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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
  • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3271—Hydroxyamines
  • C08G18/3275—Hydroxyamines containing two hydroxy 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
  • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3271—Hydroxyamines
  • C08G18/3278—Hydroxyamines containing at least three hydroxy 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
  • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
  • C08G18/348—Hydroxycarboxylic acids
• • 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
  • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether 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
  • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
  • C08G64/0208—Aliphatic polycarbonates saturated
• • 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
  • C08G64/18—Block or graft polymers
  • C08G64/183—Block or graft polymers containing polyether sequences
• • 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
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/305—General preparatory processes using carbonates and alcohols
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/08—Saturated oxiranes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/08—Polyurethanes from polyethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
  • C09D5/022—Emulsions, e.g. oil in water

Definitions

• the present invention relates to polycarbonate polyols containing oxyethylene structures and uses thereof.
• polyurethane resins have been used in a wide range of fields such as synthetic leather, artificial leather, adhesives, furniture paints, and automotive paints.
• polyether polyols, polyester polyols, and polycarbonate polyols are used as polyol components to be reacted with isocyanate.
• polyurethane resins that use polycarbonate polyol as the polyol component have superior durability in terms of heat and humidity resistance, solvent resistance, sunscreen resistance, and scratch resistance than polyurethane resins that use polyether polyols or polyester polyols. It is known.
• Patent Document 1 discloses a polycarbonate diol composition that has excellent water dilutability.
• Patent Document 2 discloses a polycarbonate/polyoxyethylene block polymer for aqueous compositions that has excellent water dilutability and can be used as an aqueous composition.
• Patent Document 3 discloses a polycarbonate diol composition that enables the formation of a coating film with excellent stain resistance and chemical resistance.
• the base agent and hardener are mixed before painting, but the base agent and hardener are stored separately until painting.
• products may be stored for long periods at temperatures above room temperature.
• Patent Document 1 Patent Document 2, and Patent Document 3 do not describe the stability of an aqueous dispersion of a water-dispersible polycarbonate polyol when stored at room temperature or higher. However, there is still room for improvement.
• polycarbonate polyols are sometimes used in combination with ether polyols, but due to compatibility issues, the number average molecular weight of the polycarbonate polyols is 500 or less. In some cases, it may be limited.
• Patent Document 1 Patent Document 2, and Patent Document 3 do not mention the compatibility between water-dispersible polycarbonate polyol and ether polyol, and there is still room for improvement.
• an object of the present invention is to provide an oxyethylene structure-containing polycarbonate polyol that has excellent stability in aqueous dispersion and/or compatibility with ether polyol.
• An oxyethylene structure-containing polycarbonate polyol having a hydroxyl value of 10 to 400 mgKOH/g Contains a structural unit represented by the following formula (A), a structural unit represented by the following formula (B), and a structural unit represented by the following formula (BB),
• the molar amount of the structural unit represented by the formula (A) is 30 to 90 with respect to the total molar amount of the structural unit represented by the formula (A) and the structural unit represented by the formula (B). is mole%
• the molar amount of the structural unit represented by the formula (B) is 10 to 70 with respect to the total molar amount of the structural unit represented by the formula (A) and the structural unit represented by the formula (B).
• R is a divalent aliphatic hydrocarbon group that may contain a heteroatom, and/or a divalent aromatic hydrocarbon group that may contain a heteroatom, R 1 is each independently hydrogen or an aliphatic hydrocarbon group having 1 to 5 carbon atoms
• A is the molar amount of the structural unit represented by the formula (A)
• B is the molar amount of the structural unit represented by the formula (B)
• BB is the molar amount of the structural unit represented by the above formula (BB)
• Mn is the number average molecular weight of the polycarbonate polyol containing an oxyethylene structure
• the polyvalent hydroxy compounds obtained by hydrolyzing the oxyethylene structure-containing polycarbonate polyol include 1,2-propanediol, 1,3-propanediol, 2 - At least one selected from the group consisting of methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol
• a paint comprising the oxyethylene structure-containing polycarbonate polyol according to any one of [1] to [9].
• the paint according to [10], wherein the paint is a water-based paint.
• an oxyethylene structure-containing polycarbonate polyol that has excellent stability in aqueous dispersion and/or compatibility with an ether polyol.
• FIG. 1 shows an NMR spectrum of a polycarbonate polyol containing an oxyethylene structure.
• this embodiment a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. Note that the present invention is not limited to the following description, and can be implemented with various modifications within the scope of the gist.
• the oxyethylene structure-containing polycarbonate polyol of this embodiment is The hydroxyl value is 10 to 400 mgKOH/g, Contains a structural unit represented by the following formula (A), a structural unit represented by the following formula (B), and a structural unit represented by the following formula (BB), The molar amount of the structural unit represented by the formula (A) is 30 to 90 with respect to the total molar amount of the structural unit represented by the formula (A) and the structural unit represented by the formula (B).
• the molar amount of the structural unit represented by the formula (B) is 10 to 70 with respect to the total molar amount of the structural unit represented by the formula (A) and the structural unit represented by the formula (B). is mole%,
• the value obtained by the following formula (i) is 150.0 to 400.0.
• R is a divalent aliphatic hydrocarbon group that may contain a heteroatom, and/or a divalent aromatic hydrocarbon group that may contain a heteroatom, R 1 is each independently hydrogen or an aliphatic hydrocarbon group having 1 to 5 carbon atoms
• A is the molar amount of the structural unit represented by the formula (A)
• B is the molar amount of the structural unit represented by the formula (B)
• BB is the molar amount of the structural unit represented by the above formula (BB)
• Mn is the number average molecular weight of the polycarbonate polyol containing an oxyethylene structure
• the oxyethylene structure-containing polycarbonate polyol of this embodiment may be a mixture of multiple polyols. In this case, it is sufficient that some of the plurality of polyols have an oxyethylene structure.
• formula (B) has the same structure as a part of formula (BB), formula (B) and formula (BB) do not overlap and are different from each other. That is, if a structure in which the terminal carbon of the structure of formula (B) is bonded to a carbonyl group via oxygen exists in the polycarbonate polyol containing an oxyethylene structure, this is not the formula (B) but the structure of the formula (B). It is determined that (BB).
• formula (B) may have the same structure as a part of formula (A), but formula (B) and formula (A) are not overlapping but different.
• the oxyethylene structure-containing polycarbonate polyol of the present embodiment has the above structure, and thus has excellent stability of an aqueous dispersion and compatibility with an ether polyol.
• the total amount of structural units represented by formula (A), formula (B), and formula (BB) is preferably 35 to 100 mol%, More preferably 45 to 100 mol%, still more preferably 50 to 100 mol%, even more preferably 55 to 100 mol%, even more particularly preferably 60 to 100 mol%, even more particularly preferably 70 to 100 mol%, and even more preferably 80 to 100 mol%. 100 mol% is even more preferred, and 90 to 100 mol% is most preferred.
• the aqueous dispersion tends to have excellent stability and durability, and The durability of coating films, polyurethane films, and/or water-based polyurethanes obtained from such oxyethylene structure-containing polycarbonate polyols tends to be better.
• the lower limit of the hydroxyl value of the oxyethylene structure-containing polycarbonate polyol of the present embodiment is 10 mgKOH/g or more, preferably 15 mgKOH/g or more, more preferably 20 mgKOH/g or more, even more preferably 25 mgKOH/g or more, and 30 mgKOH/g or more. It is even more preferably at least 35 mgKOH/g, particularly preferably at least 35 mgKOH/g, and extremely preferably at least 40 mgKOH/g.
• the upper limit is 400 mgKOH/g or less, preferably 350 mgKOH/g or less, more preferably 300 mgKOH/g or less, even more preferably 275 mgKOH/g or less, even more preferably 250 mgKOH/g or less, particularly 200 mgKOH/g or less.
• 150 mgKOH/g or less is extremely preferable.
• the numerical range may be defined by appropriately combining the lower limit and the upper limit.
• the range of hydroxyl value is 10 to 400 mgKOH/g, 15 to 350 mgKOH/g, 20 to 300 mgKOH/g, 25 to 275 mgKOH/g, 30 to 250 mgKOH/g, 35 to 200 mgKOH/g, or 40 to 150 mgKOH/g.
• the method for controlling the hydroxyl value of the oxyethylene structure-containing polycarbonate polyol of the present embodiment within the above range is not particularly limited, but for example, when producing the oxyethylene structure-containing polycarbonate polyol, the hydroxyl value may be controlled within the above range. It is controlled by a method of charging a polycarbonate polyol as a raw material and a polyhydric hydroxy compound having a structure represented by formula (B), or by adding and/or extracting a polyhydric hydroxy compound during the production of the polycarbonate polyol containing an oxyethylene structure. There are several methods.
• the hydroxyl value can be calculated using the method described in Examples described later.
• R is a divalent aliphatic hydrocarbon group that may contain a hetero atom, and/or a divalent aromatic hydrocarbon group that may contain a hetero atom. It is the basis.
• the aliphatic hydrocarbon group may be linear, branched, or cyclic.
• a plurality of R's may be the same or different.
• R is a divalent linear aliphatic hydrocarbon group which may contain a heteroatom
• the lower limit of the molecular weight of R is preferably 10 or more, more preferably 20 or more.
• the upper limit of the molecular weight of R is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2200 or less.
• the molecular weight range of R may be, for example, 10-3000, 20-2500, or 20-2200.
• R is an ethylene group (-CH 2 -CH 2 -)
• R is a divalent linear aliphatic hydrocarbon group which may contain a heteroatom
• specific examples include, but are not limited to, a methylene group, an ethylene group, a propylene group, a butylene group
• Examples include pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, oxyethylene group, oxytetramethylene group, polyoxyethylene group, polyoxytetramethylene group, fluoroalkyl group, perfluoroalkyl group, etc.
• methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptalene group, octylene group, nonylene group, decylene group are preferable, and methylene group, ethylene group, propylene group, butylene group group is more preferred.
• R is a divalent branched aliphatic hydrocarbon group which may contain a heteroatom
• the lower limit of the molecular weight of R is preferably 10 or more, more preferably 20 or more.
• the upper limit of the molecular weight of R is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2200 or less.
• the molecular weight range of R may be, for example, 10-3000, 20-2500, or 20-2200.
• R is a divalent branched aliphatic hydrocarbon group which may contain a heteroatom
• specific examples thereof include, but are not limited to, an isopropylene group, an isobutylene group, a tert-butylene group
• Examples include isopentylene group, 2,2-dimethyltrimethylene group, isohexylene group, isoheptylene group, isooctylene group, oxy1-methylethylene group, oxy2,2-dimethyltrimethylene group, polyoxy1-methylethylene group, and the like.
• isopropylene group, isobutylene group, isopentylene group, 2,2-dimethyltrimethylene group or isohexylene group, and oxy-1-methylethylene group are preferable.
• R is a divalent cyclic aliphatic hydrocarbon group which may contain a heteroatom
• the lower limit of the molecular weight of R is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more.
• the upper limit of the molecular weight of R is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2200 or less.
• the molecular weight range of R may be, for example, 10-3000, 20-2500, or 30-2200.
• R is a divalent cyclic aliphatic hydrocarbon group which may contain a heteroatom
• specific examples thereof include, but are not limited to, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, etc. Examples include groups.
• R may be a divalent aromatic hydrocarbon group that may contain a heteroatom.
• the lower limit of the molecular weight of R is preferably 50 or more, more preferably 60 or more, and even more preferably 70 or more.
• the upper limit of the molecular weight of R is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2200 or less.
• the molecular weight range of R may be, for example, 50-3000, 60-2500, or 70-2200.
• R is preferably a divalent linear, branched, or cyclic aliphatic hydrocarbon group that may contain a heteroatom and has a lower limit of R's molecular weight of 10 or more.
• a divalent linear aliphatic hydrocarbon group is more preferable, and a divalent linear aliphatic hydrocarbon group in which R has a molecular weight of 10 or more is even more preferable, and a divalent linear aliphatic hydrocarbon group in which R has a molecular weight of 20 or more is more preferable. Hydrogen groups are even more preferred. Further, R is preferably a divalent linear, branched or cyclic aliphatic hydrocarbon group which may contain a heteroatom and has an upper limit of the molecular weight of R of 3000 or less; is 2,500 or less, or a divalent branched chain that may contain a heteroatom, and the upper limit of the molecular weight of R is 2,500 or less.
• a divalent linear aliphatic hydrocarbon group is more preferable, a divalent linear aliphatic hydrocarbon group in which the upper limit of the molecular weight of R is 2000 or less, and a divalent linear aliphatic hydrocarbon group in which the upper limit of the molecular weight of R is 1500 or less.
• a divalent linear aliphatic hydrocarbon group in which the upper limit of the molecular weight of R is 1000 or less is particularly preferable.
• R 1 is hydrogen or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
• the aliphatic hydrocarbon group may be linear, branched, or cyclic.
• a plurality of R 1 's may be the same or different.
• aliphatic hydrocarbon group for R 1 are not particularly limited, but include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, isopropyl group, isobutyl group, tert-butyl group, isopentyl group, etc. Can be mentioned.
• R 1 is preferably hydrogen, methyl group, ethyl group, propyl group, butyl group, pentyl group, isopropyl group, or isobutyl group, more preferably hydrogen, methyl group, ethyl group, propyl group, or butyl group, hydrogen, A methyl group, an ethyl group, and a propyl group are more preferred, hydrogen, a methyl group, and an ethyl group are even more preferred, hydrogen and a methyl group are particularly preferred, and hydrogen is particularly preferred.
• the structural unit represented by formula (A) has durability, the structural unit represented by formula (B) has hydrophilicity, and the structure represented by formula (BB) has hydrophilicity and ether Compatible with polyols.
• the structural unit represented by formula (A) tends to be less hydrophobic and less compatible with ether polyols, and the structural unit represented by formula (B) tends to become hydrophilic due to a change in steric structure due to heating.
• the structure represented by formula (BB) tends to have lower hydrophilicity than formula (B).
• the structural unit represented by the formula (A), the structural unit represented by the formula (B), etc. , and the structural units represented by formula (BB) are essential, and it is necessary that these structural units fall within a certain range, that is, the range of values obtained by formula (i) is within the above range.
• cases where the value obtained by formula (i) is less than the lower limit of the above range include cases where there are few structural units represented by formula (BB), and in this case, the oxyethylene structure-containing polycarbonate polyol is , the stability of the aqueous dispersion and the compatibility with the ether polyol tend to decrease.
• the value obtained by formula (i) exceeds the upper limit of the above range, there is a case where there are few structural units represented by formula (B), and in this case, the oxyethylene structure-containing polycarbonate polyol has low hydrophilicity and tends to have poor dispersibility in water.
• formula (i) when the value obtained by formula (i) exceeds the upper limit of the above range, there is a case where there are few structural units represented by formula (A), and in this case, the oxyethylene structure-containing polycarbonate polyol is a tendency for durability to decrease.
• A is the molar amount of the structural unit represented by formula (A)
• B is the molar amount of the structural unit represented by formula (B)
• BB is the molar amount of the structural unit represented by formula (B).
• ) is the molar amount of the structural unit represented by
• the molar ratio of [BB/A] and the molar ratio of [B/(A+B)] in formula (i) can be measured by nuclear magnetic resonance (NMR) measurement as described in the Examples below.
• Mn represents the number average molecular weight of the oxyethylene structure-containing polycarbonate polyol, and can be measured by GPC measurement as described in the Examples below.
• the range of values obtained by formula (i) is 150.0 to 400.0.
• the lower limit of the value obtained by formula (i) is preferably 155.0 or more, more preferably 160.0 or more, and even more preferably 165.0 or more.
• the upper limit is preferably 350.0 or less, more preferably 300.0 or less, and even more preferably 275.0 or less.
• the numerical range may be defined by appropriately combining the lower limit and the upper limit.
• the range of values obtained by formula (i) may be 155.0 to 350.0, 160.0 to 300.0, or 165.0 to 275.0.
• the lower limit of the number average molecular weight (Mn) of the oxyethylene structure-containing polycarbonate polyol of the present embodiment is preferably 300 or more, more preferably 400 or more, even more preferably 500 or more, even more preferably 700 or more, and especially 900 or more. Preferably, 1000 or more is more particularly preferable.
• the upper limit of the number average molecular weight (Mn) of the oxyethylene structure-containing polycarbonate polyol of this embodiment is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 5,000 or less, even more preferably 4,500 or less, and even more preferably 4,000 or less.
• the number average molecular weight of the polycarbonate polyol containing an oxyethylene structure may be set to 300 to 10,000, 400 to 8,000, 500 to 5,000, 700 to 4,500, 900 to 4,000, 1,000 to 3,800, 1,000 to 3,500, or 1,000 to 3,200. good.
• the oxyethylene structure-containing polycarbonate polyol of the present embodiment has excellent compatibility with and ether polyol. Paints, polyurethanes, and/or water-based polyurethanes tend to have better durability.
• the method for controlling the number average molecular weight (Mn) of the oxyethylene structure-containing polycarbonate polyol of the present embodiment within the above range is not particularly limited, but for example, when producing the oxyethylene structure-containing polycarbonate polyol, the number average molecular weight (Mn ) is within the above range, a method of preparing a raw material polycarbonate polyol and a polyhydric hydroxy compound having a structure represented by formula (B), or adding a polyhydric hydroxy compound during the production of the polycarbonate polyol containing an oxyethylene structure. and/or a method of controlling by extracting.
• the number average molecular weight (Mn) of the oxyethylene structure-containing polycarbonate polyol can be calculated by GPC measurement described in Examples described below.
• the lower limit of the molecular weight distribution (Mw/Mn) of the oxyethylene structure-containing polycarbonate polyol of this embodiment is preferably 1.50 or more, more preferably 1.60 or more, even more preferably 1.70 or more, and 1.80 or more. is even more preferable, and 1.90 or more is particularly preferable.
• the upper limit is preferably 5.00 or less, more preferably 4.00 or less, even more preferably 3.50 or less, even more preferably 2.75 or less, and particularly preferably 2.50 or less.
• the numerical range may be defined by appropriately combining the lower limit and the upper limit.
• the molecular weight distribution range of the polycarbonate polyol containing an oxyethylene structure is set to 1.50 to 5.00, 1.60 to 4.00, 1.70 to 3.50, 1.80 to 2.75, or 1. It may be set to 90 to 2.50.
• the oxyethylene structure-containing polycarbonate polyol of this embodiment has excellent stability of an aqueous dispersion and compatibility with an ether polyol. Coating compositions using structure-containing polycarbonate polyols tend to have better flexibility and chemical resistance, and polyurethanes and/or water-based polyurethanes using such oxyethylene structure-containing polycarbonate polyols tend to have better flexibility and chemical resistance. They tend to have better chemical properties.
• the method for controlling the molecular weight distribution (Mw/Mn) of the oxyethylene structure-containing polycarbonate polyol of the present embodiment within the above range is not particularly limited, but for example, when producing the oxyethylene structure-containing polycarbonate polyol, the molecular weight distribution (Mw /Mn) is within the above range, the raw material polycarbonate polyol and the polyhydric hydroxy compound having the structure represented by formula (B) are charged, or the polyhydric hydroxy compound is added during the production of the oxyethylene structure-containing polycarbonate polyol.
• One example is a method of controlling by adding and/or extracting.
• the number average molecular weight (Mn) and weight average molecular weight (Mw) of the oxyethylene structure-containing polycarbonate polyol can be calculated by GPC measurement described in the Examples described later, and the calculated number average
• the molecular weight distribution (Mw/Mn) can be determined by the following formula (II) using the molecular weight (Mn) and the weight average molecular weight (Mw).
• Molecular weight distribution (Mw/Mn) weight average molecular weight (Mw)/number average molecular weight (Mn)...(II)
• the average carbon number of the polyvalent hydroxy compounds excluding the polyvalent hydroxy compounds having an oxyethylene structure has a lower limit of 2. 0 or more is preferable, 2.5 or more is more preferable, 3.0 or more is still more preferable, 3.2 or more is even more preferable, 3.5 or more is particularly preferable, 3.8 or more is particularly preferable, 4.0
• the upper limit is preferably 15.0 or less, more preferably 12.0 or less, even more preferably 10.0 or less, even more preferably 8.0 or less, particularly preferably 6.5 or less, and 6.0 or less.
• the numerical range may be defined by appropriately combining the lower limit and the upper limit.
• the average carbon number range of polyvalent hydroxy compounds (excluding polyvalent hydroxy compounds having an oxyethylene structure) is 2.0 to 15.0, 2.5 to 12.0, 3.0 to 10.0. , 3.2 to 8.0, 3.5 to 6.5, 3.8 to 6.0, 4.0 to 5.5, or 4.0 to 5.2.
• the oxyethylene structure-containing polycarbonate polyol of this embodiment has excellent flexibility and durability. Coating compositions using polycarbonate polyols containing an oxyethylene structure tend to have a better balance between flexibility and durability, and polyurethanes and/or water-based polyurethanes using polycarbonate polyols containing an oxyethylene structure tend to have a better balance between flexibility and durability. tend to have better flexibility and durability.
• the polyhydric hydroxy compound obtained by hydrolyzing the oxyethylene structure-containing polycarbonate polyol of this embodiment is a 1,2- Propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6- It preferably contains at least one selected from the group consisting of hexanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, It is more preferable to contain at least one selected from the group consisting of 3-methyl-1,5-pentanediol, 1,6-hexanediol, and 1,3-propanedio
• the lower limit of the number average molecular weight of the polyvalent hydroxy compound having an oxyethylene structure is preferably 300 or more, and more preferably 400 or more. It is preferably 500 or more, even more preferably 600 or more, particularly preferably 700 or more, even more preferably 800 or more, and extremely preferably 900 or more. Further, the upper limit is preferably 3,000 or less, more preferably 2,800 or less, even more preferably 2,500 or less, even more preferably 2,200 or less, particularly preferably 2,000 or less, even more preferably 1,800 or less, extremely preferably 1,500 or less, and 1,300 or less. is even more preferable.
• the numerical range may be defined by appropriately combining the lower limit and the upper limit.
• the number average molecular weight range of the polyvalent hydroxy compound having an oxyethylene structure is set to 300 to 3000, 400 to 2800, 500 to 2500, 600 to 2200, 700 to 2000, 800 to 1800, 900 to 1500, or 900 to It may be set to 1300.
• the oxyethylene structure-containing polycarbonate polyol of this embodiment has excellent stability of the aqueous dispersion and compatibility with the ether polyol, Coating compositions using such oxyethylene structure-containing polycarbonate polyols tend to have a better balance between flexibility and chemical resistance, and polyurethanes using such oxyethylene structure-containing polycarbonate polyols and/or Water-based polyurethanes tend to have better flexibility and chemical resistance.
• polyhydric hydroxy compound having an oxyethylene structure is preferably polyethylene glycol.
• the oxyethylene structure-containing polycarbonate polyol of this embodiment can have a hydrophilic structure other than the oxyethylene structure.
• the hydrophilic structure include, but are not limited to, nonionic hydrophilic groups, anionic hydrophilic groups, cationic hydrophilic groups, and the like. Among them, from the viewpoint of versatility, nonionic hydrophilic groups and anionic hydrophilic groups are preferred.
• the nonionic hydrophilic group is not particularly limited, specific examples thereof include glycoside groups and the like.
• the anionic hydrophilic group is not particularly limited, but specific examples thereof include a sulfonic acid group and a carboxyl group.
• the lower limit of the content of the hydrophilic structure in the polycarbonate polyol containing an oxyethylene structure is not particularly limited. It is preferable to contain a hydrophilic structure, and it is more preferable to contain a hydrophilic structure so that the evaluation of water dispersibility described in the examples described later gives a rating of ⁇ .
• the upper limit is preferably 50 mol% or less, more preferably 35 mol% or less, even more preferably 30 mol% or less, even more preferably 25 mol% or less, particularly preferably 20 mol% or less, even more particularly preferably 15 mol% or less, and Highly preferred.
• the oxyethylene structure-containing polycarbonate polyol of this embodiment tends to be able to be dispersed in water. Coating compositions and polyurethanes obtained from structure-containing polycarbonate polyols tend to have excellent durability.
• the oxyethylene structure-containing polycarbonate polyol of this embodiment is preferably dispersible in water. If the oxyethylene structure-containing polycarbonate polyol of this embodiment can be dispersed in water, the stability of the water-based coating composition and/or the stability of the water-based polyurethane using the oxyethylene structure-containing polycarbonate polyol will be improved. There is a tendency.
• the dispersibility of the oxyethylene structure-containing polycarbonate polyol in water can be determined based on the water dispersibility described in the Examples below.
• the oxyethylene structure-containing polycarbonate polyol of the present embodiment can be obtained, for example, by reacting a polycarbonate polyol with a polyhydric hydroxy compound having a structure represented by formula (B) in the presence of a transesterification catalyst described below. can.
• the oxyethylene structure-containing polycarbonate polyol may become cloudy or become easily colored by heating. Furthermore, when producing polyurethane, the reaction may be inhibited or excessively accelerated. Too little catalyst is not preferred because the reaction tends to slow down.
• the amount of catalyst remaining in the oxyethylene structure-containing polycarbonate polyol is not particularly limited, but the lower limit is preferably 0.00001% by mass or more, more preferably 0.00005% by mass or more as the content in terms of catalyst metal. It is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, and even more preferably 0.0005% by mass or more. Further, the upper limit is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, even more preferably 0.03% by mass or less, even more preferably 0.02% by mass or less, and even more preferably 0.015% by mass. The following is particularly preferred, 0.01% by mass or less is particularly preferred, and 0.005% by mass or less is extremely preferred.
• the chromaticity (APHA) of the raw material used in producing the oxyethylene structure-containing polycarbonate polyol of this embodiment is preferably 100 or less, more preferably 80 or less, even more preferably 50 or less, and even more preferably 30 or less. , 20 or less is particularly preferred. When the APHA of the raw material is below the above value, the APHA of the resulting oxyethylene structure-containing polycarbonate polyol tends to be excellent.
• the polyhydric hydroxy compound having the structure represented by formula (B) used in producing the oxyethylene structure-containing polycarbonate polyol of this embodiment is not particularly limited, but includes diethylene glycol, triethylene glycol, tetraethylene glycol, Examples include heptaethylene glycol, hexaethylene glycol, heptaethylene glycol, and the "Polyethylene Glycol" series manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• the transesterification catalyst is not particularly limited, but includes, for example, alkali metals and alkaline earth metals, alcoholates thereof, hydrides thereof, oxides thereof, amides thereof, hydroxides thereof, and salts thereof.
• Salts of alkali metals and alkaline earth metals are not particularly limited, and include, for example, carbonates, nitrogen-containing borates, basic salts with organic acids, and the like.
• Alkali metals include, but are not particularly limited to, lithium, sodium, potassium, and the like.
• alkaline earth metals include, but are not particularly limited to, magnesium, calcium, strontium, barium, and the like.
• Transesterification catalysts using metals other than alkali metals and alkaline earth metals include, but are not particularly limited to, metals other than alkali metals and alkaline earth metals, salts thereof, alcoholates thereof, and Examples include organic compounds containing metals.
• metals other than alkali metals and alkaline earth metals are not particularly limited, but include, for example, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, Examples include molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, and ytterbium.
• transesterification catalysts can be used alone or in combination of two or more.
• the transesterification reaction to obtain an oxyethylene structure-containing polycarbonate polyol is better carried out, and when the obtained oxyethylene structure-containing polycarbonate polyol is used, there is less influence on the urethane reaction.
• One or more metals selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, titanium, manganese, zirconium, tin, lead, and ytterbium, or salts thereof, alkoxides thereof, or organic materials containing these metals.
• one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, manganese, ytterbium, tin, zinc and zirconium are more preferred, consisting of lithium, magnesium, calcium, titanium, manganese and ytterbium. More preferably one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium and manganese, even more preferably one or more metals selected from the group consisting of lithium, calcium, titanium and manganese.
• One or more metals selected from the group consisting of lithium, titanium, and manganese are particularly preferable, and one or more metals selected from the group consisting of titanium and manganese are particularly preferable. is particularly preferred.
• transesterification catalysts include, for example, organic compounds of titanium, organic compounds of magnesium, organic compounds of zinc, organic compounds of ytterbium, organic compounds of zirconium, and organic compounds of manganese.
• the organic compound of titanium is not particularly limited, but includes, for example, titanium tetra-n-butoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, and the like.
• organic compound of magnesium examples include, but are not particularly limited to, magnesium acetate, magnesium (II) acetylacetonate, 2,2,6,6-tetramethyl-3,5-heptanedionatomagnesium (II) dihydrate Examples include things.
• organic compound of zinc examples include, but are not particularly limited to, zinc acetate, zinc (II) acetylacetonate, zinc (II) 2,2,6,6-tetramethyl-3,5-heptanedionato, and the like.
• organic compounds of ytterbium include, but are not limited to, ytterbium (III) isopropoxide, ytterbium (III) trifluoromethanesulfonate, tris(cyclopentadienyl) ytterbium (III), acetylacetonate ytterbium (III).
• examples include hydrates.
• Examples of the organic compound of zirconium include, but are not limited to, zirconium (IV) acetylacetone, zirconium (IV) tetrapropoxide, zirconium (IV) tetrabutoxide, zirconium (IV) acetylacetonate, and the like.
• the organic compound of manganese is not particularly limited, but includes, for example, manganese (II) acetate, manganese (II) acetylacetonate, and the like.
• the lower limit of the amount of the transesterification catalyst used is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, based on the total mass of the raw materials.
• the upper limit is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, even more preferably 0.025% by mass or less, even more preferably 0.015% by mass or less, and even more preferably 0.01% by mass. The following are particularly preferred.
• the transesterification reaction can be carried out by mixing the raw materials and stirring while heating.
• the temperature of the transesterification reaction is not particularly limited, but the lower limit is preferably 120°C or higher, more preferably 140°C or higher, and the upper limit is preferably 250°C or lower, more preferably 200°C or lower.
• reaction temperature By setting the reaction temperature to the above lower limit or higher, the transesterification reaction can be carried out in a shorter time, resulting in excellent economic efficiency.
• reaction temperature By controlling the reaction temperature to be below the above upper limit, coloring of the resulting oxyethylene structure-containing polycarbonate polyol can be more effectively prevented.
• the reaction pressure for the transesterification reaction is not particularly limited, but is preferably at least normal pressure and at most 1 MPa. By setting the reaction pressure within the above range, the reaction can be carried out more easily. Furthermore, when using auxiliary raw materials, the transesterification reaction can be promoted more efficiently by pressurizing them to a certain extent, taking into account their vapor pressures and the like.
• a step of dehydrating the raw material to be used may be performed as a pretreatment before the above-described transesterification reaction.
• a step of adding the above-mentioned catalyst poison to the transesterification catalyst may be performed as a post-treatment.
• the polycarbonate polyol used in producing the oxyethylene structure-containing polycarbonate polyol of this embodiment is not particularly limited, but can be obtained, for example, by the method for producing polycarbonate polyol described below.
• commercially available products can also be used, including, but not limited to, T6002, T6001, T5652, T5651, T5650J, T5650E, G4672, T4672, T4671, G3452, G3450J, GE502, GE501 manufactured by Asahi Kasei Corporation. Examples include the Duranol (trade name) series.
• the method for producing the polycarbonate polyol used to produce the oxyethylene structure-containing polycarbonate polyol of this embodiment is not particularly limited, and any known method may be employed.
• a polycarbonate polyol can be obtained by reacting a carbonate compound and a polyhydric hydroxy compound in the presence of a transesterification catalyst.
• Carbonate compounds used in the production of polycarbonate polyols include, but are not limited to, alkylene carbonates, dialkyl carbonates, diaryl carbonates, and the like.
• alkylene carbonate examples include, but are not limited to, ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1,2-pentylene carbonate, and the like. It will be done.
• dialkyl carbonate examples include, but are not limited to, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, and the like.
• the diaryl carbonate is not particularly limited, and examples include diphenyl carbonate.
• the carbonate compound used in the production of polycarbonate polyol is preferably dimethyl carbonate, diethyl carbonate, ethylene carbonate, or diphenyl carbonate, more preferably dimethyl carbonate, ethylene carbonate, or diphenyl carbonate, even more preferably ethylene carbonate or diphenyl carbonate, and ethylene carbonate. Carbonates are even more preferred.
• polyvalent hydroxy compound used in the production of polycarbonate polyols are not limited to the following, but include, for example, linear polyvalent hydroxy compounds, branched polyvalent hydroxy compounds, cyclic polyvalent hydroxy compounds, and compounds having an aromatic ring. Examples include polyhydric hydroxy compounds.
• the linear polyhydric hydroxy compound is not particularly limited, but includes, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycol, poly Examples include tetraethylene glycol.
• Branched polyhydric hydroxy compounds include, but are not particularly limited to, 2-methyl-1,8-octanediol, neopentyl glycol, 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, trimethylolpropane, pentaerythritol, polypropylene glycol etc.
• Examples of the cyclic polyhydric hydroxy compound include, but are not limited to, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-bis(4-hydroxycyclohexyl)-propane isosol. Examples include byde and the like.
• a transesterification reaction catalyst can be used in the production of polycarbonate polyol.
• the transesterification catalyst is not particularly limited, but includes, for example, alkali metals and alkaline earth metals, alcoholates thereof, hydrides thereof, oxides thereof, amides thereof, hydroxides thereof, and salts thereof.
• Salts of alkali metals and alkaline earth metals are not particularly limited, and include, for example, carbonates, nitrogen-containing borates, basic salts with organic acids, and the like.
• Alkali metals include, but are not particularly limited to, lithium, sodium, potassium, and the like.
• alkaline earth metals include, but are not limited to, magnesium, calcium, strontium, barium, and the like.
• Transesterification catalysts using metals other than alkali metals and alkaline earth metals include, but are not particularly limited to, metals other than alkali metals and alkaline earth metals, salts thereof, alcoholates thereof, and Examples include organic compounds containing metals.
• metals other than alkali metals and alkaline earth metals are not particularly limited, but include, for example, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, Examples include molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, and ytterbium.
• transesterification catalysts can be used alone or in combination of two or more.
• lithium, sodium, potassium, magnesium, One or more metals selected from the group consisting of calcium, titanium, manganese, zirconium, tin, lead and ytterbium, salts thereof, alkoxides thereof, or organic compounds containing these metals are preferred; lithium, magnesium, One or more metals selected from the group consisting of calcium, titanium, manganese, ytterbium, tin, zinc, and zirconium are more preferable, and one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, manganese, and ytterbium.
• one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, and manganese are even more preferable, and one or more metals selected from the group consisting of lithium, calcium, titanium, and manganese are even more preferable.
• Metals are particularly preferred, one or more metals selected from the group consisting of lithium, titanium and manganese are even more particularly preferred, and one or more metals selected from the group consisting of titanium and manganese are even more particularly preferred.
• transesterification catalysts include, for example, organic compounds of titanium, organic compounds of magnesium, organic compounds of zinc, organic compounds of ytterbium, organic compounds of zirconium, and organic compounds of manganese.
• the organic compound of titanium is not particularly limited, but includes, for example, titanium tetra-n-butoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, and the like.
• organic compound of magnesium examples include, but are not particularly limited to, magnesium acetate, magnesium (II) acetylacetonate, 2,2,6,6-tetramethyl-3,5-heptanedionatomagnesium (II) dihydrate Examples include things.
• organic compound of zinc examples include, but are not particularly limited to, zinc acetate, zinc (II) acetylacetonate, zinc (II) 2,2,6,6-tetramethyl-3,5-heptanedionato, and the like.
• organic compounds of ytterbium include, but are not limited to, ytterbium (III) isopropoxide, ytterbium (III) trifluoromethanesulfonate, tris(cyclopentadienyl) ytterbium (III), acetylacetonate ytterbium (III).
• examples include hydrates.
• Examples of the organic compound of zirconium include, but are not limited to, zirconium (IV) acetylacetone, zirconium (IV) tetrapropoxide, zirconium (IV) tetrabutoxide, zirconium (IV) acetylacetonate, and the like.
• the organic compound of manganese is not particularly limited, but includes, for example, manganese (II) acetate, manganese (II) acetylacetonate, and the like.
• the lower limit of the amount of the transesterification catalyst used is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, based on the total mass of the raw materials.
• the upper limit is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, even more preferably 0.025% by mass or less, even more preferably 0.015% by mass or less, and even more preferably 0.01% by mass. The following are particularly preferred.
• the transesterification catalyst used in the transesterification reaction is not consumed in the transesterification reaction when heat treatment is performed subsequent to the production of polycarbonate polyol, so it can be calculated based on the amount of transesterification catalyst used.
• the amount of metal in the transesterification catalyst contained in the polycarbonate polyol is determined by measuring by ICP (inductively coupled plasma).
• polycarbonate polyol used in this embodiment can also be produced by transesterification of a polycarbonate polyol and a diol compound, or of two or more types of polycarbonate polyols.
• the raw material polycarbonate polyol contains catalyst poisons from the transesterification catalyst used during its production, the transesterification reaction usually tends to be difficult to proceed. Therefore, when producing a polycarbonate polyol, the above-mentioned transesterification catalyst can be newly added in the required amount.
• the transesterification reaction in this embodiment usually tends to proceed easily.
• the same transesterification catalyst as used in the production of polycarbonate polyol as a raw material can be employed.
• the transesterification reaction can be carried out by mixing the raw materials and stirring while heating.
• the temperature of the transesterification reaction is not particularly limited, but the lower limit is preferably 120°C or higher, more preferably 140°C or higher, and the upper limit is preferably 250°C or lower, more preferably 200°C or lower.
• reaction temperature By setting the reaction temperature to the above lower limit or higher, the transesterification reaction can be carried out in a shorter time, resulting in excellent economic efficiency.
• reaction temperature By controlling the reaction temperature to be below the above upper limit, coloring of the obtained polycarbonate polyol can be more effectively prevented.
• the reaction pressure for the transesterification reaction is not particularly limited, but is preferably at least normal pressure and at most 1 MPa. By setting the reaction pressure within the above range, the reaction can be carried out more easily. Furthermore, when using auxiliary raw materials, the transesterification reaction can be promoted more efficiently by pressurizing them to a certain extent, taking into account their vapor pressures and the like.
• the progress and completion of the transesterification reaction can be confirmed by GPC measurement.
• the peak derived from the raw material becomes smaller over time, which can be confirmed by the disappearance of the peak.
• a step of dehydrating the raw material to be used may be performed as a pretreatment.
• a step of adding the above-mentioned catalyst poison to the transesterification catalyst may be performed as a post-treatment.
• the paint of this embodiment contains the above-mentioned oxyethylene structure-containing polycarbonate polyol.
• the coating material of this embodiment has excellent compatibility with ether polyol, flexibility, and durability because it contains the above-mentioned oxyethylene structure-containing polycarbonate polyol.
• the paint of this embodiment is preferably a water-based paint.
• a water-based paint is a paint that contains water as a main component as a solvent or dispersion medium.
• volatile organic compounds VOC
• the paint of this embodiment may contain other components in addition to the above-mentioned oxyethylene structure-containing polycarbonate polyol.
• Other components include, but are not particularly limited to, curable compositions, polyhydric alcohol compounds, polyester polyols, acrylic polyols, polyether polyols, polyolefin polyols, fluorine polyols, etc. described in JP-A-2018-012769. Examples include polyols.
• the paint (paint composition) of this embodiment may also include, for example, a curing accelerator (catalyst), a matting agent, an anti-settling agent, a leveling agent, a filler, a dispersant, etc., depending on various uses.
• a curing accelerator catalyst
• a matting agent such as a glycerol, a glycerol, a glycerol, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium
• the paint of this embodiment can also be obtained using polyurethane or water-based polyurethane, which will be described later.
• the polyurethane of this embodiment is obtained using the above-mentioned oxyethylene structure-containing polycarbonate polyol.
• the polyurethane of this embodiment has excellent flexibility and durability because it is obtained using the above-mentioned oxyethylene structure-containing polycarbonate polyol.
• the water-based polyurethane of this embodiment is obtained using the above-mentioned oxyethylene structure-containing polycarbonate polyol.
• the water-based polyurethane of this embodiment is obtained using the above-mentioned oxyethylene structure-containing polycarbonate polyol, and thus has excellent emulsion particle stability, flexibility, and durability.
• water-based polyurethane means a polyurethane dispersion containing water as a dispersion medium.
• the method for obtaining the polyurethane of this embodiment is not particularly limited, but for example, after synthesizing an NCO group-terminated prepolymer using the above-mentioned oxyethylene structure-containing polycarbonate polyol and an isocyanate compound, a polyhydric alcohol and/or a polyamine
• a prepolymer method two-step method in which the chain is extended by adding a polycarbonate polyol, and a one-shot method (one-step method) in which the above-mentioned oxyethylene structure-containing polycarbonate polyol is simultaneously polymerized with an isocyanate compound and a polyhydric alcohol and/or a polyamine.
• a prepolymer method two-step method in which the chain is extended by adding a polycarbonate polyol
• a one-shot method one-step method in which the above-mentioned oxyethylene structure-containing polycarbonate polyol is simultaneously polymerized with an isocyanate compound and a polyhydric alcohol and/or a
• the method for obtaining the water-based polyurethane of the present embodiment is not particularly limited, but includes, for example, the method described in Examples of JP-A-2017-71685.
• the artificial leather of this embodiment is obtained using the above-mentioned polyurethane or water-based polyurethane.
• the artificial leather of this embodiment has excellent flexibility and durability because it is obtained using the above-mentioned polyurethane or water-based polyurethane.
• the synthetic leather of this embodiment is obtained using the above-mentioned polyurethane or water-based polyurethane.
• the synthetic leather of this embodiment has excellent flexibility and durability because it is obtained using the above-mentioned polyurethane or water-based polyurethane.
• the coating film of this embodiment is obtained from the above-mentioned paint. Since the coating film of this embodiment is obtained from the above-mentioned coating material, it has excellent flexibility, durability, and coating film appearance when used in combination with an ether polyol.
• hydroxyl value [Measurement of hydroxyl value (OHV)]
• the hydroxyl value was measured by the following method. Using a volumetric flask, pyridine was added to 12.5 g of acetic anhydride to make 50 mL to prepare an acetylation reagent. 1.0 to 10.0 g of the sample was accurately weighed and placed in a 100 mL eggplant flask. 5 mL of acetylation reagent and 10 mL of toluene were added to the eggplant flask using a whole pipette to obtain a solution. Thereafter, a cooling tube was attached to the eggplant flask, and the solution was stirred and heated at 100° C. for 1 hour.
• the number average molecular weight (Mn) and weight average molecular weight (Mw) of the oxyethylene structure-containing polycarbonate polyol were measured by GPC using the following method. Oxyethylene structure-containing polycarbonate polyols obtained in Examples and Comparative Examples described below were used as samples. The concentration of the measurement sample was adjusted with tetrahydrofuran (hereinafter referred to as THF) to be 0.5% by mass, and the number average molecular weight (Mn) and weight average molecular weight (Mw) were measured in terms of standard polystyrene using the GPC device below. .
• THF tetrahydrofuran
• GPC device Tosoh Corporation HLC-8320 Analytical column: TSKgel G4000H 1 piece G3000H 1 piece G2000H 2 pieces Guard column: TSKgel guardcolumn H XL -L Reference column: TSKgel SuperH-RC Eluent: Tetrahydrofuran (THF) Flow rate: 1.0mL/min Column temperature: 40°C RI detector: RI (equipment HLC-8320 built-in) Calibration curve: Standard polystyrene (manufactured by Tosoh Corporation)
• dimers to decamers were calculated from A-500 and A-1000.
• Dimer molecular weight: 266)
• Trimer molecular weight: 370
• Tetramer molecular weight: 474)
• Pentamer molecular weight: 578)
• Hexamer molecular weight: 682
• Heptamer molecular weight: 786
• Octamer molecular weight: 890
• Nonamer molecular weight: 994) Decamer (molecular weight: 1098)
• Calibration curve formula 3rd order polynomial
• the analysis was carried out using a gas chromatography GC-2014 (manufactured by Shimadzu Corporation) equipped with DB-WAX (manufactured by J&W) as a column and a flame ionization detector (FID) as a detector.
• the temperature profile of the column was such that after being held at 60°C for 5 minutes, the temperature was raised to 250°C at a rate of 10°C/min.
• the molar ratio of the polyvalent hydroxy compound (excluding the polyvalent hydroxy compound having an oxyethylene structure) was calculated from the weight percent obtained by the above gas chromatography and the molecular weight of each polyvalent hydroxy compound.
• the average carbon number was calculated from the molar ratio of the polyvalent hydroxy compound (excluding the polyvalent hydroxy compound having an oxyethylene structure) after hydrolysis using the following formula (IV). ⁇ [Number of carbon atoms in a polyvalent hydroxy compound (excluding polyvalent hydroxy compounds having an oxyethylene structure) x molar fraction of the polyvalent hydroxy compound]...(IV)
• the polyvalent hydroxy compounds include 2-methyl-1,3-propanediol (92 mol%), 1 ,6-hexanediol (8 mol%), the average carbon number is 4.16 (4 ⁇ 0.92+6 ⁇ 0.08).
• NMR device JEOL-ECZ500 Observation core: 1H Waiting time: 5 seconds Accumulation: 128 times Solvent: CDCl 3 Measurement temperature: Room temperature Chemical shift standard: TMS 0.00ppm
• the integral values of the following signals were divided by the number of hydrogen atoms, and the molar ratios [BB/A] and [B/(A+B)] were determined from the values.
• the number of hydrogen atoms in a1 was determined by identifying polyvalent hydroxy compounds (excluding polyvalent hydroxy compounds having an oxyethylene structure) after hydrolysis.
• the polyhydric hydroxy compounds include 1,6-hexanediol (60 mol%), 1,2 In the case of -propanediol (40 mol%), the number of hydrogen atoms in a1 is 2 ⁇ 0.6+1.5 ⁇ 0.4, which is 1.8.
• each peak can be identified and the molar ratios [BB/A] and [B/(A+B)] can be calculated as follows.
• the spectrum shown in FIG. 1 is obtained when polycarbonate polyol is measured by NMR.
• the number average molecular weight of the polycarbonate polyol was determined to be 1283 by GPC measurement.
• the polyhydric hydroxy compounds obtained by hydrolyzing the polycarbonate polyol were identified as 1,6-hexanediol, 1,5-pentanediol, and polyethylene glycol (molecular weight approximately 1000), with an average carbon number of It was 5.5.
• the structural quantity expressed by formula (A) is obtained from (a1 integral value)/(number of hydrogens in a1), and the structural quantity expressed by formula (B) is that the b1 and a5 peaks overlap.
• the structural quantity expressed by formula (BB) is obtained from (bb1 integral value)/(number of hydrogens in bb1) Desired.
• [Hydrophilic structure] [Water dispersibility], which will be described later, was carried out to confirm whether the sample could be dispersed in water. When the evaluation result was ⁇ or ⁇ , it was determined that the sample had a hydrophilic structure. Moreover, the hydrophilic structure was determined by the following methods 1), 2) and/or 3). 1) Determined based on the structure of the raw materials used. 2) Confirmation was made by identifying the hydrophilic structure from various spectra obtained by subjecting the sample to mass spectrometry, FT-IR measurement, 1 H-NMR measurement and/or 13 C-NMR.
• Step 1 A sample and polytetramethylene glycol (number average molecular weight 2000) were weighed out in a glass container so that the weight ratio was 90/10, and the mixture was stirred at 60° C. using a stirrer.
• Step 2 The contents were transferred from the glass container to a colorless and transparent glass bottle, and left standing at 60° C. for 24 hours or more.
• Step 3 The contents in the colorless and transparent glass bottle were confirmed and evaluated according to the following criteria.
• a coating composition was prepared according to the steps 1 to 3 below.
• Step 1 A solvent was weighed out in a plastic container so that the solid content of the base agent and the coating composition was 20%, and the resulting solution was stirred using a stirrer until it was uniformly dispersed.
• Step 2 Weigh the catalyst, leveling agent, matting agent, and anti-settling agent into the plastic container according to the above-mentioned mixing conditions, and stir the resulting solution using a stirrer until it is uniformly dispersed. did.
• Ta A solvent was weighed out in a plastic container so that the solid content of the base agent and the coating composition was 20%, and the resulting solution was stirred using a stirrer until it was uniformly dispersed.
• Step 2 Weigh the catalyst, leveling agent, matting agent, and anti-
• the coating composition applied onto the polycarbonate plate was baked at 60° C. for 2 hours to obtain a polyurethane coating.
• the obtained polyurethane coating film was evaluated for various physical properties by the methods described below.
• sunscreen resistance was evaluated using a commercially available sunscreen cream.
• the coating film obtained by the above method for producing a polyurethane coating film was cured for one day in an atmosphere of 23°C and 50% RH, and a sunscreen agent (Neutrogena Ultra Sheer DRY-TOUCH SUNSCREEN Broad Spectrum) was applied on the cured coating film.
• SPF 45 was applied to the surface of the coating film at a concentration of 0.5 g/9 cm 2 and heated at 55° C. for 1 hour. Thereafter, the surface of the coating film was thoroughly washed to remove the sunscreen agent using a small amount of neutral detergent, and the coating was dried on a horizontal table in an atmosphere of 23° C. and 50% RH.
• the obtained coating film was subjected to the following appearance evaluation and pencil hardness method evaluation, and the chemical resistance was evaluated according to the following criteria. Chemical resistance is one of the indicators of durability. In addition, since it is difficult to evaluate with reproducibility, if the appearance of the coating film obtained by the method for producing a polyurethane coating film was "x", evaluation was not possible.
• - DBTDL was prepared at a concentration of 100 ppm based on the total amount of Polyol, IPDI, and DMPA. If necessary, DBTDL can be diluted with toluene and charged (eg, 5% DBTDL-toluene solution).
• ⁇ MEK was prepared so that the solid content in the prepolymer process was 65%. However, if the viscosity becomes high in the prepolymer step, MEK may be added as appropriate to adjust the solid content.
• ⁇ Pure water was charged so that the final solid content after the MEK removal step was 30%. However, if the viscosity becomes high in the chain extension step, pure water may be added as appropriate to adjust the solid content.
• the number average molecular weight (Mn) of the water-based polyurethanes obtained in Application Examples and Application Comparative Examples described below was measured by the following method.
• the concentration of the measurement sample was adjusted with N,N-dimethylformamide (hereinafter referred to as DMF) to be 0.5% by mass, and the number average molecular weight (Mn) was measured in terms of standard polystyrene using the GPC device shown below.
• DMF N,N-dimethylformamide
• GPC device Tosoh Corporation HLC-8320 Analytical column: TSKgel SuperHM-H 4 pieces Guard column: TSKgel guardcolumn H-H Reference column: 2 TSKgel SuperH-RC Eluent: N,N-dimethylformamide (hereinafter referred to as DMF) Flow rate: 1.0mL/min Column temperature: 40°C RI detector: RI (equipment HLC-8320 built-in) Calibration curve: Standard polystyrene (manufactured by Tosoh Corporation)
• FT-IR measurement Using oxyethylene structure-containing polycarbonate polyols obtained in the Examples and Comparative Examples described below as samples, the infrared absorption spectrum absorbance of the samples was measured using an FT-IR (Fourier transform infrared spectrophotometer) in the following manner. A measurement sample was spread thinly on a rock salt plate (NaCl plate, 35 x 35 x 5 mm), and the infrared absorption spectrum absorbance of the sample was measured by FT-IR using the following equipment and conditions.
• FT-IR Fastier transform infrared spectrophotometer
• FI-IR device FT/IR-4600typeA (JASCO Corporation)
• Light source Standard light source Detector: TGS Accumulated number of times: 16 Decomposition: 4cm -1
• Filter Auto (30000Hz)
• polycarbonate polyol P-2 (740 g).
• the obtained polycarbonate polyol P-2 had an average carbon number of 5.0 and a hydroxyl value of 56.1 mgKOH/g.
• the reactor was directly connected to a condenser, and after the reaction temperature was set to 165 to 175, the pressure was gradually lowered and further reaction was carried out to obtain polycarbonate polyol P-3 (559 g).
• the obtained polycarbonate polyol P-3 had an average carbon number of 3.03 and a hydroxyl value of 56.2 mgKOH/g.
• polycarbonate polyol P-4 (866 g).
• the obtained polycarbonate polyol P-4 had an average carbon number of 7.0 and a hydroxyl value of 56.5 mgKOH/g.
• Polymerization example 5 A 1 L glass flask (reactor) equipped with a stirring device was charged with 800 g of polycarbonate polyol P-1 obtained in Polymerization Example 1, 55 g of 1,5-pentanediol, and 62 g of 1,6-hexanediol. is. Next, these were heated while stirring, and the temperature inside the reactor was maintained at about 165° C. for 6 hours. Regarding the reaction, GPC measurements were performed on the reaction solution over time, and the progress of the reaction was confirmed by checking the disappearance of peaks originating from raw materials and the appearance of peaks originating from products over time. The obtained polycarbonate polyol P-5 had an average carbon number of 5.5 and a hydroxyl value of 224.0 mgKOH/g.
• Example 1 In a 1.0 L glass flask (reactor) equipped with a stirring device, 90 parts by mass (360 g) of polycarbonate diol P-1 obtained in Polymerization Example 1 and polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) were added. , "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) was charged in an amount of 10 parts by mass (40 g). Next, these were heated while being stirred, and the transesterification reaction was carried out at a temperature within the reactor of approximately 145°C.
• Example 2 In a 0.5 L glass flask (reactor) equipped with a stirring device, 360 g of polycarbonate polyol P-2 obtained in Polymerization Example 2 and polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000") were added. (trade name), number average molecular weight: approximately 1000) was charged. Next, these were heated while being stirred, and the transesterification reaction was carried out at a temperature within the reactor of approximately 145°C. In addition, by measuring the reaction solution with GPC over time, the reaction continues even after the peak derived from the raw material disappears, and by measuring the reaction solution with NMR over time, the structure represented by formula (BB) can be detected.
• BB reaction solution with NMR over time
• Example 3 In a 0.5 L glass flask (reactor) equipped with a stirring device, 270 g of polycarbonate polyol P-3 obtained in Polymerization Example 3 and polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000”) were added. ” (trade name), number average molecular weight: approximately 1000) was charged. Next, these were heated while being stirred, and the transesterification reaction was carried out at a temperature within the reactor of approximately 145°C. In addition, by measuring the reaction solution with GPC over time, the reaction continues even after the peak derived from the raw material disappears, and by measuring the reaction solution with NMR over time, the structure represented by formula (BB) can be detected.
• BB reaction solution with NMR over time
• Example 4 In a 0.5 L glass flask (reactor) equipped with a stirring device, 360 g of polycarbonate polyol P-4 obtained in Polymerization Example 4 and polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 2000”) were added. (trade name), number average molecular weight: approximately 2000) was charged. Next, these were heated while being stirred, and the transesterification reaction was carried out at a temperature within the reactor of approximately 145°C. In addition, by measuring the reaction solution with GPC over time, the reaction continues even after the peak derived from the raw material disappears, and by measuring the reaction solution with NMR over time, the structure represented by formula (BB) can be detected.
• BB reaction solution with NMR over time
• Example 5 In a 0.5 L glass flask (reactor) equipped with a stirring device, 300 g of polycarbonate polyol P-1 obtained in Polymerization Example 1 and polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000”) were added. ” (trade name), number average molecular weight: approximately 1000) was charged. Next, these were heated while being stirred, and the transesterification reaction was carried out at a temperature within the reactor of approximately 145°C. In addition, by measuring the reaction solution with GPC over time, the reaction continues even after the peak derived from the raw material disappears, and by measuring the reaction solution with NMR over time, the structure represented by formula (BB) can be detected.
• BB reaction solution with NMR over time
• Example 6 In a 0.5 L glass flask (reactor) equipped with a stirring device, 360 g of polycarbonate polyol P-5 obtained in Polymerization Example 5 and polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 600") were added. ” (trade name), number average molecular weight: approximately 600) was charged. Next, these were heated while being stirred, and the transesterification reaction was carried out at a temperature within the reactor of approximately 145°C. In addition, by measuring the reaction solution with GPC over time, the reaction continues even after the peak derived from the raw material disappears, and by measuring the reaction solution with NMR over time, the structure represented by formula (BB) can be detected.
• BB reaction solution with NMR over time
• Example 7 In a 0.5 L glass flask (reactor) equipped with a stirring device, 252 g of polycarbonate polyol P-5 obtained in Polymerization Example 5 and polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000") were added. (trade name), number average molecular weight: approximately 1000) was charged. Next, these were heated while being stirred, and the transesterification reaction was carried out at a temperature within the reactor of approximately 145°C. In addition, by measuring the reaction solution with GPC over time, the reaction continues even after the peak derived from the raw material disappears, and by measuring the reaction solution with NMR over time, the structure represented by formula (BB) can be detected.
• BB reaction solution with NMR over time
• a urethane group-containing polycarbonate polyol was obtained using the same method as in Applied Example 3, except that the oxyethylene structure-containing polycarbonate polyol HP-1 obtained in Comparative Example 1 was used as the oxyethylene structure-containing polycarbonate polyol.
• the evaluation results are shown in Table 4. The progress of the reaction was confirmed by performing the above-mentioned FT-IR measurement on the reaction solution, and the infrared absorption spectrum absorbance (Abs) peak around the wave number 2271 cm -1 , which is derived from the NCO group, disappeared.
• a urethane group-containing polycarbonate polyol was obtained using the same method as in Application Example 4, except that the oxyethylene structure-containing polycarbonate polyol HP-2 obtained in Comparative Example 2 was used as the oxyethylene structure-containing polycarbonate polyol.
• the evaluation results are shown in Table 4. The progress of the reaction was confirmed by performing the above-mentioned FT-IR measurement on the reaction solution, and the infrared absorption spectrum absorbance (Abs) peak around the wave number 2271 cm -1 , which is derived from the NCO group, disappeared.
• the oxyethylene structure-containing polycarbonate polyol of this example has excellent stability of aqueous dispersion and compatibility with ether polyol, and also has excellent stability and compatibility of aqueous polyurethane obtained using this example. It was also confirmed that the stability of the aqueous dispersion of the urethane group-containing polycarbonate polyol was also excellent.
• the oxyethylene structure-containing polycarbonate polyol of the present invention can be used for automobiles, buses, railway vehicles, construction machinery, agricultural machinery, floors, walls and roofs of buildings, metal products, mortar and concrete products, wood products, plastic products, calcium silicate plates, etc. It can be suitably used in a wide range of fields, such as paints for ceramic building materials such as gypsum boards, and/or polyurethane.

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