KR102340924B1 - A resin composition with improved impact strength - Google Patents

Abstract

The present invention relates to an impact resistant resin composition. According to the present invention, there is provided an impact-resistant phthalonitrile-based resin composition that has excellent processability and improved impact strength, and can be suitably used as a durable agent for airplanes, ships, automobiles, and the like.

Description

Resin composition having improved impact strength {A RESIN COMPOSITION WITH IMPROVED IMPACT STRENGTH}

The present invention relates to a phthalonitrile-based resin composition having improved impact strength.

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 in 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.

_{The process window is one measure of the processability of the resin, and the processing temperature (T p} ), which is a temperature at which the mixture of the phthalonitrile monomer and the curing agent or the prepolymer formed by the reaction of the mixture exists in a processable state, and curing It can be expressed as an absolute value of the difference (T _c -T _p ) of the temperature (T _{c ).}

Since the phthalonitrile resin has a solid hardened structure by triazine generated through high temperature curing, mechanical properties such as impact strength are very weak.

Therefore, in order to expand the applicable range of the phthalonitrile-based resin, it is required to supplement the impact strength while minimizing the loss of the process window for securing workability.

The present invention is to provide a phthalonitrile-based resin having excellent processability and improved impact strength.

According to the present invention,

(a) a resin binder comprising a phthalonitrile compound and a curing agent thereof, and

(b) MAX phase composite particles surface-modified with polyethyleneimine

It provides an impact-resistant resin composition comprising a.

Hereinafter, the impact-resistant resin composition 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.

The meaning of 'comprising' as used herein 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

As a result of continuous research by the present inventors, it was confirmed that the phthalonitrile-based resin composition including the composite particles of the MAX phase surface-modified with polyethyleneimine can exhibit improved impact strength while having excellent processability.

The resin composition having the above properties makes it possible to provide a durable agent that can be suitably used for airplanes, ships, automobiles, and the like.

According to one embodiment of the invention,

(a) a resin binder comprising a phthalonitrile compound and a curing agent thereof, and

(b) MAX phase composite particles surface-modified with polyethyleneimine

It provides an impact-resistant resin composition comprising a.

Hereinafter, components that may be included in the impact-resistant resin composition will be described.

(a) resin binder

The impact-resistant resin composition includes a resin binder including a phthalonitrile compound and a curing agent thereof.

* 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 phthalonitrile compound may be a compound represented by the following Chemical 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 of the following formula P2, or a group of the following formula P3 , 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 to be,

[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 term “alkyl group” may be straight-chain or branched. 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.

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 present invention, the phthalonitrile compound may be a compound represented by the following Chemical 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, in Formula P1′, a compound in which L ^P2 is -O- and L ^P3 is a direct bond or a methylene group may be used as the phthalonitrile compound.

Meanwhile, the curing agent is a compound capable of reacting with the phthalonitrile oligomer to form a phthalonitrile resin.

For example, the curing agent may be a compound including a functional group capable of reacting with a cyano group of the phthalonitrile oligomer in a molecule.

Preferably, the curing agent may be a compound having at least one functional group selected from the group consisting of an amine group, a hydroxyl group, and an imide group.

Specifically, the curing agent may be a compound represented by the following Chemical Formula C1.

[Formula C1]

In Formula C1, R ^C11 to R ^C16 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, an amine group, or a group represented by the following formula C2, At ^{least two of R C11} to R ^C16 are an amine group or a group represented by the following formula C2,

[Formula C2]

In the formula C2,

L ^C20 is a direct bond, a C _1-5 alkylene group, -O-, or -S-;

R ^C21 to R ^C25 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, or an amine group, wherein at least one of ^{R C21} to R ^{C25 is an amine} it's gi

As a non-limiting example, the curing agent may be a compound represented by the following Chemical Formula C1'.

[Formula C1']

In the formula C1'

R ^C11 , R ^C13 , R ^C14 , and R ^C15 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group,

L ^C20 is a direct bond, a C _1-5 alkylene group, -O-, or -S-,

R ^C21 to R ^C25 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, or an amine group, wherein at least one of ^{R C21} to R ^{C25 is an amine} it's a gimmick

In addition, the curing agent may be a compound represented by the following Chemical Formula C3.

[Formula C3]

In the formula C3,

M is a tetravalent radical derived from a compound represented by any one of the following formulas C4 to C6,

X ^C31 and X ^C32 are independently a divalent radical derived from a compound represented by any one of the following formulas C7 and C8;

n is a number greater than or equal to 1;

[Formula C4]

In Formula C4, R ^C40 to R ^C45 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group;

[Formula C5]

In Formula C5, R ^C50 to R ^C57 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group;

[Formula C6]

In the formula C6,

R ^C60 to R ^C69 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group,

X ⁶⁰ is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C( =O)-OL ¹ -OC(=O)-, -L ² -C(=O)-OL ³ -, -L ⁴ -OC(=O)-L ⁵ -, or -L ⁶ -Ar ¹ - L ⁷ -Ar ² -L ⁸ -; wherein L ¹ to L ⁸ are each independently a direct bond, —O—, or a C _1-5 alkylene group; Ar ¹ and Ar ² are each independently a C _6-30 arylene group;

[Formula C7]

*

In Formula C7, R ^C70 to R ^C75 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 C8]

In the formula C8,

R ^C80 to R ^C89 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,

X ^C80 is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -NR ^a -, -S(=O)-, -S(=O) ₂ -, -L ⁹ -Ar ³ -L ¹⁰ -, or -L ¹¹ -Ar ⁴ -L ¹² -Ar ⁵ -L ¹³ -; 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 ⁹ to L ¹³ 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.

As a non-limiting example, the curing agent may be a compound represented by the following Chemical Formula C3' or the following Chemical Formula C''.

[Formula C3']

[Formula C3'']

In the above formulas C3' and C3'',

X and X' are each independently a direct bond, a C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C(=O)-OL ¹ -OC(=O)-, -L ² -C(=O)-OL ³ -, -L ⁴ -OC(=O)-L ⁵ -, or -L ⁶ -Ar ¹ -L ⁷ -Ar ² -L ⁸ -; wherein L ¹ to L ⁸ are each independently a direct bond, —O—, or a C _1-5 alkylene group; The Ar ¹ and Ar ² are each independently a C _6-30 arylene group,

R ⁹⁰ to R ⁹⁹ 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.

The content of the curing agent may be adjusted within a range in which curability to be imparted to the resin binder can be secured.

As a non-limiting example, the curing agent may be included in a molar ratio of 0.01 to 1.5 moles per 1 mole of the phthalonitrile compound.

If the molar ratio of the curing agent is increased, the process window may be narrowed and processability may be deteriorated or high temperature curing conditions may be required. And, when the molar ratio of the curing agent is lowered, curability may become insufficient.

(b) surface-modified MAX phase composite particles

The impact-resistant resin composition includes a composite particle of the MAX phase surface-modified with polyethyleneimine.

The composite particle is one in which a part or all of the surface on MAX is modified with polyethyleneimine.

The MAX phase is stacked hexagonal carbide and nitride represented by the following formula (1).

[Formula 1]

M _n+1 AX _n

In Formula 1,

M is a transition metal,

A is at least one element selected from the group consisting of group 13 and group 14 elements,

X is at least one element selected from the group consisting of carbon and nitrogen,

n is 1 to 3.

The known MAX _{phases are Ti 2} CdC, Sc ₂ InC, Ti ₂ AlC, Ti ₂ GaC, Ti ₂ InC, Ti ₂ TlC, V ₂ AlC, V ₂ GaC, Cr ₂ GaC, Ti ₂ AlN, Ti ₂ GaN, Ti ₂ InN, V ₂ GaN, Cr ₂ GaN, Ti ₂ GeC, Ti ₂ SnC, Ti ₂ PbC, V ₂ GeC, Cr ₂ AlC, Cr ₂ GeC, V ₂ PC, V ₂ AsC, Ti ₂ SC, Zr ₂ InC , Zr ₂ TlC, Nb ₂ AlC, Nb ₂ GaC, Nb ₂ InC, Mo ₂ GaC, Zr ₂ InN, Zr ₂ TlN, Zr ₂ SnC, Zr ₂ PbC, Nb ₂ SnC, Nb ₂ PC, Nb ₂ AsC, Zr ₂ SC, Nb ₂ SC, Hf ₂ InC, Hf ₂ TlC, Ta ₂ AlC, Ta ₂ GaC, Hf ₂ SnC, Hf ₂ PbC, Hf ₂ SnN, Hf ₂ SC, Zr ₂ AlC, Ti ₃ AlC ₂ , Ti ₃ GaC ₂ , Ti ₃ InC ₂ , V ₃ AlC ₂ , Ti ₃ SiC ₂ , Ti ₃ GeC ₂ , Ti ₃ SnC ₂ , Ta ₃ AlC ₂ , Zr ₃ AlC ₂ , Ti ₄ AlN ₃ , V ₄ AlC ₃ , Ti ₄ GaC ₃ , Ti ₄ SiC ₃ , Ti ₄ GeC ₃ , Nb ₄ AlC ₃ , Ta ₄ AlC ₃ , and the like can be exemplified.

Preferably, the composite particle is one selected from the group consisting _{of Ti 3} AlC ₂ , Ti ₃ GaC ₂ , Ti ₃ InC ₂ , Ti ₃ SiC ₂ , Ti ₃ GeC ₂ , and Ti ₃ SnC _{2 MAX (MAX)} can have an award.

As a non-limiting example, the composite particles may be obtained by milling the MAX phase and polyethyleneimine in an appropriate organic solvent. By the milling, the size of the MAX phase is adjusted to an appropriate level, and at the same time, the surface of the MAX phase may be modified with polyethyleneimine.

According to an embodiment of the invention, the composite particles preferably have a particle diameter of 0.01 μm to 100 μm. Specifically, the composite particles may have a particle diameter of 0.01 μm to 100 μm, preferably 0.5 μm or less. As a non-limiting example, the max phase used in the preparation of the composite particles may have a particle diameter of 100 μm or less or 5 to 100 μm.

When the particle diameter of the composite particle is too large, there may be a problem in that it acts as a defect that causes a decrease in strength from the viewpoint of the cured structure of the resin. Therefore, it is preferable that the particle diameter of the composite particles be 100 μm or less.

However, composite particles having too small a particle diameter may have limitations in manufacturing. Therefore, the particle size of the composite particles is preferably controlled within the above range.

According to an embodiment of the invention, the polyethyleneimine included in the composite particles is preferably included in an amount of 0.1 to 10% by weight based on the total weight of the composite particles.

Specifically, the content of the polyethyleneimine included in the composite particles may be 0.1 to 10% by weight based on the total weight of the composite particles.

When the content of the polyethyleneimine included in the composite particles is too large, there may be a problem of deterioration in heat resistance due to an increase in the content of decomposable organic matter. Therefore, the content of the polyethyleneimine is preferably 10% by weight or less.

However, when the content of the polyethyleneimine included in the composite particles is too small, the effect of preventing milling and re-agglomeration may not be sufficient, so that it may be difficult to control the particle size of the particles. Therefore, the content of the polyethyleneimine is preferably 0.1% by weight or more.

According to an embodiment of the invention, the composite particles may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the resin binder.

Specifically, with respect to 100 parts by weight of the resin binder, the composite particles are included in 0.1 to 20 parts by weight, or 0.5 to 20 parts by weight, or 0.5 to 15 parts by weight, or 1 to 15 parts by weight, or 1 to 10 parts by weight. can

When the content of the composite particles is too small, the impact resistance improvement effect cannot be expressed in the resin composition. In addition, when the content of the composite particles is too large, a problem of acting as a defect causing a decrease in strength from the viewpoint of the cured structure of the resin may appear.

(c) additives

According to an embodiment of the invention, the impact-resistant 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 impact-resistant 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.

Physical properties of the resin composition

The impact-resistant resin composition may exhibit improved impact strength while having excellent processability.

As an example, the impact-resistant resin composition may have an impact strength of 400 J/m or more according to ASTM D256 (23°C) test method.

And, the impact-resistant resin composition may have a process window of 50 ℃ or more. Specifically, the process window of the impact-resistant resin composition may be 50 °C or higher, or 50 °C to 210 °C, or 55 °C to 205 °C.

The process window is one measure of the processability of the resin, and the difference (T _c -T _p ) _{between the processing temperature (T p} ), which is a temperature at which the impact-resistant resin composition exists in a processable state, and the curing temperature (T _{c )} It can be expressed as an absolute value of

The processing temperature (T _p ) refers to a temperature at which the impact-resistant resin composition exists in a processable state, and may be exemplified by a _{glass transition temperature (T g} ) or a melting temperature (T _{m ).} The curing temperature (T _c ) may be exemplified by an exothermic onset temp., T _{o ) of the impact-resistant resin composition.}

Meanwhile, the impact-resistant resin composition may be provided in a prepolymer state.

The prepolymer state is a state in which the reaction between the phthalonitrile compound constituting the resin binder and the curing agent has occurred to some extent (for example, the so-called A or B stage polymerization state), but in a completely polymerized state It may mean a state in which processing is possible by showing appropriate fluidity without reaching.

According to the present invention, there is provided an impact-resistant phthalonitrile-based resin composition that has excellent processability and improved impact strength, and can be suitably used as a durable agent for airplanes, ships, automobiles, and the like.

^{1 and 2 show 1} H-NMR data for the compounds according to Preparation Examples 1 and 2.

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.

^One H-NMR (Nuclear Magnetic Resonance) analysis

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

Preparation Example 1. Synthesis of phthalonitrile compound (PN1)

Compound (PN1) of Formula A1 was synthesized by the following method.

32.7 g of the compound of Formula A2 and 120 g of DMF (Dimethyl Formamide) were put into a 3-neck round bottom flask (RBF), and dissolved by stirring at room temperature. Then, 51.9 g of a compound of Formula A3 was added, and 50 g of DMF was added thereto, followed by stirring to dissolve. Then, 62.2 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85 °C while stirring. After reacting in the above state for about 5 hours, it was cooled to room temperature. The cooled reaction solution was poured into an aqueous hydrochloric acid solution having a concentration of 0.2N for neutralization and precipitation, followed by filtering and washing with water. Thereafter, the filtered reactant was dried in a vacuum oven at 100° C. for 1 day, and after removing water and residual solvent, the compound of Formula A1 (PN1) was obtained in a yield of about 80% by weight. ¹ H-NMR analysis results of the obtained compound of formula A1 (PN1) are shown in FIG. 1 .

[Formula A1]

[Formula A2]

[Formula A3]

Preparation Example 2. Synthesis of curing agent compound (CA1)

Compound (CA1) of formula A14 below was synthesized by dehydration condensation of diamine and dianhydride. 24 g of 4,4'-oxydianiline and 40 g of N-methyl-pyrrolidone (NMP) 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 8.7 g of the compound of Formula A15 was slowly divided into 3 portions and added together with 40 g of NMP. When all the added compounds were dissolved, 16 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. 4.2 mL of pyridine was added as a dehydration condensation catalyst, 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 compound (CA1) of Formula A14 in a yield of about 85% by weight. ^{The result of 1} H-NMR analysis of the obtained compound of formula A14 (CA1) is shown in FIG. 2 .

[Formula A14]

[Formula A15]

Preparation Example 3. Preparation of Composite Particles (PM1)

TiC, Al, and Ti were mixed at a molar ratio of 2:1.2:1.2 and calcined at 1425° C. in an Ar atmosphere for 15 minutes to obtain a MAX phase represented by _{Ti 3} AlC _{2 .} The prepared Max phase was pulverized using a grinder, and then classified through a 400 mesh sieve to obtain Max phase particles having a particle size of 5 to 30 μm.

In a container of a Planetary Ball Mill apparatus (PM 400, Retsch GmbH), 7.2 g of the max phase particles having a particle diameter of 5 to 30 μm, 0.82 g of polyethyleneimine (TCI Chemicals, 30% in water, Mw 25000 g/mol), 0.5 mm in particle size 110 g of ZrO ₂ beads, 25 ml of a solvent (isopopyl alcohol), and milling for 2 hours.

Through the above method, composite particles of Max phase surface-modified with polyethyleneimine were obtained (particle diameter of 0.1 to 0.5 μm, containing 3.4 wt% of polyethyleneimine based on the total weight of the composite particles).

Preparation Example 4. Preparation of Max Phase Particles (M2)

TiC, Al, and Ti were mixed at a molar ratio of 2:1.2:1.2 and calcined at 1425° C. in an Ar atmosphere for 15 minutes to obtain a MAX phase represented by _{Ti 3} AlC _{2 .} The prepared Max phase was pulverized using a grinder, and then classified through a 400 mesh sieve to obtain Max phase particles having a particle size of 5 to 30 μm.

Preparation Example 5. Preparation of Max Phase Particles (M3)

TiC, Al, and Ti were mixed at a molar ratio of 2:1.2:1.2 and calcined at 1425° C. in an Ar atmosphere for 15 minutes to obtain a MAX phase represented by _{Ti 3} AlC _{2 .} The prepared Max phase was pulverized using a grinder, and then classified through a 140 to 270 mesh sieve to obtain Max phase particles having a particle diameter of 53 to 100 μm.

Preparation Example 6. Preparation of Max Phase Particles (M4)

TiC, Al, and Ti were mixed at a molar ratio of 2:1.2:1.2 and calcined at 1425° C. in an Ar atmosphere for 15 minutes to obtain a MAX phase represented by _{Ti 3} AlC _{2 .} The prepared Max phase was pulverized using a grinder, and then classified through a 400 mesh sieve to obtain Max phase particles having a particle size of 5 to 30 μm.

The max phase particles having a particle diameter of 5 to 30 μm were aluminum etched in 1M NaOH solution for 48 hours to obtain max phase particles (particle diameter 5 to 10 μm) having a _{TiO 2 layer formed on the particle surface.}

*

Preparation Example 7. Preparation of Max Phase Particles (M5)

_{The max phase particles having TiO 2} layer formed on the particle surface obtained in Preparation Example 6 were mixed with p-aminophenyltrimethoxysilane, and a silane coupling reaction was performed.

Through the above method, max phase composite particles surface-modified with amine were obtained (particle diameter of 5 to 10 μm, containing 1-2 wt% of amine based on the total weight of the particles).

Example 1

A resin binder was prepared by mixing 100 parts by weight of the compound (PN1) of Preparation Example 1 and about 0.18 moles of the compound (CA1) of Preparation Example 2 relative to 1 mole of the compound (PN1).

100 parts by weight of the resin binder and 1 part by weight of the composite particles (PM1) of Preparation Example 3 were added to a container of an internal batch mixer, and then mixed to prepare a resin composition.

* Comparative Example 1

A resin composition was prepared by mixing 100 parts by weight of the compound (PN1) of Preparation Example 1 and about 0.18 moles of the compound (CA1) of Preparation Example 2 relative to 1 mole of the compound (PN1).

Comparative Example 2

A resin binder was prepared by mixing 100 parts by weight of the compound (PN1) of Preparation Example 1 and about 0.18 moles of the compound (CA1) of Preparation Example 2 relative to 1 mole of the compound (PN1).

100 parts by weight of the resin binder and 1 part by weight of the max phase particles (M2) of Preparation Example 4 were added to a container of an internal batch mixer, and then mixed to prepare a resin composition.

Comparative Example 3

A resin binder was prepared by mixing 100 parts by weight of the compound (PN1) of Preparation Example 1 and about 0.18 mol of the compound (CA1) of Preparation Example 2 relative to 1 mole of the compound (PN1).

100 parts by weight of the resin binder and 0.5 parts by weight of the max phase particles (M2) of Preparation Example 4 were added to a container of an internal batch mixer, and then mixed to prepare a resin composition.

Comparative Example 4

A resin binder was prepared by mixing 100 parts by weight of the compound (PN1) of Preparation Example 1 and about 0.18 mol of the compound (CA1) of Preparation Example 2 relative to 1 mole of the compound (PN1).

100 parts by weight of the resin binder and 3 parts by weight of the max phase particles (M2) of Preparation Example 4 were added to a container of an internal batch mixer, and then mixed to prepare a resin composition.

Comparative Example 5

A resin binder was prepared by mixing 100 parts by weight of the compound (PN1) of Preparation Example 1 and about 0.18 mol of the compound (CA1) of Preparation Example 2 relative to 1 mole of the compound (PN1).

100 parts by weight of the resin binder and 5 parts by weight of the max phase particles (M2) of Preparation Example 4 were added to a container of an internal batch mixer, and then mixed to prepare a resin composition.

Comparative Example 6

A resin binder was prepared by mixing 100 parts by weight of the compound (PN1) of Preparation Example 1 and about 0.18 mol of the compound (CA1) of Preparation Example 2 relative to 1 mole of the compound (PN1).

100 parts by weight of the resin binder and 1 part by weight of the max phase particles (M3) of Preparation Example 5 were added to a container of an internal batch mixer, and then mixed to prepare a resin composition.

Comparative Example 7

A resin binder was prepared by mixing 100 parts by weight of the compound (PN1) of Preparation Example 1 and about 0.18 mol of the compound (CA1) of Preparation Example 2 relative to 1 mole of the compound (PN1).

100 parts by weight of the resin binder and 1 part by weight of the max phase particles (M4) of Preparation Example 6 were added to a container of an internal batch mixer, and then mixed to prepare a resin composition.

Comparative Example 8

A resin binder was prepared by mixing 100 parts by weight of the compound (PN1) of Preparation Example 1 and about 0.18 mol of the compound (CA1) of Preparation Example 2 relative to 1 mole of the compound (PN1).

100 parts by weight of the resin binder and 1 part by weight of the max phase particles (M5) of Preparation Example 7 were added to a container of an internal batch mixer, and then mixed to prepare a resin composition.

phthalonitrile hardener particle Example 1 PN1 CA1 PM1 (1 part by weight) Comparative Example 1 PN1 CA1 - Comparative Example 2 PN1 CA1 M2 (1 part by weight) Comparative Example 3 PN1 CA1 M2 (0.5 parts by weight) Comparative Example 4 PN1 CA1 M2 (3 parts by weight) Comparative Example 5 PN1 CA1 M2 (5 parts by weight) Comparative Example 6 PN1 CA1 M3 (1 part by weight) Comparative Example 7 PN1 CA1 M4 (1 part by weight) Comparative Example 8 PN1 CA1 M5 (1 part by weight)

Test Example Using the resin composition of the above Examples and Comparative Examples to produce a specimen without a notch of ASTM D256 standard, using a Digital impact tester (QM (700A)), the impact strength according to ASTM D256 (23 ℃) test method (J/m) was measured. The results are shown in Table 2 below.

Impact strength (J/m) Example 1 453.4 Comparative Example 1 353.3 Comparative Example 2 360.8 Comparative Example 3 205.2 Comparative Example 4 340.0 Comparative Example 5 197.1 Comparative Example 6 231.8 Comparative Example 7 361.8 Comparative Example 8 354.2

Referring to Table 2, it was confirmed that the specimen to which the resin composition of Example 1 is applied has significantly superior impact strength compared to the comparative examples. And, even in the Max phase of the same composition, when particles having a large particle size distribution are applied, impact strength was found to decrease. In addition, compared to Comparative Example 7 to which the aluminum etched Max phase was applied and Comparative Example 8 to which the Max phase surface-treated with a silane coupling agent was applied, remarkably excellent impact strength could be expressed in Example 1 to which the Max phase surface-treated with polyethyleneimine was applied. it was confirmed that there is

Claims (9)

(a) a resin binder comprising a phthalonitrile compound and a curing agent thereof, and
(b) comprising composite particles in the MAX phase surface-modified with polyethyleneimine,
The composite particles have a particle diameter of 0.1 μm to 0.5 μm, Ti ₃ AlC ₂ , Ti ₃ GaC ₂ , Ti ₃ InC ₂ , Ti ₃ SiC ₂ , Ti ₃ GeC ₂ , and Ti ₃ SnC ₂ 1 selected from the group consisting of I have the Max (MAX) image of the kind,
An impact-resistant resin composition.
The method of claim 1,
The phthalonitrile compound is a compound represented by the following formula (P1), the impact resistance 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 of the following formula P2, or a group of the following formula P3 , 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 to be,
[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 curing agent is a compound represented by the following formula C1, impact resistance resin composition.
[Formula C1]

In Formula C1, R ^C11 to R ^C16 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, an amine group, or a group represented by the following formula C2, At ^{least two of R C11} to R ^C16 are an amine group or a group represented by the following formula C2,
[Formula C2]

In the formula C2,
L ^C20 is a direct bond, a C _1-5 alkylene group, -O-, or -S-;
R ^C21 to R ^C25 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, a C _6-30 aryl group, or an amine group, wherein at least one of ^{R C21} to R ^{C25 is an amine} it's gi
The method of claim 1,
The curing agent is a compound represented by the following formula C3, impact resistance resin composition.
[Formula C3]

In the formula C3,
M is a tetravalent radical derived from a compound represented by any one of the following formulas C4 to C6,
X ^C31 and X ^C32 are independently a divalent radical derived from a compound represented by any one of the following formulas C7 and C8;
n is a number greater than or equal to 1;
[Formula C4]

In Formula C4, R ^C40 to R ^C45 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group;
[Formula C5]

In Formula C5, R ^C50 to R ^C57 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group;
[Formula C6]

In the formula C6,
R ^C60 to R ^C69 are each independently hydrogen, a C _1-5 alkyl group, a C _1-5 alkoxy group, or a C _6-30 aryl group,
X ⁶⁰ is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -C( =O)-OL ¹ -OC(=O)-, -L ² -C(=O)-OL ³ -, -L ⁴ -OC(=O)-L ⁵ -, or -L ⁶ -Ar ¹ - L ⁷ -Ar ² -L ⁸ -; wherein L ¹ to L ⁸ are each independently a direct bond, —O—, or a C _1-5 alkylene group; Ar ¹ and Ar ² are each independently a C _6-30 arylene group;
[Formula C7]

In Formula C7, R ^C70 to R ^C75 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 C8]

In the formula C8,
R ^C80 to R ^C89 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,
X ^C80 is a direct bond, C _1-5 alkylene group, -O-, -S-, -C(=O)-, -NR ^a -, -S(=O)-, -S(=O) ₂ -, -L ⁹ -Ar ³ -L ¹⁰ -, or -L ¹¹ -Ar ⁴ -L ¹² -Ar ⁵ -L ¹³ -; 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 ⁹ to L ¹³ 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,
The curing agent is included in a molar ratio of 0.01 to 1.5 moles per 1 mole of the phthalonitrile compound, the impact resistance resin composition.
delete delete The method of claim 1,
The polyethyleneimine is contained in an amount of 0.1 to 10% by weight based on the total weight of the composite particles, the impact resistance resin composition.
The method of claim 1,
The composite particles are included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the resin binder, the impact resistance resin composition.

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