CN102344358B - Method for preparing C2-C11 organic acid by taking tung oil as raw material - Google Patents
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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 that C prepared by raw material with tung oil
2~ C
11organic acid method.
Background technology
The grease that tung oil is the aleurites fordii of China's special product oil plant seeds-Euphorbiaceae class, Aleurites montana or other tung oil tree seed squeeze, 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 exclusive status, account for 80% of Gross World Product.
Tung oil is the grease with very high industrial Development volue in all vegetables oil, have that fast drying, light specific gravity, glossiness are good, strong adhesion, heat-resisting, acid and alkali-resistance, the characteristic such as antirust, non-conductive, also there is good water-repellancy.Its main fatty acid contained has: Palmiticacid (16:0), stearic acid (18:0), eicosanoic acid (20:0), behenic 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 account for altogether up to about 95%, and especially alpha-eleostearic acid just account for 70 ~ 83%.Alpha-eleostearic acid is suitable, and instead, trans-9,11,13-punicic acids, because having three double bond structures, its Nature comparison is active, can produce more addition, polyreaction, derives very many Chemicals.The organic acid content in natural fats and oils with triene structures is so many also only has tung oil just to have, and this also just determines tung oil and compares other grease and have unique trait.But alpha-eleostearic acid chemical property is active, is easy to that isomerization occurs and becomes anti-, instead, the β-eleostearic acid of trans-9,11,13-punicic acid structures, in atmosphere can be oxidized and aggregate into complicated hard film.In a word, tung oil chemical structure is special, chemical property active, it is high to be worth, purposes is wide, many Chemicals can be synthesized, it is the important sources of the dependable petroleum replacing raw material of chemical industry, it is the natural regeneration raw material of Sustainable Exploitation, the aspects such as building, machinery, printing, electronic industry can be widely used in, also can make oilcloth, oilpaper, soap, nauseants, agrochemical.
The binary of middle short chain, unitary organic acid are important chemical industry, the medical materials of a class, can derive endless product.Be that raw material can prepare C with tung oil
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 a class purposes, can production cold resistant plasticizer, senior lubricant, senior nylon rubber and fine perfumery, not only there is special chemical industry purposes, and constantly expand out more purposes in electronics, medicine and household chemicals field.
The deep processing application aspect of tung oil derivative, patent CN100563959C, CN101255304A, CN86108060A mainly develop the application of paint and coating; Patent CN1031877C, CN1035259C, CN1035258C, CN1238402C, CN1017058B, CN101508861A, CN101701055A, CN101353405A, CN1202497A are then more partial to the modification studying resol class; Also have patent CN1594288A to develop sterilant, CN1310883C, CN101074152A have carried out additive kind modification, and CN101235303A, CN100526440C have carried out the trial research of biomass energy.But all not relating to direct is that C prepared by raw material with tung oil
2~ C
11organic binary, monocarboxylic acid.
In crude vegetal preparation, the organic acid of short chain, particularly prepares C
2~ C
11organic acid aspect, patent CN1075711A, CN1566064A, CN1680253A, CN101077856A, CN1415593A, CN1927806A, CN101200735A, CN1680254A, CN1192134A, CN1616393A, CN1616394A, CN101244998A, CN101250101A, CN101062891A have prepared nonane diacid, n-nonanoic acid mainly through changing the modes such as catalyzer, solvent and oxidizing condition, but raw material sources are all the oleic acid that vegetable and animals oils is extracted, and add purification, separating technology; Suitability for industrialized production propanedioic acid, oxalic acid, 11 carbon diacid, caproic acid, valeric acid and propionic acid are then the method by chemosynthesis more.
Prior art research natural fats and oils is short chain organic acid in raw material preparation, and particularly developing tung oil is that in raw material preparation, the binary of short chain and unitary organic acid still exist blank, returns its reason to be:
(1) deep processing of tung oil does not all also have very large breakthrough both at home and abroad all the time, mainly because external tung oil resource shortage, domestic modification, the low-end product such as printing and property-modifying additive being mainly used for coating, epoxy and resol, 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; The all oxidizable isomery of tung oil itself and autohemagglutination, when more easily autohemagglutination and crosslinking reaction occurring when short chain binary and unitary organic acid in oxicracking preparation.
(3) tungoxyn cracking is large for middle short chain binary and unitary organic acid technology difficulty, and extract cracking again after the partially disposed of unsaturated acid, complex technical process, conditional request is high, is difficult to realize industrialized scale operation.
Summary of the invention
The present invention selects tung oil to be that to prepare carbon chain lengths be C to raw material
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, without under any purification & isolation polyunsaturated fatty acid ester or free acid esters situation, by a step direct oxidation cracking tung oil.The oleic acid (18:1) of monoene obtains nonane diacid and n-nonanoic acid, the linolic acid (18:2) of diene obtains nonane diacid, propanedioic acid and caproic acid, the linolenic acid (18:3) of triolefin 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 unitary organic acid yield is 50 ~ 85%.
The present invention relates to tung oil is that C prepared by raw material
2~ C
11organic acid method, by the following technical solutions:
(1) dark color of 100 parts of weight or light tung oil raw material are dissolved in the polarity of 100 ~ 500 parts of weight or non-polar solvent or both mixed solvents, stir 15 ~ 20 minutes at 0 ~ 20 DEG C, add 50 ~ 250 parts of weight distilled water and with the speed high-speed stirring of 300 ~ 1000 revs/min, add the stabilized free fundamental mode composite polymerzation inhibitor accounting for tung oil raw material weight 0.5 ~ 3% more successively, the solid acid catalyst of 0.5 ~ 3% or heteropolyacid catalyst or solid acid catalyst are 1: 0.5 ~ 2 mixed catalysts mixed with heteropolyacid catalyst by weight, continue stirring 2 ~ 10 hours,
(2) temperature of reaction stirring liquid is raised to 80 ~ 100 DEG C from 20 DEG C, temperature rise rate is 0.1 ~ 1 DEG C/min, adds oxygenant and carry out oxicracking in temperature-rise period, keeps outlet temperature to continue reaction and obtains mix products in 1 ~ 6 hour;
(3) mix products obtains by water hot extraction, underpressure distillation or rectificating method the C that yield is 75 ~ 85% successively
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 dimethylbenzene or pentamethylene or normal hexane or hexanaphthene or octane-iso or heptane or sherwood oil, and mixed solvent is polarity is 1: 0.5 ~ 2 solution mixed with non-polar solvent by weight.
Described stabilized free fundamental mode composite polymerzation inhibitor is 1, the bitter hydrazine (DPPH) of 1-phenylbenzene-2-or 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP) or organic copper salt or quaternary amine or sulphur, or two or more stoppers above-mentioned are the solution of 1: 1 mixing by weight.
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.
The oxygenant added in step (2) refers to and adds 100 ~ 350 parts of weight, concentration is the hydrogen peroxide of 30 ~ 60% or adds 150 ~ 400 parts of weight, concentration is the Peracetic Acid of 10 ~ 30% or two or more mixing approach any of passing in oxygen or the ozone passing into concentration 15 ~ 50% or more four kinds of approach of concentration 95 ~ 99.9%, namely weight ratio is hydrogen peroxide and the Peracetic Acid mixed solution of 1: 0.5 ~ 2, or add hydrogen peroxide and pass into oxygen simultaneously, or add hydrogen peroxide and pass into ozone simultaneously, or add hydrogen peroxide and pass into oxygen and ozone simultaneously, or add Peracetic Acid and pass into oxygen simultaneously, or add Peracetic Acid and pass into ozone simultaneously, or add Peracetic Acid and pass into oxygen and ozone simultaneously, or add hydrogen peroxide and Peracetic Acid mixed solution passes into oxygen simultaneously, or add hydrogen peroxide and Peracetic Acid mixed solution passes into ozone simultaneously, or add hydrogen peroxide and Peracetic Acid mixed solution passes into oxygen and ozone simultaneously.
The present invention has simple to operate, non-environmental-pollution, organic acid comprehensive yield is high and be suitable for the features such as large-scale industrial production:
(1) raw material selected is reproducible crude vegetal, and tung oil raw material without the need to through any purification or isolate undersaturated lipid acid and carry out oxicracking again and obtain organic acid, directly can carry out oxicracking to tung oil and double bond does not occur be cross-linked.
(2) raw material is extensive, and it is the aleurites fordii of the Euphorbiaceae class being suitable for China's warm area growth, Aleurites montana or other tung oil tree by the tung oil that machine squeezes, solvent extraction method obtains dark color or light-coloured transparent.
(3) oxicracking of tung oil has selected composite polymerization inhibitor and mixed catalyst, and processing condition adopt low temperature to high temperature successive reaction, hydrogen peroxide, Peracetic Acid, oxygen and ozone mixed pyrolysis; Should allow tungoxyn cracking that tung oil can not be made again to occur oxidation cross-linked.
(4) raw material selected is novel, and method is simple, and oxidised form is environment friendly and pollution-free, and organic acid yield is high, is suitable for the large-scale industrial production developing tung oil renewable resource.
Embodiment
Embodiment can make the present invention of those skilled in the art complete understanding below, but does not limit the present invention in any way.
Embodiment 1
(1) raw material: the light yellow tung oil raw material choosing 100 parts of weight, the grease that the aleurites fordii of raw material sources in Guangxi province is squeezed, 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: tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%, 20 minutes are stirred the reactor high speed of 20 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add the stabilized free fundamental mode composite polymerzation inhibitor 2 accounting 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 stirring 2 hours; The temperature of reaction of reactor is raised to 80 DEG C from 20 DEG C, temperature rise rate is 0.1 DEG C/min, add 100 parts of weight with 3 seconds speed of 1 in temperature-rise period, concentration be 30% oxidant hydrogen peroxide carry out oxicracking, continue when arriving 80 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 6 hours, obtain mixed solution system.
(3) purification & isolation: poured into by the mixing solutions obtained in separatory still and leave standstill, gets oil phase part boiling water and carries out 3 extractions, and the water layer of separation and liquid phase part above mix; The too high vacuum decompression distillation of remaining oil phase part lease making, collects 3 kinds of water white transparencies or lurid cut respectively; By the aqueous portion of mixing again through high vacuum underpressure distillation, collect 6 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the propionic 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, the valeric acid of 20 parts of weight and 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 choosing 100 parts of weight, the grease that the aleurites fordii that raw material comes from In 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: tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%, 20 minutes are stirred the reactor high speed of 20 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add the stabilized free fundamental mode composite polymerzation inhibitor 2 accounting 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 stirring 2 hours; The temperature of reaction of reactor is raised to 80 DEG C from 20 DEG C, temperature rise rate is 0.1 DEG C/min, add 100 parts of weight with 3 seconds speed of 1 in temperature-rise period, concentration be 30% oxidant hydrogen peroxide carry out oxicracking, continue when arriving 80 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 6 hours, obtain mixed solution system.
(3) purification & isolation: poured into by the mixing solutions obtained in separatory still and leave standstill, gets oil phase part boiling water and carries out 3 extractions, and the water layer of separation and liquid phase part above mix; The too high vacuum decompression distillation of remaining oil phase part lease making, collect 3 kinds of water white transparencies or lurid cut respectively, the aqueous portion of mixing collects 6 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the propionic 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, the valeric acid of 23 parts of weight and 0.2 part of weight, its C
2~ C
11binary and the yield of unary organic carboxylic acid be 71 ~ 80%.
Embodiment 3
(1) raw material: the light tung oil raw material choosing 100 parts of weight, the grease that the aleurites fordii that raw material comes from Central Region 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: tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%, 20 minutes are stirred the reactor high speed of 20 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add the stabilized free fundamental mode composite polymerzation inhibitor 2 accounting 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 stirring 2 hours; The temperature of reaction of reactor is raised to 80 DEG C from 20 DEG C, temperature rise rate is 0.1 DEG C/min, add 100 parts of weight with 3 seconds speed of 1 in temperature-rise period, concentration be 30% oxidant hydrogen peroxide carry out oxicracking, continue when arriving 80 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 6 hours, obtain mixed solution system.
(3) purification & isolation: poured into by the mixing solutions obtained in separatory still and leave standstill, gets oil phase part boiling water and carries out 3 extractions, and the water layer of separation and liquid phase part above mix; The too high vacuum decompression distillation of remaining oil phase part lease making, collect 3 kinds of water white transparencies or lurid cut respectively, the aqueous portion of mixing collects 6 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the propionic 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, the valeric acid of 21 parts of weight and 0.2 part of weight, its C
2~ C
11binary and the yield of unary organic carboxylic acid be 60 ~ 80%.
Embodiment 4
(1) raw material: the light tung oil raw material choosing 100 parts of weight, the grease that raw material comes from North Shaanxi Province of China, the aleurites fordii of 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: tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%, 20 minutes are stirred the reactor high speed of 20 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add the stabilized free fundamental mode composite polymerzation inhibitor 2 accounting 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 stirring 2 hours; The temperature of reaction of reactor is raised to 80 DEG C from 20 DEG C, temperature rise rate is 0.1 DEG C/min, add 100 parts of weight with 3 seconds speed of 1 in temperature-rise period, concentration be 30% oxidant hydrogen peroxide carry out oxicracking, continue when arriving 80 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 6 hours, obtain mixed solution system.
(3) purification & isolation: poured into by the mixing solutions obtained in separatory still and leave standstill, gets oil phase part boiling water and carries out 3 extractions, and the water layer of separation and liquid phase part above mix; The too high vacuum decompression distillation of remaining oil phase part lease making, collect 3 kinds of water white transparencies or lurid cut respectively, the aqueous portion of mixing collects 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the propionic 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, the valeric acid of 22 parts of weight and 0.18 part of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be 65 ~ 80%.
Embodiment 5
(1) raw material: the light tung oil raw material choosing 100 parts of weight, the grease that raw material comes from Eastern China, the aleurites fordii of 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: tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%, 20 minutes are stirred the reactor high speed of 20 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add the stabilized free fundamental mode composite polymerzation inhibitor 2 accounting 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 stirring 2 hours; The temperature of reaction of reactor is raised to 80 DEG C from 20 DEG C, temperature rise rate is 0.1 DEG C/min, add 100 parts of weight with 3 seconds speed of 1 in temperature-rise period, concentration be 30% oxidant hydrogen peroxide carry out oxicracking, continue when arriving 80 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 6 hours, obtain mixed solution system.
(3) purification & isolation: poured into by the mixing solutions obtained in separatory still and leave standstill, gets oil phase part boiling water and carries out 3 extractions, and the water layer of separation and liquid phase part above mix; The too high vacuum decompression distillation of remaining oil phase part lease making, collect 3 kinds of water white transparencies or lurid cut respectively, the aqueous portion of mixing collects 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the propionic 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, the valeric acid of 21 parts of weight and 0.19 part of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be 65 ~ 80%.
Embodiment 6
(1) raw material: the dark tung oil raw material choosing 100 parts of weight, the grease that the Aleurites montana that raw material comes from 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: tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%, 20 minutes are stirred the reactor high speed of 20 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add the stabilized free fundamental mode composite polymerzation inhibitor 2 accounting 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 stirring 2 hours; The temperature of reaction of reactor is raised to 80 DEG C from 20 DEG C, temperature rise rate is 0.1 DEG C/min, add 100 parts of weight with 3 seconds speed of 1 in temperature-rise period, concentration be 30% oxidant hydrogen peroxide carry out oxicracking, continue when arriving 80 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 6 hours, obtain mixed solution system.
(3) purification & isolation: poured into by the mixing solutions obtained in separatory still and leave standstill, gets oil phase part boiling water and carries out 3 extractions, and the water layer of separation and liquid phase part above mix; The too high vacuum decompression distillation of remaining oil phase part lease making, collect 3 kinds of water white transparencies or lurid cut respectively, the aqueous portion of mixing collects 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the valeric 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, the caproic acid of 2.2 parts of weight and 23 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be 68 ~ 78%.
Embodiment 7
(1) raw material: the dark tung oil raw material choosing 100 parts of weight, the grease that other tung oil tree seed that raw material comes from CHINESE REGION genus Euphorbiaceae class squeezes, 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: tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%, 20 minutes are stirred the reactor high speed of 20 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add the stabilized free fundamental mode composite polymerzation inhibitor 2 accounting 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 stirring 2 hours; The temperature of reaction of reactor is raised to 80 DEG C from 20 DEG C, temperature rise rate is 0.1 DEG C/min, add 100 parts of weight with 3 seconds speed of 1 in temperature-rise period, concentration be 30% oxidant hydrogen peroxide carry out oxicracking, continue when arriving 80 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 6 hours, obtain mixed solution system.
(3) purification & isolation: poured into by the mixing solutions obtained in separatory still and leave standstill, gets oil phase part boiling water and carries out 3 extractions, and the water layer of separation and liquid phase part above mix; The too high vacuum decompression distillation of remaining oil phase part lease making, collect 3 kinds of water white transparencies or lurid cut respectively, the aqueous portion of mixing collects 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the valeric 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, the caproic acid of 2.2 parts of weight and 24 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be 65 ~ 80%.
Embodiment 8
(1) raw material: the dark tung oil raw material choosing 100 parts of weight, raw material comes from the grease that tung oil tree seed that South American region belongs to Euphorbiaceae class squeezes, 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: tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%, 20 minutes are stirred the reactor high speed of 20 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add the stabilized free fundamental mode composite polymerzation inhibitor 2 accounting 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 stirring 2 hours; The temperature of reaction of reactor is raised to 80 DEG C from 20 DEG C, temperature rise rate is 0.1 DEG C/min, add 100 parts of weight with 3 seconds speed of one in temperature-rise period, concentration be 30% oxidant hydrogen peroxide carry out oxicracking, continue when arriving 80 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 6 hours, obtain mixed solution system.
(3) purification & isolation: poured into by the mixing solutions obtained in separatory still and leave standstill, gets oil phase part boiling water and carries out 3 extractions, and the water layer of separation and liquid phase part above mix; The too high vacuum decompression distillation of remaining oil phase part lease making, collect 3 kinds of water white transparencies or lurid cut respectively, the aqueous portion of mixing collects 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the valeric 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, the caproic acid of 2.2 parts of weight and 17 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be between 50 ~ 70%.
Embodiment 9
(1) raw material: the dark tung oil raw material choosing 100 parts of weight, raw material comes from the grease that tung oil tree seed that Japan Area belongs to Euphorbiaceae class squeezes, 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: tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%, 20 minutes are stirred the reactor high speed of 20 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add the stabilized free fundamental mode composite polymerzation inhibitor 2 accounting 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 stirring 2 hours; The temperature of reaction of reactor is raised to 80 DEG C from 20 DEG C, temperature rise rate is 0.1 DEG C/min, add 100 parts of weight with 3 seconds speed of one in temperature-rise period, concentration be 30% oxidant hydrogen peroxide carry out oxicracking, continue when arriving 80 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 6 hours, obtain mixed solution system.
(3) purification & isolation: poured into by the mixing solutions obtained in separatory still and leave standstill, gets oil phase part boiling water and carries out 3 extractions, and the water layer of separation and liquid phase part above mix; The too high vacuum decompression distillation of remaining oil phase part lease making, collect 3 kinds of water white transparencies or lurid cut respectively, the aqueous portion of mixing collects 5 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, and the organic acid finally obtained has the valeric acid of the oxalic acid of the nonane diacid of 23 parts of weight, 14 parts of weight, the n-nonanoic acid of 1.5 parts of weight and 14 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be between 50 ~ 70%.
Embodiment 10
(1) raw material: the dark-brown tung oil raw material choosing 100 parts of weight, the grease that raw material sources squeeze in the tung oil tree seed of the Euphorbiaceae class of CHINESE REGION, because the 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: tung oil raw material is dissolved in the polar solvent acetic acid of 500 parts of weight, concentration 15%, 20 minutes are stirred the reactor high speed of 20 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add the stabilized free fundamental mode composite polymerzation inhibitor 2 accounting 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 stirring 2 hours; The temperature of reaction of reactor is raised to 80 DEG C from 20 DEG C, temperature rise rate is 0.1 DEG C/min, add 100 parts of weight with 3 seconds speed of 1 in temperature-rise period, concentration be 30% oxidant hydrogen peroxide carry out oxicracking, continue when arriving 80 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 6 hours, obtain mixed solution system.
(3) purification & isolation: poured into by the mixing solutions obtained in separatory still and leave standstill, gets oil phase part boiling water and carries out 3 extractions, and the water layer of separation and liquid phase part above mix; The too high vacuum decompression distillation of remaining oil phase part lease making, collect 3 kinds of water white transparencies or lurid cut respectively, the aqueous portion of mixing collects 4 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the propionic 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, the valeric acid of 17 parts of weight and 0.15 part of weight, and its yield is between 65 ~ 75%.
Embodiment 11
(1) raw material: the light yellow tung oil raw material choosing 100 parts of weight, the grease that the Euphorbiaceae class tung oil tree seed of raw material sources in CHINESE REGION squeezes, 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: tung oil raw material is dissolved in the non-polar solvent hexanaphthene of 500 parts of weight, 20 minutes are stirred the reactor high speed of 10 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add successively the more bitter hydrazine (DPPH) of stabilized free fundamental mode composite polymerzation inhibitor 1, the 1-phenylbenzene-2-accounting for tung oil raw material weight 0.5%, 0.5% heteropolyacid catalyst H
2wO
4, continue stirring 2 hours; The temperature of reaction of reactor is raised to 90 DEG C from 10 DEG C, temperature rise rate is 0.5 DEG C/min, add 100 parts of weight with 3 seconds speed of 1 in temperature-rise period, concentration is the oxidant hydrogen peroxide of 30%, pass into oxygen simultaneously and carry out oxicracking, continue when arriving 90 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 4 hours, obtain mixed solution system.
(3) purification & isolation: poured into by the mixing solutions obtained in separatory still and leave standstill, gets oil phase part boiling water and carries out 3 extractions, and the water layer of separation and liquid phase part above mix; Remaining oil phase part is divided through rectifying, collects 3 kinds of water white transparencies or lurid cut respectively; By the aqueous portion of mixing again through high vacuum underpressure distillation, collect 6 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the propionic 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, the valeric acid of 20 parts of weight and 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 choosing 100 parts of weight, the grease that raw material sources squeeze in the tung oil tree seed of the Euphorbiaceae class of CHINESE REGION, because the 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: identical with oxicracking condition with the reagent selected by embodiment 10.
(3) purification & isolation: processing condition are identical with embodiment 10, collects 3 kinds of water white transparencies or lurid cut respectively in oil phase, the aqueous portion of mixing collects 4 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the valeric 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, the caproic acid of 2.1 parts of weight and 16 parts of weight, and its yield is between 55 ~ 75%.
Embodiment 13
(1) raw material: identical with the tung oil raw material selected by embodiment 11.
(2) oxidizing reaction: tung oil raw material is dissolved in 500 parts of weight by weight 1: 2 mixing formic acid and heptane solvent in, 15 minutes are stirred the reactor high speed of 5 DEG C, add the distilled water of 100 parts of weight and continue high-speed stirring, add successively again the bitter hydrazine (DPPH) of 1,1-phenylbenzene-2-by weight 1: 1 mixing that accounts for tung oil raw material weight 1% and benzyltriethylammoinium chloride stabilized free fundamental mode composite polymerzation inhibitor, 0.5% H
3pMo
12o
40heteropolyacid catalyst, continues stirring 1.5 hours; The temperature of reaction of reactor is raised to 90 DEG C from 5 DEG C, temperature rise rate is 0.5 DEG C/min, add 150 parts of weight with 3 seconds speed of 1 in temperature-rise period, concentration be 30% oxygenant Peracetic Acid, pass into oxygen simultaneously and carry out oxicracking, continue when arriving 90 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 4 hours, obtain mixed solution system.
(3) purification & isolation: processing condition are identical with embodiment 11, collects 3 kinds of water white transparencies or lurid cut respectively in oil phase, the aqueous portion of mixing does not collect 6 kinds of water white transparencies or lurid cut product.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the valeric 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, the caproic acid of 2.2 parts of weight and 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: identical with the tung oil raw material selected by embodiment 12.
(2) oxidizing reaction: identical with oxicracking condition with the reagent selected by embodiment 13.
(3) purification & isolation: processing condition are identical with embodiment 11, collects 3 kinds of water white transparencies or lurid cut respectively in oil phase, the aqueous portion of mixing collects 4 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the valeric 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, the caproic acid of 2 parts of weight and 15 parts of weight, and its yield is between 50 ~ 70%.
Embodiment 15
(1) raw material: identical with the tung oil raw material selected by embodiment 11.
(2) oxidizing reaction: tung oil raw material is dissolved in 400 parts of weight by weight 1: 1 mixing acetic acid and toluene solvant in, 15 minutes are stirred the reactor high speed of 10 DEG C, add the distilled water of 50 parts of weight and continue high-speed stirring, add successively again and account for mix by weight 1: 12 of tung oil raw material weight 1%, 2,6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP) and benzyltriethylammoinium chloride stabilized free fundamental mode composite polymerzation inhibitor, 1% the H by weight 1: 1 mixing
3pO
4/ SiO
2and H
2wO
4catalyzer, continues stirring 1 hour; The temperature of reaction of reactor is raised to 90 DEG C from 10 DEG C, temperature rise rate is 0.1 DEG C/min, the concentration by weight 1: 1 mixing adding 200 parts of weight with 3 seconds speed of 1 in temperature-rise period is the oxidant hydrogen peroxide of 30% and the mixed solution of Peracetic Acid, the ozone simultaneously passing into oxygen and concentration 15% carries out oxicracking, continue when arriving 90 DEG C of temperature of reaction to keep outlet temperature high-speed stirring to react 2 hours, obtain mixed solution system.
(3) purification & isolation: processing condition are identical with embodiment 11, collects 3 kinds of water white transparencies or lurid cut respectively in oil phase, the aqueous portion of mixing collects 6 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the valeric 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, the caproic acid of 2.2 parts of weight and 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: identical with the tung oil raw material selected by embodiment 12.
(2) oxidizing reaction: identical with oxicracking condition with the reagent selected by embodiment 15.
(3) purification & isolation: processing condition are identical with embodiment 11, collects 3 kinds of water white transparencies or lurid cut respectively in oil phase, the aqueous portion of mixing collects 4 kinds of water white transparencies or lurid cut product respectively.
(4) product analysis: gained cut product is respectively by mass spectroscopy and Fourier's infrared detection, the organic acid finally obtained has the valeric 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, the caproic acid of 2.1 parts of weight and 20 parts of weight, and its yield is between 50 ~ 75%.
Embodiment 17
The temperature-time of this example and the tung oil raw material selected by embodiment 11, oxygenant, oxicracking, the method for purification & isolation are identical.Unlike the polar solvent dimethyl formamide that solvent selected in oxicracking process is 250 parts of weight, catalyzer is the benzyltriethylammoinium chloride and the MoO that account for tung oil raw material weight 2%
3the cut that last rectifying obtains has 7 kinds, through mass spectroscopy and Fourier's infrared detection, Determination of Organic Acids is the valeric acid of the nonane diacid of 43 parts of weight, the propanedioic acid of 1.6 parts of weight, the oxalic acid of 29 parts of weight, the n-nonanoic acid of 2.4 parts of weight, the caproic acid of 2.2 parts of weight and 24 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be between 50 ~ 70%.
Embodiment 18
The temperature-time of this example and the tung oil raw material selected by embodiment 11, oxygenant, oxicracking, the method for purification & isolation are identical.Unlike solvent selected in oxicracking process be 300 parts of weight be the ethyl acetate of 1: 1 and the mixed solution of octane-iso by weight, catalyzer is the SiO accounting 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, Determination of Organic Acids is the valeric acid of the nonane diacid of 44.5 parts of weight, the propanedioic acid of 1.7 parts of weight, the oxalic acid of 28 parts of weight, the n-nonanoic acid of 2.4 parts of weight, the caproic acid of 2.1 parts of weight and 23 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be between 50 ~ 75%.
Embodiment 19
The temperature-time of this example and the tung oil raw material selected by embodiment 11, oxygenant, catalyzer, oxicracking, the method for purification & isolation are identical.Be that the polar solvent of 100 parts of weight is sad unlike solvent selected in oxicracking process, stabilized free fundamental mode composite polymerzation inhibitor is the neutralized verdigris accounting for tung oil raw material weight 3%, the cut that last rectifying obtains has 7 kinds, through mass spectroscopy and Fourier's infrared detection, Determination of Organic Acids is the valeric acid of the nonane diacid of 44 parts of weight, the propanedioic acid of 1.6 parts of weight, the oxalic acid of 29 parts of weight, 11 carbon diacid of 0.2 part of weight, the n-nonanoic acid of 2.3 parts of weight, the caproic acid of 2 parts of weight and 22 parts of weight, its C
2~ C
11binary and the yield of unary organic carboxylic acid be between 50 ~ 70%.
Embodiment 20
The temperature-time of this example and the tung oil raw material selected by embodiment 11, oxygenant, catalyzer, oxicracking, the method for purification & isolation are identical.Unlike the non-polar solvent methylene dichloride that solvent selected in oxicracking process is 200 parts of weight, stabilized free fundamental mode composite polymerzation inhibitor is the benzyltriethylammoinium chloride accounting for tung oil raw material weight 2%, the cut that last rectifying obtains has 5 kinds, through mass spectroscopy and Fourier's infrared detection, Determination of Organic Acids is the valeric acid of the nonane diacid of 40 parts of weight, the propanedioic acid of 1.6 parts of weight, the oxalic acid of 30 parts of weight, the n-nonanoic acid of 2.3 parts of weight and 21 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be between 50 ~ 70%.
Embodiment 21
The method of the stabilized free fundamental mode composite polymerzation inhibitor of this example and the tung oil raw material selected by embodiment 11, oxicracking, oxygenant, catalyzer, purification & isolation is identical.Temperature unlike oxicracking is 0 DEG C, in a kettle. high-speed stirring 20 minutes, and temperature of reaction is raised to 100 DEG C from 0 DEG C, and temperature rise rate is 1 DEG C/min, and at 100 DEG C, high-speed stirring is reacted and obtained mix products in 2 hours; The cut that last rectifying obtains has 5 kinds, and through mass spectroscopy and Fourier's infrared detection, Determination of Organic Acids is the valeric acid of the nonane diacid of 42 parts of weight, the propanedioic acid of 1.6 parts of weight, the oxalic acid of 27 parts of weight, the n-nonanoic acid of 2.4 parts of weight and 21 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be between 50 ~ 75%.
Embodiment 22
The method of the stabilized free fundamental mode composite polymerzation inhibitor of this example and the tung oil raw material selected by embodiment 11, oxicracking, catalyzer, purification & isolation is identical.Temperature unlike oxicracking is 5 DEG C, high-speed stirring 20 minutes in a kettle., temperature of reaction is raised to 80 DEG C from 0 DEG C, and temperature rise rate is 0.1 DEG C/min, pass into the oxidant, ozone of concentration 15%, at 80 DEG C, high-speed stirring is reacted and is obtained mix products in 6 hours simultaneously; The cut that last rectifying obtains has 6 kinds, through mass spectroscopy and Fourier's infrared detection, Determination of Organic Acids is the valeric acid of the nonane diacid of 43 parts of weight, the propanedioic acid of 1.6 parts of weight, the oxalic acid of 28 parts of weight, the n-nonanoic acid of 2.5 parts of weight, the caproic acid of 2.1 parts of weight and 23 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be between 50 ~ 80%.
Embodiment 23
The temperature-time of this example and the tung oil raw material selected by embodiment 12, stabilized free fundamental mode composite polymerzation inhibitor, oxygenant, oxicracking, the method for purification & isolation are identical.Unlike the ethanol of 1: 0.5 and the mixed solution of sherwood oil by weight that solvent selected in oxicracking process is 500 parts of weight, catalyzer is the solid acid catalyst MoO accounting 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, Determination of Organic Acids is the valeric acid of the nonane diacid of 42 parts of weight, the propanedioic acid of 1.8 parts of weight, the oxalic acid of 29 parts of weight, the n-nonanoic acid of 2.4 parts of weight and 23 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be between 52 ~ 78%.
Embodiment 24
The temperature-time of this example and the tung oil raw material selected by embodiment 12, stabilized free fundamental mode composite polymerzation inhibitor, oxygenant, oxicracking, the method for purification & isolation are identical.Unlike solvent selected in oxicracking process be 300 parts of weight by weight the methyl alcohol of 1: 1 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, Determination of Organic Acids is the nonane diacid of 44 parts of weight, the propanedioic acid of 1.8 parts of weight, the oxalic acid of 27 parts of weight, 11 carbon diacid of 0.2 part of weight, the n-nonanoic acid of 2.4 parts of weight and the valeric acid of 22 parts of weight, its C
2~ C
11binary and the yield of unary organic carboxylic acid be between 55 ~ 80%.
Embodiment 25
The method of the stabilized free fundamental mode composite polymerzation inhibitor of this example and the tung oil raw material selected by embodiment 12, oxicracking, catalyzer, purification & isolation is identical.Temperature unlike oxicracking is 10 DEG C, high-speed stirring 15 minutes in a kettle., temperature of reaction is raised to 90 DEG C from 10 DEG C, and temperature rise rate is 0.5 DEG C/min, pass into the oxygen that concentration is 95%, at 90 DEG C, high-speed stirring is reacted and is obtained mix products in 4 hours simultaneously; The cut that last rectifying obtains has 6 kinds, through mass spectroscopy and Fourier's infrared detection, Determination of Organic Acids is the valeric acid of the nonane diacid of 43 parts of weight, the propanedioic acid of 1.5 parts of weight, the oxalic acid of 27 parts of weight, the n-nonanoic acid of 2.5 parts of weight, the caproic acid of 2 parts of weight and 23 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be between 50 ~ 80%.
Embodiment 26
The method of the stabilized free fundamental mode composite polymerzation inhibitor of this example and the tung oil raw material selected by embodiment 12, oxicracking, catalyzer, purification & isolation is identical.Temperature unlike oxicracking is 15 DEG C, high-speed stirring 15 minutes in a kettle., temperature of reaction is raised to 100 DEG C from 15 DEG C, temperature rise rate is 1 DEG C/min, pass into simultaneously concentration be 95% oxygen and concentration be the ozone of 15%, at 100 DEG C, high-speed stirring is reacted and is obtained mix products in 1 hour; The cut that last rectifying obtains has 5 kinds, and through mass spectroscopy and Fourier's infrared detection, Determination of Organic Acids is the valeric acid of the nonane diacid of 46 parts of weight, the oxalic acid of 30 parts of weight, the n-nonanoic acid of 2.6 parts of weight, the caproic acid of 2.2 parts of weight and 23 parts of weight, its C
2~ C
9binary and the yield of unary organic carboxylic acid be between 60 ~ 80%.
Claims (6)
1. one kind is that C prepared by raw material with tung oil
2~ C
11organic acid method, is characterized in that:
(1) tung oil of 100 parts of weight is dissolved in the polarity of 100 ~ 500 parts of weight or non-polar solvent or both mixed solvents, stir 15 ~ 20 minutes at 0 ~ 20 DEG C, add the distilled water of 50 ~ 250 parts of weight and stir with the speed of 300 ~ 1000 revs/min, add successively again and account for the stabilized free fundamental mode composite polymerzation inhibitor of tung oil weight 0.5 ~ 3%, the solid acid catalyst of 0.5 ~ 3% or heteropolyacid catalyst or solid acid catalyst with heteropolyacid catalyst by weight the catalyzer mixed for 1:0.5 ~ 2, continuation stirring 2 ~ 10 hours;
(2) temperature of reaction stirring liquid is raised to 80 ~ 100 DEG C from 0 ~ 20 DEG C, temperature rise rate is 0.1 ~ 1 DEG C/min, adds oxygenant and carry out oxicracking in temperature-rise period, keeps outlet temperature to continue reaction and obtains mix products in 1 ~ 6 hour;
(3) mix products obtains by water hot extraction, underpressure distillation or rectificating method the C that yield is 50 ~ 85% successively
2~ C
11binary and unary organic carboxylic acid.
2. one according to claim 1 is that C prepared by raw material with tung oil
2~ C
11organic 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 dimethylbenzene or pentamethylene or normal hexane or hexanaphthene or octane-iso or heptane or sherwood oil, mixed solvent be polarity with non-polar solvent by weight the solution mixed for 1:0.5 ~ 2.
3. one according to claim 1 is that C prepared by raw material with tung oil
2~ C
11organic acid method, it is characterized in that: described stabilized free fundamental mode composite polymerzation inhibitor is 1, the bitter hydrazine (DPPH) of 1 – bis-Ben Ji – 2 – or 2,2,6,6 – tetramethyl piperidine nitrogen oxygen free radicals (TMP) or organic copper salt or quaternary ammonium salt or sulphur, or above-mentioned two kinds of stoppers are by weight the solution mixed for 1:1.
4. one according to claim 1 is that C prepared by raw material with tung oil
2~ C
11organic 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. one according to claim 1 is that C prepared by raw material with tung oil
2~ C
11organic acid method, it is characterized in that: the oxygenant added in step (2) adds 100 ~ 350 parts of weight, concentration is the hydrogen peroxide of 30 ~ 60% or adds 150 ~ 400 parts of weight, concentration is the Peracetic Acid of 10 ~ 30% or two or more mixing approach of passing in oxygen or the ozone passing into concentration 15 ~ 50% or more four kinds of approach of concentration 95 ~ 99.9%, wherein said mixing approach is: add hydrogen peroxide and Peracetic Acid mixed solution that weight ratio is 1:0.5 ~ 2, or add hydrogen peroxide and pass into oxygen simultaneously, or add hydrogen peroxide and pass into ozone simultaneously, or add hydrogen peroxide and pass into oxygen and ozone simultaneously, or add Peracetic Acid and pass into oxygen simultaneously, or add Peracetic Acid and pass into ozone simultaneously, or add Peracetic Acid and pass into oxygen and ozone simultaneously, or add hydrogen peroxide and Peracetic Acid mixed solution passes into oxygen simultaneously, or add hydrogen peroxide and Peracetic Acid mixed solution passes into ozone simultaneously, or add hydrogen peroxide and Peracetic Acid mixed solution passes into oxygen and ozone simultaneously.
6. one according to claim 1 is that C2 ~ C11 organic acid method prepared by raw material with tung oil, it is characterized in that: the binary of described C2 ~ C11 and unary organic carboxylic acid are that nonane diacid is or/and propanedioic acid is or/and oxalic acid is or/and 11 carbon diacid are or/and n-nonanoic acid is or/and caproic acid is or/and valeric acid is or/and propionic acid.
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| FR2997949A1 (en) * | 2012-11-09 | 2014-05-16 | Arkema France | SELECTIVE EXTRACTION OF OMEGA-FUNCTIONALIZED ACID AFTER OXIDIZING CUT OF UNSATURATED FATTY ACID AND DERIVATIVES |
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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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