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CN101006124B - 聚合薄膜 - Google Patents

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CN101006124B
CN101006124B CN2005800283654A CN200580028365A CN101006124B CN 101006124 B CN101006124 B CN 101006124B CN 2005800283654 A CN2005800283654 A CN 2005800283654A CN 200580028365 A CN200580028365 A CN 200580028365A CN 101006124 B CN101006124 B CN 101006124B
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film
alkylene oxide
multipolymer
oxide homo
crosslinked
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CN101006124A (zh
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V·Y·何
R·L·施米特
P·源
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Union Carbide Chemicals and Plastics Technology LLC
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Abstract

本发明涉及包含环氧烷均聚物或共聚物的聚合薄膜，其中该薄膜包含交联环氧烷均聚物或共聚物的连贯图案和非交联环氧烷均聚物或共聚物区域，其可用作粘合膜或用于制备粘合膜。

Description

聚合薄膜
本发明涉及包含环氧烷均聚物或共聚物的聚合薄膜。
发明背景
环氧烷聚合物可用于多种用途。美国专利3,264,202公开了通过电离辐射处理交联的聚环氧烷。美国专利3,419,006公开了包含一层亲水聚合物凝胶(例如通过辐射交联的环氧乙烷聚合物)的透明伤口敷料。M.Doytcheva等人在J.Appl.Polym.Sci 64：2299-2307，1997中的文章“Ultraviolet-Induced Crosslinking of Solid Poly(ethylene oxide)”描述了使用和不使用二苯甲酮作为光引发剂的紫外线辐射。该文章公开表示，交联聚(环氧乙烷)可用作伤口敷料、控释药物体系、相转移催化剂、半透膜或电池的固体电解质。
交联聚(环氧乙烷)通常不溶于水，且没有表现出明显的粘合性质。但是，对于伤口敷料或控释药物体系之类的某些用途，需要提供包含交联C2-4环氧烷均聚物或共聚物并具有粘合性质的薄膜。
发明概述
本发明的一个方面是包含环氧烷均聚物或共聚物的聚合薄膜，其中该薄膜包含i)交联环氧烷均聚物或共聚物的连贯图案和ii)在该薄膜的一面或两面上的非交联环氧烷均聚物或共聚物区域。
本发明的另一方面是包含上述薄膜的复合制品。
本发明的再一方面是制备上述薄膜的方法，包括下列步骤a)制备包含环氧烷均聚物或共聚物的薄膜，b)在该薄膜的一面或两面上在所选区域遮蔽薄膜以避免辐射，从而留下未遮蔽的薄膜材料的连贯图案，和c)在薄膜的一面或两面上对薄膜进行辐射。
本发明的再一方面是上述薄膜作为粘合膜或用于制备粘合膜的用途。
本发明的再一方面是上述薄膜制备伤口敷料薄膜或给药薄膜的用途。
附图简述
图1和2代表本发明的薄膜的两种优选实施方案上的示意图。
图3显示了本发明的薄膜在水存在下的溶胀。
发明详述
本发明的薄膜包含交联环氧烷均聚物或共聚物的连贯图案和非交联环氧烷均聚物或共聚物区域。
交联环氧烷均聚物或共聚物包含分子内和分子间的碳-碳交联键，从而使交联聚合物不溶于水并在氧存在下稳定。本文使用的术语“不溶于水”是指在25℃和1大气压下小于5克，优选小于2克，更优选小于1克的交联聚合物可溶于100克蒸馏水。交联聚合物形成基体，也称作连续相，其通常在水中可溶胀但不可溶，且即使薄膜与水接触也具有足够的薄膜强度。
非交联环氧烷均聚物或共聚物区域在与水接触时具有粘合性质。在交联聚合物基体中的非交联聚合物粘合区域的尺寸、数量和图案可以大程度变化并调节至适于所需最终用途。通过提供包含交联环氧烷均聚物或共聚物的连贯图案和非交联环氧烷均聚物或共聚物区域的薄膜，实现水存在下的薄膜完整性和粘合性的最佳组合。此外，下述本发明的方法能够制造下述薄膜——其中，水存在下的薄膜完整性和薄膜粘合性可以受控并调节至适于所需最终用途。非交联亚烷基均聚物或共聚物通常具有在25℃和1大气压下在100克蒸馏水中至少5克，优选至少10克的水溶性。非交联亚烷基均聚物或共聚物优选具有100,000至8,000,000，更优选600,000至5,000,000，最优选900,000至4,000,000的通过凝胶渗透色谱法测得的重均分子量。
可用于本发明的薄膜的环氧烷均聚物或共聚物优选为C2-4环氧烷均聚物或共聚物，例如环氧乙烷、环氧丙烷、1，2-butene epoxide、二甲基环氧乙烷(isobutylene oxide)的均聚物或共聚物。本发明的薄膜最优选包含环氧乙烷均聚物或共聚物。其它可用的聚合物是脂环族环氧化物(例如1，2-cyclohexene epoxide)、乙烯基环己烯化氧(例如4-乙烯基-1-环己烯-1，2-环氧化物、环氧基环己烯或4-乙烯基-1-环己烯二环氧化物)；dipentene epoxide、不饱和缩水甘油醚(例如乙烯基缩水甘油醚或烯丙基缩水甘油醚)；烷基缩水甘油醚(例如甲基缩水甘油醚、乙基缩水甘油醚、异丙基缩水甘油醚、异丁基缩水甘油醚、叔丁基缩水甘油醚、正己基缩水甘油醚或正辛基缩水甘油醚)；1，3-双环氧丁烷、氧化苯乙烯、苯基缩水甘油醚或烷基苯基缩水甘油醚的均聚物和共聚物。
环氧烷共聚物可以是通过至少两种环氧烷的混合物的聚合制成的无规共聚物。其它可用的环氧烷共聚物是通过连续添加一种以上的环氧烷制成的嵌段共聚物，其中在添加随后的单体之前，每一环氧烷几乎完全消耗。或者，环氧烷共聚物可以包含共聚形式的环氧烷和另一可共聚单体，例如丙烯酸甲酯、丙烯酸乙酯、己内酯、碳酸亚乙酯、碳酸三亚甲酯、1，3-二氧戊环、二氧化碳、硫化羰、四氢呋喃、异氰酸甲酯或甲胩。优选环氧烷共聚物是环氧乙烷与表氯醇的共聚物，或环氧乙烷与环己基化氧的共聚物。环氧烷共聚物通常含有至少50摩尔％，优选至少70摩尔％，更优选至少85摩尔％的环氧烷单元。最优选的环氧烷聚合物是环氧乙烷共聚物或更优选环氧乙烷均聚物。
本发明的薄膜优选含有至少40wt％，更优选至少60wt％，最优选至少90wt％的环氧烷均聚物或共聚物，以薄膜的总重量计。
薄膜可以包含一种或多种其它聚合物，优选水溶性聚合物，例如一种或多种树胶，例如阿拉伯树胶、黄原胶或瓜耳胶；角叉菜聚糖、葡聚糖、明胶、藻酸盐、果胶、瓜耳胶衍生物、黄原胶衍生物或多糖，例如淀粉、淀粉衍生物、纤维素醚或纤维素酯。优选的是羧基-C1-C3-烷基纤维素、或羧基-C1-C3-烷基羟基-C1-C3-烷基纤维素、羟基-C1-3-烷基纤维素，例如羟乙基纤维素；C1-C3-烷基纤维素，例如甲基纤维素或乙基纤维素；C1-C3-烷基羟基-C1-3-烷基纤维素，例如羟乙基甲基纤维素、羟丙基甲基纤维素或乙基羟乙基纤维素。可用聚合物的其它例子是乙烯亚胺、不饱和酸(例如丙烯酸)或其盐、不饱和酰胺(例如丙烯酰胺)、乙烯基聚合物(例如乙烯醇)、乙烯酯(例如乙酸乙烯酯)、乙烯基吡咯烷酮、乙烯基噁唑烷酮、乙烯基甲基噁唑烷酮、乙烯磺酸、乙烯胺、乙烯基吡啶或烷基甘醇的均聚物或共聚物。本发明的薄膜可以包含一种或多种增强材料，例如尼龙纱布、嫘萦网、涤纶或纤维素网。这类其它聚合物或增强材料的量优选不超过60％，更优选不超过40％，最优选不超过10％，以薄膜的总重量计。
本发明的薄膜优选包含光引发剂，例如苯偶姻、苯偶姻甲醚、苯乙酮、四甲基二氨基二苯甲酮(米蚩酮)或Ciba-Geigy SpecialtyChemicals，Switzerland以商标IRGACURE或DAROCUR出售的光引发剂。优选光引发剂是二苯甲酮。如果存在光引发剂，其在薄膜中的重量优选最多为10％，更优选0.4至5％，最优选1至2％，以环氧烷均聚物或共聚物的总重量计。
本发明的薄膜可以包含其它添加剂，例如一种或多种填料或活性成分，例如化学治疗剂或药剂。可用治疗剂和其它添加剂是，例如，美国专利3,419,006的栏目7，行30-57中所列的那些，该专利的内容经此引用并入本文。如果存在，它们的量通常不超过20％，在多数情况下不超过10％，以薄膜的总重量计。
薄膜优选具有20微米至5毫米，更优选100微米至2.5毫米，最优选200至500微米的厚度。薄膜可以具有任何形状，例如板状或条状。
本发明的薄膜可以在包括下列步骤的方法中制造：a)制备包含环氧烷均聚物或共聚物的薄膜，b)在该薄膜的一面或两面上在所选区域遮蔽薄膜以避免辐射，从而留下未遮蔽的薄膜材料的连贯图案，和c)在薄膜的一面或两面上对薄膜进行辐射。
该方法的步骤a)可以以已知方式进行。例如，可以通过将任选与一种或多种添加剂掺合的环氧烷均聚物或共聚物压塑或挤出以制造薄膜。或者，可以将任选与一种或多种添加剂掺合的环氧烷均聚物或共聚物溶于水或有机溶剂，例如氯化烃，如二氯甲烷；或醇，例如乙醇；或它们的混合物。然后可以通过已知的溶剂浇注方法从溶液中浇注薄膜。
在本发明的方法的步骤b)中，在所选区域遮蔽薄膜以避免辐射，从而留下未遮蔽的薄膜材料的连贯图案。可以按照已知方式在一面或两面遮蔽薄膜。例如，所选区域可以被胶布覆盖，该胶布的材料基本不会被辐射处理中所用的辐射束透过，例如纸板、玻璃或不透明塑料材料。
图1中显示了遮蔽薄膜以产生所需部分辐射图案的一种优选图案。在交联之后，薄膜在薄膜背面包含非交联区域1，在薄膜正面包含非交联区域2。这些非交联区域为薄膜提供粘合性质。交联之后，薄膜还包含交联聚合物的连贯图案3，其提供所需的薄膜完整性。如果薄膜在薄膜的两个面上均包含非交联区域，这些区域优选以交错方式排列，从而从至少一面对每一薄膜区域进行辐射。非交联区域的交错图案提供了薄膜粘合性和薄膜完整性的最佳组合。
本发明的方法的明显优点在于，非交联和交联聚合物区域可以大程度变化并可以调节至适于特定的薄膜最终用途。根据预计最终用途，可能需要仅在薄膜的一面遮蔽所选薄膜区域以避免辐射。本发明的这种优选实施方案显示在图2中，其中薄膜在薄膜正面包含非交联区域2，还包含交联聚合物的连贯图案3。
在本发明的方法的步骤c)中，对薄膜进行辐射。可用的辐射处理是，例如，γ或电子束、电离辐射，包括来自Van De Graff和其它高压加速器的α粒子、β粒子、X-射线、γ射线和电子。优选处理是用紫外线辐射。辐射薄膜的至少一个，优选两个面。为薄膜辐射提供有效的能量剂量在技术人员的知识范围内。例如，当使用市售Fusion SystemEPIQ 6000设备时，可以使用600mJ/cm2至19,000mJ/cm2，更优选1,200mJ/cm2至10,000mJ/cm2，最优选3,000至6,000mJ/cm2的能量剂量使薄膜交联。优选选择交联用的能量以使薄膜交联区域中的环氧烷均聚物或共聚物具有在25℃和1大气压下在100克蒸馏水中小于5克，优选小于2克，更优选小于1克的水溶度。
本发明的薄膜可用作stand-alone薄膜和作为复合制品的一部分，例如作为伤口敷料、用于给药、例如用于皮肤病、和用作控释给药体系；用作相转移催化剂、用作半透膜；和用作粘合剂。
复合制品可以例如含有本发明的薄膜和第二聚合材料(例如聚偏二氯乙烯、聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚酰胺、聚氯乙烯、乙酸纤维素及其衍生物、聚二甲基丁二烯、聚氨酯、聚乙烯醇、硅氧烷橡胶或聚丙烯酸)背衬。由于本发明的薄膜的粘合性质，通常不必使用附加粘合剂来将本发明的薄膜固定到第二聚合材料上。
通过下列实施例对本发明进行举例说明，这些实施例不被视为限制本发明的范围。除非另行说明，所有份数和百分比均按重量计。
实施例1和2和对比例A-C
薄膜样品的制备和交联
将62.4份重均分子量为大约2,000,000且作为2wt％水溶液测得的粘度为大约3,000mPa.s的聚环氧乙烷和1.2份二苯甲酮在低剪切掺合机中干混5分钟。聚环氧乙烷可以以商标POLYOX N-60K Water SolubleResin购自Amerchlo Corporation。在粉末混合物中添加0.1份维生素E在9.1份异丙醇中的溶液。干混之后，将混合物在95℃加入Brabender混合罐中。在Brabender混合罐中在混合物中添加18.2份水和9.1份甘油作为增塑剂。然后将熔融混合物转移到液压机中并在95℃和2500psi(17.2MPa)压塑成10密耳(0.25毫米)薄膜。在压机中在室温冷却之后，收集薄膜样品并保存在聚乙烯袋中。
将1.2毫米圆形纸板交替贴到薄膜样品的两面上以产生部分辐射的所需图案。图案显示在图1中。将每一薄膜样品放在传送带上，并从Fusion System EPIQ 6000中的紫外线灯下穿过以进行紫外线固化。对每一辐射过程选择1050mJ/cm2的能级和20英尺/分钟(608厘米/分钟)的传送带速度。辐射两组薄膜。对于第一组，使薄膜的每一面从紫外线灯下穿过5次，以使总固化能量为5250mJ/cm2。这第一组薄膜在下文中被称作5/5薄膜样品或实施例1。对于第二组，使薄膜的每一面从紫外线灯下穿过3次，以使总固化能量为3150mJ/cm2。这第二组薄膜在下文被称作3/3薄膜样品或实施例2。
粘合性质
使用来自Texture Technologies Corporation的Texture Analyzer测量所得薄膜样品的粘合性质。为了进行该试验，将2英寸×2英寸(5厘米×5厘米)部分交联薄膜用双面胶带粘到平台上。将薄膜表面用水润湿两次。在30秒水合时间之后，将1英寸(2.5厘米)直径的丙烯酸圆柱探针以500克的力压在薄膜样品上10秒。将薄膜样品与探针对齐以使薄膜中心的非交联环与探针中心对齐。在10秒接触时间之后，在将丙烯酸圆柱探针从薄膜上拉开时进行粘合强度测量。下表I概括了试验结果。
表1
  (对比)实施例   A    1    2   B
  样品   5/5完全交联<sup>*</sup>    5/5部分交联    3/3部分交联   3/3完全交联<sup>*</sup>
                           粘合(克)
  (对比)实施例   A    1    2   B
  1   66.4    841.1    665.8   77.3
  2   80.1    513.1    638.2   194.9
  3   77.6    379.7    422.8   79.3
  4   112.7    701.8    469.9   63.6
  5   61.8    364.8    872.3   93.2
  6   84.4    454.1    584.7   189.5
  7   23.7    395.1    636.3   145.0
  8   8.5    283.0    523.9   51.0
  平均   64.4    491.6    601.7   111.7
*在不遮蔽薄膜任何区域的情况下通过紫外线辐射进行交联
实施例1和2的薄膜具有良好的粘合性质，但是对比例A和B的薄膜具有对需要薄膜粘合性的许多最终用途而言太低的粘合值。
薄膜溶度和溶胀比
图3显示了实施例1和2的部分交联薄膜与没有进行辐射的对比例C的非交联薄膜相比的水溶性。在水接触之前，通过首先测量干燥薄膜样品的面积(长×宽)来产生数据。然后，将每一干燥薄膜样品放在金属丝网筛上并在试验过程中完全浸在水中。以指定时间间隔测量湿薄膜的面积。薄膜的溶胀比是指在指定时间间隔下，溶胀薄膜样品的面积除以干燥薄膜样品的面积。图3表明，对比例C的非交联薄膜迅速溶于水。其不可用于要求薄膜完整性的最终用途。

Claims (11)

1.一种包含环氧烷均聚物或共聚物的聚合薄膜，其中该薄膜包含i)交联环氧烷均聚物或共聚物的连贯图案和ii)在该薄膜的一面或两面上的非交联环氧烷均聚物或共聚物区域。
2.根据权利要求1所述的薄膜，其中所述环氧烷均聚物或共聚物是C2-4环氧烷均聚物或共聚物。
3.根据权利要求1所述的薄膜，其包含至少40wt％的环氧乙烷均聚物或共聚物，以薄膜总重量计。
4.根据权利要求1至3任一项所述的薄膜，还包含光引发剂。
5.根据权利要求4所述的薄膜，其中所述光引发剂是二苯甲酮。
6.根据权利要求4所述的薄膜，包含0.4至5wt％的光引发剂，以环氧烷均聚物或共聚物总重量计。
7.一种包含权利要求1至6任一项所述的薄膜的复合制品。
8.一种制备权利要求1至6任一项所述的薄膜的方法，包括下列步骤a)制备包含环氧烷均聚物或共聚物的薄膜，b)在该薄膜的一面或两面上在所选区域遮蔽薄膜以避免辐射，从而留下未遮蔽的薄膜材料的连贯图案，和c)在薄膜的一面或两面上对薄膜进行辐射。
9.根据权利要求8所述的方法，其中在薄膜的两面上均辐射薄膜。
10.权利要求1至6任一项所述的薄膜作为粘合膜或用于制备粘合膜的用途。
11.权利要求1至6任一项所述的薄膜用于制备伤口敷料薄膜或给药薄膜的用途。
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