Phthalonitrile compound

Abstract

The present application can provide a phthalonitrile compound and a use thereof. The phthalonitrile compound has a novel structure, and can exhibit an excellent effect in a use to which the phthalonitrile compound can be applied. An example of the use of the phthalonitrile compound may be a raw material or precursor for, so-called, a phthalonitrile resin, a phthalocyanine dye, a fluorescent whitening agent, a photographic sensitizer, an acid anhydride, or the like.

Claims

1. A phthalonitrile resin comprising polymerized units derived from a compound represented by Formula 1 below: ##STR00005## wherein, P.sub.1 and P.sub.2 are the same or different aryl groups from each other, A.sub.1 and A.sub.2 are the same or different arylene groups from each other, L.sub.1 to L.sub.3 are each independently an alkylene group, an alkylidene group, an alkenylene group or an alkynylene group, and P.sub.1, P.sub.2, A.sub.1 and A.sub.2 are each substituted with at least one substituent represented by Formula 2 below, ##STR00006## wherein, L.sub.4 is an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, and R.sub.1 to R.sub.5 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.

2. The resin according to claim 1, wherein L.sub.1 to L.sub.3 are each independently an alkylene group or alkylidene group having 1 to 4 carbon atoms.

3. The resin according to claim 1, wherein P.sub.1, P.sub.2, A.sub.1 and A.sub.2 are each substituted with at least one alkyl group.

4. The resin according to claim 1, wherein A.sub.1 and A.sub.2 are a phenylene group.

5. The resin according to claim 4, wherein L.sub.1 is bonded to the meta position based on the position combined with L.sub.2 in A.sub.1, and L.sub.3 is bonded to the meta position based on the position combined with L.sub.2 in A.sub.2.

6. The resin according to claim 4, wherein the substituent of Formula 2 is substituted at the meta or para position based on to the position combined with L.sub.2 in A.sub.1, and the substituent of Formula 2 is substituted at the meta or para position based on the position combined with L.sub.2 in A.sub.2.

7. The resin according to claim 4, wherein the alkyl group having 1 to 4 carbon atoms is substituted at the meta or para position based on to the position combined with L.sub.2 in A.sub.1, and the alkyl group having 1 to 4 carbon atoms is substituted at the meta or para position based on the position combined with L.sub.2 in A.sub.2.

8. The resin according to claim 1, wherein P.sub.1 and P.sub.2 are a phenyl group.

9. The resin according to claim 8, wherein the substituent of Formula 2 is substituted at the otho or meta position based on the position combined with L.sub.1 in P.sub.1, and the substituent of Formula 2 is substituted at the otho or meta position based on the position combined with L.sub.3 in P.sub.2.

10. The resin according to claim 8, wherein the alkyl group having 1 to 4 carbon atoms is substituted at the otho or meta position based on the position combined with L.sub.1 in P.sub.1, and the alkyl group having 1 to 4 carbon atoms is substituted at the otho or meta position based on the position combined with L.sub.3 in P.sub.2.

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

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIGS. 1 and 2 are NMR analysis results of the compounds prepared in Preparation Examples 1 and 2, respectively.

BEST MODE

(2) Hereinafter, 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.

MODE FOR INVENTION

(3) 1. Nuclear Magnetic Resonance (NMR) Analysis

(4) 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.

(5) 2. DSC (Differential Scanning Calorimetry) Analysis

(6) The DSC analysis was performed in N2 flow atmosphere, while raising the temperature from 35 C. to 450 C. at a rate of temperature increase of 10 C./min using a Q20 system from TA instrument.

(7) 3. TGA (Thermogravimetric Analysis) Analysis

(8) 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)

(9) The compound of Formula A below was synthesized in the following manner. 103.09 g of 4,4-methylenebis[2-[(2-hydroxy-5-methylphenyl)methyl]-6-methyl-phenol and 152.39 g of 4-nitrophthalonitrile were introduced into a three-necked reaction flask together with 145.95 g of potassium carbonate and 605.9 g of DMF (dimethyl formamide). As the reaction flask, a 1000 ml flask equipped with a mechanical stirrer, a distillation apparatus and a nitrogen inlet was used. Subsequently, a nitrogen stream was passed through the reaction flask, and the mixture was heated and stirred at a temperature of about 85 C. for about 5 hours. Subsequently, the mixture in the flask was cooled to room temperature (about 20 C. to 25 C.), and the mixture was precipitated in 4 L of an aqueous hydrochloric acid solution (concentration: 0.2N) and then filtered to remove residual inorganic salts and DMF. The powder obtained after filtration was dispersed again in methanol (1 L), filtered again to remove organic materials, and the reaction product was vacuum-dried in an oven at 50 C. to yield a target product. The results of NMR analysis carried out on the target product were attached to FIG. 1.

(10) ##STR00002##

Preparation Example 2. Synthesis of Compound (PN2)

(11) The compound of Formula B below was synthesized in the following manner. 27.9 g of 4,4-biphenol and 100 mL of DMF (dimethyl formamide) were introduced into a 3 neck RBF (round bottom flask) and dissolved by stirring at room temperature. 51.9 g of 4-nitrophthalonitrile was added and 50 g of DMF was added, and then dissolved by stirring. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF (dimethyl formamide) were introduced together, and then the temperature was raised to 85 C. while stirring. After reacting the mixture for about 5 hours, the reactant was cooled to room temperature (about 20 C. to 25 C.), and neutralized and precipitated in an aqueous hydrochloric acid solution (concentration: 0.2N). After filtering, it was washed with water. Then, the filtered reactant was vacuum-dried in an oven at 100 C., and after removal of water and residual solvent, the compound of Formula B below was obtained. The results of NMR analysis carried out on the target product were attached to FIG. 2.

(12) ##STR00003##

Example 1

(13) To the compound of Formula A in Preparation Example 1, 18 mol % of a curing agent was added relative to the used amount of the compound of Formula A and mixed well to prepare a polymerizable composition. Here, as the curing agent, the compound of Formula C below was used, which is known to be usable in preparing the phthalonitrile resin. The results of DSC and TGA analyses carried out on the composition were shown in Table 1 below. A prepolymer can be prepared by heating the polymerizable composition at 240 C. for several minutes. The prepared prepolymer is heated for about 10 hours while again raising the temperature from 240 C. to about 375 C. to complete the thermosetting, whereby a phthalonitrile resin can be prepared.

(14) ##STR00004##

Example 2

(15) A polymerizable composition was prepared using the compound of Formula A in Preparation Example 1 without further additives. The results of DSC and TGA analyses carried out on the composition were shown in Table 1 below. The prepolymer can be prepared by heating the polymerizable composition at 240 C. for several minutes. The prepared prepolymer is heated for about 10 hours while again raising the temperature from 240 C. to about 375 C. to complete the thermosetting, whereby a phthalonitrile resin can be prepared.

Comparative Example 1

(16) 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 in Preparation Example 1. The results of DSC and TGA analyses carried out on the composition were shown in Table 1 below.

(17) The results of DSC and TGA analyses carried out on the compositions of Examples and Comparative Examples are shown in Table 1 below.

(18) TABLE-US-00001 TABLE 1 Exothermal Processing onset Press temperature temperature window Residue (%) ( C.) ( C.) ( C.) at 800 C. Example 1 107 277 170 78.4 Example 2 110 338 228 79.1 Comparative 233 261 28 78.92 Example 1

(19) From the results of Table 1, it can be confirmed that in the case of using the compound of the present invention the composition has a low processing temperature, so that it is possible to process the composition at low temperature or to prepare the prepolymer, the wide process window of 100 C. or more is secured and the composition exhibits excellent heat resistance. In addition, as confirmed from the case of Example 2, it can be confirmed that the self-curing of the compound of Formula 1 is possible, even when no curing agent is used.