CN1212304C - Method for preparing long-chain dicarboxylic dialkyl ester - Google Patents
Method for preparing long-chain dicarboxylic dialkyl ester Download PDFInfo
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- CN1212304C CN1212304C CN 02144952 CN02144952A CN1212304C CN 1212304 C CN1212304 C CN 1212304C CN 02144952 CN02144952 CN 02144952 CN 02144952 A CN02144952 A CN 02144952A CN 1212304 C CN1212304 C CN 1212304C
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- dicarboxylic acid
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Abstract
The present invention discloses a preparation method of a long-chain dicarboxylic dialkyl ester. Dicarboxylic acid of C8 to C18 and excessive monohydric alcohol of C6 to C18 are used as raw materials, proper acidic resin is used as a catalyst, and the esterification reaction is carried out at high temperature. Simultaneously, the generated moisture is evaporated out. The reaction conversion rate is increased, and reaction liquid is purified through processes, such as distillation, etc. The method of the present invention has the advantages of short flow path, high esterification rate, short operating period, low energy consumption, etc., and is suitable for preparing a long-chain dicarboxylic high-carbon dialkyl ester.
Description
Technical field
The present invention relates to a kind ofly prepare the method for dialkyl, particularly a kind of method for preparing the long-chain fat dicarboxylic acid dialkyl esters by long-chain fat dicarboxylic acid and higher alcohols by dicarboxylic acid and alkyl alcohol.
Background technology
The long chain dicarboxylic acid dialkyl as the important organic chemical industry's intermediate of a class mainly as plastics with low temperature resistant softening agent, synthesize aircraft oil, water base machining oil, synthetic perfume etc.Esterification takes place by dicarboxylic acid and alcohol and obtains in dicarboxylic acid dialkyl esters.Esterification generally need be carried out in the presence of an acidic catalyst, and the catalyzer that generally uses is inorganic acid such as the vitriol oil, hydrochloric acid etc., though this an acidic catalyst catalytic efficiency height, price is low, but corrodibility is strong, needs after reaction finishes to remove with the alkali neutralization, cause the three wastes, contaminate environment.Especially the vitriol oil has oxidisability and causes charing, side reactions such as dehydration etherificate, polymerization, is not suitable for the reaction that bigger carboxylic acid of molecular weight and higher alcohols esterification prepare dialkyl.
The Japanese Patent spy opens clear 50-25518 and discloses a kind of method for preparing the dodecanedioic acid dialkyl, be characterized in using positive titanic acid ester or titanic acid ester as catalyzer, excellent catalytic effect, but because the titanate ester catalyzer has only and just have catalytic activity when temperature of reaction reaches more than 180 ℃, so temperature of reaction height, thereby caused the generation of some high temperature oxidation scission reactions, the ester color of preparation is darker, after esterification finishes, the catalyzer reaction that need be hydrolyzed becomes titanyl compound and removes, produced titaniferous waste water, contaminate environment.For this reason, U.S. Pat 6,087,527 have proposed the method that a kind of solid acid catalyst prepares dicarboxylic acid dialkyl esters, specific practice is a catalyzer with commercially available " Diaion " PK-200 strong-acid ion exchange resin, adopt the multistep esterification, when the first step esterification reaches certain transformation efficiency, for further reaction will have special step to remove water generation reaction.At first reaction mass is filtered, concentrates and remove unreacted pure and mild water generation reaction, and the thick ester that obtains adds raw alcohol again and catalyzer continues new round reaction, and until obtaining satisfied transformation efficiency, such step can repeat repeatedly.Though this method can obtain satisfied transformation efficiency, operation steps is many, and technology is loaded down with trivial details, the expense height, and the time is long, and this resin catalyst can only be used for producing long chain dicarboxylic acid short chain dialkyl, and suitable alkyl alcohol is C
1～C
4Positive isomery alcohol, be not suitable for by long chain dicarboxylic acid and higher alcohols prepared in reaction long chain dicarboxylic acid dialkyl, and because the catalyst tolerates warm nature is poor, and esterification reaction temperature can only maintain 60～80 ℃, surpassing 100 ℃ of catalyzer will lose activity.Cross low temperature of reaction and greatly reduce esterification reaction rate, the water that reaction is generated is in time removed.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of preparation method of long chain dicarboxylic acid high-carbon dialkyl, the inventive method flow process is short, and the esterification yield height has shortened the operational cycle, has reduced energy consumption, and production cost is low.
The inventive method process comprises the steps:
A. long chain dicarboxylic acid and higher alcohols carry out esterification at a certain temperature in the presence of solid acid catalyst, steam the moisture content of generation in esterification, generate long chain dicarboxylic acid high-carbon dialkyl;
B. filter and tell solid acid catalyst, obtain containing the ester reaction solution;
C. the above-mentioned ester reaction solution that contains of normal pressure or underpressure distillation to remove remaining raw alcohol, obtains product long chain dicarboxylic acid high-carbon dialkyl.
Behind above-mentioned steps C, as containing the acid or the unreacted diprotic acid of catalyst loss in the fruit product, available this product of diluted alkaline water washing washes with water and makes it to be neutral, removes remaining moisture content with distillating method then.
Prepared as stated above long chain dicarboxylic acid dialkyl product, extent of purification difference with use long chain dicarboxylic acid raw material, the alkyl ester product can have deep mixed color, according to different requirements to the dialkyl product, can be after above-mentioned technology B step to the reaction solution processing of decolouring, to satisfy the requirement of product to color and luster.
The solid acid catalyst that the inventive method is used is weakly acidic cation-exchange resin or storng-acid cation exchange resin, storng-acid cation exchange resin is because acid strong, good catalytic activity, especially " DNW " (trade(brand)name) sulfonic acid ion exchange resin catalytic effect of producing with Dandong No.3 Chemical Factory is the best.
The long carbochain dicarboxylic acid that is suitable for the inventive method can be straight chain or the dicarboxylic acid with produced in several ways that has side chain, and preferably is the straight chain saturated alpha of producing with biofermentation method, and the omega-long chain aliphaticdicarboxylic acid has HOOC (CH
2)
nThe general molecular formula of COOH, wherein n=6～16 more generally are n=8～14, both can be the dicarboxylic acid of single component, also can be the hybrid long chain aliphaticdicarboxylic acids of two or more any component arbitrary proportion composition.The higher alcohols that are suitable for the inventive method are C
6～C
18Saturated straight chain or branched monobasic alcohol, be more suitable for for C
8～C
15Monohydroxy-alcohol.
Esterification condition of the present invention is, under agitation is heated to temperature of reaction and carries out esterification, and temperature of reaction remains on 80～150 ℃, is preferably 100～130 ℃, reaction 2～5h.Evaporate the moisture content of production in reaction process, the mode that can adopt condensation to reclaim is measured the moisture content that evaporates, and water generation reaction is near theoretical aquifer yield and when no longer including water and steaming, and reaction finishes.
For long chain dicarboxylic acid is reacted completely as far as possible, need to add excessive monohydroxy-alcohol, the acid alcohol mol ratio is 1: 2～10, be preferably 1: 3～8, the resin catalyst add-on is the 4wt%～14wt% of acid alcohol total amount, is preferably 6wt%～10wt%.
The inventive method compared with prior art has the following advantages:
(1) adopt the non-corrosiveness solid acid catalyst, easily separated, pollution-free, no carbonization phenomenon, side reaction can remain on minimum, and catalyzer is reusable.
(2) the present invention has adopted the catalyzer of good heat resistance, can keep moderate temperature of reaction, has both improved esterification reaction rate, helps again in time removing the water that reaction generates, and has shortened the reaction times.
(3) saved dehydrating step special in the esterification reaction process, esterification can be finished in a step, simplified technological process, shortened the operational cycle, reduced energy consumption, thereby help reducing production costs.
Embodiment
Being suitable for the long-chain fat dicarboxylic acid that the present invention is used to prepare long carbochain dicarboxylic acid dialkyl esters generally produces with biofermentation method, both can use the purified long chain dicarboxylic acid that extraction obtains from fermented liquid, and also can select for use the thick dicarboxylic acid that contains microbial cells to prepare dialkyl.
If adopt the thick dicarboxylic acid that contains microbial cells to prepare the long chain dicarboxylic acid dialkyl, its concrete technology comprises:
1) under the heating condition, has the dicarboxylic acid of microbial cells, and add the decolorizing adsorbent processing of decolouring with higher alcohols dissolvings;
2) alcoholic solution of the above-mentioned dicarboxylic acid of filtration is removed decolorizing adsorbent, microbial cells and other insoluble impurities;
3) add solid acid catalyst in the alcoholic solution of above-mentioned dicarboxylic acid, under temperature of reaction, carry out esterification;
4) after esterification finished, filtering reacting liquid was told solid acid catalyst, obtains containing the ester reaction solution;
5) the above-mentioned ester reaction solution that contains of normal pressure or underpressure distillation to remove remaining raw alcohol, obtains product.
As required,, wash with water again and make it to be neutral, remove remaining moisture content with distillating method then with this product of diluted alkaline water washing.
Be applicable to that the typical dicarboxylic acid of the inventive method comprises long-chain dicarboxylic acid or their mixtures such as sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, tetradecane diacid, pentadecane diacid, Thapsic acid, pentadecane dicarboxylic acid.Be applicable to that the typical monohydroxy-alcohol of the inventive method comprises high-carbon monohydroxy-alcohols such as octanol, isooctyl alcohol, nonyl alcohol, isononyl alcohol, decyl alcohol, isodecyl alcohol, undecyl alcohol, different undecyl alcohol, lauryl alcohol, different lauryl alcohol, tridecanol, different tridecanol.
In order to obtain the long-chain fat dicarboxylic acid dialkyl esters product that carbochain is longer, viscosity is higher, also can use a spot of low-carbon (LC) dibasic alcohol to participate in reaction, to make the multiple ester of long chain dicarboxylic acid dialkyl group, this ester is suitable as the base oil of synthetic aircraft oil most.Available dibasic alcohol is C
2～C
4Dibasic alcohol, wherein suitable have ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,3 butylene glycol, 1, a 4-butyleneglycol etc.The concrete usage quantity of dibasic alcohol is 0～8mol% of diprotic acid.
If use the thick dicarboxylic acid that contains microbial cells to prepare dialkyl, thick acid and alcohol are joined in the reactor, add decolorizing adsorbent again, be heated to 70～100 ℃ of absorption of decolouring under stirring.Bleaching time is preferably 0.5～1h, and filtered while hot is removed decolorizing adsorbent, microbial cells and insoluble impurities then, obtains water white dicarboxylic acid alcoholic solution, adds resin catalyst again, carries out esterification according to above-described method and condition.
Decolorizing adsorbent is gac or the atlapulgite with vesicular structure, and add-on is 0.2wt%～10wt%, is preferably 1wt%～7wt%, and stirring velocity is generally 40～120r/min, is preferably 60～100r/min.
According to the inventive method, after esterification finishes, filtering reacting liquid is told catalyzer, obtain containing the reaction solution of ester, normal pressure or underpressure distillation are to remove unreacted alcohol, in order to remove acid remaining in the thick ester then, improve the stability of dialkyl product, the thick ester that need obtain with the weak base water washing of 50～60 ℃ of heat divides sub-cloud alkali lye layer, and the thick ester on upper strata uses 50～60 ℃ hot wash to neutral again.First-selected weak base is Na
2CO
3Or NaHCO
3, the about 2N of concentration.
The above-mentioned product that obtains just obtains highly purified long-chain fat dicarboxylic acid dialkyl acid product after simple distillation removes moisture content.
Below will the present invention will be further described by embodiment.
Embodiment 1
" DNW " Zeo-karb adding 1000ml that the refining dodecanedioic acid of 60g, 480g2-ethylhexanol and 22g Dandong No.3 Chemical Factory are produced has in the there-necked flask that distills receiving system, stir down reacting by heating liquid to 120 ℃, carry out esterification in this temperature, reaction process constantly has water to steam, be collected in the receiving bottle, reaction 3.5h, no longer include water and steam this moment, finishes reaction.The underpressure distillation reaction solution reclaims unreacted alcohol, uses the NaHCO of 50ml 2N then
3The thick ester that solution (being preheating to 60 ℃) washing obtains, the hot wash of using 60 ℃ again is to neutral.Boil off the remaining moisture content in the thick ester under the 50kPa vacuum tightness, promptly obtain product dodecanedioic acid two (2-ethylhexyl) ester 106.3g, esterification rate of recovery 94.6wt%.
Embodiment 2
Pentadecane diacid (pentadecane diacid content 89.0%), the different tridecanol of 300g and brilliance timber mill, 4.2g Beijing " GH-88 " Powdered Activated Carbon that 70g is had a thalline join 1000ml and have in the there-necked flask of reflux exchanger, be heated to 80 ℃ under stirring, decolouring absorption 1h, stirring velocity 80r/min.Filtered while hot obtains the alcoholic solution of dicarboxylic acid then, filtrate joins 500ml and has in the there-necked flask that distills receiving system, and " DNW " Zeo-karb of adding 28g Dandong No.3 Chemical Factory production, stir down reacting by heating liquid to 130 ℃, the water that reaction process is steamed is received in the receiving bottle, when not having water to distillate, finish reaction, reaction times 3.2h.Remaining Step By Condition makes pentadecane diacid two isotridecanol 136.2g, esterification rate of recovery 93.2wt% with embodiment 1.
Embodiment 3
With 60g purified undecane dicarboxylic acid, 350g isodecyl alcohol, 2g1, " DNW " Zeo-karb that 2-butyleneglycol and 50g Dandong No.3 Chemical Factory produce joins and has in the 1000ml there-necked flask that distills receiving system, stir down reacting by heating liquid to 100 and ℃ carry out esterification, stopped reaction when not having water to steam, reaction times 4.6h.Method according to embodiment 1 reclaims unreacted isodecyl alcohol then, and alkali cleaning, washing, dehydration make the multiple ester 118.2g of undecane dicarboxylic acid two isodecyls ester-undecane dicarboxylic acid butyleneglycol, esterification rate of recovery 93.8wt%.
Claims (11)
1, a kind of preparation method of long chain dicarboxylic acid dialkyl is characterized in that comprising the steps:
A) long chain dicarboxylic acid and higher alcohols carry out esterification under 80～150 ℃ in the presence of solid acid catalyst, steam the moisture content of generation in esterification, generate long chain dicarboxylic acid high-carbon dialkyl; Described solid acid catalyst is weakly acidic cation-exchange resin or storng-acid cation exchange resin;
B) solid acid catalyst is told in filtration, obtains containing the ester reaction solution;
C) the above-mentioned ester reaction solution that contains of normal pressure or underpressure distillation to remove remaining raw alcohol, obtains product long chain dicarboxylic acid high-carbon dialkyl;
The general formula of wherein above-mentioned long chain dicarboxylic acid is HOOC (CH
2)
nA kind of or mixed dicarboxylic acid among the COOH, wherein n=6～16; Above-mentioned higher alcohols are C
6～C
18Saturated straight chain or branched monobasic alcohol.
2, in accordance with the method for claim 1, it is characterized in that behind described step C,, wash with water again and make it to be neutral, remove remaining moisture content with distillating method then with this product of diluted alkaline water washing.
3, in accordance with the method for claim 1, it is characterized in that behind the described step B the reaction solution processing of decolouring.
4, in accordance with the method for claim 1, it is characterized in that the n in the described long chain dicarboxylic acid general formula is 8～14.
5, in accordance with the method for claim 1, it is characterized in that described higher alcohols are C
8～C
15Saturated straight chain or branched monobasic alcohol.
6, in accordance with the method for claim 1, it is characterized in that described esterification reaction temperature is 100～130 ℃, the reaction times is 2～5 hours, and reaction is under agitation carried out.
7, in accordance with the method for claim 1, it is characterized in that the long chain dicarboxylic acid of esterification and the mol ratio of monohydroxy-alcohol are 1: 2～10, the catalyzer add-on is the 4wt%～14wt% of acid alcohol total amount.
8, in accordance with the method for claim 7, it is characterized in that described acid alcohol mol ratio is 1: 3～8, the catalyzer add-on is the 6wt%～10wt% of acid alcohol total amount.
9, in accordance with the method for claim 1, it is characterized in that the higher alcohols of esterification raw material contain the C of 0～8mol%
2～C
4Dibasic alcohol.
10, in accordance with the method for claim 3, it is characterized in that the discoloring agent that described decolouring is handled is gac or atlapulgite, add-on is 0.2wt%～10wt%.
11, in accordance with the method for claim 2, it is characterized in that described diluted alkaline water is Na
2CO
3Or NaHCO
3Solution.
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| CN 02144952 CN1212304C (en) | 2002-12-19 | 2002-12-19 | Method for preparing long-chain dicarboxylic dialkyl ester |
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|---|---|---|---|
| CN 02144952 CN1212304C (en) | 2002-12-19 | 2002-12-19 | Method for preparing long-chain dicarboxylic dialkyl ester |
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| CN1212304C true CN1212304C (en) | 2005-07-27 |
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| US8984338B2 (en) | 2009-07-06 | 2015-03-17 | Lg Electronics Inc. | Home appliance diagnosis system, and method for operating same |
| US8983798B2 (en) | 2009-07-24 | 2015-03-17 | Lg Electronics Inc. | Diagnostic system and method for home appliance |
| US9013320B2 (en) | 2012-07-09 | 2015-04-21 | Lg Electronics Inc. | Home appliance and its system |
| US9054953B2 (en) | 2008-06-16 | 2015-06-09 | Lg Electronics Inc. | Home appliance and home appliance system |
| US9197437B2 (en) | 2011-08-02 | 2015-11-24 | Lg Electronics Inc. | Home appliance, home appliance diagnostic system, and method |
| US9495859B2 (en) | 2012-07-03 | 2016-11-15 | Lg Electronics Inc. | Home appliance and method of outputting signal sound for diagnosis |
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| CN109678657A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The method that high carbon dicarboxylic acid continuously hydrogen adding prepares high-carbon dihydric alcohol |
| CN112079713B (en) * | 2019-06-13 | 2023-10-13 | 上海凯赛生物技术股份有限公司 | Method for treating mixtures containing long-chain dibasic acids and use thereof |
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2002
- 2002-12-19 CN CN 02144952 patent/CN1212304C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9054953B2 (en) | 2008-06-16 | 2015-06-09 | Lg Electronics Inc. | Home appliance and home appliance system |
| US8984338B2 (en) | 2009-07-06 | 2015-03-17 | Lg Electronics Inc. | Home appliance diagnosis system, and method for operating same |
| US8983798B2 (en) | 2009-07-24 | 2015-03-17 | Lg Electronics Inc. | Diagnostic system and method for home appliance |
| US9197437B2 (en) | 2011-08-02 | 2015-11-24 | Lg Electronics Inc. | Home appliance, home appliance diagnostic system, and method |
| US9495859B2 (en) | 2012-07-03 | 2016-11-15 | Lg Electronics Inc. | Home appliance and method of outputting signal sound for diagnosis |
| US9013320B2 (en) | 2012-07-09 | 2015-04-21 | Lg Electronics Inc. | Home appliance and its system |
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| CN1508117A (en) | 2004-06-30 |
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