两亲性氟硅嵌段共聚物的胶束化及其在纳米金制备中的应用
发布时间：2018-07-17 16:12
【摘要】：两亲性嵌段共聚物胶束在热力学和动力学上比较稳定，可以作为“纳米反应器”用于制备各种无机纳米粒子。然而，对于两亲性共聚物的溶液自组装，，聚集体的形态取决于聚集体核与壳之间的界面能、核链段的伸展及壳链段间的排斥，因此两亲性嵌段共聚物组成的改变将影响其胶束形态与胶束化规律。 含有有机硅氧烷链段的两亲性共聚物，无论在水溶液还是在非水溶液中都具有很高的表面活性，能形成各种不同形状的聚集体。但是，若在含有机硅的两亲性嵌段共聚物中引入含氟基团，将影响链段之间的相互作用力，从而可能影响含氟硅共聚物的在溶液中的聚集态结构与自组装行为。本文藉此开展了含氟聚硅氧烷与聚(甲基)丙烯酸嵌段共聚物的合成、胶束化及其在纳米金制备中的应用研究。 主要研究成果如下： 一、合成得到一系列结构可控的聚[甲基(3,3,3-三氟丙基)硅氧烷]-block-聚(甲基)丙烯酸（PMTFPS-b-P(M)AA）嵌段共聚物。 1.通过结合氟硅单体1,3,5-三甲基-1,3,5-三（3′,3′,3′-三氟丙基）环三硅氧烷（F3）的阴离子开环聚合（ROP），以及丙烯酸叔丁酯（tBA）或甲基丙烯酸叔丁酯（tBMA）的原子转移自由基聚合（ATRP），得到一系列分子组成可设计的聚[甲基(3,3,3-三氟丙基)硅氧烷]-block-聚(甲基)丙烯酸叔丁酯（PMTFPS-b-PtB(M)A）嵌段共聚物。 2.通过NaI/((TMS)Cl)水解法，在不破坏聚合物主链的前提下，成功水解了PMTFPS-b-PtB(M)A嵌段共聚物，获得了两亲性PMTFPS-b-P(M)AA嵌段共聚物，且水解率可达84.6%。 二、成功实现了两亲性PMTFPS-b-P(M)AA嵌段共聚物的溶液胶束化，获得球形、珍珠链状、囊泡状等多种形态的聚集体。 1.采用芘（pyrene）荧光探针技术研究发现，PMTFPS-b-PAA嵌段共聚物的临界胶束浓度为0.05wt%左右。 2.两亲性PMTFPS-b-PAA嵌段共聚物的溶液胶束化研究发现，在丙酮/水混合溶剂中，嵌段共聚物的组成、聚合物浓度、水量、加水时间等因素影响共聚物胶束的形态。通过调控这些影响因素，可制备得到球形、珍珠链状等多种形态的聚集体。 3.两亲性PMTFPS-b-PMAA嵌段共聚物在丙酮/水混合溶剂中，通过改变聚合物浓度、水量等自组装制备条件，可获得球形、珍珠链状等聚集体；而在二氧六环/水溶剂体系中，得到了不同于丙酮/水溶液的囊泡及复合囊泡。 三、本文利用两亲性PMTFPS-b-P(M)AA嵌段共聚物胶束，成功制备得到稳定的小尺寸金纳米粒子。 1.本文利用PMTFPS-b-PAA在丙酮/水体系中形成的球形胶束作为“微/纳米反应器”，以聚环氧乙烷（PEO）为还原剂，成功制备得到尺寸在2-6nm的金纳米粒子，且所得纳米金溶胶体系稳定性较好。 2.研究发现，在PMTFPS-b-PAA胶束中，氯金酸可快速被PEO还原为金纳米粒子，但利用纯PEO即使在较长的时间（48h）下也无法令全部氯金酸还原，这说明PMTFPS-b-PAA胶束可为氯金酸的还原提供微反应场所，使其快速完成还原反应。 3.利用荧光与激光共聚焦（CLSM）分析技术研究表明，本文制备得到的金纳米粒子在一定的激发条件下会发出绿色荧光，而且分散、稳定在胶束内部。 4.此外，本文利用两亲性PMTFPS-b-PMAA嵌段共聚物胶束，成功将预先还原的金纳米粒子包裹、稳定在胶束中。
[Abstract]:The two amphiphilic block copolymer micelles are relatively stable in thermodynamics and kinetics, and can be used as "nano reactors" for the preparation of various inorganic nanoparticles. However, for the self assembly of the solution of the two amphiphilic copolymers, the morphology of the aggregates depends on the boundary energy between the core and the shell, the extension of the nuclear chain segments and the rejection between the shell segments. Therefore, the change of the composition of two affinity block copolymers will affect the micelle morphology and micellation rule.
Two amphiphilic copolymers containing organosiloxane segments have high surface activity in both aqueous and non aqueous solutions, and can form aggregates of various shapes. However, if fluorinated groups are introduced into the two amphiphilic block copolymers containing organic silicon, the interaction between the segments will affect the interaction between the segments, which may affect the content of the polymer. The aggregation structure and self-assembly behavior of the Fluorosilicic copolymer in the solution. The synthesis, micelization of the fluorinated polysiloxane and poly (methyl) acrylic acid block copolymer, and its application in the preparation of gold nanoparticles were studied in this paper.
The main research results are as follows:
First, a series of controllable poly (methyl 3,3,3- (three fluoro propyl) siloxane]-block- poly (methyl) acrylic acid (PMTFPS-b-P (M) AA) block copolymers were synthesized.
1. by combining the anion opening polymerization (ROP) of the fluorosilicon monomer 1,3,5- three methyl -1,3,5- three (3 ', 3', 3 '- three fluorpropyl) ring three siloxane (F3), as well as the atomic transfer radical polymerization (ATRP) of tert butyl acrylate (tBA) or tertiary butyl methacrylate (tBMA), a series of molecular composition can be designed for poly [methyl (3,3,3- three fluoro propyl)). Siloxane]-block- poly (methyl) tert butyl acrylate (PMTFPS-b-PtB (M) A) block copolymer.
2. by NaI/ ((TMS) Cl) hydrolysis, the PMTFPS-b-PtB (M) A block copolymer was successfully hydrolyzed without destroying the main chain of the polymer, and two Pro PMTFPS-b-P (M) AA block copolymers were obtained, and the hydrolysis rate could reach 84.6%..
Two, the micelllization of two affinity PMTFPS-b-P (M) AA block copolymer was successfully achieved, and spherical, pearl chain and vesicle aggregates were obtained.
1. using pyrene (pyrene) fluorescence probe technology, it is found that the critical micelle concentration of PMTFPS-b-PAA block copolymer is about 0.05wt%.
2. the solution micellization of 2. two amphiphilic block copolymers found that the composition of the block copolymer, the concentration of the polymer, the amount of water, the time of adding water and so on influenced the morphology of the copolymer micelles in the acetone / water mixed solvent. By controlling these factors, the aggregates of various forms such as spherical and pearl chain could be prepared.
3. two amphiphilic PMTFPS-b-PMAA block copolymers can obtain spherical and pearl chain aggregates by altering the polymer concentration, water and other self assembly conditions in the acetone / water mixed solvent, and the vesicles and composite vesicles different from the acetone / water solution are obtained in the two oxygen six ring / water solvent system.
Three, by using two affinity PMTFPS-b-P (M) AA block copolymer micelles, stable small size gold nanoparticles were successfully prepared.
1. in this paper, the spherical micelle formed in the acetone / water system was used as a "micro / nano reactor", and polyepoxide (PEO) was used as a reducing agent. The gold nanoparticles with size in 2-6nm were prepared successfully, and the stability of the nanoscale colloid system was better.
2. the study found that chloro gold acid can quickly be reduced to gold nanoparticles by PEO in PMTFPS-b-PAA micelles, but the use of pure PEO can not reduce all chlorchloric acid even at a long time (48h), which indicates that the PMTFPS-b-PAA micelles can provide a micro reaction place for the reduction of chlorauric acid and make it complete the reduction reaction quickly.
3. the study of fluorescence and laser confocal (CLSM) analysis shows that the gold nanoparticles prepared in this paper will send out green fluorescence under certain excitation conditions, and are dispersed and stable in the micelles.
4. in addition, the two affinity PMTFPS-b-PMAA block copolymer micelles were successfully applied to encapsulate the pre reduced gold nanoparticles and stabilize them in micelles.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ131.23;O631.1
本文编号：2130202
[Abstract]:The two amphiphilic block copolymer micelles are relatively stable in thermodynamics and kinetics, and can be used as "nano reactors" for the preparation of various inorganic nanoparticles. However, for the self assembly of the solution of the two amphiphilic copolymers, the morphology of the aggregates depends on the boundary energy between the core and the shell, the extension of the nuclear chain segments and the rejection between the shell segments. Therefore, the change of the composition of two affinity block copolymers will affect the micelle morphology and micellation rule.
Two amphiphilic copolymers containing organosiloxane segments have high surface activity in both aqueous and non aqueous solutions, and can form aggregates of various shapes. However, if fluorinated groups are introduced into the two amphiphilic block copolymers containing organic silicon, the interaction between the segments will affect the interaction between the segments, which may affect the content of the polymer. The aggregation structure and self-assembly behavior of the Fluorosilicic copolymer in the solution. The synthesis, micelization of the fluorinated polysiloxane and poly (methyl) acrylic acid block copolymer, and its application in the preparation of gold nanoparticles were studied in this paper.
The main research results are as follows:
First, a series of controllable poly (methyl 3,3,3- (three fluoro propyl) siloxane]-block- poly (methyl) acrylic acid (PMTFPS-b-P (M) AA) block copolymers were synthesized.
1. by combining the anion opening polymerization (ROP) of the fluorosilicon monomer 1,3,5- three methyl -1,3,5- three (3 ', 3', 3 '- three fluorpropyl) ring three siloxane (F3), as well as the atomic transfer radical polymerization (ATRP) of tert butyl acrylate (tBA) or tertiary butyl methacrylate (tBMA), a series of molecular composition can be designed for poly [methyl (3,3,3- three fluoro propyl)). Siloxane]-block- poly (methyl) tert butyl acrylate (PMTFPS-b-PtB (M) A) block copolymer.
2. by NaI/ ((TMS) Cl) hydrolysis, the PMTFPS-b-PtB (M) A block copolymer was successfully hydrolyzed without destroying the main chain of the polymer, and two Pro PMTFPS-b-P (M) AA block copolymers were obtained, and the hydrolysis rate could reach 84.6%..
Two, the micelllization of two affinity PMTFPS-b-P (M) AA block copolymer was successfully achieved, and spherical, pearl chain and vesicle aggregates were obtained.
1. using pyrene (pyrene) fluorescence probe technology, it is found that the critical micelle concentration of PMTFPS-b-PAA block copolymer is about 0.05wt%.
2. the solution micellization of 2. two amphiphilic block copolymers found that the composition of the block copolymer, the concentration of the polymer, the amount of water, the time of adding water and so on influenced the morphology of the copolymer micelles in the acetone / water mixed solvent. By controlling these factors, the aggregates of various forms such as spherical and pearl chain could be prepared.
3. two amphiphilic PMTFPS-b-PMAA block copolymers can obtain spherical and pearl chain aggregates by altering the polymer concentration, water and other self assembly conditions in the acetone / water mixed solvent, and the vesicles and composite vesicles different from the acetone / water solution are obtained in the two oxygen six ring / water solvent system.
Three, by using two affinity PMTFPS-b-P (M) AA block copolymer micelles, stable small size gold nanoparticles were successfully prepared.
1. in this paper, the spherical micelle formed in the acetone / water system was used as a "micro / nano reactor", and polyepoxide (PEO) was used as a reducing agent. The gold nanoparticles with size in 2-6nm were prepared successfully, and the stability of the nanoscale colloid system was better.
2. the study found that chloro gold acid can quickly be reduced to gold nanoparticles by PEO in PMTFPS-b-PAA micelles, but the use of pure PEO can not reduce all chlorchloric acid even at a long time (48h), which indicates that the PMTFPS-b-PAA micelles can provide a micro reaction place for the reduction of chlorauric acid and make it complete the reduction reaction quickly.
3. the study of fluorescence and laser confocal (CLSM) analysis shows that the gold nanoparticles prepared in this paper will send out green fluorescence under certain excitation conditions, and are dispersed and stable in the micelles.
4. in addition, the two affinity PMTFPS-b-PMAA block copolymer micelles were successfully applied to encapsulate the pre reduced gold nanoparticles and stabilize them in micelles.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ131.23;O631.1
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相关博士学位论文 前1条
1 陈碧;聚硅氧烷聚醚两亲性嵌段共聚物的合成及其溶液自组装[D];浙江大学;2008年
本文编号：2130202
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