CN1221600C - 包含亮氨酸的颜色改善的稳定化组合物 - Google Patents
包含亮氨酸的颜色改善的稳定化组合物 Download PDFInfo
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- CN1221600C CN1221600C CNB028053354A CN02805335A CN1221600C CN 1221600 C CN1221600 C CN 1221600C CN B028053354 A CNB028053354 A CN B028053354A CN 02805335 A CN02805335 A CN 02805335A CN 1221600 C CN1221600 C CN 1221600C
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- butyl
- phenyl
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- dimethyl ethyl
- tert
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种稳定剂组合物，其包含a)至少一种位阻酚，b)至少一种含磷的第二抗氧化剂，和c)至少一种亮氨酸化合物。其中组分(a)∶组分(b)∶组分(c)的重量比为1∶5∶3-2∶0.5∶0.1，用于聚烯烃基热塑性聚合物的稳定化，以对抗由于暴露于热和/或光、特别是在氧气存在下引起的降解，交联和/或变色。
Description
本发明涉及包含亮氨酸的颜色改善的稳定化组合物，其用于聚烯烃基热塑性聚合物的加工。
热塑性组合物在加工成制品的过程中要经受高温和高压，这会对聚合物的分子量和物理性质以及由这些聚合物制造的制成品的外观造成不利影响。因此，需要抗氧化剂和颜色稳定化添加剂来使氧化作用和变色作用最小化。
常见的稳定剂体系由有机亚磷酸酯和有机亚膦酸酯以及位阻酚抗氧化剂和/或任选的胺类化合物组成，其能够防止或延迟变质的过程。
在聚合物内部，降解的过程与各种结构特性变化伴随发生，如由共轭亚乙烯基和羰基组成的共轭官能团的形成。而且，含有位阻酚抗氧化剂的聚合物的变色是受含有醌型结构的这些添加剂的颜色转变产物的影响。[参见：P.P.Klemchuk和P.-L.Horng的Po1ym.Degr.Stab.，7，131(1984)；T.J.Herman的“Development in PolymerStabilization”，第1部，G.Scott编，Appl.Sci.Publ.Ltd.，London，第39页(1979)；J.Scheirs，S.W.Bigger和O.Delatycki的Polymer30，2080(1989)]。其程度取决于酚的结构和使用量。聚烯烃的变色特别受到与水或NOx气体的持续接触的影响。颜色的另一个来源被认为是氧化还原反应和/或来源于与稳定剂或稳定剂过渡产物形成聚合物所用的催化剂的金属残留物的成络合物作用。
尽管将有机亚磷酸酯和/或-亚膦酸酯与位阻酚化合物适当组合能改善变色作用这是个事实，但仍需进一步减轻这一问题以满足技术要求。
本发明的目的是提供一种用来稳定聚烯烃基热塑性聚合物的改进的稳定剂组合物，以使最终产品的颜色稳定性得到改善。
该目的通过下述的稳定剂组合物来实现。令人吃惊地发现向已知的添加剂体系中加入较少量的氨基酸，特别是亮氨酸产生了出人意料的协同效应并导致对聚烯烃基热塑性聚合物产生了有效的稳定化作用，以抵抗由于向热或光暴露，特别在氧气存在下产生的变色作用。本发明的稳定剂组合物包含三类已知添加剂中的至少一种，其性能显著优于本领域内已知的添加剂体系。
因此，本发明提供了一种用于聚烯烃基热塑性聚合物的颜色改善的稳定剂组合物，包含：
a)至少一种位阻酚，
b)至少一种含磷的第二抗氧化剂，和
c)至少一种亮氨酸化合物。
其中组分(a)∶组分(b)∶组分(c)的重量比为1∶5∶3-2∶0.5∶0.1，优选为1∶3∶2-1∶1∶0.2。
如果在本发明的稳定剂组合物中存在一种以上组分(a)，(b)或(c)的化合物，重量比的定义总是指组分(a)，(b)或(c)的总量。
术语“亮氨酸化合物”指具有亮氨酸基本结构的任何化合物。
还公开了不同化学结构的亮氨酸如其异构体异亮氨酸。
环境友好的，GRAS列出的化合物(GRAS＝通常认为是安全的)，特别是亮氨酸，能够以低浓度用作聚烯烃熔体加工中的颜色改善化合物。这一能力意味着各种聚烯烃加工上的一个总体的显著技术改进。
其它氨基酸如蛋氨酸、胱氨酸和半胱氨酸也有利于熔体稳定化工艺，与它们相比，从根本上来讲亮氨酸的熔体稳定化效率要低得多，但其具有显著的颜色改善作用。
本文所使用的术语“位阻酚”指优选衍生自2，6-二叔丁基苯酚，2-叔丁基-6-甲基苯酚，2-叔丁基-5-甲基苯酚或其它受阻酚的那些化合物。
此类化合物的优选实例是：2，2′-双[3，5-[3，5-双(1，1-二甲基乙基)-4-羟苯基]-1-氧代丙氧基]甲基-1，3-丙烷二基-3，5-双(1，1-二甲基乙基)-4-羟基苯丙酸酯；十八烷基-3，5-双(1，1-二甲基乙基)-4-羟基苯丙酸酯；1，3，5-三[[3，5-双(1，1-二甲基乙基)-4-羟苯基]甲基]-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮；4，4′，4″-[2，4，6-三甲基-1，3，5-苯三基]三-(亚甲基)]三[2，6-双(1，1-二甲基乙基)苯酚；乙烷二基-3，5-双(1，1-二甲基乙基)-4-羟基-硫代二-2，1-苯丙酸酯；单乙基-[[3，5-双(1，1-二甲基乙基)-4-羟苯基]甲基]-膦酸酯的2∶1钙盐；2-[3-[3，5-双-(1，1-二甲基乙基)4-羟基-苯基]-1-氧代-丙基]酰肼-3，5-双(1，1-二甲基-乙基)-4-羟基-苯丙酸；2，2′-草酰氨基-双[乙基-3-(3，5-二叔丁基-4-羟苯基)丙酸酯]或它们的混合物。
本文还使用的术语“含磷的第二抗氧化剂”指的是氢过氧化物分解的剂化合物，即能够与氢过氧化物反应产生非自由基产物的化合物，其基本上将氢过氧化物分解为稳定的副产物。此类化合物的例子是亚磷酸的三酯(亚磷酸酯)和亚磷酸的二酯(亚膦酸酯)。
含磷的第二抗氧化剂具体优选的是三苯基亚磷酸酯，三异癸基亚磷酸酯；三(壬基苯基)亚磷酸酯；双十八烷基五赤藓醇二亚磷酸酯；2，4，6-三叔丁基苯基-2-丁基-2-乙基-1，3-丙二醇亚磷酸酯；双(2，4-二-叔丁基苯基)-五赤藓醇二亚磷酸酯；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；二[2，4-二叔丁基-6-甲基-苯基]乙基亚磷酸酯；2，2′-亚乙基-双-(4，6-二叔丁基苯基)-氟代亚磷酸酯；三-(2，4-二叔丁基苯基)亚磷酸酯；4，6-二叔丁基-间甲酚与联苯和三氯化磷的福瑞德克莱福特反应产物的缩合产物；四[2，4-二叔丁基苯基]-4，4′-二亚苯基-二亚膦酸酯；2，4-二叔丁基苯酚与联苯和PCl3的福瑞德-克莱福特反应产物的缩合产物。
适合本发明进行稳定化的聚烯烃基热塑性聚合物举例如下：
1、单烯烃和二烯烃的聚合物，例如聚丙烯，聚异丁烯，聚1-丁烯，聚-4-甲基-1-戊烯，聚异戊二烯或聚丁二烯，以及环烯烃的聚合物，例如环戊烯或降冰片烯；还有聚乙烯(其可任选被交联)；例如，高密度聚乙烯(HDPE)，高密度且高摩尔量的聚乙烯(HDPE-HMW)，高密度和超高摩尔量聚乙烯(HDPE-UHMW)，中密度聚乙烯(HMDPE)，低密度聚乙烯(LDPE)，线型低密度聚乙烯(LLDPE)，支化低密度聚乙烯(BLDPE)。
2、1)中提及的聚合物的混合物，例如聚丙烯与聚异丁烯，聚乙烯与聚异丁烯，聚丙烯与聚乙烯(例如PP/HDPE/LDPE)的混合物以及不同类型的聚乙烯(例如LDPE/HDPE)两两形成的混合物。
3、单烯烃和二烯烃相互之间或与其它乙烯基单体形成的共聚物，例如乙烯-丙烯共聚物，线型低密度聚乙烯(LLDPE)及其与低密度聚乙烯(LDPE)的混合物，丙烯-1-丁烯共聚物，丙烯-异丁烯共聚物，乙烯-1-丁烯共聚物，乙烯-己烯共聚物，乙烯-甲基戊烯共聚物，乙烯-戊烯共聚物，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-醋酸乙烯酯共聚物以及它们与一氧化碳的共聚物或乙烯-丙烯酸共聚物及其盐(离聚物)以及乙烯与丙烯和一种二烯如己二烯，二环戊二烯或亚乙基-降冰片烯形成的三元共聚物；和这些共聚物两两之间和与1)中述及的聚合物形成的混合物，例如聚丙烯-乙烯-丙烯共聚物，LDPE-乙烯-醋酸乙烯酯共聚物，LDPE-乙烯-丙烯酸共聚物，LLDPE-乙烯-醋酸乙烯酯共聚物，LLDPE-乙烯-丙烯酸共聚物和交替的或无规的聚亚烷基-一氧化碳共聚物及它们与其它聚合物例如聚酰胺形成的混合物。
以上所公开的亚磷酸酯、亚膦酸酯以及位阻酚化合物可以通过本领域内所熟知的方法由已知的化合物来合成。它们可商购获得。化合物包括它们的商品名以及化学结构式的选择列在表1中。
本发明的稳定剂组合物可以这样生产：按所需重量比，根据已知的方法，将化合物(a)，(b)和(c)简单地进行物理混合。优选的方法是各组分干混合，得到一种可自由流动的混合物，该混合物可进一步通过预挤出步骤来获得均质和易于处理的粒料。制造稳定剂组合物的方法是本发明的另外一个方面。
包含本发明的稳定剂组合物和与要被稳定化的热塑性聚合物相一致或相容的热塑性材料的母料组合物同样是本发明的一个目的。本发明的母料组合物包含10-80wt％，优选5-25wt％的稳定剂组合物和90wt％-20wt％，优选95-75wt％的上述热塑性材料。
本发明还提供了一种提高聚烯烃基热塑性聚合物的颜色稳定性的方法，包括：以任何适当的加工状态，向其中加入稳定量的稳定剂组合物。这可以按照已知的方法来实施并涉及稳定剂组合物的加入，以原样或以上述母料的形式加入。还有，各个组分可以按正确比率分别加入。
稳定剂组合物的浓度为0.001-5wt％，优选0.01-1wt％，更优选0.1-0.5wt％，基于要被稳定化的聚烯烃基热塑性材料的重量计。
本发明还包含稳定化的聚烯烃基热塑性聚合物和由其制造的任何制品，通过加入稳定化量的本发明的稳定剂组合物而将其稳定化。
所述聚合物可以包含其它组分如有机磷烷化合物(Organophosphanes)，苯并呋喃基加工稳定剂，多酚化合物和/或羟基苯并二氢吡喃-衍生物，其它氨基酸基稳定剂，位阻哌啶基的光和热稳定剂(HA[L]S)，光学增白剂，紫外吸收剂，紫外猝灭剂，酸清除剂，金属钝化剂，成核剂，填料，抗静电剂，增塑剂，润滑剂，染料，颜料，乳化剂，阻燃剂，发泡剂，交联剂，防粘剂，滑爽剂，硫代增效剂和加工助剂。
本发明还涉及以纳米颗粒形式使用的那些述及的添加剂。
表1
用于实施例的稳定剂组合物中各组分的商品名，化学名和化学结构式。
以下的非限制性实施例将更详细地说明本发明。
实施例
聚乙烯-LLD的加工
100重量份的线型低密度聚乙烯(PE-LLD)，类别为F-30 FG-N，制造商为Mitsubishi(内部代码为LL96-2)[MFI：0.9g/10min/190℃/2.16Kg]在用购自Kenwood的实验用搅拌器进行搅拌下，混合入0.03重量份的Hostanox 0 16，0.05重量份的硬脂酸锌，0.04重量份Sandostab P-EPQ和0.01重量份的D，L-亮氨酸。然后，用Collin型单螺杆挤出机(螺杆压缩比1∶3，模口直径3毫米，螺杆转速80rpm)在210℃进行预挤出。采用带有4个加热区，每个均在240℃的GottfertExtrusimeter型单螺杆挤出机(螺杆压缩比为1∶3，70rpm，模口直径为4毫米)进行主挤出(第1-第5)。按照DIN 6167，采用Minolta光谱色度仪测量颜色。下面的表2中列出了对应的颜色的结果。YI代表黄度指数，度量在技术上不希望的泛黄现象，低的数字表示高的颜色稳定性。YI后的数字是挤出通道数。
根据本方法得到的结果示于表2-4中。所有涉及稳定化化合物的量的数字都是重量份数。
表2
颜色(YI)数据
| 稳定剂配方(基础稳定化作用：0.03Hostanox 016；0.05 Zn-硬脂酸锌) | 第1通道 | 第3通道 | 第5通道 |
| 0.04 Sandostab P-EPQ(参考1) | 1.75 | 2.56 | 2.78 |
| 0.05 Sandostab P-EPQ(参考2) | 1.63 | 2.20 | 2.44 |
| 0.07 Sandostab P-EPQ(参考3) | 1.46 | 2.64 | 2.34 |
| 0.04 Sandostab P-EPQ+0.01 D，L-亮氨酸 | 0.52 | 1.18 | 1.77 |
表3
在220℃下通过多通道挤出加工PE-LLD
| 稳定剂浓度 | 稳定剂 | 黄度指数 | |||
| 0.05000 | 硬脂酸锌 | ||||
| 0.03000 | HOSTANOX 016 | Y10 | Y11 | Y13 | Y15 |
| 0.05000 | SANDOSTAB P-EPQ ref. | -1,08 | -0,65 | 2,04 | 4,40 |
| 0.0500 | 硬脂酸锌 | ||||
| 0.0300 | HOSTANOX 016 | Y10 | Y11 | Y13 | Y15 |
| 0.0800 | SANDOSTAB P-EPQ ref. | -1,56 | -0,40 | 1,95 | 3,04 |
| 0.0500 | 硬脂酸锌 | ||||
| 0.0300 | HOSTANOX 016 | ||||
| 0.0450 | SAN DOSTAB P-EPQ ref. | Y10 | Y11 | Y13 | Y15 |
| 0.0050 | DL-亮氨酸 | -1,29 | -0,80 | 1,06 | 1,84 |
| 0.0500 | 硬脂酸锌 | ||||
| 0.0300 | HOSTANOX 016 | ||||
| 0.0400 | SANDOSTAB P-EPQ ref. | Y10 | Y11 | Y13 | Y15 |
| 0.0050 | DL-亮氨酸 | -1,15 | -1.53 | 1.17 | 4,63 |
| 0.0050 | DL-ALPHA-生育酚 E 307 | ||||
| 0.0500 | 硬脂酸锌 | ||||
| 0.0300 | HOSTANOX 016 | ||||
| 0.0400 | SAN DOSTAB P-EPQ ref | Y10 | Y11 | Y13 | Y15 |
| 0.0025 | DL-亮氨酸 | -0,28 | -0,67 | 1,82 | 4.83 |
| 0.0075 | DL-ALPHA-生育酚 E 307 | ||||
| 0.0500 | 硬脂酸锌 | ||||
| 0.0300 | HOSTANOX 016 | ||||
| 0.0400 | SANDOSTAB P-EPQ ref. | Y10 | Y11 | Y13 | Y15 |
| 0.0075 | DL-亮氨酸 | -1.16 | -1.37 | 0.95 | 4.04 |
| 0.0025 | DL-ALPHA-生育酚 E 307 | ||||
表4
在220℃通过多通道挤出加工PE-LLD
| 稳定剂浓度 | 稳定剂 | 黄度指数 | |||
| 0.0500 | 硬脂酸锌 | ||||
| 0.0300 | HOSTANOX 016 | Y10 | Y11 | Y13 | Y15 |
| 0.0500 | SANDOSTAB P-EPQ ref. | -1,06 | 0,55 | 3,44 | 4,87 |
| 0.0500 | 硬脂酸锌 | ||||
| 0.0300 | HOSTANOX 016 | ||||
| 0.0400 | SANDOSTAB P-EPQ ref. | ||||
| 0.0025 | 茶多酚淡绿 | Y10 | Y11 | Y13 | Y15 |
| 0.0075 | DL-亮氨酸 | -0,19 | 0,58 | 1,92 | 2,91 |
| 0.0500 | 硬脂酸锌 | ||||
| 0.0300 | HOSTANOX 016 | ||||
| 0.0400 | SANDOSTAB P-EPQ ref. | ||||
| 0.0050 | 茶多酚淡绿 | Y10 | Y11 | Y13 | Y15 |
| 0.0050 | DL-亮氨酸 | 3,49 | 3,09 | 4,02 | 4,58 |
| 0.0500 | 硬脂酸锌 | ||||
| 0.0300 | HOSTANOX 016 | ||||
| 0.0400 | SANDOSTAB P-EPQ ref. | ||||
| 0.0075 | 茶多酚淡绿 | Y10 | Y11 | Y13 | Y15 |
| 0.0025 | DL-亮氨酸 | 8,78 | 9,65 | 8,86 | 9,13 |
亮氨酸的加入明显改善了颜色稳定性。即使是在Sandostab P-EPQ部分地用α-生育酚或茶多酚淡绿(从草本植物提取物获得的天然多酚化合物，如绿茶提取物)进行替换的颜色稳定性较差的体系中，增加亮氨酸的量仍会导致颜色稳定性的改善。
聚丙烯的加工
100重量份的聚丙烯(PP)，Eltex P型，制造商为Solvay(内部代码为PP 99-10)[MFI：3.3g/10min/230℃/2.16Kg]在用购自Kenwood的实验用搅拌器进行搅拌下，混合入0.05重量份的Hostanox 0 10，0.05重量份的硬脂酸钙，0.05重量份的Sandostab P-EPQ和0.01重量份D，L-亮氨酸。作为替换使用的磷基加工(助剂)是0.5重量份的Ultranox 626或替换地将0.025重量份的Sandostab P-EPQ与0.025重量份的Hostanox PAR 24与0.005份的α-生育酚一起使用。然后采用Haendl e KPS 25型单螺杆挤出机(螺杆压缩比为1∶3，模口直径4毫米，螺杆转速80rpm)在220℃进行预挤出。采用带有4个加热区，每个为240℃或替换地为270℃或替换地为300℃的GottfertExtrusimeter型单螺杆挤出机(螺杆压缩比为1∶3，50rpm，模口直径为4毫米，螺杆转速80rpm)进行主挤出(第1-第5)。按照DIN 6167采用Minolta光谱色度仪测量颜色。选择的对应颜色的结果列于下面的表5A-C中。
表5A
在T＝240℃用多通道挤出加工聚丙烯
| 0.1000 | 硬脂酸钙DW | ||||
| 0.0500 | HOSTANOX O 10 | ||||
| 0.0450 | Ultranox 626 | Y10 | Y11 | Y13 | Y15 |
| 0.0050 | α-生育酚 | 2.03 | 2.53 | 5.23 | 10.22 |
| 0.1000 | 硬脂酸钙DW | ||||
| 0.0500 | HOSTANOX O 10 | ||||
| 0.0450 | Ultranox 626 | ||||
| 0.0050 | α-生育酚 | Y10 | Y11 | Y13 | Y15 |
| 0.0100 | DL-亮氨酸 | 1.24 | 1.74 | 4.83 | 8.02 |
表5B
在T＝270℃用多通道挤出加工聚丙烯
| 稳定剂浓度 | 稳定剂 | 黄度指数 | |||
| 0.1000 | 硬脂酸钙DW | ||||
| 0.0500 | HOSTANOX O 10 | ||||
| 0.0225 | SANDOSTAB P-EPQ ref. | ||||
| 0.0225 | HostanoxPAR 24 | Y10 | Y11 | Y13 | Y15 |
| 0.0050 | α-生育酚 | 3.27 | 5.00 | 9.52 | 15.47 |
| 0.1000 | 硬脂酸钙DW | ||||
| 0.0500 | HOSTANOX O 10 | ||||
| 0.0225 | SANDOSTAB P-EPQ ref. | ||||
| 0.0225 | Hostanox PAR 24 | ||||
| 0.0050 | α-生育酚 | Y10 | Y11 | Y13 | Y15 |
| 0.0100 | DL-亮氨酸 | 2.15 | 3.11 | 8.85 | 12.54 |
| 0.1000 | 硬脂酸钙DW | ||||
| 0.0500 | HOSTANOX O 10 | ||||
| 0.0450 | Ultranox 626 | Y10 | Y11 | Y13 | Y15 |
| 0.0050 | α-生育酚 | 2.11 | 5.20 | 9.85 | 13.40 |
| 0.1000 | 硬脂酸钙DW | ||||
| 0.0500 | HOSTANOX O 10 | ||||
| 0.0450 | Ultranox 626 | ||||
| 0.0050 | α-生育酚 | Y10 | Y11 | Y13 | Y15 |
| 0.0100 | DL-亮氨酸 | 1.44 | 2.45 | 7.18 | 12.91 |
表5C
在T＝300℃用多通道挤出加工聚丙烯
| 稳定剂浓度 | 稳定剂 | 黄度指数 | |||
| 0.1000 | 硬脂酸钙DW | ||||
| 0.0500 | HOSTANOX O 10 | ||||
| 0.0225 | SANDOSTAB P-EPQ ref. | ||||
| 0.0225 | Hostanox PAR 24 | Y10 | Y11 | Y13 | Y15 |
| 0.0050 | α-生育酚 | 2.91 | 4.91 | 9.70 | 13.14 |
| 0.1000 | 硬脂酸钙DW | ||||
| 0.0500 | HOSTANOX O 10 | ||||
| 0.0225 | SAN DOSTAB P-E PQ ref. | ||||
| 0.0225 | Hostanox PAR 24 | ||||
| 0.0050 | α-生育酚 | Y10 | Y11 | Y13 | Y15 |
| 0.0100 | DL-亮氨酸 | 1.82 | 3.28 | 7.23 | 10.25 |
| 0.1000 | 硬脂酸钙DW | ||||
| 0.0500 | HOSTANOX O 10 | ||||
| 0.0450 | Ultranox 626 | Y10 | Y11 | Y13 | Y15 |
| 0.0050 | α-生育酚 | 2.51 | 5.00 | 10.76 | 14.55 |
| 0.1000 | 硬脂酸钙DW | ||||
| .0500 | HOSTANOX O 10 | ||||
| 0.0450 | Ultranox 626 | ||||
| 0.0050 | α-生育酚 | Y10 | Y11 | Y13 | Y15 |
| 0.0100 | DL-亮氨酸 | 1.10 | 2.02 | 6.88 | 12.40 |
结果清楚地显示在聚丙烯中本发明的稳定剂组合物也会导致显著改善的颜色稳定性。
Claims (9)
1.用于聚烯烃基热塑性聚合物的颜色改善稳定剂组合物，包含
a)至少一种位阻酚，其中的位阻酚是2，2′-双[3，5-[3，5-双(1，1-二甲基乙基)-4-羟苯基]-1-氧代丙氧基]甲基-1，3-丙烷二基-3，5-双(1，1-二甲基乙基)-4-羟基苯丙酸酯；十八烷基-3，5-双(1，1-二甲基乙基)-4-羟基苯丙酸酯；1，3，5-三[[3，5-双(1，1-二甲基乙基)-4-羟苯基]甲基]-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮；4，4′，4″-[2，4，6-三甲基-1，3，5-苯三基]三-(亚甲基)]三[2，6-双(1，1-二甲基乙基)苯酚；乙烷二基-3，5-双(1，1-二甲基乙基)-4-羟基-硫代二-2，1-苯丙酸酯；单乙基-[[3，5-双(1，1-二甲基乙基)-4-羟苯基]甲基]-膦酸酯的2∶1钙盐；2-[3-[3，5-双-(1，1-二甲基乙基)-4-羟基-苯基]-1-氧代丙基]酰肼-3，5-双(1，1-二甲基乙基)-4-羟基苯丙酸；2，2′-草酰氨基-双-[乙基-3-(3，5-二-叔丁基-4-羟苯基)丙酸酯]或它们的混合物；
b)至少一种含磷的第二抗氧化剂，其中的含磷的第二抗氧化剂是三苯基亚磷酸酯，三异癸基亚磷酸酯；三(壬基苯基)亚磷酸酯；双十八烷基五赤藓醇二亚磷酸酯；2，4，6-三叔丁基苯基-2-丁基-2-乙基-1，3-丙二醇亚磷酸酯；双(2，4-二-叔丁基苯基)-五赤藓醇基二亚磷酸酯；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；二[2，4-二叔丁基-6-甲基-苯基]乙基亚磷酸酯]，2，2′-亚乙基-双-(4，6-二-叔丁基苯基)-氟代亚磷酸酯；三-(2，4-二叔丁基苯基)亚磷酸酯；4，6-二叔丁基-间甲酚与联苯和三氯化磷的福瑞德克莱福特反应产物的缩合产物；四[2，4-二叔丁基苯基]-4，4′-二亚苯基-二亚膦酸酯；2，4-二叔丁基苯酚与联苯和PCl3的福瑞德-克莱福特反应产物的缩合产物；和
c)至少一种亮氨酸化合物，其中的亮氨酸化合物是亮氨酸，
其中组分(a)∶组分(b)∶组分(c)的重量比为1∶5∶3-2∶0.5∶0.1。
2.权利要求1的组合物，其中组分(a)∶组分(b)∶组分(c)的重量比为1∶3∶2-1∶1∶0.2。
3.提高聚烯烃基热塑性聚合物的颜色稳定性的方法，包括在加工前或在加工过程中向其中加入基于热塑性聚合物计为0.001-5wt％的权利要求1或2中的稳定剂组合物。
4.权利要求3的方法，其中稳定剂组合物加入的量为0.01-1wt％，基于热塑性聚合物计。
5.权利要求3的方法，其中稳定剂组合物加入的量为0.1-0.5wt％，基于热塑性聚合物计。
6.制造权利要求1或2的稳定剂组合物的方法，包括将组分(a)，(b)和(c)按权利要求1或2中给定的重量比混合。
7.包含权利要求1或2的稳定剂组合物和热塑性材料的母料组合物。
8.权利要求7的母料组合物，包含10-80wt％的稳定剂组合物和90-20wt％的所述热塑性材料。
9.权利要求7的母料组合物，包含5-25wt％的稳定剂组合物和95-75wt％的所述热塑性材料。
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| Application Number | Priority Date | Filing Date | Title |
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| GBGB0104371.0A GB0104371D0 (en) | 2001-02-22 | 2001-02-22 | Color improving stabilizing compositions comprising leucine |
| GB0104371.0 | 2001-02-22 |
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| EP (1) | EP1373392B1 (zh) |
| JP (1) | JP3877068B2 (zh) |
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| KR20070033042A (ko) * | 2004-07-22 | 2007-03-23 | 제이에스알 가부시끼가이샤 | 중합체 조성물 및 그의 제조 방법 |
| DK2081761T3 (da) | 2006-11-08 | 2010-06-07 | Frans Nooren Afdichtingssystem | Fremgangsmåde til forsyning af en forlænget rørformet genstand med et korrosionsbeskyttende coatingsystem, som har selvreparerende egenskaber |
| CN105168114A (zh) | 2008-08-15 | 2015-12-23 | 硬木药品公司 | 适合口服给药的鸟苷酸环化酶-c受体激动剂多肽的稳定的固体制剂 |
| US8067490B2 (en) * | 2008-09-24 | 2011-11-29 | Chemtura Corporation | Blended phosphite or phosphonite compositions having improved hydrolytic stability |
| WO2011017502A2 (en) * | 2009-08-06 | 2011-02-10 | Ironwood Pharmaceuticals, Inc. | Linaclotide-containing formulations for oral administration |
| AU2011218009B2 (en) | 2010-02-17 | 2016-11-03 | Ironwood Pharmaceuticals, Inc | Treatments for gastrointestinal disorders |
| EP3626253B8 (en) | 2010-08-11 | 2022-04-20 | Ironwood Pharmaceuticals, Inc. | Stable formulations of linaclotide |
| HUE032237T2 (en) | 2011-08-17 | 2017-09-28 | Ironwood Pharmaceuticals Inc | Treatment of gastrointestinal disorders |
| US9926630B2 (en) | 2012-07-13 | 2018-03-27 | Frans Nooren Afdichtingssystemen B.V. | Process for the protection against corrosion of an article in a wet environment and composition therefore |
| CA2886424A1 (en) * | 2012-09-28 | 2014-04-03 | Clariant Finance (Bvi) Limited | Process for preparing a polypropylene-based object having an increased surface energy |
| CN104250394B (zh) * | 2013-06-26 | 2017-08-01 | 合肥杰事杰新材料股份有限公司 | 一种改性聚丙烯材料及其制备方法 |
| CN107903412A (zh) * | 2017-11-15 | 2018-04-13 | 苏州博云塑业有限公司 | 一种能够提高颜色稳定性的抗静电色母粒 |
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-
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| JP3877068B2 (ja) | 2007-02-07 |
| ATE317872T1 (de) | 2006-03-15 |
| DE60209215D1 (de) | 2006-04-20 |
| EP1373392A1 (en) | 2004-01-02 |
| GB0104371D0 (en) | 2001-04-11 |
| ES2256448T3 (es) | 2006-07-16 |
| EP1373392B1 (en) | 2006-02-15 |
| DE60209215T2 (de) | 2006-07-20 |
| WO2002066551A1 (en) | 2002-08-29 |
| US20040072932A1 (en) | 2004-04-15 |
| CN1492901A (zh) | 2004-04-28 |
| KR100845352B1 (ko) | 2008-07-09 |
| RU2003128101A (ru) | 2005-02-27 |
| JP2004521979A (ja) | 2004-07-22 |
| RU2276166C2 (ru) | 2006-05-10 |
| TW567206B (en) | 2003-12-21 |
| KR20030084943A (ko) | 2003-11-01 |
| US6995200B2 (en) | 2006-02-07 |
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