【摘要】：具有弱鍵結(jié)構(gòu)的化合物受熱易分解產(chǎn)生自由基,可作為自由基聚合的引發(fā)劑或炭材料的改性劑。將弱鍵結(jié)構(gòu)引入苯乙烯單體或聚合物對(duì)復(fù)雜精細(xì)結(jié)構(gòu)聚合物合成方法學(xué)以及高分子材料改性具有重要意義。相比于鏈端和主鏈中弱鍵聚合物,側(cè)基為弱鍵結(jié)構(gòu)的聚合物具有官能化程度高、結(jié)構(gòu)控制準(zhǔn)確、后續(xù)反應(yīng)不會(huì)影響主鏈結(jié)構(gòu)等特點(diǎn)。本文在綜合分析及研究多種模型化合物熱解行為的基礎(chǔ)上,設(shè)計(jì)合成了三種含有碳-碳或碳-氮弱鍵結(jié)構(gòu)的苯乙烯衍生物,以其為構(gòu)筑單元設(shè)計(jì)合成了多種側(cè)基含弱鍵結(jié)構(gòu)的聚合物及其他復(fù)雜精細(xì)結(jié)構(gòu)高分子。基于碳材料表面對(duì)自由基的捕捉機(jī)理將所制備的側(cè)基弱鍵官能化溶聚丁苯橡膠應(yīng)用于對(duì)炭黑(CB)和石墨烯(GNS)等碳基填料的原位接枝改性,制備了兩種具有高分散、強(qiáng)界面作用的碳基填料/橡膠復(fù)合材料。主要研究工作及取得的成果如下:(1)含弱鍵結(jié)構(gòu)苯乙烯衍生物的設(shè)計(jì)合成。基于弱鍵化合物1,1,2-三苯乙烷(TPE)結(jié)構(gòu)以及化學(xué)鍵鍵能的分析,設(shè)計(jì)并合成了另外兩種與TPE結(jié)構(gòu)相似的化合物1,1,1,2-四苯乙烷(TEPE)和N,N-二苯基芐基胺(DPBA)。研究了 TEPE和DPBA熱解機(jī)理。結(jié)果表明,TEPE/DPBA在85℃以上的時(shí)候可以裂解產(chǎn)生芐基自由基和二苯甲基/二苯胺基自由基,并引發(fā)MMA自由基聚合。在此基礎(chǔ)上,以對(duì)氯甲基苯乙烯為母體,設(shè)計(jì)合成了側(cè)基分別為TPE、DPBA、TEPE的新型苯乙烯衍生物:4-(1,1-二苯乙基)苯乙烯(DPES)、4-(N, N-二苯胺基甲基)苯乙烯(DPAMS)和4-(1,1,1-三苯乙基)苯乙烯(TPES)。(2)含弱鍵結(jié)構(gòu)苯乙烯衍生物的聚合物的設(shè)計(jì)合成。分別通過(guò)DPES、TPES、DPAMS的負(fù)離子聚合,制備了側(cè)基為弱鍵結(jié)構(gòu)的聚合物,并研究了上述苯乙烯衍生物最佳的負(fù)離子聚合反應(yīng)條件。研究結(jié)果表明,DPES在環(huán)己烷與四氫呋喃混合溶劑(V環(huán)己烷/V四氫呋喃=20)、n-BuLi聚合體系中的負(fù)離子聚合反應(yīng)為活性聚合,反應(yīng)所得PDPES分子量和結(jié)構(gòu)精確可控;TPES在有機(jī)溶劑中溶解性差,無(wú)法通過(guò)負(fù)離子聚合得到分子量可控分子量分布窄的PTPES; DPAMS在四氫呋喃、-78℃、sec-BuLi聚合體系中的負(fù)離子聚合反應(yīng)可控性強(qiáng),所得PDPAMS分子量可控,分子量分布較窄。上述側(cè)基弱鍵聚合物與烯烴單體一同加熱到90℃以上,弱鍵聚合物熱解產(chǎn)生聚合物自由基引發(fā)烯烴單體聚合,從而得到不同結(jié)構(gòu)的接枝聚合物。根據(jù)上述機(jī)理提出了一種基于陰離子-自由基機(jī)理轉(zhuǎn)換制備接枝聚合物的方法,并成功合成了PMMA-g-PDPES 和 hypergrafted PDPAMS。這種合成PMMA-g-PDPES的聚合體系,反應(yīng)條件溫和,適用單體種類廣泛,可用于制備更多種類的極性-非極性接枝聚合物。這種方法制備的hypergrafted PDPAMS,側(cè)鏈為超支化結(jié)構(gòu),并且改變主鏈PDPAMS的分子量可對(duì)hypergrafted PDPAMS的分子量進(jìn)行調(diào)控。(3)弱鍵官能化丁苯共聚物在碳基填料增強(qiáng)橡膠中的應(yīng)用。利用含碳-碳弱鍵苯乙烯衍生物(DPES/TPES)、苯乙烯和丁二烯的負(fù)離子共聚合方法合成了不同DPES含量的官能化丁苯橡膠(SBDR)和不同TPES含量的官能化丁苯橡膠(SBTR)。SBDR鏈中DPES的含量和SBTR鏈中TPES的含量可由單體的投料比和n-BuLi的用量進(jìn)行調(diào)控。另外,弱鍵官能化溶聚丁苯橡膠負(fù)離子聚合條件接近負(fù)離子工業(yè)化產(chǎn)品生產(chǎn)條件,具有很好的工業(yè)適用性。通過(guò)SBDR與炭黑(CB)的接枝反應(yīng)證明了 SBDR與CB之間的共價(jià)鍵結(jié)合。研究了DPES引入SBDR鏈中對(duì)于CB填充SBDR硫化膠性能的影響,結(jié)果表明隨著DPES在SBDR鏈中含量的升高,CB在SBDR基體中的分散性變好,CB/SBDR硫化膠的力學(xué)性能提高,0℃的tanδ升高,60℃的tanδ降低,表明材料具有高強(qiáng)度、高抗?jié)窕�、低滾動(dòng)阻力的性能,可用于綠色環(huán)保輪胎。硫化曲線以及XPS測(cè)試結(jié)果說(shuō)明,SBTR與石墨烯(GNS)熱處理后生成含SP3碳原子的共價(jià)鍵。研究了 TPES引入SBTR鏈中對(duì)GNS填充SBTR硫化膠性能的影響,結(jié)果表明隨TPES在SBTR中含量的升高,GNS與SBTR基體之間的界面結(jié)合增強(qiáng),GNS在SBTR基體中的分散性改善,GNS/SBTR硫化膠的力學(xué)性能提高。本論文設(shè)計(jì)合成的弱鍵官能化溶聚丁苯橡膠不含雜原子,實(shí)現(xiàn)了 CB和GNS增強(qiáng)橡膠體系的原位接枝改性。
[Abstract]:Compounds with weak bond structure can be easily decomposed to produce free radicals by heating and can be used as initiator of free radical polymerization or modifier of carbon materials.The introduction of weak bond structure into styrene monomer or polymer is of great significance to synthesis methodology of complex fine structure polymers and modification of polymer materials. Polymers with weakly bonded side groups have the characteristics of high functionalization, accurate structure control and no influence on the structure of the main chain. Based on the comprehensive analysis and study of the pyrolysis behavior of various model compounds, three styrene derivatives with weakly bonded carbon-carbon or carbon-nitrogen structure were designed and synthesized. Polymers with weakly bonded side groups and other complex fine structures were synthesized by unit design. Based on the free radical trapping mechanism on the surface of carbon materials, the prepared weakly bonded side group functionalized SBR was applied to in-situ grafting modification of carbon-based fillers such as carbon black (CB) and graphene (GNS). The main research work and achievements are as follows: (1) Design and synthesis of styrene derivatives with weak bond structure. Based on the analysis of the structure of weak bond compound 1,1,2-triphenylethane (TPE) and the bond energy of chemical bond, two other compounds 1,1,1,1,1 similar to TPE were designed and synthesized. 2-tetraphenylethane (TEPE) and N,N-diphenylbenzylamine (DPBA). The pyrolysis mechanism of TEPE and DPBA was studied. The results showed that benzyl radical and diphenylmethyl/diphenylamine radical could be produced by the pyrolysis of TEPE/DPBA at above 85 C, and MMA radical polymerization was initiated. On this basis, p-CHLOROMETHYLSTYRENE was used as the parent material to design and synthesize the side. New styrene derivatives with TPE, DPBA and TEPE groups: 4-(1,1-diphenylethyl) styrene (DPES), 4-(N, N-diphenylaminomethyl) styrene (DPAMS) and 4-(1,1,1-triphenylethyl) styrene (TPES). (2) Design and synthesis of styrene derivatives with weak bond structure. Side groups were prepared by anionic polymerization of DPES, TPES and DPAMS, respectively. The results showed that the anionic polymerization of DPES in the mixed solvent of cyclohexane and tetrahydrofuran (V-cyclohexane/V-tetrahydrofuran=20) and n-BuLi system was active polymerization, and the molecular weight and structure of PDPES obtained by the reaction were accurate and feasible. Controlled; TPES is poorly soluble in organic solvents and can not be obtained by anionic polymerization with narrow controllable molecular weight distribution; DPAMS is highly controllable in tetrahydrofuran, - 78 C, sec-BuLi polymerization system, resulting in controllable molecular weight and narrow molecular weight distribution of PDPAMS. The graft copolymers with different structures were synthesized by the free radical polymerization of weakly bonded polymers which were heated above 90 C. Based on the above mechanism, a method of preparing graft copolymers based on anion-free radical mechanism conversion was proposed. PMMA-g-PDPES and hypergrafted PDPAMS were successfully synthesized. Polymerization system of PMMA-g-PDPES was synthesized under mild reaction conditions and suitable for a wide range of monomers. It can be used to prepare more kinds of polar-nonpolar graft polymers. The hypergrafted PDPAMS prepared by this method has hyperbranched side chains, and the molecular weight of the hypergrafted PDPAMS can be controlled by changing the molecular weight of the main chain. Application of bonded functionalized styrene-butadiene copolymers in carbon-based filler reinforced rubber. The functionalized styrene-butadiene rubber (SBDR) with different DPES contents and functionalized styrene-butadiene rubber (SBTR) with different TPES contents were synthesized by anionic copolymerization of carbon-carbon weakly bonded styrene derivatives (DPES/TPES), styrene and butadiene. The content of TPES in BTR chain can be controlled by the ratio of monomers and the amount of n-BuLi. In addition, the weak-bond functionalized SSBR has good industrial applicability because its anionic polymerization conditions are close to the production conditions of anionic industrial products. The covalent bonding between SBDR and CB is proved by the grafting reaction of SBDR and CB. The effect of DPES on the properties of CB-filled SBDR vulcanizates was investigated. The results showed that with the increase of DPES content in SBDR chain, the dispersion of CB in SBDR matrix was improved, the mechanical properties of CB/SBDR vulcanizates were improved, the tan_ _ _ _ _uuuuuuuuuuu The curing curve and XPS test results showed that the covalent bond containing SP3 carbon atom was formed between SBTR and graphene (GNS) after heat treatment. The mechanical properties of GNS/SBTR vulcanizates were improved with the improvement of dispersion in SBR matrix. The weak bond functionalized SBR was designed and synthesized without heteroatoms, and the in-situ grafting modification of CB and GNS reinforced rubber systems was realized.
【學(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O632.13;TQ330.1

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本文編號(hào)：2210982