羟基功能化3,4-聚2-芳基-1,3-丁二烯的合成  

Synthesis of Hydroxyl-functionalized 3,4-Poly(2-aryl-1,3-butadiene)s

作　　者：黄立贤 桑丽鹏[3] 苏高攀 郭翔[3] 李世辉[1,2] Li-xian Huang;Li-peng Sang;Gao-pan Su;Xiang Guo;Shi-hui Li(State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022;School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026;Science and Technology on Aerospace Chemical Power Laboratory,Hubei Institute of Aerospace Chemotechonology,Xiangyang 441003)

机构地区：[1]中国科学院长春应用化学研究所高分子物理与化学国家重点实验室,长春130022 [2]中国科学技术大学应用化学与工程学院,合肥230026 [3]湖北航天化学技术研究所航天化学动力技术重点实验室,襄阳441003

出　　处：《高分子学报》2024年第2期153-160,共8页Acta Polymerica Sinica

基　　金：国家自然科学基金面上项目(基金号52073275);航天化学动力技术重点实验室开放基金(基金号STACPL120221B03)资助项目。

摘　　要：采用(C13H8CH_(2)CH_(2)(NCHCCHN)■)Lu(CH_(2)SiMe_(3))2(1)、Ph_(2)P(=NDip)(NDip)Lu■(THF)(Dip=■)、Ph_(2)P(=NDip)(■)Lu(CH_(2)SiMe_(3))2(THF)(3)和Ph_(2)P(=NDip)(■)Sc(CH_(2)SiMe_(3))2(THF)(4)4种稀土催化剂,催化2-对甲基苯基-1,3-丁二烯(2-MPBD)均聚合.通过核磁共振(NMR)、凝胶渗透色谱(GPC)和示差扫描量热法(DSC)等对聚合物的微观结构和热性能进行了表征.催化剂1对2-MPBD聚合活性低,3,4-选择性低(65.2%);催化剂2几乎无催化活性;催化剂3和4表现出非常高的催化活性(2 min转化率达100%)和3,4-选择性(分别为98.1%和>99%).催化剂4对催化2-MPBD聚合具有活性聚合特征,产生的3,4-聚2-MPBD分子量随单体投入量呈线性增加,分子量分布介于1.12~1.25之间.对于苯基、间甲基苯基、4-戊基苯基、4-氟苯基和4-氯苯基取代的1,3-丁二烯单体,催化剂4也表现出较高的催化活性和3,4-选择性.3,4-聚芳基1,3-丁二烯侧链双键与硼烷、双氧水和氢氧化钠反应之后,转变为醇羟基功能化的3,4-聚芳基1,3-丁二烯.The polymerization of 2-(4-methylphenyl)-1,3-butadiene(2-MPBD)is performed using[C13H8CH_(2)CH_(2)-(NCHCCHN)C_(6)H_(2)Me_(3)-2,4,6]Lu(CH_(2)SiMe_(3))2(1),Ph_(2)P(=NDip)(NDip)Lu(CH_(2)Si-Me_(3))2(THF)(Dip=C_(6)H_(3)-2,6-iPr2;2),Ph_(2)P(=NDip)(NC_(6)H_(3)-2-Et)Lu(CH_(2)SiMe_(3))2(THF)(3)and Ph_(2)P(=NDip)(NC_(6)H_(3)-2-Et)Sc(CH_(2)SiMe_(3))2(THF)(4).The microstructures and thermal properties of resultant polymers are characterized by nuclear magnetic resonance spectroscopy(1H-NMR,13C-NMR),gel permeation chromatography(GPC)and differential scanning calorimetry(DSC).Complex 1,activated by[Ph3C][B(C_(6)F5)4]and AliBu3,shows low catalytic activity and 3,4-selectivity(65.2%)for 2-MPBD polymerization.Under the same conditions,complex 2 is nearly inert.In contrast,complexes 3 and 4 demonstrate high 3,4-selectivity(98.1%and>99%,respectively)and enable 100%conversion of 200 equivalents of 2-MPBD into polymers at 20℃with 2 min.The resultant molecular weights increase with monomer-to-catalyst ratios varying from 200:1 to 600:1 with narrow molecular weight distributions of 1.12-1.25.Furthermore,complex 4 also shows high catalytic activity and high 3,4-selectivity for the polymerizations of 2-phenyl-1,3-butadiene,2-(3-methylphenyl)-1,3-butadiene,2-(4-pentylphenyl)-1,3-butadiene,2-(4-fluorophenyl)-1,3-butadiene and 2-(4-chlorophenyl)-1,3-butadiene.The resultant 3,4-poly(2-aryl-1,3-butadiene)s are readily transformed into hydroxyl functionalized polymers by the treatment of BH_(3) and H_(2)O_(2).

关 键 词：稀土催化剂 功能化聚烯烃 3 4-选择性 共轭双烯 反应性功能化法 

分 类 号：TQ325.1[化学工程—合成树脂塑料工业] TQ426