Compounds containing a binaphthalene skeleton and methods for manufacturing compounds containing a binaphthalene skeleton

Abstract

A compound having a binaphthalene skeleton is a compound having a binaphthalene skeleton represented by the following formula (1), (where R1 and R2 are each independent and are hydrogen atoms, halogen atoms, hydrocarbon groups with 1 to 12 carbon atoms that may contain aromatic groups, Ar1 and Ar2 are aromatic groups with 6 to 10 carbon atoms that may contain substituents, L1 and L2 are alkyl groups with 1 to 12 carbon atoms, j and k are each independent and are integers from 0 to 5, m1, m2, n1, and n2 are each independent and represent integers from 0 to 4, m1 + m2 ≥ 1, but m1 + n1 is an integer less than 4, and m2 + n2 is an integer less than 2) and the palladium content in the compound having a binaphthalene skeleton satisfies the following formula (2), the compound having a binaphthalene skeleton has a low content of specific metals such as palladium in the raw material alcohol or a low content of specific compounds, and the raw material or the resin using the raw material has excellent hue or various properties (optical properties, heat resistance, formability, etc.). 0≦Pd≦50ppm (2)

Description

[Technical Field] This invention relates to a compound having a binaphthyl skeleton, suitable as a monomer for forming thermoplastic resins constituting optical components such as optical lenses or optical films; and a method for manufacturing the compound having a binaphthyl skeleton. [Previous Technology] In recent years, thermoplastic resins such as polycarbonate and polyester, made from alcohols with a binaphthalene skeleton, such as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BN2EO), have attracted attention as optical components such as optical lenses or optical sheets due to their excellent optical properties, heat resistance, and formability. For example, Patent Document 1 discloses a polyester resin made from an alcohol containing BN2EO. Although it is recorded that the refractive index of the polyester resin using this alcohol is 1.67, with the rapid technological innovation in recent years, the aforementioned properties need to be further improved. Therefore, with the goal of further increasing the refractive index, Patent Document 2 developed a polycarbonate resin copolymerized from BN2EO and 9,9-bis[6-(2-hydroxyethoxy)2-naphthyl]fluorene (BNEF). However, the resin described in this patent document still has room for improvement in terms of refractive index. Incidentally, regarding the manufacturing methods of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthol, Patent Document 3 describes a method of reacting 1,1'-binaphthol with ethylene carbonate, and Patent Document 4 describes a method of reacting 1,1'-binaphthol with ethylene carbonate or ethylene oxide. Although high-purity products with less coloring can be obtained, the optical properties of thermoplastic resin materials using this alcohol as a raw material are still unsatisfactory, and there is still room for improvement. Furthermore, other literature describes compounds with superior optical properties obtained by substituting the 6,6' position of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthylene (Patent Document 5). Patent Document 5 discloses a method for synthesizing 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthylene. Although it mentions that the 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthylene obtained by the method described in this document is of high purity, this high purity is achieved through repeated purification or washing, thus resulting in a low yield. [Previous Art Documents] [Patent Documents] Patent Document 1: Japanese Patent Application Publication No. 2017-171885; Patent Document 2: International Publication No. 2018 / 016516; Patent Document 3: Japanese Patent No. 6083900; Patent Document 4: Japanese Patent No. 6083901; Patent Document 5: International Publication No. 2019 / 043060. [Summary of the Invention] [The problem that the invention aims to solve] The purpose of the following compound of formula (1) designed by molecular design in this invention is to provide a new compound with a binaphthyl skeleton, low content of specific metals such as palladium, and excellent hue or various properties (optical properties, heat resistance, formability, etc.) of the raw material or the resin using the raw material. Furthermore, the present invention aims to provide a method for producing high-purity binaphthyl compounds with excellent color in good yield. [Means for solving the problem] This invention was made to address the problems of the prior art described above, and provides a compound with a binaphthyl skeleton that has certain qualities and is excellent as a polymer raw material. Specifically, this invention relates to the compound with a binaphthyl skeleton disclosed below. [1] A compound having a binaphthyl skeleton, which is a compound having the binaphthyl skeleton represented by the following formula (1), [picture] (In the formula, R1 and R2 are independent and are hydrogen atoms, halogen atoms, hydrocarbon groups with 1 to 12 carbon atoms that may contain aromatic groups, Ar1 and Ar2 are aromatic groups with 6 to 10 carbon atoms that may contain substituents, L1 and L2 are alkyl groups with 1 to 12 carbon atoms, j and k are independent and are integers from 0 to 5, m1, m2, n1, and n2 are independent and represent integers from 0 to 4, m1 + m2 ≥ 1, but m1 + n1 is an integer less than 4, and m2 + n2 is an integer less than 2) and the palladium content in the compound having the binaphthalene skeleton satisfies the following formula (2) 0 ≦ Pd ≦ 50 ppm (2). [2] The compound having the binaphthalene skeleton as in the preceding item 1, wherein the aforementioned formula (1) is at least one of the following formulas (1a) to (1f), [picture] [picture] [picture] [picture] [picture] [picture] (In the formula, R3 to R14 are independent and represent hydrogen atoms, halogen atoms, and hydrocarbon groups with carbon numbers of 1 to 12 that may contain aromatic groups. Ar1 and Ar2, L1 and L2, j and k are the same as the aforementioned formula (1). [3] For compounds with a binaphthalene skeleton as described in the preceding item 2, the aforementioned formula (1) is the aforementioned formula (1d). [4] Any compound having a naphthyl skeleton as described in any of the preceding items 1 to 3, wherein Ar1 or Ar2 in the aforementioned formula (1) is phenyl or naphthyl. [5] The method of using compounds with a binaphthyl skeleton as described in paragraph 1 above is as a raw material for thermoplastic resins. [6] A method for producing a compound represented by formula (II), comprising reacting a compound represented by formula (I) with ethylene carbonate to produce a compound represented by formula (II), and including the following steps 1 and 2: Step 1: reacting the compound represented by formula (I) with ethylene carbonate in an amount (molar ratio) of 1:1.9 to 1:2.9 Step 2: after the reaction in step 1 is completed, adding an aqueous alkaline solution of 3% by weight or more to the resulting reaction mixture solution, and heating and stirring at a temperature of 50°C or higher. [picture] [picture] (In formulas (I) and (II), X1 to X4 are independent and are aromatic groups with 4 to 36 carbon atoms that may contain heteroatoms and may have substituents; n1 and n2 are independent and are integers from 1 to 4; n3 and n4 are independent and are integers from 0 to 2). [7] The method of manufacturing the compound as described in paragraph 6 above, wherein n1 and n2 in formulas (I) and (II) are 1, and n3 and n4 are 0. [8] The method of manufacturing the compound as described in paragraph 6 or 7 above, wherein formula (II) is the following formula (II-A). [picture] [9] A compound represented by the following formula (II-A) wherein the APHA of a solution of 0.5 g of the compound represented by the following formula (II-A) dissolved in 10 ml of dimethylformamide is 100 or less. [Image][Effects of the Invention] The binaphthyl compound produced by this invention has a high refractive index. By appropriately adjusting the amount of palladium-based catalyst used in the synthesis, the content of specific metals such as palladium is reduced, making them easily removed by activated carbon treatment or similar metal removal processes. Therefore, compounds with a low metal content and a binaphthyl skeleton can be produced very efficiently. Furthermore, this binaphthyl compound has two highly reactive hydroxyl groups, making it suitable as a monomer component for thermoplastic resins (such as polyester resins, polycarbonate resins, polyester carbonate resins, polyurethane resins, etc.). Furthermore, according to the manufacturing method of the present invention, high-purity naphthalene compounds with excellent color can be obtained in good yield.

Implementation Method

Claims

1. A compound having a binaphthyl skeleton, which is represented by at least one of the following formulas (1d), 1. (In the formula, R3~R6 are each independent hydrogen atoms, Ar1 is phenyl or naphthyl, L1 and L2 are ethyl, j and k represent 1) and the content of palladium from tetra(triphenylphosphine)palladium in compounds with a binaphthalene skeleton satisfies the following formula (2): 0.01≦Pd≦50ppm (2).

2. The compound having a binaphthyl skeleton as claimed in claim 1, wherein the compound having a binaphthyl skeleton is at least one of the compounds represented by formulas (1-a) to (1-c) below.

3. A method of using a compound having a binaphthyl skeleton as claimed in claim 1, which is used as a raw material for a thermoplastic resin.

4. A method for producing a compound represented by formula (II), comprising reacting a compound represented by formula (I) with ethylene carbonate to produce a compound represented by formula (II), and including the following steps 1 and 2: Step 1: reacting the compound represented by formula (I) with ethylene carbonate in an amount (molar ratio) of 1:1.9 to 1:2.9, and using dimethylformamide as a non-reactive solvent in a mixture of 0.1 to 10 parts by weight relative to the compound represented by formula (I); Step 2: after the reaction in step 1 is completed, adding an aqueous alkaline solution of 3% or more by weight to the resulting reaction mixture solution, and heating and stirring at a temperature of 50°C or higher.

4. (In formulas (I) and (II), X1~X4 are each independently phenyl or naphthyl, n1 and n2 are 1, and n3 and n4 are 0).

5. A method for manufacturing the compound of claim 4, wherein formula (II) is the following formula (II-A), 6. A compound represented by formula (II-A) wherein 0.5 g of the compound represented by formula (II-A) dissolved in 10 ml of dimethylformamide has an APHA of 100 or less.

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