环辛二烯氘代、开环易位聚合及其聚合物的固相催化加成  

Deuterated and Ring-opening Metathesis Polymerization of Cyclooctadiene,and Solid-state Catalytic Addition of Its Polymers

作　　者：杜杰[1] 刘孟[1] 王丽萍[1] 郭彪 谭欣欣[1] 罗文华[1] Jie Du;Meng Liu;Li-ping Wang;Biao Guo;Xin-xin Tan*;Wen-hua Luo*(Institute of Materials,China Academy of Engineering Physics,Mianyang 621907)

机构地区：[1]中国工程物理研究院材料研究所,绵阳621907

出　　处：《高分子学报》2024年第6期738-749,共12页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21604075);中国工程物理研究院材料研究所特聘人才基金(基金号TP02201607)资助

摘　　要：氘(氚)代聚合物是一类很有前景的惯性约束聚变靶材料.为制备具有较多加氚位点的氘代聚合物,开展了环辛二烯的氘代及开环易位聚合实验研究.对1,5-环辛二烯反应过程中间产物组分进行分析,研究了其氘代反应机理.通过核磁共振波谱(1H-NMR、2H-NMR、13C-NMR)分析,表明环辛二烯氘代后的副产物为氘代环辛烯.研究了温度、添加剂、反应时间对产物氘代率及副产物生成率的影响,获得了优化的反应条件,并制备了氘代率高达96%的氘代1,3-环辛二烯.开展了(氘代)1,3-环辛二烯的开环易位聚合实验,其中大量连续共轭双键的存在导致聚合物结晶使得其溶解性较差.在5 wt%的Pd/BaSO4与Grubbs二代催化剂的存在下,开展了聚1,3-环辛二烯、氘代1,3-环辛二烯与氘代环辛烯共聚物的固相催化加氘实验,均可加氘至接近饱和,在此过程中伴随着明显的氢同位素交换反应.发展了一种均相固相催化氢同位素加成的方法,有望实现在已成型的氘代聚合物靶丸上直接加氚,从而制备氘-氚代聚合物靶丸.Deuterated(tritiated)polymers are a type of promissing target materials for inertial confinement fusion.To prepare deuterated polymers with more tritium addition sites,in this work,the deuteration and ring-opening metathesis polymerization of cyclooctadiene was investigated.The mechanism for deuteration reaction of 1,5-cyclooctadiene was studied by analyzing the components of intermediate products during the reaction process.The results of magnetic resonance spectroscopy(1H-NMR,2H-NMR and 13C-NMR)showed that the by-product of deuterated cyclooctadiene was deuterated cyclooctadiene.The effects of temperature,additives and reaction time on the deuteration rate of products and the yields of by-products were studied,and then the optimized reaction conditions were obtained.Deuterated 1,3-cyclooctadiene with a high deuteration rate up to 96%was prepared.The experiment of ring-opening metathesis polymerization of(deuterated)1,3-cyclooctadiene was carried out.The existence of a large number of continuous conjugated double bonds led to the crystallization of the polymer,resulting in a poor solubility.In the presence of 5 wt%Pd/BaSO4 and Grubbs second generation catalyst,solid-state catalytic deuteration experiments of poly(1,3-cyclooctadiene)and the copolymers of deuterated 1,3-cyclooctadiene and deuterated cyclooctadiene were carried out.The polymer chain can be added to near saturation with D2,accompanied by obvious hydrogen isotope exchange reaction.A homogeneous solid-phase catalytic hydrogen isotope addition method has been developed.By this method,the well processed deuterated polymer target pellets can be added with tritium directly,and thus the deuterium-tritiated polymer target pellets can be prepared.

关 键 词：氘代机理 氘代聚合物 开环易位聚合 固相催化氘化 

分 类 号：TL627[核科学技术—核技术及应用] TQ316.3[化学工程—高聚物工业]