环保型氟碳化学品一氯一氟乙烯的制备与应用

doi:10.11949/0438-1157.20250134

摘要/Abstract

摘要：

一氯一氟乙烯（HCFO-1131）是一种含氟原子、氯原子及碳碳双键官能团的功能性化合物，其独特的分子结构赋予其特殊的物理化学性质。作为合成铁电性/压电性含氟聚合物P(VDF-TrFE-CFE) 的核心单体（质量占比达7%~10%），该材料在智能传感、固态制冷及新能源器件领域展现出巨大应用潜力，预计未来市场需求有望呈指数级增长。综述了HCFO-1131的合成路径及其在智能材料领域的应用拓展。HCFO-1131的主要合成路线包括含氯烯烃的氟化法、氟氯烷烃锌粉还原脱卤法以及多卤代烷烃液碱/热/催化脱HCl法。然而，上述方法普遍存在转化率低、选择性差、三废排放量高等缺陷，严重制约其规模化量产进程。针对环境友好性与材料性能的协同需求，亟需优化现有工艺或开发新型合成策略，以实现HCFO-1131的绿色高效制备，进而推动其在生物医学柔性器件、固态制冷芯片及储能复合材料等前沿领域的应用，为下一代智能装备提供关键材料支撑。

关键词: 催化, 合成, 聚合物单体, 电活性聚合物, 电子材料, 氟

Abstract:

Chlorofluoroethylene (HCFO-1131), containing fluorine atom, chlorine atom, and CC double bond, exhibits a unique molecular configuration that endows it with exceptional physicochemical properties. As the core monomer (7%—10% by mass) for the synthesis of ferroelectric/piezoelectric fluorinated polymers P(VDF-TrFE-CFE), this material shows great application potential in the fields of smart sensors, solid-state refrigeration and new energy devices, and the market demand is expected to grow exponentially in the future. This paper reviews the synthetic pathways of HCFO-1131 and its application in intelligence materials. Current synthetic routes primarily involve: halogen exchange reactions of chlorinated olefins, zinc-mediated reductive dehalogenation of fluorochlorocarbons, and dehydrochlorination of polyhalogenated hydrocarbons. However, these methodologies suffer from intrinsic drawbacks such as slow conversions, low selectivities, and large amount of waste, severely limiting their scalability in contemporary manufacturing. There is an urgent need to optimize existing processes or develop novel synthetic strategies to achieve green and efficient preparation of HCFO-1131, facilitating its applications in cutting-edge materials.

Key words: catalysis, synthesis, polymer monomers, electroactive polymer, electronic materials, fluorine

中图分类号:

TQ 9

李玲, 周鑫枭, 马超峰, 吴建, 于万金, 刘武灿, 张建君. 环保型氟碳化学品一氯一氟乙烯的制备与应用[J]. 化工学报, 2025, 76(10): 5003-5014.

Ling LI, Xinxiao ZHOU, Chaofeng MA, Jian WU, Wanjin YU, Wucan LIU, Jianjun ZHANG. Preparation and applications of eco-friendly fluorocarbon chemical chlorofluoroethylene[J]. CIESC Journal, 2025, 76(10): 5003-5014.

图/表 7

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序号	CH₃CFCl₂流量/(mol/h)	反应温度/℃	接触时间/s	CH₃CFCl₂含量/%	产物含量/%		CH₂CFCl 收率/%
序号	CH₃CFCl₂流量/(mol/h)	反应温度/℃	接触时间/s	CH₃CFCl₂含量/%	CH₂CFCl	CH₂CCl₂	CH₂CFCl 收率/%
1	0.62	500	35	12.9	64.5	8.6	74
2	1.85	500	12	44.8	39.5	7.6	71.5
3	0.50	400	49	64.9	12.4	7.7	35.3
4	1.95	600	10	0	27.4	0	27.4

序号	CH₃CFCl₂流量/(mol/h)	反应温度/℃	接触时间/s	CH₃CFCl₂含量/%	产物含量/%		CH₂CFCl 收率/%
序号	CH₃CFCl₂流量/(mol/h)	反应温度/℃	接触时间/s	CH₃CFCl₂含量/%	CH₂CFCl	CH₂CCl₂	CH₂CFCl 收率/%
1	0.62	500	35	12.9	64.5	8.6	74
2	1.85	500	12	44.8	39.5	7.6	71.5
3	0.50	400	49	64.9	12.4	7.7	35.3
4	1.95	600	10	0	27.4	0	27.4

催化剂	反应温度/℃	选择性/%
催化剂	反应温度/℃	CF₂CH₂	CFClCH₂
Al₂O₃	200	—	1.8
	300	1.3	91.0
	400	7.6	90.6
SiO₂	400	14.5	75.5
Al₂O₃-SiO₂	200	1.1	52.2
	300	36.6	63.2
	400	78.6	2.1
TiO₂	300	2.0	88.0
TiO₂	400	67.2	11.8
AlF₃-Al₂O₃	300	10.4	79.5
AlF₃-Al₂O₃	400	12.4	83.4
活性炭	300	93.5	3.2
无催化剂	500	5.9	—

催化剂	反应温度/℃	选择性/%
催化剂	反应温度/℃	CF₂CH₂	CFClCH₂
Al₂O₃	200	—	1.8
	300	1.3	91.0
	400	7.6	90.6
SiO₂	400	14.5	75.5
Al₂O₃-SiO₂	200	1.1	52.2
	300	36.6	63.2
	400	78.6	2.1
TiO₂	300	2.0	88.0
TiO₂	400	67.2	11.8
AlF₃-Al₂O₃	300	10.4	79.5
AlF₃-Al₂O₃	400	12.4	83.4
活性炭	300	93.5	3.2
无催化剂	500	5.9	—

反应途径	原料	优点	缺点
金属还原	1,1-二氯-2-溴-1-氟乙烷[式（4）] 1,1,2-三氯-1-氟乙烷[式（5）]	条件温和，原料易得	“三废”量高，操作复杂
碱液脱卤化氢	1,2-二氯-1-氟乙烷[式（6）、式（7）] 1,1-二氯-1-氟乙烷^[31]	条件温和，转化率和选择性优异	产生大量碱性废液
热解	1-氯-1,1-二氟乙烷^[34]	气相反应连续进料，“三废”量少	反应速率慢，选择性低，反应温度高
催化热解	1-氯-1,1-二氟乙烷[式（8）] 1,1,1-三氯乙烷[式（9）] 1,1-二氯-1-氟乙烷[式（10）]	在热解途径的基础上提升反应速率，降低反应温度	催化剂易失活，选择性较低，反应温度较高