CN104447457A - 4,4'-methylene bis(dialkyl dithioformamide) preparation method - Google Patents
4,4'-methylene bis(dialkyl dithioformamide) preparation method Download PDFInfo
- Publication number
- CN104447457A CN104447457A CN201310422369.7A CN201310422369A CN104447457A CN 104447457 A CN104447457 A CN 104447457A CN 201310422369 A CN201310422369 A CN 201310422369A CN 104447457 A CN104447457 A CN 104447457A
- Authority
- CN
- China
- Prior art keywords
- preparation
- temperature
- secondary alkylamine
- sodium hydroxide
- hour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a 4,4'-methylene bis(dialkyl dithioformamide) preparation method, which comprises: (1) adding di-n-butylamine to a mixed solution of carbon disulfide and sodium hydroxide in a dropwise manner, maintaining the temperature between 0-30 DEG C, heating to a temperature of 40-60 DEG C after completing the adding of the di-n-butylamine, and continuously reacting for 1-6 h; and (2) adding methylene chloride to the obtained solution in a dropwise manner, heating to a temperature of 50-90 DEG C after completing the adding of the methylene chloride, reacting for 0.5-8 h, and carrying out separation purification to obtain the product. With the method of the present invention, the feeding way of the material is changed, the high risk level carbon disulfide is not required to be added in the dropwise manner, other solvents are not required to be added, the reaction time and the operation steps are saved, the yield is significantly improved, and the product performance is excellent.
Description
Technical field
The invention belongs to organic chemistry filed, relate to a kind of 4, the preparation method of 4 '-methylene-bis (dialkyl dithio methane amide).Specifically, the present invention relates to and secondary for raw material alkylamine, aqueous sodium hydroxide solution, dithiocarbonic anhydride, methylene dichloride are reacted in two steps, prepare the method for lubricating oil additive dialkyl dithio amino formate.
Background technology
Along with the prosperity day by day of the raising of Mechanization Level, particularly automotive industry, lubricating oil industry development is also risen thereupon.But, oil product in use, due to the friction of metallic surface, high temperature, the reason such as moisture and illumination, inevitably oxidizing reaction occur and go bad, thus causing acid value of lubricating oil to increase, viscosity increases, generate greasy filth or precipitation, lubricity reduces greatly; Along with the develop rapidly of modern engine machine technology, the raising of lubricating oil use temperature, accelerates oxidation of lubricating oil reaction; Meanwhile, the strict implement of relevant environmental regulation makes lubricating oil face higher antioxidant property requirement.In oil product, add antioxygen anti-wear agent, effectively can suppress the metamorphic process of oil product, extend the work-ing life of oil product, improve the use properties of oil product.Therefore, develop the lubricating oil additive with antioxidant and antiwear property and become an important topic.
Dialkyl dithio methane amide and metallic salt thereof are the good antioxygen antiwear lubricating oil additives of a class, use in oil product, there are outstanding antioxidant property and good abrasion resistance and extreme pressure property, also there is good oil soluble and the feature such as ashless, without phosphorus simultaneously, be widely used in turbine oil, I. C. engine oil, hydraulic efficiency oil, gear wet goods oil products and lubricating grease.
There are some patents about this product and report both at home and abroad, general is all carry out reacting obtained dialkyl dithio methane amide with secondary alkylamine and methylene dichloride, alkaline solution and dithiocarbonic anhydride, operating process is more loaded down with trivial details, and dithiocarbonic anhydride volatilization is serious, has larger impact to environmental protection and health.
US Patent No. 5744629 discloses the method preparing dialkyl dithio methane amide.First, the aqueous solution of sodium hydroxide and Di-n-Butyl Amine and dithiocarbonic anhydride are reacted in autoclave, control temperature, not higher than 15 DEG C, reacts 0.5 hour, more slowly instills excessive methylene dichloride, and raised temperature gradually, 75 ~ 80 DEG C of reactions 2 hours.After reaction terminates, carry out underpressure distillation in two steps, the first step, carry out at 45 ~ 100 DEG C of temperature and under the pressure of 5 ~ 50kPa, be then separated at 35 ~ 50 DEG C, second step, isolated organic phase is carried out underpressure distillation again, finally can obtain the product that ASlM color is less than 2.The method main purpose improves product colour, adopts low temperature to drip CS
2reaction, the mode of follow-up twice underpressure distillation organic phase reduces colourity, but operation is comparatively loaded down with trivial details.In addition, we test by the method, find that product yield does not have the so high of patent description when material quantity is less.US 3876550 adopts two-step approach to prepare dialkyl dithio methane amide.When considering low-temp reaction, the large mixing of material viscosity is uneven, reaction can be had influence on, so adopt interpolation toluene and Virahol to play diluting effect as solvent, reduce the viscosity of reaction system, but product yield is not high, only have about 40%, add the operating process of solvent recuperation simultaneously, also have partial solvent remaining influence quality product in product in addition.Chinese patent CN 1364759A introduces a kind of with ethanol as solvent, be 10 ~ 60 DEG C of mixed solution and dripping dithiocarbonic anhydride to methylene dichloride, secondary alkylamine and the NaOH aqueous solution three kinds of raw materials in temperature, react 0.5 ~ 5 hour, be warming up to 50 ~ 100 DEG C and continue reaction 1 ~ 12 hour, be separated and obtain product.The method main purpose shortens raw material time for adding, but need to add solvent, to yield and all restricted factor of process costs.
Can find out, prior art is all generally be added drop-wise in secondary amine and sodium hydroxide solution by dithiocarbonic anhydride, the obtained sodium salt of reaction under low temperature, and then adds methylene dichloride and carry out alkylated reaction, and the reaction times is longer, and yield is not high yet.Some also needs separately to add other organic solvents, adds production cost and operation steps.Particularly drip in dithiocarbonic anhydride process, because dithiocarbonic anhydride belongs to inflammable and explosive hazardous chemical, boiling point is low, foul smelling, is difficult to avoid it to volatilize in dropping process, so have very large hidden danger to environment and health.The problems such as in addition, product performance prepared by a lot of method have much room for improvement, and as on the low side in purity, color and luster is bad.
Summary of the invention
The object of the invention is to change charging process thus optimized fabrication method, provide a kind of 4, the novel preparation method of 4 '-methylene-bis (dialkyl dithio methane amide).
The present invention relates to a kind of 4, the preparation method of 4 '-methylene-bis (dialkyl dithio methane amide), adopt two-step synthesis method, in a first step, alkylamine is instilled in dithiocarbonic anhydride and the NaOH aqueous solution, low temperature stirring reaction, generate the sodium salt of dialkyldithiocarbamacompositions, reaction equation is as follows:
In second step, the sodium salt of above-mentioned preparation and methylene dichloride are carried out alkylation coupling and obtains target product, reaction equation is as follows:
Main technical schemes of the present invention: 4, the preparation method of 4 '-methylene-bis (dialkyl dithio methane amide), it is characterized in that the secondary alkylamine of mixed solution and dripping to dithiocarbonic anhydride and sodium hydroxide, maintain the temperature between 0 ~ 30 DEG C, after secondary alkylamine drips off, temperature is risen to 40 ~ 60 DEG C, continue reaction 1 ~ 6 hour; In solution, drip methylene dichloride again, be warming up to 50 ~ 90 DEG C after completing, react 0.5 ~ 8 hour, leave standstill separatory after washing, underpressure distillation obtains product.
A kind of preferred preparation method: to the secondary alkylamine of mixed solution and dripping of dithiocarbonic anhydride and sodium hydroxide under ice bath, maintain the temperature between 0 ~ 25 DEG C, after secondary alkylamine drips off, temperature is risen to 40 ~ 60 DEG C, continue reaction 1 ~ 5 hour; In solution, drip methylene dichloride again, be then warming up to 60 ~ 90 DEG C, react 1 ~ 6 hour, leave standstill separatory after washing, underpressure distillation obtains product.
Usually, the speed control of material dropping dripped off at 0.5 ~ 4 hour; Reaction terminates rear standing separatory, the organic phase deionized water wash obtained 2 ~ 3 times, and vacuum distilling filtration from sodium chloride obtain satisfactory product.Described distillation pressure is 0 ~ 10KPa, and distillation temperature is 40 ~ 100 DEG C.
Described secondary alkylamine is the dialkylamine of carbonatoms 1 ~ 20, preferred Di-n-Butyl Amine.Because secondary alkylamine boiling point is higher, remain and not easily remove in the product, can quality product be affected, so the ratio of other raw material suitably should be increased, to make secondary alkylamine complete, the mol ratio of secondary alkylamine and dithiocarbonic anhydride can be 1:1 ~ 1.7, preferred 1:1 ~ 1.4.The mol ratio of secondary alkylamine and sodium hydroxide can be 1:1 ~ 1.6, preferred 1:1 ~ 1.3.The mol ratio of secondary alkylamine and methylene dichloride can be 1:0.5 ~ 1.0, preferred 1:0.5 ~ 0.8.The mass concentration of aqueous sodium hydroxide solution can be 10% ~ 75%, preferably 13% ~ 50%.
The inventive method changes the feeding manner of material, and without the need to dripping the high dithiocarbonic anhydride of harmful grade, do not need separately to add other solvents, save reaction times and operation steps, yield is significantly increased, and product performance are excellent.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.It should be noted that, these embodiments are not for limiting the scope of the invention, and protection scope of the present invention is as the criterion with appending claims.
Embodiment 1: by 242g(3.15mol) dithiocarbonic anhydride and 636g aqueous sodium hydroxide solution (massfraction is 20%) join in four-hole bottle, start after stirring to drip 394g(3mol) Di-n-Butyl Amine, control temperature is at about 10 DEG C, after 2 hours, Di-n-Butyl Amine drips off, temperature is risen to 50 DEG C, continue reaction 2 hours; 140g(1.65mol is dripped again in solution) methylene dichloride, be warming up to 70 DEG C after within 2 hours, dripping off, react 2.5 hours, reaction terminates.Separatory after washing, under 5KPa condition and 70 DEG C of conditions, underpressure distillation obtains light yellow clear oily liquids, yield 94.3%.Its kinematic viscosity 15.16cSt, nitrogen content 6.81, colourity 0.5.
Embodiment 2: by 251g(3.3mol) dithiocarbonic anhydride and 636g aqueous sodium hydroxide solution (massfraction is 20%) join in four-hole bottle, start after stirring to drip 394g(3mol) Di-n-Butyl Amine, react under ice bath, and maintain the temperature at about 10 DEG C, after 2 hours, Di-n-Butyl Amine drips off, temperature is risen to 50 DEG C, continue reaction 2 hours; 140g(1.65mol is dripped again in solution) methylene dichloride, be warming up to 75 DEG C after within 2 hours, dripping off, react 2.5 hours, reaction terminates.Separatory after washing, under 5KPa condition and 70 DEG C of conditions, underpressure distillation obtains light yellow clear oily liquids, yield 95.1%.Its kinematic viscosity 15.29cSt, nitrogen content 6.78, colourity 1.0.
Embodiment 3: by 242g(3.15mol) dithiocarbonic anhydride and 848g aqueous sodium hydroxide solution (massfraction is 15%) join in four-hole bottle, start after stirring to drip 394g(3mol) Di-n-Butyl Amine, about 15 DEG C are maintained the temperature under ice bath, after 1.8 hours, Di-n-Butyl Amine drips off, temperature is risen to 50 DEG C, continue reaction 2 hours; 187g(1.8mol is dripped again in solution) methylene dichloride, be warming up to 75 DEG C after within 2 hours, dripping off, react 2.5 hours, reaction terminates.Separatory after washing, under 3KPa condition and 75 DEG C of conditions, underpressure distillation obtains light yellow clear oily liquids, yield 95.8%.Its kinematic viscosity 15.56cSt, nitrogen content 6.78, colourity 0.5.
Embodiment 4: by 323g(4.2mol) dithiocarbonic anhydride and 875g aqueous sodium hydroxide solution (massfraction is 20%) join in four-hole bottle, start after stirring to drip 526g(4mol) Di-n-Butyl Amine, maintain the temperature at about 15 DEG C, after 2 hours, Di-n-Butyl Amine drips off, temperature is risen to 55 DEG C, continue reaction 2 hours; 187g(2.2mol is dripped again in solution) methylene dichloride, be warming up to 80 DEG C after within 2 hours, dripping off, react 2 hours, reaction terminates.Separatory after washing, under 3KPa condition and 75 DEG C of conditions, underpressure distillation obtains light yellow clear oily liquids, yield 95.3%.Its kinematic viscosity 15.46cSt, nitrogen content 6.78, colourity 0.5.
Embodiment 5: by 323g(4.2mol) dithiocarbonic anhydride and 875g aqueous sodium hydroxide solution (massfraction is 20%) join in four-hole boiling flask, start after stirring to drip 526g(4mol) Di-n-Butyl Amine, maintain the temperature at about 10 DEG C, after 2 hours, Di-n-Butyl Amine drips off, temperature is risen to 55 DEG C, continue reaction 2.5 hours; 187g(2.2mol is dripped again in solution) methylene dichloride, be warming up to 75 DEG C after within 2 hours, dripping off, react 2.5 hours, reaction terminates.Separatory after washing, under 5KPa condition and 75 DEG C of conditions, underpressure distillation obtains light yellow clear oily liquids, yield 94.9%.Its kinematic viscosity 15.36cSt, nitrogen content 6.72, colourity 1.0.
Comparative example 1: by 394g(3mol) Di-n-Butyl Amine and 636g aqueous sodium hydroxide solution (massfraction is 20%) join in four-hole boiling flask, start after stirring to drip 242g(3.15mol) dithiocarbonic anhydride, about 15 DEG C are maintained the temperature under ice bath, after 2 hours, dithiocarbonic anhydride drips off, temperature is risen to 50 DEG C, continue reaction 2 hours; 187g(1.8mol is dripped again in solution) methylene dichloride, be warming up to 75 DEG C after within 2 hours, dripping off, react 2.5 hours, reaction terminates.Separatory after washing, under 3KPa condition and 75 DEG C of conditions, underpressure distillation obtains red-brown transparent oily liquid, yield 89.2%.Its kinematic viscosity 15.13cSt, nitrogen content 6.65, colourity 2.0.
Comparative example 2: the method illustrated according to US Patent No. 5744629, by 64g(1.6mol) NaOH, 206.8g(1.6mol) Di-n-Butyl Amine and 416g water joins in four-hole bottle, and under agitation mixture is cooled to 5 DEG C.Under agitation by 121.6g(1.6mol) dithiocarbonic anhydride is slowly added in mixture, and makes temperature be no more than 15 DEG C, after adding dithiocarbonic anhydride, continues stirring 0.5 hour.Then 81.6g(excessive 20% is added) methylene dichloride, and temperature is slowly risen to 45 DEG C and carry out alkylated reaction, then react 2 hours at 75 DEG C.Carry out first time underpressure distillation after reaction terminates, steam part water and unreacted material.Carry out underpressure distillation again after standing separation aqueous phase, after washing, obtain light yellow product.Because product is directly that rear separation of washing obtains, the transparency is poor, need distill again and just become clarification.Product yield is 88.1%, its kinematic viscosity 14.11cSt, nitrogen content 6.19, colourity 1.5.
Claims (10)
1. one kind 4, the preparation method of 4 '-methylene-bis (dialkyl dithio methane amide), is characterized in that adding secondary alkylamine in the mixing solutions of dithiocarbonic anhydride and sodium hydroxide, maintains the temperature between 0 ~ 30 DEG C, after secondary alkylamine adds, temperature is risen to 40 ~ 60 DEG C, continue reaction 1 ~ 6 hour; In solution, drip methylene dichloride again, be warming up to 50 ~ 90 DEG C after completing, react 0.5 ~ 8 hour, leave standstill separatory after washing, underpressure distillation obtains product.
2. preparation method according to claim 1, it is characterized in that, in the mixing solutions of dithiocarbonic anhydride and sodium hydroxide, add secondary alkylamine under ice bath, maintain the temperature between 0 ~ 25 DEG C, after secondary alkylamine adds, temperature is risen to 40 ~ 60 DEG C, continue reaction 1 ~ 5 hour; In solution, add methylene dichloride again, be then warming up to 60 ~ 90 DEG C, react 1 ~ 6 hour, leave standstill separatory after washing, underpressure distillation obtains product.
3. preparation method according to claim 1 and 2, is characterized in that, wherein said distillation pressure is 0 ~ 10KPa, and distillation temperature is 40 ~ 100 DEG C.
4. preparation method according to claim 1, is characterized in that, said secondary alkylamine is the secondary alkylamine of carbonatoms 1 ~ 20.
5. the preparation method according to claim 1 or 4, is characterized in that, said secondary alkylamine is Di-n-Butyl Amine.
6. according to the preparation method of claims 1 or 2, it is characterized in that, the speed control that material adds added at 0.5 ~ 4 hour.
7. preparation method according to claim 1, is characterized in that, the mol ratio of secondary alkylamine and dithiocarbonic anhydride is 1:1 ~ 1.7, and the mol ratio of secondary alkylamine and sodium hydroxide is 1:1 ~ 1.6, and the mol ratio of secondary alkylamine and methylene dichloride is 1:0.5 ~ 1.0.
8. according to the preparation method that claim 7 is stated, it is characterized in that, is 1:1 ~ 1.4 with the mol ratio of dithiocarbonic anhydride, and the mol ratio of secondary alkylamine and sodium hydroxide is 1:1 ~ 1.3, and the mol ratio of secondary alkylamine and methylene dichloride is 1:0.5 ~ 0.8.
9. preparation method according to claim 1, is characterized in that, the massfraction of aqueous sodium hydroxide solution used is 10% ~ 75%.
10. according to the preparation method that claim 9 is stated, it is characterized in that, the massfraction of aqueous sodium hydroxide solution used is 13 ~ 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310422369.7A CN104447457B (en) | 2013-09-17 | 2013-09-17 | A kind of preparation method of 4,4 '-di-2-ethylhexylphosphine oxide (dialkyl dithio Methanamide) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310422369.7A CN104447457B (en) | 2013-09-17 | 2013-09-17 | A kind of preparation method of 4,4 '-di-2-ethylhexylphosphine oxide (dialkyl dithio Methanamide) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104447457A true CN104447457A (en) | 2015-03-25 |
| CN104447457B CN104447457B (en) | 2016-09-28 |
Family
ID=52894291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310422369.7A Active CN104447457B (en) | 2013-09-17 | 2013-09-17 | A kind of preparation method of 4,4 '-di-2-ethylhexylphosphine oxide (dialkyl dithio Methanamide) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104447457B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001137A (en) * | 2015-08-13 | 2015-10-28 | 新乡市瑞丰新材料股份有限公司 | Method for preparing dialkyl dithio carbamic acid ester |
| CN107200703A (en) * | 2016-03-18 | 2017-09-26 | 中国石油化工股份有限公司 | The method that Keywords dibutyl dithiocarbamate is prepared using supergravity reactor |
| CN110551047A (en) * | 2019-07-30 | 2019-12-10 | 上海裕诚化工有限公司 | Preparation method of dialkyl dithiocarbamate |
| CN111321028A (en) * | 2018-12-13 | 2020-06-23 | 中国石油天然气股份有限公司 | Ashless antioxidant lubricating oil additive, compound lubricating oil additive and lubricating oil composition containing additives |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015368A (en) * | 1990-06-15 | 1991-05-14 | The Lubrizol Corporation | Ore flotation process using carbamate compounds |
| CN1137518A (en) * | 1995-02-03 | 1996-12-11 | 匈牙利莫尔奥拉加齐帕里有限公司 | Improved process for manufacturing methylene-bis (dibutyl-dithiocarbamate) with ASTM colour less than colour |
| JP2011012043A (en) * | 2009-07-03 | 2011-01-20 | Kawaguchi Kagaku Kogyo Kk | New vulcanization accelerator imparting dynamic durability to vulcanized rubber composition |
-
2013
- 2013-09-17 CN CN201310422369.7A patent/CN104447457B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015368A (en) * | 1990-06-15 | 1991-05-14 | The Lubrizol Corporation | Ore flotation process using carbamate compounds |
| CN1137518A (en) * | 1995-02-03 | 1996-12-11 | 匈牙利莫尔奥拉加齐帕里有限公司 | Improved process for manufacturing methylene-bis (dibutyl-dithiocarbamate) with ASTM colour less than colour |
| JP2011012043A (en) * | 2009-07-03 | 2011-01-20 | Kawaguchi Kagaku Kogyo Kk | New vulcanization accelerator imparting dynamic durability to vulcanized rubber composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001137A (en) * | 2015-08-13 | 2015-10-28 | 新乡市瑞丰新材料股份有限公司 | Method for preparing dialkyl dithio carbamic acid ester |
| CN107200703A (en) * | 2016-03-18 | 2017-09-26 | 中国石油化工股份有限公司 | The method that Keywords dibutyl dithiocarbamate is prepared using supergravity reactor |
| CN107200703B (en) * | 2016-03-18 | 2019-06-04 | 中国石油化工股份有限公司 | The method for preparing Keywords dibutyl dithiocarbamate using supergravity reactor |
| CN111321028A (en) * | 2018-12-13 | 2020-06-23 | 中国石油天然气股份有限公司 | Ashless antioxidant lubricating oil additive, compound lubricating oil additive and lubricating oil composition containing additives |
| CN110551047A (en) * | 2019-07-30 | 2019-12-10 | 上海裕诚化工有限公司 | Preparation method of dialkyl dithiocarbamate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104447457B (en) | 2016-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI408167B (en) | Cyclic diol-derived blocked mercaptofunctional silane compositions | |
| CN104447457A (en) | 4,4'-methylene bis(dialkyl dithioformamide) preparation method | |
| CN102459161A (en) | Process for preparation of alkyl sulfone compounds | |
| CN104736509A (en) | Process for preparing a salt of a sulfurized alkyl-substituted hydroxyaromatic composition | |
| CN106519212A (en) | Polyether sulfonate anionic surfactant, and preparation method and application thereof | |
| US9006482B2 (en) | Process for preparing methylene bis-(dialkylamino-dithioformate) in one step | |
| CN102731349A (en) | Aromatic sulfinic acid compound preparation method | |
| CN105541683A (en) | Method for preparing tetrathioperoxydicarbamic acid | |
| CN105503535A (en) | Mixed base catalyst catalysis-based bisphenol anti-oxidant preparation method and use | |
| CN113430031B (en) | Lubricating grease and preparation method thereof | |
| CN105348161A (en) | Methylene bis(dialkyldithiocarboxamide) production method | |
| CN102807505A (en) | Method for producing phenylhydrazine | |
| CN110194751B (en) | Preparation method of thiadiazole derivative | |
| CN107200703B (en) | The method for preparing Keywords dibutyl dithiocarbamate using supergravity reactor | |
| CN105777537B (en) | A kind of alkylation of salicylic acid method | |
| CN111303060A (en) | Preparation method of metal deactivator | |
| CN112899059A (en) | Chlorine-free low-base-number calcium sulfonate detergent and preparation method thereof | |
| CN105503676A (en) | Safe production method for low-chroma methylene bis(dialkyldithioformamide) | |
| US20090030233A1 (en) | Process for the production of biphenyls | |
| CN103923062B (en) | The precision processing technique of high pressure sulfide isobutene | |
| CN110590702A (en) | Novel method for preparing 2-mercaptobenzothiazole | |
| JPS60127396A (en) | Preparation of detergent of basic alkali earth metal salicylate type | |
| CN115247090B (en) | Ultrahigh-base-number magnesium alkylbenzenesulfonate detergent and preparation method thereof | |
| JP5889030B2 (en) | Method for producing polycyclic aromatic compound | |
| CN107880071A (en) | A kind of preparation method of sulphur phosphoric acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |
|
| CP01 | Change in the name or title of a patent holder |