Page 51 - 《精细化工》2022年第4期

第 4 期 权恒道，等: 环保型替代物：1-氯-3,3,3-三氟丙烯的合成与应用 ·687·

行业、医疗器械、珠宝和制表业等领域 [70-71] 。 US20110201853A1[P]. 2011-08-18.
HCFO-1233zd(Z)和环状氢氯氟烯烃的组合物 [8] POKROVSKI K A, MERKEL D C, TUNG H S. Continuous
low-temperature process to produce trans-1-chloro-trifluoropropene:
对电子设备上常用的 15#切削油和 100#拉伸油具有 US20120059199A1[P]. 2012-03-08.
更好的溶解度，可应用于精密电子清洗领域 [72] 。 [9] WANG H Y, TUNG H S. Process for producing 1-chloro-3,3,3-
trifluoropropene in an ionic liquid: US20150105596A1[P]. 2015-04-16.
3 结束语与展望 [10] POKROVSKI K A, MERKEL D C, WANG H Y, et al. Integrated
process to coproduce trans-1-chloro-3,3,3-trifluoropropene, trans-
1,3,3,3-tetrafluoropropene, and 1,1,1,3,3-penrafluopropane:
HCFO-1233zd(E)的异构化路线是生产 HCFO- US20130261353A1[P]. 2013-10-03.
1233zd(Z)最具工业化价值的路线，但原料 HCFO- [11] MERKEL D C, TUNG H S. Process for the production of 1-chloro-
3,3,3-trifluoropropene (HCFO-1233zd): US10000431B1[P]. 2018-
1233zd(E)价格昂贵，其获取是该路线能否实现产业 06-19.
化的关键之一。一般来说，HCFO-1233zd(Z)生产企 [12] MERKEL D C, TUNG H S. Process for the production of 1-chloro-
业会采取自主生产 HCFO-1233zd(E)的途径来获取 3,3,3-trifluoropropene (HCFO-1233zd): US9994502B1[P]. 2018-06-12.
[13] SAKYU F, YOSHIKAWA S, OKAMOTO S, et al. Process for
该原料。在 HCFO-1233zd(E)的诸多合成路线中，氟- producing 1,3,3,3-tetrafluoropropene: EP2341040B1[P]. 2017-09-06.
氯交换反应是极为重要的合成路线，其核心技术是 [14] HONG J Y, YANG B, ZHAO Y, et al. Method for co-producing
low-carbon foaming agents: US20200039902A1[P]. 2020-02-06.
铬基催化剂。铬基催化剂是目前氟-氯交换反应中应
[15] CHENG H (程昊), XIAO Y L (肖玉岭), XIA K (夏凯). A method for
用最广泛的氟化催化剂，其催化活性高、易于再生， the co-production of trans-1-chloro-3,3,3-trifluoropropene and
3+
但在应用过程中铬基催化剂中的 Cr 易被氧化为高 2,3,3,3-tetrafluoropropene: CN108383679A[P]. 2018-08-10.
6+
致癌性的 Cr 。因此，开发高活性、高安全性的非 [16] JIA X Q (贾晓卿), ZHANG N (张妮), DONG L (董利), et al.
Preparation method of (E)-1-halo-3,3,3-trifluoropropene:
铬催化剂来替代铬基催化剂用于氟-氯交换反应，显 CN112723985B[P]. 2021-07-09.
得尤为 迫切 ，是同 时关 系到 HCFO-1233zd(E)和 [17] QUAN H D, YANG H E, TAMURA M, et al. Preparation of
1,1,1,3,3-pentafluoropropane (HFC-245fa) by using a SbF 5-attached
HCFO-1233zd(Z)生产的重要纽带和技术关键，是氟 catalyst[J]. Journal of Fluorine Chemistry, 2007, 128(3): 190-195.
化工领域举足轻重的研究重点之一。目前，国内学 [18] OKAMOTO S, IMURA H, OKAMOTO M, et al. Method for
者研究发现，在气相氟-氯交换合成系列含氟烯烃的 producing 3,3,3-trifluoropropyne: JP6032085B2[P]. 2016-11-24.
[19] HAMASAKI H, HIBINO Y. Process for producing fluorinated
反应中，钨基催化剂和钼基催化剂作为非铬催化剂， propene: EP2327680A1[P]. 2011-06-01.
具有比铬基催化剂更高的催化活性，同时钨和钼比 [20] SUN X H. Compositions and processes for producing
铬更环保和安全 [73-74] 。这将为非铬催化剂替代铬基 chlorofluoroalkenes: WO2020036836A1[P]. 2020-02-20.
[21] RAO V N M, SIEVERT A C. Processes for the production of
催化剂，从而实现氟化工行业的绿色生产提供可能。 fluoropropanes and halopropenes and azeotropic compositions of
另外，现有关于 HCFO-1233zd 的主流应用专利基本 2-chloro-3,3,3-trifluoro-1-propene with HF of 1,1,1,2,2-
pentafluoropropane with HF: WO2008054781A1[P]. 2008-05-08.
被国外公司垄断。对 HCFO-1233zd 的新应用技术进 [22] MERKEL D C, JOHNSON R, TUNG H S. Integrated process to
行开发，加强其应用方面知识产权的申请和保护， co-produce trans-1-chloro-3,3,3-trifluoropropene and trans-1,3,3,3-
也是中国今后发展 HCFO-1233zd 领域的重点之一。 tetrafluoropropene: US20110245549A1[P]. 2011-10-06.
[23] WANG H Y, TUNG H S. Process for producing trans-1233zd:
参考文献： US20120271069A1[P]. 2012-10-25.
[24] HASZELDINE R N. 550. Reactions of fluorocarbon radicals. Part
[1] GUO Q, CHEN L, MIZUKADO J. Atmospheric degradation Ⅴ . Alternative syntheses for trifluoromethylacetylene (3,3,3-
mechanism of Z/E-CF 3CF==CHCl, CF 3CF==CCl 2, and CF 2==CFCl trifluoropropyne), and the influence of polyfluoro-groups on adjacent
initiated by OH radicals using a smog chamber with long-path FTIR hydrogen and halogen atoms[J]. Journal of the Chemical Society,
at 298 K[J]. Atmospheric Environment, 2019, 218: 116991. 1951. DOI: 10.1039/JR9510002495.
[2] PIGAMO A, COLLIER B. Compositions based on 1,1,3,3- [25] WANG H Y, TUNG H S. Methods for producing 1-chloro-
tetracholoropropene: US20180148394A1[P]. 2018-05-31. 3,3,3-trifluoropropene from 2-chloro-3,3,3-trifluoropropene:
[3] PIGAMO A, WISMER J, COLLIER B. (E)-1-chloro-3,3,3- US20130310614A1[P]. 2013-11-21.
trifluoropropene production process from 1,1,3,3-tetrachloropropene: [26] IMURA H, OKAMOTO S, OKAMOTO M, et al. Method for
US20150197467A1[P]. 2015-07-16. producing 1-chloro-3,3,3-trifluoro-1-propene and 1,3,3,3-
[4] POKROVSKI K A, MERKEL D C, WANG H Y, et al. Integrated tetrafluoropropene: US20150099907A1[P]. 2015-04-09.
process to coproduce trans-1-chloro-3,3,3-trifluoropropene, trans- [27] JUNGONG C, MERKEL D C. Process for catalytic of mixtures of
1,3,3,3-tetrafluoropropene, and 1,1,1,3,3-pentafluoropropane: HCFO-1233zd(Z) and HCFC-244fa into HCFO-1233zd(E):
US20120059200A1[P]. 2012-03-08. US10118879B1[P]. 2018-11-06.
[5] HIBINO Y, YOSHIKAWA S, SAKYU F. Production method for [28] MCGUINNESS C E, SHARRATT A P. Process for isomerization of
1-chloro-3,3,3-trifluoropropene: EP2799413B1[P]. 2016-10-12. C3-7(hydro)(halo)fluoroalkenes: WO2015059500A1[P]. 2015-04-30.
[6] TUNG H S, WANG H Y, MERKEL D C. Process for the preparation [29] HONG J Y, YANG B, ZHANG Y, et al. Method for co-producing
of 1-chloro-3,3,3-trifluoropropene using a phase transfer catalyst: various alkenyl halides and hydrofluoroalkanes:
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[7] TUNG H S, JOHNSON R, POKROVSKI K A. Integrated process [30] OKAMOTO S, SAKYU F. Method for producing trans-1-chloro-
and methods of producing (E)-1-chloro-3,3,3-trifluoropropene: 3,3,3-trifluoropropene: EP2778150B1[P]. 2016-05-18.