CN109400449B - Method for preparing alkyl phenyl alcohol polyoxyethylene ether - Google Patents

Method for preparing alkyl phenyl alcohol polyoxyethylene ether Download PDF

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CN109400449B
CN109400449B CN201811145290.3A CN201811145290A CN109400449B CN 109400449 B CN109400449 B CN 109400449B CN 201811145290 A CN201811145290 A CN 201811145290A CN 109400449 B CN109400449 B CN 109400449B
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olefin
alcohol
polyoxyethylene ether
benzyl alcohol
catalyst
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CN109400449A (en
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刘晓臣
王晓朋
霍月清
牛金平
韩亚明
韩向丽
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China Daily Chemical Research Institute Co ltd
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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
    • 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
    • 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 process for preparing alkylphenyl alcohol polyethenoxy ether includes reaction between olefin, benzyl alcohol or phenethyl alcohol and solid acid catalyst at 80-200 deg.C for 10-300 min, filtering reaction liquid to remove catalyst, vacuum distilling to remove unreacted raw material to obtain alkylphenyl alcohol, and reaction with epoxy ethane to obtain alkylphenyl alcohol polyethenoxy ether. The invention has the advantages of simple and convenient process and easy realization of industrialization.

Description

Method for preparing alkyl phenyl alcohol polyoxyethylene ether
Technical Field
The invention relates to a method for preparing an alkyl phenyl alcohol polyoxyethylene ether nonionic surfactant.
Background
Alkylphenol polyoxyethylene (APEO for short)nN represents the number of ethoxy groups, and the structural formula is as follows) is a nonionic surfactant obtained by ethoxylation of alkylphenol. The molecular structure of the surfactant is highly adjustable, different performances can be expressed by changing the length of an alkyl chain or the EO number so as to meet different applications, and the surfactant has wide application in the fields of coatings, textiles, rubber and the like due to the advantages.
Figure BDA0001816680410000011
About APEO in the 80 s of the 20 th centurynFound that APEO nProducts after biodegradation (alkylphenols, short EO chain APEOn) Has high toxicity and can be accumulated in organism. Thus, APEOnThe problems of biodegradability and toxicity have attracted attention. The uk environmental protection agency published in 1997 alkylphenol as one of the chemicals of 70 environmental hormones. Due to APEOnPoisoning of degradation productsPoor sex and biodegradability and the influence of environmental hormones, APEO was treated in 2003 in the European UnionnAre subject to corresponding restrictions and regulations. As the ecological environment safety consciousness grows, APEOnWill become a necessary trend to find effective replacements for APEOnAre receiving increasing attention. At present, the widely researched substitutes mainly comprise fatty alcohol-polyoxyethylene ether, isomeric alcohol-polyoxyethylene ether, fatty acid methyl ester ethoxylate and the like. These alternatives with APEOnIn contrast, the molecule lacks a benzene ring, which is a functional group with weak polarity, and has a certain difference in performance. Therefore, a method for producing APEOnAPEO with similar structure, namely not only keeping benzene ring structure, but also avoiding the problems of biodegradability and toxicity brought by alkylphenol structurenHave become the focus of research.
Patent CN106187714A and document 1[ glume, liuxuefeng, cristobalite, synthesis and performance of dodecyl benzyl alcohol polyoxyethylene ether, daily chemical industry, 2012, 42 (2): 79-83 ] dodecyl benzene is used as a raw material, and is synthesized into dodecyl benzyl alcohol through halomethylation and hydrolysis reaction, and then the dodecyl benzyl alcohol is subjected to addition reaction with ethylene oxide to obtain dodecyl benzyl alcohol polyoxyethylene ether. Document 2[ wangshenhan, zhangchuanrong, songxinwang, et al. synthesis and surface activity of p- (lauryl) benzyl homogeneous polyoxyethylene ether propane sodium sulfonate, fine chemical industry, 2007, 24 (2): 145-148 takes fatty acid as a hydrophobic group source, and the p-alkyl-benzyl homogeneous polyoxyethylene ether is obtained through Friedel-crafts acylation reaction, Huang Minlon reduction reaction, Blank reaction and Williamson etherification reaction.
The structural difference between the products of the above 3 documents, namely the alkylphenol polyoxyethylene ether and the alkylphenol polyoxyethylene ether, is that the former replaces the phenoxy group with the benzyloxy group, so that the problem of toxicity in the degradation process can be fundamentally solved, and the product is potential APEOnThe two routes have multiple synthesis steps and complex process routes, and are not beneficial to industrial popularization.
Disclosure of Invention
The invention aims to provide a process for preparing alkyl phenyl alcohol polyoxyethylene ether, which is simple and convenient in process and easy to realize industrialization.
The invention relates to a process for preparing alkyl phenyl alcohol polyoxyethylene ether, which comprises the following specific operation steps:
(1) alkylation
Adding olefin, benzyl alcohol or phenethyl alcohol and a solid acid catalyst into a reactor, wherein the dosage of the catalyst is 0.1-20% of the total mass of the olefin and the benzyl alcohol or the phenethyl alcohol, the molar ratio of the benzyl alcohol or the phenethyl alcohol to the olefin is 1:1-5:1, reacting at 80-200 ℃ for 10-300 min, filtering reaction liquid to remove the catalyst, and carrying out reduced pressure distillation to remove unreacted raw materials so as to obtain alkyl benzyl alcohol;
(2) ethoxylation
And reacting the alkyl phenyl alcohol with ethylene oxide to obtain the alkyl phenyl alcohol polyoxyethylene ether. The ethoxylation process is carried out according to the prior process for preparing alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
The olefins as described above comprise alpha-olefins or internal olefins.
The carbon chain of the olefin as described above may be C8～C24Any one or a mixture of several of them.
The olefins may be olefins obtained from petrochemical products or olefin/paraffin mixtures obtained by Fischer-Tropsch synthesis from indirect liquefaction of coal.
The solid acid catalyst as described above may be HY molecular sieve, perfluorosulfonic acid resin, activated clay or sulfated zirconia.
The alkyl phenyl alcohol polyoxyethylene ether prepared by the invention has the following structural formula:
Figure BDA0001816680410000021
in the formula, R is C8-C24Alkyl groups of (a); m is 1, 2; n represents the number of EO groups, and n is 1 to 20.
Compared with the prior art for preparing alkyl phenyl alcohol, the method has the following advantages:
(1) the process for preparing the alkylphenyl alcohol can be completed by only one-step alkylation reaction, and has the advantages of short process route, low cost and easy industrial popularization.
(2) The process for preparing the alkyl phenyl alcohol is heterogeneous reaction, and the post-treatment process is simple.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1: adding sulfated zirconia, benzyl alcohol and octene into a reactor, wherein the dosage of a catalyst is 0.1 percent of the total weight of the benzyl alcohol and olefin, the molar ratio of the benzyl alcohol to the olefin is 1:1, reacting for 100min at 80 ℃, filtering reaction liquid, and then removing unreacted benzyl alcohol and olefin by reduced pressure distillation to obtain octyl benzyl alcohol with the yield of 70 percent; octyl benzyl alcohol and ethylene oxide were reacted (molar ratio of the former to the latter was 1:1) to obtain octyl benzyl alcohol polyoxyethylene ether (EO ═ 1).
Example 2: adding activated clay, benzyl alcohol and dodecene into a reactor, wherein the dosage of a catalyst is 20 percent of the total weight of the benzyl alcohol and the olefin, the molar ratio of the benzyl alcohol to the olefin is 5:1, reacting for 200min at 200 ℃, filtering reaction liquid, and then removing unreacted benzyl alcohol and olefin by reduced pressure distillation to obtain dodecyl benzyl alcohol with the yield of 76 percent; dodecyl benzyl alcohol and ethylene oxide are reacted (the molar ratio of the two materials is 1:12) to obtain dodecyl benzyl alcohol polyoxyethylene ether (EO is 12).
Example 3: adding HY molecular sieve, benzyl alcohol and C into a reactor14-16Olefin, the dosage of the catalyst is 5 percent of the total weight of the benzyl alcohol and the olefin, the molar ratio of the benzyl alcohol to the olefin is 2:1, the reaction is carried out for 10min at 190 ℃, the reaction solution is filtered, and then the unreacted benzyl alcohol and the olefin are removed by reduced pressure distillation to obtain C14-16Alkyl benzyl alcohol, yield 56%; c14-16Alkyl benzyl alcohol and ethylene oxide are reacted (the molar ratio of the front material to the rear material is 1:15) to obtain C14-16Alkyl benzyl alcohol polyoxyethylene ether (EO ═ 15).
Example 4: adding perfluorinated sulfonic acid resin, benzyl alcohol and octadecene into a reactor, wherein the dosage of a catalyst is 10% of the total weight of the benzyl alcohol and the olefin, the molar ratio of the benzyl alcohol to the olefin is 2.5:1, reacting for 40min at 160 ℃, filtering reaction liquid, and then removing unreacted benzyl alcohol and olefin through reduced pressure distillation to obtain octadecylbenzyl alcohol with the yield of 53%; octadecyl benzyl alcohol and ethylene oxide were reacted (molar ratio of the former to the latter was 1:20) to obtain octadecyl benzyl alcohol polyoxyethylene ether (EO 20).
Example 5: adding HY molecular sieve, phenethyl alcohol and dodecene into a reactor, wherein the dosage of the catalyst is 3% of the total weight of the phenethyl alcohol and olefin, the molar ratio of the phenethyl alcohol to the olefin is 1:1, reacting for 30min at 170 ℃, filtering reaction liquid, and then removing unreacted phenethyl alcohol and olefin by reduced pressure distillation to obtain dodecyl phenethyl alcohol with the yield of 74%; and (3) reacting the dodecylbenzene ethanol with ethylene oxide (the molar ratio of the two materials is 1:12) to obtain the dodecylbenzene ethanol polyoxyethylene ether (EO is 12).
Example 6: adding sulfated zirconia, phenethyl alcohol and decene into a reactor, wherein the dosage of a catalyst is 2 percent of the total weight of the phenethyl alcohol and olefin, the molar ratio of the phenethyl alcohol to the olefin is 2:1, reacting for 60min at 130 ℃, filtering reaction liquid, and then removing unreacted phenethyl alcohol and olefin by reduced pressure distillation to obtain decyl phenethyl alcohol with the yield of 78 percent; decyl phenethyl alcohol and ethylene oxide are reacted (the molar ratio of the two materials is 1:5), and decyl phenethyl alcohol polyoxyethylene ether (EO is 5) is obtained.
Example 7: adding sulfated zirconia, phenethyl alcohol and C obtained by rectifying Fischer-Tropsch synthesis heavy oil into a reactor8-C10Olefin/alkane mixture, the catalyst amount is 4% of the total weight of phenethyl alcohol and olefin, the mol ratio of the phenethyl alcohol to the olefin is 4:1, the reaction is carried out for 300min at 110 ℃, the reaction liquid is filtered, and then the unreacted raw material is removed by reduced pressure distillation to obtain C8-10Alkylphenylethanol, yield 81%; c8-10The alkyl phenethyl alcohol and the ethylene oxide are reacted (the molar ratio of the front material to the rear material is 1:9) to obtain C8-10Alkyl phenethyl alcohol polyoxyethylene ether (EO ═ 9).
Example 8: adding activated clay, phenethyl alcohol and hexadecanoic internal olefin into a reactor, wherein the dosage of a catalyst is 15 percent of the total weight of the phenethyl alcohol and the olefin, the molar ratio of the phenethyl alcohol to the olefin is 1:1, reacting for 60min at 180 ℃, filtering reaction liquid, and then removing unreacted phenethyl alcohol and olefin by reduced pressure distillation to obtain the hexadecyl phenethyl alcohol, wherein the yield is 70 percent; and reacting the hexadecylphenethyl alcohol with ethylene oxide (the molar ratio of the two materials is 1:18) to obtain hexadecyl phenethyl alcohol polyoxyethylene ether (EO ═ 18).
Example 9: adding perfluorinated sulfonic acid resin, phenethyl alcohol and C into a reactor20-24Olefin, the dosage of the catalyst is 10 percent of the total weight of the phenethyl alcohol and the olefin, the mol ratio of the phenethyl alcohol to the olefin is 3:1, the reaction is carried out for 120min at 160 ℃, reaction liquid is filtered, and then unreacted phenethyl alcohol and olefin are removed by reduced pressure distillation to obtain C20-24Alkyl phenyl ethanol, yield 50%; c20-24The alkyl phenethyl alcohol and the ethylene oxide are reacted (the molar ratio of the front material to the rear material is 1:20) to obtain C20-24Alkyl phenethyl alcohol polyoxyethylene ether (EO ═ 20).

Claims (3)

1. A method for preparing alkyl phenyl alcohol polyoxyethylene ether is characterized by comprising the following steps:
(1) alkylation
Adding olefin, benzyl alcohol or phenethyl alcohol and a solid acid catalyst into a reactor, wherein the dosage of the catalyst is 0.1-20% of the total mass of the olefin and the benzyl alcohol or the phenethyl alcohol, the molar ratio of the benzyl alcohol or the phenethyl alcohol to the olefin is 1:1-5:1, reacting at 80-200 ℃ for 10-300 min, filtering reaction liquid to remove the catalyst, and carrying out reduced pressure distillation to remove unreacted raw materials so as to obtain alkyl benzyl alcohol;
the solid acid catalyst is HY molecular sieve, perfluorinated sulfonic acid resin, activated clay or sulfated zirconia; the olefin is obtained by taking petrochemical products as raw materials, or an olefin/alkane mixture obtained by indirect liquefaction of coal and Fischer-Tropsch synthesis;
(2) Ethoxylation
Reacting alkyl phenyl alcohol with ethylene oxide to obtain alkyl phenyl alcohol polyoxyethylene ether; the ethoxylation process is carried out according to the prior process for preparing alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
2. The method of claim 1, wherein the olefin comprises an alpha-olefin or an internal olefin.
3. The method for preparing alkylphenyl alcohol polyoxyethylene ether as claimed in claim 2, wherein the carbon chain of the olefin is C8～C24Any one or a mixture of several of them.
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CN111039750B (en) * 2019-12-30 2020-12-22 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

Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1868984A (en) * 2005-05-24 2006-11-29 浙江工业大学 Preparation method of linear alkylbenzene
CN101234953A (en) * 2007-12-21 2008-08-06 王伟松 Method for synthesizing hexade/octode mixing alcohol polyoxyethylene
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
CN106187713A (en) * 2016-07-19 2016-12-07 南通市晗泰化工有限公司 Alkylbenzene methanol polyoxyethylene ether hydroxypropyl allyl ether and derivant and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1868984A (en) * 2005-05-24 2006-11-29 浙江工业大学 Preparation method of linear alkylbenzene
CN101234953A (en) * 2007-12-21 2008-08-06 王伟松 Method for synthesizing hexade/octode mixing alcohol polyoxyethylene
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
CN106187713A (en) * 2016-07-19 2016-12-07 南通市晗泰化工有限公司 Alkylbenzene methanol polyoxyethylene ether hydroxypropyl allyl ether and derivant and preparation method thereof

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