EP2951227A1 - Verfahren zur polymerisation von -caprolactam - Google Patents
Verfahren zur polymerisation von -caprolactamInfo
- Publication number
- EP2951227A1 EP2951227A1 EP14701191.0A EP14701191A EP2951227A1 EP 2951227 A1 EP2951227 A1 EP 2951227A1 EP 14701191 A EP14701191 A EP 14701191A EP 2951227 A1 EP2951227 A1 EP 2951227A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radical
- caprolactam
- branched
- cio
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000000379 polymerizing effect Effects 0.000 title abstract 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000012041 precatalyst Substances 0.000 claims abstract description 20
- -1 propylene- Chemical class 0.000 claims description 47
- 238000006116 polymerization reaction Methods 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 20
- 150000003254 radicals Chemical class 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- 150000007942 carboxylates Chemical class 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 claims description 9
- 238000010107 reaction injection moulding Methods 0.000 claims description 9
- 239000002841 Lewis acid Substances 0.000 claims description 8
- 150000007517 lewis acids Chemical class 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000004753 textile Substances 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 7
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 150000005840 aryl radicals Chemical class 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000001721 transfer moulding Methods 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims description 2
- GJWHXWMUGWZNTO-UHFFFAOYSA-N 2,2-dimethylpropane Chemical compound [CH2]C(C)(C)C GJWHXWMUGWZNTO-UHFFFAOYSA-N 0.000 claims description 2
- NJQFCQXFOHVYQJ-PMACEKPBSA-N BF 4 Chemical compound C1([C@@H]2CC(=O)C=3C(O)=C(C)C4=C(C=3O2)[C@H](C(C)C)C2=C(O4)C(C)=C(C(C2=O)(C)C)OC)=CC=CC=C1 NJQFCQXFOHVYQJ-PMACEKPBSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000000 cycloalkoxy group Chemical group 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
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Chemical group 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000004104 aryloxy group Chemical group 0.000 claims 1
- 238000010348 incorporation Methods 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 108090000623 proteins and genes Proteins 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 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 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000006239 protecting group Chemical group 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XXHOUENSQJMAET-UHFFFAOYSA-N 1,3-dicyclohexyl-1,3-diazinan-1-ium-2-carboxylate Chemical compound [O-]C(=O)C1N(C2CCCCC2)CCC[NH+]1C1CCCCC1 XXHOUENSQJMAET-UHFFFAOYSA-N 0.000 description 4
- UQLWWTIXIOMHGO-UHFFFAOYSA-N 1,3-dicyclohexylimidazol-1-ium-2-carboxylate Chemical compound [O-]C(=O)C=1N(C2CCCCC2)C=C[N+]=1C1CCCCC1 UQLWWTIXIOMHGO-UHFFFAOYSA-N 0.000 description 4
- CJDLCKAHUNULNN-UHFFFAOYSA-N 1,3-ditert-butylimidazol-1-ium-2-carboxylate Chemical compound CC(C)(C)N1C=C[N+](C(C)(C)C)=C1C([O-])=O CJDLCKAHUNULNN-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 2
- OTPDWCMLUKMQNO-UHFFFAOYSA-N 1,2,3,4-tetrahydropyrimidine Chemical class C1NCC=CN1 OTPDWCMLUKMQNO-UHFFFAOYSA-N 0.000 description 2
- SEBGKIFYWXLMPU-UHFFFAOYSA-N 1,3-di(propan-2-yl)-1,3-diazinan-1-ium-2-carboxylate Chemical compound CC(C)N1CCC[NH+](C(C)C)C1C([O-])=O SEBGKIFYWXLMPU-UHFFFAOYSA-N 0.000 description 2
- ARVVOEJBGNPOFH-UHFFFAOYSA-N 1,3-di(propan-2-yl)imidazol-1-ium-2-carboxylate Chemical compound CC(C)N1C=C[N+](C(C)C)=C1C([O-])=O ARVVOEJBGNPOFH-UHFFFAOYSA-N 0.000 description 2
- LLYASHBWCNIKEH-UHFFFAOYSA-N 1,3-ditert-butylimidazolidin-1-ium-2-carboxylate Chemical compound CC(C)(C)N1CC[NH+](C(C)(C)C)C1C([O-])=O LLYASHBWCNIKEH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001409 amidines Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- SUEYDWMINMMAOF-UHFFFAOYSA-N (2,4,6-trimethylphenyl) 4,5-dihydro-1h-imidazole-2-carboxylate Chemical compound CC1=CC(C)=CC(C)=C1OC(=O)C1=NCCN1 SUEYDWMINMMAOF-UHFFFAOYSA-N 0.000 description 1
- SOZFIIXUNAKEJP-UHFFFAOYSA-N 1,2,3,4-tetrafluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1F SOZFIIXUNAKEJP-UHFFFAOYSA-N 0.000 description 1
- LRANPJDWHYRCER-UHFFFAOYSA-N 1,2-diazepine Chemical class N1C=CC=CC=N1 LRANPJDWHYRCER-UHFFFAOYSA-N 0.000 description 1
- HOOKQVAAJVEFHV-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-1-ium;chloride Chemical compound [Cl-].CC1=CC(C)=CC(C)=C1N1C[NH+](C=2C(=CC(C)=CC=2C)C)CC1 HOOKQVAAJVEFHV-UHFFFAOYSA-N 0.000 description 1
- RKZIPFOHRUCGGS-UHFFFAOYSA-N 4,5-dihydroimidazole-1-carboxylic acid Chemical class OC(=O)N1CCN=C1 RKZIPFOHRUCGGS-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 101000957333 Homo sapiens Muscleblind-like protein 3 Proteins 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 102100038751 Muscleblind-like protein 3 Human genes 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000006657 acyloin condensation reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009745 resin transfer moulding Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
- C08G69/20—Anionic polymerisation characterised by the catalysts used
Definitions
- the invention relates to a process for the polymerization of ⁇ -caprolactam using precatalysts in the form of protected N-heterocyclic carbenes.
- Lactams are converted to polyamides on a million-ton scale worldwide.
- Important monomers are in particular ⁇ -caprolactam ( ⁇ -CLA) and laurolactam for the preparation of PA6 or PA12.
- the polymerization can be carried out in principle by three routes: cationic, hydrolytic or anionic polymerization. The last two procedures are technically used.
- hydrolytic process a defined amount of water (5-10%) is added and a portion of the monomer hydrolyzed to the open-chain amino acid. Propagation then occurs by ring opening and by condensation of the amino acids.
- the reaction times are usually several hours (12-24 h) at temperatures well above 200 ° C.
- the anionic polymerization can be conducted at lower temperatures.
- bases for example, alkali metals, amides or Grignard compounds have been used.
- the choice of base is important: weak bases generate little lactanion since the pK s value of ⁇ -CLA is 27.2 (in DMSO at 25 ° C). Strong bases can lead to side reactions (for example, protons of the CH unit can alpha-constantly abstract to carbonyl).
- the mechanism runs on the so-called "activated monomer" (lactamanion). Anionic polymerizations proceed very fast, typically within a few minutes. Usually isocyanates or N-acyl lactams are added as activators.
- Polyamides can z. B. either with the screw-injection molding technique or as cast polyamides z. B. be processed by the reaction injection molding (RIM process).
- RIM process reaction injection molding
- molten polymer is filled under pressure into molds
- monomeric melt is filled without pressure into molds.
- the polymerization then takes place.
- injection molding processes are characterized by shorter tool life.
- cast polyamides can be used for more complex components because the monomer melt is a significant shows better flow behavior than the polymer melt (lower melting point, lower viscosity).
- N-heterocyclic carbenes have been known for some time as polymerization catalysts.
- epoxides, terephthalaldehyde or acrylates can be polymerized.
- the prior art according to DE 10 2006 038 934 AI should be mentioned, in particular on imidazolium umcarboxylat adducts and a method for the use of catalytic amounts of imidazolium and Imidazoliniumcarboxylat adducts in the acyloin reaction of aldehydes for the preparation of hydroxyketones.
- the object of the invention was to propose a process for the polymerization of ⁇ -caprolactam, in which readily manageable catalysts can be used.
- the catalyst and ⁇ -caprolactam should form a directly usable, high-performance one-component system which can be polymerized in a targeted temperature range in a targeted manner, wherein the polymerization temperature should be greater than the melting temperature of the ⁇ -caprolactam / catalyst mixture, in particular also Reaction Injection Molding (RIM) or Resin Transfer Molding (RTM).
- RIM Reaction Injection Molding
- RTM Resin Transfer Molding
- catalysts for the mentioned polymerization proposed by ⁇ -caprolactam which are significantly more active compared to known catalysts.
- the above object is achieved by a process for the polymerization of ⁇ -caprolactam, which is initiated and carried out in the presence of precatalysts in the form of protected N-heterocyclic carbenes, wherein said precatalysts are selected from the following compounds: 1.) Compounds of general formula (I): -D
- Ri is a straight or branched Ci-Cio-alkyl, in particular, dC 7 alkyl a linear or branched C 2 -C 0 alkenyl, in particular C 2 -C 7 alkenyl, a C 3 -C 2 cycloalkyl, in particular C 3 -C 6 cycloalkyl, a geradket term or branched C 6 -Cioo-polyoxyalkylene, in particular C 6 -C 3 o polyoxyalkylene, a C 5 -C 0 aryl, or C 5 -C 0 - hetaryl radical,
- R 2 is a straight or branched Ci-Cio-alkoxy, in particular Ci-C 7 - alkoxy, C 5 -C 2 cycloalkoxy, especially C 5 -C 6 cycloalkoxy, C 6 linear or branched-polyoxyalkylene -Cioo -, in particular C 6 -C 3 O-polyoxyalkylene, C 5 -C 0 - aryloxy, linear or branched Ci-Cio-perfluoroalkyl, in particular Ci- C 7 perfluoroalkyl, linear or branched Ci-Cio-perchloroalkyl , in particular C 1 -C 7 perchloroalkyl, straight-chain or branched partially fluorinated C 1 -C 10 -alkyl, in particular partially fluorinated C 1 -C 7 -alkyl, straight-chain or branched partially chlorinated C 1 -C 10 -alkyl, in particular partially fluorin
- X is oxygen, sulfur or -NR 3 '-, wherein R 3 ' has the meaning given above for Ri, or
- R 4 is the one in formula (I) to Ri, X 'to X, A' to A and D 'have the meaning given to D, or 3.) compounds of general formula III with Lewis acids, in particular the base of magnesium, calcium, yttrium, lanthanum, titanium, zirconium, manganese, iron, cobalt, zinc, aluminum, tin, bismuth or boron cations with anions from the fluoride series, chloride, bromide, sulfate, hydrogen sulfate, Trif- luormethansulfonat, methanesulfonate, benzenesulfonate, BF 4 ", PF 6", SbF 6, para-toluene sulfonate, trifluoroacetate, carboxylate (Ci-Cio-alkyl), (C 3 -C 0 cycloalkyl) carboxylate, (C 2 -C 0 alkenyl) carboxylate, (C
- R 5 has the formula (I) above in Ri, X 'to X, A' to A and D 'have the meaning given to D.
- These compounds can be used individually or in a mixture of more than one of these compounds.
- a precatalyst is understood as meaning a compound which is in a form which is the monomer, a monomer mixture or a monomer solution before the initiation of the polymerization and the actual polymerization. is added. Under the polymerization conditions, the precursor forms the actual catalyst, a free carbene.
- the above process is preferably characterized in that the straight-chain or branched C 1 -C 10 -alkyl radical is a methyl, ethyl, n-propyl, isopropyl, tert-butyl or neopentyl radical which C 3 -C 2 -cycloalkyl radical is a cyclohexyl radical
- the C 5 -C 0 aryl radical represents a phenyl, 2,6-dimethylphenyl, 2,6-Diisopropylphenyl- or mesityl radical.
- An equally advantageous embodiment of the method according to the invention is represented by the fact that the straight-chain or branched C 1 -C 10 -alkoxy radical is a methoxy, ethoxy, isopropoxy, tert-butyloxy, isobutoxy or 2-ethylhexyloxy radical radical
- the C 5 -C 0 aryloxy radical means a phenyloxy radical, C 5 -C 2 cycloalkoxy radical a cyclohexyloxy group
- the Ci-Cio perfluoroalkyl radical is a CF 3 group
- the Ci Cio-perchloroalkyl radical a CCI 3 - radical
- the perfluorinated C 5 -C 0 aryl radical represents a pentaflu
- the process according to the invention is particularly suitably configured by using the concretely designated precatalysts described below, represented below by the formulas (Ih), (Im), (Io), (Ib) and (Iq):
- the syntheses of the precatalysts are in principle known from the literature (Iglesias, M., Beetstra, D. X; Knight, J. C; Ooi, LL; Stasch, A.; Coles, S.; Male, L.; Hursthouse, MB; Cavell, K.X; Dervisis, A.; Fallis, IA Organometallics 2008, 27, 3279-3289).
- the cyclization of amidines allows rapid access to different ring sizes.
- the deprotonation then takes place with a strong, sterically hindered base, for example lithium or potassium hexamethyldisilazide (LiHMDS or KHM DS) in a solvent such as.
- C0 2 , CS 2 an alcohol, a haloform (CH F 3 , CHCl 3 ) or a penta- or tetrafluorobenzene.
- the polymerization of ⁇ -caprolactam is carried out in compliance with the usual process parameters, whereby preferred process routes of the invention, as shown below, can be taken. It is expedient that the protected N-heterocyclic carbenes are easily activated at the particular temperature of the polymerization of ⁇ -caprolactam. It is further preferred that the polymerization of the ⁇ -caprolactam is carried out at a temperature of at least 70 ° C, in particular of at least 100 ° C. It is particularly preferred that the ⁇ -caprolactam is polymerized at a temperature of 100 ° C to 250 ° C, in particular 130 ° C to 200 ° C.
- the polymerization of ⁇ -caprolactam with protected N-heterocyclic carbenes proceeds in such a way that at elevated temperature the respective protective group, eg. As C0 2 , CS 2 , pentafluorobenzene, an alcohol, a Lewis acid 0- of a haloform, is cleaved off and the free N-heterocyclic carbene is formed.
- This deprotonated ⁇ -caprolactam then starts the polymerization.
- molar ratio of ⁇ -caprolactam to protected N-heterocyclic carbene It is also expedient to optimize the molar ratio of ⁇ -caprolactam to protected N-heterocyclic carbene. It is preferred that this is at least about 100, in particular at least 175. As an advantageous framework condition for the molar ratio can be given 200 to 500.
- the poly-s-caprolactam precipitates in high yield within a few minutes.
- the time-outs or the polymer! - Ons Anlagenen also depend on the used protected N-heterocyclic carbene or precatalyst. It should be emphasized that in particular the use of alkyl-substituted tetrahydropyrimidinium-based carbenes leads to a rapid polymerization.
- the frame is 17 ⁇ pK a ⁇ 28.
- the particular value of the invention lies in the fact that the polymerization reaction in the context of a reaction injection molding process (RIM) or a resin transfer molding process (RTM) is performed.
- RIM reaction injection molding process
- RTM resin transfer molding process
- the process according to the invention also makes it possible, which is advantageous, that the ⁇ -caprolactam to be polymerized contains additives, in particular nano- and micro-scale metal oxides, in particular SiO 2 , Al 2 O 3 , TiO 2 or ZrO 2 , and the corresponding organic compounds surface-modified metal oxides, reinforcing elements, in particular textile structures, nanoscale or microscale inorganic or organic substances.
- the textile structures are based on continuous fibers, short fibers or staple fibers, yarns and / or textile fabrics.
- the usable textile fabrics In particular, woven, knitted, knitted, braided, scrim, which are present as a winding or as a nonwoven fabric.
- the process according to the invention can also be further developed by not carrying out a RIM or RTM process, but rather coatings based on poly-s-caprolactams, adhesives, sealants, porous moldings or foams, in particular with the omission of a degassing or incorporating foaming agents, or varnishes.
- thermally labile, protected N-heterocyclic carbenes comprises in particular imidazolium, imidazolinium, tetrahydropyrimidinium and diazepinium compounds.
- Advantageous protective groups can be used in this case, as described above, for example C0 2 , CS 2 and metal salts or Lewis acids or it is possible to produce structures which correspond to the abovementioned formula (I).
- a 1-component system can be realized, which allows to polymerize prefabricated ⁇ -caprolactam / precatalyst mixtures at any time by raising the temperature.
- Advantageous areas of application of the invention are, in particular, reaction injection molding (RIM) and resin transfer molding (RTM).
- the polymerization may be metal-free if precatalysts such as NHC-C0 2 or NHC-CS 2 are used.
- the protected N-heterocyclic carbenes used according to the invention thus lead to the mentioned advantages, in particular those NHCs which have a strong basicity.
- the N-heterocyclic carbenes used according to the invention can be stored without loss of activity and accumulate as powder or crystalline solids. These can be easily mixed with the ⁇ -caprolactam and packaged.
- N-heterocyclic carbenes in the context of the polymerization process according to the invention in the practical implementation great benefits. Only when the active species is needed, for example, from the C0 2 - and metal NHC complexes, ie, the mixture is to be polymerized, this is done by raising the temperature.
- the protected N-heterocyclic carbenes can be easily mixed with ⁇ -caprolactams and packaged as a polymerization-ready mixture.
- NHC carboxylates offer the possibility of a completely metal-free reaction. If metal salts are used as protective groups, they can accelerate the polymerization by virtue of their function as Lewis acids (increase in electron poverty on the carbonyl carbon of the ⁇ -caprolactam).
- a particular advantage of the invention is that it can be controlled variably, in each case with regard to the desired polymerization process, ie, for example, compounds of the formula (III) are used, in which the protective group is based on Lewis acids.
- the Lewis acids liberated in the activation of Lewis acid-protected NHCs can basically coordinate to the carbonyl oxygen of ⁇ -caprolactam and thus increase the electrophilicity of ⁇ -caprolactam and thus its reactivity.
- Lewis acid-protected NHCs can thus function as "dual" catalysts after their decomposition: The liberated Lewis acids increase the electrophilicity of ⁇ -caprolactam and the free NHCs formed deprotonate ⁇ -caprolactam to the corresponding nucleophilic anion.
- metal-free protected N-heterocyclic carbenes is in principle advantageous if metal-free poly (s-caprolactam) is to be obtained.
- metal-free poly s-caprolactam
- the invention represents a considerable advance in comparison to other published systems.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
Description
Claims
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DE102013001439 | 2013-01-29 | ||
PCT/EP2014/051327 WO2014118076A1 (de) | 2013-01-29 | 2014-01-23 | VERFAHREN ZUR POLYMERISATION VON ε-CAPROLACTAM |
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CN105646876B (zh) * | 2016-04-08 | 2018-06-19 | 南京工业大学 | 一种有机催化制备聚酯酰胺的方法 |
EP3892668A1 (de) | 2020-04-07 | 2021-10-13 | Universität Stuttgart | Latente katalysatorsysteme und verfahren zur herstellung von polyamiden |
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US7635747B2 (en) * | 2004-11-09 | 2009-12-22 | E.I. Du Pont De Nemours And Company | Polymerization of cyclic amides using N-heterocyclic carbene and metal amide and metal alkoxide catalysts |
US7514499B2 (en) | 2004-11-09 | 2009-04-07 | E. I. Du Pont De Nemours And Company | Ring opening polymerization of cyclic amides using N-heterocyclic carbene catalysts |
DE102006038934A1 (de) | 2006-08-18 | 2008-02-21 | Evonik Degussa Gmbh | Herstellung von α-Hydroxyketonen über Carbenkatalysierte Umpolungsreaktion von Aldehyden |
CN101665567B (zh) * | 2008-09-01 | 2011-11-23 | 南京工业大学 | 卡宾衍生物催化的环状化合物可调控开环聚合方法 |
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