WO2008011763A1 - Durcisseur pour revêtement en poudre et procédé de préparation du polyanhydride d'acide dicarboxylique à chaîne longue utilisé dans ce revêtement en poudre - Google Patents

Durcisseur pour revêtement en poudre et procédé de préparation du polyanhydride d'acide dicarboxylique à chaîne longue utilisé dans ce revêtement en poudre Download PDF

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WO2008011763A1
WO2008011763A1 PCT/CN2006/002341 CN2006002341W WO2008011763A1 WO 2008011763 A1 WO2008011763 A1 WO 2008011763A1 CN 2006002341 W CN2006002341 W CN 2006002341W WO 2008011763 A1 WO2008011763 A1 WO 2008011763A1
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Prior art keywords
dibasic acid
carbon chain
long carbon
chain dibasic
polyanhydride
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PCT/CN2006/002341
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English (en)
Chinese (zh)
Inventor
Bingbing Qin
Rongfu Zhang
Jinsheng Zhong
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Cathay R & D Center
Cathay Biotech Ltd.
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Priority to JP2009519777A priority Critical patent/JP2009543905A/ja
Publication of WO2008011763A1 publication Critical patent/WO2008011763A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6409—Fatty acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/54—Preparation of carboxylic acid anhydrides
    • C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/54—Preparation of carboxylic acid anhydrides
    • C07C51/573—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13—Dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D5/033—Powdery paints characterised by the additives

Definitions

  • the invention relates to the technical field of powder coating curing agents, in particular to a high quality long carbon chain dibasic acid polyanhydride curing agent prepared by bioconversion and chemical polymerization starting from an alkane or a fatty acid.
  • This product is a new curing agent for powder coatings.
  • the invention also provides a preparation process of the long carbon chain dibasic acid polyanhydride curing agent, which starts from an alkane or a fatty acid, and produces a long carbon chain dibasic acid by a biological fermentation method, after a special purification process, in the catalyst Dehydration under the action of a polyanhydride. Background technique
  • Thermosetting powder coatings are environmentally friendly coatings with very little or no solvent emissions.
  • Europe and the United States the market for powder coatings is growing steadily due to increasingly stringent requirements for voc (volatile organic compounds).
  • a long carbon chain dibasic acid having 9 to 18 carbon atoms or an anhydride thereof is a commonly used curing agent for epoxy powder coatings and acrylic powder coatings.
  • Epoxy coatings are the most widely used and widely used coatings in powder coatings. They are generally cured with amines, acid or anhydride curing agents. It is stated in the patents US 665 291, US Pat. No. 6,448,345, EP 0 299 420 that the use of long carbon chain dibasic anhydride as a curing agent for epoxy coatings greatly improves the flexibility, crack resistance, and coating of epoxy powder coatings. Excellent mechanical and anti-aging properties.
  • Acrylic powder coatings are a class of high-grade weatherable powder coatings.
  • Common acrylic powder coating curing agents are polycarboxylic acids or their anhydrides, polyamines, polyhydric phenols, polyhydroxy compounds, and the like.
  • the aliphatic dicarboxylic acid and its anhydride are the best curing agents, and are the mainstream of acrylic powder coatings.
  • the long carbon chain dibasic acid itself has a relatively high melting point and requires a relatively high curing temperature when used as a curing agent for acrylic powder coatings. This imposes limitations on the application of acrylic powder coatings.
  • long carbon chain dibasic acid polyanhydrides have been developed as curing agents for acrylic powder coatings.
  • thermosetting powder coating composition disclosed in Chinese Patent No. CN1456616, and the coating method and coating method thereof
  • the film indicates that the long carbon chain dibasic acid polyanhydride has a lower melting point and a higher reactivity than the long carbon chain dibasic acid. Therefore, powder coatings based on long carbon chain polyanhydrides have a thin coating thickness, outstanding flexibility, scratch resistance and low temperature curing properties. These properties are considered to be the focus of recent automotive coating research.
  • long carbon chain polyanhydrides are used in high-grade epoxy or acrylic powder coatings, there is a high demand for the quality of long carbon chain polyanhydrides, especially their ash, color and yellowing resistance. If the ash content of the long carbon chain dibasic acid polyanhydride is high, the appearance properties of the powder coating film will be deteriorated, and the increase in impurities will be observed, and at the same time, the long-term yellowing resistance and aging property of the coating film will also be affected. If the color of the long carbon chain polyanhydride product is yellow and the yellowing resistance is poor, it will have a great influence on the appearance, gloss and long-term weather resistance of the powder coating film, thereby limiting the application of polyanhydride in high-grade powder coating. . According to the relevant literature and industrial practice, the ash content of polyanhydride is kept below 100 ppm, and the color less than 2 (Gardner color) is a suitable index.
  • the long carbon chain dibasic acid polyanhydride has poor ash, color or yellowing resistance, and has a great relationship with the content of easily oxidized impurities in the polyanhydride and the production process.
  • due to the small industrial production scale of polyanhydrides there are few studies on the production process and quality of polyanhydrides, and there is almost no literature or report on this.
  • the former long carbon chain dibasic acid polyanhydride is mostly produced by a chemically produced 12-carbon dibasic acid.
  • the chemical acid's dibasic acid price is relatively high, the production and application of polyanhydride is greatly limited.
  • the long carbon chain dibasic acid produced by the chemical method contains intermediates or by-product impurities with a ketone group or a nitric acid group, and the heating of these materials has a great influence on the color of the finished polyanhydride.
  • an alkane or a fatty acid is used as a raw material, and it is converted into a long carbon chain dibasic acid by a biological method, thereby successfully achieving the burst of a high quality long carbon chain dibasic acid polyanhydride.
  • the biological method for producing long carbon chain dibasic acid has the characteristics of environmental protection and energy saving, good product quality, and the cost and price are obviously lower than the chemical method dibasic acid, which provides a possibility for the industrialization of polyanhydride.
  • the present invention generally relates to the production of long carbon chain dibasic acid polyanhydrides using biologically derived dibasic acids as starting materials.
  • long carbon chain dibasic acid has low purity, high residual amount of ash and nitrogen substances, and is not suitable for the production of long carbon chain dibasic acid polyanhydride, and the obtained polyanhydride product is The ash and yellowing resistance are completely incompatible with the requirements of high-grade powder coatings.
  • the nitrogen content of biologically long carbon chain dibasic acids can have a large impact on polyanhydrides.
  • Long-chain carbonic acid produced by biological fermentation which is affected by the fermentation broth, generally has some proteins and other Nitrogen organic substances remain.
  • nitrogen-containing substances are easily oxidized and yellowed, which in turn affects the color of the finished product.
  • polyaniline with high nitrogen content will also deteriorate the long-term weather resistance and yellowing resistance of powder coating film, which in turn limits the application of polyanhydride as a curing agent in special-purpose powder coatings.
  • the purity of the long carbon chain dibasic acid also affects the quality of the polyanhydride.
  • the existing biological method has a purity of dibasic acid of generally 97% (gas phase method), an uncontrolled impurity and nitrogen content, and a large fluctuation range, which is completely unsuitable for the production of a long carbon chain dibasic acid polyanhydride.
  • thermosetting powder coating composition disclosed in the patent CN1456616, a method for producing the coating film thereof, and a coating film, after the finished product of the polyanhydride is heated, dissolved in an isobutyl acetate solvent, and activated carbon is used.
  • the long carbon chain dibasic acid polyanhydride itself is a very unstable polymer, which is very easy to absorb water and degrade.
  • the distillation is easy to yellow at high temperature, and the solubility varies greatly with the degree of polymerization, so that the method of dissolving and filtering is industrial. It is difficult to achieve.
  • the quality of the finished poly-anhydride is not guaranteed and cannot be applied to the quality coatings on a large scale.
  • the invention adopts a unique dibasic acid fermentation technology, and controls the purity, ash content and nitrogen content of the raw materials through strict binary acid purification technology, thereby obtaining a high-quality long carbon chain dibasic acid polyanhydride.
  • the product is fully compliant with the requirements of the powder coating manufacturer.
  • the reactants such as long carbon chain dibasic acid and dehydrating agent are generally heated and atmospherically distilled in the reaction vessel, and then vacuum distilled at 160 to 180 ° C for a long time.
  • the finished polyanhydride is obtained.
  • a common problem in this process is that the distillation temperature is too high in the later stages of the process, and the reaction time is too long, which directly leads to the yellowing of the final polyanhydride product.
  • the temperature and the distillation time of the distillation are strictly controlled under high vacuum conditions, or the distillation by the membrane evaporation device is used to maximize the color and quality of the product.
  • One of the technical problems to be solved by the present invention is to provide a powder coating curing agent which has low impurity content, light color, good yellowing resistance, and meets or far exceeds the requirements of the powder coating for the curing agent.
  • the second technical problem to be solved by the present invention is to provide a method for preparing a long carbon chain dibasic acid polyanhydride used for preparing the above curing agent, which is a method for producing a long carbon chain dibasic acid by a biological fermentation method starting from an alkane or a fatty acid. After a special purification process, it is dehydrated by the action of a catalyst to form a polyanhydride.
  • the prepared long carbon chain dibasic acid polyanhydride has low impurity content, light color and good yellowing resistance.
  • the curing agent contains a terpene hydrocarbon or a fatty acid as a starting point A long carbon chain dibasic acid polyanhydride prepared by a biological method.
  • the long carbon dibasic acid polyanhydride has a long chain diacid carbon number of between eleven and eighteen.
  • the long carbon chain dibasic acid polyanhydride in the present invention means that the color is less than 2 (Gardner color), the ash content is below 80 ppra, the nitrogen content is less than 60 ppm, and the total dibasic acid content after hydrolysis of the polyanhydride is not less than 98%.
  • Long carbon chain dibasic acid polyanhydride Its light color and outstanding yellowing resistance can fully meet the requirements of high-grade powder coatings for curing agents.
  • the preparation method of the long carbon chain dibasic acid polyanhydride according to the second aspect of the present invention comprises a polymerization step and a purification step, wherein the polymerization step is first to produce a long carbon chain (or fatty acid) having a specific carbon chain length by biological fermentation. a carbon chain dibasic acid, which is purified to meet specific specifications, and then a suitable amount of long carbon chain dibasic acid and other reactive materials are treated according to the polyanhydride of the existing polyanhydride curing agent.
  • the composition and molecular weight control the proportion of feed is put into the atmospheric distillation still, heated to 100 ⁇ 140 ° C under the protection of inert gas, the low molecular substance is distilled off at normal pressure, and the distillation time is 1 to 6 hours; the purification step
  • the vacuum is ⁇ 15mmHg, the temperature is 110 ⁇ 140°C, and the product is obtained by distillation under reduced pressure; or in the wiped film evaporation device, the distillation is performed to remove the small molecular substance, and the finished product of the polyanhydride is obtained, and the vacuum of the wiped film evaporation device is obtained.
  • the range is below 2mmHg, the evaporation temperature is 120 ⁇ 180°C, and the material residence time is less than 5 minutes.
  • the wiped film evaporation device used is a vertical evaporator or a horizontal evaporator.
  • the long carbon chain dibasic acid used has gas phase purity
  • the long carbon chain dibasic acid used is a saturated dibasic acid having a carbon number of from eleven to eighteen carbons produced by a bio-fermentation method.
  • the long carbon chain dibasic acid used is prepared by a biological method, which comprises the following steps:
  • Fermentation conversion conversion to a corresponding long-chain dibasic acid by microbial fermentation using C11 ⁇ C18 alkane or fatty acid as a substrate;
  • the formula of the fermenter is: KH2P04: 0. 2 ⁇ 1. 5%; NaCl: 0 ⁇ 0. 2%; yeast extract: 0. 1 ⁇ 2. 0%; Urea: 0. 2 ⁇ 1. 5%; Glucose: 1. 0 ⁇ 5. 0%; (NH4) 2S04: 0 ⁇ 2. 0%; MgS04 ⁇ 7H20: 0 ⁇ 0. 3%; Agent: 0. 005%;
  • Fermentation conditions are: inoculum: 20%; tank temperature: 29. 0 ⁇ 1. 0 ° C ; ventilation: 1 : 1. 0 ⁇ 0. 2vvm ; tank pressure: 0. 05 ⁇ 0. 1Mpa; pH: fermentation 5 ⁇ 8. 5; Peining in the middle and late stages of fermentation 7. 0 ⁇ 8. 5; Raising time: 120 ⁇ 170 hours;
  • dibasic acid adjust the pH of the fermentation broth to 8 ⁇ 11 with alkali, heat to 60 ⁇ ; ⁇ , then separate the cells, the diacid solution and the substrate of the fermentation residue by centrifugation or membrane filtration.
  • the obtained dibasic acid solution is added with activated carbon not exceeding 5% of the volume of the clear liquid, and is decolorized at 60 to 95 Torr for 20 to 180 minutes, and the activated carbon is removed by filtration, and then the decoloring liquid is heated to 60 to 100 ° C, using acid.
  • the oxidizing agent is heated to 30 ⁇ 100 Torr for oxidative decolorization for 1-8 hours.
  • the pH is adjusted to 3. 0-4.
  • the long carbon chain dibasic acid is crystallized, centrifuged or used. The product was collected by plate and frame filtration, washed several times with distilled water, and dried to obtain a finished product.
  • the alkali solution is sodium hydroxide, potassium hydroxide, aqueous ammonia or other inorganic alkali solution.
  • the oxidizing agent is hydrogen peroxide or ozone.
  • the acid is an inorganic acid such as sulfuric acid or hydrochloric acid, or an organic acid such as acetic acid.
  • the long carbon chain dibasic acid polyanhydride of the invention has light color and outstanding yellowing resistance, and can fully meet the requirements of high-grade powder coatings for curing agents. ' Description of the drawings
  • Figure 1 is a process flow diagram of the present invention. detailed description
  • a powder coating curing agent containing a long carbon chain dibasic acid polyanhydride prepared by a biological method starting from an alkane or a fatty acid.
  • the long-chain dibasic acid carbon atoms used in the long carbon chain dibasic acid polyanhydride are between eleven and eighteen.
  • the long carbon chain dibasic acid polyanhydride used means that the color is less than 2 (Gardner color) and the ash content is 80 ppm.
  • the long carbon chain dibasic acid polyanhydride having a nitrogen content of less than 60 ppm and a total dibasic acid content after hydrolysis of the polyanhydride is not less than 98%. Its light color and outstanding yellowing resistance can fully meet the requirements of high-grade powder coatings for curing agents.
  • a method for preparing a long carbon chain dibasic acid polyanhydride comprising a polymerization step and a purification step, wherein the polymerizing step is first to produce a long carbon chain dibasic acid by biological fermentation of a specific carbon chain length alkane or fatty acid, The dibasic acid is purified to meet specific specifications, and then a suitable amount of long carbon chain dibasic acid and other reactive materials are treated, and the composition and molecular weight of the polyanhydride of the existing polyanhydride curing agent are controlled.
  • the proportion of the feed is put into an atmospheric distillation still, heated to 100 ⁇ 140 ° C, and the low molecular substance is distilled off at a normal pressure, and the distillation time is 1 to 6 hours; then, the vacuum degree is ⁇ 15 mmHg, the temperature is 110 to 140 ° C, and the pressure is reduced. Distillation to obtain a finished product; or in a wiped film evaporation apparatus, steaming is carried out to remove small molecular substances, thereby obtaining a finished polyanhydride.
  • the wiper evaporator has a vacuum range of less than 2 mmHg and an evaporation temperature of 120 to 18 (TC, material residence time of less than 5 minutes.
  • the wiped film evaporation device used is a vertical evaporator or a horizontal evaporator.
  • the long carbon chain dibasic acid used has a gas phase purity of >98%, an ash content of ⁇ 60 ppm, a nitrogen content of ⁇ 50 ppm, and a color ⁇ 2 (Gardner color) to achieve a polyanhydride curing agent for the dibasic acid.
  • Claim For example, a saturated dibasic acid having a carbon number of from eleven to eighteen carbons produced by a bio-fermentation process.
  • the method of biologically producing a long chain dibasic acid comprises the following steps -
  • the formula of the fermenter medium is: KH2P04: 0. 2 ⁇ 1. 5 0 / 0 ; NaCl: 0 ⁇ 0 . 2%; yeast extract: 0. 1 ⁇ 2. 0%; Urea: 0. 2 ⁇ : 1. 5%; Glucose: 1. 0 ⁇ 5. 0%; (NH4) 2S04: 0 ⁇ 2. 0%; MgS04 ⁇ 7H20: 0 ⁇ 0. 3% ; 'Antifoaming agent: 0. 005%, MnS04 0. 0001-0. 001%, CuS04 0. 0001-0. 001%;
  • Fermentation conditions are: Inoculum: 20%; Tank temperature: 29. 0 ⁇ 1. 0 ⁇ ; Ventilation: 1 : 1. 0 ⁇ 0. 2vvm; Tank pressure: 0. 05 ⁇ 0. 1Mpa; pH: Pre-fermentation bacteria 5 ⁇ 6. 5; Cultivation time: 140 ⁇ 170 hours; body growth 3. 5 ⁇ 6. 5;
  • a hydrocarbon/fatty acid When the growth density of the cells (OD600) is greater than 0.6, the addition of 5 to 10% of the alkane or fatty acid is started, and then the alkane fatty acid is added to control the concentration of the alkane or fatty acid in the fermentation broth to 2 ⁇ 10. %, before the end of fermentation Stop feeding in 2 hours;
  • Dibasic acid extraction The operation process of re-purifying the biological method long carbon chain dibasic acid product is as follows: The fermentation liquid or the enzymatic reaction liquid is adjusted to pH 8 to 11 by alkali, and heated to 60 to 100 ° C, Then, the cells, the dibasic acid solution and the substrate of the fermentation residue are separated by centrifugation or membrane filtration; the obtained dibasic acid solution is optionally added with 0 to 5% of activated carbon, and decolorized at 60 to 95 ° C.
  • the activated carbon was removed by filtration, and then the decoloring liquid was heated to 60 to 100 ° C, and the pH was adjusted to 2 to 5 by H 2 SO 4 to carry out acidification crystallization, and the acidified crystal solution was filtered through a plate frame to obtain a crude dibasic acid;
  • Dibasic acid purification Dissolve the long carbon chain dibasic acid with an alkali solution. After the dibasic acid is fully dissolved, add the oxidizing agent and heat to 30 ⁇ 100 Torr for oxidative decolorization for 1-8 hours for oxidative decolorization. After the reaction, the pH is adjusted to 3. 0-4. 0, the long carbon chain dibasic acid crystallizes, and the product is collected by centrifugation or filtration through a plate frame, washed with distilled water several times, and dried to obtain a finished product.
  • the alkali solution used is sodium hydroxide solution or potassium hydroxide solution or ammonia water or other inorganic alkali solution; preferably sodium hydroxide solution.
  • the oxidizing agent used is hydrogen peroxide or ozone, preferably hydrogen peroxide, the concentration of hydrogen peroxide is generally 5 to 50%, and the amount of the oxidizing agent is the number of moles of the oxidizing agent: the number of moles of the dibasic acid is ⁇ 2. ⁇
  • the acid solution used in the acidification is generally an inorganic acid such as sulfuric acid or hydrochloric acid, or an organic acid such as acetic acid. It is preferably sulfuric acid.
  • the purified long carbon chain dibasic acid product of the present invention requires a gas phase purity of >98%, an ash content of ⁇ 60 ppm, and a nitrogen content of ⁇ 50 ppm to meet the requirements of the polyanhydride curing agent for the dibasic acid.
  • seed liquid was introduced to start fermentation. 5 ⁇
  • the fermentation medium composition glucose 1.5. /. , KH2P04 1. 5%, yeast extract 1. 0%, corn syrup 0. 5%, urea 0. 35%, NaCl 0. 1%, KN03 0. 7%, pH natural, 121 °C sterilization. Hydrocarbons and feed sugars are eliminated.
  • the culture was carried out under the condition of OMpa at a pressure of 0. 5 vvm at 29 ⁇ .
  • the pH is natural 20 hours before fermentation, and the growth of the cells is dominant.
  • the C11 hydrocarbon is added to control the concentration of C11 hydrocarbon in the fermentation liquid to be maintained at 5%.
  • the pH is adjusted to 7. 0, 48-72 hours, with a NaOH solution every 4 hours.
  • the pH is adjusted to 8.0 with NaOH solution every 4 hours.
  • the pH is adjusted to 8.0 by the NaOH solution every 4 hours.
  • the obtained fermentation broth was diluted with water and doubled.
  • the pH was adjusted to 8.0 by adding alkali, heated to 90 Torr, and centrifuged to remove bacteria and residual hydrocarbons. After centrifugation with 2.5% activated carbon for 20 minutes, the activated carbon was filtered off, and the pH was adjusted to 2. 0 with sulfuric acid.
  • the acidified crystal was cooled, cooled to room temperature, filtered, washed to neutral, dried at 80 ° for 12 hours. 8% ⁇
  • the product was analyzed, the total acid was 99.0%, DC11 gas chromatographic purity was 96.8%.
  • a 200 M3 fermentor containing 100 M3 of medium seed liquid was introduced to start fermentation.
  • the composition of the fermentation medium is: glucose 3. 0%, KH2P04 0. 5%, yeast extract 2%, corn syrup 1. 5%, urea 0. 25%, NaCl 0. 2%, KN03 0. 5%, tap water preparation , pH natural, 121 °C sterilization. C12 terpene and feed sugar are eliminated.
  • tank pressure l. OMpa culture The pH is natural 20 hours before fermentation, and the growth of the cells is dominant. When the growth density (0D) of the cells is greater than 0.
  • the obtained fermentation broth was diluted twice with water, adjusted to pH 9.0 with alkali, heated to 90 ° C, and centrifuged to remove bacteria and residual hydrocarbons. After centrifugation, the activated carbon was decolorized by adding 5% activated carbon for 20 minutes, and the activated carbon was filtered off, and the pH was adjusted to 3. 5 with sulfuric acid. The acidified crystal was cooled to room temperature, filtered, washed to neutral, dried at 80 ° for 12 hours. 8% ⁇ The product was analyzed, the total acid was 99.0%, DC12 gas chromatographic purity was 96.8%.
  • the introduced secondary seed solution was started to ferment.
  • the sucrose is 4. 0%, KH2P04 0. 8%, yeast extract 1. 0%, corn syrup 0. 5%, urea 0. 35%, NaCl 0. 1%, KN03 0. 7%,
  • the pH is natural and the sterilization is eliminated at 121 °C. Hydrocarbons and feed sugars are eliminated.
  • the culture was carried out under the condition of OMpa at a gas pressure of 0. 6 vvm at 29 ° C.
  • the pH is natural 20 hours before fermentation, and the growth of the cells is dominant.
  • the C13 alkane is added in batches of 5%, and then the hydrocarbon-controlled fermentation broth is added every 8 hours.
  • the concentration of the intermediate alkane is maintained at about 5%, while adjusting the pH to 6.5 and self-control, 48 hours of pH control 7. 0, 72 hours, 11 automatic control 7. 5, 120 hours, 11 automatic control 7. 8, 120 hours to the can , pH control 8. 0. Fermentation to 18, 32,
  • the amount of the DC13 content of the fermentation solution was determined to be 165.4 g/L by the extraction of NaOH titration with diethyl ether.
  • the obtained fermentation broth was diluted twice with water, adjusted to pH 9.5 with alkali, heated to 90 ° C, and centrifuged to remove bacteria and residual hydrocarbons. After centrifugation, add 0.3% activated carbon for 20 minutes, then filter off the activated carbon, adjust the pH to 4.8 with sulfuric acid, acidify the crystal, cool the acidified crystal solution to room temperature, filter, wash to neutral, 80 °C drying 12 0% ⁇ The purity of the gas chromatographic purity was 96.0%.
  • the secondary seed solution was added to start the fermentation.
  • the composition of the fermentation medium is: glucose 2%, KH2P04 0. 6%, yeast paste 0. 7%, corn paddle 1. 0%, urea 0. 25%, NaCl 0. 1%, pH natural, 121 °C sterilization Even disappear. Alkanes and feed sugars are eliminated. Incubate at 29 ⁇ ventilation volume 0. 6vvm, tank pressure l. OMpa condition. 20 hours before fermentation, the pH is natural, mainly based on bacterial growth, when the growth density (0D) of the cells is greater than
  • the obtained fermentation broth was diluted twice with water, adjusted to pH 10.5 with alkali, heated to 90 ° C, and centrifuged to remove bacteria and residual hydrocarbons. After centrifugation, add 0.4% activated carbon for 20 minutes, then filter off the activated carbon, adjust the pH to 3.8 with sulfuric acid, acidify the crystal, cool the acidified crystal solution to room temperature, filter, wash to neutral, dry at 80 °C 2% ⁇ The purity of the gas chromatographic purity was 97.2%.
  • the secondary seed solution was introduced to start the fermentation.
  • the composition of the fermentation medium is: sucrose 2%, KH2P04 1. 5%, yeast extract 1. 0%, corn syrup 0. 45%, urea 0.1%, tap water preparation, pH natural, sterilization at 121 °C for 20 minutes. C18 alkane and feed sugar are eliminated.
  • Ventilation 0. 8vvm tank pressure
  • the obtained fermentation broth was diluted twice with water, adjusted to pH 11. 0 with alkali, heated to 90 ° C, and 0.2 ⁇ m ceramic membrane was microfiltered to remove bacteria and residual hydrocarbons. After centrifugation, add 4.0% activated carbon for 30 minutes, then remove the activated carbon, adjust the pH to 5.0 with sulfuric acid, acidify the crystal, cool the acidified crystal solution to room temperature, filter, wash to neutral, dry at 80 °C. 3% ⁇ The purity of the gas chromatographic purity was 96.3%.
  • the seed solution was introduced to start fermentation.
  • the composition of the fermentation medium is: glucose 1%, KH2P04 1. 5%, yeast extract 1. 0%, corn syrup 0. 5%, urea 0. 45%, NaCl 0. 1%, KN03 0. 7%, pH naturally , Sterilization at 121 °C. Fatty acids and feed sugars are eliminated. Ventilation at 29 ° C 0. 5vvm, tank pressure 1. Culture under OMpa conditions. The pH was natural for 20 hours before fermentation, and the growth of the cells was dominant.
  • the lauric acid (C12) was started to flow, and the concentration of lauric acid in the fermentation broth was maintained at 5%.
  • the pH is adjusted to 7.5, 72-120 hours, every 4 hours with NaOH solution to adjust the pH to 7.5, 72-120 hours, every 4 hours.
  • the pH is adjusted to 7.8 with a NaOH solution every 4 hours. Fermentation to 24, 48, 72 hours batch plus 1% glucose. From the inoculation to the end of the fermentation, the total incubation time was 167 hours, and the DC12 content of the fermentation stock solution was determined to be 30 g/L by diethyl ether extraction and NaOH titration.
  • the obtained fermentation broth was diluted twice with water, adjusted to pH S 10. 0 by alkali, heated to 90 ° C, and 0.2 ⁇ m ceramic membrane was microfiltered to remove the cells. Centrifuge the supernatant plus 2. 5 ° /. After decolorization of activated carbon for 20 minutes, the activated carbon was filtered off, and the pH was adjusted to 3.5 with sulfuric acid. The acidified crystal was cooled to room temperature, filtered, washed to neutral, dried at 80 ° C for 12 hours to obtain a product, and analyzed for total acid. 0% ⁇ The purity of the gas chromatographic purity of 97.0%.
  • the seed liquid was introduced to start fermentation.
  • the fermentation medium components were: sucrose 2%, KH 2 P0 4 1.5%, yeast extract 1.0%, corn syrup 0.45%, urea 1.0%, tap water preparation, pH natural, sterilization at 121 °C for 20 minutes.
  • the culture was carried out at 29 ° C, aeration rate of 0.8 wm, and pot pressure of 1.0 MPa.
  • the pH is natural 20 hours before fermentation, and the growth of the cells is dominant.
  • the palmitate (C16) is added at 5%, and then palmitic acid is added every 12 hours during the fermentation.
  • the pH was adjusted to 6.8 with NaOH solution every 4 hours for 72-120 hours, 120 hours to the can, and the pH was adjusted to 7.5 with NaOH solution every 4 hours. From the end of fermentation was inoculated to a total culture time of 166 hours, including measured by titration with NaOH and extracted with diethyl ether fermentation raw material solution 06 The amount is 32.3 g/L.
  • the obtained fermentation broth was diluted twice with water, adjusted to pH 10. 0 with alkali, heated to 90 ° C, and centrifuged to remove bacteria. After centrifugation with 2.5% activated carbon for 20 minutes, the activated carbon was filtered off, and the pH was adjusted to 4.5 with sulfuric acid. The acidified crystal was cooled, cooled to room temperature, filtered, washed to neutral, dried at 80 ° C. 8% ⁇ The product was analyzed, the total acid was 98.1%, the purity of the DC16 gas chromatogram was 96.8%.
  • the mixture was poured into a horizontal wiped film evaporator, and continuously distilled under a pressure of 2 mmHg at a temperature of 160 ° C to obtain a polyanhydride, which was cooled under nitrogen to obtain a finished product.
  • Example 7 Under the protection of nitrogen, 100 parts of DC12 and 30 parts of acetic anhydride in the purification example 6 of the long carbon chain dibasic acid were placed in the reaction vessel, and the temperature was raised and stirred. After one hour, the temperature of the material rose to 13 CTC, and small molecules were distilled off. The mixture was distilled under normal pressure for 2 to 4 hours until no product was distilled off. The mixture was poured into a horizontal wiped film evaporator, and continuously distilled under a pressure of 0.1 mmHg under a temperature of 120 Torr to obtain a polyanhydride, which was cooled under nitrogen to obtain a finished product.
  • the color stability of the polyanhydride in this experiment was determined as follows: 100 g of the polyanhydride sample was weighed and placed in a crucible, placed in a 120-inch oven, and oxygen was introduced into the bottom of the sample, continuously bubbling for one hour, and then taken out and cooled. Detect the color of the sample.
  • the inventors believe that the polyanhydride product obtained in the present invention has a good appearance, and the color, ash and thermal oxidative yellowing performance is higher than that of the long carbon chain diacid acid produced by the chemical method.
  • Anhydride far superior to the conventional bio-process long carbon chain dibasic acid preparation of polyanhydride, fully meets the requirements of high-grade powder coatings for curing agents. Same At the time, the cost is greatly reduced relative to the chemical dibasic acid, which lays a foundation for the industrial expansion of the long carbon chain dibasic acid polyanhydride.

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Abstract

La présente invention concerne un produit durcisseur de polyanhydride d'acide dicarboxylique à chaîne longue de grande qualité préparé selon un processus biologique utilisant un alcane ou un acide gras comme matière première de départ. Le durcisseur de polyanhydride d'acide dicarboxylique peut être utilisé pour faire durcir le revêtement en poudre. Cette invention concerne également un procédé de fabrication du durcisseur de polyanhydride d'acide dicarboxylique à chaîne longue qui consiste d'abord à produire un acide dicarboxylique à chaîne longue à partir d'un alcane ou d'un acide gras au moyen d'un procédé de fermentation biologique, puis à obtenir l'acide dicarboxylique souhaité au moyen d'un procédé de purification particulier. L'acide dicarboxylique est ensuite soumis à une réaction de déshydratation à pression normale combinée à un autre réactif, la température du mélange ainsi obtenu étant comprise entre 100 et 140°C, la durée de distillation étant comprise entre 1 et 6 heures. Le produit final est obtenu par distillation sous vide à une température comprise entre 110 et 140°C, le vide étant inférieur à 15mmHg, ou par distillation dans un évaporateur à film raclé afin d'éliminer les substances à petites molécules. Le produit durcisseur de polyanhydride d'acide dicarboxylique à chaîne longue préparé selon cette invention présente une chromaticité Gardner inférieure à 2, une teneur en cendres n'excédant pas à 80 ppm et une teneur en azote résiduel n'excédant pas 60 ppm. Le point de fusion du produit durcisseur peut être ajusté en fonction de l'application pratique souhaitée. Le durcisseur présente une excellente résistance au jaunissement et répond suffisamment aux critères exigés d'un durcisseur utilisé dans un revêtement en poudre.
PCT/CN2006/002341 2006-07-20 2006-09-11 Durcisseur pour revêtement en poudre et procédé de préparation du polyanhydride d'acide dicarboxylique à chaîne longue utilisé dans ce revêtement en poudre WO2008011763A1 (fr)

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CN110541008A (zh) * 2018-05-29 2019-12-06 上海凯赛生物技术股份有限公司 一种长链二元酸铵的制备方法及其应用

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CN103589283B (zh) * 2013-11-10 2015-07-15 湖南至诚涂料有限公司 一种薄涂粉末涂料的制备方法及产品
CN104844440B (zh) * 2014-02-17 2019-05-31 上海凯赛生物技术研发中心有限公司 一种长链混合二元酸的精制方法
CN110512213B (zh) * 2014-02-17 2022-01-07 上海凯赛生物技术股份有限公司 一种长链混合二元酸的提纯方法
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CN106242960B (zh) * 2016-07-18 2018-09-21 天津市安凯特科技发展有限公司 一种不使用硫酸生产长链二元酸的方法
CN107325022B (zh) * 2017-08-09 2021-06-18 无锡殷达尼龙有限公司 一种长碳链氰基酸的制备方法
CN114181073A (zh) * 2017-12-28 2022-03-15 凯赛（金乡）生物材料有限公司 一种长链二元酸氧化脱色工艺
CN111138273A (zh) * 2019-12-24 2020-05-12 上海凯赛生物技术股份有限公司 一种长链二元酸的精制工艺及系统

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CN110541008A (zh) * 2018-05-29 2019-12-06 上海凯赛生物技术股份有限公司 一种长链二元酸铵的制备方法及其应用

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