PHTHALONITRILE RESIN

Abstract

The present application relates to a phthalonitrile resin, a polymerizable composition, a prepolymer, a composite, and a preparation method and use thereof. The present application can provide phthalonitrile, and a polymerizable composition and prepolymer using the same, which can have excellent curability, exhibit a suitable processing temperature and a wide window process, and form a composite having excellent physical properties.

Claims

1. A phthalonitrile resin comprising a polymerized unit derived from a compound of Formula 1 below: ##STR00014## wherein, R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group or a substituent of Formula 2 below, provided that at least one of R.sub.1 to R.sub.5 is a substituent of Formula 2 below and at least one of R.sub.6 to R.sub.10 is a substituent of Formula 2 below, and X is an alkylene group or an alkylidene group, ##STR00015## wherein, L is an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom.

2. The phthalonitrile resin according to claim 1, wherein the polymerized unit derived from the compound of Formula 1 comprises polymerized units of two or more compounds of Formulas 3 to 5 below: ##STR00016## wherein, R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, X is an alkylene group or an alkylidene group, and L is an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom.

3. The phthalonitrile resin according to claim 2, wherein the polymerized unit derived from the compound of Formula 1 comprises the polymerized unit derived from the compound of Formula 3 and the polymerized unit of the compound of Formula 4 or 5.

4. The phthalonitrile resin according to claim 2, wherein the polymerized unit derived from the compound of Formula 1 comprises the polymerized unit derived from the compound of Formula 3, the polymerized unit derived from the compound of Formula 4 and the polymerized unit of the compound of Formula 5.

5. The phthalonitrile resin according to claim 2, wherein the polymerized unit derived from the compound of Formula 1 comprises 1 to 200 parts by weight of the polymerized unit derived from the compound of Formula 4 or 5 relative to 100 parts by weight of the polymerized unit derived from the compound of Formula 3.

6. The phthalonitrile resin according to claim 1, further comprising a polymerized unit of an aromatic amine compound.

7. A polymerizable composition comprising a compound of Formula 1 below and a curing agent: ##STR00017## wherein, R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group or a substituent of Formula 2 below, provided that at least one of R.sub.1 to R.sub.5 is a substituent of Formula 2 below and at least one of R.sub.6 to R.sub.10 is a substituent of Formula 2 below, and X is an alkylene group or an alkylidene group, ##STR00018## wherein, L is an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom.

8. The polymerizable composition according to claim 7, comprising two or more compounds of Formulas 3 to 5 below and a curing agent: ##STR00019## wherein, R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, X is an alkylene group or an alkylidene group, and L is an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom.

9. The polymerizable composition according to claim 8, comprising the compound of Formula 3; the compound of Formula 4 or 5; and a curing agent.

10. The polymerizable composition according to claim 8, comprising the compound of Formula 3, the compound of Formula 4, the compound of Formula 5 and a curing agent.

11. The polymerizable composition according to claim 7, wherein the curing agent is an aromatic amine compound, a phenol compound, an inorganic acid, an organic acid, a metal or a metal salt.

12. The polymerizable composition according to claim 7, wherein the polymerizable composition has a processing temperature in a range of 50 C. to 200 C.

13. The polymerizable composition according to claim 12, wherein the polymerizable composition has an absolute value of a difference between the processing temperature and a curing reaction onset temperature of 50 C. or more.

14. A prepolymer which is a reactant of the polymerizable composition of claim 7.

15. A composite comprising the phthalonitrile resin of claim 1.

16. The composite according to claim 15, further comprising a filler.

17. A method for preparing a composite comprising a step of curing a precursor comprising the polymerizable composition of claim 7.

18. A method for preparing a composite comprising a step of curing a precursor comprising the-prepolymer of claim 14.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0064] FIGS. 1 to 3 are NMR analysis results for the compounds prepared in Preparation Examples.

MODE FOR INVENTION

[0065] 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.

[0066] 1. NMR (Nuclear Magnetic Resonance) Analysis

[0067] NMR analysis 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.

[0068] 2. DSC (Differential Scanning Calorimetry) Analysis

[0069] 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.

[0070] 3. TGA (Thermogravimetric Analysis) Analysis

[0071] 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.

PREPARATION EXAMPLE 1

Synthesis of Compound (PN1)

[0072] A compound of Formula A below was synthesized in the following manner. First, 28 g of 4,4-bis(hydroxyphenylmethane) and 150 mL of DMF (dimethyl formamide) were introduced to a 500 mL 3 neck RBF (round-bottom flask) and dissolved by stirring at room temperature. 48.5 g of 4-nitrophthalonitrile was added thereto and 50 g of DMF was added thereto, and then dissolved by stirring. Subsequently, 58.1 g of potassium carbonate and 50 g of DMF were added together and then the temperature was raised to 85 C. while stirring. After reaction for about 5 hours, the reactant is cooled to room temperature. The cooled reaction solution was neutralized and precipitated by pouring it into a 0.2 N hydrochloric acid aqueous solution. After filtering, 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 desired compound was obtained in a yield of 85 wt %.

[0073] The NMR analysis results of the prepared compound of Formula A were shown in FIG. 1, and the DSC and TGA analysis results were summarized in Table 1.

##STR00008##

PREPARATION EXAMPLE 2

Synthesis of Mixture (PN2)

[0074] A mixture of the compound of Formula A above, a compound of Formula B below and a compound of Formula C below was synthesized in the following manner. First, 28 g of a mixture of 4,4-bis(hydroxyphenylmethane), 2,4-bis(hydroxyphenylmethane) and 2,2-bis(hydroxyphenylmethane) and 150 ml of DMF (dimethyl formamide) were introduced to a 500 mL 3 neck RBF (round-bottom flask) and dissolved by stirring at room temperature. In the mixture, the weight ratio of 4,4-bis(hydroxyphenylmethane), 2,4-bis(hydroxyphenylmethane) and 2,2-bis(hydroxyphenylmethane) was 60:35:5 (4,4-bis(hydroxyphenylmethane): 2,4-bis(hydroxyphenylmethane): 2,2-bis(hydroxyphenylmethane)). 48.5 g of 4-nitrophthalonitrile was added thereto, and 50 g of DMF was added and then dissolved by stirring. Subsequently, 58.1 g of potassium carbonate and 50 g of DMF were added together and then the temperature was raised to 85 C. while stirring. After reaction for about 5 hours, the reactant is cooled to room temperature. The cooled reaction solution was neutralized and precipitated by pouring it into a 0.2 N hydrochloric acid aqueous solution. After filtering, 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 desired mixture was obtained in a yield of 80 wt %.

[0075] The NMR analysis results of the prepared mixture of the compound of Formula A, the compound of Formula B and the compound of Formula C were shown in FIG. 2, and the DSC and TGA analysis results were summarized in Table 1.

##STR00009##

PREPARATION EXAMPLE 3

Synthesis of Compound (PN3)

[0076] 25.3 g of 4,4-dihydroxybiphenyl ether and 100 mL of DMF (dimethyl formamide) were introduced to a 3 neck RBF (round-bottom flask) and dissolved by stirring at room temperature. 43.3 g of 4-nitropthalonitrile was added thereto, and 70 g of DMF was added and then dissolved by stirring. Subsequently, 51.8 g of potassium carbonate and 50 g of DMF were added together and then the temperature was raised to 85 C. while stirring. After reaction for about 5 hours, the reactant is cooled to room temperature. The cooled reaction solution was neutralized and precipitated by pouring it into a 0.2 N hydrochloric acid aqueous solution. After filtering, 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 D below (PN3) was obtained in a yield of 88 wt %.

[0077] The NMR results for the compound were shown in FIG. 3, and the DSC and TGA analysis results were summarized in Table 1.

##STR00010##

PREPARATION EXAMPLE 4

Synthesis of Compound (PN4)

[0078] 27.9 g of 4,4-dihydroxybiphenyl 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 4-nitropthalonitrile was added thereto, and 50 g of DMF was added and then dissolved by stirring. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together and then the temperature was raised to 85 C. while stirring. After reaction for about 5 hours, the reactant is cooled to room temperature. The cooled reaction solution was neutralized and precipitated by pouring it into a 0.2 N hydrochloric acid aqueous solution. After filtering, 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 (PN4) was obtained in a yield of 83 wt %. The NMR results for the compound were shown in FIG. 4, and the DSC and TGA analysis results were summarized in Table 1.

##STR00011##

PREPARATION EXAMPLE 5

Synthesis of Compound (PN5)

[0079] 50.4 g of 4,4-bis(4-hydroxyphenyl)hexafluoropropane and 150 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 4-nitropthalonitrile was added thereto, and 50 g of DMF was added and then dissolved by stirring. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together and then the temperature was raised to 85 C. while stirring. After reaction for about 5 hours, the reactant is cooled to room temperature. The cooled reaction solution was neutralized and precipitated by pouring it into a 0.2 N hydrochloric acid aqueous solution. After filtering, 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 F below (PN5) was obtained in a yield of 87 wt %. The NMR results for the compound were shown in FIG. 5, and the DSC and TGA analysis results were summarized in Table 1.

##STR00012##

[0080] Compound (CA)

[0081] A compound of Formula G below used as a curing agent was obtained from a commercial product from TCI (Tokyo Chemical Industry Co., Ltd.) and used without further purification.

##STR00013##

[0082] DSC and TGA analysis results for the compounds (PN1, PN2 and PN3) of Preparation Examples 1 to 5 are summarized in Table 1 below. From the results in Table 1 below, the compound or mixture of Preparation Example 1 or 2 according to the present application has a low processing temperature, and thus it can be predicted that it is possible to prepare a prepolymer at a low temperature, whereby it can secure a wide process window and exhibit excellent heat resistance characteristics.

[0083] On the other hand, in Table 1 below, in the case of the mixture of Preparation Example 2, it was in a form of a mixture and thus the melting temperature (Tm) was confirmed to be two. In the case of the mixture, since the melting temperature was lowered over a single compound, it was confirmed to be advantageous in terms of processability.

[0084] Also, from the following results, it can be confirmed that the compound or the mixture itself of Preparation Example 1 or 2 has superior heat resistance characteristics to the compounds of Preparation Examples 3 to 5.

TABLE-US-00001 TABLE 1 Processing temperature (melting Residue temperature) at 800 C. ( C.) (%) Preparation Example 1 (compound) PN1 195 66.3 Preparation Example 2 (mixture) PN2 132, 174 66.7 Preparation Example 3 (compound) PN3 193 10.2 Preparation Example 4 (compound) PN4 235 1.1 Preparation Example 5 (compound) PN5 231 0.6

EXAMPLE 1

[0085] A polymerizable composition was prepared by compounding the curing agent (CA1, 1,3-bis(3-aminophenoxy)benzene) in the compound (PN1) of Preparation Example 1 such that about 0.15 mole per mole of the compound (PN1) was present. The results of performing DSC and TGA analyses of the composition are described in Table 2 below.

[0086] The composition was heated at each temperature of 220 C., 250 C., 280 C., 310 C. and 340 C. by 2 hours for a total of 10 hours and cured in an oven. The TGA analysis results performed on the composition after curing were summarized in Table 3 below.

EXAMPLE 2

[0087] A polymerizable composition was prepared in the same manner as in Example 1, except that the mixture (PN2) of Preparation Example 2 was used instead of the compound (PN1) of Preparation Example 1. The results of performing DSC and TGA analyses of the composition are described in Table 2 below.

[0088] The composition was heated at each temperature of 220 C., 250 C., 280 C., 310 C. and 340 C. by 2 hours for a total of 10 hours and cured in an oven. The TGA analysis results performed on the composition after curing were summarized in Table 3 below.

COMPARATIVE EXAMPLE 1

[0089] A polymerizable composition was prepared in the same manner as in Example 1, except that the compound (PN3) of Preparation Example 3 was used instead of the compound (PN1) of Preparation Example 1. The results of performing DSC and TGA analyses of the composition are described in Table 2 below.

[0090] The composition was heated at each temperature of 220 C., 250 C., 280 C., 310 C. and 340 C. by 2 hours for a total of 10 hours and cured in an oven. The TGA analysis results performed on the composition after curing were summarized in Table 3 below.

COMPARATIVE EXAMPLE 2

[0091] A polymerizable composition was prepared in the same manner as in Example 1, except that the compound (PN4) of Preparation Example 4 was used instead of the compound (PN1) of Preparation Example 1. The results of performing DSC and TGA analyses of the composition are described in Table 2 below.

[0092] The composition was heated at each temperature of 220 C., 250 C., 280 C., 310 C. and 340 C. by 2 hours for a total of 10 hours and cured in an oven. The TGA analysis results performed on the composition after curing were summarized in Table 3 below.

COMPARATIVE EXAMPLE 3

[0093] A polymerizable composition was prepared in the same manner as in Example 1, except that the compound (PN5) of Preparation Example 5 was used instead of the compound (PN1) of Preparation Example 1. The results of performing DSC and TGA analyses of the composition are described in Table 2 below.

[0094] The composition was heated at each temperature of 220 C., 250 C., 280 C., 310 C. and 340 C. by 2 hours for a total of 10 hours and cured in an oven. The TGA analysis results performed on the composition after curing were summarized in Table 3 below.

[0095] The results of performing DSC and TGA analyses of the compositions of Examples and Comparative Examples are described in Table 2 below.

TABLE-US-00002 TABLE 2 Processing temperature Exothermal (melting onset Process temperature) temperature Window Exothermic ( C.) ( C.) ( C.) energy (J/g) Example 1 188 293 105 200 Example 2 164 281 154 235 Comparative 190 292 102 41 Example 1 Comparative 229 289 60 47 Example 2 Comparative 226 361 135 11 Example 3

TABLE-US-00003 TABLE 3 5% 10% decomposition decomposition temperature temperature Residue at ( C.) ( C.) 800 C. (%) Example 1 496 540 77.6 Example 2 496 540 77.8 Comparative Example 1 481 493 67.0 Comparative Example 2 496 539 76.5 Comparative Example 3 495 521 65.3

[0096] From the results in Table 2, the present application has a low processing temperature, and thus it can be confirmed that it is possible to prepare a prepolymer at a low temperature, the wide process window is secured and it exhibits excellent heat resistance characteristics.

[0097] In addition, reviewing the curing exothermic energy measured by the DSC, it can be seen that in the case of Examples, the exothermic energy is higher than that of Comparative Examples, which means that one reaction of heat has efficiently progressed and the curing degree has increased.

[0098] Furthermore, from the results in Table 3, it can be confirmed that Examples 1 and 2 exhibit excellent heat resistance characteristics as compared with Comparative Examples.