Method for depolymerizing resin with fluorene framework, product and application thereof

Abstract

The present disclosure relates to depolymerizing a fluorene-containing resin having a fluorene backbone and ester and / or carbonate bonds by a depolymerization process comprising reacting the fluorene-containing resin with a carbonate in the presence of a hydrolysis catalyst to decompose the fluorene-containing resin to obtain a decomposed product. The depolymerization method can simply or easily depolymerize the fluorene-containing resin. The decomposition product may comprise a monocarbonate form of a diol and / or a dicarbonate form of a diol. In the depolymerization process, the decomposition product may be reacted with an alcohol to obtain a diol.

Description

Technical Field

[0001] The present invention relates to the depolymerization of a resin having a fluorene skeleton and an ester bond and / or a carbonate bond. Background Art

[0002] In recent years, achieving a decarbonized society has become a global priority, and the Sustainable Development Goals (SDGs) have been set as specific goals. As part of this, the recycling (reuse) of waste plastics has also been promoted. In particular, polyester resins represented by polyethylene terephthalate (PET) are circulated in large quantities as beverage bottles or textiles, so there is a great demand for recycling. As a method of recycling plastics, it is known to chemically decompose plastics into low molecular weight compounds and prepare plastics from the decomposed low molecular weight compounds. Chemical recycling has attracted attention from the perspective of the high quality of the recycled products and the fact that the recycled products can be reused repeatedly.

[0003] As a method of chemical recovery, Japanese Patent Application Laid-Open No. 2003-128600 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2003-119316 (Patent Document 2) disclose a method of adding an excess of ethylene glycol to decompose PET to produce terephthalic acid.

[0004] WO2004 / 041917 (Patent Document 3) discloses a method of decomposing polyester into monomers or oligomers by hydrolysis using subcritical water or supercritical water.

[0005] Green Chem, 2021, 23, 9412-9416 (non-patent document 1) records that methanol, dimethyl carbonate (DMT), and lithium methoxide are mixed in a suitable ratio in a sheet of PET, and the mixture is reacted at 28°C for 5 hours to produce dimethyl terephthalate at a yield of 74%. When the reaction temperature is changed to 50°C, PET is completely decomposed within 5 hours. This method generates dimethyl terephthalate and ethylene carbonate by decomposition reaction. The document records that dimethyl carbonate acts as an ethylene glycol scavenger, and since the ethylene carbonate generated by the above reaction is a stable 5-membered ring structure, the decomposition reaction proceeds. Prior art literature

[0006] Patent Literature Patent Document 1: Japanese Patent Application Publication No. 2003-128600 Patent Document 2: Japanese Patent Application Publication No. 2003-119316 Patent Document 3: WO2004 / 041917

[0007] Non-patent literature Non-patent literature 1: Shinji Tanaka et al., “Capturing ethylene glycol with dimethyl carbonate towards depolymerisation of polyethylene terephthalate at ambient temperature”, Green Chem, 2021, 23, 9412-9416 Summary of the invention Problems to be solved by the invention

[0008] However, the depolymerization methods of Patent Documents 1 to 3 require the reaction to be carried out under high temperature and high pressure conditions. For example, in any method, the reaction temperature is above 200° C., and monomers cannot be prepared easily, resulting in low productivity.

[0009] On the other hand, the depolymerization method of Non-Patent Document 1 can depolymerize PET at low temperature, but does not describe polyester resins other than PET. For example, in recent years, polyester resins having a fluorene skeleton have been used for optical applications, but due to the large volume of the fluorene skeleton, the structure of the polyester resin having a fluorene skeleton is very different from that of widely used polyesters such as PET, and the chemical behavior is different due to the different properties of the fluorene skeleton. However, Non-Patent Document 1 does not describe polyester resins having a fluorene skeleton.

[0010] Therefore, an object of the present disclosure is to provide a method for easily or simply depolymerizing a resin having a fluorene skeleton and an ester bond and / or a carbonate bond in a molecule and use of the resin.

[0011] Another object of the present disclosure is to provide a method for preparing a novel carbonate compound by depolymerizing a resin having a fluorene skeleton and an ester bond and / or a carbonate bond. Means of solving problems

[0012] The present inventors have conducted intensive research to achieve the above-mentioned problems and have found that by reacting a resin having a fluorene skeleton and an ester bond and / or a carbonate bond with a carbonate in the presence of a hydrolysis catalyst, the above-mentioned resin can be decomposed (depolymerized) in a simple or easy manner. The present disclosure is completed based on the above-mentioned discovery.

[0013] That is, one aspect of the present disclosure (aspect [1]) is A method for depolymerizing a fluorene-containing resin, wherein the fluorene-containing resin has a fluorene skeleton and an ester bond and / or a carbonate bond (hereinafter, the resin is sometimes referred to as "fluorene-containing resin" for short), the method comprising: reacting the fluorene-containing resin with a carbonate in the presence of a hydrolysis catalyst to obtain or provide a decomposition product.

[0014] One aspect of the present disclosure may be an aspect wherein the decomposition product in aspect [1] comprises a monocarbonate form of a diol and / or a dicarbonate form of a diol (aspect [2]) or an aspect wherein the decomposition product in aspect [2] further comprises a dicarboxylic acid and / or an ester thereof (aspect [3]).

[0015] One aspect of the present disclosure may be an aspect in which any one of aspects [1] to [3] further comprises reacting the decomposition product with an alcohol to obtain a diol (aspect [4]).

[0016] One aspect of the present disclosure may be an aspect (aspect [5]) in which the fluorene-containing resin in any one of aspects [1] to [4] is a polyester-based resin containing a dicarboxylic acid component represented by the following formula (1) and / or a diol represented by the following formula (2) as a polymerization component.

[0017] [Chemistry 1]

[0018] (Where, Ring Z 1 and Ring Z 2 independently represent an aromatic hydrocarbon ring, R 1 and R 2 independently represent a substituent, m1 and m2 independently represent an integer greater than 0, n1 and n2 independently represent an integer from 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 k1 and k2 independently represent an integer of 0 to 4.

[0019] [Chemistry 2]

[0020] (Where, Ring Z 3 and Ring Z 4 independently represent an aromatic hydrocarbon ring, A 3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer from 0 to 8. )

[0021] One aspect of the present disclosure may be that the fluorene-containing resin in aspect [5] is a polyester-based resin containing a dicarboxylic acid component represented by the formula (1) as a polymerization component, wherein n1 and n2 are each 0, or n1 and n2 are each 1, and ring Z 1 and Ring Z 2 An aspect in which the condensed polycyclic aromatic hydrocarbon rings are independently represented (aspect [6]) or an aspect in which the fluorene-containing resin in aspect [5] or [6] is a polyester resin containing the diol represented by the formula (2) as a polymerization component (aspect [7]).

[0022] One aspect of the present disclosure may be an aspect (aspect [8]) in which the fluorene-containing resin in any one of aspects [1] to [4] is a polycarbonate-based resin containing a diol represented by the following formula (2) as a polymerization component.

[0023] [Chemistry 3]

[0024] (Where, Ring Z 3 and Ring Z 4 independently represent an aromatic hydrocarbon ring, A 3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer of 0 to 8. )

[0025] One aspect of the present disclosure may be an aspect (aspect [9]) in which the fluorene-containing resin in any one of the aspects [1] to [8] contains a diol represented by the following formula (5) as a polymerization component. [Chemistry 4]

[0027] (Where, 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 greater than 0, R11 and R 12 independently represent substituents, q1 and q2 independently represent an integer from 0 to 6.)

[0028] One aspect of the present disclosure (aspect

[10] ) is a method for preparing a fluorene skeleton-containing dicarboxylic acid (or a dicarboxylic acid having a fluorene skeleton) and / or its ester, the method comprising reacting a polyester resin containing a fluorene skeleton-containing dicarboxylic acid component (or a dicarboxylic acid component having a fluorene skeleton) as a polymerization component with a carbonate in the presence of a hydrolysis catalyst to decompose the polyester resin.

[0029] One aspect of the present disclosure (aspect

[11] ) is a method for preparing a fluorene skeleton-containing diol (or a diol having a fluorene skeleton), the method comprising: reacting a polyester resin containing a fluorene skeleton-containing diol (fluorene-containing diol) as a polymerization component with a carbonate in the presence of a hydrolysis catalyst to decompose the polyester resin to obtain a first decomposition product containing a dicarboxylic acid and / or an ester thereof, a monocarbonate form of a diol, and / or a dicarbonate form of a diol; and A second decomposition step is performed by reacting the first decomposition product with an alcohol to obtain a diol.

[0030] One aspect of the present disclosure (aspect

[12] ) is a method for recovering a monomer component containing a fluorene skeleton (a monomer component having a fluorene skeleton), the method comprising: a first decomposition step of reacting a polyester resin having a fluorene skeleton and an ester bond with a carbonate in the presence of a hydrolysis catalyst to decompose the polyester resin to obtain a decomposition product containing a dicarboxylic acid and / or an ester thereof, a monocarbonate form of a diol, and / or a dicarbonate form of a diol; and A second decomposition step is to react the decomposition product with an alcohol to obtain a diol.

[0031] One aspect of the present disclosure (aspect

[13] ) is a method for recovering a monomer component containing a fluorene skeleton, the method comprising: a first decomposition step of reacting a polycarbonate resin having a fluorene skeleton and a carbonate bond with a carbonate in the presence of a hydrolysis catalyst to decompose the polycarbonate resin to obtain a first decomposition product containing a monocarbonate form of a diol and / or a dicarbonate form of a diol, and A second decomposition step is performed by reacting the first decomposition product with an alcohol to obtain a diol.

[0032] One aspect of the present disclosure (aspect

[14] ) is a monocarbonate form of a diol represented by the following formula (3),

[0033] [Chemistry 5]

[0034] (Where, Ring Z3 and Ring Z 4 independently represent an aromatic hydrocarbon ring, A 3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 8 represents a hydrocarbon group, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer of 0 to 8. )

[0035] One aspect of the present disclosure (aspect

[15] ) is a dicarbonate form of a diol represented by the following formula (4),

[0036] [Chemistry 6]

[0037] (Where, Ring Z 3 and Ring Z 4 independently represent an aromatic hydrocarbon ring, A 3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 9 and R 10 independently represent a hydrocarbon group, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer of 0 to 8. )

[0038] One aspect of the present disclosure (aspect

[16] ) is a method for preparing a monocarbonate form of the diol of aspect

[14] , the method comprising: reacting a fluorene-containing resin having a fluorene skeleton and an ester bond and / or a carbonate bond with a carbonate in the presence of a hydrolysis catalyst to decompose the fluorene-containing resin, The fluorene-containing resin is a fluorene-containing resin containing a diol represented by the following formula (2) as a polymerization component,

[0039] [Chemistry 7]

[0040] (Where, Ring Z 3 and Ring Z 4 independently represent an aromatic hydrocarbon ring, A3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer of 0 to 8. )

[0041] One aspect of the present disclosure (aspect

[17] ) is a method for preparing a dicarbonate form of the diol of aspect

[15] , the method comprising: reacting a fluorene-containing resin having a fluorene skeleton and an ester bond and / or a carbonate bond with a carbonate in the presence of a hydrolysis catalyst to decompose the fluorene-containing resin, The fluorene-containing resin is a fluorene-containing resin containing a diol represented by the following formula (2) as a polymerization component,

[0042] [Chemistry 8]

[0043] (Where, Ring Z 3 and Ring Z 4 Independently represents an aromatic ring A 3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer of 0 to 8. )

[0044] One aspect of the present disclosure (aspect

[18] ) is a method for recovering a fluorene-containing resin having a fluorene skeleton and an ester bond and / or a carbonate bond, the method comprising: a depolymerization step of reacting the fluorene-containing resin with a carbonate in the presence of a hydrolysis catalyst to obtain a decomposition product, and A polymerization step of polymerizing the decomposition product obtained in the depolymerization step to obtain a newly generated fluorene-containing resin.

[0045] One aspect (aspect

[19] ) of the present disclosure may be an aspect in which the monomer raw material of the newly produced fluorene-containing resin is supplemented in the polymerization step of the aspect

[18] .

[0046] In the specification and claims of the present application, the number of carbon atoms in a substituent etc. may be expressed as C1, C6, C 10For example, "C1 alkyl" refers to an alkyl group with 1 carbon number, and "C 6-10 The term "aryl group" refers to an aryl group having 6 to 10 carbon atoms. Effects of the Invention

[0047] According to the method for depolymerizing a fluorene-containing resin disclosed herein, a resin having a fluorene skeleton and an ester bond and / or a carbonate bond in a molecule, such as a polyester resin or a polycarbonate resin, can be simply or easily depolymerized. BRIEF DESCRIPTION OF THE DRAWINGS [ Figure 1 ] Figure 1 This is a graph showing the molecular weight distribution of the polyester obtained in Comparative Example 1 before depolymerization. [ Figure 2 ] Figure 2 This is a graph showing the molecular weight distribution of the decomposition product obtained by depolymerizing the polyester obtained in Comparative Example 1. [ Figure 3 ] Figure 3 This is a graph showing the molecular weight distribution of the polyester obtained in Comparative Example 2 before depolymerization. [ Figure 4 ] Figure 4 This is a graph showing the molecular weight distribution of the decomposition product obtained by depolymerizing the polyester obtained in Comparative Example 2. DETAILED DESCRIPTION

[0049] [Fluorene-containing resin] In the present disclosure, the resin to be depolymerized is a fluorene-containing resin [or a (carbonate) ester bond-containing resin] having a fluorene skeleton and an ester bond and / or a carbonate bond in the molecule. In addition, in the specification and claims of the present application, a (carbonate) ester bond refers to an ester bond and / or a carbonate bond.

[0050] Examples of the resin having a (carbonic acid) ester bond in the molecule include polyester, polyester polycarbonate (polyester carbonate), and polycarbonate.

[0051] The fluorene skeleton may be located in the main chain or side chain of the fluorene-containing resin. In addition, the fluorene skeleton is directly connected to the (carbonic acid) ester bond from the fluorene skeleton or via a divalent linking group. The (carbonic acid) ester bond or the divalent linking group may be connected to any position of the fluorene skeleton, and the bonding position is not particularly limited, preferably 9,9 position and 2,7 position of the fluorene ring, and particularly preferably 9,9 position of the fluorene ring. The above-mentioned divalent linking group may be a linking group containing at least a hydrocarbon group.

[0052] Among the fluorene-containing resins, preferred are: fluorene-containing resins containing at least an ester bond formed by polymerization of at least a dicarboxylic acid component and a diol component, and fluorene-containing resins containing at least a carbonate bond formed by polymerization of at least a diol component. Examples of such fluorene-containing resins include: fluorene-containing polyester resins represented by fluorene-containing polyester resins and fluorene-containing polyester carbonate resins; preferably, fluorene-containing polycarbonate resins represented by fluorene-containing polycarbonate resins; more preferably, fluorene-containing polyester resins and fluorene-containing polycarbonate resins; and particularly preferably, fluorene-containing polyester resins.

[0053] [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 fluorene skeleton-containing component.

[0054] (Fluorene-containing dicarboxylic acid component) When the dicarboxylic acid component as a polymerization component contains a dicarboxylic acid component containing a fluorene skeleton (fluorene-containing dicarboxylic acid component), the fluorene-containing dicarboxylic acid component is not particularly limited, but is preferably a dicarboxylic acid component represented by the above formula (1).

[0055] In the above formula (1), as ring Z 1 and Ring Z 2 Examples of the aromatic hydrocarbon ring represented by include monocyclic aromatic hydrocarbon rings such as a benzene ring, polycyclic aromatic hydrocarbon rings, and the like; examples of the polycyclic aromatic hydrocarbon ring include condensed polycyclic aromatic hydrocarbon rings, ring-aggregated aromatic hydrocarbon rings, and the like.

[0056] Examples of the condensed polycyclic aromatic hydrocarbon ring include condensed bicyclic aromatic hydrocarbon rings, and specific examples include condensed bicyclic C cyclopentane rings such as a naphthalene ring and an indene ring. 10-16 Aromatic hydrocarbon rings, etc.; condensed tricyclic aromatic hydrocarbon rings, condensed two to four ring aromatic hydrocarbon rings, etc. Examples of condensed tricyclic aromatic hydrocarbon rings include anthracene rings, phenanthrene rings, and condensed tricyclic C 14-20 Aromatic hydrocarbon rings, etc. Preferred fused polycyclic aromatic hydrocarbon rings are fused bicyclic C 10-14 Aromatic hydrocarbon ring. Examples of the ring-aggregated aromatic ring include biphenyl ring, phenylnaphthalene ring, binaphthyl ring and other biaryl hydrocarbon rings; terphenyl ring and other triaryl hydrocarbon rings. Preferred ring-aggregated aromatic rings are C 12-18 Biaryl ring.

[0057] Preferred ring Z 1 and Z 2 C 6-14 Aromatic hydrocarbon ring, preferably benzene ring, naphthalene ring, biphenyl ring, etc. 6-12 Aromatic hydrocarbon ring, more preferably benzene ring, naphthalene ring, etc. 6-10 Aromatic hydrocarbon ring, most preferably naphthalene ring.

[0058] Ring Z 1 and Z 2The types can vary, but are usually the same.

[0059] In addition, Ring Z 1 and Z 2 Each of them can be substituted at any position of 1 to 4, 5 to 8 of the fluorene ring, usually at 2, 3 and / or 7, 8. Preferred substitution positions (or bonding positions) are 1, 8, 2, 7, 3, 6, 4, 5, etc. of the fluorene ring, which are symmetrical on the paper in the above formula (1), especially 2, 7. 1 , Z 2 When it is a naphthalene ring, the 1-position or 2-position of the naphthalene ring can be bonded to the fluorene ring. From the viewpoint of improving heat resistance, it is particularly preferred that the 1-position of the naphthalene ring is bonded to the fluorene ring. From the viewpoint of preparing a resin that satisfies a high refractive index, a low Abbe number and a low birefringence (or a large negative birefringence) in a well-balanced manner, it is particularly preferred that the 2-position of the naphthalene ring is bonded to the fluorene ring.

[0060] As R 1 and R 2 The substituent represented by includes a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acyl group, a nitro group, a cyano group, a mono- or di-substituted amino group, and the like.

[0061] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0062] The alkyl group includes a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, and the like. 1-10 Alkyl, preferably C 1-6 Alkyl, more preferably C 1-4 Examples of the aryl group include C phenyl, alkylphenyl, biphenyl, naphthyl, etc. 6-12 Aryl; methylphenyl (or tolyl), dimethylphenyl (or xylyl) and other mono- or tri-C 1-4 Alkyl-phenyl, etc.

[0063] Examples of the alkoxy group include methoxy, ethoxy, propoxy, n-butoxy, tert-butoxy and the like. 1-10 Examples of the acyl group include C 1-6 Alkyl-carbonyl, etc.

[0064] Examples of the mono- or di-substituted amino group include mono- or di-C 1-4 Alkylamino; diacetylamino and other di(C 1-4 alkyl-carbonyl)amino.

[0065] As a representative group R 1 and R 2 , and examples thereof include alkyl, aryl, alkoxy, acyl, nitro, cyano, etc. Preferred groups R1 and R 2 is an alkyl group (specifically a methyl group, etc. 1-6 Alkyl); Alkoxy (specifically methoxy, etc. C 1-4 Alkoxy) ; particularly preferably methyl etc. C 1-4 Alkyl. It is noted that when the group R 1 and R 2 When it is an aromatic group, the group R 1 and R 2 Can be respectively with ring Z 1 and Z 2 Together the above rings form an aromatic hydrocarbon ring.

[0066] 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 further preferably 0. When m1 and m2 are integers of 2 or more, two or more groups R 1 and R 2 The types can be the same or different.

[0067] The substitution numbers n1 and n2 can be selected from an integer range of 0 to 4, for example, an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and more preferably 1. If a compound in which n1 and n2 are each 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.

[0068] As group A 1 and A 2 The alkylene group represented by the present invention includes C groups such as methylene, ethylene, trimethylene, propylene, 1,4-butanediyl, and 2-methylpropane-1,3-diyl. 1-8 Among them, C 1-6 Alkylene, more preferably C 2-4 Alkylene, more preferably ethylene, propylene, etc. 2-3 Alkylene, most preferably ethylene.

[0069] As X 1 and X 2 Examples of the alkoxy groups include methoxy, ethoxy, propoxy, tert-butoxy, and the like. 1-4 Alkoxy, etc., preferably C 1-2 Examples of the halogen atom include a chlorine atom and a bromine atom. Preferred X 1 and X 2 is a hydroxyl group, a methoxy group, or an ethoxy group. For reaction at low temperature, a halogen atom such as a chlorine atom is also preferred. Among them, a methoxy group, an ethoxy group, or the like is more preferred. 1-2 Alkoxy, most preferably methoxy.

[0070] As R 3 and R4 The substituent represented by the above-mentioned group includes an alkyl group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, a cyano group, etc. As the alkyl group, there are C groups such as a methyl group, an ethyl group, and a tert-butyl group. 1-6 Alkyl etc. Preferred R 3 and R 4 It is methyl etc. 1-4 alkyl.

[0071] R 3 and R 4 The substitution position of R can be the 1st, 2nd, 7th, 3rd, 6th, 4th, 5th or 2nd, 7th position of the fluorene ring. 3 and R 4 The substitution numbers k1 and k2 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, and further preferably 0. When k1 and k2 are integers of 2 or more, 2 or more R 3 and R 4 The types of the substituents may be the same or different.

[0072] Representative examples of the fluorene-containing dicarboxylic acid components represented by the above formula (1) include: dicarboxylic acid components wherein n1 and n2 are each 0, i.e., 9,9-bis(carboxyalkyl)fluorenes; and dicarboxylic acid components wherein n1 and n2 are each 1, i.e., 9,9-bis(carboxyalkyl)-diarylfluorenes.

[0073] That is, a preferred fluorene-containing dicarboxylic acid component may be a dicarboxylic acid component represented by the following formula (1a), (1b) or (1c).

[0074] [Chemistry 9]

[0075] (In the formula, A 1 , A 2 , X 1 , X 2 , R 3 , R 4 , k1 and k2 are respectively the same as those defined in the above formula (1).

[0076] Examples of the compound wherein n1 and n2 in formula (1) are each 0 [9,9-bis(carboxyalkyl)fluorenes corresponding to formula (1a)] include 9,9-bis(2-carboxyethyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene, and the like. 2-6 Alkyl) fluorene, etc., preferably 9,9-bis (carboxyl C 2-4 9,9-bis(carboxyl C 2-39,9-bis(2-carboxyethyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene, and most preferably 9,9-bis(2-carboxyethyl)fluorene. These compounds may be ester-forming derivatives, preferably C esters such as methyl esters or ethyl esters. 1-4 Alkyl esters, most preferably methyl esters, etc. 1-4 Alkyl esters.

[0077] In the specification and claims of the present application, the ester-forming derivatives are meant to include halogenated carboxylic acids such as acid chlorides, alkyl esters such as methyl esters, and acid anhydrides.

[0078] Examples of the compounds (9,9-bis(carboxyalkyl)-diarylfluorenes) in which n1 and n2 in formula (1) are each 1 include 9,9-bis(carboxyalkyl)-diphenylfluorenes corresponding to the above formula (1b), 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-diphenylfluorene and the like. 2-6 9,9-bis(carboxyalkyl)-dinaphthylfluorene corresponding to the above 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(2-carboxypropyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-di(1-naphthyl)fluorene, etc. 2-6 These compounds may be ester-forming derivatives, preferably methyl esters or ethyl esters, etc. 1-4 Alkyl esters, most preferably methyl esters, etc. 1-4 Alkyl esters.

[0079] 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 above formula (1), 9,9-bis(2-carboxyethyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene and the like are preferred. 2-4 9,9-bis(2-carboxyethyl)-2,7-diphenylfluorene, 9,9-bis(2-carboxypropyl)-2,7-diphenylfluorene, etc. 2-49,9-bis(2-carboxyethyl)-2,7-dinaphthylfluorene, 9,9-bis(2-carboxypropyl)-2,7-dinaphthylfluorene, etc. 2-4 9,9-bis(carboxy C 2-4 Alkyl)-2,7-dinaphthylfluorene. In 9,9-bis(carboxyl C 2-4 In the 2,7-dinaphthylfluorene, the naphthyl group may be 1-naphthyl (i.e., 9,9-bis(carboxyl C 2-4 alkyl)-2,7-di(1-naphthyl)fluorene), but preferably 2-naphthyl (i.e., 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(carboxy C 2-4 These compounds may be ester-forming derivatives, preferably methyl esters or ethyl esters, etc. 1-4 Alkyl esters, most preferably methyl esters, etc. 1-4 Alkyl esters.

[0080] The fluorene-containing dicarboxylic acid component represented by the above formula (1) and its preparation method are well known. The compound wherein n1 and n2 are each 0 can be prepared by reacting 9H-fluorene with the corresponding group [-A 1 -CO-X 1 ] and [-A 2 -CO-X 2 ] components, such as (meth) acrylic acid or its ester, etc., wherein n1 and n2 are each 1 or more, and the compound can be prepared by making the 9,9 positions have a group [-A 1 -CO-X 1 ] and [-A 2 -CO-X 2 ] containing a fluorene skeleton compound and a corresponding ring Z 1 The compound of the aromatic hydrocarbon ring and the corresponding ring Z 2 or by coupling the benzene ring of 9H-fluorene with the corresponding ring Z 1 The compound of the aromatic hydrocarbon ring and the corresponding ring Z 2 The resulting compound (compound having a 9H-fluorene skeleton) is coupled to a compound having an aromatic hydrocarbon ring, and the corresponding group [-A 1 -CO-X 1 ] and [-A 2 -CO-X 2] components such as (meth)acrylic acid or its esters.

[0081] (Fluorene-containing diol) When the diol component as the polymerization component contains a fluorene skeleton-containing diol (or a diol having a fluorene skeleton or a fluorene-containing diol), the fluorene-containing diol is not particularly limited, but is preferably a diol represented by the above formula (2).

[0082] In formula (2), as Z 3 and Z 4 The aromatic hydrocarbon ring represented by the formula (1) may be: 1 and Z 2 The same aromatic ring. Ring Z 3 and Z 4 The types may be the same or different from each other, usually mostly the same. 3 and Z 4 Among them, a benzene ring, a naphthalene ring, a biphenyl ring, etc. are preferred. 6-12 Aromatic ring, more preferably benzene ring, naphthalene ring, etc. 6-10 Aromatic ring.

[0083] It should be noted that ring Z 3 and Z 4 The bonding position relative to the 9-position of the fluorene ring is not particularly limited. For example, ring Z 3 and Z 4 When it is a naphthalene ring, the bonding position is 1 or 2, preferably 2, and ring Z 3 and Z 4 In the case of a biphenyl ring, the bonding position is any of the 2-position, 3-position and 4-position, and is preferably the 3-position.

[0084] As a substituent R 7 , may be a non-reactive substituent that is inert to the reaction, for example, a cyano group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom; a hydrocarbon group such as an alkyl group and an aryl group; etc. Examples of the aryl group include C 6-10 Aryl etc. As the preferred group R 7 , is a cyano group, a halogen atom or an alkyl group, particularly an alkyl group. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and the like. 1-12 Alkyl, preferably C 1-8 Alkyl, more preferably C 1-6 Alkyl, more preferably methyl, etc. 1-4 alkyl.

[0085] It should be noted that the base R 7 When the number of substitution u is 2 or more, in the two benzene rings constituting the fluorene ring, the two or more groups R substituted on the same benzene ring 7The types may be the same or different, and the two or more groups R substituted on different benzene rings 7 The types of R can be the same or different. 7 The bonding position (substitution position) of is not particularly limited as long as it is the 1-8 position of the fluorene ring, and examples thereof include the 2-position, 7-position, 2,7-position, and the like of the fluorene ring.

[0086] The number of substitutions 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, and most preferably 0. 7 The numbers of substitution may be different from each other, but are preferably the same.

[0087] As R 5 and R 6 The substituent represented by the above formula (1) may be, for example, the following: 1 and R 2 The same group as the substituent (halogen atom; alkyl group, aryl group; alkoxy group; acyl group; nitro group; cyano group; mono- or di-substituted amino group, etc.), cycloalkyl group, aralkyl group, etc.

[0088] Preferred groups R 5 and R 6 Examples include alkyl groups, aryl groups, and alkoxy groups, and more preferably C groups such as methyl groups are included. 1-6 Alkyl, phenyl, etc. C 6-14 Aryl, methoxy, etc. 1-4 Among these substituents, alkyl and aryl groups are preferred, and methyl and other C 1-4 Alkyl, phenyl, etc. 6-10 Aryl. It should be noted that when the group R 5 or R 6 When it is an aromatic group, the group R 5 or R 6 Can also be used with Ring Z 3 or Z 4 Together the above rings form an aromatic hydrocarbon ring.

[0089] The substitution numbers t1 and t2 are respectively integers greater than 0, and can be determined according to the 3 or Z 4 The number of substitutions t1 and t2 is selected according to the type, for example, it can be an integer of 0 to 8, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, 0 or 1, and most preferably 0. When the number of substitutions t1 and t2 is an integer of 2 or more, two or more groups R 5 and R 6 The types can be the same or different.

[0090] It should be noted that when the number of substitutions t1 and t2 is 1, ring Z 3 and Z4 It can be a benzene ring, a naphthalene ring or a biphenyl ring, and the group R 5 and R 6 It can be methyl. When t1 and t2 are 2, ring Z 3 and Z 4 It can be a benzene ring, group R 5 and R 6 It may be methyl. The group R 5 and R 6 The substitution position is not particularly limited, but is usually 3 and Z 4 The ether-containing groups [-O-(A 3 O) s1 -H] or [-O-(A 4 O) s2 -H] is substituted at least at the ortho position (or substituted on the carbon atom adjacent to the bonding position of the above-mentioned ether bond-containing group).

[0091] As alkylene A 3 and A 4 , C groups such as ethylene, propylene (1,2-propylene), trimethylene, 1,2-butanediyl, and tetramethylene can be mentioned. 2-6 Alkylene, etc., preferably C 2-4 Alkylene, more preferably ethylene, propylene, etc. 2-3 Alkylene, most preferably ethylene.

[0092] The repeating numbers s1 and s2 are respectively 0 or more, for example, can be selected from the integer range of 0 to 15, and in order to promote the esterification reaction, are 1 or more, preferably an integer of 1 to 10, an integer of 1 to 8, an integer of 1 to 6, an integer of 1 to 4, an integer of 1 to 3, 1 or 2, and most preferably 1. It should be noted 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, two or more alkylene groups A 3 and A 4 In the specification and claims of the present application, "repetition number (addition mole number)" may be an average value (arithmetic mean, arithmetic mean) or an average addition mole number, and a preferred embodiment is the same as the above preferred range (the range of the above integer).

[0093] The group [-O-(A 3 O) s1 -] and [-O-(A 4 O) s2 -] (also called ether-containing group) in ring Z 3 and Z 4 The substitution position on the ring is not particularly limited. 3 and Z 4When the ring Z is a benzene ring, the above ether-containing group is usually substituted at any position of the 2nd, 3rd, or 4th position of the phenyl group connected to the 9th position of the fluorene ring, preferably at the 3rd or 4th position, especially at the 4th position; 3 and Z 4 When the ring Z is a naphthalene ring, the 1-position or 2-position of each naphthalene ring is bonded to the 9-position of the fluorene ring (the fluorene ring has a 1-naphthyl or 2-naphthyl substituent), and each ether-containing group is substituted on each naphthalene ring in the relationship of 1,5-position or 2,6-position, especially 2,6-position relative to the bonding position. 3 and Z 4 For a biphenyl ring (or ring Z 3 and Z 4 is a benzene ring, t1 and t2 are 1, R 5 and R 6 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 may be the 6 position or 4′ position of the biphenyl ring, especially the 6 position.

[0094] Examples of the fluorene-containing diol include 9,9-bis(hydroxyaryl)fluorenes wherein s1 and s2 in the above formula (2) are 0, and 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes wherein s1 and s2 in the above formula (2) are 1 or more, for example, 1 to 10.

[0095] Preferred fluorene-containing diols may include a compound represented by the following formula (2a) or (2b).

[0096] [Chemistry 10]

[0097] (In the formula, A 3 , A 4 ,s1,s2,R 5 , R 6 , t1, t2, R 7 and u are respectively the same as those defined in the above formula (2).

[0098] Examples of the 9,9-bis(hydroxyphenyl)fluorenes corresponding to the above formula (2a) include: 9,9-bis(hydroxyphenyl)fluorene such as 9,9-bis(4-hydroxyphenyl)fluorene; 9,9-bis(alkyl-hydroxyphenyl)fluorene, specifically 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, etc. 1-4 9,9-bis(aryl-hydroxyphenyl)fluorene, specifically 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, etc. 6-10Aryl-hydroxyphenyl)fluorene, etc.

[0099] In addition, examples of 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorenes corresponding to formula (2a) include alkylene oxide (or alkylene carbonate, halogenated alkyl alcohol) adducts of the above-mentioned 9,9-bis(hydroxyphenyl)fluorenes, for example, 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene, specifically 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropyloxy)phenyl]fluorene, and the like. 2-4 9,9-bis[(mono- or di-)C 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[4-(2-hydroxypropoxy)-3-methylphenyl]fluorene, etc. 1-4 Alkyl-hydroxy (mono to ten) C 2-4 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene, specifically 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)-3-phenylphenyl]fluorene, 9,9-bis(4-(2-hydroxypropyloxy)-3-phenylphenyl)fluorene, etc. 9,9-bis[C 6-10 Aryl-Hydroxy(mono-decyl)C 2-4 Alkoxy-phenyl]fluorene, etc.

[0100] Examples of the 9,9-bis(hydroxynaphthyl)fluorenes corresponding to the above formula (2b) include 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(5-hydroxy-1-naphthyl)fluorene and the like. Examples of the 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorenes include 9,9-bis[6-(2-hydroxyethoxy)-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[6-(2-hydroxypropoxy)-2-naphthyl]fluorene and the like. 2-4 Alkoxy-naphthyl]fluorene, etc.

[0101] These fluorene-containing diols may be used alone or in combination of two or more. Among them, 9,9-bis[hydroxy(mono-hexa)C 2-4 Alkoxy C 6-129,9-bis[hydroxy(poly)alkoxyaryl]fluorene, more preferably 9,9-bis[hydroxy(mono- or di-)C 2-4 Alkoxy-C 6-12 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[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (BOPPEF), 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF), and the like are more preferred. 2-3 Alkoxy-C 6-12 [aryl] fluorene, among which BPEF, BOPPEF and BNEF are particularly preferred, and BPEF and BNEF are most preferred.

[0102] (Other dicarboxylic acid components) The dicarboxylic acid component may contain other dicarboxylic acid components (dicarboxylic acid components other than the fluorene-containing dicarboxylic acid component) in addition to the fluorene-containing dicarboxylic acid component. When the diol component contains a fluorene-containing diol, the dicarboxylic acid component may be another dicarboxylic acid component alone.

[0103] Other dicarboxylic acid components include aliphatic dicarboxylic acid components, alicyclic dicarboxylic acid components, aromatic dicarboxylic acid components and the like.

[0104] Examples of the aliphatic dicarboxylic acid component include alkane dicarboxylic acids, unsaturated aliphatic dicarboxylic acids, or ester-forming derivatives thereof. Examples of the alkane dicarboxylic acids include malonic acid, succinic acid, adipic acid, and the like. 1-20 Alkane-dicarboxylic acids, etc. Examples of unsaturated aliphatic dicarboxylic acids include maleic acid, fumaric acid, etc. 2-10 Olefin-dicarboxylic acids, etc.

[0105] Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids, crosslinked cyclic cycloalkane dicarboxylic acids, cycloolefin dicarboxylic acids, crosslinked cyclic cycloolefin dicarboxylic acids, or ester-forming derivatives thereof. Examples of the cycloalkane dicarboxylic acids include cyclohexane dicarboxylic acids, and the like. 4-12 Examples of cross-linked cycloalkane dicarboxylic acids include (bi- or tri-)cyclic C 7-10 Examples of cycloolefin dicarboxylic acids include cyclopentene dicarboxylic acid and the like. 5-10 Examples of crosslinked cyclic cycloolefin dicarboxylic acids include (bi- or tri-)cyclic C 7-10 Olefin-dicarboxylic acids, etc.

[0106] Examples of the aromatic dicarboxylic acid component include monocyclic aromatic dicarboxylic acids, polycyclic aromatic dicarboxylic acids, or ester-forming derivatives thereof. Examples of the monocyclic aromatic dicarboxylic acid component include phthalic acid, isophthalic acid, terephthalic acid, and other benzene dicarboxylic acids; 5-methylisophthalic acid, and other C 1-4 Alkyl-benzenedicarboxylic acid, etc. Examples of the polycyclic aromatic dicarboxylic acid component include condensed polycyclic aromatic dicarboxylic acids, ring-aggregated aromatic dicarboxylic acids, etc. Examples of the condensed polycyclic aromatic dicarboxylic acid include 1,2-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, condensed polycyclic C 10-24 Aromatic dicarboxylic acids, etc. Examples of the ring-aggregated aromatic dicarboxylic acids include biphenyl dicarboxylic acids such as 2,2'-biphenyl dicarboxylic acid, 3,3'-biphenyl dicarboxylic acid, and 4,4'-biphenyl dicarboxylic acid. 6-10 Aromatic hydrocarbons - dicarboxylic acids, etc.

[0107] These other dicarboxylic acid components may be used alone or in combination of two or more. Among them, aromatic dicarboxylic acid components are preferred, and benzene dicarboxylic acids such as terephthalic acid are particularly preferred.

[0108] (Other glycol components) The diol component may contain other diol components (diol components other than the fluorene-containing diol) in addition to the fluorene-containing diol. When the dicarboxylic acid component contains a fluorene-containing dicarboxylic acid component, the diol component may be another diol component alone.

[0109] Other diol components include linear aliphatic diols, alicyclic diols, aromatic diols and the like.

[0110] Examples of the linear aliphatic diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, and neopentyl glycol. 2-10 Alkanediol; diethylene glycol, dipropylene glycol, triethylene glycol and other di- or tri-C 2-4 Alkanediol, etc.

[0111] Examples of the alicyclic diol include cyclohexanediol and the like. 5-8 Cycloalkanediol; cyclohexanedimethanol and other di(hydroxy C 1-4 Alkyl)C 5-8 Cycloalkanes, etc.

[0112] Examples of the aromatic diol include: dihydroxy aromatic hydrocarbons such as hydroquinone and resorcinol; aromatic aliphatic diols such as benzyl alcohol; bisphenols such as bisphenol F, bisphenol AD, bisphenol A, bisphenol C, bisphenol G, and bisphenol S; bisphenols such as p,p'-bisphenol; binaphthols such as binaphthol; and C of these diol components. 2-4Alkylene oxide (or alkylene carbonate, halogenated alkanol) adducts, etc. The binaphthols may be diols represented by the formula (5) described below.

[0113] These other diol components can be used alone or in combination of two or more. Among them, low molecular weight aliphatic diols (chain aliphatic diols) such as alkanediols are preferred, and C 2+ diols such as ethylene glycol are more preferred. 2-4 Alkanediol.

[0114] (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 also contains a carbonate bond forming component as a polymerization component for forming a carbonate unit. It should be noted that in the specification and claims of the present application, "carbonate unit" refers to a structural unit derived from a carbonate bond forming component, i.e., a carbonyl [-C(=O)-], which forms a carbonate bond together with the terminal oxygen atom of the structural unit from the two diol components bonded adjacent to the carbonyl. Therefore, as a carbonate bond forming component, as long as it is a compound that can form a carbonate bond by reacting with two diol components, as a representative carbonate bond forming component, for example, phosgenes such as phosgene and triphosgene, carbonic acid diesters such as diphenyl carbonate, etc. are cited. From the viewpoint of safety, carbonic acid diesters such as diphenyl carbonate are preferred.

[0115] In the fluorene-containing polyester carbonate resin, the ratio of the total amount of the dicarboxylic acid component and the carbonate bond forming component to the diol component is the former / the latter (molar ratio) = 1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, preferably approximately equimolar. In addition, the ratio of the dicarboxylic acid component to the carbonate bond forming component can be selected from the range of the former / the latter (molar ratio) = 99 / 1 to 1 / 99, preferably 95 / 5 to 10 / 90, 90 / 10 to 20 / 80, 80 / 20 to 30 / 70, 70 / 30 to 40 / 60. When the ratio of the carbonate bond forming component is too much, the refractive index or heat resistance may be reduced.

[0116] (Characteristics of fluorene-containing polyester resin) In the fluorene-containing polyester resin, the proportion of the polymer component containing the fluorene skeleton in the total polymer components containing the dicarboxylic acid component and the diol component can be 10 mol% or more, preferably 30 mol% or more, 30 to 99 mol%, 40 to 98 mol%, 50 to 95 mol%, 70 to 93 mol%, 80 to 90 mol%, 82 to 88 mol%. The present disclosure enables the fluorene-containing polyester resin with a large proportion of fluorene skeleton, especially the fluorene-containing polyester resin, to be efficiently depolymerized, and the useful monomer component (monomer) containing the fluorene skeleton can be efficiently recovered.

[0117] In the specification and claims of the present application, the ratio (molar ratio) of the polymerized components means the ratio (molar ratio) of the structural units in the fluorene-containing resin.

[0118] The weight average molecular weight of the fluorene-containing polyester resin can be selected from the 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, and most preferably 45,000 to 60,000.

[0119] In the specification and claims of the present application, the weight average molecular weight of the fluorene-containing polyester resin can be measured by gel permeation chromatography by converting a standard substance into polystyrene.

[0120] 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., and most preferably 135 to 190° C. In the specification and claims of the present application, the glass transition temperature can be measured using a differential scanning calorimeter, and more specifically, can be measured using the method described in the examples described below.

[0121] The fluorene-containing polyester resin may be amorphous.

[0122] In the fluorene-containing polyester resins such as the fluorene-containing polyester resin, the proportion of the fluorene-containing dicarboxylic acid component is not particularly limited. When the diol component contains a fluorene-containing diol, the dicarboxylic acid component may not contain a fluorene-containing dicarboxylic acid component, but the proportion of the fluorene-containing dicarboxylic acid component in the dicarboxylic acid component is preferably 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, respectively, and most preferably 100 mol%.

[0123] The proportion of fluorene-containing diol is not particularly limited. When the dicarboxylic acid component contains a fluorene-containing dicarboxylic acid component, the diol component may not contain fluorene-containing diol, but the proportion of fluorene-containing diol in the diol component is preferably 1 mol% or more, 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%.

[0124] The dicarboxylic acid component and / or diol component of the fluorene-containing polyester resin such as the fluorene-containing polyester resin only need to have a fluorene skeleton, preferably at least the diol component has a fluorene skeleton, and most preferably both the dicarboxylic acid component and the diol component have a fluorene skeleton. The polyester resin in which both the dicarboxylic acid component and the diol component have a fluorene skeleton has a high-density, bulky fluorene skeleton, and is greatly different from the widely used polyester resin in not only structure but also behavior, but in the depolymerization method disclosed in the present invention, useful monomers having a fluorene skeleton can be effectively recovered.

[0125] In particular, the diol component preferably contains not only a fluorene-containing diol but also other diol components (especially C 2-4 Fluorene-containing diols in combination with aliphatic diols such as alkylene glycols.

[0126] In fluorene-containing polyester resins such as fluorene-containing polyester resins, the molar ratio of fluorene-containing diols to other diol components (especially aliphatic diols) can be selected from the range of the former / the latter = 100 / 0 to 30 / 70. The preferred ranges are 99 / 1 to 40 / 60, 95 / 5 to 50 / 50, 90 / 10 to 55 / 45, 80 / 20 to 60 / 40, and 75 / 25 to 65 / 35 are the most preferred.

[0127] (A) First decomposition step In the depolymerization method of the fluorene-containing polyester resin disclosed herein, in the first decomposition step, the fluorene-containing polyester resin is reacted with a carbonate in the presence of a first hydrolysis catalyst to decompose the fluorene-containing polyester resin to obtain a decomposition product (first decomposition product) containing a dicarboxylic acid and / or its ester, a monocarbonate form of a diol, and / or a dicarbonate form of a diol.

[0128] (Carbonate) Carbonate acts as a depolymerizing agent for fluorene-containing polyester resins. Carbonate includes carbonic acid diesters such as dialkyl carbonate (dialkanol carbonate) and diaryl carbonate. Examples of dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, di-tert-butyl carbonate, etc. Examples of diaryl carbonate include diphenyl carbonate and tolylphenyl carbonate, etc.

[0129] These carbonates can be used alone or in combination of two or more. 1-4 Alkyl, more preferably di-C 1-3 Alkyl ester, more preferably di-C 1-2 Alkyl esters, most preferably dimethyl carbonate.

[0130] The ratio of carbonate to 1 mole of fluorene-containing polyester resin (the number of moles corresponding to the number average molecular weight) can be 1 mole or more, for example, 1 to 50 moles, preferably 2 to 30 moles, more preferably 3 to 20 moles, further preferably 5 to 15 moles, and most preferably 8 to 12 moles. Relative to 100 parts by mass of fluorene-containing polyester resin, the ratio of carbonate can be, for example, 50 parts by mass or more, for example, 50 to 1000 parts by mass, preferably 100 to 500 parts by mass, more preferably 120 to 400 parts by mass, further preferably 150 to 380 parts by mass, and most preferably 180 to 350 parts by mass. If the ratio of carbonate is too small, depolymerization may not proceed rapidly.

[0131] (First hydrolysis catalyst) The first hydrolysis catalyst may be any commonly used hydrolysis catalyst, and may be an acid catalyst, but is preferably a base catalyst. Base catalysts include inorganic bases, organic bases, and the like.

[0132] Examples of the inorganic base 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; alkali metal oxides such as sodium oxide and potassium oxide; alkaline earth metal oxides such as magnesium oxide, calcium oxide and barium oxide; alkali or alkaline earth metal carbonates such as cesium carbonate and sodium carbonate; alkali or alkaline earth metal hydrogen carbonates such as sodium hydrogen carbonate; ammonia, etc.

[0133] Examples of the organic base include: carboxylic acid bases or alkaline earth metal salts such as sodium acetate and calcium acetate; alkali metal alkoxides such as lithium methoxide, sodium methoxide, potassium methoxide, sodium ethoxide, sodium propoxide, and sodium tert-butoxide; organic metal compounds such as butyl lithium, phenyl lithium, isopropyl magnesium chloride, cyclohexyl magnesium bromide, phenyl magnesium bromide, sodium amide, and lithium diisopropylamide; amines, etc.

[0134] These base catalysts can be used alone or in combination of two or more. Among them, alkali metal C 1-6 Alkoxide, more preferably an alkali metal C 1-4 Alkoxide, more preferably an alkali metal C 1-3 Alkoxide, most preferably C 1-2 Alkali metal C such as lithium alcoholate 1-2 Alcohol salt.

[0135] The ratio of the first hydrolysis catalyst to 1 mol of the fluorene-containing polyester resin may be, for example, 0.01 mol or more, preferably 0.01 to 0.3 mol, more preferably 0.03 to 0.2 mol, further preferably 0.05 to 0.15 mol, and most preferably 0.08 to 0.12 mol. The ratio of the first hydrolysis catalyst to 100 parts by mass of the fluorene-containing polyester resin may be, for example, 0.1 parts by mass or more, preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, further preferably 0.3 to 2 parts by mass, and most preferably 0.5 to 1.5 parts by mass. If the ratio of the first hydrolysis catalyst is too small, depolymerization may not proceed rapidly. These ratios of the first hydrolysis catalyst may be ratios of a base catalyst.

[0136] (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, further preferably 50 to 75°C, and most preferably 60 to 70°C.

[0137] The reaction time may be 10 minutes or longer, for example 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 to 5 hours, and further preferably 2 to 4 hours.

[0138] The reaction can be carried out in the presence of an inert or inert gas, but is preferably carried out in the atmosphere from the perspective of convenience. In addition, the reaction can be carried out under reduced pressure, but is preferably carried out under atmospheric pressure from the perspective of convenience.

[0139] (1st decomposition product) The first decomposition product in the first decomposition step includes dicarboxylic acid and / or its ester, and monocarbonate form of diol and / or dicarbonate form of diol. Therefore, the present disclosure also includes a method for preparing monocarbonate form of diol and / or dicarbonate form of diol by the above-mentioned first decomposition step.

[0140] The ester of the dicarboxylic acid may be an alkyl ester. As the alkyl ester form, preferably the methyl ester form, the ethyl ester form, etc. 1-3 When the dicarboxylic acid and / or its ester is the dicarboxylic acid component represented by the above formula (1), the dicarboxylic acid and / or its ester can be X in the above formula (1). 1 and X 2 Represents C 1-4 The alkoxy dicarboxylic acid component is preferably X 1 and X 2 Indicates methoxyl group etc. 1-2 The dicarboxylic acid component of the alkoxy group is particularly preferably X 1 and X 2 represents a methoxy group. 1 and X2 C 1-2 When an alkoxy group is present, newly generated fluorene-containing resins can be prepared with high productivity in chemical recycling. 1 and X 2 The alkyl group contained in the alkoxy group may be an alkyl group derived from the base catalyst.

[0141] The monocarbonate form of the diol and / or the dicarbonate form of the diol can be converted into a diol by performing the second decomposition step in the next step, and the resulting diol can be reused as a raw material for the fluorene-containing polyester resin. The monocarbonate form of the diol and / or the dicarbonate form of the diol can be used as a carbonate compound without performing the second decomposition step.

[0142] Examples of the monocarbonate form of the diol include the monocarbonate form of the diol represented by the above formula (3). This monocarbonate form is a novel compound and can be used as a raw material for polycarbonate resins, a reaction regulator, a resin additive, and the like.

[0143] The monocarbonate form of the diol represented by the above formula (3) is a monocarbonate form obtained by adding carbonate to only one of the hydroxyl groups of the diol represented by the above formula (2).

[0144] In the above formula (3), R 8 The hydrocarbon group represented by may include alkyl, aryl, etc. Among them, alkyl and phenyl are preferred, and alkyl is particularly preferred. As alkyl, methyl, ethyl, propyl, isopropyl, butyl, etc. may be used alone or in combination of two or more. Among them, C 1-4 Alkyl, more preferably C 1-3 Alkyl, more preferably C 1-2 Alkyl, most preferably methyl.

[0145] Examples of the dicarbonate form of the diol include the dicarbonate form of the diol represented by the above formula (4), etc. This dicarbonate form is also a novel compound and can be used as a raw material for a polycarbonate resin, a resin additive, and the like.

[0146] The dicarbonate form of the diol represented by the formula (4) is a dicarbonate form in which carbonate is added to the two hydroxyl groups of the diol represented by the above formula (2).

[0147] In the above formula (4), R 9 and R 10 The hydrocarbon group represented by may include alkyl, aryl, etc. Among them, alkyl and phenyl are preferred, and alkyl is particularly preferred. As alkyl, methyl, ethyl, propyl, isopropyl, butyl, etc. may be used alone or in combination of two or more. Among them, C 1-4 Alkyl, more preferably C 1-3 Alkyl, more preferably C1-2 Alkyl, most preferably methyl.

[0148] In the first decomposition step, the total ratio of the monocarbonate form and the dicarbonate form is, for example, 0.1 to 5 mol, preferably 0.2 to 3 mol, more preferably 0.3 to 2 mol, and further preferably 0.5 to 1.5 mol per 1 mol of the dicarboxylic acid component.

[0149] The ratio of the monocarbonate form to 1 mol of the dicarbonate form is, for example, 0.1 to 1 mol, preferably 0.2 to 0.9 mol, more preferably 0.3 to 0.8 mol, and even more preferably 0.4 to 0.6 mol.

[0150] The first decomposition product may further include a diol. The diol may be a diol corresponding to the monocarbonate form and the dicarbonate form. The ratio of the diol relative to 1 mole of the total of the dicarboxylic acid and its ester is about 0.2 moles or less, for example, 0.1 moles or less, preferably 0.05 moles or less, and more preferably 0.01 to 0.03 moles.

[0151] The first decomposition product can be subjected to conventional purification treatment. Conventional purification treatments include, for example, neutralizing and washing the mixture containing the decomposition product as required, and then removing impurities from the mixture by filtration or the like. When a monomer component is precipitated in the above mixture, a good solvent for the monomer component can be used to completely dissolve the monomer component, followed by neutralization and washing.

[0152] In the first decomposition step, dicarboxylic acids and / or their esters and monocarbonate forms of diols and / or dicarbonate forms of diols are mainly obtained. Therefore, when the target fluorene skeleton-containing monomer component is a dicarboxylic acid component, or when a new carbonate compound is a target compound, the depolymerization method of the present disclosure may be a depolymerization method in which the decomposition step includes only the first decomposition step and does not include the second decomposition step described later.

[0153] (B) Second decomposition step The depolymerization method of the fluorene-containing polyester resin disclosed herein may further include a second decomposition step for obtaining a second decomposition product in addition to the first decomposition step. In the second decomposition step, the first decomposition product is reacted with an alcohol to obtain a diol. Specifically, in the second decomposition step, the monocarbonate form of the diol and / or the dicarbonate form of the diol are reacted with the alcohol to obtain the diol. In this way, in the second decomposition step, since the monocarbonate form of the diol and / or the dicarbonate form of the diol can be converted into a diol, it is particularly effective when the diol containing a fluorene skeleton is recovered as a monomer component.

[0154] (alcohol) Examples of the alcohol include methanol, ethanol, isopropanol, propanol, butanol, and the like. 1-4 These alcohols can be used alone or in combination of two or more. Among them, C 1-3 Alkanol, more preferably C 1-2 The alkanol is most preferably methanol. In the second decomposition step, the decomposition reaction proceeds in the presence of a dicarboxylic acid component, so it is preferred to use an alcohol corresponding to the alkoxide used as the first hydrolysis catalyst in the first decomposition step.

[0155] The proportion of the alcohol may be 50 parts by mass or more, for example, 50 to 1000 parts by mass, preferably 80 to 500 parts by mass, more preferably 100 to 300 parts by mass, further preferably 120 to 250 parts by mass, and most preferably 150 to 200 parts by mass, relative to 100 parts by mass of the first decomposition product. If the proportion of the alcohol is too small, the yield of the diol component may decrease.

[0156] (Second hydrolysis catalyst) As the second hydrolysis catalyst, there can be mentioned: the hydrolysis catalysts exemplified as the first hydrolysis catalyst, etc. 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.

[0157] The ratio of the second hydrolysis catalyst to 100 parts by mass of the first decomposition product may be 1 part by mass or more, for example, 1 to 30 parts by mass, preferably 5 to 25 parts by mass, and more preferably 10 to 20 parts by mass. If the ratio of the second hydrolysis catalyst is too small, the yield of the diol component may be reduced. These ratios of the second hydrolysis catalyst may be the ratios of the base catalyst.

[0158] (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, further preferably 50 to 75°C, and most preferably 60 to 70°C.

[0159] The reaction time may be 5 minutes or longer, for example, 5 minutes to 5 hours, preferably 10 minutes to 3 hours, more preferably 30 minutes to 2 hours, and further preferably 40 minutes to 1.5 hours.

[0160] The reaction can be carried out in the presence of an inert or inert gas, but is preferably carried out in the atmosphere from the perspective of convenience. In addition, the reaction can be carried out under reduced pressure, but is preferably carried out under atmospheric pressure from the perspective of convenience.

[0161] (Second decomposition product) The second decomposition product in the second decomposition step includes dicarboxylic acid and / or its ester and diol. That is, in the depolymerization method of the present disclosure including the second decomposition step, all raw materials of 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, and the recoverability of the fluorene-containing polyester resin can be improved.

[0162] (C) Purification step The mixture containing dicarboxylic acid and / or its ester and diol obtained in the second decomposition step can be separated into dicarboxylic acid and / or its ester and diol by a conventional method, and each component can be subjected to a purification step.

[0163] For example, dicarboxylic acid and / or its ester and diol can be separated by filtration or the like using a solvent that acts as a good solvent for diol and acts as a poor solvent for dicarboxylic acid and / or its ester. 1-4 Alkyl alcohol.

[0164] Alternatively, a good solvent for dicarboxylic acid and / or its ester and a good solvent for diol incompatible with the good solvent may be used to extract the dicarboxylic acid and / or its ester and the diol. 1-4 The solvent extraction method is effective when the dicarboxylic acid and / or its ester is in a good solvent such as a diol such as an alkanol. Examples of the good solvent for the dicarboxylic acid and / or its ester include aliphatic hydrocarbons such as heptane.

[0165] The separated monomer components (dicarboxylic acid and / or its ester, diol) can be purified by conventional methods. As the purification method, conventional methods such as filtration, concentration, crystallization, and column chromatography can be appropriately combined. Among them, the purification method including crystallization is preferred.

[0166] As a method of crystallization, it is preferred to crystallize the monomer component using a crystallization solvent containing an aromatic hydrocarbon and / or a polar solvent.

[0167] As aromatic hydrocarbons, mono- or di-C 1-2 Alkyl-benzenes, particularly preferably toluene.

[0168] As the polar solvent, water, ethanol, isopropanol, etc. are preferred. 1-4 aliphatic ketones having more than 3 carbon atoms, such as acetone and methyl isobutyl ketone, particularly preferably: water, C 2-3 Alkanol; aliphatic ketones with 4 to 8 carbon atoms.

[0169] Among the crystallization solvents, good solvents include aromatic hydrocarbons and aliphatic ketones having 4 or more carbon atoms. Poor solvents include water, C 1-4 Alkanols, etc.

[0170] 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, and further preferably 20 to 50 parts by mass, relative to 100 parts by mass of the good solvent.

[0171] The proportion of the crystallization solvent is, for example, 10 to 3000 parts by mass, preferably 50 to 2000 parts by mass, more preferably 100 to 1000 parts by mass, and most preferably 200 to 500 parts by mass, based on 100 parts by mass of the monomer component.

[0172] In the crystallization treatment, by dissolving the monomer component in the above-mentioned crystallization solvent and cooling, a monomer component with higher purity can be precipitated (precipitated) or crystallized. The temperature at which the monomer component is dissolved in the above-mentioned crystallization solvent is a temperature lower than the boiling point of the solvent, for example, 30 to 200° C., preferably 50 to 150° C., and more preferably 60 to 100° C. The monomer component treated by crystallization can be washed and dried by a conventional method.

[0173] [Fluorene-containing polycarbonate resin] The fluorene-containing polycarbonate-based resin disclosed herein contains a diol component as a polymerization component, and the diol component contains a fluorene-containing diol.

[0174] (Fluorene-containing diol) The fluorene-containing diol is not particularly limited, but is preferably a diol component represented by the above formula (2) described in the section of the fluorene-containing polyester resin. Examples of the diol represented by the above formula (2) include the diol represented by the above formula (2) exemplified in the section of the fluorene-containing polyester resin. The above diol components may be used alone or in combination of two or more.

[0175] Among the above diol components, 9,9-bis(4-hydroxyphenyl)fluorene (BPF), 9,9-bis[(mono- or di-)C 1-4 Alkyl-hydroxyphenyl]fluorene, 9,9-bis(C 6-10 9,9-bis(hydroxyphenyl)fluorenes such as 9,9-bis(hydroxyphenyl)fluorenes; 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF) and other 9,9-bis(hydroxynaphthyl)fluorenes; 9,9-bis[hydroxy(one to six)C 2-4 Alkoxy C 6-12 9,9-bis[hydroxy(poly)alkoxyaryl]fluorene, more preferably: 9,9-bis[hydroxy(mono- or di-)C 2-4 Alkoxy-C 6-12 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, BOPPEF, BNEF and the like are more preferred.2-3 Alkoxy-C 6-12 [aryl] fluorene, among which BPF, BNF, BPEF, BOPPEF, BNEF are particularly preferred, and BPEF is most preferred.

[0176] (binaphthyl diols) The diol component may include a diol represented by the following formula (5) as a diol having a bis (or binaphthyl) skeleton (binaphthyl-containing diol) in addition to the fluorene-containing diol.

[0177] [Chemistry 11]

[0178] (Where, A 5 represents a direct bond (single bond) or an alkylene group, A 6 and A 7 p1 and p2 independently represent an integer greater than 0, R 11 and R 12 independently represent a substituent, and q1 and q2 independently represent an integer of 0 to 6.)

[0179] In the above formula (5), the substituent R 11 and R 12 The substituent R may be selected from the substituents R exemplified in the above formula (2) 5 and R 6 The same groups (including preferred groups).

[0180] R 11 and R 12 The substitution numbers q1 and q2 can be integers of about 0 to 5, preferably integers of 0 to 4, 0 to 3, and 0 to 2, respectively, more preferably 0 or 1, and particularly preferably 0. q1 and q2 may be different from each other, but are preferably the same. In addition, when q1 is 2 or more, two or more R 11 The types can be the same or different from each other, q1 and R 11 The same relationship applies to q2 and R 12 In addition, R 11 and R 12 The types may be the same or different from each other.

[0181] R 11 and R 12 The substitution position is as long as the A in the two naphthalene ring skeletons 5 and (poly)oxyalkylene [-O-(A 6 O) p1 -] and [-O-(A 7 O) p2-], there is no particular restriction on the position other than the substitution position of A 5 The 1-position of the two naphthalene ring skeletons bonded together, R 11 and R 12 The substitution position of is preferably 3 to 8. For example, in A 5 In the case of a direct bond (single bond), R 11 and R 12 It is preferably bonded to any of the 3-8 position and the 3'-8' position of the 1,1'-binaphthyl skeleton.

[0182] As A 5 The alkylene group represented by the present invention includes C groups such as methylene, ethylene, propylene, trimethylene, 1,2-butanediyl, and tetramethylene. 1-4 From the viewpoint of optical properties such as high refractive index, low Abbe number, and low birefringence, the preferred A 5 Is it a direct bond or a methylene bond? 1-2 The alkylene group is particularly preferably a direct bond (single bond).

[0183] Alkylene A 6 and A 7 It can be selected from the alkylene groups A exemplified in the above formula (2) 3 and A 4 The same groups (including preferred groups) as the repeating numbers p1 and p2 can be selected from the same numbers (including preferred numbers) as the repeating numbers s1 and s2 in the above formula (2).

[0184] In the above formula (5), the (poly)oxyalkylene group [—O—(A 6 O) p1 -] and [-O-(A 7 O) p2 -] is not particularly limited, and may be, for example, 2,2', 4,4', etc., relative to the 1,1'-binaphthyl skeleton, but the bonding position is preferably 2,2' from the viewpoint of easy preparation (synthesis) or supply to improve productivity, and from the viewpoint of easy realization of a high refractive index due to the conformational relationship. Therefore, the binaphthyl-containing diol represented by the above formula (5) preferably includes a binaphthyl-containing diol represented by the following formula (5a).

[0185] [Chemistry 12]

[0186] (In the formula, A 6 , A 7 , p1, p2, R 11 , R 12 , q1 and q2 are respectively the same as those in the above formula (5).

[0187] Representative examples of the binaphthyl-containing diols represented by the formula (5a) include dihydroxy-1,1'-binaphthyl such as 2,2'-dihydroxy-1,1'-binaphthyl and bis[hydroxy(poly)alkoxy]-1,1'-binaphthyl and the like. Examples of bis[hydroxy(poly)alkoxy]-1,1'-binaphthyl include 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxypropoxy)-1,1'-binaphthyl, 2,2'-bis[2-(2-hydroxyethoxy)ethoxy]-1,1'-binaphthyl and the like. 2-4 Alkoxy]-1,1'-binaphthyl, etc.

[0188] These binaphthyl-containing diols may be used alone or in combination of two or more. Among them, the diol represented by the above formula (5a) is preferred, and 2,2'-dihydroxy-1,1'-binaphthyl, 2,2'-bis[hydroxy(mono-tetra)C 2-4 Alkoxy]-1,1'-binaphthyl, most preferably 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl and other 2,2'-bis[hydroxy(mono-tri)C 2-3 [alkoxy]-1,1'-binaphthyl.

[0189] (Other glycol components) The diol component may further contain other diol components. As other diol components, the same as other diol components (except binaphthols) of the fluorene-containing polyester-based resin, including preferred other diol components.

[0190] (Carbonate bond forming component) The fluorene-containing polycarbonate resin disclosed herein contains, in addition to the diol component, a carbonate bond-forming component as a polymerization component for forming carbonate units. Representative carbonate bond-forming components include, for example, phosgenes such as phosgene and triphosgene, and carbonic acid diesters such as diphenyl carbonate. From the viewpoint of safety, carbonic acid diesters such as diphenyl carbonate are preferred.

[0191] (Characteristics of fluorene-containing polycarbonate resin) In the fluorene-containing polycarbonate resin of the present disclosure, the proportion of the fluorene-containing diol in the diol component can be 10 mol% or more, preferably 30 mol% or more, 50 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, and 100 mol% or more. The present disclosure enables the fluorene-containing polycarbonate resin with a large proportion of fluorene skeleton, especially the fluorene-containing polycarbonate resin, to be efficiently depolymerized, and the useful monomer component (monomer) having a fluorene skeleton can be efficiently recovered.

[0192] When the diol component contains a binaphthyl diol in addition to the fluorene-containing diol, the molar ratio of the fluorene-containing diol to the binaphthyl diol can be selected from the range of the former / the latter = about 99 / 1 to 10 / 90, and the preferred ranges are 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, and most preferably 60 / 40 to 40 / 60. The ratio of the two can be the former / the latter = 93 / 7 to 40 / 60, preferably 90 / 10 to 50 / 50, and more preferably 80 / 20 to 60 / 40.

[0193] In the fluorene-containing polycarbonate resin disclosed herein, the total proportion of the olefin-containing diol and the binaphthyl-containing diol in the diol component can be 50 mol% or more, preferably 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, and 100 mol% in that order.

[0194] In the fluorene-containing polycarbonate resin disclosed herein, the total proportion of the diol component and the carbonate bond-forming component in all polymer components can be 50 mol% or more, preferably 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, and 100 mol% in that order.

[0195] The weight average molecular weight of the fluorene-containing polycarbonate-based resin is, for example, 20,000 to 100,000, preferably 25,000 to 80,000, more preferably 30,000 to 70,000, and most preferably 35,000 to 60,000.

[0196] In the specification and claims of the present application, the weight average molecular weight of the fluorene-containing polycarbonate resin can be measured by gel permeation chromatography by converting a standard substance into polystyrene.

[0197] The fluorene-containing polycarbonate-based resin may be amorphous.

[0198] (A) First decomposition step In the depolymerization method of the fluorene-containing polycarbonate resin disclosed herein, in the first decomposition step, the fluorene-containing polycarbonate resin is reacted with a carbonate in the presence of a first hydrolysis catalyst to decompose the fluorene-containing polycarbonate resin to obtain a first decomposition product in the form of a monocarbonate of a diol and / or a dicarbonate of a diol.

[0199] (Carbonate) The carbonate ester functions as a depolymerizing agent for the fluorene-containing polycarbonate-based resin. The carbonate ester is the same as the carbonate ester described for the fluorene-containing polyester-based resin, including preferred carbonate esters.

[0200] The ratio of carbonate to 1 mol (the number of moles corresponding to the number average molecular weight) of the fluorene-containing polycarbonate resin may be 1 mol or more, for example, 0.1 to 50 mol, preferably 0.5 to 30 mol, more preferably 1 to 10 mol, further preferably 1.5 to 5 mol, and most preferably 2 to 3 mol. The ratio of carbonate to 100 parts by mass of the fluorene-containing polycarbonate resin 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, more preferably 20 to 80 parts by mass, further preferably 30 to 70 parts by mass, and most preferably 40 to 60 parts by mass. If the ratio of carbonate is too small, depolymerization may not proceed rapidly.

[0201] (First hydrolysis catalyst) The first hydrolysis catalyst may be selected from the same catalysts as the first hydrolysis catalyst for the fluorene-containing polyester resin, including the preferred catalysts. The first hydrolysis catalysts may be used alone or in combination of two or more.

[0202] The ratio of the first hydrolysis catalyst to 1 mol of the fluorene-containing polycarbonate resin may be, for example, 0.01 mol or more, preferably 0.01 to 0.5 mol, more preferably 0.03 to 0.3 mol, further preferably 0.05 to 0.25 mol, and most preferably 0.1 to 0.2 mol. The ratio of the first hydrolysis catalyst to 100 parts by mass of the fluorene-containing polycarbonate resin may be, for example, 0.1 parts by mass or more, preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, further preferably 0.5 to 4 parts by mass, and most preferably 1 to 3 parts by mass. If the ratio of the hydrolysis catalyst is too small, depolymerization may not proceed rapidly. These ratios of the first hydrolysis catalyst may be the ratios of a base catalyst.

[0203] (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, further preferably 50 to 75°C, and most preferably 60 to 70°C.

[0204] The reaction time may be 10 minutes or longer, for example, 10 minutes to 10 hours, preferably 30 minutes to 8 hours, and more preferably 1 to 5 hours.

[0205] The reaction can be carried out in the presence of an inert or inert gas, but is preferably carried out in the atmosphere from the perspective of convenience. In addition, the reaction can be carried out under reduced pressure, but is preferably carried out under atmospheric pressure from the perspective of convenience.

[0206] (1st decomposition product) The first decomposition product in the first decomposition step includes a monocarbonate form of a diol and / or a dicarbonate form of a diol. Therefore, the present disclosure also includes: similar to the above-mentioned fluorene-containing polyester resin, for the fluorene-containing polycarbonate resin, the monocarbonate form of a diol and / or a dicarbonate form of a diol is also prepared by the above-mentioned first decomposition step.

[0207] The monocarbonate form of the diol and / or the dicarbonate form of the diol can be converted into the diol by performing the second decomposition step as the next step, and the obtained diol can be reused as the raw material of the fluorene-containing polycarbonate resin. The monocarbonate form of the diol and / or the dicarbonate form of the diol can also be utilized as a carbonate compound without performing the second decomposition step.

[0208] The monocarbonate form of the diol and the dicarbonate form of the diol may include the same forms as the monocarbonate form of the diol and the dicarbonate form of the diol of the fluorene-containing polyester-based resin, including preferred forms.

[0209] The ratio of the monocarbonate form to 1 mol of the dicarbonate form is, for example, 0.1 to 30 mol, preferably 0.5 to 10 mol, more preferably 1 to 5 mol, and even more preferably 2 to 4 mol.

[0210] The first decomposition product may further include a diol. The diol may be a diol corresponding to the above-mentioned monocarbonate form and the above-mentioned dicarbonate form.

[0211] In the first decomposition step, the total ratio of the monocarbonate form and the dicarbonate form relative to 1 mol of the diol in the first decomposition product is, for example, 0.1 to 5 mol, preferably 0.5 to 3 mol, more preferably 1 to 2 mol, and further preferably 1.2 to 1.7 mol.

[0212] In the first decomposition step, the total ratio of the monocarbonate form, the dicarbonate form and the diol to 1 mol of the carbonate bond-forming component is, for example, 0.1 to 5 mol, preferably 0.2 to 3 mol, more preferably 0.3 to 2 mol, and further preferably 0.5 to 1.5 mol.

[0213] The first decomposition product can be subjected to conventional purification treatment. Conventional purification treatments include, for example, neutralizing and washing the mixture containing the decomposition product with water as needed, and then removing impurities from the mixture by filtration, etc. In the case where a monomer component is precipitated in the above mixture, a good solvent for the monomer component can be used to completely dissolve it, followed by neutralization and washing with water.

[0214] In the first decomposition step, the monocarbonate form of the diol and / or the dicarbonate form of the diol are mainly obtained. Therefore, when the new carbonate compound is the target compound, the depolymerization method of the present disclosure may be a depolymerization method in which the decomposition step only includes the first decomposition step and does not include the second decomposition step described later.

[0215] (B) Second decomposition step The depolymerization method of the fluorene-containing polycarbonate resin disclosed herein may also have a second decomposition step for obtaining a second decomposition product in addition to the first decomposition step. In the second decomposition step, the first decomposition product is reacted with an alcohol to obtain a diol. Specifically, in the second decomposition step, the monocarbonate form of the above-mentioned diol and / or the dicarbonate form of the diol are reacted with the above-mentioned alcohol to obtain a diol component. In this way, since the second decomposition step can convert the monocarbonate form of the above-mentioned diol and / or the dicarbonate form of the diol into a diol, the second decomposition step is particularly effective when recovering the diol component containing a fluorene skeleton as a monomer component.

[0216] (alcohol) The alcohol may be selected from the same alcohols as those used in the second decomposition step of the fluorene-containing polyester resin, including preferred alcohols. The above alcohols may be used alone or in combination of two or more.

[0217] The proportion of the alcohol may be 50 parts by mass or more, for example, 50 to 1000 parts by mass, preferably 80 to 500 parts by mass, more preferably 100 to 300 parts by mass, and further preferably 120 to 200 parts by mass, relative to 100 parts by mass of the first decomposition product. If the proportion of the alcohol is too small, the yield of the diol component may decrease.

[0218] (Second hydrolysis catalyst) As the second hydrolysis catalyst, there can be mentioned: the hydrolysis catalysts exemplified as the first hydrolysis catalyst for the fluorene-containing polyester resin, etc. The above-mentioned second hydrolysis catalyst can be used alone or in combination of two or more. Among the above-mentioned second hydrolysis catalysts, alkali metal hydroxides and alkaline earth metal hydroxides are preferred, and alkali metal hydroxides such as potassium hydroxide are particularly preferred.

[0219] The ratio of the second hydrolysis catalyst to 100 parts by mass of the first decomposition product may be 1 part by mass or more, for example, 1 to 30 parts by mass, preferably 5 to 20 parts by mass, and more preferably 5 to 10 parts by mass. If the ratio of the base catalyst is too small, the yield of the diol component may be reduced. These ratios of the second hydrolysis catalyst may be the ratios of the base catalyst.

[0220] (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 may be room temperature.

[0221] The reaction time may be 5 minutes or longer, for example, 5 minutes to 5 hours, preferably 10 minutes to 3 hours, more preferably 30 minutes to 2 hours, and further preferably 40 minutes to 1.5 hours. The reaction can be carried out in the presence of an inert or inert gas, but is preferably carried out in the atmosphere from the perspective of convenience. In addition, the reaction can be carried out under reduced pressure, but is preferably carried out under atmospheric pressure from the perspective of convenience.

[0223] (Second decomposition product) The second decomposition product in the second decomposition step contains diols. That is, when the depolymerization method of the present disclosure includes the second decomposition step, the raw material of the fluorene-containing resin can be recovered. Therefore, the obtained monomer component can be used as it is to newly synthesize the fluorene-containing resin, and the recyclability of the fluorene-containing resin can be improved. The fluorene-containing resin can be a fluorene-containing polyester resin or a fluorene-containing polycarbonate resin.

[0224] (C) Purification step The second decomposition product containing diol obtained in the second decomposition step can be subjected to a conventional purification treatment. As a conventional purification treatment, for example, the mixture containing the second decomposition product can be neutralized and washed with water as necessary, and then impurities can be removed from the mixture by filtration or the like, followed by crystallization.

[0225] As a method of crystallization, it is preferred to use a crystallization solvent containing an aromatic hydrocarbon as a crystallization solvent to crystallize the monomer component.

[0226] As the aromatic hydrocarbons, preferably: toluene, xylene, ethylbenzene or the like or di-C 1-2 Alkyl-benzenes, particularly preferably toluene.

[0227] The proportion of the crystallization solvent is, for example, 10 to 3000 parts by mass, preferably 50 to 2000 parts by mass, more preferably 100 to 1000 parts by mass, and most preferably 200 to 500 parts by mass, relative to 100 parts by mass of the diol.

[0228] In the crystallization treatment, by dissolving the diol in the above-mentioned crystallization solvent and cooling, a diol with higher purity can be precipitated (precipitated) or crystallized. The temperature for dissolving the diol in the above-mentioned crystallization solvent is a temperature lower than the boiling point of the solvent, for example, 30 to 200° C., preferably 50 to 150° C., and more preferably 60 to 100° C. The diol after the crystallization treatment can be washed and dried by a conventional method.

[0229] [Recovery method of fluorene-containing resin] The decomposition product obtained by the depolymerization method of the present invention can be used as a monomer raw material for a fluorene-containing resin having a fluorene skeleton and an ester bond and / or a carbonate bond to obtain a newly produced fluorene-containing resin, so the decomposition product can be recycled. That is, the recycling method of the present invention includes: a depolymerization step of reacting the above-mentioned fluorene-containing resin with a carbonate to obtain a decomposition product, and a polymerization step (repolymerization step) of polymerizing the decomposition product obtained in the above-mentioned depolymerization step to obtain a newly produced fluorene-containing resin. The above-mentioned decomposition product can be the first decomposition product or the second decomposition product, preferably the second decomposition product.

[0230] In the recovery method of the present disclosure, the decomposition product obtained in the depolymerization step may be purified and the purified product may be subjected to the polymerization step, or the polymerization step may be subjected to the decomposition product without purification. In addition, in the polymerization step, a new monomer raw material may be added to the monomer raw material as the decomposition product. Depending on the composition of the decomposition product, the newly added monomer raw material may be a insufficient monomer raw material.

[0231] In the polymerization step, as a method for polymerizing the fluorene-containing resin using the decomposition product, a conventional method can be used according to the type of the fluorene-containing resin. As a method for polymerizing a fluorene-containing polyester resin, for example, the method described in Japanese Patent Publication No. 2013-064117, Japanese Patent Publication No. 2013-064118, Japanese Patent Publication No. 2014-218645, Japanese Patent Publication No. 2016-069643, Japanese Patent No. 7016976, etc. can be used. As a method for polymerizing a fluorene-containing polycarbonate resin, for example, the method described in Japanese Patent Publication No. 2018-104691, Japanese Patent Publication No. 2021-134216, etc. can be mentioned. Example

[0232] Hereinafter, the present disclosure will be described in more detail based on examples, but the present disclosure is not limited to these examples. In addition, the details of the materials used in the examples and the evaluation methods in the examples are as follows.

[0233] [Material] FDP-m: 9,9-bis(2-methoxycarbonylethyl)fluorene represented by the following formula (synthesized in the same manner as in Example 1 of JP-A-2005-89422 except that methyl acrylate [37.9 g (0.44 mol)] was used instead of tert-butyl acrylate)

[0234] [Chemistry 13]

[0235] DNFDP-m: 9,9-bis(2-methoxycarbonylethyl)-2,7-di(2-naphthyl)fluorene represented by the following formula (synthesized according to Example 1A of International Publication No. 2020 / 213470)

[0236] [Chemistry 14]

[0237] 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, manufactured by Osaka Gas Chemical Co., Ltd. BOPPEF: 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, manufactured by Osaka Gas 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 Fujifilm Wako Pure Chemical Industries, Ltd.

[0238] [LC-MS generation ratio] Using the HPLC (high performance or high speed liquid chromatography) apparatus "Nexera XR" manufactured by Shimadzu Corporation, the MS unit "LCMS-2020", and the chromatographic column "Kinetex C-18" manufactured by Phenomenex, the sample was dissolved in acetonitrile and measured, and the LC-MS generation ratio was calculated from the area % ratio of HPLC.

[0239] [Yield] The diol component and dicarboxylic acid component of the polyester resin are the former: the latter = 50:50 (molar ratio), which is calculated based on the ratio of each monomer component and the molecular weight of each monomer. In addition, the diol component and carbonate bond forming component of the polycarbonate resin are the former: the latter = 50:50 (molar ratio), which is calculated based on the ratio of each monomer component and the molecular weight of each monomer.

[0240] [LC purity] Using the above-mentioned HPLC apparatus, the purity [area %] was calculated.

[0241] [Glass transition temperature (Tg)] The measurement was performed using a differential scanning calorimeter ("DISCOVERY DSC25" manufactured by TA Instruments) at a temperature increase rate of 10°C / min in a nitrogen atmosphere.

[0242] [Molecular weight distribution] The sample was dissolved in THF for measurement using a GPC (gel permeation chromatography) apparatus "HLC-8320GPC" manufactured by Tosoh Corporation and a column "TSKgel" manufactured by Tosoh Corporation, and the molecular weight was calculated in terms of polystyrene.

[0243] [Refractive index] The sample was hot pressed at 200-240°C to form a film with a thickness of 200-300 μm. The film was cut into strips of 20-30 mm in length and 10 mm in width to obtain test pieces. The obtained test pieces were measured for the refractive index nD at 589 nm (D line) 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.

[0244] [Abbe number] The refractive indexes nF and nC were measured in the same manner as the refractive index nD, except that the measurement wavelengths were changed to 486 nm (F line) and 656 nm (C line) using the test piece for which the refractive index nD at 589 nm (D line) was measured. The Abbe number was calculated by the following formula from the refractive indices nF, nD and nC obtained at each wavelength.

[0245] (Abbe number) = (nD-1) / (nF-nC).

[0246] [Birefringence (3x stretch)] The sample was hot pressed at 200-240°C to form a film with a thickness of 200-600 μm. The film was cut into a strip of 10 mm in length and 50 mm in width, and the strip was uniaxially stretched at a speed of 25 mm / min at a temperature of glass transition temperature Tg+10°C to a stretching ratio of 3 times to obtain a test piece. The obtained test piece was measured for retardation using a parallel Nicol rotation method at a measurement temperature of 20°C and a measurement wavelength of 600 nm using a phase difference film and optical material inspection device ("RETS-100" manufactured by Otsuka Electronics Co., Ltd.), and the obtained value was divided by the thickness of the measurement site to calculate the birefringence (or triple birefringence).

[0247] Example 1 (Preparation of polymer A) According to a conventional method, according to Production Example 2 in the Examples of Japanese Patent No. 7016976, a polymer A was prepared, wherein the structural unit derived from DNFDP-m in the dicarboxylic acid unit was 100 mol%, the structural unit derived from BPEF in the diol unit was 70 mol%, and the structural unit derived from EG in the diol unit was 30 mol%.

[0248] (1st decomposition step) 90.1 g of dimethyl carbonate and 4.58 g of a methanol solution containing LiOMe at a concentration of 10% by mass were added to 45.82 g of the mixed and pulverized polymer A (the total amount of monomers incorporated in the polymer A was equivalent to about 0.1 mol), and the mixture was reacted at 65° C. for 3 hours. 18 g of water and 3.5 g of a 10% by mass HCl aqueous solution were added to the obtained reaction mixture, and the mixture was stirred at 65° C. for 15 minutes, and the organic phase of the separation was recovered and filtered to remove the insoluble components. The obtained organic phase was analyzed by LC-MS, and the results were as follows.

[0249] BPEF: 1.880 area% BPEF monocarbonate represented by the following formula: 11.265 area %

[0250] [Chemistry 15]

[0251] BPEF dicarbonate represented by the following formula: 18.499 area %

[0252] [Chemistry 16]

[0253] DNFDP-m: 51.131 area %.

[0254] (Second decomposition step) The organic phase was concentrated to obtain a crude product, to which 80.1 g of methanol and 7.0 g of potassium hydroxide were added, and the mixture was reacted under reflux conditions at 65° C. for 1 hour. The reaction mixture was filtered at a temperature of 60° C. or higher, and washed with 150 g of methanol at 40° C. to obtain 30.1 g of crude crystals of DNFDP-m as a filtration residue. In addition, the filtrate obtained by this filtration contained BPEF as a main component.

[0255] (Purification of DNFDP-m) 75.1 g of toluene was added to 30.1 g of crude crystals, and after complete dissolution at 80°C, 20 g of water and 5 g of 10% by mass HCl aqueous solution were added, and the resulting mixture was stirred at 80°C for 15 minutes. The mixture was allowed to stand, and after the aqueous phase was removed, 20 g of water was added to the organic phase, and the operation of washing with water was carried out three times. The organic phase at 80°C was cooled to room temperature, stirred at room temperature for 1 hour, and then filtered, and the resulting residue was washed with toluene and methanol in sequence. The filtered residue after washing was dried under reduced pressure at 80°C for 12 hours to obtain 14.7 g of a white solid containing DNFDP-m (yield 50%, LC purity 97.4%).

[0256] (Purification of BPEF) The filtrate containing BPEF as the main component was stirred at 5-10°C for 1 hour, then filtered and washed with methanol at 10°C to obtain 15.1 g of crude crystals. 52.8 g of toluene was added to the obtained crude crystals, and after complete dissolution at 80°C, 20 g of water and 5 g of a 10% by mass HCl aqueous solution were added, and the obtained mixture was stirred at 80°C for 15 minutes. The mixture was allowed to stand, and after the aqueous phase was removed by separation, 20 g of water was added to the organic phase, and washing was performed three times. The organic phase at 80°C was cooled to room temperature, stirred at 5-10°C for 1 hour, and then filtered, and the obtained residue was washed with toluene at 10°C. The filtered residue after washing 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%).

[0257] Example 2 (Preparation of polymer B) According to the conventional method, according to Preparation Example 2 in the Examples of Japanese Patent No. 7016976, a polymer B was prepared, wherein the structural unit derived from DNFDP-m in the dicarboxylic acid unit was 100 mol%, and the structural unit derived from BPEF in the diol unit was 10 mol% and the structural unit derived from EG was 90 mol%.

[0258] (1st decomposition step) To 3.45 g of the mixed and pulverized polymer B (the total amount of monomers incorporated in the polymer B is equivalent to about 0.01 mol), 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, and the mixture was reacted at 65° C. for 3 hours. 10 g of toluene was added to the obtained reaction mixture, and after the mixture was completely dissolved at 65° C., 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. The aqueous phase of the separation was removed, and the organic phase was washed with water three times, and then the washed organic phase was filtered to remove the insoluble components, and concentrated to obtain a crude product.

[0259] (Second decomposition step) To the crude product were added 6.4 g of methanol and 0.56 g of potassium hydroxide, and the mixture was reacted under reflux conditions at 65° C. for 1 hour. The reaction mixture was filtered at 50° C. and washed with 15 g of methanol at 40° C. to obtain 3.35 g of crude crystals of DNFDP-m as a filtration residue. The filtrate obtained by this filtration contained BPEF as a main component.

[0260] (Purification of DNFDP-m) 8.13 g of toluene was added to 3.35 g of crude crystals, and after complete dissolution at 80°C, 3.0 g of water and 0.6 g of 10% by mass HCl aqueous solution were added, and the mixture was stirred at 80°C for 15 minutes. The mixture was allowed to stand, and after the aqueous phase was removed, 3.0 g of water was added to the organic phase, and the water washing operation was repeated 3 times. The organic phase at 80°C was cooled to room temperature and stirred at 5-10°C for 1 hour. After filtering and washing the obtained residue with methanol, the washed filtration residue was dried under reduced pressure at 50°C for 12 hours to obtain 2.48 g of a white solid containing DNFDP-m (yield 84%, LC purity 93.7%).

[0261] (Purification of BPEF) 0.6 g of 10 mass % HCl aqueous solution and 5 g of water were added to the filtrate B, stirred at 5-10°C for 1 hour, and then filtered. The residue was washed with 10°C methanol to obtain 0.09 g of crude crystals. 2.25 g of toluene was added to the obtained crude crystals, and after complete dissolution at 80°C, the mixture was cooled and stirred at 5-10°C for 1 hour. After filtering, the filtered residue was washed with 10°C toluene, and the washed filtered residue was dried under reduced pressure at 50°C for 12 hours to obtain 0.04 g of a white solid containing BPEF (yield 18%, LC purity 94.2%).

[0262] Example 3 (Preparation of Polymer C) According to Example 16 of JP-A-2016-069643, a polymer C was prepared according to a conventional method, wherein the structural unit derived from FDP-m in the dicarboxylic acid unit was 100 mol %, and the structural unit derived from BNEF in the diol unit was 70 mol % and the structural unit derived from EG was 30 mol %.

[0263] (1st decomposition step) 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 to 3.67 g of the mixed and pulverized polymer C (the total amount of monomers incorporated in the polymer C was equivalent to about 0.01 mol), and the mixture was reacted at 65° C. for 2 hours. 0.9 g of water and 0.37 g of a 10% by mass HCl aqueous solution were added to the obtained reaction mixture, and after the mixture was stirred at 65° C. for 15 minutes, the organic phase of the separation was recovered and filtered to remove the insoluble components. The obtained organic phase was analyzed by LC-MS, and the results were as follows.

[0264] BNEF: 4.400 area% BNEF monocarbonate in the form of the following formula: 22.806 area %

[0265] [Chemistry 17]

[0266] BNEF dicarbonate in the form of the following formula: 37.648 area %

[0267] [Chemistry 18]

[0268] FDP-m: 18.616 area %.

[0269] (Second decomposition step) The organic phase was concentrated to obtain a crude product, 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. for 1 hour under reflux conditions. After the reaction was completed, 9.6 g of heptane was added to the reaction mixture, and the resulting mixture was stirred at 65° C. for 10 minutes, and the resulting lower phase (containing methanol and BNEF) and upper phase (containing heptane and FDP-m) were recovered respectively.

[0270] (Purification of FDP-m) The upper phase was concentrated, and the obtained concentrate was dried under reduced pressure at 50°C for 12 hours to obtain 0.13 g of a white solid containing FDP-m (yield 8%, LC purity 92.2%).

[0271] (Purification of BNEF) To the lower phase, 10 g of toluene, 4 g of 10% by mass HCl aqueous solution, and 3 g of water were added, and the mixture was stirred at 80° C., cooled to room temperature, stirred at room temperature for 1 hour, and then filtered, and the resulting 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 a white solid containing BNEF (yield 45%, LC purity 96.0%).

[0272] Example 4 (Preparation of polymer D) According to a conventional method, according to Reference Example 6 of JP-A-2013-064117, a polymer D was prepared in which the structural unit derived from DMT in the dicarboxylic acid unit was 100 mol %, and the structural unit derived from BPEF in the diol unit was 70 mol % and the structural unit derived from EG was 30 mol %.

[0273] (1st decomposition step) 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 to 2.60 g of the mixed and pulverized polymer D (the total amount of monomers incorporated in the polymer D was equivalent to about 0.01 mol), and the mixture was reacted at 65° C. for 3 hours. 0.9 g of water, 0.26 g of a 10% by mass HCl aqueous solution, and 5 g of ethyl acetate were added to the obtained reaction mixture, and the mixture was stirred at 65° C. for 15 minutes, and the separated organic phase was recovered and filtered to remove the insoluble components.

[0274] (Second decomposition step) The organic phase was concentrated to obtain a crude product, 9.6 g of methanol and 0.56 g of potassium hydroxide were added to the crude product, and the mixture was reacted for 1 hour under reflux conditions at 65° C. After the reaction was completed, 3 g of a 10% by mass HCl aqueous solution was added to the reaction mixture, and the resulting mixture was stirred at 5 to 10° C. for 30 minutes.

[0275] (Purification of BPEF) The stirred mixture was filtered, and the obtained 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 a white solid containing BPEF (yield 98%, LC purity 93.6%).

[0276] Example 5 (Preparation of Polymer E) According to Example 3 of JP-A-2014-218645, polymer E was prepared by a conventional method, wherein the structural unit derived from FDP-m in the dicarboxylic acid unit was 100 mol %, and the structural unit derived from BPEF in the diol unit was 80 mol % and the structural unit derived from EG was 20 mol %.

[0277] (1st decomposition step) 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 to 3.50 g of the mixed and pulverized polymer E (the total amount of monomers incorporated in the polymer E was equivalent to about 0.01 mol), and the mixture was reacted at 65° C. for 3 hours. 0.9 g of water and 0.37 g of a 10% by mass HCl aqueous solution were added to the obtained reaction mixture, and the mixture was stirred at 65° C. for 15 minutes, and the separated organic phase was recovered and filtered to remove the insoluble components.

[0278] (Second decomposition step) The organic phase was concentrated to obtain a crude product, 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. for 1 hour under reflux conditions. After the reaction was completed, 9.6 g of heptane was added to the reaction mixture, and the resulting mixture was stirred at 65° C. for 10 minutes, and the resulting lower phase (containing methanol and BPEF) and upper phase (containing heptane and FDP-m) were recovered separately.

[0279] (Purification of FDP-m) The upper phase was concentrated, and the obtained concentrate was dried under reduced pressure at 50°C for 12 hours to obtain 0.10 g of a white solid containing FDP-m (yield 6%, LC purity 94.9%).

[0280] (Purification of BPEF) To the lower phase, 8 g of toluene and 3 g of 10% by mass HCl aqueous solution were added, the mixture was stirred at 60°C, slowly cooled to room temperature, and stirred at room temperature for 1 hour, the mixture was filtered, and the residue was washed with methanol to obtain 1.63 g of crude crystals. 6.52 g of toluene was added to the crude crystals, dissolved at 85°C, and then cooled to room temperature to crystallize. Filtering was performed, and the residue was washed with methanol. The washed residue was dried under reduced pressure at 50°C for 12 hours to obtain 0.31 g of a white solid containing BPEF (yield 18%, LC purity 94.4%).

[0281] Example 6 (1st decomposition step) 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 to 4.582 g of the mixed and pulverized polymer A (the total amount of monomers incorporated in the polymer A was equivalent to about 0.01 mol), and the mixture was reacted at 65° C. for 2 hours. 1.5 g of water and 0.55 g of a 10% by mass HCl aqueous solution were added to the obtained reaction mixture, and after the mixture was stirred at 65° C. for 15 minutes, the organic phase of the separation was recovered and filtered to remove the insoluble components.

[0282] (Second decomposition step) The organic phase was concentrated to obtain a crude product, 8.01 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. The reaction mixture was filtered while being maintained at 60° C. or higher, and the resulting residue was washed with 15.0 g of methanol at 40° C. to obtain 4.4 g of crude crystals of DNFDP-m. The filtrate obtained by this filtration contained BPEF as a main component.

[0283] (Purification of DNFDP-m) 10.9 g of toluene was added to 4.4 g of crude crystals. After the mixture was completely dissolved at 80°C, 5 g of water and 0.5 g of 10% by mass HCl aqueous solution were added to the solution, and the resulting mixture was stirred at 80°C for 15 minutes. The mixture was allowed to stand, and after the aqueous phase was removed, 5 g of water was added to the organic phase, and the operation of washing with water was carried out three times. The organic phase at 80°C was cooled to room temperature, stirred at 5-10°C for 1 hour, and then filtered. The resulting residue was washed with toluene and methanol in sequence. The washed residue was dried under reduced pressure at 50°C for 12 hours to obtain 1.56 g of a white solid containing DNFDP-m (yield 53%, LC purity 96.4%).

[0284] (Purification of BPEF) The filtrate F was stirred at 5-10°C for 1 hour, then filtered, and the residue was washed with methanol at 10°C to obtain 1.03 g of crude crystals. 3.08 g of toluene was added to the crude crystals, and after the mixture was completely dissolved 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 at 80°C for 15 minutes. The mixture was allowed to stand, and after the aqueous phase was removed, 1 g of water was added to the organic phase, and the washing operation was performed three times. The organic phase at 80°C was cooled to room temperature, stirred at 5-10°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 a white solid containing BPEF (yield 29%, LC purity 98.1%).

[0285] Example 7 (Preparation of Polymer F) According to Example 7 of JP-A-2013-064118, polymer F was prepared by a conventional method, wherein the structural unit derived from FDP-m in the dicarboxylic acid unit was 100 mol %, and the structural unit derived from BOPPEF in the diol unit was 70 mol % and the structural unit derived from EG was 30 mol %.

[0286] (1st decomposition step) To 4.12 g of the mixed and pulverized polymer F (the total amount of monomers incorporated in the polymer F was equivalent to about 0.01 mol) were added 9.01 g of dimethyl carbonate and 0.41 g of a methanol solution containing LiOMe at a concentration of 10% by mass, and the mixture was reacted at 65° C. for 4 hours. To the obtained reaction mixture were added 0.9 g of water and 0.41 g of a 10% by mass HCl aqueous solution, and the mixture was stirred at 65° C. for 15 minutes, and then the separated organic phase was recovered and filtered to remove the insoluble components.

[0287] (Second decomposition step) The organic phase was concentrated to obtain a crude product, 11.2 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. After the reaction was completed, the reaction 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. In addition, the filtrate obtained by this filtration contained FDP-m as the main component.

[0288] (Purification of FDP-m) To the filtrate containing the above-mentioned FDP-m as the main component was added 25 g of heptane, and the mixture was stirred at 40°C for 1 hour. The upper phase was concentrated and dried under reduced pressure at 50°C for 12 hours to obtain 0.21 g of a white solid containing FDP-m (yield 12%, LC purity 96.3%).

[0289] (Purification of BOPPEF) To the crude crystals were added 11.4 g of toluene, 5 g of water, and 0.2 g of a 10% by mass HCl aqueous solution, and the mixture was stirred at 60°C, and then washed with 5 g of water. The washed mixture was slowly cooled to room temperature to crystallize. The residue was filtered and washed with methanol, and then dried under reduced pressure at 80°C for 12 hours to obtain 1.99 g of a white solid containing BOPPEF (yield 84%, LC purity 97.2%).

[0290] Table 1 shows the composition of the base polymer, 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 for Examples 1 to 7.

[0291] From the results in Table 1, it is understood that in any of Examples 1 to 7, a new monocarbonate form and a dicarbonate are generated in the first decomposition step, and further, the dicarboxylic acid ester and the diol can be recovered through the second decomposition step and the purification step.

[0292] Example 8 (Preparation of polymer G) According to the conventional method, according to Example 6 of Japanese Patent Gazette No. 2013-064118, a polymer G was prepared, wherein the structural unit derived from DMN in the dicarboxylic acid unit was 30 mol%, the structural unit derived from FDP-m was 70 mol%, and the structural unit derived from BPEF in the diol unit was 85 mol%, and the structural unit derived from EG was 15 mol% (the composition ratio of polymer G is shown in Table 2).

[0293] (Depolymerization of Polyester G) To 346.10 g of the granular polymer G (the total amount of monomers incorporated in the polymer G is equivalent to about 1.0 mol), 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, and the mixture was reacted 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 to the obtained reaction mixture, and after the mixture was stirred at 65° C., the obtained aqueous phase was removed. The remaining organic phase was washed with water until the conductivity of the obtained aqueous phase was 10 μS / cm or less, and then the obtained organic phase was filtered to remove the insoluble components. The organic phase was concentrated to obtain a crude product, 480 g of methanol and 50.5 g of potassium hydroxide were added to the crude product, and the mixture was reacted at room temperature for 2 hours. 100 g of a 10% by mass HCl aqueous solution and 300 g of water were added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The stirred mixture was filtered and the residue was washed with warm water at 60°C until the conductivity of the filtrate was below 10 μS / cm. The washed residue was then dried under reduced pressure at 50°C to obtain 291 g of a white solid (molar ratio calculated based on HPLC measurement: BPEF / DMN / FDP-m=0.850 / 0.280 / 0.316).

[0294] (Repolymerization) To achieve the composition ratio of polymer G as shown in Table 2, insufficient monomer components (supplementary components in Table 2) were newly added to 68.70 g of the obtained depolymerized sample, and a polymer repolymerization product was prepared according to Example 6 of JP-A-2013-064118.

[0295] Example 9 In order to achieve the composition ratio of polymer G, as shown in Table 2, insufficient monomer components (supplementary components in Table 2) were newly added to 20.00 g of the depolymerized sample obtained in Example 8, and a repolymerized product of the polymer was prepared according to Example 6 of JP-A-2013-064118.

[0296] Example 10 In order to achieve the composition ratio of polymer G, as shown in Table 2, insufficient monomer components (supplementary components in Table 2) were newly added to 10.00 g of the depolymerized sample obtained in Example 8, and a repolymerized product of the polymer was prepared according to Example 6 of Japanese Patent Application Publication No. 2013-064118.

[0297] Embodiment 11 In order to achieve the composition ratio of polymer G, as shown in Table 2, insufficient monomer components (supplementary components in Table 2) were newly added to 5.00 g of the depolymerized sample obtained in Example 8, and a repolymerized product of the polymer was prepared according to Example 6 of JP-A-2013-064118.

[0298] Example 12 (Depolymerization of polymer G) To 173.05 g of the particulate polymer G obtained in Example 8 (the total amount of monomers incorporated in the polymer G is equivalent to about 0.5 mol) were added 315.28 g of dimethyl carbonate, 3.461 g of NaOMe, and 31.149 g of methanol, and the mixture was 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 to the obtained reaction mixture, and after the mixture was stirred at 60°C, the obtained aqueous phase was removed. The remaining organic phase was washed with water until the conductivity of the obtained aqueous phase was 10 μS / cm or less, and then the obtained organic phase was filtered to remove the insoluble components. The organic phase was concentrated to obtain a crude product, and 288 g of methanol and 25.2 g of potassium hydroxide were added to the crude product, and the mixture was reacted at room temperature for 2 hours. 50 g of a 10% by mass HCl aqueous solution and 150 g of water were added to the obtained reaction mixture, and the mixture was stirred at room temperature for 1 hour. The stirred mixture was filtered and the residue was washed with warm water until the conductivity of the filtrate was below 10 μS / cm. The washed residue was then dried under reduced pressure at 50°C to obtain 140 g of a white solid (molar ratio calculated based on HPLC measurement: BPEF / DMN / FDP-m=0.850 / 0.248 / 0.306).

[0299] (Repolymerization) To achieve the composition ratio of polymer G as shown in Table 3, insufficient monomer components (supplemental components in Table 3) were newly added to 69.81 g of the obtained depolymerized sample, and a repolymerized polymer product was prepared according to Example 6 of JP-A-2013-064118.

[0300] Example 13 In order to achieve the composition ratio of polymer G, as shown in Table 3, insufficient monomer components (supplementary components in Table 3) were newly added to 20.00 g of the depolymerized sample obtained in Example 12, and a repolymerized product of the polymer was prepared according to Example 6 of JP-A-2013-064118.

[0301] Embodiment 14 In order to achieve the composition ratio of polymer G, as shown in Table 3, insufficient monomer components (supplementary components in Table 3) were newly added to 10.00 g of the depolymerized sample obtained in Example 12, and a repolymerized product of the polymer was prepared according to Example 6 of JP-A-2013-064118.

[0302] Embodiment 15 In order to achieve the composition ratio of polymer G, as shown in Table 3, insufficient monomer components (supplementary components in Table 3) were newly added to 5.00 g of the depolymerized sample obtained in Example 12, and a repolymerized product of the polymer was prepared according to Example 6 of JP-A-2013-064118.

[0303] Example 16 (Depolymerization of polymer G) To 242.27 g of the particulate polymer G obtained in Example 8 (the total amount of monomers incorporated in the polymer G is equivalent to about 0.7 mol) were added 441.39 g of dimethyl carbonate and 24.227 g of a methanol solution containing LiOMe at a concentration of 10% by mass, and the mixture was reacted at 60° C. for 2 hours. To the obtained reaction mixture were added 63 g of water and 24 g of a 10% by mass HCl aqueous solution, and after the mixture was stirred at 65° C., the obtained organic phase was filtered to remove insoluble components. The organic phase was concentrated to obtain a crude product, and 359 g of methanol and 39.3 g of potassium hydroxide were added to the crude product, and the mixture was reacted at room temperature for 2 hours. To the reaction mixture were added 105 g of a 10% by mass HCl aqueous solution and 280 g of water, and the mixture was stirred at room temperature for 1 hour. The stirred mixture was suction filtered, the residue was washed with water and then dried under reduced pressure at 50°C to obtain 238 g of a white solid (molar ratio calculated from HPLC measurement: BPEF / DMN / FDP-m=0.850 / 0.382 / 0.486).

[0304] (Repolymerization) To achieve the composition ratio of polymer G as shown in Table 4, insufficient monomer components (supplementary components in Table 4) were newly added to 20.00 g of the obtained depolymerized sample, and a repolymerized polymer was prepared according to Example 6 of JP-A-2013-064118.

[0305] Embodiment 17 In order to achieve the composition ratio of polymer G, as shown in Table 4, insufficient monomer components (supplementary components in Table 4) were newly added to 10.00 g of the depolymerized sample obtained in Example 16, and a repolymerized product of the polymer was prepared according to Example 6 of JP-A-2013-064118.

[0306] Embodiment 18 In order to achieve the composition ratio of polymer G, as shown in Table 4, insufficient monomer components (supplementary components in Table 4) were newly added to 5.00 g of the depolymerized sample obtained in Example 16, and a repolymerized product of the polymer was prepared according to Example 6 of JP-A-2013-064118.

[0307] The evaluation results of Examples 8 to 18 are shown in Tables 2 to 4. In addition, Table 5 shows the evaluation results of polymer G as a blank.

[0308]

[0309]

[0310]

[0312] Table 5

[0312] From the results in Tables 2 to 5, it is understood that by appropriately supplementing the insufficient monomer raw material to the decomposition product obtained in the depolymerization step, the molecular weight of the polymer in the repolymerization can be increased, and a polymer with excellent optical properties can be obtained.

[0313] Comparative Example 1 (Depolymerization of polymer G) According to the methods described in Patent Documents 1 and 2, EG was added to the particulate polymer G obtained in Example 8, and the mixture was heated at 200 to 250° C. for about 3 hours to depolymerize the polyester F. The molecular weight distribution of the polymer G before depolymerization is as follows: Figure 1 As shown, the molecular weight distribution of the decomposition products after depolymerization is as follows Figure 2 As shown. Figure 1 and Figure 2 The comparison of the above data shows that a certain decomposition product obtained after depolymerization has a broader molecular weight distribution, which indicates that polymer G is not decomposed into monomer units.

[0314] That is, it was demonstrated that the conventional method involving the excessive addition of a solvent (ethylene glycol) and heating at a high temperature allows the depolymerization of widely used polyesters such as PET, but the conventional method does not allow the depolymerization of a fluorene skeleton-containing polymer.

[0315] 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 particulate 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 depolymerize the polyester G. The molecular weight distribution of the polymer G before depolymerization is as follows: Figure 3 The molecular weight distribution of the decomposition products obtained after depolymerization is shown in Figure 4 As shown. Figure 3 and Figure 4 It can be seen from the comparison that a certain decomposition product obtained after depolymerization has a wider molecular weight distribution, which indicates that polymer G is not decomposed into monomer units.

[0316] That is, it was demonstrated that the conventional method (hydrolysis method) involving hydrolysis with subcritical water allows depolymerization of widely used polyesters such as PET, but the conventional method does not allow depolymerization of polymers containing a fluorene skeleton.

[0317] From the results of Comparative Examples 1 and 2, it can be understood that, unlike widely used polyesters such as PET, polyester resins containing a fluorene skeleton are difficult to depolymerize by conventional methods.

[0318] Embodiment 19 (Preparation of Polymer H) According to a conventional method, a polymer H having a carbonate bond was prepared, wherein the structural unit derived from BPEF in the diol unit accounted for 100 mol %.

[0319] (1st decomposition step) To 46.618 g of polymer H (the total amount of monomers incorporated in the polymer was equivalent to about 0.1 mol) were added 22.52 g of dimethyl carbonate, 0.9324 g of NaOMe, and 8.3912 g of methanol, and the mixture was reacted at 65° C. for 1 hour. To the obtained reaction mixture were added 60 g of toluene, 40 g of water, and 4.6 g of a 10% by mass HCl aqueous solution, and the mixture was stirred at 75° C. for 15 minutes, and then liquid-liquid separation was performed, and the separated (separated) organic phase was washed with 40 g of water, and the water washing step was repeated 3 times, and then the washed product was filtered to remove insoluble components.

[0320] (Second decomposition step) The organic phase was concentrated to obtain a crude product (first decomposition product), to which 96 g of methanol and 4.49 g of potassium hydroxide were added, and the mixture was reacted at room temperature for 1 hour. 8 g of a 10% by mass HCl aqueous solution and 30 g of water were added to the reaction mixture, and the resulting mixture was stirred at 5 to 10° C. for 1 hour, and then filtered to obtain 55 g of crude crystals of BPEF.

[0321] (Purification steps of BPEF) 165 g of toluene was added to the crude crystals, and the mixture was completely dissolved at 75°C, then the mixture was slowly cooled to room temperature and stirred at 5-10°C for 1 hour. The mixture was filtered and the residue was dried under reduced pressure at 80°C for 12 hours to obtain 22.9 g of white solid BPEF (yield 52%, LC purity 98.3%).

[0322] Table 6 shows the composition of the first decomposition product, and the yield and purity of the diol (BPEF) after the BPEF purification step for Example 19.

[0323] [Table 6]

[0324] From the results in Table 6, it is understood that in Example 19, new monocarbonate forms and dicarbonate were generated in the first decomposition step, and diols could be recovered by further undergoing the second decomposition step and the purification step.

[0325] Embodiment 20 (Preparation of Polymer I) According to a conventional method, a polymer I having a carbonate bond was prepared, wherein the structural unit derived from BPEF in the diol unit accounted for 50 mol % and the structural unit derived from BINOL-2EO accounted for 50 mol %.

[0326] (1st decomposition step) To 20.324 g of polymer I (the total amount of monomers incorporated in the polymer was equivalent to about 0.05 mol) were added 11.26 g of dimethyl carbonate, 0.4065 g of NaOMe, and 3.6583 g of methanol, and the mixture was reacted at 65° C. for 2 hours. To the obtained reaction mixture were added 35 g of toluene, 20 g of water, and 2.3 g of a 10% by mass HCl aqueous solution, and the mixture was stirred at 75° C. for 15 minutes, and then liquid-liquid separation was performed, and the separated (separated) organic phase was washed with 20 g of water, and the water washing step was repeated 3 times, and then the washed product was filtered to remove insoluble components.

[0327] (Second decomposition step) The organic phase was concentrated to obtain a crude product (the first decomposition product), 48 g of methanol and 2.24 g of potassium hydroxide were added to the crude product, and the mixture was reacted at room temperature for 1 hour. 4 g of a 10% by mass HCl aqueous solution and 15 g of water were added to the obtained reaction mixture, and the obtained mixture was stirred at 5 to 10° C. for 1 hour, and then the mixture was filtered, and the filtration residue was dried under reduced pressure at 50° C. to obtain 17.4 g of a white solid (a mixture of BPEF and BINOL-2EO) (LC purity 94.7%, yield 85% (as the purity and yield of the above mixture).

[0328] Embodiment 21 (Preparation of Polymer J) According to a conventional method, a polymer J having a carbonate bond was prepared, wherein the structural unit derived from BOPPEF in the diol unit accounted for 50 mol % and the structural unit derived from BINOL-2EO accounted for 50 mol %.

[0329] (1st decomposition step) To 24.129 g of polymer J (the total amount of monomers incorporated in the polymer was equivalent to about 0.05 mol) were added 11.26 g of dimethyl carbonate, 0.4826 g of NaOMe, and 4.324 g of methanol, and the mixture was reacted at 65° C. for 2 hours. To the resulting reaction mixture were added 35 g of toluene, 20 g of water, and 2.3 g of a 10% by mass HCl aqueous solution, and the mixture was stirred at 75° C. for 15 minutes, then liquid-liquid separation was performed, and the separated (separated) organic phase was washed with 20 g of water, and the water washing step was repeated 3 times, and then the washed product was filtered to remove insoluble components.

[0330] (Second decomposition step) The organic phase was concentrated to obtain a crude product, 48 g of methanol and 2.24 g of potassium hydroxide were added to the crude product, and the mixture was reacted at room temperature for 1 hour. 4 g of a 10% by mass HCl aqueous solution and 15 g of water were added to the obtained reaction mixture, and the obtained mixture was stirred at 5 to 10° C. for 1 hour, and then the mixture was filtered, and the filtration residue was dried under reduced pressure at 50° C. to obtain 21.7 g of a white solid (a mixture of BOPPEF and BINOL-2EO) (LC purity 98.2%, yield 90% (as the purity of the above mixture). Industrial Applicability

[0331] 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, and can be used as a raw material or additive for polyester resins or polycarbonate resins in various fields such as the optical field. Furthermore, the new carbonate form of the diol obtained in the process of the depolymerization method of the present disclosure can be used as a raw material for polycarbonate resins, a reaction regulator, a resin additive, and other additives.

Claims

1. A method for depolymerizing a fluorene-containing resin, wherein: The fluorene-containing resin has a fluorene skeleton and an ester bond and / or a carbonate bond. The method includes reacting the fluorene-containing resin with a carbonate in the presence of a hydrolysis catalyst to obtain a decomposition product.

2. The depolymerization method according to claim 1, wherein: The decomposition products include monocarbonate forms of diols and / or dicarbonate forms of diols.

3. The depolymerization method according to claim 2, wherein: The decomposition products also contain dicarboxylic acids and / or esters thereof.

4. The depolymerization method according to claim 1 or 2, further comprising reacting the decomposition product with an alcohol to obtain a diol.

5. The depolymerization method according to claim 1 or 2, wherein: The fluorene-containing resin is a polyester resin containing a dicarboxylic acid component represented by the following formula (1) and / or a diol represented by the following formula (2) as a polymerization component. In the formula, Ring Z 1 and Ring Z 2 independently represent an aromatic hydrocarbon ring, R 1 and R 2 independently represent a substituent, m1 and m2 independently represent an integer greater than 0, n1 and n2 independently represent an integer from 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, and k1 and k2 independently represent an integer of 0 to 4, In the formula, Ring Z 3 and Ring Z 4 independently represent an aromatic hydrocarbon ring, A 3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer of 0 to 8.

6. The depolymerization method according to claim 5, wherein: 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 each 0, or n1 and n2 are each 1, and ring Z 1 and Ring Z 2 independently represent a fused polycyclic aromatic hydrocarbon ring.

7. The depolymerization method according to claim 5, wherein: The fluorene-containing resin is a polyester-based resin containing the diol represented by the formula (2) as a polymerization component.

8. The depolymerization method according to claim 1 or 2, wherein: The fluorene-containing resin is a polycarbonate-based resin containing a diol represented by the following formula (2) as a polymerization component. In the formula, Ring Z 3 and Ring Z 4 independently represent an aromatic hydrocarbon ring, A 3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer of 0-8.

9. The depolymerization method according to claim 1 or 2, wherein: The fluorene-containing resin contains a diol represented by the following formula (5) as a polymerization component, In the formula, A 5 represents a direct bond (single bond) or an alkylene group, A 6 and A 7 p1 and p2 independently represent an integer greater than 0, R 11 and R 12 independently represent a substituent, and q1 and q2 independently represent an integer of 0-6.

10. A method for producing a fluorene skeleton-containing dicarboxylic acid and / or an ester thereof, the method comprising reacting a polyester resin containing a fluorene skeleton-containing dicarboxylic acid component as a polymerization component with a carbonate in the presence of a hydrolysis catalyst to decompose the polyester resin.

11. A method for preparing a diol containing a fluorene skeleton, the method comprising: a first decomposition step of reacting a polyester resin containing a fluorene skeleton-containing diol as a polymerization component with a carbonate in the presence of a hydrolysis catalyst to decompose the polyester resin to obtain a first decomposition product containing a dicarboxylic acid and / or an ester thereof, a monocarbonate form of a diol, and / or a dicarbonate form of a diol; and In the second decomposition step, the first decomposition product is reacted with an alcohol to obtain a diol.

12. A method for recovering a monomer component containing a fluorene skeleton, the method comprising: a first decomposition step of reacting a polyester resin having a fluorene skeleton and an ester bond with a carbonate in the presence of a hydrolysis catalyst to decompose the polyester resin to obtain a decomposition product containing a dicarboxylic acid and / or an ester thereof, a monocarbonate form of a diol, and / or a dicarbonate form of a diol; and In the second decomposition step, the decomposition product is reacted with an alcohol to obtain a diol.

13. A method for recovering a monomer component containing a fluorene skeleton, the method comprising: a first decomposition step of reacting a polycarbonate resin having a fluorene skeleton and a carbonate bond with a carbonate in the presence of a hydrolysis catalyst to decompose the polycarbonate resin to obtain a first decomposition product containing a monocarbonate form of a diol and / or a dicarbonate form of a diol, and In the second decomposition step, the first decomposition product is reacted with an alcohol to obtain a diol.

14. A monocarbonate form of a diol represented by the following formula (3), In the formula, Ring Z 3 and Ring Z 4 independently represent an aromatic hydrocarbon ring, A 3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 8 represents a hydrocarbon group, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer of 0-8.

15. A dicarbonate ester of a diol represented by the following formula (4), In the formula, Ring Z 3 and Ring Z 4 independently represent an aromatic hydrocarbon ring, A 3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 9 and R 10 independently represent a hydrocarbon group, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer of 0-8.

16. A method for preparing the monocarbonate form of the diol according to claim 14, comprising reacting a fluorene-containing resin having a fluorene skeleton and ester bonds and / or carbonate bonds with a carbonate in the presence of a hydrolysis catalyst to decompose the fluorene-containing resin, in, The fluorene-containing resin is a fluorene-containing resin containing a diol represented by the following formula (2) as a polymerization component, In the formula, Ring Z 3 and Ring Z 4 independently represent an aromatic hydrocarbon ring, A 3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer of 0-8.

17. A method for preparing the dicarbonate form of the diol according to claim 15, comprising reacting a fluorene-containing resin having a fluorene skeleton and ester bonds and / or carbonate bonds with a carbonate in the presence of a hydrolysis catalyst to decompose the fluorene-containing resin, in, The fluorene-containing resin is a fluorene-containing resin containing a diol represented by the following formula (2) as a polymerization component, In the formula, Ring Z 3 and Ring Z 4 independently represent an aromatic hydrocarbon ring, A 3 and A 4 independently represent an alkylene group, s1 and s2 independently represent an integer greater than 0, R 5 and R 6 independently represent a substituent, t1 and t2 independently represent an integer greater than 0, R 7 represents a substituent, and u represents an integer of 0-8.

18. A method for recovering a fluorene-containing resin having a fluorene skeleton and an ester bond and / or a carbonate bond, the method comprising: a depolymerization step of reacting the fluorene-containing resin with a carbonate in the presence of a hydrolysis catalyst to obtain a decomposition product, and A polymerization step of polymerizing the decomposition product obtained in the depolymerization step to obtain a newly generated fluorene-containing resin.

19. The recycling method according to claim 18, wherein: The monomer feed for the newly produced fluorene-containing resin is replenished in the polymerization step.

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