CN102458797A - 包含evoh的膜的制备方法 - Google Patents

包含evoh的膜的制备方法 Download PDF

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CN102458797A
CN102458797A CN2010800242373A CN201080024237A CN102458797A CN 102458797 A CN102458797 A CN 102458797A CN 2010800242373 A CN2010800242373 A CN 2010800242373A CN 201080024237 A CN201080024237 A CN 201080024237A CN 102458797 A CN102458797 A CN 102458797A
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Prior art keywords
evoh
film
cavitation
reagent
polymer composition
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K·M·多诺万
D·A·列斯特曼
R·弗吉斯
E·T·格尔
R·F·布雷
J·T·福特
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Film Usa LLC
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ExxonMobil Oil Corp
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    • B29C55/02Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

本说明书涉及制备聚合物膜的方法,该方法包括(a)共挤出(i)具有非有机空化试剂的第一聚合物组合物;(ii)具有EVOH的第二聚合物组合物以形成多层片材;以及b)使所述多层片材沿MD、TD或者两个方向取向以形成所述多层膜,其中第一聚合物组合物和/或第二聚合物组合物进一步包含具有EVOH以及非有机空化试剂的循环聚合物组合物。

Description

包含EVOH的膜的制备方法
相关申请的交叉引用
本申请要求2009年6月4日提交的申请号为61/184,121的美国临时申请的权益,其内容整体引入作为参考。
技术领域
本公开内容涉及包含乙烯乙烯醇共聚物(EVOH)的膜的制备方法。尤其是,该方法包括循环通过在线修整和/或回收膜材料产生的包含EVOH的材料。
背景技术
聚合物膜用于包装或者标签用途。用于包装或者标签的聚合物膜包含一个或多个聚合物层,该一个或多个聚合物层通过挤出或者共挤出聚合物树脂以形成聚合物片材,该聚合物片材经受更进一步的加工比如沿纵向(MDO)或者横向(TDO)或者两个方向取向而制备。对于某些用途,至少单层的膜用适合它预定用途的空化试剂空化。包括用拉幅机法取向的取向膜条带在内的取向膜的粗边缘通常在线修整或者离线修整以及循环返回该挤出加工。在取向和/或后取向加工期间产生的或者因为任何质量原因而丢弃的膜废料,也通常碾碎、通过独立加工再造粒、以及返回该挤出加工中再利用。
包含EVOH的空化膜由于EVOH共聚物的羟基提供的功能而尤其可用于包装或者标签。然而,用聚对苯二甲酸丁二醇酯(PBT)作为空化试剂空化的包含EVOH的膜难以再利用。通过回收用PBT空化的包含EVOH膜修整下来的边角料而制备的膜由于回收材料降解而趋向于破裂以及难以保持技术规范上的规格。无循环步骤,该膜制备方法效益低的无法接受以及该膜产品成本高。
对于开发高效的制造包含EVOH的空化膜的方法存在需求,该方法包括循环包含EVOH的膜的修整边缘以及再造粒废料。
发明内容
在一些实施方案中,本公开内容涉及聚合物膜的制备方法,该方法包括:
a)共挤出:
i)具有非有机空化试剂的第一聚合物组合物;
ii)具有EVOH的第二聚合物组合物以形成多层片材;以及
b)使所述多层片材沿MD、TD或者两个方向取向,
其中第一聚合物组合物和/或第二聚合物组合物包含具有EVOH以及非有机空化试剂的循环聚合物组合物。
在其它的实施方案中,循环聚合物组合物由步骤(b)的取向膜的修整边缘或者具有EVOH和非有机空化试剂的回收膜材料生产。
发明详述
本申请公开各种的具体实施方案、型式、以及实例,包括示范性的实施方案和采用以便理解发明请求权项的定义。尽管以下详细说明给出具体的优选实施方案,然而本领域技术人员会理解这仅是示范性的实施方案,因而本发明可按照其它方式实施。说明书范围会借助所附权利要求的任何一个或更多个,包括它们的同等物,以及与列举那些同等的要素或者限制在内来确定侵权。″本发明″任何所提及的可涉及一个或多个、但未必是权利要求限定的全部发明。
如本文所用,该术语″单体″是小分子,其可化学键连至其它的单体以形成聚合物。单体实例包括烯属单体、比如乙烯、丙烯、丁烯、1-己烯、苯乙烯和1-辛烯。
如本文所用,该术语″聚合物″指聚合反应产物,以及包括均聚物、共聚物、三元共聚物等。
如本文所用,除非另外说明,该术语″共聚物″由至少两种聚合不同的单体形成的聚合物。举例来说,该术语″共聚物″包括丙烯和α-烯烃,比如乙烯的共聚反应产物。然而,该术语″共聚物″也包括,例如,多于两种单体比如乙烯-丙烯-丁烯混合物的共聚合。
如本文所用,重量%(″wt.%″),除非另外指示,意指特定组分基于包含该组分的混合物总重量的重量百分数。举例来说,如果混合物或者掺混物包含3克的化合物A和1克的化合物B,那么化合物A占该混合物的75wt.%以及化合物B占25wt.%。如本文所用,百万分之份(ppm),除非另外指示,意指按重量计算的百万分之。
空化层以及空化试剂
本公开内容多层膜的空化层包含聚合物和至少一种非有机空化试剂。优选,该空化层包含聚丙烯、聚丙烯以及高密度聚乙烯(″HDPE″)中的至少一种。
如本文所用该术语″非有机空化试剂″意指包含小于10wt.%有机物的空化试剂。在空化试剂中有机物的数量通过测量10克空化试剂在24小时空气燃烧以后(250℃以及空气流速10ml/min下)的失重百分比(不计失水量)而计量。
优选,本说明书的非有机空化试剂具有低于5wt.%,以及更优选低于1wt.%有机物。
合适的空化试剂实例包括如下物质的至少一种:氧化铁、碳黑、铝、二氧化钛、碳酸钙、玻璃球、钙-镁碳酸盐、白云石、硅酸盐、硫酸钡、碳黑、板岩粉、氯氧化铋、二氧化硅、水合氧化铝、高岭土、硅藻土、云母、沸石以及滑石。在一些实施方案中,该空化试剂的粒度为约0.5至约15微米。在优选实施方案中,该空化层具有的空化试剂浓度范围为10-70wt.%。
该空化层可以另外包含一种或多种添加剂。用于该空化层的上述添加剂包括,但是不局限于,烃类树脂,烃蜡,不透明剂,或者着色剂以及滑爽添加剂。
EVOH层
第二聚合物组合物包含EVOH。EVOH指乙烯乙烯醇共聚物,众所周知其显示出优良的氧气阻隔性能。上述乙烯乙烯醇共聚物已经公开在包括专利号为US3,975,463和US4,468,427的美国专利在内的许多专利中,这二者引入本文作为参考。该高阻隔层优选包含至少约55重量%,优选至少约80重量%,更优选至少约90重量%的EVOH共聚物,该EVOH共聚物包含至少约48mol.%的乙烯共聚单体。可用于制备本发明高阻隔层的可商购的EVOH共聚物包括EVALTM G156B,G176,F104或者L101,其可以从EVALCA获得。
取向
挤出片材可以是单向或者双向拉伸。沿挤出方向取向被称为纵向取向。沿垂直于挤出方向取向被称为横向取向。通过首先沿MD,任选地继之以TD拉伸或者牵引膜完成取向。取向可以顺序或者同时进行,这取决于所要求的膜特征。
在一些实施方案中,该片材在拉幅机中相对它的原始大小沿纵向拉伸3-7倍,继之以相对它的原始大小沿横向拉伸5-10倍。然后该膜在线或者离线修整以除去不合规范的部分、如侧边缘。然后该膜卷绕在卷轴上。
本公开内容的膜可以用诸如卷取以及吹塑比之类的控制参数通过吹制而取向。流延膜可以通过卷取速度沿MD方向以及应用拉幅机设备沿TD取向。吹塑膜或者流延膜也可在膜挤出加工之后通过拉幅机-框架定向而沿一个或者两个方向取向。一般的工业的取向加工是双向拉伸聚丙烯(BOPP)拉幅机工艺以及LISIM技术。
循环材料
诸如侧边之类的从膜修整下的材料包含EVOH以及非有机空化试剂二者。用过的膜可以回收作为再利用材料,其包含EVOH以及非有机空化试剂二者。这些材料可被用于本公开内容制造方法的循环步骤。
工业用途
在一些实施方案中,由本说明书方法制造的膜可以用于软包装以及标签用途。
按照本说明书所述的膜可通过诸如涂布、印刷、切割、或者其它转化方法之类的进一步处理,用于它打算的用途。
本说明书参照以下实施例更详细解释,而非限制本说明书范围。
本发明的实施例以及对比实施例
用于本发明实施例的EVOH从Kuraray Co.按Eval 176G获得。
本发明的实施例和对比实施例都是采用由PBT(对比实施例)或者碳酸钙(本发明的实施例)空化的聚丙烯芯层以及EVOH共挤出层制备的五层膜。对比实施例以及本发明的实施例用5台独立的总产量约2200kg/小时的挤出机260℃共挤出。该共挤出物用冷却辊以及水浴骤冷,二者调节至45℃,然后沿MD按4.7倍以及沿TD按9.0倍双轴拉伸。修整膜的侧边缘以及在线回收返回到该挤出机。
使用PBT作为空化试剂,所制备的该膜具有不均匀的厚度以及过程控制问题。对比实施例膜破裂以及具有缺陷,比如,空穴和凝胶斑点。在仅12小时制备之后,通过该定高线测量扫描器测量的该平均厚度变化增加到无法接受的6%或更多,需要花费高昂的设备关闭清洗,导致生产效率低,质量不合格率高,在随后加工中(比如涂布和切割)材料等级降低,以及产品成本高。
用碳酸钙作为空化试剂,所制备的该膜具有均匀厚度以及无过程控制问题。本发明实施例的膜无破裂和无缺陷,可归因于空化试剂具有极好的轮廓控制性以及仅有典型的加工扰乱性。通过该定高线测量扫描器测量的该平均厚度变化小于3%、即使在多于24小时制备以后,导致生产效率优良、产物质量高,并且产品成本低。
再经加工的废料以及生产包含EVOH和PBT膜中所产生的修整下来的材料在本发明的实施例中再利用、直至2.4%EVOH在该膜结构芯层中而无破裂或者膜质量缺陷比如空穴或者凝胶。对比实施例中,在该膜芯层中合并EVOH以及PBT,使在该芯层中EVOH为0.2%,导致无法接受的质量缺陷、比如膜平面度均一性。
用非有机空化试剂,比如CaCO3替换PBT空化试剂解决该再利用过程扰乱问题以及容许该工艺过程包括包含EVOH以及非有机空化试剂的在线修整回收物。
由此,尽管已经公开了目前据信为本发明的优选实施方案,本领域技术人员会认识本发明可作各种的变化以及改变,只要没有背离上述本发明的精神。因此,属于本发明范围的全部上述的改变以及改进都要求权利。

Claims (10)

1.制备多层膜的方法,该方法包括:
a)共挤出:
i)具有非有机空化试剂的第一聚合物组合物;
ii)具有EVOH的第二聚合物组合物以形成多层片材;以及
b)使所述多层片材沿MD、TD或者两个方向取向以形成所述多层膜,其中第一聚合物组合物和/或第二聚合物组合物进一步包含具有EVOH以及非有机空化试剂的循环聚合物组合物。
2.权利要求1的方法,其中所述非有机空化试剂是碳酸钙。
3.权利要求1或者2的方法,其中所述第一聚合物组合物包含聚丙烯。
4.前述任一项权利要求的方法,其中所述具有EVOH的循环聚合物组合物包括所述多层膜的修整边缘、回收的包含EVOH的材料、再造粒的包含EVOH的材料、或者其任何结合。
5.前述任一项权利要求的方法,进一步包括在线修整所述多层膜的边缘的步骤。
6.权利要求5的方法,进一步包括将修整的边缘循环到共挤出步骤的步骤。
7.前述任一项权利要求的方法,其中所述第一聚合物组合物包含至少0.5wt.%来自所述循环聚合物组合物的EVOH。
8.前述任一项权利要求的方法,其中所述第一聚合物组合物包含至少1wt.%来自所述循环聚合物组合物的EVOH。
9.前述任一项权利要求的方法,其中所述第一聚合物组合物包含小于2.4wt.%来自所述循环聚合物组合物的EVOH。
10.由前述任一项权利要求制备的膜。
CN2010800242373A 2009-06-04 2010-05-20 包含evoh的膜的制备方法 Pending CN102458797A (zh)

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