CN1181056C - 4-酰基氨基哌啶n-氧化物 - Google Patents
4-酰基氨基哌啶n-氧化物 Download PDFInfo
- Publication number
- CN1181056C CN1181056C CNB96192697XA CN96192697A CN1181056C CN 1181056 C CN1181056 C CN 1181056C CN B96192697X A CNB96192697X A CN B96192697XA CN 96192697 A CN96192697 A CN 96192697A CN 1181056 C CN1181056 C CN 1181056C
- Authority
- CN
- China
- Prior art keywords
- formyl radical
- oxide compound
- alkyl
- group
- amino piperidine
- 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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- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 4
- -1 amino piperidine N-oxide compound Chemical class 0.000 claims description 66
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000011368 organic material Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 230000006641 stabilisation Effects 0.000 claims description 7
- 238000011105 stabilization Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000002832 nitroso derivatives Chemical class 0.000 claims description 4
- 150000003053 piperidines Chemical class 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 230000002939 deleterious effect Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 2
- 229940073608 benzyl chloride Drugs 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 125000006178 methyl benzyl group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004344 phenylpropyl group Chemical group 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- NIBFJPXGNVPNHK-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-4-carbaldehyde Chemical group C1=CC(C=O)=C2OC(F)(F)OC2=C1 NIBFJPXGNVPNHK-UHFFFAOYSA-N 0.000 claims 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 abstract 1
- 230000009931 harmful effect Effects 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 239000002585 base Substances 0.000 description 22
- 150000002148 esters Chemical class 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OUMHVZFFFUEQOA-UHFFFAOYSA-N C(C)(CC)C1=C(C=CC=C1)O.[N+](=O)([O-])C1=CC(=CC=C1)[N+](=O)[O-] Chemical compound C(C)(CC)C1=C(C=CC=C1)O.[N+](=O)([O-])C1=CC(=CC=C1)[N+](=O)[O-] OUMHVZFFFUEQOA-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 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 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 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
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[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
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 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
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 1
- PDOIGRRPKSYVKH-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O.OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O PDOIGRRPKSYVKH-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([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
- 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 1
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-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
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 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
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- RZKYEQDPDZUERB-UHFFFAOYSA-N Pindone Chemical group C1=CC=C2C(=O)C(C(=O)C(C)(C)C)C(=O)C2=C1 RZKYEQDPDZUERB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
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Abstract
式A1B1的4-酰基氨基哌啶N-氧化物,其中A1是氢或有机基团和B1是通式IIa所示的基团,其中R1-R4各自是C1-C4-烷基,和一方面R1和R2,另一方面R3和R4可进一步键接而形成5元环或6元环,R5是H或C1-C4-烷基和R6是H或C1-C18-烷基。该化合物用于稳定有机材料抵抗自由基的有害作用,特别是用于蒸馏能进行自由基聚合反应的单体,尤其是苯乙烯。
Description
本发明涉及由通式Ia表示的新的4-酰基氨基哌啶N-氧化物
A1B1 (Ia)
其中A1是氢或有机基团和B1是通式IIa所示的基团
其中
R1-R4各自是C1-C4-烷基,和一方面R1和R2,另一方面R3和R4可进一步键接而形成5元环或6元环,
R5是H或C1-C4-烷基和
R6是H或C1-C18-烷基。
本发明还涉及制备化合物Ia的方法,用于稳定有机材料抵抗自由基的有害作用(特别是在苯乙烯的蒸馏过程中)的化合物的用途,化合物Ia或Ib与硝基或亚硝基芳族化合物或取代的酚类的结合使用,和含有化合物Ia的液体或固体有机材料。
这种稳定有机材料以抵抗自由基(如在光或热的作用下形成的)的损害的作用一般是已知的。从包括2,2,6,6,-四甲基化哌啶各种衍生物的N-氧化物的各类物质中选择的化合物已被建议作为此目的的稳定剂。
从4-氨基-2,2,6,6,-四甲基哌啶N-氧化物衍生而来的这种类型的一种化合物是己二酸的双酰胺
它描述在SU-A 1 139 722中。类似的已知化合物包含酯或氨基甲酸酯基(分别见EP-A 0 581 737和SU-A 1 027 150)而不是甲酰氨基。
而且,EP-A 0 581 737公开了,如果N-氧化物与硝基芳族化合物一起使用,则会增加N-氧化物的稳定性作用。
此外,EP-B 0 316 582公开了,具有以下结构单元的非自由基哌啶衍生物
它适合作为有机材料的稳定剂。
因为到目前为止N-氧化物的作用不尽人意,所以本发明的目的是提供具有改进了的特性的新颖N-氧化物。
已经发现,此目的可通过开始所定义的4-酰基氨基哌啶N-氧化物来实现。
我们还发现一种制备化合物Ia和Ib的方法,这些化合物用于稳定有机材料的用途,它们与其它稳定剂的结合使用,和含有化合物Ia和Ib的液体或固体有机材料。
起稳定作用的化合物Ia的结构单元是通式IIa的B1部分。
在这通式中,R1-R4是烷基,如甲基,乙基,丙基或丁基,甲基是特别优选的。其中R1和R2或R3和R4一起形成四亚甲基或1,5亚戊基基团的脂环基也是合适的。
R5同样可为烷基,如甲基,乙基,丙基或丁基,但氢是优选的。
合适的基团R6是低级烷基,如甲基,乙基,丙基,丁基或至多18个碳原子的长链基团。然而,R6优选的是氢,因此,在这种情况下,氨基基团载有甲酰基。
A1部分特别起着使化合物的化学和物理性能适应于各种用途的作用。通过改变A1部分,例如,能够影响在各种有机材料中的溶解度,挥发性和与其它助剂的相容性。
除了氢外,A1可以为,例如,
-C1-C22-烷基,如甲基,乙基,正丙基,异丙基,正丁基,异丁基,正戊基,异戊基,己基,辛基,癸基,十二烷基,十八烷基,三甲基乙酰,3,3-二甲基丁-2-基,新戊基,4-甲基戊-2-基或2-乙基己基,
-C3-C22-链烯基,如烯丙基,丁烯基,戊烯基或油基,
-C3-C12-环烷基,如环丙基,环丁基,环戊基,环己基,甲基环己基,环庚基,环辛基,环十二烷基或二环庚基,特别是环戊基或环己基,
-氰基-,羟基-或烷氧基羰基取代的C2-C22-烷基,如氰基甲基,羟基乙基,羟基丙基,羟基丁基,甲氧基羰基乙基或乙氧基羰基乙基,
-C4-C22-烷基,它被醚式氧或氮间断或被羟基取代,如-(CH2)3N(CH3)2,-(CH2)3N(C2H5)2,-(CH2)3-OCH3,-(CH2)3-O-CH(CH3)2,-(CH2)2O(CH2)2-OH,-CH2-(CH2)2-CH2-N(CH2)3,-(CH2)2-N[CH(CH3)2]2,-(CH2)2-N-(C2H5)2,-(CH2)2N(CH3)2,-(CH2)2OCH3,或-(CH2)2OCH2CH3,
-未取代的或取代的C7-C22-苯基和C13-C22-二苯基烷基基团,如苄基,异构的甲氧基苄基,甲基苄基,乙基苄基,异丙基苄基,三甲基苄基,氟苄基,氯苄基,亚甲二氧基苄基,苯基乙基,苯基丙基和苯基丁基,二甲基氨基苄基,二苯基甲基和1,3-二苯基丙-2-基,
-芳基,如苯基,甲苯基或C1-C4-烷氧基羰基-取代的苯基,
-带有杂环结构的C1-C22-烷基,如
-含磷基团,如具有烷基残基的磷酰胺、膦酸衍生物或磷酸衍生物或脂族,芳族或杂环性质的含氮和/或含氧的有机基团。
优选的化合物Ia是其中A1本身进一步带有基团IIa的那些化合物。因此,一方面化合物可获得大大减少它们挥发性的分子量和另一面两种活性稳定剂基团的存在增加了该化合物的稳定作用。在通式Ia的化合物中,特别是通式Ib的化合物具有这些特性。
除了IIa部分以外,化合物Ib还含有IIb部分,其中R7是氢,羟基或C-或O-有机基团。特别地,甲酰基,O-烷基,O-芳基,O-烃基,O-氨基甲酰基,氰基甲基或取代的链烯基也可用作这些基团。对于R1-R6所适用的可能性和优选条件与对于IIa部分所指出的那些相同。
合适的A2部分的实例是下列基团:
-C2-C22-亚烷基和C5-C22-亚环烷基,如-(CH2)p-CH2-(其中p是1-21)
和
C8-C14-亚苯基烷基和亚苯基,如
其中q是0-4
-被醚式氧,氮或杂环结构间断的亚烷基,如
-(CH2)3O(CH2)4O(CH2)3-,-(CH2)3O(CH2)2O(CH2)2O(CH2)3-,
-(C3H6O)r-C3H6-其中r是1-33,
或
其中s是0-7,
-有磷作为杂原子的含碳-,氧-和/或氮的桥基,如
-(CH2)-O-P(O)Ph-O-(CH2)2-,-(CH2)2-O-P(O)OPh-O-(CH2)2-,
特别优选的化合物是通式Ib的化合物,其中所有B2部分是N-氧(oxyl)哌啶基(coxyl)团和A2部分是具有2-8个碳原子的短链亚烷基,如-CH2-CH2-,-(CH2)4-,-(CH2)6-,或-(CH2)8-。
这种新型的化合物可通过用过氧化氢氧化相应折哌啶化合物来制备。所使用的哌啶化合物和它们的制备方法描述在,例如,EP-A 0 316 582中或能够按本身已知的方式来制备。氧化反应优选在添加有有机溶剂的情况下进行。
优选地,所使用的有机溶剂是至少部分与水互溶的这些溶剂,例如极性质子溶剂,如醇类,特别是甲醇,乙醇,丙醇,正丁醇和异丁醇,和极性非质子传递溶剂,如二甲基甲酰胺,二甲基乙酰胺,N-甲基吡咯烷酮和四氢噻吩二氧化物。
氧化反应优选在6.5-11的pH范围内,特别优选7.0-8.5范围,更特别优选7.5-8.0范围内的PH值下进行,能够通过缓冲化合物如碳酸钠,碳酸氢钠,磷酸一氢或二氢钾或钠,或硫酸氢钠或硫酸氢钾,或有机酸,如乙酸,甲酸,氰基乙酸,丙二酸或乳酸调节pH值至所需范围并保持恒定。无机酸,如盐酸,硫酸或磷酸和无机碱如氢氧化钠,氢氧化锂或特别优选氢氧化钾(它们以水或醇的溶液形式被使用)也适合于调节PH值。
催化量的镁、钙或锌的氧化物,氢氧化物或盐的存在也是优选的,合适的阴离子是氮离子,溴离子,硫酸根和磷酸根。例如用硫酸镁可以获得良好的结果。硼酸,它们的盐和这些盐的水合物也可有利地被用作催化剂。这些盐的浓度是0.01-10mol%,优选0.1mol%,基于酰基氨基哌啶的量。
氧化反应优选在40-100℃的温度范围内进行,特别是在60-80℃的温度范围。反应0.5-约24小时后,优选地,将反应混合物冷却至室温,并添加水,所得到的反应产物按本身已知的方法以固体形式分离出来。特别是,对于存在易挥发性溶剂,例如甲醇、乙醇或异丙醇的反应,反应混合物可在添加或不添加水的情况下,蒸馏除去溶剂进行处理。氧化反应的条件是如此温和的和选择性的,以致没有消去敏感性基团,例如酰基,R6-CO-。氧化反应完成后,分解多余的过氧化氢是优选的。这可通过例如用铁或锰盐,优选硫酸铁(II),在略带碱性的PH条件下,如在9-10的PH值下处理反应混合物来完成。
氧化反应是否彻底完成不是重要的。即使部分氧化的哌啶化合物也具有良好的活性。
新型的4-酰基氨基哌啶N-氧化物适合于稳定有机材料并保护它们免受光和热的有害作用。被该化合物稳定的有机材料包括所有类型的塑料,例如聚丙烯,聚乙烯,丙烯腈/丁二烯/苯乙烯共聚物,聚酰胺,聚氨酯和含颜料的聚烯烃。脂肪类,油类和表面涂料也可用这种新型的化合物来稳定。
稳定剂Ia和Ib特别理想地用于稳定进行自由基聚合反应的单体,如丙烯酸和异丁烯酸的酯和酰胺以及这些酸本身,丙烯腈,甲基丙烯腈,氯乙烯和苯乙烯。
优选地,新型化合物特别是在储存和蒸馏过程中发挥稳定作用的。该新型的化合物Ia和Ib在对聚合反应敏感的苯乙烯的蒸馏过程中是非常重要的。
这种新型的化合物Ia和Ib,特别是其中R6是氢的那些化合物,本身已具有非常好的稳定作用。这种作用可通过与芳族硝基化合物或芳族亚硝基化合物或取代的酚类结合而进一步加以提高。可以使用的芳族硝基化合物的实例是
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,
3-碘代-4-氰基-5-硝基苯酚,
特别优选的是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。
合适的芳族亚硝基化合物的实例是
对-亚硝基苯酚,
对-亚硝基-邻-甲基苯酚,和
对-亚硝基-N,N-二乙基苯胺。
合适的取代酚类是:
4-叔丁基焦儿茶酚,
甲氧基对苯二酚,
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,
1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸酯,
1,3,5-三[β-(3,5-二叔丁基-4-羟基苯基)丙酰氧基乙基]异氰尿酸酯,
1,3,5-三(2,6-二甲基-3-羟基-4-叔丁基苄基)异氰尿酸酯,和季戊四醇-四[β-(3,5-二叔丁基-4-羟基苯基)丙酸酯],
4-酰基氨基哌啶N-氧化物Ia和Ib,如果需要,也可与其它N-氧化物
以任何所需的结合方式使用。例如,与以下化合物结合使用:
二叔丁基-硝酰基,
1-氧(oxyl)-2,2,6,6-四甲基哌啶,
1-氧-2,2,6,6-四甲基哌啶-4-醇,
1-氧-2,2,6,6-四甲基哌啶-4-酮,
乙酸1-氧-2,2,6,6-四甲基哌啶-4-基酯,
2-乙基己酸1-氧-2,2,6,6-四甲基哌啶4-基酯,
硬脂酸1-氧-2,2,6,6-四甲基哌啶-4-基酯,
苯甲酸1-氧-2,2,6,6-四甲基哌啶-4-基酯,
4-叔丁基苯甲酸1-氧-2,2,6,6-四甲基哌啶-4-基酯,
琥珀酸双(1-氧-2,2,6,6-四甲基哌啶-4-基酯),
己二酸双(1-氧-2,2,6,6-四甲基哌啶-4-基酯),
癸二酸双(1-氧-2,2,6,6-四甲基哌啶-4-基酯),
n-丁基丙二酸双(1-氧-2,2,6,6-四甲基哌啶-4-基酯),
邻苯二甲酸双(1-氧-2,2,6,6-四甲基哌啶-4-基酯),
间苯二甲酸双(1-氧-2,2,6,6-四甲基哌啶-4-基酯),
对苯二甲酸双(1-氧-2,2,6,6-四甲基哌啶-4-基酯),
六氢化对苯二甲酸双(1-氧-2,2,6,6-四甲基哌啶-4-基酯),
N,N′-双(1-氧-2,2,6,6-四甲基哌啶-4-基)己二酰胺
N-(1-氧-2,2,6,6-四甲基哌啶-4-基)己内酰胺
N-(1-氧-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-2,2,6,6-四甲基哌啶-4-基)]-均-三嗪,和
4,4′-亚乙基双(1-氧-2,2,6,6-四甲基哌嗪-3-酮)。
与位阻胺,如2,2,6,6-四甲基哌啶的衍生物,的结合也是优选的。这些包括用于新型化合物的非氧化起始化合物。
在所有这些情况中,至多50wt%的Ia和Ib可以被其它氧化合物取代。
为了达到稳定的目的,优选以下列浓度使用新型化合物:
-对于塑料的稳定:
仅使用Ia或Ib:0.01-5wt%,优选0.02-1wt%,基于塑料的量。
-对于脂肪类,油类,和表面涂料的稳定:
0.01-5wt%,优选0.02-1wt%。
-对于能进行自由基聚合反应的单体的储存:
0.0002-0.1wt%,优选0.0005-0.01wt%
-对于能进行自由基聚合反应的单体的蒸馏:
0.0005-0.5wt%,优选0.005-0.05wt%。
Ia和Ib与作为助稳定剂的芳族硝基或亚硝基化合物或取代的酚结合:0.0005-0.5wt%,优选0.005-0.05wt%的Ia或Ib加上0.001-0.5wt%的助稳定剂
实施例
实施例1
在70℃的温度下,用2小时的时间,向540克(1.37摩尔)的N,N′-双[2,2,6,6-四甲基哌啶-4-基]-N,N′-双甲酰基-1,6-二氨基己烷,800ml水,150ml异丁醇和200mgMgSO4的悬浮液中加入600ml 30wt%的过氧化氢溶液(19.6摩尔),混合物在此温度下再保持16小时。然后,混合物被冷却至室温并将沉淀产物用常用的方式分离。产品不仅含有二-N-氧化物,而且还含有作为副产品的单-N-氧化物。
产率:85%,熔点:169-170℃。
用与实施例1相似的方式,但使用甲醇代替水/异丁醇作为溶剂来制备下列化合物实施例:
实施例5
实施例1的化合物在苯乙烯中的稳定作用:
将实施例1的稳定剂和,作为比较,各种常用的稳定剂以120ppm的浓度溶于苯乙烯中。在氮气下,在反应釜中,将500ml此溶液加热到110℃。将相同的溶液以250g/h的速度连续地加入到该加热的苯乙烯溶液中,并连续排出相同的量。在出口测得平衡时聚合物的含量。测得以下结果:
稳定剂 | 聚合物含量,% |
本发明:实施例1的化合物 | 0.10 |
对比:癸二酸双(1-氧-2,2,6,6-四甲基哌啶-4-基酯),对亚硝基苯酚, | 0.240.18 |
对亚硝基-邻-甲基苯酚 | 0.30 |
无稳定剂: | >5.00* |
*在建立平衡之前终上。
实施例6
实施例1的化合物与共稳定剂结合的稳定作用:
将实施例1的稳定剂和用作对比的常用的稳定剂以浓度120ppm溶于苯乙烯中。此外,将2,4-二硝基-仲丁基苯酚作为共稳定剂以浓度240ppm也溶于此苯乙烯中。如实施例5那样,对溶液进行试验,再次在出口测定聚合物的含量。
发现以下结果:
稳定剂 | 聚合物含量,% |
本发明:实施例1的化合物+2,4-二硝基-仲丁基苯酚 | 0.04 |
对比癸二酸双(1-氧-2,2,6,6-四甲基哌啶-4-基酯)+2,4-二硝基-仲丁基苯酚 | 0.07 |
实施例7
实施例1的化合物在丙烯酸中的稳定作用:
将添加有50ppm实施例1的稳定剂和用作对比的各种常用稳定剂的丙烯酸熔融,将熔融物恒温在80℃。测定直至聚合反应开始的诱导期。测得以下结果:
稳定剂 | 诱导期[h] |
本发明:实施例1的化合物 | 502 |
对比癸二酸双(1-氧-2,2,6,6-四甲基哌啶-4-基酯)吩噻嗪 | 470170 |
无稳定剂 | 1 |
Claims (17)
1.由通式Ia表示的4-甲酰基氨基哌啶N-氧化物
A1B1 (Ia)
其中A1是有机基团,其选自下述基团:
C1-C22-烷基,
C3-C22-链烯基,
C3-C12-环烷基,
氰基-,羟基-或烷氧基羰基取代的C2-C22-烷基,
被醚式氧或氮间断或被羟基取代的C4-C22-烷基,
未取代的或取代的C7-C22-苯基烷基和C13-C22-二苯基烷基基团,所述取代基选自甲氧基、甲基、乙基、异丙基、氟、氯、亚甲二氧基或二甲基氨基,
芳基,
带有杂环结构的C1-C22-烷基,
具有烷基残基的磷酰胺、膦酸衍生物或磷酸衍生物,
和B1是通式IIa所示的基团
其中
R1至R4各自是C1-C4-烷基,和一方面R1和R2,另一方面R3和R4也可被键接而形成5元环或6元环,
R5是H和
R6是H,
但化合物4-[N-甲酰基-N-(3-羟基丙基)氨基]-2,2,6,6-四甲基哌啶-1-氧化物被排除在外。
2.根据权利要求1的通式Ia的4-甲酰基氨基哌啶N-氧化物,其中A1是苄基,异构的甲氧基苄基,甲基苄基,乙基苄基,异丙基苄基,三甲基苄基,氟苄基,氯苄基,亚甲二氧基苄基,苯基乙基,苯基丙基和苯基丁基,二甲基氨基苄基,二苯基甲基和1,3-二苯基丙-2-基。
4.根据权利要求3的4-甲酰基氨基哌啶N-氧化物,其中R7定义中的O-烃基为O-烷基、O-芳基。
5.根据权利要求1-4中任何一项所要求的4-甲酰基氨基哌啶N-氧化物,其中R1至R4各自是甲基。
6.根据权利要求3或4所要求的4-甲酰基氨基哌啶N-氧化物,其中A2是具有2-8个碳原子的α,ω-亚烷基。
7.N,N′-双(1-氧-2,2,6,6-四甲基哌啶-4-基)-N,N′-双甲酰基-1,6-二氨基己烷。
8.制备根据权利要求1-7中任何一项所要求的4-甲酰基氨基哌啶N-氧化物的方法,其中用过氧化氢氧化相应的N-未取代的哌啶。
9.根据权利要求1-7中任何一项所要求的4-甲酰基氨基哌啶N-氧化物用于稳定有机材料抵抗自由基的有害作用的用途。
10.根据权利要求9所要求的4-甲酰基氨基哌啶N-氧化物的用途,用于稳定能进行自由基聚合反应的单体。
11.根据权利要求10中所要求的4-甲酰基氨基哌啶N-氧化物的用途,用于稳定苯乙烯。
12.根据权利要求9-11中任何一项所要求的4-甲酰基氨基哌啶N-氧化物的用途,所述N-氧化物是与芳族硝基或亚硝基化合物或取代的酚类或者这些化合物的混合物一起使用。
13.一种通过蒸馏被污染单体来提纯能进行自由基聚合反应的单体的方法,在该方法中蒸馏是在权利要求1-7中任何一项所要求的4-甲酰基氨基哌啶N-氧化物存在下进行的。
14.根据权利要求13所要求的方法,它用于提纯苯乙烯。
15.根据权利要求13所要求的方法,其中所述N-甲酰基氨基哌啶N-氧化物是与芳族硝基或亚硝基化合物或取代的酚类或者这些化合物的混合物一起使用。
16.权利要求1-7中任何一项所要求的4-甲酰基氨基哌啶N-氧化物与芳族硝基或亚硝基化合物或者取代的酚类的混合物。
17.含有根据权利要求1-7中任何一项所要求的4-甲酰基氨基哌啶N-氧化物的塑料、表面涂料、油或脂肪或能进行自由基聚合反应的单体。
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DE19725519A1 (de) | 1997-06-17 | 1998-12-24 | Basf Ag | Stoffmischung, enthaltend vinylgruppenhaltige Verbindungen und Stabilisatoren |
US6447644B1 (en) | 1997-07-23 | 2002-09-10 | Ciba Specialty Chemicals Corporation | Inhibition of pulp and paper yellowing using nitroxides, hydroxylamines and other coadditives |
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CN100441551C (zh) * | 2000-10-16 | 2008-12-10 | 尤尼罗亚尔化学公司 | 作为聚合抑制剂的c-亚硝基苯胺化合物及其共混物 |
US6685823B2 (en) * | 2000-10-16 | 2004-02-03 | Uniroyal Chemical Company, Inc. | C-nitrosoaniline compounds and their blends as polymerization inhibitors |
DE10223613B4 (de) * | 2002-05-27 | 2006-01-05 | Basf Ag | Verfahren zur anionischen Polymerisation von Styrolmonomeren und deren Verwendung |
US7696290B2 (en) * | 2004-12-03 | 2010-04-13 | Crompton Corporation | Aromatic sulfonic acids, amines, and nitrophenols in combination with nitroxyl radical-containing compounds or C-nitrosanilines as polymerization inhibitors |
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KR100413167B1 (ko) | 2004-04-28 |
TW326446B (en) | 1998-02-11 |
MX9706337A (es) | 1998-07-31 |
ATE212014T1 (de) | 2002-02-15 |
EA199700246A1 (ru) | 1998-02-26 |
ES2171659T3 (es) | 2002-09-16 |
NO974336L (no) | 1997-09-19 |
SK108497A3 (en) | 1998-03-04 |
DE19510184A1 (de) | 1996-09-26 |
AU5144496A (en) | 1996-10-08 |
PL322309A1 (en) | 1998-01-19 |
BG101836A (en) | 1998-09-30 |
EP0815082A1 (de) | 1998-01-07 |
JPH11502212A (ja) | 1999-02-23 |
CA2211902A1 (en) | 1996-09-26 |
DE59608597D1 (de) | 2002-02-21 |
CN1179150A (zh) | 1998-04-15 |
WO1996029311A1 (de) | 1996-09-26 |
EP0815082B1 (de) | 2002-01-16 |
KR19980703127A (ko) | 1998-10-15 |
NO974336D0 (no) | 1997-09-19 |
JP4152435B2 (ja) | 2008-09-17 |
BR9607652A (pt) | 1998-06-16 |
CZ274397A3 (cs) | 1998-01-14 |
US5922244A (en) | 1999-07-13 |
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