POLYMERIZABLE COMPOSITION

Abstract

The present application relates to a polymerizable composition, a prepolymer, a phthalonitrile resin, a composite, a process for preparing the same, and a use thereof. The present application can provide a polymerizable composition comprising a curing agent which has excellent heat resistance and does not cause defects such as voids that may adversely affect physical properties. In addition, the present application allows for the polymerizable composition to exhibit appropriate curing properties, processing temperatures and process windows and to be capable of forming a composite of excellent physical properties. The present application can provide a resin having both advantages of a phthalonitrile resin and a polyimide by curing a phthalonitrile compound as a raw material monomer with a curing agent having a polyimide structure.

Claims

1. A polymerizable composition comprising a phthalonitrile compound and a compound of Formula 1 below: ##STR00024## wherein, M is a tetravalent radical, X.sub.1 and X.sub.2 are each independently an alkylene group, an alkylidene group or an aromatic divalent radical, and n is a number of 2 or more.

2. The polymerizable composition according to claim 1, wherein the tetravalent radical is a tetravalent radical derived from an aliphatic, alicyclic or aromatic compound.

3. The polymerizable composition according to claim 1, wherein the tetravalent radical is a tetravalent radical derived from an alkane, alkene or alkyne, or a tetravalent radical derived from a compound represented by any one of Formulas 2 to 7 below: ##STR00025## wherein, R.sub.1 to R.sub.6 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group; ##STR00026## wherein, R.sub.1 to R.sub.8 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group; ##STR00027## wherein, R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, X is a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, S(O), S(O).sub.2, C(O)O-L.sub.1-OC(O), -L.sub.2-C(O)O-L.sub.3-, -L.sub.4-OC(O)-L.sub.5- or -L.sub.6-Ar.sub.1-L.sub.7-Ar.sub.2-L.sub.8- , where L.sub.1 to L.sub.8 are each independently a single bond, an oxygen atom, an alkylene group or an alkylidene group and Ar.sub.1 and Ar.sub.2 are each independently an arylene group; ##STR00028## wherein, R.sub.1 to R.sub.4 are each independently hydrogen, an alkyl group or an alkoxy group, and A is an alkylene group or an alkenylene group (provided that two of R.sub.1 to R.sub.4 may be also linked to each other to form an alkylene group, and the alkylene group or alkenylene group of A may contain one or more oxygen atoms as a hetero atom); ##STR00029## wherein, R.sub.1 to R.sub.4 are each independently hydrogen, an alkyl group or an alkoxy group, and A is an alkylene group; ##STR00030## wherein, R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group or an alkoxy group.

4. The polymerizable composition of claim 1, wherein each of X.sub.1 and X.sub.2 is an aromatic divalent radical.

5. The polymerizable composition according to claim 4, wherein the aromatic divalent radical is a divalent radical derived from an aromatic compound having 6 to 28 carbon atoms.

6. The polymerizable composition according to claim 1, wherein each of X.sub.1 and X.sub.2 is a divalent radical derived from a compound represented by any one of Formulas 8 to 10 below: ##STR00031## 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 a carboxyl group; ##STR00032## wherein, R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group or an aryl group and X is a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, -NR.sub.11-, S(O), S(O).sub.2-, -L.sub.9-Ar.sub.3-L.sub.10- or -L.sub.9-Ar.sub.3-L.sub.10-Ar.sub.4-L.sub.11-, where R.sub.11 is hydrogen, an alkyl group, an alkoxy group or an aryl group, Ar.sub.3 and Ar.sub.4 are an arylene group, and L.sub.9 to L.sub.11 are each independently a single bond, an oxygen atom, an alkylene group or an alkylidene group; ##STR00033## wherein, R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group or an aryl group.

7. The polymerizable composition of claim 1, wherein n is a number in a range of 2 to 200.

8. The polymerizable composition according to claim 1, wherein the compound of Formula 1 has a decomposition temperature of 350 C. or higher.

9. The polymerizable composition according to claim 1, wherein a processing temperature (Tp) is in a range of 150 C. to 350 C.

10. The polymerizable composition according to claim 1, further comprising a filler.

11. The polymerizable composition according to claim 1, wherein the compound of Formula 1 is contained in an amount of about 0.02 moles to about 1.5 moles per mole of the phthalonitrile compound.

12. A prepolymer which is a reactant of the polymerizable composition of claim 1.

13. The prepolymer according to claim 12, wherein a processing temperature (Tp) is in a range of 150 C. to 350 C.

14. A phthalonitrile resin which is a polymer of the polymerizable composition of claim 1.

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

16. The composite according to claim 15, wherein the filler is a metal material, a ceramic material, glass, a metal oxide, a metal nitride or a carbon-based material.

17. A process for preparing a composite comprising a step of curing the polymerizable composition of claim 1.

18. A process for preparing a composite comprising a step of curing the prepolymer of claim 12.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0075] FIGS. 1 to 7 are the NMR measurement results for compounds prepared in Production Examples.

MODE FOR INVENTION

[0076] Hereinafter, the polymerizable composition or the like of the present application will be specifically described by way of Examples and Comparative Examples, but the scope of the polymerizable composition and the like is not limited to the following Examples.

[0077] 1. NMR (Nuclear Magnetic Resonance) Analysis

[0078] The NMR analysis of the compound was performed according to the manufacturer's manual using an Agilent 500 MHz NMR instrument. A sample for measuring NMR was prepared by dissolving a compound in DMSO (dimethyl sulfoxide)-d6.

[0079] 2. DSC (Differential Scanning Calorimetry) Analysis

[0080] The DSC analysis was performed in an N2 flow atmosphere using a Q20 system from TA Instrument with increasing the temperature from 35 C. to 450 C. at a rate of 10 C./min

[0081] 3. TGA (Thermogravimetric Analysis) Analysis

[0082] The TGA analysis was performed using a TGA e850 instrument from Mettler-Toledo. The TGA analysis was performed in an N.sub.2 flow atmosphere with increasing the temperature for the sample from about 25 C. to 800 C. at a rate of 10 C./min.

PRODUCTION EXAMPLE 1

Synthesis of Compound (CA1)

[0083] The compound of Formula 14 below was synthesized by dehydration and condensation of a diamine and a dianhydride. 24 g of the compound of Formula 12 (4,4-oxydianiline) and 60 g of NMP (N-methyl pyrrolidone) were charged into an RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 12.3 g of the compound of Formula 13 below was divided into three times and slowly added thereto together with 60 g of NMP. When all the added compounds were dissolved, 24 g of toluene was added to the reactant for the azeotrope reaction. A Dean Stark unit and a reflux condenser were installed, and the Dean Stark unit was charged with toluene added. 4.2 mL of pyridine was added as a catalyst for dehydration and condensation, followed by raising the temperature to 170 C. and stirring for 3 hours. The reactant was further stirred for 2 hours while removing water generated as imide rings were formed, with the Dean Stark unit, and the residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was subjected to soxhlet extraction with methanol to remove the residual reactant and dried in a vacuum oven to obtain the compound of Formula 14 in a yield of about 87% by weight. The NMR analysis results of the compound of Formula 14 are shown in FIG. 1.

##STR00016##

PRODUCTION EXAMPLE 2

Synthesis of Compound (CA2)

[0084] The compound of Formula 15 below was synthesized by dehydration and condensation of a diamine and a dianhydride. 15 g of the compound of Formula 12 (4,4-oxydianiline) in Production Example 1 and 40 g of NMP (N-methyl pyrrolidone) were added to an RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 20.5 g of the compound of Formula 13 in Production Example 1 was divided into three times and slowly added thereto together with 30 g of NMP. When all the added compounds were dissolved, 14 g of toluene was added to the reactant for the azeotrope reaction. A Dean Stark unit and a reflux condenser were installed, and the Dean Stark unit was charged with toluene added. 5.2 mL of pyridine was added as a catalyst for dehydration and condensation, followed by raising the temperature to 170 C. and stirring for 3 hours. The reactant was further stirred for 2 hours while removing water generated as imide rings were formed, with the Dean Stark unit, and the residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was subjected to soxhlet extraction with methanol to remove the residual reactant and dried in a vacuum oven to obtain the compound of Formula 15 in a yield of about 92% by weight. The NMR analysis results of the compound of Formula 15 are shown in FIG. 2.

##STR00017##

[0085] In Formula 15, n is about 3.

PRODUCTION EXAMPLE 3

Synthesis of Compound (CA3)

[0086] The compound of Formula 16 below was synthesized by dehydration and condensation of a diamine and a dianhydride. 20 g of the compound of Formula 12 (4,4-oxydianiline) in Production Example 1 and 50 g of NMP (N-methyl pyrrolidone) were added to an RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 30.7 g of the compound of Formula 13 in Production Example 1 was divided into three times and slowly added thereto together with 50 g of NMP. When all the added compounds were dissolved, 20 g of toluene was added to the reactant for the azeotrope reaction. A Dean Stark unit and a reflux condenser were installed, and the Dean Stark unit was charged with toluene added. 5.2 mL of pyridine was added as a catalyst for dehydration and condensation, followed by raising the temperature to 170 C. and stirring for 3 hours. The reactant was further stirred for 2 hours while removing water generated as imide rings were formed, with the Dean Stark unit, and the residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was subjected to soxhlet extraction with methanol to remove the residual reactant and dried in a vacuum oven to obtain the compound of Formula 16 in a yield of about 88% by weight. The NMR analysis results of the compound of Formula 16 are shown in FIG. 3.

##STR00018##

[0087] In Formula 16, n is about 5.

PRODUCTION EXAMPLE 4

Synthesis of Compound (CA4)

[0088] The compound of Formula 19 below was synthesized by dehydration and condensation of a diamine and a dianhydride. 13.5 g of the compound of Formula 17 (m-phenylene diamne) and 70 g of NMP (N-methyl pyrrolidone) were charged into an RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 26 g of the compound of Formula 18 below was divided into three times and slowly added thereto together with 60 g of NMP. When all the added compounds were dissolved, 26 g of toluene was added to the reactant for the azeotrope reaction. A Dean Stark unit and a reflux condenser were installed, and the Dean Stark unit was charged with toluene added. 5.2 mL of pyridine was added as a catalyst for dehydration and condensation, followed by raising the temperature to 170 C. and stirring for 3 hours. The reactant was further stirred for 2 hours while removing water generated as imide rings were formed, with the Dean Stark unit, and the residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in deionized water and recovered. The recovered precipitate was subjected to soxhlet extraction with methanol to remove the residual reactant and dried in a vacuum oven to obtain the compound of Formula 19 in a yield of about 83% by weight. The NMR analysis results of the compound of Formula 19 are shown in FIG. 4.

##STR00019##

PRODUCTION EXAMPLE 5

Synthesis of Compound (CA5)

[0089] The compound of Formula 20 below was synthesized by dehydration and condensation of a diamine and a dianhydride. 8.1 g of the compound of Formula 17 (m-phenylene diamine) in Production Example 4 and 50 g of NMP (N-methyl pyrrolidone) were added to an RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 26 g of the compound of Formula 18 in Production Example 4 was divided into three times and slowly added thereto together with 60 g of NMP. When all the added compounds were dissolved, 23 g of toluene was added to the reactant for the azeotrope reaction. A Dean Stark unit and a reflux condenser were installed, and the Dean Stark unit was charged with toluene added. 5.2 mL of pyridine was added as a catalyst for dehydration and condensation, followed by raising the temperature to 170 C. and stirring for 3 hours. The reactant was further stirred for 2 hours while removing water generated as imide rings were formed, with the Dean Stark unit, and the residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was subjected to soxhlet extraction with methanol to remove the residual reactant and dried in a vacuum oven to obtain the compound of Formula 20 in a yield of about 93% by weight. The NMR analysis results of the compound of Formula 20 are shown in FIG. 5.

##STR00020##

[0090] In Formula 20, n is about 3.

PRODUCTION EXAMPLE 6

Synthesis of Compound (CA6)

[0091] The compound of Formula 21 below was synthesized by dehydration and condensation of a diamine and a dianhydride. 6.5 g of the compound of Formula 17 (m-phenylene diamine) in Production Example 4 and 50 g of NMP (N-methyl pyrrolidone) were added to an RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 23.4 g of the compound of Formula 18 in Production Example 4 was divided into three times and slowly added thereto together with 60 g of NMP. When all the added compounds were dissolved, 23 g of toluene was added to the reactant for the azeotrope reaction. A Dean Stark unit and a reflux condenser were installed, and the Dean Stark unit was charged with toluene added. 5.2 mL of pyridine was added as a catalyst for dehydration and condensation, followed by raising the temperature to 170 C. and stirring for 3 hours. The reactant was further stirred for 2 hours while removing water generated as imide rings were formed, with the Dean Stark unit, and the residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was subjected to soxhlet extraction with methanol to remove the residual reactant and dried in a vacuum oven to obtain the compound of Formula 21 in a yield of about 95% by weight. The NMR analysis results of the compound of Formula 21 are shown in FIG. 6.

##STR00021##

[0092] In Formula 21, n is about 4.

PRODUCTION EXAMPLE 7

Synthesis of Compound (CA7)

[0093] As the compound of Formula 22 below, a commercially available product from TCI (Tokyo Chemical Industry Co., Ltd.) was obtained and used without further purification.

##STR00022##

PRODUCTION EXAMPLE 8

Synthesis of Compound (PN1)

[0094] The compound of Formula 23 below was synthesized in the following manner. 32.7 g of the compound of Formula 25 below and 120 g of DMF (Dimethyl Formamide) were added to an RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. Subsequently, 51.9 g of the compound of Formula 24 above was further added, and 50 g of DMF was added thereto, followed by dissolving with stirring. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85 C. with stirring. After reacting in the above state for about 5 hours, the reactant was cooled to room temperature. The cooled reaction solution was poured into a 0.2N hydrochloric acid aqueous solution, neutralized and precipitated, followed by filtering and then washing with water. The filtered reactant was then dried in a vacuum oven at 100 C. for 1 day, and after removal of water and the residual solvent, the compound of Formula 23 below was obtained in a yield of about 80% by weight. The NMR results for the compound of Formula 23 were shown in FIG. 7.

##STR00023##

[0095] TGA analysis results for the compounds of Production Examples 1 to 7 were shown in Table 1 below. From Table 1, it can be confirmed that the compounds (CA1 to CA6) of Production Examples 1 to 6 represent heat resistance characteristics superior to the compound (CA7) of Production Example 7. While the compound of CA7 is fully decomposed near 300 C., the compounds of CA1 to CA6 have much higher decomposition temperatures (Td10%) than 300 C., and thus it can be confirmed that thermal decomposition will hardly occur even in high temperature calcination. In addition, the single molecules CA1 and CA4 have excellent heat resistance characteristics as compared to CA7, but the heat resistance characteristics are lower than those of CA2, CA3, CA5 and CA6, and thus it can be confirmed that even in the case of the same monomer, the heat resistance tends to increase as the molecular weight increases. In the following Table 1, the glass transition temperature (Tg) or melting temperature (Tm) confirmed through DSC analysis was described as the processing temperature. From the results shown in Table 1, it can be seen that the lower the molecular weight, the lower the processing temperature is confirmed. However, the increase in the processing temperature is low as compared with the increase in the molecular weight, and thus it can be predicted that even in the case of a material having a high molecular weight such as CA3 or CA6, the processing temperature is not high, the melt compatibility with the monomer is good, the curing efficiency is good, the process window is wide and the workability is good.

TABLE-US-00001 TABLE 1 Processing temperature Residue (Tm or Tg) Td10% at 800 C. Td100% Production .sup.147 C. 390 C. 41.9% Example1(CA1) Production 162.6 C. 420 C. 46.6% Example2(CA2) Production 171.5 C. 428 C. 46.0% Example3(CA3) Production .sup.124 C. 366 C. 47.8% Example4(CA4) Production 176.2 C. 513 C. 53.9% Example5(CA5) Production 188.8 C. 513 C. 54.8% Example6(CA6) Production .sup.108 C. 264 C. 0% 331 C. Example7(CA7)

EXAMPLE 1

[0096] The compound (PN1) of Production Example 8 and the compound (CA2) of Production Example 2 were mixed for about 0.2 moles of the compound (CA2) of Production Example 2 per mole of the compound (PN1) of Production Example 8 to be present. Then, through the TGA analysis, a residue at 300 C. and a Td10% (a temperature at a weight loss of 10%) of the mixture were confirmed.

EXAMPLE 2

[0097] The compound (PN1) of Production Example 8 and the compound (CA3) of Production Example 3 were mixed for about 0.2 moles of the compound (CA3) of Production Example 2 per mole of the compound (PN1) of Production Example 8 to be present. Then, through the TGA analysis, a residue at 300 C. and a Td10% (a temperature at a weight loss of 10%) of the mixture were confirmed.

EXAMPLE 3

[0098] The compound (PN1) of Production Example 8 and the compound (CA5) of Production Example 5 were mixed for about 0.2 moles of the compound (CA5) of Production Example 5 per mole of the compound (PN1) of Production Example 8 to be present. Then, through the TGA analysis, a residue at 300 C. and a Td of 10% (a temperature at a weight loss of 10%) of the mixture were confirmed.

EXAMPLE 4

[0099] The compound (PN1) of Production Example 8 and the compound (CA6) of Production Example 6 were mixed for about 0.2 moles of the compound (CA6) of Production Example 6 per mole of the compound (PN1) of Production Example 8 to be present. Then, through the TGA analysis, a residue at 300 C. and a Td10% (a temperature at a weight loss of 10%) of the mixture were confirmed.

COMPARATIVE EXAMPLE 1

[0100] The compound (PN1) of Production Example 8 and the compound (CA1) of Production Example 1 were mixed for about 0.2 moles of the compound (CA1) per mole of the compound (PN1) of Production Example 8 to be present. Then, through the TGA analysis, a residue at 300 C. and a Td10% (a temperature at a weight loss of 10%) of the mixture were confirmed.

COMPARATIVE EXAMPLE 2

[0101] The compound (PN1) of Production Example 8 and the compound (CA4) of Production Example 4 were mixed for about 0.2 moles of the compound (CA4) of Production Example 4 per mole of the compound (PN1) of Production Example 8 to be present. Then, through the TGA analysis, a residue at 300 C. and a Td10% (a temperature at a weight loss of 10%) of the mixture were confirmed.

COMPARATIVE EXAMPLE 3

[0102] The compound (PN1) of Production Example 8 and the compound (CA7) of Production Example 7 were mixed for about 0.2 moles of the compound (CA7) of Production Example 7 per mole of the compound (PN1) of Production Example 8 to be present. Then, through the TGA analysis, a residue at 300 C. and a Td10% (a temperature at a weight loss of 10%) of the mixture were confirmed.

[0103] The analytical results of the compounds of the above Examples and Comparative Examples were summarized and described in Table 2 below.

TABLE-US-00002 TABLE 2 Composition Residue at 300 C. Td10% Example 1 PN1 + CA2 98.2% .sup.402 C. 2 PN1 + CA3 97.7% .sup.402 C. 3 PN1 + CA5 99.4% 407.1 C. 4 PN1 + CA6 98.9% 408.7 C. Comparative 1 PN1 + CA1 97.7% 390.6 C. Example 2 PN1 + CA4 98.2% 397.5 C. 3 PN1 + CA7 96.1% 384.8 C.

[0104] From the results of Table 2, since the thermal decomposition temperature is very low and thus the thermal stability is lowered in the case of using a general curing agent CA7, it can be confirmed, in the case of using this (Comparative Example 3), that a considerable amount of pyrolysis has already occurred at 300 C. and the temperature of Td10% is also the lowest point. It can be confirmed that when the same monomer is applied, the case where the compounds of CA2, CA3, CAS and CA6 are applied (Examples 1 to 4) has more excellent thermal stability as compared with the case where the compound of CA1 or CA4 is applied (Comparative Examples 1 and 2). From these results, it can be confirmed that when the compounds of the present application are applied, excellent heat stability is ensured to prevent out gassing in high temperature processes, whereby voids or defects may be minimized during processing.