CN101240102A - 含有特定抗氧化剂的湿可交联聚合组合物 - Google Patents

含有特定抗氧化剂的湿可交联聚合组合物 Download PDF

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CN101240102A
CN101240102A CNA2008100829052A CN200810082905A CN101240102A CN 101240102 A CN101240102 A CN 101240102A CN A2008100829052 A CNA2008100829052 A CN A2008100829052A CN 200810082905 A CN200810082905 A CN 200810082905A CN 101240102 A CN101240102 A CN 101240102A
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polymeric composition
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M·B·比斯科利奥
K·T·德夫林
M·埃塞格尔
L·H·格罗斯
D·L·小麦克丹尼尔
S·F·舒罗特
M·小科茨
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Abstract

本发明涉及湿可交联聚合组合物，所述组合物包括(a)硅烷官能化烯属聚合物，(b)酸性甲硅烷醇缩合催化剂，和(c)抗氧化剂，该抗氧化剂不具有叔烷基取代的芳基或酚基，其中，所述的聚合组合物不会产生大量的恶臭气味的或易燃的气体。或者，所述抗氧化剂基本没有在酸性甲硅烷醇缩合催化剂及传统生产条件下易发生脱烷基化的取代基。本发明还包括制备所述湿可交联聚合组合物的方法。所述的湿可交联聚合组合物可作为涂料应用在电线或电缆上。

Description

含有特定抗氧化剂的湿可交联聚合组合物
本申请是申请号为200480017558.5，申请日为2004年6月22日，发明名称为“含有特定抗氧化剂的湿可交联聚合组合物”的中国专利申请的分案申请。
技术领域
本发明涉及不会产生大量恶臭气味气体、易燃气体，或两者都不产生的湿可交联(moisture-crosslinkable)聚合组合物。所述的聚合组合物适用于电线电缆的应用中。
背景技术
使用酸性甲硅烷醇缩合催化剂能改进湿可交联聚合组合物的固化速率。可惜的是某些酸性甲硅烷醇缩合催化剂如亚砜酸性催化剂在高温条件下(＞100摄氏度)不稳定或不能作为催化剂进行选择性反应。结果，在特定的反应条件下，这些亚砜酸可能会释放出亚砜气体或与聚合组合物中的其它添加剂发生反应。释放出的气体中或反应产物的一些具有强烈的气味，并且是易燃的，和/或负面影响从聚合组合物生产的加热老化制品的可拉伸性质。产生的气体也会导致在从湿可交联聚合组合物生产的制品上出现空隙或表面瑕疵。
需要一种不会产生大量恶臭气味气体或易燃气体的湿可交联聚合组合物。而且还需要对其进一步改进从而不会负面影响(a)酸性甲硅烷醇缩合催化剂的催化性能或(b)从聚合组合物生产的加热老化制品的可拉伸性质。
发明内容
本发明涉及湿可交联聚合组合物，所述组合物包括(a)硅烷官能化烯属聚合物，(b)酸性甲硅烷醇缩合催化剂，和(c)抗氧化剂，该抗氧化剂不具有叔烷基取代的芳基或酚基，其中，所述的聚合组合物不会产生大量的恶臭气味的或易燃的气体。或者，所述抗氧化剂基本没有在酸性甲硅烷醇缩合催化剂及传统生产条件下易发生脱烷基化的取代基。所述的湿可交联聚合组合物可用作涂层应用在电线或电缆上。本发明还包括制备所述湿可交联聚合组合物的方法。
具体实施方式
本发明的湿可交联聚合组合物包括(a)硅烷官能化烯属聚合物，(b)酸性甲硅烷醇缩合催化剂，和(c)抗氧化剂，该抗氧化剂不具有叔烷基取代的芳基或酚基，其中，所述的聚合组合物不会产生大量的恶臭气味气体、易燃气体，或都不产生。
适用的硅烷官能化烯属聚合物包括硅烷官能化聚乙烯聚合物、硅烷官能化聚丙烯聚合物，及它们的混合物。优选地，硅烷官能化烯属聚合物选自(i)乙烯与可水解硅烷的共聚物，(ii)下列物质的共聚物：乙烯、可水解硅烷，和一种或多种C3或更高级α-烯烃和不饱和酯，(iii)乙烯均聚物，在其骨架上接枝有可水解的硅烷，和(iv)下列物质的共聚物：乙烯和一种或多种C3或更高级α-烯烃和不饱和酯，并且在共聚物上接枝有可水解硅烷。
这里所使用的术语聚乙烯聚合物是乙烯均聚物或乙烯与少量的具有3-12个碳原子的，优选具有4-8个碳原子的α-烯烃，和任选的二烯的共聚物，或者所述均聚物和共聚物的混合物。混合物可以机械共混或原位共混。α-烯烃的例子为丙烯、1-丁烯、1-己烯、4-甲基-1-戊烯和1-辛烯。聚乙烯也可以是乙烯与不饱和酯的共聚物，所述不饱和酯例如为乙烯酯(如乙酸乙烯酯或丙烯酸酯或甲基丙烯酸酯)。
聚乙烯可以是均匀的或非均匀的。均匀聚乙烯通常具有的多分散性(Mw/Mn)的范围为1.5-3.5，并且具有基本均匀的共聚单体分布，特征在于当通过差式扫描量热器测量时其具有单一而相对较低的熔点。非均匀聚乙烯的多分散性(Mw/Mn)通常大于3.5，并且缺少均匀的共聚单体分布。Mw定义为重均分子量，Mn定义为数均分子量。
聚乙烯可具有的密度范围为0.860-0.970克/立方厘米，优选的密度范围为0.870-0.930克/立方厘米。它们的熔融指数的范围为0.1-50克/10分钟。如果所述聚乙烯为均聚物，则其熔融指数优选在0.75-3克/10分钟范围内。熔融指数是在ASTM D-1238，条件E下，并且在190摄氏度和2160克下测量的。
低或高压工艺可生产聚乙烯。它们也可采用传统技术通过气相工艺或液相工艺生产(即，溶液或淤浆工艺)。低压工艺典型的是在小于1000磅/平方英尺(“psi”)的压力下进行，而高压工艺典型的是在大于15,000psi的压力下进行。
用于制备这些聚乙烯的典型催化剂体系包括镁/钛基催化剂体系、钒基催化剂体系、铬基催化剂体系、金属茂催化剂体系，和其它过渡金属催化剂体系。往往将这些催化剂体系中的许多体系参考为齐格勒-纳塔催化剂体系或菲利普斯催化剂体系。适用的催化剂体系包括使用负载于二氧化硅-氧化铝载体上的铬或钼催化剂。
适用的聚乙烯包括通过高压工艺生产的低密度乙烯均聚物(HP-LDPE)、线性低密度聚乙烯(LLDPE)、非常低密度聚乙烯(VLDPE)、极低密度聚乙烯(ULDPE)、中等密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)和金属茂共聚物。
高压工艺典型的为自由基引发的聚合反应，在管状反应器或搅拌的高压釜中进行。在管状反应器中反应时，压力范围为25,000到45,000psi，温度范围为200到350摄氏度。在搅拌的高压釜中反应时，压力范围为10,000到30,000psi，温度范围为175到250摄氏度。
已知的，由乙烯和不饱和酯组成的共聚物可通过传统的高压技术制备。不饱和酯可以是丙烯酸烷基酯、甲基丙烯酸烷基酯，或羧酸乙烯酯。烷基基团可具有1-8个碳原子，优选具有1-4个碳原子。羧酸基团可具有2-8个碳原子，优选具有2-5个碳原子。以聚合物的重量计，共聚物中酯共聚单体的含量为5-50wt％，优选为15-40wt％。丙烯酸酯和甲基丙烯酸酯的例子为丙烯酸乙基酯、丙烯酸甲基酯、甲基丙烯酸甲基酯、丙烯酸叔丁基酯、丙烯酸正丁基酯、甲基丙烯酸正丁基酯和丙烯酸2-乙基己基酯。羧酸乙烯酯的例子包括乙酸乙烯酯、丙酸乙烯酯和丁酸乙烯酯。乙烯/不饱和酯共聚物的熔融指数的范围为0.5-50克/10分钟，优选的范围为2-25克/10分钟。
也可使用乙烯和乙烯基硅烷的共聚物。合适的硅烷的例子为乙烯基三甲氧基硅烷和乙烯基三乙氧基硅烷。这些聚合物典型地利用高压工艺来生产。当需要生产湿可交联组合物时，使用这类聚合物是合意的。
VLDPE或者ULDPE可以是乙烯与具有3-12个碳原子，优选具有3-8个碳原子的一个或多个α-烯烃的共聚物。VLDPE或者ULDPE的密度范围为0.870到0.915克/立方厘米。VLDPE或者ULDPE的熔融指数的范围为0.1到20克/10分钟，优选为0.3到5克/10分钟。以共聚物的重量计，VLDPE或者ULDPE中除了乙烯之外的共聚单体的含量范围为1到49wt％，优选为15到40wt％。
还可以包括第三种共聚单体，如另一种α-烯烃或二烯，如亚乙基降冰片烯、丁二烯、1，4-己二烯或二环戍二烯。乙烯/丙稀共聚物通常参考为EPR，乙烯/丙稀/二烯三元共聚物通常参考为EPDM。以共聚物的重量计，第三种共聚单体的量为1-15wt％，优选为1-10wt％。优选的，包括乙烯在内，共聚物包括两种或三种的共聚单体。
LLDPE可包括VLDPE、ULDPE和MDPE，该LLDPE也可为线性的，但是通常其密度的范围为0.916到0.925克/立方厘米。所述的LLDPE可为乙烯与一种或多种具有3-12个碳原子，优选具有3-8个碳原子的α-烯烃的共聚物。熔融指数的范围为1到20克/10分钟，优选范围为3到8克/10分钟。
任何聚丙稀都可用于这些组合物中。例子包括丙稀均聚物、丙稀和其它烯烃的共聚物以及丙稀、乙烯和二烯(如降冰片烯和癸二烯(decadiene))的三元共聚物。此外，可将聚丙稀分散到或与其它聚合物(如EPR或EPDM)共混。合适的聚丙稀包括TPE、TPO和TPV。聚丙稀的例子在POLYPROPYLENE HANDBOOK：POLYMERIZATIONCHARACTERIZATION，PROPERTIES，PROCESSING，APPLICATIONs3-14，113-176(E.Moore，Jr.ed.，1996)中进行了描述。
乙烯基烷氧硅烷类(如，乙烯基三甲氧基硅烷和乙烯基三乙氧基硅烷)为适用于接枝或共聚反应的硅烷化合物，从而生成硅烷官能化的烯属聚合物。
合适的酸性甲硅烷醇缩合催化剂包括(a)有机磺酸及其可水解前体，(b)有机膦酸及其可水解的前体，和(c)卤酸。优选地，酸性甲硅烷醇缩合催化剂为有机磺酸。更优选地，酸性甲硅烷醇缩合催化剂选自烷基芳基磺酸、芳基烷基磺酸或烷基化的芳基二磺酸。甚至更优选地，酸性甲硅烷醇缩合催化剂选自取代的苯磺酸或取代的萘磺酸。最优选地，酸性甲硅烷醇缩合催化剂为十二烷基苄基磺酸或二壬基萘基磺酸。
合适的抗氧化剂包括(a)酚抗氧化剂，(b)硫基抗氧化剂，(c)磷酸盐基抗氧化剂，和(d)肼基金属减活化剂。合适的酚抗氧化剂包括甲基取代的酚。其它具有伯或仲羰基取代基的酚也是合适的抗氧化剂。优选的酚抗氧化剂为异亚丁基双(4，6-二甲基酚)。优选的肼基金属减活化剂为草酰双(亚苄基酰肼)。优选地，抗氧化剂存在的量为聚合组合物的0.05wt％到10wt％。
此外，组合物还可含有其它添加剂如着色剂、防腐剂、润滑剂、抗阻滞剂、阻燃剂和加工助剂。
在一个优选的实施方案中，本发明为湿可交联聚合组合物，所述组合物包括(a)硅烷官能化烯属聚合物，该聚合物选自(i)乙烯和可水解硅烷的共聚物，(ii)下列物质的共聚物：乙烯、可水解硅烷和一种或多种C3或更高级α-烯烃和不饱和酯，(iii)乙烯均聚物，并且在其骨架上接枝有可水解硅烷，和(iv)乙烯和一种或多种C3或更高级α-烯烃和不饱和酯的共聚物，该共聚物在其骨架上接枝有可水解硅烷，(b)酸性甲硅烷醇缩合催化剂，所述催化剂选自烷基芳基磺酸、芳基烷基磺酸或烷基化的芳基二磺酸；和(c)抗氧化剂，所述抗氧化剂不具有叔烷基取代的芳基或酚基，并且该抗氧化剂选自(i)酚抗氧化剂，(ii)硫基抗氧化剂，(iii)磷酸盐基抗氧化剂，和(iv)肼基金属减活化剂，其中聚合组合物不会产生大量恶臭气味的气体、易燃气体，或两者都不会产生。
实施例
下列非限制性的实施例可以解释本发明。
50克样品的较低爆炸极限(LEL)
本发明的三个样品对照6个对比实施例进行评估。将所有示例性的聚合组合物制备成50克重量，并使用46.33wt％AMPLIFY EA100TM乙烯丙烯酸乙酯共聚物、46.33wt％线性低密度聚乙烯(“LLDPE”)、4％NACURETMB201烷基芳基磺酸和3.34wt％评估的抗氧化剂。
AMPLIFY EA100TM乙烯丙烯酸乙酯共聚物从Dow ChemicalCompany购得，熔融指数为1.5克/10分钟，并且具有15wt％的丙烯酸乙酯浓度。LLDPE为1-丁烯和乙烯的共聚物，熔融指数为0.7克/10分钟，密度为0.92克/立方厘米。NACURETMB201烷基芳基磺酸购自KingIndustries，Inc.
对于每一个示例性的聚合组合物，将50克组合物放在密封的32-盎司瓶中，该瓶在其盖子处具有橡胶隔膜。将所述的瓶子及其内容物在180摄氏度加热30分钟。在瓶子冷却到室温后，将隔膜移开，并将Eagle检测仪放入瓶中来测量生成的气体的量。
使用PKI仪器Eagle系列便携式多气体监测仪来测量生成的气体。将仪器校准，以0到100％LEL比例来检测甲烷，对应于0到50,000份/100万(ppm)甲烷。利用甲烷气体比例将LEL百分数记录为代表所有检测到的气体。
                表1
 实施例No.   抗氧化剂  LEL百分数
 实施例1   DSTDP  7
 实施例2   Lowinox22IB46  8
 实施例3   OABH  9
 对比实施例4   Cyanox1790  40
 对比实施例5   Irganox1010  46
 对比实施例6   Irganox1035  24
 对比实施例7   Irganox3114  59
 对比实施例8   LowinoxAH25  37
 对比实施例9   TBM6  18
DSTDP为二硬脂酰基-3-3-硫代二丙酸酯，从Great Lakes ChemicalCorporation购得。Lowinox22IB46为异亚丁基双-(4，6-二甲基酚)，从Great Lakes Chemical Corporation购得的抗氧化剂。OABH为草酰双(亚苄基酰肼)，从Eastman Chemical company购得的金属减活化剂。Cyanox1790TM为从Cytec Industries购得的三(4-叔丁基-3-羟基-2，6-二甲基苄基)-s-三嗪-2，4，6-(1H，3H，5H)三酮。Irganox1010TM为四亚甲基(3，5-二叔丁基-4-羟基氢化桂皮酸酯)甲烷，Irganox1035TM为硫代二亚乙基-双(3，5-二叔丁基-4-羟基桂皮酸酯)，Irganox3114TM为1，3，5-三[3，5-双(1，1-二甲基乙基)-4-羟基苯基]甲基]-1，3，5-三嗪-2，4，6(1H，3H，5H)-三酮，它们都是从Ciba Specialty Chemicals Inc.购得的。Lowinox AH25TM为2，5-二叔戊基氢醌，从Great Lakes Chemical Corporation购得的。TBM6为4，4-硫代双(2-叔丁基-5-甲基苯酚)，从Great Lakes Chemical Corporation购得的。
50磅样品的较低爆炸极限
对照2个对比实施例对本发明的实施例进行评估。将所有示例性的聚合组合物制备成50磅重量，并含有4.0wt％NACURETMB201烷基芳基磺酸。每一组分的重量百分比如表2所示。
对于每一个示例性的聚合组合物及其随后的混和物，将50磅的50摄氏度的组合物放置并密封在20千克箔袋中，所述箔袋总体积的10％为空气。24小时之后，将Eagle检测仪放入箔袋中来测量生成的气体的量。
                            表2
  组分   实施例10   对比实施例11   对比实施例12
  AMPLIFY EA100TM   46.18   48.00   45.50
  LLDPE   46.18   48.00   45.50
  Irganox 1010   3.33
  Irganox 1024   1.67
  Lowinox 22IB46   3.34
  OABH   0.30
  LEL百分数   9   14   ＞100
Irganox1024TM为1，2-双(3，5-二叔丁基-4-羟基氢化肉桂酰基)肼，从Ciba Specialty Chemicals Inc购得。

Claims (1)

1.一种湿可交联聚合组合物，所述组合物包括
(a)硅烷官能化烯属聚合物，
(b)酸性甲硅烷醇缩合催化剂，和
(c)抗氧化剂，所述抗氧化剂基本没有在酸性甲硅烷醇缩合催化剂
存在下易发生脱烷基化的取代基，
其中，所述的聚合组合物不会产生大量的恶臭气味气体、易燃的气体，或两者都不产生。
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