Phthalonitrile-based resin with improved impact strength

Abstract

Provided is a phthalonitrile-based resin, comprising repeat units formed by the reaction of a phthalonitrile compound and a curing agent, wherein the phthalonitrile compound comprises 4,4-bis(3,4-dicyanophenoxy)diphenyloxide of the following Chemical Formula 1 and 4,4-bis(3,4-dicyanophenoxy)biphenyl of the following Chemical Formula 2 at a weight ratio of 30:70 to 90:10: ##STR00001##

Claims

1. A phthalonitrile-based resin, comprising repeat units formed by the reaction of a phthalonitrile compound and a curing agent, wherein the phthalonitrile compound comprises 4,4-bis(3,4-dicyanophenoxy)diphenyloxide of the following Chemical Formula 1 and 4,4-bis(3,4-dicyanophenoxy)biphenyl of the following Chemical Formula 2 at a weight ratio of 30:70 to 90:10, and wherein the curing agent is an imide-based compound of the following Chemical Formula 3: ##STR00023## wherein in Chemical Formula 3: M is a tetravalent radical derived from an aliphatic, alicyclic or aromatic compound; each of X.sup.1 and X.sup.2 is independently an alkylene group, an alkylidene group, or a divalent radical derived from an aromatic compound; and n is a number equal to or greater than 1.

2. The phthalonitrile-based resin according to claim 1, wherein M in Chemical Formula 3 is a tetravalent radical derived from alkane, alkene, or alkyne, or a tetravalent radical derived from a compound of any one of the following Chemical Formulas 4 to 9: ##STR00024## wherein in Chemical Formula 4, each of R.sup.40 to R.sup.45 is independently hydrogen, an alkyl group, an alkoxy group, or an aryl group; ##STR00025## wherein in Chemical Formula 5, each of R.sup.50 to R.sup.57 is independently hydrogen, an alkyl group, an alkoxy group, or an aryl group; ##STR00026## wherein in Chemical Formula 6: each of R.sup.60 to R.sup.69 is independently hydrogen, an alkyl group, an alkoxy group, or an aryl group; X is a single bond, an alkylene group, an alkylidene group, O, S, C(?O), S(?O), S(?O).sub.2, C(?O)O-L.sup.1-OC(?O), -L.sup.2-C(?O)O-L.sup.3-, -L.sup.4-O-C(?O)-L.sup.5-, or -L.sup.6-Ar.sup.1-L.sup.7-Ar.sup.2-L.sup.8-; each of L.sup.1 to L.sup.8 is independently a single bond, O, an alkylene group, or an alkylidene group; and each of Ar.sup.1 and Ar.sup.2 is independently an arylene group; ##STR00027## wherein in Chemical Formula 7: each of R.sup.70 to R.sup.73 s independently hydrogen, an alkyl group, or an alkoxy group, and two of R.sup.70 to R.sup.73 an be connected to each other to form an alkylene group; and A is an alkylene group or an alkenylene group, and the alkylene group or alkenylene group of A can comprise one or more oxygen atoms as a hetero atom; ##STR00028## wherein in Formula 8: each of R.sup.80 to R.sup.83 is independently hydrogen, an alkyl group, or an alkoxy group; and A is an alkylene group; ##STR00029## wherein in Chemical Formula 9, each of R.sup.90 to R.sup.99 is independently hydrogen, an alkyl group, or an alkoxy group.

3. The phthalonitrile-based resin according to claim 1, wherein in Chemical Formula 3, each of X.sup.1 and X.sup.2 is independently a divalent radical derived from a C6-40 aromatic compound.

4. The phthalonitrile-based resin according to claim 1, wherein in Chemical Formula 3, each of X.sup.1 and X.sup.2 is independently a compound of one of the following Chemical Formulas 10 to 12: ##STR00030## wherein in Chemical Formula 10, each of R.sup.100 to R.sup.105 is independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, or a carboxyl group; ##STR00031## wherein in Chemical Formula 11: each of R.sup.100 to R.sup.119 is independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, or a carboxyl group: X is a single bond, an alkylene group, an alkylidene group, O, S, C(?O), NR.sup.a, S(?O), S(?O).sub.2, -L.sup.9-Ar.sup.3-L.sup.10 or -L.sup.11-Ar.sup.4-L.sup.12-Ar.sup.5-L.sup.13-; R.sup.a is hydrogen, an alkyl group, an alkoxy group, or an aryl group; each of L.sup.9 to L.sup.13 is independently a single bond, 0, an alkylene group, or an alkylidene group; and each of Ar.sup.3 to Ar.sup.5 is independently an arylene group; ##STR00032## wherein in Chemical Formula 12, each of R.sup.120 to R.sup.129 is independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, or a carboxyl group.

5. The phthalonitrile-based resin according to claim 1, wherein the resin has impact strength of 350 MPa to 500 MPa according to a ASTM D256 (23? C.) test method.

6. A molded article comprising the phthalonitrile-based resin of claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1 to 3 respectively show the .sup.1HNMR data of the compounds according to Preparation Examples 1 to 3.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(2) Hereinafter, preferable examples are presented for better understanding of the present invention. However, these examples are presented only as the illustrations of the present invention, and the scope of the present invention is not limited thereby.

PREPARATION EXAMPLE 1

Synthesis of a Phthalonitrile Compound (PN1)

(3) 25.3 g of 4,4-dihydroxybiphenyl and 145.0 g of DMF(dimethyl formamide) were introduced into a 3 neck round bottom flask, and stirred at room temperature to dissolve. Subsequently, 43.3 g of 4-nitrophthalonitrile was added, 70.0 g of DMF was added, and then, stirred to dissolve. Subsequently, 36.3g of potassium carbonate and 30.0 g of DMF were introduced together, and the temperature was raised to 85? C. while stirring. After reacting for about 5 hours, the solution was cooled to room temperature. The cooled reaction solution was poured into the aqueous solution of 0.2 N hydrochloric acid to neutralize and precipitate, and after filtering, washed with water. Thereafter, the filtered reactant was dried in a vacuum oven of 100? C. for a day, and water and remaining solvents were removed, thus obtaining a PN1 compound(4,4-bis(3,4-dicyanophenoxy)diphenyloxide) of the following Chemical Formula 1 with the yield of 91 wt %.

(4) The .sup.1H-NMR analysis result for the obtained compound of the compound PN1 is shown in FIG. 1.

(5) ##STR00020##

PREPARATION EXAMPLE 2

Synthesis of a Phthalonitrile Compound (PN2)

(6) 23.3 g of 4,4-dihydroxybiphenyl and 140 g of DMF(dimethyl formamide) were introduced into a 3 neck round bottom flask, and stirred at room temperature to dissolve. Subsequently, 43.3 g of 4-nitrophthalonitrile was added, 70.0 g of DMF was added, and then, stirred to dissolve. Subsequently, 36.3g of potassium carbonate and 30.0 g of DMF were introduced together, and the temperature was raised to 85? C. while stirring. After reacting for about 5 hours, the solution was cooled to room temperature. The cooled reaction solution was poured into the aqueous solution of 0.2 N hydrochloric acid to neutralize and precipitate, and after filtering, washed with water. Thereafter, the filtered reactant was dried in a vacuum oven of 100? C. for a day, and water and remaining solvents were removed, thus obtaining a PN2 compound(4,4-bis(3,4-dicyanophenoxy)biphenyl) of the following Chemical Formula 2 with the yield of 90 wt %.

(7) The .sup.1H-NMR analysis result for the obtained compound of the compound PN2 is shown in FIG. 2.

(8) ##STR00021##

PREPARATION EXAMPLE 3

Synthesis of a Curing Agent Compound (CA1)

(9) 24 g of a compound of the following Chemical Formula a and 45 g of NMP (N-methyl-pyrrolidone) were introduced into a 3 neck round bottom flask, and stirred at room temperature to dissolve. The solution was cooled with a water bath, and 12.4 g of a compound of the following Chemical Formula b was gradually introduced in three portions together with 45 g of NMP. When the introduced compounds were completely dissolved, 18 g of toluene was added to the reactant to form an azeotrope. Dean-Stark equipment and a reflux condenser were installed, and the Dean-Stark equipment was filled with toluene. 4.2 mL of pyridine was introduced as a dehydrogenation condensation catalyst, a temperature was raised to 170? C., and the solution was stirred for 3 hours.

(10) While removing water generated with the formation of an imide ring with the Dean Stark equipment, the solution was additionally stirred for 2 hours, and the remaining toluene and pyridine were removed. The reaction product was cooled to room temperature, and precipitated in methanol to recover. The recovered precipitate was extracted with methanol to remove remaining reactants, and dried in a vacuum oven to obtain a compound CA1 of Chemical Formula c with the yield of 81 wt %.

(11) The .sup.1H-NMR analysis results of the obtained compound CA1 is shown in FIG. 3.

(12) ##STR00022##

EXAMPLE 1

(13) As a phthalonitrile compound, a mixture of 75 wt % of the PN1 compound of Preparation Example 1 and 25 wt % of the PN2 compound of Preparation Example 2 was prepared.

(14) The CA1 compound of Preparation Example 3 was mixed at 0.15 mole per one mole of the phthalonitrile compound to prepare a polymerizable composition.

(15) The polymerizable composition was cured through heating in an oven at a temperature of 220? C., 250? C., 280? C., and 310? C. for a total of 3 hours, thus preparing phthalonitrile-based resin.

EXAMPLE 2

(16) As a phthalonitrile compound, a mixture of 60 wt % of the PN1 compound of Preparation Example 1 and 40 wt % of the PN2 compound of Preparation Example 2 was prepared.

(17) The CA1 compound of Preparation Example 3 was mixed at 0.15 mole per one mole of the phthalonitrile compound to prepare a polymerizable composition.

(18) The polymerizable composition was cured by heating in an oven at a temperature of 220? C., 250? C., 280? C., and 310? C. for a total of 3 hours, thus preparing phthalonitrile-based resin.

Example 3

(19) As a phthalonitrile compound, a mixture of 50 wt % of the PN1 compound of Preparation Example 1 and 50 wt % of the PN2 compound of Preparation Example 2 was prepared.

(20) The CA1 compound of Preparation Example 3 was mixed at 0.15 mole per one mole of the phthalonitrile compound to prepare a polymerizable composition.

(21) The polymerizable composition was cured by heating in an oven at a temperature of 220? C., 250? C., 280? C., and 310? C. for a total of 3 hours, thus preparing phthalonitrile-based resin.

EXAMPLE 4

(22) As a phthalonitrile compound, a mixture of 40 wt % of the PN1 compound of Preparation Example 1 and 60 wt % of the PN2 compound of Preparation Example 2 was prepared.

(23) The CA1 compound of Preparation Example 3 was mixed at 0.15 mole per one mole of the phthalonitrile compound to prepare a polymerizable composition.

(24) The polymerizable composition was cured by heating in an oven at a temperature of 220? C., 250? C., 280? C., and 310? C. for a total of 3 hours, thus preparing phthalonitrile-based resin.

EXAMPLE 5

(25) As a phthalonitrile compound, a mixture of 30 wt % of the PN1 compound of Preparation Example 1 and 70 wt % of the PN2 compound of Preparation Example 2 was prepared.

(26) The CA1 compound of Preparation Example 3 was mixed at 0.15 mole per one mole of the phthalonitrile compound to prepare a polymerizable composition.

(27) The polymerizable composition was cured by heating in an oven at a temperature of 220? C., 250? C., 280? C., and 310? C. for a total of 3 hours, thus preparing phthalonitrile-based resin.

EXAMPLE 6

(28) As a phthalonitrile compound, a mixture of 90 wt % of the PN1 compound of Preparation Example 1 and 10 wt % of the PN2 compound of Preparation Example 2 was prepared.

(29) The CA1 compound of Preparation Example 3 was mixed at 0.15 mole per one mole of the phthalonitrile compound to prepare a polymerizable composition.

(30) The polymerizable composition was cured by heating in an oven at a temperature of 220? C., 250? C., 280? C., and 310? C. for a total of 3 hours, thus preparing phthalonitrile-based resin.

COMPARATIVE EXAMPLE 1

(31) As a phthalonitrile compound, the PN1 compound of Preparation Example 1 was prepared.

(32) The CA1 compound of Preparation Example 3 was mixed at 0.15 mole per one mole of the phthalonitrile compound to prepare a polymerizable composition.

(33) The polymerizable composition was cured by heating in an oven at a temperature of 220? C., 250? C., 280? C., and 310? C. for a total of 3 hours, thus preparing phthalonitrile-based resin.

COMPARATIVE EXAMPLE 2

(34) As a phthalonitrile compound, the PN2 compound of Preparation Example 2 was prepared.

(35) The CA1 compound of Preparation Example 3 was mixed at 0.15 mole per one mole of the phthalonitrile compound to prepare a polymerizable composition.

(36) The polymerizable composition was cured by heating in an oven at a temperature of 220? C., 250? C., 280? C., and 310? C. for a total of 3 hours, thus preparing phthalonitrile-based resin.

COMPARATIVE EXAMPLE 3

(37) As a phthalonitrile compound, a mixture of 10 wt % of the PN1 compound of Preparation Example 1 and 90 wt % of the PN2 compound of Preparation Example 2 was prepared.

(38) The CA1 compound of Preparation Example 3 was mixed at 0.15 mole per one mole of the phthalonitrile compound to prepare a polymerizable composition.

(39) The polymerizable composition was cured by heating in an oven at a temperature of 220? C., 250? C., 280? C., and 310? C. for a total of 3 hours, thus preparing phthalonitrile-based resin.

COMPARATIVE EXAMPLE 4

(40) As a phthalonitrile compound, a mixture of 25 wt % of the PN1 compound of Preparation Example 1 and 75 wt % of the PN2 compound of Preparation Example 2 was prepared.

(41) The CA1 compound of Preparation Example 3 was mixed at 0.15 mole per one mole of the phthalonitrile compound to prepare a polymerizable composition.

(42) The polymerizable composition was cured by heating in an oven at a temperature of 220? C., 250? C., 280? C., and 310? C. for a total of 3 hours, thus preparing phthalonitrile-based resin.

COMPARATIVE EXAMPLE 5

(43) As a phthalonitrile compound, a mixture of 95 wt % of the PN1 compound of Preparation Example 1 and 5 wt % of the PN2 compound of Preparation Example 2 was prepared.

(44) The CA1 compound of Preparation Example 3 was mixed at 0.15 mole per one mole of the phthalonitrile compound to prepare a polymerizable composition.

(45) The polymerizable composition was cured by heating in an oven at a temperature of 220? C., 250? C., 280? C., and 310? C. for a total of 3 hours, thus preparing phthalonitrile-based resin.

EXPERIMENTAL EXAMPLE 1

.SUP.1.H-NMR(Nuclear Magnetic Resonance) Analysis

(46) For the compounds synthesized in Preparation Examples 1 to 3, .sup.1H-NMR analysis was conducted. The results were shown in FIGS. 1 to 3.

(47) The NMR analysis for the compounds prepared below was conducted according to the manual of the manufacturing company using 500 MHz NMR equipment of Agilent Inc. The sample for NMR measurement was prepared by dissolving the compound in DMSO(dimethyl sulfoxide)-d6.

EXPERIMENTAL EXAMPLE 2

DSC (Differential Scanning Calorimetry) Analysis

(48) For the phthalonitrile-based resin obtained in Examples and Comparative Examples, DSC analysis was conducted. From the DSC thermogram, information about the glass transition temperature (T.sub.g), melting temperature (T.sub.m), and exothermic onset temp. (T.sub.o) was obtained. The results were shown in the following Table 1. In the Table 1, a process window (PW) is an absolute value of a difference between the smaller value among T.sub.g and T.sub.m and T.sub.o.

(49) The DSC analysis was conducted under N.sub.2 flow atmosphere while raising temperature from 35? C. to 450? C. at a temperature rise speed of 10? C/min using Q20 system of TA instruments.

EXPERIMENTAL EXAMPLE 3

Measurement of Impact Strength

(50) A specimen without a notch of ASTM D256 standard was manufactured, and using a Digital impact tester (QM(700A)), the impact strength (IS) of the phthalonitrile-based was measured according to a ASTM D256 (23? C.) test method. The results were shown in the following Table 1.

EXPERIMENTAL EXAMPLE 4

Observation of the State of Resin After Curing

(51) It was observed with unaided eyes whether or not a void exists in the phthalonitrile-based resin obtained in Examples and Comparative Examples.

(52) Through relative evaluation, in case a void does not exist, it was classified as ?, in case many voids exist, it was classified as X, and in case a little voids exist, it was classified as ?. The results were shown in the following Table 1.

(53) TABLE-US-00001 TABLE 1 T.sub.g (? C.) T.sub.m (? C.) T.sub.o (? C.) PW (? C.) IS (MPa) Void Example 1 69 278 209 430 ? Example 2 69 277 208 454 ? Example 3 71 206 277 206 459 ? Example 4 69 209 274 65 440 ? Example 5 68 215 273 65 437 ? Example 6 64 278 214 415 ? Comparative 63 189 283 94 297 ? Example 1 Comparative 75 229 289 60 232 X Example 2 Comparative 225 273 48 235 ? Example 3 Comparative 217 273 56 331 ? Example 4 Comparative 64 278 214 302 ? Example 5

(54) Referring to Table 1, it was confirmed that the phthalonitrile-based resins according to Examples exhibit wide process window and excellent impact strength, and do not have void in the resin.