CN111978507A - 一种pH响应变色聚氨酯水凝胶的制备方法 - Google Patents

一种pH响应变色聚氨酯水凝胶的制备方法 Download PDF

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CN111978507A
CN111978507A CN202010698918.3A CN202010698918A CN111978507A CN 111978507 A CN111978507 A CN 111978507A CN 202010698918 A CN202010698918 A CN 202010698918A CN 111978507 A CN111978507 A CN 111978507A
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田赛琦
丁昇
朱一凡
陈银燕
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Abstract

本发明提供一种pH响应变色聚氨酯水凝胶的制备方法。该方法在聚氨酯水凝胶的合成阶段添加兼具pH响应变色和抑菌作用的花青素。该聚氨酯水凝胶具有良好的pH响应性，可随pH的改变呈现不同的颜色，且在15～30s内颜色达到稳定，对环境酸碱响应十分灵敏，可用于伤口敷料，通过观察颜色变化监测伤口pH值，从而了解伤口的愈合程度及是否发生感染。

Description

一种pH响应变色聚氨酯水凝胶的制备方法
技术领域
本发明涉及高分子材料制备技术领域，尤其是一种pH响应变色聚氨酯水凝胶的制备方法。
背景技术
皮肤是身体最重要的器官，也是人体和外部环境之间最重要的屏障，任何形式的损伤都会导致体内平衡的失调，如果修复速度缓慢、缺乏充足水分、电解质紊乱和感染可能会导致伤口愈合时间延长，严重残疾，甚至死亡。故需要适当的伤口敷料来保护皮肤伤口防止进一步受损，并加速愈合和控制释放药物。
人体伤口愈合的过程中，皮肤的pH值呈现动态变化。研究表明，健康皮肤和已愈合的伤口皮肤的pH值在5～6，呈弱酸性，发炎阶段伤口的pH值偏碱性，通常大于7。如果在伤口愈合过程中酸碱度升高，偏向碱性，则说明可能发生了感染。整个愈合过程中，pH应该是由弱酸转向碱性再回到弱酸性，因此，通过监测伤口pH值，可了解伤口的愈合程度及是否发生感染。
聚氨酯水凝胶兼具优异的机械性能和出色的生物相容性，作为医用创面敷料已经得到广泛应用。设计并制备出pH响应变色的聚氨酯水凝胶，并将其用于伤口敷料，使其一定程度上具有抗菌和变色的指示的双重功能，具有十分重要的现实意义。
发明内容
本发明的目的是提供一种pH响应变色聚氨酯水凝胶的制备方法，将兼具pH响应变色和对细菌、真菌有良好抑制作用的花青素添加进水凝胶中，从而赋予聚氨酯水凝胶抗菌和变色的指示的双重功能。
为实现上述目的，本发明提供了一种pH响应变色聚氨酯水凝胶的制备方法，包括以下步骤，
步骤(1)pH响应变色聚氨酯乳液的制备，将设置在烘干条件下的真空烘箱中烘干过夜的聚合物二元醇、二异氰酸酯、小分子二元醇扩链剂和催化剂加入反应容器，在氮气气氛保护下持续搅拌，于65-85℃下反应2-3h，加入交联剂，保持65-85℃继续反应1h，继续加入溶剂溶解的亲水扩链剂和花青素，维持体系温度在65-85℃继续搅拌2-3h，降温至40℃后加入三乙胺，在高剪切力作用下，加入去离子水，高速乳化后，继续搅拌2-3h，减压蒸馏脱去溶剂，制得pH响应变色聚氨酯乳液，其中各组分的用量比为，聚合物二元醇80-100份、二异氰酸酯40-50份、小分子二元醇扩链剂3-5份、催化剂0.05-0.2份、溶剂10-20份、亲水扩链剂6-7份、花青素0.7-0.8份、三乙胺4-6份、去离子水280-350份；
步骤(2)pH响应变色聚氨酯水凝胶的制备，取20份步骤(1)制备好的pH响应变色聚氨酯乳液置于成膜板中，室温下空气干燥72h，取出成膜，再放入60℃烘箱中干燥，至薄膜质量不再变化，得到干凝胶，将干凝胶泡在去离子水中溶胀7天，每隔12h换水一次，制得pH响应变色聚氨酯水凝胶。
作为本发明的进一步设置，步骤(1)中所述的聚合物二元醇为数均分子量为1000-2000的聚丙二醇、聚乙二醇或聚四氢呋喃二醇中的任一种或其组合。
作为本发明的进一步设置，步骤(1)中所述的二异氰酸酯为异佛二酮二异氰酸酯、2,4-甲苯二异氰酸酯、1,6-己基二异氰酸酯、二苯基甲烷二异氰酸酯或4,4'-二环己基甲烷二异氰酸酯中的任一种。
作为本发明的进一步设置，步骤(1)中所述的小分子二元醇扩链剂为乙二醇、1,3-丙二醇、1,4-丁二醇、新戊二醇、1,6-己二醇、或一缩二乙二醇中的任一种。
作为本发明的进一步设置，步骤(1)中所述的催化剂为新癸酸铋、月桂酸铋、异辛酸铋、环烷酸铋、双二甲氨基乙基醚或二甲基环己胺中的任一种。
作为本发明的进一步设置，步骤(1)中所述的有机溶剂为丙酮或丁酮的任一种。
作为本发明的进一步设置，步骤(1)中所述的亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸中的任一种。
作为本发明的进一步设置，步骤(1)中所述的交联剂为三羟甲基丙烷或蓖麻油中的任一种。
作为本发明的进一步设置，步骤(1)中所述的烘干条件为120℃和0.1atm。
这样设置的有益效果是，本发明所提供的pH响应变色聚氨酯水凝胶具有优异的机械性能及生物相容性，花青素的引入赋予水凝胶抑菌性，能很好的阻挡细菌的侵入；这里的花青素是自然界一类广泛存在于植物中的水溶性天然色素，花青素对细菌和真菌具有良好的抑制作用。此外，在不同pH条件下，花青素染料的化学结构发生自发变化。当pH值为4～5时，花青素以红黄色熔盐正离子与蓝色醌型碱的形式存在，呈蓝紫色。当pH值为6～7时，部分红黄色熔盐阳离子转化为无色假醇基，蓝色为主色。随着pH值的持续升高，浅黄色查尔酮缓慢形成。结合蓝色醌碱，海绵呈墨绿色、军绿色。颜色变化可在15～30s内达到稳定，对环境酸碱响应十分灵敏。同时本发明所采用的花青素本身对人体无害，且具有良好的pH响应性，在人体体液变化范围内的颜色变化十分明显，在15～30s内颜色达到稳定，对环境酸碱响应十分灵敏；本发明所提供的pH响应变色聚氨酯水凝胶可通过观察颜色变化监测伤口pH值，从而了解伤口的愈合程度及是否发生感染。
附图说明
图1为本发明实施例的变色机理图。
具体实施方式
本发明一种pH响应变色聚氨酯水凝胶的制备方法的第一个实施方式包括以下步骤，步骤(1)pH响应变色聚氨酯乳液的制备，将100份数均分子量为2000的聚丙二醇(120℃，0.1atm真空烘箱烘干过夜)、50份4,4'-二环己基甲烷二异氰酸酯、3份1,4-丁二醇和0.2份新癸酸铋催化剂加入反应容器，在持续搅拌和氮气气氛保护下，升温至85℃反应2h，加入0.2份三羟甲基丙烷，保持85℃继续反应1h，加入20份丙酮溶解的7份二羟甲基丙酸和0.8份花青素，维持在85℃继续反应2h，然后加入6份三乙胺，在高剪切力作用下，加入350份去离子水，高速乳化2h，即得pH响应变色聚氨酯乳液；
步骤(2)pH响应变色聚氨酯水凝胶的制备，取20份步骤(1)制备好的聚氨酯乳液置于成膜板中，室温下空气干燥72h，取出成膜，再放入60℃烘箱中干燥，至薄膜质量不再变化，得到干凝胶。将干凝胶泡在去离子水中溶胀7天，每隔12h换水一次，得pH响应变色聚氨酯水凝胶。
本发明一种pH响应变色聚氨酯水凝胶的制备方法的第二个实施方式包括以下步骤，步骤(1)pH响应变色聚氨酯乳液的制备，将40份数均分子量为1000的聚乙二醇、40份数均分子量为1000的聚四氢呋喃二醇(120℃，0.1atm真空烘箱烘干过夜)、40份2,4-甲苯二异氰酸酯、4份乙二醇和0.05份异辛酸铋催化剂加入反应容器，在持续搅拌和氮气气氛保护下，升温至65℃反应2.5h，加入2份蓖麻油，保持65℃继续反应1h，加入10份丁酮溶解的6份二羟甲基丁酸和0.7份花青素，维持在65℃继续反应3h，然后加入4份三乙胺，在高剪切力作用下，加入280份去离子水，高速乳化2.5h，即得pH响应变色聚氨酯乳液；
步骤(2)pH响应变色聚氨酯水凝胶的制备，取20份步骤(1)制备好的聚氨酯乳液置于成膜板中，室温下空气干燥72h，取出成膜，再放入60℃烘箱中干燥，至薄膜质量不再变化，得到干凝胶。将干凝胶泡在去离子水中溶胀7天，每隔12h换水一次，得pH响应变色聚氨酯水凝胶。
本发明一种pH响应变色聚氨酯水凝胶的制备方法的第二个实施方式包括以下步骤，步骤(1)pH响应变色聚氨酯乳液的制备，将90份数均分子量为2000的聚四氢呋喃二醇(120℃，0.1atm真空烘箱烘干过夜)、45份异佛二酮二异氰酸酯、5份一缩二乙二醇和0.1份二甲基环己胺催化剂加入反应容器，在持续搅拌和氮气气氛保护下，升温至80℃反应3h，加入0.4份三羟甲基丙烷，保持80℃继续反应1h，向所得预聚体中加入15份丙酮的6.5份二羟甲基丙酸和0.75份花青素，维持在80℃继续反应2.5h，然后加入5份三乙胺中和预聚体，在高剪切力作用下，加入330份去离子水，高速乳化3h，即得pH响应变色聚氨酯乳液；
步骤(2)pH响应变色聚氨酯水凝胶的制备，取20份步骤(1)制备好的聚氨酯乳液置于成膜板中，室温下空气干燥72h，取出成膜，再放入60℃烘箱中干燥，至薄膜质量不再变化，得到干凝胶。将干凝胶泡在去离子水中溶胀7天，每隔12h换水一次，得pH响应变色聚氨酯水凝胶。
以上实例，只是本发明优选地具体实例的一种，本领域技术人员在本发明技术方案范围内进行的通常变化和替换都包含在本发明的保护范围内。

Claims (9)

1.一种pH响应变色聚氨酯水凝胶的制备方法，其特征在于：包括以下步骤，
步骤(1)pH响应变色聚氨酯乳液的制备，将设置在烘干条件下的真空烘箱中烘干过夜的聚合物二元醇、二异氰酸酯、小分子二元醇扩链剂和催化剂加入反应容器，在氮气气氛保护下持续搅拌，于65-85℃下反应2-3h，加入交联剂，保持65-85℃继续反应1h，继续加入溶剂溶解的亲水扩链剂和花青素，维持体系温度在65-85℃继续搅拌2-3h，降温至40℃后加入三乙胺，在高剪切力作用下，加入去离子水，高速乳化后，继续搅拌2-3h，减压蒸馏脱去溶剂，制得pH响应变色聚氨酯乳液，其中各组分的用量比为，聚合物二元醇80-100份、二异氰酸酯40-50份、小分子二元醇扩链剂3-5份、催化剂0.05-0.2份、溶剂10-20份、亲水扩链剂6-7份、花青素0.7-0.8份、三乙胺4-6份、去离子水280-350份；
步骤(2)pH响应变色聚氨酯水凝胶的制备，取20份步骤(1)制备好的pH响应变色聚氨酯乳液置于成膜板中，室温下空气干燥72h，取出成膜，再放入60℃烘箱中干燥，至薄膜质量不再变化，得到干凝胶，将干凝胶泡在去离子水中溶胀7天，每隔12h换水一次，制得pH响应变色聚氨酯水凝胶。
2.根据权利要求1所述的一种pH响应变色聚氨酯水凝胶的制备方法，其特征在于：步骤(1)中所述的聚合物二元醇为数均分子量为1000-2000的聚丙二醇、聚乙二醇或聚四氢呋喃二醇中的任一种或其组合。
3.根据权利要求1所述的一种pH响应变色聚氨酯水凝胶的制备方法，其特征在于：步骤(1)中所述的二异氰酸酯为异佛二酮二异氰酸酯、2,4-甲苯二异氰酸酯、1,6-己基二异氰酸酯、二苯基甲烷二异氰酸酯或4,4'-二环己基甲烷二异氰酸酯中的任一种。
4.根据权利要求1所述的一种pH响应变色聚氨酯水凝胶的制备方法，其特征在于：步骤(1)中所述的小分子二元醇扩链剂为乙二醇、1,3-丙二醇、1,4-丁二醇、新戊二醇、1,6-己二醇、或一缩二乙二醇中的任一种。
5.根据权利要求1所述的一种pH响应变色聚氨酯水凝胶的制备方法，其特征在于：步骤(1)中所述的催化剂为新癸酸铋、月桂酸铋、异辛酸铋、环烷酸铋、双二甲氨基乙基醚或二甲基环己胺中的任一种。
6.根据权利要求1所述的一种pH响应变色聚氨酯水凝胶的制备方法，其特征在于：步骤(1)中所述的有机溶剂为丙酮或丁酮的任一种。
7.根据权利要求1所述的一种pH响应变色聚氨酯水凝胶的制备方法，其特征在于：步骤(1)中所述的亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸中的任一种。
8.根据权利要求1所述的一种pH响应变色聚氨酯水凝胶的制备方法，其特征在于：步骤(1)中所述的交联剂为三羟甲基丙烷或蓖麻油中的任一种。
9.根据权利要求1所述的一种pH响应变色聚氨酯水凝胶的制备方法，其特征在于：步骤(1)中所述的烘干条件为120℃和0.1atm。
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