Synthesis and application of five-membered ring fluoride

doi:10.11949/0438-1157.20200582

Abstract

Abstract:

The synthetic routes for a series of five-membered ring fluorides by using dicyclopentadiene (DCPD), hexachlorocyclopentadiene (HCCPD) or octachlorocyclopentene (OCP) as starting materials are reviewed, including 1,2-dichlorohexafluorocyclopentene (F6-12), 1,3-dichlorohexafluorocyclopentene (F6-13), 1-chlorohepta-fluorocyclopentene (F7-1), 1,1,2,2,3,3,4-heptafluorocyclopentane (F7A), 1,1,2,2,3,3-hexafluorocyclopentane (F6A), cis-1,1,2,2,3,3,4,5-octafluorocyclopentane (cis-F8A), octafluorocyclopentene (F8E), 3,3,4,4,5,5-hexafluorocyclopentene (F6E), 1,3,3,4,4,5,5-heptafluorocyclopentene (F7E) and the application of five-membered ring fluorides in electronic cleaning, electronic etching, and synthesis of electronic fluoride solutions. It is proposed that the synthesis research of five-membered ring fluorides mainly focus on the development of novel synthetic routes, catalysts with high activity and no harm to human health, and green manufacturing. Furthermore, the application research focus on the development of the electronic grade products and the downstream products of five-membered ring fluorides.

Key words: five-membered ring fluoride, 1,1,2,2,3,3,4-heptafluorocyclopentane, electronic cleaning, electronic etching, electronic fluorinated liquid, catalysis, catalyst, catalyst activation

摘要：

综述了以双环戊二烯（DCPD）、六氯环戊二烯（HCCPD）或八氯环戊烯（OCP）为起始原料合成1,2-二氯六氟环戊烯（F6-12）、1,3-二氯六氟环戊烯（F6-13）、1-氯七氟环戊烯（F7-1）、1,1,2,2,3,3,4-七氟环戊烷（F7A）、1,1,2,2,3,3-六氟环戊烷（F6A）、顺式-1,1,2,2,3,3,4,5-八氟环戊烷（cis-F8A）、八氟环戊烯（F8E）、3,3,4,4,5,5-六氟环戊烯（F6E）、1,3,3,4,4,5,5-七氟环戊烯（F7E）等系列五元环氟化物的合成路线，以及五元环氟化物在电子清洗、电子刻蚀、合成电子氟化液的应用。提出了五元环氟化物的合成研究重点是新型合成路线的开发、高催化活性且对人体健康无害的过程催化剂的开发，以及无污染化工艺过程的开发，而应用研究重点是开发五元环氟化物的电子级产品以及开发五元环氟化物的下游产品。

关键词: 五元环氟化物, 1,1,2,2,3,3,4-七氟环戊烷, 电子清洗, 电子刻蚀, 电子氟化液, 催化, 催化剂, 催化剂活化

CLC Number:

TQ 203.2

Chengping ZHANG, Feiyao QING, Xiaoqing JIA, Hengdao QUAN. Synthesis and application of five-membered ring fluoride[J]. CIESC Journal, 2020, 71(9): 3963-3978.

张呈平, 庆飞要, 贾晓卿, 权恒道. 五元环氟化物的合成及应用[J]. 化工学报, 2020, 71(9): 3963-3978.

Figures/Tables 10

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项目	F7A	HCFC-141b	HFC-365mfc	HFC-4310mee	HFE-449s1
分子式	C₅H₃F₇	C₂H₃Cl₂F	C₄H₅F₅	C₅H₂F₁₀	C₄F₉OCH₃
沸点/℃	82.5	32.05	40.2	55	61
饱和蒸气压/kPa	8.3（20℃）	7.9（25℃）	37.77（25℃）	24.8（25℃）	38.4（25℃）
黏度/(mPa·s)	0.7（45℃）	0.4（25℃	0.4（25℃）	0.67（25℃）	0.61（25℃）
液体密度/(g/ml)	1.58（21℃）	1.25（21℃）	1.263（21℃）	1.58（21℃）	1.52（21℃）
汽化潜热/(kJ/kg)	144.21	234.50	176.81	129.58	125.82
比热容/(J/(g·℃))	1.21	1.17	1.46	1.13	1.18
表面张力/(mN/m)	18（45℃）	18.7（20℃）	15（20℃）	14.1（25℃）	13.6（25℃）
KB值	14	56	13	12	10
可接受暴露局限/(mg/kg)，8h/12h	123	500	1000	200	750
燃烧下限/ % (vol)	无(常温）	无	无	无	无
闪点/℃	无	无	-27	无	无
可燃性	不可燃	不可燃	可燃	不可燃	不可燃
ODP值	0	0.11	0	0	0
大气寿命/a	3.4	9.4	8.7	16.1	4.7
GWP₁₀₀值	195	630	804	1650	297

项目	F7A	HCFC-141b	HFC-365mfc	HFC-4310mee	HFE-449s1
分子式	C₅H₃F₇	C₂H₃Cl₂F	C₄H₅F₅	C₅H₂F₁₀	C₄F₉OCH₃
沸点/℃	82.5	32.05	40.2	55	61
饱和蒸气压/kPa	8.3（20℃）	7.9（25℃）	37.77（25℃）	24.8（25℃）	38.4（25℃）
黏度/(mPa·s)	0.7（45℃）	0.4（25℃	0.4（25℃）	0.67（25℃）	0.61（25℃）
液体密度/(g/ml)	1.58（21℃）	1.25（21℃）	1.263（21℃）	1.58（21℃）	1.52（21℃）
汽化潜热/(kJ/kg)	144.21	234.50	176.81	129.58	125.82
比热容/(J/(g·℃))	1.21	1.17	1.46	1.13	1.18
表面张力/(mN/m)	18（45℃）	18.7（20℃）	15（20℃）	14.1（25℃）	13.6（25℃）
KB值	14	56	13	12	10
可接受暴露局限/(mg/kg)，8h/12h	123	500	1000	200	750
燃烧下限/ % (vol)	无(常温）	无	无	无	无
闪点/℃	无	无	-27	无	无
可燃性	不可燃	不可燃	可燃	不可燃	不可燃
ODP值	0	0.11	0	0	0
大气寿命/a	3.4	9.4	8.7	16.1	4.7
GWP₁₀₀值	195	630	804	1650	297

项目	F8E	四氟甲烷	六氟乙烷	八氟环丁烷
分子式	C₅F₈	CF₄	C₂F₆	C₄F₈
ODP值	0	0	0	0
GWP₁₀₀值	90	6630	11000	9540
大气寿命/a	1	50000	10000	3200
对SiO₂刻蚀速率/(nm/min)	176^[83]	—	—	272^[83]
对SiO₂/基底的刻蚀选择比	3.78^[83]	较差	较差	2.00^[83]

项目	F8E	四氟甲烷	六氟乙烷	八氟环丁烷
分子式	C₅F₈	CF₄	C₂F₆	C₄F₈
ODP值	0	0	0	0
GWP₁₀₀值	90	6630	11000	9540
大气寿命/a	1	50000	10000	3200
对SiO₂刻蚀速率/(nm/min)	176^[83]	—	—	272^[83]
对SiO₂/基底的刻蚀选择比	3.78^[83]	较差	较差	2.00^[83]

项目	PE-1	PE-2	PE-3	FC-43	FC-70
分子式	C₁₀F₁₇N	C₉F₁₅N	C₉F₁₅NO	C₁₂F₂₇N	C₁₅F₃₃N
ODP值	0	0	0	0	0
GWP₁₀₀值	416	—	—	>5000	>5000
倾点/℃	-34	-33	-49	-50	-25
介电常数(1 kHz)	1.98	—	—	1.90	1.98