CN102503824B - Process for synthesizing long chain acylation citric acid ester - Google Patents
Process for synthesizing long chain acylation citric acid ester Download PDFInfo
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- CN102503824B CN102503824B CN201110350388.4A CN201110350388A CN102503824B CN 102503824 B CN102503824 B CN 102503824B CN 201110350388 A CN201110350388 A CN 201110350388A CN 102503824 B CN102503824 B CN 102503824B
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Abstract
The invention discloses a process for synthesizing long chain acylation citric acid ester. The process comprises the following steps of: 1) synthesizing the citric acid ester, namely adding (hydrated) citric acid, alcohol and an acid catalyst into a reactor, performing an esterification reaction at the temperature of between 130 and 160 DEG C, removing the alcohol to obtain a citric acid ester crude product, and directly performing a step 3) or performing an acylation reaction in the step 3) after a step 2) is performed; 2) refining the citric acid ester; and 3) synthesizing the long chain acylation citric acid ester, namely adding acid anhydride of carboxylic acid with more than 3 carbon atoms and activated carbon into the citric acid ester crude product obtained in the step 1), or adding the acid anhydride, the activated carbon and the acid catalyst into finished citric acid ester obtained in the step 2), performing the acylation reaction at the temperature of between 60 and 100 DEG C, cooling, filtering the activated carbon, recycling acid, performing aftertreatment, and thus obtaining finished long chain acylation citric acid ester. By the process, the long chain acylation citric acid ester can be prepared; the long chain acylation citric acid ester serving as a plasticizer has high performance, the catalyst has low using amount and high efficiency, and a product has a good quality index; and the process has a short production period, is integrated, simple and low in cost and is suitable for industrialization application.
Description
Technical field
The present invention relates to a kind of synthetic method of green plasticization agent acylated citrate esters, particularly relate to a kind of synthetic method of citrate of long-chain acidylate, belong to chemosynthesis and technology field.
Background technology
Traditional plasticizer phthalic acid ester class may be brought out carcinogenic, and the restriction of abroad having made laws is used.Citric acid ester type compound is as " green " environment-friendly plasticizer, having obtained U.S. food and Drug Administration (FDA) approval uses, there is nontoxic, tasteless, anti-mildew, the advantage such as plasticizing effect is good, cold-resistant, fast light, water-fast, volatility is little, be widely used in the fields such as food product pack, medical article, toy for children, become the first-selected product that substitutes phthalic ester plasticizer.
Citric acid ester plasticizer domestic market vacancy is huge at present, mainly comprise citrate and acetyl citrate, principal item comprises triethyl citrate (TEC), acetyl triethyl citrate (ATEC), tributyl citrate (TBC), tributyl acetylcitrate (ATBC), citric acid three ester (THC), acetyl tributyl citrate three ester, the different monooctyl ester of citric acid three (TOC), the different monooctyl ester of acetyl tributyl citrate three (ATOC) and butyryl citrate etc. just just.Conventional TBC and ATBC.
Acetyl citrate is easily separated out, and pollutes products to be packaged, and the citrate of long-chain acidylate can reduce the property separated out, and strengthens plasticising performance.
About citric acid ester type compound preparation method's report, mainly concentrate on the research of synthetic method and the acetylize method of citrate.Acetyl citrate preparation technology of the prior art, is first taking citric acid and alcohol as raw material, under catalyst action, makes citrate finished product through esterification, neutralization, washing, de-alcohol and water, decolouring; And then make acetyl citrate finished product through acetylize, depickling, neutralization, washing, dehydration, decolouring.The shortcoming of this technique is: complex technical process, production cycle length, product loss are large, facility investment is large, " three wastes " discharge is large, contaminate environment.
CN201010583409.2, CN200610024372.3, CN200810195075.4 and CN200510030100.X etc. disclose the method that tributyl citrate is prepared in heterogeneous catalysis, catalyzer building-up process complexity in these methods, after esterification through filtering, the aftertreatment such as water (alkali) washes, distillation can obtain tributyl citrate.For obtaining tributyl acetylcitrate, by the tributyl citrate making further acidylate under the katalysis such as the vitriol oil, tosic acid, technical process is long, complicated operation, and product yield is low.
Aforesaid method all can be described as " two-step approach ".The synthesis technique of traditional two-step approach acetyl citrate will experience twice neutralization, washing, decolorization, and technical process is long, and the three wastes are many, and productive rate is low, and to improving product purity and reducing product colourity without obvious Beneficial Effect.Except acetylize, about other the synthetic rarely seen all of acylated citrate esters openly reports.
Therefore,, for overcoming acetylize citrate shortcoming, the preparation method of exploitation long chain acylation citric acid ester and succinct technique are split an environment-friendly plasticizer acylated citrate esters and are had important practical value.
Summary of the invention
The object of the present invention is to provide a kind of technique of synthetic long chain acylation citric acid ester, long chain acylation citric acid ester has better performance than acetyl citrate; The present invention simultaneously can adopt integral process; after esterification, do not remove catalyzer; direct acidylate after dealcoholysis; save the refining link of citrate, overcome the existing complex process of citrate process for acylating in prior art, the shortcoming such as the production cycle is long, product loss is large, " three wastes " are many, contaminate environment.
The technical solution adopted in the present invention is as follows:
A technique for synthetic long chain acylation citric acid ester, comprises the following steps:
1) citrate is synthetic
In reactor, add (hydration) citric acid, alcohol and acid catalyst, stirring reaction 3h ~ 6h at 130 DEG C ~ 160 DEG C, reclaims alcohol, obtains citrate crude product; The citrate crude product making directly carries out acylation reaction or first carry out step 2 by step 3)) after carry out again step 3).
2) citrate is refining
Step 2) after the citrate crude product refining that makes citrate finished product.
3) long chain acylation citric acid ester is synthetic
In the citrate crude product making to step 1), add acid anhydrides and the gac of the above carboxylic acid of C3; or to step 2) add acid anhydrides, gac and acid catalyst in the citrate finished product that makes; at 60 DEG C ~ 100 DEG C, react 0.5h ~ 3.5h; cooled and filtered gac; the filtrate recovered acid that adds water, aftertreatment makes long chain acylation citric acid ester finished product.
Described acid catalyst is tetrabutyl titanate, sulfonic acid type organic acid or mineral acid, as sulfuric acid, sodium pyrosulfate, tosic acid, Phenylsulfonic acid, methanesulfonic, trifluoromethayl sulfonic acid etc.Optimization methane sulfonic acid or trifluoromethayl sulfonic acid, or the mixture of the two arbitrary proportion, it is little that this catalyzer has catalyst levels, the advantage that catalytic efficiency is high.During step 1) citrate is synthetic, methanesulfonic or trifluoromethayl sulfonic acid catalyst levels are 0.01% ~ 2.0% of (hydration) citric acid quality, preferably 0.05% ~ 1.0%; In the time that acylation reaction adopts citrate finished product, the catalyst levels adding when acetylize in step 3) is 0.005% ~ 2.0% of citrate final product quality, preferably 0.01% ~ 1.0%.
Described alcohol is fatty n-alcohol or the branched-chain alcoho that in molecule, total carbon number is 2 ~ 13.
Described (hydration) citric acid and the mol ratio of alcohol are 1:3 ~ 7, preferably 1:4 ~ 5.
Described acid anhydrides is preferably propionic anhydride, butyryl oxide or valeric anhydride.
Described (hydration) citric acid and the mol ratio of acid anhydrides are 1:1 ~ 2, preferably 1:1.1 ~ 1.5.
The inventive method both can adopt integrated synthetic method, i.e. the step 1) esterification reaction product citrate crude product that only dealcoholysis makes, the direct acidylate of citrate crude product is synthesized acylated citrate esters, and acidylate and decolouring carry out simultaneously; Also can be as prior synthesizing method, after citric acid crude product refining, carry out again acylation reaction, acylation reaction is added catalyzer, and acidylate is still carried out with decolouring simultaneously.
Step 2) in, citric acid crude product refining can adopt method of the prior art, comprises the processes such as neutralization, washing, dehydration, decolouring.
In step 3), when acylation reaction, add activated carbon decolorizing.The preferred wood activated charcoal of described gac, as craboraffin, the consumption of gac is 0.2% ~ 0.8% of citrate quality.
In step 3), described aftertreatment comprises alkali neutralization, washing and dehydration.
The present invention, for the preparation of long chain acylation citric acid ester, has better performance as softening agent than acetyl citrate, also has following useful technique effect:
(1) integral process of the present invention has saved refining citrate link in traditional technology, directly carries out acylation reaction after dealcoholysis, can reduce " three wastes ", reduces costs, and improves product yield.
(2) esterification and acylation reaction adopt same catalyzer, and while particularly adopting methanesulfonic and/or trifluoromethayl sulfonic acid catalyzer, catalyst levels is few, excellent catalytic effect.
(3) acidylate is carried out with decolouring simultaneously, and activated carbon dosage few (citrate quality 0.2% ~ 0.8%), has saved independent decolouring step.
(4) reaction conditions gentleness, Energy Intensity Reduction, equipment corrosion obviously reduces, with short production cycle, the three wastes " discharge is less.
(5) the inventive method esterification yield high (>=98.5%), good product quality, acylated citrate esters purity >=99.3%, color and luster≤15#(platinum-cobalt).
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
Embodiment
Embodiment 1
A technique for synthesizing propionyl tributyl citrate, adopts integral method, comprises the following steps:
1) tributyl citrate is synthetic
Add monohydrate potassium 21.0kg(100mol to the reaction flask of being furnished with agitator, thermometer, water trap and prolong), propyl carbinol 29.7kg(400mol) and catalyst sulfuric acid 210g(monohydrate potassium quality 1.0%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesizing citric acid tri-n-butyl, press GB 1668-81 and survey acid number, esterification yield >=98.5%, product obtains tributyl citrate crude product after dealcoholysis.
2) propionyl tributyl citrate is synthetic
In the tributyl citrate crude product (35.5kg) making to step 1), add propionic anhydride 15.6kg(120.0mol) and craboraffin 180g, at 70 DEG C, react 1.5h, synthesizing propionyl tributyl citrate, then filter activity charcoal, filtrate is reclaimed propionic acid after adding water and being hydrolyzed propionic anhydride, with 5% sodium carbonate alkali lye neutralization, washing, dehydration, obtain propionyl tributyl citrate finished product.
Prepared propionyl tributyl citrate finished product product purity >=99.3%, acid number≤0.020mgKOH/g, color and luster≤15#(platinum-cobalt), moisture≤0.020%.
Embodiment 2
A technique for synthetic butyryl tributyl citrate, adopts integral method, comprises the following steps:
1) tributyl citrate is synthetic
Add monohydrate potassium 21.0kg(100mol to the reaction flask of being furnished with agitator, thermometer, water trap and prolong), propyl carbinol 29.7kg(400mol) and catalyzer tosic acid 168.0g(monohydrate potassium quality 0.8%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesizing citric acid tri-n-butyl, press GB 1668-81 and survey acid number, esterification yield >=98.5%, product obtains tributyl citrate crude product after dealcoholysis.
2) butyryl tributyl citrate is synthetic
In the tributyl citrate crude product (35.5kg) making to step 1), add butyryl oxide 19.0kg(120.0mol) and craboraffin 180g, at 70 DEG C, react 1.5h, synthetic butyryl tributyl citrate, then filter activity charcoal, filtrate is reclaimed butyric acid after adding water and being hydrolyzed butyryl oxide, with 5% sodium carbonate alkali lye neutralization, washing, dehydration, obtain butyryl tributyl citrate finished product.
Prepared butyryl tributyl citrate finished product product purity >=99.3%, acid number≤0.020mgKOH/g, color and luster≤15#(platinum-cobalt), moisture≤0.020%.
Embodiment 3
A technique for synthetic butyryl tributyl citrate, adopt integral method, substantially the same manner as Example 2, difference be used catalyst be tetrabutyl titanate 105.0g(monohydrate potassium quality 0.5%).
Embodiment 4
A technique for synthetic valeryl tributyl citrate, adopts integral method, comprises the following steps:
1) tributyl citrate is synthetic
Add monohydrate potassium 21.0kg(100mol to the reaction flask of being furnished with agitator, thermometer, water trap and prolong), propyl carbinol 29.7kg(400mol) and catalyst methane sulfonic acid 84.0g(monohydrate potassium quality 0.4%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesizing citric acid tri-n-butyl, press GB 1668-81 and survey acid number, esterification yield >=98.5%, product obtains tributyl citrate crude product after dealcoholysis.
2) valeryl tributyl citrate is synthetic
In the tributyl citrate crude product (35.5kg) making to step 1), add valeric anhydride 22.4kg(120.0mol) and craboraffin 180g, at 70 DEG C, react 1.5h, synthetic valeryl tributyl citrate, then filter activity charcoal, filtrate is reclaimed valeric acid after adding water and being hydrolyzed valeric anhydride, with 5% sodium carbonate alkali lye neutralization, washing, dehydration, obtain valeryl tributyl citrate finished product.
Prepared valeryl tributyl citrate finished product product purity >=99.3%, acid number≤0.020mgKOH/g, color and luster≤15#(platinum-cobalt), moisture≤0.020%.
Embodiment 5
A technique for synthesizing propionyl tripentyl citrates, adopts integral method, comprises the following steps:
1) tripentyl citrates is synthetic
Add monohydrate potassium 21.0kg(100mol to the reaction flask of being furnished with agitator, thermometer, water trap and prolong), Pentyl alcohol 35.3kg(400mol), catalyzer trifluoromethayl sulfonic acid 21.0g(monohydrate potassium quality 0.1%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesizing citric acid triamyl, press GB 1668-81 and survey acid number, esterification yield >=98.5%, product obtains tripentyl citrates crude product after de-amylalcohol.
2) propionyl tripentyl citrates is synthetic
In the tripentyl citrates crude product (39.4kg) making to step 1), add propionic anhydride 15.6kg(120mol) and craboraffin 72g, at 70 DEG C, react 1.5h, synthesizing propionyl tripentyl citrates, then filter activity charcoal, filtrate is reclaimed propionic acid after adding water and being hydrolyzed propionic anhydride, with 5% sodium carbonate alkali lye neutralization, washing, dehydration, obtain propionyl tripentyl citrates finished product.
Prepared propionyl tripentyl citrates finished product product purity >=99.3%, acid number≤0.020mgKOH/g, color and luster≤15#(platinum-cobalt), moisture≤0.020%.
Embodiment 6
A technique for synthetic butyryl tripentyl citrates, adopts integral method, comprises the following steps:
1) tripentyl citrates is synthetic
To being furnished with agitator, thermometer, the reaction flask of water trap and prolong adds monohydrate potassium 21.0kg(100mol), propyl carbinol 29.7kg(400mol) and catalyst methane sulfonic acid 29.4g(monohydrate potassium quality 0.14%) and trifluoromethayl sulfonic acid 12.6g(monohydrate potassium quality 0.06%, the total consumption of catalyzer account for monohydrate potassium quality 0.20%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesizing citric acid tri-n-butyl, press GB 1668-81 and survey acid number, esterification yield >=98.5%, product obtains tributyl citrate crude product after dealcoholysis.
2) butyryl tripentyl citrates is synthetic
In the tripentyl citrates crude product (39.4kg) making to step 1), add butyryl oxide 19.0kg(120mol) and craboraffin 72g, at 75 DEG C, react 1.5h, synthetic butyryl tripentyl citrates, then filter activity charcoal, filtrate is reclaimed butyric acid after adding water and being hydrolyzed butyryl oxide, with 5% sodium carbonate alkali lye neutralization, washing, dehydration, obtain butyryl tripentyl citrates finished product.
Prepared butyryl tripentyl citrates finished product product purity >=99.3%, acid number≤0.020mgKOH/g, color and luster≤15#(platinum-cobalt), moisture≤0.020%.
Embodiment 7
A technique for synthetic valeryl tripentyl citrates, adopts integral method, comprises the following steps:
1) tripentyl citrates is synthetic
Add monohydrate potassium 21.0kg(100mol to the reaction flask of being furnished with agitator, thermometer, water trap and prolong), propyl carbinol 29.7kg(400mol) and catalyzer trifluoromethayl sulfonic acid 16.8g(monohydrate potassium quality 0.08%), stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C, synthesizing citric acid tri-n-butyl, press GB 1668-81 and survey acid number, esterification yield >=98.5%, product obtains tributyl citrate crude product after dealcoholysis.。
2) valeryl tripentyl citrates is synthetic
In the tripentyl citrates crude product (39.4kg) making to step 1), add valeric anhydride 22.4kg(120mol) and craboraffin 72g, at 75 DEG C, react 1.5h, synthetic valeryl tripentyl citrates, then filter activity charcoal, filtrate is reclaimed valeric acid after adding water and being hydrolyzed valeric anhydride, with 5% sodium carbonate alkali lye neutralization, washing, dehydration, obtain valeryl tripentyl citrates finished product.
Prepared valeryl tripentyl citrates finished product product purity >=99.3%, acid number≤0.020mgKOH/g, color and luster≤15#(platinum-cobalt), moisture≤0.020%.
Claims (5)
1. a technique for synthetic long chain acylation citric acid ester, comprises the following steps:
1) citrate is synthetic
In reactor, add (hydration) citric acid, alcohol and acid catalyst, described alcohol is fatty n-alcohol or the branched-chain alcoho that in molecule, total carbon number is 2 ~ 13, and described (hydration) citric acid and the mol ratio of alcohol are 1:3 ~ 7; Described acid catalyst is sulfuric acid, tosic acid, tetrabutyl titanate, methanesulfonic or trifluoromethayl sulfonic acid, and stirring reaction 3.0h ~ 6.0h at 130 DEG C ~ 160 DEG C reclaims alcohol, obtains citrate crude product;
2) long chain acylation citric acid ester is synthetic
In the citrate crude product making to step 1), add acid anhydrides and the gac of the above carboxylic acid of C3, described (hydration) citric acid and the mol ratio of acid anhydrides are 1:1 ~ 2, and the consumption of gac is 0.2% ~ 0.8% of citrate quality; At 60 DEG C ~ 100 DEG C, react 0.5h ~ 3.5h, cooled and filtered gac, the filtrate recovered acid that adds water, aftertreatment makes acylated citrate esters finished product.
2. the technique of synthetic long chain acylation citric acid ester according to claim 3; it is characterized in that: described acid catalyst is methanesulfonic or trifluoromethayl sulfonic acid; or the mixture of the two arbitrary proportion, in step 1), consumption is 0.01% ~ 2.0% of (hydration) citric acid quality.
3. the technique of synthetic long chain acylation citric acid ester according to claim 1, is characterized in that: described acid anhydrides is propionic anhydride, butyryl oxide or valeric anhydride.
4. the technique of synthetic long chain acylation citric acid ester according to claim 1, is characterized in that: described gac is wood activated charcoal.
5. the technique of synthetic long chain acylation citric acid ester according to claim 1, is characterized in that: step 2) in, described aftertreatment comprises alkali neutralization, washing and dehydration.
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| CN104650335A (en) * | 2015-02-04 | 2015-05-27 | 南京航空航天大学 | Technology for preparing long-chain acylated citric acid ester by distributed control continuous integration technique |
| CN113072869B (en) * | 2021-03-04 | 2022-05-06 | 广州鸿泰新材料科技有限公司 | Polyurethane waterproof coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1049332A (en) * | 1989-08-08 | 1991-02-20 | 纳贝斯高·布兰股伦有限公司 | The preparation method of neoalkyl triol triesters |
| CN101125814A (en) * | 2007-09-17 | 2008-02-20 | 李祥庆 | Method for synthesizing acetyl tributyl citrate by using ion type catalyst |
| CN101830803A (en) * | 2010-01-25 | 2010-09-15 | 西北师范大学 | Method for synthesizing citric acid ester type compound |
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| DE10106627C1 (en) * | 2001-02-13 | 2002-09-19 | Celanese Chem Europe Gmbh | Process for the preparation of esters of citric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049332A (en) * | 1989-08-08 | 1991-02-20 | 纳贝斯高·布兰股伦有限公司 | The preparation method of neoalkyl triol triesters |
| CN101125814A (en) * | 2007-09-17 | 2008-02-20 | 李祥庆 | Method for synthesizing acetyl tributyl citrate by using ion type catalyst |
| CN101830803A (en) * | 2010-01-25 | 2010-09-15 | 西北师范大学 | Method for synthesizing citric acid ester type compound |
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