KR102313378B1 - A phthalonitrile-based curable resin composition having excellent heat resistance and a prepolymer thereof - Google Patents

Abstract

The present invention relates to a phthalonitrile-based curable resin composition and a prepolymer thereof. According to the present invention, there is provided a phthalonitrile-based curable resin composition that is easy to manufacture and has excellent heat resistance and can be applied to more diverse fields.

Description

Phthalonitrile-based curable resin composition having excellent heat resistance and prepolymer thereof

The present invention relates to a phthalonitrile-based curable resin composition and a prepolymer thereof.

Phthalonitrile-based resins are known as thermosetting resins having excellent heat resistance and flame retardancy. A resin composition in which a phthalonitrile-based resin and additives such as glass fiber and carbon fiber are mixed may be used as a durable material for airplanes, ships, automobiles, and the like.

The phthalonitrile-based resin is generally formed by polymerization and high-temperature curing by applying a phthalonitrile compound having two or more phthalonitrile groups and a curing agent thereof.

In general, the phthalonitrile compound has many aromatic groups and thus has high rigidity and large molecular weight. Accordingly, the mixture of the phthalonitrile compound and the curing agent or the prepolymer formed by the reaction of the mixture has a very narrow process window. Therefore, in order to expand the applicable range of the phthalonitrile-based resin, it is required to improve the process window for securing workability.

On the other hand, in order to obtain a phthalonitrile-based resin having required physical properties, the curing agent is also considered as an important factor.

In general, an aromatic imide compound having an amine terminus has been used as the curing agent. And, in order to ensure compatibility with the phthalonitrile compound, the curing agent having a low molecular weight is required.

However, in order to synthesize an amine-terminated aromatic imide compound having a low molecular weight as the curing agent, a very large amount of an aromatic amine compound is required compared to the dianhydride compound, which reduces the production efficiency of the phthalonitrile-based resin and the raw material price. There are limits to the rise.

An object of the present invention is to provide a phthalonitrile-based curable resin composition that can be cured at a relatively low temperature and has improved heat resistance.

And, the present invention is to provide a prepolymer as a reactant of the curable resin composition.

According to the present invention, there is provided a curable resin composition comprising (a) a phthalonitrile compound and (b) a curing agent that is a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

M is a tetravalent radical derived from an aliphatic, cycloaliphatic or aromatic compound,

Ar ^{1 To} Ar ⁴ are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy a group, a C _6-30 aryloxy group, or _{a C 6-50} arylene group that is unsubstituted or substituted with a _{C 6-30} aryl group,

n is 1 or 2.

And, according to the present invention, a prepolymer as a reactant of the curable resin composition is provided.

Hereinafter, a curable resin composition and a prepolymer thereof according to embodiments of the present invention will be described in detail.

Prior to that, unless explicitly stated herein, terminology is for the purpose of referring to specific embodiments only, and is not intended to limit the present invention.

As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite.

As used herein, the meaning of 'comprising' specifies a particular characteristic, region, integer, step, operation, element and/or component, and other specific characteristic, region, integer, step, operation, element, component, and/or group. It does not exclude the existence or addition of

표시는 해당 그룹이 다른 그룹에 연결되는 위치를 의미한다.In the formula of this specification

The mark indicates a location where the corresponding group is linked to another group.

I. Curable Resin Composition

According to one embodiment of the present invention, there is provided a curable resin composition comprising (a) a phthalonitrile compound and (b) a curing agent which is a compound represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1,

M is a tetravalent radical derived from an aliphatic, cycloaliphatic or aromatic compound,

Ar ^{1 To} Ar ⁴ are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy a group, a C _6-30 aryloxy group, or _{a C 6-50} arylene group that is unsubstituted or substituted with a _{C 6-30} aryl group,

n is 1 or 2.

As a result of continuous research by the present inventors, it was confirmed that the curable resin composition including the compound represented by Formula 1 as a curing agent can perform a curing process at a relatively low temperature and exhibit improved heat resistance.

The compound represented by Formula 1 facilitates the curing process of the curable resin composition by appropriately lowering an onset temperature of the curable resin composition.

The compound represented by Formula 1 has an amide bond in the molecule, so that hydrogen bonding between the curing agents is possible in the curable resin composition. This is considered to be a factor enabling the curable resin composition to exhibit improved heat resistance.

Furthermore, the curing agent, which is a compound represented by Formula 1, has a chemical structure that can be synthesized by reaction of 2 equivalents of a diamine compound compared to a dianhydride compound. That is, unlike the previous curing agent that required the use of a very large amount of the diamine compound compared to the dianhydride compound, the curing agent, which is the compound represented by Formula 1, has a chemical structure that can be synthesized using a small amount of the diamine compound.

Hereinafter, components that may be included in the curable resin composition will be described.

(a) phthalonitrile compounds

According to an embodiment of the present invention, the curable resin composition includes a phthalonitrile compound.

The phthalonitrile compound may include those well known in the art to which the present invention pertains.

As a non-limiting example, the phthalonitrile compound includes US Pat. No. 4,408,035, US Pat. No. 5,003,039, US Pat. No. 5,003,078, US Pat. No. 5,004,801, US Pat. No. 5,132,396, US Pat. No. 5,139,054, US Pat. The compounds disclosed in U.S. Patent No. 5,208,318, U.S. Patent No. 5,237,045, U.S. Patent No. 5,292,854, or U.S. Patent No. 5,350,828 can be exemplified.

Preferably, the (a) phthalonitrile compound may be a compound represented by the following formula P1.

[Formula P1]

In Formula P1, R ^P11 to R ^P16 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, a group P2 below, or a group P3 below , at ^{least two of R P11} to R ^P16 are a group of the following formula P2 or a group of the following formula P3,

[Formula P2]

In the above formula P2,

L ^P2 is a direct bond, a C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, or -S(=O) ₂ -;

R ^P21 to R ^P25 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, or a cyano group, wherein at ^{least two of R P21} to R ^P25 are a cyano group am,

[Formula P3]

In the formula P3,

L ^P3 is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C( CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-,

R ^P31 to R ^P35 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, and a group of Formula P2, wherein at least one of ^{R P31} to R ^{P35 is} It is a group of the above formula P2.

As used herein, the "alkyl group" may be a straight-chain or branched chain. Preferably, the alkyl group has 1 to 5 carbon atoms or 1 to 3 carbon atoms. Specifically, the alkyl group is methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n- pentyl, isopentyl, neopentyl, and tert-pentyl, and the like.

As used herein, the "aryl group" may be a monocyclic aryl group or a polycyclic aryl group. Preferably, the aryl group has 6 to 30 carbon atoms. Specifically, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, and a fluorenyl group.

As used herein, the term “direct bond” means that no atoms are present in the group and that the groups on both sides are directly connected to each other.

According to an embodiment of the invention, the (a) phthalonitrile compound may be a compound represented by the following formula P1'.

[Formula P1']

In the formula P1',

L ^P2 and L ^P3 are each independently a direct bond, a C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-.

As a non-limiting example, a compound in which L ^P2 is -O- and L ^P3 is a direct bond or a methylene group in Formula P1' may be used as the phthalonitrile compound (a).

(b) curing agent

According to an embodiment of the present invention, the curable resin composition includes (b) a curing agent, which is a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

M is a tetravalent radical derived from an aliphatic, cycloaliphatic or aromatic compound,

Ar ^{1 To} Ar ⁴ are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy a group, a C _6-30 aryloxy group, or _{a C 6-50} arylene group that is unsubstituted or substituted with a _{C 6-30} aryl group,

n is 1 or 2.

As used herein, the term "substituted or unsubstituted" includes unsubstituted or single or multiple substitution with one or more substituents.

Specifically, in Formula 1, M may be a tetravalent radical derived from a compound represented by any one of Formulas 2 to 5 below.

[Formula 2]

In Formula 2, R ²⁰ to R ²⁵ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group;

[Formula 3]

In Formula 3, R ³⁰ to R ³⁵ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group;

[Formula 4]

In Formula 4, R ⁴⁰ to R ⁴⁷ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group;

[Formula 5]

In Formula 5,

R ⁵⁰ to R ⁵⁹ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group,

X ⁵⁰ is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C( CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, -C(=O)-OL ⁵⁰ -OC(=O)-, -L ⁵¹ -C(=O) -OL ⁵² -, -L ⁵³ -OC(=O)-L ⁵⁴ -, or -L ⁵⁵ -Ar ⁵⁰ -L ⁵⁶ -Ar ⁵¹ -L ⁵⁷ -; wherein L ⁵⁰ to L ⁵⁷ are each independently a direct bond, -O-, or a C _1-5 alkylene group; Ar ⁵⁰ and Ar ⁵¹ are each independently a C _6-30 arylene group.

Preferably, M may be a tetravalent group represented by any one of the following Chemical Formulas 2' to 5'.

[Formula 2']

[Formula 3']

[Formula 4']

[Formula 5']

In Formula 5', X ^50' is a direct bond, a C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-.

Meanwhile, in Formula 1, Ar ¹ to Ar ⁴ may each independently be a divalent radical derived from a compound represented by any one of Formulas 6 and 7.

[Formula 6]

In Formula 6, R ⁶⁰ to R ⁶⁵ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, a hydroxy group, or a carboxyl group;

[Formula 7]

In Formula 7,

R ⁷⁰ to R ⁷⁹ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, a hydroxyl group, or a carboxyl group,

X ⁷⁰ is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -NR ^a -, -S(=O)-, -S(=O) ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, -L ⁷⁰ -Ar ³ -L ⁷¹ -, or -L ⁷² -Ar ⁴ -L ⁷³ -Ar ⁵ -L ⁷⁴ -; wherein R ^a is hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group; wherein L ⁷⁰ to L ⁷⁴ are each independently a direct bond, -O-, or a C _1-5 alkylene group; The Ar ³ to Ar ⁵ are each independently a C _6-30 arylene group.

Preferably, the Ar ¹ to Ar ⁴ may be a divalent group represented by any one of Formulas 6′ and 7′ below.

[Formula 6']

[Formula 7']

In Formula 7', X ^70' is a direct bond, a C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-.

According to an embodiment of the invention, the (b) curing agent may be a compound represented by the following Chemical Formula 1-a or the following Chemical Formula 1-b.

[Formula 1-a]

[Formula 1-b]

In Formulas 1-a and 1-b,

n is 1 or 2,

X ^50' is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C (CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-.

In Formula 1, n is 1 or 2.

According to an embodiment of the present invention, the curable resin composition may include a mixture of a compound having n=1 and a compound having n=2 in Formula 1 as the curing agent (b).

Meanwhile, the curing agent, which is the compound represented by Formula 1, may be synthesized using 2 equivalents of the diamine compound represented by Formula 1-Am below compared to the dianhydride compound represented by Formula 1-Ah.

[Formula 1-Ah]

[Formula 1-Am]

In Formulas 1-Ah and 1-Am, M, Ar ¹ and Ar ² are each as defined in Formula 1 above.

Specifically, in Formula 1-Ah, M may be a tetravalent radical derived from a compound represented by any one of Formulas 2 to 5.

Preferably, M in Formula 1-Ah may be a tetravalent group represented by any one of Formulas 2' to 5'.

And, in Formula 1-Am, Ar ¹ and Ar ² may each independently be a divalent radical derived from a compound represented by any one of Formulas 6 and 7.

Preferably, in Formula 1-Am, Ar ¹ and Ar ² may each independently be a divalent group represented by any one of Formulas 6′ and 7′.

In the diamine compound represented by Formula 1-Am, aromatic amine groups at both ends have different reactivity. ^{The aromatic amine group (-Ar 2} -NH ₂ ) connected to -NH- of the anilide group in Formula 1-Am exhibits a relatively high nucleophilicity and preferentially reacts with the dianhydride compound of Formula 1-Ah to form an imide form a ring ^{In addition, the aromatic amine group (-Ar 1} -NH ₂ ) connected to -C(=O)- of the anilide group in Formula 1-Am exhibits relatively low nucleophilicity, and thus the dianhydride compound of Formula 1-Ah and doesn't react However, in Formula 1-Am, the aromatic amine group (-Ar ¹ -NH ₂ ) linked to -C(=O)- of the anilide group is cured in reaction with the phthalonitrile group of the (a) phthalonitrile compound. It was confirmed that it enables the expression of the effect of lowering the starting temperature.

On the other hand, the content of the (b) curing agent may be adjusted in a range that can secure the curability to be imparted to the curable resin composition.

For example, the (b) curing agent may be included in an amount of 0.01 to 1.5 moles based on 1 mole of the (a) phthalonitrile compound.

When the content of the curing agent is too high, the process window of the curable resin composition may be narrowed and processability may be deteriorated or high temperature curing conditions may be required. When the content of the curing agent is too low, curability of the curable resin composition may be insufficient.

(c) additives

According to an embodiment of the invention, the curable resin composition may further include additives depending on the field of application and use thereof.

The kind of the said additive is not specifically limited.

And, the content of the additive may be adjusted within a range that does not impair the physical properties of the curable resin composition.

By way of non-limiting example, the additive includes reinforcing fibers such as metal fibers, carbon fibers, glass fibers, aramid fibers, potassium titanate fibers, celluloid fibers, sepiolite fibers, ceramic fibers, and acrylic fibers; inorganic fillers such as barium sulfate, calcium carbonate, zirconia, alumina, zirconium silicate, and silicon carbide; A lubricant such as graphite, polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and milled carbon fiber may be applied.

II. prepolymer

According to another embodiment of the present invention, a prepolymer that is a reactant of the above-described curable resin composition is provided.

The prepolymer is in a state in which the reaction between the phthalonitrile compound and the curing agent in the curable resin composition has occurred to some extent (for example, the so-called A or B stage polymerization state), but does not reach a fully cured state. It indicates fluidity and means that it is in a state where processing is possible.

The prepolymer has a low onset temperature and a wide process window, so it can be applied to more diverse fields.

According to the present invention, there is provided a phthalonitrile-based curable resin composition that is easy to manufacture and has excellent heat resistance and can be applied to more diverse fields.

^{1 to 5 show 1} H-NMR spectra of the compounds prepared in Preparation Examples 1 to 5, respectively.

Hereinafter, preferred embodiments are presented to help the understanding of the present invention. However, the following examples are only for illustrating the invention, and the present invention is not limited thereto.

*

Preparation Example 1. Synthesis of curing agent (CA-1)

A compound represented by the following formula CA-1 (n=1 to 2) was synthesized by the following method.

22.73 g of 4,4'-diaminobenzanilide and 100 g of DMF (dimethylformamide) were put into a 3-neck round bottom flask (RBF), and dissolved by stirring at room temperature. The above was cooled with a water bath, and 14.7 g of 2,3,3',4'-biphenyl tetracarboxylic dianhydride was slowly divided into three portions and added together with 80 g of DMF. When all of the added compounds were dissolved, 35 g of toluene was added to the reactant for azeotrope. A Dean-Stark device and a reflux capacitor were installed, and toluene was added to the Dean-Stark device to fill it. As a dehydration condensation catalyst, 5.3 mL of pyridine was added, the temperature was raised to 170° C., and the mixture was stirred for 3 hours.

While the water generated while the imide ring was formed was removed with a Dean-Stark apparatus, the mixture was further stirred for 2 hours, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature, and recovered by precipitation in methanol. The recovered precipitate was extracted with methanol to remove residual reactants, and dried in a vacuum oven to obtain the compound represented by Chemical Formula CA-1 in a yield of 85% by weight.

¹ H-NMR analysis results for the compound CA-1 are shown in FIG. 1 .

Preparation Example 2. Synthesis of curing agent (CA-2)

A compound represented by the following formula CA-2 in the same manner as in Preparation Example 1, except that 1,2,4,5-cyclohexanetetracarboxylic dianhydride was used instead of 2,3,3',4'-biphenyl tetracarboxylic dianhydride (n = 1-2) were synthesized.

¹ H-NMR analysis results for the compound CA-2 are shown in FIG. 2 .

Preparation Example 3. Synthesis of curing agent (CA-3)

A compound represented by the following formula CA-3 (n = 1 to 2) was synthesized.

¹ H-NMR analysis results for the compound CA-3 are shown in FIG. 3 .

Preparation Example 4. Synthesis of curing agent (CA-4)

A compound represented by the following formula CA-4 (n=1 to 4) was synthesized by the following method.

12.04 g of 4,4'-oxydianiline and 70 g of dimethylformamide (DMF) were put into a 3-neck round bottom flask (RBF), and dissolved by stirring at room temperature. The above was cooled with a water bath, and 9.31 g of 4,4'-oxydiphthalic anhydride was gradually divided into three portions and added together with 70 g of DMF. When all of the added compounds were dissolved, 28 g of toluene was added to the reactant for azeotrope. A Dean-Stark device and a reflux capacitor were installed, and toluene was added to the Dean-Stark device to fill it. As a dehydration condensation catalyst, 3.1 mL of pyridine was added, the temperature was raised to 170° C., and the mixture was stirred for 3 hours.

While the water generated while the imide ring was formed was removed with a Dean-Stark apparatus, the mixture was further stirred for 2 hours, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature, and recovered by precipitation in methanol. The recovered precipitate was extracted with methanol to remove residual reactants, and dried in a vacuum oven to obtain the compound represented by Chemical Formula CA-4 in a yield of 85% by weight.

¹ H-NMR analysis results for the compound CA-4 are shown in FIG. 4 .

In Preparation Example 4, the synthesis was performed using 2 equivalents of a diamine compound as in Preparation Examples 1 to 3, but melting points and ¹ H-NMR analysis indicated by DSC analysis that a large amount of the compound of n=4 or more was produced was confirmed through

As in Preparation Example 4, the high molecular weight curing agent of n=4 or more has poor compatibility with the phthalonitrile monomer during the preparation of the prepolymer, which causes defects such as voids in the resin after curing, thereby causing various mechanical problems including heat resistance. negatively affect the physical properties.

Preparation 5. Synthesis of phthalonitrile compound (PN-1)

[PN-1]

30.04 g of Bisphenol F95 (a mixture of 95% by weight of 4,4'-dihydroxydiphenylmethane and 5% by weight of 2,4-dihydroxydiphenylmethane and 2,2'-dihydroxydiphenylmethane), 34.63 g of 4-nitrophthalonitrile and 197.1 g of DMF (Dimethylformamide) were mixed with 3-neck RBF (3 neck round bottom flask), and stirred at room temperature to dissolve. After all of the added compounds were dissolved, _{41.46 g of K 2} CO _{3 as a} base catalyst was added, the temperature was raised to 85° C., and the mixture was stirred for 12 hours.

After the reaction product was cooled to room temperature, K ₂ CO ₃ was removed using a filtration device, and the reaction product was recovered by precipitation in water. The recovered precipitate was extracted with methanol to remove residual reactants, and dried in a vacuum oven to obtain the compound represented by Formula PN-1 in a yield of 90% by weight.

¹ H-NMR analysis results for the compound PN-1 are shown in FIG. 5 .

Test Example 1: ^One H-NMR (nuclear magnetic resonance) analysis

1H-NMR analysis was performed on the compounds synthesized in Preparation Examples 1 to 5. The results are shown in FIGS. 1 to 5 .

The ¹ H-NMR analysis was performed according to the manufacturer's manual using Bruker's 500 MHz NMR equipment. A sample for NMR measurement was prepared by dissolving the compound in DMSO (dimethyl sulfoxide)-d6.

Test Example 2: DSC (differential scanning calorimetry) analysis

DSC analysis was performed on the compounds obtained in Preparation Examples 1 to 4. Information on whether the synthesized compound is a mixture or a single substance was obtained from the number of melting temperature (T _{m ) peaks in the DSC thermogram.} The results are shown in Table 1 below.

The DSC analysis was performed in _{an N 2} flow atmosphere while the temperature was increased from 35 °C to 450 °C at a temperature increase rate of 10 °C/min using the Q20 system of TA instrument.

manufacturing example compound melting temperature One CA-1 416.6 2 CA-2 329.6 3 CA-3 385.5 4 CA-4 219.8; 244.8; 265.5; 296.1; 319.9

Examples and Comparative Examples to the components shown in Table 2 (a): (b) = 1: is mixed at a ratio of 0.2 mole for each of Examples and Comparative Examples, the curable resin composition was prepared.

Specifically, the (a) phthalonitrile compound was completely melted on a hot plate at 240 °C using an aluminum dish. Herein, the (b) curing agent was added in the above molar ratio. In addition, the prepolymer was prepared by uniformly mixing on a hot plate at 240 °C and cooling.

The prepolymer was cured in an oven by heating at each temperature of 220 ˚C, 250 ˚C, 280 ˚C, 310 ˚C, and 340 ˚C for 2 hours for a total of 10 hours.

(a) phthalonitrile compounds (b) curing agent Example 1 PN-1 CA-1 Example 2 PN-1 CA-2 Example 3 PN-1 CA-3 Comparative Example 1 PN-1 CA-4

Test Example 3: Evaluation of the state of the resin after curing The cured resins obtained in Examples and Comparative Examples were visually observed to evaluate the state of the resin after curing according to the following criteria. The results are shown in Table 3 below.

○: No voids were observed under normal pressure and pressure.

Δ: Voids were observed under normal pressure, but not under pressure.

X: Void observed under normal pressure

Resin state after curing Example 1 ○ Example 2 ○ Example 3 ○ Comparative Example 1 ○

Test Example 4: Dynamic mechanical analysis of resin The cured resin obtained in Examples and Comparative Examples was subjected to dynamic mechanical analysis (DMA). By measuring the storage modulus and loss modulus in the DMA, the temperature of the tan δ peak of the resin can be known, and the temperature value has a characteristic proportional to the heat resistance of the resin. The tan δ values of each Example and Comparative Example are shown in Table 4 below.

The DMA was performed in a method conforming to ASTM D4065 using DMA Q800 equipment from TA Instruments. A single cantilever was used for the measurement mode, and the temperature condition was set at a temperature increase rate of 10 °C/min in the range of 25 ~ 400 °C. The measurement frequency was set to 1 Hz.

tan δ (℃) Example 1 362 Example 2 378 Example 3 350 Comparative Example 1 334

Referring to Table 4, it was confirmed that the curable resin compositions of Examples 1 to 3 had a higher tan δ value than Comparative Example 1 and could exhibit excellent heat resistance.

Claims (10)

(a) a phthalonitrile compound and (b) a curable resin composition comprising a curing agent which is a compound represented by the following formula (1).
[Formula 1]

In Formula 1,
M is a tetravalent radical derived from an aliphatic, cycloaliphatic or aromatic compound,
Ar ^{1 To} Ar ⁴ are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy a group, a C _6-30 aryloxy group, or _{a C 6-50} arylene group that is unsubstituted or substituted with a _{C 6-30} aryl group,
n is 1 or 2.
The method of claim 1,
Wherein M is a tetravalent radical derived from a compound represented by any one of the following formulas 2 to 5, the curable resin composition.
[Formula 2]

In Formula 2, R ²⁰ to R ²⁵ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group;
[Formula 3]

In Formula 3, R ³⁰ to R ³⁵ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group;
[Formula 4]

In Formula 4, R ⁴⁰ to R ⁴⁷ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group;
[Formula 5]

In Formula 5,
R ⁵⁰ to R ⁵⁹ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group,
X ⁵⁰ is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C( CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, -C(=O)-OL ⁵⁰ -OC(=O)-, -L ⁵¹ -C(=O) -OL ⁵² -, -L ⁵³ -OC(=O)-L ⁵⁴ -, or -L ⁵⁵ -Ar ⁵⁰ -L ⁵⁶ -Ar ⁵¹ -L ⁵⁷ -; wherein L ⁵⁰ to L ⁵⁷ are each independently a direct bond, -O-, or a C _1-5 alkylene group; Ar ⁵⁰ and Ar ⁵¹ are each independently a C _6-30 arylene group.
The method of claim 1,
Wherein M is a tetravalent group represented by any one of Formulas 2' to 5', the curable resin composition.
[Formula 2']

[Formula 3']

[Formula 4']

[Formula 5']

In Formula 5', X ^50' is a direct bond, a C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-.
The method of claim 1,
Wherein Ar ^{1 To} Ar ^{4 Are} each independently a divalent radical derived from a compound represented by any one of Formulas 6 and 7, the curable resin composition.
[Formula 6]

In Formula 6, R ⁶⁰ to R ⁶⁵ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, a hydroxy group, or a carboxyl group;
[Formula 7]

In Formula 7,
R ⁷⁰ to R ⁷⁹ are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, a hydroxyl group, or a carboxyl group,
X ⁷⁰ is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -NR ^a -, -S(=O)-, -S(=O) ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, -L ⁷⁰ -Ar ³ -L ⁷¹ -, or -L ⁷² -Ar ⁴ -L ⁷³ -Ar ⁵ -L ⁷⁴ -; wherein R ^a is hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group; wherein L ⁷⁰ to L ⁷⁴ are each independently a direct bond, -O-, or a C _1-5 alkylene group; The Ar ³ to Ar ⁵ are each independently a C _6-30 arylene group.
The method of claim 1,
Wherein Ar ^{One To} Ar ⁴ Is a divalent group represented by any one of Formulas 6' and 7', the curable resin composition.
[Formula 6']

[Formula 7']

In Formula 7', X ^70' is a direct bond, a C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-.
The method of claim 1,
The (b) curing agent is a compound represented by the following Chemical Formula 1-a or the following Chemical Formula 1-b, the curable resin composition.
[Formula 1-a]

[Formula 1-b]

In Formulas 1-a and 1-b,
n is 1 or 2,
X ^50' is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C (CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-.
The method of claim 1,
The (a) phthalonitrile compound is a compound represented by the following formula (P1), the curable resin composition.
[Formula P1]

In Formula P1, R ^P11 to R ^P16 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, a group P2 below, or a group P3 below , at ^{least two of R P11} to R ^P16 are a group of the following formula P2 or a group of the following formula P3,
[Formula P2]

In the above formula P2,
L ^P2 is a direct bond, a C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, or -S(=O) ₂ -;
R ^P21 to R ^P25 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, or a cyano group, wherein at ^{least two of R P21} to R ^P25 are a cyano group am,
[Formula P3]

In the formula P3,
L ^P3 is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C( CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-,
R ^P31 to R ^P35 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, and a group of Formula P2, wherein at least one of ^{R P31} to R ^{P35 is} It is a group of the above formula P2.
The method of claim 1,
The (a) phthalonitrile compound is a compound represented by the following formula P1', the curable resin composition.
[Formula P1']

In the formula P1',
L ^P2 and L ^P3 are each independently a direct bond, a C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -C(=O)NH-.
The method of claim 1,
The (b) curing agent is contained in an amount of 0.01 to 1.5 moles based on 1 mole of the (a) phthalonitrile compound, the curable resin composition.
A prepolymer which is a reactant of the curable resin composition according to claim 1 .

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