CN105061158A - Preparation method of 2,4,6-tricumylphenol - Google Patents
Preparation method of 2,4,6-tricumylphenol Download PDFInfo
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Abstract
The invention relates to a preparation method of 2,4,6-tricumylphenol. The method comprises the following steps: phenol and a catalytic amount of aluminum powder have a reaction at certain temperature under nitrogen protection, a certain amount of ionic liquid is added to serve as a promoter after the aluminum powder disappears completely, then alpha-methylstyrene is added, HPLC (high performance liquid chromatography) is adopted to monitor a reaction, dilute sulphuric acid is added to terminate the reaction when the content of 2,4,6-tricumylphenol is not increased continuously, a reaction product is extracted with toluene, trace moisture in toluene is removed through atmospheric distillation, white crystals are dissolved out after cooling, and a crude product is obtained through filtering; the crude product is recrystallized for the second time by toluene, and 2,4,6-tricumylphenol with the content higher than 99% is obtained. The yield of the preparation method is about 64%, certain amount of phenol and a composite catalyst are supplemented to recrystallization mother liquor after the recrystallization mother liquor is subjected to solvent removal, reaction is performed continuously, and after the mother liquor is recovered, the yield can be higher than 95% in terms of the total feeding capacity.
Description
Technical field
The present invention relates to a kind of preparation method of 2,4,6-tri-cumylphenol, belong to fine chemistry industry production technical field.
Background technology
2,4,6-tri-cumylphenol is a kind of new fine chemical material, and technical research result shows the production that can be used for the fine chemicals such as plastics additive, tensio-active agent, antioxidant for lubricant oil.Along with the development of the said products and the exploitation of three cumylphenol utilisation technologies, particularly along with the technological development for auto parts machinery plastics, the market demand of 2,4,6-tri-cumylphenol will constantly increase.Up to the present, 2,4, the preparation method of 6-tri-cumylphenol has two kinds, and one is under lewis acid catalyst exists, and obtains 4-cumylphenol, 2 by the alkylated reaction of phenol and alpha-methyl styrene, 4-di-(1-phenylisopropyl) phenol and 2,4,6-tri-cumylphenol mixture, also has a certain amount of α-methylstyrenedimer to generate simultaneously.Mixture removes most of low-boiling point material by the method for underpressure distillation, and resistates appropriate solvent recrystallization obtains product.Another kind of technique is that obtain the mixture of three kinds of isomer and α-methylstyrenedimer equally, separation method is the same with phenol aluminium for reacting under catalyzer alkaline condition.Concrete reaction equation is as follows:
The maximum defect of the synthesis technique of bibliographical information is that the selectivity of reaction is bad, the α-methylstyrenedimer of 10-20% is also had while generating 3 kinds of cumylphenol isomer, because α-methylstyrenedimer must be removed by underpressure distillation, and 3 kinds of cumylphenols are all heat-labile compounds, so the yield of two kinds of technique three cumylphenols is maximum only have 46%.
Summary of the invention
It is poor to the object of the invention is for solving reaction preference in three cumylphenol production technique, the problem that yield is low, and proposes a kind of preparation method of 2,4,6-tri-cumylphenols.
The preparation method of a kind of 2,4,6-tri-cumylphenols of the present invention, it carries out according to following steps:
One, reaction process: after the ratio being 0.001 ~ 0.05:1 in mass ratio by aluminium powder and phenol mixes, obtain phenol aluminium; Then after the ratio being 1:0.01 ~ 0.5 in the mass ratio of phenol aluminium and ionic liquid is uniformly mixed, drip alpha-methyl styrene, controlling rate of addition makes system temperature maintain 110 ~ 130 DEG C, after dripping alpha-methyl styrene, react, 2,4 of question response generation, the content of 6-tri-cumyl phenol does not continue to increase, then add dilute sulphuric acid termination reaction;
Two, treating process: with toluene extractive reaction product, then air distillation is transparent to distillate, then crystallisation by cooling, filters, and collects filter cake, and carries out second time recrystallization with toluene, obtain 2,4,6-tri-cumylphenol;
Three, disposing mother liquor: twice recrystallization mother liquor in step 2 is merged after removing toluene, add aluminium powder and phenol, then after the ratio being 1:0.01 ~ 0.5 in mass ratio by mixture and ionic liquid is uniformly mixed, drip alpha-methyl styrene, controlling rate of addition makes system temperature maintain 110 ~ 130 DEG C, after dripping alpha-methyl styrene, react, question response generates, and 4, the content of 6-tri-cumyl phenol does not continue to increase, add dilute sulphuric acid termination reaction, repeating step two, obtains 2,4,6-tri-cumylphenol; Wherein, described phenol and alpha-methyl styrene mol ratio are 1:2.5 ~ 5; The total mass adding aluminium powder and phenol is 30% ~ 50% of the residuum total mass after removing toluene.
Know-why of the present invention is: the catalyst system that the present invention selects can significantly improve optionally reason and mainly contain 2 points: after one, aluminium powder and phenol reactant generate phenol aluminium, due to metallic aluminium can effectively with the hydrogen atom coordination in the c h bond at phenolic hydroxyl group ortho position, thus be conducive to hydrogen ion by electrophilic reagent (C
+) replace, the introducing of metallic aluminium in other words, has optionally activated the ortho position of phenolic hydroxyl group; Two, the introducing of ionic liquid, be equivalent to introduce a stronger external electric field in reaction system, external electric field can strengthen the degree of polarization of C=C in electrophilic reagent alkene, namely make alkene α-C with positive charge increase, and then enhance the ability of alkene attack substrate.Ability just because of alpha-methyl styrene attack phenol strengthens, so the probability of himself dimerization just obviously reduces.Experimental result shows, when phenol and alpha-methyl styrene material ratio are 1:2.8 (mol), in reaction mixture 2,4,6-tri-cumylphenol component concentration is greater than 75%, and unreacted alpha-methyl styrene and α-methylstyrenedimer component sum are less than 3%.
The present invention comprises following beneficial effect:
1, the composite catalyst using phenol aluminium and imidazole type ion liquid to form, substitutes traditional phenol aluminium or lewis acid catalyst, can significantly improve the selectivity of 2,4,6-tri-cumylphenol.Use the selectivity of 2,4,6-tri-cumylphenols when phenol aluminium or lewis acid catalyst only to have 40% ~ 55%, and the catalyzer that the present invention uses make the selectivity of 2,4,6-tri-cumylphenols reach more than 75%.
2, the content that the selectivity of composite catalyst that the present invention uses also is embodied in by product α-methylstyrenedimer reduces greatly, use phenol aluminium or lewis acid catalyst, when phenol and alpha-methyl styrene material ratio are 1:3, the content of α-methylstyrenedimer is 10-20%, and when using catalyzer of the present invention, again in identical material ratio situation, the content of α-methylstyrenedimer is less than 3%, if rate of addition control is suitable even can be reduced to about 1%.
3, because α-methylstyrenedimer content is lower, reaction mixture does not need underpressure distillation to be separated lower-boiling impurity (mainly unreacted alpha-methyl styrene and α-methylstyrenedimer), direct recrystallization to three cumylphenol products, eliminate the thermolysis phenomenon of three cumylphenols in vacuum distillation process, improve the one-pass yield of three cumylphenols.
4, because α-methylstyrenedimer content in reaction mixture is lower, the mixture that recrystallization mother liquor obtains after steaming and desolventizing forms primarily of 3 kinds of cumylphenol isomer, they can not be reused as raw material by treated Returning reacting system, and the earth improve the total recovery of reaction.
5, by product all reclaims by last handling process, continues to participate in reaction, and making whole process almost without containing phenol waste discharge, is a kind of synthetic method of environmental protection.
Accompanying drawing explanation
Fig. 1 is 2,4,6-tri-cumyl phenols prepared by embodiment one
1hNMR spectrogram;
Fig. 2 is 2,4,6-tri-cumyl phenol nucleus magnetic resonance prepared by embodiment one
13cNMR spectrogram;
Fig. 3 is 2,4,6-tri-cumyl phenol HPLC spectrograms prepared by embodiment one;
Fig. 4 is 2,4,6-tri-cumyl phenol infrared spectrums prepared by embodiment one.
Embodiment
Embodiment one: the preparation method of one 2,4,6-tri-cumylphenol of present embodiment, it carries out according to following steps:
One, reaction process: after the ratio being 0.001 ~ 0.05:1 in mass ratio by aluminium powder and phenol mixes, obtain phenol aluminium; Then after the ratio being 1:0.01 ~ 0.5 in the mass ratio of phenol aluminium and ionic liquid is uniformly mixed, drip alpha-methyl styrene, controlling rate of addition makes system temperature maintain 110 ~ 130 DEG C, after dripping alpha-methyl styrene, react, 2,4 of question response generation, the content of 6-tri-cumyl phenol does not continue to increase, then add dilute sulphuric acid termination reaction;
Two, treating process: with toluene extractive reaction product, then air distillation is transparent to distillate, then crystallisation by cooling, filters, and collects filter cake, and carries out second time recrystallization with toluene, obtain 2,4,6-tri-cumylphenol;
Three, disposing mother liquor: twice recrystallization mother liquor in step 2 is merged after removing toluene, add aluminium powder and phenol, then after the ratio being 1:0.01 ~ 0.5 in mass ratio by mixture and ionic liquid is uniformly mixed, drip alpha-methyl styrene, controlling rate of addition makes system temperature maintain 110 ~ 130 DEG C, after dripping alpha-methyl styrene, react, question response generates, and 4, the content of 6-tri-cumyl phenol does not continue to increase, add dilute sulphuric acid termination reaction, repeating step two, obtains 2,4,6-tri-cumylphenol; Wherein, described phenol and alpha-methyl styrene mol ratio are 1:2.5 ~ 5; The total mass adding aluminium powder and phenol is 30% ~ 50% of the residuum total mass after removing toluene.
Embodiment two: present embodiment and embodiment one unlike: described ionic liquid is the halogenide of alkyl imidazole, and its general formula is:
other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one unlike: in step one, phenol aluminium is prepared in the following manner: under nitrogen atmosphere, after the ratio being 0.001 ~ 0.05:1 in mass ratio by aluminium powder and phenol mixes, mixture is warming up to 100 DEG C of reactions, after not having gas to overflow, be incubated 0.5h again, obtain phenol aluminium.Other is identical with embodiment one.
Embodiment four: present embodiment and embodiment one unlike: in step one, the mass ratio of aluminium powder and phenol is 0.005 ~ 0.05:1.Other is identical with embodiment one.
Embodiment five: present embodiment and embodiment one unlike: in step one, the mass ratio of aluminium powder and phenol is 0.008 ~ 0.05:1.Other is identical with embodiment one.
Embodiment six: present embodiment and embodiment one unlike: in step one, the mass ratio of aluminium powder and phenol is 0.01 ~ 0.05:1.Other is identical with embodiment one.
Embodiment seven: present embodiment and embodiment one unlike: in step one, the mass ratio of aluminium powder and phenol is 0.02 ~ 0.05:1.Other is identical with embodiment one.
Embodiment eight: present embodiment and embodiment one unlike: in step one, the mass ratio of aluminium powder and phenol is 0.03 ~ 0.05:1.Other is identical with embodiment one.
Embodiment nine: present embodiment and embodiment one unlike: in step one, the mass ratio of aluminium powder and phenol is 0.04 ~ 0.05:1.Other is identical with embodiment one.
Embodiment ten: present embodiment and embodiment one unlike: in step one, the mass ratio of phenol aluminium and ionic liquid is 1:0.2 ~ 0.5.Other is identical with embodiment one.
Embodiment 11: present embodiment and embodiment one unlike: in step one, the mass ratio of phenol aluminium and ionic liquid is 1:0.3 ~ 0.5.Other is identical with embodiment one.
Embodiment 12: present embodiment and embodiment one unlike: in step one, the mass ratio of phenol aluminium and ionic liquid is 1:0.4 ~ 0.5.Other is identical with embodiment one.
Embodiment 13: present embodiment and embodiment one unlike: control rate of addition in step one and make system temperature maintain 120 DEG C.Other is identical with embodiment one.
Embodiment 14: present embodiment and embodiment one unlike: in step one, phenol and alpha-methyl styrene mol ratio are 1:3 ~ 5.Other is identical with embodiment one.
Embodiment 15: present embodiment and embodiment one unlike: in step one, phenol and alpha-methyl styrene mol ratio are 1:4 ~ 5.Other is identical with embodiment one.
Embodiment 16: present embodiment and embodiment one are prepared in the process of 2,4,6-tri-cumylphenol head product unlike: step 2 and adopted high performance liquid chromatography detection reaction.Other is identical with embodiment one.
Embodiment 17: present embodiment and embodiment one unlike: the volumetric concentration of dilute sulphuric acid is 1 ~ 10%.Other is identical with embodiment one.
Embodiment 18: present embodiment and embodiment one unlike: phenol aluminium and ionic liquid public as catalyst preparing head product.Other is identical with embodiment one.
Embodiment 19: present embodiment and embodiment one unlike: in step 3, mixture is prepared in the following manner: under nitrogen atmosphere, to remove after the mother liquor after toluene mixes with aluminium powder and phenol, be warming up to 100 DEG C of reactions, after not having gas to overflow, be incubated 0.5h again, obtain mixture; Wherein, aluminium powder and phenol obtain that total mass is 2,4,6-tri-cumylphenol head product quality after removing toluene 30% ~ 50%.Other is identical with embodiment one.
Embodiment 20: present embodiment and embodiment one unlike: in step 3, the mass ratio of mixture and ionic liquid is 1:0.05 ~ 0.5.Other is identical with embodiment one.
Embodiment 21: present embodiment and embodiment one unlike: in step 3, the mass ratio of mixture and ionic liquid is 1:0.1 ~ 0.5.Other is identical with embodiment one.
Embodiment 22: present embodiment and embodiment one unlike: in step 3, the mass ratio of mixture and ionic liquid is 1:0.2 ~ 0.5.Other is identical with embodiment one.
Embodiment 23: present embodiment and embodiment one unlike: in step 3, the mass ratio of mixture and ionic liquid is 1:0.3 ~ 0.5.Other is identical with embodiment one.
Embodiment 24: present embodiment and embodiment one unlike: in step 3, the mass ratio of mixture and ionic liquid is 1:0.4 ~ 0.5.Other is identical with embodiment one.
Embodiment 25: present embodiment and embodiment one unlike: control rate of addition in step 3 and make system temperature maintain 120 DEG C.Other is identical with embodiment one.
Content of the present invention is not limited only to the content of the respective embodiments described above, and the combination of one of them or several embodiment equally also can realize the object of inventing.
Beneficial effect of the present invention is verified by following examples:
Embodiment one:
The preparation method of one 2,4,6-tri-cumylphenol of the present embodiment, it carries out according to following steps:
One, get phenol 94g (1mol), aluminium flake 0.3g, be warming up to 100 DEG C of reactions under nitrogen protection, 0.5h is incubated again in time not having gas to overflow, add 2g chlorodimethyl imidazoles, start after stirring and dissolving to drip 330g (2.8mol) alpha-methyl styrene, system automatic heating during dropping, controlling rate of addition makes system temperature maintain about 120 DEG C, after alpha-methyl styrene dropwises, continue reaction 1h, period, adopt high performance liquid chromatography detection reaction mixture, wherein 2, 4, the massfraction of 6-tri-cumylphenol is 75.8%, 2, 4-di-(1-phenylisopropyl) phenol is 16.7%, single cumylphenol is 5.2%, alpha-methyl styrene polymer is 2.2%, the aqueous sulfuric acid adding 10% is neutralized to pH2 ~ 3, termination reaction,
Two, 1000mL toluene extractive reaction product is at twice added; Toluene layer merges, in air distillation removing toluene solution, contained micro-moisture (is distilled to distillate transparent, approximately steam 100mL toluene), crystallisation by cooling, filters, and thick product directly adds 500mL toluene second time recrystallization, obtain white needle-like crystals 288g, be 2,4,6-tri-cumylphenol.
2,4,6-tri-cumylphenol productive rates prepared by the present embodiment are 67.9% (calculating with phenol input amount, identical below), and it is 99.8% that HPLC detects 2,4,6-tri-cumylphenol purity.2,4,6-tri-cumylphenol structure detection data and corresponding spectrogram as follows:
1hNMR (300MHz, CDCl
3, unit: ppm) and (as shown in Figure 1): δ 7.35 ~ 7.12 (m, 17H, Ar-H); 3.79 (s, 1H, O-H); 1.80 (s, 6H, CH
3); 1.56 (s, 12H, CH
3).
13cNMR (75MHz, CDCl
3, unit: ppm) and (as shown in Figure 2): δ 151.56,149.92,141.54,136.04,128.52,127.94,126.84,125.81,124.21,43.12,42.25,31.28,29.98.HPLC (C18 post; Determined wavelength UV=274nm; Moving phase: methyl alcohol: water=94:6; Flow velocity: 1.2ml/min): retention time: 4-cumyl phenol t
r=3.20min; Alpha-methyl styrene t
r=3.80min; 2,4-dicumyl phenol t
r=4.62min; 2,4,6-tri-cumyl phenol t
r=11.08min.IR:(KBr compressing tablet, cm
-1) (as shown in Figure 4): 3494,3084,3019,2969,2868,1597,1492,1205,765,698,551.
Embodiment two:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, and just the add-on of aluminium flake changes 0.15g into.The result of high performance liquid chromatography detection reaction mixture is, the massfraction of 2,4,6-tri-cumylphenol is 66.5%, 2,4-di-(1-phenylisopropyl) phenol is 19.7%, and single cumylphenol is 6.1%, and alpha-methyl styrene polymer is 7.6%.
Final white needle-like crystals 248g, 2,4,6-tri-cumylphenol productive rate be 58.5%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.1%.
Embodiment three:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, and just the add-on of aluminium flake changes 0.5g into.The result of high performance liquid chromatography detection reaction mixture is, the massfraction of 2,4,6-tri-cumylphenol is 76.5%, 2,4-di-(1-phenylisopropyl) phenol is 15.6%, and single cumylphenol is 6.0%, and alpha-methyl styrene polymer is 1.6%.
Final white needle-like crystals 290g, 2,4,6-tri-cumylphenol productive rate be 68.4%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.2%.
Embodiment four:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, and just the add-on of aluminium flake changes 1g into.The result of high performance liquid chromatography detection reaction mixture is, the massfraction of 2,4,6-tri-cumylphenol is 76.3%, 2,4-di-(1-phenylisopropyl) phenol is 15.9%, and single cumylphenol is 5.8%, and alpha-methyl styrene polymer is 1.8%.
Final white needle-like crystals 292g, 2,4,6-tri-cumylphenol productive rate be 68.7%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.5%.
Embodiment five:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, and just the add-on of chlorodimethyl imidazoles changes 1g into.The result of high performance liquid chromatography detection reaction mixture is, the massfraction of 2,4,6-tri-cumylphenol is 66.3%, 2,4-di-(1-phenylisopropyl) phenol is 20.7%, and single cumylphenol is 7.1%, and alpha-methyl styrene polymer is 5.8%.
Final white needle-like crystals 249g, 2,4,6-tri-cumylphenol productive rate be 58.7%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.0%.
Embodiment six:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, and just the add-on of chlorodimethyl imidazoles changes 4g into.The result of high performance liquid chromatography detection reaction mixture is, the massfraction of 2,4,6-tri-cumylphenol is 76.1%, 2,4-di-(1-phenylisopropyl) phenol is 16.2%, and single cumylphenol is 5.2%, and alpha-methyl styrene polymer is 2.4%.
Final white needle-like crystals 289g, 2,4,6-tri-cumylphenol productive rate be 68.2%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.4%.
Embodiment seven:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, and just ionic liquid changes bromination methylimidazole into, and add-on changes 2g into.The result of high performance liquid chromatography detection reaction mixture is, the massfraction of 2,4,6-tri-cumylphenol is 74.1%, 2,4-di-(1-phenylisopropyl) phenol is 14.5%, and single cumylphenol is 8.2%, and alpha-methyl styrene polymer is 2.9%.
Final white needle-like crystals 285g, 2,4,6-tri-cumylphenol productive rate be 67.2%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.2%.
Embodiment eight:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, and just ionic liquid changes Tetrafluoroboric acid methylimidazole salt into, and add-on changes 2g into.The result of high performance liquid chromatography detection reaction mixture is, the massfraction of 2,4,6-tri-cumylphenol is 75.9%, 2,4-di-(1-phenylisopropyl) phenol is 15.5%, and single cumylphenol is 7.2%, and alpha-methyl styrene polymer is 1.3%.
Final white needle-like crystals 291g, 2,4,6-tri-cumylphenol productive rate be 68.6%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.5%.
Embodiment nine:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, and just ionic liquid changes p-methyl benzenesulfonic acid methylimidazole salt into, and add-on changes 2g into.The result of high performance liquid chromatography detection reaction mixture is the massfraction of 2,4,6-tri-cumylphenol be 76.7%, 2,4-di-(1-phenylisopropyl) phenol is 14.8%, and single cumylphenol is 7.3%, and alpha-methyl styrene polymer is 1.1%.
Final white needle-like crystals 292g, 2,4,6-tri-cumylphenol productive rate 68.7%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.6%.
Embodiment ten:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, and just ionic liquid changes methyl chloride ethyl imidazol(e) into, and add-on changes 2g into.The result of high performance liquid chromatography detection reaction mixture is, the massfraction of 2,4,6-tri-cumylphenol is 75.6%, 2,4-di-(1-phenylisopropyl) phenol is 15.8%, and single cumylphenol is 6.4%, and alpha-methyl styrene polymer is 2.1%.
Final white needle-like crystals 291g, 2,4,6-tri-cumylphenol productive rate be 68.6%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.5%.
Embodiment 11:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, temperature of reaction is 100 DEG C, the result of high performance liquid chromatography detection reaction mixture is, the massfraction of 2,4,6-tri-cumylphenol is 72.1%, 2,4-di-(1-phenylisopropyl) phenol is 16.7%, and single cumylphenol is 9.3%, and alpha-methyl styrene polymer is 1.8%.
Final white needle-like crystals 261g, 2,4,6-tri-cumylphenol productive rate be 61.6%%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.4%.
Embodiment 12:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, temperature of reaction is 130 DEG C, the result of high performance liquid chromatography detection reaction mixture is, the massfraction of 2,4,6-tri-cumylphenol is 76.4%, 2,4-di-(1-phenylisopropyl) phenol is 14.7%, and single cumylphenol is 6.1%, and alpha-methyl styrene polymer is 2.8%.
Final white needle-like crystals 287g, 2,4,6-tri-cumylphenol productive rate 67.7%%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.5%.
Embodiment 13:
Twice recrystallization mother liquor of gained in embodiment one merges by the present embodiment, thick recrystallization resistates 130g (total charging capacity 424g is obtained after decompression steams toluene, obtain product 288g, total yield 98.9%), the component that high performance liquid chromatography detects this resistates is: 2,4,6-tri-cumylphenol 24.6%, 2,4-di-(1-phenylisopropyl) phenol is 52.4%, single cumylphenol is 16.3%, and alpha-methyl styrene polymer is 7.0%.
Get phenol 50g; aluminium flake 0.3g; 100 DEG C of reactions are warming up under nitrogen protection; 0.5h is incubated again in time not having gas to overflow; add 2g chlorodimethyl imidazoles, 130g recrystallization resistates, mix and start to drip 220g (in the phenol newly added and recrystallization resistates monosubstituted and two replace components and generate 93% of alpha-methyl styrene amount needed for three cumylphenols) afterwards; alpha-methyl styrene, all the other operations are identical with embodiment one.
High performance liquid chromatography detection reaction mixture, wherein the massfraction of 2,4,6-tri-cumylphenols is 75.4%, 2,4-di-(1-phenylisopropyl) phenol is 11.7%, and single cumylphenol is 4.8%, and alpha-methyl styrene polymer is 8.1%.
Final white needle-like crystals 261g, 2,4,6-tri-cumylphenol productive rate 65.2%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.3%.
Embodiment 14:
Twice recrystallization mother liquor of gained in embodiment 13 merges by the present embodiment, obtains thick recrystallization resistates 135g after decompression steams toluene.The component that high performance liquid chromatography detects this resistates is, 2,4,6-tri-cumylphenol 29.2%, 2,4-di-(1-phenylisopropyl) phenol is 33.7%, and single cumylphenol is 13.8%, and alpha-methyl styrene polymer is 23.3%.
By this resistates underpressure distillation (vacuum tightness is-0.095MPa), recovered temperature stops distillation when getting to 160 DEG C, collect vinasse 99g, the component that high performance liquid chromatography detects this resistates is, 2,4,6-tri-cumylphenol 39.4%, 2,4-di-(1-phenylisopropyl) phenol is 43.8%, single cumylphenol is 15.8%, and alpha-methyl styrene polymer is 0.9%.
Get phenol 60g; aluminium flake 0.3g; 100 DEG C of reactions are warming up under nitrogen protection; 0.5h is incubated again in time not having gas to overflow; add 2g chlorodimethyl imidazoles; recrystallization resistates after 99g underpressure distillation, mix and start to drip 250g (in the phenol newly added and recrystallization resistates monosubstituted and two replace components and generate about 93% of alpha-methyl styrene amount needed for three cumylphenols) alpha-methyl styrene afterwards, all the other operations are identical with embodiment one.
High performance liquid chromatography detection reaction mixture, wherein the massfraction of 2,4,6-tri-cumylphenols is 76.4%, 2,4-di-(1-phenylisopropyl) phenol is 16.2%, and single cumylphenol is 4.4%, and alpha-methyl styrene polymer is 2.9%.
Final white needle-like crystals 271g, 2,4,6-tri-cumylphenol productive rate be 66.3%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.4%.
Embodiment 15:
All experiment conditions of the present embodiment are identical with embodiment one with treatment process, just do not add ionic liquid.The result of high performance liquid chromatography detection reaction mixture is, the massfraction of 2,4,6-tri-cumylphenol is 56.1%, 2,4-di-(1-phenylisopropyl) phenol is 17.3%, and single cumylphenol is 14.7%, and alpha-methyl styrene polymer is 11.3%.
Final white needle-like crystals 199g, 2,4,6-tri-cumylphenol productive rate be 46.9%.Liquid chromatographic detection 2,4,6-tri-cumylphenol purity: 99.1%.
Embodiment 16:
The preparation method of one 2,4,6-tri-cumylphenol of the present embodiment, it carries out according to following steps:
Get phenol 94g (1mol); add 2g tosic acid; 100 DEG C are warming up under nitrogen protection; drip 330g (2.8mol) alpha-methyl styrene; system automatic heating during dropping; controlling rate of addition makes system temperature maintain about 120 DEG C, after alpha-methyl styrene dropwises, continues reaction 1h.High performance liquid chromatography detection reaction mixture, wherein the massfraction of 2,4,6-tri-cumylphenols is 45.3%, 2,4-di-(1-phenylisopropyl) phenol is 26.2%, and single cumylphenol is 9.4%, and alpha-methyl styrene polymer is 18.5%.
Add 800ml toluene, in 1g anhydrous sodium acetate and tosic acid, 100ml water washing, after dividing water-yielding stratum, air distillation removes contained micro-moisture (be distilled to distillate transparent, approximately steam 200ml toluene) in toluene solution, crystallisation by cooling, filter, thick product directly adds 300ml toluene secondary recrystallization, obtains white needle-like crystals 156g, productive rate 36.8%.Liquid chromatographic detection purity: 99.3%.
Claims (10)
1. the preparation method of tri-cumylphenols, is characterized in that it carries out according to following steps:
One, reaction process: after the ratio being 0.001 ~ 0.05:1 in mass ratio by aluminium powder and phenol mixes, obtain phenol aluminium; Then after the ratio being 1:0.01 ~ 0.5 in the mass ratio of phenol aluminium and ionic liquid is uniformly mixed, drip alpha-methyl styrene, controlling rate of addition makes system temperature maintain 110 ~ 130 DEG C, after dripping alpha-methyl styrene, react, 2,4 of question response generation, the content of 6-tri-cumyl phenol does not continue to increase, then add dilute sulphuric acid termination reaction;
Two, treating process: with toluene extractive reaction product, then air distillation is transparent to distillate, then crystallisation by cooling, filters, and collects filter cake, and carries out second time recrystallization with toluene, obtain 2,4,6-tri-cumylphenol;
Three, disposing mother liquor: the mother liquor of twice recrystallization in step 2 is merged after removing toluene, add aluminium powder and phenol, obtain mixture after mixing; Then after the ratio being 1:0.01 ~ 0.5 in mass ratio by mixture and ionic liquid is uniformly mixed, drip alpha-methyl styrene, controlling rate of addition makes system temperature maintain 110 ~ 130 DEG C, after dripping alpha-methyl styrene, react, question response generates, and 4, the content of 6-tri-cumyl phenol does not continue to increase, and adds dilute sulphuric acid termination reaction; Then repeating step two operates, and obtains 2,4,6-tri-cumylphenol; Wherein, described phenol and alpha-methyl styrene mol ratio are 1:2.5 ~ 5; The total mass adding aluminium powder and phenol is 30% ~ 50% of the residuum total mass after removing toluene.
2. the preparation method of a kind of 2,4,6-tri-cumylphenols according to claim 1, it is characterized in that described ionic liquid is the halogenide of alkyl imidazole, its general formula is:
R＝C
2H
5n-C
4H
9
X＝Cl,Br,I。
3. according to claim 1 a kind of 2,4, the preparation method of 6-tri-cumylphenol, it is characterized in that in step one, phenol aluminium is prepared in the following manner: under nitrogen atmosphere, after the ratio being 0.001 ~ 0.05:1 in mass ratio by aluminium powder and phenol mixes, mixture is warming up to 100 DEG C of reactions, after not having gas to overflow, is incubated 0.5h again, obtains phenol aluminium.
4. the preparation method of a kind of 2,4,6-tri-cumylphenols according to claim 1, is characterized in that the mass ratio of aluminium powder and phenol in step one is 0.005 ~ 0.05:1.
5. the preparation method of a kind of 2,4,6-tri-cumylphenols according to claim 1, is characterized in that the mass ratio of phenol aluminium and ionic liquid in step one is 1:0.1 ~ 0.5.
6. the preparation method of a kind of 2,4,6-tri-cumylphenols according to claim 1, is characterized in that controlling rate of addition in step one makes system temperature maintain 120 DEG C.
7. the preparation method of a kind of 2,4,6-tri-cumylphenols according to claim 1, is characterized in that in step one, phenol and alpha-methyl styrene mol ratio are 1:3 ~ 5.
8. the preparation method of a kind of 2,4,6-tri-cumylphenols according to claim 1, is characterized in that step 2 is prepared in the process of 2,4,6-tri-cumylphenol head product and adopts high performance liquid chromatography detection reaction.
9. the preparation method of a kind of 2,4,6-tri-cumylphenols according to claim 1, is characterized in that the volumetric concentration of dilute sulphuric acid is 1 ~ 10%.
10. the preparation method of a kind of 2,4,6-tri-cumylphenols according to claim 1, is characterized in that phenol aluminium and ionic liquid jointly as catalyst preparing target product 2,4,6-tri-cumylphenol.
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| CN109679116A (en) * | 2019-01-07 | 2019-04-26 | 哈尔滨理工大学 | A kind of preparation method and applications of thixotropic emulsification silicone grease |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4906791A (en) * | 1987-02-23 | 1990-03-06 | Mitsubishi Petrochemical Co., Ltd. | Process for preparing p-cumylphenol |
| US5091058A (en) * | 1990-02-20 | 1992-02-25 | Aristech Chemical Corporation | Purified para-cumylphenol |
| CN1884245A (en) * | 2005-06-22 | 2006-12-27 | 中国石油化工股份有限公司 | Process for preparing 2,4-dicumyl phenol |
-
2015
- 2015-08-11 CN CN201510489793.2A patent/CN105061158B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4906791A (en) * | 1987-02-23 | 1990-03-06 | Mitsubishi Petrochemical Co., Ltd. | Process for preparing p-cumylphenol |
| US5091058A (en) * | 1990-02-20 | 1992-02-25 | Aristech Chemical Corporation | Purified para-cumylphenol |
| CN1884245A (en) * | 2005-06-22 | 2006-12-27 | 中国石油化工股份有限公司 | Process for preparing 2,4-dicumyl phenol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679116A (en) * | 2019-01-07 | 2019-04-26 | 哈尔滨理工大学 | A kind of preparation method and applications of thixotropic emulsification silicone grease |
| CN109679116B (en) * | 2019-01-07 | 2021-12-31 | 哈尔滨理工大学 | Preparation method and application of thixotropic emulsified silicone grease |
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