本文選題：聚烯烴 + 有機硅��； 參考：《浙江大學(xué)》2017年碩士論文

【摘要】：聚烯烴材料因具有機械性能好、性價比高、加工性能優(yōu)良等優(yōu)點,一直都是備受關(guān)注的高分子材料之一,但分子中極性官能團的缺乏限制了其應(yīng)用范圍,因此,聚烯烴材料的功能化改性及其性能拓展具有極為深遠的意義。有機硅材料作為一種同時含有“有機”和“無機”結(jié)構(gòu)的特殊材料,集耐熱性、潤滑性、耐候性、疏水性等優(yōu)異性能于一身,但其與碳基材料的相容性和機械性能較差。若能將聚烯烴與有機硅化合物相結(jié)合,即用有機硅材料對聚烯烴進行改性,則有可能制備兼具兩種材料特性的共聚物。因此,本課題期望通過最直接的配位接枝共聚方法向聚烯烴分子中引入功能性的乙氧基硅烷基團,探究其聚合行為及共聚物的結(jié)構(gòu)性能,由此將聚烯烴和有機硅材料的特性相結(jié)合,并拓展有機硅聚烯烴共聚物的用途。在第二章中,本文首先設(shè)計并合成了一種含有功能性基團的有機硅極性單體——7-辛烯基乙氧基二甲基硅烷(OEMS),在吡咯亞胺釩系催化劑(VCIP)的催化作用下,通過乙烯與該極性單體配位共聚,制得含功能性乙氧基硅烷的乙烯共聚物(PE-co-OEMS)。共聚物的結(jié)構(gòu)組成和性能通過核磁共振氫譜和碳譜(1H NMR和13CNMR)、高溫凝膠滲透色譜(HT-GPC)和熱分析(DSC)等手段進行表征,結(jié)果顯示,當(dāng)共單體OEMS的投料量增大至60mmol/L時,共聚反應(yīng)活性仍可保持在1.2 kg·mmolv-1.h-1 OEMS單體插入率為1.3 mol%;此外,OEMS投料量對于共聚物的重均分子量(Mw)和分子量分布指數(shù)(PDI)均具有較大的影響,當(dāng)OEMS投料量為30mmol/L時,共聚物Mw為16.9kg·mol-1,PDI為2.1;若繼續(xù)增大共單體的投料量,共聚物分子量增大且分子量分布變寬。熔點(Tm)和結(jié)晶焓(△Hc)隨著OEMS插入率的增大而降低,Tm為120.84～130.64℃,△Hc為120.3～176.0 J.g-1。在三氟甲磺酸作用下,PE-co-OEMS交聯(lián)后凝膠含量接近100%。在第二章的研究基礎(chǔ)之上,第三章向乙烯/OEMS二元共聚體系中加入了長鏈α-烯烴單體——1-己烯或1-辛烯作為第三單體,成功合成了 一系列的乙烯/1-己烯(或1-辛烯)/OEMS三元共聚物。采用與第二章相同的測試手法對三元共聚物進行表征,結(jié)果顯示,三元共聚的反應(yīng)活性為1.34～5.41 kg.mmolv-1·h-1,共聚產(chǎn)物的 Mw 為 15.3～36.2 kg.mol-1,PDI 為 2～3,OEMS 插入率可在 0.29～2.24 mol%范圍內(nèi)調(diào)控;共聚物熔點Tm為107.13～120.35℃,結(jié)晶焓△Hc為59.6～119.1 J·g-1。若保持其他實驗條件完全相同,與二元共聚體系相比,增加第三單體的投料濃度可使得共聚反應(yīng)活性提高,數(shù)均分子量(Mn)和重均分子量(Mw)增大,熔點(Tm)、結(jié)晶溫度(Tc)、熔融焓(AHm)和結(jié)晶焓(△Hc)降低;當(dāng)OEMS采用較高濃度加料量時(如≥60mmol/L),三元共聚物交聯(lián)后的產(chǎn)物凝膠含量可達到98%。
[Abstract]:Polyolefin materials have been one of the most concerned polymer materials because of their good mechanical properties, high cost performance and good processing properties. However, the lack of polar functional groups in the molecules limits their application. The functional modification and property development of polyolefin materials are of great significance. As a special material with "organic" and "inorganic" structure, organosilicon has excellent properties such as heat resistance, lubricity, weathering resistance and hydrophobicity, but its compatibility and mechanical properties with carbon-based materials are poor. If polyolefin can be combined with organosilicon, that is to say, polyolefin can be modified with silicone material, it is possible to prepare copolymers with both properties. Therefore, the aim of this study is to introduce functional ethoxylsilane groups into polyolefin molecules by the most direct coordination graft copolymerization, and to investigate the polymerization behavior and the structure and properties of the copolymers. Therefore, the properties of polyolefin and silicone materials are combined, and the use of organosilicon polyolefin copolymers is expanded. In the second chapter, a novel organosilicon polar monomer, 7-octenyl ethoxy dimethylsilane, was designed and synthesized, which was catalyzed by pyrroleimide vanadium catalyst (VCIP). Ethylene copolymers containing functional ethoxysilane were synthesized by coordination copolymerization of ethylene with this polar monomer. The structure and properties of the copolymers were characterized by 1H NMR and 13C NMR spectra, high temperature gel permeation chromatography (HT-GPC) and thermal analysis. The results showed that when the feed amount of OEMS was increased to 60mmol/L, The copolymerization activity can still be maintained at 1.2kg mmolv-1.h-1 OEMS monomer insertion rate of 1.3mol / L, and the amount of OEMS feed has a great influence on the weight average molecular weight (MW) and molecular weight distribution index (Mw) of the copolymer. When the OEMS feed amount is 30mmol/L, the copolymerization activity can be maintained at 1.3mol / L. The copolymer MW was 16.9kg mol-1 and PDI was 2.1, and the molecular weight and molecular weight distribution of the copolymers increased with increasing the feed amount of the copolymers. The melting point Tm) and the crystallization enthalpy (HCC) decreased with the increase of the OEMS insertion rate. The Tm was 120.84 (130.64 鈩，

本文編號：1841611