PHTHALONITRILE COMPOUND

Abstract

The present application can provide a phthalonitrile compound and a use thereof. The present application can provide a phthalonitrile compound capable of forming a phthalonitrile resin by self-curing or of serving as a curing agent after being mixed with another phthalonitrile compound, and a use of the phthalonitrile compound. The phthalonitrile compound can form a phthalonitrile resin by rapid self-curing even at a low temperature and does not create any defects resulting from the use of a conventional curing agent. Also, the phthalonitrile compound can be applied as a curing agent after being mixed with another compound, in which case, even if the content of the compound applied as a curing agent increases, the total content of the phthalonitrile resin obtained does not decrease, and thus a resin exhibiting an excellent degree of cure can be provided.

Claims

1. A compound of Formula 1 below: ##STR00012## wherein, Ar.sub.1 and Ar.sub.2 are each independently an aromatic divalent radical substituted with at least one amino group or hydroxy group, L, L.sub.1 and L.sub.2 are each independently a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom or S(O).sub.2, and 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 compound according to claim 1, wherein the aromatic divalent radical in Formula 1 is a divalent radical derived from an aromatic compound represented by Formula 2 below: ##STR00013## wherein, R.sub.1 to R.sub.6 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group or an amino group, provided that at least two of R.sub.1 to R.sub.6 form radicals, and at least one of R.sub.1 to R.sub.6 is a hydroxy group or an amino group.

3. The compound according to claim 1, wherein the aromatic divalent radical in Formula 1 is a divalent radical derived from an aromatic compound represented by Formula 3 below: ##STR00014## wherein, R.sub.1 to R.sub.8 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group or an amino group, provided that at least two of R.sub.1 to R.sub.8 form radicals, and at least one of R.sub.1 to R.sub.8 is a hydroxy group or an amino group.

4. The compound according to claim 1, wherein the aromatic divalent radical in Formula 1 is a divalent radical derived from an aromatic compound represented by Formula 4 below: ##STR00015## wherein, R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group or an amino group, provided that at least two of R.sub.1 to R.sub.10 form radicals, L is an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, and at least one of R.sub.1 to R.sub.10 is a hydroxy group or an amino group.

5. (canceled)

6. The compound according to claim 2, wherein the substituent at the meta or para position based on the substituent forming a covalent bond with L of Formula 1 among R.sub.1 to R.sub.6 of Formula 2 is a hydroxy group or an amino group.

7. The compound according to claim 1, wherein L in Formula 1 is a single bond, an alkylene group, an alkylene group substituted with a halogen atom, an alkylidene group, an alkylidene group substituted with a halogen atom, or S(O).sub.2.

8. The compound according to claim 1, wherein L.sub.1 and L.sub.2 in Formula 1 are an oxygen atom.

9. A phthalonitrile resin comprising polymerized units derived from the compound of claim 1.

10. A polymerizable composition comprising the compound of claim 1.

11. The polymerizable composition according to claim 10, wherein the polymerizable composition does not comprise a compound containing an amine group or a hydroxy group except for the compound of Formula 1.

12. The polymerizable composition of claim 10, further comprising a phthalonitrile compound other than the compound of Formula 1.

13. A prepolymer which is a reactant of the polymerizable composition of claim 10.

14. A composite comprising the phthalonitrile resin of claim 9 and a filler.

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

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

17. A precursor of a photographic sensitizer containing the compound of claim 1.

18. An acid anhydride derived from the compound of claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0057] FIGS. 1 to 6 are each NMR analysis results for the compounds prepared in Preparation Examples 1 to 6.

MODE FOR INVENTION

[0058] 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.

[0059] 1. Nuclear Magnetic Resonance (NMR) Analysis

[0060] The NMR analysis was performed according to the manufacturer's manual using a 500 MHz NMR instrument from Agilent. A sample for NMR measurement was prepared by dissolving the compound in DMSO (dimethyl sulfoxide)-d6.

[0061] 2. DSC (Differential Scanning Calorimetry) Analysis

[0062] The DSC analysis was performed in N.sub.2 flow atmosphere, while raising the temperature from 35 C. to 450 C. at a rate of temperature increase of 10 C./min with a Q20 system from TA instrument.

[0063] 3. TGA (Thermogravimetric Analysis) Analysis

[0064] The TGA analysis was performed using a TGA e850 instrument from Mettler-Toledo. In the case of the compounds prepared in Preparation Examples, they were analyzed in N2 flow atmosphere, while raising the temperature from 25 C. to 800 C. at a rate of temperature increase of 10 C./min.

PREPARATION EXAMPLE 1

Synthesis of Compound (PN1)

[0065] The compound (PN1) of Formula A below was synthesized in the following manner. 54.9 g of the compound of Formula B below and 150 g of DMF (dimethyl formamide) were put into a 3 neck RBF (round bottom flask), stirred at room temperature and dissolved. Subsequently, 51.9 g of the compound of Formula C below was added thereto, and 50 g of DMF was added thereto, and then the mixture was stirred and dissolved. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added thereto together and the mixture was reacted in a state where the temperature was raised to 85 C. with stirring, and then cooled to room temperature. The cooled reaction solution was poured into 0.2N hydrochloric acid aqueous solution to be neutralized and precipitated, followed by filtering and then washing with water. Thereafter, the filtered reactant was dried in a vacuum oven at 100 C. for 1 day, and after removal of water and residual solvent, the compound of Formula A below was obtained in a yield of about 85% by weight. The NMR results for the compound of Formula A were described in FIG. 1.

##STR00005##

PREPARATION EXAMPLE 2

Synthesis of Compound (PN2)

[0066] The compound (PN2) of Formula D below was synthesized in the following manner. 32.4 g of the compound of Formula E below and 130 g of DMF (dimethyl formamide) were put into a 3 neck RBF (round bottom flask), stirred at room temperature and dissolved. Subsequently, 51.9 g of the compound of Formula C in Preparation Example 1 above was added thereto, and 50 g of DMF was added thereto, and then the mixture was stirred and dissolved. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added thereto together and the temperature was raised to 85 C. with stirring. The mixture was reacted in this state for about 5 hours, and then cooled to room temperature. The cooled reaction solution was poured into 0.2N hydrochloric acid aqueous solution to be neutralized and precipitated, followed by filtering and then washing with water. Thereafter, the filtered reactant was dried in a vacuum oven at 100 C. for 1 day, and after removal of water and residual solvent, the compound of Formula D below was obtained in a yield of about 80% by weight. The NMR results for the compound of Formula D were described in FIG. 2.

##STR00006##

PREPARATION EXAMPLE 3

Synthesis of Compound (PN3)

[0067] The compound (PN3) of Formula F below was synthesized in the following manner. 42 g of the compound of Formula G below and 200 g of DMF (dimethyl formamide) were put into a 3 neck RBF (round bottom flask), stirred at room temperature and dissolved. Subsequently, 51.9 g of the compound of Formula C in Preparation Example 1 above was added thereto, and 50 g of DMF was added thereto, and then the mixture was stirred and dissolved. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added thereto together and the temperature was raised to 85 C. with stirring. The mixture was reacted in this state for about 5 hours, and then cooled to room temperature. The cooled reaction solution was poured into 0.2N hydrochloric acid aqueous solution to be neutralized and precipitated, followed by filtering and then washing with water. Thereafter, the filtered reactant was dried in a vacuum oven at 100 C. for 1 day, and after removal of water and residual solvent, the compound of Formula F below was obtained in a yield of about 82% by weight. The NMR results for the compound of Formula F were described in FIG. 3.

##STR00007##

PREPARATION EXAMPLE 4

Synthesis of Compound (PN4)

[0068] The compound (PN4) of Formula H below was synthesized in the following manner. 27.9 g of the compound of Formula I below and 100 g of DMF (dimethyl formamide) were put into a 3 neck RBF (round bottom flask), stirred at room temperature and dissolved. Subsequently, 51.9 g of the compound of Formula C in Preparation Example 1 above was added thereto, and 50 g of DMF was added thereto, and then the mixture was stirred and dissolved. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added thereto together and the temperature was raised to 85 C. with stirring. The mixture was reacted in this state for about 5 hours, and then cooled to room temperature. The cooled reaction solution was poured into 0.2N hydrochloric acid aqueous solution to be neutralized and precipitated, followed by filtering and then washing with water. Thereafter, the filtered reactant was dried in a vacuum oven at 100 C. for 1 day, and after removal of water and residual solvent, the compound of Formula H below was obtained in a yield of about 83% by weight. The NMR results for the compound of Formula H were described in FIG. 4.

##STR00008##

PREPARATION EXAMPLE 5

Synthesis of Compound (PN5)

[0069] 50.4 g of the compound of Formula K below and 150 g of DMF (dimethyl formamide) were put into a 3 neck RBF (round bottom flask), stirred at room temperature and dissolved. Subsequently, 51.9 g of the compound of Formula C in Preparation Example 1 above was added thereto, and 50 g of DMF was added thereto, and then the mixture was stirred and dissolved. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added thereto together and the temperature was raised to 85 C. with stirring. The mixture was reacted in this state for about 5 hours, and then cooled to room temperature. The cooled reaction solution was poured into 0.2N hydrochloric acid aqueous solution to be neutralized and precipitated, followed by filtering and then washing with water. Thereafter, the filtered reactant was dried in a vacuum oven at 100 C. for 1 day, and after removal of water and residual solvent, the compound (PN5) of Formula J below was obtained in a yield of about 87% by weight. The NMR results for the compound of Formula J were described in FIG. 5.

##STR00009##

PREPARATION EXAMPLE 6

Synthesis of Compound (PN6)

[0070] The compound of Formula L below was synthesized in the following manner. 32.7 g of the compound of Formula M below and 120 g of DMF (dimethyl formamide) were put into a 3 neck RBF (round bottom flask), stirred at room temperature and dissolved. Subsequently, 51.9 g of the compound of Formula C in Preparation Example 1 above was added thereto, and 50 g of DMF was added thereto, and then the mixture was stirred and dissolved. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added thereto together and the temperature was raised to 85 C. with stirring. The mixture was reacted in this state for about 5 hours, and then cooled to room temperature. The cooled reaction solution was poured into 0.2N hydrochloric acid aqueous solution to be neutralized and precipitated, followed by filtering and then washing with water. Thereafter, the filtered reactant was dried in a vacuum oven at 100 C. for 1 day, and after removal of water and residual solvent, the compound (PN6) of Formula L below was obtained in a yield of about 80% by weight. The NMR results for the compound of Formula L were described in FIG. 5.

##STR00010##

PREPARATION EXAMPLE 7

Synthesis of Compound (CA)

[0071] As the compound (CA) of Formula N below, a commercial product from TCI (Tokyo Chemical Industry Co., Ltd.) was purchased and used without further purification.

##STR00011##

EXAMPLE 1

[0072] The exothermal onset temperature and exothermal maximum temperature of the compound (PN1) of Preparation Example 1 were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the compound (PN1) of Preparation Example 1 was cured at 240 C. for 2 hours using an IR curing oven.

EXAMPLE 2

[0073] The exothermal onset temperature and exothermal maximum temperature of the compound (PN2) of Preparation Example 2 were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the compound (PN2) of Preparation Example 2 was cured at 240 C. for 2 hours using an IR curing oven.

EXAMPLE 3

[0074] The exothermal onset temperature and exothermal maximum temperature of the compound (PN3) of Preparation Example 3 were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the compound (PN3) of Preparation Example 3 was cured at 240 C. for 2 hours using an IR curing oven.

EXAMPLE 4

[0075] The compound (PN1) of Preparation Example 1 and the compound (PN4) of Preparation Example 4 were mixed so that the compound (PN1) of Preparation Example 1 was present in about 0.2 moles per mole of the compound (PN4) of Preparation Example 4. Then, the exothermal onset temperature and the exothermal maximum temperature of the mixture were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the mixture was cured at 240 C. for 2 hours using an IR curing oven.

EXAMPLE 5

[0076] The compound (PN1) of Preparation Example 1 and the compound (PN5) of Preparation Example 5 were mixed so that the compound (PN1) of Preparation Example 1 was present in about 0.2 moles per mole of the compound (PN5) of Preparation Example 5. Then, the exothermal onset temperature and the exothermal maximum temperature of the mixture were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the mixture was cured at 240 C. for 2 hours using an IR curing oven.

EXAMPLE 6

[0077] The compound (PN1) of Preparation Example 1 and the compound (PN6) of Preparation Example 6 were mixed so that the compound (PN1) of Preparation Example 1 was present in about 0.2 moles per mole of the compound (PN6) of Preparation Example 6. Then, the exothermal onset temperature and the exothermal maximum temperature of the mixture were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the mixture was cured at 240 C. for 2 hours using an IR curing oven.

COMPARATIVE EXAMPLE 1

[0078] The exothermal onset temperature and exothermal maximum temperature of the compound (PN4) of Preparation Example 4 were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the compound (PN4) of Preparation Example 4 was cured at 240 C. for 2 hours using an IR curing oven.

COMPARATIVE EXAMPLE 2

[0079] The exothermal onset temperature and exothermal maximum temperature of the compound (PN5) of Preparation Example 5 were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the compound (PN5) of Preparation Example 5 was cured at 240 C. for 2 hours using an IR curing oven.

COMPARATIVE EXAMPLE 3

[0080] The exothermal onset temperature and exothermal maximum temperature of the compound (PN6) of Preparation Example 6 were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the compound (PN6) of Preparation Example 6 was cured at 240 C. for 2 hours using an IR curing oven.

COMPARATIVE EXAMPLE 4

[0081] The compound (PN4) of Preparation Example 4 and the compound (CA) of Preparation Example 7 were mixed so that the compound (CA) of Preparation Example 7 was present in about 0.2 moles per mole of the compound (PN4) of Preparation Example 4. Then, the exothermal onset temperature and the exothermal maximum temperature of the mixture were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the mixture was cured at 240 C. for 2 hours using an IR curing oven.

COMPARATIVE EXAMPLE 5

[0082] The compound (PN5) of Preparation Example 5 and the compound (CA) of Preparation Example 7 were mixed so that the compound (CA) of Preparation Example 7 was present in about 0.2 moles per mole of the compound (PN5) of Preparation Example 5. Then, the exothermal onset temperature and the exothermal maximum temperature of the mixture were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the mixture was cured at 240 C. for 2 hours using an IR curing oven.

COMPARATIVE EXAMPLE 6

[0083] The compound (PN6) of Preparation Example 6 and the compound (CA) of Preparation Example 7 were mixed so that the compound (CA) of Preparation Example 7 was present in about 0.2 moles per mole of the compound (PN6) of Preparation Example 6. Then, the exothermal onset temperature and the exothermal maximum temperature of the mixture were confirmed through the DSC analysis. In addition, the residue at Td 10% and 800 C. was confirmed through the TGA analysis for the material in which the mixture was cured at 240 C. for 2 hours using an IR curing oven.

[0084] The measurement results of Examples and Comparative Examples above were summarized and described in Table 1 below.

TABLE-US-00001 TABLE 1 Exothermal Exothermal Onset Maximum Residue at Temperature Temperature Td 10% 800 C. Example 1 255 261 472 59.6 2 238 245 444 69 3 166 194 369 60.2 4 258 265 502 70 5 260 268 473 58.6 6 248 256 479 63.7 Comparative 1 455 20.2 Example 2 422 7.3 3 430 6.4 4 279 283 508 69.5 5 358 376 496 60.4 6 301 304 478 63.4

[0085] In Table 1, first, comparing the results of Examples 1 to 3 and Comparative Examples 1 to 3, curing peaks in the case of Examples 1 to 3 where each was even in a state of a single compound were confirmed so that exothermal onset temperatures and the exothermal maximum temperatures could be confirmed, whereas in Comparative Examples 1 to 3, no curing peak could be confirmed even in a state where the temperature was raised to 450 C. Also, in the case of Examples 1 to 3, as a result of curing in the IR curing oven, cross-linking reaction occurred even within a relatively short time (2 hours), so that the residue at 800 C. was 60 to 70% and exhibited high heat resistance, but in the case of Comparative Examples 1 to 3, even after being maintained in the curing oven, the residue at 800 C. was in a level of 6 to 20%.

[0086] In the case of Examples 4 to 6, which were the mixtures of the compounds of Comparative Examples 1 to 3 and the compound of Example 1, respectively, it could be seen from the result of confirming DSC that the curing of the compounds of Comparative Examples 1 to 3, in which the curing reaction did not proceed alone, occurred, whereby the residue at 800 C. was greatly improved to 60 to 70%.

[0087] On the other hand, comparing the results of Comparative Examples 4 to 6 and Examples 4 to 6, it was confirmed that the curing in Examples 4 to 6, to which the compound (PN1) of Preparation Example 1 was applied, was initiated at a lower temperature over Comparative Examples 4 to 6 to which the compound (CA) of Preparation Example 7 as the known curing agent was applied, whereby it could be seen that Examples 4 to 6 exhibited more excellent rapid curability.

[0088] From these results, it can be seen that self-curability can be ensured through the use of the compound of the present invention, thereby avoiding the void problem or the like which occurs when a mono-molecular curing agent or the like is introduced. In addition, it is possible to secure a higher cure degree by preventing the decrease of the monomer ratio or the like due to the content of the curing agent from the above characteristics, thereby expecting an improved result even in terms of thermal and mechanical properties and increasing the productivity through reduction of the process time by lowering the curing temperature and shortening the curing time.