KR101985800B1 - Phthalonitrile compound - Google Patents

Abstract

The present application relates to novel phthalonitrile compounds and uses thereof. The phthalonitrile compound has a novel structure and can exhibit an excellent effect in a known application in which a phthalonitrile compound can be applied. Examples of the use of such a phthalonitrile compound include raw materials or precursors such as a so-called phthalonitrile resin, a phthalocyanine dye, a fluorescent whitening agent, a photosensitizer or an acid anhydride.

Description

Phthalonitrile compound < RTI ID = 0.0 >

The present application relates to a phthalonitrile compound, a phthalonitrile resin, a polymerizable composition, a prepolymer, a complex, a precursor thereof, and a production method and use thereof.

Phthalonitrile can be used in a variety of applications. For example, a composite formed by impregnating a resin (phthalonitrile resin) prepared using the phthalonitrile as a monomer into a filler such as glass fiber or carbon fiber is used as a material for automobiles, airplanes or ships Can be used. The process for producing the composite may include, for example, a process of mixing a prepolymer formed by the reaction of a mixture of phthalonitrile and a curing agent or a mixture thereof with a filler and then curing the mixture (see, for example, Patent Document 1 Reference). In order for the composite preparation to be effective, the polymerizable composition or prepolymer is required to have appropriate meltability and fluidity and to have a so-called process window.

Other uses of phthalonitrile compounds include the use of phthalocyanine pigments as precursors. For example, a phthalonitrile compound may be compounded with a metal and applied as a pigment.

The phthalonitrile compound may also be applied as a fluorescent brightener or a precursor of a photographic sensitizer or a precursor of an acid anhydride. For example, the phthalonitrile compound can be converted to an acid anhydride via an appropriate oxidation and dehydration process, which acid anhydride may be used as a precursor, such as polyamic acid or polyimide.

Korean Patent No. 0558158

The present application provides novel phthalonitrile compounds and uses thereof. Uses of such compounds may include most applications known to be applicable to phthalonitrile compounds, and examples thereof include phthalonitrile resins, polymerizable compositions, prepolymers, composites, pigments, fluorescent brighteners, photo sensitizers, The precursor or raw material of the acid anhydride can be exemplified.

The present application is directed to a phthalonitrile compound. The compound may be represented by the following general formula (1).

[Chemical Formula 1]

In formula 1 A ₁ is wherein q is an aromatic radical, A ₂ is (1 + n) is an aromatic radicals, A ₃ is (1 + m) is an aromatic radical, L ₁ and L ₂ are alkylene groups, each independently, an alkylidene group, an oxygen atom or a sulfur atom, X _1, X ₂ and X ₃ are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, are each independently hydrogen, R, and R ₂ to R _16, At least two of R ₂ to R ₆ are a cyano group, at least two of R ₇ to R ₁₁ are a cyano group, at least two of R ₁₂ to R ₁₆ are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a cyano group, And q is a number of (3 + p), m is a number of 2 or more, n is a number of 2 or more, and p is a number of 3 or more.

In formula (1), q is an arbitrary number corresponding to 3 + p, and may be any number within the range of, for example, 6 to 25, 6 to 20, 6 to 15, or 6 to 12. In the formula (1), m is an arbitrary number of 2 or more, for example, 2 to 5, 2 to 4, 3 or 2. In formula (1), n is an arbitrary number of 2 or more, for example, 2 to 5, 2 to 4, 3 or 2. On the other hand, in the general formula (1), p is an arbitrary number corresponding to q-3, and may be any number within the range of 3 or more, 3 to 22, 3 to 17, 3 to 12 or 3 to 9.

The term aromatic radical in the present application may mean a radical derived from a benzene, a compound comprising a benzene structure, or a derivative of any of the above, unless otherwise specified. As the benzene-containing compound described above, compounds having two or more benzene rings each having a structure in which two carbon atoms are mutually bonded or condensed or linked by an appropriate linker can be exemplified. An aromatic radical may include, for example, 6 to 25, 6 to 20, 6 to 15, or 6 to 12 carbon atoms and may optionally be substituted with one or more substituents.

In the meantime, the term radical or radical formation in the present application means that the benzene, the compound containing benzene structure, or a derivative thereof may be substituted with other substituents such as R, L ₁ , L ₂ , X ₁ , X ₂ and / Or forming a covalent bond with X < ₃ >. Thus, in the present application, the term n radicals (where n is an arbitrary number) may mean the case where there are n covalent bonds.

In one example, the aromatic radical may be a radical derived from an aromatic compound of any of formulas (2) to (4).

(2)

When the radical formed by formula (2) is A ₁ in formula (1), R _a to R _f in formula (2) are each independently a radical forming a covalent bond with L ₁ , L ₂ , X ₃ or R in formula of the formula (2) when a radical formed by the formula (2) is a ₂ of the formula 1 R _a to R _f each independently represent a hydrogen, an alkyl group, are an alkoxy group or an aryl odd, R _a to R _f (1 + n) the number of the corresponding (wherein n is a n defined in formula (1).) of the substituents is a radical to form a L ₁ or X ₁ and covalent bonds of formula (1), the a is formula (I) the radical formed by the general formula (2) ₃ , R _a to R _f each independently represent a hydrogen, an alkyl group, an alkoxy group or an aryl group, and a number corresponding to (1 + m) in R _a to R _f m is defined.) to form a substituent of the L ₂ or X ₂ is covalently bonded to the general formula (1) Radical.

(3)

When the radical formed by the formula (3) is A ₁ in formula (1), R _a to R _h in formula (2) are each independently a radical forming a covalent bond with L ₁ , L ₂ , X ₃ or R in formula (1) of the formula is a radical formed by the general formula (3) in the case of a ₂ of the general formula 1 3 R _a to R _h is (1 + n) of each independently represent a hydrogen, an alkyl group, are an alkoxy group or an aryl odd, R _a to R _h the number of the corresponding (wherein n is a n defined in formula (1).) of the substituents is a radical to form a L ₁ or X ₁ and covalent bonds of formula (1), the a is formula (I) the radical formed by the general formula (3) ₃ , R _a to R _h in formula (3) are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, and a number corresponding to (1 + m) in R _a to R _h m is defined.) to form a substituent of the L ₂ or X ₂ is covalently bonded to the general formula (1) Radical.

[Chemical Formula 4]

In the formula (4), L is an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, and when the radical formed by the formula (4) is A ₁ in formula (1), R _a to R _j in formula of L _1, L _2, is a radical forming a covalent bond X ₃ or R, and, R _a to R _j are each independently hydrogen, of the formula (4) when a radical formed by the formula (4) in a ₂ in formula (1), alkyl group, and alkoxy group or an aryl marvelous being, R _a to be corresponding to R _j of the (1 + n) (in the n is m as defined in formula (I).) substituents L ₁ or of the general formula (I) of X ₁ a radical forming a covalent bond when the radical is formed by a general formula (4) of a ₃ in the formula (1) formula IV of R _a to R _j each independently is hydrogen, an alkyl group, are an alkoxy group or an aryl marvelous in, R _a to R _j of the number corresponding to (1 + m) (in which m is as defined in formula (I) Substituent group is a m.) Is a radical forming a covalent bond with X ₂ or L ₂ in the formula (I).

In one example, the aromatic radical of A ₁ in formula (1) can be formed by the aromatic compound of formula (2). Of formula (2) in this case R _a to R _f in X ₃ covalently bonded substituents present in at least ortho (ortho) position relative to the substituent to form the the L ₁ and / or a radical one to form the L ₂ is covalently bonded to . In some cases, two substituents present at the ortho position of Formula 2 may form covalent bonds with L ₁ and L ₂ , respectively. Further, in the above case, R is hydrogen, alkyl, alkoxy or aryl may date, at least from R _a to R _f in the general formula (2) based on the substituent to form an X ₃ and covalently bonded in the para (para) position R is a substituent other than hydrogen, for example, an alkyl group, an alkoxy group or an aryl group; Or an alkyl group.

Further, in one example, the aromatic radical of A ₂ or A ₃ of formula (1) can also be formed by an aromatic compound of formula (2). Substituent to form an L ₁ and a covalent bond from R _a to R _f in the general formula (2) in this case (in the case of A ₂₎ or each of at least ortho relative to the substituent (in the case of A ₃₎ to form an L ₂ and a covalent bond ( at least two of the substituents present at the ortho, meta and para positions may form a covalent bond with X ₁ (in case of A ₂ ) or X ₂ (in case of A ₃ ) , At least two of the substituents present in at least the ortho and para positions may form a covalent bond with X ₁ (in case of A ₂ ) or X ₂ (in case of A ₃ ). In another example, at least the substituents present in the para position form a covalent bond with X ₁ (in the case of A ₂ ) and X ₂ (in the case of A ₃ ), and the substituents present in the ortho position One of the substituents may form a covalent bond with X ₁ (in case of A ₂ ) and X ₂ (in case of A ₃ ), respectively. In this case, the substituent other than the substituent forming the covalent bond in the formula (2) may be hydrogen, an alkyl group, an alkoxy group or an aryl group, or may be a hydrogen atom or an alkyl group.

In formula (1), L ₁ and L ₂ are an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, and L ₁ and L ₂ may be the same or different from each other. Suitable examples of L < _{1 >} and L < ₂ > include, but are not limited to, an alkylene group or an alkylidene group.

In formula (1), X ₁ to X ₃ each independently may be an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, and suitable examples include an alkylene group, an alkylidene group or an oxygen atom; Or an oxygen atom.

At least two of the formula 1 R ₂ to R ₁₆ each independently represent a hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano nogiyi being, R ₂ to R ₆ is cyano group, R ₇ to R ₁₁ and at least two of the Cyano group, and at least two of R ₁₂ to R ₁₆ are cyano groups. Suitable examples of R ₂ to R _{16 which} are not cyano groups include hydrogen, an alkyl group or an alkoxy group; Or a hydrogen or an alkyl group. In one example, R ₄ , R ₅ , R ₉ , R ₁₀ , R _14, and R ₁₅ are cyano groups and the remaining substituents (R ₂ , R ₃ , R ₆ , R ₇ , R ₈ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₆ ) are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group; Hydrogen, an alkyl group or an alkoxy group; Or hydrogen or an alkyl group.

The alkyl group in the present application 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, where necessary, may be substituted by one or more substituents.

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 groups may be linear, branched or cyclic and, where necessary, may be substituted by one or more substituents.

In addition, the term aryl group in the present application may mean a monovalent residue derived from benzene, a compound containing a benzene structure or any one of the derivatives described in the aromatic radical item, unless otherwise specified. The aryl group may comprise, for example, 6 to 25, 6 to 20, 6 to 15 or 6 to 12 carbon atoms. Specific examples of the aryl group include, but are not limited to, a phenyl group, a benzyl group, a biphenyl group, or a naphthalenyl group. In addition, in the scope of the aryl group in the present application, not only a functional group commonly referred to as an aryl group but also an aralkyl group or an arylalkyl group may be included.

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

Examples of substituents which may optionally be substituted in the alkyl group, alkoxy group, aryl group, aromatic radical, alkylene group or alkylidene group in the present application include halogen such as chlorine or fluorine, glycidyl group, epoxyalkyl group, glycidoxyalkyl group Or an epoxy group such as 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, but the present invention is not limited thereto.

Specific examples of the compound represented by the formula (1) include a compound represented by the following formula (5).

[Chemical Formula 5]

In formula 5 X ₃ represents an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, R ₂ to R ₆ each independently represent a hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano nogiyi being, R ₂ to R ₆ of at least R ₁₇ to R ₂₁ each independently represent hydrogen, an alkyl group, an alkoxy group, an aryl group or a substituent of the following formula (6), and R ₁₇ to R ₂₁ At least two of them are substituents of the following formula (6).

[Chemical Formula 6]

In the formula 6 L ₄ represents an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, A ₄ is a phenylene group, X ₄ represents an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, R ₂₂ to R ₂₆ is An alkyl group, an alkoxy group, an aryl group or a cyano group, at least two of R ₂₂ to R ₂₆ are cyano groups, and t is 2 or 3;

Suitable examples of X < ₃ > in formula (5) include an alkylene group, an alkylidene group or an oxygen atom; Or an oxygen atom.

In formula (5), R ₂ to R ₆ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group or a cyano group, and at least two of R ₂ to R ₆ are cyano groups. Suitable examples of R ₂ to R _{6 which} are not cyano groups include hydrogen, an alkyl group or an alkoxy group; Or a hydrogen or an alkyl group. In one example, R ₄ and R ₅ in formula (5) are cyano groups and the remaining substituents (R ₂ , R ₃ and R ₆ ) are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group; Hydrogen, an alkyl group or an alkoxy group; Or hydrogen or an alkyl group.

In one example, R ₁₇ to R ₂₁ in Formula 5 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a substituent of Formula 6, and at least two of R ₁₇ to R ₂₁ are substituents of Formula 6 . For example in this case, and R ₁₇ to R _21, at least R ₁₇ and R ₂₁ is a substituent of the formula (6) from, the other substituents (R _18, R ₁₉ and R ₂₀₎ is hydrogen, alkyl, alkoxy or aryl date have. In this case, for example, R ₁₈ and R ₂₀ may be hydrogen, and R ₁₉ may be an alkyl group, an alkoxy group, an aryl group, or an alkyl group.

는, 그 부위가 화학식 1에 연결되는 것을 의미한다.In formula (6)

Means that the moiety is linked to the formula (1).

Suitable examples of L ₄ in formula (6) include, but are not limited to, an alkylene group or an alkylidene group. Suitable examples of X < ₄ > in formula (6) include an alkylene group, an alkylidene group or an oxygen atom; Or an oxygen atom.

In formula (6), A ₄ is phenylene. At least one of the hydrogen atoms in the part of the phenylene except for the part bonded to L ₄ and X ₄ may be substituted or unsubstituted with an alkyl group, an alkoxy group or an aryl group. In addition, X ₄ may be bonded to at least ortho or para positions based on the position of the phenylene linked with L ₄ . In one example, X ₄ is bonded to any one of two para positions on the basis of a site connected to L ₄ in the phenylene and two ortho sites based on a site connected to L ₄ Be able to be

In formula (6), R ₂₂ to R ₂₆ each independently represent hydrogen, an alkyl group, an alkoxy group, an aryl group or a cyano group, and at least two of R ₂₂ to R ₂₆ are cyano groups. Suitable examples of R ₂₂ to R ₂₆ , which are not cyano groups, include hydrogen, an alkyl group or an alkoxy group; Or a hydrogen or an alkyl group. In one example, in Formula 6, R ₂₃ and R ₂₄ are cyano groups and the remaining substituents (R ₂₂ , R _25, and R ₂₆ ) are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group; Hydrogen, an alkyl group or an alkoxy group; Or hydrogen or an alkyl group.

The compound of formula (1) or (5) has an appropriate processing temperature and is excellent in reactivity with a curing agent. The term processing temperature in the present application may mean the temperature at which the compound, the following polymerizable composition or prepolymer containing it, etc. are present in a processable state. Such a processing temperature may be, for example, a melting temperature (Tp) or a glass transition temperature (Tg).

Accordingly, the compound can provide a polymerizable composition and a prepolymer capable of forming a complex having excellent curability, a suitable processing temperature, a wide process window, and excellent physical properties.

In one example, the processing temperature of the compound may be in the range of 50 ° C to 250 ° C, 80 ° C to 200 ° C, or 90 ° C to 150 ° C. This range is advantageous for realizing a polymerizable composition or prepolymer capable of exhibiting appropriate flowability and processability, securing a wide process window, and capable of forming a complex of excellent physical properties.

The compounds of formula (I) or (V) can be effectively used in a variety of applications where the so-called phthalonitrile compounds are known to be applicable. For example, the phthalonitrile compound can be effectively used as a raw material or a precursor capable of producing a so-called phthalonitrile resin. The compound exhibits a suitable melting temperature, is excellent in reactivity with a curing agent, exhibits a wide process window, and can be effectively applied to the application. The compound may be used as a precursor of a dye such as a phthalocyanine pigment, a fluorescent brightener, a photographic sensitizer, or a precursor or raw material of an acid anhydride, in addition to the above-mentioned uses.

The compound represented by the formula (1) or (5) can be synthesized according to the synthesis method of a known organic compound. For example, the compound of formula (1) or (5) can be synthesized by a method of reacting an aromatic compound having a phenolic hydroxy group with an aromatic compound having at least two cyano groups (e.g., a nitro displacement method). In the field of organic chemistry, the aromatic compounds capable of forming the structures of the compounds of the above formula (1) or (5) are known, and these compounds can be applied to the preparation of the above compounds in consideration of the desired structure.

The present application also relates to the use of such compounds. Examples of the use of the compound include a raw material or a precursor of a phthalonitrile resin, a phthalocyanine dye, a fluorescent whitening agent, a photosensitizer or an acid anhydride as described above. As an example of such use, for example, the present application may be directed to a phthalonitrile resin. The phthalonitrile resin may contain a polymerization unit derived from the compound of the above formula (1) or (5). The term polymerized unit derived from a certain compound in the present application may mean the skeleton of the polymer formed by polymerization or curing of the compound.

The phthalonitrile resin may further comprise polymerized units of other phthalonitrile compounds in addition to the polymerized units of the compounds of the general formula (1) or (5). The kind of the phthalonitrile compound that can be selected and used in such a case is not particularly limited, and known compounds known to be useful for the formation of the phthalonitrile resin and the control of its physical properties can be applied. Examples of such compounds are disclosed in U.S. Patent Nos. 4,408,035, 5,003,039, 5,003,078, 5,004,801, 5,132,396, 5,139,054, 5,208,318, 5,237,045, US 5,292,854, or US 5,350,828, but are not limited thereto.

In the phthalonitrile resin, the polymerization unit of the compound of the formula (1) or (5) may be a polymerization unit formed by the reaction of the compound and the curing agent. The kind of the curing agent which can be used in this case is not particularly limited as far as it is capable of reacting with the compound of the formula (1) or (5) to form a polymer, and for example, any compound known to be useful for the formation of a phthalonitrile resin Can also be used. Such curing agents are known in a variety of documents including the above-mentioned U. S. patents.

In one example, an amine compound or a hydroxy compound such as an aromatic amine compound can be used as a curing agent. In the present application, the hydroxy compound may mean a compound containing at least one or two hydroxy groups in the molecule. Curing agents capable of curing a phthalonitrile compound to form a resin are variously known, and these curing agents can be applied in most cases in the present application.

The present application is also directed to polymerizable compositions. The polymerizable composition may comprise the compound of formula (1) or (5) described above. The polymerizable composition may further comprise a curing agent together with the compound of the above formula (1) or (5).

As the curing agent contained in the polymerizable composition, for example, a curing agent such as those already described can be used.

The proportion of the curing agent in the polymerizable composition is not particularly limited. The ratio can be adjusted so that the desired curability can be ensured in consideration of, for example, the ratio or kind of the curable component such as the compound of the formula (1) or (5) contained in the composition. For example, the curing agent may be included in an amount of about 0.02 to 2.5 moles, about 0.02 to 2.0 moles, or about 0.02 to 1.5 moles per mole of the compound of Formula 1 or 5 contained in the polymerizable composition. However, the above ratios are only examples of the present application. Usually, the proportion of the curing agent in the polymerizable composition tends to be high, but the process window tends to become narrow. When the proportion of the curing agent is low, the curability tends to become insufficient. have.

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

In one example, the processing temperature of the polymerizable composition may be in the range of from 50 캜 to 250 캜, from 80 캜 to 200 캜, or from 90 캜 to 150 캜. In this case, the absolute value of the difference (Tc-Tp) between the curing temperature (Tc-Tp) of the process window of the polymerizable composition, i.e., the processing temperature Lt; RTI ID = 0.0 > 100 C < / RTI > In one example, the curing temperature Tc may be higher than the processing temperature Tp. Such a range may be advantageous for securing proper processability in the process of producing a complex to be described later, for example, using a polymerizable composition. The absolute value of the difference (Tc-Tp) between the processing temperature (Tp) and the curing temperature (Tc) is not more than 400 ° C, not more than 300 ° C, or not more than 200 ° C .

The polymerizable composition may further contain various additives including a phthalonitrile compound and the like in addition to the compound of the formula (1) or (5). Examples of such additives include various fillers. The kind of the material that can be used as the filler is not particularly limited, and any known filler suitable for the intended use may be used. Exemplary fillers include, but are not limited to, metal materials, ceramic materials, glass, metal oxides, metal nitrides or carbon-based materials. The form of the filler is not particularly limited, and may be a fibrous material such as aramid fiber, glass fiber or ceramic fiber, or a woven fabric, nonwoven fabric, string or string formed by the material, particulate, polygonal or other amorphous And the like. Examples of the carbon-based material include graphite, graphene, carbon nanotubes, derivatives thereof such as oxides thereof, and isomers thereof. However, the components that the polymerizable composition may further contain are not limited to the above, and various monomers known to be applicable to the production of so-called engineering plastics such as polyimide, polyamide or polystyrene, Additives may also be included without limitation depending on the purpose.

The present application is also directed to a prepolymer formed by the reaction of the polymerizable composition, that is, the polymerizable composition comprising the compound of formula 1 or 5 and a curing agent.

The term " prepolymer state " in the present application is a state in which the compound of formula (1) or (5) and the curing agent are present in a certain degree of occurrence (for example, State, and exhibits appropriate fluidity, and can mean, for example, a state in which the composite body can be processed as described later. In one example, the prepolymer state may be a solid state such as a powder or powder at room temperature of the composition in which the polymerization of the polymerizable composition proceeds to some extent. The term ambient temperature in the present application is intended to mean a temperature of natural or unheated or unheated temperature, for example, from about 10 to 30 캜, from about 15 캜 to 30 캜, from about 20 캜 to 30 캜, Lt; / RTI >

The prepolymer may also exhibit excellent curability, a suitable processing temperature and a wide process window.

For example, the processing temperature of the prepolymer may be in the range of 50 ° C to 250 ° C, 80 ° C to 200 ° C, or 90 ° C to 150 ° C. In this case, the absolute value of the difference (Tc-Tp) between the processing temperature Tp of the prepolymer and the curing temperature Tc of the prepolymer may be 30 ° C or more, 50 ° C or more, or 100 ° C or more. In one example, the curing temperature Tc may be higher than the processing temperature Tp. Such a range may be advantageous for securing appropriate processability in the process of preparing a complex to be described later, for example, using a prepolymer. The absolute value of the difference (Tc-Tp) between the processing temperature (Tp) and the curing temperature (Tc) is not more than 400 DEG C, not more than 300 DEG C or not more than 200 DEG C ≪ / RTI >

The prepolymer may further contain any known additives in addition to the above components. Examples of such additives include, but are not limited to, the above-mentioned fillers and the like.

The present application is also directed to a composite. The composite may include the above-described phthalonitrile resin and filler. As described above, the compound of the formula (1) or (5) of the present invention can achieve excellent curing properties, a suitable processing temperature and a wide process window, A reinforced polymer composite can be easily formed. The composite thus formed may contain the phthalonitrile resin and filler and may be applied to various uses including durables for automobiles, airplanes or ships, and the like.

The kind of the filler is not particularly limited and may be suitably selected in consideration of the intended use. Specific examples of the filler are as described above, but are not limited thereto.

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

The present application is also directed to a precursor for making the composite, which may comprise, for example, the polymeric composition described above and the filler, or the prepolymer described above and the filler.

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

In one example, the precursor may be prepared by blending the polymerizable composition prepared by compounding the compound of formula (1) or (5) described above with a curing agent in a molten state or by blending the prepolymer with the filler in a molten state by heating or the like . For example, the precursor produced as described above may be molded into a desired shape and then cured to make the composite as described above. The polymerizable composition or prepolymer has a proper processing temperature and a wide process temperature and is excellent in curability, so that molding and curing can be efficiently performed in the above process.

A method of forming a prepolymer or the like in the above process, a method of compounding such a prepolymer with a filler, and processing and curing the composite to prepare a composite may be carried out according to a known method.

The present application may also be directed to a precursor of a phthalocyanine dye comprising said compound, a precursor of a fluorescent brightener or a precursor of a photosensitizer, or to an acid anhydride derived from said compound. The method of forming the precursor using the above compound or the method of producing the acid anhydride is not particularly limited and any known method known to be capable of producing the precursor or acid anhydride using the phthalonitrile compound is applied .

The present application provides phthalonitrile compounds and their uses. The phthalonitrile compound has a novel structure and can exhibit an excellent effect in a known application in which a phthalonitrile compound can be applied. Examples of the use of such a phthalonitrile compound include raw materials or precursors such as a so-called phthalonitrile resin, a phthalocyanine dye, a fluorescent whitening agent, a photosensitizer or an acid anhydride.

1 and 2 are NMR analysis results of the compound prepared in the Production Example of the Example.

The phthalonitrile resin and the like of the present application will be specifically described by way of examples and comparative examples, but the range of the resins and the like is not limited to the following examples.

Manufacturing example  One.

The compound of formula (A) was synthesized in the following manner. 15.9 g of BIR-PC (commercial name, produced by Asahi Organic Chemicals Industry Co.) and 39 g of 4-nitro phthalonitrile were reacted with 46.6 g of potassium carbonate and 188 g of DMF (dimethylformamide) Lt; / RTI > The reaction flask used was a 500 mL reactor equipped with a mechanical stirrer, a distillation apparatus and a nitrogen inlet. Then, a nitrogen stream was passed through the reaction flask, and the mixture was heated and stirred at a temperature of about 85 캜 for about 5 hours. Subsequently, the mixture in the flask was cooled to room temperature (20 캜 to 25 캜), and the mixture was precipitated in 2 L of an aqueous hydrochloric acid solution (concentration: 0.2 N), followed by filtration to remove residual inorganic salts and DMF. The powder obtained after filtration was dispersed in 1M methanol (1L), filtered again to remove organic matter, and the reaction product was vacuum-dried in an oven of 50 to obtain a target product.

NMR analysis was performed on an object using an Agilent 500 Megahertz nuclear magnetic resonance apparatus (using solvent: DMSO (d6) (dimethyl sulfoxide-d6)) using an NMR instrument (Agilent 500 MHz NMR device) 1 and 2, respectively.

(A)

Example  One.

(APB, 1,4-bis (4-aminophenoxy) benzene) was present in the compound of the formula (A) synthesized in Preparation Example 1 in such a manner that 0.03 moles per one mole of the compound of the formula (A) was present. The physical properties of the composition were evaluated using DSC (differential scanning calorimetry). Specifically, the heating rate was set at 10 ° C / min using DSC equipment, and the calories were measured while raising the temperature from 25 ° C to 400 ° C. As a result of the measurement, the melting temperature (processing temperature) of the polymerizable composition was about 115.6 캜, and the curing temperature was about 223 캜. Thus, the process window was about 107.4 캜 (223 캜 - 115.6 캜). The curability of the composition was evaluated by integrating the amount of heat released during curing in the DSC analysis. In the case of the polymerizable composition of Example 1, the integrated value of the calories was about 238.5 J / g.

Comparative Example  One.

A polymerizable composition was prepared in the same manner as in Example 1 except for using BP-PN (4,4'-bis (3,4-dicyanophenoxy) biphenyl) instead of the compound of the formula (A). As a result of the evaluation, the melting temperature was about 233.3 ° C, the curing start temperature was about 261.3 ° C, and thus the process window was about 28 ° C. It was confirmed that the value obtained by integrating the heat quantity for the evaluation of the curability was about 19.45 J / g, indicating very poor curability compared with the examples.

Claims (20)

A compound of formula
[Chemical Formula 1]

In formula 1, A ₁ is wherein q is an aromatic radical, A ₂ is (1 + n) is an aromatic radical, A ₃ is (1 + m) is an aromatic radical, L ₁ and L ₂ are each independently C 1 -C X &_lt; ₂ > and X &_lt; ₃ > are each independently an oxygen atom or a sulfur atom, and each R independently represents hydrogen, an alkyl group having 1 to 4 carbon atoms , Or an alkoxy group having 1 to 4 carbon atoms, and each of R ₂ to R ₁₆ is independently hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a cyano group, at least two of R ₂ to R ₆ At least two of R ₇ to R ₁₁ are cyano groups, at least two of R ₁₂ to R ₁₆ are cyano groups, q is a number of (3 + p), and m is N is a number in the range of 2 to 4, p is a number in the range of 3 to 9, to be. delete delete The method of claim 1 wherein, A ₁ is a compound of the alkane radical derived from an aromatic compound of formula (II) to the formula (1):
(2)

In formula (2), each of R _a to R _f independently represents a radical forming a covalent bond with L ₁ , L ₂ , X ₃ or R in formula (1). 5. The compound according to claim 4, wherein the substituent present at the otho position based on the substituent forming a covalent bond with X < ₃ > in the formula (1) among R _a to R _f in formula (2) forms a covalent bond with L ₁ or L ₂ in formula Lt; / RTI > The compound according to claim 1, wherein L ₁ and L ₂ are each independently a straight or branched alkylene group having 1 to 4 carbon atoms. The compound according to claim 1, wherein X ₁ to X ₃ are oxygen atoms. The method of claim 1, wherein, R _4, in the formula _{1 R 5, R 9, R} 10, R 14 and R ₁₅ is cyano _{group, R 2, R 3, R} 6, R 7, R 8, R 11, R ₁₂ , R ₁₃ and R ₁₆ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Compounds of formula 5:
[Chemical Formula 5]

In formula 5 X ₃ is an oxygen atom or a sulfur atom, R ₂ to R ₆ are each independently hydrogen, alkyl of 1 to 4 carbon atoms, an alkoxy group or a cyano been nogiyi of 1 to 4 carbon atoms, R ₂ to R ₆ of at least R ₁₇ to R ₂₁ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a substituent group represented by the following formula (6), at least two of R ₁₇ to R ₂₁ are Is a substituent of the formula (6)
[Chemical Formula 6]

In formula (6), L ₄ represents a linear or branched alkylene group having 1 to 4 carbon atoms, an oxygen atom or a sulfur atom, A ₄ is phenylene, X ₄ is an oxygen atom or a sulfur atom, and R ₂₂ to R ₂₆ are At least two of R ₂₂ to R ₂₆ are cyano groups, and t is 2 or 3; and R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cyano group. A compound according to claim 9, wherein in Formula 5, X ₃ is an oxygen atom, R ₄ and R ₅ are cyano groups, R ₂ , R ₃ and R ₆ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, Lt; / RTI > to 4 carbon atoms. The compound according to claim 9, wherein R ₁₇ and R ₂₁ in Formula 5 are substituents of Formula 6, and R ₁₈ , R ₁₉ and R ₂₀ are hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. [10] The method according to claim 9, wherein the para position on the basis of the moiety connected to L ₄ in the phenylene (A ₄ ) of formula (6) and the two os moieties on the basis of the moiety linked to L ₄ are X ₄ ≪ / RTI > A phthalonitrile resin comprising polymerized units derived from the compound of claims 1 or 9. A polymerizable composition comprising a compound of claim 1 or 9 and a curing agent. A prepolymer which is a reactant of the polymerizable composition of claim 14. A composite comprising the phthalonitrile resin of claim 13 and a filler. The composite according to claim 16, wherein the filler is a metal material, a ceramic material, a glass, a metal oxide, a metal nitride or a carbonaceous material. The polymerizable composition of claim 14; And a filler. A prepolymer of claim 15; And a filler. 19. A method of making a composite comprising curing the precursor of claim 18 or 19.

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