WO2016080762A1 - Phthalonitrile resin - Google Patents

Abstract

The present application relates to a phthalonitrile resin, a polymerizable composition, a prepolymer, a composite, a preparation method therefor, and a use thereof. The present application can provide: phthalonitrile having excellent curability, exhibiting a suitable process temperature and a wide process window, and capable of forming a composite having excellent physical properties; a polymerizable composition using the same; and a prepolymer.

Description

Phthalonitrile resin

The present application relates to phthalonitrile resins, polymerizable compositions, prepolymers, composites, methods of making and uses thereof.

The phthalonitrile resin can be used for various applications. For example, a composite formed by impregnating a phthalonitrile resin into a filler such as glass fiber or carbon fiber may be used as a material for automobiles, airplanes, ships, and the like. The manufacturing process of the composite may include, for example, curing after mixing a filler and a prepolymer formed by a mixture of a phthalonitrile and a curing agent or a mixture thereof. Such contents are disclosed in Korean Patent No. 0558158 and the like.

In order to be effective in the production process of the composite, it is required that the monomer phthalonitrile or the polymerizable composition or prepolymer formed therefrom have appropriate meltability and fluidity, and a so-called process window is wide.

In addition, when the mixture or prepolymer of the phthalonitrile and the curing agent contains voids or when voids are generated during processing or curing, such problems may also be considered.

The present application provides a phthalonitrile resin, a polymerizable composition, a prepolymer, a composite, a precursor of the composite, and a method and use of the preparation.

The present application provides a phthalonitrile, a polymerizable composition and a prepolymer using the same, which exhibits excellent curability, exhibits a suitable processing temperature and a wide process window, and can form a composite of excellent physical properties.

The present application is directed to phthalonitrile resins. The phthalonitrile resin may include a polymerized unit derived from the compound of formula (1). In the present application, the term “polymerized unit derived from a compound” may refer to a skeleton of a polymer formed by polymerization or curing of the compound.

[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, at least two of R ¹ to R ⁵ are cyano groups, and at least two of R ⁶ to R ¹⁰ are Is a cyano group, X ¹ and X ² are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, Ar ¹ , Ar ² and Ar ³ are the same or different aromatic divalent radicals, n is one or more Wherein m is one or more numbers, L ¹ is an alkylene group or an alkylidene group, and L ² is an alkylene group or alkylidene group substituted with a monovalent radical of formula (2):

[Formula 2]

In Formula 2, R ¹¹ to R ¹⁵ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano group, at least two of R ¹¹ to R ¹⁵ are cyano groups, X ³ is an alkylene group, an alkylidene group, Is an oxygen atom or a sulfur atom, and Ar ⁴ is an aromatic divalent radical.

In the present application, the term alkyl group may be an alkyl 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 substituted by one or more substituents if necessary.

The term alkoxy group in the present application may be an 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 alkoxy group may be linear, branched or cyclic and may be substituted by one or more substituents if necessary.

The term aryl group in the present application may mean a monovalent moiety derived from a benzene ring, a compound containing a benzene ring, or a derivative of any one of the above, unless otherwise specified. As the compound including the benzene ring, it may mean a compound having a structure in which two or more benzene rings are condensed while sharing one or two carbon atoms, or are directly connected or connected by an appropriate linker. As such a compound, biphenyl, naphthalene, etc. can be illustrated. 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 may include, but are not limited to, a phenyl group, benzyl group, biphenyl group or naphthalenyl 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 or an arylalkyl group.

In the present application, the term aromatic divalent radical means a benzene ring, a compound containing a benzene ring, or a divalent moiety derived from any one of the above-mentioned derivatives unless otherwise specified. Can be. The aromatic divalent radical may include, for example, 6 to 25, 6 to 20, or 6 to 12 carbon atoms. Representative types of aromatic divalent radicals include, but are not limited to, phenylene groups.

The term alkylene group or alkylidene group in the present application means an alkylene group or alkylidene 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. can do. The alkylene group or alkylidene group may be linear, branched or cyclic. In addition, the alkylene group or alkylidene group may be optionally substituted with one or more substituents.

In the present application, as the substituent which may be optionally substituted with the alkyl group, alkoxy group, aryl group, aromatic divalent radical, alkylene group or alkylidene group, halogen, glycidyl group, epoxyalkyl group, glyci such as chlorine or fluorine Epoxy groups, such as a doxyalkyl group or an alicyclic epoxy group, acryloyl group, methacryloyl group, an isocyanate group, a thiol group, an alkyl group, an alkoxy group, or an aryl group etc. can be illustrated, but it is not limited to these.

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, at least two of R ¹ to R ⁵ are cyano groups, and at least two of R ⁶ to R ¹⁰ It is a cyano group. In another example, R ¹ to R ^{10 which} are not a cyano group are each independently hydrogen, an alkyl group, or an alkoxy group, or may be hydrogen or an alkyl group. In one example, in Formula 1, R ³ , R ⁴ , R ⁸ and R ⁹ are cyano groups, and R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R ¹⁰ are each independently hydrogen, an alkyl group, alkoxy It may be a group or an aryl group, hydrogen, an alkyl group, or an alkoxy group, or hydrogen or an alkyl group.

X ¹ and X ² in Formula 1 are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, and in another example, may be an alkylene group, an alkylidene group or an oxygen atom, or may be an oxygen atom.

Ar ¹ , Ar ^2, and Ar ³ in Formula 1 may be the same or different aromatic divalent radicals, and the aromatic divalent radical may be, for example, phenylene, but is not limited thereto. In addition, the substitution position of L ¹ based on X ¹ in Ar ¹ of Formula 1 may be an ortho, meta, or para position, for example, a para position. have. In addition, the substitution position of L ² based on L ¹ in Ar ² of Formula 1 may be an ortho, meta, or para position, for example, a para position. Can be. In addition, in Ar ³ of Formula 1, the substitution position of X ² based on L ² may be an ortho, meta, or para position, for example, a para position. have.

N may be any number of one or more, and m may be any number of one or more. The fact that n and m are at least one at the same time allows the compound to exhibit excellent curing properties and to exhibit appropriate processing temperature and process window characteristics. When n and m in the formula (1) at the same time at least 1, while maintaining the number of phthalonitrile groups participating in the curing reaction is appropriate, the structure of the overall compound can be maintained advantageously to the processing temperature and process window properties. For example, when m is 0, the number of phthalonitrile groups included in the compound of Formula 1 is limited, and at the same time, the structure of the core portion of the compound may exhibit symmetry. This results in an increase in processing temperature, such as melting temperature, and at the same time deteriorates process window characteristics. On the other hand, when n is 0 in Formula 1, the structure of the compound of Formula 1 may exhibit symmetry that facilitates intermolecular overlap, and this symmetry causes an increase in crystallinity, resulting in processing temperature (ex. ) And deterioration of the process window characteristics can be induced.

N in Formula 1 may be in the range of 1 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 to 3, or 1 or 2 in another example.

M in formula 1 may be in the range of 1 to 10, 1 to 8, 1 to 6, 1 to 4 or 1 to 3, or 1 or 2.

In Formula 1, L ¹ may be an alkylene group or an alkylidene group, and L ² may be an alkylene group or an alkylidene group substituted with the monovalent radical of Formula 2 above.

In Formula 2, R ¹¹ to R ¹⁵ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano group, and at least two of R ¹¹ to R ¹⁵ are cyano groups. In another example, R ¹ to R ^{5 which} are not cyano groups are each independently hydrogen, an alkyl group or an alkoxy group, or may be hydrogen or an alkyl group. In one example, in Formula 2, R ¹³ and R ¹⁴ are cyano groups, and R ¹¹ , R ¹² and R ¹⁵ are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, a hydrogen, an alkyl group or an alkoxy group, or It may be hydrogen or an alkyl group.

X ³ in Formula 2 is an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, and in another example, may be an alkylene group, an alkylidene group or an oxygen atom, or may be an oxygen atom.

Meanwhile, in Formula 2, Ar ⁴ is an aromatic divalent radical, and the aromatic divalent radical may be, for example, phenylene, but is not limited thereto. In addition, the substitution position of X3 based on the site linked to L ² of Formula 1 in Ar ⁴ of Formula ² may be an ortho, meta, or para position, for example, para (para) location.

는 그 부위가 화학식 1의 L에 연결되는 것을 의미할 수 있다.Sign in formula (2)

May mean that the site is linked to L in the general formula (1).

Suitable compounds in one example are compounds in which X ¹ and X ² in formula 1 are oxygen atoms, Ar ¹ , Ar ² and Ar ³ are phenylene groups, n is 1 or 2 and m is 1 or 2 Can be. In the above structure, Ar ⁴ in Formula 2 may be a phenylene group, and X ³ may be an oxygen atom. In the above compounds, the above descriptions may be applied to specific types of R1 to R15 and substitution positions of L ¹ , L ² , X ² and X ³ in the phenylene group.

Compounds of the same structure as Formula 1 have a bulky structure and increased free volumne, and exhibit an appropriate processing temperature. Moreover, since the number of the phthalonitrile structures corresponding to a curable functional group is at least 3, the reactivity of the hardening | curing agent mentioned later is excellent.

Accordingly, the compound may provide a polymerizable composition and a prepolymer excellent in curability, exhibiting an appropriate processing temperature and a wide process window, and capable of forming a complex of excellent physical properties.

In one example, the processing temperature of the compound may be, for example, in the range of 100 ° C. to 250 ° C. or 100 ° C. to 200 ° C. The term processing temperature in the present application may mean a temperature at which the compound, the following polymerizable composition or prepolymer including the same, and the like exist in a processable state. Such a processing temperature may be, for example, a softening point, a melting temperature (Tm) or a glass transition temperature (Tg). This range is advantageous for implementing a polymerizable composition or prepolymer that exhibits proper fluidity and processability, ensures a wide process window, and can form a composite of good physical properties.

The compound of formula 1 can be synthesized according to the synthesis method of known organic compounds. For example, the compound of Formula 1 may be reacted with a reaction known as a nitro displacement reaction, for example, a compound containing a hydroxy group and a compound containing a nitrile group in the presence of a basic catalyst or the like. Can be synthesized.

The phthalonitrile resin may further include a polymerization unit of another phthalonitrile compound in addition to the polymerization unit of the compound of the formula (1). In this case, the kind of phthalonitrile compound that can be selected and used is not particularly limited, and known compounds known to be useful for the formation of phthalonitrile resins and the control of their physical properties can be applied. Examples of such compounds include U.S. Patent 4,408,035, U.S. Patent 5,003,039, U.S. Patent 5,003,078, U.S. Patent 5,004,801, U.S. Patent 5,132,396, U.S. Patent 5,139,054, U.S. Patent 5,208,318, U.S. Patent Compounds known from US Pat. No. 5,237,045, US Pat. No. 5,292,854, US Pat. No. 5,350,828, and the like can be exemplified, and various compounds known in the art other than those described above can be included in the examples.

In one example, the phthalonitrile resin may include a polymer unit of the compound of Formula 1 or a polymer unit of a phthalonitrile compound including the compound as a main component. In the present specification, the inclusion of any component as a main component means that the component is 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more by weight. Or 95% or more. The upper limit of the ratio is not particularly limited and may be, for example, 100% or less, less than 100%, 95% or less, or 90% or less by weight.

In the phthalonitrile resin, the polymer unit of the compound of Formula 1 may be a polymer unit formed by the reaction of the compound of Formula 1 and a curing agent. The type of curing agent that can be used in this case is not particularly limited as long as it can react with the compound of Formula 1 to form a polymer. For example, any compound may be used as long as it is a compound known to be useful for forming a phthalonitrile resin. Can be. Such hardeners are known in various documents, including the US patents described above.

In one example, an amine compound or a hydroxy compound such as an aromatic amine compound may be used as a curing agent. 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 such curing agents can be applied to most of the present application.

The present application also relates to polymerizable compositions. The polymerizable composition may include the compound of Formula 1 described above. The polymerizable composition may further include a curing agent together with the compound of Formula 1.

The type of curing agent that can be used above is not particularly limited, and for example, a curing agent as described above can be used.

The proportion of the curing agent in the polymerizable composition is not particularly limited. For example, the ratio may be adjusted to ensure the desired curability in consideration of the ratio or type of the curable component such as the compound of Formula 1 included in the composition. For example, the curing agent may be included in an amount of about 0.02 mol to 1.5 mol per mol of the compound of Formula 1 included in the polymerizable composition. However, the ratio is only an example of the present application. Usually, the ratio of the curing agent in the polymerizable composition is high, but the process window is narrow, and when the ratio of the curing agent is low, the curing property tends to be insufficient, so in view of this point, an appropriate ratio of curing agent can be selected. have.

The polymerizable composition of the present application can exhibit an appropriate processing temperature and a wide process window while being excellent in curability.

In one example, the processing temperature of the polymerizable composition, that is, the melting temperature or the glass transition temperature, may be in the range of 100 ° C to 250 ° C or 100 ° C to 200 ° C. In this case, the absolute value of the process window of the polymerizable composition, i.e., the difference between the processing temperature (Tp) and the curing temperature (Tc) of the compound of Formula 1 and the curing agent (Tc) is 50 ° C or more, 70 ° It may be above C or above 100 ° C. In one example, the curing temperature (Tc) may be higher than the processing temperature. This range may be advantageous to secure appropriate processability in the process of producing a composite, for example, which will be described later using the polymerizable composition. In the above, the upper limit of the process window is not particularly limited, but for example, the absolute value of the difference (Tc-Tp) between the processing temperature (Tp) and the curing temperature (Tc) may be 300 ° C or less or 200 ° C or less. have.

The polymerizable composition may further include various additives including other phthalonitrile compounds in addition to the compound of Chemical Formula 1. Examples of such additives may include, but are not limited to, fillers or dispersants such as glass fibers, carbon fibers, graphene, or carbon nanotubes as described below.

In one example, the polymerizable composition may include a compound of Formula 1 or a phthalonitrile compound including the compound as a main component. Accordingly, the polymerizable composition may contain at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80% of the compound of Formula 1 or the phthalonitrile compound including the compound by weight. 85% or more, 90% or more, or 95% or more. The upper limit of the ratio is not particularly limited and may be, for example, 100% or less, less than 100%, 95% or less, or 90% or less by weight.

The present application also relates to a prepolymer formed by the reaction of the polymerizable composition, that is, the polymerizable composition comprising the compound of Formula 1 and a curing agent.

In the present application, the term prepolymer state refers to a state in which the compound of Formula 1 and a curing agent occur to some extent in the polymerizable composition (for example, a state in which polymerization of the A or B stage stage occurs), It can mean the state which can process a composite_body | complex mentioned later, for example, showing appropriate fluidity, without reaching | attaining it. In one example, the prepolymer state may refer to a state in which polymerization of the polymerizable composition is performed to some extent.

The prepolymer may also exhibit good curability, suitable processing temperatures and a 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, for example, glass transition temperature or melting temperature, may be in the range of 100 ° C to 250 ° C or 100 ° C to 200 ° C. In this case the absolute value of the process window of the prepolymer, i.e. the difference (Tc-Tp) between the processing temperature (Tp) and the curing temperature (Tc) of the prepolymer, should be at least 50 ° C, at least 70 ° C or at least 100 ° C. Can be. In one example, the curing temperature Tc may be higher than the processing temperature Tp. This range may be advantageous to ensure appropriate processability using a prepolymer, for example, in the preparation of the composite described below. In the above, the upper limit of the process window is not particularly limited, but for example, the absolute value of the difference (Tc-Tp) between the processing temperature (Tp) and the curing temperature (Tc) may be 300 ° C or less or 200 ° C or less. have.

The prepolymer may further comprise any known additive in addition to the above components. Examples of such an additive may include, but are not limited to, the aforementioned fillers.

The present application also relates to composites. The composite may include the phthalonitrile resin and filler described above. As described above, through the compound of Formula 1 of the present application, it is possible to achieve excellent curing properties, proper processing temperature and wide process window, and thus, a so-called reinforced resin composite having excellent physical properties including various fillers ( Reinforced polymer composite can be easily formed. The composite formed as described above may include the phthalonitrile resin and the filler, and may be applied to various applications including, for example, durable materials such as automobiles, airplanes, or ships.

The type of filler is not particularly limited and may be appropriately selected in consideration of the intended use. Fillers that can be used include fibrous materials such as carbon fibers, aramid fibers, glass fibers or ceramic fibers, or carbon nanomaterials such as woven fabrics, nonwovens, strings or strings or carbon nanotubes or graphemes formed by the materials. Etc. may be exemplified, but is not limited thereto.

The proportion of the filler is also not particularly limited and may be set in an appropriate range depending on the intended use.

The present application also relates to a precursor for preparing the composite, which precursor may comprise, for example, the polymerizable composition and the filler described above, or may comprise the prepolymer and the filler described above.

The composite can be prepared in a known manner using the precursor. For example, the composite may be formed by curing the precursor.

In one example, the precursor is a polymerizable composition comprising the compound of Formula 1 and a curing agent, or the filler, if necessary, in a state in which the prepolymer formed by temporarily curing the polymerizable composition is melted by heating or the like. It can mix and manufacture. For example, the precursor prepared as described above may be molded into a desired shape and then cured to prepare the above-described composite. The polymerizable composition or prepolymer has an appropriate processing temperature and a wide process temperature, and excellent curing property, so that molding and curing can be efficiently performed in the process.

In the above process, a method of forming a prepolymer or the like, a method of mixing the prepolymer or the like with filler, processing and curing to prepare a composite, and the like may be performed according to a known method.

In the present application, it is possible to provide a phthalonitrile, a polymerizable composition using the same, and a prepolymer having excellent curability, exhibiting an appropriate processing temperature and a wide process window, and capable of forming a complex of excellent physical properties.

1 is an NMR analysis result of the compound (PN1) prepared in Preparation Example 1.

2 is an NMR analysis result of the compound (PN2) prepared in Preparation Example 2.

3 is a result of NMR analysis for the compound (PN3) prepared in Preparation Example 3.

4 is a result of NMR analysis for the compound (PN3) prepared in Preparation Example 3.

Hereinafter, the phthalonitrile resin and the like of the present application will be described in detail with reference to Examples and Comparative Examples, but the scope of the resin and the like is not limited to the following Examples.

1. NMR (Nuclear magnetic resonance) analysis

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 the measurement of NMR were prepared by dissolving the compound in dimethyl sulfoxide (dSO) -d6.

2. Differential scanning calorimetry (DSC) analysis

DSC analysis was performed in a N2 flow atmosphere using a TA instrument Q20 system at a rate of temperature rise of 10 ° C / min from 35 ° C to 450 ° C.

3. Thermogravimetric Analysis (TGA) analysis

TGA analysis was performed using a TGA e850 instrument from Mettler-Toledo. In the case of the compound prepared in Preparation Example was analyzed in an N2 flow atmosphere while raising the temperature at a temperature increase rate of 10 ° C / min from 25 ° C to 800 ° C, in the case of the composition prepared in Examples or Comparative Examples of 375 ° C After post-curing at the temperature was analyzed in the N2 flow atmosphere while raising the temperature at a temperature rising rate of 10 ° C / min from 25 ° C to 900 ° C.

Preparation Example 1 Synthesis of Compound (PN1)

38.2 g of a compound of Formula A (CAS No. 110726-28-8) and 100 mL of DMF (dimethyl formamide) were added to a three neck round-bottom flast (RBF), followed by stirring at room temperature to dissolve. To this was added 46.7 g of 4-nitrophthalonitrile of formula B, 50 g of DMF was added, followed by stirring to dissolve. Then 56.0 g of potassium carbonate and 50 g of DMF were added together, and then the temperature was raised to 85 ° C. while stirring. After reacting for about 5 hours, the mixture is cooled to room temperature. The cooled reaction solution was poured into 0.2N aqueous hydrochloric acid to neutralize 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 the water and the residual solvent, the compound of formula C (PN1) was obtained in a yield of 85% by weight.

[Formula A]

[Formula B]

[Formula C]

Results of NMR analysis for the compound of formula C are shown in FIG. 1. DSC analysis of the compound of Formula C showed that the processing temperature (softening point) was about 104 ° C. In the TGA analysis, the residue at 800 ° C. was found to be as high as 42% by weight, indicating that it had excellent thermal stability.

Preparation Example 2 Synthesis of Compound (PN2)

27.9 g of Compound D and 100 mL of DMF (dimethyl formamide) were added to a three neck round-bottom flast (RBF), and the mixture was stirred at room temperature to dissolve. 51.9 g of 4 nitro phthalonitrile of the formula (B) used in Preparation Example 1 was added, and 50 g of DMF was added, followed by stirring to dissolve. Then 62.2 g of potassium carbonate and 50 g of DMF were added together, and then 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 0.2N aqueous hydrochloric acid to neutralize 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 (PN2) of the formula (E) was obtained in a yield of 83% by weight.

[Formula D]

[Formula E]

The NMR analysis of the compound of Formula E is shown in FIG. 2. The analytical results for the compound are summarized in Table 1.

Preparation Example 3 Synthesis of Compound (PN3)

50.4 g of the compound of Formula F and 150 mL of DMF (dimethyl formamide) were added to a three neck round-bottom flast (RBF), followed by stirring at room temperature to dissolve. 51.9 g of 4-nitrophthalonitrile of the formula (B) used in Preparation Example 1 was added thereto, and 50 g of DMF was added thereto, followed by stirring to dissolve it. Then 62.2 g of potassium carbonate and 50 g of DMF were added together, and then the temperature was raised to 85 ° C. while stirring. After reacting for about 5 hours, the mixture is cooled to room temperature. The cooled reaction solution was poured into 0.2N aqueous hydrochloric acid to neutralize 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 formula G was obtained in a yield of 87% by weight.

Formula F]

[Formula G]

The NMR analysis of the compound of Formula G is shown in FIG. 3. The analytical results for the compound are summarized in Table 1.

Preparation Example 4 Synthesis of Compound (PN4)

27.6 g of Compound (H) and 100 mL of DMF (dimethyl formamide) were added to a three neck round bottom flask (RBF), and the mixture was stirred at room temperature to dissolve. 46.7 g of the compound of Chemical Formula B of Preparation Example 1 was further added thereto, and 50 g of DMF was added thereto, followed by stirring to dissolve it. Subsequently, 56.0 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 about 5 hours, the mixture was cooled to room temperature. The cooled reaction solution was neutralized precipitated with 0.2 N aqueous hydrochloric acid solution and washed with water after filtration. Thereafter, the filtered reaction was dried in a vacuum oven at 100 ° C. for one day, and water and residual solvent were removed to obtain a compound of formula (I) (PN4) in a yield of about 87% by weight.

[Formula H]

[Formula I]

The NMR analysis of the compound of Formula I is shown in FIG. 4. The analytical results for the compound are summarized in Table 1.

Preparation Example 5 Synthesis of Compound (CA1)

The compound of formula J (CA1) was obtained from TCI (Tokyo Chemical Industry Co., Ltd.) and used without further purification.

[Formula J]

DSC and TGA analysis results for the compounds of Preparation Examples 1 to 4 (PN1, PN2, PN3, PN4) are summarized in Table 1 below.

TABLE 1

Example 1.

6 mole% of the compound of Preparation Example 5 (CA1) was added to the compound (PN1) of Formula C in Preparation Example 1, and mixed well to prepare a polymerizable composition. The results of performing DSC and TGA analysis on the composition are listed in Table 2 below. The polymerizable composition may be melted at 150 ° C. and stirred for 5 minutes to prepare a prepolymer.

Comparative Example 1.

6 mole% of the compound of Preparation Example 5 (CA1) was added to the compound (PN2) of Formula E in Preparation Example 2, and mixed well to prepare a polymerizable composition. The results of performing DSC and TGA analysis on the composition are listed in Table 2 below. The polymerizable composition may be melted at 240 ° C. and stirred for 5 minutes to prepare a prepolymer.

Comparative Example 2.

6 mole% of the compound of Preparation Example 5 (CA1) was added to the compound of Formula G (PN3) in Preparation Example 3, and mixed well to prepare a polymerizable composition. The results of performing DSC and TGA analysis on the composition are listed in Table 2 below. The polymerizable composition may be melted at 240 ° C. and stirred for 5 minutes to prepare a prepolymer.

Comparative Example 3.

To the compound of formula (I) of Preparation Example 4 (PN4) 6 mol% of compound of Preparation Example 5 (CA1) was added to the amount of the compound of formula (I) and mixed well to prepare a polymerizable composition. The results of performing DSC and TGA analysis on the composition are listed in Table 2 below. The polymerizable composition may be melted at 240 ° C. and stirred for 5 minutes to prepare a prepolymer.

The results of performing DSC and TGA analysis on the compositions of Examples and Comparative Examples are shown in Table 2 below.

TABLE 2

From the results of Table 2, when using the compound of Formula 1 of the present application, it can be seen that showing a significantly wider process window, while showing a lower processing temperature than the comparative example.

That is, in the case of Example 1 using a compound having a structure of m and n in the formula (1) while having three phthalonitrile groups, much lower processing compared to the case of Comparative Examples 1 and 2 having two phthalonitrile groups It can be seen that it is possible to prepare the prepolymer at a low temperature with a temperature, to secure a wide process window of 100 ° C. or more, and to exhibit excellent heat resistance.

In addition, in the case of Comparative Example 3, it has three phthalonitrile groups as in the case of Example 1, but due to the symmetry of the core structure, the crystallinity is increased, thereby increasing the processing temperature, as a result the process window It was confirmed very narrowly.

Claims (20)

Phtharonitrile resin comprising a polymerized unit derived from a compound of formula (I): [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, at least two of R ¹ to R ⁵ are cyano groups, and at least two of R ⁶ to R ¹⁰ Is a cyano group, X ¹ and X ² are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, Ar ¹ , Ar ² and Ar ³ are the same or different aromatic divalent radicals, n is one or more Wherein m is one or more numbers, L ¹ is an alkylene group or an alkylidene group, and L ² is an alkylene group or alkylidene group substituted with a monovalent radical of formula (2): [Formula 2]

In Formula 2, R ¹¹ to R ¹⁵ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano group, at least two of R ¹¹ to R ¹⁵ are cyano groups, X ³ is an alkylene group, an alkylidene group, Is an oxygen atom or a sulfur atom, and Ar ⁴ is an aromatic divalent radical. The compound of claim 1, wherein in Formula 1, R ¹ to R ¹⁰ are each independently hydrogen or an alkyl 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. Phthalonitrile resins. The compound according to claim 1, wherein in Formula 1, R ³ , R ⁴ , R ⁸ and R ⁹ are cyano groups, and R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R ¹⁰ are each independently hydrogen or an alkyl group. Phosphorous phthalonitrile resin. The phthalonitrile resin of claim 1, wherein Ar ¹ , Ar ² and Ar ³ in Formula 1 are phenylene. The method of claim 4, wherein the substitution position of L ¹ on the basis of X ¹ in Ar ¹ of formula (1) is the para position, the substitution position of the L ² based on the L ¹ in Ar ² is the para position, in Ar ³ the substitution position of X ^2, based on the L ² is the para position of the phthalonitrile resin. The phthalonitrile resin according to claim 1, wherein n is a number in the range of 1 to 10, and m is a number in the range of 1 to 10. The phthalonitrile resin according to claim 1, wherein in Formula 2, R ¹¹ to R ¹⁵ are each independently hydrogen or an alkyl group, and at least two of R ¹¹ to R ¹⁵ are cyano groups. The phthalonitrile resin according to claim 1, wherein in the formula (2), R ¹³ and R ¹⁴ are cyano groups, and R ¹¹ , R ¹² and R ¹⁵ are each independently hydrogen or an alkyl group. The phthalonitrile resin of claim 1, wherein Ar ⁴ in Formula 2 is phenylene. 10. The phthalonitrile resin of claim 9, wherein the substitution position of X ³ based on the moiety linked to Ar ² in Formula ² is para position. The compound of claim 1, wherein in Formula 1, X ¹ and X ² are oxygen atoms, Ar ¹ , Ar ² and Ar ³ are phenylene groups, n is 1 or 2, m is 1 or 2, and Ar in Formula 2 ⁴ is a phenylene group, X ³ is an phthalonitrile resin which is an oxygen atom. A polymerizable composition comprising a compound of formula 1 and a curing agent: [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, at least two of R ¹ to R ⁵ are cyano groups, and at least two of R ⁶ to R ¹⁰ Is a cyano group, X ¹ and X ² are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, Ar ¹ , Ar ² and Ar ³ are the same or different aromatic divalent radicals, n is one or more Wherein m is one or more numbers, L ¹ is an alkylene group or an alkylidene group, and L ² is an alkylene group or alkylidene group substituted with a monovalent radical of formula (2): [Formula 2]

In Formula 2, R ¹¹ to R ¹⁵ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano group, at least two of R ¹¹ to R ¹⁵ are cyano groups, X ³ is an alkylene group, an alkylidene group, Is an oxygen atom or a sulfur atom, and Ar ⁴ is an aromatic divalent radical. The polymerizable composition according to claim 12, wherein the processing temperature is in the range of 100 ° C to 250 ° C, and the absolute value of the difference between the processing temperature and the curing temperature (Tc) is 50 ° C or more. A prepolymer which is a reactant of the polymerizable composition of claim 12. The prepolymer of claim 14, wherein the processing temperature is in the range of 100 ° C. to 250 ° C., and the absolute value of the difference between the processing temperature and the curing temperature (Tc) is 50 ° C. or more. A composite comprising the phthalonitrile resin of claim 1. 17. The composite of claim 16 further comprising a filler. 18. The composite of claim 17, wherein the filler is a fibrous material or a carbon nano material. A precursor of the complex of claim 17 comprising the polymerizable composition of claim 12 or the prepolymer of claim 14. 20. A method of making a composite comprising curing the precursor of claim 19.

Images