鐵系催化劑催化共軛二烯烴(共)聚合的研究
發(fā)布時(shí)間:2018-02-05 22:30
本文關(guān)鍵詞: 鐵催化劑 1 3-丁二烯 異戊二烯 聚丁二烯 共聚 出處:《揚(yáng)州大學(xué)》2017年碩士論文 論文類型:學(xué)位論文
【摘要】:目前,作為替代天然橡膠的選擇,合成橡膠主要在主要用于制造輪胎。制造兼具安全性及高使用性能的輪胎時(shí),要求作為原料材料的合成橡膠同時(shí)具有抗?jié)窕院偷蜐L動(dòng)阻力兩種性能。眾所周知,輪胎的抗?jié)窕院蜐L動(dòng)阻力是兩種相互矛盾的性能。丁苯橡膠抗?jié)窕阅芎?但滾動(dòng)阻力大;順丁橡膠具有優(yōu)異的耐磨性和彈性,但抗?jié)窕阅懿?因此通過(guò)順丁橡膠與丁苯橡膠并用已成為兼顧高抗?jié)窕院偷蜐L動(dòng)阻力一種有效途徑。此外,1,2-結(jié)構(gòu)的聚丁二烯不但具有優(yōu)良的牽引性能、拉伸強(qiáng)度、抗撕裂性、低滾動(dòng)阻力,而且其抗?jié)窕耘c丁苯橡膠相當(dāng),故而,控制1,2-結(jié)構(gòu)的聚丁二烯在合成輪胎用橡膠時(shí)異常重要。催化劑在控制合成1,2-聚丁二烯至關(guān)重要,并且催化劑種類繁多。其中鐵系催化劑因含量豐富、經(jīng)濟(jì)性和環(huán)境友好性,在合成橡膠催化領(lǐng)域得到了越來(lái)越多的關(guān)注,但鐵系催化劑合成1,2-聚丁二烯,由于熔點(diǎn)較高,制約了其發(fā)展。為了解決這一問(wèn)題,本文著力研究以鐵系催化劑催化,配位聚合制備丁二烯、異戊二烯共聚物及丁二烯均聚物,并得到主要結(jié)論如下:(1)以異辛酸鐵/三異丁基鋁/亞磷酸二乙酯催化組分(Fe(2-EHA)3/Al(i-Bu)3/DEP)在較高溫度(50℃)下、正己烷溶液中合成了丁二烯、異戊二烯共聚物。通過(guò)控制催化劑組份的配比,可制備兩種不同的共聚物,即含間同1,2-結(jié)構(gòu)聚丁二烯鏈段或無(wú)規(guī)1,2-結(jié)構(gòu)聚丁二烯鏈段的共聚物。其中含間同1,2-結(jié)構(gòu)的共聚物熔點(diǎn)在155℃。并且此催化體系成功制備了高1,2-結(jié)構(gòu)和3,4-結(jié)構(gòu)的丁二烯異戊二烯共聚物。其中異戊二烯鏈節(jié)中3,4結(jié)構(gòu)含量為56.5%,而丁二烯鏈節(jié)中1,2結(jié)構(gòu)含量為51.1%。(2)以異辛酸鐵/(三異丁基鋁、三乙基鋁)/亞磷酸二乙酯催化組分(Fe(2-EHA)3/[Al(i-Bu)3、AlEt3]/DEP),在較高溫度(50℃)下、正己烷溶液中,合成了丁二烯均聚物。該體系在用混鋁做助催化劑下仍保持單一活性中心和高1,2選擇性。通過(guò)調(diào)節(jié)兩種助催化劑的比例,得到一系列具有不同微觀結(jié)構(gòu)的1,2丁二烯均聚物。丁二烯的熔點(diǎn)隨助催化劑中乙基鋁摩爾含量的增加而下降,從168.7℃降低到123.2℃,從而增加了聚丁二烯的可加工性。
[Abstract]:At present, as an alternative to natural rubber, synthetic rubber is mainly used in the manufacture of tyres, the manufacture of tyres with both safety and high performance. It is well known that synthetic rubber, which is used as raw material, has both wet-slip resistance and low rolling resistance. The wet skid resistance and rolling resistance of tire are two kinds of contradictory properties. Cis-butadiene rubber has excellent wear resistance and elasticity, but its wet-slip resistance is poor, so the combination of cis-butadiene rubber and styrene-butadiene rubber has become an effective way to give consideration to both high wet-slip resistance and low rolling resistance. The 2-structure polybutadiene not only has good traction properties, tensile strength, tear resistance, low rolling resistance, but also its wet-slip resistance is equivalent to that of styrene-butadiene rubber, so control 1. 2-structure polybutadiene is very important in the synthesis of rubber for tire. Catalyst is very important in controlling the synthesis of 1 / 2-polybutadiene, and there are many kinds of catalysts, among which the iron catalyst is rich in content. Economy and environmental friendliness have attracted more and more attention in the field of synthetic rubber catalysis, but the high melting point of iron catalyst for the synthesis of 1h2- polybutadiene has restricted its development. In order to solve this problem. In this paper, the preparation of butadiene, isoprene copolymer and butadiene homopolymer by coordination polymerization catalyzed by iron catalyst was studied. The main conclusions are as follows: (1) Fe _ 2O _ 2-EHAN _ 3 / Al _ 2O _ 3 / DEP _ (3 / DEP) was used to catalyze Fe _ 2O _ 2-EHA _ 2 / diethyl phosphite at higher temperatures (P < 0.05). 50 鈩,
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