CN111109300B - 一种pH响应型松香/纳米颗粒Pickering乳液及其制备方法 - Google Patents
一种pH响应型松香/纳米颗粒Pickering乳液及其制备方法 Download PDFInfo
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Abstract
本发明提供一种pH响应型松香/纳米颗粒Pickering乳液及其制备方法,该制备方法包括如下步骤:(1)将松香和纳米颗粒分散到水溶液中,制成松香质量浓度为0.001%~0.1%、纳米颗粒质量浓度为0.1%~2%的水相;(2)在水相中加入油相,乳化均匀即得pH响应型松香/纳米颗粒Pickering乳液。本发明利用极少量松香即可对纳米颗粒进行疏水性改性,所得到的乳液具有pH响应性能,在pH为6.5~10.5时,不同电荷的纳米颗粒和松香可形成电荷密度为零左右的团聚物,不仅提高了纳米颗粒的疏水性,而且该团聚物可紧密不可逆地吸附在油水界面,可形成稳定的Pickering乳液;当pH降低或升高时,则发生破乳。
Description
技术领域
本发明属于乳液制备技术领域,特别涉及一种pH响应型松香/纳米颗粒Pickering乳液及其制备方法。
背景技术
乳液在食品、化妆品、农药及矿物开采等领域具有广泛的用途,乳液的稳定及功能性影响着乳液的应用。一般需要在体系中加入较多的表面活性剂或具有表面活性的高分子聚合物才能稳定乳液,然而过多的有机合成分子存在环境和健康风险。
Pickering乳液是以超细固体颗粒作为乳化剂而得到的乳液。相对于传统的乳液,由于具有表面活性的颗粒尤其是纳米颗粒在油水界面具有不可逆的吸附,Pickering乳液在颗粒或者经表面修饰的作用下颗粒展现出更高的物理、化学稳定性,并且在大多数领域可以替代传统乳液,具有更广的应用领域。
然而,一般的颗粒具有较强的亲水能力,很难吸附在油水界面上,影响均匀的Pickering乳液的形成。近些年来,越来越多的人们关注利用有机分子或表面活性剂修饰颗粒的表面来改变其亲疏水性,并利用具有环境刺激响应的有机分子来构建智能型Pickering乳液。即,利用具有环境刺激响应的有机分子通过共价键或非共价键来修饰颗粒,从而使该颗粒在刺激作用下在表面活性与表面无活性之间的转变,从而影响乳液的稳定性,例如具有光响应的、CO2/N2、氧化还原、温度及pH响应性的Pickering乳液。但是目前这些智能型Pickering乳液的构建大多需要复杂的步骤来合成有机分子。
为了省去合成有机分子的复杂操作,目前越来越多的研究开始致力于生物可再生资源来修饰颗粒,例如海藻酸钠、黄原胶、植物蛋白、木质素等,但这些可再生资源缺少刺激响应性。然而在某些情况下,乳液的形成只是在生产的某些环节起作用,一旦这些环节完成,乳液的稳定性就需要通过物理或化学的方法消除,即进行破乳,以防止带来不必要的伤害,因此现有可再生资源修饰颗粒形成的乳液缺少刺激响应性的性质无法满足特定情况的下对乳液的要求。
发明内容
本发明的目的在于解决现有以再生资源修饰颗粒作为乳化剂形成的Pickering乳液缺少刺激响应性的问题,提供一种pH响应型松香/纳米颗粒Pickering乳液及其制备方法。
本发明的pH响应型松香/纳米颗粒Pickering乳液的制备方法包括如下步骤:
(1)将松香和纳米颗粒分散到水中,制成松香质量浓度为0.001%~0.1%、纳米颗粒质量浓度为0.1%~2%的水相;
(2)在水相中加入油相,乳化均匀即得pH响应型松香/纳米颗粒Pickering乳液。
进一步,所述纳米颗粒的粒径为10~500nm。
进一步,所述纳米颗粒选自纳米氧化铝、纳米二氧化钛和纳米氧化锌中的任意一种。
进一步,所述水相的pH为6.5~10.5。在该pH条件下,所述pH响应型松香/纳米颗粒Pickering乳液具有高稳定性;当pH小于6.5或高于10.5时,可实现pH响应型松香/纳米颗粒Pickering乳液的破乳。
进一步,所述松香的主要成分包括左旋海松酸、新枞酸、长叶枞酸和枞酸,具有较丰富的羧基基团。
进一步,所述油相相对于水相的体积分数为10%~80%,优选50%。
进一步,所述油相选自正己烷、正庚烷、正癸烷、正十六烷、甲苯、二氯甲烷、液体石蜡和乙酸乙酯中的任意一种。
进一步,所述乳化过程为:在10000~25000rpm的转速下剪切乳化2~4min,优选13000~15000rpm。
本发明还提供由上述制备方法制得的pH响应型松香/纳米颗粒Pickering乳液。
本发明将再生资源松香与纳米颗粒共同作为乳化剂,在不同的pH条件下,纳米颗粒表面电荷和松香的电离程度不同。当pH为6.5~10.5时,不同电荷的纳米颗粒和松香通过静电作用可形成电荷密度为零左右的团聚物,不仅提高了纳米颗粒的疏水性,而且该团聚物可紧密不可逆地吸附在油水界面,可形成稳定的Pickering乳液。当pH小于6.5或高于10.5时,纳米颗粒与松香的电荷相同或者静电相互作用弱,纳米颗粒亲疏水性变化小,再结合静电斥力,并不能在油水界面紧密分布,导致无法形成稳定的Pickering乳液,发生破乳,使油相和水相分离;而当将pH再调回6.5~10.5时,体系可重新形成稳定的Pickering乳液,具有可逆性。
因此,本发明制备的pH响应型松香/纳米颗粒Pickering乳液具有pH响应性,能够在不同pH下实现乳液的稳定或者破乳。而且使用质量浓度低至0.001%的松香即可实现纳米颗粒的改性,形成稳定的Pickering乳液,用量远远低于现有技术,在实际应用中可大幅度降低成本。同时,本发明的Pickering乳液中的松香和纳米颗粒都具有良好杀菌特性,所以该类环保响应型Pickering乳液的构建有助于实现松香的高附加值利用并丰富新型绿色杀菌乳液的种类。
附图说明
图1为实施例1中不同pH下制成的pH响应型松香/纳米颗粒Pickering乳液照片;
图2为实施例1中pH为6.5~10.5时pH响应型松香/纳米颗粒Pickering乳液的显微镜图;
图3表示实施例1的pH响应型松香/纳米颗粒Pickering乳液随着pH改变在稳定状态与不稳定状态之间的转变;
图4为实施例2不同松香质量浓度下的pH响应型松香/纳米颗粒Pickering乳液照片,其中(a)对应松香质量浓度为0.0001%,(b)对应松香浓度为0.001%,(c)对应松香浓度为0.01%,(d)对应松香浓度为0.1%,(e)对应松香浓度为1%;
图5为实施例2不同松香质量浓度下的pH响应型松香/纳米颗粒Pickering乳液显微镜图,其中(a)对应松香质量浓度为0.001%,(b)对应松香浓度为0.01%,(c)对应松香浓度为0.1%,(d)对应松香浓度为1%;
图6为实施例2不同纳米氧化铝质量浓度下的pH响应型松香/纳米颗粒Pickering乳液照片,其中(a)对应纳米氧化铝质量浓度为0.05%,(b)对应纳米氧化铝质量浓度为0.1%,(c)对应纳米氧化铝质量浓度为0.5%,(d)对应纳米氧化铝质量浓度为1%,(e)对应纳米氧化铝质量浓度为1.5%,(f)对应纳米氧化铝质量浓度为3%;
图7为实施例2不同纳米氧化铝质量浓度下的pH响应型松香/纳米颗粒Pickering乳液显微镜图,其中(a)对应纳米氧化铝质量浓度为0.1%,(b)对应纳米氧化铝质量浓度为0.5%,(c)对应纳米氧化铝质量浓度为1%,(d)对应纳米氧化铝质量浓度为1.5%,(e)对应纳米氧化铝质量浓度为3%;
图8为纳米氧化铝质量浓度为2%,pH=9.5条件下,不同质量浓度的松香与纳米颗粒团聚物的接触角,其中(a)对应松香质量浓度为0,(b)对应松香浓度为0.0001%,(c)对应松香浓度为0.001%,(d)对应松香浓度为0.01%,(e)对应松香浓度为0.1%,(f)对应松香浓度为1%;
图9为实施例3~5的pH响应型松香/纳米颗粒Pickering乳液,其中(a)表示实施例3,(b)表示实施例4,(c)表示实施例5。
具体实施方式
本发明将松香和纳米颗粒分散到水溶液中,制成松香质量浓度为0.001%~0.1%、纳米颗粒质量浓度为0.1%~2%的水相;再在水相中加入油相,乳化均匀得到pH响应型松香/纳米颗粒Pickering乳液,利用松香即可对纳米颗粒进行疏水性改性,所得到的乳液具有pH响应性能。以下结合具体实施例详细说明本发明的技术方案。
实施例1
本实施例提供一种由松香和纳米氧化铝形成的pH响应型松香/纳米颗粒Pickering乳液,其制备方法包括如下步骤:
(1)将主要成分包括左旋海松酸、新枞酸、长叶枞酸和枞酸的松香和粒径为15nm的纳米氧化铝颗粒分散到水中,使用5%HCl溶液调节pH至4.5,得到松香质量浓度为0.1%、纳米氧化铝质量浓度为2%的水相;
(2)在水相中加入相对水相体积分数为50%的葵烷(油相),使用IKA T18高速剪切机对油相和水相的混合物乳化3min,转速为13000rpm,得到pH响应型松香/纳米颗粒Pickering乳液。
作为比较,将松香和纳米氧化铝分散在pH分别为1.5、3.5、5.5、6.5、7.5、8.5、9.5、10.5、11.5或12.5的水溶液中形成浓度相同的水相,然后在相同的制备方法下分别制得相应的pH响应型松香/纳米颗粒Pickering乳液。
上述不同pH的水溶液条件下制得的pH响应型松香/纳米颗粒Pickering乳液照片如图1所示。图1反映,发现水溶液pH在1.5~5.5区间内,乳液完全分相;当水溶液pH增加至6.5~10.5,可形成稳定的Pickering乳液;然而当水溶液pH继续增高时,乳液又出现分相。同时图2所示pH为6.5、7.5、8.5、9.5、10.5的Pickering乳液的显微镜图进一步反映了pH为6.5~10.5时Pickering乳液的稳定、均匀状态。说明在低pH或高pH下,纳米颗粒与松香分子相互作用弱,而水溶液pH为6.5~10.5时纳米氧化铝与松香发生了相互作用,使纳米氧化铝发生了疏水改性。
此外,在以pH为1.5的水溶液制成的pH响应型松香/纳米颗粒Pickering乳液中加入5%NaOH溶液调节乳液的pH至9.5,再继续调节至乳液pH为12.5;接着用5%HCl溶液将乳液的pH调节回9.5,最后再将乳液的pH调回至1.5,其间乳液的状态变化如图3所示。图3反映,松香和纳米氧化铝形成的Pickering乳液体系随着pH的不同实现在稳定均匀状态和不稳定、分相状态之间的转变,说明该体系具有双pH响应性,在低pH和高pH下都可以发生乳液破乳,并且具有可逆性。
实施例2
本实施例提供一种由松香和纳米氧化铝形成的pH响应型松香/纳米颗粒Pickering乳液,其制备方法包括如下步骤:
(1)将松香和粒径为15nm的纳米氧化铝颗粒分散到水中,调节pH为9.5,得到松香质量浓度为0.001%、纳米氧化铝质量浓度为2%的水相;
(2)在水相中加入相对水相体积分数为50%的葵烷(油相),使用IKA T18高速剪切机对油相和水相的混合物乳化3min,转速为13000rpm,得到pH响应型松香/纳米颗粒Pickering乳液。
作为对比,在保持纳米氧化铝质量浓度为2%的情况下,将松香质量浓度分别替换成0.0001%、0.01%、0.1%、1%,在相同的制备方法下分别制得相应的pH响应型松香/纳米颗粒Pickering乳液。
作为另一对比,在保持松香质量浓度为0.001%的情况下,将纳米氧化铝的质量浓度分别改成0.05%、0.1%、0.5%、1%、1.5%、3%,在相同的制备方法下分别制得相应的pH响应型松香/纳米颗粒Pickering乳液。
上述松香质量浓度分别为0.0001%、0.001%、0.01%、0.1%和1%条件下制得的pH响应型松香/纳米颗粒Pickering乳液如图4和图5所示,其中图4表示pH响应型松香/纳米颗粒Pickering乳液的宏观照片,图5表示pH响应型松香/纳米颗粒Pickering乳液的显微镜图。从图4可以看出,随着松香浓度的不断增加,乳液下层的水相不断减小;而且图5反映乳液颗粒密度逐渐增大,乳液颗粒粒径趋向均匀化,说明体系的乳化能力逐渐增强。
图6和图7表示纳米氧化铝为0.05%、0.1%、0.5%、1%、1.5%、3%制备的Pickering乳液,发现纳米氧化铝的量低至0.1%仍能形成稳定的Pickering乳液。
同时,固定纳米氧化铝质量浓度为2%,pH=9.5条件下,不同质量浓度的松香与纳米颗粒团聚物的接触角如图8所示。图8(a)反映没有加入松香时纳米氧化铝颗粒团聚物的接触角为11.9°~12.4°;松香质量浓度为0.0001%时,发现该浓度的松香对纳米氧化铝颗粒的改性并不明显,接触角为11.9°~18.8°,和改性前类似;在松香质量浓度为0.001%时,接触角仅为16.3°~16.7°;而将松香浓度继续增加至0.01%后,接触角则增加至24.3°~25.8°;在松香质量浓度增加至0.1%时,接触角增加至60.5°~61.7°,说明松香浓度越高对纳米氧化铝的疏水改性越强;但当松香质量浓度增加至1%时,发现更高浓度的松香反而接触角会下降,降至45.3°~45.9°,这可能是因为过多的松香分子在团聚物中引入过多的电荷,疏水性减弱,如图8(f)所示。
实施例3
本实施例提供一种由松香和纳米二氧化钛形成的pH响应型松香/纳米颗粒Pickering乳液,其制备方法包括如下步骤:
(1)将松香和粒径为80nm的纳米二氧化钛分散到水中,调节pH为9.5,得到松香质量浓度为0.1%、纳米二氧化钛质量浓度为0.1%的水相;
(2)在水相中加入相对水相体积分数为50%的甲苯(油相),使用IKA T18高速剪切机对油相和水相的混合物乳化3min,转速为13000rpm,得到pH响应型松香/纳米颗粒Pickering乳液。
所得的pH响应型松香/纳米颗粒Pickering乳液中水相和油相均匀、稳定混合在一起,如图9(a)所示。
实施例4
本实施例提供一种由松香和纳米二氧化钛形成的pH响应型松香/纳米颗粒Pickering乳液,其制备方法包括如下步骤:
(1)将松香和粒径为450nm的纳米二氧化钛分散到水中,调节pH为9.5,得到松香质量浓度为0.1%、纳米二氧化钛质量浓度为0.1%的水相;
(2)在水相中加入相对水相体积分数为50%的正己烷(油相),使用IKA T18高速剪切机对油相和水相的混合物乳化4min,转速为15000rpm,得到pH响应型松香/纳米颗粒Pickering乳液。
所得的pH响应型松香/纳米颗粒Pickering乳液中水相和油相均匀、稳定混合在一起,如图9(b)所示。
实施例5
本实施例提供一种由松香和纳米氧化锌形成的pH响应型松香/纳米颗粒Pickering乳液,其制备方法包括如下步骤:
(1)将松香和粒径为60nm的纳米氧化锌分散到水中,调节pH为9.5,得到松香质量浓度为0.1%、纳米氧化锌质量浓度为0.01%的水相;
(2)在水相中加入相对水相体积分数为50%的正十六烷(油相),使用IKA T18高速剪切机对油相和水相的混合物乳化4min,转速为15000rpm,得到pH响应型松香/纳米颗粒Pickering乳液。
所得的pH响应型松香/纳米颗粒Pickering乳液中水相和油相均匀、稳定混合在一起,如图9(c)所示。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (4)
1.一种pH响应型松香/纳米颗粒Pickering乳液的制备方法,其特征在于:包括如下步骤:
(1)将松香和纳米颗粒分散到水中,制成松香质量浓度为0.001%~0.1%、纳米颗粒质量浓度为0.1%~2%的水相;所述纳米颗粒的粒径为10~500nm,所述纳米颗粒选自纳米氧化铝、纳米二氧化钛和纳米氧化锌中的任意一种;所述水相的pH为6.5~10.5;
(2)在水相中加入油相,乳化均匀即得pH响应型松香/纳米颗粒Pickering乳液;所述油相相对于水相的体积分数为10%~80%;所述油相选自正己烷、正庚烷、正癸烷、正十六烷、甲苯、二氯甲烷、液体石蜡和乙酸乙酯中的任意一种。
2.根据权利要求1所述pH响应型松香/纳米颗粒Pickering乳液的制备方法,其特征在于:所述松香含有左旋海松酸、新枞酸、长叶枞酸和枞酸。
3.根据权利要求1所述pH响应型松香/纳米颗粒Pickering乳液的制备方法,其特征在于:所述乳化过程为:在10000~25000rpm的转速下剪切乳化2~4min。
4.一种pH响应型松香/纳米颗粒Pickering乳液,其特征在于:由权利要求1~3任一项所述的制备方法制备得到。
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