CN1729099A - 可共挤出多层聚合物 - Google Patents

可共挤出多层聚合物 Download PDF

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Publication number
CN1729099A
CN1729099A CNA2003801067009A CN200380106700A CN1729099A CN 1729099 A CN1729099 A CN 1729099A CN A2003801067009 A CNA2003801067009 A CN A2003801067009A CN 200380106700 A CN200380106700 A CN 200380106700A CN 1729099 A CN1729099 A CN 1729099A
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China
Prior art keywords
polymer
weight
skin
copolymer
multiple layer
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Pending
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CNA2003801067009A
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English (en)
Inventor
G·H·霍夫曼恩
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of CN1729099A publication Critical patent/CN1729099A/zh
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Abstract

本发明提供一种多层聚合物组合物，它包含一个极性外层和一个非极性第二外层。极性外层优选是PVC以及非极性外层优选是聚丙烯。胶粘剂连结层是共聚酯弹性体、非极性聚合物和含有能与共聚酯弹性体的端官能基反应的官能基且与第二外层中的非极性聚合物完全或部分混溶的共聚物的特殊共混物。该多层聚合物能方便地进行共挤出。非极性外层能包含所制零件的主体，只带一薄层极性聚合物，因此能以较低成本提供所期望的极性聚合物的特性。

Description

可共挤出多层聚合物
                     发明背景
发明领域
本发明涉及多层聚合物组合物，它们包含两个外层和一个胶粘剂连结层。本发明特别涉及一种多层聚合物组合物：它包含一种极性聚合物如聚氯乙烯(PVC)，作为第一外层，一种非极性聚合物如聚丙烯，作为第二外层以及一种特殊的聚合物共混物，作为胶粘层连结层，后者可以使组合物容易且方便地共挤出。
背景技术
常常希望粘结极性聚合物与非极性聚合物。非极性聚烯烃如聚乙烯和聚丙烯一直是成本低于极性聚合物的传统商品。用非极性聚合物作制件的主体，仅在表面带一薄层极性聚合物，能以较低的总成本提供极性聚合物的特性。
作为一个具体实例，住房建筑工业中所用的PVC侧板的尺寸稳定性一般都不好。由于其低玻璃化转变温度Tg和柔软性，在室温下会交替地膨胀与收缩，这在用作住房侧板时就成为一个问题。为尽量减轻这个问题，只能用热反射浅色。
为克服尺寸稳定性不良的问题，可以将PVC与聚丙烯和/或玻璃纤维增强或填充聚丙烯厚基底组合起来，这种组合体在所有温度下刚度更高，尺寸更稳定。这样还能降低成本，因为较昂贵的PVC可以比传统侧板中所用的薄得多。随着尺寸稳定性问题的解决，也就可以用深色PVC。
但是，要以结构良好且成本效益高的方式来粘结极性聚合物如PVC与非极性聚合物如聚丙烯仍然是一个问题。
过去一直在努力解决这一问题。例如，U.S.专利6,045,732(Nakatsuji等)公开了一种含氯乙烯树脂皮层和聚丙烯树脂芯的多层模塑制品。它们公开了一种用来组合氯乙烯树脂与聚丙烯树脂芯的胶粘剂层(A)，它含有两层，一层(聚酯树脂和含环氧基乙烯共聚物)与氯乙烯树脂粘结，一层(至少一种选自乙烯共聚物和含环氧基共聚物的共聚物)与聚丙烯树脂芯粘结。或者，也可以用胶粘剂层(B)，它包含一种乙烯树脂组合物，该组合物含一种多元羧酸和一种含环氧基共聚物。但是这类多层制品必须在热和压力作用下的模塑才能形成最终多层制品。胶粘剂层是在一个分立步骤中预先形成的，方法是：对于胶粘挤层(A)，共挤出该胶粘剂层；对于胶粘剂层(B)，用粉末模塑法、吹胀模塑或挤出法。
                    发明内容
本发明在此提供一种多层聚合，它包含
(1)一个第一外层，
(2)一个第二外层以及
(3)一个介于两外层之间的胶粘剂层，
其中，第一外层包含一种极性聚合物，第二外层包含一种非极性聚合物，以及胶粘剂连结层包含：
(a)一种与极性聚合物完全或部分混溶的共聚酯弹性体，
(b)一种与第二外层中非极性聚合物完全或部分混溶的非极性聚合物，以及
(c)一种含有能与组分(a)的端官能基反应的官能基且与第二外层中非极性聚合物完全或部分混溶的共聚物。
该胶粘剂连结层中的组分(c)优选包含一种通式为E/X/Y的乙烯共聚物，其中
E是由乙烯形成的基团，且构成该乙烯共聚物的约40-90重量％，
X是由
Figure A20038010670000071
形成的基团，其中
R1是一个含1～8个碳原子的烷基，
R2选自下列一组：H、CH3或C2H5，以及X构成该乙烯共聚物的约0～40重量％以及
Y选自甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯，以及Y构成该乙烯共聚物的0.1～20重量％。
该多层聚合物宜作建筑物的外侧板及其它制品。而且，本发明还提供由共挤出或层合法制造多层聚合物的方法。
                     附图简述
图1A和1B代表能使3股熔体流汇聚并被共挤出的共挤出供料头内插件的示意图。
                   具体实施方式
定义
术语“共聚物”是指由两种或多种单体聚合而成的聚合物，因此包括三元共聚物在内，或者更精确地说，是指含两种或多种重复单元的聚合物。
术语“均聚物”是指由一种单体加聚而成或由两种单体(例如一种二醇和一种二酸(或二酸的甲酯))缩聚而成的聚合物，或更精确地说，是指含一种重复单元的聚合物。
术语“完全或部分混溶”能解释如下。术语“混溶”能用来描述其行为类似于对单相体系预期行为的聚合物-聚合物共混物。在大多数情况下，关键性能将是玻璃化转变温度；有一个玻璃化转变温度的共混物可归类为“完全混溶”。用混溶性聚合物混合物，能确保力学相容性因而实现组分间的性能折衷。但是，大多数聚合物对在混合后会形成两相共混物，通常从这类非常大分子的小混合熵可以证明。这类共混物的一般特征是不透明、分立的热转变和不良的力学性能。通常在聚合物-聚合物界面上能观察到至少部分混合，导致两个玻璃化转变的加宽，因此能把这类共混物看作是“部分混溶”的。
本发明涉及一种能便利而容易地用共挤出法成形的多层聚合物。本发明克服了粘结极性聚合物与非极性聚合物的普遍问题，且以成本效益高和有用的方法实现了这一点。该多层聚合物具有价格较贵的极性聚合物的理想物理性能，成本远低于单独使用极性聚合物的成本。所得多层聚合物在多方面有用，例如，建筑物的外侧板、各种建筑材料、汽车车内零件、船壳和其它水下零件、玩具等。
本发明的第一实施方案提供一种多层聚合物，它包含(1)一个第一外层，(2)一个第二外层和(3)一个介于两外层之间的胶粘剂连结层。第一外层包含一种极性聚合物。该极性聚合物优选选自聚氯乙烯(PVC)均聚物与共聚物、丙烯腈-丁二烯-苯乙烯(ABS)、聚偏氯乙烯(PVDC)、聚对苯二甲酸乙二醇酯(PET)均聚物或共聚物、聚酰胺、聚碳酸酯、乙烯乙烯醇(EVOH)均聚物与共聚物、酸共聚物、离聚物、液晶聚合物、聚缩醛、缩醛共聚物和聚乳酸。非常优选PVC作为极性聚合物。第一外层所用的典型厚度范围是约2-10密耳(0.05～0.25mm)。
第二外层包含一种非极性聚合物。非极性聚合物优选是聚烯烃，更优选选自聚丙烯均聚物与共聚物以及聚乙烯均聚物与共聚物。非极性聚合物非常优选含或不含玻璃纤维或其它矿物(如滑石)增强剂的聚丙烯均聚物。
胶粘剂连接层包含(a)一种与极性聚合物完全或部分混溶的共聚酯弹性体，(b)一种与第二外层中非极性聚合物完全或部分混溶的非极性聚合物以及(c)一种含有能与组分(a)的端官能基反应的官能基且与第二外层中非极性聚合物完全或部分混溶的共聚物。
本发明优选的共聚酯弹性体可购自杜邦公司(Wilmington，Delaware)，商品名为Hytrel，以不同级别出售。Hytrel是一种兼具橡胶性能和塑料力学行为的热塑性醚-酯弹性体。弹性体的聚醚段较柔软，而聚酯段较刚硬。为实现不同性能，可改变各段的量。共聚酯弹性体的极性有利于它与第一外层中极性聚合物的部分混溶性。
更具体地说，共聚酯弹性体包含一种嵌段热塑性共聚酯，它包含许多个通过酯键头-尾连接的重复长链酯单元和短链酯单元。长链酯单元由下式代表
Figure A20038010670000091
短链酯单元由下式代表
Figure A20038010670000101
其中G是一个从分子量约为400～6000、碳与氧之比约为2.0～4.3的聚烯化氧二醇除去端羟基后留下的二价基团，。R是一个从分子量低于约300的二元羧酸上除去羧基后留下的二价基团。D是一个从分子量低于约250的二元醇除去羟基后留下的二价基团。短链酯单元的量占共聚酯的约15～95重量％，至少约50％所述短链酯单元是相同的。该共聚酯弹性体在U.S.专利4,739,012、3,651,014、3,763,109和3,755,146中有进一步描述，这些专利包括于此供参考。
虽然并非共聚酯弹性体的主要组分，但可以混合进不同量的任意种传统填料或复合组分。这类组分的实例包括各种炭黑、粘土、二氧化硅、氧化铝、碳酸钙、二氧化钛、玻璃纤维、抗氧剂、防降解剂、增稠剂、加工助剂如润滑剂和蜡，以及增塑剂如二烷基对苯二甲酸酯、三烷基苯六甲酸酯、二烷基酯如己二酸、壬二酸和戊二酸的二烷基酯、以及聚酯齐聚体。用量至少部分取决于组合物内其它组分的量以及对组合物期望的性能。此外，还可以加入少量其它饱和与不饱和聚合物，如α-烯烃，以降低成本或改善组合物的性能。
Hytrel4069和4056是本发明优选用作共聚酯弹性体的高性能级热塑性醚-酯弹性体。它们包含聚亚丁基二醇(PTMEG)软段且一般具有约55或更低的邵氏D硬度。
胶粘剂连结层中的组分(b)是一种与第二外层中非极性聚合物完全或部分混溶的非极性聚合物。组分(b)优选是一种聚烯烃，更优选聚丙烯均聚物或共聚物，或聚乙烯均聚物或共聚物。非常优选组分(b)与第二外层中所含的非极性聚合物相同。
胶粘剂连结层中的组分(c)包含一种共聚物，它含有能与组分(a)的端官能基(即羟和酸端基)反应的官能基且与第二外层中的非极性聚合物部分或完全混溶。能与组分(a)的端官能基反应的优选官能基包括环氧基和酸酐官能基，环氧官能度与酸酐官能基的优选量可由本领域内的技术人员通过试验确定。官能度太高会使共聚酯弹性体交联并使共聚酯弹性体难以流过挤出机。共聚酯弹性体的官能度太少将反应不充分，从而使两相缺少合适强度所需的共价键结合。
组分(c)优选包含一种通式如E/X/Y的乙烯共聚物，其中E是由乙烯形成的基团，X是由
Figure A20038010670000111
形成的基团。
其中R1是一个含1～8个碳原子的烷基，R2选自H、CH3或C2H5，或者，X是乙酸乙烯酯，以及Y选自甲基丙烯酸缩水甘油酯或丙烯酸的缩水甘油酯。E优选占约40～90重量％，X优选占约0～40重量％，以及Y优选占约0.1～20重量％，其中所有的重量百分数均以乙烯共聚物的总重量为基准计算。更优选E/X/Y共聚物选自下列一组共聚物：乙烯-丙烯酸正丁酯-甲基丙烯酸缩水甘油酯(EnBAGMA)、乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯(EBAGMA)、乙烯-甲基丙烯酸缩水甘油酯(EGMA)、乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯(EMAGMA)、乙烯-丙烯酸乙酯-甲基丙烯酸缩水甘油酯(EEAGMA)、乙烯-丙烯酸丙酯-甲基丙烯酸缩水甘油酯(EPAGMA)以及乙烯-乙酸乙烯酯-甲基丙烯酸缩水甘油酯(EVAGMA)。非常优选E/X/Y共聚物是EnBAGMA。
组分(c)也可优选包含一种酸共聚物或衍生自酸共聚物的酸酐。在该实施方案中，组分(c)更优选包含马来酸酐接枝聚丙烯。
至于胶粘剂连结层的整个组合物，优选组分(a)占约25～65重量％，组分(b)占约0～65重量％以及组分(c)占约10～50重量％，其中所有重量％均以胶粘剂层的总重量为基准计算。更优选组分(b)占约25～65重量％。
在本发明多层聚合物的一个优选实施方案中，第一外层包含PVC，第二外层包含聚丙烯均聚物以及胶粘剂连结层包含约25～65重量％Hytrel4069，更优选约30～46重量％，非常优选约38重量％；约0～65重量％聚丙烯均聚物，更优选约10～50重量％，非常优选约35～55重量％；和约10～50重量％EnBAGMA，更优选约25～65重量％，非常优选约15～20重量％，其中重量％均以胶粘剂连结层的总重量为基准计算。
一般地说，包含本发明多层聚合物的任何聚合物还可含有任何种传统添加剂，包括填料、复合组分、抗氧剂、防降解剂、增稠剂、加工助剂如润滑剂、蜡、增塑剂和本领域内的技术人员所知的其它添加剂。
或者，在本文多层聚合物的另一个实施方案中，胶粘剂连结层可包含一个双层结构，它可以在连接第一和第二外层之前先用共挤出或模塑法成形。在该实施方案中，胶粘剂连接层中只用上述组分(c)和(a)；各层作为其本身的次层。例如，可以用EnBAGMA作为组分(c)并形成双层胶粘剂连接层中的一个次层以及可以用一种共聚酯如嵌段热塑性醚-酯作为组分(a)并形成另一个次层。然后将该胶粘剂层层合或共挤出到第一与第二外层上，使EnBAGMA层接触第二外层以及共聚酯接触第一外层。
本发明还提供一种制造多层聚合物的方法，它包含一个共挤出上述第一外层、第二外层和胶粘剂连接层的步骤。本发明的一个优点是，该多层聚合物能容易地用共挤出法成形并避免了本领域内大多数类似多层聚合物中的多步工艺。共挤出能利用挤出机口模内的一个如图1A与1B所示的内插件来实现，该插件允许不同厚度的3股聚合物流被挤出成形为一个三层结构。聚合物流将通过口模内插件40的顶部流进并通过底部50流出。该口模插件有3个开口，第一个10是一个能用于第一外层入流的开口，第二开口20将过滤第二外层的入流，以及第三开口30将引导胶粘剂连接层的入流。所有这3股料流将作为一个多层聚合物流出口模。加工条件是本领域内技术人员能得知的。
此外，如果需要，本发明的多层聚合物还可以用层合法成形。在此情况下，将分别挤出第一与第二外层及胶粘剂层。然后对3个挤出层施以足够的热和压力以熔融这些层并形成一个性多层聚合物。所需的热和压力是本领域内的技术人员能得知的。
本发明将通过下述实施例进一步阐明，这些实施例仅是纯例证性的。
                         实施例
可共挤出胶粘剂配方
表1-7描述了试验配方的范围，其中极性树脂要粘结到非极性聚烯烃基底上。
                         表1
                可共挤出胶粘剂共混物
             W&P双螺杆(30mm)按比例扩大运行
  组分(份数)   1A   1B   1C
  HYTREL4069(1)   60   60   60
  PP(2)   30   30   30
  EBAGMA(3)   10   20   30
  其它
  性能
  拉伸屈服强度(磅/英寸2)   1261   1088   1043
  (MPa)   8.7   7.5   7.2
  屈服伸长率(％)   10   11   11
  拉伸断裂强度(磅/英寸2)   1043   1107   1121
  (MPa)   7.2   7.0   7.7
  断裂伸长率(％)   57   61   55
  熔体指数(4)   0.2   0.4   0.4
  熔体指数(5)   66   108   112
(1)在2.16KG下MI＝0；在21.6KG下MI＝17(200℃)
(2)PROFAX6823(MI＝0.2)
(3)EP4934-6(MI＝15)
(4)200℃，2160GR
(5)200℃，21.60KG
                           表2
                    可共挤出胶粘剂共混物
                W&P双螺杆(30mm)按比例扩大运行
  组分(份数)   2A   2B   2C
  HYTREL4069(1)   60   60   60
  PP(2)   30   30   30
  EGMA(3)   10   20   30
  其它
  性能
  拉伸屈服强度(磅/英寸2)   1053   1677   1475
  (MPa)   7.3   11.6   10.2
  屈服伸长率(％)   7   7   7
  拉伸断裂强度(磅/英寸2)   1488   1692   1710
  (MPa)   10.3   11.7   11.8
  断裂伸长率(％)   17   52   18
  熔体指数(4)   0.1   0.8   0.6
  熔体指数(5)   54   67   105
(1)在2.16KG下MI＝0；在21.6KG下MI＝17(200℃)
(2)PROFAX6823(MI＝0.2)
(3)EP4934-8(MI＝4)
(4)200℃，2160GR
(5)200℃，21.60KG
                        表3
                可共挤出胶粘剂共混物
            W&P双螺杆(30mm)按比例扩大运行
  组分(份数)   3A   3B   3C
  HYTREL4069(1)   60   60   60
  PP(2)   30   30   30
  EBAGMA(3)   10   20   30
  其它
  性能
  拉伸屈服强度(磅/英寸2)   1110   1556   1000
  (MPa)   7.6   10.7   6.9
  屈服伸长率(％)   9   10   12
  拉伸断裂强度(磅/英寸2)   1157   1520   1008
  (MPa)   7.8   10.5   6.9
  断裂伸长率(％)   25   77   68
  熔体指数(4)   0.0   0.0   0.0
  熔体指数(5)   20   15   19
(1)在2.16KG下MI＝0；在21.6KG下MI＝17(200℃)
(2)PROFAX6823(MI＝0.2)
(3)ELVALOY4170(MI＝8)
(4)200℃，2160GR
(5)200℃，21.60KG
                                表4
                        可共挤出胶粘剂共混物
                    W&P双螺杆(30mm)按比例扩大运行
  组分(份数)   4A   4B   4C   4D
  HYTREL4069   42   42   42   42
  PP(1)   38   44   50   56
  EGMA(2)   20   20   20   20
  其它
  性能
  拉伸屈服强度(磅/英寸2)   2118   2005   1969   2261
  (MPa)   14.6   13.8   13.6   15.6
  屈服伸长率(％)   13   7   7   12
  拉伸断裂强度(磅/英寸2)   1841   2116   2312   1974
  (MPa)   12.7   14.6   15.9   13.6
  断裂伸长率(％)   175   28   18   50
  熔体指数(3)   0.3   0.4   0.4   0.3
  熔体指数(4)   60.0   60.0   59.0   46
(1)PROFAX6823(MI＝0.2)
(2)EP4934-8(MI＝4)
(3)200℃，2160GR
(4)200℃，21.60KG
                            表5
                    可共挤出胶粘剂共混物
                W&P双螺杆(30mm)按比例扩大运行
  组分(份数)   5A   5B   5C   5D
  HYTREL4056   42   42   42   42
  PP(1)   3B   44   50   56
  EGMA(2)   20   20   20   20
  其它
  性能
  拉伸屈服强度(磅/英寸2)   2291   1975   2881   2878
  (MPa)   15.8   13.6   19.9   19.8
  屈服伸长率(％)   15   5   18   16
  拉伸断裂强度(磅/英寸2)   1807   2282   2008   2432
  (MPa)   12.5   15.7   13.8   16.8
  断裂伸长率(％)   148   25   352   276
  熔体指数(3)   3.2   2.8   2.4   2.2
  熔体指数(4)   169   179   190   159
(1)PROFAX6823(MI＝0.2)
(2)EP4934-8(MI＝4)
(3)200℃，2160GR
(4)200℃，21.60KG
                                    表6
                            可共挤出胶粘剂共混物
                        W&P双螺杆(30mm)按比例扩大运行
  组分(份数)   6A   6B   6C   6D
  HYTREL4069   42   42   42   42
  PP(1)   38   44   50   56
  PP-g-MAH(2)   20   20   20   20
  其它
  性能
  拉伸屈服强度(磅/英寸2)   1530   1719   2183   2838
  (MPa)   10.5   11.8   15.0   19.6
  屈服伸长率(％)   4   5   6   11
  拉伸断裂强度(磅/英寸2)   2300   2388   2671   2817
  (MPa)   15.8   16.5   18.4   19.4
  断裂伸长率(％)   10   12   24   123
  熔体指数(3)   0.6   0.6   0.5   0.4
  熔体指数(4)   173   161   140   103
(1)PROFAX6823(MI＝0.2)
(2)FUSABONDP353D(MI＝280)
(3)200℃，2160GR
(4)200℃，21.60KG
                                表7
                        可共挤出胶粘剂共混物
                    W&P双螺杆(30mm)按比例扩大运行
  组分(份数)   7A   7B   7C   7D
  HYTREL4069   42   42   42   42
  PP(1)   42   42   42   42
  PP-g-MAH(2)   20   20   20   20
  PP(3)   14   28   42   56
  性能
  拉伸屈服强度(磅/英寸2)   2837   3045   3097   3190
  (MPa)   19.5   21.0   21.3   22.0
  屈服伸长率(％)   19   17   19   17
  拉伸断裂强度(磅/英寸2)   5238   5021   3006   2639
  (MPa)   36.1   34.6   20.7   18.2
  断裂伸长率(％)   857   772   547   468
  熔体指数(4)   0.5   0.5   0.4   0.4
  熔体指数(5)   133   158   95   76
(1)PROFAX6823(MI＝0.2)
(2)FUSABONDP 353D(MI＝280)
(3)PROFAX 6823，在第二喂料口内
(4)200℃，2160GR
(5)200℃，21.60KG
可共挤出胺粘剂的熔体复合
将包括杜邦Hytrel共聚酯弹性体(在70℃真空烘箱内烘干)在内的所有组分进行颗粒共混并喂进一台30mm Werner和Pleiderer同向旋转双螺杆挤出机。该挤出机由9个料筒组成，总长870mm，螺杆设计如表8所示。喂料口在第一个料筒上，抽真空口在料筒8上。一个每孔直径为3/16英寸(1.27cm)的双孔口模在料筒9的末端。当胶粘剂熔体从口模流出时，料条要在水浴中淬火，然后切割成颗粒。烘干产物(在70℃真空烘箱内)并第二次再挤出以确保官能化增容剂与Hytrel充分反应。料筒的温度分布是从200℃～250℃的上升图，使熔体温度达到约250℃。螺杆转速为150rpm，挤出速率为30磅/小时(14kg/小时)。
                 表8
            挤出机螺杆设计
  轴套   说明   编号
  42/42R   喂料   2   84
  42/21R   1   105
  28/28R   3   189
  KB2BN   2   245
  20/10L   1   255
  42/42R   2   339
  KB28N   2   395
  20/10L   1   405
  42/42R   2   489
  28/28R   1   517
  KB14R   1   531
  14/14R   1   545
  20/10L   2   565
  42/42R   4   733
  42/21R   1   754
  20/10L   1   764
  28/28R   3   848
  20/10R   1   858
  20/20R   1   878
            **符号RH和LH表示螺距/长度**
搭剪试验(ASTM D 3163-96)
用3英寸(7.62cm)长、1英寸宽(2.54cm)×1/8英寸(0.32cm)厚的底基(即极性与非极性外层)制备搭剪试样。将极性底基与非极性底基的一个搭在另一个之上，使它们的搭接面积为1英寸2(2.542cm2)；在它们搭接处，用一层0.01英寸(0.025cm)厚的胶粘剂连结层将它们连接起来。在上底基与搭接端相反的另一端的下面放一块垫片。
在一台预热的压机上，于两块不锈钢板间制备样品，用1/8英寸(0.32cm)垫片(如上所述)支撑上底基并使连接/搭接面在压制期间保持水平。用约0.26英寸(0.67cm)厚的其它垫片使试样能在压机上以接触压力制备。压机要预热到200℃。加压5分钟后，让样品冷却到室温后从压机上取下。
从压机上取下样品，修去挤出的胶粘剂以给出真正1英寸2(2.542cm2)试验面积并在23℃和50相对湿度下过夜。然后在Instron上用手拧无滑动夹具以0.2英寸/分钟(0.5cm/min)的十字头速度进行试验。标距长度约1.75英寸(4.45cm)。
表9概括了在聚烯烃(聚丙烯和聚乙烯)与宽阔范围极性树脂之间有胶粘剂时所获得的搭剪值。在所有情况下，观察到无胶粘剂连接层的样品无粘结性。
                            表9
                    共挤出胶粘剂搭剪值(1)
实施例   极性聚合物   非极性聚合物   搭剪强度(磅/英寸2)   搭剪强度(MPa)
  1A   PVC(2)   聚丙烯(3)   353   2.4
  1B   ″   ″   182   1.3
  1C   ″   ″   200   1.4
  2A   ″   ″   292   2.0
  2B   ″   ″   188   1.3
  2C   ″   ″   49   0.3
  3A   ″   ″   105   0.7
  3B   ″   ″   202   1.4
  3C   ″   ″   161   1.1
  4A   ″   ″   100   0.7
  4B   ″   ″   110   0.8
  4C   ″   ″   152   1.0
  4D   ″   ″   148   1.0
  5A   ″   ″   297   2.0
  5B   ″   ″   203   1.4
  5C   ″   ″   349   2.4
  5D   ″   ″   250   1.7
  6A   ″   ″   228   1.6
  6B   ″   ″   105   0.7
  6C   ″   ″   180   1.2
  6D   ″   ″   170   1.2
  7A   ″   ″   185   1.3
  7B   ″   ″   228   1.6
  7C   ″   ″   114   0.8
  7D   ″   ″   65   0.4
  6C   聚碳酸酯(4)   ″   75   0.5
  ″   EVOH(5)   ″   230   1.6
  ″   离聚物(6)   ″   151   1.0
  ″   PBT(7)   ″   80   0.6
  ″   尼龙6(8)   ″   284   2.0
  ″   LCP共混物(9)   ″   104   0.7
  ″   ″   聚乙烯(10)   120   0.8
(1)在两片聚合物片(每片厚125密耳(0.32cm))之间用10密耳(0.025cm)胶粘剂薄膜，搭接1英寸(2.54cm)，在200℃压机上不加压加热5分钟。在25℃调节22小时。
由此法压制的无胶粘层的聚合物片脱开
(零剪切强度值)
(2)GEON87416
(3)PROFAX6823
(4)LEXAN134R
(5)SELAROH 4416
(6)SURLYN8140
(7)CRASTIN6129
(8)CAPRON8202
(9)ZENITE400/HYTREL4556(85/15)
(10)SCLAIR2909
剥离强度试验(ASTM D903-98)
从共挤出层合板上沿机器方向和横向切割试样。试样宽1英寸(25mm)，长约6英寸(152mm)。3层的厚度，如表10所示，要在PVC层从底基(聚丙烯)层上剥开后测量。在50％相对湿度和23℃调节22小时后，将试样装在Instron拉伸试验机上，以下夹头夹住聚丙烯底基，上夹头夹住剥离开的原先毗邻的PVC层。
这就允许粘结面以约180°角分离。剥离强度是使粘结面上的一个表面与另一个表面逐渐剥开所需的单位宽度粘结线的平均裁荷。
用2英寸/min(5.1cm/min)和10英寸/min(25.4cm/min)的分离速率产生剥离强度值，单位是磅/英寸(kg/mm)，如表10所示
                            表10
                    共挤出片材的剥离粘结值
                   层厚(密耳/mm)   粘结性(3)
  实施 例   PP(1)   胶粘剂   PVC(2)   2″/MIN    10″/MIN.
  (5.1cm/min)   (25.4cm/min)
  磅/英寸kg/mm  磅/英寸   kg/mm
  4A   71/1.8   8/0.20   9/0.23   2-6   0.04-0.11   3-8   0.05-0.14
  4B   74/1.9   7/0.18   9/0.23   2-6   0.04-0.11   4-6   0.07-0.11
  4C   77/2.0   6/0.15   7/0.18   4-5   0.07-0.09   4-7   0.07-0.13
  4D   77/2.0   6/0.15   3/0.08   2-3   0.04-0.05   3-5   0.05-0.09
  6A   73/1.9   6/0.15   3/0.0B   1-2   0.03-0.04   3-4   0.05-0.07
  6B   74/1.9   6/0.15   2/0.051   1-6   0.02-0.11   3-7   0.05-0.13
  6C   74/1.9   7/0.18   2/0.051   4-6   0.07-0.11   5-8   0.09-0.14
  6D   70/1.8   1/0.02   3/0.08   3-5   0.05-0.09   6-9   0.11-0.13
  7A   74/1.9   8/0.20   4/0.10   3-4   0.05-0.07   6-7   0.11-0.13
  7B   73/1.9   8/0.20   3/0.08   4-7   0.07-0.13   5   0.09
  7C   74/1.9   9/0.23   3/0.08   5   0.09   6   0.11
  7D   71/1.8   9/0.23   3/0.08   3-4   0.05-0.07   4-6   0.07-0.11
(1)PROFAX6823
(2)GEON83974BROWN 3830
(3)180°，磅/英寸(kg/mm)：在整个幅宽上沿机器方向与横向拉伸的数值范围
1英寸(2.54cm)样品
无胶粘剂对比样品无粘结性(脱开)
共挤出工艺
概述
下文解释用来生产实施例共挤出样品的共挤出工艺。将3台挤出机通过传料线联接到供料头，供料头又与一个平膜口模联接。将共挤出膜喂到由一对夹辊和随后流延辊组成的三辊堆。之后又是由2个橡胶夹辊与随后收集终产物的收膜辊组成的引出辊。
挤出机A 
该挤出机用来熔化并喂进非极性聚烯烃树脂。Killion ExtrudersInc.制造，螺杆长36英寸(91cm)，直径1.5英寸(3.81cm)。螺杆上有一个长20英寸(51cm)的混合段。
挤出机B
该挤出机来自挤出机A的同一制造厂，配备有一根长24英寸(61cm)、直径1英寸(2.54cm)的螺杆且按通用螺杆设计。挤出机B用来熔化并喂入可共挤出胶粘剂。
挤出机C
该挤出机也来自同一制造厂并配备有一根长30英寸(76cm)、直径1.25英寸(3.2cm)的螺杆。该螺杆也是通用螺杆，用来熔化并喂入极性树脂，如PVC树脂。
供料头
汇聚进3股熔体流的挤出机供料头配备有一个内插件，它把3股熔体带到一起，以PVC为顶层，胶粘剂为中间层和聚烯烃为底层。图1A和1B示意了该插件的设计。
口模
口模由Extrusion Dies，Inc.制造，且具有带可调节唇口的“衣架式”设计，宽为14英寸(35.6cm)。
工艺条件
挤出机A以131rpm运行，料筒温度的设置要使聚丙烯熔体温度达200～212℃。挤出机B以30～36rpm运行，料筒温度的设置要使胶粘剂熔体温度达197～209℃。挤出机C以31～37rpm运行，料筒温度的设置要使PVC熔体温度达198～203℃。传料线的温度设在195～210℃，口模温度设在195℃。用1.7英尺/分钟(52cm/min)的产物收集速率。
产物性能
表10概括了从不同共挤出样品生产的3层膜的性能。相对于无胶粘剂因而无粘结性的对比样品，所有样品都具有良好粘结性。

Claims (22)

1.一种多层聚合物，包含：
(1)一个第一外层，
(2)一个第二外层和
(3)一个介于两外层之间的胶粘剂连结层
其中，第一外层包含一种极性聚合物，第二外层包含一种非极性聚合物，以及胶粘剂连结层包含
(a)一种与所述极性聚合物完全或部分混溶的共聚酯弹性体，
(b)一种与第二外层中非极性聚合物完全或部分混溶的非极性聚合物，以及
(c)一种含有能与组分(a)的端官能基反应的官能基且与第二外层中非极性聚合物完全或部分混溶的共聚物。
2.权利要求1的多层聚合物，其中胶粘剂连结层中的组分(c)包含一种通式为E/X/Y的乙烯共聚物，其中
E是由乙烯形成的基团且构成该乙烯共聚物的约40～90重量％，
X是由
Figure A2003801067000002C1
形成的基团，其中R1是一个含1～8个碳原子的烷基，R2选自H、CH3或C2H5，X构成该乙烯共聚物的约0-40重量％，Y选自甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯，以及Y构成该乙烯共聚物的0.1～20重量％。
3.权利要求1的多层聚合物，其中胶粘层连结层中的组分(c)包含一种通式为E/X/Y的乙烯共聚物，其中
E是由乙烯形成的基团且构成该乙烯共聚物的约40～90重量％，
X是乙酸乙烯酯，且构成该乙烯共聚物的约0-40重量％，以及
Y选自甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯，以及Y构成该乙烯共聚物的0.1～20重量％。
4.权利要求1的多层聚合物，其中，胶粘剂连结层包含约25～65重量％组分(a)，约0～65重量％组分(b)以及约10～50重量％组分(c)，所有百分数都以胶粘剂连结层的总重量为基准计算。
5.权利要求1的多层聚合物，其中胶粘剂连结层包含约25～65重量％组分(a)，约25～65重量％组分(b)以及约10～50重量％组分(c)，所有百分数都以胶粘剂连结层的总重量为基准计算。
6.权利要求1的多层聚合物，其中，第一外层包含一种选自下列一组的极性聚合物：聚氯乙烯均聚物和共聚物，丙烯腈-丁二烯-苯乙烯(ABS)、聚偏氯乙烯(PVDC)、聚对苯二甲酸乙二醇酯(PET)均聚物或共聚物、聚酰胺、聚碳酸酯、乙烯乙烯醇均聚物和共聚物、酸共聚物、离聚物、液晶聚合物、聚缩醛、缩醛共聚物和聚乳酸。
7.权利要求1的多层聚合物，其中第二外层包含一种选自下列一组的非极性聚合物：聚丙烯均聚物和共聚物，以及聚乙烯均聚物和共聚物。
8.权利要求1的多层制品，其中共聚酯弹性体包含一种其软段还包含聚亚丁基二醇(PTMEG)的嵌段热塑性醚-酯弹性体，以及共聚酯弹性体的邵氏D硬度为约55或更低。
9.权利要求1的多层聚合物，其中E/X/Y共聚物是选自下列一组的共聚物：乙烯-丙烯酸正丁酯-甲基丙烯酸缩水甘油酯(EnBAGMA)、乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯(EBAGMA)、乙烯-甲基丙烯酸缩水甘油酯(EGMA)、乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯(EMAGMA)、乙烯-丙烯酸乙酯-甲基丙烯酸缩水甘油酯(EEAGMA)、乙烯-丙烯酸丙酯-甲基丙烯酸缩水甘油酯(EPAGMA)以及乙烯-乙酸乙烯酯-甲基丙烯酸缩水甘油酯(EVAGMA)。
10.权利要求1的多层聚合物，其中第一外层包含PVC以及第二外层包含聚丙烯均聚物。
11.权利要求10的多层聚合物，其中胶粘剂连结层包含约25～65重量％共聚酯弹性体，约10～50重量％聚丙烯以及约25～65重量％EnBAGMA，所有重量％均以胶粘剂连结层总重量为基准计算，所述共聚酯弹性体包含一种其软段包含聚亚丁基二醇(PTMEG)的嵌段热塑性醚-酯弹性体，其邵氏D硬度为约55或更低。
12.权利要求11的多层聚合物，其中，多层聚合物的剥离强度，用ASTM#D903-98测量时，高于约5磅/英寸宽(0.09kg/mm宽)。
13.包含权利要求11的多层聚合物的建筑物外侧板。
14.权利要求13的外侧板，其中第一外层PVC构成侧板的外表面。
15.一种包含权利要求11的多层聚合物的制品，其中该制品选自下列一组：建筑材料、汽车车内零件和玩具。
16.权利要求11的多层聚合物，其中聚合物由选自下列一组的方法制成：共挤出和层合。
17.权利要求1的多层聚合物，其中组分(c)包含一种酸共聚物或衍生自酸共聚物的酸酐。
18.权利要求17的多层聚合物，其中组分(c)包含马来酸酐接枝聚丙烯。
19.一种制造多层聚合物的方法，包含共挤出下列各层以形成多层聚合物的步骤：
(1)一个第一外层，
(2)一个第二外层和
(3)一个介于两外层之间的胶粘剂连结层，
其中，第一外层包含一种极性聚合物，第二外层包含一种非极性聚合物，以及胶粘剂连结层包含
(a)一种与极性聚合物完全或部分混溶的共聚酯弹性体，
(b)一种与第二外层中非极性聚合物完全或部分混溶的非极性聚合物，以及
(c)一种含有能与组分(a)的官能端基反应的官能基且与第二外层中非极性聚合物完全或部分混溶的共聚物。
20.权利要求19的方法，其中，第一外层包含PVC，第二外层包含聚丙烯均聚物以及胶粘剂连结层包含约25～65重量％共聚酯弹性体，约10～50重量％聚丙烯和约25～65重量％EnBAGMA，其中所有重量％均以胶粘剂连结层的总重量为基准计算，所述弹性体包含一种其软段包含聚亚丁基二醇(PTMEG)的嵌段热塑性醚-酯弹性体，其邵氏D硬度为约55或更低。
21.一种制造多层聚合物的方法，包含层合下列各层的步骤：
(1)一个第一外层，
(2)一个第二外层以及
(3)一个介于两外层之间的胶粘剂连结层，
所述层合在足够的热与压力作用下进行以使上述各层融化并形成多层聚合物，
其中，第一外层包含一种极性聚合物，第二外层包含一种非极性聚合物以及胶粘剂连结层包含
(a)一种与极性聚合物完全或部分混溶的共聚酯弹性体，
(b)一种与第二外层中非极性聚合物完全或部分混溶的非极性聚合物，以及
(c)一种含有能与组分(a)的端官能基反应的官能基且与第二外层中非极性聚合物完全或部分混溶的共聚物。
22.权利要求21的方法，其中第一外层包含PVC，第二外层包含聚丙烯均聚物以及胶粘剂连结层包含约25～65重量％共聚酯弹性体，约10～50重量％聚丙烯以及约25～65重量％EnBAGMA，其中所有重量％均以胶粘剂层总重量为基准计算，所述共聚酯弹性体包含一种其软段包含聚亚丁基二醇(PTMEG)的嵌段热塑性醚-酯弹性体，其邵氏D硬度约为55或更低。
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