CN1132813C - Dithiocarbamate derivative and its prepn and application - Google Patents
Dithiocarbamate derivative and its prepn and application Download PDFInfo
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- CN1132813C CN1132813C CN 00107809 CN00107809A CN1132813C CN 1132813 C CN1132813 C CN 1132813C CN 00107809 CN00107809 CN 00107809 CN 00107809 A CN00107809 A CN 00107809A CN 1132813 C CN1132813 C CN 1132813C
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Abstract
The present invention relates to a dithiocarbamate derivant with a structure as the right formula. The dithiocarbamate derivant is prepared by reacting the organic ammonium salt of N, N-dialkyl-dithiocarbamic acid or metal salt and 3, 5-dialkyl-4-hydroxyl phenyl propionyl chloride, and can be used as antioxygen antiwear additive in lubricating oil and lubricating grease.
Description
The present invention relates to contain the dithiocarbamate derivative that shields phenol, its preparation method and as the application of lubricating oil additive.
Lubricating oil in use, oxidizing reaction will inevitably take place in the reasons such as friction, high temperature, moisture and light owing to the metallic surface, thereby causes that acid value of lubricating oil increases, viscosity increases, greasy filth forms, lubricity degenerates; The existence of metallic surface metal ion simultaneously, catalysis oxidizing reaction, further quicken the process of ruining of lubricating oil.When the loss of this lubricity acquires a certain degree, will cause the corrosion and the damage of parts, finally may cause scrapping of whole instrument device.As seen, the antioxidant property of lubricating oil is extremely important.Adding oxidation inhibitor is a kind of simple but effective method.T501 oxidation inhibitor (2,6 di tert butyl 4 methyl phenol) as adding 0.5% in transformer oil just can be brought up to thousands of hours from tens hours with its oxidation induction period.
Along with the develop rapidly of modern engine technology, the oxidation of lubricating oil reaction has been quickened in the raising of lubricating oil use temperature; Simultaneously, environmental regulation more strictness and engine exhaust recycles The Application of Technology, also makes lubricating oil face higher antioxidant property requirement.These variations make the development of the better oxidation inhibitor of performance become an important topic.
Ashless dithiocarbamate and metallic salt thereof are antioxygen wear preventive additives preferably.US5,019,284 discloses a kind of dialkyl dithio amino formate derivative that contains bound phosphate groups; US5,120,457 disclose a kind of organic ammonium salt of dialkyl dithio amino formate or the derivative of metal-salt and benzene sulfonyl chloride reaction generation.
The shielding phenolic compound is that a class is used very early but highly effective oxidation inhibitor, as: Industrial products such as T501, T502.But this kind antioxidant is under high-temperature situation, and antioxygen property can descend.The trade mark that Ciba-Geige company produces be the oxidation inhibitor of L-135 by the combining of shielding phenol and alkyl carboxylic acid ester, improved the use temperature of oxidation inhibitor.
Be to the object of the invention to provide a kind of dithiocarbamate derivative that shields phenol that contains.
Another object of the present invention provides the preparation method of above-claimed cpd.
A further object of the present invention provides the application method of above-claimed cpd.
Compound provided by the invention has following structure:
Wherein, R
1, R
2Be identical or different C
3～C
16Alkyl, preferred alkyl, aryl and cycloalkyl, more preferably C
3～C
12Alkyl, R
3, R
4Be identical or different C
1～C
10Alkyl, preferred C
1～C
8Alkyl.
Compound provided by the invention has two kinds of preparation methods, and first kind of preparation method comprises:
Make N, the organic ammonium salt of N-dialkyl-dithiocarbamic acid and 3,5-dialkyl group-4-hydroxybenzene propionyl chloride are at 10～150 ℃, and preferred 40～120 ℃ were reacted preferred 4～9 hours 1～12 hour.
The organic ammonium salt of said dialkyldithiocarbamates can be reacted in organic solvent by tertiary amine, secondary amine and dithiocarbonic anhydride and make.Tertiary amine wherein can be triethylamine, Tributylamine, piperidines, can stand pyridine etc., preferred triethylamine.Said secondary amine can be dialkylamine, diarylamine, cycloaliphatic amines, heterocyclic amine or its mixture, preferred two-2 ethyl hexylamine, Di-n-Butyl Amine, diethyl nonyl amine, two positive nonyl amines, two n-Decylamines and cyclohexyl hexylamine etc.Said organic solvent can be benzene,toluene,xylene, hexane etc.
Is example with triethylamine as raw material, and the reaction formula of preparation compound (I) is as follows:
Second kind of preparation method comprises:
Make N, the metal-salt of N-dialkyl-dithiocarbamic acid and 3,5-dialkyl group-4-hydroxybenzene propionyl chloride are at 10～150 ℃, and preferred 50～120 ℃ were reacted preferred 2～10 hours 1～12 hour.
The metal-salt of said dialkyldithiocarbamates can be reacted in the aqueous solution by corresponding metal oxyhydroxide, secondary amine and dithiocarbonic anhydride and make.Said metal hydroxides is basic metal or alkaline earth metal hydroxides.Said secondary amine is identical with the definition of secondary amine among first kind of preparation method.
Is example with sodium hydroxide as raw material, and the reaction formula of preparation compound (I) is as follows:
3,5-dialkyl group-4-hydroxybenzene propionyl chloride be prepared as routine techniques, can be by 3,5-dialkyl group-4-hydroxy phenylpropionic acid reacts with thionyl chloride and makes.Alkyl wherein is C
1～C
10Alkyl, preferred C
1～C
8Alkyl, more preferably methyl, the tertiary butyl and uncle's octyl group.
The compounds of this invention will shield the phenol antioxidant group and combine with the dithiocarbamate with abrasion resistance, have antioxygen and abrasion resistance simultaneously, can be used as the antioxygen wear preventive additive in lubricating oil and the lubricating grease.
Below by embodiment the present invention is further described.
Embodiment 1
Present embodiment is the preparation of the organic ammonium salt of dialkyldithiocarbamates.
Be equipped with in the there-necked flask of agitator, thermometer, temperature regulator and return line at 250ml, add Di-n-Butyl Amine 12.9g (0.1mol) and triethylamine 10.1g (0.1mol), and adding 100ml toluene, mix, slowly drip dithiocarbonic anhydride 9.2g (0.12mol), dropwised in 40 minutes, be warmed up to 60 ℃, continued stirring reaction 2 hours, stopped reaction, solution for later use.
Embodiment 2
Present embodiment is the preparation of the organic ammonium salt of dialkyldithiocarbamates.
Replace Di-n-Butyl Amine with the 0.1mol nonyl amine, other reaction conditions is with embodiment 1.
Embodiment 3
Present embodiment is the preparation of the organic ammonium salt of dialkyldithiocarbamates.
Replace Di-n-Butyl Amine with 0.1mol cyclohexyl hexylamine, other reaction conditions is with embodiment 1.
Embodiment 4
Present embodiment is the preparation of the metal-salt of dialkyldithiocarbamates.
Be equipped with in the there-necked flask of agitator, thermometer, temperature regulator and return line at 250ml, add Di-n-Butyl Amine 12.9g (0.1mol) and sodium hydroxide 4.0g (0.1mol), and add 100ml toluene, mix, slowly drip dithiocarbonic anhydride 9.2g (0.12mol), dropwised in 40 minutes, and be warmed up to 60 ℃, continued stirring reaction 2.5 hours, stopped reaction, solution uses dried over mgso stand-by with the extraction of 200ml toluene, branch vibration layer, toluene layer.
Embodiment 5
Present embodiment is the preparation of the metal-salt of dialkyldithiocarbamates.
Replace Di-n-Butyl Amine with 0.1mol cyclohexyl hexylamine, other reaction conditions is with embodiment 4.
Embodiment 6
Present embodiment is 3, the preparation of 5-di-t-butyl-4-hydroxybenzene propionyl chloride.
Be equipped with agitator, thermometer, temperature regulator, return line, be connected with in the there-necked flask of gas absorption cell at 250ml, add 3,5-di-t-butyl-4-hydroxy phenylpropionic acid 27.8g (0.1mol), benzene 100ml, thionyl chloride 13.1g (0.13mol), dropwise half an hour, is warming up to 80 ℃ of reactions 4 hours, stopped reaction, solution is preserved with the moisture proof device.
Embodiment 7
Present embodiment is the preparation of compound (I).
Be equipped with in the there-necked flask of agitator, thermometer, temperature regulator and return line at 250ml, add the solution that embodiment 6 obtains, slowly drip the solution that embodiment 1 obtains then, in 2 hours, dropwise, occur white precipitate in the flask, be warming up to 90 ℃, react 6 hours stopped reaction, be chilled to room temperature, remove by filter precipitation, filtrate water is washed till neutrality, use dried over mgso, remove and desolvate, promptly get red-brown transparent liquid compd A, through the field desorptiion mass spectroscopy, molecular weight is 463.
Embodiment 8
Present embodiment is the preparation of compound (I).
Be equipped with in the there-necked flask of agitator, thermometer, temperature regulator and return line at 250ml, add the solution that embodiment 6 obtains, slowly drip the solution that embodiment 2 obtains then, in 2 hours, dropwise, occur white precipitate in the flask.Be warming up to 70 ℃, react 8 hours stopped reaction.Be chilled to room temperature, remove by filter precipitation, filtrate water is washed till neutrality, uses dried over mgso, removes and desolvates, and gets a red-brown transparent liquid compd B, and through the field desorptiion mass spectroscopy, molecular weight is 603.
Embodiment 9
Present embodiment is the preparation of compound (I).
Be equipped with in the there-necked flask of agitator, thermometer, temperature regulator and return line at 250ml, add the solution that embodiment 6 obtains, slowly drip the solution that embodiment 3 obtains then, in 2 hours, dropwise, occur white precipitate in the flask.Be warming up to 50 ℃, react 9 hours stopped reaction.Be chilled to room temperature, remove by filter precipitation, filtrate water is washed till neutrality, uses dried over mgso, removes and desolvates, and gets a red-brown transparent liquid Compound C, and through the field desorptiion mass spectroscopy, molecular weight is 420.
Embodiment 10
Present embodiment is the preparation of compound (I).
Be equipped with in the there-necked flask of agitator, thermometer, temperature regulator and return line at 250ml, add the solution that embodiment 6 obtains, slowly drip the solution that embodiment 4 obtains then, in 2 hours, dropwise, occur white precipitate in the flask.Be warming up to 50 ℃, react 10 hours stopped reaction.Be chilled to room temperature, remove by filter precipitation, filtrate water is washed till neutrality, uses dried over mgso, removes and desolvates, and gets a red-brown transparent liquid compd A, and through the field desorptiion mass spectroscopy, molecular weight is 463.
Embodiment 11
Present embodiment is the preparation of compound (I).
Be equipped with in the there-necked flask of agitator, thermometer, temperature regulator and return line at 250ml, add the solution that embodiment 6 obtains, slowly drip the solution that embodiment 5 obtains then, in 2 hours, dropwise, occur white precipitate in the flask.Be warming up to 90 ℃, react 10 hours stopped reaction.Be chilled to room temperature, remove by filter precipitation, filtrate water is washed till neutrality, uses dried over mgso, removes and desolvates, and gets a red-brown transparent liquid Compound C, and through the field desorptiion mass spectroscopy, molecular weight is 603.
Embodiment 12
Present embodiment is the antioxygen property test.
Prepared compd A, B, C are joined in the HVIS150SN base oil with 0.5% heavy dosage respectively, be rotated its antioxygen of oxygen bomb measuring, contrast with the base oil that does not add oxidation inhibitor.Experiment condition: oil sample weight 50 grams, catalyzer is a copper wire, oxygen pressure 0.62MPa/m
2, 150 ℃ of experimental temperatures.The results are shown in Table 1.
Table 1
| Prescription | Oil sample | Additive | Inductive phase (minute) |
| 1 | Base oil | Do not have | 34 |
| 2 | Base oil | Compd A | 107 |
| 3 | Base oil | Compd B | 110 |
| 4 | Base oil | Compound C | 98 |
As can be seen from Table 1, The compounds of this invention has tangible antioxidant effect.
Embodiment 11
Present embodiment is the abrasion resistance test.
Prepared compd A, B, C are joined in the HVIS1 50SN base oil with 1.0% heavy dosage respectively, carry out the experiment of four balls.Experiment condition: 20 kilograms of loads, 60 ℃ of temperature, 60 minutes time, 1200 rev/mins of rotating speeds.The results are shown in Table 2.
Table 2
| Prescription | Oil sample | Additive | Wear scar diameter (millimeter) |
| 1 | Base oil | Do not have | 0.82 |
| 2 | Base oil | Compd A | 0.40 |
| 3 | Base oil | Compd B | 0.38 |
| 4 | Base oil | Compound C | 0.46 |
As can be seen from Table 2, The compounds of this invention has tangible wear-resistant effect.
Claims (13)
1. dithiocarbamate derivative has following structure:
Wherein, R
1, R
2Be identical or different C
3～C
16Alkyl, R
3, R
4Be identical or different C
1～C
10Alkyl.
2. compound according to claim 1 is characterized in that R
1, R
2Be C
3～C
12Alkyl, R
3, R
4Be C
1～C
8Alkyl.
3. the preparation method of the described compound of claim 1, be to make N, the organic ammonium salt of N-dialkyl-dithiocarbamic acid and 3,5-dialkyl group-4-hydroxybenzene propionyl chloride were 10～150 ℃ of reactions 1～12 hour, and said organic ammonium salt is made by tertiary amine, secondary amine and dithiocarbonic anhydride reaction.
4. preparation method according to claim 3 is characterized in that 40～120 ℃ of temperature of reaction, 4～9 hours reaction times.
5. preparation method according to claim 3 is characterized in that said tertiary amine is selected from triethylamine, Tributylamine, piperidines, can stands pyridine.
6. preparation method according to claim 3 is characterized in that, said secondary amine is selected from dialkylamine, diarylamine, cycloaliphatic amines, heterocyclic amine or its mixture.
7. according to claim 3 or 6 described preparation methods, it is characterized in that said secondary amine is selected from two-2 ethyl hexylamine, Di-n-Butyl Amine, diethyl nonyl amine, two positive nonyl amines, two n-Decylamines and cyclohexyl hexylamine.
8. the preparation method of the described compound of claim 1, be to make N, the metal-salt of N-dialkyl-dithiocarbamic acid and 3,5-dialkyl group-4-hydroxybenzene propionyl chloride is at 10～150 ℃, reacted 1～12 hour, said metal-salt is made by corresponding metal oxyhydroxide, secondary amine and dithiocarbonic anhydride reaction.
9. preparation method according to claim 8 is characterized in that 50～120 ℃ of temperature of reaction, 2～10 hours reaction times.
10. preparation method according to claim 8 is characterized in that said metal hydroxides is basic metal or alkaline earth metal hydroxides.
11. preparation method according to claim 8 is characterized in that, said secondary amine is selected from dialkylamine, diarylamine, cycloaliphatic amines, heterocyclic amine or its mixture.
12. according to Claim 8 or 11 described preparation methods, it is characterized in that said secondary amine is selected from two-2 ethyl hexylamine, Di-n-Butyl Amine, diethyl nonyl amine, two positive nonyl amines, two n-Decylamines and cyclohexyl hexylamine.
13. the described application of compound of claim 1 is as the antioxygen wear preventive additive in lubricating oil and the lubricating grease.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00107809 CN1132813C (en) | 2000-06-22 | 2000-06-22 | Dithiocarbamate derivative and its prepn and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00107809 CN1132813C (en) | 2000-06-22 | 2000-06-22 | Dithiocarbamate derivative and its prepn and application |
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| Publication Number | Publication Date |
|---|---|
| CN1332156A CN1332156A (en) | 2002-01-23 |
| CN1132813C true CN1132813C (en) | 2003-12-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00107809 Expired - Lifetime CN1132813C (en) | 2000-06-22 | 2000-06-22 | Dithiocarbamate derivative and its prepn and application |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272892B (en) * | 2014-06-05 | 2019-01-29 | 中国石油化工股份有限公司 | A kind of shielding phenolic compounds, its manufacturing method and its application as antioxidant |
| CN105315183B (en) * | 2014-06-05 | 2019-02-01 | 中国石油化工股份有限公司 | A kind of shielding phenolic compounds, its manufacturing method and its application as antioxidant |
| CN105481741A (en) * | 2015-12-28 | 2016-04-13 | 山东源根石油化工有限公司 | Hindered-phenol-containing phenylenediaminothioformate, antioxidant containing compound and application thereof in gas engine lubricating oil |
| CN108048163B (en) * | 2018-01-19 | 2021-02-26 | 东莞理工学院 | Dithiocarbamic acid group s-triazine derivative multifunctional lubricating oil additive and preparation method and application thereof |
| CN109928978B (en) * | 2019-05-05 | 2021-04-23 | 湖南科技大学 | 5,10,15, 20-tetraaryl-3-sulfur-2-nitrogen-21-carbon chlorophyll compound and preparation method thereof |
-
2000
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