WO2022083018A1 - 一种反式 -1 ， 2- 二氯乙烯抑制闪点的方法及应用 - Google Patents

一种反式 -1 ， 2- 二氯乙烯抑制闪点的方法及应用 Download PDF

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WO2022083018A1
WO2022083018A1 PCT/CN2021/072973 CN2021072973W WO2022083018A1 WO 2022083018 A1 WO2022083018 A1 WO 2022083018A1 CN 2021072973 W CN2021072973 W CN 2021072973W WO 2022083018 A1 WO2022083018 A1 WO 2022083018A1
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trans
dichloroethylene
flash point
chloro
trifluoropropene
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PCT/CN2021/072973
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English (en)
French (fr)
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郑法瑞
郑亚威
菅盘铭
郑子涵
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淄博雷玛国际贸易有限公司
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Priority to US17/799,929 priority Critical patent/US11649418B2/en
Publication of WO2022083018A1 publication Critical patent/WO2022083018A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen
    • C11D7/30—Halogenated hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • B08B3/106—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by boiling the liquid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5018—Halogenated solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B2230/00—Other cleaning aspects applicable to all B08B range
    • B08B2230/01—Cleaning with steam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

  • a method and application for inhibiting the flash point of trans-1,2-dichloroethylene belong to the technical field of inhibiting the flash point of trans-1,2-dichloroethylene.
  • trans-1,2-dichloroethylene Because of its zero ODP and GWP, trans-1,2-dichloroethylene (T-DCE) has been widely used in the field of industrial cleaning agents and solvents for metal parts, substrates, electronic devices, and electronic circuit boards. Cleaning, degreasing, degreasing, dry cleaning of clothing and leather, and dilution of silicone oil, fluorine oil, and rust inhibitor.
  • trans-1,2-dichloroethylene itself has a flash point
  • trans-1,2-dichloroethylene brings a safety problem to practical application, inhibiting trans-1,2-dichloroethylene The flash point has become an unavoidable problem in its application.
  • T-DCE When it is actually used in an environment with a temperature of 45°C and above, T-DCE is also close to or reaches its boiling point. (about 47.7°C), so that the concentration of T-DCE near the liquid surface also increases sharply, the partial pressure of HCFO-1233zd decreases, and the concentration per unit volume near the liquid surface decreases. Those skilled in the art can imagine that in this case, the two substances are completely separated and lost. The effect of inhibiting the flash point, the flash point of T-DCE drops rapidly, so it is more suitable for foaming at ordinary temperature, but not suitable for applications in closed environment steam cleaning. In view of the low boiling point of HCFO-1233zd, in The higher temperature environment is more likely to escape from the closed environment, so it is especially not suitable for repeated cleaning and use in the machine cleaning system.
  • the technical problem to be solved by the present invention is: to overcome the deficiencies of the prior art, and to provide a kind of stably suppressing the flash point of trans-1,2-dichloroethylene under various temperature environments to realize trans-1,2- The method and application of trans-1,2-dichloroethylene for inhibiting the flash point of trans-1,2-dichloroethylene without the danger of potentially enhancing the greenhouse effect and low cost when applying dichloroethylene to steam cleaning objects.
  • the technical scheme adopted by the present invention to solve the technical problem is: a method for inhibiting the flash point of trans-1,2-dichloroethylene, which is characterized in that: combining trans-1,2-dichloroethylene with 1-chloroethylene -2,3,3-trifluoropropene (HCFO-1233yd (E/Z)) is mixed so that 1-chloro-2,3,3-trifluoropropene accounts for 3% to 90% by weight in the mixed solution.
  • HCFO-1233yd (E/Z) 1-chloro-2,3,3-trifluoropropene
  • 1-chloro-2,3,3-trifluoropropene itself has a boiling point of 54°C, especially the boiling point of trans-1-chloro-2,3,3-trifluoropropene is 48 °C, compared with 15°C of HCFO-1233zd, it is closer to the boiling point of trans-1,2-dichloroethylene, which makes it possible to form an azeotrope when mixed with trans-1,2-dichloroethylene Or an approximate azeotropic mixed system, the mixed solution can ensure that trans-1,2-dichloroethylene and 1-chloro-2,3,3-trichloroethylene in the gas near the liquid surface at any ambient temperature or system temperature
  • concentration of fluoropropene and the mixed liquid are in the same ratio, so as to achieve the same effect of inhibiting the flash point of trans-1,2-dichloroethylene under all temperature conditions, and there will be no occurrence of the temperature far exceeding a certain component.
  • the boiling point causes the two components to be completely separated in the gas phase, which further leads to different effects of different temperatures in inhibiting the flash point and even loses the effect of inhibiting the flash point when the boiling point of trans-1,2-dichloroethylene is near;
  • the two components are always mixed uniformly, which can also meet the requirements of repeated use of cleaning agents in machine cleaning systems; at the same time, 1-chloro-2,3,3-trifluoropropene itself has extremely low ozone-depleting potential and greenhouse effect. It has high environmental friendliness and will not affect other properties of trans-1,2-dichloroethylene.
  • trans-1,2-dichloroethylene is mixed with 1-chloro-2,3,3-trifluoropropene, so that 1-chloro-2,3,3-trifluoropropene is in the mixed solution by weight Accounting for 5% to 50%.
  • trans-1,2-dichloroethylene is mixed with 1-chloro-2,3,3-trifluoropropene, so that 1-chloro-2,3,3-trifluoropropene is in the mixed solution by weight Accounting for 10% to 20%.
  • the volatilized vapor of the mixed solution can be maintained at a two-component ratio that is close to the mixed solution at any system temperature, that is, under any environment or system temperature, the mixed solution can maintain a stable and uniform flash point. and the approximate azeotropic temperature of the mixed solution is closest to the boiling point of trans-1,2-dichloroethylene, that is, the steam of the mixed solution has the best cleaning of trans-1,2-dichloroethylene Effect.
  • the chromium-based catalysts are catalysts such as chromium-supported activated carbon, zirconium oxychloride, and the like.
  • the above method can be used to prepare 1-chloro-2,3,3-trifluoropropene with a boiling point of around 54°C, which can effectively inhibit trans-1,2 after compounding with trans-1,2-dichloroethylene.
  • the flash point of dichloroethylene especially when the compound composition of trans-1,2-dichloroethylene and 1-chloro-2,3,3-trifluoropropene reaches the approximate azeotrope temperature, it can still maintain the reverse
  • the flash point of formula-1,2-dichloroethylene has no detectable flash point in the higher range.
  • the said mixture has no flash point before boiling. Since the ratio of the two components remains stable at various temperatures before the mixture is boiled, it can be achieved that the approximate azeotrope, that is, when the temperature of the mixture is around 47°C, still has a good effect of suppressing the flash point.
  • the 1-chloro-2,3,3-trifluoropropene is trans-1-chloro-2,3,3-trifluoropropene.
  • 1-Chloro-2,3,3-trifluoropropene is actually a mixture of cis and trans coexistence, namely 1-chloro-2,3,3-trifluoropropene (E/Z), and the present invention utilizes
  • the main is that the boiling point of trans-1-chloro-2,3,3-trifluoropropene is 48°C, which is closer to the boiling point of trans-1,2-dichloroethylene at 47.67°C, which is higher than that of 1-chloro-2,3 , the proportion of trans-1-chloro-2,3,3-trifluoropropene in the 3-trifluoropropene (E/Z) mixture, it is easier to reflect its advantages of inhibiting flash point and approximate azeotrope.
  • the proportion of -1-chloro-2,3,3-trifluoropropene is greater than or equal to 95%, adjust its ratio in trans-1,2-dichloroethylene and 1-chloro-2,3,3-trifluoropropene
  • the proportion of the composition can be more easily adjusted to obtain cleaning agents with different cleaning values (KB value) of 44-124, which can meet the cleaning requirements of different cleaning objects.
  • trans-1,2-dichloroethylene characterized in that: a mixed solution prepared by using the above-mentioned method for inhibiting flash point of trans-1,2-dichloroethylene is used as a cleaning agent.
  • the constituent components in the composition are all excellent new environmentally friendly cleaning agent solvents, so the composition can be used as a spray cleaning agent, a dry cleaning agent for leather clothes, a machine cleaning agent, a silicone oil fluorine oil diluent, a rust preventive diluent, etc. It is suitable for various cleaning fields, and can be widely used in low temperature extraction, deinking, degreasing and other solvent fields.
  • the mixed solution cleaning agent is placed in a closed space and heated to 45-50° C., and the object to be cleaned is placed above the liquid surface in a cooling state for steam washing.
  • the present invention considers the application of trans-1,2-dichloroethylene in middle and high-end industrial cleaning, that is, machine cleaning. Since the method for inhibiting the flash point of trans-1,2-dichloroethylene found in the present invention can be applied to The system temperature inhibits the flash point when it is close to the boiling point of trans-1,2-dichloroethylene, so the machine parts with special requirements can be cleaned by heating and evaporation; in view of the trans-1,2-dichloroethylene Its excellent cleaning effect, combined with the temperature effect of steam and high permeability, can achieve better cleaning effect.
  • the objects to be cleaned are mechanical parts and electronic parts.
  • 1-Chloro-2,3,3-trifluoropropene can have better cleaning effect for mechanical parts by steam cleaning.
  • the present invention has the beneficial effect that the flash point of trans-1,2-dichloroethylene can be completely suppressed before reaching the approximate azeotropic point of the composition, so that the trans- -The mixture of 1,2-dichloroethylene and 1-chloro-2,3,3-trifluoropropene is heated and evaporated by boiling, and the various objects are fully and repeatedly cleaned by steam washing to achieve better cleaning effect, and
  • the cleaning agent vapor condenses into liquid after being cooled, and enters repeated Cleaning, so that it is not easy to escape, does not need to be replenished, and also reduces the damage to the environment, especially the ozone layer.
  • Embodiment 10 is the best embodiment of the present invention, and the present invention will be further described below with reference to the embodiments.
  • the manufacturer of the main component, trans-1,2-dichloroethylene T-DCE, is China Ningxia Purui Chemical Co., Ltd., and the main content is greater than or equal to 99.9%.
  • the reaction temperature is 275°C
  • the space velocity is 240h -1
  • the catalyst adopts Cr-Co-Zn produced by Shandong Feiyuan Chemical Co., Ltd.
  • the composite catalyst has a reaction temperature of 300°C, a space velocity of 220h -1 , and a charging ratio of hydrogen fluoride to 1,2-dichloro-3,3-difluoropropene 4:1.
  • a method for inhibiting flash point of trans-1,2-dichloroethylene mix trans-1,2-dichloroethylene and 1-chloro-2,3,3-trifluoropropene to make 1-chloro- 2,3,3-trifluoropropene accounts for 3% to 90% by weight in the mixed solution.
  • the mixing ratio of trans-1,2-dichloroethylene and 1-chloro-2,3,3-trifluoropropene in each example is shown in Table 1 below.
  • T-DCE is trans-1,2-dichloroethylene
  • 1233yd is the 1-dichloroethylene without separation of cis and trans obtained by the above-mentioned 1-chloro-2,3,3-trifluoropropene preparation method.
  • Chloro-2,3,3-trifluoropropene, T-DEC/1233yd is the weight ratio of trans-1,2-dichloroethylene to 1-chloro-2,3,3-trifluoropropene.
  • trans-1,2-dichloroethylene An application of trans-1,2-dichloroethylene.
  • the mixed solution of trans-1,2-dichloroethylene and 1-chloro-2,3,3-trifluoropropene (E/Z) obtained in Example 1 was placed in a closed constant temperature box, and the volume accounted for about 30% of the box volume. %, the weight ratio of trans-1,2-dichloroethylene and 1-chloro-2,3,3-trifluoropropene (E/Z) is 90:10, heated to keep the temperature at 47°C, and the top of the box is fixed
  • the hollow steel pipe with a diameter of 1mm and a 90° angle and a length of 15cm is blocked by organic oil and dirt.
  • the height is 30cm from the liquid surface. , the two ends are connected.
  • Embodiments 9-13 A kind of method for inhibiting flash point of trans-1,2-dichloroethylene.
  • the preparation method of 1-chloro-2,3,3-trifluoropropene described in Example 1 was repeated, and the prepared 1-chloro-2,3,3-trifluoropropene was rectified to obtain a boiling point of 47.67°C of trans-1-chloro-2,3,3-trifluoropropene, mix trans-1,2-dichloroethylene with the resulting 1-chloro-2,3,3-trifluoropropene to make 1-chloro- -2,3,3-trifluoropropene accounts for 3% to 90% by weight in the mixed solution.
  • the proportions of each embodiment are shown in Table 2 below. 1233yd(E) is trans-1-chloro-2,3,3-trifluoropropene.
  • Performance Test 1 Test the mixture of trans-1,2-dichloroethylene and 1-chloro-2,3,3-trifluoropropene according to "National Standard of the People's Republic of China" GB/T 5208-2008 / ISO 3679:2004 closed cup flash point.
  • the samples obtained in the above examples and comparative examples were placed in a room at 0° C., and then the room temperature was lowered to -18° C. and the humidity was 45%.
  • the flash point was measured 3 times at the set test temperature point, and the test results were recorded in Table 3, where N/A means that the flash point has been reached, so no further testing was performed.
  • the method for inhibiting the flash point of trans-1,2-dichloroethylene of the present invention accounts for 3% by weight of 1-chloro-2,3,3-trifluoropropene in the mixed solution. In 90% of the cases, it can have an excellent effect of inhibiting the flash point. When it accounts for only 1 ⁇ 2%, the effect of inhibiting the flash point will be reduced by a cliff.
  • the known boiling point of trans-1,2-dichloroethylene is about 47 ⁇ 48 °C, and according to Examples 2 ⁇ 8, it can be seen that when the mixed solution has boiled, it still has the ability to inhibit trans-1, The effect of 2-dichloroethylene.
  • 1-chloro-2,3,3-trifluoropropene accounts for more than 90% by weight in the mixed solution, due to the low content of trans-1,2-dichloroethylene, its own cleaning effect will be significantly falling.
  • the vapor obtained after the evaporation of the mixed solution contains trans-1,2-difluoropropene.
  • the mixing ratio of vinyl chloride and 1-chloro-2,3,3-trifluoropropene is closer to the mixing ratio of the mixed liquid, so the effect closer to the approximate azeotrope can be obtained, that is, the better effect of suppressing the flash point can be obtained.

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Abstract

一种反式-1，2-二氯乙烯抑制闪点的方法及应用。反式-1，2-二氯乙烯具有优良的清洁效果并且环境友好性极佳，但是却因其闪点较低存在巨大的安全隐患而不能充分发挥其作用。现有技术中采用HCFO-1233zd来抑制其闪点，但是因这两种物质实际上沸点相差较大，在略高的环境温度下两种物质极易分离，而因HCFO-1233zd沸点极低，HCFO-1233zd则会迅速逃逸，导致失去抑制闪点的效果。本发明利用反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯混合制成混合液，能够有效的在各种环境温度下保持抑制反式-1，2-二氯乙烯闪点的效果，从而得以利用反式-1，2-二氯乙烯加热蒸发后的蒸汽进行清洗等作业。

Description

一种反式-1，2-二氯乙烯抑制闪点的方法及应用 技术领域
一种反式-1，2-二氯乙烯抑制闪点的方法及应用，属于抑制反式-1，2-二氯乙烯闪点技术领域。
 背景技术
反式-1，2-二氯乙烯（T-DCE）由于其ODP和GWP为零，所以已经被广泛地用在工业清洗剂和溶剂领域中对金属部件、基材、电子器件、电子线路板的清洗、除油、脱脂，对衣物、皮革的干洗及对硅油、氟油、防锈剂的稀释。但是，反式-1，2-二氯乙烯由于反式-1，2-二氯乙烯本身有闪点，给实际应用带来了安全方面的问题，抑制反式-1，2-二氯乙烯的闪点成为其应用中不能回避的问题。
抑制反式-1，2-二氯乙烯的闪点，此前有许多的专利文献。美国3M公司发明了反式-1，2-二氯乙烯与HFE-7100、HFE-7200、HFE-7300等氢氟醚类组合物的多个抑制方案；美国科慕开发了反式-1，2-二氯乙烯与HFC-4310组合物、反式-1，2-二氯乙烯+HFC-4310+HFX-110等的抑制方案，由于都是用氢氟醚类化合物来抑制反式-1，2-二氯乙烯的闪点，以致普遍存在价格高于市场的接受能力，成为市场应用的严重阻碍。
文献WO2011/089344和专利 CN 105802584 B都描述了反式-1，2-二氯乙烯和1-氯-3，3，3-三氟丙烯（HCFO-1233zd）作为清洁组合物及其对闪点的抑制，因此可以理解此技术方案为在常温下，将HCFO-1233zd与T-DCE混合，降低空气中T-DCE浓度实现抑制闪点的作用，但是，反式1-氯-3，3，3-三氟丙烯的沸点仅在15℃左右，常温下可以挥发为高浓度的气态，而真正使其用于45℃及以上温度的环境下时，此时T-DCE也接近或达到其沸点（47.7℃左右），以致液面附近T-DCE浓度也急剧升高，HCFO-1233zd分压降低，液面附近单位体积浓度下降，本领域技术人员可以想到此情况下两种物质彻底分离，失去抑制闪点的作用，T-DCE闪点迅速下降，因此更适用于普通常温下的发泡，而不适用于在密闭环境蒸汽清洗方面的应用，鉴于HCFO-1233zd沸点较低的情况下，在温度较高环境更容易从密闭环境逃逸，因此尤其不适用于机器清洗系统中多次的重复清洗使用。
 技术问题
本发明所要解决的技术问题是：克服现有技术的不足，提供一种能够在各种温度环境下稳定抑制反式-1，2-二氯乙烯闪点以实现将反式-1，2-二氯乙烯应用于蒸汽清洗物体，没有潜在增强温室效应危险且成本低的反式-1，2-二氯乙烯抑制闪点的方法及应用。
 技术解决方案
本发明解决其技术问题所采用的技术方案是：一种反式-1，2-二氯乙烯抑制闪点的方法，其特征在于：将反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯（HCFO-1233yd （E/Z））混合，使1-氯-2，3，3-三氟丙烯在混合液中按重量计占3%~90%。
发明人发现1-氯-2，3，3-三氟丙烯（E/Z）其本身沸点为54℃，尤其是反式-1-氯-2，3，3-三氟丙烯的沸点为48℃，相比较于HCFO-1233zd的15℃更接近反式-1，2-二氯乙烯的沸点，这就使其在与反式-1，2-二氯乙烯混合的情况下能够形成共沸或近似共沸的混合体系，该混合液能够保证在任意的环境温度或体系温度下液面附近的气体中反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯的浓度与混合液均为相同的比例，从而实现在所有温度条件下均有相同的抑制反式-1，2-二氯乙烯闪点的作用，不会出现由于温度远超某一成分沸点而导致两种成分在气相中彻底分离，进一步导致不同温度抑制闪点效果不同甚至在反式-1，2-二氯乙烯沸点附近时失去抑制闪点作用的情况；鉴于本发明所述的两种成分始终混合均一，也能满足机器清洗系统中清洗剂重复使用的要求；同时1-氯-2，3，3-三氟丙烯本身的破坏臭氧层潜值与温室效应潜值也极低，具备较高的环境友好性，也不会影响反式-1，2-二氯乙烯的本身其它性能。
优选的，将反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯混合，使1-氯-2，3，3-三氟丙烯在混合液中按重量计占5%~50%。1-氯-2，3，3-三氟丙烯在混合液中含量越高则对反式-1，2-二氯乙烯的闪点抑制作用越强，而含量越低则清洁作用相应升高。
优选的，将反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯混合，使1-氯-2，3，3-三氟丙烯在混合液中按重量计占10%~20%。此比例范围内可使混合液挥发出的蒸汽在任意体系温度下均保持与混合液较为接近的两成份比例，即在任意环境或体系温度下，所述的混合液均保持对闪点稳定统一的抑制作用，且混合液的近似共沸温度最接近反式-1，2-二氯乙烯的沸点，即：使混合液的蒸汽具有最佳的反式-1，2-二氯乙烯的清洗效果。
所述的1-氯-2，3，3-三氟丙烯制备方法包括以下步骤：1）1，1，2，3，3-五氯丙烷为原料与氟化氢在铬基催化剂催化下生成1，2-二氯-3，3-二氟丙烯（E、Z）（CHCl=CCl-CHF2）(HCFO-1232aa)，反应温度200~350℃，空速60~570h -1，氟化氢与1，1，2，3，3-五氯丙烷投料比5~25：1；2）1，2-二氯-3，3-二氟丙烯与氟化氢反应生成1-氯-2，3，3-三氟丙烯（E/Z）(CHCl=CF-CHF2)(HCFO-1233yd)，主催化剂为氟化氢处理的铬基催化剂，辅催化剂为Zn、Co、Ni和Cu元素之一，反应温度250~400℃，空速50~550h -1，氟化氢与1，2-二氯-3，3-二氟丙烯投料比1~8：1。
其中，所述的铬基催化剂为负载铬的活性炭、氧氯化锆等催化剂。
利用上述方法可以制得沸点在54℃附近的1-氯-2，3，3-三氟丙烯，与反式-1，2-二氯乙烯复配组合后能够有效抑制反式-1，2-二氯乙烯的闪点，尤其在反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯的复配组合物到达近似共沸点温度附近时依然能保持反式-1，2-二氯乙烯闪点在较高范围检测不到闪点。
所述的混合液沸腾前无闪点。由于混合液在沸腾前的各个温度时，两种组分的比例均保持稳定，因此可以实现在近似共沸，即混合液温度在47℃附近时依然具备良好的抑制闪点效果。
优选的，所述的1-氯-2，3，3-三氟丙烯为反式-1-氯-2，3，3-三氟丙烯。
1-氯-2，3，3-三氟丙烯实际为一种顺式和反式共存的混合物，即1-氯-2，3，3-三氟丙烯（E/Z），而本发明利用的主要是反式-1-氯-2，3，3-三氟丙烯的沸点为48℃，更接近反式-1，2-二氯乙烯的沸点47.67℃，提高1-氯-2，3，3-三氟丙烯（E/Z）混合物中反式-1-氯-2，3，3-三氟丙烯的占比，更容易体现其抑制闪点、近似共沸的优势，当反式-1-氯-2，3，3-三氟丙烯的占比大于等于95%时，调整其在反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯的组合物中的占比，可以更容易的调整得到44—124不同清洁值（KB值）的清洗剂，满足对不同清洗对象的清洗要求。
一种反式-1，2-二氯乙烯的应用，其特征在于：利用上述反式-1，2-二氯乙烯抑制闪点的方法配成的混合液做清洗剂。
组合物中的构成组分都是优良的新型环保清洗剂溶剂，所以，该组合物既可以用作喷雾清洗剂、皮革衣物干洗剂、机器清洗剂、硅油氟油稀释剂、防锈稀释剂等适用于各各清洗领域，并且可以广泛用于低温萃取、脱墨、脱脂等溶剂领域。在以上所述的反式-1，2-二氯乙烯抑制闪点的方法下，真正实现了在多种温度环境下相同的抑制反式-1，2-二氯乙烯闪点的效果，从而得以用于使用反式-1，2-二氯乙烯蒸汽来清洗各种物体，从而实现对各种死角、缝隙充分清洗。
优选的，所述的混合液清洗剂置于密闭空间中并升温45~50℃，待清洗物置于液面上方处于冷却状态进行蒸洗。
本发明考虑到了反式-1，2-二氯乙烯在中高端工业清洗，即机器清洗中的应用，由于本发明发现的抑制反式-1，2-二氯乙烯闪点的方法可以适用于体系温度在接近反式-1，2-二氯乙烯沸点时抑制了闪点，因此可以采用加热蒸发的方式对有特殊要求的机器零部件进行清洗；鉴于反式-1，2-二氯乙烯本身的优秀清洗效果，配合蒸汽的温度效果与高渗透性，可以实现更好的清洗效果。采用这种方法能使精密或对其它介质敏感的器件能够重复、充分且安全的得到清洗，并且依托于1-氯-2，3，3-三氟丙烯与反式-1，2-二氯乙烯的沸点接近，在利用沸腾蒸发的蒸汽清洗时两种气体在蒸汽中均匀混合，不会出现分压不均，因此1-氯-2，3，3-三氟丙烯难以逃逸，补充量小，整个清洗体系可以重复进行，满足了清洗要求，能够大大节约使用成本，也减轻对臭氧层等环境的污染。
优选的，所述的待清洗物为机械零部件、电子零器件。1-氯-2，3，3-三氟丙烯对于机械零部件采用蒸汽清洗可以具有更好的清洗效果。
 有益效果
与现有技术相比，本发明所具有的有益效果是：反式-1，2-二氯乙烯闪点可以在达到组合物近似共沸点前被完全被抑制，从而得以利用该特性将反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯的混合物升温沸腾蒸发，使用蒸汽蒸洗的方式对各种对象充分重复清洗，达到更好的清洗效果，并且反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯在清洗物件时因机器的密封和清洗物件的冷却，清洗剂蒸汽遇冷后凝为液体，进入反复清洗，从而不容易逃逸，无需补充，也降低对环境尤其是臭氧层等的破坏。
 本发明的最佳实施方式
实施例10是本发明的最佳实施例，下面结合实施例对本发明做进一步说明。
 本发明的实施方式
主要组分反式-1，2-二氯乙烯T-DCE的生产厂家是中国宁夏普瑞化工有限责任公司，主含量为大于等于99.9%。
实施例 1~8 与对比例 1~3   一种1-氯-2，3，3-三氟丙烯制备方法，包括以下步骤：1）1，1，2，3，3-五氯丙烷为原料与氟化氢在山东飞源化工有限公司生产的F-Cr 2o 3催化下生成1，2-二氯-3，3-二氟丙烯（E/Z）（CHCl=CCl-CHF2）(HCFO-1232aa)，反应温度275℃，空速240h -1，氟化氢与1，1，2，3，3-五氯丙烷投料比15：1；2）1，2-二氯-3，3-二氟丙烯与氟化氢反应生成1-氯-2，3，3-三氟丙烯（E/Z）(CHCl=CF-CHF2)(HCFO-1233yd)，催化剂采用山东飞源化工有限公司生产的Cr-Co-Zn复合催化剂，反应温度300℃，空速220h -1，氟化氢与1，2-二氯-3，3-二氟丙烯投料比4：1。
一种反式-1，2-二氯乙烯抑制闪点的方法：将反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯混合，使1-氯-2，3，3-三氟丙烯在混合液中按重量计占3%~90%。各实施例反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯的混合比例见下表1。其中，T-DCE为反式-1，2-二氯乙烯，1233yd为采用上述1-氯-2，3，3-三氟丙烯制备方法制得的未经分离顺式与反式的1-氯-2，3，3-三氟丙烯，T-DEC/1233yd为反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯的重量比。
一种反式-1，2-二氯乙烯的应用。将实施例1所得反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯（E/Z）的混合液放入密闭恒温箱内，体积约占箱容积30%，反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯（E/Z）的重量比90：10，加热至温度保持在47℃，箱内顶部固定口径1mm长15cm的90°弯角空心钢管，内部有机油污垢堵塞，距离液面高度30cm，对钢管进行冷却并保持到低于25℃，进行蒸洗1h，取出观察钢管内部机油已大部分溶解，两端实现连通。
在仅30%总容积的混合液情况下，全程不需要补液，以此可以证明1-氯-2，3，3-三氟丙烯没有发生逃逸，而蒸洗效果良好证明在蒸汽中反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯（E/Z）也没有发生分离，依然保持良好的近似共沸的效果。以此，反式-1，2-二氯乙烯可以用于大规模的特殊零件或机械的充分清洗。
表1 混合比例。
Figure 956151dest_path_image001
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实施例 9~13    一种反式-1，2-二氯乙烯抑制闪点的方法。重复实施例1所述的1-氯-2，3，3-三氟丙烯制备方法，将制得的1-氯-2，3，3-三氟丙烯采用精馏方式，得到沸点为47.67℃的反式-1-氯-2，3，3-三氟丙烯，将反式-1，2-二氯乙烯与所得1-氯-2，3，3-三氟丙烯混合，使1-氯-2，3，3-三氟丙烯在混合液中按重量计占3%~90%。各实施例配比如下表2所示。其中1233yd（E）为反式-1-氯-2，3，3-三氟丙烯。
表2 反式-1，2-二氯乙烯与1233yd（E）混合比例。
Figure 23464dest_path_image002
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性能测试 1  按照《 中华人民共和国国家标准》  GB/T  5208-2008 / ISO 3679:2004测试反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯的混合液的闭杯闪点。将以上实施例与对比例所得试样分别放入0℃的室，然后使室温度降至-18℃，湿度45%。在设定的测试温度点测量闪点3次，将测试结果计入表3，其中N/A为已达到闪点因此不再测试。
表3 闪点测试。
Figure 837837dest_path_image003
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根据表3可知本发明所述的反式-1，2-二氯乙烯抑制闪点的方法，在1-氯-2，3，3-三氟丙烯在混合液中按重量计占3%~90%情况下都能够起到优良的抑制闪点的效果，当仅占1~2%时会出现断崖式的抑制闪点效果下降。同时根据已知的反式-1，2-二氯乙烯的沸点约为47~48℃附近，而根据实施例2~8可知在混合液已经沸腾的情况下，依然具备抑制反式-1，2-二氯乙烯的效果。对于1-氯-2，3，3-三氟丙烯在混合液中按重量计占90%以上时，由于反式-1，2-二氯乙烯含量过低则其本身的清洗效果会有显着下降。
性能测试 2   采用中国石油化工股份公司齐鲁石化研究院设计的共沸点测试装置测试反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯的混合液的共沸点，该装置由精馏平衡釜、纯水沸点计、汞压计、冷凝器、二个缓冲瓶、自动平衡控制仪、二个继电器、二个电磁阀、若干玻璃管组合而成，另外配合气相色谱仪及数据处理机，给出测试数据积分结果。选用上述实施例1~13与对比例2~3在该装置上近似共沸蒸馏进行测试，结果计入表4。
表4 近似共沸温度测试。
Figure 112829dest_path_image004
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根据表4可知，利用本申请所述的反式-1，2-二氯乙烯抑制闪点的方法，在反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯的混合液达到沸点，即近似共沸点时，所得到的塔顶蒸汽中两种成分的比例依然保持与混合液近似，即可以证明在环境温度使反式-1，2-二氯乙烯沸腾蒸发时，1-氯-2，3，3-三氟丙烯依然可以保持稳定的抑制闪点的作用，从而得以利用其蒸汽进行清洁等其它特殊作用。其中，在同等的原料混合比例下，当用纯反式的1-氯-2，3，3-三氟丙烯做闪点抑制剂，混合液蒸发后所得蒸汽中反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯的混合比例更接近混合液体的混合比例，因此可以获得更接近于近似共沸的效果，即更佳的抑制闪点作用。
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。

Claims (9)

  1. 一种反式-1，2-二氯乙烯抑制闪点的方法，其特征在于：将反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯混合，使1-氯-2，3，3-三氟丙烯在混合液中按重量计占3%~90%。
  2. 根据权利要求1所述的反式-1，2-二氯乙烯抑制闪点的方法，其特征在于：将反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯混合，使1-氯-2，3，3-三氟丙烯在混合液中按重量计占5%~50%。
  3. 根据权利要求2所述的反式-1，2-二氯乙烯抑制闪点的方法，其特征在于：将反式-1，2-二氯乙烯与1-氯-2，3，3-三氟丙烯混合，使1-氯-2，3，3-三氟丙烯在混合液中按重量计占10%~20%。
  4. 根据权利要求1所述的反式-1，2-二氯乙烯抑制闪点的方法，其特征在于：所述的1-氯-2，3，3-三氟丙烯制备方法包括以下步骤：
    1）1，1，2，3，3-五氯丙烷为原料与氟化氢在铬系催化剂催化下生成1，2-二氯-3，3-二氟丙烯，反应温度200~350℃，空速60~570h -1，氟化氢与1，1，2，3，3-五氯丙烷投料比5~25：1；
    2）1，2-二氯-3，3-二氟丙烯与氟化氢反应生成1-氯-2，3，3-三氟丙烯，主催化剂为氟化氢处理的铬基催化剂，辅催化剂为Zn、Co、Ni和Cu元素之一，反应温度250~400℃，空速50~550h -1，氟化氢与1，2-二氯-3，3-二氟丙烯投料比1~8：1。
  5. 根据权利要求1所述的反式-1，2-二氯乙烯抑制闪点的方法，其特征在于：所述的混合液沸腾前无闪点。
  6. 根据权利要求1所述的反式-1，2-二氯乙烯抑制闪点的方法，其特征在于：所述的1-氯-2，3，3-三氟丙烯为反式-1-氯-2，3，3-三氟丙烯。
  7. 一种反式-1，2-二氯乙烯的应用，其特征在于：利用权利要求1~6任一项所述的抑制闪点的方法配成的混合液制作清洗剂。
  8. 根据权利要求7所述的反式-1，2-二氯乙烯的应用，其特征在于：所述的清洗剂置于密闭空间中并升温45~50℃，待清洗物置于液面上方进行蒸洗。
  9. 根据权利要求8所述的反式-1，2-二氯乙烯的应用，其特征在于：所述的待清洗物为机械零部件、电子器件。
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