CN101108928A - Powder paint solidifying agent and method of manufacturing used long chain carbon polyanhydride - Google Patents
Powder paint solidifying agent and method of manufacturing used long chain carbon polyanhydride Download PDFInfo
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- CN101108928A CN101108928A CNA200610029191XA CN200610029191A CN101108928A CN 101108928 A CN101108928 A CN 101108928A CN A200610029191X A CNA200610029191X A CN A200610029191XA CN 200610029191 A CN200610029191 A CN 200610029191A CN 101108928 A CN101108928 A CN 101108928A
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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Abstract
The invention discloses the long carbochain biatomic acid polyanhydrides curing agent with high quality using the alkane or the fatty acid as raw material and prepared by biological method. The biatomic acid polyanhydrides curing agent can be used for the curing of the powder coating. The invention also provides the preparation process of the long carbochain biatomic acid polyanhydrides curing agent. The process is started from the alkane or the fatty acid. First the biological fermentation method is applied to produce the long carbochain biatomic acid to gain the biatomic acid conforming to the requirements after special purification process. The biatomic acid carries out dehydration under normal pressure with other reactant under the material temperature of 100 DEG C. to 140 DEG C. and distillation time of 1h to 6h, and is decompressed and distilled to gain the finished product under the condition of the vacuum degree less than 15mmHg and temperature of 110 DEG C. to 140 DEG C., or is distilled in a wiped film vaporization device to remove the substance with small molecules to gain the polyanhydrides curing agent finished product. The long carbochain polyanhydrides curing agent gained by the invention has product color less than (Gardner chroma), ash not higher than 80ppm and nitrogen content not higher than 60ppm, melting point capable of being adjusted according to the requirement of the actual application, good resistance to yellow changing and completely meets the requirement of the high-grade powder coating on the curing agent.
Description
Technical field
The present invention relates to the powder paint solidifying agent technical field, providing a kind of especially is the high-quality long carbochain biatomic acid polyanhydride solidifying agent product that raw material prepares by bio-transformation and chemical polymerization that sets out with alkane or lipid acid.This product is a kind of novel solidifying agent of powder coating.The present invention provides the preparation technology of this long carbochain biatomic acid polyanhydride solidifying agent simultaneously, this technology is set out by alkane or lipid acid, method with biological fermentation is produced long carbochain biatomic acid, and through behind the special purifying technique, dehydration generates polyanhydride under the effect of catalyzer.
Background technology
Thermosetting powder coating(s) is the environment-friendly type coating that a kind of solvent output is considerably less or do not have.In the Europe and the U.S., because voc (volatile organic compound, volatile organic compounds) is required under the more and more stricter situation, the market of powder coating is just in steady-state growth.
Carbonatoms is an epoxies powder coating and acrylic acid or the like powder coating solidifying agent commonly used at nine to 18 long carbochain biatomic acid or its acid anhydrides.
The long carbochain biatomic acid acid anhydride is the epoxies powder coating as a class coating of solidifying agent.Epoxy resin coating is that kind is maximum in the powder coating, and most widely used coating variety is generally used amine, and acids or acid anhydride type curing agent are cured.At patent US665291, US 6448345, all point out among the EP 0299420, with the solidifying agent of long carbochain biatomic acid acid anhydride as epoxy coating, can improve the snappiness of epoxies powder coating greatly, anti-cracking performance, making films has good machinery and ageing resistance.
The long carbochain biatomic acid acid anhydride is the acrylic acid or the like powder coating as the another kind of coating of solidifying agent.Acrylic powder coating is the weathering resistance powder coating of a class top grade.Common acrylic powder coating solidifying agent has polycarboxylic acid or its acid anhydrides, polyamine, polyphenol, multi-hydroxy compound etc.But from the over-all properties of filming, aliphatic dicarboxylic acid and its acid anhydrides are best solidifying agent, are the main flows of acrylic acid or the like powder coating.
The fusing point of long carbochain biatomic acid own is higher, when being used as the solidifying agent of acrylic acid or the like powder coating, needs higher solidification value.This application to the acrylic acid or the like powder coating causes restriction.In order to improve the long carbochain biatomic acid curing agents, people have developed the solidifying agent of long carbochain biatomic acid polyanhydride as the acrylic acid or the like powder coating.
Point out that as disclosed powdered thermosetting compositions for coatings and method of forming coating film thereof among the Chinese patent CN1456616 with in filming compare with long carbochain biatomic acid, the long carbochain biatomic acid polyanhydride has lower fusing point, high reaction activity and high.Therefore, based on the powder coating of long carbochain polyanhydride, has thin coating thickness, outstanding flexility, scratch resistance performance and low-temperature curing performance.And these performances all are considered to the focus of recent car paint research.
Be used in the high-grade epoxies or acrylic acid or the like powder coating because grow the carbochain polyanhydride, so, very high requirement is arranged growing the quality, particularly its ash, color and luster and anti-yellowing property of carbochain polyanhydride more.If the ash height of long carbochain biatomic acid polyanhydride, the appearance property that powder coating is filmed worsens, and visible impurity increases, and simultaneously, also will exert an influence to the long-term anti-yellowing property and the aging resistance of filming.If the color jaundice of long carbochain polyanhydride product, anti-yellowing property is poor, will produce considerable influence to outward appearance, glossiness and the long-term weatherability that powder coating is filmed, and then limit the application of polyanhydride in the middle of high-grade powder coating.According to pertinent literature and industrial practice, the ash of polyanhydride remains on below the 100ppm, and color is proper index less than 2 (Gardner colourities).
The ash of long carbochain biatomic acid polyanhydride, color or anti-yellowing property are poor, with easy oxidation impurities content and production technique in the polyanhydride much relations are arranged.But because of the commercial production scale of former polyanhydride is little, therefore polyanhydride production technique and final product quality are studied seldom, almost do not had this respect document and report.
The xanthochromic source of long carbochain biatomic acid polyanhydride color mainly contains two, is coloring matter or the easy oxidation impurities that contains in the raw material diprotic acid on the one hand; Another is that polyanhydride reacts under comparatively high temps for a long time, and the color of the finished product is affected in the process of producing.
From raw material, the many SL-AH with chemical method production of former long carbochain biatomic acid polyanhydride are raw material.But because the diprotic acid price comparison height of chemical method is very restricted the production application of polyanhydride.Simultaneously, contain the intermediate or the by-product impurities of band ketone group or nitric acid group in the long carbochain biatomic acid of chemical method production, and can produce very big influence to the color of polyanhydride finished product after these material heating.
Be raw material with alkane or lipid acid among the present invention, utilize biological process to be translated into long carbochain biatomic acid, thus successful realization the exploitation of high-quality long carbochain biatomic acid polyanhydride.Biological process is produced long carbochain biatomic acid and is had environmental protection and energy saving, the characteristics of good product quality, and cost and price is obviously low than chemical method diprotic acid, expanding for the industrialization of polyanhydride provides possibility.It is the production of the long carbochain biatomic acid polyanhydride of raw material that the present invention relates generally to the biological process diprotic acid.
But existing commercially available biological process long carbochain biatomic acid, product purity is low, ash and nitrogen class material residual quantity height are not suitable for the production of long carbochain biatomic acid polyanhydride, and resulting polyanhydride product is in the requirement that does not reach high-grade powder coating aspect ash, the anti-yellowing property fully.
According to pertinent literature and industrial practice, nitrogen content can cause very big influence to polyanhydride in the biological process long carbochain biatomic acid.The long carbochain biatomic acid that biological fermentation is produced is subjected to the influence of fermented liquid, generally all can have partial protein and other nitrogenous type organic matter residual.In producing the process of polyanhydride, the easy oxidation of nitrogenous substances and xanthochromia, and then influence the color of finished product.Simultaneously, the polyanhydride that nitrogen content is high also can worsen long-term weatherability and the anti-yellowing property that powder coating is filmed, so limited polyanhydride as solidifying agent in the application aspect the special purpose powder coating.
Simultaneously, as patent CN1456616 expenditure, the purity of long carbochain biatomic acid also can exert an influence to the quality of polyanhydride.
Generally below 97% (vapor phase process), impurity and nitrogen content are uncontrolled for prior biological method diprotic acid purity, and fluctuation range is big, is not suitable for the production of long carbochain biatomic acid polyanhydride fully.
In order to address this problem, in disclosed powdered thermosetting compositions for coatings of patent CN1456616 and method of forming coating film thereof and the middle proposition of filming, after obtaining the finished product of polyanhydride, heating for dissolving is in the isobutyl acetate kind solvent, use activated carbon adsorption, under 110 ℃ of conditions, filter distillation and obtain the purification thing of polyanhydride.But the long carbochain biatomic acid polyanhydride itself is a kind of very unsettled polymkeric substance, very easy suction degraded, and high temperature is the easy xanthochromia of distillation down, and solubility property is with polymerization degree variation difference very greatly, causes the method for dissolution filter to be difficult to realize in industry.The polyanhydride final product quality do not guarantee, can't large-scale application in the middle of high-quality coating.
The present invention uses unique diacid fermentation technology, by the diprotic acid purification techniques of strictness, and indexs such as the purity of control raw material, ash, nitrogen content, and then obtained high-quality long carbochain biatomic acid polyanhydride.Product meets the requirement of powder coating producer fully.
In addition, in the production process of polyanhydride, generally be in reactor, reactants such as long carbochain biatomic acid, dewatering agent to be heated and air distillation, long-time vacuum distilling under 160～180 ℃ of conditions then obtains the polyanhydride finished product at last.
Common problem is that technology later stage distillation temperature is too high in this technology, and the reaction times is long, directly causes final polyanhydride finished color jaundice.In order to address this problem, under high vacuum condition, distillatory temperature and distillation time are controlled in strictness among the present invention, or utilize the film evaporator distillation, and the shade and quality of product is guaranteed to greatest extent.
Summary of the invention
One of technical problem to be solved by this invention is to provide a kind of powder paint solidifying agent, and this solidifying agent foreign matter content is low, of light color, and yellowing resistance can be good, reaches or considerably beyond the requirement to solidifying agent of powder coating.
Two of technical problem to be solved by this invention is to provide the employed long carbochain biatomic acid polyanhydride of the above-mentioned solidifying agent of a kind of preparation method, this method is set out by alkane or lipid acid, method with biological fermentation is produced long carbochain biatomic acid, through behind the special purifying technique, dehydration generates polyanhydride under the effect of catalyzer.The long carbochain biatomic acid polyanhydride foreign matter content of preparation is low, of light color, and anti-yellowing property is good.
As the powder paint solidifying agent of first aspect present invention, it is the long carbochain biatomic acid polyanhydride that raw material prepares by biological process that sets out that described solidifying agent contains with alkane or lipid acid.
The used long-chain biatomic acid carbonatoms of described long carbochain biatomic acid polyanhydride is between 11 to 18.
The polyanhydride of long carbochain biatomic acid described in the present invention is meant color less than 2 (Gardner colourities), and the ash content of coal is below 80ppm, and nitrogen content is less than 60ppm, and total dicarboxylic acid content is not less than 98% long carbochain biatomic acid polyanhydride after the polyanhydride hydrolysis.It is of light color, and anti-yellowing property is outstanding, can satisfy the requirement of high-grade powder coating to solidifying agent fully.
Preparation method as the long carbochain biatomic acid polyanhydride of second aspect present invention, comprise polymerization procedure and purification step, wherein polymerization procedure is at first the alkane (or lipid acid) of particular carbon chain length to be produced long carbochain biatomic acid by the method for biological fermentation, this diprotic acid is carried out purification processes to reach specific specification requirement, then with long carbochain biatomic acid and other reactive material of the appropriate amount handled well, composition and molecular weight control according to the polyanhydride that has the polyanhydride solidifying agent now, ingredient proportion is put in the air distillation still, under protection of inert gas, be heated to 100～140 ℃, normal pressure steams lower-molecular substance, and distillation time is 1～6 hour; Described purification step is at vacuum tightness＜15mmHg, 110～140 ℃ of temperature, underpressure distillation and obtain finished product; Or in the wiped film vaporization device, distill, remove small-molecule substance after, obtain the polyanhydride finished product, the vacuum range of wiped film vaporization device is below 2mmHg, vaporization temperature is at 120～180 ℃, residence time of material was less than 5 minutes.
In the wiped film vaporization process, employed wiped film vaporization device is vertical-type evaporator or horizontal-type evaporator.
In the preparation method of long carbochain biatomic acid polyanhydride of the present invention, employed long carbochain biatomic acid, its gas phase purity＞98%, ash＜60ppm, nitrogen content＜50ppm, color＜2 (Gardner colourity) is to reach the requirement of polyanhydride solidifying agent to diprotic acid.
Particularly employed long carbochain biatomic acid is the monounsaturated dicarboxylic acid by carbonatoms from 11 to 18 carbon of biological fermentation process production.
In the preparation method of long carbochain biatomic acid polyanhydride of the present invention, employed this employing of long carbochain biatomic acid biological process is prepared from, and it may further comprise the steps:
1) fermentation method transforms: alkane or lipid acid with C11～C18 are substrate, are converted into the corresponding long chain diprotic acid by microbe fermentation method;
Wherein, microorganism is adopted candida tropicalis (Candida Tropicalis), and the prescription of fermentation tank culture medium is: KH2PO4:0.2～1.5%; NaCl:0～0.2%; Yeast extract paste: 0.1～2.0%; Urea: 0.2～1.5%; Glucose: 1.0～5.0%; (NH4) 2SO4:0～2.0%; MgSO47H2O:0～0.3%; Defoamer: 0.005%;
Fermentation condition is: inoculum size: 20%; Jar temperature: 29.0 ± 1.0 ℃; Ventilation: 1: 1.0～0.2vvm; Tank pressure: 0.05～0.1Mpa; PH: earlier fermentation thalli growth 3.5～6.5; The fermentation middle and later periods transforms 7.0～8.5; Incubation time: 120～170 hours;
The feed supplement controlled variable:
One alkane/lipid acid: as thalli growth optical density(OD) (OD
600) greater than 0.6, begin to add 5～10% alkane or lipid acid, adding in the alkane lipid acid control fermented liquid alkane or fatty acid concentration thereafter is 2～10%, fermentation ends stopped feed supplement in preceding 24 hours;
2) extraction of diprotic acid: fermented liquid is added adjusting PH with base to 8～11, be heated to 60～100 ℃, utilize centrifuging or membrane filter method separating thallus then, diprotic acid clear liquid and the remaining substrate of fermentation; The diprotic acid clear liquid that obtains adds the gac that is no more than clear liquid volume 5% content according to circumstances, 60～95 ℃ of decolourings 20～180 minutes, remove by filter gac, destainer is heated to 60～100 ℃ then, carry out acidizing crystal with acid for adjusting pH to 2～5, acidizing crystal liquid obtains the long carbochain biatomic acid crude product through filter press again; With alkaline solution dissolving long carbochain biatomic acid crude product, after treating that diprotic acid fully dissolves, add the oxygenant of oxygenant mole number and be heated to 30～100 ℃ and carried out oxidative decoloration 1-8 hour, treat oxidizing reaction finish the back with acid for adjusting pH value to 3.0-4.0, the long carbochain biatomic acid crystallization is separated out, centrifugal or collect product with Plate Filtration, after repeatedly washing with distilled water, drying obtains finished product.
Described alkaline solution is sodium hydroxide, potassium hydroxide, ammoniacal liquor or other inorganic alkali solutions.
Described oxygenant is hydrogen peroxide or ozone.
Described acid is organic acids such as mineral acids such as sulfuric acid or hydrochloric acid, or acetate.
Long carbochain biatomic acid polyanhydride of the present invention is of light color, and anti-yellowing property is outstanding, can satisfy the requirement of high-grade powder coating to solidifying agent fully.
Description of drawings
Further specify the present invention below in conjunction with the drawings and specific embodiments.
Fig. 1 is a process flow sheet of the present invention.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with embodiment, further set forth the present invention.
It is the long carbochain biatomic acid polyanhydride that raw material prepares by biological process that sets out that powder paint solidifying agent, described solidifying agent contain with alkane or lipid acid.The used long-chain biatomic acid carbonatoms of long carbochain biatomic acid polyanhydride is between 11 to 18.
And the long carbochain biatomic acid polyanhydride that uses is meant color less than 2 (Gardner colourities), and the ash content of coal is below 80ppm, and nitrogen content is less than 60ppm, and total dicarboxylic acid content is not less than 98% long carbochain biatomic acid polyanhydride after the polyanhydride hydrolysis.It is of light color, and anti-yellowing property is outstanding, can satisfy the requirement of high-grade powder coating to solidifying agent fully.
The preparation method of its long carbochain biatomic acid polyanhydride, this method comprises polymerization procedure and purification step, wherein polymerization procedure is at first the alkane or the lipid acid of particular carbon chain length to be produced long carbochain biatomic acid by the method for biological fermentation, this diprotic acid is carried out purification processes to reach specific specification requirement, then with long carbochain biatomic acid and other reactive material inputs of the appropriate amount handled well, composition and molecular weight control according to the polyanhydride that has the polyanhydride solidifying agent now, ingredient proportion is put in the air distillation still, be heated to 100～140 ℃, normal pressure steams lower-molecular substance, and distillation time is 1～6 hour; Then at vacuum tightness＜15mmHg, 110～140 ℃ of temperature, underpressure distillation and obtain finished product; Or in the wiped film vaporization device, distill, remove small-molecule substance after, obtain the polyanhydride finished product.
The vacuum range of wiped film vaporization device is below 2mmHg, and vaporization temperature is at 120～180 ℃, and residence time of material was less than 5 minutes.
In the wiped film vaporization process, employed wiped film vaporization device is vertical-type evaporator or horizontal-type evaporator.
Employed long carbochain biatomic acid, its gas phase purity＞98%, ash＜60ppm, nitrogen content＜50ppm, color＜2 (Gardner colourity) is to reach the requirement of polyanhydride solidifying agent to diprotic acid.As be the monounsaturated dicarboxylic acid of carbonatoms from 11 to 18 carbon produced by biological fermentation process.
Below, the preparation method of specific description long carbochain biatomic acid polyanhydride of the present invention.
The method that biological process is produced long-chain biatomic acid may further comprise the steps:
1) fermentation method transforms: alkane or lipid acid with C11～C18 are substrate, are converted into the corresponding long chain diprotic acid by microbe fermentation method;
Wherein, microorganism is adopted candida tropicalis (Candida Tropicalis), and the prescription of fermentation tank culture medium is: KH2PO4:0.2～1.5%; NaCl:0～0.2%; Yeast extract paste: 0.1～2.0%; Urea: 0.2～1.5%; Glucose: 1.0～5.0%; (NH4) 2SO4:0～2.0%; MgSO47H2O:0～0.3%; Defoamer: 0.005%, MnSO40.0001-0.001%, CuSO4 0.0001-0.001%;
Fermentation condition is: inoculum size: 20%; Jar temperature: 29.0 ± 1.0 ℃; Ventilation: 1: 1.0～0.2vvm; Tank pressure: 0.05～0.1Mpa; PH: earlier fermentation thalli growth 3.5～6.5; The fermentation middle and later periods transforms 7.0～8.5; Incubation time: 140～170 hours;
The feed supplement controlled variable:
--alkane/lipid acid: when thalli growth optical density(OD) (OD600) greater than 0.6, begin to add 5～10% alkane or lipid acid, adding in the alkane lipid acid control fermented liquid alkane or fatty acid concentration thereafter is 2～10%, fermentation ends stopped feed supplement in preceding 24 hours;
2) diprotic acid extracts: as follows to the operating procedure that biological process long carbochain biatomic acid product is purified once more:
Fermented liquid or enzyme process reaction solution are added adjusting PH with base to 8～11, be heated to 60～100 ℃, utilize centrifuging or membrane filter method separating thallus then, diprotic acid clear liquid and the remaining substrate of fermentation; The diprotic acid clear liquid that obtains adds 0～5% gac according to circumstances, 60～95 ℃ of decolourings 20～180 minutes, removes by filter gac, destainer is heated to 60～100 ℃ then, uses H
2SO
4Regulate pH to 2～5 and carry out acidizing crystal, acidizing crystal liquid obtains the diprotic acid crude product through filter press again;
3) diprotic acid is purified: with alkaline solution dissolving long carbochain biatomic acid crude product, after treating that diprotic acid fully dissolves, add oxygenant and be heated to 30～100 ℃ and carried out oxidative decoloration 1-8 hour, carry out oxidative decoloration, treat oxidizing reaction finish the back with acid for adjusting pH value to 3.0-4.0, the long carbochain biatomic acid crystallization is separated out, centrifugal or collect product with Plate Filtration, after repeatedly washing with distilled water, drying obtains finished product.
In the purifying technique process, employed alkaline solution is sodium hydroxide solution or potassium hydroxide solution or ammoniacal liquor or other inorganic alkali solutions; Be preferably sodium hydroxide solution.
Employed oxygenant is hydrogen peroxide or ozone, is preferably hydrogen peroxide, and the concentration of hydrogen peroxide is generally 5～50%, and the consumption of oxygenant is the oxygenant mole number: diprotic acid mole number＜2.
The acid solution that is adopted during acidifying is generally mineral acids such as sulfuric acid or hydrochloric acid, or organic acid such as acetate.Be preferably sulfuric acid.
Long carbochain biatomic acid finished product after purifying among the present invention requires gas phase purity＞98%, ash＜60ppm, and nitrogen content＜50ppm is to reach the requirement of polyanhydride solidifying agent to diprotic acid.
By above strict process control, can obtain satisfied polyanhydride finished product.
Embodiment
In following embodiment,,, all be as the criterion with weight if there is not special mark with regard to " part " and " % ".The present invention includes but be not limited to following example:
1, the fermentative preparation example 1 of long carbochain biatomic acid
In the 200M3 fermentor tank of 100M3 substratum is housed, inserts seed liquor and begin fermentation.The fermentation culture based component is: glucose 1.5%, and KH2PO4 1.5%, yeast extract paste 1.0%, corn steep liquor 0.5%, urea 0.35%, NaCl 0.1%, KNO30.7%, the pH nature, 121 ℃ of sterilizations even disappear.Alkane and feed supplement sugar disappear.Under 29 ℃ of air flow 0.5vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH nature that ferments, based on thalli growth, when thalli growth optical density(OD) (OD600) greater than 0.6, begin stream and add C11 alkane, C11 alkane concentration maintains about 5% in the control fermented liquid, regulates pH to 7.0 simultaneously, in 48 hours, regulate pH to 7.0 with NaOH solution in per 4 hours, and 48-72 hour, regulated pH to 7.5 with NaOH solution in per 4 hours, 72-120 hour, regulated pH to 7.8 with NaOH solution in per 4 hours, 120 hours to putting jar, regulated pH to 8.0 with NaOH solution in per 4 hours.Fermentation to 24,48,72 hours batches of formulas were added 1% glucose, and 2% yeast extract paste was added in fermentation to 96 hours.From being inoculated into fermentation ends, total incubation time is 167 hours, is 120.4g/L with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC11 content.
One times of the fermented liquid thin up that obtains adds adjusting PH with base to 8.0, is heated to 90 ℃, and is centrifugal while hot, removes thalline and residual hydrocarbon.Centrifugal clear liquid adds 2.5% activated carbon decolorizing elimination gac after 20 minutes, regulate pH to 2.0 with sulfuric acid and carry out acidizing crystal, acidizing crystal liquid is cooled to room temperature, filter, wash to neutral, dried 12 hours for 80 ℃, obtain product, analyzing total acid is 99.0%, and the DC11 gas chromatographic purity is 96.8%.
2, the fermentative preparation example 2 of long carbochain biatomic acid
In the 200M3 fermentor tank of 100M3 substratum is housed, inserts seed liquor and begin fermentation.The fermentation culture based component is: glucose 3.0%, and KH2PO4 0.5%, yeast extract paste 2%, corn steep liquor 1.5%, urea 0.25%, NaCl 0.2%, and KNO3 0.5%, the tap water preparation, the pH nature, 121 ℃ of sterilizations even disappear.C12 alkane and feed supplement sugar disappear.Under 29 ℃ of air flow 0.5vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH natures ferment, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, begin batch formula and add C12 alkane 8%, after this added that alkane concentration maintains about 5% in alkane control fermented liquid in per 8 hours, regulate pH to 6.5 simultaneously, after 48 hours, regulate pH to 7.0 with NaOH solution in per 4 hours, and 48-72 hour, regulated pH to 7.5 with NaOH solution in per 4 hours, 72-120 hour, regulated pH to 7.8 with NaOH solution in per 4 hours, 120 hours to putting jar, regulated pH to 8.0 with NaOH solution in per 4 hours.Fermentation to 24,48,72 hours batches of formulas are added 1% glucose, and from being inoculated into fermentation ends, total incubation time is 138 hours, is 148.4g/L with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC12 content.
One times of the fermented liquid thin up that obtains adds adjusting PH with base to 9.0, is heated to 90 ℃, and is centrifugal while hot, removes thalline and residual hydrocarbon.Centrifugal clear liquid adds 1.5% activated carbon decolorizing elimination gac after 20 minutes, regulate pH to 3.5 with sulfuric acid and carry out acidizing crystal, acidizing crystal liquid is cooled to room temperature, filter, wash to neutral, dried 12 hours for 80 ℃, obtain product, analyzing total acid is 99.0%, and the DC12 gas chromatographic purity is 96.8%.
3, the fermentative preparation example 3 of long carbochain biatomic acid
In the 200M3 fermentor tank of 100M3 substratum was housed, the secondary seed solution of access began fermentation.The fermentation culture based component is: glucose 4.0%, and KH2PO4 0.8%, yeast extract paste 1.0%, corn steep liquor 0.5%, urea 0.35%, NaCl 0.1%, and KNO3 0.7%, the pH nature, 121 ℃ of sterilizations even disappear.Alkane and feed supplement sugar disappear.Under 29 ℃ of air flow 0.6vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH nature that ferments, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, begin batch formula and add C13 alkane 5%, after this added that alkane concentration maintains about 5% in alkane control fermented liquid in per 8 hours, regulate pH to 6.5 and automatic control simultaneously, pH automatic control 7.0 in 48 hours, 72 hours, pH automatic control 7.5,120 hours, pH automatic control 7.8,120 hours to putting jar, pH automatic control 8.0.Fermentation to 18,32,96 hours batches of formulas are added 1% glucose, and from being inoculated into fermentation ends, total incubation time is 160 hours, is 165.4g/L with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC13 content.
One times of the fermented liquid thin up that obtains adds adjusting PH with base to 9.5, is heated to 90 ℃, and is centrifugal while hot, removes thalline and residual hydrocarbon.Centrifugal clear liquid adds 3.0% activated carbon decolorizing elimination gac after 20 minutes, regulate pH to 4.8 with sulfuric acid and carry out acidizing crystal, acidizing crystal liquid is cooled to room temperature, filter, wash to neutral, dried 12 hours for 80 ℃, obtain product, analyzing total acid is 99.2%, and the DC13 gas chromatographic purity is 96.0%.
4, the fermentative preparation example 4 of long carbochain biatomic acid
In the 200M3 fermentor tank of 100M3 substratum is housed, inserts secondary seed solution and begin fermentation.The fermentation culture based component is: glucose 2%, and KH2PO4 0.6%, yeast extract paste 0.7%, corn steep liquor 1.0%, urea 0.25%, NaCl 0.1%, the pH nature, 121 ℃ of sterilizations even disappear.Alkane and feed supplement sugar disappear.Under 29 ℃ of air flow 0.6vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH nature that ferments, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, begin batch formula and add C14 alkane 5%, after this added that alkane concentration maintains about 5% in alkane control fermented liquid in per 8 hours, regulate pH to 6.5 and automatic control simultaneously, pH automatic control 7.0 in 48 hours, 72 hours, pH automatic control 7.5,120 hours, pH automatic control 7.8,120 hours to putting jar, pH automatic control 8.0.Fermentation to 20,38,68 hours batches of formulas are added 1% glucose, and from being inoculated into fermentation ends, total incubation time is 143 hours, mends 28.235 tons of C14 alkane altogether, is 194.6g/L with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC14 content.
One times of the fermented liquid thin up that obtains adds adjusting PH with base to 10.5, is heated to 90 ℃, and is centrifugal while hot, removes thalline and residual hydrocarbon.Centrifugal clear liquid adds 4.0% activated carbon decolorizing elimination gac after 20 minutes, regulate pH to 3.8 with sulfuric acid and carry out acidizing crystal, acidizing crystal liquid is cooled to room temperature, filter, wash to neutral, dried 12 hours for 80 ℃, obtain product, analyzing total acid is 98.7%, and the DC14 gas chromatographic purity is 97.2%.
5, the fermentative preparation example 5 of long carbochain biatomic acid
In the 5M3 fermentor tank of 3M3 substratum is housed, inserts secondary seed solution and begin fermentation.The fermentation culture based component is: sucrose 2%, and KH2PO4 1.5%, yeast extract paste 1.0%, corn steep liquor 0.45%, urea 0.1%, the tap water preparation, the pH nature was sterilized 20 minutes for 121 ℃.C18 alkane and feed supplement sugar disappear.Under 29 ℃, air flow 0.8vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH natures ferment, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, begin to add C18 alkane 10%, added that alkane concentration maintains about 8% in alkane control fermented liquid in per during the fermentation then 12 hours, regulate pH to 7.0 simultaneously, in 48 hours, regulate pH to 7.0 with NaOH solution in per 4 hours, and 48-72 hour, regulated pH to 7.8 with NaOH solution in per 4 hours, 72-120 hour, regulated pH to 8.0 with NaOH solution in per 4 hours, 120 hours to putting jar, regulated pH to 8.5 with NaOH solution in per 4 hours.From being inoculated into fermentation ends, total incubation time is 166 hours, is 122.3g/L with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC15 content.
One times of the fermented liquid thin up that obtains adds adjusting PH with base to 11.0, is heated to 90 ℃, and 0.2 micrometer ceramics membrane microfiltration is removed thalline and residual hydrocarbon.Centrifugal clear liquid adds 4.0% activated carbon decolorizing elimination gac after 30 minutes, regulate pH to 5.0 with sulfuric acid and carry out acidizing crystal, acidizing crystal liquid is cooled to room temperature, filter, wash to neutral, dried 12 hours for 80 ℃, obtain product, analyzing total acid is 98.1%, and the DC18 gas chromatographic purity is 96.3%.
6, the fermentative preparation example 6 of long carbochain biatomic acid
In the 10L fermentor tank of 5L substratum is housed, inserts seed liquor and begin fermentation.The fermentation culture based component is: glucose 1%, and KH2PO4 1.5%, yeast extract paste 1.0%, corn steep liquor 0.5%, urea 0.45%, NaCl 0.1%, and KNO3 0.7%, the pH nature, 121 ℃ of sterilizations even disappear.Lipid acid and feed supplement sugar disappear.Under 29 ℃ of air flow 0.5vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH natures ferment, based on thalli growth, when thalli growth optical density(OD) (OD600) greater than 0.6, begin stream and add lauric acid (C12), lauric acid concentration maintains about 5% in the control fermented liquid, regulate pH to 7.0 simultaneously, in 48 hours, regulate pH to 7.0 with NaOH solution in per 4 hours, and 48-72 hour, regulated pH to 7.5 with NaOH solution in per 4 hours, 72-120 hour, regulated pH to 7.6 with NaOH solution in per 4 hours, 120 hours to putting jar, regulated pH to 7.8 with NaOH solution in per 4 hours.Fermentation to 24,48,72 hours batches of formulas are added 1% glucose.From being inoculated into fermentation ends, total incubation time is 167 hours, is 30g/L with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC12 content.
One times of the fermented liquid thin up that obtains adds adjusting PH with base to 10.0, is heated to 90 ℃, and 0.2 micrometer ceramics membrane microfiltration is removed thalline.Centrifugal clear liquid adds 2.5% activated carbon decolorizing elimination gac after 20 minutes, regulate pH to 3.5 with sulfuric acid and carry out acidizing crystal, acidizing crystal liquid is cooled to room temperature, filter, wash to neutral, dried 12 hours for 80 ℃, obtain product, analyzing total acid is 98.4%, and the DC12 gas chromatographic purity is 97.0%.
7, the fermentative preparation example 7 of long carbochain biatomic acid
In the 10L fermentor tank of 5L substratum is housed, inserts seed liquor and begin fermentation.The fermentation culture based component is: sucrose 2%, KH
2PO
41.5%, yeast extract paste 1.0%, corn steep liquor 0.45%, urea 1.0%, the tap water preparation, the pH nature was sterilized 20 minutes for 121 ℃.Under 29 ℃, air flow 0.8vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH natures ferment, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, begin to add palmitinic acid (C16) 5%, added that palmitinic acid concentration maintains about 4% in palmitinic acid control fermented liquid in per during the fermentation then 12 hours, regulate pH to 7.0 simultaneously, in 48 hours, regulate pH to 6.0 with NaOH solution in per 4 hours, and 48-72 hour, regulated pH to 6.2 with NaOH solution in per 4 hours, 72-120 hour, regulated pH to 6.8 with NaOH solution in per 4 hours, 120 hours to putting jar, regulated pH to 7.5 with NaOH solution in per 4 hours.From being inoculated into fermentation ends, total incubation time is 166 hours, with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC
16Content is 32.3g/L.
One times of the fermented liquid thin up that obtains adds adjusting PH with base to 10.0, is heated to 90 ℃, and is centrifugal while hot, removes thalline.Centrifugal clear liquid adds 2.5% activated carbon decolorizing elimination gac after 20 minutes, regulate pH to 4.5 with sulfuric acid and carry out acidizing crystal, acidizing crystal liquid is cooled to room temperature, filter, wash to neutral, dried 12 hours for 80 ℃, obtain product, analyzing total acid is 98.1%, and the DC16 gas chromatographic purity is 96.8%.
8, the purification example 1 of long carbochain biatomic acid
In 500 liters pool glass decolouring crystallizer, adds 200 kilogram 20% sodium hydroxide solution, get 100 kilograms of the DC11 crude products that obtain in the front fermentative preparation example 1, slowly add, stirring is dissolved it fully.50 kilograms in the hydrogen peroxide of adding 30% stirs and kept one hour, slowly heats up, and reaches 80 ℃ after 2 hours, and one hour rear decoloring of holding temperature finishes.Reduce temperature, with sulphur acid for adjusting pH value to 2.0,11 carbon dicarboxylic acids are all separated out.Filter, filter cake with distilled water wash repeatedly, drying.11 carbon dicarboxylic acid gas phase purity 98.1%, ash 40ppm, nitrogen content 40ppm.
9, the purification example 2 of long carbochain biatomic acid
In 1000 liters pool glass decolouring crystallizer, adds 200 kilogram 20% sodium hydroxide solution, slowly add the front and obtain 100 kilograms of the long carbochain biatomic acid DC12 that obtain in the fermentative preparation example 2, stirring is dissolved it fully.200 kilograms in the hydrogen peroxide of adding 5% stirs and kept one hour, slowly heats up, and reaches 60 ℃ after 2 hours, and one hour rear decoloring of holding temperature finishes.Reduce temperature, regulate pH value to 3.5 with sulfuric acid.Filter and repeatedly drying with the distilled water wash filter cake.Product SL-AH gas phase purity 98.3%, ash 20ppm, nitrogen content 15ppm.
10, the purification example 3 of long carbochain biatomic acid
In 1000 liters pool glass decolouring crystallizer, adds 100 kilogram 20% potassium hydroxide solution, slowly add, slowly add the front and obtain 100 kilograms of the long carbochain biatomic acid DC13 that obtain in the fermentative preparation example 3, stirring is dissolved it fully.300 kilograms in the hydrogen peroxide of adding 30% stirs and kept one hour, slowly heats up, and reaches 100 ℃ after 6 hours, and one hour rear decoloring of holding temperature finishes.Reduce temperature, with salt acid for adjusting pH value to 4.0.Filter and repeatedly drying with the distilled water wash filter cake.Product tridecanyldicarboxylic acid gas phase purity 98.1%, ash 60ppm, nitrogen content 35ppm.
11, the purification example 4 of long carbochain biatomic acid
In 1000 liters pool glass decolouring crystallizer, adds 100 kilogram 20% sodium hydroxide solution, slowly add the front and obtain 100 kilograms of the long carbochain biatomic acid DC14 that obtain in the fermentative preparation example 4, stirring is dissolved it fully.200 kilograms in the hydrogen peroxide of adding 30% stirs and kept one hour, slowly heats up, and reaches 30 ℃ after 2 hours, and 2 hours rear decolorings of holding temperature finish.Reduce temperature, with sulphur acid for adjusting pH value to 3.0.Filter and repeatedly drying with the distilled water wash filter cake.Product ten four-carbon dicarboxylic acid gas phase purity 98.2%, ash 70ppm, nitrogen content 40ppm.
12, the purification example 5 of long carbochain biatomic acid
In 500 liters pool glass decolouring crystallizer, adds 100 kilogram 20% sodium hydroxide solution, slowly add the front and obtain 40 kilograms of the long carbochain biatomic acid DC18 that obtain in the fermentative preparation example 5, stirring is dissolved it fully.140 kilograms in the hydrogen peroxide of adding 30% stirs and kept one hour, slowly heats up, and reaches 60 ℃ after 3 hours, and three hours rear decolorings of holding temperature finish.Reduce temperature, regulate pH value to 4.5 with sulfuric acid.Filter and repeatedly drying with the distilled water wash filter cake.Product 18 carbon dicarboxylic acid gas phase purity 98.0%, ash 40ppm, nitrogen content 20ppm.
13, the purification example 6 of long carbochain biatomic acid
In 1 liter beaker, add the Dilute Ammonia Solution of 300g 20%, slowly add the front and obtain long carbochain biatomic acid DC12 150 grams that obtain in the fermentative preparation example 6, stir it is dissolved fully.Feed ozone, flow 10ml/min slowly heats up, and reaches 80 ℃ after 2 hours, and one hour rear decoloring of holding temperature finishes.Reduce temperature, regulate pH value to 3.5 with hydrochloric acid.Filter and repeatedly drying with the distilled water wash filter cake.Product SL-AH gas phase purity 98.5%, ash 40ppm, nitrogen content 15ppm.
14, the purification example 7 of long carbochain biatomic acid
In 1 liter beaker, add the potassium hydroxide solution of 300g 20%, slowly add the front and obtain long carbochain biatomic acid DC16 50 grams that obtain in the fermentative preparation example 7, stir it is dissolved fully.Feed ozone, flow 5ml/min slowly heats up, and reaches 80 ℃ after 2 hours, and one hour rear decoloring of holding temperature finishes.Reduce temperature, regulate pH value to 4.0 with hydrochloric acid.Filter and repeatedly drying with the distilled water wash filter cake.Product 16-dicarboxylic acid gas phase purity 98.2%, ash 50ppm, nitrogen content 25ppm.
15, the preparation example 1 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, 100 parts of DC11 in the purification example 1 of long carbochain biatomic acid and 60 parts of diacetyl oxides, 2 parts of butanols are added in the air distillation still, heat up and also stir.Temperature of charge rises to 120 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 6 hours, until there not being product to steam, at this moment feed temperature rises to 140 ℃.The mixture cooling.
Mixture is dropped into horizontal luwa evaporator, under 2mmHg pressure, steam continuously under 160 ℃ of conditions of temperature, obtain polyanhydride, nitrogen protection cooling down obtains finished product.
Physical indexs such as the color of detection polyanhydride, ash, stability.
16, the preparation example 2 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, 100 parts of DC12 in the purification example 2 of long carbochain biatomic acid and 40 parts of diacetyl oxides, 10 parts of acetate are added in the air distillation still, heat up and also stir.Temperature of charge rises to 100 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 4-6 hour, until there not being product to steam, at this moment feed temperature rises to 140 ℃.System vacuumizes, and gas clean-up is kept about 3.5 hours nitrogen vacuum breaker, cooling discharge to 15mmHg gradually.
Physical indexs such as the color of detection polyanhydride, ash, stability.
17, the preparation example 3 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, 100 parts of DC12 and 50 parts of diacetyl oxides in the purification example 2 of long carbochain biatomic acid are added in the air distillation still, heat up and stirring.Temperature of charge rises to 120 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 1～4 hour, until there not being product to steam, at this moment feed temperature rises to 140 ℃.Mixture is dropped into horizontal luwa evaporator, under 2mmHg pressure, steam continuously under 160 ℃ of conditions of temperature, obtain polyanhydride, nitrogen protection cooling down obtains finished product.
Physical indexs such as the color of detection polyanhydride, ash, stability.
18, the preparation example 4 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, 100 parts of DC14 and 50 parts of diacetyl oxides in the purification example 4 of long carbochain biatomic acid are added in the air distillation still, heat up and stirring.Temperature of charge rises to 110 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 4～6 hours, until there not being product to steam.System vacuumizes, and gas clean-up is kept about 2 hours nitrogen vacuum breaker, cooling discharge to 2mmHg gradually.
Physical indexs such as the color of detection polyanhydride, ash, stability.
19, the preparation example 5 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, 100 parts of DC18 in the purification example 5 of long carbochain biatomic acid and 50 parts of diacetyl oxides, 8 parts of isopropylcarbinols are added in the air distillation still, heat up and also stir.Temperature of charge rises to 110 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 4～6 hours, until there not being product to steam.System vacuumizes, and gas clean-up is kept about 2 hours nitrogen vacuum breaker, cooling discharge to 2mmHg gradually.
Physical indexs such as the color of detection polyanhydride, ash, stability.
20, the preparation example 6 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, 100 parts of DC16 in the purification example 7 of long carbochain biatomic acid and 30 parts of diacetyl oxides, 10 parts of acetate are added in the there-necked flask, heat up and also stir.Temperature of charge rises to 120 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 4～6 hours, until there not being product to steam.System vacuumizes, and gas clean-up is kept about 4 hours nitrogen vacuum breaker, cooling discharge to 15mmHg gradually.
Physical indexs such as the color of detection polyanhydride, ash, stability.
21, the preparation example 7 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, 100 parts of DC12 and 30 parts of diacetyl oxides in the purification example 6 of long carbochain biatomic acid are added in the reactor, heat up and stirring.Temperature of charge rises to 130 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 2～4 hours, until there not being product to steam.Mixture is dropped into horizontal luwa evaporator, under 0.1mmHg pressure, steam continuously under 120 ℃ of conditions of temperature, obtain polyanhydride, nitrogen protection cooling down obtains finished product.
Physical indexs such as the color of detection polyanhydride, ash, stability.
22, the preparation example 8 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, with 100 parts of DC13 and 30 parts of diacetyl oxides in the purification example 3 of long carbochain biatomic acid, 4 parts of butanols add in the air distillation still, heat up and stirring.Temperature of charge rises to 130 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 4 hours, until there not being product to steam.System vacuumizes, and gas clean-up is kept about 6 hours to 5mmHg gradually, and nitrogen breaks tool extremely, cooling discharge.
Physical indexs such as the color of detection polyanhydride, ash, stability.
23, the preparation example 9 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, with 100 parts of DC13 and 40 parts of diacetyl oxides in the purification example 3 of long carbochain biatomic acid, 3 parts of acetate, 4 parts of butanols add in the air distillation still, heat up and stirring.Temperature of charge rises to 120 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 4 hours, until there not being product to steam.System vacuumizes, and gas clean-up is kept about 6 hours nitrogen vacuum breaker, cooling discharge to 10mmHg gradually.
Physical indexs such as the color of detection polyanhydride, ash, stability.
24, the preparation example 10 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, with 100 parts of DC13 and 35 parts of diacetyl oxides in the purification example 3 of long carbochain biatomic acid, 10 parts of acetate add in the air distillation still, heat up and stirring.Temperature of charge rises to 130 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 3 hours, until there not being product to steam.System vacuumizes, and gas clean-up is kept about 2 hours nitrogen vacuum breaker, cooling discharge to 1mmHg gradually.
Physical indexs such as the color of detection polyanhydride, ash, stability.
25, the preparation example 11 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, with 50 parts of DC12 and the 40 parts of diacetyl oxides in 50 parts of DC11 purification examples 2 in the purification example 1 of long carbochain biatomic acid, 3 parts of butanols add in the air distillation stills, heat up and also stir.Temperature of charge rises to 135 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 3.5 hours, until there not being product to steam.System vacuumizes, and gas clean-up is kept about 5 hours nitrogen vacuum breaker, cooling discharge to 10mmHg gradually.
Physical indexs such as the color of detection polyanhydride, ash, stability.
26, the preparation example 12 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, with 50 parts of DC14 and the 30 parts of diacetyl oxides in 50 parts of DC13 purification examples 4 in the purification example 3 of long carbochain biatomic acid, 2 parts of isopropylcarbinols add in the air distillation stills, heat up and also stir.Temperature of charge rises to 130 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 2 hours, until there not being product to steam.System vacuumizes, and gas clean-up is kept about 1.5 hours nitrogen vacuum breaker, cooling discharge to 2mmHg gradually.
Physical indexs such as the color of detection polyanhydride, ash, stability.
27, the preparation example 13 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, with 100 parts of SL-AH and 30 parts of diacetyl oxides that chemical method prepares, 4 parts of butanols add in three mouthfuls of beakers of normal pressure, heat up and also stir.Temperature of charge rises to 130 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 2.5 hours, until there not being product to steam.System vacuumizes, and gas clean-up is kept about 4 hours nitrogen vacuum breaker, cooling discharge to 2mmHg gradually.
28, the preparation example 14 of long carbochain biatomic acid polyanhydride:
Under nitrogen protection, with 100 parts of commercial biological process SL-AH and 30 parts of diacetyl oxides, 4 parts of butanols add in three mouthfuls of beakers of normal pressure, heat up and also stir.Temperature of charge rises to 130 ℃ after one hour, has small-molecule substance to steam simultaneously.Keep normal pressure and steamed 2.5 hours, until there not being product to steam.System vacuumizes, and gas clean-up is kept about 4 hours nitrogen vacuum breaker, cooling discharge to 2mmHg gradually.
Physical indexs such as the color of detection polyanhydride, ash, stability.
Part polyanhydride product detected result sees the following form:
| SL-AH polyanhydride sample | SL-AH polyanhydride sample | 11 carbon dicarboxylic acid polyanhydride samples | SL-AH polyanhydride sample | Mix 11 and SL-AH polyanhydride sample | Ten four-carbon dicarboxylic acid polyanhydride samples | 18 carbon dicarboxylic acid polyanhydride samples | |
| The diprotic acid source | Chemical process/outsourcing | Fermentation method/outsourcing | Fermentation method/self-control | Fermentation method/self-control | Fermentation method/self-control | Fermentation method/self-control | Fermentation method/self-control |
| The polyanhydride operational path | Prepare according to traditional route oneself | Prepare according to traditional route oneself | Long carbochain biatomic acid polyanhydride preparation example 1 | Long carbochain biatomic acid polyanhydride preparation example 2 | Long carbochain biatomic acid polyanhydride preparation example 11 | Long carbochain biatomic acid polyanhydride preparation example 4 | Long carbochain biatomic acid polyanhydride preparation example 5 |
| The polyanhydride outward appearance | White | Yellow-white | Oyster white | Oyster white | Oyster white | White | White |
| Polyanhydride color (Gardner) | 2 ? | 4 ? | 2 ? | 1 ? | 1 ? | 1.5 ? | 1 ? |
| * polyanhydride colour stability (Gardner) | 4 ? ? | 10 ? ? | 3 ? ? | 2 ? ? | 3 ? ? | 4 ? ? | 1.5 ? ? |
| Polyanhydride ash (ppm) | 100 ? | 300 ? | 70 ? | 30 ? | 35 ? | 80 ? | 20 ? |
| Polyanhydride nitrogen content (ppm) | 40 ? | 500 ? | 60 ? | 25 ? | 20 ? | 50 ? | 15 ? |
| Long carbochain biatomic acid total content (%) after the hydrolysis | 98.3 ? ? | 96.5 ? ? | 98.5 ? ? | 98.6 ? ? | 98.5 ? ? | 98.1 ? ? | 98.4 ? ? |
The measuring method of polyanhydride colour stability is as follows in this experiment: take by weighing 100 gram polyanhydride samples and be placed in the crucible, be built in 120 ℃ of baking ovens, oxygen feeds the sample bottom, and continuously uniform bubbling one hour takes out postcooling.The color of test sample.
From above experiment and other experiments that we carry out, the contriver thinks, the polyanhydride product appearance that obtains among the present invention is better, color, ash and be subjected to the xanthochromic performance of thermooxidizing to be higher than the long carbochain biatomic acid polyanhydride that chemical method is produced, be far superior to the polyanhydride that conventional biological process long carbochain biatomic acid prepares, meet of the requirement of high-grade powder coating fully solidifying agent.Simultaneously, with respect to the chemical method diprotic acid, cost has great reduction, for the industrialization expansion of long carbochain biatomic acid polyanhydride is laid a good foundation.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (15)
1. it is the long carbochain biatomic acid polyanhydride that the step of raw material by bio-transformation and chemical polymerization prepare that sets out that powder paint solidifying agent, wherein said solidifying agent contain with alkane or lipid acid.
2. powder paint solidifying agent according to claim 1, the used long-chain biatomic acid carbonatoms of wherein said long carbochain biatomic acid polyanhydride is between 11 to 18.
3. powder paint solidifying agent according to claim 1, wherein said long carbochain biatomic acid polyanhydride is meant color less than 2 (Gardner colourities), and the ash content of coal is below 80ppm, nitrogen content is less than 60ppm, and total dicarboxylic acid content is not less than 98% long carbochain biatomic acid polyanhydride after the polyanhydride hydrolysis.
4. the preparation method of a long carbochain biatomic acid polyanhydride, comprise polymerization procedure and purification step, wherein polymerization procedure is at first the alkane of particular carbon chain length to be produced long carbochain biatomic acid by the method for biological fermentation, this diprotic acid is carried out purification processes to reach specific specification requirement, then with long carbochain biatomic acid and other reactive material of the appropriate amount handled well, composition and molecular weight control according to the polyanhydride that has the polyanhydride solidifying agent now, ingredient proportion is put in the air distillation still, under protection of inert gas, be heated to 100～140 ℃, normal pressure steams lower-molecular substance, and distillation time is 1～6 hour; Described purification step is at vacuum tightness＜15mmHg, 110～140 ℃ of temperature, underpressure distillation and obtain finished product.
5. the preparation method of long carbochain biatomic acid polyanhydride according to claim 4, wherein said purification step is in the wiped film vaporization device, distill, after removing small-molecule substance, obtain the polyanhydride finished product, the vacuum range of wiped film vaporization device is below 2mmHg, and vaporization temperature is at 120～180 ℃, and residence time of material was less than 5 minutes.
6. the preparation method of long carbochain biatomic acid polyanhydride according to claim 5, wherein in the wiped film vaporization process, employed wiped film vaporization device is vertical-type evaporator or horizontal-type evaporator.
7. the preparation method of long carbochain biatomic acid polyanhydride according to claim 4, wherein employed long carbochain biatomic acid, its gas phase purity＞98%, ash＜60ppm, nitrogen content＜50ppm, color＜2 (Gardner colourity) is to reach the requirement of polyanhydride solidifying agent to diprotic acid.
8. the preparation method of long carbochain biatomic acid polyanhydride according to claim 7, wherein employed long carbochain biatomic acid is the monounsaturated dicarboxylic acid by carbonatoms from 11 to 18 carbon of biological fermentation process production.
9. the preparation method of long carbochain biatomic acid polyanhydride according to claim 4, wherein employed this employing of long carbochain biatomic acid biological process is prepared from, and it may further comprise the steps:
1) fermentation method transforms: alkane or lipid acid with C11～C18 are substrate, are converted into the corresponding long chain diprotic acid by microbe fermentation method;
Wherein, microorganism is adopted candida tropicalis (Candida Tropicalis), and the prescription of fermentation tank culture medium is: KH2PO4:0.2～1.5%; NaCl:0～0.2%; Yeast extract paste: 0.1～2.0%; Urea: 0.2～1.5%; Glucose: 1.0～5.0%; (NH4) 2SO4:0～2.0%; MgSO47H2O:0～0.3%; Defoamer: 0.005%;
Fermentation condition is: inoculum size: 20%; Jar temperature: 29.0 ± 1.0 ℃; Ventilation: 1: 1.0～0.2vvm; Tank pressure: 0.05～0.1Mpa; PH: earlier fermentation thalli growth 3.5～6.5; The fermentation middle and later periods transforms 7.0～8.5; Incubation time: 120～170 hours;
The feed supplement controlled variable:
--alkane/lipid acid: as thalli growth optical density(OD) (OD
600) greater than 0.6, begin to add 5～10% alkane or lipid acid, adding in the alkane lipid acid control fermented liquid alkane or fatty acid concentration thereafter is 2～10%, fermentation ends stopped feed supplement in preceding 24 hours;
2) extraction of diprotic acid: fermented liquid is added adjusting PH with base to 8～11, be heated to 60～100 ℃, utilize centrifuging or membrane filter method separating thallus then, diprotic acid clear liquid and the remaining substrate of fermentation; The diprotic acid clear liquid that obtains adds the gac that is no more than clear liquid volume 5% content according to circumstances, 60～95 ℃ of decolourings 20～180 minutes, remove by filter gac, destainer is heated to 60～100 ℃ then, carry out acidizing crystal with acid for adjusting pH to 2～5, acidizing crystal liquid obtains the long carbochain biatomic acid crude product through filter press again; With alkaline solution dissolving long carbochain biatomic acid crude product, after treating that diprotic acid fully dissolves, add the oxygenant of oxygenant mole number and be heated to 30～100 ℃ and carried out oxidative decoloration 1-8 hour, treat oxidizing reaction finish the back with acid for adjusting pH value to 3.0-4.0, the long carbochain biatomic acid crystallization is separated out, centrifugal or collect product with Plate Filtration, after repeatedly washing with distilled water, drying obtains finished product.
10. the preparation method of long carbochain biatomic acid polyanhydride according to claim 9, wherein said alkaline solution is sodium hydroxide, potassium hydroxide, ammoniacal liquor or other inorganic alkali solutions.
11. the preparation method of long carbochain biatomic acid polyanhydride according to claim 9, wherein said alkaline solution is a sodium hydroxide solution.
12. the preparation method of long carbochain biatomic acid polyanhydride according to claim 9, wherein said oxygenant is hydrogen peroxide or ozone.
13. the preparation method of long carbochain biatomic acid polyanhydride according to claim 9, wherein said oxygenant is a hydrogen peroxide, and the concentration of hydrogen peroxide is 5～50%.
14. the preparation method of long carbochain biatomic acid polyanhydride according to claim 9, wherein said acid is organic acids such as mineral acids such as sulfuric acid or hydrochloric acid or acetate.
15. the preparation method of long carbochain biatomic acid polyanhydride according to claim 9, wherein said acid is sulfuric acid.
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| CNA200610029191XA CN101108928A (en) | 2006-07-20 | 2006-07-20 | Powder paint solidifying agent and method of manufacturing used long chain carbon polyanhydride |
| PCT/CN2006/002341 WO2008011763A1 (en) | 2006-07-20 | 2006-09-11 | A curing agent for powder coating and the preparation method of the long chain dicarboxylic acid polyanhydride used in said powder coating |
| JP2009519777A JP2009543905A (en) | 2006-07-20 | 2006-09-11 | Powder coating curing agent and long carbon chain polyanhydride preparation method used |
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| US5055524A (en) * | 1987-07-16 | 1991-10-08 | Ppg Industries, Inc. | Polyol-modified polyanhydride curing agent for polyepoxide powder coatings |
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| DE60306576T2 (en) * | 2002-05-07 | 2007-07-05 | Mitsui Chemicals, Inc. | Thermosetting powder coating composition, process for producing a coating film with the composition and coating film |
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| CN1292072C (en) * | 2004-05-12 | 2006-12-27 | 上海凯赛生物技术研发中心有限公司 | Long chain normal dibasic acid production method |
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| JP2009543905A (en) | 2009-12-10 |
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