CN1170004A - 烯属不饱和单体的压缩 - Google Patents
烯属不饱和单体的压缩 Download PDFInfo
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- CN1170004A CN1170004A CN97113515A CN97113515A CN1170004A CN 1170004 A CN1170004 A CN 1170004A CN 97113515 A CN97113515 A CN 97113515A CN 97113515 A CN97113515 A CN 97113515A CN 1170004 A CN1170004 A CN 1170004A
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- Prior art keywords
- under
- ethylenically unsaturated
- acid
- condition
- compress
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- 239000000178 monomer Substances 0.000 title claims abstract description 29
- 238000007906 compression Methods 0.000 title claims abstract description 18
- 230000006835 compression Effects 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 36
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- 239000001301 oxygen Substances 0.000 claims description 36
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000007858 starting material Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- SYNHCENRCUAUNM-UHFFFAOYSA-N Nitrogen mustard N-oxide hydrochloride Chemical compound Cl.ClCC[N+]([O-])(C)CCCl SYNHCENRCUAUNM-UHFFFAOYSA-N 0.000 claims description 4
- 230000002028 premature Effects 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002832 nitroso derivatives Chemical class 0.000 claims description 2
- 150000002990 phenothiazines Chemical class 0.000 claims description 2
- 150000004053 quinones Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 2
- -1 propylene, butylene Chemical group 0.000 description 30
- 150000002148 esters Chemical class 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 2
- SYDNSSSQVSOXTN-UHFFFAOYSA-N 2-nitro-p-cresol Chemical compound CC1=CC=C(O)C([N+]([O-])=O)=C1 SYDNSSSQVSOXTN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NWHVZAGJLOWTDI-UHFFFAOYSA-N C1=CC(=CC=C1O)C.[N+](=O)([O-])C1=CC=CC(=C1)[N+](=O)[O-] Chemical compound C1=CC(=CC=C1O)C.[N+](=O)([O-])C1=CC=CC(=C1)[N+](=O)[O-] NWHVZAGJLOWTDI-UHFFFAOYSA-N 0.000 description 2
- XMLIDAXSKMAYCJ-UHFFFAOYSA-N CC1=CC=CC=C1O.[N+](=O)([O-])C1=CC=CC(=C1)[N+](=O)[O-] Chemical compound CC1=CC=CC=C1O.[N+](=O)([O-])C1=CC=CC(=C1)[N+](=O)[O-] XMLIDAXSKMAYCJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 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 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- JASHYFWBPRVTNZ-UHFFFAOYSA-N 1-[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical class CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)NC(=O)NC1=O JASHYFWBPRVTNZ-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N 2,2,4,6,6-pentamethylheptane Chemical compound CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical group CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- MCRZWYDXIGCFKO-UHFFFAOYSA-N 2-butylpropanedioic acid Chemical compound CCCCC(C(O)=O)C(O)=O MCRZWYDXIGCFKO-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- SXGXVOZDLWXVKM-UHFFFAOYSA-N 3-dodecylpyrrolidine-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)NC1=O SXGXVOZDLWXVKM-UHFFFAOYSA-N 0.000 description 1
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 description 1
- JSTCPNFNKICNNO-UHFFFAOYSA-N 4-nitrosophenol Chemical compound OC1=CC=C(N=O)C=C1 JSTCPNFNKICNNO-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CUWJKUDBPCMCIZ-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCC.C(CC)(=O)O Chemical compound CCCCCCCCCCCCCCCCCC.C(CC)(=O)O CUWJKUDBPCMCIZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- ZIMZZHQJEXWKFT-UHFFFAOYSA-N OC1=CC=CC2=CC=CC=C12.[N+](=O)([O-])C1=CC=CC(=C1)[N+](=O)[O-] Chemical class OC1=CC=CC2=CC=CC=C12.[N+](=O)([O-])C1=CC=CC(=C1)[N+](=O)[O-] ZIMZZHQJEXWKFT-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种在200—5000巴的压力下,在没有聚合引发剂的条件下压缩烯属不饱和单体的方法,包括在位阻胺衍生物存在的条件下进行压缩。
Description
本发明涉及一种在没有聚合引发剂的情况下在200-5000巴的压力下压缩烯属不饱和单体的方法。
本发明还涉及一种通过这种压缩继而聚合制备共聚物的方法，可由这种方法得到的共聚物以及在这类压缩方法中位阻胺的衍生物的用途。
长期以来，位阻胺的衍生物被认为是塑料和可游离基聚合单体的稳定剂。
EP-A-178168公开了一种在蒸馏过程中抑制α、β-烯属不饱和一元羧酸如丙烯酸聚合的方法。
US-5449724描述了一种在游离基引发剂和稳定的游离基化合物存在的条件下，在40-500℃和在500-5000巴下制备热塑性乙烯均聚物和共聚物的方法。这里存在的稳定的游离基化合物，特别是2，2，6，6-四甲基哌啶-N-氧基的衍生物导致使分子量分布特别窄，特别是影响与分子量分布有关的物理特性。
将烯属不饱和单体压缩到500-5000巴高压，特别是乙烯和丙烯酸或丙烯酸衍生物的单体混合物的压缩，常常伴随着(甚至在聚合作用引发之前)在压缩机和预压缩机中过早聚合的情况，导致沉积物的形成并且在短的时间间隔经常需要清除压缩机。使用常规的阻聚剂如甲基氢醌和氢醌，对于高浓度的阻聚剂，只能达到低的抑制效果。
因此，本发明的目的是提供一种压缩烯属不饱和单体的方法，该单体在压缩过程中减少了由于过早聚合作用而形成的沉积物。
我们已经发现在没有聚合引发剂存在的条件下，在200-5000巴压力下通过压缩烯属不饱和单体的方法达到了这个目的，该方法包括在位阻胺衍生物存在的条件下进行压缩。
按照该新方法，可压缩所有常规的烯属不饱和单体。合适单体的例子是乙烯、丙烯、丁烯和丁二烯，C2-C18-链烷羧酸乙烯酯如乙酸乙烯酯和丙酸乙烯酯，丙烯酸和甲基丙烯酸的C2-C18-烷基酯如甲基、乙基、丙基、丁基和2-乙基己基的丙烯酸酯和甲基丙烯酸酯，单烯属不饱和二羧酸酯如马来酸和富马酸单酯和二酯，单烯属不饱和羧酸如丙烯酸、甲基丙烯酸、马来酸和富马酸，单烯属不饱和羧酸的酰胺如丙烯酰胺、甲基丙烯酰胺、N-单-(C1-C18-烷基)丙烯酰胺、N-单-(C1-C18-烷基)甲基丙烯酰胺、N-二-(C1-C18-烷基)丙烯酰胺和N-二-(C1-C18-烷基)甲基丙烯酰胺，单烯属不饱和醇，C1-C4-烷基乙烯基醚和N-乙烯基-杂环化合物如N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、N-乙烯基咪唑，以及N-乙烯基甲酰胺。
该新方法特别适合于压缩用于共聚作用的单体混合物。特别适合的单体混合物是除了乙烯、丙烯、丁烯和丁二烯外包括上述共聚单体的单体混合物。
特别适合的共聚单体是丙烯酸和甲基丙烯酸的衍生物和这些酸本身。适合的这些酸衍生物的例子是C1-C18 烷基酯、C1-C18-单和双烷基酰胺和未取代的酰胺。适合的C1-C18-烷基的例子是甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、叔戊基、新戊基和各种同分异构己基、庚基、辛基、壬基、癸基、十-烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基和十八烷基。
特别优选的是，按照该新方法可压缩乙烯和丙烯酸和/或甲基丙烯酸的混合物。
按照本发明，在位阻胺衍生物存在的条件下压缩烯属不饱和单体。术语位阻胺是指所有的仲胺，在与胺的氮原子相邻的碳原子上的取代基确保了在其上无氢原子。优选的是在位置4或在胺的氮原子上取代的2，2，6，6-四甲基哌啶衍生物。
优选的位阻胺的衍生物是羟基胺。特别优选的位阻胺的衍生物是N-氧基。
适合的胺N-氧基的例子是其中每个R分别是烷基、环烷基、芳烷基或芳基，它们也可以成双连接形成环系，而Y是需要完成5-或6-元环的基团。R的例子是C1-C20烷基，特别是C1-C8-烷基，C5-或C6-环烷基，苄基或苯基。Y的例子是亚烷基-(CH2)2-或-(CH2)3-。
适合的N-氧基化合物例如是其中每个芳环也可以带1-3个惰性取代基例如C1-C4-烷基、C1-C4-烷氧基或氰基。
优选的是使用环胺的位阻胺衍生物，例如哌啶或吡咯烷化合物，在其环上可包括其他杂原子如氮、氧或硫，这些杂原子与位阻胺的氮原子不相邻。位阻是由与胺的氮原子邻位的取代基提供，适合的取代基是取代α-CH2基团的所有4个氢原子的烃基。可能的取代基的例子是苯基、C3-C6-环烷基、苄基和尤其是C1-C6-烷基，其中与同一个α碳原子相连的烷基也可以相互连接形成5-或6-元环。特别优选的是在定义R1和R2列出的基团。作为位阻胺的N-氧基，优选的是使用2，2，6，6-四烷基哌啶的衍生物。
在新的单体组合物中，优选的N-氧基化合物是式II的化合物
其中R1和R2是C1-C4-烷基或苯基，或它们与碳原子连接在一起成为5-或6-元饱和烃环。R3 是氢、羟基、氨基或通过氧或氮连接的m-价有机基团、或与R4一起是氧或下面R4定义的环结构。R4 是氢或C1一C12-烷基，或与R3一起是氧，或与R3一起和碳原子连接形成环结构
其中，如果R3和R4结合形成一个基团，那么m是1R5 是氢、C1-C12-烷基或-(CH2)z-COOR6，R6是相同的或不同的C1-C18-烷基，k 是0或1，Z和p 是1-12，和m 是1-100。
R1和R2的例子是C1-C4-烷基，如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基，或它们一起形成四亚甲基-或1，5-亚戊基。R1和R2优选地是甲基。
适合的基团R4是氢，上述的C1-C4-烷基，以及戊基、仲戊基、叔戊基、新戊基、己基、2-甲基戊基、庚基、2-甲基己基、辛基、异辛基、2-乙基-己基、壬基、2-甲基壬基、异壬基、2-甲基辛基、癸基、异癸基、2-甲基壬基、十一烷基、异十一烷基、十二烷基和异十二烷基(命名的异辛基、异壬基和异十一烷基是俗名，由羰基合成法获得的羰基化合物衍生来的；参见Ullmanns Encyclopedia of IndustrialChemistry，第5版，第A1卷，第290-293页，和第A10卷，第284和285页)。
p优选地是6-12，特别优选地是9。
z优选地是1-4，特别优选地是2。
除了氢以外，R5的例子还有上述的C1-C12-烷基。R5优选地是氢、C1-C4-烷基或-(CH2)z-COO(C1-C6-烷基)，特别优选地是-CH2-CH2-COO(CH2)11-CH3或-CH2-CH2-COO(CH2)13-CH3。
R6的例子包括上述C1-C12-烷基和十三烷基、异十三烷基、十四烷基、十五烷基、十六烷基、十七烷基或十八烷基。优选地是十二烷基和十六烷基。
优选的基团R3的例子是下面m-价基团 
其中R7 是C1-C12-烷基或-(CH2)z-COOR6，R8 是氢或C1-C18-烷基，R9 是C1-C18-烷基、乙烯基或异丙烯基，R10 是C8-C22-烷基，R11 是氢或初始单体的游离基聚合通常形成的有机基团，k 是0或1，x 是1～12，和n 为偶数m。其中R3是基团，R4优选地是氢。在这种情况下m可以是1-100。m优选地是1，2，3，4或10-50的数，通常使用其混合物，特别是在低聚或聚合基团R3的情况下。
适合基团R7与R5定义的相同。R7优选地是C1-C4-烷基。
除了氢以外，适合的基团R8与R6定丈的相同。R8优选地是氢。
特别适合的基团R9是乙烯基、异丙烯基或C15-C17-烷基。
适合基团R10的例子是上述C8～C18-烷基和十九烷基、二十烷基、二十一烷基二十二烷基。在这种情况下，优选的是碳链长度不同的基团R10的混合物。
R11是氢或初始单体的游离基聚合获得的有机基团，在这种情况下，是乙烯衍生物和马来酰亚胺衍生物，即由聚合引发剂形成或由作为中间体形成的游离基形成的，或由对于熟练的技术人员来说类似的其他这类基团形成的。
其他优选的硝酰基化合物是：
1-氧基-2，2，6，6-四甲基哌啶，
1-氧基-2，2，6，6-四甲基哌啶-4-醇，
1-氧基-2，2，6，6-四甲基哌啶-4-酮，
乙酸1-氧基-2，2，6，6-四甲基哌啶-4-基酯，
2-乙基已酸1-氧基-2，2，6，6-四甲基哌啶-4-基酯，
硬脂酸1-氧基-2，2，6，6-四甲基哌啶-4-基酯，
苯甲酸1-氧基-2，2，6，6-四甲基哌啶-4-基酯，
(4-叔丁基)苯甲酸1-氧基-2，2，6，6-四甲基哌啶-4-基酯，
琥珀酸双(1-氧基-2，2，6，6-四甲基哌啶-4-基)酯，
己二酸双(1-氧基-2，2，6，6-四甲基哌啶-4-基)酯，
癸二酸双(1-氧基-2，2，6，6-四甲基哌啶-4-基)酯，
正丁基丙二酸双(1-氧基-2，2，6，6-四甲基哌啶-4-基)酯，
邻苯二甲酸双(1-氧基-2，2，6，6-四甲基哌啶-4-基)酯，
间苯二甲酸双(1-氧基-2，2，6，6-四甲基哌啶-4-基)酯，
对苯二甲酸双(1-氧基-2，2，6，6-四甲基哌啶-4-基)酯，
六氢化对苯二甲酸双(1-氧基-2，2，6，6-四甲基哌啶-4-基)酯。
N，N′-双(1-氧基-2，2，6，6-四甲基哌啶-4-基)已二酰二胺，
N-(1-氧基-2，2，6，6-四甲基哌啶-4-基)己内酰胺，
N-(1-氧基-2，2，6，6-四甲基哌啶-4-基)十二烷基-琥珀酰亚胺，
2，4，6-三[N-丁基-N-(1-氧基-2，2，6，6-四甲基哌啶-4-基)]-s-三嗪，
4，4′-亚乙基-双(1-氧基-2，2，6，6-四甲基哌嗪-3-酮)和亚磷酸三(2，2，6，6-十四甲基-1-氧基哌啶-4-基)酯。特别优选的N-氧基衍生物是式I的衍生物其中A是2-20碳原子的二价有机基团。
适合的基团A的例子是α，ω-亚烷基，其碳链可以是直链或支链和由醚官能团中的氧原子、由亚氨基或C1-C4-烷基亚氨基断开。例如在早期的德国专利申请19510184.7中分别描述了这类亚烷基基团。优选的基团A是具有2-10碳原子的直链α，ω-亚烷基；特别优选地是六亚甲基。
适合的位阻胺的羟基胺衍生物是上述的所有N-氧基衍生物，但在每种情况下用羟基胺基团代替其中的N-氧基。
除了位阻胺的衍生物外，在新的方法中也可以使用辅助稳定剂。适合的辅助稳定剂的例子是芳族硝基或亚硝基化合物和羟基胺，包括没有位阻的化合物。
可以使用的芳族硝基化合物的例子是1，3-二硝基苯、1，4-二硝基苯、2，6-二硝基-4-甲基苯酚、2-硝基 4-甲基苯酚、2，4，6-三硝基苯酚，2，4-二硝基-1-萘酚、2，4-二硝基-6-甲基苯酚、2，4-二硝基氯苯、2，4-二硝基苯酚、2，4-二硝基-6-仲-丁基苯酚、4-氰基-2 硝基苯酚和3-碘-4-氰基-5-硝基苯酚，优选2，6-二硝基-4-甲基苯酚、2-硝基-4-甲基苯酚、2，4-二硝基-6-仲-丁基苯酚和2，4-二硝基-6-甲基苯酚。
适合的芳族亚硝基化合物的例子是对亚硝基苯酚、对亚硝基-邻甲苯酚和对亚硝基-N，N′-二乙基苯胺。
可以使用的其他辅助稳定剂是醌类、吩噻嗪类和酚美化合物。
适合的取代的酚的例子是：
4-叔丁基邻苯二酚、甲氧基氢醌、2，6-二-叔丁基-4-甲基苯酚、β-(3，5-二-叔丁基-4-羟基苯基)丙酸正十八烷基酯、1，1，3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、1，3，5-三甲基-2，4，6-三(3，5-二-叔丁基-4-羟基苄基)苯、三(3，5-二-叔丁基-4-羟基苄基)异氰脲酸酯、三[β-(3，5-二-叔丁基-4-羟基苯基)丙酰氧基乙基]异氰脲酸酯、三(2，6-二甲基-3-羟基-4-叔丁基苄基)异氰脲酸酯和季戊四醇四[β-(3，5-二-叔丁基-4-羟基苯基)丙酸酯]。
在新的压缩方法中，位阻胺衍生物的使用浓度为0.00001-1％(重量)(按欲压缩的单体量计)。优选地是0.0001-0.1％(重量)。这种浓度范围对于上述的辅助稳定剂也适用。
按照新方法，将单体压缩到200-5000巴的压力，压缩最好是分步进行，最后压力优选为1000-4000巴，特别优选1500-3000巴下进行压缩。
压缩温度优选地为20-140℃，特别优选地为30-100℃。
按照本发明，在压缩过程中没有聚合引发剂存在。在这里，聚合引发剂是加入单体中引发游离基聚合的所有化合物，例如偶氮化合物、有机过氧化物和氢过氧化物。对于本发明的目的来说，压缩混合物中存在的氧不认为是聚合引发剂。
新的压缩方法优选地是构成高压共聚方法的一部分，该方法包括按照新方法压缩单独的或作为混合物的共聚单体，然后在50-350℃下加入聚合引发剂进行聚合。
优选的聚合温度是150-300℃，优选的压力是1000-4000巴，特别优选地是2000-3000巴。
用常规的方法例如可以在管式反应器或压力釜中进行聚合反应，在聚合混合物中可以加入任何常用添加剂-例如分子量调节剂、溶剂等。
新的聚合方法的优点是不仅压缩装置使用时间较长，而且也改进了聚合产品。例如在乙烯与丙烯酸的共聚中，特别是丙烯酸单体在压缩过程中有过早聚合的趋势。这导致在共聚物中有一定比例或至少部分的丙烯酸均聚物存在，因此对产品的均质性和该方法的再现性不利。相反，由本发明方法获得的共聚物具有较高的均质性。
实施例
在预压缩机中，将乙烯压缩到220巴的压力。60分钟内，将85升的丙烯酸和异癸烷(体积比为1∶1)的混合物(稳定剂N，N′-双-(2，2，6，6-四甲基哌啶-1-氧基-4-基)-N，N′-二甲酰基六亚甲基二胺按照表中的量溶解其中)，泵送到压缩气体流(1400千克/小时)中。使混合物在后压缩机中压缩到2300巴并连续输送到35升径流的钢压力釜中。通过加入0.0025摩尔％(以单体的全部摩尔量为基准)的过新戊酸叔丁酯来引发聚合。反应温度为220℃。当在后压缩机上由沉积引起的气体泄漏量超过50千克/小时时，反应结束。
示范试验的结果在下表中表示：
| 实施例 | 抑制剂浓度(％重量) | 运行时间(小时) |
| 1 | 0.020 | ＞168 |
| 2 | 0.010 | ＞168 |
| 3 | 0.005 | 124 |
| 对比例 | 0 | 27 |
Claims (11)
1.一种在200-5000巴压力下，在没有聚合引发剂存在的条件下压缩烯属不饱和单体的方法，包括在位阻胺衍生物存在的条件下进行压缩。
2.根据权利要求1的方法，其中使用包括乙烯、丙烯或丁二烯的混合物作为烯属不饱和单体。
3.根据权利要求1或2的方法，其中使用包括丙烯酸、甲基丙烯酸的衍生物或这些酸本身的混合物作为烯属不饱和单体。
4.根据权利要求1-3的任何一项的方法，其中使用包括乙烯和丙烯酸的混合物作为烯属不饱和单体。
5.根据权利要求1-4的任何一项的方法，其中在位阻胺的N-氧基衍生物存在的条件下进行压缩。
6.根据权利要求1-5的任何一项的方法，其中在式I化合物存在的条件下进行压缩其中A是2-20碳原子的二价有机基团
7.根据权利要求1-6的任何一项的方法，其中在羟基胺或芳族硝基或亚硝基化合物存在的条件下进行压缩。
8.根据权利要求1-6的任何一项的方法，其中在醌类、吩噻嗪类和酚类化合物存在的条件下进行压缩。
9.一种制备共聚物的方法，包括按照权利要求1-8任何一项的方法压缩单个单体或单体混合物，然后加入聚合引发剂在50-350℃下进行聚合。
10一种可按照权利要求9的方法获得的共聚物。
11.位阻胺的衍生物在将烯属不饱和单体压缩到200-5000巴的压力下的过程中防止其过早聚合的用途。
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| DE19622441A DE19622441A1 (de) | 1996-06-05 | 1996-06-05 | Verfahren zum Verdichten ethylenisch ungesättigter Monomerer |
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| AT (1) | ATE299847T1 (zh) |
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| TWI246519B (en) * | 1998-06-25 | 2006-01-01 | Ciba Sc Holding Ag | Use of 2,2,6,6 tetraalkylpiperidine-N-oxyl radicals having long alkyl chains as polymerization regulators |
| US6864313B2 (en) * | 1998-06-25 | 2005-03-08 | Ciba Specialty Chemicals Corp. | Use of 2,2,6,6 tetraalkylpiperidine-N-oxyl radicals having long alkyl chains as polymerization regulators |
| US6734269B1 (en) | 1998-10-06 | 2004-05-11 | Atofina | Method for controlled free radical polymerization or copolymerization of ethylene under high pressure in the presence of an initiator-controller |
| DE19859391A1 (de) | 1998-12-22 | 2000-06-29 | Basf Ag | Verfahren zum Verdichten ethylenisch ungesättigter Monomerer |
| FR2791687A1 (fr) * | 1999-03-31 | 2000-10-06 | Atochem Elf Sa | Procede de polymerisation ou copolymerisation radicalaire controlee |
| FR2804118B1 (fr) * | 2000-01-26 | 2003-08-22 | Atofina | Procede de polymerisation ou copolymerisation radicalaire controlee de l'ethylene sous haute pression en presence de radicaux libres amorceurs et de radicaux nitroxydes indoliniques controleurs |
| DE10006900A1 (de) * | 2000-02-16 | 2001-08-23 | Basell Polyolefine Gmbh | Verfahren zur radikalischen Ethylen-Hochdruckpolymerisation unter Vermeidung unerwünschter Polymerablagerungen |
| US20030225182A1 (en) * | 2001-01-04 | 2003-12-04 | Dentsply Detrey Gmbh | Dental composition with improved light stability |
| US20040225029A1 (en) * | 2000-02-17 | 2004-11-11 | Uwe Walz | Dental composition with improved light stability |
| US8026295B2 (en) * | 2000-02-17 | 2011-09-27 | Dentsply International, Inc. | Dental composition with improved light stability |
| US20020002213A1 (en) * | 2000-02-17 | 2002-01-03 | Uwe Walz | Dental composition with improved light stability |
| EP1563821B1 (en) * | 2000-02-17 | 2006-11-22 | Dentsply International, Inc. | Dental composition with light stability |
| WO2002013767A2 (en) * | 2000-08-11 | 2002-02-21 | Dentsply International Inc. | Polyaminoester and their application in dental compositions |
| US20040171716A1 (en) * | 2002-12-03 | 2004-09-02 | Uwe Walz | Dental compositions comprising bisacrylamides and use thereof |
| US20030069327A1 (en) * | 2001-08-09 | 2003-04-10 | Uwe Walz | Dental compostions comprising bisacrylamides and use thereof |
| ATE307552T1 (de) * | 2001-08-13 | 2005-11-15 | Dentsply Int Inc | Kegel zur füllung von zahnwurzelkanälen |
| US20040209990A1 (en) * | 2003-04-15 | 2004-10-21 | Uwe Walz | Low shrinking polymerizable dental material |
| DE10354652A1 (de) | 2003-11-22 | 2005-07-07 | Clariant Gmbh | Verfahren zur Veresterung von Alkoholen mit olefinisch ungesättigten Carbonsäuren |
| US20100210800A1 (en) | 2004-03-24 | 2010-08-19 | Ciba Corporation | Method of preparing ethylene polymers by controlled high pressure polymerization |
| CN101454359A (zh) * | 2006-05-23 | 2009-06-10 | 巴斯夫欧洲公司 | 乙烯共聚物的制备方法 |
| PL2239283T3 (pl) | 2009-11-10 | 2012-07-31 | Basell Polyolefine Gmbh | Wysokociśnieniowy LDPE (polietylen niskiej gęstości) do zastosowań medycznych |
| EP2589612A1 (en) | 2011-11-03 | 2013-05-08 | Basell Polyolefine GmbH | Process for polymerizing or copolymerizing ethylenically unsaturated monomers in the presence of free-radical polymerization initiators |
| CN104185644A (zh) | 2012-04-02 | 2014-12-03 | 北欧化工股份公司 | 使用抑制剂的乙烯聚合方法 |
| WO2021202278A1 (en) * | 2020-03-31 | 2021-10-07 | Dow Global Technologies Llc | Antifoulant and process |
| BR112022017050A2 (pt) * | 2020-03-31 | 2022-11-16 | Dow Global Technologies Llc | Anti-incrustante e processo |
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| US3634346A (en) * | 1969-08-15 | 1972-01-11 | Union Carbide Corp | Oxidation of cyclic amines to lactams |
| US4016198A (en) * | 1974-01-25 | 1977-04-05 | Monsanto Company | Stabilization of unsaturated carboxylic acid esters with mixtures of polyalkylene-amines and arylenediamines |
| US4284692A (en) * | 1980-04-28 | 1981-08-18 | Exxon Research & Engineering Co. | Compositions for stabilizing electrolytes in Li/TiS2 systems |
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| US4665185A (en) * | 1984-03-22 | 1987-05-12 | Ciba-Geigy Corporation | Process for preparing nitroxyls of sterically hindered amines |
| US4668721A (en) * | 1984-07-23 | 1987-05-26 | Ciba-Geigy Corporation | Polyolefin compositions stabilized against degradation using hydroxylamine derivatives |
| US4691015A (en) * | 1984-07-23 | 1987-09-01 | Ciba-Geigy Corporation | Hydroxylamines derived from hindered amines |
| DE3575418D1 (de) * | 1984-10-10 | 1990-02-22 | Amoco Corp | Verfahren zur reinigung von methacrylsaeure. |
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| US4912247A (en) * | 1989-01-19 | 1990-03-27 | Betz Laboratories, Ltd. | Enhancement of aromatic amine inhibition of acrylate monomer polymerization by addition of mannich products |
| DE69108626T2 (de) * | 1990-07-20 | 1995-08-24 | Ciba Geigy Ag | Stabilisierte Monomerenzusammensetzungen. |
| DE69112735T2 (de) * | 1990-07-20 | 1996-02-22 | Ciba Geigy Ag | Stabilisierte Monomerenzusammensetzungen. |
| US5290888A (en) * | 1990-07-20 | 1994-03-01 | Ciba-Geigy Corporation | Process for stabilizing ethylenically unsaturated compounds and stabilized monomer compositions |
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| KR100193146B1 (ko) * | 1990-07-20 | 1999-06-15 | 월터 클리웨인, 한스-피터 위트린 | 안정화된 단량체 조성물 |
| IT1243402B (it) * | 1990-11-30 | 1994-06-10 | Enichem Sintesi | Procedimento per la preparazione dei radicali nitrosilici delle amminestericamente impedite. |
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| DE19510184A1 (de) * | 1995-03-21 | 1996-09-26 | Basf Ag | 4-Acylaminopiperidin-N-oxyle |
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- 1997-05-30 DE DE59712364T patent/DE59712364D1/de not_active Expired - Lifetime
- 1997-05-30 AT AT97108677T patent/ATE299847T1/de not_active IP Right Cessation
- 1997-06-02 US US08/867,041 patent/US5872252A/en not_active Expired - Lifetime
- 1997-06-03 JP JP14438297A patent/JP3774779B2/ja not_active Expired - Fee Related
- 1997-06-04 CN CN97113515A patent/CN1096441C/zh not_active Expired - Fee Related
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| Publication number | Publication date |
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| DE59712364D1 (de) | 2005-08-25 |
| US5914379A (en) | 1999-06-22 |
| CN1096441C (zh) | 2002-12-18 |
| EP0811590A1 (de) | 1997-12-10 |
| ATE299847T1 (de) | 2005-08-15 |
| DE19622441A1 (de) | 1997-12-11 |
| US5872252A (en) | 1999-02-16 |
| EP0811590B1 (de) | 2005-07-20 |
| JPH1060018A (ja) | 1998-03-03 |
| JP3774779B2 (ja) | 2006-05-17 |
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