CN1554638A - Catalytic alcohol acid esterizing method - Google Patents
Catalytic alcohol acid esterizing method Download PDFInfo
- Publication number
- CN1554638A CN1554638A CNA2003101234855A CN200310123485A CN1554638A CN 1554638 A CN1554638 A CN 1554638A CN A2003101234855 A CNA2003101234855 A CN A2003101234855A CN 200310123485 A CN200310123485 A CN 200310123485A CN 1554638 A CN1554638 A CN 1554638A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- chain
- reaction
- alkyl
- coo
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 239000002253 acid Substances 0.000 title abstract description 10
- 239000002608 ionic liquid Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- -1 alkyl pyridine Chemical compound 0.000 claims abstract description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000001261 hydroxy acids Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 230000006837 decompression Effects 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000032050 esterification Effects 0.000 description 11
- 238000005886 esterification reaction Methods 0.000 description 11
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001577 simple distillation Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 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 description 2
- CQGJCHXPMCFGQJ-UHFFFAOYSA-N CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC Chemical class CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC CQGJCHXPMCFGQJ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The catalytic alcohol acid esterizing process features that ionic liquid in the form of A+B- is used as catalyst, where A is alkyl pyridine, imidazole and other nitrous compound; and B is TA (CF3COO), HB (C3F7COO), TfO (CF3SO3), etc. and A may be in the form shown in expression (1) and B may be in the form shown in expression (2). The present invention features that the ionic liquid has simple synthesis process and low cost, and the catalytic esterizing reaction has high selectivity, simple process, simple separation of final product from the catalyst, easy recovering, high product purity, reuse of the catalyst and easy industrial application.
Description
Technical field
The present invention relates to a kind of catalytic hydroxy acid esterifying process, it is characterized by ionic liquid as catalyzer, ion liquid form is: A
+B
-, wherein A is a nitrogen-containing heterocycle compound, comprises alkyl pyridine or 1,3 alkyl imidazole, the chain length of alkyl is C
1To C
15B is simple haloid element fluorine, chlorine, bromine or TA
-(CF
3COO
-), HB
-(C
3F
7COO
-), TfO
-(CF
3SO
3 -), NfO
-(C
4F
9SO
3 -), Tf
2N
-((CF
3SO
2)
2N)
-, Beti
-((C
2F
3SO
2)
2N
-), Tf
3C
-((CF
3SO
2 -)
3C
-), CB
11H
12 -(and substituent), CH
3COO
-, NO
3 -, SO
4 -, NO
2 -, HSO
3 -Deng; A also can be the form shown in (1), is abbreviated as: [PR
1R
2R
3R
4]
+, R wherein
1R
2R
3R
4Branched-chain or straight-chain alkyl for any chain length; B is the form shown in (2) simultaneously, and R is the branched-chain or straight-chain alkyl of any chain length.
Background technology
The ester class can be used as spices, foodstuff additive, softening agent, defoamer and good organic solvent, is a kind of crucial organic compound.The esterification process of background technology adopts protonic acid, solid acid, ion exchange resin etc. to realize as catalyzer mostly.Protonic acid easily makes organic matter carbonizing, oxidation as catalyzer, so side reaction increases, the ester products color and luster is dark, and productive rate is influenced.Protonic acid is understood etching apparatus in addition, and a large amount of spent acid discharge then contaminate environment.For solid catalysts such as solid acid, the ion exchange resin alcoholic acid esterification catalysts of new generation of protonic acid as an alternative, all be successful exploration, but deficiency is also arranged, as solid super-strong acid as catalyzer, by product is more, and lose easily in the active centre, the reaction process more complicated; The use temperature that resin cation (R.C.) allowed is lower, and the scope of application also is subjected to certain restriction.Therefore seek environmental friendliness, efficient, economic catalyzer is significant.Advantages such as ionic liquid is the eco-friendly novel material of greatly being paid close attention in recent years of a class, has good stability, and is non-volatile.Patent CN 1247856A has reported and has utilized ionic liquid-catalyzed esterification method, but the ionic liquid that this patent is used as metal or non-metallic halide formation, the ionic liquid poor stability that metal halide constitutes, and meet water and be easy to decompose, its shortcoming is also embodied in must have certain restriction to feed way.Patent CN 1405140A has reported and has utilized ionic liquid [Hmim]
+BF
4The method of catalytic esterification, but the ionic liquid that contains F is met water and is easy to decompose report (the Richard P.Swatloski that generates HF, Greem Cheistry, 2003 (5): 361-363.) proved that such ionic liquid does not have environment friendly, and this patent is in implementation process, ion liquid usage quantity is big (being equal to reactant) basically too, is not suitable as catalyzer.
The ionic liquid that the present invention uses, form is: A
+B
-, wherein A is a nitrogen-containing heterocycle compound, comprises alkyl pyridine or 1,3 alkyl imidazole, the chain length of alkyl is C
1To C
15B is simple haloid element fluorine, chlorine, bromine or TA
-(CF
3COO
-), HB
-(C
3F
7COO
-), TfO
-(CF
3SO
3 -), NfO
-(C
4F
9SO
3 -), Tf
2N
-((CF
3SO
2)
2N)
-, Beti
-((C
2F
3SO
2)
2N
-), Tf
3C
-((CF
3SO
2 -)
3C
-), CB
11H
12 -(and substituent), CH
3COO
-, NO
3 -, SO
4 -, NO
2 -, HSO
3 -Deng; A also can be the form shown in (1), is abbreviated as: [PR
1R
2R
3R
4]
+, R wherein
1R
2R
3R
4Branched-chain or straight-chain alkyl for any chain length; B is the form shown in (2) simultaneously, and R is the branched-chain or straight-chain alkyl of any chain length, and is synthetic very easy, and meets water and do not decompose environmental friendliness.
Summary of the invention
The purpose of this invention is to provide a kind of environmental friendliness, the simple esterification process of technology.
The present invention realizes by following measure:
The ionic liquid that the present invention uses, form is: A
+B
-, wherein A is a nitrogen-containing heterocycle compound, comprises alkyl pyridine or 1,3 alkyl imidazole, the chain length of alkyl is C
1To C
15B is simple haloid element fluorine, chlorine, bromine or TA
-(CF
3COO
-), HB
-(C
3F
7COO
-), TfO
-(CF
3SO
3 -), NfO
-(C
4F
9SO
3 -), Tf
2N
-((CF
3SO
2)
2N)
-, Beti
-((C
2F
3SO
2)
2N
-), Tf
3C
-((CF
3SO
2 -)
3C
-), CB
11H
12 -(and substituent), CH3COO
-, NO
3 -, SO
4 -, NO
2 -, HSO
3 -Deng; A also can be the form shown in (1), is abbreviated as: [PR
1R
2R
3R
4]
+, R wherein
1R
2R
3R
4Branched-chain or straight-chain alkyl for any chain length; B is the form shown in (2) simultaneously, and R is the branched-chain or straight-chain alkyl of any chain length
The process of this esterification process is: in two mouthfuls of round-bottomed flasks of reflux condensation mode, water trap and thermometer are housed, reactant alcohol, acid and a certain amount of ionic liquid are added together, addition sequence in no particular order.Stir and be warming up to suitable temperature of reaction (according to the needs of reactant).The boiling reflux reaction divides water until anhydrous generation.Stop heating, stir, static for some time, esterification products and ionic liquid natural layering, the upper strata is an esterification products, remaining ionic liquid is recycled.The present invention compares with background technology, and the present invention has advantage:
What 1, the present invention used is ionic liquid-catalyzed active high, does not need to add other auxiliary agent or organic solvent, the product purity height.
2, the method for synthesizing ionic liquid of the present invention's use is easy, with low cost.
3, the ionic liquid chance water of the present invention's use does not decompose, and stable in properties to the equipment non-corrosiveness, has realized eco-friendly catalytic process.
Embodiment
Embodiment one: with 0.02 mole of ionic liquid [P
666,14LABS] and acetate and 0.25 mole of propyl carbinol of 0.25 mole put into reaction flask, stir, heating, controlled temperature 100-130 ℃ of reaction 2 hours, reaction is left standstill, and tells the esterification products n-butyl acetate by separatory, transformation efficiency is 94%, selectivity is 99%.After dewatering, the ionic liquid simple distillation of lower floor recycles.[P
666,14LABS] name be called: trihexyl (tetradecyl) phosphonium dodecylbenzenesulfonates molecular formula is:
Embodiment two: with 0.04 mole of ionic liquid [P
666,14LABS] and acetate and 0.25 mole of propyl carbinol of 0.25 mole put into reaction flask, stir, heating, controlled temperature 100-130 ℃ of reaction 2 hours, reaction is left standstill, and tells the esterification products n-butyl acetate by separatory, transformation efficiency is 97%, selectivity is 99%.After dewatering, the ionic liquid simple distillation of lower floor recycles.[P
666,14LABS] name be called: trihexyl (tetradecyl) phosphonium dodecylbenzenesulfonates molecular formula is:
Embodiment three: acetate and 0.25 mole of propyl carbinol of 0.04 mole of ionic liquid [BmimCl] and 0.25 mole are put into reaction flask, stir, heat, controlled temperature 100-130 ℃ was reacted 2 hours, reaction is left standstill, tell the esterification products n-butyl acetate by separatory, transformation efficiency is 96%, and selectivity is 99%.After dewatering, the ionic liquid simple distillation of lower floor recycles.[BmimCl] molecular formula is:
Claims (4)
1, a kind of catalytic hydroxy acid esterifying process is characterized in that ionic liquid as catalyzer, and ion liquid form is: A
+B
-, wherein A is a nitrogen-containing heterocycle compound, comprises alkyl pyridine or 1,3 alkyl imidazole, the chain length of alkyl is C
1To C
15B is simple haloid element fluorine, chlorine, bromine or TA
-(CF
3COO
-), HB
-(C
3F
7COO
-), TfO
-(CF
3SO
3 -), NfO
-(C
4F
9SO
3 -), Tf
2N
-((CF
3SO
2)
2N)
-, Beti
-((C
2F
3SO
2)
2N
-), Tf
3C
-((CF
3SO
2 -)
3C
-), CB
11H
12 -(and substituent), CH
3COO
-, NO
3 -, SO
4 -, NO
2 -, HSO
3 -Deng; A also can be the form shown in (1), is abbreviated as: [PR
1R
2R
3R
4]
+, R wherein
1R
2R
3R
4Branched-chain or straight-chain alkyl for any chain length; B is the form shown in (2) simultaneously, and R is the branched-chain or straight-chain alkyl of any chain length.
2, the method for claim 1, it is characterized in that the used ionic liquid of the present invention (perhaps ionic liquid mixture) has stronger katalysis, catalytic reaction deionization liquid does not need to add other catalyzer, auxiliary agent or reaction outward again and promotes medium; Stable in properties, not facile hydrolysis.
3, the method for claim 1, the add-on of the used ionic liquid of the present invention (perhaps ion liquid mixture), the amount of haloid element fluorine, chlorine, bromine, metal or non-metallic element in the ionic liquid of pressing is calculated, by the 0.1-20% (mole) of adding reactant alcohol, sour total mole number; Temperature of reaction is 50-200 ℃, and under normal pressure or the decompression, the reaction times is 0.5-5 hour.
4, the method for claim 1 is characterized in that, among the present invention, can random order add ionic liquid (perhaps ion liquid mixture) and reactant, and reaction is not had influence.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310123485 CN1232497C (en) | 2003-12-29 | 2003-12-29 | Catalytic alcohol acid esterizing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310123485 CN1232497C (en) | 2003-12-29 | 2003-12-29 | Catalytic alcohol acid esterizing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1554638A true CN1554638A (en) | 2004-12-15 |
| CN1232497C CN1232497C (en) | 2005-12-21 |
Family
ID=34338890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310123485 Expired - Lifetime CN1232497C (en) | 2003-12-29 | 2003-12-29 | Catalytic alcohol acid esterizing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1232497C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355745C (en) * | 2005-03-18 | 2007-12-19 | 清华大学 | Method for synthesizing D,L-alpha-tocopherol catalyzed by ion-liquid |
| CN100404495C (en) * | 2005-09-30 | 2008-07-23 | 清华大学 | Tributyl citrate preparation method using ion liquid catalysis |
| CN101857608A (en) * | 2010-05-28 | 2010-10-13 | 中国科学院过程工程研究所 | Imidazole ionic liquid phosphine ligand and application of coordination compound thereof in hydroesterification |
| CN101456844B (en) * | 2007-12-13 | 2010-12-08 | 中国科学院兰州化学物理研究所 | Room temperature ion liquid containing sulfonic acid ester base side chain as well as preparation method and use thereof |
| CN102773118A (en) * | 2012-08-14 | 2012-11-14 | 南京大学 | Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling |
| CN106905150A (en) * | 2017-02-10 | 2017-06-30 | 长春工业大学 | A kind of synthetic method of n-butyl acetate |
| CN106939014A (en) * | 2016-01-04 | 2017-07-11 | 中化化工科学技术研究总院 | A kind of quaternary phosphonium salt ionic liquid and its production and use |
| CN112979463A (en) * | 2019-12-13 | 2021-06-18 | 中化化工科学技术研究总院有限公司 | Method for synthesizing ester by catalytic esterification of ionic liquid |
-
2003
- 2003-12-29 CN CN 200310123485 patent/CN1232497C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355745C (en) * | 2005-03-18 | 2007-12-19 | 清华大学 | Method for synthesizing D,L-alpha-tocopherol catalyzed by ion-liquid |
| CN100404495C (en) * | 2005-09-30 | 2008-07-23 | 清华大学 | Tributyl citrate preparation method using ion liquid catalysis |
| CN101456844B (en) * | 2007-12-13 | 2010-12-08 | 中国科学院兰州化学物理研究所 | Room temperature ion liquid containing sulfonic acid ester base side chain as well as preparation method and use thereof |
| CN101857608A (en) * | 2010-05-28 | 2010-10-13 | 中国科学院过程工程研究所 | Imidazole ionic liquid phosphine ligand and application of coordination compound thereof in hydroesterification |
| CN102773118A (en) * | 2012-08-14 | 2012-11-14 | 南京大学 | Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling |
| CN102773118B (en) * | 2012-08-14 | 2015-06-10 | 南京大学 | Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling |
| CN106939014A (en) * | 2016-01-04 | 2017-07-11 | 中化化工科学技术研究总院 | A kind of quaternary phosphonium salt ionic liquid and its production and use |
| CN106939014B (en) * | 2016-01-04 | 2019-05-17 | 中化化工科学技术研究总院有限公司 | A kind of quaternary phosphonium salt ionic liquid and its preparation method and application |
| CN106905150A (en) * | 2017-02-10 | 2017-06-30 | 长春工业大学 | A kind of synthetic method of n-butyl acetate |
| CN112979463A (en) * | 2019-12-13 | 2021-06-18 | 中化化工科学技术研究总院有限公司 | Method for synthesizing ester by catalytic esterification of ionic liquid |
| CN112979463B (en) * | 2019-12-13 | 2023-03-28 | 中化化工科学技术研究总院有限公司 | Method for synthesizing ester by catalytic esterification of ionic liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1232497C (en) | 2005-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1326826C (en) | Continuous method for preparing ethyl lactate | |
| CN101812039B (en) | Method for generating 5-hydroxymethylfurfural by using ionic liquid catalysis | |
| CN1232497C (en) | Catalytic alcohol acid esterizing method | |
| CN105408299B (en) | Pass through the method for the esterification continuous production light acrylate of thick ester level acrylic acid | |
| CN102001936A (en) | Continuous production method of propyl acetate | |
| CN103030564A (en) | Method for carrying out high-efficiency catalytic alcoholysis on polyethylene terephthalate (PET) by multi-component catalyst | |
| CN102108047B (en) | Method for preparing 2,3,5-trimethylhydroquinone | |
| CN101391956B (en) | Method for synthesizing methyl oleate and epoxy methyl oleate in ion liquid medium | |
| CN101977922B (en) | Method for preparation of anhydrosugar ethers | |
| CN102311360B (en) | Method for preparing N-ethoxy oxalyl alanine ethyl ester | |
| CN102267898A (en) | Method for preparing diethyl succinate by using pyridine ionic liquid as catalyst | |
| CN103709039B (en) | Method for synthesizing methyl (ethyl) gallate through catalysis of Cu-mordenite | |
| CN100567259C (en) | A kind of method for preparing glycol sulfite | |
| CN103664628A (en) | Method for preparing organic carbonate through aliphatic chloride indirect phosgene method | |
| CN103524402A (en) | Preparation method of efficient stable inhibitor | |
| CN101993371A (en) | Preparation method of allyl acrylate | |
| CN104829457A (en) | Method for Bronsted-Lewis acidic ionic liquid catalyzed synthesis of di(glycol monoalkyl ether)terephthalate | |
| CN111153794A (en) | Method for synthesizing ethyl palmitate by using dodecyl trimethyl ammonium chloride-based eutectic solvent catalyst | |
| CN102363609A (en) | Efficient stable polymerization inhibitor and preparation method thereof | |
| CN101863782A (en) | Method for synthesizing ultraviolet photoinitiator of p-dimethylamin benzoic ether compounds | |
| CN103214368A (en) | Method for preparing alkyl diol alkyl ether (meth)acrylate | |
| CN1301237C (en) | Method for producing fluorobromobenzene using fluorobenzene | |
| CN1247856A (en) | Clean catalytic hydroxy acid esterifying process | |
| CN103524337A (en) | Preparation method of butyl levulinate by use of biomass based furfuryl alcohol | |
| KR101346370B1 (en) | Effective preparation method for (meth)acrylate |
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 | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20051221 |