KR20170065952A

KR20170065952A - Phthalonitrile compound

Info

Publication number: KR20170065952A
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: 2017-06-14
Also published as: KR102041817B1

Abstract

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.

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.

The phthalonitrile compound can be applied in various applications. For example, a phthalonitrile compound can be used as a raw material of a so-called phthalonitrile resin. For example, a composite formed by impregnating a phthalonitrile resin with a filler such as glass fiber or carbon fiber can be used as a material for an automobile, an airplane, or a ship. 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).

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 can provide novel phthalonitrile compounds and their uses. Examples of the above applications include a phthalonitrile resin, a polymerizable composition or prepolymer for producing the same, a complex, a precursor of the complex, a pigment, a fluorescent whitening agent, a photosensitizer or an acid anhydride precursor or a raw material.

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

[Chemical Formula 1]

Wherein L ₁ , L ₂ , L ₃ and L ₄ are an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, R ₁ , A ₂ , A ₃ and A ₄ are aromatic divalent radicals, 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 are cyano groups, and at least two of R ₁₆ to R ₂₀ may be cyano groups.

In the _{Ar, A 1, A 2,} A 3 and A ₄ may be identical to or different from one _{another, L 1, L 2, L} 3 and L ₄ may also be identical to or different from each other.

The term aromatic divalent radical in the present application may, unless otherwise specified, mean a divalent moiety derived from a compound comprising benzene, benzene, or any derivative thereof. The benzene-containing compound as described above may mean a compound having two or more benzene rings which are condensed while sharing two carbon atoms or are linked by a suitable linker. An aromatic divalent radical may, for example, comprise 6 to 25, 6 to 20, 6 to 15 or 6 to 12 carbon atoms and may optionally be substituted by one or more substituents .

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

(2)

In formula (2), R ₁ to R ₆ are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, and at least two of R ₁ to R ₆ form a radical.

(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.

[Chemical 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, L is an alkylene group, an alkylidene group, Or a sulfur atom.

R ₁ to R _6, R ₁ to R ₈ or R ₁ to R ₁₀ each independently represent a hydrogen, an alkyl group or an aryl Kii are, two or more of each of the formula (IV) of formula (3) of the general formula (2) is the radical . The formation of a radical in the above may mean that the moiety is linked to another moiety of formula (1). For example, in the case of Ar in formula (1), the radical forming sites are connected to the carbon atoms on both sides, and in the case of A ₁ , the radical forming sites 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 radical-forming moiety may be connected to carbon atoms on both sides and L < ₄ >. Each of the substituents not forming a radical may be hydrogen, an alkyl group or an alkoxy group; 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, an alkyl group or an alkoxy group; 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 , 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 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, an alkyl group or an alkoxy group; 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, an alkylene group, an alkylidene group or an oxygen atom, or an oxygen atom.

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, unless otherwise specified, may mean a monovalent residue derived from a benzene or benzene structure compound described in the above aromatic divalent radicals or a derivative of any of the above have. 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 the substituent which may be optionally substituted in the alkyl group, alkoxy group, aryl group, aromatic divalent radical, alkylene group or alkylidene group in the present application include halogen such as chlorine or fluorine, glycidyl 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. Examples of the alkoxy group include a methoxy group, an ethoxy group, an ethoxy group,

In the general 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, an alkylene group, an alkylidene group or an oxygen atom or an oxygen atom.

At least two of the formula 1 R ₁ to R ₂₀ each independently represent a hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano nogiyi be, R ₁ to R ₅ is a cyano group, R ₆ to R ₁₀ and at least two of the 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. In another example, R ₁ to R ₂₀ , which are not cyano groups, are each independently hydrogen, an alkyl group or an alkoxy group; Or hydrogen or an alkyl group. In one example, 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, an alkyl group or an alkoxy group; Or hydrogen or an alkyl group.

The compounds of formula (I) can be used effectively in a variety of applications where it is known that the so-called phthalonitrile compounds can be applied. 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 low melting temperature, is excellent in reactivity with a curing agent, exhibits a wide process window, and can be effectively applied to such use. 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 of the formula (1) can be synthesized according to the synthesis method of a known organic compound. For example, the compound of the formula (1) is a reaction known as a so-called nitro displacement reaction. For example, an aromatic compound containing a hydroxy group and an aromatic compound containing a nitro group are reacted in the presence of a basic catalyst or the like And the like.

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 formula (1). 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 compound of formula (1). 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 formula (1) may be a polymerization unit formed by the reaction of the above compound with a curing agent. The kind of the curing agent that can be used in this case is not particularly limited as long as it can react with the compound of the formula (1) to form a polymer. For example, any compound known to be useful for the formation of the phthalonitrile resin . 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) described above. The polymerizable composition may further comprise a curing agent together with the compound of the formula (1).

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) contained in the composition. For example, the curing agent may be included in the polymerizable composition in an amount of about 0.02 mol to about 2 mol or about 0.02 mol to about 1.5 mol per mol of the compound of formula (1). However, the above ratios are only examples of the present application. Usually, when the ratio of the curing agent in the polymerizable composition is high, the process window tends to be narrowed, and if 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 a low melting temperature and a wide process window.

The polymerizable composition may further contain various additives including a phthalonitrile compound and the like in addition to the compound of the formula (1). 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 a fibrous material such as aramid fiber, glass fiber, carbon fiber or ceramic fiber, or a woven fabric, a nonwoven fabric, a string or a string formed by the material, Or other amorphous forms. 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 and a curing agent.

The term " prepolymer state " in the present application means a state in which the compound of formula (1) and the curing agent are in a certain degree of occurrence (for example, in a state in which so-called A or B stage polymerization is carried out) And can exhibit a suitable fluidity, for example, a state in which the composite body can be processed as described later.

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

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) of the present application is capable of achieving excellent curability, a low melting temperature and a wide process window, and accordingly, a so-called reinforced resin composite 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. Fillers that may be used include fibrous materials such as carbon fibers, aramid fibers, glass fibers or ceramic fibers, or carbon nanomaterials such as woven, non-woven, string or string formed by the materials, or carbon nanotubes or grapheme And the like, but the present invention is 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) described above with a curing agent in the molten state or 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 low melting temperature and a wide process temperature, and is superior 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 .

Figure 1 shows the NMR results of the compounds prepared in the examples.

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.

1. Nuclear magnetic resonance (NMR) analysis

NMR analysis was performed according to the manufacturer's manual using an Agilent 500 MHz NMR instrument. A sample for NMR measurement was prepared by dissolving the compound in DMSO (dimethyl sulfoxide) -d6.

2. Differential scanning calorimetry (DSC) analysis

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

3. Thermogravimetric analysis (TGA) analysis

TGA analysis was performed using a Mettler-Toledo TGA e850 instrument. In the case of the compound prepared in Preparation Example, the temperature was elevated from 25 ° C to 800 ° C at a rate of 10 ° C / min and analyzed in a N 2 flow atmosphere.

Example 1. Synthesis of Compound (PN1)

14.2 g of a compound represented by the following formula (A) (CAS No. 18066-45-0) and 50 g of dimethylformamide (DMF) were put into a 3 neck round bottom flask (RBF) and dissolved by stirring at room temperature. 20.8 g of 4-nitropthalonitrile of the following formula (B) was added, and 30 g of DMF was added and dissolved by stirring. Subsequently, 24.9 g of potassium carbonate and 30 g of DMF were added together, and the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours, cool to room temperature. The cooled reaction solution was poured into 0.2N hydrochloric acid aqueous solution to neutralize and precipitate. After filtering, it was washed with water. The filtered reaction was then dried in a vacuum oven at 100 캜 for one day. After removal of water and residual solvent, the compound of formula C (PN1) was obtained in a yield of 84% by weight.

(A)

[Chemical Formula B]

&Lt; RTI ID = 0.0 &

The NMR analysis results for the compound of formula (C) are shown in FIG. As a result of DSC analysis on the compound of the formula (C), it was confirmed that the softening point and the melting point were as low as 169.5 ° C and 247 ° C, respectively, and thus a wide process window was secured. In the TGA analysis, residues at 800 ° C were as high as 44% by weight, indicating excellent thermal stability.

Claims

A compound of formula
[Chemical Formula 1]

In the formula _{1 Ar, A 1, A 2} , A 3 and A ₄ is an aromatic divalent radical that may be the same or different from each _{other, L 1, L 2, L} 3 and L ₄ is alkyl, which may be identical or different, 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 a cyano group, 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 compound according to claim 1, wherein the aromatic divalent radical in the formula (1) is a divalent radical derived from an aromatic compound represented by any one of the following formulas (2) to (4)
(2)

In Formula 2, R ₁ to R ₆ are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group, and at least two of R ₁ to R ₆ form a radical:
(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:
[Chemical 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, L is an alkylene group, an alkylidene group, Sulfur atom.

The method of claim 2, wherein the R ₁ and R ₄ or R ₁ and R ₃ in formula (2) to form a radical, and the remaining substituents are each independently selected from the group consisting of hydrogen, an alkyl group or an aryl group, R _1, R in the formula (3) ₆ , R ₇ and R ₈ and 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, , Any one of R ₁ to R ₅ and any of R ₆ to R ₁₀ forms a radical, and the remaining substituents are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group.

According to claim 1, R _3, in formula _{1 R 4, R 8, R} 9, R 13, R 14, R 18 and R ₁₉ is cyano _{group, 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 according to claim 1, wherein L ₁ , L ₂ , L ₃ and L ₄ in the general formula (1) are oxygen atoms.

A phthalonitrile resin comprising a polymerization unit derived from the compound of claim 1.

A polymerizable composition comprising a 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 photosensitizer containing a compound of claim 1.

An acid anhydride derived from the compound of claim 1.