CN1135477A - 双酚酯衍生物 - Google Patents
双酚酯衍生物 Download PDFInfo
- Publication number
- CN1135477A CN1135477A CN96101362A CN96101362A CN1135477A CN 1135477 A CN1135477 A CN 1135477A CN 96101362 A CN96101362 A CN 96101362A CN 96101362 A CN96101362 A CN 96101362A CN 1135477 A CN1135477 A CN 1135477A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- phenyl
- cycloalkyl
- substituted
- hydrogen
- 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
- 150000002148 esters Chemical class 0.000 title description 35
- 239000011368 organic material Substances 0.000 claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000006731 degradation reaction Methods 0.000 claims abstract description 8
- -1 methylene, ethylidene Chemical group 0.000 claims description 127
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 97
- 239000000203 mixture Substances 0.000 claims description 64
- 229910052739 hydrogen Inorganic materials 0.000 claims description 63
- 239000001257 hydrogen Substances 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 46
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 40
- 150000002431 hydrogen Chemical class 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 125000000081 (C5-C8) cycloalkenyl group Chemical group 0.000 claims description 12
- 229920002857 polybutadiene Polymers 0.000 claims description 12
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
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- 239000005864 Sulphur Substances 0.000 claims description 4
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- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 10
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 34
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- 239000002585 base Substances 0.000 description 28
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- WFOVEDJTASPCIR-UHFFFAOYSA-N 3-[(4-methyl-5-pyridin-4-yl-1,2,4-triazol-3-yl)methylamino]-n-[[2-(trifluoromethyl)phenyl]methyl]benzamide Chemical compound N=1N=C(C=2C=CN=CC=2)N(C)C=1CNC(C=1)=CC=CC=1C(=O)NCC1=CC=CC=C1C(F)(F)F WFOVEDJTASPCIR-UHFFFAOYSA-N 0.000 description 10
- 239000005062 Polybutadiene Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 10
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- 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 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 239000004700 high-density polyethylene Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical class CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 7
- 239000007859 condensation product Substances 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 229920001903 high density polyethylene Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 229920006324 polyoxymethylene Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 229940035422 diphenylamine Drugs 0.000 description 6
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
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- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
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- 238000004458 analytical method Methods 0.000 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
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- 238000004132 cross linking Methods 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 5
- 235000019439 ethyl acetate Nutrition 0.000 description 5
- IIYFAKIEWZDVMP-UHFFFAOYSA-N linear paraffin C13 Natural products CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 5
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
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- 229940116351 sebacate Drugs 0.000 description 5
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical class OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 4
- FOVKHTSFPJLUQN-UHFFFAOYSA-N 1-ethoxy-1,3,5-triazinane-2,4,6-trione Chemical class CCON1C(=O)NC(=O)NC1=O FOVKHTSFPJLUQN-UHFFFAOYSA-N 0.000 description 4
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- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical compound C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 4
- BGQNNKZAJXZSPQ-UHFFFAOYSA-N 5,6-dimethylheptane-1,6-diol Chemical compound CC(O)(C)C(C)CCCCO BGQNNKZAJXZSPQ-UHFFFAOYSA-N 0.000 description 4
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Abstract
式I的新型化合物,式中A为式IIa或IIb的基团,Y为氧、亚甲基、亚乙基或>C=C(CH3)2,Z为氮、或,R1和R2例如为C1-C5烷基、R3和R4例如为氢或甲基,R5、R6、R7、R8、R9、R10、R11、R12、R13和R14例如为氢,该化合物适用于使有机材料对氧化、热或光引发的降解作用稳定。
Description
本发明涉及新型双酚酯衍生物,涉及它们的应用以及涉及用这些化合物使有机材料对氧化、热和光引发的降解作用稳定。
已公开了某些双酚酯衍生物作为稳定剂的应用,如在JP-A-平4308581、DE-A-3718751、EP-A-479560和US-A-4414408中。式中,A为式IIa或IIb的基团Y为氧、亚甲基、亚乙基或>C=C(CH3)2基,Z为氮,
或
R1各自独立为C1-C25烷基、C2-C24链烯基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、C5-C12环烯基、C1-C4烷基取代的C5-C12环烯基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基或-CH2-S-X1,R2各自独立为氢、C1-C25烷基、C2-C24链烯基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、C5-C12环烯基、C1-C4烷基取代的C5-C12环烯基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基、-CH2-S-X1、-(CH2)pCOO-X2或-(CH2)qO-X3,R3各自独立为氢或C1-C4烷基,R4为氢或C1-C8烷基,R5为氢、C1-C10烷基、苯基、-CH2-COO-X4或CN,R6为氢、C1-C4烷基、苯基、-COO-X5、-CN或-CON(X6)(X7),R7为氢或C1-C10烷基,R8、R9和R10各自独立为氢或C1-C4烷基,R11和R12各自独立为氢、C1-C4烷基或苯基,R13和R14各自独立为氢或C1-C4烷基,X1为C1-C25烷基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基或-(CH2)rCOO-Y1,X2、X4和X5各自独立为C1-C25烷基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、苯基、C1-C4烷基取代的苯基或C7-C9苯烷基,X3为C1-C25烷基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基、C1-C25烷酰基、C3-C25链烯酰基、氧、硫或>N-Y2间断的C3-C25烷酰基、C6-C9环烷基羰基、苯甲酰基、C1-C4烷基取代的苯甲酰基、噻吩甲酰基或糠酰基,X6和X7各自独立为氢、C1-C25烷基、C2-C24链烯基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、C5-C12环烯基、C1-C4烷基取代的C5-C12环烯基、苯基、C1-C4烷基取代的苯基或C7-C9苯烷基,Y1为C1-C25烷基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、苯基、C1-C4烷基取代的苯基或C7-C9苯烷基,Y2为氢或C1-C8烷基,p为0、1或2,q为0-8中的一个整数,r为1或2。
有至多25个碳原子的烷基,优选有至多18个碳原子的烷基,更优选有至多10个碳原子的烷基例如为甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、2-乙基丁基、正戊基、叔戊基、异戊基、1-甲基戊基、1,3-二甲基丁基、正己基、1-甲基己基、正庚基、异庚基、 1,1,3,3-四甲基丁基、1-甲基庚基、3-甲基庚基、正辛基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、壬基、癸基、十一烷基、1-甲基-十一烷基、十二烷基、1,1,3,3,5,5-六甲基己基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、二十烷基或二十二烷基。
R1和R2中优选的基团之一为有至多10个碳原子的支链烷基,更优选有至多5个碳原子的支链烷基,如叔丁基或叔戊基。
R4中优选的基团之一为C1-C4烷基,特别是甲基。
Y2中优选的基团之一为C1-C4烷基,特别是甲基。
有至多24个碳原子的链烯基,特别是有至多18个碳原子的链烯基例如为乙烯基、丙烯基、异丙烯基、2-丁烯基、3-丁烯基、异丁烯基、3-甲基-丁-2-烯基、正辛-2-烯基、正癸-2-烯基、异癸烯基、正十八-2-烯基或正十八-4-烯基。在1位上碳原子是饱和的链烯基是优选的。C3-C18链烯基是特别优选的。
未取代的或C1-C4烷基取代的C5-C12环烷基例如为环戊基、环己基、环庚基、环辛基、环十二烷基、2-或4-甲基环己基、二甲基环己基、三甲基环己基或叔丁基环己基。未取代的或C1-C4烷基取代的C5-C8环烷基。特别是环己基是优选的。
未取代的或C1-C4烷基取代的C5-C12环烯基的例子,优选C5-C8环烯基的例子为环己-2-烯基、环庚-3-烯基和4-叔丁基环己-2-烯基。环己烯基是优选的。
C1-C4烷基取代的苯基例如为甲基苯基、二甲基苯基、三甲基苯基、乙基苯基、二乙基苯基、异丙基苯基、叔丁基苯基、二叔丁基苯基或甲基-二叔丁基苯基。
未取代的或苯环被C1-C4烷基取代的C7-C9苯烷基的例子为苄基、苯乙基、3-苯丙基、α-甲基苄基、α,α-二甲基苄基、甲基苄基、二甲基苄基、三甲基苄基和叔丁基苄基。
有至多25个碳原子的烷酰基例如为甲酰基、乙酰基、丙酰基、丁酰基、戊酰基、己酰基、庚酰基、辛酰基、壬酰基、癸酰基、十一烷酰基、十二烷酰基、十三烷酰基、十四烷酰基、十五烷酰基、十六烷酰基、十八烷酰基、十九烷酰基或二十烷酰基。C1-C18烷酰基是优选的。
被氧、硫或>N-Y2间断的C3-C25烷酰基的例子是-CO-CH2CH2-S-(C1-C10烷基)、-CO-CH2CH2-O-(C1-C10烷基)和-CO-CH2CH2-N(Y2)-(C1-C10烷基)。被氧或>N-Y2间断的C3-C25烷酰基是优选的。
C3-C25链烯酰基的例子为丙烯酰基、甲基丙烯酰基、巴豆酰基、异巴豆酰基和油酰基。C3-C18链烯酰基是优选的。
C6-C9环烷基羰基例如为环戊基羰基、环己基羰基、环庚基羰基或环辛基羰基。
C1-C4烷基取代的苯甲酰基例如为甲基苯甲酰基或叔丁基苯甲酰基。
优选以下式I化合物,其中R1各自独立为C1-C18烷基、C2-C18链烯基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、C5-C8环烯基、C1-C4烷基取代的C5-C8环烯基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基或-CH2-S-X1,R2各自独立为氢、C1-C18烷基、C2-C18链烯基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、C5-C8环烯基、C1-C4烷基取代的C5-C8环烯基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基、-CH2-S-X1、-(CH2)pCOO-X2或-(CH2)qO-X3,R5为氢、C1-C10烷基、苯基或CN,R6为氢、C1-C4烷基或苯基,X1为C1-C18烷基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基或-(CH2)rCOO -Y 1 ,X2为C1-C18烷基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、苯基、C1-C4烷基取代的苯基或C7-C9苯烷基,X3为C1-C18烷基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基、C1-C18烷酰基、C3-C18烯酰基、被氧或>N-Y2间断的C3-C18烷酰基、C6-C9环烷基羰基、苯甲酰基、C1-C4烷基取代的苯甲酰基、噻吩甲酰基或糠酰基、以及Y1为C1-C18烷基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、苯基、C1-C4烷基取代的苯基或C7-C9苯烷基。
同样优选以下式I的化合物,其中R1各自独立为C1-C10烷基、C2-C18链烯基、C5-C8环烷基、C5-C8环烯基、苯基、C7-C9苯烷基或-CH2-S-X1,R2各自独立为氢、C1-C10烷基、C2-C18链烯基、C5-C8环烷基、C5-C8环烯基、苯基、C7-C9苯烷基、-CH2-S-X1、-(CH2)pCOO-X2或-(CH2)qO-X3,R3为氢,R4为氢或C1-C4烷基,R5为氢、C1-C4烷基,苯基或CN,R6为氢、C1-C4烷基或苯基,R7为氢或C1-C4烷基,X1为C1-C10烷基、C5-C8环烷基、苯基、C7-C9苯烷基或-(CH2)rCOO-Y1,X2为C1-C10烷基、C5-C8环烷基、苯基或C7-C9苯烷基,X3为C1-C10烷基、C5-C8环烷基、苯基、C7-C9苯烷基、C1-C10烷酰基、C3-C18烯酰基、被氧间断的C3-C18烷酰基或苯甲酰基,以及Y1为C1-C10烷基、C5-C8环烷基、苯基或C7-C9苯烷基。R8、R9、R10、R11、R12、R13和R14优选为氢。
同样优选以下式I的化合物,其中R1各自独立为C1-C5烷基或C5-C8环烷基,R2各自独立为C1-C5烷基,R3为氢,以及R4为氢或C1-C4烷基。
同样优选以下式I的化合物,其中R1各自独立为支链的C3-C5烷基,R2为相同的,并为C1-C5烷基,R3为氢,以及R4为氢或C1-C4烷基。
特别优选以下式I的化合物,其中Y为氧或亚甲基,Z为
基,R1为相同的,并为支链的C3-C5烷基,R2为相同的,并为C1-C5烷基,R3为氢,R4为氢或C1-C4烷基,R5为氢、C1-C4烷基或CN,以及R6、R7、R8、R9、R10、R11、R12、R13和R14为氢。
特别优选下式化合物
式I的化合物可用以下方法制备,这些方法都是已知的方法:
方法A:
式a化合物与适合的式b-1或c的化合物反应(如在“Com-prehensive Organic Synthesis,Vol,IV,315(1991),PergamonPress,or Chem,Rev.1993,93,741-761”中描述的狄尔斯-阿德式中可变化的基团为如上规定的。
这一狄尔斯-阿德耳热反应例如可通过两种反应物在适合的溶剂中,在室温至反应混合物的沸点之间的温度下混合的方法来进行。该反应优选在没有氧的情况下进行。可能的溶剂为传统的烃类(例如甲苯、己烷或环己烷)、卤代烃类(例如二氯甲烷、二氯乙烷或氯苯)、醚类(例如乙醚、四氢呋喃或二甲氧基乙烷)、醇类(例如甲醇、乙醇或异丙醇)、水或水/醇或水/醚混合物。
如果Y为亚甲基和Z为
或
,那么式b-l的化合物可用式b-2的二聚物代替在这种情况下,在高温如180-220℃(二聚物如双环戊二烯的裂化温度)下,在密闭体系(高压釜)中,在压力(如l-5巴)下进行这一反应是有利的。反应也可在没有溶剂的情况下进行。
此外,该反应也可在路易士酸作为催化剂存在下,在低温(如0-50℃)下进行。催化剂的用量优选为2~50%(摩尔),特别是2-10%(摩尔)。适合的路易士酸的例子为R-Al-Cl2或(R)2-AlCl(其中R为甲基、乙基、正丙基或异丙基)或AlCl3、SnCl4、ZnCl2、ZnI2、FeCl3或TiCl4。
方法B:
式d或e的羧酸衍生物与式f的双酚的酯转移反应,
反应可按已知的方式进行,例如将两种反应物中的一种加到第二种原料中,并将两种反应物混合,优选在没有氧的情况下进行。反应可在有或没有溶剂(如甲苯)的情况下进行。温度例如可在反应混合物的熔点和沸点之间。例如在-50至150℃之间,优选在0至150℃之间。生成的产物同样可用已知的方法纯化,例如通过溶剂蒸发和粗产物结晶或用水/HCl洗涤,用有机溶剂萃取、结晶和/或色谱分离。萃取和色谱分离纯化的优选溶剂是已烷、乙酸乙酯或其混合物。
如果在反应中所用的式d或e的羧酸衍生物是酰基氯(X=Cl),那么酸受体也可加到反应混合物中。适合的酸受体的例子是胺类,如吡啶或三乙胺。酸受体的用量优选至少相当于酰基氯的用量。按酰基氯计,例如为1-2当量,特别是1.2-1.7当量。
酰基氯也可原位制备。在这种情况下,将式d或e的羧酸(X=OH)、式f的双酚和酸受体(如三乙胺)送入反应器,然后将磷酰氯加入,类似于例如在US-A-5128398中公开的方法。
此外,还可首先制备式f的双酚的单钠、单钾或单锂酚盐,然后再让它与酰基氯反应。必需的酚盐用氢化物、碱金属、碱土金属氢氧化物、碱金属醇盐或烷基锂化合物为基础来制备。
如果式d或e的羧酸(X=OH)和式f的双酚直接用作原料,那么反应宜用能吸收所释放的水的试剂如双环己基碳二亚胺进行。
用于上述方法的原料是已知的,其中一些可商购,或用与已知方法类似的方法制备。
式I的化合物以异构体混合物形成(桥式、挂式、顺式或反式等)生成,它们随制备方法而变化。
式I化合物的例子列入下表1。
表1
表1(续)
表1(续)
表1(续)
式I化合物适用于使有机材料对热、氧化或光引发的降解作用稳定。这样的材料的例子如下:
1.单烯烃和二烯烃的聚合物,例如聚丙烯、聚异丁烯、聚丁-1-烯、聚4-甲基戊-1-烯、聚异戊二烯或聚丁二烯,以及环烯烃如环戊烯或降冰片烯的聚合物,聚乙烯(它必要时可交联),例如高密度聚乙烯(HDPE)、高密度和高分子量聚乙烯(HDPE-HMW)、高密度和超高分子量聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、线型低密度聚乙烯(LLDPE)、支链的低密度聚乙烯(BLDPE)。
聚烯烃,即前一段中例举的单烯烃的聚合物,优选聚乙烯和聚丙烯,可用不同的方法制备,特别是用以下的方法制备:
a)自由基聚合(通常在高压和升温下进行)。
b)使用通常含有元素周期表第IVb、Vb、VIb或VIII族的一种或多种金属的催化剂的催化聚合。这些金属通常有一个或多个配体,它们通常是π或σ配位的氧化物、卤化物、醇盐、酯类、醚类、胺类、烷基、链烯基和/或芳基。这些金属配合物可成游离形式或固定在基质上,通常在活性氯化镁、氯化钛(III)、氧化铝或氧化硅上。这些催化剂可溶于或不溶于聚合介质中。在聚合中可就使用催化剂本身,或者还可使用活化剂,通常是金属烷基化物、金属氢化物、金属烷基卤化物、金属烷基氧化物或金属烷基恶烷,所述的金属是元素周期表第Ia、IIa和/或IIIa族元素。活化剂宜用另外的酯、醚、胺或甲硅烷基醚基团改性。这些催化剂体系通常称为Phillips催化剂、StandardOil Indiana催化剂、Ziegler(-Natta)催化剂、TNZ(DuPont)催化剂、金属茂催化剂或单活性中心催化剂(SSC)。
2.1中提到的聚合物的混合物,例如聚丙烯与聚异丁烯的混合物、聚丙烯与聚乙烯的混合物(如PP/HDPE,PP/LDPE)和不同类型聚乙烯的混合物(如LDPE/HDPE)。
3.单烯烃和二烯烃彼此的共聚物或与其它乙烯基单体的共聚物,如乙烯/丙烯共聚物、线型低密度聚乙烯(LLDPE)及其混合物与低密度聚乙烯(LDPE)的共聚物、丙烯/丁-1-烯共聚物、丙烯/异丁烯共聚物、乙烯/丁-1-烯共聚物、乙烯/己烯共聚物、乙烯/甲基戊烯共聚物、乙烯/庚烯共聚物、乙烯/辛烯共聚物、丙烯/丁二烯共聚物、异丁烯/异戊二烯共聚物、乙烯/丙烯酸烷基酯共聚物、乙烯/甲基丙烯酸烷基酯共聚物、乙烯/乙酸乙烯基酯共聚物及其与一氧化碳的共聚物或乙烯/丙烯酸共聚物及其盐(异构体)以及乙烯与丙烯和二烯烃如己二烯、双环戊二烯或亚乙基-降冰片烯的三元聚合物;这些共聚物与另外共聚物和与上面1中提到的聚合物的混合物,如聚丙烯/乙烯-丙烯共聚物、LDPE/乙烯-乙酸乙烯基酯共聚物(EVA)、LDPE/乙烯-丙烯酸共聚物(EAA)、LLDPE/EVA、LLD-PE/EAA和交替的或无规聚亚烷基/一氧化碳共聚物及其与其他聚合物如聚酰胺的混合物。
4.包括对其卤化改性的烃类树脂(如C5-C9)(例如增粘剂)和聚亚烷基和淀粉的混合物。
5.聚苯乙烯、聚(对甲基苯乙烯)、聚(α-甲基苯乙烯)。
6.苯乙烯或α-甲基苯乙烯与二烯烃或丙烯酸衍生物的共聚物,例如苯乙烯/丁二烯、苯乙烯/丙烯腈、苯乙烯/甲基丙烯酸烷基酯、苯乙烯/丁二烯/丙烯酸烷基酯、苯乙烯/丁二烯/甲基丙烯酸烷基酯、苯乙烯/马来酸酐、苯乙烯/丙烯腈/丙烯酸甲酯;苯乙烯共聚物和另外的聚合物,如聚丙烯酸酯、二烯烃聚合物或乙烯/丙烯/二烯烃三元聚合物的高抗冲强度混合物;苯乙烯嵌段共聚物如苯乙烯/丁二烯/苯乙烯、苯乙烯/异戊二烯/苯乙烯、苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯/乙烯/丙烯/苯乙烯。
7.苯乙烯或α-甲基苯乙烯的接枝共聚物,如苯乙烯在聚丁二烯上、苯乙烯在聚丁二烯-苯乙烯上或在聚丁二烯-丙烯腈共聚物上;苯乙烯和丙烯腈(或甲基丙烯腈)在聚丁二烯上;苯乙烯、丙烯腈和甲基丙烯酸甲酯在聚丁二烯上;苯乙烯和马来酸酐在聚丁二烯上;苯乙烯、丙烯腈和马来酸酐或马来酰亚胺在聚丁二烯上;苯乙烯和马来酰亚胺在聚丁二烯上;苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯在聚丁二烯上;苯乙烯和丙烯腈在乙烯/丙烯/二烯烃三元聚合物上;苯乙烯和丙烯腈在聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯上;苯乙烯和丙烯腈在丙烯酸酯/丁二烯共聚物上;以及它们与6中所列共聚物的混合物,如称为ABS、MBS、ASA或AES聚合物的共聚物混合物。
8.含卤素的聚合物,如聚氯丁二烯、氯化橡胶、氯化的和溴化的异丁烯-异戊二烯共聚物(卤代丁基橡胶)、氯化的或磺氯化的聚乙烯、乙烯和氯化乙烯的共聚物、表氯醇均聚物和共聚物,特别是含卤素的乙烯基化合物的聚合物如聚氯乙烯、聚偏氯乙烯、聚氟乙烯、聚偏氟乙烯、及其共聚物如氯乙烯/偏氯乙烯共聚物、氯乙烯/乙酸乙烯基酯共聚物或偏氯乙烯/乙酸乙烯基酯共聚物。
9.由α,β-不饱和酸及其衍生物制得的聚合物,如聚丙烯酸酯和聚甲基丙烯酸酯;用丙烯酸丁酯改性冲击强度的聚甲基丙烯酸甲酯、聚丙烯酰胺和聚丙烯腈。
10.9中提到的单体彼此的共聚物或与其他不饱和单体的共聚物,如丙烯腈/丁二烯共聚物、丙烯腈/丙烯酸烷基酯共聚物、丙烯腈/丙烯酸烷氧基烷基酯或丙烯腈/乙烯基卤共聚物或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元聚合物。
11.由不饱和醇和胺或其酰基衍生物或其缩醛制得的聚合物,如聚乙烯醇、聚乙酸乙烯酯、聚硬脂酸乙烯酯、聚苯甲酸乙烯酯、聚马来酸乙烯酯、聚乙烯醇缩丁醛、聚邻苯二甲酸烯丙酯或聚烯丙基密胺;以及它们与上面1中提到的烯烃的共聚物。
12.环醚的均聚物和共聚物,如聚亚烷基二醇、聚环氧乙烷、聚环氧丙烷或它们与二缩水甘油醚的共聚物。
13.聚缩醛类,如聚氧亚甲基和含有环氧乙烷作为共聚单体的聚氧亚甲基;用热塑性聚氨酯类、丙烯酸酯类或MBS改性的聚缩醛类。
14.聚苯氧类和聚苯硫类,以及聚苯氧与苯乙烯聚合物或聚酰胺的混合物。
15.由一端是羟基封端的聚醚、聚酯或聚丁二烯,另一端是脂族或芳族聚异氰酸酯以及它们的前体得到的聚氨酯。
16.由二胺和二羧酸和/或由氨基羧酸或相应的内酰胺制得的聚酰胺和共聚酰胺,如聚酰胺4、聚酰胺6、聚酰胺6/6、6/10、6/9、6/12、4/6、12/12、聚酰胺11、聚酰胺12、由间二甲苯二胺和己二酸得到的芳族聚酰胺;由六亚甲基二胺和间苯二甲酸或/和对苯二甲酸得到的聚酰胺(有或没有弹性体作改性剂),如聚2,4,4-三甲基六亚甲基对苯二甲酰胺或聚间亚苯基间苯二甲酰胺;上述聚酰胺与聚烯烃、烯烃共聚物、离子单体或化学键联的或接枝的弹性体的嵌段共聚物,或与聚醚的嵌段共聚物,如与聚乙二醇、聚丙二醇或聚丁二醇的嵌段共聚物;以及用EPDM或ABS改性的聚酰胺或共聚酰胺;和在加工过程中缩聚的聚酰胺(RIM聚酰胺体系)。
17.聚脲、聚酰亚胺、聚酰胺-亚酰胺、聚醚酰亚胺、聚酯酰亚胺、聚海因和聚苯并咪唑。
18.由二元羧酸和二元醇和/或由羟基羧酸或对应的内酯制得的聚酯,如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸1,4-二羟甲基环己烷酯和聚羟基苯甲酸酯以及由羟基封端的聚醚得到的嵌段共聚醚酯;还有用聚碳酸酯或MBS改性的聚酯。
19.聚碳酸酯和聚酯碳酸酯。
20.聚砜、聚醚砜和聚醚酮。
21.由一头是醛和另一头是酚、脲和密胺得到的交联聚合物,如酚醛树脂、脲醛树脂和密胺醛树脂。
22.干燥和未干燥的醇酸树脂。
23.由饱和的和不饱和的二元羧酸与多元醇的共聚物制得的不饱和聚酯树脂,乙烯基化合物作交联剂,含其卤素改性剂使它有低的可燃性。
24.由取代的丙烯酸酯得到的可交联的丙烯酸树脂,如环氧丙烯酸酯、聚氨酯丙烯酸酯或聚酯丙烯酸酯。
25.与三聚氰胺树脂、尿醛树脂、异氰酸酯、异氰脲酸酯、聚异氰酸酯或环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸酯树脂。
26.由脂族、环脂族、杂环族或芳族缩水甘油基化合物得到的交联环氧树脂,如双酚A和双酚F的缩水甘油醚的产物,它们与常用的硬化剂如酸酐或胺类交联,含有或没有促进剂。
27.天然聚合物,如纤维素、橡胶、明胶及其化学改性的均匀衍生物,如乙酸纤维素、丙酸纤维素和丁酸纤维素,或纤维素醚如甲基纤维素;以及松脂及其衍生物。
28.上述聚合物的共混物(共混聚合物),如PP/EPDM、聚酰胺/EPDM或ABS、PVC/EVA、PVC/ABS、PVC/MBS、PC/ABS、PBTP/ABS、PC/ASA、PC/PBT、PVC/CPE、PVC/丙烯酸酯、POM/热塑性PUR、PC/热塑性PUR、POM/丙烯酸酯、POM/MBS、PPO/HIPS、PPO/PA6.6和共聚物、PA/HDPE、PA/PP、PA/PPO、PBT/PC/ABS或PBT/PET/PC。
29.天然存在的和合成的有机材料,它们是纯的单体化合物或这些化合物的混合物,如矿物油、动物和植物脂肪、油和蜡,或以合成酯(如邻苯二甲酸酯、己二酸酯、磷酸酯或偏苯三酸酯)和合成酯与矿物油以任何重量比的混合物为基础的油、脂肪和蜡,通常它们用作纺丝组合物,以及这些材料的含水乳状液。
30.天然或合成橡胶的含水乳状液,如天然乳胶或羧化的苯乙烯/丁二烯共聚物的胶乳。
所以,本发明还涉及一种含有对氧化、热或光引发的降解作用敏感的有机材料和至少一种式I化合物的组合物。
有机材料优选为合成聚合物,特别是上面给出的那几类。聚烯烃和溶液聚合的聚丁二烯橡胶是特别优选的。同样,特别优选的是溶液聚合的苯乙烯-丁二烯共聚物和苯乙烯-丁二烯嵌段共聚物,其中苯乙烯与共轭丁二烯之比例如为5∶95至95∶5。在这些共聚物中,聚丁二烯的比例优选为5-30%。
通常,将按要稳定的材料的总重计0.01-10%的式I化合物加到要稳定的有机材料中,优选0.01-5%,特别优选0.05-0.5%。
可用已知的方法将新型化合物加到有机材料中,例如在成型前或成型过程中,或将溶解或分散的化合物加到有机材料中,如果需要的话,随后可蒸去溶剂。可以粉末、颗粒的形式或以母料的形式将新型化合物加到要稳定的材料中,母料含有这些化合物,例如浓度为2.5-25%(重)。
也可在聚合以前或在聚合过程中或在交联以前将式I的化合物加入,例如在溶液聚合过程中,在蒸发溶剂以前。
用这一方法稳定的材料可以各种形式应用,如薄膜、纤维、带材、模制组合物、型材或作为表面涂层的粘结剂、粘合剂或腻子。
本发明稳定的有机材料还可含有各种传统的添加剂,例如:
1抗氧化剂类
1.1烷基化单酚类,如2,6-二叔丁基-4-甲基酚、2-叔丁基-4,6-二甲基酚、2,6-二叔丁基-4-乙基酚、2,6-二叔丁基-4-正丁基酚、2,6-二叔丁基-4-异丁基酚、2,6-二环戊基-4-甲基酚、2-(α-甲基环己基)-4,6-二甲基酚、2,6-二(十八烷基)-4-甲基酚、2,4,6-三环己基酚、2,6-二叔丁基-4-甲氧甲基酚、侧链为直链或支链的壬基酚如2,6-二壬基-4-甲基酚、2,4-二甲基-6-(1′-甲基-十一烷-1′-基)酚、2,4-二甲基-6-(1′-甲基-十七烷-1′-基)酚、2,4-二甲基-6-(1′-甲基-十三烷-1′-基)酚及其混合物。
1.2烷基硫甲基酚类,如2,4-二辛基硫甲基-6-叔丁基酚、2,4-二辛基硫甲基-6-甲基酚、2,4-二辛基硫甲基-6-乙基酚、2,6-二(十二烷基)硫甲基-4-壬基酚。
1.3氢醌和烷基化氢醌类,如2,6-二叔丁基-4-甲氧基酚、2,5-二叔丁基氢醌、2,5-二叔戊基氢醌、2,6-二苯基-4-十八烷氧基酚、2,6-二叔丁基氢醌、2,5-二叔丁基-4-羟基苯甲醚、3,5-二叔丁基-4-羟基苯甲醚、3,5-二叔丁基-4-羟苯基硬脂酸酯、双-(3,5-二叔丁基-4-羟苯基)己二酸酯。
1.4生育酚类,如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚和它们的混合物(维生素E)。
1.5羟化的硫代二苯基醚类,如2,2′-硫代双(6-叔丁基-4-甲基酚)、2,2′-硫代双(4-辛基酚)、4,4′-硫代双(6-叔丁基-3-甲基酚)、4,4′-硫代双(6-叔丁基-2-甲基酚)、4,4′-硫代双-(3,6-二仲戊基酚)、4,4′-双(2,6-二甲基-4-羟苯基)二硫醚。
1.6亚烷基双酚类,如2,2′-亚甲基双(6-叔丁基-4-甲基酚)、2,2′-亚甲基双(6-叔丁基-4-乙基酚)、2,2′-亚甲基双〔4-甲基-6-(α-甲基环己基)酚〕、2,2′-亚甲基双(4-甲基-6-环己基酚)、2,2′-亚甲基双(6-壬基-4-甲基酚)、2,2′-亚甲基双(4,6-二叔丁基酚)、2,2′-亚乙基双(4,6-二叔丁基酚)、2,2′-亚乙基双(6-叔丁基-4-异丁基酚)、2,2′-亚甲基双〔6-(α-甲基苄基)-4-壬基酚〕、2,2′-亚甲基双〔6-(α,α-二甲基苄基)-4-壬基酚〕、4,4′-亚甲基双(2,6-二叔丁基酚)、4,4′-亚甲基双(6-叔丁基-2-甲基酚)、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷、2,6-双(3-叔丁基-5-甲基-2-羟苄基)-4-甲基酚、1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷、1,1-双(5-叔丁基-4-羟基-2-甲基-苯基)-3-正十二烷基巯基丁烷、乙二醇双〔3,3,-双(3′-叔丁基-4′-羟苯基)丁酸酯〕、双(3-叔丁基-4-羟基-5-甲基-苯基)双环戊二烯、双〔2-(3′-叔丁基-2′-羟基-5′-甲基苄基)-6-叔丁基-4-甲基苯基〕对苯二甲酸酯、1,1-双-(3,5-二甲基-2-羟苯基)丁烷、2,2-双(3,5-二叔丁基-4-羟苯基)丙烷、2,2-双-(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷、1,1,5,5-四-(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7氧-、氮-和硫-苄基化合物,如3,5,3′,5′-四叔丁基-4,4′-二羟基-二苄基醚、十八烷基-4-羟基-3,5-二甲基苄基巯基乙酸酯、十三烷基-4-羟基-3,5-二叔丁基苄基巯基乙酸酯、三(3,5-二叔丁基-4-羟基苄基)-胺、双(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫代对苯二甲酸酯、双(3,5-二叔丁基-4-羟基苄基)硫醚、异辛基-3,5-二叔丁基-4-羟基-苄基巯基乙酸酯。
1.8羟苄基化丙二酸酯类,如二(十八烷基)-2,2-双(3,5-二叔丁基-2-羟基苄基)丙二酸酯、二(十八烷基)-2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸酯、二(十二烷基)巯基乙基-2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸酯、双〔4-(1,1,3,3-四甲基丁基)苯基〕-2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸酯。
1.9芳族羟苄基化合物,如1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲苯、1,4-双(3,5-二叔丁基-4-羟基苄基)-2,3,5,6-四甲苯、2,4,6-三(3,5-二叔丁基-4-羟基苄基)酚。
1.10三嗪化合物,如2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氧基)-1,3,5-三嗪、2,4,6-三(3,5-二叔丁基-4-羟基苯氧基)-1,2,3-三嗪、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰酸酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、2,4,6-三(3,5-二叔丁基-4-羟苯基乙基)-1,3,5-三嗪、1,3,5-三(3,5-二叔丁基-4-羟苯基丙酰基)-六氢-1,3,5-三嗪、1,3,5-三(3,5-二环己基-4-羟苄基)异氰酸酯。
1.11苄基瞵酸酯,如二甲基-2,5-二叔丁基-4-羟苄基膦酸酯、二乙基-3,5-二叔丁基-4-羟苄基膦酸酯、二(十八烷基)-3,5-二叔丁基-4-羟苄基膦酸酯、二(十八烷基)-5-叔丁基-4-羟基-3-甲基苄基-膦酸酯、3,5-二叔丁基-4-羟苄基-膦酸单乙酯钙盐。
1.12酰胺基酚类,如4-羟基月桂酰苯胺、4-羟基硬脂酰苯胺、辛基-N-(3,5-二叔丁基-4-羟苯基)氨基甲酸酯。
1.13β-(3,5-二叔丁基-4-羟苯基)丙酸与一元醇或多元醇的酯,如与甲醇、乙醇、正辛醇、异辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N′-双(羟乙基)草酰胺、3-硫杂十一醇、3-硫杂十五醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环〔2.2.2〕辛烷的酯。
1.14 β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与一元醇或多元醇的酯、如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N′-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环〔2.2.2〕辛烷的酯。
1.15 β-(3,5-二环己基-4-羟苯基)丙酸与一元醇或多元醇的酯,如与甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N′-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环〔2.2.2〕辛烷的酯。
1.16 3,5-二叔丁基-4-羟苯基乙酸与一元醇或多元醇的酯,如与甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N′-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧双环〔2.2.2〕辛烷的酯。
1.17 β-(3,.5-二叔丁基-4-羟苯基)丙酸的酰胺,如N,N′-双(3,5-二叔丁基-4-羟苯基丙酰基)六亚甲基二胺、N,N′-双(3,5-二叔丁基-4-羟苯基丙酰基)三亚甲基二胺、N,N′-双(3,5-二叔丁基-4-羟苯基丙酰基)肼。
1.18抗坏血酸(维生素C)
1.19胺类抗氧化剂,如N,N′-二异丙基-对亚苯基二胺、N,N′-二仲丁基-对亚苯基二胺、N,N′-双(1,4-二甲基戊基)对亚苯基二胺、N,N′-双(1-乙基-3-甲基戊基)对亚苯基二胺、N,N′-双(1-甲基庚基)对亚苯基二胺、N,N′-双环己基-对亚苯基二胺、N,N′-二苯基-对亚苯基二胺、N,N′-双(2-萘基)对亚苯基二胺、N-异丙基-N′-苯基-对亚苯基二胺、N-(1,3-二甲基丁基)-N′-苯基-对亚苯基二胺、N-(1-甲基庚基)-N′-苯基-对亚苯基二胺、N-环己基-N′-苯基-对亚苯基二胺、4-(对甲苯氨磺酰基)二苯基胺、N,N′-二甲基-N,N′-二仲丁基-对亚苯基二胺、二苯基胺、N-烯丙基二苯基胺、4-异丙氧基二苯基胺、N-苯基-1-萘基胺、N-(4-叔辛基苯基)-1-萘基胺、N-苯基-2-萘基胺、辛基化二苯基胺如对,对′-二叔辛基二苯基胺、4-正丁氨基苯酚、4-丁酰氨基苯酚、4-壬酰氨基苯酚、4-十二烷酰氨基苯酚、4-十八烷酰氨基苯酚、双(4-甲氧基苯基)胺、2,6-二叔丁基-4-二甲氨基甲基苯酚、2,4′-二氨基二苯基甲烷、4,4′-二氨基二苯基甲烷、N,N,N′,N′-四甲基-4,4′-二氨基二苯基甲烷、1,2-双〔(2-甲基苯基)氨基〕乙烷、1,2-双(苯氨基)丙烷、(邻-甲苯基)双胍、双〔4-(1′,3′-二甲基丁基)苯基〕胺、叔辛基化N-苯基-1-萘基胺、单烷基化和二烷基化叔丁基/叔辛基二苯基胺的混合物、单烷基化和二烷基化壬基二苯基胺的混合物、单烷基化和二烷基化十二烷基二苯基胺的混合物、单烷基化和二烷基化异丙基/异己基二苯基胺的混合物、单烷基化和二烷基化叔丁基二苯基胺的混合物、2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪、吩噻嗪、单烷基化和二烷基化叔丁基/叔辛基吩噻嗪的混合物、单烷基化和二烷基化叔辛基吩噻嗪的混合物、N-烯丙基吩噻嗪、N,N,N′,N′-四苯基-1,4-二氨基丁-2-烯、N,N-双(2,2,6,6-四甲基哌啶-4-基-六亚甲基二胺、双(2,2,6,6-四甲基哌啶-4-基)癸二酸酯、2,2,6,6-四甲基哌啶-4-酮、2,2,6,6-四甲基哌啶-4-醇。
2.紫外线吸收剂和光稳定剂
2.1 2-(2′-羟苯基)苯并三唑类,如2-(2′-羟基-5′-甲基苯基)-苯并三唑、2-(3′,5′-二叔丁基-2′-羟苯基)苯并三唑、2-(5′-叔丁基-2′-羟苯基)苯并三唑、2-(2′-羟基-5′-(1,1,3,3-四甲基丁基)苯基)苯并三唑、2-(3′,5′-二叔丁基-2′-羟苯基)-5-氯-苯并三唑、2-(3′-叔丁基-2′-羟基-5′-甲基苯基)-5-氯-苯并三唑、2-(3′-仲丁基-5′-叔丁基-2′-羟苯基)苯并三唑、2-(2′-羟基-4′-辛氧基苯基)苯并三唑、2-(3′,5′-二叔戊基-2′-羟苯基)苯并三唑、2-(3′,5′-双(α,α-二甲基苄基)-2′-羟苯基)苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰乙基)苯基)-5-氯-苯并三唑、2-(3′-叔丁基-5′-〔2-(2-乙基己氧基)-羰乙基〕-2′-羟苯基)-5-氯-苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰乙基)苯基)-5-氯-苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰乙基)苯基)苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰乙基)苯基)苯并三唑、2-(3′-叔丁基-5′-〔2-(2-乙基己氧基)羰乙基〕-2′-羟苯基)苯并三唑、2-(3′-十二烷基-2′-羟基-5′-甲基苯基)苯并三唑和2-(3′-叔丁基-2′-羟基-5′-(2-异辛氧基羰乙基)苯基苯并三唑的混合物、2,2′-亚甲基-双〔4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基酚〕;2-〔3′-叔丁基-5′-(2-甲氧基羰乙基)-2′-羟苯基〕-2H-苯并三唑与聚乙二醇300的酯基转移产物;〔R-CH2CH2-COO(CH2)3〕2,其中R=3′-叔丁基-4′-羟基-5′-2H-苯并三唑-2-基苯基。
2.2 2-羟基二苯酮,如4-羟基、4-甲氧基、4-辛氧基、4-癸氧基、4-十二烷氧基、4-苄氧基、4,2′,4′-三羟基和2′-羟基-4,4′-二甲氧基衍生物。
2.3取代的和未取代的苯甲酸的酯,如水杨酸4-叔丁基苯基酯、水杨酸苯酯、水杨酸辛苯基酯、二苯甲酰基间苯二酚、双(4-叔丁基苯甲酰基)间苯二酚、苯甲酰基间苯二酚、3,5-二叔丁基-4-羟基苯甲酸2,4-二叔丁基苯基酯、3,5-二叔丁基-4-羟基苯甲酸十六烷基酯、3,5-二叔丁基-4-羟基苯甲酸十八烷基酯、3,5-二叔丁基-4-羟基苯甲酸2-甲基-4,6-二叔丁基苯基酯。
2.4丙烯酸酯,如α-氰基-β,β-二苯基丙烯酸乙酯、α-氰基-β,β-二苯基丙烯酸异辛酯、α-甲酯基肉桂酸甲酯、α-氰基-β-甲基-对甲氧基肉桂酸甲酯、α-氰基-β-甲基-对甲氧基肉桂酸丁酯、α-甲氧甲酰-对甲氧基肉桂酸甲酯和N-(β-甲氧甲酰-β-氰乙烯基)-2-甲基二氢吲哚。
2.5镍化合物,如2,2′-硫代-双〔4-(1,1,3,3-四甲基丁基)苯酚〕的镍配合物如1∶1或1∶2配合物,有或没有另外的配位体如正丁胺、三乙醇胺或N-环己基二乙醇胺、二丁基二硫代氨基甲酸镍、单烷基酯的镍盐如4-羟基-3,5-二叔丁基苄基膦酸甲酯或乙酯的镍盐、酮肟的镍配合物如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物、1-苯基-4-月桂酰基-5-羟基吡唑的镍配合物,有或没有另外的配位体。
2.6空间受阻的胺类,如双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)正-丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯、1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合物,N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、1,1′-(1,2-联二甲基)双(3,3,5,5-四甲基哌嗪酮)、4-苯甲酰基-2,2,6,6-四甲基哌啶、4-硬脂氧基-2,2,6,6-四甲基哌啶、双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺〔4.5〕癸-2,4-二酮、双(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯、N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉代-2,6-二氯-1,3,5-三嗪的缩合物、2-氯-4,6-双(4-正丁氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨丙基氨基)乙烷的缩合物、2-氯-4,6-二(4-正丁氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-双-(3-氨丙基氨基)乙烷的缩合物、8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺〔4.5〕癸-2,4-二酮,3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮、4-十六烷氧基和4-十八烷氧基-2,2,6,6-四甲基哌啶的混合物、N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合产物、1,2-双(3-氨丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪的缩合产物以及4-丁氨基-2,2,6,6-四甲基哌啶(CAS Reg.No〔136504-96-6〕);N-(2,2,6,6-四甲基-4-哌啶基)-正十二烷基琥珀酰亚胺、N-(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基琥珀酰亚胺、2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧-螺〔4,5〕癸烷、7,7,9,9-四甲基-2-环十二烷基-1-氧杂-3,8-二氮杂-4-氧螺〔4,5〕癸烷和表氯醇的反应产物。
2.7草酰胺类,如4,4′-二辛氧基草酰二苯胺、2,2′-二乙氧基草酰二苯胺、2,2′-二辛氧基-5,5′-二叔丁草酰二苯胺、2,2′-二(十二烷氧基)-5,5′-二叔丁基草酰二苯胺、2-乙氧基-2′-乙基草酰二苯胺、N,N′-双(3-二甲氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2′-乙草酰二苯胺和它与2-乙氧基-2′-乙基-5,4′-二叔丁草酰二苯胺的混合物和邻-和对-甲氧基-二取代的草酰二苯胺的混合物以及邻-和对-乙氧基-二取代的草酰二苯胺的混合物。
2.8 2-(2-羟苯基)-1,3,5-三嗪类,如2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2,4-二羟苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十三烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-〔2-羟基-4-(2-羟基-3-丁氧基-丙氧基)苯基〕-4,6-双(2,4-二甲基)-1,3,5-三嗪、2-〔2-羟基-4-(2-羟基-3-辛氧基-丙氧基)苯基〕-4,6-双(2,4-二甲基)-1,3,5-三嗪、2-〔4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟基-苯基〕-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-〔2-羟基-4-(2-羟基-3-十二烷氧基-丙氧基)苯基〕-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪、2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪、2,4,6-三〔2-羟基-4-(3-丁氧基-2-羟基-丙氧基)苯基〕-1,3,5-三嗪、2-(2-羟苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪。
3.金属钝化剂,例如N,N′-二苯基草酰胺、N-水杨基-N′-水杨酰基肼、N,N′-双(水杨酰基)肼、N,N′-双(3,5-二叔丁基-4-羟苯基-丙酰基)肼、3-水杨酰氨基-1,2,4-三唑、双(亚苄基)草酰基二酰肼、草酰二苯胺、间苯二甲酰基二酰肼、癸二酰双苯基酰肼、N,N′-二乙酰基己二酰基二酰肼、N,N′-双(水杨酰基)草酰基二酰肼、N,N′-双(水杨酰基)-硫代丙酰基二酰肼。
4.亚磷酸酯和膦酸酯,如亚磷酸三苯酯、亚磷酸二苯基烷基酯、亚磷酸苯基二烷基酯、亚磷酸三(壬基苯基)酯、亚磷酸三月桂酯、亚磷酸三(十八烷基)酯、二亚磷酸二硬脂基季戊四醇酯、亚磷酸三(2,4-二叔丁基苯基)酯、二亚磷酸二异癸基季戊四醇酯、二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯、二亚磷酸双(2,6-二叔丁基-4-甲基苯基)-季戊四醇酯、二亚磷酸二异癸氧基季戊四醇酯、二亚磷酸双(2,4-二叔丁基-6-甲基苯基)季戊四醇酯、二亚磷酸双(2,4,6-三(叔丁基苯基)季戊四醇酯、三亚磷酸三硬脂基山梨醇酯、二膦酸四(2,4-二叔丁基苯基)4,4′-二亚苯基酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并〔d,g〕-1,3,2-二氧杂phos-phocin、6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并〔d,g〕-1,3,2-二氧杂phosphocin、双(2,4-二叔丁基-6-甲基苯基)甲基亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯。
5.羟基胺类,如N,N-二苄基羟基胺、N,N-二乙基羟基胺、N,N-二辛基羟基胺、N,N-二月桂基羟基胺、N,N-二(十四烷基)羟基胺、N,N-二(十六烷基)羟基胺、N,N-二(十八烷基)羟基胺、N-十六烷基-N-十八烷基羟基胺、N-十七烷基-N-十八烷基羟基胺、由氢化牛脂胺得到的N,N-二烷基羟基胺。
6.硝酮类,如N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-十八烷基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十六烷基硝酮、由氢化牛脂胺得到的N,N-二烷基羟基胺制得的硝酮。
7.硫代增效剂,如硫代二丙酸二月桂酯或硫代二丙酸二硬脂基酯。
8.过氧化物清除剂,如β-硫代二丙酸的酯类,如月桂基酯、硬脂基酯、肉豆蔻基酯或十三烷基酯、巯基苯并咪唑或2-巯基苯并咪唑的锌盐、二丁基二硫代氨基甲酸锌、二(十八烷基)二硫醚、四(β-十二烷基巯基)丙酸季戊四醇酯。
9.聚酰胺稳定剂,如铜盐与碘化物和/或磷化合物结合和二价锰的盐。
10.碱性助稳定剂,如密胺、聚乙烯基吡咯烷酮、双氰胺、氰脲酸三烯丙酯、脲衍生物、肼衍生物、胺类、聚酰胺类、聚氨酯、高级脂肪酸的碱金属盐和碱土金属盐如硬脂酸钙、硬脂酸锌、山萮酸镁、硬脂酸镁、蓖麻醇酸钠及棕榈酸钾、焦儿茶酚锑或焦儿茶酚锡。
11.成核剂,如无机物质如滑石、金属氧化物(如二氧化钛或氧化镁)、磷酸盐、碳酸盐或硫酸盐,特别优选碱土金属盐;有机化合物如一元羧酸或多元羧酸及其盐如4-叔丁基苯甲酸、己二酸、二苯基乙酸、琥珀酸钠或苯甲酸钠;聚合化合物如离子键共聚物(“离子聚合物”)。
12.填充剂和增强剂,如碳酸钙、硅酸盐、玻璃纤维、玻璃球、石棉、滑石、高岭土、云母、硫酸钡、金属氧化物和氢氧化物、炭黑、石墨、木粉以及其他天然产品的粉或纤维、合成纤维。
13.其他添加剂,如增塑剂、润滑剂,乳化剂、颜料、流变添加剂、催化剂、流动控制剂、增白剂、阻燃剂、抗静电剂和鼓泡剂。
14.苯并呋喃酮和二氢吲哚酮,例如在US-A-4325863、US-A-4338244、US-A-5175312、US-A-5216052、US-A-5252643、DE-A-4316611、DE-A-4316622、DE-A-4316876、EP-A-0589839或EP-A-0591102中公开的那些,或者3-〔4-(2-乙酰氧基乙氧基)苯基〕-5,7-二叔丁基-苯并呋喃-2-酮、5,7-二叔丁基-3-〔4-(2-硬脂酰氧基乙氧基)苯基〕苯并呋喃-2-酮、3,3′-双〔5,7-二叔丁基-3-(4-〔2-羟基乙氧基〕-苯基)苯并呋喃-2-酮〕、5,7-二叔丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮、3-(4-乙酰氧基-3,5-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(3,5-二甲基-4-新戊酰氧基苯基)-5,7-二叔丁基苯并呋喃-2-酮。
新型化合物与传统添加剂的重量比例如可为1∶0.5至1∶5。
本发明还涉及式I的化合物用于使有机材料对氧化、热或光引发的降解作用稳定的应用。
以下实施例更详细地说明本发明。除非另加说明,所有的数量都按重量计。
实施例1
化合物101的制备
将1.5克(3毫摩尔)2,2′-亚乙基双〔4,6-二叔丁基苯酚〕单丙烯酸酯(制备方法例如类似EP-A-500323)和1.4克(21毫摩尔)环戊二烯在40毫升甲苯中的混合物加热到90℃,并在这一温度下搅拌2小时。随后在真空旋转蒸发器中将反应混合物蒸发。生成的粗产品从乙腈中结晶,得到1.5克化合物101白色粉末(异构体混合物,理论值的91%)。
熔点:150-154℃
无素分析: C% H%
计算值: 81.67 9.74
测定值: 81.86 9.68
实施例2
化合物101的制备
将4.93克(10毫摩尔)2,2′-亚乙基双〔4,6-二叔丁基苯酚〕单丙烯酸酯和4.6克(70毫摩尔)环戊二烯在20毫升异丙醇和20毫升水中的混合物加热到90℃,并在这一温度下搅拌2小时。随后在旋转蒸发器中将反应混合物蒸发,并将残留物倒入水中,并用乙酸乙酯萃取两次。合并有机相,在硫酸钠上干燥,然后在真空旋转蒸发器中蒸发。残留物从乙腈中结晶,得到3.9克化合物101白色粉末(异构体混合物,理论值的71%)。
熔点:148-150℃
元素分析: C% H%
计算值: 81.67 9.74
测定值: 81.69 9.68
实施例3
化合物101的制备
将9.85克(20毫摩尔)2,2′-亚乙基双〔4,6-二叔丁基苯酚〕单丙烯酸酯、0.6毫升(1.08毫摩尔=5%(摩尔))1.8M乙基二氯化铝甲苯溶液和50毫升甲苯在N2气氛下送入100毫升圆底烧瓶中。在室温下将1.8毫升(22毫摩尔)环戊二烯滴加到该悬浮液中,并将混合物搅拌2.5小时。随后将得到的有机溶液倒入50毫升盐酸(1M)中,并用乙酸乙酯萃取混合物两次。合并有机相,用NaCl饱和水溶液洗涤,在硫酸钠上干燥,然后在真空旋转蒸发器中蒸发。残留物(10.5克)从乙腈中结晶,得到8.5克化合物101白色粉末(异构体混合物,理论值的77%)。
熔点:146-150℃
元素分析: C% H%
计算值: 81.67 9.74
测定值: 81.70 9.87
实施例4
化合物101的制备
将49.3克(0.1摩尔)2,2′-亚乙基双〔4,6-二叔丁基苯酚〕单丙烯酸酯、7.9克(0.06摩尔)双环戊二烯和50毫升甲苯送入0.3升高压釜中。用惰性气体(N2)吹扫高压釜,并在200℃下加热8小时(最大压力3巴)。随后将得到的黄色溶液冷却到室温,并在真空旋转蒸发器中蒸发。残留物从乙腈中结晶,得到44.5克化合物101白色粉末(异构体混合物,理论值的80%)。
熔点:157-160℃
元素分析: C% H%
计算值: 81.67 9.74
测定值: 81.81 9.85
实施例5
化合物101的制备
将4.4克(10毫摩尔)2,2′-亚乙基双〔4,6-二叔丁基苯酚〕和2克(13毫摩尔)降冰片-5-烯-2-碳酰氯(制备方法例如类似J.0rg.Chem.38,642(1973))的混合物加热到140℃,并在这一温度下搅拌5分钟。从125℃开始放出HCl。将混合物冷却到约110℃,加入15毫升乙腈,并将混合物冷却到室温。过滤结晶出的产品,并在高真空中干燥,得到4.2克化合物101白色粉末(异构体混合物,理论值的70%)。
熔点:152-155℃
元素分析: C% H%
计算值: 81.67 9.74
测定值: 81.65 9.96
用实施例3中公开的方法,分别由亚甲基双〔4-甲基-6-叔丁基苯酚〕单丙烯酸酯和2,2′-亚乙基双〔4,6-二叔戊基苯酚〕单丙烯酸酯和环戊二烯制备化合物102和103。
用类似于实施例4中公开的方法,由甲基环戊二烯二聚物和2,2′-亚乙基双〔4,6-二叔丁基苯酚〕单丙烯酸酯制备化合物102。
实施例6
化合物104的制备
将18毫升(29毫摩尔)1.6N丁基锂/己烷溶液在N2气氛下缓慢滴加到冷却到5~10℃的12.7克(29毫摩尔)2,2′-亚乙基双〔4,6-二叔丁基苯酚〕于50毫升四氢呋喃中的溶液中。将混合物搅拌15分钟,随后将6.5克(38毫摩尔)2-甲基降冰片-5-烯碳酰氯(制备方法例如类似于A.F.Jacobine et al.,J.of Appl.Polym.Sci.45,471(1992))于6毫升四氢呋喃中的溶液滴加入。将混合物回流过夜。冷却到室温后,反应混合物通过Hyflo过滤,并在真空旋转蒸发器中蒸发。残留物从乙腈中结晶,得到11.7克化合物104白色粉末(异构体混合物,理论值的70%)。
熔点:132-140℃
实施例7
化合物105的制备
将39.5克(0.09摩尔)2,2′-亚乙基双〔4,6-二叔丁基苯酚〕和11.84克(0.12毫摩尔)三乙胺于200毫升甲苯中的溶液在N2气氛下送入500毫升圆底烧瓶中。将16.5克(0.1摩尔)7-氧杂双环〔2.2.1〕庚-5-烯-2-碳酰氯(制备方法例如类似Bull.Chem.Soc.Jpn.57,3339-40(1984))在-20℃下滴加到该无色溶液中。将混合物在-20℃下搅拌30分钟,然后在2小时内加热到室温。过滤出盐,滤液在真空旋转蒸发器中蒸发。残留物在硅胶上进行色谱分离,冲洗剂为80∶1己烷/乙酸乙酯,得到11.2克化合物105白色粉末(异构体混合物,理论值的22%)。
熔点:95-96℃。
实施例8
化合物106的制备
将6.6克(15毫摩尔)2,2′-亚乙基双〔4,6-二叔丁基苯酚〕和4.2克(15.7毫摩尔)9,10-二氢-9,10-桥亚乙基蒽-11-碳酰氯(制备方法例如类似于J.A.C.S.94,1193(1972)的方法)于100毫升甲苯中的溶液在N2气氛下送入250毫升圆底烧瓶中。将2.7毫升(19.5毫摩尔)三乙胺在约5℃下滴加到该溶液中。将混合物在5℃下搅拌2小时,然后倒入水中,并用乙酸乙酯萃取两次。合并有机相,用NaCl饱和水溶液洗涤,在硫酸钠上干燥,并在真空旋转蒸发器中蒸发。残留物从甲醇中结晶,得到6.6克化合物106浅黄色粉末(异构体混合物,理论值的62%)。
熔点:217-219℃。
实施例9
聚丙烯在多次挤塑过程中的稳定
1.3千克用0.025%3-〔3,5-二叔丁基-4-羟苯基〕丙酸正十八烷基酯预稳定的,在230℃和2.16千克下熔体流动指数为3.2的聚丙烯粉(RProfax 6501)与0.05%四〔3-(3,5-二叔丁基-4-羟苯基)丙酸〕季戊四醇酯、0.05%硬脂酸钙、0.03%dihydrotalcite〔Mg4.5Al2(OH)13CO3·3.5H2O〕和0.05%表1的化合物混合。在机筒直径为20毫米和长度为400毫米的挤塑机中,在100转/分钟下将混合物挤塑,将3个加热段确定到以下温度:260、270和280℃。通过牵引经水浴使挤塑物冷却,随后造粒。将这些颗粒挤塑数次。3次挤塑后,测量熔体流动指数(在230℃和2.16千克下)。熔体流动指数较大的增加表明有明显的链降解,即稳定性差。结果列入表2。
表2
表1的化合物 | 3次挤塑后的熔体流动指数 |
-101104 | 20.06.87.2 |
实施例10
弹性体的稳定(布拉本德试验)
将苯乙烯-丁二烯-苯乙烯弹性体(RFinaprene 902)与表3所示的稳定剂混合,并在布拉本德塑度绘迹仪中,在200℃、60转/分钟下配混。连续以扭矩记录配混阻力。由于聚合物交联的结果,在配混过程中,扭矩在最初保持不变后出现迅速增加。从扭矩保持不变的时间可得出稳定剂的效果。所得到的数值列入表3。
表3
0.25%表1的稳定剂 | 扭矩增加前的时间(分钟) |
-101104 | 24.25362 |
实施例11
苯乙烯-丁二烯嵌段聚合物的稳定
在苯乙烯-丁二烯嵌段聚合物热/氧化损坏过程中,在橡胶相中出现交联。这一交联使熔体粘度增加,所以在挤塑机中或在注塑机中加工过程中挤出压力增加。
苯乙烯-丁二烯嵌段聚合物的加工稳定性常常在毛细管流变仪中测试。在这一测试中,强制聚合物熔体以类似的方式通过喷嘴挤塑。
将25克含有0.2%3-〔3′,5′-二叔丁基-4′-羟苯基〕丙酸正十八烷基酯和0.6%亚磷酸三〔壬基苯基〕酯的苯乙烯-丁二烯嵌段聚合物颗粒(RK-Resin KR-01,RPhillips Petroleum公司生产)在室温下溶于250毫升环己烷中。
将表4所示的稳定剂量溶于甲苯中,并与聚合物溶液混合。随后在60℃、0.013巴下蒸出环己烷。
在180℃下压制得到的聚合物,得到厚度为2毫米的片材,由它冲压成直径8毫米的圆形样品。将该样品送入RKeyeness GalaxyV毛细管流变仪的样品槽中,在250℃、剪切速率14.594秒-1下进行测量。流动时间6分钟后,记录30分钟内表观剪切速率随时间的变化。这一曲线的斜率(Δη/Δt帕·秒/分钟)是聚合物交联度的量度,所以直接与稳定剂的效果有关。这一数值越小,稳定剂越有效。结果列入表4。
表4
0.15%表1的稳定剂 | Δη(帕·秒)Δt(分钟) |
-101102103104105 | 2357424 |
Claims (14)
1.一种式I的化合物,式中,A为式IIa或IIb的基团,Y为氧、亚甲基、亚乙基或>C=C(CH3)2,Z为氮、
或
R1各自独立为C1-C25烷基、C2-C24链烯基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、C5-C12环烯基、C1-C4烷基取代的C5-C12环烯基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基或-CH2-S-X1,R2各自独立为氢、C1-C25烷基、C2-C24链烯基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、C5-C12环烯基、C1-C4烷基取代的C5-C12环烯基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基、-CH2-S-X1、-(CH2)pCOO-X2或-(CH2)qO-X3,R3各自独立为氢或C1-C4烷基,R4为氢或C1-C8烷基,R5为氢、C1-C10烷基、苯基、-CH2-COO-X4或CN,R6为氢、C1-C4烷基、苯基、-COO-X5、-CN或-CON(X6)(X7),R7为氢或C1-C10烷基,R8、R9和R10各自独立为氢或C1-C4烷基,R11和R12各自独立为氢、C1-C4烷基或苯基,R13和R14各自独立为氢或C1-C4烷基,X1为C1-C25烷基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基或-(CH2)rCOO-Y1,X2、X4和X5各自独立为C1-C25烷基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、苯基、C1-C4烷基取代的苯基或C7-C9苯烷基,X3为C1-C25烷基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基、C1-C25烷酰基、C3-C25烯酰基、被氧、硫或>N-Y2间断的C3-C25烷酰基、C6-C9环烷基羰基、苯甲酰基、C1-C4烷基取代的苯甲酰基、噻吩甲酰基或糠酰基,X6和X7各自独立为氢、C1-C25烷基、C2-C24链烯基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、C5-C12环烯基、C1-C4烷基取代的C5-C12环烯基、苯基、C1-C4烷基取代的苯基或C7-C9苯烷基,Y1为C1-C25烷基、C5-C12环烷基、C1-C4烷基取代的C5-C12环烷基、苯基、C1-C4烷基取代的苯基或C7-C9苯烷基,Y2为氢或C1-C8烷基,p为0、1或2,q为0-8中的一个整数,以及r为1或2。
2.根据权利要求1的化合物,其中R1各自独立为C1-C18烷基、C2-C18链烯基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、C5-C8环烯基、C1-C4烷基取代的C5-C8环烯基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基或-CH2-S-X1,R2各自独立为氢、C1-C18烷基、C2-C18链烯基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、C5-C8环烯基、C1-C4烷基取代的C5-C8环烯基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基、-CH2-S-X1、-(CH2)pCOO-X2或-(CH2)qO-X3,R5为氢、C1-C10烷基、苯基或CN,R6为氢、C1-C4烷基或苯基,X1为C1-C18烷基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基或-(CH2)rCOO-Y1,X2为C1-C18烷基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、苯基、C1-C4烷基取代的苯基或C7-C9苯烷基,X3为C1-C18烷基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、苯基、C1-C4烷基取代的苯基、C7-C9苯烷基、C1-C18烷酰基、C3-C18烯酰基、被氧或>N-Y2间断的C3-C18烷酰基、C6-C9环烷基羰基、苯甲酰基、C1-C4烷基取代的苯甲酰基、噻吩甲酰基或糠酰基、以及Y1为C1-C18烷基、C5-C8环烷基、C1-C4烷基取代的C5-C8环烷基、苯基、C1-C4烷基取代的苯基或C7-C9苯烷基。
3.根据权利要求1的化合物,其中R1各自独立为C1-C10烷基、C2-C18链烯基、C5-C8环烷基、C5-C8环烯基、苯基、C7-C9苯烷基或-CH2-S-X1,R2各自独立为氢、C1-C10烷基、C2-C18链烯基、C5-C8环烷基、C5-C8环烯基、苯基、C7-C9苯烷基、-CH2-S-X1、-(CH2)pCOO-X2或-(CH2)qO-X3,R3为氢,R4为氢或C1-C4烷基,R5为氢、C1-C4烷基,苯基或CN,R6为氢、C1-C4烷基或苯基,R7为氢或C1-C4烷基,X1为C1-C10烷基、C5-C8环烷基、苯基、C7-C9苯烷基或-(CH2)rCOO-Y1,X2为C1-C10烷基、C5-C8环烷基、苯基或C7-C9苯烷基,X3为C1-C10烷基、C5-C8环烷基、苯基、C7-C9苯烷基、C1-C10烷酰基、C3-C18烯酰基、被氧间断的C3-C18烷酰基或苯甲酰基,以及Y1为C1-C10烷基、C5-C8环烷基、苯基或C7-C9苯烷基。
4.根据权利要求1的化合物,其中R8、R9、R10、R11、R12、R13和R14为氢。
5.根据权利要求1的化合物,其中R1各自独立为C1-C5烷基或C5-C8环烷基,R2各自独立为C1-C5烷基,R3为氢,以及R4为氢或C1-C4烷基。
6.根据权利要求1的化合物,其中
R1为相同基团,为支链的C3-C5烷基,R2为相同基团,为C1-C5烷基,R3为氢,以及R4为氢或C1-C4烷基。
7.根据权利要求1的化合物,其中Y为氧或亚甲基,Z为
R1为相同基团,为支链的C3-C5烷基,R2为相同基团,为C1-C5烷基,R3为氢,R4为氢或C1-C4烷基,R5为氢、C1-C4烷基或CN,以及R6、R7、R8、R9、R10、R11、R12、Rl3和R14为氢。
8.根据权利要求1的化合物
9.一种含有对氧化、热或光引发的降解作用敏感的有机材料和至少一种根据权利要求1的式I化合物的组合物。
10.根据权利要求9的组合物,其中有机材料为合成聚合物。
11.根据权利要求9的组合物,其中有机材料为聚烯烃。
12.根据权利要求9的组合物,其中有机材料为溶液聚合的聚丁二烯橡胶。
13.根据权利要求9的组合物,其中有机材料为溶液聚合的苯乙烯-丁二烯共聚物或苯乙烯-丁二烯嵌段共聚物。
14.一种用于使有机材料对氧化、热或光引发的降解作用稳定的方法,该法包括将至少一种权利要求1的化合物加到所述的有机材料中。
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AU (1) | AU696080B2 (zh) |
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CA (1) | CA2168922A1 (zh) |
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DE59808737D1 (de) * | 1997-08-19 | 2003-07-24 | Ciba Sc Holding Ag | Stabilisatoren für Pulverlacke |
DE59806917D1 (de) * | 1997-09-29 | 2003-02-20 | Ciba Sc Holding Ag | Stabilisatorgemisch für organische Materialien |
US6995181B2 (en) | 2002-07-18 | 2006-02-07 | Bristol-Myers Squibb Co. | Modulators of the glucocorticoid receptor and method |
US7569689B2 (en) * | 2004-01-16 | 2009-08-04 | Bristol-Myers Squibb Company | Modulators of the glucocorticoid receptor, AP-1, and/or NF-κB activity and use thereof |
US7273881B2 (en) * | 2004-01-16 | 2007-09-25 | Bristol-Myers Squibb Company | Modulators of glucocorticoid receptor, AP-1, and/or NF-κB activity and use thereof |
US7605264B2 (en) * | 2004-01-16 | 2009-10-20 | Bristol-Myers Squibb Company | Heterocyclic modulators of the glucocorticoid receptor, AP-1, and/or NF-κB activity and use thereof |
US7253283B2 (en) * | 2004-01-16 | 2007-08-07 | Bristol-Myers Squibb Company | Tricyclic modulators of the glucocorticoid receptor, AP-1, and/or NF-κB activity and use thereof |
US7326728B2 (en) * | 2004-01-16 | 2008-02-05 | Bristol-Myers Squibb Company | Modulators of glucocorticoid receptor, AP-1, and/or NF-κβ activity and use thereof |
US7625921B2 (en) * | 2004-01-16 | 2009-12-01 | Bristol-Myers Squibb Company | Modulators of the glucocorticoid receptor, AP-1, and/or NF-κB activity and use thereof |
US7642273B2 (en) * | 2005-01-13 | 2010-01-05 | Bristol-Myers Squibb Company | Modulators of the glucocorticoid receptor, AP-1, and/or NF-κB activity and use thereof |
US7317024B2 (en) | 2005-01-13 | 2008-01-08 | Bristol-Myers Squibb Co. | Heterocyclic modulators of the glucocorticoid receptor, AP-1, and/or NF-κB activity and use thereof |
US7411071B2 (en) * | 2005-01-13 | 2008-08-12 | Bristol-Myers Squibb Company | Modulators of the glucocorticoid receptor, AP-1, and/or NF-κB activity and use thereof |
US7361654B2 (en) | 2005-01-13 | 2008-04-22 | Bristol-Myers Squibb Co. | Substituted heteroaryl amide modulators of glucocorticoid receptor, AP-1, and/or NF-κB activity and use thereof |
JP5125453B2 (ja) * | 2007-11-29 | 2013-01-23 | 住友化学株式会社 | ビスフェノールモノエステル化合物、該化合物を有効成分とする安定剤及び該安定剤を含有する熱可塑性ポリマー組成物 |
ES2372567T3 (es) | 2008-01-28 | 2012-01-23 | Basf Se | Mezclas de aditivos para polímeros estirénicos. |
JP5327428B2 (ja) * | 2008-05-31 | 2013-10-30 | 川崎化成工業株式会社 | 9,10−ジヒドロ−9,10−エタノアントラセン骨格を有する新規なアクリレート化合物及びその製造法 |
JP5330904B2 (ja) * | 2009-06-12 | 2013-10-30 | 住友化学株式会社 | 粒状物質の製造方法 |
CN117050094B (zh) * | 2023-08-15 | 2024-07-05 | 锦州医科大学 | 基于Azamonardine荧光团用于检测生物硫醇中半胱氨酸的荧光探针及应用 |
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DE2948969C2 (de) * | 1978-12-06 | 1982-03-18 | Asahi Kasei Kogyo K.K., Osaka | Monoester von 3,5;3',5'-kernsubstituierten gem.-Di-(2-hydroxyphenyl)-alkanen, Verfahren zu ihrer Herstellung und deren Verwendung |
US4414408A (en) * | 1980-09-30 | 1983-11-08 | The Goodyear Tire & Rubber Company | Phenolic antioxidants |
JPS6399050A (ja) * | 1986-06-25 | 1988-04-30 | Sumitomo Chem Co Ltd | ビスフエノ−ル誘導体およびその製造法 |
US5128398A (en) * | 1987-12-23 | 1992-07-07 | Sumitomo Chemical Company, Limited | Phenolic compound and its use as stabilizer for butadiene polymer |
JPH04142365A (ja) * | 1990-10-02 | 1992-05-15 | Sumitomo Chem Co Ltd | 安定化された熱可塑性樹脂組成物 |
CA2060787C (en) * | 1991-02-18 | 2002-07-02 | Kikumitsu Inoue | Production of bisphenol monoester |
JPH04308581A (ja) * | 1991-04-04 | 1992-10-30 | Mitsubishi Petrochem Co Ltd | 新規ピペラジン誘導体 |
-
1996
- 1996-01-30 EP EP96810063A patent/EP0727410A1/de not_active Ceased
- 1996-01-31 US US08/594,199 patent/US5616780A/en not_active Expired - Fee Related
- 1996-02-01 AU AU43309/96A patent/AU696080B2/en not_active Ceased
- 1996-02-06 CZ CZ96353A patent/CZ35396A3/cs unknown
- 1996-02-06 CA CA002168922A patent/CA2168922A1/en not_active Abandoned
- 1996-02-07 CN CN96101362A patent/CN1135477A/zh active Pending
- 1996-02-07 BR BR9600340A patent/BR9600340A/pt active Search and Examination
- 1996-02-07 ZA ZA96962A patent/ZA96962B/xx unknown
- 1996-02-08 JP JP8046699A patent/JPH08277248A/ja active Pending
- 1996-02-08 KR KR1019960002970A patent/KR960031423A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
US5616780A (en) | 1997-04-01 |
ZA96962B (en) | 1996-08-28 |
JPH08277248A (ja) | 1996-10-22 |
CZ35396A3 (en) | 1996-08-14 |
BR9600340A (pt) | 1998-01-27 |
AU696080B2 (en) | 1998-09-03 |
EP0727410A1 (de) | 1996-08-21 |
AU4330996A (en) | 1996-08-15 |
KR960031423A (ko) | 1996-09-17 |
CA2168922A1 (en) | 1996-08-09 |
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