CN103992458A - 一种超高强度的聚氨酯脲超分子水凝胶及其制备方法 - Google Patents
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Abstract
本发明公开了一种超高强度的聚氨酯脲超分子水凝胶及其制备方法:同时加入聚乙二醇(PEG)、聚酯二元醇(PBA)、亲水型扩链剂二羟甲基丁酸(DMBA)以及二异氰酸酯,反应一定时间后用小分子扩链剂如1,4丁二醇(BDO)扩链,最后用水作为扩链剂进一步扩链,得到产物。其中,PEG︰聚酯二元醇︰DMBA︰BDO︰二异氰酸酯︰H2O的摩尔比为2.5∶2.5︰4∶5∶X︰X-14。本发明提供的聚氨酯脲水凝胶具有超高的拉伸强度,达到3.3-34MPa,其拉伸断裂伸长率为695-2411%。该水凝胶还具有形状记忆的功能特点,并可采用静电或熔融纺丝制备纤维。
Description
技术领域
本发明涉及功能高分子材料和超分子化学领域,具体涉及的是一种超高强度的聚氨酯脲超分子水凝胶及其制备方法。
背景技术
水凝胶是化学或物理交联的三维网状结构的高分子, 不溶于水,但能吸收大量的水或生物体液,并在溶胀之后能够继续保持其原有结构。 超分子水凝胶是一种由氢键、疏水聚集作用力、离子键、主-客体相互作用力等非共价键力交联的具有不溶于水但可被水溶胀的三维网络结构功能高分子材料。这种动态可逆、非共价交联的特性赋予超分子水凝胶诸多的优异性能, 如刺激响应性凝胶-溶胶转变行为及自修复性能等。但由于弱的非共价键力特点,超分子水凝胶多呈果冻或浆糊状,往往表现出弱且脆的物理机械特性,使其诸多潜在应用大为受限。因此,生物及化学家们一直致力于提高和控制水凝胶的机械性能,努力使其可以应用在医疗设备、药物传递系统和组织器官等方面。
聚氨酯是一类具有良好血液相容性和生物相容性的功能高分子材料。 它由软链段和硬链段交替组成,因而通过选择适当的软、硬链段结构及其比例,可以合成出具有良好的物理机械性能, 如优良的韧性和弹性的高分子材料,是制作各类弹性体制品的首选材料。然而,与其它类型的超分子水凝胶一样,聚氨酯水凝胶的机械性能也很差。 因此,如何制备出高性能的聚氨酯水凝胶具有重要的理论意义与应用价值。
发明内容
本发明的目的在于克服现有技术存在的以上问题,提供一种超高强度的聚氨酯脲超分子水凝胶的制备方法,所得的水凝胶具有优良机械性能且可进行静电纺丝。
为实现上述技术目的,达到上述技术效果,本发明通过以下技术方案实现:
一种超高强度的聚氨酯脲超分子水凝胶,水凝胶为聚乙二醇、聚酯二元醇、亲水型扩链剂、二异氰酸酯、小分子扩链剂,以及水的共聚物,其结构示意式为:
式中,R为二异氰酸酯中两个异氰酸根之间的烷基或芳香基、R1为聚酯二元醇、R2为聚乙二醇、R3为亲水型扩链剂、R4为小分子扩链剂。
进一步的,其拉伸断裂伸长率为695 - 2411 %、拉伸强度为3.3 - 34 MPa。
一种超高强度的聚氨酯脲超分子水凝胶的制备方法,包括如下步骤:
步骤1)将聚乙二醇、聚酯二元醇、亲水型扩链剂溶解于溶剂中,再加入二异氰酸酯和催化剂,PEG︰聚酯二元醇︰亲水型扩链剂︰二异氰酸酯的摩尔比为2.5∶2.5︰4∶X,在温度为70 - 80 ℃的条件下反应2-4小时;
步骤2)按摩尔比PEG︰聚酯二元醇︰亲水型扩链剂︰二异氰酸酯︰小分子扩链剂= 2.5∶2.5︰4︰X∶5加入小分子扩链剂, 在温度为50 - 70 ℃,搅拌反应1 -2小时;
步骤3)按PEG︰聚酯二元醇︰亲水型扩链剂︰二异氰酸酯︰小分子扩链剂︰H2O的摩尔比为2.5∶2.5︰4∶X∶ 5︰X-14,加入扩链剂水,在温度为50 - 60 ℃,搅拌反应16 - 72小时;
步骤4)反应结束后将产物倒入模具中成型,待溶剂挥发后,在蒸馏水中溶胀直至达到溶胀平衡,得到产物。
进一步的,步骤1中所述溶剂为丙酮。
进一步的,步骤1中所述溶剂为二甲基甲酰胺、氯仿、二氯甲烷、二氯乙烷中的一种或一种以上,步骤3中得到的产物置于乙醚中沉淀,得到白色絮状固体,干燥后溶于丙酮中,倒入模具中成型,待溶剂挥发完后,在蒸馏水中溶胀直至达到溶胀平衡,从而得到聚氨酯脲水凝胶。
进一步的,所述聚乙二醇的分子量为1000~6000 g/mol、聚酯二元醇的分子量为1000~6000 g/mol,所述催化剂为CT-E229、辛酸亚锡、二月桂酸二丁基锡中的一种或一种以上。
进一步的,所述聚酯二元醇为聚己二酸-1,4-丁二醇酯、 聚己二酸-1,6-丁二醇酯、聚ε-己内酯、聚碳酸酯二元醇、聚四氢呋喃醚中的一种或一种以上。
进一步的,所述二异氰酸酯为脂肪族的二异氰酸酯ONC-(CH2)4-NCO、ONC-(CH2)6-NCO(HDI)、ONC-(CH2)8-NCO、ONC-(CH2)12-NCO、1,5-二异氰酸-2-甲基戊烷中的一种或一种以上,或为脂环族的二异氰酸酯、、(IPDI)、中的一种或一种以上,或为芳香族的二异氰酸酯、、、、中的一种或一种以上。
进一步的,所述小分子扩链剂为1,4丁二醇(BDO)、HO-(CH2)2-OH、 、、H2N-(CH2)2-NH2、H2N-(CH2)6-NH2、H2N-(CH2)8-NH2、H2N-(CH2)10-NH2中的一种或一种以上。
本发明的有益效果是:
1、由于引入了大量的氨基甲酸酯基团及脲基,它们之间能够形成多重氢键。这种较强的分子间作用力能有效提供水凝胶所需的机械性能。其拉伸断裂伸长率范围在695 - 2411 %之间,拉伸强度范围在3.3 - 34 MPa之间。这是迄今报道的最高强度的聚合物水凝胶。
2、由于合成的产物为超分子聚合物,可溶于诸多有机溶剂,如丙酮、甲醇、DMF等中,从而可进行溶液纺丝(如溶液静电纺丝)、熔融纺丝或其它加工,因而它的加工性能优越。
3、本发明合成的聚氨酯脲水凝胶具有温度响应形状记忆功能。原因在于所制备的水凝胶拉伸性能优越以及PEG和聚酯二元醇具有结晶相转变,从而促使凝胶膜形变的产生、固定和恢复。
附图说明
图1是本发明提供的制备聚氨酯脲水凝胶的红外谱图;
图2是本发明提供的聚氨酯脲水凝胶膜的承重、双向拉伸及压缩照片;
图3、4、5是本发明提供的聚氨酯脲水凝胶拉伸试验的应力-应变图、流变测试图及压缩试验的应力-应变图;
图6是本发明提供的聚氨酯脲水凝胶静电纺丝照片;
图7是本发明提供的聚氨酯脲水凝胶形状记忆材料不同温度热响应过程的形变产生、固定和恢复的照片图。
具体实施方式
下面将参考附图并结合实施例,来详细说明本发明。
一种超高强度的聚氨酯脲超分子水凝胶,水凝胶为聚乙二醇、聚酯二元醇、亲水型扩链剂、二异氰酸酯、小分子扩链剂,以及水的共聚物,其结构示意式为:
式中,R为二异氰酸酯中两个异氰酸根之间的烷基或芳香基、R1为聚酯二元醇、R2为聚乙二醇、R3为亲水型扩链剂、R4为小分子扩链剂。
进一步的,其拉伸断裂伸长率为695- 2411 %、拉伸强度为3.3 -34 MPa。
一种超高强度的聚氨酯脲超分子水凝胶的制备方法,包括如下步骤:
步骤1)将聚乙二醇、聚酯二元醇、亲水型扩链剂溶解于溶剂中,再加入二异氰酸酯和催化剂,PEG︰聚酯二元醇︰亲水型扩链剂︰二异氰酸酯的摩尔比为2.5∶2.5︰4∶X,在温度为70 - 80 ℃的条件下反应2- 4小时;
步骤2)按摩尔比PEG︰聚酯二元醇︰亲水型扩链剂︰二异氰酸酯︰小分子扩链剂= 2.5∶2.5︰4︰X∶5加入小分子扩链剂, 在温度为50 - 70 ℃,搅拌反应1 - 2小时;
步骤3)按PEG︰聚酯二元醇︰亲水型扩链剂︰二异氰酸酯︰小分子扩链剂︰H2O的摩尔比为2.5∶2.5︰4∶X∶ 5︰X-14,加入扩链剂水,在温度为50 - 60 ℃,搅拌反应16 - 72小时;
步骤4)反应结束后将产物倒入模具中成型,待溶剂挥发后,在蒸馏水中溶胀直至达到溶胀平衡,得到产物,合成工艺路线:
。
进一步的,步骤1中所述溶剂为丙酮。
进一步的,步骤1中所述溶剂为二甲基甲酰胺、氯仿、二氯甲烷、二氯乙烷中的一种或一种以上,步骤3中得到的产物置于乙醚中沉淀,得到白色絮状固体,干燥后溶于丙酮中,倒入模具中成型,待溶剂挥发完后,在蒸馏水中溶胀直至达到溶胀平衡,从而得到聚氨酯脲水凝胶。
进一步的,所述聚乙二醇的分子量为1000~6000 g/mol、聚酯二元醇的分子量为1000~6000 g/mol,所述催化剂为CT-E229、辛酸亚锡、二月桂酸二丁基锡中的一种或一种以上。
进一步的,所述聚酯二元醇为聚己二酸-1,4-丁二醇酯、 聚己二酸-1,6-丁二醇酯、聚ε-己内酯、聚碳酸酯二元醇、聚四氢呋喃醚中的一种或一种以上。
进一步的,所述二异氰酸酯为脂肪族的二异氰酸酯ONC-(CH2)4-NCO、ONC-(CH2)6-NCO(HDI)、ONC-(CH2)8-NCO、ONC-(CH2)12-NCO、1,5-二异氰酸-2-甲基戊烷中的一种或一种以上,或为脂环族的二异氰酸酯、、(IPDI)、中的一种或一种以上,或为芳香族的二异氰酸酯、、、、中的一种或一种以上。
进一步的,所述小分子扩链剂为1,4丁二醇(BDO)、HO-(CH2)2-OH、 、、H2N-(CH2)2-NH2、H2N-(CH2)6-NH2、H2N-(CH2)8-NH2、H2N-(CH2)10-NH2中的一种或一种以上。
实施例1
其合成路线为:
合成的具体步骤为:实验前先将PEG 2k和PBA 2k升温至120℃,真空脱水1h,倒入装有温度计、回流冷凝管和搅拌棒的四口烧瓶中,60℃保温;然后向其中加入IPDI和DMBA的丙酮溶液扩链,匀速搅拌10min,加催化剂CT-E229,升温到75℃,继续反应3h;待滴定和红外监测结果达到理论NCO含量时,加入BDO扩链1h。同样待达到理论NCO含量时,加入水进行扩链,直到NCO消失(红外监测)。反应结束后将得到的溶液倒入模具中成型,待溶剂挥发后,将聚合物膜放在蒸馏水中溶胀直至达到溶胀平衡,就得到了聚氨酯脲的水凝胶。
本实施例的特点在于:先用过量的脂环族二异氰酸酯(IPDI)来合成聚氨酯预聚体,然后二异氰酸酯再与小分子扩链剂BDO反应进行扩链,最后剩余的二异氰酸酯与水反应、进一步扩链得到线型的大分子聚氨酯脲。
参见附图1,它是本实施提供的聚氨酯脲水凝胶的红外谱图。图中还附有其它原材料的红外谱图。从NCO基(2270cm-1)的消失可以判断反应完全。
参见附图2,它是本实施提供的聚氨酯脲水凝胶膜的承重、双向拉伸、及压缩照片;75×15×1.5 mm的水凝胶膜可承载6.2 kg的载荷仍不断且可基本恢复其原状。该超分子水凝胶具有良好的透明性,且60×60×1.5 mm的膜可双向拉伸而无撕裂。直径为24mm,高度为21.5mm的水凝胶圆柱能够承受1.6吨的重量而不会破损,且10min后基本可以回复原状。
参见附图3,它是本实施提供的聚氨酯脲水凝胶的拉伸测试曲线图,由图中可以看出,其拉伸断裂伸长率为1706%、拉伸强度为21MPa。也就是,这种水凝胶可以拉到原长的17倍左右才会发生断裂,并且最高承受的拉伸强度为21MPa。
参见附图4,它是本实施提供的聚氨酯脲水凝胶的流变测试图;横坐标是角速度,纵坐标为模量(kPa)。从图中可以看出,当角速度是10 rad/s时,所制超分子水凝胶的存储模量(G')和损耗模量(G”)分别达到540和160 kPa , 反映出该水凝胶很好的强度。
参见附图5,它是本实施提供的聚氨酯脲水凝胶的压缩测试曲线图,由图中可以看出,其压缩形变为90.7 %、强度为36.8 MPa。也就是,这种水凝胶圆柱能够承受1.6吨的重量而不会破损。这种高强度的水凝胶有可能应用于组织工程支架以及软骨的替换等生物材料。
参见附图6,它是本实施提供的聚氨酯脲水凝胶静电纺丝纤维的显微照片。 以丙酮和DMF为混合溶剂,配置质量分数为20%的纺丝液。工艺参数为:纺丝孔直径0.7mm,推进速度0.5ml/h, 纺丝孔与接收板的距离20 cm,纺丝电压16 kV。可见,本发明制备的聚氨酯脲水凝胶除了极佳的力学性能外,它的加工性能也很优越。
实施例2
本实施例提供一种高强度且具有形状记忆功能聚氨酯脲水凝胶的合成方法,具体步骤如下:
在PEG 2k、 PCL 4k和DMBA的丙酮溶液中加入IPDI,再加入5 μl催化剂二月桂酸二丁基锡,75 ℃下反应3 h。然后再向反应瓶中加入乙二胺,30 ℃氮气保护下搅拌反应1h。最后加入水进行扩链,直到NCO消失。反应结束后将得到的溶液倒入模具中成型,待溶剂挥发后,将聚合物膜放在蒸馏水中溶胀直至达到溶胀平衡,就得到了聚氨酯脲水凝胶。
本实施例的特点是先合成基于PCL 2k和PEG 4k为混合软段的聚氨酯预聚体,然后再用小分子扩链剂乙二胺扩链。 最后,剩余的二异氰酸酯与水进行反应、进一步扩链得到线型的大分子聚氨酯脲。其水凝胶具有形状记忆功能。
参见附图7,它是本实施提供的聚氨酯脲水凝胶形状记忆材料不同温度热响应过程的形变产生、固定和恢复的照片图。由图7可以看出,水凝胶热响应的形状记忆过程是:将聚氨酯脲水凝胶在室温下溶胀后设计成初始形状;对其施加拉伸外力形成临时形状,将临时形状固定后得到具有临时形状的干态凝胶;需要恢复时,将具有临时形状的干态凝胶放入37℃的水中,其形状恢复到一定程度,然后继续放入70℃的水中,瞬间完全回复到具有初始形状的水凝胶,实现形状记忆的功能。
实施例3
本实施例提供一种高强度聚氨酯脲水凝胶的合成方法,具体步骤如下:
在PEG 4k、PCL 4k和DMBA的DMF溶液中加入HDI, 再加入5 μl催化剂辛酸亚锡,75℃下反应3 h。然后再向反应瓶中加入辛二胺,30 ℃下搅拌反应1h。最后加入水进一步扩链,直到NCO消失。反应结束后将得到的溶液在乙醚中沉淀出来,得到白色絮状固体。将产物干燥后溶于甲醇中,然后倒入模具中成型,待溶剂挥发后,将聚合物膜放在蒸馏水中溶胀直至达到溶胀平衡,就得到了聚氨酯脲水凝胶。
本实施例的特点是使用脂肪族的二异氰酸酯HDI与PEG 4k、 PCL 4k在DMF中反应,然后再用辛二胺扩链,最后剩余的二异氰酸酯与水进行反应、进一步扩链。所得产物先沉淀后溶胀得到线型的大分子聚氨酯脲水凝胶。
实施例4
本实施例提供一种高强度聚氨酯脲水凝胶的合成方法,具体步骤如下:
在PEG 2k和PBA 2k的丙酮溶液中加入二异氰酸酯IPDI,再加入5 μl催化剂二月桂酸二丁基锡,75 ℃下反应3 h。然后再向反应瓶中加入1,2-二羟基-3-丙磺酸钠(DHPA)的水溶液,50 ℃下搅拌反应1h,直到NCO消失。反应结束后将得到的溶液倒入模具中成型,待溶剂挥发后,将聚合物膜放在蒸馏水中溶胀直至达到溶胀平衡,得到聚氨酯脲水凝胶。
本实施例的特点是先合成基于PBA 2k和PEG 2k为混合软段的聚氨酯预聚体,然后再与磺酸型亲水性扩链剂DHPA(替代传统的羧酸型亲水性扩链剂二羟甲基丁酸)及水进一步反应、扩链得到线型的大分子聚氨酯脲水凝胶。
实施例5
本实施例提供一种高强度聚氨酯脲水凝胶的合成方法,具体步骤如下:
在PEG 2k、聚四氢呋喃醚(PTMEG 2k)和DMBA的丙酮溶液中加入二异氰酸酯IPDI,再加入5 μl催化剂二月桂酸二丁基锡,75 ℃下反应3 h。然后再向反应瓶中加入乙二胺双-2-羟基丙磺酸钠(EDHPS)的水溶液,50 ℃下搅拌反应1h,直到NCO消失。反应结束后将得到的溶液倒入模具中成型,溶剂挥发后,将聚合物膜放在蒸馏水中溶胀直至达到溶胀平衡,就得到了聚氨酯脲水凝胶。
本实施例的特点是先合成基于PBA 2k和PTMEG 2k为混合软段的聚氨酯预聚体,然后再与磺酸型亲水性扩链剂EDHPS及水进一步反应、扩链得到线型的大分子聚氨酯脲。此实施例中,同时用到了磺酸型亲水性扩链剂EDHPS和传统的羧酸型亲水性扩链剂二羟甲基丁酸。
Claims (9)
1.一种超高强度的聚氨酯脲超分子水凝胶,其特征在于:水凝胶为聚乙二醇、聚酯二元醇、亲水型扩链剂、二异氰酸酯、小分子扩链剂,以及水的共聚物,其结构示意式为:
式中,R为二异氰酸酯中两个异氰酸根之间的烷基或芳香基、R1为聚酯二元醇、R2为聚乙二醇、R3为亲水型扩链剂、R4为小分子扩链剂。
2.根据权利要求1所述的超高强度的聚氨酯脲超分子水凝胶,其特征在于:其拉伸断裂伸长率为695 - 2411 %、拉伸强度为3.3 - 34 MPa。
3.一种超高强度的聚氨酯脲超分子水凝胶的制备方法,其特征在于,包括如下步骤:
步骤1)将聚乙二醇、聚酯二元醇、亲水型扩链剂溶解于溶剂中,再加入二异氰酸酯和催化剂,PEG︰聚酯二元醇︰亲水型扩链剂︰二异氰酸酯的摩尔比为2.5∶2.5︰4∶X,在温度为70 - 80 ℃的条件下反应2-4小时;
步骤2)按摩尔比PEG︰聚酯二元醇︰亲水型扩链剂︰二异氰酸酯︰小分子扩链剂= 2.5∶2.5︰4︰X∶5加入小分子扩链剂, 在温度为50 - 70 ℃,搅拌反应1 - 2小时;
步骤3)按PEG︰聚酯二元醇︰亲水型扩链剂︰二异氰酸酯︰小分子扩链剂︰H2O的摩尔比为2.5∶2.5︰4∶X∶ 5︰X-14,加入扩链剂水,在温度为50 - 60 ℃,搅拌反应16 - 72小时;
步骤4)反应结束后将产物倒入模具中成型,待溶剂挥发后,在蒸馏水中溶胀直至达到溶胀平衡,得到产物。
4.根据权利要求3所述的超高强度的聚氨酯脲超分子水凝胶的制备方法,其特征在于:步骤1)中所述溶剂为丙酮。
5.根据权利要求3所述的超高强度的聚氨酯脲超分子水凝胶的制备方法,其特征在于:步骤1)中所述溶剂为二甲基甲酰胺、氯仿、二氯甲烷、二氯乙烷中的一种或一种以上,步骤3中得到的产物置于乙醚中沉淀,得到白色絮状固体,干燥后溶于丙酮中,倒入模具中成型,待溶剂挥发完后,在蒸馏水中溶胀直至达到溶胀平衡,从而得到聚氨酯脲水凝胶。
6.根据权利要求3所述的超高强度的聚氨酯脲超分子水凝胶的制备方法,其特征在于:所述聚乙二醇的分子量为1000~6000 g/mol、聚酯二元醇的分子量为1000~6000 g/mol,所述催化剂为CT-E229、辛酸亚锡、二月桂酸二丁基锡中的一种或一种以上。
7.根据权利要求3所述的超高强度的聚氨酯脲超分子水凝胶的制备方法,其特征在于:所述聚酯二元醇为聚己二酸-1,4-丁二醇酯、 聚己二酸-1,6-丁二醇酯、聚ε-己内酯、聚碳酸酯二元醇、聚四氢呋喃醚中的一种或一种以上。
8.根据权利要求3所述的超高强度的聚氨酯脲超分子水凝胶的制备方法,其特征在于:所述二异氰酸酯为脂肪族的二异氰酸酯ONC-(CH2)4-NCO、ONC-(CH2)6-NCO(HDI)、ONC-(CH2)8-NCO、ONC-(CH2)12-NCO、1,5-二异氰酸-2-甲基戊烷中的一种或一种以上,或为脂环族的二异氰酸酯、、(IPDI)、中的一种或一种以上,或为芳香族的二异氰酸酯、、、、中的一种或一种以上。
9.根据权利要求3所述的超高强度的聚氨酯脲超分子水凝胶的制备方法,其特征在于:所述小分子扩链剂为1,4丁二醇(BDO)、HO-(CH2)2-OH、 、、H2N-(CH2)2-NH2、H2N-(CH2)6-NH2、H2N-(CH2)8-NH2、H2N-(CH2)10-NH2中的一种或一种以上。
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CN112979912A (zh) * | 2021-02-25 | 2021-06-18 | 苏州大学 | 超强韧聚乳酸基聚氨酯脲及其制备方法 |
CN112979912B (zh) * | 2021-02-25 | 2022-07-12 | 苏州大学 | 超强韧聚乳酸基聚氨酯脲及其制备方法 |
CN113754856A (zh) * | 2021-09-18 | 2021-12-07 | 天津中杰超润医药科技有限公司 | 自组装胶束、弥散增强耐磨耐疲劳仿生半月板及制备方法 |
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