CN102344358A - Method for preparing C2-C11 organic acid by taking tung oil as raw material - Google Patents
Method for preparing C2-C11 organic acid by taking tung oil as raw material Download PDFInfo
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Abstract
The invention belongs to the technical field of organic chemistry, and particularly relates to a method for preparing a C2-C11 organic acid by taking tung oil as a raw material, which comprises the following steps: dissolving natural tung oil into a solvent of 0-20 DEG C; adding a stable free radical-type compound polymerization inhibitor accounting for 0.5-3 percent of the weight of the tung oil and an oxidation catalyst; then, enabling the temperature to rise to 80-100 DEG C; simultaneously, carrying out oxicracking on hydrogen peroxide or peracetic acid, oxygen or ozone to obtain a mixed product; and then, carrying out hot water extraction, reduced pressure distillation or rectification to obtain binary organic acids, such as an azelaic acid, a propandioic acid, an oxalic acid, an undecendioic acid and the like of which the yield is 50-85 percent and unitary organic acids, such as an n-nonanoic acid, a caproic acid, a valeric acid, a propionic acid and the like. The method for preparing the C2-C11 organic acid by taking tung oil as the raw material has the characteristics of simple operation, no environmental pollution, high comprehensive yield of the organic acids, and is suitable for large-scale industrial production for exploiting and utilizing tung oil renewable resources.
Description
Technical field
The invention belongs to technical field of organic chemistry, being specifically related to a kind of is feedstock production C with tung oil
2～C
11The organic acid method.
Background technology
Tung oil is the grease that aleurites fordii, Aleurites montana or other tung oil tree seed of China special product oil plant seeds-Euphorbiaceae class squeezed; Be the traditional exporting of China, its output ranks first in the world, and enjoys a very good reputation in the international market always; Be in and monopolize the status, account for 80% of Gross World Product.
Tung oil is to have the grease that very high commercial exploitation is worth in all vegetables oil, has that fast drying, light specific gravity, glossiness are good, strong adhesion, heat-resisting, acid and alkali-resistance, a characteristic such as antirust, non-conductive, also has excellent waterproofness.Its main lipid acid that contains has: Palmiticacid (16:0), stearic acid (18:0), eicosanoic acid (20:0), mountain Yu acid (22:0), oleic acid (18:1), linolic acid (18:2), linolenic acid (18:3), alpha-eleostearic acid (18:3), peanut diolefinic acid (20:2); Wherein unsaturated fatty acids has accounted for up to about 95% altogether, and especially alpha-eleostearic acid has just accounted for 70～83%.Alpha-eleostearic acid is suitable, and is anti-, anti--9,11, the 13-punicic acid, and because of having three double bond structures, its character is more active, can produce more addition, polyreaction, the Chemicals more than deriving very.The organic acid content that in natural fats and oils, has a triolefin structure is so many also to have only tung oil just to have, and this has also just determined tung oil to compare other grease to have unique trait.But the alpha-eleostearic acid chemical property is active, is easy to take place isomerization and becomes instead, and is anti-, anti--9,11, and the β-eleostearic acid of 13-punicic acid structure can be oxidized in air and aggregate into complicated hard film.In a word; The tung oil chemical structure is special, chemical property active, it is high to be worth, purposes is wide; Can synthesize many Chemicals; It is the important source of the dependable alternative petroleum of chemical industry; It is the natural regenerative raw materials of sustainable exploitation; Aspects such as building, machinery, printing, electronic industry can be widely used in, also oilcloth, oilpaper, soap, nauseants, agrochemical can be made.
Binary, the monobasic organic acid of middle short chain are one type of important chemical, medical material, can derive endless product.With tung oil is that raw material can prepare C
2～C
11Binary and unary organic carboxylic acid, mainly can obtain nonane diacid, propanedioic acid, oxalic acid, 11 carbon diacid, n-nonanoic acid, caproic acid, valeric acid and propionic acid.These organic acids are the very extensive and important fine chemical materials of one type of purposes; Can the production cold resistant plasticizer, senior lubricant, senior nylon rubber and senior spices; Not only have special chemical industry purposes, and constantly expand out more purposes in electronics, medicine and household chemicals field.
The deep processing application facet of tung oil derivative, patent CN100563959C, CN101255304A, CN86108060A mainly are the application of having developed paint and coating; Patent CN1031877C, CN1035259C, CN1035258C, CN1238402C, CN1017058B, CN101508861A, CN101701055A, CN101353405A, CN1202497A then more are partial to study the modification of resol class; Also have patent CN1594288A to develop sterilant, CN1310883C, CN101074152A have carried out the additive kind modification, and CN101235303A, CN100526440C have carried out the trial research of biomass energy.But all do not relate to directly is feedstock production C with tung oil
2～C
11Organic binary, monocarboxylic acid.
The organic acid of short chain particularly prepares C in the crude vegetal preparation
2～C
11The organic acid aspect; Patent CN1075711A, CN1566064A, CN1680253A, CN101077856A, CN1415593A, CN1927806A, CN101200735A, CN1680254A, CN1192134A, CN1616393A, CN1616394A, CN101244998A, CN101250101A, CN101062891A have mainly prepared nonane diacid, n-nonanoic acid through changing modes such as catalyzer, solvent and oxidizing condition; But raw material sources all are the oleic acid that vegetable and animals oils is extracted, and have increased purification, separating technology; Suitability for industrialized production propanedioic acid, oxalic acid, 11 carbon diacid, caproic acid, valeric acid and propionic acid then are the method through chemosynthesis more.
Prior art research natural fats and oils is a short chain organic acid in the feedstock production, and particularly exploitation tung oil is that binary and the monobasic organic acid of short chain in the feedstock production still exists blank, Gui Qiyuan because of:
(1) deep processing of tung oil does not both at home and abroad all also have very large breakthrough all the time; Mainly be because external tung oil resource shortage; Domestic mainly is to be used for low-end products such as coating, epoxy and STUDY ON THE MODIFICATION OF PENOLIC RESIN, printing and property-modifying additive, and added value is not high.
(2) tung oil complicated component, unsaturated fatty acid content is high, and particularly trienic acid accounts for major portion, causes its chemical property active; Tung oil itself all is prone to oxidation isomery and autohemagglutination, when autohemagglutination and crosslinking reaction take place when short chain binary and monobasic organic acid in the oxicracking preparation more easily.
(3) the short chain binary is big with monobasic organic acid technical difficulty in the tung oil oxicracking preparation, extracts cracking again after the partially disposed of unsaturated acid, complex technical process, and conditional request is high, is difficult to the industrialized scale operation of realization.
Summary of the invention
The present invention is that to select tung oil for use be C for the feedstock production carbon chain lengths
2～C
11Binary or unary organic carboxylic acid.The carbon chain lengths with monoene and polyene structure that natural tung oil contains up to about 95% is C
18～C
20Unsaturated triacylglycerol is under any purification separating saturated fatty acid ester or free acid esters situation, through step direct oxidation cracking tung oil.The oleic acid of monoene (18:1) obtains nonane diacid and n-nonanoic acid; The linolic acid of diene (18:2) obtains nonane diacid, propanedioic acid and caproic acid; The linolenic acid of triolefin (18:3) obtains nonane diacid, propanedioic acid and propionic acid; Eleostearic acid (18:3) obtains nonane diacid, oxalic acid and valeric acid; Peanut diolefinic acid (20:2) obtains nonane diacid, propanedioic acid and caproic acid, obtains binary organic acid and monobasic organic acid yield is 50～85%.
The present invention relates to tung oil is feedstock production C
2～C
11The organic acid method, adopt following technical scheme:
(1) the dark or light tung oil raw material with 100 parts of weight is dissolved in the polarity or non-polar solvent or both mixed solvents of 100～500 parts of weight; Stirred 15～20 minutes down at 0～20 ℃; Add the distilled water of 50～250 parts of weight and with 300～1000 rev/mins speed high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor that accounts for tung oil raw material weight 0.5～3% more successively; 0.5～3% solid acid catalyst or heteropolyacid catalyst or solid acid catalyst and heteropolyacid catalyst by weight being 1: 0.5～2 blended mixed catalysts, continue to stir 2～10 hours;
(2) temperature of reaction that will stir liquid is raised to 80～100 ℃ from 20 ℃, and temperature rise rate is 0.1～1 ℃/minute, adds oxygenant in the temperature-rise period and carries out oxicracking, keeps outlet temperature to continue reaction and obtains mix products in 1～6 hour;
(3) to obtain yield through water hot extraction, underpressure distillation or rectificating method successively be 75～85% C to mix products
2～C
11Binary and unary organic carboxylic acid.
Described polar solvent is water or dimethyl formamide or methyl alcohol or ethanol or Virahol or the trimethyl carbinol or propyl carbinol or ethyl acetate or ether or formic acid or acetic acid or propionic acid or valeric acid or caproic acid or sad or n-nonanoic acid; Non-polar solvent is methylene dichloride or chloroform or toluene or xylenes or pentamethylene or normal hexane or hexanaphthene or octane-iso or heptane or sherwood oil, and mixed solvent is that polarity and non-polar solvent are by weight being 1: 0.5～2 blended solution.
Described stabilized free fundamental mode composite polymerzation inhibitor is 1; The bitter hydrazine (DPPH) or 2,2,6 of 1-phenylbenzene-2-; 6-tetramethyl piperidine nitrogen oxygen free radical (TMP) or organic copper salt or quaternary amine or sulphur, or above-mentioned two or more stoppers are by weight being 1: 1 blended solution.
Described solid acid catalyst is MoO
3Or SiO
2-Al
2O
3Or H
3PO
4/ SiO
2Or Al
2O
3/ Fe
3O
4Heteropolyacid catalyst is H
2WO
4Or H
3PW
12O
40Or H
4PVW
11O
40Or H
4SiW
12O
40Or H
3PMo
12O
40Or H
3GeW
12O
40
The oxygenant that adds in the step (2) is meant and adds 100～350 parts of weight; Concentration is 30～60% ydrogen peroxide 50 or adds 150～400 parts of weight; Concentration is 10～30% Peracetic Acid or feeds the oxygen of concentration 95～99.9% or feed the ozone of concentration 15～50% or any two or more mixing approach in above four kinds of approach; Be that weight ratio is 1: 0.5～2 ydrogen peroxide 50 and Peracetic Acid mixed solution; Or add ydrogen peroxide 50 aerating oxygen simultaneously; Or add ydrogen peroxide 50 and feed ozone simultaneously; Or add ydrogen peroxide 50 simultaneously aerating oxygen and ozone; Or add Peracetic Acid aerating oxygen simultaneously; Or add Peracetic Acid and feed ozone simultaneously; Or add Peracetic Acid simultaneously aerating oxygen and ozone; Or add ydrogen peroxide 50 and Peracetic Acid mixed solution aerating oxygen simultaneously; Or add ydrogen peroxide 50 and the Peracetic Acid mixed solution feeds ozone simultaneously, or add ydrogen peroxide 50 and Peracetic Acid mixed solution aerating oxygen and ozone simultaneously.
That the present invention has is simple to operate, non-environmental-pollution, the comprehensive yield of organic acid is high and be suitable for characteristics such as large-scale industrial production:
(1) raw material of selecting for use is reproducible crude vegetal, and the tung oil raw material need not through any purification or isolates undersaturated lipid acid and carry out oxicracking again and obtain organic acid, and can be directly tung oil being carried out oxicracking, that two keys do not take place is crosslinked.
(2) raw material is extensive, and it is to be suitable for aleurites fordii, Aleurites montana or other tung oil tree of Euphorbiaceae class of the warm area growth of China through machine presses, the solvent extraction method obtains dark color or light-coloured transparent tung oil.
(3) oxicracking of tung oil has been selected composite polymerization inhibitor and mixed catalyst for use, and processing condition adopt low temperature to the high temperature successive reaction, ydrogen peroxide 50, Peracetic Acid, oxygen and ozone mixed pyrolysis; It is oxidation cross-linked to allow the tung oil oxicracking that tung oil is taken place.
(4) raw material of selecting for use is novel, and method is simple, and oxidised form is environment friendly and pollution-free, and the organic acid yield is high, is suitable for developing the large-scale industrial production of tung oil renewable resource.
Embodiment
Following embodiment can make the present invention of those skilled in the art complete understanding, but does not limit the present invention in any way.
Embodiment 1
(1) raw material: the light yellow tung oil raw material of choosing 100 parts of weight; The raw material sources grease that geographic aleurites fordii is squeezed in Guangxi; Detecting its iodine number is 171; Content of unsaturated acid is 94.8%, wherein alpha-eleostearic acid content is 80%, oleic acid content is 5.4%, linoleic acid content is 7.8%, linolenic acid content be 0.98% and peanut diolefinic acid content be 0.62%.
(2) oxidizing reaction: the tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%; Stirred 20 minutes 20 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor 2 that accounts for tung oil raw material weight 0.5% more successively; 2; 6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), 0.5% SiO
2-Al
2O
3Solid acid catalyst continues to stir 2 hours; The temperature of reaction of reaction kettle is raised to 80 ℃ from 20 ℃; Temperature rise rate is 0.1 ℃/minute; Adding 100 parts of weight, concentration with 3 seconds speed of 1 in the temperature-rise period is that 30% oxidant hydrogen peroxide is carried out oxicracking; Continue when arriving 80 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 6 hours, obtain mixed solution system.
(3) purification separates: the mixing solutions that obtains is poured in the separatory still left standstill, get the oil phase part and carry out 3 extractions with boiling water, isolating water layer and front liquid phase part mix; 3 kinds of water white transparencies or lurid cut are collected in the too high vacuum decompression distillation of remaining oil phase part lease making respectively; The blended aqueous portion is passed through the high vacuum underpressure distillation again, collect 6 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the valeric acid of the caproic acid of the n-nonanoic acid of 11 carbon diacid of the oxalic acid of the propanedioic acid of the nonane diacid of 46.3 parts of weight, 1.5 parts of weight, 35 parts of weight, 0.2 part of weight, 2 parts of weight, 2.5 parts of weight, 20 parts of weight and the propionic acid of 0.2 part of weight, and its yield is respectively 70.8%, 72.1%, 71.4%, 54.1%, 69%, 80.6%, 71.4% and 80%.
Embodiment 2
(1) raw material: the light yellow tung oil raw material of choosing 100 parts of weight; Raw material comes from the grease that the geographic aleurites fordii of Southwest China is squeezed; Detecting its iodine number is 175; Content of unsaturated acid is 95.2%, wherein alpha-eleostearic acid content is 80.2%, oleic acid content is 5.4%, linoleic acid content is 7.9%, linolenic acid content be 1.05% and peanut diolefinic acid content be 0.65%.
(2) oxidizing reaction: the tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%; Stirred 20 minutes 20 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor 2 that accounts for tung oil raw material weight 0.5% more successively; 2; 6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), 0.5% SiO
2-Al
2O
3Solid acid catalyst continues to stir 2 hours; The temperature of reaction of reaction kettle is raised to 80 ℃ from 20 ℃; Temperature rise rate is 0.1 ℃/minute; Adding 100 parts of weight, concentration with 3 seconds speed of 1 in the temperature-rise period is that 30% oxidant hydrogen peroxide is carried out oxicracking; Continue when arriving 80 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 6 hours, obtain mixed solution system.
(3) purification separates: the mixing solutions that obtains is poured in the separatory still left standstill, get the oil phase part and carry out 3 extractions with boiling water, isolating water layer and front liquid phase part mix; 3 kinds of water white transparencies or lurid cut are collected in the too high vacuum decompression distillation of remaining oil phase part lease making respectively, and the blended aqueous portion is collected 6 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the valeric acid of the caproic acid of the n-nonanoic acid of 11 carbon diacid of the oxalic acid of the propanedioic acid of the nonane diacid of 48 parts of weight, 1.7 parts of weight, 34.5 parts of weight, 0.22 part of weight, 2 parts of weight, 2.6 parts of weight, 23 parts of weight and the propionic acid of 0.2 part of weight, its C
2～C
11Binary and unary organic carboxylic acid's yield be 71～80%.
Embodiment 3
(1) raw material: the light tung oil raw material of choosing 100 parts of weight; Raw material comes from the grease that the geographic aleurites fordii of central China is squeezed; Detecting its iodine number is 169; Content of unsaturated acid is 93.3%, wherein alpha-eleostearic acid content is 75.4%, oleic acid content is 7.8%, linoleic acid content is 8.45%, linolenic acid content be 0.9% and peanut diolefinic acid content be 0.75%.
(2) oxidizing reaction: the tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%; Stirred 20 minutes 20 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor 2 that accounts for tung oil raw material weight 0.5% more successively; 2; 6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), 0.5% SiO
2-Al
2O
3Solid acid catalyst continues to stir 2 hours; The temperature of reaction of reaction kettle is raised to 80 ℃ from 20 ℃; Temperature rise rate is 0.1 ℃/minute; Adding 100 parts of weight, concentration with 3 seconds speed of 1 in the temperature-rise period is that 30% oxidant hydrogen peroxide is carried out oxicracking; Continue when arriving 80 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 6 hours, obtain mixed solution system.
(3) purification separates: the mixing solutions that obtains is poured in the separatory still left standstill, get the oil phase part and carry out 3 extractions with boiling water, isolating water layer and front liquid phase part mix; 3 kinds of water white transparencies or lurid cut are collected in the too high vacuum decompression distillation of remaining oil phase part lease making respectively, and the blended aqueous portion is collected 6 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the valeric acid of the caproic acid of the n-nonanoic acid of 11 carbon diacid of the oxalic acid of the propanedioic acid of the nonane diacid of 41 parts of weight, 1.2 parts of weight, 30.5 parts of weight, 0.12 part of weight, 1.9 parts of weight, 2.1 parts of weight, 21 parts of weight and the propionic acid of 0.2 part of weight, its C
2～C
11Binary and unary organic carboxylic acid's yield be 60～80%.
Embodiment 4
(1) raw material: the light tung oil raw material of choosing 100 parts of weight; Raw material comes from the grease that the aleurites fordii of Chinese northern Shensi, central plain area is squeezed; Detecting its iodine number is 170; Content of unsaturated acid is 93.92%, wherein alpha-eleostearic acid content is 77.4%, oleic acid content is 7.4%, linoleic acid content is 7.85%, linolenic acid content be 0.72% and peanut diolefinic acid content be 0.55%.
(2) oxidizing reaction: the tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%; Stirred 20 minutes 20 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor 2 that accounts for tung oil raw material weight 0.5% more successively; 2; 6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), 0.5% SiO
2-Al
2O
3Solid acid catalyst continues to stir 2 hours; The temperature of reaction of reaction kettle is raised to 80 ℃ from 20 ℃; Temperature rise rate is 0.1 ℃/minute; Adding 100 parts of weight, concentration with 3 seconds speed of 1 in the temperature-rise period is that 30% oxidant hydrogen peroxide is carried out oxicracking; Continue when arriving 80 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 6 hours, obtain mixed solution system.
(3) purification separates: the mixing solutions that obtains is poured in the separatory still left standstill, get the oil phase part and carry out 3 extractions with boiling water, isolating water layer and front liquid phase part mix; 3 kinds of water white transparencies or lurid cut are collected in the too high vacuum decompression distillation of remaining oil phase part lease making respectively, and the blended aqueous portion is collected 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the valeric acid of the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 43 parts of weight, 1.4 parts of weight, 33 parts of weight, 2 parts of weight, 2.4 parts of weight, 22 parts of weight and the propionic acid of 0.18 part of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be 65～80%.
Embodiment 5
(1) raw material: the light tung oil raw material of choosing 100 parts of weight; Raw material comes from the grease that the aleurites fordii of Eastern China, southeast is squeezed; Detecting its iodine number is 168; Content of unsaturated acid is 93.22%, wherein alpha-eleostearic acid content is 74.4%, oleic acid content is 7.6%, linoleic acid content is 7.8%, linolenic acid content be 0.92% and peanut diolefinic acid content be 0.45%.
(2) oxidizing reaction: the tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%; Stirred 20 minutes 20 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor 2 that accounts for tung oil raw material weight 0.5% more successively; 2; 6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), 0.5% SiO
2-Al
2O
3Solid acid catalyst continues to stir 2 hours; The temperature of reaction of reaction kettle is raised to 80 ℃ from 20 ℃; Temperature rise rate is 0.1 ℃/minute; Adding 100 parts of weight, concentration with 3 seconds speed of 1 in the temperature-rise period is that 30% oxidant hydrogen peroxide is carried out oxicracking; Continue when arriving 80 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 6 hours, obtain mixed solution system.
(3) purification separates: the mixing solutions that obtains is poured in the separatory still left standstill, get the oil phase part and carry out 3 extractions with boiling water, isolating water layer and front liquid phase part mix; 3 kinds of water white transparencies or lurid cut are collected in the too high vacuum decompression distillation of remaining oil phase part lease making respectively, and the blended aqueous portion is collected 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the valeric acid of the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 42 parts of weight, 1.2 parts of weight, 31 parts of weight, 2 parts of weight, 2.1 parts of weight, 21 parts of weight and the propionic acid of 0.19 part of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be 65～80%.
Embodiment 6
(1) raw material: the dark tung oil raw material of choosing 100 parts of weight; Raw material comes from the grease that the Aleurites montana of CHINESE REGION is squeezed; Detecting its iodine number is 163; Content of unsaturated acid is 92.22%, wherein alpha-eleostearic acid content is 73.1%, oleic acid content is 7.8%, linoleic acid content is 9.86%, linolenic acid content be 0.94% and peanut diolefinic acid content be 0.52%.
(2) oxidizing reaction: the tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%; Stirred 20 minutes 20 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor 2 that accounts for tung oil raw material weight 0.5% more successively; 2; 6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), 0.5% SiO
2-Al
2O
3Solid acid catalyst continues to stir 2 hours; The temperature of reaction of reaction kettle is raised to 80 ℃ from 20 ℃; Temperature rise rate is 0.1 ℃/minute; Adding 100 parts of weight, concentration with 3 seconds speed of 1 in the temperature-rise period is that 30% oxidant hydrogen peroxide is carried out oxicracking; Continue when arriving 80 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 6 hours, obtain mixed solution system.
(3) purification separates: the mixing solutions that obtains is poured in the separatory still left standstill, get the oil phase part and carry out 3 extractions with boiling water, isolating water layer and front liquid phase part mix; 3 kinds of water white transparencies or lurid cut are collected in the too high vacuum decompression distillation of remaining oil phase part lease making respectively, and the blended aqueous portion is collected 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 40 parts of weight, 1.3 parts of weight, 30 parts of weight, 2 parts of weight, 2.2 parts of weight and the valeric acid of 23 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be 68～78%.
Embodiment 7
(1) raw material: the dark tung oil raw material of choosing 100 parts of weight; Raw material comes from the grease that other tung oil tree seed that CHINESE REGION belongs to the Euphorbiaceae class is squeezed; Detecting its iodine number is 163; Content of unsaturated acid is 92.3%, wherein alpha-eleostearic acid content is 73%, oleic acid content is 8%, linoleic acid content is 9.78%, linolenic acid content be 0.98% and peanut diolefinic acid content be 0.54%.
(2) oxidizing reaction: the tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%; Stirred 20 minutes 20 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor 2 that accounts for tung oil raw material weight 0.5% more successively; 2; 6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), 0.5% SiO
2-Al
2O
3Solid acid catalyst continues to stir 2 hours; The temperature of reaction of reaction kettle is raised to 80 ℃ from 20 ℃; Temperature rise rate is 0.1 ℃/minute; Adding 100 parts of weight, concentration with 3 seconds speed of 1 in the temperature-rise period is that 30% oxidant hydrogen peroxide is carried out oxicracking; Continue when arriving 80 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 6 hours, obtain mixed solution system.
(3) purification separates: the mixing solutions that obtains is poured in the separatory still left standstill, get the oil phase part and carry out 3 extractions with boiling water, isolating water layer and front liquid phase part mix; 3 kinds of water white transparencies or lurid cut are collected in the too high vacuum decompression distillation of remaining oil phase part lease making respectively, and the blended aqueous portion is collected 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 42 parts of weight, 1.4 parts of weight, 30 parts of weight, 2.3 parts of weight, 2.2 parts of weight and the valeric acid of 24 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be 65～80%.
Embodiment 8
(1) raw material: the dark tung oil raw material of choosing 100 parts of weight; Raw material comes from the grease that tung oil tree seed that South American region belongs to the Euphorbiaceae class is squeezed; Detecting its iodine number is 161; Content of unsaturated acid is 88.3%, wherein alpha-eleostearic acid content is 70%, oleic acid content is 8.7%, linoleic acid content is 7.78%, linolenic acid content be 1.03% and peanut diolefinic acid content be 0.79%.
(2) oxidizing reaction: the tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%; Stirred 20 minutes 20 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor 2 that accounts for tung oil raw material weight 0.5% more successively; 2; 6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), 0.5% SiO
2-Al
2O
3Solid acid catalyst continues to stir 2 hours; The temperature of reaction of reaction kettle is raised to 80 ℃ from 20 ℃; Temperature rise rate is 0.1 ℃/minute; Adding 100 parts of weight, concentration with 3 seconds speed of one in the temperature-rise period is that 30% oxidant hydrogen peroxide is carried out oxicracking; Continue when arriving 80 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 6 hours, obtain mixed solution system.
(3) purification separates: the mixing solutions that obtains is poured in the separatory still left standstill, get the oil phase part and carry out 3 extractions with boiling water, isolating water layer and front liquid phase part mix; 3 kinds of water white transparencies or lurid cut are collected in the too high vacuum decompression distillation of remaining oil phase part lease making respectively, and the blended aqueous portion is collected 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the caproic acid of the n-nonanoic acid of the oxalic acid of the nonane diacid of 36 parts of weight, 20 parts of weight, 2.2 parts of weight, 2.2 parts of weight and the valeric acid of 17 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be between 50～70%.
Embodiment 9
(1) raw material: the dark tung oil raw material of choosing 100 parts of weight; Raw material comes from the grease that tung oil tree seed that Japan Area belongs to the Euphorbiaceae class is squeezed; Detecting its iodine number is 158; Content of unsaturated acid is 79.8%, wherein alpha-eleostearic acid content is 65%, oleic acid content is 6.7%, linoleic acid content is 7.2%, linolenic acid content be 0.85% and peanut diolefinic acid content be 0.5%.
(2) oxidizing reaction: the tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%; Stirred 20 minutes 20 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor 2 that accounts for tung oil raw material weight 0.5% more successively; 2; 6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), 0.5% SiO
2-Al
2O
3Solid acid catalyst continues to stir 2 hours; The temperature of reaction of reaction kettle is raised to 80 ℃ from 20 ℃; Temperature rise rate is 0.1 ℃/minute; Adding 100 parts of weight, concentration with 3 seconds speed of one in the temperature-rise period is that 30% oxidant hydrogen peroxide is carried out oxicracking; Continue when arriving 80 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 6 hours, obtain mixed solution system.
(3) purification separates: the mixing solutions that obtains is poured in the separatory still left standstill, get the oil phase part and carry out 3 extractions with boiling water, isolating water layer and front liquid phase part mix; 3 kinds of water white transparencies or lurid cut are collected in the too high vacuum decompression distillation of remaining oil phase part lease making respectively, and the blended aqueous portion is collected 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection, and the organic acid that obtains at last has the n-nonanoic acid of the oxalic acid of the nonane diacid of 23 parts of weight, 14 parts of weight, 1.5 parts of weight and the valeric acid of 14 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be between 50～70%.
Embodiment 10
(1) raw material: the dark-brown tung oil raw material of choosing 100 parts of weight; The grease that raw material sources are squeezed in the tung oil tree seed of the Euphorbiaceae class of CHINESE REGION; Because of throw outs such as β-eleostearic acid have appearred in some reason generation oxidation; Detecting its iodine number is 170; Content of unsaturated acid is 94.6%, wherein alpha-eleostearic acid content is 75%, alpha-eleostearic acid content is 4.6%, oleic acid content is 5.58%, linoleic acid content is 7.9%, linolenic acid content be 0.96% and peanut diolefinic acid content be 0.56%.
(2) oxidizing reaction: the tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%; Stirred 20 minutes 20 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor 2 that accounts for tung oil raw material weight 0.5% more successively; 2; 6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), 0.5% SiO
2-Al
2O
3Solid acid catalyst continues to stir 2 hours; The temperature of reaction of reaction kettle is raised to 80 ℃ from 20 ℃; Temperature rise rate is 0.1 ℃/minute; Adding 100 parts of weight, concentration with 3 seconds speed of 1 in the temperature-rise period is that 30% oxidant hydrogen peroxide is carried out oxicracking; Continue when arriving 80 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 6 hours, obtain mixed solution system.
(3) purification separates: the mixing solutions that obtains is poured in the separatory still left standstill, get the oil phase part and carry out 3 extractions with boiling water, isolating water layer and front liquid phase part mix; 3 kinds of water white transparencies or lurid cut are collected in the too high vacuum decompression distillation of remaining oil phase part lease making respectively, and the blended aqueous portion is collected 4 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the valeric acid of the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 42 parts of weight, 1.5 parts of weight, 30 parts of weight, 2 parts of weight, 2.1 parts of weight, 17 parts of weight and the propionic acid of 0.15 part of weight, and its yield is between 65～75%.
Embodiment 11
(1) raw material: the light yellow tung oil raw material of choosing 100 parts of weight; The grease that raw material sources are squeezed in the Euphorbiaceae class tung oil tree seed of CHINESE REGION; Detecting its iodine number is 171; Content of unsaturated acid is 94.8%, wherein alpha-eleostearic acid content is 80%, oleic acid content is 5.4%, linoleic acid content is 7.8%, linolenic acid content be 0.98% and peanut diolefinic acid content be 0.62%.
(2) oxidizing reaction: the tung oil raw material is dissolved in the non-polar solvent hexanaphthene of 500 parts of weight; Stirred 20 minutes 10 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add the stabilized free fundamental mode composite polymerzation inhibitor 1 account for tung oil raw material weight 0.5% more successively, the bitter hydrazine (DPPH) of 1-phenylbenzene-2-, 0.5% heteropolyacid catalyst H
2WO
4, continue to stir 2 hours; The temperature of reaction of reaction kettle is raised to 90 ℃ from 10 ℃; Temperature rise rate is 0.5 ℃/minute; Adding 100 parts of weight, concentration with 3 seconds speed of 1 in the temperature-rise period is 30% oxidant hydrogen peroxide; Aerating oxygen carries out oxicracking simultaneously; Continue when arriving 90 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 4 hours, obtain mixed solution system.
(3) purification separates: the mixing solutions that obtains is poured in the separatory still left standstill, get the oil phase part and carry out 3 extractions with boiling water, isolating water layer and front liquid phase part mix; Remaining oil phase part is divided through rectifying, collects 3 kinds of water white transparencies or lurid cut respectively; The blended aqueous portion is passed through the high vacuum underpressure distillation again, collect 6 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the valeric acid of the caproic acid of the n-nonanoic acid of 11 carbon diacid of the oxalic acid of the propanedioic acid of the nonane diacid of 48 parts of weight, 1.3 parts of weight, 27 parts of weight, 0.2 part of weight, 2.2 parts of weight, 2 parts of weight, 20 parts of weight and the propionic acid of 0.15 part of weight, and its yield is respectively 73.4%, 62.5%, 53.6%, 54.1%, 75.9%, 64.5%, 71.4%, 60%.
Embodiment 12
(1) raw material: the dark-brown tung oil raw material of choosing 100 parts of weight; The grease that raw material sources are squeezed in the tung oil tree seed of the Euphorbiaceae class of CHINESE REGION; Because of throw outs such as β-eleostearic acid have appearred in some reason generation oxidation; Detecting its iodine number is 170; Content of unsaturated acid is 94.6%, wherein alpha-eleostearic acid content is 75%, alpha-eleostearic acid content is 4.6%, oleic acid content is 5.58%, linoleic acid content is 7.9%, linolenic acid content be 0.96% and peanut diolefinic acid content be 0.56%.
(2) oxidizing reaction: the reagent selected with embodiment 10 is identical with the oxicracking condition.
(3) purification separates: processing condition are identical with embodiment's 10, collect 3 kinds of water white transparencies or lurid cut in the oil phase respectively, and the blended aqueous portion is collected 4 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 44 parts of weight, 1.5 parts of weight, 25 parts of weight, 2.2 parts of weight, 2.1 parts of weight and the valeric acid of 16 parts of weight, and its yield is between 55～75%.
Embodiment 13
(1) raw material: the tung oil raw material selected with embodiment 11 is identical.
(2) oxidizing reaction: with the tung oil raw material be dissolved in 500 parts of weight in 1: 2 blended formic acid and heptane solvent; Stirred 15 minutes 5 ℃ reaction kettle high speeds; Add the distilled water of 100 parts of weight and continue high-speed stirring; Add successively again account for tung oil raw material weight 1% by weight 1: 1 blended 1, bitter hydrazine (DPPH) of 1-phenylbenzene-2-and benzyltriethylammoinium chloride stabilized free fundamental mode composite polymerzation inhibitor, 0.5% H
3PMo
12O
40Heteropolyacid catalyst continues to stir 1.5 hours; The temperature of reaction of reaction kettle is raised to 90 ℃ from 5 ℃; Temperature rise rate is 0.5 ℃/minute; Adding 150 parts of weight, concentration with 3 seconds speed of 1 in the temperature-rise period is 30% oxygenant Peracetic Acid; Aerating oxygen carries out oxicracking simultaneously; Continue when arriving 90 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 4 hours, obtain mixed solution system.
(3) purification separates: processing condition are identical with embodiment's 11, collect 3 kinds of water white transparencies or lurid cut in the oil phase respectively, and the blended aqueous portion is not collected 6 kinds of water white transparencies or lurid cut product.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 49 parts of weight, 1.4 parts of weight, 25 parts of weight, 2.2 parts of weight, 2.2 parts of weight and the valeric acid of 22 parts of weight, and its yield is respectively 74.9%, 67.3%, 49.6%, 75.9%, 71%, 78.5%.
Embodiment 14
(1) raw material: the tung oil raw material selected with embodiment 12 is identical.
(2) oxidizing reaction: the reagent selected with embodiment 13 is identical with the oxicracking condition.
(3) purification separates: processing condition are identical with embodiment's 11, collect 3 kinds of water white transparencies or lurid cut in the oil phase respectively, and the blended aqueous portion is collected 4 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 41 parts of weight, 1.4 parts of weight, 25 parts of weight, 2.1 parts of weight, 2 parts of weight and the valeric acid of 15 parts of weight, and its yield is between 50～70%.
Embodiment 15
(1) raw material: the tung oil raw material selected with embodiment 11 is identical.
(2) oxidizing reaction: with the tung oil raw material be dissolved in 400 parts of weight in 1: 1 blended acetic acid and toluene solvant; Stirred 15 minutes 10 ℃ reaction kettle high speeds; Add the distilled water of 50 parts of weight and continue high-speed stirring; Add successively again account for tung oil raw material weight 1% by weight 1: 1 blended 2; 2; 6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP) and benzyltriethylammoinium chloride stabilized free fundamental mode composite polymerzation inhibitor, 1% by weight 1: 1 blended H
3PO
4/ SiO
2And H
2WO
4Catalyzer continues to stir 1 hour; The temperature of reaction of reaction kettle is raised to 90 ℃ from 10 ℃; Temperature rise rate is 0.1 ℃/minute; What add 200 parts of weight with 3 seconds speed of 1 in the temperature-rise period is 30% the oxidant hydrogen peroxide and the mixed solution of Peracetic Acid by weight 1: 1 blended concentration; The ozone of aerating oxygen and concentration 15% carries out oxicracking simultaneously; Continue when arriving 90 ℃ of temperature of reaction to keep outlet temperature high-speed stirring reaction 2 hours, obtain mixed solution system.
(3) purification separates: processing condition are identical with embodiment's 11, collect 3 kinds of water white transparencies or lurid cut in the oil phase respectively, and the blended aqueous portion is collected 6 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 50 parts of weight, 1.5 parts of weight, 26 parts of weight, 2.2 parts of weight, 2.2 parts of weight and the valeric acid of 22 parts of weight, and its yield is respectively 76.4%, 72.1%, 51.6%, 75.9%, 71%, 78.5%.
Embodiment 16
(1) raw material: the tung oil raw material selected with embodiment 12 is identical.
(2) oxidizing reaction: the reagent selected with embodiment 15 is identical with the oxicracking condition.
(3) purification separates: processing condition are identical with embodiment's 11, collect 3 kinds of water white transparencies or lurid cut in the oil phase respectively, and the blended aqueous portion is collected 4 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively through mass spectroscopy and Fourier's infrared detection; The organic acid that obtains at last has the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 43 parts of weight, 1.4 parts of weight, 26 parts of weight, 2.1 parts of weight, 2.1 parts of weight and the valeric acid of 20 parts of weight, and its yield is between 50～75%.
Embodiment 17
The selected tung oil raw material of this example and embodiment 11, oxygenant, the temperature-time of oxicracking, the isolating method of purifying are identical.Different is that solvent selected in the oxicracking process is the polar solvent dimethyl formamide of 250 parts of weight, and catalyzer is benzyltriethylammoinium chloride and the MoO that accounts for tung oil raw material weight 2%
3The cut that last rectifying obtains has 7 kinds; Through mass spectroscopy and Fourier's infrared detection, the organic acid composition is the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 43 parts of weight, 1.6 parts of weight, 29 parts of weight, 2.4 parts of weight, 2.2 parts of weight and the valeric acid of 24 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be between 50～70%.
Embodiment 18
The selected tung oil raw material of this example and embodiment 11, oxygenant, the temperature-time of oxicracking, the isolating method of purifying are identical.Solvent selected in the oxicracking process is 300 parts of weight that different is by weight being 1: 1 the ethyl acetate and the mixed solution of octane-iso, catalyzer is the SiO that accounts for tung oil raw material weight 2%
2-Al
2O
3And H
4PVW
11O
40The cut that last rectifying obtains has 6 kinds; Through mass spectroscopy and Fourier's infrared detection, the organic acid composition is the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 44.5 parts of weight, 1.7 parts of weight, 28 parts of weight, 2.4 parts of weight, 2.1 parts of weight and the valeric acid of 23 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be between 50～75%.
Embodiment 19
The selected tung oil raw material of this example and embodiment 11, oxygenant, catalyzer, the temperature-time of oxicracking, the isolating method of purifying are identical.The polar solvent of solvent selected in the oxicracking process is 100 parts of weight that different is is sad; Stabilized free fundamental mode composite polymerzation inhibitor is the neutralized verdigris that accounts for tung oil raw material weight 3%; The cut that last rectifying obtains has 7 kinds; Through mass spectroscopy and Fourier's infrared detection; The organic acid composition is the caproic acid of the n-nonanoic acid of 11 carbon diacid of the oxalic acid of the propanedioic acid of the nonane diacid of 44 parts of weight, 1.6 parts of weight, 29 parts of weight, 0.2 part of weight, 2.3 parts of weight, 2 parts of weight and the valeric acid of 22 parts of weight, its C
2～C
11Binary and unary organic carboxylic acid's yield be between 50～70%.
Embodiment 20
The selected tung oil raw material of this example and embodiment 11, oxygenant, catalyzer, the temperature-time of oxicracking, the isolating method of purifying are identical.Different is that solvent selected in the oxicracking process is the non-polar solvent methylene dichloride of 200 parts of weight; Stabilized free fundamental mode composite polymerzation inhibitor is the benzyltriethylammoinium chloride that accounts for tung oil raw material weight 2%; The cut that last rectifying obtains has 5 kinds; Through mass spectroscopy and Fourier's infrared detection; The organic acid composition is the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 40 parts of weight, 1.6 parts of weight, 30 parts of weight, 2.3 parts of weight and the valeric acid of 21 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be between 50～70%.
Embodiment 21
Selected tung oil raw material, the stabilized free fundamental mode composite polymerzation inhibitor of oxicracking, oxygenant, catalyzer, the isolating method of purification of this example and embodiment 11 is identical.The temperature of different is oxicracking is 0 ℃, stirs 20 minutes in the reaction kettle high speed, and temperature of reaction is raised to 100 ℃ from 0 ℃, and temperature rise rate is 1 ℃/minute, obtains mix products in 2 hours 100 ℃ of following high-speed stirring reactions; The cut that last rectifying obtains has 5 kinds, and through mass spectroscopy and Fourier's infrared detection, the organic acid composition is the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 42 parts of weight, 1.6 parts of weight, 27 parts of weight, 2.4 parts of weight and the valeric acid of 21 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be between 50～75%.
Embodiment 22
Selected tung oil raw material, the stabilized free fundamental mode composite polymerzation inhibitor of oxicracking, catalyzer, the isolating method of purification of this example and embodiment 11 is identical.The temperature of different is oxicracking is 5 ℃; Stirred 20 minutes in the reaction kettle high speed, temperature of reaction is raised to 80 ℃ from 0 ℃, and temperature rise rate is 0.1 ℃/minute; Feed the oxidant, ozone of concentration 15% simultaneously, obtained mix products in 6 hours 80 ℃ of following high-speed stirring reactions; The cut that last rectifying obtains has 6 kinds; Through mass spectroscopy and Fourier's infrared detection; The organic acid composition is the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 43 parts of weight, 1.6 parts of weight, 28 parts of weight, 2.5 parts of weight, 2.1 parts of weight and the valeric acid of 23 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be between 50～80%.
Embodiment 23
The selected tung oil raw material of this example and embodiment 12, stabilized free fundamental mode composite polymerzation inhibitor, oxygenant, the temperature-time of oxicracking, the isolating method of purifying are identical.Solvent selected in the oxicracking process is 500 parts of weight that different is by weight 1: 0.5 the ethanol and the mixed solution of sherwood oil, catalyzer is the solid acid catalyst MoO that accounts for tung oil raw material weight 2%
3, the cut that last rectifying obtains has 5 kinds, and through mass spectroscopy and Fourier's infrared detection, the organic acid composition is the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 42 parts of weight, 1.8 parts of weight, 29 parts of weight, 2.4 parts of weight and the valeric acid of 23 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be between 52～78%.
Embodiment 24
The selected tung oil raw material of this example and embodiment 12, stabilized free fundamental mode composite polymerzation inhibitor, oxygenant, the temperature-time of oxicracking, the isolating method of purifying are identical.Solvent selected in the oxicracking process is 300 parts of weight that different is by weight 1: 1 the methyl alcohol and the mixed solution of pentamethylene, catalyzer be account for tung oil raw material weight 1% by weight 1: 1 MoO
3And H
4SiW
12O
40Mixed solution; The cut that last rectifying obtains has 6 kinds; Through mass spectroscopy and Fourier's infrared detection; The organic acid composition is the n-nonanoic acid of 11 carbon diacid of the oxalic acid of the propanedioic acid of the nonane diacid of 44 parts of weight, 1.8 parts of weight, 27 parts of weight, 0.2 part of weight, 2.4 parts of weight and the valeric acid of 22 parts of weight, its C
2～C
11Binary and unary organic carboxylic acid's yield be between 55～80%.
Embodiment 25
Selected tung oil raw material, the stabilized free fundamental mode composite polymerzation inhibitor of oxicracking, catalyzer, the isolating method of purification of this example and embodiment 12 is identical.The temperature of different is oxicracking is 10 ℃; Stirred 15 minutes in the reaction kettle high speed, temperature of reaction is raised to 90 ℃ from 10 ℃, and temperature rise rate is 0.5 ℃/minute; Feed concentration simultaneously and be 95% oxygen, obtained mix products in 4 hours 90 ℃ of following high-speed stirring reactions; The cut that last rectifying obtains has 6 kinds; Through mass spectroscopy and Fourier's infrared detection; The organic acid composition is the caproic acid of the n-nonanoic acid of the oxalic acid of the propanedioic acid of the nonane diacid of 43 parts of weight, 1.5 parts of weight, 27 parts of weight, 2.5 parts of weight, 2 parts of weight and the valeric acid of 23 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be between 50～80%.
Embodiment 26
Selected tung oil raw material, the stabilized free fundamental mode composite polymerzation inhibitor of oxicracking, catalyzer, the isolating method of purification of this example and embodiment 12 is identical.The temperature of different is oxicracking is 15 ℃; Stirred 15 minutes in the reaction kettle high speed; Temperature of reaction is raised to 100 ℃ from 15 ℃; Temperature rise rate is 1 ℃/minute; Feed concentration simultaneously and be 95% oxygen and concentration and be 15% ozone, obtained mix products in 1 hour 100 ℃ of following high-speed stirring reactions; The cut that last rectifying obtains has 5 kinds, and through mass spectroscopy and Fourier's infrared detection, the organic acid composition is the caproic acid of the n-nonanoic acid of the oxalic acid of the nonane diacid of 46 parts of weight, 30 parts of weight, 2.6 parts of weight, 2.2 parts of weight and the valeric acid of 23 parts of weight, its C
2～C
9Binary and unary organic carboxylic acid's yield be between 60～80%.
Claims (6)
1. one kind is feedstock production C with tung oil
2～C
11The organic acid method is characterized in that:
(1) tung oil with 100 parts of weight is dissolved in the polarity or non-polar solvent or both mixed solvents of 100～500 parts of weight; Stirred 15～20 minutes down at 0～20 ℃; Add the distilled water of 50～250 parts of weight and stir with 300～1000 rev/mins speed; Add the stabilized free fundamental mode composite polymerzation inhibitor account for tung oil weight 0.5～3%, 0.5～3% solid acid catalyst or heteropolyacid catalyst or solid acid catalyst and heteropolyacid catalyst more successively by weight being 1: 0.5～2 blended catalyzer, continue stirring 2～10 hours;
(2) temperature of reaction that will stir liquid is raised to 80～100 ℃ from 0～20 ℃, and temperature rise rate is 0.1～1 ℃/minute, adds oxygenant in the temperature-rise period and carries out oxicracking, keeps outlet temperature to continue reaction and obtains mix products in 1～6 hour;
(3) to obtain yield through water hot extraction, underpressure distillation or rectificating method successively be 50～85% C to mix products
2～C
11Binary and unary organic carboxylic acid.
2. according to claim 1 a kind of be feedstock production C with tung oil
2～C
11The organic acid method; It is characterized in that: described polar solvent is water or dimethyl formamide or methyl alcohol or ethanol or Virahol or the trimethyl carbinol or propyl carbinol or ethyl acetate or ether or formic acid or acetic acid or propionic acid or valeric acid or caproic acid or sad or n-nonanoic acid; Non-polar solvent is methylene dichloride or chloroform or toluene or xylenes or pentamethylene or normal hexane or hexanaphthene or octane-iso or heptane or sherwood oil, and mixed solvent is that polarity and non-polar solvent are by weight being 1: 0.5～2 blended solution.
3. according to claim 1 a kind of be feedstock production C with tung oil
2～C
11The organic acid method; It is characterized in that: described stabilized free fundamental mode composite polymerzation inhibitor is 1; The bitter hydrazine (DPPH) or 2 of 1-phenylbenzene-2-; 2; 6; 6-tetramethyl piperidine nitrogen oxygen free radical (TMP) or organic copper salt or quaternary amine or sulphur, or above-mentioned two or more stoppers are by weight being 1: 1 blended solution.
4. according to claim 1 a kind of be feedstock production C with tung oil
2～C
11The organic acid method is characterized in that: described solid acid catalyst is MoO
3Or SiO
2-Al
2O
3Or H
3PO
4/ SiO
2Or Al
2O
3/ Fe
3O
4, heteropolyacid catalyst is H
2WO
4Or H
3PW
12O
40Or H
4PVW
11O
40Or H
4SiW
12O
40Or H
3PMo
12O
40Or H
3GeW
12O
40
5 according to claim 1, wherein the kind of tung oil as raw material C
2 ~ C
11 organic acids, characterized in that: in step (2) was added oxidant is added to 100 to 350 parts by weight, a concentration of 30 to 60% of hydrogen peroxide or by adding 150 to 400 parts by weight, a concentration of 10 to 30% peracetic acid or pass into the concentration of 95 to 99.9% of oxygen or pass into the concentration of 15 to 50% of ozone or any of the above four channels of two or more channels, the weight ratio of 1:0.5 to 2 mixture of hydrogen peroxide and peracetic acid , or add hydrogen peroxide also leads to oxygen, or ozone plus hydrogen peroxide simultaneously pass into, or add hydrogen peroxide simultaneously leads to oxygen and ozone, or add peracetic acid simultaneously leads to oxygen, or add peracetic acid also pass into the ozone, or add too peracetic acid and ozone also leads to oxygen, or add a mixture of hydrogen peroxide and peracetic acid also leads to oxygen, or add a mixture of hydrogen peroxide and peracetic acid also pass into the ozone, or add a mixture of hydrogen peroxide and peracetic acid also leads to oxygen and ozone.
6. according to claim 1 a kind of be feedstock production C2～C11 organic acid method with tung oil, it is characterized in that: the binary of described C2～C11 and unary organic carboxylic acid be nonane diacid or/and propanedioic acid or/and oxalic acid or/and 11 carbon diacid or/and n-nonanoic acid or/and caproic acid or/and valeric acid or/and propionic acid.
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| CN102795988A (en) * | 2012-09-13 | 2012-11-28 | 重庆油桐产业研究中心 | Method for preparing nonane diacid and biomass diesel from tung oil |
| CN104797552A (en) * | 2012-11-09 | 2015-07-22 | 阿克马法国公司 | Selective extraction of an omega-functionalised acid after oxidative cleavage of an unsaturated fatty acid and derivatives |
| CN110157545A (en) * | 2019-05-19 | 2019-08-23 | 北京化工大学 | The method that tungsten-based catalyst is catalyzed natural oil oxicracking preparation Short-Chain Fatty Acids and its derivative |
| CN116836051A (en) * | 2023-07-04 | 2023-10-03 | 青岛金牛油脂科技有限公司 | Safe and environment-friendly azelaic acid production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1566064A (en) * | 2003-06-27 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Process for preparing azelaic acid by oleic acid phase transfer catalytic oxidation |
| CN1680254A (en) * | 2005-02-03 | 2005-10-12 | 中国科学院新疆理化技术研究所 | Oxosynthesis of azelaic acid and nonoic acid with mixed ozone solvent |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566064A (en) * | 2003-06-27 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Process for preparing azelaic acid by oleic acid phase transfer catalytic oxidation |
| CN1680254A (en) * | 2005-02-03 | 2005-10-12 | 中国科学院新疆理化技术研究所 | Oxosynthesis of azelaic acid and nonoic acid with mixed ozone solvent |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795988A (en) * | 2012-09-13 | 2012-11-28 | 重庆油桐产业研究中心 | Method for preparing nonane diacid and biomass diesel from tung oil |
| CN104797552A (en) * | 2012-11-09 | 2015-07-22 | 阿克马法国公司 | Selective extraction of an omega-functionalised acid after oxidative cleavage of an unsaturated fatty acid and derivatives |
| CN110157545A (en) * | 2019-05-19 | 2019-08-23 | 北京化工大学 | The method that tungsten-based catalyst is catalyzed natural oil oxicracking preparation Short-Chain Fatty Acids and its derivative |
| CN116836051A (en) * | 2023-07-04 | 2023-10-03 | 青岛金牛油脂科技有限公司 | Safe and environment-friendly azelaic acid production method |
| CN116836051B (en) * | 2023-07-04 | 2024-02-09 | 青岛金牛油脂科技有限公司 | Safe and environment-friendly azelaic acid production method |
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