WO2024014448A1

WO2024014448A1 - Depolymerization method for resin having fluorene skeleton, and product and application thereof

Info

Publication number: WO2024014448A1
Application number: PCT/JP2023/025537
Authority: WO
Inventors: 寛吉村
Original assignee: 大阪ガスケミカル株式会社
Priority date: 2022-07-15
Filing date: 2023-07-11
Publication date: 2024-01-18

Abstract

According to the present invention, in the presence of a hydrolysis catalyst, a fluorene-containing resin having a fluorene skeleton and an ester bond and/or a carbonic acid ester bond is reacted with carbonic acid ester to decompose the fluorene-containing resin, and the fluorene-containing resin is depolymerized by a depolymerization method that obtains a decomposition product. According to this depolymerization method, the fluorene-containing resin can be simply depolymerized. The decomposition product may include a mono-carbonate of diol and/or a di-carbonate of diol. In the depolymerization method, alcohol may be reacted with the decomposition product to obtain diol.

Description

Depolymerization method of resin having fluorene skeleton, its products and uses

The present disclosure relates to the depolymerization of a resin having a fluorene skeleton and an ester bond and/or a carbonate bond.

In recent years, the realization of a decarbonized society has become an urgent issue on a global scale, and SDGs (Sustainable Development Goals) have been set as specific goals, and as part of this, the reuse (recycling) of used plastics is also being promoted. has been done. In particular, since polyester resins represented by polyethylene terephthalate (PET) are distributed in large quantities as beverage bottles and textile products, there is a strong demand for recycling. As a method for recycling plastics, chemical recycling is known, in which plastics are chemically decomposed into low-molecular compounds and plastics are manufactured from the decomposed low-molecular compounds. Chemical recycling is attracting attention because of the high quality of recycled products and the fact that recycled products can be used repeatedly.

As a chemical recycling method, JP-A No. 2003-128600 (Patent Document 1) and JP-A No. 2003-119316 (Patent Document 2) disclose that PET is decomposed by adding an excessive amount of ethylene glycol, and terephthalic acid is decomposed. A method of manufacturing is disclosed.

WO2004/041917 (Patent Document 3) discloses a method of decomposing polyester into monomers or oligomers by hydrolysis using subcritical water or supercritical water.

Green Chem, 2021, 23, 9412-9416 (Non-Patent Document 1), involves mixing methanol, dimethyl carbonate (DMT), and lithium methoxide in an appropriate ratio with flaky PET, and reacting at 28°C for 5 hours. It is described that when this is done, dimethyl terephthalate is produced in a yield of 74%, and when the reaction temperature is changed to 50° C., PET is completely decomposed in 5 hours. In this method, dimethyl terephthalate and ethylene carbonate are produced by a decomposition reaction. This document describes that dimethyl carbonate functions as a scavenger for ethylene glycol and that the decomposition reaction proceeds because the ethylene carbonate produced by the reaction has a stable five-membered ring structure.

Japanese Patent Application Publication No. 2003-128600 Japanese Patent Application Publication No. 2003-119316 WO2004/041917

However, in the depolymerization methods disclosed in Patent Documents 1 to 3, it is necessary to carry out the reaction under high temperature and high pressure conditions. low gender.

On the other hand, in the depolymerization method in Non-Patent Document 1, PET can be depolymerized at low temperatures, but polyester resins other than PET are not described. For example, in recent years, polyester resins with a fluorene skeleton have been used in optical applications, etc. However, due to the bulky fluorene skeleton, polyester resins with a fluorene skeleton have a structure that is significantly different from general-purpose polyesters such as PET. Coupled with the specificity of the fluorene skeleton, they exhibit different chemical behavior. However, Non-Patent Document 1 does not describe a polyester resin having a fluorene skeleton.

Therefore, an object of the present disclosure is to provide a method for easily depolymerizing a resin having a fluorene skeleton, an ester bond, and/or a carbonate bond in the molecule, and uses thereof.

Another object of the present disclosure is to provide a novel method for producing a carbonate ester compound by depolymerizing a resin having a fluorene skeleton and an ester bond and/or a carbonate ester bond.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have discovered that by reacting a resin having a fluorene skeleton and an ester bond and/or a carbonate ester bond with a carbonate ester in the presence of a hydrolysis catalyst, the resin The present disclosure was completed based on the discovery that it is possible to depolymerize (depolymerize) by a simple method.

That is, one aspect (aspect [1]) of the present disclosure is
A fluorene-containing resin having a fluorene skeleton and an ester bond and/or a carbonate ester bond (hereinafter, this resin may be simply referred to as a "fluorene-containing resin") is reacted with a carbonate ester in the presence of a hydrolysis catalyst. , a method for depolymerizing fluorene-containing resins to obtain decomposition products.

One aspect of the present disclosure is an aspect (aspect [2]) in which the decomposition product includes a diol monocarbonate ester and/or a diol dicarbonate ester in the aspect [1], and the aspect [2]. The decomposition product may further include a dicarboxylic acid and/or an ester thereof (aspect [3]).

One embodiment of the present disclosure may be an embodiment (aspect [4]) in which the decomposition product and alcohol are reacted to obtain a diol in any of the embodiments [1] to [3].

One aspect of the present disclosure is that in any of the aspects [1] to [4], the fluorene-containing resin has the following formula (1).

(In the formula,
Ring Z ¹ and Ring Z ² independently represent arene rings,
R ¹ and R ² independently represent a substituent, m1 and m2 independently represent an integer of 0 or more,
n1 and n2 independently represent integers of 0 to 4,
A ¹ and A ² independently represent an alkylene group,
X ¹ and X ² independently represent a hydroxyl group, an alkoxy group or a halogen atom,
R ³ and R ⁴ independently represent a substituent, k1 and k2 independently represent an integer from 0 to 4)
A dicarboxylic acid component represented by and/or the following formula (2)

(In the formula,
Ring Z ³ and Ring Z ⁴ independently represent arene rings,
^A3 and ^A4 independently represent an alkylene group, s1 and s2 independently represent an integer of 0 or more,
^R5 and ^R6 independently represent a substituent, t1 and t2 independently represent an integer of 0 or more,
R ⁷ represents a substituent, and u represents an integer of 0 to 8)
It may be an embodiment (aspect [5]) of a polyester resin containing a diol represented by as a polymerization component.

One aspect of the present disclosure is
In the aspect [5], the fluorene-containing resin is a polyester resin containing a dicarboxylic acid component represented by the formula (1) as a polymerization component, and in the formula (1), n1 and n2 are 0. or an embodiment in which n1 and n2 are 1 and ring Z ¹ and ring Z ² are independently fused polycyclic arene rings (aspect [6]), or in the above embodiment [5] or [6] , the fluorene-containing resin may be a polyester resin containing the diol represented by the formula (2) as a polymerization component (aspect [7]).

One aspect of the present disclosure is that in any of the aspects [1] to [4], the fluorene-containing resin has the following formula (2):

(In the formula,
Ring Z ³ and Ring Z ⁴ independently represent arene rings,
^A3 and ^A4 independently represent an alkylene group, s1 and s2 independently represent an integer of 0 or more,
^R5 and ^R6 independently represent a substituent, t1 and t2 independently represent an integer of 0 or more,
R ⁷ represents a substituent, and u represents an integer of 0 to 8)
It may be an embodiment (aspect [8]) of a polycarbonate resin containing a diol represented by as a polymerization component.

One aspect of the present disclosure is that in any of the aspects [1] to [8], the fluorene-containing resin has the following formula (5).

(In the formula,
A ⁵ represents a direct bond (single bond) or an alkylene group,
A ⁶ and A ⁷ independently represent an alkylene group, p1 and p2 independently represent an integer of 0 or more,
R ¹¹ and R ¹² independently represent a substituent, and q1 and q2 independently represent an integer from 0 to 6)
An embodiment (aspect [9]) including a diol represented by as a polymerization component may also be used.

One aspect (aspect [10]) of the present disclosure is to react a polyester resin containing a dicarboxylic acid component having a fluorene skeleton (a fluorene-containing dicarboxylic acid component) as a polymerization component with a carbonate ester in the presence of a hydrolysis catalyst. This is a method for producing a dicarboxylic acid having a fluorene skeleton and/or an ester thereof by decomposing the polyester resin.

One aspect (aspect [11]) of the present disclosure is to react a polyester resin containing a diol having a fluorene skeleton (a fluorene-containing diol) as a polymerization component with a carbonate ester in the presence of a hydrolysis catalyst. a first decomposition step to obtain a first decomposition product containing a dicarboxylic acid and/or its ester, and a diol monocarbonate and/or diol dicarbonate;
This is a method for producing a diol having a fluorene skeleton through a second decomposition step in which the first decomposition product and alcohol are reacted to obtain a diol.

One aspect (aspect [12]) of the present disclosure is that a polyester resin having a fluorene skeleton and an ester bond is reacted with a carbonate ester in the presence of a hydrolysis catalyst to decompose the polyester resin, and a dicarboxylic acid and/or or a first decomposition step to obtain a decomposition product containing the ester thereof and a diol monocarbonate ester and/or a diol dicarbonate ester;
In this method, a monomer component having a fluorene skeleton is recovered through a second decomposition step in which the decomposition product and alcohol are reacted to obtain a diol.

One aspect (aspect [13]) of the present disclosure is to react a polycarbonate resin having a fluorene skeleton and a carbonate bond with a carbonate ester in the presence of a hydrolysis catalyst to decompose the polycarbonate resin. , a first decomposition step to obtain a first decomposition product containing a diol monocarbonate ester and/or a diol dicarbonate ester;
In this method, a monomer component having a fluorene skeleton is recovered through a second decomposition step in which a diol is obtained by reacting the first decomposition product with an alcohol.

One aspect (aspect [14]) of the present disclosure is
The following formula (3)

(In the formula,
Ring Z ³ and Ring Z ⁴ independently represent arene rings,
^A3 and ^A4 independently represent an alkylene group, s1 and s2 independently represent an integer of 0 or more,
R ⁸ represents a hydrocarbon group,
^R5 and ^R6 independently represent a substituent, t1 and t2 independently represent an integer of 0 or more,
R ⁷ represents a substituent, and u represents an integer of 0 to 8)
It is a monocarbonate ester of diol represented by

One aspect (aspect [15]) of the present disclosure is
The following formula (4)

(In the formula,
Ring Z ³ and Ring Z ⁴ independently represent arene rings,
^A3 and ^A4 independently represent an alkylene group, s1 and s2 independently represent an integer of 0 or more,
R ⁹ and R ¹⁰ independently represent a hydrocarbon group,
^R5 and ^R6 independently represent a substituent, t1 and t2 independently represent an integer of 0 or more,
R ⁷ represents a substituent, and u represents an integer of 0 to 8)
It is a dicarbonate ester of diol represented by

One aspect (aspect [16]) of the present disclosure is to react a fluorene-containing resin having a fluorene skeleton and an ester bond and/or a carbonate ester bond with a carbonate ester in the presence of a hydrolysis catalyst to produce the fluorene-containing resin. A method for producing a diol monocarbonate ester according to aspect [14] by decomposition, comprising:
The fluorene-containing resin has the following formula (2)

(In the formula,
Ring Z ³ and Ring Z ⁴ independently represent arene rings,
^A3 and ^A4 independently represent an alkylene group, s1 and s2 independently represent an integer of 0 or more,
^R5 and ^R6 independently represent a substituent, t1 and t2 independently represent an integer of 0 or more,
R ⁷ represents a substituent, and u represents an integer of 0 to 8)
This method uses a fluorene-containing resin containing a diol represented by as a polymerization component.

One aspect (aspect [17]) of the present disclosure is to react a fluorene-containing resin having a fluorene skeleton and an ester bond and/or a carbonate ester bond with a carbonate ester in the presence of a hydrolysis catalyst to produce the fluorene-containing resin. A method for producing a dicarbonate ester of a diol according to aspect [15] by decomposition, comprising:
The fluorene-containing resin has the following formula (2)

One aspect (aspect [18]) of the present disclosure is
A method for recycling a fluorene-containing resin having a fluorene skeleton, an ester bond and/or a carbonate bond, the method comprising:
a depolymerization step in which the fluorene-containing resin and carbonate ester are reacted in the presence of a hydrolysis catalyst to obtain a decomposition product;
This recycling method includes a polymerization step of polymerizing the decomposition product obtained in the depolymerization step to obtain a new fluorene-containing resin.

In one aspect (aspect [19]) of the present disclosure, the monomer raw material for the new fluorene-containing resin may be replenished in the polymerization step of the aspect [18].

Further, in this specification and claims, the number of carbon atoms in substituents, etc. may be indicated as C ₁ , C ₆ , C ₁₀ , etc. For example, "C ₁ alkyl group" means an alkyl group having 1 carbon number, and "C _6-10 aryl group" means an aryl group having 6 to 10 carbon atoms.

According to the depolymerization method of a fluorene-containing resin of the present disclosure, a resin having a fluorene skeleton and an ester bond and/or a carbonate bond in the molecule, such as a polyester resin or a polycarbonate resin, can be used. Resins can be easily depolymerized.

FIG. 1 is a chart showing the molecular weight distribution of the polyester obtained in Comparative Example 1 before depolymerization. FIG. 2 is a chart showing the molecular weight distribution of the decomposition product obtained by depolymerizing the polyester obtained in Comparative Example 1. FIG. 3 is a chart showing the molecular weight distribution of the polyester obtained in Comparative Example 2 before depolymerization. FIG. 4 is a chart showing the molecular weight distribution of the decomposition product obtained by depolymerizing the polyester obtained in Comparative Example 2.

[Fluorene-containing resin]
In the present disclosure, the resin to be depolymerized is a fluorene-containing resin [or (carbonate) ester bond-containing resin] that has a fluorene skeleton and an ester bond and/or a carbonate bond in the molecule. Furthermore, in this specification and claims, a (carbonate) ester bond means an ester bond and/or a carbonate ester bond.

Examples of the resin having a (carbonate) ester bond in the molecule include polyester, polyester polycarbonate (polyester carbonate), and polycarbonate.

The fluorene skeleton may be present in either the main chain or the side chain of the fluorene-containing resin. Further, the fluorene skeleton is connected to the (carbonate) ester bond directly from the fluorene skeleton or via a divalent linking group. The (carbonic acid) ester bond or the divalent linking group may be bonded to any part of the fluorene skeleton, and the bonding position is not particularly limited, but preferably the 9, 9-, 2-, The 7th position is particularly preferred, and the 9th and 9th positions of the fluorene ring are particularly preferred. The divalent linking group may be a linking group containing at least a hydrocarbon group.

Among the fluorene-containing resins, fluorene-containing resins containing at least an ester bond formed by polymerizing at least a dicarboxylic acid component and a diol component, and fluorene-containing resins containing at least a carbonate ester bond formed by polymerizing at least a diol component are preferable. Such fluorene-containing resins are preferably fluorene-containing polyester resins such as fluorene-containing polyester resins and fluorene-containing polyester carbonate resins; fluorene-containing polycarbonate resins such as fluorene-containing polycarbonate resins; Fluorene-containing polyester resins and fluorene-containing polycarbonate resins are more preferred, and fluorene-containing polyester resins are particularly preferred.

[Fluorene-containing polyester resin]
The fluorene-containing polyester resin may contain a dicarboxylic acid component and a diol component as polymerization components, and at least one of the dicarboxylic acid component and the diol component may contain a component having a fluorene skeleton.

(Fluorene-containing dicarboxylic acid component)
When the dicarboxylic acid component as a polymerization component includes a dicarboxylic acid component having a fluorene skeleton (fluorene-containing dicarboxylic acid component), the fluorene-containing dicarboxylic acid component is, but is not particularly limited to, a dicarboxylic acid represented by the above formula (1). Ingredients are preferred.

In the formula (1), the arene rings (aromatic hydrocarbon rings) represented by ring Z ¹ and ring Z ² include monocyclic arene rings such as benzene rings, polycyclic arene rings, etc.; Examples of the polycyclic arene ring include a fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring), a ring assembled arene ring (ring assembled polycyclic aromatic hydrocarbon ring), and the like.

Examples of fused polycyclic arene rings include fused bicyclic arene rings, specifically fused bicyclic C _10-16 arene rings such as naphthalene rings and indene rings; or a tetracyclic arene ring. Examples of the fused tricyclic arene ring include fused tricyclic C _14-20 arene rings such as anthracene ring and phenanthrene ring. Preferred fused polycyclic arene rings are fused bicyclic C _10-14 arene rings, such as naphthalene rings. Examples of the ring assembly arene rings include biarene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene rings such as terphenyl ring. A preferred ring assembly arene ring is a C _12-18 biarene ring such as a biphenyl ring.

Preferred rings Z ¹ and Z ² are C _6-14 arene rings, preferably C _6-12 arenes such as benzene rings, naphthalene rings, and biphenyl rings, and more preferably C _6-10 arenes such as benzene rings and naphthalene rings. rings, most preferably naphthalene rings.

The types of rings Z ¹ and Z ² may be different from each other, but are usually the same.

Furthermore, rings Z ¹ and Z ² may be substituted at any of the 1st to 4th positions and the 5th to 8th positions of the fluorene ring, and are usually substituted at the 2nd, 3rd and/or 7th and 8th positions. It is. Preferred substitution positions (or bonding positions) are positions that are symmetrical on the paper in the above formula (1), such as the 1, 8-position, 2, 7-position, 3, 6-position, 4, 5-position of the fluorene ring, especially the 2-position. , 7th place. In addition, when rings Z ¹ and Z ² are naphthalene rings, they may be at either the 1st or 2nd position of the naphthalene ring, and from the viewpoint of improving heat resistance, it is the 1st position of the naphthalene ring and has a high refractive index. From the viewpoint of preparing a resin that satisfies a well-balanced low Abbe number and low birefringence (or high birefringence on the negative side), the 2-position of the naphthalene ring is particularly preferable.

Examples of the substituent represented by R ¹ and R ² include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a mono- or di-substituted amino group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group includes a straight-chain or branched alkyl group, and is preferably a C _1-10 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, or a t-butyl group. Examples include C _1-6 alkyl groups, more preferably C _1-4 alkyl groups. Examples of the aryl group include C _6-12 aryl groups such as phenyl, alkylphenyl, biphenylyl and naphthyl groups; mono- to tri-C ₁ such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl) groups; Examples include _-4 alkyl-phenyl group.

Examples of the alkoxy group include C _1-10 alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, and t-butoxy group. Examples of the acyl group include C _1-6 alkyl-carbonyl groups such as an acetyl group.

Examples of the mono- or di-substituted amino group include mono- or di-C _1-4 alkylamino groups such as dimethylamino group; bis(C _1-4 alkyl-carbonyl) amino groups such as diacetylamino group.

Representative groups R ¹ and R ² include alkyl groups, aryl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and the like. Preferred groups R ¹ and R ² are alkyl groups, in particular C _1-6 alkyl groups such as methyl groups; alkoxy groups, in particular C _1-4 alkoxy groups such as methoxy groups; especially Preferably it is a C _1-4 alkyl group such as a methyl group. In addition, when the groups R ¹ and R ² are aryl groups, the groups R ¹ and R ² may form the above ring assembly arene ring together with the ring Z ¹ or Z ² , respectively.

The number of substitutions m1 and m2 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and more preferably 0. When m1 and m2 are integers of 2 or more, the types of the two or more groups R ¹ and R ² may be the same or different.

The substitution numbers n1 and n2 can be selected from the range of integers from 0 to 4, for example, from 0 to 3, preferably from 0 to 2, more preferably from 0 or 1, and more preferably from 1. When a compound in which n1 and n2 are 1 or more is used, the refractive index and glass transition temperature of the fluorene-containing polyester resin can be increased, and the Abbe number and the absolute value of birefringence can be reduced.

Examples of the alkylene group represented by groups A ¹ and A ² include C _1- such as methylene group, ethylene group, trimethylene group, propylene group, 1,4-butanediyl group, and 2-methylpropane-1,3-diyl group. ₈ alkylene group, etc. Among these, a C _1-6 alkylene group is preferred, a C _2-4 alkylene group is more preferred, a C _2-3 alkylene group such as an ethylene group or a propylene group is more preferred, and an ethylene group is most preferred.

Examples of the alkoxy group represented by X ¹ and X ² include C _1-4 alkoxy groups such as methoxy group, ethoxy group, propoxy group, and t-butoxy group, with C _1-2 alkoxy group being preferred. Examples of the halogen atom include a chlorine atom and a bromine atom. Preferred X ¹ and X ² are a hydroxyl group, a methoxy group, and an ethoxy group, and halogen atoms such as a chlorine atom are also preferred in order to cause the reaction to occur at low temperatures. Among these, C _1-2 alkoxy groups such as methoxy group and ethoxy group are more preferred, and methoxy group is most preferred.

Examples of the substituents represented by R ³ and R ⁴ include alkyl groups, halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, and cyano groups; examples of the alkyl groups include methyl groups, ethyl groups, and t- Examples include C _1-6 alkyl groups such as butyl groups. Preferred R ³ and R ⁴ are C _1-4 alkyl groups such as methyl group.

The substitution positions of R ³ and R ⁴ may be the 1-position, 2-position, 7-position, 3,6-position, 4,5-position or 2,7-position of the fluorene ring. The numbers of substitutions k1 and k2 of R ³ and R ⁴ can be selected from integers of 0 to 4, for example, integers of 0 to 3, preferably integers of 0 to 2, more preferably 0 or 1, more preferably 0. . When k1 and k2 are integers of 2 or more, the types of substituents of two or more R ³ and R ⁴ may be the same or different.

Typical fluorene-containing dicarboxylic acid components represented by the formula (1) include dicarboxylic acid components in which n1 and n2 are 0, that is, 9,9-bis(carboxyalkyl)fluorenes; n1 and n2 are 1; Examples include dicarboxylic acid components, ie, 9,9-bis(carboxyalkyl)-diarylfluorenes.

That is, the preferred fluorene-containing dicarboxylic acid component may be a dicarboxylic acid component represented by the following formula (1a), (1b), or (1c).

(In the formula, A ¹ , A ² , X ¹ , X ² , R ³ , R ⁴ , k1 and k2 are each the same as in the above formula (1)).

Compounds in which n1 and n2 are 0 in formula (1) [9,9-bis(carboxyalkyl)fluorenes corresponding to formula (1a) above] include 9,9-bis(2-carboxyethyl)fluorene, Examples include 9,9-bis(carboxy C _2-6 alkyl) fluorene such as 9,9-bis(2-carboxypropyl) fluorene, preferably 9,9-bis(carboxy C _2-4 alkyl) fluorene, More preferably 9,9-bis(carboxyC _2-3 alkyl)fluorene, more preferably 9,9-bis(2-carboxyethyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene, most preferably 9,9-bis(2-carboxyethyl)fluorene. These compounds may be ester-forming derivatives, with C _1-4 alkyl esters such as methyl ester and ethyl ester being preferred, and C _1-4 alkyl esters such as methyl ester being most preferred.

In this specification and claims, the term ester-forming derivative is used to include halocarboxylic acids such as acyl chloride, alkyl esters such as methyl ester, and acid anhydrides.

Examples of compounds (9,9-bis(carboxyalkyl)-diarylfluorenes) in which n1 and n2 are 1 in formula (1) include 9,9-bis(carboxyalkyl)-diphenyl corresponding to formula (1b) above; Fluorene, specifically 9,9-bis(2-carboxyethyl)-1,8-diphenylfluorene, 9,9-bis(2-carboxyethyl)-2,7-diphenylfluorene, 9,9-bis (2-carboxyethyl)-3,6-diphenylfluorene, 9,9-bis(2-carboxyethyl)-4,5-diphenylfluorene, 9,9-bis(2-carboxypropyl)-2,7-diphenyl 9,9-bis(carboxyC _2-6 alkyl)-diphenylfluorene such as fluorene; 9,9-bis(carboxyalkyl)-dinaphthylfluorene corresponding to the formula (1c), specifically, 9, 9-bis(2-carboxyethyl)-1,8-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene, 9,9- Bis(2-carboxyethyl)-3,6-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-4,5-di(2-naphthyl)fluorene, 9,9-bis( 9,9-bis(carboxypropyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-di(1-naphthyl)fluorene, etc. Examples include C _2-6 alkyl)-dinaphthylfluorene. These compounds may be ester-forming derivatives, with C _1-4 alkyl esters such as methyl ester and ethyl ester being preferred, and C _1-4 alkyl esters such as methyl ester being most preferred.

These fluorene-containing dicarboxylic acid components may be used alone or in combination of two or more. Among the dicarboxylic acid components represented by the formula (1), 9,9-bis(carboxyC 9,9- such as 9,9-bis(2-carboxyethyl)-2,7-diphenylfluorene and 9,9-bis(2 _- carboxypropyl)-2,7-diphenylfluorene; Bis(carboxyC _2-4 alkyl)-2,7-diphenylfluorene; 9,9-bis(2-carboxyethyl)-2,7-dinaphthylfluorene, 9,9-bis(2-carboxypropyl)-2 ,7-dinaphthylfluorene is preferable, and 9,9-bis(carboxy C _2-4 alkyl)-2,7-dinaphthylfluorene such as 9,9-bis(carboxyC 2-4 alkyl)-2,7-dinaphthylfluorene is preferable, and 9,9-bis (Carboxy C _2-4 alkyl)-2,7-dinaphthylfluorene is particularly preferred. In 9,9-bis(carboxyC _2-4alkyl )-2,7-dinaphthylfluorene, the naphthyl group is a 1-naphthyl group (i.e., 9,9-bis(carboxyC _2-4alkyl )-2, 7-di(1-naphthyl)fluorene), but preferably 2-naphthyl group (i.e., 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene) 9,9-bis(carboxyC _2-4alkyl )-2,7-di(2-naphthyl)fluorene). These compounds may be ester-forming derivatives, with C _1-4 alkyl esters such as methyl esters and ethyl esters being preferred, and C _1-4 alkyl esters such as methyl esters being most preferred.

The fluorene-containing dicarboxylic acid component represented by the above formula (1) and its production method are known, and the compound in which n1 and n2 are 0 can be prepared using 9H-fluorenes according to the method described in JP-A No. 2005-89422. and components corresponding to the groups [-A ¹ -CO-X ¹ ] and [-A ² -CO-X ² ], such as (meth)acrylic acid or its ester, and n1 and n2 is 1 or more, a fluorene compound having groups [-A ¹ -CO-X ¹ ] and -A ² -CO-X ² ] at the 9,9-position according to the method described in International Publication No. 2020/213470 A method of coupling a compound having a skeleton with a compound having an arene ring corresponding to rings Z ¹ and Z ² ; a method in which a benzene ring of 9H-fluorenes has an arene ring corresponding to rings Z ¹ and Z ² By coupling the compounds and using the method described in JP-A-2005-89422, the resulting compound (a compound having a 9H-fluorene skeleton) and the groups [-A ¹ -CO-X ¹ ] and [ -A ² -CO-X ² ] and a component corresponding to it, such as (meth)acrylic acid or its ester.

(Fluorene-containing diol)
When the diol component as a polymerization component contains a diol having a fluorene skeleton (fluorene-containing diol), the fluorene-containing diol is not particularly limited, but a diol represented by the above formula (2) is preferable.

In the formula (2), the arene rings represented by Z ³ and Z ⁴ include, for example, the same arene rings as the rings Z ¹ and Z ² in the formula (1). The types of rings Z ³ and Z ⁴ may be the same or different, and are usually the same. Among rings Z ³ and Z ⁴ , C _6-12 arene rings such as benzene ring, naphthalene ring and biphenyl ring are preferred, and C _6-10 arene rings such as benzene ring and naphthalene ring are more preferred.

Note that the bonding positions of rings Z ³ and Z ⁴ to the 9-position of the fluorene ring are not particularly limited. For example, when the rings Z ³ and Z ⁴ are naphthalene rings, the bonding positions are the 1-position or the 2-position, preferably the 2-position. and when rings Z ³ and Z ⁴ are biphenyl rings, it is at any of the 2-, 3-, and 4-positions, preferably the 3-position.

The substituent R ⁷ may be a non-reactive substituent that is inert to the reaction, such as a cyano group; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a hydrocarbon such as an alkyl group or an aryl group. Examples include groups. Examples of the aryl group include C _6-10 aryl groups such as phenyl group. Preferred groups R ⁷ are cyano groups, halogen atoms, or alkyl groups, especially alkyl groups. Examples of the alkyl group include C _1-12 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl, preferably C _1-8 alkyl, and Preferably a C _1-6 alkyl group, more preferably a C _1-4 alkyl group such as a methyl group.

In addition, when the number of substitutions u of the group ^R7 is 2 or more, the types of the two or more groups ^R7 substituted on the same benzene ring among the two benzene rings constituting the fluorene ring are the same or different. The types of the two or more groups R ⁷ substituted on different benzene rings may be the same or different. Further, the bonding position (substitution position) of the group R ⁷ is not particularly limited as long as it is at the 1st to 8th positions of the fluorene ring, and examples thereof include the 2nd, 7th, 2, and 7th positions of the fluorene ring.

The substitution number u may be, for example, an integer of 0 to 6, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, 0 or 1, most preferably is 0. In addition, in the two benzene rings constituting the fluorene ring, the number of substitutions of each group R ⁷ may be different from each other, but is preferably the same.

Examples of the substituents represented by R ⁵ and R ⁶ include the same groups as the substituents exemplified as R ¹ and R ² in the above formula (1) (halogen atom; alkyl group, aryl group; alkoxy group; acyl nitro group; cyano group; mono- or di-substituted amino group, etc.), cycloalkyl group, aralkyl group, etc.

Preferred groups R ⁵ and R ⁶ are alkyl groups, aryl groups, and alkoxy groups, more preferably C _1-6 alkyl groups such as methyl groups, C _{6-14 aryl groups such as phenyl groups, and C 6-14} aryl groups such as methoxy groups. Examples include _1-4 alkoxy groups. Among these substituents, alkyl groups and aryl groups are preferred, with C _1-4 alkyl groups such as methyl groups and C _6-10 aryl groups such as phenyl groups being particularly preferred. In addition, when the group R ⁵ or R ⁶ is an aryl group, the group R ⁵ or R ⁶ may form the above-mentioned ring assembly arene ring together with the ring Z ³ or Z ⁴ .

The substitution numbers t1 and t2 are each an integer of 0 or more, and can be selected depending on the type of ring Z ³ or Z ⁴ , and may be, for example, an integer of 0 to 8, preferably 0 to 8 in stages. An integer of 4, an integer of 0 to 3, an integer of 0 to 2, 0 or 1, most preferably 0. When the numbers of substitutions t1 and t2 are integers of 2 or more, the types of the two or more groups R ⁵ and R ⁶ may be the same or different.

In addition, when the numbers of substitutions t1 and t2 are 1, rings Z ³ and Z ⁴ may be benzene rings, naphthalene rings or biphenyl rings, groups R ⁵ and R ⁶ may be methyl groups, and when t1 and t2 are 2, In some cases, rings Z ³ and Z ⁴ may be benzene rings and groups R ⁵ and R ⁶ may be methyl groups. The substitution positions of groups R ⁵ and R ⁶ are not particularly limited, and usually, in rings Z ³ and Z ⁴ , the group [-O-(A ³ O) _s1 -H] or [-O-(A ⁴ O) _s2 -H] is often substituted at least at the ortho position to the ether bond-containing group (the carbon atom adjacent to the bonding position of the ether bond-containing group).

Examples of the alkylene groups A ³ and A ⁴ include C _2-6 alkylene groups such as ethylene group, propylene group (1,2-propanediyl group), trimethylene group, 1,2-butanediyl group, and tetramethylene group. , preferably a C _2-4 alkylene group, more preferably a C _2-3 alkylene group such as an ethylene group or a propylene group, and most preferably an ethylene group.

The repetition numbers s1 and s2 are each 0 or more, and can be selected from the range of integers from 0 to 15, for example, and in order to promote the esterification reaction, the repetition numbers s1 and s2 are 1 or more, preferably an integer from 1 to 10 in stages. , an integer from 1 to 8, an integer from 1 to 6, an integer from 1 to 4, an integer from 1 to 3, 1 or 2, and most preferably 1. Note that the repeating numbers s1 and s2 may be the same or different from each other; when s1 and s2 are integers of 2 or more, the types of the 2 or more alkylene groups ^A3 and ^A4 may be the same or different. . In the present specification and claims, the "number of repeats (number of moles added)" may be an average value (arithmetic mean value, arithmetic mean value) or an average number of moles added, and preferred embodiments include the above-mentioned preferred This is the same as the range (range of integers above).

The substitution positions of the groups [-O-(A ³ O) _s1 -] and [-O-(A ⁴ O) _s2 -] (also referred to as ether-containing groups) on rings Z ³ and Z ⁴ are not particularly limited, When rings Z ³ and Z ⁴ are benzene rings, the phenyl group bonded to the 9-position of the fluorene ring is at any of the 2-, 3-, and 4-positions, preferably the 3-position or the 4-position, especially the 4-position. Often substituted; When rings Z ³ and Z ⁴ are naphthalene rings, the 1- or 2-position of the naphthalene ring is bonded to the 9-position of the fluorene ring (1-naphthyl or 2-naphthyl relationship). ), and substitution is often made at the 1,5-position, 2,6-position, etc., particularly at the 2,6-position, with respect to this bonding position. Furthermore, when rings Z ³ and Z ⁴ are biphenyl rings (or rings Z ³ and Z ⁴ are benzene rings, t1 and t2 are 1, and R ⁵ and R ⁶ are phenyl groups), The 3-position or 4-position of the biphenyl ring may be bonded, and when the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene ring, the substitution position of the ether-containing group is the 6-position or 4' position of the biphenyl ring. It may be substituted at the 6-position, especially at the 6-position.

Examples of fluorene-containing diols include 9,9-bis(hydroxyaryl)fluorenes in which s1 and s2 are 0 in the formula (2); 9,9-bis(hydroxyaryl)fluorenes in which s1 and s2 are 1 or more, for example 1 to 10 Examples include [hydroxy(poly)alkoxyaryl]fluorenes.

The preferred fluorene-containing diol may include a compound represented by the following formula (2a) or (2b).

(In the formula, A ³ , A ⁴ , s1, s2, R ⁵ , R ⁶ , t1, t2, R ⁷ and u are each the same as in the above formula (2)).

Examples of the 9,9-bis(hydroxyphenyl)fluorenes corresponding to the formula (2a) include 9,9-bis(hydroxyphenyl)fluorene such as 9,9-bis(4-hydroxyphenyl)fluorene; -Bis(alkyl-hydroxyphenyl)fluorene, specifically 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9 9,9-bis[(mono- or di)C _1-4alkyl -hydroxyphenyl]fluorene such as ,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene; 9,9-bis(aryl- hydroxyphenyl)fluorene, specifically 9,9-bis(C _6-10 aryl-hydroxyphenyl)fluorene such as 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene.

Further, as the 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorenes corresponding to formula (2a), alkylene oxides (or alkylene carbonates, haloalkanols) of the 9,9-bis(hydroxyphenyl)fluorenes adducts, such as 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene, specifically 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4 -9,9-bis[hydroxy(mono- to deca)C _2- such as (2-(2-hydroxyethoxy)ethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene _4- alkoxy-phenyl]fluorene, etc.; 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene, specifically 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl] Fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl ] Fluorene, 9,9-bis[(mono or di)C _1-4 alkyl-hydroxy (mono to deca)C such as 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]fluorene 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene, specifically 9,9-bis(4-(2-hydroxyethoxy)-3-phenyl ₎ phenyl)fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)-3-phenylphenyl]fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-phenylphenyl) ) 9,9-bis[C _6-10 aryl-hydroxy (mono to deca) C _2-4 alkoxy-phenyl] fluorene such as fluorene.

Examples of the 9,9-bis(hydroxynaphthyl)fluorenes corresponding to the formula (2b) include 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(5-hydroxy-1- Examples of 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene include 9,9-bis[6-(2-hydroxyethoxy)fluorene; )-2-naphthyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, 9,9-bis[6-(2-(2-hydroxyethoxy)ethoxy)-2 -naphthyl]fluorene, 9,9-bis[hydroxy(mono- to deca) _C2-4alkoxy -naphthyl]fluorene such as 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene, etc. Can be mentioned.

These fluorene-containing diols can be used alone or in combination of two or more. Among these, 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes such as 9,9-bis[hydroxy(mono- to hexa)C _2-4alkoxyC _6-12aryl ]fluorene are preferred; 9-bis[hydroxy(mono- or di)C _2-4 alkoxy-C _6-12 aryl]fluorene is more preferred, and 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 9, 9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis[ 9,9-bis[ such as 4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (BOPPEF), 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) HydroxyC _2-3 alkoxy-C _6-12 aryl]fluorene is more preferred, BPEF, BOPPEF, and BNEF are particularly preferred, and BPEF and BNEF are most preferred.

(Other dicarboxylic acid components)
In addition to the fluorene-containing dicarboxylic acid component, the dicarboxylic acid component may include other dicarboxylic acid components (dicarboxylic acid components other than the fluorene-containing dicarboxylic acid component). When the diol component includes a fluorene-containing diol, the dicarboxylic acid component may be another dicarboxylic acid component alone.

Other dicarboxylic acid components include aliphatic dicarboxylic acid components, alicyclic dicarboxylic acid components, aromatic dicarboxylic acid components, and the like.

Examples of the aliphatic dicarboxylic acid component include alkanedicarboxylic acids, unsaturated aliphatic dicarboxylic acids, and ester-forming derivatives thereof. Examples of the alkanedicarboxylic acid include C _1-20 alkane-dicarboxylic acids such as malonic acid, succinic acid, and adipic acid. Examples of unsaturated aliphatic dicarboxylic acids include C _2-10 alkene-dicarboxylic acids such as maleic acid and fumaric acid.

Examples of the alicyclic dicarboxylic acid component include cycloalkanedicarboxylic acids, bridged cyclic cycloalkanedicarboxylic acids, cycloalkenedicarboxylic acids, bridged cyclic cycloalkenedicarboxylic acids, or ester-forming derivatives thereof. Examples of the cycloalkanedicarboxylic acid include C _4-12 cycloalkanedicarboxylic acids such as cyclohexanedicarboxylic acid. Examples of the bridged cyclic cycloalkanedicarboxylic acid include (bi- or tri)cycloC _7-10 alkane-dicarboxylic acids such as norbornanedicarboxylic acid. Examples of the cycloalkenedicarboxylic acid include C _5-10 cycloalkenedicarboxylic acids such as cyclopentenedicarboxylic acid. Examples of the bridged cyclic cycloalkenedicarboxylic acid include (bi- or tri)cycloC _7-10 alkene-dicarboxylic acids such as norbornenedicarboxylic acid.

Examples of the aromatic dicarboxylic acid component include monocyclic aromatic dicarboxylic acids, polycyclic aromatic dicarboxylic acids, and ester-forming derivatives thereof. Examples of the monocyclic aromatic dicarboxylic acid component include benzenedicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; and C _1-4 alkyl-benzenedicarboxylic acids such as 5-methylisophthalic acid. Examples of the polycyclic arenedicarboxylic acid component include fused polycyclic arenedicarboxylic acids, ring assembled arenedicarboxylic acids, and the like. Examples of the fused polycyclic arene dicarboxylic acids include naphthalene dicarboxylic acids such as 1,2-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid; anthracene dicarboxylic acid; ; fused polycyclic C _10-24 arene-dicarboxylic acids such as phenanthenedicarboxylic acid; Examples of ring assembled arene dicarboxylic acids include biC _6-10 arene dicarboxylic acids such as 2,2'-biphenyl dicarboxylic acid, 3,3'-biphenyl dicarboxylic acid, and 4,4'-biphenyl dicarboxylic acid.

These other dicarboxylic acid components can be used alone or in combination of two or more. Among these, aromatic dicarboxylic acid components are preferred, and benzene dicarboxylic acids such as terephthalic acid are particularly preferred.

(Other diol components)
In addition to the fluorene-containing diol, the diol component may include other diol components (diol components other than the fluorene-containing diol), and when the dicarboxylic acid component includes a fluorene-containing dicarboxylic acid component, the diol component may contain other diol components. The component may be used alone.

Other diol components include chain aliphatic diols, alicyclic diols, aromatic diols, and the like.

Examples of chain aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3- C _2-10 alkanediols such as pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol; di- or tri-C _2-4 alkanediols such as diethylene glycol, dipropylene glycol, triethylene glycol, etc. can be mentioned.

Examples of the alicyclic diol include C _5-8 cycloalkanediols such as cyclohexanediol; di(hydroxyC _1-4 alkyl)C _5-8 cycloalkanes such as cyclohexanedimethanol; and the like.

Aromatic diols include dihydroxyarenes such as hydroquinone and resorcinol; aromatic aliphatic diols such as benzenedimethanol; bisphenols such as bisphenol F, bisphenol AD, bisphenol A, bisphenol C, bisphenol G, and bisphenol S; p, p' - biphenols such as biphenol; binaphthols such as binaphthol; and C _2-4 alkylene oxide (or alkylene carbonate, haloalkanol) adducts of these diol components. Binaphthols may be diols represented by formula (5) described below.

These other diol components can be used alone or in combination of two or more. Among these, low molecular weight aliphatic diols (chain aliphatic diols) such as alkanediols are preferred, and C _2-4 alkanediols such as ethylene glycol are more preferred.

(Carbonate bond forming component)
When the fluorene-containing polyester resin is a fluorene-containing polyester carbonate resin, in addition to the dicarboxylic acid component and the diol component, it contains a carbonate bond-forming component as a polymerization component for forming carbonate units. In this specification and claims, the term "carbonate unit" refers to a structural unit derived from a carbonate bond-forming component, that is, a carbonyl group [-C(=O)-], and this carbonyl group forms a carbonate ester bond with the terminal oxygen atoms of the constituent units derived from the two diol components that are bonded adjacent to each other. Therefore, the carbonate bond-forming component may be any compound that can form a carbonate bond by reaction with two diol components, and typical carbonate bond-forming components include phosgene, triphosgene, etc. Examples include phosgenes and carbonic acid diesters such as diphenyl carbonate. Carbonic diesters such as diphenyl carbonate are preferred from the viewpoint of safety.

In the fluorene-containing polyester carbonate resin, the ratio of the total amount of the dicarboxylic acid component and carbonate bond forming component to the diol component is the former/latter (molar ratio) = 1/0.8 to 1/1.2, preferably The ratio is 1/0.9 to 1/1.1, preferably approximately equimolar. Further, the ratio of the dicarboxylic acid component and the carbonate bond forming component may be selected from the range of former/latter (molar ratio) = 99/1 to 1/99, preferably 95/5 in the following steps. ~10/90, 90/10~20/80, 80/20~30/70, 70/30~40/60. If the proportion of the carbonate bond-forming component is too high, there is a risk that the refractive index and heat resistance will decrease.

(Characteristics of fluorene-containing polyester resin)
In the fluorene-containing polyester resin, the proportion of the polymer component having a fluorene skeleton may be 10 mol % or more in the total polymer components including the dicarboxylic acid component and the diol component, and preferably 30 mol % or more in steps below. , 30 to 99 mol%, 40 to 98 mol%, 50 to 95 mol%, 70 to 93 mol%, 80 to 90 mol%, and 82 to 88 mol%. In the present disclosure, even fluorene-containing polyester resins with a high proportion of fluorene skeletons, especially fluorene-containing polyester resins, can be efficiently depolymerized and useful monomer components (monomers) having fluorene skeletons can be efficiently recovered. can.

In this specification and claims, the ratio (mole ratio) of polymerized components means the ratio (mole ratio) as a structural unit in the fluorene-containing resin.

The weight average molecular weight of the fluorene-containing polyester resin can be selected, for example, from a range of about 15,000 to 100,000, for example 20,000 to 80,000, preferably 30,000 to 70,000, more preferably 40, 000 to 65,000, most preferably 45,000 to 60,000.

Note that in this specification and claims, the weight average molecular weight of the fluorene-containing polyester resin can be measured by gel permeation chromatography using polystyrene as a standard substance.

The glass transition temperature (Tg) of the fluorene-containing polyester resin can be selected from a range of about 100 to 250°C, for example, 110 to 230°C, preferably 120 to 210°C, more preferably 130 to 200°C, most preferably The temperature is 135-190°C. Note that in this specification and claims, the glass transition temperature can be measured using a differential scanning calorimeter, and more specifically, by the method described in the Examples below.

The fluorene-containing polyester resin may be amorphous.

In a fluorene-containing polyester resin such as a fluorene-containing polyester resin, the proportion of the fluorene-containing dicarboxylic acid component is not particularly limited, and when the diol component contains a fluorene-containing diol, the dicarboxylic acid component does not contain a fluorene-containing dicarboxylic acid component. However, it is preferable that the dicarboxylic acid component contains 10 mol% or more, preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more in the following steps. , 100 mol% is most preferred.

The proportion of the fluorene-containing diol is not particularly limited, and when the dicarboxylic acid component contains a fluorene-containing dicarboxylic acid component, the diol component does not need to contain the fluorene-containing diol, but it is preferably contained at 1 mol% or more in the diol component. , preferably 5 mol % or more, 10 to 99 mol %, 30 to 95 mol %, 40 to 90 mol %, 50 to 85 mol %, and most preferably 60 to 80 mol %.

In a fluorene-containing polyester resin such as a fluorene-containing polyester resin, it is sufficient that the dicarboxylic acid component and/or the diol component have a fluorene skeleton, but it is preferable that at least the diol component has a fluorene skeleton. Most preferably both components have a fluorene backbone. A polyester resin in which both the dicarboxylic acid component and the diol component have a fluorene skeleton has a large density of bulky fluorene skeletons, and is significantly different from general-purpose polyester resins not only in structure but also in behavior. Legally, monomers with useful fluorene skeletons can be efficiently recovered.

In particular, it is particularly preferred that the diol component not only comprises a fluorene-containing diol, but also is combined with other diol components (particularly aliphatic diols such as C _2-4 alkanediols).

In a fluorene-containing polyester resin such as a fluorene-containing polyester resin, the molar ratio of the fluorene-containing diol and other diol components (especially aliphatic diol) is selected from a range of about 100/0 to 30/70 (former/latter). The preferred ranges are 99/1 to 40/60, 95/5 to 50/50, 90/10 to 55/45, 80/20 to 60/40, most preferably 75 /25 to 65/35.

(A) First decomposition step In the method for depolymerizing a fluorene-containing polyester resin of the present disclosure, in the first decomposition step, the fluorene-containing polyester resin and carbonate ester are combined in the presence of a first hydrolysis catalyst. The fluorene-containing polyester resin is reacted and decomposed to produce a decomposition product (first decomposition product) containing a dicarboxylic acid and/or its ester, and a diol monocarbonate and/or diol dicarbonate. ).

(carbonate ester)
The carbonate ester acts as a depolymerization agent for the fluorene-containing polyester resin. Carbonic acid esters include carbonic diesters such as dialkyl carbonate (dialkanoyl carbonate) and diaryl carbonate. Examples of dialkanol carbonate include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, di-t-butyl carbonate, and the like. Examples of the diaryl carbonate include diphenyl carbonate and tolylphenyl carbonate.

These carbonate esters can be used alone or in combination of two or more. Among these, di-C _1-4 alkyl carbonate is preferred, di-C _1-3 alkyl carbonate is more preferred, di-C _1-2 alkyl carbonate is more preferred, and dimethyl carbonate is most preferred.

The proportion of the carbonate ester may be 1 mole or more per mole of the fluorene-containing polyester resin (the number of moles corresponding to the number average molecular weight), for example, 1 to 50 moles, preferably 2 to 30 moles, and more preferably is 3 to 20 mol, more preferably 5 to 15 mol, most preferably 8 to 12 mol. The proportion of the carbonate ester may be, for example, 50 parts by mass or more, for example, 50 to 1000 parts by mass, preferably 100 to 500 parts by mass, and more preferably 120 to 400 parts by mass, based on 100 parts by mass of the fluorene-containing polyester resin. Parts by weight, more preferably 150 to 380 parts by weight, most preferably 180 to 350 parts by weight. If the proportion of carbonate ester is too small, there is a risk that depolymerization will not proceed quickly.

(First hydrolysis catalyst)
The first hydrolysis catalyst may be any conventional hydrolysis catalyst, and may be an acid catalyst, but is preferably an alkali catalyst. Alkaline catalysts include inorganic bases, organic bases, and the like.

Inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; sodium oxide, and potassium oxide. alkali metal oxides such as; alkaline earth metal oxides such as magnesium oxide, calcium oxide, barium oxide; alkali or alkaline earth metal carbonates such as cesium carbonate, sodium carbonate; alkali or alkaline earth metal oxides such as sodium hydrogen carbonate. Examples include metal hydrogen carbonate and ammonia.

Organic bases include alkali or alkaline earth metal carboxylates such as sodium acetate and calcium acetate; alkali metals such as lithium methoxide, sodium methoxide, potassium methoxide, sodium ethoxide, sodium propoxide, and sodium t-butoxide. Alkoxides; organometallic compounds such as butyllithium, phenyllithium, isopropylmagnesium chloride, cyclohexylmagnesium bromide, phenylmagnesium bromide, sodium amide, lithium diisopropylamide; and amines.

These alkali catalysts can be used alone or in combination of two or more. Among these, alkali metal C _1-6 alkoxides are preferred, alkali metal C _1-4 alkoxides are more preferred, alkali metal C _1-3 alkoxides are more preferred, and alkali metal C _{1-2 alkoxides such as lithium C 1-2} alkoxides _are more preferred. Alkoxides are most preferred.

The proportion of the first hydrolysis catalyst may be, for example, 0.01 mol or more, preferably 0.01 to 0.3 mol, more preferably 0.03 mol, per 1 mol of the fluorene-containing polyester resin. ~0.2 mole, more preferably 0.05 to 0.15 mole, most preferably 0.08 to 0.12 mole. The proportion of the first hydrolysis catalyst may be, for example, 0.1 parts by mass or more, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the fluorene-containing polyester resin. 2 to 3 parts by weight, more preferably 0.3 to 2 parts by weight, most preferably 0.5 to 1.5 parts by weight. If the proportion of the first hydrolysis catalyst is too small, there is a risk that depolymerization will not proceed quickly. These proportions of the first hydrolysis catalyst may be proportions of an alkaline catalyst.

(Reaction conditions)
The reaction temperature may be 20°C or higher, for example 20 to 85°C, preferably 25 to 83°C, more preferably 30 to 80°C, more preferably 50 to 75°C, most preferably 60 to 70°C. be.

The reaction time may be 10 minutes or more, for example 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 to 5 hours, and more preferably 2 to 4 hours.

Although the reaction may be carried out in the presence of an inert gas, it is preferably carried out in the atmosphere from the standpoint of simplicity. Although the reaction may be carried out under reduced pressure, it is preferably carried out under atmospheric pressure from the viewpoint of simplicity.

(First decomposition product)
The first decomposition product in the first decomposition step includes a dicarboxylic acid and/or its ester, and a diol monocarbonate and/or diol dicarbonate. Therefore, the present disclosure also includes a method for producing a diol monocarbonate ester and/or a diol dicarbonate ester by the first decomposition step.

The dicarboxylic acid ester may be an alkyl ester. As the alkyl ester, C _1-3 alkyl esters such as methyl ester and ethyl ester are preferred, and methyl ester is particularly preferred. When the dicarboxylic acid and/or its ester is a dicarboxylic acid component represented by the above formula (1), in the above formula (1), X ¹ and X ² are C _1-4 alkoxy groups. A dicarboxylic acid component in which X ¹ and X ² are C _1-2 alkoxy groups such as a methoxy group is preferred, and a methoxy group is particularly preferred. When X ¹ and X ² are C _1-2 alkoxy groups, a new fluorene-containing resin can be produced with high productivity in chemical recycling. The alkyl group contained in the alkoxy group of X ¹ and X ² may be an alkyl group derived from an alkali catalyst.

The diol monocarbonate ester and/or diol dicarbonate ester may be reused as a raw material for fluorene-containing polyester resin by subjecting it to the second decomposition step, which is the next step, and converting it into diol. , it may be used as a carbonate ester compound without being subjected to the second decomposition step.

Examples of the diol monocarbonate ester include the diol monocarbonate ester represented by the above formula (3). This monocarbonate ester is a new compound and can be used as a raw material for polycarbonate resin, a reaction regulator, a resin additive, and the like.

The monocarbonate ester of the diol represented by the formula (3) is a monocarbonate ester in which a carbonate ester is added to only one hydroxyl group of the diol represented by the formula (2).

In the formula (3), examples of the hydrocarbon group represented by R ⁸ include an alkyl group and an aryl group. Among these, alkyl groups and phenyl groups are preferred, and alkyl groups are particularly preferred. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, and butyl group. These alkyl groups can be used alone or in combination of two or more. Among these, a C _1-4 alkyl group is preferred, a C _1-3 alkyl group is more preferred, a C _1-2 alkyl group is more preferred, and a methyl group is most preferred.

Examples of dicarbonate esters of diol include dicarbonate esters of diol represented by the above formula (4). This dicarbonate ester is also a new compound and can be used as a raw material for polycarbonate resin, a resin additive, and the like.

The dicarbonate ester of the diol represented by formula (4) is a dicarbonate ester in which a carbonate ester is added to both hydroxyl groups of the diol represented by formula (2).

In the formula (4), examples of the hydrocarbon group represented by R ⁹ and R ¹⁰ include an alkyl group and an aryl group. Among these, alkyl groups and phenyl groups are preferred, and alkyl groups are particularly preferred. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, and butyl group. These alkyl groups can be used alone or in combination of two or more. Among these, a C _1-4 alkyl group is preferred, a C _1-3 alkyl group is more preferred, a C _1-2 alkyl group is more preferred, and a methyl group is most preferred.

In the first decomposition step, the total proportion of the monocarbonate ester and the dicarbonate ester is, for example, 0.1 to 5 mol, preferably 0.2 to 3 mol, with respect to 1 mol of the dicarboxylic acid component. The amount is preferably 0.3 to 2 mol, more preferably 0.5 to 1.5 mol.

The proportion of the monocarbonate ester is, for example, 0.1 to 1 mol, preferably 0.2 to 0.9 mol, more preferably 0.3 to 0.8 mol, and more, per 1 mol of the dicarbonate ester. Preferably it is 0.4 to 0.6 mol.

The first decomposition product may further contain a diol. The diol may be a diol corresponding to the monocarbonate ester and the dicarbonate ester. The proportion of diol is about 0.2 mol or less, for example 0.1 mol or less, preferably 0.05 mol or less, more preferably 0.01 to 0. 03 mole.

The first decomposition product may be subjected to a conventional purification treatment. Conventional purification treatments include, for example, neutralizing and washing a mixture containing decomposition products with water as necessary, and then removing impurities from the mixture by filtration or the like. If a monomer component is precipitated in the mixture, it may be completely dissolved using a good solvent for the monomer component, and then neutralized and washed with water.

In the first decomposition step, dicarboxylic acids and/or their esters, and diol monocarbonate esters and/or diol dicarbonate esters are mainly obtained. Therefore, when the target monomer component having a fluorene skeleton is a dicarboxylic acid component or when the target compound is a new carbonate ester compound, the depolymerization method of the present disclosure requires only the first decomposition step. The depolymerization method may be a depolymerization method that does not include the second decomposition step described below.

(B) Second decomposition step The method for depolymerizing a fluorene-containing polyester resin of the present disclosure includes, in addition to the first decomposition step, a second decomposition step for obtaining a second decomposition product. You can. In the second decomposition step, the first decomposition product and alcohol are reacted to obtain a diol. Specifically, in the second decomposition step, the diol is obtained by reacting the monocarbonate ester of the diol and/or the dicarbonate ester of the diol with the alcohol. In this way, in the second decomposition step, the diol monocarbonate ester and/or diol dicarbonate ester can be converted into diol, so it is particularly effective when recovering a diol having a fluorene skeleton as a monomer component. be.

(alcohol)
Examples of the alcohol include C _1-4 alkanols such as methanol, ethanol, isopropanol, propanol, and butanol. These alcohols can be used alone or in combination of two or more. Among these, C _1-3 alkanols are preferred, C _1-2 alkanols are more preferred, and methanol is most preferred. Also in the second decomposition step, since the decomposition reaction proceeds in the presence of the dicarboxylic acid component, it is preferable to use an alcohol corresponding to the alkoxide of the first hydrolysis catalyst used in the first decomposition step.

The proportion of alcohol may be 50 parts by mass or more based on 100 parts by mass of the first decomposition product, for example 50 to 1000 parts by mass, preferably 80 to 500 parts by mass, more preferably 100 to 300 parts by mass. , more preferably 120 to 250 parts by weight, most preferably 150 to 200 parts by weight. If the proportion of alcohol is too small, there is a risk that the yield of the diol component will decrease.

(Second hydrolysis catalyst)
Examples of the second hydrolysis catalyst include the hydrolysis catalysts exemplified as the first hydrolysis catalyst. The second hydrolysis catalyst can be used alone or in combination of two or more. Among the second hydrolysis catalysts, alkali metal hydroxides and alkaline earth metal hydroxides are preferred, and alkali metal hydroxides such as potassium hydroxide are particularly preferred.

The proportion of the second hydrolysis catalyst may be 1 part by mass or more, for example 1 to 30 parts by mass, preferably 5 to 25 parts by mass, more preferably It is 10 to 20 parts by mass. If the proportion of the second hydrolysis catalyst is too small, the yield of the diol component may decrease. These proportions of the second hydrolysis catalyst may be proportions of the alkaline catalyst.

The reaction time may be 5 minutes or more, for example 5 minutes to 5 hours, preferably 10 minutes to 3 hours, more preferably 30 minutes to 2 hours, and more preferably 40 minutes to 1.5 hours.

(Second decomposition product)
The second decomposition product in the second decomposition step includes a dicarboxylic acid and/or an ester thereof and a diol. That is, in the depolymerization method of the present disclosure including the second decomposition step, all the raw materials for the fluorene-containing polyester resin can be recovered, so the obtained monomer components can be used as they are to newly synthesize the fluorene-containing polyester resin. The recyclability of fluorene-containing polyester resins can be improved.

(C) Purification step The mixture containing the dicarboxylic acid and/or its ester and the diol obtained in the second decomposition step is separated into the dicarboxylic acid and/or its ester and the diol by a conventional method, Each component may be subjected to a purification step.

For example, the dicarboxylic acid and/or its ester is separated from the diol by filtration using a solvent that acts as a good solvent for the diol and as a poor solvent for the dicarboxylic acid and/or its ester. You may. As a solvent having such a function, a C _1-4 alkanol such as methanol can be used.

Alternatively, solvent extraction may be performed using a good solvent for dicarboxylic acids and/or their esters and a good solvent for diols that are incompatible with this good solvent. The solvent extraction method is effective when the dicarboxylic acid and/or its ester is also dissolved in a good solvent for the diol such as the C _1-4 alkanol. Good solvents for dicarboxylic acids and/or esters thereof include aliphatic hydrocarbons such as heptane.

The separated monomer component (dicarboxylic acid and/or its ester, diol) may be purified by a conventional method. As a purification method, conventional methods such as filtration, concentration, crystallization, and columns can be appropriately combined. Among these, purification methods including crystallization are preferred.

As for the crystallization method, it is preferable to crystallize the monomer component using a crystallization solvent containing an aromatic hydrocarbon and/or a polar solvent as a crystallization solvent.

As the aromatic hydrocarbons, mono- or di-C _1-2 alkyl-benzenes such as toluene, xylene, and ethylbenzene are preferred, with toluene being particularly preferred.

As the polar solvent, water, C _1-4 alkanols such as ethanol and isopropanol; aliphatic ketones having 3 or more carbon atoms such as acetone and methyl isobutyl ketone are preferable; water, C _2-3 alkanols; carbon atoms 4-8 Particularly preferred are aliphatic ketones.

Among the crystallization solvents, examples of good solvents include aromatic hydrocarbons and aliphatic ketones having 4 or more carbon atoms. Examples of the poor solvent include water, C _1-4 alkanol, and the like.

The proportion of the poor solvent may be, for example, 100 parts by mass or less, for example, 0 to 100 parts by mass, preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, with respect to 100 parts by mass of the good solvent. More preferably, it is 20 to 50 parts by mass.

The proportion of the crystallization solvent is, for example, 10 to 3000 parts by weight, preferably 50 to 2000 parts by weight, more preferably 100 to 1000 parts by weight, and most preferably 200 to 500 parts by weight, based on 100 parts by weight of the monomer component. .

In the crystallization treatment, a monomer component with higher purity can be precipitated or crystallized by dissolving the monomer component in the crystallization solvent and cooling it. The temperature at which the monomer component is dissolved in the crystallization solvent is a temperature below the boiling point of the solvent, for example, 30 to 200°C, preferably 50 to 150°C, more preferably 60 to 100°C. The crystallized monomer component may be washed and then dried by a conventional method.

[Fluorene-containing polycarbonate resin]
The fluorene-containing polycarbonate resin of the present disclosure includes a diol component as a polymerization component, and the diol component includes a fluorene-containing diol.

(Fluorene-containing diol)
The fluorene-containing diol is not particularly limited, but a diol component represented by the formula (2) described in the section of the fluorene-containing polyester resin is preferred. Examples of the diol represented by the above formula (2) include the diols represented by the above formula (2) exemplified in the section of the fluorene-containing polyester resin. The diol components can be used alone or in combination of two or more.

Among the diol components, 9,9-bis(4-hydroxyphenyl)fluorene (BPF), 9,9-bis[(mono- or di)C _1-4 alkyl-hydroxyphenyl]fluorene, 9,9-bis( 9,9-bis(hydroxyphenyl)fluorenes such as C _6-10 aryl-hydroxyphenyl)fluorene; 9,9-bis(hydroxyphenyl)fluorenes such as 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF); 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes such as 9,9-bis[hydroxy(mono- to hexa)C _2-4alkoxyC _6-12aryl ]fluorene are preferred; 9,9-bis[hydroxy(mono- or di)C _2-4 alkoxy-C _6-12 aryl]fluorene is more preferred, and BPF, BNF, BPEF, 9,9-bis[4-(2-hydroxyethoxy)- 9,9-bis[hydroxyC _2-3 alkoxy-C such as 3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, BOPPEF, BNEF, etc. _6-12 aryl]fluorene is more preferred, BPF, BNF, BPEF, BOPPEF, and BNEF are particularly preferred, and BPEF is most preferred.

(Binaphthalene-containing diol)
In addition to the fluorene-containing diol, the diol component may include a diol represented by the following formula (5) as a diol having a bi(or bis)naphthalene skeleton (binaphthalene-containing diol).

(In the formula,
A ⁵ represents a direct bond (single bond) or an alkylene group,
A ⁶ and A ⁷ independently represent an alkylene group, p1 and p2 independently represent an integer of 0 or more,
R ¹¹ and R ¹² independently represent a substituent, and q1 and q2 independently represent an integer from 0 to 6).

In the formula (5), the substituents R ¹¹ and R ¹² can be selected from the same substituents R ⁵ and R ⁶ exemplified in the formula (2), including preferred embodiments.

The numbers of substitutions q1 and q2 of R ¹¹ and R ¹² may each be an integer of about 0 to 5, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, in the following stepwise order. It is an integer, more preferably 0 or 1, especially 0. q1 and q2 may be different from each other, but are preferably the same. Further, when q1 is 2 or more, the types of two or more R ¹¹ may be the same or different from each other, and the same applies to q2 and R ¹² . Moreover, the types of R ¹¹ and R ¹² may be the same or different from each other.

The substitution positions of R ¹¹ and R ¹² are A ⁵ and (poly)oxyalkylene groups [-O-(A ⁶ O) _p1 -] and [-O-(A ⁷ O) _p2 -] in the two naphthalene ring skeletons. There is no particular restriction as long as the substitution position is other than the substitution position, and the 3rd to 8th positions relative to the 1st position of the two naphthalene ring skeletons bonded to A ⁵ are preferable. For example, when A ⁵ is a direct bond (single bond), it is preferably at positions 3 to 8 or 3' to 8' of the 1,1'-binaphthyl skeleton.

Examples of the alkylene group represented by A ⁵ include C _1-4 alkylene groups such as methylene group, ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group. From the viewpoint of optical properties such as high refractive index, low Abbe number, and low birefringence, ^A5 is preferably a direct bond or a C _1-2 alkylene group such as a methylene group, and a direct bond (single bond) is particularly preferable. .

Alkylene groups A ⁶ and A ⁷ can be selected from the same alkylene groups A ³ and A ⁴ exemplified in formula (2) above, including preferred embodiments. The repetition numbers p1 and p2 can also be selected from the same numbers of repetitions s1 and s2 in the above formula (2), including preferred embodiments.

In the formula (5), the bonding positions of the (poly)oxyalkylene groups [-O-(A ⁶ O) _p1 -] and [-O-(A ⁷ O) _p2 -] are not particularly limited, and for example, 1 , 1'-binaphthyl skeleton, 2, 2', 4, 4', etc. positions may be used. The 2,2' position is preferable since it is easy to increase the refractive index. Therefore, the binaphthalene-containing diol represented by the formula (5) above preferably includes a binaphthalene-containing diol represented by the following formula (5a).

(In the formula, A ⁶ , A ⁷ , p1, p2, R ¹¹ , R ¹² , q1 and q2 are each the same as in the above formula (5)).

Typical binaphthalene-containing diols represented by the formula (5a) include dihydroxy-1,1'-binaphthyl such as 2,2'-dihydroxy-1,1'-binaphthyl; bis[hydroxy(poly)alkoxy] Examples include -1,1'-binaphthyl. Bis[hydroxy(poly)alkoxy]-1,1'-binaphthyl includes 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxypropoxy) 2,2'-bis[hydroxy (mono to deca)C _2- such as -1,1'-binaphthyl, 2,2'-bis[2-(2-hydroxyethoxy)ethoxy]-1,1'-binaphthyl _4alkoxy ]-1,1'-binaphthyl and the like.

These binaphthalene-containing diols can be used alone or in combination of two or more. Among these, diols represented by the above formula (5a) are preferred, such as 2,2'-dihydroxy-1,1'-binaphthyl, 2,2'-bis[hydroxy (mono to tetra) C _2-4 alkoxy] -1,1'-binaphthyl is more preferred, and 2,2'-bis[hydroxy(mono- to tri)C _2-3 alkoxy such as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl ]-1,1'-binaphthyl is most preferred.

(Other diol components)
The diol component may further contain other diol components. Other diol components, including preferred embodiments, are the same as other diol components (excluding binaphthols) of the fluorene-containing polyester resin.

(Carbonate bond forming component)
In addition to the diol component, the fluorene-containing polycarbonate-based resin of the present disclosure includes a carbonate bond-forming component as a polymerization component for forming carbonate units. Typical carbonate bond-forming components include, for example, phosgenes such as phosgene and triphosgene, and carbonate diesters such as diphenyl carbonate. Carbonic diesters such as diphenyl carbonate are preferred from the viewpoint of safety.

(Characteristics of fluorene-containing polycarbonate resin)
In the fluorene-containing polycarbonate resin of the present disclosure, the proportion of the fluorene-containing diol may be 10 mol% or more in the diol component, preferably in the following steps: 30 mol% or more, 50 mol% or more, 80 mol% or more. It is mol% or more, 90 mol% or more, 95 mol% or more, and 100 mol%. In the present disclosure, even fluorene-containing polycarbonate resins having a high proportion of fluorene skeletons, especially fluorene-containing polycarbonate resins, can be efficiently depolymerized and useful monomer components (monomers) having fluorene skeletons. can be collected efficiently.

When the diol component further contains a binaphthalene-containing diol in addition to the fluorene-containing diol, the molar ratio of the fluorene-containing diol and the binaphthalene-containing diol can be selected from a range of about 99/1 to 10/90, which is preferable. The range is as follows: 97/3 to 20/80, 95/5 to 30/70, 90/10 to 35/65, 80/20 to 40/60, 70/30 to 40/60. , most preferably 60/40 to 40/60. The ratio of the former/latter may be 93/7 to 40/60, preferably 90/10 to 50/50, and more preferably 80/20 to 60/40.

In the fluorene-containing polycarbonate resin of the present disclosure, the total proportion of the fluorene-containing diol and the binaphthalene-containing diol may be 50 mol% or more in the diol component, preferably 60 mol% or more, 70 mol% or more in the diol component. The content is mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, and 100 mol%.

In the fluorene-containing polycarbonate-based resin of the present disclosure, the total proportion of the diol component and the carbonate bond-forming component may be 50 mol% or more in the total polymerization components, preferably 60 mol% or more in the following steps. , 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, and 100 mol%.

The weight average molecular weight of the fluorene-containing polycarbonate resin is, for example, 20,000 to 100,000, preferably 25,000 to 80,000, more preferably 30,000 to 70,000, most preferably 35,000 to 60,000.

In the present specification and claims, the weight average molecular weight of the fluorene-containing polycarbonate resin can be measured by gel permeation chromatography using polystyrene as a standard substance.

The fluorene-containing polycarbonate resin may be amorphous.

(A) First decomposition step In the method for depolymerizing a fluorene-containing polycarbonate resin of the present disclosure, in the first decomposition step, the fluorene-containing polycarbonate resin is The fluorene-containing polycarbonate resin is decomposed by reacting with a carbonate ester to obtain a first decomposition product containing a diol monocarbonate ester and/or a diol dicarbonate ester.

(carbonate ester)
The carbonate ester acts as a depolymerization agent for the fluorene-containing polycarbonate resin. The carbonate ester is the same as the carbonate ester of the fluorene-containing polyester resin, including preferred embodiments.

The ratio of the carbonate ester may be 1 mole or more per mole of the fluorene-containing polycarbonate resin (the number of moles corresponding to the number average molecular weight), for example, 0.1 to 50 moles, preferably 0.5 ~30 moles, more preferably 1 to 10 moles, more preferably 1.5 to 5 moles, most preferably 2 to 3 moles. The proportion of the carbonate ester may be, for example, 5 parts by mass or more, for example, 5 to 1000 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 parts by mass, based on 100 parts by mass of the fluorene-containing polycarbonate ester resin. ~80 parts by weight, more preferably 30-70 parts by weight, most preferably 40-60 parts by weight. If the proportion of carbonate ester is too small, there is a risk that depolymerization will not proceed quickly.

(First hydrolysis catalyst)
The first hydrolysis catalyst can be selected from the same catalysts as the first hydrolysis catalyst for fluorene-containing polyester resins, including preferred embodiments. The first hydrolysis catalyst can be used alone or in combination of two or more.

The proportion of the first hydrolysis catalyst may be, for example, 0.01 mol or more, preferably 0.01 to 0.5 mol, more preferably 0.01 to 0.5 mol, per 1 mol of the fluorene-containing polycarbonate resin. 0.03 to 0.3 mole, more preferably 0.05 to 0.25 mole, most preferably 0.1 to 0.2 mole. The proportion of the first hydrolysis catalyst may be, for example, 0.1 parts by mass or more, preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the fluorene-containing polycarbonate resin. 0.3 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, most preferably 1 to 3 parts by weight. If the proportion of the hydrolysis catalyst is too small, there is a risk that depolymerization will not proceed quickly. These proportions of the first hydrolysis catalyst may be proportions of an alkaline catalyst.

The reaction time may be 10 minutes or more, for example 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 to 5 hours.

Although the reaction may be carried out in the presence of an inert gas, it is preferably carried out in the atmosphere from the viewpoint of simplicity. Although the reaction may be carried out under reduced pressure, it is preferably carried out under atmospheric pressure from the viewpoint of simplicity.

(First decomposition product)
The first decomposition product in the first decomposition step includes a diol monocarbonate ester and/or a diol dicarbonate ester. Therefore, in the same way as in the fluorene-containing polyester resin, the present disclosure also provides for the first decomposition step to produce a diol monocarbonate ester and/or a diol dicarbonate ester in the fluorene-containing polycarbonate resin. Also includes methods of manufacturing.

The diol monocarbonate ester and/or diol dicarbonate ester may be reused as a raw material for fluorene-containing polycarbonate resin by subjecting it to the second decomposition step, which is the next step, and converting it into diol. However, it may be used as a carbonate ester compound without being subjected to the second decomposition step.

The diol monocarbonate ester and diol dicarbonate ester are the same as the diol monocarbonate ester and diol dicarbonate ester of the fluorene-containing polyester resin, including preferred embodiments.

The proportion of the monocarbonate ester is, for example, 0.1 to 30 mol, preferably 0.5 to 10 mol, more preferably 1 to 5 mol, more preferably 2 to 4 mol, per 1 mol of the dicarbonate. be.

The first decomposition product may further contain a diol. The diol may be a diol corresponding to the monocarbonate ester and the dicarbonate ester.

In the first decomposition step, the total proportion of the monocarbonate ester and the dicarbonate ester is, for example, 0.1 to 5 mol, preferably 0.1 to 5 mol, per 1 mol of diol in the first decomposition product. The amount is 5 to 3 mol, more preferably 1 to 2 mol, and even more preferably 1.2 to 1.7 mol.

In the first decomposition step, the total proportion of the monocarbonate ester, the dicarbonate ester, and diol is, for example, 0.1 to 5 mol, preferably 0.2 to 5 mol, per mol of the carbonate bond forming component. The amount is 3 mol, more preferably 0.3 to 2 mol, and even more preferably 0.5 to 1.5 mol.

In the first decomposition step, a monocarbonate of diol and/or a dicarbonate of diol are mainly obtained. Therefore, when a novel carbonate ester compound is the target compound, the depolymerization method of the present disclosure is a depolymerization method in which the decomposition step is only the first decomposition step and does not include the second decomposition step described below. There may be.

(B) Second decomposition step The method for depolymerizing a fluorene-containing polycarbonate resin of the present disclosure includes, in addition to the first decomposition step, a second decomposition step for obtaining a second decomposition product. You may do so. In the second decomposition step, the first decomposition product and alcohol are reacted to obtain a diol. Specifically, in the second decomposition step, the diol component is obtained by reacting the diol monocarbonate ester and/or diol dicarbonate ester with the alcohol. In this way, in the second decomposition step, the diol monocarbonate ester and/or diol dicarbonate ester can be converted into diol, which is particularly effective when recovering a diol component having a fluorene skeleton as a monomer component. It is.

(alcohol)
The alcohol, including preferred embodiments, can be selected from the same alcohols as those used in the second decomposition step of the fluorene-containing polyester resin. The alcohols can be used alone or in combination of two or more.

The proportion of alcohol may be 50 parts by mass or more based on 100 parts by mass of the first decomposition product, for example 50 to 1000 parts by mass, preferably 80 to 500 parts by mass, more preferably 100 to 300 parts by mass. , more preferably 120 to 200 parts by mass. If the proportion of alcohol is too small, there is a risk that the yield of the diol component will decrease.

(Second hydrolysis catalyst)
Examples of the second hydrolysis catalyst include the hydrolysis catalysts exemplified as the first hydrolysis catalyst for fluorene-containing polyester resins. The second hydrolysis catalyst can be used alone or in combination of two or more. Among the second hydrolysis catalysts, alkali metal hydroxides and alkaline earth metal hydroxides are preferred, and alkali metal hydroxides such as potassium hydroxide are particularly preferred.

The proportion of the second hydrolysis catalyst may be 1 part by mass or more, for example 1 to 30 parts by mass, preferably 5 to 20 parts by mass, more preferably It is 5 to 10 parts by mass. If the proportion of the alkali catalyst is too small, the yield of the diol component may decrease. These proportions of the second hydrolysis catalyst may be proportions of the alkaline catalyst.

(Reaction conditions)
The reaction temperature may be 0°C or higher, for example 5 to 80°C, preferably 10 to 50°C, more preferably 15 to 40°C, or room temperature.

(Second decomposition product)
The second decomposition product in the second decomposition step includes a diol. That is, in the depolymerization method of the present disclosure including the second decomposition step, the raw materials for the fluorene-containing resin can be recovered, so the obtained monomer components can be used as they are to newly synthesize the fluorene-containing resin, and the fluorene-containing resin can be recycled. You can improve your sexuality. The fluorene-containing resin may be a fluorene-containing polyester resin or a fluorene-containing polycarbonate resin.

(C) Purification Step The second decomposition product containing the diol obtained in the second decomposition step may be subjected to a conventional purification treatment. As a conventional purification treatment, for example, the mixture containing the second decomposition product may be neutralized and washed with water as necessary, and then impurities may be removed from the mixture by filtration or the like, followed by crystallization.

As for the crystallization method, it is preferable to crystallize the monomer component using a crystallization solvent containing aromatic hydrocarbons as a crystallization solvent.

The proportion of the crystallization solvent is, for example, 10 to 3000 parts by weight, preferably 50 to 2000 parts by weight, more preferably 100 to 1000 parts by weight, and most preferably 200 to 500 parts by weight, based on 100 parts by weight of diol.

In the crystallization treatment, a diol with higher purity can be precipitated or crystallized by dissolving the diol in the crystallization solvent and cooling it. The temperature at which the diol is dissolved in the crystallization solvent is a temperature below the boiling point of the solvent, for example 30 to 200°C, preferably 50 to 150°C, more preferably 60 to 100°C. The crystallized diol may be washed and then dried by a conventional method.

[How to recycle fluorene-containing resin]
The decomposition product obtained by the depolymerization method of the present disclosure is used as a monomer raw material for a fluorene-containing resin having a fluorene skeleton and an ester bond and/or a carbonate ester bond to produce a new fluorene-containing resin. It can be recycled. That is, the recycling method of the present disclosure includes a depolymerization step in which the fluorene-containing resin and carbonate ester are reacted to obtain a decomposition product, and a depolymerization step in which the decomposition product obtained in the depolymerization step is polymerized to generate new fluorene. It includes a polymerization step (repolymerization step) to obtain the containing resin. The decomposition product may be a first decomposition product or a second decomposition product, but the second decomposition product is preferred.

In the recycling method of the present disclosure, a purified product of the decomposition product obtained in the depolymerization step may be subjected to the polymerization step, or the decomposition product may be subjected to the polymerization step without being purified. Further, in the polymerization step, the monomer raw material as a decomposition product may be supplemented with a new monomer raw material. The newly replenished monomer raw material may be the monomer raw material that is in short supply depending on the composition of the decomposition product.

In the polymerization step, a conventional method can be used to polymerize the fluorene-containing resin using the decomposition product, depending on the type of the fluorene-containing resin. Examples of methods for polymerizing fluorene-containing polyester resins include JP2013-064117A, JP2013-064118A, JP2014-218645A, JP2016-069643A, and Japanese Patent No. 7016976. Methods described in publications can be used, and examples of methods for polymerizing the fluorene-containing polycarbonate resin include methods described in JP 2018-104691A, JP 2021-134216A, and the like.

Hereinafter, the present disclosure will be described in more detail based on Examples, but the present disclosure is not limited to these Examples. The details of the materials used in the examples and the evaluation methods used in the examples are as follows.

[material]
FDP-m: 9,9-bis(2-methoxycarbonylethyl)fluorene represented by the following formula (other than using methyl acrylate [37.9 g (0.44 mol)] in place of t-butyl acrylate) , synthesized in the same manner as Example 1 of JP-A No. 2005-89422)

DNFDP-m: 9,9-bis(2-methoxycarbonylethyl)-2,7-di(2-naphthyl)fluorene (synthesized according to Example 1A of International Publication No. 2020/213470)

DMT: Dimethyl terephthalate DMN: Dimethyl 2,6-naphthalene dicarboxylate BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, manufactured by Osaka Gas Chemical Co., Ltd. BNEF: 9,9-bis[ 6-(2-hydroxyethoxy)-2-naphthyl]fluorene, Osaka Gas Chemical Co., Ltd. BOPPEF: 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, Osaka Gas Chemical Co., Ltd. Co., Ltd. EG: Ethylene glycol BINOL-2EO: 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (synthesized according to Synthesis Example 2 described in JP-A-2018-59074)
Dimethyl carbonate: manufactured by Tokyo Chemical Industry Co., Ltd. LiOMe: lithium methoxide, manufactured by Tokyo Chemical Industry Co., Ltd. NaOMe: sodium methoxide, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.

[LC-MS generation ratio]
Using "Nexera XR" manufactured by Shimadzu Corporation as the HPLC (high performance or high performance liquid chromatography) device, "LCMS-2020" as the MS unit, and "Kinetex C-18" manufactured by Phenomenex as the column, the sample was converted to acetonitrile. It was measured after dissolving and calculated from the area % ratio of HPLC.

[yield]
The diol component and dicarboxylic acid component of the polyester resin were the former: the latter = 50:50 (mole ratio), and were calculated from the blending ratio of each monomer component and the molecular weight of the monomer. Further, the diol component and the carbonate bond-forming component of the polycarbonate ester resin were set at a molar ratio of 50:50 (mole ratio) of the former and calculated from the blending ratio of each monomer component and the molecular weight of the monomer.

[LC purity]
Purity [area %] was calculated using the HPLC device described above.

[Glass transition temperature (Tg)]
Measurement was performed using a differential scanning calorimeter (DISCOVERY DSC25 manufactured by TA Instruments Co., Ltd.) at a temperature increase rate of 10° C./min in a nitrogen atmosphere.

[Molecular weight distribution]
Using "HLC-8320GPC" manufactured by Tosoh Corporation as a GPC (gel permeation chromatography) device and "TSKgel" manufactured by Tosoh Corporation as a column, the sample was dissolved in THF and measured, and the molecular weight was determined in terms of polystyrene. Calculated.

[Refractive index]
A film having a thickness of 200 to 300 μm was formed by hot pressing the sample at 200 to 240°C. This film was cut into strips measuring 20 to 30 mm in length and 10 mm in width to obtain test pieces. The obtained test piece was measured using a multi-wavelength Abbe refractometer (“DR-M4 (circulating constant temperature water bath 60-C3)” manufactured by Atago Co., Ltd.) at a measurement temperature of 20°C and using diiodomethane as a contact liquid. The refractive index nD at 589 nm (D line) was measured.

[Abbe number]
Using the test piece whose refractive index nD was measured at 589 nm (D line), the refractive index nF, nC was obtained in the same manner as the refractive index nD except that the measurement wavelength was changed to 486 nm (F line) and 656 nm (C line). were measured respectively. The Abbe number was calculated from the obtained refractive indexes nF, nD, and nC at each wavelength using the following formula.

(Abbe number) = (nD-1)/(nF-nC).

[Birefringence (3x stretching)]
A film having a thickness of 200 to 600 μm was formed by hot pressing the sample at 200 to 240°C. This film was cut into a strip of 10 mm long x 50 mm wide, and uniaxially stretched at 25 mm/min at a stretching ratio of 3 times at a glass transition temperature Tg + 10° C. to obtain a test piece. The obtained test piece was subjected to parallel Nicol rotation using a retardation film/optical material inspection device (“RETS-100” manufactured by Otsuka Electronics Co., Ltd.) at a measurement temperature of 20°C and a measurement wavelength of 600 nm. Retardation was measured and the value was divided by the thickness of the measurement site to calculate birefringence (or triple birefringence).

Example 1
(Preparation of polymer A)
According to the conventional method, according to Production Example 2 in the Examples of Patent No. 7016976, the dicarboxylic acid unit accounts for 100 mol % of the structural unit derived from DNFDP-m, and 70 mol % of the structural unit derived from BPEF in the diol unit. %, and 30 mol % of structural units derived from EG. Polymer A was prepared.

(First decomposition step)
45.82 g of the mixer-pulverized polymer A (the total number of monomers incorporated into polymer A corresponds to approximately 0.1 mole), 90.1 g of dimethyl carbonate, and 4.58 g of a methanol solution containing LiOMe at a concentration of 10% by mass. was added and reacted at 65°C for 3 hours. To the resulting reaction mixture were added 18 g of water and 3.5 g of a 10% by mass HCl aqueous solution, and after stirring at 65° C. for 15 minutes, the separated organic phase was collected, and insoluble matter was removed by filtration. The results of LC-MS analysis of the organic phase were as follows.

BPEF: 1.880 area%
BPEF monocarbonate expressed by the following formula: 11.265 area%

BPEF dicarbonate expressed by the following formula: 18.499 area%

DNFDP-m: 51.131 area%.

(Second decomposition step)
The organic phase was concentrated, and 80.1 g of methanol and 7.0 g of potassium hydroxide were added to the crude product, followed by reaction at 65° C. for 1 hour under reflux conditions. By filtering at a temperature of 60° C. or higher and washing with 150 g of methanol at 40° C., 30.1 g of crude crystals of DNFDP-m were obtained as a filtration residue. Moreover, the filtrate of the main filtration contains BPEF as a main component.

(Purification of DNFDP-m)
75.1 g of toluene was added to 30.1 g of crude crystals and completely dissolved at 80° C., then 20 g of water and 5 g of a 10% by mass HCl aqueous solution were added, and the mixture was stirred again at 80° C. for 15 minutes. After leaving to stand still and removing the separated aqueous phase, 20 g of water was added to the organic phase and washing was performed three times. The organic phase at 80°C was allowed to cool to room temperature, stirred at room temperature for 1 hour, and then filtered, and the residue was washed successively with toluene and methanol. The washed filtration residue was dried under reduced pressure at 80° C. for 12 hours to obtain 14.7 g of white solid DNFDP-m (yield 50%, LC purity 97.4%).

(Purification of BPEF)
The filtrate containing BPEF as a main component was stirred at 5 to 10°C for 1 hour, filtered, and washed with methanol at 10°C to obtain 15.1 g of crude crystals. After adding 52.8 g of toluene to the obtained crude crystals and completely dissolving them at 80°C, 20 g of water and 5 g of a 10% by mass HCl aqueous solution were added, and the mixture was stirred again at 80°C for 15 minutes. After leaving to stand and removing the separated aqueous phase, a water washing operation of adding 20 g of water to the organic phase and washing was carried out three times. The organic phase at 80°C was allowed to cool to room temperature, further stirred at 5 to 10°C for 1 hour, filtered, and the residue was washed with toluene at 10°C. The washed filtration residue was dried under reduced pressure at 80° C. for 12 hours to obtain 10.7 g of white solid BPEF (yield 70%, LC purity 98.9%).

Example 2
(Preparation of polymer B)
According to the conventional method, according to Production Example 2 in the Examples of Patent No. 7016976, the dicarboxylic acid unit accounts for 100 mol% of the structural unit derived from DNFDP-m, and the structural unit of the diol unit is 10 mol % of the structural unit derived from BPEF. %, and 90 mol % of structural units derived from EG. Polymer B was prepared.

(First decomposition step)
To 3.45 g of mixer-pulverized polymer B (the total number of monomers incorporated in polymer B corresponds to approximately 0.01 mole), 9.01 g of dimethyl carbonate and 0.35 g of a methanol solution containing LiOMe at a concentration of 10% by mass were added. The mixture was added and reacted at 65°C for 3 hours. To the obtained reaction mixture, 10 g of toluene was added and dissolved completely at 65°C, then 3.0 g of water and 0.34 g of a 10% by mass HCl aqueous solution were added, and the mixture was stirred at 65°C for 15 minutes. After removing the separated aqueous phase and washing the organic phase with water three times, insoluble matter was removed by filtration and concentrated to obtain a crude product.

(Second decomposition step)
6.4 g of methanol and 0.56 g of potassium hydroxide were added to the crude product, and the mixture was reacted under reflux conditions at 65° C. for 1 hour. By filtering at 50°C and washing with 15g of methanol at 40°C, 3.35g of crude crystals of DNFDP-m were obtained as a filtration residue. Moreover, the filtrate of the main filtration contains BPEF as a main component.

(Purification of DNFDP-m)
8.13 g of toluene was added to 3.35 g of crude crystals and completely dissolved at 80°C, then 3.0 g of water and 0.6 g of a 10% by mass HCl aqueous solution were added, and the mixture was stirred at 80°C for 15 minutes. After allowing the mixture to stand and removing the separated aqueous phase, 3.0 g of water was added to the organic phase and the operation of washing with water was repeated three times. The organic phase at 80°C was allowed to cool to room temperature and stirred at 5-10°C for 1 hour. After filtration and washing the residue with methanol, the washed filtration residue was dried under reduced pressure at 50°C for 12 hours to obtain 2.48 g of white solid DNFDP-m (yield 84%, LC purity 93.7%). Ta.

(Purification of BPEF)
Add 0.6 g of a 10% by mass HCl aqueous solution and 5 g of water to filtrate B, stir at 5 to 10°C for 1 hour, filter, and wash the residue with methanol at 10°C to obtain 0.09 g of crude crystals. Ta. 2.25 g of toluene was added to the obtained crude crystals and completely dissolved at 80°C, then allowed to cool and stirred at 5 to 10°C for 1 hour. After filtering and washing the filtration residue with toluene at 10°C, the washed filtration residue was dried under reduced pressure at 50°C for 12 hours to obtain 0.04g of white solid BPEF (yield 18%, LC purity 94.2). %)Obtained.

Example 3
(Preparation of Polymer C)
According to the conventional method, based on Example 16 of JP-A-2016-069643, the dicarboxylic acid unit accounts for 100 mol% of the structural unit derived from FDP-m, and 70 mol% of the structural unit derived from BNEF among the diol units. , Polymer C having 30 mol % of structural units derived from EG was prepared.

(First decomposition step)
To 3.67 g of mixer-pulverized polymer C (the total number of monomers incorporated into polymer C corresponds to approximately 0.01 mole), 9.01 g of dimethyl carbonate and 0.37 g of a methanol solution containing LiOMe at a concentration of 10% by mass were added. The mixture was added and reacted at 65°C for 2 hours. To the resulting reaction mixture, 0.9 g of water and 0.37 g of a 10% by mass HCl aqueous solution were added, and after stirring at 65° C. for 15 minutes, the separated organic phase was collected, and insoluble matter was removed by filtration. The results of LC-MS analysis of the organic phase were as follows.

BNEF: 4.400 area%
BNEF monocarbonate expressed by the following formula: 22.806 area%

BNEF dicarbonate expressed by the following formula: 37.648 area%

FDP-m: 18.616 area%.

(Second decomposition step)
The organic phase was concentrated, and 3.2 g of methanol and 0.56 g of potassium hydroxide were added to the crude product, and the mixture was reacted at 65° C. under reflux conditions for 1 hour. After the reaction was completed, 9.6 g of heptane was added and stirred at 65° C. for 10 minutes, and then the lower phase (containing methanol and BNEF) and the upper phase (containing heptane and FDP-m) were collected.

(Purification of FDP-m)
The above-mentioned upper phase was concentrated and dried under reduced pressure at 50° C. for 12 hours to obtain 0.13 g of white solid FDP-m (yield 8%, LC purity 92.2%).

(Purification of BNEF)
10 g of toluene, 4 g of 10% by mass HCl aqueous solution, and 3 g of water were added to the lower phase, stirred at 80°C, allowed to cool to room temperature, stirred at room temperature for 1 hour, filtered, and the residue was washed with 2-propanol. . The washed filtration residue was dried under reduced pressure at 50° C. for 12 hours to obtain 0.85 g of white solid BNEF (yield 45%, LC purity 96.0%).

Example 4
(Preparation of Polymer D)
According to the conventional method, based on Reference Example 6 of JP-A-2013-064117, the dicarboxylic acid unit is 100 mol% of the structural unit derived from DMT, and the diol unit is 70 mol% of the structural unit derived from BPEF, EG Polymer D having 30 mol % of structural units derived from the above was prepared.

(First decomposition step)
To 2.60 g of mixer-pulverized polymer D (the total number of monomers incorporated in polymer D corresponds to approximately 0.01 mole), 9.01 g of dimethyl carbonate and 0.26 g of a methanol solution containing LiOMe at a concentration of 10% by mass were added. The mixture was added and reacted at 65°C for 3 hours. To the obtained reaction mixture, 0.9 g of water, 0.26 g of 10% by mass HCl aqueous solution, and 5 g of ethyl acetate were added, and after stirring at 65°C for 15 minutes, the separated organic phase was collected, and insoluble matter was removed by filtration. did.

(Second decomposition step)
The organic phase was concentrated, and 9.6 g of methanol and 0.56 g of potassium hydroxide were added to the crude product, and the mixture was reacted at 65° C. under reflux conditions for 1 hour. After the reaction was completed, 3 g of 10% by mass HCl aqueous solution was added, and the mixture was stirred at 5 to 10°C for 30 minutes.

(Purification of BPEF)
Filtration was performed and the residue was washed with methanol. The washed filtration residue was dried under reduced pressure at 80° C. for 12 hours to obtain 1.5 g of white solid BPEF (yield 98%, LC purity 93.6%).

Example 5
(Preparation of Polymer E)
According to the conventional method, based on Example 3 of JP-A-2014-218645, the dicarboxylic acid unit accounts for 100 mol% of the structural unit derived from FDP-m, and 80 mol% of the structural unit derived from BPEF among the diol units. , Polymer E having 20 mol % of structural units derived from EG was prepared.

(First decomposition step)
To 3.50 g of mixer-pulverized polymer E (the total number of monomers incorporated in polymer E corresponds to approximately 0.01 mole), 9.01 g of dimethyl carbonate and 0.35 g of a methanol solution containing LiOMe at a concentration of 10% by mass were added. The mixture was added and reacted at 65°C for 3 hours. To the resulting reaction mixture, 0.9 g of water and 0.37 g of a 10% by mass HCl aqueous solution were added, and after stirring at 65° C. for 15 minutes, the separated organic phase was collected, and insoluble matter was removed by filtration.

(Second decomposition step)
The organic phase was concentrated, and 3.2 g of methanol and 0.56 g of potassium hydroxide were added to the crude product, followed by reaction at 65° C. for 1 hour under reflux conditions. After the reaction was completed, 9.6 g of heptane was added and stirred at 65° C. for 10 minutes, and then the lower phase (containing methanol and BPEF) and the upper phase (containing heptane and FDP-m) were collected.

(Purification of FDP-m)
The above-mentioned upper phase was concentrated and dried under reduced pressure at 50° C. for 12 hours to obtain 0.10 g of white solid FDP-m (yield 6%, LC purity 94.9%).

(Purification of BPEF)
8 g of toluene and 3 g of 10% by mass HCl aqueous solution were added to the lower phase, stirred at 60°C, slowly cooled to room temperature, stirred at room temperature for 1 hour, filtered, and the residue was washed with methanol to obtain crude crystals. 1.63g was obtained. 6.52 g of toluene was added to the crude crystals, and after dissolving at 85° C., the mixture was allowed to cool to room temperature and crystallized. It was filtered, the residue was washed with methanol, and the washed residue was dried under reduced pressure at 50° C. for 12 hours to obtain 0.31 g of white solid BPEF (yield 18%, LC purity 94.4%).

Example 6
(First decomposition step)
To 4.582 g of mixer-pulverized polymer A (the total number of monomers incorporated into polymer A corresponds to approximately 0.01 mole), 9.01 g of dimethyl carbonate and 0.916 g of a methanol solution containing NaOMe at a concentration of 10% by mass were added. The mixture was added and reacted at 65°C for 2 hours. To the obtained reaction mixture, 1.5 g of water and 0.55 g of a 10% by mass HCl aqueous solution were added, and after stirring at 65° C. for 15 minutes, the separated organic phase was collected, and insoluble matter was removed by filtration.

(Second decomposition step)
The organic phase was concentrated, and 8.01 g of methanol and 0.56 g of potassium hydroxide were added to the crude product, and the mixture was reacted at 65° C. under reflux conditions for 1 hour. The mixture was filtered at 60°C or above, and the residue was washed with 15.0g of methanol at 40°C to obtain 4.4g of DNFDP-m crude crystals. Moreover, the filtrate of the main filtration contains BPEF as a main component.

(Purification of DNFDP-m)
10.9 g of toluene was added to 4.4 g of crude crystals and completely dissolved at 80° C., then 5 g of water and 0.5 g of a 10% by mass HCl aqueous solution were added, and the mixture was stirred again at 80° C. for 15 minutes. After leaving to stand still and removing the separated aqueous phase, 5 g of water was added to the organic phase and washing with water was performed three times. The organic phase at 80°C was allowed to cool to room temperature, further stirred at 5 to 10°C for 1 hour, filtered, and the residue was washed successively with toluene and methanol. The washed residue was dried under reduced pressure at 50° C. for 12 hours to obtain 1.56 g of white solid DNFDP-m (yield 53%, LC purity 96.4%).

(Purification of BPEF)
Filtrate F was stirred at 5 to 10° C. for 1 hour, filtered, and the residue was washed with methanol at 10° C. to obtain 1.03 g of crude crystals. After adding 3.08 g of toluene to the obtained crude crystals and completely dissolving them at 80°C, 1 g of water and 0.5 g of a 10% by mass HCl aqueous solution were added, and the mixture was stirred again at 80°C for 15 minutes. After leaving to stand and removing the separated aqueous phase, 1 g of water was added to the organic phase and washing with water was performed three times. The organic phase at 80°C was allowed to cool to room temperature, further stirred at 5 to 10°C for 1 hour, filtered, and the residue was washed with methanol at 10°C. The washed residue was dried under reduced pressure at 50° C. for 12 hours to obtain 0.45 g of white solid BPEF (yield 29%, LC purity 98.1%).

Example 7
(Preparation of polymer F)
According to the conventional method, based on Example 7 of JP-A-2013-064118, the dicarboxylic acid unit accounts for 100 mol% of the structural unit derived from FDP-m, and 70 mol% of the structural unit derived from BOPPEF among the diol units. , Polymer F having 30 mol % of structural units derived from EG was prepared.

(First decomposition step)
To 4.12 g of mixer-pulverized polymer F (the total number of monomers incorporated in polymer F corresponds to approximately 0.01 mole), 9.01 g of dimethyl carbonate and 0.41 g of a methanol solution containing LiOMe at a concentration of 10% by mass were added. The mixture was added and reacted at 65°C for 4 hours. To the resulting reaction mixture, 0.9 g of water and 0.41 g of a 10% by mass HCl aqueous solution were added, and after stirring at 65° C. for 15 minutes, the separated organic phase was collected, and insoluble matter was removed by filtration.

(Second decomposition step)
The organic phase was concentrated, and 11.2 g of methanol and 0.56 g of potassium hydroxide were added to the crude product, followed by reaction at 65° C. for 1 hour under reflux conditions. After the reaction was completed, the mixture was slowly cooled to room temperature, filtered, and washed with 15.0 g of methanol to obtain 3.3 g of crude crystals of BOPPEF. Furthermore, the filtrate of the main filtration contains FDP-m as a main component.

(Purification of FDP-m)
25 g of heptane was added to the above-mentioned filtrate containing FDP-m as a main component, and after stirring at 40°C for 1 hour, the upper phase was concentrated and dried under reduced pressure at 50°C for 12 hours to obtain white solid FDP-m. 0.21 g (yield 12%, LC purity 96.3%) was obtained.

(Purification of BOPPEF)
To the above-mentioned crude crystals, 11.4 g of toluene, 5 g of water, and 0.2 g of a 10% by mass HCl aqueous solution were added, and after stirring at 60° C., a washing operation was carried out with 5 g of water, and the mixture was allowed to cool slowly to room temperature to crystallize. After filtering and washing the residue with methanol, it was dried under reduced pressure at 80° C. for 12 hours to obtain 1.99 g of white solid BOPPEF (yield: 84%, LC purity: 97.2%).

For Examples 1 to 7, the raw material polymer composition, the composition of the product after the first decomposition step, and the yield and purity of the dicarboxylic acid ester and diol after the purification step after the second decomposition step are shown in Table 1.

As is clear from the results in Table 1, in any of Examples 1 to 7, novel monocarbonic esters and dicarbonate esters were produced in the first decomposition step, and further in the second decomposition step and purification step. Through this process, dicarboxylic acid ester and diol could be recovered.

Example 8
(Preparation of polymer G)
According to a conventional method, based on Example 6 of JP-A No. 2013-064118, the dicarboxylic acid unit contains 30 mol% of the structural unit derived from DMN, 70 mol% of the structural unit derived from FDP-m, and diol Polymer G (polymer G having the composition ratio shown in Table 2) was prepared, in which the units contained 85 mol% of the structural units derived from BPEF and 15 mol% of the structural units derived from EG.

(Depolymerization of polyester G)
630.56 g of dimethyl carbonate and 34.610 g of a methanol solution containing LiOMe at a concentration of 10% by mass were added to 346.10 g of pelleted polymer G (the total number of monomers incorporated in polymer G corresponds to approximately 1.0 mol), The reaction was carried out at 65°C for 3 hours. 250 g of water, 34 g of a 10% by mass HCl aqueous solution, and 600 g of toluene were added, and after stirring at 65° C., the aqueous phase was removed. After performing a water washing operation until the conductivity of the aqueous phase became 10 μS/cm or less, the organic phase was filtered to remove insoluble matter. The organic phase was concentrated, and 480 g of methanol and 50.5 g of potassium hydroxide were added to the crude product, followed by reaction at room temperature for 2 hours. 100 g of a 10% by mass HCl aqueous solution and 300 g of water were added, and the mixture was stirred at room temperature for 1 hour. After suction filtration and washing with warm water at 60°C until the conductivity of the filtrate becomes 10 μS/cm or less, drying under reduced pressure at 50°C produces a white solid (molar ratio calculated from HPLC measurement: BPEF/DMN/FDP). -m=0.850/0.280/0.316) was obtained.

(repolymerization)
Using 68.70 g of the obtained depolymerized sample, as shown in Table 2, insufficient monomer components (additional portions in Table 2) were newly added to make the composition ratio of Polymer G, and JP-A-2013 A repolymerized product was produced in accordance with Example 6 of JP-A-064118.

Example 9
Using 20.00 g of the depolymerized sample obtained in Example 8, as shown in Table 2, insufficient monomer components (additional portions in Table 2) were newly added to make the composition ratio of Polymer G. A repolymerized product was produced according to Example 6 of JP-A No. 2013-064118.

Example 10
Using 10.00 g of the depolymerized sample obtained in Example 8, as shown in Table 2, insufficient monomer components (additional portions in Table 2) were newly added to make the composition ratio of Polymer G. A repolymerized product was produced according to Example 6 of JP-A No. 2013-064118.

Example 11
Using 5.00 g of the depolymerized sample obtained in Example 8, as shown in Table 2, insufficient monomer components (additional portions in Table 2) were newly added to make the composition ratio of Polymer G. A repolymerized product was produced according to Example 6 of JP-A No. 2013-064118.

Example 12
(Depolymerization of polymer G)
315.28 g of dimethyl carbonate, 3.461 g of NaOMe, and 31.149 g of methanol were added to 173.05 g of the pelleted polymer G obtained in Example 8 (the total number of monomers incorporated into the polymer G corresponds to approximately 0.5 mol). The mixture was added and reacted at 60°C for 2 hours. 125 g of water, 17 g of a 10% by mass HCl aqueous solution, and 300 g of toluene were added, and after stirring at 60° C., the aqueous phase was removed. After performing a water washing operation until the conductivity of the aqueous phase became 10 μs/cm or less, the organic phase was filtered to remove insoluble matter. The organic phase was concentrated, and 288 g of methanol and 25.2 g of potassium hydroxide were added to the crude product, followed by reaction at room temperature for 2 hours. 50 g of a 10% by mass HCl aqueous solution and 150 g of water were added, and the mixture was stirred at room temperature for 1 hour. After suction filtration and washing with warm water until the conductivity of the filtrate becomes 10 μs/cm or less, drying under reduced pressure at 50°C produces a white solid (mole ratio calculation from HPLC measurement: BPEF/DMN/FDP-m= 0.850/0.248/0.306) was obtained.

(repolymerization)
Using 69.81 g of the obtained depolymerized sample, as shown in Table 3, the monomer components that were insufficient to achieve the composition ratio of Polymer G (additional amount in Table 3) were newly added, and JP-A-2013 A repolymerized product was produced in accordance with Example 6 of JP-A-064118.

Example 13
Using 20.00 g of the depolymerized sample obtained in Example 12, as shown in Table 3, insufficient monomer components (additional portions in Table 3) were newly added to achieve the composition ratio of Polymer G. A repolymerized product was produced according to Example 6 of JP-A No. 2013-064118.

Example 14
Using 10.00 g of the depolymerized sample obtained in Example 12, as shown in Table 3, insufficient monomer components (additional portions in Table 3) were newly added to obtain the composition ratio of Polymer G. A repolymerized product was produced according to Example 6 of JP-A No. 2013-064118.

Example 15
Using 5.00 g of the depolymerized sample obtained in Example 12, as shown in Table 3, insufficient monomer components (additional portions in Table 3) were newly added to obtain the composition ratio of Polymer G. A repolymerized product was produced according to Example 6 of JP-A No. 2013-064118.

Example 16
(Depolymerization of polymer G)
242.27 g of the pelleted polymer G obtained in Example 8 (the total number of monomers incorporated into the polymer G corresponds to approximately 0.7 mol), 441.39 g of dimethyl carbonate, and methanol containing LiOMe at a concentration of 10% by mass. 24.227 g of the solution was added and reacted at 60°C for 2 hours. 63 g of water and 24 g of a 10% by mass HCl aqueous solution were added, and after stirring at 65° C., the organic phase was filtered to remove insoluble matter. The organic phase was concentrated, and 359 g of methanol and 39.3 g of potassium hydroxide were added to the crude product, followed by reaction at room temperature for 2 hours. 105 g of a 10% by mass aqueous HCl solution and 280 g of water were added, and the mixture was stirred at room temperature for 1 hour. After suction filtration, washing with water, and drying under reduced pressure at 50°C, a white solid (molar ratio calculated from HPLC measurement: BPEF/DMN/FDP-m = 0.850/0.382/0.486) was obtained. 238g was obtained.

(repolymerization)
Using 20.00 g of the obtained depolymerized sample, as shown in Table 4, insufficient monomer components (additional portions in Table 4) were newly added to make the composition ratio of Polymer G, and JP-A-2013 A repolymerized product was produced in accordance with Example 6 of JP-A-064118.

Example 17
Using 10.00 g of the depolymerized sample obtained in Example 16, as shown in Table 4, insufficient monomer components (additional portions in Table 4) were newly added to obtain the composition ratio of Polymer G. A repolymerized product was produced according to Example 6 of JP-A No. 2013-064118.

Example 18
Using 5.00 g of the depolymerized sample obtained in Example 16, as shown in Table 4, insufficient monomer components (additional portions in Table 4) were newly added to make the composition ratio of Polymer G. A repolymerized product was produced according to Example 6 of JP-A No. 2013-064118.

The evaluation results of Examples 8 to 18 are shown in Tables 2 to 4. Furthermore, the evaluation results for Polymer G are shown in Table 5 as a blank.

As is clear from the results in Tables 2 to 5, by appropriately replenishing the decomposition products obtained in the depolymerization process with insufficient monomer raw materials, the molecular weight of the polymer during repolymerization can be improved. A polymer with excellent optical properties was obtained.

Comparative example 1
(Depolymerization of polymer G)
According to the method described in Patent Documents 1 and 2, EG was added to the pellets of Polymer G obtained in Example 8, and polyester F was depolymerized by heating at 200 to 250 ° C. for about 3 hours. . The molecular weight distribution of Polymer G before depolymerization is shown in FIG. 1, and the molecular weight distribution of the decomposition product after depolymerization is shown in FIG. As is clear from the comparison between FIG. 1 and FIG. 2, some decomposition products were obtained after depolymerization, but a wide molecular weight distribution was observed and the decomposition products were not decomposed into monomer units.

In other words, in the conventional method of adding an excessive amount of solvent (ethylene glycol) and heating at high temperature, depolymerization progressed with general-purpose polyesters such as PET, but depolymerization of polymers with a fluorene skeleton did not proceed sufficiently. It turned out that it wasn't progressing.

Comparative example 2
(Depolymerization of polymer G)
According to the method described in Patent Document 3, 20 g of water was added to 10 g of the pelleted polymer G obtained in Example 8, and the mixture was treated with subcritical water at 300°C and 8 MPa nitrogen atmosphere for 2 hours to obtain polyester G. Depolymerized. The molecular weight distribution of Polymer G before depolymerization is shown in FIG. 3, and the molecular weight distribution of the decomposition product after depolymerization is shown in FIG. As is clear from the comparison between FIG. 3 and FIG. 4, some decomposition products were obtained after depolymerization, but a wide molecular weight distribution was observed and the decomposition products were not decomposed into monomer units.

In other words, in the conventional method of hydrolysis using subcritical water (hydrolysis method), while depolymerization progressed with general-purpose polyesters such as PET, depolymerization of polyesters with a fluorene skeleton did not progress sufficiently. There was found.

From the results of Comparative Examples 1 and 2, it can be understood that unlike general-purpose polyesters such as PET, it is difficult to depolymerize polyester resins having a fluorene skeleton using conventional methods.

Example 19
(Preparation of polymer H)
Polymer H having a carbonate ester bond in which diol units accounted for 100 mol % of constitutional units derived from BPEF was prepared according to a conventional method.

(First decomposition step)
22.52 g of dimethyl carbonate, 0.9324 g of NaOMe, and 8.3912 g of methanol were added to 46.618 g of Polymer H (the total number of monomers incorporated into the polymer corresponds to approximately 0.1 mole), and the mixture was reacted at 65° C. for 1 hour. . To the resulting reaction mixture, 60 g of toluene, 40 g of water, and 4.6 g of a 10% by mass HCl aqueous solution were added, and after stirring at 75° C. for 15 minutes, the washing step of washing the separated organic phase with 40 g of water was repeated three times. Thereafter, insoluble matter was removed by filtration.

(Second decomposition step)
The organic phase was concentrated, and 96 g of methanol and 4.49 g of potassium hydroxide were added to the obtained crude product (first decomposition product), and the mixture was reacted at room temperature for 1 hour. To the resulting reaction mixture, 8 g of a 10% by mass HCl aqueous solution and 30 g of water were added, and after stirring at 5 to 10° C. for 1 hour, 55 g of crude crystals of BPEF were obtained by filtration.

(BPEF purification process)
165 g of toluene was added to the above-mentioned crude crystals, and after complete dissolution at 75°C, the mixture was allowed to cool slowly to room temperature and stirred at 5 to 10°C for 1 hour. By filtering and drying under reduced pressure at 80° C. for 12 hours, 22.9 g of white solid BPEF (yield 52%, LC purity 98.3%) was obtained.

Regarding Example 19, the composition of the first decomposition product, the yield and purity of the diol (BPEF) after the BPEF purification step are shown in Table 6.

As is clear from the results in Table 6, in Example 19 as well, new monocarbonate and dicarbonate were produced in the first decomposition step, and further, through the second decomposition step and purification step, diol was able to be recovered.

Example 20
(Preparation of Polymer I)
According to a conventional method, Polymer I having a carbonate ester bond in which the diol units were 50 mol % of the constitutional units derived from BPEF and 50 mol % of the constitutional units derived from BINOL-2EO was prepared.

(First decomposition step)
11.26 g of dimethyl carbonate, 0.4065 g of NaOMe, and 3.6583 g of methanol were added to 20.324 g of Polymer I (the total number of monomers incorporated into the polymer corresponded to approximately 0.05 mol), and the mixture was reacted at 65° C. for 2 hours. To the resulting reaction mixture, 35 g of toluene, 20 g of water, and 2.3 g of a 10% by mass HCl aqueous solution were added, and after stirring at 75° C. for 15 minutes, the washing step of washing the separated organic phase with 20 g of water was repeated three times. Thereafter, insoluble matter was removed by filtration.

(Second decomposition step)
The organic phase was concentrated, and 48 g of methanol and 2.24 g of potassium hydroxide were added to the obtained crude product (first decomposition product), and the mixture was reacted at room temperature for 1 hour. To the resulting reaction mixture, 4 g of a 10% by mass HCl aqueous solution and 15 g of water were added, stirred at 5 to 10°C for 1 hour, filtered, and the filtration residue was dried under reduced pressure at 50°C to obtain a white solid (BPEF, BINOL). -2EO mixture) was obtained (LC purity 94.7%, yield 85% (purity and yield as the mixture)).

Example 21
(Preparation of Polymer J)
According to a conventional method, a polymer J having a carbonate ester bond in which the diol units were 50 mol % of constitutional units derived from BOPPEF and 50 mol % of constitutional units derived from BINOL-2EO was prepared.

(First decomposition step)
11.26 g of dimethyl carbonate, 0.4826 g of NaOMe, and 4.324 g of methanol were added to 24.129 g of Polymer J (the total number of monomers incorporated into the polymer corresponded to approximately 0.05 mol), and the mixture was reacted at 65° C. for 2 hours. To the resulting reaction mixture, 35 g of toluene, 20 g of water, and 2.3 g of a 10% by mass HCl aqueous solution were added, and after stirring at 75° C. for 15 minutes, the washing step of washing the separated organic phase with 20 g of water was repeated three times. Thereafter, insoluble matter was removed by filtration.

(Second decomposition step)
The organic phase was concentrated, and 48 g of methanol and 2.24 g of potassium hydroxide were added to the obtained crude product, and the mixture was reacted at room temperature for 1 hour. To the obtained reaction mixture, 4 g of a 10% by mass HCl aqueous solution and 15 g of water were added, stirred at 5 to 10°C for 1 hour, filtered, and the filtration residue was dried under reduced pressure at 50°C to obtain a white solid (BOPPEF, BINOL). -2EO mixture) was obtained (LC purity 98.2%, yield 90% (purity as the mixture)).

The dicarboxylic acid component and/or diol component obtained by the depolymerization method of the present disclosure has a fluorene skeleton and has excellent heat resistance and optical properties. It can be used as a resin raw material or additive. Furthermore, the novel diol carbonate obtained in the process of the depolymerization method of the present disclosure can be used as a raw material for polycarbonate resin, a reaction regulator, a resin additive, and other additives.

Claims

A method for depolymerizing a fluorene-containing resin, in which a fluorene-containing resin having a fluorene skeleton and an ester bond and/or a carbonate ester bond is reacted with a carbonate ester in the presence of a hydrolysis catalyst to obtain a decomposition product.
The depolymerization method according to claim 1, wherein the decomposition product includes a diol monocarbonate ester and/or a diol dicarbonate ester.
The depolymerization method according to claim 2, wherein the decomposition product further contains a dicarboxylic acid and/or an ester thereof.
The depolymerization method according to claim 1 or 2, wherein the decomposition product and alcohol are reacted to obtain a diol.
The fluorene-containing resin has the following formula (1)

(In the formula,
Ring Z 1 and Ring Z 2 independently represent arene rings,
R 1 and R 2 independently represent a substituent, m1 and m2 independently represent an integer of 0 or more,
n1 and n2 independently represent integers of 0 to 4,
A 1 and A 2 independently represent an alkylene group,
X 1 and X 2 independently represent a hydroxyl group, an alkoxy group or a halogen atom,
R 3 and R 4 independently represent a substituent, k1 and k2 independently represent an integer from 0 to 4)
A dicarboxylic acid component represented by and/or the following formula (2)

(In the formula,
Ring Z 3 and Ring Z 4 independently represent arene rings,
A3 and A4 independently represent an alkylene group, s1 and s2 independently represent an integer of 0 or more,
R5 and R6 independently represent a substituent, t1 and t2 independently represent an integer of 0 or more,
R 7 represents a substituent, and u represents an integer of 0 to 8)
The depolymerization method according to claim 1 or 2, which is a polyester resin containing a diol represented by as a polymerization component.
The fluorene-containing resin is a polyester resin containing a dicarboxylic acid component represented by the formula (1) as a polymerization component, and in the formula (1), n1 and n2 are 0, or n1 and n2 are 1, and ring Z 1 and ring Z 2 are independently fused polycyclic arene rings.
The depolymerization method according to claim 5, wherein the fluorene-containing resin is a polyester resin containing a diol represented by the formula (2) as a polymerization component.
The fluorene-containing resin has the following formula (2)

(In the formula,
Ring Z 3 and Ring Z 4 independently represent arene rings,
A3 and A4 independently represent an alkylene group, s1 and s2 independently represent an integer of 0 or more,
R5 and R6 independently represent a substituent, t1 and t2 independently represent an integer of 0 or more,
R 7 represents a substituent, and u represents an integer of 0 to 8)
The depolymerization method according to claim 1 or 2, which is a polycarbonate resin containing a diol represented by as a polymerization component.
The fluorene-containing resin has the following formula (5)

(In the formula,
A 5 represents a direct bond (single bond) or an alkylene group,
A 6 and A 7 independently represent an alkylene group, p1 and p2 independently represent an integer of 0 or more,
R 11 and R 12 independently represent a substituent, and q1 and q2 independently represent an integer from 0 to 6)
The depolymerization method according to claim 1 or 2, which contains a diol represented by as a polymerization component.
In the presence of a hydrolysis catalyst, a polyester resin containing a dicarboxylic acid component having a fluorene skeleton as a polymerization component is reacted with a carbonate ester to decompose the polyester resin, thereby producing a dicarboxylic acid having a fluorene skeleton and/or its ester. How to manufacture.
In the presence of a hydrolysis catalyst, a polyester resin containing a diol having a fluorene skeleton as a polymerization component is reacted with a carbonate ester, and the polyester resin is decomposed to form a dicarboxylic acid and/or its ester and a monocarbonate ester of the diol. a first decomposition step to obtain a first decomposition product containing a dicarbonate and/or a dicarbonate of a diol;
A method for producing a diol having a fluorene skeleton through a second decomposition step of reacting the first decomposition product with an alcohol to obtain a diol.
In the presence of a hydrolysis catalyst, a polyester resin having a fluorene skeleton and an ester bond is reacted with a carbonate ester to decompose the polyester resin, and a dicarboxylic acid and/or its ester and a diol monocarbonate and/or or a first decomposition step to obtain a decomposition product containing a dicarbonate ester of diol;
A method of recovering a monomer component having a fluorene skeleton through a second decomposition step of reacting the decomposition product with an alcohol to obtain a diol.
In the presence of a hydrolysis catalyst, a polycarbonate resin having a fluorene skeleton and a carbonate bond is reacted with a carbonate ester to decompose the polycarbonate resin, resulting in a monocarbonate of diol and/or a diol diol. a first decomposition step to obtain a first decomposition product containing a carbonate ester;
A method of recovering a monomer component having a fluorene skeleton through a second decomposition step of reacting the first decomposition product with an alcohol to obtain a diol.
The following formula (3)

(In the formula,
Ring Z 3 and Ring Z 4 independently represent arene rings,
A3 and A4 independently represent an alkylene group, s1 and s2 independently represent an integer of 0 or more,
R 8 represents a hydrocarbon group,
R5 and R6 independently represent a substituent, t1 and t2 independently represent an integer of 0 or more,
R 7 represents a substituent, and u represents an integer of 0 to 8)
A monocarbonate ester of diol represented by
The following formula (4)

(In the formula,
Ring Z 3 and Ring Z 4 independently represent arene rings,
A3 and A4 independently represent an alkylene group, s1 and s2 independently represent an integer of 0 or more,
R 9 and R 10 independently represent a hydrocarbon group,
R5 and R6 independently represent a substituent, t1 and t2 independently represent an integer of 0 or more,
R 7 represents a substituent, and u represents an integer of 0 to 8)
A dicarbonate ester of diol represented by
In the presence of a hydrolysis catalyst, a fluorene-containing resin having a fluorene skeleton and an ester bond and/or a carbonate ester bond is reacted with a carbonate ester to decompose the fluorene-containing resin, thereby producing the diol monocarbonate ester according to claim 14. A method of manufacturing a body, the method comprising:
The fluorene-containing resin has the following formula (2)

(In the formula,
Ring Z 3 and Ring Z 4 independently represent arene rings,
A3 and A4 independently represent an alkylene group, s1 and s2 independently represent an integer of 0 or more,
R5 and R6 independently represent a substituent, t1 and t2 independently represent an integer of 0 or more,
R 7 represents a substituent, and u represents an integer of 0 to 8)
A method in which the fluorene-containing resin contains a diol represented by as a polymerization component.
In the presence of a hydrolysis catalyst, a fluorene-containing resin having a fluorene skeleton and an ester bond and/or a carbonate ester bond is reacted with a carbonate ester to decompose the fluorene-containing resin, thereby producing a dicarbonate ester form of a diol according to claim 15. A method of manufacturing,
The fluorene-containing resin has the following formula (2)

(In the formula,
Ring Z 3 and Ring Z 4 independently represent arene rings,
A3 and A4 independently represent an alkylene group, s1 and s2 independently represent an integer of 0 or more,
R5 and R6 independently represent a substituent, t1 and t2 independently represent an integer of 0 or more,
R 7 represents a substituent, and u represents an integer of 0 to 8)
A method in which the fluorene-containing resin contains a diol represented by as a polymerization component.
A method for recycling a fluorene-containing resin having a fluorene skeleton, an ester bond and/or a carbonate bond, the method comprising:
a depolymerization step in which the fluorene-containing resin and carbonate ester are reacted in the presence of a hydrolysis catalyst to obtain a decomposition product;
A recycling method comprising a polymerization step of polymerizing the decomposition product obtained in the depolymerization step to obtain a new fluorene-containing resin.
The recycling method according to claim 18, wherein in the polymerization step, monomer raw materials for the new fluorene-containing resin are replenished.