CN1084353C - 热塑性弹性体组合物及其制备方法 - Google Patents

热塑性弹性体组合物及其制备方法 Download PDF

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CN1084353C
CN1084353C CN94103319A CN94103319A CN1084353C CN 1084353 C CN1084353 C CN 1084353C CN 94103319 A CN94103319 A CN 94103319A CN 94103319 A CN94103319 A CN 94103319A CN 1084353 C CN1084353 C CN 1084353C
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M·D·艾鲁
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Abstract

通过向结晶聚烯烃均聚物或共聚物与烯烃类橡胶的共混物中加入适宜的低分子量酯增塑剂，得到了改进低温性能的热塑性弹性体。本组合物中的橡胶组分是至少部分固化的。

Description

热塑性弹性体组合物及其制备方法
本发明涉及改进了低温性能的热塑性弹性体。热塑性弹性体通常定义为可用与传统热塑性材料相同的方法加工和回收、同时在试用温度下具有与硫化橡胶相近的性能的聚合物或聚合物共混物。在制备高性能热塑性弹性体时，塑料与弹性橡胶的共混物或合金变得日趋重要，特别是在各种应用中代替热固性橡胶。
通常是将热塑性聚烯烃与弹性组合物共混，使弹性体作为微粒分散相紧密且均匀地分散于热塑性塑料连续相中，制得既具有热塑性又具有弹性的聚合物共混物。使用硫化组合物的早期工作见于美国专利No.3,037,954，它除公开了静态硫化方法以外，还公开了动态硫化方法，即：使可硫化弹性体分散于热塑性树脂聚合物中，在不断混合和剪切聚合物共混物时，使弹性体硫化。所得组合物是硫化弹性体如丁基橡胶、氯化丁基橡胶、聚丁二烯或聚异丁烯在未硫化母体热塑性聚合物如聚丙烯中的微粒凝胶分散体。该专利方法在组合物中使用了得自煤焦油、松焦油或石油的油添加剂。
美国专利No.Re.32,028公开了包括热塑性烯烃树脂与烯烃类共聚物橡胶的聚合物共混物，其中将橡胶动态硫化至部分硫化。所得组合物可再加工。为改进组合物的挤出质量，该方法向硫化共混物中加入约1份/百份树脂(phr)各种润滑剂。
美国专利Nos.4,130,534和4,130,535公开了热塑性弹性体组合物，它们分别包括丁基橡胶和聚烯烃树脂、烯烃类橡胶和聚烯烃树脂。用动态硫化方法制备该组合物，并使橡胶组分硫化至基本不溶于传统溶剂的程度。建议向共混物中加入增塑剂和芳烃、环烷烃和链烷烃增量油。它没有给出具体选择哪一组或类型的增塑剂。众所周知，不同的橡胶只与不同类型的增塑剂相容，不是所有增塑剂适用于所有橡胶。
美国专利No.5,157, 081公开了动态硫化的共混物，它包括在聚烯烃树脂母体中的丁基橡胶基弹性体和乙烯—丙烯聚合物弹性体。可以加入得自石油馏分的橡胶操作油，只是建议可以使用有机酯和其它合成增塑剂。
本发明发现：将某类低分子量酯增塑剂混入结晶聚烯烃均聚物或共聚物与烯烃类橡胶的共混物中，可以得到改进低温性能的热塑性弹性体组合物。组合物中的橡胶组分通常以很小颗粒(即微粒)存在于热塑性塑料母体中，且优选它至少部分硫化。也可能是共连续相形态。出人意料地发现，该组合物含有这些有机酯以后，使热塑性弹性体在保持其在宽的温度范围内压缩变形小、撕裂强度高和动力学性能好之优良性能的同时，还显著降低了橡胶相和聚烯烃相的玻璃化转变温度(Tg)、改进了低温下的抗冲击强度并提高了耐磨性能。该组合物可用作恒速接合套管(boots)、齿轮齿条套管、汽车弹性塑料零件和需在低温如-40℃下使用的橡胶-塑料(热塑性弹性体)机械制品。
因此，一方面本发明提供一种热塑性弹性体组合物，它包括：
(a).以聚烯烃均聚物或共聚物与烯烃类橡胶的总重量为基准计，10～90％重量的热塑性结晶聚烯烃均聚物或共聚物；
(b).以聚烯烃均聚物或共聚物与烯烃类橡胶的总重量为基准计，90～10％重量的烯烃类橡胶，所述橡胶选自乙烯、丙烯和非共轭二烯的三元共聚物橡胶、乙烯-丙烯共聚物橡胶、丁基橡胶、卤化丁基橡胶、异单烯烃与对-烷基苯乙烯的共聚物、天然橡胶、聚异戊二烯及其混合物；和
(c).基于每100重量份所述橡胶，1～250重量份的可与聚烯烃和橡胶都相容的低分子量酯或醚酯增塑剂；
其中，所述橡胶至少部分交联。
另一方面，本发明提供一种热塑性弹性体的制备方法，它包括：
(a).在高于聚烯烃熔点的温度下，将90％～10％重量烯烃类橡胶与10％～90％重量热塑性结晶聚烯烃均聚物或共聚物共混，所述橡胶选自乙烯、丙烯和非共轭二烯的三元共聚物橡胶、乙烯-丙烯共聚物橡胶、丁基橡胶、卤化丁基橡胶、异单烯烃与对-烷基苯乙烯的共聚物、天然橡胶、聚异戊二烯及其混合物，所述重量百分数以聚烯烃均聚物或共聚物与烯烃类橡胶的总重量为基准计；
(b).基于每100重量份所述橡胶，向共混物中加入1～250重量份的可与橡胶和聚烯烃都相容的低分子量酯或醚酯增塑剂；和
(c).在所得混合物中，使橡胶交联。
聚烯烃
适用于本发明组合物的聚烯烃包括热塑性结晶聚烯烃均聚物和共聚物。它们通常由C3-C6单烯属单体制备，如丙烯、1-丁烯、异丁烯、1-戊烯等，优选丙烯。本说明书如权利要求书中，“聚丙烯”包括丙烯均聚物和聚丙烯的反应器共聚物，后者可含有约1％wt至约20％wt乙烯或C4-C18α-烯烃共聚单体及其混合物。内烯可以是高结晶度的等规或间同立构聚丙烯，其玻璃化转变温度(Tg)通常很窄。工业品聚烯烃可用于本发明的实践中。
组合物中聚烯烃的用量通常占橡胶和聚烯烃总重的约10％wt至约90％wt、优选约60％wt至约90％wt。
烯烃类橡胶
适宜的单烯烃共聚物橡胶包括两种或多种α-单烯烃的非极性、基本非结晶橡胶共聚物，优选与至少一种多烯、通常为二烯的共聚物。可以使用饱和的单烯类共聚物橡胶，例如乙烯-丙烯共聚物橡胶(EPM)。但是，不饱和单烯类橡胶如EPDM橡胶更适宜。EPDM是乙烯、丙烯和非共轭二烯的三元共聚物。适宜的非共轭二烯包括5-亚乙基-2-降冰片烯(ENB)、1，4-已二烯、5-亚甲基-2-降冰片烯(MNB)、1，6-辛二烯、5-甲基-1，4-己二烯、3，7-二甲基-1，6-辛二烯、1，3-环戊二烯，1，4-环己二烯.二聚环戊二烯(DCPD)等。
丁基橡胶也可用于本发明组合物中。本说明书和权利要求书中，″丁基橡胶″包括：异烯烃与共轭多烯烃的二元共聚物，异烯烃、共轭多烯烃与二乙烯基芳烃单体的三元共聚物，这些二元和三元共聚物的卤化衍生物。适用的丁基橡胶共聚物由占大部分的异稀烃与少量、通常底于30％wt的共轭多烯烃制备。优选的共聚物含有约85～99.5％wt异烯烃如异丁烯和约15～0.5％wt的C4-C14多烯如异戊二烯、丁二烯、二甲基丁二烯和1，3-戊二烯。用于本发明的工业品丁基橡胶是异丁烯与少量异戊二烯的共聚物。美国专利NO.4,916,180说明了其它二元和三元共聚物丁基橡胶(通过引用，并入本文)。
属于本发明的烯烃类橡胶的另一种适宜共聚物是C4-C7异单烯烃与对—烷基苯乙烯的共聚物和(优选)其卤化衍生物。在共聚物中，主要是在对—烷基苯乙烯上的卤素量为约0.1～10％wt。一个优选的例子是异丁烯与对—甲基苯乙烯的共聚物的溴化物。美国专利No.5,162,445更完全地描述了这些共聚物(通过引用，并入本文)。
适用于本发明的另一烯烃类橡胶是天然橡胶，其主要成份是线型顺式-1，4-聚异戊二烯，工业上通常以烟片和绉片的形式得到。也可以使用合成聚异戊二烯。
除了上述单一烯烃类橡胶以外，还可使用它们的共混物。
在制备本发明组合物时，烯烃类橡胶的用量通常占橡胶和聚烯烃总重的约90％wt至约10％wt，优选约40％wt至约10％wt。
酯增塑剂
本发明组合物中，某些低至中等分子量(＜10,000)的有机酯或烷基醚酯的加入，显著降低了聚烯烃组分、橡胶组分和整个组合物的Tg，并改进了低温性能，特别是柔软性和强度。这可能是由于该酯配分入组合物的聚烯烃和橡胶组分中而引起的。特别适宜的酯包括单体酯和平均分子量低于约2000、优选低于约600的低聚酯。该酯与组合物的聚烯烃和橡胶组分都是相容的或可混溶的，即它可与其它组分混合成单一相是非常重要的。最适宜的酯或是脂肪单酯或双酯，或是低聚脂肪酯或烷基醚酯。聚合脂肪酯及芳酯不太有效，磷酸脂效果最差。
通过简单地试验酯溶胀聚烯烃如聚丙烯的能力，鉴定它们的适用性。在本发明实践中，将聚丙烯样品(2.0×20×50mm)浸于各种酯增塑剂或非酯稀释剂如矿物油中，在125℃下溶胀(通常约24小时)，并测定其重量，如果重量的总增量大于40％，则认为该稀释剂与聚丙烯很好地相容，因而适于制备改进低温性能的组合物。
适用于本发明的酯的例子包括树脂酸异辛酯、油酸异辛酯、树脂酸正丁酯、油酸正丁酯、油酸丁氧基乙酯、癸二酸二辛酯、癸二酸二(2-乙基己酯)、壬二酸二辛酯、十二烷二酸二异辛酯、戊二酸烷基醚二酯及其低聚物。预计可用于本发明的其它类似物包括：单己二酸和双己二酸的烷醚酯，己二酸、戊二酸、癸二酸、壬二酸的单烷酯和双烷酯，蓖麻油或妥尔油的酯衍生物，以及用它们制得的低聚单酯和双酯、或单烷醚酯和双烷醚酯。特别优选树脂酸异辛酯和树脂酸正丁酯。这些酯可在组合物中单独使用，或不同的酯混合使用，或者与传统烃油稀释剂或操作油如石蜡油一起使用。组合物中，酯增塑剂的量通常低于约250phr，优选低于约低于175phr。
添加剂
除了组分聚烯烃、橡胶和酯以外，本发明组合物还包括固化剂，还可能包括增强或非增强填料、抗氧化剂、稳定剂、橡胶操作油、增量油、润滑剂、防粘连试剂、抗静电剂、蜡、发泡剂、颜料、阻燃剂和橡胶共混领域已知的其它加工助剂。这些添加剂的量至多占组合物总量的50％wt。可使用的填料和增量剂包括传统无机物，如碳酸钙、粘土、二氧化硅、滑石、二氧化钛、炭黑等。橡胶操作油通常为得自石油馏分的链烷烃、环烷烃或芳烃油。操作油的种类根据组合物中具体的橡胶或橡胶混合物而定，其用量以橡胶总量计为0至几百phr。但是，本发明的重要之处在于，组合物中不需要操作油，实际上它可完全被组合物中的酯增塑剂组分代替。换言之，根据本发明热塑性弹性体所希望的性能，该组合物中可以不含操作油，或者含有操作油与酯的组合物。
加工方法
虽然根据橡胶组分与塑料组分的相对量、橡胶的硫化系统或硫化程度，两种组分也可能呈共连续相或者换相，但是通常是烯烃类橡胶组分作为小颗粒即微粒分散于连续的聚烯烃母体中。希望橡胶至少部分交联，并优选完全或彻底交联。通过向聚烯烃与橡胶的共混物中加入适宜的橡胶硫化剂，并在传统硫化条件下使橡胶硫化至希望的程度，可以使橡胶部分或完全交联。但是，优选用动态硫化方法使橡胶交联。在本说明书和权利要求书中，″动态硫化″指含于热塑性弹性体组合物中的橡胶的一种硫化或固化方法，即，在高剪切、温度高于聚烯烃组分熔点的条件下，使橡胶硫化。这样，橡胶在交联的同时即呈微粒分散于聚烯烃母体中，但也可以呈上述其它形态。在升高的温度下，在传统混合装置如辊炼机、Banbury混合机、Brabender混合机、连续混合机、混合挤出机等中，将热塑性弹性体的组分混合，进行动态硫化。动态硫化组合物的独到之处在于，无论橡胶组分是部分硫化还是完全硫化，都可以用传统塑料加工方法如挤出、注塑成型和压缩成型加工和再加工该组合物。切屑和边皮可以回收和再加工。
进行橡胶硫化时，需要的硫化系统的适宜用量、类型及硫化条件对本领域普通技术人员是已知的。采用不同的硫化剂量、温度和硫化时间使橡胶硫化，以达到最适交联度。只要在硫化条件下适用于所用的烯烃类橡胶或橡胶组合物及聚烯烃，任意已知的橡胶固化系统均可使用。这些硫化剂包括硫、硫给体、金属氧化物、树脂系统、基于过氧化物的系统等，用和不用促进剂与助剂都可以。这些硫化系统在弹性体硫化领域是熟知的，
在本说明书和权利要求书中，所用术语″彻底硫化″和″完全硫化″意指被硫化的橡胶组分硫化至这样的程度，即交联橡胶的弹性性能类似于其在传统硫化状态(不在热塑性弹性体组合物中)时的性能。硫化程度可用胶凝量或用与之相对应的可提取成分量表示。另外，硫化程度也可以用交联密度表示。所有这些是本领域已知的，例如在美国专利Nos.5,100,947和5,157,081(通过引用，并入本文)中。
如下实施例所示，用下述概述方法制备本发明热塑性弹性体。将聚烯烃和橡胶与适量酯和其它需要的添加剂一起放入加热密闭式混合机中。该混合物加热至足以熔化聚烯烃组分的温度，素炼该混合物并在素炼时加入硫化剂。搅拌力矩最大、表明硫化已发生后，补加酯，继续搅拌，直至达到希望的硫化度。可以改变各种组分的加料顺序。然后从混合机中取出组合物，成型，测试它们的物理性能。
下面非限定性的实施例进一步说明本发明。
实施例1
用上述溶胀试验筛选稀释剂以后，制备组合物，以证明热塑性弹性体中含有某些酯的影响(与矿物油相比)。将橡胶、塑料、酚醛类硫化剂和添加剂在容积为65～80cm3、搅拌速率为100rpm、温度为120～190℃的电加热Brabender混合机中共混。聚烯烃组分熔化以前，向共混物中加入一种Lewis酸，并继续搅拌。发现温度随时间而变化，在约185℃发生硫化时，搅拌力矩迅速增加。力矩相对恒定时，停止搅拌。从混合机中取出组合物，在190℃下成片以测量物理性能。
确定增塑剂改进热塑性弹性体低温性能之效率的关键性能是橡胶组分和塑料组分的Tg。使用Rheometrics RDAII动态力学分光计(使用扭转型)测定Tg。动态应变为0.5％，使用了自应变功能(autostrain feature)；频率为10Hz。
参比共混物″A″不含酯增塑剂，其组成如下：
       组分                ％                 phr
EPDM(Vistalon 8600)        25.71              100
等规聚丙烯                 56.34              219.10
填料：
     活性炭(40％)          4.96               19.28
     粘土                  10.29              40.00
硫化剂                     2.70               10.50
其它共混物含有酯增塑剂或传统操作油，组合物B的组成如下：
       组分                ％                 phr
EPDM(Vistalon 8600)        19.28              100
等规聚丙烯                 42.22              219.10
填料：
     活性炭(40％)          3.72               19.28
     粘土                  7.71               40.00
硫化剂                     2.03               10.50
油/酯增塑剂                25.05              130
组合物的Tg列于表1。用上述溶胀实验选择油和增塑剂。
                表I共混物     油/酯                     橡胶Tg，℃      塑料Tg，℃A          无                            -41            +10B1         Amoco Rycon润滑酯             -47            -1B2         Sunpar 150M石蜡油             -46            -5B3         Parapol 750聚丁烯             -47            -5B4         Cyclolube 213环烷油           -48            -5B5         Cyclolube 4053环烷油          -50            -5B6         Cyclolube 410环烷油           -51            -5B7         Amoco 9012聚丙烯              -45            -10B8         戊二酸烷醚烷二酯(Plasthall    -55            -11
       7041)B9         十二烷二酸二异辛酯(Plasthall  -56            -14
       D10DD)B10       壬二酸二辛酯(Plasthall DOZ)    -60            -22B11       癸二酸二辛酯(Plasthall DOS)    -60            -18B12       油酸丁氧基乙酯(Plasthall 325)  -66            -20B13       油酸正丁酯(Plasthall 914)      -71            -24B14       树脂酸正丁酯(Plasthall 503)    -70            -24B15       树脂酸异辛酯(Plasthall 100)    -75            -26
表中的商品名的组成及生产厂商如下所述：Amoco Rycon润滑酯是一种加有聚脲增稠剂的重质石蜡烃馏分，由Amoco Corporation生产；Sunpar 150M是一种石蜡油，由Sun Chemical Company生产；Parapol 750是一种很低分子量的异丁烯聚合物，由Exxon Chemical Company生产；Cyclolube系列产品均是环烷油，由Witco Chemical Company生产；Plasthall系列产品是C.P.Hall Company生产的各种酯增塑剂，具体化学组成见表I。
上述结果表明，与传统操作油和润滑油相比，向动态硫化的热塑性弹性体中加入有机烷酯和烷基醚酯，显著降低了橡胶组分和塑料组分的Tg。
实施例2
将含有高分子量(聚合)酯增塑剂的组合物与本发明组合物比较，以证明聚合酯不能很有效地降低Tg。除了酯增塑剂的量是70phr以外，采用与组合物″B″相同的组成，按实施例1的方法制备共混物。
                 表2共混物    酯增塑剂    平均分子量   橡胶的Tg(℃)  塑料的Tg(℃)B16       树脂酸正丁酯       ＜400      -65          -15B17       聚(己二酸酯)        6000      -41          +5
      (ParaplexR G-40，由C.P.Hall Company生产)A         无                            -41          +10
很明显，与单体酯如树脂酸正丁酯相比，聚合酯不能降低热塑性弹性体中橡胶组分和塑料组分的Tg至同样的程度。这与单体酯的混合结合熵增加较大有关。这样，用单体酯时，有大的负混合自由能，这有利于混溶，而聚合酯时没有这么大。因而，本实施例说明了稀释剂分子量和可混溶性对其最佳效果的重要性。
实施例3
按实施例1，根据组合物″B″制备共混物，其中，向热塑性弹性体中加入低分子量酯与石蜡油的组合物，并测定Tg。
                表3
共混物      石蜡油        树脂酸正        橡胶的       塑料的
            (phr)         丁酯(phr)       Tg(℃)       Tg(℃)
A              0              0             -41         +10
B18            0              130           -74         -24
B19            30             100           -70         -20
B20            60             70            -60         -14
B21            70             60            -60         -14
B22            100            30            -55         -16
B2             130            0             -46         -5
稀释剂总量一定时(在本实验中，增塑剂和/或油为130phr)，可以使酯增剂与适量橡胶操作油混合使用，以控制Tg的降低。不同酯的混合物也可以与油一起使用。
实施例4
研究低分子量酯的加入对热塑性弹性体冲击强度的影响，并与传统操作油比较。使用1300cm3 Banbury混合机，根据组合物″A″和指明的添加剂(phr)，制备共混物。按照ASTM D256-84规定的方法，使用厚度为3.17mm模压片的切片样品，测定每个组合物在-40℃的缺口伊佐德抗冲击强度。
               表4
共混物                A1    A2    A3    A4    A5    A6    A7
碳黑(N326)            0     100   0     0     100   0     0
二氧化硅(Hisil233)    0     0     100   0     0     100   0
树脂酸正丁酯          0     0     0     130   130   130   0
石蜡油(Sunpar150M)    130   130   130   0     0     0     0
树脂酸异辛酯          0     0     0     0     0     0     100
硬度(Shore D)         38    38    36    37    37    36    35
缺口伊佐德冲击        82    76    93    414   489   424   427
强度(J/m±G)          ±48  ±35  ±52  ±48  ±40  ±32  ±47
注：Hisil 233是由PPG Chemicals生产的一种二氧化硅。
可以发现以烷基单酯代替石蜡油，可以大大改进在-40℃下的韧性，至少增加4倍。这些组合物比用烃操作油制备的组合物柔韧得多，并且提高了低温下抗断裂性能。
实施例5
改变酯增塑剂的加入时机，按照实施例1的方法制备组合物。采用组合物″A″，按下列方式加入树脂酸正丁酯增塑剂(130phr)。
组合物″C″—全部增塑剂在EPDM橡胶在聚丙烯中动态硫化之前加入。
组合物″D″—动态硫化之前加入一半增塑剂(65phr)，动态硫化之后加入一半增塑剂。
组合物″E″—全部增塑剂在动态硫化之后加入。
测定组合物的Tg和物理性能，并列于下表。
               表5
                      C          D         E
EPDM相的Tg℃         -76         -        -71
聚丙烯相的Tg，℃     -20         -        -25
密度，gm/cm3        0.952       0.952    0.953
(ASTM D297)
断裂应力，MPa        13.40       13.24    11.64
(ASTM D412)
断裂应变，％         372         316      249
(ASTM D412)
压缩变形，2hr/       72          -        66
100℃，％(ASTM
D395B)
重量变化，24hr/      59          -        51
125℃，AST-
M3，％(ASTM
D471)
ACR粘度，泊          1389        1286     872
上述结果表明，热塑性弹性体的性能可通过改变增塑剂的加入时机(相对于固化步骤)而改变。
实施例6
使用两个不同的酯增塑剂、一个传统橡胶操作油和一个酯和操作油的混合物，按照实施例1的方法，制备基于丁基橡胶和聚丙烯的热塑性弹性体。在这次实验中，约90％的稀释剂在硫化前加入。表6给出其组成(phr)及物理性能。
除了降低Tg和改进低温性能以外，应注意到，如测量的23℃的损耗角正切所示，本发明组合物还改进(降低)了阻尼性能。相反，使用操作油提高了23℃下的损耗角正切。
                      表6组合物         E       G       H        I       J丁基橡胶       100     100     100      100     100(PolysarButyl301，由Bayer公司生产)聚丙烯         20      20      20       20      20(AristechFP200F，由Aristech Corp.生产)聚丙烯(Rex-    180     180     180      180     180ene 51S07A，由Equistar Chemicals，LP生产)树脂酸异辛酯   100     0       50       0       0(PlasthallP100)树脂酸正丁酯   0       0       0        100     0(PlasthallP503)石蜡油(Sun-    0       100     50       0       0par 150M)硫化系统1     11      11      11       11      11硬脂酸         1       1       1        1       1活性炭40％     20      20      20       20      20丁基橡胶相     -76     -52     -57      -75     -56Tg，℃聚丙烯相       -22     0       -16      -25     +10Tg，℃损耗角正切     0.0537  0.0800  0.0581   0.0386  0.063823℃硬度(Shore     36      37      35       34      51D)2断裂应力，     10.0    12.1    11.4     9.6     16.6MPa断裂应变，％3 246     308     282      258     593撕裂强度，     54      66      60       54      -KJ/m24压缩变形(22    72      60      61       79      78小时/125℃)重量变化，％   62      46      51       58      91(ASTM3，24小时/125℃)1酚醛树脂(5phr)，SnCl2(1phr)，氧化锌(5phr)2ASTM D22403ASTM D4123ASTM D624实施例7
研究酯的浓度对RPDM橡胶—聚丙烯热塑性弹性体的Tg及物理性能的影响。使用组合物″A″，并根据实施例1的方法。组合物中树脂酸正丁酯的浓度为0～219phr，结果列于表7。
                         表7组合物      A     A8     A9     A10     A11     A12     A13树脂酸正    0     15     30     70      100     130     219丁酯(phr)橡胶相      -41   -50    -55    -65     -70     -74     -75Tg，℃聚丙烯      +10   +4.6   -4.8   -15     -16     -24     -25Tg，℃硬  度      58    50     49     42      38      37      27(ShoreD)100％模     16.2  16.2   15.0   11.7    15.5    11.6    6.5量，MPa断裂应      22.3  22.9   17.7   18.5    21.1    14.3    6.6力，MPa断裂应      467   442    334    493     452     345     110变，％重量增      61    58     55     55      47      45      27量％(24hr/125℃，ASTM3)压缩变      -     62     63     64      66      63      59形％22hr/100℃)
可见，几乎在所有的酯浓度范围内，都可有效地降低Tg。
实施例8
按照实施例1的方法，使用20升Banbury混合机搅拌，制备含有天然橡胶、EPDM橡胶或充油EDPM橡胶的软(低模量)热塑性弹性体。测量酯增塑剂对Tg、磨擦系数及物理性能的影响。结果列于表8A。组成的浓度单位为phr。
                  表8A组合物     K       L      M      N      O      P      O橡胶相     -50     -60    -76    -35    -55    -77    -51Tg，℃硬度       54      53     53     85     67     64     85(ShoreA)100％应    1.8     1.7    1.5    5.9    2.7    2.5    4.5变应力，MPa断裂应     4.89    4.17   1.90   7.33   4.86   4.50   4.46力，MPa断裂应     347     347    270    184    257    219    178变，％重量增     87      109    -      204    123    121    200量，％(24hr/125℃，ASTM3)与聚丙烯的摩擦系数静态       1.80    1.54   1.07   1.53   1.00   1.13   1.40动态       1.62    1.66   1.19   1.55   1.08   1.33   1.22`
                      表8组合物      K     L     M     N     O      P      Q充油        200   200   0     0     0      0      0EPDM1天然橡      0     0     0     0     100    100    100胶2EPDM        0     0     100   100   0      0      0橡胶3粘土        43.46 43.46 43.46 43.46 0      0      0无机填料    0     0     0     0     50     50     50氧化锌      1.98  1.98  1.98  1.98  5      5      5硬脂酸      0     0     0     0     1      1      1聚丙烯      24    24    40    40    0      0      0A4聚丙烯      7     7     7     7     0      0      0B5聚丙烯      0     0     0     0     46.8   46.8   46.8C6石蜡油7    50    0     0     0     97.5   0      0树脂酸异    0     50    150   0     0      97.5   0辛酯颜料浓缩    3.25  3.25  3.25  3.25  3.25   3.25   3.25物8固化剂      4     4     4     4     0      0      0A9固化剂      0     0     0     0     11.7   11.7   11.7B10SnCl2      1.68  1.68  1.68  1.68  0      0      0抗氧化      0     0     0     0     1      1      1剂11 1Epsyn P597橡胶，用100份石蜡油增量
 (Copolymer Rubber & Chemical Co.)2CV60天然橡胶，Mooney 60(Golden Hope Plantations)3Vistalon 8600(Exxon Chemical Co.)4Rexene聚丙烯(Rexene Corp.)5Aristech FP100F(Aristech Corp.)6Aristech D008M(Aristech Corp.)7Sunpar 150(Sun Chemical)8Americhem 21065 R-19SP-1045(Schenectady International Inc.)10HRJ 10518(一种酚醛树脂，Schenectady International Inc.)11Irganox 1010(General Electric Co.)
从实施例8可见，本发明热塑性弹性体在保持其它优良物理性质的同时，显著降低了Tg。
上述实施例只是给出本发明的最佳及优选实施方案，但不限制本发明的范围，其范围由随后的权利要求书限定。

Claims (12)

1.一种热塑性弹性体组合物，它包括：
(a).以聚烯烃均聚物或共聚物与烯烃类橡胶的总重量为基准计，10～90％重量的热塑性结晶聚烯烃均聚物或共聚物；
(b).以聚烯烃均聚物或共聚物与烯烃类橡胶的总重量为基准计，90～10％重量的烯烃类橡胶，所述橡胶选自乙烯、丙烯和非共轭二烯的三元共聚物橡胶、乙烯-丙烯共聚物橡胶、丁基橡胶、卤化丁基橡胶、异单烯烃与对-烷基苯乙烯的共聚物、天然橡胶、聚异戊二烯及其混合物；和
(c).基于每100重量份所述橡胶，1～250重量份的可与聚烯烃和橡胶都相容的低分子量酯或醚酯增塑剂；
其中，所述橡胶至少部分交联。
2.权利要求1的组合物，其中所述聚烯烃是C2-C6单体或共聚单体的聚合物。
3.权利要求1的组合物，其中，所述酯增塑剂的分子量不大于2000。
4.权利要求1的组合物，其中，所述增塑剂选自烷单酯或双醚或其低聚物、烷醚单酯或双酯或其低聚物。
5.权利要求1的组合物，其中所述橡胶是完全交联的。
6.一种热塑性弹性体的制备方法，它包括：
(a).在高于聚烯烃熔点的温度下，将90％～10％重量烯烃类橡胶与10％～90％重量热塑性结晶聚烯烃均聚物或共聚物共混，所述橡胶选自乙烯、丙烯和非共轭二烯的三元共聚物橡胶、乙烯-丙烯共聚物橡胶、丁基橡胶、卤化丁基橡胶、异单烯烃与对-烷基苯乙烯的共聚物、天然橡胶、聚异戊二烯及其混合物，所述重量百分数以聚烯烃均聚物或共聚物与烯烃类橡胶的总重量为基准计；
(b).基于每100重量份所述橡胶，向共混物中加入1～250重量份的可与橡胶和聚烯烃都相容的低分子量酯或醚酯增塑剂；和
(c).在所得混合物中，使橡胶交联。
7.权利要求6的方法，其中所述聚烯烃是C2-C6单体或共聚单体的聚合物。
8.权利要求6的方法，其中，所述增塑剂的分子量不大于2000。
9.权利要求6的方法，其中，所述增塑剂选自烷单酯或双酯或其低聚物、烷醚单酯或双酯或其低聚物。
10.权利要求6的方法，其中，所述橡胶在步骤(c)中完全交联。
11.权利要求1的组合物，其中，所述增塑剂为脂肪酯或醚酯。
12.权利要求1的组合物，其中，所述增塑剂选自十二烷二酸二异辛酯、癸二酸二辛酯、油酸丁氧基乙酯、油酸正丁酯、树脂酸正丁酯、油酸异辛酯、树脂酸异辛酯和壬二酸二辛酯。
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EP0621308B1 (en) 1997-06-25
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EP0621308A2 (en) 1994-10-26
KR100301925B1 (ko) 2001-10-22
US5290886A (en) 1994-03-01
US6326426B1 (en) 2001-12-04
BR9400646A (pt) 1994-11-22
JPH06306217A (ja) 1994-11-01
CA2112173A1 (en) 1994-10-21
JP3354686B2 (ja) 2002-12-09
EP0621308A3 (en) 1995-03-01
DE69403931T2 (de) 1998-01-15
US5397832A (en) 1995-03-14
CN1094070A (zh) 1994-10-26
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ES2103517T3 (es) 1997-09-16
AU5932094A (en) 1994-10-27

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