CN101128529A - 多元醇或聚氨酯组合物的耐热氧化的稳定化 - Google Patents
多元醇或聚氨酯组合物的耐热氧化的稳定化 Download PDFInfo
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- CN101128529A CN101128529A CNA2006800063112A CN200680006311A CN101128529A CN 101128529 A CN101128529 A CN 101128529A CN A2006800063112 A CNA2006800063112 A CN A2006800063112A CN 200680006311 A CN200680006311 A CN 200680006311A CN 101128529 A CN101128529 A CN 101128529A
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
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- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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- SPDZFJLQFWSJGA-UHFFFAOYSA-N uredepa Chemical compound C1CN1P(=O)(NC(=O)OCC)N1CC1 SPDZFJLQFWSJGA-UHFFFAOYSA-N 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- 239000002076 α-tocopherol Substances 0.000 description 1
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- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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Abstract
本发明涉及组合物,其包括对热降解敏感的聚酯多元醇、聚醚多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇、官能化聚醚和/或聚氨酯,和至少一种通式(101)和/或(102)的抗氧化剂和任选地其它抗氧化剂。本发明还涉及上述稳定剂(共混物)在所述多元醇、官能化聚醚和/或聚氨酯的耐热降解的用途,以及借助上述稳定剂(共混物)来稳定所述多元醇、官能化聚醚和/或聚氨酯耐热降解的方法。
Description
本发明涉及组合物,其包括对热降解敏感的聚酯多元醇、聚醚多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇、官能化聚醚和/或聚氨酯,和两种特定的抗氧化剂中的至少一种和任选地其它抗氧化剂。本发明还涉及上述稳定剂(共混物)在所述多元醇、官能化聚醚和/或聚氨酯的耐热降解的用途,以及借助上述稳定剂(共混物)来稳定所述多元醇、官能化聚醚和/或聚氨酯耐热降解的方法。
US 2002/086743涉及组合物,其包括双(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯和聚醚多元醇、聚酯多元醇或聚氨酯。
US 4721531涉及组合物,其包括双(1,2,2,6,6-五甲基4-哌啶基)-[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯、颜料和聚醚多元醇或聚酯多元醇。
EP714931A涉及组合物,其包括双(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯、UV吸收剂和聚氨酯。
US2004/096666描述了聚氨酯中的双(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯和季戊四醇四(3-(3,5-二叔丁基-4-羟苯基)丙酸酯)的结合。
JP08165323的DN125:198068涉及组合物,其包括双(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯、亚乙基双(氧基亚乙基)双-(3-(5-叔丁基-4-羟基-间甲苯基)-丙酸酯)、着色剂和聚醚多元醇。
WO 2002/044258涉及聚醚多元醇中的双(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯。
WO2004/068217描述了在光致变色的聚氨酯薄膜或光致变色的聚酯多元醇中的双(1,2,2,6,6-五甲基4-哌啶基)-[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯和季戊四醇四(3-(3,5-二叔丁基-4-羟苯基)丙酸酯)的结合。
JP2000/129145A的CA 2000:300943涉及在具有被取代的甲硅烷基的聚醚多元醇中的双(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯和亚乙基-双(氧基亚乙基)双(3-(5-叔丁基-4-羟基-间甲苯基)-丙酸酯)的结合。
Bellatini等人在Cellular Polymers 3(1984),241-247中描述了在聚氨酯中的双(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯。
JP09141809的DN 127:96261涉及聚氨酯中的(((1,1-二甲基乙基)-4-羟苯基)甲基)乙基膦酸酯。
DN 110:76695涉及组合物,其包括聚氨酯、UV吸收剂、双(1,2,2,6,6-五甲基4-哌啶基)-[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯和季戊四醇四(3-(3,5-二叔丁基-4-羟苯基)丙酸酯)或亚乙基-双(氧基亚乙基)双(3-(5-叔丁基-4-羟基-间甲苯基)-丙酸酯)。所述文件还描述了包括(((1,1-二甲基乙基)-4-羟苯基)甲基)乙基膦酸酯和聚氨酯的组合物。
含本发明抗氧化剂或本发明抗氧化剂共混物的多元醇、官能化聚醚和/或聚氨酯组合物,就热稳定性和存储稳定性来说,显示出极好的稳定性。
本发明涉及组合物,其包括
(a)聚酯多元醇、聚醚多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇、官能化聚醚和/或聚氨酯,和
(b)通式(101)和/或(102)的抗氧化剂,
(双(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯;TINUVIN144;CAS No.63843-89-0)
((((1,1-二甲基乙基)-4-羟苯基)甲基)乙基膦酸根的钙盐;IRGANOX1425;CAS No.65140-91-2)
和
(c)任选地其它耐热降解的抗氧化剂,
前提条件是
如果组分(b)是通式(101)的抗氧化剂,那么该组合物包含其它抗氧化剂(c),
如果组分(a)是聚氨酯并且组分(b)是通式(102)的抗氧化剂,那么组分(c)存在于组合物中,
如果抗氧化剂是通式(101)和(103)或(101)和(104)的化合物的结合,那么组分(a)不是聚酯多元醇、聚醚多元醇或聚氨酯
(季戊四醇四(3-(3,5-二叔丁基-4-羟苯基)丙酸酯);IRGANOX1010;CAS No.6683-19-8)
(亚乙基双(氧基亚乙基)双(3-(5-叔丁基-4-羟基-间甲苯基)-丙酸酯);IRGANOX245;CAS No.36443-68-2)。
在下文列表的1.抗氧化剂中给出了其它抗氧化剂的实例。
例如,在本发明组合物中组分(b)是通式(101)的抗氧化剂。
本发明组合物的实例是,其中组分(b)是通式(102)的抗氧化剂。
本发明实施方案是这样的组合物,其中组分(b)是通式(101)和(102)的抗氧化剂的结合。
本发明的另一实施方案是这样的组合物,其中存在组分(c)。
令人感兴趣的是这样的组合物,其中组分(c)是酚类或胺类抗氧化剂。酚类抗氧化剂的实例在下文列表的第1.1-1.17项中给出,特别是第1.1、1.13和1.14项,胺类抗氧化剂的实例在下文列表的第1.19项中给出。
其它令人感兴趣的是这样的组合物,其中其它抗氧化剂(c)是通式(103)-(108)的化合物。
(IRGANOX1076;CAS No.2082-79-3或1827-68-1)
(IRGANOX1135;CAS No.125643-61-0)
(BHT;CAS No.128-37-0)
(IRGANOX5057;CAS No.68411-46-1)。
例如,该组合物包含组分(c),由此组分(b)是通式(101)的抗氧化剂,而组分(c)是通式(103)-(108)的其它抗氧化剂。
例如,该组合物包含组分(c),由此组分(b)是通式(102)的抗氧化剂,而组分(c)是通式(103)-(108)的其它抗氧化剂。
优选是这样的组合物,其中抗氧化剂(b)和其它抗氧化剂(c)是
i)组分(101)和(102)的结合,
ii)组分(101)和(103)的结合,
iii)组分(101)和(104)的结合,
iv)组分(102)和(103)的结合,或
v)组分(102)和(104)的结合。
适用于本发明的聚酯多元醇、聚醚多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇、官能化聚醚和/或聚氨酯可以是,例如,
聚酯多元醇:聚丁二醇己二酸酯、聚己二醇己二酸酯、酞酐型聚酯多元醇,
由己内酯制成的聚酯多元醇;
聚醚多元醇:聚氧乙二醇、聚氧丙二醇、聚四亚甲基醚二醇、聚(氧化乙烯-co-氧化丙烯)-二醇;
丙烯酸类多元醇:获自烯丙基醇、烷基丙烯酸酯或甲基丙烯酸酯,和任选地乙烯基共聚单体如乙烯基芳族化合物、乙烯基醚和乙烯基酯的自由基共聚作用;烯丙基醇是烯丙醇、甲代烯丙醇、烯丙醇丙氧基化物、和/或烯丙醇乙氧基化物;烷基丙烯酸酯可以是甲基丙烯酸酯和/或丙烯酸正丁酯;或者这些丙烯酸类多元醇是聚丙烯酸酯多元醇或聚甲基丙烯酸酯多元醇;
聚碳酸酯多元醇:获自二醇如1,3-丙二醇、1,4-丁二醇、1,6-己二醇、二甘醇、三甘醇、四甘醇和其混合物与二芳基碳酸酯如二苯基碳酸酯或者光气的反应;
聚丁二烯多元醇;
氢化聚丁二烯多元醇;
官能化聚醚:甲硅烷基封端的聚醚
聚氨酯:一方面来源于羟基封端的聚醚、聚酯或者聚丁二烯,另一方面脂族或者芳族聚异氰酸酯,以及其前体。
例如,组分(a)不是甲硅烷基封端的聚醚,例如不是官能化聚醚。
令人感兴趣的本发明的组合物是,其中组分(a)是聚酯多元醇和/或聚醚多元醇,特别是上述的那些。
优选地,本发明的组合物包括其它添加剂。
其它添加剂的实例汇编在以下列表中。
1.抗氧化剂
1.1.烷基化单酚,例如2,6-二-叔丁基-4-甲基苯酚、2-叔丁基-4,6-二甲苯酚、2,6-二-叔丁基-4-乙基苯酚、2,6-二-叔丁基-4-正丁基苯酚、2,6-二-叔丁基-4-异丁基苯酚、2,6-二-叔丁基-4-仲丁基苯酚、2,6-二-叔丁基-4-壬基苯酚、2,6-二环戊基-4-甲基苯酚、2-(α-甲基环己基)-4,6-二甲基苯酚、2,6-双十八烷基-4-甲基苯酚、2,4,6-三环己基苯酚、2,6-二-叔丁基-4-甲氧基甲基苯酚、侧链中是直链或支链的壬基苯酚,例如,2,6-二-壬基-4-甲基苯酚、2,4-二甲基-6-(1′-甲基十一烷-1′-基)苯酚、2,4-二甲基-6-(1′-甲基十七烷-1′-基)苯酚、2,4-二甲基-6-(1′-甲基十三烷-1′-基)苯酚和其混合物。
1.2.烷基硫基甲基苯酚,例如2,4-二辛基硫基甲基-6-叔丁基苯酚、2,4-二辛基硫基甲基-6-甲基苯酚、2,4-二辛基硫基甲基-6-乙基苯酚、2,6-二-十二烷基硫基甲基-4-壬基苯酚。
1.3.氢醌和烷基化氢醌,例如2,6-二-叔丁基-4-甲氧基苯酚、2,5-双叔丁基氢醌、2,5-双叔戊基氢醌、2,6-二苯基-4-十八烷基氧基苯酚、2,6-二-叔丁基氢醌、2,5-双叔丁基-4-羟基茴香醚、3,5-二叔丁基-4-羟基茴香醚、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,例如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚和其混合物(维生素E)。
1.5.羟基化的硫基二苯醚,例如2,2′-硫基双(6-叔丁基-4-甲基苯酚)、2,2′-硫基双(4-辛基苯酚)、4,4′-硫基双(6-叔丁基-3-甲基苯酚)、4,4′-硫基双(6-叔丁基-2-甲基苯酚)、4,4′-硫基双(3,6-双仲-戊基苯酚)、4,4′-双(2,6-二甲基-4-羟苯基)二硫化物。
1.6亚烷基双酚,例如2,2′-亚甲基双(6-叔丁基-4-甲基苯酚)、2,2′-亚甲基双(6-叔丁基-4-乙基苯酚)、2,2′-亚甲基双[4-甲基-6-(α-甲基环己基)苯酚]、2,2′-亚甲基双(4-甲基-6-环己基苯酚)、2,2′-亚甲基双(6-壬基-4-甲基苯酚)、2,2′-亚甲基双(4,6-双叔丁基苯酚)、2,2′-亚乙基双(4,6-双叔丁基苯酚)、2,2′-亚乙基双(6-叔丁基-4-异丁基苯酚)、2,2′-亚甲基双[6-(α-甲基苄基)-4-壬基苯酚]、2,2′-亚甲基双[6-(α,α-二甲苯甲基)-4-壬基苯酚]、4,4′-亚甲基双(2,6-二-叔丁基苯酚)、4,4′-亚甲基双(6-叔丁基-2-甲基苯酚)、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-羟基苄基)-4-甲基苯酚、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.O-、N-和S-苄基化合物,例如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)二硫基对苯二甲酸酯、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.羟基苄基化丙二酸酯,例如双十八烷基-2,2-双(3,5-二叔丁基-2-羟基苄基)丙二酸酯、双十八烷基-2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸酯、双十二烷基巯基乙基-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.芳族羟基苄基化合物,例如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)苯酚。
1.10.三嗪化合物,例如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)异氰脲酸酯、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-羟基苯乙基)-1,3,5-三嗪、1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰基)-六氢-1,3,5-三嗪、1,3,5-三(3,5-二环己基-4-羟基苄基)异氰脲酸酯。
1.11.苄基膦酸酯,例如二甲基-2,5-二叔丁基-4-羟基苄基膦酸酯、二乙基-3,5-二叔丁基-4-羟基苄基膦酸酯、双十八烷基-3,5-二叔丁基-4-羟基苄基膦酸酯、双十八烷基-5-叔丁基-4-羟基-3-甲基苄基膦酸酯。
1.12.酰基氨基苯酚,例如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。
1.13.β-(3,5-二叔丁基-4-羟苯基)丙酸与下列醇的酯:单元醇或者多元醇,例如甲醇、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、硫基二甘醇、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-硫代十一醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷;β-(3,5-二叔丁基-4-羟苯基)丙酸的C13-C15烷基酯(CAS-No.171090-93-0)。
1.14.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与下列醇的酯:单元醇或者多元醇,例如甲醇、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、硫基二甘醇、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-硫代十一醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷;3,9-双[2-{3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基}-1,1-二甲基乙基]-2,4,8,10-四氧杂螺[5.5]十一烷。
1.15.β-(3,5-二环己基-4-羟苯基)丙酸与下列醇的酯:单元醇或者多元醇,例如甲醇、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、硫基二甘醇、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-硫代十一醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.16.3,8-二叔丁基-4-羟苯基乙酸与下列醇的酯:单元醇或者多元醇,例如甲醇、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、硫基二甘醇、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-硫代十一醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.17.β-(3,5-二叔丁基-4-羟苯基)丙酸的酰胺例如N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)己二酰胺、N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)丙二酰胺、N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)酰肼、N,N′-双[2-(3-[3,5-二叔丁基-4-羟苯基]丙酰氧基)乙基]草酰胺(NaugardXL-1,由Uniroyal供应)。
1.18.抗坏血酸(维生素C)
1.19.胺类抗氧化剂,例如N,N′-二异丙基-对苯二胺、N,N′-二仲丁基-对苯二胺、N,N′-双(1,4-二甲基戊基)-对苯二胺、N,N′-双(1-乙基-3-甲基戊基)-对苯二胺、N,N′-双(1-甲基庚基)-对苯二胺、N,N′-二环己基-对苯二胺、N,N′-二苯对苯二胺、N,N′-双(2-萘基)-对苯二胺、N-异丙基-N′-苯基-对苯二胺、N-(1,3-二甲基丁基)-N′-苯基-对苯二胺、N-(1-甲基庚基)-N′-苯基-对苯二胺、N-环己基-N′-苯基-对苯二胺、4-(p-甲苯氨磺酰)二苯胺、N,N′-二甲基-N,N′-二仲丁基-对苯二胺、二苯胺、N-烯丙基二苯胺、4-异丙氧基二苯胺、N-苯基-1-萘胺、N-(4-叔辛基苯基)-1-萘胺、N-苯基-2-萘胺、4,4’-双(α,α-二甲基苄基)二苯胺、N-苯基苯胺与异丁烯和2,4,4-三甲基戊烯的反应产物、辛基化二苯胺如对,对′-二叔辛基二苯胺、4-正-丁基氨基酚、4-丁酰基氨基苯酚、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-4-二甲基氨基甲酚、2,4′-二氨基二苯甲烷、4,4′-二氨基二苯甲烷、N,N,N′,N′-四甲基-4,4′-二氨基二苯甲烷、1,2-双[(2-甲基苯基)氨基]乙烷、1,2-双(苯基氨基)丙烷、(邻甲苯基)缩二胍、双[4-(1′,3′-二甲基丁基)苯基]胺、叔辛基化N-苯基-1-萘胺、单和二烷基化叔丁基/叔辛基二苯胺的混合物、单和二烷基化壬基二苯胺的混合物、单和二烷基化十二烷基二苯胺的混合物、单和二烷基化异丙基/异己基二苯胺的混合物、单和二烷基化叔丁基二苯胺的混合物、2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪、吩噻嗪、单和二烷基化叔丁基/叔辛基吩噻嗪的混合物、单和二烷基化叔辛基-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。
2.UV吸收剂和光稳定剂
2.1.2-(2′-羟苯基)苯并三唑,例如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′-辛基氧基苯基)苯并三唑、2-(3′,5′-二叔戊基-2′-羟苯基)苯并三唑、2-(3′,5′-二(α,α-二甲基苯甲基)-2′-羟苯基)苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-辛基氧基羰基乙基)苯基)-5-氯-苯并三唑、2-(3′-叔丁基-5′-[2-(2-乙基己氧基)-羰基乙基]-2′-羟苯基)-5-氯-苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)-5-氯-苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-辛基氧基羰基乙基)苯基)苯并三唑、2-(3′-叔丁基-5′-[2-(2-乙基己氧基)羰基乙基]-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、2-(3′-叔丁基-2′-羟基-5′-(2-异辛基氧基羰基乙基)苯基苯并三唑、2,2′-亚甲基-双[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚];2-[3′-叔丁基-5′-(2-甲氧基羰基乙基)-2′-羟苯基]-2H-苯并三唑与聚乙二醇300的酯交换产物;
[R-CH2CH2-COO-CH2CH22,
其中R=3′-叔丁基-4′-羟基-5′-2H-苯并三唑-2-基苯基、2-[2′-羟基-3′-(α,α-二甲基苯甲基)-5′-(1,1,3,3-四甲基丁基)-苯基]苯并三唑;2-[2′-羟基-3′-(1,1,3,3-四甲基丁基)-5′-(α,α-二甲基苯甲基)-苯基]苯并三唑。
2.2.2-羟基二苯甲酮,例如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.被取代的和未被取代的苯甲酸的酯,例如4-叔丁基苯基水杨酸酯、苯基水杨酸酯、辛基苯基水杨酸酯、二苯甲酰间苯二酚、双(4-叔丁基苯甲酰)间苯二酚、苯甲酰基间苯二酚、2,4-二-叔丁基苯基3,5-二叔丁基-4-羟基苯甲酸酯、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、2-甲基-4,6-二叔丁基苯基3,5-二叔丁基-4-羟基苯甲酸酯。
2.4.丙烯酸酯,例如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-甲氧甲酰基肉桂酸甲酯、α-氰基-β-甲基-p-甲氧基肉桂酸甲酯、α-氰基-β-甲基-p-甲氧基-肉桂酸丁酯、α-甲氧甲酰-p-甲氧基肉桂酸甲酯、N-(β-甲氧甲酰-β-氰基乙烯基)-2-甲基二氢吲哚、四(α-氰基-β,β-二苯基丙烯酸新戊酯。
2.5.镍化合物,例如2,2′-硫代-双[4-(1,1,3,3-四甲基丁基)苯酚]的镍络合物(如1∶1或者1∶2络合物,有或者没有额外的配位体如正丁胺、三乙醇胺或者环己基二乙醇胺)、二丁基二硫代氨基甲酸镍、单烷基酯如4-羟基-3,5-二叔丁基苄基膦酸的甲酯或者乙酯的镍盐、酮肟的镍络合物如2-羟基-4-甲基苯基十一烷基酮肟的镍盐、1-苯基-4-月桂酰-5-羟基吡唑的镍络合物(有或者没有额外的配位体)。
2.6.位阻胺,例如双(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、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)己二胺和4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、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-乙烷二基)-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、4-十八烷氧基-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-双叔丁基苄基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-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)己二胺和4-吗啉代-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物、2-氯-4,6-二(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物、8-乙酰-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-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)己二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合物、1,2-双(3-氨基丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪以及4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS登记号[136504-96-6]);1,6-己二胺和2,4,6-三氯-1,3,5-三嗪以及N,N-二丁胺和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS登记号[192268-64-7]);N-(2,2,6,6-四甲基-4-哌啶基)-正十二烷基丁二酰亚胺、N-(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基丁二酰亚胺、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-环十一烷基-1-氧杂-3,8-二氮杂-4-氧代螺-[4,5]癸烷和表氯醇的反应产物、1,1-双(1,2,2,6,6-五甲基4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯、N,N′-双甲酰基-N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺、4-甲氧基亚甲基丙二酸与1,2,2,6,6-五甲基4-羟基哌啶的二酯、聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷、马来酸酐-α-烯烃共聚物与2,2,6,6-四甲基-4-氨基哌啶或者1,2,2,6,6-五甲基-4-氨基哌啶的反应产物、2,4-双[N-(1-环己基氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁氨基]-6-(2-羟乙基)氨基-1,3,5-三嗪、1-(2-羟基-2-甲基丙氧基)-4-十八烷酰氧基-2,2,6,6-四甲基哌啶、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、Sanduvor(Clariant;CAS登记号106917-31-1]、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、2,4-双[(1-环己基氧基-2,2,6,6-哌啶-4-基)丁氨基]-6-氯-s-三嗪与N,N′-双(3-氨丙基)乙二胺)的反应产物、1,3,5-三(N-环己基-N-(2,2,6,6-四甲基哌嗪-3-酮-4-基)氨基)-s-三嗪、1,3,5-三(N-环己基-N-(1,2,2,6,6-五甲基哌嗪-3-酮-4-基)氨基)-s-三嗪。
2.7.草酰胺,例如4,4′-二辛氧基草酰二苯胺、2,2’-二乙氧基草酰二苯胺、2,2′-二辛基氧基-5,5′-二-叔丁基草酰二苯胺(tert-butoxanilide)、2,2’-二癸基氧基-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(3-二甲基氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2′-乙基草酰二苯胺(ethoxanilide)和其与2-乙氧基-2′-乙基-5,4′-二-叔丁基草酰二苯胺的混合物、邻和对甲氧基二取代的草酰二苯胺的混合物和邻和对乙氧基-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,例如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-丙基氧基苯基)-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/十三烷基氧基-2-羟基丙氧基)-2-羟苯基]-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、2-{2-羟基-4-[3-(2-乙基己基-1-氧基)-2-羟基丙氧基]苯基}-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2,4-双(4-[2-乙基己氧基]-2-羟苯基)-6-(4-甲氧基苯基)-1,3,5-三嗪。
3.金属钝化剂,例如N,N′-二苯基草酰胺、N-水杨醛-N′-水杨酰肼、N,N′-双(水杨酰)肼、N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼、3-水杨酰氨基-1,2,4-三唑、双(亚苄基)草酰二酰肼、草酰二苯胺、间苯二甲酰肼、癸二酰二苯基酰肼、N,N′-双乙酰己二酰二酰肼、N,N′-双(水杨酰)草酰二酰肼、N,N′-双(水杨酰)硫基丙酰二酰肼。
4.亚磷酸酯和亚膦酸酯(phosphonite),例如亚磷酸三苯酯、二苯基烷基亚磷酸酯、苯基二烷基亚磷酸酯、三(壬基苯基)亚磷酸酯、三(十二烷基)亚磷酸酯、三(十八烷基)亚磷酸酯、二硬脂酰季戊四醇二亚磷酸酯、三(2,4-二-叔丁基苯基)亚磷酸酯、二异癸基季戊四醇二亚磷酸酯、双(2,4-二-叔丁基苯基)季戊四醇二亚磷酸酯、双(2,4-二-枯基苯基)季戊四醇二亚磷酸酯、双(2,6-二-叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、二异癸基氧基季戊四醇二亚磷酸酯、双(2,4-二-叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三(叔丁基苯基)季戊四醇二亚磷酸酯、三硬脂酰山梨糖醇三亚磷酸酯、四(2,4-二-叔丁基苯基)4,4′-亚联苯基二亚膦酸酯(phosphonite)、6-异辛基氧基-2,4,8,10-四叔丁基-12H-二苯[d,g]-1,3,2-二氧杂磷杂环辛烯、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、6-氟-2,4,8,10-四-叔丁基-12-甲基-二苯[d,g]-1,3,2-二氧杂磷杂环辛烯、2,2′,2″-次氮基[三乙基三(3,3′,5,5′-四叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯]、2-乙基己基(3,3′,5,5′-四叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯、5-丁基-5-乙基-2-(2,4,6-三叔丁基苯氧基)-1,3,2-二氧杂磷杂环丙烷。
以下亚磷酸酯是特别优选的:
三(2,4-二-叔丁基苯基)亚磷酸酯(Irgafos168,Ciba SpecialtyChemicals Inc.)、三(壬基苯基)亚磷酸酯、
5.羟胺,例如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-双十二烷基羟基胺、N,N-双十四烷基羟基胺、N,N-双十六烷基羟基胺、N,N-双十八烷基羟基胺、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、衍生自氢化牛脂胺的N,N-二烷基羟基胺。
6.硝酮,例如,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、来源于衍生自氢化牛脂胺的N,N-二烷基羟基胺的硝酮。
7.硫基增效剂,例如硫代二丙酸双十二烷基酯、硫代二丙酸双十四烷基酯、硫代二丙酸双十八烷基酯或者双十八烷基二硫化物。
8.过氧化物清除剂,例如β-硫代二丙酸的酯,例如十二烷基、十八烷基,十四烷基或者十三烷基酯、巯基苯并咪唑或者2-巯基苯并咪唑的锌盐、二丁基二硫基氨基甲酸锌、双十八烷基二硫化物、季戊四醇四(β-十二烷基巯基)丙酸酯。
9.聚酰胺稳定剂,例如与碘化物和/或磷化合物结合的铜盐和二价锰的盐。
10.碱性助稳定剂,例如三聚氰胺、聚乙烯吡咯烷酮、双氰胺、氰脲酸三烯丙酯、脲衍生物、肼衍生物、胺、聚酰胺、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、山嵛酸镁、硬脂酸镁、蓖麻醇酸钠和棕榈酸钾、邻苯二酚锑或者邻苯二酚锌。
11.成核剂,例如无机物如滑石、金属氧化物如二氧化钛或者氧化镁、优选碱土金属的,磷酸盐、碳酸盐或硫酸盐;有机化合物,如单或多元羧酸和其盐,例如4-叔丁基苯甲酸、己二酸、二苯基乙酸、琥珀酸钠或者苯甲酸钠;聚合物,如离子共聚物(离聚物)。特别优选是1,3:2,4-双(3’,4’-二甲基亚苄基)山梨糖醇、1,3:2,4-二(对甲基二亚苄基)山梨糖醇和1,3:2,4-二(亚苄基)山梨糖醇。
12.填料和增强剂,例如碳酸钙、硅酸盐、玻璃纤维、玻璃珠、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、木屑和其它天然产物的粉末或纤维、合成纤维。
13.其它添加剂,例如增塑剂、润滑剂、乳化剂、颜料、流变助剂、催化剂、流动调节剂、光学增白剂、抗静电剂和起泡剂。
14.苯并呋喃酮和二氢吲哚酮,例如公开在以下文献中的那些:U.S.4,325,863;U.S.4,338,244;U.S.5,175,312;U.S.5,216,052;U.S.5,252,643;DE-A-4316611;DE-A-4316622;DE-A-4316876;EP-A-0589839,EP-A-0591102;EP-A-1291384或3-[4-(2-乙酸基乙氧基)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-乙氧苯基)苯并呋喃-2-酮、3-(4-乙酸基-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、3-(3,4-二甲基苯基)-5,7-二-叔丁基苯并呋喃-2-酮、3-(2,3-二甲基苯基)-5,7-二-叔丁基苯并呋喃-2-酮、3-(2-乙酰-5-异辛基苯基)-5-异辛基苯并呋喃-2-酮。
15.阻燃剂,例如,卤化苯、联苯、苯酚、其醚或酯、双酚、二苯醚、芳族羧酸或其多酸、酸酐、酰胺或酰亚胺;有机环脂族或聚环脂族卤代化合物;和有机脂族卤代化合物如卤化链烷烃、寡聚物或聚合物、烷基磷酸酯或烷基异氰脲酸酯。这些组分在本领域中是已知的,参见例如美国专利4,579,906(如第3列第30-41行)、5,393,812;还参见PlasticsAdditives Handbook,H.Zweifel编辑,第5版,Hanser Publ.,Munich2001,第681-698页;或四苯基间苯二酚二亚磷酸酯(FYROFLEXRDP,Akzo Nobel)、磷酸氯烷基酯(ANTIBLAZEAB-100,Albright&Wilson;FYROLFR-2,Akzo Nobel)、多溴二苯醚(DE-60F,Great Lakes Corp.)、十溴二苯醚(DBDPO;SAYTEX102E)、三[3-溴-2,2-双(溴甲基)丙基]磷酸酯(PB 370,FMC Corp.)、双酚A的双(2,3-二溴丙基醚)(PE68)、溴化环氧树脂、亚乙基-双(四溴邻苯二甲酰亚胺)(SAYTEXBT-93),双(六氯环戊二烯)环辛烷(DECLORANE PLUS)、氯化链烷烃、1,2-双(三溴苯氧基)乙烷(FF680)、四溴双酚A(SAYTEXRB100 or SAYTEX CP-2000)、亚乙基双(二溴-降冰片烷二甲酰亚胺)(SAYTEXBN-451)、双(六氯环戊二烯)环辛烷(DECLORANE Plus)、三(2,3-二溴丙基)-异氰脲酸酯、亚乙基-双四溴邻苯二甲酰亚胺、1,2,5,6,9,10-六溴环-十二烷、乙烷-1,2-双(五溴苯基)、四溴双酚A-双-(烯丙醚)、二溴环己烷、三溴苯酚-氰尿酸酯(DeadSeaFR-245)、三(2-氯乙基)磷酸酯、三(2,3-二溴丙基)磷酸酯、三(2,3-二氯丙基)磷酸酯、氯菌酸、四氯邻苯二甲酸、四溴邻苯二甲酸、双(N,N′-羟乙基)四氯-苯二胺、聚-β-氯乙基三膦酸酯(phosponate)-混合物、八溴二苯醚、六氯环戊二烯-衍生物、亚乙基-双(二溴降冰片烷二甲酰亚胺)(SaytexBN-451)、双(六氯环戊二烯)-环辛烷、聚四氟乙烯(TeflonGC)添加或者未添加锑增效剂如Sb2O3;四苯基间苯二酚二亚磷酸酯(FYROFLEXRDP,Akzo Nobel)、磷酸三苯酯、聚磷酸铵(APP或HOSTFLAMAP750)、间苯二酚二磷酸酯寡聚物(RDP)、乙二胺二磷酸酯(EDAP)、磷酸三辛酯、磷酸三甲苯酯、四(羟甲基)磷硫醚、二乙基-N,N-双(2-羟基-乙基)-氨甲基膦酸酯、磷酸的羟基烷基酯、磷腈类阻燃剂;氢氧化镁;氧化锌、三氧化钼、Sb2O5、Sb2O3;三聚氰胺磷酸酯(MELAPURMP)、焦磷酸三聚氰胺、三聚氰胺聚磷酸铵、三聚氰胺焦磷酸铵、三聚氰胺氰尿酸酯(MELAPURMC)、三聚氰胺硼酸酯、三聚氰胺多磷酸酯(Melapur200)、三聚氰胺氰尿酸酯(MelapurMC50);或2,4-双[(1-环己基氧基-2,2,6,6-哌啶-4-基)丁基氨基]-6-氯-s-三嗪与N,N′-双(3-氨丙基)乙二胺)的反应产物[CAS 191680-81-6]、1-(2-羟基-2-甲基丙氧基)-4-十八烷酰氧基-2,2,6,6-四甲基哌啶;或三水氧化铝、二乙基膦酸的铝盐(DEPAL);或硼酸锌;或寡聚二异丙苯、二氧化硅、硅酮、硅酸钙、硅酸镁、硫酸钙或碳酸镁。
添加剂,特别是本文中所提及的抗氧化剂大部分是市售可得的。
例如,相对于本发明组合物的总重量,以浓度0.01-10%添加除阻燃剂以外的其它添加剂。例如,相对于本发明组合物的总重量,阻燃剂以浓度0.1-20%,特别是0.1-10%添加。
令人感兴趣的是这样的组合物,其包括作为其它添加剂的不同于(b)和(c)的抗氧化剂、光稳定剂、加工稳定剂、阻燃剂、抗微生物剂、抗气体褪色剂和/或光学增白剂,例如以上所列举的那些。
更令人感兴趣的是这样的组合物,其包括作为其它添加剂的不同于(b)和(c)的酚类和/或胺类抗氧化剂、受阻胺光稳定剂、UV-吸收剂、亚磷酸酯、亚膦酸酯(phosphonite)、苯并呋喃酮和/或阻燃剂,特别是以上所列举的那些。
最令人感兴趣的是这样的组合物,其包括作为其它添加剂的受阻胺光稳定剂和/或UV-吸收剂,例如以上第2项所列举的那些。
优选的是这样的组合物,其中组分(b)和(c)的总量是0.01%-5%,例如0.5%-2%,基于组合物的重量计。
令人感兴趣的是这样的组合物,其中组分(b)∶(c)或者通式(101)∶(102)化合物的比值分别为10∶1-1∶10,特别是3∶1-1∶3。
其它令人感兴趣的是在(a)聚酯多元醇、聚醚多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇、官能化聚醚和/或聚氨酯中如上所定义的通式(101)和/或(102)的抗氧化剂(b)和任选地其它抗氧化剂(c)作为稳定剂的耐热降解的用途。
前提条件是
如果组分(b)是通式(101)的抗氧化剂并且组分(c)不存在,那么组分(a)不是聚氨酯。
优选地,上述前提条件是如果组分(b)是通式(101)的抗氧化剂,那么该组合物包含其它的抗氧化剂(c),
如果组分(a)是聚氨酯并且组分(b)是通式(102)的抗氧化剂,那么组分(c)存在于组合物中,
如果抗氧化剂是通式(101)和(103)的化合物的结合,那么组分(a)不是聚酯多元醇或聚氨酯,并且
如果抗氧化剂是通式(101)和(104)的化合物的结合,那么组分(a)不是聚醚多元醇或聚氨酯。
最优选地,上述前提条件是如果组分(b)是通式(101)的抗氧化剂,那么该组合物包含其它的抗氧化剂(c),
如果组分(a)是聚氨酯并且组分(b)是通式(102)的抗氧化剂,那么组分(c)存在于组合物中,和
如果抗氧化剂是通式(101)和(103)或(101)和(104)的化合物的结合,那么组分(a)不是聚酯多元醇、聚醚多元醇或聚氨酯。
优选地,组分(a)和(b)是如上所述的那些。
一种实例是使用抗氧化剂(b)和任选地其它抗氧化剂(c)以及至少一种其它添加剂,特别是如上所述的其它添加剂。
本发明的另一实施方案是使用耐热降解的(b)通式(101)和/或(102)的抗氧化剂和(c)任选地其它抗氧化剂使(a)聚酯多元醇、聚醚多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇、官能化聚醚和/或聚氨酯稳定以耐热降解的方法。
前提条件是
如果组分(b)是通式(101)的抗氧化剂并且组分(c)不存在,那么组分(a)不是聚氨酯。
对于其它前提条件和/或组分(a)和(b),优选的是如上所给出的。
另一实例是本发明方法,其中抗氧化剂(b)和任选的其它抗氧化剂(c)与至少一种其它添加剂,特别是如上所述的其它添加剂,一起使用。
本发明的聚酯多元醇、聚醚多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇、官能化聚醚和/或聚氨酯组合物也可以是泡沫体(柔性的、刚性的、整体的)、微孔泡沫塑料、铸塑PU、PU表皮、PU热熔性胶粘剂、甲硅烷基化的聚氨酯(SPUR)、甲硅烷基-封端的聚醚、热塑性聚氨酯(TPU)、PU弹性体、人造革、PU表皮、PU杂散涂层或反应注塑品(RIM)。
例如,本发明的聚醚多元醇、聚酯多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇、官能化聚醚和/或聚氨酯组合物不起泡。
例如,丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇和官能化聚醚是市售可得的。
例如,通过使聚醚、聚酯和聚丁二烯(其包含末端羟基,即多元醇)与脂族或芳族聚异氰酸酯反应而获得聚氨酯。
具有末端羟基的聚醚和聚酯是已知的,并且例如,通过使环氧化物如环氧乙烷、环氧丙烷、环氧丁烷、四氢呋喃、氧化苯乙烯或者表氯醇例如在BF3存在下与其自身进行聚合,或者通过这些环氧化物,单独地或者以混合物的形式或者相继地,与含活泼氢原子的起始组分如醇、氨或胺,例如乙二醇、1,3-和1,2-丙二醇、三羟甲基丙烷、4,4′-二羟二苯丙烷、苯胺、乙醇胺或乙二胺的加成反应而制备。根据本发明,蔗糖聚醚也是合适的。在很多情况下,优选的是主要含伯OH基团(高达90wt%,基于聚醚中存在的全部OH基团)的那些聚醚。此外,通过乙烯基聚合物改性的聚醚,如在聚醚存在下例如通过聚合苯乙烯和丙烯腈而形成的,是合适的,含OH基团的聚丁二烯同样合适。
这些化合物通常的分子量为40,并且是多羟基化合物,特别是含2-8个羟基的化合物,特别是分子量为800-10000、优选1000-6000的那些,例如含至少2个、通常2-8个、但优选2-4个羟基的聚醚,其对于制备均质聚氨酯和泡沫状聚氨酯来说是已知的。
当然可以使用含至少两个异氰酸酯-活泼氢原子的,特别是分子量为400-10000的上述化合物的混合物。
合适的聚异氰酸酯是脂族、环脂族、芳脂族、芳族和杂环聚异氰酸酯,例如亚乙基二异氰酸酯、1,4-丁基二异氰酸酯、1,6-己基二异氰酸酯、1,12-十二烷二异氰酸酯、环丁烷1,3-二异氰酸酯、环己烷1,3-和-1,4-二异氰酸酯以及这些异构体的任何所期望的混合物、1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷、2,4-和2,6-六氢甲苯二异氰酸酯以及这些异构体的任何所期望的混合物、六氢-1,3-和/或-1,4-苯撑二异氰酸酯、全氢-2,4′-和/或-4,4′-二苯甲烷二异氰酸酯、1,3-和1,4-苯撑二异氰酸酯、2,4-和2,6-甲苯二异氰酸酯、以及这些异构体的任何所期望的混合物、二苯甲烷2,4′-和/或-4,4′-二异氰酸酯、亚萘基1,5-二异氰酸酯、三苯甲烷4,4′,4″-三异氰酸酯、聚苯-聚亚甲基聚异氰酸酯(通过苯胺-甲醛缩合随后光气化获得的)、间和对异氰酸根合苯磺酰异氰酸酯、全氯化芳基聚异氰酸酯、含碳二亚胺基团的聚异氰酸酯、含脲基甲酸酯基团的聚异氰酸酯、含异氰脲酸酯基团的聚异氰酸酯、含尿烷基团的聚异氰酸酯、含酰化尿素基团的聚异氰酸酯、含缩二脲基团的聚异氰酸酯、含酯基的聚异氰酸酯、以上异氰酸酯与缩醛的反应产物、和含聚合脂肪酸自由基的聚异氰酸酯。
还可以使用含异氰酸酯基团的蒸馏残余物,因为它们是或者溶于一种或多种以上聚异氰酸酯,其在工业制备异氰酸酯的过程中获得。另外可以使用以上聚异氰酸酯的任何所期望的混合物。
一般特别优选的是可易于工业获取的聚异氰酸酯,例如芳族异氰酸酯如2,4-和2,6-甲苯二异氰酸酯和这些异构体的任何所期望的混合物(“TDI”)、聚苯基-聚亚甲基-聚异氰酸酯(如通过苯胺-甲醛缩合随后光气化制备的,“粗MDI”)、和含碳二亚胺、尿烷、脲基甲酸酯、异氰脲酸酯、尿素或缩二脲基团的聚异氰酸酯(“改性聚异氰酸酯”)。
聚氨酯优选从液体起始组分制备,即在一步法中将待彼此反应的原料混合在一起。
将添加剂和/或稳定剂共混物加入到聚酯多元醇、聚醚多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇、官能化聚醚和/或聚氨酯中是通过已知的方法进行的,例如在配混、挤出、共挤出之前或之中,或者可以在聚合之前或之中或者在交联之前进行添加。如果添加剂和/或稳定剂共混物在聚合前添加的话,可以将它们溶解在一个或全部的反应物中。优选将它们溶于聚酯多元醇、聚醚多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇或氢化聚丁二烯多元醇。
在提供聚氨酯(PU)化合物、热塑性PU、铸塑PU、反应注塑品(RIM)、喷涂层、PU表皮方面,本发明的组合物将有助于满足聚氨酯工业的需要和/或需求。
根据本发明的组合物可以有利地被用于各种用途并且用于制备各种成形制品。实例是:
V)粘合剂、涂层和弹性体
V-1)PU弹性体
V-1-A)电气和电子工业
套管、电缆接头、用于电气控制和调节的部件、电磁开关、硬而有弹性的密封材料、电动车辆用变速器的索缆铸造物(gear shift cablecastings for motor vehicle electrics)、绝缘材料、印刷电路、封装材料(potting)、半导体、开关、变速齿轮(switchgears)、中等和高压变压器。
V-1-B)重型工业
轮、传送带、筛和衬垫。
V-1-C)休闲用品
滑板滚轴。
V-2)粘合剂
V-2-A)汽车
将织物粘合到泡沫塑料上,车辆挡风板的无窗框安装,玻璃窗替换,各种汽车部件的加固,将箔片真空层压至纤维板。
V-2-B)建筑和土木工程
粘合夹层绝缘板,地板,屋顶,停车场的密封,混凝土路面,工业楼板,一种用于垂直接缝的元件密封剂(预制混凝土板、伸缩接缝),用于垂直面的可浇注的接缝密封剂(地板-墙壁接缝)。
V-2-C)木工业
家具装配和木材-塑料的型材层压(profile lamination)
V-2-D)软包装
薄膜-薄膜和薄膜-箔片层压。
V-2-E)鞋类
粘合鞋底。
V-2-F)一般工业
电子工业、日用商品、扬声器隔音板、办公器具、金属窗框、空调系统、公共汽车、容器、卡车、金属/金属薄板结构、火车车厢、污水作业、筒仓和通风系统。
V-2-G)保温玻璃窗
V-2-H)橡胶碎屑
用于再捏炼橡胶废料的粘合剂;该复合材料主要用作成形瓷砖、运动场(就地)、跑道(就地)。
V-2-J)夹层结构
将相似基材粘合在一起或者粘合到其它材料如金属、塑料和硬质泡沫;用于各种层压板,如用于建筑物、大篷车、隔断墙、冷藏卡车、货柜和冷藏库的板。
V-3)聚氨酯热熔粘合剂
V-3-A)汽车应用,特别地作为仪表组、隔音材料、地毯、座位、装饰物品、外部应用如挡风雨条、外部装饰物、灯透镜设备、和防风罩组件、娱乐车侧壁。
V-3-B)织物应用,特别地层压、型材包裹。
V-3-C)家具制造业,特别地用于粘结粘合固体木材、木材复合物、金属五金器具和装饰塑料层压板。
V-3-D)建筑业,特别地门窗框组件和用于漆布地面的拐角覆盖物。
VI)TPU
VI-1)粘合剂种类
用于鞋(向上粘合到鞋底)、鞋头(粉末)、家具、自己动手(doityourself)和汽车的粘合剂。
VI-2)挤出物种类
VI-2-A)电缆和导线应用
家用电器电缆、露天电缆、工业电缆和导线。
VI-2-B)软管和管道
气动输送系统、通风系统、气动控制单元、气动止动、液压管、波纹管、消防管、真空吸尘器管。
VI-2-C)型材应用
圆形绳索、齿状带、垫圈、软钢索(bowdencable)、剥离器刀刃、电缆。
VI-3)薄膜和薄板
这些由芳族和脂族TPU制成。一般的应用是阻挡膜、粘性膜、缝口带、安全玻璃隔层。
VI-3-A)脂族TPU的光学应用
安全层压板、安全显示屏。
VI-3-B)脂族TPU的非光学应用
交通和警戒标志、用于表面汽车应用的保护膜、工业带材、工业船舶和气球、用于食品包装的薄膜、航天技术。
VI-3-C)熔融涂层
食物输送带和工业制品。
VI-4)注塑
VI-4-A)一般用途
耳标、车轮、马掌、塞子、手表带。
VI-4-B)高性能/专用化合物
运动鞋的透明鞋底、滑雪护目镜框、工业零件、筛(采矿)。
VI-4-C)汽车应用
变速器旋钮、轴承承窝、电缆插头、轴衬、套管、摩擦轴承。
VI-4-D)密封应用
液压密封、剥离器环、垫圈、气压密封、膜。
VII)汽车应用
减震器、仪表板、电池、前后衬板、遮光板下的模塑零件、顶板架(hatshelf)、车厢衬板、内衬板、气袋罩、配件(灯)的电子模塑制品、仪表板嵌板、顶灯玻璃、仪表盘、外衬板、室内装饰品、汽车灯、头灯、驻车灯、尾灯、制动灯、内和外部装饰;门心板;储气罐;玻璃窗正面;后窗玻璃;椅背、外板、绝缘导线、用于密封的型材挤出制品、包层、柱罩、底盘部分、排气系统、燃料过滤器/填料、燃油泵、燃料箱、体侧模塑制品、可改变的顶、车外后视镜、外部装饰、扣件/固定件、前端组件、玻璃、铰链、锁系统、行李/行李架、压制/冲压零件、密封、侧面碰撞保护、隔音材料/绝缘体和遮阳篷顶。
VII-1)弹性泡沫塑料,特别地扶手、头部保护装置、吸声泡沫地毯、座位。
VII-2)半硬质泡沫塑料,特别地屋顶衬板、帽架、门心板、扶手、仪表盘、头部撞击、侧部撞击。
VII-3)硬质泡沫,特别地空腔泡沫填料。
VII-4)弹性整体泡沫塑料,特别地方向盘、空气过滤器、变速器旋钮、阻流板、电缆薄板、头部保护装置。
VII-5)RIM,特别地减震器、遮阳篷顶、前后侧板、门槛擦板。
VII-6)TPU,特别地前后侧板、门槛防擦板、电缆薄板、变速器旋钮、仪表盘。
VII-7)铸塑PU系统,特别地辅助弹簧、隔振弹簧、阻尼座、顶部固定件、转动限制器、应急车轮、主体装配、门系统止动。
VIII)鞋类
鞋/鞋底(鞋垫、鞋罩、粘合剂、结构粘合剂)。
IX)家具
X)配套设备
用于闲暇时间的物品如运动和健身装置、体操垫、滑雪靴、直排旱冰鞋、滑雪板、大脚(big foot)、运动场地表面(例如网球场地)。
XI)其它
复合板、绝缘板和块、工业绝缘体、绝热管壳、食物盒(水果、蔬菜、肉、鱼)、合成纸、瓶子标签、长椅、人用人造关节、印刷版(苯胺印刷)、印刷电路板、显示器技术、螺旋顶盖、用于瓶子的盖子和塞子、和罐。
例如
1)PU弹性体
2)PU表皮
3)PU喷涂层
4)热塑性聚氨酯(TPU)
5)PU人造革
6)甲硅烷基化聚氨酯(SPUR)
7)PU热熔性粘合剂
8)铸塑PU
9)PU泡沫塑料(弹性的、刚性的、整体的)
10)PU微孔体
11)反应注塑品(RIM)。
除非另有说明,百分比是重量%。
实施例1
混合
在65℃在玻璃容器中将30g的聚酯多元醇(聚丁二醇己二酸酯)与0.3%的下表中提及的添加剂混合(对于对比例,无添加剂)。然后在65℃搅拌该混合物30分钟,随后冷却到环境温度。
DSC测量:
一种通常已知的并且用于确定多元醇的抗氧化能力的方法是DSC(差示扫描量热法)。放热峰的形状指出了热氧化反应的开始。在测试期间,在氧气下,温度范围是50℃-280℃,加热速率为5℃/分钟。确定起始温度。该温度定义为氧化诱导温度(OIT)。
表1:测量由抗氧化剂得到的聚酯多元醇(聚丁二醇己二酸酯)的氧化诱导温度(OIT)。(加热速率5℃/分钟,在氧气下)。15mg样品
制剂 | % | 添加剂 | OIT(℃) |
1(对比例) | 没有抗氧化剂 | 225 | |
2 | 0.30 | IRGANOX1425 | 262 |
3 | 0.30 | TINUVIN144 | 272 |
Claims (14)
2.根据权利要求1的组合物,其中组分(c)存在。
3.根据权利要求2的组合物,其中组分(c)是酚类或胺类抗氧化剂。
5.根据权利要求4的组合物,其中抗氧化剂(b)和其它抗氧化剂(c)是
i)组分(101)和(102)的结合,
ii)组分(101)和(103)的结合,
iii)组分(101)和(104)的结合,
iv)组分(102)和(103)的结合,或
v)组分(102)和(104)的结合。
6.根据权利要求1的组合物,其包括其它添加剂。
7.根据权利要求6的组合物,其包括作为其它添加剂的不同于(b)和(c)的抗氧化剂、光稳定剂、加工稳定剂、阻燃剂、抗微生物剂、抗气体褪色剂和/或光学增白剂。
8.根据权利要求7的组合物,其包括作为其它添加剂的酚类和/或胺类抗氧化剂、受阻胺光稳定剂、UV-吸收剂、亚磷酸酯、亚膦酸酯、苯并呋喃酮和/或阻燃剂。
9.根据权利要求1的组合物,其中组分(b)和(c)的总量是0.01%-5%,基于组合物的重量计。
10.根据权利要求1的组合物,其中组分(b)∶(c)或者通式(101)∶(102)化合物的比值分别为10∶1-1∶10。
11.在(a)聚酯多元醇、聚醚多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇、官能化聚醚和/或聚氨酯中如权利要求1中定义的通式(101)和/或(102)的抗氧化剂(b)和任选地其它抗氧化剂(c)作为稳定剂的耐热降解的用途,
前提条件是
如果组分(b)是通式(101)的抗氧化剂并且组分(c)不存在,那么组分(a)不是聚氨酯。
12.根据权利要求11的抗氧化剂(b)和任选地其它抗氧化剂(c)结合至少一种其它添加剂的用途。
13.使用(b)如权利要求1中限定的通式(101)和/或(102)的抗氧化剂和(c)任选地耐热降解的其它抗氧化剂使(a)聚酯多元醇、聚醚多元醇、丙烯酸类多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、氢化聚丁二烯多元醇、官能化聚醚和/或聚氨酯稳定以耐热降解的方法,
前提条件是
如果组分(b)是通式(101)的抗氧化剂并且组分(c)不存在,那么组分(a)不是聚氨酯。
14.根据权利要求13的方法,其中抗氧化剂(b)和任选地其它抗氧化剂(c)与至少一种其它添加剂结合使用。
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KR (1) | KR20070107071A (zh) |
CN (1) | CN101128529A (zh) |
AR (1) | AR055036A1 (zh) |
AT (1) | ATE471961T1 (zh) |
BR (1) | BRPI0607564A2 (zh) |
CA (1) | CA2598498A1 (zh) |
DE (1) | DE602006015037D1 (zh) |
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Cited By (3)
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CN101815751B (zh) * | 2007-08-01 | 2013-08-14 | 连锁添加剂有限两合公司 | 用作阻燃剂的含磷三嗪化合物 |
CN104497253A (zh) * | 2014-12-14 | 2015-04-08 | 天津利安隆新材料股份有限公司 | 一种多元醇组合物 |
CN108997557A (zh) * | 2018-09-11 | 2018-12-14 | 界首永恩机电科技有限公司 | 一种环保tpu的制备方法 |
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DE102007027801A1 (de) * | 2007-06-16 | 2008-12-18 | Bayer Materialscience Ag | Reaktive Polyurethan-Hotmelts |
US9200122B2 (en) | 2007-08-01 | 2015-12-01 | J. M. Huber Corporation | Triazine compounds containing phosphorous as flame retardants |
DE102009014411A1 (de) † | 2009-03-26 | 2010-09-30 | Lanxess Deutschland Gmbh | Stabilisierung von Polyolen |
US9469798B1 (en) | 2009-09-10 | 2016-10-18 | Line-X Llc | Mine seal |
JP5875584B2 (ja) | 2010-07-22 | 2016-03-02 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 封止剤用途のための組合せ添加剤 |
TW201520253A (zh) | 2013-11-21 | 2015-06-01 | Double Bond Chemical Ind Co | 穩定劑以及包括該穩定劑的組成物 |
JP2015137310A (ja) * | 2014-01-22 | 2015-07-30 | 株式会社オートネットワーク技術研究所 | ポリウレタン組成物およびこれを用いた絶縁電線 |
JP2017513993A (ja) * | 2014-04-24 | 2017-06-01 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトCovestro Deutschland Ag | ポリエーテルカーボネートポリオール系ポリウレタンフォーム |
TWI662083B (zh) * | 2015-07-28 | 2019-06-11 | 日商橫浜橡膠股份有限公司 | Rubber composition, rubber composition metal laminate, and vulcanized rubber product |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
US11822117B2 (en) * | 2019-10-08 | 2023-11-21 | Corning Incorporated | Primary coating compositions with improved microbending performance |
EP4015551A1 (de) * | 2020-12-18 | 2022-06-22 | Covestro Deutschland AG | Thermoplastische formmasse mit guten mechanischen eigenschaften |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101815751B (zh) * | 2007-08-01 | 2013-08-14 | 连锁添加剂有限两合公司 | 用作阻燃剂的含磷三嗪化合物 |
CN104497253A (zh) * | 2014-12-14 | 2015-04-08 | 天津利安隆新材料股份有限公司 | 一种多元醇组合物 |
CN104497253B (zh) * | 2014-12-14 | 2017-08-11 | 天津利安隆新材料股份有限公司 | 一种多元醇组合物 |
CN108997557A (zh) * | 2018-09-11 | 2018-12-14 | 界首永恩机电科技有限公司 | 一种环保tpu的制备方法 |
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CA2598498A1 (en) | 2006-09-08 |
ATE471961T1 (de) | 2010-07-15 |
EP1853660A1 (en) | 2007-11-14 |
TW200641017A (en) | 2006-12-01 |
AR055036A1 (es) | 2007-08-01 |
JP2008531801A (ja) | 2008-08-14 |
US20090137699A1 (en) | 2009-05-28 |
WO2006092363A1 (en) | 2006-09-08 |
US20080161454A1 (en) | 2008-07-03 |
KR20070107071A (ko) | 2007-11-06 |
EP1853660B1 (en) | 2010-06-23 |
BRPI0607564A2 (pt) | 2009-09-15 |
US20100204370A1 (en) | 2010-08-12 |
DE602006015037D1 (de) | 2010-08-05 |
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