CN1146775A - 易降解的星形嵌段共聚物 - Google Patents

易降解的星形嵌段共聚物 Download PDF

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CN1146775A
CN1146775A CN95192679A CN95192679A CN1146775A CN 1146775 A CN1146775 A CN 1146775A CN 95192679 A CN95192679 A CN 95192679A CN 95192679 A CN95192679 A CN 95192679A CN 1146775 A CN1146775 A CN 1146775A
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polylactide
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T·M·福特
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EIDP Inc
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EI Du Pont de Nemours and Co
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Abstract

含有分子量有限的聚己内酯和聚交酯嵌段的星形嵌段共聚物是韧性易降解的聚合物。这种共聚物是非结晶性的，其玻璃化温度接近或低于室温，可用于多种包装材料和其它用途。

Description

易降解的星形嵌段共聚物
                     发明领域
这里公开的是容易水解和生物降解的己内酯和交酯的星形嵌段共聚物。这种共聚物即使分子量较低也是坚韧的类弹性材料。
                     技术背景
聚合物，特别是热塑性塑料，从理论上讲是可重复使用的，但是由于收集、分类和纯化这些回用塑料需要相当的费用，所以通常不加以回收使用。因此，大多数塑料和其它聚合物，如弹性体，与其它废物一起废弃在例如垃圾垫土中，在此它们的化学性质很稳定，极少降解。减少垃圾垫土及类似地方稳定聚合物数量的一种方法是生产可通过水解、生物降解或类似过程而降解的聚合物。
已经知道，在适当条件下，聚交酯是可生物降解的，因此含有这种重复单元的聚合物被认为是理想的。然而，大多数聚交酯聚合物都是塑料，也就是说，其玻璃化温度(Tg)在室温以上，且这类聚合物可能是结晶的。含有交酯重复单元但仍具有类弹性体性质的聚合物也是理想的。
美国专利5,210,108叙述了一种由含有交酯重复单元的星形聚合物制成的泡沫。所制得的泡沫是刚性的，不是弹性的。
D.W.Grijpma等人，Makoromol.chem.Rapid Comun.，第14卷，第155-161页(1992)报导了含有聚交酯嵌段和碳酸三亚甲基酯或碳酸三亚甲基酯和另一种内酯嵌段的混合物的星形嵌段共聚物的合成方法。这类共聚物中聚交酯的Tg为50-55℃。
                    发明概述
本发明涉及一种主要由一个芯层、连接到所述芯层上的3至约20个聚己内酯内臂和连接到所述内臂上的聚交酯外臂构成的星形嵌段共聚物，其条件是：
所述聚交酯占所述共聚物重量的至少50％；
所述聚己内酯占所述共聚物重量的约10％-约50％；
所述聚己内酯和聚交酯在熔融加工时不结晶；和
所述交酯的玻璃化温度小于35℃。
                   发明详述
本发明的共聚物是一种含有聚己内酯和聚交酯嵌段的星形共聚物。这种共聚物也含有一个芯层，它通常是共聚物的“起点”。该芯层起初是一种多官能材料，通常含有与星形共聚物具有的臂数目相同的官能基团。在本情形中，所谓官能基团是指能通过自身或通过基团的反应形成一个引发一个共聚物链(星的一个臂)的部位的基团。在本情况下，它将引发己内酯的聚合反应。
适用于芯层的官能基团包括羟基、氨基和硫氢基。这些基团可按照标准方法用来引发己内酯的聚合。例如，可以使用诸如辛酸锡之类的催化剂。这类聚合反应可参阅欧洲专利申请117,538，该文献入本文作为参考。该聚合反应可以在纯态(无溶剂)下或在溶剂存在下进行。
这里聚己内酯是由单体ε-己内酯形成的。这里聚己内酯形成了共聚物的“内臂”。一个内臂就是附在或连接在该芯层上的聚合物。由于聚己内酯的Tg很低(低于0℃)，这种性质一般不影响本发明产品的刚性。但是，如果聚己内酯的分子量足够高的话，它就会部分结晶。因此，聚己内酯嵌段的分子量必须低到足以使得在熔融加工时不发生这样的结晶。对聚己内酯内臂而言，有效的分子量范围是数均分子量为约800-约4000。较好的是聚己内酯占共聚物重量的约10％-约40％，更好是占共聚物重量的约15％-约30％，特别好的是占共聚物重量的约18％-约22％。
当己内酯聚合时，端基通常是羟基，羟基可以用来维持引发交酯的聚合反应。因此，交酯聚合物嵌段变成连接到(附在)聚己内酯嵌段的端部，该嵌段在此称为外臂。D型、L型或内消旋型的交酯，或其任何组合都可用于形成聚交酯嵌段。交酯均聚物是半结晶的，其Tg为约55-60℃。因此，聚交酯嵌段必须小(分子量低)到足以使得Tg为35℃或更低，较好30℃或更低。聚交酯嵌段大小的典型有效范围是数均分子量约1,000-约12,000，但这个范围随聚己内酯嵌段的大小不同可以有或多或少的改变。较好的是，每个聚交酯嵌段的数均分子量为约3,000或更高。如果聚交酯占共聚物重量的至少70％，则也是较好的。
聚交酯嵌段是由交酯本身的聚合而形成的。这种聚合反应可按照许多方法进行，但通常在催化剂存在下进行。辛酸锡是一种有效的催化剂，但优选的催化剂选自稀土金属化合物，如美国专利5,028,667和5,292,859公开的那些催化剂，这两篇专利文献均列入本文作为参考。后一专利公开的催化剂尤其优选。这类聚合以纯态或在溶剂存在下进行，但以纯态(无溶剂存在)聚合为优选。聚合温度不严格，0℃-约200℃是方便的范围。己内酯和交酯的聚合可按顺序步骤在同一反应器中进行，或者可将聚己内酯(附在芯层上)星形聚合物分离，然后与要聚合的交酯混合生成最终共聚物。
本发明的星形嵌段共聚物具有3-20个臂，较好3-10个臂，更好3-6个臂，且特别优选4个臂。
本发明所述的共聚物是相当坚韧的类似弹性体的材料，适用于许多用途。这些用途包括液体食品包装材料，例如牛奶袋、汁袋、冷藏液体用涂布盒的涂层，以及加工肉食的包装材料；干食品包装材料，例如盒装食品的外包装材料，作为部分多层包装薄膜，以及作为冷冻食品涂布挡板的涂料；用于快餐食品如饮料杯涂布纸板的涂料；其它消费品如作为尿布用非织造吸收材料、用于尿布的软性柔韧背衬、化妆用具及化妆品用的外包装薄膜，以及个人护理用品；农产品，如覆盖膜；医药品，如柔韧的伤口敷料及低膜量手术植入物；作为其它聚合物，如用于泡沫材料体或吹塑的聚合物的增韧添加剂，和作为要纺制成纤的聚合物的改性剂，用以改善伸长率和韧性；以及其它用途，例如粘合剂、动物饲料添加剂的外包装薄膜以及人造雪。本文公开的共聚物由于具有生物可降解性、韧性、撕裂强度和柔软手感，所以在上述用途中特别有用。
本发明的共聚物必须是不结晶的，即在熔融加工时用差示扫描量热法(见下面的Tg测试)测试时熔化热不大于3J/g。用于这种试验的样品是这样来制备的：在模温约10℃，共聚物熔体温度(出螺杆套筒)约150℃的条件下将所讨论一些共聚物用注射膜塑法制成3.2mm厚的板。
本文中分子量是用凝胶渗透色谱法以聚苯乙烯为标准样测定的。聚交酯外臂的平均分子量等于共聚物的数均分子量乘以共聚物中聚交酯的重量分数，再除以共聚物的名义臂数。类似地，聚己内酯内臂的平均分子量等于共聚物的数均分子量乘以共聚物中聚己内酯的重量分数，再除以共聚物的名义臂数。
共聚物(尤其是聚交酯嵌段)的玻璃化温度(Tg)是按如下方法测定的。约0.5g共聚物溶解在5ml二氯甲烷中，将所形成的溶液滴加到50ml快速搅拌的甲醇中(这样做是为了除去共聚物中存在的起增塑剂作用的任何交酯)。通过过滤和/或倾析收集沉淀出的絮状物，然后在室温下进行真空干燥。用300MHz的1H-NMR分析来确定共聚物中不残留交酯。用TA Instruments 2100型分析仪对装在带盖、密封的标准铝盘中的5-10mg样品进行差示扫描量热(DSC)测定。加热速率为10℃/分钟。取这级转变的中点作为Tg。如果共聚中聚交酯的Tg为30℃或更低，则是比较好的。
在下列实例中，Mn是数均分子量，Mw是重均分子量。
                       常规分析详述
用粒度排阻色谱法(SEC，GPC)以聚苯乙烯为校准标准在四氢呋喃(THF)溶剂中测定分子量。残留交酯单体含量及总己内酯含量用300MHz处的1H-NMR分析测定。物理性能用实验室微系统测试仪以9.1kg满刻度载荷范围和5.1cm/分钟的十字头速度测定。所报告的值是至少5次测定的平均值。薄膜样品(0.025-0.050mm厚)用压缩模塑法制备，温度为150-180℃，压力为6.9-34.5Mpa，取决于各个聚合物样品的流动特性。
                       实例1
含14％己内酯4-臂星形嵌段聚交酯的合成
在氩气保护下往充分干燥的HeliconeC2V混合器(大西洋研究公司制造)中加入7g聚己内酯四醇(tetrol)(得自联合碳化物公司，批号#17360-10，Mn 7240)、41.3g  L-丙交酯和1.7g D、L-丙交酯，并保持在164℃。搅拌10分钟后通过注射器加入0.657ml 0.45M的La(2，2，6，6-四甲基-庚烷-3，5-二酮酸盐)3·双(乙氧基乙基醚)催化剂溶液(得自Unocal的140 Solvent 66/3，以下称为AMSCO140)。经15分钟后，将淡黄色粘稠聚合物熔体排入水中骤冷。由1H-NMR测定的交酯转化率及己内酯含量分别为92.4和11％，Tg为27℃。Mn为40,000，Mw/Mn为1.4。对压缩模塑薄膜测定的抗张强度、伸长率(％)及模量(以下称为TEM)分别为103MPa、137％、448MPa。
                          实例2
含10％己内酯3-臂星形嵌段聚交酯的合成
在氩气保护下往充分干燥的HeliconeC2V混合器(大西洋研究公司制造)中加入5g聚己内酯三醇(得自联合碳化物公司，批号#16874-95，Mn5260)、43.2g L-丙交酯和1.8g D，L-丙交酯，并保持在164℃。搅拌10分钟后通过注射器加入0.687ml 0.45M的La(2，2，6，6-四甲基庚烷-3，5-二酮酸盐)3·双(乙氧基乙基醚)催化剂溶液(AMSCO 140)。经15分钟后，将淡黄色粘稠聚合物熔体排入水中骤冷。Tg为19℃。Mn为39,000，Mw/Mn为1.6。TEM＝3.5MPa、210％、82.7MPa。
                         实例3
含20％己内酯3-臂星形嵌段聚交酯的合成
在氩气保护下往充分干燥的HeliconeC2V混合器(大西洋研究公司制造)中加入10g聚己内酯三醇(得自联合碳化物公司，批号#16874-95，Mn5260)、38.4g L-丙交酯和1.6g D，L-丙交酯，并保持在167℃。搅拌10分钟后通过注射器加入0.615ml 0.45M的La(2，2，6，6-四甲基庚烷-3，5-二酮酸盐)3·双(乙氧基乙基醚)催化剂溶液(AMSCO 140)。经15分钟后，将淡黄色粘稠聚合物熔体排入水中骤冷。Tg为20℃。Mn为63,000，Mw/Mn为1.2。TEM＝3.5MPa、123％、110MPa。
                         实例4
含20％己内酯4-臂星形嵌段聚交酯的合成
在氩气保护下往充分干燥的HeliconeC2V混合器(大西洋研究公司制造)中加入10g聚己内酯三醇(得自联合碳化物公司，批号#17360-10，Mn7240)、43.2g L-丙交酯和1.8g D，L-丙交酯，并保持在161℃。搅拌10分钟后通过注射器加入0.615ml  0.45M的La(2，2，6，6-四甲基庚烷-3，5-二酮酸盐)3·双(乙氧基乙基醚)催化剂溶液(AMSCO 140)。经15分钟后，将淡黄色粘稠聚合物熔体排入水中骤冷。Tg为10℃。Mn为36,400，Mw/Mn为1.3。TEM＝11.7MPa、247％、303MPa。
                         实例5
玻璃转变与组成关系的研究
将聚己内酯四醇(tetrol)(#臂数＝4；得自联合碳化物公司，批号#17360-10，Mn7240)和不同量的丙交酯加入到置于充有氮气的手套箱中的经火焰干燥的派热克斯硬玻璃试管中，用橡胶隔膜盖住，并在140℃或166℃的蒸汽浴中加热。经过5分钟让熔融单体混合物达到温度后在强烈摇动下通过长针微注射器加入La(2，2，6，6-四甲基庚烷-3，5-二酮酸盐)3·双(乙氧基乙基醚)催化剂。当由高粘度证实聚合反应完成时，取出少量样品放入水中骤冷，然后干燥。在室温下将聚合物溶于二氯甲烷中，并快速搅拌倒入到5倍体积的甲醇中，以除去残留的交酯单体。组成和分析结果列于下表。
  四醇                    催化剂   反应温度    Mn     Tg样品  (g)    丙交酯％  CL1   (μL)      (℃)    (GPC)   (℃)1    2.8     7.2     25.6      74       140     36000    252    2.6     7.4     24.3      76       140     38100    233    2.4     7.6     20.4      78       140     42400    254    2.2     7.8     20.5      80       140     46200    285    2.0     8.0     19.7      82       140     45000    306    1.8     8.2     16.7      84       140     51500    347    1.6     8.4     14.7      86       140     54400    36由1H-NMR测定的己内酯重量％
                        实例6
含22％己内酯4-臂星形嵌段聚交酯的合成
在氩气保护下往充分干燥的HeliconeC2V混合器(大西洋研究公司制造)中加入11g聚己内酯四醇(tetrol)(得自联合碳化物公司，批号#17360-10，Mn7240)和39g L-丙交酯，并保持在167℃。搅拌10分钟后通过注射器加入0.615ml 0.45M的La(2，2，6，6-四甲基庚烷-3，5-二酮酸盐)3·双(乙氧基乙基醚)催化剂溶液(AMSCO140)。经15分钟后，将淡黄色粘稠聚合物熔体排入水中骤冷。由1H-NMR测得的交酯转化率和己内酯含量分别为95.1和22％，Tg＝18℃。Mn为34,200，Mw/Mn＝1.3。TEM＝13.1MPa、94％、351MPa。
                     实例7
含24％己内酯4-臂星形嵌段聚交酯的合成
在氩气保护下往充分干燥的HeliconeC2V混合器(大西洋研究公司制造)中加入12g聚己内酯四醇(tetrol)(得自联合碳化物公司，批号#17360-10，Mn7240)和38g L-丙交酯，并保持在163℃。搅拌10分钟后通过注射器加入0.615ml 0.45M的La(2，2，6，6-四甲基庚烷-3，5-二酮酸盐)3·双(乙氧基乙基醚)催化剂溶液(AMSCO140)。经15分钟后，将淡黄色粘稠聚合物熔体排入水中骤冷。由1H-NMR测得的交酯转化率和己内酯含量分别为92.8和25％，Tg＝16℃。Mn为32,200，Mw/Mn＝1.3。TEM＝9.7MPa、84％、214MPa。
                    实例8
含20％己内酯4-臂星形嵌段聚交酯的合成
在氩气保护下往充分干燥的HeliconeC2V混合器(大西洋研究公司制造)中加入10g聚己内酯四醇(tetrol)(得自联合碳化物公司，批号#17360-10，Mn7240)和40g L-丙交酯，并保持在167℃。搅拌15分钟后通过注射器加入0.615ml 0.45M的La(2，2，6，6-四甲基庚烷-3，5-二酮酸盐)3·双(乙氧基乙基醚)催化剂溶液(AMSCO140)。经15分钟后，将淡黄色粘稠聚合物熔体排入水中骤冷。由1H-NMR测得的交酯转化率和己内酯含量分别为94.8和21％，Tg＝23℃。Mn为38,300，Mw/Mn＝1.4。TEM＝14.5MPa、316％、503MPa。
                        实例9
含20％己内酯4-臂星形嵌段聚交酯的合成(辛酸锡催化剂)
将1g聚己内酯四醇(tetrol)(得自联合碳化物公司，批号#17360-10，Mn7240)和4g L-丙交酯加入到置于充有氮气的手套箱中的经火焰干燥的派热克斯硬玻璃试管中，用橡胶隔膜盖住，并在166℃的蒸汽浴中加热。经过5分钟让熔融单体混合物达到温度后在强烈摇动下通过长针微注射器加入37微升0.49M辛酸锡催化剂的甲苯溶液。当由高粘度证实聚合反应完成时，取出少量样品放入水中骤冷，然后干燥。由1H-NMR测得的交酯转化率和己内酯含量分别为94.3和17.8％，Tg＝25℃。Mn＝49,100，Mw/Mn＝1.2。

Claims (13)

1.一种主要由一个芯层、连接到所述芯层上的3至约20个聚己内酯内臂和连接到所述内臂上的聚交酯外臂构成的星形嵌段共聚物，其条件是：
所述聚交酯占所述共聚物重量的至少50％；
所述聚己内酯占所述共聚物重量的约10％-约50％；
所述聚己内酯和聚交酯在熔融加工时不结晶；和
所述交酯的玻璃化温度小于35℃。
2.按照权利要求1的星形嵌段共聚物，其中每个聚己内酯内臂的数均分子量为约800-约4000。
3.按照权利要求1的星形嵌段共聚物，其中聚己内酯占该星形嵌段共聚物重量的约15％-约30％。
4.按照权利要求2的星形嵌段共聚物，其中聚己内酯占该星形嵌段共聚物重量的约18％-约22％。
5.按照权利要求1的星形嵌段共聚物，其中每个聚交酯外臂的数均分子量为约1,000-约12,000。
6.按照权利要求5的星形嵌段共聚物，其中每个聚交酯外臂的数均分子量为约3,000或更高。
7.按照权利要求1的星形嵌段共聚物，其中聚交酯占该共聚物重量的至少70％。
8.按照权利要求1的星形嵌段共聚物，其中该星形嵌段共聚物具有3-10个臂。
9.按照权利要求8的星形嵌段共聚物，其中该星形嵌段共聚物具有3-6个臂。
10.按照权利要求9的星形嵌段共聚物，其中该星形嵌段共聚物具有4个臂。
11.按照权利要求4的星形嵌段共聚物，其中该星形嵌段共聚物具有4个臂。
12.按照权利要求1的星形嵌段共聚物，其中所述玻璃化温度是30℃或更低。
13.按照权利要求11的星形嵌段共聚物，其中所述玻璃化温度是30℃或更低。
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