PHTHALONITRILE RESIN

Abstract

The present application relates to a phthalonitrile resin, a polymerizable composition, a prepolymer, a composite, a preparation method therefor, and a use thereof. The present application can provide: phthalonitrile having excellent curability, exhibiting a suitable process temperature and a wide process window, and capable of forming a composite having excellent physical properties; a polymerizable composition using the same; and a prepolymer.

Claims

1. A phthalonitrile resin comprising polymerized units derived from a compound of Formula 1 below: ##STR00009## wherein R.sup.1 to R.sup.10 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano group, provided that at least two of R.sup.1 to R.sup.5 are a cyano group and at least two of R.sup.6 to R.sup.10 are a cyano group, X.sup.1 and X.sup.2 are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, Ar.sup.1, Ar.sup.2 and Ar.sup.3 are the same or different aromatic divalent radical from one another, n is a number of 1 or more, m is a number of 1 or more, L.sup.1 is an alkylene group or an alkylidene group, and L.sup.2 is an alkylene group or an alkylidene group, substituted with a monovalent radical of Formula 2 below: ##STR00010## wherein R.sup.11 to R.sup.15 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano group, provided that at least two of R.sup.11 to R.sup.15 are a cyano group, X.sup.3 is an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, and Ar.sup.4 is an aromatic divalent radical.

2. The phthalonitrile resin according to claim 1, wherein in Formula 1 R.sup.1 to R.sup.10 are each independently hydrogen or an alkyl group, provide that at least two of R.sup.1 to R.sup.5 are a cyano group and at least two of R.sup.6 to R.sup.10 are a cyano group.

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

4. The phthalonitrile resin according to claim 1, wherein in Formula 1 Ar.sup.1, Ar.sup.2 and Ar.sup.3 are phenylene.

5. The phthalonitrile resin according to claim 4, wherein in Ar.sup.1 of Formula 1, a substitution position of L.sup.1 is a para position based on X.sup.1, in Ar.sup.2, a substitution position of L.sup.2 is a para position based on L.sup.1, and in Ar.sup.3, a substitution position of X.sup.2 is a para position based on L.sup.2.

6. The phthalonitrile resin according to claim 1, wherein in Formula 1 n is a number in a range of 1 to 10 and m is a number in a range of 1 to 10.

7. The phthalonitrile resin according to claim 1, wherein in Formula 2 R.sup.11 to R.sup.15 are each independently hydrogen or an alkyl group, provided that at least two of R.sup.11 to R.sup.15 are a cyano group.

8. The phthalonitrile resin according to claim 1, wherein in Formula 2 R.sup.13 and R.sup.14 are a cyano group and R.sup.11, R.sup.12 and R.sup.15 are each independently hydrogen or an alkyl group.

9. The phthalonitrile resin according to claim 1, wherein in Formula 2 Ar.sup.4 is phenylene.

10. The phthalonitrile resin according to claim 9, wherein in Ar.sup.4 of Formula 2 a substitution position of X.sup.3 is a para position based on a site linked to L.sup.2 of Formula 1.

11. The phthalonitrile resin according to claim 1, wherein in Formula 1 X.sup.1 and X.sup.2 are an oxygen atom, Ar.sup.1, Ar.sup.2 and Ar.sup.3 are a phenylene group, n is 1 or 2 and m is 1 or 2, and in Formula 2 Ar.sup.4 is a phenylene group and X.sup.3 is an oxygen atom.

12. A polymerizable composition comprising a compound of Formula 1 below and a curing agent: ##STR00011## wherein R.sup.1 to R.sup.10 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano group, provided that at least two of R.sup.1 to R.sup.5 are a cyano group and at least two of R.sup.6 to R.sup.10 are a cyano group, X.sup.1 and X.sup.2 are each independently an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, Ar.sup.1, Ar.sup.2 and Ar.sup.3 are the same or different aromatic divalent radical from one another, n is a number of 1 or more, m is a number of 1 or more, L.sup.1 is an alkylene group or an alkylidene group, and L.sup.2 is an alkylene group or an alkylidene group, substituted with a monovalent radical of Formula 2 below: ##STR00012## wherein R.sup.11 to R.sup.15 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano group, provided that at least two of R.sup.11 to R.sup.15 are a cyano group, X.sup.3 is an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, and Ar.sup.4 is an aromatic divalent radical.

13. The polymerizable composition according to claim 12, wherein a process temperature is in a range of 100° C. to 250° C. and an absolute value of a difference of said process temperature and a curing temperature (Tc) is 50° C. or more.

14. A prepolymer being a reactant of the polymerizable composition of claim 12.

15. The prepolymer according to claim 14, wherein a process temperature is in a range of 100° C. to 250° C. and an absolute value of a difference of said process temperature and a curing temperature (Tc) is 50° C. or more.

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

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

18. The composite according to claim 17, wherein the filler is a fibrous material or a carbon nanomaterial.

19. A precursor comprising the polymerizable composition of claim 12.

20. A method for preparing a composite comprising a step of curing the precursor of claim 19.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0056] FIG. 1 is a result of NMR analysis on the compound (PN1) prepared in Preparation Example 1.

[0057] FIG. 2 is a result of NMR analysis on the compound (PN2) prepared in Preparation 2.

[0058] FIG. 3 is a result of NMR analysis on the compound (PN3) prepared in Preparation Example 3.

[0059] FIG. 4 is a result of NMR analysis on the compound (PN3) prepared in Preparation Example 3.

MODE FOR INVENTION

[0060] Hereinafter, the phthalonitrile resin will be specifically explained through Examples and Comparative Examples, but the scope of the resin and the like is not limited to the following examples.

1. NMR (Nuclear Magnetic Resonance) Analysis

[0061] NMR analyses on the compounds synthesized in Preparation Examples 1 to 3 were performed by using a 500 MHz NMR equipment from Agilent Co. as the manufacturer's manual. Samples for measurement of NMR were prepared by dissolving the compounds in DMSO (dimethyl sulfoxide)-d6.

2. DSC (Differential Scanning Calorimetry) Analysis

[0062] The DSC analysis was performed in an N2 flow atmosphere, while elevating the temperature from 35° C. to 450° C. at a rate of temperature rise of 10° C./min using a Q20 system from TA Instrument Co.

3. TGA (Thermogravimetric Analysis) Analysis

[0063] The TGA analysis was performed using an equipment of TGA e850 from Mettler-Toledo Co. The compounds prepared in Preparation Examples were analyzed in an N2 flow atmosphere while elevating the temperature from 25° C. to 800° C. at a rate of temperature rise of 10° C./min, and the compositions prepared in Examples or Comparative Examples were analyzed in an N2 flow atmosphere, while elevating the temperature from 25° C. to 900° C. at a rate of temperature rise of 10° C./min after post-curing them at a temperature of 375° C.

Preparation Example 1

Synthesis of Compound (PN1)

[0064] 38.2 g of a compound of Formula A below (CAS No. 110726-28-8) and 100 mL of DMF (dimethyl formamide) were introduced into a 3-neck RBF (3-neck round-bottom flask), stirred at room temperature and dissolved. 46.7 g of 4-nitro-phthalonitrile of Formula B below was added thereto and 50 g of DMF was added thereto, and then stirred and dissolved. Subsequently, 56.0 g of potassium carbonate and 50 g of DMF were introduced together thereto, and then the temperature was raised to 85° C. with stirring. After reaction for about 5 hours, the reactant was cooled to room temperature. The cooled reaction solution was poured into an aqueous solution of 0.2N hydrochloric acid to be neutralized and precipitated. After filtering, the residue was washed with water. Then, the filtered reactant was dried in a vacuum oven at 100° C. for a day. After removing water and the residual solvent, a compound of Formula C below (PN1) was obtained in a yield of 85% by weight.

##STR00004##

[0065] The NMR analysis results on the compound of Formula C are shown in FIG. 1. From the DSC analysis results about the compound of Formula C, its process temperature (softening point) was about 104° C. or so. It could be confirmed that on TGA analysis, the residue at 800° C. represents as high as 42% by weight, and thus it has excellent thermal stability.

Preparation Example 2

Synthesis of Compound (PN2)

[0066] 27.9 g of a compound of Formula D below and 100 mL of DMF (dimethyl formamide) were introduced into a 3-neck RBF (3-neck round-bottom flask), stirred at room temperature and dissolved. 51.9 g of 4-nitro-phthalonitrile of Formula B used in Preparation Example 1 above was added thereto and 50 g of DMF was added thereto, and then stirred and dissolved. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were introduced together thereto, and then the temperature was raised to 85° C. with stirring. After reaction for about 5 hours, the reactant was cooled to room temperature. The cooled reaction solution was poured into an aqueous solution of 0.2N hydrochloric acid to be neutralized and precipitated. After filtering, the residue was washed with water. Then, the filtered reactant was dried in a vacuum oven at 100° C. for a day. After removing water and the residual solvent, a compound of Formula E below (PN2) was obtained in a yield of 83% by weight.

##STR00005##

[0067] The NMR analysis results on the compound of Formula E are shown in FIG. 2. The analysis results on the compound are summarized in Table 1.

Preparation Example 3

Synthesis of Compound (PN3)

[0068] 50.4 g of a compound of Formula F below and 150 mL of DMF (dimethyl formamide) were introduced into a 3-neck RBF (3-neck round-bottom flask), stirred at room temperature and dissolved. 51.9 g of 4-nitro-phthalonitrile of Formula B used in Preparation Example 1 above was added thereto and 50 g of DMF was added thereto, and then stirred and dissolved. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were introduced together thereto, and then the temperature was raised to 85° C. with stirring. After reaction for about 5 hours, the reactant was cooled to room temperature. The cooled reaction solution was poured into an aqueous solution of 0.2N hydrochloric acid to be neutralized and precipitated. After filtering, the residue was washed with water. Then, the filtered reactant was dried in a vacuum oven at 100° C. for a day. After removing water and the residual solvent, a compound of Formula G below (PN3) was obtained in a yield of 87% by weight.

##STR00006##

[0069] The NMR analysis results on the compound of Formula G are shown in FIG. 3. The analysis results on the compound are summarized in Table 1.

Preparation 4

Synthesis of Compound (PN4)

[0070] 27.6 g of a compound of Formula H below and 100 mL of DMF (dimethyl formamide) were introduced into a 3-neck RBF (3-neck round-bottom flask), stirred at room temperature and dissolved. 46.7 g of the compound of Formula B used in Preparation Example 1 above was additionally introduced thereto and 50 g of DMF was added thereto, and then stirred and dissolved. Subsequently, 56.0 g of potassium carbonate and 50 g of DMF were introduced together thereto, and then the temperature was raised to 85° C. with stirring. After reaction for about 5 hours, the reactant was cooled to room temperature. The cooled reaction solution was neutralized with an aqueous solution of 0.2N hydrochloric acid to be precipitated, filtered and then washed with water. Then, the filtered reactant was dried in a vacuum oven at 100° C. for a day. After removing water and the residual solvent, a compound of Formula I below (PN4) was obtained in a yield of about 87% by weight.

##STR00007##

[0071] The NMR analysis results on the compound of Formula I are shown in FIG. 4. The analysis results on the compound are summarized in Table 1.

Preparation Example 5

Synthesis of Compound (CA1)

[0072] A commercial product from TCI (Tokyo Chemical Industry Co., Ltd.) was obtained as a compound of Formula J below (CA1) and used without further purification.

##STR00008##

[0073] DSC and TGA analysis results on the compounds (PN1, PN2, PN3, PN4) of Preparation Examples 1 to 4 are summarized in Table 1 below.

TABLE-US-00001 TABLE 1 Process temperature Residue (%) at (° C.) 800° C. Preparation Example 1 PIN 1 104 42 Preparation Example 2 PIN 2 235 1.1 Preparation Example 3 PIN 3 231 0 Preparation Example 4 PIN 4 217 38

EXAMPLE 1

[0074] To the compound of Formula C (PN1) in Preparation Example 1, 6 mol % of the compound of Preparation Example 5 (CA1) was added compared to the usage of the compound of Formula C and mixed well to prepare a polymerizable composition. Results performing DSC and TGA analyses on the composition are described in Table 2 below. A prepolymer can be prepared by melting the polymerizable composition at 150° C. and stirring it for 5 minutes.

Comparative Example 1

[0075] To the compound of Formula E (PN2) in Preparation Example 2, 6 mol % of the compound of Preparation Example 5 (CA1) was added compared to the usage of the compound of Formula E and mixed well to prepare a polymerizable composition. Results performing DSC and TGA analyses on the composition are described in Table 2 below. A prepolymer can be prepared by melting the polymerizable composition at 240° C. and stirring it for 5 minutes.

Comparative Example 2

[0076] To the compound of Formula G (PN3) in Preparation Example 3, 6 mol % of the compound of Preparation Example 5 (CA1) was added compared to the usage of the compound of Formula G and mixed well to prepare a polymerizable composition. Results performing DSC and TGA analyses on the composition are described in Table 2 below. A prepolymer can be prepared by melting the polymerizable composition at 240° C. and stirring it for 5 minutes.

Comparative Example 3

[0077] To the compound of Formula I (PN4) in Preparation Example 4, 6 mol % of the compound of Preparation Example 5 (CA1) was added compared to the usage of the compound of Formula I and mixed well to prepare a polymerizable composition. Results performing DSC and TGA analyses on the composition are described in Table 2 below. A prepolymer can be prepared by melting the polymerizable composition at 240° C. and stirring it for 5 minutes.

[0078] Results performing DSC and TGA analyses on the compositions of Example and Comparative Examples are described in Table 2 below.

TABLE-US-00002 TABLE 2 Process Exothermal onset Process temperature temperature window Residue (%) at (° C.) (° C.) (° C.) 900° C. Example 1 103 275 172 73 Comparative 233 263 30 64 Example 1 Comparative 230 280 50 52 Example 2 Comparative 218 258 40 — Example 3

[0079] It can be confirmed from the results of Table 2 that when the compound of Formula 1 of the present application is used, the composition exhibit a significantly wide process window, while showing a low process temperature compared to Comparative Examples.

[0080] That is, the case of Example 1 using the compound of a structure in which m and n in Formula 1 are 1, while having three phthalonitrile groups, has much lower process temperature compared to the cases of Comparative Examples 1 and 2 having two phthalonitrile groups, and thus it can be confirmed that a prepolymer may be prepared at a low temperature, a wide process window of 100° C. or more and it shows a good heat-resistant property.

[0081] In addition, although the case of Comparative Example 3 has three phthalonitrile groups as in the case of Example 1, crystallinity increased due to symmetry of the core part structure and accordingly the process temperature highly increased, so that the process window was confirmed to be very narrow.