CN108169176A - 一种测定不同温度两亲性嵌段共聚物临界胶束浓度的方法 - Google Patents
一种测定不同温度两亲性嵌段共聚物临界胶束浓度的方法 Download PDFInfo
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Abstract
本发明涉及一种测定不同温度两亲性嵌段共聚物临界胶束浓度的方法,包括:(1)将样品放入动态激光光散射仪样品池中检测;(2)将不同浓度的聚合物溶液的光散射强度与对应的浓度作图。本发明使用带有控温系统的动态激光光散射仪测定聚合物的临界胶束浓度,因此可以不受外界环境温度干扰,可测定控温系统温度范围内任一特定温度的临界胶束浓度,这是其他测试临界胶束浓度的方法很难做到的;本发明操作简单,快速灵敏,可以准确确定两亲性嵌段共聚物临界胶束浓度。
Description
技术领域
本发明属于临界胶束浓度检测方法领域,特别涉及一种测定不同温度两亲性嵌段共聚物临界胶束浓度的方法。
背景技术
两亲性嵌段共聚物在生物医药方面具有重要的应用前景,如用于药物控制释放,靶向给药的载体,其作为药物载体,具有生物相容性好,胶束载体内外稳定,对溶解度小的药物有增溶作用等优点。
两亲性嵌段共聚物就是不同的链段对溶剂具有不同的亲和性,即一部分亲水,而另一部分亲油,所以也被称为高分子表面活性。和小分子表面活性剂类似,在水溶液中,两亲性嵌段聚合物由于亲疏水变化可以自组装形成胶束,相对于小分子表面活性剂胶束,两亲性嵌段聚合物胶束具有较低的临界胶束浓度和较慢的胶束-单分子交换速率。准确测定两亲性嵌段聚合物的临界胶束浓度对于研究其自组装及其对后续应用具有非常重要的意义,因此找到一种快速精确测量其临界胶束浓度的方法很有意义。
目前测定两亲性嵌段共聚物临界胶束浓度最常用的方法是荧光测定法,基于荧光探针在临界胶束浓度前后明显不同的荧光性质从而得到临界胶束浓度,但由于很难找到适合的荧光探针,并且测定易受外界温度条件的影响,该方法具有一定的局限性。因此,有必要找到一种方法快速准确的测定不同温度两亲性嵌段共聚物临界胶束浓度的方法。
发明内容
本发明所要解决的技术问题是提供一种测定不同温度两亲性嵌段共聚物临界胶束浓度的方法,该方法操作简单,快速灵敏,结果准确,使用带有控温系统的动态激光光散射仪测定聚合物的临界胶束浓度,可以不受外界环境温度干扰,可测定控温系统温度范围内任一特定温度的临界胶束浓度,这是其他测试临界胶束浓度的方法很难做到的。
本发明利用带有温控装置的动态激光光散射仪可测定不同温度下两亲性嵌段共聚物临界胶束浓度。
本发明的一种测定不同温度两亲性嵌段共聚物临界胶束浓度的方法,具体步骤为:
(1)将两亲性嵌段共聚物PMEO2MA-b-POVNG溶于超纯水中得到聚合物胶束溶液,再用超纯水稀释成不同浓度的聚合物溶液,转移到样品瓶中,其中再用超纯水稀释后的聚合物溶液浓度为0.001-0.5mg/mL;
(2)在设定温度下,分别将步骤(1)中装有不同浓度的聚合物溶液的样品瓶放入动态激光光散射仪样品池中,经过平衡后,在波长532nm下测定其光散射强度;
(3)将不同浓度下聚合物溶液的光散射强度与对应的浓度作图,所得两条直线的相交点对应的横坐标浓度即为聚合物在设定温度下的临界胶束浓度。
所述步骤(1)中两亲性嵌段共聚物PMEO2MA-b-POVNG的制备方法为:将乙烯基己二酸半乳糖酯OVNG与链转移剂PMEO2MA以摩尔比为4-7:1溶于溶剂中,加入引发剂,在氮气保护下搅拌反应,得到两亲性嵌段共聚物PMEO2MA-b-POVNG,其中PMEO2MA与引发剂的摩尔比为40-50:1,OVNG与PMEO2MA的总质量与溶剂的质量比为1:1-4。
所述溶剂为N,N-二甲基甲酰胺DMF;引发剂为偶氮二异丁腈AIBN;加入引发剂是在温度为70-80℃时进行的。
所述搅拌反应的时间为40-48h。
所述步骤(1)中聚合物胶束溶液的浓度为1-2mg/mL。
所述步骤(2)中平衡时间为15min;测定时间为2min。
本发明由可逆加成断裂链转移(RAFT)聚合法制得两亲性嵌段聚合物PMEO2MA-b-POVNG。
本发明使用动态激光光散射仪测定聚合物临界胶束浓度,当光线通过聚合物溶液时,若溶液中有胶束存在,则一部分光线将被胶束粒子所散射,因此测定散射光强度,可反映聚合物溶液中胶束形成,当聚合物在溶液中达到或超过一定浓度时,会由单个分子缔合成聚集体,即形成胶束,随聚合物浓度的增大,缔合分子不断增多,胶束聚集数不断增加,则其光散射强度不断增加,达临界胶束浓度时,光散射强度急剧增加,由浓度-光散射强度曲线即可得到临界胶束浓度。
有益效果
(1)本发明使用带有水循环控温系统的动态激光光散射仪测定聚合物的临界胶束浓度,因此可以不受外界环境温度干扰,可测定控温系统温度范围内任一特定温度的临界胶束浓度,这是其他测试临界胶束浓度的方法很难做到的;
(2)本发明操作简单,快速灵敏,可以准确确定两亲性嵌段共聚物临界胶束浓度。
附图说明
图1是实施例2中不同浓度PMEO2MA-b-POVNG水溶液在24℃下光散射强度随聚合物水溶液浓度变化的关系图;
图2是实施例3中不同浓度PMEO2MA-b-POVNG水溶液在29℃下光散射强度随聚合物水溶液浓度变化的关系图;
图3是实施例4中不同浓度PMEO2MA-b-POVNG水溶液在38℃下光散射强度随聚合物水溶液浓度变化的关系图;
图4是实施例5中PDEGMA-b-POVNG水溶液在不同温度下的临界胶束浓度变化曲线;
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
(1)将乙烯基己二酸半乳糖酯OVNG(5.71×10-4mol,0.191g)与链转移剂PMEO2MA(9.07×10-5mol,0.301g)溶于2mL N,N-二甲基甲酰胺DMF中,在70℃条件下加入引发剂AIBN(2.1×10-6mol,0.35mg),在氮气保护下搅拌反应48h,得到两亲性嵌段共聚物PMEO2MA-b-POVNG。
(2)将上述制得的两亲性嵌段共聚物PMEO2MA-b-POVNG溶于超纯水中配置成浓度为1mg/mL的聚合物胶束溶液。
实施例2
(1)将实施例1中1mg/mL的两亲性嵌段共聚物PMEO2MA-b-POVNG胶束溶液用超纯水稀释成不同浓度的聚合物水溶液,浓度分别为0.001,0.003,0.005,0.008,0.01,0.03,0.05,0.08,0.1,0.2,0.3,0.4,0.5mg/mL,通过0.45微米的水相微孔过滤器过滤到样品瓶中。
(2)将步骤(1)中样品瓶放入动态激光光散射仪样品池中平衡15min,在532nm波长处分别测试不同浓度聚合物水溶液在24℃的光散射强度,测试时间为2min。
(3)以浓度为横轴,光散射强度为纵轴,做光散射强度随聚合物水溶液浓度变化的关系图,所得两条直线的相交点对应的横坐标浓度即为该聚合物在24℃下的临界胶束浓度。
图1表明:在24℃下PMEO2MA-b-POVNG的临界胶束浓度为0.11mg/mL。
实施例3
(1)将实施例1中1mg/mL的两亲性嵌段共聚物PMEO2MA-b-POVNG胶束溶液用超纯水稀释成不同浓度的聚合物水溶液,浓度分别为0.001,0.003,0.005,0.008,0.01,0.03,0.05,0.08,0.1,0.2,0.3,0.4,0.5mg/mL,通过0.45微米的水相微孔过滤器过滤到样品瓶中。
(2)将步骤(1)中样品瓶放入动态激光光散射仪样品池中平衡15min,在532nm波长处分别测试不同浓度聚合物水溶液在29℃的光散射强度,测试时间为2min。
(3)以浓度为横轴,光散射强度为纵轴,做光散射强度随聚合物水溶液浓度变化的关系图,所得两条直线的相交点对应的横坐标浓度即为该聚合物在29℃下的临界胶束浓度。
图2表明:在29℃下PMEO2MA-b-POVNG的临界胶束浓度为0.041mg/mL。
实施例4
(1)将实施例1中1mg/mL的两亲性嵌段共聚物PMEO2MA-b-POVNG胶束溶液用超纯水稀释成不同浓度的聚合物水溶液,浓度分别为0.001,0.003,0.005,0.008,0.01,0.03,0.05,0.08,0.1,0.2,0.3,0.4,0.5mg/mL,通过0.45微米的水相微孔过滤器过滤到样品瓶中。
(2)将步骤(1)中样品瓶放入动态激光光散射仪样品池中平衡15min,在532nm波长处分别测试不同浓度聚合物水溶液在38℃的光散射强度,测试时间为2min。
(3)以浓度为横轴,光散射强度为纵轴,做光散射强度随聚合物水溶液浓度变化的关系图,所得两条直线的相交点对应的横坐标浓度即为该聚合物在38℃下的临界胶束浓度。
图3表明:在38℃下PMEO2MA-b-POVNG的临界胶束浓度为0.018mg/mL。
实施例5
根据实施例2,3,4的方法同样可以得出在21.6℃,26.7℃,32.4℃,35.2℃下的临界胶束浓度分别为0.171mg/mL,0.058mg/mL,0.025mg/mL,0.022mg/mL。以温度为横坐标,不同温度下的临界胶束浓度为纵坐标,得到PDEGMA-b-POVNG的临界胶束浓度随温度的变化曲线,如图4,可以看出随温度升高PDEGMA-b-POVNG水溶液的临界胶束浓度逐渐降低,温度大于32℃后变化不大。
Claims (5)
1.一种测定不同温度两亲性嵌段共聚物临界胶束浓度的方法,具体步骤为:
(1)将两亲性嵌段共聚物PMEO2MA-b-POVNG溶于超纯水中得到聚合物胶束溶液,再用超纯水稀释成不同浓度的聚合物溶液,转移到样品瓶中,其中再用超纯水稀释后的聚合物溶液浓度为0.001-0.5mg/mL;
(2)在设定温度下,分别将步骤(1)中装有不同浓度的聚合物溶液的样品瓶放入动态激光光散射仪样品池中,经过平衡后,在波长532nm下测定其光散射强度;
(3)将不同浓度下聚合物溶液的光散射强度与对应的浓度作图,所得两条直线的相交点对应的横坐标浓度即为聚合物在设定温度下的临界胶束浓度。
2.按照权利要求1所述的一种测定不同温度两亲性嵌段共聚物临界胶束浓度的方法,其特征在于,所述步骤(1)中两亲性嵌段共聚物PMEO2MA-b-POVNG的制备方法为:将乙烯基己二酸半乳糖酯OVNG与链转移剂PMEO2MA以摩尔比为4-7:1溶于溶剂中,加入引发剂,在氮气保护下搅拌反应,得到两亲性嵌段共聚物PMEO2MA-b-POVNG,其中PMEO2MA与引发剂的摩尔比为40-50:1,OVNG与PMEO2MA的总质量与溶剂的质量比为1:1-4。
3.按照权利要求2所述的一种测定不同温度两亲性嵌段共聚物临界胶束浓度的方法,其特征在于,所述溶剂为N,N-二甲基甲酰胺DMF;引发剂为偶氮二异丁腈AIBN;加入引发剂是在温度为70-80℃时进行的;搅拌反应的时间为40-48h。
4.按照权利要求1所述的一种测定不同温度两亲性嵌段共聚物临界胶束浓度的方法,其特征在于,所述步骤(1)中聚合物胶束溶液的浓度为1-2mg/mL。
5.按照权利要求1所述的一种测定不同温度两亲性嵌段共聚物临界胶束浓度的方法,其特征在于,所述步骤(2)中平衡时间为15min;测定时间为2min。
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CN111239053A (zh) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | 一种动态质量重置法检测化合物临界聚合浓度的方法 |
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