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

Abstract

To provide a tricyclodecanedimethanol composition having superior storage stability.SOLUTION: A tricyclodecanedimethanol composition comprising chiral compounds A to D, one of enantiomers of which is represented by the following Formulae (I) to (IV), respectively, wherein when the number of moles of the chiral compound A, the number of moles of the chiral compound B, and the total number of moles of the chiral compounds A to D as measured by nuclear magnetic resonance spectrometry are defined as Xa, Xb, and Xt, respectively, the composition satisfies Xa / Xt≤0.430 and Xb / Xt≥0.016.SELECTED DRAWING: None

Description

[Technical Field]

[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. [Background technology]

[0002] Tricyclodecane dimethanol (hereinafter abbreviated as "TCDDM") is a dihydric alcohol with 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 Document 1, Patent Document 2, Patent Document 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 with 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. TCDDM has therefore attracted attention as a synthetic raw material for molding materials such as polyesters and polycarbonates. Derivatives of TCDDM, such as diacrylate derivatives, dimethacrylate derivatives, and urethane acrylates, synthesized using TCDDM as a raw material, are used as ultraviolet-curable compositions. Cured products using such ultraviolet-curable compositions exhibit excellent performance in terms of surface hardness, heat resistance (glass transition temperature), thermal decomposition resistance, and development resistance, due to the alicyclic structure of TCDDM. Therefore, they are attracting attention as electronic materials such as hard coats, antifouling coats, and resists, as well as display device components.

[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") mainly composed of multiple isomers with different bonding positions of the hydroxymethyl group in the five-membered ring (Non-Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-132624 [Patent Document 2] Patent Publication No. 2021-520401 [Patent Document 3] International Publication No. 2023 / 277347 [Non-patent literature]

[0006] [Non-Patent Document 1] Hitachi Chemical Technical Report, No. 51 (2008-7), pp. 7-12 [Non-patent document 2] Applied Catalyst,Vol.19,pp259-273(1985) Summary of the Invention [Problem to be solved by the invention]

[0007] The present inventors have newly discovered that, depending on the composition of the TCDDM composition, even if the TCDDM composition obtained by distillation purification after a hydrogen reduction reaction has fluidity immediately after distillation, the fluidity may decrease during storage, resulting in poor handleability, i.e., the TCDDM composition may have poor storage stability.

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

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

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

[0011] The present inventors have found that in a TCDDM mixture composed mainly of four isomers differing in the position of the hydroxymethyl group bond, it is effective to appropriately control the isomer ratio. More specifically, the inventors have found that a TCDDM composition with 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 higher, 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 lower.

[0012] The present invention provides the following.

[0013] [1] A chiral compound A, one of whose enantiomers is represented by the following formula (I), a chiral compound B, one of whose enantiomers is represented by the following formula (II), a chiral compound C, one of whose enantiomers is represented by the following formula (III), and a chiral compound D, one of whose enantiomers is represented by the following formula (IV), The tricyclodecane dimethanol composition, 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 satisfy Xa / Xt≦0.430 and Xb / Xt≧0.016, as measured by nuclear magnetic resonance spectroscopy.

[0014] [ka]

[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 molar number Xc of the chiral compound C and the 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 molar number Xd of the chiral compound D and the Xt, as detected by an NMR method, satisfy Xd / Xt≧0.240. [8] The tricyclodecane dimethanol composition according to any one of [1] to [7], wherein Xa, Xb, the number of moles of the chiral compound C, Xc, and the number of moles of the chiral compound D, Xd, as 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 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 volume: 0.3μL Oven temperature: 160°C (no holding time) → Heat at 5°C / min → 300°C (holding time 2 min) Inlet temperature: 200℃ 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: a step of hydroformylating dicyclopentadiene to obtain tricyclodecane dicarbaldehyde; a step of subjecting the tricyclodecane dicarbaldehyde to a reduction reaction to obtain a crude reaction solution containing tricyclodecane dimethanol; and a step of purifying the crude reaction solution by distillation to obtain the tricyclodecane dimethanol composition according to any one of [1] to

[10] .

[16] 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 higher and 350°C or lower, The method for producing a tricyclodecane dimethanol composition according to

[15] , wherein the distillation conditions in the distillation purification satisfy the following formula (1): (Ya-Za)×T / S×100≦1.65 (1) (In formula (1), Ya: mass fraction 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 fraction of chiral compound A in the distillate removed from the distillation column during the distillation purification process (unit: dimensionless number) T: The total weight (unit: g) of chiral compounds A, B, C, and D in the distillate removed from the distillation column during the distillation purification process. [Effects of the Invention]

[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 showing no decrease in fluidity even after long-term storage can be provided. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is a gas chromatogram of the TCDDM composition obtained in Example 2. [Figure 2] Figure 2(a) shows the C-NMR spectrum of the TCDDM composition obtained in Example 2. Figure 2(b) shows the C-NMR spectrum of the TCDDM composition obtained in Comparative Example 1. In Figures 2(a) and 2(b), the subscripts "A," "B," "C," and "D" added to the NMR peaks indicate that the peaks correspond to "chiral compound A," "chiral compound B," "chiral compound C," and "chiral compound D," respectively. DETAILED DESCRIPTION OF THE INVENTION

[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 ​​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 specific component contained in a total amount of 100 mass %. "mass %" and "weight %" have the same meaning. As used herein, "optional" or "optionally" means that the subsequently described situation may or may not occur, and therefore the description includes both the occurrence and non-occurrence of the situation.

[0026] As used herein, the term "about" means that the stated value can be included above and below 20%. 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 stated 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] As represented by the following general formulas (I) to (IV), the chiral compounds A, B, C, and D each have one hydroxymethyl group (CHOH group) in the six-membered ring portion of a norbornane ring and another hydroxymethyl group in the five-membered ring portion.

[0030] [ka]

[0031] As described above, chiral compound A, chiral compound B, chiral compound C, and chiral compound D in the present invention exist as R- and S-enantiomers (also called 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 as an endo isomer and an exo isomer, 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). The details of the method for measuring Xa, Xb, Xc and Xd in the present invention will be described in the Examples section.

[0034] <Xa / Xtについて> 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 the Xa / Xt ratio 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 it 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 obtained TCDDM composition.

[0038] <Xb / Xtについて> 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, it can be set to Xb / Xt≦0.13. 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 X / X value is not particularly limited, and a person skilled in the art can control the X / X value by appropriately optimizing the production conditions according to well-known techniques. For example, the X / X value can be controlled by optimizing the hydroformylation reaction conditions, the distillation conditions for distilling and purifying the resulting TCDDM composition, and the like.

[0042] <Xc / Xtについて> 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 arbitrarily. For example, in the TCDDM composition of the present invention, Xc / Xt is not particularly limited, but can be 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 it 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, the distillation conditions for distilling and purifying the obtained TCDDM composition, and the like.

[0046] <Xd / Xtについて> 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 it by appropriately optimizing 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] <Xb / (Xa+Xc+Xd)について> 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 greater (Xb / (Xa+Xc+Xd)≧0.010), preferably 0.023 or greater, more preferably 0.027 or greater, and even more preferably 0.032 or greater.

[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] The upper and lower limits can be combined in any way. 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 obtained 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 using gas chromatography (GC) under the following measurement conditions. In the TCDDM composition of the present invention, the chiral compound A is a compound detected within the range of retention times of 13.85 to 14.05 minutes when the composition is measured under the following measurement conditions using gas chromatography (GC).

[0055] (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 volume: 0.3 μL Oven temperature: 160°C (no hold time) → temperature increase at 5°C / min → 300°C (hold time 2 minutes) Inlet temperature: 200°C Detector: Flame ionization detector (temperature 300°C) [[ID=​​​​​​​​​​​​​

[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 a mixture of tricyclodecane dicarbaldehydes is obtained, which are precursors of chiral compound A, chiral compound B, chiral compound C, and chiral compound D. Then, 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 of dicyclopentadiene> The method for hydroformylating dicyclopentadiene is not particularly limited, and 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 the following reaction formula (V), to produce tricyclodecane dicarbaldehyde.

[0063] [ka]

[0064] The rhodium compound used in this hydroformylation step can be any precursor, as long as it forms a complex with an organophosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide. These compounds include Rh(acac)(CO)2, Rh2O3, and Rh4(CO). 12 , Rh6(CO) 16 Alternatively, a catalyst precursor such as Rh(NO3)3 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 effective in the hydroformylation reaction of dicyclopentadiene, and is therefore selected from the group consisting of phosphites represented by the general formula P(-OR 1 )(-OR 2 )(-OR 3 )(wherein, R 1 , R 2 and R 3 and each represent an optionally substituted aryl group or alkyl group. R 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 is in the range of 1 to 400 times by mole, preferably 3 to 200 times by mole, relative to the rhodium metal in the hydroformylation reaction solution, 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. When rhodium is used at 50 ppm or more, it becomes necessary to recover the catalyst.

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

[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 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 is preferably 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 will decrease.

[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, and the product tricyclodecane dicarbaldehyde is extracted into the alcohol while the catalyst components remain 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. 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 preferably used because they have a relatively low boiling point, 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 by using an extraction solvent with a low volume ratio (extraction solvent / reaction product solution). The higher the concentration of the product, the higher the volume ratio (extraction solvent / reaction product solution) required to extract tricyclodecane dicarbaldehyde 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 in the range of 10:1 to 1:10. In order 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 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] There is no particular limitation on the temperature at which the extraction operation is carried out, but it is practical to carry out the operation at a temperature equal to or lower than the hydroformylation reaction temperature. After the reaction, an extraction solvent may be added to the hydroformylation reactor to carry out the extraction operation, 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 directly adding the extraction solvent to the hydroformylation reactor, and then retain the catalyst components in the hydroformylation reactor to carry 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 extraction procedure can produce 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 produced.

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

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

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

[0096] [ka]

[0097] The amount of water present in the hydrogenation reduction reaction is preferably equal to or greater than the amount of 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 aforementioned effects of having water present in the hydrogenation reaction system can be effectively obtained. The addition of water 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, 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 loading of 12% and a chromium loading of 2% disclosed in Example 1 of JP-A-2005-279587 can be used.

[0099] As the reaction mode for the hydrogenation reduction reaction, a method in which the catalyst is charged as a slurry in a stirred reactor, the reaction is carried out in a batch system, 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, may be appropriately adopted. The amount of catalyst used is not particularly limited as long as it enables TCDDM to be produced with industrially advantageous productivity.

[0100] The reaction temperature for the hydrogenation reduction reaction can be set within a 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) and the content ratio of chiral compound B (Xb / Xt) in the resulting TCDDM composition within a 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 be 0.016 or greater, the lower limit of the reaction temperature for the hydroreduction reaction is preferably 125°C or greater, more preferably 130°C or greater, even more preferably 140°C or greater, particularly preferably 145°C or greater, and most preferably 150°C or greater. 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 less, more preferably 300°C or less, even more preferably 250°C or less, particularly preferably 200°C or less, and most preferably 180°C or less.

[0101] The above upper and lower limits can be combined arbitrarily. 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 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. Meanwhile, the lower limit of this reaction pressure is usually 1 MPaG.

[0103] <Removal of residual metals> The crude reaction mixture obtained by the above hydrogenation-reduction reaction procedure contains metal elements derived from the hydrogenation catalyst as eluted components. By removing the metal elements from the crude reaction mixture prior to distillation purification, thermal decomposition of TCDDM caused by the metal elements during the distillation purification process can be suppressed.

[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 better 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 solution to be subjected to distillation purification is preferably within the range of 6 to 8. A pH lower limit of 6 or higher is preferred because it can suppress the by-production of low-boiling compounds thought to result from dehydration of TCDDM and high-boiling compounds thought to result from dimerization such as etherification. A pH upper limit of 8 or lower is preferred because it 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 is subjected to treatment to remove 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 and 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 in the distillation purification step are not particularly limited, and distillation purification can be performed, for example, using a purification system equipped with one or more distillation columns. Specifically, distillation purification can be performed 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 distillation 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 by distillation purification under conditions that satisfy the following formula (1):

[0115] (Ya-Za)×T / S×100≦1.65 (1) (In formula (1), Ya: mass fraction 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 fraction of chiral compound A in the distillate removed from the distillation column during the distillation purification process (unit: dimensionless number) T: The total weight (unit: g) of chiral compounds A, B, C, and D in the distillate removed from the distillation column during the distillation purification process. )

[0116] In this specification, the phrase "distilled outside the purification system" means that the bottom distillate and / or 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 equipped with 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 that represents the proportion of chiral compound A that is distilled out of the purification system during the distillation purification process. The smaller the value of (Ya-Za), the less chiral compound A is contained in the obtained TCDDM composition, and the smaller the value of Xa / Xt tends to be. In the formula (1), T / S is an index value that represents the proportion of chiral compounds B, C, and 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 T / S value, the less chiral compound A is contained in the obtained TCDDM composition, and the smaller the Xa / Xt value tends to be.

[0119] In other words, the value of (Ya-Za) x T / S x 100, expressed by the above formula (1), is an index value showing the proportion of chiral compound A that is distilled off (discharged) from the distillation column to the outside of the purification system during the distillation purification process. By adopting distillation conditions that reduce this value, the content 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 tends to be economically disadvantageous as it becomes necessary to increase the number of theoretical plates and the reflux ratio of the distillation column. The above upper and lower limits can be combined in any way. 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 the distillation purification, the bottom temperature of the distillation column is not particularly limited, but it can be preferably set within the range of 150°C or higher and 300°C or lower. If the lower limit of the distillation column bottom temperature is 150°C or higher, TCDDM can be efficiently volatilized. The lower limit of the distillation column bottom temperature 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 distillation column bottom temperature 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 distillation column bottom temperature 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 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 distillation column used for distillation purification has a lower limit of the number of theoretical plates of 5 or more, it is easy to separate the impurities from the product. The lower limit of the number of theoretical plates of the distillation column is 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, so the heat load of the equipment is reduced. The upper limit of the number of theoretical plates of the distillation column is 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 can be combined arbitrarily.

[0123] There are no particular limitations on other distillation column conditions for distillation purification, but distillation is typically carried out at a pressure of 0.1 kPaA or more and 100 kPaA or less, and a reflux ratio of approximately 1 or more and 30 or less. In particular, by controlling the reflux ratio and the distillate amount, it is 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, distillation column 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. Such distillation purification can usually produce a TCDDM composition with a TCDDM purity of 98% or more in high yield.

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

[0126] There is no particular limitation on the method for producing the ultraviolet-curable composition, and it can be produced according to a conventional method. In general, it is desirable to use tricyclodecane dimethanol in the TCDDM composition as a raw material to produce and use a derivative such as a di(meth)acrylic acid ester derivative or a urethane acrylate.

[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 reacting TCDDM with (meth)acrylic acid, subjecting TCDDM to an ester exchange reaction with a (meth)acrylic acid ester, and 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 a di(meth)acrylic acid ester derivative is produced 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; and hydroxides such as potassium hydroxide and sodium hydroxide, and any of these can be selected and used. 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, from the viewpoint of reducing the load on the production equipment and reducing raw material costs.

[0133] Examples of the catalyst include catalysts known 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, 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.

[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, and phenyl-β-naphthylamine. The amount of the polymerization inhibitor used is preferably 10 to 100,000 ppm based on 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 may 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 thereof 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 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, there is no particular upper limit to the content, and a higher content is preferable.

[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 their hydrogenated derivatives, 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. Furthermore, methacrylate compounds in which the acrylate in the above 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, and the like; diols having an alicyclic structure such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, and the like; diols having an aromatic group such as xylylene glycol, 1,4-dihydroxyethylbenzene, 4,4'-methylenebis(hydroxyethylbenzene), and the like; polyols such as glycerin, trimethylolpropane, and pentaerythritol; 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] In order to prevent thermal polymerization of the monohydroxyacrylate compound or the like, it is preferable to add a polymerization inhibitor. 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 the polymerization inhibitor used is preferably 10 to 100,000 ppm based on 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 may 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 thereof 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 exhibits excellent coating stability without impairing the performance inherently required of a UV-curable composition. Therefore, the UV-curable composition of the present invention is suitable for use as a hard coat material, an antifouling coat material, a resist material, an inkjet ink, a material for 3D printers, and the like.

[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 ultraviolet-curable composition of the present invention can be suitably used for applications such as hard coat materials, antifouling coat 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 ultraviolet-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 includes 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 ultraviolet-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 polymer 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, it may be a polymer composition obtained by purifying a composition containing a polymer obtained by polymerization by appropriate removal of impurities, or may be a polymer composition obtained by further adding, as necessary, appropriate additives such as storage stabilizers (such as ultraviolet absorbers and antioxidants), colorants, antistatic agents, lubricants, fillers, flame retardants, foaming agents, etc., within a range that does not affect the performance of the polymer obtained by polymerization. That is, the polymer composition of the present invention is not particularly limited as long as it contains a polymer obtained by polymerizing the TCDDM composition of the present invention or the ultraviolet-curable composition of the present invention, and there are no particular limitations on the form or component composition thereof.

[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 whose main component is a polyethylene polymer such as polyethylene terephthalate (PET). The polyethylene polymer is not particularly limited, and refers to, for example, a polymer that contains structural units derived from a polyol mainly containing glycol and structural units derived from a terephthalic acid compound, and also contains 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 resin refers to a resin containing a polycarbonate polymer as a main component. The polycarbonate polymer is not particularly limited, and examples thereof include polymers containing structural units derived from bisphenol compounds, 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. [Example]

[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 Corporation) · Acetylacetonato dicarbonyl rhodium (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 Corporation) · Ruthenium supported carbon (dry base Ru content 5%, water content 56%) (trade name: Ru / C, manufactured by N.E. Chemcat Corporation) · Nickel supported diatomaceous earth catalyst (manufactured by the company itself according to the description of Example 1 of JP-A-2005-279587, nickel supported diatomaceous earth with a nickel loading of 12% and a chromium loading of 2%) · Catalyst containing copper oxide and aluminum oxide (trade name: HySat, tablet size: 3×3 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 the TCDDM composition> Chiral compounds A to D contained in the TCDDM compositions obtained in the examples and comparative examples were calculated by the following procedure using nuclear magnetic resonance spectroscopy measurement.

[0164] A sample of the TCDDM composition was dissolved in deuterated chloroform (CDCl3, containing 0.03 v / v% TMS), and the sample solution was transferred to an NMR sample tube with an outer diameter of 5 mm. Using a nuclear magnetic resonance spectroscopy measuring device (trade name: AVANCE NEO 600 type NMR, manufactured by Bruker), the 1 1H-NMR, 13 13C-NMR, DEPT, COSY, TOCSY, NOESY, 1 1H- 13 13C HSQC, 1 1H- 13 13C HMBC spectra of the sample solution were measured. 1The measurement conditions for 1H-NMR were as follows: resonance frequency 600 MHz, flip angle 45°, data acquisition time 3 s, pulse repetition time 10 s, number of accumulations 16, and measurement temperature 25°C. The reference for chemical shift was set such that the signal of TMS was 0.00 ppm. 13 The measurement conditions for 13C-NMR were as follows: resonance frequency 151 MHz, flip angle 45°, data acquisition time 2 s, pulse repetition time 5 s, number of accumulations 10000, and temperature 25°C. The reference for chemical shift was set such that the signal of TMS was 0.00 ppm. The structure was identified from the signal correlations.

[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, the number of moles Xd of chiral compound D, and the total number of moles Xt (= Xa + Xb + Xc + Xd) of chiral compounds 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 the following procedure using nuclear magnetic resonance spectroscopy (NMR) measurement method.

[0166] 65 mg of a sample of the TCDDM composition was transferred to a sample tube, and 0.75 mL of deuterated chloroform (CDCl3 containing 0.03 v / v% TMS (tetramethylsilane)) was added, and this was used as a sample for NMR measurement. Since the sample of Comparative Example 1 became turbid when deuterated chloroform was added, 83 μL of deuterated dimethyl sulfoxide (DMSO-d6 containing 0.05 v / v% TMS) was further added to the sample, and when it was made into a mixed solution of CDCl3:DMSO-d6 = 9:1, it became transparent, and this mixed solution was used as a sample for NMR measurement. The sample for NMR measurement was transferred to an NMR sample tube with an outer diameter of 5 mm, and using a nuclear magnetic resonance spectrometer (trade name: AVANCE NEO 600 type NMR, manufactured by Bruker) 1 3 a 13C-NMR spectrum was measured. 13The 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. The TCDDM compositions obtained in Example 2 and Comparative Example 1 13 The C-NMR spectra are shown in Figure 2(a) and Figure 2(b), respectively.

[0167] The number of moles (Xa, Xb, Xc, Xd) and Xt (=Xa+Xb+Xc+Xd) of each of chiral compounds A, B, C, and D 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). In addition, only for chiral compound A in Comparative Example 1, the signal of carbon α on the norbornane ring overlapped with other signals. Therefore, as shown in the following structural formula (2), 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.

[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, the signal of the 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] [ka]

[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) Measurement equipment: Gas chromatograph (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 volume: 0.3 μL Oven temperature (heating conditions): 160°C (no holding time) → Heat at 5°C / min → 300°C (holding time 2 min) Inlet temperature: 200℃ Ion source temperature: 300℃ Split ratio: 1 / 30 Detector: Flame ionization detector (temperature 300°C)

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

[0173] <Mass spectrometry of the TCDDM composition> For the TCDDM compositions obtained in the examples and comparative examples, in order to confirm that TCDDM was produced, m / z and the fragmentation pattern were measured by gas chromatography - mass spectrometry using the following procedure. (Gas chromatography - mass spectrometry conditions)

[0174] Measuring device: Gas chromatogram measuring 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 (temperature - rising condition): 160°C → temperature rising at 5°C / min → 300°C (holding time 2 minutes) 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 composition was measured by dynamic light scattering analysis using the following procedure. Also, during the above measurement, the fluidity of the TCDDM composition was visually observed.

[0176] A sample of the TCDDM composition placed in a glass reagent bottle was immersed in an oil bath set to a temperature of 60°C, and the sample was heated while being stirred 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, the dynamic light scattering intensity was measured and the fluidity was visually observed under the measurement conditions described below. The dynamic light scattering intensity measurements and visual observation of fluidity were carried out 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) Measurement device: Dynamic light scattering measurement device (product name: Zetasizer Nano ZS, manufactured by Malvern Panalytical) Detection method: 173° backscattering detection method (a scattered light detector is placed 173° behind the sample.) Sample temperature: 60℃ Cell: Glass

[0178] Furthermore, the storage stability of the TCDDM composition was evaluated according to the following criteria. The fluidity was assessed 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 up 10 cm. If the composition exhibited spinnability, it was assessed as "fluidity present," and if it did not exhibit spinnability, it was assessed as "no fluidity." (Judgment criteria) A: The TCDDM composition exhibited fluidity after 196 hours, and the dynamic light scattering intensity was 3500 or less. B: The TCDDM composition was fluid after 196 hours and had a dynamic light scattering intensity of over 3500. C: The TCDDM composition showed fluidity after 96 hours, but after 175 hours it showed no fluidity and the dynamic light scattering intensity exceeded 100,000. D: The TCDDM composition showed no flowability after 96 hours and had a dynamic light scattering intensity of over 100,000.

[0179] [Example 1] <Hydroformylation reaction> In a 500 mL autoclave reactor (up-and-down stirring type), 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 under a nitrogen atmosphere. 69 g of methylcyclohexane and 89 g of dicyclopentadiene were then sequentially charged as organic solvents. The temperature of the reaction solution in the reactor was then raised to 70 °C while stirring. Next, a hydrogen and carbon monoxide mixed gas (hydrogen:carbon monoxide = 1:1 (molar ratio)) was quickly introduced through the gas inlet valve to a pressure of 3 MPaG in the reactor, and the reaction was allowed to proceed for 1 hour. The temperature of the reaction solution was then raised to 100 °C, and the reaction was allowed to proceed 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 operation> To 172 g of the obtained hydroformylation reaction product liquid, 51 g of methanol and 35 g of water were added and stirred for 30 minutes under a nitrogen atmosphere. After that, the mixture was left to stand for 30 minutes, separated into two phases, and then subjected to an extraction operation. 6.6 g of methylcyclohexane was added to the obtained lower phase (a1), and the mixture was stirred for 30 minutes. After that, the mixture was left to stand for 30 minutes, separated into two phases, and then subjected to an extraction operation, and 202.3 g of lower phase (a2) was obtained. The composition of the resulting lower phase (a2) was analyzed by gas chromatography, and was found to be 52 mass % tricyclodecane dicarbaldehyde, 27 mass % methanol, 14 mass % water, 2 mass % methylcyclohexane, and 5 mass % other components.

[0181] <Hydrogenation reduction reaction> A 500 mL autoclave reactor was charged with 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, 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 became 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 the reaction was completed, the reaction solution in the reactor was cooled to room temperature, the remaining gas in the reactor was released, and the ruthenium-supported carbon was filtered using a 5 μm pore size filter to obtain 176 g of reaction product solution. The amount of the raw material compound tricyclodecane dicarbaldehyde contained in the reaction solution before the reaction and the amount of TCDDM produced as the product in the reaction product solution after the reaction were analyzed by gas chromatography. The yield of TCDDM was 98%.

[0182] <Distillation and purification> 170 g of the reaction product liquid after the hydrogenation reduction reaction was charged into a batch distillation column (four-neck flask with an internal volume of L) equivalent to five plates of structured packing, and 80.2 g of low-boiling components mainly composed of the solvent were distilled off at a minimum internal column pressure of 10 kPaA and a maximum column bottom temperature of 100°C. Then, the internal column pressure was increased to 0.3 kPaA and the column bottom temperature to 120°C, and distillation was continued 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 single 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, which was then recovered as a first fraction and a main fraction. The amount of TCDDM composition recovered as a main fraction was 64.6 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.

[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] The hydrogenation reduction 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, to obtain 175 g of a reaction product liquid. The yield of TCDDM obtained by the hydrogenation reduction reaction was 99%. Next, 170 g of the reaction product liquid after the hydrogenation reduction 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)×(T / S)×100 in the distillation purification of Example 1 were changed as shown in Table 1. The amount of the TCDDM composition recovered as the main fraction after the distillation purification was 754 g. The evaluation results of the obtained TCDDM composition are shown in Table 2.

[0185] [Example 3] The hydrogenation reduction 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, to obtain 176 g of a reaction product solution. The yield of TCDDM obtained by the hydrogenation reduction reaction was 99%. Next, 170 g of the reaction product liquid after the hydrogenation reduction 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)×(T / S)×100 in the distillation purification of Example 1 were changed as shown in Table 1. The amount of the TCDDM composition recovered as the main fraction after the distillation purification was 65.3 g. The evaluation results of the obtained TCDDM composition are shown in Table 2.

[0186] [Example 4] The hydrogenation reduction 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, to obtain 174 g of a reaction product liquid. The yield of TCDDM obtained by the hydrogenation reduction reaction was 99%. Next, in the distillation purification of Example 1, a distillation column equivalent to 15 structured packing plates (a four-neck flask with an internal volume of 3 L) was used instead of the batch distillation column equivalent to 5 structured packing plates, and low-boiling components mainly composed of the solvent were distilled off from 170 g of the reaction product liquid after the hydrogenation reduction reaction. The distillation was then 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. Next, the distillation column equivalent to 15 structured packing plates was 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 four-neck flask with an internal volume of 3 L) was used instead of the batch distillation column equivalent to 5 structured packing plates. Light-boiling components, mainly 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 amount of 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 in this distillation purification are shown in Table 1. The evaluation results of the obtained TCDDM composition are shown in Table 2.

[0188] Comparative Example 2 The hydrogenation reduction 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 hydrogenation reduction reaction was 98%. Next, 170 g of the reaction product liquid after the hydrogenation reduction 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 of Example 1 were changed as shown in Table 1. The amount of the 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 liquid. The yield of the obtained tricyclodecane dicarbaldehyde was 98%. Next, 193 g of the obtained hydroformylation reaction product liquid was subjected to extraction, hydrogenation reduction, and distillation purification under the same conditions as in Example 1, except that the values ​​of S, T, Ya, Za, and (Ya-Za)×(T / S)×100 in the distillation purification of Example 1 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 all cases 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] [Table 1]

[0192] [Table 2]

[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 better storage stability. The TCDDM compositions obtained in Comparative Examples 1 and 3 had large Xa / Xt values ​​and therefore poor storage stability. Furthermore, the TCDDM composition obtained in Comparative Example 2 had a small Xb / Xt value and therefore was poor in storage stability.

[0194] Although the present invention has been described in detail with reference to 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 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, the entire contents of which are incorporated by reference.

Claims

1. The chiral compound A includes 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), The tricyclodecane dimethanol composition, 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 compound A, the chiral compound B, the chiral compound C, and the chiral compound D, as measured by nuclear magnetic resonance spectroscopy, satisfy Xa / Xt≦0.430 and Xb / Xt≧0.

016. 【Chemical 1】

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

020.

3. 2. 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. 2. The tricyclodecane dimethanol composition according to claim 1, wherein Xa and Xt satisfy Xa / Xt<0.

350.

6. 2. The tricyclodecane dimethanol composition according to claim 1, wherein the number of moles Xc of the chiral compound C and Xt, as measured by nuclear magnetic resonance spectroscopy, satisfy Xc / Xt≧0.

300.

7. 2. The tricyclodecane dimethanol composition according to claim 1, wherein the number of moles Xd of the chiral compound D and Xt, as measured by nuclear magnetic resonance spectroscopy, satisfy Xd / Xt≧0.

240.

8. 2. The tricyclodecane dimethanol composition according to claim 1, wherein Xa, Xb, the number of moles of chiral compound C, Xc, and the number of moles of chiral compound D, Xd, as measured by nuclear magnetic resonance spectroscopy, 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 volume: 0.3μL Oven temperature: 160°C (no holding time) → heating at 5°C / min → 300°C (holding time 2 min) Inlet temperature: 200℃ 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-curable composition derived from the tricyclodecane dimethanol composition according to any one of claims 1 to 10.

12. The ultraviolet-curable composition according to claim 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.

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

18. 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 higher and 350°C or lower, The method for producing a tricyclodecane dimethanol composition according to claim 17, wherein the distillation conditions in the distillation purification satisfy the following formula (1): (Ya-Za)×T / S×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 ratio of chiral compound A in the distillate distilled out of the purification system from the distillation column in the distillation purification process (unit: dimensionless number) 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 It is.)

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