WO2012070747A2 - Procédé de production d'acide polylactique et de polymère de conductivité élevée et appareil pour la production de polymère d'acide polylactique de conductivité élevée - Google Patents

Procédé de production d'acide polylactique et de polymère de conductivité élevée et appareil pour la production de polymère d'acide polylactique de conductivité élevée Download PDF

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WO2012070747A2
WO2012070747A2 PCT/KR2011/006143 KR2011006143W WO2012070747A2 WO 2012070747 A2 WO2012070747 A2 WO 2012070747A2 KR 2011006143 W KR2011006143 W KR 2011006143W WO 2012070747 A2 WO2012070747 A2 WO 2012070747A2
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polylactic acid
producing
weight
lactic acid
highly conductive
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WO2012070747A3 (fr
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위순명
다카무라다카츠구
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Priority claimed from KR1020110030276A external-priority patent/KR101290309B1/ko
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Priority to CN2011800030694A priority Critical patent/CN102712745A/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00779—Baffles attached to the stirring means

Definitions

  • the present invention relates to a method for producing a polylactic acid and a highly conductive polylactic acid polymer, and an apparatus for manufacturing the same, and more particularly, to increase production yield and reduce costs, and to more easily produce a high molecular weight polylactic acid according to a use.
  • the present invention relates to a method for producing a polylactic acid and a method for producing a highly conductive polylactic acid polymer, which is economical in terms of time and cost, and an apparatus for manufacturing the same.
  • Plastic materials have contributed to modern people's abundant daily life and industrial development with various excellent functions and low prices, while environmental hormone leakage and intoxication caused by incineration or landfill of various waste vinyl, styrofoam, plastic containers, etc. Is a cause of serious environmental pollution such as detection of dioxins and air pollution caused by incomplete combustion of waste.
  • In order to solve the problem of plastic waste research is being conducted to solve the problem of plastic convenience and environmental pollution by adding a function of degradability after use while maintaining the processability, durability and mechanical properties of the plastic. .
  • degradable plastics are photodegradable plastics caused by chemical reactions such as photooxidation by photovoltaic light and ketone photolysis, oxidatively decomposed plastics which are decomposed by oxidation reactions under the influence of temperature, plastics and microorganisms decomposed by hydrolysis reaction. And plastics decomposed by enzymes and the like.
  • biodegradable polymers made of plant-derived natural polymers such as cellulose, pectin, hemicellulose, lignin, starch and rice straw are called natural polymer biodegradable polymers.
  • Starch is applied to starch foam containers, starch foam packaging materials, cushioning materials, etc. using foaming properties of foaming using its own adhesiveness, heat, or water.
  • Poly-Lactic Acid (PLA) which is chemically synthesized using L-lactic acid, fermented with microorganisms using starch, as a monomer, is cheaper than conventional PLA, and is used in a large amount. Processed PLA also has excellent hydrolysis resistance.
  • the polylactic acid has a problem in that the pH of the reaction solution is lowered during the fermentation of the lactic acid, and the activity of the lactic acid bacteria is often inhibited, so that lactic acid at a high concentration cannot be efficiently obtained. Therefore, it was necessary to strictly adjust the pH and temperature, in particular, the time required to liquefy and shorten the starch takes only 24 to 35 hours, there was a problem that it is expensive.
  • FIG. 1 is a conceptual diagram showing a conventional electrodialysis apparatus, as shown in the manufacturing process of the polylactic acid, there is an electrodialysis process of the lactic acid, conventionally the process is a device for performing the process of separating the lactate from the fermentation broth and lactate the lactate again There was a problem in that the equipment cost is high because it must be equipped with a separate device that functions to decompose and sodium hydroxide.
  • lactic refining process since the extracted and separated lactic acid by the electrodialysis apparatus contains various organic acids, it is necessary to remove them and to refine the pure lactic acid. This process is called lactic refining process. Conventionally, the process has been performed by ion adsorption separation method or electrodialysis method which focuses on selective adsorption of ion exchange resins, but there is a limitation that the process such as pretreatment must be divided into several times.
  • the present invention has been made to solve the above problems, the object of the present invention is not affected by the pH of the reaction in the lactic acid effect tablet, the temperature range is wide, the process time and cost of the efficient polylactic acid It is to provide a manufacturing method.
  • an object of the present invention can be carried out in one process and apparatus to separate the lactate from the fermentation broth and the process of separating the lactic acid and sodium hydroxide in the electrodialysis process of lactic acid, and does not require pretreatment, such as more efficient poly It is to provide a method for producing a lactic acid.
  • Another object of the present invention is to provide an apparatus for producing a highly conductive polylactic acid polymer capable of carrying out a substitution reaction and a polymerization reaction using a single device.
  • Method for producing a polylactic acid according to the present invention in order to achieve the above object is a gelatinization process of mixing the vegetable starch with water and then heated to gelatinize; A liquefaction step of adding lactic acid to the gelatinized starch and liquefying it by heating; A saccharification step of decomposing the liquefied starch into a monosaccharide liquid using a saccharifying enzyme; A fermentation step of lactically fermenting the monosaccharide solution to produce a fermentation broth; Electrodialysis step of separating and concentrating the lactate from the fermentation broth and separating the lactic acid from the lactate; Lactic acid purification process of heating the separated lactic acid to remove moisture and impurities; A lactide producing step of mixing the purified lactic acid with a metal oxide to produce lactide; A polymerization step of polymerizing the lactide to generate polylactic acid; And an impurity evaporation step of evaporating the unreacted material that is not polymerized by heating the polylactic acid.
  • the gelatinization process in the method for producing a polylactic acid according to the present invention is mixed with 70 to 80 parts by weight of water with respect to 20 to 30 parts by weight of the starch and heated to 90 to 105 °C while stirring at 70 to 100 RPM, 15 It is characterized by stirring for ⁇ 120 minutes.
  • the liquefaction process in the method of producing a polylactic acid according to the present invention is characterized by heating to 110 ⁇ 130 °C while stirring for 4-10 hours by adding 0.1 ⁇ 1.0% by weight of the lactic acid to the weight of the gelatinized starch. It is done.
  • the glycosylase is 0.1 to 1.0% amylase with respect to the weight of the starch
  • the temperature of the liquefied starch is 50 to 65 °C
  • pH is adjusted to 6.0 to 6.5
  • the pH is characterized by using an aqueous ammonia solution.
  • the fermentation process is based on the weight of the monosaccharide solution having a sugar content of 20 to 30, 0.01 to 0.1% of salt, 0.01 to 0.5% of manganese sulfate, 0.01 to 0.1% of ammonium phosphate, 0.1 to 1.0% skim milk powder, 0.1 to 1.0% soy milk, 0.1 to 1.0% waste molasses, 0.01 to 0.05% surfactant, 2 to 5% of the lactic acid bacteria culture medium is mixed with the above monosaccharide solution for 20 to 35 hours at 70 to 100 RPM It is characterized by stirring.
  • the fermentation process in the method of producing a polylactic acid according to the present invention is characterized in that it uses a fermentation apparatus equipped with a mechanism for concentrating the lactic acid produced by the fermentation.
  • the electrodialysis process is performed using an electrodialysis apparatus including an electrolytic chamber, a partition by a diaphragm, a solution circulation means, and an electrode, and the electrolytic chamber is an anolyte chamber and a fermentation broth. And a lactate / lactic acid generating chamber, a sodium hydroxide generating chamber, and a catholyte chamber, each electrolytic chamber being partitioned into an anionic permeable membrane and / or a cationic permeable membrane, wherein the electrode comprises an anode, a cathode, an auxiliary anode, and an auxiliary cathode. It is characterized by.
  • the lactic acid refining process in the method for producing a polylactic acid according to the present invention is dehydrated by heating to 120 ⁇ 130 °C while stirring the lactic acid at 70 ⁇ 100RPM in a pressure-resistant vessel and stirred for 1 to 2 hours at 150 ⁇ 160 °C Continuing to produce low molecular weight polylactic acid; And when the low molecular weight polylactic acid is produced, the stirring is stopped, the mixture is cooled to room temperature, crystallized, heated to 150 to 160 ° C, and the pressure in the pressure vessel is reduced to 70 to 100 RPM for 1 to 2 hours to reduce impurities. Transpiration to obtain a purified lactic acid; characterized in that it comprises a.
  • the lactide production process is carried out in a vanadium, nickel, iron, aluminum, titanium, selium, silicon, zircon, ruthenium, manganese, chromium, cobalt, platinum, thorium, palladium in a pressure resistant container.
  • Mixing 0.5-1% of at least one metal oxide in tin; Heating and stirring the lactic acid at 170 to 190 ° C. for 3 to 5 hours; And slowly cooling and crystallizing the lactic acid to produce lactide.
  • the polymerization process is stirred at a rate of 70 to 100 RPM while heating the lactide to a melting temperature, and the organic tin compound is 0.1 to 1% based on the weight of the lactide, Adding 0.1 to 1% of silalcohol and mixing for 3 to 5 hours at atmospheric pressure; Reducing the pressure while injecting an inert gas into the pressure resistant vessel, and heating and stirring the lactide at 160 to 170 ° C; And promoting the polymerization by using the polymerization promoter.
  • the impurity is a low molecular polylactic acid or lactide
  • the transpiration process may be performed at 70 to 100 RPM while reducing the pressure inside the pressure vessel and heating the temperature of the polylactic acid to 180 to 190 ° C. It is characterized by stirring for 1 to 2 hours.
  • the method for producing a polylactic acid according to the present invention is a gelatinization step of mixing the vegetable starch with water and then heating it to gelatinize; A liquefaction step of adding 0.2-1.0% of lactic acid to the weight of the gelatinized starch and liquefying by heating to 110-130 ° C .; A saccharification step of decomposing the liquefied starch into a monosaccharide liquid using a saccharifying enzyme; 0.01 to 0.1% of sodium salt, 0.01 to 0.5% of manganese sulfate, 0.01 to 0.1% of ammonium phosphate, 0.1 to 1.0% of skimmed milk powder, 0.1 to 1.0% of soy milk, 0.1 to 1.0% of waste molasses, Fermentation step of producing a fermentation broth by lactic acid fermentation by mixing 0.01 ⁇ 0.05% surfactant, 2 ⁇ 5% lactic acid bacteria culture medium to the monosaccharide solution; Electrodialysis step of neutralizing the lactic acid of the fermentation broth with sodium hydro
  • a lactide generation step of generating a tide A polymerization process of adding polylactic acid by ring-opening condensation polymerization by adding 0.1-1% of organotin compound and 0.1-1% of dodecyl alcohol to the weight of the lactide; And an impurity evaporation step of evaporating the unreacted material which is not polymerized by heating the temperature of the polylactic acid to 180 to 190 ° C.
  • Method for producing a highly conductive polylactic acid according to the present invention is added to 100 parts by weight of polylactic acid, 10 to 20 parts by weight of lactide and 5 to 10 parts by weight of polyglycolic acid in the reaction vessel, step S1, the reaction vessel 5 to 10 parts by weight of serine and 0.1 to 1 part by weight of dodecyl alcohol, followed by S2 step of adding an inert gas and irradiating electromagnetic waves and adding 0.1 to 1 part by weight of cerium acetate to the reaction vessel, and then stirring S3 step. Characterized in that.
  • step S1 to step S3 is characterized in that it is made at a temperature of 160 ⁇ 190 °C.
  • the step S1 is performed under reduced pressure at 0.1 to 0.5 atm, and the steps S2 and S3 are pressurized at 1 to 5 atm by adding nitrogen as an inert gas. Characterized in that the state is made.
  • the polylactic acid in the method for producing a highly conductive polylactic acid according to the present invention is characterized in that the molecular weight of 5,000 ⁇ 10,000.
  • step S1 in the method for producing a highly conductive polylactic acid according to the present invention is characterized by further adding 0.1-10 parts by weight of ammonium vanadate as a catalyst and 0.1-10 parts by weight of vanadium oxide.
  • the step of adding an inert gas to pressurized to 2 to 3 atm characterized in that it further comprises a step S5 to discharge the reactants in the reactor.
  • the method of maintaining the temperature of the steps S1 to S3 in the method for producing a highly conductive polylactic acid according to the present invention is characterized in that the heat medium is heated by a heater, heat is transferred to the reaction vessel through the heated heat medium. do.
  • the apparatus for producing a highly conductive polylactic acid the upper portion is provided with a raw material inlet, nitrogen / electromagnetic inlet and nitrogen outlet, the lower portion is equipped with a reaction vessel, a stirrer for stirring the reactants in the reaction vessel, reaction A heat supply unit for heating the vessel, a nitrogen / electromagnetic wave inlet connected to a nitrogen / electromagnetic inlet for supplying electromagnetic waves and nitrogen gas to a reactant in the reaction vessel, and a decompression pump for reducing the inside of the reaction vessel in connection with a nitrogen outlet; do.
  • the heat supply part surrounds the side and bottom surfaces of the reaction vessel and includes a heat transfer jacket having a heat medium embedded therein, and a heater for supplying heat to the heat transfer jacket. It is characterized in that the oil.
  • the nitrogen / electromagnetic wave supply part is located in the reaction vessel through the nitrogen / electromagnetic inlet and supplies a nitrogen and electromagnetic wave to the reactant, and is connected to the horn antenna and the nitrogen inlet It characterized in that it comprises a waveguide and a magnetron oscillator is connected to the waveguide and generates an electromagnetic wave.
  • the nitrogen / electromagnetic inlet in the manufacturing apparatus of the highly conductive polylactic acid according to the present invention is characterized in that installed at a position separated by 3/8 of the diameter of the reaction vessel (D) in the center of the reaction vessel.
  • the production method of the polylactic acid according to the present invention can reduce the equipment required for the production of polylactic acid, thereby increasing the production yield and the effect of reducing the cost.
  • the polylactic acid production method according to the present invention has the effect of optimizing the frequency and output of the electromagnetic wave in the synthesis step to produce a polylactic acid having a desired molecular weight in a short time.
  • the manufacturing method and apparatus for manufacturing a highly conductive polylactic acid polymer according to the present invention can ensure high conductivity by applying the optimum conditions of temperature, pressure and weight ratio that can be commercialized polylactic acid in electronic components, efficiency This is excellent in effect of reducing the manufacturing cost.
  • the method for producing a highly conductive polylactic acid polymer according to the present invention and its manufacturing apparatus have an effect that can be easily and efficiently produced.
  • the manufacturing method and apparatus for manufacturing the highly conductive polylactic acid polymer according to the present invention can perform the substitution reaction and the polymerization reaction in a single device, and are economical in terms of time and cost.
  • FIG. 1 is a conceptual diagram showing the structure of a conventional electrodialysis apparatus.
  • Figure 2 is a process diagram showing one embodiment of a method for producing a polylactic acid according to the present invention.
  • FIG 3 is a cross-sectional view showing the structure of the saccharification apparatus of the method for producing a polylactic acid according to the present invention.
  • Figure 4 is a graph showing the change in pH and the number of lactic acid bacteria of fermentation broth in the method of producing a polylactic acid according to the present invention.
  • 5A and 5B are cross-sectional views showing the structure of a fermentation apparatus equipped with a mechanism for concentrating lactic acid in the method for producing polylactic acid according to the present invention.
  • Figure 6 is a conceptual diagram showing the structure of the electrodialysis apparatus in the method of producing a polylactic acid according to the present invention.
  • FIG. 7 is a cross-sectional view showing the structure of a fermentation apparatus equipped with a mechanism for concentrating a legacy showing the structure of the polymerization apparatus in the method for producing a polylactic acid according to the present invention.
  • FIG. 8 is a graph showing the lactic acid purification process in the method for producing a polylactic acid according to the present invention as a change in reaction time and temperature.
  • FIG. 9 is a process chart showing the yield of the lactic acid purified in the method for producing a polylactic acid according to the present invention.
  • FIG. 10 is a graph illustrating a process of lactide production and polymerization of polymer polylactic acid in the method for producing polylactic acid according to the present invention.
  • FIG. 11 is a cross-sectional view showing the positional relationship between a polymerization apparatus and a polymerization accelerator in the method for producing a polylactic acid according to the present invention.
  • FIG. 12 is a cross-sectional view showing the structure of a polymerization accelerator in the method for producing a polylactic acid according to the present invention.
  • FIG. 13 is a graph showing data obtained by measuring the electromagnetic wave intensity distribution of the polymerization accelerator in the polymerization method according to the present invention by inserting a measurement probe inside the polymerization apparatus.
  • FIG. 14 is a cross-sectional view showing the structure of the measurement probe used in FIG. 13.
  • FIG. 15 is a conceptual diagram illustrating a moving state of contents in a polymerization apparatus in the method for producing a polylactic acid according to the present invention.
  • FIG. 16 is a graph showing data obtained by measuring molecular weight by irradiating electromagnetic waves in a polymerization apparatus in the method of producing a polylactic acid according to the present invention.
  • 17 is a process chart showing one embodiment of a method for producing a highly conductive polylactic acid polymer according to the present invention.
  • FIG. 18 is a conceptual diagram showing a high conductivity polylactic acid polymer manufacturing apparatus according to the present invention.
  • FIG. 19 is a conceptual diagram illustrating a nitrogen / electromagnetic wave supply unit of the highly conductive polylactic acid polymer production apparatus according to the present invention.
  • 20 is a conceptual view illustrating the position of the nitrogen / electromagnetic inlet of the high conductivity polylactic acid polymer manufacturing apparatus according to the present invention.
  • FIG. 21 is a conceptual diagram illustrating a state in which a reactant moves in a reaction container of the apparatus for preparing a highly conductive polylactic acid polymer according to the present invention.
  • FIG. 2 is a process diagram showing an embodiment of a method for producing a polylactic acid according to the present invention, the gelatinization step of mixing the vegetable starch with water and then heated to gelatinization as shown (S10); A liquefaction process of adding lactic acid to the gelatinized starch and liquefying by heating; A saccharification step (S30) of decomposing the liquefied starch into a monosaccharide liquid using a saccharifying enzyme; Fermentation process (S40) for producing a fermentation broth by lactic fermentation of the monosaccharide solution; Electrodialysis step (S50) of separating and concentrating the lactate from the fermentation broth and separating the lactic acid from the lactate; Lactic acid refining process (S60) for removing the water and impurities by heating the separated lactic acid; A lactide generating step (S70) of generating the lactide by mixing the purified lactic acid with a metal oxide; A polymerization step of polymerizing the lactide to form
  • Gelatinization process is a mixture of vegetable starch with water in a stirring apparatus and gelatinization by heating
  • starch is a rice starch
  • cassava (cassava) starch sweet potato starch, potato starch, wheat starch, Corn starch (corn starch) or the like can be used.
  • the gelatinization process is heated to 90 ⁇ 105 °C, preferably 95 ⁇ 100 °C while stirring at 70 ⁇ 100 RPM by mixing 70 to 80 parts by weight of water with respect to 20 to 30 parts by weight of starch, the temperature of the starch is 90 °C When it reaches 15-120 minutes, Preferably it is made to stir and heat at 70-100 RPM for 30 to 60 minutes, and gelatinizes.
  • the liquefaction step (S20) is to liquefy by adding lactic acid to the gelatinized starch, heating.
  • the lactic acid is a 50% solution of L-lactic acid having a molecular weight of 800 to 1000.
  • the liquefaction process is added to 0.1 ⁇ 1.0% by weight of L-Lactic acid (L-Latic Acid) to the weight of the gelatinized starch while stirring for 4 to 10 hours to 110 ⁇ 130 °C, preferably 120 ⁇ 150 °C It is heated and liquefied by stirring for 5 to 10 hours, preferably 7 to 8 hours in a pressurized environment of 1.2 to 2.0 kg / cm 2.
  • L-Lactic acid L-Latic Acid
  • the saccharification step (S30) is to decompose the liquefied starch into monosaccharide liquid using a saccharifying enzyme.
  • the glycosylase is 0.1 to 1.0% by weight of amylase, preferably glycoamylase, based on the weight of starch.
  • amylase preferably glycoamylase
  • the use of Amanose AF-6 results in a reaction time of 10-15 hours compared to Amanose T-10S. This can be reduced to 7-8 hours at.
  • the temperature of the liquefied starch is set to 50-65 ° C., preferably 50-65 ° C., and the pH is adjusted to 6.0-6.5, and the pH is preferably adjusted by adjusting the hydrogen ion concentration (pH) using an aqueous ammonia solution.
  • 0.1 to 1.0% by weight of the glycated enzyme is added to the added starch and stirred for 5 to 12 hours, preferably 6 to 10 hours, more preferably 7 to 8 hours to monosaccharide.
  • the hydrolysis method by lactic acid of the present invention it is possible to use the lactic acid solution obtained by the lactic acid fermentation or electrodialysis step or the lactic acid solution obtained by the lactic acid purification step as it is, and the cost and reaction time can be shortened.
  • FIG. 3 is a cross-sectional view showing the structure of the saccharification device of the polylactic acid production method according to the present invention, as shown in the saccharification device 200 is largely a container 210, the stirring blade 232 for stirring the contents and It is composed of a stirring apparatus 230 and an electric heater 250 and a water cooling jacket 270 that can adjust the temperature, the upper side of the vessel is provided with a condenser 290 and a condensate reservoir 292.
  • a gelatinization process, a liquefaction process, and a saccharification process may be continuously performed.
  • Fermentation process is to produce a fermentation broth by lactic fermentation of a monosaccharide solution.
  • the fermentation step is 0.01 to 0.1% by weight of salt, 0.01 to 0.5% by weight of manganese sulfate, 0.01 to 0.1% by weight of ammonium phosphate, 0.1 to 1.0% by weight of skim milk powder, soy milk, based on the total weight of the monosaccharide solution having a sugar content of 20 to 30.
  • 0.1 to 1.0% by weight, 0.1 to 1.0% by weight of molasses, 0.01 to 0.05% by weight of surfactant, 2 to 5% by weight of lactic acid bacteria culture medium is preferably mixed with the above monosaccharide solution and stirred at 70 to 100 RPM for 20 to 35 hours.
  • lactic acid bacteria and additives are added to the liquid sugar of 20 ⁇ 30 Brix, and the nutrients (for example, manganese, nitrogen, polyphenols, etc.) and corona precipitation required for propagation of monosaccharides and lactic acid bacteria in the fermentation apparatus in the process of lactic acid fermentation.
  • the surfactant eg, sucrose fatty acid ester, etc.
  • the hydrogen ion concentration (pH) is adjusted to a neutral region (pH 6.5 to 7.5) using ammonia It is preferable.
  • the temperature of the contents was adjusted to 38-42 ° C., which is suitable for the growth of lactic acid bacteria, and 2-5% by weight of Lactobacillus L Plantarm culture medium (3-5 billion cells of viable bacteria in 1 g of culture solution) was added at 70-100 RPM. Stir.
  • the growth of bacteria is inhibited by the lactic acid in the fermentation broth, so it is preferable to adjust the pH using sodium hydroxide so that the pH of the fermentation broth is not lower than 3.5.
  • Figure 4 is a graph showing a change in the pH and the number of lactic acid bacteria of fermentation broth in the method of producing a polylactic acid according to the present invention, as shown in the fermentation is close to the end of the starch in the fermentation broth is less proliferation of lactic acid bacteria Since the lactic acid production rate is extremely slow, the lactic acid enrichment apparatus will be described later.
  • Figure 5a and 5b is a cross-sectional view showing the structure of the fermentation apparatus equipped with a mechanism for concentrating the lactic acid in the method for producing a polylactic acid according to the present invention, a negative electrode which is a net-shaped electrode formed in the center of the fermentation apparatus as shown
  • an acidic salt mainly through a cylindrical diaphragm 324 (such as a cationic permeable membrane) with the cathode 328 and the fermentation chamber 322 interposed therebetween.
  • Sodium lactate moves inside the diaphragm 324.
  • the concentration chamber 326 provided inside the diaphragm 324.
  • lactate is concentrated in the concentration chamber 326 inside the diaphragm.
  • the volume ratio between the fermentation chamber 322 and the concentration chamber 326 is about 10: 1
  • the volume ratio of 1: 1-20: 1 is sufficient to perform the function.
  • the ratio is large and the fermentation efficiency is also improved. In practice, it is preferable to set the upper limit to about 30: 1.
  • Electrodialysis process is to separate and concentrate the lactate in the fermentation broth, and to separate the lactic acid from the lactate.
  • FIG. 6 is a conceptual diagram showing the structure of the electrodialysis apparatus in the method for producing a polylactic acid according to the present invention, as shown in the electrodialysis process is an electrolytic chamber 410, anion permeable membrane 451, cationic permeable membrane ( 453), an electrodialysis apparatus including a solution circulation means and an electrode, wherein the electrolytic chamber 410 includes an anolyte chamber 412, a fermentation broth 414, a lactate / lactic acid solution chamber 416, and sodium hydroxide.
  • the solution chamber 418 and the catholyte chamber 419 are sequentially arranged, and each electrolytic chamber is partitioned into an anion permeable membrane 451 and / or a cationic permeable membrane 453, and the electrode is an anode 431 and a cathode. 433, the auxiliary anode 435, and the auxiliary cathode 437 are preferable.
  • a sodium sulfate solution having a concentration of 10 to 20% as an electrolyte is circulated in the anolyte chamber 412 and the catholyte chamber 419 in the same circulation circuit to circulate the filtered fermentation broth in the fermentation broth 414.
  • clear water is circulated in the lactate / lactic acid solution chamber 416 and 0.1N sodium hydroxide solution is circulated in the sodium hydroxide solution chamber 418.
  • the auxiliary anode 435 and the auxiliary cathode 437 conduct a DC current between the anode 431 and the cathode 433 in a floating (no connection) state.
  • the hydroxyl ion (OH ⁇ ) in the fermentation broth 414 passes through the anion permeable membrane 451 separating the anolyte chamber 412 and the fermentation broth 414 and moves toward the electrode liquid chamber 412.
  • H + hydrogen ions
  • the lactate in the fermentation broth passes through the cationic permeation membrane 453 separating the fermentation broth 414 and the lactate / lactic acid solution chamber 416 and moves toward the lactate / lactic acid solution chamber 416.
  • the sodium ions are transferred from the lactate solution to the sodium hydroxide solution chamber 418, thereby releasing the lactate / lactic acid solution chamber 416. Lactic acid solution of) becomes lactic acid solution.
  • the sodium hydroxide concentrated in the sodium hydroxide solution chamber 418 may be used for neutralizing the fermentation broth in the fermentation process.
  • the electrodialysis apparatus of the present invention has the function of separating the lactate from the fermentation broth and the function of decomposing the lactate into lactic acid and sodium hydroxide at the same time, so that the process using two electrodialysis apparatuses in the past can be completed in one unit, which is reasonable and equipment cost. You can make about half.
  • Lactic acid purification process is to remove the water and impurities by heating the separated lactic acid. This is because the lactic acid extracted and separated by the electrodialysis process includes various organic acids, and thus it is necessary to purify the lactic acid (crude acid).
  • FIG. 7 is a cross-sectional view showing the structure of a fermentation apparatus equipped with a mechanism for concentrating a legacy showing the structure of the polymerization apparatus in the method for producing a polylactic acid according to the present invention, wherein the polymerization apparatus continuously stirs the contents as shown.
  • Possible stirring device 530 and stirring blade 532, electric heater 550 capable of heating the contents at 190 ° C or higher, inert gas injection device (not shown), pressure reduction device (not shown) in the vessel, evaporate cooling recovery device (Not shown) is provided with a pressure-resistant container 510, the pressure-resistant container 510 is a polymerization promoter 560 is connected. It is possible to continuously perform lactic acid purification, lactide production, polymer polylactic acid (PLA) polymerization, polylactic acid purification, etc. using the polymerization apparatus 500.
  • PLA polymer polylactic acid
  • Figure 8 is a graph showing the lactic acid purification process in the production method of the polylactic acid according to the present invention as a change in the reaction time and temperature, as shown in the lactic acid purification process is agitation of the lactic acid at 70 ⁇ 100 RPM in the pressure vessel Dehydrating by heating to 120 ⁇ 130 °C while continuing stirring for 1 to 2 hours at 150 ⁇ 160 °C to produce a low molecular polylactic acid; And when the low molecular weight polylactic acid is produced, the stirring is stopped, the mixture is cooled to room temperature, crystallized, and then heated again to 150 to 160 ° C. At this time, if the temperature is higher than 160 ° C, not only impurities but also evaporation of the lactic acid are purified. The yield of the inherited heritage becomes bad.
  • Figure 9 is a process chart showing the yield of the lactic acid is purified in the method for producing a polylactic acid according to the present invention, as shown in the water of 10 ⁇ 15wt% in the process of heating and dehydrating crude oil in the lactic refining process, In the process of producing polylactic acid (PLA), it can be seen that 5 to 6 wt% of water is discharged during the reheating process. The refined lactic acid is 75-80 wt% of the crude oil added.
  • the lactide generating step (S70) is to mix the purified lactic acid with a metal oxide to produce lactide.
  • FIG. 10 is a graph illustrating a process of lactide generation and polymerization of a polymer polylactic acid in the method for preparing polylactic acid according to the present invention.
  • FIG. 7 or FIG. 1 to 2 by mixing 0.5-1 wt% of one or more metal oxides of vanadium, nickel, iron, aluminum, titanium, selium, silicon, zircon, ruthenium, manganese, chromium, cobalt, platinum, thorium, palladium and tin in the container Stirring for sufficient time to mix well;
  • the inert gas is injected into the pressure-resistant container at atmospheric pressure to atmospheric pressure + 50 mmHg, and the contents are cooled and crystallized to produce lactide.
  • the lactide is an ester compound in which two molecules of ⁇ -hydroxy acid are cyclized between a carboxyl group and a hydroxy group, and there are three isomers of D-, L-, and DL-lactide.
  • FIG. 11 is a cross-sectional view showing the positional relationship between a polymerization apparatus and a polymerization accelerator in the method for producing a polylactic acid according to the present invention
  • FIG. 12 is a cross-sectional view showing the structure of the polymerization accelerator in a method for producing a polylactic acid according to the present invention.
  • the polymerization step (S80) is to polymerize the lactide to form a polylactic acid.
  • the polymerization process is stirred at a rate of 70 ⁇ 100 RPM while heating the lactide to the melting temperature, 0.1 to 1% by weight of the organic tin compound, 0.1 to 1% by weight of dodecyl alcohol with respect to the weight of the lactide
  • the polymerization process is stirred at a rate of 70 ⁇ 100 RPM while heating the lactide to the melting temperature, 0.1 to 1% by weight of the organic tin compound, 0.1 to 1% by weight of dodecyl alcohol with respect to the weight of the lactide
  • the polymerization promoter 560 By mixing at atmospheric pressure for 3 to 5 hours; Decompressing -20 to -50 mmHg while injecting an inert gas into the pressure resistant container, and heating and stirring the lactide at 160 to 170 ° C; And promoting the polymerization by using the polymerization promoter 560.
  • the frequency of the electromagnetic wave is 2 to 3 GHz, preferably 2.4 to 2.5 GHz, more preferably 2.45 GHz, and the output is preferably 10 to 30 W per kg of contents.
  • FIG. 13A, 13B, and 13C are graphs showing data obtained by measuring the electromagnetic wave intensity distribution of the polymerization accelerator in the polymerization apparatus by inserting a measurement probe inside the polymerization apparatus, and FIG. 14 is used in FIG. 13.
  • FIG. 14 is used in FIG. 13.
  • As a sectional view showing the structure of the measurement probe it can be seen that the intensity distribution of the electromagnetic wave varies depending on the degree to which the polymerization accelerator 560 is separated from the center of the polymerization vessel.
  • the electromagnetic wave emitted from the horn-shaped antenna 567 not only directly irradiates the surface of the contents but also reflects the reflected waves reflected inside the polymerization vessel, and the contents are moved while being stirred from the stirring device 530.
  • the polymerization accelerator 560 is installed at the position described above, the contents can be uniformly irradiated.
  • a member e.g., mica plate, etc.
  • the nitrogen gas inlet 563 is provided to the waveguide 561. It is desirable to install.
  • the other end of the waveguide 561 is connected to the inside of the polymerization apparatus 500. Nitrogen gas flows into the waveguide 561 and is supplied from the opening of the horn antenna 567 to the inside of the polymerization apparatus. Accordingly, it is possible to prevent vapor from the inside of the waveguide 561 from entering and to supply the inside of the polymerization apparatus without loss of electromagnetic waves.
  • the exhaust condenser and the vacuum pump are connected to the polymerization apparatus to reduce the pressure, and since nitrogen gas flows, steam of the contents does not penetrate and solidify inside the waveguide.
  • FIG. 15 is a conceptual diagram illustrating a moving state of contents in a polymerization apparatus in the method for producing a polylactic acid according to the present invention. As shown in FIG. While swirling to move to the right, the outer edge portion is faster compared to the center, so the electromagnetic wave distribution shown in Figure 13c it is possible that the contents are uniformly irradiated.
  • FIG. 16 is a graph showing data obtained by measuring molecular weight by irradiating electromagnetic waves in a polymerization apparatus in the method of preparing polylactic acid according to the present invention.
  • PLA polymerization was performed under the same conditions using the polymerization apparatus of the present invention.
  • the reaction time to 65,000dt which is the lower limit of the practical molecular weight, is 18 to 20 hours, whereas it can be seen that 28 to 32 hours are required when the electromagnetic wave is not irradiated.
  • the molecular weight reached at the reaction time of 32 hours was 70,000 to 75,000dt when the electromagnetic wave was not irradiated.
  • 100,000 to 110,000dt was found to be well polymerized.
  • Magnetron oscillator with 10KW output generates 2.45GHz electromagnetic wave
  • the variable reactance type regulator adjusts the electromagnetic radiation output to output 10, 30, 50, 100 (W / kg) per kilot of lactide.
  • the change of molecular weight was tested while changing, and the result was shown as follows.
  • Impurity evaporation step (S90) is to heat the polylactic acid to evaporate unreacted material that is not polymerized.
  • the impurity is a low molecular polylactic acid or lactide
  • the transpiration process is to reduce the pressure inside the pressure vessel -50 ⁇ 100mmHg and stirred for 1 to 2 hours at 70 ⁇ 100RPM while heating the temperature of the polylactic acid to 180 ⁇ 190 °C It is preferable.
  • a method for producing a polylactic acid according to the present invention is a gelatinization process of mixing the vegetable starch with water and then heating it to gelatinize;
  • a liquefaction step of adding 0.2-1.0 wt% of lactic acid to the weight of the gelatinized starch and liquefying by heating to 110-130 ° C .;
  • a saccharification step of decomposing the liquefied starch into a monosaccharide liquid using a saccharifying enzyme; 0.01 to 0.1% by weight of salt, 0.01 to 0.5% by weight of manganese sulfate, 0.01 to 0.1% by weight of ammonium phosphate, skim milk powder 0.1 to 1.0% by weight, soy milk 0.1 to 1.0% by weight, waste molasses 0.1
  • a fermentation step of producing a fermentation broth by lactic fermentation by mixing 1.0 wt%, 0.01 to 0.05 wt% surfactant, and 2 to 5 wt% of lactic acid bacteria culture medium to the monosaccharide solution
  • a lactide producing step of generating lactide A polymerization step of forming a polylactic acid by adding ringing-condensation polymerization by adding 0.1-1% by weight of organotin compound and 0.1-1% by weight of dodecyl alcohol to the weight of the lactide; And an impurity evaporation step of evaporating the unreacted material that is not polymerized by heating the temperature of the polylactic acid to 180 to 190 ° C.
  • FIG. 17 is a process diagram showing an embodiment of a method for producing a highly conductive polylactic acid polymer according to the present invention, as shown in the manufacturing method of the highly conductive polylactic acid polymer according to the present invention is 100 parts by weight of polylactic acid in the reaction vessel S1 step of adding 10 to 20 parts by weight of lactide and 5 to 10 parts by weight of polyglycolic acid, followed by stirring; S2 step of adding 5 to 10 parts by weight of serine and 0.1 to 1 part by weight of dodecyl alcohol in the reaction vessel, inert gas and irradiating electromagnetic waves; And S3 step of adding 0.1-1 part by weight of cerium acetate to the reaction vessel, followed by stirring.
  • step S1 step is to put a raw material, such as 100 parts by weight of polylactic acid, 10 to 20 parts by weight of lactide and 5 to 10 parts by weight of polyglycolic acid (glycollic acid) in the reaction vessel, and then stirred. And the step S1 can be made in a reduced pressure at a temperature of 160 ⁇ 190 °C and 0.1 ⁇ 0.5 atm.
  • a raw material such as 100 parts by weight of polylactic acid, 10 to 20 parts by weight of lactide and 5 to 10 parts by weight of polyglycolic acid (glycollic acid)
  • the step S1 according to the present invention may be made by adding 0.1 to 10 parts by weight of ammonium vanadate (NH 4 VO 3) as a catalyst and 0.1 to 10 parts by weight of vanadium oxide.
  • the vanadium oxide according to the present invention is one selected from vanadium monoxide (VO), vanadium dioxide (VO 2 ), vanadium trioxide (V 2 O 3 ) and vanadium pentoxide (V 2 O 5 ).
  • Lactide according to the present invention is an ester compound in which two molecules of ⁇ -hydroxy acid are cyclized between a carboxy group and a hydroxyl group, and all three isomers of D-, L-, and DL-lactide can be used.
  • Formula 1 shows a state in which a lactic acid is converted into a polylactic acid.
  • the polylactic acid (PLA, Poly Lactic Acid) according to the present invention has lactide (Lactid) coexisting, and the lactide forms a ring-shaped peptide. Since it can form, it is preferable to use the low molecular weight polylactic acid whose average molecular weight is 2,000-10,000, Preferably 5,000-10,000.
  • step S2 5-10 parts by weight of serine and 0.1-1 part by weight of dodecyl alcohol are added to the reaction vessel, and an inert gas is added thereto to irradiate electromagnetic waves. Irradiating electromagnetic waves to the reactants according to the present invention promotes N-H substitution reactions and condensation polymerization reactions that are converted from lactide to cyclic peptides.
  • step S2 may be made in a state pressurized to 1 to 5 atm by adding nitrogen as an inert gas.
  • Serine (serine) is a-amino acid, the chemical formula is HOCH 2 CH (NH 2 ) COOH, one kind of amino acid that is soluble in water but not soluble in alcohol or ether.
  • any of hydrophilic amino acids asparagine, cysteine, glutamine, glycine, threonine, tyrosine, lysine, aspartic acid, glutamic acid, arginine, and histidine may be used in addition to serine.
  • Formula 2 shows a state in which a lactide is converted into a cyclic peptide, and the cyclic peptide has a plurality of side chains, thereby facilitating the bonding of metal atoms to be described later.
  • R is an amino acid
  • S3 step according to the present invention is to add 0.1 to 1 parts by weight of cerium acetate (Acetic Acid cerium, Ce) to the reaction vessel, and then stirred.
  • Cerium according to the present invention is one of the rare earth elements belonging to the lanthanide group of the periodic table.
  • any one of cerium nitrate, cerium ammonium nitrate, and cerium chloride may be selected and used instead of cerium acetate.
  • a compound containing other rare earth elements can be used.
  • step S3 may be made in a state pressurized to 1 to 5 atm by adding nitrogen as an inert gas.
  • Formula 3 shows a metal atom group bonded to the side chain of the cyclic polypeptide, and a metal atom group such as cerium may be bonded to the amino acid (R) of the polypeptide to generate a highly conductive polylactic acid polymer.
  • M is a metal atom group
  • R is an amino acid
  • S4 step according to the present invention is to maintain a temperature of 160 ⁇ 190 °C in a state in which the agitation of the step S3 is stopped and reduced to 0.1 to 0.5 atm.
  • step S5 after the step S4 is completed, an inert gas is added to pressurize to 2 to 3 atmospheres to discharge the reactants in the reactor.
  • Step S1 to S3 of the present invention is made at a reaction temperature of 160 ⁇ 190 °C, if less than 160 °C may not be a smooth reaction or the reaction proceeds slowly. And when the steps S1 to S3 is more than 190 ° C evaporation of the reactants a lot, the reaction does not proceed smoothly.
  • the apparatus for producing a highly conductive polylactic acid polymer according to the present invention includes a raw material inlet 112a and 112b, a nitrogen / electromagnetic inlet 114 and a nitrogen outlet 116 in the upper portion, and a reactant outlet 118 in the lower portion.
  • Reaction vessel 110 is provided; An agitator (130) for stirring the reactants in the reaction vessel (110); A heat supply unit 150 for heating the reaction vessel 110; A nitrogen / electromagnetic wave supply unit 170 connected to the nitrogen / electromagnetic wave inlet 114 to supply electromagnetic waves and nitrogen gas to a reactant in the reaction vessel 110; And a decompression pump 190 connected to the nitrogen outlet 116 to depressurize the inside of the reaction vessel 110.
  • the heat supply unit 150 surrounds the side and bottom surfaces of the reaction vessel 110 and has a heat transfer jacket 152 having a heat medium therein, and a heater 154 for supplying heat to the heat transfer jacket 152. Include.
  • the heat medium uses a silicone-based oil having a smaller specific heat than the reactant, and the heat transferred to the reactant is indirectly made through the heat medium.
  • the nitrogen / electromagnetic wave supply unit 170 is a reaction vessel 110 through a nitrogen / electromagnetic wave inlet 114.
  • a horn antenna 172 for supplying nitrogen and electromagnetic waves to a reactant
  • a waveguide 176 connected to the horn antenna 172 and provided with a nitrogen inlet 174
  • a waveguide 176 and an electromagnetic wave It may include a magnetron oscillator 178 to generate.
  • pressurization in the reaction vessel 110 is performed by injecting nitrogen gas which is an inert gas, and decompression is performed by a pressure reduction pump 190 connected with the reaction vessel 110.
  • a heat exchanger 180 is provided between the reaction vessel 110 and the decompression pump 190 to adjust the temperature of the gas flowing into the decompression pump 190.
  • Figure 20 is a conceptual diagram illustrating the position of the nitrogen / electromagnetic inlet of the high conductivity polylactic acid polymer manufacturing apparatus according to the present invention, as shown, the nitrogen / electromagnetic inlet 114 is based on the center of the reaction vessel 110 It can be installed at a position 3/8 of the diameter (D) of the reaction vessel, when installed in this position, the amount of electromagnetic radiation is uniformly distributed over the entire surface of the reactant.
  • electromagnetic waves radiated from the horn-shaped horn antenna 172 not only directly irradiate the surface of the reactant but also reflect the reflected wave reflected from the inside of the reaction vessel, and the reactant is uniformly moved by being stirred by the stirrer 130.
  • a survey will be available.
  • a member e.g., mica plate, etc.
  • a member having a low transmission loss of electromagnetic waves is installed to physically shield the magnetron oscillator and the waveguide 176, and the nitrogen inlet port of the waveguide 176. It is desirable to install 174.
  • Nitrogen gas according to the present invention flows into the waveguide 176 and is supplied to the reaction vessel through the horn horn antenna 567. As the nitrogen gas is supplied, the vapor of the reactant may be prevented from infiltrating into the waveguide 176, the pressure control required for the reaction may be performed, and the cyclic polypeptide may be generated.
  • FIG. 21 is a conceptual diagram illustrating a state in which a reactant moves in a reaction container of the apparatus for preparing a highly conductive polylactic acid polymer according to the present invention. As shown in FIG. However, the entire reactant is swirled to the right in the polymerization apparatus, but the outer edge portion is faster than the center, so it is possible to receive the electromagnetic wave uniformly.
  • step S1 100 parts by weight of polylactic acid having an average molecular weight of 5,000 to 10,000, 5 to 10 parts by weight of polyglycolic acid, and 10 to 20 parts by weight of lactide are added. And 0.1-10 weight part of ammonium vanadate which is a catalyst, and 0.1-10 weight part of vanadium oxides which are a catalyst are added and stirred to a reaction container. At this time, by operating a heater to heat the temperature in the reaction vessel to 160 ⁇ 190 °C, the pressure in the reaction vessel is adjusted to 0.1 ⁇ 0.5 atm using a pressure reducing pump.
  • step S2 5-10 parts by weight of serine and 0.1-1 part by weight of dodecyl alcohol are added to the reaction vessel, and nitrogen and electromagnetic waves are supplied to the reactants through a nitrogen / electromagnetic wave supply part.
  • the electromagnetic wave is irradiated with a frequency of 2.45 GHz from a magnetron oscillator with a rated output of 3 kW and 30 to 100 W per kg of reactant, and during irradiation, the temperature in the reaction vessel is maintained at 160 to 190 ° C. and the pressure is 1 to 5 atm.
  • step S3 0.1-1 part by weight of dodecyl alcohol and 0.1-1 part by weight of cerium acetate are added and stirred.
  • step S4 the temperature of 160-190 ° C. is maintained while the supply and stirring of electromagnetic waves and nitrogen are stopped, and the pressure is reduced to 0.1 to 0.5 atm.
  • the reactant discharged according to Example 1 is a highly conductive polylactic acid combined with cerium (metal atom group) To prepare.
  • reaction vessel 112a, 112b raw material inlet
  • stirring blade 150 heat supply
  • stirring blade 250 electric heater
  • condenser 292 condensate storage
  • body 312 lactic acid concentrate outlet
  • concentration chamber 328 cathode
  • stirring device 332 stirring blade
  • thermal insulation jacket 400 electrodialysis apparatus
  • electrolytic cell 412 anolyte chamber
  • fermentation broth 416 lactate / lactic acid solution chamber

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Abstract

La présente invention concerne un procédé de production d'acide polylactique, et plus particulièrement, un procédé de production d'acide polylactique, qui permet d'augmenter le rendement de production et de réduire les coûts, et qui permet de produire de manière plus appropriée un acide polylactique de poids moléculaire élevé conformément à l'utilisation de celui-ci. De même, la présente invention concerne un procédé de production d'un polymère d'acide polylactique de conductivité élevée, qui est économique en termes de temps et de coût étant donné qu'un acide polylactique de conductivité élevée peut être produit efficacement, et un appareil de production du polymère d'acide polylactique de conductivité élevée. Selon la présente invention, le procédé de production de l'acide polylactique de conductivité élevée comprend : une étape S1 d'addition et de mélange de 100 parties en poids d'acide polylactique, 10 à 20 parties en poids de lactide, et 5 à 10 parties en poids d'acide polyglycolique dans une cuve de réaction ; une étape S2 d'addition de 5 à 10 parties en poids de sérine et 0,1 à 1 partie en poids d'alcool de dodécyle dans la cuve de réaction, et ensuite d'alimentation de cette dernière en gaz inerte et d'irradiation de celle-ci avec des ondes électromagnétiques ; et une étape S3 d'addition de 0,1 à 1 partie en poids de sélénium acide acétique dans la cuve de réaction, et ensuite de mélange.
PCT/KR2011/006143 2010-11-26 2011-08-19 Procédé de production d'acide polylactique et de polymère de conductivité élevée et appareil pour la production de polymère d'acide polylactique de conductivité élevée Ceased WO2012070747A2 (fr)

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CN115491003A (zh) * 2022-09-14 2022-12-20 包头稀土研究院 稀土氨基酸配合物的用途、聚乳酸组合物及其制备方法
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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2546552B2 (ja) * 1991-05-16 1996-10-23 富士通株式会社 磁気ディスク装置
JP3267391B2 (ja) * 1993-06-30 2002-03-18 三井化学株式会社 分解性ポリマー
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DE10020898B4 (de) * 2000-04-20 2004-02-05 Inventa-Fischer Gmbh Verfahren zur Herstellung von Polymilchsäure und Vorrichtung hierzu
JP3734821B1 (ja) * 2004-09-30 2006-01-11 株式会社グリーン環境テクノロジー ポリ乳酸の製造方法、及びポリ乳酸製造装置
KR100603649B1 (ko) * 2006-03-31 2006-07-24 가부시키가이샤 그린칸쿄테크놀로지 폴리유산 제조장치 및 방법

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EP3650453A4 (fr) * 2017-07-04 2021-03-31 Optimizer Inc. Poly(acide lactique) modifié, poly(acide lactique) modifié polymerisé, et procédé et appareil pour sa production
CN115491003A (zh) * 2022-09-14 2022-12-20 包头稀土研究院 稀土氨基酸配合物的用途、聚乳酸组合物及其制备方法
CN115491003B (zh) * 2022-09-14 2023-08-15 包头稀土研究院 稀土氨基酸配合物的用途、聚乳酸组合物及其制备方法
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CN117887229B (zh) * 2024-03-13 2024-05-31 上海宝柏新材料股份有限公司 一种生物降解塑料

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