Due to its inertness and solubility in vinylidene fluoride, (VF2), supercritical carbon dioxide is used as a replacement solvent for producing polyvinylidene fluoride (PVDF). tert-butyl peroxyacetate (TBPA) was evaluated for the first time as a free radical initiator for radical chain polymerization of VF2 producing PVDF without use of a dispersion agent in a semibatch reactor using supercritical carbon dioxide. Diethyl peroxydicarbonate (DEPDC) at 75°C has been evaluated in many publications as an initiator in batch and continuous reactors for polymerization of VF2 in supercritical carbon dioxide. The effects of monomer and initiator concentration, agitation, and reaction time upon average molecular weight and polydispersity were evaluated using TBPA as an initiator at 104°C and compared with DEPDC initiated polymerization. It was found that as agitation rate, monomer concentration, and reaction time increased, the average molecular weight of PVDF using TBPA as an initiator increased. Lower concentrations of TBPA were needed compared to DEPDC to produce comparable molecular weights of PVDF. Using TBPA as an initiator at the conditions investigated resulted in lower polydispersity at similar monomer concentrations compared to DEPDC. Average molecular weights using TBPA ranged from 49,900 g/mol to 1.3 million g/mol and polydispersity ranged from 1.3 to 5.4. POLYM. ENG. SCI., 56:435–440, 2016. © 2016 Society of Plastics Engineers

中文翻译：

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过氧乙酸叔丁酯引发的1,1-二氟乙烯在超临界二氧化碳中的半间歇聚合

由于其在偏二氟乙烯（VF2）中的惰性和溶解性，超临界二氧化碳被用作生产聚偏二氟乙烯（PVDF）的替代溶剂。在使用超临界二氧化碳的半间歇反应器中，在不使用分散剂的情况下，首次评估了过氧乙酸叔丁基酯（TBPA）作为生产VF2的PVDF自由基链聚合的自由基引发剂。在许多出版物中已评估了75°C下的过氧化二碳酸二乙酯（DEPDC）作为在超临界二氧化碳中聚合VF2的间歇式和连续式反应器的引发剂。使用TBPA作为引发剂，在104℃下评估单体和引发剂浓度，搅拌和反应时间对平均分子量和多分散度的影响，并与DEPDC引发的聚合反应进行比较。发现随着搅拌速率，单体浓度和反应时间的增加，使用TBPA作为引发剂的PVDF的平均分子量增加。与DEPDC相比，需要较低浓度的TBPA才能生产可比较分子量的PVDF。在相似的单体浓度下，与DEPDC相比，在研究的条件下使用TBPA作为引发剂会导致较低的多分散性。使用TBPA的平均分子量为49,900g / mol至130万g / mol，多分散度为1.3至5.4。POLYM。ENG。SCI。，56：435–440，2016.©2016塑料工程师协会 与DEPDC相比，需要较低浓度的TBPA才能生产可比较分子量的PVDF。在相似的单体浓度下，与DEPDC相比，在研究的条件下使用TBPA作为引发剂会导致较低的多分散性。使用TBPA的平均分子量为49,900g / mol至130万g / mol，多分散度为1.3至5.4。POLYM。ENG。SCI。，56：435–440，2016.©2016塑料工程师协会 与DEPDC相比，需要较低浓度的TBPA才能生产可比较分子量的PVDF。与DEPDC相比，在研究的条件下使用TBPA作为引发剂可在相似的单体浓度下降低多分散性。使用TBPA的平均分子量为49,900g / mol至130万g / mol，多分散度为1.3至5.4。POLYM。ENG。SCI。，56：435–440，2016.©2016塑料工程师协会