Bifunctional compound and method for producing bifunctional compound

Abstract

The objective of the present invention is to provide a novel bifunctional compound having a norbornane skeleton in the molecule and having a bulky substituent at a C2 asymmetric position.　The above problem is solved by the following bifunctional compound. More specifically, the bifunctional compound according to the present invention is represented by formula (1). In formula (1), Cy represents a cyclohexyl group, and n represents 0 or 1.

Description

Difunctional compounds and methods for producing difunctional compounds

[0001] The present invention relates to a bifunctional compound and a method for producing a bifunctional compound.

[0002] Bifunctional compounds containing a norbornane skeleton may be used as adhesives, resin raw materials, etc.

[0003] For example, Patent Document 1 describes an active energy ray curable adhesive composition containing specific requirements (A) to (E). Patent Document 2 describes an invention relating to a method for producing tricyclodecanedialdehyde and tricyclodecanedimethylol. Patent Document 3 describes a practical method for producing tricyclodecanedimethanol and / or pentacyclopentadecanemethanol. Patent Documents 4 and 5 describe a bifunctional compound represented by a specific formula.

[0004] Japanese Patent Publication No. 5-125329, British Patent No. 1170226, Japanese Patent Publication No. 2001-10999, International Publication No. 2015-147242, International Publication No. 2016-153018

[0005] Applications of difunctional compounds include paint additives, adhesives, and resin raw materials. It is known that using difunctional compounds with bulky substituents at C2 asymmetric (i.e., non-molecularly symmetric) positions can modify the properties of paints, adhesives, resins, etc. Therefore, novel difunctional compounds are desired from the viewpoints of modification, property improvement, and functionalization.

[0006] In other words, the problem that one embodiment of the present invention aims to solve is to provide a novel bifunctional compound having a norbornane skeleton within the molecule and a bulky substituent at a C2 asymmetric position.

[0007] The present invention includes the following embodiments: <1> A bifunctional compound represented by the following formula (1).

[0008] In formula (1), Cy represents a cyclohexyl group, and n represents 0 or 1.

[0009] <2> A method for producing a bifunctional compound, comprising a step of producing a bifunctional compound, wherein a compound represented by the following formula (2a) or (2b) is reduced in the presence of a catalyst having hydrogenation ability and hydrogen to obtain the bifunctional compound described in <1>.

[0010] In formulas (2a) and (2b), Ph represents a phenyl group.

[0011] <3> A method for producing a bifunctional compound according to <2>, comprising: a cinnamon alcohol reaction step in which cinnamon alcohol and dicyclopentadiene are reacted before the bifunctional compound production step to obtain a compound represented by the following formula (3a) or the following formula (3b); and a hydroformylation step in which the compound represented by the following formula (3a) or the following formula (3b) is hydroformylated with carbon monoxide and hydrogen gas in the presence of a rhodium compound and an organophosphorus compound to obtain a compound represented by the following formula (2a) or the following formula (2b).

[0012]

[0013] <4> A method for producing a bifunctional compound according to <3>, wherein in the cinnamon alcohol reaction step, cinnamon alcohol and dicyclopentadiene are reacted at a temperature of 150°C to 300°C. <5> A method for producing a bifunctional compound according to <3> or <4>, for example, <3>, wherein the hydroformylation reaction is carried out under a pressure of 1.0 MPa to 12.0 MPa. <6> A method for producing a bifunctional compound according to any one of <2> to <5>, for example, <2>, wherein the catalyst having hydrogenation ability comprises at least one selected from the group consisting of copper, chromium, iron, zinc, aluminum, nickel, cobalt, palladium, and ruthenium.

[0014] According to one embodiment of the present invention, a novel bifunctional compound having a norbornane skeleton within the molecule and a bulky substituent at a C2 asymmetric position can be provided.

[0015] The results of the 1H-NMR measurement of the compound represented by formula (1a) obtained in Example 1 are shown. The results of the 13C-NMR measurement of the compound represented by formula (1a) obtained in Example 1 are shown. The results of the GC-MS measurement of the compound represented by formula (1a) obtained in Example 1 are shown. The results of the GC-TOFMS measurement of the compound represented by formula (1a) obtained in Example 1 are shown. The results of the 1H-NMR measurement of the compound represented by formula (1'a) obtained in Example 1 are shown. The results of the 13C-NMR measurement of the compound represented by formula (1'a) obtained in Example 1 are shown. The results of the GC-MS measurement of the compound represented by formula (1'a) obtained in Example 1 are shown. The results of the GC-TOFMS measurement of the compound represented by formula (1'a) obtained in Example 1 are shown. The results of the 1H-NMR measurement of the compound represented by formula (2a) obtained in Example 1 are shown. The results of the 13C-NMR measurement of the compound represented by formula (2a) obtained in Example 1 are shown. The results of the GC-MS measurement of the compound represented by formula (2a) obtained in Example 1 are shown. The results of the GC-TOFMS measurement of the compound represented by formula (2a) obtained in Example 1 are shown. The results of the ¹H-NMR measurement of the compound represented by formula (3a) obtained in Example 1 are shown. The results of the ¹³C-NMR measurement of the compound represented by formula (3a) obtained in Example 1 are shown. The results of the GC-MS measurement of the compound represented by formula (3a) obtained in Example 1 are shown. The results of the GC-TOFMS measurement of the compound represented by formula (3a) obtained in Example 1 are shown. The results of the ¹H-NMR measurement of the compound represented by formula (1b) obtained in Example 2 are shown. The results of the ¹³C-NMR measurement of the compound represented by formula (1b) obtained in Example 2 are shown. The results of the GC-MS measurement of the compound represented by formula (1b) obtained in Example 2 are shown. The results of the GC-TOFMS measurement of the compound represented by formula (1b) obtained in Example 2 are shown. The results of the ¹H-NMR measurement of the compound represented by formula (1'b) obtained in Example 2 are shown. The results of the ¹³C-NMR measurement of the compound represented by formula (1'b) obtained in Example 2 are shown. The results of the GC-MS measurement of the compound represented by formula (1'b) obtained in Example 2 are shown. The results of the GC-TOFMS measurement of the compound represented by formula (1'b) obtained in Example 2 are shown. The results of the 1H-NMR measurement of the compound represented by formula (2b) obtained in Example 2 are shown.The results of the 13C-NMR measurement of the compound represented by formula (2b) obtained in Example 2 are shown. The results of the GC-MS measurement of the compound represented by formula (2b) obtained in Example 2 are shown. The results of the GC-TOFMS measurement of the compound represented by formula (2b) obtained in Example 2 are shown. The results of the 1H-NMR measurement of the compound represented by formula (3b) obtained in Example 2 are shown. The results of the 13C-NMR measurement of the compound represented by formula (3b) obtained in Example 2 are shown. The results of the GC-MS measurement of the compound represented by formula (3b) obtained in Example 2 are shown. The results of the GC-TOFMS measurement of the compound represented by formula (3b) obtained in Example 2 are shown.

[0016] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). This embodiment is illustrative for explaining the present invention and is not intended to limit the present invention to the following content. The present invention can be implemented by modifying it as appropriate within the scope of its gist.

[0017] <<Bifunctional Compound>> The bifunctional compound of this embodiment is a compound represented by the following formula (1).

[0018]

[0019] In formula (1), Cy represents a cyclohexyl group, and n represents 0 or 1.

[0020] The bifunctional compound having a norbornane skeleton represented by formula (1) exhibits particularly excellent performance when used as a paint additive, adhesive, resin raw material, etc.

[0021] The bifunctional compound of this embodiment may be produced by carrying out the reaction shown in the following reaction formula. As shown in the following reaction formula, the bifunctional compound of this embodiment can be synthesized using cinnamon alcohol (i.e., 3-phenyl-2-propen-1-ol) as a starting material.

[0022]

[0023] In the above reactions, reaction (1-1) represents the Diels-Alder reaction, reaction (1-2) represents the oxo reaction, and reaction (1-3) represents the reduction reaction (including hydrogenation and nuclear hydrogenation).

[0024] ≪Compounds≫ The compounds of this embodiment may be intermediates in the process of synthesizing the bifunctional compounds of this embodiment. The compounds of this embodiment include the following embodiments.

[0025] <First Embodiment> (Compound of the First Embodiment) The compound of the first embodiment is represented by the following formula (3a) or formula (3b). As shown in these formulas, the compound of the first embodiment is a cyclic olefin compound having a hydroxyl group and a benzene ring.

[0026] The phenyl groups in formulas (3a) and (3b) may each have substituents. Examples of substituents include C1-C4 alkyl groups, C1-C4 alkoxy groups, C1-C4 alkenyl groups, halogens, and hydroxyl groups. The phenyl group may contain 0-5 substituents, for example, 1-3 substituents, or 1 or 2 substituents.

[0027] The compound of the first embodiment is obtained by reaction (1-1), which represents the Diels-Alder reaction in the reaction formula for producing the bifunctional compound of this embodiment described above. This will be explained in more detail below.

[0028] (Method for producing the compound of the first embodiment) The method for producing the compound of the first embodiment includes a cinnamon alcohol reaction step in which cinnamon alcohol and dicyclopentadiene are reacted to obtain the compound of the first embodiment. By including the cinnamon alcohol reaction step in the method for producing the compound of the first embodiment, the compound of the first embodiment can be obtained as an intermediate.

[0029] [Cinnamon Alcohol Reaction Step] The cinnamon alcohol reaction step is a step in which cinnamon alcohol and dicyclopentadiene are reacted to obtain the compound of the first embodiment. The dicyclopentadiene used in the Diels-Alder reaction between cinnamon alcohol and dicyclopentadiene in this embodiment is preferably high-purity dicyclopentadiene. The purity of the dicyclopentadiene is preferably 90% or higher, and more preferably 95% or higher. Furthermore, dicyclopentadiene can depolymerize under heating conditions to become cyclopentadiene (so-called monocyclopentadiene). Therefore, cyclopentadiene may be used instead of dicyclopentadiene.

[0030] In the cinnamon alcohol reaction step, the reaction temperature is preferably 150°C or higher and 300°C or lower. In order to efficiently carry out the Diels-Alder reaction, it is desirable that cyclopentadiene be present in the reaction system. A reaction temperature of 150°C or higher makes it easier for dicyclopentadiene to supply cyclopentadiene, thus making it easier to obtain the compound of the first embodiment. From the above viewpoint, a reaction temperature of 165°C or higher is more preferable. A reaction temperature of 170°C or higher or 175°C or higher is even more preferable. A reaction temperature of 300°C or lower can suppress the formation of high-boiling by-products. From the above viewpoint, a reaction temperature of 250°C or lower is more preferable. A reaction temperature of 220°C or lower or 200°C or lower is even more preferable.

[0031] In the cinnamon alcohol reaction step, the reaction time is preferably 3.0 hours to 10.0 hours, and more preferably 5.0 hours to 8.0 hours.

[0032] Suitable reaction solvents include hydrocarbons, alcohols, and esters. Among these, aliphatic hydrocarbons with six or more carbon atoms, cyclohexane, toluene, xylene, ethylbenzene, mesitylene, propanol, and butanol are preferred.

[0033] The Diels-Alder reaction in this embodiment can be carried out in various ways, including a batch reaction using a tank reactor, a semi-batch reaction in which substrates or substrate solutions are supplied to a tank reactor under reaction conditions, and a continuous flow reaction in which substrates are flowed through a tubular reactor under reaction conditions. The reaction product obtained in the Diels-Alder reaction in this embodiment may be used as is as a raw material for the subsequent hydroformylation reaction, or it may be purified by methods such as distillation, extraction, or crystallization before being used as a raw material for the subsequent hydroformylation reaction.

[0034] In the cinnamon alcohol reaction step, the reaction between cinnamon alcohol and dicyclopentadiene may be carried out in a single step or in multiple steps.

[0035] <Second Embodiment> (Compound of the Second Embodiment) The compound of the second embodiment is represented by the following formula (2a) or formula (2b).

[0036]

[0037] In formulas (2a) and (2b), Ph represents a phenyl group. The compounds of the second embodiment are cyclic aldehyde compounds having a hydroxyl group and a benzene ring, as shown in these formulas. The phenyl groups in formulas (2a) and (2b) may each have substituents. Examples of substituents include C1-C4 alkyl groups, C1-C4 alkoxy groups, C1-C4 alkenyl groups, halogens, and hydroxyl groups. The phenyl group may contain 0-5 substituents, for example, 1-3 substituents, or 1 or 2 substituents.

[0038] The compound of the second embodiment is obtained by reaction (1-2) in the reaction formula for producing the bifunctional compound of the above embodiment, which represents an oxo reaction (e.g., a hydroformylation reaction). This will be described in more detail below.

[0039] (Method for Producing Compound of Second Embodiment) The method for producing the compound of the second embodiment includes a hydroformylation step of subjecting the compound of the first embodiment, carbon monoxide, and hydrogen gas to a hydroformylation reaction in the presence of a rhodium compound and an organic phosphorus compound to obtain the compound of the second embodiment. By including the hydroformylation step in the method for producing the compound of the second embodiment, the compound of the second embodiment as an intermediate can be obtained.

[0040] [Hydroformylation Step] The hydroformylation step is a step of subjecting the compound of the first embodiment, carbon monoxide, and hydrogen gas to a hydroformylation reaction in the presence of a rhodium compound and an organic phosphorus compound to obtain the compound of the second embodiment.

[0041] The rhodium compound used in the hydroformylation reaction of the present embodiment is not particularly limited as long as it forms a complex with the organic phosphorus compound and exhibits hydroformylation activity in the presence of carbon monoxide and hydrogen. Examples of the rhodium compound include rhodium acetylacetonate dicarbonyl (hereinafter also referred to as Rh(acac)(CO) ２ ), Rh ２ O ３ , Rh ４ (CO) １２ , Rh ６ (CO) １６ , Rh(NO ３ ) ３ , etc.

[0042] The rhodium compound may be introduced into the reaction mixture together with the organic phosphorus compound to form a rhodium metal hydride carbonyl phosphorus complex having catalytic activity in the reaction vessel, or a rhodium metal hydride carbonyl phosphorus complex may be prepared in advance and introduced into the reactor. Specific examples include, for example, a method in which Rh(acac)(CO) ２ is reacted with an organic phosphorus compound in the presence of a solvent and then introduced into the reactor together with an excess of the organic phosphorus compound to obtain a rhodium-organic phosphorus complex having catalytic activity.

[0043] Examples of the organic phosphorus compound include those represented by the general formula P(−R １ )(−R ２ )(−R ３) represented by phosphine or P(-OR １ )(-OR ２ )(-OR ３ Examples include phosphites represented by ). １ , R ２ , and R ３ Specific examples include aryl groups which may be substituted with C1-C4 alkyl or alkoxy groups, and alicyclic alkyl groups which may be substituted with C1-C4 alkyl or alkoxy groups. Among these, triphenylphosphine and triphenylphospite are preferably used.

[0044] The hydroformylation reaction in this embodiment can be carried out without a solvent, but a solvent that is inert to the reaction can be used. There are no particular restrictions on the solvent as long as it dissolves each of the above-mentioned components. Specifically, examples include hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons; esters such as aliphatic esters, alicyclic esters, and aromatic esters; alcohols such as aliphatic alcohols and alicyclic alcohols; and aromatic halides. Among the above, hydrocarbons are preferably used, and alicyclic hydrocarbons and aromatic hydrocarbons are more preferably used.

[0045] In the hydroformylation step, the reaction temperature is preferably 50°C to 170°C, and more preferably 100°C to 150°C. Even more preferably, the reaction temperature in the hydroformylation step is 105°C to 135°C or 110°C to 140°C. When the reaction temperature is 50°C or higher, a sufficient reaction rate can be obtained, and the residue of the compound from the first embodiment, which is the raw material, can be suppressed. Furthermore, by setting the reaction temperature to 170°C or lower, the residue of the compound from the first embodiment, which is the raw material, and the generation of by-products derived from the reaction product can be suppressed.

[0046] In this embodiment, the hydroformylation reaction involves carbon monoxide (hereinafter also referred to as "CO") and hydrogen (hereinafter referred to as "H") ２ This is performed under gas pressure (also known as CO / H). ２The gases can be introduced into the reaction system individually or as a pre-prepared mixed gas. ２ Gas molar ratio (= CO / H) ２ ) is preferably 0.2 to 5, more preferably 0.5 to 2, and even more preferably 0.8 to 1.2. CO / H ２ By keeping the gas molar ratio within the above range, the reaction activity of the hydroformylation reaction and the selectivity of the target aldehyde are excellent. CO / H introduced into the reaction system ２ As the gas decreases as the reaction progresses, the pre-prepared CO / H ２ In some cases, reaction control can be easily performed by using gas.

[0047] In the hydroformylation step, the pressure is preferably 1.0 MPa to 12.0 MPa, more preferably 1.2 MPa to 9.0 MPa, and even more preferably 1.5 MPa to 5.0 MPa. The pressure in the hydroformylation step is particularly preferably 1.8 MPa to 3.0 MPa. By setting the pressure to 1.0 MPa or higher, a sufficient reaction rate can be obtained, and the residue of the compound of the first embodiment, which is the raw material, can be suppressed. Furthermore, by setting the pressure to 12.0 MPa or lower, the reaction can be easily carried out without using expensive equipment with excellent pressure resistance.

[0048] In this embodiment, batch reactions and semi-batch reactions are preferred as reaction methods for the hydroformylation reaction. In a semi-batch reaction, for example, a rhodium compound, an organophosphorus compound, and the above solvent are added to a reactor, and CO / H ２ This can be carried out by pressurizing and heating with gas to achieve the reaction conditions described above, and then supplying the compound of the first embodiment or its solution, which is the raw material, to the reactor. The reaction product obtained in the hydroformylation reaction of this embodiment can be purified by, for example, distillation, extraction, crystallization, etc.

[0049] In the hydroformylation step, the reaction time is preferably 3.0 hours to 10.0 hours, and more preferably 5.0 hours to 8.0 hours.

[0050] ≪Method for Producing a Bifunctional Compound≫ The method for producing a bifunctional compound according to this embodiment includes a step for producing a bifunctional compound by reducing the compound of the second embodiment (i.e., the compound represented by formula (2a) or formula (2b)) in the presence of a catalyst having hydrogenation ability and hydrogen to obtain the bifunctional compound of this embodiment.

[0051] The method for producing the bifunctional compound of this embodiment preferably includes the above-described cinnamon alcohol reaction step, in which cinnamon alcohol and dicyclopentadiene are reacted to obtain a compound represented by the following formula (3a) or (3b) before the above-described bifunctional compound production step, and the above-described hydroformylation step, in which the compound represented by formula (3a) or (3b), carbon monoxide, and hydrogen gas are hydroformylated in the presence of a rhodium compound and an organophosphorus compound to obtain a compound represented by formula (2a) or (2b).

[0052] The catalyst having hydrogenation ability preferably contains at least one selected from the group consisting of copper, chromium, iron, zinc, aluminum, nickel, cobalt, palladium, and ruthenium. Specifically, examples of catalysts having hydrogenation ability include Cu-Cr catalysts, Cu-Zn catalysts, Cu-Zn-Al catalysts, Ru-Al catalysts, etc. Raney-Ni catalysts, Raney-Co catalysts, etc. may also be used.

[0053] The total amount of catalyst used is preferably 1 to 100% by mass, more preferably 2 to 50% by mass, and even more preferably 2 to 40% by mass, 3 to 35% by mass, or 5 to 30% by mass, relative to the total amount of the compound in the second embodiment. By setting the amount of catalyst used within the above range, the reduction reaction can be suitably carried out.

[0054] The process for producing a bifunctional compound may include: a hydrogenation step of reducing the compound of the second embodiment (i.e., the compound represented by formula (2a) or formula (2b)) in the presence of a hydrogenating catalyst and hydrogen to obtain a compound represented by the following formula (1'); and a nuclear hydrogenation step of reducing the compound represented by the above formula (1') after the hydrogenation step in the presence of a hydrogenating catalyst and hydrogen to obtain the bifunctional compound of this embodiment.

[0055]

[0056] In formula (1'), Ph represents a phenyl group, and n represents 0 or 1. In formula (1'), n is preferably 1. Each phenyl group in formula (1') may have substituents. Examples of substituents include C1-C4 alkyl groups, C1-C4 alkoxy groups, C1-C4 alkenyl groups, halogens, hydroxyl groups, and the like. The phenyl group may contain 0-5 substituents, for example, 1-3 substituents, or 1 or 2 substituents.

[0057] In the hydrogenation process, specific catalysts with hydrogenation ability may include Cu-Cr catalysts, Cu-Zn catalysts, Cu-Zn-Al catalysts, etc. It is also preferable to use Raney-Ni catalysts, Raney-Co catalysts, etc.

[0058] In the hydrogenation step, the amount of catalyst used is preferably 1 to 10% by mass, and more preferably 2 to 7% by mass, relative to the total amount of the compound of the second embodiment.

[0059] In the nuclear hydrogenation process, it is preferable to use a Ru-Al catalyst or the like as the catalyst having hydrogenation ability.

[0060] In the nuclear hydrogenation process, the amount of catalyst used is preferably 10 to 90% by mass, more preferably 20 to 75% by mass, and even more preferably 30 to 60% by mass, relative to the total amount of the compound represented by formula (1').

[0061] The reaction temperature for the reduction reaction in this embodiment is preferably 80 to 250°C, and more preferably 100 to 230°C. The reaction temperature for the reduction reaction is even more preferably 100 to 180°C, 100 to 150°C, or 105 to 120°C. By setting the reaction temperature to 250°C or lower, the occurrence of side reactions and decomposition reactions can be suppressed, and the target product can be obtained in high yield. Furthermore, by setting the reaction temperature to 80°C or higher, the reaction can be completed in a reasonable amount of time, thereby avoiding a decrease in productivity and a decrease in the yield of the target product.

[0062] The pressure for the reduction reaction in this embodiment is preferably 1 to 20 MPa, more preferably 1.5 to 10 MPa or 2 to 15 MPa. By keeping the pressure below 20 MPa, the occurrence of side reactions and decomposition reactions is suppressed, and the target product can be obtained in high yield. Furthermore, by keeping the pressure above 1 MPa, the reaction can be completed in a suitable amount of time, thus avoiding a decrease in productivity and a decrease in the yield of the target product.

[0063] In the reduction reaction of this embodiment, a solvent can be used. Examples of solvents include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and alcohols. Among these, alicyclic hydrocarbons, aromatic hydrocarbons, and alcohols are preferred. Specific examples of solvents include cyclohexane, toluene, xylene, methanol, ethanol, 1-propanol, and cyclohexanol.

[0064] The reaction method for the reduction reaction in this embodiment can be a batch method using a tank reactor, a semi-batch method in which a substrate or substrate solution is supplied to a tank reactor under reaction conditions, or a continuous flow method in which a substrate or substrate solution is flowed through a tubular reactor filled with a molded catalyst under predetermined reaction conditions. The reaction product obtained in the reduction reaction of this embodiment can be purified by, for example, distillation, extraction, crystallization, etc.

[0065] ≪Thermoplastic Resin≫ The thermoplastic resin of this embodiment contains a constituent unit (A) derived from the compound represented by formula (1) above. The thermoplastic resin of this embodiment may be manufactured using the bifunctional compound of this embodiment as the raw material monomer. As long as it contains the predetermined constituent unit, there are no particular limitations on the type of thermoplastic resin, but the thermoplastic resin is preferably a polycarbonate resin, a polyester carbonate resin, or a polyester resin. The thermoplastic resin may also be a mixture of two or more types, such as polycarbonate resin, polyester carbonate resin, and polyester resin.

[0066] The thermoplastic resin may be a homopolymer, or a copolymer such as a random copolymer or a block copolymer. Alternatively, the thermoplastic resin may be a mixture of copolymers such as a homopolymer, a random copolymer, or a block copolymer.

[0067] <Constituent Unit (A) of Thermoplastic Resin> Constituent unit (A) is derived from the compound represented by the following formula (1).

[0068]

[0069] In formula (1), Cy represents a cyclohexyl group, and n represents 0 or 1. Each of these cyclohexyl groups may have substituents. Examples of substituents include C1-C4 alkyl groups, C1-C4 alkoxy groups, C1-C4 alkenyl groups, halogens, and hydroxyl groups. The cyclohexyl group may contain 0-5 substituents, for example, 1-3 substituents, or 1 or 2 substituents.

[0070] In formula (1), n ​​represents 0 or 1, and n is preferably 1. Thus, a preferred specific example of a constituent unit (A) derived from a compound in formula (1) where n is 1 is a constituent unit derived from a compound represented by the following formula (1-2) (hereinafter also referred to as D-NPDM).

[0071]

[0072] In thermoplastic resins, the content of constituent unit (A) is preferably 10 to 100 mol%, based on the total number of moles of constituent units. The content of constituent unit (A) in thermoplastic resins based on the total number of moles is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, and even more preferably 15 to 80 mol%. The content of constituent unit (A) in thermoplastic resins may also be 30 to 90 mol%, 40 to 90 mol%, 45 to 90 mol%, 40 to 85 mol%, 45 to 85 mol%, 55 to 85 mol%, 60 to 85 mol%, 60 to 80 mol%, or 65 to 80 mol%, etc. Furthermore, all constituent units in the thermoplastic resin may be constituent unit (A).

[0073] <Constituent units (B) of thermoplastic resin> The thermoplastic resin may further contain constituent units (B) derived from a diol compound as a monomer represented by the following formula (6).

[0074]

[0075] In equation (6), R ａ and R ｂ Each of these independently comprises a hydrogen atom, a halogen atom, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxyl group, an optionally substituted C5-C20 cycloalkyl group, an optionally substituted C5-C20 cycloalkoxyl group, an optionally substituted C6-C20 aryl group, an optionally substituted C6-C20 heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S, an optionally substituted C6-C20 aryloxy group, and -C≡C-R ｈ Selected from the group consisting of the above R ｈ This represents an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group having 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N, and S.

[0076] R in equation (6) ａ and R ｂ Preferably, the group is selected from a hydrogen atom, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxyl group, an optionally substituted C5-C20 cycloalkyl group, or an optionally substituted C6-C20 aryl group, and more preferably, from a hydrogen atom, an optionally substituted C1-C20 alkyl group, or an optionally substituted C6-C20 aryl group. ａ and R ｂ More preferably, it is selected from a hydrogen atom and an aryl group having 6 to 20 carbon atoms, which may have substituents.

[0077] In formula (6), X is a single bond or an alkylene group having 3 or fewer carbon atoms which may have substituents, preferably a single bond or an alkylene group having 2 or fewer carbon atoms which may have substituents, more preferably a single bond or an alkylene group having 1 carbon atom which may have substituents, and particularly preferably a single bond. In formula (6), A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have substituents, preferably an alkylene group having 1 to 3 carbon atoms which may have substituents, more preferably an alkylene group having 2 or 3 carbon atoms, an alkylene group having 1 or 2 carbon atoms, etc. In formula (6), m and n each independently represent an integer from 0 to 6, preferably an integer from 0 to 3, and more preferably 0 or 1. In formula (6), a and b each independently represent an integer from 0 to 10, preferably an integer from 0 to 5, more preferably an integer from 0 to 3, and particularly preferably 0 or 1.

[0078] R in equation (6) ａ and R ｂ Of the options, the number of carbon atoms in the C1-C20 alkyl group which may have substituents and the C1-C20 alkoxyl group which may have substituents is preferably 1-10, more preferably 1-6, and even more preferably 1-3, or 1, respectively. ａ and R ｂ Of the options, the number of carbon atoms in the cycloalkyl group having 5 to 20 carbon atoms, which may have substituents, and the cycloalkoxyl group having 5 to 20 carbon atoms, which may have substituents, is preferably 5 to 10, more preferably 6 to 8, and even more preferably 6 or 7. In formula (6), R ａ and R ｂ Among the options, the carbon number of the substituted heteroaryl group having 6 to 20 carbon atoms and the substituted aryloxy group having 6 to 20 carbon atoms, which include one or more heterocyclic atoms selected from O, N, and S, is preferably 6 to 12, more preferably 6 to 10, and even more preferably 6 to 8 or 6, respectively.

[0079] The substituents that may be included in the constituent unit (B) of formula (6) above include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, amide groups having 1 to 10 carbon atoms, alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, cycloalkyloxy groups having 5 to 10 carbon atoms, alkyloxycarbonyl groups having 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups having 5 to 10 carbon atoms, aryloxycarbonyl groups having 7 to 15 carbon atoms, alkylcarbonyloxy groups having 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups having 5 to 10 carbon atoms, arylcarbonyloxy groups having 7 to 15 carbon atoms, hydroxyalkylcarbonyl groups having 2 to 10 carbon atoms, and glycidyloxycarbonyl groups. The number of carbon atoms in formula (1) also includes the number of carbon atoms in the substituents.

[0080] Preferred specific examples of monomers that form the above-mentioned constituent unit (B) include, for example, 2,2'-bis(hydroxy(poly)alkoxy)-diaryl-1,1'-binaphthalenes and 2,2'-bis(hydroxy(poly)alkoxy)-dinaphthyl-1,1'-binaphthalenes. Of these monomer compounds, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxymethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxymethoxy)-6,6'-di(naphthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxypropoxy)-6,6'-diphenyl-1,1'-binaphthalene, and 2,2'-bis(2-hydroxypropoxy)-6,6'-di(naphthalen-1-yl)-1,1'-binaphthalene are preferred. The monomer compounds described above may be used individually or in combination of two or more to form a constituent unit (B).

[0081] Specific examples of monomer compounds of constituent unit (B) include compounds having the following molecular structures.

[0082]

[0083] The thermoplastic resin may be a copolymer having both the constituent unit (A) and the constituent unit (B) described above. In such a copolymer thermoplastic resin, the content of constituent unit (B) is, for example, 1 to 99 mol% or 10 to 80 mol%, preferably 20 to 70 mol% or 25 to 60 mol%, and more preferably 30 to 50 mol%, based on the total number of moles of constituent units.

[0084] <Constituent Unit (C) of Thermoplastic Resin> The thermoplastic resin may further contain constituent units (C) derived from a diol compound as a monomer represented by formula (7).

[0085]

[0086] In equation (7), R ｃ and R ｄ Each of these is independently selected from the group consisting of a hydrogen atom, a halogen atom, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxyl group, an optionally substituted C5-C20 cycloalkyl group, an optionally substituted C5-C20 cycloalkoxyl group, and an optionally substituted C6-C20 aryl group.

[0087] R in equation (7) ｃ and R ｄ Preferably, each is independently selected from a hydrogen atom, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxyl group, an optionally substituted C5-C20 cycloalkyl group, and an optionally substituted C6-C20 aryl group, and more preferably, each is selected from a hydrogen atom, an optionally substituted C1-C20 alkyl group, and an optionally substituted C6-C20 aryl group. ｃ and R ｄ More preferably, it is selected from a hydrogen atom and an aryl group having 6 to 20 carbon atoms, which may have substituents.

[0088] R in equation (7) ｃ and Rｄ Of the options, the number of carbon atoms in the C1-C20 alkyl group which may have substituents and the C1-C20 alkoxyl group which may have substituents is preferably 1-10, more preferably 1-6, and even more preferably 1-3, or 1, respectively. ｃ and R ｄ Of the options, the number of carbon atoms in the cycloalkyl group having 5 to 20 carbon atoms, which may have substituents, and the cycloalkoxyl group having 5 to 20 carbon atoms, which may have substituents, is preferably 5 to 10, more preferably 6 to 8, and even more preferably 6 or 7. R in formula (7) ｃ and R ｄ Of these options, the number of carbon atoms in the aryl group having 6 to 20 carbon atoms, which may have substituents, is preferably 6 to 12, more preferably 6 to 10, and even more preferably 6 to 8, or 6.

[0089] In equation (7), Y １ is a single bond, a fluorene group which may have substituents, or any of the structural formulas represented by the following formulas (8) to (15), preferably Y １ This is either a single bond or a fluorene group.

[0090]

[0091]

[0092]

[0093] In equations (8), (14), and (15), R ６１ , R ６２ , R ７１ , R ７２ , R ８１ and R ８２ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R ６１ and R ６２ , or R ７１ and R ７２represents a carbocyclic or heterocyclic ring having 4 to 20 carbon atoms, which may have a substituent, formed by bonding to each other. In addition, in formulas (12) and (14), r and s each independently represent an integer of 0 to 5000. Note that Y in formula (7) １ In the above formulas (8) to (15) showing the options of ６１ R ６２ R ７１ R ７２ R ８１ R ８２ and R

[0094] In formulas (8), (14) and (15), the straight lines at both ends not bonded to any of the substituents of ６１ R ６２ R ７１ R ７２ R ８１ R ８２ and R ６１ R ６２ R ７１ R ７２ R ８１ R ８２ and R ６１ R ６２ R ７１ R ７２ Rm ８１ R ８２ and R

[0095] In formula (7), A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have substituents, preferably an alkylene group having 1 to 3 carbon atoms which may have substituents, more preferably an alkylene group having 2 or 3 carbon atoms, an alkylene group having 1 or 2 carbon atoms, and so on. In formula (7), p and q each independently represent an integer from 0 to 4, preferably an integer from 0 to 3, and more preferably 0 or 1. In formula (7), a and b each independently represent an integer from 0 to 10, preferably an integer from 0 to 5, more preferably an integer from 0 to 3, and particularly preferably 0 or 1.

[0096] The substituents that may be included in the constituent unit (C) of formula (7) above include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, amide groups having 1 to 10 carbon atoms, alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, cycloalkyloxy groups having 5 to 10 carbon atoms, alkyloxycarbonyl groups having 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups having 5 to 10 carbon atoms, aryloxycarbonyl groups having 7 to 15 carbon atoms, alkylcarbonyloxy groups having 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups having 5 to 10 carbon atoms, arylcarbonyloxy groups having 7 to 15 carbon atoms, hydroxyalkylcarbonyl groups having 2 to 10 carbon atoms, and glycidyloxycarbonyl groups. The number of carbon atoms in formula (7) also includes the number of carbon atoms in the substituents.

[0097] Preferred examples of monomers that form the above-mentioned structural unit (C) include BNEF (9,9-bis(6-(2-hydroxyethoxy)naphthalene-2-yl)fluorene), BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene), BCFL (biscresol fluorene), and BPM (bisphenol M). The above-mentioned monomer compounds may be used individually or in combination of two or more to form structural unit (C). Specific examples of monomer compounds for structural unit (C) include compounds having the following molecular structures.

[0098]

[0099] The thermoplastic resin may be a copolymer having both the constituent unit (A) and the constituent unit (C) described above. In such a copolymer thermoplastic resin, the content of constituent unit (C) is, for example, 1 to 99 mol% or 10 to 80 mol%, preferably 20 to 70 mol% or 25 to 60 mol%, and more preferably 30 to 50 mol%, based on the total number of moles of constituent units.

[0100] <Constituent units (D) of thermoplastic resin> The thermoplastic resin may further contain constituent units (D) derived from a diol compound as a monomer represented by formula (2).

[0101]

[0102] In equation (2), Z is H, CH ３ or C ２ H ５ Z represents H or CH, where Z is preferably H or CH. ３ The result is H, and more preferably H. In formula (2), t represents 0 or 1, and preferably 1.

[0103] The monomer compound of formula (2) above may have substituents, and examples of substituents include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, amide groups having 1 to 10 carbon atoms, alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, cycloalkyloxy groups having 5 to 10 carbon atoms, alkyloxycarbonyl groups having 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups having 5 to 10 carbon atoms, aryloxycarbonyl groups having 7 to 15 carbon atoms, alkylcarbonyloxy groups having 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups having 5 to 10 carbon atoms, arylcarbonyloxy groups having 7 to 15 carbon atoms, hydroxyalkylcarbonyl groups having 2 to 10 carbon atoms, and glycidyloxycarbonyl groups.

[0104] A preferred specific example of a monomer that forms the above-mentioned constituent unit (D) is D-NDM, as shown in the following formula.

[0105]

[0106] The thermoplastic resin may be, for example, a copolymer having both the above-described structural unit (A) and structural unit (D). In such a thermoplastic resin which is a copolymer, based on the total number of moles of the structural units, the content of the structural unit (D) is, for example, 1 to 99 mol% or 10 to 95 mol%, preferably 30 to 90 mol% or 50 to 85 mol%, and more preferably 70 to 85 mol% or the like.

[0107] <Other structural units> In the thermoplastic resin, structural units other than the above-described structural units (A) to (D) may be included. For example, in the thermoplastic resin, structural units derived from a monomer represented by the following formula may further be included.

[0108]

[0109] In the above formula, R １ and R ２ each independently represent a hydrogen atom, a methyl group or an ethyl group. R １ and R ２ are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. In the above formula, R ３ and R ４ each independently represent an aryl group, a hydrogen atom, a methyl group, an ethyl group or an alkylene glycol having 2 to 5 carbon atoms. R ３ and R ４ are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. In the above formula, i and ii each independently represent an integer of 1 to 3. i and ii are preferably 1 or 2, and more preferably 1.

[0110] In the thermoplastic resin, based on the total number of moles of the structural units, the content of the above-described other structural units is, for example, 1 to 99 mol% or 10 to 80 mol%, preferably 20 to 70 mol% or 25 to 60 mol%, and more preferably 30 to 50 mol% or the like.

[0111] Thermoplastic resins may contain a certain amount of impurities. For example, alcohol compounds such as phenolic compounds that may be produced as by-products during the manufacture of polycarbonate resins, unreacted diol components, or diester carbonates may be present as impurities in thermoplastic resins. However, since alcohol compounds such as phenolic compounds and diester carbonates, which are impurities, can reduce the strength of the thermoplastic resin when it is molded and can cause odor generation, it is preferable to keep their content as low as possible.

[0112] The content of residual phenolic compounds in the thermoplastic resin is preferably 3,000 ppm by mass or less, more preferably 1,000 ppm by mass or less, and particularly preferably 300 ppm by mass or less, based on 100% by mass of the thermoplastic resin. The content of residual diol components is preferably 1,000 ppm by mass or less, more preferably 100 ppm by mass or less, and particularly preferably 10 ppm by mass or less, based on 100% by mass of the thermoplastic resin. The content of residual diester carbonate is preferably 1,000 ppm by mass or less, more preferably 100 ppm by mass or less, and particularly preferably 10 ppm by mass or less, based on 100% by mass of the thermoplastic resin. In particular, it is preferable that the content of compounds such as phenol and t-butylphenol be low, and it is preferable that these compounds be within the above ranges.

[0113] The content of phenolic compounds remaining in thermoplastic resins can be measured by analyzing phenolic compounds extracted from the thermoplastic resin using gas chromatography. Similarly, the content of alcoholic compounds remaining in thermoplastic resins can be measured by analyzing alcoholic compounds extracted from the thermoplastic resin using gas chromatography. The content of diol components and diester carbonates remaining in thermoplastic resins can also be measured by extracting these compounds from the thermoplastic resin and analyzing them using gas chromatography.

[0114] The content of by-product alcohol compounds such as phenolic compounds, diol components, and diester carbonates may be reduced to an undetectable level, but from a productivity standpoint, they may be present in small amounts as long as they do not impair the effect. Furthermore, small amounts can improve plasticity during resin melting.

[0115] The content of each of the remaining phenolic compounds, diol components, or diester carbonates may be, for example, 0.01 ppm or more, 0.1 ppm or more, or 1 ppm or more, based on 100% by mass of the thermoplastic resin. The content of the remaining alcoholic compounds may be, for example, 0.01 ppm or more, 0.1 ppm or more, or 1 ppm or more, based on 100% by mass of the thermoplastic resin.

[0116] The content of by-product alcohol compounds such as phenolic compounds, diol components, and diester carbonates in thermoplastic resins can be adjusted to fall within the above range by appropriately adjusting the polycondensation conditions and equipment settings. It can also be adjusted by the conditions of the extrusion process after polycondensation.

[0117] For example, the residual amount of by-product alcohol compounds, such as phenolic compounds, is related to the type of diester carbonate used in the polymerization of thermoplastic resins, as well as the polymerization reaction temperature and polymerization pressure. By adjusting these factors, the residual amount of by-product alcohol compounds, such as phenolic compounds, can be reduced.

[0118] For example, when thermoplastic resins such as polycarbonate are manufactured using dialkyl carbonates such as diethyl carbonate, the molecular weight does not increase easily, resulting in a low molecular weight thermoplastic resin, and the content of by-product alkyl alcohol compounds tends to increase. Such alkyl alcohols are highly volatile, and if they remain in the thermoplastic resin, the moldability of the resin tends to deteriorate. In addition, if a large amount of by-product alcohol compounds such as phenolic compounds remain, there is a possibility of odor problems during resin molding, and a cleavage reaction of the resin skeleton may proceed during compounding, leading to a decrease in molecular weight. Therefore, it is preferable that the content of residual by-product alcohol compounds in the obtained thermoplastic resin is 3000 ppm by mass or less relative to the thermoplastic resin (100% by mass). The content of residual alcohol compounds is preferably 3000 ppm by mass or less, more preferably 1000 ppm by mass or less, and particularly preferably 300 ppm by mass or less, relative to 100% by mass of the thermoplastic resin.

[0119] ≪Thermoplastic Resin Composition≫ The thermoplastic resin described above may be used as a thermoplastic resin composition containing components other than the thermoplastic resin. The thermoplastic resin composition may contain, for example, at least one additive selected from mold release agents, antioxidants, etc. In the thermoplastic resin composition, the content of secondary components such as additives other than the thermoplastic resin is preferably 20% by weight or less, more preferably 15% by weight or less or 10% by weight or less, even more preferably 7% by weight or less or 5% by weight or less, and particularly preferably 3% by weight or less or 2% by weight or less, based on the total weight. Furthermore, the content of secondary components such as additives other than the thermoplastic resin in the thermoplastic resin composition is, for example, 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more or 1% by weight or more, based on the total weight of the thermoplastic resin composition.

[0120] Specific examples of additives included in thermoplastic resin compositions are as follows:

[0121] <Antioxidants> Examples of antioxidants include phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, and polyphenolic antioxidants.

[0122] Specifically, 2,6-di-tert-butyl-4-methylphenol, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 4,4'-butylidenebis-(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-ter [t-butyl-4-hydroxy-5-methylphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N' -Hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphoate, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxy Examples include bis(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), hexamethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol.Examples of phenolic antioxidants include "Irganox 1010" (registered trademark, hereinafter the same) and "Irganox 1076" manufactured by BASF, and "Adeka Stab AO-50" and "Adeka Stab AO-60" manufactured by Adeka.

[0123] The amount of antioxidant added is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, per 100 parts by mass of the thermoplastic resin composition. The antioxidant may contain only one type or two or more types. If two or more types are included, it is preferable that the total amount is within the above range.

[0124] <Release Agents> Examples of release agents include carboxylic acid esters, polysiloxane compounds, and paraffin wax (polyolefin-based). Specifically, at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils can be mentioned. Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic monovalent, divalent, or trivalent carboxylic acids. Here, aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and more preferably aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms. Specific examples of aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, glutaric acid, adipic acid, and azelaic acid. The same aliphatic carboxylic acids as those mentioned above can be used as the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid with an alcohol. On the other hand, saturated or unsaturated monohydric or polyhydric alcohols can be used as the alcohol. These alcohols may have substituents such as fluorine atoms or aryl groups. Among these, monohydric or polyhydric saturated alcohols with 30 or fewer carbon atoms are preferred, and aliphatic saturated monohydric or polyhydric alcohols with 30 or fewer carbon atoms are more preferred. Here, alicyclic compounds are also included in the term aliphatic. Specific examples of alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol.

[0125] The ester compounds described above may contain aliphatic carboxylic acids and / or alcohols as impurities, and may be mixtures of multiple compounds. Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture mainly composed of myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate. Examples of aliphatic hydrocarbons with a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Here, alicyclic hydrocarbons are also included in aliphatic hydrocarbons. Furthermore, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or partially oxided polyethylene wax are preferred, with paraffin wax and polyethylene wax being more preferred. The number average molecular weight is preferably 200 to 5000. These aliphatic hydrocarbons may be a single substance or a mixture of substances with various components and molecular weights, as long as the main component is within the above range. Examples of polysiloxane-based silicone oils include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.

[0126] The proportion of the release agent added is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the thermoplastic resin composition. Only one type of release agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0127] Thermoplastic resin compositions may contain deactivators. Deactivators may be used to remove or deactivate polymerization catalysts after the completion of the polymerization reaction for the production of the thermoplastic resin contained in the thermoplastic resin composition, in order to maintain the thermal stability and hydrolysis stability of the resin. Typically, known acidic substances can be used as deactivators. For example, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate, aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate, organic halides such as stearate chloride, benzoyl chloride, and p-toluenesulfonic acid chloride, alkyl sulfuric acids such as dimethyl sulfate, and organic halides such as benzyl chloride can be used as deactivators.

[0128] The amount of inactivator added is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 2 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of the thermoplastic resin composition. Only one type of inactivator may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0129] ≪Methods for Manufacturing Thermoplastic Resins and Thermoplastic Resin Compositions≫ The following describes methods for manufacturing thermoplastic resins and the like. The thermoplastic resins mentioned above can be manufactured by known methods. For example, thermoplastic resins can be manufactured by carrying out a polymerization reaction in a reaction system containing a monomer compound and a catalyst under conditions of a polymerization temperature of 200 to 250°C and a pressure of 760 mmHg to 200 mmHg. For example, a thermoplastic resin such as polycarbonate resin can be manufactured by melt polycondensation using monomer compounds that form the above-mentioned constituent units, such as constituent unit (A), and carbonate precursors such as diester carbonate as raw materials, in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst containing both, or in the absence of a catalyst.

[0130] Thermoplastic resin compositions can be produced, for example, by melt-kneading one or more types of thermoplastic resins with the aforementioned secondary components, such as additives. Alternatively, they may be produced by dissolving the thermoplastic resins and additives in a solvent, blending them, and then volatilizing the solvent. Suitable solvents include, for example, halogenated organic solvents and THF. Thermoplastic resin compositions can be produced by a manufacturing method that includes such a mixing step. In the mixing step, additives may be mixed with the thermoplastic resins using known methods.

[0131] <<Applications>> The bifunctional compound of this embodiment can be used in a variety of applications. For example, it can be used as a monomer for optical materials, a raw material monomer for polycarbonate, etc. Examples of the optical materials include eyeglass lenses and camera lenses, with camera lenses being preferred and smartphone camera lenses being more preferred.

[0132] The embodiment will be described in more detail below with reference to examples, but this embodiment is not limited to these examples.

[0133] (Example 1) 1700 g (12.67 mol) of cinnamon alcohol and 433 g (3.27 mol) of dicyclopentadiene were charged into a 3 L stainless steel reactor, and the reaction was carried out at 185°C for 6.5 hours. As a result of the above reaction, a reaction solution containing 178 g of the compound represented by the following formula (3a) was obtained, and this was purified by distillation. This operation was repeated several times to obtain 774 g of the compound represented by the following formula (3a).

[0134] Using a 3L stainless steel reactor, CO and H ２ CO / H mixed ２ Gas (CO / H ２ Using a molar ratio of 1), the hydroformylation reaction of the compound represented by the following formula (3a), which had been purified by distillation, was carried out. 774 g of the compound represented by the following formula (3a), 774 g of 2-octanol, 2.70 g of triphenyl phosphite, and separately prepared Rh(acac)(CO) were added to the reactor. ２ One mL of 2-octanol solution (concentration 0.009 mol / L) was added. Nitrogen and CO / H ２After performing gas substitution three times each, CO / H ２ The system was pressurized with gas, and the reaction was carried out at 125°C and 2 MPa for 6 hours. After the reaction was complete, gas chromatography analysis of the reaction solution was performed, and it was confirmed that the reaction solution contained 766 g of the compound represented by formula (2a) (conversion rate > 99%, selectivity 89%). Subsequently, a portion was used in the following reaction.

[0135] 1400 g of the above reaction solution (including 700 g of the compound represented by formula (2a) below) and 20 g of sponge nickel catalyst (manufactured by Nikko Rica Co., Ltd.: R-200M) were added to a 3 L stainless steel reactor. The system was then pressurized with hydrogen gas and the reaction was carried out at 2 MPa and 120°C for 12 hours. After the reaction, the obtained slurry was filtered through a membrane filter with a pore size of 0.45 μm to remove the catalyst. Analysis by gas chromatography and GC-MS confirmed that it contained 662 g of the compound represented by formula (1'a) below with a molecular weight of 298 (main product yield 95%).

[0136] Further, 450 g of this mixture (including 215 g of the compound represented by formula (1'a) below) and 92 g of Ru / Al catalyst (manufactured by N.E. Chemcat Co., Ltd.) were added to a 1 L stainless steel reactor. The system was then pressurized with hydrogen gas, and the reaction was carried out at 5 MPa and 130°C for 5.5 hours. After the reaction, the resulting slurry was filtered through a 0.45 μm pore size membrane filter to remove the catalyst. Analysis by gas chromatography and GC-MS confirmed the presence of 202 g of the main product with a molecular weight of 304 represented by formula (1a) (main product yield 92%). This was further purified by distillation to obtain the main product.

[0137]

[0138] NMR analysis was performed on each component obtained in Example 1. The NMR spectra of the compound represented by formula (1a) are shown in Figures 1-2, the GCMS spectrum in Figure 3, and the GC-TOFMS spectrum in Figures 4(a) and (b). The NMR spectra of the compound represented by formula (1'a) are shown in Figures 5-6, the GCMS spectrum in Figure 7, and the GC-TOFMS spectrum in Figures 8(a) and (b). The NMR spectra of the compound represented by formula (2a) are shown in Figures 9-10, the GCMS spectrum in Figure 11, and the GC-TOFMS spectrum in Figures 12(a) and (b). The NMR spectra of the compound represented by formula (3a) are shown in Figures 13-14, the GCMS spectrum in Figure 15, and the GC-TOFMS spectrum in Figures 16(a) and (b). The measurement conditions for NMR analysis, GCMS, and GC-TOFMS are as follows.(NMR Measurement Conditions) ・Apparatus: JEOL Ltd., JNM-ECA500 (500MHz) ・Measurement Mode: ¹H-NMR, ¹³C-NMR ・Solvent: CDCl₃ (deuterated chloroform) ・Internal Standard: Tetramethylsilane (GCMS Measurement Conditions) Compounds of formulas (1a, 2a) ・Analytical Instrument: Agilent Technologies, Inc., 7890B / 5977A GC / MSD ・Ionization Voltage: 70eV ・Analytical Column: Agilent Technologies, DB-1 (φ0.25mm * 30m * t0.25um) ・Oven ​​Temperature: 60℃ (0.5 min) - Heating Rate 15℃ / min - 280℃ (11 min) ・Detector Temperature: 300℃ Compounds and analyzers for formula (1'a, 2'a, 1b, 2b, 3a, 3b): Agilent Technologies, Inc., 7890B / 5977A GC / MSD; Ionization voltage: 70 eV; Analytical column: Agilent Technologies, HP-5MS (φ0.25 mm * 30 m * t0.25 um); Oven temperature: 60°C (0.5 min) - heating rate 15°C / min - 280°C (6 min); Detector temperature: 300°C (GC-TOFMS measurement conditions); GC: JEOL JMS-T200GC; Column: DB-1 (φ0.25 mm * 30 m * t0.25 um) Oven temperature: 80°C (5 min) - 20°C / min - 280°C (5 min) Injection volume: 1 ul (split ratio 1:40) Injection temperature: 280°C Carrier: 1.0 ml / min (He) Measurement mode: MS Scan range: 33-700 / 0.2 sec Ionization: 70 ev (EI+).

[0139] From the results of GC-MS analysis, NMR analysis, and GC-TOFMS analysis, it was confirmed that each product obtained in Example 1 was the main product, the compound of formula (1a), and the intermediate compounds represented by formulas (1'a), (2a), and (3a), respectively. Furthermore, the final obtained compound of formula (1a) was a mixture of nearly equal amounts of two positional isomers of hydroxyl groups, and it is thought that the ratio of the endo isomer to the exo isomer was approximately 70:30 to 10:90. In the distillation process described above for the compound of formula (1a), it was not easy to reliably separate the endo and exo isomers, which have slightly different boiling points. However, in the initial distillation, a component rich in the endo isomer was obtained, and in the secondary distillation, a component rich in the exo isomer was distilled off. Thus, it is possible to obtain a component rich in either the endo or exo isomer, and according to the above process, a mixture with an endo isomer to exo isomer ratio in the range of approximately 70:30 to 10:90 can be obtained. Furthermore, based on the results of peak analysis in the GC chart, it is estimated that the ratio of the endo-isomer to the exo-isomer in the compound (3a) above was approximately 30:70.

[0140] (Example 2) 1700 g (12.67 mol) of cinnamon alcohol and 433 g (3.27 mol) of dicyclopentadiene were charged into a 3 L stainless steel reactor, and the reaction was carried out at 185°C for 6.5 hours. From the above reaction, a reaction solution containing 603 g of monoolefin represented by the following formula (3b) was obtained, and this was purified by distillation. This operation was repeated several times to obtain 641 g of the compound represented by the following formula (3b).

[0141] Using a 3L stainless steel reactor, CO and H ２ CO / H mixed ２ Gas (CO / H ２ Using a molar ratio of 1), the hydroformylation reaction of the compound represented by the following formula (3b), which had been purified by distillation, was carried out. In the reactor, 641 g of the compound represented by formula (3b), 455 g of 2-octanol, 1.50 g of triphenyl phosphite, and separately prepared Rh(acac)(CO) ２ 1.2 mL of 2-octanol solution (concentration 0.008 mol / L) was added. Nitrogen and CO / H ２ After performing gas substitution three times each, CO / H２ The system was pressurized with gas, and the reaction was carried out at 120°C and 2 MPa for 6 hours. After the reaction was complete, gas chromatography analysis of the reaction solution was performed, and it was confirmed that the reaction solution contained 669 g of the compound represented by the following formula (2b) (conversion rate > 99%, selectivity 91%). Subsequently, a portion was used in the following reaction.

[0142] 1400 g of the above reaction solution (including 669 g of the compound represented by formula (2b) below) and 16 g of sponge nickel catalyst (manufactured by Nikko Rica Co., Ltd.: R-200M) were added to a 3 L stainless steel reactor. The system was then pressurized with hydrogen gas and the reaction was carried out at 2 MPa and 105°C for 7 hours. After the reaction, the obtained slurry was filtered through a membrane filter with a pore size of 0.45 μm to remove the catalyst. Analysis by gas chromatography and GC-MS confirmed that it contained 679 g of the compound represented by formula (1'b) with a molecular weight of 232 (main product yield 92%).

[0143] Further, 690 g of this mixture (including 363 g of the compound represented by formula (1'b) below) and 19 g of nickel diatomaceous earth catalyst (manufactured by Nikkei Catalysis Chemicals Co., Ltd.) were added to a 1 L stainless steel reactor. The system was then pressurized with hydrogen gas, and the reaction was carried out at 5 MPa and 200°C for 8 hours. After the reaction, the resulting slurry was filtered through a membrane filter with a pore size of 0.45 μm to remove the catalyst. Analysis by gas chromatography and GC-MS confirmed that it contained 262 g of the main product with a molecular weight of 238 represented by formula (1b) (main product yield 92%). This was further purified by distillation to obtain the main product.

[0144]

[0145] NMR analysis was performed on each component obtained in Example 2. The NMR spectra of the compound represented by formula (1b) are shown in Figures 17-18, the GCMS spectrum in Figure 19, and the GC-TOFMS spectrum in Figures 20(a) and (b). The NMR spectra of the compound represented by formula (1'b) are shown in Figures 21-22, the GCMS spectrum in Figure 23, and the GC-TOFMS spectrum in Figures 24(a) and (b). The NMR spectra of the compound represented by formula (2b) are shown in Figures 25-26, the GCMS spectrum in Figure 27, and the GC-TOFMS spectrum in Figures 28(a) and (b). The NMR spectra of the compound represented by formula (3b) are shown in Figures 29-30, the GCMS spectrum in Figure 31, and the GC-TOFMS spectrum in Figures 32(a) and (b).

[0146] GC-MS and NMR analyses confirmed that the products obtained in Example 2 were the main product, the compound of formula (1b), and the intermediate compounds represented by formulas (1'b), (2b), and (3b), respectively. Furthermore, the final compound of formula (1b) was a mixture of nearly equal amounts of two positional isomers of hydroxyl groups, with an endo:exo ratio of approximately 70:30 to 10:90. In the distillation process described above for the compound of formula (1b), although it was not easy to reliably separate the endo and exo isomers, which have slightly different boiling points, a component rich in the endo isomer was obtained in the initial distillation, and a component rich in the exo isomer was distilled in the secondary distillation. Thus, it is possible to obtain a component rich in either the endo or exo isomer, and according to the above process, a mixture with an endo:exo ratio in the range of approximately 70:30 to 10:90 can be obtained. Furthermore, based on the results of peak analysis in the GC chart, it is estimated that the ratio of the endo-isomer to the exo-isomer in the compound (3b) above was approximately 60:40.

[0147] The bifunctional compound of this embodiment has industrial applicability in applications such as monomers for optical materials and raw material monomers for polycarbonates.

Claims

1. A bifunctional compound represented by the following formula (1). In formula (1), Cy represents a cyclohexyl group, and n represents 0 or 1.

2. A method for producing a bifunctional compound, comprising a step of producing a bifunctional compound, in which a compound represented by the following formula (2a) or the following formula (2b) is reduced in the presence of a catalyst having hydrogenation ability and hydrogen to obtain the bifunctional compound described in claim 1. In formulas (2a) and (2b), Ph represents a phenyl group.

3. A method for producing a bifunctional compound according to claim 2, comprising: a cinnamon alcohol reaction step of reacting cinnamon alcohol with dicyclopentadiene to obtain a compound represented by the following formula (3a) or (3b) prior to the bifunctional compound production step; and a hydroformylation step of hydroformylating the compound represented by the following formula (3a) or (3b) with carbon monoxide and hydrogen gas in the presence of a rhodium compound and an organophosphorus compound to obtain a compound represented by the following formula (2a) or (2b).

4. The method for producing a bifunctional compound according to claim 3, wherein in the cinnamon alcohol reaction step, cinnamon alcohol and dicyclopentadiene are reacted at a temperature of 150°C to 300°C.

5. A method for producing a bifunctional compound according to claim 3, wherein the hydroformylation reaction is carried out under a pressure of 1.0 MPa to 12.0 MPa.

6. The method for producing a bifunctional compound according to claim 2, wherein the catalyst having hydrogenation ability comprises at least one selected from the group consisting of copper, chromium, iron, zinc, aluminum, nickel, cobalt, palladium, and ruthenium.

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