KR102118628B1 - Phthalonitrile resin - Google Patents

Abstract

[화학식 2]

상기 화학식 1 및 2에서, 각 치환기는 명세서 중에서 정의한 바와 같다.In the present invention, the first structural unit derived from the compound of Formula 1; And by including a second structural unit derived from the compound of Formula 2, the cure density is reduced, and as a result, a phthalonitrile resin capable of exhibiting excellent impact strength properties is provided:
[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2, each substituent is as defined in the specification.

Description

Phthalonitrile Resin {PHTHALONITRILE RESIN}

The present invention relates to a phthalonitrile resin exhibiting excellent impact strength properties by controlling the curing density.

Phthalononitrile resin (PNR) is a thermosetting resin with excellent heat resistance and flame retardancy, and is used as a durable material for airplanes, ships, automobiles, etc. by forming a complex with glass fibers or carbon fibers. The manufacturing process of the composite may include, for example, a process of mixing a mixture of a phthalonitrile and a curing agent or a prepolymer and a filler formed by reaction of the mixture, followed by curing.

Since phthalonitrile resin has a solid curing structure by triazine produced through high temperature curing, there is a disadvantage in that impact strength is very weak due to strong brittleness.

Korean Registered Patent No. 0558158

Accordingly, the present invention is to solve the problems of the prior art, and to provide a polymerizable composition comprising a phthalonitrile resin and its manufacturing method, the phthalonitrile resin showing excellent impact strength by controlling the curing density .

In order to solve the above problems, according to an embodiment of the present invention,

A first structural unit derived from the compound of Formula 1, and

A phthalonitrile resin comprising a second structural unit derived from the compound of Formula 2 is provided:

[Formula 1]

In Chemical Formula 1,

Ar ₁ and Ar ₂ are each independently an aromatic divalent radical,

X is an alkylene group or an alkylidene group,

Y ₁ and Y ₂ are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom,

R ₁₁ to R ₂₀ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a cyano group, at least two of R ₁₁ to R ₁₅ , and at least two of R ₁₆ to R ₂₀ are cyano groups,

[Formula 2]

In Chemical Formula 2,

R ₂₁ is each independently selected from the group consisting of halogen group, alkyl group, cycloalkyl group, alkoxy group, aryl group, arylalkyl group, alkylaryl group, alkylcycloalkyl group, (cycloalkyl)alkyl group, alkoxyalkyl group, and haloalkyl group,

m is an integer from 0 to 4.

In addition, according to another embodiment of the present invention, there is provided a polymerizable composition comprising the compound of Formula 1, the compound of Formula 2 and a curing agent, and a prepolymer that is a reactant thereof.

According to another embodiment of the present invention, there is provided a method for producing a phthalonitrile resin, comprising the step of curing the polymerizable composition or prepolymer.

The phthalonitrile resin according to the present invention can exhibit excellent impact strength characteristics by controlling the curing density.

1 is a graph showing the results of nuclear magnetic resonance (NMR) analysis for the compound (1a-1) prepared in Preparation Example 1.
2 is a graph showing the results of NMR analysis for the compound (3a) prepared in Preparation Example 2.

The terminology used herein is only used to describe exemplary embodiments, and is not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, the terms "include", "have" or "have" are intended to indicate that an implemented feature, step, component or combination thereof exists, one or more other features or steps, It should be understood that the possibility of the presence or addition of components, or combinations thereof, is not excluded in advance.

The present invention can be applied to various changes and may have various forms, and specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosure form, and it should be understood that it includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, the phthalonitrile resin of the present invention, a polymerizable composition and a prepolymer comprising the same, and a method of manufacturing the same will be described in detail.

Phthalonitrile resin according to an embodiment of the present invention,

A first structural unit derived from the compound of Formula 1 below; And

A second structural unit derived from the compound of Formula 2 is included:

[Formula 1]

In Chemical Formula 1,

Ar ₁ and Ar ₂ are each independently an aromatic divalent radical,

X is an alkylene group or an alkylidene group,

Y ₁ and Y ₂ are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom,

R ₁₁ to R ₂₀ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a cyano group (CN), wherein at least two of R ₁₁ to R ₁₅ , and at least two of R ₁₆ to R ₂₀ are cyano groups ego,

[Formula 2]

In Chemical Formula 2,

R ₂₁ is each independently selected from the group consisting of halogen group, alkyl group, cycloalkyl group, alkoxy group, aryl group, arylalkyl group, alkylaryl group, alkylcycloalkyl group, (cycloalkyl)alkyl group, alkoxyalkyl group, and haloalkyl group,

m is an integer from 0 to 4.

As described above, the phthalonitrile resin according to an embodiment of the present invention is a monomolecular compound having a monomer-like structure having a smaller number of reactive functional groups in a monomer compound of Formula 1 having four polymerizable functional groups during production By using a mixture, it is possible to reduce the cure density by forming a non-continuous section of the net structure in the cure structure, and as a result, significantly improve the impact strength properties of the phthalonitrile resin.

Meanwhile, in the present specification, the “structural unit” derived from a given compound may mean a skeleton of a polymer formed by polymerization or curing of the compound. For example, the polymerization unit derived from the compound of Formula 1 may have a structure in which the cyano group of the compound of Formula 1 is reacted with a functional group present in a curing agent such as an amino group or a hydroxyl group.

In addition, in this specification, a halogen group means fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

Further, in the present specification, the alkyl group may be straight-chain or branched-chain, and may be substituted by one or more substituents as necessary. In addition, the number of carbon atoms of the alkyl group is not particularly limited, but may be 1 to 40, or 1 to 20, or 1 to 12, or 1 to 8, or 1 to 4. Specific examples of the alkyl group are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In addition, in the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

In addition, in the present specification, alkoxy may be represented by an -ORa group, wherein Ra is as previously defined as an alkyl group. Specific examples include methoxy, ethoxy, phenyloxy or cyclohexyloxy, but are not limited thereto.

In addition, in the present specification, the aryl group may mean a benzene ring, a compound containing a benzene ring, or a monovalent residue derived from any one of the derivatives. In the above, a compound containing a benzene ring may mean a compound having a structure in which two or more benzene rings are condensed while sharing one or two carbon atoms, or a structure directly connected or linked by an appropriate linker. Biphenyl, naphthalene, or the like can be exemplified as the above compound. The aryl group may include 6 to 30, or 6 to 20, or 6 to 12 carbon atoms. Specific examples of the aryl group include, but are not limited to, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylene group, fluorenyl group, and the like.

In the present specification, an alkylene group or an alkylidene group means an alkylene group or an alkylidene group having 1 to 20 carbon atoms, or 1 to 12 carbon atoms, or 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. Can be. The alkylene group or alkylidene group may be linear, branched or cyclic, and may be optionally substituted with one or more substituents.

In the present specification, the description of the aryl group described above may be applied to arylene except that it is an aromatic divalent radical.

In addition, in the present specification, unless otherwise specified, the alkyl group, cycloalkyl group, alkoxy group, aryl group, arylalkyl group, alkylaryl group, alkylcycloalkyl group, (cycloalkyl)alkyl group, alkoxyalkyl group, alkylene group or alkylidene The group is at least one such as an epoxy group such as halogen group, glycidyl group, epoxy alkyl group, glycidoxy alkyl group or alicyclic epoxy group, acryloyl group, methacryloyl group, isocyanate group, thiol group, alkyl group, alkoxy group or aryl group. It may be substituted with a substituent.

In addition, in this specification, an n-valent radical (where n is any number) may mean an n-valent residue derived from a given compound, unless otherwise specified. For example, Ar ₁ in Formula 1 may be a divalent radical derived from an aromatic compound, and in this case, Ar ₁ or Ar ₂ is a radical formed by separation of two hydrogen atoms from the aromatic compound, and X in Formula 1 It may have a structure that is connected to each of Y ₁ .

Specifically, in the phthalonitrile-based resin according to the embodiment, the first structural unit includes a structure derived from a compound in which Ar ₁ and Ar ₂ in Chemical Formula 1 are each independently a phenylene group, wherein the phenyl The Ren group may be substituted with one or more substituents as defined above, or unsubstituted.

In addition, in the first structural unit, X in Chemical Formula 1 may be an alkylene group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, and more specifically, a methylene group. Can be.

In addition, in the first structural unit, Y ₁ and Y ₂ in Chemical Formula 1 may be each independently an oxygen atom or a sulfur atom, and more specifically an oxygen atom.

In addition, in the first structural unit, R ₁₁ to R ₂₀ in Formula 1 are each independently a hydrogen atom; An alkyl group or an alkoxy group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms; An aryl group having 6 to 30 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms; Or a cyano group, at least two of R ₁₁ to R ₁₅ , and at least two of R ₁₆ to R ₂₀ may be a cyano group. More specifically, at least two of R ₁₁ to R ₁₅ and at least two of R ₁₆ to R ₂₀ are cyano groups, and the remaining functional groups may be hydrogen.

More specifically, considering the superiority of the effect of improving the impact strength and reducing the curing density according to the optimization of the first structural unit, the first structural unit may be derived from the compound of Formula 1a:

[Formula 1a]

In Formula 1a, X is an alkylene group having 1 to 4 carbon atoms such as methylene and ethylene, Y ₁ and Y ₂ are each independently an oxygen atom, and R ₃₁ to R ₃₈ are each independently hydrogen; Alkyl groups having 1 to 4 carbon atoms such as methyl and ethyl; Alkoxy groups having 1 to 4 carbon atoms such as methoxy groups and ethoxy groups; Or it may be a phenyl group having 6 carbon atoms, and more specifically, R ₃₁ to R ₃₈ may all be hydrogen.

As an example, the first structural unit may be derived from a compound of Formula 1a-1:

[Formula 1a-1]

Meanwhile, the second structural unit may specifically include a structure derived from a compound selected from the group consisting of compounds of the following Chemical Formulas 2a to 2c, and unlike the structure of Chemical Formula 1a-1 in which functional groups at both terminals are both connected. When the molecular length is short and the substituent position is in meta- or para-, and the structural unit derived from the compound of the following formula 2a or 2b is difficult to form a more robust structure than before, the effect of reducing cure density and improving impact strength will be more remarkable. Can be.

The first structural unit derived from the compound of Formula 1 and the second structural unit derived from the compound of Formula 2 may be included in an equivalent ratio of 1:2 to 2:1 in the phthalonitrile resin according to the embodiment. When included within the above content ratio range, the cure density is reduced, and accordingly, excellent impact strength can be exhibited. In addition, considering the remarkable effect of controlling the content range of the first and second structural units, the first structural unit and the second structural unit may be more specifically included in an equivalent ratio of 1:1 to 2:1. .

Meanwhile, in the phthalonitrile resin according to the embodiment, the first and second structural units are polymerization units formed by reaction of the compound of Formula 1 or 2 with a curing agent. Therefore, the phthalonitrile resin may further include a structural unit derived from a curing agent as a polymerization unit.

At this time, the curing agent is an aromatic amine compound, a phenol compound, an inorganic acid, an organic acid, a metal or a metal salt, such as reacting the compound of formula 1 and 2, and the like if it can form a phthalonitrile resin, can be used without particular limitation, the present invention According to one embodiment of the compound, the compound of Formula 3 may be used as the curing agent:

[Formula 3]

In Formula 3, M is a tetravalent radical,

Z ₁ and Z ₂ are each independently an alkylene group, an alkylidene group, or an aromatic divalent radical.

The compound of Formula 3 has a high boiling point and does not volatilize or decompose at high temperature, and as a result, voids capable of stably maintaining the curability of the polymerizable composition and adversely affecting the physical properties of the composite during high temperature processing and curing. (void) is not formed. In addition, the compound of Formula 3 is the central element M, but the process window of the polymerizable composition itself by the selection of the linker Z ₁ or Z ₂ , that is, the difference between the melting temperature and the curing temperature of the polymerizable composition or a prepolymer formed therefrom Since it can be easily adjusted, it can act as a curing agent for various properties according to the use.

Specifically, in the compound of Formula 3, M may be a substituted or unsubstituted, tetravalent radical derived from an aliphatic, alicyclic or aromatic compound, and more specifically, a tetravalent derived from a compound represented by the following Formulas 4a to 4f It can be a radical:

[Formula 4a]

In Formula 4a, R _a1 to R _a6 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.

[Formula 4b]

In Formula 4b, R _b1 to R _b8 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.

[Formula 4c]

In Formula 4c, R _c1 to R _c10 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group, and W ₁ is a single bond, an alkylene group, a haloalkylene group, an alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group (-C(=O)-), -A ₁ -OC(=O)- A ₂ -,-A ₁ -C(=O)-O- A ₂ -, -S(=O)- or -S (=O) ₂ -, wherein A ₁ and A ₂ may be each independently a single bond or an alkylene group.

[Formula 4d]

In Chemical Formula 4d, R _d1 to R _d4 may be each independently hydrogen, an alkyl group, or an alkoxy group, or two adjacent groups may be connected to each other to form an alicyclic ring structure, and W ₂ includes one or more oxygen atoms, or It does not contain an alkylene group or an alkenylene group.

[Formula 4e]

In the above formula 4e, R _e1 to R _e4 are each independently hydrogen, an alkyl group or an alkoxy group, and W ₃ is an alkylene group.

[Formula 4f]

In Formula 4f, R _f1 to R _f10 are each independently hydrogen, an alkyl group, or an alkoxy group.

In addition, specifically, in the compound of Formula 3, Z ₁ and Z ₂ may each independently be a divalent radical derived from a compound selected from the group consisting of compounds of Formulas 5a to 5c:

[Formula 5a]

In Formula 5a, R _g1 to R _g6 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, or a carboxyl group.

[Formula 5b]

In Formula 5b, R _h1 to R _h10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, or an aryl group, and W ₄ is a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, and a carbo Nyl group, -NR-, -S(=O)- or -S(=O) ₂ -, wherein R is hydrogen, an alkyl group, an alkoxy group or an aryl group.

[Formula 5c]

In Formula 5c, R _i1 to R _i10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, or an aryl group.

More specifically, each of Z ₁ and Z ₂ may be independently a divalent radical derived from the compound of Formula 5a, wherein the substitution position of the amino group based on the region connected to N in Z ₁ and Z ₂ of Formula 3 May be an ortho, meta or para position, respectively.

In addition, the compound of Formula 3 may have a decomposition temperature of 300°C or higher, 400°C or higher, or 500°C or higher, and 1,000°C or lower. In the present specification, the decomposition temperature means a temperature at which the decomposition rate of the compound of Formula 3 is maintained in a range of 10% or less, 5% or less, or 1% or less.

As a specific example, the compound of Formula 3 may include a compound of Formulas 3a to 3h below, and any one or a mixture of two or more of them may be used.

(3a)

(3a)

(3b)

(3b)

(3c)

(3c)

(3d)

(3d)

(3e)

(3e)

(3f)

(3f)

(3g)

(3 g)

(3h)

(3h)

Meanwhile, the content of the structural unit derived from the curing agent in the phthalonitrile resin is not particularly limited. However, when the ratio of the curing agent in the polymerizable composition is high, the process window tends to be narrowed, and when the ratio of the curing agent is low, the curability tends to be insufficient. Can be appropriately determined. According to an embodiment of the present invention, considering the effect of reducing the cure density of the final produced phthalonitrile resin and thus improving the impact strength properties, the structural unit derived from the curing agent is the total sum of the first structural unit and the second structural unit. 0.05 to 5 moles, or 0.1 to 2 moles, based on moles.

The phthalonitrile resin according to one embodiment as described above exhibits reduced cure density by including the first structural unit derived from the compound of Formula 1 and the second structural unit derived from the compound of Formula 2, and the first and second structures Through control of the content ratio of the unit, it is possible to optimize the curing density so as to exhibit better impact strength characteristics.

On the other hand, the phthalonitrile resin according to the above embodiment is a compound of Formula 1 to provide the first structural unit, a compound of Formula 2 to provide a second structural unit, and a compound of Formula 1 and a compound of Formula 2 It can be prepared by curing a polymerizable composition comprising a curing agent for curing after the polymerization reaction, or a prepolymer that is a reactant thereof. Accordingly, according to another embodiment of the present invention, there is provided a method for preparing the phthalonitrile resin described above, a polymerizable composition and a prepolymer useful for the preparation of the phthalonitrile resin.

In the polymerizable composition, the compounds of Chemical Formulas 1 and 2 may exhibit an appropriate processing temperature and a process window in the production process of a phthalonitrile resin due to its structural characteristics, and exhibit excellent reactivity to a curing agent. Can be.

Specifically, the processing temperature of the polymerizable composition containing the compounds of Formula 1 and 2 may be 50°C to 200°C, or 100°C to 200°C. As used herein, "processing temperature" means a temperature at which the compounds of Formulas 1 and 2, a polymerizable composition or a prepolymer containing them, etc. are present in a processable state, and specific examples include softening point, melting temperature (Tm), or glass. It may be a transition temperature (Tg).

When the polymerizable composition in the present invention satisfies the above-described processing temperature range, the difference between the process window (ie, the processing temperature (Tp), the compound of Formula 1, and the curing reaction initiation temperature (To) of the curing agent (To − The absolute value of Tp) may be 50°C or higher, 70°C or higher, or 100°C or higher. As used herein, "curing reaction initiation temperature" means a temperature at which polymerization or curing of a polymerizable composition or a prepolymer described later starts. For example, the curing reaction initiation temperature (To) may be higher than the processing temperature, and in this case, appropriate processability may be secured. In addition, the absolute value of the difference (To-Tp) between the processing temperature (Tp) and the initiation temperature (To) of the curing reaction may be 600°C or less, 500°C or less, 400°C or less, 300°C or less, or 200°C or less. When satisfying the above temperature conditions, it exhibits proper fluidity and processability, a wide process window is secured, and it is possible to manufacture a phthalonitrile resin having excellent impact strength characteristics.

In the polymerizable composition, the compound of Formula 1 is as described above, and may be prepared using a known organic reaction. For example, the compound of Formula 1 may be prepared through a nitro substitution reaction, and specifically, may be prepared by reacting a compound containing a hydroxy group and a compound containing a nitrile group in the presence of a basic catalyst or the like.

In addition, the type and content of the compound of Formula 2 and the curing agent are also as described above, and can be prepared using a known chemical reaction or commercially available.

In addition, the polymerizable composition may further include one or more additives depending on the purpose to improve physical properties.

The additive may specifically be a filler, and the filler is not particularly limited, and all suitable fillers may be used depending on the intended use. Specifically, the filler may include metal materials, ceramic materials, glass, metal oxides, metal nitrides, or carbon-based materials, and any one or a mixture of two or more of them may be used. In addition, as the carbon-based material, graphite, graphene or carbon nanotubes, derivatives such as oxides, or isomers may be used.

The polymerizable composition may further include various monomers or other additives known to be applicable to the production of so-called engineering plastics, such as polyimide, polyamide or polystyrene, depending on the purpose.

According to another embodiment of the present invention, a prepolymer formed by the reaction of the polymerizable composition described above is provided.

The prepolymer is a state in which the reaction of the compound of Formulas 1 and 2 and a curing agent in the polymerizable composition occurs to a certain extent (for example, a so-called A or B stage polymerization occurs), but in a fully polymerized state, It does not lead to an appropriate fluidity, and for example, refers to a state in which the composite can be processed as described below. As an example, the prepolymer is a state in which polymerization of the polymerizable composition has progressed to some extent, and the melt viscosity measured at any one of the ranges of about 150°C to 250°C for the composition is 100 cP to 10,000 cP, 100 cP to It may mean a state in the range of 5,000 cP or 100 cP to 3,000 cP.

The prepolymer can also exhibit excellent curing properties, low melting temperature and a wide process window, along with low cure density and good impact strength properties. For example, the processing temperature of the prepolymer may be in the range of 150°C to 350°C. In this case, the absolute value of the process window of the prepolymer, that is, the difference (Tc-Tp) between the processing temperature (Tp) and the curing temperature (Tc) of the prepolymer is 30°C or higher, 50°C or higher, or 100°C or higher, and 400°C Or less or 300°C. In one example, the curing temperature (Tc) may be higher than the processing temperature (Tp), in this case may exhibit a better processability.

The prepolymer may further contain any known additive in addition to the above components. Examples of such additives may include, for example, the above-described filler, but are not limited thereto.

According to another embodiment of the present invention, a composite comprising the aforementioned phthalonitrile resin, more specifically, a reinforced polymer composite is provided.

The composite may include a phthalonitrile resin and a filler, and may exhibit low cure density and excellent impact strength through the compounds of Formulas 1 and 2, and the like. Accordingly, it can be applied to various uses including durable goods such as automobiles, airplanes, or ships.

The composite may include the polymerizable composition and filler described above, or may be prepared by curing a precursor comprising the prepolymer and filler. The precursor is a polymerizable composition comprising a compound of Formulas 1 and 2 and a curing agent, or the prepolymer formed by temporarily curing the polymerizable composition is melted by heating or the like, and is prepared by mixing with the filler if necessary. Can be. For example, it is possible to prepare the above-mentioned composite by curing the precursor prepared as described above into a desired shape and then curing it. At this time, the filler is as described above.

The polymerizable composition or prepolymer has an appropriate processing temperature and a wide process temperature, and is excellent in curing property, so that molding and curing can be efficiently performed in the process. In addition, a method of forming a prepolymer or the like in the above process, a method of mixing such a prepolymer with a filler, processing and curing to prepare a composite, etc. may be performed according to a known method.

Hereinafter, preferred embodiments are provided to help understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the contents of the present invention are not limited thereby.

Manufacturing example 1. Synthesis of Compound (1a-1)

The following compound of Formula 1a-1 was synthesized in the following manner.

(1a-1)

(1a-1)

First, 28 g of 4,4'-bis (hydroxyphenylmethane) and 150 mL of dimethyl formamide (DMF) were added to 500 mL of 3 neck round-bottom flast (RBF), and dissolved by stirring at room temperature. To this, 48.5 g of 4-nitro phthalonitrile was added, and 50 g of DMF was added, followed by stirring to dissolve. Subsequently, 58.1 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85°C while stirring. After reacting for 5 hours, it is cooled to room temperature. The cooled reaction solution was poured into 0.2N aqueous hydrochloric acid solution to neutralize and precipitate. After filtering, it was washed with water. Thereafter, the filtered reaction was obtained by drying in a vacuum oven at 100°C for one day.

The results of NMR analysis of the compound of Formula 1a-1 are shown in FIG. 1.

Manufacturing example 2. Synthesis of Compound (3a)

The following compound of Formula 3a was synthesized in the following manner.

(3a)

(3a)

4,4'-oxydiphthalic anhydride and 4,4'-oxydianiline with a solid content of 15 wt% in NMP solvent were added and dissolved in a 1:4 equivalent amount. After dissolution, r-valerolactone, pyridine, and toluene were added to react at 185°C for 3 hours, and then cooled to room temperature. After cooling, the reaction solution was poured into methanol, precipitated, and then filtered to obtain a solid compound 3a.

2 shows the results of NMR analysis of the compound of Formula 3a.

Example One

About 0.2 mol of the compound of Formula 3a prepared in Preparation Example 2 with respect to 1 mol of the composition of the compound of Formula 1a-1 prepared in Preparation Example 1 and the compound of Formula 2a in 1 to 1 equivalent amount After adding and mixing to react, a phthalonitrile resin was prepared.

(2a)

(2a)

Example 2

About 0.2 mol of the compound of Formula 3a prepared in Preparation Example 2 is added to 1 mol of the composition of the compound of Formula 1a-1 prepared in Preparation Example 1 and the compound of Formula 2b in 1 to 1 equivalent amount. After mixing and reacting to prepare a phthalonitrile resin.

(2b)

(2b)

Example 3

About 0.2 mol of the compound of Formula 3a prepared in Preparation Example 2 is added to and mixed with 1 mol of the composition in which the compound of Formula 1a-1 prepared in Preparation Example 1 and the compound of Formula 2b are mixed in a 2 to 1 equivalent amount. After reacting, a phthalonitrile resin was prepared.

Comparative example  One

About 0.2 mol of the compound of Formula 3a prepared in Preparation Example 2 was added and mixed with respect to 1 mol of the compound of Formula 1a-1 prepared in Preparation Example 1, and then reacted to prepare a phthalonitrile resin.

Test example 1: Impact strength evaluation

Impact strengths of the phthalonitrile resins prepared in Examples 1 to 3 and Comparative Example 1 were evaluated.

Specifically, the specimen for impact strength measurement was prepared as a specimen without a notch of ASTM D256 standard, and was conducted at room temperature based on the above test method at the Korea Polymer Testing Laboratory.

IZOD impact strength (J/m) Psalm 1 Psalm 2 Psalm 3 Average Example 1 244.6 299.0 299.0 280.8 Example 2 317.4 314.3 309.3 313.6 Example 3 199.0 183.6 199.0 193.9 Comparative Example 1 133.4 204.6 157.0 165.0

As a result of the experiment, the phthalonitrile resins of Examples 1 and 2 further comprising a compound of Formula 2a or 2b in the composition of Comparative Example 1 exhibited improved impact strength characteristics of about 2 times or more compared to Comparative Example 1.

Claims (17)

A first structural unit derived from the compound of Formula 1 below; And
A second structural unit derived from the compound of Formula 2
Phthalonitrile resin comprising:
[Formula 1]

In Chemical Formula 1,
Ar ₁ and Ar ₂ are each independently an aromatic divalent radical,
X is an alkylene group or an alkylidene group,
Y ₁ and Y ₂ are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom,
R ₁₁ to R ₂₀ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a cyano group, at least two of R ₁₁ to R ₁₅ , and at least two of R ₁₆ to R ₂₀ are cyano groups,
[Formula 2]

In Chemical Formula 2,
R ₂₁ is each independently selected from the group consisting of halogen group, alkyl group, cycloalkyl group, alkoxy group, aryl group, arylalkyl group, alkylaryl group, alkylcycloalkyl group, (cycloalkyl)alkyl group, alkoxyalkyl group, and haloalkyl group,
m is an integer from 0 to 4.
According to claim 1,
A phthalonitrile resin in which Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted phenylene group.
According to claim 1,
The X is an alkylene group having 1 to 20 carbon atoms, a phthalonitrile resin.
According to claim 1,
The Y ₁ and Y ₂ are each independently an oxygen atom or a sulfur atom, a phthalonitrile resin.
According to claim 1,
The first structural unit is a phthalonitrile resin, which is derived from the compound of Formula 1a:
[Formula 1a]

In Formula 1a,
X is an alkylene group having 1 to 4 carbon atoms,
Y ₁ and Y ₂ are each independently an oxygen atom or a sulfur atom,
R ₃₁ to R ₃₈ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.
According to claim 1,
The first structural unit is a phthalonitrile resin, which is derived from the compound of Formula 1a-1:
[Formula 1a-1]

According to claim 1,
The second structural unit is a phthalonitrile resin, which is a structural unit derived from a compound of Formula 2a or 2b.

According to claim 1,
The first structural unit and the second structural unit are included in an equivalent ratio of 1:1 to 2:1, phthalonitrile resin.
According to claim 1,
A phthalonitrile resin further comprising a structural unit derived from the compound of Formula 3:
[Formula 3]

In Chemical Formula 3, M is a tetravalent radical,
Z ₁ and Z ₂ are each independently an alkylene group, an alkylidene group, or an aromatic divalent radical.
A compound of Formula 1,
A compound of Formula 2, and
Hardener
Polymerizable composition comprising:
[Formula 1]

In Chemical Formula 1,
Ar ₁ and Ar ₂ are each independently an aromatic divalent radical,
X is an alkylene group or an alkylidene group,
Y ₁ and Y ₂ are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom,
R ₁₁ to R ₂₀ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a cyano group, at least two of R ₁₁ to R ₁₅ , and at least two of R ₁₆ to R ₂₀ are cyano groups,
[Formula 2]

In Chemical Formula 2,
R ₂₁ is each independently selected from the group consisting of halogen group, alkyl group, cycloalkyl group, alkoxy group, aryl group, arylalkyl group, alkylaryl group, alkylcycloalkyl group, (cycloalkyl)alkyl group, alkoxyalkyl group, and haloalkyl group,
m is an integer from 0 to 4.
The method of claim 10,
The compound of Formula 1 and the compound of Formula 2 are included in an equivalent ratio of 1:1 to 2:1, the polymerizable composition.
The method of claim 10,
The curing agent comprises a compound of Formula 3, a polymerizable composition:
[Formula 3]

In Chemical Formula 3, M is a tetravalent radical,
Z ₁ and Z ₂ are each independently an alkylene group, an alkylidene group, or an aromatic divalent radical.
The method of claim 12,
M is a tetravalent radical derived from the compounds of the following formulas 4a to 4f,
The Z ₁ and Z ₂ are each independently a divalent radical derived from a compound selected from the group consisting of compounds of Formulas 5a to 5c, wherein the polymerizable composition:
[Formula 4a]

In Formula 4a, R _a1 to R _a6 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.
[Formula 4b]

In Formula 4b, R _b1 to R _b8 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.
[Formula 4c]

In Formula 4c, R _c1 to R _c10 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group, and W ₁ is a single bond, an alkylene group, a haloalkylene group, an alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group (-C(=O)-), -A ₁ -OC(=O)- A ₂ -,-A ₁ -C(=O)-O- A ₂ -, -S(=O)- or -S (=O) ₂ -, wherein A ₁ and A ₂ may be each independently a single bond or an alkylene group.
[Formula 4d]

In Formula 4d, R _d1 to R _d4 are each independently hydrogen, an alkyl group, or an alkoxy group, or two adjacent groups may be connected to each other to form an alicyclic ring structure, and W ₂ includes one or more oxygen atoms, or It does not contain an alkylene group or an alkenylene group.
[Formula 4e]

In the above formula 4e, R _e1 to R _e4 are each independently hydrogen, an alkyl group or an alkoxy group, and W ₃ is an alkylene group.
[Formula 4f]

In Formula 4f, R _f1 to R _f10 are each independently hydrogen, an alkyl group, or an alkoxy group.
[Formula 5a]

In Formula 5a, R _g1 to R _g6 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, or a carboxyl group.
[Formula 5b]

In Formula 5b, R _h1 to R _h10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, or an aryl group, and W ₄ is a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, and a carbo Nyl group, -NR-, -S(=O)- or -S(=O) ₂ -, wherein R is hydrogen, an alkyl group, an alkoxy group or an aryl group.
[Formula 5c]

In Formula 5c, R _i1 to R _i10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, or an aryl group.
The method of claim 10,
The curing agent comprises any one or two or more selected from the group consisting of compounds of the following formula 3a to 3h, polymerizable composition:

(3a)

(3b)

(3c)

(3d)

(3e)

(3f)

(3 g)

(3h)
The method of claim 10,
The curing agent is contained in a ratio of 0.05 to 5 moles based on the total moles of the compound of Formula 1 and the compound of Formula 2, a polymerizable composition.
A prepolymer that is a reactant of the polymerizable composition of claim 10.
A method of producing a phthalonitrile resin comprising the step of curing the polymerizable composition of claim 10 or the prepolymer of claim 16.

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