CN111978567A - 聚甲基丙烯酸-2-羟乙酯/n-乙烯基吡咯烷酮二元共聚水凝胶及其制备方法 - Google Patents
聚甲基丙烯酸-2-羟乙酯/n-乙烯基吡咯烷酮二元共聚水凝胶及其制备方法 Download PDFInfo
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Abstract
本发明提供一种聚甲基丙烯酸‑2‑羟乙酯/N‑乙烯基吡咯烷酮二元共聚水凝胶及其制备方法，包括步骤：(1)在反应容器中加入甲基丙烯酸‑2‑羟乙酯、N‑乙烯基吡咯烷酮、交联剂、助剂和溶剂并搅拌均匀得到混合物A，其中，所述助剂的用量为0‑2mL；(2)对所述混合物A进行加热，升温至一定温度；(3)达到预设温度后，加入引发剂，当聚合物反应形成凝胶状时，停止反应；(4)将聚合物取出浸泡在水中一段时间，制得聚甲基丙烯酸‑2‑羟乙酯/N‑乙烯基吡咯烷酮二元共聚水凝胶。通过该方法制备的聚甲基丙烯酸‑2‑羟乙酯/N‑乙烯基吡咯烷酮二元共聚水凝胶具有良好的平衡含水量、拉伸强度和耐溶剂性能。
Description
技术领域
本发明涉及水凝胶的制备技术领域，尤其是涉及一种聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶及其制备方法。
背景技术
水凝胶顾名思义，它是一类凝胶状的高分子，以水作为分散介质，其分子结构当中含有大量的亲水性的基团，使之能够与水具有很强的结合能力，结构上来说，具有交联的三维立体网状结构从而使大量的水中能够充满在大分子中，具有很好的黏弹性。
随着科研人员对水凝胶的研究的不断深入，水凝胶的应用领域正在不断地扩大，对其研究的前景也非常被看好。应用在不同领域上的水凝胶，所用的原料也是不同的。例如，聚甲基丙烯酸羟乙酯水凝胶(PHEMA)，它是一种非常适宜作眼角角膜移植的材料，同时，它还可以应用在涂料以及粘合剂的应用方面等，PHEMA水凝胶现在在作为相关的组织的替代物和药物的控制释放体系等临床医学方面已经得到了非常广泛的应用了，而通过化学交联的方法制备的PHEMA水凝胶，当与黑色素形成互穿网络的结构时，可以被用来作为眼内植入物来排汇紫外线。目前，PHEMA水凝胶在平衡含水量和耐溶剂性能等方面，还有待提高。
发明内容
本发明的目的之一是提供一种聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法，通过该方法制备的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶具有良好的平衡含水量、拉伸强度和耐溶剂性能。
本发明的目的之二是提供一种采用上述方法制得的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶。
为实现上述目的，本发明提供了一种聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法，包括步骤：
(1)在反应容器中加入甲基丙烯酸-2-羟乙酯、N-乙烯基吡咯烷酮、交联剂、助剂和溶剂并搅拌均匀得到混合物A；
(2)对所述混合物A进行加热，升温至一定温度；
(3)达到预设温度后，加入引发剂，当聚合物反应形成凝胶状，停止反应；
(4)将聚合物取出浸泡在水中一段时间，制得聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶。
与现有技术相比，本申请的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法借助甲基丙烯酸-2-羟乙酯、N-乙烯基吡咯烷酮、交联剂助剂、溶剂和引发剂进行反应，制得聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶。N-乙烯基吡咯烷酮的亲水能力非常强，其分子结构中含有乙烯基的结构，容易与甲基丙烯酸-2-羟乙酯发生聚合反应形成二元聚合物，通过引入亲水性的单体N-乙烯基吡咯烷酮，提高二元共聚水凝胶的平衡含水量和耐溶剂性能。
进一步的，甲基丙烯酸-2-羟乙酯的用量可为但不限于0.5-3mL、N-乙烯基吡咯烷酮的用量可为但不限于0.5-3mL、交联剂的用量可为但不限于0.5-3mL、助剂的用量可为但不限于0-2mL和溶剂的用量可为但不限于0.5-5mL；引发剂的用量可为但不限于0.01g-0.1g。
进一步的，溶剂可为但不限于蒸馏水。
进一步的，步骤(2)中，加热过程中采用磁力搅拌，使物质完全混合均匀，升温均匀。
进一步的，步骤(2)中，采用油浴进行加热。
进一步的，步骤(2)中，温度为70-80℃。
进一步的，引发剂选自过硫酸胺或1-羟基环己基苯丙酮。优选地，采用1-羟基环己基苯丙酮，由于1-羟基环己基苯丙酮的活性较好，在该体系中充分促使自由基聚合反应，从而形成化学键，以提高反应速率，且产品转化率高。
进一步的，所述交联剂选自二甲基丙烯酸乙二醇酯或N,N-亚甲基双丙烯酰胺。试验表明，本体系中采用N,N-亚甲基双丙烯酰胺得到的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶在拉伸强度方面有所提高，可能是N,N-亚甲基双丙烯酰胺作为交联剂时，其活性基团更适合该体系，交联效率高，可形成稳定的三维立体的交联网络结构。
进一步的，所述助剂选自甲基丙烯酸甲酯，甲基丙烯酸-2-羟乙酯与甲基丙烯酸甲酯相互作用，可有效弥补因引入亲水性的单体N-乙烯基吡咯烷酮而降低共聚物的力学性能(主要指拉伸强度)的缺陷，以使得该水凝胶具有优良的拉伸强度。
进一步的，浸泡时间为0.5-6h。
相应地，本申请还提供了一种聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶，采用上述的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法制得。该聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶具有良好的平衡含水量、拉伸强度和耐溶剂性能。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案，但不构成对本发明的任何限制。
实施例1
一种聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法，包括步骤：
(1)用小试管称取1.75mL的甲基丙烯酸-2-羟乙酯(HEMA)、1.75mL的N-乙烯基吡咯烷酮(NVP)、0.5mL的甲基丙烯酸甲酯，倒入到小烧杯中，然后加入0.05mL的交联剂，再加入1.25mL的蒸馏水作为溶剂，用手轻轻摇动烧杯，使烧杯中的物质混合均匀，得到混合物A。
(2)将小烧杯固定在油浴锅中进行加热，设定温度为70℃，在磁力的不断搅拌下，以便烧杯中的各种反应物能够充分混合；
(3)等到油浴锅达到设定的温度的时候，用电子天平称取0.01905g的引发剂倒入在小烧杯，等到反应至生成的聚合物具有一定的硬度的时候，将磁子取出，继续反应至形成凝胶状，然后停止反应；
(4)将聚合物取出，用水浸泡1小时，制得聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶。
实施例2-8
实施例2～8的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备原料及含量如表1所示，制备步骤同实施例1相同。
对比例1
一种聚甲基丙烯酸-2-羟乙酯水凝胶的制备方法，包括步骤：
(1)用小试管称取1.75mL的甲基丙烯酸-2-羟乙酯(HEMA)、0.5mL的甲基丙烯酸甲酯，倒入到小烧杯中，然后加入0.05mL的交联剂，再加入1.25mL的蒸馏水作为溶剂，用手轻轻摇动烧杯，使烧杯中的物质混合均匀，得到混合物A。
(2)将小烧杯固定在油浴锅中进行加热，设定温度为70℃，在磁力的不断搅拌下，以便烧杯中的各种反应物能够充分混合；
(3)等到油浴锅达到设定的温度的时候，用电子天平称取0.01905g的引发剂倒入在小烧杯，等到反应至生成的聚合物具有一定的硬度的时候，将磁子取出，继续反应至形成凝胶状，然后停止反应；
(4)将聚合物取出，用水浸泡1小时，制得聚甲基丙烯酸-2-羟乙酯水凝胶。
表1实施例1-8及对比例1的制备原料及含量
对实施例1-8和对比例1制备的水凝胶性能测试，测试结果见表2。
其中，测试项目及条件如下：
平衡含水量的测试：水凝胶的平衡含水量通常定义为将水凝胶浸入在水中，使其能够充分的吸收水分，此时其体积就会不断的膨胀，当水凝胶的体积不再发生变化，也不再吸收水分时，就达到了溶胀平衡的状态，记下此时凝胶的重量为wt，将吸水膨胀达到溶胀平衡状态的水凝胶放入烘箱中进行干燥，当被干燥的凝胶的重量不再发生变化时，记下此时的重量为wd，计算公式如下：
EWC(％)＝(wt-wd)×100％/wd
拉伸强度测试：用剪刀剪取水凝胶样品，用蒸馏水浸泡，使其达到溶胀平衡，然后将样品放进烘箱当中进行烘干，直至达到恒重，然后取出材料，冷却至室温，用C型裁刀截取试样，将样品裁剪形成亚铃型的形状，然后用电子拉力机测定其拉伸强度，将温度设为25℃，拉伸速度设为10mm/min，水凝胶的拉伸强度按照如下公式进行计算：
σ＝F/(b×d)
其中，σ表示拉伸强度(MPa)；F表示试样所受到的作用力(N)；b表示试样工作部分的宽度(mm)；d表示试样工作部分的厚度(mm)。
抗溶剂性能测试：用剪刀剪取已经达到溶胀平衡状态的水凝胶样品，重量约为1.0g，用蒸馏水冲洗待测样品的表面，然后将样品置于60℃的烘箱当中烘干直至恒重。从烘箱当中取出样品，将其剪碎尽量平均分成四份，并做到形状大致相同，然后分别浸入到装有3ml的无水乙醇、丙酮、氯仿、四氢呋喃的有机溶剂的小试管中，密闭，避光保存，于一周之后观察实验现象。
表2性能测试结果
| 平衡含水量/％ | 拉伸强度/MPa | 抗溶剂性能 | |
| 实施例1 | 67.55 | 0.437 | 均不溶解 |
| 实施例2 | 70.92 | 0.415 | 均不溶解 |
| 实施例3 | 66.76 | 0.422 | 均不溶解 |
| 实施例4 | 74.38 | 0.346 | 均不溶解 |
| 实施例5 | 79.25 | 0.259 | 均不溶解 |
| 实施例6 | 65.97 | 0.429 | 均不溶解 |
| 实施例7 | 66.23 | 0.382 | 均不溶解 |
| 实施例8 | 65.98 | 0.317 | 均不溶解 |
| 对比例1 | 52.34 | 0.634 | 均不溶解 |
从表1的实施例1-3可知，当甲基丙烯酸-2-羟乙酯、N-乙烯基吡咯烷酮、交联剂、助剂和蒸馏水的用量一定时，随着引发剂含量的增加，聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的平衡含水量先上升后下降。当引发剂的含量小于一定数值的时候，聚合反应中N-乙烯基吡咯烷酮的反应速率比甲基丙烯酸-2-羟乙酯要大，因此，进入到共聚物当中的N-乙烯基吡咯烷酮单体的数量就多于HEMA，而N-乙烯基吡咯烷酮的亲水能力非常强，故其平衡含水量也随之升高，但当引发剂的含量超过该值的时候，甲基丙烯酸-2-羟乙酯的反应速度要比N-乙烯基吡咯烷酮的大,使得共聚物的平衡含水量出现下降的现象。
从表1的实施例1、实施例4-5及对比例1可知，当甲基丙烯酸-2-羟乙酯、交联剂、助剂、引发剂和蒸馏水的用量一定时，随着N-乙烯基吡咯烷酮含量的增加，聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的拉伸强度是逐渐降低的。因为N-乙烯基吡咯烷酮是亲水性的单体，容易与极性的水分子发生相互作用，因此使甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮形成的聚合物网络，结构就会变得比较松散，因此其拉伸强度会随N-乙烯基吡咯烷酮含量的增加而逐渐下降。
从实施例1、实施例8和对比例1可知，甲基丙烯酸甲酯的引入，可有效弥补因引入亲水性的单体N-乙烯基吡咯烷酮而降低共聚物的力学性能的缺陷，以使得该水凝胶具有优良的拉伸强度。
应当指出，以上具体实施方式仅用于说明本发明而不用于限制本发明的范围，在阅读了本发明之后，本领域技术人员对本发明的各种等价形式的修改均落入本申请所附权利要求限定的范围。
Claims (9)
1.一种聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法，其特征在于，包括步骤：
(1)在反应容器中加入甲基丙烯酸-2-羟乙酯、N-乙烯基吡咯烷酮、交联剂、助剂和溶剂并搅拌均匀得到混合物A，其中，所述助剂的用量为0-2mL；
(2)对所述混合物A进行加热，升温至一定温度；
(3)达到预设温度后，加入引发剂，当聚合物反应形成凝胶状时，停止反应；
(4)将聚合物取出浸泡在水中一段时间，制得聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶。
2.根据权利要求1所述的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法，其特征在于，步骤(2)中，加热过程中采用磁力搅拌。
3.根据权利要求1所述的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法，其特征在于，步骤(2)中，采用油浴进行加热。
4.根据权利要求1所述的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法，其特征在于，步骤(2)中，温度为70-80℃。
5.根据权利要求1所述的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法，其特征在于，所述引发剂选自过硫酸胺或1-羟基环己基苯丙酮。
6.根据权利要求1所述的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法，其特征在于，所述交联剂选自二甲基丙烯酸乙二醇酯或N,N-亚甲基双丙烯酰胺。
7.根据权利要求1所述的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法，其特征在于，所述助剂选自甲基丙烯酸甲酯。
8.根据权利要求1所述的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法，其特征在于，所述甲基丙烯酸-2-羟乙酯的用量为0.5-3mL、所述N-乙烯基吡咯烷酮的用量为0.5-3mL、所述交联剂的用量为0.5-3mL、所述溶剂的用量为0.5-5mL；所述引发剂的用量为0.01g-0.1g。
9.一种聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶，其特征在于，采用如权利要求1-8任一项所述的聚甲基丙烯酸-2-羟乙酯/N-乙烯基吡咯烷酮二元共聚水凝胶的制备方法制得。
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