异辛醇改性三氯氧钒催化体系催化乙烯/丙烯共聚合
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摘要
以异辛醇改性三氯氧钒(VOCl_3·3(2-ethyl-hexanol))为催化剂前体,倍半乙基铝(EASC)为助催化剂,三氯乙酸乙酯(ETCA)为活化剂进行乙烯/丙烯共聚合,并与传统VOCl_3体系进行对比。考察了EASC和ETCA用量、反应温度对聚合的影响。随EASC用量的增加,2种催化体系活性均先增加后下降,VOCl_3·3(2-ethyl-hexanol)和VOCl_3体系分别在[Al]/[V]比为40和30时达到最高催化活性6. 15 kg EPR/g V·h和4. 97 kg EPR/g V·h。2种催化体系活性均随聚合温度的升高呈下降的趋势,VOCl_3·3(2-ethyl-hexanol)体系的下降幅度低于VOCl_3体系,表明异辛醇有效地稳定了生成的活性中心。差示扫描量热分析和核磁共振碳谱分析表明以VOCl_3·3(2-ethyl-hexanol)体系所合成的共聚物较VOCl_3体系有更高的丙烯插入率和更为无规的结构。
2-Ethylhexanol modified vanadium oxytrichloride [VOCl_3·3( 2-ethyl-hexanol) ]as catalyst precursor was examined for ethylene/propylene copolymerization with ethylaluminium sesquichloride( EASC) as cocatalyst and ethyl trichloroacetate( ETCA) as reactivator,along with the traditional VOCl_3-based system for comparison. The influences of EASC and ETCA loading levels as well as reaction temperature on the polymerization were investigated. With increasing the EASC dosage,the activities of both the systems increase and then decrease. The highest activities of VOCl_3·3( 2-ethyl-hexanol) and VOCl_3-based systems,6. 15 kg EPR/gV·h and 4. 97 kg EPR/gV·h,are observed at [Al]/[V]ratio of 40 and 30,respectively. While the catalytic activity of both systems decreases by increasing the polymerization temperature,the decline rate in the VOCl_3·3( 2-ethyl-hexanol) system is much lower than that in the VOCl_3 system.These results indicate that the presence of 2-ethyl-hexanol effectively stablizes the generated acive species. Determined by DSC and13C-NMR,the ethylene-propylene copolymer obtained with VOCl_3·3( 2-ethyl-hexanol) system has a higher propylene incorporation and more random structures than that prepared with the VOCl_3 system.
2-Ethylhexanol modified vanadium oxytrichloride [VOCl_3·3( 2-ethyl-hexanol) ]as catalyst precursor was examined for ethylene/propylene copolymerization with ethylaluminium sesquichloride( EASC) as cocatalyst and ethyl trichloroacetate( ETCA) as reactivator,along with the traditional VOCl_3-based system for comparison. The influences of EASC and ETCA loading levels as well as reaction temperature on the polymerization were investigated. With increasing the EASC dosage,the activities of both the systems increase and then decrease. The highest activities of VOCl_3·3( 2-ethyl-hexanol) and VOCl_3-based systems,6. 15 kg EPR/gV·h and 4. 97 kg EPR/gV·h,are observed at [Al]/[V]ratio of 40 and 30,respectively. While the catalytic activity of both systems decreases by increasing the polymerization temperature,the decline rate in the VOCl_3·3( 2-ethyl-hexanol) system is much lower than that in the VOCl_3 system.These results indicate that the presence of 2-ethyl-hexanol effectively stablizes the generated acive species. Determined by DSC and13C-NMR,the ethylene-propylene copolymer obtained with VOCl_3·3( 2-ethyl-hexanol) system has a higher propylene incorporation and more random structures than that prepared with the VOCl_3 system.
引文
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[3]Baier M C,Zuideveld M A,Mecking S.Post-metallocenes in the industrial production of polyolefins[J].Angew.Chem.Int.Ed.,2014,53:9722-9744.
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[6]Knauf Thomas F,Osman A,Padliya D.Reduced fouling in process for production:EP,652234[P].1999-01-13.
[7]罗裕基.无机化学丛书:第八卷[M].北京:科学出版社,1998:219-221.
[8]张学全,姜连升,万雄,等.用于合成三元乙丙橡胶的钒系催化剂及制备方法:中国,200710055981.X[P].2012-01-25.
[9]高巍,吕云霞,田柏森,等.用于乙丙橡胶生产的钒醇配体催化剂的制备研究[J].弹性体,2013,23(6):38-40.Gao W,LüY X,Tian B S,et al.Preparation research of vanadium alcohol ligand catalyst for ethylene propylene rubber production[J].China Elastomerics,2013,23(6):38-40.
[10]Zhang X Q,Chen H,Zhou Z N,et al.DSC and C-13 NMR-studies of ethylene-propene copolymers prepared by a highly-active and stereospecific catalyst[J].Macromol.Chem.Phys.,1994,195:1063-1073.
[11]周子南,李三喜,田文静,等.取代基效应(SCS)与乙烯-α-烯烃共聚物的序列结构-Ⅰ.乙烯-丙烯共聚物[J].波谱学杂志,1990,7(4):439-444.Zhou Z N,Li S X,Tian W J,et al.Substituent chemical shift(SCS)and the sequence structure of ethylene-α-olefine copolymersⅠ.ethylene-propylene copolymers[J].Chinese Journal of Magnetic Resonance,1990,7(4):439-444.
[12]李三喜,马瑞春,张帆.乙丙共聚物的13C-NMR研究[J].波谱学杂志,1998,15(2):109-116.Li S X,Ma R C,Zhang F.13C-NMR studies of ethylene-propylene copolymers synthesized with supproted Ziegler-Natta catalyst made by chemical reaction method[J].Chinese Journal of Magnetic Resonance,1998,15(2):109-116.
[13]Hao X F,Zhang C D,Li L,et al.Use of vanadium complexes bearing naphthalene-bridged nitrogen-sulfonate ligands as catalysts for copolymerization of ethylene and propylene[J].Polymers,2017,9:325.
[14]黄葆同,欧阳均.络合催化聚合合成橡胶[M].北京:科学出版社,1981:321.