Phthalonitrile compound

Abstract

The present application relates to a novel phthalonitrile compound and a use thereof. The phthalonitrile compound has a novel structure and can exhibit excellent effects in a use known for which a phthalonitrile compound can be applied. The use of the phthalonitrile compound can be exemplified by a material or a precursor such as a phthalonitrile resin, a phthalonitrile dye, a fluorescent whitening agent, a photographic sensitizer, or an acid anhydride.

Claims

1. A phthalonitrile resin comprising a polymerized unit derived from a compound of Formula 1 below: ##STR00011## wherein, A is an alkylene group or an alkylidene group, having 1 to 20 carbon atoms, Q.sub.1 and Q.sub.2 are an aromatic divalent radical substituted with at least one alkyl group, L.sub.1 and L.sub.2 are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group or a cyano group, provided that at least two of R.sub.1 to R.sub.5 are a cyano group and at least two of R.sub.6 to R.sub.10 are a cyano group.

2. The phthalonitrile resin according to claim 1, wherein Q.sub.1 and Q.sub.2 in Formula 1 are each independently a radical derived from an aromatic compound of Formula 2 below: ##STR00012## wherein, R.sub.a to R.sub.f are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, where two of R.sub.a to R.sub.f form a covalent bond, provided that any one of two forming said covalent bond forms a covalent bond with L.sub.1 or L.sub.2 in Formula 1 and the other forms a covalent bond with A in Formula 1, and at least one of the substituents not forming said covalent bond among R.sub.a to R.sub.f is an alkyl group.

3. The phthalonitrile resin according to claim 2, wherein the substituent present in the para position on the basis of the substituent forming a covalent bond with A in Formula 1 among R.sub.a to R.sub.f in Formula 2 forms a covalent bond with L.sub.1 or L.sub.2 in Formula 1.

4. The phthalonitrile resin according to claim 3, wherein at least one of the substituents present in the ortho or meta position on the basis of the substituent forming a covalent bond with A in Formula 1 among R.sub.a to R.sub.f in Formula 2 is an alkyl group.

5. The phthalonitrile resin according to claim 3, wherein at least one of the substituents present in the meta position on the basis of the substituent forming a covalent bond with A in Formula 1 among R.sub.a to R.sub.f in Formula 2 is an alkyl group.

6. The phthalonitrile resin according to claim 3, wherein two substituents present in the meta position on the basis of the substituent forming a covalent bond with A in Formula 1 among R.sub.a to R.sub.f in Formula 2 are an alkyl group.

7. The phthalonitrile resin according to claim 1, wherein L.sub.1 and L.sub.2 are each independently an alkylene group, an alkylidene group or an oxygen atom.

8. The phthalonitrile resin according to claim 1, wherein in Formula 1, any two of R.sub.2 to R.sub.4 are a cyano group and any two of R.sub.7 to R.sub.9 are a cyano group.

9. A polymerizable composition comprising the compound as defined in claim 1 and a curing agent.

10. A prepolymer which is reaction product of the polymerizable composition of claim 9.

11. A composite comprising the phthalonitrile resin of claim 1 and a filler.

12. The composite according to claim 11, wherein the filler is a metal material, a ceramic material, glass, a metal oxide, a metal nitride or a carbon-based material.

13. A precursor comprising the polymerizable composition of claim 9; and a filler.

14. A method for producing a composite comprising a step of curing the precursor of claim 13.

15. A precursor comprising the prepolymer of claim 10; and a filler.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 shows NMR results of the compound of Preparation Example 1.

(2) FIG. 2 shows NMR results of the compound of Preparation Example 2.

(3) FIG. 3 shows NMR results of the compound of Preparation Example 3.

MODE FOR INVENTION

(4) The phthalonitrile resins of the present application and the like will be specifically described by way of Examples and Comparative Examples, but the scope of the resins and the like is not limited to the following examples.

(5) 1. NMR, DSC and TGA Analyses

(6) The NMR analysis was carried out using an equipment (Agilent 500 MHz NMR device) according to the manufacturer's manual (solvent used: DMSO (d6) (dimethylsulfoxide-d6)).

(7) In addition, for the DSC (differential scanning calorimetry) analysis, it was measured in N.sub.2 flow atmosphere while raising the temperature from 35 C. to 450 C. at a rate of about 10 C./min using a Q20 system from TA Instrument.

(8) Furthermore, for the TGA (thermogravimetric analysis) analysis, the compound was measured in N.sub.2 flow atmosphere while raising the temperature from 25 C. to 800 C. at a rate of about 10 C./min and the polymerizalbe composition was measured in N.sub.2 flow atmosphere while raising the temperature from 25 C. to 900 C. at a rate of about 10 C./min, using a TGA e850 from Mettler-Toledo.

Preparation Example 1

(9) The compound of Formula A below was synthesized by a nitro displacement reaction. 41.0 g of bis(4-hydroxy-3,5-dimethylphenyl)methane (CAS No. 5384-21-4) and 150 mL of DMF (dimethyl formamide) were placed in a 500 mL flask (3 neck round-bottom flask) and stirred at room temperature. To the mixture, 55.4 g of 4-nitrophthalonitrile was added and dissolved by further adding 50 g of DMF thereto and stirring the mixture. 66.3 g of potassium carbonate was added thereto together with 50 g of DMF, and the temperature was raised to 85 C. with stirring. After reaction for about 5 hours, followed by cooling to room temperature, the cooled reaction solution was poured into 0.2N hydrochloric acid aqueous solution to be neutralized and precipitated, and the precipitate was filtered and then washed with water. The filtered product was dried in a vacuum oven at 100 C. for one day to remove water and residual solvent, and the desired compound was obtained. The NMR analysis results for the prepared compound were shown in FIG. 1.

(10) ##STR00007##

Preparation Example 2

(11) The compound of Formula B below was also synthesized by a nitro displacement reaction. 27.9 g of 4,4-dihydroxybiphenyl and 100 mL of DMF (dimethyl formamide) were placed in a 500 mL flask (3 neck round-bottom flask) and stirred at room temperature. To the mixture, 51.9 g of 4-nitrophthalonitrile was added and dissolved by further adding 50 g of DMF thereto and stirring the mixture. 62.2 g of potassium carbonate was added thereto together with 50 g of DMF, and the temperature was raised to 85 C. with stirring. After reaction for about 5 hours, followed by cooling to room temperature, the cooled reaction solution was poured into 0.2N hydrochloric acid aqueous solution to be neutralized and precipitated, and the precipitate was filtered and then washed with water. The filtered product was dried in a vacuum oven at 100 C. for one day to remove water and residual solvent, and the desired compound was obtained. The NMR analysis results for the prepared compound were shown in FIG. 2.

(12) ##STR00008##

Preparation Example 3

(13) The compound of Formula C below was also synthesized by a nitro displacement reaction. 0.4 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 150 mL of DMF (dimethyl formamide) were placed in a 500 mL flask (3 neck round-bottom flask) and stirred at room temperature. To the mixture, 51.9 g of 4-nitrophthalonitrile was added and dissolved by further adding 50 g of DMF thereto and stirring the mixture. 62.2 g of potassium carbonate was added thereto together with 50 g of DMF, and the temperature was raised to 85 C. with stirring. After reaction for about 5 hours, followed by cooling to room temperature, the cooled reaction solution was poured into 0.2N hydrochloric acid aqueous solution to be neutralized and precipitated, and the precipitate was filtered and then washed with water. The filtered product was dried in a vacuum oven at 100 C. for one day to remove water and residual solvent, and the desired compound was obtained. The NMR analysis results for the prepared compound were shown in FIG. 3.

(14) ##STR00009##

Preparation Example 4

(15) As the compound of Formula D below (m-APB), a product from TCI was purchased and used without further purification.

(16) ##STR00010##

(17) The physical properties such as the melting temperature (Tm) of the compounds of Preparation Examples 1 to 3 are summarized in Table 1 below.

(18) TABLE-US-00001 TABLE 1 Tm (unit: C.) Residue at 800 C. (unit: %) Preparation Example 1 193 73 Preparation Example 2 235 1.1 Preparation Example 3 183 0.5

Example 1

(19) A polymerizable composition was prepared by compounding a curing agent (compound of Preparation Example 4) to 4 g of the compound of Formula A synthesized in Preparation Example 1 so that 12 moles of the curing agent was present per mole of the compound of Formula A. The mixture can be melted at about 200 C. and rapidly cooled for 5 minutes to prepare a precursor (prepreg).

Comparative Example 1

(20) A polymerizable composition was prepared in the same manner as in Example 1, except that the compound of Formula B in Preparation Example 2 was used instead of the compound of Formula A synthesized in Preparation Example 1, and the physical properties were evaluated.

Comparative Example 2

(21) A polymerizable composition was prepared in the same manner as in Example 1, except that the compound of Formula C in Preparation Example 3 was used instead of the compound of Formula A synthesized in Preparation Example 1, and the physical properties were evaluated.

(22) The physical properties measured for the results of Example 1 and Comparative Examples 1 and 2 above are summarized in Table 2 below.

(23) TABLE-US-00002 TABLE 2 Exothermal Onset Process Residue Tm Temperature Window at 900 C. (unit: C.) (unit: C.) (unit: C.) (unit: %) Example 1 186 296 110 75 C. Example 1 233 263 30 64 C. Example 2 230 280 70 52 (C. Example: Comparative Example)

(24) From the results of Tables 1 and 2, it can be confirmed that the compound of the specific formula of the present application exhibits a low processing temperature (melting temperature, Tm) and an appropriate onset temperature, and a wide process window, and it can be seen that the compound has excellent heat resistance.