CN88100643A - 生产聚四氟乙烯和硅氧烷高弹体的纤化半互穿网络聚合物及其成型产品的方法 - Google Patents

生产聚四氟乙烯和硅氧烷高弹体的纤化半互穿网络聚合物及其成型产品的方法 Download PDF

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CN88100643A
CN88100643A CN88100643.2A CN88100643A CN88100643A CN 88100643 A CN88100643 A CN 88100643A CN 88100643 A CN88100643 A CN 88100643A CN 88100643 A CN88100643 A CN 88100643A
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silicone elastomer
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约瑟·A·狄龙
马克·E·狄龙
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Abstract

生产聚四氟乙烯和硅氧烷高弹体半互穿网络聚合物的方法：(1)充分掺混主要量的未烧结且未纤化粒状聚四氟乙烯分散树脂和次要量的(A)烃类液体和(B)可加成硫化硅氧烷组合物(含有链烯不饱和性的聚二有机硅氧烷，有机氢聚硅氧烷交联剂，促聚硅氧烷交联的催化剂及催化反应的抑制剂)；(2)使掺混料形成可挤塑形状；(3)将掺混料双轴挤塑穿过模头，使之形成有随机纤化结构的成型挤塑产物；(4)蒸发烃类液体，使催化剂活化，以便得到包括纤化挤塑物结构的硫化硅氧烷高弹体和聚四氟乙烯半互穿网络聚合物。由此方法生产的产品的物理性质得到了改进。

Description

本发明涉及新的组合物，该组合物包括聚四氟乙烯和硅氧烷高弹体的半互穿网络聚合物，制备这些组合物的方法及由这些组合物形成的成形产品。更具体地说，本发明涉及以下列程序制备的组合物：
（1）将下列材料充分掺混;主成份为未烧结和未纤化的聚四氟乙烯分散树脂颗粒，次要量的（A）烃类液体和（B）基本上由带有链烯不饱和性的聚二有机硅氧烷，有机氢聚硅氧烷交联剂，促进所说聚硅氧烷交联的催化剂，以及该催化反应的抑制剂组成的可加成硫化的聚硅氧烷组合物;（2）将所说掺混物制成可挤塑的形状;（3）将所说掺混物通过模头进行双轴挤塑成为无规纤化结构的成形产品;（4）蒸发所说烃类液体，并将所说催化剂活化以便产生具有所说纤化结构的硫化硅氧烷高弹体和聚四氟乙烯半互穿网络聚合物。
在本文的参考文献美国专利3，315，020中公开了制备双轴纤化聚四氟乙烯片状制品的方法，该制品尽管是未烧结态，但却在片材平面上的所有方向均有高度的伸长率和强度。在该工艺中，使经过压制的未纤化分散级聚四氟乙烯（PTFE）颗粒的较大的圆柱状体挤压通过带有两个串联孔的模具。第一个孔是圆形，方形或长方形的孔，第二个孔是长狭缝形的孔。将有机液体润滑剂与压紧的PTFE颗粒预掺混有助于颗粒状PTFE的挤塑，这些润滑剂的例子有：煤油，油漆溶剂油，和异构烷烃油。经此挤塑产生用挥发有机液体部分饱和的双轴取向纤化结构的PTFE连续片材。在一定加工条件下，在进一步加工PTFE片材（如：烧结）前，将烃蒸发。就本发明的目的而言，双轴纤化属于美国专利3，315，020所公开的挤塑方法。尽管未烧结（即：未经过高于327℃加热）过的PTFE分散级树脂是高度结晶的（近95%）并具有很高的熔融粘度，但当加热到高于327℃的温度时，破坏了某些PTFE结晶，因此聚合物中的无定形成份增加。经过这样的加热，并随之将聚合物冷却至327℃以下，即可产生烧结态PTFE。在保持形状的同时将成形的未烧结PTFE结构烧结便可对该聚合物产生热固效应，由此可使形状保持。
就双轴纤化分散级PTFE树脂的工艺而言，出于经济和质量的原因，采用较低的挤塑压力是理想的。将给定PTFE树脂压入模具所需要的压力取决于下列因素：模具的构型，模压片截面面积与模具孔面积的比例（成反比），挤塑速度以及润滑剂的量。但是像通过加入过量的润滑剂来降低压力这样浅显的方法是不可取的。挤塑的材料在沿着机器的方向会产生过度的取向并大大降低其横向强度。但是，当过分蒸发掉润滑剂时，则会造成不留任何有取向残余结构的空洞，由此造成强度降低。或许过量润滑之最重要的唯一问题是引起挤塑件软化，由此严重地影响下一步加工，如轧光和拉伸。
通常在挤塑物仍含有烃润滑剂的同时完成对连续双轴纤化PTFE挤塑物的轧光，这包括在预先确定的距离从空间分开的两辊之间压缩及随后延伸。一般继之在合适的时间内将挤塑物加热至适于烃润滑剂安全蒸发的温度。就制造管螺纹密封带而言，通过在干燥材料或仍含有烃润滑剂的材料上用不同速度的辊进行直线拉伸，由此完成挤塑物的进一步取向。就制备微孔PTFE膜而言，采用像绷架或类似装置进一步赋于双轴纤化加工过的直线取向挤塑物以横向取向。一般将由此而获得的膜加热至327℃以上，继之冷却，以达到烧结的目的。
在改进双轴纤化PTFE挤塑物性能的先有工艺中，其困难之处在于不易生产具有满意取向纤化材料的均匀的挤塑物，以便于适当的横向拉伸。造成这一困难的原因之一就是直线取向过的材料固有的低横向拉伸率。美国专利4，187，390叙述了这些困难的实例。
本文作者意外地发现：可以改进双轴纤化PTFE的先有工艺，以便生产具有强度更高，均匀度更好的PTFE和硫化硅氧烷高弹体的双轴纤化半互穿网络聚合物的新产品。这些产品有利于生产具有相似于微孔PTFE带和膜的功能的拉伸的烧结的最终产品，本发明的产品具有与其配方原料完全不同的性能。
本文附图是由本发明工艺生产的成型产品之电子扫描显微图像。
本发明工艺中的第一步是将下列成份的混合物充分掺混，这些成份为做为主要量的有未烧结并未纤化的颗粒状PTFE分散级树脂和作为次要量的（A）烃类液体和（B）基本上由下列组份组成的可加成硫化的硅氧烷组合物：带有链烯不饱和性的聚二有机硅氧烷、有机氢聚硅氧烷、促进所说聚硅氧烷交联的催化剂，和催化反应抑制剂。该混合物必须通过固-液掺混器，或通过罐式滚混来掺混，以避免PTFE分散树脂发生实质性的剪切。
适宜的未烧结和未纤化PTFE分散树脂由E.I.du    Pont    de    Nemours    &    Co.，Inc.制备，其牌号为TEFLON    6和6C;以及由Imperial    Chemical    Industries制备，其牌号为FLUON    CD1，CD123和CD525。
在实施本发明中所使用的代表性的含链烯基聚二有机硅氧烷在25°的粘度高达100，000，000厘泊或更高，例如与Bobear的美国专利4，061，609所介绍的情况一致。现已发现：当含链烯基聚硅氧烷的粘度约为500-50，000厘泊（25℃）时，尤其是约为3000-6000厘泊（25℃）时，可获得十分满意的结果。
可用于本发明的有机氢聚硅氧烷可以是线性物或树脂状物，其粘度约为25-10000厘泊（25℃）最好是约100-1000厘泊（25℃）。
硫化催化剂既可以是有机过氧化物也可以是含贵金属材料。适宜的有机过氧化物为：过氧化二苯甲酰，过氧化双-2，4-二氯苯甲酰，过氧化二-叔丁基，2，5-二甲基-2，5-二（叔丁基过氧化）己烷，过氧化二异丙基。含贵金属催化剂中的贵金属为铑，钌，钯，锇，铱，铂。尤其可取的是下列专利文献中所介绍的作为催化剂使用的铂金属配合物;例如：Ashby，U.S.3，159，601;3，159，662;Lamoreaux，U.S.3，220，970;Karstedt，U.S.3，814，730;Modic，U.S.3，516，946。
在一特别优选的实施例中，可加成硫化硅氧烷组合物还包括下述美国专利所介绍的增强有机聚硅氧烷树脂，这些专利包括：Nelson，U.S.3，284，406或Modic，U.S.3，436，366。简言之，这些树脂分别是下列单元的共聚物，这些单元包括：SiO2单元，（CH3）3SiO0.5单元和（CH3）2＝CHSiO0.5单元;SiO2单元，（CH3）3SiO0.5单元和（CH3）（CH2＝CH）SiO单元。特别优选的有机聚硅氧烷树脂是MDQ树脂，该树脂在单官能硅氧烷单元，双官能硅氧烷单元，或两者同时具有乙烯基不饱和基团。当含链烯基聚二有机硅氧烷的粘度低于约5000厘泊（25℃）时尤其需要使用这种增强有机聚硅氧烷树脂。
同样需要考虑的是在该组合物中应加入常用的增量剂和/或增强填料。现已发现气相法白炭黑是特别有效的增强填料。
在本发明另一十分优选的实例中，可加成硫化硅氧烷组合物也可以含有既可以作为抑制剂又可以作为增粘剂的硅烷或聚硅氧烷。Berger等人在美国专利3，759，968中将一个这种组合物描述为功能硅烷或硅氧烷的马来酸酯或富马酸酯。Eckberg在美国专利4，256，870，Bobear在美国专利4，061，609中公开了仅作为抑制剂有效的组合物。其他适宜的抑制剂对熟悉本领域的人来说是显而易见的。
另外还要求所说的聚硅氧烷可以是可缩合硫化硅氧烷组合物。一般适用的缩合硫化聚硅氧烷组合物可是单组分或双组分的，该组合物中包括①：具有可水解末端基团的聚二有机硅氧烷，如：羟基或烷氧基端基，②：促进缩合硫化的催化剂。例如，Bessmer等在美国专利3，888，815中所述，这类组合物是本领域众所周知的。
另外，将具有下列通式的硅烷水解也可制得聚硅氧烷网络，该通式为：
Y-Si-（OX）3
式中每个X分别选自下列基团：氢，烷基，羟基烷基，烷氧基烷基，羟基烷氧基烷基;Y是烷基，OX中X定义如前，或是氨基或取代胺基。Foscante等人在美国专利4，250，074中更具体详细地讨论了带有可水解形成互穿网络聚硅氧烷基团的硅烷的用途。
烃类液体最好是溶剂，如：油漆溶剂油，异构烷烃油和煤油。
较少量的烃类液体和可加成硫化硅氧烷组合物在本发明方法的第一步中两者均对PTFE颗粒起润滑剂的作用，因此必须要小心使用以避免所说的过分润滑问题。但是，当加到掺混料中的可加成硫化硅氧烷组合物的重量少到2%时，所引起的挤塑压力就会低于单独使用烃类液体和PTFE分散树脂的掺混物时的压力。在掺混物中掺入可加成硫化硅氧烷组合物的重量含量达到7%时，挤塑压力可降低多达56%。
在本发明方法的第二步中，将掺混料压制成适于双轴纤化工艺要求所必须的形状的预成形制品（如美国专利3，315，020所述）。
在本发明方法的第三步中，用美国专利3，315，020所述的公知的双轴纤化方法对预成形的掺混料进行糊料挤塑。
在本发明方法的第四步中，蒸发掉掺混料中所含的烃类液体，与此同时或在其后将用于硅氧烷交联反应的催化剂活化，由此，以双轴纤化挤塑物的形式得到硫化硅氧烷高弹体和聚四氟乙烯半互穿网络聚合物。
实施例1
制得了下列可硫化硅氧烷组合物
重量比
乙烯基N-终止的聚二甲基硅氧烷（3500厘泊，25℃）    68.2
MDQ硅氧烷树脂掺混料    22.7
二甲基乙烯基硅氧烷树脂掺混料    8.2
马来酸双（三甲氧基硅丙基）酯    0.9
Lamoreaux铂催化剂    10ppm
该可硫化硅氧烷组合物与FLUON    CD123级聚四氟乙烯分散树脂及油漆溶剂油按下列方法混合：
用固-液掺混器制备下列两种配料;硅氧烷油漆溶剂油/PTFE分散级树脂（5∶1∶1）掺混料和油漆溶剂油/PTFE（1∶1）掺混料。将所得掺混料压制成圆柱形预成形品并挤压使其通过一个带有圆形孔并且缩比为900∶1的模头进行挤塑。表Ⅰ给出了所得念珠状挤塑物所要求的挤塑压力。从表Ⅰ可以看出由于加入了少量的可硫化硅氧烷聚合物，挤塑压力大幅度降低，而且所有挤塑的样品肉眼看外观相同，并有PTFE分散级树脂挤塑物的正常手感。由于减少了有机润滑剂的含量，当分别与样品2，3时相比，样品5和6所需挤塑压力增加。
实施例2
使用固-液掺混器和实例1中的硅氧烷组合物及PTFE树脂制备了下列2种掺混料：煤油/PTFE分散级树脂（3∶1）掺混料，和硅氧烷/煤油/PTFE分散级树脂（4∶1∶1）掺混料。将所得掺混料压制成圆柱形预成形件并挤塑穿过美国专利3，315，020所述的用于获得双轴纤化的模头。将样品2-1，2-2，2-3，2-4压延至厚度为5密耳，将样品2-5，2-6，2-7压延至厚度为4密耳。将每个挤塑物在310至320°F加热以便蒸掉煤油，并使硅氧烷高弹体硫化。表2列出了挤塑条件和挤塑物的物理性质。将样品2-1，2-2，2-5与样品2-3，2-4，2-7比较，可以发现：掺有硅氧烷高弹性的挤塑物密度与可比的PTFE挤塑物的密度相比，前者比后者高出28%。还可以看出：在双轴纤化挤塑物中掺入硅氧烷高弹体改善了断裂前的横向延伸性，比未掺入硅氧烷高弹体提高了37.5%。
实施例3
使用绷架横向拉伸按实施例2所得到的挤塑物。在拉伸期间将掺入硅氧烷高弹体的样品在约120℃加热，同时，在拉伸期间将PTFE挤塑物在175℃加热。表3列出了所得微孔膜的物理性质，从各实例中可以看出掺入硅氧烷高弹体沿机器方向和沿横向均增加了被拉伸产品的拉伸强度。将拉伸样品2-3的电子扫描显微图放大5000倍，并附于附图上。所显示的随机纤化物厚度为1.0微米。
实施例4
将实施例1中所规定的可硫化硅氧烷组合物的低臭煤油溶液，以递增的硅氧烷浓度（2.5%，5.0%，10.0%，15.0%，20.0%）连续15秒喷洒在5份按照实施例3制造的样品号为3-6的微孔膜上。喷洒并待溶剂蒸发后，于150℃将样品硫化15分钟。表4显示了由本发明聚合物网络组合物制得的微孔膜产品经硫化硅氧烷高弹体浸渍后对该膜不透明度（与未处理膜相比）的令人惊奇的影响。表4显示出了这些产品类似的其他物理性质也是类似的。
实施例5
用液-固掺混器将下列成份掺混在一起：
238.4g    实施例1硅氧烷组合物
238.4g    碳酸钙
2701.3g    PTFE分散级树脂
730.9g    煤油
将所得掺混料压制成圆柱形坯料，并将其挤塑穿过在挤塑样品2-1至2-4中所用的模头。挤塑压力为3000psi，将挤塑物压延至厚度为5密耳，在310至320°F加热以蒸去煤油并使硅氧烷高弹体硫化。从这一实施例可明显地看出：可将本发明工艺用于生产PTFE和硅氧烷高弹体的填充的半互穿网络聚合物。
Figure 88100643_IMG1
Figure 88100643_IMG2
Figure 88100643_IMG3
Figure 88100643_IMG4

Claims (6)

1、生产聚四氟乙烯和硅氧烷高弹体的半互穿网络聚合物的方法，该方法包括以下步骤：(1)将主要量的未烧结并未纤化的颗粒状聚四氟乙烯分散树脂和次要量的(A)烃类液体和(B)主要由下列成份组成的可加成硫化硅氧烷组合物的混合物进行充分掺混，(B)的主要成份包括：具有链烯基不饱和性的聚二有机硅氧烷，有机氢聚硅氧烷交联剂，用于促进所说聚硅氧烷交联的催化剂，该催化反应的抑制剂；(2)将所说掺混料制成可挤塑的形状；(3)将所说掺混料进行双轴挤塑穿过模头使之形成具有随机纤化结构的成形挤塑产品；(4)蒸发所说烃类液体，并使所说催化剂活化，以便形成包括所说纤化挤塑物结构的硫化硅氧烷高弹体和聚四氟乙烯半互穿网络聚合物。
2、权利要求1的方法，其进一步的特征在于将成形挤塑产品压延成均匀的厚度。
3、权利要求1的方法，其中在聚四氟乙烯，烃类液体和可加成硫化硅氧烷组合物的混合物中，可加成硫化硅氧烷组合物在重量上占该混合物的至少2%。
4、权利要求1的方法，其中步骤（1）中的混合物另外还包括较少量的碳酸钙。
5、权利要求1的方法所制备的产品。
6、聚四氟乙烯聚合物和硅氧烷高弹体的半互穿网络聚合物，所说硅氧烷高弹体包括具有链烯不饱和性的聚二有机硅氧烷和有机氢聚硅氧烷的交联反应产物。
CN88100643A 1987-01-05 1988-01-05 生产聚四氟乙烯和硅氧烷高弹体的纤化半互穿网络聚合物成型产品的方法 Expired CN1014795B (zh)

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