WO2015137103A1 - Procédé de production de polymère - Google Patents

Procédé de production de polymère Download PDF

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Publication number
WO2015137103A1
WO2015137103A1 PCT/JP2015/055024 JP2015055024W WO2015137103A1 WO 2015137103 A1 WO2015137103 A1 WO 2015137103A1 JP 2015055024 W JP2015055024 W JP 2015055024W WO 2015137103 A1 WO2015137103 A1 WO 2015137103A1
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Prior art keywords
ring
polymerizable monomer
catalyst
polymer
opening polymerizable
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PCT/JP2015/055024
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English (en)
Japanese (ja)
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竜也 森田
田中　千秋
之弘 今永
晋 千葉
陽子 新井
Original Assignee
株式会社リコー
竜也 森田
田中　千秋
之弘 今永
晋 千葉
陽子 新井
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Publication of WO2015137103A1 publication Critical patent/WO2015137103A1/fr

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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
    • C08G63/02—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable

Definitions

  • the present invention relates to a polymer production method for producing a polymer by ring-opening polymerization of a ring-opening polymerizable monomer.
  • a method for producing a polymer by ring-opening polymerization of a ring-opening polymerizable monomer using a metal catalyst is known.
  • a method for producing polylactic acid by reacting a polymerization raw material mainly containing lactide as a ring-opening polymerization monomer in a molten state to produce polylactic acid is disclosed (for example, see Patent Document 1).
  • tin octylate is used as the metal catalyst, the reaction temperature is set to 195 ° C., and lactide is reacted and polymerized in a molten state.
  • a method for ring-opening polymerization of the ring-opening polymerizable monomer at a low temperature for example, a method of ring-opening polymerization of the ring-opening polymerizable monomer using a compressed gas solvent of hydrochlorofluorocarbon (HCFC-22) is disclosed.
  • HCFC-22 hydrochlorofluorocarbon
  • polylactide is obtained by using tin octoate as a catalyst, carrying out a polymerization at a reaction temperature of 100 ° C. and a pressure of 270 bar in a high pressure reactor for 2 hours.
  • This invention makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, according to the present invention, a monomer residual ratio is small, a sufficiently high molecular weight polymer can be obtained even at a low temperature for a short time, and the metal atom content can be reduced by reducing the amount of catalyst used. And it aims at providing the manufacturing method of the polymer which can obtain the polymer without coloring.
  • the polymer production method of the present invention includes a ring-opening polymerization step of bringing a ring-opening polymerizable monomer into contact with a raw material containing a ring-opening polymerizable monomer and a compressive fluid, and ring-opening polymerization of the ring-opening polymerizable monomer.
  • a ring-opening polymerization step an organic catalyst containing no metal atom and a catalyst containing a metal atom are used.
  • the present invention it is possible to solve the conventional problems and achieve the object, and to obtain a polymer having a sufficiently high molecular weight even with a low monomer residual rate and a low temperature, short time reaction. Further, it is possible to provide a method for producing a polymer that can reduce the content of metal atoms by reducing the amount of the catalyst used and obtain a polymer without coloring.
  • FIG. 1 is a general phase diagram showing the state of a substance with respect to temperature and pressure.
  • FIG. 2 is a phase diagram for defining the range of the compressible fluid in the present embodiment.
  • FIG. 3 is a system diagram showing an example of the polymerization process.
  • FIG. 4 is a system diagram showing an example of the polymerization process.
  • FIG. 5 is a system diagram showing an example of the polymerization process.
  • FIG. 6A is a schematic diagram illustrating an example of a complex production system.
  • FIG. 6B is a schematic diagram illustrating an example of a complex production system.
  • FIG. 7 is a schematic diagram showing an example of a complex production system.
  • the method for producing a polymer of the present invention includes at least a ring-opening polymerization step, and includes other steps as necessary.
  • the ring-opening polymerization step is a step of bringing the ring-opening polymerizable monomer into ring-opening polymerization by bringing a raw material containing the ring-opening polymerizable monomer into contact with a compressive fluid.
  • the ring-opening polymerizable monomer is subjected to ring-opening polymerization using an organic catalyst containing no metal atom and a catalyst containing a metal atom.
  • an organic catalyst that does not contain the metal atom and a catalyst that contains the metal atom are used.
  • a catalyst that contains the metal atom are used.
  • research is being conducted to reduce the amount of catalyst used. In the situation, it is extremely rare to use both catalysts.
  • the present inventors in the ring-opening polymerization step of bringing the ring-opening polymerizable monomer into contact with the raw material containing the ring-opening polymerizable monomer and melting the ring-opening polymerizable monomer to perform ring-opening polymerization,
  • the organic catalyst containing no metal atom and the catalyst containing the metal atom are used in combination, the amount of use of both catalysts can be extremely suppressed, and even when these are added together, several steps from the amount of normal catalyst used. It has been found that a polymer having a sufficiently high molecular weight can be produced in a short time with a small amount.
  • the raw material refers to a material from which a polymer is produced and is a material constituting a polymer component.
  • the raw material includes the ring-opening polymerizable monomer and, if necessary, polymerization initiation. Contains additives and additives.
  • -Ring-opening polymerizable monomer- There is no restriction
  • ring-opening polymerizable monomers include cyclic esters, cyclic carbonates, and cyclic amides.
  • Examples of the compound represented by the general formula (1) include an enantiomer of lactic acid, an enantiomer of 2-hydroxybutanoic acid, an enantiomer of 2-hydroxypentanoic acid, and an enantiomer of 2-hydroxyhexanoic acid. , 2-hydroxyheptanoic acid enantiomer, 2-hydroxyoctanoic acid enantiomer, 2-hydroxynonanoic acid enantiomer, 2-hydroxydecanoic acid enantiomer, 2-hydroxyundecanoic acid enantiomer And enantiomers of 2-hydroxydodecanoic acid.
  • enantiomers of lactic acid are particularly preferable from the viewpoint of reactivity or availability.
  • These cyclic dimers can be used alone or in admixture of several kinds.
  • examples of the cyclic ester include aliphatic lactones.
  • examples of the aliphatic lactone include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -hexanolactone, ⁇ -octanolactone, ⁇ eta-valerolactone, ⁇ -hexalanolactone, ⁇ - Examples include octanolactone, ⁇ -caprolactone, ⁇ -dodecanolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -valerolactone, glycolide, lactide, and p-dioxanone.
  • ⁇ -caprolactone is particularly preferable from the viewpoints of reactivity and availability.
  • the cyclic carbonate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene carbonate and propylene carbonate.
  • the cyclic amide is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ⁇ -caprolactam and lauryl lactam. These ring-opening polymerizable monomers may be used alone or in combination of two or more.
  • the raw material may contain a polymerization initiator (hereinafter also referred to as an initiator) as necessary.
  • the polymerization initiator is not particularly limited as long as it is an initiator that gives a branched structure to the polymer product, and can be appropriately selected according to the purpose.
  • any of monoalcohol, dialcohol, and polyhydric alcohol can be used. It may be either saturated alcohol or unsaturated alcohol.
  • Examples of the monoalcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol.
  • Examples of the dialcohol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, nonanediol, tetramethylene glycol, and polyethylene glycol. Etc.
  • polyhydric alcohol examples include glycerol, sorbitol, xylitol, ribitol, erythritol, triethanolamine, and the like.
  • unsaturated alcohol examples include methyl lactate and ethyl lactate.
  • a polymer having an alcohol residue at the terminal such as polycaprolactone diol or polytetramethylene glycol, may be used as the polymerization initiator.
  • a diblock or triblock copolymer is synthesized.
  • the amount of the polymerization initiator used is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05 mol% or more and 5 mol% or less with respect to the ring-opening polymerizable monomer. In order to prevent the polymerization from starting unevenly, it is desirable that the initiator is well mixed with the monomer in advance before the monomer contacts the polymerization catalyst.
  • the said raw material may contain an additive as needed.
  • the additive include surfactants, antioxidants, stabilizers, antifogging agents, ultraviolet absorbers, pigments, colorants, inorganic particles, various fillers, thermal stabilizers, flame retardants, crystal nucleating agents, and charging agents.
  • limiting in particular as the usage-amount of the said additive Although it can select suitably according to the objective and the kind of additive, 0 to 5 mass parts is preferable with respect to 100 mass parts of polymer compositions.
  • the surfactant those that melt into the compressive fluid and have affinity for both the compressive fluid and the ring-opening polymerizable monomer are preferably used. By using such a surfactant, the polymerization reaction can be progressed uniformly, and a product having a narrow molecular weight distribution can be obtained, and effects such as easy to obtain a particulate polymer can be expected.
  • a surfactant it may be added to the compressive fluid or to the ring-opening polymerizable monomer.
  • a surfactant having a parent carbon dioxide group and a parent monomer group in the molecule is used. Examples of such surfactants include fluorine-based surfactants and silicon-based surfactants.
  • the stabilizer for example, epoxidized soybean oil, carbodiimide and the like are used.
  • the antioxidant for example, 2,6-di-t-butyl-4-methylphenol, butylhydroxyanisole and the like are used.
  • the antifogging agent include glycerin fatty acid ester and monostearyl citrate.
  • the filler for example, an ultraviolet absorber, a heat stabilizer, a flame retardant, an internal mold release agent, clay having an effect as a crystal nucleating agent, talc, silica, or the like is used.
  • the pigment for example, titanium oxide, carbon black, ultramarine blue and the like are used.
  • FIG. 1 is a phase diagram showing the state of a substance with respect to temperature and pressure.
  • FIG. 2 is a phase diagram for defining the range of the compressible fluid in the present embodiment.
  • the compressible fluid means a fluid in a state existing in one of the regions (1), (2), and (3) shown in FIG. 2 in the phase diagram shown in FIG. .
  • a supercritical fluid is a fluid that exists as a non-condensable high-density fluid in a temperature and pressure region that exceeds the limit (critical point) at which gas and liquid can coexist, and does not condense even when compressed.
  • the substance when the substance is present in the region (2), it becomes a liquid, but in this embodiment, it is obtained by compressing a substance that is in a gaseous state at normal temperature (25 ° C.) and normal pressure (1 atm). Represents liquefied gas.
  • the substance is present in the region (3), it is in a gaseous state, but in the present embodiment, it represents a high pressure gas whose pressure is 1/2 (1/2 Pc) or more of the critical pressure (Pc).
  • the substance constituting the compressive fluid examples include carbon monoxide, carbon dioxide, dinitrogen monoxide, nitrogen, methane, ethane, propane, 2,3-dimethylbutane, and ethylene.
  • carbon dioxide is preferable in that it has a critical pressure of about 7.4 MPa and a critical temperature of about 31 ° C., can easily create a supercritical state, and is nonflammable and easy to handle.
  • These compressive fluids may be used alone or in combination of two or more.
  • Organic catalyst not containing metal atoms The organic catalyst not containing a metal atom (hereinafter also referred to as an organic catalyst) is not particularly limited and may be appropriately selected depending on the purpose.
  • the organic catalyst does not contain a metal atom and What contributes to the ring-opening polymerization reaction and forms an active intermediate with the ring-opening polymerizable monomer and then desorbs and regenerates by reaction with an alcohol is preferable.
  • the organic catalyst when polymerizing a ring-opening polymerizable monomer having an ester bond, is preferably a (nucleophilic) compound that functions as a basic nucleophile, and more preferably a compound containing a nitrogen atom.
  • a cyclic compound containing a nitrogen atom is particularly preferred.
  • Examples thereof include a compound, a heterocyclic aromatic organic compound containing a nitrogen atom, and N-heterocyclic carbene.
  • a cationic organic catalyst is used for ring-opening polymerization. In this case, hydrogen is extracted from the polymer main chain (back-biting), so that the molecular weight distribution becomes wide and it is difficult to obtain a high molecular weight product.
  • Examples of the cyclic monoamine include quinuclidine.
  • Examples of the cyclic diamine include 1,4-diazabicyclo- [2.2.2] octane (DABCO), 1,5-diazabicyclo (4,3,0) -5-nonene.
  • Examples of the cyclic diamine compound having an amidine skeleton include 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and diazabicyclononene.
  • Examples of the cyclic triamine compound having a guanidine skeleton include 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), diphenylguanidine (DPG), and the like.
  • heterocyclic aromatic organic compound containing a nitrogen atom examples include N, N-dimethyl-4-aminopyridine (DMAP), 4-pyrrolidinopyridine (PPY), pyrocholine, imidazole, pyrimidine, purine and the like. Can be mentioned.
  • N-heterocyclic carbene examples include 1,3-di-tert-butylimidazol-2-ylidene (ITBU).
  • DABCO, DBU, DPG, TBD, DMAP, PPY, and ITBU are preferable because they are less affected by steric hindrance and have high nucleophilicity or have a boiling point that can be removed under reduced pressure.
  • organic catalysts for example, DBU is liquid at room temperature and has a boiling point.
  • the organic catalyst can be almost quantitatively removed from the polymer product by subjecting the obtained polymer product to a reduced pressure treatment.
  • the kind of organic catalyst and the presence or absence of a removal process are determined according to the use purpose of a product, etc.
  • the type and amount of the organic catalyst vary depending on the combination of the compressive fluid and the ring-opening polymerizable monomer, and thus cannot be specified unconditionally.
  • the amount of the organic catalyst used is 45 ppm to 500 ppm is preferable, 45 ppm to 500 ppm is more preferable, and 50 ppm to 200 ppm is particularly preferable with respect to 1 part by mass of the ring-opening polymerizable monomer.
  • the catalyst containing the metal atom (hereinafter also referred to as a metal catalyst) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a tin compound, an aluminum compound, a titanium compound, a zirconium compound examples thereof include compounds and antimony compounds.
  • the tin compound include tin octylate, tin dibutyrate, and di (2-ethylhexanoic acid) tin.
  • the aluminum compound include aluminum acetylacetonate and aluminum acetate.
  • the titanium compound include tetraisopropyl titanate and tetrabutyl titanate.
  • the zirconium-based compound include zirconium isoprooxide.
  • the antimony compound include antimony trioxide.
  • the type and amount of the metal catalyst vary depending on the combination of the compressive fluid and the ring-opening polymerizable monomer, and thus cannot be specified unconditionally. However, in terms of stability and coloring, the amount of the metal catalyst used depends on the amount of the metal catalyst. 1 ppm to 200 ppm is preferable, 50 ppm to 200 ppm is more preferable, and 50 ppm to 100 ppm is particularly preferable with respect to 1 part by mass of the ring polymerizable monomer.
  • the combination of the organic catalyst and the metal catalyst is appropriately selected according to the purpose.
  • a plurality of the organic catalyst and the metal catalyst may be mixed.
  • the mass ratio of the amount used of the organic catalyst and the metal catalyst is appropriately selected depending on the nature of the catalyst to be mixed, but in terms of safety, 50:50 to 99: 1 70:30 to 99: 1 are more preferable.
  • the total amount used of the organic catalyst and the metal catalyst cannot be generally specified because it varies depending on the compressive fluid used in the production, the ring-opening polymerizable monomer, or the combination of catalysts to be mixed. In terms of coloring, 50 ppm to 500 ppm is preferable with respect to 1 part by mass of the ring-opening polymerizable monomer, and 50 ppm to 200 ppm is more preferable.
  • FIGS. 3 to 5 are system diagrams showing an example of the polymerization process.
  • the continuous polymerization reaction apparatus 100 shown in FIG. 3 includes a supply unit 100 a that supplies a raw material such as a ring-opening polymerizable monomer and a compressive fluid, and a continuous polymerization that polymerizes the ring-opening polymerizable monomer supplied by the supply unit 100 a. And a polymerization reaction apparatus main body 100b as an example of the apparatus.
  • the supply unit 100a has a tank (1, 3, 5, 7, 11), a measuring feeder (2, 4), and a measuring pump (6, 8, 12).
  • the polymerization reaction device main body 100b includes a melt mixing device 9, a liquid feed pump 10, a reaction vessel 13, a metering pump 14, and the other end of the polymerization reaction device main body 100b provided at one end of the polymerization reaction device main body 100b. And an extrusion die 15 provided on the surface.
  • melting means a state in which a raw material or a produced polymer comes into contact with a compressive fluid and is plasticized or liquefied while swelling.
  • the “melt mixing device” is a device that melts raw materials by bringing the compressive fluid into contact with the raw materials.
  • the tank 1 of the supply unit 100a stores a ring-opening polymerizable monomer.
  • the ring-opening polymerizable monomer to be stored may be a powder or a molten state.
  • the tank 3 stores a solid (powder or granular) one of the initiator and the additive.
  • the tank 5 stores a liquid one of the initiator and the additive.
  • the tank 7 stores a compressible fluid.
  • the tank 7 may store a gas (gas) or a solid that becomes a compressible fluid in a process of being supplied to the melt mixing device 9 or heated or pressurized in the melt mixing device 9. . In this case, the gas or solid stored in the tank 7 is heated or pressurized, and the state of (1), (2), or (3) in the phase diagram of FIG. Become.
  • the measuring feeder 2 measures the ring-opening polymerizable monomer stored in the tank 1 and continuously supplies it to the melt mixing device 9.
  • the weighing feeder 4 measures the solid stored in the tank 3 and continuously supplies it to the melt mixing device 9.
  • the metering pump 6 measures the liquid stored in the tank 5 and continuously supplies it to the melt mixing device 9.
  • the metering pump 8 continuously supplies the compressive fluid stored in the tank 7 to the melt mixing device 9 at a constant pressure and flow rate.
  • supplying continuously is a concept with respect to the method of supplying for every batch, and means supplying so that the polymer which carried out ring-opening polymerization may be obtained continuously. In other words, each material may be supplied intermittently or intermittently as long as the ring-opened polymer is continuously obtained.
  • the polymerization reaction apparatus 100 may not include the tank 5 and the metering pump 6. Similarly, when both the initiator and the additive are liquid, the polymerization reaction apparatus 100 may not include the tank 3 and the metering feeder 4.
  • each apparatus of the polymerization reaction apparatus main body 100b is connected as shown in FIG. 3 by a pressure-resistant piping 30 that transports raw materials, a compressive fluid, or a generated polymer.
  • each of the melt mixing device 9, the liquid feeding pump 10, and the reaction vessel 13 of the polymerization reaction device has a tubular member through which the above raw materials and the like pass.
  • the melt mixing device 9 of the polymerization reaction device main body 100b includes raw materials such as ring-opening polymerizable monomers, initiators and additives supplied from the tanks (1, 3, 5), and a compressive fluid supplied from the tank 7. Is a device having a pressure-resistant container for melting the raw materials.
  • the raw material such as the ring-opening polymerizable monomer and the compressive fluid can be continuously contacted at a constant concentration ratio, the raw material can be efficiently melted into the compressive fluid. it can.
  • the shape of the container of the melt mixing device 9 may be a tank type or a cylindrical type, but a cylindrical type in which raw materials are supplied from one end and the mixture is taken out from the other end is preferable.
  • an inlet 9 a for introducing the compressive fluid supplied from the tank 7 by the metering pump 8 and an inlet for introducing the ring-opening polymerizable monomer supplied from the tank 1 by the metering feeder 2 are introduced.
  • 9b, an inlet 9c for introducing the powder supplied from the tank 3 by the measuring feeder 4, and an inlet 9d for introducing the liquid supplied from the tank 5 by the measuring pump 6 are provided.
  • each inlet (9a, 9b, 9c, 9d) is comprised by the coupling which connects the container of the melt mixing apparatus 9, and each piping which conveys each raw material or compressive fluid.
  • This joint is not particularly limited, and known joints such as reducers, couplings, Y-type joints, T-type joints, and outlets are used.
  • the melt mixing apparatus 9 has a heater for heating each supplied raw material and compressive fluid.
  • the melt mixing device 9 may have a stirring device for stirring raw materials, compressive fluids, and the like.
  • the stirrer When the melt mixing device 9 has a stirrer, the stirrer includes a uniaxial screw, a biaxial screw meshing with each other, a biaxial mixer having a large number of meshing elements meshing with or overlapping each other, and a helical stirring element meshing with each other.
  • a kneader, a static mixer or the like having the above is preferably used.
  • a biaxial or multiaxial agitation device that meshes with each other is preferable because there is little adhesion of reactants to the agitation device or the container and there is a self-cleaning action.
  • a pressure resistant pipe is preferably used as the melt mixing device 9.
  • the melt mixing apparatus 9 does not have a stirring apparatus, in order to mix each material in the melt mixing apparatus 9 reliably, the ring-opening polymerizable monomer supplied to the melt mixing apparatus 9 is in a molten state. It is preferable.
  • the liquid feed pump 10 sends each raw material melted by the melt mixing device 9 to the reaction vessel 13.
  • the tank 11 stores a catalyst.
  • the metering pump 12 measures the catalyst stored in the tank 11 and supplies it to the reaction vessel 13.
  • FIG. 3 shows an example in which one tank 11 is used.
  • two types of catalyst ie, an organic catalyst and a metal catalyst are used. Therefore, after using an organic catalyst in the tank 11, the metal catalyst is inserted again.
  • the number of tanks 11 may be one.
  • two or more tanks 11 can be used. In that case, piping for supplying the catalyst to the reaction vessel 13 via the metering pump 12 and the inlet 13b is provided for each number of tanks 11.
  • the reaction container 13 is a pressure-resistant container for mixing the melted raw materials fed by the liquid feed pump 10 and the catalyst supplied by the metering pump 12 to cause the ring-opening polymerizable monomer to undergo ring-opening polymerization. It is.
  • the shape of the reaction vessel 13 may be a tank type or a cylindrical type, but a cylindrical type with little dead space is preferable.
  • the reaction vessel 13 has an introduction port 13a for introducing each material mixed by the melt mixing device 9 into the vessel, and an introduction port 13b for introducing the catalyst supplied from the tank 11 by the metering pump 12 into the vessel.
  • each inlet (13a, 13b) is comprised by the coupling which connects the reaction container 13 and each piping which conveys each raw material.
  • This joint is not particularly limited, and known joints such as reducers, couplings, Y-type joints, T-type joints, and outlets are used.
  • the reaction vessel 13 may be provided with a gas outlet for removing the evaporated material.
  • the reaction vessel 13 has a heater for heating the fed raw material.
  • the reaction vessel 13 may have a stirring device that stirs the raw materials, the compressive fluid, and the like.
  • the reaction vessel 13 has a stirrer, the polymer particles can be prevented from settling due to the difference in density between the raw material and the produced polymer, so that the polymerization reaction can proceed more uniformly and quantitatively.
  • a stirring device for the reaction vessel 13 a twin shaft having a screw which meshes with each other, a stirring element such as a 2-flight (oval) or a 3-flight (triangular shape), a disc or a multi-leaf type (clover-shaped) stirring blade. Or the thing of a multi-axis is preferable from a viewpoint of self-cleaning.
  • a static mixer that performs multi-stage division and combination (merging) of the flow with a guide device can also be applied to the stirring device.
  • static mixers those disclosed in Japanese Patent Publication Nos. 47-15526, 47-15527, 47-15528, 47-15533, etc. (multilayer mixer), and disclosed in JP-A-47-33166. And the like (Kenix type) and similar mixing devices without moving parts.
  • pressure-resistant piping is preferably used as the reaction vessel 13.
  • FIG. 3 shows an example in which the number of reaction vessels 13 is one, but two or more reaction vessels 13 can also be used.
  • the reaction (polymerization) conditions for each reaction vessel 13, that is, temperature, catalyst concentration, pressure, average residence time, stirring speed, etc. may be the same. It is preferable to select the optimum conditions.
  • the number of stages is preferably 1 or more and 4 or less, particularly preferably 1 or more and 3 or less.
  • the degree of polymerization of the polymer obtained and the amount of residual monomer are unstable and easily fluctuate, and are not suitable for industrial production. This is considered to be caused by instability due to mixing of a polymerization raw material having a melt viscosity of several poise to several tens of poise and a polymerized polymer having a melt viscosity of about 1,000 poise in the same container. .
  • the raw material and the produced polymer are melted (liquefied), it becomes possible to reduce the difference in viscosity in the reaction vessel 13 (also referred to as a polymerization system), so that the conventional polymerization Even if the number of stages is reduced as compared with the reactor, the polymer can be produced stably.
  • the metering pump 14 sends the polymer product P polymerized in the reaction vessel 13 out of the reaction vessel 13 from an extrusion die 15 as an example of a polymer discharge port.
  • the polymer product P can be sent out from the reaction vessel 13 without using the metering pump 14 by utilizing the pressure difference between the inside and outside of the reaction vessel 13.
  • the pressure adjusting valve 16 can be used as shown in FIG.
  • the polymerization reaction apparatus 400 includes a tank 407, a metering pump 408, an addition pot 411, a reaction vessel 413, and valves (421, 422, 423, 424, 425). .
  • Each of the above devices is connected by a pressure resistant pipe 430 as shown in FIG.
  • the pipe 430 is provided with joints (430a, 430b).
  • the tank 407 stores a compressible fluid.
  • the tank 407 may store a gas (gas) or solid that is heated and pressurized in the supply path supplied to the reaction vessel 413 or the reaction vessel 413 to become a compressible fluid.
  • the gas or solid stored in the tank 407 is heated or pressurized to be in the state (1), (2), or (3) in the phase diagram of FIG. .
  • the metering pump 408 supplies the compressive fluid stored in the tank 407 to the reaction vessel 413 at a constant pressure and flow rate.
  • the addition pot 411 stores a catalyst added to the raw material in the reaction vessel 413.
  • the valves (421, 422, 423, 424) open and close each, thereby supplying a compressive fluid stored in the tank 407 to the reaction vessel 413 via the addition pot 411, and the addition pot 411.
  • the route for supplying to the reaction vessel 413 without switching through is switched.
  • FIG. 5 shows an example in which the addition pot 411 is one. However, in this embodiment, since two types of catalyst, an organic catalyst and a metal catalyst, are used, if an organic catalyst is put in the addition pot 411, then a metal catalyst is added.
  • the number of addition pots 411 may be one. However, when both catalysts are used simultaneously or when both catalysts are stored in a tank, two or more addition pots 411 can be used. In that case, piping for supplying the catalyst to the reactor 413 is provided for each number of the addition pots 411 through the joints (430a, 430b) and the valves (423, 424).
  • the reaction vessel 413 contains a ring-opening polymerizable monomer and an initiator in advance before starting the polymerization. As a result, the reaction vessel 413 is brought into contact with the ring-opening polymerizable monomer and initiator stored in advance, the compressive fluid supplied from the tank 407, and the catalyst supplied from the addition pot 411. It is a pressure-resistant container for ring-opening polymerization of a functional monomer. Note that the reaction vessel 413 may be provided with a gas outlet for removing evaporated substances.
  • the reaction vessel 413 has a heater for heating the raw materials and the compressive fluid. Furthermore, the reaction vessel 413 includes a stirring device that stirs the raw materials and the compressive fluid.
  • the valve 425 is opened after the completion of the polymerization reaction to discharge the compressive fluid and the product (polymer) in the reaction vessel 413.
  • the reaction vessel 413 may have a valve 432 for taking out the compressive fluid out of the reaction vessel in the middle of the polymerization process.
  • Continuous polymerization method and batch polymerization method >> About the continuous polymerization method of the ring-opening polymerizable monomer in the present embodiment using the polymerization reactor 100, and the batch type polymerization method of the ring-opening polymerizable monomer in the present embodiment using the polymerization reactor 400, respectively. Will be described in detail.
  • each inlet (9a, 9b, 9c, 9d) are continuously introduced into the container of the melt mixing device 9 from each inlet (9a, 9b, 9c, 9d).
  • solid (powder or granular) raw materials may have lower measurement accuracy than liquid raw materials.
  • the solid raw material may be previously melted and stored in the tank 5 in a liquid state, and introduced into the container of the melt mixing device 9 by the metering pump 6.
  • the order in which each metering feeder (2, 4), metering pump 6 and metering pump 8 are operated is not particularly limited, but when the initial raw material is sent to the reaction vessel 13 without contacting the compressed fluid, it solidifies due to a decrease in temperature. Therefore, it is preferable to operate the metering pump 8 first.
  • Each feed rate of each raw material by the metering feeders (2, 4) and the metering pump 6 is adjusted to be a constant ratio based on a predetermined ratio of the ring-opening polymerizable monomer, the initiator, and the additive.
  • the total mass of raw materials supplied per unit time by the metering feeders (2, 4) and the metering pump 6 is the desired polymer properties and reaction time. It is adjusted based on etc.
  • the mass of the compressible fluid supplied per unit time by the metering pump 8 (supply rate of the compressible fluid (feed amount), (g / min)) is based on desired polymer physical properties, reaction time, and the like. Adjusted.
  • the ratio of the feed rate of the raw material and the feed rate of the compressible fluid represented by the following inequality is preferably 0.50 or more and less than 1.00, and is 0.65 or more and 0.99. Or less, more preferably 0.80 or more and 0.95 or less.
  • the feed ratio is less than 0.5, the amount of the compressive fluid used is not economical, and the density of the ring-opening polymerizable monomer is lowered, so that the polymerization rate may decrease. Further, when the feed ratio is less than 0.5, the mass of the compressive fluid becomes larger than the mass of the raw material, so that the melt phase in which the ring-opening polymerizable monomer is melted and the ring-opening polymerizable monomer is in the compressive fluid The fluid phase dissolved in the coexistence may coexist and the reaction may not easily proceed.
  • the reaction is performed in a state where the concentration of the raw material and the generated polymer (so-called solid content concentration) is high. proceed.
  • the solid content concentration in the polymerization system at this time is the solid content concentration of the polymerization system when polymerizing by dissolving a small amount of ring-opening polymerizable monomer in an overwhelming amount of compressive fluid in the conventional production method.
  • the polymerization reaction proceeds efficiently and stably even in a polymerization system having a high solid content concentration.
  • the feed ratio exceeds 0.99, the ability of the compressive fluid to melt the ring-opening polymerizable monomer may be insufficient, and the target reaction may not proceed uniformly.
  • each raw material and compressive fluid are continuously introduced into the container of the melt mixing device 9, they are in continuous contact with each other. As a result, the raw materials such as the ring-opening polymerizable monomer, the initiator, and the additive are melted in the melt mixing device 9.
  • the melt mixing device 9 has a stirring device, the raw materials and the compressive fluid may be stirred.
  • the temperature and pressure in the container of the reaction vessel 13 are controlled to a temperature and pressure at least above the triple point of the compressive fluid. This control is performed by adjusting the output of the heater of the melt mixing device 9 or the supply amount of the compressive fluid.
  • the temperature at which the ring-opening polymerizable monomer is melted may be a temperature equal to or lower than the melting point at normal pressure of the ring-opening polymerizable monomer. This is considered to be due to the high pressure in the melt mixing device 9 in the presence of the compressive fluid, and the melting point of the ring-opening polymerizable monomer being lower than the melting point at normal pressure. For this reason, even when the amount of the compressive fluid with respect to the ring-opening polymerizable monomer is small, the ring-opening polymerizable monomer is melted in the melt mixing device 9.
  • the timing of applying heat and stirring to each raw material and compressive fluid may be adjusted by the melt mixing device 9 so that each raw material is efficiently melted.
  • heat or stirring may be applied, or heat or stirring may be applied while bringing each raw material into contact with the compressive fluid.
  • the ring-opening polymerizable monomer and the compressive fluid may be brought into contact with each other after the ring-opening polymerizable monomer is previously melted by applying heat equal to or higher than the melting point.
  • the melt mixing device 9 is a biaxial mixing device
  • the above-described embodiments are arranged in an arrangement of screws, the arrangement of the inlets (9a, 9b, 9c, 9d), the temperature of the heater of the melt mixing device 9 This is realized by setting as appropriate.
  • the additive is supplied to the melt mixing device 9 separately from the ring-opening polymerizable monomer, but the additive may be supplied together with the ring-opening polymerizable monomer. Moreover, you may supply an additive after a polymerization reaction. In this case, after taking out the polymer product obtained from the reaction vessel 13, the additive can be added while melt-kneading.
  • each material melted by the melt mixing device 9 is fed by the feed pump 10 and supplied to the reaction vessel 13 from the inlet 13a.
  • the catalyst in the tank 11 is measured by the metering pump 12 and supplied to the reaction vessel 13 through the introduction port 13b.
  • the catalyst is added after the raw material is melted in the compressive fluid because the catalyst can act at room temperature.
  • the catalyst may be added before or after contacting the ring-opening polymerizable monomer with the compressive fluid.
  • the contact of the catalyst and the compressive fluid may be before or after the addition to the ring-opening polymerizable monomer.
  • two types of organic catalyst and metal catalyst are used. Even if the polymer intermediate is first produced using the organic catalyst and then the polymer product is produced using the metal catalyst, the metal catalyst is first produced.
  • the catalyst may be used to produce a polymer intermediate followed by an organic catalyst to produce a polymer product, or simultaneously an organic catalyst and a metal catalyst to produce a polymer product.
  • the order of addition of the catalyst is appropriately selected according to the purpose, but the raw material containing the ring-opening polymerizable monomer and the compressive fluid are brought into contact with each other in the presence of the organic catalyst not containing the metal atom.
  • a method in which the ring-opening polymerizable monomer is subjected to ring-opening polymerization and then further polymerized in the presence of the metal atom-containing catalyst is more preferable from the viewpoint of improving the conversion rate.
  • the materials fed by the feed pump 10 and the catalyst supplied by the metering pump 12 are sufficiently stirred by the stirring device of the reaction vessel 13 as necessary, and heated to a predetermined temperature by the heater. Thereby, the ring-opening polymerizable monomer undergoes ring-opening polymerization in the presence of the catalyst in the reaction vessel 13 (polymerization step).
  • the lower limit of the temperature (polymerization reaction temperature) for ring-opening polymerization of the ring-opening polymerizable monomer is not particularly limited, but is preferably 40 ° C, more preferably 50 ° C, and particularly preferably 60 ° C.
  • the polymerization reaction temperature is less than 40 ° C., depending on the ring-opening polymerizable monomer species, it takes a long time to melt by the compressive fluid, the melting is insufficient, or the activity of the catalyst is lowered. As a result, the reaction rate tends to decrease during polymerization, and the polymerization reaction may not proceed quantitatively.
  • the upper limit of the polymerization reaction temperature is not particularly limited, but is 100 ° C. or 30 ° C. higher than the melting point of the ring-opening polymerizable monomer, whichever is higher.
  • the upper limit of the polymerization reaction temperature is preferably 90 ° C. or the higher melting point of the ring-opening polymerizable monomer, and preferably 80 ° C. or 20 ° C. lower than the melting point of the ring-opening polymerizable monomer. Temperature is more preferred. When the polymerization reaction temperature exceeds 30 ° C.
  • the depolymerization reaction which is the reverse reaction of the ring-opening polymerization, tends to occur in equilibrium, and the polymerization reaction is difficult to proceed quantitatively.
  • the polymerization reaction temperature may be 30 ° C. higher than the melting point in order to increase the activity of the catalyst. Even in this case, the polymerization reaction temperature is preferably 100 ° C. or lower.
  • the polymerization reaction temperature is controlled by a heater provided in the reaction vessel 13 or heating from the outside of the reaction vessel 13. Moreover, when measuring polymerization reaction temperature, you may use the polymer product obtained by polymerization reaction.
  • ring-opening polymerizable monomers were polymerized using a large amount of supercritical carbon dioxide.
  • the ring-opening polymerizable monomer is subjected to ring-opening polymerization at an unprecedented high concentration.
  • the pressure in the reaction vessel 13 becomes high in the presence of the compressive fluid, and the glass transition temperature (Tg) of the produced polymer is lowered.
  • Tg glass transition temperature
  • the polymerization reaction time (average residence time in the reaction vessel 13) is set according to the target molecular weight, but is usually preferably within 1 hour, more preferably within 45 minutes, and within 30 minutes. Is particularly preferred. According to the production method of the present embodiment, the polymerization reaction time can be set to 20 minutes or less. This is a short time that is unprecedented in the polymerization of ring-opening polymerizable monomers in a compressible fluid.
  • the pressure at the time of polymerization that is, the pressure of the compressive fluid is such that the compressive fluid supplied from the tank 7 is a liquefied gas ((2) in the phase diagram of FIG. 2) or a high-pressure gas ((3) in the phase diagram of FIG. 2).
  • the pressure that becomes the supercritical fluid (1) in the phase diagram of FIG. 2) is preferable.
  • the pressure is preferably 3.7 MPa or more, more preferably 5 MPa or more, and a critical pressure of 7.4 MPa or more, considering efficiency of the reaction, polymer conversion rate, and the like. Particularly preferred.
  • the temperature is 25 degreeC or more for the same reason.
  • the water content in the reaction vessel 13 is preferably 4 mol% or less, more preferably 1 mol% or less, and particularly preferably 0.5 mol% or less with respect to the ring-opening polymerizable monomer.
  • the amount of water exceeds 4 mol%, the water itself contributes as an initiator, so that it may be difficult to control the molecular weight.
  • an operation for removing water contained in the ring-opening polymerizable monomer and other raw materials may be added as a pretreatment as necessary.
  • the polymer product P that has completed the ring-opening polymerization reaction in the reaction vessel 13 is sent out of the reaction vessel 13 by the metering pump 14.
  • the rate at which the metering pump 14 delivers the polymer product P is preferably constant in order to obtain a uniform polymerized product by operating at a constant pressure in the polymerization system filled with the compressive fluid. Therefore, the liquid feeding mechanism inside the reaction vessel 13 and the liquid feeding amount of the liquid feeding pump 10 are controlled so that the back pressure of the metering pump 14 is constant. Similarly, the feeding speed of the liquid feeding mechanism, the metering feeders (2, 4), and the metering pumps (6, 8) in the melt mixing device 9 are controlled so that the back pressure of the liquid pump 10 is constant. .
  • the control method may be an ON-OFF type, that is, an intermittent feed type, but a continuous or step method in which the rotational speed of a pump or the like is gradually increased or decreased is often more preferable. In any case, a uniform polymer product can be stably obtained by such control.
  • a batch polymerization method for ring-opening polymerizable monomers using the polymerization reaction apparatus 400 will be described.
  • a raw material containing a ring-opening polymerizable monomer and a compressive fluid are brought into contact with each other at a predetermined mixing ratio, and the ring-opening polymerizable monomer is subjected to ring-opening polymerization in the presence of a catalyst.
  • the metering pump 408 is operated and the valves (421, 422) are opened, whereby the compressive fluid stored in the tank 407 is supplied to the reaction vessel 413 without going through the addition pot 411.
  • the ring-opening polymerizable monomer and initiator stored in advance in the reaction vessel 413 come into contact with the compressive fluid supplied from the tank 407, and are stirred by the stirring device to be ring-opening polymerizable monomer. And other raw materials melt.
  • the ring-opening polymerizable monomer is preferably melted by bringing a raw material containing the ring-opening polymerizable monomer into contact with a compressive fluid.
  • the mass ratio between the raw material and the compressive fluid in the reaction vessel 413 (hereinafter also referred to as a mixing ratio) is not particularly limited, but is more preferably in the range of the following inequality.
  • the raw material in the above formula includes a ring-opening polymerizable monomer and an initiator.
  • limiting in particular as said mixing ratio Although it can select suitably according to the objective, 0.5 or more are preferable, 0.7 or more are more preferable, 0.85 or more are especially preferable.
  • the upper limit of the mixing ratio is preferably less than 1, and if the mixing ratio is less than 0.5, it is not economical because the amount of compressive fluid used increases, Since the density decreases, the polymerization rate may decrease.
  • the mixing ratio is less than 0.5, the mass of the compressive fluid becomes larger than the mass of the raw material, so that the melt phase in which the ring-opening polymerizable monomer is melted and the ring-opening polymerizable monomer is in the compressive fluid
  • the fluid phase dissolved in the coexistence may coexist and the reaction may not easily proceed.
  • the temperature and pressure at which the ring-opening polymerizable monomer is melted in the reaction vessel 413 is set to a temperature and pressure at least equal to or higher than the triple point of the compressive fluid in order to prevent the supplied compressive fluid from turning into a gas. Be controlled. This control is performed by adjusting the output of the heater of the reaction vessel 413 or the opening / closing degree of the valves (421, 422).
  • the temperature at which the ring-opening polymerizable monomer is melted may be a temperature equal to or lower than the melting point at normal pressure of the ring-opening polymerizable monomer.
  • each raw material and compressive fluid in the reaction vessel 413 may be adjusted so that each raw material is efficiently melted.
  • heat or stirring may be applied, or heat or stirring may be applied while bringing each raw material into contact with the compressive fluid.
  • the ring-opening polymerizable monomer may be brought into contact with the compressive fluid after previously melting the ring-opening polymerizable monomer by applying heat equal to or higher than the melting point.
  • the valves (423 and 424) are opened, and the catalyst in the addition pot 411 is supplied into the reaction vessel 413.
  • the catalyst supplied to the reaction vessel 413 is sufficiently stirred by a stirring device of the reaction vessel 413 as necessary, and heated to a predetermined temperature by a heater.
  • the ring-opening polymerizable monomer is subjected to ring-opening polymerization in the presence of a catalyst to produce a polymer.
  • two types of organic catalyst and metal catalyst are used. Even if the polymer intermediate is first produced using the organic catalyst and then the polymer product is produced using the metal catalyst, the metal catalyst is first produced.
  • the catalyst may be used to produce a polymer intermediate followed by an organic catalyst to produce a polymer product, or simultaneously an organic catalyst and a metal catalyst to produce a polymer product.
  • the order of addition of the catalyst is appropriately selected according to the purpose, but the raw material containing the ring-opening polymerizable monomer and the compressive fluid are brought into contact with each other in the presence of the organic catalyst not containing the metal atom.
  • a method of further polymerizing the ring-opening polymerizable monomer in the presence of the metal catalyst after ring-opening polymerization of the ring-opening polymerizable monomer is more preferable in terms of improving the conversion.
  • the lower limit of the temperature (polymerization reaction temperature) for ring-opening polymerization of the ring-opening polymerizable monomer is preferably 50 ° C. lower than the melting point of the ring-opening polymerizable monomer, and 40 ° C. lower than the melting point. Is more preferable.
  • the upper limit is preferably a temperature that is 50 ° C. higher than the melting point of the ring-opening polymerizable monomer, and more preferably a temperature that is 40 ° C. higher than the melting point. If the polymerization reaction temperature is less than 50 ° C. lower than the melting point of the ring-opening polymerizable monomer, the reaction rate tends to decrease, and the polymerization reaction may not proceed quantitatively.
  • the ring-opening polymerizable monomer may be subjected to ring-opening polymerization at a temperature other than the above range.
  • the temperature may be higher than the above range in order to increase the activity of the catalyst.
  • the polymerization reaction temperature is preferably 150 ° C. or lower, and more preferably 100 ° C. or lower.
  • ring-opening polymerizable monomers were polymerized using a large amount of supercritical carbon dioxide.
  • the ring-opening polymerizable monomer is subjected to ring-opening polymerization at a high mixing ratio that has not been conventionally obtained.
  • the inside of the reaction vessel 413 becomes a high pressure in the presence of the compressive fluid, and the glass transition temperature (Tg) of the produced polymer is lowered.
  • Tg glass transition temperature
  • the polymerization reaction time is set according to the target molecular weight.
  • the target weight average molecular weight is 3,000 to 500,000, the polymerization reaction time is completed within 2 hours.
  • the pressure at the time of polymerization is such that the compressive fluid supplied from the tank 407 is a liquefied gas ((2) in the phase diagram of FIG. 2) or a high-pressure gas ((3 in the phase diagram of FIG. 2). )) May be used, but a pressure which becomes a supercritical fluid ((1) in the phase diagram of FIG. 2) is preferable.
  • the pressure is preferably 3.7 MPa or more, more preferably 5 MPa or more, and a critical pressure of 7.4 PMa or more in consideration of efficiency of the reaction, polymer conversion rate, and the like. Particularly preferred.
  • the temperature is 25 degreeC or more for the same reason.
  • the amount of water in the reaction vessel 413 is preferably 4 mol% or less, more preferably 1 mol% or less, and particularly preferably 0.5 mol% or less with respect to the ring-opening polymerizable monomer.
  • the amount of water exceeds 4 mol%, the water itself contributes as an initiator, so that it may be difficult to control the molecular weight.
  • an operation for removing water contained in the ring-opening polymerizable monomer and other raw materials may be added as a pretreatment as necessary.
  • urethane bond or an ether bond can be introduced by adding an isocyanate compound or a glycidyl compound and carrying out a polyaddition reaction in a compressive fluid, like the ring-opening polymerizable monomer.
  • a method in which the compound is added and reacted after completion of the polymerization reaction of the ring-opening polymerizable monomer is more preferable.
  • the isocyanate compound used in the polyaddition reaction is not particularly limited, and examples thereof include polyfunctional isocyanate compounds such as isophorone diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and cyclohexane diisocyanate.
  • polyfunctional isocyanate compounds such as isophorone diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and cyclohexane diisocyanate.
  • the glycidyl compound is not particularly limited, and examples thereof include polyfunctional glycidyl compounds such as diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and diglycidyl terephthalate. .
  • the polymer P that has completed the ring-opening polymerization reaction in the reaction vessel 413 is discharged from the valve 425 and sent out of the reaction vessel 413.
  • the following treatment may be added.
  • the ring-opening polymerizable monomer is subjected to ring-opening polymerization
  • at least one of an organic catalyst not containing the metal atom and a catalyst containing the metal atom may be held in the reaction vessel in advance. That is, a reaction in which at least one of the organic catalyst containing no metal atom and the catalyst containing the metal atom is retained by bringing the raw material containing the ring-opening polymerizable monomer into contact with the compressive fluid.
  • the ring-opening polymerizable monomer may be subjected to ring-opening polymerization in a container.
  • each raw material after melting in a reaction vessel in which a solid metal catalyst is applied in advance each raw material after melting in a reaction vessel in which a solid metal catalyst is applied in advance.
  • An organic catalyst may be supplied to cause the ring-opening polymerizable monomer to undergo ring-opening polymerization.
  • the ring-opening polymerization step may further include a treatment for removing at least one of the organic catalyst containing no metal atom and the catalyst containing the metal atom. Good.
  • the catalyst remaining in the polymer product obtained by the polymer production method is removed if necessary.
  • the removal method is not particularly limited.For example, if it is a compound having a boiling point, it is distilled off under reduced pressure, or a method of removing the catalyst by using a substance that dissolves the catalyst as an entrainer, For example, a method of adsorbing and removing a catalyst by a column may be used.
  • the method for removing the catalyst may be a batch method in which the polymer product is removed after being taken out from the reaction vessel, or a method in which the polymer product is continuously treated without being taken out.
  • the reduced pressure condition is set based on the boiling point of the catalyst.
  • the temperature during decompression is 100 ° C. or higher and 120 ° C. or lower, and the catalyst can be removed at a temperature lower than the temperature at which the polymer product is depolymerized.
  • a step for removing the organic solvent after extraction of the catalyst may be required. For this reason, it is preferable to use a compressed fluid as a solvent also in extraction operation.
  • a known technique such as extraction of a fragrance can be diverted. More specifically, the raw material containing the ring-opening polymerizable monomer is brought into contact with the compressive fluid to open the ring-opening polymerizable monomer in the presence of the organic catalyst not containing the metal atom. After the polymerization, the organic catalyst not containing the metal atom remaining in the produced polymer intermediate is removed, and then further polymerized in the presence of the catalyst containing the metal atom to obtain a polymer product. From the viewpoint of improving the conversion rate.
  • the use of a compressive fluid enables a polymerization reaction at a low temperature as described above, so that the depolymerization reaction is greatly suppressed as compared with conventional melt polymerization. it can.
  • the polymer conversion rate can be 97 mol% or more, preferably 98 mol% or more.
  • the thermal characteristics as the polymer product may be insufficient, and an operation for separately removing the ring-opening polymerizable monomer may be required.
  • the polymer conversion rate means the ratio of the ring-opening polymerizable monomer that has contributed to the formation of the polymer with respect to the ring-opening polymerizable monomer as a raw material.
  • the amount of the ring-opening polymerizable monomer that contributed to the production of the polymer can be obtained by subtracting the amount of the unreacted ring-opening polymerizable monomer (residual ring-opening polymerizable monomer) from the amount of the produced polymer.
  • the number average molecular weight of the polymer obtained by this embodiment can be adjusted by the amount of the initiator.
  • the number average molecular weight is generally from 12,000 to 200,000. When the number average molecular weight is larger than 200,000, it may not be economical due to a deterioration in productivity accompanying an increase in viscosity. When the number average molecular weight is less than 12,000, the strength as a polymer may be insufficient, which may not be preferable.
  • the value obtained by dividing the weight average molecular weight of the polymer obtained by this embodiment by the number average molecular weight is preferably in the range of 1.0 to 2.5, and more preferably in the range of 1.0 to 2.0. When this value is larger than 2.0, there is a high possibility that the polymerization reaction is performed non-uniformly, and it is difficult to control the physical properties of the polymer.
  • the organic product obtained by this embodiment is produced by a production method that does not use an organic solvent, the organic product is substantially free of an organic solvent, and the content of metal atoms can be reduced by using a very small amount of a metal catalyst. Since the amount of residual monomer is as low as 1000 ppm or less, it is excellent in safety and stability. Moreover, as a result of carrying out the polymerization reaction by reducing the amount of the catalyst used at a low temperature for a short time, a polymer product having no coloration is obtained, which is excellent in practicality. Therefore, the polymer product of the present embodiment is widely applied for uses such as daily necessities, pharmaceuticals, cosmetics, and electrophotographic toners.
  • the organic solvent is an organic solvent used for ring-opening polymerization.
  • substantially free of organic solvent means that the content of the organic solvent in the polymer product measured by the following measurement method is below the detection limit.
  • the polymer product obtained by the method for producing a polymer of the present invention is excellent in safety and stability because it has a small metal content and a small amount of residual monomer. Therefore, the polymer product obtained by the production method of the present embodiment is widely applied to various uses such as an electrophotographic developer, printing ink, architectural paint, cosmetics, and medical materials. At that time, various additives may be used for the purpose of improving moldability, secondary processability, decomposability, tensile strength, heat resistance, storage stability, crystallinity, weather resistance and the like.
  • the organic solvent means a liquid organic compound used for dissolving the ring-opening polymerizable monomer.
  • a composite is synthesized by appropriately setting the timing of adding several types of ring-opening polymerizable monomers using the polymer product produced by the production method of the first embodiment.
  • the composite is obtained by polymerizing a copolymer or monomer having two or more polymer segments obtained by polymerizing monomers in a plurality of series. It means a mixture of two or more polymers.
  • two methods for synthesizing a stereo complex will be described.
  • FIGS. 6A and 6B are schematic views showing a complex production system used in the first method.
  • a polymer is produced by the production method of the first embodiment in series 1 in the complex production system 200 of FIG. 6A, and the obtained polymer product P and the newly introduced second product are used.
  • a composite product PP (final polymer product) is produced by contacting the ring-opening polymerizable monomer in series 2 and mixing continuously in the presence of a compressive fluid.
  • the complex product PP which has a 3 or more types of segment can also be obtained by repeating the series similar to the series 2 in the complex manufacturing system 200 of FIG. 6A in series.
  • the complex production system 200 includes a polymerization reaction device 100, tanks (21, 27), a metering feeder 22, a metering pump 28, a melt mixing device 29, and a reaction similar to those used in the first embodiment.
  • a container 33 and a pressure adjusting valve 34 are provided.
  • the polymer introduction port 33 a of the reaction vessel 33 is connected to the discharge port of the polymerization reaction apparatus 100 via the pressure resistant pipe 31.
  • the outlet of the polymerization reaction apparatus 100 means the outlet of the reaction vessel 13, the metering pump 14 (FIG. 3), or the pressure regulating valve 16 (FIG. 4).
  • the polymer product P generated in each polymerization reaction apparatus 100 can be supplied to the reaction vessel 33 in a molten state without returning to normal pressure.
  • Tank 21 stores the second ring-opening polymerizable monomer.
  • the second ring-opening polymerizable monomer is an optical isomer of the ring-opening polymerizable monomer stored in the tank 1.
  • the tank 27 stores a compressible fluid.
  • the compressive fluid stored in the tank 27 is not particularly limited, but is preferably the same type as the compressive fluid stored in the tank 7 in order to advance the polymerization reaction uniformly.
  • the tank 27 may store a gas (gas) or a solid that is a compressible fluid in the course of being supplied to the melt mixing device 29, or heated or pressurized in the melt mixing device 29. . In this case, the gas or solid stored in the tank 27 is heated or pressurized to be in the state of (1), (2), or (3) in the phase diagram of FIG. Become.
  • the metering feeder 22 measures the second ring-opening polymerizable monomer stored in the tank 21 and continuously supplies it to the melt mixing device 29.
  • the metering pump 28 continuously supplies the compressive fluid stored in the tank 27 to the melt mixing device 29 at a constant pressure and flow rate.
  • the melt mixing device 29 is a pressure-resistant container for continuously bringing the second ring-opening polymerizable monomer supplied from the tank 21 and the compressive fluid supplied from the tank 27 into contact with each other to melt the raw materials. It is a device that has.
  • the introduction port 29 a for introducing the compressive fluid supplied from the tank 27 by the metering pump 28 and the second ring-opening polymerizable monomer supplied from the tank 21 by the metering feeder 22 are introduced. And an introduction port 29b.
  • the melt mixing device 29 the same one as the melt mixing device 9 is used.
  • the reaction vessel 33 is obtained by polymerization in the polymerization reactor 100, and the polymer product P as an intermediate melted in the compressive fluid, and a second opening that is melted in the compressive fluid by the melt mixing device 29. It is a pressure-resistant container for polymerizing a ring polymerizable monomer.
  • the inlet 33a for introducing the molten polymer product P as an intermediate into the vessel and the molten second ring-opening polymerizable monomer are introduced into the vessel.
  • An introduction port 33b is provided.
  • the same reaction vessel 33 as the reaction vessel 13 is used.
  • the pressure adjusting valve 34 sends out the complex product PP polymerized in the reaction vessel 33 to the outside of the reaction vessel 33 by utilizing the pressure difference between the inside and outside of the reaction vessel 33.
  • a ring-opening polymerizable monomer for example, L-lactide
  • an optical isomer as an example of the second ring-opening polymerizable monomer.
  • the ring-opening polymerizable monomer for example, D-lactide
  • This method is very useful because the reaction can proceed at a temperature below the melting point of the ring-opening polymerizable monomer with a small amount of residual monomer, so that racemization hardly occurs and the reaction is obtained in a one-step reaction.
  • FIG. 7 is a schematic diagram showing a complex production system used in the second method.
  • a composite product PP is produced by continuously mixing a plurality of polymer products produced by the production method of the first embodiment in the presence of a compressive fluid.
  • the plurality of polymer products are obtained by polymerizing ring-opening polymerizable monomers of optical isomers to each other.
  • the complex manufacturing system 300 includes a plurality of polymerization reaction devices 100, a mixing device 41, and a pressure adjustment valve 42.
  • the polymer inlet 41 a of the mixing device 41 is connected to the outlet of each polymerization reaction device 100 via the pressure resistant pipe 31.
  • the outlet of the polymerization reaction apparatus 100 means the outlet of the reaction vessel 13, the metering pump 14 (FIG. 3), or the pressure regulating valve 16 (FIG. 4).
  • the polymer product P generated in each polymerization reaction device 100 can be supplied to the mixing device 41 in a molten state without returning to normal pressure.
  • each polymer product P has a reduced viscosity in the presence of the compressed fluid, so that the mixing device 41 can mix two or more types of polymer products P at a lower temperature.
  • FIG. 7 shows an example in which the piping 31 has one joint 31a so that two polymerization reaction apparatuses 100 are provided in parallel. However, by providing a plurality of joints, the polymerization reaction apparatus 100 can be connected in three in parallel. You may have more than one.
  • the mixing device 41 is not limited as long as it can mix a plurality of polymer products supplied from the respective polymerization reaction devices 100, and includes a stirring device.
  • a stirring device As the agitation device, a uniaxial screw, a biaxial screw meshing with each other, a biaxial mixer having a large number of meshing elements meshing with each other or overlapping, a kneader having helical stirring elements meshing with each other, a static mixer, etc. are preferably used.
  • the temperature (mixing temperature) at which each polymer product is mixed by the mixing device 41 can be set similarly to the polymerization reaction temperature in the reaction vessel 13.
  • the mixing device 41 may have a mechanism for supplying a compressive fluid separately to the polymer product to be mixed.
  • the pressure adjusting valve 42 is a device for adjusting the flow rate of the composite product PP obtained by mixing the polymer product with the mixing device 41.
  • L-type and D-type monomers are polymerized in advance in the compressive fluid in the polymerization reaction apparatus 100 in advance. Furthermore, the polymer product obtained by polymerization is blended in a compressive fluid to obtain a stereoblock copolymer.
  • polymers such as polylactic acid often decompose when heated and dissolved again, even when the residual monomer is extremely small.
  • the second method is useful because, by blending low-viscosity polylactic acid melted with a compressive fluid at a melting point or lower, racemization and thermal degradation can be suppressed as in the first method.
  • the first method and the second method a case where a stereocomplex is produced by polymerizing ring-opening polymerizable monomers that are optical isomers to each other has been described.
  • the ring-opening polymerizable monomers used in this embodiment do not need to be optical isomers.
  • Ppm in each table indicates a mass fraction.
  • the molecular weight, polymer conversion rate, YI value, and residual catalyst amount of the polymer products obtained in Examples and Comparative Examples were determined as follows.
  • ⁇ Conversion rate of polymers other than lactide Polymers other than lactide were measured in the same manner as described above, and the ratio of the quadruple peak area on the low magnetic field side from the monomer to the quadruple peak area on the high magnetic field side from the polymer was calculated. Then, 100 times this was taken as the amount of unreacted monomer (mol%).
  • the polymer conversion rate is a value obtained by subtracting the amount of unreacted monomer calculated from 100.
  • ⁇ Remaining catalyst amount The amount of organic catalyst remaining in the polymer product (polylactic acid) is determined by uniformly dissolving the polymer product such as polylactic acid in dichloromethane and adding an acetone / cyclohexane mixed solution (mass ratio 1/1). The supernatant obtained by re-precipitation was subjected to a gas chromatograph (GC) with a hydrogen flame detector (FID), the remaining catalyst was separated, and the amount of the remaining catalyst in the polymer product was measured by quantifying by an internal standard method. . Gas chromatography (GC) measurement was performed under the following conditions.
  • the metal catalyst was measured under the following conditions by ICP emission spectroscopy (high frequency inductively coupled plasma emission spectroscopy), and the amount of residual catalyst was determined based on the measurement results.
  • ICP emission spectroscopic analyzer ICP-OES / ICP-AES
  • a sample (polymer product) made by SPS5100, SII Nanotechnology was decomposed by heating with sulfuric acid and nitric acid (heating temperature is 230 ° C.), and then the volume was measured with ultrapure water to prepare a test solution. Quantitative analysis of Sn in the test solution was performed by ICP-AES method.
  • Example 1 Ring-opening polymerization of L-lactide (purity 99.5 wt%) was performed using the polymerization reactor 100 of FIG. The structure of the polymerization reaction apparatus 100 is shown.
  • Tank 1 weighing feeder 2: Plunger pump NP-S462 made by Nippon Seimitsu Tank 1 was filled with molten lactide as a ring-opening polymerizable monomer.
  • Tank 3 weighing feeder 4: Intelligent spectrometer pump (PU-2080) manufactured by JASCO Tank 3 was filled with lauryl alcohol as an initiator.
  • Tank 5 metering pump 6: Not used in this example.
  • Tank 7 Carbon dioxide cylinder tank 11, metering pump 12: Intelligent spectrometer pump (PU-2080) manufactured by JASCO
  • the tank 11 was filled with DBU (organic catalyst).
  • Melt mixing device 9 biaxial stirring device with screws that mesh with each other Cylinder inner diameter 30 mm Cylinder set temperature 100 °C Two shafts rotating in the same direction Rotating speed 30rpm
  • Reaction vessel 13 Biaxial kneader Cylinder inner diameter 40mm Cylinder set temperature Raw material supply part 100 °C Tip part 80 °C Two shafts rotating in the same direction Rotation speed 60rpm
  • the melt mixing device 9 and the reaction vessel 13 were operated under the above set conditions.
  • the weighing feeder 2 quantitatively supplied the molten lactide in the tank 1 into the container of the melt mixing device 9.
  • the measuring feeder 4 has 0.07 mol of lauryl alcohol in the tank 3 such that the amount of initiator relative to the ring-opening polymerizable monomer is 0.07 mol%, that is, 1 mol of lactide is supplied.
  • a fixed amount was supplied into the container of the melt mixing apparatus 9.
  • the metering pump 8 is placed in the pipe of the melt mixing device 9 so that the carbon dioxide (carbon dioxide) as a compressive fluid from the tank 7 becomes 10 parts by mass with respect to 90 parts by mass of the raw material supplied per unit time. Continuously fed.
  • the raw materials are lactide which is a ring-opening polymerizable monomer and lauryl alcohol added as an initiator.
  • the feed amount of the raw material was 10 g / min. It supplied so that the pressure in the container of the melt mixing apparatus 9 might be set to 15 MPa. As a result, the melt mixing device 9 continuously brings the raw materials of lactide and lauryl alcohol supplied from the tanks (1, 3, 7) and the compressive fluid into contact with each other and mixes them with a screw. Was melted.
  • Each material melted by the melt mixing device 9 was sent to the reaction vessel 13 by the liquid feed pump 10.
  • the metering pump 12 supplied the organic catalyst (DBU) in the tank 11 to the raw material supply hole of the biaxial kneader as the reaction vessel 13 so as to be 200 ppm with respect to 1 part by mass of lactide.
  • DBU organic catalyst
  • each material fed by the liquid feed pump 10 and DBU supplied by the metering pump 12 were mixed, and lactide was subjected to ring-opening polymerization.
  • the tank 11 is filled with a metal catalyst (bis (2-ethylhexanoic acid) tin (II)), and the metering pump 12 is charged with metal catalyst (bis ( 2-Ethylhexanoic acid) tin (II)) was supplied to the raw material supply hole of the twin-screw kneader as the reaction vessel 13 so as to be 200 ppm.
  • a metal catalyst bis (2-ethylhexanoic acid) tin (II)
  • metal catalyst bis ( 2-Ethylhexanoic acid) tin (II)
  • Example 2 Ring-opening polymerization of L-lactide (purity 99.5 wt%) was performed using the polymerization reactor 100 of FIG.
  • the structure of the polymerization reaction apparatus 100 is shown.
  • Tank 1, weighing feeder 2: Plunger pump NP-S462 made by Nippon Seimitsu Tank 1 was filled with molten lactide as a ring-opening polymerizable monomer.
  • Tank 5 metering pump 6: Not used in this example.
  • Tank 7 Carbon dioxide cylinder tank 11
  • metering pump 12 Intelligent spectrometer pump (PU-2080) manufactured by JASCO Tank 11 was filled with metal catalyst bis (2-ethylhexanoate) tin.
  • Melt mixing device 9 biaxial stirring device with screws that mesh with each other Cylinder inner diameter 30 mm Cylinder set temperature 150 °C Two shafts rotating in the same direction Rotating speed 30rpm
  • Reaction vessel 13 Biaxial kneader Cylinder inner diameter 40mm Cylinder set temperature Raw material supply part 150 ° C Tip part 80 ° C Two shafts rotating in the same direction Rotation speed 60rpm
  • the melt mixing device 9 and the reaction vessel 13 were operated under the above set conditions.
  • the weighing feeder 2 quantitatively supplied the molten lactide in the tank 1 into the container of the melt mixing device 9.
  • the measuring feeder 4 quantitatively supplied the lauryl alcohol in the tank 3 into the container of the melt mixing device 9 so as to be 0.07 mol per mol of lactide supplied.
  • the metering pump 8 is placed in the pipe of the melt mixing device 9 so that the carbon dioxide (carbon dioxide) as a compressive fluid from the tank 7 becomes 10 parts by mass with respect to 90 parts by mass of the raw material supplied per unit time. Continuously fed.
  • the raw materials are lactide which is a ring-opening polymerizable monomer and lauryl alcohol added as an initiator.
  • the feed amount of the raw material was 10 g / min. It supplied so that the pressure in the container of the melt mixing apparatus 9 might be set to 15 MPa. As a result, the melt mixing device 9 continuously brings the raw materials of lactide and lauryl alcohol supplied from the tanks (1, 3, 7) and the compressive fluid into contact with each other and mixes them with a screw. Was melted.
  • Each material melted by the melt mixing device 9 was sent to the reaction vessel 13 by the liquid feed pump 10.
  • the metering pump 12 supplied the metal catalyst (bis (2-ethylhexanoic acid) tin) in the tank 11 to the raw material supply hole of the twin-screw kneader as the reaction vessel 13 so as to be 200 ppm with respect to 1 part by mass of lactide. .
  • each material fed by the liquid feeding pump 10 and bis (2-ethylhexanoic acid) tin supplied by the metering pump 12 were mixed to perform ring-opening polymerization of lactide.
  • the tank 11 is filled with DBU (organic catalyst), and the feed pump of the biaxial kneader as the reaction vessel 13 so that the metering pump 12 becomes 200 ppm of DBU with respect to 1 part by mass of lactide. Supplied.
  • DBU organic catalyst
  • Example 3 Experiments were conducted in the same manner as in (Example 1) except that the catalyst type used in Example 1 was changed to the material shown in Table 1 instead of DBU.
  • physical property values Mn, Mw, polymer conversion rate, YI value, catalyst residual amount
  • Example 6 Example 6 to (Example 8)
  • Example 2 the experiment was performed in the same manner as in (Example 2) except that the catalyst type used was changed to the material shown in Table 1 instead of DBU.
  • physical property values Mn, Mw, polymer conversion rate, YI value, catalyst residual amount
  • Example 9 Experiments were conducted in the same manner as in (Example 1) except that the amount of lauryl alcohol added in Example 1 was changed as shown in Table 1. With respect to the obtained polymer product, physical property values (Mn, Mw, polymer conversion rate, YI value, catalyst residual amount) were determined by the above method. The results are shown in Table 1.
  • Example 10 Experiments were conducted in the same manner as in (Example 1) except that the types of monomers used in Example 1 were changed as shown in Tables 1 to 3.
  • Example 16 For the combinations of the two types of monomers (Example 16) to (Example 23), each of the monomers was synthesized one by one and charged into the reaction vessel 100 of FIG. went.
  • physical property values Mn, Mw, polymer conversion rate, YI value, catalyst residual amount
  • Example 24 The experiment was performed in the same manner as in (Example 1) except that the order of the catalyst to be added was changed so as to be mixed at the same time in Example 1. With respect to the obtained polymer product, physical property values (Mn, Mw, polymer conversion rate, YI value, catalyst residual amount) were determined by the above method. The results are shown in Table 3.
  • Example 25 In Example 1, the experiment was performed in the same manner as in (Example 1) except that the amount of the initiator to be added was 0.01 mol with respect to 1 mol of lactide. With respect to the obtained polymer product, physical property values (Mn, Mw, polymer conversion rate, YI value, catalyst residual amount) were determined by the above method. The results are shown in Table 3.
  • Example 26 In Example 1, tin oxide (manufacturer name: Aldrich cat, no24, 464-3. Tin (ii)) which was previously sieved on the wall of the tube of the reaction vessel 13 in FIG. Oxide, 99-%) was applied uniformly to 1 g, and the same experiment as in Example 1 was conducted except that the metal catalyst (bis (2-ethylhexanoic acid) tin (II)) was not used. Went. With respect to the obtained polymer product, physical property values (Mn, Mw, polymer conversion rate, YI value, catalyst residual amount) were determined by the above method. The results are shown in Table 3.
  • Example 27 Ring-opening polymerization of L-lactide was performed using the polymerization reaction apparatus 400 of FIG. The structure of the polymerization reaction apparatus 400 is shown.
  • Tank 407 Carbon dioxide cylinder addition pot 411: A 1/4 inch SUS316 pipe was sandwiched between valves 423 and 424 and used as an addition pot. DBU was previously filled to 200 ppm with respect to 1 part by mass of lactide.
  • Reaction vessel 413 100 mL pressure vessel made of SUS316 Preliminarily lactide in a liquid state as a ring-opening polymerizable monomer, Mixture with lauryl alcohol as initiator (molar ratio 100/3) 108 g was charged.
  • the carbon dioxide stored in the tank 407 was supplied to the reaction vessel 413 without going through the addition pot 411.
  • carbon dioxide was charged until the pressure in the reaction vessel 413 reached 15 MPa.
  • the valve (423, 424) was opened, and the DBU in the addition pot 411 was supplied into the reaction vessel 413.
  • a polymerization reaction of lactide was performed in the reaction vessel 413 for 1 hour.
  • a metal catalyst bis (2-ethylhexanoic acid) tin (II)
  • the metering pump 408 was operated and the valves (421, 422) were opened to supply the carbon dioxide stored in the tank 407 to the reaction vessel 413 without going through the addition pot 411.
  • carbon dioxide was charged until the pressure in the reaction vessel 413 reached 15 MPa.
  • the valve (423, 424) is opened, and the metal catalyst (bis (2-ethylhexanoic acid) tin (II)) in the addition pot 411 is placed in the reaction vessel 413. Supplied. Thereafter, a polymerization reaction of lactide was performed in the reaction vessel 413 for 1 hour.
  • the valve 425 was opened, the temperature and pressure in the reaction vessel 413 were gradually returned to room temperature and normal pressure, and after 3 hours, the polymer product (polylactic acid) in the reaction vessel 413 was taken out.
  • Example 28 Ring-opening polymerization of L-lactide was performed using the polymerization reaction apparatus 400 of FIG. The structure of the polymerization reaction apparatus 400 is shown.
  • Tank 407 Carbon dioxide cylinder addition pot 411: A 1/4 inch SUS316 pipe was sandwiched between valves 423 and 424 and used as an addition pot.
  • a metal catalyst bis (2-ethylhexanoic acid) tin (II)
  • Reaction vessel 413 100 ml pressure vessel made of SUS316 Preliminarily liquid lactide as a ring-opening polymerizable monomer, Mixture with lauryl alcohol as initiator (molar ratio 100/3) 108 g was charged.
  • the carbon dioxide stored in the tank 407 was supplied to the reaction vessel 413 without going through the addition pot 411 by operating the metering pump 408 and opening the valves (421, 422). After replacing the space in the reaction vessel 413 with carbon dioxide, carbon dioxide was charged until the pressure in the reaction vessel 413 reached 15 MPa. After raising the temperature in the reaction vessel 413 to 150 ° C., the valve (423, 424) is opened, and the metal catalyst (bis (2-ethylhexanoic acid) tin (II)) in the addition pot 411 is placed in the reaction vessel 413. Supplied to. Thereafter, a polymerization reaction of lactide was performed in the reaction vessel 413 for 1 hour.
  • Example 29 In Example 27, an experiment was performed in the same manner as in (Example 27) except that the following catalyst extraction operation was performed after the addition of the catalyst.
  • ⁇ Catalyst extraction process> In the reaction apparatus 413 of FIG. 5, supercritical carbon dioxide (100 ° C., 10 MPa, 332 kg / m 3 ) and 2 mL for 30 minutes with a metering pump 408 while the obtained polymer intermediate is kept at 100 ° C. And was discharged from the valve 432, and the operation was performed so as to keep the system at 10 MPa. The polymer intermediate comes into contact with the compressive fluid, and unreacted monomer and catalyst contained in the polymer intermediate are dissolved in the compressible fluid and removed through valve 432.
  • the temperature in the reaction vessel is increased to 150 ° C., and the reaction is performed again by adding a metal catalyst in the same manner as in (Example 27).
  • the pressure was restored, and the polymer product (polylactic acid) in the reaction vessel was taken out from the valve 425 to obtain a polymer product.
  • Example 30 In Example 29, the experiment was performed in the same manner as in (Example 29) except that the time for circulating supercritical carbon dioxide was 60 minutes in the extraction step. With respect to the obtained polymer product, physical property values (Mn, Mw, polymer conversion rate, YI value, catalyst residual amount) were determined by the above method. The results are shown in Table 4.
  • ⁇ 1> comprising a ring-opening polymerization step of bringing the ring-opening polymerizable monomer into contact with a raw material containing a ring-opening polymerizable monomer and a compressive fluid;
  • a ring-opening polymerization step an organic catalyst containing no metal atom and a catalyst containing a metal atom are used.
  • ⁇ 2> The method for producing a polymer according to ⁇ 1>, wherein the raw material containing the ring-opening polymerizable monomer is brought into contact with the compressive fluid at a mixing ratio of the following formula.
  • ⁇ 3> The method for producing a polymer according to ⁇ 1>, wherein the raw material containing the ring-opening polymerizable monomer is continuously brought into contact with the compressive fluid.
  • ⁇ 4> The method for producing a polymer according to ⁇ 3>, wherein the raw material containing the ring-opening polymerizable monomer and the compressive fluid are continuously supplied and contacted under the following conditions.
  • ⁇ 5> Any one of ⁇ 1> to ⁇ 4>, wherein the total amount of the organic catalyst containing no metal atom and the catalyst containing the metal atom is 50 ppm to 500 ppm based on the ring-opening polymerizable monomer This is a method for producing the polymer.
  • ⁇ 6> From the above ⁇ 1> to ⁇ 5>, wherein the mass ratio (organic catalyst: metal catalyst) of the organic catalyst containing no metal atom and the catalyst containing the metal atom is 50:50 to 99: 1 It is a manufacturing method of the polymer in any one.
  • the ring-opening polymerization step the ring-opening polymerizable monomer is subjected to ring-opening polymerization in the presence of an organic catalyst not containing a metal atom, and then further polymerized in the presence of a catalyst containing a metal atom.
  • ⁇ 8> Any one of ⁇ 1> to ⁇ 7>, wherein the ring-opening polymerization step is performed in a reaction vessel in which at least one of an organic catalyst containing no metal atom and a catalyst containing a metal atom is held.
  • ⁇ 9> The method for producing a polymer according to any one of ⁇ 1> to ⁇ 8>, wherein the compressive fluid contains carbon dioxide.

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Abstract

L'invention concerne un procédé de production d'un polymère, qui comprend une étape de polymérisation par ouverture de cycle pour une polymérisation par ouverture de cycle d'un monomère polymérisable par ouverture de cycle en amenant un matériau de départ qui contient le monomère polymérisable par ouverture de cycle en contact avec un fluide comprimé. Un catalyseur organique ne contenant pas d'atomes de métal et un catalyseur contenant des atomes de métal sont utilisés dans l'étape de polymérisation par ouverture de cycle.
PCT/JP2015/055024 2014-03-14 2015-02-23 Procédé de production de polymère WO2015137103A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013189616A (ja) * 2012-02-14 2013-09-26 Ricoh Co Ltd ポリマーの製造方法、及びポリマー生成物
JP2013189620A (ja) * 2011-07-29 2013-09-26 Ricoh Co Ltd ポリマーの製造方法、ポリマー連続製造装置、複合体連続製造装置、及びポリマー生成物
JP2014040560A (ja) * 2012-02-14 2014-03-06 Ricoh Co Ltd ポリマーの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013189620A (ja) * 2011-07-29 2013-09-26 Ricoh Co Ltd ポリマーの製造方法、ポリマー連続製造装置、複合体連続製造装置、及びポリマー生成物
JP2013189616A (ja) * 2012-02-14 2013-09-26 Ricoh Co Ltd ポリマーの製造方法、及びポリマー生成物
JP2014040560A (ja) * 2012-02-14 2014-03-06 Ricoh Co Ltd ポリマーの製造方法

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