光聚合法制备高分子微球及其性能研究
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摘要
光聚合作为一种重要的聚合物材料的合成技术，与传统的热聚合相比，具有环境污染小、能耗低、聚合速度快、聚合温度低、设备简单以及易于工业化生产等优点。随着全球化经济的飞速发展，环境污染问题和能源危机日趋严重，而光聚合环境污染小和生产能耗低的优点正符合聚合技术未来发展方向，具有极为广阔的应用前景。
高分子微球因其特殊尺寸和结构在许多领域如医学工程、生物工程、电子信息、化学工程、化妆品等等领域有广泛的应用。高分子微球的合成方法很多，如乳液聚合、悬浮聚合、分散聚合、沉淀聚合，已经形成粒径在0.01-100μm范围内尺寸均一的微球制备体系。但是，这些聚合方法基本采用热引发聚合体系，聚合温度较高。而光聚合可以在低温进行，聚合速度快，在高分子微球的制备方面具有独特的优势。高分子微球的制备方法中，分散聚合和乳液聚合是适用面最广的制备高分子微球的经典方法，分散聚合适合于制备纳米级和微米级微球，而乳液聚合适合于纳米级微球，所制备的微球分布均匀，制备方法简单，在高分子微球制备技术中占有极为重要的地位。本论文研究了将光聚合应用于高分子微球制备，通过光引发分散聚合和无皂乳液聚合分别合成不同结构、不同粒径和不同形态的高分子微球，对微球聚合过程中的影响因素进行了较为系统的研究。在合成得到的高分子微球上分别进行金属纳米颗粒的负载研究，所得的复合微球分别表现出一定程度的催化性、抗菌性和荧光增强作用。主要研究内容如下:
（1）光引发分散聚合法制备P(NIPAAm-g-St)微球
首先是大分子单体的合成，以巯基乙醇为链转移剂，采用链转移自由基聚合法制备末端带羟基的N-异丙基丙烯酰胺低聚物(PNIPAAm)，再通过端基置换反应得到末端带双键的PNIPAAm大分子单体，分别采用凝胶渗透色谱（GPC）、紫外-可见分光光谱（UV-Vis）、傅里叶转换红外线光谱（FT-IR）和氢核磁共振波谱(1H-NMR)对大分子单体进行表征，所得大分子单体分子量为4000，末端双键的引入率为60%；其次是P(NIPAAm-g-St)微球的合成，以2，2-二甲氧基-2-苯基苯乙酮为光引发剂，PNIPAAm大分子单体作为共聚单体和分散稳定剂，在乙醇和水（7/3，V/V）的混合介质中通过紫外光辐照进行分散光聚合得到P(NIPAAm-g-St)微球。微球的形态、粒径和粒径分布采用扫描电镜(SEM)和激光光散射(LLS)进行表征。结果显示在低辐照条件下制备的高分子微球粒径分布明显小于高辐照条件下制备的微球，探讨了光辐照强度、大分子单体的浓度和聚合温度对合成微球的粒径的影响，结果表明辐照强度越大、单分子单体浓度越高、聚合反应温度越低，所得微球的粒径越大，聚合反应速度表现为先快后慢直至停止反应，聚合转化率可达到70%以上。
（2）光引发分散聚合法制备Pd/PNVA-g-PAN/PSt
首先是PNVA大分子单体的合成，通过退化链转移自由基聚合和端基置换成功制备末端带双键的PNVA大分子单体，再以St、AN和大分子单体PNVA为共聚单体，PNVA大分子单体同时也是分散稳定剂，在乙醇和水（7/3，V/V）的混合溶剂中通过光引发分散聚合制备PNVA-g-PAN/PSt微球，所得微球结构通过FT-IR、1H-NMR进行表征，微球的粒径和形态采用SEM表征，所得微球粒径在范围500-800nm内可控，微球为表面带花瓣的球形结构；然后是Pd/PNVA-g-PAN/PSt复合微球的制备，以PdCl2为金属源通过原位还原的方法在合成高分子微球表面进行Pd纳米颗粒负载，得到Pd/PNVA-g-PAN/PSt复合微球，复合微球形态采用透射电镜(TEM)表征，通过热失重分析（TGA）测试得到复合微球Pd负载量在15-30%，XRD图谱显示Pd纳米颗粒结构为立方晶体结构，Pd纳米颗粒的粒径为9nm，与TEM表征结果相符。最后对复合微球的催化性能进行研究，以复合微球为催化剂，分别对葡萄糖的氧化反应和对碘代苯与丙烯酸的交叉偶联反应进行研究，结果表明复合微球在这两种反应中具有良好的催化性能，且复合微球能够回收利用。
（3）光引发剂分散聚合法制备Ag/P(St-co-MMA)复合微球
首先是P(St-co-MMA)的制备，以2，2-二甲氧基-2-苯基苯乙酮（BDK）为光引发剂，PVP为分散剂，在乙醇和水的混合介质中通过光引发分散聚合制备P(St-co-MMA)高分子微球。微球的结构采用FT-IR表征,粒径和粒径分布采用LLS表征，形态采用SEM表征，结果显示，所得高分子微球粒径在200-500nm内可控。其次是Ag/P(St-co-MMA)复合微球的制备，以AgNO3为金属源，分别以NaBH4和紫外光还原法通过原位还原将纳米Ag负载在P(St-co-MMA)微球表面，复合微球结构分别通过UV-vis, TEM和XRD进行表征，微球表面负载Ag纳米颗粒粒径在10-20nm，晶型为立方晶系，并发现采用NaBH4还原法制备的复合微球中的Ag纳米颗粒粒径更小。最后是复合微球的性能研究，分别研究了复合微球对金色葡萄球菌的抗菌性、对荧光素的荧光增强性质和对亚甲基蓝的光催化降解性，结果显示复合微球具有优良的抗菌性，对亚甲基蓝（MB）光降解反应具有一定的催化活性，对荧光素的荧光性能有一定增强作用和。
（4）光引发无皂乳液聚合法制备P(St-co-MMA-co-AA)微球
以水溶性的2-羟基-4-(2-羟乙氧基)-2-甲基苯丙酮为光引发剂，水为分散介质，通过无皂乳液聚合法成功制备P(St-co-MMA-co-AA)微球。微球的结构通过FT-IR进行表征，微球的形态通过SEM表征，微球的粒径和粒径分布通过LLS表征，采用测量电导率的方法来测量微球表面羧基含量。结果表明光引发无皂乳液聚合法制备的P(St-co-AA)微球粒径为180nm，粒径分布较窄，改变共聚单体配比能控制所得高分子微球的粒径大小，共聚单体丙烯酸用量越大，所得共聚物微球的粒径越低，聚合转化率达到90%，高于光引发剂分散聚合产率；以P(St-co-MMA-co-AA)微球为载体负载Ag纳米颗粒，通过UV-vis, TEM和XRD进行表征。
Photopolymerization is an important synthesis technology in polymer material，andcompared to thermal-initiated polymerization, The typical characteristic ofPhotopolymerization lies in that it can be carried out at low temperature,high reaction rate，energy saving, simple equipment, easy to implement industrial production and so on. With therapid development of global economy，the threats of energy and environment problem areincreasingly serious； Photopolymerization has tremendous advantages on sustainabledevelopment strategy.
Polymer microspheres are finding to be increasing applications in various fields, such asmedicines, biotechnologies, electronics, chemical technologies, cosmetics and so on. Variousmethods have been employed to prepare polymer microspheres, such as emulsionpolymerization, suspension polymerization, and dispersion polymerization. However, thesemethods must be proceeded at high temperature by thermal-initiated polymerization, whichare energy-consuming and often difficult to prepare in low temperature. The thesis hasreviewed the photopolymerization technology was applied in the preparation polymermicrospheres. The main contents of this paper are as follows.
(1) P(St-g-NIPAAM) microspheres were synthesized through dispersionPhotopolymerization. Taking2,2-dimethoxy-2-phenylacetophenone (BDK) as photoinitiator,PNIPAAM with a vinyl end groupas stabilizer,the mixture of ethanol and water asdispersion medium，P(St-g-NIPAAM) microspheres with narrow size distribution weresynthesized under the irradiation of UV-lamp．The obtained microspheres were characterizedby scanning electron microscopy (SEM) and laser light scattering (LLS). The monodispersionP(St-g-NIPAAM) nanospheres were obtained by UV photo-initiated polymerization of St andPNIPAAM in the ethanol-water media at low UV illumination. The results show that the sizeof microspheres can be controlled by changing the UV illumination, concentration ofmacromoners, and the polymerization temperature.
(2) Pd/PNVA-g-PAN/PSt composite microspheres were synthesized successfully.Firstly, PNVA-g-PAN/PSt microspheres were prepared by dispersion photocopolymerizationof acrylonitrile (AN) with styrene (St) in the mixture of ethanol and water using dispersionmedium, PNVA macromonomer as reaction stabilizer. PNVA-g-PAN/PSt microsphereswere characterized FT-IR and1H-NMR. The diameter range of microspheres were controledin range from500-1000nm.Next, palladium nanoparticles were located onto the surfaces ofmicrospheres in the mixture of ethanol and water by in-situ reduction method using PdCl2as metal source and ethanol as reducing agent at90℃. The sizes of PdNPs were around9nmby TEM observations, The weight percents of PdNPs immobilized onto the microsphereswere15to30%, depending on the feed amount of Pd2+ions based on determination of TGA.XRD pattern showed that PdNPs were of face-centered cubic crystal structures. PdNPsshowed high activity and selectivity to catalyze the cross-coupling reaction of iodobenzenewith acrylic acid.
(3) Ag/P(St-co-MMA) composite microspheres were synthesized. Firstly,P(St-co-MMA) microspheres were prepared by dispersion Photocopolymerization of Styrene(St) and methyl methacrylate (MMA) in a mixture of ethanol and water(Vethanol/Vwater=7/3) using BDK and polyvinylpyrrolidone (PVP) as the initiator andstabilizer, respectively. The structure of microspheres were characterized by FTIR, The sizeand size distribution of microspheres were characterized by LLS, The shape of microsphereswere characterized TEM. The results show that the size of P(St-co-MMA) microspheres canbe controlled in range from500to800nm. Next, Ag nanoparticles were located evenly ontosurface of the microspheres above. Taking silver nitrate (AgNO3) as metal source, Theultrafine dispersed nanoparticles of Ag can be located surface of the microspheres via thereduction of corresponding silver ions (Ag+) by sodium borohydride (NaBH4) or ultraviolet(UV) light. The composite microspheres were characterized by UV-vis, TEM and X-raydiffractometry (XRD). The composite microspheres had good antibacterial property andphotocatalytic. The composite microspheres on the fluorescent properties of fluorescein (FL)were also investigated. With the increase of Ag nanoparticles concentrations, the fluorescenceenhancement efficiency had a maximum.
(4) P(St-co-AA) microspheres were prepared by Soap-free EmulsionPhotocopolymerization of St and acrylic acid (AA) in water using2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone. The structure of microspheres werecharacterized by FTIR, The shape of microspheres were characterized TEM,The size and sizedistribution of microspheres were characterized by LLS, The sizes of microspheres werearound70nm, Conversion rate of photopolymerization is up to86%.
高分子微球因其特殊尺寸和结构在许多领域如医学工程、生物工程、电子信息、化学工程、化妆品等等领域有广泛的应用。高分子微球的合成方法很多，如乳液聚合、悬浮聚合、分散聚合、沉淀聚合，已经形成粒径在0.01-100μm范围内尺寸均一的微球制备体系。但是，这些聚合方法基本采用热引发聚合体系，聚合温度较高。而光聚合可以在低温进行，聚合速度快，在高分子微球的制备方面具有独特的优势。高分子微球的制备方法中，分散聚合和乳液聚合是适用面最广的制备高分子微球的经典方法，分散聚合适合于制备纳米级和微米级微球，而乳液聚合适合于纳米级微球，所制备的微球分布均匀，制备方法简单，在高分子微球制备技术中占有极为重要的地位。本论文研究了将光聚合应用于高分子微球制备，通过光引发分散聚合和无皂乳液聚合分别合成不同结构、不同粒径和不同形态的高分子微球，对微球聚合过程中的影响因素进行了较为系统的研究。在合成得到的高分子微球上分别进行金属纳米颗粒的负载研究，所得的复合微球分别表现出一定程度的催化性、抗菌性和荧光增强作用。主要研究内容如下:
（1）光引发分散聚合法制备P(NIPAAm-g-St)微球
首先是大分子单体的合成，以巯基乙醇为链转移剂，采用链转移自由基聚合法制备末端带羟基的N-异丙基丙烯酰胺低聚物(PNIPAAm)，再通过端基置换反应得到末端带双键的PNIPAAm大分子单体，分别采用凝胶渗透色谱（GPC）、紫外-可见分光光谱（UV-Vis）、傅里叶转换红外线光谱（FT-IR）和氢核磁共振波谱(1H-NMR)对大分子单体进行表征，所得大分子单体分子量为4000，末端双键的引入率为60%；其次是P(NIPAAm-g-St)微球的合成，以2，2-二甲氧基-2-苯基苯乙酮为光引发剂，PNIPAAm大分子单体作为共聚单体和分散稳定剂，在乙醇和水（7/3，V/V）的混合介质中通过紫外光辐照进行分散光聚合得到P(NIPAAm-g-St)微球。微球的形态、粒径和粒径分布采用扫描电镜(SEM)和激光光散射(LLS)进行表征。结果显示在低辐照条件下制备的高分子微球粒径分布明显小于高辐照条件下制备的微球，探讨了光辐照强度、大分子单体的浓度和聚合温度对合成微球的粒径的影响，结果表明辐照强度越大、单分子单体浓度越高、聚合反应温度越低，所得微球的粒径越大，聚合反应速度表现为先快后慢直至停止反应，聚合转化率可达到70%以上。
（2）光引发分散聚合法制备Pd/PNVA-g-PAN/PSt
首先是PNVA大分子单体的合成，通过退化链转移自由基聚合和端基置换成功制备末端带双键的PNVA大分子单体，再以St、AN和大分子单体PNVA为共聚单体，PNVA大分子单体同时也是分散稳定剂，在乙醇和水（7/3，V/V）的混合溶剂中通过光引发分散聚合制备PNVA-g-PAN/PSt微球，所得微球结构通过FT-IR、1H-NMR进行表征，微球的粒径和形态采用SEM表征，所得微球粒径在范围500-800nm内可控，微球为表面带花瓣的球形结构；然后是Pd/PNVA-g-PAN/PSt复合微球的制备，以PdCl2为金属源通过原位还原的方法在合成高分子微球表面进行Pd纳米颗粒负载，得到Pd/PNVA-g-PAN/PSt复合微球，复合微球形态采用透射电镜(TEM)表征，通过热失重分析（TGA）测试得到复合微球Pd负载量在15-30%，XRD图谱显示Pd纳米颗粒结构为立方晶体结构，Pd纳米颗粒的粒径为9nm，与TEM表征结果相符。最后对复合微球的催化性能进行研究，以复合微球为催化剂，分别对葡萄糖的氧化反应和对碘代苯与丙烯酸的交叉偶联反应进行研究，结果表明复合微球在这两种反应中具有良好的催化性能，且复合微球能够回收利用。
（3）光引发剂分散聚合法制备Ag/P(St-co-MMA)复合微球
首先是P(St-co-MMA)的制备，以2，2-二甲氧基-2-苯基苯乙酮（BDK）为光引发剂，PVP为分散剂，在乙醇和水的混合介质中通过光引发分散聚合制备P(St-co-MMA)高分子微球。微球的结构采用FT-IR表征,粒径和粒径分布采用LLS表征，形态采用SEM表征，结果显示，所得高分子微球粒径在200-500nm内可控。其次是Ag/P(St-co-MMA)复合微球的制备，以AgNO3为金属源，分别以NaBH4和紫外光还原法通过原位还原将纳米Ag负载在P(St-co-MMA)微球表面，复合微球结构分别通过UV-vis, TEM和XRD进行表征，微球表面负载Ag纳米颗粒粒径在10-20nm，晶型为立方晶系，并发现采用NaBH4还原法制备的复合微球中的Ag纳米颗粒粒径更小。最后是复合微球的性能研究，分别研究了复合微球对金色葡萄球菌的抗菌性、对荧光素的荧光增强性质和对亚甲基蓝的光催化降解性，结果显示复合微球具有优良的抗菌性，对亚甲基蓝（MB）光降解反应具有一定的催化活性，对荧光素的荧光性能有一定增强作用和。
（4）光引发无皂乳液聚合法制备P(St-co-MMA-co-AA)微球
以水溶性的2-羟基-4-(2-羟乙氧基)-2-甲基苯丙酮为光引发剂，水为分散介质，通过无皂乳液聚合法成功制备P(St-co-MMA-co-AA)微球。微球的结构通过FT-IR进行表征，微球的形态通过SEM表征，微球的粒径和粒径分布通过LLS表征，采用测量电导率的方法来测量微球表面羧基含量。结果表明光引发无皂乳液聚合法制备的P(St-co-AA)微球粒径为180nm，粒径分布较窄，改变共聚单体配比能控制所得高分子微球的粒径大小，共聚单体丙烯酸用量越大，所得共聚物微球的粒径越低，聚合转化率达到90%，高于光引发剂分散聚合产率；以P(St-co-MMA-co-AA)微球为载体负载Ag纳米颗粒，通过UV-vis, TEM和XRD进行表征。
Photopolymerization is an important synthesis technology in polymer material，andcompared to thermal-initiated polymerization, The typical characteristic ofPhotopolymerization lies in that it can be carried out at low temperature,high reaction rate，energy saving, simple equipment, easy to implement industrial production and so on. With therapid development of global economy，the threats of energy and environment problem areincreasingly serious； Photopolymerization has tremendous advantages on sustainabledevelopment strategy.
Polymer microspheres are finding to be increasing applications in various fields, such asmedicines, biotechnologies, electronics, chemical technologies, cosmetics and so on. Variousmethods have been employed to prepare polymer microspheres, such as emulsionpolymerization, suspension polymerization, and dispersion polymerization. However, thesemethods must be proceeded at high temperature by thermal-initiated polymerization, whichare energy-consuming and often difficult to prepare in low temperature. The thesis hasreviewed the photopolymerization technology was applied in the preparation polymermicrospheres. The main contents of this paper are as follows.
(1) P(St-g-NIPAAM) microspheres were synthesized through dispersionPhotopolymerization. Taking2,2-dimethoxy-2-phenylacetophenone (BDK) as photoinitiator,PNIPAAM with a vinyl end groupas stabilizer,the mixture of ethanol and water asdispersion medium，P(St-g-NIPAAM) microspheres with narrow size distribution weresynthesized under the irradiation of UV-lamp．The obtained microspheres were characterizedby scanning electron microscopy (SEM) and laser light scattering (LLS). The monodispersionP(St-g-NIPAAM) nanospheres were obtained by UV photo-initiated polymerization of St andPNIPAAM in the ethanol-water media at low UV illumination. The results show that the sizeof microspheres can be controlled by changing the UV illumination, concentration ofmacromoners, and the polymerization temperature.
(2) Pd/PNVA-g-PAN/PSt composite microspheres were synthesized successfully.Firstly, PNVA-g-PAN/PSt microspheres were prepared by dispersion photocopolymerizationof acrylonitrile (AN) with styrene (St) in the mixture of ethanol and water using dispersionmedium, PNVA macromonomer as reaction stabilizer. PNVA-g-PAN/PSt microsphereswere characterized FT-IR and1H-NMR. The diameter range of microspheres were controledin range from500-1000nm.Next, palladium nanoparticles were located onto the surfaces ofmicrospheres in the mixture of ethanol and water by in-situ reduction method using PdCl2as metal source and ethanol as reducing agent at90℃. The sizes of PdNPs were around9nmby TEM observations, The weight percents of PdNPs immobilized onto the microsphereswere15to30%, depending on the feed amount of Pd2+ions based on determination of TGA.XRD pattern showed that PdNPs were of face-centered cubic crystal structures. PdNPsshowed high activity and selectivity to catalyze the cross-coupling reaction of iodobenzenewith acrylic acid.
(3) Ag/P(St-co-MMA) composite microspheres were synthesized. Firstly,P(St-co-MMA) microspheres were prepared by dispersion Photocopolymerization of Styrene(St) and methyl methacrylate (MMA) in a mixture of ethanol and water(Vethanol/Vwater=7/3) using BDK and polyvinylpyrrolidone (PVP) as the initiator andstabilizer, respectively. The structure of microspheres were characterized by FTIR, The sizeand size distribution of microspheres were characterized by LLS, The shape of microsphereswere characterized TEM. The results show that the size of P(St-co-MMA) microspheres canbe controlled in range from500to800nm. Next, Ag nanoparticles were located evenly ontosurface of the microspheres above. Taking silver nitrate (AgNO3) as metal source, Theultrafine dispersed nanoparticles of Ag can be located surface of the microspheres via thereduction of corresponding silver ions (Ag+) by sodium borohydride (NaBH4) or ultraviolet(UV) light. The composite microspheres were characterized by UV-vis, TEM and X-raydiffractometry (XRD). The composite microspheres had good antibacterial property andphotocatalytic. The composite microspheres on the fluorescent properties of fluorescein (FL)were also investigated. With the increase of Ag nanoparticles concentrations, the fluorescenceenhancement efficiency had a maximum.
(4) P(St-co-AA) microspheres were prepared by Soap-free EmulsionPhotocopolymerization of St and acrylic acid (AA) in water using2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone. The structure of microspheres werecharacterized by FTIR, The shape of microspheres were characterized TEM,The size and sizedistribution of microspheres were characterized by LLS, The sizes of microspheres werearound70nm, Conversion rate of photopolymerization is up to86%.
引文
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