CN109620747B - 一种具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备方法 - Google Patents

一种具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备方法 Download PDF

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CN109620747B
CN109620747B CN201811623640.2A CN201811623640A CN109620747B CN 109620747 B CN109620747 B CN 109620747B CN 201811623640 A CN201811623640 A CN 201811623640A CN 109620747 B CN109620747 B CN 109620747B
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齐丽云
张萌
包浩
方云
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Abstract

本发明公开了一种具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备方法，属于胶体界面化学领域。具体公开的是以两性表面活性剂α‑羧基十三烷基二甲基氧化胺和α‑羧基十五烷基二甲基氧化胺配制混合溶液，在25～70℃温度条件下，pH值在5.5～7.5区间内，两种表面活性剂的混合比在2/1～1/8范围内，总表面活性剂浓度达到1～10%时即可获得稳定区间较宽的高粘弹性的蠕虫状胶束。该蠕虫状胶束原料来源于天然油脂衍生物，制备方法简单，体系粘弹性能突出，产品温和无刺激，pH响应迅速，在环境保护、油田开采、纺织印染、工业清洗以及高档化妆品方面制备均有广阔的应用前景。

Description

一种具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备 方法
技术领域
本发明涉及胶体界面化学领域，具体地说涉及一种具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备方法。
背景技术
表面活性剂是具有表面活性的特殊小分子两亲化合物，能够自组装形成球状胶束、短棒状胶束、蠕虫状胶束、囊泡和层状液晶等多种形态的有序结构。蠕虫状胶束，是指在一定条件下，溶液中具有特定结构的表面活性剂自组装胶束的尺寸沿着一维方向增加，同时这种胶束能够相互缠绕交叠，构成柔性的三维网络空间结构，宏观上表现出类似聚合物凝胶的黏弹性，同时不断发生破坏-重组而构成动态平衡。因此，蠕虫状胶束也被称为“活聚合物”或“平衡聚合物”。若在表面活性剂分子中引入环境刺激响应基团或在体系中引入能参与胶束组装且具有环境响应的组分或基团，外界环境条件（温度、pH、电解质、浓度、光、电场等）发生微小变化时，其微观聚集结构可相应发生转变从而引起宏观流变性能的可控响应。与其它调控手段如光、热、磁、电等相比，pH 响应具有成本低、高效、方便、响应快速、可逆等显著特点，在药物运输、流体减阻、油田采气、生物工程、化妆品等领域的应用前景广阔，受到广泛关注。
分子中含有氧化胺基和羧基的α-羧基长链烷基二甲基氧化胺表面活性剂具有对pH响应的两个基团，可由天然脂肪酸经氯代、胺解和氧化三步简单反应合成，原料来源广泛、制备方法简单、成本经济，而且表面活性优良、性能温和、容易降解。在一定条件下，α-羧基十三烷基二甲基氧化胺和α-羧基十五烷基二甲基氧化胺均可形成蠕虫状胶束，但形成蠕虫状胶束的pH响应区间较窄，实际应用中需要在一定pH范围内粘弹性保持稳定的应用受到限制。
发明内容
本发明所要解决的技术问题是提供一种具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备方法，以及根据该方法制得的胶束的应用。
为了解决上述技术问题，本发明采用如下技术方案：一种具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备方法，包括以下步骤：在25～70℃温度条件下，将α-羧基十三烷基二甲基氧化胺和α-羧基十五烷基二甲基氧化胺加入到水中配制成溶液，并调节溶液的pH值保持在5.5～7.5区间内，即得所述具有pH响应的高粘弹性表面活性剂蠕虫状胶束。
进一步地，α-羧基十三烷基二甲基氧化胺与α-羧基十五烷基二甲基氧化胺的质量比在2/1～1/8范围内，质量百分比浓度之和为1～10%。在此浓度范围内，所得溶液具有显著的剪切稀释特征，零剪切粘度可达到在1～120 Pa·s。
进一步地，所得溶液具有剪切稀释特征，其零剪切粘度保持在1～120 Pa·s范围内。
进一步地，所得溶液当其pH值偏离蠕虫状胶束形成条件0.2时，粘度值降低至0.01Pa·s以下。
本发明还提供根据上述方法制得的具有pH响应的高粘弹性表面活性剂蠕虫状胶束在在制备化妆品中的应用。因该胶束pH范围与人体皮肤pH值吻合，有利于保持活性成分的稳定性及润肤、保湿的持久作用，可达到增强产品粘度和保持有效成分持久性的作用。
本发明的有益效果体现在：
本发明通过两种表面活性剂分子大小及pH响应差异导致的分子自组装协同效应，拓宽了蠕虫状胶束粘弹性的稳定存在的pH区间，改善了单独表面活性剂蠕虫状胶束存在pH范围较窄的缺陷，胶束具备明显的剪切稀释性能，能够保持稳定的粘弹性。
本发明所用的α-羧基十三烷基二甲基氧化胺与α-羧基十五烷基二甲基氧化胺来源于天然油脂，原料来源广泛，制备方法简单易行，成本低廉，制得的产品温和无刺激。
本发明得到的蠕虫状胶束pH响应灵敏迅速，加入酸或碱搅拌均匀后，pH值达到既定值即完成流变响应，在环境保护、油田开采、纺织印染、工业清洗以及制备化学品方面均有广阔的应用前景。
具体实施方式
下面结合实施例对本发明作进一步描述：
以下实施例所使用的各种原料，如未作特别说明，均为本领域公知的原料。
下述实施例中涉及的检测方法如下：流变性能实验采用Discovery DHR-2型流变仪(美国TA公司)进行测试，采用直径为40 mm和锥角为2o的锥板作为测试系统，且锥板与平台间隙为48 μm。为确保样品处于平衡状态，在测试前将样品溶液置于恒温水浴中1 h，测试时在平台上恒温3 min。稳态剪切实验采用速率控制模式，剪切速率范围为0.001 ~ 100 s-1；动态剪切实验采用剪切振荡模式，用两种方式测定：(1) 固定振荡频率为1 Hz，在0.1 ~100 Pa时进行应力扫描以确定体系的线性粘弹性应力区；(2) 选择一个在线性粘弹区的应力值，在0.01 ~ 100 rad/s时进行剪切速率扫描，得到储能模量(G’)和损耗模量(G”)随应力、剪切速率的变化规律。
实施例1
具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备
分别称取α-羧基十三烷基二甲基氧化胺0.1g和α-羧基十五烷基二甲基氧化胺0.1g，于25℃水浴条件下加入到蒸馏水中，超声振荡使其溶解，制得质量浓度1.1%的水溶液，测定该水溶液的pH值为6.42。
该溶液具有显著的剪切稀释性，测得其零剪切粘度为8Pa·s，当角频率低于特征角频率时，与损耗模量G’’ 大于储能模量G’，体系表现为黏性；当角频率高于特征角频率时，储能模量G’大于损耗模量Ｇ”，体系表现为弹性。因此，该溶液具有明显的粘弹性流体行为，证明为具有pH响应的高粘弹性表面活性剂蠕虫状胶束。
实施例2
具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备
将α-羧基十三烷基二甲基氧化胺和α-羧基十五烷基二甲基氧化胺按照质量比1:8的比例，于45℃水浴条件下加入到蒸馏水中，通过磁力搅拌使其溶解，制得质量浓度9.8%的水溶液，测得该水溶液的pH值为6.8。
该水溶液呈凝胶状，选用剪切率为0.01 ~ 100 1/s的扫描范围，采用稳态模式对所得水溶液进行扫描，测得其在一定剪切率范围内出现牛顿平台，溶液粘度不随剪切率的变化而变化，表现为典型的牛顿流体行为；当剪切率超过临界值时具有显著的剪切稀释性，其零剪切粘度为116Pa·s，证明为具有pH响应的高粘弹性表面活性剂蠕虫状胶束。
另外，取该胶束用0.05mol/L的NaOH溶液调节其pH值，得到pH值分别为7.0、7.4的样品溶液。实验测试表明，得到的两份溶液样品均具有显著的剪切稀释性，测得零剪切粘度分别为53Pa·s和45Pa·s。
实施例3
具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备
将α-羧基十三烷基二甲基氧化胺和α-羧基十五烷基二甲基氧化胺按照质量比2:1的比例，于70℃水浴条件下加入到pH为5.8的缓冲溶液中，通过加热搅拌使其溶解，制得质量浓度2.5%的水溶液。
所得溶液经流变性能测定，表明溶液具有流变稀释行为，零剪切粘度为4.3Pa·s，表明为具有pH响应的高粘弹性表面活性剂蠕虫状胶束。
应当理解本文所述的例子和实施方式仅为了说明，并不用于限制本发明，本领域技术人员可根据它做出各种修改或变化，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (3)

1.一种具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备方法，其特征在于：包括以下步骤：在45℃温度条件下，将α-羧基十三烷基二甲基氧化胺和α-羧基十五烷基二甲基氧化胺按照质量比1:8的比例加入到水中配制成质量浓度9.8%的水溶液，水溶液的pH为6.8，即得所述具有pH响应的高粘弹性表面活性剂蠕虫状胶束；
所得溶液具有剪切稀释特征，其零剪切粘度为116Pa·s。
2.根据权利要求1所述的具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备方法，其特征在于：所得溶液当其pH值偏离蠕虫状胶束形成条件0.2时，粘度值降低至0.01Pa·s以下。
3.根据权利要求1或2所述的具有pH响应的高粘弹性表面活性剂蠕虫状胶束的制备方法制得的具有pH响应的高粘弹性表面活性剂蠕虫状胶束在制备化妆品中的应用。
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