Polymerizable Composition

Abstract

A polymerizable composition, a prepolymer, a phthalonitrile resin, or a composite provided herein has excellent heat resistance and does not cause defects that may adversely affect physical properties. In addition, the polymerizable composition exhibits appropriate curing properties, processing temperatures and process windows and to be capable of forming a composite of excellent physical properties.

Claims

1. A polymerizable composition comprising a phthalonitrile compound and a compound of Formula 1 below: ##STR00027## wherein M is a tetravalent radical, and X.sub.1 and X.sub.2 are each independently an alkylene group, an alkylidene group or an aromatic divalent radical.

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: ##STR00028## wherein R.sub.1 to R.sub.6 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group; ##STR00029## wherein R.sub.1 to R.sub.8 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group; ##STR00030## 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, -A.sub.1-OC(O)-A.sub.2-, -A.sub.1-C(O)O-A.sub.2-, S(O), or S(O).sub.2, wherein A.sub.1 and A.sub.2 are each independently a single bond or an alkylene group; ##STR00031## 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, wherein two of R.sub.1 to R.sub.4 are linked to each other to form an alkylene group, and the alkylene group or the alkenylene group of A contains one or more oxygen atoms as a hetero atom; ##STR00032## 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; ##STR00033## 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 40 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: ##STR00034## 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; ##STR00035## 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, -A.sub.1-OC(O)-A.sub.2-, -A.sub.1-C(O)O-A.sub.2-, NR.sub.11, S(O) or S(O).sub.2, wherein R.sub.11 is hydrogen, an alkyl group, an alkoxy group or an aryl group, and A.sub.1 and A.sub.2 are each independently a single bond or an alkylene group; ##STR00036## 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 the compound of Formula 1 has a 10 wt % decomposition temperature of 300 C. or higher.

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

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

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

11. A prepolymer which is formed by a reaction of the polymerizable composition of claim 1.

12. The prepolymer according to claim 11, wherein a melt viscosity of the prepolymer at any one temperature in a range of 150 C. to 250 C. is in a range of 100 cP to 10,000 cP.

13. The prepolymer according to claim 11, wherein a processing temperature (Tp) of the prepolymer 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 fibrous materials or carbon nanomaterials.

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

Description

BRIEF DESCRIPTION OF DRAWINGS

[0068] FIGS. 1 to 10 are the NMR analysis results for compounds prepared in Production Examples.

[0069] FIG. 11 is the FT-IR analysis results for polymerizable compositions of Examples and Comparative Examples.

MODE FOR INVENTION

[0070] 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.

[0071] 1. TGA (Thermogravimetric Analysis)

[0072] The TGA analysis was performed using a TGA e850 instrument from Mettler-Toledo. The 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.

[0073] 2. FT-IR(Fourier-Transform Infrared Spectroscopy)

[0074] The FT-IR analysis was performed by ATR (Attenuated Total Reflectance) method using the equipment from Varian. As a sample, a prepolymer of Examples or Comparative Examples was thermally cured, pulverized and powdered, and then measured, where the FT-IR peaks were measured as an absorption wavelength over wavelengths of 400 cm.sup.1 to 4000 cm.sup.1.

Production Example 1. Synthesis of Compound (PN1)

[0075] The compound of Formula I below was synthesized in the following manner. 27.9 g of the compound of Formula II below and 100 g of DMF (Dimethyl Formamide) were added to a 3 neck RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. Subsequently, 51.9 g of the compound of Formula III below 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 I below was obtained in a yield of about 83% by weight. The NMR result for the compound of Formula I was shown in FIG. 1.

##STR00016##

Production Example 2. Synthesis of Compound (PN2)

[0076] 50.4 g of the compound of Formula IV below and 150 g of DMF (Dimethyl Formamide) were added to a 3 neck RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. Then, 51.9 g of the compound of Formula III in Production Example 1 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 V below (PN2) was obtained in a yield of about 87% by weight. The NMR result for the compound of Formula V was shown in FIG. 2.

##STR00017##

Production Example 3. Synthesis of Compound (CA1)

[0077] The compound of Formula IIX below was synthesized in the following manner. First, 24 g of the compound of Formula VI and 45 g of NMP (N-methyl-pyrrolidone) were charged into a 3 neck RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 12.4 g of the compound of Formula VII below was slowly divided into three times and added thereto together with 45 g of NMP. When all the added compounds were dissolved, 18 g of toluene was added to the reactant for azeotrope. 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 extraction with methanol to remove the residual reactant and dried in a vacuum oven to obtain the compound of Formula IIX in a yield of about 81% by weight. The NMR analysis result of the compound of Formula IIX was shown in FIG. 3.

##STR00018##

Production Example 4. Synthesis of Compound (CA2)

[0078] The compound of Formula X below was synthesized in the following manner. First, 13 g of the compound of Formula IX below and 33 g of NMP (N-methyl-pyrrolidone) were charged into a 3 neck RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 12.4 g of the compound of Formula VII in Production Example 3 was slowly divided into three times and added thereto together with 30 g of NMP. When all the added compounds were dissolved, 13 g of toluene was added to the reactant for azeotrope. 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 extraction with methanol to remove the residual reactant and dried in a vacuum oven to obtain the compound of Formula X in a yield of about 78% by weight. The NMR analysis result of the compound of Formula X was shown in FIG. 4.

##STR00019##

Production Example 5. Synthesis of Compound (CA3)

[0079] The compound of Formula XII below was synthesized in the following manner. First, 13 g of the compound of Formula XI below and 33 g of NMP (N-methyl-pyrrolidone) were charged into a 3 neck RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 12.4 g of the compound of Formula VII in Production Example 3 was slowly divided into three times and added thereto together with 30 g of NMP. When all the added compounds were dissolved, 13 g of toluene was added to the reactant for azeotrope. 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 extraction with methanol to remove the residual reactant and dried in a vacuum oven to obtain the compound of Formula XII in a yield of about 80% by weight. The NMR analysis result of the compound of Formula XII was shown in FIG. 5.

##STR00020##

Production Example 6. Synthesis of Compound (CA4)

[0080] 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 VI (4,4-oxydianiline) in Production Example 3 and 40 g of NMP (N-methyl-pyrrolidone) were charged into a 3 neck RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 8.7 g of the compound of Formula 13 below was slowly divided into three times and added thereto together with 40 g of NMP. When all the added compounds were dissolved, 16 g of toluene was added to the reactant for azeotrope. 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 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 85% by weight. The NMR analysis result of the compound of Formula 14 was shown in FIG. 6.

##STR00021##

Production Example 7. Synthesis of Compound (CA5)

[0081] The compound of Formula 16 below was synthesized by dehydration and condensation of a diamine and a dianhydride. 24 g of the compound of Formula VI (4,4-oxydianiline) in Production Example 3 and 45 g of NMP (N-methyl-pyrrolidone) were charged into a 3 neck RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 11.8 g of the compound of Formula 15 below was slowly divided into three times and added thereto together with 45 g of NMP. When all the added compounds were dissolved, 18 g of toluene was added to the reactant for azeotrope. 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 16 in a yield of about 77% by weight. The NMR analysis result of the compound of Formula 16 was shown in FIG. 7.

##STR00022##

Production Example 8. Synthesis of Compound (CA6)

[0082] The compound of Formula 18 below was synthesized by dehydration and condensation of a diamine and a dianhydride. 24 g of the compound of Formula VI (4,4-oxydianiline) in Production Example 3 and 45 g of NMP (N-methyl-pyrrolidone) were charged into a 3 neck RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 11.8 g of the compound of Formula 17 below was slowly divided into three times and added thereto together with 45 g of NMP. When all the added compounds were dissolved, 18 g of toluene was added to the reactant for azeotrope. 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 18 in a yield of about 87% by weight. The NMR analysis result of the compound of Formula 18 was shown in FIG. 8.

##STR00023##

Production Example 9. Synthesis of Compound (CA7)

[0083] The compound of Formula 20 below was synthesized by dehydration and condensation of a diamine and a dianhydride. 24 g of the compound of Formula VI (4,4-oxydianiline) in Production Example 3 and 45 g of NMP (N-methyl-pyrrolidone) were charged into a 3 neck RBF (3 neck round bottom flask) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 9 g of the compound of Formula 19 below was slowly divided into three times and added thereto together with 41 g of NMP. When all the added compounds were dissolved, 18 g of toluene was added to the reactant for azeotrope. 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 20 in a yield of about 75% by weight. The NMR analysis result of the compound of Formula 20 was shown in FIG. 9.

##STR00024##

Production Example 10. Synthesis of Compound (CA8)

[0084] The compound of Formula 22 below was synthesized by dehydration and condensation of a diamine and a dianhydride. 24 g of the compound of Formula VI (4,4-oxydianiline) in Production Example 3 and 60 g of NMP (N-methyl-pyrrolidone) were charged into a 3 neck 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 21 below was slowly divided into three times and 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 azeotrope. 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 22 in a yield of about 87% by weight. The NMR analysis result of the compound of Formula 22 was shown in FIG. 10.

##STR00025##

Production Example 11. Synthesis of Compound (CA9)

[0085] As the compound of Formula 23 below (CA9), a commercially available product from TCI (Tokyo Chemical Industry Co., Ltd.) was obtained and used without further purification.

##STR00026##

[0086] TGA analysis results for the compounds of Production Examples 3 to 11 were summarized and shown in Table 1 below. From Table 1, it can be confirmed that the compounds (CA1 to CA8) of Production Examples 3 to 10 represent heat resistance characteristics superior to the compound (CA9) of Production Example 11. While the compound of CA9 is fully decomposed near 330 C., the compounds of CA1 to CA8 have a Td10% of 300 C. or higher, and thus it can be seen that thermal decomposition hardly occurs even in high temperature calcination.

TABLE-US-00001 TABLE 1 Td10% Residue at 800 C. Td100% Production Example 3 (CA1) 303 C. 43.3% Production Example 4 (CA2) 356 C. 48.9% Production Example 5 (CA3) 382 C. 44.3% Production Example 6 (CA4) 354 C. 29.1% Production Example 7 (CA5) 319 C. 45.1% Production Example 8 (CA6) 393 C. 50.8% Production Example 9 (CA7) 436 C. 29.1% Production Example 10 (CA8) 390 C. 41.9% Production Example 11 (CA9) 264 C. 0% 331 C.

Example 1

[0087] About 6 mol % of the compound (CA1) of Production Example 3 relative to the used amount of the compound (PN1) in Production Example 1 was added to the compound (PN1) and mixed well to prepare a polymerizable composition. The results of performing the FT-IR analysis on the composition were shown in FIG. 11. When the polymerizable composition is melted at 240 and stirred for 5 minutes, it is possible to prepare a prepolymer. As shown in FIG. 11, the imide stretching peaks were observed at 1720 cm.sup.1 and 1770 cm.sup.1 from the FR-IR analysis result and thus it can be confirmed that the polymerizable composition exhibits excellent heat resistance and the like (the graph of Example 1 is the second graph at the top of FIG. 11).

Example 2

[0088] About 6 mol % of the compound (CA1) of Production Example 3 relative to the used amount of the compound (PN2) in Production Example 2 was added to the compound (PN2) and mixed well to prepare a polymerizable composition. The results of performing the FT-IR analysis on the composition were shown in FIG. 11. When the polymerizable composition is melted at 240 and stirred for 5 minutes, it is possible to prepare a prepolymer. As shown in FIG. 11, the imide stretching peaks were observed at 1720 cm.sup.1 and 1770 cm.sup.1 from the FR-IR analysis result and thus it can be confirmed that the polymerizable composition exhibits excellent heat resistance and the like (the graph of Example 2 is the top graph of FIG. 11).

Example 3

[0089] A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA2) of Production Example 4 was used instead of the compound (CA1) of Production Example 3. Also, in the case of Example 3, the imide stretching peaks can be observed at 1720 cm.sup.1 and 1770 cm.sup.1 from the FT-IR analysis.

Example 4

[0090] A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA3) of Production Example 5 was used instead of the compound (CA1) of Production Example 3. Also, in the case of Example 4, the imide stretching peaks can be observed at 1720 cm.sup.1 and 1770 cm.sup.1 from the FT-IR analysis.

Example 5

[0091] A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA4) of Production Example 6 was used instead of the compound (CA1) of Production Example 3. Also, in the case of Example 5, the imide stretching peaks can be observed at 1720 cm.sup.1 and 1770 cm.sup.1 from the FT-IR analysis.

Example 6

[0092] A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA5) of Production Example 7 was used instead of the compound (CA1) of Production Example 3. Also, in the case of Example 6, the imide stretching peaks can be observed at 1720 cm.sup.1 and 1770 cm.sup.1 from the FT-IR analysis.

Example 7

[0093] A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA6) of Production Example 8 was used instead of the compound (CA1) of Production Example 3. Also, in the case of Example 7, the imide stretching peaks can be observed at 1720 cm.sup.1 and 1770 cm.sup.1 from the FT-IR analysis.

Example 8

[0094] A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA7) of Production Example 9 was used instead of the compound (CA1) of Production Example 3. Also, in the case of Example 8, the imide stretching peaks can be observed at 1720 cm.sup.1 and 1770 cm.sup.1 from the FT-IR analysis.

Example 10

[0095] A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA8) of Production Example 10 was used instead of the compound (CA1) of Production Example 3. Also, in the case of Example 10, the imide stretching peaks can be observed at 1720 cm.sup.1 and 1770 cm.sup.1 from the FT-IR analysis.

Comparative Example 1

[0096] About 6 mol % of the compound (CA9) of Production Example 11 relative to the used amount of the compound (PN1) in Production Example 1 was added to the compound (PN1) and mixed well to prepare a polymerizable composition. The results of performing the FT-IR analysis on the composition were shown in FIG. 11. When the polymerizable composition is melted at 240 and stirred for 5 minutes, it is possible to prepare a prepolymer. As shown in FIG. 11, no imide stretching peak was observed from the FR-IR analysis result and thus it can be confirmed that the polymerizable composition has poor physical properties such as heat resistance as compared with Examples (the graph of Comparative Example 1 is the fourth graph at the top of FIG. 11).

Comparative Example 2

[0097] About 6 mol % of the compound (CA9) of Production Example 11 relative to the used amount of the compound (PN2) in Production Example 2 was added to the compound (PN2) and mixed well to prepare a polymerizable composition. The results of performing the FT-IR analysis on the composition were shown in FIG. 11. When the polymerizable composition is melted at 240 and stirred for 5 minutes, it is possible to prepare a prepolymer. As shown in FIG. 11, no imide stretching peak was observed from the FR-IR analysis result and thus it can be confirmed that the polymerizable composition has poor physical properties such as heat resistance as compared with Examples (the graph of Comparative Example 2 is the third graph at the top of FIG. 11).