CN112341641A - 一种双网络颗粒凝胶及其制备方法 - Google Patents
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Abstract
本发明公开了一种双网络颗粒凝胶及其制备方法,该颗粒凝胶包括第一重分子网络和第二重分子网络,第一重分子网络以葫芦脲为主体分子,以甲基紫精‑苯硼酸双官能团功能化的聚乙烯醇、萘酚功能化的羟乙基纤维素和萘酚功能化的超支化聚乙二醇二丙烯酸酯为客体分子;第二重分子网络包括超支化的聚乙二醇二丙烯酸酯交联网络。制备方法包括合成甲基紫精‑苯硼酸双官能团功能化的聚乙烯醇、萘酚功能化的羟乙基纤维素、萘酚功能化的超支化的聚乙二醇二丙烯酸酯;将前述三种产物混合形成预混合液,与葫芦脲进行超分子组装反应,通过凝胶反应制得双网络颗粒凝胶。本发明的颗粒凝胶微具有高强韧、剪切稀化、多重响应、自修复特性及生物相容性良好的特点。
Description
技术领域
本发明涉及一种水凝胶材料及其制备方法,尤其涉及一种双网络颗粒凝胶及其制备方法。
背景技术
颗粒凝胶是由微米级水凝胶粒子组成的一类新型颗粒材料,它不仅具备常规水凝胶含水量高、生物相容性好的特点,还呈现出颗粒材料独有的静力学和动力学特征。颗粒凝胶具有保护、传递和局部释放药物(小分子药物或生长因子)的能力,因此对于药物输送具有广阔的前景。同时颗粒凝胶现已用于生物制造生产复杂生物组织的体外或者可植入模型并也能够作为挤出式打印设备的生物墨水。
双网络水凝胶是一种新型的水凝胶材料,具有三维网络结构的高分子聚合物,其机械性能优越,具备较高的强度,可以承受高水平的拉伸和压缩变形。利用超分子作用和共价键作用形成的双网络水凝胶不但具有较高的强度而且具有剪切稀化、多重响应性和自修复特性。超分子作用是指分子间通过非共价键(氢键、配位键、范德华力、π-π堆积作用、静电作用和疏水作用)发生相互作用后形成具有有序和特定功能的化学体系。其中由于非共价键的可逆特性使得某种外界的刺激会促使超分子聚合物在结构和形态上发生可逆性的转变,同时为超分子聚合构建了一个具有简便与稳定的平台。与传统的高分子材料不同,超分子聚合物通过非共价键结合使其在自组装技术、结构和性能方面具有不同的特性。
发明内容
发明目的:本发明的第一个目的是提供一种具有高强韧、剪切稀化、多重响应性和自修复特性的双网络颗粒凝胶;
本发明的第二个目的是提供一种双网络颗粒凝胶的制备方法。
技术方案:本发明所述的双网络颗粒凝胶,包括第一重分子网络和第二重分子网络,所述第一重分子网络以葫芦脲为主体分子,以甲基紫精-苯硼酸双官能团功能化的聚乙烯醇、萘酚功能化的羟乙基纤维素和萘酚功能化的超支化聚乙二醇二丙烯酸酯为客体分子;所述第二重分子网络包括超支化的聚乙二醇二丙烯酸酯交联网络。
优选地,所述第一重分子网络和第二重分子网络相互穿插形成所述双网络颗粒凝胶;分子结构的第一重网络为以葫芦脲[8]为主体分子、甲基紫精苯硼酸双官能团化的聚乙烯醇和萘酚功能化的超支化高分子为客体分子构成,该超分子结构动态网络使的水凝胶具有含水量高、可剪切稀化、多重响应性、和自修复特性;分子结构的第二重网络为超支化高分子残留的自由基聚合交联形成的共价键网络,使得水凝胶具有高强度和高韧性的特征。
优选地,所述甲基紫精-苯硼酸为1-硼苄基-1'-甲基-[4,4'-联吡啶]-1,1'-溴化碘化二碘;所述1-硼苄基-1'-甲基-[4,4'-联吡啶]-1,1'-溴化碘化二碘选自1-(2-硼苄基)-1'-甲基-[4,4'-联吡啶]-1,1'-溴化碘化二碘、1-(3-硼苄基)-1'-甲基-[4,4'-联吡啶]-1,1'-溴化碘化二碘、1-(4-硼苄基)-1'-甲基-[4,4'-联吡啶]-1,1'-溴化碘化二碘中的至少一种。
上述的双网络颗粒凝胶的制备方法,包括以下步骤:
(1)制备甲基紫精-苯硼酸双官能团功能化的聚乙烯醇;
(2)制备萘酚功能化的羟乙基纤维素;
(3)制备萘酚功能化的超支化的聚乙二醇二丙烯酸酯;
(4)将步骤(1)、(2)、(3)的产物混合形成预混合液;
(5)将所述预混合溶液与葫芦脲进行超分子组装反应,并通过凝胶反应制得所述双网络颗粒凝胶。
优选地,所述步骤(3)具体包括:合成带双键的萘酚,将带双键的萘酚与聚乙二醇二丙烯酸酯进行ATRP活性聚合反应得到萘酚功能化的超支化聚乙二醇二丙烯酸酯。
优选地,所述步骤(1)具体包括:合成甲基紫精-苯硼酸,将甲基紫精-苯硼酸与PVA在碱性条件下形成硼酸酯键得到甲基紫精-苯硼酸功能化的聚乙烯醇溶液。
优选地,所述步骤(2)具体包括:将2-萘基异氰酸酯与羟乙基纤维素在无水条件下反应得到萘酚功能化的羟乙基纤维素。
优选地,步骤(4)中,所述预混合溶液中甲基紫精、萘酚和葫芦脲的摩尔比为1~3:1:1。
优选地,步骤(4)中,所述预混合溶液中甲基紫精及苯硼酸双官能团功能化的聚乙烯醇、萘酚功能化的羟乙基纤维素、萘酚功能化的超支化的聚乙二醇二丙烯酸酯的浓度比为2~6:0~2:2~20。
优选地,步骤(2)中,所述凝胶反应为悬浮聚合、微流控或膜乳化法。
优选地,在步骤(5)之后对所述双网络颗粒凝胶进行固化,得到强度增强的双网络颗粒凝胶。
有益效果:本发明与现有技术相比,取得如下显著效果:1、第一重网络的超分子主客体动态化学结构结合第二重网络的共价键交联结构,使得本发明的双网络颗粒凝胶不仅具有高强韧的力学性能、剪切变稀行为和自修复性能,并且具有多重刺激响应性能;2、水凝胶微球的结构使得双网络结构更加稳定;3、制备方法简单易行、所使用的材料具有良好的生物相容性。4、拓宽了自修复水凝胶材料的应用范围,有望应用于3D打印墨水、可穿戴的柔性电子器件、软体机器人、生物医学等领域。
附图说明
图1是本发明双网络颗粒凝胶形成机理图;
图2是合成的Np-HB-PEGDA核磁共振氢谱图;
图3是合成的HEC-Np核磁共振氢谱图;
图4是双网络水凝胶自修复性能的应力-应变曲线;
图5是采用微流控技术制备的具有单分散性的超分子凝胶微球。
具体实施方式
下面结合说明书附图对本发明作进一步详细描述。
实施例1
(1)甲基紫精-苯硼酸的合成:将10.0g 4,4′-联吡啶溶解在150mL二氯甲烷中,然后在搅拌下滴加5mL甲基碘的50mL二氯甲烷溶液,将所得混合物回流1h,粗产物通过抽滤收集,通过甲醇重结晶纯化产物,并用乙醚洗涤,得到4.49毫米黄色晶体,即产率为24%的1-甲基-4,4'-联吡啶二氨基碘化物。将0.894g 1-甲基-4,4'-联吡啶二氨基碘化物,0.645g 4(溴甲基)苯基硼酸和30mL N-N-二甲基甲酰胺加入两口烧瓶。将混合物置于80℃的条件下并以转速为500rpm的速率搅拌约48h,之后将混合物冷却至室温后,将烧瓶中的沉淀物过滤并用50mL丙酮和50mL二氯甲烷洗涤。最后将洗涤后的物质置于40℃的真空干燥箱中干燥48h,得到0.867g甲基紫精-苯硼酸,记为MV2+-苯硼酸。
(2)带双键萘酚的合成:将4.3251g 2-萘酚,2.5293g 2-[2-(2-氯乙氧基)乙氧基]乙醇、4.1463g碳酸钾及4.89g碘化钾加入到规格为250mL的烧瓶中后,再加入150mL乙腈,搅拌至完全溶解,用盐水塞密封,并缠上封口膜;将氩气通入混合物中,通过鼓泡的方式将烧瓶中的空气置换为氩气。将内部充满氩气的混合物置于70℃的环境中并以转速为300rpm的速率搅拌反应36h后,停止反应,冷却至室温,减压干燥。用硅胶柱层析的方法纯化产物,第一次用己烷洗脱,第二次用体积比为2:3己烷及乙酸乙酯混合液洗脱。收集产物,减压干燥,得到第一步合成产物,为公式(1)中的a。
取2.0016g第一步合成产物a和1.5mL三乙胺加入规格为100mL烧杯中后,再加入50mL乙醚并搅拌至完全溶解,放入低温槽中冷却至-20℃。将0.8mL甲基丙烯酰氯溶于5mL乙醚中,逐滴缓慢滴加至烧瓶中并搅拌,滴加速度100μL/min。在室温条件下搅拌24h。过滤除去三乙基氯化铵盐,减压除去溶剂。用硅胶柱层析的方法纯化产物,用体积比为4:1的己烷及乙酸乙酯混合液洗脱。收集产物,减压干燥,得到带双键萘酚,为公式(1)的b。
(3)HEC-Np的合成:量取75mL无水N-甲基吡咯烷酮于规格为250mL烧瓶中加热至110℃,加入0.4998g羟乙基纤维素,在110℃条件下以400rpm的速度搅拌6h至羟乙基纤维素完全溶解。停止加热,将烧瓶从油浴中取出,继续搅拌自然冷却至室温。加入14.9mg酚醛-异氰酸酯Np-NCO和50μL二月桂酸二丁基锡,在室温下搅拌24h,300mL丙酮沉淀3次,收集沉淀40℃下真空干燥24小时得到萘酚功能化的羟乙基纤维素,即HEC-Np。如公式(2)所示,通过图中的化学反应合成了带有萘酚官能团的羟乙基纤维素。
(4)Np-HB-PEGDA的合成:将11.5g平均Mn为575g·mol-1的PEGDA单体和2.0633g带双键萘酚加入到烧杯中,再加入150mL丁酮后,搅拌至完全溶解,之后获得单体浓度为0.4mol·L-1的溶液。然后将0.1839g偶氮二异丁腈和0.2372g二硫化四乙基秋兰姆加入烧瓶中,用盐水塞将烧瓶密封,并缠上封口膜,将氩气通入混合物中鼓泡1h。将油浴预热至70℃后,将充满氩气的混合物置于70℃下进行聚合并将转速设置为300rpm。在反应6h后停止反应,通入空气,将混合物冷却至室温。用体积比为1:2的己烷及乙醚混合溶液沉淀三次来纯化聚合物,其中己烷及乙醚混合溶液优选在冰箱中预冷6h;然后减压干燥产物,在真空烘箱中干燥48h以除去残留的溶剂,得到萘酚功能化的超支化的聚乙二醇二丙烯酸酯,即Np-HB-PEGDA。如公式(3)所示,通过热引发的方式生成链转移剂CTA,然后在链转移剂CTA的作用下,将功能性带双键萘酚接枝到聚乙二醇二丙烯酸酯PEGDA上,生成萘酚功能化的超支化的聚乙二醇二丙烯酸酯Np-HB-PEGDA。
(5)配制质量分数为6wt%的PVA的溶液,将溶液的pH调至碱性。配制10mM MV2+-苯硼酸、3mM葫芦脲混合溶液。将6wt%的PVA的溶液与MV2+-苯硼酸、葫芦脲CB[8]的溶液体积比1:1混合,得到混合溶液A。配制5%Np-HB-PEGDA的溶液,并加入0.01%光引发剂,得到混合溶液B。
使用PDMS芯片,以含2%的道康宁0749的硅油为连续相,以混合溶液A和B为分散相,调节流速,混合溶液A和B的流速比为1:1,得到1μm~1000μm范围的超分子水凝胶微球。
(6)将超分子水凝胶微球置于365nm的光照下固化,用正己烷洗去乳化剂和硅油,并分散到少量纯水中,经过离心对微球悬浮液进行浓缩,获得离散态的物质体系即为双网络颗粒凝胶。
图1中的(a)反应了功能性高分子构筑单元的结构,其中ⅰ反应了紫精功能化PVA的形成以及紫精与主体分子葫芦脲CB[8]的主客体组装;ⅱ和ⅲ分别表示功能性高分子构筑单元HEC-Np和Np-HB-PEGDA的化学结构以及示意图;图1中的(b)反应了分子超分子水凝胶的成胶机理:将修饰的支化高分子、主体分子葫芦脲CB[8]和PVA混合通过微流控或者膜乳化的方法在紫外光照射下制成超分子凝胶微球。
从图2可以看出合成了带有萘酚官能团的多烯烃支化聚合物。化学位移在6附近为双键峰,化学位移在6-8之间为萘酚的特征峰。从图3可以看出合成了带有萘酚官能团的羟乙基纤维素,化学位移在7.6附近为萘酚的特征峰。
从图4可以看出本发明合成的超分子水凝胶具有良好的自愈合性能。
图5为制备的单分散超分子凝胶微球:图5(a)为凝胶微球分散在氟油7500连续相中的显微图片,图5(b)为将凝胶微球从油中洗出置于微量水中制备得到的超分子凝胶颗粒材料。
实施例2
基本步骤与实施例1相同,与实施例1不同的是,混合溶液A和B的混合液中甲基紫精、萘酚和葫芦脲的摩尔比为1:1:1。
实施例3
基本步骤与实施例1相同,与实施例1不同的是,混合溶液A和B的混合液中甲基紫精、萘酚和葫芦脲的摩尔比为3:1:1。
实施例4
基本步骤与实施例1相同,与实施例1不同的是,所述预混合溶液中甲基紫精及苯硼酸双官能团功能化的聚乙烯醇、萘酚功能化的羟乙基纤维素、萘酚功能化的超支化的聚乙二醇二丙烯酸酯的浓度比为2:2:20。
实施例5
基本步骤与实施例1相同,与实施例1不同的是,所述预混合溶液中甲基紫精及苯硼酸双官能团功能化的聚乙烯醇、萘酚功能化的羟乙基纤维素、萘酚功能化的超支化的聚乙二醇二丙烯酸酯的浓度比为6:2:2。
实施例6
基本步骤与实施例1相同,与实施例1不同的是,所述预混合溶液中甲基紫精及苯硼酸双官能团功能化的聚乙烯醇、萘酚功能化的羟乙基纤维素、萘酚功能化的超支化的聚乙二醇二丙烯酸酯的浓度比为2:0:2。
Claims (10)
1.一种双网络颗粒凝胶,其特征在于,所述双网络颗粒凝胶包括第一重分子网络和第二重分子网络,所述第一重分子网络以葫芦脲为主体分子,以甲基紫精-苯硼酸双官能团功能化的聚乙烯醇、萘酚功能化的羟乙基纤维素和萘酚功能化的超支化聚乙二醇二丙烯酸酯为客体分子;所述第二重分子网络包括超支化的聚乙二醇二丙烯酸酯交联网络。
2.根据权利要求1所述的双网络颗粒凝胶,其特征在于,所述甲基紫精-苯硼酸为1-硼苄基-1'-甲基-[4,4'-联吡啶]-1,1'-溴化碘化二碘;所述1-硼苄基-1'-甲基-[4,4'-联吡啶]-1,1'-溴化碘化二碘选自1-(2-硼苄基)-1'-甲基-[4,4'-联吡啶]-1,1'-溴化碘化二碘、1-(3-硼苄基)-1'-甲基-[4,4'-联吡啶]-1,1'-溴化碘化二碘、1-(4-硼苄基)-1'-甲基-[4,4'-联吡啶]-1,1'-溴化碘化二碘中的至少一种。
3.一种权利要求1所述的双网络颗粒凝胶的制备方法,其特征在于,包括以下步骤:
(1)制备甲基紫精-苯硼酸双官能团功能化的聚乙烯醇;
(2)制备萘酚功能化的羟乙基纤维素;
(3)制备萘酚功能化的超支化的聚乙二醇二丙烯酸酯;
(4)将步骤(1)、(2)、(3)的产物混合形成预混合液;
(5)将所述预混合溶液与葫芦脲进行超分子组装反应,并通过凝胶反应制得所述双网络颗粒凝胶。
4.根据权利要求3所述的双网络颗粒凝胶的制备方法,其特征在于,所述步骤(3)具体包括:合成带双键的萘酚,将带双键的萘酚与聚乙二醇二丙烯酸酯进行ATRP活性聚合反应得到萘酚功能化的超支化聚乙二醇二丙烯酸酯。
5.根据权利要求3所述的双网络颗粒凝胶的制备方法,其特征在于,所述步骤(1)具体包括:合成甲基紫精-苯硼酸,将甲基紫精-苯硼酸与PVA在碱性条件下形成硼酸酯键得到甲基紫精-苯硼酸功能化的聚乙烯醇溶液。
6.根据权利要求3所述的双网络颗粒凝胶的制备方法,其特征在于,所述步骤(2)具体包括:将2-萘基异氰酸酯与羟乙基纤维素在无水条件下反应得到萘酚功能化的羟乙基纤维素。
7.根据权利要求3所述的双网络颗粒凝胶的制备方法,其特征在于,步骤(4)中,所述预混合溶液中甲基紫精、萘酚和葫芦脲的摩尔比为1~3:1:1。
8.根据权利要求3所述的双网络颗粒凝胶的制备方法,其特征在于,步骤(4)中,所述预混合溶液中甲基紫精及苯硼酸双官能团功能化的聚乙烯醇、萘酚功能化的羟乙基纤维素、萘酚功能化的超支化的聚乙二醇二丙烯酸酯的浓度比为2~6:0~2:2~20。
9.根据权利要求3所述的双网络颗粒凝胶的制备方法,其特征在于,步骤(2)中,所述凝胶反应为悬浮聚合、微流控或膜乳化法。
10.根据权利要求3所述的双网络颗粒凝胶的制备方法,其特征在于,在步骤(5)之后对所述双网络颗粒凝胶进行固化,得到强度增强的双网络颗粒凝胶。
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