CN104326906B - Arylalkyl carboxylic acids's monoesters and its preparation method and application - Google Patents

Arylalkyl carboxylic acids's monoesters and its preparation method and application Download PDF

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CN104326906B
CN104326906B CN201410467957.7A CN201410467957A CN104326906B CN 104326906 B CN104326906 B CN 104326906B CN 201410467957 A CN201410467957 A CN 201410467957A CN 104326906 B CN104326906 B CN 104326906B
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acid
carboxylic acids
monoesters
arylalkyl
arylalkyl carboxylic
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CN104326906A (en
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刘春德
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DALIAN DONGFANG INNOVATION SCIENCE & TECHNOLOGY Co Ltd
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    • 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

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Abstract

The present invention provides a kind of arylalkyl carboxylic acids's monoesters, there is logical structure shown in formula I, preparation method be arylalkyl carboxylic acids's monoesters be that alkene-carboxylic acid and aromatic hydrocarbon are alkylated, obtain arylalkyl carboxylic acids, again arylalkyl carboxylic acids is esterified with monohydric alcohol, obtains arylalkyl carboxylic acids's monoesters；Can also be alkylated with aromatic hydrocarbon by alkene-carboxylic acid's methyl esters, obtain arylalkyl carboxylic acids's methyl esters, arylalkyl carboxylic acids's methyl esters also can carry out ester exchange with other monohydric alcohols, obtains arylalkyl carboxylic acids's monoesters of 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, is mainly used as surfactant, wetting agent, bleeding agent, cosolvent, water resistant Agent, the tough agent of resin, have as the lubricant in ore, cutting, textile oil class and antirust agent, be used as many trees Fat adds the in-lubricant in man-hour.Fatty-acid monoester is also used as papermaking plasticizer, advanced lubrication oil additive etc..
Fatty-acid monoester is mainly derived from animal and plant fat, is with C12To C18Aliphatic acid be main.
Conventional fatty-acid monoester such as methyl stearate condensation point-2 DEG C, methyl behenate fusing point 54-56 DEG C, oleic acid Methyl esters condensation point-19.9 DEG C, butyl stearate condensation point 20-22 DEG C, butyl oleate condensation point-26.4 DEG C etc..It can be seen that The fusing point of saturated acid monoesters is the highest, although and oleic acid condensation point is relatively low, but double bond has extremely strong reactivity, in atmosphere Can react with oxygen so that heat endurance and oxidation stability are poor.
Collateralization fatty acid ester, due to its splendid physical characteristic, occupies and critical role in fields such as lube base oils. But, the synthesis technique of collateralization fatty acid ester is complex, causes relatively costly, it 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 describes and uses acid clay as the dimethylbenzene of catalyst with oily Acid reaction, obtains arylalkyl carboxylic acids, but at high temperature reaction forms substantial amounts of dimer and heavy acid.
United States Patent (USP) 5,840,942 discloses a kind of prepares the substituted aliphatic acid of aryl or the method for fatty acid ester.The party Method is directed to use with zeolite or specific clay catalyst.
United States Patent (USP) 5,034,161 discloses the first being catalyzed by the Nafion catalyst n R-50 deriving from E.I.du Pont Reaction between benzene, dimethylbenzene, phenol and oleic acid.
All these methods all have the shortcoming that conversion ratio is low, it is difficult to realize industrialization.
Summary of the invention
The purpose of the present invention aims to provide a kind of arylalkyl carboxylic acids's monoesters, arylalkyl carboxylic acids's monoesters of the present invention, tool There is below general 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, meta-xylene base, paraxylene base, ortho-xylene base, ethylbenzene, n-propylbenzene Base, 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, more preferably 15, and p is preferred For 1-15 positive integer, q is preferably 1, and R is preferably meta-xylene.
Further, in technique scheme, described arylalkyl carboxylic acids's monoesters, preferred structure is meta-xylene base Octadecane carboxylate, has a formula:
Wherein: m+n is 15 positive integers.
Further, in technique scheme, described arylalkyl carboxylic acids's monoesters, diformazan between more preferably structure is The different monooctyl ester of phenyl octadecane carboxylic acid, has a formula:
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 in acidity Under catalyst action, aromatic hydrocarbon and the double bond generation Friedel-Crafts alkylation of alkene-carboxylic acid, synthesize formula II statement Arylalkyl carboxylic acids:
Wherein: m+n is 0-30 positive integer.
Arylalkyl carboxylic acids carries out esterification with monohydric alcohol again, obtains arylalkyl carboxylic acids's monoesters of formula I.
Further, in technique scheme, alkene-carboxylic acid and aromatic hydrocarbon, the mol ratio of acidic catalyst be 1:1.5～ 3.5:1.15～2.0；Reaction temperature 100-135 DEG C.
Further, in technique scheme, arylalkyl carboxylic acids is 1:1.05～8.0 with the mol ratio of monohydric alcohol, Solid acid catalyst accounts for the 0.3～3.0% of total quality of material, metallic tin catalyst account for total quality of material 0.3～ 2.0%.
Further, in technique scheme, described alkene-carboxylic acid is selected from undecenoic acid: CH2=CH (CH2)8COOH, oleic acid: CH3(CH2)7CH=CH (CH2)7COOH, erucic acid: cis One or more in-13-docosenoic acid, preferably oleic acid.
Further, in technique scheme, described monohydric alcohol, preferably carbon number are the branched-chain alcoho of 3-9.
Further, in technique scheme, described for aromatic hydrocarbon selected from benzene, toluene, meta-xylene, to diformazan Benzene, ortho-xylene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, isobutyl-benzene, tert-butyl benzene, naphthalene, Methyl naphthalene, dimethylnaphthalene, ethylnaphthalene, propyl group naphthalene, dibutyl naphthalene, biphenyl, the one in phenol.
Further, in technique scheme, formula II synthesisingtypeⅠcompound it is to enter under catalyst action OK, described catalyst is solid acid catalyst or metallic tin catalyst, and described solid acid catalyst is selected from cation Any one or a few in exchanger resin, Supported on Zeolite liquid acid or slaine, preferably D001-CC resin, HZSM-5 type molecular sieve, solid phosphoric acid, carbonyl solid acid, zirconium sulfate, D061 resin, HY, USY, ReY, Any one or a few in H-Beta, modenite, phosphoric acid, silico-tungstic acid；Described metallic tin catalyst is selected from Any one or a few in stannous oxide, stannous chloride or stannous oxalate, preferential oxidation stannous.
Another technical scheme preparing arylalkyl carboxylic acids's monoesters of the present invention is under acidic catalyst effect, aromatic hydrocarbon With the double bond generation Friedel-Crafts alkylation of alkene-carboxylic acid's methyl esters, synthesize the arylalkyl carboxylic acids of below general formula III statement Methyl esters:
Wherein: m+n is 0-30 positive integer.
Arylalkyl carboxylic acids's methyl esters carries out ester exchange reaction with other monohydric alcohols again, obtains the arylalkyl carboxylic acids of formula I Monoesters.Other monohydric alcohols described are to remove the monohydric alcohol outside methyl alcohol.
Further, in technique scheme, alkene-carboxylic acid's methyl esters with the mol ratio of aromatic hydrocarbon, acidic catalyst is 1:1.5～3.5:1.15～2.0 reaction temperatures 100-135 DEG C.
Further, in technique scheme, arylalkyl carboxylic acids's methyl esters with the mol ratio of other monohydric alcohols is 1:1.05～8.0, solid acid catalyst accounts for the 0.3～3.0% of total quality of material, and metallic tin catalyst accounts for total material matter The 0.3～2.0% of amount.
Further, in technique scheme, described alkene-carboxylic acid's methyl esters is selected from methyl undecylenate, oleic acid first One or more in ester, methyl erucate, preferably methyl oleate.
Further, in technique scheme, described monohydric alcohol, preferably carbon number are the branched-chain alcoho of 3-9.
Further, in technique scheme, general formula III synthesisingtypeⅠcompound it is to enter under catalyst action OK, described catalyst is solid acid or base catalyst or organotin catalysts, and described solid acid alkali catalytic agent is selected from methyl alcohol In sodium, caustic alcohol, potassium carbonate, sodium carbonate, potassium hydroxide, NaOH, sulfuric acid or potassium sulfate any one or Several；Described organotin catalysts is selected from Monobutyltin, stannous octoate, stannous methide, dioctyl tin, tetraphenyltin In any one or a few, preferably sodium methoxide.
Further, in technique scheme, synthesis formula II, III statement acidic catalyst choosing used by compound From the TFMS root of sulfuric acid, hydrofluoric acid, pyrovinic acid, TFMS, metal salts of trifluoromethane sulphonic acid or load, Any one or a few in heteropoly acid, solid super-strong acid, acid zeolite, perfluorinated resin, ionic liquid, preferably The TFMS root of pyrovinic acid, metal salts of trifluoromethane sulphonic acid or load, more preferably pyrovinic acid.
Further, in technique scheme, the R in formula I, formula II, general formula III, preferably meta-xylene.
Another object of the present invention be to provide a kind of arylalkyl carboxylic acids's monoesters described above surfactant, wetting agent, The tough agent of bleeding agent, cosolvent, water repellent agent, resin, lubricant, papermaking plasticizer, advanced lubrication oil additive side The application in face.
The beneficial outcomes of the present invention is:
Arylalkyl carboxylic acids's monoesters the most of the present invention solves the defect of double bond poor stability, heat endurance and oxidation stability It is largely increased；
2. arylalkyl carboxylic acids's monoesters condensation point of the present invention is less than-30 DEG C, and application 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 relatively big, and compound property is good；
4. arylalkyl carboxylic acids's monoesters preparation method conversion ratio of the present invention is high, is suitable for industrialization and produces.
Accompanying drawing explanation
Accompanying drawing 4 width of the present invention,
Fig. 1 is the infrared spectrogram of the meta-xylene base octadecane carboxylic acid that embodiment 1 prepares；
Fig. 2 is the meta-xylene base octadecane carboxylate methyl ester infrared spectrogram that embodiment 2 prepares；
Fig. 3 is meta-xylene base octadecane carboxylate's infrared spectrogram that embodiment 1 prepares；
Fig. 4 is the meta-xylene base octadecane carboxylic acid different monooctyl ester infrared spectrogram that embodiment 2 prepares.
Detailed description of the invention
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 meta-xylene base octadecane carboxylate, comprises the following steps:
1. Friedel-Crafts alkylation:
1. reaction equation
Wherein: m+n=15.
2. raw material specification
Technical grade high-purity oleic acid C18:1 content >=75.0%, iodine number (gI2/ 100g) 80-100, water content≤0.5%, mistake Oxidation number≤10 (mg/Kg).
Technical grade methyl sulfonic acid, clear, content >=98.0%, ion concentration≤100ppm.
Technical grade meta-xylene, content >=99.0%.
3. raw material proportioning
Oleic acid: pyrovinic acid: meta-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 meta-xylenes and 225 Kilogram pyrovinic acid, reactor inflated with nitrogen protects, stirring, is warming up to 125 DEG C, starts constant speed and add industrial high-purity oil Acid, control reaction temperature, at 130 DEG C, adds 440.6 kilograms of high-purity oleic acid of industry in 5 hours altogether, and oleic acid continues after adding Reaction 2h.
5. post-processing approach
It is cooled under room temperature, proceeds to material, in another 3000 liters of enamel reaction stills, be slowly added under stirring 200 kilograms of deionized waters, the deionized water joining day, at about 60min, then proceedes to stir about 60min, quiet Only more than 2 hours, separate lower layer of water and pyrovinic acid.
The water separated and pyrovinic acid reclaim pyrovinic acid, the methyl sulphur of recovery by falling film evaporation thickening and rectifying Acid recycles.
Reaction mass deionized water agitator treating three times, neutral to pH value.
Material falling liquid film after washing steams meta-xylene and residual water, and after natural layering, meta-xylene recycles.
Material removes unreacted oleic acid (including saturated fatty acid), vacuum 1Pa, temperature 150 DEG C through molecular clock.
Material decolours (vacuum 1Pa, temperature 210 DEG C) through molecular clock, obtains meta-xylene base octadecane carboxylic acid.
Gas-chromatography and liquid-phase chromatographic analysis, oleic acid conversion >=93%.
6. structural characterization and product property
Meta-xylene base octadecane carboxylic acid infrared spectrogram is shown in Fig. 1.
At Fig. 1 it may be seen that 1710cm-1(carboxylic acid dimerization's 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 face excurvation Qu Zhendong)；1502cm-1(phenyl ring skeleton C=C stretching vibration), 877cm-1(on phenyl ring, having isolated hydrogen), 817cm-1 (phenyl ring skeleton C=C out-of-plane bending vibration), 725cm-1(disubstituted C-H out-of-plane bending vibration between on phenyl ring)； 2925cm-1(CH2Alkane antisymmetric stretching vibration), 2853cm-1(CH2Alkane symmetrical stretching vibration), 1463cm-1 (CH2Alkane angle vibrate), 1377cm-1(CH3Symmetric deformation vibrates).
Meta-xylene base octadecane carboxylic acid indices: content >=95%, iodine number≤10 (gI2/ 100g), pour point-21 DEG C, Flash-point 238 DEG C (opening), density 0.923 (g/cm2)。
2. esterification:
1. reaction equation
Wherein: m+n=15.
2. raw material specification
Meta-xylene base octadecane carboxylic acid: content >=95%, iodine number≤10 (gI2/ 100g), pour point-21 DEG C, flash-point 238 DEG C (opening), density 0.923 (g/cm2)。
Technical grade isobutanol, content >=98%, moisture≤0.1%.
Technical grade stannous oxide, content >=90%.
3. raw material proportioning
Initially feeding intake: meta-xylene base octadecane carboxylic acid: isobutanol=1:3.0 (mol ratio), stannous oxide is total The 0.8% of quality of material.
4. synthesis technique
2000 liters of reactor band reflux condensers and feed supplementing device, be separately added into 700 kilograms of meta-xylene base octadecane carboxylics Acid, 400 kilograms of isobutanols, 10 kilograms of stannous oxides, 115 DEG C～135 DEG C stirring reactions, condenser reclaims and evaporates Isobutanol and water, be spaced the isobutanol supplementing equal quality toward reactor according to the amount of the isobutanol evaporated and water, The acid number of detection product, stops reaction when product acid number≤0.5 (mgKOH/g).
5. post-processing approach
Thick product is filtered to remove stannous oxide.
Falling liquid film removes the isobutanol in product and residual water, isobutanol and the mixture of water in rectifying separation building-up process, Isobutanol recycles.
Product decolours (vacuum 1Pa, temperature 230 DEG C) through molecular clock, obtains meta-xylene base octadecane carboxylic acid different Butyl ester.
6. structural characterization and product property
Meta-xylene base octadecane carboxylate's infrared spectrogram is shown in Fig. 3.
At Fig. 3 it may be seen that 1739cm-1(ester carbonyl group C=O stretching vibration), 1171cm-1(fatty acid ester C-O-C antisymmetric stretching vibration), 1116cm-1((CH3)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(have isolated on phenyl ring Hydrogen), 817cm-1(phenyl ring skeleton C=C out-of-plane bending vibration), 722cm-1(disubstituted C-H face between on phenyl ring Outside sweep is vibrated)；2925cm-1(CH2Alkane antisymmetric stretching vibration), 2854cm-1(CH2Alkane symmetry is stretched Vibration), 1465cm-1(CH2Alkane angle vibrate), 1378cm-1 (CH3Symmetric deformation vibrates).
Meta-xylene base octadecane carboxylate's indices: content >=95%, acid number≤0.5 (mgKOH/g), Iodine number≤10 (gI2/ 100g), pour point-33 DEG C, flash-point 258 DEG C (opening), density 0.88 (g/cm2), motion Viscosity (40 DEG C of mm/s) 37.61, kinematic viscosity (100 DEG C of mm/s) 5.99, viscosity index (VI) 103.
Embodiment 2.
The preparation method of the meta-xylene base different monooctyl ester of octadecane carboxylic acid, comprises the following steps:
1. Friedel-Crafts alkylation:
Wherein: m+n=15.
2. raw material specification
The high-purity methyl oleate of technical grade: C18:1 content >=75.0%, iodine number (gI2/ 100g) 80-100, aqueous≤0.5%, Acid number≤0.5 (mgKOH/g), peroxide value≤10 (mg/Kg).
Technical grade methyl sulfonic acid, clear, content >=98.0%, ion concentration≤100ppm.
Technical grade meta-xylene, content >=99.0%.
3. raw material proportioning
Methyl oleate: pyrovinic acid: meta-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 meta-xylenes and 225 Kilogram pyrovinic acid, reactor inflated with nitrogen protects, stirring, is warming up to 125 DEG C, starts constant speed and add industrial high-purity oil Acid methyl esters, control reaction temperature, at 130 DEG C, adds 462.5 kilograms of high-purity methyl oleates of industry, oleic acid first in 5 hours altogether Ester continues reaction 2h after adding.
5. post-processing approach
It is cooled under room temperature, proceeds to material, in another 3000 liters of enamel reaction stills, be slowly added under stirring 200 kilograms of deionized waters, the deionized water joining day, at about 60min, then proceedes to stir about 60min, quiet Only more than 2 hours, separate lower layer of water and pyrovinic acid.
The water separated and pyrovinic acid reclaim pyrovinic acid, the methyl sulphur of recovery by falling film evaporation thickening and rectifying Acid recycles.
Reaction mass deionized water agitator treating three times, neutral to pH value.
Material falling liquid film after washing steams meta-xylene and residual water, and after natural layering, meta-xylene recycles.
Material removes unreacted methyl oleate (including saturated fatty acid methyl ester), vacuum 1Pa, temperature through molecular clock Spend 140 DEG C.
Material decolours (vacuum 1Pa, temperature 200 DEG C) through molecular clock, obtains meta-xylene base octadecane carboxylic acid first Ester.
Gas-chromatography and liquid-phase chromatographic analysis, methyl oleate conversion ratio >=93%.
6. structural characterization and product property
Meta-xylene base octadecane carboxylate methyl ester infrared spectrogram is shown in Fig. 2.
At Fig. 2 it may be seen that 1742cm-1(carboxylate 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(aliphatic acid Ester C-O-C symmetrical stretching vibration)；1502cm-1(phenyl ring skeleton C=C stretching vibration), 873cm-1(on phenyl ring Have isolated hydrogen), 817cm-1(phenyl ring skeleton C=C out-of-plane bending vibration), 723cm-1(disubstituted between on phenyl ring C-H out-of-plane bending vibration)；2925cm-1(CH2Alkane antisymmetric stretching vibration), 2853cm-1(CH2Alkane pair Claim stretching vibration) 1462cm-1(CH2Alkane angle vibrate), 1376cm-1(CH3Symmetric deformation vibrates).
Meta-xylene base octadecane carboxylate methyl ester indices: content >=95%, acid number≤0.5 (mgKOH/g), iodine Value≤10 (gI2/ 100g), pour point-24 DEG C, flash-point 226 DEG C (opening), density 0.895 (g/cm2), motion is viscous Degree (40 DEG C of mm/s) 30.21, kinematic viscosity (100 DEG C of mm/s) 5.25, viscosity index (VI) 100.
1. reaction equation
Wherein: m+n=15.
2. raw material specification
Meta-xylene base octadecane carboxylate methyl ester indices: content >=95%, acid number≤0.5 (mgKOH/g), iodine Value≤10 (gI2/100g)。
Technical grade isooctanol content >=98% moisture≤0.1%.
Industrial grade benzenemethanol sodium content >=50%.
3. raw material proportioning
Meta-xylene base octadecane carboxylate methyl ester: isooctanol=1:3.0 (mol ratio), sodium methoxide is total quality of material 1.0%.
4. synthesis technique
2000 liters of reactor band reflux condensers, be separately added into 604 kilograms of meta-xylene base octadecane carboxylate methyl esters, 586 Kilogram isooctanol, 23.78 kilograms of sodium methoxides (50% content), 125 DEG C～135 DEG C stirring reactions, condenser reclaims and steams The methyl alcohol sent, the acid number of detection product, when product acid number≤0.5 (mgKOH/g), stop reaction.
5. post-processing approach
Thick product solids removed by filtration.
Falling film evaporation removes the isooctanol of excess.
Product decolours (vacuum 1Pa, temperature 260 DEG C) through molecular clock, obtains meta-xylene base octadecane carboxylic acid different Monooctyl ester.
6. structural characterization and product property
Meta-xylene base octadecane carboxylic acid different monooctyl ester infrared spectrogram is shown in Fig. 4.
At Fig. 4 it may be seen that 1738cm-1(ester carbonyl group C=O stretching vibration), 1244cm-1((CH3)2CR Antisymmetric stretching vibration), 1172cm-1(fatty acid ester C-O-C antisymmetric stretching vibration), 1118cm-1((CH3)2CHR Stretching vibration), 1030cm-1(fatty acid ester C-O-C symmetrical stretching vibration；1502cm-1(phenyl ring skeleton C=C stretches Contracting vibration), 817cm-1(phenyl ring skeleton C=C out-of-plane bending vibration), 724cm-1(disubstituted C-H between on phenyl ring Out-of-plane bending vibration)；2926cm-1(CH2Alkane antisymmetric stretching vibration), 2854cm-1(CH2Alkane symmetry is stretched Contracting vibration), 1463cm-1(CH2Alkane angle vibrate), 1378cm-1(CH3Symmetric deformation vibrates).
Meta-xylene base octadecane carboxylic acid different monooctyl ester indices: content >=95%, acid number≤0.5 (mgKOH/g), Iodine number≤10 (gI2/ 100g), pour point-37 DEG C, flash-point 268 DEG C (opening), density 0.865 (g/cm2), motion Viscosity (40 DEG C of mm/s) 46.61, kinematic viscosity (100 DEG C of mm/s) 7.204, viscosity index (VI) 114.
Application examples 1
The different monooctyl ester of meta-xylene base octadecanoid 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 is not adding the situation of pour-point depressant Under there is high pour point.
The viscosity index (VI) of arylalkyl carboxylic acids's ester has exceeded 100, when configuring lubricating oil perhaps without adding thickener, And the existence of polymer base thickener or improver may cause shear stable sex chromosome mosaicism in the lubricating oil of configuration.
Generally, it is contemplated that arylalkyl carboxylic acids's monoesters of the present invention has in terms of their oxidation stability and cryogenic property The advantage being better than other plant based lubricating oil.

Claims (13)

1. arylalkyl carboxylic acids's monoesters, it is characterised in that there is logical structure shown in formula I:
Wherein: m+n is 8,15,19, q is 1；-OCpH2P+q is the alkane that the branched-chain alcoho of carbon number 3-9 is corresponding Epoxide；
R is phenyl, tolyl, meta-xylene base, paraxylene base, ortho-xylene base, ethylbenzene, n-propylbenzene Base, 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.
Arylalkyl carboxylic acids's monoesters the most according to claim 1, it is characterised in that: include meta-xylene base 18 Alkane carboxylate, the meta-xylene base different monooctyl ester of octadecane carboxylic acid, such as the structure of following formula:
Wherein: m+n is the positive integer of 15.
The preparation method of a kind of arylalkyl carboxylic acids's monoesters the most as claimed in claim 1, it is characterised in that: include following Step:
Friedel-Crafts alkylation: the alkylated reaction that alkene-carboxylic acid and aromatic hydrocarbon are carried out under acidic catalyst effect, To arylalkyl carboxylic acids；
Esterification: again by arylalkyl carboxylic acids and monohydric alcohol under solid acid catalyst or metallic tin catalyst effect The dehydration condensation carried out, obtains arylalkyl carboxylic acids's monoesters.
A kind of preparation method of arylalkyl carboxylic acids's monoesters, it is characterised in that: described alkene One or more in undecenoic acid, oleic acid, erucic acid of yl carboxylic acid；Described monohydric alcohol is 3-9's selected from carbon number Branched-chain alcoho.
A kind of preparation method of arylalkyl carboxylic acids's monoesters, it is characterised in that: described acid Property catalyst selected from sulfuric acid, hydrofluoric acid, pyrovinic acid, TFMS, metal salts of trifluoromethane sulphonic acid or the three of load Any one in fluorine methanesulfonate, heteropoly acid, solid super-strong acid, acid zeolite, perfluorinated resin, ionic liquid Or it is several.
A kind of preparation method of arylalkyl carboxylic acids's monoesters, it is characterised in that: described solid Body acid catalyst is selected from any one or a few in cationic ion-exchange resin, Supported on Zeolite liquid acid or slaine； Described metallic tin catalyst is selected from any one in stannous oxide, stannous chloride or stannous oxalate.
A kind of preparation method of arylalkyl carboxylic acids's monoesters, it is characterised in that: include oil The alkylated reaction that acid is carried out under pyrovinic acid is catalyzed with meta-xylene, reaction equation is as follows:
Wherein: m+n is=15.
A kind of preparation method of arylalkyl carboxylic acids's monoesters, it is characterised in that: include with Lower step:
Friedel-Crafts alkylation: the alkylation that alkene-carboxylic acid's methyl esters is carried out under acidic catalyst effect with aromatic hydrocarbon is anti- Should, obtain arylalkyl carboxylic acids's methyl esters；
Ester exchange reaction: arylalkyl carboxylic acids's methyl esters under solid base acid catalyst or organotin catalysts are catalyzed with other Monohydric alcohol carries out ester exchange reaction, obtains arylalkyl carboxylic acids's monoesters of other structures.
A kind of preparation method of arylalkyl carboxylic acids's monoesters, it is characterised in that: described alkene One or more in methyl undecylenate, methyl oleate, methyl erucate of yl carboxylic acid methyl esters；Described monohydric alcohol It is the branched-chain alcoho of 3-9 selected from carbon number.
A kind of preparation method of arylalkyl carboxylic acids's monoesters, it is characterised in that: described acid Property catalyst selected from sulfuric acid, hydrofluoric acid, pyrovinic acid, TFMS, metal salts of trifluoromethane sulphonic acid or the three of load Any one in fluorine methanesulfonate, heteropoly acid, solid super-strong acid, acid zeolite, perfluorinated resin, ionic liquid Or it is several.
The preparation method of 11. a kind of arylalkyl carboxylic acids's monoesters, it is characterised in that: described Solid acid alkali catalytic agent selected from sodium methoxide, caustic alcohol, potassium carbonate, sodium carbonate, potassium hydroxide, NaOH, sulphur Acid or potassium sulfate in any one, described organotin catalysts selected from Monobutyltin, stannous octoate, stannous methide, Any one or a few in dioctyl tin, tetraphenyltin.
The preparation method of 12. a kind of arylalkyl carboxylic acids's monoesters, it is characterised in that: include The alkylated reaction that methyl oleate is carried out under pyrovinic acid is catalyzed with meta-xylene, reaction equation is as follows:
Wherein: m+n is 15.
13. arylalkyl carboxylic acids's monoesters as claimed in claim 1 or 2 surfactant, wetting agent, bleeding agent, Application in the tough agent of cosolvent, water repellent agent, resin, lubricant, papermaking plasticizer, advanced lubrication oil additive.
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