Oxetanyl-modified polycarbonate polyol

Abstract

Provided is an oxetanyl-modified polycarbonate polyol that, when used as an additive for producing a cationically-curable resin, can provide good solvent resistance to the resin.

Description

Oxetanyl-modified polycarbonate polyol

[0001] The present invention relates to an oxetanyl-modified polycarbonate polyol.

[0002] It is known to add polycarbonate polyol (hereinafter also referred to as "PCP") to improve the flexibility (deflection) of cationically curable resins (Patent Document 1). Also, polycarbonate polyols having a branched structure formed by using polyhydric alcohols are used as polycarbonate polyols (Patent Document 2).

[0003] International Publication No. 2019 / 015335 Japanese Patent Application Laid-Open No. 2012-184380

[0004] However, when conventional polycarbonate polyols are used as additives for cationically curable resins, the solvent resistance may be insufficient.

[0005] An object of the present invention is to provide a novel polycarbonate polyol that, when used as an additive in the production of a cationically curable resin, can improve the solvent resistance of the resin.

[0006] The present invention includes the following aspects: [Item 1] A compound of the following formula 1: [In the formula, R １ are each independently a single bond or a divalent to tetravalent aliphatic or alicyclic hydrocarbon group having 3 to 15 carbon atoms.], a terminal hydroxyl group, and a repeating unit represented by the following formula 2: [In the formula, R ２ are each independently a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms; R ３are each independently a divalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, and the dashed line represents a bonding site with the repeating unit represented by (Formula 1).] An oxetanyl-modified polycarbonate polyol containing a compound (X) having a terminal oxetanyl group represented by the following formulas (A) and (B): (A) 0.10≦c≦30 (B) 0.015≦(b / 2−c) / (c+d)≦0.050 [wherein the formulas are the values ​​of the oxetanyl-modified polycarbonate polyol measured at 400 MHz using deuterated chloroform as a solvent and tetramethylsilane as a reference substance. １ In H-NMR, when the integral value from 4.00 to 4.30 ppm is set as the reference integral value a=1000, b is the integral value from 4.35 to 4.48 ppm relative to the reference integral value a, c is the integral value from 3.71 to 3.76 ppm relative to the reference integral value a, and d is the integral value from 3.44 to 3.65 ppm relative to the reference integral value a. [Item 2] An oxetanyl-modified polycarbonate polyol that satisfies the following formula 1: [In the formula, R １ are each independently a single bond or a divalent to tetravalent aliphatic or alicyclic hydrocarbon group having 3 to 15 carbon atoms.], a terminal hydroxyl group, and a repeating unit represented by the following formula 2: [In the formula, R ２ are each independently a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms; R ３ are each independently a divalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, and the dashed line represents a bonding site with the repeating unit represented by (Formula 1).] An oxetanyl-modified polycarbonate polyol containing a compound (X) having a terminal oxetanyl group represented by the following formula (C): (C) 2.5≦b / 2−c≦20 [wherein the formula is a measurement of the oxetanyl-modified polycarbonate polyol at 400 MHz using deuterated chloroform as a solvent and tetramethylsilane as a reference substance. １In H-NMR, when the integral value from 4.00 to 4.30 ppm is set as the reference integral value a=1000, b is the integral value from 4.35 to 4.48 ppm relative to the reference integral value a, and c is the integral value from 3.71 to 3.76 ppm relative to the reference integral value a. [Item 3] R １ are each independently an alkylene group having 5 or 6 carbon atoms. [Item 4] The oxetanyl-modified polycarbonate polyol according to any one of Items 1 to 3, having 2.5 to 4.0 terminal hydroxyl groups. [Item 5] The oxetanyl-modified polycarbonate polyol according to any one of Items 1 to 4, comprising a structure α derived from an aliphatic or alicyclic diol and a structure β derived from a polyhydric alcohol, wherein the polyhydric alcohol is trimethylolpropane. [Item 6] The oxetanyl-modified polycarbonate polyol according to any one of Items 1 to 5, having a hydroxyl value of 35 to 450 mg KOH / g. [Item 7] The oxetanyl-modified polycarbonate polyol according to any one of Items 1 to 6, having a number average molecular weight of 400 to 4,500 g / mol. [Item 8] The oxetanyl-modified polycarbonate polyol according to any one of items 1 to 7, having a viscosity of 50 to 1000 mPa·s at 75°C. [Item 9] A compound represented by the following formula 3: [In the formula, R ａ is a monovalent aliphatic or alicyclic hydrocarbon having 1 to 6 carbon atoms; R ｂ is a monovalent organic group having 1 to 6 carbon atoms.] and the oxetanyl-modified polycarbonate polyol according to any one of Items 1 to 8. [Item 10] A composition comprising an oxetane compound represented by the formula: ａ and the molar concentration M of hydroxyl groups derived from the oxetanyl-modified polycarbonate polyol contained in the composition. ｂ Relative to M ａ / M ｂItem 11. A cationically curable resin composition comprising the oxetanyl-modified polycarbonate polyol according to any one of items 1 to 8, and an epoxy compound and / or an oxetane compound. [Item 12] A polyurethane resin comprising a structure derived from the oxetanyl-modified polycarbonate polyol according to any one of items 1 to 8. [Item 13] A urethane (meth)acrylate comprising a structure derived from the oxetanyl-modified polycarbonate polyol according to any one of items 1 to 8. [Item 14] A method for producing the oxetanyl-modified polycarbonate polyol according to any one of Items 1 to 8, comprising the following steps (i) to (iv): steps (i) and (iv); steps (i), (ii) and (iv); steps (i), (iii) and (iv); or steps (i) to (iv): (i) the following steps (A) or (B): (A) mixing an aliphatic or alicyclic diol, a polyhydric alcohol, and a carbonate ester to obtain a mixture; (B) mixing a polycarbonate polyol and a polyhydric alcohol, or mixing a polycarbonate polyol, a polyhydric alcohol, and a carbonate ester to obtain a mixture; (ii) heating the mixture obtained in step (i) at 90 to 210°C under 96 to 608 kPa to obtain a first product containing a polycarbonate polyol; (iii) heating the first product obtained in step (i) or (ii) at 150 to 210°C under a pressure of 2.7 to 40 kPa to obtain a second product in which the carbonate ester and / or carbonate ester-derived by-product alcohol is reduced; (iv) heating the mixture or product obtained in step (i), (ii) or (iii) at 180 to 200°C under a pressure of less than 2.7 kPa to obtain an oxetanyl-modified polycarbonate polyol.

[0007] According to the present invention, it is possible to provide a novel oxetanyl-modified polycarbonate polyol that, when used as an additive in producing a cationically curable resin, can impart good solvent resistance to the resin.

[0008] <Definition of Terms> As used herein, the term "monovalent organic group" refers to a monovalent group containing carbon. The monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. Note that when simply referring to an "organic group," it refers to a monovalent organic group. Furthermore, the term "divalent organic group" refers to a divalent group containing carbon. Examples of such divalent organic groups include divalent groups obtained by eliminating one more hydrogen atom from an organic group. Similarly, a trivalent or higher organic group refers to a group obtained by eliminating a predetermined number of hydrogen atoms from an organic group.

[0009] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C １－２０ Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents. The phrase "independently in each occurrence" means that, for each repeating structural unit, each group may be independently the same or different.

[0010] As used herein, the term "reactive group" refers to a functional group that is more reactive than an aliphatic saturated hydrocarbon group in various reactions, such as nucleophilic attack, electrophilic attack, substitution reaction, elimination reaction, rearrangement reaction, and radical reaction. Examples of such functional groups include, but are not limited to, epoxy groups, chloromethyl groups, bromomethyl groups, iodomethyl groups, isocyanate groups, blocked isocyanate groups, hydroxyl groups, amino groups, carboxylic acid groups, sulfonic acid groups, phosphate groups, alkali metal or alkaline earth metal bases of carboxylic acid, sulfonic acid, and phosphate, ammonium bases with chlorine, bromine, or iodine ions as counter anions, and other ionic groups. The reactive group may be linear, branched, or cyclic, and may be saturated or unsaturated. The reactive group may also contain one or more ring structures. The reactive group may be substituted with one or more substituents.

[0011] As used herein, "good solvent resistance" means that the weight of a cured cationic curable resin product changes little when immersed in an organic solvent, and the tensile strength at break and modulus of elasticity of the cured cationic curable resin product after immersion in an organic solvent are high.

[0012] It is to be understood that the chemical structures described herein do not encompass chemical structures that would be recognized by those skilled in the art as being chemically impossible or extremely unstable.

[0013] Embodiments of the present invention will be described in detail below. Polymeric compounds such as the oxetanyl-modified polycarbonate polyol of the present invention are obtained by the reaction of multiple types of raw material compounds to produce products with a variety of structures. Therefore, even if the numerous structures encompassed by a polymeric compound can be described by a general formula, the polymeric compound cannot be uniquely represented by that structure. Furthermore, it is difficult to directly measure and identify its physical properties by instrumental analysis or to distinguish it from existing compounds. Therefore, in the present invention, polymeric compounds such as "oxetanyl-modified polycarbonate polyol" and compositions containing the compounds are identified by their production methods, as necessary.

[0014] [Oxetanyl-modified polycarbonate polyol] In one embodiment, the oxetanyl-modified polycarbonate polyol (hereinafter also referred to as "the polycarbonate polyol of the present invention") is a polycarbonate polyol represented by the following formula 1: [In the formula, R １ are each independently a single bond or a divalent to tetravalent aliphatic or alicyclic hydrocarbon group having 3 to 15 carbon atoms.], a terminal hydroxyl group (terminal hydroxy group), and a repeating unit represented by the following formula 2: [In the formula, R ２ are each independently a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms; R ３ are each independently a divalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, and the wavy line represents a bonding site with the repeating unit represented by (Formula 1).] The oxetanyl-modified polycarbonate polyol contains a compound (X) having an oxetanyl group represented by the following formulas (A) and (B): (A) 0.10≦c≦30 (B) 0.015≦(b / 2−c) / (c+d)≦0.050 [wherein the formulas, the β- １ In H-NMR, when the integral value from 4.00 to 4.30 ppm is set as the reference integral value a=1000, b is the integral value from 4.35 to 4.48 ppm relative to the reference integral value a, c is the integral value from 3.71 to 3.76 ppm relative to the reference integral value a, and d is the integral value from 3.44 to 3.65 ppm relative to the reference integral value a.] is satisfied.

[0015] In another embodiment, the oxetanyl-modified polycarbonate polyol contains a compound (X) having a repeating unit represented by the above formula 1, a terminal hydroxyl group, and an oxetanyl group represented by the above formula 2, and has the following formula (C): (C) 2.5≦b / 2−c≦20 [wherein the value of the oxetanyl-modified polycarbonate polyol measured at 400 MHz using deuterated chloroform as a solvent and tetramethylsilane as a standard substance] １In H-NMR, when the integral value from 4.00 to 4.30 ppm is set as the reference integral value a=1000, b is the integral value from 4.35 to 4.48 ppm relative to the reference integral value a, and c is the integral value from 3.71 to 3.76 ppm relative to the reference integral value a.

[0016] Furthermore, the oxetanyl-modified polycarbonate polyol of the present invention may contain a compound (Y) having a repeating unit represented by the above formula 1 and a terminal hydroxyl group (terminal hydroxy group), but not having an oxetanyl group represented by the above formula 2.

[0017] In formula 1, R １ are each independently a single bond or a divalent to tetravalent aliphatic or alicyclic hydrocarbon group having 3 to 15 carbon atoms.

[0018] In one embodiment, R １ is a single bond. When the group represented by (Formula 2) is R １ When bonded to R １ can be a single bond.

[0019] In one embodiment, R １ are each independently a divalent to tetravalent aliphatic or alicyclic hydrocarbon group having 3 to 15 carbon atoms. １ When bonded to R １ can be a divalent to tetravalent aliphatic or alicyclic hydrocarbon group.

[0020] In one embodiment, R １ are each independently a divalent to tetravalent aliphatic hydrocarbon group having 3 to 15 carbon atoms.

[0021] In one embodiment, R １ are each independently a divalent to tetravalent alicyclic hydrocarbon group having 3 to 15 carbon atoms.

[0022] R １ The aliphatic or alicyclic hydrocarbon group may have 3 to 15 carbon atoms, for example, 3 to 15, 3 to 12, 3 to 10, 3 to 8, 3 to 6, 3 to 4, 4 to 15, 4 to 10, 4 to 5, 5 to 15, 5 to 10, 5 to 6, 6 to 15, 6 to 10, 6 to 7, etc. The number of carbon atoms is preferably 5 or 6.

[0023] R １ is a divalent to tetravalent group. The valence of the group is preferably divalent to trivalent. １ may be linear or branched. １ may be a substituted or unsubstituted alkylene group. １ When R is a substituted alkylene group, it preferably does not contain a reactive group. １ are each independently selected, and it is preferred that, for example, both divalent and trivalent groups are present.

[0024] In one embodiment, R １is a divalent aliphatic or alicyclic hydrocarbon group having 3 to 15 carbon atoms. Examples of such groups include n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, 2,2-dimethylpropylene group, 2-methylbutylene group, 3-methylbutylene group, 3-methyl-2-butylene group, n-pentylene group, 2-pentylene group, 3-pentylene group, 3-dimethyl-2-butylene group, 3,3-dimethylbutylene group, 3,3 -dimethyl-2-butylene group, 2-ethylbutylene group, n-hexylene group, 2-hexylene group, 3-hexylene group, 2-methylpentylene group, 2-methyl-2-pentylene group, 2-methyl-3-pentylene group, 3-methylpentylene group, 3-methyl-2-pentylene group, 3-methyl-3-pentylene group, 4-methylpentylene group, 4-methyl-2-pentylene group, 2,2-dimethyl-3-pentylene group ethylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl-2-pentylene group, 3-ethyl-3-pentylene group, n-heptylene group, 2-heptylene group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6-methyl Examples of such groups include 2-heptylene, 4-methyl-3-heptylene, octylene, 2-octylene, 3-octylene, 2-propylpentylene, 2,4,4-trimethylpentylene, decaoctylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,5-cyclooctylene, 1,4-cyclohexanedimethylene, and 1,3-cyclohexanedimethylene.

[0025] In a preferred embodiment, R １are each independently a divalent alkylene group having 5 or 6 carbon atoms. Examples of such groups include 2,2-dimethylpropylene, 2-methylbutylene, 3-methylbutylene, 3-methyl-2-butylene, n-pentylene, 2-pentylene, 3-pentylene, 3-dimethyl-2-butylene, 3,3-dimethylbutylene, 3,3-dimethyl-2-butylene, 2-ethylbutylene, n-hexylene, 2-hexylene, 3-hexylene, 2-methylpentylene, 2-methyl-2-pentylene, 2-methyl-3-pentylene, 3-methylpentylene, 3-methyl-2-pentylene, 3-methyl-3-pentylene, 4-methylpentylene, and 4-methyl-2-pentylene groups, with n-pentylene or n-hexylene being particularly preferred.

[0026] In another embodiment, R １ is a trivalent to tetravalent aliphatic or alicyclic hydrocarbon group having 3 to 15 carbon atoms. １ When is trivalent or tetravalent, it may be linear or branched, but is preferably branched, and is preferably an aliphatic hydrocarbon group.

[0027] R １ is trivalent or tetravalent, R １ is the following formula: [In the formula, R １１ are each independently a single bond or a divalent aliphatic or alicyclic hydrocarbon group, １２ is a monovalent or divalent aliphatic or alicyclic hydrocarbon group.]

[0028] R １１ are each independently a single bond or a divalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms.

[0029] In one embodiment, R １１ is a single bond.

[0030] In one embodiment, R １１are each independently a divalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms. Such groups are not particularly limited, but examples thereof include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a 2,2-dimethylpropylene group, a 2-methylbutylene group, a 3-methylbutylene group, a 3-methyl-2-butylene group, an n-pentylene group, a 2-pentylene group, a 3-pentylene group, a 3-dimethyl-2-butylene group, a 3,3-dimethylbutylene group, a 3, Examples include a 3-dimethyl-2-butylene group, a 2-ethylbutylene group, an n-hexylene group, a 2-hexylene group, a 3-hexylene group, a 2-methylpentylene group, a 2-methyl-2-pentylene group, a 2-methyl-3-pentylene group, a 3-methylpentylene group, a 3-methyl-2-pentylene group, a 3-methyl-3-pentylene group, a 4-methylpentylene group, a 4-methyl-2-pentylene group, a 1,3-cyclopentylene group, and a 1,4-cyclohexylene group.

[0031] In a preferred embodiment, R １１ is a methylene group.

[0032] R １２ is a monovalent or divalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms.

[0033] R １２ is a monovalent group, R １ is a trivalent group. １２ is a divalent group, R １ is a tetravalent group. １２ is preferably monovalent.

[0034] In one embodiment, R １２is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms. Such groups are not particularly limited, but examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 3-methyl-2-butyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 3-dimethyl-2-butyl group, a 3,3-dimethylbutyl group, a 3,3-dimethyl-2-butyl group, a 2-ethylbutyl group, an n-hexyl group, a 2-hexyl group, a 3-hexyl group, a 2-methylpentyl group, a 2-methyl-2-pentyl group, a 2-methyl-3-pentyl group, a 3-methylpentyl group, a 3-methyl-2-pentyl group, a 3-methyl-3-pentyl group, a 4-methylpentyl group, a 4-methyl-2-pentyl group, a 1,3-cyclopentyl group, and a 1,4-cyclohexyl group.

[0035] In a preferred embodiment, R １２ is an ethyl group.

[0036] R ２ are each independently a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms.

[0037] R ２ is preferably an aliphatic hydrocarbon group, more preferably an alkyl group. The alkyl group may be linear or branched. The alkyl group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms. In a particularly preferred embodiment, R ２ is an ethyl group.

[0038] R ３are each independently a divalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms. Examples of such groups include, but are not limited to, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a 2,2-dimethylpropylene group, a 2-methylbutylene group, a 3-methylbutylene group, a 3-methyl-2-butylene group, an n-pentylene group, a 2-pentylene group, a 3-pentylene group, a 3-dimethyl-2-butylene group, a 3,3-dimethylbutylene group, a 3, Examples include a 3-dimethyl-2-butylene group, a 2-ethylbutylene group, an n-hexylene group, a 2-hexylene group, a 3-hexylene group, a 2-methylpentylene group, a 2-methyl-2-pentylene group, a 2-methyl-3-pentylene group, a 3-methylpentylene group, a 3-methyl-2-pentylene group, a 3-methyl-3-pentylene group, a 4-methylpentylene group, a 4-methyl-2-pentylene group, a 1,3-cyclopentylene group, and a 1,4-cyclohexylene group.

[0039] In one embodiment, the polycarbonate polyol of the present invention has a molecular weight of 1000 or more and a molecular weight of 1000 or more, which satisfy the following formulas (A) and (B): (A) 0.10≦c≦30 (B) 0.015≦(b / 2−c) / (c+d)≦0.050 [wherein the formulas are the values ​​of the molecular weight of the oxetanyl-modified polycarbonate polyol measured at 400 MHz using deuterated chloroform as a solvent and tetramethylsilane as a standard substance. １ In H-NMR, when the integral value from 4.00 to 4.30 ppm is set as the reference integral value a=1000, b is the integral value from 4.35 to 4.48 ppm relative to the reference integral value a, c is the integral value from 3.71 to 3.76 ppm relative to the reference integral value a, and d is the integral value from 3.44 to 3.65 ppm relative to the reference integral value a.] is satisfied.

[0040] c is 0.10 to 30, preferably 0.80 to 20.0, and more preferably 1.0 to 3.8.

[0041] In another embodiment, c is 0.10 to 30, preferably 1.0 to 30, and more preferably 1.5 to 30. Alternatively, c may be 10 to 30, 15 to 30, or the like.

[0042] (b / 2-c) / (c+d) is 0.015 to 0.050, preferably 0.015 to 0.030.

[0043] In another embodiment, (b / 2-c) / (c+d) is 0.015 to 0.050, preferably 0.018 to 0.040, and may also be 0.020 to 0.050, 0.033 to 0.040, etc.

[0044] In another embodiment, the polycarbonate polyol of the present invention has a molecular weight of 1.0 or more, and a molecular weight of 1.0 or more, as measured at 400 MHz using deuterated chloroform as a solvent and tetramethylsilane as a standard substance, represented by the following formula (C): (C) 2.5≦b / 2−c≦20 １ In H-NMR, when the integral value from 4.00 to 4.30 ppm is set as the reference integral value a=1000, b is the integral value from 4.35 to 4.48 ppm relative to the reference integral value a, and c is the integral value from 3.71 to 3.76 ppm relative to the reference integral value a.

[0045] b / 2-c is 2.5 to 20, preferably 3.0 to 15, and more preferably 3.5 to 10.

[0046] Regarding the above a, b, c, and d, a can be derived from a group (e.g., a methylene group) adjacent to the carbonate group of the polycarbonate polyol of the present invention. b can be derived from a group (e.g., a methylene group) adjacent to the ether oxygen of the oxetanyl group and oxetane compound of compound (X) contained in the polycarbonate polyol of the present invention. c can be derived from a group (e.g., a methylene group) adjacent to the hydroxy group of the oxetane compound that can be contained in the polycarbonate polyol of the present invention. d can be derived from a group (e.g., a methylene group) adjacent to the terminal hydroxyl group of the oxetanyl-modified polycarbonate polyol of the present invention.

[0047] Therefore, for the oxetanyl-modified polycarbonate polyol of the present invention, the average number of terminal oxetanyl groups per molecule is n １ , the average number of terminal hydroxyl groups per molecule is n ２Then, (b / 2-c) / (c+d) in the above formula (B) is the number of terminal oxetanyl groups n １ and the number of terminal hydroxyl groups n ２ The ratio of １ / n ２ Therefore, a larger value of (b / 2−c) / (c+d) can mean that more of the terminal hydroxyl groups of the polycarbonate polyol of the present invention have been modified with oxetanyl.

[0048] Furthermore, b / 2-c in the above formula (C) can mean the number of terminal oxetanyl groups of the compound (X) per 500 carbonate groups of the compound (X).

[0049] The above a, b, c, and d are measured by measuring the polycarbonate polyol of the present invention at 400 MHz using deuterated chloroform as a solvent and tetramethylsilane as a standard substance. １ The number of times of accumulation in the measurement is not particularly limited, but is preferably 64 or more, or 128 or more.

[0050] The above b, c, and d are integral values ​​in a predetermined integral range when the integral value from 4.00 to 4.30 ppm is set as the reference integral value a = 1000. For example, if the peak area from 4.00 to 4.30 ppm is S, then the value b is obtained by multiplying the peak area from 4.35 to 4.48 ppm by 1000 / S. Values ​​c and d can also be calculated by performing similar calculations in the integral ranges of 3.71 to 3.76 ppm and 3.44 to 3.65 ppm, respectively.

[0051] In a preferred embodiment, the number of terminal hydroxyl groups in the polycarbonate polyol of the present invention is n ２ is 2.5 to 4.0, more preferably 2.75 to 3.50, and even more preferably 2.90 to 3.10.

[0052] In addition, the number of terminal hydroxyl groups in the polycarbonate polyol of the present invention, n ２ may be 2.75 to 4.0, 3.1 to 3.75, 3.2 to 3.5, etc.

[0053] In the present invention, the number of terminal hydroxyl groups, n ２ teeth, １It can be calculated by H-NMR analysis.

[0054] (Method for measuring the number of terminal hydroxyl groups) Number of terminal hydroxyl groups n ２ The specific calculation procedure is as follows: (i) of the polycarbonate polyol of the present invention １ In the H-NMR spectrum, the molar ratio (H) of terminal OH groups calculated from peaks derived from groups (e.g., methylene groups) bonded to the terminal hydroxy groups of the polycarbonate polyol of the present invention, and the molar ratio (T) of polyfunctional polyol calculated from peaks derived from the polyfunctional polyol structure are calculated; (ii) the value of 2+2T / (H-T) is the number of terminal hydroxyl groups.

[0055] The molar ratio (H) of terminal OH calculated from the peak derived from the group bonded to the terminal hydroxy group is a value obtained by dividing the integral value of the group bonded to the terminal hydroxy group by its number of protons. For example, when the group bonded to the terminal hydroxy group is a methylene group, it is obtained by dividing the integral value of the methylene group by the number of protons, 2. The molar ratio (T) of polyfunctional polyol calculated from the peak derived from the polyfunctional polyol structure is a value obtained by dividing the integral value of a peak derived from the polyfunctional polyol structure by its number of protons. For example, when a methylene group is used as the peak derived from the polyfunctional polyol structure, it is obtained by dividing the integral value of the methylene group by the number of protons, 2.

[0056] In the present invention, the number of terminal oxetanyl groups and the number of terminal hydroxyl groups of a polycarbonate polyol are values ​​determined by the above-mentioned measurement method and calculation formula. The values ​​obtained by the above-mentioned method may be the average value of the numbers of terminal oxetanyl groups or terminal hydroxyl groups of multiple polycarbonate polyol molecules, and therefore the values ​​may not be integers.

[0057] In one embodiment, the polycarbonate polyol of the present invention comprises a structure α derived from an aliphatic or alicyclic diol and a structure β derived from a polyhydric alcohol. Such a structure can be formed by reacting an aliphatic or alicyclic diol and a polyhydric alcohol with a carbonate ester to produce a polycarbonate polyol. The total number m of the structures α is αand the total number m of the above structures β β Relative to m α / m β is preferably 2.5 to 3.5. In this specification, the term "polyhydric alcohol" refers to an alcohol having a valence of three or more. Dihydric alcohols are simply called "diols."

[0058] (Aliphatic or Alicyclic Diol) Examples of the aliphatic or alicyclic diol that can be used include: linear aliphatic diols such as 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, and 1,12-dodecanediol; branched aliphatic diols such as 2-methyl-1,3-propanediol, 2- or 3-methyl-1,5-pentanediol, 2,2,4- or 2,4,4-trimethylhexanediol, and 1,5-hexanediol; and alicyclic diols such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. These may be used alone or in combination of two or more.

[0059] In a preferred embodiment, the structure α is a structure derived from 1,6-hexanediol.

[0060] (Polyhydric Alcohol) Examples of the polyhydric alcohol include compounds having three or more hydroxyl groups in one molecule, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. These may be used alone or in combination of two or more.

[0061] In a preferred embodiment, the structure β is a structure derived from trimethylolpropane.

[0062] (Carbonate Ester) Examples of the carbonate ester include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; diaryl carbonates such as diphenyl carbonate; and cyclic carbonates such as ethylene carbonate, propylene carbonate (4-methyl-1,3-dioxolan-2-one), trimethylene carbonate, butylene carbonate (4-ethyl-1,3-dioxolan-2-one), tetramethylene carbonate, and 5-methyl-1,3-dioxan-2-one, with dimethyl carbonate, diethyl carbonate, and ethylene carbonate being preferred. These may be used alone or in combination of two or more.

[0063] In a preferred embodiment, dimethyl carbonate is used as the carbonate ester.

[0064] The amount of the carbonate ester used is preferably 0.25 to 0.65 mol, more preferably 0.30 to 0.60 mol, per mol of the "total hydroxyl groups of the polyhydric alcohol and aliphatic diol" used. By using this range, the target oxetanyl-modified polycarbonate polyol can be obtained efficiently at a sufficient reaction rate.

[0065] Total number of structures α m α and the total number m of structures β β can be determined, for example, by completely hydrolyzing the polycarbonate polyol of the present invention, and identifying and quantifying the aliphatic or aliphatic diol and polyhydric alcohol by means of gas chromatography, mass spectrometry, NMR measurement, etc. The "total number of structures α" or "total number of structures β" means the average value of the total number of structures α or β contained in compounds (X) and (Y) contained in the polycarbonate polyol of the present invention.

[0066] (Hydroxyl Value (OH Value)) In a preferred embodiment, the hydroxyl value of the polycarbonate polyol of the present invention is 35 to 450 mgKOH / g, more preferably 50 to 300 mgKOH / g, and even more preferably 70 to 175 mgKOH / g.

[0067] In another preferred embodiment, the hydroxyl value of the polycarbonate polyol of the present invention is 35 to 450 mgKOH / g, more preferably 50 to 400 mgKOH / g, and even more preferably 70 to 350 mgKOH / g.

[0068] The hydroxyl value of the polycarbonate polyol of the present invention may be 150 to 500 mgKOH / g, or 200 to 390 mgKOH / g, for example.

[0069] The hydroxyl value of the polycarbonate polyol of the present invention can be calculated by the following procedure. 0.9 g of oxetanyl-modified polycarbonate polyol and 10 mL of a phthalating agent (a mixture of 160 g of phthalic anhydride, 24 g of imidazole, and 1000 mL of pyridine) are reacted at around 100°C for 30 minutes. Next, 4 mL of water and 20 mL of pyridine are added to this reaction solution, and the mixture is titrated with a 0.5 mol / L potassium hydroxide-ethanol solution. The phthalating agent was titrated with a 0.5 mol / L potassium hydroxide-ethanol solution (this was a blank test to determine a blank value). The hydroxyl value is calculated based on the titration amount obtained using the following formula (1): Hydroxyl value (mg KOH / g) = [B (mL) - A (mL)] × f × 28.05 / S (g) + acid value (mg KOH / g) ...Equation (1) A: Amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution required to titrate the sample B: Amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution required to titrate the blank f: Titer of the 0.5 mol / L potassium hydroxide ethanol solution S: Weight of sample (g) The acid value can be calculated using the following method: 10 g of sample was dissolved in a 50 / 50 (weight ratio) solution of toluene / ethanol to prepare a solution, which was then titrated with 0.1 N KOH ethanol solution. The acid value (mg KOH / g) can be calculated using the following equation (2): 5.61 × (C - B1) × f / s ...Equation (2) where B1 is the amount (mL) of 0.1 N KOH ethanol standard solution required to neutralize the blank, C is the amount (mL) of 0.1 N KOH ethanol standard solution required to neutralize the sample, f is the factor of the 0.1 N KOH ethanol standard solution, and s is the weight (g) of the sample.

[0070] (Number Average Molecular Weight (Mn)) In a preferred embodiment, the number average molecular weight (Mn) of the compound (X) contained in the polycarbonate polyol of the present invention is 400 to 4,500 g / mol, more preferably 600 to 3,000 g / mol, and even more preferably 750 to 1,500 g / mol. The number average molecular weight (Mn) can be measured using gel permeation chromatography (GPC) with a viscosity detector. In the present application, the number average molecular weight was measured according to the procedures described in the following examples.

[0071] In another preferred embodiment, the number average molecular weight (Mn) of the compound (X) contained in the polycarbonate polyol of the present invention is 400 to 4,500 g / mol, more preferably 450 to 3,000 g / mol, and even more preferably 480 to 1,500 g / mol.

[0072] The number average molecular weight (Mn) of the compound (X) contained in the polycarbonate polyol of the present invention may be 300 to 3,000 g / mol, or 350 to 900 g / mol, for example.

[0073] (Viscosity) In a preferred embodiment, the viscosity of the polycarbonate polyol of the present invention at 75°C may be 50 mPa·s or more, or 100 mPa·s or more. The viscosity of the polycarbonate polyol of the present invention at 75°C may be 1500 mPa·s or less, 1000 mPa·s or less, 800 mPa·s or less, 600 mPa·s or less, or 470 mPa·s or less. It is preferably 50 to 1500 mPa·s, more preferably 240 to 1000 mPa·s, and even more preferably 240 to 600 mPa·s. The viscosity of the polycarbonate polyol of the present invention can be measured by the method described in the Examples.

[0074] In another preferred embodiment, the viscosity of the polycarbonate polyol of the present invention at 75° C. is preferably 50 to 1500 mPa·s, more preferably 75 to 1000 mPa·s, and even more preferably 100 to 500 mPa·s.

[0075] In the oxetanyl-modified polycarbonate polyol of the present invention, some of the terminals may be unsaturated bonds (for example, terminal ethylene) or ether bonds (for example, terminal methoxy groups or terminal phenoxy groups) other than hydroxyl groups and oxetanyl groups.

[0076] Here, the ratio of terminal hydroxyl groups in the terminal structure contained in the oxetanyl-modified polycarbonate polyol of the present invention is １ This can be measured by H-NMR, and is preferably 90% or more, more preferably 95% or more. By being in this range, for example, it is possible to increase the molecular weight of the urethanization reaction using the polycarbonate polyol of the present invention. Furthermore, the proportion of primary terminal hydroxyl groups among the terminal hydroxyl groups is preferably 95% or more. By being in this range, for example, the urethanization reaction using the polycarbonate polyol of the present invention proceeds smoothly.

[0077] (Other Components) The polycarbonate polyol of the present invention may contain 0.3 to 300 ppm by mass of lithium and / or titanium. The metal components, lithium and / or titanium, may be derived from lithium hydroxide and / or titanium tetrabutoxide. These are components derived from the catalyst described below and may be generated in the post-treatment process described below. The content of the metal components may be, for example, 0.3 ppm by mass or more, 1 ppm by mass or more, or 300 ppm by mass or less, 150 ppm by mass or less, or 100 ppm by mass or less, relative to the total amount of the polycarbonate polyol of the present invention. By setting the content within this range, it is possible to easily control the polyurethane-forming reaction and the reaction to obtain the cationic curable resin composition. The metal content can be measured by, but is not particularly limited to, ICP (inductively coupled plasma) emission spectroscopy, and indicates the content of the metal element. Therefore, the content of counter ions of the metal components is not taken into consideration.

[0078] Next, the composition of the present invention will be described.

[0079] The composition of the present invention has the following formula 3: [In the formula, R ａis a monovalent aliphatic or alicyclic hydrocarbon having 1 to 6 carbon atoms; R ｂ is a monovalent organic group having 1 to 6 carbon atoms.] and an oxetanyl-modified polycarbonate polyol.

[0080] R ａ is a monovalent aliphatic or alicyclic hydrocarbon having 1 to 6 carbon atoms.

[0081] R ａ is preferably an aliphatic hydrocarbon group, more preferably an alkyl group. The alkyl group may be linear or branched. The alkyl group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms. In a particularly preferred embodiment, R ａ is an ethyl group.

[0082] R ａ is R in Equation 2 ２ For example, R ａ is an ethyl group, R of the oxetanyl-modified polycarbonate polyol contained in the composition ２ may also be an ethyl group.

[0083] R ｂ is a monovalent organic group having 1 to 6 carbon atoms.

[0084] The monovalent organic group may be any monovalent organic group as long as the compound represented by formula 3 can exist stably.

[0085] In one embodiment, R ｂ may have one or more of various functional groups and / or bonds. The type of such functional group is not particularly limited, but examples thereof include alkyl groups, cycloalkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, alkylene groups, hydroxy groups, alkoxy groups, aldehyde groups, carboxyl groups, carbonyl groups, nitro groups, amino groups, cyano groups, sulfo groups, aryl groups, and (meth)acrylic groups. The type of such bond is not particularly limited, but examples thereof include ether bonds, ester bonds, and amide bonds. In one embodiment, R ｂhas a hydroxy group. ｂ has an ether bond.

[0086] In a preferred embodiment, R ｂ is -R ｂ１ -OH, preferably -CH ２ OH. R ｂ１ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms.

[0087] The composition of the present invention may contain one or more of the above oxetane compounds, and may contain one or more of the above oxetanyl-modified polycarbonate polyols.

[0088] In a preferred embodiment, the molar concentration M of the oxetane compound contained in the composition ａ and the molar concentration M of hydroxyl groups of the polycarbonate polyol contained in the composition. ｂ Relative to M ａ / M ｂ is 0.001 to 0.04. The ratio may be, for example, 0.001 or more, 0.008 or more, or 0.01 or more. The ratio may be, for example, 0.04 or less, 0.02 or less, or 0.015 or less.

[0089] In another preferred embodiment, M ａ / M ｂ is 0.001 to 0.04, and may be 0.04 or less, 0.039 or less, or 0.038 or less.

[0090] (molar concentration M ａ and M ｂ Measurement method for the molar concentration M of the oxetane compound ａ and the concentration of hydroxyl groups in PCP, M ｂ The ratio of M to M can be calculated from the NMR integral value using the following formula: ａ / M ｂ = c / d

[0091] (Production of Oxetanyl-Modified Polycarbonate Polyol) The polycarbonate polyol of the present invention can be produced, for example, by a method comprising the following steps (i) to (iv): steps (i) and (iv); steps (i), (ii) and (iv); steps (i), (iii) and (iv); or steps (i) to (iv): (i) the following steps (A) or (B): (A) mixing an aliphatic or alicyclic diol, a polyhydric alcohol, and a carbonate ester to obtain a mixture; (B) mixing a polycarbonate polyol with a polyhydric alcohol, or mixing a polycarbonate polyol with a polyhydric alcohol and a carbonate ester to obtain a mixture; (ii) heating the mixture obtained in step (i) at 90 to 210°C under 96 to 608 kPa to obtain a first product containing a polycarbonate polyol; (iii) heating the first product obtained in step (i) or (ii) at 150 to 210°C under a pressure of 2.7 to 40 kPa to obtain a second product in which the carbonate ester and / or carbonate ester-derived by-product alcohol is reduced; and (iv) heating the mixture or product obtained in step (i), (ii) or (iii) at 180 to 200°C under a pressure of less than 2.7 kPa to obtain an oxetanyl-modified polycarbonate polyol.

[0092] The polycarbonate polyol of the present invention can be produced by carrying out step (iv) following step (i) (A), or by carrying out step (i) (B) following step (iv). The conditions for each step for producing the polycarbonate polyol of the present invention will be described below.

[0093] Step (i)-(A) In step (i)-(A), an aliphatic or alicyclic diol, a polyhydric alcohol, and a carbonate ester are mixed to obtain a mixture.

[0094] The aliphatic or alicyclic diol, polyhydric alcohol, and carbonate ester used as raw materials in this step may be any of the various compounds exemplified above.

[0095] The blending ratio of the aliphatic or alicyclic diol may be, for example, 5% by mass or more, 10% by mass or more, 20% by mass or more, 40% by mass or more, 50% by mass or more, or 60% by mass or more, relative to the total mass of the mixture.

[0096] The blending ratio of the polyhydric alcohol may be, for example, 1% by mass or more, 3% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, or 15% by mass or more, relative to the total mass of the mixture.

[0097] The blending ratio of the carbonate ester may be, for example, 5% by mass or more, 10% by mass or more, 20% by mass or more, 40% by mass or more, 50% by mass or more, or 60% by mass or more relative to the total mass of the mixture.

[0098] Step (i)-(B) In step (i)-(B), a mixture is obtained by mixing a polycarbonate polyol with a polyhydric alcohol, or by mixing a polycarbonate polyol, a polyhydric alcohol, and a carbonate ester.

[0099] The polyhydric alcohol and carbonate ester used as raw materials in this step can be any of the various compounds exemplified above. The type of PCP used as a raw material in this step is not particularly limited, and various PCPs can be used, such as any commercially available PCP (including polycarbonate diol) and the PCP described in JP 2012-184380 A.

[0100] The blending ratio of the polycarbonate polyol may be, for example, 5 mass % or more, 10 mass % or more, 20 mass % or more, 40 mass % or more, 50 mass % or more, or 60 mass % or more relative to the total mass of the raw material mixture.

[0101] Step (ii) In step (ii), the mixture is heated at 90 to 210°C under 96 to 608 kPa to obtain a first product containing a polycarbonate polyol which may have a hydroxyl terminal. In this specification, "normal pressure" refers to a pressure of 101 kPa ± 5%, i.e., 96 to 106 kPa.

[0102] The pressure in this step is 96 to 608 kPa, preferably 97 to 105 kPa, and the temperature in this step is 90 to 210°C, preferably 100 to 190°C.

[0103] The polycarbonate polyol contained in the first product may have terminal hydroxyl groups. The terminal groups other than hydroxyl groups may be oxetanyl groups, unsaturated bonds (e.g., terminal ethylene), alkyl carbonates, or ether bonds (e.g., terminal methoxy groups or terminal phenoxy groups), and for example, 80% or more, 90% or more, 95% or more, or 98% or more of the total number of terminal groups of the polycarbonate polyol may be hydroxyl groups.

[0104] The content of the polycarbonate polyol contained in the first product can be, for example, 10% by mass or more, 20% by mass or more, 30% by mass or more, or 50% by mass or more, based on the total mass of the first product.

[0105] Furthermore, the first product may contain an oxetane compound (a compound represented by the above formula 3) in addition to the polycarbonate polyol and the unreacted raw material mixture. The content of the oxetane compound may be, for example, 0.1 mass % or more, 0.4 mass % or more, 2 mass % or more, or 5 mass % or more relative to the total mass of the first product.

[0106] Step (iii) In the step (iii), the first product is heated at 150 to 210°C under a pressure of 2.7 to 40 kPa to react the raw materials remaining in the first product, and unreacted carbonate ester and / or by-produced alcohol derived from the carbonate ester are distilled off, thereby obtaining a second product in which these are reduced.

[0107] The pressure in this step is 2.7 to 40 kPa, preferably 3.3 to 16 kPa, and more preferably 12 to 15 kPa, and the temperature in this step is 150 to 210°C, and preferably 160 to 200°C.

[0108] This step may be carried out consecutively in the same vessel as step (i) and step (ii), that is, in a one-pot manner.

[0109] The polycarbonate polyol contained in the second product may also have hydroxyl groups at its terminals, similar to the polycarbonate polyol contained in the first product. The terminal groups other than hydroxyl groups may be oxetanyl groups, unsaturated bonds (e.g., terminal ethylene) alkyl carbonate, or ether bonds (e.g., terminal methoxy groups or terminal phenoxy groups), and for example, 80% or more, 90% or more, 95% or more, or 98% or more of the total number of terminal groups of the polycarbonate polyol may be hydroxyl groups.

[0110] The content of the polycarbonate polyol in the second product may be, for example, 30% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more, based on the total mass of the second product.

[0111] The second product contains an oxetane compound in addition to the polycarbonate polyol and the unreacted raw material mixture. The content of the oxetane compound may be, for example, 2% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, based on the total mass of the second product.

[0112] Step (iv) In step (iv), the mixture obtained in step (i), the first product obtained in step (ii), or the second product obtained in step (iii) is heated at 180 to 200°C under a pressure of less than 2.7 kPa, whereby the oxetane compound and the polycarbonate polyol react with each other, thereby obtaining the target oxetanyl-modified polycarbonate polyol.

[0113] The pressure in step (iv) is less than 2.7 kPa, preferably 2.0 kPa or less, and the temperature in this step is 180 to 200°C, preferably 185 to 195°C.

[0114] Step (iv) may be carried out consecutively in the same vessel as step (i), step (ii) or step (iii), that is, in a one-pot manner.

[0115] A catalyst may be used in the reaction to obtain the polycarbonate polyol of the present invention. Known transesterification catalysts can be used as such catalysts, including metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, zirconium, cobalt, germanium, tin, and cerium, as well as their hydroxides, alkoxides, carboxylates, carbonates, hydrogencarbonates, sulfates, phosphates, nitrates, and organic metals. From the viewpoint of efficiently obtaining the target oxetanyl-modified polycarbonate polyol, lithium hydroxide, sodium hydride, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltin dimethoxide, and dibutyltin oxide are preferably used, and lithium hydroxide and titanium tetrabutoxide are more preferably used. These catalysts may be used alone or in combination.

[0116] In step (i), the catalyst may be added in its entirety to the mixture before the start of the reaction in one go, or a part of the catalyst may be added to the mixture before the start of the reaction, and then added in two or more divided portions after the start of the reaction.

[0117] The amount of the catalyst added is not particularly limited, but may be, for example, 0.3 ppm by mass or more, 1 ppm by mass or more, or 3 ppm by mass or more, and 300 ppm by mass or less, 150 ppm by mass or less, or 100 ppm by mass or less, relative to the total amount of synthesis raw materials. By setting the amount within this range, the target oxetanyl-modified polycarbonate polyol can be obtained efficiently at a sufficient reaction rate.

[0118] When a catalyst is used in the reaction to obtain a polycarbonate polyol, the catalyst may remain, making it impossible to control the reaction during the polyurethane-forming reaction or the reaction to obtain a cationic curable resin composition. In order to suppress the influence of this remaining catalyst, a phosphoric acid-based deactivator may be added after step (iv) (referred to as a post-treatment step). Furthermore, by performing a heat treatment after adding the phosphoric acid-based deactivator, the remaining catalyst can be efficiently deactivated. Examples of phosphoric acid-based deactivators used to deactivate the catalyst include inorganic phosphoric acids such as phosphoric acid and phosphorous acid, and organic phosphoric acid esters such as dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, and triphenyl phosphite. These may be used alone or in combination of two or more.

[0119] As a result of various investigations by the applicant, it has been found that the above-mentioned production method can produce oxetanyl-modified polycarbonate polyol. The mechanism of this reaction is thought to be as follows.

[0120] It is known that when polycarbonate polyol is synthesized by transesterification with dimethyl carbonate and trimethylolpropane, an oxetane compound is by-produced by the following reaction (J. Am. Chem. Soc., 79, 3455 (1957)).

[0121] In the production method according to the present invention, an oxetane compound is by-produced by the reaction during any of the steps. Thereafter, the terminal hydroxyl groups of the polycarbonate polyol, which is the main product of the step, react with the oxetane compound, which is the by-product, in step (iii) and / or step (iv), thereby producing an oxetanyl-modified polycarbonate polyol.

[0122] On the other hand, conventional methods for producing polycarbonate polyols (for example, the method described in JP-A-5-9434) do not produce oxetanyl-modified polycarbonate polyols. The reason for this is thought to be that the conventional methods include a step of reacting a carbonate ester with a polyhydric alcohol under reduced pressure and then distilling off by-products including an oxetane compound, and therefore, in the step corresponding to step (iii) and / or step (iv) of the present invention, substantially no oxetane compound capable of reacting with the terminal hydroxyl group is present in the system.

[0123] (Cationically curable resin composition) The present invention also relates to a cationically curable resin composition containing any of the above polycarbonate polyols and an epoxy compound and / or an oxetane compound. A cured resin product obtained by curing such a composition can have better solvent resistance than when conventional polycarbonate polyols are used.

[0124] The cationically curable resin composition of the present invention contains any of the above polycarbonate polyols and an epoxy compound and / or an oxetane compound.

[0125] As the epoxy compound, any compound preferably used as a cationically polymerizable organic compound can be used as long as it contains an epoxy group. Examples of such epoxy compounds include, but are not limited to, alicyclic epoxy compounds, aliphatic epoxy compounds, and aromatic epoxy compounds, with alicyclic epoxy compounds and aliphatic epoxy compounds being more preferred. Specifically, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate and diglycidyl ether of hydrogenated bisphenol A are preferred.

[0126] The oxetane compound is not particularly limited as long as it contains an oxetane group, and compounds such as those exemplified by formula 3 above can be used.

[0127] The cationically curable resin composition of the present invention contains an epoxy compound and / or an oxetane compound, and preferably contains both an epoxy compound and an oxetane compound. By containing both compounds, the rate of the cationic polymerization reaction is increased, and it becomes easier to achieve a desired curing rate in the curing step of the cationically curable resin composition.

[0128] The total content of the epoxy compound and the oxetane compound in the resin composition of the present invention is not particularly limited, and may be, for example, 1 mass % or more, 5 mass % or more, 15 mass % or more, 20 mass % or more, or 25 mass % or more, and may be 70 mass % or less, 60 mass % or less, or 50 mass % or less, relative to the total amount of the composition.

[0129] The resin composition of the present invention can be used in a wide range of applications, for example, in 3D printers. Among 3D printers, it is more preferable to use it in a stereolithography method, and particularly in a free surface stereolithography (SLA) method.

[0130] <Acid Generator> The cationically curable resin composition of the present invention may contain an acid generator. In the present invention, the acid generator can be any compound or composition that can serve as a source of acid that serves as an initiator for cationic polymerization of an epoxy compound and / or an oxetane compound. Among them, photoacid generators that can release acid when irradiated with active energy rays such as ultraviolet rays are preferred, and onium salts that can release protons are particularly preferred. Such onium salts are not particularly limited, but examples thereof include oxonium salts, ammonium salts, phosphonium salts, sulfonium salts, and iodonium salts.

[0131] <Sensitizer> In order to promote the polymerization reaction, the cationic curable resin composition of the present invention may contain, if necessary, a photosensitizer such as pyrene, perylene, acridine orange, benzophenone, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, benzoin alkyl ether, thioxanthone, 1-chloro-4-propoxy-9H-thioxanthone-9-one, or 2-chlorothioxanthone, together with the cationic polymerization initiator.

[0132] <Radical Polymerizable Compound> The cationically curable resin composition of the present invention preferably contains a radically polymerizable compound for the purpose of stabilizing the shape of the cured product. In this specification, the radically polymerizable compound refers to a compound that undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with active energy rays in the presence of a radical polymerization initiator, and any compound such as a radically polymerizable resin, a monofunctional monomer having radical polymerizability, or a polyfunctional monomer can be used. The resin composition of the present invention may contain only one type of such radically polymerizable compound, or may contain two or more types.

[0133] <Radical Polymerization Initiator> When the resin composition of the present invention contains a radical polymerizable compound, it is preferable that the resin composition contain a radical polymerization initiator. In the present invention, any polymerization initiator that can initiate radical polymerization of a radical polymerizable compound when irradiated with active energy rays can be used as the radical polymerization initiator. Examples of the radical polymerization initiator include aromatic ketone compounds such as benzil or its dialkyl acetal compounds, phenyl ketone compounds, acetophenone compounds, benzoin or its alkyl ether compounds, benzophenone compounds, phosphine oxide compounds, and thioxanthone compounds.

[0134] (Method for producing a cured cationically curable resin product) The cured cationically curable resin product of the present invention is produced by curing the cationically curable resin composition of the present invention. Here, in this specification, "curing" refers to cationic polymerization of the epoxy compound and / or oxetane compound in the composition.

[0135] Examples of the cationic polymerization method include a method in which cationic species, which are active species, are generated by heating or irradiation with active energy rays, and the method using irradiation with active energy rays is particularly preferred.

[0136] The active energy rays irradiated to the cationically curable resin composition of the present invention are not particularly limited, and examples thereof include ultraviolet rays, electron beams, X-rays, radioactive rays, and high-frequency waves. From an economical viewpoint, ultraviolet rays having a wavelength of 300 to 410 nm are preferably used. In this case, examples of the light source that can be used include ultraviolet lasers (e.g., semiconductor-pumped solid-state lasers, Ar lasers, He—Cd lasers, etc.), high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, xenon lamps, halogen lamps, metal halide lamps, ultraviolet LEDs (light-emitting diodes), and ultraviolet fluorescent lamps.

[0137] (Polyurethane Resin) The present invention also relates to a polyurethane resin containing a structure derived from the polycarbonate polyol of the present invention. "Polyurethane resin containing a structure derived from the polycarbonate polyol of the present invention" means a compound or composition obtained by reacting the polycarbonate polyol of the present invention with a polyisocyanate (hereinafter also referred to as "polyurethane reaction").

[0138] <Polyisocyanate> The polyisocyanate can be appropriately selected depending on the purpose and application. For example, aromatic aliphatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenylisocyanate, xylylene diisocyanate (XDI), and phenylene diisocyanate; and aliphatic diisocyanates such as 4,4'-methylenebiscyclohexyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,3-diylbis(methylene)diisocyanate, and trimethylhexamethylene diisocyanate may be used. These polyisocyanates may be used alone or in combination of two or more, and part or all of the structure may be derivatized by isocyanuration, carbodiimide conversion, biuretization, or the like.

[0139] The amount of polyisocyanate used can be designed based on the molar ratio (isocyanate group / hydroxyl group (mol)) of the isocyanate group of the polyisocyanate to the hydroxyl group of the highly branched polycarbonate polyol composition, and is preferably an amount such that the molar ratio is 0.8 to 1.5, more preferably 0.9 to 1.3.

[0140] <Chain extender> In the polyurethane-forming reaction, a chain extender can be used for the purpose of increasing the molecular weight. The chain extender to be used can be appropriately selected depending on the purpose and application.

[0141] (Urethane (meth)acrylate) The present invention also relates to a urethane (meth)acrylate containing a structure derived from the polycarbonate polyol of the present invention. "A urethane (meth)acrylate containing a structure derived from the polycarbonate polyol of the present invention" means a compound or composition obtained by reacting the polycarbonate polyol of the present invention with a polyisocyanate and a hydroxyl group-containing (meth)acrylate or an isocyanato group-containing (meth)acrylate. The polyisocyanate has the same meaning as defined above.

[0142] <Hydroxyl Group-Containing (Meth)acrylate> The structure derived from a hydroxyl group-containing (meth)acrylate refers to a structure derived from a hydroxyl group-containing (meth)acrylate other than the bonding group in the polyurethane (meth)acrylate. Examples of hydroxyl group-containing monofunctional (meth)acrylates include hydroxyethyl (meth)acrylate.

[0143] Examples of hydroxyl group-containing polyfunctional (meth)acrylates include pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane di(meth)acrylate, or ethyleneoxy-modified, propyleneoxy-modified, or lactone-modified products thereof. Note that a plurality of types of these hydroxyl group-containing (meth)acrylates or hydroxyl group-containing polyfunctional (meth)acrylates may be used in combination.

[0144] <Isocyanato Group-Containing (Meth)acrylate> The structure derived from an isocyanato group-containing (meth)acrylate refers to a structure derived from an isocyanato group-containing (meth)acrylate other than the bonding group in the polyurethane (meth)acrylate. Suitable examples of the isocyanato group-containing (meth)acrylate include 2-acryloyloxyethyl isocyanate (trade name: Karenz AOI (registered trademark) manufactured by Showa Denko K.K., etc.) and 2-methacryloyloxyethyl isocyanate (trade name: Karenz MOI (registered trademark) manufactured by Showa Denko K.K., etc.). It is also possible to use a combination of two or more of these isocyanato group-containing (meth)acrylates.

[0145] The resulting polyurethane or urethane (meth)acrylate can be made into a flexible polyurethane foam, a rigid polyurethane foam, a thermoplastic polyurethane, a solvent-based polyurethane solution, an aqueous polyurethane resin dispersion, etc. These can also be processed into molded articles such as artificial leather, synthetic leather, heat insulating materials, cushioning materials, adhesives, paints, coating agents, and films.

[0146] The polycarbonate polyol of the present invention is useful as a raw material for polyurethane compositions. In addition, since the polycarbonate polyol of the present invention can provide a polyurethane composition excellent in tensile strength at break, elongation, and durability, it is industrially useful as a raw material for obtaining various materials to which polyurethane is applied, such as artificial leather, synthetic leather, heat insulating materials, cushioning materials, adhesives, paints, coating agents, and molded articles such as films.

[0147] Next, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to these examples.

[0148] The tests and evaluations carried out in the examples and comparative examples were as follows.

[0149] The hydroxyl value, number average molecular weight, number of terminal hydroxyl groups, terminal oxetanyl group / terminal hydroxyl group, and ratio of oxetanyl terminals to carbonate groups were measured by the methods described above. The weight loss rate by acetone extraction, tensile strength at break, and elastic modulus of the cationically curable resin formulation were measured as follows.

[0150] [Hydroxyl value] The hydroxyl value was determined by titration in accordance with JIS K 1557. Here, the unit of the hydroxyl value is mgKOH / g.

[0151] [Number Average Molecular Weight] The number average molecular weight Mn is calculated based on the hydroxyl value measured in accordance with JIS K 1557. The hydroxyl value is measured, and the number average molecular weight Mn is calculated by the terminal group determination method using (56.1 x 1000 x valence) / hydroxyl value (in this formula, the unit of hydroxyl value is [mgKOH / g]). In the formula, the valence is the number of hydroxyl groups in one molecule.

[0152] [Viscosity] The viscosity was measured using a Brookfield LVDV II + Pro with a cone spindle CPE-41 under the condition of melting at 75°C.

[0153] [NMR] 0.05 g of a PCP sample was dissolved in 0.6 ml of deuterated chloroform, and NMR was performed on a Bruker 54 Ascend 400 MHz (console: AVANCE III HD) with 128 accumulations. １ H-NMR was measured. The integrals of the following peaks were measured. Integral value a is the integral value from 4.00 to 4.30 ppm, and this value was set as the reference integral value a = 1000. Integral value b is the integral value of the peak from 4.35 to 4.48 ppm. Integral value c is the integral value of the peak from 3.71 to 3.76 ppm. Integral value d is the integral value of the peak from 3.44 to 3.65 ppm. Integral value e is the integral value of the peak from 0.74 to 0.96 ppm.

[0154] The peaks are assigned as follows: 4.00 to 4.30 ppm (a): CH adjacent to the carbonate group of PCP ２ 4.35 to 4.48 ppm (b): Oxetanyl terminal and CH of EHO ２ -O-CH ２3.71 to 3.76 ppm (c): CH adjacent to OH of EHO ２ 3.44 to 3.65 ppm (d): Peak of CH2 adjacent to the terminal OH of the polycarbonate polyol. 0.74 to 0.96 ppm (e): Peak of CH in the trimethylolpropane-derived structure of the polycarbonate polyol. ３ In addition, EHO is a peak of R in the above formula 3. ａ is an ethyl group, R ｂ is -R ｂ１ -OH, and R ｂ１ is a methylene group, and is 3-ethyl-3-hydroxymethyloxetane.

[0155] [Number of terminal hydroxyl groups] １ In H-NMR, CH adjacent to the terminal OH ２ The molar ratio (D) of terminal OH calculated from the peak and the molar ratio (T) of polyfunctional polyol calculated from the peak derived from the polyfunctional polyol structure are calculated. The number of terminal hydroxyl groups was calculated as 2 + 2T / (D-T). In the examples using hexanediol and trimethylolpropane, the number of terminal hydroxyl groups was calculated as 2 + 2T / (D-T) = 2 + 2(e / 3) / ((a / 2)-(e / 3)).

[0156] [Number of terminal oxetanyl groups n １ and the number of terminal hydroxyl groups n ２ Ratio to n １ / n ２ ] １ H-NMR revealed that １ / n ２ = (b / 2-c) / (c+d).

[0157] [Ratio of oxetanyl terminal groups to carbonate groups] １ Calculated as (b / 2-c) by H-NMR.

[0158] [the molar concentration of the oxetane compound M ａ and the concentration of hydroxyl groups in PCP, M ｂ Ratio to １ H-NMR revealed that M ａ / M ｂ = c / d.

[0159] [Weight Loss Rate Due to Acetone Extraction] A test piece of a 0.2 mm thick cationically curable resin cured film was weighed and immersed in acetone at 25°C for 7 days for extraction. The test piece was then dried at 120°C for 2 days and the weight was measured. The weight loss rate was calculated using the formula {(original film weight) - (film weight after extraction and drying)} / (original film weight) x 100.

[0160] [Tensile Breaking Strength and Elastic Modulus] Measurements were carried out under an environment of a temperature of 23° C. and a humidity of 50%. After measuring the weight loss rate due to acetone extraction, a test piece of the cationically curable resin cured product film having a thickness of 0.2 mm and a width of 15 mm was pulled at a distance of 10 mm between grippers and a test speed of 0.5 mm / min to measure the tensile breaking strength and elastic modulus.

[0161] Example 1 (Synthesis of Oxetanyl-Modified Polycarbonate Polyol, Formulation of Cationic Curable Resin Blend, Evaluation of Cationic Curable Resin Blend) Synthesis of Oxetanyl-Modified Polycarbonate Polyol (Synthesis Step 1) 134 g of trimethylolpropane, 709 g of 1,6-hexanediol, 731 g of dimethyl carbonate, and 0.044 g of lithium hydroxide were placed in a glass reactor equipped with a distillation column, a stirrer, a thermometer, and a nitrogen inlet tube, and mixed. The DMC / methanol azeotropic components were distilled off at 90 to 190°C under normal pressure until distillation stopped. (Synthesis Step 2) The reaction was carried out at 190°C and 13 kPa for 10 hours, while distilling off DMC and methanol, a by-product alcohol derived from DMC. (Synthesis Step 3) The reaction was carried out at 190°C and 1.3 kPa for 2 hours, while distilling off the unreacted raw material HDL. (Post-treatment step) Dibutyl phosphate in an amount equimolar to lithium hydroxide was added, and the mixture was heated at 100°C for 2 hours to obtain an oxetanyl-modified polycarbonate polyol. The hydroxyl value and NMR measurement of the obtained oxetanyl-modified polycarbonate polyol were performed. Note that synthesis step 1 corresponds to the above steps (i) and (ii), synthesis step 2 corresponds to the above step (iii), and synthesis step 3 corresponds to the above step (iv).

[0162] [Preparation of Cationic Curable Resin Formulation] 30 parts by mass of EHO, 30 parts by mass of Celloxide (registered trademark) 2021P, 40 parts by mass of the obtained oxetanyl-modified polycarbonate polyol, and 4 parts by mass of CPI (registered trademark)-101A were mixed and stirred at room temperature until homogeneous, to obtain a cationic curable resin formulation.

[0163] [Evaluation of cationically curable resin formulation] The obtained cationically curable resin formulation was placed in a space formed by a glass plate, a PET film, and a silicone rubber mold, and irradiated with 20 mW / cm 365 nm UV-LED (manufactured by HOYA). ２ The film was irradiated with UV light for 12 seconds, followed by heating at 65°C for 2 hours and then at 150°C for 1 hour to cure. It was then left to stand for 1 day at a temperature of 23°C and a humidity of 50%, yielding a 0.2 mm-thick cured cationically curable resin product. The weight of the resulting cured product was measured, and it was immersed in acetone and left to stand at 25°C for 7 days to extract the soluble components. It was then removed from the acetone, dried at 120°C for 2 days, and re-weighed. The weight loss due to acetone extraction was calculated. After measuring the weight loss due to acetone extraction, a tensile test was conducted on a test piece of the cured cationically curable resin film, and the tensile strength at break and modulus of elasticity were measured.

[0164] Examples 2 to Comparative Example The same procedure as in Example 1 was carried out except that the conditions were changed as shown in Table 1. However, in Examples 4, 5 and the Comparative Example, synthesis step 3 was not carried out.

[0165] The manufacturing conditions for Examples 1 to 5 and Comparative Examples 1 and 2 are shown in Table 1 below. The abbreviations in the table are as follows: TMP: trimethylolpropane, HDL: hexanediol, DMC: dimethyl carbonate

[0166] The polycarbonate polyols produced in each of the Examples and Comparative Examples were subjected to the measurement and evaluation of the above physical properties. The results are shown in Table 2 below.

[0167] A comparison between Examples 1 to 3 and Comparative Example 1 revealed that when the above formula (B) is satisfied, the weight loss rate of the cured cationic curable resin product due to acetone extraction is small, and the tensile strength at break and tensile modulus of the cured product after acetone extraction are large, i.e., excellent solvent resistance. A comparison between Examples 1 to 3 and Comparative Example 2 revealed that when the above formula (A) is satisfied, the weight loss rate of the cured cationic curable resin product due to acetone extraction is small, i.e., excellent solvent resistance. A comparison between Examples 1 to 3 and Comparative Example 1 revealed that when the above formula (C) is satisfied, the weight loss rate of the cured cationic curable resin product due to acetone extraction is small, and the tensile strength at break and tensile modulus of the cured product after acetone extraction are large, i.e., excellent solvent resistance.

[0168] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0169] The present invention provides a novel oxetanyl-modified polycarbonate polyol that, when used as an additive in the production of cationically curable resins, can improve the solvent resistance of the resins. Such resins can be used in a wide range of applications, such as 3D printer applications.

Claims

1. The following formula 1: [In the formula, R １ are each independently a single bond or a divalent to tetravalent aliphatic or alicyclic hydrocarbon group having 3 to 15 carbon atoms.], a terminal hydroxyl group, and a repeating unit represented by the following formula 2: [In the formula, R ２ are each independently a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms; R ３ are each independently a divalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, and the dashed line represents a bonding site with the repeating unit represented by (Formula 1).] An oxetanyl-modified polycarbonate polyol containing a compound (X) having a terminal oxetanyl group represented by the following formulas (A) and (B): (A) 0.10≦c≦30 (B) 0.015≦(b / 2−c) / (c+d)≦0.050 [wherein the formulas are the values ​​of the oxetanyl-modified polycarbonate polyol measured at 400 MHz using deuterated chloroform as a solvent and tetramethylsilane as a reference substance. １ In H-NMR, when the integral value from 4.00 to 4.30 ppm is set as the reference integral value a=1000, b is the integral value from 4.35 to 4.48 ppm relative to the reference integral value a, c is the integral value from 3.71 to 3.76 ppm relative to the reference integral value a, and d is the integral value from 3.44 to 3.65 ppm relative to the reference integral value a.

2. The following formula 1: [In the formula, R １ are each independently a single bond or a divalent to tetravalent aliphatic or alicyclic hydrocarbon group having 3 to 15 carbon atoms.], a terminal hydroxyl group, and a repeating unit represented by the following formula 2: [In the formula, R ２ are each independently a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms; R ３ are each independently a divalent aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, and the dashed line represents a bonding site with the repeating unit represented by (Formula 1).] An oxetanyl-modified polycarbonate polyol containing a compound (X) having a terminal oxetanyl group represented by the following formula (C): (C) 2.5≦b / 2−c≦20 [wherein the formula is a measurement of the oxetanyl-modified polycarbonate polyol at 400 MHz using deuterated chloroform as a solvent and tetramethylsilane as a reference substance. １ In H-NMR, when the integral value from 4.00 to 4.30 ppm is set as the reference integral value a=1000, b is the integral value from 4.35 to 4.48 ppm relative to the reference integral value a, and c is the integral value from 3.71 to 3.76 ppm relative to the reference integral value a.

3. R １ and each independently represent an alkylene group having 5 or 6 carbon atoms.

4. The oxetanyl-modified polycarbonate polyol according to claim 1 or 2, wherein the number of terminal hydroxyl groups is 2.5 to 4.

0.

5. The oxetanyl-modified polycarbonate polyol according to claim 1 or 2, comprising a structure α derived from an aliphatic or alicyclic diol and a structure β derived from a polyhydric alcohol, wherein the polyhydric alcohol is trimethylolpropane.

6. The oxetanyl-modified polycarbonate polyol according to claim 1 or 2, which has a hydroxyl value of 35 to 450 mg KOH / g.

7. The oxetanyl-modified polycarbonate polyol according to claim 1 or 2, which has a number average molecular weight of 400 to 4,500 g / mol.

8. The oxetanyl-modified polycarbonate polyol according to claim 1 or 2, which has a viscosity at 75°C of 50 to 1,000 mPa·s.

9. The following equation 3: [In the formula, R ａ is a monovalent aliphatic or alicyclic hydrocarbon having 1 to 6 carbon atoms; R ｂ is a monovalent organic group having 1 to 6 carbon atoms.] and the oxetanyl-modified polycarbonate polyol according to claim 1 or 2.

10. The molar concentration M of the oxetane compound contained in the composition ａ and the molar concentration M of hydroxyl groups derived from the oxetanyl-modified polycarbonate polyol contained in the composition. ｂ Relative to M ａ / M ｂ The composition according to claim 9, wherein is 0.001 to 0.

04.

11. A cationically curable resin composition comprising the oxetanyl-modified polycarbonate polyol according to claim 1 or 2, and an epoxy compound and / or an oxetane compound.

12. A polyurethane resin containing a structure derived from the oxetanyl-modified polycarbonate polyol according to claim 1 or 2.

13. A urethane (meth)acrylate containing a structure derived from the oxetanyl-modified polycarbonate polyol according to claim 1 or 2.

14. A method for producing the oxetanyl-modified polycarbonate polyol according to claim 1 or 2, comprising, among the following steps (i) to (iv): steps (i) and (iv); steps (i), (ii) and (iv); steps (i), (iii) and (iv); or steps (i) to (iv): (i) the following steps (A) or (B): (A) mixing an aliphatic or alicyclic diol, a polyhydric alcohol, and a carbonate ester to obtain a mixture; (B) mixing a polycarbonate polyol with a polyhydric alcohol, or mixing a polycarbonate polyol with a polyhydric alcohol and a carbonate ester to obtain a mixture; (ii) heating the mixture obtained in step (i) at 90 to 210°C under 96 to 608 kPa to obtain a first product containing a polycarbonate polyol; (iii) heating the first product obtained in step (i) or (ii) at 150 to 210°C under a pressure of 2.7 to 40.0 kPa to obtain a second product in which the carbonate ester and / or carbonate ester-derived by-product alcohol is reduced; (iv) heating the mixture or product obtained in step (i), (ii) or (iii) at 180 to 200°C under a pressure of less than 2.7 kPa to obtain an oxetanyl-modified polycarbonate polyol.

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