CN107922670A - 泡沫成型用加工助剂，包含其的基于氯乙烯树脂的泡沫成型组合物以及泡沫成型产品 - Google Patents

泡沫成型用加工助剂，包含其的基于氯乙烯树脂的泡沫成型组合物以及泡沫成型产品 Download PDF

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CN107922670A
CN107922670A CN201680048183.1A CN201680048183A CN107922670A CN 107922670 A CN107922670 A CN 107922670A CN 201680048183 A CN201680048183 A CN 201680048183A CN 107922670 A CN107922670 A CN 107922670A
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M·T·彼得
P·万里宁
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Abstract

提供一种泡沫成型用加工助剂，其包含通过聚合以下各项而获得的共聚物：总共50到100重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体以及0到50重量％其它可共聚单体，所述共聚物具有以下性质：(a)根据ASTM D2857在1mg/mL下在氯仿中在25℃下测量的大于8dL/g的减小的粘度，和(b)等于或小于77℃的Tg。

Description

泡沫成型用加工助剂，包含其的基于氯乙烯树脂的泡沫成型 组合物以及泡沫成型产品
技术领域
本发明涉及一种泡沫成型用加工助剂，一种使用所述加工助剂的泡沫成型方法，一种包含所述加工助剂的基于氯乙烯树脂的泡沫成型组合物，以及一种所形成的泡沫成型芒品。
背景技术
在建筑业中，聚(氯乙烯)(PVC)常用于发泡成型。泡沫是通过用化学发泡剂和高分子量加工助剂配制而成的。在挤出期间，发泡剂分解产生溶解在高压PVC熔体中的气体。当它离开模具并且压力下降时，气体形成气泡，使PVC膨胀至其原始体积的两到三倍。此时，PVC泡沫破裂，所以加入高分子量加工助剂以增加熔体粘度并提供缠结以防止PVC熔体松弛以及提供额外的模头溶胀和进一步的泡沫膨胀。商业泡沫加工助剂是极高分子量(通常1-20Mg/mol)的具有高达30％其它聚丙烯酸的聚(甲基丙烯酸甲酯)共聚物。
影响泡沫加工助剂效率的主要有三个变量：分子量、分子结构和玻璃化转变温度(Tg)。一般来说，较高分子量产生较高的泡沫膨胀，因为它具有较高的熔体粘度并提供更多的缠结，且较少的支化和交联产生较高的泡沫膨胀，因为聚合物可以更好地混入PVC中。另一方面，似乎有一个最佳的Tg以提供高的熔体粘度，但在挤出过程中仍能够解开。通常，为了提供这些性质，使用总共15-20％的丙烯酸乙酯(EA)和/或丙烯酸丁酯(BA)。无论EA还是BA，所得共聚物的分子量均低于任何组成性均聚物，因为MMA与EA或BA的交叉传播非常缓慢。BA促进了显著的交联，因为聚合物骨架中的叔氢容易被夺取。因此，所述领域中仍然需要改进的发泡助剂。
发明内容
在第一实施例中，本公开提供一种泡沫成型用加工助剂，其包含通过聚合以下各项而获得的共聚物：总共50到100重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体以及0到50重量％其它可共聚单体，所述共聚物具有以下性质：(a)根据ASTM D2857在1mg/mL下在氯仿中在25℃下测量的大于8dL/g的减小的粘度，和(b)等于或小于77℃的Tg。
在第二实施例中，本公开提供一种基于氯乙烯树脂的泡沫成型组合物，其包含100重量份氯乙烯树脂和1到25重量份根据本文所公开的任何实施例使用的泡沫成型用加工助剂。
在第三实施例中，本公开提供一种泡沫成型产品，其由根据本文所公开的任何实施例的基于氯乙烯树脂的泡沫成型组合物形成。
具体实施方式
泡沫成型用加工助剂包含共聚物，所述共聚物通过聚合总共50重量％到100重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体而获得。本文中包括并公开从50到100重量％的所有个别值和子范围；例如一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体的总重量百分比可能在以下范围内：下限50、60、70、80或90重量％到上限55、65、75、85、95或100重量％。泡沫成型用加工助剂包含通过聚合以下获得的共聚物：总共50重量％到100重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体，或在替代方案中总共50重量％到75重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体，或在替代方案中总共75重量％到100重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体，或在替代方案中总共60重量％到90重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体，或在替代方案中总共50重量％到95重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体，或在替代方案中总共50重量％到98重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体，或在替代方案中总共50重量％到小于100重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体。
泡沫成型用加工助剂包含通过聚合0到50重量％其它可共聚单体而获得的共聚物。本文中包括并公开从0到50重量％其它可共聚单体的所有个别值和子范围；例如，其它可共聚单体的重量百分比可能在以下范围内：下限0、10、20、30或40％到上限5、15、25、35、45或50重量％。泡沫成型用加工助剂包含通过聚合以下而获得的共聚物：0到50重量％其它可共聚单体，或在替代方案中0到25重量％其它可共聚单体，或在替代方案中25到50重量％其它可共聚单体，或在替代方案中10到40重量％其它可共聚单体，或在替代方案中5到50重量％其它可共聚单体，或在替代方案中2到50重量％其它可共聚单体，或在替代方案中大于0到50重量％其它可共聚单体。
其它可共聚单体包括能与甲基丙烯酸酯共聚合的任何单体。此类单体包括例如丙烯酸烷基酯、甲基丙烯酸烷基酯、交联剂和接枝键联剂。示例性单体包括甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸乙基己酯(EHA)、丙烯酸辛酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、甲基丙烯酸戊酯、甲基丙烯酸己酯、甲基丙烯酸乙基己酯(EHMA)、甲基丙烯酸辛脂、苯乙烯、乙酸乙烯酯、甲基丙烯酸乙酰乙酰氧基乙酯、丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺、甲基丙烯酸缩水甘油酯、顺丁烯二酸酐。
在一个具体实施例中，共聚物是通过在不存在任何其它可共聚单体的情况下聚合50到100重量％甲基丙烯酸丙酯和0到50重量％甲基丙烯酸甲酯而获得的。
在一个具体实施例中，共聚物是通过在不存在任何其它可共聚单体的情况下聚合80到100重量％甲基丙烯酸乙酯和0到20重量％甲基丙烯酸甲酯而获得的。
在又另一实施例中，本公开提供一种泡沫成型用加工助剂，其由通过聚合以下获得的共聚物组成：总共50重量％到100重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体，和0到50重量％其它可共聚单体，所述共聚物具有以下特性：(a)根据ASTM D2857在1mg/mL下在氯仿中在25℃下测量的大于8dL/g的减小的粘度，和(b)等于或小于77℃的Tg。
在又另一实施例中，本公开提供一种泡沫成型用加工助剂，其基本上由通过聚合以下获得的共聚物组成：总共50重量％到100重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体，和0到50重量％其它可共聚单体，所述共聚物具有以下特性：(a)根据ASTM D2857在1mg/mL下在氯仿中在25℃下测量的大于8dL/g的减小的粘度，和(b)等于或小于77℃的Tg。
所得泡沫成型用加工助剂展现根据ASTM D2857在1mg/mL下在氯仿中在25℃下测量的大于8dL/g的减小的粘度。本文中包括并公开大于8dL/g的所有个别值和子范围。举例来说，泡沫成型用加工助剂可能展现大于8dL/g，或在替代方案中大于9dL/g，或在替代方案中大于10dL/g，或在替代方案中大于11dL/g，或在替代方案中大于14dL/g，或在替代方案中大于17dL/g的减小的粘度。
泡沫成型用加工助剂可以使用任何已知的乳液聚合方法制得。
最常见的挤出操作涉及从模具中自由发泡，然后进行一些类型的校准以及Celuka或整合的蒙皮工艺。这些PVC发泡工艺和典型的配制成分的描述可见于《聚合泡沫和泡沫技术手册(Handbook of Polymeric Foams and Foam Technology)》，Klemper，D.，Sendijarevic，V.编，第2版，慕尼黑汉泽出版社(Hanser Publishers，Munich)，2004第9章。
在一个替代实施例中，泡沫成型用加工助剂使用多阶段乳液聚合方法制得。此类工艺公开在美国专利申请公开案2015/0183944和2014/0371396中，所述公开案的公开内容以引入的方式并入本文中。
泡沫成型用加工助剂通常经过分离以形成自由流动的粉末或球粒，粉末粒子的平均直径为50-500微米。
本文中公开的基于氯乙烯树脂的泡沫成型组合物包含100重量份氯乙烯树脂和1到25重量份根据本文所公开的任何实施例使用的泡沫成型用加工助剂。本文中公开并包括从1到25重量份加工助剂的所有个别值和子范围；例如基于氯乙烯的泡沫成型组合物中的加工助剂的量可以在以下范围内：下限1、3、6、9、12、15或18重量份到上限2、5、8、11、14、17、20或25重量份。举例来说，基于氯乙烯的泡沫成型组合物中的加工助剂的量可能是1到25重量份，或在替代方案中1到12重量份，或在替代方案中12到25重量份，或在替代方案中8到18重量份。
在替代实施例中，基于氯乙烯树脂的泡沫成型组合物可以包含一种或多种选自由以下组成的群组的添加剂：热稳定剂、润滑剂、冲击改性剂、填充剂、颜料或其它着色剂、或影响除发泡以外性质的其它加工助剂。
本公开进一步提供一种泡沫成型产品，其由根据本文所公开的任何实施例的基于氯乙烯树脂的泡沫成型组合物形成。
在一个具体实施例中，泡沫成型产品是发泡结构部件。
在替代实施例中，本公开提供根据本文所公开的任何实施例的泡沫成型用加工助剂、基于氯乙烯树脂的泡沫成型组合物和泡沫成型产品，除了基于氯乙烯树脂的泡沫成型组合物展现等于或大于130％的泡沫膨胀。本文中包括并公开等于或大于130％的所有个别值和子范围。举例来说，基于氯乙烯树脂的泡沫成型组合物可能展现等于或大于130％，或在替代方案中等于或大于132％，或在替代方案中等于或大于135％，或在替代方案中等于或大于138％的泡沫膨胀。
本公开进一步提供一种使氯乙烯树脂泡沫成型的方法，所述方法包含挤出根据本文所公开的任何实施例的基于氯乙烯树脂的泡沫成型组合物，其包含100重量份氯乙烯树脂和1到25重量份加工助剂。
实例
以下实例说明本发明，但并不打算限制本发明的范围。
所有实例均如下使用错误！参考来源未找到中的不同单体组成制备。
使用乳液聚合制备泡沫加工助剂。将单体乳液DOWFAX 2A1和水混合并添加到反应烧瓶中。在使内容物惰化之后，使用铁盐催化的甲醛次硫酸钠和过硫酸钠氧化还原引发剂系统引发聚合反应。聚合完成后，将乳胶冷却并干燥。DOWFAX 2A1是可从陶氏化学公司(TheDow Chemical Company，美国密歇根州米德兰(Midland，MI，USA))商购获得的烷基二苯醚二磺酸盐表面活性剂。
泡沫成型用加工助剂，本发明实例1-2和比较实例1-5用于使聚氯乙烯树脂泡沫成型，如PCT公开案WO 2013/095876中所述，所述公开案的公开内容以全文引用的方式并入本文中。加工助剂以7.2phr的量添加。PCT公开案WO 2013/095876进一步描述本文中所用的测量泡沫膨胀的方法。表1进一步提供各示例加工助剂的泡沫膨胀结果。减小的粘度根据ASTMD2857在1mg/mL下在氯仿中在25℃下测量。表2提供某些本发明实例和比较实例的减小的粘度测量值。
表1.示例单体组成和泡沫膨胀.
实例ID 组成 泡沫膨胀
本发明实例1 100％EMA 155％
本发明实例2 20％MMA 80％EMA 150％
比较实例1 82％MMA 18％BA 128％
比较实例2 82％MMA 18％EA 134％
比较实例3 83.5％MMA 4.9％BA 11.6％EA 138％
比较实例4 84％MMA 16％EHA 116％
比较实例5 72％MMA 28％EHMA 132％
表2.示例单体组成和减小的粘度.
实例ID 组成 减小的粘度(dL/g)
本发明实例1 100％EMA 19.04
本发明实例2 20％MMA 80％EMA 18.79
比较实例1 82％MMA 18％BA 14.20
比较实例2 82％MMA 18％EA 18.90
比较实例5 72％MMA 28％EHMA 17.17

Claims (9)

1.一种泡沫成型用加工助剂，其包含通过聚合以下各项而获得的共聚物：总共50到100重量％一种或多种选自由甲基丙烯酸乙酯和甲基丙烯酸丙酯组成的群组的单体以及0到50重量％其它可共聚单体，所述共聚物具有以下性质：(a)根据ASTM D2857在1mg/mL下在氯仿中在25℃下测量的大于8dL/g的减小的粘度，和(b)等于或小于77℃的Tg。
2.根据权利要求1所述的加工助剂，其中所述共聚物是通过在不存在任何其它可共聚单体的情况下聚合50到100重量％甲基丙烯酸丙酯和0到50重量％甲基丙烯酸甲酯而获得的。
3.根据权利要求1所述的加工助剂，其中所述共聚物是通过在不存在任何其它可共聚单体的情况下聚合80到100重量％甲基丙烯酸乙酯和0到20重量％甲基丙烯酸甲酯而获得的。
4.一种基于氯乙烯树脂的泡沫成型组合物，包含100重量份氯乙烯树脂和1到25重量份根据权利要求1使用的泡沫成型用加工助剂。
5.根据权利要求4所述的基于氯乙烯树脂的泡沫成型组合物，其中所述组合物展现等于或大于130％的泡沫膨胀。
6.根据权利要求4所述的基于氯乙烯树脂的泡沫成型组合物，其中所述组合物展现等于或大于135％的泡沫膨胀。
7.一种泡沫成型产品，由根据权利要求4所述的基于氯乙烯树脂的泡沫成型组合物形成。
8.根据权利要求7所述的泡沫成型产品，其中所述产品是发泡结构部件。
9.一种使氯乙烯树脂泡沫成型的方法，包含挤出根据权利要求4所述的基于氯乙烯树脂的泡沫成型组合物。
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