CN108130620A - 医用材料用支撑纤维及其制备方法 - Google Patents

医用材料用支撑纤维及其制备方法 Download PDF

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CN108130620A
CN108130620A CN201711163724.8A CN201711163724A CN108130620A CN 108130620 A CN108130620 A CN 108130620A CN 201711163724 A CN201711163724 A CN 201711163724A CN 108130620 A CN108130620 A CN 108130620A
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medical material
mass ratio
fibre
olefin
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彭代信
宋晓静
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SUZHOU YIKETAI ELECTRONIC MATERIAL CO Ltd
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Abstract

本发明公开了一种医用材料用支撑纤维及其制备方法，采用丝素纤维作为医用材料的表面，其具有优异的生物相容性，可用于伤口处理、组织包扎，同时利用合成纤维作为支撑材料，克服了丝素纤维力学强度差的缺陷，通过胶黏剂将丝素纤维与支撑纤维结合，成为稳定的整体，同时胶黏剂成膜后还具有阻隔作用，一方面防止丝素纤维被污染，另外防止组织液、血液等渗透。本发明的医用材料VOC小于0.5g/L；附着力为1级；24小时杀菌率(大肠杆菌)为99％以上；耐磨达1万次以上；断裂强度超过60MPa。

Description

医用材料用支撑纤维及其制备方法
本发明属于专利申请号为201610495789.1，专利申请日为2016年6月21日，专利名称为医用材料的分案申请，属于产品的制备方法部分技术方案。
技术领域
本发明属于高分子技术领域，具体涉及一种医用材料用支撑纤维及其制备方法。
背景技术
高分子纤维的制备一般包括原料改性得到改性物，再进行纺丝；或者改性物再与其他添加剂混合后再进行纺丝。现有的医用材料一般为棉纤维，因为其生物相容性较好；但是棉纤维都为短纤，力学性能较差，而且耐磨性低。烯烃纤维产量较大，成本很低，但是由于其惰性强、生物相容性差，而无法用作医用材料。因此需要对其改性，利用新的技术，在烯烃基础上制备出生物相容性好、耐磨性强、成本低的复合纤维产品作为医用材料。
发明内容
本发明的目的是提供一种医用材料，具有优异的生物相容性。
为达到上述发明目的，本发明采用的技术方案是：
一种医用材料，由以下方式制备得到：
(1)将聚乙烯、聚丙烯、次甲基丁二酸和环氧预聚体混合均匀，经螺杆熔融挤出加工，制备得到烯烃粒子；然后将烯烃粒子与二甲基氧化锡、2-丙烯酰胺基-2-甲基丙磺酸、叔丁基锂、异构十三醇聚氧乙烯醚混合均匀，得到烯烃组合物，再经熔融纺丝得到烯烃纤维；将聚四氟乙烯粒子与五水合硝酸铋、十二水磷酸氢二钠、聚脲甲醛、丙烯酰胺、碳酸钾混合后采用熔融纺丝法，制备得到聚四氟乙烯纤维；将烯烃纤维、聚四氟乙烯纤维按照4∶1的质量比进行混纺，得到支撑纤维；
将双酚A型氰酸酯单体加入到反应器中，90～95℃反应10～12分钟，加入三缩水甘油基三聚异氰酸酯单体，升温至120～125℃，加入壬基酚聚氧乙烯醚与α-蒎烯，反应30～35分钟制备环氧预聚体；
(2)蚕丝脱胶后溶解在混合液中，1～1.5小时后红外干燥得到膜；然后将膜置入碳酸氢钠水溶液中，20～30分钟后再置入清水中，透析1小时得到丝素蛋白溶液；调整丝素蛋白溶液的质量浓度为35～40％；然后加入壬基酚聚氧乙烯醚、四乙氧基硅烷以及丙烯酸丁酯，搅拌40～55分钟；然后加入壳聚糖，搅拌10分钟得到纺丝液，再经过静电纺得到蚕丝纤维；所述混合液由甲酸、水、溴化锂以及三羟甲基氨基甲烷缓冲液组成；
(3)将透明质酸加入4-(2-羟乙基)-1-哌嗪乙烷磺酸半钠盐缓冲液中，搅拌15～25分钟后加入聚乙二醇以及改性纳米贝壳粉，搅拌35～55分钟后加入三氟甲磺酸镧和咪唑，于80℃搅拌1小时，得到胶黏剂；
所述改性纳米贝壳粉由以下方式制备得到：将生贝壳粉与二氧化钛混合均匀后在700℃烧结45～55分钟，然后粉碎成平均粒径为40纳米的粉末；将粉末放入容器中，加入粉末重量10倍的乙醇以及粉末重量0.6％的端羟基聚硅氧烷，搅拌35～45分钟，然后加入粉末重量0.4％的对羟基苯甲酸甲酯，搅拌55～65分钟，最后干燥即得到改性纳米贝壳粉；
(4)将胶黏剂涂覆于支撑纤维表面，70℃加热5～8分钟；然后与蚕丝纤维复合，热压得到复合纤维，最后将复合纤维进行灭菌处理得到医用材料；所述胶黏剂位于支撑纤维与蚕丝纤维之间；所述热压的压力为0.1MPa，温度为85℃，时间为18～22分钟。
上述技术方案中，步骤(1)中，螺杆熔融挤出加工的反应挤出温度为180～200℃，螺杆转速控制为110～115转/分，物料在螺杆内的停留时间为5～6分钟；熔融纺丝得到烯烃纤维时温度为210～220℃，纺丝速度为800～900米/分；熔融纺丝得到聚四氟乙烯纤维时温度为315～330℃，纺丝速度为600～700米/分；聚乙烯、聚丙烯、次甲基丁二酸和环氧预聚体的质量比为1∶0.6∶0.32∶0.22；烯烃粒子与二甲基氧化锡、2-丙烯酰胺基-2-甲基丙磺酸、叔丁基锂、异构十三醇聚氧乙烯醚的质量比为1∶0.002∶0.2∶0.005∶0.15；聚四氟乙烯粒子与五水合硝酸铋、十二水磷酸氢二钠、聚脲甲醛、丙烯酰胺、碳酸钾的质量比为1∶0.08∶0.12∶0.18∶0.22∶0.11；双酚A型氰酸酯单体、三缩水甘油基三聚异氰酸酯单体、壬基酚聚氧乙烯醚与α-蒎烯的质量比为1∶1.6∶0.3∶0.1。
上述技术方案中，步骤(2)中，所述静电纺的工艺参数为：电压15～25千伏，接收距离8～12厘米，溶液流量为0.3～0.4mL/h；碳酸氢钠水溶液的质量浓度为8％；丝素蛋白、壬基酚聚氧乙烯醚、四乙氧基硅烷、丙烯酸丁酯、壳聚糖的质量比为1∶0.4∶0.3∶0.1∶0.3；甲酸、水、溴化锂以及三羟甲基氨基甲烷缓冲液的质量比为1∶5∶0.6∶2。
上述技术方案中，步骤(3)中，生贝壳粉与二氧化钛的质量比为5∶2；端羟基聚硅氧烷的分子量为900～1100；透明质酸、4-(2-羟乙基)-1-哌嗪乙烷磺酸半钠盐缓冲液、聚乙二醇、改性纳米贝壳粉、三氟甲磺酸镧、咪唑的质量比为1∶5∶0.6∶0.01∶0.005∶0.1。本发明的端羟基聚硅氧烷为线性结构，两端含有羟基，具有高的粘接性能，用以对无机材料的表面处理，可以增强无机物与其余有机成分的相容性；本发明对聚硅氧烷的分子量有要求，分子量过低会影响胶黏剂的粘接特性，过高则影响改性贝壳粉的分散均匀性。本发明采用丝素纤维作为医用材料的表面，其具有优异的生物相容性，可用于伤口处理、组织包扎，同时利用合成纤维作为支撑材料，克服了丝素纤维力学强度差的缺陷，通过胶黏剂将丝素纤维与支撑纤维结合，成为稳定的整体，同时胶黏剂成膜后还具有阻隔作用，一方面防止丝素纤维被污染，另外防止组织液、血液等渗透。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
(1)本发明采用以聚乙烯、聚丙烯为主要原料，通过添加合理的材料，熔融纺丝得到烯烃纤维，解决了现有烯烃纤维加工性较差、力学强度低的问题，特别是改性后的烯烃纤维具有一定的生物相容性，而且添加剂对人体或者动物体无害，克服了现有聚乙烯或者聚丙烯改性粒子存在的添加剂泄露致毒问题；环氧预聚体造粒，改善了烯烃聚合物的分子链刚度，提高其力学性能以及耐热性，利用次甲基丁二酸可以增加烯烃与环氧预聚体的相容性，提整个聚合物的稳定性；再利用小分子改性剂在熔纺时对烯烃改性，可以在不降低烯烃力学性能的基础上提高其生物相容性以及耐老化性。
(2)本发明利用聚四氟乙烯纤维极大的提高了医用材料的耐磨性，同时在熔纺过程中利用添加成分一方面在聚四氟乙烯纤维表面形成微孔，一方面增加了其表面活性，解决了现有聚四氟乙烯纤维惰性强、无法与其他纤维相容的问题，胶黏剂可以渗透进入微孔，提高了丝素纤维与支撑纤维的结合力，增加了医用材料的稳定性与受力平衡性。
(3)本发明的医用材料通过合理的设计，功能面具有优异的生物相容性，辅助面具有良好的力学性能以及耐磨性；而且制备方便，通过熔纺、静电纺设备，即可容易制备；利于工业化应用。
具体实施方式
下面结合实施例对本发明作进一步描述：
实施例一 一种医用材料，由以下方式制备得到：
(1)将质量比为1∶0.6∶0.32∶0.22的聚乙烯、聚丙烯、次甲基丁二酸和环氧预聚体混合均匀，经螺杆熔融挤出得到烯烃粒子；然后将质量比为1∶0.002∶0.2∶0.005∶0.15的烯烃粒子、二甲基氧化锡、2-丙烯酰胺基-2-甲基丙磺酸、叔丁基锂、异构十三醇聚氧乙烯醚混合均匀，得到烯烃组合物，再经熔融纺丝得到烯烃纤维；将质量比为1∶0.08∶0.12∶0.18∶0.22∶0.11的聚四氟乙烯粒子、五水合硝酸铋、十二水磷酸氢二钠、聚脲甲醛、丙烯酰胺、碳酸钾混合后采用熔融纺丝法，制备得到聚四氟乙烯纤维；将烯烃纤维、聚四氟乙烯纤维按照4∶1的质量比进行混纺，得到支撑纤维；将双酚A型氰酸酯单体加入到反应器中，95℃反应10分钟，加入三缩水甘油基三聚异氰酸酯单体，升温至125℃，加入壬基酚聚氧乙烯醚与α-蒎烯，反应30分钟制备环氧预聚体；双酚A型氰酸酯单体、三缩水甘油基三聚异氰酸酯单体、壬基酚聚氧乙烯醚与α-蒎烯的质量比为1∶1.6∶0.3∶0.1；上述螺杆熔融挤出加工的反应挤出温度为180～200℃，螺杆转速控制为110转/分，物料在螺杆内的停留时间为6分钟；熔融纺丝得到烯烃纤维时温度为210～220℃，纺丝速度为800米/分；熔融纺丝得到聚四氟乙烯纤维时温度为315～330℃，纺丝速度为700米/分；
(2)蚕丝脱胶后溶解在混合液中，1小时后红外干燥得到膜；然后将膜置入质量浓度为8％的碳酸氢钠水溶液中，30分钟后再置入清水中，透析1小时得到丝素蛋白溶液；调整丝素蛋白溶液的质量浓度为35％；然后加入壬基酚聚氧乙烯醚、四乙氧基硅烷以及丙烯酸丁酯，搅拌55分钟；然后加入壳聚糖，搅拌10分钟得到纺丝液，再经过静电纺得到蚕丝纤维；所述混合液由质量比为1∶5∶0.6∶2的甲酸、水、溴化锂以及三羟甲基氨基甲烷缓冲液组成；丝素蛋白、壬基酚聚氧乙烯醚、四乙氧基硅烷、丙烯酸丁酯、壳聚糖的质量比为1∶0.4∶0.3∶0.1∶0.3；上述静电纺的工艺参数为：电压15千伏，接收距离12厘米，溶液流量为0.3mL/h；
(3)将透明质酸加入4-(2-羟乙基)-1-哌嗪乙烷磺酸半钠盐缓冲液中，搅拌15分钟后加入聚乙二醇以及改性纳米贝壳粉，搅拌～55分钟后加入三氟甲磺酸镧和咪唑，于80℃搅拌1小时，得到胶黏剂；透明质酸、4-(2-羟乙基)-1-哌嗪乙烷磺酸半钠盐缓冲液、聚乙二醇、改性纳米贝壳粉、三氟甲磺酸镧、咪唑的质量比为1∶5∶0.6∶0.01∶0.005∶0.1；
将质量比为5∶2的生贝壳粉与二氧化钛混合均匀后在700℃烧结55分钟，然后粉碎成平均粒径为40纳米的粉末；将粉末放入容器中，加入粉末重量10倍的乙醇以及粉末重量0.6％的端羟基聚硅氧烷，搅拌35分钟，然后加入粉末重量0.4％的对羟基苯甲酸甲酯，搅拌65分钟，最后干燥即得到改性纳米贝壳粉；端羟基聚硅氧烷的分子量为900～1100；
(4)将胶黏剂涂覆于支撑纤维表面，70℃加热8分钟；然后与蚕丝纤维复合，热压得到复合纤维，灭菌处理得到医用材料；所述胶黏剂位于支撑纤维与蚕丝纤维之间；所述热压压力0.1MPa，温度85℃，时间18分钟。
实施例二 一种医用材料，由以下方式制备得到：
(1)将质量比为1∶0.6∶0.32∶0.22的聚乙烯、聚丙烯、次甲基丁二酸和环氧预聚体混合均匀，经螺杆熔融挤出加工，制备得到烯烃粒子；然后将质量比为1∶0.002∶0.2∶0.005∶0.15的烯烃粒子、二甲基氧化锡、2-丙烯酰胺基-2-甲基丙磺酸、叔丁基锂、异构十三醇聚氧乙烯醚混合均匀，得到烯烃组合物，再经熔融纺丝得到烯烃纤维；将质量比为1∶0.08∶0.12∶0.18∶0.22∶0.11的聚四氟乙烯粒子、五水合硝酸铋、十二水磷酸氢二钠、聚脲甲醛、丙烯酰胺、碳酸钾混合后采用熔融纺丝法，制备得到聚四氟乙烯纤维；将烯烃纤维、聚四氟乙烯纤维按照4∶1的质量比进行混纺，得到支撑纤维；将双酚A型氰酸酯单体加入到反应器中，90℃反应12分钟，加入三缩水甘油基三聚异氰酸酯单体，升温至120℃，加入壬基酚聚氧乙烯醚与α-蒎烯，反应30分钟制备环氧预聚体；双酚A型氰酸酯单体、三缩水甘油基三聚异氰酸酯单体、壬基酚聚氧乙烯醚与α-蒎烯的质量比为1∶1.6∶0.3∶0.1；上述螺杆熔融挤出加工的反应挤出温度为180～200℃，螺杆转速控制为115转/分，物料在螺杆内的停留时间为6分钟；熔融纺丝得到烯烃纤维时温度为210～220℃，纺丝速度为800米/分；熔融纺丝得到聚四氟乙烯纤维时温度为315～330℃，纺丝速度为600米/分；
(2)蚕丝脱胶后溶解在混合液中，1小时后红外干燥得到膜；然后将膜置入质量浓度为8％的碳酸氢钠水溶液中，30分钟后再置入清水中，透析1小时得到丝素蛋白溶液；调整丝素蛋白溶液的质量浓度为40％；然后加入壬基酚聚氧乙烯醚、四乙氧基硅烷以及丙烯酸丁酯，搅拌40分钟；然后加入壳聚糖，搅拌10分钟得到纺丝液，再经过静电纺得到蚕丝纤维；所述混合液由质量比为1∶5∶0.6∶2的甲酸、水、溴化锂以及三羟甲基氨基甲烷缓冲液组成；丝素蛋白、壬基酚聚氧乙烯醚、四乙氧基硅烷、丙烯酸丁酯、壳聚糖的质量比为1∶0.4∶0.3∶0.1∶0.3；上述静电纺的工艺参数为：电压25千伏，接收距离8厘米，溶液流量为0.4mL/h；
(3)将透明质酸加入4-(2-羟乙基)-1-哌嗪乙烷磺酸半钠盐缓冲液中，搅拌15分后加入聚乙二醇以及改性纳米贝壳粉，搅拌55分钟后加入三氟甲磺酸镧和咪唑，80℃搅拌1小时得到胶黏剂；透明质酸、4-(2-羟乙基)-1-哌嗪乙烷磺酸半钠盐缓冲液、聚乙二醇、改性纳米贝壳粉、三氟甲磺酸镧、咪唑的质量比为1∶5∶0.6∶0.01∶0.005∶0.1；将质量比为5∶2的生贝壳粉与二氧化钛混合后在700℃烧结55分钟，然后粉碎成平均粒径为40纳米的粉末；将粉末放入容器中，加入粉末重量10倍的乙醇以及粉末重量0.6％的端羟基聚硅氧烷，分子量为900～1100，搅拌35分，然后加入粉末重量0.4％的对羟基苯甲酸甲酯，搅拌65分钟，干燥得到改性纳米贝壳粉；
(4)将胶黏剂涂覆于支撑纤维表面，70℃加热8分钟；然后与蚕丝纤维复合，热压得到复合纤维，灭菌处理得到医用材料；所述热压的压力为0.1MPa，温度为85℃，时间为18分钟。
上述医用材料VOC小于0.5g/L；附着力为1级；24小时杀菌率(大肠杆菌)为99％以上；耐磨达1万次以上；断裂强度超过60MPa。

Claims (4)

1.一种医用材料用支撑纤维的制备方法，包括以下步骤：
将聚乙烯、聚丙烯、次甲基丁二酸和环氧预聚体混合均匀，经螺杆熔融挤出加工，制备得到烯烃粒子；然后将烯烃粒子与二甲基氧化锡、2-丙烯酰胺基-2-甲基丙磺酸、叔丁基锂、异构十三醇聚氧乙烯醚混合均匀，得到烯烃组合物，再经熔融纺丝得到烯烃纤维；将聚四氟乙烯粒子与五水合硝酸铋、十二水磷酸氢二钠、聚脲甲醛、丙烯酰胺、碳酸钾混合后采用熔融纺丝法，制备得到聚四氟乙烯纤维；将烯烃纤维、聚四氟乙烯纤维按照4∶1的质量比进行混纺，得到支撑纤维；
将双酚A型氰酸酯单体加入到反应器中，90～95℃反应10～12分钟，加入三缩水甘油基三聚异氰酸酯单体，升温至120～125℃，加入壬基酚聚氧乙烯醚与α-蒎烯，反应30～35分钟制备环氧预聚体。
2.根据权利要求1所述医用材料用支撑纤维的制备方法，其特征在于：螺杆熔融挤出加工的反应挤出温度为180～200℃，螺杆转速控制为110～115转/分，物料在螺杆内的停留时间为5～6分钟；熔融纺丝得到烯烃纤维时温度为210～220℃，纺丝速度为800～900米/分；熔融纺丝得到聚四氟乙烯纤维时温度为315～330℃，纺丝速度为600～700米/分。
3.根据权利要求1所述医用材料用支撑纤维的制备方法，其特征在于：聚乙烯、聚丙烯、次甲基丁二酸和环氧预聚体的质量比为1∶0.6∶0.32∶0.22；烯烃粒子与二甲基氧化锡、2-丙烯酰胺基-2-甲基丙磺酸、叔丁基锂、异构十三醇聚氧乙烯醚的质量比为1∶0.002∶0.2∶0.005∶0.15；聚四氟乙烯粒子与五水合硝酸铋、十二水磷酸氢二钠、聚脲甲醛、丙烯酰胺、碳酸钾的质量比为1∶0.08∶0.12∶0.18∶0.22∶0.11；双酚A型氰酸酯单体、三缩水甘油基三聚异氰酸酯单体、壬基酚聚氧乙烯醚与α-蒎烯的质量比为1∶1.6∶0.3∶0.1。
4.根据权利要求1所述医用材料用支撑纤维的制备方法制备的医用材料用支撑纤维。
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