CN1051717C - 聚氨酯矫形绷带材料 - Google Patents

聚氨酯矫形绷带材料 Download PDF

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CN1051717C
CN1051717C CN92108533A CN92108533A CN1051717C CN 1051717 C CN1051717 C CN 1051717C CN 92108533 A CN92108533 A CN 92108533A CN 92108533 A CN92108533 A CN 92108533A CN 1051717 C CN1051717 C CN 1051717C
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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Abstract

本发明公开了一种新的、不同以往的，用作骨科外固定的水固化型聚氨酯矫形绷带材料及其制备方法，主要成分聚氨酯预聚体中的稳定剂是马来酐，以及混合催化剂是α－(吗啉代乙氧基－乙氧基)－β－吗啉代乙烷和无水碳酸钾。由于，含有共轭双键的马来酐能吸附予聚体中微量水份和水溶性碱性水合物并与异氰酸根生成的凝胶基团反应后呈酸性的马来酸衍生物，从而阻止了矫形绷带材料在使用之前即贮存期间的早期固化现象。

Description

聚氨酯矫形绷带材料
本发明是涉及医用材料领域，尤其是一种不同以往的用作骨科外固定的水固化聚氨酯矫形绷带材料及其制备方法。
近年来，美国专利4376438首先提出在织物上浸渍水固定型聚氨酯预聚体制成绷带材料以取代骨折治疗中的石膏绷带，这种绷带使用方法与石膏绷带相同，浸水后，即在病人肢体上包扎，水能使预聚体发生聚合即对病人起固化定形作用，由于，该绷带材料具有重量轻，强度大，透气性好，能抗水，X线能透过，使用方便等优点已被世界各国医疗卫生部门广泛应用，为了使绷带得到临床使用所要求在15分钟内迅速固化，必须在聚氨酯预聚体中掺入适当的催化剂，由于在预聚体中的催化剂存在以及绷带制备和包装过程中带入微量水份，导致绷带在使用之前，即贮存期间聚氨酯预聚体发生凝胶的付反应，而使绷带过早地固化以致不能使用。
为了阻止绷带材料早期固化现象，提高绷带的贮存稳定性，美国专利4433680和4655208，中国专利89103603.2提出在聚氨酯预聚体中掺入苯甲酰氯作为稳定剂，但是，苯甲酰氯是一种腐蚀性很大，又极易分解液体，即使加入量很少，也会使绷带材料带有刺激性气味，作为医用材料难以被医务人员接受。
美国专利4574793，中国专利90102934.3，提出在聚氨酯预聚体中加入少量甲基磺酸作为稳定剂，然而，甲基磺酸是一种强酸，在制备聚氨酯预聚体过程中，一旦混入即迅速与聚醚中的OH基团结合，而降低预聚体的稳定性。
PCT/GB8700716(WO88/02636)提出有机酸酐作为稳定剂，在制备聚氨酯预聚体过程中加入能起稳定作用，但是，丁二酸酐是以磨成＜75μm细颗粒固体形式掺入预聚体中，由于，不能完全充分混和而影响了预聚体的稳定效果。
本发明的目的旨在提供一种稳定性好，使用性能可靠的聚氨酯矫形绷带材料及其制备方法。本发明的技术方案提出含有共轭双键的马来酐能吸附在预聚体中的微量水份和水溶性的碱性基团，并与预聚体甲少量异氰酸根生成的凝胶基团相互反应后呈酸性的马来酸衍生物，预聚体材料在这样的酸性环境中，有效地阻止了矫形绷带材料之前，既贮存期间的早期固化现象，由于，马来酐能溶于丙酮、氯仿、乙醚等有机溶剂中，聚氨酯预聚体制备中，马来酐以溶液形式均匀分散在预聚体中，充分地显示对预聚体的稳定作用，克服了其它稳定剂存在的缺点，显著地提高了矫形绷带的贮存稳定性。马来酐稳定剂的含量基重量百分比浓度为0.1-5.0％，推荐的含量为0.5-2.0％。本发明所用的混合催化剂包括液相和固相二部分，其中液相催化剂是由二氯二乙氧基乙烷与吗啉合成制取的一种新的双吗啉结构化合物，即α-(吗啉代乙氧基--乙氧基)-β-吗啉代乙烷，合成反应式如下：
Figure C9210853300051
+2HCL
分子式：C14H28N2O4
分子量：288
沸  程：145-150℃/1-2mHG
性  能：无色、无味、无毒、不挥发的透明粘稠液体，易溶于水和苯、甲苯、丙酮、氯仿、乙酸乙酯、乙醚等有机溶剂。
采用这一种双吗啉结构化合物作为聚氨酯预聚体的催化剂，由此引起的付反应形成速率较以往所用其它叔胺类催化剂要低得多，在确保临床所需固化时间的前提下，绷带的贮存稳定性有明显的提高，其含量其重量百分比浓度为0.1-10.0％，推荐含量为0.5-2.0％。
其中固相催化剂是无水碳酸钾，并磨成小于100μm微细颗粒分散聚酯预聚体中。由于，该化合物不溶于聚氨酯预聚体，使用前在预聚体中十分稳定，使用时，绷带一旦遇水，碳酸钾立即溶于水中成为碱性催化溶液，使绷带迅速固化。无水碳酸钾的含量其重量百分比浓度为1-10％，推荐含量为4-6％。
本发明的聚氨酯预聚体中的芳香族异氰酸酯可以是聚氨酯化学中阐述的确任何一种芳香族异氰酸酯，例如Interscience出版社，1962年出版的《聚氨酯化学和工艺学》一书中阐述的化合物。
芳香族异氰酸酯包括甲苯二异氰酸酯(TDI)，二苯基甲烷二异氰酸酯(MDI)或含碳二亚胺基团的改性的二苯基甲烷二异氰酸酯，即液体MDI。既：
Figure C9210853300061
其中R是
Figure C9210853300062
本发明中的聚氨酯预聚体中的多羟基化合物为二羟基聚醚或二羟基聚醚与三羟基聚醚的混合物，其分子量从500至1500。聚氨酯预聚体中的NCO∶OH为3∶1至9∶1，含量在10～15％。
本发明所涉及的聚氨酯矫形绷带的制备方法是在一严格控制的低湿度干燥N2环境中，系统中含水量小于100PPm，在适当温度下，定量的聚氨酯预聚体涂复在基材上。
矫形绷带的贮存期是反映聚氨酯预聚体稳定性的重要指标，它的稳定性通常依赖于其化学反应结构和链的离解能，由于，聚氨酯预聚体不是单一的均聚物，所以，提高贮存温度实际上是提高链的离解能，促进热反应加速固化，热老化快速实验方法是评论聚氨酯材料的稳定性，使用期和贮存期的有效评定方法，但是，至今国际上尚未有一个统一的标准实验方法，所以实验温度和条件相差甚大，通常选择实验温度比实际工作温度高出20～40℃，本发明的聚氨酯绷带热老化实验温度选在40℃，在这一温度条件下存放124天不固化，相当于室温20℃中，可贮存二年。
下面给出本发明的实施例：一、聚氨酯预聚体的制备：
配方：
二羟基聚醚Pluracol 710，OH＝150，                 6410克
液体MDI Lupranate MM-103，                     3580克
NCO∶OH＝4.2∶1                                20克
消泡硅油
马来酐                                         100克
α-(吗啉代乙氧基-乙氧基)-β-吗啉代乙烷         80克
无水碳酸钾                                     500克
在分别装有温度计，搅拌器，加液器和N2进口的10立升反应器中，按配方先加入二羟聚醚，和马来酐丙酮溶液预混均匀，然后加热升温至55℃，在30分钟内滴加液体MDI，控制温度在60℃，反应1.5小时后，加入混合催化剂α-(吗啉代乙氧基-乙氧基)-β-吗啉代乙烷和＜100μm的无水碳酸钾，充分搅拌混和10分钟，冷却40℃，在N2保护下出料放入容器内待用，预聚体的特征粘度50℃时为2500厘泊，NCO含量13.9％。二、聚氨酯矫形绷带的制备：
取5000克上述制备的聚氨酯预聚体加热至50℃，在含水量50PPm低湿度干燥N2环境下，采用双辊筒涂复法，将预聚体涂复在网眼基材上，每卷4英寸宽，3.6米长，涂复量18克/米，透气率：8层绷带：510公升/公尺/秒，压缩强度：Instron1122型实验机，实验机速度：100mm/min，8层绷带：160N，固化时间为8分钟，绷带放入40℃条件下加速热老化实验，贮存192天仍未固化，相当于在室温20℃中，可贮存二年以上。

Claims (4)

1、一种用作骨科外固定的水固化型聚氨酯矫形绷带材料，其特征在于主要成份聚氨酯预聚体中包含：(1)含有共轭双键的马来酐，重量百分比浓度为0.1-5.0％，马来酐的化学结构式为：
Figure C9210853300021
(2)由α-(吗啉代乙氧基--乙氧基)β-吗啉代乙烷，重量百分比浓度为0.1-10.0％，和无水碳酸钾重量百分比浓度为1.0-10.0％组成的混合催化剂。α-(吗啉代乙氧基-乙氧基)-β-吗啉代乙烷的化学结构式为：(3)芳香族异氰酸酯(4)多羟基化合物
2、根据权利要求1所述的聚氨酯矫形绷带材料，其特征在于无水碳酸钾以小于100μm的固体微小颗粒形式渗和在聚氨酯预聚体中。
3、根据权利要求1所述的聚氨酯矫形绷带材料，其特征在于芳香族异氰酸酯是含碳化二亚胺改性的二苯基甲烷二异氰酸酯，即液体MDI。
其化学结构式为：
Figure C9210853300023
其中R是
Figure C9210853300031
4、根据权利要求1所述的聚氨酯矫形绷带材料，其特征在于多羟基化合物为二羟基聚醚或二羟基聚醚与三羟基聚醚混合物组成。NCO∶OH之当量比为3∶1至9∶1
CN92108533A 1992-08-14 1992-08-14 聚氨酯矫形绷带材料 Expired - Fee Related CN1051717C (zh)

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CN92108533A CN1051717C (zh) 1992-08-14 1992-08-14 聚氨酯矫形绷带材料
US08/106,337 US5455294A (en) 1992-08-14 1993-08-13 Polyurethane orthopedic cast material and the method of its preparation
JP5201507A JPH08154966A (ja) 1992-08-14 1993-08-13 ポリウレタン整形用包帯材料およびその調製方法
FR9310101A FR2694695B1 (fr) 1992-08-14 1993-08-13 Matière de bandage orthopédique en polyuréthane et son procédé de préparation.
DE4327498A DE4327498A1 (de) 1992-08-14 1993-08-16 Orthopädisches Polyurethan-Verbandsmaterial und sein Herstellungsverfahren

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US5455294A (en) 1995-10-03
FR2694695B1 (fr) 1995-04-14
DE4327498A1 (de) 1994-02-24
CN1073881A (zh) 1993-07-07
JPH08154966A (ja) 1996-06-18

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