细乳液法制备无机/聚合物纳米复合微球
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摘要
细乳液聚合作为一种新型的聚合方法,在最近几十年的发展中,已得到了充分的认可和广泛的推广,在国外,细乳液聚合方法已经运用到工业化生产中。随着细乳液聚合机理逐渐被人们所深度发掘,其优点也逐渐显现出来。相比较于常规乳液聚合,细乳液聚合能够将乳胶粒的粒径进一步减小到50-500nm,这在要求小粒径的产品领域,将是一个很大的突破。另外,随着各国环保法规的日趋严格和人们环保意识的加强,乳液聚合中表面活性剂的使用量已成为人们关注的一个重要要素。常规乳液聚合中需使用较大量的表面活性剂,这在最终的产品使用中不仅影响产品的性能,而且较多的表面活性剂会造成对环境的污染。而细乳液聚合工艺能使表面活性剂的使用量降到最低限度,却不影响其乳液的稳定性,并且保证了粒子的较小粒径。尤其是可聚合高分子表面活性剂在细乳液中的应用,使得细乳液聚合在某种程度上,可以称为绿色聚合工艺。
本文第一章以细乳液聚合为主线,分别介绍了细乳液法制备无机／聚合物复合微球的研究进展,另外还介绍了WPU表面活性剂在细乳液聚合中的应用进展,以及细乳液聚合制备仿生材料的研究进展。
本文第二章介绍了SiO2/PMMA复合微球的细乳液法制备。采用异佛尔酮二异氰酸酯(IPDI)、聚醚二元醇N210和二羟甲基丙酸(DMPA)为主要反应原料,合成出羧酸型水性聚氨酯,并以甲基丙烯酸羟乙酯(HEMA)对其进行C=C封端,然后使用该水性聚氨酯作为可聚合表面活性剂,采用双原位细乳液法,不同引发剂体系引发聚合,制备出Si02/聚甲基丙烯酸甲酯复合微球。通过TEM、FTIR和TGA等测试方法对所得产物进行了表征分析。结果表明,使用水性聚氨酯表面活性剂所制备的Si02/聚甲基丙烯酸甲酯复合微球形貌,不同于传统小分子表面活性剂所制得产物的形貌,而且引发剂类型对Si02/聚甲基丙烯酸甲酯复合微球形貌有较大影响。
本文第三章介绍了nHA/PMMA复合微球的细乳液原位仿生合成方法。采用细乳液法合成出表而功能化的聚合物纳米粒子,并以其为模板,利用纳米粒子表面的离子对Ca2+的静电吸附作用,在一定的pH条件下,进行水相中纳米羟基磷灰石(nHA)在聚合物纳米粒子表面的原位仿生矿化,制备出nHA/聚合物复合微球。通过FT-IR、XRD和TEM等测试对所得产物进行了表征分析,并考察了nHA/聚合物复合微球对水杨酸药物的吸附作用。结果表明,复合微球上的无机组分为类似于人骨生物磷灰石的nHA,同时复合微球能够对水杨酸产生吸附作用,并且吸附性能随着水杨酸初始浓度的增大而增加,吸附速度快,5h即达到吸附平衡,这为骨组织再生、药物传递以及载药骨材料提供了潜在的应用可能性。
本文第四章介绍了一种窄粒径分布的SiO2/PAM杂化中空微球的双原位反相细乳液法制备。首先使用丙烯酰胺(AM)和二乙烯苯(DVB)的原位反相细乳液共聚合,制备出交联的聚合物纳米胶囊作为模板,通过硅酸乙酯(TEOS)的原位界面水解和沉淀,制备出窄粒径分布的杂化中空微球。通过使用SPAN-80和CTAB作为表面活性剂经均化器制备出pH可控的亲水性反相细乳液液滴,TEOS直接加入到反相细乳液的连续相中。由于二氧化硅通过界面溶胶凝胶过程,沉积在聚合物纳米胶囊表面形成了二氧化硅壳层。杂化中空微球形貌通过透射电子显微镜(TEM)直观观察,动态光散射(DLS)考察了粒径及粒径分布,热性能及Si02含量通过热分析(TGA)测试确定。结果表明制备出的杂化中空微球粒径分布较窄,大小为230-350nm,并且具有空心和双层壳结构,聚合物层为30nm, SiO2层为20nm。
As a novel method, miniemulsion polymerization has gained sufficient ratification and extensive spread in late decades. It has applied in industry abroad. Its advantages appear gradually, with the mechanism of miniemulsion being explored. Compared with common emulsion polymerization, miniemulsion has a smaller size of50-500nm, which is a great breakthrough in the area of smaller size. Moreover, as the more strict requirements of environmental protection and enhanced environment protecting consciousness, the amount of surfactant used in emulsion polymerization has been an important factor. A mass of surfactant used in emulsion polymerization affects the property of the final products, and pollutes the environment. But miniemulsion uses the least amount of surfactant, and guarantees the stability of latex. Especially, the polymerizable macromolecule surfactant used in miniemulsion makes it being green polymerization.
In the first chapter, the research process of preparation of inorganic/polymer composite microsphere via miniemulsion is introduced, with miniemulsion polymerization as the main clues. Applied process of waterborne polyurethane as surfactants in miniemulsion polymerization, together with miniemulsion preparation of biomimetic materials are also introduced.
In the second chapter, the preparation of SiO2/PMMA composite microspheres via miniemulsion polymerization was introduced. The carboxylic waterborne polyurethane was synthesized with isophorone diisocyanate(IPDI), polyether glycol(N210) and2,2-bis(hydroxymethyl)propionic acid(DMPA) as the major materials, and terminated by C=C from β-hydroxyethyl methacrylate(HEMA). SiO2/PMMA composite microspheres were prepared with different type of initiators by double in situ miniemulsion polymerization, in which the waterborne polyurethane was used as a polymerizable surfactant. The prepared products were characterized by TEM, FTIR and TGA, respectively. The results indicate that morphologies of the SiO2/PMMA composite microsphere prepared by waterborne polyurethane surfactant are different from those prepared by conventional micromolecule surfactants. The type of initiators affects significantly on the morphologies of the SiO2/PMMA.
In the third chapter, the method of in situ biomimetic synthesis of nHA/PMMA composite microspheres was introduced. nHA/polymer composite microspheres with the size of250nm were in situ biomimetic synthesized in the aqueous phase at37℃for7days by using the surface-functionalized polymeric nanoparticles as templates. A miniemulsion process was adopted to prepare the cross-linked templates via the co-polymerization of methyl methacrylate (MMA) and methyl acrylic acid (MAA). The functional groups (-COOH) were bound on the surface of polymeric nanoparticles. By utilizing the-COOH groups absorbing Ca+followed by HPO42-in certain pH conditions, hydroxyapatite (HA) crystal nucleus formed and grew up to be rod-like crystals on the surface in this system. Thus, nHA/polymer composite microspheres are successfully obtained, and studied by Fourier transform-infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), and transmission electron microscopy (TEM). The morphology of the polymeric nanoparticles and composite microspheres was investigated by (TEM). In the TEM images of polymeric templates, plenty of nanoparticles about200nm were observed. And some unsmooth nanoparticles with the larger size of250nm were presented in the TEM images of composite microspheres. The inorganic component, increased in size of the50nm in composite microspheres, confirmed to be low crystallized HA in nanoscale by XRD, which is similar to that of skeleton. Together with FT-IR, they showed that nHA was fabricated on the surface of polymer microspheres. Also, its adsorption studies on salicylic acid (SA) are investigated. The composite microspheres were dispersed in SA solution under constant stirring. After the SA adsorbed by the composite microspheres in certain time, the content of residual SA was detected using UV. It's also revealed that SA can be absorbed by composite microspheres. The intensity of absorption increases with the increase of the initial concentration of SA, and the absorption reaches equilibrium after5h at a fast speed. These nHA/polymer composite microspheres have great potential in bone tissue regeneration, drug delivery and bone materials loaded with drugs.
In the fourth chapter, the preparation of narrowly size-distributed hybrid hollow microspheres via double in-situ inverse miniemulsion polymerization and interfacial sol-gel process was introduced. Hybrid hollow microspheres with a narrow size distribution were successfully prepared via in-situ interfacial hydrolysis and condensation reactions of tetraethoxysilane (TEOS) based on the templates of cross-linked polymer nanocapsules, which were synthesized via in-situ inverse miniemulsion copolymerization of acrylamide (AM) and divinylbenzene (DVB). The inverse miniemulsions containing pH-controlled hydrophilic droplets were first prepared via homogenizer by using Span-80and cetyltrimethylarnmonium bromide (CTAB) as surfactants. TEOS was directly introduced to the continuous phase of an inverse miniemulsion. The silica shell was formed via interfacial sol-gel process by the deposition of silica on the surface of polymer nanocapsules. The formation of hybrid hollow microspheres morphology was confirmed by transmission electron microscopy (TEM), and the size and size distribution were measured by dynamic light scattering (DLS). The thermal performance and SiO2content were verified by thermogravimetric analysis (TGA). The results show that the prepared hybrid hollow microspheres have narrow size distributions in range of230-350nm. And they have a real empty core and a two-layer shell structure, with a thickness of30nm of the polymer layer and20nm of the silica layer.
本文第一章以细乳液聚合为主线,分别介绍了细乳液法制备无机／聚合物复合微球的研究进展,另外还介绍了WPU表面活性剂在细乳液聚合中的应用进展,以及细乳液聚合制备仿生材料的研究进展。
本文第二章介绍了SiO2/PMMA复合微球的细乳液法制备。采用异佛尔酮二异氰酸酯(IPDI)、聚醚二元醇N210和二羟甲基丙酸(DMPA)为主要反应原料,合成出羧酸型水性聚氨酯,并以甲基丙烯酸羟乙酯(HEMA)对其进行C=C封端,然后使用该水性聚氨酯作为可聚合表面活性剂,采用双原位细乳液法,不同引发剂体系引发聚合,制备出Si02/聚甲基丙烯酸甲酯复合微球。通过TEM、FTIR和TGA等测试方法对所得产物进行了表征分析。结果表明,使用水性聚氨酯表面活性剂所制备的Si02/聚甲基丙烯酸甲酯复合微球形貌,不同于传统小分子表面活性剂所制得产物的形貌,而且引发剂类型对Si02/聚甲基丙烯酸甲酯复合微球形貌有较大影响。
本文第三章介绍了nHA/PMMA复合微球的细乳液原位仿生合成方法。采用细乳液法合成出表而功能化的聚合物纳米粒子,并以其为模板,利用纳米粒子表面的离子对Ca2+的静电吸附作用,在一定的pH条件下,进行水相中纳米羟基磷灰石(nHA)在聚合物纳米粒子表面的原位仿生矿化,制备出nHA/聚合物复合微球。通过FT-IR、XRD和TEM等测试对所得产物进行了表征分析,并考察了nHA/聚合物复合微球对水杨酸药物的吸附作用。结果表明,复合微球上的无机组分为类似于人骨生物磷灰石的nHA,同时复合微球能够对水杨酸产生吸附作用,并且吸附性能随着水杨酸初始浓度的增大而增加,吸附速度快,5h即达到吸附平衡,这为骨组织再生、药物传递以及载药骨材料提供了潜在的应用可能性。
本文第四章介绍了一种窄粒径分布的SiO2/PAM杂化中空微球的双原位反相细乳液法制备。首先使用丙烯酰胺(AM)和二乙烯苯(DVB)的原位反相细乳液共聚合,制备出交联的聚合物纳米胶囊作为模板,通过硅酸乙酯(TEOS)的原位界面水解和沉淀,制备出窄粒径分布的杂化中空微球。通过使用SPAN-80和CTAB作为表面活性剂经均化器制备出pH可控的亲水性反相细乳液液滴,TEOS直接加入到反相细乳液的连续相中。由于二氧化硅通过界面溶胶凝胶过程,沉积在聚合物纳米胶囊表面形成了二氧化硅壳层。杂化中空微球形貌通过透射电子显微镜(TEM)直观观察,动态光散射(DLS)考察了粒径及粒径分布,热性能及Si02含量通过热分析(TGA)测试确定。结果表明制备出的杂化中空微球粒径分布较窄,大小为230-350nm,并且具有空心和双层壳结构,聚合物层为30nm, SiO2层为20nm。
As a novel method, miniemulsion polymerization has gained sufficient ratification and extensive spread in late decades. It has applied in industry abroad. Its advantages appear gradually, with the mechanism of miniemulsion being explored. Compared with common emulsion polymerization, miniemulsion has a smaller size of50-500nm, which is a great breakthrough in the area of smaller size. Moreover, as the more strict requirements of environmental protection and enhanced environment protecting consciousness, the amount of surfactant used in emulsion polymerization has been an important factor. A mass of surfactant used in emulsion polymerization affects the property of the final products, and pollutes the environment. But miniemulsion uses the least amount of surfactant, and guarantees the stability of latex. Especially, the polymerizable macromolecule surfactant used in miniemulsion makes it being green polymerization.
In the first chapter, the research process of preparation of inorganic/polymer composite microsphere via miniemulsion is introduced, with miniemulsion polymerization as the main clues. Applied process of waterborne polyurethane as surfactants in miniemulsion polymerization, together with miniemulsion preparation of biomimetic materials are also introduced.
In the second chapter, the preparation of SiO2/PMMA composite microspheres via miniemulsion polymerization was introduced. The carboxylic waterborne polyurethane was synthesized with isophorone diisocyanate(IPDI), polyether glycol(N210) and2,2-bis(hydroxymethyl)propionic acid(DMPA) as the major materials, and terminated by C=C from β-hydroxyethyl methacrylate(HEMA). SiO2/PMMA composite microspheres were prepared with different type of initiators by double in situ miniemulsion polymerization, in which the waterborne polyurethane was used as a polymerizable surfactant. The prepared products were characterized by TEM, FTIR and TGA, respectively. The results indicate that morphologies of the SiO2/PMMA composite microsphere prepared by waterborne polyurethane surfactant are different from those prepared by conventional micromolecule surfactants. The type of initiators affects significantly on the morphologies of the SiO2/PMMA.
In the third chapter, the method of in situ biomimetic synthesis of nHA/PMMA composite microspheres was introduced. nHA/polymer composite microspheres with the size of250nm were in situ biomimetic synthesized in the aqueous phase at37℃for7days by using the surface-functionalized polymeric nanoparticles as templates. A miniemulsion process was adopted to prepare the cross-linked templates via the co-polymerization of methyl methacrylate (MMA) and methyl acrylic acid (MAA). The functional groups (-COOH) were bound on the surface of polymeric nanoparticles. By utilizing the-COOH groups absorbing Ca+followed by HPO42-in certain pH conditions, hydroxyapatite (HA) crystal nucleus formed and grew up to be rod-like crystals on the surface in this system. Thus, nHA/polymer composite microspheres are successfully obtained, and studied by Fourier transform-infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), and transmission electron microscopy (TEM). The morphology of the polymeric nanoparticles and composite microspheres was investigated by (TEM). In the TEM images of polymeric templates, plenty of nanoparticles about200nm were observed. And some unsmooth nanoparticles with the larger size of250nm were presented in the TEM images of composite microspheres. The inorganic component, increased in size of the50nm in composite microspheres, confirmed to be low crystallized HA in nanoscale by XRD, which is similar to that of skeleton. Together with FT-IR, they showed that nHA was fabricated on the surface of polymer microspheres. Also, its adsorption studies on salicylic acid (SA) are investigated. The composite microspheres were dispersed in SA solution under constant stirring. After the SA adsorbed by the composite microspheres in certain time, the content of residual SA was detected using UV. It's also revealed that SA can be absorbed by composite microspheres. The intensity of absorption increases with the increase of the initial concentration of SA, and the absorption reaches equilibrium after5h at a fast speed. These nHA/polymer composite microspheres have great potential in bone tissue regeneration, drug delivery and bone materials loaded with drugs.
In the fourth chapter, the preparation of narrowly size-distributed hybrid hollow microspheres via double in-situ inverse miniemulsion polymerization and interfacial sol-gel process was introduced. Hybrid hollow microspheres with a narrow size distribution were successfully prepared via in-situ interfacial hydrolysis and condensation reactions of tetraethoxysilane (TEOS) based on the templates of cross-linked polymer nanocapsules, which were synthesized via in-situ inverse miniemulsion copolymerization of acrylamide (AM) and divinylbenzene (DVB). The inverse miniemulsions containing pH-controlled hydrophilic droplets were first prepared via homogenizer by using Span-80and cetyltrimethylarnmonium bromide (CTAB) as surfactants. TEOS was directly introduced to the continuous phase of an inverse miniemulsion. The silica shell was formed via interfacial sol-gel process by the deposition of silica on the surface of polymer nanocapsules. The formation of hybrid hollow microspheres morphology was confirmed by transmission electron microscopy (TEM), and the size and size distribution were measured by dynamic light scattering (DLS). The thermal performance and SiO2content were verified by thermogravimetric analysis (TGA). The results show that the prepared hybrid hollow microspheres have narrow size distributions in range of230-350nm. And they have a real empty core and a two-layer shell structure, with a thickness of30nm of the polymer layer and20nm of the silica layer.
引文
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