Diol-containing composition, polycarbonate diol, and polyurethane

Abstract

To provide a diol-containing composition that enables production of a polycarbonate diol excellent in quality such as color tone, and further enables production of a polyurethane having excellent mechanical properties with suppressed variation in the mechanical properties.SOLUTION: A diol-containing composition used in a step for producing a polycarbonate diol comprises at least one selected from primary and secondary amines, and a diol (1) represented by the general formula (1) in the figure. (In the general formula (1), R represents a hydrocarbon group having 2 to 20 carbon atoms, which may have a substituent or a heteroatom.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a diol-containing composition. Furthermore, the present invention relates to a polycarbonate diol made from the diol-containing composition, and a polyurethane made from the polycarbonate diol. [Background technology]

[0002] Diols such as 1,6-hexanediol and 1,4-butanediol are widely used as raw materials for polycarbonate diols, polyether polycarbonate diols, polyester polycarbonate diols, and the like (Non-Patent Document 1). For example, polyurethanes that use polycarbonate diol as a raw material for the soft segment portion are considered to have the best durability grade in terms of heat resistance and hydrolysis resistance, and are widely used in durable films, artificial leather for automobiles, (water-based) paints, and adhesives. In addition, in order to improve the flexibility, crystallinity, strength, etc. of polyurethane, polycarbonate diols, which are diols such as 1,6-hexanediol combined with other diols, are sometimes used.

[0003] For example, Patent Document 1 discloses a technology in which a tertiary amino alcohol having a specific structure is blended into a polycarbonate diol-containing composition to suppress coloration of the resulting polycarbonate, and also to appropriately improve the reactivity with a polyisocyanate compound, thereby improving the efficiency of polyurethane production. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-053072 [Non-patent literature]

[0005] [Non-Patent Document 1] "Fundamentals and Applications of Polyurethanes" pp. 96-106, edited by Katsuji Matsunaga, CMC Publishing Co., Ltd., published November 2006 Summary of the Invention [Problem to be solved by the invention]

[0006] However, Patent Document 1 only focuses on the tertiary amine contained in the polycarbonate diol-containing composition, and specifically discloses only 8-dimethylamino-1-octanol. Furthermore, Patent Document 1 does not mention at all that by adding an amine other than a tertiary amine to a diol-containing composition, variations in mechanical properties can be suppressed and polyurethanes of uniform quality can be obtained.

[0007] An object of the present invention is to provide a diol-containing composition that can produce polyurethane having uniform quality, good mechanical properties, and good chemical resistance while maintaining good color tone of the resulting polycarbonate diol and suppressing variations in mechanical properties. Another object of the present invention is to provide a polycarbonate diol-containing composition that can produce polyurethane with reduced variation in mechanical properties, uniform quality, and excellent mechanical properties and chemical resistance. Another object of the present invention is to provide a polyurethane having reduced variations in mechanical properties, uniform quality, and good mechanical properties and chemical resistance. [Means for solving the problem]

[0008] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by using a diol-containing composition containing a primary amine or a secondary amine as a raw material for polycarbonate diol.

[0009] The present invention provides the following.

[0010] [1] A diol-containing composition used in a process for producing a polycarbonate diol, the diol-containing composition comprising at least one of a primary amine and a secondary amine and a diol (1) represented by the following general formula (I):

[0011] [ka]

[0012] (In the above general formula (I), R represents a hydrocarbon group having 2 to 20 carbon atoms, which may have a substituent or a heteroatom.)

[0013] [2] The diol-containing composition according to [1], wherein the diol (1) comprises a diol (1a) represented by the following general formula (Ia):

[0014] [ka]

[0015] (In the above general formula (1), n ​​is an integer of 2 to 20.)

[0016] [3] The diol-containing composition according to [2], wherein the diol (1) includes at least one selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

[0017] [4] The diol-containing composition according to any one of [1] to [3], wherein the primary amine and the secondary amine contain one or more amino groups and one or more functional groups, and the functional groups include at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a formyl group, and an amino group.

[0018] [5] The diol-containing composition according to any one of [1] to [4], wherein the primary amine and the secondary amine include an amine represented by the following general formula (II):

[0019] [ka]

[0020] (In the above general formula (II), R 1 represents an alkyl group having 2 to 20 carbon atoms and having r substituents X, which may have substituents other than X. X represents a hydroxyl group, a carboxyl group, a formyl group, or an amino group. r is an integer of 1 to 6. R 2 represents an alkyl group having 1 to 20 carbon atoms, which may have a substituent, or a hydrogen atom.

[0021] [6] The diol-containing composition according to [5], wherein the primary amine or secondary amine includes at least one selected from 6-amino-1-hexanol, 6-methylamino-1-hexanol, and 6-ethylamino-1-hexanol.

[0022] [7] The diol-containing composition according to any one of [1] to [6], wherein the total content of the primary amine and the secondary amine contained in the diol-containing composition is 1 mass ppm or more in terms of nitrogen atoms, relative to the total mass of the diol-containing composition.

[0023] [8] The diol-containing composition according to any one of [1] to [7], wherein the total content of the primary amine and the secondary amine contained in the diol-containing composition is 1500 mass ppm or less in terms of nitrogen atoms, relative to the total mass of the diol-containing composition.

[0024] [9] The diol-containing composition according to any one of [1] to [8], wherein the diol (1) includes a biomass-derived diol.

[0025]

[10] A polycarbonate diol obtained from the diol-containing composition according to any one of [1] to [9] and a carbonate compound as raw materials.

[0026]

[11] A polyurethane made from the polycarbonate diol described in

[10] and an isocyanate compound. [Effects of the Invention]

[0027] According to the present invention, there can be provided a diol-containing composition used for producing a polycarbonate diol, which can maintain the color tone of the resulting polycarbonate diol well, and further can be used to produce a polyurethane having uniform quality, good mechanical properties, and good chemical resistance, with reduced variation in mechanical properties, using the polycarbonate diol as a raw material. Furthermore, according to the present invention, it is possible to provide a polycarbonate diol-containing composition that can produce polyurethane with reduced variation in mechanical properties, uniform quality, and excellent mechanical properties and chemical resistance. Furthermore, according to the present invention, it is possible to provide polyurethanes with reduced variations in mechanical properties, uniform quality, and good mechanical properties and chemical resistance. DETAILED DESCRIPTION OF THE INVENTION

[0028] The present invention will be described in detail below. The present invention is not limited to the following description, and can be practiced in any modified form without departing from the gist of the present invention.

[0029] Unless otherwise specified, in this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits, and "A to B" means A or more and B or less.

[0030] In this specification, "A or B" means "A," "B," and "A and B," unless otherwise specified. For example, "including A or B" means "including A," "including B," and "including A and B," unless otherwise specified.

[0031] In this specification, "% by mass" indicates the content of a given component in a total amount of 100% by mass. In this specification, "mass %" and "weight %", "mass ppm" and "weight ppm", and "parts by mass" and "parts by weight" are synonymous. Furthermore, when simply written as "ppm", it means "ppm by weight".

[0032] In this specification, the term "structural unit" refers to a unit derived from a raw material compound used in the production of a polycarbonate diol, formed by polymerization of the raw material compound, and refers to a partial structure sandwiched between any linking groups in the obtained polymer. It also includes a partial structure at the terminal portion of a polymer, one of which is a linking group and the other of which is a polymerization reactive group. The structural unit may be a unit formed directly by a polymerization reaction, or may be a unit obtained by converting a part of the unit into another structure by treating the obtained polymer.

[0033] As used herein, "optional" or "optionally" means that the subsequently described circumstance may or may not occur, and thus the description includes both the occurrence and non-occurrence of the circumstance.

[0034] As used herein, the term "about" can mean above and below 20% of the stated value. For example, about 75°C encompasses the range of 60°C to 90°C.

[0035] In this specification, the term "obtained polycarbonate diol" refers to a polycarbonate diol produced using the diol-containing composition of the present invention and a carbonate compound as raw materials. In this specification, the term "obtained polyurethane" refers to a polyurethane produced using the polycarbonate diol of the present invention and an isocyanate compound as raw materials.

[0036] In this specification, the "diol-containing composition of the present invention," the "polycarbonate diol of the present invention," and the "polyurethane of the present invention" are collectively referred to as "the present invention."

[0037] All steps described herein can be performed in any suitable order unless otherwise stated herein or clearly contradicted by context.

[0038] <Diol-containing composition> The diol-containing composition of the present invention is a composition containing at least one amine selected from primary amines and secondary amines (hereinafter referred to as a "primary amine or secondary amine" or a "primary or secondary amine") and a diol (1) described below. The diol-containing composition of the present invention can be used in a process for producing a polycarbonate diol. The diol-containing composition of the present invention is substantially composed of a diol and a trace amount of a primary or secondary amine, and therefore may be generally referred to as a "diol." However, since it is not composed of only a diol, which is a single component, it is referred to as a "diol-containing composition."

[0039] The primary amine or secondary amine will be described in detail later.

[0040] The diol-containing composition of the present invention contains the primary or secondary amine, and the polycarbonate diol produced from this diol-containing composition maintains its color well enough to be practically usable. Furthermore, the polyurethane produced from the polycarbonate diol has reduced variations in mechanical properties, is of uniform quality, and has good mechanical properties and chemical resistance.

[0041] <Diol (1)> In the present invention, the diol (1) is a compound represented by the following general formula (I), and is one of the components constituting the diol-containing composition of the present invention.

[0042] [ka]

[0043] (In the above general formula (I), R represents a hydrocarbon group having 2 to 20 carbon atoms, which may have a substituent or a heteroatom.)

[0044] By including the diol (1) in the diol-containing composition of the present invention, a polyurethane having good mechanical properties and chemical resistance can be obtained using a polycarbonate diol produced using the diol-containing composition as a raw material.

[0045] In the diol-containing composition of the present invention, the diol (1) is not particularly limited, and known dihydroxy compounds used as raw materials for polycarbonate diols can be appropriately selected and used depending on the use of the polycarbonate diol, production conditions, etc.

[0046] Examples of the diol (1) include diols having no side chains, such as 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, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, and 1,20-eicosanediol, from the viewpoint of providing the resulting polyurethane with excellent chemical resistance and mechanical strength. Among these, from the viewpoint of providing a polyurethane with an excellent balance of flexibility, low-temperature properties, and chemical resistance, at least one compound selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,10-decanediol is preferred, and at least one compound selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol is more preferred. These compounds may be used alone or in combination of two or more.

[0047] Alternatively, the diol (1) may be optionally selected from the following compounds within the range not impairing the effects of the present invention: Diols having a side chain such as 1,3-butanediol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,8-octanediol, 2,2-dimethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol; cyclic diols such as 1,4-cyclohexanedimethanol and 2-bis(4-hydroxycyclohexyl)-propane; oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol; and diols having a cyclic ether structure such as isosorbide, isomannide, and isoidet, which are stereoisomers. These compounds may be used alone or in combination of two or more.

[0048] Furthermore, the diol-containing composition of the present invention may contain, as necessary, a polyol having three or more hydroxyl groups per molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, or pentaerythritol, within a range that does not impair the effects of the present invention.

[0049] The content of diol (1) in the diol-containing composition of the present invention is not particularly limited, and from the viewpoint of improving the handleability of the obtained polycarbonate diol and the flexibility and low-temperature properties of the obtained polyurethane, it is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 96% by mass or more, relative to 100% total mass of the diol-containing composition. On the other hand, the upper limit of the content of diol (1) in the diol-containing composition is not particularly limited, and it can be preferably less than 100% by mass, more preferably 99% by mass or less, even more preferably 98% by mass or less, and particularly preferably 97% by mass or less, relative to 100% total mass of the diol-containing composition. The above upper and lower limits can be combined in any combination. For example, the content of diol (1) in the diol-containing composition of the present invention can be set to 85% by mass or more and less than 100% by mass, more preferably 90% by mass or more and 99% by mass or less, still more preferably 95% by mass or more and 98% by mass or less, and particularly preferably 96% by mass or more and 97% by mass or less, based on 100% by mass of the total mass of the diol-containing composition.

[0050] The diol (1) may contain a diol (1a) represented by the following general formula (Ia), if necessary.

[0051] [ka]

[0052] (In the above general formula (1), n ​​is an integer of 2 to 20.)

[0053] When the diol (1) contains the diol (1a), a polyurethane having better mechanical properties and chemical resistance can be obtained.

[0054] In the diol (1a) represented by the general formula (Ia), the lower limit of n is not particularly limited, and is 2 or more, preferably 3 or more, and more preferably 4 or more. On the other hand, the upper limit of n is 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less. The upper and lower limits can be combined in any combination. For example, in the diol (1a) represented by the general formula (Ia), n is 2 or more and 20 or less, preferably 3 or more and 15 or less, more preferably 4 or more and 10 or less, and even more preferably 4 or more and 6 or less. Among these, the diol (1) is preferably at least one selected from 1,4-butanediol (n=4), 1,5-pentanediol (n=5), and 1,6-hexanediol (n=6). The diol (1) may be used alone or in combination of two or more kinds.

[0055] The content of diol (1a) in the diol (1) is not particularly limited, and from the viewpoint of improving the handleability of the polycarbonate diol and the flexibility and low-temperature properties of the resulting polyurethane, it is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 70% by mass or more, relative to 100% total mass of the diol (1). This content may also be 90% by mass or more. On the other hand, the upper limit of the content of diol (1a) in the diol (1) is not particularly limited, and may be 100% by mass, or may be preferably less than 100% by mass, more preferably 99% by mass or less, even more preferably 98% by mass or less, and particularly preferably 97% by mass or less, relative to 100% total mass of the diol (1). The upper and lower limits can be combined arbitrarily. For example, the content of diol (1a) in diol (1) can be 100% by mass, or preferably 10% by mass or more but less than 100% by mass, more preferably 30% by mass or more but 99% by mass, even more preferably 50% by mass or more but 98% by mass, and particularly preferably 70% by mass or more but 97% by mass, based on 100% by mass of the total mass of the polycarbonate diol.

[0056] The diol-containing composition of the present invention can achieve the Sustainable Development Goals (SDGs) by using a diol-containing composition containing a biomass-derived diol as the diol (1). Specifically, a biomass-derived diol alone or a mixture containing a biomass-derived diol and a fossil fuel-derived diol can be used. Biomass-derived diols are diols derived from non-edible biomass and / or non-fossil fuels.

[0057] When the diol (1) is obtained by fermenting biomass resources such as sugars with fungal cells, primary amines or secondary amines may be produced as by-products. In the present invention, by using a biomass-derived diol as the diol (1), the primary amines and secondary amines produced as by-products are effectively utilized, and the resulting polyurethane has reduced variation in mechanical properties, uniform quality, and good mechanical properties and chemical resistance.

[0058] In the present invention, non-edible biomass refers to resources made from non-edible grasses or trees. Specific examples include, but are not limited to, cellulose, hemicellulose, lignin, etc. obtained from woody biomass such as coniferous and broad-leaved trees, bioethanol and biodiesel obtained from herbaceous biomass such as corn and sugarcane stalks, soybeans, and rapeseed, and plant-derived waste oil. In the present invention, the term "non-fossil fuel" refers to, for example, hydrogen or organic matter derived from plants or animals that is not derived from fossil fuels or non-edible biomass. Specific examples include, but are not limited to, methane and sugar ethanol obtained from firewood, charcoal, dried livestock manure, etc.

[0059] In the present invention, the diol (1) derived from a fossil fuel refers to at least one selected from the group consisting of diol (1) derived from petroleum, diol (1) derived from coal, and diol (1) derived from natural gas.

[0060] The biomass-derived diol (1) may contain the primary or secondary amine described above depending on its origin. Therefore, the effects of the present invention can be achieved by producing the diol-containing composition of the present invention by controlling the content of the primary or secondary amine in the diol (1) or by controlling the content of the primary or secondary amine in the diol-containing composition produced using the diol (1).

[0061] In the diol-containing composition of the present invention, 1,6-hexanediol derived from fossil fuels can be used alone as the diol (1a). Alternatively, the diol-containing composition of the present invention uses, as the diol (1a), 1,6-hexanediol including biomass-derived 1,6-hexanediol, specifically biomass-derived 1,6-hexanediol alone, or a mixture containing biomass-derived 1,6-hexanediol and fossil fuel-derived 1,6-hexanediol, thereby achieving the Sustainable Development Goals (SDGs). Biomass-derived 1,6-hexanediol is 1,6-hexanediol derived from non-edible biomass and / or non-fossil fuels.

[0062] In the present invention, 1,6-hexanediol derived from a fossil fuel refers to at least one selected from petroleum-derived 1,6-hexanediol, coal-derived 1,6-hexanediol, and natural gas-derived 1,6-hexanediol.

[0063] The above-mentioned biomass-derived 1,6-hexanediol may contain the above-mentioned primary or secondary amines depending on its origin. Therefore, the above-mentioned effects of the present invention can be obtained by producing the diol-containing composition of the present invention by controlling the content of the primary or secondary amines in the 1,6-hexanediol.

[0064] <Primary amine or secondary amine> The primary amine or secondary amine in the present invention is one component constituting the diol-containing composition of the present invention.

[0065] By including at least one of the primary and secondary amines in the diol-containing composition of the present invention, the color tone of the obtained polycarbonate diol is well maintained, and the variation in mechanical properties of the obtained polyurethane is suppressed, the quality is uniform, and the mechanical properties and chemical resistance can be improved.

[0066] The primary or secondary amine in the present invention is not particularly limited, and any known amine compound can be used.

[0067] For example, as a first embodiment, the primary or secondary amine in the present invention can include an amine compound in which some or all of the hydroxy groups of the diol (1) are substituted with amino groups. This can further improve the effects of suppressing variations in mechanical properties, uniform quality, and good mechanical properties and chemical resistance in the obtained polyurethane while maintaining good color tone of the obtained polycarbonate diol. Specifically, when the diol (1) is the diol (1a) represented by the general formula (Ia), examples of the primary or secondary amine include those described below. When n=3, primary amine compounds such as 3-amino-1-propanol and 1,3-diaminopropane, and secondary amine compounds such as 3-methylamino-1-propanol; When n=4, primary amine compounds such as 4-amino-1-butanol and 1,4-diaminobutane, and secondary amine compounds such as 4-methylamino-1-butanol; When n=5, primary amine compounds such as 5-amino-1-pentanol and 1,5-diaminopentane, and secondary amine compounds such as 5-methylamino-1-pentanol; When n=6, examples include primary amine compounds such as 6-amino-1-hexanol and 1,6-diaminohexane, and secondary amine compounds such as 6-methylamino-1-hexanol and 6-ethylamino-1-hexanol. These compounds may be used alone or in combination of two or more.

[0068] In a second embodiment, the primary or secondary amine in the present invention contains one or more amino groups and one or more functional groups, and the functional group can contain at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a formyl group, and an amino group. This can further improve the effects of suppressing variation in mechanical properties, achieving uniform quality, and improving mechanical properties and chemical resistance in the obtained polyurethane while maintaining good color tone of the obtained polycarbonate diol.

[0069] As a third embodiment, the primary or secondary amine in the present invention can include an amine represented by the following general formula (II): This can further improve the effects of suppressing variations in mechanical properties, uniform quality, and good mechanical properties and chemical resistance in the obtained polyurethane while maintaining good color tone of the obtained polycarbonate diol.

[0070] [ka]

[0071] (In the above general formula (II), R 1 represents an alkyl group having 2 to 20 carbon atoms and having r substituents X, which may have substituents other than X. X represents a hydroxyl group, a carboxyl group, a formyl group, or an amino group. r is an integer of 1 to 6. R 2 represents an alkyl group having 1 to 20 carbon atoms, which may have a substituent, or a hydrogen atom.

[0072] In the above general formula (II), NHR 2and X react with the carbonate bond or hydroxyl group of the polycarbonate diol, or with the isocyanate compound used as a raw material for polyurethane. If an excessive number of substituents X are present, a crosslinked structure is formed in the polyurethane during the polymerization process in producing the polyurethane, causing gelation and impairing polymerization stability. Therefore, r, which represents the number of substituents X, is preferably 1 or 2, and more preferably 1. R 1 The number of carbon atoms in R is 2 to 20. From the viewpoint that the mechanical properties of the polyurethane obtained by using the polycarbonate diol of the present invention are good, R 1 The number of carbon atoms is preferably 3 to 10, more preferably 3 to 6, and even more preferably 4 to 6. R 2 is an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. From the viewpoint of improving the mechanical properties of the polyurethane obtained by using the polycarbonate diol of the present invention, R 2 is preferably an alkyl group having 3 to 10 carbon atoms or a hydrogen atom, more preferably an alkyl group having 3 to 6 carbon atoms or a hydrogen atom, and even more preferably an alkyl group having 4 to 6 carbon atoms or a hydrogen atom.

[0073] Specific examples of the amine represented by the general formula (II) include those described below. R 1 is a propylene group having 3 carbon atoms, primary amine compounds such as 3-amino-1-propanol, secondary amine compounds such as 3-methylamino-1-propanol; R 1 is a butylene group having 4 carbon atoms, primary amine compounds such as 4-amino-1-butanol, secondary amine compounds such as 4-methylamino-1-butanol; R 1 When is a pentylene group having 5 carbon atoms, primary amine compounds such as 5-amino-1-pentanol, secondary amine compounds such as 5-methylamino-1-pentanol, etc. R 1When is a hexylene group having 6 carbon atoms, examples of the amine compounds include primary amine compounds such as 6-amino-1-hexanol, and secondary amine compounds such as 6-methylamino-1-hexanol and 6-ethylamino-1-hexanol. Among these, at least one selected from 6-amino-1-hexanol, 6-methylamino-1-hexanol, and 6-ethylamino-1-hexanol is preferred. These compounds may be used alone or in combination of two or more.

[0074] The upper limit of the total content of the primary or secondary amines (when primary and secondary amines are contained, the total content of these) contained in the diol-containing composition of the present invention is preferably 1500 mass ppm or less in terms of nitrogen atoms relative to the total mass of the diol-containing composition, from the viewpoints of suppressing coloration of the obtained polycarbonate diol to achieve a good color tone and improving the yield during polycarbonate diol polymerization. If the content of the primary or secondary amines is too high, depending on the conditions for producing the polycarbonate diol, the primary or secondary amines may inhibit catalytic activity or exhibit coloring effects, thereby impairing the yield and color tone of the polycarbonate diol. The upper limit of the content of the primary or secondary amines is more preferably 1400 mass ppm or less in terms of nitrogen atoms, even more preferably 1200 mass ppm or less, particularly preferably 1000 mass ppm or less, and especially preferably 500 mass ppm or less. On the other hand, the lower limit of the total content of the primary or secondary amines contained in the diol-containing composition of the present invention is not particularly limited. From the viewpoint of economic efficiency such as the production cost required for purifying the diol-containing composition, and from the viewpoint of appropriately widening the molecular weight distribution of the resulting polyurethane to improve the mechanical properties of the polyurethane and suppressing the variation in the mechanical properties, the total content of the primary or secondary amines, calculated as nitrogen atoms, relative to the total mass of the diol-containing composition, is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, even more preferably 50 ppm by mass or more, particularly preferably 100 ppm by mass or more, and particularly preferably 200 ppm by mass or more. The above upper and lower limits can be combined arbitrarily. For example, the total content of the primary or secondary amines contained in the diol-containing composition of the present invention is, in terms of nitrogen atoms, preferably 1 mass ppm to 1500 mass ppm, more preferably 10 mass ppm to 1400 mass ppm, still more preferably 50 mass ppm to 1200 mass ppm, particularly preferably 100 mass ppm to 1000 mass ppm, and particularly preferably 200 mass ppm to 500 mass ppm, relative to the total mass of the diol-containing composition.

[0075] The method for controlling the total content of the primary amine or secondary amine in the diol-containing composition of the present invention is not particularly limited. As described above, for example, when sugar or the like is used as a biomass resource and the diol (1) is obtained by fermenting the biomass resource with bacterial cells, the primary amine or secondary amine is by-produced, and the total content can be controlled by adjusting the type of bacterial cells, the fermentation time, the distillation and purification conditions, etc.

[0076] <Polycarbonate diol> The polycarbonate diol of the present invention is a polycarbonate diol compound produced using the diol-containing composition of the present invention and a carbonate compound as raw materials.

[0077] The polycarbonate diol of the present invention can contain the structural unit (1-1) described below and the structural unit (2) described below.

[0078] (Structural unit (1-1)) The above-mentioned structural unit (1-1) is a structural unit represented by the following general formula (I-1) derived from the diol (1) contained in the structure of the polycarbonate diol of the present invention.

[0079] [ka]

[0080] (In the above general formula (I-1), R has the same meaning as R in the above formula (I) and represents a hydrocarbon group having 2 to 20 carbon atoms, which may have a substituent or a hetero atom.)

[0081] The diol (1) in the polycarbonate diol of the present invention is treated as having the same meaning as the diol (1) mentioned in the description of the diol-containing composition of the present invention.

[0082] The polycarbonate diol of the present invention contains the structural unit (1-1) derived from the diol (1), and the obtained polyurethane has good mechanical properties and chemical resistance.

[0083] The lower limit of the content of the structural unit (1-1) in the polycarbonate diol of the present invention is not particularly limited, and from the viewpoint of obtaining good mechanical properties and chemical resistance of the resulting polyurethane, it is preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 75% by mass or more, and particularly preferably 80% by mass or more, relative to 100% by mass of the total mass of the polycarbonate diol. On the other hand, the upper limit of the content of the structural unit (1-1) is not particularly limited, and it may correspond to 100% by mass of the mass of the structural unit other than the structural unit (2) in the polycarbonate diol of the present invention, or may be less than 100% by mass. Alternatively, from the viewpoint of maintaining good chemical resistance of the resulting polyurethane, it is more preferably 98% by mass or less, even more preferably 95% by mass or less, and particularly preferably 90% by mass or less, relative to 100% by mass of the total mass of the polycarbonate diol. The upper and lower limits can be combined arbitrarily. For example, the content of the structural unit (1) in the polycarbonate diol of the present invention is preferably 40% by mass or more and less than 100% by mass, more preferably 60% by mass or more and 98% by mass or less, still more preferably 75% by mass or more and 95% by mass or less, and particularly preferably 80% by mass or more and 90% by mass or less, relative to 100% by mass of the total mass of the polycarbonate diol.

[0084] In the polycarbonate diol of the present invention, the structural unit (1-1) preferably contains a structural unit represented by the following general formula (Ia-1) derived from the diol (1a), from the viewpoint of improving the mechanical properties and chemical resistance of the resulting polyurethane.

[0085] [ka]

[0086] (In the above general formula (Ia-1), n ​​has the same meaning as n in the above formula (Ia) and is an integer of 2 to 20.)

[0087] The diol (1a) in the polycarbonate diol of the present invention is treated as having the same meaning as the diol (1a) mentioned in the description of the diol-containing composition of the present invention.

[0088] In the general formula (Ia-1), the lower limit of n is not particularly limited, and is 2 or more, preferably 3 or more, and more preferably 4 or more. On the other hand, the upper limit of n is 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less. The upper and lower limits can be combined in any combination. For example, in the diol (1a) represented by the general formula (Ia), n is 2 or more and 20 or less, preferably 3 or more and 15 or less, more preferably 4 or more and 10 or less, and even more preferably 4 or more and 6 or less. The structural unit (1) may be used alone or in combination of two or more types.

[0089] (Structural unit (2)) The structural unit (2) is a structural unit derived from at least either a primary amine or a secondary amine, as described above, which is contained in the structure of the polycarbonate diol of the present invention.

[0090] The primary or secondary amine in the polycarbonate diol of the present invention is treated as having the same meaning as the primary or secondary amine mentioned in the description of the diol-containing composition of the present invention.

[0091] The polycarbonate diol of the present invention contains the structural unit (2), and therefore, in a polyurethane obtained using this polycarbonate diol, the variation in mechanical properties is suppressed, the quality is uniform, and the mechanical properties and chemical resistance are good.

[0092] Furthermore, the structural unit (2) may contain a structural unit (2-1) represented by the following general formula (II-1).

[0093] [ka]

[0094] (In the above general formula (II-1), m is R 1 R is an integer of 2 to 20. 2 is R in the formula (II). 2 and represents an optionally substituted alkyl group having 1 to 20 carbon atoms or a hydrogen atom.)

[0095] The polycarbonate diol of the present invention can contain a structural unit represented by the following general formula (IIIa) or the following general formula (IIIb) as a terminal structure.

[0096] [ka]

[0097] (In the above general formula (IIIa), m is an integer of 2 to 20. R 2 is R in the formula (II). 2 and represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent.)

[0098] [ka]

[0099] (In the above general formula (IIIb), m is an integer of 2 to 20. R 2 is R in the formula (II). 2 and represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent.)

[0100] Furthermore, since the polycarbonate diol of the present invention contains the structural unit (2-1), the color tone of the obtained polycarbonate diol is well maintained, and the obtained polyurethane has reduced variation in mechanical properties, uniform quality, and good mechanical properties and chemical resistance.

[0101] In the polycarbonate diol of the present invention, the upper limit of the content of the structural unit (2-1) is not particularly limited, and when the diol-containing composition of the present invention is used, the upper limit is preferably 1200 mass ppm or less, more preferably 1000 mass ppm or less, and even more preferably 900 mass ppm or less, calculated as nitrogen atoms, relative to the total mass of the polycarbonate diol. A concentration of 700 ppm by mass or less is particularly preferred, and a concentration of 500 ppm by mass or less is especially preferred. On the other hand, the lower limit of the content of the structural unit (2-1) is not particularly limited, and when the diol-containing composition of the present invention is used, the content is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, even more preferably 50 ppm by mass or more, particularly preferably 100 ppm by mass or more, and especially preferably 150 ppm by mass or more, calculated as nitrogen atoms, relative to the total mass of the polycarbonate diol. The upper and lower limits can be combined arbitrarily. For example, the content of the structural unit (2-1) in the polycarbonate diol of the present invention is, in terms of nitrogen atoms, preferably 1 mass ppm to 1,200 mass ppm, more preferably 10 mass ppm to 1,000 mass ppm, even more preferably 50 mass ppm to 900 mass ppm, particularly preferably 100 mass ppm to 700 mass ppm, and particularly preferably 150 mass ppm to 500 mass ppm, relative to the total mass of the polycarbonate diol.

[0102] (Molecular weight of polycarbonate diol) The lower limit of the number average molecular weight (Mn) of the polycarbonate diol of the present invention is not particularly limited, and from the viewpoint of good mechanical properties of the obtained polyurethane, it is preferably 250 or more, more preferably 300 or more, and even more preferably 400 or more. On the other hand, the upper limit of the number average molecular weight (Mn) is not particularly limited, and from the viewpoint of keeping the viscosity of the polycarbonate diol of the present invention to a certain level and maintaining good handleability, and from the viewpoint of maintaining good chemical resistance of the obtained polyurethane, it is preferably 5000 or less, more preferably 4000 or less, and even more preferably 3000 or less. The above upper and lower limits can be combined in any combination. For example, the number average molecular weight (Mn) of the polycarbonate diol in the present invention is preferably 250 or more and 5,000 or less, more preferably 300 or more and 4,000 or less, and even more preferably 400 or more and 3,000 or less. The number average molecular weight (Mn) is a molecular weight calculated from the hydroxyl value, and the measurement conditions are as described in the examples below.

[0103] <Method for producing polycarbonate diol> The method for producing the polycarbonate diol of the present invention is not particularly limited, and for example, known methods for producing polycarbonate diols described in Schnell, Polymer Reviews, Vol. 9, pp. 9-20 (1994) and WO 2015 / 199070 can be used.

[0104] A specific embodiment of the method for producing the polycarbonate diol of the present invention includes a method in which the diol-containing composition of the present invention containing the primary or secondary amine and a carbonate compound described later are polycondensed by a transesterification reaction, if necessary, in the presence of a catalyst described later, to obtain a polycarbonate diol. As an example of the method for producing the polycarbonate diol of the present invention, a method using diphenyl carbonate as the carbonate will be described below. The production of the polycarbonate diol can be carried out in two stages.

[0105] In the first-stage reaction, the diol-containing composition of the present invention and diphenyl carbonate are mixed in a molar ratio of 20:1 to 1:10, preferably 10:1 to 1:2, and after adding a Mg catalyst as a transesterification catalyst, the mixture is reacted at 100 to 250°C under normal pressure, and the phenol produced is removed from the reaction system to obtain a low-molecular-weight polycarbonate diol. In the second-stage reaction, the reaction product of the first stage is heated at 130 to 250°C under reduced pressure, and the phenol and unreacted diol (1) are removed from the reaction system while the low-molecular-weight polycarbonate diol is self-condensed to obtain a polycarbonate diol of a predetermined molecular weight.

[0106] (carbonate compounds) The carbonate compound that can be used to produce the polycarbonate diol of the present invention is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate; diaryl carbonates such as diphenyl carbonate; alkylene carbonates such as ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate; etc. One or more carbonates from these can be used as raw materials. Among these, from the viewpoints of reactivity with the diol (1), ease of availability, and ease of setting polymerization reaction conditions, it is preferable to use one or more carbonate compounds selected from dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, and ethylene carbonate. The amount of carbonate compound used is not particularly limited, and for example, the conditions described in WO 2015 / 199070 can be appropriately optimized by a person skilled in the art according to known techniques.

[0107] (primary or secondary amine) The primary or secondary amine in the production of the polycarbonate diol of the present invention can be treated as synonymous with the primary or secondary amine mentioned in the description of the diol-containing composition of the present invention, particularly the primary or secondary amine mentioned in the first, second, and third embodiments.

[0108] Furthermore, as the primary or secondary amine in the production of the polycarbonate diol of the present invention, the amines that form the structural unit (2) mentioned in the description of the polycarbonate diol of the present invention can be used.

[0109] (catalyst) In producing the polycarbonate diol of the present invention, when the diol in the diol-containing composition of the present invention and a carbonate compound are polycondensed by a transesterification reaction to obtain the polycarbonate diol, a known transesterification catalyst (hereinafter sometimes referred to as "catalyst") used in the synthesis of polycarbonate diol can be used as a catalyst for promoting the transesterification reaction. In this case, if an excessive amount of catalyst remains in the obtained polycarbonate diol, the reaction may be inhibited or excessively promoted when producing a polyurethane using the polycarbonate diol. The type and amount of the catalyst, and the amount of catalyst remaining in the polycarbonate diol are not particularly limited. As the catalyst, for example, the conditions described in WO 2015 / 199070 can be appropriately optimized by a person skilled in the art according to known techniques and used.

[0110] (Catalyst deactivator) As mentioned above, when a catalyst is used in the polymerization reaction, the catalyst usually remains in the obtained polycarbonate diol, and the remaining catalyst may cause an increase in molecular weight or a change in composition when the polycarbonate diol is heated, or may make it impossible to control the polyurethane-forming reaction. In order to suppress the influence of this remaining catalyst, a catalyst deactivator such as a phosphorus-based compound can be added, if necessary, in an amount approximately equimolar to the transesterification catalyst used to inactivate the transesterification catalyst. Furthermore, after the addition, the transesterification catalyst can be efficiently inactivated by heat treatment or the like. The type and amount of the catalyst deactivator and the conditions for the heat treatment are not particularly limited. For example, the conditions described in WO 2015 / 199070 can be appropriately optimized by a person skilled in the art according to known techniques.

[0111] <Applications of Polycarbonate Diol> The polycarbonate diol of the present invention can be used as a raw material for thermoplastic elastomers such as polyurethane or polyester, and as a constituent material for paints or adhesives. In particular, when the polycarbonate diol of this embodiment is used as a raw material for polyurethane or thermoplastic elastomer, a polyurethane or thermoplastic elastomer having a smooth surface and a good balance of various mechanical properties, chemical resistance, and other performance characteristics can be obtained. Furthermore, when the polycarbonate diol of the present invention is used as a constituent material for paints or adhesives, a coating film having a smooth surface and a good balance of various mechanical properties, chemical resistance, and other performance characteristics can be obtained.

[0112] <Polyurethane> The polyurethane of the present invention is produced using the polycarbonate diol of the present invention and an isocyanate compound as raw materials. The method for producing the polyurethane of the present invention is not particularly limited, and those skilled in the art can use known polyurethane reaction conditions described in, for example, WO 2015 / 016261 and WO 2018 / 088575, by optimizing them as appropriate in accordance with known techniques.

[0113] For example, the polyurethane of the present invention can be produced by reacting the polycarbonate diol of the present invention with a polyol other than the polycarbonate diol of the present invention, which is used if necessary, an isocyanate compound described below, and a chain extender described below, which is also used if necessary, at a temperature ranging from room temperature to 200°C.

[0114] When a chain extender is used, the chain extender may be added from the beginning of the reaction or during the reaction. For example, the polyurethane of the present invention can be produced by first reacting the polycarbonate diol of the present invention with an excess amount of polyisocyanate to produce a prepolymer having an isocyanate group at its terminal, and then adding a chain extender to react with the prepolymer to increase the degree of polymerization of the polymer.

[0115] (Isocyanate compounds) As the isocyanate compound used in the production of the polyurethane of the present invention, known isocyanate compounds used in the production of polyurethanes can be used. The isocyanate compound is not particularly limited, and for example, the isocyanate compounds described in WO 2015 / 016261 and WO 2018 / 088575 can be used. Specific examples include known aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, and known alicyclic diisocyanates such as hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate. These may be used alone or in combination of two or more.

[0116] (Chain extender) As the chain extender used in the production of the polyurethane of the present invention, any known chain extender used in the production of polyurethanes can be used. The chain extender is not particularly limited, and examples thereof include diols, amines, water, and the like described in WO 2015 / 016261 and WO 2018 / 088575. Specific examples include linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol; branched diols such as 2,2-dimethyl-1,3-propanediol; diols having an ether group such as diethylene glycol and propylene glycol; diols having an alicyclic structure such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 1,4-dihydroxyethylcyclohexane; diols having an aromatic group such as xylylene glycol, 1,4-dihydroxyethylbenzene, and 4,4'-methylenebis(hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane, and pentaerythritol; hydroxyamines such as N-methylethanolamine and N-ethylethanolamine; polyamines such as ethylenediamine, hexamethylenediamine, isophoronediamine, xylylenediamine, diphenyldiamine, and diaminodiphenylmethane; and water. These chain extenders may be used alone or in combination of two or more.

[0117] (chain terminator) When producing the polyurethane of the present invention, a known chain terminator used in the production of polyurethanes can be used, if necessary, for the purpose of controlling the molecular weight of the polyurethane. The chain terminator is not particularly limited, and examples thereof include compounds having one active hydrogen group, such as monohydric alcohols and secondary amines, as described in WO 2015 / 016261 and WO 2018 / 088575. Specific examples include monohydric alcohols such as methanol, ethanol, propanol, butanol, and hexanol, and secondary amines such as diethylamine, dibutylamine, di-n-propylamine, n-butylamine, monoethanolamine, and diethanolamine. These may be used alone or in combination of two or more.

[0118] (catalyst) When producing the polyurethane of the present invention, any known catalyst used in the production of polyurethanes can be used. The catalyst is not particularly limited, and examples of the catalyst that can be used include known polymerization catalysts such as tertiary amines and organic metal salts of tin, titanium, and the like, as described in International Publication Nos. 2015 / 016261 and 2018 / 088575.

[0119] (solvent) When producing the polyurethane of the present invention, a solvent may be used, if necessary. The solvent is not particularly limited, and examples thereof include the solvents described in WO 2015 / 016261 and WO 2018 / 088575. Specific examples include dimethylformamide, diethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene, ethyl cellosolve, etc. These may be used alone or in combination of two or more.

[0120] (Amount / How to use) In the method for producing a polyurethane of the present invention, the amounts and methods of use of the polyisocyanate, chain extender, chain terminator, catalyst, and solvent are not particularly limited, and a person skilled in the art can use the conditions described in WO 2015 / 016261 and WO 2018 / 088575 by optimizing them as appropriate in accordance with known techniques.

[0121] (Polyurethane weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)) The weight average molecular weight (Mw) of the polyurethane of the present invention is not particularly limited, and from the viewpoint of achieving a good balance between the mechanical properties and chemical resistance of the resulting polyurethane, it is preferably from 50,000 to 500,000, more preferably from 100,000 to 300,000, and even more preferably from 150,000 to 200,000. The molecular weight distribution (Mw / Mn) of the polyurethane of the present invention is not particularly limited, and from the viewpoint of achieving a good balance between the mechanical properties and chemical resistance of the resulting polyurethane, it is preferably from 1.50 to 4.00, more preferably from 2.00 to 3.00, and even more preferably from 2.50 to 2.90. The Mw and Mw / Mn are measured by gel permeation chromatography (GPC measurement), and the measurement conditions are as described in the examples below.

[0122] <Polyurethane applications> The polyurethane of the present invention has suppressed variation in mechanical properties, is uniform in quality, and has good mechanical properties and chemical resistance, and therefore can be widely used in foams, elastomers, elastic fibers, paints such as water-based polyurethane paints, fibers, pressure-sensitive adhesives, adhesives, flooring materials, sealants, medical materials, artificial leather, synthetic leather, coating agents, active energy radiation-curable polymer compositions, and the like.

[0123] [Action and effect] Since the diol-containing composition of the present invention contains a primary amine or a secondary amine, the color tone of the obtained polycarbonate diol is well maintained, and the variation in mechanical properties of the obtained polyurethane is suppressed, the quality is uniform, and the mechanical properties and chemical resistance are good. Although the reason for this is not clear, it is presumed as follows. According to the investigations of the present inventors, the polycarbonate diol of the present invention, which is produced using a diol-containing composition containing a primary amine or a secondary amine as a raw material, and the polycarbonate diol contained in the polycarbonate diol composition of the present invention, contain the structural unit (2) derived from a primary amine or a secondary amine.

[0124] When polyurethane is produced using the polycarbonate diol of the present invention as a raw material, the structural unit (2) in the polycarbonate diol is considered to be incorporated into the polyurethane in the form of an amide bond. It is presumed that the improved interaction between polyurethane molecules due to hydrogen bonds via the amide bonds causes the amide bond moieties to act as crosslinking points or crystalline hard segment structures, thereby improving the mechanical properties and chemical resistance of the polyurethane.

[0125] Furthermore, in the resulting polyurethane, the interaction between polyurethane molecules due to hydrogen bonding via the amide bond is improved, thereby improving the viscosity of the polyurethane or polyurethane-containing composition. As a result, it becomes possible to efficiently improve the uniformity of the polyurethane composition by stirring. Furthermore, a moderate improvement in the viscosity improves the coating stability and molding stability of the polyurethane or polyurethane-containing composition. As a result, the dimensional stability of the resulting film-like material, fiber-like material, and other molded articles is improved, which is presumably suppressing variation in the mechanical properties of the resulting polyurethane products and resulting in uniform quality. [Example]

[0126] The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to these examples as long as the gist of the invention is not exceeded.

[0127] [Raw materials used] The abbreviations for the raw materials used in the examples and comparative examples are as follows: 16HD: 1,6-Hexanediol (BASF Japan Ltd.) 14BG: 1,4-butanediol (Mitsubishi Chemical Corporation) ISB: Isosorbide (manufactured by Rocket Co., Ltd.) 6-Amino-1-hexanol (Tokyo Chemical Industry Co., Ltd.) DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation) Mg catalyst: Magnesium acetate tetrahydrate (Fujifilm Wako Pure Chemical Industries, Ltd.) MDI: Diphenylmethane diisocyanate (Tokyo Chemical Industry Co., Ltd.) U-830: Dioctyltin monodecanoate (product name: Neostan U-830, manufactured by Nitto Kasei Co., Ltd.) DMF: Dehydrated N,N-dimethylformamide (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0128] [Evaluation method] In the following, the evaluation methods for each physical property value are as follows.

[0129] [Evaluation method: Diol-containing composition] <Amine content> The content of primary or secondary amine in 1,6-hexanediol used as the diol-containing composition in the examples and comparative examples was measured according to the following procedure. In this evaluation, the definition of "amine content" is as described above.

[0130] 1,6-Hexanediol was dissolved in CDCl3, and 1H-NMR measurement was carried out using a nuclear magnetic resonance spectrometer (400 MHz, manufactured by JEOL Ltd., model name: ECZ400S) at a measurement temperature of 30°C and an accumulation number of 32.

[0131] From the obtained 1H-NMR measurement results, the amine content (unit: mass%) in the diol-containing composition relative to 100% of the total mass of the diol-containing composition was calculated using the integral value a of the peak of the 2H proton of the α-methylene group at the amine terminal present at δ 3.15 to 3.05 ppm, the integral value b of the peak of the 2H proton of the α-methylene group at the hydroxyl group terminal present at δ 3.69 to 3.50 ppm, and the following formula:

[0132]

number

[0133] In the above formula, "M(amine)" represents the molecular weight of the primary amine 6-amino-1-hexanol (=117), and "M(16HD)" represents the molecular weight of 1,6-hexanediol (=118).

[0134] The calculated amine content (unit: mass %) and the following formula were used to calculate the amine content (unit: mass ppm) converted to nitrogen atoms.

[0135]

number

[0136] Similarly, the content ratio of amine in the diol-containing composition used in the examples, which contains 1,6-hexanediol, 1,4-butanediol, and isosorbide as diols, is as follows: 1 From the H-NMR measurement results, the nitrogen atom-equivalent content (unit: ppm by mass) of the amine in the diol-containing composition was calculated relative to 100% by total mass of the diol-containing composition using the integral value of the α-methylene group proton peak in the amine (6-amino-1-hexanol), the integral value of the α-methylene group proton peak in each diol, the molecular weight of each diol, and a formula similar to the above formula. In this calculation, "M(14BG)" was used as the molecular weight of 1,4-butanediol (= 90), and "M(ISB)" was used as the molecular weight of isosorbide (= 146).

[0137] [Evaluation method: Polycarbonate diol] <Content of structural units derived from amines> The content of structural units derived from primary or secondary amines (hereinafter referred to as "amine-derived structural units") contained in the structure of the polycarbonate diols (hereinafter sometimes abbreviated as "PCD") obtained in the Examples and Comparative Examples was measured according to the following procedure.

[0138] Polycarbonate diol was dissolved in CDCl3, and a nuclear magnetic resonance spectrometer (400 MHz, manufactured by JEOL Ltd., model name: ECZ400S) was used to measure the polycarbonate diol at a measurement temperature of 30°C and an accumulation number of 64. 1 H-NMR measurements were carried out. obtained 1 From the H-NMR measurement results, three peaks observed at the following signal positions were identified, and integral values ​​A to C of each peak were obtained. Integral value of 2H proton of α-methylene group of amine-derived structural unit present at δ 3.15-3.05 ppm = A The integral value of the 2H proton peak of the methylene group next to the hydroxyl group terminal in the polycarbonate diol present at δ 3.69-3.50 ppm = B The integral value of the 4H proton peak of the γ methylene group of the structure derived from 1,6-hexanediol in polycarbonate diol present at δ 1.49-1.30 ppm = C

[0139] The integral value of the peak derived from the amine-derived structural unit was designated as "AM." Similarly, the integral value of the peak of the structural unit of the polycarbonate diol terminal derived from 1,6-hexanediol (hereinafter abbreviated as "16HD") is referred to as "16HD". m The integral value of the peak of the structural unit derived from 16HD in the polycarbonate diol other than the polycarbonate diol terminal was defined as "16HD o " Taking into account the number of protons in each region, the integral per proton was calculated using the following formula: AM=A÷2 16HD m =B÷2 16HD o =(C-16HD m ×4)÷4

[0140] Next, the number average molecular weight M(PCD) of the polycarbonate diol was calculated using the following formula from the ratio (number of diol units) of the total amount of structural units derived from 16HD to the total amount of structural units at the terminals of the polycarbonate diol derived from 16HD and the molecular weight of each structural unit of the polycarbonate diol.

[0141]

number

[0142] In the above formula, M(16HD o ) refers to the molecular weight of the structural unit derived from 16HD in the polycarbonate diol other than the polycarbonate diol terminal (=116), and M (carbonyl group) refers to the molecular weight of the carbonyl group (=28).

[0143] Using the above value and the following formula, the content ratio (unit: mass %) of the amine-derived structural unit contained in the structure of the polycarbonate diol relative to 100% of the total mass of the polycarbonate diol was calculated.

[0144]

number

[0145] In the above formula, "M (amine)" represents the molecular weight (=117) of 6-amino-1-hexanol, which is a primary amine.

[0146] Next, using the above value and the following formula, the content ratio (unit: mass ppm) of the amine-derived structural unit contained in the structure of the polycarbonate diol was calculated in terms of nitrogen atoms.

[0147]

number

[0148] Similarly, the content ratio of amine-derived structural units in polycarbonate diols containing 1,6-hexanediol, 1,4-butanediol (hereinafter abbreviated as "14BG"), and isosorbide (hereinafter abbreviated as "ISB") as dihydroxy compounds used in the examples was 1 From the H-NMR measurement results, the content ratio (unit: mass ppm) of the amine-derived structural unit in the polycarbonate diol in terms of nitrogen atoms relative to 100% of the total mass of the polycarbonate diol was calculated using the integrated value of the peak derived from the structural unit at the polycarbonate diol terminal, the integrated value of the peak derived from the structural unit in the polycarbonate diol other than the polycarbonate diol terminal, the number average molecular weight M(PCD) of the polycarbonate diol, and an equation similar to the above equation.

[0149] At that time, M(14BG o ) is the molecular weight (=88) of the structural unit derived from 14BG in the polycarbonate diol other than the polycarbonate diol terminal, and similarly, M(ISB o ) was used as the molecular weight of the structural unit derived from ISB (=144).

[0150] <color tone> As an index of coloration suppression, i.e., color tone, of the polycarbonate diol obtained in Examples and Comparative Examples, the APHA value of the polycarbonate diol sample was measured by comparing it with a standard solution placed in a colorimetric tube in accordance with JIS K0071-1 (1998). The reagent used was a chromaticity standard solution 1000 degrees (1 mg Pt / mL) (manufactured by Kishida Chemical Co., Ltd.).

[0151] <Number average molecular weight of polycarbonate diol (M(PCD))> The polycarbonate diols obtained in the examples and comparative examples were dissolved in CDCl3 and analyzed using a nuclear magnetic resonance spectrometer (400 MHz, manufactured by JEOL Ltd., model name: ECZ400S). 1 H-NMR was measured, and the number average molecular weight (M(PCD)) was calculated from the signal positions of each component using the above calculation method.

[0152] <Number average molecular weight (Mn) calculated from the hydroxyl value of the polycarbonate diol after distillation> The hydroxyl value (unit: mgKOH / g) of the polycarbonate diols obtained in the examples and comparative examples was measured by a method using an acetylation reagent in accordance with JIS K1557-1. Then, the number average molecular weight (Mn) of the polycarbonate polyol was calculated from the obtained hydroxyl value using the following formula. Number average molecular weight (Mn) = (molecular weight of KOH) x 2000 / hydroxyl value

[0153] [Evaluation method: Polyurethane] <Weight average molecular weight (Mw) and number average molecular weight (Mn)> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyurethanes obtained in the examples and comparative examples were determined by gel permeation chromatography (GPC measurement) according to the following procedure. The polyurethane sample was dissolved in dimethylacetamide (containing 0.3% by mass of anhydrous lithium bromide) to a polyurethane concentration of 0.07% by mass, and this was used as the sample for GPC measurement. GPC measurement was performed using a GPC system (Tosoh Corporation, model name: HLC-8420, column: Tosoh Corporation TSKgel SuperAWM-H x 2) with a sample injection volume of approximately 40 μL, a column temperature of 40°C, a measurement solvent (mobile phase) of dimethylacetamide (containing 0.3% by mass of anhydrous lithium bromide), and a flow rate of 0.6 mL / min. The molecular weight of the polyurethane was measured as the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) in terms of standard polystyrene using a commercially available monodisperse polystyrene solution as a standard sample.

[0154] <Solution viscosity> The viscosity of the polyurethane solutions obtained in the examples and comparative examples was measured at 40°C using an E-type viscometer (device name: TV-100EH, cone: 3°×R 1 4, manufactured by Toki Sangyo Co., Ltd.) was used for the measurement.

[0155] <Mechanical properties> As an index of the mechanical properties of polyurethane, tensile tests were carried out on polyurethane using the following methods to evaluate various mechanical properties. The polyurethane solutions obtained in the examples and comparative examples were applied to a 0.1 mm thick fluororesin sheet (product name: Fluorine Tape "Nitoflon 900", manufactured by Nitto Denko Corporation) using an applicator with a clearance of 500 μm. The sheet was dried at 80°C for 1 hour, then at 100°C for 0.5 hours, and then at 100°C under vacuum for 1.0 hour to dry off the solvent (DMF). The sheet was then left to stand at a constant temperature and humidity of 23°C and 55% RH for at least 12 hours to obtain a laminated film with a polyurethane layer formed on the surface of the fluororesin sheet. The thickness of the polyurethane layer after drying was 100 μm. After peeling the polyurethane layer from the resulting laminated film, a rectangular polyurethane film (length 150 mm, width 10 mm, thickness 100 μm) was cut out and used as a sample piece for a tensile test.

[0156] (Tensile test) Tensile tests were carried out on the above tensile test specimens in accordance with JIS K6301 (2010) using a bench-top precision universal testing machine (Shimadzu Corporation, product name: Autograph AGS-X) with a chuck distance of 50 mm, a tensile speed of 500 mm / min, and a temperature of 23°C (relative humidity of 60%). Measurements were carried out using four tensile test specimens, and the 300% modulus, as well as the average value and standard deviation of the stress (breaking strength) and elongation (breaking elongation) at the time the specimens broke, were measured. The coefficients of variation of breaking strength and breaking elongation were calculated using the following formulas. Coefficient of variation (%) = (standard deviation / average value) x 100

[0157] <Chemical resistance of polyurethane> As an index of the chemical resistance of polyurethane, the mass change rate when the polyurethane was immersed in a test solution was measured using the following method. The polyurethane solutions obtained in the examples and comparative examples were applied to a 0.1 mm thick fluororesin sheet (product name: Fluorine Tape "Nitoflon 900", manufactured by Nitto Denko Corporation) using an applicator with a clearance of 500 μm, and the solvent (DMF) was removed by drying at 80°C for 1 hour, then at 100°C for 0.5 hours, and then at 100°C in a vacuum for 1.0 hour, to obtain a laminated film in which a polyurethane layer was formed on the surface of the fluororesin sheet. The thickness of the polyurethane layer after drying was 100 μm. After peeling the polyurethane layer from the resulting laminated film, a square polyurethane film (3 cm long, 3 cm wide, 100 μm thick) was cut out and used as a sample piece for chemical resistance testing.

[0158] (Ethanol resistance test) The weight of the above chemical resistance test specimen was measured using a precision balance, and then it was placed in a glass Petri dish with an inner diameter of 10 cm containing 50 mL of ethanol as the test solvent and immersed for 1 hour at room temperature of approximately 23°C. After the test, the specimen was removed and lightly wiped on both sides with a paper wiper, and then the mass was measured using a precision balance. The mass change rate (rate of increase) was calculated from the change in mass of the specimen before and after the test. A mass change rate closer to 0% indicates better ethanol resistance.

[0159] (Ethyl acetate resistance test) The weight of the above chemical resistance test specimen was measured using a precision balance, and then it was placed in a glass Petri dish with an inner diameter of 10 cm containing 50 mL of ethyl acetate as the test solvent and immersed for 20 minutes at room temperature of approximately 23°C. After the test, the specimen was removed and lightly wiped on both sides with a paper wiper. The mass was then measured using a precision balance, and the mass change rate (rate of increase) was calculated from the change in mass of the specimen before and after the test. A mass change rate closer to 0% indicates better ethyl acetate resistance.

[0160] [Production and Evaluation of Polycarbonate Diol] Example 1 A 1L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator was charged with 323 g of 16HD containing 0.6 g of 6-amino-1-hexanol as the raw material diol-containing composition, 527 g of DPC as the carbonate compound, and 1.4 mL of an aqueous Mg catalyst solution (concentration: 8.4 g / L magnesium acetate tetrahydrate) as the transesterification catalyst. After replacing the atmosphere in the flask with nitrogen, the contents in the flask were heated to 160 °C while stirring, and the contents were dissolved. The pressure in the flask at this time was 101 kPa. The pressure in the flask was then gradually reduced from 101 kPa to 24 kPa over 2 minutes, and the reaction was carried out for 90 minutes while the produced phenol was removed from the reaction system. Next, the pressure in the flask was gradually reduced to 9.3 kPa over 90 minutes, and then further reduced to 0.7 kPa over 30 minutes to continue the reaction, and then the temperature of the content was raised to 170°C, and the reaction was continued for another 120 minutes while removing phenol and unreacted dihydroxy compound from the reaction system. Thereafter, the temperature of the content was allowed to cool to room temperature to obtain 368 g of a polycarbonate diol-containing composition. The obtained polycarbonate diol was named "PCD2." The evaluation results of this PCD2 are shown in Table 1.

[0161] <Comparative Example 1> The reaction was carried out under the same conditions as in Example 1, except that 323 g of 16HD containing no 6-amino-1-hexanol was used as the diol-containing raw material composition. The obtained polycarbonate diol was designated "PCD1." The evaluation results of this PCD1 are shown in Table 1.

[0162] <Example 2> The reaction was carried out under the same conditions as in Example 1, except that 16HD containing 6-amino-1-hexanol in the amount shown in Table 1 was used as the diol-containing raw material composition. The obtained polycarbonate diol was named "PCD3." The evaluation results of this PCD3 are shown in Table 1.

[0163] Example 3 The reaction was carried out under the same conditions as in Example 1, except that 16HD containing 6-amino-1-hexanol in the amount shown in Table 1 was used as the diol-containing raw material composition. The obtained polycarbonate diol was named "PCD4." The evaluation results of this PCD4 are shown in Table 1.

[0164] Example 4 In Example 1, 16HD and 14BG containing 6-amino-1-hexanol in the amounts shown in Table 1 were used as the diol-containing raw material compositions, and the reaction was carried out under the same conditions as in Example 1, except that the 16HD, 14BG, DPC, and aqueous Mg catalyst solution were added in the amounts shown in Table 1. The obtained copolymeric polycarbonate diol was designated "PCD5." The evaluation results of this PCD5 are shown in Table 1.

[0165] <Example 5> In Example 1, 16HD and ISB containing 6-amino-1-hexanol in the amounts shown in Table 1 were used as the diol-containing raw material composition, and the reaction was carried out under the same conditions as in Example 1, except that the 16HD, ISB, DPC, and aqueous Mg catalyst solution were added in the amounts shown in Table 1. The obtained copolymeric polycarbonate diol was named "PCD6." The evaluation results of this PCD6 are shown in Table 1.

[0166] Example 6 In Example 1, 16HD and ISB containing 6-amino-1-hexanol in the amounts shown in Table 1 were used as the diol-containing raw material composition, and the reaction was carried out under the same conditions as in Example 1, except that the 16HD, ISB, DPC, and aqueous Mg catalyst solution were added in the amounts shown in Table 1. The obtained copolymeric polycarbonate diol was named "PCD7." The evaluation results of this PCD7 are shown in Table 1.

[0167] [Table 1]

[0168] The polycarbonate diols obtained in Examples 1 to 6 using the diol-containing compositions of the present invention as raw materials all had a color tone (APHA) of 70 or less, which was at an industrially acceptable level.

[0169] [Production and evaluation of polyurethane] <Purification of Polycarbonate Diol> To remove phenol contained in the polycarbonate diols (PCD1-4) obtained in Comparative Example 1 and Examples 1-3, 0.3 g of a 0.85 mass % aqueous solution of phosphoric acid was first added to 220 g of polycarbonate diol to deactivate magnesium acetate. Then, the solution was sent to a thin-film distillation apparatus at a flow rate of 20 g / min, and thin-film distillation (temperature: 180-190°C, pressure: 40-67 Pa) was carried out. The thin-film distillation apparatus had a diameter of 50 mm, a height of 200 mm, and an area of ​​0.0314 m. 2 The molecular distillation apparatus used was a special model MS-300 manufactured by Shibata Scientific Co., Ltd., equipped with an internal condenser and a jacket. Hereinafter, PCD1 to 4 after thin-film distillation will be referred to as PCD1A to 4A, respectively. Table 2 shows the content ratios of amine-derived structural units in PCD1A to 4A obtained by thin-film distillation.

[0170] <Comparative Example 1-2> A separable flask equipped with a thermocouple and a condenser was charged with 69.8 g of PCD1A preheated to 80°C, 6.30 g of 14BG as a chain extender, 0.02 g of U-830 as a catalyst, and 239 g of DMF as a reaction solvent, and the flask was immersed in an oil bath set to 55°C. The flask was stirred at a stirring speed of 60 rpm until the mixture was homogenous. The amount of water in the reaction solution in the flask was measured, and the amount of MDI consumed by the water was calculated. The amount of sampled and extracted was also recorded, and the amount of each raw material charged was corrected. To the reaction solution, MDI equivalent to an NCO / OH molar ratio of 0.900 (including water content correction) was added in a solid state using a funnel, as an isocyanate compound, and the mixture was stirred at a stirring speed of 60 rpm until homogenous. In this specification, the "NCO / OH molar ratio" refers to the ratio (molar ratio) of the total amount of substance (number of moles) of MDI to the value obtained by subtracting the total amount of substance (number of moles) of water contained from the total amount of substance (number of moles) of polycarbonate diol and 14BG when MDI is added. Immediately after the addition of MDI, an exothermic peak accompanied by a rise in the temperature of the reaction solution of +10 to +15°C was observed, and 5 minutes after the exothermic peak subsided, the temperature of the oil bath was set to 70°C and the temperature was increased. One hour after adding the MDI, the molecular weight of the polyurethane in the reaction solution was measured to confirm whether the target molecular weight (MW = 170,000-180,000) had been reached. If the target molecular weight had not been reached, additional MDI equivalent to an NCO / OH ratio of 0.005-0.015 was added, and the reaction was continued for another 30 minutes or more, after which the molecular weight of the polyurethane in the reaction solution was measured. The addition of MDI and molecular weight measurement were repeated until the target Mw was reached. Finally, a polyurethane solution containing polyurethane with a total NCO / OH ratio of 0.990 and an Mw of 170,032 was obtained. The evaluation results of the resulting polyurethane solution are shown in Table 2.

[0171] <Example 1-2> In Comparative Example 1-2, PCD2A was used instead of PCD1A, and the amounts of each raw material were changed to the amounts listed in Table 2. Except for this, polyurethane polymerization was carried out under the same conditions and in the same manner as in Comparative Example 1-2, and a polyurethane solution was obtained. The evaluation results of the resulting polyurethane solution are shown in Table 2.

[0172] <Example 2-2> In Comparative Example 1-2, PCD3A was used instead of PCD1A, and the amounts of each raw material were changed to the amounts listed in Table 2. Except for this, polyurethane polymerization was carried out under the same conditions and in the same manner as in Comparative Example 1-2, and a polyurethane solution was obtained. The evaluation results of the resulting polyurethane solution are shown in Table 2.

[0173] <Example 3-2> In Comparative Example 1-2, PCD4A was used instead of PCD1A, and the amounts of each raw material were changed to the amounts listed in Table 2. Except for this, polyurethane polymerization was carried out under the same conditions and in the same manner as in Comparative Example 1-2, and a polyurethane solution was obtained. The evaluation results of the resulting polyurethane solution are shown in Table 2.

[0174] [Table 2]

[0175] Table 2 reveals the following: The polyurethanes obtained in Examples 1-2 to 3-2 had less variation in mechanical properties, were of uniform quality, and had good mechanical properties and chemical resistance compared to the polyurethane obtained in Comparative Example 1-2. On the other hand, the polyurethane obtained in Comparative Example 1-2 had a lower breaking strength than those of Examples 1-2 to 3-2, and the variation (coefficient of variation) of the mechanical properties was large, because the polycarbonate diol used as a raw material did not contain an amine-derived structural unit. From the above, it is clear that by using the diol-containing composition of the present invention for producing a polycarbonate diol, it is possible to produce polyurethane with reduced variation in mechanical properties, uniform quality, and good maintenance of mechanical properties and chemical resistance, using the obtained polycarbonate diol.

Claims

1. A diol-containing composition used in a process for producing a polycarbonate diol, A diol-containing composition comprising at least one of a primary amine and a secondary amine and a diol (1) represented by the following general formula (I): 【Chemical 1】 (In the above general formula (I), R represents a hydrocarbon group having 2 to 20 carbon atoms, which may have a substituent or a heteroatom.)

2. The diol-containing composition according to claim 1, wherein the diol (1) comprises a diol (1a) represented by the following general formula (Ia): 【Chemistry 2】 (In the above general formula (1), n ​​is an integer of 2 to 20.)

3. The diol-containing composition according to claim 2, wherein the diol (1) comprises at least one selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

4. 2. The diol-containing composition according to claim 1, wherein the primary amine and the secondary amine contain one or more amino groups and one or more functional groups, and the functional groups include at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a formyl group, and an amino group.

5. The diol-containing composition according to claim 1 , wherein the primary amine and the secondary amine include an amine represented by the following general formula (II): 【Chemistry 3】 (In the above general formula (II), R １ represents an alkyl group having 2 to 20 carbon atoms and r substituents X, which may have substituents other than X. X represents a hydroxyl group, a carboxyl group, a formyl group, or an amino group. r is an integer of 1 to 6. R ２ represents an alkyl group having 1 to 20 carbon atoms, which may have a substituent, or a hydrogen atom.

6. The diol-containing composition according to claim 5, wherein the primary amine or secondary amine comprises at least one selected from 6-amino-1-hexanol, 6-methylamino-1-hexanol, and 6-ethylamino-1-hexanol.

7. The diol-containing composition according to claim 1, wherein the total content of the primary amine and the secondary amine contained in the diol-containing composition is 1 mass ppm or more in terms of nitrogen atoms, relative to the total mass of the diol-containing composition.

8. 2. The diol-containing composition according to claim 1, wherein the total content of the primary amine and the secondary amine contained in the diol-containing composition is 1,500 ppm by mass or less in terms of nitrogen atoms, relative to the total mass of the diol-containing composition.

9. The diol-containing composition according to claim 1 , wherein the diol (1) comprises a biomass-derived diol.

10. A polycarbonate diol obtained from the diol-containing composition according to any one of claims 1 to 9 and a carbonate compound.

11. A polyurethane made from the polycarbonate diol according to claim 10 and an isocyanate compound.

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