CN106631707A - Method for preparing p-cresol dicyclopentadiene butylation product - Google Patents
Method for preparing p-cresol dicyclopentadiene butylation product Download PDFInfo
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- CN106631707A CN106631707A CN201611017005.0A CN201611017005A CN106631707A CN 106631707 A CN106631707 A CN 106631707A CN 201611017005 A CN201611017005 A CN 201611017005A CN 106631707 A CN106631707 A CN 106631707A
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- paracresol
- reaction
- tert
- butyl alcohol
- dicyclopentadiene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
Abstract
The invention discloses a method for preparing a p-cresol dicyclopentadiene butylation product. After tert butyl alcohol and p-cresol-dicyclopentadiene are weighed in proportion, then even heating and mixing are performed, and a strong acid catalyst is added for reaction; after reaction is completed, a catalyst is removed through separation, washing is performed to reach a neutral state, an organic phase is removed through distillation, and the a p-cresol dicyclopentadiene butylation product is obtained, wherein the male ratio of the tert butyl alcohol to p-cresol dicyclopentadiene resin is 4:1 to 50:1, the reaction temperature is 20-83 DEG C, and the reaction time is 2-12 hours. The method for preparing the p-cresol dicyclopentadiene butylation product adopts the tert butyl alcohol high in safety as a raw material to perform butylation reaction, and potential safety hazards caused by usage of butylation raw materials such as isobutene and tert-butyl methyl ether low in safety are avoided.
Description
Technical field
The present invention relates to chemosynthesis technical field, more particularly to one kind prepares paracresol dicyclopentadiene butylation product
Method.
Background technology
Paracresol dicyclopentadiene butylation product antioxidant is several nontoxic, nothings few in number in phenolic antioxidant
One of shallow antioxidant kind of taste, color, is widely used in rubber, plastics, fiber, adhesive etc., prevents the aging of material, extends
The service life of material, is also used for suppressing the increase of viscosity and acidity in fuel oil industry, prevents in food and feed industry
Food spoilage.
Paracresol dicyclopentadiene butylation product antioxidant product is and double generally with p-methyl phenol as primary raw material
Generation phenolic Petropols are said and reacted to cyclopentadiene, then be alkylated reaction with isobutene and be obtained.Such as pass through first
Base phenol and dicyclopentadiene carry out condensation reaction and generate phenolic Petropols, then carry out phenolic Petropols with isobutene
Alkylated reaction, rear distillation after being finally neutralized with soda ash obtains paracresol cyclopentadiene isobutyl resin antioxidant.Or
Person is obtained after phenolic Petropols are generated by reacting with t-butyl methyl ether.Such as p-cresol, dicyclopentadiene, non-aqueous
Property solvent first carries out reaction under organic composite sulfonic acid catalyst and anhydrous condition and obtains p-cresol dcpd resin, so
T-butyl methyl ether is added to obtain paracresol cyclopentadiene isobutyl resin afterwards.However, isobutene, t-butyl methyl ether are safety
The relatively low butylation raw material of property.
The content of the invention
In order to overcome shortcoming and defect of the prior art, do invention and prepare paracresol dicyclopentadiene fourth there is provided one kind
The method of base product, carries out butylation reaction and prepares paracresol dicyclopentadiene using the safe tert-butyl alcohol as raw material
Butylation product, the excessive tert-butyl alcohol is easy to reaction controlling as reaction dissolvent, and catalyst is separated with reaction system to be simply easy to
Recycle.
The present invention is achieved by the following technical solutions：A kind of side for preparing paracresol dicyclopentadiene butylation product
Method, after the tert-butyl alcohol and paracresol-dcpd resin are weighed in proportion, heating is well mixed, and adds strongly acidic catalyst anti-
Should；Reaction is separated off catalyst and washs to neutrality after terminating, and organic phase is distilled off, and obtains paracresol dicyclopentadiene fourth
Base product；The tert-butyl alcohol is 4 with the mol ratio of paracresol-dcpd resin:1～50:1, the reaction temperature is
20～83 DEG C, the reaction time is 2～12h.
Further, the strongly acidic catalyst is sulfuric acid, and the tert-butyl alcohol is 20 with the mass ratio of sulfuric acid:1～1:5.
Further, the mass concentration of the sulfuric acid is 60%～98%.
Further, the mass concentration of the sulfuric acid is 80%～93%.
Further, the tert-butyl alcohol and the mass ratio of sulfuric acid are 5:1～2:1.
Further, the tert-butyl alcohol and the mol ratio of paracresol-dcpd resin are 8:1～20:1.
Further, the reaction temperature is 30～70 DEG C, and the reaction time is 4～8h.
The method for preparing paracresol dicyclopentadiene butylation product of the present invention, is made using the higher tert-butyl alcohol of security
Butylation reaction is carried out for raw material, it is to avoid the safety using the low butylation raw material of the securities such as isobutene, t-butyl methyl ether is hidden
Suffer from.In the preparation method, used as reaction dissolvent, reaction raw materials are simply easy to control reaction to the excessive tert-butyl alcohol, and keep away
Other toxic solvents such as toluene (or dimethylbenzene) are exempted from.In the preparation method of the present invention, catalyst is easily isolated with reaction system,
Solve the problems, such as catalyst recycling.Additionally, the paracresol dicyclopentadiene fourth prepared by the method for the present invention
The butyl rate of base product is not less than 99%.
Specific embodiment
The method for preparing paracresol dicyclopentadiene butylation product of the present invention is mainly：Weigh in proportion the tert-butyl alcohol and
After paracresol-dcpd resin mixing, heating is well mixed, and reacts under strongly acidic catalyst effect.After reaction terminates
It is separated off catalyst and washs to neutrality, organic phase is distilled off, obtains faint yellow solid product paracresol dicyclopentadiene
Butylation product.Butylation reaction is carried out as raw material using the higher tert-butyl alcohol of security, safe operation is greatly avoided
Potential safety hazard.
The tert-butyl alcohol is 4 with the mol ratio of paracresol-dcpd resin:1～50:1, preferably 8:1～20:1.Cross
The tert-butyl alcohol of amount as reaction dissolvent, reaction raw materials be simply easy to control reaction, and avoid toluene (or dimethylbenzene) etc. its
His toxic solvent.The excessive tert-butyl alcohol can reclaim in follow-up still-process, it is to avoid the waste of raw material.The tert-butyl alcohol with
The reaction temperature of paracresol-dcpd resin is 20～83 DEG C, preferably 30～70 DEG C.The reaction time is 2～12h,
It is preferred that 4～8h.
The strongly acidic catalyst is sulfuric acid.The tert-butyl alcohol is 20 with the mass ratio of sulfuric acid:1～1:5, preferably 5:1～
2:1.The mass concentration of the sulfuric acid is 60%～98%, preferably 80%～93%.Sulfuric acid is easily isolated with reaction system, solves
The problem of catalyst recycling.
The method for preparing paracresol dicyclopentadiene butylation product of the present invention, is made using the higher tert-butyl alcohol of security
Butylation reaction is carried out for raw material, it is to avoid the safety using the low butylation raw material of the securities such as isobutene, t-butyl methyl ether is hidden
Suffer from.In the preparation method, used as reaction dissolvent, reaction raw materials are simply easy to control reaction to the excessive tert-butyl alcohol, and keep away
Other toxic solvents such as toluene (or dimethylbenzene) are exempted from.In the preparation method of the present invention, catalyst is easily isolated with reaction system,
Solve the problems, such as catalyst recycling.Additionally, the paracresol dicyclopentadiene fourth prepared by the method for the present invention
The butyl rate of base product is not less than 99%.
The structural formula of the paracresol-dcpd resin is as follows, in the present invention, adopts mean molecule quantity for 538
Paracresol dcpd resin, but be not limited to this.
N=0, the integer such as 1,2,3...
The structural formula of the paracresol dicyclopentadiene butylation product prepared by the preparation method is as follows.
N=0, the integer such as 1,2,3...
Embodiment 1
In the tetra- mouthfuls of reaction bulbs of 1000mL equipped with stirring, thermometer and condenser pipe, addition 296g (4mol) tert-butyl alcohol,
269g (0.5mol) paracresol-dcpd resin (mean molecule quantity is 538) be heated to 80 DEG C make the tert-butyl alcohol and paracresol-
Dcpd resin is well mixed, and then cools to 65～70 DEG C, and (h 2 so 4 concentration is to be slowly added dropwise 148g sulfuric acid
80%), 1h adds sulfuric acid, adds rear insulation reaction 4h.Reaction terminates rear stratification, divides and removes lower catalyst agent sulfuric acid, upper strata
Organic phase is washed to neutrality with 5% sodium bicarbonate aqueous solution.Then organic phase is distilled, is reclaimed and is removed Excess t-butanol, obtain light
Yellow solid product paracresol dicyclopentadiene butylation product, product weight 320g, yield 98.5%.Fourth is analyzed by HPLC
Base rate is 99.2%.
Embodiment 2
In the tetra- mouthfuls of reaction bulbs of 1000mL equipped with stirring, thermometer and condenser pipe, addition 390g (5mol) tert-butyl alcohol,
134.5g (0.25mol) paracresol-dcpd resin (mean molecule quantity is 538) is heated to 80 DEG C makes the tert-butyl alcohol and to first
Phenol-dcpd resin is well mixed, and then cools to 30～35 DEG C, and (h 2 so 4 concentration is to be slowly added dropwise 78g sulfuric acid
93%), 1h is added, and adds rear insulation reaction 8h.Reaction terminates rear stratification, separates lower catalyst agent sulfuric acid, and upper strata is organic
Mutually washed to neutrality with 5% sodium bicarbonate aqueous solution.Then organic phase is distilled, is reclaimed and is removed Excess t-butanol, obtain faint yellow
Solid product paracresol dicyclopentadiene butylation product, product weight 159g, yield 97.8%, HPLC analyzes butyl rate and is
99.0%.
Embodiment 3
In the tetra- mouthfuls of reaction bulbs of 1000mL equipped with stirring, thermometer and condenser pipe, addition 390g (5mol) tert-butyl alcohol,
269g (0.5mol) paracresol-dcpd resin (mean molecule quantity is 538) be heated to 80 DEG C make the tert-butyl alcohol and paracresol-
Dcpd resin is well mixed, and then cools to 40～45 DEG C, and (h 2 so 4 concentration is to be slowly added dropwise 146g sulfuric acid
85%), 1h is added, and adds rear insulation reaction 5h.Reaction terminates rear stratification, separates lower catalyst agent sulfuric acid, and upper strata is organic
Mutually washed to neutrality with 5% sodium bicarbonate aqueous solution.Then organic phase is distilled, is reclaimed and is removed Excess t-butanol, obtain faint yellow
Solid product paracresol dicyclopentadiene butylation product, product weight 321g, yield 98.8%, HPLC analyzes butyl rate and is
99.5%.
Embodiment 4
In the tetra- mouthfuls of reaction bulbs of 1000mL equipped with stirring, thermometer and condenser pipe, addition 555g (7.5mol) tert-butyl alcohol,
269g (0.5mol) paracresol-dcpd resin (mean molecule quantity is 538) be heated to 80 DEG C make the tert-butyl alcohol and paracresol-
Dcpd resin is well mixed, and then cools to 50～55 DEG C, and (h 2 so 4 concentration is to be slowly added dropwise 123g sulfuric acid
88%), 1h is added, and adds rear insulation reaction 6h.Reaction terminates rear stratification, separates lower catalyst agent sulfuric acid, and upper strata is organic
Mutually washed to neutrality with 5% sodium bicarbonate aqueous solution.Then organic phase is distilled, is reclaimed and is removed Excess t-butanol, obtain faint yellow
Solid product paracresol dicyclopentadiene butylation product, product weight 316g, yield 97.2%, HPLC analyzes butyl rate and is
99.1%.
Embodiment 5
In the tetra- mouthfuls of reaction bulbs of 1000mL equipped with stirring, thermometer and condenser pipe, addition 444g (6mol) tert-butyl alcohol,
269g (0.5mol) paracresol-dcpd resin (mean molecule quantity is 538) be heated to 80 DEG C make the tert-butyl alcohol and paracresol-
Dcpd resin is well mixed, and then cools to 60～65 DEG C, and (h 2 so 4 concentration is to be slowly added dropwise 120g sulfuric acid
90%), 1h is added, and adds rear insulation reaction 4.5h.Reaction terminates rear stratification, separates lower catalyst agent sulfuric acid, and upper strata has
Machine is mutually washed to neutrality with 5% sodium bicarbonate aqueous solution.Then organic phase is distilled, is reclaimed and is removed Excess t-butanol, obtain yellowish
Color solid product paracresol dicyclopentadiene butylation product, product weight 319g, yield 98.2%, HPLC analysis butyl rates
For 99.3%.
Embodiment 6
In the tetra- mouthfuls of reaction bulbs of 1000mL equipped with stirring, thermometer and condenser pipe, addition 592g (8mol) tert-butyl alcohol,
86g (0.16mol) paracresol-dcpd resin (mean molecule quantity is 538) be heated to 80 DEG C make the tert-butyl alcohol and paracresol-
Dcpd resin is well mixed, and then cools to 20～25 DEG C, and (h 2 so 4 concentration is to be slowly added dropwise 29.6g sulfuric acid
98%), 1h is added, and adds rear insulation reaction 12h.Reaction terminates rear stratification, separates lower catalyst agent sulfuric acid, and upper strata is organic
Mutually washed to neutrality with 5% sodium bicarbonate aqueous solution.Then organic phase is distilled, is reclaimed and is removed Excess t-butanol, obtain faint yellow
Solid product paracresol dicyclopentadiene butylation product, product weight 95.2g, yield 91.5%, HPLC analysis butyl rates
For 91.1%.
Embodiment 7
In the tetra- mouthfuls of reaction bulbs of 2000mL equipped with stirring, thermometer and condenser pipe, addition 148g (2mol) tert-butyl alcohol,
269g (0.5mol) paracresol-dcpd resin (mean molecule quantity is 538) be heated to 83 DEG C make the tert-butyl alcohol and paracresol-
Dcpd resin is well mixed, and is slowly added dropwise 740g sulfuric acid (h 2 so 4 concentration is 60%), and 1h is added, and is incubated after adding
Reaction 2h.Reaction terminates rear stratification, separates lower catalyst agent sulfuric acid, and upper organic phase is washed with 5% sodium bicarbonate aqueous solution
Wash to neutrality.Then organic phase is distilled, is reclaimed and is removed Excess t-butanol, obtain faint yellow solid product paracresol dicyclopentadiene
Butylation product, product weight 292g, yield 89.8%, HPLC analysis butyl rates are 88.6%.
Above-mentioned embodiment is the invention is not limited in, if the various changes or deformation to the present invention are without departing from the present invention
Spirit and scope, if these change and deformation belong to the present invention claim and equivalent technologies within the scope of, then this
It is bright to be also intended to comprising these changes and deform.
Claims (7)
1. a kind of method for preparing paracresol dicyclopentadiene butylation product, it is characterised in that：Weigh in proportion the tert-butyl alcohol and
After paracresol-dcpd resin, heating is well mixed, and adds strongly acidic catalyst reaction；Reaction is separated off after terminating
Catalyst is simultaneously washed to neutrality, and organic phase is distilled off, and obtains paracresol dicyclopentadiene butylation product；The tert-butyl alcohol with
The mol ratio of paracresol-dcpd resin is 4:1～50:1, the reaction temperature is 20～83 DEG C, the reaction time
For 2～12h.
2. the method for preparing paracresol dicyclopentadiene butylation product according to claim 1, it is characterised in that：It is described
Strongly acidic catalyst is sulfuric acid, and the tert-butyl alcohol is 20 with the mass ratio of sulfuric acid:1～1:5.
3. the method for preparing paracresol dicyclopentadiene butylation product according to claim 2, it is characterised in that：It is described
The mass concentration of sulfuric acid is 60%～98%.
4. the method for preparing paracresol dicyclopentadiene butylation product according to claim 3, it is characterised in that：It is described
The mass concentration of sulfuric acid is 80%～93%.
5. the method for preparing paracresol dicyclopentadiene butylation product according to claim 2, it is characterised in that：It is described
The tert-butyl alcohol is 5 with the mass ratio of sulfuric acid:1～2:1.
6. the side for preparing paracresol dicyclopentadiene butylation product according to any claim in claim 1-5
Method, it is characterised in that：The tert-butyl alcohol is 8 with the mol ratio of paracresol-dcpd resin:1～20:1.
7. the method for preparing paracresol dicyclopentadiene butylation product according to claim 6, it is characterised in that：It is described
Reaction temperature is 30～70 DEG C, and the reaction time is 4～8h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446121A (en) * | 2017-08-18 | 2017-12-08 | 广东新华粤石化集团股份公司 | One pot process paracresol dicyclopentadiene butylation product |
| CN112939741A (en) * | 2021-02-03 | 2021-06-11 | 广东希必达新材料科技有限公司 | Novel antioxidant co-production p-cresol and dicyclopentadiene butylated product and BHT production process |
| CN113620785A (en) * | 2021-09-23 | 2021-11-09 | 广东希必达新材料科技有限公司 | Preparation method of antioxidant |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446121A (en) * | 2017-08-18 | 2017-12-08 | 广东新华粤石化集团股份公司 | One pot process paracresol dicyclopentadiene butylation product |
| CN112939741A (en) * | 2021-02-03 | 2021-06-11 | 广东希必达新材料科技有限公司 | Novel antioxidant co-production p-cresol and dicyclopentadiene butylated product and BHT production process |
| CN113620785A (en) * | 2021-09-23 | 2021-11-09 | 广东希必达新材料科技有限公司 | Preparation method of antioxidant |
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