WO1998007779A9 - Compositions thermoplastiques comportant de l'oxyde de zinc et des homo ou copolymeres de tetrafluoroethylene et articles façonnes a partir de celles-ci - Google Patents
Compositions thermoplastiques comportant de l'oxyde de zinc et des homo ou copolymeres de tetrafluoroethylene et articles façonnes a partir de celles-ciInfo
- Publication number
- WO1998007779A9 WO1998007779A9 PCT/US1997/014510 US9714510W WO9807779A9 WO 1998007779 A9 WO1998007779 A9 WO 1998007779A9 US 9714510 W US9714510 W US 9714510W WO 9807779 A9 WO9807779 A9 WO 9807779A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- zinc oxide
- iii
- polymer
- weight percent
- Prior art date
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 47
- BFKJFAAPBSQJPD-UHFFFAOYSA-N Tetrafluoroethylene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229920001577 copolymer Polymers 0.000 title claims abstract description 11
- 229920001169 thermoplastic Polymers 0.000 title claims description 12
- 229920001519 homopolymer Polymers 0.000 title description 2
- 239000004416 thermosoftening plastic Substances 0.000 title description 2
- 239000002245 particle Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 229920001721 Polyimide Polymers 0.000 claims description 37
- 239000004642 Polyimide Substances 0.000 claims description 28
- -1 aromatic diol Chemical class 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000009719 polyimide resin Substances 0.000 claims description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-Hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- BGNXCDMCOKJUMV-UHFFFAOYSA-N TBHQ Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 239000011528 polyamide (building material) Substances 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N 2,6-Naphthalenedicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N cyclohexane-1,4-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 32
- 239000004810 polytetrafluoroethylene Substances 0.000 description 28
- 239000000654 additive Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4,4'-Oxydianiline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 7
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229920000106 Liquid crystal polymer Polymers 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 229920005575 poly(amic acid) Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 230000000996 additive Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000006159 dianhydride group Chemical group 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000003754 machining Methods 0.000 description 4
- PGNWIWKMXVDXHP-UHFFFAOYSA-L zinc;1,3-benzothiazole-2-thiolate Chemical compound [Zn+2].C1=CC=C2SC([S-])=NC2=C1.C1=CC=C2SC([S-])=NC2=C1 PGNWIWKMXVDXHP-UHFFFAOYSA-L 0.000 description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching Effects 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 229940018564 M-PHENYLENEDIAMINE Drugs 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N M-Phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N P-Phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000023298 conjugation with cellular fusion Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- 230000021037 unidirectional conjugation Effects 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- LCJRHAPPMIUHLH-UHFFFAOYSA-N 1-$l^{1}-azanylhexan-1-one Chemical compound [CH]CCCCC([N])=O LCJRHAPPMIUHLH-UHFFFAOYSA-N 0.000 description 1
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- 229920000122 Acrylonitrile butadiene styrene Polymers 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N BPDA Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229920000840 ETFE Polymers 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N Hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N Isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N Molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004957 Zytel Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated Effects 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- VOLSCWDWGMWXGO-UHFFFAOYSA-N cyclobuten-1-yl acetate Chemical compound CC(=O)OC1=CCC1 VOLSCWDWGMWXGO-UHFFFAOYSA-N 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 230000000877 morphologic Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 235000015108 pies Nutrition 0.000 description 1
- 229920002496 poly(ether sulfone) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000069 poly(p-phenylene sulfide) Polymers 0.000 description 1
- 229920002492 poly(sulfones) Polymers 0.000 description 1
- 229920002530 poly[4-(4-benzoylphenoxy)phenol] polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005587 polyester-imide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002195 synergetic Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Definitions
- thermoplastic polymers alone and blends of such polymers with other polymers such as polyimides, and polyimide precursor resins are injection moldable and provide a unique combination of properties.
- the outstanding performance characteristics of these polymers under stress have made them useful in the form of bushings, seals, compressor vanes and impellers, pistons and piston rings, gears, thread guides, cams, brake linings, and clutch faces.
- the present invention solves the aforementioned problems by providing a polymeric composition having uniformly dispersed therein controlled amounts of zinc oxide and non-fibrillating tetrafluoroethylene homopolymers and copolymers of tetrafluoroethylene, collectively referred to herein as PTFE, in finely divided form.
- the zinc oxide must be of a selected particle size, and the PTFE must have a controlled molecular weight.
- the two ingredients are present in the composition in a selected weight ratio. When used in accordance with the present invention, these additives disperse uniformly throughout the polymer matrix and give molding compositions of exceptional uniformity. Shaped articles prepared therefrom exhibit improved wear properties.
- Polymeric blends of this invention comprise from about 40 to 98 weight percent of at least one thermoplastic polymer which is melt processible at temperatures of less than about 400°C, from about 1 to 38 weight percent of zinc oxide having a mean particle size of less than 3.7 ⁇ m, preferably at least 25% having a particle size of less than 2 ⁇ , and from about 38 to 1 weight percent of PTFE in finely divided powder form having a molecular weight in the range from about 80,000 to 1,000,000.
- the PTFE has a mean particle size of from about 1.8 ⁇ m to about 150 ⁇ m. Preferably the size is from 4to 20 ⁇ m.
- the zinc oxide and PTFE particles are present in a ratio of from about 95 parts PTFE/5 parts of zinc oxide to about 10 parts PTFE/90 parts zinc oxide.
- compositions of this invention may also be comprised of blends of the thermoplastic polymers with other polymers such as polyimides and polyimide precursor resins. These blends may contain from about 40 to 93weight percent of thermoplastic polymer and from about 5 to 40 weight percent of a polyimide or polyimide precursor resin, preferably 10-30 weight percent of the polyimide or polyimide precursor resin is used.
- the polyimide may or may not be melt processible.
- FIG. 1 is a photomicrograph of a polymeric composition which is outside to scope of the present invention and is described in Sample VI of Example 3 showing poor dispersion of PTFE in the sample.
- FIG. 2 is a photomicrograph of a polymeric composition of this invention
- melt processible polymers can be blended with the zinc oxide and PTFE particles.
- Polyamides which can be used include nylon 6, nylon 6,6, nylon 610
- the melt processible polyesters are preferably in the form of liquid crystalline polymers (LCPs).
- LCPs are generally polyesters including, but not limited to polyesteramides and polyesterimides.
- LCPs are described in Jackson et al. in U.S. Pat. Nos. 4,169,933, 4,242,496, and 4,238,600, as well as in "Liquid Crystal Polymers: VI Liquid Crystalline Polyesters of Substituted Hydroquinones", Contemporary Topics in Polymer Science, 1984, Vol. 5, pp. 177-208. Others are described in Calundann, U.S. Pat. No. 4,219,461.
- LCPs are prepared from monomers such as phenyl hydroquinone, hydroquinone, t-butyl hydroquinone, 1 ,4-benzene dicarboxylic acid, 1,3-benzene dicarboxylic acid, 4-hydroxybenzoic acid, terephthalic acid and 2,6-napthalene dicarboxylic acid in varying ratios.
- Preferred LCP compositions are disclosed in U.S. Pat. Nos. 4,664,972 and 5,1 10, 896 which is incorporated by reference herein.
- compositions of the first-mentioned patent consist essentially of (I) an aromatic diol consisting essentially of 95 to 55 mole % t- butylhydroquinone and 5 to 45 mole % of one or more polyaromatic diols, (II) a dicarboxylic acid component selected from "para” or “meta” oriented aromatic dicarboxylic or 1 ,4-cyclohexane dicarboxylic acid or mixtures thereof, provided that no more than 80 mole % of the dicarboxylic acid component comprises a naphthalene dicarboxylic acid, and (III) an aromatic hydroxycarboxylic acid component selected from 4-(4"-hydroxyphenyl)benzoic acid or mixtures thereof; where said copolyester contains equal chemical equivalents of components (I) and (II) and contain about 20 to 60 mole %, based on total moles (I)+(II)+ (III) of component (III).
- compositions of the second mentioned patent consist essentially of recurring units derived from (I) hydroquinone, (II) 4,4'- dihydroxyphenyl, (III) terephthalic acid, (IV) 2,6-naphthalene dicarboxylic acid, and (V) 4— hydroxybenzoic acid wherein the mole ratio of (I): (II) is from 65:35 to 40:60, preferably 60:40 to 40:60, wherein the molar ratio of (III) to (IV) is from 85: 15 to 50:50, preferably 85: 15 to 60:40, wherein the molar ratio of (I) to (II) to the total of (III) to (IV) is substantially 1 : 1 , preferably 0.95-1.05 : 1.00, and wherein there are 200 to 600, preferably 200 to 450 moles of (V) per 100 moles of (I) plus (II).
- LCPs useful in this invention consist essentially of repeating units derived from (I) t-butylhydroquinone and terephthalic acid, ( II) t- butylhydroquinone and 2,6-naphthalene carboxylic acid, and (III) 4- hydroxybenzoic acid, the molar ration of (I):(II) being about 4: 1 to about 1 :4, more preferably about 3: 1 to 1 :3 with the molar ratio of (I)+(II):(III) being about 3: 1 to about 2:3.
- Aromatic polyimides such as those described in Edwards, U.S. Pat. No. 3,179,614, and Manwiller and Anton, U.S. Pat. No. 4,755,555, can be used.
- polyimides have been found to be particularly satisfactory in the present invention, namely, those having a rigid polymeric structure.
- rigid polymeric materials are those prepared using aromatic diamines and anhydrides such as m-phenylene diamine (MPD); bis- 4,4'(3 aminophenoxy)biphenyl; 3,4-oxydianiline (3,4-ODA); oxydianiline (ODA); p-phenylene diamine (PPD); benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA); bis phenol-A-diphthalicanhydride (BPADA); pyromellitic dianhydride (PMDA); and 3,3'4,4'-biphenyltetracarbocyclic dianhydride (BPDA).
- MPD m-phenylene diamine
- BPADA bis- 4,4'(3 aminophenoxy)biphenyl
- 3,4-ODA 3,4-oxydianiline
- ODA p-
- the dianhydride and the aromatic diamine may be reacted in substantially equimolar quantities. However, excesses of dianhydride or diamine can be used to beneficially modify the properties of the final polyimide.
- the reaction product of the dianhydride and the aromatic diamine is a polyimide precursor resin, containing polyamic acid which can be thermally or chemically converted to polyimide according to known techniques. Recently, Kaku, in U.S. Pat. No. 5,346,969, described blends of polyimide precursor resin such as described in Endrey, U.S. Pat. No. 3,179,631 and Gall, U.S. Pat. No. 3,249,588, with at least one polyamide or polyester, preferably in the form of liquid crystalline polymer (LCP).
- LCP liquid crystalline polymer
- Blends of polyimide precursor with at least one polymer which is melt processible at a temperature of less than about 400°C. are combined to provide polyimides with injection molding capability. At least one polymer which is melt processible at temperatures of less than about 400°C. is blended with the polyimide resin. Melt processible is used in its conventional sense, that the polymer can be processed in extrusion apparatus at the indicated temperatures without substantial degradation of the polymer.
- the zinc oxide and PTFE particles are included in the blending operation.
- the zinc oxide particles may be prepared from commercially available crystalline zinc oxide by grinding and screening the oxide to obtain the required particle size distribution.
- Nonfibrillating tetrafluoroethylene polymers and copolymers such as tetrafluoroethylene/hexafluoropropylene are commercially available in micropowder form. E.I.du Pont de Nemours and Company sells such materials under its trademark, Teflon® MP. Preparation of such copolymers is described in Morgan, U.S. 4,879,362. Such copolymers have recurring units of tetrafluoroethylene and a comonomer selcted from the group consisting of hexafluoroproplyene, perfluoro(alkyl vinyl ether) where the alkyl group has 1-4 carbons and mixtures of the comonomers.
- the present polymeric compositions may include additives in addition to zinc oxide and PTFE, such as molybdenum disulfide, glass fibers, carbon fibers and carbonaceous fillers such as graphite.
- additives in addition to zinc oxide and PTFE such as molybdenum disulfide, glass fibers, carbon fibers and carbonaceous fillers such as graphite.
- the particular additive selected will depend on the effect desired.
- Suitable materials include coupling agents such as titanate-, silane-, zirconaluminate-, and alumina-type coupling agents, silylating agents, silanol- modified silicone oil, alkoxy-modified silicone oil, and SiH-modified silicone oil. Less than 2 weight percent of the coating material is generally used with from about 0.2 to about 1 weight percent based on the weight of the zinc oxide being preferred.
- Examples wear specimens were prepared by machining test blocks of the composition described. A 6.35mm (0.25") wide contact surface of a wear/friction test block was machined to such a curvature that it conformed to the outer circumference of a 35mm (1.38”) diameter X 8.74mm (0.34") wide metal mating ring. The blocks were oven dried and maintained over desiccant until tested. Wear tests were performed using a Falex No. 1 Ring and Block Wear and
- Friction Tester The equipment is described in ASTM Test method D2714. After weighing, the dry block was mounted against the rotating metal ring and loaded against it with the selected test pressure. Rotational velocity of the ring was set at the desired speed. No lubricant was used between the mating surfaces.
- the rings were SAE 4620 steel, Re 58-63, 6-12 RMS. A new ring was used for each test.
- Test time was 24 hours, except when friction and wear were high, in which case the test was terminated early.
- the friction force was recorded continuously.
- the block was dismounted, weighed, and the wear calculated by the following calculation:
- Wear Volume Calculation wear volume(cc/hr) weight loss (grams) material density(g/cc)X test duration(hr)
- PV (pressure X velocity) limit tests were performed using the same Falex No. 1 Ring and Block Wear and Friction Tester. In these tests, wear blocks and rings were started at a given PV. At intervals of 10-20 minutes, the PV was increased in increments by increasing the velocity to a maximum of 2.67 mps
- SEM/EDX Scanning Electron Microscopy/Energy Dispersive X-ray analysis was used in determining dispersion of PTFE in the samples of the Examples.
- This analytical technique provides morphological and elemental composition information from the sample surface. Using commercially available microscopes and x-ray analyzers, the sample is placed in a vacuum chamber, and a primary beam of electrons is rastered across the surface. Images are obtained from the remission of electrons. Elemental information is derived from the emission of x-rays whose energy levels are characteristic of each element. Mapping of individual elements is achieved by limiting detection to desired energy level. The analyzer then applies a light dot on a grid location each time an x-ray of that energy is detected. As the primary beam rasters across the sample surface, a map of the x-ray sources, representing the corresponding element, is generated. The resolution of the elemental map can be improved by multiple passes over the sample surface and averaging the acquired signals.
- the pellets were molded into standard 6.4 mm thick ASTM (D638) tensile test bars using a 170 g capacity, 145 ton clamping pressure injection molding machine.
- the profile was as follows: Rear 313°C, Center 334°C, Front 335°C and Nozzle 332°C; Boost 1 sec, Injection 20 sec, Hold 20 sec, Injection Pressure 3.4 MPa, Ram Speed fast, Screw Speed 107 rpm and Back Pressure minimum.
- the pellets were molded into standard 6.4 mm thick ASTM (D638) tensile test bars using a 170 g capacity, 145 ton clamping pressure injection molding machine.
- the profile was as follows: Rear 313°C, Center 334°C, Front 335°C and Nozzle 332°C; Boost 1 sec, Injection 20 sec, Hold 20 sec, Injection Pressure 3.4 MPa, Ram Speed fast, Screw Speed 107 rpm and Back Pressure minimum.
- Example 2 The same method for sample preparation as used in Example 2 was utilized except the polyimide resin prepared from pyromellitic dianhydride and 4,4' -oxydianiline was individual component is documented in the table below.
- Samples XVII, XVIII, and XIX were prepared as in Example 1 using 56 parts of Zenite® 6000 and 24 parts of polyamic acid, except that the zinc oxide used was 503R obtained from Zinc Corporation of America having a mean particle size of 3.7 ⁇ m after coating and no discernible unique structure.
- Sample XVIII utilized a zinc oxide coated according to the following procedure: To a 5 L round bottom flask 2L of distilled water and 500 g zinc oxide were added with agitation. The dispersion was heated to 75°C, and the pH was adjusted to 8.7.
- Sample XIX utilized a zinc oxide coated according to the following procedure: To a 5 L round bottom flask 3L of distilled water and 500 g zinc oxide was added with agitation. The dispersion was heated to 75°C and the pH was adjusted to 9.5 with 30% sodium hydroxide solution. 42.5g Kasil (Vinnings VSA-38) diluted to 100 ml with distilled water was added over a 30 minute period keeping the pH at 9.5 with 17.5% HCl solution. The dispersion was stirred for 30 minutes. The pH was adjusted to 8.2 with 17.5% HCl solution, and 40 ml of alumina was added over a 30 minute period while maintaining a pH of 8.2 with a 17.5% solution of hydrochloric acid. The dispersion was stirred for 30 minutes then filtered, washed with distilled water and placed in an oven at 110°C until dried. The sample was sonified to the desired particle size.
- Sample XX was prepared according to Example 1 using 56 parts of Zenite® 6000 and 24 parts of polyamic acid precursor. WZ-511 Zinc oxide powder was used as received from the supplier.
- HTN HTN blended with 10 parts zinc oxide additive (obtained from Matsushita as WZ-51 1 powder) having a starting mean particle size of 2.1 ⁇ m, 10 parts PTFE (DuPont Teflon® MP-1600 micropowder) and 24 parts polyimide resin prepared from pyromellitic dianhydride and 4,4' -oxydianiline (present as its precursor, polyamic acid) in such quantity as to yield the percentages shown in the table below. This was accomplished using a 30mm twin screw extruder with barrels set to 320°C and the die at 335°C. Quenching was accomplished using a water spray. The strand was cut into pellets using a standard rotating blade cutter.
- the pellets were molded into standard 6.4 mm thick ASTM (D638) tensile test bars using a 170 g capacity, 145 ton clamping pressure injection molding machine.
- the profile was as follows: Rear 315°C, Center 335°C, Front 335°C and Nozzle 335°C; Boost 0.5 sec, Injection 20 sec, Hold 20 sec, Injection Pressure 4.8 MPa, Ram Speed fast, Screw Speed 120 rpm and 0.34 MPa Back Pressure.
- Sample XXIV utilized imidized polyimide powder resin prepared from pyromellitic dianhydride and 4,4' -oxydianiline.
- Samples were prepared as in Example 1 using 10 parts of zinc oxide to 10 parts of PTFE.
- the compounded resin was injection molded into a 1.5mm thick by 50.8mm diameter disk for use as a hysterisis washer.
- the conditions utilized to accomplish this were as follows: Barrel temperatures 320°C. rear, 335°C. front, 335°C. nozzle: Mold 100°C; Cycle 1 sec boost, 15 sec inject, 20 sec cool; Pressure 0.3MPa back, 2.7MPa boost, 2.4MPa Inject; Ram speed, fast; Screw 84rpm.
- the washer performed as required with little evidence of wear after 10,000 kilometers of service.
Abstract
L'invention concerne des compositions polymères comportant des quantités contrôlées de particules d'oxyde de zinc uniformément dispersées à l'intérieur de celles-ci, des polymères et copolymères de tétrafluoroéthylène de dimension et de poids moléculaire sélectionnés, qui permettent d'obtenir des article façonnés dotés de propriétés d'usure améliorées.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002263323A CA2263323A1 (fr) | 1996-08-19 | 1997-08-19 | Compositions thermoplastiques comportant de l'oxyde de zinc et des homo ou copolymeres de tetrafluoroethylene et articles faconnes a partir de celles-ci |
JP51087098A JP2001524992A (ja) | 1996-08-19 | 1997-08-19 | 酸化亜鉛およびテトラフルオロエチレンのホモポリマーまたはコポリマーを含有する熱可塑性組成物ならびにそれから調製された成形品 |
EP97937306A EP0918816A1 (fr) | 1996-08-19 | 1997-08-19 | Compositions thermoplastiques comportant de l'oxyde de zinc et des homo ou copolymeres de tetrafluoroethylene et articles fa onnes a partir de celles-ci |
AU39849/97A AU3984997A (en) | 1996-08-19 | 1997-08-19 | Thermoplastic compositions including zinc oxide and tetrafluoroethylene homo or copolymers and shaped articles prepared therefrom |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US69704996A | 1996-08-19 | 1996-08-19 | |
US08/697,049 | 1996-08-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1998007779A1 WO1998007779A1 (fr) | 1998-02-26 |
WO1998007779A9 true WO1998007779A9 (fr) | 1998-07-02 |
Family
ID=24799587
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/014510 WO1998007779A1 (fr) | 1996-08-19 | 1997-08-19 | Compositions thermoplastiques comportant de l'oxyde de zinc et des homo ou copolymeres de tetrafluoroethylene et articles façonnes a partir de celles-ci |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0918816A1 (fr) |
JP (1) | JP2001524992A (fr) |
KR (1) | KR20000068198A (fr) |
CN (1) | CN1228796A (fr) |
AU (1) | AU3984997A (fr) |
CA (1) | CA2263323A1 (fr) |
WO (1) | WO1998007779A1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6013719A (en) * | 1998-06-15 | 2000-01-11 | E. I. Du Pont De Nemours And Company | Applications of low melt viscosity polytetrafluorethylene |
WO2014199322A2 (fr) * | 2013-06-12 | 2014-12-18 | Sabic Innovative Plastics Ip B.V. | Compositions résistantes à l'usure avec une faible contamination particulaire et procédé de préparation de ces compositions |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3908038A (en) * | 1973-03-28 | 1975-09-23 | Allied Chem | Thermoplastic molding compositions |
US3994814A (en) * | 1973-07-12 | 1976-11-30 | Garlock Inc. | Low friction bearing material and method |
JP2531307B2 (ja) * | 1991-01-08 | 1996-09-04 | 住友化学工業株式会社 | 全芳香族ポリエステル樹脂組成物およびオ―ブンウエア |
JP3041071B2 (ja) * | 1991-04-05 | 2000-05-15 | 松下電器産業株式会社 | 静電気拡散性摺動部材用樹脂組成物 |
JP3142673B2 (ja) * | 1992-12-25 | 2001-03-07 | エヌティエヌ株式会社 | 複写機用分離爪 |
US5567770A (en) * | 1993-05-28 | 1996-10-22 | E. I. Du Pont De Nemours And Company | Liquid crystalline polymer blends with improved wear properties |
JPH08104803A (ja) * | 1994-10-03 | 1996-04-23 | Idemitsu Petrochem Co Ltd | 樹脂組成物 |
-
1997
- 1997-08-19 AU AU39849/97A patent/AU3984997A/en not_active Abandoned
- 1997-08-19 EP EP97937306A patent/EP0918816A1/fr not_active Withdrawn
- 1997-08-19 JP JP51087098A patent/JP2001524992A/ja active Pending
- 1997-08-19 KR KR1019997001322A patent/KR20000068198A/ko not_active Application Discontinuation
- 1997-08-19 CN CN97197392A patent/CN1228796A/zh active Pending
- 1997-08-19 CA CA002263323A patent/CA2263323A1/fr not_active Abandoned
- 1997-08-19 WO PCT/US1997/014510 patent/WO1998007779A1/fr not_active Application Discontinuation
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