超高分子量聚α-烯烃的高效合成及其减阻性能研究  

Efficient Synthesis and Drag Reduction Properties of Ultra-high Molecular Weight Poly-α-olefin

作　　者：姜子豪 李鑫源 回立为 康宇泽 王菲 蔡浩 潘莉 李悦生[1] Zi-hao Jiang;Xin-yuan Li;Li-wei Hui;Yu-ze Kang;Fei Wang;Hao Cai;Li Pan;Yue-sheng Li(School of Materials Science and Engineering,Tianjin University,Tianjin 300350;Sino Oil King Shine Chemical Co.,Ltd.,Langfang 065000)

机构地区：[1]天津大学材料科学与工程学院,天津300350 [2]廊坊开发区中油科新化工有限责任公司,廊坊065000

出　　处：《高分子学报》2024年第4期419-427,共9页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号52130307)资助项目。

摘　　要：利用第四代Ziegler-Natta催化体系——负载在MgCl_(2)上的TiCl_(4)为主催化剂,三乙基铝(Et_(3)Al)为助催化剂,甲基环己基二甲氧基硅烷(CHMDMS)为外给电子体,在磁力搅拌和机械搅拌2种条件下催化1-辛烯和1-癸烯共聚合,制得了一系列高减阻性能聚α-烯烃(Poly-alpha-olefin,PAO)类减阻剂.利用高温凝胶渗透色谱仪测得聚合物的重均分子量(M_(w))在3×10^(6)以上,分子量分布指数(PDI)基本在3.04以内.进一步通过低温机械搅拌可实现更窄的聚合物分子量分布(1.27~1.90).通过核磁共振(^(13)C-NMR)对聚合物进行分子结构表征,结果表明得到了目标产物、无单体残留,且聚合物中单体比例与投料比基本一致.示差扫描量热法(DSC)和X射线衍射(XRD)测试结果表明,成功合成了无结晶行为的聚合物.热重分析(TGA)结果表明,该聚合物在氮气气氛下的热分解温度在300℃以上,远高于使用温度.环路管道循环实验表明,随着聚合物分子量增加,减阻效率整体呈增加趋势,共聚物的减阻效率大于均聚物;随着单体与催化剂的摩尔比增加,减阻效率先升高后降低.相较已有报道,减阻性能有较大提升,最高减阻率可达50%.Using 1-octene and 1-decene as monomers,and a catalytic system of TiCl_(4)(a fourth-generation Ziegler-Natta catalyst)loaded on MgCl_(2)as the main catalyst,triethylaluminium(Et_(3)Al)as a co-catalyst,and methylcyclohexyldimethoxysilane(CHMDMS)as the external electron donor,under both magnetic stirring and mechanical stirring conditions,respectively,a series of poly-α-olefin(PAO)-based drag reducer were successfully prepared.As proven by high-temperature gel permeation chromatography,the newly obtained polymers not only had very high molecular weight,(weight average molecular weight of most of the polymers was higher than 3×10^(6)),but also had very narrow molecular weight distribution(polymer dispersity index was lower than 3.0 for most of the polymers),suggesting a uniform distribution of all polymer chains.The obtained polymers were characterized by ^(13)C-nuclear magnetic resonance(^(13)C-NMR),differential scanning calorimetry(DSC),thermal gravimetric analyzer(TGA)and X-ray diffraction(XRD),respectively.It turned out that target polymers with expected composition were obtained.Most of the polymers were amorphous,making them well-soluble in oils.All polymers showed high decomposition temperature beyond 300℃,much higher than working temperature of drag reducers.The loop pipeline cycling experiment indicated that the drag reduction efficiency of the newly obtained polymers was greatly improved compared with those of commercial products and previous reports.

关 键 词：减阻剂 聚Α-烯烃 减阻率 ZIEGLER-NATTA催化剂 

分 类 号：TQ325.1[化学工程—合成树脂塑料工业]