WO2013061834A1 - 高分子量化された脂肪族ポリエステルの製造方法 - Google Patents
高分子量化された脂肪族ポリエステルの製造方法 Download PDFInfo
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- WO2013061834A1 WO2013061834A1 PCT/JP2012/076786 JP2012076786W WO2013061834A1 WO 2013061834 A1 WO2013061834 A1 WO 2013061834A1 JP 2012076786 W JP2012076786 W JP 2012076786W WO 2013061834 A1 WO2013061834 A1 WO 2013061834A1
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—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
- C08G2101/00—Manufacture of cellular products
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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
- C08G2230/00—Compositions for preparing biodegradable polymers
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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
- C08G2310/00—Agricultural use or equipment
Definitions
- the present invention relates to a continuous and efficient method for producing a high molecular weight aliphatic polyester.
- the resulting high molecular weight polyester is a high quality resin.
- a high molecular weight is advanced by removing the desorbed component out of the system.
- the system is generally brought to a high temperature and high vacuum condition, and the desorbed component is distilled off.
- a glycol component and an aliphatic dicarboxylic acid are esterified, and the resulting polyester diol is present in the presence of a catalyst at a temperature of 180 to 230 ° C. and a high vacuum of 0.005 to 0.1 mmHg.
- a method for producing a high molecular weight aliphatic polyester that undergoes a deglycolization reaction is disclosed.
- an aliphatic polyester prepolymer having a terminal hydroxyl group is substantially a hydroxyl group in a molten state at or above its melting point. It has been proposed to increase the molecular weight of an aliphatic polyester by adding a diisocyanate having an isocyanate group equivalent to 10 to 2 equivalents.
- the high molecular weight aliphatic polyester obtained by this method is a resin having a weight average molecular weight (Mw) of 200,000 or more, which is not obtained by a conventional direct polymerization method, and has good moldability and physical properties such as a film. It is known that there is.
- Mw weight average molecular weight
- the present inventors added isocyanate to the polymerization tank at a temperature higher than the melting point of the aliphatic polyester prepolymer for high molecular weight. Then, the isocyanate was evaporated at a high temperature, and not all of the added amount contributed to the reaction, and the evaporated isocyanate was found to adhere to the reaction vessel wall surface in the gas phase.
- the present invention prevents the diisocyanate from evaporating when the diisocyanate is mixed with the aliphatic polyester prepolymer which is melted at a melting point or higher and is in a liquid phase, and the diisocyanate and the aliphatic polyester prepolymer are uniformly mixed.
- Another object of the present invention is to provide a method for efficiently producing a high molecular weight aliphatic polyester.
- the present inventors have injected diisocyanate into an aliphatic polyester prepolymer that has been melted at a melting point or higher and is in a liquid phase, and this is sufficiently stirred and mixed. It has been found that a high-quality high-molecular weight aliphatic polyester in which gelation or fish eyes are suppressed can be obtained by performing a coupling reaction after the components become uniform.
- the present invention (1) (i) An aliphatic polyester prepolymer having a number-average molecular weight of 5000 or more, a terminal group is a hydroxyl group, and at least one kind of acid component is succinic acid is added to a mixing tank having a press-in part of diisocyanate.
- a method for producing a high molecular weight aliphatic polyester (2) The method for producing a high molecular weight aliphatic polyester according to (1), wherein the step (ii) further comprises stirring the aliphatic polyester prepolymer and the diisocyanate, (3) The process (iii) is performed in a mixing tank, (1) or (2) the method for producing a high molecular weight aliphatic polyester, (4) Production of a high molecular weight aliphatic polyester according to (1) or (2), wherein a thickening reaction tank connected to the mixing tank is provided, and the step (iii) is performed in the thickening reaction tank.
- Method (5) The method for producing a high molecular weight aliphatic polyester according to any one of (1) to (4), wherein the reaction in the step (iii) is performed with stirring. (6) The method for producing a high molecular weight aliphatic polyester according to (5), wherein the reaction in the step (iii) is performed while stirring with a helical ribbon blade or a twisted lattice blade, (7) The method for producing a high molecular weight aliphatic polyester according to any one of (1) to (6), wherein at least one of the polyhydric alcohol components in the aliphatic polyester is ethylene glycol, and (8) aliphatic The method for producing a high molecular weight aliphatic polyester according to any one of (1) to (6), wherein at least one of the polyhydric alcohol components in the polyester is 1,4-butanediol.
- the production method of the present invention when an aliphatic polyester is made to have a high molecular weight, it is possible to produce a high-quality high-molecular weight aliphatic polyester with minimal gelation and fish eye generation.
- the production method of the present invention has high control accuracy of the melt flow rate (MFR) of the high molecular weight aliphatic polyester obtained.
- This is a method for stably and industrially producing a high molecular weight aliphatic polyester by press-fitting and adding a diisocyanate having an isocyanate group equivalent to 1/10 to 2 equivalents of a hydroxyl group.
- the succinic acid used in the present invention is succinic acid or a derivative thereof (diester, monoester, anhydride, etc.).
- succinic acid examples include succinic acid; succinic acid esters such as dimethyl succinate and diethyl succinate; and succinic anhydride.
- succinic acid, dimethyl succinate, and succinic anhydride are preferable.
- Succinic acid or a derivative thereof can be used alone or in combination of two or more.
- a part of the acid component may be substituted with dicarboxylic acids other than succinic acid.
- dicarboxylic acids having a linear or branched alkylene group such as adipic acid, suberic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, and dimer acid;
- esters of the above dicarboxylic acids such as dimethyl and dimethyl malonate; acid anhydrides such as maleic anhydride, itaconic anhydride and adipic anhydride; oxycarboxylic acids such as malic acid, tartaric acid and citric acid.
- adipic acid derivatives such as adipic acid or dimethyl adipate are preferred.
- the amount of the dicarboxylic acid component other than the succinic acid is about 0 to 35 mol%, preferably about 0 to 30 mol% of the whole dicarboxylic acid as the acid component.
- Glycol is used as the polyhydric alcohol for producing the aliphatic polyester used in the production method of the present invention.
- ethylene glycol 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5 -Pentanediol, 1,2-pentanediol, 2,4-pentanediol, 1,6-hexanediol, 1,2-hexanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.
- Aliphatic glycols having a linear or branched alkylene group having a linear or branched alkylene group; epoxides corresponding to 1,2-glycols; trivalent or higher alcohols such as trimethylolpropane; diepoxides.
- ethylene glycol and 1,4-butanediol are preferable, and 1,4-butanediol is more preferable.
- the amount of the glycol component used varies depending on the desired physical properties of the polyester, but is generally 1.02 to 1.5 mol, preferably 1.03 to 1.2 mol, relative to 1 mol of the dicarboxylic acid component. . When the amount is less than 1.02 mol, the content of the aliphatic polyester prepolymer having a hydroxyl group at the end group is decreased.
- the aliphatic polyester prepolymer formation is usually performed in the presence of a catalyst.
- a catalyst can be used individually or in combination of 2 or more types.
- a wide variety of catalysts used for transesterification can be used.
- a protonic acid such as sulfuric acid, p-toluenesulfonic acid, phosphoric acid or a derivative thereof, or Li, Mg, Ca, Ba, La, Ce, Ti, Zr, Hf, V, Mn, Fe, Metal compounds containing metals such as Co, Ir, Ni, Zn, Ge, Sn, for example, organic metal compounds such as organic acid salts, metal alkoxides, metal complexes (acetylacetonate, etc.); metal oxides, metal hydroxides And inorganic metal compounds such as carbonate, phosphate, sulfate, nitrate and chloride.
- titanium compounds particularly organic titanium compounds such as titanium alkoxides such as titanium tetraethoxide, titanium tetraisopropoxide, and titanium tetrabutoxide are preferable.
- the amount of these metal compound catalysts used is about 0.005 to 1 mol, preferably about 0.01 to 0.3 mol, per 100 mol of the total amount of the acid components.
- an organic or inorganic phosphorus compound can be used in combination with the metal compound catalyst (for example, an organic titanium compound) as a catalyst.
- the metal compound catalyst for example, an organic titanium compound
- a high molecular weight polymer can be obtained in a short polymerization time.
- organic or inorganic phosphorus compounds include the following.
- Phosphoric acid and organic esters thereof As commercially available products, phosphoric acid, alkyl or aryl acidic phosphates (alkyl group or aryl group is methyl, isopropyl, butyl, octyl, phenyl, naphthyl group, etc.), etc. There is.
- Phosphonic acid and organic esters thereof Commercially available products include methylphosphonic acid, ethylphosphonic acid, arylphosphonic acid such as phenylphosphonic acid and naphthylphosphonic acid, and dibutylbutylphosphonate.
- the aromatic ring of the arylphosphonic acid includes, for example, an alkyl group (C1-4 alkyl group such as methyl group), a halogen atom (fluorine, chlorine atom, etc.), an alkoxy group (C1-4 alkoxy group such as methoxy group, etc.) ), A substituent such as a nitro group may be bonded.
- C Phosphorous acid and organic esters thereof: for example, dibutyl hydrogen phosphite, triphenyl phosphite, diphenylisodecyl phosphite, trisisodecyl phosphite and the like.
- the amount of the organic or inorganic phosphorus compound used is 1 to 100 mol with respect to 100 mol of the metal compound catalyst (eg, organic titanium compound), The amount is preferably 5 to 33 mol.
- diisocyanate used for this invention
- examples thereof include 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, P, P'-diphenyl di- Isocyanate, 1,6-naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate.
- FIG. 1 is an example of a scheme of the production method of the present invention.
- an invention in which both steps (ii) and (iii) of the present invention are performed in the mixing tank 6 is shown.
- a metering hopper 1 that supplies an acid component containing succinic acid to the esterification tank 3, a glycol storage tank 2 that supplies a glycol component to the esterification tank 3, and an acid component and a glycol component are mixed and esterified.
- the mixing tank 6 having a press-fitting part for press-fitting diisocyanate is described as a pelletizer 7 for pelletizing the finally obtained high molecular weight aliphatic polyester.
- the glycol storage tank 2 and the esterification tank 3 are connected by a pipe 8a
- the esterification tank 3 and the transesterification reaction tank 4 are connected by a pipe 8b
- the transesterification tank 4 and the mixing tank 6 are connected by a pipe 8c.
- the diisocyanate storage tank 5 is connected to the press-fitting portion of the mixing tank 6 through the pipe 8d, and the mixing tank 6 and the pelletizer 7 are connected by the pipe 8e.
- FIG. 2 shows an embodiment in which step (ii) in the present invention is performed in the mixing tank 6 and step (iii) is performed in the thickening reaction tank 10.
- the mixing tank 6 is connected to the thickening reaction tank 10 by a pipe 8f, and this thickening reaction tank 10 is connected to the pelletizer 7 by a pipe 8g. .
- An acid component containing succinic acid is supplied from the weighing hopper 1 to the esterification tank 3.
- a mixture with succinic acid can be prepared in advance and supplied to the esterification tank 3 from the weighing hopper 1, or a succinic acid can be used by using another weighing hopper. It can supply to the esterification tank 3 separately.
- the catalyst is added to the esterification tank 3 from a tank (not shown) for supplying the catalyst.
- the catalyst used by each reaction may be added to the esterification tank 3 collectively, and the said catalyst required in the transesterification reaction tank 4 may be added.
- Glycol is supplied to the esterification tank 3 through the pipe 8a.
- the pipe 8a is provided with a pump 9a. Further, a meter for measuring the amount of glycol supplied is installed, and the supply of the pump can be automatically stopped. Examples of the pump used here include a centrifugal pump, a turbine pump, and a propeller pump.
- the pipe 8a is set at a temperature equal to or higher than the melting point of glycol in order to prevent crystallization of glycol. Although the temperature varies depending on the type of glycol, it is generally desirable to maintain it at 30 ° C. to 50 ° C.
- the esterification tank 3 it is preferable to carry out the reaction while stirring the raw materials in order to carry out the reaction efficiently.
- the esterification tank 3 is preferably provided with a stirring blade.
- a vertical stirring tank provided with a stirring blade having a vertical rotation axis (for example, a paddle blade, a turbine blade, etc.) is used.
- an ester reaction is performed in a nitrogen gas atmosphere.
- the temperature during the reaction is generally 140 ° C. to 250 ° C., preferably 145 ° C. to 245 ° C. At temperatures lower than 140 ° C., the reaction rate is slow and the practicality is poor. Further, when the temperature exceeds 250 ° C., the produced polymer may be thermally decomposed.
- the reaction pressure is usually atmospheric pressure, but in order to shorten the reaction time, the inside of the system can be reduced in the latter half of the reaction, for example, 5 mmHg to 100 mmHg (665 Pa to 13300 Pa).
- the reaction time is not particularly limited, but is generally 6 to 12 hours. In this way, the aliphatic polyester prepolymer obtained in the esterification tank 3 has a number average molecular weight of about 500 to 5,000.
- the aliphatic polyester prepolymer obtained in the esterification tank 3 is quickly transferred to the transesterification reaction tank 4 through the pipe 8b. If necessary, the catalyst is added to conduct a transesterification reaction. In this process, an increase in the molecular weight is promoted mainly by an ester exchange reaction (deglycol condensation reaction) between aliphatic polyester prepolymers, an aliphatic polyester prepolymer having a number average molecular weight of 5000 or more and a terminal group having a hydroxyl group. Produces.
- the temperature in the transesterification here is 200 ° C. to 250 ° C., preferably 210 ° C. to 240 ° C.
- the reaction time becomes long and the production efficiency tends to decrease.
- the polymerization temperature is too high, the polymer may be colored or a decomposition product may be easily generated.
- the final pressure at the end of the reaction is 0.1 mmHg to 5.0 mmHg (13 Pa to 666 Pa), and the reaction time is about 5 to 10 hours.
- esterification reaction and transesterification reaction in the present invention are bulk polymerization without using a solvent, a solvent may be used if necessary.
- a polymerization apparatus or a high-viscosity polymerization apparatus that is usually used when producing an aliphatic polyester prepolymer such as the esterification tank 3 described above can be used.
- a polymerization apparatus include a vertical stirring tank equipped with a stirring blade having a vertical rotation axis (for example, a double helical ribbon blade, a twisted lattice blade, etc.).
- the aliphatic polyester prepolymer having a number average molecular weight of 5000 or more and having a hydroxyl group at the end group is transferred to the mixing tank 6 through the pipe 8c.
- the aliphatic polyester prepolymer obtained through the transesterification has a number average molecular weight of 5000 to 30,000, preferably 10,000 to 20,000.
- the pipe 8c may be provided with a pump 9b for adjusting the transfer rate of the aliphatic polyester prepolymer.
- the pump used here is preferably a positive displacement pump, and is preferably a rotary pump that can be used even at high viscosity.
- examples of the rotary pump include a gear pump, a screw pump, and a vane pump. Among these, a gear pump that has high quantitativeness and is most suitable for transferring a highly viscous fluid is preferable.
- the flow rate may be controlled by driving the pump with a servo motor.
- the mixing tank 6 is provided with an inlet (press-in part) through which diisocyanate can be press-fitted.
- This press-fitting portion is provided on the bottom or side surface of the mixing tank 6.
- the position of the press-fitting part may be a position where the aliphatic polyester prepolymer can be filled thereabove, and is preferably lower than the bottom or the center of the side surface of the mixing tank 6.
- the aliphatic polyester prepolymer here has a high viscosity, in order to mix with the diisocyanate, it is necessary to raise the temperature and melt it into a liquid phase. If the aliphatic polyester prepolymer in the molten state and the diisocyanate are simply mixed, the diisocyanate is vaporized and unevenly distributed in the head space of the mixing tank, and cannot be uniformly mixed at a predetermined ratio. Moreover, since diisocyanate adheres to the wall surface of the mixing tank in the gas phase and diisocyanate does not contribute to the reaction, it is impossible to achieve a sufficiently high molecular weight.
- the mixing tank 6 is provided with an injection port (press-in portion) into which diisocyanate can be injected, and the isocyanate is passed through the gas phase portion into the aliphatic polyester prepolymer filled to a position exceeding the press-in portion. Without direct injection into the aliphatic polyester prepolymer, vaporization of the diisocyanate can be suppressed.
- the diisocyanate is connected from the diisocyanate storage tank 5 through the pipe 8d at the press-fitting portion of the mixing tank 6.
- the pipe 8d is provided with a metering pump 9c, and diisocyanate can be quantitatively and continuously supplied to the aliphatic polyester prepolymer.
- a metering pump 9c As the metering pump to be used, a non-pulsating metering pump is desirable, and in this case, a reciprocating pump suitable for a low-viscosity fluid transported in a small amount is preferable, and a diaphragm pump, a piston pump, and a plunger pump are exemplified. In order to stabilize the flow rate and improve the accuracy, it is also preferable to use a multiple plunger pump.
- the flow rate may be controlled by driving the quantitative pump with a servo motor.
- the non-pulsating pump is a pump in which a plurality of pumps are arranged in parallel and the sum of the flow rates of the plurality of pumps is constant, that is, the flow rate is non-pulsating, and is widely used at present.
- Diisocyanate is injected in an amount equivalent to 1/10 to 2 equivalents of the hydroxyl group of the aliphatic polyester prepolymer. At this time, a pressure of 0.5 to 1 MPa is applied to the diisocyanate in the pipe 8d at room temperature using the pump.
- mixing tank 6 diisocyanate and aliphatic polyester prepolymer are mixed.
- a polymerization apparatus or a high viscosity polymerization apparatus that can be used in the transesterification reaction tank 4 can be used as the mixing tank.
- examples of such a polymerization apparatus include a vertical stirring tank equipped with a stirring blade having a vertical rotation axis (for example, a double helical ribbon blade, a twisted lattice blade, etc.). It is preferable to sufficiently stir the diisocyanate and the aliphatic polyester prepolymer using the stirring means.
- the mixing tank 6 In the mixing tank 6, the aliphatic polyester prepolymer needs to be in a liquid phase. For this reason, the mixing tank 6 is set to a temperature suitable for mixing with the diisocyanate at a temperature equal to or higher than the melting point of the aliphatic polyester prepolymer.
- the temperature here varies depending on the molecular weight of the aliphatic polyester prepolymer, but is generally 130 ° C. to 210 ° C.
- a reaction for increasing the molecular weight is performed.
- a reaction for increasing the molecular weight is performed in the mixing tank 6 (FIG. 1).
- the reaction temperature here is 130 ° C. to 210 ° C., preferably 160 ° C. to 200 ° C. If the reaction temperature is too low, the prepolymer will crystallize and lose fluidity and cannot be stirred. If the temperature is too high, the reaction rate will be too high and sufficient stirring will not be possible.
- the reaction is carried out under normal pressure and under the above temperature conditions generally for 2 to 10 hours, preferably 3 to 8 hours.
- crystal nucleating agent pigment, dye, heat stabilizer, antioxidant, weathering agent, lubricant, antistatic agent, filler, reinforcing agent, flame retardant, plasticizer, etc.
- a polymer or the like may be added.
- the high molecular weight aliphatic polyester produced by the above method is transferred to the pelletizer 7 through the pipe 8e, and is cut into a desired shape (for example, a pellet shape). Further, since the high molecular weight aliphatic polyester has a high viscosity, the pipe 8e is provided with a pump 9d. A pump similar to the pump 9b can be used as the pump 9d.
- a thickening reaction tank 10 connected to the mixing tank 6 is provided, where a high molecular weight reaction is performed.
- Figure 2 the conditions until the aliphatic polyester prepolymer is prepared and transferred to the mixing tank 6 through the pipe 8c are the same as those in the above embodiment.
- the mixing tank 6 used in this embodiment is provided with an injection port (press-in portion) through which diisocyanate can be injected as described above.
- This press-fitting portion is provided on the bottom or side surface of the mixing tank 6.
- the polymerization apparatus may be used as the mixing tank 6, or a conventional vertical mixer having a stirring blade on the stirring shaft may be used. Two or more types of these agitators may be combined, including propeller type, paddle type, turbine type, ribbon type, special paddle type, etc.
- the mixing tank 6 In the mixing tank 6, the aliphatic polyester prepolymer needs to be in a liquid phase as in the above embodiment. For this reason, the mixing tank 6 is set to a temperature suitable for mixing with the diisocyanate at a temperature equal to or higher than the melting point of the aliphatic polyester prepolymer.
- the temperature here is set in the same range as the temperature of the above embodiment.
- the aliphatic polyester prepolymer When the diisocyanate is injected, the aliphatic polyester prepolymer needs to be present up to a position higher than the indented portion.
- the discharge port of the mixing tank 6 is closed and the aliphatic polyester prepolymer is allowed to flow to a position exceeding the press-fitting portion, and then diisocyanate is injected. Can do.
- the mixing tank 6 may be passed at a constant speed without closing the outlet.
- the inflow rate of the aliphatic polyester prepolymer into the mixing tank 6 is controlled by using the pump 9d so that the aliphatic polyester prepolymer exists up to the position exceeding the press-fitted portion.
- the diisocyanate is injected in an amount equivalent to 1/10 to 2 equivalents of the hydroxyl groups of the aliphatic polyester prepolymer.
- a pressure of 0.5 to 1 MPa is applied to the diisocyanate in the pipe 8d at room temperature using the pump.
- the fatty acid polyester prepolymer mixed with diisocyanate can be stirred in the mixing tank 6 with the stirring blade.
- stirring in the mixing tank 6 is not essential, and stirring may be performed in the subsequent thickening reaction tank 10.
- the aliphatic polyester prepolymer mixed with diisocyanate is transferred to the thickening reactor 10 through the pipe 8f.
- a polymerization apparatus that can be used in the transesterification reaction tank 4 or a high viscosity polymerization apparatus can be used.
- examples of such a polymerization apparatus include a vertical stirring tank equipped with a stirring blade having a vertical rotation axis (for example, a double helical ribbon blade, a twisted lattice blade, etc.).
- the thickening reaction tank 10 can be reacted without stirring, but in that case, the stirring blade of the stirring tank may be used without rotating, or a reaction tank without the stirring blade may be used. .
- the reaction temperature in the thickening reactor 10 is 130 ° C. to 210 ° C., preferably 160 ° C. to 200 ° C. If the reaction temperature is too low, the prepolymer will crystallize and lose fluidity and cannot be stirred. If the temperature is too high, the reaction rate will be too high and sufficient stirring will not be possible.
- the reaction is carried out under normal pressure and under the above temperature conditions generally for 2 to 10 hours, preferably 3 to 8 hours.
- crystal nucleating agent pigment, dye, heat stabilizer, antioxidant, weathering agent, lubricant, antistatic agent, filler, reinforcing agent, flame retardant, plasticizer, etc.
- a polymer or the like may be added.
- the high molecular weight aliphatic polyester produced by the above method is transferred to the pelletizer 7 through the pipe 8g, and is cut into a desired shape (for example, pellet shape). Further, since the high molecular weight aliphatic polyester has a high viscosity, the pipe 8g is provided with a pump 9e. A pump similar to the pump 9d can be used as the pump 9e.
- the high molecular weight aliphatic polyester obtained by the production method of the present invention can be formed into a film, a sheet, a fiber, a foam, or other molded articles by a conventional molding method such as injection molding, hollow molding, or extrusion molding. .
- a conventional molding method such as injection molding, hollow molding, or extrusion molding.
- the high molecular weight aliphatic polyester obtained by the production method of the present invention has biodegradability, it can be used for garbage bags, agricultural films, containers for cosmetics and detergents, fishing lines, fishing nets, ropes, surgical threads, foods. Suitable for applications such as packaging materials and medical containers.
- Gel ⁇ FE gelation, fish eye
- a film having a thickness of 30 ⁇ m is formed by inflation molding at a molding temperature of 180 ° C. and cut into 50 cm ⁇ 50 cm.
- Gel and FE (0.2 mm or more) in the center 30 cm ⁇ 30 cm square of the cut out film are counted visually.
- Ns (N ⁇ 25) / T T: Film thickness ( ⁇ m), N: Number of Gel and FE of 0.5 mm or more Evaluation 1: Ns ⁇ 1 2: 1 ⁇ Ns ⁇ 3 3: 3 ⁇ Ns ⁇ 10 4: 10 ⁇ Ns ⁇ 20 5: 20 ⁇ Ns
- Example 1 An aliphatic polyester was produced according to the production flow shown in FIG. (Esterification reaction) Under a nitrogen atmosphere, 3589 kg of 1,4-butanediol (39.8 ⁇ 10 3 mol: glycol excess 104.4%) was swirled from the glycol storage tank 2 into a vertical stirring tank with a paddle blade (esterification tank 3). It was supplied using a pump, 4500 kg (38.1 ⁇ 10 3 mol) of succinic acid was supplied from the weighing hopper 1, and 810 g of titanium tetraisopropoxide was supplied from a catalyst supply tank (not shown), and charged in a lump. The esterification reaction was performed by stirring at a temperature of 145 ° C. to 225 ° C.
- Comparative Example 1 In Comparative Example 1, the esterification reaction step and the transesterification reaction were completed in the same manner as in Example 1, and the obtained aliphatic polyester prepolymer was transferred to the mixing tank 6 according to the flow shown in FIG. (Speed: 3,000 kg / hr, total amount: 6500 kg). After completion of the transfer, a predetermined amount (70.3 kg) of hexamethylene diisocyanate was injected from the upper part (gas phase part) of the mixing tank, mixed and stirred with a helical ribbon blade, held at 180 ° C. for 8 hours, and then pelletizer 7 Was carried out to obtain a high molecular weight aliphatic polyester.
- the diisocyanate storage tank 5 was weighed and charged with diisocyanate, and this was pressure-fed under nitrogen pressure. (Because nitrogen pressure can be adjusted and transferred, diisocyanate can be quantitatively transferred without using a pump here.)
- Table 1 shows the actual values of MFR, Gel, and FE when this polymerization operation is repeated 10 times.
- the target value of MFR is 1 g / 10 min.
- the variance is small and the average value of 10 times is a value that is relatively close to the target value.
- the variance is large and deviates greatly from the target value.
- Gel, FE and foreign matters tend to become worse as the number of polymerizations is repeated, and this also shows that it is difficult to maintain the quality when continuously produced.
- 1 Metering hopper
- 2 Glycol storage tank
- 3 Esterification tank
- 4 Transesterification reaction tank
- 5 Diisocyanate storage tank
- 6 Mixing tank
- 7 Pelletizer
- 8a-g Piping
- 9a-e Pump 10: Reaction tank for thickening
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Abstract
Description
近年、環境保護等の観点から、一般に生分解性を有するとされる脂肪族ポリエステルが注目されている。この脂肪族ポリエステルを製造する方法としては、脂肪族ジカルボン酸と脂肪族ジオールとを直接エステル化させるか、又は脂肪族ジカルボン酸のアルキルエステルまたはその無水物と脂肪族ジオールとをエステル交換させてグリコールエステル又はその低重合体を得、次いでこれを高真空下で加熱攪拌して重縮合させる方法が知られている。
従って、本発明は、融点以上で溶融されて液相の状態である脂肪族ポリエステルプレポリマーにジイソシアネートを混合するに際して、ジイソシアネートが蒸発することを防止し、ジイソシアネートと脂肪族ポリエステルプレポリマーが均一に混合されて、高分子量化された脂肪族ポリエステルを効率的に製造する方法を提供することを目的とする。
(1)(i)ジイソシアネートの圧入部を備える混合槽に、数平均分子量が5000以上で、末端基がヒドロキシル基であり、酸成分の少なくとも一種類がコハク酸類である脂肪族ポリエステルプレポリマーを該圧入部を超える位置まで流入させる工程であって、ここで、流入した脂肪族ポリエステルプレポリマーは融点以上の温度で溶融されて液相の状態である、工程、
(ii)該脂肪族ポリエステルプレポリマーのヒドロキシル基の1/10~2当量相当のジイソシアネートを、該圧入部から圧入する工程、および
(iii)脂肪族ポリエステルプレポリマーとジイソシアネートを反応させる工程を含む、高分子量化された脂肪族ポリエステルの製造方法、
(2)前記工程(ii)が前記脂肪族ポリエステルプレポリマーおよびジイソシアネートを攪拌することをさらに含む、(1)の高分子量化された脂肪族ポリエステルの製造方法、
(3)前記工程(iii)は混合槽で行われる、(1)または(2)の高分子量化された脂肪族ポリエステルの製造方法、
(4)前記混合槽に接続する増粘用反応槽を設け、前記工程(iii)を該増粘用反応槽で行う、(1)または(2)の高分子量化された脂肪族ポリエステルの製造方法、
(5)前記(iii)の工程での反応を攪拌しながら行う、(1)~(4)のいずれかの高分子量化された脂肪族ポリエステルの製造方法、
(6)前記(iii)の工程での反応をヘリカルリボン翼又はねじり格子翼で攪拌しながら行う、(5)の高分子量化された脂肪族ポリエステルの製造方法、
(7)脂肪族ポリエステル中の多価アルコール成分の少なくともひとつがエチレングリコールである、(1)~(6)のいずれかの高分子量化された脂肪族ポリエステルの製造方法、および
(8)脂肪族ポリエステル中の多価アルコール成分の少なくともひとつが1,4-ブタンジオールである、(1)~(6)のいずれかの高分子量化された脂肪族ポリエステルの製造方法である。
本発明で使用するコハク酸類は、コハク酸もしくはその誘導体(ジエステル、モノエステル、無水物など)である。具体例としては、コハク酸;コハク酸ジメチル、コハク酸ジエチルなどのコハク酸エステル;無水コハク酸などが挙げられる。これらの中でも、コハク酸、コハク酸ジメチル、無水コハク酸が好ましい。コハク酸またはその誘導体は単独で又は2種以上を組み合わせて使用できる。
(a)リン酸およびその有機エステル類:入手可能な市販品としては、リン酸、アルキルまたはアリール酸性ホスフェート類(アルキル基またはアリール基がメチル、イソプロピル、ブチル、オクチル、フェニル、ナフチル基など)などがある。
(b)ホスホン酸およびその有機エステル類:入手可能な市販品としては、メチルホスホン酸、エチルホスホン酸、フェニルホスホン酸やナフチルホスホン酸等のアリールホスホン酸、ジブチルブチルホスホネートなどがある。前記アリールホスホン酸の芳香環には、例えば、アルキル基(メチル基などのC1-4アルキル基等)、ハロゲン原子(フッ素、塩素原子等)、アルコキシ基(メトキシ基などのC1-4アルコキシ基等)、ニトロ基等の置換基が結合していてもよい。
(c)亜リン酸およびその有機エステル類:例えば、ジブチル水素ホスファイト、トリフェニルホスファイト、ジフェニルイソデシルホスファイト、トリスイソデシルホスファイトなどが挙げられる。
それらの例としては、例えば2,4-トリレンジイソシアナート、2、4-トリレンジイソシアナートと2、6-トリレンジイソシアナートとの混合体、ジフェニルメタンジイソシアナート、P,P´-ジフェニルジイソシアナート、1,6-ナフチレンジイソシアナート、キシリレンジイソシアナート、水素化キシリレンジイソシアナート、イソホロンジイソシアナート、ヘキサメチレンジイソシアナートである。
本明細書では、コハク酸類を含む酸成分をエステル化槽3に供給する計量ホッパー1、グリコール成分をエステル化槽3に供給するグリコール貯槽タンク2、酸成分とグリコール成分とを混合しエステル化するエステル化槽3、エステル化槽3で形成された脂肪族ポリエステルプレポリマーをエステル交換反応で脱グリコール化するエステル交換反応槽4、ジイソシアネート貯槽タンク5、脂肪族ポリエステルプレポリマーとジイソシアネートを混合するための、ジイソシアネートを圧入する圧入部を備えた混合槽6、最終的に得られた高分子量化脂肪族ポリエステルをペレット化するペレタイザー7として記載する。
また、グリコール貯槽タンク2とエステル化槽3は配管8aで接続され、エステル化槽3とエステル交換反応槽4は配管8bで接続され、エステル交換反応槽4と混合槽6は配管8cで接続され、ジイソシアネート貯槽タンク5は配管8dを介して混合槽6の圧入部に接続され、混合槽6とペレタイザー7は配管8eで接続される。
この実施形態では、図1で示した実施形態に加え、混合槽6が配管8fで増粘用反応槽10に接続され、この増粘用反応槽10は、配管8gでペレタイザー7に接続される。
また、触媒は触媒を供給するためのタンク(図示せず)からエステル化槽3に添加される。なお、各反応で使用する触媒を一括してエステル化槽3に添加してもよく、エステル交換反応槽4で必要な前記触媒を添加してもよい。
また、配管8aはグリコールの結晶化を予防するために温度をグリコールの融点以上に設定してある。グリコールの種類によりその温度は異なるが、一般に30℃~50℃に維持しておくことが望ましい。
このようにして、エステル化槽3で得られる脂肪族ポリエステルプレポリマーは、数平均分子量が500~5,000程度である。
ここでのエステル交換反応における温度は、200℃~250℃、好ましくは210℃~240℃である。重合温度が低すぎると反応時間が長くなり、生産効率が低下しやすい。また、重合温度が高すぎるとポリマーが着色したり、分解生成物が生じやすくなったりする。脱グリコール縮合反応を進行させるためには、系内を減圧にする必要がある。反応終了時の最終到達圧力は0.1mmHg~5.0mmHg(13Pa~666Pa)であり、反応時間は、5~10時間程度である。
なお、本発明におけるエステル化反応及びエステル交換反応は溶媒を用いない塊状重合であるが、必要により溶媒を使用してもよい。
配管8cには脂肪族ポリエステルプレポリマーの移送速度を調整するためにポンプ9bが備えられてもよい。ここで使用するポンプは、容積ポンプが好ましく、高粘度でも使用可能な回転式ポンプが好ましい。具体的には、回転式ポンプとして、ギヤポンプ、ねじポンプ、ベーンポンプが挙げられる。これらの中でも定量性が高く、高粘度流体を移送するのに最も適しているギヤポンプが好ましい。
定量性をより高めるため、ポンプをサーボモーター駆動にして流量制御してもよい。
ここでの脂肪族ポリエステルプレポリマーは粘度が高いため、ジイソシアネートと混合するためには温度を上げて溶融されて液相の状態にする必要がある。溶融状態下の脂肪族ポリエステルプレポリマーとジイソシアネートを単純に混合すると、ジイソシアネートが気化して混合槽のヘッドスペースに偏在し、所定の割合で均一に混合することができない。また、気相部の混合槽壁面にジイソシアネートが付着し、ジイソシアネートが反応に寄与しないため、十分な高分子量化が不可能になる。
そのため、本発明では混合槽6にジイソシアネートの圧入できる注入口(圧入部)を設け、その圧入部を超える高さの位置まで充填された脂肪族ポリエステルプレポリマーに、イソシアネートを気相部を通過せずに脂肪族ポリエステルプレポリマーへ直接注入することでジイソシアネートの気化を抑えることができる。
なお、無脈動ポンプとは、複数のポンプを並列配置し、複数のポンプの流量の総和が一定となる、すなわち流量が無脈動となるポンプを言い、現在多岐にわたり使用されている。
また、高分子量化された脂肪族ポリエステルは高粘度であるため、配管8eにはポンプ9dが備えられる。ポンプ9dは、上記ポンプ9bと同様なポンプが使用可能である。
この場合では、脂肪族ポリエステルプレポリマーを調製し、配管8cを通じて混合槽6に移送させるまでは、前記の実施形態の条件と同じである。
また、別の実施形態として、混合槽6の排出口を閉じることなく、一定速度で通過させてもよい。ただし、この場合、ジイソシアネートを圧入時、ポンプ9dを用いて、混合槽6への脂肪族ポリエステルプレポリマーの流入速度を制御して、脂肪族ポリエステルプレポリマーが圧入部を超える位置まで存在させる。
ジイソシアネートが混合された脂肪酸ポリエステルプレポリマーを混合槽6において前記攪拌翼で攪拌することができる。ただし、混合槽6での攪拌は必須ではなく、後の増粘用反応槽10で攪拌してもよい。
また、高分子量化された脂肪族ポリエステルは高粘度であるため、配管8gにはポンプ9eが備えられる。ポンプ9eは、上記ポンプ9dと同様なポンプが使用可能である。
分子量測定は次のGPC測定により行った。
Shodex GPC SYSTEM-11(昭和電工社製)
溶離液:CF3COONa 5mM/HFIP(ヘキサフロロイソプロパノール)
サンプルカラム:HFIP-800PおよびHFIP-80M×2本
リファレンスカラム:HFIP-800R×2本
ポリマー溶液:0.1wt%HFIPsol.、200μl
カラム温度:40℃ 流量 1.0ml/分 圧力 30kg/cm2
検出器:Shodex RI
分子量スタンダード:PMMA(Shodex STANFARD M-75)
MFR(メルトフローレート)測定は、JIS-K-7210に準拠し、温度190℃、荷重2.16kgにて行った。
Ns=(N×25)/T
T:フィルム厚み(μm)、N:0.5mm以上のGel、FEの数
評価1: Ns<1
2: 1≦Ns<3
3: 3≦Ns<10
4:10≦Ns<20
5:20≦Ns
A:0.1mm以下10個以下、0.1~0.5mm5個以下、0.5mm以上1個以下
B:0.1mm以下20個以下、0.1~0.5mm10個以下、0.5mm以上2個以下
C:0.1mm以下30個以下、0.1~0.5mm20個以下、0.5mm以上3個以下
D:0.1mm以下31個以上、0.1~0.5mm50個以下、0.5mm以上3個以下
E:0.1mm以下31個以上、0.1~0.5mm51個以上、0.5mm以上4個以上
図1に示す製造フローに従って脂肪族ポリエステルを製造した。
(エステル化反応)
窒素雰囲気下、パドル翼を備えたジャケット付き縦型攪拌槽(エステル化槽3)に、1,4-ブタンジオール3589kg(39.8×103mol:グリコール過剰率104.4%)をグリコール貯槽タンク2から渦巻きポンプを使用して供給し、また計量ホッパー1からコハク酸4500kg(38.1×103mol)を、触媒供給用タンク(図示せず)からチタンテトライソプロポキシド810gを供給し、一括仕込みした。常圧下、145℃~225℃の温度にて攪拌し、エステル化反応を行った。エステル化反応にしたがって生成する水を留去し、その留出液の量が1390kgを超えたところで、60mmHg(8000Pa)まで減圧し、1時間保持して、エステル化反応工程を終了し、反応液をリボン翼を備えたジャケット付き縦型攪拌槽(エステル交換反応槽4)に移送した。移送された反応液を225℃~240℃の温度にて攪拌し、最終的に2mmHg(267Pa)以下にまで減圧し、10時間経過したところで、冷却を開始し、190℃に達した時点で減圧を解除し、窒素雰囲気下とした。その後、イルガノックス1010(BASF製:ヒンダードフェノール系酸化防止剤)を3.28kg添加し、さらに180℃まで冷却して亜燐酸を1.05kg添加して脱グリコール反応(エステル交換反応)を行った。GPC測定による平均分子量は10,600であった。
前記エステル交換反応工程で得られた脂肪族ポリエステルプレポリマーを混合槽6に移送した(移送速度:3,000kg/hr、総量:6500kg)。移送完了後、所定量(70.3kg)のヘキサメチレンジイソシアネートを増粘槽の下部(液相部)から圧入し、ヘリカルリボン翼により混合攪拌を実施した(混合工程)。さらに、180℃で8時間保持した後、ペレタイザー7によってペレタイズを実施し、高分子量脂肪族ポリエステルを得た。
この一連の重合操作を反応装置の分解、清掃を行うことなく、10回繰り返したときのMFRとGel、FEの実績値を表1に示す。
比較例1では、エステル化反応工程とエステル交換反応を実施例1と同様に終了し、図3に示されたフローにしたがって、得られた脂肪族ポリエステルプレポリマーを混合槽6に移送した(移送速度:3,000kg/hr、総量:6500kg)。移送完了後、所定量(70.3kg)のヘキサメチレンジイソシアネートを混合槽の上部(気相部)から注入し、ヘリカルリボン翼により混合攪拌を実施し、180℃で8時間保持した後、ペレタイザー7によってペレタイズを実施し、高分子量脂肪族ポリエステルを得た。
なお、ここではジイソシアネート貯層タンク5にジイソシアネートを計量した後仕込み、これを窒素加圧して圧送した。(窒素の圧力を調整して移送できるため、ここではポンプを使用しなくても定量的にジイソシアネートを移送できる。)
この重合操作を10回繰り返したときのMFRとGel、FEの実績値を表1に示す。
Claims (8)
- (i)ジイソシアネートの圧入部を備える混合槽に、数平均分子量が5000以上で、末端基がヒドロキシル基であり、酸成分の少なくとも一種類がコハク酸類である脂肪族ポリエステルプレポリマーを該圧入部を超える位置まで流入させる工程であって、ここで、流入した脂肪族ポリエステルプレポリマーは融点以上の温度で溶融されて液相の状態である、工程、
(ii)該脂肪族ポリエステルプレポリマーのヒドロキシル基の1/10~2当量相当のジイソシアネートを、該圧入部から圧入する工程、および
(iii)脂肪族ポリエステルプレポリマーとジイソシアネートを反応させる工程を含む、高分子量化された脂肪族ポリエステルの製造方法。 - 前記工程(ii)が前記脂肪族ポリエステルプレポリマーおよびジイソシアネートを攪拌することをさらに含む、請求項1に記載の高分子量化された脂肪族ポリエステルの製造方法。
- 前記工程(iii)は混合槽で行われる、請求項1または2に記載の高分子量化された脂肪族ポリエステルの製造方法。
- 前記混合槽に接続する増粘用反応槽を設け、前記工程(iii)を該増粘用反応槽で行う、請求項1または2に記載の高分子量化された脂肪族ポリエステルの製造方法。
- 前記(iii)の工程での反応を攪拌しながら行う、請求項1~4のいずれかに記載の高分子量化された脂肪族ポリエステルの製造方法。
- 前記(iii)の工程での反応をヘリカルリボン翼又はねじり格子翼で攪拌しながら行う、請求項5に記載の高分子量化された脂肪族ポリエステルの製造方法。
- 脂肪族ポリエステル中の多価アルコール成分の少なくともひとつがエチレングリコールである、請求項1~6のいずれかに記載の高分子量化された脂肪族ポリエステルの製造方法。
- 脂肪族ポリエステル中の多価アルコール成分の少なくともひとつが1,4-ブタンジオールである、請求項1~6のいずれかに記載の高分子量化された脂肪族ポリエステルの製造方法。
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US14/353,647 US9175127B2 (en) | 2011-10-24 | 2012-10-17 | Method for producing an aliphatic polyester having increased molecular weight |
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KR101529446B1 (ko) | 2015-06-16 |
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JPWO2013061834A1 (ja) | 2015-04-02 |
EP2772504B1 (en) | 2016-06-22 |
TWI568761B (zh) | 2017-02-01 |
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US9175127B2 (en) | 2015-11-03 |
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