CN1871193A - 反－1,2－二氯乙烯的稳定化 - Google Patents

反－1,2－二氯乙烯的稳定化 Download PDF

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CN1871193A
CN1871193A CNA2004800310267A CN200480031026A CN1871193A CN 1871193 A CN1871193 A CN 1871193A CN A2004800310267 A CNA2004800310267 A CN A2004800310267A CN 200480031026 A CN200480031026 A CN 200480031026A CN 1871193 A CN1871193 A CN 1871193A
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让-皮埃尔·拉利尔
杰希卡·贝恩斯
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Abstract

本发明涉及为了在固体表面处理中应用反－1，2－二氯乙烯(TDCE)而对其进行的稳定化。稳定溶液包含至少一种除酸剂、至少一种自由基清除剂、至少一种路易斯碱和至少一种缓冲化合物。

Description

反-1，2-二氯乙烯的稳定化
本发明涉及反-1，2-二氯乙烯(TDCE)的稳定化，其稳定化的目的是为了将其用于固体表面处理中，更具体地说，用于清洁、脱脂、去除焊剂或者干燥金属。
1，2-二氯乙烯是一种广泛应用于固体表面处理的工业溶剂，例如用于清洁固体表面、金属组件的脱脂或者去除印制电路的焊剂。
1，2-二氯乙烯以两种同分异构的形式存在，即顺-1，2-二氯乙烯和反-1，2-二氯乙烯。1，2-二氯乙烯的这两种异构体具有截然不同的化学和物理性能。具体地说，反式异构体与顺式异构体相比具有较低的沸点、较低的密度、较低的粘度和较低的表面张力。这就是为什么反-1，2-二氯乙烯(其表示为TDCE)在溶剂清洁应用中为优选异构体的原因。1，2-二氯乙烯的这两种异构体能够通过分馏来进行分离。然而，在存储期间，由于顺式异构体在热力学上更加稳定，因此TDCE会自发地转化为顺式异构体，除非它被稳定化。专利US6153575公开了少量的脂肪族醛腙的使用，任选地与环氧化物组合，从而在存储期间抑制TDCE异构化为顺式异构体。
TDCE存储时的稳定性是它在从几星期到几个月的时期内，在常规的存储容器中，在一般不超过50℃的温度下耐转化或分解的能力。
在它作为用于固体表面处理的溶剂使用时，TDCE常常会遇到其它的能够导致它分解的侵袭(attack)，这些侵袭与处理装置的操作方法有关。因此，TDCE的使用所产生的这些问题不同于那些在存储期间所遇到的问题。
在TDCE使用过程中，例如在用于金属组件脱脂的设备中，侵袭TDCE的主要来源是：空气、水、金属和热。这是因为金属脱脂一般通过把待脱脂的组件放入到适当的设备中来进行，该设备位于含有保持回流的TDCE的容器(tank)的液面上方。TDCE蒸汽凝结在金属组件上，并且冷凝物重复循环使用。在这种条件下，TDCE发生各种各样的反应，例如被空气氧化、被来自于大气水蒸气冷凝的水水解、热分解或者与金属接触发生催化反应。
在文献中，提供了各种各样的解决方法来稳定某些遇到相同侵袭来源的卤代烃。在专利US3043888中，推荐了在金属脱脂过程中，加入各种各样的稳定剂来稳定包含1到3个碳原子的卤代烃，更具体地为三氯乙烯。某些醛腙非常有效，并且能够和其它化合物(例如包括羟基的芳香族化合物、胺、有机环氧化物、一元羧酸酯、醇或者不饱和化合物)组合使用。在抑制由金属催化的甲基氯仿的分解中，特别有效的化合物被描述为1，3-二氧戊环及其烷基同系物或1，4-二烷(参见专利US4026956；US3251891；US4418231；和US2811252)。
然而，在文献所提供的解决办法中，用于稳定例如卤代烃的溶剂的体系并不具备作为稳定剂所应具备的所有特性，并且特别是在使用TDCE的现有技术中，相对于空气、水、金属和热，没有完备的用于稳定化的体系被公开。
首先，该稳定体系优选具有双重作用：预防作用，更具体地为抑制副反应，和补救(curative)作用，也就是说原位抑制(trap)不期望的效果。随后，为了促进稳定溶剂的使用，该稳定体系有利地具有相似于溶剂沸点的沸点，它有利地存在于液相和气相中，它不溶或仅微溶于水，并且优选地它不改变溶剂的性质。为了不改变溶剂使用危险性的标签(labelling)，稳定化配料有利地是无毒的。最后，出于经济原因，优选地，稳定化配料由便宜的工业产品构成。
现在已经发现，在TDCE中加入几种添加剂构成了能够完全满足上面所提标准的稳定体系，其中每一种添加剂起到例如酸性接受体、自由基清除剂、路易斯碱或者具有缓冲作用的化合物的作用，添加剂的加入也使得获得稳定的TDCE溶液成为可能，该TDCE溶液在其被用于金属的处理时，表现出好的抗分解性能。
在延长的使用过程中，在相同TDCE进料的热条件下，特别是当金属组件是由铝或者铁构成的时候，空气中的水分、油脂、油、尘土和细微的金属粒子在TDCE中积累，并且它们是各种各样导致TDCE分解的反应的原因。这是因为，基于TDCE的化学结构，它主要能进行三种类型的反应，它们是双键的打开、氯的双峰反应(reactivity of the doublet)和自由基的产生。TDCE的分解一般导致盐酸或自由基的形成。在金属的存在下，更具体地说，在氯或者铁的存在下，盐酸能够反应形成氯化铝(AlCl3)或者氯化铁(FeCl3)，另外它们是TDCE放热缩合反应的催化剂。例如酸性接受体、自由基清除剂、路易斯碱或缓冲剂的稳定剂的加入使得对于这些各种反应进行预防和/或补救成为可能。
因此，本发明的主题是反-1，2-二氯乙烯(TDCE)的稳定溶液，该溶液包括，作为添加剂的至少一种酸性接受体、至少一种自由基清除剂、至少一种路易斯碱和至少一种具有缓冲作用的化合物。
根据本发明，在能够被用于稳定溶液的酸性接受体中，更具体地说可以提及有机环氧化物。作为非限定性的例子，可以提及环氧乙烷、环氧丙烷、环氧丁烷、一氧化丁二烯、二氧化丁二烯、表氯醇、缩水甘油、1，1-二甲基环氧乙烷或异丙基缩水甘油醚。优选环氧丙烷、环氧丁烷或异丙基缩水甘油醚。
在本发明的上下文中，作为自由基清除剂，可以使用各种有机化合物，例如烯烃、杂环或者酚衍生物。作为烯烃的非限定性例子，可以提及二异丁烯、戊烯、异戊二烯或α-甲基苯乙烯。作为杂环的非限定性的例子，可以提及吡咯、1，4-二烷或呋喃，其中吡咯更具体地为N-甲基吡咯，呋喃更具体地为四氢呋喃。作为酚衍生物的非限定性例子，可以提及苯酚、百里酚或紫罗兰醇。
将第一自由基清除剂用于气相和将第二自由基清除剂用于液相不会超出本发明的范围。例如，异戊二烯能够用作用于气相的自由基清除剂，且二异丁烯能够用作用于液相的自由基清除剂。两种清除剂的这种结合具有对于液态的TDCE和对于气态的TDCE同时有效的优点，这对于此处面对的应用是很必要的。
路易斯碱(给出电子对的化合物)可使金属的路易斯酸性点饱和，从而抑制形成AlCl3或者FeCl3的反应。根据本发明的能够被用于稳定溶液的路易斯碱实际上有很多种。可以提及缩醛、酮、硝基化合物、羧酸酯或者醚。作为缩醛，优选甲缩醛。作为酮的非限定性例子，可以提及丙酮和甲基乙基酮。作为硝基化合物的非限定性例子，可以提及硝基甲烷或者硝基乙烷。作为羧酸酯的非限定性例子，可以提及甲酸甲酯、乙酸甲酯或者乙酸异丙酯。作为醚，优选叔丁基甲基醚。
在能够被用于本发明的具有缓冲作用的化合物中，更具体地说，胺是适合的。胺使得获得限制溶剂分解动力的足够碱性的PH值，并保持相对固定的PH值成为可能。任何胺均可使用，并且优选使用三乙胺、N-甲基吗啉、二乙胺或者N，N-二异丙胺。
在AlCl3或者FeCl3可能形成后，除了上面提到的化合物外，使用醇来抑制AlCl3或者FeCl3也在本发明的范围之内。例如，合适的醇可以是甲醇、乙醇、正-丁醇或者叔-丁醇。
一般来说，存在于稳定体系中的添加剂具有与TDCE沸点相近的沸点。然而，比TDCE的挥发性稍低的化合物能够被选用来特别稳定TDCE的液相，或者相反，挥发性更高的化合物能够被选用来有效地稳定TDCE的气相。
存在于TDCE稳定溶液中的每一种添加剂的量能够大幅度变化，但是稳定溶液中每一种添加剂的含量优选在10-10000ppm之间，更优选在10-1000ppm之间。在通常用于金属处理的条件下，添加剂的总量应该能够充分抑制TDCE的分解，而不损害溶剂的性能。据认为，添加剂的总的含量少于50000ppm，优选少于5000ppm，可以同时获得在金属处理中有效稳定的TDCE溶液和最大可能的经济利益。
更具体地说，稳定溶液包括200-800ppm的酸性接受体、100-700ppm的自由基清除剂或者多种自由基清除剂的混合物、10-100ppm的路易斯碱和10-50ppm的具有缓冲作用的化合物。
根据本发明的TDCE的稳定溶液包括环氧丁烷、二异丁烯、异戊二烯、丙酮和二乙胺。更具体地说，稳定溶液包括200-800ppm优选530ppm的环氧丁烷、50-500ppm优选200ppm的二异丁烯、50-200ppm优选100ppm的异戊二烯、10-100ppm优选50ppm的丙酮和10-50ppm优选10ppm的二乙胺。
实验部分
各种测试被用来评价对TDCE稳定作用的有效性，其原理陈述如下：
水解测试
该测试为在100小时的加热回流过程中，监视待测稳定溶液PH值的变化，其中该稳定溶液加入了1％的水。为了完成测试，采用上部装有(surmount)温度计和李比希(Liebig)冷凝器的500ml三口烧瓶。第三个口装有隔膜，可通过隔膜使用注射器对试样进行提取。247.5ml的待测溶液被注入到装有2.5ml水的圆底烧瓶中。该溶液被加热回流100小时。每2-3小时提取大约5-10ml的试样，并且在提取的试样中加入等量的PH值为7的水后，测量提取的溶液的PH值。如果随着时间的推移PH值的变化不显著，那么水解测试的结果是否定的(negative)。
刮痕测试：该测试以ASTM D 2943-96.2000标准为基础。其为在预先刮过的铝片存在下评价氯化溶剂的稳定性。如果没有腐蚀性反应发生，则该刮痕测试的结果是否定的。
BAM(Bundesanstalt für Materialprüfung-柏林)测试
对于铝的形成的稳定作用借助于BAM测试进行测量，该测试被分为几个实验。
采用上部装有李比希冷凝器的500ml三口烧瓶。试样的温度通过使用探针进行测量。
待测的100ml溶液被引入到装有100ml甲苯、18g铝粉和0.7g无水AlCl3的三口烧瓶中。该混合物(称为BAM1)加热回流2次9小时。观察是否发生着色变化或者放热反应。
在BAM1混合物中加入1g的硬脂酸锌后，在和上面相同的实验条件下进行第二实验。其为BAM2反应介质。
以这样的混合物进行第三实验，该混合物通过向BAM1混合物中一次(this time)加入10ml的油酸而制备。这种反应混合物被称作BAM3。
如果在以3种混合物BAM1、BAM2和BAM3进行测试的过程中，没有观察到着色变化或者如果没有放热反应发生，那么进行称作BAM4的实验。其为通过蒸馏，将待测溶液分为等量的三个馏份。体积为100ml的每个馏份中加入100ml的甲苯、18g的铝粉和0.7g的无水AlCl3，然后这三个馏份均加热回流2次9小时。如果在加热过程中没有反应发生并且如果没有出现着色变化，那么该测试的结果是否定的。
下面的例子进一步阐述本发明，而不是对其进行限定。
实施例1(比较)
水解测试是以来自PPG Industries的TDCE溶液进行的，其中该溶液包括30ppm的环氧丁烷。在经过100小时后，观察到PH值从7.17的初始值到7.97的值的变化。因此该溶液不能被认为是稳定的。
实施例2
来自PPG Industries的TDCE被用于制备稳定的TDCE溶液，其中该溶液包括530ppm的环氧丁烷、300ppm的二异丁烯、50ppm的丙酮和10ppm的N-甲基吗啉。
水解测试显示在经过100小时后，PH值仅仅发生了在7.8和7.94之间的轻微的变化。
在刮痕测试中，没有观察到反应；在测试条件下，铝没有被溶液侵蚀(attack)。
在BAM测试的条件下，在BAM1、BAM2和BAM3中的任一种反应介质中，溶液都没有发生反应，因为没有观察到放热反应。仅仅观察到在BAM1介质中轻微的半透明黄色着色和在BAM2介质中的浅绿色着色。根据BAM4测试，分别在39-41℃、41-41.3℃和41.3-44℃三个温度范围下，收集大约等量的三个馏份。这三个馏份在反应介质中均没有发生反应。没有观察到放热反应，仅观察到了第一个馏份的轻微的浅绿色着色。
实施例3
来自PPG Industries的TDCE被用于制备稳定的TDCE溶液，其中该溶液包括530ppm的环氧丁烷、200ppm的二异丁烯、100ppm的异戊二烯、50ppm的丙酮和10ppm的二乙胺。
在以该溶液进行水解测试的过程中，PH值保持恒定：PH初始值为8.75。100小时后其为8.79。该溶液比实施例2中的溶液的碱性更大。在刮痕测试过程中，没有观察到反应；在测试条件下，铝没有被溶液侵蚀。
在BAM测试条件下，在BAM1、BAM2和BAM3中的任一种反应介质中，溶液都没有发生反应，因为没有观察到放热反应。仅仅观察到在BAM1介质和BAM2介质中的轻微的半透明黄色着色。根据BAM4测试，分别在36.5-37.8℃、37.8-38℃和38-38.2℃三个温度范围下，收集大约等量的三个馏份。从任何一个馏份都没有观察到放热反应或者着色变化。

Claims (19)

1、反-1，2-二氯乙烯的稳定溶液，包含作为添加剂的至少一种酸性接受体、至少一种自由基清除剂、至少一种路易斯碱和至少一种具有缓冲作用的化合物。
2、根据权利要求1中所述的溶液，其特征在于在所述稳定溶液中的每一种添加剂的含量均在10ppm和10000ppm之间，优选在10ppm和1000ppm之间。
3、根据权利要求1或2中所述的溶液，其特征在于添加剂的总含量小于50000ppm，优选小于5000ppm。
4、根据前述权利要求中任一项所述的溶液，其特征在于所述溶液包含200-800ppm的酸性接受体、100-700ppm的自由基清除剂或者自由基清除剂的混合物、10-100ppm的路易斯碱和10-50ppm的具有缓冲作用的化合物。
5、根据前述权利要求中任一项所述的溶液，其特征在于所述酸性接受体是有机环氧化物，优选为环氧丙烷、环氧丁烷或者异丙基缩水甘油醚。
6、根据前述权利要求中任一项所述的溶液，其特征在于所述自由基清除剂是烯烃、杂环或者酚衍生物。
7、根据权利要求6中所述的溶液，其特征在于所述烯烃是二异丁烯、戊烯、异戊二烯或者α-甲基苯乙烯。
8、根据权利要求6中所述的溶液，其特征在于所述杂环是N-甲基吡咯、1，4-二烷或者四氢呋喃。
9、根据权利要求6中所述的溶液，其特征在于所述酚衍生物是苯酚、百里酚或者紫罗兰醇。
10、根据前述权利要求中任一项所述的溶液，其特征在于所述路易斯碱是缩醛、酮、硝基化合物、羧酸酯或者醚。
11、根据权利要求10中所述的溶液，其特征在于所述缩醛是甲缩醛。
12、根据权利要求10中所述的溶液，其特征在于所述酮是丙酮或者甲基乙基酮。
13、根据权利要求10中所述的溶液，其特征在于所述硝基化合物是硝基甲烷或者硝基乙烷。
14、根据权利要求10中所述的溶液，其特征在于所述羧酸酯是甲酸甲酯、乙酸甲酯或者乙酸异丙酯。
15、根据权利要求10中所述的溶液，其特征在于所述醚是叔丁基甲基醚。
16、根据前述权利要求中任一项所述的溶液，其特征在于所述具有缓冲作用的化合物是胺。
17、根据权利要求16中所述的溶液，其特征在于所述胺是三乙胺、N-甲基吗啉、二乙胺或者N，N-二异丙胺。
18、根据权利要求1-4中任一项所述的溶液，其特征在于所述溶液包含环氧丁烷、二异丁烯、异戊二烯、丙酮和二乙胺。
19、根据权利要求18中所述的溶液，其特征在于所述溶液包含200-800ppm的环氧丁烷、100-500ppm的二异丁烯、50-200ppm的异戊二烯、10-100ppm的丙酮和10-50ppm的二乙胺。
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