CN102027056A - 用于乳液聚合的橡胶的基本稳定体系 - Google Patents
用于乳液聚合的橡胶的基本稳定体系 Download PDFInfo
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- CN102027056A CN102027056A CN2009801174578A CN200980117457A CN102027056A CN 102027056 A CN102027056 A CN 102027056A CN 2009801174578 A CN2009801174578 A CN 2009801174578A CN 200980117457 A CN200980117457 A CN 200980117457A CN 102027056 A CN102027056 A CN 102027056A
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- Prior art keywords
- butyl
- component
- composition
- alkyl
- phenyl
- Prior art date
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- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
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- 229910052736 halogen Inorganic materials 0.000 claims description 8
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 abstract description 13
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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 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
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- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 6
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- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 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 5
- 229920000642 polymer Polymers 0.000 description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 4
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- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
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- 229910052759 nickel Inorganic materials 0.000 description 4
- RZJRJXONCZWCBN-NJFSPNSNSA-N octadecane Chemical class CCCCCCCCCCCCCCCCC[14CH3] RZJRJXONCZWCBN-NJFSPNSNSA-N 0.000 description 4
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- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明涉及一种组合物，其含有：a)经受氧化降解、热降解、动态降解和/或光诱导降解的乳液生橡胶、合成胶乳或天然橡胶胶乳；b)式I的化合物，其中R1是C8-C12烷基，R2是氢、C1-C12烷基、环己基、1-甲基环己基、苄基、α-甲基苄基、α，α-二甲基苄基或-CH2-S-R1，R3是C1-C12烷基、苄基、α-甲基苄基、α，α-二甲基苄基或-CH2-S-R1，R4是氢或甲基；和c)式II的苯乙烯化二苯基胺。
Description
本发明涉及含有经受氧化降解、热降解、动态降解和/或光诱导降解的乳液生橡胶、合成胶乳或天然橡胶胶乳和作为稳定剂的选自烷基硫代甲基酚类型化合物和苯乙烯化二苯基胺中的混合物的组合物，以及涉及它们作为颜色稳定和不脱色稳定剂用于稳定乳液生橡胶、合成胶乳或天然橡胶胶乳以抵抗氧化降解、热降解、动态降解和/或光诱导降解的用途，还涉及一种稳定乳液生橡胶、合成胶乳或天然橡胶胶的方法，在该方法中引入或施用至少选自烷基硫代甲基酚类型化合物和苯乙烯化二苯基胺中的混合物。
生橡胶，与所有聚合物一样，易于发生氧化降解、热降解、动态降解和/或光诱导降解。对于各种级别的生橡胶，例如粘合剂类型的，相应的食品接触标准是强制性的。烷基硫代甲基酚类型化合物例如Irganox 1520(RTM，Ciba Inc.)符合这些要求，但是在例如含卤素的凝结体系中存在技术缺陷。
US 6,383,992公开了可生物降解的植物油组合物，其含有苯乙烯化的二苯基胺，例如能与食品接触的Wingstay 29(RTM，Goodyear)。
现在发现选自烷基硫代甲基酚类型化合物和苯乙烯化二苯基胺中的混合物尤其适合作为稳定剂用于对氧化降解、热降解、动态降解和/或光诱导降解敏感的乳液生橡胶、合成胶乳或天然橡胶胶乳。
本发明因此涉及含有以下组分的组合物：
a)经过氧化降解、热降解、动态降解和/或光诱导降解的乳液生橡胶、合成胶乳或天然橡胶胶乳，和
b)式I的化合物：
其中
R1是C8-C12烷基，
R2是氢、C1-C12烷基、环己基、1-甲基环己基、苄基、α-甲基苄基、α，α-二甲基苄基或-CH2-S-R1，
R3是C1-C12烷基、苄基、α-甲基苄基、α，α-二甲基苄基或-CH2-S-R1，
R4是氢或甲基，和
c)式II的苯乙烯化二苯基胺
乳液橡胶是通过乳液聚合制备的。乳液聚合在水中用氧化还原引发剂在低温(冷橡胶)或较高温度(热橡胶)下用有机过氧化物或过硫酸盐引发，产生可以原样使用的胶乳，或加工得到固体橡胶。乳液SBR的分子量是在约250,000-800,000g/mol的范围内；冷橡胶和热橡胶的区别在于支化度。橡胶原样销售或与油共混或用碳黑填充，并构成最重要的合成橡胶。
天然橡胶和许多类型的合成橡胶可以商购。聚合物胶乳是橡胶或塑性材料在含水体系中的胶态分散体。聚合物材料可以是小型烯属(烯烃)单体或二烯单体的聚合物，或两种或多种这些单体的共聚物。这些胶乳的机械稳定性主要取决于表面活性物质在聚合物粒子和水相之间的界面上的存在。
大多数合成胶乳包含苯乙烯-丁二烯、苯乙烯-丙烯酸、丙烯酸酯、乙酸乙烯酯-丙烯酸酯或丁二烯-丙烯腈共聚物。羧基化的胶乳例如羧基化的SBR另外含有例如最多5％的含有羧基或相应羧酸酯的单体单元。有利的是用做有机酸的不饱和单羧酸和二羧酸，例如丙烯酸、甲基丙烯酸和例如亚甲基琥珀酸(衣康酸)。作为羧酸酯，其用做例如乙酸乙烯酯的共聚单体，主要使用富马酸二乙酯、马来酸二乙酯、丙烯酸甲酯、丙烯酸正丁酯或丙烯酸2-乙基己基酯。
使用的有机酸在一定程度上决定了在约60-100℃的反应温度下获得的羧基化SBR的性能。可以提到例如水溶性或最终的加工性能，这基本上受在胶乳表面上的羧基数目的影响。各组分的典型混合物和它们的性能例如参见Polymer Latices and their Application(Applied Science Publishers Ltd.，London 1982；Editor K.O.Calvrt)，第29-31页。这些X-SBR的主要应用是在造纸工业、粘合剂工业以及在纺织工业中，并且在后一种情况下，尤其用于地毯工业中。在造纸工业中，羧基化胶乳例如用于纸用表面涂料；在粘合剂工业中例如用于分散粘合剂，在染料工业中它们用于例如分散染料。
从胶乳生产的制品必须通过抗氧化剂的作用对热和氧稳定。
感兴趣的是这样的组合物，其中R1是C8烷基或C12烷基，
尤其感兴趣的是这样的组合物，其中：
R2是C1-C8烷基、苄基或α-甲基苄基，
R3是C1-C9烷基或-CH2-S-R1，和
R4是氢或甲基。
特别感兴趣的是这样的组合物，其中：
R2是C1-C4烷基或苄基，
R3是C1-C4烷基或-CH2-S-R2，和
R4是氢或甲基。
优选这样的组合物，其中：
R1是C8烷基或C12烷基，
R2是甲基，
R3是-CH2-S-R2，且R2是C8烷基或C12烷基，和
R4是氢。
式I和II的组分(b)和(c)的组合显示出对要稳定的基质有协同作用，也就是说对由其生产的乳液生橡胶、合成胶乳或天然橡胶胶乳而言。
具有最多20个碳原子的烷基表示支化或未支化的烷基，例如甲基、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、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、十八烷基或二十烷基。
在本发明组合物中的式I化合物是文献中已知的，它们的制备方法例如参见US4,857,572。
式II的苯乙烯化二苯基胺是在文献中已知的，例如参见US6,383,992，可以作为Wingstay 29(RTM)(Goodyear)获得。
式I化合物与式II化合物组合使用特别适用于稳定乳液生橡胶、合成胶乳或天然橡胶胶乳，尤其也适用于浅色乳液生橡胶、浅色合成胶乳或浅色天然橡胶胶乳抵抗氧化降解、热降解、动态降解和/或光诱导降解。
根据常规方法之一从乳液生橡胶生产的弹性体(硫化，例如用硫或过氧化物)理解为表示大分子材料，其在室温下在低应力下显著形变之后能快速恢复到基本上其原始形状。也可以参见Hans-Georg Elias，聚合物科学简介(An Introduction to Polymer Science)，第12章，弹性体(Elastomers)，第388-393页，1997，VCH Verlagsgesellschaft mbH，Weinheim，德国；或Ullmanns Encyclopedia of Industrial Chemistry，第5版，完全修订版，第A23卷，第221-440页(1993)。
本发明的组合物可以含有乳液生橡胶，例如以下材料：
1.二烯烃的聚合物，例如聚丁二烯或聚异戊二烯。
2.单烯烃和二烯烃彼此之间或与其它乙烯基单体之间的共聚物，例如丙烯-异丁烯共聚物、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-乙酸乙烯酯共聚物、丙烯腈-丁二烯共聚物，以及乙烯与丙烯和二烯的三元共聚物，二烯是例如己二烯、二聚环戊二烯或亚乙基降冰片烯。
3.苯乙烯或α-甲基苯乙烯与二烯或与丙烯酸类衍生物的共聚物，例如苯乙烯-丁二烯、苯乙烯-丁二烯-丙烯酸烷基酯和甲基丙烯酸烷基酯；以及苯乙烯的嵌段共聚物，例如苯乙烯-丁二烯-苯乙烯或苯乙烯-异戊二烯-苯乙烯共聚物。
4.含卤素的聚合物，例如聚氯丁二烯、氯化橡胶、异丁烯-异戊二烯的氯化和溴化共聚物(卤代丁基橡胶)。
5.天然橡胶。
6.天然或合成橡胶的水乳液，例如天然橡胶胶乳或羧基化苯乙烯-丁二烯共聚物的胶乳。
要保护的乳液生橡胶优选聚二烯乳液生橡胶或含卤素的聚二烯乳液生橡胶，尤其是苯乙烯-丁二烯共聚物乳液生橡胶。
本发明的组合物可以含有胶乳，例如以下材料：
1.单烯烃和二烯烃与其它乙烯基单体形成的共聚物，例如乙烯-丙烯酸烷基酯共聚物、乙烯-甲基丙烯酸烷基酯共聚物、乙烯-乙酸乙烯酯共聚物以及丙烯腈-丁二烯共聚物。
2.苯乙烯或α-甲基苯乙烯与二烯或与丙烯酸型衍生物的共聚物，例如苯乙烯-丁二烯、苯乙烯-丁二烯-丙烯酸烷基酯和甲基丙烯酸烷基酯共聚物。
3.天然橡胶。
4.天然或合成橡胶的水乳液，例如天然橡胶胶乳、苯乙烯-丁二烯胶乳或羧基化苯乙烯-丁二烯共聚物的胶乳。
要保护的胶乳优选是羧基化苯乙烯-丁二烯共聚物、苯乙烯-丙烯酸、乙酸乙烯酯-丙烯酸酯或羧基化丁二烯-丙烯腈共聚物。特别感兴趣的是羧基化苯乙烯-丁二烯胶乳(X-SBR)。
感兴趣的是乳液生橡胶，其已经用含卤素的体系凝结。含卤素的凝结体系含有卤素的碱金属盐和碱土金属盐，例如氯化钠和氯化钙。
非常感兴趣的是乳液苯乙烯-丁二烯橡胶(ESBR)或腈丁二烯橡胶(NBR)。
将式I的组分(b)加入要稳定的乳液生橡胶、合成胶乳或天然橡胶胶乳中，添加量有利地是0.01-10％，例如0.02-5％，优选0.05-1.0％，基于要稳定的乳液生橡胶、合成胶乳或天然橡胶胶乳的干固含量计。
将式II的组分(c)与式I的组分(b)一起加入要稳定的乳液生橡胶、合成胶乳或天然橡胶胶乳中，添加量有利地是0.01-10％，例如0.02-5％，优选0.05-1.0％，基于要稳定的乳液生橡胶、合成胶乳或天然橡胶胶乳的干固含量计。
除了组分(a)、(b)和(c)之外，本发明的组合物可以含有其它添加剂，例如以下添加剂：
1.抗氧化剂
1.1.烷基化的单酚，例如2，6-二叔丁基-4-甲基苯酚、2-丁基-4，6-二甲基苯酚、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；直链或侧链支化的壬基苯酚，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.氢醌和烷基化氢醌，例如：2，6-二叔丁基-4-甲氧基苯酚、2，5-二叔丁基氢醌、2，5-二叔戊基氢醌、2，6-二苯基-4-十八烷氧基苯酚、2，6-二叔丁基氢醌、2，5-二叔丁基-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-羟基苯基硬脂酸酯和双(3，5-二叔丁基-4-羟基苯基)己二酸酯。
1.3.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)。
1.4.羟基化硫代二苯基醚，例如：2，2’-硫代双(6-叔丁基-4-甲基苯酚)、2，2’-硫代双(4-辛基苯酚)、4，4’-硫代双(6-叔丁基-3-甲基苯酚)、4，4’-硫代双(6-叔丁基-2-甲基苯酚)、4，4’-硫代双(3，6-二仲戊基苯酚)和4，4’-双(2，6-二甲基-4-羟基苯基)二硫化物。
1.5.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(4，6-二叔丁基苯酚)、2，2’-亚乙基双(4，6-二叔丁基苯酚)、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-二甲基苄基)-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’-羟基苯基)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-羟基苯基)丁烷、2，2-双(3，5-二叔丁基-4-羟基苯基)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。
1.6.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、4-羟基-3，5-二甲基苄基巯基乙酸十八烷酯、4-羟基-3，5-二叔丁基苄基巯基乙酸十三烷酯、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、二(3，5-二叔丁基-4-羟基苄基)硫化物、3，5-二叔丁基-4-羟基苄基巯基乙酸异辛酯。
1.7.羟基苄基化丙二酸酯，例如：2，2-二(3，5-二叔丁基-2-羟基苄基)丙二酸双十八烷酯、2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸双十八烷酯、巯基乙基-2，2-二(3，5-二叔丁基-4-羟基苄基)丙二酸双十二烷酯和2，2-二(3，5-二叔丁基-4-羟基苄基)丙二酸双[4-(1，1，3，3-四甲基丁基)苯基]酯。
1.8.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)-2，4，6-三甲基苯、1，4-二(3，5-二叔丁基-4-羟基苄基)-2，3，5，6-四甲基苯和2，4，6-三(3，5-二叔丁基-4-羟基苄基)苯酚。
1.9.三嗪化合物，例如2，4-二(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-4，6-二(3，5-二叔丁基-4-羟基苯胺基)-1，3，5-三嗪、2-辛基巯基-4，6-二(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-羟基苯基乙基)-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。
1.10.苄基膦酸酯，例如2，5-二叔丁基-4-羟基苄基膦酸二甲酯、3，5-二叔丁基-4-羟基苄基膦酸二乙酯、3，5-二叔丁基-4-羟基苄基膦酸双十八烷酯、5-叔丁基-4-羟基-3-甲基苄基膦酸双十八烷酯、3，5-二叔丁基-4-羟基苄基膦酸单乙酯的钙盐。
1.11.酰基氨基酚，例如：4-羟基金酸苯胺、4-羟基硬脂酸酰苯胺、N-(3，5-二叔丁基-4-羟基苯基)氨基甲酸辛酯。
1.12.β-(3，5-二叔丁基-4-羟基苯基)丙酸与单羟基或多羟基醇形成的酯，例如与甲醇、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(羟基乙基)异氰脲酸酯、N，N’-二(羟基乙基)草酸二酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷和4-羟基甲基-1-磷杂-2，6，7-三氧杂双环[2.2.2]辛烷形成的酯。
1.13.β-(3，5-二环己基-4-羟基苯基)丙酸与单羟基或多羟基醇形成的酯，例如与甲醇、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(羟基乙基)异氰脲酸酯、N，N’-二(羟基乙基)草酸二酰胺、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-羟基甲基-1-磷杂-2，6，7-三氧杂双环[2.2.2]辛烷形成的酯。
1.14.3，5-二叔丁基-4-羟基苯基乙酸与单羟基或多羟基醇形成的酯，例如与甲醇、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(羟基乙基)异氰脲酸酯、N，N’-二(羟基乙基)草酸二酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷和4-羟基甲基-1-磷杂-2，6，7-三氧杂双环[2.2.2]辛烷形成的酯。
1.15.β-(3，5-二叔丁基4-羟基苯基)丙酸的酰胺，例如：N，N’-二(3，5-二叔丁基-4-羟基苯基丙酰基)六亚甲基二酰胺、N，N’-二(3，5-二叔丁基-4-羟基苯基丙酰基)三亚甲基二酰胺、N，N’-二(3，5-二叔丁基-4-羟基苯基丙酰基)酰肼、N，N’-二[2-(3-[3，5-二叔丁基-4-羟基苯基]丙酰基氧基)乙基]草酰胺(来自Uniroyal的NaugardXL-1)。
1.16.抗坏血酸(维生素C)
1.17.胺类抗氧剂，例如：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’-二(1，4-二甲基戊基)-对-亚苯基二胺、N，N’-二(1-乙基-3-甲基戊基)-对-亚苯基二胺、N，N’-二(1-甲基庚基)-对-亚苯基二胺、N，N’-二环己基-对-亚苯基二胺、N，N’-二苯基-对-亚苯基二胺、N，N’-二(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、辛基化的二苯基胺(例如对，对’-二叔辛基二苯基胺)、4-正丁基氨基苯酚、4-丁酰基氨基苯酚、4-壬酰基氨基苯酚、4-十二烷酰基氨基苯酚、4-十八烷酰基氨基苯酚、二(4-甲氧基苯基)胺、2，6-二叔丁基-4-二甲基氨基甲基苯酚、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、1，2-二[(2-甲基苯基)氨基]乙烷、1，2-二(苯基氨基)丙烷、邻-甲苯基双胍、二[4-(1’，3’-二甲基丁基)苯基]胺、叔辛基化的N-苯基-1-萘基胺、单和双烷基化的叔丁基/叔辛基二苯基胺的混合物、单和双烷基化的壬基二苯基胺的混合物、单和双烷基化的十二烷基二苯基胺的混合物、单和双烷基化的异丙基/异己基二苯基胺的混合物、单和双烷基化的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、单和双烷基化的叔丁基/叔辛基吩噻嗪的混合物、单和双烷基化的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
2.12-(2′-羟基苯基)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′-羟基苯基)苯并三唑，2-(5′-叔丁基-2′-羟基苯基)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′-羟基苯基)-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′-羟基-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′-羟基苯基)苯并三唑，2-(3′，5′-二(α，α-二甲基苄基)-2′-羟基苯基)苯并三唑，2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)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)-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′-羟基苯基)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-异辛氧基羰基乙基)苯基-苯并三唑，2，2′-亚甲基-二[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′-羟基苯基]-苯并三唑与聚乙二醇300的酯交换产物；[R-CH2CH2-COO-CH2CH2-]2-，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-二甲基苄基)-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-二甲基苄基)苯基]-苯并三唑。
2.2.2-羟基二苯酮，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、2′-羟基-4，4′-二甲氧基衍生物。
2.3.未取代或取代的苯甲酸的酯，例如4-叔丁基苯基水杨酸酯，水杨酸苯基酯，辛基苯基水杨酸酯，二苯甲酰基间苯二酚，二(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，例如α-氰基-β，β-二苯基丙烯酸乙基酯或异辛基酯，α-甲氧基羰基肉桂酸甲基酯，α-氰基-β-甲基-p-甲氧基肉桂酸甲基酯或丁基酯，α-甲氧基羰基-p-甲氧基肉桂酸甲基酯，N-(β-甲氧基羰基-β-氰基乙烯基)-2-甲基吲哚。
2.5.镍化合物，例如：2，2’-硫代二[4-(1，1，3，3-四甲基丁基)苯酚]的镍络合物，如1∶1或1∶2络合物，任选地使用其它配体，如正丁胺、三乙醇胺或N-环己基二乙醇胺，二硫代氨基甲酸二丁酯镍、4-羟基-3，5-二叔丁基苄基膦酸单烷基酯(例如甲酯或乙酯)的镍盐、酮肟(例如2-羟基-4-甲基苯基十一烷基酮肟)的镍络合物、和1-苯基-4-十二烷酰基-5-羟基吡唑的镍络合物，任选地使用其它配体。
2.6.位阻胺，例如：癸二酸二(2，2，6，6-四甲基-4-哌啶基)酯、琥珀酸二(2，2，6，6-四甲基-4-哌啶基)酯、癸二酸二(1，2，2，6，6-五甲基-4-哌啶基)酯、癸二酸二(1-辛氧基-2，2，6，6-四甲基-4-哌啶基)酯、正丁基-3，5-二叔丁基-4-羟基苄基丙二酸二(1，2，2，6，6-五甲基-4-哌啶基)酯、1-羟基乙基-2，2，6，6-四甲基-4-羟基哌啶与琥珀酸的缩合产物，N，N’-二(2，2，6，6-四甲基-4-哌啶基)六亚甲基二胺与4-叔辛基氨基-2，6-二氯-1，3，5-三嗪的线性或环状缩合产物，次氮基三乙酸三(2，2，6，6-四甲基-4-哌啶基)酯、1，2，3，4-丁烷四羧酸四(2，2，6，6-四甲基-4-哌啶基)酯、1，1’-(1，2-乙烷二基)二(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-硬脂酰基-2，2，6，6-四甲基哌啶、2-正丁基-2-(2-羟基-3，5-二叔丁基苄基)丙二酸二(1，2，2，6，6-五甲基哌啶基)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、癸二酸二(1-辛氧基-2，2，6，6-四甲基哌啶基)酯、琥珀酸二(1-辛氧基-2，2，6，6-四甲基哌啶基)酯，N，N’-二(2，2，6，6-四甲基-4-哌啶基)六亚甲基二胺与4-吗啉基-2，6-二氯-1，3，5-三嗪的线性或环状缩合产物，2-氯-4，6-二(4-正丁基氨基-2，2，6，6-四甲基哌啶基)-1，3，5-三嗪与1，2-二(3-氨基丙基氨基)乙烷的缩合产物，2-氯-4，6-二(4-正丁基氨基-1，2，2，6，6-五甲基哌啶基)-1，3，5-三嗪与1，2-二(3-氨基丙基氨基)乙烷的缩合产物，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-硬脂酰氧基-2，2，6，6-四甲基哌啶的混合物，N，N’-二(2，2，6，6-四甲基-4-哌啶基)六亚甲基二胺与4-环己基氨基-2，6-二氯-1，3，5-三嗪的缩合产物，1，2-二(3-氨基丙基氨基)乙烷与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产物(CAS登记序号[136504-96-6])；1，6-二氨基己烷与2，4，6-三氯-1，3，5-三嗪以及N，N-二丁基胺与4-丁基氨基-2，2，6，6-四甲基哌啶的缩合物(CAS登记序号[192268-64-7])；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-环十一烷基-1-氧杂-3，8-二氮杂-4-氧螺[4.5]癸烷和表氯醇的反应产物、1，1-二(1，2，2，6，6-五甲基-4-哌啶氧基羰基)-2-(4-甲氧基苯基)乙烯、N，N’-二甲酰基-N，N’-二(2，2，6，6-四甲基-4-哌啶基)六亚甲基二胺，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-4-(2，2，6，6-四甲基-4-哌啶基)]硅氧烷，马来酸酐/α-烯烃共聚物和2，2，6，6-四甲基-4-氨基哌啶或1，2，2，6，6-五甲基-4-氨基哌啶的反应产物。
2.7.草酸二酰胺，例如4，4′-二辛氧基-N，N’-草酰二苯胺，2，2′-二乙氧基-N，N’-草酰二苯胺，2，2′-二辛氧基-5，5′-二叔丁基-N，N’-草酰二苯胺，2，2′-双十二烷氧基-5，5′-二叔丁基-N，N’-草酰二苯胺，2-乙氧基-2′-乙基-N，N’-草酰二苯胺，N，N′-二(3-二甲基氨基丙基)-N，N’-草酰二苯胺，2-乙氧基-5-叔丁基-2′-乙基-N，N’-草酰二苯胺以及它们与2-乙氧基-2′-乙基-5，4′-二叔丁基-N，N’-草酰二苯胺的混合物，o-和p-甲氧基-以及o-和p-乙氧基-二取代的-N，N’-草酰二苯胺的混合物。
2.8.2-(2-羟基苯基)-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)-4，6-二(2，4-二甲基苯基)-1，3，5-三嗪，2-(2，4-二羟基苯基)-4，6-二(2，4-二甲基苯基)-1，3，5-三嗪，2，4-二(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)-4，6-二(4-甲基苯基)-1，3，5-三嗪，2-(2-羟基-4-十二烷氧基苯基)-4，6-二(2，4-二甲基-苯基)-1，3，5-三嗪，2-(2-羟基-4-十三烷氧基苯基)-4，6-二(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]-4，6-二(2，4-二甲基苯基)-1，3，5-三嗪，2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4，6-二(2，4-二甲基-苯基)-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]-4，6-二(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]-4，6-二(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-羟基苯基)-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}-4，6-二(2，4-二甲基苯基)-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’-二(水杨酰)肼、N，N’-二(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、二(亚苄基)草酰二酰肼、N，N’-草酰二苯胺、间苯二甲酰二酰肼、癸二酰二苯基酰肼、N，N’-二乙酰基己二酸二酰肼、N，N’-二(水杨酰)草酸二酰肼、N，N’-二(水杨酰)硫代丙酸二酰肼。
4.亚磷酸酯和亚膦酸酯，例如：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、亚磷酸三月桂基酯、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、二亚磷酸二(2，4-二叔丁基苯基)季戊四醇酯、二亚磷酸二(2，4-二枯基苯基)季戊四醇酯、二亚磷酸二(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、二亚磷酸二(2，4-二叔丁基-6-甲基苯基)季戊四醇酯、二亚磷酸二(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、4，4’-二亚苯基二亚膦酸四(2，4-二叔丁基苯基)酯、6-异辛氧基-2，4，8，10-四叔丁基-12H-二苯并[d，g][1，3，2]二氧杂亚膦酸酯(phosphocin)、二(2，4-二叔丁基-6-甲基苯基)甲基亚磷酸酯、二(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-二苯并[d，g][1，3，2]二氧杂亚膦酸酯、2，2’，2”-次氮基[三乙基三(3，3’，5，5’-四叔丁基-1，1’-二苯基-2，2’-二基)亚磷酸酯]、亚磷酸2-乙基己基(3，3’，5，5’-四叔丁基-1，1’-二苯基-2，2’-二基)酯、5-丁基-5-乙基-2-(2，4，6-三叔丁基苯氧基)-1，3，2-二氧杂磷烷。
5.羟基胺，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-二月桂基羟基胺、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、衍生自氢化牛油胺的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、从衍生自氢化牛油胺的N，N-二烷基羟基胺制备的硝酮。
7.硫代协同化合物，例如硫代二丙酸二月桂基酯、硫代二丙酸二硬脂基酯或式I’的化合物：
其中
R1是氢、C1-C12烷基、环己基、苯基或苄基，
R2是氢或C1-C4烷基，和
n是0、1或2。
8.过氧化物清除剂，例如：β-硫代二丙酸的酯，例如月桂基、硬脂基、十四烷基或十三烷基酯，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，双十八烷基二硫化物，四(β-十二烷基巯基)丙酸季戊四醇酯。
9.碱性助稳定剂，例如：三聚氰胺、聚乙烯基吡咯烷酮、二氰基二酰胺、氰脲酸三烯丙基酯、脲衍生物、肼衍生物、胺、聚酰胺、聚氨酯、高级脂肪酸的碱金属和碱土金属盐，例如硬脂酸钙、硬脂酸锌、山嵛酸镁、硬脂酸镁、蓖麻醇酸钠、棕榈酸钾，邻苯二酚锑或邻苯二酚锌。
10.成核剂，例如无机物质，例如滑石，金属氧化物，例如二氧化钛或氧化镁，优选碱土金属的磷酸盐、碳酸盐或硫酸盐；有机化合物，例如单羧酸或多羧酸以及它们的盐，例如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，例如离子共聚物(离聚物)。尤其优选的是1，3：2，4-二(3’，4’-二甲基亚苄基)山梨醇，1，3：2，4-二(五甲基二亚苄基)山梨醇，和1，3：2，4-二(亚苄基)山梨醇。
11.填料和增强剂，例如碳酸钙，硅酸盐，玻璃纤维，玻璃珠，滑石，高岭土，云母，硫酸钡，金属氧化物和氢氧化物，碳黑，石墨，木粉，以及其它天然产物的粉末或纤维，合成纤维。
12.其它添加剂，例如增塑剂、润滑剂、乳化剂、颜料、流变添加剂、催化剂、流动控制剂、荧光增白剂、阻燃剂、抗静电剂和发泡剂。
13.苯并呋喃酮和吲哚满酮(内酯)，例如：US4,325,863、US4,338,244、US5,175,312、US5,216,052、US 5,252,643、DE-A-4316611、DE-A-4316622、DE-A-4316876、EP-A-0589839、EP-A-0591102、EP-A-1291384中所描述的那些，或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’-二[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-甲氧基苯基)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、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-乙酰基-5-异辛基苯基)-5-异辛基苯并呋喃-2-酮。
尤其优选的苯并呋喃-2-酮(内酯)是例如5，7-二叔丁基-3-苯基-苯并呋喃-2-酮、5，7-二叔丁基-3-(3，4-二甲基苯基)苯并呋喃-2-酮；5，7-二叔丁基-3-(2，3-二甲基苯基)苯并呋喃-2-酮，5，7-二叔丁基-3-(4-甲氧基苯基)苯并呋喃-2-酮、5-叔辛基-3-(2-乙酰基-5-叔辛基苯基)-苯并呋喃-2-酮，或式B-1或B-2的化合物，或它们的混合物。
苯并呋喃-2-酮稳定剂(内酯)是文献中已知的，例如公开在US5,516,920中。
根据本发明优选的组合物另外含有作为其它添加剂的选自以下的一种或多种组分：颜料，染料，填料，流动助剂，分散剂，增塑剂，硫化活化剂，硫化促进剂，硫化剂，电荷控制剂，粘合促进剂，光稳定剂或抗氧化剂，例如酚类抗氧化剂(上述列表中的1.1至1.15)或胺抗氧化剂(上述列表中的1.17)，有机亚磷酸酯或亚膦酸酯(上述列表中的4)，内酯和/或硫代协同化合物(上述列表中的7)。
额外添加剂的使用浓度是例如0.01-10％，基于要稳定的乳液生橡胶、合成胶乳或天然橡胶胶乳的干固含量计。
组分(b)和(c)以及任选其它添加剂向乳液生橡胶、合成胶乳或天然橡胶胶乳中的引入操作是按照公知方法进行的，优选在聚合之后或在制备所述混合物期间或在成型之前或期间，任选地随后通过蒸发除去溶剂。组分(b)和(c)以及任选其它添加剂也可以以含这些组分的母炼胶的形式加入要稳定的乳液生橡胶中，例如浓度各自为2.5-25重量％。
组分(b)和(c)以及任选其它添加剂尤其优选在合成乳液生橡胶的聚合之前或期间加入，或在向橡胶胶乳的聚合已经停止之后。
组分(b)和(c)以及任选其它添加剂可以在胶乳的聚合之前或期间或者交联之前加入。
组分(b)和(c)以及任选其它添加剂可以以纯形式或包封在蜡、油或聚合物中的形式引入要稳定的乳液生橡胶、合成胶乳或天然橡胶胶乳。
所得的稳定化的乳液生橡胶可以进一步以广泛的形式使用，例如是条、模塑材料、型材、输送带或轮胎的形式使用，这通过将它们按照常规方法之一与常规的配料成分混合并硫化它们来进行(例如与硫或过氧化物)。
所得的稳定化的胶乳可以进一步以广泛的形式使用，例如是膜、条、模塑材料的形式，用于造纸工业中，例如在纸涂料中；在粘合剂工业中，例如在分散粘合剂中；在染料工业中用于分散染料以及在纺织工业中，和在后一种情况下，尤其在地毯领域中，通过将胶乳与常规配料成分按照常规方法之一混合，将它们例如施用到地毯的反面，并干燥它们。
本发明还涉及一种使经受氧化降解、热降解、动态降解和/或光诱导降解的乳液生橡胶、合成胶乳或天然橡胶胶乳稳定化的方法，在此方法中至少组分(b)和组分(c)与所述材料混合或施用到其上。
本发明的另一个实施方案是组分(b)和组分(c)用于使经受氧化降解、热降解、动态降解和/或光诱导降解的乳液生橡胶、合成胶乳或天然橡胶胶乳稳定化的用途。
对于上述用途和方法而言优选的组分(b)和组分(c)是与用于含有乳液生橡胶、合成胶乳或天然橡胶胶乳的组合物所述相同的那些。
以下实施例进一步说明本发明。百分比涉及重量，除非另有说明。
实施例1：乳液生橡胶的稳定化
商购的热NBR胶乳已经用于检测。将添加剂体系以乳液的形式引入胶乳中。胶乳然后使用以下工序凝结：
1400g的含有NBR胶乳的稳定剂已经在搅拌下缓慢地加入2800g的凝结乳清中，这由2786g的软化水和14g的氯化钙组成。凝结温度是50℃。在凝结后收集的橡胶团块在软化的中性水中在65℃下洗涤。湿团块通过经过橡胶覆盖的辊机而脱水，然后在50℃下在真空烘箱中过夜干燥。将湿橡胶压塑成10mm片材，并将这些片材在烘箱中于80℃老化。用0(无色)到10(深棕色)的颜色标准每周一次目测颜色。结果列在表1中。
表1：
a)Irganox 1520(RTM)(Ciba Inc.)是4，6-二(辛基硫代甲基)-邻甲酚。
b)Wingstay 29(RTM)(Goodyear)是式II的苯乙烯化二苯基胺。
Claims (15)
1.一种组合物，其含有：
a)经受氧化降解、热降解、动态降解和/或光诱导降解的乳液生橡胶、合成胶乳或天然橡胶胶乳，和
b)式I的化合物：
其中
R1是C8-C12烷基，
R2是氢、C1-C12烷基、环己基、1-甲基环己基、苄基、α-甲基苄基、α，α-二甲基苄基或-CH2-S-R1，
R3是C1-C12烷基、苄基、α-甲基苄基、α，α-二甲基苄基或-CH2-S-R1，
R4是氢或甲基，和
c)式II的苯乙烯化二苯基胺
2.权利要求1的组合物，其中R1是C8烷基或C12烷基。
3.权利要求1或2的组合物，其中
R1是C8烷基或C12烷基，
R2是甲基，
R3是-CH2-S-R1，且R1是C8烷基或C12烷基，和
R4是氢。
4.权利要求1-3的组合物，其含有0.01-10重量％的式I的组分(b)，基于组分(a)的干固含量的重量计。
5.权利要求1-4的组合物，其含有0.01-10重量％的式II的组分(c)，基于组分(a)的干固含量的重量计。
6.权利要求1-5的组合物，其中组分(a)是浅色乳液生橡胶、浅色合成胶乳或浅色天然橡胶胶乳。
7.权利要求1-6的组合物，其中组分(a)是聚二烯乳液生橡胶、含卤素的聚二烯乳液生橡胶或苯乙烯-丁二烯共聚物乳液生橡胶。
8.权利要求1-6的组合物，其中组分(a)是羧基化苯乙烯-丁二烯、苯乙烯-丙烯酸、乙酸乙烯酯-丙烯酸酯或羧基化丁二烯-丙烯腈。
9.权利要求1-6的组合物，其中组分(a)是乳液生橡胶，其已经用含卤素的体系凝结。
10.权利要求1-7或9的组合物，其中组分(a)是乳液苯乙烯-丁二烯橡胶(ESBR)或腈丁二烯橡胶(NBR)。
11.权利要求1-10的组合物，其中除了组分(a)、(b)和(c)之外还含有其它添加剂。
12.权利要求1-11的组合物，其中另外含有作为其它添加剂的选自以下的一种或多种组分：颜料，染料，填料，流动助剂，分散剂，增塑剂，电荷控制剂，粘合促进剂，其它抗氧化剂和/或光稳定剂。
13.权利要求1-12的组合物，其中另外含有作为其它添加剂的酚类抗氧化剂、胺类抗氧化剂、有机亚磷酸酯或亚膦酸酯、内酯和/或硫代协同化合物。
14.一种使经受氧化降解、热降解、动态降解和/或光诱导降解的乳液生橡胶、合成胶乳或天然橡胶胶乳稳定化的方法，在此方法中将根据权利要求1的至少组分(b)和组分(c)与所述材料混合或施用到其上。
15.根据权利要求1的组分(b)和组分(c)的混合物用于使经受氧化降解、热降解、动态降解和/或光诱导降解的乳液生橡胶、合成胶乳或天然橡胶胶乳稳定化的用途。
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| PCT/EP2009/055460 WO2009138342A1 (en) | 2008-05-15 | 2009-05-06 | Basic stabilisation systems for emulsion polymerised rubbers |
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| CN111253621A (zh) * | 2020-03-06 | 2020-06-09 | 天津利安隆新材料股份有限公司 | 一种用于生橡胶的液体抗氧化剂组合物 |
| CN114929792A (zh) * | 2019-05-24 | 2022-08-19 | 瑞士新集团有限公司 | 用于乳液聚合橡胶的抗氧化剂共混物 |
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| CN102027056B (zh) * | 2008-05-15 | 2013-09-18 | 巴斯夫欧洲公司 | 用于乳液聚合的橡胶的基本稳定体系 |
| JP5485528B2 (ja) * | 2008-09-29 | 2014-05-07 | 日本ゼオン株式会社 | 共役ジエンゴム組成物 |
| JP5561410B2 (ja) * | 2013-06-25 | 2014-07-30 | 日本ゼオン株式会社 | 共役ジエンゴム組成物 |
| BR112016017570B1 (pt) * | 2014-02-03 | 2021-06-08 | Arlanxeo Deutschland Gmbh | borracha estabilizada, processo para preparar as borrachas estabilizadas, mistura vulcanizável, processo para a preparação da mistura vulcanizável, processo para preparar vulcanizados da mistura vulcanizável, e, vulcanizado |
| EP4119609B1 (en) | 2014-02-03 | 2024-08-28 | Aquaspersions Ltd. | Antioxidant stabiliser for polymers |
| EP3507331A1 (en) * | 2016-08-30 | 2019-07-10 | Basf Se | A liquid antioxidant composition for raw rubbers |
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- 2009-05-06 EP EP09745675A patent/EP2285887A1/en not_active Withdrawn
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114929792A (zh) * | 2019-05-24 | 2022-08-19 | 瑞士新集团有限公司 | 用于乳液聚合橡胶的抗氧化剂共混物 |
| CN111253621A (zh) * | 2020-03-06 | 2020-06-09 | 天津利安隆新材料股份有限公司 | 一种用于生橡胶的液体抗氧化剂组合物 |
| CN111253621B (zh) * | 2020-03-06 | 2022-05-31 | 天津利安隆新材料股份有限公司 | 一种用于生橡胶的液体抗氧化剂组合物 |
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| US9309379B2 (en) | 2016-04-12 |
| EP2285887A1 (en) | 2011-02-23 |
| JP2011521035A (ja) | 2011-07-21 |
| US20170096544A1 (en) | 2017-04-06 |
| WO2009138342A1 (en) | 2009-11-19 |
| TW200951144A (en) | 2009-12-16 |
| BRPI0912632B1 (pt) | 2019-10-01 |
| TWI480289B (zh) | 2015-04-11 |
| US9562148B2 (en) | 2017-02-07 |
| US20160046789A1 (en) | 2016-02-18 |
| KR101693875B1 (ko) | 2017-01-17 |
| CN102027056B (zh) | 2013-09-18 |
| US20110077333A1 (en) | 2011-03-31 |
| BRPI0912632A2 (pt) | 2016-01-26 |
| KR20110007248A (ko) | 2011-01-21 |
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