中用作阻燃剂。塑料在这里包括所有已知塑料。这些包括热塑性模塑组合物,例如聚乙烯(PE),聚丙烯(PP),聚氯乙烯(PVC),聚酰胺(PA),聚对苯二甲酸乙二醇酯(PET),聚对苯二甲酸乙二醇酯二醇(PETG),聚对苯二甲酸丁二醇酯(PBT),聚甲醛(POM),聚碳酸酯(PC),聚甲基丙烯酸甲酯(PMMA)、聚(醚)砜(PES),可热塑性加工的聚氨酯(TPU),聚苯醚(PPO),可发泡和/或已发泡聚丙烯,或所述聚合物中两种或更多种的混合物。本发明的聚碳酸酯也可以用于交联性聚合物中,例如用于聚氨酯如聚氨酯泡沫中。
若本发明包含至少一个含磷基团的聚碳酸酯用于热塑性材料中,包括用于热塑性聚氨酯中,则本发明包含至少一个含磷基团的聚碳酸酯优选包含小于10%,特别优选小于2%的游离OH基团,尤其不包含游离OH基团,在每种情况下基于含磷基团和OH基团的总和。这经由本发明聚碳酸酯与通式(I)的化合物以合适比反应而实现。
对本发明而言,聚氨酯包括所有已知的多异氰酸酯加聚产物。这些包括异氰酸酯和醇的加合物,并且它们也包括可以包含异氰脲酸酯结构、脲基甲酸酯结构、脲结构、碳二亚胺结构、二氮杂环丁酮亚胺(uretonimine)结构和缩二脲结构并且包含其他异氰酸酯加合物的改性聚氨酯。本发明的这些聚氨酯尤其包括固体多异氰酸酯加聚产物,例如热固性树脂,以及基于多异氰酸酯加聚产物的泡沫,例如软质泡沫、半硬质泡沫、硬质泡沫或整体泡沫,还有聚氨酯涂料和粘合剂。对本发明而言,术语聚氨酯还包括包含聚氨酯和其他聚合物的聚合物共混物,还有由所述聚合物共混物制成的泡沫。优选将本发明包含至少一个含磷基团的聚碳酸酯用于生产聚氨酯泡沫。
对本发明而言,聚氨酯泡沫是根据DIN 7726的泡沫。本发明软质聚氨酯泡沫在10%压缩下的压缩应力值或这些泡沫根据DIN 53421/DIN ENISO 604的抗压强度为15kPa或更小,优选1-14kPa,尤其是4-14kPa。本发明半硬质聚氨酯泡沫根据DIN 53421/DIN EN ISO 604在10%压缩下的压缩应力值为大于15kPa至小于80kPa。本发明半硬质聚氨酯泡沫和本发明软质聚氨酯泡沫根据DIN ISO 4590的开孔因子优选大于85%,特别优选大于90%。有关本发明软质聚氨酯泡沫和本发明半硬质聚氨酯泡沫的其他细节在“Kunststoffhandbuch,Band 7,Polyurethane”[塑料手册,第7卷,聚氨酯],Carl Hanser Verlag,第3版,1993,第5章中找到。
本发明硬质聚氨酯泡沫在10%压缩下的压缩应力值大于或等于80kPa,优选大于或等于120kPa,特别优选大于或等于150kPa。此外,硬质聚氨酯泡沫根据DIN ISO 4590的闭孔因子大于80%,优选大于90%。有关本发明硬质聚氨酯泡沫的其他细节在“Kunststoffhandbuch,Band 7,Polyurethane”[塑料手册,第7卷,聚氨酯],Carl Hanser Verlag,第3版,1993,第6章中找到。
对本发明而言,弹性聚氨酯泡沫是根据DIN 7726的如下聚氨酯泡沫,其中这些泡沫在根据DIN 53577短暂形变至其厚度的50%之后10分钟不显示出超过其初始厚度2%的残留形变。该泡沫可以是硬质聚氨酯泡沫、半硬质聚氨酯泡沫或软质聚氨酯泡沫。
聚氨酯整体泡沫是根据DIN 7726的如下聚氨酯泡沫,其由于成型方法而具有密度高于芯中密度的边缘区。在芯和边缘区上平均的总体密度在这里优选大于100g/L。对本发明而言,聚氨酯整体泡沫可以再次为硬质聚氨酯泡沫、半硬质聚氨酯泡沫或软质聚氨酯泡沫。有关本发明聚氨酯整体泡沫的其他细节在“Kunststoffhandbuch,Band 7,Polyurethane”[塑料手册,第7卷,聚氨酯],Carl Hanser Verlag,第3版,1993,第7章中找到。
聚氨酯在这里通过将异氰酸酯(a)与多元醇(b)、根据权利要求1-8中任一项的聚碳酸酯(c)和任选发泡剂(d)、催化剂(e)及其他助剂和添加剂(f)混合以得到反应混合物并使反应完全而得到。
用于生产本发明聚氨酯的多异氰酸酯组分(a)包括所有对生产聚氨酯已知的多异氰酸酯。这些包括由现有技术已知的脂族、脂环族和芳族二-或多官能异氰酸酯,还有其任何所需混合物。实例是二苯基甲烷-2,2′-、2,4′-和4,4′-二异氰酸酯,单体二苯基甲烷二异氰酸酯和具有更大数目的环的二苯基甲烷二异氰酸酯同系物(聚合物MDI)的混合物,异佛尔酮二异氰酸酯(IPDI)及其低聚物,甲苯-2,4-或2,6-二异氰酸酯(TDI)及其混合物,四亚甲基二异氰酸酯及其低聚物,六亚甲基二异氰酸酯(HDI)及其低聚物,萘二异氰酸酯(NDI),以及它们的混合物。
优选使用甲苯-2,4-和/或2,6-二异氰酸酯(TDI)或其混合物,单体二苯基甲烷二异氰酸酯和/或具有更大数目的环的二苯基甲烷二异氰酸酯同系物(聚合物MDI)的混合物及其混合物。其他可能的异氰酸酯例如给于“Kunststoffhandbuch,Band 7,Polyurethane”[塑料手册,第7卷,聚氨酯],Carl Hanser Verlag,第3版,1993,第3.2和3.3.2章中。
多异氰酸酯组分(a)可以以多异氰酸酯预聚物形式使用。所述多异氰酸酯预聚物可以通过使过量的上述多异氰酸酯(成分(a-1))与多元醇(成分(a-2))例如在30-100°C,优选约80°C的温度下反应以得到该预聚物而得到。
多元醇(a-2)对本领域熟练技术人员是已知的且例如描述于“Kunststoffhandbuch,7,Polyurethane”[塑料手册,第7卷,聚氨酯],Carl Hanser Verlag,第3版,1993,第3.1章中。因此,例如所用多元醇也可以包含下面在(b)下所述多元醇。在这里的一个特殊实施方案中,多异氰酸酯预聚物也可以包含本发明包含至少一个含磷基团的聚碳酸酯。
可以使用的多元醇包括所有对于聚氨酯生产已知且具有至少两个反应性氢原子的化合物(b),实例是官能度为2-8且分子量为400-15000的那些。因此,例如可以使用选自聚醚多元醇、聚酯多元醇及其混合物的多元醇。
例如,聚醚醇通过使用含有活性氢的起始剂化合物,例如脂族醇、酚、胺、羧酸、水或基于中性物质的化合物,例如蔗糖、山梨醇或甘露糖醇在使用催化剂下由环氧化物,如氧化丙烯和/或氧化乙烯,或四氢呋喃生产。这里可以提到碱性催化剂或双金属氰化物催化剂,例如如PCT/EP2005/010124、EP 90444或WO 05/090440所述。
例如,聚酯醇由脂族或芳族二羧酸和多官能醇、聚硫醚多元醇、聚酯酰胺、含羟基的聚缩醛和/或含羟基的脂族聚碳酸酯,优选在酯化催化剂存在下生产。其他可能的多元醇例如在“Kunststoffhandbuch,Band 7,Polyurethane”[塑料手册,第7卷,聚氨酯],Carl Hanser Verlag,第3版,1993,第3.1章中给出。
多元醇(b)也包含扩链剂和交联剂。扩链剂和交联剂的摩尔质量小于400g/mol,并且这里对具有两个对异氰酸酯呈反应性的氢原子的分子所用术语是扩链剂,而对具有不止两个对异氰酸酯呈反应性的氢原子的分子所用术语是交联剂。尽管这里可以省略扩链剂或交联剂,但加入扩链剂或交联剂或任选其混合物已经证明对于改性机械性能,例如硬度是有利的。
若使用扩链剂和/或交联剂,则可以使用对于聚氨酯的生产已知的扩链剂和/或交联剂。这些优选为具有对异氰酸酯呈反应性的官能基团的低分子量化合物,实例是甘油、三羟甲基丙烷、二醇和二胺。其他可能的低分子量扩链剂和/或交联剂例如给于“Kunststoffhandbuch,Band 7,Polyurethane”[塑料手册,第7卷,聚氨酯],Carl Hanser Verlag,第3版,1993,第3.2和3.3.2章中。
此外,将本发明包含至少一个含磷基团的聚碳酸酯用作组分(c)。这里对下文也称为聚碳酸酯(c)的包含至少一个含磷基团的聚碳酸酯(c)没有限制且主要取决于待实现的阻燃程度。聚碳酸酯的比例在这里例如可以为0.1-50重量%,优选1-40重量%,特别优选2-30重量%,在每种情况下基于组分(a)-(e)的总重量。成品聚氨酯中的磷含量在这里优选为0.01-10重量%,特别优选0.05-5重量%,尤其是0.1-5重量%,在每种情况下基于聚氨酯的总重量。
希望若聚氨酯呈聚氨酯泡沫形式,则本发明反应混合物优选还包含发泡剂(d)。在这里可以使用对生产聚氨酯已知的任何发泡剂。这些可以包括化学发泡剂和/或物理发泡剂。这些发泡剂例如描述于“Kunststoffhandbuch,Band 7,Polyurethane”[塑料手册,第7卷,聚氨酯],Carl Hanser Verlag,第3版,1993,第3.4.5章中。术语化学发泡剂在这里用于经由与异氰酸酯反应形成气态产物的化合物。这些发泡剂的实例是水和羧酸。术语物理发泡剂在这里用于已经溶解或乳化在聚氨酯生产用原料且在聚氨酯形成条件下蒸发的化合物。例如,这些为烃、卤代烃和其他化合物,例如全氟链烷烃,如全氟己烷、氟氯烃,以及醚、酯、酮、缩醛和/或液体形式的二氧化碳。发泡剂在这里的用量可以根据需要确定。发泡剂的用量优选应使所得聚氨酯泡沫的密度为10-1000g/L,特别优选20-800g/L,尤其是25-200g/L。
所用催化剂(e)可以包括任何常用于聚氨酯生产的催化剂。这些催化剂例如描述于“Kunststoffhandbuch,Band 7,Polyurethane”[塑料手册,第7卷,聚氨酯],Carl Hanser Verlag,第3版,1993,第3.4.1章中。这里所用那些的实例是有机金属化合物,优选有机锡化合物,例如有机羧酸的亚锡盐,例如乙酸亚锡、辛酸亚锡、乙基己酸亚锡和月桂酸亚锡,以及有机羧酸的二烷基锡(IV)盐,例如二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二乙酸二辛基锡,还有羧酸铋,如新癸酸铋(III)、2-乙基己酸铋和辛酸铋,或混合物。其他可能的催化剂是碱性胺催化剂。这些的实例是脒类,如2,3-二甲基-3,4,5,6-四氢嘧啶,叔胺如三乙胺、三丁胺、二甲基苄基胺、N-甲基-和N-乙基-N-环己基吗啉、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四甲基丁二胺、N,N,N',N'-四甲基己二胺、五甲基二亚乙基三胺、四甲基二氨基乙基醚、二(二甲基氨基丙基)脲、二甲基哌嗪、1,2-二甲基咪唑、1-氮杂双环[3.3.0]辛烷,以及优选1,4-二氮杂双环[2.2.2]辛烷,以及链烷醇胺化合物,如三乙醇胺、三异丙醇胺、N-甲基-和N-乙基二乙醇胺以及二甲基乙醇胺。催化剂可以单独或以混合物形式使用。所用催化剂(e)任选包括金属催化剂和碱性胺催化剂的混合物。
特别是若使用较大过量的多异氰酸酯,则可以使用的其他催化剂是三(二烷基氨基烷基)-s-六氢三嗪,优选三(N,N-二甲基氨基丙基)-s-六氢三嗪,四烷基氢氧化铵,如四甲基氢氧化铵,碱金属氢氧化物,如氢氧化钠,以及碱金属醇盐,如甲醇钠和异丙醇钾,还有羧酸的碱金属或铵盐,例如甲酸钾或甲酸铵,或对应的乙酸酯或辛酸酯。
可以使用的催化剂(e)的浓度实例以催化剂或催化剂组合形式基于组分(b)的重量为0.001-5重量%,尤其是0.05-2重量%。
还可以使用助剂和/或添加剂(f)。此时可以使用任何对生产聚氨酯已知的助剂和添加剂。例如可以提到表面活性物质、泡沫稳定剂、泡孔调节剂、脱模剂、填料、染料、颜料、阻燃剂、水解稳定剂以及真菌抑制和细菌抑制物质。这些物质例如描述于“Kunststoffhandbuch,Band 7,Polyurethane”[塑料手册,第7卷,聚氨酯],Carl Hanser Verlag,第3版,1993,第3.4.4和3.4.6-3.4.11章中。
当生产本发明的聚氨酯时,多异氰酸酯(a)、多元醇(b)、聚碳酸酯(c)和任选发泡剂(d)的反应量通常应使得多异氰酸酯(a)的NCO基团与组分(b)、(c)和任选(d)的反应性氢原子总数的当量比为0.75-1.5:1,优选0.80-1.25:1。若泡孔状塑料包含至少一些异氰脲酸酯基团,则多异氰酸酯(a)的NCO基团与组分(b)、(c)以及任选(d)和(f)中反应性氢原子总数的所用比例通常为1.5-20:1,优选1.5-8:1。1:1的比例在这里对应于异氰酸酯指数为100。
当待生产的本发明聚氨酯为热塑性聚氨酯、软质泡沫、半硬质泡沫、硬质泡沫或整体泡沫时,分别在用于生产本发明聚氨酯的具体原料(a)-(f)之间存在非常小的量和质的差异。因此,例如实心聚氨酯的生产不使用发泡剂,而对于热塑性聚氨酯而言所用原料主要是严格双官能的。例如还可以使用具有至少两个反应性氢原子的较高分子量化合物的官能度和链长来改变本发明聚氨酯的弹性和硬度。这类改性对本领域熟练技术人员而言是已知的。
例如,生产实心聚氨酯的原料描述于EP 0989146或EP 1460094中,生产软质泡沫的原料描述于PCT/EP2005/010124和EP 1529792中,生产半硬质泡沫的原料描述于“Kunststoffhandbuch,Band 7,Polyurethane”[塑料手册,第7卷,聚氨酯],Carl Hanser Verlag,第3版,1993,第5.4章中,生产硬质泡沫的原料描述于PCT/EP2005/010955中,而生产整体泡沫的原料描述于EP 364854、US 5506275或EP 897402中。在每种情况下,此时也将聚碳酸酯(c)加入所述文献中所述的原料中。
此时在本发明的一个实施方案中,使用具有小于10%,特别优选小于2%的游离OH基团,尤其是没有游离OH基团的聚碳酸酯(c),在每种情况下基于含磷基团和OH基团的总和。
在本发明的另一实施方案中,聚碳酸酯(c)具有OH基团。此时聚碳酸酯(c)优选就官能度和OH值进行改变以使得仅轻微损害所得聚合物的机械性能,或者优选事实上使其改善。同时,使对加工特性的改变最小化。这类改变例如可以因化合物(c)的OH值和官能度在用于聚氨酯生产的多元醇的OH值和官能度范围内而实现。
若聚碳酸酯(c)具有OH基团,则软质聚氨酯泡沫的生产优选使用OH值为2-100mg KOH/g,特别优选10-80mg KOH/g,尤其是20-50mg KOH/g,OH官能度优选为2-4,特别优选2.1-3.8,尤其是2.5-3.5的化合物作为聚碳酸酯(c)。
若聚碳酸酯(c)具有OH基团,则硬质聚氨酯泡沫的生产优选使用OH值优选为2-800mg KOH/g,特别优选50-600mg KOH/g,尤其是100-400mgKOH/g,OH官能度优选为2-8,特别优选2-6的化合物作为聚碳酸酯(c)。
若聚碳酸酯(c)具有OH基团,则热塑性聚氨酯(TPU)的生产优选使用OH值为2-800mg KOH/g,特别优选10-600mg KOH/g,尤其是20-400mgKOH/g,OH官能度优选为1.8-2.2,特别优选2.9-2.1,尤其是2.0的化合物作为聚碳酸酯(c)。
若使用多异氰酸酯(a)的NCO基团与组分(b)、(c)以及任选(d)和(f)中反应性氢原子总数的比例为1.5-20:1生产多异氰脲酸酯泡沫,则组分(c)的OH官能度优选为2-3,OH值优选为20-800mg KOH/g,特别优选50-600mgKOH/g,尤其是100-400mg KOH/g。
然而,还可以在所有情况下使用任何聚碳酸酯(c)。
优选包含至少一个含磷基团的聚碳酸酯(c)可溶于多元醇(b)中。“可溶”在这里是指在50°C下放置24小时后在比例对应于随后用于生产聚氨酯的量的多元醇组分(b)和组分(c)的混合物中不形成裸眼可见的第二相。溶解性在这里例如经由例如通过使用氧化烯官能化组分(c)或本发明聚碳酸酯而改进。
下面使用实施例说明本发明。
聚碳酸酯的合成
将2400g三羟甲基丙烷×1.2氧化丙烯、1417.5g碳酸二乙酯和0.6g作为催化剂的K2CO3(250ppm催化剂,基于醇的质量)在装有搅拌器、回流冷凝器和内部温度计的4L三颈烧瓶中用作初始料。将该混合物加热至120-140°C并在该温度下搅拌2小时。随着反应时间增加,反应混合物的温度因所释放的乙醇蒸发冷却而降低。然后将回流冷凝器替换为倾斜冷凝器,通过蒸馏除去乙醇,并将反应混合物的温度缓慢升至160°C。此时得到795g乙醇。
分析:
然后通过凝胶渗透色谱法分析反应产物,以二甲基乙酰胺作为洗脱剂和聚甲基丙烯酸甲酯(PMMA)作为标准。测定的值为:
Mn:827g/mol
Mw:1253g/mol
OH值根据DIN 53240测定:
OH值:416mg KOH/g
使用二苯基次膦酰氯()磷酸化聚碳酸酯:
在氩气惰性化下在装有特氟隆搅拌器、回流冷凝器、温度计和滴液漏斗的2L四颈烧瓶中将403.5g来自实施例1的高度支化聚碳酸酯溶于400mL甲苯中。一次加入379.5g三乙胺。将该混合物加热至90°C,并在120分钟内滴加710.5g二苯基次膦酰氯。然后继续在80°C下搅拌该混合物12小时。借助如31P NMR所示的酰氯定量转化控制转化率。
在冷却至室温之后,将反应混合物用1升浓度为10重量%的碳酸氢钠溶液萃取两次并用500mL水萃取一次。有机相在硫酸钠上干燥。在真空除去挥发性成分之后以深黄色油形式分离产物(聚合物1)。
分析:
OH值:2mg KOH/g
通过首先混合除金属催化剂和异氰酸酯外所有组分如表1和表2生产聚氨酯泡沫。然后任选加入金属催化剂并同样通过搅拌掺混。分开称重异氰酸酯,然后加入多元醇组分中。混合该混合物直到反应开始,然后倾入衬有塑料薄膜的金属箱中。该批料的总量在每种情况下为1800g。泡沫过夜完成其反应并通过锯开而分离,得到测试样品。
表1:
表2:
注释:
多元醇1:聚氧丙烯/聚氧乙烯多元醇;OH值:35;官能度:2.7
多元醇2:基于苯乙烯-丙烯腈的接枝多元醇;固体含量:45%;聚氧丙烯-氧乙烯多元醇;OH值:20;官能度:2.7
催化剂体系1:由金属催化剂和胺催化剂制成的标准催化剂体系
催化剂体系2:由甲酸部分封端的胺催化剂
异氰酸酯1:甲苯-2,4-和2,6-二异氰酸酯的混合物
HB多元醇1:部分与氯代磷酸二苯基酯(chlordiphenylphosphat)反应的超支化聚碳酸酯;OH值:12;6.6重量%P
HB多元醇2:与氯代磷酸二苯基酯反应的超支化聚碳酸酯;OH值:0;4.8重量%P
HB多元醇3:部分与氯代二苯基次膦酰氯()反应的超支化聚碳酸酯;OH值:2;9.1重量%P
HB多元醇4:部分与氯代二苯基次膦酰氯反应的超支化聚碳酸酯;OH值:19;9.0重量%P
HB多元醇5:部分与氯代二苯基氧化膦反应的超支化聚碳酸酯;OH值:43;7.7重量%P
TPP:磷酸三苯酯;9.5重量%P(Chemtura)
BDP:双酚A二(磷酸二苯酯)/磷酸三苯酯)bisphenol Abis(diphenylphosphat)/triphenylphosphat);8.9-9重量%P(Supresta)
6:二(2-羟基乙基氨基)甲烷膦酸二乙酯;12重量%P(Supresta)
使用下列方法测定性能:
密度,kg/m3:DIN EN ISO 845
抗压强度,kPa:DIN EN ISO 3386
回弹性,%:DIN EN ISO 8307
空气渗透性,dm3/s:DIN EN ISO 7231
阻燃性:California TB 117A
由该表可见本发明不含卤素的软质聚氨酯泡沫呈现非常好的阻燃性,与使用具有类似或甚至更高磷含量的市售样品的对比泡沫类似或更好。还发现泡沫的机械性能改善而不是受损,尽管存在可结合阻燃剂。
对比例4表明使用市售样品并不一定如此,此时弹性显著受损。在低密度下,本发明结构比对比例3的市售样品具有更好效果,但是磷含量相同或轻微更高。尽管使用磷酸三苯酯作为阻燃剂的聚氨酯(对比例2)就阻燃性和机械性能而言呈现与超支化的含磷聚碳酸酯相同的质量,但低分子量化合物此时显著促进来自泡沫的释放物。若将表2的结果与使用最广泛使用的市售阻燃剂(磷酸三(氯异丙基)酯(TCPP))获得的结果比较,则可见结果完全相当。使用磷酸三氯异丙酯的泡沫此时具有相同磷含量,但还包含1.7%氯。因此,这不是实现阻燃性的无卤方法。结果表明磷酸化的超支化聚碳酸酯是替代卤代材料磷酸三(氯异丙基)酯的合适阻燃剂。惊人的是,尽管不含氯,此时仍无需提高磷含量以实现相同效果。
也如表3生产硬质聚氨酯泡沫:
表3
所用原料如下:
多元醇3:邻苯二甲酸酐和二甘醇的酯化产物,OHN=220mg KOH/g
多元醇4:聚乙二醇,OHN=200mg KOH/g
稳定剂1:B 8467(Evonik Goldschmidt GmbH)
HB多元醇5:部分与氯代磷酸二苯基酯反应的超支化聚碳酸酯;OHN=19mg KOH/g,磷含量10.3重量%
发泡剂1:正戊烷
发泡剂2:甲酸(85重量%)
发泡剂3:水和二丙二醇的混合物,重量比为3:2
催化剂1:甲酸钾(36重量%,在乙二醇中)
催化剂2:二(2-二甲基氨基乙基)醚(70重量%,在二丙二醇中)
异氰酸酯1:聚合MDI
指压干时间在这里定义为混合方法开始至在棒等接触泡沫表面时几乎觉察不到粘性的时刻之间的时段。指压干时间为氨基甲酸酯反应的有效性的度量。
BKZ5测试:根据Vereinigung Kantonaler Feuerversicherungen[州火灾保险协会]发布的Swiss测试和分类标准测定建筑材料可燃性的焰色试验。
硬质PU泡沫通过将所用多元醇、稳定剂、阻燃剂、催化剂和发泡剂混合,然后将这些与异氰酸酯混合并发泡得到硬质PU泡沫而生产。
由表3可见当使用本发明的含磷聚碳酸酯时,可以通过BKZ5测试而对泡沫体系的反应性没有任何影响。然而,不象常规市售阻燃剂如TCPP,本发明阻燃剂不含卤素。
Claims (28)
1.一种包含至少一个含磷基团的聚碳酸酯,其可以通过使含有OH基团的聚碳酸酯与如下通式的化合物反应而得到:
其中X为Cl、Br、I、烷氧基或H,
Y为O或S,
t为0或1,
R1和R2相互独立地为氢、C1-C16烷基、C2-C16链烯基、C2-C16炔基、C1-C16烷氧基、C2-C16链烯氧基、C2-C16炔氧基、C3-C10环烷基、C3-C10环烷氧基、芳基、芳氧基、C6-C10芳基-C1-C16烷基、C6-C10芳基-C1-C16烷氧基、C1-C16-(S-烷基)、C2-C16-(S-链烯基)、C2-C16-(S-炔基)、C3-C10-(S-环烷基)、S-芳基、NHC1-C16烷基、NH芳基、SR3、COR4、COOR5或CONR6R7,并且基团R3、R4、R5、R6和R7相互独立地为C1-C16烷基、C2-C16链烯基、C2-C16炔基、C3-C10环烷基、芳基、芳基-C1-C16烷基、C1-C16-(S-烷基)、C2-C16-(S-链烯基)、C2-C16-(S-炔基)或C3-C10-(S-环烷基),或者基团R1和R2与磷原子一起形成环,并且其中所述聚碳酸酯为超支化聚碳酸酯。
2.根据权利要求1的聚碳酸酯,其中R1与R2相同,且R1和R2各自为甲氧基苯基、甲苯基、环己基、苯基、苯氧基、乙氧基或甲氧基。
3.根据权利要求1的聚碳酸酯,其包含至少3重量%磷。
4.根据权利要求2的聚碳酸酯,其包含至少3重量%磷。
5.根据权利要求1的聚碳酸酯,其不包含OH基团。
6.根据权利要求2的聚碳酸酯,其不包含OH基团。
7.根据权利要求3的聚碳酸酯,其不包含OH基团。
8.根据权利要求4的聚碳酸酯,其不包含OH基团。
9.根据权利要求1的聚碳酸酯,其包含至少一个OH基团。
10.根据权利要求2的聚碳酸酯,其包含至少一个OH基团。
11.根据权利要求3的聚碳酸酯,其包含至少一个OH基团。
12.根据权利要求4的聚碳酸酯,其包含至少一个OH基团。
13.根据权利要求9的聚碳酸酯,其OH值为2-800mg KOH/g。
14.根据权利要求10的聚碳酸酯,其OH值为2-800mg KOH/g。
15.根据权利要求11的聚碳酸酯,其OH值为2-800mg KOH/g。
16.根据权利要求12的聚碳酸酯,其OH值为2-800mg KOH/g。
17.根据权利要求1-16中任一项的聚碳酸酯,其包含氧化丙烯单元和/或氧化乙烯单元。
18.根据权利要求1-16中任一项的聚碳酸酯,其中至少三元醇(B)和任选二元醇(B')用于生产所述聚碳酸酯,其中二元醇(B')的比例基于至少三元醇(B)和二元醇(B')的总重量为0-39.9重量%。
19.根据权利要求17的聚碳酸酯,其中至少三元醇(B)和任选二元醇(B')用于生产所述聚碳酸酯,其中二元醇(B')的比例基于至少三元醇(B)和二元醇(B')的总重量为0-39.9重量%。
20.根据权利要求1-16中任一项的聚碳酸酯,其在碳酸酯骨架中不包含芳族成分。
21.根据权利要求17的聚碳酸酯,其在碳酸酯骨架中不包含芳族成分。
22.根据权利要求18的聚碳酸酯,其在碳酸酯骨架中不包含芳族成分。
23.根据权利要求19的聚碳酸酯,其在碳酸酯骨架中不包含芳族成分。
24.根据权利要求1-23中任一项的聚碳酸酯作为阻燃剂的用途。
25.一种塑料,包含权利要求1-23中任一项的聚碳酸酯。
26.一种生产聚氨酯的方法,包括将异氰酸酯(a)与多元醇(b)、根据权利要求1-23中任一项的聚碳酸酯(c)和任选发泡剂(d)、催化剂(e)及其他助剂和添加剂(f)混合以得到反应混合物并使反应完全以得到所述聚氨酯。
27.根据权利要求26的生产聚氨酯的方法,其中所述聚氨酯为聚氨酯泡沫。
28.可以根据权利要求26或27得到的聚氨酯。
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Publication number | Priority date | Publication date | Assignee | Title |
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US8987357B2 (en) | 2011-05-27 | 2015-03-24 | Basf Se | Thermoplastic molding composition |
WO2013017417A1 (de) | 2011-07-29 | 2013-02-07 | Basf Se | Polymeres flammschutzmittel |
CN102558542B (zh) * | 2011-12-09 | 2014-06-11 | 东南大学 | 一种蔗糖型聚醚碳酸酯多元醇的制备方法 |
US9580540B2 (en) | 2011-12-20 | 2017-02-28 | Adhesys Medical Gmbh | Hydroxy amino polymer and use thereof in polyurea/polyurethane tissue adhesives |
CN104640909B (zh) * | 2012-09-20 | 2018-11-13 | 巴斯夫欧洲公司 | 超支化磷酸酯 |
DE102012023513A1 (de) * | 2012-11-30 | 2014-06-05 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymere Flammschutzmittel, Verfahren zu deren Herstellung und flammgeschützte Polymersysteme |
JP2016521269A (ja) * | 2013-04-16 | 2016-07-21 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | リン含有難燃剤 |
CN105542140A (zh) * | 2016-01-07 | 2016-05-04 | 甘肃银光聚银化工有限公司 | 一种含磷阻燃聚碳酸酯的制备方法及其制备的含磷阻燃聚碳酸酯 |
EP3385295A1 (de) * | 2017-04-05 | 2018-10-10 | Covestro Deutschland AG | Flammgeschützte phosphorfunktionelle polyethercarbonatpolyole und verfahren zu deren herstellung |
WO2018191612A1 (en) * | 2017-04-14 | 2018-10-18 | Sabic Global Technologies B.V. | Synthesis of a phosphorous containing monomer and the incorporation in polycarbonate by interfacial polymerization thereof |
EP3606976B1 (en) * | 2017-07-24 | 2022-03-30 | ICL-IP America Inc. | Reactive flame retardants for flexible polyurethane foams |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU551979B2 (en) | 1982-03-31 | 1986-05-15 | Shell Internationale Research Maatschappij B.V. | Epoxy polymerisation catalysts |
DE3835193A1 (de) | 1988-10-15 | 1990-04-19 | Basf Ag | Verfahren zur herstellung von formkoerpern mit einer verdichteten randzone und einem zelligen kern, vorzugsweise schuhsohlen |
DE4113157A1 (de) | 1990-09-06 | 1992-03-12 | Bayer Ag | Hochverzweigte polyphosphonate auf melamin-basis |
US5506275A (en) | 1995-05-15 | 1996-04-09 | Basf Corporation | 1,1,1,2-tetrafluoroethane as a blowing agent in integral skin polyurethane shoe soles |
DE4329533A1 (de) | 1993-09-02 | 1995-03-09 | Schneider Manfred Prof Dr | Dibenzyl-N,N-dialkylphosphorigsäureamide als Phosphorylierungsreagenzien sowie ein Verfahren zu ihrer Herstellung |
WO1996017853A1 (en) | 1994-12-07 | 1996-06-13 | Akzo Nobel N.V. | Process for making hydrocarbyl (dihydrocarbyl) phosphates |
US20030158277A1 (en) * | 1995-07-03 | 2003-08-21 | Blanpied Robert H. | Method of producing rigid foams and products produced therefrom |
RU2101288C1 (ru) | 1996-01-04 | 1998-01-10 | Волгоградское акционерное общество открытого типа "Химпром" | Способ получения дифенил-2-этилгексилфосфита |
DE19618392A1 (de) | 1996-05-08 | 1997-11-13 | Basf Ag | Verfahren zur Herstellung von elastischen Polyurethan-Formkörpern mit kompakter Oberfläche und zelligem Kern |
GB2324797A (en) | 1997-05-02 | 1998-11-04 | Courtaulds Coatings | Hyperbranched polymers |
JP4147637B2 (ja) | 1998-09-21 | 2008-09-10 | 東ソー株式会社 | ポリウレタン製造用の触媒 |
DE10122495A1 (de) * | 2001-03-26 | 2002-10-10 | Bayer Ag | Schmelzepolycarbonat mit verbesserter Hydrolysebeständigkeit |
DE10138216A1 (de) | 2001-08-03 | 2003-02-20 | Bayer Ag | Aliphatische Polycarbonathomo- und -copolymere durch DMC-Katalyse |
DE10147712A1 (de) | 2001-09-27 | 2003-04-17 | Basf Ag | Verfahren zur Herstellung aliphatischer Polycarbonate |
EP2166013B1 (en) | 2001-10-04 | 2018-01-24 | Akzo Nobel N.V. | Oligomeric, hydroxy-terminated phosphonates |
JP2003206350A (ja) * | 2002-01-15 | 2003-07-22 | Nippon Chem Ind Co Ltd | 含リンポリカーボネート、その製造方法及び樹脂組成物 |
AR038161A1 (es) | 2002-01-24 | 2004-12-29 | Basf Ag | Procedimiento para separar acidos de mezclas de reaccion quimicas con la ayuda de liquidos ionicos |
FR2840622B1 (fr) | 2002-06-11 | 2004-07-23 | Rhodia Chimie Sa | Composition pour le traitement des articles en fibres textiles comprenant un polymere dendritique |
FR2851565B1 (fr) | 2003-02-26 | 2005-04-01 | Commissariat Energie Atomique | Dendrimeres phosphores, leur procede de preparation et leur utilisation pour l'extraction des actinides et des lanthanides |
EP1460094B1 (en) | 2003-03-18 | 2007-01-31 | Tosoh Corporation | Catalyst composition for production of a polyurethane resin, and method for producing a polyurethane resin |
DE502004009535D1 (de) | 2003-09-12 | 2009-07-09 | Basf Se | Hochfunktionelle, hoch- oder hyperverzweigte polycarbonate sowie deren herstellung und verwendung |
DE10352876A1 (de) | 2003-11-10 | 2005-06-23 | Basf Ag | Verfahren zur Herstellung von Polyurethan-Weichschaumstoffen |
FR2862651B1 (fr) | 2003-11-24 | 2006-03-31 | Rhodia Cons Spec Ltd | Nouveaux dendrimeres a terminaisons bisphosphoniques et derives, leur procede de preparation et leur utilisation |
DE102004013408A1 (de) | 2004-03-18 | 2005-10-06 | Basf Ag | Polyetheralkohole und Verfahren zur Herstellung von Polyetheralkoholen zur Polyurethansynthese |
US8552079B2 (en) * | 2005-12-01 | 2013-10-08 | Bayer Materialscience Llc | Water-blown, flame retardant rigid polyurethane foam |
WO2007066383A1 (ja) | 2005-12-06 | 2007-06-14 | Toyo Boseki Kabushiki Kaisha | リン含有ハイパーブランチポリマーおよび難燃性樹脂組成物 |
JP2007161928A (ja) * | 2005-12-15 | 2007-06-28 | Mitsubishi Chemicals Corp | 超分岐ポリカーボネート及びその製造方法 |
DE102006012990A1 (de) * | 2006-03-22 | 2007-09-27 | Bayer Materialscience Ag | Flammgeschützte schlagzähmodifizierte Polycarbonat-Zusammensetzungen |
KR101503947B1 (ko) * | 2007-07-04 | 2015-03-18 | 우베 고산 가부시키가이샤 | 인-함유 폴리카르보네이트 폴리올, 이의 제조 방법 및 인-함유 폴리카르보네이트 폴리우레탄 |
-
2010
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---|
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CN102939317A (zh) | 2013-02-20 |
BR112012029455A2 (pt) | 2017-03-07 |
ES2462169T3 (es) | 2014-05-22 |
KR101453643B1 (ko) | 2014-10-22 |
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