WO2023054271A1 - 再生ポリエステル樹脂の製造方法 - Google Patents
再生ポリエステル樹脂の製造方法 Download PDFInfo
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- WO2023054271A1 WO2023054271A1 PCT/JP2022/035753 JP2022035753W WO2023054271A1 WO 2023054271 A1 WO2023054271 A1 WO 2023054271A1 JP 2022035753 W JP2022035753 W JP 2022035753W WO 2023054271 A1 WO2023054271 A1 WO 2023054271A1
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- WIPO (PCT)
- Prior art keywords
- polyester resin
- aluminum
- acid
- recycled polyester
- phosphorus
- Prior art date
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 198
- 239000004645 polyester resin Substances 0.000 title claims abstract description 198
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- -1 aluminum compound Chemical class 0.000 claims abstract description 130
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 71
- 229920000728 polyester Polymers 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 145
- 229910052698 phosphorus Inorganic materials 0.000 claims description 108
- 239000011574 phosphorus Substances 0.000 claims description 108
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 52
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 50
- 150000005846 sugar alcohols Polymers 0.000 claims description 35
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052787 antimony Inorganic materials 0.000 claims description 15
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
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- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 10
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
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- 238000005481 NMR spectroscopy Methods 0.000 description 6
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- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 5
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
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- 125000001424 substituent group Chemical group 0.000 description 4
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- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 125000003545 alkoxy group Chemical group 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
Definitions
- the present invention relates to a method for producing recycled polyester resin.
- Polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are excellent in mechanical properties, chemical stability, heat resistance, gas barrier properties, transparency, etc., and are inexpensive. It is widely used in the manufacture of containers, etc.
- Polyethylene terephthalate which is produced using an antimony catalyst or a germanium catalyst, is often used as a polymerization catalyst for the polyester used in the production of containers because of its cost.
- containers are being manufactured using polyester obtained by recycling used and collected polyester containers by various methods.
- a recycling method methods such as the following chemical recycling and mechanical recycling are known.
- Chemical recycling refers to the method of decomposing the recovered polyester down to the monomer level and polymerizing it again to obtain polyester resin.
- chemical recycling requires a large amount of energy and the process is complicated, so a large cost was required for recycling.
- Mechanical recycling involves sorting, pulverizing, and washing the collected polyester to remove contaminants and foreign matter to obtain flakes, which are further treated at high temperature and under reduced pressure for a certain period of time to remove contaminants inside the resin.
- polyester obtained by mechanical recycling has the advantages of low environmental load and low cost.
- mechanically recycled polyester has problems such as coloration and deterioration in quality due to increased amounts of acetaldehyde and cyclic trimers.
- polyethylene terephthalate is decomposed by a reaction with a low-molecular-weight polyol, and then the decomposed product and a polybasic acid are subjected to a condensation reaction to produce a terephthalic acid-based polyester polyol.
- Patent Document 1 Japanese Patent Document 1
- Patent Document 1 aims to produce polyester polyol for polyurethane resin, suppression of coloring of the recycled polyester was not considered.
- polyethylene terephthalate is decomposed by a reaction with a low-molecular-weight polyol and then subjected to a condensation reaction. Further cost reduction is desired by reducing the number.
- the present invention has been made to solve the problems of the prior art, and an object thereof is to provide a low-cost method for producing recycled polyester with suppressed coloration.
- the recovered polyester resin (A), polycarboxylic acid (B), and polyhydric alcohol (C) are mixed to depolymerize and esterify. and a second step of further polycondensing the reaction product of the first step to increase the molecular weight, and by using the recovered polyester resin and aluminum catalyst in a predetermined ratio , It was found that a recycled polyester resin with suppressed coloring can be produced at low cost.
- the present invention consists of the following configurations.
- the polycondensation in the second step is carried out in the presence of an aluminum compound, and the aluminum compound is 5 to 100 ppm by mass in terms of aluminum element with respect to the reactant.
- the polycondensation in the second step is carried out in the presence of a phosphorus compound, and the amount of the phosphorus compound is 3 to 1000 ppm by mass in terms of phosphorus element with respect to the reactant.
- the method for producing the recycled polyester resin according to . 4. The above 1. wherein the polyester resin (A) has a dicarboxylic acid unit derived from an aromatic dicarboxylic acid and a diol unit derived from an alkylene glycol having 2 to 6 carbon atoms. ⁇ 3.
- a recycled polyester resin is produced by a production method having a second step of increasing the molecular weight, and in the production method, by using the recovered polyester resin and an aluminum catalyst in a predetermined ratio, coloring is reduced at low cost. Inhibited recycled polyester resins can be produced.
- FIG. 1 shows a schematic diagram of a chart measured with a differential scanning calorimeter.
- the method for producing the recycled polyester resin (hereinafter referred to as the recycled polyester resin (D)) of the present invention comprises mixing the recovered polyester resin (A), the polyhydric carboxylic acid (B), and the polyhydric alcohol (C). , a first step of depolymerizing and esterifying, and a second step of further polycondensing the reaction product of the first step to increase the molecular weight.
- the recovered polyester resin (A) may be simply referred to as "polyester resin (A)".
- the polyester resin (A) is a used polyester resin and/or a recovered polyester resin that is not used and is generated in the process of manufacturing polyester products.
- the polyester resin (A) is a polymer formed from at least one selected from polyhydric carboxylic acids and ester-forming derivatives thereof and at least one selected from polyhydric alcohols and ester-forming derivatives thereof.
- the main polycarboxylic acid component constituting the polyester resin (A) preferably contains more than 50 mol%, more preferably 70 mol% or more, in 100 mol% of the total polycarboxylic acid component. It is more preferably contained in an amount of mol % or more, and particularly preferably in an amount of 90 mol % or more.
- the main polycarboxylic acid component constituting the polyester resin (A) refers to the polycarboxylic acid component having the highest molar ratio, and the main polycarboxylic acid component constituting the polyester resin (A)
- the component is a dicarboxylic acid or a formable derivative thereof.
- Dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1, 3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc.
- saturated aliphatic dicarboxylic acids exemplified in or ester-forming derivatives thereof; unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid, or ester-forming derivatives thereof; terephthalic acid, 5-(alkali metal)sulfoisophthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'- Aromatic dicarboxylic acids such as dicarboxylic acid, pa
- the main polycarboxylic acid component is terephthalic acid or its ester-forming derivative, naphthalene dicarboxylic acid or its ester-forming derivative, or furandicarboxylic acid or its ester-forming derivative.
- the content is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more.
- the main polyhydric alcohol component constituting the polyester resin (A) preferably contains more than 50 mol%, more preferably 70 mol% or more, and 80 mol% or more in 100 mol% of the polyhydric alcohol component. It is more preferably contained, particularly preferably at least 90 mol %, most preferably at least 95 mol %.
- the main polyhydric alcohol component constituting the polyester resin (A) refers to the polyhydric alcohol component having the highest molar ratio, and the main polyhydric alcohol component constituting the polyester resin (A) is Glycol is preferred, and ethylene glycol is more preferred.
- Glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,3-butylene glycol, 4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediol alkylene glycols exemplified by methanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol; polyethylene glycol; Aliphatic glycols
- alkylene glycol is preferred, and ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, or 1,4-cyclohexanedimethanol are more preferred.
- the alkylene glycol may contain a substituent or an alicyclic structure in the molecular chain, and two or more of them may be used at the same time.
- the polyester resin (A) preferably has a dicarboxylic acid unit derived from an aromatic dicarboxylic acid and a diol unit derived from an alkylene glycol having 2 to 6 carbon atoms.
- the aromatic dicarboxylic acid preferably contains at least one of terephthalic acid and naphthalenedicarboxylic acid, and the alkylene glycol having 2 to 6 carbon atoms contains at least one of ethylene glycol, trimethylene glycol, and tetramethylene glycol. is preferred, and ethylene glycol is more preferred.
- the polyester resin (A) preferably contains at least one of ethylene terephthalate units, ethylene furanoate units, and ethylene naphthalate units.
- the total content of ethylene terephthalate units, ethylene furanoate units, and ethylene naphthalate units is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and 90 mol% or more. is particularly preferable, and it is most preferable to contain 95 mol % or more.
- the polyester resin (A) preferably contains ethylene terephthalate units, more preferably 50 mol% or more of ethylene terephthalate units, still more preferably 70 mol% or more, and even more preferably 80 mol% or more. , is particularly preferably at least 90 mol %, most preferably at least 95 mol %.
- the polyester resin (A) may contain a large amount of ethylene naphthalate units. is more preferable, more preferably 80 mol% or more, particularly preferably 90 mol% or more, most preferably 95 mol% or more.
- the polyester resin (A) preferably contains at least one element selected from antimony, titanium, and germanium. That is, the polyester resin (A) is preferably produced using a catalytic amount of at least one polymerization catalyst selected from antimony compounds, titanium compounds, and germanium compounds.
- the polyester resin produced using at least one polymerization catalyst selected from antimony compounds, titanium compounds, and germanium compounds in the polyester resin (A) is preferably 50 mol% or more, and preferably 70 mol% or more. is more preferable, and 80 mol % or more is even more preferable.
- a polyester resin produced using at least one polymerization catalyst selected from an antimony compound, a titanium compound, and a germanium compound is easily colored when recycled, but when recycled by the production method of the present invention, the recycled polyester resin (D) coloring can be suppressed.
- the total content of the antimony element, titanium element, and germanium element in the polyester resin (A) is, for example, 2 to 500 mass ppm, preferably 5 to 400 mass ppm, and 10 to 300 mass ppm. is more preferable, and 50 to 250 ppm by mass is even more preferable. If it exceeds 500 ppm by mass, there is a possibility that coloring of the recycled polyester resin (D) cannot be suppressed.
- mass ppm means 10 ⁇ 4 mass %.
- the intrinsic viscosity (IV) of the polyester resin (A) is preferably 0.5-0.8 dl/g, more preferably 0.7-0.8 dl/g. If the intrinsic viscosity of the polyester resin (A) is less than the above, the mechanical strength and impact resistance of the recycled polyester resin (D) produced using the polyester resin (A) may be insufficient. If the intrinsic viscosity of the resin (A) exceeds the above range, molding may become difficult.
- polyvalent carboxylic acid (B) and polyhydric alcohol (C) As the polyhydric carboxylic acid (B) and the polyhydric alcohol (C), the components described in the above polyester resin (A) can be used.
- the polycarboxylic acid (B) preferably contains 70 mol% or more of the main polycarboxylic acid component constituting the polyester resin (A), more preferably 80 mol% or more, and preferably contains 90 mol% or more. More preferred.
- the polyhydric alcohol (C) preferably contains 70 mol% or more of the main polyhydric alcohol component constituting the polyester resin (A), more preferably 80 mol% or more, even more preferably 90 mol% or more. , 95 mol % or more is particularly preferred.
- the main polycarboxylic acid component constituting the polyester resin (A) is preferably a dicarboxylic acid, and the polycarboxylic acid (B) is also preferably a dicarboxylic acid as a main component.
- a polyvalent carboxylic acid having a valence of 3 or more or a hydroxycarboxylic acid may be used in combination as long as the amount is small, and a polyvalent carboxylic acid having a valence of 3 to 4 is preferred.
- polyvalent carboxylic acids examples include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3′,4′-biphenyltetracarboxylic acid, and these and ester-forming derivatives.
- Trivalent or higher polycarboxylic acid is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less in 100 mol% of the total polycarboxylic acid (B) component. is.
- B total polycarboxylic acid
- Hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or these and ester-forming derivatives of
- the hydroxycarboxylic acid content is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less in 100 mol% of the total polycarboxylic acid (B) component. When two or more hydroxycarboxylic acids are used, the total is preferably within the above range.
- ester-forming derivatives of polyvalent carboxylic acids or hydroxycarboxylic acids include their alkyl esters, acid chlorides, acid anhydrides, and the like.
- the main polyhydric alcohol component constituting the polyester resin (A) is preferably glycol, and the polyhydric alcohol (C) is also preferably glycol as the main component. If so, a trihydric or higher polyhydric alcohol may be used in combination, and trihydric to tetrahydric polyhydric alcohols are preferred. Trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like are examples of trihydric or higher polyhydric alcohols.
- the trihydric or higher polyhydric alcohol is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less in 100 mol% of the total polyhydric alcohol (C) component. .
- the total is preferably within the above range.
- Cyclic esters include ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -methyl- ⁇ -propiolactone, ⁇ -valerolactone, glycolide, lactide and the like.
- ester-forming derivatives of polyhydric alcohols include esters of polyhydric alcohols with lower aliphatic carboxylic acids such as acetic acid.
- the cyclic ester is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less. In addition, when using two or more cyclic esters, it is preferable that the total of them is within the above range.
- the intrinsic viscosity of the recycled polyester resin (D) is preferably 0.50 to 0.90 dl/g, more preferably 0.55 to 0.80 dl/g. If the intrinsic viscosity of the recycled polyester resin (D) is less than 0.50 dl/g, the mechanical strength and impact resistance of the recycled polyester resin (D) may become insufficient. On the other hand, if the intrinsic viscosity of the recycled polyester resin (D) exceeds 0.90 dl/g, there is a possibility that the economic efficiency will decrease.
- the reduced viscosity of the recycled polyester resin (D) is preferably 0.50-0.90 dl/g, more preferably 0.55-0.80 dl/g. If the reduced viscosity of the recycled polyester resin (D) is less than 0.50 dl/g, the mechanical strength and impact resistance of the recycled polyester resin (D) may become insufficient. On the other hand, when the reduced viscosity of the recycled polyester resin (D) exceeds 0.90 dl/g, there is a possibility that the economic efficiency may decrease.
- the ratio of the polyester resin (A) used in the production method of the present invention is 5 to 80 parts by mass, preferably 7 to 70 parts by mass, with respect to 100 parts by mass of the recycled polyester resin (D). Parts by mass are more preferred. By setting it within the above range, coloring of the recycled polyester resin (D) and reduction in molecular weight can be suppressed.
- the blending ratio of the polyester resin (A) exceeds 80 parts by mass, the esterification reaction is sufficiently performed when the polyester resin (A), the polycarboxylic acid (B) and the polyhydric alcohol (C) are mixed. Since it does not progress, it becomes incompatible.
- the blending ratio of the polyester resin (A) is less than 5 parts by mass, there is a possibility that the effect of suppressing coloration will saturate and the economy will decrease.
- the acid value of the recycled polyester resin (D) is 100 eq/ton or less, preferably 70 eq/ton or less, more preferably 3 to 60 eq/ton.
- the recycled polyester resin (D) is obtained by further polycondensing the reactant obtained in the first step to increase the molecular weight. is done below.
- the recycled polyester resin (D) is produced using a polymerization catalyst containing an aluminum compound, and is produced using a catalytic amount of the polymerization catalyst containing an aluminum compound.
- the polycondensation of the recycled polyester resin (D) is preferably carried out in the presence of an aluminum compound and a phosphorus compound, that is, it is produced using a polymerization catalyst comprising an aluminum compound and a phosphorus compound. preferable.
- the aluminum compound that constitutes the polymerization catalyst for the recycled polyester resin (D) is not limited as long as it dissolves in a solvent, and known aluminum compounds can be used without limitation.
- Aluminum compounds such as aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, citric acid Carboxylate such as aluminum, aluminum tartrate, aluminum salicylate; inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxychloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, aluminum phosphonate; aluminum methoxide , aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum t-butoxide, etc.
- At least one selected from carboxylates, inorganic acid salts, and chelate compounds is preferred, and among these, aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetate more preferably at least one selected from aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetonate, aluminum acetate and a base At least one selected from the group consisting of aluminum acetates is particularly preferred, and basic aluminum acetate is most preferred.
- the above aluminum compound is preferably an aluminum compound that is solubilized in a solvent such as water or glycol.
- Solvents that can be used in the production of the recycled polyester resin (D) are water and alkylene glycols.
- Alkylene glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylene glycol, ditrimethylene glycol, tetramethylene glycol, ditetramethylene glycol, neopentyl glycol, and the like.
- it is at least one selected from water, ethylene glycol, trimethylene glycol, and tetramethylene glycol, and more preferably water or ethylene glycol.
- the content of aluminum element in the recycled polyester resin (D) is 5 to 100 mass ppm, preferably 7 to 60 mass ppm, more preferably 10 to 50 mass ppm, still more preferably 12 to 40 mass ppm. . If the amount of aluminum element is less than 5 ppm by mass, the polymerization activity may not be sufficiently exhibited. On the other hand, if it exceeds 100 ppm by mass, the amount of aluminum-based contaminants may increase.
- the phosphorus compound that constitutes the polymerization catalyst of the regenerated polyester resin (D) is not particularly limited, but it is preferable to use a phosphonic acid-based compound or a phosphinic acid-based compound because the effect of improving the catalytic activity is large. It is preferable to use a compound based on the above because the effect of improving the catalytic activity is particularly large.
- a phosphorus compound having a phosphorus element and a phenol structure in the same molecule is preferable.
- a phosphorus compound having a phosphorus element and a phenol structure in the same molecule but a phosphonic acid compound having a phosphorus element and a phenol structure in the same molecule, and a phosphine having a phosphorus element and a phenol structure in the same molecule
- R 1 represents a hydrocarbon group of 1 to 50 carbon atoms containing a phenol moiety, a substituent such as a hydroxyl group, a halogen group, an alkoxyl group or an amino group, and a hydrocarbon group of 1 to 50 carbon atoms containing a phenol structure.
- R 4 represents a hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms containing a substituent such as a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
- R 2 and R 3 each independently represent hydrogen, a hydrocarbon group of 1 to 50 carbon atoms, a hydrocarbon group of 1 to 50 carbon atoms containing a substituent such as a hydroxyl group or an alkoxyl group.
- the hydrocarbon group may contain a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl. The ends of R 2 and R 4 may be bonded together.
- Phosphorus compounds having a phosphorus element and a phenol structure in the same molecule include, for example, p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, diphenyl p-hydroxyphenylphosphonate, bis (p-hydroxyphenyl)phosphinic acid, methyl bis(p-hydroxyphenyl)phosphinate, phenyl bis(p-hydroxyphenyl)phosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, p-hydroxyphenyl and phenyl phosphinate.
- a phosphorus element and a hindered phenol structure an alkyl group having a tertiary carbon (preferably a t-butyl group, thexyl An alkyl group having a tertiary carbon such as a group at the benzylic position; a neopentyl group, etc.) is bonded to one or two ortho positions of a hydroxyl group).
- the phosphorus compound used in the production of the recycled polyester resin (D) is preferably dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate represented by the following (chemical formula B),
- modified forms of dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate may also be included. Details of the modified product will be described later.
- X 1 and X 2 each represent hydrogen and an alkyl group having 1 to 4 carbon atoms.
- a polyester resin in which at least one hindered phenol structure can be detected by the P-NMR measurement method of a solution dissolved in a hexafluoroisopropanol-based solvent is referred to as "having a hindered phenol structure.” That is, the recycled polyester resin (D) is preferably a polyester resin produced using a phosphorus compound having a phosphorus element and a hindered phenol structure in the same molecule as a polymerization catalyst. A method for detecting the hindered phenol structure in the recycled polyester resin (D) (P-NMR measurement method) will be described later.
- both X 1 and X 2 are preferably alkyl groups having 1 to 4 carbon atoms, more preferably alkyl groups having 1 to 2 carbon atoms.
- the ethyl ester having 2 carbon atoms is preferable because Irganox 1222 (manufactured by BASF) is commercially available and easily available.
- the phosphorus compound after heat-treating it in a solvent. Details of the heat treatment will be described later.
- the phosphorus compound when dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, which is the phosphorus compound shown in the above (Chemical Formula B), is used, in the above heat treatment, the reaction shown in (Chemical Formula B) A part of dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, which is a phosphorus compound, undergoes a structural change.
- the phosphorus compound includes structurally modified phosphorus compounds in addition to dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate represented by (Chemical Formula B).
- elimination of the t-butyl group remarkably occurs at high temperature in the polymerization process.
- diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate when diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate is used as the phosphorus compound, part of diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate has the structure Nine phosphorus compounds that have been altered are shown. The component amount of each structurally-changed phosphorus compound in the glycol solution can be quantified by the P-NMR measurement method.
- 3,5-di-tert-butyl-4-hydroxybenzylphosphonate 3,5-di-tert-butyl-4-hydroxy 3,5-di-tert-butyl-4-hydroxy compounds represented by the above nine chemical formulas can be used as phosphorus compounds in the present invention.
- Modified dialkyl benzylphosphonates may also be included.
- the polyester resin contains 9 types of phosphorus compound residues shown in Table 1 below.
- the recycled polyester resin (D) has a phosphorus element and a hindered phenol structure in the same molecule. It can be said that it is a polyester resin produced by using a phosphorus compound having and as a polymerization catalyst. By using a phosphorus compound having a hindered phenol structure, sufficient polymerization activity can be exhibited while suppressing the cost of the catalyst.
- the content of the phosphorus element in the recycled polyester resin (D) is preferably 3 to 1000 mass ppm, more preferably 5 to 500 mass ppm, even more preferably 10 to 200 mass ppm. ⁇ 100 ppm by weight is particularly preferred, and 30 to 80 ppm by weight is most preferred. If the elemental phosphorus content is less than 3 ppm by mass, the polymerization activity may decrease and the amount of aluminum-based contaminants may increase. On the other hand, if it exceeds 1000 ppm by mass, there is a possibility that the polymerization activity may be lowered and the added amount of the phosphorus compound may be increased, resulting in an increase in catalyst cost.
- the molar ratio of the phosphorus element to the aluminum element is preferably 0.60 to 5.00, and preferably 0.75 to It is more preferably 4.00, still more preferably 0.80 to 3.50, and particularly preferably 0.90 to 3.00.
- the aluminum element and the phosphorus element in the recycled polyester resin (D) are respectively derived from the aluminum compound and the phosphorus compound used as the polymerization catalyst for the recycled polyester resin (D).
- the resin produced using a polymerization catalyst consisting of an aluminum compound and a phosphorus compound has a higher catalyst cost (higher production cost) than a polyester resin produced using a catalyst such as an antimony catalyst.
- a catalyst such as an antimony catalyst.
- the aluminum compound and the phosphorus compound together in a specific ratio it is possible to exhibit sufficient polymerization activity while suppressing the cost of the catalyst, and further suppress the coloring of the recycled polyester resin (D).
- the residual molar ratio of elemental phosphorus to elemental aluminum is less than 0.60, the thermal stability and thermal oxidation stability may decrease, and the amount of aluminum-based contaminants may increase.
- the residual molar ratio of elemental phosphorus to elemental aluminum exceeds 5.00, the amount of the phosphorus compound added becomes too large, which may increase the catalyst cost.
- the polymerization catalyst (polymerization catalyst added to the intermediate) used in the production of the recycled polyester resin (D) in addition to the aluminum compound and phosphorus compound described above, other polymerization catalysts such as antimony compounds, germanium compounds, and titanium compounds are used.
- the recycled polyester resin (D) may be used in combination within a range that does not cause problems in the properties, workability, color tone, etc. of the product.
- the amounts of antimony element, germanium element, and titanium element added to the intermediate are preferably 3 ppm by mass or less. However, it is preferable not to use the above other polycondensation catalysts as much as possible.
- the method for producing the recycled polyester resin (D) of the present invention includes mixing the recovered polyester resin (A), the polyhydric carboxylic acid (B), and the polyhydric alcohol (C) to depolymerize and It has a first step of esterification and a second step of further polycondensing the reaction product of the first step to increase the molecular weight.
- the amount of the reactant (lower condensate) obtained in the first step is the total amount of the polyester resin (A), the polyhydric carboxylic acid (B), and the polyhydric alcohol (C), and the reactant is sometimes called an "intermediate".
- the content of the aluminum compound in the recycled polyester resin (D) is 5 to 100 mass ppm in terms of aluminum element (2)
- the content of the phosphorus compound in the recycled polyester resin (D) is 3 to 1000 ppm by mass in terms of phosphorus element (3)
- the residual molar ratio of the phosphorus element to the aluminum element in the recycled polyester resin (D) is 0.60 or more and 5.00 or less
- the recovered polyester resin (A), polycarboxylic acid (B), and polyhydric alcohol (C) are mixed to obtain the polyester resin (A), polycarboxylic acid (B), and polyhydric alcohol (B).
- the polyhydric alcohol (C) By putting the polyhydric alcohol (C) in the same container, while depolymerizing the polyester resin (A), the depolymerized polyester or its oligomer, the polyhydric carboxylic acid (B) and the polyhydric alcohol (C) are used for esterification to form intermediates.
- depolymerization is preferably carried out under pressurized conditions, and the pressure is preferably 0.1 to 0.4 MPa.
- the amount (mass) of the recycled polyester resin (D) to be produced can be calculated from the masses of the polyester resin (A), the polycarboxylic acid (B), and the polyhydric alcohol (C).
- the solution S in which the aluminum compound is dissolved it is preferable to add to the intermediate after the first step and before the second step. Further, when the polycondensation in the second step is performed in the presence of an aluminum compound and a phosphorus compound, a solution S in which an aluminum compound is dissolved in the intermediate after the first step and before the second step It is preferable to add a solution T in which a phosphorus compound is dissolved.
- Polyvalent carboxylic acids and ester-forming derivatives thereof, hydroxycarboxylic acids that may be added in small amounts and ester-forming derivatives thereof, and cyclic esters that may be added in small amounts used in the production of the recycled polyester resin (D) are polymerized Since almost 100% of the amount initially added to the system as a catalyst remains in the recycled polyester resin (D) produced by polymerization, from these charged amounts The mass of "produced recycled polyester resin (D)" can be calculated.
- aluminum compounds and phosphorus compounds are used as catalysts, they are preferably added in the form of a slurry or a solution, more preferably a solution dissolved in a solvent such as water or glycol, and a solution dissolved in water and/or glycol is used. more preferably, and most preferably a solution in ethylene glycol is used.
- the content (residual amount) of the solution S in which the aluminum compound is dissolved and the solution T in which the phosphorus compound is dissolved in the recycled polyester resin (D) at any stage up to the start of the polymerization reaction in the manufacturing process of the recycled polyester resin (D) is preferably added so as to satisfy the above (1) to (3).
- the amount of aluminum element to be added to the intermediate should be 5 to 100 mass ppm, preferably 7 to 60 mass ppm, more preferably 10 to 50 mass ppm, and still more preferably 12 to 40 mass ppm.
- the amount of phosphorus element added to the intermediate is preferably 5 to 1500 mass ppm.
- the content of phosphorus element in the recycled polyester resin (D) can be 3 to 1000 ppm by mass.
- the amount of elemental phosphorus added to the reactant in the first step is more preferably 10 to 500 mass ppm, still more preferably 20 to 200 mass ppm, and particularly preferably 30 to 150 mass ppm.
- the molar ratio of the added amount of phosphorus element to the added amount of aluminum atoms is preferably 1.00 to 7.00, more preferably 1.50 to 6.00, and more preferably 2.00 to 5.00. 00 is more preferred.
- the solution S in which the aluminum compound is dissolved and the solution T in which the phosphorus compound is dissolved it is a more preferable embodiment to prepare a mixed liquid by mixing in and add the one-liquid mixed liquid to the intermediate.
- the method of making one solution in advance include a method of mixing the respective solutions in a tank, a method of joining the pipes to which the catalyst is added in the middle and mixing the solutions, and the like.
- the solution S in which the aluminum compound is dissolved and the solution T in which the phosphorus compound is dissolved are added to the intermediate after the first step and before the second step, from the viewpoint of suppressing the amount of aluminum-based foreign matter. It is preferable to add the solution S in which the compound is dissolved and the solution T in which the phosphorus compound is dissolved. Further, the solution S in which the aluminum compound is dissolved is preferably a glycol solution in which the aluminum compound is dissolved, and the solution T in which the phosphorus compound is dissolved is preferably a glycol solution in which the phosphorus compound is dissolved.
- the phosphorus compound used for producing the recycled polyester resin (D) is preferably heat-treated in a solvent.
- the solvent to be used is not limited as long as it is at least one selected from the group consisting of water and alkylene glycol.
- alkylene glycol it is preferable to use a solvent that dissolves a phosphorus compound, and a polyester resin such as ethylene glycol ( It is more preferable to use glycol as a component of B).
- the heat treatment in the solvent is preferably performed after dissolving the phosphorus compound, but it does not have to be completely dissolved.
- the heat treatment temperature is preferably 170 to 196°C, more preferably 175 to 185°C, and still more preferably 175 to 180°C.
- the heat treatment time is preferably 30 to 240 minutes, more preferably 50 to 210 minutes.
- the concentration of the phosphorus compound during the heat treatment is preferably 3 to 10% by mass.
- the acidity of the phosphorus compound contained in the glycol solution can be made constant, the polymerization activity is improved by using it together with the aluminum compound, and the amount of aluminum-based foreign matter caused by the polymerization catalyst is suppressed.
- the amount of the phosphorus compound distilled off in the polymerization process can be suppressed, and the economic efficiency can be improved. Therefore, it is preferable to perform the above heat treatment.
- Apparatus Fourier transform nuclear magnetic resonance apparatus (BRUKER, AVANCE NEO600) 1H resonance frequency: 600.13MHz Lock solvent: heavy chloroform Flip angle: 30° Data acquisition time: 4 seconds Delay time: 1 second Measurement temperature: 30°C Accumulated times: 128 times
- Acid value Recycled polyester resin (a) described later or 20 mg of a sample was dissolved in 0.6 ml of a mixed solvent in which heavy hexafluoroisopropanol and heavy chloroform were mixed at a ratio of 1:9 (volume ratio), and centrifuged. . After that, the supernatant was collected, and after adding 35 ⁇ L of a mixed solvent in which triethylamine was mixed with heavy chloroform so as to have a concentration of 0.2 mol/L, H-NMR measurement was performed under the following conditions.
- Apparatus Fourier transform nuclear magnetic resonance apparatus (BRUKER, AVANCE NEO600) 1H resonance frequency: 600.13MHz Lock solvent: heavy chloroform Flip angle: 30° Data acquisition time: 4 seconds Delay time: 1 second Measurement temperature: 30°C Accumulated times: 128 times
- Measurement method JIS Z8722 compliant Transmitted light 0 degree, -0 degree method
- Detection element Silicon photodiode array
- Light source Halogen lamp 12V100W 2000H
- Measurement area transmission 25mm ⁇ Humidity and temperature conditions: 25°C, RH50%
- Measurement cell ⁇ 35mm, height 25mm
- rotary type (pellet) Measurement details: X, Y, Z tristimulus values
- recovered polyester resin (a) As the recovered polyester resin (a) (hereinafter referred to as recycled polyester resin (a)), recovered polyester resin flakes provided by Kyoei Sangyo Co., Ltd. were used. As a result of composition analysis, the recovered polyester resin flakes contained 98 mol % of terephthalic acid and 2 mol % of isophthalic acid as polyvalent carboxylic acid components, and 98 mol % of ethylene glycol as polyhydric alcohol components. It was confirmed that 2 mol % of diethylene glycol was contained. The recovered polyester resin flakes had an intrinsic viscosity of 0.750 dl/g and a glass transition temperature of 76°C.
- the content of antimony in the recovered polyester resin flakes was 200 mass ppm, and the content of germanium and titanium was less than 1 mass ppm. From the contents of the elements antimony, germanium, and titanium, it can be confirmed that the recovered polyester resin flakes are mainly composed of hollow moldings using a polyester resin produced with an antimony catalyst. rice field.
- recovered polyester resin (b) As the recovered polyester resin (b) (hereinafter referred to as "recycled polyester resin (b)"), recovered polyester resin pellets obtained by recovering waste films from polyethylene naphthalate film production and re-pelletizing were used. As a result of composition analysis, the recovered polyester resin pellets contained 100 mol% of naphthalene dicarboxylic acid as the polyvalent carboxylic acid component, and 98 mol% of ethylene glycol and 2 mol% of diethylene glycol as the polyhydric alcohol component. I confirmed that The recovered polyester resin pellets had an intrinsic viscosity of 0.520 dl/g and a glass transition temperature of 118°C. In addition, the content of antimony in the recovered polyester resin pellets was 200 mass ppm, and the content of germanium and titanium was less than 1 mass ppm.
- Example 1 375.5 g of high-purity terephthalic acid, 333.0 g of ethylene glycol, and 39.8 g of recycled polyester resin (a) were added all at once to a 2 L stainless steel autoclave equipped with a stirrer, and the temperature was raised to 260° C. under a pressurized atmosphere of 0.25 MPa. Then, a polyester oligomer having an esterification rate of 90% was obtained. The resulting oligomer was transparent and had an acid value of 705 eq/ton and a hydroxyl value of 1860 eq/ton.
- the mixed solution was prepared so that the aluminum element and the phosphorus element were 14 mass ppm and 30 mass ppm, respectively, relative to the weight of the oligomer.
- the added molar ratio of elemental phosphorus to elemental aluminum was 1.87.
- the amount of the recycled polyester resin (d-1) to be produced can be calculated from the amounts of terephthalic acid and PET resin to be added.
- the mixed liquid is added so that the aluminum element and the phosphorus element are 14 mass ppm and 30 mass ppm, respectively.
- a recycled polyester resin (d-1) having an acid value of 8 eq/ton was obtained.
- the residual amount of aluminum element in the recycled polyester resin (d-1) was 14 mass ppm, the residual amount of phosphorus element was 20 mass ppm, and the residual molar ratio of phosphorus element to aluminum element was 1.25.
- the recycled polyester resin (d-1) had an L value of 59.0, a b value of 5.3, and a glass transition temperature of 76°C.
- Example 2 to 5 Comparative Example 1, Reference Example 1 Recycled polyester resins (d-2) to (d-5) and (d'-1) were prepared in the same manner as in Example 1, except that the amount of the recycled polyester resin (a) was changed to the amount shown in Table 2. got However, in Comparative Example 1, the ratio of the recycled polyester resin (a) was too high, so the recycled polyester resin could not be produced. Moreover, in Example 5, 10 mol % of the glycol component to be added was changed to diethylene glycol in addition to the above changes.
- Example 6 249.0 g of naphthalene dicarboxylic acid, 340.0 g of ethylene glycol, and 90.0 g of recycled polyester resin (b) were added all at once to a 2 L stainless steel autoclave equipped with a stirrer, and the temperature was raised to 260° C. in a pressurized atmosphere of 0.25 MPa. , a transparent polyester oligomer A was obtained. Thereafter, 106.8 g of naphthalene dicarboxylic acid was added, and additional treatment was performed under a pressure atmosphere of 0.25 MPa to obtain polyester oligomer B having an esterification rate of 90%.
- Polyester oligomer B was transparent and had an acid value of 650 eq/ton and a hydroxyl value of 1430 eq/ton.
- a mixed liquid obtained by mixing the aluminum-containing ethylene glycol solution s and the phosphorus-containing ethylene glycol solution t prepared by the above method to form a one-liquid mixture.
- the mixed solution was prepared so that the aluminum element and the phosphorus element were 30 mass ppm and 74 mass ppm, respectively, relative to the weight of the oligomer.
- the added molar ratio of elemental phosphorus to elemental aluminum was 2.15.
- the amount of the recycled polyester resin (d-7) to be produced can be calculated from the amount of the naphthalene dicarboxylic acid and the PEN resin to be added.
- the mixed liquid is added so that the aluminum element and the phosphorus element are 30 mass ppm and 74 mass ppm, respectively. After that, the temperature of the system was raised to 290° C. in 1 hour, and the pressure of the system was gradually reduced to 0.15 kPa during this time.
- a recycled polyester resin (d-7) having an acid value of 33 eq/ton was obtained.
- the residual amount of aluminum element in the recycled polyester resin (d-7) was 30 mass ppm, the residual amount of phosphorus element was 54 mass ppm, and the residual molar ratio of phosphorus element to aluminum element was 1.56.
- the recycled polyester resin (d-7) had an L value of 62.2, a b value of 6.2, and a glass transition temperature of 118°C.
- Comparative Example 1 the ratio of the recycled polyester resin (a) was too high, so it was incompatible.
- Comparative Example 2 since an antimony catalyst was used, the L value was lower than in Examples 1 to 5, and the regenerated polyester resin (d-6) was markedly colored.
- Example 6 ⁇ When recycled polyester resin (b) is used> In Example 6, since the recycled polyester resin (b) and the aluminum catalyst are used in a predetermined ratio in the manufacturing process, the L value, which is a measure of darkening, remains high, and the b value, which is a measure of yellowness, remains high. It was possible to obtain a recycled polyester resin (d-7) in which the was still low.
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Abstract
Description
1.再生ポリエステル樹脂の製造方法であって、回収されたポリエステル樹脂(A)、多価カルボン酸(B)、及び多価アルコール(C)を混合して、解重合及びエステル化する第1工程と、第1工程の反応物をさらに重縮合して高分子量化する第2工程とを有し、前記ポリエステル樹脂(A)の割合は、前記再生ポリエステル100質量部に対し、5~80質量部であり、前記第2工程における重縮合はアルミニウム化合物の存在下で行われ、前記アルミニウム化合物は前記反応物に対してアルミニウム元素換算で5~100質量ppmであることを特徴とする再生ポリエステル樹脂の製造方法。
2.前記第2工程における重縮合がリン化合物の存在下で行われ、前記リン化合物が前記反応物に対してリン元素換算で3~1000質量ppmである上記1.に記載の再生ポリエステル樹脂の製造方法。
3.前記リン化合物が、同一分子内にリン元素とフェノール構造を有する化合物である上記2.に記載の再生ポリエステル樹脂の製造方法。
4.前記ポリエステル樹脂(A)が、芳香族ジカルボン酸に由来のジカルボン酸単位と炭素数2~6のアルキレングリコールに由来のジオール単位とを有する上記1.~3.のいずれかに記載の再生ポリエステル樹脂の製造方法。
5.前記ポリエステル樹脂(A)が、アンチモン、チタン、及びゲルマニウムから選ばれる少なくとも一種の元素を含む上記1.~4.のいずれかに記載の再生ポリエステル樹脂の製造方法。
6.前記ポリエステル樹脂(A)中におけるアンチモン元素、チタン元素、及びゲルマニウム元素の合計の含有量が2~500質量ppmである上記5.に記載の再生ポリエステル樹脂の製造方法。
ポリエステル樹脂(A)は使用済みのポリエステル樹脂及び/又はポリエステル製品を製造する工程で発生する未採用のポリエステル樹脂が回収されたものである。ポリエステル樹脂(A)は、多価カルボン酸およびそのエステル形成性誘導体から選ばれる少なくとも一種と多価アルコールおよびそのエステル形成性誘導体から選ばれる少なくとも一種により形成された重合体である。
多価カルボン酸(B)及び多価アルコール(C)としては、上述するポリエステル樹脂(A)に記載の成分が使用可能である。多価カルボン酸(B)は、ポリエステル樹脂(A)を構成する主たる多価カルボン酸成分を70モル%以上含むことが好ましく、80モル%以上含むことがより好ましく、90モル%以上含むことがさらに好ましい。多価アルコール(C)は、ポリエステル樹脂(A)を構成する主たる多価アルコール成分を70モル%以上含むことが好ましく、80モル%以上含むことがより好ましく、90モル%以上含むことがさらに好ましく、95モル%以上含むことが特に好ましい。
再生ポリエステル樹脂(D)の固有粘度は0.50~0.90dl/gであることが好ましく、0.55~0.80dl/gであることがより好ましい。再生ポリエステル樹脂(D)の固有粘度が0.50dl/g未満である場合は、再生ポリエステル樹脂(D)の機械的強度や耐衝撃性が不十分になるおそれがある。一方で、再生ポリエステル樹脂(D)の固有粘度が0.90dl/gを超えた場合は、経済性が低下するおそれがある。
再生ポリエステル樹脂(D)の重合触媒を構成するアルミニウム化合物は溶媒に溶解するものであれば限定されず、公知のアルミニウム化合物が限定なく使用できる。アルミニウム化合物として、例えば、ギ酸アルミニウム、酢酸アルミニウム、塩基性酢酸アルミニウム、プロピオン酸アルミニウム、シュウ酸アルミニウム、アクリル酸アルミニウム、ラウリン酸アルミニウム、ステアリン酸アルミニウム、安息香酸アルミニウム、トリクロロ酢酸アルミニウム、乳酸アルミニウム、クエン酸アルミニウム、酒石酸アルミニウム、サリチル酸アルミニウムなどのカルボン酸塩;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、硝酸アルミニウム、硫酸アルミニウム、炭酸アルミニウム、リン酸アルミニウム、ホスホン酸アルミニウムなどの無機酸塩;アルミニウムメトキサイド、アルミニウムエトキサイド、アルミニウムn-プロポキサイド、アルミニウムイソプロポキサイド、アルミニウムn-ブトキサイド、アルミニウムt-ブトキサイドなどアルミニウムアルコキサイド;アルミニウムアセチルアセトネート、アルミニウムエチルアセトアセテート、アルミニウムエチルアセトアセテートジiso-プロポキサイドなどのキレート化合物;トリメチルアルミニウム、トリエチルアルミニウムなどの有機アルミニウム化合物およびこれらの部分加水分解物、アルミニウムのアルコキサイドやアルミニウムキレート化合物とヒドロキシカルボン酸からなる反応生成物、酸化アルミニウム、超微粒子酸化アルミニウム、アルミニウムシリケート、アルミニウムとチタンやケイ素やジルコニウムやアルカリ金属やアルカリ土類金属などとの複合酸化物などが挙げられる。これらのうちカルボン酸塩、無機酸塩、およびキレート化合物から選ばれる少なくとも1種が好ましく、これらの中でも酢酸アルミニウム、塩基性酢酸アルミニウム、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、及びアルミニウムアセチルアセトネートから選ばれる少なくとも1種がより好ましく、酢酸アルミニウム、塩基性酢酸アルミニウム、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、及びアルミニウムアセチルアセトネートから選ばれる少なくとも1種がさらに好ましく、酢酸アルミニウム及び塩基性酢酸アルミニウムから選ばれる少なくとも1種が特に好ましく、塩基性酢酸アルミニウムが最も好ましい。
再生ポリエステル樹脂(D)の重合触媒を構成するリン化合物としては、特に限定はされないが、ホスホン酸系化合物、ホスフィン酸系化合物を用いると触媒活性の向上効果が大きいため好ましく、これらの中でもホスホン酸系化合物を用いると触媒活性の向上効果が特に大きいためより好ましい。
次に、再生ポリエステル樹脂(D)の製造方法について説明する。上述のとおり、本発明の再生ポリエステル樹脂(D)の製造方法は、回収されたポリエステル樹脂(A)、多価カルボン酸(B)、及び多価アルコール(C)を混合して、解重合及びエステル化する第1工程と、第1工程の反応物をさらに重縮合して高分子量化する第2工程とを有する。なお、第1工程により得られる反応物(低次縮合物)の量は、ポリエステル樹脂(A)、多価カルボン酸(B)、及び多価アルコール(C)の合計量であり、前記反応物のことを「中間体」ということがある。下記(1)を満たしていればよく、下記(1)の他に下記(2)と(3)の少なくとも一方を満たすことが好ましく、下記(1)~(3)を全て満たすことがより好ましい。
(1)再生ポリエステル樹脂(D)中におけるアルミニウム化合物の含有量がアルミニウム元素換算で5~100質量ppm
(2)再生ポリエステル樹脂(D)中におけるリン化合物の含有量がリン元素換算で3~1000質量ppm
(3)再生ポリエステル樹脂(D)中におけるアルミニウム元素に対するリン元素の残存モル比が0.60以上5.00以下
なお、反応容器に添加する場合には、反応容器の撹拌を高くすることが好ましい。反応容器間の配管に添加する場合には、インラインミキサーなどを設置して、添加された触媒溶液が速やかに均一混合されるようにすることが好ましい。
アルミニウム化合物を溶解した溶液Sとリン化合物を溶解した溶液Tとを別々に添加した場合、アルミニウム化合物に起因する異物が多く発生しやすく、昇温結晶化温度が低くなったり、降温結晶化温度が高くなったり、十分な触媒活性が得られなくなる場合がある。アルミニウム化合物とリン化合物を同時に添加することで、重合活性をもたらすアルミニウム化合物とリン化合物の複合体が速やかに無駄なく生成できるが、別々に添加した場合には、アルミニウム化合物とリン化合物の複合体の生成が不十分であり、また、リン化合物との複合体を生成できなかったアルミニウム化合物が異物として析出するおそれがある。
また、アルミニウム化合物を溶解した溶液Sとリン化合物を溶解した溶液Tとは、アルミニウム系異物量を抑制する観点から、前記第1工程後であって前記第2工程の前に前記中間体にアルミニウム化合物を溶解した溶液Sとリン化合物を溶解した溶液Tを添加することが好ましい。また、アルミニウム化合物を溶解した溶液Sは、アルミニウム化合物を溶解したグリコール溶液であることが好ましく、リン化合物を溶解した溶液Tは、リン化合物を溶解したグリコール溶液であることが好ましい。
再生ポリエステル樹脂(D)の製造に使用するリン化合物は溶媒中で熱処理されたものであることが好ましい。使用する溶媒としては、水およびアルキレングリコールからなる群から選ばれる少なくとも1種であれば限定されないが、アルキレングリコールとしては、リン化合物を溶解する溶媒を用いることが好ましく、エチレングリコール等のポリエステル樹脂(B)の構成成分であるグリコールを用いることがより好ましい。溶媒中での加熱処理は、リン化合物を溶解してから行うのが好ましいが、完全に溶解していなくてもよい。
(1)リサイクルポリエステル樹脂(a)の組成分析
後述するリサイクルポリエステル樹脂(a)20mgを重ヘキサフルオロイソプロパノールと重クロロホルムとを1:9(容量比)で混ぜた混合溶媒0.6mlに溶解し、遠心分離を行った。その後、上澄み液を採取し、重クロロホルムにトリエチルアミンが0.2mol/Lとなるように混合した混合溶媒35μLを添加した後、下記の条件でH-NMR測定を行った。
装置:フーリエ変換核磁気共鳴装置(BRUKER社製、AVANCE NEO600)
1H共鳴周波数:600.13MHz
ロック溶媒:重クロロホルム
フリップ角:30°
データ取り込み時間:4秒
遅延時間:1秒
測定温度:30℃
積算回数:128回
白金製るつぼにリサイクルポリエステル樹脂(a)を秤量し、電気コンロでの炭化の後、マッフル炉で550℃、8時間の条件で灰化した。灰化後のサンプルを1.2M塩酸に溶解し、試料溶液とした。調製した試料溶液を下記の条件で測定し、高周波誘導結合プラズマ発光分析法によりリサイクルポリエステル樹脂(a)中におけるアンチモン元素、ゲルマニウム元素、及びチタン元素の濃度を求めた。同様に後述する各実施例及び比較例で得られる再生ポリエステル樹脂(d-1)~(d-6)並びに各参考例で得られるポリエステル樹脂(d’-1)~(d’-2)中におけるアンチモン元素、ゲルマニウム元素、及びチタン元素の濃度を求め、表2に記載した。なお、含有量が1質量ppm未満である元素については記載を省略した。
装置:SPECTRO社製 CIROS-120
プラズマ出力:1400W
プラズマガス:13.0L/min
補助ガス:2.0L/min
ネブライザー:クロスフローネブライザー
チャンバー:サイクロンチャンバー
測定波長:167.078nm
各実施例及び比較例で得られる再生ポリエステル樹脂(d)並びに各参考例で得られるポリエステル樹脂(d’)を試料とし、試料を硫酸、硝酸、過塩素酸で湿式分解を行った後、アンモニア水で中和した。調製した溶液にモリブデン酸アンモニウムおよび硫酸ヒドラジンを加えた後、紫外可視吸光光度計(島津製作所社製、UV-1700)を用いて、波長830nmでの吸光度を測定した。あらかじめ作製した検量線から、試料中のリン元素の濃度を求めた。なお、以下の測定方法では、試料とは各実施例及び比較例で得られる再生ポリエステル樹脂(d-1)~(d-7)並びに各参考例で得られるポリエステル樹脂(d’-1)~(d’-2)のことを指す。
試料またはそのプリフォームを約3g凍結粉砕して140℃15分間乾燥した後、0.20g計量し、1,1,2,2-テトラクロロエタンとp-クロロフェノールとを1:3(質量比)で混ぜた混合溶媒を20ml用いて100℃で60分間撹拌して完全に溶解して室温まで冷却した後グラスフィルターを通して溶液を準備した。30℃に温調されたウベローデ粘度計(離合社製)を用いて上記溶液および溶媒の落下時間を計測し、固有粘度及び還元粘度を測定した。なお、固有粘度は以下の式により算出することもできる。
[η]=(-1+√(1+4K’ηSp))/2K’C
ηSp=(τ-τ0)τ0
ここで、
[η]:固有粘度(dl/g)
ηSp:比粘度(-)
K’:ハギンスの恒数(=0.33)
C:濃度(=1g/dl)
τ:試料の落下時間(sec)
τ0:溶媒の落下時間(sec)
後述するリサイクルポリエステル樹脂(a)又は試料20mgを重ヘキサフルオロイソプロパノールと重クロロホルムとを1:9(容量比)で混ぜた混合溶媒0.6mlに溶解し、遠心分離を行った。その後、上澄み液を採取し、重クロロホルムにトリエチルアミンが0.2mol/Lとなるように混合した混合溶媒35μLを添加した後、下記の条件でH-NMR測定を行った。
装置:フーリエ変換核磁気共鳴装置(BRUKER社製、AVANCE NEO600)
1H共鳴周波数:600.13MHz
ロック溶媒:重クロロホルム
フリップ角:30°
データ取り込み時間:4秒
遅延時間:1秒
測定温度:30℃
積算回数:128回
セイコー電子工業社製の示差走査熱量分析計「DSC220型」にて、後述するリサイクルポリエステル樹脂(a)又は試料5mgをアルミパンに入れ、蓋を押さえて密封した。次いで、一度250℃で5分ホールドした後、液体窒素で急冷して、その後-100℃から250℃まで、20℃/minの昇温速度で測定した。得られた曲線においての図1に示したようなDSCで変極点が表れる部分の変極点前のベースラインから得られる接線(1)と変極点後のベースラインから得られる接線(2)の交点(図内丸印)をガラス転移温度とした。
試料の非晶ペレットを測定セルに詰め込み(約50g)回転させながら測定を実施した。
装置:東京電色社製 精密型分光光度色彩計TC-1500SX
測定方法:JIS Z8722準拠 透過光 0度、-0度法
検出素子:シリコンフォトダイオードアレー
光源:ハロゲンランプ 12V100W 2000H
測定面積:透過25mmφ
湿温度条件:25℃、RH50%
測定セル:φ35mm、高さ25mm 回転式(ペレット)
測定内容:X,Y,Z3刺激値 CIE色度座標 x=X/X+Y+Z y=Y/X+Y+Z
ハンターLab表色系
塩基性酢酸アルミニウムの20g/L水溶液に対して、等量(容量比)のエチレングリコールをともに調合タンクに仕込み、室温(23℃)で数時間撹拌した後、減圧(3kPa)下、50~90℃で数時間撹拌しながら系から水を留去し、アルミニウム化合物が20g/L含まれたアルミニウム含有エチレングリコール溶液sを調製した。
リン化合物として、Irganox1222(ビーエーエスエフ社製)を、エチレングリコールとともに調合タンクに仕込み、窒素置換下撹拌しながら175℃で150分熱処理し、リン化合物が50g/L含まれたリン含有エチレングリコール溶液tを調製した。
回収されたポリエステル樹脂(a)(以下、リサイクルポリエステル樹脂(a)という)として、協栄産業株式会社より提供された回収ポリエステル樹脂フレークを用いた。該回収ポリエステル樹脂フレークは、組成分析の結果、多価カルボン酸成分は、テレフタル酸が98モル%、イソフタル酸が2モル%含まれており、多価アルコール成分は、エチレングリコールが98モル%、ジエチレングリコールが2モル%含まれていること確認した。該回収ポリエステル樹脂フレークの固有粘度は0.750dl/g、ガラス転移温度は76℃であった。また、上記回収ポリエステル樹脂フレーク中におけるアンチモン元素の含有率は200質量ppm、ゲルマニウム元素の含有率及びチタン元素の含有率は1質量ppm未満であった。アンチモン、ゲルマニウム、チタンの各元素の含有率から、上記回収ポリエステル樹脂フレークは、アンチモン触媒で製造されたポリエステル樹脂を用いた中空成形体を主体とした回収ポリエステル樹脂フレークであることを裏付けることができた。
回収されたポリエステル樹脂(b)(以下、リサイクルポリエステル樹脂(b)という)として、ポリエチレンナフタレートフィルム製造時の屑フィルムを回収し、再度ペレタイズした回収ポリエステル樹脂ペレットを用いた。該回収ポリエステル樹脂ペレットは、組成分析の結果、多価カルボン酸成分は、ナフタレンジカルボン酸が100モル%含まれており、多価アルコール成分は、エチレングリコールが98モル%、ジエチレングリコールが2モル%含まれていること確認した。該回収ポリエステル樹脂ペレットの固有粘度は0.520dl/g、ガラス転移温度は118℃であった。また、上記回収ポリエステル樹脂ペレット中におけるアンチモン元素の含有率は200質量ppm、ゲルマニウム元素の含有率及びチタン元素の含有率は1質量ppm未満であった。
撹拌機付き2Lステンレス製オートクレーブに、高純度テレフタル酸375.5gとエチレングリコール333.0gとリサイクルポリエステル樹脂(a)39.8gとを一括で加え、0.25MPa加圧雰囲気で260℃まで昇温し、エステル化率が90%のポリエステルオリゴマーを得た。得られたオリゴマーは透明であり、酸価が705eq/ton、水酸基価が1860eq/tonであった。
得られたオリゴマーに、上記方法で調製したアルミニウム含有エチレングリコール溶液sおよびリン含有エチレングリコール溶液tを混合し一液化した混合液を添加した。該混合液は、それぞれオリゴマーの質量に対して、アルミニウム元素およびリン元素として14質量ppmおよび30質量ppmとなるように作製した。アルミニウム元素に対するリン元素の添加モル比は1.87であった。なお、生成される再生ポリエステル樹脂(d-1)の量は、添加するテレフタル酸及びPET樹脂の量より算出可能であり、本実施例では、生成される再生ポリエステル樹脂(d-1)500gに対してアルミニウム元素およびリン元素として14質量ppmおよび30質量ppmとなるように混合液が添加されている。
その後、1時間で系の温度を280℃まで昇温して、この間に系の圧力を徐々に減じて0.15kPaとし、この条件下で重縮合反応を行い、IVが0.59dl/g、酸価が8eq/tonの再生ポリエステル樹脂(d-1)を得た。再生ポリエステル樹脂(d-1)におけるアルミニウム元素の残存量は14質量ppm、リン元素の残存量は20質量ppm、アルミニウム元素に対するリン元素の残存モル比は1.25であった。再生ポリエステル樹脂(d-1)のL値は59.0であり、b値は5.3、ガラス転移温度は76℃であった。
リサイクルポリエステル樹脂(a)の量を表2に記載の量に変更した以外は、実施例1と同様の方法で再生ポリエステル樹脂(d-2)~(d-5)、(d’-1)を得た。ただし、比較例1では、リサイクルポリエステル樹脂(a)の割合が高すぎるため、再生ポリエステル樹脂を作製することができなかった。また、実施例5では、上記変更の他に、添加するグリコール成分のうち、10モル%をジエチレングリコールに変更した。
アルミニウム含有エチレングリコール溶液sおよびリン含有エチレングリコール溶液tを添加する代わりに、生成される再生ポリエステル樹脂(d-6)500gに対してアンチモン元素として300質量ppmとなるようにアンチモン触媒を添加する以外は、実施例1と同様の方法で再生ポリエステル樹脂(d-6)を得た。
アルミニウム含有エチレングリコール溶液sおよびリン含有エチレングリコール溶液tを添加する代わりに、生成される再生ポリエステル樹脂(d’-2)500gに対してアンチモン元素として250質量ppmとなるようにアンチモン触媒を添加する以外は、参考例1と同様の方法で再生ポリエステル樹脂(d’-2)を得た。
撹拌機付き2Lステンレス製オートクレーブに、ナフタレンジカルボン酸249.0gとエチレングリコール340.0gとリサイクルポリエステル樹脂(b)90.0gとを一括で加え、0.25MPa加圧雰囲気で260℃まで昇温し、透明なポリエステルオリゴマーAを得た。その後、ナフタレンジカルボン酸を106.8g添加し、0.25MPa加圧雰囲気下で追加処理し、エステル化率90%の得られたポリエステルオリゴマーBを得た。ポリエステルオリゴマーBは透明であり、酸価が650eq/ton、水酸基価が1430eq/tonであった。
得られたオリゴマーに、上記方法で調製したアルミニウム含有エチレングリコール溶液sおよびリン含有エチレングリコール溶液tを混合し一液化した混合液を添加した。該混合液は、それぞれオリゴマーの質量に対して、アルミニウム元素およびリン元素として30質量ppmおよび74質量ppmとなるように作製した。アルミニウム元素に対するリン元素の添加モル比は2.15であった。なお、生成される再生ポリエステル樹脂(d-7)の量は、添加するナフタレンジカルボン酸及びPEN樹脂の量より算出可能であり、本実施例では、生成される再生ポリエステル樹脂(d-7)500gに対してアルミニウム元素およびリン元素として30質量ppmおよび74質量ppmとなるように混合液が添加されている。
その後、1時間で系の温度を290℃まで昇温して、この間に系の圧力を徐々に減じて0.15kPaとし、この条件下で重縮合反応を行い、IVが0.51dl/g、酸価が33eq/tonの再生ポリエステル樹脂(d-7)を得た。再生ポリエステル樹脂(d-7)におけるアルミニウム元素の残存量は30質量ppm、リン元素の残存量は54質量ppm、アルミニウム元素に対するリン元素の残存モル比は1.56であった。再生ポリエステル樹脂(d-7)のL値は62.2であり、b値は6.2、ガラス転移温度は118℃であった。
アルミニウム含有エチレングリコール溶液sおよびリン含有エチレングリコール溶液tを添加する代わりに、生成される再生ポリエステル樹脂(d-8)500gに対してアンチモン元素として300質量ppmとなるようにアンチモン触媒を添加する以外は、実施例6と同様の方法で再生ポリエステル樹脂(d-8)を得た。
リサイクルポリエステル樹脂(b)の量を表2に記載の量に変更した以外は、実施例6と同様の方法で再生ポリエステル樹脂(d’-3)を得た。
アルミニウム含有エチレングリコール溶液sおよびリン含有エチレングリコール溶液tを添加する代わりに、生成される再生ポリエステル樹脂(d’-4)500gに対してアンチモン元素として300質量ppmとなるようにアンチモン触媒を添加する以外は、参考例3と同様の方法で再生ポリエステル樹脂(d’-4)を得た。
実施例1~実施例5では、製造工程でリサイクルポリエステル樹脂(a)及びアルミニウム触媒を所定の割合で用いているため、黒ずみの尺度であるL値が高いままであり、かつ、黄色みの尺度であるb値が低いままである再生ポリエステル樹脂(d-1)~(d-5)を得ることができた。
実施例6では、製造工程でリサイクルポリエステル樹脂(b)及びアルミニウム触媒を所定の割合で用いているため、黒ずみの尺度であるL値が高いままであり、かつ、黄色みの尺度であるb値が低いままである再生ポリエステル樹脂(d-7)を得ることができた。
Claims (6)
- 再生ポリエステル樹脂の製造方法であって、
回収されたポリエステル樹脂(A)、多価カルボン酸(B)、及び多価アルコール(C)を混合して、解重合及びエステル化する第1工程と、
第1工程の反応物をさらに重縮合して高分子量化する第2工程とを有し、
前記ポリエステル樹脂(A)の割合は、前記再生ポリエステル100質量部に対し、5~80質量部であり、
前記第2工程における重縮合はアルミニウム化合物の存在下で行われ、前記アルミニウム化合物は前記反応物に対してアルミニウム元素換算で5~100質量ppmであることを特徴とする再生ポリエステル樹脂の製造方法。 - 前記第2工程における重縮合がリン化合物の存在下で行われ、前記リン化合物が前記反応物に対してリン元素換算で3~1000質量ppmである請求項1に記載の再生ポリエステル樹脂の製造方法。
- 前記リン化合物が、同一分子内にリン元素とフェノール構造を有する化合物である請求項2に記載の再生ポリエステル樹脂の製造方法。
- 前記ポリエステル樹脂(A)が、芳香族ジカルボン酸に由来のジカルボン酸単位と炭素数2~6のアルキレングリコールに由来のジオール単位とを有する請求項1又は2に記載の再生ポリエステル樹脂の製造方法。
- 前記ポリエステル樹脂(A)が、アンチモン、チタン、及びゲルマニウムから選ばれる少なくとも一種の元素を含む請求項1又は2に記載の再生ポリエステル樹脂の製造方法。
- 前記ポリエステル樹脂(A)中におけるアンチモン元素、チタン元素、及びゲルマニウム元素の合計の含有量が2~500質量ppmである請求項5に記載の再生ポリエステル樹脂の製造方法。
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KR (1) | KR20240070509A (ja) |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH10101784A (ja) * | 1996-09-30 | 1998-04-21 | Nippon Ester Co Ltd | スクラップ利用ポリエステルの製造法 |
JP2000191766A (ja) | 1998-12-25 | 2000-07-11 | Nippon Polyurethane Ind Co Ltd | テレフタル酸系ポリエステルポリオ―ルの製造方法 |
JP2008266359A (ja) * | 2007-04-16 | 2008-11-06 | Toyobo Co Ltd | ポリエステル重合触媒およびこれを用いて製造されたポリエステルならびにポリエステルの製造方法 |
JP2021161890A (ja) | 2020-03-31 | 2021-10-11 | いすゞ自動車株式会社 | 収納管 |
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- 2022-09-26 JP JP2023511599A patent/JPWO2023054271A1/ja active Pending
- 2022-09-26 CN CN202280061212.3A patent/CN117999305A/zh active Pending
- 2022-09-26 KR KR1020247006230A patent/KR20240070509A/ko unknown
- 2022-09-28 TW TW111136640A patent/TW202330715A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10101784A (ja) * | 1996-09-30 | 1998-04-21 | Nippon Ester Co Ltd | スクラップ利用ポリエステルの製造法 |
JP2000191766A (ja) | 1998-12-25 | 2000-07-11 | Nippon Polyurethane Ind Co Ltd | テレフタル酸系ポリエステルポリオ―ルの製造方法 |
JP2008266359A (ja) * | 2007-04-16 | 2008-11-06 | Toyobo Co Ltd | ポリエステル重合触媒およびこれを用いて製造されたポリエステルならびにポリエステルの製造方法 |
JP2021161890A (ja) | 2020-03-31 | 2021-10-11 | いすゞ自動車株式会社 | 収納管 |
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CN117999305A (zh) | 2024-05-07 |
JPWO2023054271A1 (ja) | 2023-04-06 |
KR20240070509A (ko) | 2024-05-21 |
TW202330715A (zh) | 2023-08-01 |
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