KR102332452B1 - Di-functional thermosetting resin comprising aziridine derivatives - Google Patents

Abstract

The present invention relates to a bifunctional thermosetting resin comprising an aziridine derivative represented by the following [Formula I], has a fast curing rate, a high degree of curing even under low energy conditions, and various substrates by controlling the substituents introduced into aziridine It is characterized in that it has a selective reactivity with respect to
[Formula Ⅰ]

Description

Di-functional thermosetting resin comprising aziridine derivatives

The present invention relates to a bifunctional thermosetting resin containing an aziridine derivative, and to a bifunctional thermosetting resin having a fast curing rate, substrate selectivity to a curing agent, and a high degree of curing even under low energy conditions.

In the case of epoxide, which is the most commonly used tricyclic heterocyclic compound, as shown below, the ring-opening reaction is easy due to significant ring strain, and DGEBA (Diglycidyl Ether of DGEBA), a bisphenol-type resin containing an epoxide functional group, is Bisphenol A) is currently the most commonly used resin in the polymer epoxy industry.

However, in the case of the epoxy resin most commonly used in industry at present, there are problems in that the curing rate is slow, the curing degree is low at a low temperature, and the substrate selectivity for the curing agent is very low.

Therefore, there is an urgent need to develop a new source material to solve the problem of existing epoxy-based coating materials. In particular, polymerization can proceed under low energy conditions compared to epoxy, and it is difficult to secure a material that can cure faster than epoxy. necessary.

Accordingly, in order to solve the above problems, an object of the present invention is to provide a thermosetting resin having a high curing rate, a substrate selectivity to a curing agent, and a high degree of curing even under low energy conditions.

The present invention provides a thermosetting resin (Diaziridyl Ether of Bisphenol A, DzEBA) represented by the following [Formula I] in order to solve the above problems.

[Formula Ⅰ]

The characteristics of the [Formula I] and the definition of R will be described later.

The thermosetting resin according to the present invention has the advantage of having a fast curing rate, substrate selectivity to a curing agent, and a high degree of curing even under low energy conditions. can In addition, it is possible to control the reactivity of various chemical species to the substrate, enabling the development of various new materials.

1 is a graph showing the results of curing reaction of Bn-DzEBA and DGEBA with dodecanedioic acid at 80° C. and DMSO solvent conditions, respectively.
2 is a graph showing the results of curing reaction of Ts-DzEBA and DGEBA with ethylene diamine at 80° C. and DMSO solvent conditions, respectively.
3 is a graph showing the results of curing reaction of Ts-DzEBA with ethylene diamine at room temperature, 40°C, 60°C, and 80°C using DMSO as a solvent, respectively.
4 is a thermosetting resin according to the present invention, Bn-DzEBA introducing an electron donor group (EDG) as a functional group substituted for nitrogen of aziridine, and Ts-DzEBA introducing an electron withdrawing group (EWG) at 80 ° C. , It is a graph showing the result of curing reaction with dodecanedioic acid in DMSO solvent condition.
5 is a thermosetting resin according to the present invention, Bn-DzEBA introducing an electron donor group (EDG) as a functional group substituted for nitrogen of aziridine, and Ts-DzEBA introducing an electron withdrawing group (EWG) at 80 ° C. , It is a graph showing the result of curing reaction with ethylene diamine in DMSO solvent condition.
6 is a representative view showing the structure of the bifunctional thermosetting resin according to the present invention.

Hereinafter, the present invention will be described in more detail.

The resin to which the substituted aziridine according to the present invention is introduced is represented by the following [Formula I], (i) characterized in that an aziridine structure is introduced, and by this structural feature, it has a fast curing rate even at a low temperature characterized in that In addition, (ii) the functional group binding to the nitrogen of aziridine is adjusted to an electron donor group (EDG) or an electron withdrawing group (EWG) to increase the selectivity for the substrate.

[Formula Ⅰ]

In the [Formula I],

R is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 Any one selected from an aryl group and the following [Structural Formula 1].

[Structural Formula 1]

In the [Structural Formula 1],

R ₁ and R ₂ are each independently hydrogen, deuterium, a halogen group, a nitrile group, a hydroxy group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 alkenyl group, a substituted or unsubstituted Any one selected from an alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms and a heteroaryl group having 3 to 20 carbon atoms.

On the other hand, the substituted or unsubstituted means that R, R ₁ and R ₂ are each independently deuterium, a halogen group, a nitrile group, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 3 to 20 carbon atoms. It is selected from a cycloalkyl group, an aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms, and is substituted with one or more selected substituents, or substituted with a substituent to which two or more of the substituents are connected, or any substituents means not having

For specific examples, the substituted aryl group means that a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, etc. are substituted with other substituents do.

In the present invention, examples of the substituents will be described in detail below, but the present invention is not limited thereto.

In the present invention, the alkyl group may be linear or branched, and specific examples include a methyl group, an ethyl group, a propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group , sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1 -Methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentyl group methyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but is not limited thereto.

In the present invention, the aryl group may be monocyclic or polycyclic, and examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and a stilbene group, and examples of the polycyclic aryl group include a naphthyl group and an anthracenyl group. , a phenanthrenyl group, a pyrenyl group, and the like, but the scope of the present invention is not limited to these examples.

In the present invention, the alkenyl group may be linear or branched, and specific examples include a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group. , 2-pentenyl group, 3-pentenyl group, and the like, but are not limited thereto.

In the present invention, the heteroaryl group is a heterocyclic group containing O, N or S as a heteroatom, and examples thereof include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, Triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, etc., but limited to these it's not going to be

In the present invention, the cycloalkyl group is not particularly limited, but specifically, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, 4-methylcyclohexyl group, and the like, but is not limited thereto.

In the present invention, examples of the halogen group include fluorine, chlorine, bromine or iodine.

As a specific example of [Formula I] according to the present invention, the following [Formula 1] or [Formula 2] may be mentioned, which is a specific example showing one functional group introduced into the nitrogen of aziridine, and the scope of the present invention is It is not limited thereto.

[Formula 1]

[Formula 2]

Hereinafter, the present invention will be described in more detail through Examples and Experimental Examples. These Examples and Experimental Examples are only for specifically illustrating the present invention, and the scope of the present invention is not limited by these Examples and Experimental Examples.

Synthesis Example 1: Benzyl Diaziridyl Ether of Bisphnol A (Bn-DzEBA)

(1) Synthesis of intermediate S3

Bromine (5.14 mL, 99.88 mmol) was added dropwise to a solution of ethyl acrylate (10.63 mL, 99.88 mmol) (DCM 75 mL) at 0 °C for 20 min in an inert atmosphere, and the reaction mixture was stirred at 0 °C for 1 hour. Then, the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the mixture was quenched with saturated Na ₂ S ₂ O ₃ aqueous solution, the mixture was extracted with DCM and water, and the organic layer was separated to obtain S3 compound.

(2) Synthesis of intermediate S4

Ethyl2,3-dibromopropanoate (15 g, 57.71 mmol) and trimethylamine (16 mL, 69.6 mmol) were added sequentially to a solution of benzylamine in heavy (120 mL anhydrous ethanol) at 0 °C in a nitrogen atmosphere. . The reaction mixture was stirred at 60 °C for 1 h. The solvent of the mixture was evaporated, the crude product was extracted with dichloromethane, the organic phase was dried over magnesium sulfate, the solvent was removed under reduced pressure at room temperature, and purified by column chromatography to obtain a white solid product S4.

(3) Synthesis of intermediate S5

Lithium aluminum hydride (1.849 g, 48.72 mmol) was slowly added to a solution of ethyl 1-benzylaziridine-2-carboxylate (5 g, 24.36 mmol) (130 mL of diethyl ether), followed by stirring at room temperature for 3 hours. did. The reaction mixture was quenched with water (1.9 mL) and 15% aqueous NaOH solution (1.9 mL) followed by water (5.6 mL). After filtration of the mixture, the crude compound was extracted with ethyl acetate. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure to give S5 yellow powder.

(4) Synthesis of intermediate S5

To a solution of (1-benzylaziridin-2-yl)methanol (1 g, 6.127 mmol) (triethylamine 3.0 mL, 21.64 mmol) p-toluene sulfonyl chloride (1.402 g, 7.352 mmol), dichloromethane (15 mL) ) was added at 0 °C in a nitrogen atmosphere, and the mixture was stirred at 0 °C for 2 hours. The crude product of the reaction product was extracted with dichloromethane, the organic phase was dried over magnesium sulfate, the solvent was removed under reduced pressure at room temperature, and purified by column chromatography to obtain a white solid product S6.

(4) Synthesis of Benzyl Diaziridyl Ether of Bisphnol A (S1, Bn-DzEBA)

(1-benzylaziridin-2-yl)methyl in a solution of bisphenol A (108 mg, 0.436 mmol), 18-crown-ether (15.5 mg, 0.0586 mmol) and KOH (135 mg, 2.398 mmol) (THF 15 mL) 4-Methylbenzenesulfonate (277 mg, 0.872 mmol) was added and the mixture was refluxed for 17 h. The reaction solution was cooled to room temperature and extracted with _{CH 2} Cl _{2 .} The combined organic layers were dried over anhydrous MgSO _{4 ,} filtered and concentrated in vacuo. The crude product was purified by column chromatography (EA : hexane = 2 : 1) to obtain S1 compound as a yellow oil.

Synthesis Example 2: Tosyl Diaziridyl Ether of Bisphenol A (Ts-DzEBA)

(1) Synthesis of intermediate S7

Using DMSO as a solvent, potassium carbonate (6.09 g, 44.06 mmol), p-toluenesulfonamide (5.03 g, 29.37 mmol), diglycidyl ether-bisphenol A (5 g, 14.69 mmol) and 18-crown-6 ( 233 mg, 0.8814 mmol) was stirred with heating at 100 °C for 2 h. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate and washed with distilled water. The organic layer was anhydrous Na ₂ SO ₄ dried over and concentrated under reduced pressure. The crude product was purified by column chromatography (EA : hexane = 3 : 1) to obtain S7 as a yellow oil.

(2) Synthesis of intermediate S8

N,N'-(((propane-2,2-diylbis(4,1-phenylene))bis(oxy)bis(2-hydroxypropane-3,1-diyl)bis(4-methylbenzenesulfone To a solution of amide) and triethylamine (120.9 mg, 1.195 mmol) was added methanesulfonylchloride (40.3 mg, 0.3515 mmol) at 0 ° C. The mixture was heated at room temperature and stirred for 5 hours. The mixture was quenched with distilled water and extracted with ethyl acetate, then the organics were washed with brine and Na ₂ SO ₄ dried over and concentrated under reduced pressure. The crude product was purified by column chromatography (EA: hexane = 1:1) to obtain S8 as a yellow oil.

(3) Synthesis of Tosyl Diaziridyl Ether of Bisphenol A (S2, Ts-DzEBA)

((propane-2,2-diylbis(4,1-phenylene))bis(oxy)bis(1-(4-ethylphenylsulfonamido)propane-3,2-diyl)dimethanesulfonate, carbonic acid Potassium and acetonitrile solution was stirred at room temperature for 16 hours.The reaction mixture was diluted with ethyl acetate, poured into distilled water, and extracted with ethyl acetate.The crude product was subjected to column chromatography (EA: hexane = 1: 2). Purification gave the S1 compound as a yellow oil.

Experimental Example 1

(1) A thermosetting resin having an epoxide functional group having the same skeleton (Bisphnol A) as the aziridine thermosetting resin compound (Benzyl Diaziridyl Ether of Bisphnol A, Bn-DzEBA) according to the present invention prepared according to Synthesis Example 1 (Diglycidyl) Ether of Bisphnol A, DGEBA) was used as a comparative example to confirm the degree of curing reaction.

1 is a result of curing reaction of Bn-DzEBA and DGEBA with dodecanedioic acid in DMSO solvent conditions at 80 ° C., compared to DGEBA. (Ring Opening Polymerization) can be confirmed.

[Diglycidyl Ether of Bisphnol A, DGEBA]

(2) A thermosetting resin having an epoxide functional group having the same skeleton (Bisphnol A) as the aziridine thermosetting resin compound (Tosyl Diaziridyl Ether of Bisphenol A, Ts-DzEBA) according to the present invention prepared according to Synthesis Example 2 (Diglycidyl) Ether of Bisphnol A, DGEBA) was used as a comparative example to confirm the degree of curing reaction.

Figure 2 is the result of curing reaction of Ts-DzEBA and DGEBA with ethylene diamine, respectively, in a DMSO solvent condition at 80 ° C. Compared to DGEBA, the thermosetting resin (DzEBA) containing aziridine according to the present invention has a faster ring-opening reaction. (Ring Opening Polymerization) can be confirmed.

Experimental Example 2

The curing reaction of the aziridine thermosetting resin compound (Tosyl Diaziridyl Ether of Bisphenol A, Ts-DzEBA) according to the present invention prepared according to Synthesis Example 2 with ethylene diamine was confirmed by varying the temperature in DMSO solvent conditions.

Figure 3 is the result of curing reaction of Ts-DzEBA with ethylene diamine at room temperature, 40 ℃, 60 ℃, 80 ℃ using DMSO as a solvent, in the case of the thermosetting resin according to the present invention, the ring-opening reaction was You can check the completion.

In particular, when compared with the results of Figure 3 and the results of Figure 2, it can be seen that it has an improved curing performance than DGEBA even at room temperature or below 80 ℃.

Experimental Example 3

With respect to the thermosetting resin (Bn-DzEBA, Ts-DzEBA) according to the present invention, a thermosetting resin (Diglycidyl Ether of Bisphnol A, DGEBA) having an epoxide functional group having the same backbone (Bisphnol A) as a comparative example for various substrates The curing reaction was confirmed.

4 is a thermosetting resin according to the present invention, Bn-DzEBA introducing an electron donor group (EDG) as a functional group substituted for nitrogen of aziridine, and Ts-DzEBA introducing an electron withdrawing group (EWG) at 80 ° C. , the result of curing reaction with dodecanedioic acid in DMSO solvent conditions.

Referring to FIG. 4 , it can be seen that when the substrate is carboxylic acid (dodecanedioic acid), the curing reaction is better than when the electron donor group is introduced.

5 is a thermosetting resin according to the present invention, Bn-DzEBA introducing an electron donor group (EDG) as a functional group substituted for nitrogen of aziridine, and Ts-DzEBA introducing an electron withdrawing group (EWG) at 80 ° C. , the result of curing reaction with ethylene diamine in DMSO solvent conditions.

Referring to FIG. 5 , it can be seen that when the substrate is ethylene diamine, the curing reaction is better than when an electron withdrawing group is introduced.

The following [Table 1] shows the reaction progress (%) as a result of the ring-opening reaction of each of Bn-DzEBA, Ts-DzEBA, and DGEBA for 24 hours on various substrates.

substrate Bn-DzEBA Ts-DzEBA DGEBA Carboxylic
acid

100% 0% 97%

100% 100% 62% Alcohol

52% 100% 0%

17% 100% 0% Amine

0% 100% 77%

87% 100% 64%

Looking at [Table 1], it can be seen that the thermosetting resin according to the present invention has an excellent curing reaction progress compared to the conventional DGEBA, and the curing possibility through ring-opening reaction with various functional groups is expanded, and the nitrogen atom of DzEBA is By adjusting the substituents, the selectivity for the substrate can be increased.

Claims (3)

Thermosetting resin represented by the following [Formula I]:
[Formula Ⅰ]

In the [Formula I],
R is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 Any one selected from an aryl group and the following [Structural Formula 1],
[Structural Formula 1]

In the [Structural Formula 1],
R ₁ and R ₂ are each independently hydrogen, deuterium, a halogen group, a nitrile group, a hydroxy group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 alkenyl group, a substituted or unsubstituted any one selected from a cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms. According to claim 1,
The substituted or unsubstituted means that R, R ₁ and R ₂ are each independently deuterium, a halogen group, a nitrile group, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms. , is selected from an aryl group having 6 to 20 carbon atoms and a heteroaryl group having 3 to 20 carbon atoms, and is substituted with one or more selected substituents, or is substituted with a substituent to which two or more substituents are connected among the substituents, or does not have any substituents thermosetting resin, which means that According to claim 1,
The [Formula I] is a thermosetting resin, characterized in that the following [Formula 1] or [Formula 2]:
[Formula 1]

[Formula 2]

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