CN1303055C - Catylatic synthesizing method of acetyl tri-in-butyl citrate - Google Patents
Catylatic synthesizing method of acetyl tri-in-butyl citrate Download PDFInfo
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- CN1303055C CN1303055C CNB2005100504339A CN200510050433A CN1303055C CN 1303055 C CN1303055 C CN 1303055C CN B2005100504339 A CNB2005100504339 A CN B2005100504339A CN 200510050433 A CN200510050433 A CN 200510050433A CN 1303055 C CN1303055 C CN 1303055C
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- Prior art keywords
- atbc
- tri
- butyl citrate
- water
- tributyl ester
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- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 title 1
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims abstract description 64
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims abstract description 41
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 9
- 239000003729 cation exchange resin Substances 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- -1 inorganic acid salt Chemical class 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical group [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 3
- 238000013019 agitation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a catylatic synthesizing method of O-acetylcitric acid tributyl ester, which comprises the following steps: step 1, citric acid tributyl ester, acetic anhydride and a catalyst are together added into a three-opening flask immersed in water, agitation is carried out for reaction, and a crude product of o-acetylcitric acid tributyl ester is obtained; step 2, after the crude product is sucked and filtrated and the catalyst is recovered, acetic anhydride and acetic acid are recovered by pressure-reduction distillation, the crude product is washed by deionized water and an alkaline water solution, and then is washed by water until the water phase is in neutrality, and water is removed by the pressure-reduction distillation. The method of the present invention is simple, the used catalyst is cheap and can be easily obtained, the preparation is simple, the catalytic performance is good, and the catalyst can be used in circulation. When the method of the present invention is used under a proper condition, the raw material of the citric acid tributyl ester can be basically and completely converted. The problem of the difficult separation of the citric acid tributyl ester and the O-acetylcitric acid tributyl ester is avoided. Gas-phase chromatographic analysis proves that the purity of the obtained O-acetylcitric acid tributyl ester is higher than 99%.
Description
Technical field
The present invention relates to the process for catalytic synthesis of ATBC.
Background technology
ATBC is novel nontoxic additive, the softening agent that can be used for plastic working industries such as food product pack, medical utensil, toy for children, personal hygiene article, plastics such as PVC, vinyl chloride vinyl acetate copolymer there is good consistency, it is good around song that plastics after its plasticising have low temperature, when sealing by fusing to thermally-stabilised, fast light, water-fast, cold-resistant.
In the process for catalytic synthesis of the ATBC that provides on the document, mainly be the difference of catalyzer, the effect of different catalyzer synthesis of acetyl tri-n-butyl citrate differs, and purified technology also is not quite similar.The tosic acid of employing, thionamic acid, pyridine etc. are arranged as the catalyzer synthesis of acetyl tri-n-butyl citrate, the refining more complicated of product, catalyzer and product are not easily separated, and quality product is difficult to guarantee, and catalyzer can not recycle, and production cost obviously improves; The carried superstrong solid acid of employing is also arranged as the catalyzer synthesis of acetyl tri-n-butyl citrate, the Preparation of catalysts complexity costs an arm and a leg, and the transformation efficiency of tributyl citrate is not high yet, brings difficulty to product purification; Adopt inorganic acids such as the vitriol oil, concentrated hydrochloric acid as the catalyzer synthesis of acetyl tri-n-butyl citrate in addition, but above-mentioned catalyzer is serious to equipment corrosion, side reaction is many, the refining more complicated of product, catalyzer and product are not easily separated, quality product is difficult to guarantee that catalyzer can not be recycled.
Summary of the invention
The purpose of this invention is to provide that a kind of technology is simple, product purity is high, be beneficial to the process for catalytic synthesis that reduces production costs, is fit to the ATBC of suitability for industrialized production.
The process for catalytic synthesis of ATBC of the present invention may further comprise the steps:
1) join tri-n-butyl citrate and diacetyl oxide in the there-necked flask that places water-bath together with catalyzer, the mol ratio of tri-n-butyl citrate and diacetyl oxide is 1: 1.5～3.0, catalyst consumption is 1～7% of a tributyl citrate quality, under 50 ℃～100 ℃ temperature, stirring reaction 15～120min obtains the tributyl acetylcitrate crude product;
2) with behind the above-mentioned crude product filtering recovering catalyst, diacetyl oxide and acetate are reclaimed in underpressure distillation, again through the solution washing of deionized water wash, 5%～20% alkali, be washed to water then and be neutral, moisture is removed in underpressure distillation, gets final product.
Catalyzer described in the present invention can adopt inorganic acid salt or change into the Zeo-karb of H type.Wherein inorganic acid salt can be sodium pyrosulfate or sal enixum; The Zeo-karb that changes into the H type can be H type macropore strong acid cation exchange resin, H type storng-acid cation exchange resin or H type weakly acidic cation-exchange resin.The aqueous solution of said alkali can adopt yellow soda ash, sodium hydroxide or sodium bicarbonate aqueous solution.
Filtering recovering catalyst in the aforesaid method adopts suction filtration, because the viscosity of ATBC is very big under the normal temperature, if adopt common filtration, speed is too slow.
The reaction equation of acetylation is:
The analytical procedure of the product that the present invention makes: adopt the Agilent6890N gas chromatograph to analyze the yield and the purity of ATBC.Chromatographic column: HP-55% Phenyl Methyl SiloxaneCapillary 30.0m * 320 μ m * 0.25 μ m, FID detects, 280 ℃ of detector temperatures, temperature programming, 150 ℃ keep 2min, are raised to 260 ℃ with 15 ℃/min again, splitting ratio 100: 1, air flow quantity 300ml/min, H
2Flow 30ml/min, carrier gas is 99.999%N
2, flow 1ml/min, 270 ℃ of injector temperatures.
The method of the synthesis of acetyl tri-n-butyl citrate that the present invention adopts is simple, and used catalyzer is cheap and easy to get, and preparation is simple, and catalytic performance is good, and can recycle.Adopt method of the present invention under suitable condition, the raw material tri-n-butyl citrate is transformed fully substantially, avoided the problem of tri-n-butyl citrate and ATBC separation difficulty, under simple processing condition, can obtain highly purified ATBC, the ATBC purity that obtains through gas chromatographic analysis more than 99%.
Embodiment
Further specify the present invention below in conjunction with embodiment.Following embodiment is just in order to illustrate the content of invention, rather than limits the present invention to illustrated embodiment.
Embodiment 1
By tri-n-butyl citrate and diacetyl oxide mol ratio is 1: 1.8, take by weighing tri-n-butyl citrate 18.02g, diacetyl oxide 9.18g, catalyst sulfuric acid hydrogen sodium 0.54g adds in the there-necked flask, place water-bath, keeping reacting liquid temperature is 60 ℃, stirring reaction 90min, and the yield that obtains tributyl acetylcitrate is 99.3%, the peak that does not have tri-n-butyl citrate on the gas chromatogram illustrates that tri-n-butyl citrate transforms fully.After the thick product suction filtration that reaction is obtained reclaims catalyzer, diacetyl oxide and acetate are reclaimed in underpressure distillation, again through deionized water wash, the washing of 5% aqueous sodium carbonate, be washed to water then and be neutral, moisture is removed in underpressure distillation, promptly gets ATBC.The purity of gas chromatographic analysis ATBC is more than 99%.
Embodiment 2
By tri-n-butyl citrate and diacetyl oxide mol ratio is 1: 1.5, take by weighing tri-n-butyl citrate 18.02g, diacetyl oxide 7.65g, catalyst sulfuric acid hydrogen potassium 0.90g adds in the there-necked flask, place water-bath, keeping reacting liquid temperature is 70 ℃, stirring reaction 60min, and the yield that obtains ATBC is 99.5%, the peak that does not also have tri-n-butyl citrate on the gas chromatogram illustrates that tri-n-butyl citrate transforms fully.After the thick product suction filtration that reaction is obtained reclaims catalyzer, diacetyl oxide and acetate are reclaimed in underpressure distillation, wash, be washed to then water through deionized water wash, 10% aqueous sodium hydroxide washes again and be neutral, moisture is removed in underpressure distillation, promptly gets ATBC.The purity of gas chromatographic analysis ATBC is more than 99%.
Embodiment 3
By tri-n-butyl citrate and diacetyl oxide mol ratio is 1: 1.8, take by weighing tri-n-butyl citrate 18.02g, diacetyl oxide 9.18g, catalyzer H type macropore strong acid cation exchange resin 0.54g adds in the there-necked flask, place water-bath, keeping reacting liquid temperature is 50 ℃, stirring reaction 45min, and the yield that obtains ATBC is 99.4%, the peak that does not have tri-n-butyl citrate on the gas chromatogram illustrates that tri-n-butyl citrate transforms fully.After the thick product suction filtration that reaction is obtained reclaims catalyzer, diacetyl oxide and acetate are reclaimed in underpressure distillation, again through deionized water wash, the washing of 10% sodium bicarbonate aqueous solution, be washed to water then and be neutral, moisture is removed in underpressure distillation, promptly gets ATBC.The purity of gas chromatographic analysis ATBC is more than 99%.
Embodiment 4
By tri-n-butyl citrate and diacetyl oxide mol ratio is 1: 3, take by weighing tri-n-butyl citrate 18.02g, diacetyl oxide 15.30g, catalyzer H type weakly acidic cation-exchange resin 0.90g adds in the there-necked flask, place water-bath, keeping reacting liquid temperature is 70 ℃, stirring reaction 15min, and the yield that obtains ATBC is 99.8%, the peak that does not have tri-n-butyl citrate on the gas chromatogram illustrates that tri-n-butyl citrate transforms fully.After the thick product suction filtration that reaction is obtained reclaims catalyzer, diacetyl oxide and acetate are reclaimed in underpressure distillation, wash, be washed to then water through deionized water wash, 10% aqueous sodium hydroxide washes again and be neutral, moisture is removed in underpressure distillation, promptly gets ATBC.The purity of gas chromatographic analysis ATBC is more than 99%.
Embodiment 5
By tri-n-butyl citrate and diacetyl oxide mol ratio is 1: 2, take by weighing tri-n-butyl citrate 18.02g, diacetyl oxide 10.20g, catalyzer H type storng-acid cation exchange resin 0.18g adds in the there-necked flask, place water-bath, keeping reacting liquid temperature is 80 ℃, stirring reaction 120min, and the yield that obtains ATBC is 99.6%, the peak that does not have tri-n-butyl citrate on the gas chromatogram illustrates that tri-n-butyl citrate transforms fully.After the thick product suction filtration that reaction is obtained reclaims catalyzer, diacetyl oxide and acetate are reclaimed in underpressure distillation, again through deionized water wash, the washing of 20% sodium bicarbonate aqueous solution, be washed to water then and be neutral, moisture is removed in underpressure distillation, promptly gets ATBC.The purity of gas chromatographic analysis ATBC is more than 99%.
Claims (4)
1. the process for catalytic synthesis of ATBC is characterized in that may further comprise the steps:
1) join tri-n-butyl citrate and diacetyl oxide in the there-necked flask that places water-bath together with catalyzer, the mol ratio of tri-n-butyl citrate and diacetyl oxide is 1: 1.5～3.0, catalyst consumption is 1～7% of a tri-n-butyl citrate quality, under 50 ℃～100 ℃ temperature, stirring reaction 15～120min, obtain the ATBC crude product, said catalyzer is inorganic acid salt or the Zeo-karb that changes into the H type;
2) above-mentioned crude product suction filtration is reclaimed catalyzer after, diacetyl oxide and acetate are reclaimed in underpressure distillation, again through the solution washing of deionized water wash, 5%～20% alkali, be washed to water then and be neutral, moisture is removed in underpressure distillation, gets final product.
2. the process for catalytic synthesis of ATBC according to claim 1 is characterized in that said inorganic acid salt is sodium pyrosulfate or sal enixum.
3. the process for catalytic synthesis of ATBC according to claim 1, the Zeo-karb that it is characterized in that the said H of changing into type is H type macropore strong acid cation exchange resin, H type storng-acid cation exchange resin or H type weakly acidic cation-exchange resin.
4. the process for catalytic synthesis of ATBC according to claim 1, the aqueous solution that it is characterized in that said alkali is yellow soda ash, sodium hydroxide or sodium bicarbonate aqueous solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100504339A CN1303055C (en) | 2005-06-24 | 2005-06-24 | Catylatic synthesizing method of acetyl tri-in-butyl citrate |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100504339A CN1303055C (en) | 2005-06-24 | 2005-06-24 | Catylatic synthesizing method of acetyl tri-in-butyl citrate |
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| CN1709854A CN1709854A (en) | 2005-12-21 |
| CN1303055C true CN1303055C (en) | 2007-03-07 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353305B (en) * | 2007-07-24 | 2011-09-14 | 中山联成化学工业有限公司 | Synthetic method of high-purity acetyl tributyl citrate (ATBC) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387569C (en) * | 2006-03-22 | 2008-05-14 | 浙江大学 | Device and method for catalytic synthesis of acetyl tri-n-butyl citrate by fixed bed reactor |
| CN101205185B (en) * | 2006-12-21 | 2011-05-11 | 江苏雷蒙化工科技有限公司 | Method for purifying acetyl citrate |
| CN102701975A (en) * | 2012-04-11 | 2012-10-03 | 江苏雷蒙化工科技有限公司 | Improvement of process for synthesizing acetyl tri-n-butyl citrate by activated carbon supported sulfuric acid |
| CN102659589A (en) * | 2012-05-04 | 2012-09-12 | 浙江大学 | Method for catalytically synthesizing acetyl tributyl citrate by using caprolactam acidic ionic liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557800A (en) * | 2004-02-06 | 2004-12-29 | 江南大学 | Process for preparing ethyl citrate suitable for industrialized production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557800A (en) * | 2004-02-06 | 2004-12-29 | 江南大学 | Process for preparing ethyl citrate suitable for industrialized production |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353305B (en) * | 2007-07-24 | 2011-09-14 | 中山联成化学工业有限公司 | Synthetic method of high-purity acetyl tributyl citrate (ATBC) |
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| CN1709854A (en) | 2005-12-21 |
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