本文選題：氟硅 + 嵌段共聚物��； 參考：《浙江理工大學(xué)》2017年碩士論文

【摘要】：含有氟硅鏈段的嵌段共聚物具有低表面能、化學(xué)惰性、耐熱性、耐候性等良好的物理化學(xué)性質(zhì)。研究表明,嵌段共聚物的一個(gè)主要特征就是可通過(guò)鏈段間的熱力學(xué)相互作用,形成球狀(S)、柱狀(C)、層狀(L)以及Gyroid(G)等微相分離結(jié)構(gòu),并影響其應(yīng)用性能。然而,含氟硅嵌段共聚物的微相分離行為非常特殊,氟硅鏈段與乙烯基聚合物鏈段間的Flory-Huggins相互作用參數(shù)有效值的大小及其變化規(guī)律目前尚不明確。本文藉此開(kāi)展含氟硅嵌段共聚物鏈段間相互作用參數(shù)的研究。本文利用原子轉(zhuǎn)移自由基聚合(ATRP)反應(yīng)合成一系列結(jié)構(gòu)可控的聚甲基三氟丙基硅氧烷(PMTFPS)與聚苯乙烯(PS)的嵌段共聚物(PMTFPS-b-PS)、聚甲基三氟丙基硅氧烷(PMTFPS)與聚甲基丙烯酸甲酯(PMMA)的嵌段共聚物(PMTFPS-b-PMMA),并分別考察這兩種含氟硅嵌段共聚物鏈段間相互作用參數(shù)的有效值及其變化規(guī)律。具體研究成果如下:1.以PMTFPS-Br為ATRP反應(yīng)的大分子引發(fā)劑,合成得到結(jié)構(gòu)清晰的PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物。(1)通過(guò)以氟硅單體F3的陰離子開(kāi)環(huán)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與烯丙醇進(jìn)行硅氫加成反應(yīng)引入端羥基,產(chǎn)物再與α-溴代異丁基酰溴反應(yīng)得到PMTFPS-Br。(2)在環(huán)己酮溶劑中,以溴化亞銅CuBr/N,N,N′,N″,N″-五甲基二亞乙基三胺(PMDETA)為催化體系,進(jìn)行St的ATRP反應(yīng),獲得了PMTFPS-b-PS嵌段共聚物;以CuBr/1,1,4,7,10,10-六甲基三亞乙基四胺(HMTETA)為催化體系進(jìn)行MMA的ATRP反應(yīng),獲得了PMTFPS-b-PMMA嵌段共聚物。2.進(jìn)行了PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物的微相分離行為研究。(1)研究結(jié)果表明,PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物中均有兩個(gè)明顯的玻璃化轉(zhuǎn)變溫度(Tg),這說(shuō)明嵌段共聚物可以發(fā)生微相分離,嵌段共聚物的微相分離結(jié)構(gòu)已通過(guò)透射電子顯微鏡(TEM)觀察驗(yàn)證得到。其中,PMTFPS-b-PS嵌段共聚物中PMTFPS鏈段的Tg約為㧟70~㧟73℃,PS鏈段的Tg約為86~104℃,而且發(fā)現(xiàn)只要在嵌段共聚物中含有一小段氟硅鏈段,就能產(chǎn)生微相分離;另外,PMTFPS-b-PMMA嵌段共聚物中PMTFPS鏈段的Tg約㧟74~㧟79℃,PMMA鏈段為T(mén)g約為100~116℃。(2)通過(guò)對(duì)不同分子量的PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物的高級(jí)流變拓展系統(tǒng)(ARES)測(cè)試,發(fā)現(xiàn)嵌段共聚物隨測(cè)試溫度的增加,可呈現(xiàn)有序-無(wú)序轉(zhuǎn)變(ODT),即嵌段共聚物隨溫度的增加,發(fā)生了從有微相分離結(jié)構(gòu)到無(wú)序結(jié)果的變化。3.進(jìn)行了PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物鏈段間相互作用參數(shù)有效值(χeff)及其變化規(guī)律的研究。(1)利用ARES考察了嵌段共聚物儲(chǔ)能模量(G′)隨溫度的變化關(guān)系,獲得了不同嵌段共聚物的有序-無(wú)序轉(zhuǎn)變溫度(TODT),并通過(guò)調(diào)節(jié)鏈段長(zhǎng)度(聚合度N)獲取了不同ODT臨界點(diǎn)(轉(zhuǎn)變溫度T)所對(duì)應(yīng)的χeff的準(zhǔn)確值,然后回歸出了χeff隨溫度T的變化關(guān)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)研究結(jié)果表明,在相同溫度下,PMTFPS-b-PS、PMTFPS-b-PMMA嵌段共聚物鏈段間的相互作用參數(shù)有效值遠(yuǎn)大于常規(guī)乙烯基嵌段共聚物,原因是氟硅鏈段的引入,可大大加強(qiáng)聚合物鏈段間的相互作用。此外,PS、PMMA化學(xué)結(jié)構(gòu)的不同,也會(huì)改變聚合物鏈段間的相互作用,進(jìn)而改變鏈段間的相互作用參數(shù)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.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O631.1

【參考文獻(xiàn)】

相關(guān)期刊論文 前3條

1 宋學(xué)鋒;張丹;何廷樹(shù);;氧化還原引發(fā)體系下Poly(AA-AANa-AM)吸水性樹(shù)脂的合成與表征[J];建筑材料學(xué)報(bào);2012年04期

2 袁利兵,劉海j;淺談氟硅系列材料的性能及應(yīng)用[J];有機(jī)氟工業(yè);2002年02期

3 李鯤,郭建華,李欣欣,吳平平,韓哲文;原子轉(zhuǎn)移自由基聚合合成甲基丙烯酸丁酯與丙烯酸全氟烷基乙酯兩嵌段共聚物及其性能的研究[J];高分子學(xué)報(bào);2002年02期

相關(guān)博士學(xué)位論文 前1條

1 易玲敏;乙烯基單體與氟硅氧烷二嵌段共聚物的活性陰離子聚合合成與表征[D];浙江大學(xué);2005年

，

本文編號(hào)：2111043