CN115260529A - 一种高性能、低摩擦的纳米复合水凝胶的制备方法及应用 - Google Patents
一种高性能、低摩擦的纳米复合水凝胶的制备方法及应用 Download PDFInfo
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Abstract
本发明涉及一种一种高性能、低摩擦的纳米复合水凝胶的制备方法，包括如下步骤：将单体SBMA、交联剂EGDMA、引发剂过硫酸铵APS和Ti3C2胶体水溶液，加入去离子水中混合搅拌；完全混合后，加入加速剂四甲基乙二胺TMEDA进行搅拌；然后倒入模具，静置后得到模具形状的Ti3C2‑PSBMA复合水凝胶。本发明简单易操作，反应迅速，所制备的水凝胶只会发生溶胀而不会降解，结构稳定性好。无论实验材料还是制备过程，成本均比较低。Ti3C2的加入，显著增强了纯PSBMA水凝胶的各项力学性能，摩擦学性能也比较优良。纳米复合水凝胶显示出较好的生物相容性、亲水性和热稳定性，有潜力成为关节软骨替代材料。
Description
技术领域
本发明涉及一种两性离子纳米复合水凝胶的制备方法和应用。
背景技术
水凝胶具有类似于天然关节软骨的三维网络结构，所以它具有一系列特殊的力学性质，如可承受较大形变、生物相容性好、化学性能稳定及成型性良好等，为生物医学领域的发展提供了巨大的潜力，可以考虑作为一种潜在的生物相容材料来替代天然组织，如关节软骨、肌腱和韧带。近年来，高分子水凝胶，如双网络(double network,DN)水凝胶、两性离子共聚物(zwitterionic copolymer)水凝胶和纳米复合水凝胶，在关节软骨缺损、修复方面得到了深入的研究。两性离子水凝胶因具有高亲水性、高离子密度及离子敏感性等特点而备受瞩目，并在近十余年的研究中取得了长足的发展。
近几年来对甜菜碱两性离子水凝胶研究较多的是其对外界环境的响应性能，两性离子水凝胶目前已广泛应用于生物医学领域，包括医用植入物和组织等，但两性离子水凝胶由于其机械上的脆弱而不能承受较大的力，因此迫切需要提高和调节两性离子水凝胶的机械强度和润滑性能来满足各种生物医学应用。如：通过常用化学交联剂N，N'-亚甲基双丙烯酰胺(BIS)合成的聚甲基磺基甜菜碱(polySBMA)水凝胶的断裂压缩应力不到100kPa。
PolySBMA化学凝胶的弱力学性能极大程度上限制了它的应用范围。为解决这一问题，近几年，研究者们研究了各种制备方法用来提高甜菜碱两性离子水凝胶的力学强度以扩展其应用领域。例如，通过增加交联剂的含量来提高水凝胶的机械性能。但是，由于BIS在水中的溶解度较低，很难通过增加BIS交联剂的含量来提高polySBMA水凝胶的力学性能。鉴于此原因，Kasak等制备了新型水溶性交联剂N，N-双(甲基丙烯酰氧基乙基)-N-甲基-N-(3磺基丙基)铵甜菜碱(CL1)，用于改善polySBMA水凝胶的力学性能。结果表明，通过增加CL1含量，polySBMA水凝胶的力学性能得到很大程度上的提高(当CLl含量为20mol％单体含量时，断裂时的压缩应力高达4400kPa，断裂时的压缩应变约为85％)。Zhang等人通过将物理交联与化学交联相结合的方法制备出双网络结构的polySBMA水凝胶，也在一定程度上提高了polySBMA水凝胶的力学性能。然而，尽管这两种方法可以在一定程度上提高两性离子聚合物水凝胶的力学性能，但是受共价键的限制，化学交联制备的水凝胶在较小的形变下即发生断裂，力学性能普遍较差，如通过化学交联制备的polySBMA水凝胶的拉伸断裂应力仅5kPa，而其断裂伸长率只能达到10％。
发明内容
目前来说，不论是仿生滑液的宏观润滑机理，还是仿生水凝胶材料的承载和润滑性能方面，均难以满足实际的人体关节需求，这些问题极大的限制了这些材料的生物医学应用。本发明针对上述问题，进行了一些针对性的研究，通过添加新型二维纳米材料的方式，以期获得具有优良润滑性能、足够力学性能以及良好生物相容性的两性离子纳米复合水凝胶。
为达到以上目的，本发明采取的技术方案是：
一种高性能、低摩擦的纳米复合水凝胶的制备方法，包括如下步骤：
步骤1、将两性离子单体、交联剂、引发剂和Ti3C2水溶液，加入去离子水中混合搅拌；
步骤2、完全混合后，加入加速剂进行搅拌；
步骤3、然后倒入模具，静置后得到模具形状的Ti3C2-PSBMA复合水凝胶。
两性离子单体为甲基磺基甜菜碱，交联剂为乙二醇二甲基丙烯酸酯，引发剂为过硫酸铵，加速剂为四甲基乙二胺。
两性离子单体、交联剂、引发剂、加速剂在混合溶液中的浓度分别为1-2.5mol L-1、0.2-1.5mol L-1、0.02-0.25mol L-1、0.2-1.0mol L-1。
Ti3C2在混合溶液中的质量分数为0.001-1wt％。
Ti3C2在混合溶液中的质量分数为0.005wt％，0.01wt％，0.015wt％，0.02wt％，或者0.025wt％。
步骤1中，以200-1000r/min进行恒温磁力混合搅拌至少4小时。
步骤2中，搅拌时间为1-3min。
步骤3中，静置时间为10-30min。
得到的Ti3C2-PSBMA复合水凝胶在纯水中浸泡至少3天，以去除未反应的物质。
所述Ti3C2-PSBMA复合水凝胶在关节软骨替代中的应用。
本发明的有益效果：本发明采用化学交联的方法制备了复合水凝胶。这种方法简单易操作，反应迅速，成型时间短，所制备的水凝胶只会发生溶胀而不会降解，结构稳定性好。无论实验材料还是制备过程，成本均比较低。
1.在两性离子水凝胶中引入单层Ti3C2，这是一种新型二维材料MXene，利用简单搅拌，通过自由基聚合以及物理静电吸附作用，形成了交织的纳米复合水凝胶网络。
2.Ti3C2的加入，显著增强了纯PSBMA水凝胶的各项力学性能，其抗压强度增加了320％(从0.067到0.217MPa)，抗拉强度提高了360％(从0.027到0.097MPa)。
3.使用水凝胶这种软材料与硅片进行往复摩擦运动，获得了低摩擦系数(约0.0126)。因此Ti3C2-PSBMA复合水凝胶的摩擦学性能也比较优良。
4.得到的纳米复合水凝胶显示出较好的生物相容性、亲水性和热稳定性，有潜力成为关节软骨替代材料。
进行了动态力学和应力松弛实验，在整个角频率范围内，几个浓度的样品的储能模量远大于损耗模量，这是强水凝胶的一个显著特征。同时，储能模量值随角频率的增加有微弱的增大趋势，这与天然关节软骨的性质一致。另外，几个浓度的损耗因子均在天然关节软骨的损耗因子0.01～0.1范围内波动，同时具备较高的储能模量和较低的损耗模量。
附图说明
本发明有如下附图：
图1推测的EGDMA、Ti3C2和SBMA之间水凝胶网络形成机理的示意图。
图2中，(a)图为不同浓度的Ti3C2-PSBMA复合水凝胶的压缩应力-应变图，(b)图为不同浓度的Ti3C2-PSBMA复合水凝胶的拉伸应力-应变图，(c)图为储能模量G'和损耗模量G"，(d)图为损耗因子(tanδ)，(e)图为归一化压缩松弛模量曲线。
图3中，a图为水凝胶半球和硅片作为摩擦副的摩擦系数测量图；b图为以Ti3C2浓度为实验变量，摩擦系数(COF)随时间的变化图；c图为在1N的恒定法向载荷下，摩擦系数随滑动速度的变化曲线；d图为在30mm/s的滑动速度下，摩擦系数随载荷变化图。
图4中，a图为PSBMA在100倍下扫描电镜的形貌图，b图为Ti3C2(0.005wt％)-PSBMA在100倍下扫描电镜的形貌图，c图为Ti3C2(0.015wt％)-PSBMA在100倍下扫描电镜的形貌图，d图为PSBMA在1000倍下扫描电镜的形貌图，e图为Ti3C2(0.005wt％)-PSBMA在1000倍下扫描电镜的形貌图，f图为Ti3C2(0.015wt％)-PSBMA在1000倍下扫描电镜的形貌图。
图5中，(a)图为Ti3C2-PSBMA复合水凝胶的FT-IR光谱图，(b)图为Ti3C2-PSBMA复合水凝胶的拉曼光谱图，(c)图为Ti3C2-PSBMA复合水凝胶的热重曲线图，(d)图为Ti3C2-PSBMA复合水凝胶的接触角。
图6中，a图为空白对照组的细胞形态图，b图为加入纯PSBMA水凝胶浸提液的细胞形态图，c图为阳性对照组的细胞形态图，d图为阴性对照组的细胞形态图。
具体实施方式
以下结合附图对本发明作进一步详细说明。
本发明没有采用常用的化学交联剂，比如戊二醛和环氧氯丙烷等，它们通常难以去除，且会降低水凝胶的生物相容性，影响其生物医学应用。本发明使用交联剂乙二醇二甲基丙烯酸酯(EGDMA)通过简单搅拌完成化学交联过程，并对纯PSBMA水凝胶进行了细胞毒性的测试，证明了水凝胶样品无潜在的细胞毒性。
实施例1：PSBMA水凝胶的制备方法，包括如下步骤：
将单体SBMA(279.35g mol-1)(作为水凝胶网络的聚合物链)、交联剂EGDMA(198.22g mol-1)和引发剂过硫酸铵APS(228.20gmol-1)加入水中，以600r/min进行恒温磁力混合搅拌至少4小时。完全混合后，加入加速剂四甲基乙二胺TMEDA(116.20g mol-1)搅拌1min，单体SBMA、交联剂EGDMA、引发剂过硫酸铵APS、四甲基乙二胺TMEDA在混合溶液中的浓度分别为2.5mol L-1、1mol L-1、0.22mol L-1和0.5mol L-1。然后倒入模具，静置10min后得到模具形状的PSBMA水凝胶。四种试剂的化学结构式见式a)、b)、c)、d)。
四种试剂的化学结构式：a)SBMA，b)APS，c)EGDMA，d)TMEDA。
通过类似的方法制备了Ti3C2-PSBMA复合水凝胶：将不同含量的单层Ti3C2胶体水溶液(作为纳米添加材料)在搅拌前加入混合溶液，Ti3C2是一种新型的MXene二维材料。Ti3C2的含量根据最终混合溶液的质量而定，Ti3C2在混合溶液中的质量分数可以为0.001-1wt％。
两种水凝胶的凝胶化过程维持10-30min。所得的PSBMA和Ti3C2-PSBMA复合水凝胶在纯水中浸泡至少3天，以去除未反应的物质。纯水每天换三次。
实施例2
一种高性能、低摩擦的纳米复合水凝胶的制备方法，包括如下步骤：
将单体SBMA、交联剂EGDMA、引发剂过硫酸铵APS和Ti3C2胶体水溶液加入去离子水中，以600r/min进行恒温磁力混合搅拌至少4小时。完全混合后，加入加速剂四甲基乙二胺TMEDA搅拌2min；单体SBMA、交联剂EGDMA、引发剂过硫酸铵APS、四甲基乙二胺TMEDA在混合溶液中的浓度分别为2.5mol L-1、1mol L-1、0.15mol L-1和0.5mol L-1。然后倒入模具，静置20min后得到模具形状的Ti3C2-PSBMA复合水凝胶。
所得的Ti3C2-PSBMA复合水凝胶在纯水中浸泡3天，以去除未反应的物质。纯水每天换三次。
实施例3
一种高性能、低摩擦的纳米复合水凝胶的制备方法，包括如下步骤：
将单体SBMA、交联剂EGDMA、引发剂过硫酸铵APS和Ti3C2胶体水溶液加入去离子水中，以400r/min进行恒温磁力混合搅拌至少4小时。完全混合后，加入加速剂四甲基乙二胺TMEDA搅拌1min；单体SBMA、交联剂EGDMA、引发剂过硫酸铵APS、四甲基乙二胺TMEDA在混合溶液中的浓度分别为1.5mol L-1、0.2mol L-1、0.05mol L-1和0.2mol L-1。然后倒入模具，静置10min后得到模具形状的Ti3C2-PSBMA复合水凝胶。
所得的Ti3C2-PSBMA复合水凝胶在纯水中浸泡1天，以去除未反应的物质。纯水每天换三次。
实施例4
一种高性能、低摩擦的纳米复合水凝胶的制备方法，包括如下步骤：
将单体SBMA、交联剂EGDMA、引发剂过硫酸铵APS和Ti3C2胶体水溶液加入去离子水中，以800r/min进行恒温磁力混合搅拌至少4小时。完全混合后，加入加速剂四甲基乙二胺TMEDA搅拌3min；单体SBMA、交联剂EGDMA、引发剂过硫酸铵APS、四甲基乙二胺TMEDA在混合溶液中的浓度分别为2mol L-1、1.5mol L-1、0.25mol L-1和1mol L-1。然后倒入模具，静置30min后得到模具形状的Ti3C2-PSBMA复合水凝胶。
所得的Ti3C2-PSBMA复合水凝胶在纯水中浸泡2天，以去除未反应的物质。纯水每天换三次。
我们推测，SBMA聚合物链、交联剂EGDMA和Ti3C2之间的合成机理可分为2个反应：
(1)单体SBMA和交联剂EGDMA之间通过自由基聚合实现化学结合。所谓自由基聚合(free radical polymerization)，即用自由基引发，使链增长(链生长)自由基不断增长的聚合反应。又称游离基聚合。
(2)纳米复合颗粒Ti3C2纳米片是通过强静电相互作用附着在SBMA聚合物链上。具体为单层Ti3C2表面游离羟基上带负电的氧原子与PSBMA链上每个单体中带正电的氮原子相互吸引，通过物理作用相互结合。如图1所示。
本发明成功合成了纳米复合水凝胶，旨在揭示其在化学表征、力学性能、摩擦学性能以及生物相容性方面的潜在相互作用。
图4为本发明的复合水凝胶样品达到溶胀饱和后冷冻干燥后的扫描电镜截面形貌图。
图5为本发明的复合水凝胶的一系列表征实验结果。
从图2-5可以看出，本发明制备的复合水凝胶与纯PSBMA水凝胶相比力学性能和摩擦学性能都有显著提高。其抗压强度增加了320％(从0.067到0.217MPa)，抗拉强度提高了360％(从0.027到0.097MPa)。Ti3C2加入之后，还显著增强了纯PSBMA水凝胶的消散静态载荷能力和动态力学性能。将其与硅片进行往复摩擦运动，也获得了低摩擦系数(约0.0126)。
PSBMA复合水凝胶的细胞毒性实验：
图6中，显示了加入100％PSBMA浸提液和三个对照组(包括空白对照组、阳性对照组和阴性对照组)后观察到的细胞形态图像。通过观察空白对照组(含10％FBS的MEM培养液，Hyclone)的细胞形态，发现细胞质中均为离散的细胞颗粒，且没有细胞溶解，90％以上的细胞形态良好，如a图所示。与空白对照组相比，在加入100％PSBMA水凝胶浸提液后，如b图所示，PSBMA水凝胶浸提液培养的细胞存活率在70％以上，表明PSBMA水凝胶没有潜在的细胞毒性。而在c图所示的阳性对照组(高密度聚乙烯薄膜，海门市扬子医疗器械有限公司)中，细胞层几乎完全被破坏，细胞活力也很低，仅为1.3～6.6％。在d图中，阴性对照组(用高压灭菌的植入物级GUR1020UHMWPE(超高分子量聚乙烯，Ultra-high molecular weightpolyethylene)，Hatano Research Institute，FDSC)中的细胞存活率超过80％，仅观察到少量的细胞溶解，并且几乎观察不到细胞生长被抑制的现象。
图6只给出了加入100％PSBMA浸提液的细胞形态图像，实验过程中还用不同浓度的PSBMA浸提液进行了实验，图b就是100％浓度PSBMA浸提液的实验结果。25％PSBMA浸提液，50％PSBMA浸提液，75％PSBMA浸提液，这三个结果均比100％PSBMA浸提液的更好，因此不同浓度的PSBMA水凝胶浸提液培养的细胞存活率均在70％以上，表明PSBMA水凝胶没有潜在的细胞毒性。
以上实施方式仅用于说明本发明，而并非对本发明的限制，有关技术领域的普通技术人员，在不脱离本发明的实质和范围的情况下，还可以做出各种变化和变型，因此所有等同的技术方案也属于本发明的保护范围。
本说明书中未作详细描述的内容属于本领域专业技术人员公知的现有技术。
Claims (10)
1.一种高性能、低摩擦的纳米复合水凝胶的制备方法，其特征在于，包括如下步骤：
步骤1、将两性离子单体、交联剂、引发剂和Ti3C2水溶液，加入去离子水中混合搅拌；
步骤2、完全混合后，加入加速剂进行搅拌；
步骤3、然后倒入模具，静置后得到模具形状的Ti3C2-PSBMA复合水凝胶。
2.如权利要求1所述的高性能、低摩擦的纳米复合水凝胶的制备方法，其特征在于：两性离子单体为甲基磺基甜菜碱，交联剂为乙二醇二甲基丙烯酸酯，引发剂为过硫酸铵，加速剂为四甲基乙二胺。
3.如权利要求1所述的高性能、低摩擦的纳米复合水凝胶的制备方法，其特征在于：两性离子单体、交联剂、引发剂、加速剂在混合溶液中的浓度分别为1-2.5mol L-1、0.2-1.5molL-1、0.02-0.25mol L-1、0.2-1.0mol L-1。
4.如权利要求1所述的高性能、低摩擦的纳米复合水凝胶的制备方法，其特征在于：Ti3C2在混合溶液中的质量分数为0.001-1wt％。
5.如权利要求4所述的高性能、低摩擦的纳米复合水凝胶的制备方法，其特征在于：Ti3C2在混合溶液中的质量分数为0.005wt％，0.01wt％，0.015wt％，0.02wt％，或者0.025wt％。
6.如权利要求1所述的高性能、低摩擦的纳米复合水凝胶的制备方法，其特征在于：步骤1中，以200-1000r/min进行恒温磁力混合搅拌至少4小时。
7.如权利要求1所述的高性能、低摩擦的纳米复合水凝胶的制备方法，其特征在于：步骤2中，搅拌时间为1-3min。
8.如权利要求1所述的高性能、低摩擦的纳米复合水凝胶的制备方法，其特征在于：步骤3中，静置时间为10-30min。
9.如权利要求1所述的高性能、低摩擦的纳米复合水凝胶的制备方法，其特征在于：得到的Ti3C2-PSBMA复合水凝胶在纯水中浸泡至少3天，以去除未反应的物质。
10.如权利要求1-9任一所述的方法得到的Ti3C2-PSBMA复合水凝胶在关节软骨替代中的应用。
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