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

Abstract

A tricyclodecane dimethanol composition containing one enantiomer of a chiral compound A represented by the following formula (I), one enantiomer of a chiral compound B represented by the following formula (II), one enantiomer of a chiral compound C represented by the following formula (III), and one enantiomer of a chiral compound D represented by the following formula (IV), wherein the number of moles Xa of the chiral compound A, the number of moles Xb of the chiral compound B, and the total number of moles Xt of the chiral compound A, the chiral compound B, the chiral compound C, and the chiral compound D, measured by nuclear magnetic resonance spectroscopy, satisfy Xa / Xt ≦ 0.430 and Xb / Xt ≧ 0.016. TIFF0007711852000009.tif58154

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 a tricyclodecane dimethanol composition.

Background Art

[0002] Tricyclodecane dimethanol (hereinafter abbreviated as "TCDDM") is a dihydric alcohol having an alicyclic structure. TCDDM is produced by subjecting dicyclopentadiene to a hydroformylation reaction with carbon monoxide and hydrogen in the presence of a catalyst to obtain an aldehyde form, and then subjecting this to hydrogen reduction (Patent Documents 1, 2, and 3).

[0003] In the fields of molding materials, electronic materials, and members for display devices, materials having an alicyclic molecular structure are used from the viewpoints of transparency, heat resistance, and low water absorption. In recent years, as a material having an alicyclic molecular structure, a polymer containing the above-described TCDDM as a constituent component has been known to exhibit excellent performance in terms of hardness, transparency, heat resistance, and low water absorption due to the alicyclic structure of TCDDM, and TCDDM has attracted attention as a synthetic raw material for molding materials such as polyesters and polycarbonates. Derivatives such as diacrylate esters, dimethacrylate esters, and urethane acrylates of TCDDM synthesized from TCDDM are used as ultraviolet curable compositions. A cured product using such an ultraviolet curable composition exhibits 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, and thus has attracted attention as an electronic material and a member for display devices such as hard coats, antifouling coats, and resists.

[0004] As an industrial production method of TCDDM, there is a method in which dicyclopentadiene is subjected to a hydroformylation reaction, then a hydrogen reduction reaction, and then distilled and purified to obtain TCDDM. In the hydroformylation reaction, the reactivity of the double bond in the norbornane ring of dicyclopentadiene is higher than that of the 5-membered ring double bond. Therefore, after the first formyl group is added to the norbornane ring, the second formyl group is added to the double bond of the 5-membered ring (Non-Patent Document 1). As a result, TCDDM obtained after the hydrogen reduction reaction is a mixture of TCDDM (hereinafter referred to as "TCDDM composition") mainly composed of a plurality of isomers with different bonding positions of hydroxymethyl groups in the 5-membered ring (Non-Patent Document 2).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Documents

[0006]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present inventors newly found that the TCDDM composition obtained by distillation purification after the hydrogen reduction reaction may have a decrease in fluidity during storage and a decrease in handleability depending on the composition of the TCDDM composition, that is, it is inferior in storage stability.

[0008] When the fluidity of the TCDDM composition decreases, it becomes difficult to pump the TCDDM composition or the raw material mixture containing the TCDDM composition (hereinafter referred to as "TCDDM composition etc.") with a gear pump or the like, or there are problems such as the TCDDM composition etc. deteriorating when heated to improve the fluidity of the TCDDM composition etc.

[0009] However, Patent Documents 1 to 3 do not mention at all that the storage stability of the TCDDM composition is inferior depending on the composition of the TCDDM composition, or 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 Problems

[0011] The present inventors have found that it is effective to appropriately control the isomer ratio in a mixture of TCDDM mainly composed of four types of isomers having different bonding positions of hydroxymethyl groups. More specifically, since one component among the four types of isomers has an action of improving the fluidity of the TCDDM composition, the component ratio of the said component is made into a predetermined value or more; And since the other one component has an action of reducing the fluidity of the TCDDM composition, the component ratio of the said component is made into a predetermined value or less; The knowledge that a TCDDM composition excellent in storage stability can be obtained was obtained.

[0012] The gist of the present invention is as follows.

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

[0014] [Chemical formula]

[0015] [2] The tricyclodecane dimethanol composition according to [1], wherein Xb and Xt satisfy Xb / Xt ≧ 0.020. [3] The tricyclodecane dimethanol composition according to [1] or [2], wherein Xa and Xt satisfy Xa / Xt ≦ 0.400. [4] The tricyclodecane dimethanol composition according to any one of [1] to [3], wherein Xb and Xt satisfy Xb / Xt ≧ 0.027. [5] The tricyclodecane dimethanol composition according to any one of [1] to [4], wherein Xa and Xt satisfy Xa / Xt < 0.350. [6] The tricyclodecane dimethanol composition according to any one of [1] to [5], wherein the number of moles Xc of the chiral compound C and Xt, detected by NMR method, satisfy Xc / Xt ≧ 0.300. [7] The tricyclodecane dimethanol composition according to any one of [1] to [6], wherein the number of moles Xd of the chiral compound D and Xt, detected by 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 Xc of the chiral compound C, and the number of moles Xd of the chiral compound D, measured by nuclear magnetic resonance spectroscopy, satisfy Xb / (Xa + Xc + Xd) ≧ 0.010. [9] When the composition is measured under the following measurement conditions using gas chromatography (GC), the chiral compound B is detected within the retention time range of 13.65 to 13.85 minutes, and is a tricyclodecane dimethanol composition as described in any one of [1] to [8]. (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)

[10] When the composition is measured under the above measurement conditions using gas chromatography (GC), the chiral compound A is detected within the retention time range of 13.85 to 14.05 minutes, and is a tricyclodecane dimethanol composition as described in [9].

[0016]

[11] A UV-curable composition derived from the tricyclodecane dimethanol composition described in any one of [1] to

[10] .

[0017]

[12] The UV-curable composition described in

[11] , which is used in 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 described in any one of [1] to

[10] , or the UV-curable composition described in

[11] or

[12] .

[14] The polymer in the polymer composition is at least one selected from the group consisting of polyester resins, epoxy resins, acrylate resins, polycarbonate resins, and polyurethane resins, the polymer composition according to

[13] .

[0019]

[15] A process for hydroformylating dicyclopentadiene to obtain tricyclodecane dicarbaldehyde, a process for obtaining a crude reaction solution containing tricyclodecane dimethanol by a reduction reaction of the tricyclodecane dicarbaldehyde, and a process for distilling and purifying the crude reaction solution to obtain the tricyclodecane dimethanol composition according to any one of [1] to

[10] , a method for producing a tricyclodecane dimethanol composition.

[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 more and 350 ° C or less, the distillation conditions in the distillation purification satisfy the following formula (1), the method for producing a tricyclodecane dimethanol composition according to

[15] . (Ya-Za)×T / S×100≦1.65 (1) (In formula (1), Ya: The mass ratio of chiral compound A in the crude reaction solution supplied to the distillation purification step (unit: dimensionless number) S: The total weight 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 (unit: g) Za: The mass ratio of chiral compound A in the distillate distilled out of the purification system from the distillation column in the distillation purification step (unit: dimensionless number) T: The total weight 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 (unit: g) .)

Advantages of the Invention

[0020] According to the present invention, a TCDDM composition excellent in 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, in which no decrease in fluidity is observed even after long-term storage, can be provided.

Brief Description of the Drawings

[0021]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0022] Hereinafter, the present invention will be described in detail. The present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

[0023] Unless otherwise specified, the numerical range represented by "~" in this specification means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. "A~B" means A or more and B or less.

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

[0025] In this specification, "mass%" indicates the content ratio of a predetermined component contained in the total amount of 100 mass%. "Mass%" and "weight%" are synonymous. As used herein, "optional" or "optionally" means that the subsequently described situation may or may not occur. Therefore, the description includes both the case where the situation occurs and the case where it does not occur.

[0026] As used herein, the term "about" means that it can include 20% above and below the indicated value. For example, a temperature of about 75°C based on 0°C Celsius includes the range of 60°C to 90°C. All steps described herein can be performed in any suitable order, unless otherwise specifically described herein or clearly inconsistent with the context.

[0027] Hereinafter, embodiments of the present invention will be described in detail. The description of the constituent elements described below is an example of an embodiment of the present invention, and the present invention is not limited to these contents.

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

[0029] The chiral compound A, chiral compound B, chiral compound C, and chiral compound D each have one hydroxymethyl group (CH2OH group) in the 6-membered ring part of the norbornane ring and another hydroxymethyl group in the 5-membered ring part, as shown by the following general formulas (I) to (IV).

[0030]

Chemical formula

[0031] Thus, for the chiral compounds A, B, C, and D in the present invention, although R-form and S-form exist as enantiomers (also referred to as optical isomers), regardless of their differences, both forms are included.

[0032] For the chiral compounds A, B, C, and D in the present invention, stereoisomers exist depending on whether the two hydroxymethyl groups are bonded to the same side or the opposite side of the bridgehead position of the norbornane ring. The chiral compounds A, B, C, and D in the present invention are those in which the hydroxymethyl group is bonded to the same side as the bridgehead position of the norbornane ring, as shown by formulas (I) to (IV), respectively. Further, although endo-form and exo-form exist in the tricyclodecane skeleton, the chiral compounds A, B, C, and D in the present invention represent only the endo-form. 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, by nuclear magnetic resonance spectroscopy ( 13 13C-NMR method), let the number of moles of the chiral compound A be Xa, the number of moles of the chiral compound B be Xb, the number of moles of the chiral compound C be Xc, and the number of moles of the chiral compound D be Xd. Also, let the total number of moles of the chiral compounds A, B, C, and D be Xt (= Xa + Xb + Xc + Xd). Details of the measurement methods of Xa, Xb, Xc, and Xd in the present invention are described in the Examples section.

[0034] <Regarding Xa / Xt> In the TCDDM composition of the present invention, the upper limit of Xa / Xt calculated from the above Xa and Xt is Xa / Xt ≦ 0.430 from the viewpoint of the storage stability of the TCDDM composition. It is preferable that Xa / Xt ≦ 0.400, more preferably Xa / Xt ≦ 0.370, still 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 is not particularly limited, but from the viewpoint of maintaining good handleability of the TCDDM composition, usually Xa / Xt ≧ 0.250 can be set, preferably Xa / Xt ≧ 0.270, more preferably Xa / Xt ≧ 0.290, still more preferably Xa / Xt ≧ 0.310, and particularly preferably Xa / Xt ≧ 0.330.

[0036] The above upper and lower limits can be arbitrarily combined. For example, in the TCDDM composition of the present invention, the 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, still more preferably 0.310 ≦ Xa / Xt ≦ 0.360, and particularly preferably 0.330 ≦ Xa / Xt < 0.350.

[0037] The means for controlling the value of Xa / Xt is not particularly limited, and those skilled in the art can control it by appropriately optimizing the production conditions according to well-known techniques. For example, the reaction conditions of hydroformylation and the distillation conditions when the obtained TCDDM composition is purified by distillation can be optimized to control the value of Xa / Xt.

[0038] <Regarding Xb / Xt> In the TCDDM composition of the present invention, the lower limit of Xb / Xt calculated from the above Xb and Xt is Xb / Xt ≥ 0.016 from the viewpoint of the storage stability of the TCDDM composition. The Xb / Xt is preferably Xb / Xt ≥ 0.020, more preferably Xb / Xt ≥ 0.027, still 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 good handleability by appropriately maintaining the fluidity of the TCDDM composition, Xb / Xt ≤ 0.13 can be set. The Xb / Xt is preferably Xb / Xt ≤ 0.10, more preferably Xb / Xt ≤ 0.048, still 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 arbitrarily combined. 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, still 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 value of Xb / Xt is not particularly limited, and those skilled in the art can control it by appropriately optimizing the production conditions according to well-known techniques. For example, the reaction conditions of hydroformylation, the distillation conditions when the obtained TCDDM composition is purified by distillation, etc. can be optimized to control the value of Xb / Xt.

[0042] <Regarding Xc / Xt> In the TCDDM composition of the present invention, the lower limit of Xc / Xt calculated from the above-mentioned Xc and Xt can be set to Xc / Xt ≥ 0.300 from the viewpoint of the storage stability of the TCDDM composition. The Xc / Xt is preferably Xc / Xt ≥ 0.310, more preferably Xc / Xt ≥ 0.320, and still 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. The Xc / Xt is preferably Xc / Xt ≤ 0.360, more preferably Xc / Xt ≤ 0.350, and still more preferably Xc / Xt ≤ 0.340.

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

[0045] The means for controlling the value of Xc / Xt is not particularly limited, and those skilled in the art can control it by appropriately optimizing the production conditions according to well-known techniques. For example, the reaction conditions of hydroformylation and the distillation conditions when the obtained TCDDM composition is purified by distillation can be optimized to control the value of Xc / Xt.

[0046] <Regarding Xd / Xt> In the TCDDM composition of the present invention, the lower limit of Xd / Xt calculated from the above Xd and Xt is not particularly limited, and from the viewpoint of the storage stability of the TCDDM composition, Xd / Xt ≥ 0.240 can be satisfied. It is preferable that Xd / Xt ≥ 0.250, more preferably Xd / Xt ≥ 0.260, still 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, Xd / Xt ≤ 0.370 can be satisfied. It is preferable that Xd / Xt ≤ 0.350, more preferably Xd / Xt ≤ 0.330, still more preferably Xd / Xt ≤ 0.320, and particularly preferably Xd / Xt ≤ 0.310.

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

[0049] The means for controlling the value of Xd / Xt is not particularly limited, and those skilled in the art can control it by appropriately optimizing the production conditions according to well-known techniques. For example, the reaction conditions of hydroformylation, the distillation conditions when the obtained TCDDM composition is purified by distillation, etc. can be optimized to control the value of Xd / Xt.

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

[0051] On the other hand, the upper limit of Xb / (Xa + Xc + Xd) is not particularly limited, but from the viewpoint of maintaining good handleability of the TCDDM composition, Xb / (Xa + Xc + Xd) can be 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 above upper and lower limits can be arbitrarily combined. 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 those skilled in the art can control it by appropriately optimizing the production conditions according to well-known techniques. For example, the reaction conditions of hydroformylation, the distillation conditions when the obtained TCDDM composition is purified by distillation, etc. can be optimized to control the value of Xb / (Xa + Xc + Xd).

[0054] In the TCDDM composition of the present invention, the chiral compound B is a compound detected within the range of a retention time of 13.65 to 13.85 minutes when the composition is measured under the following measurement conditions using gas chromatography (GC). In the TCDDM composition of the present invention, the chiral compound A is a compound that is detected within the range of a retention time 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 holding time) → temperature increase at 5 °C / min → 300 °C (holding time 2 minutes) Inlet temperature: 200 °C Detector: Flame ionization detector (temperature 300 °C)

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

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

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

[0059] The manufacturing method of the TCDDM composition of the present invention includes a step of hydroformylating dicyclopentadiene to obtain tricyclodecane dicarbaldehydes, a step of obtaining a crude reaction solution containing tricyclodecane dimethanol by a reduction reaction of the tricyclodecane dicarbaldehyde, and a step of distilling and purifying the crude reaction solution to obtain a tricyclodecane dimethanol composition.

[0060] At this time, in the step of introducing a formyl group by hydroformylation, isomers are generated, so tricyclodecane dicarbaldehydes, which are precursors of chiral compound A, chiral compound B, chiral compound C, and chiral compound D, are obtained as a mixture. Then, by the hydrogenation step, chiral compound A, chiral compound B, chiral compound C, and chiral compound D are obtained respectively.

[0061] The method for controlling the ratios of chiral compound A, chiral compound B, chiral compound C, and chiral compound D of the present invention is not particularly limited. The ratios of chiral compound A, chiral compound B, chiral compound C, and chiral compound D may be controlled by adjusting the reaction conditions of hydroformylation, may be controlled by isomerization using a method such as heating, or may be controlled by distilling and purifying the produced TCDDM composition.

[0062] <Hydroformylation reaction 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, in a hydroformylation reaction solvent composed of a hydrocarbon compound, in the coexistence of a catalyst composed of a rhodium compound and an organic phosphorus compound, using hydrogen and carbon monoxide, as shown in the following reaction formula (V), dicyclopentadiene can be hydroformylated to produce tricyclodecane dicarbaldehyde.

[0063]

Chemical formula

[0064] The rhodium compound used in this hydroformylation step forms a complex with an organophosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide, regardless of the form of its precursor. That is, Rh(acac)(CO)2, Rh2O3, Rh4(CO) 12 , Rh6(CO) 16 , catalyst precursor substances such as Rh(NO3)3 may be introduced into the reaction mixture together with the organophosphorus compound to form a rhodium metal hydridocarbonyl phosphorus complex having catalytic activity in the reaction vessel, or a rhodium metal hydridocarbonyl phosphorus complex catalyst may be prepared in advance and introduced into the reaction vessel.

[0065] In a preferred specific example of the present invention, Rh(acac)(CO)2 is used as a rhodium precursor substance 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 obtain a rhodium-organophosphorus complex catalyst having catalytic activity.

[0066] Examples of the organophosphorus compound that forms a catalyst for the hydroformylation reaction with the rhodium compound include phosphites and phosphines.

[0067] Among these, as the phosphite, since it is effective for the hydroformylation reaction of dicyclopentadiene, a compound represented by the general formula P(-OR 1 )(-OR 2 )(-OR 3 )(wherein R 1 , R 2 and R 3 each represent an optionally substituted aryl group or alkyl group.) is preferred. R 1 、R 2 and R 3Specific examples include aryl groups such as phenyl groups and naphthyl groups which may be substituted with, for example, a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group, a methoxy group, etc.; aliphatic alkyl groups such as a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group, etc.; alicyclic alkyl groups such as a cyclopentyl group, a cyclohexyl group, etc. which may be substituted with a lower alkyl group such as a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a 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, alkyl phosphines with particularly large steric hindrance are effective for the hydroformylation reaction of dicyclopentadiene. Representative examples include, but are not limited to, tricyclopropylphosphine, tricyclobutylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, tricycloheptylphosphine, tricyclooctylphosphine, etc. These phosphines may be used alone or in combination of two or more.

[0070] If the amount of the organophosphorus compound used is in the range of 1 to 400 molar times, preferably 3 to 200 molar times, relative to the rhodium metal in the hydroformylation reaction solution, 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 it can be more preferably carried out by using an organic solvent inert to the reaction.

[0072] As described below, after the hydroformylation reaction is completed, the reaction product solution containing tricyclodecane dicarbaldehyde is brought into contact with an alcohol, and while leaving the catalyst component in the dihydroformylation reaction solvent layer, tricyclodecane dicarbaldehyde is extracted into the extraction solvent layer composed of an alcohol, and liquid separation is performed. Therefore, the hydroformylation reaction solvent is preferably one that can be separated from the alcohol by liquid separation. Examples of such solvents include aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, and alicyclic hydrocarbon compounds.

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

[0074] Examples of aliphatic hydrocarbon compounds include pentane, hexane, heptane, octane, isooctane, dodecane, and decane. The aliphatic hydrocarbon compound only needs to be liquid at standard temperature and pressure and is not limited thereto.

[0075] Examples of alicyclic hydrocarbon compounds preferably used include cyclohexane, cyclooctane, cyclododecane, decalin, methylcyclohexane, and the like.

[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 the solvent so that the concentration of dicyclopentadiene in the reaction solution is 10 - 95% by mass, particularly about 30 - 90% by mass.

[0078] The amount of the rhodium catalyst used is usually 10 to 5000 weight ppm as rhodium metal, more preferably 50 to 2000 weight ppm, based on the raw material dicyclopentadiene. When rhodium is used at 50 ppm or more, catalyst recovery is required.

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

[0080] The above upper and lower limits can be arbitrarily combined. 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 still more preferably 1.5 MPaG or more and 3.5 MPaG or less.

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

[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 or more and 5.0 or less 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] As the reaction method of hydroformylation, a continuous feed method is adopted in which the raw material dicyclopentadiene alone or as a mixed solution of dicyclopentadiene and a solvent is supplied to a reactor in the presence of a rhodium-organophosphorus complex catalyst, a solvent, and a hydrogen / carbon monoxide mixed gas. Using this method, the generation of cyclopentadiene, which inhibits the hydroformylation reaction due to the thermal decomposition of dicyclopentadiene in the reactor, can be reduced, and a good reaction rate and yield can be maintained. In order to maintain the fluidity of dicyclopentadiene, it is preferably diluted with the above-mentioned solvent and supplied to the reactor at a temperature at which they do not depolymerize to form cyclopentadiene.

[0084] <Extraction of tricyclodecane dicarbaldehyde> After completion of the hydroformylation reaction, the reaction product solution is used as it is, or diluted with a hydrocarbon compound or other hydrocarbon compound used as the hydroformylation reaction solvent, and then contacted with an alcohol to extract the product tricyclodecane dicarbaldehyde into the alcohol while leaving the catalyst component in the hydroformylation reaction solvent layer, and layer separation is performed.

[0085] Examples of the alcohol include primary alcohols having 1 to 3 carbon atoms and polyhydric alcohols having 2 to 6 carbon atoms. Examples of the primary alcohol include methanol, ethanol, and propanol. Examples of the polyhydric alcohol 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, trimethylolpropane, etc. Among these, methanol, ethylene glycol, propanediol, and butanediol are preferably used because they have relatively low boiling points, low prices, and are easy to handle as liquids. These extraction solvents may be used alone or in combination of two or more.

[0086] Extraction may be carried out in the coexistence of water with alcohol. The addition of water makes it easier for aldehydes and catalyst components to be distributed into each layer.

[0087] It is preferable that the reaction solvent and the extraction solvent used in the hydroformylation reaction have a density difference in order to achieve effective layer separation. One preferred example of the combination of the hydroformylation reaction solvent containing tricyclodecane dicarbaldehyde and the extraction solvent is the combination of methylcyclohexane as the reaction solvent and ethylene glycol as the extraction solvent, the 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 in equilibrium. On the other hand, rhodium and the organic phosphorus compound, which are catalyst components, substantially exist only in the hydroformylation reaction solvent and exist below the analytical limit in the extraction solvent.

[0089] The volume ratio of the extraction solvent to be used and the reaction product solution is determined by the solubility of tricyclodecane dicarbaldehyde in the extraction solvent and the amount of tricyclodecane dicarbaldehyde to be extracted. For example, when the tricyclodecane dicarbaldehyde to be separated shows high solubility in the extraction solvent and exists at a low concentration in the reaction product solution, practical extraction of tricyclodecane dicarbaldehyde can be achieved 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) for extracting tricyclodecane dicarbaldehyde from the reaction product solution.

[0090] When tricyclodecane dicarbaldehyde exhibits a relatively low solubility in the extraction solution, the volume ratio (extraction solvent / reaction product solution) can vary in the range of 10:1 to 1:10. In order to increase the extraction amount of tricyclodecane dicarbaldehyde with a small amount of extraction solvent used, it is effective to divide the extraction solvent and perform the extraction operation several times. Also, in the final extraction operation, a hydroformylation reaction solvent such as methylcyclohexane may be added to the reaction product solution in an amount of about 5 to 20% by mass. The addition of the hydroformylation reaction solvent can improve the removal rate of the catalyst.

[0091] The temperature at which the extraction operation is carried out is not particularly limited, but it is practical to carry it out at a temperature not higher than the hydroformylation reaction temperature. After the reaction, the extraction solvent may be added to the hydroformylation reactor to carry out the extraction operation, or the hydroformylation reaction product solution may be withdrawn from the hydroformylation reactor and the extraction operation may be carried out in an extraction tank. It is also possible to directly add the extraction solvent to the hydroformylation reactor to carry out the extraction operation and hold the catalyst component in the hydroformylation reactor as it is to carry out the next hydroformylation reaction. When the hydroformylation reaction product solution 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 for the reaction. This process can be carried out either in a batch process or in a continuous process.

[0092] In the extraction operation as described above, a tricyclodecane dicarbaldehyde-containing solution containing 10 to 90% by mass of tricyclodecane dicarbaldehyde and 10 to 90% by mass of the extraction solvent can be obtained. When the reaction solvent is added, a tricyclodecane dicarbaldehyde-containing solution containing 5 to 90% by mass of tricyclodecane dicarbaldehyde, 5 to 90% by mass of the extraction solvent, and 5 to 90% by mass of the reaction solvent can be obtained.

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

[0094] <Hydrogenation reduction reaction> The extract (tricyclodecane dicarbaldehyde-containing solution) containing tricyclodecane dicarbaldehyde obtained by the above extraction operation 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. By doing so, the acetal compound can be quickly converted into tricyclodecane dicarbaldehyde during the hydrogenation reaction of tricyclodecane dicarbaldehyde, and TCDDM can be produced in a high yield by hydrogenating the tricyclodecane dicarbaldehyde converted from the acetal compound.

[0096]

Chemical formula

[0097] The water present in the hydrogenation reduction reaction is preferably not less than the amount of the acetal compound in the hydrogenation reduction reaction solution and in an amount such that the reaction solution does not phase-separate. In the hydrogenation reduction reaction, the water content 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 with respect to the whole reaction solution. When the water content is within the above range, water and the reaction solvent do not layer-separate, and the above-mentioned effects due to the presence of water in the hydrogenation reaction system can be effectively obtained. This addition of water may be carried out in the extraction step of separating the catalyst component and tricyclodecane dicarbaldehyde 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 with 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 of the hydrogenation reduction reaction, a method in which the catalyst is charged as a slurry into a stirred reactor, the reaction is carried out batchwise, and after the reaction, the catalyst is sedimented and filtered to be separated from the product solution, or a perfusion type reaction in which the formed catalyst is charged into a tubular reactor and the product solution and hydrogen gas are passed over the catalyst is appropriately employed. The amount of the catalyst used is not particularly limited as long as TCDDM can be produced with industrially advantageous productivity.

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

[0101] The above upper and lower limits can be arbitrarily combined. 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, still 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] Also, the reaction pressure of the hydrogenation reduction reaction is not particularly limited and can usually be 15 MPaG or lower. The higher the reaction pressure, the more a high-pressure-resistant reaction apparatus is required, resulting in a decrease in economic efficiency. Therefore, the reaction pressure is preferably 10 MPaG or lower, more preferably 7 MPaG or lower. On the other hand, the lower limit of this reaction pressure is usually 1 MPaG.

[0103] <Residual metal removal> In the crude reaction solution obtained by the above hydrogenation reduction reaction operation, metal elements derived from the hydrogenation catalyst are contained as elution components. By removing the metal elements in the crude reaction solution prior to distillation purification, thermal decomposition of TCDDM caused by the metal elements in the distillation purification process can be suppressed.

[0104] There is no particular limitation on the method for removing metal elements in the crude reaction solution and reducing their content, and examples include activated carbon treatment, cation exchange resin, silica gel adsorption, etc. Activated carbon treatment is preferred because of its high removal efficiency and the possibility of reusing the adsorbent.

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

[0106] In the case of batch treatment, the amount of activated carbon added to the crude reaction solution is appropriately determined according to the metal element adsorption capacity of the activated carbon and the metal element content ratio in the crude reaction solution. As general conditions, it is preferable to add activated carbon to the crude reaction solution at a concentration of about 0.01 to 10% by mass and stir.

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

[0108] Such activated carbon treatment may be performed multiple times. That is, the activated carbon treatment liquid obtained by subjecting the crude reaction liquid to activated carbon treatment may be subjected to activated carbon treatment again. In this case, the type and amount of activated carbon used, the treatment conditions, etc. may be changed between the first activated carbon treatment and the second activated carbon treatment.

[0109] The lower the content of metal elements in the crude reaction liquid to be subjected to the subsequent distillation purification, the more preferable it is from the viewpoint of suppressing the thermal decomposition of TCDDM. The content of metal elements in the crude reaction liquid to be subjected to distillation purification is preferably 10 mass ppm or less, particularly preferably 5 mass ppm or less, and especially preferably 1 mass ppm or less.

[0110] The pH of the crude reaction liquid to be subjected to distillation purification is preferably in the range of 6 to 8. If the lower limit of the pH is 6 or more, it is preferable because the by-production of low-boiling compounds that are presumably caused by the dehydration of TCDDM and the by-production of high-boiling compounds that are presumably caused by dimerization such as etherification can be suppressed. If the upper limit of the pH is 8 or less, it is preferable because the distillation purification equipment is less likely to be corroded by alkali.

[0111] Normally, the pH of the reaction product liquid obtained by the hydrogenation reduction reaction is 6 to 8, and even if it is subjected to the removal treatment of the hydrogenation catalyst and the removal treatment of metal elements, the pH hardly changes. However, the pH of the reaction product liquid may deviate from the range of 6 to 8 due to acids and alkali components eluted from the hydrogenation catalyst. In this case, it is preferable to adjust the pH to 6 to 8 by appropriately adding a pH adjuster such as an acid or an alkali.

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

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

[0114] In the distillation purification of the crude reaction solution, from the viewpoint of efficiently producing the tricyclodecane dimethanol composition of the present invention by controlling the content ratio (Xa / Xt) of the chiral compound A and the content ratio (Xb / Xt) of the chiral compound B in the obtained tricyclodecane dimethanol composition within a desired range, it is preferable to carry out distillation purification under conditions satisfying the following formula (1).

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

[0116] In the present specification, "distilled out of the purification system" means discharging the bottom distillate and / or the top distillate of the distillation column out of the purification system.

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

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

[0119] That is, the value of (Ya - Za) × T / S × 100 represented by the formula (1) is an index value indicating the discharge ratio of the chiral compound A discharged (distilled out) from the distillation column out of the purification system in the distillation purification step. By adopting distillation conditions such that this value becomes smaller, the content ratio of the chiral compound A contained in the obtained TCDDM composition can be reduced, and the value of Xa / Xt can be reduced.

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

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

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

[0123] There are no particular restrictions on other conditions of the distillation column in distillation purification, but usually, it is carried out at a pressure of 0.1 kPaA or more and 100 kPaA or less and a reflux ratio of about 1 or more and 30 or less. In particular, by controlling the reflux ratio and the distillate amount, it is possible to adjust the abundance ratios of chiral compound A, chiral compound B, chiral compound C, and chiral compound D in the obtained TCDDM composition. These conditions can be arbitrarily changed according to the equipment performance of the distillation column, kettle efficiency, recovery amount, etc., and there are no particular restrictions as long as a TCDDM composition having the composition defined 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. Usually, a TCDDM composition with a TCDDM purity of 98% or more can be obtained in a high yield by such distillation purification.

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

[0126] The production method of the ultraviolet curable composition is not particularly limited and can be carried out according to conventional methods. Generally, it is desirable to use tricyclodecane dimethanol in the TCDDM composition as a raw material to produce derivatives such as di(meth)acrylate derivatives or urethane acrylates for use.

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

[0128] As a method for producing a di(meth)acrylate derivative from TCDDM using the TCDDM composition as a raw material, specifically, methods such as reacting (meth)acrylic acid with TCDDM, performing a transesterification reaction between TCDDM and a (meth)acrylate ester, reacting a halide of (meth)acrylic acid such as (meth)acrylic acid chloride with TCDDM, etc. can be mentioned.

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

[0130] When producing a di(meth)acrylate derivative using (meth)acrylic acid or a (meth)acrylate ester, a catalyst can be used, and the reaction can be promoted by continuously removing the generated water or lower alcohol out of the system. Examples of the catalyst include those known as esterification catalysts such as sulfuric acid, p-toluenesulfonic acid, boron trifluoride, and organotin compounds, and these can be arbitrarily selected and used. The amount of the catalyst used is preferably 10 to 100000 ppm with respect to the total mass of the reaction substrates from the viewpoints of reducing the load on the production apparatus and reducing the catalyst cost.

[0131] When producing a di(meth)acrylate derivative using a halide of (meth)acrylic acid, it is preferable to carry out the reaction in the presence of a basic compound, and the reaction can also be promoted by using a catalyst.

[0132] Examples of the basic compound include tertiary amines such as triethylamine and N-ethyldiisopropylamine; phosphates such as potassium phosphate and sodium phosphate; carbonates such as potassium carbonate and sodium carbonate; hydroxides such as potassium hydroxide and sodium hydroxide, etc., which are known as basic compounds, and these can be arbitrarily selected and used. From the viewpoints of reducing the load on the production equipment and reducing the raw material cost, etc., the amount of the basic compound used is preferably 1.0 to 6.0 equivalents with respect to 1 equivalent of the halide of acrylic acid or methacrylic acid.

[0133] Examples of the catalyst include pyridines such as N,N-dimethyl-4-aminopyridine; imidazoles such as N-methylimidazole; tertiary amines such as triethylenediamine, etc., which are known catalysts for the esterification reaction of acid chlorides, and these can be arbitrarily selected and used. From the viewpoints of reducing the load on the production equipment and reducing the catalyst cost, etc., the amount of the catalyst used is preferably 10 to 100000 ppm with respect to the total mass of the reaction substrates.

[0134] In each of the above production methods, it is preferable to add a polymerization inhibitor in order to prevent the thermal polymerization of (meth)acrylic acid, (meth)acrylate, or the 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, p-benzoquinone, 2,5-dihydroxyp-benzoquinone, copper salts, phenothiazine, paraphenylenediamine, phenyl-β-naphthylamine, etc. 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 catalyst activity and reduction of the influence on side reactions.

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

[0137] A solvent can also be used in the reaction in each of the above production methods. The solvent is not particularly limited as long as it does not adversely affect the reaction. For example, 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 urethane acrylate using the TCDDM composition as a raw material is not particularly limited in its structure as long as it is an acrylate or methacrylate derivative containing a urethane bond.

[0139] As a method for producing urethane acrylate from TCDDM using a TCDDM composition as a raw material, specifically, a method of reacting a TCDDM composition, a polyisocyanate compound, and a monohydroxy acrylate compound in the presence of a catalyst is desirable. Further, for the purpose of adjusting the performance of the cured product, a polyol compound other than the TCDDM composition may be further added.

[0140] The content ratio of the TCDDM composition to the total mass of the reaction substrate as the 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 viewpoints of the hardness and heat resistance of the cured product. On the other hand, the upper limit of the content ratio is not particularly limited, and the higher the better.

[0141] Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl ether-4,4'-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, norbornane methane diisocyanate and their hydrides, pentamethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, etc. These allophanate forms, adduct forms, biuret forms may be used, or dimers, trimers may be used. These may be used alone or in combination of two or more.

[0142] It is preferable that the monohydroxy acrylate compound has a structural moiety connecting a hydroxy group and an acryloyloxy group composed of three carbon atoms or more atoms. Examples of such compounds include acrylate compounds of aliphatic polyols having 3 or more carbon atoms, such as hydroxypropyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, ditrimethylolpropane triacrylate, dipentaerythritol pentaacrylate, etc.; (poly)oxyalkylene modified products obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. into the molecular structure of the acrylate compound; lactone modified products obtained by introducing (poly)lactone structure into the molecular structure of the acrylate compound; diacrylate of isocyanuric acid, (poly)oxyalkylene modified products obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. into the molecular structure of diacrylate of isocyanuric acid; lactone modified products obtained by introducing (poly)lactone structure into the molecular structure of diacrylate of isocyanuric acid, and the like. Further, methacrylate compounds obtained by replacing the acrylate of the above compound group with methacrylate may be used. These may be used alone or in combination of two or more kinds.

[0143] Examples of the polyol compounds other than the TCDDM composition include linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol; branched-chain 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, dimer diol; diols having an ether group such as diethylene glycol, propylene glycol; diols having an alicyclic structure such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane; diols having an aromatic group such as xylylene glycol, 1,4-dihydroxyethylbenzene, 4,4'-methylenebis(hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane, pentaerythritol; polyether polyol, polyester polyol, polycarbonate polyol, etc. These polyol compounds may be used alone or in combination of two or more.

[0144] Examples of the catalyst include organotin compounds such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin; organobismuth compounds such as dibutylbismuth dilaurate, dioctylbismuth dilaurate; metal salts such as zinc octylate, tin octylate, cobalt naphthenate, stannous chloride, stannic chloride; amine-based 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, N-ethylmorpholine, etc.

[0145] In order to prevent thermal polymerization of monohydroxyacrylate compounds and the like, it is preferable to add a polymerization inhibitor. The polymerization inhibitor is not particularly limited as long as it inhibits the reaction, and examples include hydroquinone, paramethoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, para-benzoquinone, 2,5-dihydroxypara-benzoquinone, copper salts, phenothiazine, paraphenylenediamine, phenyl-β-naphthylamine, and the like. From the viewpoints of catalyst activity and reduction of the influence on side reactions, the amount of the polymerization inhibitor used is preferably 10 to 100,000 ppm based on the total mass of the reaction substrates.

[0146] From the viewpoints of shortening the reaction time and preventing polymerization, the reaction temperature in the above production method is preferably 30 to 120°C, more preferably 40 to 100°C. The reaction time is preferably 1 to 10 hours.

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

[0148] Since the ultraviolet curable composition of the present invention is synthesized using the TCDDM composition of the present invention as a raw material, it has excellent coating stability without impairing the performance originally required for the ultraviolet curable composition. Therefore, the ultraviolet curable composition of the present invention can be suitably used for hard coat materials, antifouling coat materials, resist materials, inkjet inks, materials for 3D printers, and the like.

[0149] In applications such as resists, a method of applying and curing the ultraviolet curable composition on a substrate using screen printing or flexographic printing methods is used. In this case, from the viewpoints of being able to apply thinly and uniformly, being able to apply thickly, and being able to print a fine pattern on a substrate with high precision, etc., the ultraviolet curable composition is required to have excellent fluidity.

[0150] In applications such as hard coats and antifouling coats, and inkjet printing, a method of applying and curing the ultraviolet curable composition on a substrate using a coater method, a spray method, or a dispenser method is used. In this case, from the viewpoint of accurately discharging the ultraviolet curable composition quantitatively, the ultraviolet curable composition is required to have excellent fluidity.

[0151] As described above, the ultraviolet curable composition of the present invention is derived from the TCDDM composition of the present invention, which is excellent in storage stability and can maintain high fluidity even after long-term storage by appropriately controlling a specific isomer ratio. Therefore, the ultraviolet curable composition of the present invention is excellent in coating stability and application stability, and there is no problem that the performance originally required for the ultraviolet curable composition is impaired because there is no need to blend additives. From these facts, the ultraviolet curable composition of the present invention can be suitably used for applications of 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 is a composition containing a polymer containing a structural unit 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 one obtained by appropriately adding or removing a solvent such as water or an organic solvent to adjust the solid content concentration, or may be one obtained by removing the solvent and drying to obtain a solid. Further, it may be a polymer composition obtained by appropriately removing impurities and purifying from a composition containing a polymer obtained by polymerization, and further, if necessary, within a range that does not affect the performance of the polymer obtained by polymerization, appropriate additives such as a storage stabilizer (such as an ultraviolet absorber or an antioxidant), a coloring agent, an antistatic agent, a lubricant, a filler, a flame retardant, a foaming agent, etc. may be added. That is, the polymer composition of the present invention only needs to contain a polymer obtained by polymerizing the TCDDM composition of the present invention or the ultraviolet curable composition of the present invention, and is not particularly limited with respect to its form, component composition, etc.

[0154] As an embodiment of the polymer constituting the polymer composition, specifically, at least one selected from the group consisting of polyester resins, epoxy resins, acrylate resins, polycarbonate resins, and polyurethane resins can be mentioned.

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

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

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

[0158] In the present invention, the polycarbonate resin is a resin mainly composed of a polycarbonate polymer. The polycarbonate polymer is not particularly limited, and examples thereof include a polymer containing a structural unit derived from a bisphenol compound, a structural unit derived from phosgene (carbonyl chloride), or a structural unit derived from diphenyl carbonate, and further containing a structural unit derived from tricyclodecane dimethanol in the TCDDM composition of the present invention.

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

Examples

[0160] Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by 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 in-house 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%) · Copper oxide-aluminum oxide-containing catalyst (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 measurement 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, and the number of moles Xd of chiral compound D, which were contained in the TCDDM compositions obtained in the examples and comparative examples, and the total number of moles Xt (= Xa + Xb + Xc + Xd) of the number of moles of the chiral compound A, the chiral compound B, the chiral compound C, and the chiral compound D were calculated by the following procedure using the 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. Note that 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 to make a mixed solution of CDCl3:DMSO-d6 = 9:1, which became transparent, and this mixed solution was used as a sample for NMR measurement. The NMR measurement sample 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 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 integrations 512, and measurement temperature 25°C. The reference for chemical shift was set such that the signal of TMS was 0.00 ppm. The 13C-NMR spectra of the TCDDM compositions obtained in Example 2 and Comparative Example 1 13 are shown in Figures 2(a) and 2(b), respectively.

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

[0168] 13 In the 13C-NMR spectrum, the signals of 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. Also, when deuterated dimethyl sulfoxide was added, they were observed at 27.8 ppm, 27.6 ppm, 28.3 ppm, and 27.4 ppm, respectively. 13 In the 13C-NMR spectrum, the signal of 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]

Chemical formula

[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 under the following measurement conditions using gas chromatography (GC).

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

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

[0173] <Mass spectrometry of TCDDM composition> For the TCDDM compositions obtained in the examples and comparative examples, in order to confirm that TCDDM was generated, the m / z and fragment pattern were measured by gas chromatography mass spectrometry according to 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 according to 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 at a temperature of 60°C, and while stirring the sample, it was heated until the measured temperature of the TCDDM composition reached 60°C. Next, the stirring of the sample was stopped, 1 mL of the TCDDM composition was sampled and placed in a measurement cell, the measurement cell was placed in a thermostatic bath equipped in a dynamic light scattering measurement device, and while maintaining the measured temperature of the TCDDM composition at 60°C, the measurement of the dynamic light scattering intensity and the visual observation of fluidity were performed under the following measurement conditions. Note that the measurement of the dynamic light scattering intensity and the visual observation of fluidity were carried out immediately before immersing the TCDDM composition sample in the oil bath (0 hours) and 96 hours, 175 hours, and 196 hours after immersing it in the oil bath.

[0177] (Measurement conditions) Measuring device: Dynamic light scattering measurement device (trade name: Zetasizer Nano ZS, manufactured by Malvern Panalytical) Detection method: 173° backscattering detection method (A scattered light detector is installed 173° behind the sample.) Sample temperature: 60°C Cell: Glass

[0178] Furthermore, the storage stability of the TCDDM composition was evaluated according to the following criteria. Regarding the determination of fluidity, with the glass reagent bottle immersed in the high-temperature bath of the dynamic light scattering measurement device, when the tip of a glass rod was immersed 10 mm into the TCDDM composition in the reagent bottle and pulled up 10 cm, if it showed drawability, it was determined as "with fluidity", and if it did not show drawability, it was determined as "without fluidity". (Determination criteria) A: The TCDDM composition showed fluidity after 196 hours and the dynamic light scattering intensity was 3500 or less. B: The TCDDM composition showed fluidity after 196 hours and the dynamic light scattering intensity exceeded 3500. C: The TCDDM composition showed fluidity after 96 hours, but after 175 hours, it did not show fluidity and the dynamic light scattering intensity exceeded 100000. The TCDDM composition did not show fluidity after 96 hours, and the dynamic light scattering intensity exceeded 100,000.

[0179] [Example 1] <Hydroformylation Reaction> Into an autoclave reactor (up-and-down stirring type) with an internal volume of 500 mL, under a nitrogen atmosphere, as raw material compounds for the hydroformylation reaction catalyst, 11 mg of acetylacetonato dirhodium carbonyl and 870 mg of tris(2,4-di-tert-butylphenyl) phosphite were weighed, 69 g of methylcyclohexane as an organic solvent, and 89 g of dicyclopentadiene were sequentially charged. Then, while stirring, the temperature of the reaction solution in the reactor was raised to 70 °C. Next, a mixed gas of hydrogen and carbon monoxide (hydrogen:carbon monoxide = 1:1 (molar ratio)) was quickly injected from the gas introduction valve so that the pressure in the reactor became 3 MPaG, and the reaction was carried out for 1 hour. Then, after raising the temperature of the reaction solution to 100 °C, the reaction was further carried out for 5 hours. During the reaction, the amount of the mixed gas consumed by the reaction was continuously introduced into the reactor while maintaining the pressure in the reactor at 3.0 MPaG. After completion of the reaction, the reaction solution in the reactor was cooled to room temperature, the residual gas in the reactor was depressurized, and 192 g of a hydroformylation reaction product solution was obtained. The amount of dicyclopentadiene, a raw material compound contained in the reaction solution before the reaction, and the production amount of tricyclodecane dicarbaldehyde, the product in the hydroformylation reaction product solution after the reaction, were analyzed by gas chromatography, and the yield of tricyclodecane dicarbaldehyde was determined. The yield was 99%.

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

[0181] <Hydrogenation reduction reaction> Into an autoclave reactor with an internal volume of 500 mL, 200 g of the lower phase (a2) obtained by the above-described extraction operation and 0.6 g of ruthenium-supported carbon as a hydrogenation reduction reaction catalyst were charged. Then, while stirring at 1200 rpm, the temperature of the reaction solution in the reactor was raised to 160°C. Next, hydrogen gas was injected from the gas introduction 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 the mixed gas consumed by the reaction was continuously introduced into the reactor so as to maintain the pressure in the reactor at 3 MPaG. After completion of the reaction, the reaction solution in the reactor was cooled to room temperature, the residual gas in the reactor was depressurized, and the ruthenium-supported carbon was filtered using a filter with a pore diameter of 5 μm to obtain 176 g of a reaction product solution. The amount of tricyclodecane dicarbaldehyde, which is the raw material compound contained in the reaction solution before the reaction, and the production amount of TCDDM, which is the product in the reaction product solution after the reaction, were analyzed by gas chromatography. The yield of TCDDM was 98%.

[0182] <Distillation purification> 170 g of the reaction product solution after the hydrogenation reduction reaction was charged into a batch distillation column equivalent to 5 stages of structured packing (a four-necked flask with an internal volume of L). At a minimum column internal pressure of 10 kPaA and a maximum column bottom temperature of 100°C, 80.2 g of light-boiling components mainly composed of a solvent were distilled off. Then, the column internal pressure was set to 0.3 kPaA and the column bottom temperature was set to 120°C, and distillation was carried out until 1.5 g of distillate was obtained from the top of the distillation column. Next, the distillation column equivalent to 5 stages of structured packing was replaced with a glass single distillation column, and by performing simple distillation at a pressure of 0.3 kPaA and a temperature of 165°C, a TCDDM composition was distilled out from the top of the column and recovered in the order of initial distillate and main distillate. The recovery amount of the TCDDM composition recovered as the main distillate was 64.6 g. In this distillation purification, the values of S, T, Ya, Za, and (Ya - Za)×(T / S)×100 are shown in Table 1.

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

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

[0185] [Example 3] In the hydrogenation reduction reaction of Example 1, 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 the ruthenium - supported carbon, and the hydrogenation reduction reaction was carried out under the same conditions as in Example 1, and 176 g of the reaction product solution was obtained. The yield of TCDDM obtained by the hydrogenation reduction reaction was 99%. Next, for 170 g of the reaction product solution after the hydrogenation reduction reaction, in the distillation purification of Example 1, the distillation purification was carried out under the same conditions as in Example 1, except that the values of S, T, Ya, Za, and (Ya - Za)×(T / S)×100 were changed as described in Table 1. The recovered amount of the TCDDM composition recovered as the main distillate after distillation purification was 65.3 g. The evaluation results of the obtained TCDDM composition are shown in Table 2.

[0186] [Example 4] In the hydrogenation reduction reaction of Example 1, a hydrogenation reduction reaction was carried out under the same conditions as in Example 1 except that a catalyst containing copper oxide and aluminum oxide was used instead of ruthenium-supported carbon, and 174 g of a reaction product solution was obtained. The yield of TCDDM obtained by the hydrogenation reduction reaction was 99%. Next, in the distillation purification of Example 1, using a distillation column equivalent to 15 stages of structured packing (a four-necked flask with an internal volume of 3 L) instead of the batch distillation column equivalent to 5 stages of structured packing, from 170 g of the reaction product solution after the hydrogenation reduction reaction, after distilling off the light-boiling components mainly composed of the solvent, the pressure inside the column was set to 0.6 kPaA and the bottom temperature was set to 185 °C, and distillation was carried out until 11.6 g of a distillate was obtained from the top of the distillation column. Next, the distillation column equivalent to 15 stages of structured packing was replaced with a glass single distillation column, and simple distillation was carried out under the same conditions as in Example 1. The recovered amount of the TCDDM composition recovered as the main distillation was 53.0 g. The values of S, T, Ya, Za, and (Ya - Za)×(T / S)×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, using a distillation column equivalent to 20 stages of structured packing (a four-necked flask with an internal volume of 3 L) instead of the batch distillation column equivalent to 5 stages of structured packing, from 170 g of the reaction product solution after the hydrogenation reduction reaction, after distilling off the light-boiling components mainly composed of the solvent, the pressure inside the column was set to 0.6 kPaA and the bottom temperature was set to 185 °C, and distillation was carried out until 11.7 g of a distillate was obtained from the top of the distillation column. Next, the distillation column equivalent to 20 stages of structured packing was replaced with a glass single distillation column, and simple distillation was carried out under the same conditions as in Example 1. The recovered amount of the TCDDM composition recovered as the main distillation was 54.8 g. The values of S, T, Ya, Za, and (Ya - Za)×(T / S)×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] In the hydrogenation reduction reaction of Example 1, a 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 120 °C, and 177 g of a reaction product solution was obtained. The yield of TCDDM obtained by the hydrogenation reduction reaction was 98%. Next, for 170 g of the reaction product solution after the hydrogenation reduction reaction, in the distillation purification of Example 1, distillation purification was carried out under the same conditions as in Example 1 except that the values of S, T, Ya, Za, and (Ya - Za)×(T / S)×100 were changed as shown in Table 1. The recovered amount of the TCDDM composition recovered as the main distillation after simple distillation was 65.1 g. The evaluation results of the obtained TCDDM composition are shown in Table 2.

[0189] [Comparative Example 3] In the hydroformylation reaction of Example 1, 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, and a hydroformylation reaction product solution was obtained. The yield of the obtained tricyclodecane dicarbaldehyde was 98%. Next, for 193 g of the obtained hydroformylation reaction product solution, in the distillation purification of Example 1, extraction operation, hydrogenation reduction reaction, and distillation purification were carried out under the same conditions as in Example 1 except that the values of S, T, Ya, Za, and (Ya - Za)×(T / S)×100 were changed as shown in Table 1. The recovered amount of the TCDDM composition recovered as the main distillation after simple distillation was 63.6 g. The evaluation results of the obtained TCDDM composition are shown in Table 2.

[0190] For the TCDDM compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3, gas chromatography - mass spectrometry was carried out by the method described above, and when the m / z and fragment patterns were measured, it was confirmed that Peaks 1 to 3 all showed the m / z and fragment patterns corresponding to TCDDM. The representative fragments observed below are described. MS(EI): 178 ([M - 18]+), 165, 147, 119, 105, 91, 81, 67

[0191]

Table 1

[0192]

Table 2

[0193] In the evaluation of storage stability, the lower the analytical value of the dynamic light scattering intensity, the lower the crystallinity and the higher the fluidity of the TCDDM composition, that is, the better the storage stability of the TCDDM composition. From Table 1, the TCDDM compositions obtained in Examples 1 to 4 were superior in storage stability to the TCDDM compositions of Comparative Examples 1 to 3. In particular, the TCDDM compositions of Examples 2 and 3 were even more excellent in storage stability. The TCDDM compositions obtained in Comparative Examples 1 and 3 were inferior in storage stability because the value of Xa / Xt was large. Also, the TCDDM composition obtained in Comparative Example 2 was inferior in storage stability because the value of Xb / Xt was small.

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

Claims

1. A tricyclodecane dimethanol composition comprising a chiral compound A in which one enantiomer is represented by the following formula (I), a chiral compound B in which one enantiomer is represented by the following formula (II), a chiral compound C in which one enantiomer is represented by the following formula (III), and a chiral compound D in which one enantiomer is represented by the following formula (IV), wherein the number of moles Xa of the chiral compound A, the number of moles Xb of the chiral compound B, and the total number of moles Xt of the chiral compound A, the chiral compound B, the chiral compound C, and the chiral compound D, 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. The tricyclodecane dimethanol composition according to claim 1, wherein Xa and Xt satisfy Xa / Xt ≤ 0.

400.

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

027.

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

350.

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

300.

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

240.

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

010.

9. The tricyclodecane dimethanol composition according to 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 under the following measurement conditions using gas chromatography (GC). (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 holding time) → temperature increase at 5 °C / min → 300 °C (holding time 2 minutes) Inlet temperature: 200 °C Detector: Flame ionization detector (temperature 300 °C)

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

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 in 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 a polyester resin, an epoxy resin, an acrylate resin, a polycarbonate resin, and a polyurethane resin.

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

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

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 step of distilling and purifying the crude reaction solution to obtain the tricyclodecane dimethanol composition according to any one of claims 1 to 10, wherein the reaction pressure of the hydroformylation is 0.5 MPaG or more and 4.5 MPaG or less, the temperature of the reduction reaction is 125 °C or more and 350 °C or less, and a method for producing a tricyclodecane dimethanol composition, 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: The mass ratio of chiral compound A in the crude reaction solution supplied to the distillation purification step (unit: dimensionless number) S: The total weight 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 (unit: g) Za: The mass ratio of chiral compound A in the distillate distilled out of the purification system from the distillation column in the distillation purification step (unit: dimensionless number) T: The total weight 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 (unit: g) is.)

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