含氟硅嵌段共聚物链段间相互作用参数的研究

发布时间：2018-07-09 23:09

本文选题：氟硅 + 嵌段共聚物　；参考：《浙江理工大学》2017年硕士论文

【摘要】：含有氟硅链段的嵌段共聚物具有低表面能、化学惰性、耐热性、耐候性等良好的物理化学性质。研究表明,嵌段共聚物的一个主要特征就是可通过链段间的热力学相互作用,形成球状(S)、柱状(C)、层状(L)以及Gyroid(G)等微相分离结构,并影响其应用性能。然而,含氟硅嵌段共聚物的微相分离行为非常特殊,氟硅链段与乙烯基聚合物链段间的Flory-Huggins相互作用参数有效值的大小及其变化规律目前尚不明确。本文藉此开展含氟硅嵌段共聚物链段间相互作用参数的研究。本文利用原子转移自由基聚合(ATRP)反应合成一系列结构可控的聚甲基三氟丙基硅氧烷(PMTFPS)与聚苯乙烯(PS)的嵌段共聚物(PMTFPS-b-PS)、聚甲基三氟丙基硅氧烷(PMTFPS)与聚甲基丙烯酸甲酯(PMMA)的嵌段共聚物(PMTFPS-b-PMMA),并分别考察这两种含氟硅嵌段共聚物链段间相互作用参数的有效值及其变化规律。具体研究成果如下:1.以PMTFPS-Br为ATRP反应的大分子引发剂,合成得到结构清晰的PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物。(1)通过以氟硅单体F3的阴离子开环聚合(AROP)并利用二甲基氯硅烷封端,合成含Si-H端基的PMTFPS(PMTFPS-H),PMTFPS-H与烯丙醇进行硅氢加成反应引入端羟基,产物再与α-溴代异丁基酰溴反应得到PMTFPS-Br。(2)在环己酮溶剂中,以溴化亚铜CuBr/N,N,N′,N″,N″-五甲基二亚乙基三胺(PMDETA)为催化体系,进行St的ATRP反应,获得了PMTFPS-b-PS嵌段共聚物;以CuBr/1,1,4,7,10,10-六甲基三亚乙基四胺(HMTETA)为催化体系进行MMA的ATRP反应,获得了PMTFPS-b-PMMA嵌段共聚物。2.进行了PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物的微相分离行为研究。(1)研究结果表明,PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物中均有两个明显的玻璃化转变温度(Tg),这说明嵌段共聚物可以发生微相分离,嵌段共聚物的微相分离结构已通过透射电子显微镜(TEM)观察验证得到。其中,PMTFPS-b-PS嵌段共聚物中PMTFPS链段的Tg约为㧟70~㧟73℃,PS链段的Tg约为86~104℃,而且发现只要在嵌段共聚物中含有一小段氟硅链段,就能产生微相分离;另外,PMTFPS-b-PMMA嵌段共聚物中PMTFPS链段的Tg约㧟74~㧟79℃,PMMA链段为Tg约为100~116℃。(2)通过对不同分子量的PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物的高级流变拓展系统(ARES)测试,发现嵌段共聚物随测试温度的增加,可呈现有序-无序转变(ODT),即嵌段共聚物随温度的增加,发生了从有微相分离结构到无序结果的变化。3.进行了PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物链段间相互作用参数有效值(χeff)及其变化规律的研究。(1)利用ARES考察了嵌段共聚物储能模量(G′)随温度的变化关系,获得了不同嵌段共聚物的有序-无序转变温度(TODT),并通过调节链段长度(聚合度N)获取了不同ODT临界点(转变温度T)所对应的χeff的准确值,然后回归出了χeff随温度T的变化关系:PMTFPS-b-PS嵌段共聚物:χ=470/T-0.735PMTFPS-b-PMMA嵌段共聚物:χ=637/T-1.04(2)研究结果表明,在相同温度下,PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物链段间的相互作用参数有效值远大于常规乙烯基嵌段共聚物,原因是氟硅链段的引入,可大大加强聚合物链段间的相互作用。此外,PS、PMMA化学结构的不同,也会改变聚合物链段间的相互作用,进而改变链段间的相互作用参数有效值的大小。
[Abstract]:The block copolymers containing Fluorosilicic segments have good physical and chemical properties, such as low surface energy, chemical inertness, heat resistance and weatherability. The main characteristic of the block copolymers is that they can form spherical (S), C, L and Gyroid (G) microphase separation structures by the thermodynamic interaction between the chain segments, and influence the structure of the microphase separation structure, such as the column (L), and the Gyroid (G). However, the microphase separation behavior of the Fluorosilicic block copolymer is very special. The size and variation of the Flory-Huggins interaction parameters between the fluorosilicsi segment and the vinyl polymer chain are not yet clear. In this paper, the intersegment interaction parameters of the fluorosilicsi block copolymers are studied. A series of structural controlled polymethyl three fluoro propyl siloxane (PMTFPS) and polystyrene (PS) block copolymer (PMTFPS-b-PS), polymethyl three fluoro propyl siloxane (PMTFPS) and polymethyl methacrylate (PMMA) block copolymer (PMTFPS-b-PMMA) were synthesized by atomic transfer radical polymerization (ATRP), and the two kinds of fluorine were investigated respectively. The effective values of the intersegment interaction parameters of the silicon block copolymers and their changing rules. The specific results are as follows: 1. the structure clear PMTFPS-b-PS, PMTFPS-b-PMMA block copolymers are synthesized with PMTFPS-Br as the ATRP reaction macroinitiator. (1) through the anionic ring polymerization (AROP) with fluorosilicon monomer F3 and the use of two methyl chlorosilicone PMTFPS (PMTFPS-H) containing Si-H terminal group was synthesized at the end of alkane, PMTFPS-H and allyl alcohol were added to the hydrosilylation of hydroxy terminal hydroxyl group, and the product was reacted with alpha bromo butyl bromide to obtain PMTFPS-Br. (2) in cyclohexanone solvent, with copper bromide CuBr/N, N, N ', N', N '- five methyl two ethylene three amine (PMDETA) as catalytic systems. The PMTFPS-b-PS block copolymer was obtained. The ATRP reaction of MMA was carried out with CuBr/1,1,4,7,10,10- six methyl Sanya ethyl four amine (HMTETA) as a catalytic system. The PMTFPS-b-PMMA block copolymer.2. was obtained for PMTFPS-b-PS and PMTFPS-b-PMMA Block Copolymer Microphase Separation Behavior. (1) the results of the study showed that PMTFPS-b-PS, PMTFPS-b-P. There are two obvious glass transition temperatures (Tg) in the MMA block copolymer, which indicates that the block copolymer can be microphase separated. The microphase separation structure of block copolymer has been verified by transmission electron microscopy (TEM). The Tg of the PMTFPS segment of the PMTFPS-b-PS block copolymer is about 70~? 73, and Tg about PS chain segments is about 86~. At 104, it is found that microphase separation can be produced as long as a small segment of fluorosilicone chain is contained in the block copolymers. In addition, the Tg of the PMTFPS segment of the PMTFPS-b-PMMA block copolymer is about 74~? 79 C, and the PMMA segment is Tg 100~116 C. (2) through the PMTFPS-b-PS of different molecular weights, the Advanced Rheology expansion system of the PMTFPS-b-PMMA block copolymer (A) RES) the test shows that the block copolymer can present an ordered disorder transition (ODT) with the increase of the test temperature. That is, the block copolymer increases with the temperature, and changes from the microphase separation structure to the disordered result of the block copolymers, and the PMTFPS-b-PS, the effective value of the intersegment interaction parameters of the PMTFPS-b-PMMA block copolymer (x eff) and the variation law of the PMTFPS-b-PMMA block copolymer (.3.) and its variation law are carried out. (1) (1) the relationship between the energy storage modulus (G ') of block copolymer (G') with the temperature was investigated by ARES. The order disordered transition temperature (TODT) of different block copolymers was obtained, and the exact value of the X eff corresponding to different ODT critical points (T) was obtained by adjusting the length of the chain segment (degree of polymerization), and then the X eff with the temperature T was returned. The change relationship: PMTFPS-b-PS block copolymer: X =470/T-0.735PMTFPS-b-PMMA block copolymer: X =637/T-1.04 (2) study results show that the effective value of the interaction parameters between the chain segments of PMTFPS-b-PS and PMTFPS-b-PMMA block copolymers is much greater than that of the conventional ethylene block copolymers at the same temperature. The reason is that the introduction of fluorosilicic chain segments can be greatly improved. The interaction between the polymer chain segments is strengthened. In addition, the different chemical structures of PS and PMMA will also change the interaction between the polymer chain segments, and then change the size of the effective values of the interaction parameters between the chains.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.1

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