CN103990475A - Composite solid acid catalyst as well as preparation method and application thereof - Google Patents
Composite solid acid catalyst as well as preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000011973 solid acid Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000741 silica gel Substances 0.000 claims abstract description 44
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 11
- 238000007598 dipping method Methods 0.000 claims abstract description 10
- 239000011592 zinc chloride Substances 0.000 claims abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 36
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 36
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 29
- 230000004913 activation Effects 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- -1 3~7 parts Chemical compound 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940100198 alkylating agent Drugs 0.000 claims description 3
- 239000002168 alkylating agent Substances 0.000 claims description 3
- 238000006424 Flood reaction Methods 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 abstract description 17
- 235000010354 butylated hydroxytoluene Nutrition 0.000 abstract description 16
- 230000035484 reaction time Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
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- 230000003213 activating effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000003407 synthetizing effect Effects 0.000 abstract 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 14
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 14
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- 238000003760 magnetic stirring Methods 0.000 description 6
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- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis and provides a composite solid acid catalyst. The composite solid acid catalyst is (SO4<2->+ZnCl2)/silica gel and is formed by compositing zinc chloride, sulfuric acid and silica gel. A preparation method of the catalyst comprises the following steps: hot pretreating the silica gel, dipping in zinc chloride solution, drying, adding into sulfuric acid solution, dipping for one night, drying and activating to obtain the (SO4<2->+ZnCl2)/silica gel composite solid acid catalyst. The composite solid acid catalyst provided by the invention has the characteristics of strong acidity, good activity, high selectivity, recyclability and environmental friendliness; when being used for synthetizing 2, 6-di-tert-butyl-4-methylphenol, the composite solid acid catalyst has the characteristics of simplicity and convenience in operation, low reaction temperature, normal pressures, no use of any organic solvent, high conversion ratio, short reaction time, high selectivity and environmental friendliness; the composite solid acid catalyst meets the requirements of green process and is very suitable for industrial production.
Description
Technical field
The invention belongs to technical field of organic synthesis, particularly a kind of composite solid-acid catalyst and preparation method thereof and the application of this catalyst in synthetic 2,6-di-tert-butyl-4-methy phenol.
Background technology
The chemical name of BHT (Butylated Hydroxytoluene) is 2,6-di-tert-butyl-4-methy phenol, (China's rubber industry custom claims age resistor to be commonly called as antioxidant 264, synthetic resin and plastic industry are accustomed to claiming antioxidant, also have the stabilizing agent of title), claim again T501.It is a kind of universal phenolic antioxidant of of many uses, large usage quantity.Can be used for the fields such as synthetic rubber, synthetic resin and plastics, oil product (lubricating oil, lubricating grease, paraffin etc.), food and feed.
BHT, since nineteen thirty-seven industrialization, has had longer developing history.Although it is an old kind in phenol antiager, because its anti ageing property is good, cheap, safe and convenient to use, stable, so lasting.More than ten, existing China, the U.S., Britain, Russia, France, Japan, Germany, Canada and Czech etc. are national at production BHT product in the world now.Domestic BHT market application structure is: what the application market of BHT antioxidant held pride of place is oil product.Another main application of BHT is as natural rubber and elastomeric antiaging agent aspect rubber.BHT is in the production and modification of synthetic resin and plastics, for primary antioxidant once must be application more widely.Aspect plastics, be used as antioxidant and the heat stabilizer of polyolefin, polyester, polystyrene, cellulose-based resin, PVC etc.Also can be used as the antioxidant of food.Synthetic material for food, medicine, cosmetic package is also made antioxidant with food stage BHT.
Because BHT has purposes so widely, therefore, improve its production technology, seek efficient, cheap, eco-friendly catalyst and production technology and be very important and highly significant.
The raw material route of synthetic BHT is a lot, for example, can from paracresol, to and a position mixture cresol, phenol, 2, the raw materials such as 6-DI-tert-butylphenol compounds start synthetic BHT.
At present, the technique of production and preparation antioxidant BHT both at home and abroad, mostly adopt isobutene to make alkylating agent, make catalyst with the concentrated sulfuric acid or aryl sulfonic acid, with paracresol at normal pressure or add to depress and react preparation (such as the patent CN1215042A that, Zhang Yue attains etc., 1999-04-28, " process for pressing preparation of 2,6-di-tert-butyl-p-cresol ").Do by traditional liquid acid (such as the concentrated sulfuric acid or hydrofluoric acid) in the process of the synthetic BHT of catalyst, exist reaction selectively low, post processing is complicated, product separation is difficult, produce a large amount of waste water, severe corrosion equipment and pipeline, catalyst can not reclaim and reuse and the drawback such as product cost height.Simultaneously contaminated environment, be difficult to adapt to the environmental requirement that day by day improves.Therefore, prior art cannot realize that yield is high, cost is low, eco-friendly target simultaneously.So, the research of alkylation solid acid catalyst is caused day by day to people's concern and attention.
In organic synthesis, substitute liquid acid with solid acid catalyst and become development trend undisputed in world wide.To use solid acid be catalyst paracresol and isobutene alkylated reaction, research and develop novel paracresol and isobutene alkylation catalyst and environment-protective process thereof, breeds just and be born under such background.Therefore, develop a kind of with simple to operate, active high, selectively good and clean environment friendly catalyst replaces traditional catalyst, is applied to organic synthesis field, to meet the needs of practical application.
Summary of the invention
The object of this invention is to provide a kind of composite solid-acid catalyst, to overcome the not high defect of catalyst activity in prior art, and the application of this catalyst in synthetic 2,6-di-tert-butyl-4-methy phenol.
For achieving the above object, the invention provides a kind of composite solid-acid catalyst, composite solid-acid catalyst is (SO
4 2-+ ZnCl
2)/silica gel, is composited by zinc chloride, sulfuric acid and silica gel; Described silica gel can be replaced with aluminium oxide, but the catalytic performance of catalyst is not as using silica gel effective.
Preferably, described (SO
4 2-+ ZnCl
2)/silica gel by weight, is prepared from by the raw material that comprises following component: 1～7 part of zinc chloride, 3～7 parts, sulfuric acid, 30 parts, silica gel.Wherein, sulfuric acid and zinc chloride can be buied in market.
The present invention also provides a kind of preparation method of above-mentioned catalyst, and silica gel, after overheated pretreatment, is placed in to liquor zinci chloridi and floods, then dry, and then joins dipping in sulfuric acid solution and spends the night, and after oven dry, activation, makes (SO
4 2-+ ZnCl
2)/silica gel composite solid-acid catalyst.
Preferably, the concentration of described liquor zinci chloridi is 0.3～1.5mol/L, and the concentration of described sulfuric acid solution is 1mol/L, and the solvent of described liquor zinci chloridi is water or absolute ethyl alcohol, and the solvent of described liquor zinci chloridi is water the best.
Preferably, the temperature of described activation is 200～500 DEG C, and further, the temperature of described activation is 200～250 DEG C.
Preferably, the time of described activation is 0.25～3h.
The present invention also provides the application of a kind of above-mentioned catalyst in preparation 2,6-di-tert-butyl-4-methy phenol.
Preferably, under 60～90 DEG C, condition of normal pressure, under the effect of described composite solid-acid catalyst, paracresol and isobutene carry out alkylated reaction and synthesize 2,6-di-tert-butyl-4-methy phenol.
Preferably, the mol ratio of paracresol and alkylating agent is 1:1～3; The mass ratio of paracresol and composite solid-acid catalyst is 1:0.01～0.08, and further, the mass ratio of paracresol and composite solid-acid catalyst is 1:0.03～0.05.
Preferably, the time of described alkylated reaction is 1～10h, and further, the time of described alkylated reaction is 4～8h.
The present invention compared with prior art, has the following advantages:
1, composite solid-acid catalyst provided by the invention has acid strong, active good, selective height, can be recycled and eco-friendly feature;
2, the present invention uses composite solid-acid catalyst for the synthesis of 2,6-di-tert-butyl-4-methy phenol, have easy and simple to handle, reaction temperature is low, normal pressure, do not use any organic solvent, conversion ratio is high, the reaction time is short, selective height, eco-friendly feature, meet friendly process requirement, be very suitable for suitability for industrialized production.
Detailed description of the invention
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.ZnCl
2and H
2sO
4can buy in market.
Embodiment 1
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
Make carrier with silica gel, taking water as solvent, taking the paracresol of question response as benchmark, according to paracresol: carrier (silica gel)=1:0.03 (mass ratio), paracresol: ZnCl
2=1:0.33% (mass ratio), paracresol: H
2sO
4=1:0.66% (mass ratio) prepares composite solid-acid catalyst.
Silica gel, after overheated pretreatment, is placed in to the ZnCl of 0.7mol/L
2in the aqueous solution, dipping spends the night, then dries.Then add the H of 1mol/L
2sO
4aqueous solution dipping spends the night, after oven dry, at 200 DEG C of activation 3h.
2,2, the preparation of 6-di-tert-butyl-4-methy phenol
In a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe, add 7.5g paracresol and by prepared the compound solid-acid [(SO of step 1 Raw proportioning
4 2-+ ZnCl
2)/silica gel] catalyst, a balloon is fixed on to condenser pipe top, play sealing and safety effect.Reactant is warmed up to 80 DEG C, stirs simultaneously; Slowly pass into high-purity isobutene gas, regulate and pass into speed, guarantee without gas overflowing reaction unit.After duration of ventilation 4h, stop ventilation, at this temperature, be incubated 0.5h.Under solid catalyst participates in, the alkylated reaction of paracresol and isobutene is carry out under normal pressure gas-solid-liquid phase reaction, reaction time 4h.
3,2, the analysis of 6-di-tert-butyl-4-methy phenol crude product
Obtain from step 22, in 6-di-tert-butyl-4-methy phenol crude product, sample, isolate clear liquid, carry out quantitative analysis with GC (gas chromatography), as shown in table 1.
Table 1 quantitative analysis results
As known from Table 1, two composite solid-acid catalyst [(SO that prepare at different times by identical conditions and method
4 2-+ ZnCl
2)/silica gel] sample, provide very approaching experimental result.Reappearance is satisfactory.
Embodiment 2
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
Make carrier with silica gel, taking water as solvent, taking the paracresol of question response as benchmark, according to paracresol: carrier (silica gel)=1:0.03 (mass ratio), paracresol: ZnCl
2=1:0.66% (mass ratio), paracresol: H
2sO
4=1:0.66% (mass ratio) prepares composite solid-acid catalyst.
Silica gel, after overheated pretreatment, is placed in to ZnCl
2the aqueous solution in flood and spend the night, then dry.Then add the H of 1mol/L
2sO
4aqueous solution dipping spends the night, after oven dry, and activation 3h, activation temperature is done contrast test with 250 DEG C, 200 DEG C and 150 DEG C respectively.
2,2, the preparation of 6-di-tert-butyl-4-methy phenol
In a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe, add 7.5g paracresol and by prepared the compound solid-acid [(SO of step 1 Raw proportioning
4 2-+ ZnCl
2)/silica gel] catalyst, a balloon is fixed on to condenser pipe top, play sealing and safety effect.Reactant is warmed up to 80 DEG C, stirs simultaneously; Slowly pass into high-purity isobutene gas, regulate and pass into speed, guarantee without gas overflowing reaction unit.Duration of ventilation reaches after 4h, stops ventilation (be that reaction temperature is 80 DEG C, the reaction time is 4h).
3,2, the analysis of 6-di-tert-butyl-4-methy phenol crude product
Obtain from step 22, in 6-di-tert-butyl-4-methy phenol crude product, sample, isolate clear liquid, carry out quantitative analysis with GC.Catalyst activation temperature changes the impact on reaction result, as shown in table 2.
The catalytic performance of institute's controlling catalyst under the different activation temperatures of table 2
As shown in Table 2,200 DEG C is compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] the more suitably activation temperature of catalyst.
Embodiment 3
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
The preparation method of catalyst is with embodiment 2, but activation temperature is 200 DEG C.
2,2, the preparation of 6-di-tert-butyl-4-methy phenol
By 7.5g paracresol with press prepared the compound solid-acid [(SO of step 1 Raw proportioning of embodiment 2
4 2-+ ZnCl
2)/silica gel] catalyst, join in a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe.One balloon is fixed on to condenser pipe top, plays sealing and safety effect.Reactant is warmed up to 80 DEG C, stirs simultaneously; Slowly pass into high-purity isobutene gas, regulate and pass into speed, guarantee without gas overflowing reaction unit.Ventilation is respectively 4h and 8h is contrast experiment, stops ventilation.
3,2, the analysis of 6-di-tert-butyl-4-methy phenol crude product
Obtain from step 22, in 6-di-tert-butyl-4-methy phenol crude product, sample, isolate clear liquid, carry out quantitative analysis with GC.The impact of alkylation differential responses time on reaction result, as shown in table 3.
The crude assay result of differential responses time in table 3 alkylated reaction
As seen from Table 3, along with the prolongation in reaction time, the yield of 2,6-di-tert-butyl-4-methy phenol improves, but extends 4h, and yield has only improved 8%.Consider, the alkylated reaction time is advisable with 4h.
Embodiment 4
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
Taking the paracresol of question response as benchmark, paracresol: carrier (silica gel)=1:0.03 (mass ratio), makes ZnCl taking water and absolute ethyl alcohol as solvent respectively
2contrast experiment is in dissolving, according to paracresol: ZnCl
2=1:0.33% (mass ratio), paracresol: H
2sO
4=1:0.33% (mass ratio) prepares composite solid-acid catalyst, and silica gel, after overheated pretreatment, is placed in to ZnCl
2in solution, dipping spends the night, then dries.Then add the H of 1mol/L
2sO
4aqueous solution dipping spends the night, after oven dry, at 200 DEG C of activation 3h.
2,2, the preparation of 6-di-tert-butyl-4-methy phenol
In a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe, add 7.5g paracresol and by prepared the compound solid-acid [(SO of step 1 Raw proportioning
4 2-+ ZnCl
2)/silica gel] catalyst.A balloon is fixed on to condenser pipe top, plays sealing and safety effect.Make reactant be warmed up to 80 DEG C, stir simultaneously; Slowly pass into high-purity isobutene gas, regulate and pass into speed, guarantee without gas overflowing reaction unit.Ventilate to 4h, stop ventilation (be that reaction temperature is 80 DEG C, the reaction time is 4h).
3,2, the analysis of 6-di-tert-butyl-4-methy phenol crude product
Obtain from step 22, in 6-di-tert-butyl-4-methy phenol crude product, sample, isolate clear liquid, carry out quantitative analysis with GC.Dissolve ZnCl with different solvents
2on the impact of reaction result, as shown in table 4.
The analysis result of table 4 different solvents
As shown in Table 4, very clear, the difference of solvent is for prepared composite solid-acid catalyst [(SO
4 2-+ ZnCl
2)/silica gel] catalytic performance almost there is no what impact.Obviously, taking use water inexpensive and that be easy to get as solvent preferably.
Embodiment 5
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
Taking the paracresol of question response as benchmark, paracresol: carrier (silica gel)=1:0.03 (mass ratio), active component (ZnCl used will prepare composite solid-acid catalyst time
2and H
2sO
4) composition change be contrast experiment, make ZnCl taking water as solvent
2dissolve.Silica gel, after overheated pretreatment, is placed in to ZnCl
2the aqueous solution in flood and spend the night, then dry.Then add the H of 1mol/L
2sO
4aqueous solution dipping spends the night, after oven dry, at 200 DEG C of activation 3h.
2,2, the preparation of 6-di-tert-butyl-4-methy phenol
By 7.5g paracresol with by step 1 and prepared the compound solid-acid [(SO of table 5 Raw proportioning
4 2-+ ZnCl
2)/silica gel] catalyst, add in a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe.One balloon is fixed on to condenser pipe top, plays sealing and safety effect.Under agitation reactant is warming up to 80 DEG C, then passes into lentamente high-purity isobutene gas, regulate and pass into speed, guarantee without gas overflowing reaction bulb.After ventilation 4h, stop ventilation (be that reaction temperature is 80 DEG C, the reaction time is 4h).
3,2, the analysis of 6-di-tert-butyl-4-methy phenol crude product
Obtain from step 22, in 6-di-tert-butyl-4-methy phenol crude product, sample, isolate clear liquid, carry out quantitative analysis with GC.While preparing composite solid-acid catalyst, the composition of active component used changes the impact on reaction result, as shown in table 5.
The impact of the composition of table 5 different activities component on reaction result
A is paracresol: ZnCl
2; B is paracresol: H
2sO
4.
As can be seen from Table 5, as the component composition of preparing composite solid-acid catalyst be more suitably: paracresol: ZnCl
2=1:0.33% (mass ratio), paracresol: H
2sO
4=1:0.66% (mass ratio).
Embodiment 6
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
The preparation method of catalyst is with embodiment 2, but only soak time is respectively 0.25h, 0.5h, 1h, 2h and 3h.
2,2, the preparation of 6-di-tert-butyl-4-methy phenol
By 7.5g paracresol with press prepared the compound solid-acid [(SO of embodiment 1 step 1 Raw proportioning
4 2-+ ZnCl
2)/silica gel] catalyst, join in a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe.One balloon is fixed on to condenser pipe top, plays sealing and safety effect.Under stirring, reactant is warmed up to 80 DEG C, slowly passes into high-purity isobutene gas, regulate and pass into speed, guarantee without gas overflowing reaction unit.Duration of ventilation 4h, stops ventilation (be that reaction temperature is 80 DEG C, the reaction time is 4h).
3,2, the analysis of 6-di-tert-butyl-4-methy phenol crude product
Obtain from step 22, in 6-di-tert-butyl-4-methy phenol crude product, sample, isolate clear liquid, carry out quantitative analysis with GC.The impact of the difference of catalyst activation time on reaction result, as shown in table 6.
Table 6 soak time is to composite solid-acid catalyst [(SO
4 2-+ ZnCl
2)/silica gel] impact of catalytic performance
As can be seen from Table 6, be 1h as the more suitably soak time of preparing composite solid-acid catalyst.
Although, above use general explanation, detailed description of the invention and test, the present invention is described in detail, on basis of the present invention, can make some modifications or improvements it, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. a composite solid-acid catalyst, is characterized in that, composite solid-acid catalyst is (SO
4 2-+ ZnCl
2)/silica gel, is composited by zinc chloride, sulfuric acid and silica gel.
2. catalyst according to claim 1, is characterized in that, described (SO
4 2-+ ZnCl
2)/silica gel by weight, is prepared from by the raw material that comprises following component: 1～7 part of zinc chloride, 3～7 parts, sulfuric acid, 30 parts, silica gel.
3. a preparation method for catalyst as claimed in claim 1 or 2, is characterized in that, silica gel, after overheated pretreatment, is placed in to liquor zinci chloridi and floods, then dry, and then joins dipping in sulfuric acid solution and spends the night, and after oven dry, activation, makes (SO
4 2-+ ZnCl
2)/silica gel composite solid-acid catalyst.
4. preparation method according to claim 3, is characterized in that, the concentration of described liquor zinci chloridi is 0.3～1.5mol/L, and the concentration of described sulfuric acid solution is 1mol/L, and the solvent of described liquor zinci chloridi is water or absolute ethyl alcohol.
5. preparation method according to claim 4, is characterized in that, the temperature of described activation is 200～500 DEG C.
6. preparation method according to claim 5, is characterized in that, the time of described activation is 0.25～3h.
7. the application of catalyst in preparation 2,6-di-tert-butyl-4-methy phenol as claimed in claim 1 or 2.
8. application according to claim 7, is characterized in that, under 60～90 DEG C, condition of normal pressure, under the effect of described composite solid-acid catalyst, paracresol and isobutene carry out alkylated reaction and synthesize 2,6-di-tert-butyl-4-methy phenol.
9. application according to claim 8, is characterized in that, the mol ratio of paracresol and alkylating agent is 1:1～3; The mass ratio of paracresol and composite solid-acid catalyst is 1:0.01～0.08.
10. application according to claim 8 or claim 9, is characterized in that, the time of described alkylated reaction is 1～10h.
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| CN111871432A (en) * | 2020-06-16 | 2020-11-03 | 南京晶典抗氧化技术研究院有限公司 | Preparation method of mesoporous solid acid catalyst and application of mesoporous solid acid catalyst in antioxidant BHT synthesis |
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