聚硅氧烷聚醚两亲性嵌段共聚物的合成及其溶液自组装
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摘要
自组装作为一种极具发展前景的制备具有纳米/微米尺寸规则结构的功能材料的方法,有着重要的研究价值。尤其是由两亲性嵌段共聚物自组装形成的囊泡结构,由于独特的形态结构,在诸如药物缓释、分离等领域存在着应用及潜在应用,近十年来,吸引了广泛的研究兴趣。
两亲性嵌段共聚物,不同于常规表面活性剂,在溶液中表现出更为复杂的自组装方式。嵌段共聚物的嵌段组成、嵌段比例以及各嵌段的键接方式对嵌段共聚物自组装结构都存在着影响。通过各影响因素的考察以及调控,可以实现具有特定形态的自组装结构的制备;同时,嵌段共聚物的组成嵌段亦可以根据具体应用领域的需求进行相应选择。因此,两亲性嵌段共聚物的自组装研究自1995年Eisenberg等人的报道以来,受到越来越多的关注。
本文从六甲基环三硅氧烷(D_3),三甲基(3,3,3)-三氟丙基环三硅氧烷(F_3)以及八甲基环四硅氧烷(D_4)出发,分别通过酸白土催化D4开环阳离子聚合以及丁基锂催化D_3/F_3开环阴离子聚合,制备得到了窄分子量分布、结构规整的双硅氢封端聚硅氧烷以及单硅氢封端聚硅氧烷。进一步通过硅氢封端聚硅氧烷与烯丙基封端聚醚的硅氢加成合成一系列窄分布,结构规整可控的二、三嵌段共聚物,分别为PDMS-b-PEO,PDMS-b-PEO-b-PDMS,PEO-b-PDMS-b-PEO,PMTFPS-b-PEO以及PMTFPS-b-PEO-b-PMTFPS。在此基础上,通过表面张力仪、质子核磁共振以及透射电镜手段对嵌段共聚物的表面活性及水溶液胶束化能力,以及水溶液自组装行为展开相应研究.概括而言,本文的主要工作可以分为两大部分,即:1、两亲性嵌段共聚物的合成;2、两亲性嵌段共聚物表面活性、溶液胶束化能力以及自组装行为的考察:
两亲性嵌段共聚物的合成工作总结如下:
1.利用酸白土催化D_4开环聚合,替代了常规液体酸催化,详细研究了酸白土非均相催化开环的反应规律及机理。认为,由于催化活性位共价键接于酸白土颗粒,酸白土催化体系不存在液体酸体系中游离存在的反离子,其链增长反应较液体酸简单,同时,酸白土颗粒的大空间位阻影响了活性链的增长方式,聚合产物表现出更窄的分子量分布。在上述研究的基础上,通过工艺条件的优化,实现了一系列具有较窄分子量分布(1.2-1.4)的双硅氢封端聚硅氧烷的绿色、可控合成。
2.为达到阴离子聚合所需的“无杂”聚合环境,建立了一套真空度达到1E-3 Pa的高真空装置,并建立了基于高纯氮气净化装置的惰气保护系统以及单体,溶剂精制装置,为反应物料的精制、转移和反应提供了条件。
3.D_3/F_3阴离子开环聚合存在严重的“反咬”及“再分布”副反应。副反应的抑制是实现聚合产物窄分布的关键。通过研究发现,低温、高单体浓度及低转化率有利于对“反咬”及“再分布”副反应的抑制。在此基础上,得到了合适的工艺条件,进行窄分布单硅氢封端聚硅氧烷的制备,产物分子量分布为1.03-1.17.
4.开环D_3、F_3分别制备得到了分子量分布为1.03-1.14,聚合度为3,6,9,12,21,30,100的单硅氢封端聚二甲基硅氧烷,以及分子量分布为1.10-1.17,聚合度为3,6,9,12,21的单硅氢封端聚甲基三氟丙基硅氧烷。
5.通过FT-IR跟踪分析,研究了Speier's催化剂对于硅氢封端硅氧烷与烯丙基封端聚氧乙烯醚(PEO)的硅氢加成反应的催化性能,合成并纯化得到了一系列聚硅氧烷与聚氧乙烯醚构建的不同结构、不同组成、不同分子量的两亲性嵌段共聚物。分别为PDMS-b-PEO,PDMS-b-PEO-b-PDMS,PEO-b-PDMS-b-PEO,PMTFPS-b-PEO以及PMTFPS-b-PEO-b-PMTFPS。
在系列两亲性嵌段共聚物顺利合成的基础上,第二部分工作主要针对相应表面活性、溶液胶束化能力以及溶液自组装行为展开考察与讨论,总结如下:
1.两亲性嵌段共聚物表面张力分析结果显示,不同于常规表面活性剂,两亲性嵌段共聚物在水溶液中的胶束化能力(以CMC值表示)在受到嵌段共聚物憎水性影响的同时,也受到嵌段共聚物几何结构、以及亲水疏水嵌段结合方式影响。
2.对三嵌段共聚物的表面活性与其结构的关系进行了考察,认为,对于三嵌段共聚物而言,在水溶液中实现胶束化或者在空气-水界面实现紧密堆积,需要一个分子链段的环化过程。中间嵌段为柔性疏水嵌段的三嵌段共聚物比中间嵌段由亲水嵌段构建的三嵌段共聚物更易在空气-水界面形成致密的保护层,从而表现出更高的表面活性。
3.对PDMS-b-PEO二嵌段共聚物溶液自组装行为进行了考察,结果显示:
a)随着嵌段共聚物憎水链段所占比例的增加,嵌段共聚物自组装聚集体表现出了由“星型”胶束向“平头”胶束转变的趋势。
b)随着纯水自组装体系中,嵌段共聚物浓度的增加,嵌段共聚物溶液出现了所谓的“第二临界胶束浓度”,初级自组装聚集体发生二次聚集,形成具有较大尺度的二次聚集体。
c)讨论了PDMS-b-PEO嵌段共聚物大复合胶束的形成过程,不同于常规理解,PDMS-b-PEO嵌段共聚物大复合胶束的形成是球状与棒状聚集体共同参与碰撞的结果,在表面能驱动下,碰撞形成的聚集体呈现球状形态。针对形成的机理,给出了合理的解释。
d)嵌段共聚物在THF/H2O混合溶剂中自组装形成的聚集体形态,随着嵌段共聚物浓度的增加,水含量的增加,表现出从球-棒-双层结构的变化趋势。
4.对PDMS-b-PEO-b-PDMS以及PEO-b-PDMS-b-PEO三嵌段共聚物的溶液自组装行为进行了考察,结果显示:
a) PDMS-b-PEO-b-PDMS三嵌段共聚物,随着嵌段共聚物溶液陈化时间的增加,其相应自组装结构更趋于热力学平衡状态,形态变得更为均一。嵌段共聚物组成对于自组装形态影响的考察显示,随着中间嵌段PEO链段的增加,自组装形态发生了由球到棒再到六角囊泡结构的转变。通过影响因素的控制,本文实现了均一囊泡结构的制备。
b) PEO-b-PDMS-b-PEO三嵌段共聚物,由于PEO嵌段为疏水性甲基封端,疏水性甲基存在逃离亲水性区域进入疏水核的趋势,因此随着陈化时间的增加,聚集体由于PEO的端基化作用,发生不同于PDMS-b-PEO-b-PDMS三嵌段共聚物的变化,小的分散的聚集体在PEO的桥联作用下,聚集形成大的聚集体.而随着嵌段共聚物浓度的增加,聚集体发生二次聚集,聚集体形态呈现出规律性变化。
c) PEO-b-PDMS-b-PEO三嵌段共聚物水溶液自组装聚集体形态随着嵌段共聚物浓度的增加,表现出从球状到椭圓状再到棒状的转变,认为,三嵌段共聚物在水溶液中的分子构象对自组装聚集体的具体形态存在影响。
5.对PMTFPS-b-PEO以及PMTFPS-b-PEO-b-PMTFPS嵌段共聚物的溶液自组装进行了考察,结果显示:
a)对于PMTFPS-b-PEO二嵌段共聚物,随着嵌段共聚物浓度的增加,聚集体二次聚集,发生相应的形态转变。随着嵌段组成亲水嵌段比例的增加,聚集形态表现出“星型”胶束向“平头”胶束的转变。随着陈化时间的增加,聚集体更趋向于达到热力学平衡状态。
b)对于PMTFPS-b-PEO-b-PMTFPS以及PMTFPS-b-PEO嵌段共聚物,在相应的自组装行为影响因素考察的基础上,均成功制备得到了均一的囊泡结构。
概括而言,本文在以下几个方面具有创新性
1.以酸白土非均相催化体系,替代了常规液体酸催化体系,开环D_4实现了具有较窄分子量分布的双硅氢封端聚二甲基硅氧烷的绿色、可控合成,产物分子量分布为1.2-1.4。
2.考察、分析了D_3、F_3阴离子开环聚合反应的规律及影响因素,优化反应条件,有效抑制了聚合过程中存在的“反咬”及“再分布”副反应,实现了单硅氢封端聚硅氧烷的窄分布合成,产物分布为1.03-1.17。
3.合成了新型PMTFPS-b-PEO以及PMTFPS-b-PEO-b-PMTFPS两亲性嵌段共聚物,并实现了均一囊泡结构的制备。
4.比较了PDMS-b-PEO-b-PDMS以及PEO-b-PDMS-b-PEO三嵌段共聚物,发现并解释了中间嵌段为柔性疏水嵌段的三嵌段共聚物具有比中间嵌段为亲水嵌段的三嵌段共聚物更高的表面活性。
5.在PDMS-b-PEO二嵌段共聚物大复合球状胶束的形成过程中,发现了棒状聚集体的参与作用,提出了关于大复合胶束形成机理的新认识。同时,在PEO-b-PDMS-b-PEO嵌段共聚物自组装形态调控研究中,发现并解释了新型的“球—棒”形态转变过程及机理。
As a very potential method to prepare advanced materials of specific functionality,especially for the preparation of functional materials with desired structure and size(nanometers to micrometers),self-assembly behavior has attracted a lot research attention.
Different from ordinary surfactants,amphiphilic copolymers behave in a much more complicated way in solution.Through proper choose of constituting blocks and appropriate control of the structure of block copolymers and the proportion of different blocks,the structure of self-assembled aggregates could be easily tuned.And meanwhile,the constituting blocks could be selected by one's will so that certain functionality introduced would qualify the applications of these copolymers in certain areas.
In this dissertation,polysiloxane(and fluoro-containing polysiloxane) and poly(ethylene oxide) were chosen respectively as the hydrophobic and hydrophilic block.A series of amphiphilic block copolymers were constructed with different block composition and different structure by hydrosilation reactions between Si-H functional polysiloxane and ally terminated PEO homopolymers.The influence of block composition and block structure on the copolymer's solution property and self-assembly was studied.The detailed works were briefed as following:
1.With the use of acid treated bentonite as the catalyst,we successfully prepared a series of functional polysiloxane hompolymers with relatively narrow molecular weight distribution.A discussion into the reaction mechanism was carried out.We thought that different from ordinary ring-opening polymerization of D4 with the catalysis of liquid acid,the current reaction system was constructed by two phases, the liquid monomer and the solid catalyst.Active sites for catalyzing are covalently bonded to the acid treated bentonite particles;therefore,the reaction system is free of free counter ions.Without the free counter ioins,the polymerization process is largely simplified.And meanwhile,because the bentonite particles serve as large counter ions,the steric hinderance provided would also influence the way the living chains grow and very probably force them to grow in a more disciplined way.By this catalysis system,we have successfully prepared functional polysiloxanes with relatively narrow molecular weight distribution(in the range of 1.2-1.4).
2.In comparison,a series of mono-functional polysiloxanes with different molecular weight were synthesized.Reaction route for the anionic ring-opening polymerization of D_3 was designed and correspondent reactors for the polymerization were constructed.High vacuum techniques were used to prepare a series of monofunctional polysiloxane homopolymers with different molecular weight and narrow molecular weight distribution.Monofunctional polysiloxanes include two separate kinds,they are respectively polydimethylsiloxanes and polymethyltrifluoropropylsiloxanes.The prepared functional polymers were carefully characterized by ~1H-NMR,FT-IR and GPC characterizations.The results show a good support for the well-defined structure and good control of the molecular weight of prepared polymers.The polydispersity index is lower than
1.1.Influence of different reaction conditions was also investigated.
3.The suitability of Speier's catalyst for the hydrosilation reaction between Si-H terminated polysiloxane and aryl terminated poly(ethyleneoxide) was investigated. For the investigated hydrosilation reactions,speier's catalyst shows high selectivity and activity.The completeness of the hydrosilation reactions was proved with conversions higher than 99%.Through hydrosilation reactions between Si-H terminated polysiloxanes and ally terminated poly(ethylene oxide) homopolymers,we have successfully prepared five series of amphiphilic block copolymers,PDMS-b-PEO,PDMS-b-PEO-b-PDMS,PEO-b-PDMS-b-PEO, PMTFPS-b-PEO and PMTFPS-b-PEO-b-PMTFPS.The synthesized copolymers were shown to be well-defined through characterizations such as GPC,~1H-NMR and FT-IR measurements.
4.Solution properties of the copolymers synthesized were studied mainly by surface tensiometer.The possible influence of copolymer structure and composition on copolymer solution property was discussed and accordingly we proposed our understandings.
5.Self-assembly behavior of different copolymers in aqueous solution was also investigated.Various morphologies of aggregates were found,including sphere, rod,vesicle and several others.Discussion into the factors which would influence the morphology of aggregates formed was carried out.And a discussion into specific shape transition was also provided,such as morphology transition from sphere-to-rod.
The originality of this dissertation lies in:
1.A more environmentally friendly synthesis route was proposed instead of traditional reaction route for the preparation of di-functional polydimethylsiloxane.With the use of insoluble acid treated bentonite,a series of narrow molecular weight distributed dihydrogen terminated polydimethylsiloxane were successfully prepared with polydispersity index ranging from 1.2-1.4
2.Effectively inhibits the "backbiting" and "redistribution" side reactions in the anionic ring-opening polymerization of D_3 and F_3.A series of mono-functional polysiloxanes were successfully prepared with polydispersity index ranging from 1.03-1.17.
3.Two kinds of novel amphiphilic copolymers PMTFPS-b-PEO and PMTFPS-b-PEO-b-PMTFPS were synthesized and vesicle formations were found from solutions of these two kinds of copolymers.
4.Structure of triblock copolymers was found to greatly influence the surface activities of correspondent copolymers.A plausible mechanism was proposed.
5.In the solution self-assembly study of PDMS-b-PEO and PEO-b-PDMS-b-PEO copolymers,novel formation process of large compound micelle and novel "sphere-to-rod" morphology transition were observed.And correspondent plausible mechanisms were proposed.
两亲性嵌段共聚物,不同于常规表面活性剂,在溶液中表现出更为复杂的自组装方式。嵌段共聚物的嵌段组成、嵌段比例以及各嵌段的键接方式对嵌段共聚物自组装结构都存在着影响。通过各影响因素的考察以及调控,可以实现具有特定形态的自组装结构的制备;同时,嵌段共聚物的组成嵌段亦可以根据具体应用领域的需求进行相应选择。因此,两亲性嵌段共聚物的自组装研究自1995年Eisenberg等人的报道以来,受到越来越多的关注。
本文从六甲基环三硅氧烷(D_3),三甲基(3,3,3)-三氟丙基环三硅氧烷(F_3)以及八甲基环四硅氧烷(D_4)出发,分别通过酸白土催化D4开环阳离子聚合以及丁基锂催化D_3/F_3开环阴离子聚合,制备得到了窄分子量分布、结构规整的双硅氢封端聚硅氧烷以及单硅氢封端聚硅氧烷。进一步通过硅氢封端聚硅氧烷与烯丙基封端聚醚的硅氢加成合成一系列窄分布,结构规整可控的二、三嵌段共聚物,分别为PDMS-b-PEO,PDMS-b-PEO-b-PDMS,PEO-b-PDMS-b-PEO,PMTFPS-b-PEO以及PMTFPS-b-PEO-b-PMTFPS。在此基础上,通过表面张力仪、质子核磁共振以及透射电镜手段对嵌段共聚物的表面活性及水溶液胶束化能力,以及水溶液自组装行为展开相应研究.概括而言,本文的主要工作可以分为两大部分,即:1、两亲性嵌段共聚物的合成;2、两亲性嵌段共聚物表面活性、溶液胶束化能力以及自组装行为的考察:
两亲性嵌段共聚物的合成工作总结如下:
1.利用酸白土催化D_4开环聚合,替代了常规液体酸催化,详细研究了酸白土非均相催化开环的反应规律及机理。认为,由于催化活性位共价键接于酸白土颗粒,酸白土催化体系不存在液体酸体系中游离存在的反离子,其链增长反应较液体酸简单,同时,酸白土颗粒的大空间位阻影响了活性链的增长方式,聚合产物表现出更窄的分子量分布。在上述研究的基础上,通过工艺条件的优化,实现了一系列具有较窄分子量分布(1.2-1.4)的双硅氢封端聚硅氧烷的绿色、可控合成。
2.为达到阴离子聚合所需的“无杂”聚合环境,建立了一套真空度达到1E-3 Pa的高真空装置,并建立了基于高纯氮气净化装置的惰气保护系统以及单体,溶剂精制装置,为反应物料的精制、转移和反应提供了条件。
3.D_3/F_3阴离子开环聚合存在严重的“反咬”及“再分布”副反应。副反应的抑制是实现聚合产物窄分布的关键。通过研究发现,低温、高单体浓度及低转化率有利于对“反咬”及“再分布”副反应的抑制。在此基础上,得到了合适的工艺条件,进行窄分布单硅氢封端聚硅氧烷的制备,产物分子量分布为1.03-1.17.
4.开环D_3、F_3分别制备得到了分子量分布为1.03-1.14,聚合度为3,6,9,12,21,30,100的单硅氢封端聚二甲基硅氧烷,以及分子量分布为1.10-1.17,聚合度为3,6,9,12,21的单硅氢封端聚甲基三氟丙基硅氧烷。
5.通过FT-IR跟踪分析,研究了Speier's催化剂对于硅氢封端硅氧烷与烯丙基封端聚氧乙烯醚(PEO)的硅氢加成反应的催化性能,合成并纯化得到了一系列聚硅氧烷与聚氧乙烯醚构建的不同结构、不同组成、不同分子量的两亲性嵌段共聚物。分别为PDMS-b-PEO,PDMS-b-PEO-b-PDMS,PEO-b-PDMS-b-PEO,PMTFPS-b-PEO以及PMTFPS-b-PEO-b-PMTFPS。
在系列两亲性嵌段共聚物顺利合成的基础上,第二部分工作主要针对相应表面活性、溶液胶束化能力以及溶液自组装行为展开考察与讨论,总结如下:
1.两亲性嵌段共聚物表面张力分析结果显示,不同于常规表面活性剂,两亲性嵌段共聚物在水溶液中的胶束化能力(以CMC值表示)在受到嵌段共聚物憎水性影响的同时,也受到嵌段共聚物几何结构、以及亲水疏水嵌段结合方式影响。
2.对三嵌段共聚物的表面活性与其结构的关系进行了考察,认为,对于三嵌段共聚物而言,在水溶液中实现胶束化或者在空气-水界面实现紧密堆积,需要一个分子链段的环化过程。中间嵌段为柔性疏水嵌段的三嵌段共聚物比中间嵌段由亲水嵌段构建的三嵌段共聚物更易在空气-水界面形成致密的保护层,从而表现出更高的表面活性。
3.对PDMS-b-PEO二嵌段共聚物溶液自组装行为进行了考察,结果显示:
a)随着嵌段共聚物憎水链段所占比例的增加,嵌段共聚物自组装聚集体表现出了由“星型”胶束向“平头”胶束转变的趋势。
b)随着纯水自组装体系中,嵌段共聚物浓度的增加,嵌段共聚物溶液出现了所谓的“第二临界胶束浓度”,初级自组装聚集体发生二次聚集,形成具有较大尺度的二次聚集体。
c)讨论了PDMS-b-PEO嵌段共聚物大复合胶束的形成过程,不同于常规理解,PDMS-b-PEO嵌段共聚物大复合胶束的形成是球状与棒状聚集体共同参与碰撞的结果,在表面能驱动下,碰撞形成的聚集体呈现球状形态。针对形成的机理,给出了合理的解释。
d)嵌段共聚物在THF/H2O混合溶剂中自组装形成的聚集体形态,随着嵌段共聚物浓度的增加,水含量的增加,表现出从球-棒-双层结构的变化趋势。
4.对PDMS-b-PEO-b-PDMS以及PEO-b-PDMS-b-PEO三嵌段共聚物的溶液自组装行为进行了考察,结果显示:
a) PDMS-b-PEO-b-PDMS三嵌段共聚物,随着嵌段共聚物溶液陈化时间的增加,其相应自组装结构更趋于热力学平衡状态,形态变得更为均一。嵌段共聚物组成对于自组装形态影响的考察显示,随着中间嵌段PEO链段的增加,自组装形态发生了由球到棒再到六角囊泡结构的转变。通过影响因素的控制,本文实现了均一囊泡结构的制备。
b) PEO-b-PDMS-b-PEO三嵌段共聚物,由于PEO嵌段为疏水性甲基封端,疏水性甲基存在逃离亲水性区域进入疏水核的趋势,因此随着陈化时间的增加,聚集体由于PEO的端基化作用,发生不同于PDMS-b-PEO-b-PDMS三嵌段共聚物的变化,小的分散的聚集体在PEO的桥联作用下,聚集形成大的聚集体.而随着嵌段共聚物浓度的增加,聚集体发生二次聚集,聚集体形态呈现出规律性变化。
c) PEO-b-PDMS-b-PEO三嵌段共聚物水溶液自组装聚集体形态随着嵌段共聚物浓度的增加,表现出从球状到椭圓状再到棒状的转变,认为,三嵌段共聚物在水溶液中的分子构象对自组装聚集体的具体形态存在影响。
5.对PMTFPS-b-PEO以及PMTFPS-b-PEO-b-PMTFPS嵌段共聚物的溶液自组装进行了考察,结果显示:
a)对于PMTFPS-b-PEO二嵌段共聚物,随着嵌段共聚物浓度的增加,聚集体二次聚集,发生相应的形态转变。随着嵌段组成亲水嵌段比例的增加,聚集形态表现出“星型”胶束向“平头”胶束的转变。随着陈化时间的增加,聚集体更趋向于达到热力学平衡状态。
b)对于PMTFPS-b-PEO-b-PMTFPS以及PMTFPS-b-PEO嵌段共聚物,在相应的自组装行为影响因素考察的基础上,均成功制备得到了均一的囊泡结构。
概括而言,本文在以下几个方面具有创新性
1.以酸白土非均相催化体系,替代了常规液体酸催化体系,开环D_4实现了具有较窄分子量分布的双硅氢封端聚二甲基硅氧烷的绿色、可控合成,产物分子量分布为1.2-1.4。
2.考察、分析了D_3、F_3阴离子开环聚合反应的规律及影响因素,优化反应条件,有效抑制了聚合过程中存在的“反咬”及“再分布”副反应,实现了单硅氢封端聚硅氧烷的窄分布合成,产物分布为1.03-1.17。
3.合成了新型PMTFPS-b-PEO以及PMTFPS-b-PEO-b-PMTFPS两亲性嵌段共聚物,并实现了均一囊泡结构的制备。
4.比较了PDMS-b-PEO-b-PDMS以及PEO-b-PDMS-b-PEO三嵌段共聚物,发现并解释了中间嵌段为柔性疏水嵌段的三嵌段共聚物具有比中间嵌段为亲水嵌段的三嵌段共聚物更高的表面活性。
5.在PDMS-b-PEO二嵌段共聚物大复合球状胶束的形成过程中,发现了棒状聚集体的参与作用,提出了关于大复合胶束形成机理的新认识。同时,在PEO-b-PDMS-b-PEO嵌段共聚物自组装形态调控研究中,发现并解释了新型的“球—棒”形态转变过程及机理。
As a very potential method to prepare advanced materials of specific functionality,especially for the preparation of functional materials with desired structure and size(nanometers to micrometers),self-assembly behavior has attracted a lot research attention.
Different from ordinary surfactants,amphiphilic copolymers behave in a much more complicated way in solution.Through proper choose of constituting blocks and appropriate control of the structure of block copolymers and the proportion of different blocks,the structure of self-assembled aggregates could be easily tuned.And meanwhile,the constituting blocks could be selected by one's will so that certain functionality introduced would qualify the applications of these copolymers in certain areas.
In this dissertation,polysiloxane(and fluoro-containing polysiloxane) and poly(ethylene oxide) were chosen respectively as the hydrophobic and hydrophilic block.A series of amphiphilic block copolymers were constructed with different block composition and different structure by hydrosilation reactions between Si-H functional polysiloxane and ally terminated PEO homopolymers.The influence of block composition and block structure on the copolymer's solution property and self-assembly was studied.The detailed works were briefed as following:
1.With the use of acid treated bentonite as the catalyst,we successfully prepared a series of functional polysiloxane hompolymers with relatively narrow molecular weight distribution.A discussion into the reaction mechanism was carried out.We thought that different from ordinary ring-opening polymerization of D4 with the catalysis of liquid acid,the current reaction system was constructed by two phases, the liquid monomer and the solid catalyst.Active sites for catalyzing are covalently bonded to the acid treated bentonite particles;therefore,the reaction system is free of free counter ions.Without the free counter ioins,the polymerization process is largely simplified.And meanwhile,because the bentonite particles serve as large counter ions,the steric hinderance provided would also influence the way the living chains grow and very probably force them to grow in a more disciplined way.By this catalysis system,we have successfully prepared functional polysiloxanes with relatively narrow molecular weight distribution(in the range of 1.2-1.4).
2.In comparison,a series of mono-functional polysiloxanes with different molecular weight were synthesized.Reaction route for the anionic ring-opening polymerization of D_3 was designed and correspondent reactors for the polymerization were constructed.High vacuum techniques were used to prepare a series of monofunctional polysiloxane homopolymers with different molecular weight and narrow molecular weight distribution.Monofunctional polysiloxanes include two separate kinds,they are respectively polydimethylsiloxanes and polymethyltrifluoropropylsiloxanes.The prepared functional polymers were carefully characterized by ~1H-NMR,FT-IR and GPC characterizations.The results show a good support for the well-defined structure and good control of the molecular weight of prepared polymers.The polydispersity index is lower than
1.1.Influence of different reaction conditions was also investigated.
3.The suitability of Speier's catalyst for the hydrosilation reaction between Si-H terminated polysiloxane and aryl terminated poly(ethyleneoxide) was investigated. For the investigated hydrosilation reactions,speier's catalyst shows high selectivity and activity.The completeness of the hydrosilation reactions was proved with conversions higher than 99%.Through hydrosilation reactions between Si-H terminated polysiloxanes and ally terminated poly(ethylene oxide) homopolymers,we have successfully prepared five series of amphiphilic block copolymers,PDMS-b-PEO,PDMS-b-PEO-b-PDMS,PEO-b-PDMS-b-PEO, PMTFPS-b-PEO and PMTFPS-b-PEO-b-PMTFPS.The synthesized copolymers were shown to be well-defined through characterizations such as GPC,~1H-NMR and FT-IR measurements.
4.Solution properties of the copolymers synthesized were studied mainly by surface tensiometer.The possible influence of copolymer structure and composition on copolymer solution property was discussed and accordingly we proposed our understandings.
5.Self-assembly behavior of different copolymers in aqueous solution was also investigated.Various morphologies of aggregates were found,including sphere, rod,vesicle and several others.Discussion into the factors which would influence the morphology of aggregates formed was carried out.And a discussion into specific shape transition was also provided,such as morphology transition from sphere-to-rod.
The originality of this dissertation lies in:
1.A more environmentally friendly synthesis route was proposed instead of traditional reaction route for the preparation of di-functional polydimethylsiloxane.With the use of insoluble acid treated bentonite,a series of narrow molecular weight distributed dihydrogen terminated polydimethylsiloxane were successfully prepared with polydispersity index ranging from 1.2-1.4
2.Effectively inhibits the "backbiting" and "redistribution" side reactions in the anionic ring-opening polymerization of D_3 and F_3.A series of mono-functional polysiloxanes were successfully prepared with polydispersity index ranging from 1.03-1.17.
3.Two kinds of novel amphiphilic copolymers PMTFPS-b-PEO and PMTFPS-b-PEO-b-PMTFPS were synthesized and vesicle formations were found from solutions of these two kinds of copolymers.
4.Structure of triblock copolymers was found to greatly influence the surface activities of correspondent copolymers.A plausible mechanism was proposed.
5.In the solution self-assembly study of PDMS-b-PEO and PEO-b-PDMS-b-PEO copolymers,novel formation process of large compound micelle and novel "sphere-to-rod" morphology transition were observed.And correspondent plausible mechanisms were proposed.
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