摘要
以1.0代聚酰胺-胺(PAMAM)与3,5-二叔丁基水杨醛水杨醛为原料,通过席夫碱反应合成一种新型树枝状水杨醛亚胺配体,并与钛络合得到一种树枝状钛金属催化剂。运用FTIR、^(1)H-NMR、UV、ESI-MS等结构分析表征方法对合成的配体及钛金属催化剂进行了结构表征分析,同时,对树枝状钛金属催化剂催化乙烯聚合性能及反应体系的相关动力学参数进行了研究。实验结果表明,树枝状配体及树枝状桥联催化剂的结构与理论结构相符,其催化乙烯聚合性能较好,活性可达312.56 kg PE/(mol·Ti·h),聚合产物为UHMWPE。其催化乙烯聚合反应的动力学曲线为速升缓降型,聚合反应级数为1.09,属于准一级反应,聚合表观速率反应方程式可以表示为R_(p)=k_(p)C^(*)C^(1.09)_(m)。在一定的反应压力和温度条件下,聚合反应速率随乙烯压力的增大而增大,随反应温度的增大而降低。根据Arrhenius公式求得树枝状3,5-二叔丁基水杨醛亚胺钛金属催化剂催化乙烯聚合反应的表观活化能为16.02 kJ/mol。
A novel dendritic salicylaldehyde imine ligand was synthesized from 1.0 generation polyamide-amine(PAMAM) and 3,5-ditert-butyl salicylaldehyde by schiff base reaction,and further complexation with titanium to obtain a dendritic titanium metal catalyst.FTIR,^(1)H-NMR,UV,ESI-MS and other structural analysis methods were used to characterize the structure of the synthesized ligands and titanium catalysts.Meanwhile,the correlation kinetic parameters of ethylene polymerization properties and reaction system catalyzed by dendritic titanium metal catalyst were investigated.The experimental results showed that the structure of dendritic ligand and dendritic bridging catalyst consistent with the theoretical structure,with excellent catalytic ethylene polymerization performance,with the activity of 312.56 kg PE/(mol·Ti·h),and the polymerization product was UHMWPE.The kinetic curve of its catalytic ethylene polymerization was of rapid rise and slow decline type,and the polymerization reaction order was 1.09,which belongs to the quasi-first-class reaction.The aggregation apparent rate reaction equation could be expressed as R_p=k_pC~*C~(1.09)_m.under certain reaction pressure and temperature,the polymerization rate increases with the increase of ethylene pressure and decreases with the increase of reaction temperature.According to Arrhenius formula,the apparent activation energy of ethylene polymerization catalyzed by dendritic 3,5-Di-tert-butyl salicylaldehyde imine titanium catalyst was 16.02 kJ/mol.
作者
兰天宇
丛珊珊
张娜
王俊
LAN Tianyu;CONG Shanshan;ZHANG Na;WANG Jun(College of Materials Science and Engineering,Qiqihar University,Qiqihar,Heilongjiang 161006,China;College of Chemistry and Chemical Engineering,Northeast Petroleum University,Daqing,Heilongjiang 163318,China;Heilongjiang Provincial Key Laboratory of Polymeric Composite Materials,Qiqihar,Heilongjiang 161006,China)
出处
《塑料》
CAS
CSCD
北大核心
2023年第4期76-81,152,共7页
Plastics
基金
973国家重点研发项目(2017YFB0306701)
黑龙江省省属高等学校基本科研业务费科研项目(135509301)。
