CN112300360A - 一种两亲性树枝状共聚物的制备 - Google Patents
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Abstract
本发明提供了一种具有良好的生物相容性的两亲性树枝状嵌段共聚物的制备方法。所述的两亲性树枝状嵌段共聚物首先由聚四氢呋喃醚二元醇、三羟甲基丙烷和异佛尔酮二异氰酸酯聚合制备了异氰酸基团官能化的预聚体嵌段，再加入亲水性的聚乙二醇单甲氧基醚反应制得。将上述共聚物和疏水性药物在溶液中溶解形成混合溶液，再避光透析制得粒径为27～35nm的纳米胶束。本发明制备方法简单、高效可控，开发提供了一种新的生物相容性良好的纳米载体，具有良好的应用前景。
Description
技术领域
本发明属于生物医用高分子聚合物材料技术领域，特别涉及一种两亲性树枝状嵌段共聚物的结构及制备方法。
背景技术
最有效的抗癌药物例如紫杉醇，阿霉素，喜树碱等是癌症化学疗法的重要组成部分。尽管如此，它们在化疗中存在着一系列显著的缺点例如严重的心脏毒性和多重耐药性。通过选择精确的聚合物纳米载体来递送化学治疗药物来治疗癌症一直是不懈的科学挑战。因此，开发纳米载体在生物医学领域的多功能特性仍然是一项紧迫的任务。最近的文献表明多功能纳米粒子可能是癌症治疗的非常有前途的工具。这些纳米体系在人体中形成精确的生物通道，该通道不仅可以获取诊断图像，还以明确有效的方式将治疗剂量的药物输送给患者。目前为止，已经报道了大量聚合物用于聚合物纳米载体的开发，以用于负载难溶性药物。由于具有良好的生物相容性且聚氨酯材料通过化学修饰的亲水性表面能够减少蛋白质吸附以及血小板的粘附是一种极具潜力的生物医药载体。
在生物医药纳米材料的开发中，生物相容性，即生命体组织对非活性材料产生反应的一种性能，仍然是主要的挑战。生物惰性材料是不会释放有毒或是发炎物质的材料，也不会触发物质与生物组织的相互作用。所以将这种材料引入到表面不会引发异物反应。为了构建生物惰性的表面，最常将掺入的为聚乙二醇类材料。
本发明公开了一种两亲性树枝状嵌段共聚物的结构及制备方法。采用嵌段共聚的合成方式，在预聚体阶段，三羟甲基丙烷和聚四氢呋喃醚的活泼氢与异氰酸酯基团进行加成共聚反应，由于三羟甲基丙烷的多支链存在形成树枝状的疏水结构；再引入聚乙二醇单甲氧基醚作为亲水结构形成一种独特的两亲性树枝状嵌段共聚物。
发明内容
本发明的目的是为了构建一种能够在正常生理环境下稳定存在的两亲性树枝状嵌段共聚物。因此本发明提供了一种两亲性树枝状嵌段共聚物的制备及应用。
本发明技术方案如下：
1、为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种两亲性树枝状嵌段共聚物。
一种两亲性树枝状嵌段共聚物，所述两亲性树枝状嵌段共聚物包括亲水链段和疏水链段，具体如下式所示结构：
其中：n’为5～20，，n为20～50。
2、一种的两亲性树枝状嵌段共聚物的制备方法，包括以下步骤：
(1)制备异氰酸基团官能化的嵌段：在三口烧瓶中加入一定比例的异佛尔酮二异氰酸酯、聚四氢呋喃醚二元醇、三羟甲基丙烷、二月桂酸二丁基锡于溶剂中，搅拌并在70～85℃下反应，反应4h得到异氰酸基团官能化的嵌段预聚体。
(2)制备两亲性树枝状嵌段共聚物：在步骤(1)制得的异氰酸基团官能化的嵌段预聚体中加入称量好的聚乙二醇单甲氧基醚，反应温度准确控制在70～85℃，转速控制在每分钟300～500转，反应3h后，温度降到室温后取出，用-15℃的正戊烷沉淀出反应物，然后35℃真空干燥24h，干燥后得到上述的两亲性树枝状嵌段共聚物。
3、根据步骤2所述的制备方法，还在于：
所述步骤(1)中反应物的摩尔份数配方如下：
| 原料 | 摩尔数 |
| 异佛尔酮二异氰酸酯 | 2～4份 |
| 聚四氢呋喃醚二元醇 | 2～3份 |
| 三羟甲基丙烷 | 0.05～0.1份 |
| 二月桂酸二丁基锡 | 0.03～0.1份 |
| 丙酮 | 50～60份 |
所述步骤(2)中反应物的摩尔份数配方如下：
| 原料 | 摩尔数 |
| 预聚体 | 1份 |
| 聚乙二醇单甲氧基醚 | 2份 |
| 丙酮 | 50～60份 |
附图说明
图1为实施例1中两亲性树枝状嵌段共聚物的合成路线。
图2为实施例1中两亲性树枝状嵌段共聚物的核磁氢谱，溶剂为氘代氯仿(CDCl3)。
图3为实施例1中两亲性树枝状嵌段共聚物的红外谱图。
具体实施方式
下面通过实施例对本发明技术方案实施方式予以说明，但又不局限于以下实施例。
下列实施例中的试剂均可从商业渠道获得。
实施例1：
(1)合成异氰酸基团官能化的嵌段预聚体
取100mL的干燥三口烧瓶，依次加入聚四氢呋喃醚二元醇(2g，2mmol)、三羟甲基丙烷(13.4mg，0.1mmol)、异佛尔酮二异氰酸酯(0.67g，3mmol)、二月桂酸二丁基锡(0.1g，0.16mmol)和50mL丙酮，80℃水浴恒温加热，搅拌速度控制在每分钟300转，反应5h得到异氰酸基团官能化的预聚体。
(2)合成两亲性树枝状嵌段共聚物
在(1)合成的异氰酸基团官能化的嵌段预聚体中加入聚乙二醇单甲氧基醚(2g，1mmol)，30mL丙酮，80℃水浴恒温加热，搅拌速度控制在每分钟300转，反应时间为3h，降到室温后取出，在室温下缓慢滴加到-15℃正戊烷中沉淀，35℃下真空干燥24h，得到两亲性树枝嵌段共聚物。
实施例2：
(1)合成异氰酸基团官能化的嵌段预聚体
取100mL的干燥三口烧瓶，依次加入聚四氢呋喃醚二元醇(2g，2mmol)、三羟甲基丙烷(26.8mg，0.2mmol)、异佛尔酮二异氰酸酯(0.67g，3mmol)、二月桂酸二丁基锡(0.1g，0.16mmol)和50mL丙酮，80℃水浴恒温加热，搅拌速度控制在每分钟300转，反应5h得到异氰酸基团官能化的预聚体。
(2)合成两亲性树枝状嵌段共聚物
在(1)合成的异氰酸基团官能化的嵌段预聚体中加入聚乙二醇单甲氧基醚(2g，1mmol)，30mL丙酮，80℃水浴恒温加热，搅拌速度控制在每分钟300转，反应时间为3h，降到室温后取出，在室温下缓慢滴加到-15℃正戊烷中沉淀，35℃下真空干燥24h，得到两亲性树枝嵌段共聚物。
实施例3：
(1)合成异氰酸基团官能化的嵌段预聚体
取100mL的干燥三口烧瓶，依次加入聚四氢呋喃醚二元醇(2g，2mmol)、三羟甲基丙烷(40.2mg，0.3mmol)、异佛尔酮二异氰酸酯(0.67g，3mmol)、二月桂酸二丁基锡(0.1g，0.16mmol)和50mL丙酮，80℃水浴恒温加热，搅拌速度控制在每分钟300转，反应5h得到异氰酸基团官能化的预聚体。
(2)合成两亲性树枝状嵌段共聚物
在(1)合成的异氰酸基团官能化的嵌段预聚体中加入聚乙二醇单甲氧基醚(2g，1mmol)，30mL丙酮，80℃水浴恒温加热，搅拌速度控制在每分钟300转，反应时间为3h，降到室温后取出，在室温下缓慢滴加到-15℃正戊烷中沉淀，35℃下真空干燥24h，得到两亲性树枝嵌段共聚物。
Claims (6)
1.一种两亲性树枝状嵌段共聚物，其特征在于：两亲性树枝状嵌段共聚物包括疏水嵌段和亲水嵌段，结构式如下：
其中：n’为5～20，，n为20～50；
R为异佛尔酮二异氰酸酯，甲苯-2,4-二异氰酸酯，六亚甲基二异氰酸酯中的至少一种。
2.一种权利要求1所述的两亲性树枝状嵌段共聚物的制备方法，其特征在于包括以下步骤:
(1)制备异氰酸基团官能化的嵌段：在三口烧瓶中加入一定比例的异佛尔酮二异氰酸酯、聚四氢呋喃醚二元醇、三羟甲基丙烷、二月桂酸二丁基锡于溶剂中，搅拌并加热反应，反应一段时间得到异氰酸基团官能化的嵌段预聚体。
(2)制备两亲性树枝状嵌段共聚物：在步骤(1)制得的异氰酸基团官能化的嵌段预聚体中加入称量好的聚乙二醇单甲氧基醚，在溶剂中搅拌加热反应，降温后取出，用极性较小的溶剂沉淀出产物，然后在真空中干燥24h，干燥后得到上述的两亲性树枝状嵌段共聚物。
3.根据权利要求2所述的两亲性树枝状嵌段共聚物的制备方法，其特征在于：
所述步骤(1)中反应物的摩尔份数配方如下：
异佛尔酮二异氰酸酯 2～4份
聚四氢呋喃醚二元醇 2～3份
三羟甲基丙烷 0.05～0.1份
二月桂酸二丁基锡 0.03～0.1份
丙酮 40～60份
所述步骤(2)中反应物的摩尔份数配方如下：
预聚体 1份
聚乙二醇单甲氧基醚 2份
丙酮 40～60份。
4.根据权利要求2所述的两亲性树枝状嵌段共聚物的制备方法，其特征在于：步骤(1)中所述的加热反应指加热到70～85℃，反应时间为4～6h，所述溶剂指丙酮，甲苯中的至少一种。
5.根据权利要求2所述的两亲性树枝状嵌段共聚物的制备方法，其特征在于：步骤(2)中所述的反应的时间为3-5h，真空干燥的温度范围在25～35℃。
6.根据权利要求2所述的两亲性树枝状嵌段共聚物的制备方法，其特征在于：步骤(2)中所述的沉淀剂是指正戊烷，正己烷中的至少一种。所述的沉淀剂的温度范围是-15～-20℃。
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| CN115403730B (zh) * | 2022-10-13 | 2023-06-27 | 江苏四新界面剂科技有限公司 | 一种食品白油乳化剂及其制备方法 |
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