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  本文選題：雙環(huán)戊二烯　切入點：開環(huán)移位聚合　出處：《河南科技大學(xué)》2017年碩士論文

【摘要】：聚雙環(huán)戊二烯(PDCPD)是一種綜合性能優(yōu)異的新型材料,它是由雙環(huán)戊二烯(DCPD)通過開環(huán)移位聚合而成。能夠催化DCPD聚合的催化劑有許多,但最常用的是烷基鋁與鎢酚化合物所組成的雙組份催化體系。主催化劑鎢酚化合物對氧氣和水汽敏感,容易失活。為了提高主催化劑在空氣中的穩(wěn)定性以及在DCPD中的溶解性,本課題采用高位阻的有機膦配體與六氯化鎢(WCl_6)配位,合成一類新型環(huán)境穩(wěn)定型的配位催化劑,并以此催化DCPD聚合制備PDCPD。本文以三苯基膦(Ph_3P)為原料,合成了一系列高位阻有機膦配體二苯基丁基膦(Ph_2PC＿4H＿9)、二苯基己基膦(Ph_2PC_6H_(13))、二苯基辛基膦(Ph_2PC_8H_(17))、二苯基癸基膦(Ph_2PC_(10)H_(21))、二苯基十二烷基膦(Ph_2PC_(12)H_(25)),并用IR、~1H-NMR、~(13)C-NMR以及31P-NMR等方法對有機膦配體的結(jié)構(gòu)進行了表征。將二苯基烷基膦和WCl_6進行配位反應(yīng),合成了五種新型二苯基烷基膦/六氯化鎢配合物,并對其進行了表征,確證得到了預(yù)期的目標產(chǎn)物。以二苯基烷基膦/六氯化鎢配合物為主催化劑(簡稱W催化劑),Et2Al Cl為助催化劑(簡稱Al催化劑)催化DCPD聚合,結(jié)果發(fā)現(xiàn)該配合物均具有較高的催化活性,并且在DCPD中溶解性較好、在空氣中穩(wěn)定性較好。系統(tǒng)地考察了主催化劑量、助催化劑量以及溫度等因素對聚合反應(yīng)的影響,探究了各催化劑催化DCPD聚合的最佳反應(yīng)條件,并比較了五種催化劑的活性。結(jié)果表明:隨著主催化劑、助催化劑量的增加以及反應(yīng)溫度的升高,DCPD聚合的凝膠時間逐漸減小;五種催化體系(碳鏈由短到長)催化DCPD聚合的最佳摩爾比(n(DCPD):n(W):n(Al))分別為:1600:1.2:24、1600:1.2:20、1600:1:20、1200:1:20、1200:1:22,由此可知,五種新型催化劑的催化活性順序為:Ph_2PC_8H_(17)/WCl_6Ph_2PC_6H_(13)/WCl_6Ph_2PC＿4H＿9/WCl_6Ph_2PC_(10)H_(21)/WCl_6Ph_2PC_(12)H_(25)/WCl_6。以Ph_2PC_8H_(17)/WCl_6配合物為主催化劑,Et2AlCl為助催化劑催化DCPD聚合制備PDCPD,并對材料的力學(xué)性能進行檢測,結(jié)果發(fā)現(xiàn)該材料的沖擊強度為30kJ/m2,拉伸強度平均值為43.75MPa。
[Abstract]:Poly (dicyclopentadiene) (PDCPD) is a new material with excellent comprehensive properties. It is prepared by ring-opening shift polymerization of dicyclopentadiene (DCPD). There are many catalysts that can catalyze the polymerization of DCPD. But the most commonly used catalyst is the two-component catalytic system composed of alkyl aluminum and tungsten phenol compounds. The main catalyst is sensitive to oxygen and water vapor and is easily deactivated. In order to improve the stability of the main catalyst in air and the solubility of the main catalyst in DCPD, In this paper, a new type of environment-stable coordination catalyst was synthesized by the coordination of high resistance organic phosphine ligands with tungsten hexachloride (WClS6), which was used to catalyze the polymerization of DCPD to prepare PDCPDs. In this paper, triphenylphosphine Phosphate (Ph3P3) was used as the raw material. A series of high resistive organic phosphine ligands, diphenyl phosphine ligands, diphenyl hexyl phosphine ligands, diphenyl hexyl phosphine ligands, diphenyl hexyl phosphine ligands, Ph2PC4H9, diphenyl hexyl phosphine, diphenyl hexyl phosphine, diphenyl hexyl phosphine, Ph2PC4H9, diphenyl hexyl phosphine, Ph2PC4H9, diphenyl hexyl phosphine, diphenyl hexyl phosphine ligands, Ph2PC4H9, diphenyl hexyl phosphine, diphenyl hexyl phosphine, Ph2PC4H9, diphenyl hexyl phosphine, diphenyl hexyl phosphine, Ph2PC4H9, diphenyl hexyl phosphine, diphenyl hexyl phosphine, diphenyl hexyl phosphine, ph2PC4H9, diphenyl hexyl phosphine, diphenyl hexyl phosph@@. The coordination reaction between diphenyl alkyl phosphine and WCl_6 was carried out. Five novel diphenyl alkyl phosphine / tungsten hexachloride complexes were synthesized and characterized. It was confirmed that the expected target product was obtained. The DCPD polymerization was catalyzed by diphenyl alkyl phosphine / tungsten hexachloride complex (W catalyst et 2AL Cl). The results showed that the complexes had higher catalytic activity, better solubility in DCPD and better stability in air. The effects of the amount of main catalyst, the amount of co-catalyst and temperature on the polymerization were systematically investigated. The optimum reaction conditions of each catalyst for DCPD polymerization were investigated, and the activity of five catalysts was compared. The results showed that the gel time of DCPD polymerization decreased with the increase of the amount of catalyst and the increase of reaction temperature. The optimum molar ratio of five catalytic systems (carbon chains from short to long) to catalyze DCPD polymerization is as follows: 1: 16 00: 1: 2: 24 16 00 1. 2: 20 20: 16 00 1: 1 1: 20 20: 1 1: 20 1: 20 20: 12: 1 22. The order of the catalytic activity of the five new types of catalysts is as follows:% Ph2PC8Hflesh 17 / WCl6Ph2PC6HJ / S / WCl6Ph2PC6H / S / S / WCl6Ph2Stud, and the results show that the impact strength of this material is 30kJ / m-2, and the average strength of the material is 43.75MPm2.The results show that the impact strength of the material is 30kJmrm2p2m2m2.The results show that the impact strength of this material is 30kJmrm2m2.The results show that the strength of the PDCPDs is 43.75MPm2.The results show that the impact strength of the PDCPDs is 30 kJs / m-2, and the average strength of the PDCPDs is 43.75MPm2.The order of the catalytic activity of the five new types of catalysts is as follows: 1: Ph2PC8Hac / WCl6Ph2AlCl as a catalyst for DCPD polymerization.
【學(xué)位授予單位】：河南科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36;O631.5

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