DESIGN AND SYNTHESIS OF POLYPROPYLENE-b-POLYPHOSPHATE BLOCK COPOLYMERS
DESIGN AND SYNTHESIS OF POLYPROPYLENE-b-POLYPHOSPHATE BLOCK COPOLYMERS
复制标题
聚丙烯-b-多磷酸酯嵌段共聚物的设计与合成
DOI：
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发表时间：
2013
影响因子：
1.9
通讯作者：
Dong, Jin-yong
中科院分区：
文献类型：
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作者：
Wang, Hong-zhen;Qin, Ya-wei;Dong, Jin-yong
合成了新型含磷聚丙烯嵌段共聚物，并通过热重分析（TGA）和微量燃烧量热法（MCC）对其热分解行为和燃烧性能进行了表征。首先，通过可控链转移反应合成了末端带有苯乙烯基的反应性聚丙烯（PP-t-St），4-二乙烯基苯与氢气在均苯丙烯聚合中的反应，然后PP-t-St与溴化氢通过Markovnikov加成反应进行准定量反应，得到1-溴代噻吩基封端的聚丙烯，（PP-t-BzBr）.含磷乙烯基单体如二乙基-（4-乙烯基苄基）膦酸酯（DEVBP）在甲苯中在高温下进行，PP-t-BzBr悬浮在反应物溶液中，CuCl/1，1，4，7，10，以10-六甲基三亚乙基四胺（HMTETA）为催化剂，通过调节聚合持续时间获得了（高达64.3wt%）。实验表明，PP-b-PP在很大程度上保留了PP的结晶度和结晶速率，TGA和MCC结果表明，与PDEVBP二嵌段共聚物相比，形成二嵌段共聚物后，焦炭残留物增加，而热释放速率降低。总的来说，这项研究可能会导致一个新的解决方案，固有的阻燃聚丙烯。
Novel phosphorus-containing polypropylene diblock copolymers were synthesized and their thermal decomposing behaviors and flammability were characterized by thermo-gravimetric analysis(TGA) and micro-scale combustion calorimetry(MCC).First,a reactive polypropylene precursor with a terminal styryl group(PP-t-St) at polymer chain end was synthesized via controlled chain transfer reaction to 1,4-divinylbenzene and hydrogen in metallocene-mediated propylene polymerization.Then PP-t-St was reacted with hydrogen bromide through Markovnikov addition in a quasi-quantitative manner,affording 1-bromoethylbenzene group-terminated polypropylene(PP-t-BzBr).ATRP of phosphorous-containing vinyl monomer such as diethyl-(4-vinylbenzyl)phosphonate(DEVBP) was carried out in toluene at elevated temperatures with PP-t-BzBr suspending in the reactant solution,with CuCl/1,1,4,7,10,10-hexamethyltriethylenetetramine(HMTETA) as catalyst.Diblock copolymers containing different amounts of DEVBP units(up to 64.3 wt%) were obtained by adjusting polymerization durations.Differential scanning calorimetry(DSC) experiments indicated that both the crystallinity and crystallization rate of PP were largely retained in PP-b-PDEVBP diblock copolymers.TGA and MCC results showed that char residues increased while heat release rates reduced upon forming the diblock copolymers as compared to the precursory PP-t-BzBr as well as PP-t-St.Overall,this research may lead to a new solution to inherently flame-retardant polypropylene.