CN104788323A - Method for synthesizing 1,4-cyclohexyldimethylamine - Google Patents
Method for synthesizing 1,4-cyclohexyldimethylamine Download PDFInfo
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- CN104788323A CN104788323A CN201410022947.2A CN201410022947A CN104788323A CN 104788323 A CN104788323 A CN 104788323A CN 201410022947 A CN201410022947 A CN 201410022947A CN 104788323 A CN104788323 A CN 104788323A
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Abstract
The invention relates to a method for synthesizing 1,4-cyclohexyldimethylamine. By an immersion method, a ruthenium-based supported catalyst is prepared; and in a batch reactor, catalytic hydrogenation is carried out on p-benzene dimethylamine in the presence of a solvent and a micro-additive so as to synthesize 1,4-cyclohexyldimethylamine. In comparison with the prior art, the invention has characteristics as follows: the technology is simple to operate; product selectivity is high; yield is high; the catalyst has long mechanical application period and high stability; and after rectification, overall yield reaches 96.8%. The method is easy to apply to industrial production by the use of an existing batch reactor.
Description
Technical field
The invention belongs to technical field of fine chemical synthesis, relate to a kind of synthetic method of epoxy curing agent, especially relate to a kind of method of synthesizing Isosorbide-5-Nitrae-cyclohexyldimethylamine.
Background technology
Isosorbide-5-Nitrae-cyclohexyldimethylamine (1.4-BAC) is mainly used in epoxy curing agent, polymeric amide and isocyanide ester starting material, urethane intermediates and corrosion prevention rust preventer.There is no the suitability for industrialized production of Isosorbide-5-Nitrae-BAC at present both at home and abroad, the self-produced PXDA of my company, the Isosorbide-5-Nitrae-BAC product for exploitation downstream has good economic advantages.Its synthetic route is mainly prepared from by p dimethylamine's (PXDA) hydrogenating reduction or para-Phthalonitrile one step hydrogenating reduction.The main patent to these two kinds of methods is introduced below.
P dimethylamine (PXDA) hydrogenating reduction: patent US4181680 with 5% supported ruthenium aluminum oxide for catalyzer, adopt batch reactor, water is solvent, and reaction pressure is 10MPa, temperature of reaction 125 DEG C, 1,4-BAC selectivity 88%, the temperature that this patent uses and pressure higher, selectivity of product is low, de-amine by-products content is high, and it is general that stability applied mechanically by catalyzer.
In patent EP1586554B1 with 2% supported ruthenium aluminum oxide for catalyzer, adopt fixed-bed reactor, exist at liquefied ammonia, 10MPa, 105 DEG C, MXDA/1, under the reaction conditions of 3-BAC=5/95, the mass yield of 1,3-BAC reaches 97.7% (after deviating from low-boiling-point substance).But current domestic main still employing batch reactor is main, and fixed-bed process exploitation is still immature.
Para-Phthalonitrile one step hydrogenation: patent US4070399 with 5% loading type Ru-Pd/C for catalyzer, with lower aliphatic alcohols, dioxane, low-grade aliphatic amines etc. are solvent, under liquefied ammonia exists, under about 100atm pressure and 100-150 DEG C of temperature, carry out hydrogenation reaction to TPN, the mass yield of Isosorbide-5-Nitrae-BAC is up to 98%.
Patent US3998881 is with the rhodium aluminum oxide of 5% loading type amount for catalyzer, and solvent uses dioxane, and tetrahydrofuran (THF), chloroform etc., liquefied ammonia is as deamination inhibitor, and reaction pressure is about 100atm, and temperature of reaction is 100-150 DEG C, and the total recovery after rectifying is 71%.
Patent EP0538865A1 is with 5% supported ruthenium aluminum oxide for catalyzer, and dioxane is solvent, and under liquefied ammonia exists, react at 150atm pressure and 140 DEG C, 1,3-BAC and Isosorbide-5-Nitrae-BAC selectivity are respectively 87.8% and 88.2%.The Pd that this method adopts, Rh catalyzer is expensive, and severe reaction conditions, and Isosorbide-5-Nitrae-BAC selectivity is low, deamination and piptonychia amine by product higher.
Summary of the invention
Object of the present invention is exactly provide the method for synthesis Isosorbide-5-Nitrae-cyclohexyldimethylamine that a kind of selectivity is high, yield is high to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
Synthesize a method for Isosorbide-5-Nitrae-cyclohexyldimethylamine, adopt pickling process to prepare ruthenium base supported catalyst, in batch reactor, under solvent and trace assistant exist, shortening is carried out to p dimethylamine, synthesis obtains Isosorbide-5-Nitrae-cyclohexyldimethylamine, specifically adopts following steps:
(1) RuCl is configured
33H
2the aqueous solution of O and transition metal or rare earth element nitrate, uses NH
3h
2the pH to 8.0 of O regulator solution, join in the aluminum oxide of saponification process or silica supports and flood, flood the catalyst precursor dried overnight at 110 DEG C obtained, then put into retort furnace roasting 4h at 400 DEG C, finally pass into hydrogen reducing and namely obtain ruthenium base supported catalyst;
(2) take p dimethylamine as raw material, raw material is put in solvent, utilize ruthenium base supported catalyst and alkali metal promoter, control temperature of reaction is 60-120 DEG C, pressure is under 4.0-10.0MPa, reaction 0.5-6h, and shortening obtains thick product, then Isosorbide-5-Nitrae-cyclohexyldimethylamine is obtained by rectifying.
Described solvent is selected from Isosorbide-5-Nitrae-cyclohexyldimethylamine, one or both of water or dioxane, and the quality proportioning that feeds intake of solvent and raw material is 5: 1-1: 5.
As preferred embodiment, solvent is the mixed solvent of Isosorbide-5-Nitrae-cyclohexyldimethylamine and water.
Described alkali metal promoter is selected from LiOH, NaOH or KOH, and charging capacity is the 0.1-5wt% of solvent, relative to the 1-50wt% of catalyzer charging capacity.
As preferred embodiment, alkali metal promoter is NaOH, and charging capacity is the 0.3-1wt% of solvent, relative to the 5-15wt% of catalyzer charging capacity.
As preferred embodiment, temperature of reaction control 80-110 DEG C, pressure is 5-7MPa, and the reaction times is 2-6h.
As the embodiment be more preferably, temperature of reaction is preferably 90-100 DEG C.
Compared with prior art, the present invention adopts water or product itself as solvent, the mixed solvent better effects if of arranging in pairs or groups with water, pass through improving technique, fine adjustment solvent, the relation between promotor and catalyst levels, reduces promotor as far as possible on the impact of support of the catalyst, play good inhibited reaction deamination and the side reaction of piptonychia amine simultaneously, strengthen catalyzer and apply mechanically cycle and stability.In order to improve catalyst activity and suppress side reaction, so generally will promotor be added, and alkaline hydrated oxide generally selected by promotor, certain solvency action is had to catalyst carrier alumina, so in order to balance the proportionlity that both will control well described in the application, this proportionlity is containing the two-layer meaning: one deck is the concentration of promotor relative solvent, and another layer is meant to the concentration of promotor relative catalyst.If not the proportionlity that the application adopts, ratio is too high, and support of the catalyst is destroyed serious, and catalyst attrition is large, and decay of activity amplitude is large, and apply mechanically poor stability, work-ing life is short; Ratio is too low, and side reaction product obviously increases, and catalyst activity also obviously reduces, and selectivity and yield all can decline to a great extent.It is simple that the present invention has technological operation, and product selectivity is high, and yield is high, and it is long that the cycle applied mechanically by catalyzer, the feature that stability is high, and after rectifying, total recovery reaches 96.8%, is easy to the suitability for industrialized production for existing batch reactor.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
Drop into 30g PXDA successively, 30g water, 0.9g NaOH, 5%Ru/Al
2o
3catalyzer 1.2g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 1-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration.Product content 99.2%.
Embodiment 2
Drop into 30g PXDA successively, 30g1,4-BAC, 0.9g NaOH, 5%Ru/Al
2o
3catalyzer 1.2g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 2-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 98.4%.
Embodiment 3
Drop into 30g PXDA successively, 15g water, 15g1,4-BAC, 0.9g NaOH, 5%Ru/Al
2o
3catalyzer 1.2g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 2-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 99.0%.
Embodiment 4
Drop into 30g PXDA successively, 60g water, 1.8g NaOH, 5%Ru/Al
2o
3catalyzer 1.2g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 1-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 98.6%.
Embodiment 5
Drop into 30g PXDA successively, 30g water, 0.9g NaOH, 5%Ru/Al
2o
3catalyzer 0.6g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 4-6h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 97.8%.
Embodiment 6
Drop into 30g PXDA successively, 60g water, 0.3g NaOH, 5%Ru/Al
2o
3catalyzer 1.2g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 1-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 97.0%.
Embodiment 7
Drop into 30g PXDA successively, 10g water, 20g1,4-BAC, 0.9g NaOH, 5%Ru/Al
2o
3catalyzer 1.2g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 2-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 98.6%.
Embodiment 8
Drop into 30g PXDA successively, 30g water, 0.24g NaOH, 5%Ru/Al
2o
3catalyzer 0.9g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 1-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 98.4%.
Embodiment 9
Drop into 30g PXDA successively, 30g water, 0.15g NaOH, 5%Ru/Al
2o
3catalyzer 1.2g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 1-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 98.4%.
Embodiment 10
Drop into 60g PXDA successively, 30g water, 0.3g NaOH, 5%Ru/Al
2o
3catalyzer 1.2g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 3-5h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 96.6%.
Embodiment 11
Drop into 60g PXDA successively, 30g water, 0.24g NaOH, 5%Ru/Al
2o
3catalyzer 2.4g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 1-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 99.4%.
Embodiment 12
Drop into 60g PXDA successively, 20g water, 0.12g NaOH, 5%Ru/Al
2o
3catalyzer 2.4g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 1-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 98.2%.
Embodiment 13
Drop into 50g PXDA successively, 10g water, 0.06g NaOH, 5%Ru/Al
2o
3catalyzer 2.0g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 1-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 95.5%.
Embodiment 14
Drop into 30g PXDA successively, 30g water, 0.21g NaOH, 5%Ru/SiO
2catalyzer 1.2g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 1-3h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, product content 98.2%.
Embodiment 15
Drop into 30g PXDA successively, 30g water, 0.9g NaOH, 5%Ru/Al
2o
3catalyzer 1.2g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 2-9h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, and filter cake (catalyzer) is applied mechanically.Apply mechanically 24 batches (containing regeneration), it is 92.5% that filtrate carries out the total recovery after precipitation rectifying.
Embodiment 16
Drop into 30g PXDA successively, 30g water, 0.9g NaOH, 5%Ru/Al
2o
3catalyzer 0.6g, close still, with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, then 5MPa is charged to, open and be heated with stirring to 80 DEG C, then fill H2 to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 4-9h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, and filter cake (catalyzer) is applied mechanically.Apply mechanically 8 batches (containing regeneration), it is 89.6% that filtrate carries out the total recovery after precipitation rectifying.
Embodiment 17
Drop into 30g PXDA successively, 30g water, 0.06g NaOH, 5%Ru/Al
2o
3catalyzer 0.6g, close still, with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, then 5MPa is charged to, open and be heated with stirring to 80 DEG C, then fill H2 to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 5-10h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, and filter cake (catalyzer) is applied mechanically.Apply mechanically 4 batches, it is 83.4% that filtrate carries out the total recovery after precipitation rectifying.
Embodiment 18
Drop into 60g PXDA successively, 30g water, 0.15g NaOH, 5%Ru/Al
2o
3catalyzer 2.4g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80 DEG C, then fill H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 2-8h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, and filter cake (catalyzer) is applied mechanically.Apply mechanically 50 batches, it is 96.5% that filtrate carries out the total recovery after precipitation rectifying.
Embodiment 19
Drop into 60g PXDA successively, 15g water, 15g1,4-BAC, 0.15g NaOH, 5%Ru/Al
2o
3catalyzer 2.4g, closes still, and with nitrogen, hydrogen is charged to 0.2MPa and replaces three times, is then charged to 5MPa, opens and is heated with stirring to 80C, then fills H
2to 7MPa, when Pressure Drop is to 6MPa, be inflated to 7MPa, repeatable operation like this, to no longer inhaling hydrogen, controls temperature of reaction between 90-100 DEG C, reaction times 2-8h.Be cooled to room temperature, emptying hydrogen, drives still, discharging, suction filtration, and filter cake (catalyzer) is applied mechanically.Apply mechanically 48 batches, it is 96.8% that filtrate carries out the total recovery after precipitation rectifying.
Claims (8)
1. synthesize a method for Isosorbide-5-Nitrae-cyclohexyldimethylamine, it is characterized in that, the method adopts pickling process to prepare ruthenium base supported catalyst, in batch reactor, under solvent and trace assistant exist, carry out shortening to p dimethylamine, synthesis obtains Isosorbide-5-Nitrae-cyclohexyldimethylamine.
2. a kind of method of synthesizing Isosorbide-5-Nitrae-cyclohexyldimethylamine according to claim 1, is characterized in that, the method adopts following steps:
(1) RuCl is configured
33H
2the aqueous solution of O and transition metal or rare earth element nitrate, uses NH
3h
2the pH to 8.0 of O regulator solution, join in the aluminum oxide of saponification process or silica supports and flood, flood the catalyst precursor dried overnight at 110 DEG C obtained, then put into retort furnace roasting 4h at 400 DEG C, finally pass into hydrogen reducing and namely obtain ruthenium base supported catalyst;
(2) take p dimethylamine as raw material, raw material is put in solvent, utilize ruthenium base supported catalyst and alkali metal promoter, control temperature of reaction is 60-120 DEG C, pressure is under 4.0-10.0MPa, reaction 0.5-6h, and shortening obtains thick product, then Isosorbide-5-Nitrae-cyclohexyldimethylamine is obtained by rectifying.
3. a kind of method of synthesizing Isosorbide-5-Nitrae-cyclohexyldimethylamine according to claim 2, is characterized in that, described solvent is selected from one or both of Isosorbide-5-Nitrae-cyclohexyldimethylamine, water or dioxane, and the quality proportioning that feeds intake of solvent and raw material is 5: 1-1: 5.
4. a kind of method of synthesizing Isosorbide-5-Nitrae-cyclohexyldimethylamine according to claim 3, is characterized in that, the mixed solvent of the preferred Isosorbide-5-Nitrae-cyclohexyldimethylamine of described solvent and water.
5. a kind of method of synthesizing Isosorbide-5-Nitrae-cyclohexyldimethylamine according to claim 2, it is characterized in that, described alkali metal promoter is selected from LiOH, NaOH or KOH, and charging capacity is the 0.1-5wt% of solvent, relative to the 1-50wt% of catalyzer charging capacity.
6. a kind of method of synthesizing Isosorbide-5-Nitrae-cyclohexyldimethylamine according to claim 5, is characterized in that, the preferred NaOH of described alkali metal promoter, and charging capacity is the 0.3-1wt% of solvent, relative to the 5-15wt% of catalyzer charging capacity.
7. a kind of method of synthesizing Isosorbide-5-Nitrae-cyclohexyldimethylamine according to claim 2, is characterized in that, temperature of reaction control 80-110 DEG C, and pressure is 5-7MPa, and the reaction times is 2-6h.
8. a kind of method of synthesizing Isosorbide-5-Nitrae-cyclohexyldimethylamine according to claim 7, it is characterized in that, temperature of reaction is preferably 90-100 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100014A (en) * | 2019-11-18 | 2020-05-05 | 名畔科技(镇江)有限公司 | Preparation method of 1, 3-cyclohexyldimethylamine |
| CN113045431A (en) * | 2021-03-01 | 2021-06-29 | 淄博尚正新材料科技有限公司 | Method for preparing 1, 3-cyclohexyl dimethylamine |
| CN117964498A (en) * | 2024-04-02 | 2024-05-03 | 鞍山七彩化学股份有限公司 | Method for preparing rich trans-1, 4-cyclohexanedimethylamine |
-
2014
- 2014-01-17 CN CN201410022947.2A patent/CN104788323A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100014A (en) * | 2019-11-18 | 2020-05-05 | 名畔科技(镇江)有限公司 | Preparation method of 1, 3-cyclohexyldimethylamine |
| CN111100014B (en) * | 2019-11-18 | 2022-05-10 | 名畔科技(镇江)有限公司 | Preparation method of 1, 3-cyclohexyldimethylamine |
| CN113045431A (en) * | 2021-03-01 | 2021-06-29 | 淄博尚正新材料科技有限公司 | Method for preparing 1, 3-cyclohexyl dimethylamine |
| CN117964498A (en) * | 2024-04-02 | 2024-05-03 | 鞍山七彩化学股份有限公司 | Method for preparing rich trans-1, 4-cyclohexanedimethylamine |
| CN117964498B (en) * | 2024-04-02 | 2024-07-09 | 鞍山七彩化学股份有限公司 | Method for preparing rich trans-1, 4-cyclohexanedimethylamine |
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Address after: 200335 Shanghai city Changning District North Zhai Road No. 785 Applicant after: SHANGHAI TAIHE INTERNATIONAL TRADE CO., LTD. Applicant after: Nantong Taihe Chemical Co., Ltd. Address before: 200335 Shanghai city Changning District North Zhai Road No. 785 Applicant before: Shanghai CAC Chemical Co.,Ltd. Applicant before: Nantong Taihe Chemical Co., Ltd. |
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Address after: 200335 Shanghai city Changning District North Zhai Road No. 785 Applicant after: SHANGHAI TAIHE INTERNATIONAL TRADE CO., LTD. Applicant after: Nantong Taihe chemical Limited by Share Ltd Address before: 200335 Shanghai city Changning District North Zhai Road No. 785 Applicant before: SHANGHAI TAIHE INTERNATIONAL TRADE CO., LTD. Applicant before: Nantong Taihe Chemical Co., Ltd. |
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| RJ01 | Rejection of invention patent application after publication |