WO2020173454A1 - 一种含八氟戊基烯烃醚的卤代烃组合溶剂及其应用 - Google Patents

一种含八氟戊基烯烃醚的卤代烃组合溶剂及其应用 Download PDF

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WO2020173454A1
WO2020173454A1 PCT/CN2020/076721 CN2020076721W WO2020173454A1 WO 2020173454 A1 WO2020173454 A1 WO 2020173454A1 CN 2020076721 W CN2020076721 W CN 2020076721W WO 2020173454 A1 WO2020173454 A1 WO 2020173454A1
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hydrocarbon
ether
octafluoropentyl
combined solvent
substituted
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刘向尧
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上海锐一环保科技有限公司
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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
    • C11D7/26—Organic compounds containing oxygen
    • 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
    • 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

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  • Halogenated hydrocarbon solvents are widely used in electronic cleaning, precision machining and other fields, as precision cleaning agents, aerosol cans, thinners and other applications. Based on the current updated regulatory requirements, users expect to find an environmentally friendly alternative that not only meets environmental protection requirements, does not consume ozone, has zero or almost zero ODP values, and has low greenhouse effect, but also meets the ever-increasing product density and function enhancement Technical requirements. As a substitute for CFCs, HCFCs, toxic chlorinated solvents, n-bromopropanes, and HFCs with high greenhouse effect GWP.
  • HCFC-141 B, HCFC225, nPB, chlorinated solvents such as dichloromethane, trichloroethane, and fluorocarbon solvents are used as cleaning agents for electronic cleaning and precision machining on the market, among these solvents, there are Some of them are transitional products of Freon, or ozone-depleting substances; some have too high GWP to meet the requirements of climate change, and some have defects such as excessive toxicity.
  • the signing of the Kyoto Protocol and the Paris climate Agreement are highly concerned about global warming, and the Kigali Amendment to the Montreal Agreement defines a timetable for the phase-out of HFCs.
  • hydrocarbon substitute solvents in the prior art are used as cleaning agents in electronic cleaning, precision machining and other fields. They are toxic and have high GWP values, are flammable, have poor safety, and cannot meet environmental protection requirements.
  • the purpose of the present invention is to provide an octafluoropentyl olefin aldehyde-containing combined hydrocarbon solvent and its application in view of the shortcomings of the prior art.
  • the halogenated hydrocarbon combined solvent containing octafluoropentyl olefin aldehyde is used for Complementary or similar comma, low toxicity, no flash point, safe operation, and strong dissolving and decontamination power, which can meet the requirements for cleaning and dissolving power, 0DP value is zero, GWP is very low, raw materials are easily available, and It is non-toxic, harmless, non-corrosive or low-corrosive, has a simple preparation process, does not pollute the environment, and has a low production cost. It is an efficient cleaning agent with great industrial value.
  • a hydrocarbon-substituting combined solvent containing octafluoropentyl olefin ether which is characterized in that it is divided into the following components to make a comma or a hydrocarbon-substituting combined solvent that is similar to a coma: trans 1, 2 -Dichloroethylene: 0.1 ⁇ 98 parts by weight Octafluoropentyl dilute awakening: 0.1 to 30 parts by weight
  • Stabilizer 0.1 to 3 parts by weight;
  • the stabilizer is one or a combination of fluoroalcohol and organic amine salt.
  • Octafluoro pentyl the woman was awake preferably 1 _ 2 _ women perfluoropropyl, 2, 2 - wake-trifluoroethyl, 2 - perfluoropropyl women -2, 2, 2 - trifluoroethyl ether, 1 , 1, 2, 3, 3, 3-hexafluoropropyl-2,2-difluorovinyl ether or a combination of two or more.
  • hydrocarbon-based combined solvent containing octafluoropentyl olefin ether which is characterized in that the combined solvent of hydrocarbon-based and alcohol is mixed at a volume ratio of 1:0.001 to 0.05 as a cleaning agent for electronic components or flux , Or a combination of halogenated hydrocarbon solvent and propellant in a volume ratio of 1: 0.1 to 0.3 mixed in the spray can, as a cleaning agent for precision machined parts
  • the alcohol is methanol, ethanol, isopropanol, and One or a combination of two or more alcohols and isomers
  • the propellant is carbon dioxide, nitrogen, compressed air, difluoromethane, trifluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, 2, 3, 3, 3-tetrafluoropropene, trans-1, 3, 3, 3-tetrafluoropropene, 1, 2, 3, 3, 3-pentafluoropropene, one of hydro
  • the present invention has stronger cleaning, dissolving, degreasing and decontamination capabilities, and is especially suitable for cleaning the surfaces of electronic components and precision machined parts to remove oil stains, as well as the removal of residues such as flux, and has high solubility.
  • the value is zero, the GWP is very low, the raw materials are easily available, and are non-toxic, harmless, non-corrosive or low-corrosive, the preparation process is simple, does not pollute the environment, and the production cost is low. It is a very industrial use A valuable and efficient cleaning agent.
  • the hydrocarbon-substituted combined solvent prepared in Example 1 has a strong degreasing ability against conventional mineral oil, P0E synthetic oil and silicone oil, and has a good cleaning effect.
  • trans-1, 2-dichloroethylene has good oil dissolving ability, it is flammable, so it is not applicable in many application environments.
  • fluorinated alkane and fluorinated aldehydes they are usually non-flammable.
  • the oil dissolving power is very poor, but the hydrocarbon-substituting combined solvents of the above components are not flammable, but they have good dissolving power and strong degreasing ability.
  • the PCBA after reflow soldering is immersed in a boiling solvent for 5 minutes, and then immersed in a second tank with a temperature lower than the boiling point for a second cleaning for 5 minutes.
  • Ultrasonic waves, spraying or stirring can be supplemented to enhance the cleaning effect;
  • the connector is put out in the low temperature tank, immersed in the steam area for steam bath washing for 2 minutes, and then condensed and dried.
  • the formulated hydrocarbon-substituted combined solvent is very effective in removing rosin flux.
  • the hydrocarbon-substituting combination solvent prepared in Example 1 or Example 2 was used to replace the HCFC-141 B cleaning agent.
  • the experiment chose a PCB board with a very narrow pin line and an IC module.
  • ultrasonic vapor phase vapor phase equipment Completed the effect test of two cleaning agents. Due to the difference in boiling point, the heating temperature needs to be adjusted to the boiling point of the hydrocarbon-substituted combined solvent prepared in Example 1 or Example 2 during the test.
  • Experimental results show that the cleaning effect of this composition is better than 141 B, and it can completely replace 141 B.
  • the 1 41 B cleaning agent which is currently used in large quantities, belongs to the hydrochlorofluorocarbon category. According to the national plan, all cleaning applications of 1 41 B will be phased out in 2025.
  • the hydrocarbon-based combined solvent and HCFC prepared in Example 1 or Example 2 -141 B cleaning agent is the same, suitable for existing cleaning equipment, cleaning power is stronger than HCFC-141 B cleaning agent, static volatilization loss is only half of 141 B, it is a very economical alternative.
  • the environmentally friendly hydrocarbon-based combination solvent containing octafluoropentyl olefin ether as azeotrope or near azeotrope has zero ODP value, very low GWP, low toxicity, no flash point, and appropriate
  • the cleaning power and volatile dryness Speed which meets and applies to existing equipment, is an economical choice at the current technological stage.
  • Unsaturated olefin ethers are hydrofluorocarbons containing unsaturated bonds and ether bonds in their molecular structure. The ozone depletion value is zero, the residence time in the atmosphere is shorter, and the greenhouse effect value is very low.
  • Hydrofluoroether is a type of hydrofluorocarbon with ether bond in its molecular structure.
  • ozone depletion value is zero, the residence time in the atmosphere is very short, and the greenhouse effect value is not high; and both of them are non-flammable, low toxicity, and good solubility.
  • trans-1,2-dichloroethylene has a strong dissolving power, which can perfectly replace 141 B of hydrochlorofluorocarbons, toxic n-bromopropanes, and chlorinated solvents such as methylene chloride and trichloro Ethylene, tetrachloroethylene, etc.
  • chlorinated solvents such as methylene chloride and trichloro Ethylene, tetrachloroethylene, etc.
  • Such a combination not only conforms to the trend of environmental protection substitution, has the advantages of fluorine-containing compounds, has no flash point, is safe to operate, and has strong solubility and decontamination power, which can meet the requirements for cleaning and dissolving power.
  • the above embodiments are only a further description of the present invention, and are not used to limit the patent of the present invention. All equivalent implementations of the present invention should be included in the scope of the claims of the present patent.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
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Abstract

一种含八氟戊基烯烃醚的卤代烃组合溶剂，是反式1,2-二氯乙烯与八氟戊基烯烃醚、1,1,2,3,3,3-六氟丙基-2,2,2-三氟乙基醚和稳定剂按0.1～98：0.1～30：0.1～98：0.1～3重量份配制的卤代烃组合溶剂，该组合溶剂与醇按1：0.001～0.05体积比混合后作为电子元器件或助焊剂的清洗剂，或与推进剂按1：0.1～0.3体积比混装于喷罐内，作为精密机加工件清洗剂。

Description

一种含八氟戍基稀经醒的 代经组合溶剂及其应用 技术领域
本发明涉及化学清洗剂技术领域， 尤其是一种含八氟戍基烯烃醚的 卤代烃组合溶剂及其应用。
背景技术
卤代烃溶剂被广泛应用于电子清洗、 精密机加工等的领域， 作 为精密清洗剂、 气雾罐、 稀释剂等应用。 基于目前更新的法规要求， 用户期望找到一款既符合环保要求， 具有不消耗臭氧， ODP值为零或 近似为零， 温室效应低的环保替代品， 又满足不断提升的产品密集 度、 功能提升的技术要求。 作为替代 CFCs、 HCFCs、 毒性大的氯化溶 剂、 正溴丙烷类， 以及温室效应 GWP值高的 HFCs 的替代品。
目前， 虽然市场上以 HCFC- 1 41 B、 HCFC225、 nPB及二氯甲烷、 三 氯乙婶等氯化溶剂， 以及氟碳溶剂等为电子清洗、 精密机加工的清 洗剂， 这些溶剂中， 有的属于氟利昂的过渡产品， 还是消耗臭氧物 质； 有的 GWP值过高， 不能满足气候变化要求， 有的存在毒性过高 等的缺陷。 京都议定书和巴黎气候协定的签署对全球变暖的高度关 注， 蒙特利尔协议的基加利修正案， 界定了 HFCs 的淘汰时间表。 对 于温室气体的排放以发达国家先期淘汰， 如欧盟的 F-ga s 法规， 从 法规层面强制替代。 而对于造成大气污染的， 有的国家地区制定空 气污染法， 限制使用； 对于危害员工健康的， 欧盟列入 SVHC名录， 我国列入职业病范畴。
现有技术的 代烃溶剂， 作为清洗剂用于电子清洗、 精密机加工 等领域， 存在毒性和 GWP值过高， 易燃，安全性差， 不能满足环保要 求。
发明内容
本发明的 目 的是针对现有技术的不足而提供的一种含八氟戍基 稀烃醒的 代烃组合溶剂及其应用， 采用含有八氟戍基稀烃醒的卤 代烃组合溶剂， 为共濟物或近似共濟物， 低毒， 无闪点， 安全操作， 而且可溶解除污力强， 可以满足对清洗溶解力的要求， 0DP值为零， GWP非常低， 原材料易得， 且无毒、 无害、 无腐蚀性或低腐蚀性， 制 备工艺简单， 不污染环境， 生产成本低， 是一种很有工业使用价值 的高效清洗剂。
实现本发明 目的的技术方案是： 一种含八氟戍基烯烃醚的 代烃组 合溶剂，其特点是按下述组分配制成共濟物或近似共濟物的 代烃组合溶剂： 反式 1 , 2 -二氯乙烯: 0. 1〜 98重量份 八氟戍基稀经醒: 0. 1〜 30重量份
1 , 1 , 2, 3, 3, 3 -六氟丙基 -2, 2, 2 -三氟乙基醚： 0. 1〜 98重量份
稳定剂： 0. 1〜 3重量份； 所述稳定剂为氟醇、 有机胺盐的一种或两种以上的组合。
所述八氟戍基婦经醒优选为 1 _全氟丙婦 _2, 2, 2 -三氟乙基醒、 2 -全氟丙婦 -2, 2, 2 -三氟乙基醚、 1 , 1 , 2, 3, 3, 3 -六氟丙基 -2, 2 -二氟乙烯醚的一种或两种以 上的组合。
一种含八氟戍基烯烃醚的 代烃组合溶剂的应用，其特点是 代烃组合溶 剂与醇按 1 : 0. 001〜 0. 05体积比混合后作为电子元器件或助焊剂的清洗剂， 或卤代烃组合溶剂与推进剂按 1 : 0. 1〜 0. 3体积比混装于喷罐内， 作为精密机 加工件清洗剂， 所述醇为甲醇、 乙醇、 异丙醇、 戍醇及异构体的一种或两种以 上的组合； 所述推进剂为二氧化碳、 氮气、 压缩空气、 二氟甲烷、 三氟甲烷、 二氟乙烷、 三氟乙烷、 四氟乙烷、 2, 3, 3, 3 -四氟丙烯、 反式 -1 , 3, 3, 3 -四氟丙 烯、 1 , 2, 3, 3, 3 -五氟丙烯、 烃类、 二甲醚的一种或两种以上的组合。
本发明与现有技术相比具有较强的清洗溶解和脱脂去污能力， 尤其满足 电子元器件、精密机加工件的表面去除油污，以及助焊剂等残余物去除的清洗， 溶解力高， 0DP值为零， GWP非常低， 原材料易得， 且无毒、 无害、 无腐蚀性 或低腐蚀性， 制备工艺简单， 不污染环境， 生产成本低， 是一种很有工业使用 价值的高效清洗剂。
具体实施方式
以下将通过具体的实施例对本发明做进一步的阐述：
实施例 1
称取 80 克反式 1， 2 -二氯乙烯与 1 0 克八氟戍基烯烃醚、 1 5 克 1 , 1 , 2, 3, 3, 3 -六氟丙基 -2, 2, 2 -三氟乙基醚和 1 克氟醇， 配制成用作油污清洗 剂的 代烃组合溶剂。将上述配制的 代烃组合溶剂按下述步骤对常规的矿物 油、 P0E合成油和硅油进行平行测试的实验：
a、 在干净的铝片上分别涂敷 68#矿物润滑油、 RL68 P0E 合成油和 DC360 硅油后再次称重， 并记录干净铝片和涂敷油脂铝片的重量；
b、 将铝片浸没入盛有上述配制的 代烃组合溶剂的烧杯里，浸泡 3分钟； c、 将铝片置于加热至沸腾的 代烃组合溶剂的上方， 蒸汽漂洗 3分钟； d、 蒸汽漂洗结束后， 在空气中干燥 1 分钟， 然后称重并计算去除的污物 的百分比；
e、 将上述称重及计算数据整理成下述表 1 :
表 1
Figure imgf000006_0001
从 上 述表 1 可以清楚的看出实施例 1 配制的 代烃组合溶剂，对常规的矿物油、 P0E 合成油和硅油具有较强的去油污能力， 清洗效果良好。 虽然反式 -1 , 2 -二氯乙 烯具有很好的溶油能力， 但可燃的， 因此在很多应用环境下是不适用的； 作为 氟化稀烃醒和氟化醒通常是不可燃的， 溶油力很差， 但上述组分的 代烃组合 溶剂不易燃， 却具备了良好的溶解力和较强的去油污能力。
实施例 2
称取 80 克反式 1， 2 -二氯乙烯与 10 克八氟戍基烯烃醚、 20 克 1 , 1 , 2, 3, 3, 3 -六氟丙基 -2, 2, 2 -三氟乙基醚、 1 克氟醇和 5克甲醇， 配制成用 作助焊剂清洗剂的 代烃组合溶剂。将上述配制的 代烃组合溶剂对回流焊后 的 PCBA接插件按下述步骤进行松香助焊剂的去除实验， 以达到品管要求： a、 回流焊后的 PCBA浸入沸腾的溶剂浸泡洗 5分钟，再浸入温度低于沸点 的第二槽二次清洗 5分钟， 可以辅以超声波、 喷淋或搅拌等以加强清洗效果； b、 从低温槽中提出接插件， 浸入蒸汽区域进行蒸汽浴洗 2分钟， 然后冷 凝干燥， 实验结果显示助焊剂残留量完全达到技术规格要求， 充分说明实施例
2
配制的 代烃组合溶剂对松香助焊剂的去除非常有效。
实施例 3
将实施例 1 或实施例 2配制的 代烃组合溶剂用于替代 HCFC-141 B清洗 剂， 实验选用插脚线很窄并带 I C模块的 PCB板， 在现有 1 41 B超声波汽相汽相 设备中完成两款清洗剂的效果测试。 由于沸点的区别， 测试时需把加热温度调 至实施例 1 或实施例 2配制的 代烃组合溶剂的沸点。 实验结果显示， 该组合 物的清洗效果好于 141 B， 完全可以替代 141 B。
现在用量较大的 1 41 B清洗剂属于氢氯氟烃类， 按照国家计划， 将于 2025 年淘汰全部的清洗用途 1 41 B， 而实施例 1 或实施例 2配制的 代烃组合溶剂 和 HCFC-141 B清洗剂一样， 适用于现有清洗设备， 清洗力比 HCFC-141 B清洗剂 更强， 静态挥发损耗量只有 141 B的一半， 是非常经济的替代方案。 在溶剂的 替代选择上，以含八氟戍基烯烃醚的环保 代烃组合溶剂为共沸物或近似共沸 物是以其 ODP值为零， GWP非常低， 低毒， 无闪点， 适当的清洗力和挥发干燥 速度， 而满足并适用于现有设备， 在当前技术阶段是一种经济性的选择。 不饱 和烯烃醚是一类分子结构中含有不饱和键和醚键的氢氟碳化合物，臭氧消耗值 为零， 其大气滯留时间更短， 温室效应值非常低。 氢氟醚是一类分子结构中含 有醚键的氢氟碳化合物， 臭氧消耗值为零， 大气滯留时间很短， 温室效应值不 高； 而两者都具有不易燃， 低毒性， 溶解性良好， 表面张力低、 粘度低、 润湿 性好、 无腐蚀性等特性。 而与氟醚组合的反式 1 , 2 -二氯乙烯， 臭氧消耗值为 零， 大气滯留时间很短， 温室效应值很低； 沸点适中； 低毒， TWA=200ppm， 符 合环保、 低毒、 环境友好要求。 同时， 反式 1 , 2 -二氯乙烯具有很强的溶解力， 可以完美替代氢氯氟烃类的 141 B、 毒性大的正溴丙烷类， 以及氯化溶剂类的 二氯甲烷、 三氯乙烯、 四氯乙烯等。 这样的组合既符合环保替代趋势， 具有含 氟化合物的优点， 无闪点， 安全操作， 而且可溶解除污力强， 可以满足对清洗 溶解力的要求。 以上各实施例只是对本发明做进一步说明， 并非用以限制本发明专利， 凡 为本发明的等效实施， 均应包含于本发明专利的权利要求范围之内。

Claims

权 利 要 求 书
1、 一种含八氟戍基稀烃醒的 代烃组合溶剂， 其特征在于： 按下述组分 配制成共濟物或近似共濟物的 代烃组合溶剂：
反式 1, 2 -二氯乙烯： 0.1〜 98重量份 八氟戍基烯烃醚： 0.1〜 30重量份
1, 1, 2, 3, 3, 3 -六氟丙基 -2, 2, 2 -三氟乙基醚： 0.1〜 98重量份 稳定剂： 0.1〜 3重量份；
所述稳定剂为氟醇、 有机胺盐的一种或两种以上的组合。
2、 根据权利要求 1 所述含八氟戍基烯烃醚的 代烃组合溶剂， 其特征在 于： 所述八氟戍基烯烃醚优选为 1-全氟丙烯 -2, 2, 2 -三氟乙基醚、 2 -全氟丙烯 -2, 2, 2 -三氟乙基醚、 1,1,2, 3, 3, 3 -六氟丙基 -2, 2 -二氟乙烯醚的一种或两种以 上的组合。
3、 一种权利要求 1 所述含八氟戍基婶烃醒的 代烃组合溶剂的应用， 其 特征在于： 代烃组合溶剂与醇按 1: 0.001〜 0.05体积比混合后作为电子元 器件或助焊剂的清洗剂， 或 代烃组合溶剂与推进剂按 1 : 0.1〜 0.3体积比混 装于喷罐内， 作为精密机加工件清洗剂， 所述醇为甲醇、 乙醇、 异丙醇、 戍醇 及异构体的一种或两种以上的组合；所述推进剂为二氧化碳、氮气、压缩空气、 二氟甲院、 三氟甲院、 二氟乙院、 三氟乙院、 四氟乙院、 2, 3, 3, 3 -四氟丙稀、 反式 -1, 3, 3, 3 -四氟丙烯、 1,2,3,3,3 -五氟丙烯、 烃类、 二甲醚的一种或两种 以上的组合。
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