KR102056593B1 - Phthalonitrile compound - Google Patents

Abstract

The present application relates to a phthalonitrile compound and a phthalonitrile resin obtained therefrom, a polymerizable composition, a prepolymer, a composite and a method for producing the composite. The phthalonitrile compound and the like of the present application are excellent in curability, and have an appropriate processing temperature and a wide process window, and thus can form a composite having excellent physical properties.

Description

Phthalononitrile compound

The present application relates to a phthalonitrile compound, a phthalonitrile resin, a polymerizable composition, a prepolymer, a composite, a precursor of the composite and a method of producing the composite.

The phthalonitrile resin containing a phthalonitrile compound is a thermosetting resin excellent in heat resistance and flame retardancy, and its use is various. In one example, the phthalonitrile resin may be impregnated with a filler such as galss fiber or carbon fiber to form a composite, which is used as a durable material for automobiles, airplanes or ships. Can be.

On the other hand, phthalonitrile resin can be obtained through a thermosetting process using an aromatic amine as a curing agent in a monomer having two phthalonitrile groups. However, due to the aromatic structure peculiar to the phthalonitrile monomer and the high molecular weight, it exists in the solid phase, and in most cases, it has a high softening point, thereby causing a problem of poor workability.

In addition, the manufacturing process of the composite containing phthalonitrile may include curing the mixture of the phthalonitrile and the curing agent, or a prepolymer formed by the reaction of the mixture with the filler and then curing (eg For example, refer to Patent Document 1), in order to effectively produce such a composite, the monomer phthalonitrile or the prepolymer formed therefrom should have appropriate meltability and fluidity, and have a wide process window.

Korean Patent No. 0558158

An object of the present application is to provide a phthalonitrile compound, a phthalonitrile resin, a polymerizable composition, a prepolymer, a composite, a precursor of the composite.

Another object of the present application is to provide a phthalonitrile resin, a polymerizable composition, a prepolymer, a composite, and a precursor of the composite having a low softening point and a wide process window.

Still another object of the present application is to provide a phthalonitrile resin, a polymerizable composition, a prepolymer, a composite, and a precursor of the composite having excellent processability.

The present application relates to phthalonitrile compounds. Phtharonitrile compound of the present application may be represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ to R ₁₀ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group or a cyano group, and X ₁ and X ₂ are each independently a single bonded alkylene group, alkylidene group, oxygen atom or sulfur Is an atom, and Ar is an aromatic divalent radical substituted with at least one alkyl group.

The alkyl group in the present application may be an alkyl or alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkyl group may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

In the present application, the alkoxy group may have 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms, unless otherwise specified. The alkoxy group may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

In the present application, unless otherwise specified, an aryl group may mean benzene, a compound containing benzene, or a monovalent radical derived from any one of the above. Examples of the compound containing benzene include compounds having a structure in which two or more benzene rings are condensed while sharing two carbon atoms, or connected by an appropriate linker. Such compounds include, but are not limited to, biphenyl and naphthalene. The aryl group may include, for example, 6 to 25, 6 to 20 or 6 to 12 carbon atoms. Specific examples of the aryl group include, but are not limited to, a phenyl group, benzyl group, biphenyl group or naphthalene group. In addition, the scope of the aryl group in the present application may include a functional group commonly referred to as an aryl group as well as a so-called aralkyl group.

In Formula 1, R ₁ to R ₁₀ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group or a cyano group, wherein at least two of R ₁ to R ₅ are cyano groups, and at least 2 of R ₆ to R ₁₀ The dog may be a cyano group. In one example, R ₂ , R ₃ , R ₇ and R ₈ of Formula 1 may be a cyano group, and R ₁ , R ₄ , R ₅ , R ₆ , R ₉ , and R ₁₀ are each independently hydrogen , An alkyl group, an alkoxy group, and an aryl group. In another example of the present application, R ₂ , R ₃ , R ₇ and R ₈ of Formula 1 are cyano groups, and R ₁ , R ₄ , R ₅ , R ₆ , R ₉ , and R ₁₀ are each independently hydrogen, It may be an alkyl group or an alkoxy group. In another example of the present application, each of R ₁ , R ₄ , R ₅ , R ₆ , R ₉ , and R ₁₀ may be independently hydrogen or an alkyl group.

In Formula 1, X ₁ and X ₂ may be each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom. In the example of the present application, X ₁ and X ₂ in Formula 1 may each independently be an alkylene group, an alkylidene group, an oxygen atom, and in another example, both X ₁ and X ₂ may be oxygen atoms. In this case, Ar of Formula 1 may be a radical derived from resorcinol.

In Formula 1, Ar, an aromatic divalent radical, may mean a benzene ring, a compound containing a benzene ring, or a divalent residue derived from any one of the derivatives described in the definition of the aryl group. The aromatic divalent radical may, for example, comprise 6 to 25, 6 to 20, 6 to 15, or 6 to 12 carbon atoms, optionally substituted by one or more substituents It may be.

In addition, in one example of the present application, Ar of Formula 1 may be a radical compound derived from the following formula (2).

[Formula 2]

In Formula 2, R ₁₁ to R ₁₆ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group, and at least two of R ₁₁ to R ₁₆ are covalently bonded to X ₁ and X ₂ of Formula 1 (single Combination). In one example of the present application, at least one of the substituents that do not form a covalent bond with X ₁ and X ₂ of R ₁₁ to R ₁₆ may be an alkyl group.

Based on the substituents which form a covalent bond with X ₁ of Formula 1 in R ₁₁ to R ₁₆ of Formula ₂ , the position of the substituent which forms a covalent bond with X ₂ is ortho, meta or para. (para) location. In an example of the present application, on the basis of the substituent which forms a covalent bond with X ₁ of Formula 1 in R ₁₁ to R ₁₆ of Formula 2, a substituent present at a meta position forms a covalent bond with X _2. can do. In particular, when the substitution position of X ₂ on the basis of X ₁ in Ar of Formula 1 is a meta position, synthesis is easier than the ortho or para position, and melting of the resin is performed. It can lower the temperature and widen the process window.

In an example of the present application, when the substitution position of X ₂ based on X ₁ in Ar of Formula 1 is a meta position, it is present at ortho and para positions of R ₁₁ to R ₁₆ . At least one of the substituents may be an alkyl group having 4 to 12 carbon atoms. Examples of the alkyl group having 4 to 12 carbon atoms include a butyl group, a pentyl group, a hexyl group, a heptane group, and the like, but are not limited thereto. In addition, in one example of the present application, in Ar in Formula 1, the substitution position of X ₂ based on X ₁ may be a meta position, and the alkyl group having 4 to 12 carbon atoms may be a hexyl group. In Ar in Formula 1, the softening point of the resin may be lower than that of the case where the substitution position of X ₂ based on X ₁ is a meta position, thereby improving processability of the compound or resin. In one example, when the alkyl group having 4 to 12 carbon atoms is a hexyl group, the substitution position of the hexyl group is not particularly limited, but the substitution position of X ₂ based on X ₁ in Ar of Formula 1 is meta In the case of a (meta) position, it may be in a para position.

In addition, in Chemical Formula 1 and Chemical Formula 2, the alkyl group, alkoxy group, aryl group, and aromatic divalent radical may be substituted with an arbitrary substituent. Examples of the optional substituent include halogen, glycine, such as chlorine or fluorine. Epoxy groups, such as a dill group, an epoxy alkyl group, a glycidoxy alkyl group, or an alicyclic epoxy group, an acryloyl group, a methacryloyl group, an isocyanate group, a thiol group, an alkyl group, an alkoxy group, or an aryl group. However, it is not limited thereto.

In one example, the compound of Formula 1 has an appropriate processing temperature, and excellent in reactivity with the curing agent. In one example of the present application, the processing temperature of the compound may be in the range of 30 ℃ to 250 ℃, preferably may be 210 ℃ or less, 150 ℃ or less, 100 ℃ or less or 50 ℃ or less. The term 'processing temperature' used in the present application means a temperature at which a compound represented by Chemical Formula 1, a resin including a polymerized unit derived from the compound, or a polymerizable composition including the same exist in a processable state. can do. Examples of such processing temperatures include softening point, melting temperature (Tm) or glass transition temperature (Tg). The processing temperature in the above range allows to secure a wide process window, thereby enabling the implementation of a polymerizable composition or a polymer that can form a composite of excellent physical properties.

In addition, the compound represented by the formula (1) of the present application, can be used in a variety of applications known that the so-called phthalonitrile compound can be applied. In particular, the compound represented by the formula (1) of the present application lowers the melting temperature than other phthalonitrile-based compounds, showing a wide process window and an appropriate processing temperature.

In one example, the compound represented by the general formula (1) of the present application, because the melt softening temperature can be lowered by more than 150 ℃ than the phthalonitrile compound containing a conventionally known resorcinol-derived unit, provides excellent processability can do.

The compound of Formula 1 may be synthesized according to a known organic compound synthesis method. For example, the compound of formula 1 can be synthesized by a reaction known as the nitro displacement reaction. For example, a compound containing a hydroxy group and a compound containing a nitrile group can be synthesized by reacting in the presence of a basic catalyst. However, it is not limited to the above method.

The present application also relates to a phthalonitrile resin comprising a polymerized unit derived from the compound of Formula 1. The term "polymerization unit derived from a compound" used in the present application may mean a polymer skeleton formed by polymerizing or curing the compound.

The phthalonitrile resin of the present application may include polymerized units of other phthalonitrile compounds in addition to the compound polymerized units of the general formula (1). The kind of phthalonitrile compound which can be used is not specifically limited, The well-known compound known to be useful for formation of a phthalonitrile resin and its physical property can be applied. Examples of such compounds include compounds known from US Pat. No. 5,003,039, US Pat. No. 5,003,078, US Pat. No. 5,004,801 and the like, and may also include various compounds known in the art.

In the phthalonitrile resin of the present application, the compound polymerization unit of Formula 1 may be a polymerization unit formed by the reaction of [Formula 1] and a curing agent. The type of curing agent that can be used is not particularly limited, and any curing agent may be used as long as it can react with the compound of Formula 1 to form a polymer. As an example of the hardening | curing agent which can be used, an amine compound or a hydroxy compound like an aromatic amine compound is mentioned. In the present application, a hydroxy compound may mean a compound including at least one or two hydroxy groups in a molecule. Curing agents capable of curing the phthalonitrile compound to form a resin are variously known, and most of such curing agents may be applied to the present application.

The present application also relates to a polymerizable composition comprising the compound of Formula 1. The polymerizable composition of the present application may further include a curing agent together with the compound of Formula 1. The kind of hardening | curing agent is not specifically limited, The above-mentioned hardening | curing agent can be used.

The content of the curing agent used in the polymerizable composition is not particularly limited. For example, in consideration of the desired physical properties (such as curing properties), the compound properties of the formula (1) included in the composition, etc., the content of the curing agent can be adjusted. In one example, the curing agent used in the polymerizable composition may be included in the range of about 0.02 to 1.5 moles per mole of the compound of Formula 1 included in the polymerizable composition. In general, when the ratio of the curing agent is high in the polymerizable composition, the process window tends to be narrowed, and when the ratio of the curing agent is low, the curing property tends to be insufficient. Can be selected.

The polymerizable composition of the present application has an appropriate processing temperature and a wide process window with excellent curability. In one example of the present application, the processing temperature of the polymerizable composition may be in the range of 30 ° C to 250 ° C, preferably 210 ° C or less, 150 ° C or less, or 100 ° C or less. In this case, the process window of the polymerizable composition may be 60 ° C. or more, 100 ° C. or more, 130 ° C. or more, or 150 ° C. or more. The process window can be defined as an absolute value for the temperature difference (Tc-Tp) between the curing temperature (Tc) and the processing temperature (Tp) of the polymerizable composition. The upper limit of the process window is not particularly limited, but for example, the upper limit may be 300 ° C. or lower or 200 ° C. or lower. When the process window satisfies the above temperature range, it is advantageous to secure appropriate processability in the process of manufacturing a composite described later.

In addition to the compound of Formula 1, the polymerizable composition of the present application may further include an additive such as a filler or a dispersant. Examples of the additive include, but are not limited to, a fibrous material such as glass fiber or carbon fiber, or a carbon nano material such as graphene or carbon nanotube, ceramic particles such as silicon nitride or silicon oxide, and the like.

The present application also relates to a prepolymer formed by the reaction of the polymerizable composition. As used herein, the term 'prepolymer' refers to a state in which the compound of Chemical Formula 1 and the curing agent are not completely polymerized in the polymerizable composition, and exhibit appropriate fluidity, and thus can be processed into a composite as described below. can do. In one example, the prepolymer may mean a state in which the polymerization of the polymerizable composition is advanced to some extent.

The prepolymer of the present application comprising the compound of Formula 1 also has excellent curability, suitable processing temperature and wide process window. In addition, the prepolymer may exhibit stability over time even when stored at room temperature for a long time.

For example, the processing temperature of the prepolymer may range from 30 ° C. to 250 ° C., preferably 210 ° C. or less, 150 ° C. or less, or 100 ° C. or less. . When the processing temperature is in the above range, the process window of the prepolymer may be at least 60 ℃, at least 100 ℃, at least 130 ℃, or at least 150 ℃. The upper limit of the process window is not particularly limited, but for example, the upper limit may be 300 ° C. or lower or 200 ° C. or lower. When the process window satisfies the above temperature range, appropriate processability may be ensured in the process of manufacturing a composite described later.

The prepolymer may further comprise any additive. Additives additionally included in the prepolymer include, but are not limited to, the aforementioned fillers, and other known additives may be used.

The present application also relates to a composite. The composite may include the phthalonitrile resin and filler described above. As described above, the compound of Formula 1 can obtain a suitable processing temperature and a wide process window for the composite, thereby providing a so-called reinforced polymer composite comprising various fillers. Such a composite can be used as a durable material for automobiles, airplanes or ships.

Examples of fillers used in the composites include, but are not limited to, fibrous materials, or woven fabrics, nonwovens, strings, or strings or carbon nanomaterials formed therefrom. Examples of the fibrous material include glass fiber, carbon fiber, aramid fiber, ceramic fiber, and the like. Examples of carbon nanomaterials include graphene or carbon nanotubes. The proportion of the filler included is not particularly limited and may be set in an appropriate range depending on the intended use.

The present application also relates to precursors for preparing the composites. Precursors of the present application may include, for example, the above-described polymerizable composition and the filler, or may include the above-described prepolymer and the filler.

In one example of the present application, the precursor is blended with the filler when necessary in a state in which a polymerizable composition comprising the compound of Formula 1 and a curing agent or a prepolymer formed by temporarily curing the polymerizable composition is melted by heating or the like. Can be prepared. For example, the above-described composite may be manufactured by curing the precursor prepared as described above into a desired shape and then curing the precursor. As mentioned above, the polymerizable composition or prepolymer has a suitable processing temperature and a wide process temperature, and excellent curability, thereby making it possible to perform the molding and curing process efficiently.

Resin containing a phthalonitrile-based compound of the present application has a low melting temperature exhibits an appropriate processing temperature and a wide process window, it can provide a composite of excellent physical properties.

1 is a result of NMR analysis for the compound PN1 of Preparation Example 1.
2 is a result of NMR analysis for the compound PN2 of Preparation Example 2.
3 is a result of NMR analysis for the compound PN3 of Preparation Example 3.
4 is a result of NMR analysis for the compound PN4 of Preparation Example 4.
5 is a result of NMR analysis for the compound PN5 of Preparation Example 5.

Hereinafter, the phthalonitrile resin of the present application will be described in detail through Examples and Comparative Examples. However, the protection scope of the present invention is not limited by the embodiments described below.

Analysis method

1.NMR (Nuclear Magnetic Resonance)

NMR analysis of the compounds synthesized in Preparation Examples 1 to 3 was performed according to the manufacturer's manual using Agilent's 500 MHz NMR equipment. Samples for NMR measurements were prepared by dissolving the compound in DMSO (dimethyl sulfoxide) -d6.

2. DSC  (Differential Scanning Calorimetry) Analysis

DSC analysis was carried out in a N2 flow atmosphere using a TA instrument Q20 system at a temperature increase rate of 10 ℃ / min from 35 ℃ to 450 ℃.

Preparation of the compound

Production Example  1.Compound PN 1 ) Synthesis

Compound PN 1 of Formula A was synthesized by a nitro displacement reaction. Specifically, 19.4 g of 4-hexylresorcinol of Formula B and 100 ml of DMF (dimethyl formamide) were added to a 500 ml flask (3 neck round-bottom flask) and stirred at room temperature. To the mixture, 34.6 g of 4-nitrophthalinitrile of formula (C) was added, 50 g of DMF was added, stirred, and dissolved. 41.5 g of potassium carbonate was added together with 50 g of DMF, and the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours and cooling to room temperature, the cooled reaction solution was poured into 0.2 N aqueous hydrochloric acid to neutralize and precipitate, and the precipitate was filtered and washed with water. The filtered product was dried in a vacuum oven at 100 ° C. for one day to remove water and residual solvent, to obtain compound PN 1 of formula A in a yield of 85% by weight. The NMR analysis of the compound of Formula A is shown in FIG. 1.

[Formula A]

[Formula B]

[Formula C]

Production Example  2. Compound ( PN 2 ) Synthesis

16.5 g of the compound of Formula E and 100 ml of DMF (dimethyl formamide) were added to a three neck round-bottom flask (RBF), and stirred at room temperature to dissolve. 51.9 g of nitrophthalonitrile of Chemical Formula C used in Preparation Example 1 was added thereto, and 50 g of DMF was added thereto, followed by stirring to dissolve it. Subsequently, after 62.6 g of potassium carbonate and 50 g of DMF were added together, the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours, the mixture was cooled to room temperature. The cooled reaction solution was poured into 0.2 N aqueous hydrochloric acid solution to neutralize precipitation. After filtering it was washed with water. The filtered reaction was then dried in a vacuum oven at 100 ° C. for one day. After removing water and residual solvent, compound (PN2) of the following formula (D) was obtained in a yield of 87% by weight. The NMR analysis of the compound of Formula D is shown in FIG. 2.

[Formula D]

[Formula E]

Production Example  3. Compound ( PN 3 ) Synthesis

50.4 g of the compound of formula G and 150 ml of DMF were added to a three neck RBF, and stirred at room temperature to dissolve. 51.9 g of 4 nitro phthalonitrile of the general formula (C) used in Preparation Example 1 was added, and 50 g of DMF was added, followed by stirring to dissolve. Subsequently, after 62.6 g of potassium carbonate and 50 g of DMF were added together, the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours, it is cooled to room temperature. The cooled reaction solution was poured into 0.2 N aqueous hydrochloric acid and neutralized to precipitate. After filtering it was washed with water. The filtered reaction was then dried in a vacuum oven at 100 ° C. for one day. After removing water and residual solvent, compound (PN3) of the formula (F) was obtained in a yield of 83% by weight. The NMR analysis of the compound of Formula F is shown in FIG. 3.

Formula F]

[Formula G]

Production Example  4. Compound ( PN 4 ) Synthesis

27.9 g of the compound of formula (I) and 100 ml DMF were added to a 3-neck RBF, and stirred at room temperature to dissolve. 51.9 g of 4 nitro phthalonitrile of Chemical Formula C used in Preparation Example 1 was added, and 50 g of DMF was added, followed by stirring to dissolve. Subsequently, after 62.6 g of potassium carbonate and 50 g of DMF were added together, the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours, the mixture was cooled to room temperature. The cooled reaction solution was poured into 0.2 N aqueous hydrochloric acid and neutralized to precipitate. After filtering it was washed with water. The filtered reaction was then dried in a vacuum oven at 100 ° C. for one day. After removing water and residual solvent, compound (PN4) of the following formula H was obtained in a yield of 83% by weight. The NMR analysis of the compound of Formula H is shown in FIG. 4.

[Formula H]

[Formula I]

Production Example  5. Compound ( PN 5 ) Synthesis

16.5 g of the compound of Formula (K) and 100 ml of DMF were added to a 2-neck RBF, and stirred at room temperature to dissolve. 51.9 g of 4 nitro phthalonitrile of the formula (C) used in Preparation Example 2 was added, and 50 g of DMF was added, followed by stirring to dissolve. Subsequently, after 62.6 g of potassium carbonate and 50 g of DMF were added together, the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours, the mixture was cooled to room temperature. The cooled reaction solution was poured into 0.2 N aqueous hydrochloric acid and neutralized to precipitate. After filtering it was washed with water. The filtered reaction was then dried in a vacuum oven at 100 ° C. for one day. After removal of water and residual solvent, the compound of formula J (PN 5) was obtained in a yield of 80% by weight. The NMR analysis of the compound of Chemical Formula J is shown in FIG. 5.

[Formula J]

[Formula K]

Production Example  6. Compound (CA1)

The compound of the following formula (m-APB) was purchased from TCI Corporation and used without further purification.

[Formula]

Experimental Example 1: compound  Softening point comparison

Melting points (Tm) or softening points (Tg) of the compounds synthesized from Preparation Examples 1 to 6 were measured by DSC and summarized in Table 1 below.

PN1 PN2 PN3 PN4 PN5 CA1 Tg or Tm
(Unit: ℃) 15 183 231 235 259 108

PN5 having a phthalonitrile group in the para position has a very high melting point of 259 ° C., whereas PN2 having a phthalonitrile group in the meta position has a melting point of 183 ° C., which is 70 ° C. or lower than PN5. This is because it is difficult to arrange the molecules regularly due to the bending of the molecular structure to the meta position, thereby lowering the softening point. Moreover, in the case of PN1 which introduce | transduced the flexible hexyl group into PN2, the softening point is measured at 15 degreeC and has a softening point which is 160 degreeC or more lower than PN2. This is because, in the case of PN1, in addition to the structure of PN2, since the flexible and large hexyl group was introduced, the intermolecular regular arrangement becomes more difficult, and thus, the intermolecular distance is determined to be converted to the liquid phase at a lower temperature.

Experimental Example  2: process of composition window  compare

Process windows were measured for the compositions prepared according to Examples 1 to 3 and Comparative Examples 1 to 4 below, and described in Table 2 below.

Example  1: curing after mixing PN1 and CA1

PN1 and CA1 were mixed so that about 0.06 mole of CA1 was present per mole of PN1. Subsequently, the processing temperature of the mixture and the initiation temperature of the curing reaction were confirmed by DSC analysis, and the process window of the composition was calculated therefrom.

Example  2: curing after mixing PN1, PN3 and CA1

To 1 mole of the composition in which PN1 and PN3 were mixed in a one-to-one equivalent, about 0.06 moles of CA1 were mixed. Subsequently, the processing temperature of the mixture and the initiation temperature of the curing reaction were confirmed by DSC analysis, and the process window of the composition was calculated therefrom.

Example  3: curing after mixing PN1, PN4 and CA1

To about 1 mole of the composition in which PN1 and PN4 were mixed in a one-to-one equivalent, about 0.06 moles of CA1 were mixed. Subsequently, the processing temperature of the mixture and the initiation temperature of the curing reaction were confirmed by DSC analysis, and the process window of the composition was calculated therefrom.

Comparative example  1: curing after mixing PN2 and CA1

PN2 and CA1 were mixed so that about 0.06 mole of CA1 was present per 1 mole of PN2. Subsequently, the processing temperature of the mixture and the initiation temperature of the curing reaction were confirmed by DSC analysis, and the process window of the composition was calculated therefrom.

Comparative example  2: curing after mixing PN3 and CA1

PN3 and CA1 were mixed so that about 0.06 mole of CA1 was present per 1 mole of PN3. Subsequently, the processing temperature of the mixture and the initiation temperature of the curing reaction were confirmed by DSC analysis, and the process window of the composition was calculated therefrom.

Comparative example  3: curing after mixing PN4 and CA1

PN4 and CA1 were mixed so that about 0.06 mole of CA1 was present per 1 mole of PN4. Subsequently, the processing temperature of the mixture and the initiation temperature of the curing reaction were confirmed by DSC analysis, and the process window of the composition was calculated therefrom.

Comparative example  4: curing after mixing PN5 and CA1

PN5 and CA1 were mixed so that about 0.06 mole of CA1 was present per 1 mole of PN5. Subsequently, the processing temperature of the mixture and the initiation temperature of the curing reaction were confirmed by DSC analysis, and the process window of the composition was calculated therefrom.

TABLE 2

From Table 2, in the case of Comparative Example 4 in which PN5 in which the phthalonitrile group is connected to the para position is used, the processing temperature is increased due to the high regularity of the core structure, so that the process window is very narrow to about 20 ° C. It can be seen that. However, in the case of Comparative Example 1 using PN2 in which the phthalonitrile group is connected to the meta position, it can be seen that the processing temperature is lowered compared to Comparative Example 4 to have a relatively wide range of process windows of about 101 ° C. Furthermore, in the case of Example 1 consisting of only PN1 having a hexyl group introduced into PN2, it can be seen that the processing temperature is very low due to the low softening point of PN1, thereby increasing the process window to about 169 ° C. This is about 70 ° C. wider process window value when compared to Comparative Example 1.

In addition, in the case of Comparative Examples 2 and 3 using PN3 and PN4, which are generally known prunonitrile monomers, respectively, the process window was measured at about 49 ° C and about 30 ° C, respectively, indicating that the processability was not good. . Nevertheless, Example 2 and Example 3, in which PN1 is mixed with PN3 and PN4, respectively, can confirm that the process windows increase to 86 ° C and 68 ° C. This indicates that when asymmetrical PN1 is mixed, the process window can improve the processability of narrow materials. That is, when including the material corresponding to Example 1 of the present invention, it can be seen that the processability of the entire composition can be improved.

Claims (20)

A compound of formula 1 wherein the softening point is 100 ° C. or less:
[Formula 1]

In Chemical Formula 1,
Ar is an aromatic divalent radical derived from an aromatic compound represented by Formula 2 and substituted with at least one alkyl group,
X ₁ and X ₂ are each independently a single bonded alkylene group, alkylidene group, oxygen atom or sulfur atom,
R ₁ to R ₁₀ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group or a cyano group, at least two of R ₁ to R ₅ are cyano groups, and at least two of R ₆ to R ₁₀ are cyano groups ;
[Formula 2]

In Chemical Formula 2,
R ₁₁ to R ₁₆ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group,
At least two of R ₁₁ to R ₁₆ are covalently bonded to X ₁ and X ₂ of Formula 1, and at least one of substituents that do not form a covalent bond with X ₁ and X ₂ of R ₁₁ to R ₁₆ is An alkyl group, and a substituent present at a meta position on the basis of a substituent which forms a covalent bond with X ₁ of Formula 1 in R ₁₁ to R ₁₆ forms a covalent bond with X ₂ ,
Based on the substituents which form a covalent bond with X ₁ of Formula 1 in R ₁₁ to R ₁₆ , at least one of substituents present in ortho and para positions is an alkyl group having 4 to 12 carbon atoms. . delete delete The compound of claim 1, wherein X ₁ and X ₂ are oxygen atoms. delete delete The compound according to claim 1, wherein the compound which is an alkyl group having 4 to 12 carbon atoms is a hexyl group. A phthalonitrile resin comprising a polymerized unit derived from a compound according to any one of claims 1, 4 and 7. delete The phthalonitrile resin of claim 8, wherein the compound of Formula 1 has a softening point of 50 ° C. or less. A polymerizable composition comprising the compound of claim 1 and a curing agent. The polymerizable composition according to claim 11, wherein the processing temperature is 100 ° C. or less and the process window is 150 ° C. or more. The polymerizable composition of claim 11, further comprising a fibrous material or a carbon nano material. A prepolymer which is a reactant of the polymerizable composition of claim 11. The prepolymer of claim 14, wherein the processing temperature is 100 ° C. or less and the process window is 150 ° C. or more. A composite comprising the phthalonitrile resin of claim 8. The composite of claim 16 further comprising a filler. The composite of claim 17, wherein the filler is at least one selected from fibrous materials, carbon nanomaterials, and ceramic particles. A precursor of the complex of claim 18 comprising the polymerizable composition of claim 11 or the prepolymer of claim 14. 20. A method of making a composite comprising curing the precursor of claim 19.

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