CN101613273B - Method for preparing dimeric acid methyl ester - Google Patents
Method for preparing dimeric acid methyl ester Download PDFInfo
- Publication number
- CN101613273B CN101613273B CN200910159634.0A CN200910159634A CN101613273B CN 101613273 B CN101613273 B CN 101613273B CN 200910159634 A CN200910159634 A CN 200910159634A CN 101613273 B CN101613273 B CN 101613273B
- Authority
- CN
- China
- Prior art keywords
- acid methyl
- methyl ester
- ionic liquid
- cation
- alkylsulfonic acid
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种双酸性离子液体催化不饱和脂肪酸甲酯二聚制备二聚酸甲酯的方法，其特征是采用烷基磺酸功能化的吡啶阳离子或烷基磺酸功能化的1，3-二烷基咪唑阳离子或烷基磺酸功能化的季铵盐阳离子与Lewis酸性的无机阴离子构成的双酸性离子液体作为催化剂；在氮气保护下、反应温度220～280℃、反应时间2～8小时催化脂肪酸甲酯聚合反应制备二聚酸甲酯，与现有技术相比：1.具有更高的聚合能力，无需加压且反应时间短。2.二聚酸甲酯产物与离子液体催化剂不相混溶而自行分层，使分离过程更为容易。3.催化剂离子液体性能稳定，可循环使用。The present invention relates to a The method for preparing dimer acid methyl ester by catalyzing the dimerization of unsaturated fatty acid methyl ester with bis-acidic ionic liquid is characterized in that it adopts alkylsulfonic acid functionalized pyridinium cation or alkylsulfonic acid functionalized 1,3-dialkylimidazole Cationic or alkylsulfonic acid functionalized quaternary ammonium salt cation and Lewis acidic inorganic anion
The bis-acidic ionic liquid is used as a catalyst; under the protection of nitrogen, the reaction temperature is 220-280 ° C, and the reaction time is 2-8 hours to catalyze the polymerization of fatty acid methyl esters to prepare dimer acid methyl esters. Compared with the prior art: 1. It has higher Excellent polymerization ability, no need to pressurize and short reaction time. 2. The dimer acid methyl ester product is immiscible with the ionic liquid catalyst and separates itself, which makes the separation process easier. 3. The catalyst ionic liquid has stable performance and can be recycled.
Description
Technical field
The present invention relates to a kind of
the application of the two acidic ion liquids of-Lewis in unsaturated fatty acids methyl esters polyreaction, relates to a kind of
the two presence of acidic ionic liquid catalyst unsaturated fatty acids methyl esters dimerization of-Lewis are prepared the novel method of dimeric acid methyl ester.
Background technology
Dimeric acid methyl ester is the intermolecular generation of two or more unsaturated fatty acid esters Diels-Alder reaction, the oligomeric compound of the dicarboxylic esters generating, it is actually by 36 carbon dimers, a small amount of 54 carbon tripolymers and mixture that more polymer polymer forms.Dimeric acid methyl ester can be used to produce polyamide resin, and its snappiness is good, adhesive power is high and have antiseptic and rustproof characteristic, can be used for manufacturing coating, tamanori etc., is widely used in the industries such as boats and ships, machinery, motor, automobile, civil construction.The polymkeric substance of dimeric acid methyl ester has good snappiness, sticking power, stopping property and water tolerance, can be used for the industries such as electronics, coating, ink.Dimeric acid methyl ester and petroleum product, organic solvent have good intermiscibility, thermostability, can be used as machining of metals oil, lubricating oil, antirust wet goods additive, also can be used as tensio-active agent for washing composition, flow agent, levelling agent, dispersion agent, static inhibitor etc.The lipid acid polymerization method of report is hot dimerization method the earliest, and this technique needs high-temperature pressurizing reaction.At present the carclazyte catalysis fatty acid methyl ester dimerization reactions that adopt are prepared dimeric acid methyl ester more, and the wilkinite of take containing 75% above polynite as US 3873585 is catalyzer; It is catalyzer that US 6187903 and US 3632822 adopt respectively the carclazyte of alkali-metal oxyhydroxide and oxide modifying; And CN101293829A employing Aluminum chloride anhydrous or Zinc Chloride Anhydrous are catalyzer, the vitriol oil is promotor.There is following shortcoming in these techniques: the consumption of heterogeneous catalyst excessive mostly, and meeting entrained product, causes the loss of product; Generally need to carry out under high pressure, reaction conditions is harsher, also higher to the requirement of conversion unit and operation.
Because having traditional molecular solvent and fused salt dual nature, ionic liquid at room temperature has been widely used in catalysis or uncatalyzed reaction as the eco-friendly green solvent of a class or catalyzer.In recent years, acid functionalization ionic liquid has become the focus in research, and its advantage is: with solid acid, compare favourably, and acid modulation more easily, meticulousr, thereby be more conducive to research and the screening of catalyst of catalytic mechanism; Similar with conventional acid, there is the advantage of fluent material, as good fluidity, the high and strength of acid of acidic site density is evenly distributed; Structure by change and modified ion liquid yin, yang ion, can realize the optimization of heterogeneous reaction system, as: simplify the separation of product, promote recycling of ionic liquid.Therefore, acid functionalization ionic liquid can replace conventional acid catalyzer, has great application potential.
Summary of the invention
The object of the invention is to replace the method that traditional acid catalysis fatty acid methyl polyisocyanate polyaddition is prepared dimeric acid methyl ester, a kind of efficient and eco-friendly catalysts is provided, under gentle reaction conditions, catalysis fatty acid methyl ester polyreaction is prepared the novel method of dimeric acid methyl ester, for dimeric acid methyl ester synthetic provides an eco-friendly operational path.
The present invention relates to a kind of preparation method of dimeric acid methyl ester, it is characterized in that adopting 1 of the pyridylium of alkylsulphonic acid functionalization or alkylsulphonic acid functionalization, the quaternary ammonium salt cationic of 3-dialkylimidazolium positively charged ion or alkylsulphonic acid functionalization and the inorganic anion of Lewis acidity form
the two acidic ion liquids of-Lewis are as catalyzer; Reaction conditions is under nitrogen protection, 200～280 ℃ of temperature of reaction, 2～8 hours reaction times, and catalysis fatty acid methyl ester polyreaction is prepared dimeric acid methyl ester.
1 of the pyridylium of alkylsulphonic acid functionalization used herein (1) or alkylsulphonic acid functionalization, the general structure of the quaternary ammonium salt cationic (3) of 3-dialkylimidazolium positively charged ion (2) or alkylsulphonic acid functionalization is as follows:
N=3～4 wherein, R
1for C
1～C
3, R
2for C
1～C
3.
The inorganic anion of Lewis acidity used herein is a kind of in chlorine zincic acid root, bromine zincic acid root, chlorine copper acid group, bromine copper acid group, chlorine ferrous acid root, bromine ferrous acid root.
Ionic liquid quality used in the present invention is 1: 30 to 1: 4 with reacting total quality of material ratio
The present invention solves this technical problem by the following technical programs:
1.
the typical production of the two acidic ion liquids of-Lewis is: by a certain amount of 1,3-propane sultone or 1, it is in the ethyl acetate of 5～10 times that 4-butane sultone is dissolved in its total mass number, be warming up to 40～60 ℃, drip equimolar N-Methylimidazole, or N-ethyl imidazol(e), or N-propyl imidazole, or pyridine, or Trimethylamine 99, or triethylamine, or tripropyl amine, dropwise, after insulation reaction 3～5 hours, filter, filter cake washs by ethyl acetate, and be dried 2 hours at 100 ℃, obtain corresponding white solid inner salt; Get a certain amount of inner salt making, be dissolved in the deionized water of 2～4 times of its total mass numbers, dripping equimolar mass concentration and be 37% hydrochloric acid or mass concentration is 40% Hydrogen bromide acidification reaction, after dropwising, is warming up to 70～90 ℃ and insulation reaction 2～3 hours; After completion of the reaction, decompression dehydration obtains light yellow viscous liquid acidifying inner salt; Get a certain amount of acidifying inner salt making, with mol ratio be 1: 1.1～3.0 zinc chloride, or zinc bromide, or cupric chloride; or cupric bromide, or iron(ic) chloride, or iron bromide mixing, under nitrogen protection; be warming up to 90～110 ℃, insulation reaction to solid all dissolves, and obtaining under room temperature is sticky liquid
the two acidic ion liquids of-Lewis.
The typical case of dimeric acid methyl ester preparation be (with
two acidic ion liquid 1-(4-sulfonic acid) butyl-3-Methylimidazole chlorozincates of-Lewis; acidifying inner salt and zinc chloride mol ratio 1: 2.5): get the ionic liquid of 1.0～2.5 parts of weight and the fatty acid methyl ester of 10～30 parts of weight; under nitrogen protection; at 200～280 ℃, polyreaction is after 2～8 hours; cooling and add appropriate solvent toluene extraction product, topple over and separate upper strata extraction phase.The supernatant liquid solvent that reduces pressure, obtains dimeric acid methyl ester product.
3. the ionic liquid that method of the present invention is used is reusable, the canonical process that ionic liquid repeats is by after the reaction solution extraction of esterification last time, because under ionic liquid low temperature, very thickness and density are greater than extraction phase, can directly pour out easily upper strata extraction phase, lower floor's ionic liquid can be used for next polyreaction without any processing, when ionic liquid consumption is reaction solution total mass 20%, to reuse 6 times, the yield of polymerisate dimeric acid methyl ester has no obvious decline.
The present invention compares with traditional catalyst, is characterized in:
1. there is higher polymerizing power, short without pressurization and reaction times.
2. product dimeric acid methyl ester look shallow, matter good, and layering voluntarily makes the separation of product and aftertreatment more easy with ionic-liquid catalyst is not miscible.
3. catalyst ion liquid properties is stable, and reaction is with can be used for reaction next time without any processing later, and catalytic performance has no reduction, recycles performance good, genus environmentally friendly technology route.
Specific implementation method
Below in conjunction with embodiment, method of the present invention being described further, is not limitation of the invention.
Embodiment mono-: by 1.0g 1-(4-sulfonic acid) butyl-3-Methylimidazole chlorozincate (wherein the mol ratio of chlorination 1-(4-sulfonic acid) butyl-3-methylimidazole salt and zinc chloride is 1: 3.0) and 30g fatty acid methyl ester under nitrogen protection; in 230 ℃ of reactions 6 hours; be cooled to room temperature; add toluene 30g extraction polymerisate and unreacted raw material; separate upper layer of extraction liquid; and deviate from toluene and unreacting material at decompression (5mmHg) 240 ℃; obtain polymerisate dimeric acid methyl ester, yield is 67%.
Embodiment bis-: by 2.0g 1-(3-sulfonic acid) propyl group-3-propyl imidazole chloro-cuprate (wherein the mol ratio of chlorination 1-(3-sulfonic acid) butyl-3-methylimidazole salt and cupric chloride is 1: 2.0) and 10g fatty acid methyl ester under nitrogen protection; in 200 ℃ of reactions 5 hours; be cooled to room temperature; add toluene 20g extraction polymerisate and unreacted raw material; separate upper layer of extraction liquid; and deviate from toluene and unreacting material at decompression (5mmHg) 240 ℃; obtain polymerisate dimeric acid methyl ester, yield is 71%.
Embodiment tri-: by 3.0g 1-(4-sulfonic acid) butyl-3-ethyl imidazol(e) bromine cuprate (wherein the mol ratio of bromination 1-(4-sulfonic acid) butyl-3-ethyl imidazol(e) salt and cupric bromide is 1: 1.1) and 12g fatty acid methyl ester under nitrogen protection; in 280 ℃ of reactions 4 hours; be cooled to room temperature; add toluene 25g extraction polymerisate and unreacted raw material; separate upper layer of extraction liquid; and deviate from toluene and unreacting material at decompression (5mmHg) 240 ℃; obtain polymerisate dimeric acid methyl ester, yield is 53%.
Embodiment tetra-: by 1.5g 4-sulfonic acid butyl-pyridinium bromine zincate (wherein the mol ratio of bromination 4-sulfonic acid butyl-pyridinium salt and zinc chloride is 1: 2.0) and 20g fatty acid methyl ester under nitrogen protection; in 200 ℃ of reactions 8 hours; be cooled to room temperature; add toluene 35g extraction polymerisate and unreacted raw material; separate upper layer of extraction liquid; and deviate from toluene and unreacting material at decompression (5mmHg) 240 ℃, and obtaining polymerisate dimeric acid methyl ester, yield is 76%.
Embodiment five: by 1.5g 3-sulfonic acid propyl group pyridinium tribromide wustite (wherein the mol ratio of bromination 3-sulfonic acid propyl group pyridinium salt and iron bromide is 1: 2.5) and 20g fatty acid methyl ester under nitrogen protection; in 250 ℃ of reactions 5 hours; be cooled to room temperature; add toluene 35g extraction polymerisate and unreacted raw material; separate upper layer of extraction liquid; and deviate from toluene and unreacting material at decompression (5mmHg) 240 ℃, and obtaining polymerisate dimeric acid methyl ester, yield is 74%.
Embodiment six: by 1.0g 3-sulfonic acid oxypropyl trimethyl amine ferricyanide (wherein the mol ratio of chlorination 3-sulfonic acid oxypropyl trimethyl amine salt and iron(ic) chloride is 1: 2.0) and 10g fatty acid methyl ester under nitrogen protection; in 280 ℃ of reactions 2 hours; be cooled to room temperature; add toluene 15g extraction polymerisate and unreacted raw material; separate upper layer of extraction liquid; and deviate from toluene and unreacting material at decompression (5mmHg) 240 ℃, and obtaining polymerisate dimeric acid methyl ester, yield is 52%.
Embodiment seven: by 1.5g 3-sulfonic acid propyl group triethylamine ferricyanide (wherein the mol ratio of chlorination 3-sulfonic acid propyl group triethyl amine salt and iron(ic) chloride is 1: 2.0) and 20g fatty acid methyl ester under nitrogen protection; in 260 ℃ of reactions 4 hours; be cooled to room temperature; add toluene 15g extraction polymerisate and unreacted raw material; separate upper layer of extraction liquid; and deviate from toluene and unreacting material at decompression (5mmHg) 240 ℃, and obtaining polymerisate dimeric acid methyl ester, yield is 64%.
Embodiment eight: by 3.0g 4-sulfonic acid butyl tripropylamine ferricyanide (wherein the mol ratio of chlorination 4-sulfonic acid butyl tripropyl amine salt and iron(ic) chloride is 1: 1.5) and 30g fatty acid methyl ester under nitrogen protection; in 230 ℃ of reactions 6 hours; be cooled to room temperature; add toluene 50g extraction polymerisate and unreacted raw material; separate upper layer of extraction liquid; and deviate from toluene and unreacting material at decompression (5mmHg) 240 ℃, and obtaining polymerisate dimeric acid methyl ester, yield is 73%.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910159634.0A CN101613273B (en) | 2009-07-25 | 2009-07-25 | Method for preparing dimeric acid methyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910159634.0A CN101613273B (en) | 2009-07-25 | 2009-07-25 | Method for preparing dimeric acid methyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101613273A CN101613273A (en) | 2009-12-30 |
| CN101613273B true CN101613273B (en) | 2014-04-16 |
Family
ID=41493184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910159634.0A Expired - Fee Related CN101613273B (en) | 2009-07-25 | 2009-07-25 | Method for preparing dimeric acid methyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101613273B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382015B (en) * | 2011-08-02 | 2013-10-30 | 常州大学 | Method for preparing sulfated methyl ester by ionic liquid catalysis method |
| CN102516128B (en) * | 2011-12-19 | 2014-03-19 | 河北工业大学 | Synthetic technology of diphenylmethane dicarbamate by adopting Bronsted-Lewis acidic ionic liquid catalysis |
| CN102557928A (en) * | 2011-12-29 | 2012-07-11 | 北京国力源高分子科技研发中心 | Method for preparing dimeric acid methyl ester by using microwaves |
| CN103204836B (en) * | 2013-03-31 | 2017-10-10 | 青岛科技大学 | A kind of method for preparing 5 hydroxymethylfurfurals |
| CN104817521B (en) * | 2015-03-03 | 2016-09-28 | 中国林业科学研究院林产化学工业研究所 | A kind of epoxy dimer (fatty acid) yl methyl ester and its preparation method and application |
| CN104789298B (en) * | 2015-03-25 | 2017-10-17 | 中国人民解放军空军油料研究所 | A kind of method for preparing aviation fuel antiwear additive |
| CN104785297B (en) * | 2015-03-25 | 2018-04-27 | 中国人民解放军空军油料研究所 | A kind of catalyst for being used to prepare aviation fuel antiwear additive |
| CN106220464B (en) * | 2016-07-05 | 2018-06-15 | 青岛科技大学 | A kind of method for being catalyzed australene dimerization reaction |
| CN111153799A (en) * | 2020-01-20 | 2020-05-15 | 浙江本立科技股份有限公司 | Preparation method of methyl 3-methoxyacrylate |
| CN118594608B (en) * | 2024-05-23 | 2025-01-28 | 安徽虹泰新材料股份有限公司 | A composite microsphere catalyst and its preparation method and phosphorus-free dimer acid preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191035A (en) * | 2007-11-16 | 2008-06-04 | 青岛科技大学 | A Brφnsted-Lewis acidic ionic liquid and its application in rosin polymerization |
| CN101293829A (en) * | 2008-06-12 | 2008-10-29 | 江苏工业学院 | The preparation method of dimer acid methyl ester and dimer acid |
| CN101391956A (en) * | 2008-11-05 | 2009-03-25 | 江南大学 | A method for synthesizing methyl oleate and epoxy methyl oleate in an ionic liquid medium |
-
2009
- 2009-07-25 CN CN200910159634.0A patent/CN101613273B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191035A (en) * | 2007-11-16 | 2008-06-04 | 青岛科技大学 | A Brφnsted-Lewis acidic ionic liquid and its application in rosin polymerization |
| CN101293829A (en) * | 2008-06-12 | 2008-10-29 | 江苏工业学院 | The preparation method of dimer acid methyl ester and dimer acid |
| CN101391956A (en) * | 2008-11-05 | 2009-03-25 | 江南大学 | A method for synthesizing methyl oleate and epoxy methyl oleate in an ionic liquid medium |
Non-Patent Citations (6)
| Title |
|---|
| Carlos W.Lee,.Diels-Alder Reactions in Chloroaluminate Ionic Liquids:Acceleration and Selectivity Enhancement.《Tetrahedron Letters》.1999,第40卷第2461-2464页. |
| Diels-Alder Reaction in Room-Temperature Ionic Liquids;T.Fischer,et al.,;《Tetrahedron Letters》;19991231;第40卷;第794-796页 * |
| Diels-Alder Reactions in Chloroaluminate Ionic Liquids:Acceleration and Selectivity Enhancement;Carlos W.Lee,;《Tetrahedron Letters》;19991231;第40卷;第2461-2464页 * |
| Ionic liquids in catalysis;Tom Welton,;《Coordination Chemistry Reviews》;20040702;第248卷;第2459-2477页 * |
| T.Fischer,et al.,.Diels-Alder Reaction in Room-Temperature Ionic Liquids.《Tetrahedron Letters》.1999,第40卷第793-796页. |
| Tom Welton,.Ionic liquids in catalysis.《Coordination Chemistry Reviews》.2004,第248卷第2459-2477页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101613273A (en) | 2009-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101613273B (en) | Method for preparing dimeric acid methyl ester | |
| CN101191035B (en) | A Br*nsted-Lewis acidic ionic liquid and its application in rosin polymerization | |
| Wei-Li et al. | Polymer grafted with asymmetrical dication ionic liquid as efficient and reusable catalysts for the synthesis of cyclic carbonates from CO2 and expoxides | |
| Liu et al. | Dimerization of fatty acid methyl ester using Brönsted–Lewis acidic ionic liquid as catalyst | |
| CN102603532B (en) | Method for preparing plasticizer terephthalate by alcoholysis of waste polyester PET | |
| CN101225028B (en) | Preparation method of alkyl aromatic aldehyde | |
| CN112920218B (en) | Tert-butylphenyl phosphate and preparation method and application thereof | |
| CN104151364A (en) | O-pyrazolyl phenyl functionalized nitrogen heterocyclic carbene palladium complex and preparation method and application thereof | |
| CN108947776A (en) | A kind of method of Catalytic lignin model aryl ether oxicracking | |
| CN104744413A (en) | Oxidation process | |
| Pandey et al. | Synthesis of value-added furan compounds from biomass derived glucose via cascade catalysis using functionalized V2O5 catalysts | |
| CN111320653B (en) | Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method | |
| CN101955849B (en) | Biological lubricant prepared with ionic liquid as catalyst and preparation method | |
| CN103508881A (en) | Method for synthesizing alkyl salicylic acid | |
| CN103706404B (en) | For catalysis CO 2with magnetic composite microsphere of epoxide cycloaddition reaction and its preparation method and application | |
| CN100582081C (en) | Method for synthesizing C10 tertiary carbon acid | |
| CN104841430B (en) | A kind of low-load amount hydrotalcite catalyst for phenol hydroxylation reaction and preparation method thereof | |
| CN103012121A (en) | Method for synthesizing biphenyl 4,4'-dicarboxylic acid from p-chlorotoluene | |
| CN104119224A (en) | Method for catalytic oxidation conversion of levulinic acid and levulinic acid ester | |
| CN104248978B (en) | A kind of preparation method of phosphomolybdate crystal catalyst | |
| CN102069010B (en) | Montmorillonite catalyst used in preparation of cyclic carbonate | |
| CN106220464B (en) | A kind of method for being catalyzed australene dimerization reaction | |
| CN102040608B (en) | Preparation method and application of 2-imine-1,10-phenanthroline ligand | |
| CN105777537B (en) | Alkylation method of salicylic acid | |
| CN104876804B (en) | A kind of preparation method of bisphenol F with high 4,4'-isomer content |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140416 Termination date: 20170725 |