Tricyclodecanedimethanol composition, uv-curable composition, polymer composition, and tricyclodecanedimethanol composition production method

Abstract

A tricyclodecanedimethanol composition containing a chiral compound A of which one enantiomer is represented by formula (I), a chiral compound B of which one enantiomer is represented by formula (II), a chiral compound C of which one enantiomer is represented by formula (III), and a chiral compound D of which one enantiomer is represented by formula (IV), wherein the number of moles Xa of the chiral compound A, the number of moles Xb of the chiral compound B, and the total number of moles Xt of the number of moles of the chiral compound A, the chiral compound B, the chiral compound C, and the chiral compound D, as measured using nuclear magnetic resonance spectrometry, satisfy Xa / Xt≤0.430 and Xb / Xt≥0.016.

Description

Tricyclodecane dimethanol composition, ultraviolet curable composition, polymer composition, and method for producing tricyclodecane dimethanol composition

[0001] The present invention relates to a tricyclodecane dimethanol composition, an ultraviolet-curable composition, a polymer composition, and a method for producing the tricyclodecane dimethanol composition.

[0002] Tricyclodecane dimethanol (hereinafter abbreviated as "TCDDM") is a dihydric alcohol having an alicyclic structure. TCDDM is produced by hydroformylating dicyclopentadiene with carbon monoxide and hydrogen in the presence of a catalyst to produce an aldehyde, which is then reduced with hydrogen (Patent Documents 1, 2, and 3).

[0003] In the fields of molding materials, electronic materials, and display device components, materials having an alicyclic molecular structure are used from the viewpoints of transparency, heat resistance, and low water absorption. In recent years, polymers containing the aforementioned TCDDM as a constituent component of a material having an alicyclic molecular structure have been known to exhibit excellent performance in terms of hardness, transparency, heat resistance, and low water absorption due to the alicyclic structure of TCDDM, and TCDDM has attracted attention as a synthetic raw material for molding materials such as polyesters and polycarbonates. Derivatives of TCDDM synthesized using TCDDM as a raw material, such as diacrylate derivatives, dimethacrylate derivatives, and urethane acrylates, are used as ultraviolet-curable compositions. Cured products using such ultraviolet-curable compositions exhibit excellent performance in surface hardness, heat resistance (glass transition temperature), thermal decomposition resistance, and development resistance due to the alicyclic structure of TCDDM, and therefore have attracted attention as electronic materials and display device components, such as hard coats, antifouling coats, and resists.

[0004] One method for industrially producing TCDDM is to subject dicyclopentadiene to hydroformylation, followed by hydrogen reduction, followed by distillation and purification to obtain TCDDM. In the hydroformylation reaction, the double bond of the norbornane ring of dicyclopentadiene is more reactive than the double bond of the five-membered ring. Therefore, after the first formyl group is added to the norbornane ring, the second formyl group is added to the double bond of the five-membered ring (Non-Patent Document 1). As a result, it is known that the TCDDM obtained after the hydrogen reduction reaction is a mixture of TCDDM (hereinafter referred to as "TCDDM composition") primarily composed of multiple isomers with different hydroxymethyl group bonding positions on the five-membered ring (Non-Patent Document 2).

[0005] JP 2020-132624 A JP 2021-520401 A International Publication No. 2023 / 277347

[0006] Hitachi Chemical Technical Report, No. 51 (2008-7), pp. 7-12; Applied Catalyst, Vol. 19, pp. 259-273 (1985)

[0007] The present inventors have newly discovered that a TCDDM composition obtained by distillation purification after a hydrogen reduction reaction may have fluidity immediately after distillation, but may lose fluidity during storage, making it difficult to handle, depending on the composition of the TCDDM composition; in other words, the TCDDM composition may have poor storage stability.

[0008] If the fluidity of the TCDDM composition decreases, it becomes difficult to pump this TCDDM composition or a raw material mixture containing the TCDDM composition (hereinafter referred to as "TCDDM composition, etc.") using a gear pump or the like, or heating the TCDDM composition, etc. to improve the fluidity of the TCDDM composition, etc. may result in deterioration of the TCDDM composition, etc., or other problems.

[0009] However, Patent Documents 1 to 3 make no mention of the poor storage stability of TCDDM compositions depending on the composition of the TCDDM composition, nor of a method for improving the storage stability of TCDDM compositions.

[0010] An object of the present invention is to provide a TCDDM composition having excellent storage stability.

[0011] The present inventors have found that in a TCDDM mixture containing four isomers, each of which has a different hydroxymethyl group bonding position, it is effective to appropriately control the isomer ratio. More specifically, the inventors have found that a TCDDM composition having excellent storage stability can be obtained by controlling the ratio of one of the four isomers, which has the effect of improving the flowability of the TCDDM composition, to a predetermined value or more, and by controlling the ratio of another component, which has the effect of reducing the flowability of the TCDDM composition, to a predetermined value or less.

[0012] The present invention provides the following.

[0013] [1] A tricyclodecane dimethanol composition comprising: a chiral compound A, one enantiomer of which is represented by the following formula (I); a chiral compound B, one enantiomer of which is represented by the following formula (II); a chiral compound C, one enantiomer of which is represented by the following formula (III); and a chiral compound D, one enantiomer of which is represented by the following formula (IV), wherein the number of moles Xa of the chiral compound A, the number of moles Xb of the chiral compound B, and the total number of moles Xt of the chiral compounds A, B, C, and D, as measured by nuclear magnetic resonance spectroscopy, satisfy Xa / Xt≦0.430 and Xb / Xt≧0.016.

[0014]

[0015] [2] The tricyclodecane dimethanol composition according to [1], wherein Xb and Xt satisfy Xb / Xt≧0.020. [3] The tricyclodecane dimethanol composition according to [1] or [2], wherein Xa and Xt satisfy Xa / Xt≦0.400. [4] The tricyclodecane dimethanol composition according to any one of [1] to [3], wherein Xb and Xt satisfy Xb / Xt≧0.027. [5] The tricyclodecane dimethanol composition according to any one of [1] to [4], wherein Xa and Xt satisfy Xa / Xt<0.350. [6] The tricyclodecane dimethanol composition according to any one of [1] to [5], wherein the number of moles Xc of the chiral compound C and Xt, as detected by an NMR method, satisfy Xc / Xt≧0.300. [7] The tricyclodecane dimethanol composition according to any one of [1] to [6], wherein the number of moles Xd of the chiral compound D and the number of moles Xt measured by NMR satisfy Xd / Xt≧0.240. [8] The tricyclodecane dimethanol composition according to any one of [1] to [7], wherein the number of moles Xc of the chiral compound C and the number of moles Xd of the chiral compound D measured by nuclear magnetic resonance spectroscopy satisfy Xb / (Xa+Xc+Xd)≧0.010. [9] The tricyclodecane dimethanol composition according to any one of [1] to [8], wherein the chiral compound B is detected within a retention time range of 13.65 to 13.85 minutes when the composition is measured by gas chromatography (GC) under the following measurement conditions:(Measurement conditions) Column: capillary column (length 30 m × inner diameter 0.25 mm × film thickness 1 μm) Liquid phase: 100% dimethylpolysiloxane Carrier gas: helium Carrier gas column flow rate: 1 mL / min Split ratio: 1 / 30 Injection amount: 0.3 μL Oven temperature: 160° C. (no retention time) → heating at 5° C. / min → 300° C. (retention time 2 min) Injection port temperature: 200° C. Detector: flame ionization detector (temperature 300° C.)

[10] The tricyclodecane dimethanol composition according to [9], wherein the chiral compound A is detected within a retention time range of 13.85 to 14.05 minutes when the composition is measured using gas chromatography (GC) under the measurement conditions.

[0016]

[11] An ultraviolet-curable composition derived from the tricyclodecane dimethanol composition according to any one of [1] to

[10] .

[0017]

[12] The ultraviolet-curable composition according to

[11] , which is used for any one of a hard coat material, an antifouling coat material, a resist material, an inkjet ink, and a material for a 3D printer.

[0018]

[13] A polymer composition derived from the tricyclodecane dimethanol composition according to any one of [1] to

[10] , or the ultraviolet-curable composition according to

[11] or

[12] .

[14] The polymer composition according to

[13] , wherein the polymer in the polymer composition is at least one selected from the group consisting of polyester-based resins, epoxy-based resins, acrylate-based resins, polycarbonate-based resins, and polyurethane-based resins.

[0019]

[15] A method for producing a tricyclodecane dimethanol composition, comprising the steps of hydroformylating dicyclopentadiene to obtain tricyclodecane dicarbaldehyde, reducing the tricyclodecane dicarbaldehyde to obtain a crude reaction solution containing tricyclodecane dimethanol, and purifying the crude reaction solution by distillation to obtain the tricyclodecane dimethanol composition according to any one of [1] to

[10] .

[16] A method for producing the tricyclodecane dimethanol composition according to

[15] , wherein the reaction pressure for the hydroformylation is 0.5 MPaG or more and 4.5 MPaG or less, the temperature for the reduction reaction is 125°C or more and 350°C or less, and the distillation conditions for the distillation purification satisfy the following formula (1): (Ya-Za) x T / S x 100≦1.65 (1) (In formula (1), Ya: mass proportion of chiral compound A in the crude reaction solution supplied to the distillation purification step (unit: dimensionless number); S: total weight (unit: g) of chiral compound A, chiral compound B, chiral compound C, and chiral compound D in the crude reaction solution supplied to the distillation purification step; Za: mass proportion (unit: dimensionless number) of chiral compound A in the distillate distilled out of the purification system from the distillation column in the distillation purification step (unit: g); and T: total weight (unit: g) of chiral compound A, chiral compound B, chiral compound C, and chiral compound D in the distillate distilled out of the purification system from the distillation column in the distillation purification step.)

[0020] According to the present invention, a TCDDM composition having excellent storage stability can be provided. More specifically, according to the present invention, by appropriately selecting a specific isomer ratio, a TCDDM composition having excellent storage stability and not exhibiting a decrease in fluidity even after long-term storage can be provided.

[0021] Figure 1 is a gas chromatogram of the TCDDM composition obtained in Example 2. Figure 2(a) is a gas chromatogram of the TCDDM composition obtained in Example 2. １３ 2(b) shows the C-NMR spectrum of the TCDDM composition obtained in Comparative Example 1. １３2(a) and 2(b), the subscripts "A," "B," "C," and "D" attached to the NMR peaks indicate that the peaks correspond to "chiral compound A," "chiral compound B," "chiral compound C," and "chiral compound D," respectively.

[0022] 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.

[0023] 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. "A to B" means A or more and B or less.

[0024] In this specification, unless otherwise specified, "including A or B" means "including A," "including B," or "including A and B."

[0025] In this specification, "mass %" indicates the content ratio of a specified component contained in a total amount of 100 mass %. "Massive %" and "weight %" have the same meaning. In this specification, "any" or "optionally" means that the situation described subsequently may or may not occur. Therefore, the description includes both cases where the situation occurs and cases where the situation does not occur.

[0026] As used herein, the term "about" means that the range can include 20% above and below the stated value. For example, a temperature of about 75° C. relative to 0° C. encompasses a range of 60° C. to 90° C. All steps described herein can be performed in any suitable order unless otherwise specified herein or clearly contradicted by context.

[0027] The following describes in detail the embodiments of the present invention. The following description of the components is an example of the embodiment of the present invention, and the present invention is not limited to these.

[0028] <Tricyclodecane Dimethanol Composition> The tricyclodecane dimethanol composition (hereinafter also referred to as "TCDDM composition") of the present invention is a composition containing tricyclodecane dimethanol (hereinafter also referred to as "TCDDM"). The TCDDM composition is a mixture containing chiral compound A, one enantiomer of which is represented by formula (I) below, chiral compound B, one enantiomer of which is represented by formula (II) below, chiral compound C, one enantiomer of which is represented by formula (III) below, and chiral compound D, one enantiomer of which is represented by formula (IV) below:

[0029] The chiral compounds A, B, C, and D each have one hydroxymethyl group (CH ２ OH group) and one other hydroxymethyl group in the five-membered ring.

[0030]

[0031] As described above, the chiral compound A, chiral compound B, chiral compound C, and chiral compound D in the present invention exist as R- and S-enantiomers (also referred to as optical isomers), but the difference between them is not particularly important and both are included.

[0032] Chiral Compound A, Chiral Compound B, Chiral Compound C, and Chiral Compound D of the present invention exist as stereoisomers depending on whether the two hydroxymethyl groups are bonded to the same side of the bridgehead position of the norbornane ring or to opposite sides. Chiral Compound A, Chiral Compound B, Chiral Compound C, and Chiral Compound D of the present invention are compounds in which the hydroxymethyl groups are bonded to the same side of the bridgehead position of the norbornane ring, as shown in Formulas (I) to (IV), respectively. Furthermore, although the tricyclodecane skeleton exists in both endo and exo isomers, Chiral Compound A, Chiral Compound B, Chiral Compound C, and Chiral Compound D of the present invention are only endo isomers. Hereinafter, "Chiral Compound A," "Chiral Compound B," "Chiral Compound C," and "Chiral Compound D" may be simply referred to as "Compound A," "Compound B," "Compound C," and "Compound D," respectively.

[0033] In the present invention, nuclear magnetic resonance spectroscopy ( １３ The number of moles of the chiral compound A measured by C-NMR is defined as Xa, the number of moles of the chiral compound B as Xb, the number of moles of the chiral compound C as Xc, and the number of moles of the chiral compound D as Xd. The total number of moles of the chiral compound A, the chiral compound B, the chiral compound C, and the chiral compound D is defined as Xt (=Xa+Xb+Xc+Xd). Details of the method for measuring Xa, Xb, Xc, and Xd in the present invention will be described in the Examples section.

[0034] <Regarding Xa / Xt> In the TCDDM composition of the present invention, the upper limit of Xa / Xt calculated from Xa and Xt is Xa / Xt≦0.430 from the viewpoint of storage stability of the TCDDM composition. Xa / Xt is preferably Xa / Xt≦0.400, more preferably Xa / Xt≦0.370, even more preferably Xa / Xt≦0.360, and particularly preferably Xa / Xt<0.350.

[0035] On the other hand, the lower limit of Xa / Xt is not particularly limited, but from the viewpoint of maintaining good handleability of the TCDDM composition, it can usually be set to Xa / Xt≧0.250, preferably Xa / Xt≧0.270, more preferably Xa / Xt≧0.290, even more preferably Xa / Xt≧0.310, and particularly preferably Xa / Xt≧0.330.

[0036] The above upper and lower limits can be combined arbitrarily. For example, in the TCDDM composition of the present invention, Xa / Xt is not particularly limited, but can be 0.250≦Xa / Xt≦0.430, preferably 0.270≦Xa / Xt≦0.400, more preferably 0.290≦Xa / Xt≦0.370, even more preferably 0.310≦Xa / Xt≦0.360, and particularly preferably 0.330≦Xa / Xt<0.350.

[0037] The means for controlling the Xa / Xt value is not particularly limited, and a person skilled in the art can control the Xa / Xt value by appropriately optimizing the production conditions according to well-known techniques. For example, the Xa / Xt value can be controlled by optimizing the reaction conditions for hydroformylation and the distillation conditions for distilling and purifying the resulting TCDDM composition.

[0038] <Regarding Xb / Xt> In the TCDDM composition of the present invention, the lower limit of Xb / Xt calculated from Xb and Xt is Xb / Xt≧0.016 from the viewpoint of storage stability of the TCDDM composition. Xb / Xt is preferably Xb / Xt≧0.020, more preferably Xb / Xt≧0.027, even more preferably Xb / Xt≧0.030, particularly preferably Xb / Xt≧0.031, and most preferably Xb / Xt≧0.032.

[0039] On the other hand, the upper limit of Xb / Xt is not particularly limited, but from the viewpoint of maintaining the fluidity of the TCDDM composition at an appropriate level and thereby maintaining good handleability, Xb / Xt≦0.13 can be set. Xb / Xt is preferably Xb / Xt≦0.10, more preferably Xb / Xt≦0.048, even more preferably Xb / Xt≦0.046, particularly preferably Xb / Xt≦0.044, and most preferably Xb / Xt≦0.042.

[0040] The above upper and lower limits can be combined arbitrarily. For example, in the TCDDM composition of the present invention, Xb / Xt is not particularly limited, but can be 0.016≦Xb / Xt≦0.13, preferably 0.020≦Xb / Xt≦0.10, more preferably 0.027≦Xb / Xt≦0.048, even more preferably 0.030≦Xb / Xt≦0.046, particularly preferably 0.031≦Xb / Xt≦0.044, and most preferably 0.032≦Xb / Xt≦0.042.

[0041] The means for controlling the Xb / Xt value is not particularly limited, and a person skilled in the art can control the Xb / Xt value by appropriately optimizing the production conditions according to well-known techniques. For example, the Xb / Xt value can be controlled by optimizing the reaction conditions for hydroformylation and the distillation conditions for distilling and purifying the resulting TCDDM composition.

[0042] <Regarding Xc / Xt> In the TCDDM composition of the present invention, the lower limit of Xc / Xt calculated from Xc and Xt can be Xc / Xt≧0.300 from the viewpoint of storage stability of the TCDDM composition. Xc / Xt is preferably Xc / Xt≧0.310, more preferably Xc / Xt≧0.320, and even more preferably Xc / Xt≧0.330.

[0043] On the other hand, the upper limit of Xc / Xt is not particularly limited, but from the viewpoint of maintaining good handleability of the TCDDM composition, it can usually be set to Xc / Xt≦0.380. Xc / Xt is preferably Xc / Xt≦0.360, more preferably Xc / Xt≦0.350, and even more preferably Xc / Xt≦0.340.

[0044] The above upper and lower limits can be combined in any manner. For example, in the TCDDM composition of the present invention, Xc / Xt is not particularly limited, but can be set to 0.300≦Xc / Xt≦0.380, preferably 0.310≦Xc / Xt≦0.360, more preferably 0.320≦Xc / Xt≦0.350, and even more preferably 0.330≦Xc / Xt≦0.340.

[0045] The means for controlling the Xc / Xt value is not particularly limited, and a person skilled in the art can control the Xc / Xt value by appropriately optimizing the production conditions according to well-known techniques. For example, the Xc / Xt value can be controlled by optimizing the reaction conditions for hydroformylation and the distillation conditions for distilling and purifying the resulting TCDDM composition.

[0046] <Regarding Xd / Xt> In the TCDDM composition of the present invention, the lower limit of Xd / Xt calculated from Xd and Xt is not particularly limited, and from the viewpoint of the storage stability of the TCDDM composition, Xd / Xt may be set to Xd / Xt≧0.240. Xd / Xt is preferably Xd / Xt≧0.250, more preferably Xd / Xt≧0.260, even more preferably Xd / Xt≧0.270, and particularly preferably Xd / Xt≧0.280.

[0047] On the other hand, the upper limit of Xd / Xt is not particularly limited, but from the viewpoint of maintaining good handleability of the TCDDM composition, it can be set to Xd / Xt≦0.370. Xd / Xt is preferably Xd / Xt≦0.350, more preferably Xd / Xt≦0.330, even more preferably Xd / Xt≦0.320, and particularly preferably Xd / Xt≦0.310.

[0048] The above upper and lower limits can be combined arbitrarily. For example, in the TCDDM composition of the present invention, Xd / Xt is not particularly limited, but can be 0.240≦Xd / Xt≦0.370, preferably 0.250≦Xd / Xt≦0.350, more preferably 0.260≦Xd / Xt≦0.330, even more preferably 0.270≦Xd / Xt≦0.320, and particularly preferably 0.280≦Xd / Xt≦0.310.

[0049] The means for controlling the Xd / Xt value is not particularly limited, and a person skilled in the art can control the Xd / Xt value by appropriately optimizing the production conditions according to well-known techniques. For example, the Xd / Xt value can be controlled by optimizing the reaction conditions for hydroformylation and the distillation conditions for distilling and purifying the resulting TCDDM composition.

[0050] <Regarding Xb / (Xa+Xc+Xd)> In the TCDDM composition of the present invention, the lower limit of Xb / (Xa+Xc+Xd), which is calculated from Xa, Xb, Xc, Xd, and Xt, is not particularly limited. However, from the viewpoint of the storage stability of the TCDDM composition, Xb / (Xa+Xc+Xd) can be set to 0.010 or more (Xb / (Xa+Xc+Xd)≧0.010), preferably 0.023 or more, more preferably 0.027 or more, and even more preferably 0.032 or more.

[0051] On the other hand, the upper limit of Xb / (Xa+Xc+Xd) is not particularly limited, but from the viewpoint of maintaining good handleability of the TCDDM composition, Xb / (Xa+Xc+Xd) can be set to 0.050 or less (Xb / (Xa+Xc+Xd)≦0.050), preferably 0.045 or less, more preferably 0.040 or less, and even more preferably 0.036 or less.

[0052] For example, in the TCDDM composition of the present invention, Xb / (Xa+Xc+Xd) is not particularly limited, but is preferably 0.010 or more and 0.050 or less, more preferably 0.023 or more and 0.045 or less, even more preferably 0.027 or more and 0.040 or less, and particularly preferably 0.032 or more and 0.036 or less.

[0053] The means for controlling the value of Xb / (Xa+Xc+Xd) is not particularly limited, and a person skilled in the art can control it by appropriately optimizing the production conditions according to well-known techniques. For example, the value of Xb / (Xa+Xc+Xd) can be controlled by optimizing the reaction conditions for hydroformylation and the distillation conditions for distilling and purifying the resulting TCDDM composition.

[0054] In the TCDDM composition of the present invention, the chiral compound B is a compound that is detected within a retention time range of 13.65 to 13.85 minutes when the composition is measured by gas chromatography (GC) under the following measurement conditions: In the TCDDM composition of the present invention, the chiral compound A is a compound that is detected within a retention time range of 13.85 to 14.05 minutes when the composition is measured by gas chromatography (GC) under the following measurement conditions:

[0055] (Measurement conditions) Column: Capillary column (length 30 m x inner diameter 0.25 mm x film thickness 1 μm) Liquid phase: 100% dimethylpolysiloxane Carrier gas: Helium Carrier gas column flow rate: 1 mL / min Split ratio: 1 / 30 Injection amount: 0.3 μL Oven temperature: 160°C (no retention time) → heating at 5°C / min → 300°C (retention time 2 min) Injection port temperature: 200°C Detector: Flame ionization detector (temperature 300°C)

[0056] The purity of the TCDDM composition of the present invention is not particularly limited as long as it satisfies the above-mentioned Xa / Xt value and Xb / Xt value, etc., and may be one whose purity has been increased by purification or the like, or may contain impurities other than TCDDM.

[0057] In the TCDDM composition of the present invention, the lower limit of the total content of chiral compound A, chiral compound B, chiral compound C, and chiral compound D is not particularly limited, but from the viewpoint of handleability of the TCDDM composition, it is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to 100% by mass of the total mass of the composition. On the other hand, the upper limit of the total content is not particularly limited, and a higher value is preferable, and it may be 100% by mass, relative to the total mass of the composition.

[0058] <Method for Producing TCDDM Composition> The method for producing the above-mentioned TCDDM composition is not particularly limited, but in one embodiment, the method for producing the TCDDM composition of the present invention can be used.

[0059] The method for producing a TCDDM composition of the present invention comprises the steps of hydroformylating dicyclopentadiene to obtain tricyclodecane dicarbaldehydes, reducing the tricyclodecane dicarbaldehyde to obtain a crude reaction solution containing tricyclodecane dimethanol, and purifying the crude reaction solution by distillation to obtain a tricyclodecane dimethanol composition.

[0060] In this case, isomers are generated in the step of introducing a formyl group by hydroformylation, and therefore a mixture of tricyclodecane dicarbaldehydes is obtained, which are precursors of chiral compound A, chiral compound B, chiral compound C, and chiral compound D. Thereafter, a hydrogenation step is carried out to obtain chiral compound A, chiral compound B, chiral compound C, and chiral compound D, respectively.

[0061] There are no particular limitations on the method for controlling the ratios of chiral compound A, chiral compound B, chiral compound C, and chiral compound D of the present invention. The ratios of chiral compound A, chiral compound B, chiral compound C, and chiral compound D may be controlled by adjusting the reaction conditions for hydroformylation, by isomerization using a method such as heating, or by distillation purification of the produced TCDDM composition.

[0062] <Hydroformylation Reaction of Dicyclopentadiene> There are no particular limitations on the method for hydroformylating dicyclopentadiene, and the hydroformylation can be carried out according to a conventional method. For example, according to the method described in JP-A-2001-10999, dicyclopentadiene can be hydroformylated using hydrogen and carbon monoxide in a hydroformylation reaction solvent comprising a hydrocarbon compound, in the presence of a catalyst comprising a rhodium compound and an organophosphorus compound, as shown in reaction formula (V) below, to produce tricyclodecane dicarbaldehyde.

[0063]

[0064] The rhodium compound used in this hydroformylation step is not limited to the form of the precursor, as long as it forms a complex with an organophosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide. ２ , Rh ２ O ３ , Rh ４ (CO) １２ , Rh ６ (CO) １６ , Rh(NO ３ ) ３ Alternatively, a catalyst precursor such as the above may be introduced into the reaction mixture together with an organophosphorus compound to form a catalytically active rhodium metal hydride carbonyl phosphorus complex in the reaction vessel, or a rhodium metal hydride carbonyl phosphorus complex catalyst may be prepared in advance and then introduced into the reaction vessel.

[0065] In a preferred embodiment of the present invention, Rh(acac)(CO) ２ is used as a rhodium precursor material and reacted with an organophosphorus compound in the presence of a solvent, and then introduced into a reactor together with an excess of free organophosphorus compound to form a catalytically active rhodium-organophosphorus complex catalyst.

[0066] The organophosphorus compounds which form catalysts for the hydroformylation reaction with rhodium compounds include phosphites and phosphines.

[0067] Among these, the phosphite is preferably a phosphite represented by the general formula P(-OR １ ) (-OR ２ ) (-OR ３ ) (wherein, R １ , R ２ and R ３ R represents an optionally substituted aryl group or an optionally substituted alkyl group. １ , R ２ and R ３Specific examples of the alkyl group include aryl groups such as phenyl and naphthyl groups which may be substituted with a methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, methoxy group, etc.; aliphatic alkyl groups such as methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, etc.; and alicyclic alkyl groups such as cyclopentyl and cyclohexyl groups which may be substituted with a lower alkyl group such as a methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, etc.

[0068] Specific examples of suitable phosphites include, but are not limited to, tris(2-t-butylphenyl)phosphite, tris(3-methyl-6-t-butylphenyl)phosphite, tris(3-methoxy-6-t-butylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, di(2-t-butylphenyl)(t-butyl)phosphite, etc. These phosphites may be used alone or in combination of two or more.

[0069] As the phosphine, alkylphosphines with large steric hindrance are particularly effective in the hydroformylation reaction of dicyclopentadiene. Representative examples include, but are not limited to, tricyclopropylphosphine, tricyclobutylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, tricycloheptylphosphine, and tricyclooctylphosphine. These phosphines may be used alone or in combination of two or more.

[0070] The amount of the organophosphorus compound used in the hydroformylation reaction solution is in the range of 1 to 400 moles, preferably 3 to 200 moles, relative to the amount of rhodium metal, so that tricyclodecane dicarbaldehyde can be obtained at a sufficient hydroformylation reaction rate.

[0071] The hydroformylation reaction of dicyclopentadiene can be carried out without using a solvent, but is more preferably carried out using an organic solvent that is inert to the reaction.

[0072] As will be described later, after completion of the hydroformylation reaction, the reaction product liquid containing tricyclodecane dicarbaldehyde is contacted with an alcohol to extract tricyclodecane dicarbaldehyde into an extraction solvent layer comprising alcohol, while leaving the catalyst components in the dihydroformylation reaction solvent layer, and then layer separation is carried out. Therefore, the hydroformylation reaction solvent is preferably one that undergoes layer separation from the alcohol. Examples of such solvents include aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, and alicyclic hydrocarbon compounds.

[0073] Examples of aromatic hydrocarbon compounds include methylbenzenes such as benzene, toluene, xylene, mesitylene, and pseudocumene, ethylbenzenes such as ethylbenzene, diethylbenzene, and triethylbenzene, and propylbenzenes such as isopropylbenzene, 1,3-diisopropylbenzene, and 1,4-diisopropylbenzene. Various other alkylbenzenes can also be suitably used.

[0074] Examples of aliphatic hydrocarbon compounds include pentane, hexane, heptane, octane, isooctane, dodecane, and decane. The aliphatic hydrocarbon compound is not limited to these, as long as it is liquid at standard temperature and pressure.

[0075] As the alicyclic hydrocarbon compound, cyclohexane, cyclooctane, cyclododecane, decalin, methylcyclohexane, etc. are preferably used.

[0076] These solvents may be used alone or in combination of two or more.

[0077] From the viewpoint of reaction efficiency, it is preferable to use a solvent so that the concentration of dicyclopentadiene in the reaction liquid is about 10 to 95% by mass, particularly about 30 to 90% by mass.

[0078] The amount of rhodium catalyst used is usually 10 to 5000 ppm by weight, more preferably 50 to 2000 ppm by weight, of rhodium metal relative to the raw material dicyclopentadiene. If rhodium is used at 50 ppm or more, it becomes necessary to recover the catalyst.

[0079] The reaction pressure of the hydroformylation of dicyclopentadiene can be set within the range of 0.5 MPaG to 4.5 MPaG from the viewpoint of controlling the content ratio of chiral compound A (Xa / Xt) to the content ratio of chiral compound B (Xb / Xt) in the resulting TCDDM composition within the desired range and efficiently producing the TCDDM composition of the present invention. That is, from the viewpoint of maintaining a good hydroformylation reaction rate, the lower limit of the reaction pressure of the hydroformylation reaction is preferably 0.5 MPaG or more, more preferably 1.0 MPaG or more, and even more preferably 1.5 MPaG or more. On the other hand, the upper limit of the reaction pressure is preferably 4.5 MPaG or less, more preferably 4.0 MPaG or less, and even more preferably 3.5 MPaG or less, from the viewpoint of controlling the Xa / Xt value of the resulting TCDDM composition to 0.430 or less.

[0080] The above upper and lower limits can be combined in any desired manner. For example, the reaction pressure of the hydroformylation reaction is preferably 0.5 MPaG or more and 4.5 MPaG or less, more preferably 1.0 MPaG or more and 4.0 MPaG or less, and even more preferably 1.5 MPaG or more and 3.5 MPaG or less.

[0081] The reaction temperature for the hydroformylation of dicyclopentadiene is not particularly limited and can usually be set within the range of 40°C to 160°C. The lower the reaction temperature, the slower the hydroformylation reaction rate tends to be. If the reaction temperature is too high, side reactions from dicyclopentadiene and the hydroformylation reaction product in the reaction solution tend to proceed, resulting in a lower yield of tricyclodecane dicarbaldehyde. The reaction temperature can preferably be set within the range of 80°C to 140°C.

[0082] The molar ratio of hydrogen to carbon monoxide in the hydrogen / carbon monoxide mixed gas used in the reaction can be selected from the range of 0.2 to 5.0 as the introduced gas composition (hydrogen / carbon monoxide). If the hydrogen / carbon monoxide mixed gas is outside this range, the reaction activity or aldehyde selectivity of the hydroformylation reaction decreases.

[0083] The hydroformylation reaction is carried out using a continuous feed method in which the raw material dicyclopentadiene is fed alone or as a mixed solution of dicyclopentadiene and a solvent to a reactor containing a rhodium-organophosphorus complex catalyst, a solvent, and a hydrogen / carbon monoxide mixed gas. This method reduces the production of cyclopentadiene, which inhibits the hydroformylation reaction due to thermal decomposition of dicyclopentadiene in the reactor, and maintains a good reaction rate and yield. To maintain the fluidity of dicyclopentadiene, it is preferable to dilute it with the aforementioned solvent and feed it to the reactor at a temperature at which it does not depolymerize to produce cyclopentadiene.

[0084] <Extraction of Tricyclodecane Dicarbaldehyde> After completion of the hydroformylation reaction, the reaction product liquid is contacted with an alcohol either as is or after being diluted with the hydrocarbon compound used as the hydroformylation reaction solvent in the reaction or with another hydrocarbon compound, to extract the product tricyclodecane dicarbaldehyde into the alcohol while leaving the catalyst components in the hydroformylation reaction solvent layer, followed by layer separation.

[0085] Examples of alcohols include primary alcohols having 1 to 3 carbon atoms and polyhydric alcohols having 2 to 6 carbon atoms. Examples of primary alcohols include methanol, ethanol, and propanol. Examples of polyhydric alcohols having 2 to 6 carbon atoms include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, isomers of pentanediol, neopentyl glycol, hexanediol, glycerin, pentaerythritol, and trimethylolpropane. Among these, methanol, ethylene glycol, propanediol, and butanediol are preferred because they have relatively low boiling points, are inexpensive, and are easy to handle as liquids. These extraction solvents may be used alone or in combination of two or more.

[0086] The extraction may be carried out in the presence of water in addition to the alcohol, which facilitates the distribution of the aldehyde and catalyst components into each layer.

[0087] It is preferable that the reaction solvent and extraction solvent used in the hydroformylation reaction have different densities to achieve effective layer separation. Suitable examples of combinations of a hydroformylation reaction solvent containing tricyclodecane dicarbaldehyde and an extraction solvent include a combination of methylcyclohexane as the reaction solvent and ethylene glycol as the extraction solvent, and a combination of methylcyclohexane as the reaction solvent and methanol and water as the extraction solvent.

[0088] The distribution of tricyclodecane dicarbaldehyde between the hydroformylation reaction solvent and the extraction solvent is equilibrium, whereas the catalyst components rhodium and organophosphorus compounds are present essentially exclusively in the hydroformylation reaction solvent and below analytical limits in the extraction solvent.

[0089] The volume ratio of the extraction solvent to the reaction product solution used is determined by the solubility of tricyclodecanedicarbaldehyde in the extraction solvent and the amount of tricyclodecanedicarbaldehyde to be extracted. For example, if the tricyclodecanedicarbaldehyde to be separated has high solubility in the extraction solvent and is present at a low concentration in the reaction product solution, practical extraction of tricyclodecanedicarbaldehyde is possible using a low volume ratio (extraction solvent / reaction product solution) of extraction solvent. The higher the product concentration, the higher the volume ratio (extraction solvent / reaction product solution) required to extract tricyclodecanedicarbaldehyde from the reaction product solution.

[0090] When tricyclodecane dicarbaldehyde exhibits relatively low solubility in the extraction solution, the volume ratio (extraction solvent / reaction product liquid) can vary within the range of 10:1 to 1:10. To increase the amount of tricyclodecane dicarbaldehyde extracted using a small amount of extraction solvent, it is effective to use separate extraction solvents and perform the extraction procedure several times. Furthermore, in the final stage of the extraction procedure, a hydroformylation reaction solvent such as methylcyclohexane may be added in an amount of approximately 5 to 20% by mass relative to the reaction product liquid. The addition of the hydroformylation reaction solvent can improve the catalyst removal rate.

[0091] The temperature at which the extraction operation is carried out is not particularly limited, but it is practical to carry out the operation at or below the hydroformylation reaction temperature. After the reaction, the extraction operation may be carried out by adding an extraction solvent to the hydroformylation reactor, or the hydroformylation reaction product liquid may be withdrawn from the hydroformylation reactor and the extraction operation may be carried out in an extraction tank. It is also possible to carry out the extraction operation by adding the extraction solvent directly to the hydroformylation reactor, and retain the catalyst components in the hydroformylation reactor while carrying out the next hydroformylation reaction. When the hydroformylation reaction product liquid is withdrawn and the operation is carried out in an extraction tank, the reaction solvent layer of the hydrocarbon compound containing the catalyst is returned to the hydroformylation reactor and used again in the reaction. This process can be carried out as either a batch process or a continuous process.

[0092] The above-described extraction procedure can provide a tricyclodecane dicarbaldehyde-containing solution containing 10 to 90 mass% tricyclodecane dicarbaldehyde and 10 to 90 mass% extraction solvent. When a reaction solvent is added, a tricyclodecane dicarbaldehyde-containing solution containing 5 to 90 mass% tricyclodecane dicarbaldehyde, 5 to 90 mass% extraction solvent, and 5 to 90 mass% reaction solvent can be obtained.

[0093] The alcohol in the extraction solvent reacts with a portion of the hydroformylation product, tricyclodecane dicarbaldehyde, to produce an acetal compound by acetalizing tricyclodecane dicarbaldehyde. The content of the acetal compound in tricyclodecane dicarbaldehyde is usually about 0.1 to 50% by mass, and preferably about 1 to 25% by mass.

[0094] <Hydrogenation Reduction Reaction> The extract containing tricyclodecane dicarbaldehyde (tricyclodecane dicarbaldehyde-containing solution) obtained by the above extraction operation is then subjected to hydrogenation reduction in the presence of a known hydrogenation catalyst to produce TCDDM according to the following reaction formula (VI).

[0095] This hydrogenation reduction reaction is preferably carried out in the presence of water and a hydrogenation catalyst, because the acetal compound can be rapidly converted into tricyclodecanedicarbaldehyde during the hydrogenation reaction of tricyclodecanedicarbaldehyde, and the tricyclodecanedicarbaldehyde converted from the acetal compound can be hydrogenated to produce TCDDM in a high yield.

[0096]

[0097] The amount of water present in the hydrogenation reduction reaction is preferably equal to or greater than the amount of the acetal compound in the hydrogenation reduction reaction solution, and is an amount that does not cause phase separation of the reaction solution. In the hydrogenation reduction reaction, the water content of the entire reaction solution is preferably 2% by mass or more, preferably 2 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 10 to 20% by mass. When the water content is within the above range, phase separation between the water and the reaction solvent does not occur, and the above-mentioned effects achieved by the presence of water in the hydrogenation reaction system can be effectively obtained. This water addition may be carried out in an extraction step in which the catalyst component and tricyclodecane dicarbaldehyde are separated from the hydroformylation reaction product solution, or water may be added to the reaction system immediately before the hydrogenation reduction reaction.

[0098] The hydrogenation catalyst used in the hydrogenation reduction reaction is not particularly limited, and for example, a ruthenium (Ru) catalyst or a nickel-supported diatomaceous earth catalyst can be used. The ruthenium (Ru) catalyst is not particularly limited, and for example, a commercially available ruthenium (Ru)-supported carbon such as Ru / C catalyst (trade name, manufactured by N.E. Chemcat Corporation) can be used. The nickel-supported diatomaceous earth catalyst is not particularly limited, and for example, a nickel-supported diatomaceous earth catalyst having a nickel support amount of 12% and a chromium support amount of 2%, as disclosed in Example 1 of JP 2005-279587 A, can be used.

[0099] The reaction mode for the hydrogenation reduction reaction may be appropriately selected from a method in which the catalyst is charged as a slurry in a stirred reactor, the reaction is carried out batchwise, and after the reaction, the catalyst is separated from the product liquid by settling and filtration, or a trickle reaction in which a molded catalyst is charged in a tubular reactor, and the product liquid and hydrogen gas are passed over the catalyst. There are no particular restrictions on the amount of catalyst used, as long as TCDDM can be produced with industrially advantageous productivity.

[0100] The reaction temperature of the hydroreduction reaction can be set within the range of 125°C or higher and 350°C or lower, from the viewpoint of controlling the content ratio of chiral compound A (Xa / Xt) to the content ratio of chiral compound B (Xb / Xt) in the resulting TCDDM composition within the desired range and efficiently producing the TCDDM composition of the present invention. That is, from the viewpoint of controlling the Xb / Xt value of the resulting TCDDM composition to 0.016 or higher, the lower limit of the reaction temperature of the hydroreduction reaction is preferably 125°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, particularly preferably 145°C or higher, and most preferably 150°C or higher. On the other hand, from the viewpoint of suppressing thermal decomposition of TCDDM and side reactions during the hydroreduction reaction, the upper limit of the reaction temperature is preferably 350°C or lower, more preferably 300°C or lower, even more preferably 250°C or lower, particularly preferably 200°C or lower, and most preferably 180°C or lower.

[0101] The above upper and lower limits can be combined in any desired manner. For example, the reaction temperature of the hydrogenation reduction reaction is preferably 125°C or higher and 350°C or lower, more preferably 130°C or higher and 300°C or lower, even more preferably 140°C or higher and 250°C or lower, particularly preferably 145°C or higher and 200°C or lower, and most preferably 150°C or higher and 180°C or lower.

[0102] The reaction pressure of the hydrogenation reduction reaction is not particularly limited, and can usually be set to 15 MPaG or less. As the reaction pressure increases, a reaction apparatus with high-pressure resistance becomes necessary, which reduces economic efficiency. Therefore, the reaction pressure is preferably 10 MPaG or less, more preferably 7 MPaG or less. On the other hand, the lower limit of this reaction pressure is usually 1 MPaG.

[0103] <Removal of Residual Metals> The crude reaction solution obtained by the above-mentioned hydrogenation reduction reaction operation contains metal elements derived from the hydrogenation catalyst as eluted components. By removing the metal elements from the crude reaction solution prior to distillation purification, it is possible to suppress thermal decomposition of TCDDM caused by the metal elements in the distillation purification step.

[0104] The method for removing metal elements from the crude reaction solution to reduce their content is not particularly limited, and examples include activated carbon treatment, cation exchange resin, silica gel adsorption, etc. Activated carbon treatment is preferred because of its removal efficiency and the ability to reuse the adsorbent.

[0105] The activated carbon treatment method may be a batch treatment in which activated carbon is added to the crude reaction solution and stirred, and then the activated carbon is subjected to solid-liquid separation by filtration or the like, or a continuous treatment in which the crude reaction solution is passed through a column packed with activated carbon.

[0106] In the case of batch treatment, the amount of activated carbon to be added to the crude reaction solution is appropriately determined depending on the metal element adsorption capacity of the activated carbon, the metal element content in the crude reaction solution, etc. As a general condition, it is preferable to add activated carbon to the crude reaction solution so as to give a concentration of about 0.01 to 10 mass % and stir the mixture.

[0107] In the case of continuous treatment, the treatment flow rate is not particularly limited, but treatment may be carried out at a space velocity (LHSV) of 1 to 10.

[0108] Such activated carbon treatment may be carried out multiple times. That is, the activated carbon-treated liquid obtained by treating the crude reaction solution with activated carbon may be treated with activated carbon again. In this case, the type, amount, treatment conditions, etc. of activated carbon used in the first activated carbon treatment and the second activated carbon treatment may be different.

[0109] The lower the metal element content of the crude reaction solution to be subjected to the next step of distillation purification, the more preferable it is from the viewpoint of suppressing thermal decomposition of TCDDM. The metal element content of the crude reaction solution to be subjected to distillation purification is preferably 10 ppm by mass or less, particularly 5 ppm by mass or less, and particularly 1 ppm by mass or less.

[0110] The pH of the crude reaction liquid to be subjected to distillation purification is preferably within the range of 6 to 8. A lower limit of pH of 6 or more is preferred because this suppresses the by-production of low-boiling compounds thought to be due to dehydration of TCDDM and high-boiling compounds thought to be due to dimerization such as etherification. An upper limit of pH of 8 or less is preferred because this makes the distillation purification equipment less susceptible to alkali corrosion.

[0111] The pH of the reaction product liquid obtained in the hydrogenation reduction reaction is usually 6 to 8, and even if this liquid is subjected to treatments for removing the hydrogenation catalyst and metal elements, the pH remains almost unchanged. However, the pH of the reaction product liquid may fall outside the range of 6 to 8 due to acid or alkali components eluted from the hydrogenation catalyst. In such cases, it is preferable to adjust the pH to 6 to 8 by adding a pH adjuster such as an acid or alkali as appropriate.

[0112] <Distillation Purification> The crude reaction liquid obtained by the above hydrogenation reduction reaction operation, or the crude reaction liquid with reduced metal element content obtained by the above residual metal removal operation, is then subjected to distillation purification.

[0113] In the method for producing a tricyclodecane dimethanol composition of the present invention, the number and type of distillation columns used in the distillation purification step are not particularly limited, and distillation purification can be carried out using, for example, a purification system equipped with one or more distillation columns. Specifically, distillation purification can be carried out by appropriately selecting and combining a solvent distillation separation column for removing the reaction solvent, a light-boiling distillation separation column for removing by-products and impurities having a boiling point lower than that of the TCDDM components, a high-boiling distillation separation column for removing by-products and impurities having a boiling point higher than that of the TCDDM components, and, if necessary, a thin-film distillation column for removing by-products and impurities having a boiling point higher than that of the TCDDM components at a relatively low temperature in a short period of time.

[0114] In the distillative purification of the crude reaction solution, it is preferable to control the content ratio of chiral compound A (Xa / Xt) and the content ratio of chiral compound B (Xb / Xt) in the resulting tricyclodecane dimethanol composition within a desired range, and to efficiently produce the tricyclodecane dimethanol composition of the present invention, to carry out the distillative purification under conditions that satisfy the following formula (1):

[0115] (Ya-Za) x T / S x 100≦1.65 (1) (In formula (1), Ya: mass proportion of chiral compound A in the crude reaction solution supplied to the distillation purification step (unit: dimensionless number); S: total weight (unit: g) of chiral compound A, chiral compound B, chiral compound C, and chiral compound D in the crude reaction solution supplied to the distillation purification step; Za: mass proportion (unit: dimensionless number) of chiral compound A in the distillate distilled out of the purification system from the distillation column in the distillation purification step (unit: g); and T: total weight (unit: g) of chiral compound A, chiral compound B, chiral compound C, and chiral compound D in the distillate distilled out of the purification system from the distillation column in the distillation purification step.)

[0116] In this specification, the phrase "distilled outside the purification system" means that the bottom distillate and / or the overhead distillate of the distillation column is discharged outside the purification system.

[0117] As described above, when distillation purification is performed using a purification system including two or more distillation columns, the values ​​of Za and T can be calculated based on the total amount of distillate distilled out of the purification system from these distillation columns.

[0118] In the formula (1), (Ya-Za) is an index value representing the proportion of chiral compound A distilled out of the purification system during the distillation purification step. The smaller the value of (Ya-Za), the less chiral compound A is contained in the obtained TCDDM composition, and the value of Xa / Xt tends to be smaller. In the formula (1), T / S is an index value representing the proportions of chiral compound B, chiral compound C, and chiral compound D, which have low boiling points, distilled out of the TCDDM distilled out of the purification system during the distillation purification step. The smaller the value of T / S, the less chiral compound A is contained in the obtained TCDDM composition, and the value of Xa / Xt tends to be smaller.

[0119] That is, the value of (Ya-Za) x T / S x 100, expressed by the above formula (1), is an index value showing the discharge rate of chiral compound A that is distilled off (discharged) from the distillation column to the outside of the purification system in the distillation purification step. By adopting distillation conditions that reduce this value, the content rate of chiral compound A in the obtained TCDDM composition can be reduced, and the value of Xa / Xt can be reduced.

[0120] The upper limit of (Ya-Za) x T / S x 100 is preferably 1.65 or less, more preferably 1.30 or less, even more preferably 1.00 or less, particularly preferably 0.65 or less, and most preferably 0.3 or less, from the viewpoint of controlling the Xa / Xt value of the resulting TCDDM composition to 0.430 or less. On the other hand, the lower limit of (Ya-Za) x T / S x 100 is preferably 0.001 or more, more preferably 0.003 or more, even more preferably 0.010 or more, particularly preferably 0.015 or more, and most preferably 0.030 or more, from the viewpoint of efficiently separating and removing by-products from the TCDDM composition. The smaller the value of (Ya-Za) x T / S x 100, the more difficult it becomes to efficiently separate and remove by-products from the TCDDM composition, which makes it necessary to increase the number of theoretical plates and the reflux ratio of the distillation column, which tends to be economically disadvantageous. The above upper and lower limits can be combined in any manner. For example, (Ya-Za) x T / S x 100 is preferably 0.001 or more and 1.65 or less, more preferably 0.003 or more and 1.30 or less, even more preferably 0.010 or more and 1.00 or less, particularly preferably 0.015 or more and 0.65 or less, and most preferably 0.030 or more and 0.3 or less.

[0121] In distillation purification, the bottom temperature of the distillation column is not particularly limited, but can preferably be in the range of 150°C or higher and 300°C or lower. If the lower limit of the bottom temperature of the distillation column is 150°C or higher, TCDDM can be efficiently volatilized. The lower limit of the bottom temperature of the distillation column is preferably 160°C or higher, more preferably 170°C or higher, and even more preferably 180°C or higher. On the other hand, if the upper limit of the bottom temperature of the distillation column is 300°C or lower, the by-production of high-boiling impurities due to dimerization of TCDDM can be suppressed. The upper limit of the bottom temperature of the distillation column is preferably 280°C or lower, more preferably 250°C or lower, and even more preferably 220°C or lower. The upper and lower limits of the bottom temperature of the distillation column described above can be combined arbitrarily.

[0122] The number of theoretical plates for distillation purification is not particularly limited, but is preferably within the range of 5 to 45 theoretical plates. If the lower limit of the number of theoretical plates of the distillation column used for distillation purification is 5 or more, impurities and the product can be easily separated. The lower limit of the number of theoretical plates of the distillation column is more preferably 6 or more, even more preferably 7 or more, particularly preferably 8 or more, and most preferably 10 or more. On the other hand, if the upper limit of the number of theoretical plates of the distillation column is 45 or less, the pressure difference between the top and bottom of the column is small, and the temperature of the bottom of the column is low, thereby reducing the heat load on the equipment. The upper limit of the number of theoretical plates of the distillation column is more preferably 35 or less, even more preferably 25 or less, particularly preferably 15 or less, and most preferably 13 or less. The upper and lower limits of the number of theoretical plates of the distillation column described above can be combined arbitrarily.

[0123] There are no particular limitations on other conditions for the distillation column in distillation purification, but distillation is usually carried out at a pressure of 0.1 kPaA or more and 100 kPaA or less, and a reflux ratio of about 1 or more and 30 or less. In particular, by controlling the reflux ratio and the distillate amount, it becomes possible to adjust the abundance ratios of chiral compound A, chiral compound B, chiral compound C, and chiral compound D in the resulting TCDDM composition. These conditions may be changed as desired depending on the equipment performance, vessel efficiency, recovery amount, etc. of the distillation column, and are not particularly limited as long as a TCDDM composition having the composition specified in the present invention is obtained.

[0124] The bottom liquid of the distillation column obtained by such distillation purification may be further subjected to simple distillation at 0.1 kPaA or more and 10 kPaA or less and 140° C. or more and 250° C. or less. By such distillation purification, a TCDDM composition having a TCDDM purity of 98% or more can usually be obtained in high yield.

[0125] <UV-curable composition> The UV-curable composition of the present invention is a UV-curable composition derived from the TCDDM composition of the present invention. More specifically, the UV-curable composition of the present invention is a UV-curable composition synthesized using the TCDDM composition of the present invention as a raw material. Even more specifically, the UV-curable composition of the present invention is a UV-curable composition synthesized using tricyclodecane dimethanol contained in the TCDDM composition of the present invention as a raw material.

[0126] The method for producing the ultraviolet-curable composition is not particularly limited and can be carried out according to a conventional method. In general, it is desirable to produce and use a di(meth)acrylic acid ester derivative or a urethane acrylate derivative from tricyclodecane dimethanol in the TCDDM composition as a raw material.

[0127] Both of the two hydroxyl groups of tricyclodecane dimethanol contained in the TCDDM composition may be used in the reaction, or one of the hydroxyl groups may be reacted and the other hydroxyl group may be left. In this case, the remaining hydroxyl group may be appropriately converted into a functional group suitable for the intended use by an organic synthetic method.

[0128] Specific methods for producing a di(meth)acrylic acid ester derivative from TCDDM using a TCDDM composition as a raw material include a method of reacting TCDDM with (meth)acrylic acid, a method of subjecting TCDDM to a transesterification reaction with a (meth)acrylic acid ester, and a method of reacting TCDDM with a halide of (meth)acrylic acid, such as (meth)acrylic acid chloride.

[0129] Suitable reaction conditions for each of the above production methods are as follows.

[0130] When producing a di(meth)acrylic acid ester derivative using (meth)acrylic acid or a (meth)acrylic acid ester, the reaction can be promoted by using a catalyst and continuously removing the produced water or lower alcohol from the system. Examples of the catalyst include known esterification catalysts such as sulfuric acid, paratoluenesulfonic acid, boron trifluoride, and organotin compounds, and any of these can be selected and used. The amount of catalyst used is preferably 10 to 100,000 ppm relative to the total mass of the reaction substrates, from the viewpoints of reducing the load on the production equipment and reducing catalyst costs.

[0131] When a di(meth)acrylic acid ester derivative is produced using a halide of (meth)acrylic acid, the reaction is preferably carried out in the presence of a basic compound, and the reaction can also be accelerated by using a catalyst.

[0132] Examples of the basic compound include known basic compounds, such as tertiary amines such as triethylamine and N-ethyldiisopropylamine; phosphates such as potassium phosphate and sodium phosphate; carbonates such as potassium carbonate and sodium carbonate; hydroxides such as potassium hydroxide and sodium hydroxide, and any of these can be selected and used. From the viewpoints of reducing the load on the production equipment and reducing raw material costs, the amount of the basic compound used is preferably 1.0 to 6.0 equivalents per equivalent of the halide of acrylic acid or methacrylic acid.

[0133] The catalyst can be arbitrarily selected from known catalysts for the esterification reaction of acid chlorides, such as pyridines such as N,N-dimethyl-4-aminopyridine, imidazoles such as N-methylimidazole, and tertiary amines such as triethylenediamine. The amount of catalyst used is preferably 10 to 100,000 ppm relative to the total mass of the reaction substrates, from the viewpoints of reducing the load on the production equipment and reducing catalyst costs.

[0134] In each of the above production methods, it is preferable to add a polymerization inhibitor to prevent thermal polymerization of (meth)acrylic acid, a (meth)acrylic acid ester, or a halide of (meth)acrylic acid.

[0135] Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, parabenzoquinone, 2,5-dihydroxyparabenzoquinone, copper salts, phenothiazine, paraphenylenediamine, phenyl-β-naphthylamine, etc. The amount of the polymerization inhibitor used is preferably 10 to 100,000 ppm relative to the total mass of the reaction substrates, from the viewpoints of catalytic activity and reducing the influence on side reactions.

[0136] In each of the above production methods, the reaction temperature is preferably −20 to 120° C., more preferably 0 to 100° C., from the viewpoint of shortening the reaction time and preventing polymerization. The reaction time is preferably 1 to 20 hours.

[0137] A solvent can also be used in the reaction in each of the above production methods. The solvent is not particularly limited as long as it does not adversely affect the reaction, and examples include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and mesitylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, and cyclooctane; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, chlorobenzene, and trifluoromethylbenzene; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, tetrahydrofuran, and dioxane; ketones such as methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and isopropyl acetate; nitriles such as acetonitrile; acyclic or cyclic amides such as dimethylformamide and N-methylpyrrolidinone; and acyclic or cyclic sulfoxides or sulfones such as dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.

[0138] The structure of the urethane acrylate made from the TCDDM composition is not particularly limited as long as it is an acrylic acid or methacrylic acid ester derivative containing a urethane bond.

[0139] A preferred method for producing a urethane acrylate from TCDDM using the TCDDM composition as a raw material is to react the TCDDM composition, a polyisocyanate compound, and a monohydroxyacrylate compound in the presence of a catalyst. Furthermore, a polyol compound other than the TCDDM composition may be added to adjust the properties of the cured product.

[0140] The content of the TCDDM composition relative to the total mass of the reaction substrate as a urethane acrylate raw material is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of hardness and heat resistance of the cured product. On the other hand, the upper limit of the content is not particularly limited, and the higher the content, the better.

[0141] Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenylether-4,4'-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, norbornanemethane diisocyanate and hydrogenated versions thereof, pentamethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and isophorone diisocyanate. These compounds may be used in the form of nurates, adducts, or biuret forms, or as dimers or trimers. These compounds may be used alone or in combination of two or more.

[0142] In the monohydroxyacrylate compound, the structural moiety that bonds the hydroxy group and the acryloyloxy group is preferably composed of three or more carbon atoms. Examples of such compounds include acrylates of aliphatic polyols having 3 or more carbon atoms, such as hydroxypropyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, ditrimethylolpropane triacrylate, and dipentaerythritol pentaacrylate; (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain, such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain, has been introduced into the molecular structure of the acrylate compound; lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the acrylate compound; isocyanuric acid diacrylate; (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain, such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain, has been introduced into the molecular structure of isocyanuric acid diacrylate; and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of isocyanuric acid diacrylate. Further, methacrylate compounds in which the acrylate of the above-mentioned compound group is replaced with methacrylate may also be used. These may be used alone or in combination of two or more kinds.

[0143] Examples of polyol compounds other than the TCDDM composition 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-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and dimer diol; diethylene glycol, and propylene glycol. diols having an ether group such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, etc.; diols having an alicyclic structure such as xylylene glycol, 1,4-dihydroxyethylbenzene, 4,4'-methylenebis(hydroxyethylbenzene), etc.; polyols such as glycerin, trimethylolpropane, pentaerythritol, etc.; polyether polyols, polyester polyols, polycarbonate polyols, etc. These polyol compounds may be used alone or in combination of two or more.

[0144] Examples of the catalyst include organic tin compounds such as dibutyltin dilaurate, trimethyltin hydroxide, and tetra-n-butyltin; organic bismuth compounds such as dibutylbismuth dilaurate and dioctylbismuth dilaurate; metal salts such as zinc octoate, tin octoate, cobalt naphthenate, stannous chloride, and stannic chloride; and amine catalysts such as triethylamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N',N'-tetramethyl-1,3-butanediamine, and N-ethylmorpholine.

[0145] It is preferable to add a polymerization inhibitor to prevent thermal polymerization of the monohydroxyacrylate compound, etc. The polymerization inhibitor is not particularly limited as long as it does not inhibit the reaction, and examples thereof include hydroquinone, paramethoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, parabenzoquinone, 2,5-dihydroxyparabenzoquinone, copper salts, phenothiazine, paraphenylenediamine, and phenyl-β-naphthylamine. The amount of polymerization inhibitor used is preferably 10 to 100,000 ppm relative to the total mass of the reaction substrates, from the viewpoints of catalytic activity and reducing the influence on side reactions.

[0146] In order to shorten the reaction time and prevent polymerization, the reaction temperature in the above production method is preferably 30 to 120° C., more preferably 40 to 100° C. The reaction time is preferably 1 to 10 hours.

[0147] A solvent can also be used in the reaction in each of the above production methods. The solvent is not particularly limited as long as it does not adversely affect the reaction, and examples include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and mesitylene; aliphatic hydrocarbons such as heptane, octane, nonane, decane, cyclohexane, and cyclooctane; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, chlorobenzene, and trifluoromethylbenzene; ethers such as diisopropyl ether, dibutyl ether, anisole, tetrahydrofuran, and dioxane; ketones such as methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and isopropyl acetate; nitriles such as acetonitrile; acyclic or cyclic amides such as dimethylformamide and N-methylpyrrolidinone; and acyclic or cyclic sulfoxides or sulfones such as dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.

[0148] The UV-curable composition of the present invention is synthesized using the TCDDM composition of the present invention as a raw material, and therefore has excellent coating stability without impairing the performance inherently required of a UV-curable composition. Therefore, the UV-curable composition of the present invention can be suitably used as a hard coat material, an antifouling coat material, a resist material, an inkjet ink, a material for a 3D printer, etc.

[0149] In applications such as resists, the ultraviolet-curable composition is applied to a substrate and then cured by screen printing, flexible printing, etc. In this case, the ultraviolet-curable composition is required to have excellent fluidity from the viewpoints of being able to apply the composition thinly and uniformly, being able to apply it thickly, and being able to print a fine pattern on the substrate with high precision.

[0150] In applications such as hard coatings, antifouling coatings, and inkjet printing, the ultraviolet-curable composition is applied to a substrate by a coater method, a spray method, or a dispenser method, followed by curing. In this case, the ultraviolet-curable composition is required to have excellent fluidity in order to accurately dispense a fixed amount of the ultraviolet-curable composition.

[0151] As described above, the UV-curable composition of the present invention is derived from the TCDDM composition of the present invention, which has excellent storage stability and can maintain high fluidity even after long-term storage by appropriately controlling the specific isomer ratio. Therefore, the UV-curable composition of the present invention has excellent coating stability and application stability, and does not require the incorporation of additives, so there is no problem of impairing the performance originally required of a UV-curable composition. For these reasons, the UV-curable composition of the present invention can be suitably used for applications such as hard coat materials, antifouling coating materials, resist materials, inkjet inks, and materials for 3D printers.

[0152] <Polymer composition> The polymer composition of the present invention is a polymer composition derived from the TCDDM composition of the present invention, or a polymer composition derived from the UV-curable composition of the present invention. More specifically, the polymer composition of the present invention is a polymer composition obtained by polymerizing the TCDDM composition of the present invention or a composition containing the TCDDM composition, and is a composition containing a polymer containing structural units derived from tricyclodecane dimethanol in the TCDDM composition. Alternatively, the polymer composition of the present invention is a composition containing a polymer obtained by polymerizing the UV-curable composition of the present invention.

[0153] One embodiment of the polymer composition of the present invention may be the polymer composition itself, or may be a composition obtained by adding or removing an appropriate amount of a solvent such as water or an organic solvent to adjust the solid content concentration, or may be a solid obtained by removing the solvent and drying. Furthermore, the polymer composition may be a polymer composition obtained by purifying a composition containing a polymer obtained by polymerization and appropriately removing impurities. If necessary, the polymer composition may further contain appropriate additives, such as storage stabilizers (such as ultraviolet absorbers and antioxidants), colorants, antistatic agents, lubricants, fillers, flame retardants, and foaming agents, within limits that do not affect the performance of the polymer obtained by polymerization. That is, the polymer composition of the present invention may be any composition containing a polymer obtained by polymerizing the TCDDM composition of the present invention or the ultraviolet-curable composition of the present invention, and is not particularly limited in terms of its form, component composition, and the like.

[0154] Specific examples of the polymer constituting the polymer composition include at least one selected from the group consisting of polyester-based resins, epoxy-based resins, acrylate-based resins, polycarbonate-based resins, and polyurethane-based resins.

[0155] In the present invention, the polyester resin refers to a resin containing a polyethylene polymer such as polyethylene terephthalate (PET) as a main component. The polyethylene polymer is not particularly limited, and refers to, for example, a polymer containing structural units derived from a polyol mainly containing glycol and structural units derived from a terephthalic acid compound, and also containing structural units derived from tricyclodecane dimethanol in the TCDDM composition of the present invention.

[0156] In the present invention, the epoxy resin is a resin containing an epoxy polymer as a main component. The epoxy polymer is not particularly limited, and examples thereof include a polymer containing structural units derived from a bisphenol compound and structural units derived from epichlorohydrin, and also containing structural units derived from tricyclodecane dimethanol in the TCDDM composition of the present invention.

[0157] In the present invention, the acrylate resin is a resin containing an acrylate polymer as a main component. The acrylate polymer is not particularly limited, and examples thereof include a polymer containing structural units derived from (meth)acrylic acid or a (meth)acrylic acid derivative, and also containing structural units derived from tricyclodecane dimethanol in the TCDDM composition of the present invention.

[0158] In the present invention, the polycarbonate-based resin refers to a resin containing a polycarbonate-based polymer as a main component. The polycarbonate-based polymer is not particularly limited, and examples thereof include a polymer containing structural units derived from a bisphenol compound, structural units derived from phosgene (carbonyl chloride), or structural units derived from diphenyl carbonate, and also containing structural units derived from tricyclodecane dimethanol in the TCDDM composition of the present invention.

[0159] In the present invention, the polyurethane resin is a resin containing a polyurethane polymer as a main component. The polyurethane polymer is not particularly limited, and examples thereof include a polymer containing structural units derived from a polyol mainly containing glycol and structural units derived from a bifunctional isocyanate, and also containing structural units derived from tricyclodecane dimethanol in the TCDDM composition of the present invention.

[0160] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0161] The compounds used in the examples and comparative examples are as follows: Dicyclopentadiene (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) Acetylacetonatodicarbonylrhodium (manufactured by N.E. Chemcat Corporation) Tris(2,4-di-tert-butylphenyl)phosphite (manufactured by Tokyo Chemical Industry Co., Ltd.) Methylcyclohexane (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) Ruthenium-supported carbon (dry basis Ru content 5%, water content 56%) (trade name: Ru / C, manufactured by N.E. Chemcat Corporation) Nickel-supported diatomaceous earth catalyst (nickel-supported diatomaceous earth with a nickel support amount of 12% and a chromium support amount of 2%, produced in-house according to the description in Example 1 of JP 2005-279587 A) Copper oxide / aluminum oxide-containing catalyst (trade name: HySat, tablet size: 3 x 3 mm, manufactured by Clariant)

[0162] The evaluations in the examples and comparative examples were carried out by the following methods.

[0163] <Identification of Chiral Compounds A to D Contained in TCDDM Compositions> Chiral compounds A to D contained in the TCDDM compositions obtained in the Examples and Comparative Examples were determined by nuclear magnetic resonance spectroscopy according to the following procedure.

[0164] Samples of the TCDDM composition were dissolved in deuterated chloroform (CDCl ３ The sample solution was transferred to an NMR sample tube with an outer diameter of 5 mm.１ H-NMR, １３ C-NMR, DEPT, COSY, TOCSY, NOESY, １ H- １３ C HSQC, １ H- １３ C HMBC spectrum was measured. １ The H-NMR measurement conditions were a resonance frequency of 600 MHz, a flip angle of 45°, a data acquisition time of 3 s, a pulse repetition time of 10 s, an accumulation number of 16, and a measurement temperature of 25° C. The chemical shift reference was set at 0.00 ppm for the TMS signal. １３ The C-NMR measurement conditions were a resonance frequency of 151 MHz, a flip angle of 45°, a data acquisition time of 2 s, a pulse repetition time of 5 s, an accumulation count of 10,000, and a temperature of 25°C. The chemical shift reference was set to the TMS signal at 0.00 ppm. The structure was identified from the signal correlation.

[0165] <Measurement of Xa, Xb, Xc, Xd, and Xt> The number of moles Xa of chiral compound A, the number of moles Xb of chiral compound B, the number of moles Xc of chiral compound C, and the number of moles Xd of chiral compound D, as well as the total number of moles Xt (=Xa+Xb+Xc+Xd) of the chiral compound A, chiral compound B, chiral compound C, and chiral compound D, contained in the TCDDM compositions obtained in the Examples and Comparative Examples, were calculated by nuclear magnetic resonance spectroscopy (NMR) measurement according to the following procedure.

[0166] A 65 mg sample of the TCDDM composition was transferred to a sample tube and diluted with deuterated chloroform (CDCl ３ 0.75 mL of DMSO-d dimethyl sulfoxide (DMSO-d dimethyl sulfoxide, containing 0.03 v / v % TMS (tetramethylsilane)) was added to the sample, and this was used as a sample for NMR measurement. ６ 83 μL of 0.05% v / v TMS was added, and CDCl ３ : DMSO-d ６The NMR measurement sample was transferred to an NMR sample tube with an outer diameter of 5 mm and analyzed using a nuclear magnetic resonance spectrometer (product name: AVANCE NEO 600 NMR, manufactured by Bruker). １ ３ The C-NMR spectrum was measured. １３ The C-NMR measurement conditions were a resonance frequency of 151 MHz, a flip angle of 45°, a data acquisition time of 2 s, a pulse repetition time of 5 s, an accumulation number of 512, and a measurement temperature of 25°C. The chemical shift reference was set to the TMS signal at 0.00 ppm. １３ The C-NMR spectra are shown in Figure 2(a) and Figure 2(b), respectively.

[0167] The molar numbers (Xa, Xb, Xc, Xd) and Xt (= Xa + Xb + Xc + Xd) of chiral compounds A, B, C, and D, respectively, were calculated using the sum of the signal intensities of carbon α on the norbornene ring in TCDDM and carbon α on the norbornane ring in the enantiomer of TCDDM, as shown in the following structural formula (1). Furthermore, for chiral compound A in Comparative Example 1 only, the signal of carbon α on the norbornane ring overlaps with other signals. Therefore, Xa, Xb, Xc, Xd, and Xt were calculated using the sum of the signal intensities of carbon β on the norbornene ring in TCDDM and carbon β on the norbornene ring in the enantiomer of TCDDM, as shown in the following structural formula (2).

[0168] １３ In the C-NMR spectra, the signals of the carbon α on the norbornane ring of chiral compounds A, B, C, and D were observed at 27.9 ppm, 27.6 ppm, 28.4 ppm, and 27.2 ppm, respectively, in deuterated chloroform, and at 27.8 ppm, 27.6 ppm, 28.3 ppm, and 27.4 ppm, respectively, when deuterated dimethyl sulfoxide was added. １３ ​In the C-NMR spectrum, a signal from carbon β on the norbornane ring of chiral compound A was observed at 30.7 ppm. Using the obtained Xa, Xb, Xc, Xd, and Xt, Xa / Xt, Xb / Xt, Xc / Xt, Xd / Xt, and Xb / (Xa+Xc+Xd) were calculated.

[0169]

[0170] <Retention Times of Chiral Compound A and Chiral Compound B> For the TCDDM compositions obtained in the Examples and Comparative Examples, the retention times of chiral compound A and chiral compound B were measured using gas chromatography (GC) under the following measurement conditions.

[0171] (Measurement conditions) Measuring device: Gas chromatograph measuring device (product name: GC-2025, manufactured by Shimadzu Corporation) Column: Capillary column (product name: DB-1, manufactured by Agilent Technologies, length 30 m × inner diameter 0.25 mm × film thickness 1.00 μm) Liquid phase: 100% dimethylpolysiloxane Carrier gas: Helium Carrier gas column flow rate: 1 mL / min Split ratio: 1 / 30 Sample amount: 0.3 μL Oven temperature (heating conditions): 160°C (no holding time) → heating at 5°C / min → 300°C (holding time 2 minutes) Injection port temperature: 200°C Ion source temperature: 300°C Split ratio: 1 / 30 Detector: Flame ionization detector (temperature 300°C)

[0172] A gas chromatogram of the TCDDM composition obtained in Example 2 below is shown in Figure 1. The peak labeled (1) between retention times 13.85 and 14.05 minutes ("Peak 1") is the peak of chiral compound A in the TCDDM composition. The peak labeled (2) between retention times 13.65 and 13.85 minutes ("Peak 2") is the peak of chiral compound B in the TCDDM composition. The peak labeled (3) between retention times 13.30 and 13.50 minutes ("Peak 3") is the peak of chiral compound D in the TCDDM composition. The peak labeled (4) between retention times 13.50 and 13.70 minutes ("Peak 4") is the peak of chiral compound C in the TCDDM composition.

[0173] <Mass Analysis of TCDDM Compositions> To confirm that TCDDM was produced, the TCDDM compositions obtained in the Examples and Comparative Examples were subjected to gas chromatography mass spectrometry to measure m / z and fragment patterns according to the following procedure (Gas chromatography mass spectrometry conditions).

[0174] Measurement device: Gas chromatogram measurement device (trade name: GCMS-QP2010 Ultra, manufactured by Shimadzu Corporation) Carrier gas: Helium, linear velocity 40 cm / sec Column: BPX-5 (manufactured by Trajan Scientific and Medical, length 60 m × inner diameter 0.32 mm × film thickness 0.25 μm) Temperature (heating conditions): 160°C → heat up at 5°C / min → 300°C (hold time 2 min) Vaporization chamber temperature: 200°C Ion source temperature: 250°C MS interface temperature: 300°C Injection volume: 0.5 μL Split ratio: 1 / 30

[0175] <Evaluation of Storage Stability> As an index of the storage stability of the TCDDM compositions obtained in the Examples and Comparative Examples, the dynamic light scattering intensity of the TCDDM compositions was measured using dynamic light scattering analysis according to the following procedure. During the measurement, the fluidity of the TCDDM compositions was also visually observed.

[0176] A sample of the TCDDM composition contained in a glass reagent bottle was immersed in an oil bath set at 60°C, and the sample was heated while stirring until the measurement temperature of the TCDDM composition reached 60°C. Next, stirring of the sample was stopped, and 1 mL of the TCDDM composition was sampled and placed in a measurement cell. The measurement cell was placed in a thermostatic bath attached to a dynamic light scattering measurement device, and while maintaining the measurement temperature of the TCDDM composition at 60°C, dynamic light scattering intensity was measured and fluidity was visually observed under the measurement conditions described below. The dynamic light scattering intensity measurement and visual observation of fluidity were performed immediately before immersion of the TCDDM composition sample in the oil bath (0 hours), and 96 hours, 175 hours, and 196 hours after immersion in the oil bath.

[0177] (Measurement conditions) Measuring device: dynamic light scattering measuring device (trade name: Zetasizer Nano ZS, manufactured by Malvern Panalytical) Detection method: 173° backscattering detection method (scattered light detector placed 173° behind the sample) Sample temperature: 60° C. Cell: glass

[0178] Furthermore, the storage stability of the TCDDM composition was evaluated according to the following criteria. The fluidity was evaluated by immersing the glass reagent bottle in a high-temperature bath of a dynamic light scattering measurement device, immersing the tip of a glass rod 10 mm into the TCDDM composition in the reagent bottle, and then lifting it 10 cm. If the composition exhibited spinnability, it was rated as "fluid." If the composition did not exhibit spinnability, it was rated as "not fluid." (Evaluation Criteria) A: The TCDDM composition exhibited fluidity after 196 hours, and the dynamic light scattering intensity was 3500 or less. B: The TCDDM composition exhibited fluidity after 196 hours, and the dynamic light scattering intensity exceeded 3500. C: The TCDDM composition exhibited fluidity after 96 hours, but lost fluidity after 175 hours, and the dynamic light scattering intensity exceeded 100,000. D: The TCDDM composition did not exhibit fluidity after 96 hours, and the dynamic light scattering intensity exceeded 100,000.

[0179] Example 1 Hydroformylation Reaction In a 500 mL autoclave reactor (vertical stirring type) under a nitrogen atmosphere, 11 mg of acetylacetonatodicarbonylrhodium and 870 mg of tris(2,4-di-tert-butylphenyl)phosphite were weighed out as raw materials for the hydroformylation catalyst, and 69 g of methylcyclohexane and 89 g of dicyclopentadiene were sequentially charged as organic solvents. The temperature of the reaction solution in the reactor was then raised to 70°C with stirring. Next, a mixed gas of hydrogen and carbon monoxide (hydrogen:carbon monoxide = 1:1 (molar ratio)) was quickly injected through the gas inlet valve to a pressure of 3 MPaG in the reactor, and the reaction was carried out for 1 hour. Thereafter, the temperature of the reaction solution was raised to 100°C, and the reaction was carried out for an additional 5 hours. During the reaction, the amount of mixed gas consumed in the reaction was continuously introduced into the reactor while maintaining the pressure in the reactor at 3.0 MPaG. After the reaction was completed, the reaction solution in the reactor was cooled to room temperature, and the remaining gas in the reactor was released to obtain 192 g of a hydroformylation reaction product solution. The amount of dicyclopentadiene, a raw material compound, contained in the reaction solution before the reaction and the amount of tricyclodecane dicarbaldehyde, a product in the hydroformylation reaction product solution after the reaction, were analyzed by gas chromatography to determine the yield of tricyclodecane dicarbaldehyde. The yield was 99%.

[0180] <Extraction Procedure> 51 g of methanol and 35 g of water were added to 172 g of the obtained hydroformylation reaction product liquid, and the mixture was stirred for 30 minutes under a nitrogen atmosphere. The mixture was then allowed to stand for 30 minutes, allowing it to separate into two phases, and an extraction procedure was then carried out. 6.6 g of methylcyclohexane was added to the obtained lower phase (a1), and the mixture was stirred for 30 minutes. The mixture was then allowed to stand for 30 minutes, allowing it to separate into two phases, and an extraction procedure was then carried out, yielding 202.3 g of lower phase (a2). The composition of the obtained lower phase (a2) was analyzed by gas chromatography, and it was found to contain 52 mass% tricyclodecane dicarbaldehyde, 27 mass% methanol, 14 mass% water, 2 mass% methylcyclohexane, and 5 mass% other components.

[0181] <Hydrogenation reduction reaction> 200 g of the lower phase (a2) obtained by the above-mentioned extraction operation and 0.6 g of ruthenium-supported carbon as a hydrogenation reduction reaction catalyst were charged into a 500 mL autoclave reactor, and the temperature of the reaction solution in the reactor was raised to 160 ° C. while stirring at 1200 rpm. Next, hydrogen gas was injected through the gas inlet valve so that the pressure in the reactor was 3 MPaG, and the reaction was carried out for 3 hours while maintaining this pressure and the temperature of the reaction solution. During the reaction, the amount of mixed gas consumed in the reaction was continuously introduced into the reactor so as to maintain the pressure in the reactor at 3 MPaG. After completion of the reaction, the reaction solution in the reactor was cooled to room temperature, the remaining gas in the reactor was depressurized, and the ruthenium-supported carbon was filtered using a filter with a pore size of 5 μm, obtaining 176 g of a reaction product solution. The amount of tricyclodecane dicarbaldehyde, a raw material compound, contained in the reaction solution before the reaction and the amount of TCDDM, a product in the reaction solution after the reaction, were analyzed by gas chromatography. The yield of TCDDM was 98%.

[0182] <Distillation Purification> 170 g of the reaction product liquid after the hydroreduction reaction was charged into a batch-type distillation column (a four-neck flask with an internal volume of L) equivalent to five structured packing plates. 80.2 g of low-boiling components, primarily solvent, were distilled off at a minimum internal column pressure of 10 kPaA and a maximum column bottom temperature of 100°C. Distillation was then continued at an internal column pressure of 0.3 kPaA and a column bottom temperature of 120°C until 1.5 g of distillate was obtained from the top of the distillation column. The distillation column equivalent to five structured packing plates was then replaced with a glass pot distillation column, and simple distillation was carried out at a pressure of 0.3 kPaA and a temperature of 165°C, distilling the TCDDM composition from the top of the column. The initial fraction and the main fraction were recovered in this order. The yield of the TCDDM composition recovered as the main fraction was 64.6 g. The values ​​of S, T, Ya, Za, and (Ya-Za) x (T / S) x 100 for this distillation purification are shown in Table 1.

[0183] The resulting TCDDM compositions were evaluated for Xa / Xt, Xb / Xt, Xc / Xt, Xd / Xt, and Xb / (Xa+Xc+Xd), as well as for storage stability. The evaluation results are shown in Table 2.

[0184] Example 2 A hydroreduction reaction was carried out under the same conditions as in Example 1, except that a nickel-supported diatomaceous earth catalyst was used instead of the ruthenium-supported carbon, and 175 g of a reaction product liquid was obtained. The yield of TCDDM obtained by the hydroreduction reaction was 99%. Next, 170 g of the reaction product liquid after the hydroreduction reaction was subjected to distillation purification under the same conditions as in Example 1, except that in the distillation purification of Example 1, the values ​​of S, T, Ya, Za, and (Ya-Za) x (T / S) x 100 were changed as shown in Table 1. The amount of TCDDM composition recovered as the main fraction after distillation purification was 754 g. The evaluation results of the obtained TCDDM composition are shown in Table 2.

[0185] Example 3 A hydroreduction reaction was carried out under the same conditions as in Example 1, except that the temperature of the reaction solution was changed from 160°C to 180°C and a nickel-supported diatomaceous earth catalyst was used instead of ruthenium-supported carbon, yielding 176 g of a reaction product solution. The yield of TCDDM obtained from the hydroreduction reaction was 99%. Next, 170 g of the reaction product solution after the hydroreduction reaction was subjected to distillation purification under the same conditions as in Example 1, except that the values ​​of S, T, Ya, Za, and (Ya-Za) x (T / S) x 100 in the distillation purification procedure of Example 1 were changed as shown in Table 1. The yield of the TCDDM composition recovered as the main fraction after distillation purification was 65.3 g. The evaluation results of the resulting TCDDM composition are shown in Table 2.

[0186] Example 4 A hydroreduction reaction was carried out under the same conditions as in Example 1, except that a copper oxide / aluminum oxide-containing catalyst was used instead of the ruthenium-supported carbon in the hydroreduction reaction of Example 1. 174 g of a reaction product was obtained. The yield of TCDDM obtained in the hydroreduction reaction was 99%. Next, in the distillation purification of Example 1, a distillation column equivalent to 15 structured packing plates (a 3-L four-neck flask) was used instead of the batch distillation column equivalent to 5 structured packing plates. Low-boiling components, mainly solvent, were distilled off from 170 g of the reaction product after the hydroreduction reaction. The distillation was continued at an internal pressure of 0.6 kPaA and a bottom temperature of 185°C until 11.6 g of distillate was obtained from the top of the distillation column. The distillation column equivalent to 15 structured packing plates was then replaced with a glass pot distillation column, and simple distillation was carried out under the same conditions as in Example 1. The amount of TCDDM composition recovered as the main fraction after simple distillation was 53.0 g. The values ​​of S, T, Ya, Za, and (Ya-Za) x (T / S) x 100 in this distillation purification are shown in Table 1. The evaluation results of the obtained TCDDM composition are shown in Table 2.

[0187] Comparative Example 1 In the distillation purification of Example 1, a distillation column equivalent to 20 structured packing plates (a 3-L four-neck flask) was used instead of the batch distillation column equivalent to 5 structured packing plates. Light-boiling components, primarily solvent, were distilled off from 170 g of the reaction product liquid after the hydrogenation reduction reaction. The distillation was continued at an internal pressure of 0.6 kPaA and a bottom temperature of 185°C until 11.7 g of distillate was obtained from the top of the distillation column. The distillation column equivalent to 20 structured packing plates was then replaced with a glass pot distillation column, and simple distillation was carried out under the same conditions as in Example 1. The yield of the TCDDM composition recovered as the main fraction after the simple distillation was 54.8 g. The values ​​of S, T, Ya, Za, and (Ya-Za) x (T / S) x 100 for this distillation purification are shown in Table 1. The evaluation results of the resulting TCDDM composition are shown in Table 2.

[0188] Comparative Example 2 A hydroreduction reaction was carried out under the same conditions as in Example 1, except that the temperature of the reaction liquid was changed from 160°C to 120°C, and 177 g of a reaction product liquid was obtained. The yield of TCDDM obtained by the hydroreduction reaction was 98%. Next, 170 g of the reaction product liquid after the hydroreduction reaction was subjected to distillation purification under the same conditions as in Example 1, except that in the distillation purification of Example 1, the values ​​of S, T, Ya, Za, and (Ya-Za) x (T / S) x 100 were changed as shown in Table 1. The amount of TCDDM composition recovered as the main fraction after simple distillation was 65.1 g. The evaluation results of the obtained TCDDM composition are shown in Table 2.

[0189] Comparative Example 3 A hydroformylation reaction was carried out under the same conditions as in Example 1, except that the amount of tris(2,4-di-tert-butylphenyl)phosphite was changed from 870 mg to 1450 mg and the pressure in the reactor was changed from 3.0 MPaG to 5.0 MPaG, to obtain a hydroformylation reaction product. The yield of tricyclodecane dicarbaldehyde obtained was 98%. Next, 193 g of the obtained hydroformylation reaction product was subjected to extraction, hydrogenation reduction, and distillation purification under the same conditions as in Example 1, except that in the distillation purification of Example 1, the values ​​of S, T, Ya, Za, and (Ya-Za) x (T / S) x 100 were changed as shown in Table 1. The amount of TCDDM composition recovered as the main fraction after simple distillation was 63.6 g. The evaluation results of the obtained TCDDM composition are shown in Table 2.

[0190] The TCDDM compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were subjected to gas chromatography mass spectrometry by the method described above to measure the m / z and fragment patterns. It was confirmed that peaks 1 to 3 in each case exhibited m / z and fragment patterns corresponding to TCDDM. Representative fragments observed are listed below. MS(EI): 178 ([M-18]+), 165, 147, 119, 105, 91, 81, 67

[0191]

[0192]

[0193] In evaluating storage stability, a lower dynamic light scattering intensity analysis value indicates lower crystallinity and higher fluidity of the TCDDM composition, i.e., better storage stability of the TCDDM composition. As can be seen from Table 1, the TCDDM compositions obtained in Examples 1 to 4 had better storage stability than the TCDDM compositions of Comparative Examples 1 to 3. In particular, the TCDDM compositions of Examples 2 and 3 had even better storage stability. The TCDDM compositions obtained in Comparative Examples 1 and 3 had poor storage stability due to their large Xa / Xt values. Furthermore, the TCDDM composition obtained in Comparative Example 2 had poor storage stability due to its small Xb / Xt value.

[0194] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application No. 2023-148245 filed on September 13, 2023 and Japanese Patent Application No. 2024-017280 filed on February 7, 2024, both of which are incorporated by reference in their entirety.

Claims

1. A tricyclodecane dimethanol composition comprising a chiral compound A having one enantiomer represented by the following formula (I), a chiral compound B having one enantiomer represented by the following formula (II), a chiral compound C having one enantiomer represented by the following formula (III), and a chiral compound D having one enantiomer represented by the following formula (IV), wherein the number of moles Xa of the chiral compound A, the number of moles Xb of the chiral compound B, and the total number of moles Xt of the chiral compounds A, B, C, and D, as measured by nuclear magnetic resonance spectroscopy, satisfy Xa / Xt≦0.430 and Xb / Xt≧0.

016.

2. The tricyclodecane dimethanol composition according to claim 1, wherein Xb and Xt satisfy Xb / Xt≧0.

020.

3. The tricyclodecane dimethanol composition according to claim 1, wherein Xa and Xt satisfy Xa / Xt≦0.

400.

4. The tricyclodecane dimethanol composition according to claim 1, wherein Xb and Xt satisfy Xb / Xt≧0.

027.

5. The tricyclodecane dimethanol composition according to claim 1, wherein Xa and Xt satisfy Xa / Xt<0.

350.

6. The tricyclodecane dimethanol composition according to claim 1, wherein the molar number Xc of the chiral compound C and the Xt satisfy Xc / Xt≧0.300 as measured by nuclear magnetic resonance spectroscopy.

7. The tricyclodecane dimethanol composition according to claim 1, wherein the number of moles Xd of the chiral compound D and Xt satisfy Xd / Xt≧0.240 as measured by nuclear magnetic resonance spectroscopy.

8. The tricyclodecane dimethanol composition according to claim 1, wherein Xa, Xb, the number of moles Xc of the chiral compound C measured by nuclear magnetic resonance spectroscopy, and the number of moles Xd of the chiral compound D satisfy Xb / (Xa+Xc+Xd)≧0.

010.

9. The tricyclodecane dimethanol composition according to claim 1, wherein the chiral compound B is detected within a retention time range of 13.65 to 13.85 minutes when the composition is measured using gas chromatography (GC) under the following measurement conditions: (Measurement conditions) Column: Capillary column (length 30 m x inner diameter 0.25 mm x film thickness 1 μm) Liquid phase: 100% dimethylpolysiloxane Carrier gas: Helium Carrier gas column flow rate: 1 mL / min Split ratio: 1 / 30 Injection amount: 0.3 μL Oven temperature: 160°C (no retention time) → heating at 5°C / min → 300°C (retention time 2 minutes) Injection port temperature: 200°C Detector: Flame ionization detector (temperature 300°C) 10. The tricyclodecane dimethanol composition according to claim 9, wherein the chiral compound A is detected within a retention time range of 13.85 to 14.05 minutes when the composition is measured using gas chromatography (GC) under the measurement conditions.

11. An ultraviolet light curable composition derived from the tricyclodecane dimethanol composition according to any one of claims 1 to 10.

12. The ultraviolet ray curable composition according to claim 11, which is used as any one of a hard coat material, an antifouling coat material, a resist material, an inkjet ink, and a material for a 3D printer.

13. A polymer composition derived from the tricyclodecane dimethanol composition according to any one of claims 1 to 10.

14. The polymer composition according to claim 13, wherein the polymer in the polymer composition is at least one selected from the group consisting of polyester-based resins, epoxy-based resins, acrylate-based resins, polycarbonate-based resins, and polyurethane-based resins.

15. A polymer composition derived from the ultraviolet curable composition of claim 11.

16. The polymer composition according to claim 15, wherein the polymer in the polymer composition is at least one selected from the group consisting of polyester-based resins, epoxy-based resins, acrylate-based resins, polycarbonate-based resins, and polyurethane-based resins.

17. A method for producing a tricyclodecane dimethanol composition, comprising: a step of hydroformylating dicyclopentadiene to obtain tricyclodecane dicarbaldehyde; a step of reducing the tricyclodecane dicarbaldehyde to obtain a crude reaction liquid containing tricyclodecane dimethanol; and a step of purifying the crude reaction liquid by distillation to obtain the tricyclodecane dimethanol composition according to any one of claims 1 to 10.

18. The method for producing a tricyclodecane dimethanol composition according to claim 17, wherein the reaction pressure of the hydroformylation is 0.5 MPaG or more and 4.5 MPaG or less, the temperature of the reduction reaction is 125°C or more and 350°C or less, and the distillation conditions in the distillation purification satisfy the following formula (1): (Ya-Za) x T / S x 100≦1.65 (1) (In formula (1), Ya: mass ratio of chiral compound A in the crude reaction solution supplied to the distillation purification step (unit: dimensionless number); S: total weight (unit: g) of chiral compound A, chiral compound B, chiral compound C, and chiral compound D in the crude reaction solution supplied to the distillation purification step; Za: mass ratio (unit: dimensionless number) of chiral compound A in the distillate distilled out of the purification system from the distillation column in the distillation purification step; and T: total weight (unit: g) of chiral compound A, chiral compound B, chiral compound C, and chiral compound D in the distillate distilled out of the purification system from the distillation column in the distillation purification step.)

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