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CN1192449A - 以共聚酰胺pa－6,1/6,t/6,6和/或pa－6,1/6,t为基的,可拉制和/或热成型的,防潮耐变形的阻挡材料 - Google Patents

以共聚酰胺pa－6,1/6,t/6,6和/或pa－6,1/6,t为基的,可拉制和/或热成型的,防潮耐变形的阻挡材料 Download PDF

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CN1192449A
CN1192449A CN98105608.3A CN98105608A CN1192449A CN 1192449 A CN1192449 A CN 1192449A CN 98105608 A CN98105608 A CN 98105608A CN 1192449 A CN1192449 A CN 1192449A
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mole
polymeric amide
blocking material
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CN1138816C (zh
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M·维尔思
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Arkema France SA
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Elf Atochem SA
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Abstract

本发明涉及防水的、可阻挡气体与液体的材料,它可以是拉制和/或热成型的单体材料或多体材料组成的薄膜或薄层型。该阻挡材料是以共聚酰胺为基的,后者主要是由己撑二胺、间苯二甲酸与对苯二甲酸、以及己二酸所组成的。该材料可用于制成复合材料,包括单层或多层的薄层、薄片和/或薄膜、管件、空心体。它们可专门用于化学品、食品、药品和/或化妆品的包装。

Description

以共聚酰胺PA-6，1/6，T/6，6和/或 PA-6，1/6，T为基的，可拉制和/或 热成形的，防潮耐变形的阻挡材料
本发明涉及可阻挡气体与液体的聚合物材料领域，特别是防水的透明材料，它可以是单体材料或多体材料组成的薄层或薄膜成型。
一些文献已记载了许多有关阻挡材料的内容，特别是非晶形的聚酰胺树脂。欧洲专利文献EP 411,601描述了用于汽油容器的多层薄膜，其中的一层是由非晶形的共聚酰胺6，1/6，T所组成的，然而，这种非晶质的共聚酰胺树脂，在成品的热成形过程中，需要较高的转变温度。当含有该非晶质的聚酰胺树脂的成品是双定向时，那么其阻挡特性会大大降低。
为了克服上述缺点，人们使非晶质的聚酰胺树脂与其他的晶质的聚酰胺树脂一起结合使用。
欧洲专利文献EP 287,839描述了一种多层的膜，其中的一层是由结晶质聚酰胺与非晶质聚酰胺的混合物(PA-6，1/6，T)所组成的。
欧洲专利文献EP 366,382描述了一种用于充气瓶或模子瓶的组合物，其中含有非晶形PA的PA-6，PA-6，6混合物，以及薄片(层)状的填料。专利文献WO 93/01108还描述了一种食品容器，其中含有几种用非晶质PA的混合物PA-6，6，薄片(层)状的填料及离子键聚合物树脂。
上述解决问题的技术方案也带来了弊病，即需要增加一个或多或少相容的树脂混合步骤，为此，有时需加入一种相容剂。
迄今广泛使用的另一种阻挡材料是由乙烯与乙烯醇的共聚物(EVOH)所组成的。然而，该EVOH，除了价格昂贵外，而且其防潮性能也较差。因此，限制了其作为单材料成品的应用。如果将其用于混合材料成品时，就必须在EVOH与潮湿介质之间，至少加入一个中间层，以防止EVOH与潮湿介质的直接接触。此外，如果根据固相的热成形方法，制备具有一个EVOH阻挡层的多层的容器或薄膜时，事实证明，在其他的多层结构的树脂进行热成形时所需的较低温度下，EVOH的热成形过程，不可能不会出现EVOH层的断裂，从而导致其阻挡性能的完全丧失。为了克服上述缺点，我们也可以使EVOH与其他的树脂一起结合使用。欧洲专利文献EP 305,146描述了根据热成形法，用EVOH(大多数)与非晶质聚酰胺的混合物，制备出多层的容器。
然而，上述文献没有一个提出了可具有充分阻挡性能，并同时可单独使用的材料，它们可以容易地使用，并可加工变形，热成形，且不降低其阻挡性能。
本发明的目的是，提出满足上述准则的阻挡材料，而且可以摆脱树脂的混合过程，以制备出可阻挡气体与液体的(单)层材料。此外，这种材料对许多树脂具有良好的粘附性，本身又具有良好的透明性。因此，它极适用于包装用途，特别是食品包装。
本发明的阻挡材料至少包含一种共聚酰胺，后者主要是由己撑二胺、间苯二甲酸与对苯二甲酸、以及可能的己二酸等衍生单元所组成的，其结晶率(Xc)至少是5％，并以至少8％为宜。其结晶率是用théta-théta型折射仪[参照Nylon plastics Handbook(尼龙塑料手册)，M.I.Kohan Hanser出版社，1995年；4.6.2结晶度，第98-100页]，按广角范围的X射线衍射法测得的。
本发明的阻挡材料至少含有三聚酰胺PA-6，1/6，T/6，6或共聚酰胺PA-6，1/6，T，下文皆称为本发明的聚酰胺。其中每100摩尔共聚酰胺中含有：
40-67摩尔的PA-6，1
30-45摩尔的PA-6，T
0-20摩尔的PA-6，6或优选地
46-62摩尔的PA-6，1
30-42摩尔的PA-6，T
6-12摩尔的PA-6，6
此外，本发明的聚酰胺还可含有直至5％(重量)的其他聚酰胺单体，例如一种或多种羧二酸和/或二胺和/或氨基酸和/或内酰胺，其中特别提及1，4-二氨基环己烷、己内酰胺、十二烷内酰胺、辛撑二胺、癸烷撑二胺、十二烷撑二胺、1，5-二氨基己烷、2、2、4-三甲基、1，6-二氨基己烷、哌嗪、3，3’-二甲基-4，4’-二氨基-二环己基甲烷、4，4’-二氨基-二环己基甲烷、2，2’-(4，4’-二氨基-二环己基甲烷)丙烷，异佛尔酮二胺、壬二酸、癸二酸、月桂二酸。
优选地，来自于二聚作用的三胺，二(6-氨基-己基)胺，及己烷撑二胺的含量比例，据质子核磁共振(RMN)测定，是低于1.5％(摩尔)。
本发明聚酰胺的特性粘度，据在25℃，在0.5克/分升的聚合物的间苯甲酚溶液中测定，大约是0.75-1.3，并以0.85-1.05为宜。
本发明的聚酰胺，可按照相似于PA-6，6的合成方法，连续或不连续地聚合而成的。
把单体(己烷撑二胺，间苯二甲酸，对苯二甲酸，以及己二酸)加入到反应器中，优选地其中前者是以含有20-40％(重量)水的含盐水溶液形式存在的。上述单体中至少一种在反应混合物中的加入量稍超过其在最终共聚物中所含的比例量。随后，在其自生压力下，加热上述反应混合物至200-240℃，并以接近220℃为宜。在反应器内的压力通常达到1.5-2.5MPa。在该温度下，搅拌上述反应混合物约30分钟。
然后，蒸发除掉反应介质中的水分，以限制表面泡沫的出现，并避免压力的急剧下降。上述反应操作过程通常持续1小时30分钟～3小时30分钟，并以接近2个小时为宜，其温度最好控制在240℃。当反应器内压力又恢复到大气压力时，则可以在降压下，或在氮气氛中，继续进行聚合作用20分钟～1个小时30分钟。此时，我们就可以得到在250℃～300℃下挤压成颗粒状的聚合物。
事实证明，本发明聚酰胺的结晶率取决于其加热过程。当把聚合与挤压成形的聚酰胺在其玻璃状转变温度与其最大熔化温度之间加热时，它的结晶率就会增长。同样地，在上述温度范围内实施剪应力和/或拉伸，也能使本发明聚酰胺的结晶度比例增长，而且提高其阻挡性能。
本发明申请人证实，某些生成物，特别是水，当它与本发明聚酰胺接触时，会降低其玻璃状转变温度。在整个加热处理过程中，考虑到这种现象是至关重要的。
除了前述的共聚酰胺和/或三聚外，本发明阻挡材料还可以含有各种添加剂和/或调节剂。它们可以是：
—色料与颜料，例如二氧化钛、炭黑、氧化钴、氧化铁、钛酸镍，有机颜料，如蒽醌与西太菁的衍生物，
—光学增亮剂，例如噻吩的衍生物，
—抗氧化剂，例如含有碘化钾的碘化铜，苯酚或位阻胺的衍生物，
—紫外线(UV)稳定剂，例如间苯二酚、苯并三唑，水杨酸盐的衍生物。
—链限制剂，例如一元羧酸或一元胺，
—增强填料，例如硅灰石、玻璃珠、滑石、云母、玻璃纤维、氮化硼、碳酸钙和/或碳酸镁。
本发明同样地涉及用上述的至少以本发明聚酰胺为基的阻挡材料，制备出复合材料、包括单层或多层的薄层、薄片和/或薄膜、管件、空心体。
上述材料也可以根据惯用技术而加以使用，这些技术是用于热塑性树脂的。
作为多层材料的实施例，我们特别提及下列结合体：
a)至少一层本发明阻挡材料，
b)至少一层聚烯烃和/或聚酯和/或丙烯酸聚合物和/或聚碳酸酯，
c)至少一层置于a)与b)层之间的粘合剂层，例如具有极性分子与活性分子的共聚合或接枝的聚烯烃，
以及可能的一层或多层的其他材料层，例如：
d)至少一层其他的阻挡材料层，如EVOH层，
e)至少一层非晶质的聚酰胺和/或半晶质的聚酰胺，如PA-6，
含有本发明阻挡材料的层可以放置于表面上或夹入在其他材料层之间。
本发明阻挡材料可以制成空心体，其中用吹塑挤压工艺，或用双轴取向的预加工成形的注射法制成的这种空心体可以是小瓶、细颈瓶、用于化学品、食品、药品和/或化妆品的包装容器。
用吹塑挤压法制成的空心体，除了包含一层本发明阻挡材料层外，还包含一层聚烯烃，例如PE或PP，以及一层EVOH，各层之间的接触结合是用共挤压粘合剂形成的。作为多层材料构成体，我们可以提及下列结合体：
—PEhd/粘合剂/EVOH/粘合剂/本发明阻挡材料，
—PE/粘合剂/本发明阻挡材料/粘合剂/PE，
—Pehd/粘合剂/本发明阻挡材料。
当本发明阻挡材料，作为上述结构体的表面层时，最好使其作为空心体的内容的接触面。
当使用预加工成形体的注射工艺时，可以使双轴取向的预加工成形体加热到接近(一定超过)该材料的玻璃状转变温度，其中该材料中含有本发明阻挡材料。然后凭用垂直于主轴线的冲头沿其它轴线拉长。这种工艺方法可以改进本发明阻挡材料的阻挡性能。
我们同样地可以通过共注射法，注射成多层的预加工成形体，以便得到核心一表皮型的预加工成形体。在这些多层的预加工成形体中，我们特别提及含有不厚的由本发明阻挡材料组成的核心，以及很厚的由聚对苯二甲酸乙酯(PET)所组成的表皮的预加工成形体。美国专利文献US5,143,733还提出制备具有4或5层的多层的预加工成形体。在其中的5层结构体中，包括了PET/本发明材料/PET/本发明材料/PET。
上述阻挡材料也同样地适合于转变成单层或多层的薄膜。根据挤压管工艺或平模挤压工艺，以及在冷辊上的淬火过程，可以制得完全透明的薄膜。
为了制得多层的薄膜，可以使本发明的材料与聚乙烯和/或EVOH和/或其他前述的阻挡材料一起结合使用。这种单层或多层的薄膜可以被双轴取向(以便改进其阻挡性能)。这种双轴取向过程可以在平板或双泡罩管中进行。
上述阻挡材料也可以通过挤压工艺制成单层和/或多层的管件。例如，经测定内径后，穿过环形压模进行加工处理。作为多层的管件，我们特别提及，它们除了包含有一层本发明的材料外，还至少含有一层聚烯烃，最好是PE层。此外，在本发明材料与聚烯烃层之间夹有粘合剂，以便形成如下的结合体：
PE/粘合剂/本发明材料，
PE/粘合剂/本发明材料/粘合剂/PE。
这种管件特别适用于输送烃类物质。
本发明阻挡材料也可以与其他的树脂一起混合使用，特别是其他的PA树脂。其中包括脂族PA，如PA-6和/或PA-6，6，非晶质PA，酞酰亚胺型的PA，等等。在本发明阻挡材料与PA-6和/或PA-6，6的混合物中，当脂族的PA占据大多数的情况下，阻挡材料的存在特别敏感地改进脂族的PA的双轴取向性能，降低其潮湿度的恢复，并改进其挤压时的转变性能(操作助剂)及其透明性。
在阻挡材料与PA-6和/或PA-6，6的混合物中，当阻挡材料占据大多数的情况下，脂族PA的存在改进了阻挡材料的单层薄膜的双轴取向性能，并改进了其刚性。
实施例1-7，本发明聚酰胺的合成
实例1
把以含盐水溶液形式存在的单体(己撑二胺、间苯二甲酸、对苯二甲酸与己二酸)放入到装有锚式搅拌器的，980升的不锈钢的压热容器中。其中，在反应混合物中的己二酸的加入量，稍超过其在最终共聚物中的比例含量，所含成分的比例量如下所示：
己撑二胺      133.0公斤
己二酸        16.8公斤
间苯二甲酸    87.0公斤
对苯二甲酸    58.0公斤
脱盐的软化水  80公斤
当反应压力在大气压与800KPa之间的范围内交互变化的情况下，用氮气净化上述反应混合物五次。然后在自生压力下，加热至220℃。在反应器内的压力达到2.3MPa时，保持该温度下，搅拌30分钟。搅拌的速度是40转/分。
接着缓慢地蒸发除掉反应介质中的水分，以限制表面泡沫的出现，并避免压力的急剧降低。上述操作过程持续2个小时30分钟，反应温度稍提高到240℃为止。然后，使反应器内盛物的压力恢复到大气压。并在氮气氛中，加热该反应介质至270℃，继续进行聚合反应约1个小时。此时的搅拌速度降至15转/分。
由此所得的熔融聚合物，通过反应器的底部阀门往外挤出。在反应器内仍留有稍超压的氮气，其中的温度是270℃。
然后在60℃下用6个小时，并继而在80℃下用6个小时对该聚合物进行干燥处理。
该聚合物的摩尔组分如下所示：
PA-6，1  0.54
PA-6，T  0.36
PA-6，6  0.115
其特性粘度是0.85～1.05g/dl(克/分升)。
用其结晶率Xc为9％的上述聚合物，通过平模的挤压，制得其厚度为50mm的薄膜。
实例2-7
根据实例1的操作模式，我们制得如表1所示的各种不同摩尔组分的三聚酰胺。其中，根据质子的RMN(核磁共振)法测得的二(6-氨基-己基)胺严格控制在1.5％以下。
根据差示扫描量热法(DSC)，我们测得各种不同树脂的玻璃状转变温度Tv，熔化高峰值Tf，以及熔化范围。其测定结果如表1中所示。
表1
   实例     摩尔组分PA-6，1/6，T/6，6     Tg℃  熔化峰点Tf℃    熔化范围℃
    2   0,54/0,40/0,06     122     236     200-277
    3   0,57/0,40/0,03     126     242     215-280
    4   0,58/0,36/0,06     121     249     219-262
    5   0,52/0,38/0,10     116     246     201-276
    6   0,54/0,34/0,12     115     240     200-250
    7   0,534/0,356/0,117     117     234     195-275
实例8-14本发明聚酰胺的用途，用作阻挡材料
实例8-10单层的薄膜
把实例1的树脂挤压制成其厚度为20-60μm(实例8)的流延薄膜。这种薄膜是完全透明的，具有光泽，没有由于凝结和/或不熔造成的明显缺陷。
把部分上述薄膜进行退火(实例9)，在密闭容器中，即在相对湿度为100％的环境中，在80℃下储存12个小时，该薄膜的结晶率Xc是14％。
作为对照，我们把非晶质聚酰胺PA-6，1/6，T挤压制成具有相同厚度的薄膜(在差示扫描量热法DSC中，未显示吸热结晶的熔化峰值，用ASTM D 3417标准进行测定，其Xc＝0％)。其中，间苯二甲酸相对于对苯二甲酸的摩尔比例是70/30(实例10)。这种树脂是以SELARPA作为商品名，由杜邦(Du pont deNemours)公司在市场上出售的。
借助于OXTRAN仪器，在相对温度(HR)的零的环境中，接着在相对湿度为75％的环境中，测出氧的渗透性(PO2)，以及氧化的或没氧化的汽油的渗透性。氧的渗透性以cm3*20μm/m2*24h*atm表示，而汽油的渗透性以g*20μm/m2*24h*atm表示，其测得结果如在表2中所示。
表2
  实例 PA-6，1/6，T/6，6摩尔组分    pO2  0％HR   pO2  75％HR   汽油C   汽油TF1
    8  0,54/0,36/0,11     60     26     2     35
    9  0,54/0,36/0,11     49     7-8     2     40
    10  0,70/0,30/0,00     50     25     5     48
汽油C：是等容积量的甲苯与异辛烷的混合物。
汽油TF1：是10％(容积)的乙醇与90％(容量)汽油C的混合物。
实例11-14多层的薄膜
借助于吹塑挤压机BEKUM，我们挤压成三层与五层的薄膜，其中的一层是实例1的树脂，其商品名为SELARPA或EVOH，后者含有29％(摩尔)的乙烯，其皂化度大于99％。用其商品名为OREVAC18032的，以马来酸酐与接枝的乙烯共聚物为基的粘结剂作为上述各相邻层间的夹入层。它自己还可以接触其流动性指数为0.3(即在190℃下，用2.16公斤负荷，根据ISO 1133标准测得的)，其密度为0.953(据ISO1133标准测得)的PEhd层。表3显示了这种薄膜的结构与厚度。在相对湿度为100％的环境中，测得其氧的渗透性。测得结果也显示于表3中。
表3
    实例     薄膜的结构与厚度(μm)   pO2(100％HR)
    11     PEhd/粘合剂/SELAR PA356/44/64     0,096
    12     PEhd/粘合剂/PA实例1318/76/44     0,065
    13     PEhd/粘合剂/PA实例1406/64/51     0,057
    14     PEhd/粘合剂/EVOH/粘合剂PEhd305/25/44/25/102     0,101

Claims (7)

1、聚酰胺，其特征是，相对于100摩尔的单体，含有
40-67    摩尔的 PA-6，1
30-45    摩尔的 PA-6，T
0-20     摩尔的 PA-6，6
其中，根据大角度范围内X射线衍射所测定的，结晶率(Xc)至少是5％，并以8％为宜。
2、根据权利要求1所述的聚酰胺，其特征是，相对于100摩尔的单体，含有
46-62    摩尔的 PA-6，1
30-42    摩尔的 PA-6，T
6-12     摩尔的 PA-6，6
3、根据权利要求1或2所确定的至少一种聚酰胺的应用，其中用于制作气体与液体的阻挡材料，以抗(防)潮湿。
4、利用根据权利要求3所述阻挡材料制成的单层成品，如薄片和/或薄膜、管件、空心体。
5、用权利要求3限定的至少一种阻挡材料制成的复合材料成品，如薄片和/或薄膜，管件，空心体。
6、权利要求4或5限定的制成品的制备方法，其特征是，在至少一个操作阶段中的操作温度，处在根据权利要求1与2的聚酰胺的玻璃状转化温度与其最高的熔融温度之间。
7、根据权利要求4与5所限定的制成品的用途，其中用于化学品、食品、药品和/或化妆品的包装。
CNB981056083A 1997-01-20 1998-01-20 以共聚酰胺pa-6,i/6,t/6,6和/或pa-6,i/6,t为基的,可拉制和/或热成形的,防潮耐变形的阻挡材料 Expired - Fee Related CN1138816C (zh)

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CN1138816C (zh) 2004-02-18
JPH10204174A (ja) 1998-08-04
FR2758564B1 (fr) 1999-03-26
CA2224501A1 (fr) 1998-07-20
EP0854161A1 (fr) 1998-07-22
DE69826904D1 (de) 2004-11-18
EP0854161B1 (fr) 2004-10-13
US6217962B1 (en) 2001-04-17
FR2758564A1 (fr) 1998-07-24

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