CN1041768A - 聚苯乙烯用的改进的可共挤塑的粘合剂及由它制得的产品 - Google Patents

聚苯乙烯用的改进的可共挤塑的粘合剂及由它制得的产品 Download PDF

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CN1041768A
CN1041768A CN89106334A CN89106334A CN1041768A CN 1041768 A CN1041768 A CN 1041768A CN 89106334 A CN89106334 A CN 89106334A CN 89106334 A CN89106334 A CN 89106334A CN 1041768 A CN1041768 A CN 1041768A
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李爰华
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Abstract

一种由乙烯醋酸乙烯酯共聚物、用含侧羧酸或侧羧酸衍生物官能度的共聚用单体接枝改性的乙烯醋酸乙烯酯共聚物、和改进了抗冲击性的聚苯乙烯组成的掺合物，它提供了一种有用的粘合剂，特别是用于将苯乙烯粘结到隔气聚合物上的粘合剂。

Description

本发明涉及一种乙烯醋酸乙烯酯共聚物、改性乙烯醋酸乙烯酯共聚物（EVA）及苯乙烯均聚物的可挤塑的粘合剂组合物，它用于使聚苯乙烯与隔气聚合物的粘结。
在现有技术中，使用含被烯属不饱和羧酸或酸酐改性的EVA的粘合剂而制成的聚苯乙烯与隔气树脂的层压物，是公知的。例如，美国专利4576995，中林等人披露了一种使乙烯/乙烯醇共聚物与聚苯乙烯粘结的粘合剂，它包含一种用一种苯乙烯类的乙烯单体和一种α，β-不饱和羧酸往一种乙烯/醋酸乙烯酯共聚物上接枝而制得的改性乙烯/醋酸乙烯酯共聚物。由此制得的层压物作为具有提高了隔气性的深度成型材料是有价值的。
日本申请53018653（如Derwent文摘26079A/14所报导的）描述了一种低温热封粘合剂，它由100份羧化的乙烯醋酸乙烯酯共聚物和3～100份分子量为500～1000的苯乙烯树脂组成。
日本申请54057582（如Derwent文摘46260B/25所报导的）披露了一种树脂层压物，它包含一层聚苯乙烯树脂，一层乙烯-醋酸乙烯酯共聚物的皂化产物，和一层含60%丁二烯的苯乙烯/丁二烯嵌段共聚物、乙烯醋酸乙烯酯共聚物（6摩尔%VA）、和马来酸酐-乙烯醋酸乙烯酯接枝共聚物（3摩尔%VA）。
日本申请58203043（如Derwent文摘84008480/02所报导的）公开了一种相似的层压物，其中粘合剂层是由聚苯乙烯，乙烯-醋酸乙烯酯共聚物（5～50%VA），和以例如马来酸酐接枝的一种聚烯烃组成的掺合物。
日本申请59055743公开了一种制造树脂层压物的方法，其特征为熔体共挤塑出一层苯乙烯基树脂，一层隔气树脂（如皂化的乙烯-醋酸乙烯酯共聚物），以及一粘结层，其中粘结层由（a）用不饱和羧酸或酸酐的接枝改性的乙烯-醋酸乙烯酯共聚物，和（b）用例如苯乙烯接枝改性的乙烯-醋酸乙烯酯共聚物，或进一步和（c）未改性的乙烯-醋酸乙烯酯共聚物所组成。
本发明提供一种可挤塑的粘结树脂组合物，主要由下述物质组成：
（a）约55～80%重量的主要由以下物质组成的乙烯醋酸乙烯酯共聚物组份：
（Ⅰ）0到约99%重量的由约60～87%重量乙烯和约13～40%重量的醋酸乙烯酯共聚用单体组成的共聚物，和
（Ⅱ）约1%到100%重量的一种共聚物，它至少含约50%重量的乙烯，约3～50%重量的醋酸乙烯酯共聚用单体，如果存在的话，此醋酸乙烯酯共聚用单体的数量是在共聚物（Ⅰ）中的醋酸乙烯酯共聚用单体的数量的约10个百分数范围内，和一含侧羧酸或侧羧酸衍生物官能度的接枝共聚用单体，共聚物中上述接枝共聚用单体的数量为组合物总重量的约0.03～0.5%，而（Ⅰ）和（Ⅱ）中共聚醋酸乙烯酯的总量则超过组合物总重量的约13.5%，和
（b）约20～45%重量的分子量大于50000的改进了抗冲击性的聚苯乙烯。
本发明还进一步提供了一种层压结构，它包括至少一结构层、至少一隔气层、和至少一层上述的树脂组合物（用作粘结层）。这种结构显示了所期待的结构强度和隔气性的综合性能，并且各层之间的粘合极好。
本发明的可挤塑粘结树脂包括一种约占55～80%重量的乙烯醋酸乙烯酯（EVA）组份和约占20～45%重量聚苯乙烯组份的掺合物。此EVA组份包括用侧羧酸或侧羧酸衍生物官能度接枝的EVA共聚物。如果需要，此接枝共聚物可与别的未接枝的EVA掺合。为了尽量减少相对较贵的接枝EVA材料的用量，同时保持组合物的极好粘合性能，这种掺合可能是合乎需要的。
未接枝EVA共聚物的用量为组合物中EVA组份的0至约99%重量，优选值为约50～97%重量。这一成份是含共聚合醋酸乙烯酯约13～40%重量，优选值为约25～35%重量的共聚物。这一共聚物的其余部分实际上是共聚合的乙烯。此共聚物的熔融指数（按ASTM        D1238，条件“E”测定）应为约0.5～40。超出这一范围，则加工变得较为困难，而且会导致流动的不稳定。
EVA成分的其余聚合物是一种与上述相似的EVA共聚物，在它上面已接枝上一含侧羧酸或侧羧酸衍生物官能度的共聚用单体。在接枝共聚物中，醋酸乙烯酯共聚用单体的含量应在约3%至约50%重量之间，优选值为约15%至约35%重量之间。为了在由本发明的粘合剂所制得的层压物中获得良好的剥离强度，接枝EVA共聚物中共聚的醋酸乙烯酯，如果出现的话，其数量应在未接枝EVA共聚物中的共聚醋酸乙烯酯数量的10个百分数范围内。这就是说，在接枝EVA共聚物中，共聚醋酸乙烯酯的百分数应在未接枝材料中的共聚醋酸乙烯酯数量的约10个绝对百分点范围内。因此，如果未接枝的EVA共聚物含28%的共聚醋酸乙烯酯，则接枝材料应含18～38%共聚醋酸乙烯酯。再者，在粘合剂中共聚的醋酸乙烯酯总含量（来自接枝和未接枝的EVA共聚物两者）应超过粘合剂的约13.5%重量。如果共聚的醋酸乙烯酯总量低于约13.5%重量，该组合物对聚苯乙烯的粘合就被削弱。此共聚物的熔融指数也应为0.5～40。
接枝单体选自由烯属不饱和的单一、双一或多羧酸和烯属不饱和羧酸酐所组成的这一组，包括这些酸或酸酐的衍生物。这些酸和酸酐的例子包括丙烯酸、甲基丙烯酸、马来酸、富马酸、衣康酸、巴豆酸、衣康酸酐、马来酸酐、和二甲基马来酸酐。合适的衍生物例子包括这些酸或酸酐的盐、酰胺、酰亚胺和酯，例如马来酸的一钠盐和二钠盐，以及富马酸二乙酯。在这些酸和酸酐之中马来酸酐和马来酸是特别有用的。
往EVA共聚物上接枝的方法可以是现有技术中熟知的任一方法。例如，接枝可以在熔融状态下进行，没有溶剂，就象1987年11月18日提出的共同待审的美国专利申请07/122359中所披露的那样或者在溶液中或分散液中进行。熔融接枝可以用一种热挤塑机，一种Brabender或Banbury混合机或其他内混合机或捏合机、辊式研磨机等等来进行。接枝可以在游离基引发剂例如合适的有机过氧化物，有机过酸酯，或有机氢过氧化物存在下进行。可通过任何将所生成的接枝聚合物加以分离或利用的方法来回收此接枝共聚物。因此，接枝共聚物可以以沉淀的蓬松物、颗粒、粉末等等的形式被回收。
被接枝在EVA共聚物上的单体数量不被特别限制，可以低达0.03%重量或高达5%重量甚至更高（以接枝EVA共聚物的重量计算）。然而接枝聚合物在整个粘合剂组合物中的总数量却是重要的，为了获得优越的粘合剂及粘结性能，它应该是整个组合物的约0.03～0.5%重量。
可挤塑粘结树脂组合物的第三组份是改进了抗冲击性的聚苯乙烯。此聚苯乙烯组份占组合物的约20-45%重量，优选值为约30～45%重量。此聚合物由一种弹性体例如聚丁二烯弹性体或聚丁二烯-苯乙烯弹性体改进了抗冲击性。它可以通过在聚丁二烯或苯乙烯-丁二烯弹性体存在下使苯乙烯单体聚合的方法而制得，结果是出现一种物理掺合物以及一种接枝共聚物。此聚苯乙烯是一种高分子量聚合物，分子量大于约50000。
除了上述的组份外，此粘合树脂可含有现有技术中通用的和已知的其他物质，例如抗氧剂、稳定剂，和填料。
通过将上述组份用任何合适的方式例如熔融掺合、挤塑等方式进行掺合，制得粘合剂树脂组合物。此组合物在含有苯乙烯型树脂层、氯乙烯树脂层、或聚碳酸酯树脂层的结构层和一隔气层（例如聚酰胺或乙烯乙烯醇共聚物层）的复合结构中，提供了极好的粘合。含有苯乙烯型树脂的结构在宽的温度范围内显示极好的挤塑性和优良的成型加工性。由这种复合结构所提供的加工性及隔气性的组合使得它们适用于例如包装材料、可随意使用的容器等方面。
实施例
粘合剂的掺合物是如此制备的：在聚乙烯袋中将各组份进行干掺合，随后在220℃到230℃于一个带真空口的28或30毫米双螺杆挤塑机中进行熔融掺合。列于表1中的每个掺合物还含有0.1%重量的Irganox        1010受阻多酚稳定剂（不单独在表1中列出）。
将每种掺合物用一个25毫米单螺杆挤塑机在转速为4到6转/分通过一个共挤塑模头进行共挤塑。在掺合物的一个侧面上，由一个转速为8到12转/分的38毫米挤塑机将一层高冲击强度聚苯乙烯（HIPS）挤出来，在掺合物的另一个侧面上，由一个转速为30到45转/分的38毫米挤塑机将一层含33%摩尔乙烯的乙烯乙烯醇共聚物挤出来。将每一挤出机的机筒温度定在230℃，将挤出物在上面通过的冷却辊维持在100℃。挤出片的牵引速度是约1.5米/分，片的厚度示于表中。
通过测量其剥离强度来评价如此制得的层压物。按ASTM        D1876-72测量剥离强度，但作了下述改动：测试在305毫米/分下进行，而不是254毫米/分，测量了每个试样的3至6个复制品，而不是10个。这一测试的结果，以“T”形式进行的则在本表中以“T”表示。对某些试样，用相似的方法进行另外的剥离强度测量，除了采用的形式是将薄片之一折回来，以致它是与层压物平行的。这些测试在表中以“180”表示。
表中的结果表明了在本发明的范围内的粘合剂组合物的优越性。实施例1-19描述使用本发明粘合剂制造的层压物。这些层压物的“T”剥离强度至少为280牛顿/米，典型值是至少为300牛顿/米。在本发明范围外制得的层压物在对比例C1-C23中描述。这些层压物的“T”剥离强度显著地低于250牛顿/米，往往是少得多。对比例1的剥离强度低，是因为用于掺合物EVA共聚物中的醋酸乙烯酯总含量低于13.5%。对比例C3的剥离强度低，是因为接枝EVA共聚物和未接枝EVA共聚物中的醋酸乙烯酯含量之差大于10个百分数。对比例C4和C5的结果不好，是因为接枝聚合物是改性聚乙烯或改性EPDM，而不是改性EVA共聚物。对比例C6的剥离强度不好，是因为接枝EVA和未接枝EVA中的醋酸乙烯酯含量的差值大于10个百分数，且聚苯乙烯的含量低于20%。对比例C7到C9的剥离强度差，是因为掺合物中所含的作为组份的聚苯乙烯少于20%。另一方面，对比例C10到C17的剥离强度差或有所变动，是因为聚苯乙烯组份大于掺合物的45%。对比例C18到C24的剥离强度低，是因为未使用改进了抗冲击性的聚苯乙烯：在对比例C18和C19中，使用了未改性的或结晶的聚苯乙烯;在对比例C19到C21中，使用了含70%丁二烯的苯乙烯氢化丁二烯三元嵌段共聚物;而在对比例C22和C23中，使用了含30%丁二烯的苯乙烯丁二烯共聚物。
Figure 89106334X_IMG2

Claims (12)

1、一种可挤塑的粘结用树脂组合物，主要含有：
(a)约55～80%重量的一种乙烯醋酸乙烯酯共聚物组份，它主要由以下组成：
(Ⅰ)0至约99%重量的一种共聚物，它含约60～87%重量乙烯和约13～40%重量醋酸乙烯酯共聚用单体，和
(Ⅱ)约1%至100%重量的一种共聚物，它至少含约50%重量乙烯，约3～50%重量醋酸乙烯酯共聚用单体，如醋酸乙烯酯共聚用单体存在的话，则其数量是在共聚物(Ⅰ)中的醋酸乙烯酯共聚用单体数量的10个百分数范围内，和一种含侧羧酸官能度或侧羧酸衍生物官能度的接枝共聚用单体，其中，上述的接枝共聚用单体的数量为组合物总量的约0.03～0.5%重量，而(Ⅰ)和(Ⅱ)中的共聚醋酸乙烯酯的总量则超过组合物总量的13.5%重量；和
(b)约20～45%重量的分子量大于50000的改进了抗冲击性的聚苯乙烯。
2、权利要求1的组合物，其中乙烯醋酸乙烯酯共聚物组份的数量是组合物的约55～70%重量，而改进了抗冲击性的聚苯乙烯的数量是组合物的约30～45%重量。
3、权利要求1的组合物，其中共聚物（Ⅰ）中的醋酸乙烯酯共聚用单体的数量是约25～35%重量。
4、权利要求1的组合物，其中共聚物（Ⅱ）中的醋酸乙烯酯共聚用单体的数量是约15～35%重量。
5、权利要求4的组合物，其中的羧酸或羧酸衍生物被接枝到共聚合物（Ⅱ）上，其数量为约0.05～5%重量。
6、权利要求5的组合物，其中的羧酸或羧酸衍生物是烯属不饱和单、双或多羧酸、酸酐、盐、酰胺、酰亚胺或酯。
7、权利要求6的组合物，其中的羧酸或羧酸衍生物是丙烯酸、甲基丙烯酸、马来酸、富马酸、衣康酸、巴豆酸、衣康酸酐、马来酸酐、二甲基马来酸酐、马来酸-钠盐、马来酸二钠盐、富马酸二乙酯。
8、权利要求6的组合物，其中的羧酸或羧酸衍生物是酸酐。
9、权利要求8的组合物，其中的酸酐是马来酸酐。
10、权利要求1的组合物，其中的改进了抗冲击性的聚苯乙烯的冲击强度至少为92J/m。
11、一种层压结构，它包括至少一层结构层、至少一层隔气层、和至少一层权利要求1的可挤塑的粘结树脂组合物的粘合层。
12、权利要求11的层压结构，其中的结构层是高冲击强度聚苯乙烯，而隔气层是乙烯乙烯醇共聚物。
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US5053457A (en) * 1989-06-13 1991-10-01 E. I. Du Pont De Nemours And Company Coextrudable adhesives and products therefrom
US5217812A (en) * 1990-06-25 1993-06-08 E. I. Du Pont De Nemours And Company Extrudable and primerless adhesives and products therefrom
US5219665A (en) * 1991-01-30 1993-06-15 E. I. Du Pont De Nemours And Company Fabricated articles with improved resistance to hydrohalocarbons
US5516583A (en) * 1994-08-29 1996-05-14 E. I. Du Pont De Nemours And Company Adhesive for tamper evident seals
US5597865A (en) * 1994-11-21 1997-01-28 Quantum Chemical Corporation Adhesive blends for polystyrene
US5709953A (en) * 1996-02-21 1998-01-20 Morton International, Inc. Extrudable resin for polystyrene and laminate
US6166142A (en) 1998-01-27 2000-12-26 E. I. Du Pont De Nemours And Company Adhesive compositions based on blends of grafted metallocene catalyzed and polar ethylene copolymers
FR2781496B1 (fr) * 1998-07-21 2002-04-05 Rapid Sa Composition thermocollante, utilisation de celle-ci et bouchon d'obturation fabrique a partir de cette composition
US6855432B1 (en) * 1999-09-03 2005-02-15 E. I. Du Pont De Nemours And Company Low activation temperature adhesive composition with high peel strength and cohesive failure
KR100437536B1 (ko) * 2000-12-20 2004-06-30 제일모직주식회사 유리섬유 강화 스티렌계 열가소성 복합재료
CA2483196A1 (en) * 2002-05-23 2003-12-04 E. I. Du Pont De Nemours And Company Toughened thermoplastic polyamide compositions
US20060148988A1 (en) * 2004-10-06 2006-07-06 Chou Richard T Miscible blends of ethylene copolymers with improved temperature resistance
US7879949B2 (en) * 2004-10-06 2011-02-01 E.I. Du Pont De Nemours And Company Blends of ethylene copolymers with high-frequency weldability
US20060073385A1 (en) * 2004-05-28 2006-04-06 Peter Andrin Novel sealant material for electrochemical cell components
EP1624515B1 (en) * 2004-05-28 2008-12-17 Du Pont Canada Inc. Unitized electrochemical cell sub-assembly and the method of making the same
US7767311B2 (en) * 2004-07-29 2010-08-03 E.I. Du Pont De Nemours And Company Adhesive compositions derived from highly functionalized ethylene copolymers
US20070071988A1 (en) * 2005-09-29 2007-03-29 Botros Maged G Adhesive blends for styrene polymers and articles
US20080039583A1 (en) * 2006-08-08 2008-02-14 I-Hwa Lee Adhesive composition
WO2013143824A1 (en) * 2012-03-30 2013-10-03 Exxonmobil Chemical Patents Inc. Process for the production of terephthalate esters
WO2019126189A1 (en) 2017-12-22 2019-06-27 E. I. Du Pont De Nemours And Company Thermoplastic adhesive composition
WO2019126129A1 (en) 2017-12-22 2019-06-27 E. I. Du Pont De Nemours And Company Thermoplastic adhesive composition
WO2019152830A1 (en) 2018-02-01 2019-08-08 Dow Silicones Corporation Composition, polymer composite article formed therewith, and method of preparing same

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JPS603098B2 (ja) * 1976-08-04 1985-01-25 東ソー株式会社 低温ヒートシール性のすぐれた樹脂組成物
US4298712A (en) * 1977-08-01 1981-11-03 Chemplex Company Adhesive blends of elastomer, polyolefin, and graft of polyethylene with unsaturated fused ring anhydrides
JPS5949191B2 (ja) * 1977-10-15 1984-12-01 旭化成株式会社 樹脂積層物
JPS58203043A (ja) * 1982-05-21 1983-11-26 大日本印刷株式会社 積層体
JPS5955743A (ja) * 1982-09-27 1984-03-30 三菱油化株式会社 樹脂積層物の製造方法
JPS6026072A (ja) * 1983-07-22 1985-02-08 Takeda Chem Ind Ltd 変性エチレン・酢酸ビニル共重合体を含有してなる接着剤および該接着剤で接着した成型品

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