CN104326906A - Aryl alkyl carboxylic monoester and preparation method and application thereof - Google Patents

Aryl alkyl carboxylic monoester and preparation method and application thereof Download PDF

Info

Publication number
CN104326906A
CN104326906A CN201410467957.7A CN201410467957A CN104326906A CN 104326906 A CN104326906 A CN 104326906A CN 201410467957 A CN201410467957 A CN 201410467957A CN 104326906 A CN104326906 A CN 104326906A
Authority
CN
China
Prior art keywords
acid
carboxylic acids
monoesters
arylalkyl
arylalkyl carboxylic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410467957.7A
Other languages
Chinese (zh)
Other versions
CN104326906B (en
Inventor
刘春德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DALIAN DONGFANG INNOVATION SCIENCE & TECHNOLOGY Co Ltd
Original Assignee
DALIAN DONGFANG INNOVATION SCIENCE & TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DALIAN DONGFANG INNOVATION SCIENCE & TECHNOLOGY Co Ltd filed Critical DALIAN DONGFANG INNOVATION SCIENCE & TECHNOLOGY Co Ltd
Priority to CN201410467957.7A priority Critical patent/CN104326906B/en
Publication of CN104326906A publication Critical patent/CN104326906A/en
Application granted granted Critical
Publication of CN104326906B publication Critical patent/CN104326906B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/34—Esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/284—Esters of aromatic monocarboxylic acids
    • C10M2207/2845—Esters of aromatic monocarboxylic acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides aryl alkyl carboxylic monoester which has a structure as shown in the general formula I. According to a preparation method of aryl alkyl carboxylic monoester, alkylation between alkenyl carboxylic acid and aromatic hydrocarbon is carried out to obtain aryl alkyl carboxylic acid, and then esterification between aryl alkyl carboxylic acid and monohydric alcohol are carried out to obtain aryl alkyl carboxylic monoester. Or alkylation between alkenyl carboxylic methyl ester and aromatic hydrocarbon is carried out to obtain aryl alkyl carboxylic methyl ester, and transesterification between aryl alkyl carboxylic methyl ester and other monohydric alcohol can be carried out to obtain aryl alkyl carboxylic monoester with other structures.

Description

Arylalkyl carboxylic acids's monoesters and its preparation method and application
Technical field
The present invention relates to a kind of arylalkyl carboxylic acids's monoesters and preparation method thereof, be applied to the field such as lubricating oil, lubricant.
Background technology
The kind of fatty acid monoester is a lot, main as tensio-active agent, wetting agent, permeate agent, solubility promoter, water repellent agent, the tough agent of resin, the lubricant be used as in ore, cutting, textile oil class and rust-preventive agent had, as internal lubricant during many resin treatment.Fatty acid monoester can also be used as papermaking softening agent, advanced lubrication oil additive etc.
Fatty acid monoester is mainly derived from animal-plant oil, is with C 12to C 18lipid acid be main.
Conventional fatty acid monoester is as methyl stearate condensation point-2 DEG C, methyl behenate fusing point 54-56 DEG C, Witconol 2301 condensation point-19.9 DEG C, butyl stearate condensation point 20-22 DEG C, butyl oleate condensation point-26.4 DEG C etc.Can find out, the fusing point of saturated acid monoesters is very high, although and oleic acid condensation point is lower, double bond has extremely strong reactive behavior, can react in atmosphere with oxygen, make thermostability and oxidative stability poor.
Collateralization fatty acid ester, due to its splendid physical property, occupies and critical role in lube base wet goods field.But the synthesis technique of collateralization fatty acid ester is comparatively complicated, causes cost higher, is difficult to large-scale promotion.
The synthesis of carboxylic acid of the low condensation point of macromolecule and derivative thereof, have special purposes in some field.
United States Patent (USP) 5,440,059 and 5,840,942 describe and use acid clay as the dimethylbenzene of catalyzer and elaidin reaction, obtain arylalkyl carboxylic acids, but at high temperature reaction form a large amount of dimers and heavy acid.
United States Patent (USP) 5,840,942 disclose and a kind ofly prepare the lipid acid or the method for fatty acid ester that aryl replaces.The method relates to use zeolite or specific clay catalyst.
United States Patent (USP) 5,034,161 disclose by the toluene of the Nafion catalyst n R-50 catalysis deriving from E.I.du Pont, dimethylbenzene, reaction between phenol and oleic acid.
All these methods all have the shortcoming of low conversion rate, are difficult to realize industrialization.
Summary of the invention
Object of the present invention aims to provide a kind of arylalkyl carboxylic acids's monoesters, arylalkyl carboxylic acids's monoesters of the present invention, has following formula I structure:
Wherein: m+n is 0-30 positive integer,
P is 1-30 positive integer,
Q is the positive integer of 1 or 0;
R is phenyl, tolyl, m-xylene base, p-Xylol base, o-Xylol base, ethylbenzene, n-propyl phenyl, isopropyl phenyl, n-butylphenyl, isobutyl phenenyl, tert-butyl-phenyl, naphthyl, methyl naphthyl, dimethyl naphthyl, ethyl naphthyl, propyl group naphthyl, butyl naphthyl, xenyl, the one in phenylol.
Further, in technique scheme, described m+n is preferably 8,15,19, and more preferably 15, p be preferably 1-15 positive integer, q is preferably 1, R and is preferably m-xylene.
Further, in technique scheme, described arylalkyl carboxylic acids's monoesters, preferred structure is m-xylene base octadecane carboxylate, has following formula structure:
Wherein: m+n is 15 positive integers.
Further, in technique scheme, described arylalkyl carboxylic acids's monoesters, more preferably structure is the different monooctyl ester of m-xylene base octadecane carboxylic acid, has following formula structure:
Wherein: m+n is 15 positive integers.
Another object of the present invention is to provide the preparation method of above-mentioned arylalkyl carboxylic acids's monoesters, and technical scheme is under an acidic catalyst effect, the double bond generation Friedel-Crafts alkylation of aromatic hydrocarbon and alkene-carboxylic acid, synthesizes the arylalkyl carboxylic acids that general formula II is stated:
Wherein: m+n is 0-30 positive integer.
Arylalkyl carboxylic acids carries out esterification with monohydroxy-alcohol again, obtains arylalkyl carboxylic acids's monoesters of formula I.
Further, in technique scheme, the mol ratio of alkene-carboxylic acid and aromatic hydrocarbon, an acidic catalyst is 1:1.5 ~ 3.5:1.15 ~ 2.0; Temperature of reaction 100-135 DEG C.
Further, in technique scheme, the mol ratio of arylalkyl carboxylic acids and monohydroxy-alcohol is 1:1.05 ~ 8.0, and solid acid catalyst accounts for 0.3 ~ 3.0% of total quality of material, and metallic tin catalyst accounts for 0.3 ~ 2.0% of total quality of material.
Further, in technique scheme, described alkene-carboxylic acid is selected from undecylenic acid: CH 2=CH (CH 2) 8cOOH, oleic acid: CH 3(CH 2) 7cH=CH (CH 2) 7cOOH, erucic acid: one or more in cis-13-docosenoic acid, preferred oleic acid.
Further, in technique scheme, described monohydroxy-alcohol, preferred carbon number is the branched-chain alcoho of 3-9.
Further, in technique scheme, be describedly selected from benzene, toluene for aromatic hydrocarbon, m-xylene, p-Xylol, o-Xylol, ethylbenzene, n-propylbenzene, isopropyl benzene, n-butylbenzene, isobutyl-benzene, tert.-butylbenzene, naphthalene, methylnaphthalene, dimethylnaphthalene, ethyl naphthalene, propyl group naphthalene, dibutyl naphthalene, biphenyl, the one in phenol.
Further, in technique scheme, carry out under catalyst action by general formula II synthesisingtypeⅠcompound, described catalyzer is solid acid catalyst or metallic tin catalyst, described solid acid catalyst be selected from Zeo-karb, Supported on Zeolite liquid acid or metal-salt any one or a few, any one or a few in preferred D001-CC resin, HZSM-5 type molecular sieve, solid phosphoric acid, carbonyl solid acid, zirconium sulfate, D061 resin, HY, USY, ReY, H-Beta, mordenite, Lin Molybdenum acid, silicotungstic acid; Described metallic tin catalyst be selected from tin protoxide, tin protochloride or stannous oxalate any one or a few, the sub-tin of preferential oxidation.
The technical scheme that another prepares arylalkyl carboxylic acids's monoesters of the present invention is under an acidic catalyst effect, the double bond generation Friedel-Crafts alkylation of aromatic hydrocarbon and alkene-carboxylic acid's methyl esters, synthesizes arylalkyl carboxylic acids's methyl esters of following general formula III statement:
Wherein: m+n is 0-30 positive integer.
Arylalkyl carboxylic acids's methyl esters carries out transesterification reaction with other monohydroxy-alcohols again, obtains arylalkyl carboxylic acids's monoesters of formula I.Other monohydroxy-alcohols described are the monohydroxy-alcohol outside removing methyl alcohol.
Further, in technique scheme, the mol ratio of alkene-carboxylic acid's methyl esters and aromatic hydrocarbon, an acidic catalyst is 1:1.5 ~ 3.5:1.15 ~ 2.0 temperature of reaction 100-135 DEG C.
Further, in technique scheme, the mol ratio of arylalkyl carboxylic acids's methyl esters and other monohydroxy-alcohols is 1:1.05 ~ 8.0, and solid acid catalyst accounts for 0.3 ~ 3.0% of total quality of material, and metallic tin catalyst accounts for 0.3 ~ 2.0% of total quality of material.
Further, in technique scheme, described alkene-carboxylic acid's methyl esters be selected from methyl undecylenate, Witconol 2301, methyl erucate one or more, preferred Witconol 2301.
Further, in technique scheme, described monohydroxy-alcohol, preferred carbon number is the branched-chain alcoho of 3-9.
Further, in technique scheme, carry out under catalyst action by general formula III synthesisingtypeⅠcompound, described catalyzer is solid acid or alkaline catalysts or organotin catalysts, described solid acid alkali catalytic agent be selected from sodium methylate, sodium ethylate, salt of wormwood, sodium carbonate, potassium hydroxide, sodium hydroxide, sulfuric acid or potassium sulfate any one or a few; Described organotin catalysts be selected from Monobutyltin, stannous octoate, tin methide, dioctyl tin, tin tetraphenyl any one or a few, particular methanol sodium.
Further, in technique scheme, synthesis general formula II, III state that compound an acidic catalyst used is selected from sulfuric acid, hydrofluoric acid, methylsulphonic acid, trifluoromethanesulfonic acid, the trifluoromethanesulfonic acid root of metal salts of trifluoromethane sulphonic acid or load, heteropolyacid, solid super-strong acid, acid zeolite, perfluorinated resin, ionic liquid any one or a few, the trifluoromethanesulfonic acid root of preferable methyl sulfonic acid, metal salts of trifluoromethane sulphonic acid or load, more preferably methylsulphonic acid.
Further, in technique scheme, the R in formula I, general formula II, general formula III, preferred m-xylene.
Another object of the present invention is to provide the application of a kind of arylalkyl carboxylic acids's monoesters described above in tensio-active agent, wetting agent, permeate agent, solubility promoter, water repellent agent, the tough agent of resin, lubricant, papermaking softening agent, advanced lubrication oil additive.
Beneficial outcomes of the present invention is:
1. arylalkyl carboxylic acids's monoesters of the present invention solves the defect of double bond poor stability, and thermostability and oxidative stability are largely increased;
2. arylalkyl carboxylic acids's monoesters condensation point of the present invention is lower than-30 DEG C, and Application Areas is expanded further;
3. arylalkyl carboxylic acids's monoesters of the present invention is due to the impact of phenyl ring, and kinematic viscosity is comparatively large, and compound property is good;
4. arylalkyl carboxylic acids's monoesters preparation method transformation efficiency of the present invention is high, is applicable to industrialization and produces.
Accompanying drawing explanation
Accompanying drawing 4 width of the present invention,
Fig. 1 is the infrared spectrogram of the m-xylene base octadecane carboxylic acid that embodiment 1 prepares;
Fig. 2 is the m-xylene base octadecane carboxylate methyl ester infrared spectrogram that embodiment 2 prepares;
Fig. 3 is the m-xylene base octadecane carboxylate infrared spectrogram that embodiment 1 prepares;
Fig. 4 is the different monooctyl ester infrared spectrogram of m-xylene base octadecane carboxylic acid that embodiment 2 prepares.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but not as a limitation of the invention.
Embodiment 1
The preparation method of m-xylene base octadecane carboxylate, comprises the following steps:
1. Friedel-Crafts alkylation:
1. reaction formula
Wherein: m+n=15.
2. raw material specification
Technical grade high-purity oleic acid C18:1 content>=75.0%, iodine number (gI 2/ 100g) 80-100, water content≤0.5%, peroxide value≤10 (mg/Kg).
Technical grade methyl sulfonic acid, clear, content >=98.0%, ion content≤100ppm.
Technical grade m-xylene, content >=99.0%.
3. proportioning raw materials
Oleic acid: methylsulphonic acid: m-xylene=1:1.5:3.0 (mol ratio).
4. synthesis technique
In sealing 2000 liters of enamel reaction stills; inflated with nitrogen displaced air; add 496.9 kilograms of m-xylenes and 225 kilograms of methylsulphonic acids; reactor inflated with nitrogen is protected, and stirs, is warming up to 125 DEG C; start constant speed and add industrial high-purity oleic acid; control temperature of reaction at 130 DEG C, within 5 hours, add 440.6 kilograms of high-purity oleic acid of industry altogether, oleic acid adds rear continuation reaction 2h.
5. post-treating method
Under being cooled to room temperature, material being proceeded in another 3000 liters of enamel reaction stills, under whipped state, slowly add 200 kilograms of deionized waters, the deionized water joining day is at about 60min, then continue to stir about 60min, static more than 2 hours, separate lower layer of water and methylsulphonic acid.
The water separated and methylsulphonic acid reclaim methylsulphonic acid by falling film evaporation thickening and rectifying, and the methylsulphonic acid of recovery recycles.
Reaction mass deionized water agitator treating three times, neutral to pH value.
Material falling liquid film after washing steams m-xylene and residual water, and after natural layering, m-xylene recycles.
Material removes unreacted oleic acid (comprising saturated fatty acid) through molecular distillation, vacuum tightness 1Pa, temperature 150 DEG C.
Material, through molecular distillation decolouring (vacuum tightness 1Pa, temperature 210 DEG C), obtains m-xylene base octadecane carboxylic acid.
Gas-chromatography and liquid-phase chromatographic analysis, oleic acid conversion >=93%.
6. structural characterization and product property
M-xylene base octadecane carboxylic acid infrared spectrogram is shown in Fig. 1.
At Fig. 1, we can see 1710cm -1(carboxylic acid dimerization C=O stretching vibration), 1614cm -1(carboxylate radical COO antisymmetric stretching vibration), 1412cm -1(carboxylate radical COO symmetrical stretching vibration), 1284cm -1(carboxylic acid C-OH stretching vibration, 1047cm -1(lactone C-O-C symmetrical stretching vibration), 938cm -1(carboxylic acid COH out-of-plane deformation vibration); 1502cm -1(phenyl ring skeleton C=C stretching vibration), 877cm -1(phenyl ring having isolated hydrogen), 817cm -1(phenyl ring skeleton C=C out-of-plane deformation vibration), 725cm -1(between on phenyl ring disubstituted C-H out-of-plane deformation vibration); 2925cm -1(CH 2alkane antisymmetric stretching vibration), 2853cm -1(CH 2alkane symmetrical stretching vibration), 1463cm -1(CH 2alkane angle vibrate), 1377cm -1(CH 3symmetric deformation vibrates).
M-xylene base octadecane carboxylic acid indices: content>=95%, iodine number≤10 (gI 2/ 100g), pour point-21 DEG C, flash-point 238 DEG C (opening), density 0.923 (g/cm 2).
2. esterification:
1. reaction formula
Wherein: m+n=15.
2. raw material specification
M-xylene base octadecane carboxylic acid: content>=95%, iodine number≤10 (gI 2/ 100g), pour point-21 DEG C, flash-point 238 DEG C (opening), density 0.923 (g/cm 2).
Technical grade isopropylcarbinol, content >=98%, moisture≤0.1%.
Technical grade tin protoxide, content >=90%.
3. proportioning raw materials
Initially feed intake: m-xylene base octadecane carboxylic acid: isopropylcarbinol=1:3.0 (mol ratio), tin protoxide is 0.8% of total quality of material.
4. synthesis technique
2000 liters of reactor band reflux exchangers and feed supplementing device, add 700 kilograms of m-xylene base octadecane carboxylic acids, 400 kilograms of isopropylcarbinols, 10 kilograms of tin protoxides respectively, 115 DEG C ~ 135 DEG C stirring reactions, condenser reclaims the isopropylcarbinol and water that evaporate, supplement the isopropylcarbinol of equal quality toward reactor according to the amount interval of the isopropylcarbinol evaporated and water, detect the acid number of product, stopped reaction when product acid number≤0.5 (mgKOH/g).
5. post-treating method
Thick product is crossed and is filtered tin protoxide.
Isopropylcarbinol in falling liquid film removing product and residuary water, the mixture of isopropylcarbinol and water in rectifying separation building-up process, isopropylcarbinol recycles.
Product, through molecular distillation decolouring (vacuum tightness 1Pa, temperature 230 DEG C), obtains m-xylene base octadecane carboxylate.
6. structural characterization and product property
M-xylene base octadecane carboxylate infrared spectrogram is shown in Fig. 3.
At Fig. 3, we can see 1739cm -1(ester carbonyl group C=O stretching vibration), 1171cm -1(fatty acid ester C-O-C antisymmetric stretching vibration), 1116cm -1((CH 3) 2cHR stretching vibration), 1011cm -1(fatty acid ester C-O-C symmetrical stretching vibration; 1502cm -1(phenyl ring skeleton C=C stretching vibration), 872cm -1(phenyl ring having isolated hydrogen), 817cm -1(phenyl ring skeleton C=C out-of-plane deformation vibration), 722cm -1(between on phenyl ring disubstituted C-H out-of-plane deformation vibration); 2925cm -1(CH 2alkane antisymmetric stretching vibration), 2854cm -1(CH 2alkane symmetrical stretching vibration), 1465cm -1(CH 2alkane angle vibrate), 1378cm -1 (CH 3symmetric deformation vibrates).
M-xylene base octadecane carboxylate indices: content>=95%, acid number≤0.5 (mgKOH/g), iodine number≤10 (gI 2/ 100g), pour point-33 DEG C, flash-point 258 DEG C (opening), density 0.88 (g/cm 2), kinematic viscosity (40 DEG C of mm/s) 37.61, kinematic viscosity (100 DEG C of mm/s) 5.99, viscosity index 103.
Embodiment 2.
The preparation method of the different monooctyl ester of m-xylene base octadecane carboxylic acid, comprises the following steps:
1. Friedel-Crafts alkylation:
Wherein: m+n=15.
2. raw material specification
The high-purity Witconol 2301 of technical grade: C18:1 content>=75.0%, iodine number (gI 2/ 100g) 80-100, moisture≤0.5%, acid number≤0.5 (mgKOH/g), peroxide value≤10 (mg/Kg).
Technical grade methyl sulfonic acid, clear, content >=98.0%, ion content≤100ppm.
Technical grade m-xylene, content >=99.0%.
3. proportioning raw materials
Witconol 2301: methylsulphonic acid: m-xylene=1:1.5:3.0 (mol ratio).
4. synthesis technique
In sealing 2000 liters of enamel reaction stills; inflated with nitrogen displaced air; add 496.9 kilograms of m-xylenes and 225 kilograms of methylsulphonic acids; reactor inflated with nitrogen is protected, and stirs, is warming up to 125 DEG C; start constant speed and add industrial high-purity Witconol 2301; control temperature of reaction at 130 DEG C, within 5 hours, add 462.5 kilograms of high-purity Witconol 2301s of industry altogether, Witconol 2301 adds rear continuation reaction 2h.
5. post-treating method
Under being cooled to room temperature, material being proceeded in another 3000 liters of enamel reaction stills, under whipped state, slowly add 200 kilograms of deionized waters, the deionized water joining day is at about 60min, then continue to stir about 60min, static more than 2 hours, separate lower layer of water and methylsulphonic acid.
The water separated and methylsulphonic acid reclaim methylsulphonic acid by falling film evaporation thickening and rectifying, and the methylsulphonic acid of recovery recycles.
Reaction mass deionized water agitator treating three times, neutral to pH value.
Material falling liquid film after washing steams m-xylene and residual water, and after natural layering, m-xylene recycles.
Material removes unreacted Witconol 2301 (comprising saturated fatty acid methyl ester) through molecular distillation, vacuum tightness 1Pa, temperature 140 DEG C.
Material, through molecular distillation decolouring (vacuum tightness 1Pa, temperature 200 DEG C), obtains m-xylene base octadecane carboxylate methyl ester.
Gas-chromatography and liquid-phase chromatographic analysis, Witconol 2301 transformation efficiency >=93%.
6. structural characterization and product property
M-xylene base octadecane carboxylate methyl ester infrared spectrogram is shown in Fig. 2.
At Fig. 2, we can see 1742cm -1(carboxylicesters C=O stretching vibration), 1436cm -1(carboxylate radical COO symmetrical stretching vibration), 1170cm -1(high carboxylic acid's ester C-O-C antisymmetric stretching vibration, 1031cm -1(fatty acid ester C-O-C symmetrical stretching vibration); 1502cm -1(phenyl ring skeleton C=C stretching vibration), 873cm -1(phenyl ring having isolated hydrogen), 817cm -1(phenyl ring skeleton C=C out-of-plane deformation vibration), 723cm -1(between on phenyl ring disubstituted C-H out-of-plane deformation vibration); 2925cm -1(CH 2alkane antisymmetric stretching vibration), 2853cm -1(CH 2alkane symmetrical stretching vibration) 1462cm -1(CH 2alkane angle vibrate), 1376cm -1(CH 3symmetric deformation vibrates).
M-xylene base octadecane carboxylate methyl ester indices: content>=95%, acid number≤0.5 (mgKOH/g), iodine number≤10 (gI 2/ 100g), pour point-24 DEG C, flash-point 226 DEG C (opening), density 0.895 (g/cm 2), kinematic viscosity (40 DEG C of mm/s) 30.21, kinematic viscosity (100 DEG C of mm/s) 5.25, viscosity index 100.
1. reaction formula
Wherein: m+n=15.
2. raw material specification
M-xylene base octadecane carboxylate methyl ester indices: content>=95%, acid number≤0.5 (mgKOH/g), iodine number≤10 (gI 2/ 100g).
Technical grade isooctyl alcohol content >=98% moisture≤0.1%.
Industrial grade benzenemethanol sodium content >=50%.
3. proportioning raw materials
M-xylene base octadecane carboxylate methyl ester: isooctyl alcohol=1:3.0 (mol ratio), sodium methylate is 1.0% of total quality of material.
4. synthesis technique
2000 liters of reactor band reflux exchangers, add 604 kilograms of m-xylene base octadecane carboxylate methyl esters, 586 kilograms of isooctyl alcohol, 23.78 kilograms of sodium methylates (50% content) respectively, 125 DEG C ~ 135 DEG C stirring reactions, condenser reclaims the methyl alcohol evaporated, detect the acid number of product, stopped reaction when product acid number≤0.5 (mgKOH/g).
5. post-treating method
Thick product solids removed by filtration.
Falling film evaporation removes excessive isooctyl alcohol.
Product, through molecular distillation decolouring (vacuum tightness 1Pa, temperature 260 DEG C), obtains the different monooctyl ester of m-xylene base octadecane carboxylic acid.
6. structural characterization and product property
The different monooctyl ester infrared spectrogram of m-xylene base octadecane carboxylic acid is shown in Fig. 4.
At Fig. 4, we can see 1738cm -1(ester carbonyl group C=O stretching vibration), 1244cm -1((CH 3) 2cR antisymmetric stretching vibration), 1172cm -1(fatty acid ester C-O-C antisymmetric stretching vibration), 1118cm -1((CH 3) 2cHR stretching vibration), 1030cm -1(fatty acid ester C-O-C symmetrical stretching vibration; 1502cm -1(phenyl ring skeleton C=C stretching vibration), 817cm -1(phenyl ring skeleton C=C out-of-plane deformation vibration), 724cm -1(between on phenyl ring disubstituted C-H out-of-plane deformation vibration); 2926cm -1(CH 2alkane antisymmetric stretching vibration), 2854cm -1(CH 2alkane symmetrical stretching vibration), 1463cm -1(CH 2alkane angle vibrate), 1378cm -1(CH 3symmetric deformation vibrates).
The different monooctyl ester indices of m-xylene base octadecane carboxylic acid: content>=95%, acid number≤0.5 (mgKOH/g), iodine number≤10 (gI 2/ 100g), pour point-37 DEG C, flash-point 268 DEG C (opening), density 0.865 (g/cm 2), kinematic viscosity (40 DEG C of mm/s) 46.61, kinematic viscosity (100 DEG C of mm/s) 7.204, viscosity index 114.
Application examples 1
The different monooctyl ester of m-xylene base octadecanoic acid is as the parameter comparison of high viscosity ester base oil:
Pour point is the most common index of low temperature behavior, and arylalkyl carboxylic acids's monoesters has high pour point when not adding pour point reducer.
The viscosity index of arylalkyl carboxylic acids's ester has exceeded 100, may not need to add thickening material when configuring lubricating oil, and the existence of polymer-based carbon thickening material or activator may cause shear stable sex chromosome mosaicism in the lubricating oil of configuration.
Usually, expect that arylalkyl carboxylic acids's monoesters of the present invention has the advantage being better than other plant based lubricating oil in their oxidative stability and low-temperature performance.

Claims (14)

1. arylalkyl carboxylic acids's monoesters, is characterized in that having formula I structure:
Wherein: m+n is 0-30 positive integer, p is 1-30 positive integer, and q is the positive integer of 1 or 0;
R is phenyl, tolyl, m-xylene base, p-Xylol base, o-Xylol base, ethylbenzene, n-propyl phenyl, isopropyl phenyl, n-butylphenyl, isobutyl phenenyl, tert-butyl-phenyl, naphthyl, methyl naphthyl, dimethyl naphthyl, ethyl naphthyl, propyl group naphthyl, butyl naphthyl, xenyl, the one in phenylol.
2. arylalkyl carboxylic acids's monoesters according to claim 1, is characterized in that: described m+n is 8,15,19, p is 1-15 positive integer, and q is 1, R is m-xylene.
3. arylalkyl carboxylic acids's monoesters according to claim 1 and 2, is characterized in that: comprise m-xylene base octadecane carboxylate, the different monooctyl ester of m-xylene base octadecane carboxylic acid, as shown in the formula structure:
Wherein: m+n is the positive integer of 15.
4. the preparation method of a kind of arylalkyl carboxylic acids's monoesters as claimed in claim 1 or 2, is characterized in that: comprise the following steps:
Friedel-Crafts alkylation: the alkylated reaction that alkene-carboxylic acid and aromatic hydrocarbon carry out under an acidic catalyst effect, obtains arylalkyl carboxylic acids;
Esterification: again by the dehydration condensation that arylalkyl carboxylic acids and monohydroxy-alcohol carry out under solid acid catalyst or metallic tin catalyst effect, obtain arylalkyl carboxylic acids's monoesters.
5. the preparation method of a kind of arylalkyl carboxylic acids's monoesters according to claim 4, is characterized in that: described alkene-carboxylic acid be selected from undecylenic acid, oleic acid, erucic acid one or more; Described monohydroxy-alcohol is selected from the branched-chain alcoho that carbon number is 3-9.
6. the preparation method of a kind of arylalkyl carboxylic acids's monoesters according to claim 4, is characterized in that: described an acidic catalyst be selected from sulfuric acid, hydrofluoric acid, methylsulphonic acid, trifluoromethanesulfonic acid, the trifluoromethanesulfonic acid root of metal salts of trifluoromethane sulphonic acid or load, heteropolyacid, solid super-strong acid, acid zeolite, perfluorinated resin, ionic liquid any one or a few.
7. the preparation method of a kind of arylalkyl carboxylic acids's monoesters according to claim 4, is characterized in that: described solid acid catalyst be selected from Zeo-karb, Supported on Zeolite liquid acid or metal-salt any one or a few; Described metallic tin catalyst be selected from tin protoxide, tin protochloride or stannous oxalate any one.
8. the preparation method of a kind of arylalkyl carboxylic acids's monoesters according to claim 4, is characterized in that: comprise the alkylated reaction that oleic acid and m-xylene carry out under methylsulphonic acid catalysis, reaction formula is as follows:
Wherein: m+n is=15.
9. a kind of preparation method of arylalkyl carboxylic acids's monoesters according to claim 1 or 2, is characterized in that: comprise the following steps:
Friedel-Crafts alkylation: the alkylated reaction that alkene-carboxylic acid's methyl esters and aromatic hydrocarbon carry out under an acidic catalyst effect, obtains arylalkyl carboxylic acids's methyl esters;
Transesterification reaction: arylalkyl carboxylic acids's methyl esters carries out transesterification reaction with other monohydroxy-alcohols under solid alkali acid catalyst or organotin catalysts catalysis, obtains arylalkyl carboxylic acids's monoesters of other structures.
10. the preparation method of a kind of arylalkyl carboxylic acids's monoesters according to claim 9, is characterized in that: described alkene-carboxylic acid's methyl esters be selected from methyl undecylenate, Witconol 2301, methyl erucate one or more; Described monohydroxy-alcohol is selected from the branched-chain alcoho that carbon number is 3-9.
The preparation method of 11. a kind of arylalkyl carboxylic acids's monoesters according to claim 9, is characterized in that: described an acidic catalyst be selected from sulfuric acid, hydrofluoric acid, methylsulphonic acid, trifluoromethanesulfonic acid, the trifluoromethanesulfonic acid root of metal salts of trifluoromethane sulphonic acid or load, heteropolyacid, solid super-strong acid, acid zeolite, perfluorinated resin, ionic liquid any one or a few.
The preparation method of 12. a kind of arylalkyl carboxylic acids's monoesters according to claim 9, it is characterized in that: described solid acid alkali catalytic agent be selected from sodium methylate, sodium ethylate, salt of wormwood, sodium carbonate, potassium hydroxide, sodium hydroxide, sulfuric acid or potassium sulfate any one, described organotin catalysts be selected from Monobutyltin, stannous octoate, tin methide, dioctyl tin, tin tetraphenyl any one or a few.
The preparation method of 13. a kind of arylalkyl carboxylic acids's monoesters according to claim 9, is characterized in that: comprise the alkylated reaction that Witconol 2301 and m-xylene carry out under methylsulphonic acid catalysis, reaction formula is as follows:
Wherein: m+n is 15.
14. application of arylalkyl carboxylic acids's monoesters as claimed in claim 1 or 2 in tensio-active agent, wetting agent, permeate agent, solubility promoter, water repellent agent, the tough agent of resin, lubricant, papermaking softening agent, advanced lubrication oil additive.
CN201410467957.7A 2014-09-12 2014-09-12 Arylalkyl carboxylic acids's monoesters and its preparation method and application Expired - Fee Related CN104326906B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410467957.7A CN104326906B (en) 2014-09-12 2014-09-12 Arylalkyl carboxylic acids's monoesters and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410467957.7A CN104326906B (en) 2014-09-12 2014-09-12 Arylalkyl carboxylic acids's monoesters and its preparation method and application

Publications (2)

Publication Number Publication Date
CN104326906A true CN104326906A (en) 2015-02-04
CN104326906B CN104326906B (en) 2016-08-17

Family

ID=52401732

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410467957.7A Expired - Fee Related CN104326906B (en) 2014-09-12 2014-09-12 Arylalkyl carboxylic acids's monoesters and its preparation method and application

Country Status (1)

Country Link
CN (1) CN104326906B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114507138A (en) * 2020-10-28 2022-05-17 中国石油化工股份有限公司 Ester compound and preparation method and application thereof
CN115992020A (en) * 2021-10-18 2023-04-21 中国石油化工股份有限公司 Industrial lubricating oil composition and preparation method thereof
CN115992025A (en) * 2021-10-18 2023-04-21 中国石油化工股份有限公司 Hydraulic oil composition and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102531846A (en) * 2010-12-17 2012-07-04 中国石油天然气股份有限公司 Aryl fatty alcohol and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102531846A (en) * 2010-12-17 2012-07-04 中国石油天然气股份有限公司 Aryl fatty alcohol and preparation method thereof

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
BOOTS, SHARON G.等: "Hypocholesterolemic agents. V: inhibition of β-hydroxy-β-methylglutaryl coenzyme A reductase by substituted 4-biphenylylalkyl carboxylic acids and methyl esters", 《JOURNAL OF PHARMACEUTICAL SCIENCES 》 *
BOOTS, SHARON G.等: "Hypocholesterolemic agents. V: inhibition of β-hydroxy-β-methylglutaryl coenzyme A reductase by substituted 4-biphenylylalkyl carboxylic acids and methyl esters", 《JOURNAL OF PHARMACEUTICAL SCIENCES》 *
EWEISS, N. F.: "Esters of isomeric arylundecanoic acids", 《JOURNAL OF THE UNIVERSITY OF KUWAIT, SCIENCE》 *
EWEISS, N. F.: "Esters of isomeric arylundecanoic acids", 《JOURNAL OF THE UNIVERSITY OF KUWAIT, SCIENCE》, vol. 9, no. 2, 31 December 1982 (1982-12-31) *
IONESCU 等: "(Phenolation of vegetable oils", 《JOURNAL OF THE SERBIAN CHEMICAL SOCIETY》 *
IONESCU 等: "Phenolation of vegetable oils", 《JOURNAL OF THE SERBIAN CHEMICAL SOCIETY》 *
于涛等: "芳基油酸酰胺羟丙基磺基甜菜碱的合成及性能", 《应用化学》 *
于涛等: "芳基油酸酰胺羟丙基磺基甜菜碱的合成及性能", 《应用化学》, vol. 21, no. 11, 30 November 2012 (2012-11-30) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114507138A (en) * 2020-10-28 2022-05-17 中国石油化工股份有限公司 Ester compound and preparation method and application thereof
CN115992020A (en) * 2021-10-18 2023-04-21 中国石油化工股份有限公司 Industrial lubricating oil composition and preparation method thereof
CN115992025A (en) * 2021-10-18 2023-04-21 中国石油化工股份有限公司 Hydraulic oil composition and preparation method thereof

Also Published As

Publication number Publication date
CN104326906B (en) 2016-08-17

Similar Documents

Publication Publication Date Title
Gholami et al. Dealing with the surplus of glycerol production from biodiesel industry through catalytic upgrading to polyglycerols and other value-added products
WO2007088702A1 (en) Process for production of fatty acid alkyl ester and production apparatus for fatty acid alkyl ester
CN102093164B (en) Method for simultaneously preparing glycol and carbonate by catalysis
WO2016166421A1 (en) Method of producing furan carboxylates from aldaric acids by using solid heterogeneous catalysts
CN101225028A (en) Preparation method of alkyl aromatic aldehyde
CN104326906A (en) Aryl alkyl carboxylic monoester and preparation method and application thereof
CN113788793B (en) Sulfonic acid functionalized imidazole ionic liquid catalyst and preparation method and application thereof
CN104231257B (en) A kind of aryl alkyl alcohol polyoxyethylene polyoxypropylene block copolymer and its preparation method and application
CN104355994B (en) A kind of aryl alkyl polyols ester and application thereof
CN101172253B (en) Esterification catalysts and esterification process of organic acid
CN108250053B (en) Method and system for preparing glycerin alkyl ether
CN101024613B (en) Method for catalyzing alochol acid esterization by sulfonic-acid-radical functionized ion liquid
Zhang et al. A review on biodiesel production by transesterification catalyzed by ionic liquid catalysts
CN103965016A (en) Method for preparing fatty alcohol through hydrogenation of fatty acid methyl ester in presence of temperature control catalytic system
CN104447324A (en) Arylalkyl methacrylate as well as preparation method and application thereof
CN109134247B (en) Preparation method and system of pentaerythritol ester
CN101024612B (en) Method for catalyzing alcohol acid esterization by acidic ion liquid
CN104326905B (en) A kind of aryl alkyl carboxylic acid polyoxyethylene ester and its preparation method and application
US20210363095A1 (en) Method capable of realizing preparation and in-situ separation of oligomeric ricinoleate
CN104262602A (en) Aryl alkyl carboxylic acid polyoxypropylene polyoxyethylene block copolymer, and preparation method and application thereof
US9255218B2 (en) Method for obtaining compositions of biosolvents by esterification and obtained compositions of biosolvents
CN107400230A (en) A kind of high efficient cryogenic petroleum demulsifier and preparation method
Zhang et al. Esterification of salicylic acid using Ce4+ modified cation-exchange resin as catalyst
CN104370729A (en) Synthesis method and system for aryl alkyl carboxylic acid (methyl ester)
CN111848402A (en) Preparation method and application of carboxylic acid isooctyl alcohol ester

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160817

Termination date: 20210912