CN112479897B - Preparation process of 1, 3-cyclohexyldimethylamine - Google Patents
Preparation process of 1, 3-cyclohexyldimethylamine Download PDFInfo
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- CN112479897B CN112479897B CN202011428693.6A CN202011428693A CN112479897B CN 112479897 B CN112479897 B CN 112479897B CN 202011428693 A CN202011428693 A CN 202011428693A CN 112479897 B CN112479897 B CN 112479897B
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Abstract
The invention discloses a preparation process of 1, 3-cyclohexyldimethylamine, which comprises the following steps: 1) Isomeric dehydrogenation of cyclohexene oxide: converting cyclohexene oxide to cyclohexenone over an isodehydrogenation catalyst; 2) Addition of cyclohexenone to hydrocyanic acid: reacting cyclohexenone under the action of hydrocyanic acid and an alkaline addition catalyst to generate 1, 3-dicyano-1-cyclohexanol; 3) Dehydration and hydrogenation of 1, 3-dicyano-1-cyclohexanol: the obtained 1, 3-dicyano-1-cyclohexanol is subjected to dehydration hydrogenation in the presence of hydrogen and a hydrogenation catalyst to produce 1, 3-cyclohexyldimethylamine. Compared with the prior art, the invention has the beneficial effects that the raw materials are cheap and easy to obtain; the reaction yield is high, and the total yield is more than or equal to 90 percent; the reaction condition is mild, and the method is suitable for industrialization.
Description
Technical Field
The invention relates to a preparation process, in particular to a preparation process of 1, 3-cyclohexyldimethylamine.
Background
1, 3-cyclohexyldimethylamine (1, 3-BAC) has important application in the fields of curing agents of epoxy resins, polyurethane intermediates and anticorrosive rust inhibitors, and the international production technology is only mastered in a few companies such as Mitsubishi gas, basff and the like at present, thereby severely restricting the application of products. The production method of 1,3-BAC is classified into IPN (isophthalonitrile) method and MXDA (m-xylylenediamine) method according to the classification of the raw materials used.
The literature techniques for producing 1,3-BAC by IPN method are shown in US5371293A, US4070399A and US3998881A, and different supported catalysts are respectively used for preparation, but generally have the disadvantage of poor selectivity. The literature techniques for producing 1,3-BAC by the MXDA method are shown in EP0703213B1 and US4181680A, but the cost for producing 1,3-BAC by the MXDA method is too high and the reaction conditions are severe. Therefore, a new process with wide raw material source and mild reaction conditions needs to be developed.
Disclosure of Invention
The invention aims to provide a preparation process of 1, 3-cyclohexyldimethylamine. The raw materials of the process are cheap and easy to obtain, the environmental pollution is small, the cost is low, and the process does not relate to the raw materials which are easy to cause potential safety hazards.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation process of 1, 3-cyclohexyldimethylamine comprises the following steps:
1) Isomeric dehydrogenation of cyclohexene oxide: converting the cyclohexene oxide shown in the formula I into cyclohexenone shown in the formula II under the action of an isomerization dehydrogenation catalyst;
2) Addition of cyclohexenone to hydrocyanic acid: reacting cyclohexenone under the action of hydrocyanic acid and an alkaline addition catalyst to generate 1, 3-dicyano-1-cyclohexanol shown in a formula III;
3) Dehydration and hydrogenation of 1, 3-dicyano-1-cyclohexanol: dehydrating and hydrogenating the obtained 1, 3-dicyano-1-cyclohexanol in the presence of hydrogen and a hydrogenation catalyst to generate the 1, 3-cyclohexyldimethylamine shown in the formula IV.
Further, the isomeric dehydrogenation catalyst in the step 1 is a lithium phosphate composite modified copper-based catalyst;
preferably, the lithium phosphate content of the isomeric dehydrogenation catalyst is from 0.1 to 60% by mass, preferably from 5 to 25% by mass, more preferably from 10 to 20% by mass, based on the total amount of the catalyst;
preferably, the isomeric dehydrogenation catalyst is prepared by the following coprecipitation method:
firstly, preparing a sodium phosphate aqueous solution (with the mass concentration of 0.01-1 mol/L, and further 0.2-0.5 mol/L) and a lithium chloride aqueous solution (with the mass concentration of 0.05-2 mol/L, and further 0.5-1.5 mol/L), then placing the copper-based catalyst powder into the sodium phosphate aqueous solution, fully shaking up, and then placing into a water bath constant temperature oscillator for processing for 10-24 h, wherein the water bath temperature is kept at 50-80 ℃, preferably about 70 ℃, and the shaking rate is 130-140 r/min. Then keeping the temperature and continuing shaking, dropping a lithium chloride aqueous solution (the molar ratio of lithium chloride to sodium phosphate is 2-4, and more preferably 3.01-3.05). Filtering, washing the obtained sample with deionized water for 3-5 times at normal temperature, drying at 100-150 ℃, preferably about 120 ℃, then roasting at 300-400 ℃, for example 320 ℃ for 5-18 hours, preferably about 8 hours, granulating and forming to obtain the isomeric hydrogenation catalyst.
The prepared catalyst needs to be activated for about 10 hours at 200 ℃ under the normal pressure of the mixed gas of hydrogen and nitrogen before use. The activation method includes, for example: filling the prepared catalyst into a reactor, introducing nitrogen under the condition of normal pressure or micro-positive pressure, slowly heating to 200 ℃, then introducing hydrogen, and in the activation stage, the temperature of the reactor is prevented from being out of control by controlling the proportion of the nitrogen and the hydrogen, and the activation time is 10 hours.
Preferably, the copper-based catalyst is a supported or unsupported catalyst; the non-supported catalyst is a mixture consisting of an active component Cu and a transition metal oxide and/or a rare earth metal oxide, wherein the transition metal oxide is selected from one or more of nickel oxide, zinc oxide, chromium oxide, iron oxide, cobalt oxide and molybdenum oxide, preferably one or two of zinc oxide and iron oxide, and the rare earth oxide is selected from one or more of cerium oxide, lanthanum oxide, samarium oxide, praseodymium oxide and yttrium oxide, preferably one or two of cerium oxide and lanthanum oxide; the supported catalyst consists of an active component Cu and a carrier, wherein the carrier is selected from one of alumina, silica, activated carbon and zeolite, and the content of the active component Cu is 0.01-50 wt%, preferably 1-20 wt%, based on the total weight of the catalyst.
Further, the reaction conditions in step 1 are as follows: the reaction temperature is 150-350 ℃, preferably 220-270 ℃, and the reaction pressure is 0-1 MPa.
Further, the mass space velocity of the raw material epoxy cyclohexane in the step 1 is 0.1-1 g/g (cat)/h, and preferably 0.2-0.5 g/g (cat)/h.
Further, the reaction process in step 1 is carried out under the condition of inert carrier gas, and the preferred carrier gas is a mixed gas of hydrogen and nitrogen. The molar ratio of the mixed gas to the raw material epoxycyclohexane may be 1 to 100, preferably 5 to 30.
Further, the molar ratio of hydrocyanic acid to cyclohexenone in the step 2 is 2-100: 1, preferably 2.01 to 2.05:1.
further, the reaction temperature in the step 2 is 80-150 ℃, preferably 90-120 ℃, and the reaction time is 4-12 hours, preferably 6-10 hours.
Further preferably, the reactor in step 1 is a fixed bed.
Further, the basic addition catalyst in step 2 is one or more of alkali metal hydroxide/carbonate, alkaline earth metal hydroxide/carbonate and ammonia, or an organic amine or a quaternary ammonium base, preferably a quaternary ammonium base, more preferably tetraethylammonium hydroxide;
because the first occurrence in step 2 is the Michael addition reaction to form 3-cyanocyclohexanone (shown in formula V), tetraethylammonium hydroxide is preferred as the catalyst in the present invention. Tetraethyl ammonium hydroxide is unstable, and can be slowly decomposed into triethylamine and ethanol in the reaction process, and the generated triethylamine serving as a catalyst can further catalyze the addition of 3-cyanocyclohexanone and hydrocyanic acid to generate 1, 3-dicyano-1-cyclohexanol.
Preferably, the basic catalyst is used in an amount of 0.001 to 10mol%, preferably 0.05 to 5mol%, more preferably 0.5 to 1mol% of the cyclohexenone;
preferably, in the step 2, hydrocyanic acid and an alkaline addition catalyst are respectively dripped into a cyclohexenone solution for reaction, and more preferably, the dripping time of hydrocyanic acid is 1.5 to 3 times of that of the catalyst;
preferably, the reaction solvent in step 2 is an ether compound, preferably tetrahydrofuran and/or dioxane. Preferably, the cyclohexenone obtained in step 1) and an organic solvent are prepared into a solution to participate in the reaction, and the mass concentration of the cyclohexenone can be 1-50 wt%, preferably 10-25 wt%.
Further preferably, the reactor in step 2 is a batch tank reactor.
Further, the hydrogenation catalyst in the step 3 comprises an active metal oxide and a carrier, wherein the mass of the active metal oxide is 8-55 wt%, preferably 20-50 wt%, and more preferably 25-40 wt% of the mass of the carrier;
preferably, the active metal in the hydrogenation catalyst is one or two or more of Fe, co, ni, ru and Rh, preferably Co and/or Ni;
preferably, the support in the hydrogenation catalyst is acidic alumina.
Preferably, the hydrogenation catalyst in step 3 is prepared by an impregnation method, specifically: preparing the salt of the active metal into a solution, dipping the solution on an acidic alumina carrier by adopting a dipping method, drying the solution for 12 to 36 hours under an infrared lamp, pressing the dried solution into a strip, and drying the strip at 550 to 600 ℃ for later use. Before use, the prepared catalyst needs to be activated by normal pressure reduction for 4 to 12 hours at 400 to 600 ℃ through a mixed gas of hydrogen and nitrogen (the volume ratio is 1 to 10). After activation, hydrogen is introduced into the reactor to react with 1, 3-dicyano-1-cyclohexanol to produce 1, 3-cyclohexyldimethylamine.
Further, the mass space velocity of the 1, 3-dicyano-1-cyclohexanol in the step 3 is 0.05 to 1g/g (cat)/h, preferably 0.1 to 0.5g/g (cat)/h.
Further, the reaction temperature is 50-180 ℃, preferably 70-140 ℃; the reaction pressure is 2 to 10MPa, preferably 4 to 7MPa.
Further, the molar ratio of the hydrogen to the 1, 3-dicyano-1-cyclohexanol in the step 3 is 10 to 150:1, preferably 20 to 50:1.
further preferably, the reactor in step 3 is a continuous stirred tank, a fixed bed or a fluidized bed, preferably a fixed bed.
Compared with the prior art, the invention has the following beneficial effects:
(1) The raw materials are cheap and easy to obtain;
(2) The reaction yield is high, and the total yield is more than or equal to 90 percent;
(3) The reaction condition is mild, and the method is suitable for industrialization.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be merely illustrative of the invention and not limiting of its scope.
The main raw materials involved in the invention are as follows:
epoxycyclohexane (purity 99%): chemical agents of the national drug group, ltd;
40% tetraethylammonium hydroxide solution: TEAH, tokyo chemical reagents ltd;
triethylamine: chemical agents of the national drug group, ltd;
acid alumina powder: beike chemical (Tianjin) Limited liability company;
copper-zinc catalyst (Cu 40%), copper-silica catalyst (Cu 30%): shanghai Xuan.
NiCl 2 ·6H 2 O: chemical agents of the national drug group, ltd.
The test instrument used in this example was: nuclear magnetic recording was measured using Bruker AV300 with 50mg samples dissolved in 0.5mL of CDCl 3 Performing the following steps; gas Chromatography (GC) was tested using Agilent7820, and the samples were diluted 3-fold with chromatographic acetonitrile and then purified using HP-5 capillary chromatography (5% phenyl Methyl Siloxan,30m X0.32 mm X0.25 μm), FID detector. The temperatures of the sample injector and the detector are both 280 ℃; column temperature is controlled by adopting programmed temperature rise: the column temperature is initially maintained at 100 ℃ for 2 minutes, and the temperature is raised to 250 ℃ at 20 ℃/min and maintained for 0.5 minute. Column pressure 8.5868psi, flow rate 1.5mL/min, retention time 1.6837 minutes. Sample introduction amount: 0.2. Mu.L.
[ PREPARATION EXAMPLE 1 ] preparation of Isotropic dehydrogenation catalysts A to F
The isomeric dehydrogenation catalysts a to F were prepared according to the different conditions in table 1, respectively, as follows:
crushing a copper-based catalyst into powder, preparing 2500mL of sodium phosphate solution with a certain concentration, adding 500g of copper-based catalyst powder into the sodium phosphate aqueous solution, fully shaking up, placing in a water bath constant temperature oscillator for processing for 24h, wherein the water bath temperature is kept at about 80 ℃ during the period, and the oscillation rate is 140r/min. And then keeping the temperature and continuing shaking, dropping 2500mL of lithium chloride solution, controlling the dropping speed to finish within 1.5h, continuing shaking for 6h at the temperature, filtering, placing the obtained sample in concentrated ammonia water, fully shaking uniformly, placing the sample in a water bath constant temperature oscillator for treating for 7.5h, and keeping the temperature of the water bath at about 30 ℃ during the period, wherein the shaking speed is 140r/min. Filtering, washing the obtained sample with deionized water for 3 times at normal temperature, drying at 120 ℃, roasting at 320 ℃ for 8 hours, and granulating to obtain the catalyst.
The total mass of the different isomeric dehydrogenation catalysts prepared by the above process and the lithium phosphate content are shown in table 1.
TABLE 1 preparation conditions and results for different isomeric dehydrogenation catalysts
[ PREPARATION EXAMPLE 2 ] preparation of hydrogenation catalysts 1 to 8, 9'-10'
According to the proportion in the table 2, the salt of the active metal is added into 500mL of water to prepare a solution, the active metal is soaked on the carrier by adopting a soaking method, and after drying for 24 hours under an infrared lamp, the active metal is pressed into a strip for forming, and is dried for a period of time at a certain temperature for later use. Specific preparation conditions and results are shown in Table 2.
TABLE 2 hydrogenation catalyst preparation conditions and results
All the following examples were carried out by using the same reaction apparatus, except for the charged catalyst and the reaction conditions in each step.
The same catalyst activation conditions were used in the same step in all the following examples.
[ example 1 ]
1, 3-cyclohexyldimethylamine is prepared according to the following steps and methods:
(1) Isomeric dehydrogenation of epoxycyclohexane
Introducing nitrogen under normal pressure, slowly heating to 200 ℃, then introducing hydrogen to activate the catalyst, controlling the proportion of the nitrogen and the hydrogen in the activation stage to avoid the temperature of the reactor from being out of control, and the activation time is 10 hours.
Mixing and vaporizing the epoxy cyclohexane with a carrier gas (the volume ratio of hydrogen to nitrogen is 1; the raw material gas mixture enters a stainless steel tube type fixed bed reactor (the inner diameter is 25mm, the length is 1000 mm) filled with 112.06g of the isomeric dehydrogenation catalyst A, and epoxy cyclohexane is converted into cyclohexenone under the conditions of normal pressure and 220 ℃, wherein the mass space velocity of the epoxy cyclohexane is 0.2g/g (cat)/h. And (3) intermittently sampling to perform GC analysis on the reaction liquid, and after the reaction is performed for 8 hours, entering a stable state, wherein the reaction conversion rate reaches 99.8 percent, and the selectivity of the cyclohexenone reaches 98.3 percent.
The nuclear magnetic spectrum data are as follows:
1 H NMR(300MHz，CDCl 3 )：1.67(m,2H),1.96(m,2H),3.16(t,2H,)，6.07(b,H)，6.57(m,H).
(2) Addition of cyclohexenone to hydrocyanic acid
100g (containing 1.00mol of cyclohexenone) of the reaction solution prepared in the step 1 and 900g of dioxane were weighed into a 3000ml three-necked flask, heated to 90 ℃, and then 28.41g of 96.09% hydrocyanic acid (1.01 mol) and 1.84g of 40% tetraethylammonium hydroxide solution (0.005 mol, accounting for 0.5% of the molar amount of cyclohexenone) were added by a advection pump, wherein the hydrocyanic acid and the catalyst were simultaneously added dropwise, the dropwise addition rate was controlled so that the hydrocyanic acid dropwise addition time was 5.5 hours, and the catalyst dropwise addition time was 2.75 hours. Keeping the reaction temperature at 90 ℃ in the dropping process, and continuing to perform heat preservation reaction for 30min after the feeding is finished to prepare the 1, 3-dicyano-1-cyclohexanol reaction liquid. The conversion was analyzed to be 99.7% and the selectivity 99.0%.
The nuclear magnetic spectrum data are as follows:
1 H NMR(300MHz，CDCl 3 )：1.58～2.34(m,8H),2.44(m,H,),3.65(brs,H).
(3) Dehydration hydrogenation
Introducing nitrogen under normal pressure, slowly heating to 400 ℃, then introducing hydrogen, activating the catalyst, controlling the ratio of the nitrogen and the hydrogen in the activation stage to avoid the temperature of the reactor from being out of control, and the activation time is 10 hours.
Continuously feeding the reaction liquid containing the 1, 3-dicyano-1-cyclohexanol prepared in the step 2 into a stainless steel tube type fixed bed reactor (the inner diameter is 25mm, the length is 1000 mm) filled with 124.78g of hydrogenation catalyst 1 through a feed pump, wherein the mass space velocity of the 1, 3-dicyano-1-cyclohexanol is 0.1g/gcat/h, and introducing hydrogen according to 20 times of the molar weight of the 1, 3-dicyano-1-cyclohexanol to perform hydrogenation reaction. The reaction temperature is 70 ℃ and the reaction pressure is 4MPa. And (3) intermittently sampling to perform GC analysis on the reaction solution, and after the reaction is performed for 8 hours, entering a stable state, wherein the reaction conversion rate reaches 99.4 percent, and the selectivity of the 1,3-BAC reaches 95.3 percent.
The nuclear magnetic spectrum data are as follows:
1 H NMR(300MHz，CDCl 3 )：1.27～1.49(m,2H),1.52(m,4H,),1.53(m,2H,)，2.48～2.73(b,2H,)，1.67(m,2H,)，5.11(brs，4H).
[ examples 2 to 11 ]
Examples 2 to 11 were carried out in the same manner as in example 1 except for the differences in the reaction conditions and results shown in Table 3.
Comparative example 1
1, 3-Cyclohexanediamine was prepared according to the method and procedure as in example 1, except that the dehydration hydrogenation process in the step 3 used the 9' # catalyst shown in Table 2 as the hydrogenation catalyst, the reaction conversion was 48% and the 1,3-BAC selectivity was 30%.
Comparative example 2
1, 3-Cyclohexanediamine was prepared according to the method and procedure as described in example 1 except that the dehydration hydrogenation process of step 3 used the 10' # catalyst shown in Table 2 as the hydrogenation catalyst, the reaction conversion was 55% and the 1,3-BAC selectivity was 44%.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be considered as the protection scope of the present invention.
Table 3, reaction conditions and results in examples 1 to 11
Claims (36)
1. A preparation process of 1, 3-cyclohexyldimethylamine is characterized by comprising the following steps:
1) Isomeric dehydrogenation of cyclohexene oxide: converting the cyclohexene oxide shown in the formula I into cyclohexenone shown in the formula II under the action of an isomerization dehydrogenation catalyst;
2) Addition of cyclohexenone to hydrocyanic acid: reacting cyclohexenone with hydrocyanic acid and an alkaline addition catalyst to generate 1, 3-dicyano-1-cyclohexanol shown in a formula III;
3) Dehydration and hydrogenation of 1, 3-dicyano-1-cyclohexanol: dehydrating and hydrogenating the obtained 1, 3-dicyano-1-cyclohexanol in the presence of hydrogen and a hydrogenation catalyst to generate the 1, 3-cyclohexyldimethylamine shown in the formula IV.
2. The process of producing 1, 3-cyclohexyldimethylamine according to claim 1, wherein said isodehydrogenation catalyst in step 1 is a lithium phosphate composite-modified copper-based catalyst.
3. The process of producing 1, 3-cyclohexyldimethylamine according to claim 2, wherein the lithium phosphate content of the isodehydrogenation catalyst is 0.1-60% by mass, based on the total amount of the catalyst.
4. The process of producing 1, 3-cyclohexyldimethylamine according to claim 3, wherein the lithium phosphate content in the isomerization-dehydrogenation catalyst is 5 to 25% by mass, based on the total amount of the catalyst.
5. The process for producing 1, 3-cyclohexyldimethylamine according to claim 4, wherein the lithium phosphate content of the isodehydrogenation catalyst is 10 to 20% by mass based on the total amount of the catalyst.
6. The process for producing 1, 3-cyclohexyldimethylamine according to claim 2, wherein said copper-based catalyst is a supported or unsupported catalyst; the non-supported catalyst is a mixture consisting of an active component Cu and a transition metal oxide and/or a rare earth metal oxide, wherein the transition metal oxide is selected from one or more of nickel oxide, zinc oxide, chromium oxide, iron oxide, cobalt oxide and molybdenum oxide, and the rare earth oxide is selected from one or more of cerium oxide, lanthanum oxide, samarium oxide, praseodymium oxide and yttrium oxide; the supported catalyst consists of an active component Cu and a carrier, wherein the carrier is selected from one of alumina, silica, activated carbon and zeolite, and the content of the active component Cu is 0.01-50 wt% based on the total weight of the catalyst.
7. The process for producing 1, 3-cyclohexyldimethylamine according to claim 6, wherein the transition metal oxide is one or two selected from zinc oxide and iron oxide, and the rare earth oxide is one or two selected from cerium oxide and lanthanum oxide.
8. The process for producing 1, 3-cyclohexyldimethylamine according to claim 6, wherein the content of Cu, an active ingredient, in the supported catalyst is 1 to 20wt% based on the total weight of the catalyst.
9. The process for producing 1, 3-cyclohexyldimethylamine according to claim 2, wherein the reaction conditions in step 1 are: the reaction temperature is 150-350 ℃, and the reaction pressure is 0-1 MPa.
10. The process for producing 1, 3-cyclohexyldimethylamine according to claim 9, wherein the reaction temperature in step 1 is 220-270 ℃.
11. The process for producing 1, 3-cyclohexyldimethylamine according to any of the claims 2-10, wherein the mass space velocity of the raw material epoxycyclohexane in step 1 is 0.1-1 g/g (cat)/h.
12. The process of claim 11, wherein the mass space velocity of the raw material cyclohexene oxide in step 1 is 0.2-0.5 g/g (cat)/h.
13. The process for producing 1, 3-cyclohexyldimethylamine according to any of the claims 1-10, wherein the molar ratio of hydrocyanic acid to cyclohexenone in step 2 is 2-100: 1.
14. the process of claim 13, wherein the molar ratio of hydrocyanic acid to cyclohexenone in the step 2 is from 2.01 to 2.05:1.
15. the process for producing 1, 3-cyclohexyldimethylamine according to claim 13, wherein the reaction temperature in step 2 is 80-150 ℃ and the reaction time is 4-12 hours.
16. The process for producing 1, 3-cyclohexyldimethylamine according to claim 15, wherein the reaction temperature in step 2 is 90-120 ℃ and the reaction time is 6-10 hours.
17. The process for producing 1, 3-cyclohexyldimethylamine according to claim 15, wherein the basic addition catalyst in step 2 is one or more of alkali metal hydroxide/carbonate, alkaline earth metal hydroxide/carbonate and ammonia, or organic amine or quaternary ammonium base.
18. The process for producing 1, 3-cyclohexyldimethylamine according to claim 17, wherein the basic addition catalyst in step 2 is quaternary ammonium hydroxide.
19. The process of producing 1, 3-cyclohexyldimethylamine according to claim 17, wherein the basic addition catalyst in step 2 is tetraethylammonium hydroxide.
20. The process for producing 1, 3-cyclohexyldimethylamine according to claim 17, wherein the amount of the basic addition catalyst is 0.001 to 10mol% based on cyclohexenone.
21. The process of claim 20, wherein the amount of the basic addition catalyst is 0.05 to 5mol% based on the cyclohexenone.
22. The process of producing 1, 3-cyclohexyldimethylamine according to claim 21, wherein the amount of the basic addition catalyst is 0.5-1 mol% based on the cyclohexenone.
23. The process of producing 1, 3-cyclohexanedimethanamine according to claim 17, wherein hydrocyanic acid and an alkaline addition catalyst are added dropwise to the cyclohexenone solution to react in step 2.
24. The process according to claim 23, wherein the hydrocyanic acid is added dropwise in the amount of 1 to 3.5 times as long as the basic addition catalyst in the step 2.
25. The process according to claim 17, wherein the reaction solvent in the step 2 is an ether compound.
26. The process for producing 1, 3-cyclohexyldimethylamine according to claim 17, wherein the reaction solvent in step 2 is tetrahydrofuran and/or dioxane.
27. The process for producing 1, 3-cyclohexyldimethylamine according to any of the claims 1-10, wherein the hydrogenation catalyst in step 3 comprises active metal oxide and carrier, wherein the mass of the active metal oxide is 8-55 wt% of the mass of the carrier.
28. The process of claim 27, wherein the mass of the active metal oxide in the hydrogenation catalyst of step 3 is 20-50 wt% of the mass of the carrier.
29. The process of claim 28, wherein the mass of the active metal oxide in the hydrogenation catalyst of step 3 is 25-40 wt% of the mass of the carrier.
30. The process according to claim 27, wherein the active metal in the hydrogenation catalyst is one or two or more selected from the group consisting of Fe, co, ni, ru and Rh.
31. The process of claim 30, wherein the active metal of the hydrogenation catalyst is Co and/or Ni.
32. The process according to claim 27, wherein the carrier in the hydrogenation catalyst is acidic alumina.
33. The process of preparing 1, 3-cyclohexyldimethylamine according to claim 27, wherein the mass space velocity of 1, 3-dicyano-1-cyclohexanol in step 3 is 0.05-1 g/g (cat)/h.
34. The process of claim 33, wherein the mass space velocity of 1, 3-dicyano-1-cyclohexanol in step 3 is 0.1-0.5 g/g (cat)/h.
35. The process for preparing 1, 3-cyclohexyldimethylamine according to claim 33, wherein said reaction temperature is 50-180 ℃; the reaction pressure is 2-10 Mpa.
36. The process for preparing 1, 3-cyclohexyldimethylamine according to claim 35, wherein said reaction temperature is between 70 ℃ and 140 ℃; the reaction pressure is 4-7 Mpa.
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| CN102911062A (en) * | 2011-08-04 | 2013-02-06 | 上海泰禾化工有限公司 | Method for preparing 1,3-cyclohexyl dimethylamine |
| CN104066730A (en) * | 2011-10-14 | 2014-09-24 | 埃姆比特生物科学公司 | Heterocyclic compounds and methods of use thereof as modulators of type III receptor tyrosine kinases |
| CN106478431A (en) * | 2016-10-13 | 2017-03-08 | 上海瀚鸿科技股份有限公司 | A kind of method of synthesis of trans hexamethylene dimethylamine |
| CN110105223A (en) * | 2019-05-15 | 2019-08-09 | 常州大学 | A kind of method that continuity method prepares 1,3- hexamethylene dimethylamine |
| CN111116381A (en) * | 2020-01-02 | 2020-05-08 | 万华化学集团股份有限公司 | Method for preparing 1, 3-cyclohexyldimethylamine by m-xylylenediamine hydrogenation |
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| CN102911062A (en) * | 2011-08-04 | 2013-02-06 | 上海泰禾化工有限公司 | Method for preparing 1,3-cyclohexyl dimethylamine |
| CN104066730A (en) * | 2011-10-14 | 2014-09-24 | 埃姆比特生物科学公司 | Heterocyclic compounds and methods of use thereof as modulators of type III receptor tyrosine kinases |
| CN106478431A (en) * | 2016-10-13 | 2017-03-08 | 上海瀚鸿科技股份有限公司 | A kind of method of synthesis of trans hexamethylene dimethylamine |
| CN110105223A (en) * | 2019-05-15 | 2019-08-09 | 常州大学 | A kind of method that continuity method prepares 1,3- hexamethylene dimethylamine |
| CN111116381A (en) * | 2020-01-02 | 2020-05-08 | 万华化学集团股份有限公司 | Method for preparing 1, 3-cyclohexyldimethylamine by m-xylylenediamine hydrogenation |
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