CN102627716A - Preparation method for polymethacrylate pour point depressant - Google Patents
Preparation method for polymethacrylate pour point depressant Download PDFInfo
- Publication number
- CN102627716A CN102627716A CN2012100874711A CN201210087471A CN102627716A CN 102627716 A CN102627716 A CN 102627716A CN 2012100874711 A CN2012100874711 A CN 2012100874711A CN 201210087471 A CN201210087471 A CN 201210087471A CN 102627716 A CN102627716 A CN 102627716A
- Authority
- CN
- China
- Prior art keywords
- preparation
- pour point
- point depressant
- rohm tech
- esterification
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method for polymethacrylate pour point depressant, which solves the problem that a traditional preparation method utilizes an organic solvent to serve as dehydrant, one of the shortcomings of the method is that in the esterification process, because of long time, pressure in a reaction kettle is high, the kettle extremely easily explode, second, dehydrant is usually a flammable and explosive product, especially toluene commonly used in the esterification process not only is flammable and explosive, but also has toxicity; and third, due to the fact the dehydrant is slightly soluble in water, certain amount of dehydrant is discharged to the natural world in the sewage discharge and causes environment pollution. The preparation method for the polymethacrylate pour point depressant is characterized in that the dehydrant is removed, esterification is performed through a method of vacuum pressure reduction, namely in the esterification process, water produced in the esterification process is absorbed from the reaction kettle by utilizing negative pressure, and the conversion of a esterification reaction is improved. The preparation method for the polymethacrylate pour point depressant has the advantage of overcoming the defects existing in the traditional method.
Description
Technical field
The invention belongs to petroleum oil additive-pour point depressant field, specifically, is a kind of esterification process of producing Rohm tech inc and treatment process of carboxylate color and luster of relating to.
Background technology
The effect of pour point depressant mainly is the condensation point that reduces oil product.Pour point depressant is a kind of polymerization or condensed products of chemosynthesis; Generally contain in its molecule polar group and with the alkyl chain of paraffinic hydrocarbon structural similitude; Absorption through wax crystal surface or with the effect of its formation eutectic, change the shape and size of wax crystallization, prevent that the wax die attachment from forming tridimensional network; Make it generate evenly loose crystal grain, thereby keep oil product flowability at low temperatures.
Rohm tech inc is a kind of functional material that adds in the blended lubricating oil process, and the function of this functional additive is to reduce the zero pour (pour point) of lubricating oil.Its conventional production methods is that starting material are carried out esterification, carboxylate is polymerized again.
Esterification is to produce the indispensable step of Rohm tech inc.Esterification is one type of organic chemical reactions, is alcohol generates ester and water with carboxylic acid or oxygen-containing inorganic acid reaction.For making the water that generates in the esterification process break away from carboxylate, traditional method is to use organic solvent as the band aqua, like benzene, toluene, hexanaphthene etc.This traditional method, its shortcoming one is incessantly reaction kettle of the esterification to be heated in the esterification process, keeps reaction kettle of the esterification at high temperature to move, and constantly produces pressure in the reaction kettle thereby make.Along with the prolongation of time, the pressure in the reaction kettle constantly raises, and very easily blasts; The 2nd, mostly the band aqua is toluene commonly used in the inflammable and explosive product, particularly esterification process, not only inflammable and explosive, and has toxicity, in use, do not note slightly combustion explosion will take place, even intoxication accident; The 3rd, because the band aqua is slightly soluble in water, in sewage discharge, has a certain amount of band aqua and be discharged into occurring in nature, cause environmental pollution.
Summary of the invention
For solving above-mentioned technological technical problem; The objective of the invention is to ban the band aqua, guarantee production safety, environmental protection, smooth running; And the quality that provides a kind of preparation method of Rohm tech inc pour point depressant, the present invention can improve the distillatory yield and improve product.
The objective of the invention is to realize: by C through following scheme
8-C
18Straight-chain fatty alcohol and methylacrylic acid through carrying out the polymkeric substance that esterification generates methylacrylic higher alcohols ester and purifies and under the initiator effect, make through distillation under acid catalysis, the negative-pressure vacuum condition.
The structural formula of the said pour point depressant of the present invention is following:
The preparation method of Rohm tech inc pour point depressant is:
(1) with C
8-C
18Straight-chain fatty alcohol mix according to the 1:1.05-1.2 mol ratio with methylacrylic acid, under the condition that stopper exists,, generate the methylacrylic higher alcohols ester bullion reaction in 95-100 ℃ of esterification 4-6 hour through acid catalysis, reduced vacuum dehydration conditions;
(2) the methylacrylic higher alcohols ester bullion that step (1) is made is neutralized to PH=7 with alkali lye, separates organic layer, and the back is with washing, and saturated common salt is washed, and the reduced vacuum dehydration is again through obtaining methylacrylic higher alcohols ester after the vacuum decompression distillation;
(3) methylacrylic higher alcohols ester that step (2) is made is in the presence of initiator, at N
2Protection in 80 ~ 140 ℃ of reactions 4-8 hours, gets the Rohm tech inc pour point depressant behind the adding thinning oil down, and wherein, methylacrylic higher alcohols ester accounts for 50 ~ 70%, and remainder is a thinning oil; The amount of said initiator is methylacrylic higher alcohols ester: initiator=100:0.1-1.0.
Compared with prior art, the present invention bans the band aqua, carries out esterification with the way of vacuum decompression, promptly in esterification process, with the water that generates in esterification process sucking-off from reaction kettle in time, promotes the conversion of esterification with negative pressure.Such advantage is:
1, in esterification process, need not add the band aqua, ban these starting material of band aqua, save the reaction times of esterification, reduce the cost of product.
2, positive pressure becomes negative pressure in the reaction kettle, and the possibility that makes blast is zero, has eliminated explosive source.
3, the existence of negative pressure of vacuum has been stopped water vapor condensation and has been back in the carboxylate, has improved the transformation efficiency of esterification and has accelerated the speed of reacting, and the reaction times shortens greatly.
4, owing to do not contain the band aqua, the water that esterification generates, aftertreatment promptly reaches emission standard after can directly being neutralized to neutrality, can discharge without the decoupled band aqua, has simplified the program of water treatment, has reduced the cost of water treatment, helps environment protection.
5, ban the band aqua and banned malicious source exactly, making the intoxication accident incidence is zero, has eliminated the hidden danger of intoxication accident.
These advantages have overcome the shortcoming that traditional esterification exists fully.
Distillation is a kind of thermodynamic (al) separating technology, and it utilizes each component boiling point difference in mixing liquid or the liquid-solid system, makes the low boiling component evaporation, and condensation is the associating of evaporation and two kinds of unit operations of condensation to separate the unit process of whole component again.With other separation means, to compare like extraction, column chromatography etc., its advantage do not need to be other solvent beyond the using system component, thereby guarantees can not introduce new impurity.
The tradition distillation of methacrylic ester all is to carry out distillatory through still; Because still distillatory continuous heat supply property is under high vacuum, the high temperature methacrylic ester for a long time, be prone to produce the autohemagglutination coking phenomenon; Greatly influence the distillatory yield, improved the cost of product.
The present invention uses thin-film evaporator that carboxylate is distilled purification; Avoided being in for a long time the pyritous drawback; On yield, improve significantly, and reduce the colourity number of carboxylate, it is light yellow or colourless that carboxylate is become by garnet; Guarantee the appearance requirement of the finished product, improved the quality of product.
Embodiment
One, esterification
Example 1: be equipped with in the 1000 mL there-necked flasks of still head one, add single C
14Fatty Alcohol(C12-C14 and C12-C18) 428g (2mol), the 2.2mol methylacrylic acid, hydroquinone of polymerization retarder 2g, catalyst sulfuric acid 6.2g slowly heats up, and when treating that temperature arrives 60 ℃, the open vacuum pump is to vacuum tightness-0.1mpa, vacuum hydro-extraction.Continue to heat up, 95-100 ℃ of esterification, after about 5 hours, quality does not change in the returnable bottle, and stopped reaction obtains methylacrylic acid tetradecyl alcohol ester bullion.After the bullion that obtains is neutralized to pH=7 with aqueous sodium hydroxide solution, separate organic layer, the organic layer washing, after the saturated common salt washing, open vacuum pump decompression dehydration obtains methylacrylic acid tetradecyl alcohol ester, transformation efficiency 97.5%.
Example 2: be equipped with in the 1000 mL there-necked flasks of still head one, add C
8-C
18Mixed fatty alcohol 417g (2mol), molecular-weight average 208.68, the 2.2mol methylacrylic acid, hydroquinone of polymerization retarder 2g, catalyst sulfuric acid 6.0 g slowly heat up, and when treating that temperature arrives 60 ℃, the open vacuum pump is to vacuum tightness-0.1mpa, vacuum hydro-extraction.Continue to heat up, 95-100 ℃ of esterification, after about 5 hours, quality does not change in the returnable bottle, and stopped reaction obtains mixed methyl vinylformic acid high-carbon alcohol ester bullion.After the bullion that obtains is neutralized to pH=7 with aqueous sodium hydroxide solution, separate organic layer, the organic layer washing, after the saturated common salt washing, open vacuum pump decompression dehydration obtains mixed methyl vinylformic acid high-carbon alcohol ester, transformation efficiency 96.8%.
Example 3:, obtain mixed methyl vinylformic acid high-carbon alcohol ester, transformation efficiency 96.5% with sulfuric acid in the tosic acid 6.0g alternative 2.
Two, distillation is purified
Example 4: start the two stage pump vacuum system, be not higher than 200pa, to the thin-film evaporator heat supply, make evaporator temperature under 180 ~ 220 ℃ of conditions by heating system at vacuum pressure, by esterifying kettle to thin-film evaporator with 0.5 m
3/ h speed is constantly back and forth supplied with methylacrylic higher alcohols ester carboxylate 1700 Kg continuously, obtains light yellow or colourless carboxylate 1630 Kg after 4 hours, distillation yield 95.88%.
Three, polyreaction
Example 5: to a volume is 2 m
3Polymeric kettle input methylacrylic higher alcohols ester carboxylate 750 kg, add initiator Lucidol 3.75 Kg, at N
2Protection in 80-140 ℃ of reaction 4-8 hours, adds the light lubricating oil thinning oil and promptly gets the Rohm tech inc pour point depressant down.
Example 6: the Lucidol with in the Diisopropyl azodicarboxylate alternative 5 of same dosage also obtains the Rohm tech inc pour point depressant.
Method of use of the present invention is: when lube oil blending, add the present invention 0.5% condensation point of the 150SN lubricant base of Dalian Petrochemical Industry Company of PetroChina Company Limited. production is descended 18 ℃; And effectively improve the low temperature flowability of oil product, reach the ability of functional agents such as domestic T803B and international Rohmax V156.
Following table be the present invention at home in the lubricant base according to the pour point depression effect of different dosage ratios
The present invention is the lubricating oil Manufacturing Co., Ltd Success in Experiment on Great Wall, Shenyang.Technology of the present invention is simple, and cost is low, reliable in quality.
Claims (8)
1. the preparation method of a Rohm tech inc pour point depressant is characterized in that it is the polymkeric substance of polymethyl acrylic acid high-carbon alcohol ester, and its preparation method is:
(1) with C
8-C
18Straight-chain fatty alcohol mix according to the 1:1.05-1.2 mol ratio with methylacrylic acid, under the condition that stopper exists,, generate the methylacrylic higher alcohols ester bullion reaction in 95-100 ℃ of esterification 4-6 hour through acid catalysis, reduced vacuum dehydration conditions;
(2) the methylacrylic higher alcohols ester bullion that step (1) is made is neutralized to PH=7 with alkali lye, separates organic layer, and the back is with washing, and saturated common salt is washed, and the reduced vacuum dehydration is again through obtaining methylacrylic higher alcohols ester after the vacuum decompression distillation;
(3) methylacrylic higher alcohols ester that step (2) is made is in the presence of initiator, at N
2Protection in 80-140 ℃ of reaction 4-8 hours, gets the Rohm tech inc pour point depressant behind the adding thinning oil down, and wherein, methylacrylic higher alcohols ester accounts for 50-70%, and remainder is a thinning oil; The amount of said initiator is methylacrylic higher alcohols ester: initiator=100:0.1-1.0.
2. according to the preparation method of the said Rohm tech inc pour point depressant of claim 1, it is characterized in that said straight-chain fatty alcohol is that average carbon number is single carbon alcohol or the mixture of 12-15.
3. according to the preparation method of the said Rohm tech inc pour point depressant of claim 1, it is characterized in that said stopper is a Resorcinol; Said acid is sulfuric acid or tosic acid; Said alkali lye is the aqueous solution of sodium hydroxide.
4. according to the preparation method of the said Rohm tech inc pour point depressant of claim 1, it is characterized in that said vacuum decompression distillation is by thin-film evaporator, two stage pump vacuum system and heating system completion.
5. according to the preparation method of the said Rohm tech inc pour point depressant of claim 4, it is characterized in that said two stage pump vacuum system provides vacuum tightness not to be higher than 200pa.
6. according to the preparation method of the said Rohm tech inc pour point depressant of claim 1, it is characterized in that said distillation temperature is not less than 180 ℃.
7. according to the preparation method of the said Rohm tech inc pour point depressant of claim 1, it is characterized in that said initiator is Lucidol or Diisopropyl azodicarboxylate.
8. according to the preparation method of the said Rohm tech inc pour point depressant of claim 1, it is characterized in that said thinning oil is a light lubricating oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100874711A CN102627716A (en) | 2012-03-29 | 2012-03-29 | Preparation method for polymethacrylate pour point depressant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100874711A CN102627716A (en) | 2012-03-29 | 2012-03-29 | Preparation method for polymethacrylate pour point depressant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102627716A true CN102627716A (en) | 2012-08-08 |
Family
ID=46586127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100874711A Pending CN102627716A (en) | 2012-03-29 | 2012-03-29 | Preparation method for polymethacrylate pour point depressant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102627716A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087235A (en) * | 2013-02-25 | 2013-05-08 | 烟台市牟平区留德润滑油销售有限公司 | Preparation method of condensation point reducer with dual functions of reducing condensation point and turbidity point |
| CN103666539A (en) * | 2013-11-22 | 2014-03-26 | 江苏汉光实业股份有限公司 | Production system for crude oil demulsifier |
| CN104356288A (en) * | 2014-11-25 | 2015-02-18 | 烟台市牟平区留德润滑油销售有限公司 | Production method of pour point depressing and turbidity reducing agent for waste oil recovered lubricant base oil |
| CN104497203A (en) * | 2014-12-12 | 2015-04-08 | 辽宁石油化工大学 | Preparation method of turbidity reducing agent |
| CN105294431A (en) * | 2015-09-14 | 2016-02-03 | 宁波市蓝润能源科技有限公司 | Synthetic ester type thickening agent and preparation method of semisynthetic gear oil using synthetic ester type thickening agent |
| CN108219042A (en) * | 2018-01-16 | 2018-06-29 | 西安石油大学 | A kind of advanced esters pour-point depressant of polymethylacrylic acid, preparation method and application |
| CN110105942A (en) * | 2018-02-01 | 2019-08-09 | 中国石油天然气股份有限公司 | Wax remover and preparation method and application thereof |
| US11028334B2 (en) | 2016-06-28 | 2021-06-08 | China Petroleum & Chemical Corporation | Gradient copolymer, its production and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034001A (en) * | 1987-12-30 | 1989-07-19 | 上海高桥石油化工公司炼油厂 | A kind of preparation method of normal chain alkyl acrylate copolymer |
| CN1168370A (en) * | 1996-02-06 | 1997-12-24 | 巴斯福股份公司 | Continuous preparation of alkyl esters of (meth) acrylic acid |
| CN1298863A (en) * | 2000-12-06 | 2001-06-13 | 北京化学工业集团有限责任公司东方化工厂 | Process for preparing octyl acrylate |
| CN1326431A (en) * | 1998-11-11 | 2001-12-12 | 巴斯福股份公司 | Method for continuous production of (METH) acrylic acid alkyl esters |
| CN1738790A (en) * | 2003-01-13 | 2006-02-22 | 罗姆两合公司 | Improved method for the continuous production of alkyl(meth)acrylates with multiple catalyst recycling |
| CN101041621A (en) * | 2006-11-24 | 2007-09-26 | 中国石油集团工程设计有限责任公司东北分公司 | Method for preparing (methyl) butyl acrylate |
-
2012
- 2012-03-29 CN CN2012100874711A patent/CN102627716A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034001A (en) * | 1987-12-30 | 1989-07-19 | 上海高桥石油化工公司炼油厂 | A kind of preparation method of normal chain alkyl acrylate copolymer |
| CN1168370A (en) * | 1996-02-06 | 1997-12-24 | 巴斯福股份公司 | Continuous preparation of alkyl esters of (meth) acrylic acid |
| CN1326431A (en) * | 1998-11-11 | 2001-12-12 | 巴斯福股份公司 | Method for continuous production of (METH) acrylic acid alkyl esters |
| CN1298863A (en) * | 2000-12-06 | 2001-06-13 | 北京化学工业集团有限责任公司东方化工厂 | Process for preparing octyl acrylate |
| CN1738790A (en) * | 2003-01-13 | 2006-02-22 | 罗姆两合公司 | Improved method for the continuous production of alkyl(meth)acrylates with multiple catalyst recycling |
| CN101041621A (en) * | 2006-11-24 | 2007-09-26 | 中国石油集团工程设计有限责任公司东北分公司 | Method for preparing (methyl) butyl acrylate |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087235A (en) * | 2013-02-25 | 2013-05-08 | 烟台市牟平区留德润滑油销售有限公司 | Preparation method of condensation point reducer with dual functions of reducing condensation point and turbidity point |
| CN103666539A (en) * | 2013-11-22 | 2014-03-26 | 江苏汉光实业股份有限公司 | Production system for crude oil demulsifier |
| CN103666539B (en) * | 2013-11-22 | 2015-03-11 | 江苏汉光实业股份有限公司 | Production system for crude oil demulsifier |
| CN104356288A (en) * | 2014-11-25 | 2015-02-18 | 烟台市牟平区留德润滑油销售有限公司 | Production method of pour point depressing and turbidity reducing agent for waste oil recovered lubricant base oil |
| CN104497203A (en) * | 2014-12-12 | 2015-04-08 | 辽宁石油化工大学 | Preparation method of turbidity reducing agent |
| CN105294431A (en) * | 2015-09-14 | 2016-02-03 | 宁波市蓝润能源科技有限公司 | Synthetic ester type thickening agent and preparation method of semisynthetic gear oil using synthetic ester type thickening agent |
| US11028334B2 (en) | 2016-06-28 | 2021-06-08 | China Petroleum & Chemical Corporation | Gradient copolymer, its production and application thereof |
| CN108219042A (en) * | 2018-01-16 | 2018-06-29 | 西安石油大学 | A kind of advanced esters pour-point depressant of polymethylacrylic acid, preparation method and application |
| CN108219042B (en) * | 2018-01-16 | 2020-07-17 | 西安石油大学 | Polymethacrylate advanced ester pour point depressant, preparation method and application |
| CN110105942A (en) * | 2018-02-01 | 2019-08-09 | 中国石油天然气股份有限公司 | Wax remover and preparation method and application thereof |
| CN110105942B (en) * | 2018-02-01 | 2021-09-28 | 中国石油天然气股份有限公司 | Wax remover and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102627716A (en) | Preparation method for polymethacrylate pour point depressant | |
| CN105368574A (en) | Deacidifying agent decreasing acid value of liquid organic mixtures and preparation technology | |
| CN104447193A (en) | Method for preparing alcohol by reducing alicyclic hydrocarbon carboxylic acid (ester) | |
| CN103937616B (en) | Method for extracting high-purity unsaturated fatty acid from soybean oil | |
| CN103980125A (en) | Synthetic method of isooctyl nitrate | |
| CN110724145A (en) | Synthetic method of medical intermediate 4-chloropyrrolopyrimidine | |
| CN101838197B (en) | Method for preparing 2,2,4-trimethyl-1,3-pentanediol single-isobutyrate | |
| CN105296024A (en) | Multifunctional diesel oil cetane number improver and preparation method thereof | |
| CN104059032A (en) | Preparation method and product of adipate epoxy plasticizer | |
| CN102504891A (en) | Preparation method of glyceryl biofuel additive | |
| CN112321561B (en) | Method for preparing 1, 3-propane sultone from 3-hydroxypropanesulfonic acid | |
| CN105085253A (en) | Preparation technique of long-chain alcohol (methyl)acrylate | |
| CN103739486A (en) | Production method for ethyl acetate crude product | |
| CN108484439B (en) | Preparation method of alpha-formyl-beta-formamido propionitrile alkali metal salt | |
| CN102718654A (en) | Preparation method of a-cyclopentyl methyl mandelate | |
| CN102533241B (en) | Pour point depressant for crude oil | |
| CN106190591A (en) | The esterification of a kind of biodiesel, ester exchange reaction method | |
| CN104530306A (en) | Synthesis method of polymethacrylate pour point depressant | |
| CN103087235A (en) | Preparation method of condensation point reducer with dual functions of reducing condensation point and turbidity point | |
| Toralles et al. | Hydrolysis of waste frying oils in subcritical water for biodiesel production by esterification using a heterogeneous catalyst | |
| CN114479060B (en) | Oil-soluble viscosity reducer for extra-heavy oil and preparation method thereof | |
| CN101314563A (en) | Process for producing pentaerythritol oleate | |
| CN102993009A (en) | Preparation method of glycerin monostearate alpha crystal | |
| CN104693352A (en) | Preparation method of wax-containing crude oil pour-point depressant | |
| CN104693328A (en) | Preparation method of pour-point depressant having dual functions of pour point reduction and turbidity lowering |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120808 |