KR102041817B1

KR102041817B1 - Phthalonitrile compound

Info

Publication number: KR102041817B1
Application number: KR1020150172374A
Authority: KR
Inventors: 김상우; 이승희; 안기호
Original assignee: 주식회사 엘지화학
Priority date: 2015-12-04
Filing date: 2015-12-04
Publication date: 2019-11-07
Also published as: KR20170065952A

Abstract

The present application can provide a phthalonitrile compound and its use. The phthalonitrile compound has a novel structure and may exhibit excellent effects in applications known to which the phthalonitrile compound can be applied. Examples of the use of such phthalonitrile compounds include raw materials or precursors such as phthalonitrile resins, phthalocyanine dyes, fluorescent brighteners, photography sensitizers, and acid anhydrides.

Description

Phthalononitrile compound

The present application is directed to phthalonitrile compounds, phthalonitrile resins, polymerizable compositions, prepolymers, composites, precursors thereof and methods of preparation and uses.

The phthalonitrile compound can be applied to various applications. For example, the phthalonitrile compound can be used as a raw material of the so-called phthalonitrile resin. 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, a process of curing after mixing a prepolymer and a filler formed by a mixture of a phthalonitrile and a curing agent or a mixture thereof (for example, Patent Document 1 Reference).

As another use of a phthalonitrile compound, use as a precursor of a phthalocyanine pigment is mentioned. For example, the phthalonitrile compound may be applied as a pigment in combination with a metal.

The phthalonitrile compound may also be applied as a precursor of fluorescent brighteners or photographic sensitizers or precursors of acid anhydrides. For example, the phthalonitrile compound may be converted into an acid anhydride through an appropriate oxidation process and dehydration process, and the acid anhydride may be used as a precursor such as polyamic acid or polyimide.

Korean Registered Patent No. 0558158

The present application can provide novel phthalonitrile compounds and their uses. Examples of the use include phthalonitrile resins, polymerizable compositions or prepolymers for producing the same, composites, precursors of the complexes, and the like, or precursors or raw materials of pigments, fluorescent brighteners, photography sensitizers or acid anhydrides.

The present application is directed to phthalonitrile compounds. The compound may be represented by Formula 1 below.

[Formula 1]

Ar, A ₁ , A ₂ , A ₃ and A ₄ in Formula 1 are aromatic divalent radicals, L ₁ , L ₂ , L ₃ and L ₄ are alkylene groups, alkylidene groups, oxygen atoms or sulfur atoms, R ₁ to R ₂₀ 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, at least two of R ₆ to R ₁₀ are cyano groups, At least two of R ₁₁ to R ₁₅ may be cyano groups, and at least two of R ₁₆ to R ₂₀ may be cyano groups.

In the above, Ar, A ₁ , A ₂ , A ₃ and A ₄ may be the same or different from each other, L ₁ , L ₂ , L ₃ and L ₄ may be the same or different from each other.

In the present application, the term aromatic divalent radical may refer to benzene, a compound containing benzene, or a divalent residue derived from any one of the above, unless otherwise specified. As the compound containing benzene in the above, it may mean a compound having a structure in which two or more benzene rings are condensed while sharing two carbon atoms or connected by an appropriate linker. Aromatic divalent radicals may include, for example, 6-25, 6-20, 6-15 or 6-12 carbon atoms, which may be optionally substituted by one or more substituents. Can be.

In one example, the aromatic divalent radical may be a radical derived from an aromatic compound of any one of Formulas 2 to 4 below.

[Formula 2]

R ₁ to R ₆ in Formula 2 each independently represent a hydrogen, an alkyl group, an alkoxy group, or an aryl group, and at least two of R ₁ to R ₆ form a radical.

[Formula 3]

In Formula 3, R ₁ to R ₈ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group, and at least two of R ₁ to R ₈ form a radical.

[Formula 4]

In Formula 4, R ₁ to R ₁₀ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group, at least two of R ₁ to R ₁₀ form a radical, and L is an alkylene group, an alkylidene group, or an oxygen atom. Or a sulfur atom.

R ₁ to R ₆ of Formula 2, R ₁ to R ₈ of Formula 3 or R ₁ to R ₁₀ of Formula 4 each independently represent a hydrogen, an alkyl group, an alkoxy group or an aryl group, each of two or more of which represents a radical Form. Forming a radical in the above may mean that the site is connected to other elements of the formula (1). For example, in the case of Ar in the formula (1), the sites forming the radicals are each connected to both carbon atoms, in the case of A ₁ the sites forming the radicals are connected to both carbon atoms and L ₁ , in the case of a ₂ is connected to a part of forming the radicals with carbon atoms, and L ₂ on both sides, in the case of a ₃ is the area to form the radical linked to a carbon atom and L ₃ of the two sides, in the case of a ₄ The site forming the radical may be connected to both carbon atoms and L ₄ . In addition, each of the substituents that do not form a radical may be hydrogen, an alkyl group or an alkoxy group; It may be hydrogen or an alkyl group. In one example, in Formula 2, R ₁ and R ₄ or R ₁ and R ₃ may form the radical, and the remaining substituents are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group; Hydrogen, alkyl or alkoxy groups; Or hydrogen or an alkyl group. In Formula 3, any one of R ₁ , R ₆ , R _7, and R ₈ and any one of R ₂ , R ₃ , R _4, and R ₅ may form the radical, and the remaining substituents are each independently hydrogen. , Alkyl group, alkoxy group or aryl group; Hydrogen, alkyl or alkoxy groups; Or hydrogen or an alkyl group. In addition, in Formula 4, any one of R ₁ to R ₅ and any one of R ₆ to R ₁₀ may form the radical, and the remaining substituents are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group; Hydrogen, alkyl or alkoxy groups; Or hydrogen or an alkyl group. In Formula 4, L may be 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 an oxygen atom.

Meanwhile, the term 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 may be substituted by one or more substituents if necessary.

In addition, 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.

In addition, the term aryl group in the present application may refer to a benzene, a compound containing a benzene structure, or a monovalent moiety derived from any one of the above-described derivatives described in the aromatic divalent radical category, unless otherwise specified. have. Aryl groups may include, for example, 6-25, 6-20, 6-15, or 6-12 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.

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, L ₁ to L ₄ may be 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 an oxygen atom.

In Formula 1, R ₁ to R ₂₀ 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, At least 2 of R <_11> -R <_15> is a cyano group, At least 2 of R <_16> -R <_20> is a cyano group. In another embodiment, R ₁ to R ₂₀ that are not cyano groups are each independently hydrogen, an alkyl group, or an alkoxy group; Or hydrogen or an alkyl group. In one example, in Formula 1, R ₃ , R ₄ , R ₈ , R ₉ , R ₁₃ , R ₁₄ , R ₁₈ and R ₁₉ are cyano groups, and the remaining substituents (R ₁ , R ₂ , R ₅ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ , R ₁₆ , R ₁₇ and R ₂₀ ) are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group; Hydrogen, alkyl or alkoxy groups; Or hydrogen or an alkyl group.

The compound of formula 1 can be effectively used in various applications in which so-called phthalonitrile compounds are known to be applicable. For example, the phthalonitrile compound can be effectively used as a raw material or precursor capable of producing a so-called phthalonitrile resin. The compound exhibits a low melting temperature, is excellent in reactivity with the curing agent, and exhibits a wide process window, so that it can be effectively applied to the application. The compound may be applied to precursors or raw materials of dyes such as phthalocyanine pigments, fluorescent brighteners, photographic sensitizers, or acid anhydrides, and the like, in addition to the above uses.

The compound of formula 1 can be synthesized according to the synthesis method of known organic compounds. For example, the compound of Formula 1 is a reaction known as a nitro displacement reaction. For example, an aromatic compound containing a hydroxy group and an aromatic compound containing a nitro group can be prepared in the presence of a basic catalyst or the like. It can synthesize | combine by the method of making it react.

The present application also relates to the use of such compounds. As the use of the compound, as described above, phthalonitrile resin, phthalocyanine dye, fluorescent brightener, photography sensitizer or raw material or precursor of an acid anhydride may be exemplified. As an example of the use, for example, the present application may be for a phthalonitrile resin. The phthalonitrile resin may include a polymer 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.

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 or US Pat. No. 5,350,828 may be exemplified, but are not limited thereto.

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 and the curing agent. In this case, the type of curing agent that can be used 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 so-called 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.

As a hardening | curing agent contained in a polymeric composition, the hardening | curing agent like having already described can be used, for example.

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 about 0.02 to 2 moles or about 0.02 to 1.5 moles per mole of the compound of Formula 1 included in the polymerizable composition. However, the ratio is only an example of the present application. 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. Therefore, an appropriate ratio of curing agent may be selected in consideration of such a point. have.

The polymerizable composition of the present application may exhibit low melting temperature and a wide process window while being excellent in curability.

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 can be exemplified by various fillers. The kind of material that can be used as the filler is not particularly limited, and all known fillers suitable for the intended use can be used. Exemplary fillers include, but are not limited to, metal materials, ceramic materials, glass, metal oxides, metal nitrides, carbon-based materials, and the like. In addition, the form of the filler is not particularly limited, and particulates, polygons including fibrous materials such as aramid fibers, glass fibers, carbon fibers or ceramic fibers, or woven fabrics, nonwoven fabrics, strings or strings, and nanoparticles formed by the materials. Or other amorphous forms. Examples of the carbon-based material may include graphite, graphene, carbon nanotubes, derivatives, isomers, and the like, such as oxides thereof. However, the components which the polymerizable composition may further include are not limited to the above, and various monomers or other known polymers that are known to be applicable to the production of so-called engineering plastics such as, for example, polyimide, polyamide or polystyrene, etc. Additives may also be included without limitation, depending on the purpose.

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.

The prepolymer may also exhibit good curability, low melting temperature and wide process window.

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, low melting 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 may be prepared by blending the polymerizable composition prepared by mixing the compound of Formula 1 described above with a curing agent in a molten state or the prepolymer in a molten state by heating or the like. 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 a low melting temperature and a wide process temperature, and is excellent in curability 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.

The present application may also be directed to precursors of phthalocyanine dyes comprising the compounds, precursors of fluorescent brighteners or precursors of photography sensitizers, or to acid anhydrides derived from such compounds. The method of preparing the precursor or the method of preparing the acid anhydride using the compound is not particularly limited, and all known methods that can be used to prepare the precursor or acid anhydride using the phthalonitrile compound are applicable. Can be.

1 is a view showing the NMR results of the compound prepared in the Example.

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 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 carried out in an N2 flow atmosphere with a temperature increase rate of 10 ° C / min from 35 ° C to 450 ° C by TA instrument Q20 system.

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 ℃ / min from 25 ℃ to 800 ℃.

Example 1 Synthesis of Compound (PN1)

14.2 g and 50 g of DMF (dimethyl formamide) were added to 14.3 g of a compound of Formula A (CAS No. 18066-45-0) in a three neck round-bottom flast (RBF), followed by stirring at room temperature to dissolve. To this was added 20.8 g of 4-nitrophthalonitrile of formula B, 30 g of DMF was added, followed by stirring to dissolve. Subsequently, after 24.9 g of potassium carbonate and 30 g of DMF were added together, 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 removal of water and residual solvent, compound (PN1) of formula C was obtained in a yield of 84% by weight.

[Formula A]

[Formula B]

[Formula C]

The NMR analysis of the compound of Formula C is shown in FIG. 1. DSC analysis of the compound of Formula C showed that the softening point and melting point were very low, such as 169.5 ° C and 247 ° C, respectively, to ensure a wide process window. In addition, during TGA analysis, the residue at 800 ° C. was found to be as high as 44 wt%, confirming that it had excellent thermal stability.

Claims

A compound of formula
[Formula 1]

Ar, A ₁ , A ₂ , A ₃ and A ₄ in Formula 1 are aromatic divalent radicals which may be the same or different from each other, and L ₁ , L ₂ , L ₃ and L ₄ are alkyl which may be the same or different from each other. A ethylene group, an alkylidene group, an oxygen atom or a sulfur atom, each of R ₁ to R ₂₀ is independently hydrogen, an alkyl group, an alkoxy group, an aryl group or a cyano group, and at least two of R ₁ to R ₅ are cyano groups, At least two of R ₆ to R ₁₀ are cyano groups, at least two of R ₁₁ to R ₁₅ are cyano groups, and at least two of R ₁₆ to R ₂₀ are cyano groups:
The aromatic divalent radical in formula (1) is a divalent radical derived from an aromatic compound represented by any one of the following formulas (2) to (4):
[Formula 2]

R ₁ to R ₆ in Formula 2 each independently represent a hydrogen, an alkyl group, an alkoxy group or an aryl group, wherein at least two of R ₁ to R ₆ form a radical:
[Formula 3]

R ₁ to R ₈ in formula (3) are each independently hydrogen, alkyl group, alkoxy group or aryl group, at least two of R ₁ to R ₈ form a radical:
[Formula 4]

In Formula 4, R ₁ to R ₁₀ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group, at least two of R ₁ to R ₁₀ form a radical, and L is an alkylene group, an alkylidene group, an oxygen atom, or Sulfur atom.

delete

The compound according to claim 1, wherein in Formula 2, R ₁ and R ₄ or R ₁ and R ₃ form a radical, and the remaining substituents are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, and R ₁ , R in Formula 3 Any one of ₆ , R ₇ and R ₈ and any one of R ₂ , R ₃ , R ₄ and R ₅ form a radical, and the remaining substituents are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, Wherein any one of R ₁ to R ₅ and any one of R ₆ to R ₁₀ form a radical, and the remaining substituents are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group.

The compound according to claim 1, wherein in Formula 1, R ₃ , R ₄ , R ₈ , R ₉ , R ₁₃ , R ₁₄ , R ₁₈ and R ₁₉ are cyano groups, and R ₁ , R ₂ , R ₅ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ , R ₁₆ , R ₁₇ and R ₂₀ are each independently hydrogen or an alkyl group.

The compound of claim 1, wherein L ₁ , L ₂ , L _3, and L ₄ of Formula 1 are oxygen atoms.

A phthalonitrile resin containing the polymerization unit derived from the compound of Claim 1.

A polymerizable composition comprising the compound of claim 1 and a curing agent.

A prepolymer which is a reactant of the polymerizable composition of claim 7.

A composite comprising the phthalonitrile resin of claim 6 and a filler.

A precursor of a phthalocyanine dye comprising the compound of claim 1.

A precursor of a fluorescent brightener comprising the compound of claim 1.

A precursor of a photography sensitizer comprising the compound of claim 1.

An acid anhydride derived from the compound of claim 1.