CN108503555B - 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol and preparation method and application thereof - Google Patents
4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol and a preparation method and application thereof. The method comprises the step of reacting byproduct 4- ((4-cyclohexylamino) methyl) cyclohexanol in the HMDA reaction process with formaldehyde and hydrogen under the action of a catalyst to obtain 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol. The obtained 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol can be used as a polyurethane foaming reaction type catalyst after being purified. The invention realizes the effective utilization of the HMDA byproduct, greatly reduces the production cost and realizes the reasonable utilization of resources. 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is used as a novel reactive catalyst for preparing polyisocyanurate/polyurethane and the like, has the characteristics of low smell and strong yellowing resistance, and the product has lower VOC.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol and a preparation method and application thereof.
Background
Diaminodicyclohexylmethane (HMDA for short) is the main raw material for producing a new generation of aging-resistant polyurethane-dicyclohexylmethane diisocyanate (HMDI) with excellent performance, and the isocyanate can be used for preparing polyurethane coatings and paints with light weight and stable performance. HMDA is also useful as an epoxy hardener and transparent nylon. The catalyst is usually prepared by using diaminodiphenylmethane (MDA) as a raw material and reacting under the action of hydrogen and a hydrogenation catalyst. However, in the preparation process of HMDA, water added in the reaction process reacts with the main product HMDA to generate the byproduct 4- ((4-cyclohexylamino) methyl) cyclohexanol. At present, no effective utilization method for the by-product exists, and only qualified environmental protection companies can be entrusted to treat the waste liquid. The production process is as follows:
the prior art has no method for utilizing byproduct 4- ((4-cyclohexylamino) methyl) cyclohexanol in the HMDA production process, and reports that 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is used as a polyurethane foam catalyst are not found.
Disclosure of Invention
The invention aims to provide a novel compound 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol and a preparation method of the compound aiming at the defects in the prior art, and particularly provides a method for preparing 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol by taking 4- ((4-cyclohexylamino) methyl) cyclohexanol as a raw material, wherein the used raw material 4- ((4-cyclohexylamino) methyl) cyclohexanol is a byproduct in a manufacturing process of diaminodicyclohexyl methane, and no effective treatment method exists at present, so that waste utilization is realized.
The invention also provides application of the novel compound, wherein 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is a reactive catalyst and can be used for preparing polyurethane foam, and the problem of unpleasant odor generated in the using process of a common polyurethane foam catalyst can be effectively avoided due to the large molecular weight.
The technical scheme of the invention is as follows:
a compound 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol has a structure shown in a formula (I):
a preparation method of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol comprises the following steps: 4- ((4-cyclohexylamino) methyl) cyclohexanol is mixed with a solvent, and then methylation reaction is carried out on the 4- ((4-dimethylamino) cyclohexyl) methyl) cyclohexanol with formaldehyde and hydrogen under the action of a catalyst, so as to obtain the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol.
Further, the 4- ((4-cyclohexylamino) methyl) cyclohexanol is a byproduct in a diaminodicyclohexylmethane (HMDA) preparation process. The purity of the 4- ((4-cyclohexylamino) methyl) cyclohexanol is more than or equal to 99.5 wt%, and the 4- ((cyclohexylamino) methyl) cyclohexanol contains a small amount of diaminodicyclohexylmethane. The method for preparing diaminodicyclohexylmethane in the invention is preferably as follows: in the presence of rhodium catalyst, 4, 4-diaminodiphenylmethane is subjected to high-temperature catalytic hydrogenation in a solvent to obtain the catalyst. Rectifying and purifying the high-temperature catalytic hydrogenation reaction liquid for preparing the diaminodicyclohexyl methane to obtain a byproduct 4- ((4-cyclohexylamino) methyl) cyclohexanol, wherein the byproduct 4- ((4-cyclohexylamino) methyl) cyclohexanol mainly comprises and also contains a small amount of diaminodicyclohexyl methane.
Further, the solvent is at least one of tetrahydrofuran, methanol, ethanol, dioxane and acetone, and tetrahydrofuran is preferred.
Further, the formaldehyde raw material is in the form of aqueous solution, namely aqueous formaldehyde solution and/or aqueous paraformaldehyde solution, wherein the concentration of formaldehyde in the aqueous solution is preferably 10-40 wt%, and most preferably 37 wt%; the aqueous paraformaldehyde solution is preferably a crude depolymerization aqueous solution of paraformaldehyde.
Further, the catalyst is selected from a supported palladium-based catalyst and/or a raney-type catalyst, preferably a supported palladium-based catalyst;
the supported palladium catalyst comprises palladium, a metal additive and a carrier;
in the supported palladium catalyst, the percentage content of palladium is 0.1-50 wt%, preferably 2-10 wt%; the percentage content of the metal auxiliary agent is 0.05-2 wt%, preferably 0.1-1.5 wt%;
the metal auxiliary agent is selected from one or more of cerium, nickel, cobalt and zinc, preferably nickel and/or cerium; when the metal auxiliary agent is nickel and cerium, the content of nickel is 0.1-1 wt% and the content of cerium is 0.3-1.5 wt% in the supported palladium catalyst;
the carrier is selected from at least one of alumina, silica gel, diatomite, zeolite molecular sieve, activated carbon, titanium dioxide, lithium aluminate and zirconia;
the supported palladium catalyst is preferably prepared by adopting an impregnation method: dissolving palladium salt and metal additive salt in deionized water to form a uniform solution, then adding a carrier, carrying out rotary impregnation, evaporating to remove water, drying, roasting, and cooling to obtain the supported palladium catalyst.
Further, the molar ratio of formaldehyde to 4- ((4-cyclohexylamino) methyl) cyclohexanol is 2-10:1, preferably 2-4: 1.
Further, the catalyst is used in an amount of 1 to 5 wt%, preferably 2 to 3 wt% of 4- ((4-cyclohexylamino) methyl) cyclohexanol.
Further, the solvent is used in an amount of 50 to 200 wt%, preferably 75 to 100 wt% of 4- ((4-cyclohexylamino) methyl) cyclohexanol.
Further, the methylation reaction is carried out at the reaction temperature of 60-180 ℃, preferably 80-140 ℃; the reaction pressure is from 0.5 to 10MPa (gauge pressure), preferably from 1 to 5MPa (gauge pressure). The end conditions of the methylation reaction were: after the formaldehyde feed was complete, the hydrogen line valve was closed and the reaction was complete when the pressure drop every 10 minutes was < 0.3 bar.
Further, in the methylation reaction, formaldehyde is fed in a semi-continuous mode, and preferably fed in 2 times.
Further, the methylation reaction is preferably in a sectional reaction mode, and specifically comprises the following steps: first feeding formaldehyde to a molar ratio of 1.1-1.5:1 with 4- ((4-cyclohexylamino) methyl) cyclohexanol at 60-110 ℃, preferably 80-100 ℃, for a time of 0.5-2h, preferably 0.7-1.5 h; after stopping feeding the formaldehyde, raising the temperature to 110-180 ℃ at a rate of 0.5-5 ℃/min, preferably 1-2 ℃/min; then adding the residual formaldehyde within the time of 0.5-2h, preferably 0.7-1.5h, and reacting at the temperature of 110-180 ℃, preferably at the temperature of 120-140 ℃ until the reaction is completed.
Further, after the methylation reaction is completed, the reaction liquid is rectified and purified to obtain the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, and the rectification and purification method is normal-pressure rectification or reduced-pressure rectification, preferably reduced-pressure rectification;
the rectification purification is carried out, and the pressure is 0.1-5KPa (absolute pressure), preferably 0.5-2KPa (absolute pressure); the theoretical plate number of the rectification column is 20-50, preferably 35; the reflux ratio is from 1 to 10:1, preferably about 5: 1.
The compound 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol disclosed by the invention can be used as a reaction type catalyst for preparing polyisocyanurate foam, polyurethane foam and the like, is particularly suitable for preparing polyurethane soft foam, polyurethane semi-hard foam and polyurethane hard foam, and reduces the odor and VOC volatilization of sponge products. The 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol not only contains tertiary amine in molecules, but also contains hydroxyl functional groups, is a reactive catalyst, and can effectively avoid the problem that the common polyurethane foam catalyst generates unpleasant odor in the use process due to the large molecular weight. Compared with the traditional catalyst, the catalyst has the characteristics of low odor, obvious environmental protection advantage and wide market prospect.
The preparation method of the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol provided by the invention takes 4- ((4-cyclohexylamino) methyl) cyclohexanol, a solvent, hydrogen and formaldehyde as raw materials, and performs methylation reaction under the action of a catalyst to obtain the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, wherein the chemical reaction equation is as follows:
as the 4- ((4-cyclohexylamino) methyl) cyclohexanol serving as the raw material is easily subjected to intermolecular deamination to form secondary amine at the temperature of more than 110 ℃, the reaction process is as follows:
the generated secondary amine can react with formaldehyde and hydrogen to generate corresponding byproduct impurities, thereby influencing the yield of the main product. According to the reaction scheme, 4- ((4-cyclohexylamino) methyl) cyclohexanol generates one methyl group and then generates another methyl group under the reaction conditions. The reaction process is as follows:
the preparation method adopts sectional reaction and controls the feeding amount of formaldehyde, 4- (4-cyclohexylamino) methylcyclohexanol can generate 4- ((4-methylaminocyclohexyl) methyl) cyclohexanol with formaldehyde and hydrogen at a low temperature section without generating secondary amine as a byproduct, and then the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is generated at a high temperature section, so that the generation of side reaction can be effectively controlled, and the yield of the product is improved.
In the production process of diaminodicyclohexyl methane, a byproduct 4- ((4-cyclohexylamino) methyl) cyclohexanol is generated, but no resource utilization method of a compound 4- ((4-cyclohexylamino) methyl) cyclohexanol exists in the prior art, and the byproduct 4- ((4-cyclohexylamino) methyl) cyclohexanol is rectified at present to be treated as waste liquid, so that the treatment cost of three wastes is increased, the waste of resources is caused, and the environment is damaged. The invention discloses a new compound 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol by comprehensively considering the factors, wherein the new compound is prepared by taking 4- ((4-cyclohexylamino) methyl) cyclohexanol as a raw material, can be used as a reaction type catalyst to be applied to the field of polyurethane foam, has high economic benefit and is suitable for industrial large-scale production.
The technical scheme of the invention has the beneficial effects that: the novel compound 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is prepared from a byproduct 4- ((4-cyclohexylamino) methyl) cyclohexanol serving as a raw material in a diaminodicyclohexylmethane production process, so that reasonable utilization of resources is realized, and the production cost is greatly reduced. The 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is a novel reactive catalyst, is used for preparing polyisocyanurate/polyurethane and the like, has the characteristics of low smell and strong yellowing resistance, and the product has lower VOC.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol prepared in example 4.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the present invention is not limited to the examples listed.
The conditions for gas chromatographic analysis in the following examples were: an Agilent DB-5 chromatographic column, wherein the injection port temperature is 300 ℃, the FID detector temperature is 300 ℃, the column flow rate is 1.5mL/min, the hydrogen flow rate is 30mL/min, the air flow rate is 300mL/min, the temperature programming mode is that the temperature is kept for 1min at 80 ℃, and the temperature is increased to 280 ℃ at 15 ℃/min and kept for 15 min.
Example 1
Preparation of palladium catalyst 1:
5.00g of palladium nitrate dihydrate, 4.96g of nickel nitrate hexahydrate and 0.93g of cerium nitrate hexahydrate are dissolved in 100mL of deionized water, heated to 80 ℃ to form a uniform solution, and then 96.7g of activated carbon (average particle size is 50 μm, specific surface area is 150 m)2(g), rotationally dipping in a water bath at 80 ℃ for 4h, gradually evaporating water, and drying in a drying oven at 120 ℃ for 12 h; and finally, moving the catalyst to a muffle furnace, heating the catalyst to 500 ℃ at the speed of 2 ℃/min in the air atmosphere, roasting the catalyst for 6 hours, and naturally cooling the catalyst to obtain the catalyst. The catalyst comprises the following components: pd 2 wt%, Ni 1 wt%, Ce 0.3 wt%, and the balance of active carbon, wherein corresponding metal elements account for the total mass of the catalyst.
Example 2
Preparation of palladium catalyst 2:
25.04g of palladium nitrate dihydrate, 0.50g of nickel nitrate hexahydrate and 1.55g of cerium nitrate hexahydrate are dissolved in 100mL of deionized water, heated to 60 ℃ to form a uniform solution, and 89.4g of alumina (average particle size 100 μm, specific surface area 180 m) is added2(g), the water is gradually evaporated after the rotary dipping is carried out for 5 hours in a water bath at the temperature of 70 ℃, and the drying is carried out for 16 hours in an oven at the temperature of 100 ℃; and finally, moving the catalyst to a muffle furnace, heating the catalyst to 550 ℃ at the speed of 3 ℃/min in the air atmosphere, roasting the catalyst for 8 hours, and naturally cooling the catalyst to obtain the catalyst. The catalyst comprises the following components: 10 wt% of Pd, 0.1 wt% of Ni, 0.5 wt% of Ce and the balance of alumina, wherein corresponding metal elements account for the total mass of the catalyst.
Example 3
Preparation of palladium catalyst 3:
12.52g of palladium nitrate dihydrate, 2.48g of nickel nitrate hexahydrate and 4.65g of cerium nitrate hexahydrate were dissolved in 100mL of deionized water, heated to 70 ℃ to form a uniform solution, and 95.5g of silica (average particle size 100 μm, specific surface area 200 m) was added2(g), rotationally dipping in a water bath at 60 ℃ for 6 hours, gradually evaporating water, and drying in a drying oven at 120 ℃ for 12 hours; and finally, moving the catalyst to a muffle furnace, heating the catalyst to 600 ℃ at the speed of 2 ℃/min in the air atmosphere, roasting the catalyst for 6 hours, and naturally cooling the catalyst to obtain the catalyst. The catalyst comprises the following components: 5 wt% of Pd, 0.5 wt% of Ni, 1.5 wt% of Ce and the balance of silicon dioxideThe elements account for the total mass of the catalyst.
Example 4
Preparation of raw material 4- ((4-cyclohexylamino) methyl) cyclohexanol: diaminodicyclohexylmethane by-product:
5g Rh/Al was added to a 2L autoclave2O3(the metal content of Rh is 5%) catalyst, sealing with a 10MPa gas seal in a reactor, if no leakage occurs, adding 500g of 4, 4-diaminodiphenylmethane and 500g of tetrahydrofuran, respectively replacing with 1MPa (gauge pressure) of nitrogen and hydrogen for three times, supplementing pressure to 4.5MPa (gauge pressure) with hydrogen, raising the temperature to 190 ℃, continuously introducing hydrogen into the reactor through a hydrogen flow controller in the reaction process, ensuring that the pressure in the reactor is maintained to 8MPa (gauge pressure), and stopping introducing the hydrogen when the instantaneous flow of the hydrogen flow controller is lower than 100 sccm. And when the pressure drop of the reaction kettle is less than 1bar/10min, stopping the reaction, reducing the temperature in the reaction kettle to 50 ℃, relieving the pressure, and filtering through a filter arranged in the reaction kettle to obtain the diaminodicyclohexylmethane reaction solution. After the reaction solution of diaminodicyclohexylmethane was added, the reaction solution was stirred at a pressure of 0.5KPa, the number of theoretical plates of a rectifying column was 35, and the reflux ratio was 5:1, carrying out vacuum rectification at the tower bottom temperature of 200 ℃ and the tower top temperature of 165 ℃ to obtain the 4- ((4-cyclohexylamino) methyl) cyclohexanol. The purity of 4- ((4-cyclohexylamino) methyl) cyclohexanol was 99.8 wt% by gas phase detection, and it contained 0.2 wt% diaminodicyclohexylmethane.
Preparation of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol:
activating the catalyst: 4g of the palladium catalyst in example 1 was charged into a 1L reactor, a tetrahydrofuran solvent was added to make a bottom, the reactor was sealed, the reaction vessel was replaced with nitrogen and hydrogen gas three times, and the catalyst was activated at 180 ℃ and a hydrogen pressure of 5MPa (gauge pressure) for 6 hours. Then cooling, decompressing and replacing with nitrogen for three times, and filtering the solvent out of the reaction kettle. Then 200g of 4- ((4-cyclohexylamino) methyl) cyclohexanol and 200g of tetrahydrofuran are added, nitrogen and hydrogen are sequentially used for replacing three times, the initial hydrogen pressure is 2MPa (gauge pressure), the stirring is started to be 700 r/min, the reaction temperature is increased to 80 ℃, the hydrogen pressure is adjusted to 4MPa (gauge pressure) and hydrogen is continuously introduced, 84g of 37 wt% aqueous formaldehyde solution is introduced into the reaction kettle at the speed of 2.5g/min by using a constant-flow pump, then the feeding of the formaldehyde is stopped, the reaction temperature is increased to 140 ℃ at the speed of 2 ℃/min, then the temperature is kept at 140 ℃, 77g of 37 wt% aqueous formaldehyde solution is continuously introduced into the reaction kettle at the speed of 2.5g/min by using the constant-flow pump, after the feeding of the formaldehyde is finished, the pipeline valve is closed, the pressure is held, and the reaction is stopped when the pressure drop every 10min is less than 0.3 bar. And then cooling, decompressing, replacing for three times by nitrogen, and filtering to obtain the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol reaction liquid.
Gas phase detection shows that the content of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol in the reaction liquid is 98.2 wt%. The reaction solution is heated and stirred under the conditions that the pressure is 1KPa, the theoretical plate number of a rectifying column is 35, the reflux ratio is 5: and (3) carrying out reduced pressure rectification at 1 to obtain 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, wherein the purity of the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is 99.5 wt% by gas phase detection.
The nuclear magnetic resonance spectrum of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is shown in figure 1,1HNMR data: (CDCl)3As solvent, TMS as internal standard), a (2.19ppm), b (2.94ppm, standing bond), b (2.58ppm, flat bond), c (1.84ppm, standing bond), c (1.55ppm, flat bond), d (1.72ppm, standing bond), d (0.91ppm, flat bond), e (1.04ppm), f (1.19ppm), g (1.81ppm, flat bond), g (1.29ppm, standing bond), h (1.58ppm, flat bond), h (1.10ppm, standing bond), i (1.78ppm, standing bond), i (1.69ppm, flat bond), j (3.94ppm, standing bond), j (3.64ppm, flat bond), k (1.53 ppm).
Example 5
Preparation of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol:
the source of 4- ((4-cyclohexylamino) methyl) cyclohexanol as a starting material and the catalyst activation method were the same as in example 4.
Adding 6g of the palladium catalyst in example 2 into a 1L reaction kettle, adding 200g of 4- ((4-cyclohexylamino) methyl) cyclohexanol and 200g of methanol after activation, sequentially replacing for three times by nitrogen and hydrogen, starting to have a hydrogen pressure of 2MPa (gauge pressure), starting stirring for 700 r/min, waiting for the reaction temperature to rise to 90 ℃, adjusting the hydrogen pressure to 3MPa (gauge pressure) and continuously introducing hydrogen, starting to introduce 115g of a 37 wt% formaldehyde aqueous solution into the reaction kettle at a speed of 2g/min by using a constant-flow pump, stopping feeding of formaldehyde, increasing the reaction temperature to 120 ℃ at a speed of 1 ℃/min, continuously introducing 115g of formaldehyde water solution with the concentration of 37 wt% into the reaction kettle by using a constant-flow pump at the speed of 2.5g/min, after the formaldehyde feeding is finished, closing the valve of the hydrogen pipeline to start pressure building, and stopping the reaction when the pressure drop every 10 minutes is less than 0.3 bar. And then cooling, decompressing, replacing for three times by nitrogen, and filtering to obtain the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol reaction liquid. Gas phase detection shows that the content of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol in the reaction liquid is 97.5 wt%.
The reaction solution is stirred at the pressure of 2KPa, the theoretical plate number of a rectifying column is 50, the reflux ratio is 10: and (3) carrying out reduced pressure rectification at 1 to obtain 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, wherein the purity of the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is 99.8 wt% by gas phase detection.
Example 6
Preparation of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol:
the source of 4- ((4-cyclohexylamino) methyl) cyclohexanol as a starting material and the catalyst activation method were the same as in example 4.
Adding 3g of the palladium catalyst in example 3 into a 1L reaction kettle, adding 200g of 4- ((4-cyclohexylamino) methyl) cyclohexanol and 150g of ethanol after activation, sequentially replacing for three times by nitrogen and hydrogen, starting to have a hydrogen pressure of 2MPa (gauge pressure), starting stirring for 700 r/min, raising the reaction temperature to 105 ℃, adjusting the hydrogen pressure to 6MPa (gauge pressure) and continuously introducing hydrogen, starting to introduce 92g of a 37 wt% formaldehyde aqueous solution into the reaction kettle at a speed of 1g/min by using a constant-flow pump, then stopping feeding of formaldehyde, raising the reaction temperature to 150 ℃ at a speed of 2 ℃/min, continuously introducing 115g of a 37 wt% formaldehyde aqueous solution into the reaction kettle at a speed of 2g/min by using an advection pump, and after the feeding of formaldehyde is finished, closing the valve of the hydrogen pipeline to start pressure building, and stopping the reaction when the pressure drop every 10 minutes is less than 0.3 bar. And then cooling, decompressing, replacing for three times by nitrogen, and filtering to obtain the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol reaction liquid.
Gas phase detection shows that the content of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol in the reaction liquid is 96.8 wt%. The reaction solution is stirred at a pressure of 0.1KPa, the theoretical plate number of a rectifying column is 20, the reflux ratio is 1: and (3) carrying out reduced pressure rectification at 1 to obtain 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, wherein the purity of the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is 99.0 wt% by gas phase detection.
Example 7
Application of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol in polyurethane foam
The raw materials used are as follows:
polyol: wanol 562, produced by Wanol chemical group, inc; wanol 2045, produced by Wanol chemical group, inc.
Diethanolamine: manufactured by west longus science corporation.
Water: and (4) self-preparing deionized water.
Foam stabilizer: b-8715LF2, winning industrial group production.
Reaction type catalyst: DPA, manufactured by Henscman corporation.
Isocyanate: wannate 8001, produced by wanhua chemical group, inc.
The foaming properties were compared using a common reactive catalyst, DPA, and 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol prepared in example 1, with the raw material ratios shown in table 1.
TABLE 1
The manual free bubble operation is carried out by adopting a one-step method: adding polyalcohol, water, a foam stabilizer, a catalyst and the like into a container according to the proportion in the table 1, and dispersing at a high speed for 5 minutes to prepare a combined material; placing the combined material and isocyanate into a constant temperature incubator to be treated for 4 hours at the constant temperature of 23 ℃; the combined material and isocyanate are sequentially added into a paper cup, and then stirred for 5 seconds at the speed of 3000 r/min by using a high-speed dispersion machine, and then placed under an ultrasonic testing head of a foam growth curve tester for testing. The results are shown in table 2 below.
TABLE 2
| Group of | A | B |
| Onset time [ s ]] | 20.7 | 32.9 |
| Rise time [ s ]] | 123.5 | 158.3 |
| Time of full cup [ s] | 77.3 | 92.8 |
| Maximum foaming height (G) [ mm] | 220.9 | 200.8 |
| Final height [ mm ]] | 210.3 | 198.5 |
As can be seen from Table 2, at the same addition level, the foam system using DPA started to invent significantly faster, and the gel later did not sufficiently support the cell structure of the foam, resulting in a foam with a shrinkage of approximately 10 mm; by comparison, the foam system using the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol of the present invention has a relatively smooth whole foaming process and relatively small foam shrinkage, although the foam system starts up later. It is thus seen that the use of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol improves the post-maturation properties of the foam.
The foams were tested for odor and VOC. The test was carried out according to PV3900-2000 parts of automobile interior odor test method with the rating given in Table 3 below.
TABLE 3 rating scale
| Score of | Evaluation of | Score of | Evaluation of |
| 1 | Not experienced | 2 | Perceptible, without hindrance |
| 3 | Perceptible but not too disturbing | 4 | Has a hindrance |
| 5 | Is greatly hindered | 6 | Intolerable |
The 5 people evaluate and average to obtain: foam A is 3 minutes; foam B is 2 minutes; from this, it was found that the use of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol of the present invention as a catalyst is effective in reducing the odor of foam. The VOC measurements of the two foams are shown in table 4 below:
TABLE 4
From table 4, it can be seen that the use of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol of the present invention as a catalyst can effectively reduce the content of amine-based catalyst in the foam VOC, and TVOC can be reduced by 42%.
Comparative example 1
With reference to example 4, the difference is that during the preparation of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, aqueous formaldehyde is added in one portion, and the methylation reaction is not staged:
adding 4g of the palladium catalyst in example 1 into a 1L reaction kettle, adding 200g of 4- ((4-cyclohexylamino) methyl) cyclohexanol and 200g of tetrahydrofuran after activation, sequentially replacing three times with nitrogen and hydrogen, starting the hydrogen pressure to be 2MPa (gauge pressure), starting stirring at 700 r/min, raising the reaction temperature to 80 ℃, adjusting the hydrogen pressure to be 4MPa (gauge pressure) and continuously introducing hydrogen, starting to introduce 161g of a 37 wt% formaldehyde aqueous solution into the reaction kettle at the speed of 2.5g/min by using a constant-flow pump, closing a hydrogen pipeline valve to start pressure holding after the formaldehyde feeding is finished, and stopping the reaction when the pressure drop every 10 minutes is less than 0.3 bar. And then cooling, decompressing, replacing for three times by nitrogen, and filtering to obtain the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol reaction liquid.
Gas phase detection shows that the content of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol in the reaction liquid is 85.3 wt%. The reaction solution is heated and stirred under the conditions that the pressure is 1KPa, the theoretical plate number of a rectifying column is 35, the reflux ratio is 5: and (3) carrying out reduced pressure rectification at 1 to obtain 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, wherein the purity of the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is 98.3 wt% by gas phase detection.
Comparative example 2
With reference to example 5, the difference is that during the preparation of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, aqueous formaldehyde is added in one portion, and the methylation reaction is not staged:
adding 6g of the palladium catalyst in the example 2 into a 1L reaction kettle, adding 200g of 4- ((4-cyclohexylamino) methyl) cyclohexanol and 200g of methanol after activation, sequentially replacing for three times by using nitrogen and hydrogen, starting to have the hydrogen pressure of 2MPa (gauge pressure), starting stirring for 700 r/min, raising the reaction temperature to 120 ℃, adjusting the hydrogen pressure to 3MPa (gauge pressure) and continuously introducing hydrogen, starting to introduce 230g of 37 wt% formaldehyde aqueous solution into the reaction kettle at the speed of 2g/min by using a constant-flow pump, closing a hydrogen pipeline valve to start pressure holding after the formaldehyde feeding is finished, and stopping the reaction when the pressure drop every 10 minutes is less than 0.3 bar. And then cooling, decompressing, replacing for three times by nitrogen, and filtering to obtain the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol reaction liquid.
Gas phase detection shows that the content of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol in the reaction liquid is 91.2 wt%. The reaction solution is stirred at the pressure of 2KPa, the theoretical plate number of a rectifying column is 50, the reflux ratio is 10: and (3) carrying out reduced pressure rectification at 1 to obtain 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, wherein the purity of the 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is 98.7 wt% by gas phase detection.
Claims (14)
1. A preparation method of a reactive catalyst 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol with a structure shown as a formula (I) is characterized by comprising the following steps: mixing 4- ((4-cyclohexylamino) methyl) cyclohexanol with a solvent, and carrying out methylation reaction on the mixture with formaldehyde and hydrogen under the action of a catalyst to obtain 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol;
the supported palladium catalyst comprises palladium, a metal additive and a carrier; the metal auxiliary agent is at least one of cerium, nickel, cobalt and zinc;
the methylation reaction adopts a sectional reaction mode, and specifically comprises the following steps: firstly, feeding formaldehyde to the reaction kettle at the temperature of between 60 and 110 ℃ within 0.5 to 2 hours until the molar ratio of the formaldehyde to the 4- ((4-cyclohexylamino) methyl) cyclohexanol is 1.1 to 1.5: 1; after stopping feeding the formaldehyde, raising the temperature to 110-180 ℃ at the speed of 0.5-5 ℃/min; then adding the residual formaldehyde within 0.5-2h, and reacting at 110-;
2. the method of claim 1, wherein: in the methylation reaction, formaldehyde is firstly fed to the reaction vessel at 80-100 ℃ within 0.5-2h until the molar ratio of the formaldehyde to the 4- ((4-cyclohexylamino) methyl) cyclohexanol is 1.1-1.5: 1.
3. The method of claim 1, wherein: the solvent is at least one of tetrahydrofuran, methanol, ethanol, dioxane and acetone; the formaldehyde raw material is in the form of aqueous solution, namely aqueous solution of formaldehyde and/or aqueous solution of paraformaldehyde.
4. The production method according to claim 3, characterized in that: the concentration of formaldehyde in the formaldehyde aqueous solution is 10-40 wt%.
5. The method of claim 4, wherein: the concentration of formaldehyde in the aqueous formaldehyde solution was 37 wt%.
6. The production method according to claim 3, characterized in that: the aqueous solution of paraformaldehyde is a crude depolymerization aqueous solution of paraformaldehyde.
7. The method of claim 1, wherein: in the supported palladium catalyst, the percentage content of palladium is 0.1-50 wt%, and the percentage content of metal additive is 0.05-2 wt%;
the metal auxiliary agent is nickel and/or cerium; when the metal auxiliary agent is nickel and cerium, the content of nickel is 0.1-1 wt% and the content of cerium is 0.3-1.5 wt% in the supported palladium catalyst;
the carrier is at least one of alumina, silica gel, diatomite, zeolite molecular sieve, activated carbon, titanium dioxide, lithium aluminate and zirconia.
8. The method of claim 7, wherein: in the supported palladium catalyst, the percentage content of palladium is 2-10 wt%; the percentage content of the metal additive is 0.1-1.5 wt%.
9. The method of claim 1, wherein: the molar ratio of the formaldehyde to the 4- ((4-cyclohexylamino) methyl) cyclohexanol is 2-10: 1; the dosage of the catalyst is 1-5 wt% of 4- ((4-cyclohexylamino) methyl) cyclohexanol; the dosage of the solvent is 50-200 wt% of 4- ((4-cyclohexylamino) methyl) cyclohexanol.
10. The method of claim 9, wherein: the molar ratio of the formaldehyde to the 4- ((4-cyclohexylamino) methyl) cyclohexanol is 2-4: 1; and/or
The dosage of the catalyst is 2-3 wt% of 4- ((4-cyclohexylamino) methyl) cyclohexanol; and/or
The solvent dosage is 75-100 wt% of 4- ((4-cyclohexylamino) methyl) cyclohexanol.
11. The method of claim 1, wherein: the methylation reaction is carried out at the reaction temperature of 60-180 ℃ and the reaction pressure of 0.5-10 MPa.
12. The method of claim 11, wherein: the methylation reaction is carried out at the reaction temperature of 80-140 ℃ and the reaction pressure of 1-5 MPa.
13. The method of claim 1, wherein: the formaldehyde is fed in 2 times by adopting a semi-continuous feeding mode.
14. The method of claim 1, wherein: the sectional reaction mode specifically comprises the following steps: firstly, feeding formaldehyde to the reaction kettle at the temperature of 80-100 ℃ in a time of 0.7-1.5h until the molar ratio of the formaldehyde to the 4- ((4-cyclohexylamino) methyl) cyclohexanol is 1.1-1.5: 1; after stopping feeding the formaldehyde, raising the temperature to 110-180 ℃ at the speed of 1-2 ℃/min; then adding the residual formaldehyde within the time of 0.7-1.5h, and reacting at the temperature of 120-140 ℃ until the reaction is completed.
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