环辛二烯氘代、开环易位聚合及其聚合物的固相催化加成

杜杰; 刘孟; 王丽萍; 郭彪; 谭欣欣; 罗文华

doi:10.11777/j.issn1000-3304.2023.23273

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环辛二烯氘代、开环易位聚合及其聚合物的固相催化加成

研究论文 | 更新时间：2024-06-05

- 环辛二烯氘代、开环易位聚合及其聚合物的固相催化加成
  增强出版
- Deuterated and Ring-opening Metathesis Polymerization of Cyclooctadiene, and Solid-state Catalytic Addition of Its Polymers
- 高分子学报 2024年55卷第6期页码：738-749
- 作者机构：
  
  中国工程物理研究院材料研究所绵阳 621907
- 作者简介：
  
  E-mail: tanxx@caep.cn
  luowenhua@caep.cn
- 基金信息：
  
  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)
- DOI：10.11777/j.issn1000-3304.2023.23273
  中图分类号：
- 纸质出版日期：2024-06-20，
  
  网络出版日期：2024-03-11，
  
  收稿日期：2023-11-23，
  
  录用日期：2024-01-12
- 稿件说明：
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杜杰, 刘孟, 王丽萍, 郭彪, 谭欣欣, 罗文华. 环辛二烯氘代、开环易位聚合及其聚合物的固相催化加成. 高分子学报, 2024, 55(6), 738-749

Du, J.; Liu, M.; Wang, L. P.; Guo, B.; Tan, X. X.; Luo, W. H. Deuterated and ring-opening metathesis polymerization of cyclooctadiene，and solid-state catalytic addition of its polymers. Acta Polymerica Sinica, 2024, 55(6), 738-749
杜杰, 刘孟, 王丽萍, 郭彪, 谭欣欣, 罗文华. 环辛二烯氘代、开环易位聚合及其聚合物的固相催化加成. 高分子学报, 2024, 55(6), 738-749 DOI： 10.11777/j.issn1000-3304.2023.23273.

Du, J.; Liu, M.; Wang, L. P.; Guo, B.; Tan, X. X.; Luo, W. H. Deuterated and ring-opening metathesis polymerization of cyclooctadiene，and solid-state catalytic addition of its polymers. Acta Polymerica Sinica, 2024, 55(6), 738-749 DOI： 10.11777/j.issn1000-3304.2023.23273.

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(

H-NMR、

C-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/BaSO

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.

Abstract

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 (

H-NMR

H-NMR and

C-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/BaSO

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

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

Keywords

Deuteration mechanismDeuterated polymerRing-opening metathesis polymerizationSolid-state catalytic deuteration

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