五元环氟化物的合成及应用

doi:10.11949/0438-1157.20200582

摘要/Abstract

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

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

中图分类号:

TQ 203.2

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.

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

图/表 10

参考文献 90

1	权恒道, 张呈平, 贾晓卿. 全氟腈的制备方法: 107935884B[P]. 2020-06-12.
	Quan H D, Zhang C P, Jia X Q. The preparation method of perfluoronitriles: 107935884B[P]. 2020-06-12.
2	权恒道, 张呈平, 庆飞要, 等. 全氟腈的制备方法: 108424375B[P]. 2020-06-02.
	Quan H D, Zhang C P, Qing F Y, et al. The preparation method of perfluoronitriles: 108424375B[P]. 2020-06-02.
3	权恒道, 张呈平, 庆飞要, 等. 气相催化制备全氟腈的方法: 109320436A[P]. 2019-02-12.
	Quan H D, Zhang C P, Qing F Y, et al. The preparation method of perfluoronitriles by gas-phase catalytic reaction: 109320436A[P]. 2019-02-12.
4	权恒道, 田村正则, 关屋章. 碳酰氟的制造方法: 101272983B[P]. 2011-11-16.
	Quan H D, Tamura M, Sekiya A. Process for production of carbonyl fluoride: 101272983B[P]. 2011-11-16.
5	刘东明, 杨光成, 毛燕超, 等. 一种同时合成三氟碘甲烷和五氟碘乙烷的方法: 101219925B[P]. 2011-01-26.
	Liu D M, Yang G C, Mao Y C, et al. Method for synthesizing trifluoroiodomethane and pentafluoroethyliodide meanwhile: 101219925B[P]. 2011-01-26.
6	张呈平, 刘冬鹏, 贾晓卿, 等. 气相制备全氟酮的方法: 109336751A[P]. 2018-02-15.
	Zhang C P, Liu D P, Jia X Q, et al. The preparation method of perfluoroketones by gas-phase reaction: 109336751A[P]. 2018-02-15.
7	Guo Q, Zhang N, Uchimaru T, et al. Atmospheric chemistry for gas-phase reactions of cyc-CF₂CF₂CF₂CHXCHX— (X = H or F) with OH radicals in the temperature range of 253—328 K[J]. Atmos. Environ., 2019, 215: 116895.
8	Guo Q, Zhang N, Uchimaru T, et al. Atmospheric chemistry of cyc-CF₂CF₂CF₂CHCH—: kinetics, products, and mechanism of gas-phase reaction with OH radicals, and atmospheric implications[J]. Atmos. Environ., 2018, 179: 69-76.
9	Zhang N, Chen L, Uchimaru T, et al. Kinetics of gas-phase reactions of cyc-CF₂CF₂CF₂CHFCH₂— and trans-cyc-CF₂CF₂CF₂CHFCHF— with OH radicals between 253 and 328 K [J]. Chem. Phys. Lett., 2018, 639: 199-204.
10	Liu D P, Qin S, Li W, et al. Atmospheric chemistry of 1H-heptafluorocyclopentene (cyc-CF₂CF₂CF₂CFCH—): rate constant, products, and mechanism of gas-phase reactions with OH radicals, IR absorption spectrum, photochemical ozone creation potential, and global warming potential[J]. J. Phys. Chem. A, 2016, 120(48): 9557-9563.
11	Otsuki N. Environmentally friendly fluorinated cleaning agent ZEORORA Ⓡ H[J]. Industrial Cleaning (Japan), 2015, 15: 29-35.
12	Kang S Y, Sawada I, Kondo Y, et al. Plasma chemistry of octafluorocyclopentene/argon/oxygen mixtures[J]. Jpn. J. Appl. Phys., 2008, 47(8): 6843-6848.
13	Jiao C Q, DeJoseph C A, Garscadden A. Ionization of octafluorocyclopentene, c-C₅F₈[J]. J. Phys. D: Appl. Phys., 2005, 38(7): 1076-1080.
14	和岛一喜, 松仓纪行, 上田宪治, 等. 热源机及其运行方法: 108368417A[P]. 2018-08-03.
	Wajima K, Matsukura N, Ueda K, et al. Heat source machine and operating method therefor: 108368417A[P]. 2018-08-03.
15	Henne A L, Zimmerschied W. Fluorinated derivatives of cyclopentene and cyclopentane[J]. J. Am. Chem. Soc., 1945, 67: 1235-1237.
16	Latif K A. Preparation of hexfluoro-1, 2-dichlorocyclopentene and a study of its reactivity[J]. J. Indian Chem. Soc., 1953, 30: 525-528.
17	Michael N, Albrecht M. Dichloro-perfluoro-mono-cyclo-olefin cpds.-prepd. by reacting perchloro-mono-cycloolefin atmos with hydrogen fluoride: DE3935493[P]. 1989-10-25.
18	Mcbee E T, Wiseman P A. Fluorination of unsaturated cyclic pentafluoro compounds: US2459783[P]. 1945-11-30.
19	Mcbee E T, Wiseman P A, Bachman G. Perfluoro dibasic acids and derivatives[J]. Ind. Eng. Chem., 1947, 39: 415-417.
20	Zhang C P, Qing F Y, Quan H D, et al. Synthesis of 1, 1, 2, 2, 3, 3, 4-heptafluorocyclopentane as a new generation of green solvent[J]. J. Fluorine Chem., 2016, 181: 11-16.
21	权恒道, 张呈平, 胡儒柱, 等. 同时制备二氯六氟环戊烯同分异构体的方法: 105601468B[P]. 2017-07-25.
	Quan H D, Zhang C P, Hu R Z, et al. The method for preparing dichlorohexafluorocyclopentene isomers simultaneously: 105601468B[P]. 2017-07-25.
22	古俣武夫, 西宫孝之, 佐久冬彦, 等. 生产全卤环戊烯的方法: 1192995C[P]. 2005-03-16.
	Komata T, Nishimiya T, Sakyu F, et al. Method for producing perhalogenated cyclopentene: 1192995C[P]. 2005-03-16.
23	张呈平. 1H, 1H, 2H-七氟环戊烷的合成研究[D]. 北京: 北京理工大学, 2017.
	Zhang C P. Investigation on synthesis of 1H, 1H, 2H-heptafluorocyclopentane[D]. Beijing: Beijing Institute of Technology, 2017.
24	Quan H D, Liu D P, Jia X Q, et al. Manufacturing method of1, 2-dichlorohexafluorocyclopentene: US10538467B2[P]. 2020-01-21.
25	张呈平, 庆飞要, 周晓猛, 等. 同时制备三氯五氟环戊烯同分异构体的方法: 105399596B[P]. 2017-06-16.
	Zhang C P, Qing F Y, Zhou X M, et al. The method for preparing trichloropentafluorocyclopentene isomers simultaneously: 105399596B[P]. 2017-06-16.
26	Zhang C P, Hu R Z, Qing F Y, et al. Isomerization of halogenated cyclopentene over a NH₄F catalyst[J]. ChemCatChem, 2016, 8: 1474-1478.
27	张呈平, 胡儒柱, 周晓猛, 等. 制备氯氟环戊烯同分异构体的方法: 105294387B[P]. 2017-04-05.
	Zhang C P, Hu R Z, Zhou X M, et al. The method for preparing chlorofluorinnated cyclopentene isomers: 105294387B[P]. 2017-04-05.
28	张呈平, 贾晓卿, 权恒道. 气相异构化反应制备卤代五元环烯烃的方法: 107445794A[P]. 2017-12-08.
	Zhang C P, Jia X Q, Quan H D. The method for preparing halogenated five-membered cyclic olefins by gas-phase isomerization: 107445794A[P]. 2017-12-08.
29	张呈平, 张妮, 庆飞要, 等. 同时制备二氯六氟环戊烯异构体的方法: 107082737B[P]. 2020-02-18.
	Zhang C P, Zhang N, Qing F Y, et al. The method for preparing dichlorohexafluorocyclopentene isomers simultaneously: 107082737B[P]. 2020-02-18.
30	Chambers R D. Fluorine in Organic Chemistry[M]. Canada: John Wiley & Sons, Inc., 1973: 15-16, 21.
31	Yang H E, Quan H D, Tamura M, et al. Investigation into antimony pentafluoride-based catalyst in preparing organo-fluorine compounds[J]. J. Mol. Catal. A Chem., 2005, 233: 99-104.
32	Frank A W. Compounds of phosphorus and fluorine(Ⅳ): Reaction of 1-chloro-2, 3, 3, 4, 4, 5, 5-heptafluorocyclopentene with trialkyl phosphites and other nucleophilic reagents1[J]. J. Org. Chem., 1966, 31(6): 1917-1920.
33	間瀬貴信, 金伊男, 山田俊郎, 等. オクタフルオロシクロペンテンの製造方法: JP2001-247493[P]. 2001-11-09.
	Mase T, Kin Y, Yamada T, et al. Method for producing octafluorocyclopentene: JP2001-247493[P]. 2001-11-09.
34	山田俊郎, 金伊男, 間瀬隆信, 等. 1－クロロヘプタフルオロシクロペンテンの製造方法: JP4271822B2[P]. 2009-06-03.
	Yamada T, Kin Y, Mase T, et al. Preparation method of 1-chloroheptafluorocyclopentene: JP4271822B2[P]. 2009-06-03.
35	张呈平, 周晓猛, 权恒道. 氟化催化剂、制备方法及用途: 104907065B[P]. 2019-08-02.
	Zhang C P, Zhou X M, Quan H D. Fluorination catalyst, preparation method and use: 104907065B[P]. 2019-08-02.
36	张呈平, 刘冬鹏, 贾晓卿, 等. 高价铬基催化剂、制备方法及用途: 106824232B[P]. 2019-08-02.
	Zhang C P, Liu D P, Jia X Q, et al. High price chromium-based catalysts, preparation method and use: 106824232B[P]. 2019-08-02.
37	权恒道, 张呈平, 贾晓卿. 高价金属氟化催化剂、制备方法及用途: 109999788A[P]. 2019-07-12.
	Quan H D, Zhang C P, Jia X Q. High price metal fluoride catalyst, preparation method and use: 109999788A[P]. 2019-07-12.
38	権恒道, 張呈平, 水門潤治, 等. 1-クロロヘプタフルオロシクロペンテン的制造方法: JP6623476B2[P]. 2019-12-25.
	Quan H D, Zhang C P, Mizukado J, et al. Manufacturing method of 1-chloroheptafluorocyclopentene: JP6623476B2[P]. 2019-12-25.
39	井村英明, 高田直門, 古俣武夫. 1－クロロヘプタフルオロシクロペンテンの製造方法: JP3897081B2[P]. 2007-03-22.
	Imura H, Takada N, Komata T. Method for producing 1-chloroheptafluorocyclopentene: JP3897081B2[P]. 2007-03-22.
40	高田直門, 金井正富, 古俣武夫. フッ素化シクロペンタンの製造方法: JP3849088B2[P]. 2006-11-22.
	Takada N, Kanai M, Komata T. Production of fluorinated cyclopentane: JP3849088B2[P]. 2006-11-22.
41	Olah G A, Prakash G K, Á Molná, et al. Superacid Chemistry [M]. 2nd ed. New Jersey: John Wiley & Sons, Inc., 2009: 25.
42	Sekiya A, Yamada T, Sugawara M. Process for the preparation of fluorinated olefin: US6211420B1[P]. 2001-04-03.
43	山田俊郎, 菅原充. フッ化炭化水素化合物の製造法: JP3873308B2[P]. 2007-01-24.
	Yamada T, Sugawara M. Production of fluorinated hydrocarbon compound: JP3873308B2[P]. 2007-01-24.
44	刘冬鹏, 庆飞要, 张呈平, 等. 八氟环戊烯的制备方法: 107188778A[P]. 2017-09-22.
	Liu D P, Qing F Y, Zhang C P, et al. Preparation method of octafluorocyclopentene: 107188778A[P]. 2017-09-22.
45	Zhang C P, Qing F Y, Quan H D, et al. Investigation on Cl-F exchange mechanism occurring at C(sp²) and C(sp³) orbitals of halogenated cyclopentene[J]. J. Fluorine Chem., 2016, 191: 84-89.
46	鈴木健文, 金伊男, 湯浅裕子, 等. 1, 1, 2, 2, 3, 3, 4－ヘプタフルオロシクロペンタンの製造方法およびその製造装置: JP4306081B2[P]. 2009-07-29.
	Suzuki T, Kin Y, Yuasa H, et al. Method and apparatus for producing1, 1, 2, 2, 3, 3, 4-heptafluorocyclopentane: JP4306081B2[P]. 2009-07-29.
47	Yamada T, Goto K, Sugimoto T. Polymer-containing solution and method for forming polymer film: EP0994089B1[P]. 2008-11-26.
48	山田俊郎, 光田康裕. 弗素化飽和炭化水素の製造法: JP3386810B2[P]. 2003-03-17.
	Yamada T, Yasuhiro M. Process for production fluorinated saturated hydrocarbon: JP3386810B2[P]. 2003-03-17.
49	佐久冬彦, 高田直門, 井村英明, 等. ヘプタフルオロシクロペンタンの製造方法: JP3856076B2[P]. 2006-12-13.
	Saku F, Takada N, Imura H, et al. Producing of heptafluorocyclopentane: JP3856076B2[P]. 2006-12-13.
50	山田俊郎, 漆间贵史, 杉本达也.含–CH2-CHF-基团的化合物的制备方法: 1127462C[P]. 2003-11-12.
	Yamada T, Uruma T, Sugimoto T. Process for the preparation of compounds having -CH2-CHF-groups: 1127462C[P]. 2003-11-12.
51	Sekiya A, Tamura M, Yamada T. Porous calcium fluoride, its producing method, catalyst for hydrogenation reaction, and method for producing trihydrofluorocarbon: US20050080303A1[P]. 2005-04-14.
52	Qing F Y, Zhang C P, Quan H D. Synthesis of hydrofluorocyclopentanes by vapor-phase catalytic hydrodehalogenation[P]. J. Fluorine Chem., 2018, 213: 61-67.
53	Sekiya A, Yamada T, Watanabe K. Process for producing fluorinated alkene and fluorinated alkane: US5847243A[P]. 1998-12-08.
54	Sekiya A, Yamada T, Uruma T, et al. Fluorinated, saturated hydrocarbons: US6403846B1[P]. 2002-06-11.
55	関屋章, 高仁孝, 田村正則, 等. ヘプタフルオロシクロペンタンの製造方法: JP4423414B2[P]. 2010-03-03.
	Sekiya A, Gao R X, Tamura M, et al. Preparation method of heptafluorocyclopentane: JP4423414B2[P]. 2010-03-03.
56	Leck T J, Saturno T F, Bell G A. Refrigerant additive compositions containing perfluoropolyethers: US7759532B2[P]. 2010-07-20.
57	Michael V D P, Belter R K, Borowski R J, et al. Reductive dehalogenation of polyhalofluorocarbons with tributyltin hydride[J]. J. Fluorine Chem., 1995, 71: 59-63.
58	Burdon J, Hodgins T M, Stephens R, et al. The isomeric 1H: 2H: 3H- and 1H: 2H: 4H-heptafluorocyclopentanes and the 1H: 2H: 3H: 4H-hexafluorocyclopentanes [J]. J. Chem. Soc., 1965: 2382-2391.
59	张呈平, 贾晓卿, 权恒道. 气相脱氟化氢制备氢氟环戊烯的方法: 107739294A[P]. 2018-02-27.
	Zhang C P, Jia X Q, Quan H D. Preparation method of hydrofluorocyclopentene by gas-phase dehydrofluorination: 107739294A[P]. 2018-02-27.
60	Zhang C P, Zhang N, Jia X Q, et al. Isomerization of hydrofluorocyclopentenes promoted by fluoride anion[J]. Green Sustain. Chem., 2018, 8: 115-129.
61	古俣武夫, 高田直門. フルオロシクロペンテン類の製造方法: JP3876951B2[P]. 2007-02-07.
	Takada N, Komata T. Production of fluorocyclopentenes: JP3876951B2[P]. 2007-02-07.
62	Martino M, Rosal R, Sastre H, et al. Hydrodechlorination of dichloromethane, trichloroethane, trichloroethylene and tetrachloroethylene over a sulfided Ni/Mo-γ-alumina catalyst[J]. Appl. Catal. B: Environ., 1999, 20: 301-307.
63	张呈平, 刘冬鹏, 贾晓卿, 等. 七氟环戊烯的制备方法: 106995362B[P]. 2020-02-18.
	Zhang C P, Liu D P, Jia X Q, et al. Preparation method of heptafluorocyclopentene: 106995362B[P]. 2020-02-18.
64	张呈平, 张文妮, 贾晓卿, 等. 卤代烯烃水解制备氢卤烯烃的方法: 202010109113.0[P]. 2020-02-21.
	Zhang C P, Zhang W N, Jia X Q, et al. Preparation method of hydrohaloolefin by hydrolysis of halogenated olefin: 202010109113.0[P]. 2020-02-21.
65	Lu K, Han X W, Yao W W, et al. DMF-promoted redox-neutral Ni-catalyzed intramolecular hydroarylation of alkene with simple arene[J]. ACS Catal., 2018, 8: 3913-3917.
66	Yang G, Zhang C P, Yang H E, et al. Synthesis of 1H-polychlorofluorocycloolefins[J]. J. Fluorine Chem., 2018, 216: 96-101.
67	Panini P, Chopra D. Understanding of noncovalent interactions involving organic fluorine[M]//Hydrogen Bonded Supramolecular Structures. German: Springer-Verlag Berlin Heidelberg, 2015: 37-63.
68	権恒道, 楊剛, 水門潤治, 等. フッ素化合物の製造方法: JP2018-115586[P]. 2018-06-18.
	Quan H D, Yang G, Mizukado J, et al. Method for manufacturing fluorine-containing compound: JP2018-115586[P]. 2018-06-18.
69	Feast W J, Perry D R A, Stephens R. Fluorocyclopentanes(Ⅴ): Lithium aluminium hydride reduction of octafluoro-, 1,2-dichlorohexafluoro-, and 1-chloroheptafluoro-cyclopentene and 1H, 2-chloro-octafluorocyclohexene[J]. Tetrahedron, 1966, 22: 433-439.
70	杉本達也. 含水素ハロゲン化シクロペンタン、及びヘプタフルオロシクロペンテンの製造方法: JP2011-144148[P]. 2011-07-28.
	Sugimoto T. Hydrogen-containing halogenated cyclopentane, and method for producing heptafluorocyclopentene: JP2011-144148[P]. 2011-07-28.
71	Sugimoto T, Suzuki T, Konagawa J. Method for producing hydrogen-containing fluoroolefin compound: WO2010007968A1[P]. 2010-01-21.
72	Heizman R J, Patric C R, Stephens R, et al. Fluorocyclopentanes (Part Ⅰ): The 1H, 2H- and 1H, 3H-octafluorocyclopentanes, and 1H, 3H/2H-heptafluorocyclopentane[J]. J. Chem. Soc., 1963: 281-289.
73	Banks R E, Barlow M G, Haszeldine R N, et al. Heterocyclic polyfluoro-compounds (Part ⅩⅣ): Catalytic hydrogenation of perfluoro-(3,6-dihydro-2-methyl-2H-1,2-oxazine) and of perfluorocyclopentene[J]. J. Chem. Soc. C, 1968: 548-550.
74	杉本達也. ヘプタフルオロシクロペンテンの異性化方法及びその利用: JP2011-105625[P]. 2011-06-02.
	Sugimoto T. Method of isomerizing heptafluorocyclopentene, and use thereof: JP2011-105625[P]. 2011-06-02.
75	杉本达也, 铃木健文, 小名川丈. 含氢氟烯烃的制造方法: 102026946B[P]. 2014-03-14.
	Sugimoto T, Suzuki T, Konagawa J. Method for producing hydrogen-containing fluoroolefin compound: 102026946B[P]. 2014-03-14.
76	张呈平, 李忠, 权恒道. 气相氟-氯交换制备七氟环戊烯的方法: 107311839B[P]. 2019-09-10.
	Zhang C P, Li Z, Quan H D. Preparation method of heptafluorocyclopentene by gas-phase fluorine-chlorine exchange: 107311839B[P]. 2019-09-10.
77	宇佐美由久, 稻垣由夫. 光信息记录盘和染料溶液的制备: 1213419C[P]. 2005-08-03.
	Usami Y, Inagaki Y. Preparation of optical information recording disc and dye solution: 1213419C[P]. 2005-08-03.
78	田沼敏弘. 固体高分子型燃料电池用膜电极接合体的制造方法: 101946350A[P]. 2011-01-12.
	Tanuma T. Process for producing membrane/electrode assembly for polymer electrolyte fuel cell: 101946350A[P]. 2011-01-12.
79	巴泰尔特. 包含七氟环戊烷的类共沸混合物: 101553561B[P]. 2011-12-21.
	Bartelt J E. Azeotrope-like mixtures comprising heptafluorocyclopentane: 101553561B[P]. 2011-12-21.
80	Yamada T, Goto K, Sugimoto T. Fluorinated hydrocarbons, detergents, deterging method, polymer-containing fluids, and method of forming polymer films: US6312759B1[P]. 2001-11-06.
81	山田千惠子, 田中和志. 硬涂层剂组合物和使用其的硬涂层薄膜: 103102793A[P]. 2013-05-15.
	Yamada C, Tanaka K. Hard coat agent composition and hard coat film using the same: 103102793A[P]. 2013-05-15.
82	DeGroot R J, Shellef D. Azeotrope compositions containing a fluorocyclopentane: US7067468B2[P]. 2006-06-27.
83	庆飞要. 氢氟环戊烷的合成及其清洗性能研究[D]. 北京: 北京理工大学, 2019.
	Qing F Y. Investigation on synthesis and cleaning performance of hydrofluorocyclopentane[D]. Beijing: Beijing Institute of Technology, 2019.
84	Ji B, Badowski P R, Motika S A, et al. Evaluating the performance of c-C₄F₈,
	c-C5F8, and C₄F₆for critical dimension dielectric etching[EB/OL]. https: //.
85	Ono T, Takahashi H, Kinoshita K, et al. Plasma etch rates of porous silica low-k films with different dielectric constants[J]. Jpn. J. Appl. Phys., 2006, 45(11): 8873-8875.
86	Kim G H, Kim S B, Kim C I. Selective etching of SiO₂ over Si₃N₄ in a C₅F₈/O₂/Ar plasma[J]. Microelectron. Eng., 2006, 83: 2504-2509.
87	Kim S B, Choi D G, Hong T E, et al. Study on self-aligned contact oxide etching using C₅F₈/O₂/Ar and C₅F₈/O₂/Ar/CH₂F₂ plasma[J]. J. Vac. Sci. Technol., 2005, 23: 953-958.
88	权恒道, 张呈平, 郭勤. 一种含氟传热流体及其制备方法和应用: 202010692380.5[P]. 2020-07-17.
	Quan H D, Zhang C P, Guo Q. Fluorine-containing heat transfer fluid, preparation method and application thereof: 202010692380.5[P]. 2020-07-17.
89	权恒道, 郭勤, 张呈平. 一种热传递装置及热传递方法: 202010692353.8[P]. 2020-07-17.
	Quan H D, Guo Q, Zhang C P. Heat transfer device and method: 202010692353.8[P]. 2020-07-17.
90	Smith S M, Bulinski M J, Costello M G, et al. Perfluoroaminoolefins and methods of making and using the same: WO2019220293A1[P]. 2019-11-21.

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