Pickering乳液为模板的特殊结构聚合物/二氧化硅复合微球的制备、表征和应用研究
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摘要
本研究的主要目标为：以Pickering乳液为模板制备超粒子结构（supracolloidal structure）聚合物/二氧化硅复合微球，并对其性能及应用进行研究。通过Pickering乳液模板法制备的超粒子结构微球具有独特的以无机粒子为壳层的核壳结构，能够赋予微球独特的功能，因此越来越引起人们的注意。我们选择不同的单体或聚合物为原料，以不同类型的Pickering乳液为模板，制备具有不同结构和性能的聚合物/二氧化硅复合微球，为有机/无机复合微球的制备与结构设计提供新的思路以及实验依据。
主要研究内容如下：
1）采用溶胶-凝胶法制备了纳米二氧化硅粒子，并使用-甲基丙烯酰氧基丙基三甲氧基硅烷（KH-570）对其进行表面改性。红外光谱和XPS分析结果证实KH-570确实接枝在纳米二氧化硅表面，接枝率可通过TGA测试结果计算；可以通过改性剂用量的不同来调节纳米二氧化硅的表面润湿性，得到适用于稳定不同类型Pickering乳液的纳米二氧化硅粒子。
研究了纳米二氧化硅颗粒的表面润湿性以及润湿顺序、颗粒浓度、体系pH值对颗粒在油/水（苯乙烯/水）体系中所处位置以及所得乳液类型的影响：过于亲水或疏水的二氧化硅颗粒均不能用作稳定剂来制备Pickering乳液，亲水性适中的纳米二氧化硅颗粒可形成O/W型乳液，对于亲水/亲油适中的二氧化硅颗粒，优先润湿性决定了其最终稳定的Pickering乳液的类型。
2）以改性二氧化硅粒子稳定的苯乙烯/水Pickering乳液为模板，成功制备了聚苯乙烯/二氧化硅复合微球。考察了二氧化硅表面润湿性、固体颗粒浓度以及引发剂种类等因素对聚苯乙烯/二氧化硅复合微球形貌的影响，结果发现在Pickering乳液聚合过程中，存在单体液滴内成核和水相成核两种成核方式，二者之间存在竞争作用，引发剂和二氧化硅粒子浓度对于微球的形成机理及最终形貌有着协同影响：当纳米二氧化硅粒子浓度较低，不能紧密包覆在液滴表面时，使用水溶性引发剂KPS，可以得到分散的PS微球，在其表面零星分布着纳米二氧化硅粒子；使用油溶性引发剂AIBN，则无法得到分散的微球。当纳米二氧化硅浓度较高，足以在液滴表面形成致密包覆层时，使用油溶性引发剂，可以得到分散性良好的微球，二氧化硅粒子在微球的表面密堆排列；若使用水溶性引发剂，所得产物微球的形状欠规整，并呈中空结构。
3）以苯乙烯作为油相，去离子水分别作为内水相和外水相，改性二氧化硅作为稳定剂，制备了水/苯乙烯/水（W/O/W）型多重乳液，并以该多重乳液为模板制备了多孔PS/SiO2复合微球。通过SEM、XPS等分析手段证实了微球内部存在多孔结构，绝大多数二氧化硅粒子富集在微球内腔壁上。TGA表征结果证实微球内部包含有水相，含量与配方中数值基本相当。可以通过改变配方中的内水相体积分数，控制PS/SiO2复合微球的内部结构。当内水相体积分数为20%时，得到的微球内部为多孔结构，且孔与孔互不连通；当内水相体积分数为70%时，则可以得到中空微球。
4）以正己烷为油相，聚乙烯醇（PVA）水溶液为水相，以及改性纳米二氧化硅粒子为稳定剂，制备了W/O型Pickering乳液，并以其为模板，通过循环冻融法制备了具有良好生物相容性的PVA/SiO2复合凝胶微球；扫描电镜和光学显微镜表征结果证实纳米二氧化硅粒子自组装在水油界面上，形成了以PVA凝胶为核，纳米二氧化硅粒子为壳的复合凝胶微球。系统研究了配方及工艺条件对PVA/SiO2复合凝胶微球形貌的影响。结果发现，当二氧化硅颗粒浓度较低时，微球粘附严重，二氧化硅颗粒浓度越高，制备的复合微球粒径越小，分散性越好；增大PVA浓度以及循环冻融次数都可以增大复合凝胶微球的机械强度，使微球干燥后形貌保持得更好。
选用亚甲蓝作为模拟药物，装载到PVA/SiO2复合凝胶微球中，探索了复合凝胶微球的控释性能。发现复合凝胶微球对亚甲蓝有缓释作用，当循环冻融次数及PVA浓度增大时，释放速率减缓，药物累计释放量减少；当纳米二氧化硅粒子浓度过低，不能对凝胶微球形成良好包覆时，释放速率较快；而当纳米二氧化硅粒子浓度较高时，增大二氧化硅粒子浓度会使凝胶微球粒径减小，也会使得释放速率增大。分别采用一级动力学、Higuchi、Weibull及Hixson-Crowell模型对PVA/SiO2复合凝胶微球的释放数据进行拟合，发现其释放曲线可以用Weibull模型描述，其释放动力学符合Fick扩散规律。
The purpose of our investigation is to prepare supracolloidal structure polymer compositemicrosphere by means of Pickering emulsion template and also carry out a research on itsapplication. Different core materials and different types of Pickering emulsion template have beenchosen to fabricate organic-inorganic composite microsphere with different structures and properties.The main contents and the results of the dissertation are as follows:
1) SiO2nanoparticles were prepared via sol-gel reaction and modified byEthacryloxypropyltrimethoxysilane (MPTMS). It was confirmed by FTIR and XPS that MPTMSwas successfully grafted to the surface of SiO2nanoparticles. The surface grafting degree of thefunctionalized SiO2nanoparticles was determined by TGA and the surface wettablity wasinvestigated through measuring the surface contact angle. The results showed that when the massratio of MPTMS to SiO2increased, the contact angle and the surface zeta potential increased, too.The surface wettablity could be tuned by controlling the grafting extent of MPTMS.
Further, Pickering emulsions (styrene/water) stabilized by SiO2nanoparticles were investigated.It was shown that the particle wettability and the priority wettability had significant effect on thetype and stability of the emulsion prepared. Stable Pickering emulsion could not be obtained withparticles which were too hydrophilic or hydrophobic. The particles of moderate hydrophilieity couldstabilize O/W emulsions. For particles of moderate hydrophilieity/hydrophilieity, the prior wettibilitydecided the type of emulsion.
2) Polystyrene/SiO2microspheres were fabricated via Pickering emulsion polymerizationstabilized by modified SiO2nanoparticles. The effect of particle wettability, particle concentrationand initiator sorts on the morphology of products was studied. It was found that at low particleconcentration, when hydrophilic initiator KPS was used, microspheres with SiO2nanoparticlesscattered on surface was obtained. Otherwise the product was aggregation when hydrophobicinitiator AIBN was used. At high particle concentration, when AIBN was applied as the initiator,dispersive microsphere with “densely packed” particle shell was prepared and when KPS was used,the products were hollow microspheres. The results showed that there were two nucleationmechanisms in the polymerizing process. The SiO2concentrations and initiator sorts wouldsynergistically impact the morphology of products corresponding to distinct formation mechanisms.
3) W/O/W (water/styrene/water) Pickering emulsion stabilized by modified SiO2nanoparticles was prepared. Then polystyrene microspheres with aqueous cores were fabricated withthe multiple Pickering emulsion as template. The final structure and constituents of the microsphereswas investigated through SEM, XPS and TGA. It was found that multi-core structure exiting in the microsphere and most of SiO2nanoparticles were adsorbed at the inner wall of the core; when thevolume fraction of inner water was0.2, the inner structure of the microspheres obtained was porousand each pore was not interconnected; when the volume fraction of inner water increased to0.7,hollow microspheres were obtained. The results showed that the size and amount of aqueous cores inthe microspheres could be tuned by the original structure of the multiple Pickering emulsions.
4) Using polyving akohol (PVA) solution as aqueous phase and Hexane as oil phase, W/OPickering emulsion stabilized modified SiO2nanoparticles was prepared. Subsequently, by applyingthe prepared Pickering emulsion as template, PVA/SiO2composite microsphere with PVA gel coresand shells of SiO2nanoparticles was fabricated through freezing-thawing method. The finalstructure and constituents of the microspheres were investigated by means of SEM, FTIR and TGA.The effect of PVA concentractoin, SiO2nanoparticles concentration and freezing-thawing cycletimes on the morphology of products was studied.
The PVA/SiO2composite microspheres were applied as a drug carrier to study their controlledrelease behaviors and methylene blue was used as a model drug. It was found that PVAconcentractoin, SiO2nanoparticles concentration and freezing-thawing cycle times had effect on therelease behaviors. All release curves were respectively fitted by Monoexponential equation, Higuchiequation, the Weibull equation and Hixson-Crowell equation. Weibull equation was found to fit thebest to the release process. The fitted results proved that the drug release from the PVA/SiO2composite microsphere followed the Fick diffusion.
主要研究内容如下：
1）采用溶胶-凝胶法制备了纳米二氧化硅粒子，并使用-甲基丙烯酰氧基丙基三甲氧基硅烷（KH-570）对其进行表面改性。红外光谱和XPS分析结果证实KH-570确实接枝在纳米二氧化硅表面，接枝率可通过TGA测试结果计算；可以通过改性剂用量的不同来调节纳米二氧化硅的表面润湿性，得到适用于稳定不同类型Pickering乳液的纳米二氧化硅粒子。
研究了纳米二氧化硅颗粒的表面润湿性以及润湿顺序、颗粒浓度、体系pH值对颗粒在油/水（苯乙烯/水）体系中所处位置以及所得乳液类型的影响：过于亲水或疏水的二氧化硅颗粒均不能用作稳定剂来制备Pickering乳液，亲水性适中的纳米二氧化硅颗粒可形成O/W型乳液，对于亲水/亲油适中的二氧化硅颗粒，优先润湿性决定了其最终稳定的Pickering乳液的类型。
2）以改性二氧化硅粒子稳定的苯乙烯/水Pickering乳液为模板，成功制备了聚苯乙烯/二氧化硅复合微球。考察了二氧化硅表面润湿性、固体颗粒浓度以及引发剂种类等因素对聚苯乙烯/二氧化硅复合微球形貌的影响，结果发现在Pickering乳液聚合过程中，存在单体液滴内成核和水相成核两种成核方式，二者之间存在竞争作用，引发剂和二氧化硅粒子浓度对于微球的形成机理及最终形貌有着协同影响：当纳米二氧化硅粒子浓度较低，不能紧密包覆在液滴表面时，使用水溶性引发剂KPS，可以得到分散的PS微球，在其表面零星分布着纳米二氧化硅粒子；使用油溶性引发剂AIBN，则无法得到分散的微球。当纳米二氧化硅浓度较高，足以在液滴表面形成致密包覆层时，使用油溶性引发剂，可以得到分散性良好的微球，二氧化硅粒子在微球的表面密堆排列；若使用水溶性引发剂，所得产物微球的形状欠规整，并呈中空结构。
3）以苯乙烯作为油相，去离子水分别作为内水相和外水相，改性二氧化硅作为稳定剂，制备了水/苯乙烯/水（W/O/W）型多重乳液，并以该多重乳液为模板制备了多孔PS/SiO2复合微球。通过SEM、XPS等分析手段证实了微球内部存在多孔结构，绝大多数二氧化硅粒子富集在微球内腔壁上。TGA表征结果证实微球内部包含有水相，含量与配方中数值基本相当。可以通过改变配方中的内水相体积分数，控制PS/SiO2复合微球的内部结构。当内水相体积分数为20%时，得到的微球内部为多孔结构，且孔与孔互不连通；当内水相体积分数为70%时，则可以得到中空微球。
4）以正己烷为油相，聚乙烯醇（PVA）水溶液为水相，以及改性纳米二氧化硅粒子为稳定剂，制备了W/O型Pickering乳液，并以其为模板，通过循环冻融法制备了具有良好生物相容性的PVA/SiO2复合凝胶微球；扫描电镜和光学显微镜表征结果证实纳米二氧化硅粒子自组装在水油界面上，形成了以PVA凝胶为核，纳米二氧化硅粒子为壳的复合凝胶微球。系统研究了配方及工艺条件对PVA/SiO2复合凝胶微球形貌的影响。结果发现，当二氧化硅颗粒浓度较低时，微球粘附严重，二氧化硅颗粒浓度越高，制备的复合微球粒径越小，分散性越好；增大PVA浓度以及循环冻融次数都可以增大复合凝胶微球的机械强度，使微球干燥后形貌保持得更好。
选用亚甲蓝作为模拟药物，装载到PVA/SiO2复合凝胶微球中，探索了复合凝胶微球的控释性能。发现复合凝胶微球对亚甲蓝有缓释作用，当循环冻融次数及PVA浓度增大时，释放速率减缓，药物累计释放量减少；当纳米二氧化硅粒子浓度过低，不能对凝胶微球形成良好包覆时，释放速率较快；而当纳米二氧化硅粒子浓度较高时，增大二氧化硅粒子浓度会使凝胶微球粒径减小，也会使得释放速率增大。分别采用一级动力学、Higuchi、Weibull及Hixson-Crowell模型对PVA/SiO2复合凝胶微球的释放数据进行拟合，发现其释放曲线可以用Weibull模型描述，其释放动力学符合Fick扩散规律。
The purpose of our investigation is to prepare supracolloidal structure polymer compositemicrosphere by means of Pickering emulsion template and also carry out a research on itsapplication. Different core materials and different types of Pickering emulsion template have beenchosen to fabricate organic-inorganic composite microsphere with different structures and properties.The main contents and the results of the dissertation are as follows:
1) SiO2nanoparticles were prepared via sol-gel reaction and modified byEthacryloxypropyltrimethoxysilane (MPTMS). It was confirmed by FTIR and XPS that MPTMSwas successfully grafted to the surface of SiO2nanoparticles. The surface grafting degree of thefunctionalized SiO2nanoparticles was determined by TGA and the surface wettablity wasinvestigated through measuring the surface contact angle. The results showed that when the massratio of MPTMS to SiO2increased, the contact angle and the surface zeta potential increased, too.The surface wettablity could be tuned by controlling the grafting extent of MPTMS.
Further, Pickering emulsions (styrene/water) stabilized by SiO2nanoparticles were investigated.It was shown that the particle wettability and the priority wettability had significant effect on thetype and stability of the emulsion prepared. Stable Pickering emulsion could not be obtained withparticles which were too hydrophilic or hydrophobic. The particles of moderate hydrophilieity couldstabilize O/W emulsions. For particles of moderate hydrophilieity/hydrophilieity, the prior wettibilitydecided the type of emulsion.
2) Polystyrene/SiO2microspheres were fabricated via Pickering emulsion polymerizationstabilized by modified SiO2nanoparticles. The effect of particle wettability, particle concentrationand initiator sorts on the morphology of products was studied. It was found that at low particleconcentration, when hydrophilic initiator KPS was used, microspheres with SiO2nanoparticlesscattered on surface was obtained. Otherwise the product was aggregation when hydrophobicinitiator AIBN was used. At high particle concentration, when AIBN was applied as the initiator,dispersive microsphere with “densely packed” particle shell was prepared and when KPS was used,the products were hollow microspheres. The results showed that there were two nucleationmechanisms in the polymerizing process. The SiO2concentrations and initiator sorts wouldsynergistically impact the morphology of products corresponding to distinct formation mechanisms.
3) W/O/W (water/styrene/water) Pickering emulsion stabilized by modified SiO2nanoparticles was prepared. Then polystyrene microspheres with aqueous cores were fabricated withthe multiple Pickering emulsion as template. The final structure and constituents of the microsphereswas investigated through SEM, XPS and TGA. It was found that multi-core structure exiting in the microsphere and most of SiO2nanoparticles were adsorbed at the inner wall of the core; when thevolume fraction of inner water was0.2, the inner structure of the microspheres obtained was porousand each pore was not interconnected; when the volume fraction of inner water increased to0.7,hollow microspheres were obtained. The results showed that the size and amount of aqueous cores inthe microspheres could be tuned by the original structure of the multiple Pickering emulsions.
4) Using polyving akohol (PVA) solution as aqueous phase and Hexane as oil phase, W/OPickering emulsion stabilized modified SiO2nanoparticles was prepared. Subsequently, by applyingthe prepared Pickering emulsion as template, PVA/SiO2composite microsphere with PVA gel coresand shells of SiO2nanoparticles was fabricated through freezing-thawing method. The finalstructure and constituents of the microspheres were investigated by means of SEM, FTIR and TGA.The effect of PVA concentractoin, SiO2nanoparticles concentration and freezing-thawing cycletimes on the morphology of products was studied.
The PVA/SiO2composite microspheres were applied as a drug carrier to study their controlledrelease behaviors and methylene blue was used as a model drug. It was found that PVAconcentractoin, SiO2nanoparticles concentration and freezing-thawing cycle times had effect on therelease behaviors. All release curves were respectively fitted by Monoexponential equation, Higuchiequation, the Weibull equation and Hixson-Crowell equation. Weibull equation was found to fit thebest to the release process. The fitted results proved that the drug release from the PVA/SiO2composite microsphere followed the Fick diffusion.
引文
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