KR20210131497A - Furan-based flame retardant epoxy compound, epoxy resin composition comprising same, and method of preparing same - Google Patents

Abstract

The present invention relates to a furan-based flame retardant epoxy compound, an epoxy resin composition including the same and a method for preparing the same. The epoxy compound is represented by structural formula 1, is based on a bio-substance and is eco-friendly, and contains furan and phosphorus to provide excellent flame retardancy. In structural formula 1: each of R^1 and R^2 independently represents a hydrogen atom or C1-C3 alkyl group; each R^3 independently represents a C1-C3 alkylene group; each of R^4 and R^5 independently represents a C1-C6 alkyl group; each R^6 independently represents a C1-C3 alkylene group; R^7 represents a hydrogen atom or structure 1; R^9 represents a C1-C3 alkylene group; R^8 represents a hydrogen atom or structure 2; and R^10 represents a C1-C3 alkylene group.

Description

A furan-based flame-retardant epoxy compound, an epoxy resin composition comprising the same, and a manufacturing method thereof

The present invention relates to a furan-based flame-retardant epoxy compound, an epoxy resin composition comprising the same, and a manufacturing method thereof, and the epoxy compound of the present invention is a bio-based compound, and has excellent flame retardancy by including furan and phosphorous .

Most of the fine chemical materials we currently use are petrochemical products derived from the Oil Refinery Process, but the international oil price is steadily rising due to a decrease in reserves and a surge in demand centered on BRICs. As an international treaty that strictly regulates gas emissions comes into effect, the use of irreversible fossil resources such as petroleum is expected to incur enormous environmental costs in the future.

Therefore, many efforts are being made to obtain fine chemical products derived from existing petroleum resources from new resources, and the most representative one is to use carbohydrate-based biomass as a source. Specifically, in order to replace the existing petroleum-derived curable adhesive material, a study for synthesizing a compound having a predetermined adhesion or adhesion property using such carbohydrate-based biomass is in progress.

Among the existing petroleum-derived fine chemical products, bisphenol-based epoxy resins are widely used in various industrial fields such as coatings, adhesives, electrical and electronic engineering, civil construction, etc. . However, bisphenol-based epoxy resins do not have excellent flame retardancy, and as polymer resins derived from petroleum resources, they can generate chemicals harmful to the human body such as environmental hormones during manufacture and use. There is a problem that causes environmental pollution.

Accordingly, although research on biomass-based polymer resins that can replace bisphenol-based epoxy resins is being conducted, there is a problem in that physical properties are deteriorated.

Therefore, there is a need for research on an epoxy compound that does not deteriorate in properties based on biomass and has a flame retardancy, a resin containing the same, and a method for preparing the same.

An object of the present invention is to solve the above problems, and to provide an epoxy compound having excellent physical properties based on bio, a resin including the same, and a method for manufacturing the same.

In addition, it is to provide an epoxy compound having a flame retardancy, a resin comprising the same, and a method for producing the same.

According to one aspect of the present invention, an epoxy compound represented by Structural Formula 1 is provided.

[Structural Formula 1]

In Structural Formula 1,

R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ³ are each independently a C1 to C3 alkylene group,

R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,

R ⁶ are each independently a C1 to C3 alkylene group,

이고,R ⁷ is a hydrogen atom or

ego,

R ⁹ is a C1 to C3 alkylene group,

이고,R ⁸ is a hydrogen atom or

ego,

R ¹⁰ is a C1 to C3 alkylene group.

In addition, in Structural Formula 1, R ⁷ may be a hydrogen atom, and R ⁸ may be a hydrogen atom.

이고, R¹⁰은 C1 내지 C3 알킬렌기일 수 있다.In addition, in Structural Formula 1, R ⁷ is a hydrogen atom, R ⁸ is

and R ¹⁰ may be a C1 to C3 alkylene group.

According to another aspect of the present invention, an epoxy compound represented by Structural Formula 1; Epoxy compound represented by Structural Formula 2; and a curing agent; is provided.

[Structural Formula 1]

In Structural Formula 1,

R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ³ are each independently a C1 to C3 alkylene group,

R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,

R ⁶ are each independently a C1 to C3 alkylene group,

이고,R ⁷ is a hydrogen atom or

ego,

R ⁹ is a C1 to C3 alkylene group,

이고,R ⁸ is a hydrogen atom or

ego,

R ¹⁰ is a C1 to C3 alkylene group,

[Structural Formula 2]

In Structural Formula 2,

R ¹¹ is each independently a C1 to C3 alkylene group.

In addition, the compound represented by Structural Formula 1 may include a compound represented by Structural Formula 1-1 below and a compound represented by Structural Formula 1-2 below.

[Structural Formula 1-1]

[Structural Formula 1-2]

In Structural Formula 1-1 or 1-2,

R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ³ are each independently a C1 to C3 alkylene group,

R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,

R ⁶ are each independently a C1 to C3 alkylene group,

R ¹⁰ is a C1 to C3 alkylene group.

In addition, the epoxy composition is 100 parts by mole of the epoxy compound represented by the Structural Formula 2; and 10 to 200 mole parts of the epoxy compound represented by Structural Formula 1;

In addition, the ratio (m ₁ :m ₂ ) of the number _{of moles (m 1} ) of the epoxy compound represented by Structural Formula 1-1 _{and the number of moles (m 2} ) of the epoxy compound represented by Structural Formula 1-2 is 30:70 to 50 It could be :50.

In addition, the curing agent may be a compound represented by the following structural formula (3).

[Structural Formula 3]

In Structural Formula 3,

R ¹² and R ¹³ are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ¹⁴ is each independently a C1 to C3 alkylene group.

In addition, the epoxy composition contains 40 to 60 mole parts of the amine group of the curing agent with respect to 100 mole parts of the epoxy group of the total epoxy compound, and the total epoxy compound is an epoxy compound represented by Structural Formula 1 and an epoxy compound represented by Structural Formula 2 may include

According to another aspect of the present invention, (a) according to Scheme 1, 5-hydroxymethylfurfural (HMF) is reacted with a compound represented by Structural Formula 11 with a compound represented by Structural Formula 12 to form a structural formula preparing a compound represented by 13; and (b) reacting a compound represented by Structural Formula 13 with a compound represented by Structural Formula 14 according to Scheme 2 to prepare an epoxy compound represented by Structural Formula 1;

[Scheme 1]

[Scheme 2]

In Scheme 1 or 2,

R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ³ are each independently a C1 to C3 alkylene group,

R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,

R ⁶ are each independently a C1 to C3 alkylene group,

이고,R ⁷ is a hydrogen atom or

ego,

R ⁹ is a C1 to C3 alkylene group,

이고,R ⁸ is a hydrogen atom or

ego,

R ¹⁰ is a C1 to C3 alkylene group,

X is F, Cl, Br or I.

In addition, in Scheme 1 or 2, R ⁷ may be a hydrogen atom, and R ⁸ may be a hydrogen atom.

이고, R¹⁰은 C1 내지 C3 알킬렌기일 수 있다.In addition, in Scheme 1 or 2, R ⁷ is a hydrogen atom, and R ⁸ is

and R ¹⁰ may be a C1 to C3 alkylene group.

_{In addition, ZnCl 2} may be used as the reaction catalyst of step (a).

In addition, tetra-n-butylammonium bromide (TBABr) may be used as the reaction catalyst of step (b).

In addition, the step (a) comprises the steps of (a-1) reacting 5-hydroxymethylfurfural (HMF) with the compound represented by the structural formula 11; and (a-2) reacting the product of step (a-1) with a compound represented by Structural Formula 12 to prepare a compound represented by Structural Formula 13;

In addition, the step (a-1) may be performed at a temperature of 10 to 80 °C, and the step (a-2) may be performed at a temperature of 50 to 100 °C.

In addition, the step (b) may be performed at a temperature of 50 to 100 ℃.

According to another aspect of the present invention, (1) preparing an epoxy composition comprising an epoxy compound represented by Structural Formula 1 and an epoxy compound represented by Structural Formula 2 and a curing agent; (2) degassing the epoxy composition; And (3) curing the defoamed epoxy composition to prepare an epoxy resin; is provided a method for producing an epoxy resin comprising a.

[Structural Formula 1]

In Structural Formula 1,

R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ³ are each independently a C1 to C3 alkylene group,

R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,

R ⁶ are each independently a C1 to C3 alkylene group,

이고,R ⁷ is a hydrogen atom or

ego,

R ⁹ is a C1 to C3 alkylene group,

이고,R ⁸ is a hydrogen atom or

ego,

R ¹⁰ is a C1 to C3 alkylene group,

[Structural Formula 2]

In Structural Formula 2,

R ¹¹ is each independently a C1 to C3 alkylene group.

In addition, the curing agent may be a compound represented by the following structural formula (3).

[Structural Formula 3]

In Structural Formula 3,

R ¹² and R ¹³ are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ¹⁴ is each independently a C1 to C3 alkylene group.

In addition, the step (3) may be performed at a temperature of 80 to 200 ℃.

The epoxy compound of the present invention and the epoxy resin containing the same are produced on a bio-based basis, so chemical substances harmful to the human body are not generated during manufacture and use, and environmental pollution is not caused when discarded, so it is eco-friendly.

In detail, if the bio-based carbon contained in the epoxy resin of the present invention is calculated theoretically based on the structural formula, the epoxy compound (FFBFE) and the bio-based carbon having 48.9 to 56.4 mol% of bio-based carbon depending on the epoxy group substitution rate It contains at least 48 mol% of bio-based carbon by including 50.0 mol% of epoxy compound (FE).

In addition, the epoxy compound of the present invention and the epoxy resin including the same have excellent flame retardancy by including furan and phosphorous.

In addition, the epoxy compound of the present invention and the epoxy resin containing the same have excellent mechanical properties.

These drawings are for reference in describing an exemplary embodiment of the present invention, and the technical spirit of the present invention should not be construed as being limited to the accompanying drawings.
1 shows the FT-IR analysis results of Examples 1 and 2 and Comparative Examples 1 and 2;
FIG. 2A shows differential scanning calorimetry (DSC) of Examples 1 and 2 and Comparative Examples 1 and 2 measured by the Kissinger method.
2B shows differential scanning calorimetry (DSC) of Examples 1 and 2 and Comparative Examples 1 and 2 measured by the Ozawa method.
3A shows the results of measuring the modulus of elasticity of Examples 1 and 2 and Comparative Examples 1 and 2;
3B shows the measurement results of tan delta, which is the ratio of the lost elastic modulus to the stored elastic modulus of Examples 1 and 2 and Comparative Examples 1 and 2;
4A shows the results of thermogravimetric analysis of Examples 1 and 2 and Comparative Examples 1 and 2;
4B is a thermogravimetric differential (DTG) curve showing the weight change rate according to temperature/time of Examples 1 and 2 and Comparative Examples 1 and 2;
5A shows the tensile strength test results of Examples 1 and 2 and Comparative Examples 1 and 2;
5B shows the tensile modulus test results of Examples 1 and 2 and Comparative Examples 1 and 2;
6A shows the total heat release (THR) of Examples 1 and 2 and Comparative Examples 1 and 2;
6b shows the heat release rate (HRR) of Examples 1 and 2 and Comparative Examples 1 and 2;
6c shows the spread of fire over time in Examples 1 to 2 and Comparative Examples 1 to 2;

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art to which the present invention pertains can easily carry out the present invention.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that a detailed description of a related known technology may obscure the gist of the present invention in describing the present invention, the detailed description thereof will be omitted. .

The terminology used herein is only used to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, element, or combination thereof described in the specification exists, but is one or more other features or It should be understood that the existence or addition of numbers, steps, acts, elements, or combinations thereof, is not precluded in advance.

In addition, terms including an ordinal number such as first, second, etc. to be used below may be used to describe various elements, but the elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

In addition, when it is said that a component is "formed" or "stacked" on another component, it may be formed or laminated directly attached to the front surface or one surface on the surface of the other component. It should be understood that other components may be present in the .

Hereinafter, the furan-based flame-retardant epoxy compound of the present invention, an epoxy resin composition comprising the same, and a manufacturing method thereof will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

The present invention provides an epoxy compound represented by Structural Formula 1.

[Structural Formula 1]

In Structural Formula 1,

R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ³ are each independently a C1 to C3 alkylene group,

R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,

R ⁶ are each independently a C1 to C3 alkylene group,

이고,R ⁷ is a hydrogen atom or

ego,

R ⁹ is a C1 to C3 alkylene group,

이고,R ⁸ is a hydrogen atom or

ego,

R ¹⁰ is a C1 to C3 alkylene group.

In addition, in Structural Formula 1, R ⁷ may be a hydrogen atom, and R ⁸ may be a hydrogen atom.

이고, R¹⁰은 C1 내지 C3 알킬렌기일 수 있다.In addition, in Structural Formula 1, R ⁷ is a hydrogen atom, R ⁸ is

and R ¹⁰ may be a C1 to C3 alkylene group.

The present invention is an epoxy compound represented by Structural Formula 1; Epoxy compound represented by Structural Formula 2; and a curing agent; provides an epoxy composition comprising.

[Structural Formula 1]

In Structural Formula 1,

R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ³ are each independently a C1 to C3 alkylene group,

R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,

R ⁶ are each independently a C1 to C3 alkylene group,

이고,R ⁷ is a hydrogen atom or

ego,

R ⁹ is a C1 to C3 alkylene group,

이고,R ⁸ is a hydrogen atom or

ego,

R ¹⁰ is a C1 to C3 alkylene group,

[Structural Formula 2]

In Structural Formula 2,

R ¹¹ is each independently a C1 to C3 alkylene group.

In addition, the compound represented by Structural Formula 1 may include a compound represented by Structural Formula 1-1 below and a compound represented by Structural Formula 1-2 below.

[Structural Formula 1-1]

[Structural Formula 1-2]

In Structural Formula 1-1 or 1-2,

R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ³ are each independently a C1 to C3 alkylene group,

R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,

R ⁶ are each independently a C1 to C3 alkylene group,

R ¹⁰ is a C1 to C3 alkylene group.

100 parts by mole of an epoxy compound in which the epoxy composition is represented by Structural Formula 2; and 10 to 200 mole parts of the epoxy compound represented by the Structural Formula 1; preferably, 100 mole parts of the epoxy compound represented by the Structural Formula 2; and 30 to 100 mole parts of the epoxy compound represented by Structural Formula 1;

When the amount of the compound represented by Structural Formula 1 is less than 30 mol parts, the mechanical properties of the epoxy resin are low, which is undesirable, and when it exceeds 100 mol parts, the compound represented by Structural Formula 1 has a low number of epoxy groups compared to the molecular weight size and low crosslinking degree It is not preferable because the physical properties of the cured product are low.

In addition, the ratio (m ₁ :m ₂ ) of the number _{of moles (m 1} ) of the epoxy compound represented by Structural Formula 1-1 _{and the number of moles (m 2} ) of the epoxy compound represented by Structural Formula 1-2 is 30:70 to 50 It could be :50.

In addition, the curing agent may be a compound represented by the following structural formula (3).

[Structural Formula 3]

In Structural Formula 3,

R ¹² and R ¹³ are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ¹⁴ is each independently a C1 to C3 alkylene group.

In addition, the epoxy composition contains 40 to 60 mole parts of the amine group of the curing agent with respect to 100 mole parts of the epoxy group of the total epoxy compound, and the total epoxy compound is an epoxy compound represented by Structural Formula 1 and an epoxy compound represented by Structural Formula 2 may include

When the curing agent is less than 40 mol parts, it is not preferable because the reaction between the epoxy compound and the curing agent is not smooth and hardening is difficult.

The present invention relates to (a) reacting 5-hydroxymethylfurfural (HMF) with a compound represented by Structural Formula 11 and a compound represented by Structural Formula 12 according to Scheme 1 to prepare a compound represented by Structural Formula 13 step; and (b) reacting the compound represented by Structural Formula 13 with the compound represented by Structural Formula 14 according to Scheme 2 to prepare an epoxy compound represented by Structural Formula 1; provides a method for producing an epoxy compound comprising.

[Scheme 1]

[Scheme 2]

In Scheme 1 or 2,

R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ³ are each independently a C1 to C3 alkylene group,

R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,

R ⁶ are each independently a C1 to C3 alkylene group,

이고,R ⁷ is a hydrogen atom or

ego,

R ⁹ is a C1 to C3 alkylene group,

이고,R ⁸ is a hydrogen atom or

ego,

R ¹⁰ is a C1 to C3 alkylene group,

X is F, Cl, Br or I.

In addition, in Scheme 1 or 2, R ⁷ may be a hydrogen atom, and R ⁸ may be a hydrogen atom.

이고, R¹⁰은 C1 내지 C3 알킬렌기일 수 있다.In addition, in Scheme 1 or 2, R ⁷ is a hydrogen atom, and R ⁸ is

and R ¹⁰ may be a C1 to C3 alkylene group.

_{In addition, ZnCl 2} may be used as the reaction catalyst of step (a).

In addition, tetra-n-butylammonium bromide (TBABr) may be used as the reaction catalyst of step (b).

In addition, the step (a) comprises the steps of (a-1) reacting 5-hydroxymethylfurfural (HMF) with the compound represented by the structural formula 11; and (a-2) reacting the product of step (a-1) with a compound represented by Structural Formula 12 to prepare a compound represented by Structural Formula 13;

In addition, the step (a-1) may be carried out at a temperature of 10 to 80 ℃, preferably 20 to 60 ℃, more preferably it may be carried out at a temperature of 30 to 50 ℃. When step (a-1) is carried out at a temperature of less than 10°C, the reaction between 5-hydroxymethylfurfural and the compound represented by the structural formula 11 does not occur, which is not preferable, and may be performed at a temperature exceeding 80°C. In this case, an addition reaction may occur, which is not preferable.

In addition, the step (a-2) may be carried out at a temperature of 50 to 100 ℃, preferably 60 to 90 ℃, more preferably it may be carried out at a temperature of 75 to 85 ℃. When step (a-2) is performed at a temperature of less than 50° C., it is not preferable because the reaction of the reactant of step (a-1) with the compound represented by the structural formula 12 does not occur, and it is performed at a temperature exceeding 100° C. If this is the case, an addition reaction may occur, which is not preferable.

In addition, the step (b) may be carried out at a temperature of 50 to 100 ℃, preferably 60 to 90 ℃, more preferably it may be carried out at a temperature of 75 to 85 ℃. When step (b) is carried out at a temperature of less than 50° C., it is not preferable because the reaction of the compound represented by the structural formula 13 with the compound represented by the structural formula 14 does not occur, and when carried out at a temperature exceeding 100° C., addition This is undesirable as a reaction may occur.

The present invention comprises the steps of (1) preparing an epoxy composition comprising an epoxy compound represented by Structural Formula 1 and an epoxy compound represented by Structural Formula 2 and a curing agent; (2) degassing the epoxy composition; And (3) curing the defoamed epoxy composition to prepare an epoxy resin; provides a method for producing an epoxy resin comprising a.

[Structural Formula 1]

In Structural Formula 1,

R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ³ are each independently a C1 to C3 alkylene group,

R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,

R ⁶ are each independently a C1 to C3 alkylene group,

이고,R ⁷ is a hydrogen atom or

ego,

R ⁹ is a C1 to C3 alkylene group,

이고,R ⁸ is a hydrogen atom or

ego,

R ¹⁰ is a C1 to C3 alkylene group,

[Structural Formula 2]

In Structural Formula 2,

R ¹¹ is each independently a C1 to C3 alkylene group.

100 parts by mole of an epoxy compound in which the epoxy composition is represented by Structural Formula 2; and 10 to 200 mole parts of the epoxy compound represented by the Structural Formula 1; preferably, 100 mole parts of the epoxy compound represented by the Structural Formula 2; and 30 to 100 mole parts of the epoxy compound represented by Structural Formula 1;

When the amount of the compound represented by Structural Formula 1 is less than 30 mol parts, the mechanical properties of the epoxy resin are low, which is undesirable, and when it exceeds 100 mol parts, the compound represented by Structural Formula 1 has a low number of epoxy groups compared to the molecular weight size and low crosslinking degree It is not preferable because the physical properties of the cured product are low.

In addition, the ratio (m ₁ :m ₂ ) of the number _{of moles (m 1} ) of the epoxy compound represented by Structural Formula 1-1 _{and the number of moles (m 2} ) of the epoxy compound represented by Structural Formula 1-2 is 30:70 to 50 It could be :50.

In addition, the curing agent may be a compound represented by the following structural formula (3).

[Structural Formula 3]

In Structural Formula 3,

R ¹² and R ¹³ are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ¹⁴ is each independently a C1 to C3 alkylene group.

In addition, the epoxy composition includes 40 to 60 mole parts of the amine group of the curing agent with respect to 100 mole parts of the epoxy group of the total epoxy compound, and the total epoxy compound is an epoxy compound represented by Structural Formula 1 and an epoxy compound represented by Structural Formula 2 may include

When the curing agent is less than 40 mol parts, it is not preferable because the reaction between the epoxy compound and the curing agent is not smooth and hardening is difficult.

In addition, the step (3) may be carried out at a temperature of 80 to 200 °C, preferably at a temperature of 100 to 180 °C, more preferably 3 at 100 °C, 140 °C, 180 °C, respectively. It can be done with step hardening performed over time. When step (3) is performed at a temperature of less than 80° C., it is not preferable because curing does not occur, and when it exceeds 200° C., an addition reaction may occur, which is not preferable.

[Example]

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes only, and the scope of the present invention is not limited thereto.

manufacturing example One: Bishydroxymethylfuran ( bis(hydroxymethyl)furan , BHF ) Produce

A three-necked round-bottom flask was prepared, 20 g (0.53 mmol) of lithium aluminum hydride (LAH) and 500 mL of tetrahydrofuran (THF) were added thereto, and after stirring, it was brought to 0 ° C in an ice bath.

Thereafter, 100 g (0.79 mmol) of 5-hydroxymethylfurfural (HMF) was diluted in tetrahydrofuran and added dropwise very slowly, followed by stirring for 24 hours.

For LAH killing, 200 mL of distilled water was slowly added dropwise, and THF was removed by concentration, washed three times with ethyl acetate, and column chromatography was performed under 100% ethyl acetate (EA) conditions to form yellow powder. 85.4 g of the reaction product (BHF yield 84.1%) was obtained.

¹ H-NMR (300 MHz, CDCl ₃ , δ ) results of the yellow powder were 6.27-6.25 (s , 2H), 4.63-4.59 ( s , 4H), and ¹³ C NMR (300 MHz, CDCl ₃ , δ ) The results were 154.1, 108.7, and 57.5, confirming that BHF was well prepared.

The reaction in the preparation of the bishydroxymethylfuran is shown in Scheme 3 below.

[Scheme 3]

manufacturing example 2: FE manufacturing

Prepare a three-necked round-bottom flask, and prepare NaOH 95.96g (2.40 mol), water (H ₂ O) 95.96g (5.33 mol), epichlorohydrin (epichlorohydrin, d=1.18g/ml) 226.57g (2.80 mol) and After adding 6.45 g (0.02 mol) of tetrabutylammonium bromide (TBABr) and stirring, a cooler was installed and an N ₂ atmosphere was created.

After diluting BHF prepared according to Preparation Example 1 in tetrahydrofuran (THF), it was added dropwise very slowly. Then, the mixture was stirred at 50° C. for 2 hours, extracted three times with ethyl acetate, and the solvent was removed by concentration. Then, column chromatography (hexane (HX): ethyl acetate (EA) = 2: 1) was performed to obtain 28 g of a yellow liquid reactant (FE yield 57%).

¹ H-NMR (300 MHz, CDCl ₃ , δ ) of the yellow liquid was 6.31-6.29 ( m , 1H), 4.58-4.47 ( m , 2H), 3.81-3.73 ( m , 1H), 3.48-3.41 ( m , 1H), 3.21-3.18 ( m , 1H), 2.81-2.76 ( m , 1H), 2.63-2.57 ( m , 1H), ¹³ C NMR (300 MHz, CDCl ₃ , δ ) result was 152.2 , 110.8, 110.6, 70.6, 65.4, 51.0, 44.5, confirming that the FE was well prepared.

The reaction during the preparation of the FE is shown in Scheme 4 below.

[Scheme 4]

manufacturing example 3: BFA Produce

Furfuryl amine 40.95 g (0.42 mol) was added to a two-necked round-bottom flask, and the temperature was adjusted to 0° C. using ice. Then, about 202.78g (1 mol) of HCl solution (18wt%) was added and the temperature was slowly raised to 25°C, a cooler was installed, and acetone was added and then the temperature was raised to 40°C.

After 2 days and 4 days later, 0.4 equivalents of acetone were further added dropwise, respectively, and the reaction was terminated after 7 days and cooled to room temperature. Then, 10mL H ₂ O was added dropwise, pH was adjusted to 10 using 15wt% NaOH solution, extracted 3 times with ethyl acetate _{, dried over MgSO 4} , and concentrated. Then, column chromatography (ethyl acetate (EA) to methanol (MeOH)) was performed to obtain 39 g of a yellow brown product (BFA yield 72.83%).

¹ H-NMR (300 MHz, CDCl ₃ , δ ) of the yellow brown product was 6.04-6.00 ( m , 2H), 5.93-5.91 ( d , 2H), 3.78-3.76 ( d , 4H), 1.63-1.61 ( s , 4H), 1.54-1.49 ( s , 6H), and ¹³ C NMR (300 MHz, CDCl ₃ , δ ): (CDCl ₃ , 75 MHz, δ ) results were 159, 155.1, 105.6, 104.5, 39, 26.1, it can be confirmed that BFA was well prepared.

The reaction during the preparation of the BFA is shown in Scheme 5 below.

[Scheme 5]

manufacturing example 4: FFBF -OH preparation

A 3-neck round bottom flask was prepared, and 33 g (0.26 mol) of 5-hydroxymethylfurfural (HMF) and 300 mL of ethanol (EtOH) were added and stirred to prepare an HMF solution. 30.57 g (0.13 mol) of BFA prepared according to Preparation Example 3 was dissolved in 250 mL of ethanol (EtOH) and slowly added dropwise to the HMF solution, a cooler was installed, and the mixture was stirred at 40° C. for 4 hours.

Then, 54.12 g (0.39 mol) of diethyl phosphite and _{1.00 g (0.01 mol) of ZnCl 2} were added and heated to 80° C. and stirred for 14 hours.

Thereafter, ethanol was removed by concentration, washed with ethyl acetate and distilled water, and column chromatography (ethyl acetate (EA):methanol (MeOH) = 5:1) was performed to increase the viscosity. 59.3 g (FFBF-OH yield 62.4%) of a high black liquid was obtained.

¹ H-NMR (300 MHz, CDCl ₃ , δ ) of the black liquid was 6.21-6.17 ( d , 2H), 6.16-6.12 ( d , 2H), 5.97-5.93 ( d , 2H), 5.82-5.78 ( d , 2H), 4.46-4.40 ( s , 2H), 4.13-3.76 ( m , 12H), 3.76-3.66 ( d , 2H), 3.53-3.43 ( d , 2H), 1.52-1.45 ( s , 6H), 1.23-1.05 ( m , 12H), and ¹³ C NMR (300 MHz, CDCl ₃ , δ ) results were 159.4, 155.2, 151.2, 148.0, 110.5, 107.8, 104.5, 62.9, 57.8, 57.1, 54.1, 52.0, 43.7, 37.3, 26.1, 18.4, 16.3, and ³¹ P NMR (300 MHz, CDCl ₃ , δ ) was 21.14, confirming that FFBF-OH was well prepared.

The reaction in the preparation of the FFBF-OH is shown in Scheme 6 below.

[Scheme 6]

manufacturing example 5: FFBFE Produce

30.00 g (0.23 mol) of FFBF-OH, 335 g (3.51 mol) of FFBF-OH prepared according to Preparation Example 4, epichlorohydrin, d=1.18 g/ml) and tetrabutylammonium bromide in a three-necked round bottom flask , TBABr) 3g (0.01 mol) was added and stirred, then a cooler was installed and an N ₂ atmosphere was created.

After heating to 80 ℃, stirred for 3 hours, and cooled to 5 ℃. 165 g (4.13 mmol) of NaOH solution (50%) was slowly added dropwise over 5 hours, followed by washing with ethyl acetate 3 times. Thereafter, column chromatography (ethyl acetate (EA):methanol (MeOH) = 10:1) was performed to obtain 26.5 g (FFBFE yield 74.3%) of the reactant in the form of an oil with high viscosity.

¹ H-NMR (300 MHz, CDCl ₃ , δ ) of the reactant was 6.57-6.38 ( m , 2H), 6.38-6.17 ( m , 2H), 6.17-5.96 ( m , 2H), 5.96-5.74 ( m ) , 2H), 4.60-4.33 ( m , 2H), 4.30-3.83 ( m , 12H), 3.83-3.68 ( m , 2H), 3.65-3.48 ( m , 2H), 3.48-3.28 ( m , 2,6H) , 3.26-3.06 ( m , 2,6H), 3.06-2.84 ( m , 2,6H), 2.84-2.73 ( m , 2,6H), 2.64-2.49 ( m , 2.6H), 1.71-1.50 ( s , 6H). 1.49-1.05 ( m , 12H), and ¹³ C NMR (300 MHz, CDCl ₃ , δ ) results were 159.0, 151,4, 150,9, 148,3, 112.2, 109.8, 109.5, 105.3, 70.6, 64.7, 63.2, 62.1, 60.5, 53.3, 52.0, 50.9, 44.0, 37.3, 31.5, 26.4, 22.7, 21.1, 16.3, 14.2, ³¹ P NMR (300 MHz, CDCl ₃ ,) results were 20.7, 19.8 It can be seen that the FFBFE was well prepared.

The reaction during the preparation of the FFBFE is shown in Scheme 7 below.

[Scheme 7]

In Scheme 7,

이고,R ⁷ is a hydrogen atom or

ego,

이다.R ⁸ is a hydrogen atom or

am.

epoxy resin

Example 1 to 2 and comparative example 1 to 2

FE prepared according to Preparation Example 2 with an epoxy compound in an amount according to Table 1 below, FFBFE and BADGE (Bisphenol A diglycidyl ether) prepared according to Preparation Example 5, and BFA prepared according to Preparation Example 3 as a curing agent were mixed with epoxy (Epoxy) ) and amine groups were mixed in a molar ratio of 2:1 and defoamed for 20 minutes using the defoaming mode of the Passte mixer. Then, poured into a silicone mold and degassed at 100° C. for 3 minutes, followed by step curing at 100° C. for 3 hours, 140° C. for 3 hours, and 180° C. for 3 hours to prepare an epoxy resin.

division epoxy compound hardener FE (g) FFBFE (g) BADGE (g) BFA (g) Example 1 0.5 0.5 - 0.5 Example 2 0.75 0.25 - 0.408 Comparative Example 1 - - 1.0 0.334 Comparative Example 2 1.0 - - 0.488

[Test Example]

test example One: FFBFE's epoxy equivalent weight measurement

The epoxy equivalent of the FFBFE prepared according to Preparation 5 was measured. The measurement was carried out using hydrogen bromide (HBr).

First, the molar concentration of hydrogen bromide (HBr) was calculated using potassium hydrogen phthalate (KHP). In detail, the molar concentration of HBr was obtained using the reaction of KHP and HBr in Scheme 8 shown below and Equation 1 below.

[Scheme 8]

KHP + HBr → H ₂ P + KBr

[Equation 1]

Next, the epoxy equivalent of FFBFE was measured using the reaction of the epoxy group of FFBFE with hydrogen bromide (HBr) as shown in Scheme 9 below and Equation 2 below.

[Scheme 9]

[Equation 2]

According to the above measurement, the epoxy equivalent of the FFBFE prepared according to Preparation 5 was 346.5, indicating that it contained one epoxy group per 346.5 g. That is, it shows that 1 mole of FFBFE contains 2.6 epoxy groups.

test example 2: FT-IR measurement

1 shows the FT-IR analysis results of Examples 1 and 2 and Comparative Examples 1 and 2;

Referring to FIG. 1 , it can be confirmed that there is no peak at ^{910 cm -1 .} Therefore, it can be confirmed that the epoxy groups disappeared as the epoxy resins prepared according to Examples 1 and 2 and Comparative Examples 1 and 2 were cured.

test example 3: Measurement of the curing kinetic reaction

2A is a diagram showing differential scanning calorimetry (DSC) of Examples 1 and 2 and Comparative Examples 1 and 2 measured by the Kissinger method, and FIG. 2B is Examples 1 and 2 and Comparative Examples 1 and 2 Different scanning calorimetry (DSC) was measured and shown by the Ozawa method. Table 2 below shows the analysis results.

division E _a (kJ/mol) R ² Kissinger Ozawa Kissinger Ozawa Example 1 46.6 50.5 0.9633 0.9722 Example 2 53.7 57.1 0.9998 0.9980 Comparative Example 1 55.5 58.5 0.9981 0.9908 Comparative Example 2 60.6 63.7 0.9987 0.9989

Referring to Figures 2a, 2b and Table 2, Comparative Example 1 using BADGE than Comparative Example 2 using only FE as the epoxy compound has better reactivity, but it can be confirmed that the reactivity increases as FFBFE is added dropwise to FE. This is confirmed by the fact that FFBFE includes dipole bonding of P-O, P=O and N-H.

test example 4: Dynamic mechanical behavior analysis (DMA)

Figure 3a shows the elastic modulus measurement results of Examples 1 to 2 and Comparative Examples 1 and 2, Figure 3b is the elastic modulus lost with respect to the stored elastic modulus of Examples 1 and 2 and Comparative Examples 1 and 2 The tan delta measurement result, which is the ratio of the coefficients, is shown. Table 3 below summarizes the DMA measurement results of Examples 1 and 2 and Comparative Examples 1 and 2.

division T _g (℃) E'(MPa) at 175℃ υ _e (mol/cm ³ ) Example 1 87.8 203 18167.2 Example 2 76.6 142 12708.1 Comparative Example 1 114.4 166 14855.9 Comparative Example 2 40.1 130 11634.1

Referring to FIGS. 3A and 3B , it can be seen that Comparative Example 2 using only FE as an epoxy compound _{has a low glass transition temperature (T g} ) and a low crosslinking density due to the flexibility of FE. On the other hand, in Examples 1 and 2, the glass transition temperature (T _g ) was increased by additionally using FFBFE in FE, the average number of epoxy groups of FFBFE was 2.6, and the crosslinking point due to hydrogen bonding increased. It can be seen that the crosslinking density also increases.

test example 5: thermogravimetric analysis( TGA )

4a shows the thermogravimetric analysis results of Examples 1 and 2 and Comparative Examples 1 and 2, and FIG. 4b is a thermogravimetric differential showing the weight change rate according to temperature/time of Examples 1 and 2 and Comparative Examples 1 and 2 (DTG) curve is shown.

4a and 4b, in the case of Examples 1 and 2 including FFBFE, the decomposition is less even when the temperature is increased compared to Comparative Examples 1 and 2 that do not include FFBFE due to the presence of phosphorus (P) present in FFBFE it can be confirmed that

test example 6: Mechanical Characterization

5A shows the tensile strength test results of Examples 1 and 2 and Comparative Examples 1 and 2, and FIG. 5B shows the tensile modulus test results of Examples 1 and 2 and Comparative Examples 1 and 2.

Referring to FIGS. 5A and 5B , it can be seen that Comparative Example 2 including only FE has a lower tensile strength value than Comparative Example 1 including only BADGE due to the flexibility of FE. However, in the case of Examples 1 and 2 containing FE and FFBFE, it can be seen that the tensile strength value is increased compared to Comparative Example 2, which is that the average number of epoxy groups of FFBFE is 2.6, and the crosslinking point due to hydrogen bonding is appears to be increasing.

In addition, it can be seen that the tensile modulus of Examples 1 and 2 containing FE and FFBFE is higher than Comparative Example 1 containing only BADGE, which is due to hydrogen bonding between FE and FFBFE.

test example 7: Flame retardant characterization

6A shows the total heat release (THR) of Examples 1 and 2 and Comparative Examples 1 and 2, and FIG. 6B shows the heat release rates of Examples 1 and 2 and Comparative Examples 1 and 2; , HRR), and FIG. 6c shows the rate of fire spread over time in Examples 1 and 2 and Comparative Examples 1 and 2.

Table 4 below shows the content of elements included in Comparative Examples 1 and 2.

division C (%) H (%) O (%) N (%) Comparative Example 1 72.21 7.22 17.06 3.51 Comparative Example 2 62.19 7.00 26.33 4.48

Referring to FIGS. 6a to 6c and Table 4, it can be seen that Comparative Example 2 includes a furan ring, thereby reducing the total heat release by 22% compared to Comparative Example 1, and thus it can be confirmed that the furan group has good flame retardancy. have.

In addition, it can be confirmed that when FFBFE is included more due to the flame retardant effect of the phosphorus (P) element, the total amount of heat release, the heat release rate, and the diffusion of fire are lowered.

Therefore, it can be confirmed that the epoxy compound according to the present invention and the epoxy resin including the same are bio-based flame retardant materials.

The scope of the present invention is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention. do.

Claims (19)

Epoxy compound represented by Structural Formula 1:
[Structural Formula 1]

In Structural Formula 1,
R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,
R ³ are each independently a C1 to C3 alkylene group,
R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,
R ⁶ are each independently a C1 to C3 alkylene group,
R ⁷ is a hydrogen atom or

ego,
R ⁹ is a C1 to C3 alkylene group,
R ⁸ is a hydrogen atom or

ego,
R ¹⁰ is a C1 to C3 alkylene group. According to claim 1,
In Structural Formula 1,
R ⁷ is a hydrogen atom,
R ⁸ is an epoxy compound, characterized in that it is a hydrogen atom. According to claim 1,
In Structural Formula 1,
R ⁷ is a hydrogen atom,
R ⁸ is

ego,
R ¹⁰ is an epoxy compound, characterized in that it is a C1 to C3 alkylene group. Epoxy compound represented by Structural Formula 1;
Epoxy compound represented by Structural Formula 2; and
hardener;
An epoxy composition comprising:
[Structural Formula 1]

In Structural Formula 1,
R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,
R ³ are each independently a C1 to C3 alkylene group,
R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,
R ⁶ are each independently a C1 to C3 alkylene group,
R ⁷ is a hydrogen atom or

ego,
R ⁹ is a C1 to C3 alkylene group,
R ⁸ is a hydrogen atom or

ego,
R ¹⁰ is a C1 to C3 alkylene group,
[Structural Formula 2]

In Structural Formula 2,
R ¹¹ is each independently a C1 to C3 alkylene group. 5. The method of claim 4,
The compound represented by Structural Formula 1 is an epoxy resin composition comprising a compound represented by Structural Formula 1-1 and a compound represented by Structural Formula 1-2 below:
[Structural Formula 1-1]

[Structural Formula 1-2]

In Structural Formula 1-1 or 1-2,
R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,
R ³ are each independently a C1 to C3 alkylene group,
R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,
R ⁶ are each independently a C1 to C3 alkylene group,
R ¹⁰ is a C1 to C3 alkylene group. 5. The method of claim 4,
the epoxy composition
100 parts by mole of an epoxy compound represented by Structural Formula 2; and
Epoxy composition comprising a; 10 to 200 mole parts of the epoxy compound represented by the structural formula (1). 6. The method of claim 5,
The ratio (m ₁ :m ₂ ) of the number _{of moles (m 1} ) of the epoxy compound represented by Structural Formula 1-1 _{and the number of moles (m 2} ) of the epoxy compound represented by Structural Formula 1-2 is 30:70 to 50:50 Epoxy composition, characterized in that. 5. The method of claim 4,
Epoxy composition, characterized in that the curing agent is a compound represented by the following structural formula 3:
[Structural Formula 3]

In Structural Formula 3,
R ¹² and R ¹³ are each independently a hydrogen atom or a C1 to C3 alkyl group,
R ¹⁴ is each independently a C1 to C3 alkylene group. 9. The method of claim 8,
The epoxy composition
40 to 60 mole parts of the amine group of the curing agent with respect to 100 mole parts of the epoxy group of the total epoxy compound;
The entire epoxy compound is an epoxy composition comprising an epoxy compound represented by the structural formula 1 and an epoxy compound represented by the structural formula 2. (a) preparing a compound represented by Structural Formula 13 by reacting 5-hydroxymethylfurfural (HMF) with a compound represented by Structural Formula 11 and a compound represented by Structural Formula 12 according to Scheme 1; and
(b) reacting the compound represented by Structural Formula 13 with the compound represented by Structural Formula 14 according to Scheme 2 to prepare an epoxy compound represented by Structural Formula 1;
Method for producing an epoxy compound comprising:
[Scheme 1]

[Scheme 2]

In Scheme 1 or 2,
R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,
R ³ are each independently a C1 to C3 alkylene group,
R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,
R ⁶ are each independently a C1 to C3 alkylene group,
R ⁷ is a hydrogen atom or

ego,
R ⁹ is a C1 to C3 alkylene group,
R ⁸ is a hydrogen atom or

ego,
R ¹⁰ is a C1 to C3 alkylene group,
X is F, Cl, Br or I. 11. The method of claim 10,
In Scheme 1 or 2,
R ⁷ is a hydrogen atom,
R ⁸ is a method for producing an epoxy compound, characterized in that the hydrogen atom. 11. The method of claim 10,
In Scheme 1 or 2,
R ⁷ is a hydrogen atom,
R ⁸ is

ego,
R ¹⁰ is a method for producing an epoxy compound, characterized in that a C1 to C3 alkylene group. 11. The method of claim 10,
Method for producing an epoxy compound, characterized in that using _{ZnCl 2} as the reaction catalyst of the step (a). 11. The method of claim 10,
Tetra-n-butylammonium bromide (TBABr) as the reaction catalyst of the step (b), characterized in that using the epoxy compound manufacturing method. 11. The method of claim 10,
The step (a) is
(a-1) reacting 5-hydroxymethylfurfural (HMF) with the compound represented by Structural Formula 11; and
(a-2) reacting the product of step (a-1) with the compound represented by Structural Formula 12 to prepare a compound represented by Structural Formula 13; Method for producing an epoxy compound comprising a. 16. The method of claim 15,
The step (a-1) is carried out at a temperature of 10 to 80 ℃,
The method for producing an epoxy compound, characterized in that the step (a-2) is carried out at a temperature of 50 to 100 ℃. 11. The method of claim 10,
The method for producing an epoxy compound, characterized in that the step (b) is carried out at a temperature of 50 to 100 ℃. (1) preparing an epoxy composition comprising an epoxy compound represented by Structural Formula 1 and an epoxy compound represented by Structural Formula 2 and a curing agent;
(2) degassing the epoxy composition; and
(3) curing the defoamed epoxy composition to prepare an epoxy resin;
Method for producing an epoxy resin comprising:
[Structural Formula 1]

In Structural Formula 1,
R ¹ and R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,
R ³ are each independently a C1 to C3 alkylene group,
R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group,
R ⁶ are each independently a C1 to C3 alkylene group,
R ⁷ is a hydrogen atom or

ego,
R ⁹ is a C1 to C3 alkylene group,
R ⁸ is a hydrogen atom or

ego,
R ¹⁰ is a C1 to C3 alkylene group,
[Structural Formula 2]

In Structural Formula 2,
R ¹¹ is each independently a C1 to C3 alkylene group. 19. The method of claim 18,
The method for producing an epoxy resin, characterized in that the step (3) is carried out at a temperature of 80 to 200 ℃.

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