JP2012236963A - Polyester, synthetic intermediate thereof and polymerizable composition including the intermediate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester having excellent heat resistance, a synthetic intermediate thereof and a polymerizable composition including the intermediate.SOLUTION: The polyester includes a structural unit represented by formula (1) [in formula, Rrepresents a single bond, an alkanediyl or alkenediyl group, Rrepresents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group, etc., A represents -S-, -S(=O)-, or -S(=O)-, and n represents 1 or 2].

Description

  The present invention relates to a polyester, a synthetic intermediate thereof, and a polymerizable composition containing the intermediate.

  Conventionally, polyesters obtained by alternately copolymerizing a specific bicyclic γ-butyrolactone and a specific epoxy compound are known as polyesters whose volume shrinkage during curing is suppressed (Patent Document 1 and Non-Patent Document 1). ~ 6).

Japanese Patent Laid-Open No. 7-62065

T. Takata, A. Tadokoro, and T. Endo Macromolecules 1992, 25,2782. A. Tadokoro, T. Takata, and T. Endo Macromolecules 1993, 26,4400. T. Takata, A. Tadokoro, K. Chung, and T. Endo Macromolecules 1995, 28, 1340. K. Chung, T. Takata, and T. Endo Macromolecules 1995, 28, 3048. K. Chung, T. Takata, and T. Endo Macromolecules 1997, 30, 2532. S. Ohsawa, K. Morino, A. Sudo, and T. Endo Macromolecules 2010, 43, 3585.

However, although the conventional polyester as described above is used as various functional polymer materials including electronic materials, the heat resistance is not sufficiently satisfactory.
Accordingly, an object of the present invention is to provide a polyester having excellent heat resistance, a synthetic intermediate thereof, and a polymerizable composition containing the intermediate.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that a polyester having a specific substituent containing a sulfur atom in a structural unit has excellent heat resistance.

  That is, this invention provides the polyester which has a structural unit (henceforth a structural unit (1)) represented by following formula (1).

[In the formula (1), R ¹ represents a single bond, an alkanediyl group or an alkenediyl group, and R ² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, or the following formula (2 )

(In the formula (2), R ⁵ represents an alkanediyl group, * represents a position bonded to A in the formula (1), and R ¹ , R ³ , R ⁴ , A and n are (It is synonymous with the thing in Formula (1).)
In which R ³ is independently a hydrogen atom, an amino group or a monovalent hydrocarbon group, and R ⁴ is an alkyl group. , Alkenyl group, alkoxy group, alkoxyalkyl group, aryloxyalkyl group or the following formula (3)

(In formula (3), R ⁶ represents a single bond or an alkanediyl group, R ⁷ represents an alkanediyl group, and ** binds to a carbon atom adjacent to R ⁴ in formula (1). And R ¹ , R ² , R ³ , A and n are as defined in formula (1).
Wherein A represents —S—, —S (═O) — or —S (═O) ₂ —, and n represents 1 Or 2 is shown. ]

  The present invention also includes a compound represented by the following formula (4) (hereinafter also referred to as compound (4)), a compound represented by the following formula (5) (hereinafter also referred to as compound (5)) and the following: The present invention provides a polymerizable composition comprising at least one compound selected from compounds represented by formula (6) (hereinafter also referred to as compound (6)).

[In the formula (4), R ⁸ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, or the following formula (7)

(In the formula (7), R ⁵ represents an alkanediyl group, *** represents a position bonded to A in the formula (4), and R ¹ , R ³ and A are as defined above. .)
Wherein R ¹ , R ³ and A are as defined above. ]

[In Formula (5), R ⁹ represents an alkyl group, an alkenyl group, an alkoxy group, an alkoxyalkyl group, or an aryloxyalkyl group, and n is as defined above. ]

[In Formula (6), R < ⁶ >, R < ⁷ > and n are synonymous with the above. ]

  Furthermore, this invention provides the compound represented by following formula (4).

[In the formula (4), R ¹ , R ³ , R ⁸ and A are as defined above. ]

The polyester of the present invention has excellent heat resistance.
Moreover, according to this invention, the compound useful as a synthetic | combination composition useful for the synthesis | combination of the said polyester and the said polyester can be provided.

It is a figure which shows the < ¹ > H-NMR spectrum of polyester S1-S4.

〔polyester〕
The polyester of the present invention has a structural unit represented by the formula (1). First, each symbol in the formula (1) will be described. In addition, this symbol is synonymous with each symbol in the formulas (2) to (7).

R ¹ represents a single bond, alkanediyl group or alkenediyl group.
Among these, an alkanediyl group and an alkenediyl group are preferable. Such alkanediyl group and alkenediyl group may be linear or branched.

The number of carbon atoms of the alkanediyl group represented by R ^1, 1 to 12, more preferably from 2 to 8, 3 to 6 is particularly preferred.
Examples of the alkanediyl group include methane-1,1-diyl group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2- Diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane- Examples include 1,4-diyl group, pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group and the like.

Moreover, as carbon number of the said alkenediyl group, 2-12 are preferable, 3-8 are more preferable, and 3-4 are especially preferable.
Examples of the alkenediyl group include an ethylene-1,1-diyl group, an ethylene-1,2-diyl group, a 2-propylene-1,1-diyl group, a 1-propylene-1,3-diyl group, and 3-butene. -1,2-diyl group, 2-pentene-1,4-diyl group and the like.

  The alkanediyl group and alkenediyl group may have a substituent. Examples of the substituent include a cycloalkyl group having 4 to 8 carbon atoms such as a cyclohexyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group. An aromatic oxy group having 6 to 12 carbon atoms such as a phenoxy group; a sulfenyl group such as a methylsulfanyl group, an ethylsulfanyl group, an isopropenylsulfanyl group, a dodecanylsulfanyl group, a cycloalkylsulfanyl group, a phenylsulfanyl group, or a benzylsulfanyl group; Groups: alkyldithio groups such as methyldithio group and ethyldithio group; alkenyldithio groups such as isopropenyldithio group; aryldithio groups such as phenyldithio group, and the like. The position and number of these substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

R ² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, or a structural unit represented by the formula (2). The alkyl group and alkenyl group may be linear or branched.

The number of carbon atoms of the alkyl group represented by R ^2, preferably 1 to 30, more preferably from 2 to 26, more preferably 4 to 20, more preferably 6 to 18, more preferably 10 to 16, 10 to 14 Is more preferable, and 12 to 14 is particularly preferable.
Examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, Examples include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group and the like. Among these, a dodecyl group is particularly preferable.

Moreover, as carbon number of the said cycloalkyl group, 3-12 are preferable, 5-8 are more preferable, and 6-7 are especially preferable.
Examples of the cycloalkyl group include a monocyclic cycloalkyl group and a polycyclic cycloalkyl group.
Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropyl group, a cyclohexyl group, and the like. Among these, a cyclohexyl group is preferable.
Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclododecanyl group, and the like.

Moreover, as carbon number of the said alkenyl group, 2-16 are preferable, 4-14 are more preferable, and 8-12 are more preferable.
Examples of the alkenyl group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group.

  Moreover, as carbon number of the said aryl group, 6-20 are preferable, 6-16 are more preferable, and 6-12 are especially preferable. Examples of such an aryl group include a phenyl group and a naphthyl group.

Moreover, as carbon number of the said aralkyl group, 7-30 are preferable, 7-24 are more preferable, 7-16 are still more preferable, and 7-10 are especially preferable.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, phenylheptyl group, phenyloctyl group, phenylnonyl group, phenyldecyl group, and naphthylmethyl group. Etc. Among these, a benzyl group is preferable.

The alkyl group, cycloalkyl group, alkenyl group, aryl group and aralkyl group may have a substituent. Examples of the substituent include the same substituents that may be substituted on the alkanediyl group represented by R ¹ . Among such substituents, a cycloalkyl group having 4 to 8 carbon atoms such as a cyclohexyl group is preferable.

Moreover, in the formula (2), examples of the alkanediyl group represented by R ⁵ include the same alkanediyl groups represented by R ¹ , but the carbon number thereof is preferably 1 to 20, and more Preferably it is 3-14, More preferably, it is 5-8.

Moreover, when R < ² > shows the structural unit represented by Formula (2), the structural unit (1) which the polyester of this invention has is represented by following formula (1-A).

(Each symbol in the formula is as defined above.)

Moreover, among R ² as described above, from the viewpoint of obtaining excellent heat resistance, the structural unit represented by the formula (2) is preferable, while sufficient heat resistance and curing while having a chemical structure with few crosslinking points. From the viewpoint of obtaining contractility, an alkyl group, a cycloalkyl group, and an aralkyl group are preferable.

R ³ each independently represents a hydrogen atom, an amino group or a monovalent hydrocarbon group. Such “monovalent hydrocarbon group” is a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The hydrocarbon group may have an unsaturated bond in the molecule and may be linear or branched.

As carbon number of the said aliphatic hydrocarbon group, 1-12 are preferable, 1-6 are more preferable, and 1-3 are especially preferable.
In addition, examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl, and an alkyl group is preferable. Examples of the alkyl group include the same alkyl groups represented by R ² .

Moreover, as carbon number of the said alicyclic hydrocarbon group, 3-12 are preferable, 3-8 are more preferable, and 3-6 are especially preferable.
Examples of the alicyclic hydrocarbon group include a cycloalkyl group and a cycloalkenyl group, and a cycloalkyl group is preferable. Examples of the cycloalkyl group include those similar to the cycloalkyl group represented by R ² .

Moreover, as carbon number of the said aromatic hydrocarbon group, 6-20 are preferable, 6-18 are more preferable, 6-12 are still more preferable, and 6-8 are especially preferable.
Moreover, as an aromatic hydrocarbon group, an aryl group is preferable. Examples of the aryl group include those similar to the aryl group represented by R ² .

  The monovalent hydrocarbon group may be substituted with a carboxyl group or a hydroxy group, and may have an ester bond, an ether bond or a carbonyl group.

Further, among R ³ as described above, a hydrogen atom and an alkyl group are preferable, and a hydrogen atom is particularly preferable.

R ⁴ represents an alkyl group, an alkenyl group, an alkoxy group, an alkoxyalkyl group, an aryloxyalkyl group or a structural unit represented by the formula (3). The alkyl chain in the alkyl group and alkenyl group, and the alkoxy group, alkoxyalkyl group, and aryloxyalkyl group may be linear or branched.

As carbon number of the alkyl group shown by R < ⁴ >, 1-16 are preferable, 1-12 are more preferable, 1-8 are still more preferable, 1-4 are especially preferable. Moreover, as carbon number of the said alkenyl group, 2-12 are preferable, 2-8 are more preferable, and 2-4 are especially preferable.
Examples of the alkyl group and alkenyl group include the same alkyl groups and alkenyl groups represented by R ² .

  Moreover, as carbon number of the said alkoxy group, 1-12 are preferable, 1-8 are preferable, and 1-4 are especially preferable. Examples of such an alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

  Moreover, as carbon number of the said alkoxyalkyl group, 1-12 are preferable, 1-8 are preferable, and 1-4 are especially preferable. Examples of such an alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, and a propoxyethyl group.

Moreover, as carbon number of the said aryloxyalkyl group, 7-30 are preferable, 7-22 are more preferable, 7-14 are still more preferable, 7-10 are especially preferable. Examples of such aryloxyalkyl groups include phenoxymethyl group, phenoxyethyl group, phenoxypropyl group, and the like. Among these, a phenoxymethyl group is preferable.
The aryloxyalkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. The position and number of the alkyl group are arbitrary, and when having two or more alkyl groups, the alkyl groups may be the same or different.

In formula (3), R ⁶ is preferably an alkanediyl group. Such an alkanediyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 2 to 3 carbon atoms. The bonding position of R ^{6 to} the benzene ring is not particularly limited, but the 4,4 ′ position is preferred.
The number of carbon atoms of the alkanediyl group represented by R ⁷ is preferably 1-12, more preferably 1-8, more preferably 1-4, particularly preferably 1 or 2. R ⁷ in formula (3) may be the same or different.
Examples of the alkanediyl group represented by R ⁶ and R ⁷ include the same alkanediyl groups represented by R ¹ .

Also, when showing the structural units R ⁴ is represented by the formula (3), structural units polyester has (1) of the present invention is represented by the following formula (1-B).

(Each symbol in the formula is as defined above.)

Among the R ⁴ as described above, from the viewpoint of obtaining excellent heat resistance, the structural unit represented by the formula (3) is preferable. On the other hand, sufficient heat resistance and cure shrinkage while having a chemical structure with few crosslinking points. From the viewpoint of obtaining the above, an alkoxyalkyl group and an aryloxyalkyl group are preferable.

A represents —S—, —S (═O) —, or —S (═O) ₂ —. Among these, -S- and -S (= O) ₂ -are preferable from the viewpoint of heat resistance.
N represents 1 or 2, but 1 is preferable.

Moreover, as a number average molecular weight ( _Mn ) of polyester of this invention, 1,000-100,000 are preferable, 2,500-50,000 are more preferable, 3,000-30,000 are especially preferable. Moreover, as _Mw / _Mn , 1-12 are preferable and 1-3 are more preferable. In addition, a number average molecular weight ( _Mn ) and _Mw / _Mn can be measured by the method as described in the Example mentioned later.
In addition, examples of the shape of the polyester of the present invention include a linear shape and a mesh shape.

Next, a method for synthesizing the polyester of the present invention will be described.
The polyester of the present invention can be synthesized by appropriately combining known reactions. For example, a polyester in which R ¹ is an alkanediyl group can be synthesized by the following method.

(Wherein R ¹ ′ represents an alkanediyl group, R ¹⁰ represents an alkenyl group, R ¹¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group; ² , R ³ and R ^{5 to} R ⁹ , A and n are as defined above.)

<Step 1-A>
Step 1-A is a step of obtaining compound (4-1-1-1) by reacting compound (8) and compound (9) in the presence of a radical initiator.

  Examples of the compound (8) used in this reaction include 2,8-dioxa-1- (isopropenyl) bicyclo [3.3.0] octane-3,7-dione.

Examples of the compound (9) used in this reaction include 1-dodecanethiol, cyclohexanethiol, benzylthiol, 1-octanethiol, cyclohexamethanethiol, 1-naphthalenethiol and the like.
In this reaction, the total amount of compound (9) used is not particularly limited, but is usually about 0.5 to 3 mol per 1 mol of compound (8).

Moreover, as a radical initiator, an azo-type thing is preferable. Examples of such radical initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate), and the like.
Moreover, although the total usage-amount of a radical initiator is not specifically limited, Usually, it is about 0.001-5 mol with respect to 1 mol of compounds (8).

In addition, this reaction is preferably performed in the presence of a solvent. Examples of the solvent include halogen solvents such as chlorobutane, bromohexane, dichloromethane, dichloroethane, chloroform, chlorobenzene, dichlorobenzene and trifluoromethylbenzene; aliphatic alkane solvents such as pentane, hexane, heptane and octane; cyclohexane and cycloheptane , Cycloalkane solvents such as decalin and norbornane; aromatic hydrocarbon solvents such as benzene, toluene, xylene and cumene; ester solvents such as ethyl acetate; ether solvents such as dibutyl ether, tetrahydrofuran and dimethoxyethane; acetone, Examples include ketone solvents such as methyl ethyl ketone; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; two or more selected from these. Among these, a halogen-based solvent is preferable from the viewpoint of reaction efficiency.
Moreover, what is necessary is just to set the total usage-amount of a solvent suitably. Usually, it is about 0.01-100 mass parts with respect to 1 mass part of compounds (8).

  The reaction time of this reaction is not particularly limited, but is usually about 0.5 to 72 hours, and the reaction temperature may be appropriately selected below the boiling point.

<Step 1-B>
Step 1-B is a step of obtaining a compound (4-1-1-2) by reacting the compound (8) and the compound (10) in the presence of a radical initiator.
Examples of the compound (10) used in this reaction include 1,6-hexanedithiol. Although the total usage-amount of compound (10) is not specifically limited, It is about 0.25-1.5 mol normally with respect to 1 mol of compounds (8).
This reaction may be performed in the same manner as in Step 1-A.

<Step 2-1>
Step 2-1 includes compound (4-1-1-1) obtained in Step 1-A or compound (4-1-1-2) obtained in Step 1-B (collectively referring to these compounds as compounds ( 4-1-1)) is converted to —S (═O) — to give compound (4-1-2).
Examples of the compound (4-1-1) used in this reaction include 2,8-dioxa-1- (2-dodecylsulfanylisopropyl) bicyclo [3.3.0] octane-3,7-dione (compound 4). -1--1-A), 2,8-dioxa-1- (2-cyclohexylsulfanylisopropyl) bicyclo [3.3.0] octane-3,7-dione (compound 4-1-1-B), 2 , 8-dioxa-1- (2-benzylsulfanylisopropyl) bicyclo [3.3.0] octane-3,7-dione (compound 4-1-1-C), 2,8-dioxa-1- (2 -Octylsulfanylisopropyl) bicyclo [3.3.0] octane-3,7-dione, 2,8-dioxa-1- (2-cyclohexylmethylsulfanylisopropyl) bicyclo [3.3.0] o Tan-3,7-dione, 2,8-dioxa-1- (2- (1-naphthyl) sulfanylisopropyl) bicyclo [3.3.0] octane-3,7-dione, bis [2- (2, 8-dioxabicyclo [3.3.0] octane-3,7-dionyl) isopropylsulfanyl] hexane (compound 4-1-1-D) and the like.

The step 2-1 is preferably performed in the presence of an oxidizing agent. The oxidizing agent is roughly classified into an organic oxidizing agent and an inorganic oxidizing agent.
Examples of the organic oxidizing agent include peroxides such as acetyl nitrate; percarboxylic acids such as peracetic acid, perbenzoic acid, and metachloroperbenzoic acid, as well as N-bromosuccinimide, iodosylbenzene, and the like. It is done. Among these, a percarboxylic acid type is preferable, and a perbenzoic acid type is more preferable.

  On the other hand, examples of the inorganic oxidizing agent include hydrogen peroxide, sodium metaperiodate, ozone, selenium dioxide, chromic acid, and dinitrogen tetroxide.

  Moreover, what is necessary is just to set the total usage-amount of an oxidizing agent suitably. Usually, it is about 0.05-1.5 mol with respect to 1 mol of compounds (4-1-1).

In addition, this reaction is preferably performed in the presence of a solvent. Examples of the solvent include the same solvents as those used in Step 1-A, and dichloromethane is particularly preferable.
Moreover, what is necessary is just to set the total usage-amount of a solvent suitably. Usually, it is about 0.01-100 mass parts with respect to 1 mass part of compounds (4-1-1).

  The reaction time of this reaction is not particularly limited, but is usually about 0.5 to 72 hours, and the reaction temperature may be appropriately selected below the boiling point, but is preferably 0 ° C. or lower.

<Step 2-2>
Step 2-2 converts -S (= O)-of the compound (4-1-2) obtained in Step 2-1 into -S (= O) _2- , and the compound (4-1-3) It is the process of obtaining. This reaction may be performed in the same manner as in Step 2-1.

  Examples of the compound (4-1-2) used in this reaction include 2,8-dioxa-1- (2-dodecylsulfinylisopropyl) bicyclo [3.3.0] octane-3,7-dione (compound 4). -1-2-A), 2,8-dioxa-1- (2-cyclohexylsulfinylisopropyl) bicyclo [3.3.0] octane-3,7-dione, 2,8-dioxa-1- (2- Benzylsulfinylisopropyl) bicyclo [3.3.0] octane-3,7-dione, 2,8-dioxa-1- (2-octylsulfinylisopropyl) bicyclo [3.3.0] octane-3,7-dione 2,8-dioxa-1- (2-cyclohexylmethylsulfinylisopropyl) bicyclo [3.3.0] octane-3,7-dione, 2,8-dioxa-1- 2- (1-naphthyl) sulfinylisopropyl) bicyclo [3.3.0] octane-3,7-dione, bis [2- (2,8-dioxabicyclo [3.3.0] octane-3,7 -Dionyl) isopropylsulfinyl] hexane and the like.

  In Step 2-1, compound (4-1-3) can also be obtained by using about 2 molar equivalents of an oxidizing agent relative to compound (4-1-1).

<Step 3-A>
Step 3-A includes compound (4-1-1), compound (4-1-2), or compound (4-1-3) (these compounds are collectively referred to as compound (4-1)), The polymerizable composition of the present invention containing the compound (5) is heated or irradiated with light to polymerize the compound (4-1) and the compound (5) (preferably copolymerization, more preferably alternating copolymerization). ). Thereby, the polyester which has a structural unit represented by Formula (1-1) is obtained.

Specific examples of the compound (4-1-1) and the compound (4-1-2) used in this reaction are as described above. In addition, examples of the compound (4-1-3) include 2,8-dioxa-1- (2-dodecylsulfonylisopropyl) bicyclo [3.3.0] octane-3,7-dione (compound 4-1). -3-A), 2,8-dioxa-1- (2-cyclohexylsulfonylisopropyl) bicyclo [3.3.0] octane-3,7-dione, 2,8-dioxa-1- (2-benzylsulfonyl) Isopropyl) bicyclo [3.3.0] octane-3,7-dione, 2,8-dioxa-1- (2-cyclohexylmethylsulfonylisopropyl) bicyclo [3.3.0] octane-3,7-dione, 2,8-dioxa-1- (2- (1-naphthyl) sulfonylisopropyl) bicyclo [3.3.0] octane-3,7-dione, bis [2- (2,8-dioxabic (B) [3.3.0] octane-3,7-dionyl) isopropylsulfonyl] hexane.
On the other hand, examples of the compound (5) used in this reaction include glycidyl phenyl ether, glycidyl (2-methylphenyl) ether, glycidyl (3-methylphenyl) ether, (4-isopropenylphenyl) (glycidyl) ether, and the like. Can be mentioned.

  This reaction is preferably performed in the presence of a polymerization initiator and a solvent described later. In such an embodiment, when the polymerizable composition described later contains a polymerization initiator and a solvent, it may be heated or irradiated with light as it is. When the polymerizable composition does not contain a polymerization initiator and a solvent, this reaction is performed. When performing, heating or light irradiation may be carried out by adding a polymerization initiator and a solvent to the polymerizable composition.

In this reaction, either heating or light irradiation may be performed, but heating is preferable. Although the temperature of this heating is not specifically limited, Usually, it is about 50-200 degreeC, Preferably, it is 80-150 degreeC.
The reaction time for this reaction is not particularly limited, but is usually about 1 to 360 hours, preferably 2 to 50 hours. Moreover, you may stop reaction with an acetic acid etc. as needed after the said heating or light irradiation.

<Step 3-B>
In step 3-B, the polymerizable composition of the present invention containing the compound (4-1) and the compound (6) is heated or irradiated with light, whereby the compound (4-1), the compound (6), and Is a step of polymerizing. Thereby, the polyester which has a structural unit represented by Formula (1-2) is obtained.
Examples of the compound (6) used in this reaction include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, 4,4′-bis (glycidyloxy) -1,1′-biphenyl, and the like.
This reaction may be performed in the same manner as in Step 3-A.

<Step 3-C>
In step 3-C, the polymerizable composition of the present invention containing the compound (4-1), the compound (5), and the compound (6) is heated or irradiated with light to thereby give the compound (4-1): In this step, the compound (5) and the compound (6) are polymerized. Thereby, polyester which has a structural unit denoted by a formula (1-3) is obtained.
This reaction may be performed in the same manner as in Steps 3-A and 3-B.

  In each of the above steps, isolation of each reaction product may be carried out by using usual means such as filtration, washing, drying, recrystallization, centrifugation, extraction with various solvents, neutralization, and chromatography as necessary. What is necessary is just to combine.

And the polyester of this invention obtained as mentioned above has sufficient joining property, and has the outstanding heat resistance.
Therefore, the polyester of the present invention can be used as various functional polymer materials including electronic materials, and in particular, in the fields of electric / electronic parts, automobiles, aircraft, construction, etc., sealants, adhesives, pressure-sensitive adhesives. It is useful as a bonding material. The compound (4) is useful as a synthetic intermediate for such polyester.

(Polymerizable composition)
Next, the polymerizable composition of the present invention will be described.
The polymeric composition of this invention contains the said compound (4) and 1 or more types chosen from the said compound (5) and the said compound (6). In addition, each of these compounds (4), compounds (5), and compounds (6) may be contained in one kind or two or more kinds.

In the formula (4), R ⁸ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group or a group represented by the formula (7).
Alkyl group represented by R ^8, cycloalkyl group, alkenyl group, aryl group, aralkyl group are the same as those represented by R ^2, respectively. R ⁸ is preferably a group represented by the formula (7) from the viewpoint of heat resistance. On the other hand, from the viewpoint of obtaining excellent heat resistance while being a linear polymer, an alkyl group, a cycloalkyl group, an aralkyl group. Is preferred.

  Moreover, as total content of a compound (4), 30-95 mass% is preferable in a polymeric composition, 40-90 mass% is more preferable, 50-80 mass% is still more preferable.

In formula (5), the alkyl group, alkenyl group, alkoxy group, alkoxyalkyl group, and aryloxyalkyl group represented by R ⁹ are the same as those represented by R ⁴ .
Note that n in the formula (6) may be the same or different.

Moreover, when R < ⁸ > shows group represented by Formula (7), the compound (4) used by this invention is represented by following formula (4-A).

(Each symbol in the formula is as defined above.)

In addition, the total content of the compound (5) and / or the compound (6) in the polymerizable composition is preferably 0.1 to 10 mol with respect to 1 mol of the compound (4) from the viewpoint of heat resistance. 0.1-5 mol is preferable and 0.1-3 mol is especially preferable.
Further, by using only the compound (5) out of the compound (5) and the compound (6), a polyester having sufficient heat resistance and curing shrinkage while having a chemical structure with few crosslinking points can be obtained. By using (6), a polyester having excellent heat resistance can be obtained.
When the compound (5) and the compound (6) are used in combination, the molar ratio of the compound (5) and the compound (6) contained in the polymerizable composition is usually 200: 1 to 1: 200. However, from the viewpoint of heat resistance and cure shrinkage, 20: 1 to 1:20 is preferable, 10: 1 to 1:10 is more preferable, 5: 1 to 1: 5 is further preferable, and 1.5: 1. ˜1: 3 is more preferred, and 1: 1 to 1: 2 is particularly preferred.

  In addition to the compounds (4) to (6), the polymerizable composition may contain a polymerization initiator (for example, a thermal polymerization initiator or a photopolymerization initiator) and a solvent. In addition, when a polymeric composition does not contain a polymerization initiator and a solvent, when synthesize | combining polyester, the polyester of this invention is compoundable by making a polymeric composition contain a polymerization initiator and a solvent.

Although the said polymerization initiator is not specifically limited, From a viewpoint of obtaining polyester efficiently, an anionic initiator is preferable.
Examples of the anion initiator include phosphine compounds such as triphenylphosphine, tricyclohexylphosphine and tri-n-butylphosphine; alkoxide compounds such as potassium tert-butoxide and sodium methoxide; potassium phenoxide and cesium phenoxide. Examples include phenoxide-based ones such as triethylamine, potassium acetate, and the like, and one or more can be used. Of these, phosphine-based ones are preferable, and triarylphosphine is more preferable. The aryl group preferably has 6 to 12 carbon atoms.

  Moreover, what is necessary is just to set the total content of the said polymerization initiator suitably. Usually, it is about 0.005-3 mol with respect to 1 mol of compound (4), Preferably it is 0.03-1 mol.

Moreover, as said solvent, the thing similar to the solvent used at the said process 1 is mentioned. Of these, ether solvents are preferable, and tetrahydrofuran is particularly preferable.
Moreover, what is necessary is just to set the total content of a solvent suitably. Usually, it is about 10 ^<-5 > -10 mass parts with respect to 1 mass part of compound (4), Preferably it is 10 ^<-5 > ^-10 < ^-1 > mass parts.

  And as above-mentioned, the polyester of this invention is easily compoundable by using the polymeric composition of this invention. Therefore, the polymerizable composition is particularly useful for bonding materials such as a sealant, an adhesive, and a pressure-sensitive adhesive.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

〔reagent〕
The reagents used in the examples are as shown below.
2,8-Dioxa-1- (2-dodecylsulfanylisopropyl) bicyclo [3.3.0] octane-3,7-dione (hereinafter referred to as isopropenyl bislactone) was obtained in Synthesis Example 1 described below. I used something.
1-dodecanethiol: manufactured by Wako Pure Chemical Industries, Ltd. cyclohexanethiol: manufactured by Tokyo Chemical Industry Co., Ltd. benzylthiol: manufactured by Tokyo Chemical Industry Co., Ltd. 1,6-hexanedithiol: Tokyo Chemical Industry Azobisisobutyronitrile (AIBN): Japanese Chlorobenzene manufactured by Kojun Pharmaceutical Co., Ltd .: Metachlorobenzoic acid manufactured by Wako Pure Chemical Industries, Ltd .: Glycidyl phenyl ether manufactured by Wako Pure Chemical Industries, Ltd .: Bisphenol A diglycidyl ether (BisA-GDE) manufactured by Tokyo Chemical Industry Co., Ltd .: Nippon Steel Chemical Co., Ltd. Triphenylphosphine: Wako Pure Chemical Industries, Ltd. Tetrahydrofuran: Wako Pure Chemical Industries, Ltd.

〔Analysis conditions〕
The conditions for each analysis in the examples are as follows.

<NMR spectrum>
^{The 1} H-NMR spectrum was measured by Varian Inova 400 (400 MHz) using CDCl ₃ as a solvent and tetramethylsilane as an internal standard substance.
^{The 13} C-NMR spectrum was measured with a Varian Inova 400 (100 MHz) using CDCl ₃ as a solvent and tetramethylsilane as an internal standard substance.

<IR spectrum>
The IR spectrum was measured by the ATR method with a NICOLET iS10 with a SMARTiTR sampling unit manufactured by Thermo Scientific.

<Molecular weight measurement>
The number average molecular weight (Mn) and dispersity (Mw / Mn) were measured at a measurement temperature of 40 ° C. by GPC (gel permeation chromatography) HLC-8320 GPC (manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent. The measured value is based on polystyrene.

<Thermogravimetric analysis>
Thermogravimetric analysis (TGA) was measured with a TG-DTA6200 manufactured by Seiko Instruments Inc. by using an aluminum pan and raising the temperature in a nitrogen stream of 50 mL / min at 10 ° C./min. In thermogravimetric analysis, T _d5 and T _d10 mean 5% weight reduction temperature and 10% weight reduction temperature of the compound, respectively.

<Differential scanning thermal analysis>
In differential scanning calorimetry (DSC), 10 mg of polyester was enclosed in an aluminum pan using a DSC6200 manufactured by Seiko Instruments Inc., and the temperature was increased from 50 ° C. to 300 ° C. at a rate of 5 ° C./min. It was measured.

Synthesis Example 1 Synthesis of Isopropenyl Bislactone In a 30 mL two-necked eggplant flask, 1.0 g (5.6 mmol) of 1,2,3-propanetricarboxylic acid and 2.6 g of bis (methacrylic acid) anhydride (17. 0 mmol), 0.14 g (1.1 mmol) of N, N-dimethyl-4-aminopyridine and 23 mg (0.17 mmol) of copper (II) chloride were added and reacted at 140 ° C. for 6 hours in a nitrogen atmosphere. . After completion of the reaction, unreacted bis (methacrylic acid) anhydride and by-product methacrylic acid were distilled off from the reaction mixture at 0.04 mmHg and 75 ° C. Next, the remaining mixture was dissolved in ethyl acetate, and this was added dropwise to 200 mL of diethyl ether to cause reprecipitation. After the precipitate was filtered off, diethyl ether was distilled off from the residue, and the residue was redissolved in ethyl acetate and separated and washed with an aqueous sodium hydrogen carbonate solution. Next, after the collected organic layer was dried with magnesium sulfate, the magnesium sulfate was filtered off, and the solvent was distilled off from the filtrate. This filtrate was dissolved in 50 mL of acetone, treated with 0.25 g of activated carbon (alkaline), and then the activated carbon was removed by filtration. Subsequently, acetone was distilled off from the filtrate, and recrystallization was performed using toluene to obtain isopropenyl bislactone in an isolated yield of 50.4%. The chemical structure of isopropenyl bislactone is shown below.

Example 1 Synthesis of 2,8-dioxa-1- (2-dodecylsulfanylisopropyl) bicyclo [3.3.0] octane-3,7-dione (Compound 4-1-1-A) In a 10 mL capacity ampoule , 0.30 g (1.65 mmol) of isopropenyl bislactone obtained in Synthesis Example 1, 0.33 g (1.63 mmol) of 1-dodecanethiol, 0.03 g (0.18 mmol) of AIBN, and 0.8 mL of chlorobenzene. After putting, it was deaerated and sealed, and reacted at 60 ° C. for 3 hours. After completion of the reaction, chlorobenzene was distilled off, and the residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 1/1) to obtain compound 4-1-1-A in an isolated yield of 89%. It was. The chemical structure and analysis results of Compound 4-1-1-A are shown below.

IR (neat): 2921, 2851, 1787, 1467, 1239, 1171, 1135, 970, 865 cm ^-1 .
¹ H NMR (CDCl ₃ , 400 MHz): δ0.88 (t, 3H, CH ₃ ), 1.20 (d, 3H, CH ₃ ), 1.25-1.57 (m, 20H, alkyl), 2.26 (m, 1H, CH), 2.40-2.65 and 2.85 (m, 2H, OCOCH ₂ and 4H SCH ₂ ), 3.03 (q, 2H, OCOCH ₂ ), 3.32 (m, 1H, CCH).
¹³ C NMR (CDCl ₃ , 100 MHz): δ14.5, 26.8, 27.0, 27.1, 31.9, 34.6, 34.7, 36.7, 37.0, 37.1, 42.1, 45.6, 117.2, 172.4, 172.5.

Example 2 Synthesis of 2,8-dioxa-1- (2-cyclohexylsulfanylisopropyl) bicyclo [3.3.0] octane-3,7-dione (compound 4-1-1-B) In a 10 mL capacity ampule After adding 0.30 g (1.65 mmol) of isopropenyl bislactone, 0.19 g (1.63 mmol) of cyclohexanethiol, 0.03 g (0.18 mmol) of AIBN, and 0.8 mL of chlorobenzene, the mixture was deaerated and sealed. Tube and react at 60 ° C. for 3 hours. After completion of the reaction, chlorobenzene was distilled off, and the residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 1/1) to obtain compound 4-1-1-B in an isolated yield of 72%. It was. The chemical structure and analysis results of Compound 4-1-1-B are shown below.

IR (neat): 2928, 1784, 1238, 1173, 1137, 1120, 1015, 969, 946, 889, 863, 794 cm ^-1 .
¹ H NMR (CDCl ₃ , 400 MHz): δ1.17 (d, 3H, CH ₃ ), 1.23-2.03 (m, 10H, cyclohexyl), 2.26 (m, 1H, CH), 2.42-2.51 (m, 1H , SCH ₂ ), 2.54 and 2.59 (m, 2H, OCOCH ₂ ), 2.57-2.67 (b, 1H, SCH), 2.88 and 2.90 (m, 1H, SCH ₂ ) 3.01 and 3.08 (m, 2H, OCOCH ₂ ) , 3.34 (m, 1H, CCH).
¹³ C NMR (CDCl ₃ , 100 MHz): δ14.5, 26.8, 27.0, 27.1, 31.9, 34.6, 34.7, 36.7, 37.0, 37.1, 42.1, 45.6, 117.2, 172.4, 172.5.

Example 3 Synthesis of 2,8-dioxa-1- (2-benzylsulfanylisopropyl) bicyclo [3.3.0] octane-3,7-dione (Compound 4-1-1-C) In a 10 mL capacity ampule After adding 0.30 g (1.65 mmol) of isopropenyl bislactone, 0.20 g (1.63 mmol) of benzylthiol, 0.03 g (0.18 mmol) of AIBN, and 0.8 mL of chlorobenzene, the mixture was deaerated and sealed. Tube and react at 60 ° C. for 6 hours. After completion of the reaction, chlorobenzene was distilled off, and the residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 1/1) to obtain compound 4-1-1-C in an isolated yield of 63%. It was. The chemical structure and analysis results of Compound 4-1-1-C are shown below.

IR (neat): 2981, 2937, 1782, 1495, 1453, 1422, 1317, 1052, 943, 863, 718, 692 cm ^-1 .
¹ H NMR (CDCl ₃ , 400 MHz): δ1.13 (d, 3H, CH ₃ ), 2.04 (m, 1H, CH), 2.33-2.39 (m, 1H, SCH ₂ ), 2.46-2.50 (m, 2H, OCOCH ₂ ), 2.74 (m, 1H, SCH ₂ ), 2.84-2.95 (m, 2H, OCOH ₂ ), 3.13 (m, 1H, CCH), 3.71 (s, 2H, SCH ₂ Ph), 7.23- 7.35 (m, 5H, Ph).
¹³ C NMR (CDCl ₃ , 100 MHz): δ13.5, 32.4, 35.3, 35.7, 35.9, 36.0, 37.2, 40.5, 116.1, 127.4, 128.8, 129.0, 138.0, 172.3, 172.4.

Example 4 Synthesis of 2,8-dioxa-1- (2-dodecylsulfinylisopropyl) bicyclo [3.3.0] octane-3,7-dione (compound 4-1-2-A) 1.16 g (3.00 mmol) of the compound 4-1-1-A obtained in Example 1 was charged into an open eggplant flask, and 30 mL of dichloromethane was poured and dissolved. Separately, 0.52 g (3.00 mmol) of metachloroperbenzoic acid (mCPBA) was charged into a 50 mL-volume eggplant flask, and 30 mL of dichloromethane was poured and dissolved. An mCPBA solution was added dropwise to the solution of compound 4-1-1-A in an ice bath, and the mixture was reacted at room temperature for 24 hours. After completion of the reaction, the solution was washed with a saturated aqueous sodium sulfite solution, a saturated aqueous sodium hydrogen carbonate solution, and water, and then the organic phase was dried over magnesium sulfate. After magnesium sulfate was filtered off and the solvent was distilled off, the residue was purified by silica gel column chromatography (eluent: ethyl acetate) to give compound 4-1-2-A in an isolated yield of 72%. The chemical structure and analysis results of Compound 4-1-2-A are shown below.

IR (neat): 2922, 2852, 1790, 1465, 1245, 1123, 1025, 972, 945 cm ^-1 .
¹ H NMR (CDCl ₃ , 400 MHz): δ 0.88 (t, 3H, CH ₃ CH ₂ CH ₂ ), 1.19-1.55 (m, 21H, CH ₂ CH ₂ CH ₂ and CH ₃ CH (-C) C) , 1.65-1.85 (m, 2H, SCH ₂ CH ₂ ), 2.50-2.85 (m, 6H, OC (= O) CH ₂ CH, CH ₃ CH (-C) C, SCH ₂ CH and SCH ₂ CH ₂ ) , 3.00-3.13 (m, 3H, OC (= O) CH ₂ CH and SCH ₂ CH), 3.25-3.39 (m, 1H, CCH (-CH ₂ ) CH ₂ ).
¹³ C NMR (CDCl ₃ , 100 MHz): δ14.2, 15.2, 16.1, 22.6, 22.8, 28.9, 29.5, 29.6, 29.7, 32.0, 53.6, 115.4, 172.3.

Example 5 Synthesis of 2,8-dioxa-1- (2-dodecylsulfonylisopropyl) bicyclo [3.3.0] octane-3,7-dione (compound 4-1-3-A) Two 50 mL volumes 0.40 g (1.00 mmol) of the compound 4-1-2-A obtained in Example 4 was charged into an open eggplant flask, and 10 mL of dichloromethane was poured and dissolved. Separately, 0.52 g (3.00 mmol) of mCPBA was charged into a 25 mL eggplant flask, and 10 mL of dichloromethane was poured and dissolved. A solution of mCPBA was added dropwise to the solution of compound 4-1-2-A in an ice bath, and the mixture was reacted at room temperature for 24 hours. After completion of the reaction, the solution was washed with a saturated aqueous sodium sulfite solution, a saturated aqueous sodium hydrogen carbonate solution, and water, and then the organic phase was dried over magnesium sulfate. After magnesium sulfate was filtered off and the solvent was distilled off, the residue was purified by silica gel column chromatography (eluent: ethyl acetate) to give compound 4-1-3-A in an isolated yield of 98%. The chemical structure and analysis results of Compound 4-1-3-A are shown below.

IR (neat): 2922, 2853, 1790, 1465, 1240, 1114, 1023, 971, 945 cm ^-1 .
¹ H NMR (CDCl ₃ , 400 MHz): δ 0.88 (t, 3H, CH ₃ CH ₂ CH ₂ ), 1.18-1.52 (m, 21H, CH ₂ CH ₂ CH ₂ and CH ₃ CH (-C) C) , 1.83 (m, 2H, SCH ₂ CH ₂ ), 2.56-2.72 (m, 2H, OC (= O) CH ₂ CH), 2.72-2.86 (m, 1H, OC (= O) CH ₂ CH), 2.92 -3.22 (m, 5H, SCH ₂ CH ₂ , SCH ₂ CH (-C) CH ₂ , OC (= O) CH ₂ CH), 3.29-3.39 (m, 1H, OC (= O) CH ₂ CH), 3.40-3.49 (m, 1H, SCH ₂ CH (-C) CH ₂ ).
¹³ C NMR (CDCl ₃ , 100 MHz): δ14.2, 14.4, 22.0, 22.7, 28.5, 29.1, 29.3, 29.4, 29.6, 29.7, 31.9, 35.3, 35.8, 35.9, 36.0, 52.6 54.8, 115.1, 172.2, 172.4.

Example 6 Synthesis of bis [2- (2,8-dioxabicyclo [3.3.0] octane-3,7-dionyl) isopropylsulfanyl] hexane (Compound 4-1-1-D) 10 mL capacity ampoule After adding 2.26 g (12.4 mmol) of isopropenyl bislactone, 983 mg (6.53 mmol) of 1,6-hexanedithiol, 102 mg (623 μmol) of AIBN, and 12.4 mL of chlorobenzene, deaeration and sealed tube And reacted at 60 ° C. for 3 hours. After completion of the reaction, chlorobenzene was distilled off, and the residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 1/1) to obtain compound 4-1-1-D in an isolated yield of 72%. It was. The chemical structure and analysis results of Compound 4-1-1-D are shown below.

IR (neat): 2928, 2853, 1785, 1459, 1237, 1168, 1035, 968, 864 cm ^-1 .
¹ H NMR (CDCl ₃ , 400 MHz): δ1.18 (d, 6H, CH ₃ ), 1.40 (m, 4H, alkyl), 1.59 (m, 4H, alkyl), 2.27 (m, 2H, CH), 2.40-2.65 and 2.85 (m, 4H, OCOCH ₂ and 8H SCH ₂ ), 3.05 (q, 4H, OCOCH ₂ ), 3.32 (m, 2H, CCH).
¹³ C NMR (CDCl ₃ , 100 MHz): δ13.5, 28.3, 29.4, 32.9, 33.1, 35.8, 36.1, 40.9, 116.2, 172.6.

Example 7 Synthesis of polyester (1)
In a 10 mL volume ampoule under a nitrogen atmosphere, the compound 4-1-1-A (92.6 mg, 0.24 mmol) obtained in Example 1, glycidyl phenyl ether (36.0 mg, 0.24 mmol), triphenylphosphine (2.5 mg, 9.0 μmol) and 0.1 mL of tetrahydrofuran were added, and after deaeration and sealing, a polymerization reaction was performed at 120 ° C. for 24 hours. After completion of the reaction, the reaction mixture was cooled, and then the reaction was stopped by adding a chloroform solution of acetic acid (1 vol%, 1 mL). This reaction solution was poured into methanol, and an oily product insoluble in methanol was collected and vacuum-dried to obtain polyester S1 with a yield of 71%. ¹ H-NMR spectrum of the obtained polyester S1 is shown in FIG. As a result of measuring the molecular weight, the number average molecular weight (Mn) of the polyester S1 was 6100, and the degree of dispersion (Mw / Mn) was 1.5. As a result of thermogravimetric analysis, T _d5 was −20 ° C. and T _d10 was 265 ° C.
Below, the chemical structure and analysis result (IR spectrum, < ¹ > H-NMR spectrum) of polyester S1 are shown.

IR (neat): 2924, 2853, 1741, 1716, 1599, 1497, 1457, 1374, 1243, 1173, 1050, 754, 691 cm ^-1 .
¹ H NMR (CDCl ₃ , 400 MHz): δ 0.88 (t, 3H, CH ₃ (dodecyl)), 1.10-1.73 (br, 23H, CH ₃ (isopropyl) and CH ₂ (alkyl)), 2.46 (br, 5H, CH ₂ COO, SCH ₂ , and CH (isopropyl)), 2.72-3.03 (br, 4H, CH ₂ COO and SCH ₂ ), 3.48 (s, 1H, CH), 4.06 (br, 2H, COOCH ₂ ) , 4.29-4.40 (br, 2H, CH ₂ OPh), 5.32 (s, 1H, COOCH), 6.87-7.26 (m, 5H, Ph).

Example 8 Synthesis of polyester (2)
In a 10 mL capacity ampoule under a nitrogen atmosphere, compound 4-1-1-B (110.3 mg, 0.37 mmol) obtained in Example 2, glycidyl phenyl ether (55.5 mg, 0.37 mmol), triphenylphosphine (3.9 mg, 14.8 μmol) and 0.2 mL of tetrahydrofuran were added, and after deaeration and sealing, a polymerization reaction was performed at 120 ° C. for 24 hours. After completion of the reaction, the reaction mixture was cooled, and then the reaction was stopped by adding a chloroform solution of acetic acid (1 vol%, 2 mL). This reaction solution was poured into methanol, and an oily product insoluble in methanol was collected and vacuum-dried to obtain polyester S2 in a yield of 80%. The ¹ H-NMR spectrum of the obtained polyester S2 is shown in FIG. As a result of measuring the molecular weight, the number average molecular weight (Mn) of the polyester S2 was 5000, and the dispersity (Mw / Mn) was 1.5. As a result of thermogravimetric analysis, T _d5 was −1 ° C. and T _d10 was 281 ° C.
Below, the chemical structure of polyester S2 and an analysis result (< ¹ > H-NMR spectrum) are shown.

¹ H NMR (CDCl ₃ , 400 MHz): δ 1.10-2.99 (m, 13H, CH ₃ (isopropyl) and CH ₂ (cyclohexyl)), 2.46-3.01 (m, 9H, CH ₂ COO, SCH ₂ , CH ( isopropyl)), 3.49 (s, 1H, CH), 4.06 (br, 2H, COOCH ₂ ), 4.19-4.45 (br, 2H, CH ₂ OPh), 5.31 (s, 1H, COOCH), 6.87-7.26 (m , 5H, Ph).

Example 9 Synthesis of polyester (3)
In a 10 mL capacity ampoule under a nitrogen atmosphere, compound 4-1-1-C (113.2 mg, 0.37 mmol) obtained in Example 3, glycidyl phenyl ether (55.5 mg, 0.37 mmol), triphenylphosphine (3.9 mg, 14.8 μmol) and 0.2 mL of tetrahydrofuran were added, and after deaeration and sealing, a polymerization reaction was performed at 120 ° C. for 24 hours. After completion of the reaction, the reaction mixture was cooled, and then the reaction was stopped by adding a chloroform solution of acetic acid (1 vol%, 2 mL). This reaction solution was poured into methanol, and an oily product insoluble in methanol was collected and vacuum-dried to obtain polyester S3 with a yield of 78%. The ¹ H-NMR spectrum of the obtained polyester S3 is shown in FIG. As a result of measuring the molecular weight, the number average molecular weight (Mn) of the polyester S3 was 4400, and the degree of dispersion (Mw / Mn) was 1.7. As a result of thermogravimetric analysis, T _d5 was 2 ° C. and T _d10 was 265 ° C.
The chemical structure and analysis result ( ¹ H-NMR spectrum) of polyester S3 are shown below.

¹ H NMR (CDCl ₃ , 400 MHz): δ 1.10 (s, 3H, CH ₃ ), 2.21-2.89 (m, CH ₂ COO, SCH ₂ , CH (isopropyl)), 3.40 (m, 1H, CH), 3.64 (s, 2H, SCH ₂ Ph), 4.05 (br, 2H, COOCH ₂ ), 4.15-4.48 (br, 2H, CH ₂ OPh), 5.31 (s, 1H, COOCH), 6.87-7.26 (m, 10H , Ph).

Example 10 Synthesis of polyester (4)
In a 10 mL capacity ampoule under a nitrogen atmosphere, compound 4-1-3-A (154.0 mg, 0.37 mmol) obtained in Example 5, glycidyl phenyl ether (55.5 mg, 0.37 mmol), triphenylphosphine (3.9 mg, 14.8 μmol) and 0.2 mL of tetrahydrofuran were added, and after deaeration and sealing, a polymerization reaction was performed at 120 ° C. for 24 hours. After completion of the reaction, the reaction mixture was cooled, and then the reaction was stopped by adding a chloroform solution of acetic acid (1 vol%, 2 mL). This reaction solution was poured into methanol, and an oily product insoluble in methanol was collected and vacuum-dried to obtain polyester S4 in a yield of 26%. FIG. 1- (d) shows the ¹ H-NMR spectrum of the obtained polyester S4. As a result of measuring the molecular weight, the number average molecular weight (Mn) of the polyester S4 was 4500, and the dispersity (Mw / Mn) was 1.3. As a result of thermogravimetric analysis, T _d5 was 6 ° C. and T _d10 was 276 ° C.
Below, the chemical structure and analysis result (IR spectrum, < ¹ > H-NMR spectrum) of polyester S4 are shown.

IR (neat): 2923, 2853, 1737, 1716, 1599, 1588, 1497, 1456, 1406, 1373, 1242, 1154, 1133, 753 cm ^-1 .
¹ H NMR (CDCl ₃ , 400 MHz): δ 0.8 (t, 3H, CH ₂ CH ₂ CH ₃ ), 1.06-1.41 (br, 21H, CH ₂ CH ₂ CH ₂ and CH ₃ CH (-C) C) , 1.62-1.83 (br, 2H, SCH ₂ CH ₂ ), 2.21-2.87 (br, 2H, OC (= O) CH ₂ CH), 3.37-3.65 (br, 1H, OC (= O) CH ₂ CH) , 3.85-4.49 (m, 5H, SCH ₂ CH ₂ , SCH ₂ CH (-C) CH ₂ , OC (= O) CH ₂ CH), 5.27 (br, 1H, CHCH ₂ OPh), 6.75-7.30 (br , 5H, Ph).

Example 11 Synthesis of polyester (5)
To a 10 mL capacity ampule, compound 4-1-1-D (380 mg, 0.739 mmol) obtained in Example 6, glycidyl phenyl ether (222 mg, 1.48 mmol), triphenylphosphine (7.75 mg, 29 0.5 μmol) and 0.74 mL of tetrahydrofuran, and then sealed and reacted at 120 ° C. for 24 hours. After completion of the reaction, the solvent and catalyst were removed by Soxhlet extraction using chloroform as a solvent, and the chloroform-insoluble part was dried to obtain polyester S5 (cured product) with an isolated yield of 93%. As a result of performing thermogravimetric analysis on the obtained polyester S5, T _d5 was 257 ° C. and T _d10 was 276 ° C. As a result of differential scanning calorimetry, the glass transition temperature (Tg) was 27 ° C.
The chemical structure and analysis result (IR spectrum) of polyester S5 are shown below.

IR (neat): 2929, 1733, 1713, 1598, 1587, 1495, 1455, 1409, 1372, 1238, 1152, 1046, 980, 886, 813, 753, 691 cm ^-1 .

Example 12 Synthesis of Polyester (6)
To a 10 mL capacity ampule, compound 4-1-1-D (380 mg, 0.739 mmol) obtained in Example 6, glycidyl phenyl ether (166 mg, 1.11 mmol), and BisA-DGE (62.8 mg, 0 .185 mmol), triphenylphosphine (7.75 mg, 29.5 μmol), and 0.74 mL of tetrahydrofuran were added, sealed, and reacted at 120 ° C. for 24 hours. After completion of the reaction, the solvent and catalyst were removed by Soxhlet extraction using chloroform as a solvent, and the chloroform-insoluble part was dried to obtain polyester S6 (cured product) with an isolation yield of 95%. As a result of performing thermogravimetric analysis on the obtained polyester S6, T _d5 was 259 ° C. and T _d10 was 280 ° C. As a result of differential scanning calorimetry, the glass transition temperature (Tg) was 36 ° C.
The chemical structure and analysis result (IR spectrum) of polyester S6 are shown below.

IR (neat): 2927, 1733, 1713, 1599, 1588, 1495, 1456, 1410, 1372, 1235, 1151, 1045, 980, 887, 813, 753, 691 cm ^-1 .

Example 13 Synthesis of Polyester (7)
A polyester was synthesized in the same manner as in Example 12 except that the amounts of glycidyl phenyl ether and BisA-DGE were changed.
That is, to a 10 mL capacity ampule, compound 4-1-1-D (380 mg, 0.739 mmol) obtained in Example 6, glycidyl phenyl ether (111 mg, 0.739 mmol), and BisA-DGE (126 mg, 0 369 mmol), triphenylphosphine (7.75 mg, 29.5 μmol) and 0.74 mL of tetrahydrofuran were added, and the tube was sealed and reacted at 120 ° C. for 24 hours. After completion of the reaction, the solvent and catalyst were removed by Soxhlet extraction using chloroform as a solvent, and the chloroform-insoluble part was dried to obtain polyester S7 (cured product) with an isolation yield of 97%. As a result of performing thermogravimetric analysis on the obtained polyester S7, T _d5 was 263 ° C. and T _d10 was 285 ° C. As a result of differential scanning calorimetry, the glass transition temperature (Tg) was 47 ° C.
Below, the analysis result (IR spectrum) of polyester S7 is shown.

IR (neat): 2928, 1732, 1713, 1599, 1506, 1495, 1412, 1372, 1224, 1151, 1045, 980, 829, 753, 691 cm ^-1 .

Example 14 Synthesis of Polyester (8)
A polyester was synthesized in the same manner as in Example 12 except that the amounts of glycidyl phenyl ether and BisA-DGE were changed.
That is, to a 10 mL capacity ampule, the compound 4-1-1-D (380 mg, 0.739 mmol) obtained in Example 6, glycidyl phenyl ether (55.5 mg, 0.369 mmol), and BisA-DGE (189 mg) were obtained. 0.554 mmol), triphenylphosphine (7.75 mg, 29.5 μmol) and 0.74 mL of tetrahydrofuran were added, sealed, and allowed to react at 120 ° C. for 24 hours. After completion of the reaction, the solvent and catalyst were removed by Soxhlet extraction using chloroform as a solvent, and the chloroform-insoluble part was dried to obtain polyester S8 (cured product) with an isolated yield of 99%. As a result of thermogravimetric analysis of the obtained polyester S8, T _d5 was 266 ° C. and T _d10 was 289 ° C. As a result of differential scanning calorimetry, the glass transition temperature (Tg) was 57 ° C.
The analysis result (IR spectrum) of polyester S8 is shown below.

IR (neat): 2928, 1733, 1712, 160, 1507, 1455, 1412, 1361, 1224, 1154, 1043, 980, 829, 751, 692 cm ^-1 .

Example 15 Synthesis of polyester (9)
To a 10 mL capacity ampule, compound 4-1-1-D (380 mg, 0.739 mmol) obtained in Example 6, BisA-DGE (251 mg, 0.739 mmol), and triphenylphosphine (7.75 mg, 29 0.5 μmol) and 0.74 mL of tetrahydrofuran, and then sealed and reacted at 120 ° C. for 24 hours. After completion of the reaction, the solvent and catalyst were removed by Soxhlet extraction using chloroform as a solvent, and the chloroform-insoluble part was dried to obtain polyester S9 (cured product) with an isolated yield of 98%. As a result of thermogravimetric analysis of the obtained polyester S9, T _d5 was 275 ° C. and T _d10 was 301 ° C. As a result of differential scanning calorimetry, the glass transition temperature (Tg) was 68 ° C.
Below, the chemical structure of polyester S9 and the analysis result (IR spectrum) are shown.

IR (neat): 2928, 1733, 1712, 1607, 1507, 1455, 1410, 1361, 1227, 1179, 1040, 982, 829, 750, 691 cm ^-1 .

  From the results of Examples 7 to 15, it was found that a polyester having excellent heat resistance can be synthesized by using a polymerizable composition containing compound (4) and compound (5) and / or compound (6). It was. Moreover, from this result, it was found that the compound (4) is useful as a synthetic intermediate for polyester.

Claims (7)

Polyester having a structural unit represented by the following formula (1).

[In the formula (1), R ¹ represents a single bond, an alkanediyl group or an alkenediyl group, and R ² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, or the following formula (2 )

(In the formula (2), R ⁵ represents an alkanediyl group, * represents a position bonded to A in the formula (1), and R ¹ , R ³ , R ⁴ , A and n are (It is synonymous with the thing in Formula (1).)
Each of R ³ independently represents a hydrogen atom, an amino group or a monovalent hydrocarbon group, and R ⁴ represents an alkyl group, an alkenyl group, an alkoxy group, an alkoxyalkyl group, Aryloxyalkyl group or the following formula (3)

(In formula (3), R ⁶ represents a single bond or an alkanediyl group, R ⁷ represents an alkanediyl group, and ** binds to a carbon atom adjacent to R ⁴ in formula (1). And R ¹ , R ² , R ³ , A and n are as defined in formula (1).
Wherein A represents —S—, —S (═O) — or —S (═O) ₂ —, and n represents 1 or 2. ] The polyester according to claim 1, wherein R ² is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a structural unit represented by formula (2). . A polymerizable composition comprising a compound represented by the following formula (4), and one or more selected from a compound represented by the following formula (5) and a compound represented by the following formula (6).

[In Formula (4), R ¹ represents a single bond, an alkanediyl group or an alkenediyl group, R ³ independently represents a hydrogen atom, an amino group or a monovalent hydrocarbon group, and R ⁸ represents , Hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, or the following formula (7)

(In Formula (7), R ⁵ represents an alkanediyl group, *** represents a position bonded to A in Formula (4), and R ¹ , R ^3, and A represent Formula (4). ) Same meaning as inside.)
And A represents —S—, —S (═O) — or —S (═O) ₂ —. ]

[In Formula (5), R ⁹ represents an alkyl group, an alkenyl group, an alkoxy group, an alkoxyalkyl group, or an aryloxyalkyl group, and n represents 1 or 2. ]

[In the formula (6), R ⁶ represents a single bond or an alkanediyl group, R ⁷ represents an alkanediyl group, and n is as defined above. ]   Furthermore, the polymeric composition of Claim 3 containing a polymerization initiator. The R ⁸ is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a group represented by the formula (7). Polymerizable composition. A compound represented by the following formula (4).

[In Formula (4), R ¹ represents a single bond, an alkanediyl group or an alkenediyl group, R ³ independently represents a hydrogen atom, an amino group or a monovalent hydrocarbon group, and R ⁸ represents , Hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, or the following formula (7)

(In Formula (7), R ⁵ represents an alkanediyl group, *** represents a position bonded to A in Formula (4), and R ¹ , R ^3, and A represent Formula (4). ) Same meaning as inside.)
And A represents —S—, —S (═O) — or —S (═O) ₂ —. ] The compound according to claim 6, wherein R ⁸ is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a group represented by formula (7).

Images