CN1199413A - 由乳液合成法制备聚合物毫微复合材料 - Google Patents

由乳液合成法制备聚合物毫微复合材料 Download PDF

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CN1199413A
CN1199413A CN96194971A CN96194971A CN1199413A CN 1199413 A CN1199413 A CN 1199413A CN 96194971 A CN96194971 A CN 96194971A CN 96194971 A CN96194971 A CN 96194971A CN 1199413 A CN1199413 A CN 1199413A
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C·W·艾尔斯帕斯
E·N·克里斯吉
D·G·派福
D·T·塞伊
J·J·克鲁德辛斯基
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ExxonMobil Technology and Engineering Co
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Abstract

本发明公开了由乳液聚合制备毫微复合材料的方法。本发明包括掺混有乳液聚合物的层状硅酸盐矿石的毫微复合材料胶乳、固体毫微复合材料以及固体毫微复合材料与其它聚合物的共混物。

Description

由乳液合成法制备聚合物 毫微复合材料
发明领域
本发明涉及对小分子如空气的透过性降低、并具有改进的机械性能的复合材料。更具体地说，本发明涉及掺混有乳液聚合物的层状硅酸盐。
技术背景
层状结构的矿石土如蒙脱石由多层厚度为约1毫微米的硅酸盐层组成。这种层状材料在聚合物中的分散体通常被称作毫微复合材料(nanocomposites)。
最近，人们越来越关注通过形成毫微复合材料来改进聚合物的机械性能。但是，在聚合物基质中掺混入矿石土并不总能显著改进聚合物的机械性能，这可能是由于层状硅酸盐材料与有机聚合物之间的亲合力不够造成的。因此，已提出借助离子间相互作用将矿石土掺混入聚合物中，此类方法例如可参见美国专利US No.4 889 885和No.4 810 734。但是，这种方法的应用有一定的局限性。事实上，迫切需要一种更直接、简便和经济的制备毫微复合材料的方法。
本发明的一个目的是提供一种包含掺混有乳液聚合物的层状硅酸盐的胶乳。
本发明的另一个目的是提供一种由层状硅酸盐和乳液聚合物的分散体胶乳形成的复合材料，该材料对小分子如空气具有减低的透过性，并具有改进的机械性能。
从下面的描述中可明显看出本发明的上述及其它目的、特征和优点。
本发明概述
在本发明的一个实施方案中，提供一种包含水和掺混有聚合物乳液的层状矿石的胶乳。
在本发明的另一个实施方案中，提供一种包含掺混有乳液聚合物的层状矿石的毫微复合材料。
本发明的另一方面包括第一种聚合物与由掺混有乳液聚合物的层状矿石组成的毫微复合材料的共混物。
制备本发明胶乳的方法包括，形成层状矿石在包含膨胀剂如鎓盐的水中的分散体，向该分散体中加入可聚合单体或单体混合物如烯烃或二烯烃以及聚合反应引发剂，然后使单体或单体混合物聚合，形成包含水和聚合物毫微复合材料的胶乳。这种制备本发明胶乳的方法也是本发明的一个方面。
由本发明胶乳形成的复合材料具有改进的机械性能，并降低了对小分子如空气的气体透过性，因而特别适于用作轮胎衬里以及内胎、隔挡层、薄膜、涂料等等。
本发明的详细描述
能够被掺混的任何天然或合成层状矿石均可用于本发明中，但优选层状硅酸盐矿石。可用于本发明中的层状硅酸盐矿石包括能够形成掺混物的天然和合成矿石。这些矿石的非限定性实例包括绿土、蒙脱石、滑石粉、拜来石、montronite、水辉石、富镁蒙脱石、蛭石和多水高岭土，其中优选蒙脱石。
用于本发明方法中的膨胀剂是能够嵌入层状矿石中、从而增大矿石层与层之间距离的任何化合物。特别优选的膨胀剂是式A-M+R1R2R3R4和A-Py+R4所示的烃基鎓盐，式中：A-表示阴离子，如卤离子、OH-、NO3 -、SO4 -等；M表示N、S、P；R1、R2、R3和R4相互独立地表示氢原子、烷基、芳基或烯丙基，它们可以相同或不同，但其中至少一个不是氢原子；Py表示吡啶鎓或烷基取代的吡啶鎓基。
可以看出，上述膨胀剂中的一些也是乳化剂。但是，在使用的膨胀剂不是乳化剂的情况下，优选在进行聚合时还使用乳化剂。当然，即使使用的膨胀剂具有乳化性能，也有可能再使用另外一种乳化剂。在上述两种情况下，所使用的乳化剂是通常用于乳液聚合中的那些乳化剂。优选阳离子型乳化剂和非离子型乳化剂。
在本文中被称作“乳液聚合物”的聚合物和共聚物是指由乳液聚合法形成的聚合物，包括基于一种或多种与水不混溶、可自由基聚合的单体的聚合物，单体例如为烯类单体，并且特别是苯乙烯或对甲基苯乙烯、丁二烯、异戊二烯、氯丁二烯和丙烯腈。特别优选的是苯乙烯橡胶共聚物，即苯乙烯与丁二烯、异戊二烯、氯丁二烯和丙烯腈的共聚物。在本发明的实践中，特别优选玻璃化转变温度低于约25℃、数均分子量高于5000g/mol、特别是高于15000g/mol的均聚物和共聚物。此外，优选的聚合物还含有不饱和位点或其它用于硫化的活性位点。
具有掺混入其中的乳液聚合物的可掺混矿石的胶乳如下制备，制成层状矿石在水中的分散体，并加入膨胀剂。一般情况下，通过向100g水中加入约0.01g至约80g、优选约0.1g至约10.0g的矿石，首先将矿石分散于水中，然后剧烈搅拌或剪切矿石和水足够的时间，使矿石分散于水中。之后在搅拌下向该分散体中加入烃基鎓盐，优选以水溶液的形式加入。
本发明方法中鎓盐的用量取决于所用层状材料和单体的类型以及操作条件。但是在一般情况下，鎓盐的用量在层状矿石的阳离子交换容量的约10％至约2000％范围内。
随后，通过在乳液聚合条件下向矿石分散体中加入乳化剂(如果希望或需要)、适宜单体或单体混合物和自由基引发剂，形成聚合物胶乳。例如，使用自由基聚合引发剂在搅拌下使苯乙烯和异戊二烯在矿石分散体中聚合，该共聚合反应通常在约25℃至约100℃范围内的温度下进行足以形成聚合物胶乳的一段时间，随后终止反应。
根据常用的方法，可将上述胶乳制成涂料或薄膜。此外，通过使胶乳絮凝并干燥，可以得到层状硅酸盐矿石和聚合物的固体毫微复合材料。然后，使用常规方法如压延或挤出，随后成型，可将该固体复合材料制成轮胎衬里或内胎。
在本发明的一个实施方案中，通过在橡胶磨上或在密闭式混合机中共混，将本发明毫微复合材料与另一种聚合物如苯乙烯橡胶共聚物掺混。优选将毫微复合材料与用于形成毫微复合材料的单体或单体混合物形成的聚合物共混。在聚合物中毫微复合材料的用量通常为约0.1％至约70％(重量)。
在制备轮胎衬里时，与本发明毫微复合材料共混的聚合物的分子量优选大于约10000，并具有一定的不饱和度或其它活性位点，从而可在本体状态硫化或交联。
以下实施例将更好地说明本发明。
实施例1
用已用氮气冲吹脱气处理过的水(450g)将层状硅酸盐蒙脱石土(18g)淤浆化。将淤浆在23℃搅拌过夜。在瓦轮(Waring)混合机中将此粘土在水中分散3分钟，然后进一步脱气。将十二烷基三甲基溴化铵(25.7g)溶解于脱气的水(250g)中，并将其加到该粘土淤浆中。将异戊二烯(35g)、苯乙烯(15g)和用作引发剂的偶氮双异丁腈(AIBN)(0.25g)混合后加到上述淤浆中。将该混合物在23℃机械搅20小时，在65℃搅拌26小时，此后用5g分成等份的2，6-二叔丁基-4-甲基苯酚(0.24g)、氢醌(1.6g)、四〔亚甲基(3，5-二叔丁基-4-羟基-氢化肉桂酸酯)〕甲烷和200ml甲醇的混合物终止聚合反应。得到含有其中掺混有苯乙烯-异戊二烯共聚物胶乳的层状硅酸盐的乳液。
实施例2
向胶乳中加入过量甲醇，从液体含水相中分离出固体，用甲醇将该固体洗涤6次，随后在60℃真空干燥约18小时，在23℃真空干燥48小时，由实施例1的胶乳制得固体毫微复合材料。
实施例3
在布雷本登(Brabender)混合机中，将一份实施例2制得的固体毫微复合材料(20g)与苯乙烯-异戊二烯共聚物(20g)在130℃熔混5分钟，所述共聚物与实施例1中的制备方法相同但没有矿石土。将毫微复合材料与无矿石土的苯乙烯-异戊二烯共聚物的共混物与硬脂酸(1phr)、氧化锌(3.9phr)和二硫化四甲基秋兰姆(促进剂)(1phr)在55℃磨炼10分钟，进行交联。然后将该共混物热压成20密耳的薄膜，并在130℃固化20分钟。将薄膜在Mocon 2/20上测试在30℃的透氧性，结果列于下表I中。表I中还列出了由相同方法合成、但没有矿石土的苯乙烯—异戊二烯共聚物制得的薄膜的测试结果(对比例1)。
使用英斯特朗(Instron)试验仪，用小的拉伸薄膜试样测量单向拉伸性能。在室温和0.51mm/分钟的拉伸速率下进行应力-应变测量，结果列于下表2中。表2还给出了被称作对比例1的拉伸性能，它是与实施例1相同的方法合成、但没有矿石土的苯乙烯-异戊二烯共聚物。
                             表1薄膜                   矿石土的wt％      透氧性
Figure A9619497100081
实施例3                  26.3            4,138对比例1                  0               12,340*Mocon 2/20@30℃
                            表2
     扯断    扯断   扬氏   100％   200％   300％    400％  扯断能
     应力    应变   模量   模量    模量    模量     模量薄膜   (psi)    (％)   (psi)  (psi)  (psi)    (psi)    (psi)  (in-Ibs.)对比例1  2001    560    2053    503    660      901     1236    12.1实施例3  2312    497    5018    699    880      1262    1727    11.3

Claims (25)

1.一种胶乳，它包含水和掺混有乳液聚合物的层状矿石。
2.根据权利要求1的胶乳，其中，所述层状矿石是选自绿土、蒙脱石、滑石粉、拜来石、montronite、水辉石、富镁蒙脱石、蛭石和多水高岭土的天然或合成矿石。
3.根据权利要求1的胶乳，其中，所述聚合物由可自由基聚合的烯类单体或单体混合物制成。
4.根据权利要求1的胶乳，其中，所述聚合物是含苯乙烯的共聚物。
5.根据权利要求4的胶乳，其中，所述共聚物含有选自丁二烯、异戊二烯、氯丁二烯和丙烯腈的共聚单体。
6.根据权利要求5的胶乳，其中，所述层状材料是蒙脱石。
7.一种胶乳，它包含水和掺混有聚合物或共聚物的天然或合成层状矿石，其中，层状矿石选自绿土、蒙脱石、滑石粉、拜来石、montronite、水辉石、富镁蒙脱石、蛭石和多水高岭土，并且聚合物或共聚物由可自由基聚合的烯类单体或单体混合物制成。
8.根据权利要求7的胶乳，其中，所述烯类单体或单体混合物选自苯乙烯、对甲基苯乙烯、丁二烯、异戊二烯、氯丁二烯和丙烯腈。
9.一种毫微复合材料，它包含掺混有乳液聚合物的层状矿石。
10.根据权利要求9的毫微复合材料，其中，所述层状矿石选自绿土、蒙脱石、滑石粉、拜来石、montronite、水辉石、富镁蒙脱石、蛭石和多水高岭土。
11.根据权利要求10的毫微复合材料，其中，所述聚合物由可自由基聚合的烯类单体或单体混合物制成。
12.根据权利要求11的毫微复合材料，其中，所述聚合物是含苯乙烯的共聚物。
13.根据权利要求12的毫微复合材料，其中，所述含苯乙烯的共聚物是苯乙烯或对甲基苯乙烯与选自丁二烯、异戊二烯、氯丁二烯和丙烯腈的单体的共聚物。
14.根据权利要求13的毫微复合材料，其中，所述层状矿石是蒙脱石。
15.一种聚合物共混物，它包含第一种聚合物以及掺混有乳液聚合物的层状矿石的毫微复合材料。
16.根据权利要求15的共混物，其中，所述第一种聚合物和乳液聚合物由相同的单体或单体混合物制成。
17.根据权利要求16的共混物，其中，所述第一种聚合物和乳液聚合物是共聚物。
18.根据权利要求17的共混物，其中，所述毫微复合材料在该共混物中的量为约0.1％-约70％(重量)。
19.根据权利要求18的共混物，其中，所述共聚物是苯乙烯或对甲基苯乙烯与选自丁二烯、异戊二烯、氯丁二烯和丙烯腈的单体的共聚物。
20.一种制备包含毫微复合材料的胶乳的方法，它包括：
将层状矿石分散于水中，形成分散体；
向该分散体中加入膨胀剂；然后
在乳液聚合条件下，在该分散体的存在下使可自由基聚合的烯类单体或单体混合物聚合，形成包含毫微复合材料的胶乳。
21.根据权利要求20的方法，其中，使两种单体进行共聚合，一种单体是苯乙烯或对甲基苯乙烯，另一种单体是丁二烯、异戊二烯、氯丁二烯或丙烯腈。
22.根据权利要求21的方法，其中，所述膨胀剂是烃基鎓盐。
23.根据权利要求22的方法，其中，所述烃基鎓盐的通式为A-M+R1R2R3R4或A-Py+R4，式中：A-为阴离子；M为N、S或P；R1、R2、R3和R4可相同或不同，相互独立地为氢原子、烷基、芳基或烯丙基；Py表示吡啶鎓基或烷基取代的吡啶鎓基。
24.根据权利要求23的方法，其中，所述聚合反应在乳化剂的存在下、在约5℃至约100℃范围内的温度下进行足以形成胶乳的时间。
25.根据权利要求24的方法，它包括，向胶乳中加入絮凝剂，使固体毫微复合材料絮凝，然后分离该固体毫微复合材料。
CN96194971A 1995-06-23 1996-05-17 由乳液合成法制备聚合物毫微复合材料 Pending CN1199413A (zh)

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Cited By (3)

* Cited by examiner, † Cited by third party
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CN1330673C (zh) * 2000-09-21 2007-08-08 罗姆和哈斯公司 改进的纳米复合材料组合物及其制备和应用方法
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