CN108503555A - 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol and preparation method and application - Google Patents
4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol and preparation method and application Download PDFInfo
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/42—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having amino groups or hydroxy groups bound to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The present invention provides 4 ((4 (dimethylamino) cyclohexyl) methyl) cyclohexanol and preparation method and application.Under the effect of the catalyst, 4 ((4 (dimethylamino) cyclohexyl) methyl) cyclohexanol are obtained by the reaction in ((4 cyclohexylamino) methyl) cyclohexanol of by-product 4 and formaldehyde, hydrogen in HMDA reaction process by this method.4 ((4 (dimethylamino) cyclohexyl) methyl) cyclohexanol of gained may be used as polyurethane foam response type catalyst after purification.The present invention realizes efficiently using for HMDA by-products, and production cost substantially reduces, and realizes the rational utilization of resource.4 ((4 (dimethylamino) cyclohexyl) methyl) cyclohexanol are as a kind of novel response type catalyst, it is used to prepare poly-isocyanurate/polyurethane etc., have the characteristics that smell is low, color inhibition ability is strong, product has lower VOC.
Description
Technical field
The invention belongs to technical field of organic synthesis, are related to 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol and system
Preparation Method and application.
Background technology
Diamino-dicyclohexyl methane (abbreviation HMDA) is-two hexamethylene of anti-aging polyurethane of production superior performance of new generation
The primary raw material of dicyclohexylmethane diisocyanate (HMDI), the isocyanates can be used for preparing the polyurethane that lightweight and performance are stablized
Coating and paint.HMDA also acts as epoxy curing agent and transparent nylon.Typically with diaminodiphenyl-methane (MDA)
For raw material, reacts and be made under the action of hydrogen and hydrogenation catalyst.But in the preparation process of HMDA, add in reaction process
The water added can react with major product HMDA and generate by-product 4- ((4- cyclohexylaminos) methyl) cyclohexanol.Current this by-product
Object does not utilize method effectively even, and qualified environmental protection company can only be entrusted as liquid waste processing.It is as follows that it generates process:
The side that the prior art is not utilized about by-product 4- in HMDA production processes ((4- cyclohexylaminos) methyl) cyclohexanol
Method, and not yet find the report that 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is used as to polyurethane foam catalyst.
Invention content
Present invention aims at aiming at the above shortcomings existing in the prior art, provide a kind of noval chemical compound 4- ((4- (two
Methylamino) cyclohexyl) methyl) and cyclohexanol and the compound preparation method, specifically with 4- ((4- cyclohexylaminos) methyl)
Cyclohexanol is that raw material prepares 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, raw materials used 4- ((4- cyclohexylaminos) first
Base) cyclohexanol is diamino-dicyclohexyl methane manufacturing process by-product, there is no effective treating method at present, realize waste profit
With.
The present invention also provides the application of the noval chemical compound, 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol simultaneously
It is a kind of response type catalyst, can be used for preparing polyurethane foam, since molecular weight is big, can effectively avoids common polyurethane
Foam catalyst leads to the problem of odour nuisance in use.
Technical solution of the present invention is as follows：
A kind of compound 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, shown in structure such as formula (I)：
A kind of preparation method of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol：4- ((4- cyclohexylaminos) methyl)
After cyclohexanol is mixed with solvent, under the effect of the catalyst, methylation reaction is carried out with formaldehyde, hydrogen, obtains 4- ((4- (diformazan ammonia
Base) cyclohexyl) methyl) cyclohexanol.
Further, 4- ((4- cyclohexylaminos) methyl) cyclohexanol is prepared for diamino-dicyclohexyl methane (HMDA)
By-product in the process.4- ((4- cyclohexylaminos) methyl) cyclohexanol, purity >=99.5wt%, wherein containing a small amount of diamino
Base dicyclohexyl methyl hydride.Diamino-dicyclohexyl methane preparation method is preferably in the present invention：In the presence of rhodium series catalysts, 4,4-
Diaminodiphenyl-methane carries out high-temperature catalytic Hydrogenation in solvent and obtains.Prepare the high-temperature catalytic of diamino-dicyclohexyl methane
Hydrogenation reaction solution obtains by-product 4- ((4- cyclohexylaminos) methyl) cyclohexanol through rectification and purification, and composition is mainly 4- ((4- hexamethylenes
Amido) methyl) cyclohexanol, also contains a small amount of diamino-dicyclohexyl methane.
Further, the solvent is at least one of tetrahydrofuran, methanol, ethyl alcohol, dioxane and acetone, preferably
Tetrahydrofuran.
Further, the formaldehyde raw material use aqueous solution form, be formalin and/or paraformaldehyde aqueous solution,
Formaldehyde in aqueous solution concentration is preferably 10-40wt%, most preferably 37wt%；The paraformaldehyde aqueous solution is preferably paraformaldehyde
Thick depolymerization aqueous solution.
Further, the catalyst is selected from load type palladium series catalysts and/or thunder Buddhist nun's type catalyst, preferably load type palladium
Series catalysts；
The load type palladium series catalysts include palladium, metal promoter and carrier；
In the load type palladium series catalysts, the percentage composition of palladium is 0.1-50wt%, preferably 2-10wt%；Metal promoted
The percentage composition of agent is 0.05-2wt%, preferably 0.1-1.5wt%；
It is one or more in the metal promoter selected from cerium, nickel, cobalt and zinc, preferably nickel and/or cerium；The metal promoter
For nickel and cerium when, in load type palladium series catalysts, the content of nickel is 0.1-1wt%, and the content of cerium is 0.3-1.5wt%；
The carrier is selected from aluminium oxide, silica, silica gel, diatomite, zeolite molecular sieve, activated carbon, titanium dioxide, aluminium
At least one of sour lithium and zirconium oxide；
The load type palladium series catalysts preferably use infusion process to prepare：The salt of palladium salt and metal promoter is dissolved in deionization
Uniform solution is formed in water, is then added carrier, and evaporating water after rotary dipping, drying, roasting obtain load type palladium after cooling
Series catalysts.
Further, the molar ratio of the formaldehyde and 4- ((4- cyclohexylaminos) methyl) cyclohexanol is 2-10:1, preferably 2-
4:1。
Further, the dosage of the catalyst is the 1-5wt%, preferably 2- of 4- ((4- cyclohexylaminos) methyl) cyclohexanol
3wt%.
Further, the solvent dosage is the 50-200wt%, preferably 75- of 4- ((4- cyclohexylaminos) methyl) cyclohexanol
100wt%.
Further, the methylation reaction, reaction temperature are 60-180 DEG C, preferably 80-140 DEG C；Reaction pressure is
0.5-10MPa (gauge pressure), preferably 1-5MPa (gauge pressure).Methylation reaction terminate condition be：Hydrogen is closed after completing formaldehyde charging
Air pipe valve is reacted as every 10 minutes pressure drop ＜ 0.3bar and is completed.
Further, the methylation reaction, formaldehyde use semicontinuous feeding manner, preferably divide 2 chargings.
Further, the methylation reaction, preferably segmented formula reactive mode, specially：First at 60-110 DEG C, preferably
At 80-100 DEG C, in 0.5-2h, preferably in the 0.7-1.5h times, formaldehyde feed to 4- ((4- cyclohexylaminos) methyl) cyclohexanol
Molar ratio be 1.1-1.5:1；After stopping formaldehyde charging, with rate for 0.5-5 DEG C/min, preferably 1-2 DEG C/min, temperature is increased
To 110-180 DEG C；Then in 0.5-2h, residual formaldehyde is preferably added in the 0.7-1.5h times, and at 110-180 DEG C, preferably
It is reacted to complete at 120-140 DEG C.
Further, the preparation method, after the completion of methylation reaction, by the way that reaction solution progress rectification and purification is obtained 4-
((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, the rectification and purification method are atmospheric distillation or rectification under vacuum, are preferably subtracted
Press rectifying；
The rectification and purification, pressure are 0.1-5KPa (absolute pressure), preferably 0.5-2KPa (absolute pressure)；Rectifying column theoretical cam curve
For 20-50 blocks, preferably 35 pieces；Reflux ratio is 1-10:1, preferably from about 5:1.
The application of the compounds of this invention 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, can be used for preparing poly- isocyanide
The response type catalyst of urea acid esters foam, polyurethane foam etc. is particularly suitable for soft polyurethane foam, polyurethane semihard foam and poly- ammonia
The preparation of ester hard bubble reduces smell and the VOC volatilizations of sponge product.4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol point
Not only contain tertiary amine in son, also contains hydroxy functional group, be a kind of response type catalyst, since molecular weight is big, can effectively keep away
Exempt from common polyurethane foam catalyst and leads to the problem of odour nuisance in use.With traditional catalyst phase
Than having the characteristics that low smell, having apparent environment-friendly advantage, market prospects are than broader.
The preparation method of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol of the present invention, with 4- ((4- cyclohexylaminos)
Methyl) cyclohexanol, solvent, hydrogen, formaldehyde be raw material, methylation reaction occurs under the effect of the catalyst, obtains 4- ((4- (two
Methylamino) cyclohexyl) methyl) cyclohexanol, chemical equation is as follows：
Since raw material 4- of the present invention ((4- cyclohexylaminos) methyl) cyclohexanol is higher than 110 DEG C in temperature, easily occur intermolecular
Deamination forms secondary amine, and reaction process is as follows：
The secondary amine of generation can with formaldehyde and the corresponding by-product impurity of hydrogen reaction generation, to influence the yield of major product.
According to the reaction mechanism mechanism of reaction, 4- ((4- cyclohexylaminos) methyl) cyclohexanol can first generate a methyl at reaction conditions, regenerate later
At another methyl.The reaction mechanism mechanism of reaction is as follows：
The inlet amount of formaldehyde is reacted using segmented and controlled to preparation method of the present invention, in low-temperature zone, 4- (4- cyclohexylamine
Base) methyl cyclohexanol can all with formaldehyde and hydrogen generation 4- ((4- Methylamino-cyclohexyls) methyl) cyclohexanol, without having pair
The generation of secondary amine is produced, regenerates 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol in high temperature section later, it can be effective
The generation for controlling side reaction, improves the yield of product.
In the production process of diamino-dicyclohexyl methane, the life of by-product 4- ((4- cyclohexylaminos) methyl) cyclohexanol is had
At, and the still not no resource utilization method about compound 4- ((4- cyclohexylaminos) methyl) cyclohexanol in the prior art, mesh
Preceding is that rectifying out works as liquid waste processing, can not only increase three-protection design cost or a kind of waste of resource in this way, and to ring
Border generates harm.Consider factors above, the invention discloses a kind of noval chemical compound 4- ((4- (dimethylamino) cyclohexyl) first
Base) cyclohexanol, which be prepared as raw material using 4- ((4- cyclohexylaminos) methyl) cyclohexanol, can be as anti-
It answers type catalyst to be applied to polyurethane foam field, there is very high economic benefit, be suitble to industrialization large-scale production.
Technical solution of the present invention advantageous effect is：A kind of noval chemical compound 4- ((4- (dimethylamino) cyclohexyl) first is provided
Base) cyclohexanol, which is ((4- cyclohexylaminos) first of by-product 4- in the production process with diamino-dicyclohexyl methane
Base) cyclohexanol is prepared for raw material, realizes the rational utilization of resource, greatly reduce production cost.4- ((4- (diformazans
Amino) cyclohexyl) methyl) cyclohexanol is a kind of novel response type catalyst, it is used to prepare poly-isocyanurate/polyurethane
Deng, have the characteristics that smell is low, color inhibition ability is strong, product have lower VOC.
Description of the drawings
Fig. 1 is the nmr spectrum of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol prepared in embodiment 4.
Specific implementation mode
Technical solution of the present invention is further detailed below by specific embodiment, but the present invention is not limited to institutes
The embodiment listed.
The condition of progress gas chromatographic analysis is in following embodiment：Agilent DB-5 chromatographic columns, injector temperature 300
DEG C, 300 DEG C, column flow rate 1.5mL/min, hydrogen flow rate 30mL/min, air velocity 300mL/min of fid detector temperature, program
Heating mode is 80 DEG C of holding 1min, is warming up to 280 DEG C with 15 DEG C/min, keeps 15min.
Embodiment 1
Prepare palladium series catalyst 1：
By bis- nitric hydrate palladiums of 5.00g, 4.96g Nickelous nitrate hexahydrates, six nitric hydrate ceriums of 0.93g be dissolved in 100mL go from
In sub- water, 80 DEG C of formation uniform solutions are heated to, 96.7g activated carbons (50 μm of average grain diameter, specific surface area 150m are added2/
G), the gradual evaporating water after rotary dipping 4h in 80 DEG C of water-bath, dries 12 hours in 120 DEG C of baking ovens；Finally move to Muffle
Stove, in air atmosphere with 2 DEG C/min be warming up to 500 DEG C roast 6 hours, catalyst is can be obtained after natural cooling.Catalyst
Group become：Pd is 2wt%, and Ni 1wt%, Ce 0.3wt%, remaining is activated carbon, and catalyst is accounted for respective metal element
Gross mass meter.
Embodiment 2
Prepare palladium series catalyst 2：
By bis- nitric hydrate palladiums of 25.04g, 0.50g Nickelous nitrate hexahydrates, six nitric hydrate ceriums of 1.55g be dissolved in 100mL go from
In sub- water, 60 DEG C of formation uniform solutions are heated to, 89.4g aluminium oxide (100 μm of average grain diameter, specific surface area 180m are added2/
G), the gradual evaporating water after rotary dipping 5h in 70 DEG C of water-bath, dries 16 hours in 100 DEG C of baking ovens；Finally move to Muffle
Stove, in air atmosphere with 3 DEG C/min be warming up to 550 DEG C roast 8 hours, catalyst is can be obtained after natural cooling.Catalyst
Group become：Pd is 10wt%, and Ni 0.1wt%, Ce 0.5wt%, remaining is aluminium oxide, and catalysis is accounted for respective metal element
Agent gross mass meter.
Embodiment 3
Prepare palladium series catalyst 3：
By bis- nitric hydrate palladiums of 12.52g, 2.48g Nickelous nitrate hexahydrates, six nitric hydrate ceriums of 4.65g be dissolved in 100mL go from
In sub- water, 70 DEG C of formation uniform solutions are heated to, 95.5g silica (100 μm of average grain diameter, specific surface area are added
200m2/ g), the gradual evaporating water after rotary dipping 6h in 60 DEG C of water-bath is dried 12 hours in 120 DEG C of baking ovens；Finally move
To Muffle furnace, in air atmosphere with 2 DEG C/min be warming up to 600 DEG C roast 6 hours, catalyst is can be obtained after natural cooling.
The group of catalyst becomes：Pd is 5wt%, and Ni 0.5wt%, Ce 1.5wt%, remaining is silica, with respective metal member
Element accounts for catalyst gross mass meter.
Embodiment 4
Prepare raw material 4- ((4- cyclohexylaminos) methyl) cyclohexanol：Diamino-dicyclohexyl methane by-product：
5g Rh/Al are added in the autoclave that volume is 2L2O3(tenor of Rh is 5%) catalyst, closes kettle 10MPa
It tests airtight, if not leaking, 500g 4 is added, 4- diaminodiphenyl-methanes and 500g tetrahydrofurans use 1MPa's (gauge pressure) respectively
After nitrogen and hydrogen are respectively replaced three times, with hydrogen ftercompction to 4.5MPa (gauge pressure), temperature is increased to 190 DEG C, is led in reaction process
The hydrogen flowing quantity controller logical hydrogen lasting into reaction kettle is crossed, ensures that the pressure in kettle is maintained to 8MPa (gauge pressure), works as hydrogen
When the instantaneous flow of flow controller is less than 100sccm, stop leading to hydrogen.When the pressure drop of reaction kettle is less than 1bar/10min
When, stop reaction, reactor temperature is reduced to 50 DEG C, diamino is obtained by filtration by reaction kettle built-in filter in pressure release
Dicyclohexyl methyl hydride reaction solution.After saving diamino-dicyclohexyl methane reaction solution, by reaction solution pressure be 0.5KPa, essence
Fractional distillation column theoretical cam curve is 35 pieces, reflux ratio 5：1 time rectification under vacuum is 200 DEG C in column bottom temperature, and tower top temperature is 165 DEG C,
Obtain 4- ((4- cyclohexylaminos) methyl) cyclohexanol.Through vapor detection, the purity of 4- ((4- cyclohexylaminos) methyl) cyclohexanol is
99.8wt%, wherein the diamino-dicyclohexyl methane containing 0.2wt%.
Prepare 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol：
Activation of catalyst：The palladium series catalyst in the embodiment 1 of 4g is added into the reaction kettle of 1L, it is molten that tetrahydrofuran is added
Agent bottoming seals reaction kettle, and nitrogen and hydrogen is used to replace respectively three times, is 180 DEG C in temperature, Hydrogen Vapor Pressure is 5MPa (gauge pressure)
Lower activated catalyst 6 hours.Cooling later, pressure release, nitrogen are replaced three times, and solvent is filtered out from reaction kettle.Later plus
Enter 4- ((4- cyclohexylaminos) methyl) cyclohexanol and 200g tetrahydrofurans of 200g, uses nitrogen and hydrogen to replace successively three times, rise
Beginning Hydrogen Vapor Pressure be 2MPa (gauge pressure), open stirring be 700 revs/min, etc. reaction temperatures rise to 80 DEG C, Hydrogen Vapor Pressure is adjusted
Lead to 4MPa (gauge pressure) and persistently hydrogen, starts the formaldehyde for leading to 37wt% into reaction kettle with the speed of 2.5g/min with constant-flux pump
Aqueous solution 84g stops the charging of formaldehyde, reaction temperature is risen to 140 DEG C with the rate of 2 DEG C/min, then keeps temperature later
At 140 DEG C, continues the formalin 77g for leading to 37wt% into reaction kettle with the speed of 2.5g/min with constant-flux pump, wait for formaldehyde
It after the completion of charging, closes hydrogen pipeline valve and starts to build the pressure, the pressure drop ＜ 0.3bar when every 10 minutes stop reaction.It drops later
Temperature, pressure release are replaced three times with nitrogen, 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol reaction solution are obtained by filtration.
Through vapor detection, the content of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is in reaction solution
98.2wt%.By reaction solution pressure be 1KPa, rectifying column theoretical cam curve be 35 pieces, reflux ratio 5：1 time rectification under vacuum obtains
To 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, through vapor detection, 4- ((4- (dimethylamino) cyclohexyl) methyl)
The purity of cyclohexanol is 99.5wt%.
4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol nmr spectrum is shown in Fig. 1,1HNMR data：(CDCl3For
Solvent, TMS are internal standard), a (2.19ppm), b (2.94ppm, axial bond), b (2.58ppm, equatorial bond), c (1.84ppm, uprightly
Key), c (1.55ppm, equatorial bond), d (1.72ppm, axial bond), d (0.91ppm, equatorial bond), e (1.04ppm), f
(1.19ppm), g (1.81ppm, equatorial bond), g (1.29ppm, axial bond), h (1.58ppm, equatorial bond), h (1.10ppm, directly
Vertical key), i (1.78ppm, axial bond), i (1.69ppm, equatorial bond), j (3.94ppm, axial bond), j (3.64ppm, it is calm
Key), k (1.53ppm).
Embodiment 5
Prepare 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol：
((4- cyclohexylaminos) methyl) the cyclohexanol sources raw material 4- and catalyst activation process are the same as embodiment 4.
The palladium series catalyst in the embodiment 2 of 6g is added into the reaction kettle of 1L, 4- ((the 4- rings of 200g are added after activation
Hexylamine base) methyl) cyclohexanol and 200g methanol, use nitrogen and hydrogen to replace successively three times, starting Hydrogen Vapor Pressure is 2MPa (tables
Pressure), open stirring be 700 revs/min, etc. reaction temperatures rise to 90 DEG C, by Hydrogen Vapor Pressure be adjusted to 3MPa (gauge pressure) and continue
Logical hydrogen is started the formalin 115g for being led to 37wt% into reaction kettle with the speed of 2g/min with constant-flux pump, stops first later
The charging of aldehyde after reaction temperature is risen to 120 DEG C with the rate of 1 DEG C/min, continues past with the speed of 2.5g/min with constant-flux pump
The formalin 115g for leading to 37wt% in reaction kettle after the completion of waiting for formaldehyde charging, closes hydrogen pipeline valve and starts to build the pressure, when
Every 10 minutes pressure drop ＜ 0.3bar stop reaction.Cooling later, pressure release are replaced three times with nitrogen, 4- ((4- are obtained by filtration
(dimethylamino) cyclohexyl) methyl) cyclohexanol reaction solution.Through vapor detection, 4- ((4- (dimethylamino) cyclohexyl) in reaction solution
Methyl) cyclohexanol content be 97.5wt%.
By reaction solution pressure be 2KPa, rectifying column theoretical cam curve be 50 pieces, reflux ratio 10：1 time rectification under vacuum obtains
To 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, through vapor detection, 4- ((4- (dimethylamino) cyclohexyl) methyl)
The purity of cyclohexanol is 99.8wt%.
Embodiment 6
Prepare 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol：
((4- cyclohexylaminos) methyl) the cyclohexanol sources raw material 4- and catalyst activation process are the same as embodiment 4.
The palladium series catalyst in the embodiment 3 of 3g is added into the reaction kettle of 1L, 4- ((the 4- rings of 200g are added after activation
Hexylamine base) methyl) cyclohexanol and 150g ethyl alcohol, use nitrogen and hydrogen to replace successively three times, starting Hydrogen Vapor Pressure is 2MPa (tables
Pressure), open stirring be 700 revs/min, etc. reaction temperatures rise to 105 DEG C, by Hydrogen Vapor Pressure be adjusted to 6MPa (gauge pressure) and continue
Logical hydrogen is started the formalin 92g for being led to 37wt% into reaction kettle with the speed of 1g/min with constant-flux pump, stops first later
Reaction temperature is risen to 150 DEG C by the charging of aldehyde with the rate of 2 DEG C/min, is continued with constant-flux pump with the past reaction of the speed of 2g/min
The formalin 115g for leading to 37wt% in kettle after the completion of waiting for formaldehyde charging, closes hydrogen pipeline valve and starts to build the pressure, when every 10
The pressure drop ＜ 0.3bar of minute stop reaction.Cooling later, pressure release are replaced three times with nitrogen, 4- ((4- (diformazans are obtained by filtration
Amino) cyclohexyl) methyl) cyclohexanol reaction solution.
Through vapor detection, the content of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is in reaction solution
96.8wt%.By reaction solution pressure be 0.1KPa, rectifying column theoretical cam curve be 20 pieces, reflux ratio 1：1 time rectification under vacuum
4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is obtained, through vapor detection, 4- ((4- (dimethylamino) cyclohexyl) first
Base) cyclohexanol purity be 99.0wt%.
Embodiment 7
4- ((4- (dimethylamino) cyclohexyl) methyl) application of cyclohexanol in polyurethane foam
The raw material of use is as follows：
Polyalcohol：Wanol 562, Wanhua Chemical Group Co., Ltd.'s production；Wanol 2045, ten thousand magnificent chemical groups
Limited liability company produces.
Diethanol amine：Xi Long science limited liability company produces.
Water：Make deionized water by oneself.
Foam stabiliser：B-8715LF2 wins wound industrial group production.
Response type catalyst：DPA, the production of Hensel Mann.
Isocyanates：Wannate 8001, Wanhua Chemical Group Co., Ltd.'s production.
The 4- ((4- (dimethylamino) cyclohexyl) methyl) prepared using common response type catalyst DPA and embodiment 1
Cyclohexanol carries out foam performance comparison, and raw material proportioning is shown in Table 1.
Table 1
It carries out freely steeping operation by hand using one-step method：By according to the ratio in Table 1s such as polyalcohol, water, foam stabiliser, catalyst
It is added to container high speed to disperse 5 minutes, combination material is made；Combination material and isocyanates are put into constant incubator in 23 DEG C
Constant temperature is handled 4 hours；Successively will combination material, isocyanates be added in dixie cup, then use high speed dispersor, 3000 turns/
It is placed under the ultrasonic tesint head of bubble growth curve tester and is tested after stirring 5s under the speed of minute.As a result such as following table
Shown in 2.
Table 2
| Group | A | B |
| Rise time [s] | 20.7 | 32.9 |
| Rise time [s] | 123.5 | 158.3 |
| The brimmer time [s] | 77.3 | 92.8 |
| Maximum foaming height (G) [mm] | 220.9 | 200.8 |
| Final height [mm] | 210.3 | 198.5 |
From table 2 it can be seen that under identical additive amount, using the foam system of DPA, rise obviously comparatively fast, the later stage is solidifying
Glue is not enough to the foam structure of support foam, there is the contraction of nearly 10mm so as to cause foam；Comparison is it is found that use 4- of the present invention
The foam system of ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, although rising later, entire foaming process is relatively more flat
Surely, foam contraction is smaller.It follows that after improving foam using 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol
Phase cures performance.
The smell and VOC of foam are tested.According to《Component _ Odor Examination side of PV3900-2000_ automotive interiors
Method》It is tested, grading system such as the following table 3.
3 grading system of table
| Score | Evaluation | Score | Evaluation |
| 1 | It cannot experience | 2 | It can experience, it is unobstructive |
| 3 | It is can obviously experiencing but without too big obstruction | 4 | There is obstruction |
| 5 | By larger obstruction | 6 | It is insufferable |
It evaluates, is averaged through 5 people：Foam A is 3 points；Foam B is 2 points；It can thus be appreciated that using 4- ((4- of the present invention
(dimethylamino) cyclohexyl) methyl) cyclohexanol can effectively reduce the smell of foam as catalyst.Above-mentioned two groups of foams
VOC testing results such as the following table 4：
Table 4
Use 4- of the present invention ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol that can have as catalyst as shown in Table 4
Effect reduces the content of amines catalyst in foam VOC, and TVOC can reduce 42%.
Comparative example 1
With reference to embodiment 4, the difference is that in 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol preparation process,
Formalin is added at one time, and methylation reaction process is not segmented：
The palladium series catalyst in the embodiment 1 of 4g is added into the reaction kettle of 1L, 4- ((the 4- rings of 200g are added after activation
Hexylamine base) methyl) cyclohexanol and 200g tetrahydrofurans, use nitrogen and hydrogen to replace successively three times, starting Hydrogen Vapor Pressure is 2MPa
(gauge pressure), open stirring be 700 revs/min, etc. reaction temperatures rise to 80 DEG C, Hydrogen Vapor Pressure is adjusted to 4MPa (gauge pressure) and is held
Continuous logical hydrogen is started the formalin 161g for being led to 37wt% into reaction kettle with the speed of 2.5g/min with constant-flux pump, waits for formaldehyde
It after the completion of charging, closes hydrogen pipeline valve and starts to build the pressure, the pressure drop ＜ 0.3bar when every 10 minutes stop reaction.It drops later
Temperature, pressure release are replaced three times with nitrogen, 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol reaction solution are obtained by filtration.
Through vapor detection, the content of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is in reaction solution
85.3wt%.By reaction solution pressure be 1KPa, rectifying column theoretical cam curve be 35 pieces, reflux ratio 5：1 time rectification under vacuum obtains
To 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, through vapor detection, 4- ((4- (dimethylamino) cyclohexyl) methyl)
The purity of cyclohexanol is 98.3wt%.
Comparative example 2
With reference to embodiment 5, the difference is that in 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol preparation process,
Formalin is added at one time, and methylation reaction process is not segmented：
The palladium series catalyst in the embodiment 2 of 6g is added into the reaction kettle of 1L, 4- ((the 4- rings of 200g are added after activation
Hexylamine base) methyl) cyclohexanol and 200g methanol, use nitrogen and hydrogen to replace successively three times, starting Hydrogen Vapor Pressure is 2MPa (tables
Pressure), open stirring be 700 revs/min, etc. reaction temperatures rise to 120 DEG C, by Hydrogen Vapor Pressure be adjusted to 3MPa (gauge pressure) and continue
Logical hydrogen is started the formalin 230g for being led to 37wt% into reaction kettle with the speed of 2g/min with constant-flux pump, waits for that formaldehyde is fed
After the completion, it closes hydrogen pipeline valve to start to build the pressure, the pressure drop ＜ 0.3bar when every 10 minutes stop reaction.Cooling later,
Pressure release is replaced three times with nitrogen, 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol reaction solution is obtained by filtration.
Through vapor detection, the content of 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is in reaction solution
91.2wt%.By reaction solution pressure be 2KPa, rectifying column theoretical cam curve be 50 pieces, reflux ratio 10：1 time rectification under vacuum obtains
To 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, through vapor detection, 4- ((4- (dimethylamino) cyclohexyl) methyl)
The purity of cyclohexanol is 98.7wt%.
Claims (10)
1. a kind of compound 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, shown in structure such as formula (I)：
The preparation method of compound 4- described in a kind of claim 1 2. ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol,
It is characterized in that：After 4- ((4- cyclohexylaminos) methyl) cyclohexanol is mixed with solvent, under the effect of the catalyst, with formaldehyde, hydrogen
Methylation reaction is carried out, 4- ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol is obtained.
3. preparation method according to claim 2, it is characterised in that：The solvent is tetrahydrofuran, methanol, ethyl alcohol, two
At least one of six ring of oxygen and acetone, preferably tetrahydrofuran；The formaldehyde raw material uses aqueous solution form, is formalin
And/or paraformaldehyde aqueous solution, formaldehyde in aqueous solution concentration are preferably 10-40wt%, most preferably 37wt%；The paraformaldehyde
Aqueous solution is preferably the thick depolymerization aqueous solution of paraformaldehyde.
4. preparation method according to claim 2, it is characterised in that：The catalyst be load type palladium series catalysts and/
Or thunder Buddhist nun's type catalyst, preferred load type palladium series catalysts.
5. preparation method according to claim 4, it is characterised in that：The load type palladium series catalysts include palladium, metal
Auxiliary agent and carrier；
In load type palladium series catalysts, the percentage composition of palladium is 0.1-50wt%, preferably 2-10wt%；The hundred of metal promoter
It is 0.05-2wt%, preferably 0.1-1.5wt% to divide content；
The metal promoter is at least one of cerium, nickel, cobalt and zinc, preferably nickel and/or cerium；The metal promoter is nickel and cerium
When, in load type palladium series catalysts, the content of nickel is 0.1-1wt%, and the content of cerium is 0.3-1.5wt%；
The carrier be aluminium oxide, silica, silica gel, diatomite, zeolite molecular sieve, activated carbon, titanium dioxide, lithium aluminate and
At least one of zirconium oxide.
6. preparation method according to claim 2, it is characterised in that：The formaldehyde and 4- ((4- cyclohexylaminos) methyl) ring
The molar ratio of hexanol is 2-10：1, preferably 2-4：1；The dosage of the catalyst is 4- ((4- cyclohexylaminos) methyl) cyclohexanol
1-5wt%, preferably 2-3wt%；The solvent dosage is the 50-200wt% of 4- ((4- cyclohexylaminos) methyl) cyclohexanol, preferably
75-100wt%.
7. preparation method according to claim 2, it is characterised in that：The methylation reaction, reaction temperature 60-180
DEG C, preferably 80-140 DEG C；Reaction pressure is 0.5-10MPa (gauge pressure), preferably 1-5MPa (gauge pressure).
8. preparation method according to claim 2, it is characterised in that：The formaldehyde uses semicontinuous feeding manner, divides 2 times
Charging.
9. preparation method according to claim 2, it is characterised in that：The methylation reaction, using segmented reaction side
Formula, specially：First at 60-110 DEG C, at preferably 80-100 DEG C, in 0.5-2h, preferably in the 0.7-1.5h times, formaldehyde charging
It is 1.1-1.5 to the molar ratio with 4- ((4- cyclohexylaminos) methyl) cyclohexanol:1；It is 0.5- with rate after stopping formaldehyde charging
5 DEG C/min, preferably 1-2 DEG C/min, temperature is increased to 110-180 DEG C；
Then in 0.5-2h, residual formaldehyde is preferably added in the 0.7-1.5h times, and at 110-180 DEG C, at preferably 120-140 DEG C
It reacts to complete.
The application of compound 4- described in a kind of claim 1 10. ((4- (dimethylamino) cyclohexyl) methyl) cyclohexanol, feature
It is：Be used to prepare polyisocyanurate foam, polyurethane foam response type catalyst, be particularly suitable for soft polyurethane foam,
The preparation of polyurethane semihard foam and hard polyurethane foam.
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