Phthalonitrile resin

Abstract

The present application relates to a phthalonitrile resin and the like. The present application can provide a phthalonitrile resin, and a polymerizable composition and prepolymer using the same, which can exhibit excellent curability, a suitable processing temperature and a wide process window, and form a composite having excellent physical properties. Also, according to the present invention, there may be provided a phthalonitrile resin, and a polymerizable composition and prepolymer using the same, which can exhibit appropriate viscosity characteristics and thus provide a final product without deterioration of mechanical physical properties or the like due to bubbles generated during processing.

Claims

1. A phthalonitrile resin comprising a polymerized unit derived from a compound of Formula 1 below and an aromatic amine compound, wherein a processing temperature of a mixture comprising the compound of Formula 1 and the aromatic amine compound is 100 C. to 250 C., the processing temperature being a melting temperature or a glass transition temperature of the mixture, and wherein an absolute value of the difference between the processing temperature and a curing temperature of the mixture is 50 C. or higher: ##STR00008## wherein in Formula 1, Ar.sub.1 and Ar.sub.2 are aromatic divalent radicals derived from an aromatic compound represented by Formula 2 below, X.sub.1 and X.sub.2 are oxygen atoms, and R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group having 1 to 4 carbon atom(s) or a cyano group, provided that at least two of R.sub.1 to R.sub.5 are each a cyano group and at least two of R.sub.6 to R.sub.10 are each a cyano group; ##STR00009## wherein in Formula 2, one of R.sub.1 and R.sub.4 of Formula 2 forms a radical linked to the sulfur atom (S) of Formula 1, and the other of R.sub.1 and R.sub.4 of Formula 2 forms a radical linked to X.sub.1 or X.sub.2 of Formula 1, and R.sub.2, R.sub.3, R.sub.5 and R.sub.6 of Formula 2 are each independently hydrogen or an alkyl group having 1 to 4 carbon atom(s).

2. The phthalonitrile resin according to claim 1, wherein in Formula 1 R.sub.3, R.sub.4, R.sub.8 and R.sub.9 are each a cyano group, and R.sub.1, R.sub.2, R.sub.5, R.sub.6, R.sub.7 and R.sub.10 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

3. A polymerizable composition comprising a compound of Formula 1 below and an aromatic amine compound, wherein a processing temperature of the polymerizable composition is 100 C. to 250 C., the processing temperature being a melting temperature or a glass transition temperature of the polymerizable composition, and wherein an absolute value of the difference between the processing temperature and a curing temperature of the polymerizable composition is 50 C. or higher: ##STR00010## wherein, in the Formula 1, Ar.sub.1 and Ar.sub.2 of the Formula 1 are aromatic divalent radicals derived from an aromatic compound represented by Formula 2 below, X.sub.1 and X.sub.2 of the Formula 1 are oxygen atoms, and R.sub.1 to R.sub.10 of the Formula 1 are each independently hydrogen, an alkyl group having 1 to 4 carbon atom(s), or a cyano group, provided that at least two of R.sub.1 to R.sub.5 of the Formula 1 are each a cyano group and at least two of R.sub.6 to R.sub.10 of the Formula 1 are each a cyano group: ##STR00011## Wherein, in the Formula 2, one of R.sub.1 and R.sub.4 of the Formula 2 forms a radical linked to the sulfur atom (S) of the Formula 1 and the other of R.sub.1 and R.sub.4 of the Formula 2 forms a radical linked to X.sub.1 or X.sub.2 of the Formula 1, and R.sub.2, R.sub.3, R.sub.5 and R.sub.6 of the Formula 2 are each independently hydrogen or an alkyl group having 1 to 4 carbon atom(s).

4. The polymerizable composition according to claim 3, wherein the compound of Formula 1 has a viscosity in a range of 100 cP to 10,000 cP at a temperature of 150 C. or higher.

5. A prepolymer which comprises a reacted product of the polymerizable composition of claim 3.

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

7. The composite according to claim 6, wherein the filler is a metal material, a ceramic material, glass, a metal oxide, a metal nitride or a carbon-based material.

Description

BRIEF DESCRIPTION OF DRAWINGS

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

MODE FOR INVENTION

(2) Hereinafter, the phthalonitrile resin and the like of the present application 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.

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

(4) NMR analysis of compounds synthesized in Preparation Examples 1 to 3 was carried out by using a 500 MHz NMR equipment from Agilent as the manufacturer's manual. A sample for NMR measurement was prepared by dissolving the compound in DMSO (dimethyl sulfoxide)-d6.

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

(6) DSC analysis was carried out in a N.sub.2 flow atmosphere using a Q20 system from TA instrument while raising the temperature from 35 C. to 450 C. at a heating rate of 10 C./min.

(7) 3. TGA (Thermogravimetric Analysis) Analysis

(8) 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 a N.sub.2 flow atmosphere while raising the temperature from 25 C. to 800 C. at a heating rate of 10 C./min, and in the case of compositions prepared in Examples and Comparative Examples, after post-curing them at a temperature of 375 C., they were analyzed in a N.sub.2 flow atmosphere while raising the temperature from 25 C. to 900 C. at a heating rate of 10 C./min.

(9) 4. Viscosity Analysis

(10) Viscosity was measured using a DHR instrument from TA. For the target of viscosity measurement, for example, the compound in each preparation example, the viscosity was measured while raising the temperature from 180 C. to 400 C. at a heating rate of about 5 C./min.

Preparation Example 1. Synthesis of Compound (PN1)

(11) The compound of Formula A below was synthesized in the following manner. First, 37.1 g of the compound of Formula B below (4,4-thiodiphenol) and 200 g of DMF (dimethyl formamide) were introduced to a 3 neck RBF (round bottom flask) and dissolved by stirring at room temperature. 58.9 g of the compound of Formula C below was added thereto, 50 g of DMF was added, and then dissolved by stirring. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were introduced together, and the temperature was raised to 85 C. while stirring. The mixture was reacted for about 5 hours and the reactant was cooled at room temperature. The cooled reaction solution was neutralized and precipitated by pouring it into 0.2 N hydrochloric acid aqueous solution, and filtered, followed by washing with water. Then, the filtered reactant was dried in a vacuum oven at 100 C. for one day, and after removal of water and residual solvent, the compound of Formula A was obtained in a yield of 80% by weight.

(12) ##STR00005##

(13) NMR analysis results for the compound of Formula A were shown in FIG. 1.

Preparation Example 2. Synthesis of Compound (PN2)

(14) 27.9 g of the compound of Formula D below and 100 mL of DMF (dimethyl formamide) were introduced to a 3 neck RBF (round bottom flask) and dissolved by stirring at room temperature. 51.9 g of the compound of Formula C (4-nitrophthalonitrile) in Preparation Example 1 was added, 50 g of DMF was added, and then dissolved by stirring. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were introduced together, and then the temperature was raised to 85 C. while stirring. The mixture was reacted for about 5 hours, and then the reactant was cooled to room temperature. The cooled reaction solution was neutralized and precipitated by pouring it into 0.2N hydrochloric acid aqueous solution. After filtration, it was washed with water. Then, the filtered reactant was dried in a vacuum oven at 100 C. for one day. After removal of water and residual solvent, the compound of Formula E below (PN2) was obtained in a yield of 83% by weight.

(15) ##STR00006##

(16) The NMR analysis results for the compound of Formula D are shown in FIG. 2. The analytical results for the above compounds are summarized in Table 1.

PREPARATION Example 3. Synthesis of Compound (CA1)

(17) The compound of Formula F below (CA1) was commercially available from TCI (Tokyo Chemical Industry Co., Ltd.) and used without further purification.

(18) ##STR00007##

(19) DSC and TGA analysis results for the compounds (PN1, PN2) in Preparation Examples 1 and 2 are summarized in Table 1 below.

(20) TABLE-US-00001 TABLE 1 Processing Residue (%) Residue (%) Temperature ( C.) at 375 C. at 800 C. Preparation PN1 182 96.4 1.1 Example 1 Preparation PN2 233.3 99.2 11.2 Example 2

Example 1

(21) To the compound (PN1) of Formula A in Preparation Example 1, 3 mol % of the compound of Preparation Example 3 (CA1, Formula F) relative to the used amount of the compound of Formula A was added and mixed well to prepare a polymerizable composition. The results of performing DSC and TGA analyses and viscosity analysis of the composition are shown in Table 2 below. The prepolymer can be prepared by heating the polymerizable composition at 240 C. for several minutes. If the prepared prepolymer is heated to about 375 C. by raising the temperature again at 240 C. to complete heat curing, the phthalonitrile resin can be prepared.

Comparative Example 1

(22) A prepolymer and a phthalonitrile resin were prepared in the same manner as in Example 1, except that the compound (PN2) of Formula E in Preparation Example 2 was used instead of the compound of Formula A. The results of DSC and TGA analyses and viscosity analysis performed on the above are shown in Table 2 below.

(23) The results of DSC and TGA analyses and viscosity analysis of the compositions of Examples and Comparative Examples are shown in Table 2 below.

(24) TABLE-US-00002 TABLE 2 Exothermal Processing Onset Temperature Temperature Process Residue (%) ( C.) ( C.) Window ( C.) at 800 C. Example 1 178 296 78 74 Comparative 233 261 28 68 Example 1

(25) From the results of Table 2, it can be confirmed that the composition in the present application has a low processing temperature and thus is capable of producing a prepolymer at a low temperature, secures a wide process window of 100 C. or higher, and exhibits excellent heat resistance characteristics. Furthermore, it can be confirmed that the composition exhibits a low viscosity in a molten state and thus a final product without comprising voids due to bubbles or the like can be formed.