C): 1.2565, its vapor and air can form an explosive mixture, which will cause combustion and explosion when exposed to open fire and high heat energy; When exposed to air, light and moisture, it gradually decomposes into highly toxic phosgene and hydrogen chloride gas, which can react strongly with oxidants and may generate explosive chloroacetylene with copper and its alloys. Trans-1 2- dichloroethylene is slightly soluble in water, but miscible with ethanol, ether, acetone, benzene and chloroform.
3.Trans-1, 2- dichloroethylene is a high-purity chlorine source, which is mainly used for accelerating oxidation and cleaning furnace tubes in the process of silicon wafer manufacturing, and is an electronic chemical required by semiconductor, discrete devices, micro-electromechanical systems (mems) and photovoltaic manufacturing industries; Trans-1, 2- dichloroethylene can also be used as a solvent for resins and paints, as well as pesticides, dry cleaners, anesthetics, low-temperature extractants, refrigerants and fungicides. Because of its zero odp and gwp, it has been widely used in the field of industrial cleaning agents and solvents, for cleaning, degreasing and degreasing metal parts, substrates, electronic devices and electronic circuit boards, as well as dry cleaning and cleaning clothes and leather.
4. Because anti 1, 2- dichloroethylene is easy to decompose, after the solution is used for a period of time, anti 1, 2- dichloroethylene will decompose to produce corrosive hydrogen chloride gas, which will corrode the cleaned equipment, and harmful gases such as phosgene generated during the decomposition process will also endanger people's health.
5. At present, there are few research contents about anti-1, 2- dichloroethylene in China, and few relevant materials can be found. Generally speaking, the formulation technology of stabilizer is mastered by foreign enterprises. Patent cn 1 871193a discloses an anti1,2- dichloroethylene stabilizer. This stabilization method is to form a stable solution of trans-1 2- dichloroethylene by adding some additives, which contains at least one acid acceptor, at least one free radical scavenger, at least one Lewis base and at least one compound with buffering effect as additives, so that trans-1 2- dichloroethylene can be better applied to fixed surface treatment, that is, cleaning and application.
6. With the development of research, the application of anti-1, 2- dichloroethylene is more and more extensive. Due to its non-destructive effect on the atmosphere, with the increasing awareness of environmental protection, it is of obvious economic and social benefits to vigorously develop anti-1, 2- dichloroethylene products and stabilizers.
Technical realization elements:
7. In order to solve the problem that the existing anti-1, 2- dichloroethylene products are easy to decompose, resulting in obvious harmfulness and pollution, which is easy to cause harm to the environment and human body. However, the existing partial stabilization methods have limitations, especially when a large number of high-concentration stabilizing components are added, which leads to serious component hybridization, and most of them introduce acid and/or alkali components, which will lead to resistance to 65438+.
8. The purpose of the present invention is:
1, realizing the stabilization of trans-1, 2- dichloroethylene in solvent; 2. Ensure the stability of anti-1, 2- dichloroethylene while retaining its original functional characteristics; Third, ensure that the function and performance of the reagent remain normal during use.
9. In order to achieve the above objectives, the present invention adopts the following technical scheme.
10. A solvent for trans-1 2- dichloroethylene, which contains trans-1 2- dichloroethylene and an antioxidant is added to it; The antioxidant is p-tert-butylcatechol.
1 1. In this scheme, p-tert-butylcatechol is used as an antioxidant, firstly because trans-1, 2- dichloroethylene decomposes to produce phosgene and hydrogen chloride gas, and this process is mainly stimulated by oxidation. Under the action of oxygen, trans-1, 2- dichloroethylene is oxidized and decomposed to produce the above toxic gas. However, after research and experiments, the results show that the mixture of the two can effectively inhibit the reactivity of trans-1, 2- dichloroethylene with oxygen, resulting in a "passivation" effect, and the passivation effects of the two are mutual. Appropriate addition of p-tert-butylcatechol can block the reaction between oxygen and them and achieve mutual stability.
12. Moreover, it is found through experiments that the anti-1 2- dichloroethylene solvent with p-tert-butylcatechol as a stable component is more effective for metal treatment and can effectively prevent metal corrosion, such as cleaning, degreasing and deoiling of non-copper metal parts, substrates and electronic devices in wafer manufacturing, but it is still not perfect for copper-containing metal parts, substrates and electronic devices.
13. Preferably, the addition amount of p-tert-butylcatechol is 0.0 1 ~ 0.02 wt% of trans-1 2- dichloroethylene.
14. Due to the interaction between them, the dosage of p-tert-butylcatechol should be controlled at ≮0.0 1.00wt% trans-1, 2- dichloroethylene, otherwise it will be passivated unilaterally. However, when the dosage of p-tert-butylcatechol is too large, it will not only inhibit the free functional characteristics of trans 1, 2- dichloroethylene, but also lead to effect saturation due to dynamic interaction, that is, the dosage is higher than 0.02 wt% of trans 1, 2- dichloroethylene, which will not produce better stability effect, and will easily lead to the stability of p-tert-butylcatechol itself.
15. A solvent for trans-1 2- dichloroethylene, which contains trans-1 2- dichloroethylene, and an antioxidant is added to it; The antioxidant is thymol.
16. Thymol is also an antioxidant, but it is different from p-tert-butylcatechol. First of all, thymol has high stability and usually has the function of indicator. However, in the technical scheme of the invention, thymol can be used as an antioxidant to block the oxidative decomposition process of trans-1, 2- dichloroethylene to a certain extent because of its reducibility. On the other hand, compared with p-tert-butylcatechol, the main effective groups of thymol are phenolic hydroxyl groups, which are in trans -65438.
17. Preferably, the addition amount of thymol is 0.03-0.05 wt% of trans-1 2- dichloroethylene.
18. To sum up, insufficient thymol addition will lead to insufficient phenolic hydroxyl groups, which can not effectively stabilize trans-1 2- dichloroethylene and prevent its oxidative decomposition. However, excessive thymol addition is stable, but it is easy to waste resources and excessively inhibit trans-1, 2- dichloroethylene.
19. In addition, thymol-stabilized anti-1 2- dichloroethylene reagent is more suitable for the preparation of dry cleaning reagents such as clothes and leather, as well as the dilution of silicone oil and fluorine oil, and the preparation of functional reagents such as resin, insecticide, anesthetic, low-temperature extractant, refrigerant and bactericide, but when used for the treatment of metal parts, the storage time cannot exceed three weeks.
20. A solvent of trans-1, 2- dichloroethylene, which contains trans-1, 2- dichloroethylene, and an antioxidant is added thereto; The antioxidant is 2,6-di-tert-butyl-p-phenol.
21.2,6-di-tert-butyl-p-phenol has higher stability than thymol and p-tert-butylcatechol in the system of the present invention, but its stabilizing effect is relatively weak. But unlike thymol and p-tert-butylcatechol, it can be very effectively used to use copper and copper alloys through trans-1, 2- dichloroethylene. Because trans-1, 2- dichloroethylene has different effects on copper and copper alloys, it reacts with oxygen to produce phosgene and hydrogen chloride, while it reacts with copper and copper alloys to produce chloroacetylene. It has been proved that thymol and p-tert-butylcatechol can delay the reaction of trans-1, 2- dichloroethylene with copper and copper alloys to a certain extent, but they cannot completely produce chloroacetylene. Therefore, the anti-1, 2- dichloroethylene reagent mixed with anti-1, 2- dichloroethylene and 2,6-di-tert-butyl-p-phenol is most suitable for the use of copper and copper alloy materials, but in other aspects, it can also be used to prepare dry cleaning agents. However, it is still the best choice for cleaning, degreasing and degreasing copper-containing metal parts, substrates and electronic devices in wafer manufacturing.
22. Preferably, the addition amount of 2,6-di-tert-butyl-p-phenol is 0.08-0.1wt% of that of trans-/kloc-0, 2- dichloroethylene.
23. Because the stabilizing effect of 2,6-di-tert-butyl-p-phenol on trans-1 2- dichloroethylene is limited, a higher concentration is needed to match it. But too high concentration will also affect the effect of anti-1, 2- dichloroethylene.
24. A solvent of trans-1, 2- dichloroethylene, which contains trans-1, 2- dichloroethylene, and an antioxidant is added thereto; The antioxidant is hydroquinone.
25. When hydroquinone is used in the anti-1, 2- dichloroethylene reagent system of the present invention, it has a relatively optimal stabilizing effect, and can also produce excellent stabilizing effect at extremely low concentration. But relatively speaking, due to its own harmfulness and stability, it is necessary to strictly control its dosage. This kind of anti-1, 2- dichloroethylene solvent is suitable for the preparation of resin, paint and leather dry cleaning agents, and is preferably used for cleaning, degreasing and degreasing non-copper metal parts, substrates and electronic devices in wafer manufacturing. The addition of hydroquinone is 0.005 ~ 0.438+of trans-65438,2-dichloroethylene.
26. The reason why the dosage of hydroquinone is controlled at a low level is that it has a good stabilizing effect on trans-1 2- dichloroethylene, and at the same time, because of its certain harmfulness, the content of control agent is required to be low.
27. An application of an anti-1, 2- dichloroethylene solvent for wafer manufacturing and/or preparation of a functional solvent.
28. The invention can be used in the application field of preparing the stable solvent of trans 1 2- dichloroethylene after the original trans 1 2- dichloroethylene is stabilized by different antioxidants.
29. Preferably, the functional solvent includes resin, paint, insecticide, dry cleaning agent, anesthetic, low-temperature extractant, refrigerant or bactericide.
30. The invention has the advantages that: 1) the stability of trans-1, 2- dichloroethylene in the solvent is realized, and the reaction and decomposition with various components are avoided; 2) The functionality of anti-1, 2- dichloroethylene is effectively maintained, and it can be effectively used in the application field of anti-1, 2- dichloroethylene.
expand on
3 1. The present invention will be described in detail through specific examples. Based on these descriptions, those skilled in the art will be able to realize the present invention. In addition, the embodiments of the present invention mentioned in the following description are usually only a part of the embodiments of the present invention, but not all the embodiments. Therefore, based on the embodiments in the present invention, all other embodiments obtained by ordinary people in the field without creative labor should belong to the protection scope of the present invention.
32. Unless otherwise specified, the raw materials used in the embodiments of the present invention are all commercially available or available to those skilled in the art; Unless otherwise specified, the methods used in the embodiments of the present invention are all methods mastered by those skilled in the art. ..
33. Example 1, 2- dichloroethylene antisolvent has the following composition ratio: Example 2 anti 1, 2- dichloroethylene solvent has the following composition ratio: Example 3 anti 1, 2- dichloroethylene solvent has the following composition ratio: The composition is as follows: Example 5 a kind of anti 1,
34. As can be seen from the above table, it is basically impossible to stabilize trans-1, 2- dichloroethylene by adding a very small amount of p-tert-butylcatechol. For example, by comparing the # 1 sample with the #0 control sample, it can be found that the mill scale corrosion trend of the two samples tends to be the same, and the solution sample remains clear within 30 days, indicating that it has anticorrosion effect from the beginning. The anti-68+0 samples and sample solutions # 2 ~ # 4 can keep the iron sheet in a normal corrosion-free state for 30 days, which shows that the anti-1, 2- dichloroethylene solvent is stable and can inhibit the corrosion of iron sheet. On the other hand, the #5 sample was corroded by iron scales on the first day 10, and the sample solution was obviously turbid on the 25th day, which indicated that the excessive addition of p-tert-butylcatechol inhibited the functionality of trans 1 2- dichloroethylene itself, and the verified corrosion finally polluted the sample solution, resulting in the turbidity of the sample solution.
35. The trans-1 2- dichloroethylene solvent in Example 6 has the following composition ratio: the trans-1 2- dichloroethylene solvent in Example 7 has the following composition ratio: the trans-1 2- dichloroethylene solvent in Example 8 has the following composition ratio: the trans-dichloroethylene solvent in Example 9.
In experiment 2, the anti-1 2- dichloroethylene solvents in the above example 6 ~ 10 were respectively numbered as # 6 ~ # 10 samples, and the anti-1 2- dichloroethylene was compared as #0 samples, and the samples were sent to # 6 ~ #/kloc-.
36. It can also be seen from the above table that the effect of thymol on stabilizing trans-1, 2- dichloroethylene increases with the increase of its concentration. However, sample #7 also shows that it is not suitable for treating metal parts like sample # 1 2, which is stabilized by p-tert-butyl catechol. When #8 sample is used to prepare leather dry cleaning agent, its use effect is basically the same as that of #0 sample, and the effective service life of leather dry cleaning agent can be extended by at least 60 days, that is, the shelf life can be extended by at least 2 months. However, when Sample #3 was used to prepare leather dry cleaning agent, it was found that some leather was damaged. Therefore, the application field of the obtained trans-1, 2- dichloroethylene should be further determined according to the selection and addition amount of stabilizer.
37. Example 1 1, 2- dichloroethylene solvent has the following composition ratio: Example 1, 2- dichloroethylene solvent has the following composition ratio: Example 1, 2- dichloroethylene solvent. The composition is as follows: Example 14 trans-1, 2- dichloroethylene solvent has the following composition ratio:
Experiment 3 The samples of anti-1, 2- dichloroethylene solvent in the above example 1 ~15 were numbered #1~ #15 respectively, and the samples were anti-15.
38. As can be seen from the data in the above table, the stability of 2,6-di-tert-butyl-p-phenol is weaker than that of p-tert-butyl catechol and thymol. Although the stable and effective time of trans 1, 2- dichloroethylene can be prolonged, the actual effect is relatively poor, even prolonged to a certain extent, as shown in sample # 1 1, which not only
39. However, the copper sheet test was carried out to determine whether chloroacetylene was produced under safe conditions. The copper sheet test is the same as the above test, except that the iron sheet is replaced by copper sheet, and it is observed, detected and recorded every 5 minutes to see if chloroacetylene is detected. Stop the test immediately after detecting chloroacetylene to ensure the safety of the test and obtain the data in the following table.
40. In the table: not detected.
*
It shows that although chloroacetylene was not detected, the copper sheet was corroded.
4 1. As can be seen from the above table, 2,6-di-tert-butyl-p-phenol-stabilized trans-1, 2- dichloroethylene is relatively stable.
Poor, it can be used to treat copper and copper-containing alloys more effectively. It solves the problem that the original treatment of copper and copper alloys with trans-1, 2- dichloroethylene has great potential safety hazards.
42. Example 1, 2- dichloroethylene solvent has the following composition ratio: Example 1, 2- dichloroethylene solvent has the following composition ratio: Example 18 trans 1. 2- dichloroethylene solvent, its composition is as follows: Example 20: An anti-/kloc-0, 2- dichloroethylene solvent, its composition is as follows: Experiment 4: The anti-1 2- dichloroethylene solvent of the above example 16 ~ 20 is numbered # 1 6 ~ respectively.
43. As can be seen from the above table, the stabilization effect of hydroquinone is better than the other three stabilizing components, and the stabilization time of trans-1 2- dichloroethylene can be prolonged by adding a small amount of # 16. But from the #20 sample and test me ~
It can be seen from some high-concentration samples in iii that in the anti-1, 2- dichloroethylene solvent of the present invention, the antioxidant and anti-1, 2- dichloroethylene keep the anti-1, 2- dichloroethylene stable through competition, so the stability will be weakened or cause anti-65433 no matter whether the stabilizer concentration is too high or too low. The functionality of 2- dichloroethylene itself is inhibited, so the selection of antioxidant types and the adjustment of dosage are the key cores of the invention. In view of the effects of different antioxidants, the technical scheme of the invention has also been studied correspondingly, and it is found that adding and using 2,6-di-tert-butyl in phenol can further make trans-1, 2- dichloroethylene effectively used in the treatment of copper and copper alloy parts.