KR20190016217A - Di-functional thermosetting resin comprising aziridine derivatives - Google Patents

Abstract

The present invention relates to a bi-functional thermosetting resin containing an aziridine derivative, represented by chemical formula 1. The bi-functional thermosetting resin has a fast curing rate, a high curing degree even in a low-energy condition, and selective reactivity to various substrates by controlling a substituent introduced into aziridine.

Description

Di-functional thermosetting resin as aziridine derivatives containing an aziridine derivative,

The present invention relates to a bifunctional thermosetting resin containing an aziridine derivative, which has a high curing rate, a substrate selectivity to a curing agent, and a high degree of curing at low energy conditions.

In the case of the epoxide Epoxide, which is the most commonly used trialkylene heterocyclic compound, the ring opening reaction is facilitated by a considerable ring strain, and the bisphenol-type resin DGEBA (diglycidyl ether of Bisphenol A) is currently the most commonly used resin in the polymeric epoxy industry.

However, the epoxy resin most commonly used in the present industry has a problem that the curing rate is low, the degree of curing at low temperature is low, and the substrate selectivity to the curing agent is very low.

Therefore, it is necessary to develop a new source material for solving the problems of existing epoxy-based coating materials. Especially, it is possible to achieve a high molecular weight at a low energy level compared to an epoxy, and to secure a material capable of accelerating the curing reaction faster than the epoxy need.

Accordingly, 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 at low energy conditions.

The present invention provides a thermosetting resin (Diaziridyl Ether of Bisphenol A, DzEBA) represented by the following formula (I).

(I)

The characteristics of the above formula (I) and the definition of R will be described later.

The thermosetting resin according to the present invention is advantageous in that it has a high curing speed, a substrate selectivity to a curing agent, a high degree of curing at low energy conditions, and a low energy process compared to an epoxide-based material. . In addition, it is possible to control the reactivity of various chemical species to the substrate, thereby enabling various new materials to be developed.

FIG. 1 is a graph showing the results of curing reaction of Bn-DzEBA and DGEBA with dodecanedioic acid at 80 ° C. in a DMSO solvent.
FIG. 2 is a graph showing the results of curing reaction of ethylene diamine with Ts-DzEBA and DGEBA at 80 DEG C under DMSO solvent conditions.
Fig. 3 is a graph showing the results of curing reaction of Ts-DzEBA with ethylene diamine at room temperature, 40 캜, 60 캜 and 80 캜 using DMSO as a solvent.
FIG. 4 is a graph showing the results of the comparison of Bn-DzEBA in which an electron donating group (EDG) is introduced as a functional group substituted with nitrogen of aziridine and Ts-DzEBA in which an electron attracting group (EWG) is introduced in a thermosetting resin according to the present invention at 80 ° C , And a graph showing the results of curing reaction with dodecanedioic acid under DMSO solvent conditions.
Fig. 5 is a graph showing the results of the comparison of the Bn-DzEBA in which an electron donating group (EDG) is introduced as a functional group substituted with nitrogen of aziridine and Ts-DzEBA in which an electron attracting group (EWG) , A graph showing the results of curing reaction with ethylene diamine under DMSO solvent conditions.
6 is a representative view showing the structure of a bifunctional thermosetting resin according to the present invention.

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

The resin having the substituted aziridine according to the present invention is represented by the following formula (I): (i) an aziridine structure is introduced, and due to such a structural feature, . Further, (ii) the functional group binding to the nitrogen of the aziridine is controlled by an electron donor group (EDG) and an electron attracting group (EWG), thereby increasing the selectivity to the substrate.

(I)

In the above formula (I)

R represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted 6 to 20 carbon atoms An aryl group, and a group represented by the following formula [1].

[Structural formula 1]

In the above formula 1,

R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, a halogen group, a nitrile group, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, A substituted or unsubstituted C 3 -C 20 cycloalkyl group, a substituted or unsubstituted C 6 -C 20 aryl group, and a C 3 -C 20 heteroaryl group.

The substitution or unsubstitution means that each of R, R ₁ and R ₂ is independently selected from the group consisting of deuterium, halogen, nitrile, hydroxyl, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, A cycloalkyl group, an aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms, and may be substituted with one or two or more selected substituents, or two or more of the substituents may be substituted with a substituent, or any substituent It does not have.

Specific examples of the substituted aryl group include a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group and an anthracenyl group substituted with other substituents do.

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

In the present invention, the alkyl group may be linear or branched, and specific examples thereof include a methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n- Methylpentyl, 4-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentyl An ethylhexyl group, a 2-ethylhexyl group, a 2-propylpentyl group, a n-nonyl group, a 2,2-dimethylheptyl group, But are not limited to, 1-ethyl-propyl group, 1,1-dimethylpropyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group and 5-methylhexyl group.

In the present invention, the aryl group may be monocyclic or polycyclic. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group and a stilbene group. Examples of the polycyclic aryl group include a naphthyl group, 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 thereof include a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl 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 pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, A pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, an acridyl group, a pyridazine group, a pyrazinyl group, a quinolinyl group, a quinazoline group and a quinoxalinyl group. It is not.

In the present invention, the cycloalkyl group is not particularly limited, but specifically includes 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 are not limited thereto.

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

As a specific example of the formula (I) according to the present invention, there can be mentioned the following formula (1) or (2), which is a specific example showing a monofunctional group to be introduced into nitrogen of an aziridine, But is not limited thereto.

[Chemical Formula 1]

(2)

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. These examples and experimental examples are only intended to illustrate the present invention in detail, 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 in an inert atmosphere for 20 minutes 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 equilibrated with a saturated Na ₂ S ₂ O ₃ aqueous solution, and the mixture was extracted with DCM and water, and then the organic layer was separated to obtain the S3 compound.

(2) Synthesis of intermediate S4

Ethyl 2,3-dibromopropanoate (15 g, 57.71 mmol) and trimethylamine (16 mL, 69.6 mmol) were sequentially added to a solution of benzylamine (120 mL of absolute ethanol) at 0 ° C in a nitrogen atmosphere . The reaction mixture was stirred at 60 < 0 > C for 1 hour. The solvent of the mixture was evaporated, the crude product was extracted with dichloromethane, the organic phase was dried with magnesium sulfate, the solvent was removed by reduced pressure at room temperature and purification by column chromatography gave 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-benzyl aziridine-2-carboxylate (5 g, 24.36 mmol) (130 mL of diethyl ether) and stirred at room temperature for 3 hours Respectively. The reaction mixture was quenched with water (1.9 mL) and 15% aqueous NaOH (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 with magnesium sulfate and the solvent was removed under reduced pressure to yield S5 yellow powder.

(4) Synthesis of intermediate S5

Toluenesulfonyl chloride (1.402 g, 7.352 mmol) and dichloromethane (15 mL) were added to a solution (1 g, 6.127 mmol) of triethylamine (3.0 mL, 21.64 mmol) ) In a nitrogen atmosphere at 0 ° C, and the mixture was stirred at 0 ° C for 2 hours. The crude product of the reaction was extracted with dichloromethane, the organic phase was dried over magnesium sulfate, the solvent was removed by reduced pressure at room temperature and purification by column chromatography gave a white solid product S6.

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

To 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) 4-Methylbenzenesulfonate (277 mg, 0.872 mmol) was added and the mixture was refluxed for 17 hours. 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 give S1 compound of yellow oil.

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

(1) Synthesis of intermediate S7

(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- 233 mg, 0.8814 mmol) was heated with stirring at 100 < 0 > C for 2 hours. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate and washed with distilled water. The organic layer over anhydrous Na ₂ SO ₄ ≪ / RTI > and concentrated under reduced pressure. The crude product was purified by column chromatography (EA: hexane = 3: 1) to give S7 as a colorless oil.

(2) Synthesis of intermediate S8

Bis (2-hydroxypropane-3,1-diyl) bis (4-methylbenzene sulfone) Amide) and triethylamine (120.9 mg, 1.195 mmol) in dichloromethane (5 mL) at 0 ° C was added methanesulfonyl chloride (40.3 mg, 0.3515 mmol) in a nitrogen atmosphere at 0 ° C. The mixture was heated at room temperature and stirred for 5 h. The mixture was extracted with distilled water and extracted with ethyl acetate. The organics were then washed with brine and washed with Na ₂ SO ₄ ≪ / RTI > and concentrated under reduced pressure. The crude product was purified by column chromatography (EA: hexane = 1: 1) to give S8 as a yellow oil.

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

Bis (1- (4-ethylphenylsulfonamido) propane-3,2-diyl) dimethanesulfonate, carbonic acid The reaction mixture was diluted with ethyl acetate, poured into distilled water and extracted with ethyl acetate. The crude product was purified by column chromatography (EA: hexane = 1: 2) Purification yielded the S1 compound of a yellow oil.

Experimental Example 1

(1) A thermosetting resin having an epoxy functional group having the same skeleton (Bisphnol A) as the aziridine thermosetting resin compound (Benzyl Diaziridyl Ether of Bisphonol A, Bn-DzEBA) prepared according to Synthesis Example 1 Ether of Bisphnol A, DGEBA) as a comparative example.

FIG. 1 shows the result of curing reaction of Bn-DzEBA and DGEBA with dodecanedioic acid at 80 ° C. in DMSO solvent. As a result, the thermosetting resin (DzEBA) according to the present invention, which contains aziridine, (Ring Opening Polymerization) is completed.

[Diglycidyl Ether of Bisphnol, DGEBA]

(2) A thermosetting resin having an epoxy functional group having the same skeleton (Bisphnol A) as that of the aziridine thermosetting resin (Tosyl Diaziridyl Ether of Bisphenol A, Ts-DzEBA) Ether of Bisphnol A, DGEBA) as a comparative example.

FIG. 2 shows the result of curing reaction of Ethylene diamine with Ts-DzEBA and DGEBA at 80 ° C in DMSO solvent. As a result, the thermosetting resin (DzEBA) according to the present invention containing aziridine, compared with DGEBA, (Ring Opening Polymerization) is completed.

Experimental Example 2

The curing reaction of the aziridine thermosetting resin (Tosyl Diaziridyl Ether of Bisphenol A, Ts-DzEBA) prepared according to Synthesis Example 2 with Ethylene diamine at different temperatures under DMSO solvent condition was confirmed.

FIG. 3 shows the result of curing reaction of Ts-DzEBA with ethylene diamine at room temperature, 40 ° C., 60 ° C. and 80 ° C. using DMSO as a solvent. In the case of the thermosetting resin according to the present invention, It can be confirmed that it is completed.

In particular, the results of FIG. 3 and the results of FIG. 2 are compared with each other, and it can be seen that the curing performance is improved below 80 DEG C and even at room temperature, as compared with DGEBA.

Experimental Example 3

As a comparative example, a thermosetting resin having an epoxide functional group (Bisphnol A) having the same skeleton (Bis-DzEBA) according to the present invention (Bn-DzEBA, Ts-DzEBA) The curing reaction was confirmed.

FIG. 4 is a graph showing the results of the comparison of Bn-DzEBA in which an electron donating group (EDG) is introduced as a functional group substituted with nitrogen of aziridine and Ts-DzEBA in which an electron attracting group (EWG) is introduced in a thermosetting resin according to the present invention at 80 ° C , And curing reaction with dodecanedioic acid under DMSO solvent conditions.

FIG. 4 shows that when the substrate is a dodecanedioic acid, the curing reaction is more excellent when an electron donor group is introduced.

Fig. 5 is a graph showing the results of the comparison of the Bn-DzEBA in which an electron donating group (EDG) is introduced as a functional group substituted with nitrogen of aziridine and Ts-DzEBA in which an electron attracting group (EWG) , And the result of curing reaction with ethylene diamine under DMSO solvent condition.

Referring to FIG. 5, when the substrate is made of ethylene diamine, the curing reaction is more excellent when the electron attracting group is introduced.

Table 1 below shows the degree of reaction progress (%) as a result of conducting the ring-opening reaction with Bn-DzEBA, Ts-DzEBA and DGEBA for various substrates for 24 hours.

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%

As shown in Table 1, it can be seen that the thermosetting resin according to the present invention is superior to the conventional DGEBA in the progress of the curing reaction and has expanded the possibility of curing through ring-opening reaction with various functional groups. The nitrogen atom of DzEBA Substituents can be controlled to increase selectivity for the substrate.

Claims (3)

A thermosetting resin represented by the following formula (I):
(I)

In the above formula (I)
R represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted 6 to 20 carbon atoms An aryl group, and a group represented by the following formula 1,
[Structural formula 1]

In the above formula 1,
R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, a halogen group, a nitrile group, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, 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. The method according to claim 1,
The substituted or non-substituted ring is the R, R ₁ and R ₂ are each independently a heavy hydrogen, a halogen group, a nitrile group, a hydroxyl group, an alkenyl group, a cycloalkyl group having 3 to 20 carbon atoms in the alkyl group having 1 to 20 carbon atoms, 2 to 20 carbon atoms , An aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms, which is substituted with one or two or more selected substituents selected from the above substituents, Thermosetting resin. The method according to claim 1,
The thermosetting resin according to any one of claims 1 to 3,
[Chemical Formula 1]

(2)

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