KR20180047288A - Compound - Google Patents

Abstract

The compounds of the present application may have 1 to 25 phthalonitrile functional groups, thereby having a curing rate and a curing density suitable for the application to which a phthalonitrile resin containing the compound of the present invention or a prepolymer thereof or a polymerizable composition forming the same can be applied. The phthalonitrile resin and the like can be applied to various applications.

Description

Compound {Compound}

This application is directed to compounds, phthalonitrile resins, polymerizable compositions, prepolymers, composites, methods of making and uses thereof.

The phthalonitrile resin can be used in a variety of applications. For example, a phthalonitrile resin is a thermosetting resin having excellent heat resistance and flame retardancy, and a composite formed by impregnating a filler such as glass fiber or carbon fiber with a phthalonitrile resin 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).

Korean Patent No. 0558158

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

The alkyl group or alkoxy group in the present application may be an alkyl group or 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 alkyl or alkoxy group may be linear, branched or cyclic, and may be optionally substituted by one or more substituents. The term alkyl group in the present application may also include a haloalkyl group described later.

The alkenyl group or alkynyl group in the present application may be an alkenyl group or an alkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms unless otherwise specified . The alkenyl or alkynyl group may be linear, branched or cyclic and, where necessary, may be substituted by one or more substituents.

The term aryl group in the present application may mean a monovalent residue derived from a benzene, a compound containing a benzene structure or a derivative of any of the above 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 single bond in the present application means that no atom is present at the site. For example, in the structure of X-Y-Z, when Y is a single bond, X and Z are directly connected to form a structure of X-Z.

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.

The term alkenyl group or alkynylene group in the present application means an alkenyl group or alkynylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, unless otherwise specified can do. The alkenyl group or alkynylene group may be straight-chain, branched-chain or cyclic. In addition, the alkenyl or alkynylene group may be optionally substituted with one or more substituents.

Examples of the substituent which may optionally be substituted in the alkyl group and the like in the present application include an epoxy group such as halogen, haloalkyl, glycidyl, glycidyl alkyl, glycidoxyalkyl or alicyclic epoxy, such as chlorine or fluorine, 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.

The present application is directed to a phthalonitrile compound. The compound of the present invention is a phthalonitrile monomer capable of controlling the number of phthalonitrile functional groups in the preparation process. The number of the phthalonitrile functional groups is controlled so that a polymerizable composition having a curing rate and a curing density Lt; RTI ID = 0.0 > phthalonitrile < / RTI >

It is possible to prepare a liquid phthalonitrile resin or a prepolymer thereof when the above compound is used alone or when an appropriate amount is contained in the blend. Such a compound can be extremely high in application of phthalonitrile resin. For example, the phthalonitrile resin can be applied to a high heat-resisting grease or a sealing material due to the above-mentioned characteristics, Or may be mixed with an appropriate additive such as epoxy to be used as an adhesive.

Such a compound of the present application may be represented by the following formula (1) having at least one substituent represented by the following formula (3).

[Chemical Formula 1]

In the general formula (1), R ¹ to R ⁵ are the same or different substituent or hydroxyl group represented by the following general formula (2) or (3). The compound of the present application has at least one substituent represented by the following general formula (3), and can be used for the phthalonitrile resin or the prepolymer described above.

(2)

In formula (2), L ₁ is an oxygen atom, -C (= O) -O- or -OC (= O) -. In one example, L < ₁ > may be -OC (= O) -.

In Formula 2, R ⁶ to R ¹⁰ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a hydroxy group or to be described later, and the substituent represented by Formula 3 or Formula 4, R ⁶ to R ¹⁰ of at least One is a substituent represented by the following general formula (4). R ⁶ to R ¹⁰ may be the substituents of formula (3), so that the compounds of the present application can be prepared by adjusting the number of phthalonitrile functional groups so that the polymerizable composition comprising the compound of the present application has a suitable curing rate and curing density .

In one example, among R ⁶ to R ¹⁰ , a substituent which is not a substituent represented by the following general formula (3) or (4) to be described later may be independently a hydrogen atom, an alkyl group, an alkoxy group or a hydroxy group, or may be a hydrogen atom or a hydroxy group have. The compound of the present application has the above-mentioned structure, so that the number of the phthalonitrile functional groups included in the compound can be easily controlled, and as a result, the curing rate and the curing density of the polymerizable composition including the compound of the present application can be used As shown in FIG.

In one example, R ⁷ or R ⁹ may be a substituent represented by Formula (4). In another example, the formula R ⁶ and R ¹⁰ is a hydrogen atom or an alkyl group, R ⁷ to R ⁹ and one R ⁷ or R ⁹ is a substituent of the formula (4), R ⁷ to R ⁹ of the substituents represented by the following general formula (4) R ⁷ to R ⁹ other than a hydroxyl group may be a hydroxy group or a substituent of the following formula (3). By virtue of the above structure, the compound of the present application is a compound wherein, in each of the five substituents which are the same as or different from each other, one of 15 substituents corresponding to R ⁷ to R ⁹ of the substituent represented by the general formula (4) To 15 of them may be a substituent represented by the general formula (3). Accordingly, the compounds of the present application contain 5 substituents represented by the following formula (4) in which 0 to 3 phthalonitrile functional groups can be connected to each other through an oxygen atom and the like. Of the substituents represented by R ⁷ to R ⁹ , 2 may contain a substituent represented by the general formula (2) in which the phthalonitrile functional group can be connected through an oxygen atom or the like, and thus may have from 1 to 25 phthalonitrile functional groups. Since the compounds of the present application may contain from 1 to 25 phthalonitrile functional groups as described above, the curing rate and the curing density of the polymerizable compositions comprising the compounds of the present application can be controlled by controlling the number of the phthalonitrile functional groups And can be suitably adjusted according to the application.

In another example, in R ¹ to R ⁵ which are the same or different from each other and represented by the general formula (2), one to ten of R ⁷ to R ⁹ , which is not a substituent represented by the general formula (4) Lt; / RTI > The compound of the present application can be easily modified in the number of the phthalonitrile functional groups included in the compound of the present invention since the substituent represented by the formula 3 can be substituted as described above, The curing rate and the curing density of the composition can be appropriately adjusted depending on the application.

 (3)

In formula (3), R ¹¹ to R ¹⁵ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group or a cyano group, and at least two of R ¹¹ to R ¹⁵ are cyano groups. In one example, substituents which are not cyano groups in R ¹¹ to R ¹⁵ may each independently be a hydrogen atom or an alkyl group. In one example, R ¹² and R ¹³ may be cyano groups. Since at least two of R ¹¹ to R ¹⁵ , particularly R ¹² and R ^13, are cyano groups, the compound of the present application may have at least one functional group derived from phthalonitrile.

 [Chemical Formula 4]

In formula (4), L ₂ is an oxygen atom, -C (= O) -O- or -OC (= O) -. In one example, L < ₂ > may be -OC (= O) -.

In formula (4), R ¹⁶ to R ²⁰ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, a hydroxy group or a substituent represented by the above-described formula (3). In one example, substituents other than the substituent represented by the general formula (3) among R ¹⁶ to R ²⁰ are each independently a hydrogen atom, an alkyl group, an alkoxy or a hydroxy group, or in another example, a hydrogen atom or a hydroxy group. The compound of the present application has the above-mentioned structure, so that the number of the phthalonitrile functional groups included in the compound can be easily controlled, and as a result, the curing rate and the curing density of the polymerizable composition including the compound of the present application can be used As shown in FIG.

The compounds of the present application may, in one example, have from 1 to 25 phthalonitrile functionalities, depending on the reaction conditions, from one starting material. For example, the compounds of the present application can be prepared via the reaction of tannic acid with 4-nitropthalonitrile. In particular, by controlling the molar ratio of the 4-nitrophthalonitrile to be reacted with the tannic acid, the number of the phthalonitrile functional groups introduced into the compound of the formula (1) is controlled to obtain a compound having 1 to 25 phthalonitrile functional groups have.

When the compound is applied to the production of a phthalonitrile resin or a prepolymer thereof, the disadvantages of the processability and the impact strength of the phthalonitrile resin can be improved, and the liquid resin, the prepolymer thereof, the resin in the form of a rubber Or forming the prepolymer, or may be utilized for various applications such as high-temperature grease, sealing materials, or adhesives.

Such compounds 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 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 above compound can be synthesized according to a synthesis method of a known organic compound.

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 include other phthalonitrile compounds in addition to the polymerized units of the above-mentioned compounds, that is, polymerized units of phthalonitrile compounds having chemical structures different from those of the above compounds. 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.

As the phthalonitrile compound which may be contained in the phthalonitrile resin as a polymerization unit in addition to the above compound, there may be mentioned a compound represented by the following general formula (5), but the present invention is not limited thereto.

[Chemical Formula 5]

In formula (5), R ²¹ to R ²⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, In formula (5), at least two, or two to three, of R ²¹ to R ²⁶ may be a substituent of the following formula (6) or (7).

The substituents of the above formula (6) or (7) in which at least two or two to three are present in the formula (5) may exist at ortho, meta or para positions with respect to each other.

[Chemical Formula 6]

In the formula 6 L ₃ is a single bond, an oxygen atom, sulfur _{atom, -S (= O) 2 -} , a carbonyl group, an alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 1} - or -X ₁ -C (= O) -, and wherein X ₁ is an oxygen atom, sulfur atom, -S (= O) ₂ -, and the alkylene, alkenylene or alkynylene group, R ²⁷ to R ³¹ are each Independently, hydrogen, an alkyl group, an alkoxy group, an aryl group or a cyano group, and two or more of R ²⁷ to R ³¹ are cyano groups. At least two cyano groups in formula (6) may be present at ortho, meta or para positions relative to each other.

(7)

In formula 7 L ₄ is a single bond, an oxygen atom, sulfur _{atom, -S (= O) 2 -} , a carbonyl group, an alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 2} - , or -X ₂ -C (= O) -, and wherein X ₂ is oxygen atom, sulfur atom, -S (= O) ₂ -, and the alkylene, alkenylene or alkynylene group, R ³² to R ³⁶ are each An alkyl group, an alkoxy group, an aryl group or a substituent of the above formula (6), provided that at least one or at least one of R ³² to R ³⁶ is a substituent of the above formula (6). The substituent of Formula 6, which is present in at least one of Formula 7, may be present at ortho, meta or para positions based on L ₄ .

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.

In one example, as the curing agent, a compound of the following formula (8) may be used.

[Chemical Formula 8]

Wherein R ³⁷ to R ⁴² are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, an amine group or a substituent group of the following formula (9), provided that at least two of R ³⁷ to R ⁴² are an amine group or Lt; / RTI >

[Chemical Formula 9]

In Formula 9 L ₅ is an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, R ⁴³ to R ⁴⁷ is hydrogen, an alkyl group, an alkoxy group, an aryl group, or an amine marvelous being, R ⁴³ to at least one of R ⁴⁷ is Amin wait.

When the substituent of formula (9) is present, L ₅ in the above structure may be linked to the benzene ring of formula (8).

In one example, the curing agent may be a compound wherein two of R ³⁷ to R ⁴² in Formula (8) are substituents of Formula (9). In this case, in the formula (8), the substituents of the above two formula (9) may be a structure in which the other one is present at the otho, meta or para position with respect to any one of them. In this case, any one of R ⁴³ to R ⁴⁷ in the substituent of Formula 9 may be an amine group.

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).

The polymerizable composition may contain another phthalonitrile compound in addition to the compound of the above formula (1). As the other phthalonitrile compound or curing agent, 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. The above ratio can be adjusted so that the desired curability can be ensured in consideration of, for example, the ratio or type of the curable component such as the compound of the formula (1) or other phthalonitrile compound contained in the composition. For example, the curing agent may be present in the polymerizable composition in an amount of from about 0.02 mole to about 2.5 moles, from about 0.02 mole to about 2.0 moles, or from about 0.02 mole to about 1.5 moles per mole of the compound of Formula 1 and the other compound and the other phthalonitrile compound May be included. 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 compositions of the present application may have a cure rate and cure density that is appropriate for the application to which they are applied. The compounds of formula (I) contained in the polymerizable compositions of the present application may contain from 1 to 25 phthalonitrile functional groups and thus may have suitable curing speeds and curing densities depending on the application to which they are applied.

The polymerizable composition may further comprise various additives. 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 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. 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 prepolymer may also have a cure rate and cure density suitable for the application to which it is applied. Since the compound of Formula 1 contained in the prepolymer may contain 1 to 25 phthalonitrile functional groups, the curing rate and the curing density of the prepolymer can be easily controlled by controlling the number of the phthalonitrile functional groups.

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, it is possible to achieve a curing rate and a curing density suitable for the application purpose through the compound of the formula (1) of the present application, and thus to provide a so-called reinforced polymer composite of excellent physical properties including various fillers 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) 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 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 compounds of the present application can have from 1 to 25 phthalonitrile functional groups and are suitable for use in applications where the phthalonitrile resin or prepolymer containing the compound of the present application or the polymerizable composition forming the same is applied, Density can be obtained. These phthalonitrile resins and the like can be applied to various applications, for example, in all fields to which so-called engineering plastics can be applied, and in addition, they can be applied to various fields such as grease, sealing materials, adhesives, pressure- Heat-resistant materials in various industries including automobile industry, electronics industry, and the like. The compound can also be applied to the production of a precursor of a phthalocyanine dye, a precursor of a fluorescent whitening agent, a precursor of a photographic sensitizer, or an acid anhydride.

1 to 6 are NMR (Nuclear Magnetic Resonance) analysis results for the compound prepared in Preparation 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.

1. Nuclear magnetic resonance (NMR) analysis

NMR analysis was performed according to the manufacturer's manual using an Agilent 500 MHz NMR instrument. Samples for determination of NMR were prepared by dissolving the compounds in DMSO (dimethyl sulfoxide) -d6 and Acetone-d6.

2. Differential scanning calorimetry (DSC) analysis

DSC analysis was performed in a nitrogen environment (N ₂ flow) using a TA instrument Q20 system at a heating rate of 10 ° C / min from 35 ° C to 450 ° C.

3. TGA ( Thermogravimetric Analysis ) analysis

TGA analysis was performed using a Mettler-Toledo TGA e850 instrument. The compound prepared in Preparation Example and the composition prepared in Example or Comparative Example were analyzed in a nitrogen atmosphere (N ₂ flow) while raising the temperature from 25 ° C to 900 ° C at a heating rate of 10 ° C / minute.

Manufacturing example  1. Synthesis of Compound (PN1)

Compound PN1 was synthesized in the following manner. 34.024 g of the compound represented by the following formula (A) was added to a 3-neck round bottom flask (RBF) containing 150 g of DMF (Dimethyl Formamide) and dissolved by stirring at room temperature. Then, 17.3 g of the compound of the following formula (B) was added and stirred until dissolved. Then, 22.1 g of calcium carbonate and 41 g of DMF (Dimethyl Formamide) were added together and the temperature was raised to 85 ° C. After reacting for about 5 hours in this state, it was cooled to room temperature and neutralized and precipitated by pouring into a hydrochloric acid aqueous solution of 0.2N concentration. The precipitate was filtered, washed with water, dried and then redispersed in chloroform to effect filtration. The filtered product was dried in a 100 < 0 > C vacuum oven to remove water and residual solvent to give compound PN1. The NMR analysis results for the compound PN1 thus prepared are shown in FIG.

(A)

[Chemical Formula B]

Manufacturing example  2. Synthesis of Compound (PN2)

Compound PN2 was synthesized in the same manner as described in Preparation Example 1 except that 34.024 g of the compound of Formula A, 34.6 g of the compound of Formula B, 35.9 g of calcium carbonate and 194.2 g of DMF (Dimethyl Formamide) . The NMR analysis results for the prepared compounds are shown in Fig.

Manufacturing example  3. Synthesis of Compound (PN3)

Compound PN3 was synthesized in the same manner as described in Preparation Example 1 except that the amount of each compound used was 15.311 g of the compound of Formula A, 24.5 g of the compound of Formula B, 28 g of calcium carbonate and 162.1 g of DMF (Dimethyl Formamide) The amount was input. The NMR analysis results for the prepared compounds are shown in Fig.

Manufacturing example  4. Synthesis of Compound (PN4)

Compound PN4 was synthesized in the same manner as described in Preparation Example 1 except that the amount of each compound used was 11.9 g of the compound of Formula A, 25.5 g of the compound of Formula B, 29 g of calcium carbonate and 164.2 g of DMF (Dimethyl Formamide) The amount was input. The NMR analysis results for the prepared compounds are shown in Fig.

Manufacturing example  5. Synthesis of Compound (PN5)

Compound PN5 was synthesized in the same manner as described in Preparation Example 1 except that the amount of each compound used was changed to 8.5 g of the compound of Formula A, 27.2 g of the compound of Formula B, 31.1 g of calcium carbonate and 173 g of DMF The amount was input. The NMR analysis results for the prepared compounds are shown in Fig.

Manufacturing example  6.

The compound of the following formula (C) was also synthesized by nitro displacement reaction. 27.9 g of 4,4'-dihydroxybiphenyl and 100 mL of dimethylformamide (DMF) were placed in a 3-neck round-bottom flask (RBF) and stirred at room temperature. 51.9 g of 4-nitrophthalonitrile was added to the mixture, and 50 g of DMF was further added and dissolved by stirring. 62.2 g of potassium carbonate was added together with 50 g of DMF, and the temperature was raised to 85 ° C with stirring. After reacting for about 5 hours and cooling to room temperature, the reaction solution at room temperature was poured into 0.2N hydrochloric acid aqueous solution to neutralize and precipitate. The precipitate was filtered and washed with water. The filtered product was dried in a 100 < 0 > C vacuum oven for one day to remove water and residual solvent, and the desired compound was obtained. The NMR analysis results for the prepared compound are shown in Fig.

≪ RTI ID = 0.0 &

The physical properties of the compounds of Preparation Examples 1 to 5 are summarized in Table 1 below.

A Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Heat generation start temperature
(Unit: ° C) - 202 214 212 219 231 Heat energy
(Unit: J / g) - 362 341 221 182 204 The residue at 900 ° C
(unit: %) 24.86 43.11 40.75 46.78 49.86 49.66

According to the results shown in Table 1, specific compounds of the present invention derived from the formula (A) in which decomposition occurs at a high temperature of 200 ° C or higher exhibit a tendency to exotherm with self-curing, and the heat resistance of the compound itself is also improved.

Example  One.

The compound of the compound PN2 synthesized in Production Example 2 was polymerized singly, and the properties thereof were evaluated.

Comparative Example  One.

The compound of the formula (C) synthesized in Production Example 6 was polymerized singly and the properties thereof were evaluated.

The physical properties measured for the results of Example 1 and Comparative Example 1 are summarized in Table 2 below.

Example 1 Comparative Example 1 The residue at 900 ° C
(unit: %) 53.76 22.20

From the results of Tables 1 and 2, it can be seen that the compound of the specific formula of the present application exhibits various exothermic tendencies by controlling the number of polyfunctional groups from one compound of formula (A) and excellent heat resistance.

Claims (13)

A compound represented by the following formula (1) having at least one substituent represented by the following formula (3):
[Chemical Formula 1]

In the general formula (1), R ¹ to R ⁵ are the same or different substituent or hydroxyl group represented by the general formula (2) or (3)
(2)

In formula (2), L ₁ is an oxygen atom, -C (= O) -O- or -OC (= O) -, and R ⁶ to R ¹⁰ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, A hydroxyl group, or a substituent represented by the following formula (3) or (4), and at least one of R ⁶ to R ¹⁰ is a substituent represented by the following formula (4)
(3)

In formula (3), R ¹¹ to R ¹⁵ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group or a cyano group, and at least two of R ¹¹ to R ¹⁵ are cyano groups;
[Chemical Formula 4]

In formula (4), L ₂ is an oxygen atom, -C (= O) -O- or -OC (= O) -, and R ¹⁶ to R ²⁰ are each independently a hydrogen atom, an alkyl group, an alkoxy group, A hydroxy group, or a substituent group represented by the above-described formula (3). The compound according to claim 1, wherein the substituent which is not a substituent represented by the general formula (3) or the formula (4) in R ⁶ to R ¹⁰ and the substituent which is not a substituent group represented by the general formula (3) in R ¹⁶ to R ²⁰ are each independently a hydrogen atom, An alkoxy group or a hydroxy group. The compound according to Claim 1, wherein the substituent which is not a substituent represented by the general formula (3) or (4) in R ⁶ to R ¹⁰ and the substituent which is not a substituent group represented by the general formula (3) in R ¹⁶ to R ²⁰ are each independently a hydrogen atom or a hydroxy group compound. The compound according to claim 1, wherein the substituent which is not a cyano group in each of R ¹¹ to R ¹⁵ is independently a hydrogen atom or an alkyl group. The compound according to claim 1, wherein R ⁷ or R ⁹ in the formula (2) is a substituent represented by the formula (4). The compound according to claim 1, wherein, in R ¹ to R ⁵ which are the same or different from each other and represented by the general formula (2), 1 to 10 of R ⁷ to R ⁹ which are not substituents represented by the general formula (4) are substituents represented by the general formula (3). The compound according to claim 1, wherein R ¹² and R ¹³ in formula (3) are cyano groups. The compound according to claim 5, wherein 1 to 15 of the 15 substituents corresponding to R ⁷ to R ⁹ of the substituent represented by the general formula (4) in each of the 5 substituents, which are the same or different, Lt; / RTI > The compound according to claim 1, which comprises 1 to 25 substituents of the formula (3). A phthalonitrile resin comprising a polymerization unit derived from the compound of Chemical Formula 1 of claim 1. A polymerizable composition comprising a compound of claim 1. A prepolymer which is a reactant of the polymerizable composition of claim 11. A composite comprising the phthalonitrile resin of claim 10 and a filler.

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