CN105503534A - Preparation method of 2-cumyl-4-tert-octylphenol - Google Patents
Preparation method of 2-cumyl-4-tert-octylphenol Download PDFInfo
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- CN105503534A CN105503534A CN201511019506.8A CN201511019506A CN105503534A CN 105503534 A CN105503534 A CN 105503534A CN 201511019506 A CN201511019506 A CN 201511019506A CN 105503534 A CN105503534 A CN 105503534A
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- octylphenol
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- exchange resin
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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
- C07C37/14—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 addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 2-cumyl-4-tert-octylphenol. The preparation method comprises the following steps: adding tert-octylphenol and a strongly-acidic cation exchange resin into a reactor, and heating to 90-140 DEG C; dropwisely adding alpha-methyl styrene; after the dropwise addition, continuing keeping the temperature at 90-140 DEG C to react; and after the reaction finishes, filtering to recover the strongly-acidic cation exchange resin, and rectifying the filtrate to obtain the 2-cumyl-4-tert-octylphenol. The preparation method is simple to operate. The catalyst can be separated from the reaction system only by simple filtration without acid washing, alkali washing, water washing or any other step capable of easily generating wastewater, and thus, is more environment-friendly. The raw material conversion rate is high, and the alpha-methyl styrene conversion rate can reach 99% or above. The product selectivity is high, and the 2-cumyl-4-tert-octylphenol selectivity is 99% or above. The catalyst can be repeatedly used and regenerated, and is suitable for industrialized clean production.
Description
Technical field
The invention belongs to the preparation method of fortified phenol, be specifically related to a kind of preparation method of 2-cumyl-4-tert-octylphenol.
Background technology
2-cumyl-4-tert-octylphenol is the key intermediate of synthesis UV light absorber UV-928 (CAS 73936-91-1).UV light absorber UV-928 is a kind of novel hydroxybenzotriazole class, is applicable to the ultraviolet absorbers of high-performance coating.This product has wider absorption characteristic, can effective supercoat and other photochromics.The characteristics such as meanwhile, it is high that this product has solubleness, and high temperature resistant and environment durability is good; be particularly suitable for the system needing hot setting; as powder coating, coil steel coating etc., itself and the composite result of use of hindered amine light stabilizer are more desirable; compounded formula can provide better protection for coating; comprise and prevent coating color-changing, tarnish, cracking; bubble, departs from substrate.
Current 2-cumyl-4-tert-octylphenol is produced primarily of external SIGroup company.In recent years, UV light absorber UV-928 was in quick growth year by year in the international market, and have very strong vitality, development prospect is wide, and therefore as the key intermediate of its building-up process, 2-cumyl-4-tert-octylphenol also just seems particularly important.
In existing preparation method, mainly contain " synthesis of the special octyl phenol of 2-cumyl-4-" (Industrial Catalysis, 2008, the 09:68-70) of Lu Yuejin etc.The document report with to tert-octylphenol and alpha-methyl styrene for raw material, with p-methyl benzenesulfonic acid, or aluminium powder, or the method that aluminium flake etc. is the special octyl phenol of catalyzer synthesis 2-cumyl-4-, wherein with aluminium flake best results.The method of document report is as follows: a certain amount of Octylphenol and catalyzer are added in the reactor being furnished with stirring, thermometer, reflux condensing tube, well heater and filling tube, be heated with stirring to required temperature of reaction, and add alpha-methyl styrene at the appointed time, reaction certain hour; This reaction mixture is cooled to about 70 DEG C, uses 15%H
2sO
4wash 2 times, to pH=1, then use 5%Na
2cO
3wash 1 time, with distillation washing 1 time, rectifying, steams Octylphenol, obtains the special octyl phenol crude product of 2-cumyl-4-, by recrystallizing methanol, separates out the special octyl phenol of 2-cumyl-4-.The method exists catalyzer cannot recycled, and last handling process is complicated, and can produce a large amount of containing acid containing alkali waste water, be unfavorable for environment protection.
In order to solve the problem, need searching last handling process simple and catalyzer that is that easily recycle.Amberlyst series storng-acid cation exchange resin not only has good pore structure, large specific surface area, and macroporous network structure makes it show good physics and chemistry stability at non-polar solvent, and has good surface acidity.In addition, such storng-acid cation exchange resin is simple as last handling process during catalyzer, only needs simple filtration, easily recycles.
Summary of the invention
The object of this invention is to provide a kind of preparation method of 2-cumyl-4-tert-octylphenol, comprise following process:
To drop in reactor tert-octylphenol and storng-acid cation exchange resin, be warming up to 90 ~ 140 DEG C, drip alpha-methyl styrene; Be added dropwise to complete rear continuation to complete 90 ~ 140 DEG C of insulation reaction, filtered and recycled storng-acid cation exchange resin, filtrate obtains 2-cumyl-4-tert-octylphenol through rectifying.
Above-mentioned storng-acid cation exchange resin can be the trade mark kinds such as AMBERLYST15DRY, AMBERLYST35DRY, AMBERLYST36DRY;
The weight ratio of above-mentioned storng-acid cation exchange resin and tert-octylphenol is 0.01 ~ 0.1:1;
The mol ratio of above-mentioned tert-octylphenol and alpha-methyl styrene is 1:0.4 ~ 0.8;
The time for adding of dropping alpha-methyl styrene preferably 2 ~ 8 hours;
90 ~ 140 DEG C of insulation reaction time≤4.
Compared with existing synthetic method, preparation method of the present invention is simple to operate, and catalyzer only needs simple filtration just can realize being separated of catalyzer and reaction system, does not need pickling, alkali cleaning and washing etc. to be easy to produce the step of waste water, environmental protection more; And feed stock conversion is high, alpha-methyl styrene transformation efficiency can reach more than 99%; Product selectivity is good, 2-cumyl-4-tert-octylphenol selectivity more than 99%; Catalyzer can repeatedly use and the advantage such as regeneration, is suitable for industrialization cleaner production.
Embodiment
Following examples will contribute to understanding the present invention, but be not limited to content of the present invention.
Embodiment 1
206.4g is dropped in reactor to tert-octylphenol and 20.6g storng-acid cation exchange resin AMBERLYST15DRY, be warming up to 90 ~ 95 DEG C, drip 94.6g alpha-methyl styrene, time for adding 8 hours, be added dropwise to complete rear continuation 90 ~ 95 DEG C of insulation reaction 2 hours, reaction completes, filtered and recycled storng-acid cation exchange resin, and filtrate obtains 2-cumyl-4-tert-octylphenol through rectifying.Filtrate gas chromatographic analysis content: 2-cumyl-4-tert-octylphenol 73.4%, to tert-octylphenol 22.5%, alpha-methyl styrene 0.18%, 2,6-dicumyl-4-tert-octylphenol 0.06%; Alpha-methyl styrene transformation efficiency is 99.4%; 2-cumyl-4-tert-octylphenol selectivity is 99.9%.
Embodiment 2
206.4g is dropped in reactor to tert-octylphenol and 10.3g storng-acid cation exchange resin AMBERLYST35DRY, be warming up to 120 ~ 125 DEG C, drip 47.3g alpha-methyl styrene, time for adding 4 hours, be added dropwise to complete rear reaction to complete, filtered and recycled storng-acid cation exchange resin, filtrate obtains 2-cumyl-4-tert-octylphenol through rectifying.Filtrate gas chromatographic analysis content: 2-cumyl-4-tert-octylphenol 37.8%, to tert-octylphenol 60.0%, alpha-methyl styrene 0.12%, 2,6-dicumyl-4-tert-octylphenol 0.12%; Alpha-methyl styrene transformation efficiency is 99.4%; 2-cumyl-4-tert-octylphenol selectivity is 99.7%.
Embodiment 3
206.4g is dropped in reactor to tert-octylphenol and 2.1g storng-acid cation exchange resin AMBERLYST36DRY, be warming up to 135 ~ 140 DEG C, drip 70.9g alpha-methyl styrene, time for adding 4 hours, be added dropwise to complete rear continuation 135 ~ 140 DEG C of insulation reaction 1 hour, reaction completes, filtered and recycled storng-acid cation exchange resin, and filtrate obtains 2-cumyl-4-tert-octylphenol through rectifying.Filtrate gas chromatographic analysis content: 2-cumyl-4-tert-octylphenol 62.3%, to tert-octylphenol 35.3%, alpha-methyl styrene 0.06%, 2,6-dicumyl-4-tert-octylphenol 0.58%; Alpha-methyl styrene transformation efficiency is 99.8%; 2-cumyl-4-tert-octylphenol selectivity is 99.1%.
Embodiment 4
206.4g is dropped in reactor to tert-octylphenol and 10.3g storng-acid cation exchange resin AMBERLYST15DRY, be warming up to 90 ~ 95 DEG C, drip 70.9g alpha-methyl styrene, time for adding 4 hours, be added dropwise to complete rear continuation 90 ~ 95 DEG C of insulation reaction 4 hours, reaction completes, filtered and recycled storng-acid cation exchange resin, and filtrate obtains 2-cumyl-4-tert-octylphenol through rectifying.Filtrate gas chromatographic analysis content: 2-cumyl-4-tert-octylphenol 63.3%, to tert-octylphenol 33.3%, alpha-methyl styrene 0.25%, 2,6-dicumyl-4-tert-octylphenol 0.10%; Alpha-methyl styrene transformation efficiency is 99.0%; 2-cumyl-4-tert-octylphenol selectivity is 99.8%.
Embodiment 5
206.4g is dropped in reactor to tert-octylphenol and 10.3g storng-acid cation exchange resin AMBERLYST36DRY, be warming up to 135 ~ 140 DEG C, drip 70.9g alpha-methyl styrene, time for adding 1 hour, be added dropwise to complete rear continuation 135 ~ 140 DEG C of insulation reaction 1 hour, reaction completes, filtered and recycled storng-acid cation exchange resin, and filtrate obtains 2-cumyl-4-tert-octylphenol through rectifying.Filtrate gas chromatographic analysis content: 2-cumyl-4-tert-octylphenol 62.8%, to tert-octylphenol 34.3%, alpha-methyl styrene 0.10%, 2,6-dicumyl-4-tert-octylphenol 0.60%; Alpha-methyl styrene transformation efficiency is 99.6%; 2-cumyl-4-tert-octylphenol selectivity is 99.1%.
Open and a kind of preparation method of 2-cumyl-4-tert-octylphenol that proposes of the present invention, those skilled in the art are by using for reference present disclosure, the links such as appropriate change condition route realize, although method of the present invention and technology of preparing are described by preferred embodiment, person skilled obviously can change Method and Technology route as herein described or reconfigure not departing from content of the present invention, spirit and scope, realizes final technology of preparing.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (7)
1. a preparation method for 2-cumyl-4-tert-octylphenol, is characterized in that: with to tert-octylphenol and alpha-methyl styrene for reaction raw materials, under the catalysis of storng-acid cation exchange resin, prepare 2-cumyl-4-tert-octylphenol through alkylated reaction.
2. preparation method as claimed in claim 1, is characterized in that: will drop in reactor tert-octylphenol and storng-acid cation exchange resin, and be warming up to 90 ~ 140 DEG C; Drip alpha-methyl styrene; Be added dropwise to complete rear continuation to complete 90 ~ 140 DEG C of insulation reaction, filtered and recycled storng-acid cation exchange resin, filtrate obtains 2-cumyl-4-tert-octylphenol through rectifying.
3. the method for claim 1, is characterized in that storng-acid cation exchange resin is the kind of AMBERLYST15DRY, AMBERLYST35DRY or AMBERLYST36DRY trade mark.
4. method as claimed in claim 2, is characterized by: the weight ratio of storng-acid cation exchange resin and tert-octylphenol is 0.01 ~ 0.1:1.
5. method as claimed in claim 2, is characterized by: the mol ratio of tert-octylphenol and alpha-methyl styrene is 1:0.4 ~ 0.8.
6. method as claimed in claim 2, is characterized by: alpha-methyl styrene time for adding 2 ~ 8 hours.
7. method as claimed in claim 2, is characterized by: insulation reaction time≤4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511019506.8A CN105503534B (en) | 2015-12-30 | 2015-12-30 | A kind of preparation method of the tert-octylphenol of 2 cumyl 4 |
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| CN201511019506.8A CN105503534B (en) | 2015-12-30 | 2015-12-30 | A kind of preparation method of the tert-octylphenol of 2 cumyl 4 |
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| CN105503534A true CN105503534A (en) | 2016-04-20 |
| CN105503534B CN105503534B (en) | 2017-08-11 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112110799A (en) * | 2020-09-25 | 2020-12-22 | 药大制药有限公司 | Preparation method of octoxynol |
| CN116253617A (en) * | 2023-02-10 | 2023-06-13 | 利安隆（中卫）新材料有限公司 | Method for preparing 2, 4-dicumyl phenol |
| CN118084626A (en) * | 2024-02-23 | 2024-05-28 | 江苏极易新材料有限公司 | Synthesis method of o-cumyl-p-tert-octylphenol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962591A (en) * | 2005-11-11 | 2007-05-16 | 中国石油化工股份有限公司 | 2,4-di-(1-phenylisopropyl) phenol preparation method |
| KR20120065836A (en) * | 2010-12-13 | 2012-06-21 | 금호석유화학 주식회사 | Method of preparing styrenated phenol |
-
2015
- 2015-12-30 CN CN201511019506.8A patent/CN105503534B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962591A (en) * | 2005-11-11 | 2007-05-16 | 中国石油化工股份有限公司 | 2,4-di-(1-phenylisopropyl) phenol preparation method |
| KR20120065836A (en) * | 2010-12-13 | 2012-06-21 | 금호석유화학 주식회사 | Method of preparing styrenated phenol |
Non-Patent Citations (1)
| Title |
|---|
| 陆跃进: "2－枯基－4－特辛基酚的合成", 《工业催化》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112110799A (en) * | 2020-09-25 | 2020-12-22 | 药大制药有限公司 | Preparation method of octoxynol |
| CN116253617A (en) * | 2023-02-10 | 2023-06-13 | 利安隆（中卫）新材料有限公司 | Method for preparing 2, 4-dicumyl phenol |
| CN118084626A (en) * | 2024-02-23 | 2024-05-28 | 江苏极易新材料有限公司 | Synthesis method of o-cumyl-p-tert-octylphenol |
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Effective date of registration: 20170629 Address after: 300480 Tianjin economic and Technological Development Zone, Hangu modern industrial zone, Mount Huangshan Road, No. 6 Applicant after: Rianlon Corporation Applicant after: Lian long (central defender) new material Co., Ltd. Address before: 300480, No. 6, Mount Huangshan Road, Hangu modern industrial district, Tianjin economic and Technological Development Zone, Hangu District, Tianjin Applicant before: Rianlon Corporation |
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