CN1045977C - 凝胶体 - Google Patents

凝胶体 Download PDF

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CN1045977C
CN1045977C CN92110281A CN92110281A CN1045977C CN 1045977 C CN1045977 C CN 1045977C CN 92110281 A CN92110281 A CN 92110281A CN 92110281 A CN92110281 A CN 92110281A CN 1045977 C CN1045977 C CN 1045977C
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J·M·赫德森
H·格劳勒斯
A·C·尼克松
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Rey Chemical Co ltd
Raychem Ltd
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Abstract

在压力下通过掺入苯乙烯-弹性体二嵌段共聚物，使这样一种凝胶具有阻油渗出的作用，其中该凝胶包括100份苯乙烯-弹性体-苯乙烯三嵌段共聚物以及大于300份能软化和增量该弹性体中链段共聚物的一种油。优选的三嵌段物是苯乙烯-乙烯/丁烯-苯乙烯，以及优选的二嵌段物是苯乙烯-乙烯/丙烯。还公开了用这类凝胶作为在压力下用来固定该凝胶的电连接线外壳的密封胶。

Description

凝胶体
本发明涉及一种凝胶组合物，特别是涉及一种柔软的、抗高温坍落的弹性凝胶组合物，该组合物指的是一种液体增量的聚合物组合物，其针入度在100-400(最好是100-350)10-1mm(用改进型ASTM D217测定，见国际专利WO 8800603(RK308)，其公开的内容编列于此以供参考)；极限伸长大于100％，明显的弹性变形(即基本上无滞后变形)达到至少100％的伸长率(用ASTM D412，WO 8800603所述的测定)；极限抗张强度小于1兆帕(WO 8800603所述的改进ASTM D412)；动态储能模量小于50000帕(WO 8800603所述的)；在120℃(较好是150℃，最好是180℃)以下的温度时无明显坍落现象。该组合物既可含有一种交联分子链(凝胶)的三维网络，又可仅仅在性能上好象含有该网络一样(准凝胶)，这两者都包含在下文“凝胶”用语之中。
本发明更加具体地涉及这样的凝胶组合物，该组合物包括一个苯乙烯-弹性链段-苯乙烯三嵌段共聚物，最好是一种有较硬的聚苯乙烯端链段和较有弹性的(最好是氢化橡胶)中链段的苯乙烯-烯烃基-苯乙烯嵌段共聚物。这类共聚物的实例包括：聚苯乙烯-聚丁二烯-聚苯乙烯(SBS)和聚苯乙烯-聚(乙烯/丁烯)-聚苯乙烯(SEBS)三嵌段共聚物。
本发明涉及的这类柔软、抗坍落的弹性三嵌段共聚物凝胶在下文中为简便起见叫做“S-凝胶”，尤其非常适合于电连接线外壳的可反复密封。这类S-凝胶的实例在WO 90/05166(RK 403)中有所描述。
在使用中，使这类凝胶在压力下粘合往往是可行的。在实验室中借助向15mm直径的凝胶圆盘施加50KPa压力来合理地模拟在实践中承受的压力。我们已发现，在这样的压力下，每100重量份胶凝嵌段共聚物含大于400重量份，特别是大于500重量份增量液(即小于20％，特别是小于16.79％共聚物)的S-凝胶往往会渗出增量液而劣化。在较高的压力下，每100重量份这类嵌段共聚物含有300重量份增量液的凝胶也会渗出增量液。共聚物含量高的凝胶受这种渗出的影响较小，但对许多实际应用来说，共聚物含量高的凝胶往往太硬。本发明在没有不合格地改变凝胶其它性能的情况下减少这种渗出，而且还减少增粘剂的添加量。这种增粘剂的例子有氢化苯乙烯增粘树脂或液态聚丁烯或液态聚异戊二烯的增粘剂。
因此，本发明提供一种凝胶组合物，该组合物含有：
(a)一种苯乙烯-弹性链段-苯乙烯三嵌段共聚物(T)；
(b)一种硬链段-弹性链段双嵌段共聚物(D)，其弹性链段与增量液E(说明如下)是相容的，D的含量足以使加压使用时，组合物的渗出液E至少减少10％；
(c)每100重量份的T＋D含有大于300，较好是大于400，最好是至少500重量份的增量液(E)，该增量液使T和D的弹性链段增量和软化。
该组合物的T含量，按全部组合物计大于3.1％(重量)，和/或该组合物的附加的氢化苯乙烯增粘树脂，特别是某些附加的增粘剂的含量，按全部组合物计小于20％(重量)。
本组合物通常具有，或者通过简单的逐次逼近法具有下列性能参数：针入度100-400(较好是100-350)10-1mm，极限伸长大于100％，明显的弹性变形达到至少100％的伸长率；极限抗张强度小于1兆帕；动态储能模量小于50000帕；在120℃以下温度时无明显坍落现象。
D∶T的重量比最好是5∶9 5-6 6∶3 4。三嵌段共聚物(T)的重均分子量(Mw)较好是至少120000，更好是至少150000，最好是至少180000，虽然对D的重均分子量(Mw)要求不如对T的严格，但是双嵌段共聚物(D)的Mw最好是100000-200000。Mw的测定法见上述的WO 90/05166。
在每100重量份的T＋D含有至少600，或至少900，或至少1300重量份的E的凝胶中双嵌段添加剂D的效益最为明显。
只要T和D的总量不大于组合物总量的25％，更好是20％(重量)，最好不大于16.7％(重量)，则D的含量最好占组合物总量的16.5％，最好是13％(重量)以下，而T的含量最好占组合物总量的23.75％，最好是19％(重量)以下。D的含量应足以使渗出物E至少减少20％，较好是至少25％，更好是至少35％，最好是至少50％。T和D加在一起最好基本上构成凝胶的全部聚合物含量。
D的硬链段和弹性链段应分另与T的硬链段和弹性链段相容，更好是分别与T的硬链段和弹性链段同一种类的重复单元。D的硬链段最好含有聚苯乙烯，T和D的一方或双方的弹性链段较好是含有聚烯烃链段，更好是聚(乙烯/丁烯)(供T用)或聚(乙烯/丙烯)(供D用)。优先选择D包括少于50％，较好小于40％，而最好小于20到39％(重量)的硬链段。优先选择T包括29到35％、更好是30或31到33％(重量)的聚苯乙烯链段。
由于提高了增量液E的渗出阻力，本发明的凝胶组合物完全适合于用在各种装置中，该装置包括一种电线，电缆或引线接线的外壳，一种凝胶组合物主体，和凝胶组合物主体夹持器，该夹持器使凝胶组合物主体在压力下紧贴并围绕着电线、电缆或引线等，使接线外壳密封和/或保护电线、电缆或引线等免受污染或腐蚀。为此目的，在安装该装置时为了在外壳上插入可以把凝胶组合物主体夹持在一种插壳中。这类装置的实例在前面提到的WO 90/05166和在WO90/05401(B161)中有所描述，其公开的内容编列于此以供参考。这类装置能够用其带有的一个或几个凝胶组合物主体围绕的一个物体进行闭合，排列凝胶主体形成凝胶-凝胶表面接触，当这种闭合时形成一种凝胶-凝胶密封，当闭合再次启通时，密封就在接触表面分开。
本发明还包括使用该凝胶组合物围绕一个物体，或在第一物体和第二物体之间形成一种密封，例如可用于防腐蚀或环境保护，最好使该凝胶组合物在压力下形成密封；本发明包括一种围绕一个物体密封一种外壳的方法，该方法包括：
(a)准备一个敞口的带有一个凝胶组合物主体的外壳构件，
(b)围绕该物体放置该外壳构件，并闭合该外壳构件，从而
(c)使一部分凝胶主体与另一部分凝胶主体，或者使一部分凝胶主体与外壳构件带有的一部分别的这种凝胶主体，或者使一部分凝胶主体与上述物体进行密封表面接触，
(d)夹紧该外壳构件，最好是在压力下将该凝胶组合物夹持在该密封接触中。
三嵌段共聚物T，除了D的其它材料，和凝胶组合物的一般性能最好是如前面提到的WO 90/05166中所述的那样，虽然一种重均分子量Mw比WO 90/05166中优选的稍低的共聚物T对某些用途说来是令人满意的。
增量剂可以是WO 90/05166中所述的那样，最好是一种基本上非芳香性的石蜡/环烷矿物油，其石蜡∶环烷的碳原子比是1.75∶1-5∶1，较好是1.77∶1-3∶1，更好是1.9∶1-2.7∶1，最好是2.2∶1-2.5∶1。
WO 90/05166中指出的那些配方的改性方法是用大量本发明的双嵌段D来替换其中列举的一部分三嵌段共聚物。该双嵌段D的添加通常会增强凝胶的粘着性，从而减少增粘剂的添加量。如果需要仍可使用WO 90/05166中所述的增粘剂，以进一步增强粘着性。附加增粘剂的用量应小于组合物总量的20％(重量)，更好是小于15％(重量)，最好是小于10％(重量)，或尽可能基本上0％(重量)。
可以添加例如组合物总量的10％以下的填充剂以改进其加工性能，合适的填充剂实例通过简单的逐次逼近法不费力地加以选定。可以使用前面提到的WO 88/00603和WO 91/05014(BK373)中所述的其它添加剂以提高高温性能和耐增塑剂能力。
双嵌段D的弹性链段必须与增量剂E相容，最好全部溶解在E中，或至少靠E而增量和软化。共聚物D应选择为基本上非迁移性的，与不合乎需要的低Mw物料的渗出对抗。这意味着弹性体链长足以保证靠链的缠结使D保留在组合物中，或意味着T和D之间的硬链段亲合力。
D在用于这类凝胶组合物的操作条件下优选地有熔融加工性，与等量的只由共聚物T形成的凝胶比较，向组合物中加入D优选地不提高，或者甚至会降低0.1Hz下测得的模量。优选的材料是带有与增量油相容链段的双嵌段共聚物。其实例包括聚苯乙烯-聚异戊二烯，聚苯乙烯-聚丁二烯〔例如聚苯乙烯含量为25％、30％或48％(重量)〕，聚苯乙烯-聚(乙烯/丁烯)，聚苯乙烯-聚(乙烯/丙烯)。在长期热稳定性方面，最好是各种氢化型〔聚苯乙烯-聚(乙烯/丁烯)或聚苯乙烯-聚(乙烯/丙烯)〕。
下列各实施例是基12％的T(硬S-凝胶)或7％的T(软S-凝胶)，并且用大量双嵌段D替换部分T。
                     材料SEBS三嵌段：             Shell Kraton G 1651
                     聚苯乙烯-聚(乙烯/丁烯)-聚苯乙烯
                     苯乙烯含量33％S-EP双嵌段1：            Shell Kraton G 1701 X
                     聚苯乙烯-聚(乙烯/丙烯)
                     苯乙烯含量37％S-EP双嵌段2：            Shell Kraton G 1702 X
                     聚苯乙烯-聚(乙烯/丙烯)
                     苯乙烯含量28％矿物油：                 FINA Vestan A 360 B
                     白石蜡油
                     粒度223mm2/秒(20℃)
                     比重0.863(20℃)抗氧化剂#1:Irganox 1010(Ciba-Geigy)抗氧化剂#2:Irganox 1076(Ciba-Geigy)UV稳定剂： Tinuvin 327(Ciba-Geigy)
               加工
全部凝胶用一个曲拐式搅拌机制造，将上述组分在195-200℃真空下搅拌50分钟。
TMA软化点(Ts)和动态储能模量(G1)是按前面提到的WO 8800603所述的方法测定的，只是该模量在0.1Hz下测定以更紧密地接近实际的最终使用条件。
增量剂的渗出：试样是凝胶圆盘(15mm直径×5mm厚度)，固定在15mm直径金属块镗孔里。每个圆盘的下表面固定在细网眼上，为增量剂损耗提供自由表面。用一个加载活塞向上表面施加一个50KPa的恒定压力。整个装置放在一个60℃的烘箱中，监控各圆盘随时间的失重。列出的M(亲合力)值是平衡时的增量剂损失质量，用原质量的百分率来表示。
A硬S-凝胶
Ⅰ对照物 II III IV V VI VII
S-EB-S三嵌段(T) 12 11 10.5 10 10.7 9.75 8.6
S-EP双嵌段(D) 0 4(G1701) 6(G1701) 8(G1701) 4(G1702) 6(G1702) 8(G1702)
矿物油 86.38 83.38 81.88 80.38 83.68 82.63 81.78
抗氧化剂1 0.12 0.12 0.12 0.12 0.12 0.12 0.12
抗氧化剂2 1.0 1.0 1.0 1.0 1.0 1.0 1.0
UV稳定剂 0.5 0.5 0.5 0.5 0.5 0.5 0.5
性能
           I          II          III          IV           V             VI           VII
G′@0.1Hz(kPa) 6.5 7.3 7.2 6.7 7.5 6.7 6.4
Ts(℃) 128 119 115 116 125 127 117
M下限(％) 28 12 5 1 10.5 6.5 3.5
B    软S-凝胶
 I对照物 II III IV V VI
S-EB-S三嵌段(T) 7 7 6.5 6.5 6 5.67
S-EP双嵌段(D) 0 2(G1702) 4(G1702) 2(G1701) 4(G1701) 2(G1701)
矿物油 91.38 89.38 87.88 89.88 88.38 90.71
抗氧化剂1 0.12 0.12 0.12 0.12 0.12 0.12
抗氧化剂2 1.0 1.0 1.0 1.0 1.0 1.0
UV稳定剂 0.5 0.5 0.5 0.5 0.5 0.5
性能
            I           II          III          IV          V           VI
G′0.1Hz(kPa) 2.0 2.0 2.1 1.9 2.0 1.6
Ts(℃) 117 109 105 103 111 104
M下限(％) 65 44 38 46 41 48

Claims (20)

1.一种凝胶组合物，该组合物含有：(a)一种苯乙烯-弹性链段-苯乙烯三嵌段共聚物T；(b)一种硬链段-弹性链段双嵌段共聚物D，其弹性链段与增量液E是相容的，D的含量足以使加压使用时，组合物中渗出的E至少减少10％；(c)每100重量份的T＋D含有大于300重量份的增量液E，该增量液使T和D的弹性链段增量和软化，该组合物的T含量，按全部组合物计大于3.1重量％，和/或该组合物的附加的氢化苯乙烯增粘树脂，或某些附加的增粘剂的含量，按全部组合物计小于20重量％。
2.按照权利要求1所述的凝胶组合物，其中该组合物的针入度为100-400 10-1mm；极限伸长大于100％，明显的弹性变形达到至少100％伸长率；极限抗张强度小于1兆帕；动态储能模量小于50000帕；在120℃以下的温度无明显坍落现象。
3.按照权利要求1或2所述的凝胶组合物，其中该组合物中附加的增粘剂含量小于15重量％，或者基本上不含增粘剂。
4.按照权利要求1或2所述的凝胶组合物，其中D∶T的重量比是5∶95-66∶34。
5.按照权利要求1或2所述的凝胶组合物，其中T的重均分子量Mw是至少120,000；和/或D的Mw是100,000-200,000。
6.按照权利要求1或2所述的凝胶组合物，其中D的含量足以使渗出的E减少至少20重量％。
7.按照权利要求1或2所述的凝胶组合物，其中T和D构成凝胶的全部聚合物含量。
8.按照权利要求1或2所述的凝胶组合物，其中该组合物每100重量份的T＋D含有至少600重量份的E。
9.按照权利要求1或2所述的凝胶组合物，其中增量液E基本上是非芳香性的石蜡/环烷矿物油，其石蜡∶环烷的碳原子比是1.75∶1-5∶1。
10.按照权利要求1或2所述的凝胶组合物，其中D的含量占全部组合物的16.5重量％以下，和/或T的含量占全部组合物的23.75重量％以下，只要T和D的总量不大于全部组合物的25重量％。
11.按照权利要求1或2所述的凝胶组合物，其中D的硬链段与T的聚苯乙烯链段是相容的。
12.按照权利要求1或2所述的凝胶组合物，其中D的弹性链段是与T的弹性链段相容的。
13.按照权利要求1或2所述的凝胶组合物，其中T的弹性链段和/或D的弹性链段含有聚烯烃基链段。
14.按照权利要求1或2所述的凝胶组合物，其中D包括少于50重量％的硬链段。
15.按照权利要求1或2所述的凝胶组合物，其中T包括29-35重量％的聚苯乙烯链段。
16.按照权利要求1或2的凝胶组合物的应用，所述应用是使该组合物围绕一个物体，或在第一物体和第二物体之间形成一种密封。
17.按照权利要求16所述的应用，其中凝胶组合物是在压力下形成密封的。
18.按照权利要求16所述的应用，所述应用是在一种装置中密封电线、电缆或引线外壳，和/或保护电线、电缆或引线免受污染和/或腐蚀，所述装置包括电线、电缆或引线接线外壳，按照权利要求1或2所述的凝胶组合物，和凝胶组合物主体夹持器，该夹持器使凝胶组合物主体在压力下紧贴和围绕着电线、电缆或引线。
19.按照权利要求18所述的应用，其中为了在外壳上插入把凝胶组合物主体夹持在一种插壳中。
20.按照权利要求18或19所述的应用，其中所述装置能够用其带有的一个或几个该凝胶组合物主体围绕的一个物体进行闭合，排列凝胶主体形成凝胶-凝胶表面接触，当这种闭合时形成一种凝胶-凝胶密封，当闭合再次启通时，密封就在接触表面分开。
CN92110281A 1991-09-06 1992-09-05 凝胶体 Expired - Lifetime CN1045977C (zh)

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