CN1323062C - Method for preparing alkyl salicylic acid - Google Patents
Method for preparing alkyl salicylic acid Download PDFInfo
- Publication number
- CN1323062C CN1323062C CNB2004100711118A CN200410071111A CN1323062C CN 1323062 C CN1323062 C CN 1323062C CN B2004100711118 A CNB2004100711118 A CN B2004100711118A CN 200410071111 A CN200410071111 A CN 200410071111A CN 1323062 C CN1323062 C CN 1323062C
- Authority
- CN
- China
- Prior art keywords
- acid
- catalyst
- salicylic acid
- preparation
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 title claims abstract description 45
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229960004889 salicylic acid Drugs 0.000 title claims abstract description 27
- -1 alkyl salicylic acid Chemical compound 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 5
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 150000001768 cations Chemical group 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种烷基水杨酸的制备方法。The invention relates to a preparation method of alkyl salicylic acid.
技术背景technical background
专利UK586461、UK1146925、EP370555揭示了烷基水杨酸传统的制备方法。就是以苯酚为原料，通过和烯烃的烷基化反应制得烷基苯酚，紧接着通过koble-schmitt反应进行羧基化反应。这个反需要较高的压力和反应温度。同时在烷基酚中存在长链烷基位于邻位和对位两种情况，其大约比例为3∶1到1∶10。而邻位的活性在koble-schmitt反应中较低，因此会导致产率比预计的产率低。Patents UK586461, UK1146925, and EP370555 disclose traditional preparation methods of alkyl salicylic acid. It is to use phenol as raw material to produce alkylphenol through alkylation reaction with olefin, followed by carboxylation reaction through koble-schmitt reaction. This reaction requires higher pressure and reaction temperature. At the same time, there are two situations in which the long-chain alkyl group is located in the ortho-position and the para-position in the alkylphenol, and the approximate ratio is 3:1 to 1:10. The activity of the ortho position is lower in the koble-schmitt reaction, thus resulting in lower than expected yields.
FR-A-2542732揭示了一种水杨酸的单链烷基化制备方法，是以浓硫酸作催化剂，让水杨酸和醚类物质进行反应。其中醚中R基的碳数为1-4个。这种方法对于小批量的生产还是可行的，但是较长碳链的醚的缺乏和昂贵使得大规模生产不可行。FR-A-2542732 discloses a single-chain alkylation preparation method of salicylic acid, using concentrated sulfuric acid as a catalyst to allow salicylic acid to react with ethers. Wherein the carbon number of the R group in the ether is 1-4. This approach is feasible for small-scale production, but the scarcity and cost of longer carbon-chain ethers make large-scale production impractical.
DD-A-269619和DD-A-293108两个制备方法都是水杨酸的直接烷基化，催化剂主要是酸性离子交换树脂和多磷酸。该方法要求水杨酸要首先变为酯，而且烷基化的链长为六个碳以下。The two preparation methods of DD-A-269619 and DD-A-293108 are the direct alkylation of salicylic acid, and the catalysts are mainly acidic ion exchange resin and polyphosphoric acid. This method requires that the salicylic acid is first converted to an ester, and that the alkylated chain length is less than six carbons.
US-A-5415792则是通过对较短链的烷基水杨酸盐进行烷基化，来制备长链烷基水杨酸，就是先让甲基水杨酸盐进行水解，得到甲基水杨酸，然后进行烷基化。但这对于以后清净剂的制备只是一个多余的步骤。US-A-5415792 is to prepare long-chain alkyl salicylic acid by alkylating shorter-chain alkyl salicylate, which is to first hydrolyze methyl salicylate to obtain methyl water sylic acid, followed by alkylation. But this is only a superfluous step for the preparation of the detergent later.
EP0771782揭示了用80％的硫酸作催化剂对水杨酸直接烷基化的制备方法，该方法硫酸的用量比较大，这样使得硫酸这种腐蚀性比较强的液体不利于处理。同时该方法选择了在缺乏溶剂的条件下进行反应，增加了反应的难度。EP0771782 discloses a method for directly alkylating salicylic acid with 80% sulfuric acid as a catalyst. The amount of sulfuric acid used in this method is relatively large, which makes sulfuric acid, a highly corrosive liquid, unfavorable for handling. At the same time, the method chooses to react under the condition of lack of solvent, which increases the difficulty of the reaction.
发明内容Contents of the invention
本发明提供了一种制备烷基水杨酸的方法。The invention provides a method for preparing alkyl salicylic acid.
本发明提供的方法包括：在有机溶剂的存在下，把碳数为6-50的烯烃与水杨酸混合，在负载杂多酸的催化作用下于50℃-150℃下进行烷基化反应。The method provided by the invention comprises: in the presence of an organic solvent, mixing an alkene with a carbon number of 6-50 and salicylic acid, and carrying out an alkylation reaction at 50°C-150°C under the catalysis of a loaded heteropolyacid .
所说的溶剂为能溶解水杨酸的有机溶剂，如正丁醚等。Said solvent is an organic solvent capable of dissolving salicylic acid, such as n-butyl ether and the like.
所说的烯烃碳数为6-50，较好的碳数为8-40，最好的范围为12-30。Said olefin has a carbon number of 6-50, preferably 8-40, most preferably 12-30.
烯烃和水杨酸可以按照完全反应所需的摩尔比投料，即1∶1。Olefin and salicylic acid can be fed according to the molar ratio required for complete reaction, ie 1:1.
所说的催化剂为负载杂多酸，优选负载磷钨酸、磷钼酸，载体可以是阳离子酸性树脂。以载体的重量为100％计，杂多酸在载体上的负载量为10-70重％，优选20-50重％。负载杂多酸催化剂的用量为水杨酸重量的3-15重％，优选5-12重％。The catalyst is a loaded heteropoly acid, preferably loaded phosphotungstic acid and phosphomolybdic acid, and the carrier can be a cationic acidic resin. Based on the weight of the carrier being 100%, the load of the heteropolyacid on the carrier is 10-70 wt%, preferably 20-50 wt%. The amount of the supported heteropolyacid catalyst is 3-15 wt%, preferably 5-12 wt%, based on the weight of salicylic acid.
负载杂多酸可以采用等体积浸渍法制备。载体选用大孔强酸性阳离子交换树脂，功能基为SO3H，先用水标定载体的等体积浸渍体积，然后称取一定量的载体，再按需要的杂多酸负载量加入相应浓度的杂多酸水溶液，使其等体积浸渍在所称量的载体上，在40-80℃水浴上浸渍4-10小时，移入40-100℃烘箱烘干6-15小时后完成制备。Loaded heteropolyacids can be prepared by equal-volume impregnation. The carrier is macroporous strong acidic cation exchange resin, and the functional group is SO 3 H. Firstly, the equal-volume impregnation volume of the carrier is calibrated with water, and then a certain amount of carrier is weighed, and then the heteropoly acid of the corresponding concentration is added according to the required heteropoly acid load The acid aqueous solution is made to impregnate an equal volume on the weighed carrier, immersed in a water bath at 40-80°C for 4-10 hours, moved into an oven at 40-100°C and dried for 6-15 hours to complete the preparation.
反应温度为50℃-150℃，最佳范围为80℃-120℃。The reaction temperature is 50°C-150°C, and the optimum range is 80°C-120°C.
反应时间为0.5-10小时，较好的反应时间为1-5小时。The reaction time is 0.5-10 hours, preferably 1-5 hours.
本发明采用负载杂多酸作为催化剂，同时引入溶剂，相比于一般的催化剂，负载杂多酸具有较强的酸性，能达到较好的反应产率，并且产物和催化剂易于分离，催化剂可以多次使用，无废酸排放问题，有利于环保。The present invention adopts the loaded heteropolyacid as the catalyst, and introduces the solvent at the same time. Compared with the general catalyst, the loaded heteropolyacid has stronger acidity, can achieve better reaction yield, and the product and the catalyst are easy to separate, and the catalyst can be more It can be used for one time, and there is no problem of waste acid discharge, which is beneficial to environmental protection.
附图说明Description of drawings
图1为实施例2得到的12烯基水杨酸的质谱图。Fig. 1 is the mass spectrogram of the 12 alkenyl salicylic acid that embodiment 2 obtains.
图2为实施例3得到的16烯基水杨酸的质谱图。Fig. 2 is the mass spectrogram of the 16 alkenyl salicylic acid that embodiment 3 obtains.
具体实施方式Detailed ways
对比例1Comparative example 1
在装有冷凝管的250ml的单口圆底烧瓶中加入水杨酸13.8g，加入正丁醚为20ml，再加入16.8g正12烯烃，然后阳离子树脂1.5g。用磁力搅拌器进行搅拌，反应温度为80℃，反应时间为4小时。然后分层过滤，进行真空蒸馏，最后得到最终产品。反应转化率为0％。Add 13.8 g of salicylic acid in a 250 ml single-necked round bottom flask equipped with a condenser, add n-butyl ether to 20 ml, then add 16.8 g of n-12 olefin, and then 1.5 g of cationic resin. Stir with a magnetic stirrer, the reaction temperature is 80° C., and the reaction time is 4 hours. Then layered filtration, vacuum distillation, and finally the final product. The reaction conversion was 0%.
实施例2Example 2
在装有冷凝管的250ml的单口圆底烧瓶中加入水杨酸13.8g，加入正丁醚为20ml，再加入16.8g正12烯烃，然后加入1.5g的负载量为30％的磷钨酸。用磁力搅拌器进行搅拌，反应温度为80℃，反应时间为4小时。然后分层过滤，进行真空蒸馏，最后得到最终产品。烯烃反应转化率为52.1％。In a 250ml single-necked round bottom flask equipped with a condenser, add 13.8g of salicylic acid, add 20ml of n-butyl ether, add 16.8g of n-12 olefin, and then add 1.5g of phosphotungstic acid with a loading capacity of 30%. Stir with a magnetic stirrer, the reaction temperature is 80° C., and the reaction time is 4 hours. Then layered filtration, vacuum distillation, and finally the final product. The conversion rate of olefin reaction was 52.1%.
实施例3Example 3
在装有冷凝管的250ml的单口圆底烧瓶中加入水杨酸13.8g，加入正丁醚为20ml，再加入22.4g正16烯烃，然后加入0.5g的负载量为20％的磷钨酸。用磁力搅拌器进行搅拌，反应温度为90℃，反应时间为3小时。然后分层过滤，进行真空蒸馏，最后得到最终产品。烯烃反应转化率为42.1％。In a 250ml single-necked round bottom flask equipped with a condenser, add 13.8g of salicylic acid, add 20ml of n-butyl ether, add 22.4g of n-16 olefin, and then add 0.5g of phosphotungstic acid with a loading capacity of 20%. Stir with a magnetic stirrer, the reaction temperature is 90° C., and the reaction time is 3 hours. Then layered filtration, vacuum distillation, and finally the final product. The conversion rate of olefin reaction was 42.1%.
实施例4Example 4
在装有冷凝管的250ml的单口圆底烧瓶中加入水杨酸13.8g，加入正丁醚为20ml，再加入33.6g碳数为20-30的混合正烯烃，然后加入1.0g的负载量为50％的磷钼酸。用磁力搅拌器进行搅拌，反应温度为100℃，反应时间为5小时。然后分层过滤，进行真空蒸馏，最后得到最终产品。反应转化率为31.4％。Add 13.8g of salicylic acid in a 250ml single-necked round bottom flask equipped with a condenser tube, add n-butyl ether to 20ml, then add 33.6g of mixed normal olefins with a carbon number of 20-30, and then add 1.0g of loading capacity of 50% phosphomolybdic acid. Stir with a magnetic stirrer, the reaction temperature is 100° C., and the reaction time is 5 hours. Then layered filtration, vacuum distillation, and finally the final product. The reaction conversion rate was 31.4%.
实施例5Example 5
反应条件同实施例1，催化剂循环使用，试验结果如表1所示。Reaction condition is the same as embodiment 1, and catalyst is recycled, and test result is as shown in table 1.
表1催化剂循环使用的效果Table 1 Effect of catalyst recycling
从表1可以发现，催化剂循环4次后，催化活性并没有降低，仍有较好的催化活性。It can be found from Table 1 that after the catalyst has been cycled for 4 times, the catalytic activity has not decreased and still has good catalytic activity.
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100711118A CN1323062C (en) | 2004-07-29 | 2004-07-29 | Method for preparing alkyl salicylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100711118A CN1323062C (en) | 2004-07-29 | 2004-07-29 | Method for preparing alkyl salicylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1727323A CN1727323A (en) | 2006-02-01 |
| CN1323062C true CN1323062C (en) | 2007-06-27 |
Family
ID=35926869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100711118A Expired - Lifetime CN1323062C (en) | 2004-07-29 | 2004-07-29 | Method for preparing alkyl salicylic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1323062C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195785B (en) * | 2006-12-07 | 2010-05-19 | 中国石油天然气股份有限公司 | Preparation method of alkyl sodium salicylate metal detergent |
| CN104387238B (en) * | 2014-10-27 | 2016-05-11 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of branched alkyl phenol |
| CN107497497A (en) * | 2017-09-26 | 2017-12-22 | 丹东明珠特种树脂有限公司 | A kind of resin catalyst and its method of modifying applied to Etherification of Light FCC Gasoline reaction |
| CN112574022A (en) * | 2020-11-23 | 2021-03-30 | 国家能源集团宁夏煤业有限责任公司 | Alkyl salicylic acid and alkyl salicylate type lubricating oil detergent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104109A (en) * | 1986-06-10 | 1988-01-20 | 住友化学工业株式会社 | Process for the preparation of hydroxyl-containing alkylaromatic compounds |
| US5734078A (en) * | 1995-11-01 | 1998-03-31 | Bp Chemicals (Additives) Limited | Alkylation process |
| CN1277894A (en) * | 1999-06-16 | 2000-12-27 | 中国科学院大连化学物理研究所 | Loading type heteropoly acid catalyst used for prepn. of linear alkyl benzene by alkylation of straight chair olefin and benzene |
-
2004
- 2004-07-29 CN CNB2004100711118A patent/CN1323062C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104109A (en) * | 1986-06-10 | 1988-01-20 | 住友化学工业株式会社 | Process for the preparation of hydroxyl-containing alkylaromatic compounds |
| US5734078A (en) * | 1995-11-01 | 1998-03-31 | Bp Chemicals (Additives) Limited | Alkylation process |
| CN1277894A (en) * | 1999-06-16 | 2000-12-27 | 中国科学院大连化学物理研究所 | Loading type heteropoly acid catalyst used for prepn. of linear alkyl benzene by alkylation of straight chair olefin and benzene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1727323A (en) | 2006-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102909077B (en) | Metal-modified cation exchange resin catalyst, preparation method and application thereof | |
| CN104437637B (en) | A kind of epoxy resin load phosphotungstic acid catalyst and preparation method and application | |
| CN101293210A (en) | Composite catalyst for direct esterification of ethyl ester and butene to prepare sec-butyl acetate | |
| CN101412663B (en) | Preparation technique for polymerization inhibitor products | |
| CN107311868A (en) | A method for preparing methyl p-tert-butylbenzoate | |
| Liu et al. | Facile synthesis of fructone from ethyl acetoacetate and ethylene glycol catalyzed by SO 3 H-functionalized Brønsted acidic ionic liquids | |
| CN102001936A (en) | Continuous production method of propyl acetate | |
| CN103508881B (en) | A kind of method of synthesizing alkyl salicylic acid | |
| CN101293824B (en) | Method for preparing sec-butyl acetate by directly esterifying acetic acid and butylene | |
| CN1323062C (en) | Method for preparing alkyl salicylic acid | |
| CN103508882B (en) | A kind of preparation method of alkyl salicylic acid | |
| CN102259025A (en) | Catalyst for preparing cyclohexanol by hydration of cyclohexene as well as preparation method and application method thereof | |
| CN104492494B (en) | Magnetic iron oxide-immobilized ionic liquid solid acid material catalyst and preparation method thereof | |
| CN102603540B (en) | A kind of preparation method of diethyldiaminotoluene | |
| CN102464574A (en) | Preparation method of p-alkyl catechol | |
| CN101985418B (en) | Method for preparing 2-methoxy-1-propanol ether acetate | |
| CN108043456A (en) | A kind of polyacid class ionic-liquid catalyst, preparation method and the method for preparing cyclohexanol with its catalysis ethyl cyclohexyl ester hydrolysis | |
| CN202519181U (en) | Device for continuously producing electronic grade propylene glycol methyl ether acetate | |
| CN101985419A (en) | Method for preparing ethylene glycol ethyl ether acetate | |
| CN111097516A (en) | Catalyst for synthesizing methyl methoxyacetate and preparation method thereof | |
| CN103524323B (en) | Method for catalytically synthesizing o-benzoylbenzoic acid by virtue of metal oxide supported solid superacid | |
| CN105037301A (en) | Preparation method for citraconic anhydride | |
| CN112657488A (en) | Polyacid type solid catalyst | |
| CN102408339A (en) | Heteropolyacid pyridinium salt ionic liquid catalyzed clean nitration of aromatic hydrocarbons | |
| CN104030925A (en) | Method for catalytically synthesizing mononitrochlorobenzene |
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 |
Granted publication date: 20070627 |
|
| CX01 | Expiry of patent term |