WO2023162303A1 - ポリエステル、及び、ポリウレタン - Google Patents

ポリエステル、及び、ポリウレタン Download PDF

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Publication number
WO2023162303A1
WO2023162303A1 PCT/JP2022/033643 JP2022033643W WO2023162303A1 WO 2023162303 A1 WO2023162303 A1 WO 2023162303A1 JP 2022033643 W JP2022033643 W JP 2022033643W WO 2023162303 A1 WO2023162303 A1 WO 2023162303A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester
polyurethane
compound
mass
adhesive
Prior art date
Application number
PCT/JP2022/033643
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
邦彦 小松崎
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2023555789A priority Critical patent/JPWO2023162303A1/ja
Publication of WO2023162303A1 publication Critical patent/WO2023162303A1/ja

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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/60—Polyamides or polyester-amides
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides

Definitions

  • the present invention relates to polyesters and polyurethanes.
  • Polyester is used for various purposes, for example, as a raw material for coating agents and adhesives.
  • the polyester there is a strong demand for a shift to a material capable of material recycling, chemical recycling, easy decomposition by external stimulation, etc., toward the realization of carbon neutrality (see, for example, Patent Document 1).
  • the problem to be solved by the present invention is to provide an easily decomposable polyester.
  • the present invention provides a polyester characterized by having a structure derived from compound (X) represented by the following formula (1).
  • R 1 represents an alkylene group having 1 to 10 carbon atoms.
  • the present invention also provides a polyurethane characterized by being a reaction product of the polyester and polyisocyanate, and an adhesive characterized by containing the polyurethane.
  • the polyester of the present invention is easily decomposable. Therefore, for example, when the polyurethane-based adhesive made from the polyester of the present invention is used for a material-recyclable fiber base material, etc., the adhesive can be easily decomposed, and the adhesive can be removed after use. However, since the fiber base material can also be recycled, it is a useful material for realizing a carbon-neutral world.
  • the polyester of the present invention has a structure derived from compound (X) represented by the following formula (1).
  • R 1 represents an alkylene group having 1 to 10 carbon atoms.
  • the hydrazide bond of the compound (X) is cleaved to impart easy degradability.
  • Examples of the method for cleaving the hydrazide bond include applying an external stimulus with an oxidizing agent such as sodium hypochlorite.
  • the compound (X) represented by the formula (1) is preferably a compound in which R 1 is an alkylene group having 2 to 10 carbon atoms, and R 1 is carbon, in order to obtain even better decomposability.
  • R 1 is an alkylene group having 2 to 10 carbon atoms
  • R 1 is carbon
  • Compounds showing an alkylene group having 3 to 5 atoms are more preferred, and adipic acid dihydrazide having 4 carbon atoms is particularly preferred.
  • a method for producing the polyester of the present invention includes, for example, a known method of transesterifying a reaction product of a polybasic acid and a compound having two or more hydroxyl groups with the compound (X).
  • polybasic acid examples include succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosadioic acid, citraconic acid, itaconic acid, citraconic anhydride, anhydrous Itaconic acid and the like can be used.
  • These polybasic acids may be used alone or in combination of two or more.
  • Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, trimethylolpropane, trimethylolethane, glycerin, and the like. can be used. These compounds may be used alone or in combination of two or more.
  • the products obtained by the transesterification include a polyester in which the compound (X) is introduced into the polyester skeleton by an amide ester structure and which has hydroxyl groups and/or NH2 groups at the ends, and two or more of the free hydroxyl groups.
  • Compositions with compounds having The obtained polyester has hydroxyl groups and/or NH2 groups at its terminals, so it can also be used as a material for polyurethane.
  • the polyester is used as a polyurethane material, if necessary, the compound having two or more free hydroxyl groups may be distilled off under reduced pressure.
  • the polyester of the present invention having a structure derived from the compound (X) is used as a raw material to form a polyurethane
  • the structure derived from the compound (X) is introduced into the soft segment of the polyurethane.
  • high degradability can be obtained.
  • the polyester is introduced into the polyurethane skeleton as a highly polar polyester component, it can be used particularly preferably as an adhesive.
  • the weight average molecular weight of the polyester is, for example, 500 to 100,000, preferably 1,000 to 10,000.
  • the weight average molecular weight of the polyester indicates a value measured by a gel permeation column chromatography (GPC) method.
  • polyurethane is obtained by reacting a polyol mixture containing the polyester with polyisocyanate.
  • polyester polyols other than the polyesters polycarbonate polyols, polyether polyols, polyacrylic polyols, polybutadiene polyols, and compounds having two or more hydroxyl groups that are raw materials for the polyesters may be used in combination.
  • the content of the polyester in the polyol mixture is preferably 20 to 80% by mass, more preferably 40 to 60% by mass, from the standpoint of easy decomposition of the polyester.
  • the number average molecular weight of compounds that can be used other than the polyester is, for example, 500 to 100,000, excluding the compounds having two or more hydroxyl groups.
  • the number average molecular weight of the said compound shows the value measured by the gel permeation column chromatography (GPC) method.
  • polyisocyanate examples include aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidated diphenylmethane polyisocyanate; hexamethylene diisocyanate, lysine diisocyanate, Aliphatic polyisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate and norbornene diisocyanate, or alicyclic polyisocyanates can be used. These polyisocyanates may be used alone or in combination of two or more.
  • the molar ratio [NCO/OH.NH] between the isocyanate groups (NC) of the polyisocyanate and the hydroxyl groups and/or NH2 groups (OH.NH) of the polyol mixture when obtaining the polyurethane is For example, 0.5 to 3 can be mentioned.
  • the polyester of the present invention is easily decomposable. Therefore, for example, when the polyurethane-based adhesive made from the polyester of the present invention is used for a material-recyclable fiber base material, etc., the adhesive can be easily decomposed, and the adhesive can be removed after use. However, since the fiber base material can also be recycled, it is a useful material for realizing a carbon-neutral world.
  • Example 1 In a flask, 100 parts by mass of a polyester having a number average molecular weight of 4,500, which is a reaction product of 1,6-hexanediol and adipic acid, and 5 parts by mass of adipic acid dihydrazide (hereinafter abbreviated as "ADH"). and reacted at 140° C. for 6 hours to obtain a polyester composition having a weight average molecular weight of 4200. The resulting polyester composition was distilled under reduced pressure at 160° C. to remove residual 1,6-hexanediol. Evaporation gave polyester (1).
  • ADH adipic acid dihydrazide
  • polyester (1) 200 parts by mass of polyester (1) obtained, 100 parts by mass of polypropylene glycol having a number average molecular weight of 1,000, and 100 parts by mass of polypropylene glycol having a number average molecular weight of 2,000 were mixed and dried under reduced pressure at 110°C. , dehydrated until the water content was 0.05% by mass or less.
  • 85 parts by mass of 4,4-diphenylmethane diisocyanate was added, the temperature was raised to 120° C., and the mixture was reacted for 2 hours until the isocyanate group content became constant to obtain polyurethane (1). .
  • an infrared spectrophotometer (“FT/IR-460Plus”, manufactured by JASCO Corporation) was used to determine an absorption peak around 1,630 cm ⁇ 1 attributed to hydrazide bonds. It was confirmed that a structure derived from dihydrazide adipic acid was introduced into the polyurethane (1).
  • Example 2 In a flask, 100 parts by mass of polyester having a number average molecular weight of 2,000 which is a reaction product of diethylene glycol, neopentyl glycol, 1,6-hexanediol, and adipic acid, and 5 parts by mass of ADH were mixed and heated at 140°C. for 6 hours to obtain a polyester composition having a weight average molecular weight of 1,900. The resulting polyester composition was distilled under reduced pressure at 160° C. to distill off residual diethylene glycol, neopentyl glycol and 1,6-hexanediol to obtain polyester (2).
  • polyester polyol reaction product of 1,6-hexanediol and adipic acid having a number average molecular weight of 4,500
  • a polyester polyol reaction product of 1,6-hexanediol and adipic acid having a number average molecular weight of 4,500
  • 75 parts by mass of 4,4-diphenylmethane diisocyanate was added, the temperature was raised to 120° C., and the mixture was reacted for 2 hours until the isocyanate group content became constant to obtain polyurethane (2).
  • an infrared spectrophotometer (“FT/IR-460Plus”, manufactured by JASCO Corporation) was used to determine an absorption peak near 1,630 cm ⁇ 1 attributed to hydrazide bonds. It was confirmed that a structure derived from dihydrazide adipic acid was introduced into the polyurethane (2).
  • polyester polyol reaction product of 1,6-hexanediol and adipic acid
  • polypropylene glycol with a number average molecular weight of 1,000 100 parts by mass of polypropylene glycol was mixed, dried under reduced pressure at 110° C., and dehydrated until the water content was 0.05% by mass or less.
  • the number average molecular weights of polyols and the like used in Examples and Comparative Examples are values obtained by measuring under the following conditions by gel permeation column chromatography (GPC).
  • Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 Book “TSKgel G2000" (7.8 mm I.D.
  • the polyester of the present invention was found to be excellent in easy degradability.
  • the polyester-based polyurethane used in Examples 1 and 2 showed a large decrease in the tensile strength of the film, indicating that these films are also excellent in easily degradable properties.
  • Comparative Examples 1 and 2 are both examples in which a polyester having no structure derived from the compound (X) represented by formula (1) was used, but both were poor in easy degradability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/JP2022/033643 2022-02-24 2022-09-08 ポリエステル、及び、ポリウレタン WO2023162303A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2023555789A JPWO2023162303A1 (enrdf_load_stackoverflow) 2022-02-24 2022-09-08

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022026540 2022-02-24
JP2022-026540 2022-02-24

Publications (1)

Publication Number Publication Date
WO2023162303A1 true WO2023162303A1 (ja) 2023-08-31

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ID=87765362

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JP (1) JPWO2023162303A1 (enrdf_load_stackoverflow)
TW (1) TW202344560A (enrdf_load_stackoverflow)
WO (1) WO2023162303A1 (enrdf_load_stackoverflow)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1386628A (en) * 1971-07-29 1975-03-12 Herberts & Co Gmbh Dr Kurt Stoving lacquer containing organic solvents and nitrogen-containing polyester resins
JPH0543792A (ja) * 1991-08-15 1993-02-23 Ajinomoto Co Inc ポリアミノ酸ウレタン樹脂及びそれを用いた製品
JPH07157557A (ja) * 1993-12-08 1995-06-20 Agency Of Ind Science & Technol 生分解性ポリエステルアミド共重合体の製造方法
JPH09188779A (ja) * 1995-12-22 1997-07-22 Bayer Ag 熱可塑的に加工可能な生分解性成形用組成物
JPH1135678A (ja) * 1997-07-25 1999-02-09 Dainippon Ink & Chem Inc 生分解性ポリエステルアミド及びその製造方法
JP2001503420A (ja) * 1996-11-07 2001-03-13 バイエル・アクチエンゲゼルシヤフト 植物処置用組成物
JP2002521276A (ja) * 1998-07-20 2002-07-16 ユーピーエム−キンメネ コーポレイション 食品包装の被覆構造
JP2006022315A (ja) * 2004-06-07 2006-01-26 Osaka Prefecture 分解性ポリアミド
JP2008222783A (ja) * 2007-03-09 2008-09-25 National Institute Of Advanced Industrial & Technology 生分解性ポリエステルアミド及びその製造方法
JP2011052075A (ja) * 2009-08-31 2011-03-17 Kanagawa Univ ポリ（ジアシルヒドラジン）の製造方法、及びポリ（ジアシルヒドラジン）
US20150267077A1 (en) * 2014-03-19 2015-09-24 Ppg Industries Ohio, Inc. Coated metal substrates and methods of preparing them

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1386628A (en) * 1971-07-29 1975-03-12 Herberts & Co Gmbh Dr Kurt Stoving lacquer containing organic solvents and nitrogen-containing polyester resins
JPH0543792A (ja) * 1991-08-15 1993-02-23 Ajinomoto Co Inc ポリアミノ酸ウレタン樹脂及びそれを用いた製品
JPH07157557A (ja) * 1993-12-08 1995-06-20 Agency Of Ind Science & Technol 生分解性ポリエステルアミド共重合体の製造方法
JPH09188779A (ja) * 1995-12-22 1997-07-22 Bayer Ag 熱可塑的に加工可能な生分解性成形用組成物
JP2001503420A (ja) * 1996-11-07 2001-03-13 バイエル・アクチエンゲゼルシヤフト 植物処置用組成物
JPH1135678A (ja) * 1997-07-25 1999-02-09 Dainippon Ink & Chem Inc 生分解性ポリエステルアミド及びその製造方法
JP2002521276A (ja) * 1998-07-20 2002-07-16 ユーピーエム−キンメネ コーポレイション 食品包装の被覆構造
JP2006022315A (ja) * 2004-06-07 2006-01-26 Osaka Prefecture 分解性ポリアミド
JP2008222783A (ja) * 2007-03-09 2008-09-25 National Institute Of Advanced Industrial & Technology 生分解性ポリエステルアミド及びその製造方法
JP2011052075A (ja) * 2009-08-31 2011-03-17 Kanagawa Univ ポリ（ジアシルヒドラジン）の製造方法、及びポリ（ジアシルヒドラジン）
US20150267077A1 (en) * 2014-03-19 2015-09-24 Ppg Industries Ohio, Inc. Coated metal substrates and methods of preparing them

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JPWO2023162303A1 (enrdf_load_stackoverflow) 2023-08-31
TW202344560A (zh) 2023-11-16

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