LOW FRICTION RESIN COMPOSITES

Abstract

The present invention relates to a low friction resin composite comprising a binder comprising phthalonitrile-based resin, and three or more kinds of fillers dispersed in the binder.

Claims

1. A low friction resin composite comprising: a binder comprising phthalonitrile-based resin; and three or more kinds of fillers dispersed in the binder.

2. The low friction resin composite according to claim 1, wherein the fillers are three or more kinds of additives selected from the group consisting of graphite, polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and milled carbon fiber.

3. The low friction resin composite according to claim 2, wherein the fillers comprise graphite, and two or more kinds of additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and milled carbon fiber.

4. The low friction resin composite according to claim 1, wherein the fillers are powder additives having a longest diameter of 0.01 to 100 m.

5. The low friction resin composite according to claim 1, comprising: 100 parts by weight of the binder comprising phthalonitrile-based resin; and 1 to 100 parts by weight of the fillers.

6. The low friction resin composite according to claim 3, wherein the composite comprises, based on 100 parts by weight of the binder comprising phthalonitrile-based resin: 15 to 30 parts by weight of graphite; and 10 to 40 parts by weight of two kinds of additives selected from the group consisting of polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, and milled carbon fiber.

7. The low friction resin composite according to claim 1, wherein the binder comprising phthalonitrile-based resin is obtained by curing a composition containing a phthalonitrile compound by one or more curing agents selected from the group consisting of an amine-based compound, a hydroxy-based compound, and an imide-based compound.

8. The low friction resin composite according to claim 7, wherein the phthalonitrile compound is a compound of the following Chemical Formula P1: ##STR00030## wherein in Chemical Formula P1, each of R.sup.P11 to R.sup.P16 is independently, hydrogen, a C.sub.1-5 alkyl group, C.sub.1-5 alkoxy group, C.sub.6-30 aryl group, a group of the following Chemical Formula P2, or a group of the following Chemical Formula P3, and two or more of R.sup.P11 to R.sup.P16 are a group of the following Chemical Formula P2 or a group of the following Chemical Formula P3: ##STR00031## wherein in Chemical Formula P2: L.sup.P2 is a direct bond, a C.sub.1-5 alkylene group, O, S, C(O), S(O), or S(O)2-; each of R.sup.P21 to R.sup.P25 is independently, hydrogen, a C.sub.1-5 alkyl group, a C.sub.1-5 alkoxy group, a C.sub.6-30 aryl group, or a cyano group; and two or more of R.sup.P21 to R.sup.P25 are cyano groups, ##STR00032## wherein in Chemical Formula P3: L.sup.P3 is a direct bond, a C.sub.1-5 alkylene group, O, S, C(O), S(O), S(O).sub.2, C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, or C(O)NH; each of R.sup.P31 to R.sup.P35 is independently, hydrogen, a C.sub.1-5 alkyl group, a C.sub.1-5 alkoxy group, a C.sub.6-30 aryl group, or the group of Chemical Formula P2; and one or more of R.sup.P31 to R.sup.P35 are the group of Chemical Formula P2.

9. The low friction resin composite according to claim 7, wherein the curing agent is an imide-based compound of the following Chemical Formula 9: ##STR00033## wherein in Chemical Formula 9: 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.

10. The low friction resin composite according to claim 9, wherein M in Chemical Formula 9 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 10 to 15: ##STR00034## wherein in Chemical Formula 10, each of R.sup.101 to R.sup.106 is independently, hydrogen, an alkyl group, an alkoxy group, or an aryl group; ##STR00035## wherein in Chemical Formula 11, each of R.sup.111 to R.sup.118 is independently, hydrogen, an alkyl group, an alkoxy group, or an aryl group; ##STR00036## wherein in Chemical Formula 12: each of R.sup.120 to R.sup.129 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-OC(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; ##STR00037## wherein in Chemical Formula 13: each of R.sup.131 to R.sup.134 is independently, hydrogen, an alkyl group, or an alkoxy group, and two of R.sup.131 to R.sup.134 can be connected to each other to form an alkylene group; 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; ##STR00038## wherein in Chemical Formula 14: each of R.sup.141 to R.sup.144 is independently, hydrogen, an alkyl group, or an alkoxy group; and A is an alkylene group; ##STR00039## wherein in Chemical Formula 15: each of R.sup.150 to R.sup.159 is independently, hydrogen, an alkyl group, or an alkoxy group.

11. The low friction resin composite according to claim 9, wherein in the Chemical Formula 9, n is a number in the range of 2 to 200.

12. The low friction resin composite according to claim 1, wherein a friction coefficient under a non-lubricated condition, measured for a thrust washer test specimen having a contact area of 1.3 cm.sup.2 against carbon steel friction subject material under PV Value of 2.3 MPa.Math.m/s according to ASTM D3702, is 0.175 or less.

13. The low friction resin composite according to claim 1, wherein a friction coefficient under a lubricated (lubricant: automobile lubricating oil) condition, measured for a thrust washer test specimen having a contact area of 1.3 cm.sup.2 against carbon steel friction subject material under PV Value of 4.6 MPa.Math.m/s according to ASTM D3702, is 0.060 or less.

14. A relative friction component material comprising the low friction resin composite of claim 1.

15. The relative friction component material according to claim 14, wherein the relative friction component material is a bearing, a bushing, a thrust washer, an oil seal, a piston ring, a sliding, or a roller.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0218] FIG. 1 is an exploded perspective view of the friction coefficient measuring apparatus for measuring a friction coefficient according to ASTM D3702.

[0219] FIGS. 2 to 4 show the .sup.1H-NMR data of the compounds prepared in Preparation Examples 1 to 3, respectively.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0220] 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.

[0221] .sup.1H-NMR (Nuclear Magnetic Resonance) Analysis

[0222] 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.

Preparation Example 1. Synthesis of a Phthalonitrile Compound (PN1)

[0223] The compound of the following Chemical Formula A1 (PN1) was synthesized as follows.

[0224] 32.7 g of the compound of the following Chemical Formula A2 and 120 g of DMF (Dimethyl Formamide) were introduced into a 3 neck round bottom flask, and stirred at room temperature to dissolve. Subsequently, 51.9 g of the compound of the following Chemical Formula A3 was added, and 50 g of DMF was added, and then, stirred to dissolve. Subsequently, 62.2 g of potassium carbonate and 50 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, water and remaining solvents were removed, and then, the compound of the following Chemical Formula A1 (PN1) was obtained with the yield of about 80 wt %. The .sup.1H-NMR analysis result for the obtained compound of Chemical Formula A1 (PN1) is shown in FIG. 2.

##STR00027##

Preparation Example 2. Synthesis of a Curing Agent Compound (CA1)

[0225] A compound of the following Chemical Formula A14 (CA1) was synthesized by dehydrogenation condensation of diamine and dianhydride. 24 g of 4,4-oxydianiline and 40 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 8.7 g of a compound of the following Chemical Formula A15 was gradually introduced together with 40 g of NMP in three portions. When the introduced compounds were completely dissolved, 16 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. 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 of the Chemical Formula A14 (CA1) with the yield of about 85 wt %. The .sup.1H-NMR analysis results of the obtained compound of Chemical Formula A14 (CA1) is shown in FIG. 3.

##STR00028##

Preparation Example 3. Synthesis of a Curing Agent Compound (CA2)

[0226] A compound of the following Chemical Formula A18 (CA2) was synthesized by dehydrogenation condensation of diamine and dianhydride. 8.1 g of a compound of the following Chemical Formula A16 (m-phenylene diamine) and 50 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 26 g of a compound of the following Chemical Formula A17 was gradually introduced together with 60 g of NMP in three portions. When the introduced compounds were completely dissolved, 23 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. 5.2 mL of pyridine was introduced as a dehydrogenation condensation catalyst, the temperature was raised to 170 C., and the solution was stirred for 3 hours. 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 soxhlet extracted with methanol to remove remaining reactants, and dried in a vacuum oven to obtain a compound of Chemical Formula A18 (CA2) with the yield of about 93 wt %. The .sup.1H-NMR analysis results of the obtained compound of the Chemical Formula A18 (CA2) is shown in FIG. 4.

##STR00029##

[0227] In Chemical Formula A18, n is about 3.

Example 1

[0228] 100 parts by weight of the compound of Preparation Example 1 (PN1), and based on 1 mole of the compound (PN1), about 0.18 moles of the compound of Preparation Example 3 (CA1) were mixed to prepare a binder.

[0229] To 100 parts by weight of the binder, 21.4 parts by weight of graphite (manufacturing company: Samchun chemicals, powder having a particle diameter of 100 m or less), 14.2 parts by weight of tungsten disulfide (WS.sub.2, manufacturing company: Zerofriction, particle diameter 800 nm), and 7.14 parts by weight of polytetrafluoroethylene (PTFE, manufacturing company: DuPont, particle diameter 4 m) were added, and then, they were thoroughly mixed to prepare a resin composite.

Example 2

[0230] 100 parts by weight of the compound of Preparation Example 1 (PN1), and based on 1 mole of the compound (PN1), about 0.18 moles of the compound of Preparation Example 3 (CA1) were mixed to prepare a binder.

[0231] To 100 parts by weight of the binder, 21.4 parts by weight of graphite (manufacturing company: Samchun chemicals, powder having a particle diameter 100 m or less), 7.1 parts by weight of molybdenum disulfide (MoS.sub.2, manufacturing company: Sigma-Aldrich, particle diameter 2 m), and 14.2 parts by weight of milled carbon fiber (mCF, manufacturing company: Zoltek, length 100 m) were added, and then, they were thoroughly mixed to prepare a resin composite.

Example 3

[0232] 100 parts by weight of the compound of Preparation Example 1 (PN1), and based on 1 mole of the compound (PN1), about 0.18 moles of the compound of Preparation Example 3 (CA1) were mixed to prepare a binder.

[0233] To 100 parts by weight of the binder, 23.1 parts by weight of graphite (manufacturing company: Samchun chemicals, powder having a particle diameter 100 m or less), 15.4 parts by weight of tungsten disulfide (WS.sub.2, manufacturing company: Zerofriction, particle diameter 800 nm), and 15.4 parts by weight of polytetrafluoroethylene (PTFE, manufacturing company: DuPont, particle diameter 4 m) were added, and then, they were thoroughly mixed well to prepare a resin composite.

Comparative Example 1

[0234] 100 parts by weight of the compound of Preparation Example 1 (PN1), and based on 1 mole of the compound (PN1), about 0.18 moles of the compound of Preparation Example 3 (CA1) were mixed to prepare a binder.

[0235] To 100 parts by weight of the binder, 17.6 parts by weight of graphite (manufacturing company: Samchun chemicals, powder having a particle diameter of 100 m or less) was added, and then, they thoroughly mixed to prepare a resin composite.

Comparative Example 2

[0236] 100 parts by weight of the compound of Preparation Example 1 (PN1), and based on 1 mole of the compound (PN1), about 0.18 moles of the compound of Preparation Example 3 (CA1) were mixed to prepare a binder.

[0237] To 100 parts by weight of the binder, 20.0 parts by weight of graphite (manufacturing company: Samchun chemicals, powder having a particle diameter of 100 m or less) and 13.3 parts by weight of polytetrafluoroethylene (PTFE, manufacturing company: DuPont, particle diameter 4 m) were added, and then, they were thoroughly mixed to prepare a resin composite.

Comparative Example 3

[0238] 100 parts by weight of the compound of Preparation Example 1 (PN1), and based on 1 mole of the compound (PN1), about 0.18 moles of the compound of Preparation Example 3 (CA1) were mixed to prepare a binder.

[0239] To 100 parts by weight of the binder, 20.0 parts by weight of graphite (manufacturing company: Samchun chemicals, powder having a particle diameter of 100 m or less) and 13.3 parts by weight of tungsten disulfide (WS.sub.2, manufacturing company: Zerofriction, particle diameter 800 nm) were added, and then, they were thoroughly mixed to prepare a resin composite.

Comparative Example 4

[0240] 100 parts by weight of the compound of Preparation Example 1 (PN1), and based on 1 mole of the compound (PN1), about 0.18 moles of the compound of Preparation Example 3 (CA1) were mixed to prepare a binder.

[0241] To 100 parts by weight of the binder, 18.8 parts by weight of graphite (manufacturing company: Samchun chemicals, powder having a particle diameter of 100 m or less) and 6.3 parts by weight of molybdenum disulfide (MoS.sub.2, manufacturing company: Sigma-Aldrich, particle diameter 2 m) were added, and then, they were thoroughly mixed to prepare a resin composite.

Comparative Example 5

[0242] 100 parts by weight of the compound of Preparation Example 1 (PN1), and based on 1 mole of the compound (PN1), about 0.18 moles of the compound of Preparation Example 3 (CA1) were mixed to prepare a binder.

[0243] To 100 parts by weight of the binder, 20.0 parts by weight of graphite (manufacturing company: Samchun chemicals, powder having a particle diameter of 100 m or less) and 13.3 parts by weight of milled carbon fiber (mCF, manufacturing company: Zoltek, length 100 m) were added, and then, they were thoroughly mixed to prepare a resin composite.

Comparative Example 6

[0244] A low friction grade product Vespel-SP21 from DuPont Company was commercially acquired and used. The Vespel-SP21 product is known to contain polyimide resin and 15 wt % of graphite (based on 100 parts by weight of PI resin, 17.6 parts by weight of graphite).

Comparative Example 7

[0245] A low friction grade product PEEK 450FC30 from Victrex Company was commercially acquired and used. The PEEK 450FC30 product is known to contain 30 parts by weight of fillers (a mixture of carbon fiber, graphite and PTFE), based on 100 parts by weight of polyetheretherketone resin.

Reference Example 1

[0246] 100 parts by weight of the compound of Preparation Example 1 (PN1), and based on 1 mole of the compound (PN1), about 0.18 moles of the compound of Preparation Example 3 (CA1) were mixed to prepare a binder.

[0247] To 100 parts by weight of the binder, 21.4 parts by weight of molybdenum disulfide (MoS.sub.2, manufacturing company: Sigma-Aldrich, particle diameter 2 m), 14.2 parts by weight of tungsten disulfide (WS.sub.2, manufacturing company: Zerofriction, particle diameter 800 nm), and 7.14 parts by weight of polytetrafluoroethylene (PTFE, manufacturing company: DuPont, particle diameter 4 m) were added, and then, they were thoroughly mixed to prepare a resin composite.

Reference Example 2

[0248] 100 parts by weight of the compound of Preparation Example 1 (PN1), and based on 1 mole of the compound (PN1), about 0.18 moles of the compound of Preparation Example 3 (CA1) were mixed to prepare a binder.

[0249] To 100 parts by weight of the binder, 21.4 parts by weight of milled carbon fiber (mCF, manufacturing company: Zoltek, length 100 m), 14.2 parts by weight of tungsten disulfide (WS.sub.2, manufacturing company: Zerofriction, particle diameter 800 nm), and 7.14 parts by weight of polytetrafluoroethylene (PTFE, manufacturing company: DuPont, particle diameter 4 m) were added, and then, they were thoroughly mixed to prepare a resin composite.

Experimental Example

[0250] Each resin composite prepared in Examples and Comparative Examples was melted at 240 C. and stirred for 5 minutes to prepare prepolymer.

[0251] The prepolymer was put in a mold and melted, and then, cured under conditions of 200 C. for 2 hours, 250 C. for 2 hours, 300 C. for 2 hours and 350 C. for 2 hours to prepare thrust washer test specimens according to ASTM D3702 standard. And, the products of Comparative Examples 5 and 6 were cut to prepare thrust washer test specimens according to ASTM D3702 standard.

[0252] As carbon steel subject material, S45C was prepared. S45C means carbon steel material for machine structure, which is steel material containing 0.45% of carbon according to JIS G4053 standard.

[0253] The friction coefficient and wear rate of the test specimens were measured using a friction coefficient measuring device (TE 92, manufactured by Phoenix Company) according to ASTM D3702. The results were shown in the following Tables 1 and 2. [0254] PV Value 1: 2.3 MPa.Math.m/s (pressure(P): 1.63 MPa(16 bar, 220 N), rotation speed(V): 1.41 m/s(1000 rpm)) [0255] PV Value 2: 4.6 MPa.Math.m/s (pressure(P): 1.63 MPa(16 bar, 220 N), rotation speed(V): 2.82 m/s(1000 rpm)) [0256] Time: 1200 s [0257] Unlubricated conditions [0258] Lubricated conditions (automobile lubricating oil, sales company: HYUNDAI MOBIS, product name: ATF SP-III)

TABLE-US-00001 TABLE 1 PV Value 1 + unlubricated Fric- Wear tion rate coeffi- (10.sup.10 Binder Filler cient m/s) Example 1 phthalonitrile graphite, WS.sub.2, PTFE 0.088 80.5 Example 2 phthalonitrile graphite, MoS.sub.2, mCF 0.164 123.9 Example 3 phthalonitrile graphite, WS.sub.2, PTFE 0.137 80.5 Comparative phthalonitrile graphite 0.230 161.7 Example 1 Comparative phthalonitrile graphite, PTFE 0.112 168.9 Example 2 Comparative phthalonitrile graphite, WS.sub.2 0.190 175.2 Example 3 Comparative phthalonitrile graphite, MoS.sub.2 0.236 167.1 Example 4 Comparative phthalonitrile graphite, mCF 0.220 Example 5 Reference phthalonitrile WS.sub.2, PTFE, MoS.sub.2 0.211 187.5 Example 1 Reference phthalonitrile WS.sub.2, PTFE, mCF 0.182 201.5 Example 2 Comparative PI graphite 0.297 360.1 Example 6 Comparative PEEK graphite, PTFE, mCF 0.180 56.9 Example 7

TABLE-US-00002 TABLE 2 PV Value 2 + lubricated Fric- Wear tion rate coeffi- (10.sup.10 binder Filler cient m/s) Example 1 phthalonitrile graphite, WS.sub.2, PTFE 0.052 Example 2 phthalonitrile graphite, MoS.sub.2, mCF 0.051 Example 3 phthalonitrile graphite, WS.sub.2, PTFE 0.053 Comparative phthalonitrile graphite 0.074 Example 1 Comparative phthalonitrile graphite, PTFE 0.110 Example 2 Comparative phthalonitrile graphite, WS.sub.2 0.108 Example 3 Comparative phthalonitrile graphite, MoS.sub.2 0.119 Example 4 Comparative phthalonitrile graphite, mCF 0.075 Example 5 Reference phthalonitrile WS.sub.2, PTFE, MoS.sub.2 0.092 Example 1 Reference phthalonitrile WS.sub.2, PTFE, mCF 0.102 Example 2 Comparative PI graphite 0.052 Example 6 Comparative PEEK graphite, PTFE, mCF 0.055 Example 7

[0259] Referring to Table 1, it is confirmed that the test specimens according to Examples 1 to 3 exhibit low friction coefficients or low wear rates, compared to the test specimens of Comparative Examples 1 to 5.

[0260] Particularly, as confirmed through Examples 1, 3 and Comparative Example 3, in case graphite and tungsten disulfide were used as filler, when applying polytetrafluoroethylene together, friction property was remarkably improved.

[0261] And, as confirmed through Example 2 and Comparative Example 4, in case graphite and molybdenum disulfide were used as filler, when applying milled carbon fiber together, friction property was remarkably improved.