WO2020004185A1 - Cyclic-carbonate-substituted propylcatechol, method for producing cyclic-carbonate-substituted propylcatechol, resin composition containing cyclic-carbonate-substituted propylcatechol, and cured resin - Google Patents

Abstract

Provided is a cyclic-carbonate-substituted propylcatechol having a structure represented by formula (1), wherein R1 and R2 are each independently a hydrogen atom or an organic group. R1 is preferably an organic group represented by formula (2), wherein n is an integer from 0 to 300. R2 is preferably an organic group represented by formula (3), wherein R3 is a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group, and n is an integer from 0 to 300.

Description

Cyclic carbonate-substituted propyl catechol, method for producing cyclic carbonate-substituted propyl catechol, resin composition containing cyclic carbonate-substituted propyl catechol, and cured resin

The present invention relates to a cyclic carbonate-substituted propyl catechol obtained from lignocellulosic biomass, a method for producing the cyclic carbonate-substituted propyl catechol, a resin composition containing the cyclic carbonate-substituted propyl catechol, and a cured resin.
Priority is claimed on Japanese Patent Application No. 2018-123508 filed on June 28, 2018, the content of which is incorporated herein by reference.

In 2016, polyurethane ("PU") material was manufactured at approximately 18 million tonnes, making it the sixth most produced polymer in the world. Most of the production was done in Asia, and its production was about 8 million tons. The polyurethane market is worth around 53 billion euros (about 6.9 trillion yen) worldwide. These PU materials are used everywhere in everyday life, such as furniture, cars, shoes, elastomers, wall coatings, and roof insulation. PU materials are used in a very wide range of fields because of their excellent mechanical strength, heat resistance, chemical resistance, adhesiveness, and low curing shrinkage.

Worldwide, these PU materials are synthesized from polyols and diisocyanates, which are highly dependent on petroleum resources. Recently, research on the use of plant-derived renewable resources has been conducted from the viewpoint of depletion of petroleum resources. Currently, commercial bio-based PU materials are made by reacting bio-based polyols obtained from castor oil, soybean oil, and sunflower oil with synthetic isocyanates. In 2012, the global pure oil-based PU market is estimated to be approximately 15 million tonnes, while the bio-based PU market for the same year is estimated to be approximately 1500 tonnes.
The growth prospects for PU materials using bio-based polyols are promising. However, this PU material is made from highly harmful diisocyanates such as methylene diphenyl diisocyanate (MDI), toluene-2,4-diisocyanate (TDI), the two most widely used isocyanates in PU production. Problem still exists. These isocyanates have detrimental effects on the human body and the environment. Prolonged exposure to these isocyanates poses serious health risks such as asthma, dermatitis, conjunctivitis, and acute poisoning (Non-Patent Documents 1 and 2). With regard to such serious health issues, environmental regulations such as the European REACH regulations restrict or prohibit the use of these diisocyanates [3]. Therefore, a major breakthrough that enables true green synthesis of PU materials is to utilize natural resources to produce bio-based synthetic equivalents of carbamate groups while avoiding reliance on diisocyanates It is obvious.

For these reasons, new methods of obtaining PU materials without the use of isocyanates have attracted attention. In this regard, the most common alternative is the polyaddition reaction of bis-5-membered cyclic carbonates and diamines, which results in polyhydroxys having primary and secondary hydroxyl groups on the carbon chain. Urethane (hereinafter, also referred to as “PHU”) is formed.
Besides the use of no diisocyanate, the advantage can be mentioned of the possible improvement of the mechanical properties, the adhesive properties and the heat resistance provided by the presence of hydroxyl groups which are not present in ordinary polyurethanes ( Non-patent document 4).

In order to produce a PHU material, a cyclic carbonate compound is required. These cyclic carbonate compounds can be obtained by various methods. Among them, the most promising is a method of carbonating an epoxy compound in the presence of CO ₂ and a catalyst. This reaction has the main advantage of using CO ₂ is a gas that causes global warming. In addition, from a sustainable development perspective, bio-based cyclic carbonate compounds can be synthesized from renewable resources such as vegetable oils, polyols, and phenols. Actually, the bio-based cyclic carbonate compound is obtained by using a vegetable seed oil such as sunflower oil, linseed oil or soybean oil as a raw material, and epoxidizing the terminal and internal double bonds of the vegetable seed oil, followed by carbonation. Synthesized. On the other hand, the flexible properties of vegetable oils often reduce the mechanical and thermal properties of PHU materials, requiring the introduction of harder segments to ensure performance comparable to conventional polyurethane resins. .
In this regard, a phenolic cyclic carbonate compound is synthesized by glycidylation of a bisphenol compound obtained by para-paracondensation of phenols with formaldehyde with epichlorohydrin, and subsequently immobilization of CO ₂ . Due to the aromatic ring of phenols, the mechanical properties and heat resistance of the PHU material produced from the phenolic cyclic carbonate compound as a raw material are improved. However, from the viewpoint of safe polyurethane production, the production of cyclic carbonate-substituted phenols involves the problem of using harmful formaldehyde. It has been known that PHU materials obtained by epoxidation and carbonation of various polyols such as glycerol, pentaerythrol, and trimethylolpropane obtained from starch and sugar purification have relatively good mechanical properties. In particular, the functional groups influence the properties. Further, the above properties are improved by having an aromatic structure.

Against this background, the thermal and mechanical properties of the PHU material obtained after the curing step with the diamine compound are, for example, the properties of the chemical structure such as the aromatic structure of the reactant, the type and number of functional groups, etc. It is thought that it greatly depends on.

Attempts to use propyl catechol as a bio-based polymer have been reported, and Non-Patent Documents 5 and 6 describe the use of propyl catechol in the synthesis of epoxy resins and polycarbonates, respectively. Propyl catechol can be obtained by known methods for demethylating bio-based 2-methoxy-4-propyl phenol. Further, the 2-methoxy-4-propylphenol can be obtained by continuous extraction of lignocellulosic biomass and selective depolymerization (hydrogenation) (Patent Document 1). On the other hand, in the production of PHU materials, the use of propyl catechol as a monomer has not been performed yet. Furthermore, propyl catechol has the advantage of having two hydroxyl groups as functional groups.

WO 2015/061802

Karol M. H., Kramarik J. A., Phenyl isocyanate is a potent chemical sensitizer, Toxicology Letters; 89, 1996, 139-146. Gupta S., padUpadhyaya R., Cancer and p21 protein expression: in relation isocyanate toxicity in cultured mammalian cells, International Journal of Pharmaceutical Research and Bio-Science; 3, 2014, 20-28. Merenyi S., REACH: Regulation (EC) 2006No 1907/2006: Consolidated versiontro (June 2012) with an introduction and future prospects regarding the area of Chemicals legislation: GRIN Verlag; 2012. Cornille, A .; Michaud, G .; Simon, F .; Fouquay, S .; Auvergne, R .; Boutevin, B .; Caillol, S., Promising mechanical and adhesive properties ofisocyanate-free poly (hydroxyurethane) European Journal; 2016, 84, 404-420. Zhao, S .; buAbu-Omar, M. M., Renewable Thermoplastics Based on Lignin-Derived Polyphenols. Macromolecules; 50, 2017, 3573-3581. Koelewijn, S. F .; Van den Bosch, S .; Renders, T .; Schutyser, W .; Lagrain, B .; Smet, M .; Thomas, J .; Dehaen, W .; Van Puyvelde, P .; Witters, H .; Sels, B. F., Sustainable bisphenols from renewable softwood lignin feedstockfor polycarbonates and cyanate ester resins. Green Chem. 2017, 19 (11), 1-22561-2570.

The present invention has been made in view of the above circumstances, and is intended to provide a starting material for PU materials obtained without using harmful isocyanate compounds such as PHU materials having excellent mechanical properties, adhesive properties, and high heat resistance. It is an object of the present invention to provide a cyclic carbonate-substituted propyl catechol derived from renewable resources such as lignocellulosic biomass that can be used as a compound (polymerizable monomer).

［式（１）中、Ｒ^１とＲ^２はそれぞれ独立に、水素原子又は有機基である。］
［２］　Ｒ^１が式（２）で表される有機基である［１］に記載の環状カーボネート置換プロピルカテコール。

［式（２）中、ｎは０～３００の整数である。＊は前記式（１）中の環状カーボネート置換プロピルカテコール構造中の酸素原子との結合部位を示す。］
［３］　Ｒ^２が式（３）で表される有機基である［１］又は［２］に記載の環状カーボネート置換プロピルカテコール。

［式（３）中、Ｒ^３は２価の脂肪族炭化水素基又は２価の芳香族炭化水素基であり、ｎは０～３００の整数である。＊は前記式（１）中の環状カーボネート置換プロピルカテコール構造中のベンゼン環との結合部位を示す。］
［４］　Ｒ^３が－ＣＲ^４Ｒ^５－で表される２価の炭化水素基であり、Ｒ^４及びＲ^５はそれぞれ独立に１価の炭化水素基であり、Ｒ^４及びＲ^５が結合して環状構造を形成していてもよい、［３］に記載の環状カーボネート置換プロピルカテコール。
［５］　Ｒ^３が式（４）で表される２価の芳香族炭化水素基である、［３］に記載の環状カーボネート置換プロピルカテコール。

［式（４）中、Ｒ^６は－ＣＲ^４Ｒ^５－で表される２価の炭化水素基であり、Ｒ^４及びＲ^５はそれぞれ独立に１価の炭化水素基である。＊は前記式（３）中の環状カーボネート置換プロピルカテコール構造中のベンゼン環との結合部位を示す。］
［６］　Ｒ^４及びＲ^５がメチル基である、［５］に記載の環状カーボネート置換プロピルカテコール。
［７］　Ｒ^３が置換基を有していてもよい、シクロアルキレン基である、［３］に記載の環状カーボネート置換プロピルカテコール。
［８］　Ｒ^３が式（５）で表される２価の脂肪族炭化水素基である、［３］又は［７］に記載の環状カーボネート置換プロピルカテコール。

［＊は前記式（３）中の環状カーボネート置換プロピルカテコール構造中のベンゼン環との結合部位を示す。］
［９］　Ｒ^３が置換基を有していてもよい、アリールアルキレン基である、［３］に記載の環状カーボネート置換プロピルカテコール。
［１０］　Ｒ^３が式（６）で表される２価の芳香族炭化水素基である、［３］又は［９］に記載の環状カーボネート置換プロピルカテコール。

［＊は前記式（３）中の環状カーボネート置換プロピルカテコール構造中のベンゼン環との結合部位を示す。］
［１１］　触媒の存在下、エポキシ化プロピルカテコールと、ＣＯ_２と、を反応させることを含む［１］～［１０］のいずれか１に記載の環状カーボネート置換プロピルカテコールの製造方法。
［１２］　［１］～［１０］のいずれか１に記載の環状カーボネート置換プロピルカテコールと、前記環状カーボネート置換プロピルカテコールポリマー以外の少なくとも１種のポリマー及び環状カーボネート置換プロピルカテコール以外の少なくとも１種のモノマーのいずれか一方又は両方と、を含む樹脂組成物。
［１３］　［１２］に記載の樹脂組成物を硬化して得られる樹脂硬化物。 The cyclic carbonate-substituted propyl catechol, the method for producing the cyclic carbonate-substituted propyl catechol, the resin composition containing the cyclic carbonate-substituted propyl catechol, and the cured resin of the present invention are as listed in the following [1] to [13].
[1] A cyclic carbonate-substituted propyl catechol having a structure represented by the formula (1).

[In the formula (1), R ¹ and R ² are each independently a hydrogen atom or an organic group. ]
[2] The cyclic carbonate-substituted propyl catechol according to [1], wherein R ¹ is an organic group represented by the formula (2).

[In the formula (2), n is an integer of 0 to 300. * Indicates a bonding site to an oxygen atom in the cyclic carbonate-substituted propyl catechol structure in the formula (1). ]
[3] The cyclic carbonate-substituted propyl catechol according to [1] or [2], wherein R ² is an organic group represented by the formula (3).

[In the formula (3), R ³ is a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group, and n is an integer of 0 to 300. * Indicates a binding site to a benzene ring in the cyclic carbonate-substituted propyl catechol structure in the formula (1). ]
[4] R ³ is a divalent hydrocarbon group represented by —CR ⁴ R ⁵ —, R ⁴ and R ⁵ are each independently a monovalent hydrocarbon group, and R ⁴ and R ⁵ are a bond The cyclic carbonate-substituted propyl catechol according to [3], which may form a cyclic structure.
[5] The cyclic carbonate-substituted propyl catechol according to [3], wherein R ³ is a divalent aromatic hydrocarbon group represented by the formula (4).

[In the formula (4), R ⁶ is a divalent hydrocarbon group represented by —CR ⁴ R ⁵ —, and R ⁴ and R ⁵ are each independently a monovalent hydrocarbon group. * Indicates a binding site to the benzene ring in the cyclic carbonate-substituted propylcatechol structure in the formula (3). ]
[6] The cyclic carbonate-substituted propyl catechol according to [5], wherein R ⁴ and R ⁵ are methyl groups.
[7] The cyclic carbonate-substituted propyl catechol according to [3], wherein R ³ is a cycloalkylene group which may have a substituent.
[8] The cyclic carbonate-substituted propyl catechol according to [3] or [7], wherein R ³ is a divalent aliphatic hydrocarbon group represented by the formula (5).

[* Indicates a binding site to the benzene ring in the cyclic carbonate-substituted propyl catechol structure in the formula (3). ]
[9] The cyclic carbonate-substituted propyl catechol according to [3], wherein R ³ is an arylalkylene group which may have a substituent.
[10] The cyclic carbonate-substituted propyl catechol according to [3] or [9], wherein R ³ is a divalent aromatic hydrocarbon group represented by the formula (6).

[* Indicates a binding site to the benzene ring in the cyclic carbonate-substituted propyl catechol structure in the formula (3). ]
[11] The method for producing cyclic carbonate-substituted propyl catechol according to any one of [1] to [10], comprising reacting epoxidized propyl catechol with CO _{2 in} the presence of a catalyst.
[12] The cyclic carbonate-substituted propyl catechol according to any one of [1] to [10], at least one polymer other than the cyclic carbonate-substituted propyl catechol polymer, and at least one other than the cyclic carbonate-substituted propyl catechol A resin composition containing one or both of the monomers.
[13] A cured resin product obtained by curing the resin composition according to [12].

The cyclic carbonate-substituted propyl catechol of the present invention is a bio-based compound obtained from lignocellulosic biomass, and is obtained by a polyaddition reaction of the cyclic carbonate-substituted propyl catechol with a polyamine which is a compound having at least two amino groups. The resulting bio-based PHU material allows for the replacement of current polyols and the current process of petroleum-based PUs made from harmful polyisocyanates. Further, since these bio-based PHU materials have a hydroxyl group as a functional group, they have excellent mechanical properties and adhesive properties, and also have high heat resistance.

<Cyclic carbonate substituted propyl catechol>
The cyclic carbonate-substituted propyl catechol of the present embodiment has a structure represented by the formula (1).

　Ｒ^１とＲ^２はそれぞれ独立に、水素原子又は有機基である。

R ¹ and R ² are each independently a hydrogen atom or an organic group.

The organic group represented by R ¹ may be a linear hydrocarbon group, a branched hydrocarbon group, or a cyclic hydrocarbon group. The organic group represented by R ¹ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The number of carbon atoms of the organic group represented by R ¹ is preferably 1 to 52, more preferably 1 to 40, and still more preferably 1 to 28.
Further, the organic group represented by R ¹ may be an organic group represented by the formula (2).

　ｎは０～３００の整数であり、０～１５０の整数が好ましく、０～１００の整数がより好ましく、１～１００の整数がさらに好ましく、１～５０の整数が特に好ましい。
　ｎは実施例に記載のＧＰＣ測定により求められた環状カーボネート置換プロピルカテコールの数平均分子量より得ることができる。得られたｎが小数である場合、四捨五入を行い整数とすればよい。
　化学式中の＊は前記式（１）中の環状カーボネート置換プロピルカテコール構造中の酸素原子との結合部位を示す。

n is an integer of 0 to 300, preferably an integer of 0 to 150, more preferably an integer of 0 to 100, further preferably an integer of 1 to 100, particularly preferably an integer of 1 to 50.
n can be obtained from the number average molecular weight of cyclic carbonate-substituted propyl catechol determined by GPC measurement described in Examples. If the obtained n is a decimal number, it may be rounded to an integer.
* In the chemical formula indicates a bonding site to an oxygen atom in the cyclic carbonate-substituted propyl catechol structure in the formula (1).

The organic group represented by R ² may be a linear hydrocarbon group, a branched hydrocarbon group, or a cyclic hydrocarbon group. The organic group represented by R ² may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The number of carbon atoms of the organic group represented by R ² is preferably 1 to 200, more preferably 1 to 150, and still more preferably 1 to 100.
Further, the organic group represented by R ² may be an organic group represented by the formula (3).

　Ｒ^３は２価の脂肪族炭化水素基又は２価の芳香族炭化水素基である。ｎは０～３００の整数であり、０～１５０の整数が好ましく、０～１００の整数がより好ましく、１～１００の整数がさらに好ましく、１～５０の整数が特に好ましい。
　ｎが１以上の場合、複数のＲ^３は全て同一でもよいし、異なっていてもよい。
　ｎは実施例に記載のＧＰＣ測定により求められた環状カーボネート置換プロピルカテコールの数平均分子量より得ることができる。得られたｎが小数である場合、四捨五入を行い整数とすればよい。
　化学式中の＊は前記式（１）中の環状カーボネート置換プロピルカテコール構造中のベンゼン環との結合部位を示す。
　本明細書において、「芳香族炭化水素基」とは、芳香環を有する炭化水素基を意味する。
　本明細書において、「脂肪族炭化水素基」とは、芳香環を有しない炭化水素基を意味する。

R ³ is a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group. n is an integer of 0 to 300, preferably an integer of 0 to 150, more preferably an integer of 0 to 100, further preferably an integer of 1 to 100, particularly preferably an integer of 1 to 50.
When n is 1 or more, all of a plurality of R ³ may be the same or different.
n can be obtained from the number average molecular weight of cyclic carbonate-substituted propyl catechol determined by GPC measurement described in Examples. If the obtained n is a decimal number, it may be rounded to an integer.
* In the chemical formula indicates a binding site to the benzene ring in the cyclic carbonate-substituted propylcatechol structure in the formula (1).
In the present specification, “aromatic hydrocarbon group” means a hydrocarbon group having an aromatic ring.
In the present specification, the “aliphatic hydrocarbon group” means a hydrocarbon group having no aromatic ring.

In the formula (3), the divalent hydrocarbon group represented by R ³ may be a methylene group, but is preferably a group represented by —CR ⁴ R ⁵ —, and R ⁴ and R ⁵ Each independently represents a monovalent hydrocarbon group, and R ⁴ and R ⁵ may combine to form a cyclic structure. Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkylalkyl group having 4 to 12 carbon atoms, and an aryl having 6 to 12 carbon atoms. Groups are mentioned as examples. The use of the group represented by -CR ⁴ R ^5- is advantageous in that no harmful formaldehyde has to be used in the production of cyclic carbonate-substituted propyl catechol.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, and the like. Examples of the cycloalkylalkyl group include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylethyl group, a cyclooctylethyl group, and the like. Aryl groups include phenyl, tolyl, ethylphenyl, xylyl, cumenyl, mesityl, o-, m- and p-methoxyphenyl, o-, m- and p-ethoxyphenyl, and naphthyl (1-naphthyl group, 2-naphthyl group, etc.), biphenyl group and the like.

Among those exemplified as R ⁴ and R ⁵ , a methyl group, an ethyl group, an isobutyl group, a phenyl group and the like are preferable, and a methyl group is particularly preferable because it is easily available, inexpensive, and easy to synthesize.

R ⁴ and R ⁵ may combine to form a cyclic structure. For example, R ⁴ and R ⁵ may be linked together such that R ³ has a cyclohexane ring structure.

In another embodiment of the present invention, in the formula (3), R ³ is preferably a cycloalkylene group which may have a substituent.

The carbon number of the cycloalkylene group is preferably from 3 to 12, more preferably from 3 to 11, and even more preferably from 3 to 10. Examples of such a cycloalkylene group include divalent groups in which one hydrogen atom is further removed from the cycloalkyl groups exemplified as R ⁴ and R ⁵ , and among them, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group , Cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cycloundecylene group, cyclododecylene group is preferred, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group is more Preferably, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group are more preferable.

The cycloalkylene group may have a substituent. That is, a hydrogen atom on the cycloalkane ring may be substituted by a monovalent hydrocarbon group. The number of substituents depends on the number of carbon atoms of the cycloalkylene group, but is preferably 1 to 12, more preferably 1 to 11, and still more preferably 1 to 10.
As the substituent, a linear or branched alkyl group is preferable. The carbon number of the alkyl group is preferably 1 to 12, more preferably 1 to 11, and still more preferably 1 to 10. Examples of such an alkyl group include the alkyl groups exemplified as R ⁴ and R ⁵ , and among them, a methyl group, an ethyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group Group, undecyl group, dodecyl group, isopropyl group, isobutyl group is preferred, methyl group, ethyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group is more preferred, methyl group, ethyl group, butyl group, isopropyl group Groups are more preferred.
When the number of substituents is two or more, all of the plurality of substituents may be the same or different.

When R ³ is a cycloalkylene group having a substituent, the total carbon number is preferably from 4 to 20, more preferably from 4 to 19, and still more preferably from 4 to 18.

シ ク ロ The cycloalkylene group which may have a substituent is particularly preferably a divalent aliphatic hydrocarbon group represented by the following formula (5).

　化学式中の＊は前記式（３）中の環状カーボネート置換プロピルカテコール構造中のベンゼン環との結合部位を示す。以下、式（４）及び式（６）においても同様である。

* In the chemical formula indicates a bonding site to the benzene ring in the cyclic carbonate-substituted propylcatechol structure in the formula (3). Hereinafter, the same applies to Expressions (4) and (6).

Preferred specific examples of the divalent aliphatic hydrocarbon group represented by R ³ include an isopropylene group and a divalent group represented by the above formula (5).

In Formula (3), the divalent aromatic hydrocarbon group represented by R ³ is preferably a divalent aromatic hydrocarbon represented by Formula (4).

　Ｒ^６は－ＣＲ^４Ｒ^５－で表される２価の炭化水素基であり、Ｒ^４及びＲ^５は式（３）での説明と同様である。

R ⁶ is a divalent hydrocarbon group represented by —CR ⁴ R ⁵ —, and R ⁴ and R ⁵ are the same as described in the formula (3).

In formula (4), R ⁴ and R ⁵ are each independently preferably a methyl group in order to improve the mechanical and thermal properties of the material.

In another embodiment of the present invention, in the formula (3), R ³ is preferably an arylalkylene group which may have a substituent.

炭素 The arylalkylene group preferably has 8 to 25 carbon atoms, more preferably has 8 to 20 carbon atoms, and still more preferably has 8 to 15 carbon atoms.

The carbon number of the aryl group in the arylalkylene group is preferably from 6 to 12, more preferably from 6 to 11, and even more preferably from 6 to 10. Examples of such an aryl group include the aryl groups exemplified for R ⁴ and R ⁵ , and among them, a phenyl group is preferable.
The arylalkylene group may have a substituent. Specifically, it is preferable that a hydrogen atom in the aryl group is substituted by a monovalent hydrocarbon group. The number of substituents depends on the number of carbon atoms in the aryl group, but is preferably 1 to 6, more preferably 1 to 5, and still more preferably 1 to 4.
As the substituent, a linear or branched alkyl group is preferable. The carbon number of the alkyl group is preferably 1 to 12, more preferably 1 to 11, and still more preferably 1 to 10. Examples of such an alkyl group include the alkyl groups exemplified as R ⁴ and R ⁵ , and among them, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group Group, decyl group, undecyl group, dodecyl group, isopropyl group, isobutyl group is preferable, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group is more preferable, methyl group, ethyl group Groups, propyl groups and isopropyl groups are more preferred. Further, the substituent may be an alkoxy group, and examples thereof include a methoxy group and an ethoxy group.
When the number of substituents is two or more, all of the plurality of substituents may be the same or different.
Examples of the aryl group having a substituent include a tolyl group, ethylphenyl group, xylyl group, o-, m- and p-cumenyl groups, mesityl group, o-, m- and p-methoxyphenyl groups, o- and m- And p-ethoxyphenyl group, more preferably phenyl group, tolyl group, ethylphenyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, and phenyl group, tolyl group, ethylphenyl group, Xylyl, o-, m- and p-cumenyl are more preferred.

The alkylene group in the arylalkylene group is linear or branched, and the number of carbon atoms of the alkylene group is preferably 1 to 12, more preferably 1 to 11, and still more preferably 1 to 10. Examples of such an alkylene group include divalent groups in which one hydrogen atom is further removed from the alkyl groups exemplified as R ⁴ and R ⁵ , and among them, a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group are exemplified. , Hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, ethylidene group is preferable, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group is more preferable, methylene group , An ethylene group and a propylene group are more preferred.

When R ³ is an arylalkylene group having a substituent, the total number of carbon atoms is preferably from 6 to 25, more preferably from 6 to 20, and even more preferably from 6 to 15.

ア リ ー ル The arylalkylene group which may have a substituent is particularly preferably a divalent aromatic hydrocarbon group represented by the following formula (6).

The cyclic carbonate-substituted propyl catechol of the present invention has at least the organic group represented by the formula (2) as R ¹ or the organic group represented by the formula (3) as R ² in the formula (1). Is preferred.
Particularly preferred cyclic carbonate-substituted propyl catechol of the present embodiment are the following (i) to (iii).
(I) a cyclic carbonate-substituted propyl catechol (R ¹ ) having an organic group represented by the formula (2), and R ² having an organic group other than the organic group represented by the formula (3) or a hydrogen atom; Hereinafter, it is referred to as “compound (A)”.)
(Ii) a cyclic carbonate-substituted propyl catechol (R ¹ ) having an organic group other than the organic group represented by the formula (2) or a hydrogen atom, and R ² having an organic group represented by the formula (3) Hereinafter, it is referred to as “compound (B)”).
(Iii) A cyclic carbonate-substituted propyl catechol having an organic group represented by the formula (2) as R ^{1 and} an organic group represented by the formula (3) as R ² (hereinafter referred to as “compound (C ) ").
In the case of the compound (A), R ² is preferably a hydrogen atom.
In the case of the compound (B), R ¹ is preferably a hydrogen atom.

The cyclic carbonate-substituted propyl catechol of the present invention can be used as a raw material (polymerizable monomer) for other polymer materials such as polyhydroxyurethane materials having excellent properties comparable to polymers made according to the prior art. it can.
For example, polyhydroxyurethane can be produced by reacting compound (A), compound (B) or compound (C) of the present invention with a polyamine. Polyamine means a compound having at least two amino groups. Further, it preferably has 2 to 6 amino groups. The polyamine may have one or both of —NH ₂ and —NHR ⁷ . R ⁷ is a monovalent hydrocarbon group. Preferably at least one of said amino groups is a -NH _2, and more preferably all of the amino group is -NH _2. The hydrocarbon constituting the polyamine may be an aliphatic hydrocarbon or an aromatic hydrocarbon, and may have a heterocyclic ring. Diamines are preferred as polyamines. Among useful polyamines including diamines such as phenylenediamine (such as p-phenylenediamine) and aliphatic diamines, diamines represented by H ₂ N— (CH ₂ ) _n —NH ₂ , wherein n is 2 Diamines of １０10 are preferred. In particular, 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, and 1,10-diaminodecane are preferred. As the diamine having an aromatic structure, xylylenediamine is preferable, and m-xylylenediamine is more preferable. The polyamine can be used as such or in the form of a salt, for example, as a hydrochloride.
The ratio of the amount of cyclic carbonate-substituted propyl catechol to the amount of polyamine used in the reaction is such that the ratio of the number of moles of cyclic carbonate in the cyclic carbonate-substituted propyl catechol to the number of moles of amino groups in the polyamine is 0.8: 1. 2 to 1.2: 0.8 may be appropriately adjusted.
Specific reaction conditions for producing polyhydroxyurethane from the cyclic carbonate-substituted propyl catechol of the present invention include known literature (Rokicki, G .; Parzuchowskia, PG; Magdalena, M. Polym. Adv. Technol. 2015, 26) , 716-721,), (Maisonneuve, L .; Lamarzelle, O .; Rix, E .; Grau, E .; Cramail, H. Chem. Rev. 2015, 115, 12407-12439) Can be adopted.
The reaction temperature is preferably from 50 to 200 ° C, more preferably from 70 to 180 ° C. The reaction can be performed at atmospheric pressure. The reaction time is preferably 1 to 48 hours, more preferably 2 to 24 hours.

Further, the hydrogen atoms at the 3- and 5-positions of the benzene ring of each catechol moiety of the cyclic carbonate-substituted propyl catechol of the present invention may be substituted with a desired substituent as long as the effects of the present invention are not impaired. . Examples of such a substituent include the monovalent hydrocarbon groups exemplified for R ⁴ and R ⁵ . Similarly, the hydrogen atom of the propyl group in each catechol moiety of the cyclic carbonate-substituted propyl catechol of the present invention may be substituted with a desired substituent as long as the effects of the present invention are not impaired. Examples of such a substituent include the monovalent hydrocarbon groups exemplified for R ⁴ and R ⁵ .

<Method for producing cyclic carbonate-substituted propyl catechol>
The method for producing the cyclic carbonate-substituted propyl catechol of the present invention is not particularly limited.
For example, cyclic carbonate-substituted propyl catechol can be produced by a method comprising reacting epoxidized propyl catechol with CO _{2 in} the presence of a catalyst.
As a specific reaction condition and a catalyst to be used, those conventionally used in a reaction for obtaining a cyclic carbonate compound from an epoxy compound and CO ₂ can be employed. For example, as reaction conditions and catalysts, known literature (Agnieszka Siewniak et al., `` An efficient method for the synthesis of cyclic carbonates from CO ₂ and epoxides using an effective two-component catalyst system: Polymer-supported quaternary onium salts and aqueous solutions of metal salts ”, Applied Catalysis A: General Volume 482, 2014, Pages 266-274), (Yanwei Ren et al.,“ Lewis acid-base bifunctional aluminum-salen catalysts: synthesis of cyclic carbonates from carbon dioxide and epoxides ”, RSC Adv ., 2016, 6, 3243-3249), (Shuai-Shuai Yu et al, “A new catalyst for the solvent-free conversion of CO ₂ and epoxides into cyclic carbonate under mild conditions”, Journal of CO ₂ Utilization, Volume 14 , June 2016, Pages 122-125), (M. Alves et al., “Organocatalyzed coupling of carbon dioxide with epoxides for the synthesis of cyclic carbonates: catalyst design and mechanistic studies”, Catal. Sci. Technol., 2017, 7 , 2651-2684) etc. Can be adopted.

For example, the epoxidation propyl catechol in the reactor can be pressurized with CO _2.
The pressure for the pressurization is 0.1 to 40 bar, preferably 1 to 30 bar, more preferably 1 to 20 bar.
The catalyst used in the reaction is not particularly limited, but may be an organic metal catalyst such as a quaternary ammonium salt, a quaternary phosphonium salt, a quaternary arsenium salt, a Lewis acid, lithium bromide, chlorostannoxanes, or an aluminum-salen complex. , And mixtures thereof. The catalyst may or may not be supported.
The solvent used in the reaction is not particularly limited, but examples include dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like.
The amount of the epoxidized propyl catechol to be used may be generally 0.1 to 1 g / mL, or 0.1 to 0.5 g / mL based on the total volume of the solvent.
The concentration of the catalyst used for synthesizing the cyclic carbonate-substituted propyl catechol of the present invention may generally be 0.1 to 20% by mass based on the total mass of the solvent and the catalyst. In another embodiment, it may be 1 to 10% by mass. In yet another embodiment, it may be 2-5% by weight.
The reaction temperature is preferably from 10 to 200 ° C, more preferably from 60 to 150 ° C. The reaction can be performed at atmospheric pressure. The reaction time is preferably 1 to 48 hours, more preferably 2 to 24 hours.

Epoxidized propyl catechol can be manufactured as follows.
R ¹ has an organic group other than that represented by the formula (2), and R ² has an organic group other than the organic group represented by the formula (3). Epoxidized propyl catechol used as a raw material for obtaining carbonate-substituted propyl catechol includes epoxidized propyl catechol produced by reacting propyl catechol with epihalohydrin in the presence of a catalyst and an alkali compound.
Epoxidized propyl catechol used as a raw material for obtaining the compound (A) includes epoxidized propyl catechol produced by reacting propyl catechol with epihalohydrin in the presence of a catalyst and an alkali compound.
As the epoxidized propyl catechol used as a raw material for obtaining the compound (B), propyl catechol is converted into bis-propyl catechol by a dimerization reaction, and the bis-propyl catechol is converted to epihalohydrin in the presence of a catalyst and an alkali compound. And epoxidized propyl catechol produced by reacting
In any case, the reaction with epihalohydrin can be carried out under reaction conditions commonly used in various epoxidation reactions.

The epihalohydrin used in the present embodiment is not particularly limited, and examples include epichlorohydrin, epibromohydrin, epiiodohydrin, and epifluorohydrin.
The epihalohydrins may be used alone or as a mixture of two or more. Of these, epichlorohydrin is preferred.
It is preferable to use 2.2 to 100 mol of epihalohydrin based on 1 mol of the propyl catechol compound.

反 応 The reaction for producing epoxidized propyl catechol is performed in the presence of a catalyst and an alkali compound, but is not limited thereto. Examples of the catalyst include quaternary ammonium salts such as benzyltriethylammonium chloride, benzyltriethylammonium bromide, tetra-n-butylammonium fluoride and tetra-n-butylammonium bromide. It is preferable to use 0.01 to 1 mol of the catalyst, more preferably 0.02 to 0.2 mol, per 1 mol of the propyl catechol compound.

Examples of the alkali compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. It is preferable to use 1.5 to 8 mol of an alkali metal compound, more preferably 2 to 4 mol, per 1 mol of a bis-propylcatechol compound.

具体 The specific procedure and conditions for this reaction are the same as in the case of producing a conventional epoxy resin using bisphenol A. For example, the reaction temperature is preferably from -20 to 200 ° C, more preferably from 0 to 150 ° C. Also, the reaction can be performed at atmospheric pressure. The reaction time is preferably 0.5 to 48 hours, more preferably 1 to 24 hours.

The dimerization reaction for producing bis-propylcatechol is not particularly limited. For example, bis-propylcatechol can be produced substantially according to the method described in Non-Patent Document 5. Specifically, it can be produced by a method comprising reacting propyl catechol with a reactant suitable for forming a desired R ³ group. For example, when R ³ is —CR ⁴ R ⁵ — described above, the reactant may be a ketone such as acetone or cyclohexanone, and R ³ is a divalent aromatic carbon represented by the above formula (4). When it is a hydrogen group, it may be an alcohol such as 1,4-bis (2-hydroxyisopropyl) benzene. When R ³ is a cycloalkylene group which may have a substituent, the reactant may be a corresponding monoterpene. Specifically, when R ³ is a divalent aliphatic hydrocarbon group represented by the above formula (5), the reactant is 1-isopropyl-4-methyl-1,4-cyclohexadiene It may be. Further, when R ³ is an optionally substituted arylalkylene group, the reactant may be the corresponding aldehyde. Specifically, when R ³ is a divalent aromatic hydrocarbon group represented by the above formula (6), the reactant may be cuminaldehyde.
The molar ratio of propyl catechol used in the reaction to the reactant suitable for forming the desired R ³ group (propyl catechol / reactant) is usually from 2 to 2.5.

Note that the use of propyl catechol derived from propyl guaiacol is also a preferred embodiment of the present invention. Propyl guaiacol can be obtained from lignocellulosic biomass. For details of the method for producing propyl catechol from lignocellulosic biomass, see, for example, known literature (Zhuohua Sun et al., “Bright Side of Lignin. Depolymerization: Toward New Platform Chemistry”, Chemical Review 118: 2, 614-678). , 2018.) is an example.

The above-mentioned dimerization reaction can be carried out in the presence of a catalyst if necessary. As the catalyst, for example, a catalyst conventionally used for producing a bisphenol compound can be used. Specifically, a strongly acidic solution such as hydrochloric acid, hydrobromic acid, phosphoric acid, and sulfuric acid, or a strongly acidic cation exchange resin such as a sulfonic acid type can be used.
It is preferable to use the strongly acidic cation exchange resin partially neutralized with a sulfur-containing amine compound. Examples of the sulfur-containing amine compound include 2- (4-pyridyl) ethanethiol, 2-mercaptoethylamine, 3-mercaptopropylamine, N, N-dimethyl-3-mercaptopropylamine, N, N-di-n-butyl- Conventional accelerators used in the synthesis of bisphenol A, such as 4-mercaptobutylamine and 2,2-dimethylthiazolidine, can be used. The amount of such an accelerator is usually 2 to 30 mol%, preferably 5 to 20 mol%, based on the acid groups (sulfonic acid groups) in the strongly acidic cation exchange resin.

The reaction conditions for the dimerization reaction may be those conventionally used for producing a bisphenol compound. Specifically, the reaction temperature of the dimerization reaction is preferably from 0 to 200 ° C, more preferably from 25 to 150 ° C. The reaction can be performed at atmospheric pressure. The reaction time is preferably 30 minutes to 48 hours, more preferably 1 to 24 hours.

In summary, for example, the compound (A) and the compound (B) of the present invention can be produced according to the following reaction scheme.

In the case of the compound (A), n, which is the number of repetitions in the formula (2), can be increased by reacting propyl catechol with an appropriate amount of glycerin before the epoxidation reaction. In the case of the compound (B), n, which is the number of repetitions in the formula (3), can be increased by reacting bis-propylcatechol with an appropriate amount of glycerin before the epoxidation reaction.

<Resin composition containing cyclic carbonate-substituted propyl catechol>
One aspect of the present invention is a cyclic carbonate-substituted propyl catechol of the present invention, and at least one polymer other than the cyclic carbonate-substituted propyl catechol polymer and at least one monomer other than the cyclic carbonate-substituted propyl catechol, or It is a resin composition containing both. In the present specification, the “cyclic carbonate-substituted propyl catechol polymer” means a polymer synthesized from the cyclic carbonate-substituted propyl catechol.
At least one kind of polymer other than the cyclic carbonate-substituted propyl catechol polymer is not particularly limited, and polystyrene, polysulfone, polymethyl methacrylate, polyacrylonitrile, polybutyl acrylate, polymethyl methacrylate, polybutadiene, polyoxymethylene (acetal), Impact polystyrene, polyamide, polybutylene terephthalate, polycarbonate, polyethylene, polyethylene terephthalate, polyetheretherketone, polyetherimide, polyethersulfone, polyphthalamide, polyphenyleneether, polyphenylenesulfide, polyurethane, polyester, poly (styrene-acrylonitrile) , And mixtures thereof.
The weight average molecular weight of the polymer used in the composition can be any suitable value. In a specific embodiment, the weight average molecular weight of the polymer in the resin composition is preferably from 344 to 20,000 g / mol, more preferably from 400 to 8000 g / mol.
At least one monomer other than the cyclic carbonate-substituted propyl catechol is not particularly limited, and examples thereof include the above-described polyamines.
The molecular weight of the monomer used in the composition is preferably from 50 to 300, more preferably from 50 to 200. The formula weight can be adopted as the molecular weight of the monomer.

環状 The content of the cyclic carbonate-substituted propyl catechol in the resin composition is not particularly limited, and can be appropriately adjusted according to the type of the polymer or the monomer, the purpose of the resin composition, and the like. For example, the content of cyclic carbonate-substituted propyl catechol in the resin composition is preferably from 1 to 99 parts by mass, more preferably from 2 to 50 parts by mass, per 100 parts by mass of the resin composition.

The resin composition may further contain a known additive. Known additives include, but are not limited to, ultraviolet stabilizers, heat stabilizers, antioxidants, colorants (eg, pigments or dyes), antistatic agents, flame retardants, smoke suppressants, foaming agents, conductive agents, Lubricants and antiwear agents are mentioned as examples. The content of the additive in the resin composition is preferably from 0.1 to 5 parts by mass, more preferably from 0.3 to 3 parts by mass, per 100 parts by mass of the resin composition.

環状 As the cyclic carbonate-substituted propyl catechol contained in the resin composition, the compound (A) or the compound (B) is preferable.

<Resin cured product>
One aspect of the present invention is a cured resin product obtained by curing the resin composition. Curing can be performed by any appropriate method depending on the type of polymer used in the resin composition. For example, it can be cured by heat, ultraviolet light or the like. If necessary, a suitable curing agent may be used.

<Analysis>
The amount (g) of a material containing 1 g equivalent of cyclic carbonate functional group, referred to as cyclic carbonate equivalent (CCEW) of cyclic carbonate substituted propyl catechol, can be obtained by ¹ H NMR spectroscopy titration described in Examples below. it can.
CCCE of the cyclic carbonate-substituted propyl catechol is preferably 100 to 600 g / equivalent, and more preferably 150 to 500 g / equivalent.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the cyclic carbonate-substituted propyl catechol can be obtained by GPC measurement described in Examples described later.
The number average molecular weight of the cyclic carbonate-substituted propyl catechol is preferably from 400 to 2000 g / mol, more preferably from 400 to 1500 g / mol.
The molecular weight distribution (Mw / Mn) of the cyclic carbonate-substituted propyl catechol is preferably from 1 to 1.5, more preferably from 1 to 1.3.
The temperature (Td _30% ) of the polyhydroxyurethane material obtained by using the cyclic carbonate-substituted propylcatechol of the present invention at a weight loss of 30% (Td _30% ) can be obtained by thermogravimetric analysis (TGA) under an argon atmosphere.
The Td _30% of the polyhydroxyurethane material is preferably from 300 to 350 ° C., more preferably from 300 to 340 ° C.
The glass transition temperature (Tg) of the polyhydroxyurethane material obtained using the cyclic carbonate-substituted propyl catechol of the present invention can be measured by differential scanning calorimetry (DSC).
The Tg of the polyhydroxyurethane material is preferably from 80 to 130 ° C, more preferably from 80 to 120 ° C.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

<Raw materials>
・ 2-methoxy-4-propylphenol (manufactured by Sigma-Aldrich)
・ Sodium hydroxide (manufactured by Sigma-Aldrich)
・ Tetrabutylammonium bromide (TBABr) (Sigmadrich)
・ Lithium bromide (LiBr) (manufactured by Sigma-Aldrich)
・ Dimethylformamide (DMF) (manufactured by Sigma-Aldrich)
・ 48% hydrobromic acid (HBr) (manufactured by Sigma-Aldrich)
・ 98% sulfuric acid (H ₂ SO ₄ ) (manufactured by Sigma-Aldrich)
・ Methanol (manufactured by Sigma-Aldrich)
・ Cuminaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ M-xylylene diisocyanate (m-XDI) (Tokyo Chemical Industry Co., Ltd.)
・ M-xylylenediamine (m-XDA) (Tokyo Chemical Industry Co., Ltd.)
・ Epichlorohydrin (Wako Pure Chemical Industries, Ltd.)
・ Anhydrous magnesium sulfate (Wako Pure Chemical Industries, Ltd.)
・ Tetrahydrofuran (Wako Pure Chemical Industries, Ltd.)
・ Ethyl acetate (Wako Pure Chemical Industries, Ltd.)
・ Deuterated solvent (DMSO-d6) (Cambridge Isotope Laboratories, Inc.)

<Analysis and evaluation method>
・ NMR
In the following Examples and Comparative Examples, the chemical structures of the molecules were determined by ¹ H and ¹³ C measured at room temperature by NMR spectroscopy using a Jeol 400 MHz spectrometer equipped with a royal probe. The external standard used was tetramethylsilane (TMS). Shifts are in ppm. NMR samples were prepared as follows. About 0.5 mL of DMSO-d6 and about 10 mg of an analyte were mixed for ¹ H and ¹³ C measurement.
In the following examples and comparative examples, the amount (g) of a material containing 1 g equivalent of cyclic carbonate functional group, called cyclic carbonate equivalent (CCEW), was determined by ¹ H NMR spectroscopy titration. First, a solution of DMSO-d6 containing toluene as an internal standard was prepared (concentration: 6.90 g / L). Next, a known amount of a cyclic carbonate-substituted propyl catechol resin or a cyclic carbonate-substituted bis-propyl catechol resin (about 60 mg) and a deuterated solution containing toluene (about 800 mg) were weighed and transferred to an NMR tube. Peaks derived from the characteristic cyclic carbonate were obtained at two places, 4.59 ppm and 5.08 ppm. The CCEW was calculated from the following equation by comparing the integral of the proton bonded to the benzene ring of _toluene (ΔH _toluene ) with the integral of the two protons of the _{cyclic carbonate} (ΔH _{cyclic carbonate} ). In the mathematical formula (1), m _{cyclic carbonate} is the mass of cyclic carbonate-substituted propyl catechol, m _toluene is the mass of toluene, and M _toluene is the molecular weight of toluene.

GPC Measurement In the following Examples and Comparative Examples, the molecular weight of a chemical substance was measured using a GPC system (manufactured by Shimadzu Corporation) equipped with two columns KF803L (manufactured by Showa Denko KK) having an exclusion limit molecular weight of 70,000. Measured. The column temperature was set at 40 ° C. and the flow rate was set at 1.0 ml / min. Tetrahydrofuran was used as eluent and RI was used as detector. In the method for calculating the molecular weight, a calibration curve was prepared using standard polystyrene (TSK standard polystyrene) having weight average molecular weights (Mw) of 96400, 37900, 18100, 9100, 5970, 2630, 1050, and 500, respectively. The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were calculated.

-Measurement of thermal stability In the following Examples and Comparative Examples, the thermal stability of the material was determined by thermogravimetric analysis (TGA) using a DTG-60 thermogravimetric analyzer (manufactured by Shimadzu Corporation). The sample was heated from room temperature to 600 ° C. in an aluminum pan under a stream of argon (50 mL / min). The measurement was performed at a heating rate of 10 ° C./min.

ガ ラ ス In the following Examples and Comparative Examples, the glass transition temperature of the material was determined by differential scanning calorimetry (DSC) using a DSC-60 calorimeter (manufactured by Shimadzu Corporation). Argon was used as the inert gas. The sample was placed in an aluminum pan and the thermal properties were recorded at 10 ° C / min.

<Synthesis>
[Production Example 1]
-Synthesis of propyl catechol Propyl catechol was obtained according to the method described in Non-Patent Document 5 and the reaction formula shown in the following formula (7).

2-Methoxy-4-propylphenol (100 g, 601.61 mmol) was added to a 48% aqueous hydrobromic acid solution (250 g, 3.09 mol). The reaction mixture was magnetically stirred at 120 ° C. for 15.5 hours and cooled to room temperature. Next, deionized water was added to the solution and the product was extracted three times with ethyl acetate (3 × 500 mL). The organic phases were combined, washed twice with deionized water (2 × 50 mL), dried over anhydrous MgSO ₄ and concentrated under reduced pressure. The product was obtained as a brown liquid in 91% yield. ¹ H and ¹³ C NMR spectra of the obtained product in deuterated dimethyl sulfoxide were as follows.
¹ H NMR (400 MHz, DMSO-d6) δ (ppm) = 8.65 (s, 1H), 8.55 (s, 1H), 6.62-6.39 (m, 3H), 2.36 ( t, 2H), 1.50 (sex, 2H), 0.85 (t, 3H)
¹³ C NMR (100 MHz, DMSO-d6) δ (ppm) = 144.93, 143.08, 132.94, 118.88, 115.71, 115.38, 36.71, 24.33, 13.65

-Synthesis of epoxidized propyl catechol resin An epoxidized propyl catechol resin was obtained according to the reaction formula shown in the following formula (8).

Propyl catechol obtained above (10.00 g, 65.84 mmol, 1.00 equiv), TBABr (1.06 g, 3.29 mmol, 0.05 equiv) and epichlorohydrin (60.91 g, 658.42 mmol) , 10 eq.) Was added to a four-necked round bottom flask equipped with magnetic stirring and a condenser. The reaction was performed at 60 ° C. for 3 hours. Then, an aqueous solution of NaOH (50% by mass, 4 equivalents) was added. The reaction was then performed at 60 ° C. for 3 hours. Next, the NaOH solution was diluted 4-fold by adding deionized water to the mixture and the same volume of ethyl acetate was added. The mixture was stirred and the aqueous phase was extracted twice more with ethyl acetate (2 × 300 mL). The organic phases are combined, rinsed with aqueous NaCl solution, dried over anhydrous MgSO _4. Ethyl acetate and excess epichlorohydrin were removed under vacuum. Epoxidized propyl catechol resin was obtained as an orange liquid in 82% yield. The ¹ H and ¹³ C NMR spectra of the obtained product in deuterated dimethyl sulfoxide were as follows.
¹ H NMR (400 MHz, DMSO-d6) δ (ppm) = 6.79-6.55 (m, 3H), 4.25-3.70 (m, 4H), 3.29 (m, 2H), 2.80 (q, 2H), 2.68 (m, 2H), 2.41 (sex, 2H), 1.54 (sept, 2H), 0.85 (t, 3H)
¹³ C NMR (100 MHz, DMSO-d5) δ (ppm) = 148.32, 146.12, 136.25, 121.38, 115.92, 74.91, 50.93, 45.85, 36.52 , 24.04, 12.98

-Synthesis of cyclic carbonate substituted propyl catechol resin According to the reaction formula shown in the following formula (9), a cyclic carbonate substituted propyl catechol resin was obtained.

The epoxidized propyl catechol resin obtained above was reacted with CO ₂ as follows. In a 100 mL round bottom flask, epoxidized propyl catechol resin (12.00 g, 45.40 mmol, 1 eq) and LiBr (0.197 g, 2.27 mmol, 0.05 eq) were dissolved in DMF (40 mL). . This solution was introduced into the reactor and replaced with CO ₂ (pressure: 5 bar). The solution was then continuously stirred at 80 ° C. for 6 hours. At the end of the reaction, DMF was removed by vacuum distillation. The resulting mixture was dissolved in ethyl acetate (150 mL) and washed several times with deionized water (3 × 30 mL) and aqueous NaCl (2 × 10 mL). The organic phases were combined, dried over anhydrous MgSO ₄ and concentrated under vacuum. The cyclic carbonate substituted propyl catechol resin was obtained as an orange viscous liquid in 70% yield. The CCW of the cyclic carbonate-substituted propyl catechol resin was determined by ¹ HNMR to be 212 g / equivalent. As a result of measuring the molecular weight (in terms of standard polystyrene) of the obtained cyclic carbonate-substituted propyl catechol resin by GPC, the number average molecular weight Mn was 554 g / mol, the weight average molecular weight Mw was 558 g / mol, and the molecular weight distribution Mw / Mn was 1. 07. Therefore, the average value of n calculated from Mn was 1.57. The ¹ H and ¹³ C NMR spectra of the obtained product in deuterated dimethyl sulfoxide were as follows.
¹ H NMR (400 MHz, DMSO-d6) δ (ppm) = 6,94-6.64 (dd, 3H), 5.11 (m, 2H), 4.63 (m, 2H), 4.43 ( m, 2H), 4.31-4.11 (m, 4H), 2.42 (t, 2H), 1.55 (oct, 2H), 0.88 (t, 3H)
¹³ C NMR (100 MHz, DMSO-d) δ (ppm) = 154.81, 148.23, 146.03, 136.30, 121.41, 115.74, 74.91, 66.03, 65.96 , 36.48, 24.14, 13.49

[Production Example 2]
-Synthesis of bis-propyl catechol Bis-propyl catechol was obtained according to the reaction formula shown in the following formula (10).

Cuminaldehyde (9.69 g, 65.38 mmol) and propyl catechol obtained above (20.00 g, 135.45 mmol) were dissolved at 5 ° C. in 20 mL of methanol in a 200 mL round bottom flask. To this reaction mixture was added dropwise an aqueous H ₂ SO ₄ solution (98% H ₂ SO ₄ , 3.22 g (36.69 mmol), previously diluted with 5 mL of methanol) while stirring. The flask was then sealed and the reaction mixture was further stirred at a temperature below 10 ° C. for 1 hour and then at 63 ° C. for 10 hours. The reaction mixture was then neutralized with saturated aqueous NaHCO ₃ and the product was extracted three times with diethyl ether (3 × 100 mL), the combined organic phases were washed with deionized water, dried over anhydrous MgSO ₄ and filtered. And concentrated under reduced pressure. The product was obtained as a brown solid in 97% yield. The ¹ H and ¹³ C NMR spectra of the obtained product in deuterated dimethyl sulfoxide were as follows.
¹ H NMR (400 MHz, DMSO-d6) δ (ppm) = 8.51 (s, 2H), 8.50 (s, 2H), 7.14-6.85 (dd, 4H), 6.52 ( s, 2H), 6.17 (s, 2H), 5.47 (s, 1H), 2.84 (sep, 1H), 2.25 (t, 4H), 1.37 (sex, 4H), 1.18 (d, 6H), 0.81 (t, 6H)
¹³ C NMR (100 MHz, DMSO-d5) δ (ppm) = 145.47, 143.04, 142.42, 142.36, 132.59, 130.53, 129.00, 125.94, 117.18 , 116.78, 47.01, 33.66, 32.88, 23.91, 23.74, 14.04.

Synthesis of epoxidized bis-propyl catechol resin An epoxidized bis-propyl catechol resin was obtained according to the reaction formula shown in the following formula (11).

Bispropyl catechol obtained above (20.00 g, 46.0 mmol, 1.00 equivalent), TBABr (1.48 g, 4.60 mmol, 0.10 equivalent) and epichlorohydrin (85.16 g, 920. (43 mmol, 20 equiv) was added to a four-necked round bottom flask equipped with magnetic stirring and a condenser. The reaction was performed at 60 ° C. for 3 hours. Then, an aqueous solution of NaOH (50% by mass, 4 equivalents) was added. The reaction was then performed at 60 ° C. for 3 hours. Next, the NaOH solution was diluted 4-fold by adding deionized water to the mixture and the same volume of ethyl acetate was added. The mixture was stirred and the aqueous phase was extracted twice more with ethyl acetate (2 × 300 mL). The organic phases are combined, rinsed with aqueous NaCl solution, dried over anhydrous MgSO _4. Ethyl acetate and excess epichlorohydrin were removed under vacuum. The epoxidized bis-propylcatechol resin was obtained as an orange solid in 90% yield. The ¹ H and ¹³ C NMR spectra of the obtained product in deuterated dimethyl sulfoxide were as follows.
¹ H NMR (400 MHz, DMSO-d6) δ (ppm) = 7.14-6.92 (dd, 4H), 6.67-6.12 (m, 4H), 5.63 (s, 1H), 5.00 (m, 0.60H), 4.29-4.00 (m, 4H), 3.83-3.59 (m, 4H), 3.15 (m, 1.5H), 2. 82 (m, 2H), 2.70 (m, 2H), 2.38 (t, 3.70H), 1.41 (sex, 4H), 1.17 (d, 6H), 0.82 (t , 6H)
¹³ C NMR (100 MHz, DMSO-d) δ (ppm) = 147.89, 146.58, 141.31, 133.79, 129.01, 126.15, 116.96, 115.62, 69.89 , 49.95, 47.31, 43.75, 33.90, 32.96, 23.96, 23.67, 14.00.

-Synthesis of cyclic carbonate substituted bis-propyl catechol resin According to the reaction formula shown in the following formula (12), cyclic carbonate substituted bis-propyl catechol resin was obtained.

The epoxidized bis-propylcatechol resin obtained above was reacted with CO ₂ as follows. In a 100 mL round bottom flask, epoxidized bis-propyl catechol resin (10.00 g, 15.18 mmol, 1 equivalent) and LiBr (0.07 g, 0.76 mmol, 0.05 equivalent) are dissolved in DMF (30 mL). I let it. This solution was introduced into the reactor and replaced with CO ₂ (pressure: 9 bar). The solution was then continuously stirred at 80 ° C. for 12 hours. At the end of the reaction, DMF was removed by vacuum distillation. The resulting mixture was dissolved in ethyl acetate (150 mL) and washed several times with deionized water (3 × 30 mL) and aqueous NaCl (2 × 10 mL). The organic phases were combined, dried over anhydrous MgSO ₄ and concentrated under vacuum. The cyclic carbonate substituted bis-propyl catechol resin was obtained as an orange solid in 87% yield. CCW of the cyclic carbonate-substituted bis-propylcatechol resin was titrated by ¹ HNMR to find that it was 409 g / equivalent. As a result of measuring the molecular weight (in terms of standard polystyrene) of the obtained cyclic carbonate-substituted bis-propylcatechol resin by GPC method, the number average molecular weight Mn was 949 g / mol, the weight average molecular weight Mw was 953 g / mol, and the molecular weight distribution Mw / Mn was 1.03. Therefore, the average value of n calculated from Mn was 1.14. The ¹ H and ¹³ C NMR spectra of the obtained product in deuterated dimethyl sulfoxide were as follows.
¹ H NMR (400 MHz, DMSO-d6) δ (ppm) = 7.17-6.93 (dd, 4H), 6.34-6.12 (m, 4H), 5.66 (s, 1H), 5.12 (m, 2H), 4.99 (m, 2H), 4.64-3.90 (m, 16H), 2.86 (quint, 1H), 2.40 (t, 4H), 1 .42 (sex, 4H), 1.17 (d, 6H), 0.85 (t, 6H)
¹³ C NMR (100 MHz, DMSO-d) δ (ppm) = 154.63, 146.18, 145.71, 145.24, 138.91, 132.73, 128.86, 126.01, 117.39. , 116.36, 74.79, 65.83, 59.89, 33.72, 32.37, 23.34, 23.33, 13.51.

<Material synthesis and evaluation>
[Comparative Example 1]
-Synthesis and evaluation of polyurethane material First, bis-propylcatechol was melted and mechanically mixed with propylcatechol in a glass pot using a speed mixer at 2,000 rpm for 4 minutes. The molar ratio of propyl catechol to bis-propyl catechol was 1: 1. Then, when a homogeneous mixture was obtained, m-XDI was added to the mixture in a stoichiometric ratio, and the mixture was stirred in a glass pot at 2000 rpm for 2 minutes using a speed mixer. The molar ratio of OH: NCO was 1: 1. Once a homogeneous mixture was obtained, the mixture was poured into an aluminum mold and cured at 100 ° C. for 3 hours and then at 150 ° C. for 1 hour. Table 1 shows Td _30% and Tg of the polyurethane material. Td _30% is the temperature at the time of 30% weight loss, and was measured by TGA under an argon atmosphere. Tg is the glass transition temperature and was measured by DSC.

[Example 1]
・ Synthesis and evaluation of polyhydroxyurethane material First, the cyclic carbonate-substituted bis-propyl catechol resin was melted, and mechanically converted to cyclic carbonate-substituted propyl catechol using a speed mixer in a glass pot at 2,000 rpm for 6 minutes. Mixed. The molar ratio between the cyclic carbonate-substituted propyl catechol and the cyclic carbonate-substituted bis-propyl catechol was 1: 1. Then, when a homogeneous mixture was obtained, m-XDA was added in a stoichiometric ratio, and the mixture was stirred in a glass pot at 2000 rpm for 2 minutes using a speed mixer. The molar ratio of cyclic carbonate: NH ₂ was 1: 1. Once a homogeneous mixture was obtained, the mixture was poured into an aluminum mold and cured at 100 ° C. for 3 hours, then at 150 ° C. for 3 hours. Table 1 shows Td _30% and Tg of the polyhydroxyurethane material. Td _30% is the temperature at the time of 30% weight loss, and was measured by TGA under an argon atmosphere. Tg is the glass transition temperature and was measured by DSC.

As shown in Table 1, polyhydroxyurethane-based materials synthesized without using harmful isocyanates had better thermal properties than polyurethane-based materials.

Claims (13)

A cyclic carbonate-substituted propyl catechol having a structure represented by the formula (1).

[In the formula (1), R ¹ and R ² are each independently a hydrogen atom or an organic group. ] The cyclic carbonate-substituted propyl catechol according to claim 1, wherein R ¹ is an organic group represented by the formula (2).

[In the formula (2), n is an integer of 0 to 300. * Indicates a bonding site to an oxygen atom in the cyclic carbonate-substituted propyl catechol structure in the formula (1). ] The cyclic carbonate-substituted propyl catechol according to claim 1 or 2, wherein R ² is an organic group represented by the formula (3).

[In the formula (3), R ³ is a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group, and n is an integer of 0 to 300. * Indicates a binding site to a benzene ring in the cyclic carbonate-substituted propyl catechol structure in the formula (1). ] R ³ is a divalent hydrocarbon group represented by —CR ⁴ R ⁵ —, R ⁴ and R ⁵ are each independently a monovalent hydrocarbon group, and R ⁴ and R ⁵ are bonded to form a cyclic group. The cyclic carbonate-substituted propyl catechol according to claim 3, which may form a structure. The cyclic carbonate-substituted propyl catechol according to claim 3, wherein R ³ is a divalent aromatic hydrocarbon group represented by the formula (4).

[In the formula (4), R ⁶ is a divalent hydrocarbon group represented by —CR ⁴ R ⁵ —, and R ⁴ and R ⁵ are each independently a monovalent hydrocarbon group. * Indicates a binding site to the benzene ring in the cyclic carbonate-substituted propylcatechol structure in the formula (3). ] The cyclic carbonate-substituted propyl catechol according to claim 5, wherein R ⁴ and R ⁵ are methyl groups. The cyclic carbonate-substituted propyl catechol according to [3], wherein R ³ is a cycloalkylene group which may have a substituent. The cyclic carbonate-substituted propyl catechol according to claim 3 or 7, wherein R ³ is a divalent aliphatic hydrocarbon group represented by the formula (5).

[* Indicates a binding site to the benzene ring in the cyclic carbonate-substituted propyl catechol structure in the formula (3). ] The cyclic carbonate-substituted propyl catechol according to claim 3, wherein R ³ is an arylalkylene group which may have a substituent. The cyclic carbonate-substituted propyl catechol according to claim 3 or 9, wherein R ³ is a divalent aromatic hydrocarbon group represented by the formula (6).

[* Indicates a binding site to the benzene ring in the cyclic carbonate-substituted propyl catechol structure in the formula (3). ] The method for producing cyclic carbonate-substituted propyl catechol according to any one of claims 1 to 10, comprising reacting epoxidized propyl catechol with CO _{2 in} the presence of a catalyst. The cyclic carbonate-substituted propyl catechol according to any one of claims 1 to 10, and at least one polymer other than the cyclic carbonate-substituted propyl catechol polymer and at least one monomer other than the cyclic carbonate-substituted propyl catechol. A resin composition containing one or both. A cured resin obtained by curing the resin composition according to claim 12.