JP2021028371A - Polymer and epoxy resin - Google Patents

Abstract

To provide a polymer which can be easily produced from inedible biomass such as lignin and has good thermal performance.SOLUTION: A polymer includes a constituent unit derived from an indane-based compound represented by formula (1). In formula (1), R1 to R6 are H, or the like, and at least one of R1 to R4 is a methoxy group.SELECTED DRAWING: None

Description

The present invention relates to polymers and, for example, epoxy resins used to obtain polymers.

Due to the limited resources of petroleum and the occurrence of global environmental problems such as carbon dioxide emissions, the use of alternative resources has been required in recent years. The use of biomass is attracting attention as an alternative resource to petroleum. As the biomass, edible biomass is mainly used from the viewpoint of handleability, but edible biomass competes with the use as food. Therefore, there is a growing demand for the use of non-edible biomass such as lignin, and various studies have been conducted.
For example, in Patent Document 1 and Non-Patent Documents 1 and 2, an alkoxybisphenol monomer is synthesized from isoeugenol, dihydroeugenol (DHE), guaiacol, etc., which can be produced from lignin, and ester, epoxy resin, and epoxy curing are performed from the monomer. It is disclosed to synthesize a polymer such as a body.

International Publication No. 2019/002503

Eric D. Hernandez et al. “Synthesis and characterization of Bio-based Epoxy Resins Derived from Vanillyl Alcohol”, ACS Sustainable Chem. Eng. April 2016, pp. 4328-4339 Shou Zhao et al. “Renewable Epoxy Networks Derived from Lignin-Based Monomers: Effect of Cross-Linking Density”, ACS Sustainable Chem. Eng. April 2016, pp. 6082-6089

However, non-edible biomass-derived components such as lignin have low degradability, so that the process for synthesizing the polymer tends to be complicated. Further, the biomass-derived polymer has a problem that the performance is inferior to that of the petrochemical-derived polymer. For example, Non-Patent Document 1 discloses that an epoxy cured product synthesized from an alkoxybisphenol monomer has a significantly lower glass transition temperature than an epoxy cured product synthesized from bisphenol, and its thermal performance is not good. .. Non-Patent Document 2 also discloses that the glass transition temperature of the epoxy cured product synthesized from the alkoxybisphenol monomer is low. That is, it is difficult to put non-edible resources such as lignin into practical use not only in terms of ease of manufacture but also in terms of performance.

Therefore, an object of the present invention is to provide a polymer that can be easily produced from non-edible biomass such as lignin and has good thermal performance.

As a result of diligent studies, the present inventors have found that the above problems can be solved by introducing a structural unit derived from an indane compound having a specific structure into a polymer and an epoxy resin, and have completed the following invention. .. The present invention provides the following [1] to [10].
[1] A polymer containing a structural unit derived from an indane-based compound represented by the following formula (1).

In the formula (1), R ¹ , R ² , R ³ and R ⁴ are independently either hydrogen atoms or methoxy groups, and R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, respectively. Although ^{either, R 1, R 2, R} 3, and at least one of ^{R 4} is a methoxy group.
[2] The polymer according to the above [1], wherein ^{at least one of R 1} and R ² is a methoxy group, and at least one of R ³ and R ^{4 is a methoxy group.}
[3] The polymer according to the above [1] or [2], wherein the methoxy group is arranged at the ortho position with respect to the OH group.
[4] The polymer according to any one of the above [1] to [3], which is any one of an epoxy cured product, a phenoxy resin, a polyester resin, and a polycarbonate resin.
[5] The polymer according to any one of the above [1] to [4], wherein the polymer is a phenoxy resin having a structural unit represented by the following formula (3).

In the formula (3), R ^{1 to} R ⁶ are the same as described above.
[6] The polymer according to any one of the above [1] to [5], wherein the polymer is a polyester resin having a structural unit represented by the following formula (4-1).

In equation (4-1), R ^{1 to} R ⁶ are the same as above.
[7] The polymer according to any one of the above [1] to [6], which has a weight average molecular weight of 5000 or more.
[8] The polymer is a cured product of an epoxy resin and a curing agent.
The polymer according to any one of the above [1] to [4], wherein the epoxy resin has a structural unit derived from the indane compound and an epoxy group.
[9] An epoxy resin having a structural unit derived from an indane compound represented by the following formula (1) and an epoxy group.

In the formula (1), R ¹ , R ² , R ³ and R ⁴ are independently either hydrogen atoms or methoxy groups, and R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, respectively. Is one of.
[10] The epoxy resin according to the above [9], which is represented by the following formula (2).

In the formula (2), R ^{1 to} R ⁶ are the same as described above. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different from each other in a molecule, respectively. n is an integer greater than or equal to 0.

In the present invention, it is possible to obtain a polymer that can be easily produced from non-edible biomass such as lignin and has good thermal performance.

^{The 1} H-NMR spectrum of diisoeugenol obtained in Synthesis Example 1 is shown. ^{The 1} H-NMR spectrum of the epoxy resin obtained in Example 1 is shown. ^{The 1} H-NMR spectrum of the phenoxy resin obtained in Example 6 is shown. ^{The 1} H-NMR spectrum of the polyester resin obtained in Example 7 is shown.

Hereinafter, the present invention will be described in more detail using embodiments.
The polymer of the present invention contains a structural unit derived from an indane compound represented by the following formula (1).

In the formula (1), R ¹ , R ² , R ³ and R ⁴ are independently either hydrogen atoms or methoxy groups, and R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, respectively. Is one of. Further, ^{at least one of R 1} , R ² , R ³ and R ⁴ is a methoxy group.
In the present invention, the thermal performance of the polymer can be improved by introducing the structure of the above formula (1) into the polymer. In addition, the indane-based compound represented by the above formula (1) can be relatively easily produced from lignin, so that the productivity is also good.

^{In the formula (1), at least one of R 1} and R ² is a methoxy group, and at least one of R ³ and R ⁴ is from the viewpoint of ease of production from lignin, performance of the polymer, and the like. It is preferably a methoxy group.
Further, in the above formula (1), the methoxy group is preferably arranged at the ortho position with respect to the OH group. That is, ^{it is preferable that R 1} , R ² , R ³ and R ⁴ are all arranged at the ortho position with respect to the OH group. Therefore, it is preferable that the indane compound is a compound represented by the following formula (1-1). In the formula (1-1), it is more preferable that ^{R 1} and R ⁴ are methosiki groups, and R ² and R ^{3 are hydrogen atoms.}
Further, in each of the formulas (1) and (1-1), ^{it is preferable that at least one of R 5} and R ⁶ is a methyl group, and it is more preferable that both are methyl groups.
The compound represented by the formula (1) is more preferably a compound represented by the following formula (1-2). The compound represented by the formula (1-2) is generally called diisoeugenol.
The indane-based compound used in the polymer may be used alone or in combination of two or more.

In equation (1-1), R ^{1 to} R ⁶ are the same as above.

(Manufacturing method of indane compound)
The indane-based compound represented by the above formula (1) can be produced, for example, by dimerizing the phenol-based compound represented by the formula (1-3) as shown in the following reaction formula. The phenolic compound represented by the following formula (1-3) can be produced from biomass, and more specifically, it can be easily obtained by decomposing lignin.

In the formula (1-3), R ¹¹ and R ¹² are independently either a hydrogen atom or a methoxy group, and R ¹³ is either a hydrogen atom or a methyl group. When R ¹³ is a methyl group, the phenolic compound may be a cis form or a trans form.

As the phenolic compound represented by the above formula (1-3), it is preferable that at least one of ^{R 11} and R ^{12 is a methoxy group from the viewpoint of ease of production from lignin and the like.} Further, the methoxy group is preferably arranged at the ortho position with respect to the OH group. Further, R ¹³ is preferably a methyl group. Therefore, the compound represented by the formula (1-3) is preferably a compound represented by the following formula (1-4). The compound represented by the formula (1-4) is a compound generally called isoeugenol. Isoeugenol may be a cis form or a trans form, but a trans form is common. When isoeugenol is used as the raw material phenolic compound, diisoeugenol represented by the above formula (1-2) can be obtained as the above-mentioned indane-based compound.

The dimerization of the phenolic compound can be carried out by a known method, but it is preferably carried out in the presence of an acid substance. By carrying out the reaction in the presence of an acid substance, the indane compound represented by the above formula (1) can be obtained in high yield. Acid substances that can be used include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid trifluoride, iron chloride (FeCl ₃ ), boron trifluoride (for example, BF ₃ and OEt ₂ ), and silica sulfuric acid (SiO _2- OSO _3). H), acidic ion exchange resin, activated clay and the like. One type of acid substance may be used alone, or two or more types may be used in combination. Among these, hydrochloric acid, sulfuric acid, and phosphoric acid are mentioned from the viewpoint of ease of production, production efficiency, and the like, and hydrochloric acid is more preferable.
The amount of the acid substance is not particularly limited, but is, for example, 0.01 to 1 mol, preferably 0.05 to 0.5 mol, and more preferably 0.08 to 0.3 mol with respect to 1 mol of the phenolic compound. Is.

The dimerization of the phenolic compound is generally carried out in a solvent, for example, an alkanol solvent such as methanol, ethanol, n-propanol and isopropanol, a polyalkylene glycol such as polyethylene glycol and polypropylene glycol, acetonitrile and tetrahydrofuran. , Monoglyme, diglyme and other polar solvents are preferable, and from the viewpoint of ease of production, production efficiency and the like, alkanol-based solvents are preferable, and methanol is particularly preferable. From the viewpoint of reactivity and production efficiency, the amount of the solvent used is preferably 0.1 to 10 and more preferably 0.5 to 3 in terms of mass ratio with respect to, for example, a phenolic compound.
The reaction temperature at the time of dimerization is preferably 0 ° C. to 100 ° C., more preferably 20 to 80 ° C. from the viewpoint of reactivity and production efficiency. The dimerization reaction is preferably carried out at the above reaction temperature for about 0.5 to 24 hours, more preferably for 1 to 15 hours.

The polymer of the present invention may contain a structural unit derived from the indane compound represented by the formula (1), but preferably contains a plurality of the structural units. The structural unit derived from the indane compound in the polymer of the present invention is preferably represented by the following formula (1-5).

In equation (1-5), R ^{1 to} R ⁶ are as described above.

Further, the polymer of the present invention preferably contains a structural unit derived from a compound other than the indane-based compound (hereinafter, also referred to as “compound (X)”). The polymer of the present invention preferably has a repeating unit represented by the following formula (1-6) by reacting compound (X) with an indane-based compound. That is, it is preferable that the polymer of the present invention is provided with the structural unit derived from the indane compound and the structural unit derived from the compound (X) alternately. In the polymer of the present invention, various performances can be imparted to the polymer by using various compounds as the compound (X).

In the formula (1-6), R ^{1 to} R ⁶ are as described above, and X is a structural unit derived from the compound (X).

The weight average molecular weight (Mw) of the polymer of the present invention is, for example, 5000 or more, preferably 7500 or more. By setting the weight average molecular weight to these lower limit values or more, the thermal performance and mechanical performance of the polymer can be improved. The weight average molecular weight (Mw) of the polymer is, for example, 2 million or less, preferably 1 million or less, from the viewpoint of improving ease of production and various performances.
The molecular weight distribution (Mw / Mn) of the polymer is not particularly limited, but is, for example, 1 to 10, preferably 1.5 to 7.
In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) described later were obtained in terms of standard polystyrene by the gel permeation chromatography (GPC) method as shown in Examples described later. It is a thing. Further, when the polymer has a three-dimensional network structure like an epoxy cured product described later, it is generally difficult to measure the weight average molecular weight (Mw) and the number average molecular weight (Mn).

The polymer of the present invention is preferably any of a cured epoxy resin, a phenoxy resin, a polyester resin, and a polycarbonate resin. By using any of these, the polymer can be easily produced, and various performances such as the thermal performance of the polymer can be easily improved.
The present invention also provides an epoxy resin having a structural unit derived from an indane compound represented by the above formula (1) and an epoxy group in order to obtain the above-mentioned cured epoxy body, phenoxy resin and the like.
Hereinafter, first, the epoxy resin will be described in detail.

[Epoxy resin]
The epoxy resin is preferably a reaction product of the indane compound represented by the above formula (1) and the epoxy compound. Since the indane-based compound represented by the formula (1) is as described above, the description thereof will be omitted. The epoxy compound may be a compound having an epoxy group and a functional group capable of reacting with a phenolic hydroxyl group, but the functional group is preferably epihalohydrin, which is a halogen group. The phenolic hydroxyl group is a hydroxyl group directly bonded to the aromatic ring. Examples of epihalohydrin include epifluorohydrin, epichlorohydrin, epibromohydrin, and epiiodohydrin, and among these, epichlorohydrin is preferable in terms of reactivity and economy.

The epoxy resin has a structural unit derived from the above-mentioned indane compound and an epoxy group. Further, the epoxy resin has a structural unit derived from an epoxy compound, and the structural unit derived from the epoxy compound has a structure in which an epoxy group is ring-opened and added to a hydroxyl group in addition to the structural unit having an epoxy group (for example). , -CH ₂ CHOHCH _2- ) may be included. The epoxy resin preferably has two or more epoxy groups, and more preferably has two epoxy groups. Epoxy groups may be present at both ends of the epoxy resin.
Specifically, the epoxy resin is preferably a compound represented by the following formula (2). As shown in the formula (2) below, the epoxy resin has a plurality of structural units derived from the indane compound when n is 1 or more, and can be said to be a polymer.

In equation (2), R ^{1 to} R ⁶ are the same as above. A plurality of R ¹ in the one molecule, may be the same as each other or may be different. R ² to R ⁶ is the same. n may be an integer of 0 or more, but n is preferably 0 to 100, more preferably 0 to 10, and even more preferably 0 to 5 from the viewpoint of the reactivity of the epoxy resin and the ease of manufacturing the epoxy resin. , Most preferably 0. The epoxy resin is preferably a compound represented by the following formula (2-1).

In equation (2-1), R ^{1 to} R ⁶ are the same as above.

In each of the formulas (2) and (2-1), it is preferable that at least one of ^{R 1} and R ² is a methoxy group and at least one of R ³ and R ^{4 is a methoxy group.}
Further, in each of the above formulas (2) and (2-1), ^{the methoxy groups of R 1} , R ² , R ³ and R ⁴ are arranged at the ortho position with respect to the oxygen atom derived from the phenolic hydroxyl group. Is preferable. Therefore, the epoxy resin is preferably a compound represented by the following formula (2-2). In the formula (2-2), it is more preferable that ^{R 1} and R ⁴ are metosiki groups, and R ² and R ^{3 are hydrogen atoms.}
Further, in each of the formulas (2), (2-1) and (2-2), ^{it is preferable that at least one of R 5} and R ⁶ is a methyl group, and it is more preferable that both are methyl groups. The epoxy resin is more preferably a compound represented by the following formula (2-3).

In equation (2-2), R ^{1 to} R ⁶ are the same as above.

The epoxy resin may be a reaction product of an indane-based compound, an epoxy compound, and a compound other than these (another compound (Z1)). That is, the epoxy resin may have a structural unit derived from an indane compound, a structural unit derived from another compound (Z1), and a structural unit derived from an epoxy compound. Examples of the other compound (Z1) include a compound having two functional groups capable of reacting with an epoxy group, and specific examples thereof include a compound having two hydroxyl groups.
When it has a structural unit derived from another compound (Z1), either a structural unit derived from an indane compound or a structural unit derived from another compound (Z1) and a structural unit derived from an epoxy compound are alternately provided. I hope it will be done. However, also in this case, it is preferable that a structural unit derived from an epoxy compound is provided at both ends and an epoxy group is provided at both ends.

The compound having two hydroxyl groups as the compound (Z1) is preferably an aromatic dihydroxy compound having two phenolic hydroxyl groups directly bonded to the aromatic ring. Specific examples of the aromatic dihydroxy compound include hydroquinone, resorcinol, 2,2'-dihydroxydiphenyl, 3,3'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl, 1,5-dihydroxynaphthalene, and 1,6-dihydroxynaphthal. Naphthalene, 1,7-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4' −Dihydroxydiphenyl ether, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4) -Hydroxyphenyl) Hexafluoropropane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) diphenylmethane, 1,1 Examples thereof include −bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and bis (4-hydroxyphenyl) sulfone (bisphenol S). The aromatic dihydroxy compound may be used alone or in combination of two or more.

The ratio of the structural unit derived from the indane compound to the total amount of the structural unit derived from the indane compound and the structural unit derived from the other compound (Z1) in the epoxy resin is preferably 50% by mass or more, more preferably 80% by mass or more. It is preferable, and 100% by mass is most preferable. By increasing the amount of the structural unit derived from the indane compound in this way, the effect of introducing the structural unit derived from the indane compound can be appropriately exhibited. In addition, the proportion of biomass-derived epoxy resin (biorate) can be increased.

(Epoxy resin manufacturing method)
The epoxy resin can be produced by reacting an indane compound with an epoxy compound. The indane compound and the epoxy compound may be mixed and reacted in a reactor, for example. In this production method, the amount of the epoxy compound added to 1 mol of the indane compound is preferably more than 1 mol. By increasing the addition amount of the epoxy compound to more than 1 mol, it becomes easy to make both ends a structural unit derived from the epoxy compound, and it becomes easy to obtain the compound represented by the above formula (2). Further, from the viewpoint of using both ends as a constituent unit derived from an epoxy compound and reducing the number of n, the amount of the epoxy compound added is preferably more than 2 mol, more preferably 5 mol or more, still more preferably. Is 10 mol or more, more preferably 15 mol or more.
Further, from the viewpoint of facilitating the removal of the unreacted epoxy compound after the reaction and increasing the production efficiency, the amount of the epoxy compound added is preferably 100 mol or less, more preferably 100 mol or less, based on 1 mol of the indane compound. It is 50 mol or less, more preferably 30 mol or less, still more preferably 25 mol or less.

The reaction between the indane compound and the epoxy compound is preferably carried out in the presence of a catalyst. Examples of the catalyst include quaternary ammonium salts such as benzyltriethylammonium chloride, benzyltriethylammonium bromide, tetra-n-butylammonium fluoride, and tetra-n-butylammonium bromide. The catalyst may be used alone or in combination of two or more. The amount of the catalyst added is preferably 0.01 to 2 mol, more preferably 0.05 to 1 mol, still more preferably 0.1 to 0.5 mol, based on 1 mol of the indane compound.
The above reaction can be carried out without a solvent, but can also be carried out in the presence of a solvent. As the reaction solvent, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogen solvent, an ester solvent, an ether solvent and the like can be used. Further, the above reaction may be carried out in the presence of a small amount of water.
The reaction is carried out, for example, at 40 to 150 ° C., preferably 60 to 100 ° C., for example, 30 minutes to 24 hours, preferably 2 to 12 hours.
When the epoxy resin contains a structural unit derived from another compound (Z1) such as a bisphenol compound, it is preferable to replace a part of the indane compound with another compound (Z1) to carry out the reaction.

[Epoxy cured product]
The epoxy cured product of the present invention is a cured product of an epoxy resin and a curing agent. The epoxy resin used for the cured epoxy product of the present invention may have a structural unit derived from the above-mentioned indane compound and an epoxy group. The details of the epoxy resin are as described above.
The curing agent that can be used in the epoxy cured product is not particularly limited as long as it can cure the epoxy resin, but a compound that reacts with the epoxy resin to form a three-dimensional network structure (network polymer) is preferable. ..

Examples of the curing agent include amine-based curing agents. Examples of the amine-based curing agent include polyamines such as aliphatic polyamines and aromatic polyamines. Examples of the aliphatic polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tetraethylenepentamine, dimethylaminopropylamine, bishexamitylenetriamine, cyclohexylaminopropylamine, aminoethylethanolamine and monohydroxyethyl. Diethylenetriamine, bishydroxyethyldiethylenetriamine, N- (2-hydroxypropyl) ethylenediamine, hexamethylenediamine, diethyleneglycolbis (3-aminopropyl) ether, diethylaminopropylamine, 3,9-bis (3-aminopropyl) -2,4 , 8,10-Tetraspoxaspiro [5,5] undecane, mentandiamine, isophoronediamine, 4,4'-methylenebis (cyclohexylamine), bis (4-amino-3-methylcyclohexyl) methane, N-aminoethyl Examples include piperazine.
The aromatic polyamine is an amine having an aromatic ring, and specific examples thereof include various xylylenediamines such as phenylenediamine, diaminodiphenylmethane, diaminoanisole, toluenediamine, and metaxylylenediamine, and diaminodiphenylsulphon. ..

Further, the amine-based curing agent may be an imidazole-based curing agent, an amidamine-based curing agent, or the like. Examples of the imidazole-based curing agent include 2-methylimidazole, 2-ethyl imidazole, 2-undecyl imidazole, 2,4-dimethyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, and 1,2-diethyl imidazole. , 2-Phenyl-4-methylimidazole, 2,4,5-triphenylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methyl Imidazole, 1-cyanoethyl-2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-aryl-4,5-diphenylimidazole, 2,4-diamino- 6- [2'-methylimidazolyl- (1)']-ethyl-S-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1)']-ethyl-S -Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1)']-ethyl-S-triazine isocyanuric acid adduct, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. Can be mentioned. Examples of the amidoamine-based curing agent include dicyandiamide.
Further, the curing agent may be other than the amine-based curing agent. Examples of the curing agent other than the amine-based curing agent include polyamide resins which are condensates of dimer or trimer acid and polyamine, Lewis acids such as boron trifluoride-amine complex, phenol or a derivative thereof. Also, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, chlorendic anhydride, dodecinyl succinic anhydride, methyltetrahydrophthalic anhydride, methylendomethylene. An acid anhydride-based curing agent such as methylhexahydrophthalic anhydride represented by tetrahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride may also be used.
These curing agents may be used alone or in combination of two or more.

As the curing agent, among the above, amine-based curing agents are preferable, and polyamines are particularly preferable. The polyamines preferably have two or more primary amino groups and secondary amino groups in total in one molecule, preferably have at least one primary amino group, and more preferably have a primary amino group. Have two or more. The total number of primary amino groups and secondary amino groups in one molecule of polyamines is not particularly limited, but is, for example, 8 or less, preferably 5 or less, and more preferably 3 or less.

The blending amount of the curing agent is, for example, 1 to 100 parts by mass, preferably 2 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin. When these lower limit values or more are set, curing can be performed appropriately. For example, when a three-dimensional network structure is formed, the structure becomes strong and the mechanical and thermal properties tend to be good. Further, by setting these upper limit values or less, it is possible to prevent the amount of the curing agent from becoming larger than necessary, and the mechanical and thermal properties tend to be improved.
The amount of the curing agent blended is adjusted to the epoxy equivalent of the epoxy resin, and when an amine-based curing agent is used, the amount of active hydrogen of the amine-based curing agent (that is, the hydrogen atom bonded to the nitrogen atom in the amino group). It may be adjusted appropriately. For example, the ratio of the number of active hydrogens to the number of epoxy groups may be adjusted to be close to 1 or 1, specifically 0.5 to 2, preferably 0.75 to 1.5, more preferably. It is 0.9 to 1.1.

The glass transition temperature (Tg) of the epoxy cured product is preferably 90 ° C. or higher. The thermal performance can be improved by setting the temperature to 90 ° C. or higher. The glass transition temperature (Tg) of the cured epoxy product is preferably 120 ° C. or higher, more preferably 135 ° C. or higher. When Tg is 135 ° C. or higher, the epoxy cured product can be imparted with thermal performance equivalent to that of petrochemical products such as those derived from bisphenol A. The glass transition temperature (Tg) of the cured epoxy product is not particularly limited, but may be, for example, 200 ° C. or lower, or 160 ° C. or lower. The glass transition temperature (Tg) may be measured by a differential scanning calorimeter as shown in Examples described later.

The epoxy cured product is not particularly limited, but can be produced by mixing an epoxy resin and a curing agent and heating them as necessary. The heating temperature is not particularly limited, but is, for example, room temperature (23 ° C.) to 300 ° C., preferably 40 ° C. to 250 ° C., and heating is performed within the above temperature range for, for example, 10 minutes to 13 hours, preferably 1 to 6 hours. Good. The heating temperature may be gradually increased as the curing progresses. Further, the mixture of the epoxy resin and the curing agent may be diluted by adding a solvent or the like. When diluted with a solvent, the solvent may be appropriately dried and removed by the above heating.

[Phenoxy resin]
The phenoxy resin of the present invention contains a structural unit derived from an indane compound and a structure in which an epoxy group is ring-opened and added to a hydroxyl group (for example, −CH ₂ CHOHCH _2- ). Specifically, it is preferable that the structural unit derived from an indane compound and the structural unit derived from an epoxy compound have a structure in which an epoxy group is ring-opened and added to a hydroxyl group. In the phenoxy resin, structural units derived from indane compounds and structural units derived from epoxy compounds are generally provided alternately. The epoxy compound used in the phenoxy resin is as described in the above epoxy resin.
The terminal of the phenoxy resin may be a structural unit derived from an indane compound or a structural unit derived from an epoxy compound. Further, the terminal may be sealed with a compound other than an indane compound or an epoxy compound such as a polymerization inhibitor. The phenoxy resin of the present invention can be used, for example, as a thermoplastic resin.

The phenoxy resin of the present invention preferably has a structural unit represented by the following formula (3).

In the formula (3), R ^{1 to} R ⁶ are the same as described above.
The phenoxy resin may have two or more repeating units having the structural unit represented by the formula (3) as a repeating unit, and the number of repeating units is preferably 10 or more, more preferably 20 or more. By setting these lower limits or more, various mechanical and thermal physical properties are improved, and the resin can be suitably used as a thermoplastic resin. The number of repeating units of the structural units in the phenoxy resin is not particularly limited, but is, for example, 50,000 or less, preferably 10,000 or less, and more preferably 5,000 or less.

In formula (3), it is more preferable that at least one of ^{R 1} and R ² is a methoxy group and at least one of R ³ and R ^{4 is a methoxy group.}
Further, in the above formula (3), it is preferable that the methoxy group is arranged at the ortho position with respect to the oxygen atom derived from the phenolic hydroxyl group. Therefore, the epoxy resin is preferably a compound having a structural unit represented by the following formula (3-1). In the formula (3-1), it is more preferable that ^{R 1} and R ⁴ are methosiki groups, and R ² and R ^{3 are hydrogen atoms.} In each of the formulas (3) and (3-1), ^{it is preferable that at least one of R 5} and R ⁶ is a methyl group, and it is more preferable that both are methyl groups. The epoxy resin is more preferably a compound having a structural unit represented by the following formula (3-2).

In equation (3-1), R ^{1 to} R ⁶ are the same as above.

Similar to the above epoxy resin, the phenoxy resin is derived from a constituent unit derived from an indan compound, a constituent unit derived from an epoxy compound, and a compound other than the epoxy compound and the indan compound (also referred to as “other compound (Z2)”). It may have a structural unit of. In this case, any of the structural units derived from the indane-based compound and the structural units derived from other compounds may be alternately provided with the structural units derived from the epoxy compound.
Examples of the other compound (Z2) include compounds having two functional groups capable of reacting with an epoxy group, and specific examples thereof include compounds having two hydroxyl groups, preferably aromatic compounds having two phenolic hydroxyl groups. It is a dihydroxy compound. Specific examples of the aromatic dihydroxy compound are as described above.
The ratio of the structural units derived from the indane compound to the total amount of the structural units derived from the indane compound and the structural units derived from other compounds in the phenoxy resin is preferably 50% by mass or more, more preferably 80% by mass or more, and 100%. Most preferably by mass%. As described above, by increasing the amount of the structural unit derived from the indane compound, the effect of introducing the structural unit derived from the indane compound can be appropriately exhibited, and the biorate in the phenoxy resin can be increased.

The glass transition temperature (Tg) of the phenoxy resin is preferably 75 ° C. or higher. The thermal performance can be improved by setting the temperature to 75 ° C. or higher. Further, from the viewpoint of improving the thermal performance, the glass transition temperature (Tg) of the phenoxy resin is preferably 85 ° C. or higher, more preferably 90 ° C. or higher. The glass transition temperature (Tg) of the phenoxy resin is not particularly limited, but is, for example, 180 ° C. or lower.

(Manufacturing method of phenoxy resin)
Like the epoxy resin, the phenoxy resin can be produced by reacting an indan compound with an epoxy compound, but it is preferably produced by reacting the above-mentioned epoxy resin with an indan compound in the presence of a catalyst. .. Here, as described above, the epoxy resin used preferably has a small n, and particularly preferably 0, from the viewpoint of reactivity and the like. Therefore, the reaction between the epoxy resin and the indane compound is preferably the following reaction formula.

In the above reaction formula, but R ¹ to R ⁶ are as defined above, R ¹ of R ¹ and indane compound of the epoxy resin may be different may be the same as each other. R ² to R ⁶ is the same.

The above reaction may be carried out by mixing, for example, an epoxy resin, an indane-based compound, and a catalyst and heating them in a reaction vessel or the like. The reaction can be carried out without solvent, but can also be carried out in the presence of solvent. As the reaction solvent, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogen solvent, an ester solvent, an ether solvent and the like can be used. The reaction is, for example, 60 to 250 ° C., preferably 100 to 200 ° C., and the reaction time is, for example, 30 minutes to 12 hours, preferably 1 to 8 hours.

Examples of the catalyst used when reacting the epoxy resin with the indan compound include a quaternary phosphonium salt, a quaternary ammonium salt, a sulfonium salt, an iodonium salt and the like, and among these, the quaternary phosphonium salt is used. preferable. Examples of the quaternary phosphonium salt include phosphonium bromide and phosphonium chloride, and phosphonium bromide is more preferable. Specific examples of the quaternary phosphonium salt include tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, methyltriphenylphosphonium bromide, methyltriphenylphosphonium chloride and the like.
Examples of the quaternary ammonium salt include benzyltriethylammonium chloride, benzyltriethylammonium bromide, tetra-n-butylammonium fluoride, tetra-n-butylammonium bromide and the like.
Examples of the sulfonium salt include trimethylsulfonium chloride, trimethylsulfonium bromide, trimethylsulfonium iodide, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium iodide and the like. Examples of the iodonium salt include diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium iodide and the like.
These catalysts may be used alone or in combination of two or more.

The amount of the quaternary phosphonium salt added in the above reaction is, for example, 0.01 to 0.5 mol, preferably 0.02 to 0.3 mol, based on 1 mol of the total amount of the epoxy resin and the indane compound. ..
The amount of the indan compound added to 1 mol of the epoxy resin is, for example, 0.5 to 2 mol, preferably 0.7 to 1.4 mol, and more preferably 0.9 to 1.1 mol.

When the phenoxy resin has a structural unit derived from the other compound (Z2), in the above method, at least a part of the indane-based compound is used, and the other compound (Z2) (specifically, a compound having two hydroxyl groups). ) And the above reaction should be performed.
Further, an epoxy resin having a structural unit derived from another compound (Z2) is synthesized, and the epoxy resin is replaced with at least a part of the epoxy resin having the structural unit represented by the above formula (1) to carry out the above reaction. May be good.
Further, at least a part of the indane-based compound is replaced with another compound (Z2), and an epoxy resin having a structural unit derived from the other compound (Z2) is an epoxy resin having a structural unit represented by the above formula (1). The above reaction may be carried out by substituting at least a part of.

[Polyester resin]
The polyester resin of the present invention is a polycondensate of a dihydroxy compound and a dicarboxylic acid, and the dihydroxy compound contains the above-mentioned indane compound. Therefore, the polyester resin has a structural unit derived from an indane compound and a structural unit derived from a dicarboxylic acid. Specifically, the polyester resin preferably has a structural unit represented by the following formula (4).

In the formula (4), R ^{1 to} R ⁶ are the same as described above, and the structural unit represented by −CO−Y−CO− is a structural unit derived from a dicarboxylic acid.

Examples of the dicarboxylic acid include a dicarboxylic acid having 3 to 18 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. Examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-methylterephthalic acid, and naphthalenedicarboxylic acid, malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid. , Sebacic acid, aliphatic dicarboxylic acid such as decandicarboxylic acid and the like. Further, a furancarboxylic acid such as 2,5-furandicarboxylic acid and an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid can also be mentioned.
Among the above, the dicarboxylic acid is preferably a flange carboxylic acid such as 2,5-flange carboxylic acid. Frangicarboxylic acid can be produced from biomass such as cellulosic. Therefore, by using the flange carboxylic acid, it is possible to increase the proportion of biomass-derived components in the polymer and to make all the constituent units contained in the polyester resin biomass-derived. Further, polyester having good heat resistance can be obtained.
Therefore, it is preferable that the polyester resin has a structural unit represented by the following formula (4-1).

In equation (4-1), R ^{1 to} R ⁶ are the same as above.

In each of the formulas (4) and (4-1), it is preferable that at least one of ^{R 1} and R ² is a methoxy group and at least one of R ³ and R ^{4 is a methoxy group.}
Further, in each of the formulas (4) and (4-1), it is preferable that the methoxy group is arranged at the ortho position with respect to the oxygen atom derived from the phenolic hydroxyl group. Therefore, it is preferable that the polyester resin has a structural unit represented by the following formula (4-2). In formula (4-2), ^{it is more preferable that R 1} and R ⁴ are methyl groups and R ² and R ³ are hydrogen atoms. Further, in formulas (4) and (4-1), R ⁵ and R ^{6 are respectively.} Is preferably at least one of which is a methyl group, and more preferably both of which are methyl groups.
The flange carboxylic acid is preferably a 2,5-furan carboxylic acid, and C = O constituting the ester structure is preferably bonded to the 2nd and 5th positions of the furan ring. Most preferably, the polyester resin has a repeating unit represented by the following formula (4-3).

In equation (4-2), R ^{1 to} R ⁶ are the same as above.

The polyester resin may have two or more structural units represented by the formulas (4), (4-1), (4-2) and (4-3) as repeating units, but preferably 10 or more. It is preferably 15 or more, and more preferably 50 or more. By setting these lower limits or more, various mechanical and thermal physical properties become good. The number of the repeating units in the polyester resin is not particularly limited, but is, for example, 50,000 or less, preferably 10,000 or less.

The glass transition temperature (Tg) of the polyester resin is preferably 100 ° C. or higher. The thermal performance can be improved by setting the temperature to 100 ° C. or higher. Further, from the viewpoint of improving the thermal performance, the glass transition temperature (Tg) of the polyester resin is preferably 130 ° C. or higher. The glass transition temperature (Tg) of the polyester resin is not particularly limited, but is, for example, 220 ° C. or lower.

As described above, the polyester resin of the present invention is a polycondensate of a dihydroxy compound containing an indane compound and a dicarboxylic acid, and the dihydroxy compound is preferably composed of the above indane compound. However, the dihydroxy compound may contain a dihydroxy compound (also referred to as another dihydroxy compound) other than the indane compound. Examples of other dihydroxy compounds include the above-mentioned aromatic dihydroxy compounds.
Based on the total amount of the constituent units derived from the dihydroxy compound in the polyester resin, the content of the constituent units derived from the indane compound is preferably 50% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass. By increasing the amount of the structural unit derived from the indane compound, the effect of introducing the structural unit derived from the indane compound can be appropriately exhibited. In addition, the biorate of the polyester resin can be increased.

Further, in the polyester resin of the present invention, when a flangecarboxylic acid is used as the dicarboxylic acid, the entire amount of the dicarboxylic acid may be used as the flangecarboxylic acid, but as the dicarboxylic acid, another dicarboxylic acid is used in addition to the flangecarboxylic acid. May be good. The other dicarboxylic acid may be appropriately selected from the above-mentioned dicarboxylic acids.
In the polyester resin, the content of the constituent unit derived from the flange carboxylic acid is preferably 50% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass based on the total amount of the constituent units derived from the dicarboxylic acid. As described above, by increasing the amount of the structural unit derived from the flange carboxylic acid, the biorate in the polyester resin can be increased. Further, by using a flange carboxylic acid as the total amount of the dicarboxylic acid and an indane-based compound as the total amount of the dihydroxy compound, the total amount can be derived from biomass.

(Polyester resin manufacturing method)
The polyester resin can be produced by polycondensing a dihydroxy compound containing an indane compound and a dicarboxylic acid. The polycondensation reaction may be carried out by a known method. Further, the dicarboxylic acid may be appropriately chlorinated to form a dicarboxylic acid chloride and reacted with the dihydroxy compound in order to enhance the reactivity. Further, the dihydroxy compound may be acylated with an acylating agent such as acetic anhydride, propionic anhydride, butyric anhydride or isobutyric anhydride and reacted with a dicarboxylic acid or the like to obtain a polyester resin.

[Polycarbonate resin]
The polycarbonate resin of the present invention is a polycondensate having a constituent unit derived from a dihydroxy compound and a carbonate bond, and the dihydroxy compound contains the above-mentioned indane compound. Specifically, the polycarbonate resin of the present invention has a structural unit represented by the following formula (5).

In the formula (5), R ^{1 to} R ⁶ are the same as described above.

In formula (5), it is preferable that at least one of ^{R 1} and R ² is a methoxy group and at least one of R ³ and R ^{4 is a methoxy group.}
Further, in the formula (5), it is preferable that the methoxy group is arranged at the ortho position with respect to the oxygen atom derived from the phenolic hydroxyl group. Therefore, it is preferable that the polycarbonate resin has a repeating unit represented by the following formula (5-1). In formula (5-1), it is more preferable that ^{R 1} and R ⁴ are metosiki groups, and R ² and R ^{3 are hydrogen atoms.}
Further, in each of the formulas (5) and (5-1), ^{it is preferable that at least one of R 5} and R ⁶ is a methyl group, and it is more preferable that both are methyl groups. Most preferably, the polycarbonate resin has a repeating unit represented by the following formula (5-2).

In equation (5-1), R ^{1 to} R ⁶ are the same as above.

The polycarbonate resin may have two or more structural units represented by the formulas (5), (5-1), and (5-2) as repeating units, and the number of repeating units is preferably 10 or more. It is more preferably 20 or more, and even more preferably 50 or more. By setting these lower limits or more, various mechanical and thermal physical properties become good. The number of repeating units in the polycarbonate resin is not particularly limited, but is, for example, 50,000 or less, preferably 10,000 or less.

The polycarbonate resin of the present invention has a structural unit derived from the dihydroxy compound and a carbonate bond, and the dihydroxy compound is preferably composed of the above-mentioned indane compound. However, the dihydroxy compound may contain a dihydroxy compound (also referred to as another dihydroxy compound) other than the indane compound. Examples of other dihydroxy compounds include the above-mentioned aromatic dihydroxy compounds.
Based on the total amount of the constituent units derived from the dihydroxy compound in the polycarbonate resin, the content of the constituent units derived from the indane compound is preferably 50% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass. By increasing the amount of the structural unit derived from the indane compound, the effect of introducing the structural unit derived from the indane compound can be appropriately exhibited, and the biorate of the polycarbonate resin can be increased.

(Manufacturing method of polycarbonate resin)
The polycarbonate resin is prepared by a known transesterification method in which a dihydroxy compound is reacted with a carbonic acid diester in the presence of a basic catalyst, or a known interfacial polycondensation method in which a dihydroxy compound is reacted with phosgene in the presence of an acid binder. Obtainable.

The polymer of the present invention can be used in various fields, and is not particularly limited, but can be used in any field such as an electric field, a transportation field, a civil engineering field, a construction field, a mechanical field, and a medical field. The polymer of the present invention can be used in various forms such as various molded products, adhesives, paints, fillers, films, powders, composite materials, and foams. Further, the polymer of the present invention can be used as a substitute for epoxy resin, epoxy cured product, phenoxy resin, polyester resin, polycarbonate resin and the like in the field conventionally used.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The measurement conditions in the following examples are as follows.
<Measurement conditions>
[GPC measurement]
A GPC system manufactured by Shimadzu Corporation was used, and "KF803L" x 2 (exclusion limit molecular weight 70,000) manufactured by Showa Denko KK was used as a column. The column temperature was set to 40 ° C. and the flow rate was 1.0 ml / min, tetrahydrofuran was used as the developing medium, and RI was used as the detector.
In the molecular weight calculation method, a calibration curve is created using the standard polystyrene "TSK standardPOLYSTYLENE" having a weight average molecular weight (Mw) of 96,400, 37,900, 18,100, 9,100, 5,970, 2,630, 1,050, 500, respectively, and the weight average molecular weight (Mw) is calculated. ), The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were determined.
[ ^{1 1} H-NMR spectrum measurement]
Using an NMR measuring device "ECX-400" manufactured by JEOL Ltd., measurement was performed at 23 ° C. using deuterated dimethyl sulfoxide (heavy DMSO) as a solvent.
[Glass transition temperature (Tg)]
Using a differential scanning calorimeter (DSC-60) manufactured by Shimadzu Corporation, the measurement was performed under an argon atmosphere and a heating condition of 10 ° C./min, and the midpoint of the baseline displacement was defined as the glass transition temperature.

Synthesis example 1
[Synthesis of diisoeugenol]
In a glass container, 5.00 g of isoeugenol, 0.51 g of 35 mass% hydrochloric acid, and 4.50 g of methanol were mixed and reacted at 50 ° C. for 10 hours. After completion of the reaction, a white precipitate was precipitated. The precipitate was filtered and washed with a mixed solvent of methanol / water, dissolved in ethyl acetate, and ion-exchanged water was added for washing twice. Anhydrous magnesium sulfate was added to the washed solution for dehydration, and then ethyl acetate was removed to obtain 2.68 g of the target diisoeugenol as a slightly yellow solid (yield 53.6%). Structure identification was ^{performed by 1} H-NMR measurement in heavy DMSO. FIG. 1 shows a ¹ H-NMR spectrum. The reaction formula in Synthesis Example 1 is shown below.

Example 1
[Synthesis of epoxy resin]
1.00 g of diisoeugenol obtained in Synthesis Example 1, 5.64 g of epichlorohydrin, 0.25 g of tetrabutylammonium bromide, and 0.02 g of ion-exchanged water were reacted at 80 ° C. for 6 hours. After completion of the reaction, 1.28 g of a 40 mass% sodium hydroxide aqueous solution was added dropwise while cooling the solution with ice, and then the reaction was carried out at room temperature for 3 hours. After adding 10 ml of ion-exchanged water to the solution after the reaction to dissolve the precipitated salt, 10 ml of ethyl acetate was added and mixed well to separate the aqueous phase. Anhydrous magnesium sulfate was added to the obtained organic phase for dehydration, and then ethyl acetate and residual volatile matter were removed to obtain 0.93 g of the target epoxy resin as a white solid (yield 69.4%). Structure identification was ^{performed by 1} H-NMR measurement in heavy DMSO. FIG. 2 shows the ¹ H-NMR spectrum. The reaction formula in Example 1 is shown below.

[Preparation of hardened epoxy]
Example 2
0.53 g of the epoxy resin obtained in Example 1 and 0.10 g of isophorone diamine were diluted with 0.3 g of tetrahydrofuran and mixed uniformly. Then, while evaporating tetrahydrofuran in the oven, the cured product was prepared by heating at 100 ° C. for 1 hour, 160 ° C. for 1 hour, and then 200 ° C. for 1 hour. The reaction formula in Example 2 is shown below.
The obtained cured product was finely crushed, and Tg was measured by a differential scanning calorimetry (DSC). As a result, Tg was 139 ° C., showing good heat resistance.

[Synthesis of epoxy resin]
Example 3
An epoxy resin was synthesized in the same manner as in Example 1 except that the reaction time was 4 hours, and 1.25 g of the target epoxy resin was obtained as a white solid (yield 92.7%). Structure identification was ^{performed by 1} H-NMR measurement in heavy DMSO.

[Preparation of hardened epoxy]
Example 4
0.50 g of the epoxy resin obtained in Example 3 and 0.12 g of 4,4'-methylenebis (cyclohexylamine) (BACHM) were diluted with 0.3 g of tetrahydrofuran and mixed uniformly. Then, while evaporating tetrahydrofuran in the oven, the cured product was prepared by heating at 100 ° C. for 1 hour, 160 ° C. for 1 hour, and then 200 ° C. for 1 hour. The reaction formula in Example 4 is shown below.
The obtained cured product was finely crushed, and Tg was measured by a differential scanning calorimeter (DSC). As a result, Tg was 145 ° C. The Tg of the epoxy cured product obtained by curing the guaiacol dimer (bisguaiacol diglycidyl ether), which is a raw material derived from lignin, with BACHM is 111 ° C. (DMA (Dynamic Viscoelasticity Measuring Device) tanδ peak, literature value. , Non-Patent Document 1), it can be understood that the polymer in the present invention has good heat resistance.

[Preparation of hardened epoxy]
Example 5
0.50 g of the epoxy resin obtained in Example 3 and 0.047 g of diethylenetriamine (DETA) were diluted with 0.3 g of tetrahydrofuran and mixed uniformly. Then, while evaporating tetrahydrofuran in the oven, the cured product was prepared by heating at 80 ° C. for 2 hours and then at 100 ° C. for 2 hours. The reaction formula in Example 5 is shown below.
The obtained cured product was finely crushed, and Tg was measured by a differential scanning calorimeter (DSC). As a result, Tg was 99 ° C. The Tα of the epoxy cured product obtained by curing the dihydroeugenol dimer diglycidyl ether (epoxy resin) derived from lignin with DETA is 70 ° C. (measured by DMA (dynamic viscoelasticity measuring device), literature value, Since it is (see Non-Patent Document 2), it can be understood that the polymer in the present invention has good heat resistance.

[Synthesis of phenoxy resin]
Example 6
0.10 g of the epoxy resin obtained in Example 3, 0.075 g of diisoeugenol obtained in Synthesis Example 1, 0.01 g of methyltriphenylphosphonium bromide as a catalyst, and 0.2 g of toluene were mixed and mixed at 150 ° C. It was allowed to react for 4 hours. After completion of the reaction, the mixture was diluted with 0.5 g of tetrahydrofuran, and then the reaction solution was poured into a large amount of methanol to precipitate a polymer. Then, the precipitated polymer was filtered off and dried to obtain the desired phenoxy resin. When the molecular weight was measured by GPC, it was Mn = 5300, Mw = 9800, and Mw / Mn = 1.85. When the DSC of the obtained phenoxy resin was measured, the Tg was 92 ° C., showing good heat resistance. ^{The structure was confirmed by 1} H-NMR measurement in heavy DMSO. FIG. 3 shows the ¹ H-NMR spectrum. The reaction formula in Example 6 is shown below.

[Synthesis of polyester resin]
Example 7
Triethylamine (1.3 ml, 9.1 mmol) and 2.5-francarbonyldichloride (388 mg, 2.01 mmol) were sequentially added to a solution of diisoeugenol (600 mg, 1.82 mmol) in anhydrous tetrahydrofuran (5 ml). .. The reaction mixture was magnetically stirred at 60 ° C. for 11 hours and cooled to room temperature. Next, methanol (40 ml) was added, and the obtained product was reprecipitated and then dried to obtain 710 mg of the desired polyester. When the molecular weight was measured by GPC, it was Mn = 4400, Mw = 7900, and Mw / Mn = 1.80. The DSC of the obtained polyester was measured and found to have a Tg of 165 ° C., showing very good heat resistance. ^{The structure was confirmed by 1} H-NMR measurement in heavy DMSO. FIG. 4 shows the ¹ H-NMR spectrum. The reaction formula in the examples is shown below.

Claims (10)

A polymer containing a structural unit derived from an indane compound represented by the following formula (1).

In the formula (1), R ¹ , R ² , R ³ and R ⁴ are independently either hydrogen atoms or methoxy groups, and R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, respectively. Although ^{either, R 1, R 2, R} 3, and at least one of ^{R 4} is a methoxy group. The polymer according to claim 1, wherein at least one of R ¹ and R ² is a methoxy group, and at least one of R ³ and R ^{4 is a methoxy group.} The polymer according to claim 1 or 2, wherein the methoxy group is arranged at the ortho position with respect to the OH group. The polymer according to any one of claims 1 to 3, which is any one of a cured epoxy resin, a phenoxy resin, a polyester resin, and a polycarbonate resin. The polymer according to any one of claims 1 to 4, wherein the polymer is a phenoxy resin having a structural unit represented by the following formula (3).

In the formula (3), R ^{1 to} R ⁶ are the same as described above. The polymer according to any one of claims 1 to 5, wherein the polymer is a polyester resin having a structural unit represented by the following formula (4-1).

In equation (4-1), R ^{1 to} R ⁶ are the same as above. The polymer according to any one of claims 1 to 6, which has a weight average molecular weight of 5000 or more. The polymer is a cured product of an epoxy resin and a curing agent.
The polymer according to any one of claims 1 to 4, wherein the epoxy resin has a structural unit derived from the indane compound and an epoxy group. An epoxy resin having a structural unit derived from an indane compound represented by the following formula (1) and an epoxy group.

In the formula (1), R ¹ , R ² , R ³ and R ⁴ are independently either hydrogen atoms or methoxy groups, and R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, respectively. Although ^{either, R 1, R 2, R} 3, and at least one of ^{R 4} is a methoxy group. The epoxy resin according to claim 9, which is represented by the following formula (2).

In the formula (2), R ^{1 to} R ⁶ are the same as described above. ^{R 1, R 2, R 3} , R 4, R 5, and ^{R 6} each, may be the same and in in one molecule may be different. n is an integer greater than or equal to 0.