CN105821519A - 一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法 - Google Patents

一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法 Download PDF

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CN105821519A
CN105821519A CN201610328096.3A CN201610328096A CN105821519A CN 105821519 A CN105821519 A CN 105821519A CN 201610328096 A CN201610328096 A CN 201610328096A CN 105821519 A CN105821519 A CN 105821519A
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陈意
常金明
范浩军
刘世勇
官小玉
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Sichuan University
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Abstract

本发明涉及一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法。先将明胶水溶液与封闭型水性聚氨酯乳液混合均匀，制得纺丝液；再通过干法或湿法纺丝技术将该纺丝液纺成明胶/封闭型水性聚氨酯复合纤维；在后续干燥过程中，封闭型水性聚氨酯解封闭，解封闭的异氰酸酯基团与明胶中的活性基团进一步反应，起到原位交联、大幅提升复合纤维力学性能的作用。由于水性聚氨酯与明胶的相容性好，复合纤维中明胶组分的添加量大，明胶自身的优异性能得到了充分体现；此外，水性聚氨酯无毒，对明胶交联改性后不会影响复合纤维的生物相容性；最后，本发明涉及的水性聚氨酯与明胶间存在共价反应，可大幅、持久地提升复合纤维的力学性能，在生物医用、组织工程、纺织服装等领域具有应用前景。

Description

一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法
技术领域
本发明涉及一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，属于纤维制造领域。
背景技术
明胶是一种从动物的结缔或表皮组织中的胶原部分水解出来的蛋白质，具有很好的生物相容性，在医药、生物材料领域具有广泛的应用。与胶原相比，明胶来源广泛、价格低廉、制备简单，更为重要的是，明胶在热水中具有较高的溶解度，形成的溶液可纺性强，具有制备成纤维在多种领域中应用的潜力。然而，明胶的力学强度低，通常需要交联改性，以提升其力学性能（应用性能）。一般情况下，明胶可采用小分子交联剂（如金属离子、甲醛、戊二醛等）交联改性，但存在小分子交联剂反应不完全，残留物（毒性较大）影响明胶制品生物相容性的缺陷。此外，也可以把明胶与其他大分子材料（如聚乙烯醇、纤维素等）共混以改善其力学性能，但这些大分子材料中明胶的添加量一般较少，并没有充分体现明胶材料自身的优良性能；此外，这些大分子材料与明胶间相互作用力低，在后续使用过程中（尤其是在溶液中），可能存在明胶持续溶解的问题。
发明内容
在本发明的目的是针对现有技术的不足而提供一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法。
本发明的目的由以下技术措施实现，其中所述的原料份数除特别说明外，均为重量份数。
（1）纺丝液的制备
将相对分子质量为1000-4000的聚二元醇100份加入带控温和分散装置的密封分散釜中，再依次加入二异氰酸酯35-70份、催化剂0-0.5份，于60℃-80℃反应1-3小时；再加入小分子扩链剂0.5-11份、交联剂0-5份，于60℃-80℃反应1-3小时；再加入亲水扩链剂5-16份，于60℃-80℃反应1-3小时；然后加入封闭剂6-14份反应3-5小时将多余异氰酸酯基团封闭；再降温至25℃-35℃，加入中和剂中和5-30分钟；最后加入去离子水高速搅拌乳化，制得固含量为20%-40%的封闭型水性聚氨酯乳液；
将上述封闭型水性聚氨酯乳液50-150份与100份固含量为15%-40%的明胶水溶液共混，制得纺丝液，将该纺丝液过滤、脱泡，备用；
（2）纺丝
所述纺丝方法为干法纺丝或湿法纺丝中的其中一种:
所述干法纺丝具体工艺为：将步骤（1）所得纺丝液送入计量泵，在一定压力下于80℃-90℃经喷丝头挤出，挤出的原液经过高为4-8米、热空气温度为100℃-120℃的纺丝甬道，使水分得以挥发，以一定速度导出后经拉伸1.3-3倍；
所述湿法纺丝具体工艺为：将步骤（1）所得纺丝液送入计量泵，在一定压力下于80℃-90℃经喷丝头挤出，挤出的原液细流经温度为25℃-35℃、浓度为15-35wt%的无机盐凝固浴固化；
（3）原位交联
将步骤（2）所得纤维于120℃-160℃热风干燥，封闭型异氰酸酯在高温下解封闭，解封闭的异氰酸酯基团会与明胶分子链上的氨基、羟基、羧基等发生反应，明胶纤维的物理机械性能和耐介质性能得到提升。
以上方法所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述聚二元醇为聚丙二醇、聚乙二醇、聚四氢呋喃二醇、聚碳酸酯二元醇、聚己内酯二元醇、聚己二酸乙醇酯二醇、聚己二酸新戊二醇-1,6-己二醇酯二醇、聚己二酸丁二醇酯二醇中的至少一种。
以上方法所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、氢化二苯基甲烷二异氰酸酯、异氟尔酮二异氰酸酯、六亚甲基二异氰酸酯中的至少一种。
以上方法所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述催化剂为有机铋催化剂、有机银催化剂中的至少一种。
以上方法所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述小分子扩链剂为乙二醇、1,4-丁二醇、丙二醇、1,4-环己基二甲醇、乙二胺中的至少一种。
以上方法所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述交联剂为三羟甲基丙烷、蓖麻油、丙三醇中的至少一种。
以上方法所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述亲水扩链剂为2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2-(2-氨基乙基)氨基乙磺酸钠盐、N-甲基二乙醇胺中的至少一种。
以上方法所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述封闭剂为甲乙酮肟、异羟肟酸酯、1,2,4-三唑、丁二酰亚胺、乙酰苯胺、丙二酸二乙酯、2-二苯基咪唑啉中的至少一种。
以上方法所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述中和剂为三乙胺、乙酸中的至少一种。
以上方法所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述无机盐为硫酸钠、硫酸铵、氢氧化钠中的至少一种。
本发明与现有技术相比，具有以下积极效果：
1.本专利采用封闭型水性聚氨酯对明胶进行原位交联改性，水性聚氨酯与明胶的相容性好，可以与大量的明胶组分共混形成均匀纺丝液，最后纺丝获得的复合纤维可充分体现明胶材料自身的优良性能；此外，水性聚氨酯无毒、环保，对明胶改性后不会影响产物的生物相容性。
2.本发明制备的水性聚氨酯中多余的异氰酸酯基团已被封闭，与明胶共混并纺丝后，在干燥过程中，封闭异氰酸酯基团解封闭，重新暴露的异氰酸酯基团可与明胶中的羟基、氨基、羧基等多种活性基团共价反应，对明胶起到了较普通物理共混更强的交联作用，可大幅、持久地提升明胶纤维的力学性能，获得的改性明胶纤维可制成手术缝合线、创伤敷料、止血纱布等生物医用材料，也可用于新型服装材料等，应用领域广泛。
具体实施方案
下面通过实施例对本发明进行具体描述。有必要在此指出的是本实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制。
实施例1
（1）纺丝液的制备
将100份相对分子质量为1000的聚己二酸丁二醇酯二醇加入带控温和分散装置的密封分散釜中，再依次加入4,4'-二环己基甲烷二异氰酸酯70份，于60℃反应3小时；再加入1,4-丁二醇0.5份，于80℃反应1小时；再加入2,2-二羟甲基丁酸16份，于60℃反应3小时；然后加入甲乙酮肟8份反应3小时将多余异氰酸酯基团封闭；再降温至35℃，加入三乙胺12份中和30分钟；最后加入去离子水高速搅拌乳化，制得固含量为40%的封闭型水性聚氨酯乳液；
将上述封闭型水性聚氨酯乳液50份与100份固含量为15%的明胶水溶液共混，制得纺丝液，将该纺丝液过滤、脱泡，备用；
（2）纺丝
干法纺丝具体工艺为：将步骤（1）所得纺丝液送入计量泵，在一定压力下于80℃经喷丝头挤出，挤出的原液经过高为8米、热空气温度为100℃的纺丝甬道，使水分得以挥发，以一定速度导出后经拉伸1.3倍；
（3）原位交联
将步骤（2）所得纤维于120℃热风干燥，封闭型异氰酸酯在高温下解封闭，解封闭的异氰酸酯基团会与明胶分子链上的氨基、羟基、羧基等发生反应，明胶纤维的物理机械性能和耐介质性能得到提升。
实施例2
将100份相对分子质量为2000的聚四氢呋喃二醇加入带控温和分散装置的密封分散釜中，再依次加入异佛尔酮二异氰酸酯50份、有机银催化剂0.3份，于70℃反应2小时；再加入乙二醇4份、三羟甲基丙烷1份，于75℃反应2小时；再加入N-甲基二乙醇胺7份，于75℃反应2.5小时；然后加入1,2,4-三唑6份反应4小时将多余异氰酸酯基团封闭；再降温至30℃，加入乙酸中和20分钟；最后加入去离子水高速搅拌乳化，制得固含量为30%的封闭型水性聚氨酯乳液；
将上述封闭型水性聚氨酯乳液100份与100份固含量为25%的明胶水溶液共混，制得纺丝液，将该纺丝液过滤、脱泡，备用；
（2）纺丝
10.湿法纺丝具体工艺为：将步骤（1）所得纺丝液送入计量泵，在一定压力下于85℃经喷丝头挤出，挤出的原液细流经温度为30℃、浓度为25wt%的无机盐凝固浴固化；
（3）原位交联
将步骤（2）所得纤维于140℃热风干燥，封闭型异氰酸酯在高温下解封闭，解封闭的异氰酸酯基团会与明胶分子链上的氨基、羟基、羧基等发生反应，明胶纤维的物理机械性能和耐介质性能得到提升。
实施例3
将100份相对分子质量为4000的聚己内酯二元醇加入带控温和分散装置的密封分散釜中，再依次加入六亚甲基二异氰酸酯35份、有机铋催化剂0.5份，于80℃反应1小时；再加入1,4-环己基二甲醇11份、蓖麻油5份，于60℃反应3小时；再加入2,2-二羟甲基丙酸5份，于80℃反应1小时；然后加入丙二酸二乙酯14份反应5小时将多余异氰酸酯基团封闭；再降温至25℃，加入三乙胺中和5分钟；最后加入去离子水高速搅拌乳化，制得固含量为20%的封闭型水性聚氨酯乳液；
将上述封闭型水性聚氨酯乳液150份与100份固含量为40%的明胶水溶液共混，制得纺丝液，将该纺丝液过滤、脱泡，备用；
（2）纺丝
干法纺丝具体工艺为：将步骤（1）所得纺丝液送入计量泵，在一定压力下于90℃经喷丝头挤出，挤出的原液经过高为4米、热空气温度为120℃的纺丝甬道，使水分得以挥发，以一定速度导出后经拉伸3倍；
（3）原位交联
将步骤（2）所得纤维于160℃热风干燥，封闭型异氰酸酯在高温下解封闭，解封闭的异氰酸酯基团会与明胶分子链上的氨基、羟基、羧基等发生反应，明胶纤维的物理机械性能和耐介质性能得到提升。

Claims (10)

1.一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于该方法包括以下步骤，其中所用原料以质量份数计：
（1）纺丝液的制备
将相对分子质量为1000-4000的聚二元醇100份加入带控温和分散装置的密封分散釜中，再依次加入二异氰酸酯35-70份、催化剂0-0.5份，于60℃-80℃反应1-3小时；再加入小分子扩链剂0.5-11份、交联剂0-5份，于60℃-80℃反应1-3小时；再加入亲水扩链剂5-16份，于60℃-80℃反应1-3小时；然后加入封闭剂6-14份反应3-5小时将多余异氰酸酯基团封闭；再降温至25℃-35℃，加入中和剂中和5-30分钟；最后加入去离子水高速搅拌乳化，制得固含量为20%-40%的封闭型水性聚氨酯乳液；
将上述封闭型水性聚氨酯乳液50-150份与100份固含量为15%-40%的明胶水溶液共混，制得纺丝液，将该纺丝液过滤、脱泡，备用；
（2）纺丝
所述纺丝方法为干法纺丝或湿法纺丝中的其中一种:
所述干法纺丝具体工艺为：将步骤（1）所得纺丝液送入计量泵，在一定压力下于80℃-90℃经喷丝头挤出，挤出的原液经过高为4-8米、热空气温度为100℃-120℃的纺丝甬道，使水分得以挥发，以一定速度导出后经拉伸1.3-3倍；
所述湿法纺丝具体工艺为：将步骤（1）所得纺丝液送入计量泵，在一定压力下于80℃-90℃经喷丝头挤出，挤出的原液细流经温度为25℃-35℃、浓度为15-35wt%的无机盐凝固浴固化；
（3）原位交联
将步骤（2）所得纤维于120℃-160℃热风干燥，封闭型异氰酸酯在高温下解封闭，解封闭的异氰酸酯基团会与明胶分子链上的氨基、羟基、羧基等发生反应，明胶纤维的物理机械性能和耐介质性能得到提升。
2.根据权利要求1所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述聚二元醇为聚丙二醇、聚乙二醇、聚四氢呋喃二醇、聚碳酸酯二元醇、聚己内酯二元醇、聚己二酸乙醇酯二醇、聚己二酸新戊二醇-1,6-己二醇酯二醇、聚己二酸丁二醇酯二醇中的至少一种。
3.根据权利要求1所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、氢化二苯基甲烷二异氰酸酯、异氟尔酮二异氰酸酯、六亚甲基二异氰酸酯中的至少一种。
4.根据权利要求1所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述催化剂为有机铋催化剂、有机银催化剂中的至少一种。
5.根据权利要求1所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述小分子扩链剂为乙二醇、1,4-丁二醇、丙二醇、1,4-环己基二甲醇、乙二胺中的至少一种。
6.根据权利要求1所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述交联剂为三羟甲基丙烷、蓖麻油、丙三醇中的至少一种。
7.根据权利要求1所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述亲水扩链剂为2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2-(2-氨基乙基)氨基乙磺酸钠盐、N-甲基二乙醇胺中的至少一种。
8.根据权利要求1所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述封闭剂为甲乙酮肟、异羟肟酸酯、1,2,4-三唑、丁二酰亚胺、乙酰苯胺、丙二酸二乙酯、2-二苯基咪唑啉中的至少一种。
9.根据权利要求1所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述中和剂为三乙胺、乙酸中的至少一种。
10.根据权利要求1所述的一种基于封闭型水性聚氨酯原位交联的多用途明胶纤维制备方法，其特征在于所述无机盐为硫酸钠、硫酸铵、氢氧化钠中的至少一种。
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