CN115785650A - 一种丙交酯基的弹性聚氨酯水凝胶 - Google Patents
一种丙交酯基的弹性聚氨酯水凝胶 Download PDFInfo
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Abstract
本发明涉及水凝胶材料技术领域内一种丙交酯基的弹性聚氨酯水凝胶,该聚氨酯聚合物是以含有较多活性双键乙烯基羟基硅氧烷(PMVS)为构架且为弹性段,依次引发丙交酯(LA)、丙烯酸(AA)聚合得到主要框架,其中PAA为亲水段,通过二异氰酸酯扩链得到的聚氨酯。该聚氨酯制备过程简单,不但较低温度下(室温)即可实现固化,且具有弹性,具有PAA的亲水性,保水效果好,具备聚丙交酯的生物可降解性和生物相容性。是一种具有弹性的生物可降解凝胶,可用于药物输送***,伤口敷料,隐形眼镜,用于组织工程的支架和吸水材料,以及荒漠化防治固沙等农业领域的潜在应用候选材料。
Description
技术领域
本发明涉及聚氨酯水凝胶领域,特别涉及一种弹性聚氨酯水凝胶材料。
背景技术
水凝胶是具有巨大吸水能力的三维网络,通常由亲水聚合物通过物理或化学交联制成。通过控制化学成份、改变聚合方法和调整交联密度,可以调整和定制水凝胶的网络结构和孔径,以满足所需应用的要求。聚氨酯(PU)或聚氨酯脲(PUU)水凝胶以其良好的物理机械性能和优异的生物相容性吸引了广泛的研究兴趣。
PLA作为用途广泛的生物可降解聚酯,常用作组织工程支架作为药物传送材料。现有技术中,未见将其与将其与聚氨酯材料制成水凝胶的报道。
发明内容
本发明提供了一种丙交酯基的弹性聚氨酯水凝胶,聚合物合成简单,固化温度低,以获得具有弹性的聚氨酯水凝胶。
本发明的技术方案:一种丙交酯基的弹性聚氨酯水凝胶,包括梳状结构的PMVS柔性段,主链上含有PLA可降解段和PAA亲水段,其分子结构如下:
所述梳状结构的PMVS柔性段结构如下:
n为大于1的整数;
所述PLA可降解段的结构如下:
y为大于1的整数;
所述PAA亲水段的结构如下:
m为大于1的整数。
该材料以含有较多活性双键乙烯基羟基硅氧烷(PMVS)为构架且为弹性段,引发LA开环聚合以及AA加成聚合,形成以PMVS为柔性段,具有硅氧烷的柔性,PAA为亲水段以及PLA为生物可降解和生物相容段,通过异氰酸酯以及水分子氢键聚合形成聚氨酯,因为PAA段的亲水性,从而将更多的水分锁在聚氨酯内部。该聚氨酯制备过程简单,不但较低温度下(室温)即可实现固化,且具有弹性,具有PAA的亲水性,保水效果好,具备聚丙交酯的生物可降解性和生物相容性。获得的具有弹性的生物可降解凝胶,可用于药物输送***,伤口敷料,隐形眼镜,用于组织工程的支架和吸水材料,以及荒漠化防治固沙等农业领域的潜在应用候选材料。
附图说明
图1为聚氨酯以及中间产物的红外光谱图。
图2为合成聚氨酯水凝胶弹性拉伸性能测试对比图。
具体实施方式
下面通过实施例对本发明进行具体描述。
实施例1:
称重适量PMVS和丙交酯(LA)放置于配有磁力搅拌棒的安瓿瓶中,抽真空通氮气,一定量甲苯溶剂下搅拌45min后,滴加辛酸亚锡(甲苯稀释)催化剂,升温到120℃,反应24h,反应后石油醚沉降抽滤,产物40℃真空干燥12h。将上述所得一定量产物置于三口烧瓶中,通氮气,四氢呋喃做溶剂,偶氮二异丁氰做催化剂,温度控制65℃,通过滴定漏斗滴加AA,反应5h,获得产物沉降并干燥。
将所得产物、异氰酸酯(10wt%)、去离子水(10wt%)以及二月桂酸二丁基锡催化剂溶于N,N-二甲基甲酰胺溶剂当中,然后65℃反应4h,将搅拌过的溶液倒到玻璃板上,让溶液在玻璃板上自由流延。在常温(20℃左右)和常压下溶剂自然挥发,待膜在空气中固化后,随后将膜加工成型,备用。并将其拉伸以验证其弹性。
如图1所示, 红外光谱图中,a和b分别为PMVS和PMVS-PLA的红外光谱图,b中1750cm-1处-C=O的吸收峰归因于PLLA,c为PAA-PMVS-PLA,1600cm-1处碳碳双键吸收峰消失,并且3330cm-1处羟基吸收峰变宽,说明PAA已经聚合,d曲线中3417 cm-1处-N-H吸收峰,2270 cm-1-NH-CO-的吸收峰,1630 cm-1-C=N-的吸收峰以及1332 cm-1-C-N-吸收峰说明异氰酸酯已与分子反应。采用红外表征的结果说明一种以梳状结构PMVS为柔性段,主链上含有PLA可降解段和PAA亲水段的聚氨酯已经合成。
推定其结构式如下:
图2为测试合成聚氨酯水凝胶弹性的过程,左图为拉伸前(1.5格),右图为拉伸后(4格),通过聚氨酯弹性体拉伸前后长度变化,可以很好体现其良好的弹性能。
将固化后的样品吸水直至质量不变,称量质量,置于室温,每间隔2h测试其质量,发现24h后其质量损失仅为20%,这表明,吸水后的样品具有很好的保水效果。
本发明并不局限于上述实施例,在本发明公开的技术方案的基础上,本领域的技术人员根据所公开的技术内容,不需要创造性的劳动就可以对其中的一些技术特征作出一些替换和变形,这些替换和变形均在本发明的保护范围内。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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KR20150132676A (ko) * | 2014-05-15 | 2015-11-26 | (주)삼중 | 폴리오가노실록산 변성 우레아-아크릴레이트 화합물의 제조방법, 그에 의해 제조되는 폴리오가노실록산 변성 우레아-아크릴레이트 화합물 및 이를 포함하는 코팅조성물 |
CN106977726A (zh) * | 2017-04-18 | 2017-07-25 | 长春工业大学 | 一种甲基乙烯基聚硅氧烷‑生物可降解聚酯嵌段共聚物 |
CN111548456A (zh) * | 2020-06-01 | 2020-08-18 | 长春工业大学 | 一种赋予聚乳酸水诱导形状记忆的聚合物 |
CN113881386A (zh) * | 2021-10-27 | 2022-01-04 | 张家港飞腾复合新材料股份有限公司 | 复合型热熔胶及应用该热熔胶的复合板 |
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Publication number | Priority date | Publication date | Assignee | Title |
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KR20150132676A (ko) * | 2014-05-15 | 2015-11-26 | (주)삼중 | 폴리오가노실록산 변성 우레아-아크릴레이트 화합물의 제조방법, 그에 의해 제조되는 폴리오가노실록산 변성 우레아-아크릴레이트 화합물 및 이를 포함하는 코팅조성물 |
CN106977726A (zh) * | 2017-04-18 | 2017-07-25 | 长春工业大学 | 一种甲基乙烯基聚硅氧烷‑生物可降解聚酯嵌段共聚物 |
CN111548456A (zh) * | 2020-06-01 | 2020-08-18 | 长春工业大学 | 一种赋予聚乳酸水诱导形状记忆的聚合物 |
CN113881386A (zh) * | 2021-10-27 | 2022-01-04 | 张家港飞腾复合新材料股份有限公司 | 复合型热熔胶及应用该热熔胶的复合板 |
Non-Patent Citations (1)
Title |
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YAJUN REN ET AL.: "Water-responsive shape memory PLLA via incorporating PCL-(PMVS-s-PAA)-PCL-PTMG-PCL-(PMVS-s-PAA)-PCL", 《EUROPEAN POLYMER JOURNAL》, vol. 147, pages 110252 * |
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