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CN1243848A - 具有高度气体阻挡性能的聚酯树脂共混物 - Google Patents

具有高度气体阻挡性能的聚酯树脂共混物 Download PDF

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CN1243848A
CN1243848A CN99108436A CN99108436A CN1243848A CN 1243848 A CN1243848 A CN 1243848A CN 99108436 A CN99108436 A CN 99108436A CN 99108436 A CN99108436 A CN 99108436A CN 1243848 A CN1243848 A CN 1243848A
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polyester
polymeric amide
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H·A·加塔
S·科布鲁尔
T·塞韦里尼
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Sinco Research S P A
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Abstract

包含聚酯树脂和得自含6～22个碳原子的二羧酸和间亚二甲苯基二胺的聚酰胺的具有高度气体阻挡性能的组合物,它是经下述方法制得的:在熔融状态下将与四羧酸二酐预混合的聚酯树脂与聚酰胺混合,操作在这样的条件下进行,即从流变学上看使聚合物各组分相互是相容的。该组合物适用于制备容器和双轴取向的膜。

Description

具有高度气体阻挡性能的聚酯树脂共混物
本发明涉及具有高度抗气体渗透性的双轴取向的膜和容器，并涉及用于制备所述容器和膜的聚合物材料。
芳族聚酯树脂愈来愈多地用于制造饮料容器和膜。
芳族聚酯树脂的阻挡层性能相当有限。在由所述树脂制成的用于盛放充了碳酸气的饮料的容器的情况下，保藏饮料一段足够长时间的可能性是不确定的。
聚酰胺树脂具有显著的机械性能，但它们具有会降低其性能的高吸湿性的缺点。
聚酰胺树脂通常与芳族聚酯树脂混合起来使用，以改进后者的机械性能。在混合物中存在聚酯树脂会降低聚酰胺树脂的吸湿趋势。
然而，混合树脂是困难的，原因是它们在熔融状态下的差的相容性。
为了获得较好的机械性能并避免产品中的剥离，业已提出在四羧酸二酐存在下在挤压机中混合树脂(JP 1-272660 Kokai)。
1，2，4，5-苯四酸酐是较好的化合物。
所得混合物的机械性能可通过对混合物施加固态缩聚处理而得到进一步改进(WO 94/09069)。
在聚酰胺中，最常用的聚酰胺如尼龙6和66的气体阻挡性能略优于聚酯树脂如聚对苯二甲酸乙二醇酯(PET)和包含少量的来自间苯二酸的单元的共聚对苯二甲酸乙二醇酯。
然而，已知得自间亚二甲苯基二胺和己二酸的聚酰胺(聚间亚二甲苯基己二酰二胺，聚MXD-6)具有明显优于聚对苯二甲酸乙二醇酯的相当好的气体阻挡性能(相对于氧气和二氧化碳来说)。
将这种聚酰胺用在含PET或COPET的混合物(在挤压机中获得)中，以改进它们的阻挡层性能。
当瓶得自含16重量％聚酰胺的混合物时，1.5升PET瓶(经注射吹塑制得)的氧气渗透性减少约50％，而当得自含7重量％聚酰胺的混合物时，该氧气渗透性减少约20％。
16％聚酰胺混合物的阻挡层性能与两层膜制成的瓶的相类似，所述两层膜中的一层是PET，另一层是聚酰胺。
现在意想不到地发现若熔融状态的聚酯树脂将与四羧酸二酐混合，所得的混合物仍以熔融状态再与聚酰胺如聚MXD-6混合，操作在温度和剪切力的条件下进行，并且熔融聚合物组分的粘度是这样的，即从流变学的角度来看使混合物的聚合物组分相容，从使用这种含聚酰胺如聚MXD-6的混合物形式的聚酯树脂就可能显著地改进所获得的双轴取向膜和容器的阻挡层性能。与聚酯树脂混合的二酐的量为0.01-3重量％。
1，2，4，5-苯四酸二酐是较好的。其它可以使用的二酐是1，2，3，4-环丁烷四羧酸二酐，3，3’：4，4’-二苯酮四羧酸二酐，2，2-双(2，4-二羧基苯基)醚。芳族四羧酸二酐是较好的。
聚酯树脂较好的是共聚对苯二甲酸乙二醇酯，其中达25％，较好地1-15％的来自对苯二酸的单元被来自间苯二酸或来自其与萘二甲酸混合物的单元或序列所取代。
聚酰胺较好的是聚MXD-6。其它可以使用的聚酰胺是那些得自除了己二酸外的含6-22个碳原子的脂族二羧酸与亚芳基二胺(arilene diamine)，较好为间亚二甲苯基二胺的聚酰胺。
所述的二羧酸较好是辛二酸、癸二酸和十二烷酸。
具有与聚酯相类似的结晶速度的聚酰胺优选使用。
起始聚酰胺的数均分子量(numeral molecular weight)通常为8000-50000。
起始聚酰胺的末端NH2基可与环氧化合物反应，以提高其在聚酯基体中的分散度。来自Shell Italia的Epikote是可以使用的环氧化合物的一个例子。
聚酰胺的用量较好为占混合物重量的5-30重量％。视混合物的最终性能而定，可以使用更多的量。
本发明的另一个方面是，实际上有可能按本发明的方法制备，加工可用作母炼胶的聚酰胺含量为多于50重量％，高达80-90重量％的混合物。
一种较好的混合方法包括挤压聚酯树脂同时添加二酐，随后挤压该混合物同时添加聚酰胺。
可用单一的步骤进行操作，即先在挤压机中预混合聚酯和二酐，然后在挤压机中加入聚酰胺。
为了在各聚合物组分之间达到良好的相容性，它们在熔融状态时的粘度必须非常相似。
聚酯的粘度与聚酰胺的粘度之比较好为0.2∶1-4∶1。
在上述条件下进行操作就可以获得这样的组合物，其中聚酰胺分散在聚酯基体中，其区域结构(domains)的大小为小于1微米，较好为0.2-0.4微米。微结构可用扫描电子显微镜(S.E.M.)对用甲酸处理注塑小棒以萃取聚酰胺后的断裂表面进行观察获悉。按实施例1制得的棒具有其中的分散相的大小为小于0.5微米的微结构。实施例1制得的但不使用PMDA的棒中该区域结构的平均大小为大于1.5微米。本发明的微结构尤其是聚MXD-6与PET或含达25％来自间苯二酸的单元的共聚对苯二甲酸乙二醇酯的共混物的特征。
令人惊奇的是，当在本发明的混合条件下操作时，可以获得具有比下述情况获得的物质高得多的气体阻挡性能(对于O2和CO2来说)的材料，所述物质可通过将聚酯树脂和聚酰胺在四羧酸二酐不存在的情况下进行混合而制得，或通过将混合物的三种组分同时进行混合而制得，或通过先将聚酰胺与二酐混合而后加入聚酯树脂而制得。
随聚酰胺(pMXD-6)含量的不同，平均厚度为225微米的1.5升瓶的氧气渗透性将减小4或更多倍，而二氧化碳的渗透性将减小2或更多倍。
聚酯树脂是由对苯二酸或其低级二酯与含2-12个碳原子的二元醇如乙二醇、1，4-丁二醇和1，4-环己烷二甲醇经缩聚(按已知的方法)获得的。如所述，共聚对苯二甲酸乙二醇酯是用于制备容器的较好的树脂。
可以方便地使用聚对苯二甲酸乙二醇酯均聚物来制备双轴取向的膜。
用于制备本发明组合物的起始聚酯树脂的特性粘度为0.3-0.8dl/g。初始粘度可通过下述方法得到提高：使与四羧酸二酐预混合的树脂或含聚酯树脂、聚酰胺和二酐的混合物在约150-230℃的温度下经固态缩聚处理一段时间，并在足以提高聚酯树脂粘度至少0.1个单位的温度条件下进行固态缩聚处理。
由于聚酯树脂是难以被在混合物中的溶剂萃取所分离的，所以认为混合物中聚酯树脂的特性粘度的提高与在混合物所经历的相同的温度和持续时间条件下单独处理聚酯树脂时其特性粘度的提高是相类似的。
固态缩聚处理除了提高聚酯树脂的特性粘度外，还能改进组合物的机械性能，尤其是抗冲击性。
施加到加入四羧酸二酐的聚酯树脂上的处理能使熔融状态的树脂的粘度达到与聚酰胺树脂的相类似的值，尤其是当初始聚酯树脂具有比较低的特性粘度值时。
聚酯与二酐而后与聚酰胺的混合在单或双螺杆挤压机中进行。逆转和相互啮合式的双螺杆挤压机是较好的，所用的停留时间通常为小于180秒，并在高于聚合物组分的熔融温度，通常为200-300℃的温度下进行操作。
按已知的方法来制备双轴取向的膜和容器。例如，饮料瓶可经注射拉伸吹塑法来制备；双轴取向的膜可经双泡法或经浇铸挤压随后双轴拉伸法来制备。
本发明的材料也可以用来制备包含得自本发明材料的双轴取向膜作为芯层的多层膜。
本发明共混物(其中聚酯树脂是含10％或更多来自间苯二酸的单元的共聚对苯二甲酸乙二醇酯)的另一个应用是经自由吹塑来制备适用于盛放液体如软饮料或其它的高容量袋(5升或更大)的预制件。
该袋具有高的透明度和良好的机械性能。它们易于被折叠，而不会产生断裂或应力withening的问题。
在25℃时，按ASTM标准D 4603-86测量0.5克树脂在100毫升60/40重量比的苯酚和四氯乙烷溶液中的溶液的特性粘度。
用装有2毫米毛细管的Goettfert流变仪，在280℃下以100秒-1的剪切速率进行操作，测量熔融粘度。
实施例
给出下述实施例用于举例，并非限制本发明。
实施例1
将20kg/h含4.5％间苯二酸(IPA)，IV＝0.6dl/g的共聚对苯二甲酸乙二醇酯(COPET)结晶颗粒(在140℃的真空中预干燥至少12小时)连同20g/h 1，2，4，5-苯四酸二酐(PMDA)(占COPET重量的0.1％)送到装有逆转和相互啮合螺杆式双螺杆挤压机中，而后造粒。
操作条件是：
螺杆旋转速度：100rpm
筒体温度：整个筒体都是280℃
COPET进料：20kg/h
PMDA进料：20g/h
停留时间：1.5分钟
所得的粒料在氮气流动下连续地在130℃的反应器中结晶。
挤压后的IV为0.61dl/g。
将20kg/h如上所述获得的含0.1％PMDA的结晶COPET连同2.2kg/h在280℃的熔融状态下具有某一粘度的聚MXD-6(Mitsubishi Gas Chemical-MGC-日本)送入装有逆转和相互啮合螺杆式双螺杆挤压机中，并且1000 PAS的剪切速度为100秒-1，并造粒。
制备混合物的条件与处理COPET外加PMDA所用的条件相同。
实施例2
重复实施例1制备COPET和PMDA的混合物的过程，所不同的仅是用包含重量比为92/8的含2％间苯二酸，IV＝0.8dl/g的COPET和8％聚间苯二甲酸乙二醇酯的混合物来代替含4.5％间苯二酸的COPET。
粒料的IV为0.81dl/g。粒料在130℃时在氮气下的连续操作的反应器中结晶。
然后粒料连同10重量％聚MXD-6在如实施例1的条件下进行挤压。
实施例3
重复实施例1的制备过程(将COPET与PMDA预混合，随后与10％聚MXD-6一起挤压)，所不同的仅在于所用的COPET包含2％间苯二酸，并且其IV为0.6dl/g。
实施例4
重复实施例1的制备过程，所不同的仅在于混合物包含70重量％的聚MXD-6。
实施例5
将使用包含86重量％含2％IPA的COPET(IV＝0.8dl/g)和14％聚间苯二甲酸乙二醇酯的混合物来代替含4.5％IPA的COPET，按实施例1制得的组合物(其中聚MXD的百分数为7.5重量％)用于制备40克预制件。
使用装有加热预制件到110℃的红外加热器的Sidel机，对预制件进行自由吹塑。使用压力为3巴的空气对预制件进行吹塑。所得袋的容量为5升，并且高度透明。它们可被折叠(空的时候)，并可重新盛入液体。
盛放5升水的袋可承受1米的落锤冲击。
实施例6，7
使用Husky注射装置使用实施例1-4获得的混合物来制造36克预制件。
然后将预制件放在1.5和2升模腔内进行吹塑，经拉坯吹塑制造瓶。1.5升瓶的厚度为225微米(平均值)，2升瓶的厚度为195微米(平均值)。
瓶对O2和CO2的渗透性特征列于表1中。气体渗透性是在18℃，40％RH下使用Mocon仪进行测量的。
对比例1
重复实施例1的制备过程，所不同的仅在于挤压包含重量比为90/10的COPET(含2％IPA，其IV＝0.8dl/g)和聚MXD-6的混合物，它不含PMDA。
在实施例6-7所用的条件下经注射吹塑来制备1.5升的瓶。
瓶对O2和CO2的渗透性比实施例6-7中的瓶高得多。
对比例2
使用含2％IPA并且IV＝0.8dl/g的COPET制成的树脂，在实施例6-7的条件下制备1.5升的瓶。
对O2和CO2的渗透性的数据列于表1中。
                                   表1
                                  混合物
                   对比例2    实施例1   实施例2  实施例3    实施例4聚MXD-6的重量％           0         10         10       10         70IPA的％                   2         4.5        10       2          4.5O2的渗透性1.5升瓶ml/bott/d/atm      0.53      0.13       0.1      0.122升瓶                     0.62      0.23       0.14     0.14CO2的渗透性1.5升瓶ml/bott/d/atm      18.2      7.25       5.31     7.02       2.7改进％O2的渗透性1.5升瓶                             407        550      4492升瓶                               362        578      567CO2的渗透性1.5升瓶                             251        343      250        670

Claims (25)

1.双轴取向的膜和容器，它们是使用混合熔融物质获得的材料制成的，所述熔融物质包含：
a)与0.01-3重量％四羧酸二酐预混合的芳族聚酯；
b)占a)+b)总重量的2-50％的得自间亚二甲苯基二胺和含6-22个碳原子的二羧酸的聚酰胺，聚酯和聚酰胺在温度、剪切力条件和聚合物组分的熔融粘度值下进行混合，以便从流变学的角度来看使所述各组分是相容的。
2.如权利要求1所述的容器，它是以用于盛放充了碳酸气的饮料的瓶的形式存在。
3.如权利要求1至2中任一项所述的容器，它是经注射吹塑制成的。
4.如权利要求1至3中任一项所述的容器，其特征在于芳族聚酯是包含达25％来自间苯二酸的单元或序列的共聚对苯二甲酸乙二醇酯。
5.如权利要求1至4中任一项所述的容器和膜，其特征在于聚酰胺是聚间亚二甲苯基己二酰二胺。
6.如权利要求1至5中任一项所述的容器和膜，其特征在于四羧酸二酐是1，2，4，5-苯四酸二酐。
7.如权利要求1至6中任一项所述的容器和膜，其特征在于用于制备容器的材料中起始聚酯的特性粘度为0.3-0.8dl/g。
8.如权利要求1至7中任一项所述的容器和膜，其特征在于使得自包含聚酯、聚酰胺和二酐的熔融混合物的物料经固态缩聚处理一段时间，并且温度条件足以提高聚酯的特性粘度至少0.1个单位。
9.如权利要求1至8中任一项所述的容器和膜，其特征在于使与二酐预混合的聚酯经固态缩聚处理，使初始聚酯的特性粘度提高0.1个单位。
10.如权利要求1至9中任一项所述的容器和膜，其特征在于在混合温度下测定的聚酯与聚酰胺的熔融粘度之比为0.2∶1-4∶1。
11.如权利要求1至10中任一项所述的容器和膜，其特征在于各组分在挤压机中进行混合。
12.由一种材料制成或包含该材料的容器和膜，所述材料得自包含聚酯树脂和聚酰胺的组合物，其特征在于对经注射吹塑制成的厚度为225微米的1.5升瓶测得的它们的氧气渗透性为小于0.65ml/瓶/天/atm。
13.如上述权利要求5至12中任一项所述的膜，它是对浇铸挤压制成的膜经双轴拉伸获得的。
14.如上述权利要求1和5至12中任一项所述的膜，它是使用双泡法经吹塑获得的。
15.一种适用于制备具有高抗气体渗透性特征的双轴取向膜和容器的聚合物材料，它是在使其聚合物组分在流变学上是相容的条件下混合熔融材料获得的，所述熔融材料包含：
a)与0.01-3重量％四羧酸二酐预混合的芳族聚酯树脂；
b)占a)+b)总重量的1-90％的得自间亚二甲苯基二胺和含6-22个碳原子的二羧酸的聚酰胺。
16.如权利要求15所述的材料，其特征在于聚酯树脂是包含达25％来自间苯二酸的单元的共聚对苯二甲酸乙二醇酯。
17.如权利要求15至16中任一项所述的材料，其特征在于聚酰胺是聚间亚二甲苯基己二酰二胺。
18.如权利要求15至17中任一项所述的聚合物材料，其特征在于二酐是1，2，4，5-苯四酸二酐。
19.如权利要求15至18中任一项所述的聚合物材料，其特征在于使得自包含组分a)、b)和c)的熔融混合物的物料经固态缩聚反应，直到起始聚酯的特性粘度提高至少0.1个单位。
20.如权利要求19所述的聚合物材料，其特征在于使与二酐预混合的聚酯经固态缩聚反应，直到初始聚酯的特性粘度提高至少0.1个单位。
21.如权利要求1 5至20中任一项所述的聚合物材料，其特征在于在混合温度下的聚酯与聚酰胺的熔融粘度之比为0.2∶1-4∶1。
22.如权利要求15至21中任一项所述的聚合物材料，它能制得氧气渗透性为小于0.065ml/瓶/天/atm的抗氧气渗透性的容器，所述氧气渗透性是对经注射吹塑制成的厚度为225微米的1.5升瓶测得的。
23.一种包含芳族聚酯树脂和得自二羧酸和亚芳基二胺的聚酰胺的聚合物材料，其中聚酰胺分散在聚酯树脂基体中，分散区域的平均大小为小于1微米。
24.如权利要求23所述的聚合物材料，其特征在于分散区域的平均大小为0.2-0.4微米。
25.如权利要求23至24中任一项所述的聚合物材料，其特征在于聚酯树脂是包含达25％来自间苯二酸的单元的共聚对苯二甲酸乙二醇酯，而聚酰胺是聚间亚二甲苯基己二酰二胺。
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