WO2017209223A1 - バイオpet樹脂の製造方法 - Google Patents
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- WO2017209223A1 WO2017209223A1 PCT/JP2017/020371 JP2017020371W WO2017209223A1 WO 2017209223 A1 WO2017209223 A1 WO 2017209223A1 JP 2017020371 W JP2017020371 W JP 2017020371W WO 2017209223 A1 WO2017209223 A1 WO 2017209223A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
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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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D22/00—Producing hollow articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/863—Germanium or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0056—Biocompatible, e.g. biopolymers or bioelastomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7158—Bottles
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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
- C08G2390/00—Containers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Definitions
- the present invention relates to a method for producing a polyethylene terephthalate resin derived from biomass resources using an aluminum compound or a germanium compound as a catalyst, and a method for producing a PET product (for example, a PET bottle) including processing the PET resin.
- a PET product for example, a PET bottle
- PET resin Polyethylene terephthalate (PET) resin is a crystalline resin obtained by polycondensation of ethylene glycol and terephthalic acid as main components. Molding processability, heat resistance, chemical resistance, transparency, Because of its excellent mechanical strength and gas barrier properties, it is consumed in large quantities as a material for containers (especially plastic bottles for soft drinks) for beverages, foods, cosmetics, pharmaceuticals, detergents, etc. It comes from resources. In recent years, in consideration of environmental issues such as global warming caused by carbon dioxide emissions and the depletion of petroleum resources, regulations on the environmental impact of industrial activities have become stricter, and instead of petroleum resources, carbon neutral biomass Demand for PET resin derived from resources (hereinafter referred to as “bio-PET resin”) is increasing worldwide.
- bio-PET resin carbon neutral biomass Demand for PET resin derived from resources
- Patent Document 1 a method for producing a polyterephthalic acid multicomponent glycol copolymer polyester fiber using corn-derived ethylene glycol.
- biomass resources contain trace impurities derived from organisms such as proteins and metal cations, and because they are poor in polymerization reactivity and transparency, it is difficult to commercialize them into PET resin.
- bio-PET resin derived from biomass resources.
- the bio-PET resin currently on the market is a product of about 30% by weight of ethylene glycol, one of its main components, produced from sugarcane-derived raw materials (known as “Bio-PET resin 30”).
- Patent Document 2 discloses a method for producing a PET product, which includes a step of forming at least one component of ethylene glycol or terephthalic acid from a bio-based material.
- this document does not teach at all about problems such as polymerization reactivity and transparency in the production of PET resin derived from biomass resources, and how these problems can be solved.
- the PET product disclosed in the literature is manufactured using raw materials in which both ethylene glycol and terephthalic acid are derived from biomass resources
- isophthalic acid, cyclohexane dimethanol or diethylene glycol is used as a copolymerization component in order to impart characteristics that can withstand heating.
- It cannot be a bio-PET resin derived from 100% biomass resources.
- the copolymer component such as isophthalic acid, cyclohexanedimethanol or diethylene glycol contained in the PET resin is only about several weight% (0.1 to 3 weight%). In view of the fact that is consumed, even a trace component in the PET resin cannot be ignored. For this reason, it is conceivable to produce a copolymer component such as isophthalic acid from a raw material derived from biomass resources, but in this case, the production cost becomes extremely high, which is not realistic.
- An object of the present invention is to provide a method for producing a bio-PET resin substantially derived from 100% biomass resource, using as much as possible a material derived from a carbon-neutral biomass resource instead of a material derived from a petroleum resource. There is.
- the inventors of the present invention have used an aluminum compound or a germanium compound in a polymerization process of ethylene glycol derived from biomass resources and terephthalic acid derived from biomass resources.
- a catalyst By using it as a catalyst, it is possible to produce a bio-PET resin that can withstand use as a PET product (especially a PET bottle) without adding a copolymer component such as isophthalic acid, cyclohexanedimethanol or diethylene glycol as a copolymer component. Astonishing knowledge was obtained and the present invention was completed.
- the present invention is as follows.
- a method for producing a bio-PET resin comprising the step of polymerizing ethylene glycol derived from biomass resources and terephthalic acid derived from biomass resources in the presence of a catalyst containing an aluminum compound or a germanium compound.
- Organoaluminum compound in which the aluminum compound is selected from aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum acetylacetonate, acetylacetone aluminum, aluminum oxalate, aluminum oxide or alkylaluminum Or the partial hydrolyzate thereof, or a combination thereof.
- the germanium compound is germanium tetroxide, germanium tetraethoxide, and germanium tetra n-butoxide, crystalline germanium dioxide, amorphous germanium dioxide, germanium hydroxide, germanium oxalate, germanium chloride, or germanium phosphite. The method according to 1, which is a combination thereof.
- the step of polymerizing ethylene glycol derived from biomass resources and terephthalic acid derived from biomass resources causes suspension polymerization of ethylene glycol derived from biomass resources and terephthalic acid derived from biomass resources.
- a method for producing a PET product comprising: providing a bioPET resin by a method according to any one of 1 to 12, and processing the bioPET resin into a PET product. [14] The method according to 13, wherein the PET product is a PET bottle.
- Organoaluminum compound wherein the aluminum compound is selected from aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum acetylacetonate, acetylacetone aluminum, aluminum oxalate, aluminum oxide or alkylaluminum Or use according to 15, which is a partial hydrolyzate thereof, or a combination thereof.
- the germanium compound is germanium tetroxide, germanium tetraethoxide, and germanium tetra n-butoxide, crystalline germanium dioxide, amorphous germanium dioxide, germanium hydroxide, germanium oxalate, germanium chloride, or germanium phosphite.
- Production of bio-PET resin derived from biomass resources includes a step of polymerizing ethylene glycol derived from biomass resources and terephthalic acid derived from biomass resources, ethylene glycol derived from biomass resources and biomass resources Bis ( ⁇ -hydroxyethyl) terephthalate (BHET) as an intermediate is produced by suspension polymerization of ethylene glycol derived from biomass resources and terephthalic acid derived from biomass resources.
- BHET bis ( ⁇ -hydroxyethyl) terephthalate
- bioPET resin derived from biomass resources further comprises processing the bioPET resin obtained by melt polycondensation into pellets and solid-phase polymerizing it.
- the bio-PET resin has an intrinsic viscosity (IV) of 0.7 to 0.85 dl / g.
- IV intrinsic viscosity
- the present invention provides a PET resin using as much as possible a raw material derived from a carbon-neutral biomass resource instead of a raw material derived from a petroleum resource. Since the bio-PET resin obtained by the present invention has the same properties as conventional PET resins derived from petroleum resources, it can be processed into PET products such as PET bottles using existing equipment. The recycling process can be performed together with the PET resin.
- Biomass resources are generally defined as renewable, organic organic resources that exclude petroleum resources. Since biomass resources are organic matter, carbon dioxide is emitted when burned, but the carbon contained in this is derived from carbon dioxide absorbed from the atmosphere by photosynthesis during the growth process. Even if biomass resources are used as a whole, it can be considered that the amount of carbon dioxide in the atmosphere is not increased (that is, carbon neutral). Based on this idea, as a whole, the carbon dioxide concentration in the atmosphere is not increased, so it does not cause global warming. Moreover, unlike fossil resources such as oil, biomass resources can be used without being exhausted by appropriate management.
- the biomass resource is not particularly limited as long as ethylene glycol and / or terephthalic acid can be obtained.
- waste biomass resources for example, paper, livestock manure, food waste, construction waste, black liquor, sewage sludge, garbage) Etc.
- unused biomass resources for example, rice straw, wheat straw, rice husks, forest residue, resource crops, feed crops, starch crops, etc.
- carbohydrate raw materials sucgarcane, molasses, sugar beet, etc.
- starchy raw materials corn, sorghum, potato, sweet potato, wheat, cassava, etc.
- other cellulosic plant-derived raw materials pulp waste liquor, bagasse, waste wood, etc.
- Natural fiber products or waste products thereof including unused products such as surplus stock).
- Ethylene glycol derived from biomass resources and terephthalic acid derived from biomass resources which are raw materials for bio-PET resins, are rapid thermal decomposition of catalysts, liquid phase reforming, chemical conversion using catalysts, acid hydrolysis, enzyme hydrolysis It can be produced using known methods such as microbial decomposition, fermentation-derived conversion, microbial decomposition, and hydrocracking.
- ethylene glycol derived from biomass resources can be obtained by, for example, fermenting biomass resources and extracting bioethanol, converting bioethanol obtained thereby into ethylene, and further converting into ethylene glycol via ethylene oxide.
- terephthalic acid derived from biomass resources generates xylene by catalytically pyrolyzing biomass, followed by separation and purification and isomerization to produce paraxylene, which is then subjected to a liquid phase oxidation reaction.
- terephthalic acid derived from biomass resources generates xylene by catalytically pyrolyzing biomass, followed by separation and purification and isomerization to produce paraxylene, which is then subjected to a liquid phase oxidation reaction.
- Biopolymer PET resin is produced by polymerizing ethylene glycol derived from the biomass resource and terephthalic acid derived from the biomass resource in the presence of a catalyst containing an aluminum compound or a germanium compound.
- an antimony compound such as antimony trioxide having an inexpensive and excellent catalytic activity and a titanium compound having excellent safety and reactivity are used as a catalyst.
- an antimony compound or a titanium compound it is necessary to increase the amount of addition during polymerization, so that the amount of residue in the PET resin increases and the crystallization speed increases. As a result, the transparency is impaired, or the physical properties (for example, heat resistance and pressure resistance) of the bottle are not adapted.
- a copolymerization component such as isophthalic acid, cyclohexanedimethanol, or diethylene glycol as a component that suppresses excessive crystallization.
- the copolymer component such as isophthalic acid, cyclohexanedimethanol or diethylene glycol contained in the PET resin is only a few weight percent (0.1 to 3 weight percent). Considering that it is consumed, it is clear that even if it is such a trace component, if the use of raw materials derived from petroleum resources can be avoided in its production, it will greatly contribute to the global environment. is there.
- the present inventors have recently added a copolymer component such as isophthalic acid, cyclohexanedimethanol or diethylene glycol in the production of bio-PET resin by using an aluminum compound or germanium compound having a relatively high catalytic activity as a catalyst.
- a copolymer component such as isophthalic acid, cyclohexanedimethanol or diethylene glycol
- an aluminum compound or germanium compound having a relatively high catalytic activity as a catalyst.
- aluminum compounds and germanium compounds are used as polyester polymerization catalysts in the production of PET resins using raw materials derived from petroleum resources (Patent Documents 3 to 9).
- Patent Documents 3 to 9 there has been no attempt to produce bio-PET resin derived from substantially 100% biomass resources while avoiding the addition of copolymer components such as isophthalic acid, cyclohexanedimethanol and diethylene glycol.
- the transparency and intrinsic viscosity (IV) retention rate of the PET resin is increased as compared with the case where another catalyst such as an antimony compound or a titanium compound is used. It was also found out. Such characteristics are advantageous for processing and recycling into PET products.
- Examples of the aluminum compound used in the present invention include aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum acetylacetonate, acetylacetone aluminum, aluminum oxalate, aluminum oxide, and alkylaluminum.
- An organoaluminum compound, a partial hydrolyzate thereof, and the like are exemplified, but not limited thereto.
- the aluminum compound is used such that the content as aluminum atoms in the resin is typically about 1 to about 50 ppm, preferably about 3 to about 40 ppm, and optimally about 10 to about 20 ppm.
- germanium compound used in the present invention examples include germanium tetroxide, germanium tetraethoxide, and germanium tetra n-butoxide, crystalline germanium dioxide, amorphous germanium dioxide, germanium hydroxide, germanium oxalate, germanium chloride, phosphorous acid Examples thereof include, but are not limited to, compounds such as germanium acid.
- the germanium compound is used so that the content of germanium atoms in the resin is typically about 1 ppm to 100 ppm.
- the polymerization process of the bio-PET resin can be performed in a conventionally known process.
- ethylene glycol (liquid) derived from biomass resources and terephthalic acid (powder) derived from biomass resources was subjected to suspension polymerization to obtain bis ( ⁇ -hydroxyethyl) terephthalate (BHET) and / or an oligomer thereof as an intermediate, and then at about 270 to 300 ° C. in the presence of a catalyst containing an aluminum compound or a germanium compound.
- BHET bis ( ⁇ -hydroxyethyl) terephthalate
- it comprises melt polycondensation of the BHET obtained above by performing a dehydration reaction in a high vacuum.
- a catalyst containing an aluminum compound or a germanium compound can be added to the reaction system at any stage of the polymerization reaction.
- these catalysts may be added to the reaction system at any stage before or during the esterification reaction or transesterification reaction, or at any stage immediately before or during the polycondensation reaction. However, it is preferably added immediately before the start of the polycondensation reaction.
- the addition method of the catalyst may be addition in a powder form or neat form, or may be addition in a slurry form or a solution form of a solvent such as ethylene glycol derived from biomass resources, and is not particularly limited.
- the melt polycondensation reaction may be performed in a batch reactor or may be performed in a continuous reactor.
- the melt polycondensation reaction may be performed in one stage or may be performed in multiple stages.
- a phosphorus compound may be added as a stabilizer.
- the phosphorus compound include phosphoric acid or a phosphate ester, or a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphonous acid compound, a phosphinic acid compound, or a phosphine compound.
- the phosphorus compound may be added to the polymerization system simultaneously with the catalyst, or may be added at different addition times.
- the bio-PET resin obtained by melt polycondensation is extruded and processed into pellets by a pelletizer to obtain transparent pellets.
- the melt weight obtained in this way is used for beverage bottles, especially when low acetaldehyde content or low cyclic trimer content is required, such as low flavor beverages and heat-resistant hollow molded products for mineral water.
- the condensed polyester is solid state polymerized.
- the solid-phase polymerization reaction can be performed by a batch apparatus or a continuous apparatus, and may be operated continuously with the melt polycondensation step or may be operated separately. .
- the pellets are pre-crystallized by heating at a temperature of 100 to 210 ° C.
- solid phase polymerization is carried out for a predetermined time at a temperature of 190 to 230 ° C. in an inert gas atmosphere or under reduced pressure.
- molecules of the PET resin can be polymerized to increase the strength.
- impurities such as acetaldehyde and cyclic oligomers contained in the raw material resin can be reduced by performing solid phase polymerization.
- a bioPET resin substantially derived from 100% biomass resources can be obtained.
- “Substantially derived from 100% biomass resources” means more than 97%, preferably more than 98%, more preferably more than 99%, and most preferably 99% of the components of the obtained bioPET resin. . More than 9% by weight is derived from biomass resources.
- the obtained bio-PET resin has excellent transparency and inherent viscosity (IV) retention, and is extremely useful as a material for PET products such as PET bottles.
- PET products By processing bio-PET resin into a PET product using a known method, a high-value-added PET product can be produced.
- PET products include containers for beverages, foods, cosmetics, pharmaceuticals, detergents and the like (especially plastic bottles for soft drinks), as well as clothing fibers such as photographic films, cassette tapes, and fleeces. It is not limited to.
- soft drink PET bottles include heat-resistant PET bottles, aseptic filling PET bottles, pressure-resistant PET bottles, and heat-resistant pressure pot bottles.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
特許文献2には、エチレングルコール又はテレフタル酸のうち少なくとも1つの成分をバイオベース材料から形成する工程を含む、PET製品の製造方法が開示されている。しかしながら、当該文献には、バイオマス資源に由来するPET樹脂の製造における、重合反応性や透明性などの課題や、このような課題を如何にして解決できるのかについては全く教示されていない。仮に、当該文献に開示されるPET製品が、エチレングルコールとテレフタル酸の両方がバイオマス資源に由来している原料を用いて製造されているとしても、無菌充填用ペットボトルなどのPET製品には、加熱に耐えられる特性を付与するため、モノエチレングリコールやテレフタル酸といった主成分の他に、通常、イソフタル酸、シクロヘキサンジメタノール又はジエチレングリコールなどが共重合成分として用いられていることから、実質的に100%バイオマス資源に由来するバイオPET樹脂ということはできない。例えば、PET樹脂に含有されるイソフタル酸、シクロヘキサンジメタノール又はジエチレングリコールといった共重合成分は、僅か数重量%(0.1~3重量%)程度に過ぎないが、世界中で膨大な量のPET樹脂が消費されていることを考慮すれば、PET樹脂中の微量成分であっても無視することはできない。このため、イソフタル酸などの共重合成分をバイオマス資源に由来する原料から製造することが考えられるが、この場合には製造コストが極めて高くなるため、現実的ではない。
[1] バイオPET樹脂の製造方法であって、アルミニウム化合物又はゲルマニウム化合物を含有する触媒の存在下において、バイオマス資源に由来するエチレングルコールとバイオマス資源に由来するテレフタル酸とを重合させる工程を含むことを特徴とする、方法。
[2] 共重合成分が添加されないことを特徴とする、1に記載の方法。
[3] 前記共重合成分が、イソフタル酸、シクロヘキサンジメタノール又はジエチレングリコールである、2に記載の方法。
[4] 前記アルミニウム化合物が、酢酸アルミニウム、乳酸アルミニウム、塩化アルミニウム、水酸化アルミニウム、水酸化塩化アルミニウム、アルミニウムアセチルアセトネート、アセチルアセトンアルミニウム、シュウ酸アルミニウム、酸化アルミニウムもしくはアルキルアルミニウムから選択される有機アルミニウム化合物又はその部分加水分解物、あるいはこれらの組み合せである、1に記載の方法。
[5] 前記ゲルマニウム化合物が、四酸化ゲルマニウム、ゲルマニウムテトラエトキシド、及びゲルマニウムテトラn-ブトキシド、結晶性二酸化ゲルマニウム、非晶性二酸化ゲルマニウム、水酸化ゲルマニウム、シュウ酸ゲルマニウム、塩化ゲルマニウムもしくは亜リン酸ゲルマニウム、又はこれらの組み合せである、1に記載の方法。
[6] 前記バイオマス資源が、サトウキビ、モラセスもしくはテンサイから選択される糖質原料、トウモロコシ、ソルガム、ジャガイモ、サツマイモ、麦もしくはキャッサバから選択されるデンプン質原料、パルプ廃液、バガス、廃材木、ウッドチップ、もみ殻、稲藁、果実繊維、果実核殻もしくは空果房から選択されるセルロース系植物由来原料、天然繊維製品もしくはその廃品、又はこれらの組み合せである、1~5のいずれかに記載の方法。
[7] 前記バイオマス資源に由来するエチレングルコールとバイオマス資源に由来するテレフタル酸とを重合させる工程が、バイオマス資源に由来するエチレングルコールとバイオマス資源に由来するテレフタル酸とを懸濁重合させることにより中間体としてビス(β-ヒドロキシエチル)テレフタレート(BHET)及び/又はそのオリゴマーを製造し、これにより得られたBHET及び/又はそのオリゴマーを、前記触媒の存在下において溶融重縮合させることを含む、1~6のいずれかに記載の方法。
[8] 溶融重縮合により得られたバイオPET樹脂をペレットに加工し、これを固相重合させることをさらに含む、7に記載の方法。
[9] 前記バイオPET樹脂の固有粘度(IV)が、0.7~0.85dl/gであることを特徴とする、1~8のいずれかに記載の方法。
[10] 前記バイオPET樹脂の成分の97重量%超が、バイオマス資源に由来することを特徴とする、1~9のいずれかに記載の方法。
[11] 前記バイオPET樹脂の成分の99重量%超が、バイオマス資源に由来することを特徴とする、10に記載の方法。
[12] 前記バイオPET樹脂の成分の99.9重量%超が、バイオマス資源に由来することを特徴とする、11に記載の方法。
[13] PET製品の製造方法であって、1~12のいずれかに記載の方法によりバイオPET樹脂を供し、該バイオPET樹脂をPET製品に加工することを含むことを特徴とする、方法。
[14] 前記PET製品がペットボトルであることを特徴とする、13に記載の方法。
[15] バイオマス資源に由来するバイオPET樹脂の製造における、アルミニウム化合物又はゲルマニウム化合物を含有する触媒の使用。
[16] バイオマス資源に由来するバイオPET樹脂の製造において、共重合成分が添加されないことを特徴とする、15に記載の使用。
[17]前記共重合成分が、イソフタル酸、シクロヘキサンジメタノール又はジエチレングリコールである、16に記載の使用。
[18] 前記アルミニウム化合物が、酢酸アルミニウム、乳酸アルミニウム、塩化アルミニウム、水酸化アルミニウム、水酸化塩化アルミニウム、アルミニウムアセチルアセトネート、アセチルアセトンアルミニウム、シュウ酸アルミニウム、酸化アルミニウムもしくはアルキルアルミニウムから選択される有機アルミニウム化合物又はその部分加水分解物、あるいはこれらの組み合せである、15に記載の使用。
[19] 前記ゲルマニウム化合物が、四酸化ゲルマニウム、ゲルマニウムテトラエトキシド、及びゲルマニウムテトラn-ブトキシド、結晶性二酸化ゲルマニウム、非晶性二酸化ゲルマニウム、水酸化ゲルマニウム、シュウ酸ゲルマニウム、塩化ゲルマニウムもしくは亜リン酸ゲルマニウム、又はこれらの組み合せである、15に記載の使用。
[20] 前記バイオマス資源が、サトウキビ、モラセスもしくはテンサイから選択される糖質原料、トウモロコシ、ソルガム、ジャガイモ、サツマイモ、麦もしくはキャッサバから選択されるデンプン質原料、パルプ廃液、バガス、廃材木、ウッドチップ、もみ殻、稲藁、果実繊維、果実核殻もしくは空果房から選択されるセルロース系植物由来原料、天然繊維製品もしくはその廃品、又はこれらの組み合せである、15~19のいずれかに記載の使用。
[21] バイオマス資源に由来するバイオPET樹脂の製造がバイオマス資源に由来するエチレングルコールとバイオマス資源に由来するテレフタル酸とを重合させる工程を含み、前記バイオマス資源に由来するエチレングルコールとバイオマス資源に由来するテレフタル酸とを重合させる工程が、バイオマス資源に由来するエチレングルコールとバイオマス資源に由来するテレフタル酸とを懸濁重合させることにより中間体としてビス(β-ヒドロキシエチル)テレフタレート(BHET)及び/又はそのオリゴマーを製造し、これにより得られたBHET及び/又はそのオリゴマーを、前記触媒の存在下において溶融重縮合させることを含む、15~20のいずれかに記載の使用。
[22] バイオマス資源に由来するバイオPET樹脂の製造が、溶融重縮合により得られたバイオPET樹脂をペレットに加工し、これを固相重合させることをさらに含む、21に記載の使用。
[23] 前記バイオPET樹脂の固有粘度(IV)が、0.7~0.85dl/gであることを特徴とする、15~22のいずれかに記載の使用。
[24] 前記バイオPET樹脂の成分の97重量%超が、バイオマス資源に由来することを特徴とする、15~23のいずれかに記載の使用。
[25] 前記バイオPET樹脂の成分の99重量%超が、バイオマス資源に由来することを特徴とする、24に記載の使用。
[26] 前記バイオPET樹脂の成分の99.9重量%超が、バイオマス資源に由来することを特徴とする、25に記載の使用。
Claims (14)
- バイオPET樹脂の製造方法であって、アルミニウム化合物又はゲルマニウム化合物を含有する触媒の存在下において、バイオマス資源に由来するエチレングルコールとバイオマス資源に由来するテレフタル酸とを重合させる工程を含むことを特徴とする、方法。
- 共重合成分が添加されないことを特徴とする、請求項1に記載の方法。
- 前記共重合成分が、イソフタル酸、シクロヘキサンジメタノール又はジエチレングリコールである、請求項2に記載の方法。
- 前記アルミニウム化合物が、酢酸アルミニウム、乳酸アルミニウム、塩化アルミニウム、水酸化アルミニウム、水酸化塩化アルミニウム、アルミニウムアセチルアセトネート、アセチルアセトンアルミニウム、シュウ酸アルミニウム、酸化アルミニウムもしくはアルキルアルミニウムから選択される有機アルミニウム化合物又はその部分加水分解物、あるいはこれらの組み合せである、請求項1に記載の方法。
- 前記ゲルマニウム化合物が、四酸化ゲルマニウム、ゲルマニウムテトラエトキシド、ゲルマニウムテトラn-ブトキシド、結晶性二酸化ゲルマニウム、非晶性二酸化ゲルマニウム、水酸化ゲルマニウム、シュウ酸ゲルマニウム、塩化ゲルマニウムもしくは亜リン酸ゲルマニウム、又はこれらの組み合せである、請求項1に記載の方法。
- 前記バイオマス資源が、サトウキビ、モラセスもしくはテンサイから選択される糖質原料、トウモロコシ、ソルガム、ジャガイモ、サツマイモ、麦もしくはキャッサバから選択されるデンプン質原料、パルプ廃液、バガス、廃材木、ウッドチップ、もみ殻、稲藁、果実繊維、果実核殻もしくは空果房から選択されるセルロース系植物由来原料、天然繊維製品もしくはその廃品、又はこれらの組み合せである、請求項1~5のいずれか1項に記載の方法。
- 前記バイオマス資源に由来するエチレングルコールとバイオマス資源に由来するテレフタル酸とを重合させる工程が、バイオマス資源に由来するエチレングルコールとバイオマス資源に由来するテレフタル酸とを懸濁重合させることにより中間体としてビス(β-ヒドロキシエチル)テレフタレート(BHET)及び/又はそのオリゴマーを製造し、これにより得られたBHET及び/又はそのオリゴマーを、前記触媒の存在下において溶融重縮合させることを含む、請求項1~6のいずれか1項に記載の方法。
- 溶融重縮合により得られたバイオPET樹脂をペレットに加工し、これを固相重合させることをさらに含む、請求項7に記載の方法。
- 前記バイオPET樹脂の固有粘度(IV)が、0.7~0.85dl/gであることを特徴とする、請求項1~8のいずれか1項に記載の方法。
- 前記バイオPET樹脂の成分の97重量%超が、バイオマス資源に由来することを特徴とする、請求項1~9のいずれかに記載の方法。
- 前記バイオPET樹脂の成分の99重量%超が、バイオマス資源に由来することを特徴とする、請求項10に記載の方法。
- 前記バイオPET樹脂の成分の99.9重量%超が、バイオマス資源に由来することを特徴とする、請求項11に記載の方法。
- PET製品の製造方法であって、請求項1~12のいずれか1項に記載の方法によりバイオPET樹脂を供し、該バイオPET樹脂をPET製品に加工することを含むことを特徴とする、方法。
- 前記PET製品がペットボトルであることを特徴とする、請求項13に記載の方法。
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CA3026042A CA3026042A1 (en) | 2016-05-31 | 2017-05-31 | Method for producing bio-pet resin |
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MY193173A (en) | 2022-09-26 |
MX2018014847A (es) | 2019-04-24 |
BR112018074733A2 (pt) | 2019-03-12 |
US20190135975A1 (en) | 2019-05-09 |
AU2017275297A1 (en) | 2018-12-20 |
CN109196020A (zh) | 2019-01-11 |
RU2018145805A3 (ja) | 2020-09-18 |
KR20190015241A (ko) | 2019-02-13 |
CA3026042A1 (en) | 2017-12-07 |
TW202200667A (zh) | 2022-01-01 |
RU2018145805A (ru) | 2020-07-09 |
EP3467004A4 (en) | 2019-11-20 |
AU2017275297B2 (en) | 2021-06-24 |
BR112018074733B1 (pt) | 2022-10-18 |
EP3467004A1 (en) | 2019-04-10 |
ES2935598T3 (es) | 2023-03-08 |
TW202409137A (zh) | 2024-03-01 |
EP3467004B1 (en) | 2022-12-14 |
RU2745217C2 (ru) | 2021-03-22 |
KR20220070059A (ko) | 2022-05-27 |
JPWO2017209223A1 (ja) | 2019-03-28 |
JP2023155409A (ja) | 2023-10-20 |
TW201811858A (zh) | 2018-04-01 |
JP2022009611A (ja) | 2022-01-14 |
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