WO2010123095A1 - ポリエステルの合成方法および装置 - Google Patents

ポリエステルの合成方法および装置 Download PDF

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WO2010123095A1
WO2010123095A1 PCT/JP2010/057227 JP2010057227W WO2010123095A1 WO 2010123095 A1 WO2010123095 A1 WO 2010123095A1 JP 2010057227 W JP2010057227 W JP 2010057227W WO 2010123095 A1 WO2010123095 A1 WO 2010123095A1
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Prior art keywords
esterification
reaction
butanediol
catalyst
tank
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PCT/JP2010/057227
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English (en)
French (fr)
Japanese (ja)
Inventor
俊明 松尾
将行 上川
憲一郎 岡
健之 近藤
博之 伊藤
康成 佐世
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株式会社日立プラントテクノロジー
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Priority to CN201080017827.3A priority Critical patent/CN102414247B/zh
Priority to KR1020117024871A priority patent/KR101289920B1/ko
Publication of WO2010123095A1 publication Critical patent/WO2010123095A1/ja

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a method for producing polybutylene succinate using succinic acid and 1,4-butanediol as main raw materials.
  • biomass-derived polyester has attracted attention as an alternative material for general-purpose plastics produced from petroleum-derived materials such as polypropylene and polyethylene.
  • polyethylene succinate (PES), polybutylene succinate (PBS) and the like are synthesized by condensation polymerization of biomass-derived dicarboxylic acids such as glycol and succinic acid. These are made from aliphatic glycols (ethylene glycol, 1,3-propanediol, 1,4-butanediol) and dicarboxylic acids.
  • PBS is a biodegradable biosynthesis synthesized by condensation polymerization of 1,4-butanediol (1,4-BDO) with succinic acid and transesterification of the resulting oligomer by transesterification.
  • Plastic FIG. 1.
  • the esterification reaction is a coupling reaction of a carboxyl group of dibasic acid and an OH group of glycol that occurs under an inert gas atmosphere such as nitrogen under normal pressure or weak negative pressure, and water is generated as a by-product (formula 1). Therefore, the reaction is promoted by removing water by devolatilization. Moreover, reaction is accelerated by the addition of a catalyst as needed.
  • the transesterification reaction is a reaction in which the terminal glycol of one oligomer is released and bonded to the terminal glycol of the other oligomer between oligomers produced by the esterification reaction in a reduced pressure environment and in the presence of a catalyst.
  • Glycol is produced as a by-product (Formula 2), which is devolatilized and removed to accelerate the reaction and increase the degree of polymerization.
  • the starting glycol may be deteriorated by a dehydration reaction by the catalytic action of a dibasic acid.
  • the glycol is ethylene glycol
  • diethylene glycol is generated (formula 3)
  • 1,4-BDO is formed
  • tetrahydrofuran (THF) is generated (formula 4). Since these side reactions cause a decrease in raw material yield, it is desirable to suppress them as much as possible.
  • Patent Documents 1 and 2 The esterification in the production of PBS is described in Patent Documents 1 and 2, for example.
  • Patent Document 1 discloses conditions of a temperature of 220 to 230 ° C. and a total reaction time of 3 hours
  • Patent Document 2 discloses conditions of a temperature of 160 to 230 ° C. and a reaction time of 5 to 14 hours.
  • succinic acid such as PBS
  • Non-Patent Document 1 relates to the production of polybutylene terephthalate (hereinafter referred to as PBT) using 1,4-BDO as a glycol as in PBS, and relates to a method for suppressing the formation of THF in the esterification step.
  • generation of THF in the esterification step is promoted by an acid catalyst, that is, a dibasic acid (terephthalic acid), and activation energy (32.1 kcal) related to the side reaction is a main reaction, that is, an ester. It is described that it is difficult to suppress the formation of THF by the reaction temperature because it is approximately the same as that of the conversion reaction (30.5 kcal), and that the addition of a catalyst that promotes only the main reaction is effective as a countermeasure.
  • JP 2008-94888 A Japanese Patent No. 2713108
  • the melting point of succinic acid of 185 ° C. was selected for the lower limit of the temperature.
  • the reason is that the esterification reaction proceeds mainly in the portion where succinic acid is dissolved in 1,4-butanediol at a temperature of less than 185 ° C., whereas the whole is dissolved at a temperature of 185 ° C. This is because it is miscible with butanediol and the esterification reaction is greatly accelerated.
  • the upper limit of temperature was selected based on the following.
  • the concentration of THF dissolved in the by-product (water) of the main reaction reaches about 10 wt%, Wastewater treatment mainly for separation and removal of THF is required, but if it is about 2 wt% or less, there is a possibility that it can be discharged without simple dilution treatment or wastewater treatment. Accordingly, it is desirable to make the progress of the THF formation reaction relative to the promotion of the esterification reaction 1/5 or less as compared with the case of the temperature of 230 ° C. From this result, 195 ° C.
  • the present invention includes the following inventions.
  • a process for producing polybutylene succinate comprising an esterification step in which a raw material slurry containing succinic acid and 1,4-butanediol as main raw materials is esterified to synthesize an oligomer, and a condensation polymerization step in which the oligomer is transesterified Because
  • the catalyst is added to the raw slurry in the esterification step, the esterification reaction is performed at 185 to 195 ° C., and the catalyst is additionally added in the condensation polymerization step.
  • 1 illustrates one embodiment of a process for producing a polybutylene succinate of the present invention.
  • An Arrhenius plot (temperature dependence of reaction rate constant) regarding esterification reaction of succinic acid and 1,4-butanediol is shown. The correlation between the esterification reaction temperature, the rate constant of the esterification reaction relative to 230 ° C., and the ratio of the rate constant of the tetrahydrofuran production reaction to the esterification reaction is shown.
  • 1 shows an embodiment of a process for producing polybutylene succinate in the present invention.
  • the method for producing polybutylene succinate of the present invention includes an esterification step of esterifying a raw slurry containing succinic acid and 1,4-butanediol as main raw materials to synthesize an oligomer, and an ester exchange reaction of the oligomer A polycondensation step for synthesizing polybutylene succinate.
  • the production process of polybutylene succinate usually includes a raw material slurry preparation process in which 1,4-butanediol as a raw material and succinic acid are mixed, an esterification process, a condensation polymerization process, a pelletization process, and a drying process. If necessary, melt devolatilization of the polymer is performed between the condensation polymerization step and the pelletizing step, and the solid phase polymerization step is performed after the drying step.
  • the method of the present invention is characterized in that a catalyst is added to the raw slurry in the esterification step.
  • the catalyst may be added before the esterification step, for example, in the raw slurry preparation step, or the catalyst may be added in the esterification step.
  • the catalyst may be partially deactivated by the action of a by-product (water) produced during the esterification reaction.
  • the catalyst that has avoided the deactivation usually also acts in the condensation polymerization reaction.
  • the method of the present invention is also characterized in that a catalyst is additionally added in the condensation polymerization step by transesterification.
  • a catalyst is additionally added in the condensation polymerization step by transesterification.
  • the catalyst deactivated in the esterification step can be supplemented.
  • the addition of the catalyst may be performed before or at the start of the condensation polymerization step, or may be performed during the condensation polymerization step.
  • the catalyst is deactivated due to the reaction with water generated as a by-product in the esterification step. Since loss increases, it is not preferable.
  • Esterification is often performed in an inert atmosphere at normal pressure, but moderate pressure reduction or pressure increase may be performed as necessary.
  • a mixture of water, which is a by-product generated in the esterification reaction, and raw material 1,4-butanediol is volatilized, but it is usually subjected to partial condensation to condense 1,4-butanediol and esterify it. Return to the process and release moisture out of the system.
  • the polycondensation step is usually carried out in a plurality of steps depending on the required degree of vacuum. At that time, a catalyst is additionally added in the first condensation polymerization step or in the preceding stage.
  • 1,4-butanediol which is a by-product of the reaction, water produced by the esterification reaction with partially unreacted end groups, a polymer having a low molecular weight and a relatively large vapor pressure, and the like are volatilized.
  • the gas containing volatile substances is usually washed in a wet condenser system and then discharged out of the system via a decompression device.
  • a catalyst for the esterification reaction and the condensation polymerization reaction those skilled in the art can appropriately select a suitable catalyst.
  • a catalyst containing at least one metal or metal compound selected from Group IVB of the periodic table can be used. Examples thereof include titanium compounds such as titanium dioxide and tetrapropyl titanate, and zirconium compounds such as zirconium isopropoxide.
  • a catalyst containing at least one metal or metal compound selected from Group IVA and Group VA of the periodic table can also be used.
  • Group IVA metal compounds include organotin-based catalysts (eg, tin lactate, tin tartrate, tin dicaprylate, tin dilaurate, tin dipalmitate, tin distearate, tin dioleate, tin ⁇ -naphthoate). , ⁇ -naphthoate, tin 2-ethylhexanoate, etc.) and powdered tin.
  • organotin-based catalysts eg, tin lactate, tin tartrate, tin dicaprylate, tin dilaurate, tin dipalmitate, tin distearate, tin dioleate, tin ⁇ -naphthoate). , ⁇ -naphthoate, tin 2-ethylhexanoate, etc.
  • the group VA metal compound include antimony compounds such as antimony trioxide.
  • the catalyst is in the form of a liquid or a powder, it is added to the raw material, the molten prepolymer or the like by a catalyst addition device usually used in the art, and then the mixed solution is continuously supplied to the reaction vessel, and the reaction vessel It can be added by a method of bringing it into contact with a raw material or a melted prepolymer that has been directly added and continuously supplied.
  • the polymerization vessel for proceeding the condensation polymerization is not particularly limited, but is a tank type polymerization device for oligomer condensation polymerization, that is, initial condensation polymerization, a horizontal type uniaxial polymerization vessel for intermediate condensation polymerization, that is, horizontal type for final condensation polymerization. It is desirable to use a polymerization vessel (horizontal biaxial polymerization vessel) equipped with a biaxial stirrer having excellent stirring and mixing performance. In the intermediate condensation polymerization, although the melt viscosity of the polymer rises rapidly, it does not reach the high viscosity region (> 500 Pa ⁇ s), and therefore, a uniaxial polymerization reactor may be used.
  • the low-viscosity fluid on the inlet side is moved to the outlet side by providing a weir in the polymerization vessel as necessary from the viewpoint of improving the plug flow property. It is preferable to suppress the rapid flow.
  • a horizontal biaxial polymerization apparatus capable of self-cleaning the stirring shaft. Examples of such a biaxial polymerizer include a lattice blade polymerizer (Japanese Patent No. 1899479) manufactured by Hitachi Plant Technology, and a spectacle blade polymerizer (Japanese Patent No. 4112908).
  • a method for heating the condensation polymerization apparatus a method generally used in this technical field can be used.
  • a jacket of a heat medium is installed on the outer periphery of the condensation polymerization apparatus, and the reaction liquid is heated by heat transfer through the wall surface.
  • a method of heating by heat transfer through a heat transfer tube (coil) inside the condensation polymerization device, etc. may be used alone or in combination.
  • the term “continuous” has the meaning normally used in this technical field, and the time zone during which the supply of raw materials and the like and the discharge of products and reaction liquids overlap at least partially, This includes the case where the supply is continuously performed and the product, the reaction liquid, and the like are continuously discharged.
  • Additives other than the catalyst may be added to the raw slurry and molten reaction liquid.
  • additives other than the catalyst include antioxidants, stabilizers, ultraviolet absorbers, pigments, colorants, inorganic particles, various fillers, mold release agents, plasticizers, crosslinking agents, and the like.
  • the addition ratio of these additives is arbitrary, but is preferably 50% by weight or less, particularly preferably 30% by weight or less, based on the main raw materials (succinic acid and 1,4-butanediol).
  • crosslinking by a crosslinking agent is described in Patent Documents 1 and 2, any crosslinking may be used, such as crosslinking by condensation polymerization, crosslinking due to vinyl group cleavage or terminal group urethane bonding.
  • crosslinking reaction proceeds in parallel with the progress of the main reaction.
  • a necessary crosslinking reaction is carried out after completion of the condensation polymerization.
  • the cross-linking reaction When the cross-linking reaction is carried out after completion of the condensation polymerization, the molecular weight and viscosity of the polymer are increased, so when adding the necessary chemicals, mixing is performed with a horizontal biaxial polymerizer that excels in stirring and mixing performance of highly viscous fluids. It is desirable to do.
  • a biaxial polymerizer include the above-described spectacle blade polymerizer and lattice blade polymerizer, as well as a high shear blade polymerizer manufactured by Hitachi Plant Technology (JP-A-8-252822).
  • the condenser main body in the wet condenser system is usually a mixed condenser in which a large amount of refrigerant is brought into direct contact with the gas, and any system such as a countercurrent multistage contact type or a parallel flow jet type may be used.
  • the heat exchanger in the wet condenser system is usually a partition type indirect heat exchanger, and a multi-tubular cylindrical heat exchanger is desirable.
  • the type of the fixed head of the heat exchanger there are a lid plate separation type, a bonnet type, a tube plate integrated type, a tube plate barrel integrated type, a special high pressure type, etc. Any type may be used.
  • the body portion may be of any type such as a 1-pass type, a longitudinal baffle plate 2-pass type, a diversion type, a double diversion type, a split flow type, a kettle type, or a cross flow type.
  • the hot well in the wet condenser system is usually a closed tank, but a heat medium jacket is preferably installed, and a structure capable of heating or cooling the staying liquid inside is desirable.
  • the stirring apparatus when a solid substance is dissolved in a refrigerant
  • the strainer should be installed to separate and remove insoluble solids in advance. However, if the solids are precipitated by cooling the accumulated liquid in the heat medium jacket, the solids should be separated and removed by installing a strainer. Is particularly desirable.
  • the decompression device may be any of a variety of vacuum pumps, a multistage ejector that operates with a raw material liquid, or a combination in which an ejector group is installed in the upper stage and a vacuum pump is installed in the lower stage.
  • esterification step in the method for producing polybutylene succinate of the present invention will be described in more detail. According to the present invention, it is possible to realize improvement in reduction in raw material yield due to 1,4-butanediol degradation, simplification or omission of wastewater treatment equipment, equipment cost reduction by equipment scale reduction, and energy saving by reduction of esterification reaction temperature.
  • the esterification step in the esterification tank in which the inside is maintained at a predetermined temperature and pressure, the continuously supplied raw slurry is subjected to an esterification reaction, and water as a by-product is discharged out of the system as water vapor, (Oligomer) is continuously discharged and continuously supplied to the subsequent condensation polymerization step.
  • the raw material slurry is usually prepared and supplied by mixing succinic acid and 1,4-butanediol in a raw material slurry preparation tank.
  • the tank In the raw slurry preparing tank, the tank may be heated to ensure the fluidity of the raw slurry.
  • the heating temperature is usually 25 to 150 ° C., preferably 50 to 100 ° C.
  • the tank In order to continuously supply the raw material slurry, it is desirable that the raw material slurry is once supplied to the storage tank and then continuously supplied to the esterification tank. In the storage tank, the tank may be heated to ensure fluidity of the raw slurry.
  • the heating temperature is usually 25 to 150 ° C., preferably 50 to 100 ° C.
  • an independent circulation line is provided separately from the line for feeding the slurry to the esterification tank, so that the raw slurry exceeds the succinic acid sedimentation rate. It is preferable to circulate at a flow rate of
  • the raw slurry is subjected to an esterification reaction at a predetermined temperature and pressure to produce an ester of succinic acid and 1,4-butanediol.
  • the reaction temperature is 185 to 195 ° C., preferably 189 to 191 ° C., from the viewpoint of melting point of succinic acid and reduction of THF production.
  • the esterification reaction is usually performed at normal pressure.
  • the esterification reaction is carried out until the acid value of the ester reaches 30 or less, preferably 15 or less, more preferably 10 or less.
  • a method usually used in this technical field can be used, for example, a method of heating a reaction liquid by heat transfer through a wall surface by installing a heat medium jacket on the outer periphery of the tank, Or there is a method of heating by heat transfer through a heat transfer tube (coil) inside the tank, and these may be used alone or in combination.
  • a reactor usually used for producing polyester by esterification can be used.
  • examples of such a reactor include a vertical stirring tank equipped with a stirring device having a stirring blade having a vertical rotation axis (for example, a paddle blade, a helical ribbon blade, etc.).
  • a stirring device having a stirring blade having a vertical rotation axis for example, a paddle blade, a helical ribbon blade, etc.
  • By-product water vapor and evaporated 1,4-butanediol flow into a distillation column installed at the top of the tank, and 1,4-butanediol contained in the high-boiling fraction is recovered and transferred to a raw material slurry preparation tank, etc. You may recycle and reuse.
  • the gas containing by-product or unreacted vapor discharged from the distillation column is sent to a wet condenser to which a spray of liquid 1,4-butanediol is applied for washing, and the washed gas is discharged out of the system. .
  • the drain liquid generated in the wet condenser is sent to the hot well, where the solid content is removed by the strainer at the inlet of the hot well and stored.
  • the accumulated liquid stored is sent to the filter by a liquid feed pump.
  • the filter has a plurality of systems installed in parallel, and when one is in operation, the rest is valve operated so that maintenance work can be performed.
  • FIG. 4 shows a specific example of a production process for carrying out the method for producing polybutylene succinate of the present invention.
  • the manufacturing process shown in FIG. 4 includes a raw material slurry preparation step, an esterification step, a condensation polymerization step, a melt devolatilization step, a pelletization step, a drying step, and a solid phase polymerization step.
  • the polycondensation step is performed in three steps of initial polycondensation, intermediate polycondensation, and final polycondensation, but the number of steps may be increased or decreased as required.
  • 1,4-butanediol has a melting point in the vicinity of 25 ° C. and is heated and melted and added as a liquid.
  • Succinic acid is a powder, and the piping 4 is provided with a mechanism for transferring the powder, such as a snake pump, as necessary.
  • these are sufficiently mixed to prepare a slurry, and the powder is prevented from separating from the liquid.
  • the slurry produced in the raw slurry preparing tank 7 is continuously transferred from the pipe 8 to the esterification tank 9.
  • the esterification step while the esterification tank 9 is continuously supplied with the slurry from the pipe 8, an additive such as a catalyst is continuously supplied again from the tank 10 via the pipe 11, and the reaction solution is continuously discharged from the pipe 18. .
  • the catalyst is already added in the raw slurry preparing tank, the catalyst addition to the esterification tank may be omitted.
  • the reaction is carried out at 185 to 195 ° C. for 2 to 5 hours, preferably 3 to 5 hours under pressure conditions of an inert atmosphere of normal pressure to weak negative pressure.
  • 1,4-butanediol is ester-bonded to both carboxyl groups of succinic acid to produce an oligomer (weight average degree of polymerization of about 10) and water.
  • Water, 1,4-butanediol, and oligomer are volatilized, and the vapor containing them is sent to the partial reduction device 13 through the pipe 12.
  • cooling is performed, and steam having a low boiling point and 1,4-butanediol thermally deteriorated product (tetrahydrofuran) are discharged out of the system via the pipe 15, the exhaust fan 16, and the nozzle 17.
  • the 1,4-butanediol and oligomer having a high boiling point are condensed by the partial reduction device 13 and refluxed to the esterification tank 9 via the pipe 14.
  • the reaction solution containing the oligomer is transferred from the esterification tank 9 to the initial condensation polymerization device 19 via the pipe 18.
  • the initial polycondensation unit 19 is continuously supplied with the oligomer from the pipe 18, while the catalyst is continuously supplied from the tank 20 via the pipe 21, and the reaction liquid containing the prepolymer is continuously discharged from the pipe 26.
  • heating at 200 to 250 ° C., preferably 220 to 240 ° C. is performed for 1 to 3 hours, preferably 2 hours under a pressure condition of about 10 to 40 torr, preferably about 20 to 30 torr achieved by the vacuum device 24.
  • the weight average degree of polymerization of the reaction solution becomes about 20-100.
  • the acceleration of the polycondensation reaction is due to the transesterification reaction at the end of the oligomer, and it is necessary to devolatilize 1,4-butanediol which is a by-product generated at that time.
  • the produced 1,4-butanediol is volatilized with a low molecular weight polymer mainly composed of oligomers and moisture produced by the esterification reaction of a part of the end groups, and the vapor containing these vapors passes through the pipe 22 to the wet condenser system 170. Sent to.
  • the wet condenser system 170 is supplied with 1,4-butanediol from the tank 1 via the 1,4-BDO supply pipes 57 and 58.
  • the supplied 1,4-butanediol is sprayed onto the steam sent from the pipe 22 in the wet condenser system 170, whereby the steam is cooled and condensed.
  • condensation using 1,4-butanediol, 1,4-butanediol, a low molecular weight polymer, and moisture are removed from the vapor transferred from the pipe 22, and the residual exhaust gas is supplied to the pipe 23, vacuum device 24, It discharges outside the system via the nozzle 25.
  • the 1,4-butanediol sprayed in the wet condenser system 170 mixes with the vapor condensate, and is recovered in the tank 1 through the 1,4-BDO recovery pipes 63 and 62.
  • the recovered material can be reused as a raw material for the polymer, if necessary.
  • the reaction solution containing the prepolymer generated by the condensation polymerization of the oligomer is transferred from the initial condensation polymerization device 19 to the intermediate condensation polymerization device 27 via the pipe 26.
  • the intermediate condensation polymerizer 27 continuously discharges the reaction liquid from the pipe 33 while receiving the continuous supply of the prepolymer from the pipe 26.
  • heating at 230 to 260 ° C., preferably 240 ° C. is performed for 0.5 to 2 hours, preferably about 1 hour under the pressure condition of 1 to 10 torr, preferably about 4 torr achieved by the vacuum apparatus 31. .
  • the prepolymer has a weight average degree of polymerization of about 100 to 300.
  • the acceleration of the polycondensation reaction is due to a transesterification reaction at the end of the prepolymer, and it is necessary to devolatilize 1,4-butanediol, which is a by-product generated at that time.
  • the produced 1,4-butanediol is volatilized together with the low molecular weight polymer and moisture produced by the esterification reaction of some end groups, and the vapor containing these is sent to the wet condenser system 29 via the pipe 28.
  • 1,4-Butanediol is supplied from the tank 1 through the 1,4-BDO supply pipes 57 and 59 to the wet condenser system 29.
  • the supplied 1,4-butanediol is sprayed on the steam sent from the pipe 28 in the wet condenser system 29, whereby the steam is cooled and condensed.
  • 1,4-butanediol, low molecular weight polymer and moisture are removed from the vapor transferred from the pipe 28 by condensation using 1,4-butanediol, and the residual exhaust gas is supplied to the pipe 30, vacuum device 31, nozzle 32 is discharged outside the system. Further, the reaction liquid containing the prepolymer is transferred from the intermediate condensation polymerization device 27 to the final condensation polymerization device 34 via the pipe 33.
  • the 1,4-butanediol sprayed in the wet condenser system 29 mixes with the vapor condensate and is recovered in the tank 1 through the 1,4-BDO recovery pipes 64 and 62.
  • the recovered material can be reused as a raw material for the polymer, if necessary.
  • the final condensation polymerization device 34 continuously discharges the reaction solution from the piping 40 while receiving continuous supply of the prepolymer from the piping 33.
  • heating at 230 to 260 ° C., preferably about 250 ° C. is performed for about 1 to 4 hours, preferably about 2 hours under a pressure condition of about 1 torr achieved by the vacuum device 38.
  • the weight average degree of polymerization of the polymer (polybutylene succinate) becomes about 200 to 400.
  • the acceleration of the polycondensation reaction is due to a transesterification reaction at the end of the prepolymer, and it is necessary to devolatilize 1,4-butanediol, which is a by-product generated at that time.
  • the generated 1,4-butanediol is volatilized together with the low molecular weight polymer and moisture generated by the esterification reaction of some end groups, and the vapor containing these is sent to the wet condenser system 36 via the pipe 35.
  • 1,4-Butanediol is supplied from the tank 1 via the 1,4-BDO supply pipes 57 and 60 to the wet condenser system 36.
  • the supplied 1,4-butanediol is sprayed on the steam sent from the pipe 35 in the wet condenser system 36, whereby the steam is cooled and condensed.
  • condensation using 1,4-butanediol, 1,4-butanediol, low molecular weight polymer and moisture are removed from the vapor transferred from the pipe 35, and the residual exhaust gas is supplied to the pipe 37, vacuum device 38, nozzle It is discharged out of the system via 39.
  • the 1,4-butanediol sprayed in the wet condenser system 36 mixes with the vapor condensate and is recovered in the tank 1 through the 1,4-BDO recovery pipes 65 and 62.
  • the recovered material can be reused as a raw material for the polymer, if necessary.
  • the reaction liquid containing the polymer (polybutylene succinate) produced in the final condensation polymerization step is transferred from the final condensation polymerization vessel 34 to the melt devolatilizer 41 via the pipe 40.
  • the melt devolatilizer 41 continuously discharges the reaction solution from the pipe 47 while receiving continuous supply of the polymer from the pipe 40.
  • heating is performed at 200 to 250 ° C., preferably about 230 ° C. under a pressure condition of about 0.5 to 3 torr achieved by the vacuum device 45.
  • 1,4-Butanediol is supplied from the tank 1 through the 1,4-BDO supply pipes 57 and 61 to the wet condenser system 43.
  • the supplied 1,4-butanediol is sprayed on the steam sent from the pipe 42 in the wet condenser system 43, whereby the steam is cooled and condensed.
  • the condensation using 1,4-butanediol removes 1,4-butanediol, low molecular weight polymer, and moisture from the vapor transferred from the pipe 42, and the residual exhaust gas is supplied to the pipe 44, vacuum device 45, nozzle It is discharged out of the system via 46.
  • the melt devolatilization step may be omitted.
  • the 1,4-butanediol sprayed in the wet condenser system 43 mixes with the vapor condensate, and is recovered in the tank 1 through the 1,4-BDO recovery pipes 66 and 62.
  • the recovered material can be reused as a raw material for the polymer, if necessary.
  • the melt devolatilization step can be deleted as necessary.
  • the polymer discharged from the melt devolatilization step is transferred to the pelletizing step, cooled and solidified by the water cooling device 48, pelletized by the chip cutter 49, and transferred to the drying step by the pipe 50.
  • the pellets transferred to the drying process move on the belt conveyor 51, and at that time, the water adhering to the water cooling is removed by the wind sent by the blower 52. At that time, if the wind of the blower 52 is warm, the drying effect may be improved.
  • the dried pellets are received by the tank 54 via the pipe 53 and are solid-phase polymerized by the hot air from the blower 55. Pellets subjected to solid phase polymerization are discharged from the pipe 56. Note that the solid phase polymerization step may be omitted.
  • Example 1 PBS was synthesized by the synthesizer shown in FIG.
  • tetrabutyl titanium was used as the catalyst.
  • the esterification step was carried out under the conditions of a temperature of 190 ° C., a pressure of 760 torr, a residence time of 5 hours, and a catalyst addition (titanium dioxide 100 ppm), an oligomer having an esterification rate of 92% and a weight average degree of polymerization of about 10 was obtained.
  • the prepolymer having a weight average polymerization degree of 50 was produced by allowing the catalyst to stay in an initial condensation polymerization reactor in an environment of a temperature of 230 ° C.
  • the polybutylene succinate having a weight average polymerization degree of 300 was produced by retaining this in a final condensation polymerization step in an environment of a temperature of 250 ° C. and a pressure of 1 torr for 2 hours.
  • the THF concentration in the by-product (water) discharged from the esterification tank was 2 wt%.
  • Example 1 Comparative Example 1
  • the catalyst was not added in the esterification step, and the reaction temperature was raised to 230 ° C. corresponding to the boiling point of 1,4-butanediol and reacted for 5 hours.
  • the esterification rate and the average degree of polymerization of the oligomer produced were the same as those in Example 1.
  • the THF concentration in the by-product (water) discharged from the esterification tank was 10 wt%.
  • Example 2 (Comparative Example 2) In Example 1, the catalyst was not added in the esterification step, and the reaction temperature was 180 ° C. lower than the melting point of succinic acid 185 ° C. for 6 hours. As a result, the esterification rate of the produced oligomer was as extremely low as about 30%.

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JP2016500393A (ja) * 2012-12-12 2016-01-12 サムスン ファイン ケミカルズ カンパニー リミテッドSamsungfine Chemicals Co., Ltd. 生分解性脂肪族−芳香族ポリエステル共重合体の連続製造方法
CN115558090A (zh) * 2022-10-12 2023-01-03 中国天辰工程有限公司 一种低四氢呋喃含量的聚丁二酸丁二醇酯的制备方法

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KR101992391B1 (ko) * 2012-09-04 2019-09-30 (주)새한폴리머 생분해성 지방족/방향족 폴리에스테르 공중합체의 연속 제조방법
JP2014095037A (ja) * 2012-11-09 2014-05-22 Hitachi Ltd ポリエステルの製造装置及び製造方法
JP2018150453A (ja) * 2017-03-13 2018-09-27 三菱ケミカル株式会社 ポリブチレンサクシネートの製造方法
WO2024122771A1 (ko) * 2022-12-06 2024-06-13 주식회사 엘지화학 폴리에스테르 중합체, 및 이의 제조방법, 촉매 시스템

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CN115558090A (zh) * 2022-10-12 2023-01-03 中国天辰工程有限公司 一种低四氢呋喃含量的聚丁二酸丁二醇酯的制备方法
CN115558090B (zh) * 2022-10-12 2023-08-11 中国天辰工程有限公司 一种低四氢呋喃含量的聚丁二酸丁二醇酯的制备方法

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