WO2022158606A1 - ポリカーボネートポリオール、その製造方法及びその組成物 - Google Patents

ポリカーボネートポリオール、その製造方法及びその組成物 Download PDF

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Publication number
WO2022158606A1
WO2022158606A1 PCT/JP2022/002615 JP2022002615W WO2022158606A1 WO 2022158606 A1 WO2022158606 A1 WO 2022158606A1 JP 2022002615 W JP2022002615 W JP 2022002615W WO 2022158606 A1 WO2022158606 A1 WO 2022158606A1
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polycarbonate polyol
polyurethane resin
formula
bonds
carbon atoms
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PCT/JP2022/002615
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English (en)
French (fr)
Japanese (ja)
Inventor
テチャジャルーンジット タナチャート
遼 藤本
ジッタブンルアン ドンラパン
キティヤナン アタポン
ナワカンピスット ナッタパット
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宇部興産株式会社
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Priority to CN202280008984.0A priority Critical patent/CN116710502A/zh
Priority to JP2022576779A priority patent/JPWO2022158606A1/ja
Publication of WO2022158606A1 publication Critical patent/WO2022158606A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • 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
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—Polyurethanes

Definitions

  • the present invention relates to a polycarbonate polyol, its production method and its composition.
  • polycarbonate polyols are useful as raw materials for producing polyurethane resins, raw materials for engineering plastics, adhesives, paints, etc. by reacting with polyisocyanate compounds. It is also used as a modifier such as
  • a reaction between a polycarbonate diol and a lactone is known for modification of a polycarbonate diol (for example, Patent Document 1).
  • This product has less carbonate linkages and more ester linkages than polycarbonate diols.
  • the polycarbonate diol of Patent Literature 1 lacks solvent resistance when urethanized, further improvement in solvent resistance is required.
  • the polycarbonate of Patent Document 2 has a high molecular weight of 20,000 g/mol or more, and thus has a high viscosity and is difficult to handle.
  • the presence or absence of a molecular terminal structure capable of reacting with an isocyanate such as a hydroxyl group is not clarified in the polycarbonate of Patent Document 2, and there is no mention of derivation of the polycarbonate diol into polyurethane.
  • An object of the present invention is to provide a polycarbonate polyol that is easy to handle and that improves the mechanical performance and solvent resistance of the polyurethane resin obtained from the polycarbonate diol.
  • the present invention is specifically as follows.
  • R 1 and R 2 represent a hydrocarbon group having 2 to 20 carbon atoms.
  • R 1 is a linear or branched alkylene group having 4 to 7 carbon atoms.
  • R 1 is a linear or branched alkylene group having 4 to 7 carbon atoms.
  • 9. The polycarbonate polyol according to any one of 1 to 8 above, which has a number average molecular weight of 400 to 4500 g/mol. 10.
  • 10. The polycarbonate polyol as described in any one of 1 to 9 above, which is liquid at room temperature (25° C.). 11.
  • a method for producing a polycarbonate polyol having an ester bond and a urethane bond and having an acid value of 0.01 to 5.0 mgKOH/g Polycarbonate polyol using a transesterification catalyst, at least one carbonate represented by the following formula (3), at least one diol represented by the following formula (4), and a cyclic amide represented by the following formula (5) Production method.
  • R 1 and R 2 represent a hydrocarbon group having 2 to 20 carbon atoms.
  • R 3 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 5 to 8 carbon atoms, and the same Two R3's in the molecule may be the same or different , or two R3's may together form a ring as an alkylene group having 1 to 4 carbon atoms.
  • a composition for forming a polyurethane resin comprising the polycarbonate polyol (A) according to any one of claims 1 to 10 and a polyisocyanate (C).
  • 16. 15. A coating composition comprising the polyurethane resin described in 14 above. 17. 15.
  • a coating agent composition comprising the polyurethane resin described in 14 above. 18.
  • An adhesive composition comprising the polyurethane resin of claim 14. 19.
  • a polyurethane resin film comprising the polyurethane resin described in 14 above.
  • 20. 15. Synthetic leather comprising the polyurethane resin described in 14 above.
  • 21. 15. A thermoplastic polyurethane comprising the polyurethane resin described in 14 above. 22. 15. A thermosetting/cast polyurethane containing the polyurethane resin described in 14 above.
  • the polycarbonate polyol of the present invention has an ester bond and a urethane bond and an acid value of 0.01 to 5.0 mgKOH/g. This makes it possible to provide a polycarbonate polyol which is easy to handle and improves the mechanical performance and solvent resistance of the polyurethane resin obtained from the polycarbonate polyol.
  • the polycarbonate polyol of the present invention is preferably a polycarbonate diol having hydroxyl groups at both molecular ends.
  • "easily handled” means satisfying at least one of the following 1) and 2). 1) Viscosity at 75°C is 3000 cP or less. 2) liquid at room temperature (25° C.); Due to the ease of handling, the polycarbonate polyol can be easily used as a raw material for polyurethane resins and the like.
  • the ester bond content is preferably 1.5% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and 8% by mass with respect to the total amount of the polycarbonate polyol. The above is even more preferable.
  • the content of ester bonds is preferably 15% by mass or less, more preferably 14% by mass or less, and even more preferably 12% by mass or less, relative to the total amount of the polycarbonate polyol.
  • the ester bond content is preferably 1.5 to 15% by mass, more preferably 3 to 14% by mass, and even more preferably 5 to 12% by mass, relative to the total amount of polycarbonate polyol. . Within this range, it is possible to obtain a polycarbonate polyol that is easy to handle and that improves the mechanical performance and chemical resistance of the polyurethane resin.
  • the content of urethane bonds is preferably 2% by mass or more, more preferably 4% by mass or more, still more preferably 9% by mass or more, and 13% by mass or more with respect to the total amount of polycarbonate polyol. It is even more preferred to have In addition, the content of urethane bonds is preferably 20% by mass or less, more preferably 19% by mass or less, and even more preferably 16% by mass or less, relative to the total amount of polycarbonate polyol. The content of urethane bonds is preferably 2 to 20% by mass, more preferably 4 to 19% by mass, even more preferably 9 to 16% by mass, relative to the total amount of polycarbonate polyol. Within this range, it is possible to obtain a polycarbonate polyol that is easy to handle and that improves the mechanical performance and chemical resistance of the polyurethane resin.
  • the content of carbonate bonds is preferably 3% by mass or more, more preferably 6% by mass or more, still more preferably 11% by mass or more, and 14% by mass or more with respect to the total amount of polycarbonate polyol. It is even more preferred to have Also, the content of carbonate bonds is preferably 35% by mass or less, more preferably 32% by mass or less, and even more preferably 23% by mass or less, relative to the total amount of polycarbonate polyol. The content of carbonate bonds is preferably 3 to 35% by mass, more preferably 6 to 32% by mass, even more preferably 11 to 23% by mass, relative to the total amount of polycarbonate polyol.
  • polycarbonate polyol that is easy to handle and that improves the mechanical performance and chemical resistance of the polyurethane resin.
  • the polycarbonate polyol of the present invention has an ester bond, a urethane bond, and a carbonate bond, and the content of each bond is within the above range, the general characteristics of polycarbonate can be fully exhibited while further It is particularly preferred because it provides a polycarbonate polyol with excellent chemical resistance and handleability.
  • the molar ratio of the urethane bond and the ester bond (urethane/ester) is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and 0.95 to 1.05. It is even more preferable to have Within this range, it is possible to obtain a polycarbonate polyol that is easy to handle and improves the mechanical performance and solvent resistance of the polyurethane resin. Also, the content of ester bonds and urethane bonds represented by the following formula (I) is preferably 10 to 90 mol %. Within this range, it is possible to obtain a polycarbonate polyol that is easy to handle and improves the mechanical performance and solvent resistance of the polyurethane resin.
  • the polycarbonate polyol of the present invention has an acid value of 0.01 to 5.0 mgKOH/g. Within this range, a polyurethane resin having particularly good physical properties can be obtained using this as a raw material.
  • the acid value is preferably 0.01-1.0 mgKOH/g, more preferably 0.01-0.5 mgKOH/g. Within this range, it is possible to obtain a polycarbonate polyol that is easy to handle and improves the mechanical performance and solvent resistance of the polyurethane resin.
  • the acid value is a value measured according to the indicator titration method of JIS K 1557.
  • the polycarbonate polyol of the present invention may have a hydroxyl value of 25-250 mgKOH/g. Within this range, a polyurethane resin having particularly good physical properties can be obtained using this as a raw material.
  • the polycarbonate polyol preferably has a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).
  • R 1 and R 2 represent divalent hydrocarbon groups having 2 to 20 carbon atoms.
  • R 1 is preferably a linear, branched or cyclic aliphatic hydrocarbon group having 4 to 8 carbon atoms or an aromatic hydrocarbon group having 8 to 12 carbon atoms. It is more preferably a linear, branched or cyclic alkylene group, more preferably a linear or branched alkylene group having 4 to 7 carbon atoms, and a linear alkylene group having 5 or 6 carbon atoms. is even more preferred.
  • R 2 is preferably an aliphatic or aromatic hydrocarbon group having 5 to 12 carbon atoms, more preferably a linear or branched alkylene group having 6 to 12 carbon atoms, A linear alkylene group is more preferred.
  • R 1 and R 2 may be plural kinds of the above hydrocarbon groups.
  • the polycarbonate polyol may have a repeating unit in which R 1 is an alkylene group having 5 carbon atoms and a repeating unit in which R 1 is an alkylene group having 6 carbon atoms.
  • hydrocarbon group examples include linear or branched alkylene groups having 2 to 20 carbon atoms, such as ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene and octamethylene groups.
  • cycloalkylene groups such as cyclopentylene, cyclohexylene, 1,2-dimethylenecyclopentane, 1,3-dimethylenecyclopentane, 1,2-dimethylenecyclohexane, 1 , 3-dimethylenecyclohexane group, 1,4-dimethylenecyclohexane group, 4,4′-methylenedicyclohexylene group, 2,2-dicyclohexylenepropane group, etc.; arylene groups such as phenylene group, 1,2-dimethylenebenzene group, 1,3-dimethylenebenzene group, 1,4-dimethylenebenzene group, naphthylene group, 4,4′-methylenediphenylene group, 2,
  • the polycarbonate polyol of the present invention preferably has a number average molecular weight Mn of 400 to 4500 g/mol. Within this range, fluidity (eg, viscosity of 500 to 10,000 cP) can be easily obtained under heating (eg, 75° C.), and handleability is excellent.
  • the number average molecular weight Mn is more preferably 500-3500 g/mol, still more preferably 500-3000. In this specification, the number average molecular weight Mn is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K 1577.
  • the hydroxyl value is measured and calculated using (56.1 ⁇ 1000 ⁇ valence) / hydroxyl value by the terminal group determination method (in this formula, the unit of hydroxyl value is [mgKOH / g] is).
  • the valence is the number of hydroxyl groups in one molecule.
  • the polycarbonate polyol of the present invention preferably has a weight average molecular weight Mw of 500 to 30000 g/mol.
  • the weight average molecular weight Mw is more preferably 1000-13000 g/mol.
  • the weight average molecular weight Mw is a value measured by GPC.
  • the degree of dispersion Mw/Mn is preferably 1.0 to 3.0.
  • the dispersity Mw/Mn is preferably 2.0 to 2.3. If the polydispersity is greater than 3.0, the sizes of the hard and soft segments in the resulting polyurethane may vary greatly, and the mechanical properties of the polyurethane may deteriorate.
  • the polycarbonate polyol of the present invention preferably has a water content of 1 to 10,000 ppm. If the water content is more than 10,000 ppm, the amount of urea groups produced as a by-product from the reaction between water and isocyanate during polyurethane synthesis increases, which may impair the flexibility of the polyurethane.
  • the glass transition point of the polycarbonate polyol of the present invention is preferably -80°C to +50°C. If the glass transition point is lower than -80°C, the strength of the resulting polyurethane may be insufficient, and if it is higher than 50°C, it may become brittle at around room temperature.
  • the viscosity of the polycarbonate polyol of the present invention is preferably 10 to 90,000 cP (75°C), more preferably 50 to 10,000 cP (75°C), and 100 to 3,000 cP (75°C). It is even more preferable to have If the viscosity is higher than 3,000 cP (75° C.), handleability may deteriorate when synthesizing polyurethane.
  • the production method of the present invention is a method for producing a polycarbonate polyol having an ester bond and a urethane bond and having an acid value of 0.01 to 5.0 mgKOH/g, comprising a transesterification catalyst, at least one of the following formula
  • At least one carbonate represented by the following formula (3) and at least one diol represented by the following formula (4) are reacted in the presence of a transesterification catalyst, and the obtained product and the following formula ( It is preferable that the method for producing a polycarbonate polyol comprises reacting with the cyclic amide shown in 5).
  • a method for producing a polycarbonate polyol comprising simultaneously reacting a carbonate represented by (3), at least one diol represented by the following formula (4), and a cyclic amide represented by the following formula (5). is preferred.
  • R 1 and R 2 are as defined above.
  • R 3 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 5 to 8 carbon atoms, and two R 3 in the same molecule may be the same or different, or two R 3 may together form a ring as an alkylene group having 1 to 4 carbon atoms.
  • R 3 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms.
  • diols examples include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1, Linear alkane diols having 2 to 20 carbon atoms such as 9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol can be mentioned.
  • Further examples include 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3 -branched C2-C20 alkane diols such as propanediol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis(hydroxyethyl) ) diols having an alicyclic structure having 6 to 20 carbon atoms such as cyclohexane, 2,2-bis(4-hydroxycyclohexyl)
  • Carbonates include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate; aromatic carbonate esters such as diphenyl carbonate; cyclic carbonate esters such as ethylene carbonate; is preferably an aliphatic carbonate or a cyclic carbonate, and dimethyl carbonate or ethylene carbonate is particularly preferable, because the is easy to remove.
  • Cyclic amides include aliphatic cyclic amides having 5 to 12 carbon atoms; cyclic amides such as 2-pyrrolidone, piperidone, N-methylpyrrolidone, ⁇ -caprolactam, N-methylcaprolactam and laurolactam, preferably ⁇ - is caprolactam.
  • a compound containing 5 to 12 aliphatic or aromatic hydrocarbon groups, amino groups, and carboxyl groups in the same molecule can also be used instead of the cyclic amide.
  • a catalyst can be used when producing the polycarbonate polyol of the present invention.
  • the catalyst those commonly used as transesterification catalysts can be used.
  • the transesterification catalyst are preferably alkali metal compounds, alkaline earth metal compounds, aluminum compounds, zinc compounds, manganese compounds, nickel compounds, antimony compounds, zirconium compounds, titanium compounds, organotin compounds, titanium compounds, and / or alkali metal compounds are more preferred. These catalysts may be mixed and used.
  • Alkali metal compounds include alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (lithium carbonate, sodium carbonate, potassium carbonate, etc.), and alkali metal carboxylates. (lithium acetate, sodium acetate, potassium acetate, etc.), alkali metal alkoxides (lithium methoxide, sodium methoxide, potassium t-butoxide, etc.). substances (magnesium hydroxide, etc.), alkaline earth metal alkoxides (magnesium methoxide, etc.), and the like.
  • Examples of aluminum compounds include aluminum alkoxides (aluminum ethoxide, aluminum isopropoxide, aluminum sec-butoxide, etc.), aluminum compounds such as aluminum acetylacetonate, and the like.
  • Zinc compounds include zinc carboxylates (such as zinc acetate) and zinc acetylacetonate.
  • Examples of manganese compounds include manganese carboxylates (manganese acetate, etc.), manganese acetylacetonate, and the like.
  • Nickel compounds include nickel carboxylates (nickel acetate, etc.), nickel acetylacetonate, and the like.
  • antimony compounds include antimony carboxylates (antimony acetate, etc.), antimony alkoxides, and the like.
  • Zirconium compounds include zirconium alkoxides (zirconium propoxide, zirconium butoxide, etc.), zirconium acetylacetonate, and the like.
  • Titanium compounds include titanium alkoxides (titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, tetracyclohexyl titanate, tetrabenzyl titanate, etc.), titanium acylates (tributoxytitanium stearate, isopropoxy stearate, etc.), titanium chelates (diisopropoxytitanium bisacetylacetonate, dihydroxy-bislactatotitanium, etc.) and the like.
  • Organic tin compounds include dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, and the like.
  • Each carboxylate preferably has 2 to 30 carbon atoms, more preferably 2 to 18 carbon atoms, and each alkoxide preferably has an alkoxy group with 1 to 30 carbon atoms, and 2 to 18 is more preferred.
  • titanium compounds, organotin compounds and alkali metal compounds are preferred, titanium compounds and/or alkali metal compounds are more preferred, and titanium alkoxides, alkali metal hydroxides and/or alkali metal carbonates are preferred. More preferred. These catalysts may be mixed and used.
  • titanium alkoxides titanium tetraalkoxides such as titanium tetraethoxide, titanium tetrapropoxide and titanium tetrabutoxide are more preferred, and titanium tetrabutoxide is even more preferred.
  • said diol, carbonate, cyclic amide, and catalyst can be used individually by 1 type or in combination of 2 or more types.
  • ⁇ Method> As a method for producing the polycarbonate polyol of the present invention, the following methods can be employed. 1. The diol compound represented by the formula (4), the cyclic amide represented by the formula (5), and the carbonate represented by the formula (3) are all mixed together, and produced by transesterification while extracting alcohol and the like. There is a way. 2. After transesterifying the diol compound represented by formula (4) and the carbonate represented by formula (3), the cyclic amide represented by formula (5) and, if necessary, formula (4) There is a method of adding the represented diol compound and reacting it. 3.
  • the diol compound represented by the formula (4) and the carbonate represented by the formula (3) are added to obtain There are ways to react. Among them, the method shown in 2 above uses as a common raw material one kind of polycarbonate polyol obtained by subjecting the diol compound represented by the formula (4) and the carbonate represented by the formula (3) to the transesterification reaction, using the formula (5) It is preferable from the viewpoint that various products can be synthesized by changing the addition amount of the cyclic amide represented by.
  • This production method consists of a two-stage reaction. 1st stage: The diol compound represented by the formula (4) and the carbonate represented by the formula (3) are transesterified. Second stage: To the obtained reaction solution, a cyclic amide represented by the formula (5) and, if necessary, a diol compound represented by the formula (4) are added and reacted.
  • the diol compound represented by the formula (4) and the carbonate represented by the formula (3) are preferably subjected to a transesterification reaction in the presence of a catalyst while distilling off alcohol derived from the carbonate.
  • the reaction temperature is preferably 90 to 230° C., although it varies depending on the type of diol compound and carbonate used.
  • the pressure in this reaction system is not particularly limited, but a reduced pressure of 30 to 500 mmHg is preferable.
  • the reaction can be carried out in an atmosphere of air, carbon dioxide, or an inert gas (nitrogen, argon, helium, etc.) or in an air stream, but is preferably carried out in an inert gas atmosphere or in an inert gas stream. .
  • the amount of the catalyst added is preferably 1 to 20,000 ppm with respect to the total charged amount.
  • the polycarbonate polyol of the present invention is prepared by adding a cyclic amide represented by the formula (5) and, if necessary, a diol compound represented by the formula (4) to the product (polycarbonate polyol) obtained above. It can be obtained by carrying out the reaction while distilling alcohol or the like, which is a by-product, as necessary.
  • the reaction temperature is preferably a condition under which the cyclic amide represented by formula (5) is not substantially distilled, more preferably 90 to 230°C.
  • the pressure in the reaction system for this reaction is not particularly limited, but a reduced pressure of 30 to 500 mmHg is preferred.
  • the reaction can be carried out in an atmosphere of air, carbon dioxide, or an inert gas (nitrogen, argon, helium, etc.) or in an air stream, but is preferably carried out in an inert gas atmosphere or in an inert gas stream. .
  • the above catalyst may be newly added as the catalyst, or the one used in the first-stage reaction may be used as it is.
  • the above catalyst may be newly added as the catalyst, or the one used in the first-stage reaction may be used as it is.
  • the cyclic amide compounds containing 5 to 12 aliphatic or aromatic hydrocarbon groups, amino groups and carboxyl groups in the same molecule can also be used.
  • the polycarbonate polyol (A) is used as a raw material in forming a polyurethane resin, it can be blended in a composition for forming a polyurethane resin.
  • the polyurethane resin-forming composition of the present invention comprises a polycarbonate polyol (A) and a polyisocyanate (C), wherein the polycarbonate polyol (A), the polyol (B) (excluding the polycarbonate polyol (A)) and the polyisocyanate (C) is preferably included.
  • the polyurethane resin-forming composition is classified into a one-pack type and a two-pack type.
  • the one-pack type contains the polycarbonate polyol (A), polyol (B) and polyisocyanate (C) of the present invention.
  • the ratio of polycarbonate polyol (A) to the total amount of polycarbonate polyol (A) and polyol (B) is more than 0 and 95% by mass from the viewpoint of mechanical performance when urethanized. preferably 1 to 90% by mass, even more preferably 2 to 85% by mass.
  • the two-liquid type consists of a first liquid containing the polycarbonate polyol (A) and the polyol (B), and a second liquid containing the polyisocyanate (C). Sold as a kit.
  • the polyol (B) is a polyol other than the polycarbonate polyol (A).
  • polyol (B) for example, a high-molecular-weight polyol or a low-molecular-weight polyol can be used. High molecular weight diols and low molecular weight diols are preferably used for ease of production.
  • the high molecular weight diol is not particularly limited, but preferably has a number average molecular weight of 400 to 8000 g/mol. If the number average molecular weight is within this range, suitable viscosity and good handleability can be easily obtained. It is easy to ensure the performance as a soft segment, and when a coating film is formed using the composition containing the obtained polyurethane resin, it is easy to suppress the occurrence of cracks, and further reactivity with the polyisocyanate (C). is sufficient, and the polyurethane resin can be produced efficiently.
  • Polyol (B) more preferably has a number average molecular weight of 400 to 4000 g/mol. The number average molecular weight is a value measured by the method described in Examples.
  • high-molecular-weight diols examples include polycarbonate polyols other than the polycarbonate polyol (A), polyester polyols, and polyether polyols.
  • Polycarbonate polyols other than the polycarbonate polyol (A) are preferable from the viewpoints of the obtained composition containing the polyurethane resin and the light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance of the coating film obtained therefrom.
  • Low-molecular-weight diols include, for example, the same diols as the diols represented by formula (4) above, with 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol being preferred.
  • the polyisocyanate (C) is not particularly limited, but examples include aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, and the like.
  • aromatic polyisocyanates include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4′- Diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4 '-diisocyanatodiphenylmethane, 1,5-naphthylenediisocyanate, 4,4',4''-triphenylmethanetriisocyanate, m-isocyanatophenylsulfonylisocyanate, p-isocyanatophenylsulfonylisocyanate and the like.
  • aliphatic polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate.
  • alicyclic polyisocyanates include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2 -isocyanatoethyl)-4-dichlorohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate and the like.
  • IPDI isophorone diisocyanate
  • MDI 4,4′-dicyclohexylmethane diisocyanate
  • TDI methylcyclohexylene diisocyanate
  • bis(2 -isocyanatoethyl)-4-dichlorohexene-1,2-dicarboxylate 2,5-norbornane diisocyanate, 2,
  • polyisocyanate groups having three or more isocyanate groups such as triphenylmethane triisocyanate and isocyanurate derivatives are used as long as the polyurethane resin in the present invention does not gel. Isocyanates can also be used.
  • the polyisocyanate may be used singly or in combination of two or more.
  • the polyurethane resin-forming composition may contain blocking agents, wetting agents, heat stabilizers, light stabilizers, plasticizers, inorganic fillers, lubricants, colorants, silicone oils, foaming agents, flame retardants, etc., depending on the purpose. can exist.
  • the polyurethane resin-forming composition of the present invention comprises a polycarbonate polyol (A) and a polyisocyanate (C), wherein the polycarbonate polyol (A), the polyol (B) (excluding the polycarbonate polyol (A)) and the polyisocyanate (C) is preferably included.
  • a polyurethane resin is obtained by reacting at least the polycarbonate polyol (A) and the polyisocyanate (C).
  • the polyurethane resin of the present invention has a structure derived from the polycarbonate polyol (A) and a structure derived from the polyisocyanate (C), the structure derived from the polycarbonate polyol (A), the polyol (B) (however, the polycarbonate polyol ( It preferably has a structure derived from (excluding A)) and a structure derived from polyisocyanate (C).
  • a catalyst can also be used for the reaction.
  • the catalyst is not particularly limited, for example, tin (tin)-based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.), lead-based catalysts (lead octylate, etc.), salts of metals and organic and inorganic acids, and organic metals derivatives, amine-based catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), diazabicycloundecene-based catalysts, and the like.
  • dibutyltin dilaurate and dioctyltin dilaurate are preferable from the viewpoint of reactivity.
  • the reaction temperature during the reaction is not particularly limited, but is preferably 40 to 120°C, more preferably 60 to 100°C.
  • an aqueous polyurethane resin dispersion, a coating composition, a coating agent composition, a polyurethane resin film, an adhesive composition, a synthetic leather, a thermoplastic polyurethane (TPU), A thermoset and cast polyurethane (TSU) can be obtained. That is, aqueous polyurethane resin dispersions, coating compositions, coating compositions, ink compositions, polyurethane resin films, adhesive compositions, synthetic leather, thermoplastic polyurethanes (TPU), thermosetting/cast polyurethanes (TSU) , including the polyurethane resin.
  • Acid value A 10 g sample was dissolved in a toluene/ethanol 50/50 (mass ratio) solution and titrated with a 0.1 N KOH ethanol solution. Acid value is determined by the following formula: 5.61 ⁇ (C ⁇ B 1 ) ⁇ f/s.
  • B 1 is the volume (mL) of 0.1 N KOH ethanol standard solution required to neutralize the blank
  • C is the 0.1 N KOH ethanol standard solution required to neutralize the sample.
  • f the factor of the 0.1 N KOH ethanol standard solution
  • s is the mass of the sample (g).
  • Viscosity of Polycarbonate Polyol Viscosity was measured using LVDV II + Pro cone and Brookfield plate viscometer together with spindle cone model CPE-41 under the condition of melting at 75°C. (Properties at room temperature) The properties of the polycarbonate polyol at room temperature are visually observed after a sample heated at 80° C. for 3 hours is allowed to stand at 25° C. for 24 hours. A state in which no solid is visible and the liquid is not cloudy is judged to be transparent. Judgment as to whether the polycarbonate polyol is liquid or not is made by heating the polycarbonate polyol at 80° C. for 3 hours and then allowing it to stand at 25° C. for 24 hours to check whether it is transparent and fluid.
  • Polyurethane molecular weight Polystyrene-equivalent molecular weights (number-average molecular weight and weight-average molecular weight) were measured by GPC under the following conditions. Column: TSKgel HZ1000 + Hz3000 (manufactured by Tosoh) (40°C) Mobile phase: THF, flow rate 0.6 ml/min Detector: RI (40°C)
  • Example 1 synthesis of polycarbonate polyol (1)
  • Polycarbonate diol manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) UH-200N
  • 170 g hydroxyl value: 57.6 mg KOH/g
  • 1,6-hexanediol manufactured by Ube Industries, Ltd.
  • 6.07 g ⁇ -caprolactam 94.02 g
  • 0.4991 g of tetrabutoxytitanium manufactured by TCI
  • polycarbonate polyol (1) which is solid at room temperature. rice field.
  • the fact that the desired compound was obtained was confirmed by the fact that the ⁇ -caprolactam peak of the raw material disappeared and new peaks derived from the ester bond and the urethane bond appeared by NMR.
  • the resulting polycarbonate polyol (1) had a hydroxyl value of 64.5 mgKOH/g and an acid value of 0.17 mgKOH/g.
  • Examples 2 to 11 synthesis of polycarbonate polyol
  • the reaction was carried out in the same manner as in Example 1 except that the mass of raw materials, the type and amount of catalyst, and the reaction temperature and time were changed as shown in Table 1, to obtain a polycarbonate polyol that is solid at room temperature.
  • the polycarbonate polyol obtained in Example 11 was liquid at room temperature.
  • 1 H NMR was measured for the polycarbonate polyol obtained in Example 11, and the contents of ester bonds, urethane bonds, and carbonate bonds contained in the polycarbonate polyol were quantified from the integrated values. 5 wt %, 12.9 wt % urethane bonds, 17.5 wt % carbonate bonds, and the molar ratio of urethane bonds to ester bonds (urethane/ester) was 1.0.
  • Example 12 Synthesis of one-component polyurethane resin and its film
  • the resulting polyurethane resin solution (solid content: 30% by mass) was applied onto a glass plate, dried at 60°C for 1 hour and 120°C for 4 hours, and then peeled off from the glass plate to obtain a polyurethane resin film. rice field.
  • Examples 13-15 Comparative Examples 1-3: Synthesis of one-component polyurethane resin and its film
  • a solution of a polyurethane resin was obtained in the same manner as in Example 12 except that the type of polycarbonate polyol and the mass of the raw material were changed as shown in Table 2.
  • the resulting polyurethane resin solution (solid content: 30% by mass) was applied onto a glass plate, dried at 60°C for 1 hour and 120°C for 4 hours, and then peeled off from the glass plate to obtain a polyurethane resin film. rice field.
  • Table 2 shows the evaluation results of the polyurethane resin films obtained in each example and comparative example.
  • Table 3 shows other evaluation results of the polyurethane resin films obtained in each example.
  • HDL 1,6-hexanediol PDL: 1,5-pentanediol
  • UH-200 (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) UH-200, polycarbonate diol produced from HDL and dimethyl carbonate) number average Molecular weight 2000g/mol Viscosity 2300cP (75°C)
  • UH-200N (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) UH-200N, polycarbonate diol produced from HDL and dimethyl carbonate)
  • Number average molecular weight 2000 g/mol Viscosity 2300 cP (75 ° C.) PH-200N: (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) PH-200N, polycarbonate diol produced from HDL and PDL (HDL:PDL 1:1

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polyurethanes Or Polyureas (AREA)
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JPS57100130A (en) * 1980-10-29 1982-06-22 Bayer Ag Copolymer based on fatty polycarbonate and lactam
JPS61115925A (ja) * 1984-11-13 1986-06-03 Nippon Polyurethan Kogyo Kk ポリウレタンの製造方法
JPS61163931A (ja) * 1985-01-16 1986-07-24 バイエル・アクチエンゲゼルシヤフト デユロマー状脂肪族ポリカーボネートの製造法
JPH02187477A (ja) * 1988-10-22 1990-07-23 Bayer Ag Ｐｕｒ分散液と溶媒を含むコーテイング物質並びに水蒸気透過性ｐｕｒコーテイングを製造するためのその使用
JPH0632883A (ja) * 1992-05-19 1994-02-08 Bayer Ag 水希釈しうるポリエステルポリオールおよび被覆組成物におけるその使用
WO2017150202A1 (ja) * 2016-02-29 2017-09-08 凸版印刷株式会社 感熱転写記録媒体
US20180251597A1 (en) * 2014-08-29 2018-09-06 National Cheng Kung University Copolymer based on dimethyl carbonate and method of preparing the same

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CN102333804A (zh) * 2009-02-26 2012-01-25 宇部兴产株式会社 水性聚氨酯树脂分散体及其制造方法
CN110167991B (zh) * 2017-01-10 2022-06-28 三菱化学株式会社 聚碳酸酯二醇、含有聚碳酸酯二醇的组合物、聚碳酸酯二醇的制造方法和聚氨酯

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57100130A (en) * 1980-10-29 1982-06-22 Bayer Ag Copolymer based on fatty polycarbonate and lactam
JPS61115925A (ja) * 1984-11-13 1986-06-03 Nippon Polyurethan Kogyo Kk ポリウレタンの製造方法
JPS61163931A (ja) * 1985-01-16 1986-07-24 バイエル・アクチエンゲゼルシヤフト デユロマー状脂肪族ポリカーボネートの製造法
JPH02187477A (ja) * 1988-10-22 1990-07-23 Bayer Ag Ｐｕｒ分散液と溶媒を含むコーテイング物質並びに水蒸気透過性ｐｕｒコーテイングを製造するためのその使用
JPH0632883A (ja) * 1992-05-19 1994-02-08 Bayer Ag 水希釈しうるポリエステルポリオールおよび被覆組成物におけるその使用
US20180251597A1 (en) * 2014-08-29 2018-09-06 National Cheng Kung University Copolymer based on dimethyl carbonate and method of preparing the same
WO2017150202A1 (ja) * 2016-02-29 2017-09-08 凸版印刷株式会社 感熱転写記録媒体

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