Diol compound, production method thereof, and polymer thereof

Abstract

To provide: a novel diol compound that can form a resin comprising a fluorene skeleton and an acryloyl skeleton in the main chain; a resin containing the compound as a polymerization component; and a precursor of the compound; and a method for producing these.SOLUTION: A diol compound represented by formula (1) is prepared (where R1 represents a substituent, k represents an integer of 0-2, a doublet of a solid line and a dashed line represents a single bond or a double bond, each of R2a and R2b independently represents a substituent, each of m1 and m2 independently represents an integer of 0-3, each of R3a and R3b independently represents a hydrogen atom or a substituent, and each of R4a and R4b independently represents a hydrogen atom or a substituent). In formula (1), each of R3a and R3b may be a hydrogen atom, and each of R4a and R4b may be a hydrogen atom or a hydrocarbon group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a novel diol compound (fluorene compound), a method for producing the same, and a polymer (or resin) containing the diol compound as a polymerization component.

Background Art

[0002] Fluorene produced from coal tar is an aromatic compound having a π-conjugated system, and is a unique hydrocarbon having a rigid and highly symmetric chemical structure and being rich in reactivity. Due to such structural or chemical characteristics, fluorene is used as a starting material for various fine chemical materials. For example, derivatives obtained by chemically modifying the benzene ring forming the fluorene skeleton are used as liquid crystal materials, optical functional materials, organic EL dyes, and the like. Further, a fluorene compound having two aromatic rings substituted at the 9-position can be effectively used as a functional monomer capable of preparing a polymer exhibiting excellent properties such as high heat resistance, high refractive index, and high transparency, and is industrially produced.

[0003] On the other hand, attention has been focused on the development of new fine chemical materials using the fluorene skeleton. For example, Japanese Patent Application Laid-Open No. 2011-236415 (Patent Document 1) discloses a thermoplastic resin obtained by an enethiol reaction (thiol-ene reaction) between an unsaturated compound having an aromatic skeleton and two ethylenically unsaturated bonds and a dithiol compound.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In the example of Patent Document 1, a thermoplastic resin was prepared using an unsaturated compound having a 9,9-bisphenylfluorene skeleton, and there is no description of a compound having an acryloyl skeleton (or an acryloyl skeleton which may be substituted, such as a (meth)acryloyl group) at the 1-8 positions of the fluorene skeleton, nor is there any description of a resin containing an acryloyl skeleton in the main chain.

[0006] Therefore, an object of the present invention is to provide a novel diol compound capable of forming a resin containing a fluorene skeleton and an acryloyl-based skeleton (or a vinyl ketone-based skeleton, that is, [-C(=O)-C(=CHR 3a )-] and [-C(=O)-C(=CHR 3b )-]), a resin containing the compound as a polymerization component, a precursor of the compound, and a method for producing these.

Means for Solving the Problems

[0007] As a result of intensive studies to achieve the above object, the present inventors have found that a resin containing a fluorene skeleton and an acryloyl-based skeleton in the main chain can be formed by using a diol compound (fluorene compound) having a specific chemical structure as a polymerization component, and have completed the present invention.

[0008] That is, the diol compound (fluorene compound) of the present invention is represented by the following formula (1).

[0009]

Chemical formula

[0010] (In the formula, R 1 represents a substituent, k represents an integer of 0 to 2, the double line of the solid line and the broken line represents a single bond or a double bond, R 2a and R 2b independently represent a substituent, m1 and m2 independently represent an integer of 0 to 3, R 3a and R3b each independently represents a hydrogen atom or a hydrocarbon group, R 4a and R 4b each independently represents a hydrogen atom or a substituent).

[0011] In the formula (1), R 3a and R 3b may be a hydrogen atom, and R 4a and R 4b may be a hydrogen atom or a hydrocarbon group.

[0012] The present invention includes a method for producing the diol compound by reacting a compound represented by the following formula (2) with compounds represented by the following formulas (3a) and (3b).

[0013]

Chemical formula

[0014] (In the formula, R 1 , k, R 2a and R 2b , m1 and m2, R 3a and R 3b , R 4a and R 4b and the double line of the solid line and the broken line are the same as those in the formula (1) respectively).

[0015] The present invention also includes a resin containing the diol compound as a polymerization component (a resin having the diol compound as a polymerization component). The resin may be a polyester resin containing a diol unit and a dicarboxylic acid unit, and the diol unit may contain a diol unit represented by the following formula (1P).

[0016]

Chemical formula

[0017] (In the formula, R 1 , k, R 2a and R 2b, m1 and m2, R 3a and R 3b , R 4a and R 4b and the double lines of the solid line and the broken line are the same as those in the formula (1) above, respectively.

[0018] The dicarboxylic acid unit may contain a dicarboxylic acid unit derived from an aromatic dicarboxylic acid component.

[0019] The present invention also includes a method for decomposing the resin in the presence of a base. The base may be a weak base or a nucleophile.

[0020] Furthermore, the present invention also includes a curable composition containing the resin and a cured product obtained by curing this curable composition.

[0021] In the present specification and claims, the number of carbon atoms of a substituent may be indicated by C 1 , C 6 , C 10 etc. For example, "C 1 alkyl group" means an alkyl group having 1 carbon atom, and "C 6-10 aryl group" means an aryl group having 6 to 10 carbon atoms.

[0022] Also, "diol unit" and "structural unit derived from a diol component" mean a unit (or divalent group) obtained by removing a hydrogen atom from each of the two hydroxyl groups of the corresponding diol component, and "diol component" (including the compounds exemplified as the diol component) may be used synonymously with the corresponding "diol unit" in some cases. Similarly, "dicarboxylic acid unit" and "structural unit derived from a dicarboxylic acid component" mean a unit (or divalent group) obtained by removing OH (hydroxyl group) from each of the two carboxyl groups of the corresponding dicarboxylic acid, and "dicarboxylic acid component" (including the compounds exemplified as the dicarboxylic acid component) may be used synonymously with the corresponding "dicarboxylic acid unit" in some cases.

[0023] Furthermore, the "dicarboxylic acid component" is used to mean including its ester-forming derivatives in addition to the dicarboxylic acid. Examples of the ester-forming derivatives include alkyl esters, acid halides such as acid chlorides, and acid anhydrides. Examples of the alkyl esters include lower alkyl esters, such as methyl esters, ethyl esters, and t-butyl esters, etc. C 1-4 Examples include alkyl esters. The ester-forming derivative may be a monoester (half ester) or a diester.

Advantages of the Invention

[0024] Since the novel diol compound of the present invention has a specific chemical structure, a resin containing a fluorene skeleton and an acryloyl skeleton in the main chain can be easily or efficiently formed. Further, since the resin has a specific chemical structure, it is excellent in optical properties such as high heat resistance and high refractive index.

Brief Description of the Drawings

[0025]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0026] The novel diol compound (fluorene compound) having a fluorene skeleton and an acryloyl skeleton (vinyl ketone skeleton) of the present invention is represented by the following formula (1).

[0027] [Fluorene compound represented by formula (1)]

[0028]

Chem.

[0029] (In the formula, R 1 represents a substituent, k represents an integer of 0 to 2,

[0030]

Chem.

[0031] The bond represented by (that is, the bond represented by the double line of the solid line and the broken line) represents a single bond or a double bond, R 2a and R 2b each independently represent a substituent, m1 and m2 each independently represent an integer of 0 to 3, R 3a and R 3b each independently represent a hydrogen atom or a substituent, R 4a and R 4b each independently represent a hydrogen atom or a substituent).

[0032] In the above formula (1), examples of the substituent represented by R 1 include monovalent groups such as hydrocarbon groups, substituted amino groups, halogen atoms, and divalent groups such as an oxygen atom (or oxo group [=O]).

[0033] Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, aryl groups, and groups (bonded groups) formed by combining two or more of these hydrocarbon groups.

[0034] Examples of alkyl groups include linear or branched C alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, etc. 1-20 Examples include alkyl groups, etc., preferably linear or branched C alkyl groups. 1-12 More preferably linear or branched C alkyl groups. 1-6 Examples include alkyl groups.

[0035] Examples of cycloalkyl groups include C cycloalkyl groups such as cyclopentyl group, cyclohexyl group, etc. 5-10 Examples include cycloalkyl groups, etc., preferably C cycloalkyl groups. 5-8 Examples include cycloalkyl groups.

[0036] Examples of aryl groups include C aryl groups such as phenyl group, naphthyl group (1-naphthyl group, 2-naphthyl group), biphenylyl group, anthryl group, phenanthryl group, etc. 6-14 Preferably C aryl groups. 6-10 Examples include aryl groups.

[0037] Examples of groups formed by combining two or more hydrocarbon groups (bonded groups) include alkylaryl groups, aralkyl groups, etc. Examples of alkylaryl groups include mono- or di-C alkylaryl groups such as methylphenyl group (tolyl group), dimethylphenyl group (xylyl group), etc. 1-6 Alkyl C 6-10 Examples include aryl groups, etc. Examples of aralkyl groups include C aralkyl groups such as phenylmethyl group (benzyl group), 2-phenylethyl group (phenethyl group), etc. 6-10 Aryl C 1-6 Examples include alkyl groups, etc.

[0038] Examples of the substituted amino group include an alkylamino group, an acylamino group, etc. Examples of the alkylamino group include a mono- or dialkylamino group such as a dimethylamino group, and examples of the acylamino group include a mono- or diacylamino group such as a diacetylamino group.

[0039] Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, etc.

[0040] Preferred R 1 is a hydrocarbon group such as an alkyl group, more preferably a C 1-12 alkyl group such as a methyl group, a hexyl group, a decyl group, etc., still more preferably, stepwise, a C 1-10 alkyl group, a C 1-8 alkyl group, a C 1-6 alkyl group, a C 1-4 alkyl group, a C 1-3 alkyl group, a C 1-2 alkyl group, and is a methyl group.

[0041] In addition, when R 1 is the divalent group, R 1 is bonded to the 9-position of the fluorene ring by a double bond, and k is 1; when R 1 is a monovalent group, R 1 is bonded to the 9-position of the fluorene ring by a single bond, and k is 1 or 2; when k is 0 (unsubstituted), a hydrogen atom is bonded to the 9-position of the fluorene ring. Further, when k is 2, the types of the two R 1 (monovalent groups) may be different from each other, but are preferably the same.

[0042] R 1 The coefficient k of may be any integer from 0 to 2, 0 or 2 is preferred, and 2 is still more preferred.

[0043] R 2a and R 2bExamples of the substituent represented by include substituents that do not have an acryloyl skeleton, such as hydrocarbon groups such as alkyl groups and aryl groups, a cyano group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group include linear or branched C 1-6 alkyl groups such as alkyl groups, and examples of the aryl group include C 6-10 aryl groups such as phenyl groups.

[0044] When m1 and m2 are 1 or more, preferred R 2a , R 2b are preferably an alkyl group such as a linear or branched C 1-4 alkyl group, a cyano group, or a halogen atom, more preferably an alkyl group, particularly a C 1-3 alkyl group such as a methyl group.

[0045] R 2a , R 2b The substitution numbers m1 and m2 of are, for example, integers of about 0 to 2, preferably 0 or 1, more preferably 0. m1 and m2 may be different from each other, but are preferably the same. When m1 and m2 are 1 or more, R 2a and R 2b substituted on different benzene rings constituting the fluorene skeleton may be the same as or different from each other. When m1 and m2 are 2 or more, two or more R 2a , R 2b substituted on the same benzene ring may be the same as or different from each other. Also, the substitution positions of R 2a , R 2b are not particularly limited, and may be substituted at positions other than the substitution positions of the groups [-C(=O)-CH(=CHR 3a )-CH(R 4a )-OH], [-C(=O)-CH(=CHR 3b )-CH(R 4b )-OH] (hereinafter also referred to as acryloyl skeleton-containing groups).

[0046] R3a and R 3b Examples of the substituent represented by include, for example, a hydrocarbon group and a halogen atom. Specifically, the hydrocarbon group and the halogen atom are the same as those exemplified in the item of R 1 and the like. Preferred substituents are hydrocarbon groups such as an alkyl group. Examples of the alkyl group include linear or branched C 1-10 alkyl groups such as alkyl groups, and preferably C 1-6 alkyl groups, more preferably C 1-4 alkyl groups.

[0047] Preferred R 3a and R 3b are hydrogen atoms. Note that R 3a and R 3b may be different from each other, but are preferably the same.

[0048] R 4a and R 4b Examples of the substituent represented by include, for example, an optionally substituted hydrocarbon group (a hydrocarbon group which may have a substituent). Examples of the hydrocarbon group include the same groups as those exemplified in the item of R 1 and the like. Preferred hydrocarbon groups are an alkyl group, an aryl group, and an aralkyl group, and more preferably a C 1-4 alkyl group such as a methyl group, a C 6-10 aryl group such as a phenyl group, and a C 6-10 aryl C 1-4 alkyl group such as a benzyl group and a phenethyl group. Examples of the substituent which the hydrocarbon group may have include, for example, a halogen atom, a substituted amino group, a nitro group, and the like. Examples of the halogen atom and the substituted amino group include the same groups as those exemplified in the item of R 1 and the like.

[0049] Preferred R 4a and R 4bis a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom. Note that R 4a and R 4b may be different from each other, but are preferably the same.

[0050] In the above formula (1), the substitution positions of the two acryloyl group-containing groups are not particularly limited, but are preferably the 2,7-positions.

[0051] Typical diol compounds represented by the above formula (1) include diol compounds in which R 3a and R 3b are hydrogen atoms, and R 4a and R 4b are hydrogen atoms or hydrocarbon groups such as alkyl groups. Examples include bis[α-hydroxyalkyl-acryloyl]fluorene such as 2,7-bis[α-hydroxymethyl-acryloyl]fluorene; 9,9-dialkyl-bis[α-hydroxyalkyl-acryloyl]fluorene such as 9,9-dimethyl-2,7-bis[α-hydroxymethyl-acryloyl]fluorene, etc. Preferably, 9,9-dialkyl-2,7-bis[α-hydroxyalkyl-acryloyl]fluorene such as 9,9-dimethyl-2,7-bis[α-hydroxymethyl-acryloyl]fluorene is mentioned. 1-4 alkyl-2,7-bis[α-hydroxyC 1-4 alkyl-acryloyl]fluorene is mentioned.

[0052] [Production method of the diol compound represented by formula (1)] The production method of the diol compound represented by the above formula (1) is not particularly limited. For example, it may be prepared by reacting a compound represented by the following formula (2) with compounds represented by the following formulas (3a) and (3b). As a typical method, it can be prepared by the following reaction steps using a compound represented by the following formula (5) as a starting material.

[0053]

Chemical formula

[0054] (wherein X 1a and X 1b each independently represent a leaving group, X 2a and X 2b each independently represent a halogen atom, R 1 , k, R 2a and R 2b , m1 and m2, R 3a and R 3b , R 4a and R 4b and the double lines of solid and dashed lines each include preferred embodiments and are the same as those in the above formula (1)).

[0055] (Preparation of the compound represented by formula (4)) The compound represented by the above formula (4) can be synthesized by subjecting the compound represented by the above formula (5) and the compounds represented by the above formulas (6a) and (6b) to a Friedel-Crafts acylation reaction.

[0056] Typical compounds represented by the above formula (5) include, for example, fluorenes such as 9H-fluorene and 9,9-dimethylfluorene.

[0057] In the above formulas (6a) and (6b) [and formula (4)], examples of the leaving group represented by X 1a and X 1b include, for example, a halogen atom, a hydroxyl group, an aryloxy group, an acyloxy group, a carbonate group [-O-C(=O)-O-R X1 , a carbamate group [-O-C(=O)-N(R X1 ) 2 , a sulfo group [-SO 3 H] (or a sulfoxyl group), etc. In the carbonate group and the carbamate group, R X1 each independently represents a hydrogen atom or a hydrocarbon group.

[0058] Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, etc.

[0059] Examples of the aryloxy group include a C such as a phenoxy group 6-10 aryloxy group and the like.

[0060] Examples of the acyloxy group include a C such as an acetyloxy group 2-10 acyloxy group and the like.

[0061] In the carbonate group [-O-C(=O)-O-R X1 and the carbamate group [-O-C(=O)-N(R X1 ) 2 , examples of the hydrocarbon group represented by R X1 include the same groups as the alkyl group, cycloalkyl group, aryl group, and a group formed by combining two or more of these hydrocarbon groups exemplified as R 1 in the above formula (1).

[0062] Examples of the carbonate group [-O-C(=O)-O-R X1 include a C such as a methoxycarbonyloxy group 1-10 alkoxycarbonyloxy group and the like.

[0063] Examples of the carbamate group [-O-C(=O)-N(R X1 ) 2 include a carbamoyloxy group; (mono- or di)alkyl-carbamoyloxy groups such as an N-methylcarbamoyloxy group and an N,N-dimethylcarbamoyloxy group.

[0064] Preferred X 1a and X 1b include a halogen atom, an aryloxy group, an acyloxy group, a carbonate group, a carbamate group, and a sulfo group, more preferably a halogen atom, particularly a chlorine atom. The types of X 1a and X 1b may be different from each other, but are preferably the same.

[0065] Also, in the above formulas (6a) and (6b), X 2aand X 2b Examples of the halogen atom represented by 2b include a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom is preferable. X 2a and X 2b The types of 2a and 2b may be different from each other, but the same is preferable.

[0066] Examples of the typical compounds represented by the formulas (6a) and (6b) include compounds in which R 3a and R 3b are hydrogen atoms, and specifically, 3-halopropionyl halides such as 3-chloropropionyl chloride are included. The compounds represented by the formulas (6a) and (6b) are preferably the same compound.

[0067] The total usage ratio of the compounds represented by the formulas (6a) and (6b) is, for example, 2 to 10 moles, preferably 2.2 to 5 moles, more preferably 2.3 to 3 moles, per 1 mole of the compound represented by the formula (5).

[0068] The Friedel-Crafts acylation reaction is carried out in the presence of a Lewis acid. Examples of the Lewis acid include aluminum halides such as aluminum chloride and aluminum bromide, iron(III) halides such as iron(III) chloride, zinc halides such as zinc chloride, tin(II) halides such as tin(II) chloride, boron trifluoride or its complex, specifically, boron trifluoride ether complexes such as boron trifluoride diethyl ether complex, etc.

[0069] These Lewis acids can be used alone or in combination of two or more. A preferable Lewis acid is an aluminum halide such as aluminum chloride. The usage ratio of the Lewis acid is, for example, 2 to 10 moles, preferably 2.2 to 5 moles, more preferably 2.3 to 3 moles, per 1 mole of the compound represented by the formula (5).

[0070] The Friedel-Crafts acylation reaction may be carried out in the presence or absence of a solvent. The solvent may be any solvent that is inert to the reaction, and examples thereof include halogenated alkanes such as dichloromethane, chloroform, 1,2-dichloroethane, and nitrobenzene. Among these solvents, dichloromethane is preferred. The usage ratio of the solvent is not particularly limited, and may be, for example, about 10 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the compounds represented by the above formulas (5), (6a) and (6b), and the Lewis acid.

[0071] The reaction may be carried out under an inert gas atmosphere, for example, under an atmosphere of nitrogen gas; noble gases such as helium and argon. The reaction temperature is, for example, -20°C to 50°C, preferably -10°C to 30°C. The reaction time is not particularly limited, and may be, for example, about 1 to 48 hours, preferably 12 to 24 hours. After completion of the reaction, quenching (quenching treatment) may be carried out. For example, a mixture of ice water and concentrated hydrochloric acid may be added for quenching.

[0072] After completion of the reaction, if necessary, the reaction mixture may be separated and purified by conventional separation and purification methods, for example, washing, extraction, filtration, dehydration, concentration, decantation, recrystallization, reprecipitation, chromatography, or a combination of these methods.

[0073] Typical compounds represented by the above formula (4) thus obtained include, for example, 2,7-bis(3-halopropanoyl)fluorene such as 2,7-bis(3-chloropropanoyl)fluorene; 9,9-dialkyl-2,7-bis(3-halopropanoyl)fluorene such as 9,9-dimethyl-2,7-bis(3-chloropropanoyl)fluorene.

[0074] (Preparation of the compound represented by formula (2)) The fluorene compound ((meth)acryloyl compound) represented by the formula (2) can be synthesized by subjecting the compound represented by the formula (4) to an elimination reaction. The elimination reaction is preferably an E1cb reaction. The E1cb reaction is carried out in the presence of a base. The bases can be roughly classified into inorganic bases and organic bases.

[0075] Examples of the inorganic bases include metal hydroxides, specifically hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and calcium hydroxide; metal carbonates, specifically carbonates of alkali metals or alkaline earth metals such as sodium carbonate and calcium carbonate; metal hydrogen carbonates, specifically hydrogen carbonates of alkali metals or alkaline earth metals such as sodium hydrogen carbonate.

[0076] Examples of the organic bases include amines, specifically trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic amines such as pyridine and N-methylmorpholine.

[0077] These bases may be used alone or in combination of two or more. Among these bases, amines such as trialkylamines such as triethylamine are often used. The usage ratio of the base is, for example, 1 to 10 moles, preferably 3 to 7 moles, more preferably 4 to 6 moles, per 1 mole of the compound represented by the formula (4).

[0078] The E1cb reaction may be carried out in the presence or absence of a solvent. The solvent may be any solvent inert to the reaction, and examples thereof include halogenated alkanes such as dichloromethane, chloroform, and 1,2-dichloroethane. Among these solvents, chloroform is preferred. The usage ratio of the solvent is not particularly limited, and may be, for example, about 50 to 5000 parts by mass per 100 parts by mass of the compound represented by the formula (4).

[0079] The reaction may be carried out under an inert gas atmosphere, for example, under an atmosphere of nitrogen gas; noble gases such as helium and argon. The reaction temperature is, for example, 0 to 50 °C, preferably 10 to 40 °C, more preferably 20 to 35 °C. The reaction time is not particularly limited and may be, for example, about 1 to 48 hours, preferably 12 to 36 hours.

[0080] After completion of the reaction, if necessary, the reaction mixture may be separated and purified by conventional separation and purification methods, for example, washing, extraction, filtration, dehydration, concentration, decantation, recrystallization, reprecipitation, chromatography, or a method combining these.

[0081] In addition, in order to improve the storage stability of the obtained compound represented by the formula (2), a polymerization inhibitor may be added as necessary, or the preparation (reaction) may be carried out in the presence of a polymerization inhibitor. Examples of the polymerization inhibitor include benzoquinone; hydroquinones such as hydroquinone, hydroquinone monomethyl ether (MEHQ), t-butylhydroquinone, and p-benzoquinone; catechols such as p-t-butylcatechol and 2-methoxyphenol; amines such as N,N-diethylhydroxylamine; 1,1-diphenyl-2-picrylhydrazyl; tri-p-nitrophenylmethyl; and phenothiazine. The polymerization inhibitor may be used alone or in combination of two or more. The proportion of the polymerization inhibitor may be, for example, about 0.001 to 10 parts by mass with respect to 100 parts by mass of the compound represented by the formula (2), or may be about 500 ppm with respect to the compound represented by the formula (2).

[0082] Typical compounds as the compound represented by the formula (2) thus obtained include those where R 3a and R 3b are hydrogen atoms, such as bis[(meth)acryloyl]fluorene such as 2,7-bis[(meth)acryloyl]fluorene; 9,9-dialkyl-bis[(meth)acryloyl]fluorene such as 9,9-dimethyl-2,7-bis[(meth)acryloyl]fluorene.

[0083] (Preparation of the compound represented by formula (1)) The diol compound represented by the formula (1) can be prepared by reacting the (meth)acryloyl compound represented by the formula (2) with the compounds (aldehydes) represented by the formulas (3a) and (3b), for example, by the Morita-Baylis-Hillman reaction (MBH reaction).

[0084] In the formulas (3a) and (3b), the groups R 4a and R 4b are the same as those in the formula (1) including the preferred embodiments. Also, the types of the groups R 4a and R 4b may be different from each other, but the same is preferred.

[0085] Typical compounds represented by the formulas (3a) and (3b) include, for example, compounds in which R 4a and R 4b are a hydrogen atom or an optionally substituted hydrocarbon group, and specifically, aldehydes such as formaldehyde and acetaldehyde are included, and formaldehyde is preferred. The compounds represented by the formulas (3a) and (3b) are preferably the same compound.

[0086] The total usage ratio of the compounds represented by the formulas (3a) and (3b) may be, for example, 2 to 10 moles, preferably 2.2 to 5 moles, more preferably 2.3 to 3 moles, and particularly 2.1 to 2.5 moles, based on 1 mole of the compound represented by the formula (2).

[0087] The MBH reaction is carried out in the presence of a catalyst. The catalyst is not particularly limited, and a conventional catalyst for the MBH reaction may be used, and examples include tertiary amines and tertiary phosphines, preferably tertiary amines, and more preferably cyclic tertiary amines (cyclic tertiary amines).

[0088] Examples of cyclic tertiary amines include azabicyclo[2.2.2]octanes such as 1,4-diazabicyclo[2.2.2]octane (DABCO), 1-azabicyclo[2.2.2]octane (or quinuclidine), and quinuclidin-3-ol; and cyclic amidines such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN).

[0089] These catalysts can be used alone or in combination of two or more. Preferred catalysts are cyclic tertiary amines, and azabicyclo[2.2.2]octanes such as DABCO are more preferred. The usage ratio of the catalyst may be, for example, 2 to 10 mol, preferably 2.2 to 5 mol, more preferably 2.3 to 3 mol, and particularly 2 to 2.5 mol, per 1 mol of the compound represented by the above formula (2).

[0090] The reaction may be carried out in the presence or absence of a solvent. The solvent may be any solvent inert to the reaction, and examples include halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; ethers such as diethyl ether, tetrahydrofuran, and dioxane; and nitriles such as acetonitrile. Among these solvents, halogenated alkanes such as dichloromethane are preferred. The usage ratio of the solvent is not particularly limited, and may be, for example, about 10 to 1000 parts by mass, preferably 300 to 500 parts by mass, per 100 parts by mass of the total amount of the compounds represented by the above formulas (2), (3a), and (3b), and the catalyst.

[0091] The reaction may be carried out under an air atmosphere or an inert gas atmosphere, for example, under an atmosphere of nitrogen gas; noble gases such as helium and argon. The reaction temperature is, for example, -50°C to 50°C, preferably 0 to 40°C, more preferably 10 to 30°C. The reaction time is not particularly limited and may be, for example, about 1 hour to 100 days, preferably 3 hours to 10 days, more preferably 6 to 72 hours, and particularly 5 to 60 minutes.

[0092] After the reaction is completed, if necessary, the reaction mixture may be separated and purified by conventional separation and purification methods, such as washing, extraction, filtration, dehydration, drying, concentration, decantation, crystallization (recrystallization), column chromatography, or a combination of these methods.

[0093] [Polymer (resin) containing the diol compound represented by formula (1) as a polymerization component] The diol compound represented by the above formula (1) can be suitably used as a polymerization component (monomer) of the polymer (resin). Such resins are not particularly limited as long as they contain at least the diol compound represented by the above formula (1) as a polymerization component (diol component), and examples include polyester resins, polyether resins, polyurethane resins, etc. Among these resins, polyester resins (polyconjugated ester ketone resins) are preferred.

[0094] Examples of polyester resins (polyconjugated ester ketone resins) include polyester resins, polycarbonate resins, polyester carbonate resins, etc. Among these polyester resins, polyester resins are preferred.

[0095] (Diol unit) The polyester resin (polyconjugated ester ketone resin) preferably contains a diol unit derived from the diol component and a dicarboxylic acid unit derived from the dicarboxylic acid component. Therefore, the diol unit contains at least the diol unit (first diol unit) represented by the following formula (1P) corresponding to the diol compound (first diol component) represented by the above formula (1).

[0096] [Chemical formula]

[0097] (In the formula, R 1 , k, R 2a and R 2b , m1 and m2, R 3a and R 3b , R 4aand R 4b In addition, the double lines of solid lines and broken lines are the same as those in the formula (1) including preferred embodiments respectively.

[0098] The diol unit may or may not contain another diol unit (second diol unit) different from the first diol unit represented by the formula (1P) as necessary.

[0099] Examples of the second diol component for forming the second diol unit include an aliphatic diol component, an alicyclic diol component, an aromatic diol component (excluding the compound represented by the formula (1)), and alkylene oxide (or alkylene carbonate, haloalkanol) adducts of these diol components.

[0100] Examples of the aliphatic diol component include alkylene glycol and polyalkylene glycol.

[0101] Examples of the alkylene glycol include linear or branched C such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2 - butanediol, 1,3 - butanediol, tetramethylene glycol (or 1,4 - butanediol), 1,5 - pentanediol, neopentyl glycol, 1,6 - hexanediol, 1,8 - octanediol, 1,10 - decanediol 2-12 alkylene glycol and the like. Preferably linear or branched C 2-6 alkylene glycol, more preferably linear or branched C 2-4 alkylene glycol.

[0102] Examples of the polyalkylene glycol include di - to deca - linear or branched C alkylene glycol such as diethylene glycol, dipropylene glycol, triethylene glycol 2-12 alkylene glycol and the like. Preferably di - to hexa - linear or branched C 2-6Alkylene glycol, more preferably di- to tetra-linear or branched C 2-4 Examples of the alkylene glycol include those mentioned above.

[0103] Examples of the alicyclic diol component include cycloalkanediols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; hydrogenated products of aromatic diol components described below such as the hydrogenated product of bisphenol A.

[0104] Examples of the aromatic diol component include dihydroxyarenes such as hydroquinone and resorcinol; aromatic aliphatic diols such as benzenedimethanol; bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; biphenyls such as p,p'-biphenol.

[0105] Examples of the alkylene oxide (or corresponding alkylene carbonate, haloalkanol) adducts of these diol components include C 2-4 alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, etc. of C 2-3 alkylene oxide adducts, and the number of moles added is not particularly limited. Specifically, examples include adducts obtained by adding about 2 to 10 moles of ethylene oxide to 1 mole of bisphenol A.

[0106] The diol unit (B) may contain these second diol units alone or in combination of two or more.

[0107] The proportion of the first diol unit can be selected from a range of, for example, about 10 to 100 mol% with respect to the total diol units. Preferred ranges are, step by step, 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and particularly 100 mol%. If the proportion of the first diol unit is too small, there is a risk of deterioration in heat resistance and optical properties such as refractive index.

[0108] (Dicarboxylic acid unit) The dicarboxylic acid unit is not particularly limited, but from the viewpoints of heat resistance and optical properties such as refractive index, it preferably contains at least an aromatic dicarboxylic acid unit (first dicarboxylic acid unit) derived from an aromatic dicarboxylic acid component (first dicarboxylic acid component).

[0109] Examples of the aromatic dicarboxylic acid component (first dicarboxylic acid component) include monocyclic aromatic dicarboxylic acids, polycyclic aromatic dicarboxylic acids, and ester-forming derivatives thereof. Examples of the monocyclic aromatic dicarboxylic acid include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid; alkylbenzenedicarboxylic acids, specifically, C 1-4 alkyl-benzenedicarboxylic acids such as 4-methylisophthalic acid, etc.

[0110] Examples of the polycyclic aromatic dicarboxylic acid include condensed polycyclic aromatic dicarboxylic acids, specifically, condensed polycyclic C 10-24 arene-dicarboxylic acids such as naphthalenedicarboxylic acid, anthracenedicarboxylic acid, and phenanthrenedicarboxylic acid, preferably condensed polycyclic C 10-14 arene-dicarboxylic acids, etc.; biaryl dicarboxylic acids, specifically, biC 6-10 aryl-dicarboxylic acids such as 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and 3,3'-dicarboxy-1,1'-binaphthyl, etc.; bis(carboxyalkoxy)biC 6-10 aryl, specifically, bis(carboxyC 1-4 alkoxy)biC 6-10 aryl such as 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, etc.; bis[(carboxyalkoxy)-C 6-10 aryl]alkane, specifically, bis[(carboxyC 1-4 alkoxy)-C 6-10 aryl)C 1-6Alkanes, etc.; diarylalkanedicarboxylic acids, specifically, diC such as 4,4'-diphenylmethanedicarboxylic acid 6-10 Aryl C 1-6 Alkane-dicarboxylic acids, etc.; diarylketonedicarboxylic acids, specifically, di(C such as 4,4'-diphenylketonedicarboxylic acid 6-10 Aryl)ketone-dicarboxylic acids, etc.; diaryletherdicarboxylic acids, specifically, di(C such as 4,4'-diphenyletherdicarboxylic acid 6-10 Aryl)ether-dicarboxylic acids, etc.; diarylsulfonedicarboxylic acids, specifically, di(C such as 4,4'-diphenylsulfonedicarboxylic acid 6-10 Aryl)sulfone-dicarboxylic acids, etc. may be mentioned.

[0111] Examples of the naphthalenedicarboxylic acid include 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like.

[0112] The dicarboxylic acid units may contain these aromatic dicarboxylic acid units alone or in combination of two or more. Among these aromatic dicarboxylic acid units, monocyclic aromatic dicarboxylic acid units are preferred, and benzene dicarboxylic acid units such as terephthalic acid units and isophthalic acid units are more preferred.

[0113] The dicarboxylic acid units may or may not contain other dicarboxylic acid units (second dicarboxylic acid units) different from the aromatic dicarboxylic acid units (first dicarboxylic acid units) as required.

[0114] Examples of the second dicarboxylic acid component for forming the second dicarboxylic acid units include aliphatic dicarboxylic acid components and alicyclic dicarboxylic acid components.

[0115] Examples of the aliphatic dicarboxylic acid component include alkane dicarboxylic acids, specifically C of succinic acid, adipic acid, sebacic acid, decane dicarboxylic acid, etc. 2-12 Alkane-dicarboxylic acids, etc.; unsaturated aliphatic dicarboxylic acids, specifically C of maleic acid, fumaric acid, itaconic acid, etc. 2-10 Alkene-dicarboxylic acids; and ester-forming derivatives thereof, etc.

[0116] Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids, specifically C of 1,4-cyclohexane dicarboxylic acid, etc. 5-10 Cycloalkane-dicarboxylic acids, etc.; bridged cyclic cycloalkane dicarboxylic acids, specifically bi- or tricycloalkane dicarboxylic acids such as decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.; cycloalkene dicarboxylic acids, specifically C of cyclohexene dicarboxylic acid, etc. 5-10 Cycloalkene-dicarboxylic acids, etc.; bridged cyclic cycloalkene dicarboxylic acids, specifically bi- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid; and ester-forming derivatives thereof, etc.

[0117] The proportion of the aromatic dicarboxylic acid unit (the first dicarboxylic acid unit) can be selected from a range of, for example, about 10 to 100 mol% with respect to the total dicarboxylic acid units. Preferred ranges are, step by step, 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and particularly 100 mol%. If the proportion of the first dicarboxylic acid unit is too small, there is a risk of deterioration in heat resistance and optical properties such as refractive index.

[0118] (Carbonate unit) When the resin is a polyester resin containing the diol unit, it may further contain a carbonate unit as necessary to form a polycarbonate resin or a polyester carbonate resin.

[0119] In the present specification and claims, the "carbonate unit" refers to a structural unit derived from a carbonate bond-forming component that can form a carbonate bond [-O-C(=O)-O-] by reaction with a diol component or the like, that is, it means a carbonyl group [-C(=O)-]. In other words, a carbonate bond can be formed together with the terminal oxygen atoms of two diol units that are bonded adjacent to the carbonate unit (carbonyl group).

[0120] Therefore, as the carbonate bond-forming component, any compound that can form a carbonate bond by reaction with a diol component may be used. Representative carbonate bond-forming components include, for example, phosgene such as phosgene and triphosgene, and carbonic acid diesters such as diphenyl carbonate. These carbonate bond-forming components can be used alone or in combination of two or more.

[0121] The ratio of the total amount of dicarboxylic acid units and carbonate units in the resin to the diol units is preferably such that the former / latter (molar ratio) = 1 / 0.8 to 1 / 1.2, more preferably 1 / 0.9 to 1 / 1.1, and most preferably approximately equimolar. Also, the ratio of the dicarboxylic acid units to the carbonate units can be selected from the range of the former / latter (molar ratio) = 100 / 0 to 0 / 100, and may be, for example, about 99 / 1 to 1 / 99.

[0122] (Other structural units) Note that depending on the type of resin, it may not contain other structural units different from the diol units, dicarboxylic acid units, and carbonate units, but may contain them as necessary within a range that does not impair the effects of the present invention.

[0123] Examples of other structural units include, when the resin is a polyester resin, structural units derived from a hydroxycarboxylic acid component, a corresponding lactone component, a polyfunctional polymer component having three or more polymerizable groups (carboxyl group and / or hydroxyl group), and the like.

[0124] Examples of the hydroxycarboxylic acid component include aromatic hydroxycarboxylic acids such as hydroxybenzoic acid; aliphatic hydroxycarboxylic acids (hydroxyalkanoic acids) such as lactic acid, 3-hydroxybutyric acid, and 6-hydroxyhexanoic acid; and ester-forming derivatives thereof. Examples of the corresponding lactone component include lactones corresponding to hydroxyalkanoic acids such as ε-caprolactone.

[0125] Examples of the polyfunctional polymer component having a total of three or more polymerizable groups (carboxyl group and / or hydroxyl group) include polyvalent carboxylic acids having a valence of three or more such as trimellitic acid and pyromellitic acid; polyhydric alcohols having a valence of three or more such as glycerin and pentaerythritol.

[0126] The proportion of such other structural units is, for example, 50 mol% or less, preferably in the following steps, 0 to 30 mol%, 0 to 10 mol%, 0.01 to 5 mol% with respect to the total amount of all structural units (the total amount of diol units, dicarboxylic acid units, carbonate units, and other structural units), and it is preferable to substantially contain no other structural units.

[0127] (Method for producing resin) The method for producing the resin (or polymerization) is not particularly limited except that a diol component containing at least the first diol component is used as a polymer component, and a conventional method can be used according to the type of resin and other polymer components (copolymer components).

[0128] For example, in the case of a polyester resin such as a polyester resin, it may be produced by polymerizing a polymer component containing a diol component corresponding to the aforementioned diol unit and a dicarboxylic acid component corresponding to each of the aforementioned dicarboxylic acid units, and a conventional method, specifically, a melt polymerization method such as a transesterification method or a direct polymerization method, a solution polymerization method, an interfacial polymerization method, etc. may be used.

[0129] The charging ratio of the diol component to the dicarboxylic acid component is such that the former / latter (molar ratio) = for example, 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9. Also, it is not necessarily required to be within this range, and at least one component selected from the polymerization components may be used in excess relative to the planned introduction ratio for reaction. For example, a diol component such as ethylene glycol that can be distilled out from the reaction system may be used in excess compared to the ratio (or introduction ratio) introduced into the polyester resin.

[0130] Also, when using a carbonate bond-forming component, the usage ratio of the total amount of the dicarboxylic acid component and the carbonate bond-forming component to the diol component is, for example, the former / latter (molar ratio) = 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9. Note that the carbonate bond-forming component may be used slightly in excess relative to the planned introduction ratio in consideration of volatilization and decomposition during the reaction, and relative to the total amount of the dicarboxylic acid units and carbonate units (total planned introduction amount into the resin), for example, 0.1 to 5 mol%, preferably 2 to 3 mol% excess of the carbonate bond-forming component may be used.

[0131] The reaction may be carried out in the presence of a catalyst if necessary. As the catalyst, conventional esterification catalysts such as metal catalysts can be used. As the metal catalyst, for example, alkali metals such as sodium; alkaline earth metals such as magnesium, calcium, barium; transition metals such as titanium, manganese, cobalt; Group 12 metals of the periodic table such as zinc, cadmium; Group 13 metals of the periodic table such as aluminum; Group 14 metals of the periodic table such as germanium, lead; Group 15 metals of the periodic table such as antimony, etc. are used. As the metal compound, for example, alkoxides; organic acid salts such as acetates, propionates; inorganic acid salts such as borates, carbonates; oxides, etc. may be used, and hydrates thereof may also be used. Representative metal compounds include, for example, germanium compounds such as germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, germanium-n-butoxide; antimony compounds such as antimony trioxide, antimony acetate, antimony ethylene glycolate; titanium compounds such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate (or titanium(IV) tetrabutoxide), titanium oxalate, potassium titanium oxalate; manganese compounds such as manganese acetate·4 hydrate; calcium compounds such as calcium acetate·1 hydrate, etc.

[0132] These catalysts can be used alone or in combination of two or more. When using a plurality of catalysts, each catalyst can be added according to the progress of the reaction. Among these catalysts, manganese acetate·4 hydrate, calcium acetate·1 hydrate, germanium dioxide, titanium(IV) tetrabutoxide, etc. are preferred. The amount of the catalyst used is, for example, 0.01×10 -4 ~100×10 -4 mol, preferably 0.1×10 -4 ~40×10 -4 mol.

[0133] The reaction may also be carried out in the presence of a stabilizer such as a heat stabilizer or an antioxidant, if necessary. Among these, heat stabilizers are often used. Examples of heat stabilizers include phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (or phosphoric acid dibutyl), phosphorous acid, trimethyl phosphite, and triethyl phosphite. Among these, phosphoric acid dibutyl is often used. The amount of the heat stabilizer used is, for example, 0.01×10 -4 ~100×10 -4 mol, preferably 0.1×10 -4 ~40×10 -4 mol, per 1 mol of the dicarboxylic acid component (A).

[0134] Note that the reaction may be carried out in the presence or absence of a solvent depending on the polymerization method. For example, hydrocarbons, specifically, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, etc.; halogenated hydrocarbons, specifically, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, etc.; ethers, specifically, dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane, etc.; ketones, specifically, acetone, methyl ethyl ketone, etc.; sulfoxides, specifically, dimethyl sulfoxide, etc.; amides, specifically, N,N-dimethylformamide (DMF), N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.; nitriles such as acetonitrile, etc. The solvents may be used alone or in combination of two or more. Among these solvents, halogenated hydrocarbons such as methylene chloride, ethers such as THF, and amides such as DMF are preferred.

[0135] In addition, when using an acid halide such as an acid chloride as the dicarboxylic acid component, the reaction may be carried out in the presence of a base to capture (trap) the hydrogen halide generated in the reaction. Examples of the base include inorganic bases and organic bases.

[0136] Examples of inorganic bases include metal hydroxides, specifically hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and calcium hydroxide; metal carbonates, specifically carbonates of alkali metals or alkaline earth metals such as sodium carbonate and calcium carbonate; metal hydrogen carbonates, specifically hydrogen carbonates of alkali metals or alkaline earth metals such as sodium hydrogen carbonate.

[0137] Examples of organic bases include amines, specifically trialkylamines such as triethylamine and N,N - diisopropylethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic amines such as pyridine and N - methylmorpholine. The base may be used alone or in combination of two or more.

[0138] Among these bases, amines such as trialkylamines like triethylamine and N,N - diisopropylethylamine are often used. The amount of the base used is not particularly limited. For example, it may be about 1 to 5 moles, specifically 1 to 2 moles, preferably 1.05 to 1.5 moles, more preferably 1.1 to 1.2 moles, particularly 2 to 4 moles, and especially 2 to 2.5 moles, per 1 mole of the dicarboxylic acid halide.

[0139] The reaction may be carried out in an atmosphere of an inert gas such as nitrogen gas; noble gases such as helium and argon. Also, the reaction may be under normal pressure or under reduced pressure, for example, 1×10 2 ~1×10 4It can also be carried out to a Pa degree. The transesterification reaction may be carried out in an inert gas atmosphere such as nitrogen gas, and the polycondensation reaction may be carried out under reduced pressure. The reaction temperature can be selected according to the polymerization method. For example, in the melt polymerization method, the reaction temperature is 150 to 320 °C, preferably 250 to 310 °C, more preferably 270 to 300 °C. When the dicarboxylic acid component is a dicarboxylic acid halide, the reaction temperature may be, for example, -10 °C to 30 °C, preferably 0 to 20 °C, more preferably 2 to 10 °C, or for example, 10 to 40 °C, preferably 20 to 30 °C.

[0140] After the reaction is completed, the produced resin may be separated and purified by conventional methods, such as separation and purification means such as washing, extraction, concentration, drying, reprecipitation, centrifugation, filtration, column chromatography, adsorption, etc., or means combining these.

[0141] (Properties of the resin) Since the resin of the present invention contains a diol unit represented by the above formula (1P) as a structural unit (polymerization component), it has a fluorene skeleton and an acryloyl-based skeleton (or a vinyl ketone-based skeleton, that is, [-C(=O)-C(=CHR 3a )-] and [-C(=O)-C(=CHR 3b )-]) in the main chain skeleton. Therefore, it can also exhibit high heat resistance and optical properties such as a high refractive index.

[0142] The glass transition temperature Tg of the resin may be, for example, about 50 to 200 °C. Also, the 5% mass loss temperature of the resin may be, for example, about 80 to 400 °C. The resin may be a crystalline or amorphous resin. When it is a crystalline resin, the melting point Tm may be, for example, about 100 to 300 °C. In this specification and the claims, the glass transition temperature Tg, the 5% mass loss temperature, and the melting point Tm can be measured by thermogravimetric differential thermal analysis (TG-DTA) or differential scanning calorimetry (DSC).

[0143] In addition, the refractive index of the resin may be, for example, about 1.5 to 1.7 at a temperature of 25°C and a wavelength of 589 nm. In the present specification and claims, the refractive index can be measured by a multi-wavelength Abbe refractometer.

[0144] Also, the number average molecular weight Mn of the resin may be, for example, about 1000 to 100000 (for example, 10000 to 50000), preferably in the following steps: 1000 to 50000, 3000 to 10000, 4000 to 7000. The molecular weight distribution D (Mw / Mn) of the resin may be, for example, about 1 to 5, preferably in the following steps: 1.5 to 4, 2 to 3.5, 2.5 to 3. It is preferable to appropriately adjust the number average molecular weight and the molecular weight distribution according to the use of the resin and the like.

[0145] In the present specification and claims, the number average molecular weight Mn and the molecular weight distribution D (Mw / Mn) can be measured by the method described in the examples below.

[0146] Since the resin can form a molded body having high heat resistance and optical properties such as a high refractive index, the present invention also includes a molded body containing the resin. The molded body only needs to contain at least the resin.

[0147] The molded body may contain other resins and conventional additives. Examples of conventional additives include fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, defoaming agents, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, stress-reducing agents, etc. Examples of stabilizers include antioxidants, ultraviolet absorbers, heat stabilizers, etc. Examples of stress-reducing agents include silicone oil, silicone rubber, various plastic powders, various engineering plastic powders, etc. These additives may be used alone or in combination of two or more. The total proportion of these additives is, for example, 50 parts by mass or less, preferably in the following steps: 30 parts by mass or less, 0 to 10 parts by mass, and may be about 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin.

[0148] The molded article can be manufactured using, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a compression molding method, a casting molding method, or the like.

[0149] The shape of the molded article is not particularly limited, and examples thereof include one-dimensional structures such as linear, fibrous, and thread-like shapes, two-dimensional structures such as film-like, sheet-like, and plate-like shapes, and three-dimensional structures such as concave or convex lens-like, rod-like, and hollow (tubular) shapes.

[0150] In addition, perhaps because the resin of the present invention contains a structural unit having an acryloyl skeleton, it can also be decomposed under relatively mild conditions. For example, when the resin is a polyester resin (polyconjugated ester ketone resin), instead of the ester bond, the bond between the allylic carbon atom ([- C HR 4a -] and [- C HR 4b -]) in the unit represented by the formula (1P) and the oxygen atom adjacent to this carbon atom is hydrolyzed, so that it can be easily or efficiently decomposed even at room temperature (about 20 to 30 ° C), in water, in the presence of a base, particularly in the presence of a nucleophile such as hydroxide ions, alcohol, water, thiol, ammonia, and amine. These bases or nucleophiles can be used alone or in combination of two or more. Among these bases or nucleophiles, an aqueous solution containing hydroxide ions such as an aqueous sodium hydroxide solution and a tertiary amine such as triethylamine are preferable, and it is more preferable to use both in combination. Furthermore, in some cases, the monomer components used for polymerization can be recovered from the decomposition products, and it is useful as a resin that is environmentally friendly and recyclable, that is, a cyclic polymer.

[0151] In addition, since the resin of the present invention has an acryloyl skeleton in the main chain skeleton, a curable composition may be formed by using the unsaturated bond of this acryloyl skeleton and utilizing it as a curable resin (polymerization component) or a crosslinking agent.

[0152] The curable composition only needs to contain at least the resin, and may also contain other polymerization components having unsaturated double bonds. Examples of other polymerization components include monomers (or reactive diluents) having unsaturated double bonds, specifically, aromatic vinyl monomers such as styrene, monofunctional (meth)acrylates such as methyl (meth)acrylate; curable resins such as polyfunctional (meth)acrylates, etc.

[0153] In addition to other polymerization components (or monomer components) having unsaturated double bonds, the curable composition may further contain polymerization initiators such as thermal polymerization initiators (thermal radical generators), photoinitiators (photo radical generators), photosensitizers, solvents, and the above-mentioned conventional additives.

[0154] The curable composition may be cured by applying active energy (or actinic rays) to form a cured product. The active energy is usefully thermal energy and / or light energy, for example, ultraviolet rays, X-rays, etc.

[0155] When heat treatment is carried out using thermal energy, the heating temperature is, for example, 50 to 200 °C, preferably 60 to 150 °C, more preferably 70 to 120 °C.

[0156] When light irradiation is carried out using light energy (for example, ultraviolet rays, etc.), the amount of light irradiation energy can be appropriately selected according to the use, for example, 50 to 10000 mJ / cm 2 , preferably 70 to 8000 mJ / cm 2 , more preferably 100 to 5000 mJ / cm 2 , particularly, 500 to 3000 mJ / cm 2 is.

[0157] The shape of the cured product is not particularly limited, and is the same as the shapes exemplified as the shape of the molded body.

Examples

[0158] The present invention will be described in more detail based on the following examples, but the present invention is not limited by these examples. Each evaluation method in the examples is as follows.

[0159] [Evaluation Method] (NMR Spectrum) Measurement was carried out at 25 °C using a nuclear magnetic resonance (NMR) apparatus ("AVANCE NEO" manufactured by Bruker Corporation). The measurement solvent was deuterated chloroform or deuterated dimethyl sulfoxide (DMSO-d 6 ), and the chemical shift values were calibrated with the signals of tetramethylsilane (TMS) and the solvent.

[0160] (Molecular Weight) The molecular weight (number average molecular weight Mn) and molecular weight dispersity D (Mw / Mn) of the polymer were measured using an EXTREMA chromatograph (manufactured by JASCO Corporation). Two size exclusion columns "HK-404L" (manufactured by Showa Denko K.K.) heated to 40 °C were loaded in series, and tetrahydrofuran (for high performance liquid chromatography, with stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) was flowed at 0.6 mL / min as the eluent. The chromatogram detected by an ultraviolet absorption spectrometer "UV-4070" (detected at 254 nm, manufactured by JASCO Corporation) and a differential refractive index detector (RI-4035, manufactured by JASCO Corporation) was calibrated with a cubic curve using standard polystyrene (manufactured by Tosoh Corporation, TSKgel Oligomer Kit, Mn: 1.03×10 6 , 3.89×10 5 , 1.82×10 5 , 3.68×10 4 , 1.63×10 4 , 5.32×10 3 , 3.03×10 3 , 8.73×10 2 ) and evaluated.

[0161] [Synthesis Example 1-1] Synthesis of 2,7-bis(3-chloropropanoyl)-9,9-dimethylfluorene

[0162] [Chemical Formula]

[0163] Under an argon atmosphere, dichloromethane (72 mL) was added to aluminum chloride (57.6 g, 432 mmol) in an ice bath, and a solution of 3-chloropropionyl chloride (54.6 g, 432 mmol) represented by the formula (6-1) in dichloromethane (144 mL) was added thereto over 20 minutes. Then, a solution prepared by dissolving 9,9-dimethylfluorene (35.9 g, 180 mmol) represented by the formula (5-1) in dichloromethane (90 mL) was added dropwise thereto over 20 minutes. After completion of the dropwise addition, the reaction was carried out in an ice bath for 40 minutes, and then the ice bath was removed and the reaction was carried out at room temperature for 22 hours.

[0164] After the reaction, the reaction mixture solution was poured into a reagent prepared by adding concentrated hydrochloric acid (20 mL) to ice water (190 g) for quenching. At this time, since a precipitate was formed, the solution was recovered by filtration and neutralized and washed with a saturated aqueous sodium hydrogen carbonate solution. Further, dichloromethane was added to the precipitate for washing, and the soluble part was neutralized and washed with a saturated aqueous sodium hydrogen carbonate solution. The obtained organic layers were combined, and the solvent was distilled off to obtain a solid. The solid was washed with methanol and hot hexane and dried under vacuum to obtain 2,7-bis(3-chloropropanoyl)-9,9-dimethylfluorene represented by the formula (4-1) in a yield of 63.4 g and a yield of 93.8%.

[0165] The obtained 2,7-bis(3-chloropropanoyl)-9,9-dimethylfluorene represented by the formula (4-1) 1 1H-NMR spectral data are shown in Figure 1 and below.

[0166] 1 1H-NMR(400MHz,CDCl 3 ,25℃):δ8.08(s,2H,positions 1 and 8),8.10-7.99(m,2H,positions 3 and 6),7.88-7.86(m,2H,positions 4 and 5),3.97(t,J=6.8Hz,4H,CH 2 Cl),3.54(t,J=6.8Hz,4H,C(O)CH 2 ),1.55(s,6H,CH 3 )ppm.

[0167] [Synthesis Example 1-2] Synthesis of 2,7-diacryloyl-9,9-dimethylfluorene

[0168]

Chemical formula

[0169] Under an argon atmosphere, 2,7-diacryloyl-9,9-dimethylfluorene (63.4 g, 169 mmol) represented by the formula (4-1) was dissolved in chloroform (300 mL) under an argon atmosphere. While stirring the solution at room temperature, triethylamine (82.2 g, 811 mmol) was added dropwise over 10 minutes, and the reaction was carried out at room temperature for 35 minutes.

[0170] Thereafter, the reaction solution was washed with 1M hydrochloric acid (100 mL × 2), saturated aqueous sodium hydrogen carbonate solution (100 mL × 2), distilled water (100 mL × 2), and saturated aqueous sodium chloride solution (100 mL × 1). After drying the organic layer over anhydrous sodium sulfate, it was concentrated and vacuum dried at room temperature to obtain 2,7-diacryloyl-9,9-dimethylfluorene represented by the formula (2-1) as a white solid. The yield and the recovery rate were 42.5 g and 83.1%, respectively.

[0171] The obtained 2,7-di(acryloyl)-9,9-dimethylfluorene's 1 1H-NMR spectrum data are shown in Figure 2 and below.

[0172] 1 1H-NMR (400 MHz, CDCl 3 , 25 °C): δ 8.08 (d, J = 1.5 Hz, 2H, positions 1 and 8), 7.99 (dd, J 1 = 7.9 Hz, J 2 = 1.5 Hz, 2H, positions 3 and 6), 7.87 (d, J = 7.9 Hz, 2H, positions 4 and 5), 7.24 (dd, J 1 = 17.0 Hz, J 2 = 10.5 Hz, 2H, -CH=), 6.48 (dd, J 1 = 17.0 Hz, J 2 = 1.7 Hz, 2H, CHH =),5.98(dd,J 1 =10.5Hz,J 2 =1.7Hz,2H,C H H=),1.57(s,6H,CH 3 )ppm。

[0173] [Example 1] Synthesis of 2,7-bis(α-hydroxymethyl-acryloyl)-9,9-dimethylfluorene

[0174] [Chemical formula]

[0175] Under an air atmosphere, 2,7-diacryloyl-9,9-dimethylfluorene (42.5 g, 140 mmol) represented by formula (2-1), formaldehyde (37% by mass aqueous solution, 25.1 g, 308 mmol) represented by formula (3-1), DABCO (31.4 g, 280 mmol), and tetrahydrofuran (440 mL) were mixed and reacted with stirring at room temperature for 35 minutes. After the reaction, the reaction solution was diluted with distilled water (300 mL) and extracted with ethyl acetate (200 mL×1, 100 mL×2). The organic layer was divided into two, and each organic layer was washed with a mixed solution of distilled water (100 mL) and saturated aqueous sodium chloride solution (100 mL), and then washed with saturated aqueous sodium chloride solution (100 mL). The organic layers were combined, dried over anhydrous sodium sulfate, and the solvent was distilled off. The crude product was washed with ethyl acetate and chloroform, and vacuum dried at room temperature to obtain 2,7-bis(α-hydroxymethyl-acryloyl)-9,9-dimethylfluorene represented by formula (1-1) as a white solid in a yield of 25.6 g and a yield of 55.1%.

[0176] The obtained 2,7-bis(α-hydroxymethyl-acryloyl)-9,9-dimethylfluorene 1 1H-NMR spectral data are shown in Figure 3 and below.

[0177] 1 1H-NMR(400MHz,CDCl 3, 25 °C): δ 8.08 (d, J = 7.8 Hz, 2H, positions 1 and 8), 7.98 (d, J = 1.0 Hz, 2H, positions 3 and 6), 7.80 (dd, J 1 = 7.8 Hz, J 2 = 1.0 Hz, 2H, positions 4 and 5), 6.10 (d, J = 1.0 Hz, 2H, C H H=), 5.68 (d, J = 1.0 Hz, 2H, CH H =), 5.18 (t, J = 5.7 Hz, 2H, OH), 4.33 (d, J = 5.7 Hz, 4H, allylic position), 1.52 (s, 6H, methyl group) ppm.

[0178] [Example 2] Synthesis of polyester (polyconjugated ester ketone)

[0179] [Chemical formula]

[0180] Under an argon atmosphere, triethylamine (0.28 mL, 2.0 mmol) was added to a dichloromethane (1.0 mL) solution of 2,7-bis(α-hydroxymethyl-acryloyl)-9,9-dimethylfluorene (0.362 g, 1.00 mmol) represented by formula (1-1), and the mixture was cooled in an ice bath. A dichloromethane solution (1.0 mL) of isophthaloyl chloride (0.203 g, 1.00 mmol) was added dropwise over 10 minutes, and after 30 minutes, the reaction was allowed to proceed at room temperature for 21 hours.

[0181] After the reaction, the reaction solution was diluted with dichloromethane (2 mL), added dropwise to methanol (80 mL), and the precipitate was centrifuged at 3000 rpm for 10 minutes. Vacuum drying was carried out at 50 °C, and the obtained solid was dissolved in dichloromethane (2.5 mL) and reprecipitated in methanol (50 mL). The precipitate was centrifuged at 3000 rpm for 15 minutes. Vacuum drying was carried out at 50 °C, and the obtained solid was dissolved in dichloromethane (2.5 mL) and reprecipitated in hexane (50 mL). Vacuum drying was carried out at 50 °C to obtain the polyester (polyconjugated ester ketone) represented by the above formula as a solid in a yield of 0.459 g and a yield of 93.2%.

[0182] The obtained polyester (polyconjugated ester ketone)'s 1 1H-NMR spectral data are shown in Figure 4 and below.

[0183] 1 1H-NMR (400 MHz, CDCl 3 , 25 °C): δ 8.78 (s, 1H, 2-position of isophthaloyl group), 8.26 (d, J = 7.6 Hz, 2H, 4-position and 6-position of isophthaloyl group), 7.92 (s, 2H, 1-position and 8-position of fluorene ring), 7.83 (br, 4H, 3 - 6 positions of fluorene ring), 7.54 (t, J = 7.6 H, 5-position of isophthaloyl group), 6.22 (s, 2H, C H H=), 5.93 (s, 2H, CH H =), 5.30 (s, 4H, allylic position), 1.53 (s, H, methyl group) ppm.

[0184] Also, the number average molecular weight Mn of the obtained polyester (polyconjugated ester ketone) was 4200, and the molecular weight dispersity D (Mw / Mn) was 3.34.

[0185] [Example 3] Synthesis of Polyester (Polyconjugated Ester Ketone) The experiment was carried out in the same manner as in Example 2 except that the solvent was changed from dichloromethane to tetrahydrofuran, and polyester (polyconjugated ester ketone) was obtained with a yield of 0.459 g and a yield of 93.2%. The number average molecular weight Mn of the obtained polyester (polyconjugated ester ketone) was 4900, and the molecular weight dispersity D (Mw / Mn) was 3.55.

[0186] [Example 4] Synthesis of Polyester (Polyconjugated Ester Ketone) The experiment was carried out in the same manner as in Example 2 except that the solvent was changed from dichloromethane to N,N-dimethylformamide (1 mL), and polyester (polyconjugated ester ketone) was obtained with a yield of 0.467 g and a yield of 94.8%. The number average molecular weight Mn of the obtained polyester (polyconjugated ester ketone) was 5200, and the molecular weight dispersity D (Mw / Mn) was 2.71.

[0187] [Example 5] Synthesis of Polyester (Polyconjugated Ester Ketone) The reaction was charged in the same manner as in Example 2 except that the base was changed to N,N - diisopropylethylamine (0.38 mL, 2.0 mmol) instead of triethylamine. The reaction was carried out with cooling in an ice bath for 15 minutes and then at room temperature for 21 hours. The polymerization solution was dropped into methanol (50 mL) for reprecipitation. The precipitate was collected by centrifugation (3000 rpm, 15 minutes) and dried in vacuo at 50 °C to obtain 0.463 g of polyester (polyconjugated ester ketone) with a yield of 94.1%. The number average molecular weight Mn of the obtained polyester (polyconjugated ester ketone) was 4900, and the molecular weight dispersity D(Mw / Mn) was 3.49.

[0188] [Example 6] Synthesis of Polyester (Polyconjugated Ester Ketone) In Example 4, when the solution of isophthaloyl chloride was being dropped into the solution of triethylamine and 2,7 - bis(α - hydroxymethyl - acryloyl) - 9,9 - dimethylfluorene, the operation was changed to dropping the solution of triethylamine and 2,7 - bis(α - hydroxymethyl - acryloyl) - 9,9 - dimethylfluorene into the solution of isophthaloyl chloride. Other operations were carried out in the same manner as in Example 4 to obtain 0.470 g of polyester (polyconjugated ester ketone) with a yield of 95.5%. The number average molecular weight Mn of the obtained polyester (polyconjugated ester ketone) was 2900, and the molecular weight dispersity D(Mw / Mn) was 2.99.

[0189] [Example 7] Synthesis of Polyester (Polyconjugated Ester Ketone) Polyester (polyconjugated ester ketone) was obtained in a yield of 59.5% with a yield of 0.293 g in the same manner as in Example 6 except that the amount of triethylamine was changed to 4.0 mmol instead of 2.0 mmol. The number average molecular weight Mn of the obtained polyester (polyconjugated ester ketone) was 4400, and the molecular weight dispersity D(Mw / Mn) was 2.60.

[0190] [Example 8] Degradation of Polyester (Polyconjugated Ester Ketone) 148 mg of the polyester (polyconjugated ester ketone) obtained in Example 6 was dissolved in N,N-dimethylformamide (5 mL), 0.416 mL (3.00 mmol) of triethylamine was added dropwise, and further 20 wt% aqueous sodium hydroxide solution (0.50 mL, 3.1 mmol) was added and stirred at room temperature to decompose (main chain cleavage) the polyester (polyconjugated ester ketone). After 1 hour, distilled water was added until precipitation occurred, and 63 mg of the decomposition product was obtained. The size exclusion chromatogram for evaluating the molecular weights of the polyester (polyconjugated ester ketone) before and after the decomposition reaction is shown in Fig. 5. The peak top molecular weight (Mp) before decomposition was 30200, while the peak top molecular weight (Mp) after decomposition was outside the calibration curve range (calculated to be 300 and 66), indicating a significant decrease in molecular weight.

Industrial Applicability

[0191] The novel diol compound having a fluorene skeleton and an acryloyl-based skeleton (or vinyl ketone-based skeleton, i.e., [-C(=O)-C(=CHR 3a )-] and [-C(=O)-C(=CHR 3b )-]) of the present invention can form a resin exhibiting excellent optical properties such as high heat resistance and high refractive index, and thus can be used for heat-resistant members and optical members. Further, since the resin has a plurality of acryloyl-based skeletons (or vinyl ketone-based skeletons), it can be used as a curable resin or a curing agent to form a curable composition, and can also form a cured product exhibiting excellent optical properties such as high heat resistance and high refractive index.

Claims

Claim 1 A diol compound represented by the following formula (1). 【Chemical 1】 (wherein, R １ represents an alkyl group, a cycloalkyl group, a halogen atom or an oxygen atom, k represents an integer of 0 to 2, and the double line of the solid line and the broken line represents a single bond or a double bond, R ２ａ and R ２ｂ each independently represents an alkyl group, and m1 and m2 each independently represent an integer from 0 to 3, R ３ａ and R ３ｂ each independently represents a hydrogen atom or an alkyl group, R ４ａ and R ４ｂ each independently represents a hydrogen atom or an alkyl group.) Claim 2 In the formula (1), R1 is a C1-10 alkyl group or a C5-10 cycloalkyl group, R2a and R2b are C1-6 alkyl groups, R ３ａ and R ３ｂ is a hydrogen atom or a C1-6 alkyl group, R ４ａ and R ４ｂ is a hydrogen atom or a C1-4 alkyl group, and the diol compound according to claim 1. Claim 3 A method for producing the diol compound according to Claim 1 or 2 by reacting a compound represented by the following formula (2) with compounds represented by the following formulas (3a) and (3b). [Chemical Formula 2] (wherein, R １ , k, R ２ａ and R ２ｂ , m1 and m2, R ３ａ and R ３ｂ , R ４ａ and R ４ｂ and the double lines of the solid line and the broken line are the same as those in the formula (1) described in claim 1, respectively.) Claim 4 A resin containing the diol compound according to Claim 1 or 2 as a polymerization component. Claim 5 A polyester resin containing a diol unit and a dicarboxylic acid unit, wherein the diol unit contains a diol unit represented by the following formula (1P), the resin according to Claim 4. 【Chemical Formula 3】 (wherein, R １ , k, R ２ａ and R ２ｂ , m1 and m2, R ３ａ and R ３ｂ , R ４ａ and R ４ｂ and the double lines of the solid line and the broken line are the same as the formula (1) described in claim 1, respectively.) Claim 6 The resin according to Claim 5, wherein the dicarboxylic acid unit contains a dicarboxylic acid unit derived from an aromatic dicarboxylic acid component. Claim 7 A method for decomposing the resin according to any one of Claims 4 to 6 in the presence of a base. Claim 8 The method according to Claim 7, wherein the base is a nucleophile. Claim 9 A curable composition containing the resin according to any one of Claims 4 to 6. Claim 10 A cured product obtained by curing the curable composition according to Claim 9.

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