CN101591237A - Anti-form-1, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic - Google Patents
Anti-form-1, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic Download PDFInfo
- Publication number
- CN101591237A CN101591237A CNA2009100269197A CN200910026919A CN101591237A CN 101591237 A CN101591237 A CN 101591237A CN A2009100269197 A CNA2009100269197 A CN A2009100269197A CN 200910026919 A CN200910026919 A CN 200910026919A CN 101591237 A CN101591237 A CN 101591237A
- Authority
- CN
- China
- Prior art keywords
- cyclohexane cyclohexanedimethanodibasic
- synthetic method
- terephthalic acid
- reaction
- protective material
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of anti-form-1; the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic; terephthalic acid and catalyzer, protective material and water are added in the autoclave; after feeding nitrogen replacement; feed hydrogen again; in 100-120 ℃ of following continuous hydrogenation, after reaction finishes, more successively through heat filtering, cooling, filter product.The present invention is starting raw material with the terephthalic acid, makes anti-form-1 through single step reaction, the 4-cyclohexane cyclohexanedimethanodibasic, and raw material is easy to get, and synthetic route is short, and process safety is simple, and cost is low, and yield reaches more than 95%, realizes suitability for industrialized production easily.
Description
Technical field:
The present invention relates to a kind of anti-form-1, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic.
Background technology:
The anti-form-1 of molecular formula shown in following formula, the 4-cyclohexane cyclohexanedimethanodibasic is that aliphatic dibasic acid has 1,4 is characteristics such as substituting group and alicyclic ring texture, for high-performance coating has brought many particular performances with vibrin and glass filament reinforced plastics, product is used for aspects such as automobile, transportation, industrial maintenance, aerospace, buildings, equipment and instrument and plain metal and gel coat coating.Related data is as follows:
The route of the complete synthetic target product of bibliographical information is not arranged at present as yet, and the route that can obtain approaching product-mixing-1,4 cyclohexanedicarboxylic acid has following several:
Article one, be Zhu Zhiqing etc. (CN200510028867.9) with terephthalic acid through ruthenium-aluminium sesquioxide catalysis, in 110-180 ℃, under the 2.0-5.0Mpa hydrogenation reaction 0.5-8 hour, make mixing-1.4-cyclohexane cyclohexanedimethanodibasic.This long reaction time, the temperature height.
Second is the United States Patent (USP) of U.S. Amoco company in nineteen eighty-three application preparation 1,4 cyclohexanedicarboxylic acid.This patent proposes under rhodium catalysis, in 100-110 ℃, and under the 3.4-10.2Mpa, hydrogenation 4 hours, the mixing-1,4 cyclohexanedicarboxylic acid of system.This route reaction pressure height, the dangerous enhancing.
Article three, be that US2828335, US5118841 and US5202475 have described under ruthenium catalysis, the aqueous feed solution of phthalate can high yield, well optionally be hydrogenated.The shortcoming of this technology is for reclaiming cyclohexane cyclohexanedimethanodibasic, must carry out aftertreatment with mineral acid, and the schedule of operation complexity has increased energy consumption, supplies consumption and the production cost of suitability for industrialized production greatly.
Article four, be the United States Patent (USP) of Japanese Towa chemical industry company limited in the 1,4 cyclohexanedicarboxylic acid of application in 1993.This patent is a raw material with the phthalic acid earlier, under palladium catalysis, and in 120-160 ℃, hydrogenation under the 0.19-0.95Mpa, and then carry out stripping and get mixing-1,4 cyclohexanedicarboxylic acid.This technology has increased the energy consumption and the production cost of suitability for industrialized production equally greatly.
Article five, being U.S. Eastman chemical company prepares the United States Patent (USP) of 1,4 cyclohexanedicarboxylic acid in the terephthalic acid of application in 1999, has applied for phthalic acid hydrogenant patented technology in China simultaneously.Invention has proposed to adopt the palladium catalyst that places on the carrier, in 195-230 ℃, and hydrogenation under the 4.1-4.8Mpa, product purity reaches 98%, wherein cis-content 〉=65%.
In a word, in these route synthetic 1,4 cyclohexanedicarboxylic acids, the cis product content is converted into pure trans 1,4 cyclohexanedicarboxylic acid difficulty all than higher.
Summary of the invention:
The object of the present invention is to provide a kind of raw material to be easy to get, synthetic route is short, technology is simple and safe, yield is high, cost is low, realizes the anti-form-1 of suitability for industrialized production easily, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic.
Summary of the invention:
Technical solution of the present invention is:
A kind of anti-form-1; the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic; it is characterized in that: terephthalic acid and catalyzer, protective material and water are added in the autoclave; after feeding nitrogen replacement; feed hydrogen again; in 100-120 ℃ of following continuous hydrogenation, after reaction finishes, more successively through heat filtering, cooling, filter product.
The reaction pressure of described continuous hydrogenation is 2.5～5.5Mpa, and the reaction times is 2～4 hours.
Described catalyst consumption is the 4-15% of terephthalic acid, and protectant consumption is 8～24% of a terephthalic acid.
Heat filtering filter cake and cold filtration filtrate cycle are applied mechanically.Described catalyzer is the palladium charcoal.Protective material is an ammonium hydroxide.Catalyst recirculation is applied mechanically.The protective material recycled.
Whole synthetic being shown below of the present invention:
In this formula, symbol a represents terephthalic acid, and b represents anti-form-1, the 4-cyclohexane cyclohexanedimethanodibasic.
The present invention is starting raw material with the terephthalic acid, makes anti-form-1 through single step reaction, the 4-cyclohexane cyclohexanedimethanodibasic, and raw material is easy to get, and synthetic route is short, and process safety is simple, and cost is low, and yield reaches more than 95%, realizes suitability for industrialized production easily.
The invention will be further described below in conjunction with embodiment.
Embodiment:
Embodiment 1
The 200g terephthalic acid is added autoclave; add 15g palladium catalyst charcoal and 30g protective material ammonium hydroxide; the water that adds 600g again feeds nitrogen replacement three times earlier, feeds hydrogen exchange again three times; feeding hydrogen then makes pressure rise to 4Mpa and keeps stable; stirring is warming up to 100 ℃, and the hydrogen quickening is inhaled in reaction, keeps temperature of reaction 100-120 ℃; and continuous hydrogenation, reacted 3 hours.After reaction finishes, the filtered while hot catalyzer, filter cake is applied mechanically, and the filtrate cooled and filtered gets filter cake weight in wet base 227g, oven dry 191g, yield 95.5%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 98.3%, filtrate is applied mechanically.Catalyzer can be applied mechanically 13-15 time, and protective material is recycled always.
Embodiment 2
Catalyst consumption changes 11g into, and the remaining reaction condition is with embodiment 1, final gained yield 84.3%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 98.1%.
Embodiment 3
Catalyst consumption changes 13g into, and the remaining reaction condition is with embodiment 1, final gained yield 93.1%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 98.2%.
Embodiment 4
Catalyst consumption changes 17g into, and the remaining reaction condition is with embodiment 1, final gained yield 95.6%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 98.2%.
Embodiment 5
Protectant consumption changes 25g into, and the remaining reaction condition is with embodiment 1, final gained yield 95.3%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 91.4%.
Embodiment 6
Protectant consumption changes 28g into, and the remaining reaction condition is with embodiment 1, final gained yield 95.6%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 96.7%.
Embodiment 7
Protectant consumption changes 32g into, and the remaining reaction condition is with embodiment 1, final gained yield 95.4%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 98.3%.
Embodiment 8
Reaction pressure changes 3.6MPa into, and the remaining reaction condition is with embodiment 1, final gained yield 88.3%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 98.0%.
Embodiment 9
Reaction pressure changes 3.8MPa into, and the remaining reaction condition is with embodiment 1, final gained yield 92.6%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 98.4%.
Embodiment 10
Reaction pressure changes 4.2MPa into, and the remaining reaction condition is with embodiment 1, final gained yield 94.3%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 98.1%.
Embodiment 11
Reaction times changes 2 hours into, and the remaining reaction condition is with embodiment 1, final gained yield 81.8%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 96.9%.
Embodiment 12
Reaction times changes 2.5 hours into, and the remaining reaction condition is with embodiment 1, final gained yield 90.3%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 97.8%.
Embodiment 13
Reaction times changes 3.5 hours into, and the remaining reaction condition is with embodiment 1, final gained yield 95.5%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 98.2%.
Embodiment 14
Temperature of reaction changes 60-80 ℃ into, and the remaining reaction condition is with embodiment 1, final gained yield 73.8%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 91.4%.
Embodiment 15
Temperature of reaction changes 80-100 ℃ into, and the remaining reaction condition is with embodiment 1, final gained yield 88.7%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 96.9%.
Embodiment 16
Temperature of reaction changes 120-140 ℃ into, and the remaining reaction condition is with embodiment 1, final gained yield 95.7%, anti-form-1,4-cyclohexane cyclohexanedimethanodibasic content 98.5%.
Claims (8)
1, a kind of anti-form-1; the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic; it is characterized in that: terephthalic acid and catalyzer, protective material and water are added in the autoclave; after feeding nitrogen replacement; feed hydrogen again; in 90-130 ℃ of following continuous hydrogenation, after reaction finishes, more successively through heat filtering, cooling, filter product.
2, anti-form-1 according to claim 1, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic is characterized in that: the reaction pressure of described continuous hydrogenation is 2.5～5.5Mpa, the reaction times is 2～4 hours.
3, anti-form-1 according to claim 1, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic is characterized in that: described catalyst consumption is the 4-15% of terephthalic acid, protectant consumption is 8～24% of a terephthalic acid.
4, according to claim 1,2 or 3 described anti-form-1s, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic is characterized in that: heat filtering filter cake and cold filtration filtrate cycle are applied mechanically.
5, according to claim 1,2 or 3 described anti-form-1s, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic is characterized in that: described catalyzer is the palladium charcoal.
6, according to claim 1,2 or 3 described anti-form-1s, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic is characterized in that: protective material is an ammonium hydroxide.
7, anti-form-1 according to claim 5, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic is characterized in that: catalyst recirculation is applied mechanically.
8, anti-form-1 according to claim 6, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic is characterized in that: the protective material recycled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100269197A CN101591237A (en) | 2009-05-21 | 2009-05-21 | Anti-form-1, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100269197A CN101591237A (en) | 2009-05-21 | 2009-05-21 | Anti-form-1, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101591237A true CN101591237A (en) | 2009-12-02 |
Family
ID=41406142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100269197A Pending CN101591237A (en) | 2009-05-21 | 2009-05-21 | Anti-form-1, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101591237A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103153940A (en) * | 2010-10-07 | 2013-06-12 | 三井化学株式会社 | Method for producing trans-1,4-bis(aminomethyl)cyclohexane |
| CN104945237A (en) * | 2015-05-15 | 2015-09-30 | 济南磐石医药科技有限公司 | Synthesis method of (1R, 2R)-trans-cyclohexane dicarboxylic acid |
| CN105712863A (en) * | 2015-02-12 | 2016-06-29 | 江苏永达药业有限公司 | Process for producing trans-acid |
| CN106693960A (en) * | 2016-11-16 | 2017-05-24 | 北京工业大学 | Supported palladium catalyst for synthesizing 1,4-cyclohexanedicarboxylic acid |
| WO2018066447A1 (en) * | 2016-10-04 | 2018-04-12 | 三菱瓦斯化学株式会社 | Method for producing 1, 4-dicyanocyclohexane, 1, 4-bis(aminomethyl)cyclohexane and 1, 4-cyclohexane dicarboxylic acid |
| WO2019198778A1 (en) * | 2018-04-11 | 2019-10-17 | 三菱瓦斯化学株式会社 | Production methods for cyclohexanedicarboxylic acid, dicyanocyclohexane, and bis(aminomethyl)cyclohexane |
| WO2019198779A1 (en) * | 2018-04-11 | 2019-10-17 | 三菱瓦斯化学株式会社 | Methods respectively for producing 1,4-cyclohexanedicarboxylic acid derivative, 1,4-dicyanocyclohexane and 1,4-bis(aminomethyl)cyclohexane |
| CN111032624A (en) * | 2017-08-18 | 2020-04-17 | 三菱瓦斯化学株式会社 | The production method of dicyanocyclohexane |
-
2009
- 2009-05-21 CN CNA2009100269197A patent/CN101591237A/en active Pending
Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103153940A (en) * | 2010-10-07 | 2013-06-12 | 三井化学株式会社 | Method for producing trans-1,4-bis(aminomethyl)cyclohexane |
| US8865939B2 (en) | 2010-10-07 | 2014-10-21 | Mitsui Chemicals, Inc. | Method for producing trans-1,4-bis(aminomethyl) cyclohexane |
| CN103153940B (en) * | 2010-10-07 | 2014-12-10 | 三井化学株式会社 | Method for producing trans-1,4-bis(aminomethyl)cyclohexane |
| CN105712863A (en) * | 2015-02-12 | 2016-06-29 | 江苏永达药业有限公司 | Process for producing trans-acid |
| CN104945237A (en) * | 2015-05-15 | 2015-09-30 | 济南磐石医药科技有限公司 | Synthesis method of (1R, 2R)-trans-cyclohexane dicarboxylic acid |
| CN109641833A (en) * | 2016-10-04 | 2019-04-16 | 三菱瓦斯化学株式会社 | Process for producing 1,4-dicyanocyclohexane, 1,4-bis(aminomethyl)cyclohexane and 1,4-cyclohexanedicarboxylic acid |
| WO2018066447A1 (en) * | 2016-10-04 | 2018-04-12 | 三菱瓦斯化学株式会社 | Method for producing 1, 4-dicyanocyclohexane, 1, 4-bis(aminomethyl)cyclohexane and 1, 4-cyclohexane dicarboxylic acid |
| JPWO2018066447A1 (en) * | 2016-10-04 | 2018-10-04 | 三菱瓦斯化学株式会社 | Process for producing 1,4-dicyanocyclohexane, 1,4-bis (aminomethyl) cyclohexane, and 1,4-cyclohexanedicarboxylic acid |
| KR20190059281A (en) * | 2016-10-04 | 2019-05-30 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Production method of 1,4-dicyanocyclohexane, 1,4-bis (aminomethyl) cyclohexane, and 1,4-cyclohexanedicarboxylic acid |
| KR102558413B1 (en) * | 2016-10-04 | 2023-07-24 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Method for producing 1,4-dicyanocyclohexane, 1,4-bis(aminomethyl)cyclohexane, and 1,4-cyclohexanedicarboxylic acid |
| CN109641833B (en) * | 2016-10-04 | 2022-02-22 | 三菱瓦斯化学株式会社 | Process for producing 1, 4-dicyanocyclohexane, 1, 4-bis (aminomethyl) cyclohexane and 1, 4-cyclohexanedicarboxylic acid |
| TWI727101B (en) * | 2016-10-04 | 2021-05-11 | 日商三菱瓦斯化學股份有限公司 | Method for producing 1,4-dicyanocyclohexane, and 1,4-bis(aminomethyl)cyclohexane |
| US10906865B2 (en) * | 2016-10-04 | 2021-02-02 | Mitsubishi Gas Chemical Company, Inc. | Method for producing 1,4-dicyanocyclohexane, 1,4-bis(aminomethyl)cyclohexane and 1,4-cyclohexanedicarboxylic acid |
| CN106693960A (en) * | 2016-11-16 | 2017-05-24 | 北京工业大学 | Supported palladium catalyst for synthesizing 1,4-cyclohexanedicarboxylic acid |
| CN111032624B (en) * | 2017-08-18 | 2023-06-02 | 三菱瓦斯化学株式会社 | Process for producing dicyanocyclohexane |
| CN111032624A (en) * | 2017-08-18 | 2020-04-17 | 三菱瓦斯化学株式会社 | The production method of dicyanocyclohexane |
| KR20200143375A (en) * | 2018-04-11 | 2020-12-23 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Method for producing cyclohexanedicarboxylic acids, dicyanocyclohexanes, and bis(aminomethyl)cyclohexanes |
| WO2019198779A1 (en) * | 2018-04-11 | 2019-10-17 | 三菱瓦斯化学株式会社 | Methods respectively for producing 1,4-cyclohexanedicarboxylic acid derivative, 1,4-dicyanocyclohexane and 1,4-bis(aminomethyl)cyclohexane |
| JPWO2019198779A1 (en) * | 2018-04-11 | 2021-04-22 | 三菱瓦斯化学株式会社 | Method for producing 1,4-cyclohexanedicarboxylic acid derivative, 1,4-dicyanocyclohexane, and 1,4-bis (aminomethyl) cyclohexane |
| CN111954656A (en) * | 2018-04-11 | 2020-11-17 | 三菱瓦斯化学株式会社 | Methods for producing 1,4-cyclohexanedicarboxylic acid derivatives, 1,4-dicyanocyclohexane and 1,4-bis(aminomethyl)cyclohexane |
| JPWO2019198778A1 (en) * | 2018-04-11 | 2021-05-13 | 三菱瓦斯化学株式会社 | Method for Producing Cyclohexanedicarboxylic Acids, Dicyanocyclohexanes, and Bis (Aminomethyl) Cyclohexanes |
| EP3778544A4 (en) * | 2018-04-11 | 2021-06-09 | Mitsubishi Gas Chemical Company, Inc. | METHODS FOR PRODUCING A DERIVATIVE OF 1,4-CYCLOHEXANEDICARBOXYLIC ACID, 1,4-DICYANOCYCLOHEXANE AND 1,4-BIS (AMINOMETHYL) CYCLOHEXANE, RESPECTIVELY |
| CN111886217A (en) * | 2018-04-11 | 2020-11-03 | 三菱瓦斯化学株式会社 | Process for producing cyclohexanedicarboxylic acids, dicyanocyclohexanes, and bis (aminomethyl) cyclohexanes |
| US11472765B2 (en) | 2018-04-11 | 2022-10-18 | Mitsubishi Gas Chemical Company, Inc. | Production method for 1,4-cyclohexanedicarboxylic acid derivative, 1,4-dicyanocyclohexane and 1,4-bis(aminomethyl)cyclohexane |
| US11584705B2 (en) | 2018-04-11 | 2023-02-21 | Mitsubishi Gas Chemical Company, Inc. | Production method for cyclohexanedicarboxylic acid compound, dicyanocyclohexane compound and bis(aminomethyl)cyclohexane compound |
| KR20200142004A (en) * | 2018-04-11 | 2020-12-21 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Method for producing 1,4-cyclohexanedicarboxylic acid derivative, 1,4-dicyanocyclohexane, and 1,4-bis(aminomethyl)cyclohexane |
| WO2019198778A1 (en) * | 2018-04-11 | 2019-10-17 | 三菱瓦斯化学株式会社 | Production methods for cyclohexanedicarboxylic acid, dicyanocyclohexane, and bis(aminomethyl)cyclohexane |
| JP7335555B2 (en) | 2018-04-11 | 2023-08-30 | 三菱瓦斯化学株式会社 | Method for producing cyclohexanedicarboxylic acids, dicyanocyclohexanes, and bis(aminomethyl)cyclohexanes |
| TWI822756B (en) * | 2018-04-11 | 2023-11-21 | 日商三菱瓦斯化學股份有限公司 | Method for producing cyclohexanedicarboxylic acid, dicyanocyclohexane, and bis(aminomethyl)cyclohexane |
| JP7410458B2 (en) | 2018-04-11 | 2024-01-10 | 三菱瓦斯化学株式会社 | Method for producing 1,4-cyclohexanedicarboxylic acid derivative, 1,4-dicyanocyclohexane, and 1,4-bis(aminomethyl)cyclohexane |
| TWI845505B (en) * | 2018-04-11 | 2024-06-21 | 日商三菱瓦斯化學股份有限公司 | Method for producing 1,4-cyclohexanedicarboxylic acid derivative, 1,4-dicyanocyclohexane, and 1,4-bis(aminomethyl)cyclohexane |
| CN111886217B (en) * | 2018-04-11 | 2024-09-13 | 三菱瓦斯化学株式会社 | Method for producing cyclohexanedicarboxylic acids, dicyanocyclohexanes and bis(aminomethyl)cyclohexanes |
| KR102710321B1 (en) | 2018-04-11 | 2024-09-26 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Method for producing 1,4-cyclohexanedicarboxylic acid derivatives, 1,4-dicyanocyclohexane, and 1,4-bis(aminomethyl)cyclohexane |
| KR102713181B1 (en) | 2018-04-11 | 2024-10-07 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Method for producing cyclohexanedicarboxylic acids, dicyanocyclohexanes, and bis(aminomethyl)cyclohexanes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101591237A (en) | Anti-form-1, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic | |
| CN110862310A (en) | Synthesis method of cyclopropyl methyl ketone | |
| CN116239477B (en) | Production process of diethyl toluenediamine based on carbon nano tube aluminum carrier catalyst | |
| CN101659597A (en) | Method for preparing Guerbet alcohol | |
| CN103664524A (en) | Method for preparing 1, 4-cyclohexanedimethanol through hydrogenation of 1, 4-cyclohexanedicarboxylic acid | |
| CN102924262A (en) | Adipic acid preparation method | |
| TWI602860B (en) | Method of preparing cyclohexanedicarboxylic acid from polyester | |
| CN104276959A (en) | Synthetic process of rubber anti-ageing agent 4020 | |
| CN106946668A (en) | A kind of method that phenol hydrogenation prepares cyclohexanone | |
| CN105198689A (en) | Method for preparing cis-pinane by adopting selective hydrogenation of alpha-pinene | |
| CN104193578A (en) | Method for producing decahydronaphthalene and tetrahydronaphthalene by naphthalene hydrogenation | |
| CN102584537A (en) | Method for synthesizing cyclohexanol | |
| KR20190029233A (en) | Separation method of dimethylolbutanal and preparation method of trimethylolpropane | |
| CN103724210B (en) | The production method of N-ethyl-n-butylamine | |
| CN103613785B (en) | A kind of take solid sulphuric acid as the polymeric preparation method of 2,2,4-trimethylammonium-1,2-dihyaroquinoline of catalyzer | |
| CN103965033B (en) | The method of pimelinketone is prepared in a kind of catalysis of phenol selective hydrogenation | |
| CN111018706A (en) | Synthesis method of 4, 4' -diphenyl ether dicarboxylic acid | |
| CN111533739B (en) | Process for preparing 3-alkyl-3, 9-diazaspiro [5,5] undecane | |
| CN103265439A (en) | Preparation method of diphenhydramine | |
| CN103044276A (en) | Process for preparing 4,4-diaminodiphenyl ether | |
| CN110551284B (en) | Preparation method of poly (p-phenylene-benzobisoxazole) fibers | |
| CN105859548B (en) | A kind of method for catalyzing and synthesizing 1,4 cyclohexane cyclohexanedimethanodibasics | |
| CN102659680A (en) | Method for palladium-carbon catalytic hydrogenation synthesis of analgin | |
| CN105523907A (en) | Method for directly preparing cyclohexanone from benzene | |
| CN102952032A (en) | Preparation method of acetaminophen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20091202 |