兩親性氟硅嵌段共聚物的膠束化及其在納米金制備中的應(yīng)用
發(fā)布時(shí)間：2018-07-17 16:12
【摘要】：兩親性嵌段共聚物膠束在熱力學(xué)和動力學(xué)上比較穩(wěn)定，可以作為“納米反應(yīng)器”用于制備各種無機(jī)納米粒子。然而，對于兩親性共聚物的溶液自組裝，，聚集體的形態(tài)取決于聚集體核與殼之間的界面能、核鏈段的伸展及殼鏈段間的排斥，因此兩親性嵌段共聚物組成的改變將影響其膠束形態(tài)與膠束化規(guī)律。 含有有機(jī)硅氧烷鏈段的兩親性共聚物，無論在水溶液還是在非水溶液中都具有很高的表面活性，能形成各種不同形狀的聚集體。但是，若在含有機(jī)硅的兩親性嵌段共聚物中引入含氟基團(tuán)，將影響鏈段之間的相互作用力，從而可能影響含氟硅共聚物的在溶液中的聚集態(tài)結(jié)構(gòu)與自組裝行為。本文藉此開展了含氟聚硅氧烷與聚(甲基)丙烯酸嵌段共聚物的合成、膠束化及其在納米金制備中的應(yīng)用研究。 主要研究成果如下： 一、合成得到一系列結(jié)構(gòu)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.通過結(jié)合氟硅單體1,3,5-三甲基-1,3,5-三（3′,3′,3′-三氟丙基）環(huán)三硅氧烷（F3）的陰離子開環(huán)聚合（ROP），以及丙烯酸叔丁酯（tBA）或甲基丙烯酸叔丁酯（tBMA）的原子轉(zhuǎn)移自由基聚合（ATRP），得到一系列分子組成可設(shè)計(jì)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.通過NaI/((TMS)Cl)水解法，在不破壞聚合物主鏈的前提下，成功水解了PMTFPS-b-PtB(M)A嵌段共聚物，獲得了兩親性PMTFPS-b-P(M)AA嵌段共聚物，且水解率可達(dá)84.6%。 二、成功實(shí)現(xiàn)了兩親性PMTFPS-b-P(M)AA嵌段共聚物的溶液膠束化，獲得球形、珍珠鏈狀、囊泡狀等多種形態(tài)的聚集體。 1.采用芘（pyrene）熒光探針技術(shù)研究發(fā)現(xiàn)，PMTFPS-b-PAA嵌段共聚物的臨界膠束濃度為0.05wt%左右。 2.兩親性PMTFPS-b-PAA嵌段共聚物的溶液膠束化研究發(fā)現(xiàn)，在丙酮/水混合溶劑中，嵌段共聚物的組成、聚合物濃度、水量、加水時(shí)間等因素影響共聚物膠束的形態(tài)。通過調(diào)控這些影響因素，可制備得到球形、珍珠鏈狀等多種形態(tài)的聚集體。 3.兩親性PMTFPS-b-PMAA嵌段共聚物在丙酮/水混合溶劑中，通過改變聚合物濃度、水量等自組裝制備條件，可獲得球形、珍珠鏈狀等聚集體；而在二氧六環(huán)/水溶劑體系中，得到了不同于丙酮/水溶液的囊泡及復(fù)合囊泡。 三、本文利用兩親性PMTFPS-b-P(M)AA嵌段共聚物膠束，成功制備得到穩(wěn)定的小尺寸金納米粒子。 1.本文利用PMTFPS-b-PAA在丙酮/水體系中形成的球形膠束作為“微/納米反應(yīng)器”，以聚環(huán)氧乙烷（PEO）為還原劑，成功制備得到尺寸在2-6nm的金納米粒子，且所得納米金溶膠體系穩(wěn)定性較好。 2.研究發(fā)現(xiàn)，在PMTFPS-b-PAA膠束中，氯金酸可快速被PEO還原為金納米粒子，但利用純PEO即使在較長的時(shí)間（48h）下也無法令全部氯金酸還原，這說明PMTFPS-b-PAA膠束可為氯金酸的還原提供微反應(yīng)場所，使其快速完成還原反應(yīng)。 3.利用熒光與激光共聚焦（CLSM）分析技術(shù)研究表明，本文制備得到的金納米粒子在一定的激發(fā)條件下會發(fā)出綠色熒光，而且分散、穩(wěn)定在膠束內(nèi)部。 4.此外，本文利用兩親性PMTFPS-b-PMAA嵌段共聚物膠束，成功將預(yù)先還原的金納米粒子包裹、穩(wěn)定在膠束中。
[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.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TQ131.23;O631.1
本文編號：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.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TQ131.23;O631.1
【參考文獻(xiàn)】
相關(guān)期刊論文 前2條
1 ;Sphere-to-rod transition of short-chain PEO-b-PDMS-b-PEO in aqueous solution induced by copolymer concentration[J];Chinese Chemical Letters;2008年11期
2 張慶華;陳碧;詹曉力;陳豐秋;;PDMS-b-PEO兩親性嵌段共聚物的合成及溶液性質(zhì)[J];物理化學(xué)學(xué)報(bào);2009年06期
相關(guān)博士學(xué)位論文 前1條
1 陳碧;聚硅氧烷聚醚兩親性嵌段共聚物的合成及其溶液自組裝[D];浙江大學(xué);2008年
本文編號：2130202
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