CN109400449A - A method of preparing alkyl phenyl alcohol polyoxyethylene ether - Google Patents
A method of preparing alkyl phenyl alcohol polyoxyethylene ether Download PDFInfo
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- CN109400449A CN109400449A CN201811145290.3A CN201811145290A CN109400449A CN 109400449 A CN109400449 A CN 109400449A CN 201811145290 A CN201811145290 A CN 201811145290A CN 109400449 A CN109400449 A CN 109400449A
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- polyoxyethylene ether
- alkene
- alkyl phenyl
- alcohol polyoxyethylene
- benzyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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Abstract
A kind of method preparing alkyl phenyl alcohol polyoxyethylene ether is alkene, benzyl alcohol or benzyl carbinol and solid acid catalyst in 80 DEG C~200 DEG C reaction 10 min~300min, filtering reacting liquid removes catalyst, it carries out that unreacted raw material is evaporated off, to obtain alkyl phenyl alcohol, again with reacting ethylene oxide, alkyl phenyl alcohol polyoxyethylene ether is made.The present invention has the advantages that simple process, is easily industrialized.
Description
Technical field
The present invention relates to a kind of methods for preparing alkyl phenyl alcohol polyoxyethylene ether nonionic surfactant.
Background technique
Alkyl phenol polyoxyethylene ether (abbreviation APEOn, n represents the number of ethyoxyl, and structural formula is as follows) and it is to be passed through by alkyl phenol
A kind of nonionic surfactant that ethoxylation obtains.Such surfactant molecule structure adjustability is strong, by changing
Different performance can be showed to meet different applications by becoming long alkyl chains or EO number, these advantages make its coating, weaving,
The multiple fields such as rubber, which have, to be widely applied.
In the 1980s, related APEOnThe study found that APEOnProduct (alkyl phenol, short EO chain after biodegrade
APEOn) there is high toxicity, and can accumulate in vivo.APEO as a result,nBiological degradability and toxicity problem cause people
Attention.Bureau for Environmental Protection, Britain in 1997 announces one of the chemical substance that alkyl phenol is 70 kinds of environmental hormones.Due to APEOn
The influence of the toxicity, biological degradability difference and environmental hormone of catabolite, European Union is in 2003 to APEOnUse, circulation
Corresponding limitation and regulation are made that with discharge.With the growth that ecological environment security is realized, APEOnLimitation use will become
Inexorable trend, searching can effectively substitute APEOnChemicals have been to be concerned by more and more people.It studies at present relatively broad
Substitute mainly has fatty alcohol polyoxyethylene ether, isomeric alcohol polyethenoxy ether, fatty acid methyl ester ethoxylate etc..These substitutions
Product and APEOnIt compares, the functional group of this low pole of phenyl ring is lacked in molecule, also there is certain difference in performance.Therefore,
Find a kind of and APEOnStructure is similar, i.e., not only retains benzene ring structure, and is avoided that alkyl phenol structure bring biological degradability
With the APEO of toxicity problemnSubstitute become research emphasis.
Patent CN106187714A and the [synthesis of Lu Ying, Liu Xuefeng, Fang Yun dodecyl benzylalcohol polyoxyethylene ether of document 1
And performance, daily chemical industry, 2012,42 (2): 79-83.] using detergent alkylate as raw material, it is anti-by halomethylation, hydrolysis
It should synthesize to obtain dodecyl benzyl alcohol, then carry out addition reaction with ethylene oxide and obtain dodecyl benzyl alcohol polyoxyethylene
Ether.[Wang Xianguang, Zhang Chunrong, Song Xinwang wait the conjunction of p- (lauryl) the benzyl homogeneity polyethenoxy ether propane sulfonic acid sodium of to document 2
At with surface-active fine chemistry industry, 2007,24 (2): 145-148] using fatty acid as hydrophobic group source, be acylated by friedel-craft
Reaction, Huang Min-lon reduction reaction, Blank reaction, Williamson etherification reaction have obtained p- alkyl-benzyl homogeneous polyoxy second
Alkene ether.
The product alkyl benzyl alcohol polyoxyethylene ether of above-mentioned 3 documents and the architectural difference of alkyl phenol polyoxyethylene ether are
The former replaces phenol oxygroup with benzyloxy, it is possible to fundamentally solve the toxicity problem in degradation process, be potential APEOn's
Substitute, but this two lines synthesis step is more, process route is complicated, is unfavorable for industrialization promotion.
Summary of the invention
The object of the present invention is to provide a kind of simple process, be easily industrialized prepare alkyl phenyl alcohol polyoxyethylene
The technique of ether.
The present invention is a kind of technique for preparing alkyl phenyl alcohol polyoxyethylene ether, specific steps are as follows:
(1) it is alkylated
Alkene, benzyl alcohol or benzyl carbinol is added in the reactor and solid acid catalyst, catalyst amount are alkene and benzene
The molar ratio of the 0.1%-20% of methanol or benzyl carbinol gross mass, benzyl alcohol or benzyl carbinol and alkene be 1:1-5:1,80 DEG C~
200 DEG C of reaction 10min~300min, filtering reacting liquid remove catalyst, carry out that unreacted raw material is evaporated off, from
And obtain alkyl phenyl alcohol；
(2) ethoxylation
Alkyl phenyl alcohol polyoxyethylene ether is made in alkyl phenyl alcohol and reacting ethylene oxide.Ethoxylation technique is by existing
Prepare alkyl phenol polyoxyethylene ether, the technique of fatty alcohol polyoxyethylene ether carries out.
Alkene as described above includes alpha-olefin or internal olefin.
The carbochain of alkene as described above can be C8~C24Any one or more of mixture.
It is the alkene that raw material obtains that alkene as described above, which can be petroleum chemicals, is also possible to the conjunction of ICL for Indirect Coal Liquefaction Fischer-Tropsch
At obtained mixture of olefins/paraffins.
Solid acid catalyst as described above can be HY molecular sieve, perfluorinated sulfonic resin, atlapulgite or sulphation oxygen
Change zirconium.
The skeleton symbol of alkyl phenyl alcohol polyoxyethylene ether prepared by the present invention is as follows:
In formula, R C8-C24Alkyl；M=1,2；N indicates EO group numbers, n=1~20.
With it is existing prepare alkyl phenyl alcohol technology compared with, the invention has the following advantages that
(1) technique of the present invention for preparing alkyl phenyl alcohol only needs a step alkylated reaction can be completed, technique road
Line is short, at low cost, is easy to industrialization promotion.
(2) the alkyl phenyl alcohol technique of the present invention for preparing is heterogeneous reaction, and aftertreatment technology is simple.
Specific embodiment
Embodiment 1: being added sulfated zirconia, benzyl alcohol and octene in the reactor, catalyst amount be benzyl alcohol and
The molar ratio of the 0.1% of alkene total weight, benzyl alcohol and alkene is 1:1,80 DEG C of reaction 100min, then filtering reacting liquid subtracts
Unreacted benzyl alcohol is distilled off for pressure and alkene obtains octyl benzyl alcohol, yield 70%；Octyl benzyl alcohol and ethylene oxide into
Row reaction (both front and backs molar ratio of material is 1:1), obtains octyl benzyl alcohol polyoxyethylene ether (EO=1).
Embodiment 2: it is benzyl alcohol and alkene that atlapulgite, benzyl alcohol and laurylene, catalyst amount are added in the reactor
The molar ratio of the 20% of hydrocarbon total weight, benzyl alcohol and alkene is 5:1,200 DEG C of reaction 200min, then filtering reacting liquid depressurizes
Unreacted benzyl alcohol is distilled off and alkene obtains dodecyl benzyl alcohol, yield 76%；Dodecyl benzyl alcohol and ethylene oxide
(both front and backs molar ratio of material is 1:12) is reacted, dodecyl benzyl alcohol polyoxyethylene ether (EO=12) is obtained.
Embodiment 3: HY molecular sieve, benzyl alcohol and C are added in the reactor14-16Alkene, catalyst amount be benzyl alcohol and
The molar ratio of the 5% of alkene total weight, benzyl alcohol and alkene is 2:1,190 DEG C of reaction 10min, then filtering reacting liquid depressurizes
Unreacted benzyl alcohol is distilled off and alkene obtains C14-16Alkyl benzyl alcohol, yield 56%；C14-16Alkyl benzyl alcohol and epoxy
Ethane is reacted (both front and backs molar ratio of material is 1:15), obtains C14-16Alkyl benzyl alcohol polyoxyethylene ether (EO=15).
Embodiment 4: it is benzyl alcohol that perfluorinated sulfonic resin, benzyl alcohol and octadecylene, catalyst amount are added in the reactor
With the 10% of alkene total weight, the molar ratio of benzyl alcohol and alkene is 2.5:1,160 DEG C of reaction 40min, filtering reacting liquid, then
Vacuum distillation removes unreacted benzyl alcohol and alkene obtains octadecyl benzyl alcohol, yield 53%；Octadecyl benzyl alcohol with
Ethylene oxide is reacted (both front and backs molar ratio of material is 1:20), obtains octadecyl benzyl alcohol polyoxyethylene ether (EO=
20)。
Embodiment 5: it is benzyl carbinol and alkene that HY molecular sieve, benzyl carbinol and laurylene, catalyst amount are added in the reactor
The molar ratio of the 3% of hydrocarbon total weight, benzyl carbinol and alkene is 1:1, and 170 DEG C of reaction 30min, filtering reacting liquid, then decompression is steamed
Distillation goes unreacted benzyl carbinol and alkene to obtain dodecyl benzyl carbinol, yield 74%；Dodecyl benzyl carbinol and epoxy second
Alkane is reacted (both front and backs molar ratio of material is 1:12), obtains dodecyl benzyl carbinol polyoxyethylene ether (EO=12).
Embodiment 6: being added sulfated zirconia, benzyl carbinol and decene in the reactor, catalyst amount be benzyl carbinol and
The molar ratio of the 2% of alkene total weight, benzyl carbinol and alkene is 2:1,130 DEG C of reaction 60min, then filtering reacting liquid depressurizes
Unreacted benzyl carbinol is distilled off and alkene obtains decyl benzyl carbinol, yield 78%；Decyl benzyl carbinol and ethylene oxide carry out
Reaction (both front and backs molar ratio of material is 1:5), obtains decyl benzyl carbinol polyoxyethylene ether (EO=5).
Embodiment 7: the C that sulfated zirconia, benzyl carbinol and F- T synthesis mink cell focus rectifying obtain is added in the reactor8-
C10Mixture of olefins/paraffins, catalyst amount are the 4% of benzyl carbinol and alkene total weight, and the molar ratio of benzyl carbinol and alkene is
4:1,110 DEG C of reaction 300min, filtering reacting liquid, then vacuum distillation removes unreacted raw material and obtains C8-10Alkylbenzene second
Alcohol, yield 81%；C8-10Alkyl benzyl carbinol is reacted (both front and backs molar ratio of material is 1:9) with ethylene oxide, obtains C8-10
Alkyl benzyl carbinol polyoxyethylene ether (EO=9).
Embodiment 8: it is benzyl carbinol that atlapulgite, benzyl carbinol and 16 internal olefins, catalyst amount are added in the reactor
With the 15% of alkene total weight, the molar ratio of benzyl carbinol and alkene is 1:1,180 DEG C of reaction 60min, then filtering reacting liquid subtracts
Unreacted benzyl carbinol is distilled off for pressure and alkene obtains cetyl benzyl carbinol, yield 70%；Cetyl benzyl carbinol and ring
Oxidative ethane is reacted (both front and backs molar ratio of material is 1:18), obtains cetyl benzyl carbinol polyoxyethylene ether (EO=
18)。
Embodiment 9: perfluorinated sulfonic resin, benzyl carbinol and C are added in the reactor20-24Alkene, catalyst amount are benzene second
The molar ratio of the 10% of pure and mild alkene total weight, benzyl carbinol and alkene be 3:1,160 DEG C of reaction 120min, filtering reacting liquid, so
Vacuum distillation removes unreacted benzyl carbinol afterwards and alkene obtains C20-24Alkyl benzyl carbinol, yield 50%；C20-24Alkyl benzyl carbinol
(both front and backs molar ratio of material is 1:20) is reacted with ethylene oxide, obtains C20-24Alkyl benzyl carbinol polyoxyethylene ether (EO
=20).
Claims (6)
1. a kind of method for preparing alkyl phenyl alcohol polyoxyethylene ether, it is characterised in that include the following steps:
(1) it is alkylated
Alkene, benzyl alcohol or benzyl carbinol is added in the reactor and solid acid catalyst, catalyst amount are alkene and benzyl alcohol
Or the molar ratio of the 0.1%-20% of benzyl carbinol gross mass, benzyl alcohol or benzyl carbinol and alkene is 1:1-5:1, at 80 DEG C~200 DEG C
10 min~300min is reacted, filtering reacting liquid removes catalyst, carries out that unreacted raw material is evaporated off, thus
To alkyl phenyl alcohol；
(2) ethoxylation
Alkyl phenyl alcohol and reacting ethylene oxide, are made alkyl phenyl alcohol polyoxyethylene ether, and ethoxylation technique presses existing preparation
Alkyl phenol polyoxyethylene ether, the technique of fatty alcohol polyoxyethylene ether carry out.
2. a kind of method for preparing alkyl phenyl alcohol polyoxyethylene ether as described in claim 1, it is characterised in that the alkene
Hydrocarbon includes alpha-olefin or internal olefin.
3. a kind of method for preparing alkyl phenyl alcohol polyoxyethylene ether as claimed in claim 2, it is characterised in that the alkene
The carbochain of hydrocarbon is C8~C24Any one or more of mixture.
4. a kind of method for preparing alkyl phenyl alcohol polyoxyethylene ether as described in claim 1, it is characterised in that the alkene
Hydrocarbon is that petroleum chemicals are the mixture of olefins/paraffins that the alkene that raw material obtains or ICL for Indirect Coal Liquefaction F- T synthesis obtain.
5. a kind of method for preparing alkyl phenyl alcohol polyoxyethylene ether as described in claim 1, it is characterised in that as described above
Solid acid catalyst be HY molecular sieve, perfluorinated sulfonic resin, atlapulgite or sulfated zirconia.
6. such as the alkyl phenyl alcohol polyoxyethylene ether of any one of claim 1-5 the method preparation, it is characterised in that alkylbenzene
The skeleton symbol of base alcohol polyoxyethylene ether is as follows:
In formula, R C8-C24Alkyl；M=1,2；N indicates EO group numbers, n=1~20.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111039750A (en) * | 2019-12-30 | 2020-04-21 | 盐城工学院 | Method for preparing 4-tert-butyl phenethyl alcohol |
| CN111072523A (en) * | 2020-01-06 | 2020-04-28 | 中国日用化学研究院有限公司 | Preparation process of composite sulfonic acid of alkylbenzene and 1, 1-phenyl-alkyl phenyl ethane or salt thereof |
| CN111454130A (en) * | 2020-04-20 | 2020-07-28 | 中国日用化学研究院有限公司 | Process for preparing alkyl diphenyl ether by catalyzing reaction of olefin and diphenyl ether with solid acid |
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| CN106187714A (en) * | 2016-07-19 | 2016-12-07 | 南通市晗泰化工有限公司 | Alkylbenzene methanol polyoxyethylene ether and preparation method thereof |
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| CN1868984A (en) * | 2005-05-24 | 2006-11-29 | 浙江工业大学 | Preparation method of linear alkylbenzene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039750A (en) * | 2019-12-30 | 2020-04-21 | 盐城工学院 | Method for preparing 4-tert-butyl phenethyl alcohol |
| CN111072523A (en) * | 2020-01-06 | 2020-04-28 | 中国日用化学研究院有限公司 | Preparation process of composite sulfonic acid of alkylbenzene and 1, 1-phenyl-alkyl phenyl ethane or salt thereof |
| CN111454130A (en) * | 2020-04-20 | 2020-07-28 | 中国日用化学研究院有限公司 | Process for preparing alkyl diphenyl ether by catalyzing reaction of olefin and diphenyl ether with solid acid |
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