CA1157189A - Stabilized fluoroelastomer compositions - Google Patents
Stabilized fluoroelastomer compositionsInfo
- Publication number
- CA1157189A CA1157189A CA000375773A CA375773A CA1157189A CA 1157189 A CA1157189 A CA 1157189A CA 000375773 A CA000375773 A CA 000375773A CA 375773 A CA375773 A CA 375773A CA 1157189 A CA1157189 A CA 1157189A
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- CA
- Canada
- Prior art keywords
- quinacridone
- perfluoro
- composition
- vinyl ether
- days
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
Abstract
STABILIZED FLUOROELASTOMER COMPOSITIONS
Abstract Vulcanizates of certain fluoroelastomer terpolymer compositions, wherein the terpolymer is derived from tetrafluoroethylene, perfluoro(methyl vinyl ether), and a cure-site monomer, and further wherein the composition contains non-black filler, exhibit significantly improved stability upon heat aging when small quantities of quinacridone-type pigments are incorporated therein.
Abstract Vulcanizates of certain fluoroelastomer terpolymer compositions, wherein the terpolymer is derived from tetrafluoroethylene, perfluoro(methyl vinyl ether), and a cure-site monomer, and further wherein the composition contains non-black filler, exhibit significantly improved stability upon heat aging when small quantities of quinacridone-type pigments are incorporated therein.
Description
STABILIZED FLUOROELASTOMER COMPOSITIONS
` DES`CRIP~ION
Technical Field This invention relates to certain vulcan-izable fluoroelastomer compositions, wherein thefluoroelastomer is a terpolymer derived from tetra-fluoroethylene, perfluoromethyl perfluorovinyl ether and a cute-site monomer, which terpolymers are vulcanizable to useful elastomeric materials characterized by excellent physical properties and resistance to environmental attack. These materials can be fabricated into mechanical parts such as O-rings, flange seals, gasket stock, pump diaphragms and liners and are particularly useful where extra-ordinary resistance to heat and corrosive fluids isrequired. In particular, this invention relates to improvements in st~bility of such compositions containing non-black fillersupon heat aging by incorporating therein small quantities of quinacridone-type pigments.
Back~round Art Kalb et al., "Polymerization Reactions and New Polymers", Advances in Chemistry Series, No. 129, 13-26 (1973) discloses certain copolymers of tetrafluoroethylene, perfluoro(methyl vinyl ether) and a third monomer selected from the group consisting of:
(a) perfluoro(4-cyanobutyl vinyl ether), (b) perfluoro(4-carbomethoxybutyl vinyl ether), (c) perfluoro(2-phenoxypropyl vinyl ether), and LC-2027 (d) perfluoro(3-phenoxypropyl vinyl ether).
Kalb et al also discloses the outstanding solvent and chemical resistance that can be obtained with these elastomers.
U.S. Patent 3 546 186 granted December 8, 1970 to Gladding and Sullivan, discloses certain vulcanizable copolymers of substituted perfluoro-vinyl ether. In particular, among the many and varied copolymers disclosed by Gladding and Sullivan, there are disclosed terpolymers derived from tetra-fluoroethylene, perfluoromethyl perfluorovinyl ether and a cure-site monomer which can be, among other things, perfluoro(4-cyanobutyl vinyl ether~ or perfluoro(4-carbomethoxybutyl vinyl ether).
U.S. Patent 3 467 638, granted September 16, 1969 to Pattison, discloses certain vulcanizable copolymers of substituted perfluorovinyl ethers. In particular, among the many and varied copolymers disclosed by Pattison, there are disclosed terpolymers derived from tetrafluoroethylene, perfluoromethyl perfluorovinyl ether and a cure-site monomer which can be, among other things, perfluoro(2-phenoxy-propyl vinyl ether~.
U.S. Patent 3 682 872, granted August 8, 1972 to Brizzolara and Quarles, discloses certain vulcanizable copolymers of substituted perfluoro-vinyl ethers. In particular, among the many and varied copolymers disclosed by Brizzolara and Quarles there are disclosed terpolymers derived from tetrafluoroethylene, perfluoromethyl perfluoro-yinyl ether and, as a cure-site monomer, perfluoro(3-phenoxypropyl vinyl ether).
Copending Canadian Patent Application No.
340 579, filed 1979 November 26 by Breazeale, dis-closes certain vulcanizable copolymers of tetra-fluoroethylene, perfluoromethyl perfluorovinyl ether, and a cure-site monomer which can be perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene).
~ .
1~57189 It is non-black filled fluoroelastomer compositions based on the polymers disclosed in the background art summarized above which can be improved by the incorporation therein of small quantities of 5 quinacridone-type pisments.
Disclosure of the Invention The present invention relates to certain vulcanizable fluoroelastomer compositions, wherein the fluoroelastomer is a terpolymer derived from 10 tetrafluoroethylene, perfluoromethyl perfluorovinyl ether and a cure-site monomer, and further wherein said composition contains at least one non-black filler, said compositions further containing a small quantity of at least one quinac_idone-type 15 pigments. The fluoroelastomer compositions of the present invention possess surprisingly superior stability upon heat aging as compared with prior similar compositions containing no quinacridone-type pigment.
` DES`CRIP~ION
Technical Field This invention relates to certain vulcan-izable fluoroelastomer compositions, wherein thefluoroelastomer is a terpolymer derived from tetra-fluoroethylene, perfluoromethyl perfluorovinyl ether and a cute-site monomer, which terpolymers are vulcanizable to useful elastomeric materials characterized by excellent physical properties and resistance to environmental attack. These materials can be fabricated into mechanical parts such as O-rings, flange seals, gasket stock, pump diaphragms and liners and are particularly useful where extra-ordinary resistance to heat and corrosive fluids isrequired. In particular, this invention relates to improvements in st~bility of such compositions containing non-black fillersupon heat aging by incorporating therein small quantities of quinacridone-type pigments.
Back~round Art Kalb et al., "Polymerization Reactions and New Polymers", Advances in Chemistry Series, No. 129, 13-26 (1973) discloses certain copolymers of tetrafluoroethylene, perfluoro(methyl vinyl ether) and a third monomer selected from the group consisting of:
(a) perfluoro(4-cyanobutyl vinyl ether), (b) perfluoro(4-carbomethoxybutyl vinyl ether), (c) perfluoro(2-phenoxypropyl vinyl ether), and LC-2027 (d) perfluoro(3-phenoxypropyl vinyl ether).
Kalb et al also discloses the outstanding solvent and chemical resistance that can be obtained with these elastomers.
U.S. Patent 3 546 186 granted December 8, 1970 to Gladding and Sullivan, discloses certain vulcanizable copolymers of substituted perfluoro-vinyl ether. In particular, among the many and varied copolymers disclosed by Gladding and Sullivan, there are disclosed terpolymers derived from tetra-fluoroethylene, perfluoromethyl perfluorovinyl ether and a cure-site monomer which can be, among other things, perfluoro(4-cyanobutyl vinyl ether~ or perfluoro(4-carbomethoxybutyl vinyl ether).
U.S. Patent 3 467 638, granted September 16, 1969 to Pattison, discloses certain vulcanizable copolymers of substituted perfluorovinyl ethers. In particular, among the many and varied copolymers disclosed by Pattison, there are disclosed terpolymers derived from tetrafluoroethylene, perfluoromethyl perfluorovinyl ether and a cure-site monomer which can be, among other things, perfluoro(2-phenoxy-propyl vinyl ether~.
U.S. Patent 3 682 872, granted August 8, 1972 to Brizzolara and Quarles, discloses certain vulcanizable copolymers of substituted perfluoro-vinyl ethers. In particular, among the many and varied copolymers disclosed by Brizzolara and Quarles there are disclosed terpolymers derived from tetrafluoroethylene, perfluoromethyl perfluoro-yinyl ether and, as a cure-site monomer, perfluoro(3-phenoxypropyl vinyl ether).
Copending Canadian Patent Application No.
340 579, filed 1979 November 26 by Breazeale, dis-closes certain vulcanizable copolymers of tetra-fluoroethylene, perfluoromethyl perfluorovinyl ether, and a cure-site monomer which can be perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene).
~ .
1~57189 It is non-black filled fluoroelastomer compositions based on the polymers disclosed in the background art summarized above which can be improved by the incorporation therein of small quantities of 5 quinacridone-type pisments.
Disclosure of the Invention The present invention relates to certain vulcanizable fluoroelastomer compositions, wherein the fluoroelastomer is a terpolymer derived from 10 tetrafluoroethylene, perfluoromethyl perfluorovinyl ether and a cure-site monomer, and further wherein said composition contains at least one non-black filler, said compositions further containing a small quantity of at least one quinac_idone-type 15 pigments. The fluoroelastomer compositions of the present invention possess surprisingly superior stability upon heat aging as compared with prior similar compositions containing no quinacridone-type pigment.
2~ The terpolymers use~ in the composition of the present invention are substantially as described by Kalb et al, Gladding and Sullivan, Pattison, Brizzolara and Quarles, and Breazeale in the refer-ences cited above and generally comprise copolymer-25 ized units of about 53-79.8 mole percent of tetrafluoroethylene (TFE), about 20-45 mole percent of perfluoromethyl perfluorovinyl ether (PMVE), and 0.2-2 mole percent of a cure-site monomer selected from the group consisting of:
(a) perfluoro(4-cyanobutyl vinyl ether), (b) perfluoro(4-carbomethoxybutyl vinyl ether), (c) perfluoro(2-phenoxypropyl vinyl ether), (d) perfluoro(3-phenoxypropyl vinyl ether), and (e) perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene).
~5~
Such terpolymers can be prepared by the procedures taught in the references cited above. Preferably the compositions of the present invention are based upon terpolymers in which the cure-site monomer is perfluoro(2-phenoxypropyl vinyl ether), and most preferably, they are based on such terpolymers in which the proportions of the monomers are about 65.4-73.6 mole percent TFE, 26-34 mole percent PMVE, and the remainder is perfluoro(2-phenoxypropyl vinyl ether). It should be understood that exact determina-tion of the monomer proportions is difficult and that the values given are estimates based on infrared spectra. Nevertheless, the values recited are believed reasonably accurate and precise.
As with conventional vulcanizable fluoro-elastomer compositions, it is frequently desirable to mix fillers, reinforcing agents, stabilizers, plasticizers, lubricants or processing aids with the elastomer prior to vulcanization. Although a common additive is carbon black, frequently it is desirable to use one or more non-black fillers, such as titanium dioxide, zirconium dioxide, silica, clay and asbestos.
When the fluoroelastomer composition con-tains such non-black filler, the stability upon heat aging can be significantly improved by incorporating therein a small quantity, 0.1-10 phr, preferably ~57~89 0.5-6 phr, and most preferably 1-3 phr, of at least one quinacridone-type pigment.
Quinacridone-type pigments are generally known (see, e.g., Kirk-Othmer Encyclopedia of Chemical Technology, vol. 15, pp. 581-2 (1968) and the fol-lowing U.S. Patents: 3,160,510; 3,686,009; and
(a) perfluoro(4-cyanobutyl vinyl ether), (b) perfluoro(4-carbomethoxybutyl vinyl ether), (c) perfluoro(2-phenoxypropyl vinyl ether), (d) perfluoro(3-phenoxypropyl vinyl ether), and (e) perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene).
~5~
Such terpolymers can be prepared by the procedures taught in the references cited above. Preferably the compositions of the present invention are based upon terpolymers in which the cure-site monomer is perfluoro(2-phenoxypropyl vinyl ether), and most preferably, they are based on such terpolymers in which the proportions of the monomers are about 65.4-73.6 mole percent TFE, 26-34 mole percent PMVE, and the remainder is perfluoro(2-phenoxypropyl vinyl ether). It should be understood that exact determina-tion of the monomer proportions is difficult and that the values given are estimates based on infrared spectra. Nevertheless, the values recited are believed reasonably accurate and precise.
As with conventional vulcanizable fluoro-elastomer compositions, it is frequently desirable to mix fillers, reinforcing agents, stabilizers, plasticizers, lubricants or processing aids with the elastomer prior to vulcanization. Although a common additive is carbon black, frequently it is desirable to use one or more non-black fillers, such as titanium dioxide, zirconium dioxide, silica, clay and asbestos.
When the fluoroelastomer composition con-tains such non-black filler, the stability upon heat aging can be significantly improved by incorporating therein a small quantity, 0.1-10 phr, preferably ~57~89 0.5-6 phr, and most preferably 1-3 phr, of at least one quinacridone-type pigment.
Quinacridone-type pigments are generally known (see, e.g., Kirk-Othmer Encyclopedia of Chemical Technology, vol. 15, pp. 581-2 (1968) and the fol-lowing U.S. Patents: 3,160,510; 3,686,009; and
3,748,162) and are commercially available. Such pigments may be quinacridone H O
quinacridone quinone H O O
[ ~
substituted (e.g., alkyl or halo substituted) quinacridone, substituted quinacridone quinone, and mixtures and solid solutions of such substituted and unsubstituted quinacridones and quinacridone quinones.
For example, the following quinacridone pigments have demonstrated the ability to improve the stability, upon heat aging, of non black filled fluoroelastomer compositions based on TFE/PMVE/P2PVE terpolymers:
Colour Index Orange-48, which is a solid solution of quinacridone quinone, quinacridone and dihydroquinacridone; Colour Index - Violet-l9 (C.I. no. 46 500), which can be ~L57~89 a gamma quinacridone or a beta quinacridone;
Colour Index Red-206, which is a solid solu-tion containing quinacridone; Colour Index Orange-49, which is a solid so}ution containing quinacridone quinone and dihydroquinacridone;
Monastral~ transparent Red B pigment, which is a solid solution containing quinacridone;
and Colour Index Red 202, which is a solid solution containing dichloro~uinacridone quinone.
Preferred pigments include Colour Index Orange-48, Colour Index Red-206, and Colour Index Orange-49.
The most preferred fluoroelastomer composition of the present invention is one based on a TFE/PMVE/P2PVE
terpolymer in which the monomer mole ratio is approx-imately 65.4-73.6/26-34/0.4-0.6 and which includes about 2-3 phr of Colour Index Red-206 pigment.
The following examples illustrate the fluoro-elastomer compositions of the present invention and demonstrate their improved sta~ility, upon heat aging, as compared with similar compositions that do not contain any quinacridone-type pigment. In each of the following examples, standard elastomer processing and testing procedures were employed. Compounds were milled on a standard two-roll rubber mill at 60C.
Slabs were sheeted off the mill at the desired thick-nesses. O-ring preforms were cigar-rolled on the mills. Slabs (6" x 6" x 0.080" i.e., 15.2 x 15.2 x 0.203 cm), pellets (Yerzley type, ASTM 0945, 1/2" x 3/4" i.e., 1.27 x l.gl cm) and O-rings (1" ID x 1/8" cross-sectional diameter i.e. 2.54 cm ID x 0.32 cm cross-sectional diameter) were press cured in the appropriate molds at 190C for 30 minutes. Parts were removed from the molds and post-cured for 2 or 5 days under nitrogen in an oven whose temperature was programmed to rise from 25C initially to 288C for the last 24 hours.
....
` 7 Post-cured parts were tested as follows:
small dumbbells (3-l/2" x l/4" with 5/8" wide tabs i.e., 8.89 x 0.64 cm with 1.59 cm wide tabs) were died out of the slabs and pulled on the Instron at room temperature at 10 in./min. i.e., 25.4 cm/min.
Readings for modulus at 100~ elongation (~100~' tension at break (TB), elongation at break (EB), and permanent set (PS) were taken in accordance with ASTM D-412. Pellets and O-rings were tested for compression set by ASTM D 395B (70 hours at 204C).
Hardness was measured on a Shore A type durometer.
Results are read on an arbitrary scale where O is soft and 100 is hard. Parts were heat aged in an air oven for 2-4 days at 600F (316C) and then tested as above.
These examples demonstrate the superior stability, upon heat aging, of compositions treated with a small quantity of various quinacridone pigments (Examples 2-4) as compared with an un~reated compo-sition ~Example 1):
Fluoroelastomer Composition l 2 3 4 Polymerl 100 100 100 100 18-Crown-62 3 3 3 3 TiO2 20 17 18 18 Pigment:
C.I. Orange-48 3 C.I. Violet-l9, gamma 2 C.I~ Violet-19, beta 2 l. Copolymer of tetrafluoroethylene (67.5 mole ~), perfluoromethyl perfluorovinyl ether (32 mole ~), and perfluoro(2-phenoxypropyl vinyl ether) (0.5 mole %) 2. 1,4,7,10,13,16-hexaoxacyclooctadecane 3. Dipotassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene) ~3 57189 Physical Properties Stress/Strain (Post Cure - 2 days) Initial 100' MP 10.5 12.8 9.9 10.8 TB, MPa 15.8 16.7 14.1 13.3 E~, % 140 130 130 120 PS, % 4 7 6 4 Heat Aged (2 days/316C) Mloo, MPa 5-7 7.2 6.3 6.3 TB, MPa 11.5 14.7 14.5 11.4 EB, % 250 210 240 200 PS, ~ 15 11 14 10 Heat Aged (4 days/316C) MloO' a 3.8 5.0 4.8 Not TB, MPa 6.0 11.0 8.5 EB, % 360 2gO 300 Run PS, % 34 19 21 Compression Set (70 h/204C) Pellets, %
Initial 27 28 0 24 Heat Aged 2 days 76 68 77 73 Heat Aged 4 days 92 72 89 O-Rings, %
Initial 67 71 74 76 Heat Aged 2 days 90 82 99 85 Heat Aged 4 days 100+ 100+ 100+
Hardness, Shore A 76 78 77 78 These examples demonstrate the superio-stability, upon heat aging, of compositions treated with a small quantity of various quinacridone pigments (Examples 6-9)as compared with an untreated compo-sition (Example 5):
~57~89 Fluoroelastomer Composition Polymerl loo loo loo loo 100 18-Crown-62 3 3 3 3 3 S K2AF 4.54.5 4.5 4.5 4.5 TiO2 20 17 17 17 18 Pigment:
C.I. Orange-48 3 C.I. ~ed-206 3 10 C.I. Orange-49 3 Monastral~ Transparent Red B 3 1. Copolymer of tetrafluoroethylene (67.5 mole %), perfluoromethyl perfluorovinyl ether (32 mole %), and perfluoro(2-phenoxy2ro~yl vinyl ether) (0.5 mole %) 2.. 1,4,7,10,13,16-hexaoxacyclooctadecane 3. .Dipo.tassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene) ~57~89 Physical Properties Stress/Stxain ~Post Cure - 2 days) Initial Mloo, MPa9.5 9.6 8.9 9.4 8.0 TB, MPa14.8 15.8 14.4 14.4 12.2 EB, ~ 160 150 150 130 140 PS, % 2 4 4 4 3 Heat Aged (2 days/316C) M10O,MPa 5.0 5.3 5.9 5.8 3.5 TB, MPa 10.6 12.8 12.9 12.3 10.6 EB, % 240 220 210 200 230 PS, % 11 8 7 7 8 Heat Aged (4 days/316C) Mloo, MPA 3.3 3.9 4.4 4.0 3.9 TB, MPa7.0 10.7 10.9 10.0 8.3 EB, ~360 310 290 310 300 PS, ~24 14 12 15 14 Compression Set (70 h/204C) 20 O-Rings, %
Initial 77 - 78 77 77 78 Heat aged (2 days)93 81 82 84 87 Heat aged (4 days) 100+ 95 93 100 100+
. ~ .
~ ~57~89 These examples demonstrate the superior stability, upon heat aging, of compositions treated with a small quantity of quinacridone pigments 5 (Examples 11 and 13) as compared with untreated compositions (Examples 10 and 12), wherein the cure-site monomer of the terpolymer in the fluoroelastomer composition is a cyano monomer.
Fluoroelastomer Composition Polymer4 100 100 100 100 Tetraphenyltin 3 3 3 3 DCH-18-Crown-65 TiO2 10 10 20 20 15 C.I. Red-206 ~ 3 3
quinacridone quinone H O O
[ ~
substituted (e.g., alkyl or halo substituted) quinacridone, substituted quinacridone quinone, and mixtures and solid solutions of such substituted and unsubstituted quinacridones and quinacridone quinones.
For example, the following quinacridone pigments have demonstrated the ability to improve the stability, upon heat aging, of non black filled fluoroelastomer compositions based on TFE/PMVE/P2PVE terpolymers:
Colour Index Orange-48, which is a solid solution of quinacridone quinone, quinacridone and dihydroquinacridone; Colour Index - Violet-l9 (C.I. no. 46 500), which can be ~L57~89 a gamma quinacridone or a beta quinacridone;
Colour Index Red-206, which is a solid solu-tion containing quinacridone; Colour Index Orange-49, which is a solid so}ution containing quinacridone quinone and dihydroquinacridone;
Monastral~ transparent Red B pigment, which is a solid solution containing quinacridone;
and Colour Index Red 202, which is a solid solution containing dichloro~uinacridone quinone.
Preferred pigments include Colour Index Orange-48, Colour Index Red-206, and Colour Index Orange-49.
The most preferred fluoroelastomer composition of the present invention is one based on a TFE/PMVE/P2PVE
terpolymer in which the monomer mole ratio is approx-imately 65.4-73.6/26-34/0.4-0.6 and which includes about 2-3 phr of Colour Index Red-206 pigment.
The following examples illustrate the fluoro-elastomer compositions of the present invention and demonstrate their improved sta~ility, upon heat aging, as compared with similar compositions that do not contain any quinacridone-type pigment. In each of the following examples, standard elastomer processing and testing procedures were employed. Compounds were milled on a standard two-roll rubber mill at 60C.
Slabs were sheeted off the mill at the desired thick-nesses. O-ring preforms were cigar-rolled on the mills. Slabs (6" x 6" x 0.080" i.e., 15.2 x 15.2 x 0.203 cm), pellets (Yerzley type, ASTM 0945, 1/2" x 3/4" i.e., 1.27 x l.gl cm) and O-rings (1" ID x 1/8" cross-sectional diameter i.e. 2.54 cm ID x 0.32 cm cross-sectional diameter) were press cured in the appropriate molds at 190C for 30 minutes. Parts were removed from the molds and post-cured for 2 or 5 days under nitrogen in an oven whose temperature was programmed to rise from 25C initially to 288C for the last 24 hours.
....
` 7 Post-cured parts were tested as follows:
small dumbbells (3-l/2" x l/4" with 5/8" wide tabs i.e., 8.89 x 0.64 cm with 1.59 cm wide tabs) were died out of the slabs and pulled on the Instron at room temperature at 10 in./min. i.e., 25.4 cm/min.
Readings for modulus at 100~ elongation (~100~' tension at break (TB), elongation at break (EB), and permanent set (PS) were taken in accordance with ASTM D-412. Pellets and O-rings were tested for compression set by ASTM D 395B (70 hours at 204C).
Hardness was measured on a Shore A type durometer.
Results are read on an arbitrary scale where O is soft and 100 is hard. Parts were heat aged in an air oven for 2-4 days at 600F (316C) and then tested as above.
These examples demonstrate the superior stability, upon heat aging, of compositions treated with a small quantity of various quinacridone pigments (Examples 2-4) as compared with an un~reated compo-sition ~Example 1):
Fluoroelastomer Composition l 2 3 4 Polymerl 100 100 100 100 18-Crown-62 3 3 3 3 TiO2 20 17 18 18 Pigment:
C.I. Orange-48 3 C.I. Violet-l9, gamma 2 C.I~ Violet-19, beta 2 l. Copolymer of tetrafluoroethylene (67.5 mole ~), perfluoromethyl perfluorovinyl ether (32 mole ~), and perfluoro(2-phenoxypropyl vinyl ether) (0.5 mole %) 2. 1,4,7,10,13,16-hexaoxacyclooctadecane 3. Dipotassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene) ~3 57189 Physical Properties Stress/Strain (Post Cure - 2 days) Initial 100' MP 10.5 12.8 9.9 10.8 TB, MPa 15.8 16.7 14.1 13.3 E~, % 140 130 130 120 PS, % 4 7 6 4 Heat Aged (2 days/316C) Mloo, MPa 5-7 7.2 6.3 6.3 TB, MPa 11.5 14.7 14.5 11.4 EB, % 250 210 240 200 PS, ~ 15 11 14 10 Heat Aged (4 days/316C) MloO' a 3.8 5.0 4.8 Not TB, MPa 6.0 11.0 8.5 EB, % 360 2gO 300 Run PS, % 34 19 21 Compression Set (70 h/204C) Pellets, %
Initial 27 28 0 24 Heat Aged 2 days 76 68 77 73 Heat Aged 4 days 92 72 89 O-Rings, %
Initial 67 71 74 76 Heat Aged 2 days 90 82 99 85 Heat Aged 4 days 100+ 100+ 100+
Hardness, Shore A 76 78 77 78 These examples demonstrate the superio-stability, upon heat aging, of compositions treated with a small quantity of various quinacridone pigments (Examples 6-9)as compared with an untreated compo-sition (Example 5):
~57~89 Fluoroelastomer Composition Polymerl loo loo loo loo 100 18-Crown-62 3 3 3 3 3 S K2AF 4.54.5 4.5 4.5 4.5 TiO2 20 17 17 17 18 Pigment:
C.I. Orange-48 3 C.I. ~ed-206 3 10 C.I. Orange-49 3 Monastral~ Transparent Red B 3 1. Copolymer of tetrafluoroethylene (67.5 mole %), perfluoromethyl perfluorovinyl ether (32 mole %), and perfluoro(2-phenoxy2ro~yl vinyl ether) (0.5 mole %) 2.. 1,4,7,10,13,16-hexaoxacyclooctadecane 3. .Dipo.tassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene) ~57~89 Physical Properties Stress/Stxain ~Post Cure - 2 days) Initial Mloo, MPa9.5 9.6 8.9 9.4 8.0 TB, MPa14.8 15.8 14.4 14.4 12.2 EB, ~ 160 150 150 130 140 PS, % 2 4 4 4 3 Heat Aged (2 days/316C) M10O,MPa 5.0 5.3 5.9 5.8 3.5 TB, MPa 10.6 12.8 12.9 12.3 10.6 EB, % 240 220 210 200 230 PS, % 11 8 7 7 8 Heat Aged (4 days/316C) Mloo, MPA 3.3 3.9 4.4 4.0 3.9 TB, MPa7.0 10.7 10.9 10.0 8.3 EB, ~360 310 290 310 300 PS, ~24 14 12 15 14 Compression Set (70 h/204C) 20 O-Rings, %
Initial 77 - 78 77 77 78 Heat aged (2 days)93 81 82 84 87 Heat aged (4 days) 100+ 95 93 100 100+
. ~ .
~ ~57~89 These examples demonstrate the superior stability, upon heat aging, of compositions treated with a small quantity of quinacridone pigments 5 (Examples 11 and 13) as compared with untreated compositions (Examples 10 and 12), wherein the cure-site monomer of the terpolymer in the fluoroelastomer composition is a cyano monomer.
Fluoroelastomer Composition Polymer4 100 100 100 100 Tetraphenyltin 3 3 3 3 DCH-18-Crown-65 TiO2 10 10 20 20 15 C.I. Red-206 ~ 3 3
4.copolymer of tetrafluoroethylene (69.7 mole %), perfluoromethyl perfluorovinyl ether (29.6 mole ~).
and perfluoro(~-cyano-5-methyl-3,6-diôxa-1-octene) (0.7 mole %)
and perfluoro(~-cyano-5-methyl-3,6-diôxa-1-octene) (0.7 mole %)
5. 2,5,8,15,18,21-hexao~atricycloE20.4Ø09~14]-hexacosane (i.e., dicyclohexyl-18-crown-6) 57~L89 Physical Properties 1O 1l 126 136 Stress/Strain (Post Cure - 2 days) Initial MloO' MPa 1.8 3.0 2.6 4.5 TB, MPa6.8 11.8 9.8 14.1 EB, ~ 190 200 260 200 Heat Aged(2 days/316C) (3 days/316C) M10O,MPa 1.3 1.7 2.3 2.3 TB, MPa 6.3 6.8 7.8 9.8 EB, % 300 260 310 300 Compression Set (70 h/204C) Pellets, %
Initial 47 39 - -Heat Aged 2 days 22 17 O-Rings, %
Initial - - 34 28 Heat Aged 3 days - - 38 23
Initial 47 39 - -Heat Aged 2 days 22 17 O-Rings, %
Initial - - 34 28 Heat Aged 3 days - - 38 23
6. After post cure in nitrogen for 2 days, these samples were heated for an additional day at 316C under nitrogen 13 ~;7~89 These examples demonstrate the superior stability, upon heat aging, of compositions treated with a small quantity of various quinacridone pigments 5 (Example 15) as compared with an untreated compo-ition (Example 14):
Fluoroelastomer ComPosition Polymer4 100 100 10 ~etraphenyltin 3 3 DCH-18-Crown-65 SiO2 10 10 C.I. Red-206 - 3 15 4. Copolymer of tetrafluoroethylene (69.7 mole ~), perfluoromethyl perfluorovinyl ether (29.6 mole ~), and perfluoro(8-cyano-5-methyl-3,6-dioxa-isoocta~e) (0.7 mole %) 5. 2,5,~ 5,~18,21-hexaoxatric~clo[20.4Ø09~14~-hexacosane (i.e., dicyclohexyl-18-crown-6) ~L57~89 Physical Properties Stress/Strain (Post Cure - 2 days) Initial Mloo, MPa 3.7 4.3 TB, MPa 10.0 15.1 EB, % 250 240 Heat Aged (3 days/316C) Mloo, 2.5 2.7 TB, MPa 8.1 9.5 E3, % 340 350 Compression Set (70 h/204C) O-Rings, %
In~tial 51 57 Heat Aged 3 days 60 58 6. After post cure in nitrogen for 2 days, these samples were heated for an additional day at 316C
under nitrogen These examples demonstrate the beneficial effect of quinacridone pigment over a range of pigment concentrations:
Fluoroelastomer Composition Polymerl 100 100 100 100 100 K2AF 4.5 4.5 4.5 4.5 4.5 18-Crown-62 3.0 3.0 3.0 3.0 3.0 TiO2 20 20 20 20 20 30 C.I. Red-206 0 0.5 1.5 3.0 6.0 1. Copolymer of tetrafluoroethylene (69.7 mole %), perfluoromethyl per~luorovinyl ether (29.6 mole %), and perfluoro (8-cyano-~-methyl-3,6-dioxa-1-octene) (0.7 mole %) 2. 1,4,7,10,13,16-hexaoxacyclooctadecane 3. Dipotassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene) 14 ~57~89 Physical Properties _ Stress/Strain (Post Cure - 5 days) Initial Mloo, MPa 9.69.6 9.0 10.3 9.9 TB, MPa 13.112.6 14.7 14.7 15.9 EB, % 130 120 140 140 150 Heat Aged (2 days) Mloo, MPa 4.04.7 ~.7 7.0 6.6 TB, MPa 9.1 10.5 11.6 11.7 11.3 EB, % 230 210 220 210 230 Heat Aged (4 days) ~100' MPa 2.33.1 3.9 4.3 4.4 TB, MPa 3.0 6.2 7.2 7.4 6.8 EB, ~ 370 330 310 310 300 comPression Set (70 h/204C) Pellets, %
Initial 43 43 39 39 45 Heat Aged (2 days) 83 76 74 76 79 Heat Aged (4 days) 77* 84 85 81 82 O-Rings, ~
Initial -- 73 70 67 80 Heat Aged (2 days) 97 93 91 94 93 Heat Aged (4 days) 100+ 100+ 100+ 100+ 100+
* anomalous result ~L57189 These examples demonstrate the beneficial effect of quinacridone pigment in fluoroelastomer compositions containing a variety of non-black fillers:
Fluoroelastomer Composition 2l 22 23 24 Polymerl 100 100 100 100 K2AF 3 4.5 4.5 4.5 4.5 DCH-18-Crown-6 4.0 4.0 4.0 4.0 10 TiO2 (grade l) R902 20 20 TiO2 (grade 2) R960 - - 20 20 C.I. Red-206 - 3 - 3 1. Copolymer of tetrafluoroethylene (67.5 mole %) perfluoromethyl perfluorovinyl ether (32 mole %), and perfluoro(2-phenoxypropyl vinyl ether) (0.5 mole %) 3. Dipotassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene) 0 5. 2,5,8,15,18,21-hexaoxatricyclo[20.4Ø09'l4]-hexacosane g~L57~L89 Physical Properties Stress/Strain (Post Cure - 5 days) Initial Mloo, MPa 8.69.4 7.4 10.1 TB, MPa 12.512.6 10.8 13.1 EB, % 170 140 150 130 Heat Aged (3 days) Mloo, Not 5-0 2.7 4.6 TB, MPa test-7.0 1.9 7.6 E~, % able310 350 300 Compression Set (70 h/204C) Pellets, ~
Initial 2S 39 47 40 Heat Aged (3 days) n.t.100 100+ 80 O-Rings, ~
Initial 77 73 70 70 Heat Aged (3 days) n.t. 73 100+ 89 57~89 ExA~lpLEs 25-3~
These examples demonstrate the beneficial effect of quinacridone pigment in fluoroelastomer compositions containing a variety of non-black fillers:
Fluoroelastomer Composition Polymerl 100 100 100 100 100 100 K2AF 3 4.5 4.5 4.5 4.5 4.5 4,5 DCH-18-Crown-64.0 4.0 4.0 4.0 4.0 4.0 SiO2 10 10 - - - -Talc - - 13 13 Asbestos - - - - 11.5 11.5 C.I. Red-206 - 3 - 3 _ 3 15 1. Copolymer of tetrafluoroethylene (67.5 mole %), perfluoromethyl perfluorovinyl ether (32 mole ~), and perfluoro~2-phenoxypropyl vinyl ether) (0.5 mole %) 3. Dipotassium salt of hexafluoroisopropylidene bis(4-hydroxybenzene) 5. 2,5,8,15,18,21-hexaoxatricyclo[20.4Ø09'1 ~-hexacosane -~ 18 ~S7~89 Physical Properties Stress/Strain (Post Cure - 5 days) Initial S Mloo, MPa12.712.8 10.8 11.8 - -TB, MPa13.713.0 12.5 13.6 13.1 14.1 EB, % 110 100 120 120 90 90 ~eat Aged ~2 days) Mloo, ~Pa 6.5 9.0 5.6 8.5 7.6 9.9 TB, MPalO.S12.3 7.7 lO.S 6.1 10.0 EB, % 240 170 300 200 240 160 Compression Set (70 h/204C) Pellets, ~
Initial42 43 72 55 48 48 Heat Aged (2 days) 69 65 85 68 94 70 O-Rings, ~
Initial64 57 73 70 72 69 Heat Aged (2 days) 97 84 92 87 100+ -100+
., 19 ~57~89 EXA~LES 31-34 These examples demonstrate the beneficial effect of quinacridone pigment in fluoroelastomer compositions containing a variety of non-black fillers:
Fluoroelastomer Composition Polymerl 100 100 100 100 K2AF3 4-5 4-5 3.0 3.0 10 18-Crown-6 ~ ~ 3-0 3-0 Hydrated alumina 11.2 11.2 Zr2 ~ - 26 26 C.I. Red-206 - 5 - 2 1. Copolymer of tetrafluoroethylene (67.5 mole %), perfluoromethyl perfluorovinyl ether (32 mole ~), and perfluoro(2-phenoxypropyl vinyl ether) (0.5 mole %) 2. 1,4,7,10,13,16-hexaoxacyclooctadecane 3. Dipotassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene) 5. 2,5,8,15,18,21-hexaoxatricyclo~20-4--9'1 ]~
hexacosane P~57~89 Physical Properties Stress/Strain (Post Cure - 2 days) Initial Mloo, MPa 7.3 9.2 6.5 7.7 TB, MPa 11.3 13.2 12.3 15.7 EB, % 140 160 170 180 Heat Aged (2 days) Mloo, MPA 2.4 4.5 3.2 4.8 TB, MPa 5.5 8.2 7.7 15.1 EB, % 400 290 330 280 Heat Aged (4 days) Mloo, MPa - - Not 3.3 TB, MPa - - Test- 8.0 EB~ % able 390 Compression Set (70 h/204C) Pellets, ~
Initial 39 56 41 36 Heat Aged (2 days1 - - n.t. n.t.
Heat Aged (4 days) - - n.t. n.t.
O-Rings, %
Initial n.t. 62 62 56 Heat Aged (2 days) - - 100+ 76 Heat Aged (4 days~ - - n.t. n.t.
:
~5789 EX~MPLES 35-36 These examples demonstrate the superior stability, upon heat aging, of compositions treated with a small quantity of quinacridone pigment (Example 36) as comPared with untreated compositions ~Example 35), wherein the monomer concentrations differ from that exemplified above.
Fluoroelastomer Composition Polymer7 100 100 18-Crown-62 4.0 4.0 TiO2 20 20 C.I. Red-202 0 4,0 15 2. 1~4~7~lo~l3~l6-hexaoxacyclooctadecane 3. Dipotassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene)
Fluoroelastomer ComPosition Polymer4 100 100 10 ~etraphenyltin 3 3 DCH-18-Crown-65 SiO2 10 10 C.I. Red-206 - 3 15 4. Copolymer of tetrafluoroethylene (69.7 mole ~), perfluoromethyl perfluorovinyl ether (29.6 mole ~), and perfluoro(8-cyano-5-methyl-3,6-dioxa-isoocta~e) (0.7 mole %) 5. 2,5,~ 5,~18,21-hexaoxatric~clo[20.4Ø09~14~-hexacosane (i.e., dicyclohexyl-18-crown-6) ~L57~89 Physical Properties Stress/Strain (Post Cure - 2 days) Initial Mloo, MPa 3.7 4.3 TB, MPa 10.0 15.1 EB, % 250 240 Heat Aged (3 days/316C) Mloo, 2.5 2.7 TB, MPa 8.1 9.5 E3, % 340 350 Compression Set (70 h/204C) O-Rings, %
In~tial 51 57 Heat Aged 3 days 60 58 6. After post cure in nitrogen for 2 days, these samples were heated for an additional day at 316C
under nitrogen These examples demonstrate the beneficial effect of quinacridone pigment over a range of pigment concentrations:
Fluoroelastomer Composition Polymerl 100 100 100 100 100 K2AF 4.5 4.5 4.5 4.5 4.5 18-Crown-62 3.0 3.0 3.0 3.0 3.0 TiO2 20 20 20 20 20 30 C.I. Red-206 0 0.5 1.5 3.0 6.0 1. Copolymer of tetrafluoroethylene (69.7 mole %), perfluoromethyl per~luorovinyl ether (29.6 mole %), and perfluoro (8-cyano-~-methyl-3,6-dioxa-1-octene) (0.7 mole %) 2. 1,4,7,10,13,16-hexaoxacyclooctadecane 3. Dipotassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene) 14 ~57~89 Physical Properties _ Stress/Strain (Post Cure - 5 days) Initial Mloo, MPa 9.69.6 9.0 10.3 9.9 TB, MPa 13.112.6 14.7 14.7 15.9 EB, % 130 120 140 140 150 Heat Aged (2 days) Mloo, MPa 4.04.7 ~.7 7.0 6.6 TB, MPa 9.1 10.5 11.6 11.7 11.3 EB, % 230 210 220 210 230 Heat Aged (4 days) ~100' MPa 2.33.1 3.9 4.3 4.4 TB, MPa 3.0 6.2 7.2 7.4 6.8 EB, ~ 370 330 310 310 300 comPression Set (70 h/204C) Pellets, %
Initial 43 43 39 39 45 Heat Aged (2 days) 83 76 74 76 79 Heat Aged (4 days) 77* 84 85 81 82 O-Rings, ~
Initial -- 73 70 67 80 Heat Aged (2 days) 97 93 91 94 93 Heat Aged (4 days) 100+ 100+ 100+ 100+ 100+
* anomalous result ~L57189 These examples demonstrate the beneficial effect of quinacridone pigment in fluoroelastomer compositions containing a variety of non-black fillers:
Fluoroelastomer Composition 2l 22 23 24 Polymerl 100 100 100 100 K2AF 3 4.5 4.5 4.5 4.5 DCH-18-Crown-6 4.0 4.0 4.0 4.0 10 TiO2 (grade l) R902 20 20 TiO2 (grade 2) R960 - - 20 20 C.I. Red-206 - 3 - 3 1. Copolymer of tetrafluoroethylene (67.5 mole %) perfluoromethyl perfluorovinyl ether (32 mole %), and perfluoro(2-phenoxypropyl vinyl ether) (0.5 mole %) 3. Dipotassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene) 0 5. 2,5,8,15,18,21-hexaoxatricyclo[20.4Ø09'l4]-hexacosane g~L57~L89 Physical Properties Stress/Strain (Post Cure - 5 days) Initial Mloo, MPa 8.69.4 7.4 10.1 TB, MPa 12.512.6 10.8 13.1 EB, % 170 140 150 130 Heat Aged (3 days) Mloo, Not 5-0 2.7 4.6 TB, MPa test-7.0 1.9 7.6 E~, % able310 350 300 Compression Set (70 h/204C) Pellets, ~
Initial 2S 39 47 40 Heat Aged (3 days) n.t.100 100+ 80 O-Rings, ~
Initial 77 73 70 70 Heat Aged (3 days) n.t. 73 100+ 89 57~89 ExA~lpLEs 25-3~
These examples demonstrate the beneficial effect of quinacridone pigment in fluoroelastomer compositions containing a variety of non-black fillers:
Fluoroelastomer Composition Polymerl 100 100 100 100 100 100 K2AF 3 4.5 4.5 4.5 4.5 4.5 4,5 DCH-18-Crown-64.0 4.0 4.0 4.0 4.0 4.0 SiO2 10 10 - - - -Talc - - 13 13 Asbestos - - - - 11.5 11.5 C.I. Red-206 - 3 - 3 _ 3 15 1. Copolymer of tetrafluoroethylene (67.5 mole %), perfluoromethyl perfluorovinyl ether (32 mole ~), and perfluoro~2-phenoxypropyl vinyl ether) (0.5 mole %) 3. Dipotassium salt of hexafluoroisopropylidene bis(4-hydroxybenzene) 5. 2,5,8,15,18,21-hexaoxatricyclo[20.4Ø09'1 ~-hexacosane -~ 18 ~S7~89 Physical Properties Stress/Strain (Post Cure - 5 days) Initial S Mloo, MPa12.712.8 10.8 11.8 - -TB, MPa13.713.0 12.5 13.6 13.1 14.1 EB, % 110 100 120 120 90 90 ~eat Aged ~2 days) Mloo, ~Pa 6.5 9.0 5.6 8.5 7.6 9.9 TB, MPalO.S12.3 7.7 lO.S 6.1 10.0 EB, % 240 170 300 200 240 160 Compression Set (70 h/204C) Pellets, ~
Initial42 43 72 55 48 48 Heat Aged (2 days) 69 65 85 68 94 70 O-Rings, ~
Initial64 57 73 70 72 69 Heat Aged (2 days) 97 84 92 87 100+ -100+
., 19 ~57~89 EXA~LES 31-34 These examples demonstrate the beneficial effect of quinacridone pigment in fluoroelastomer compositions containing a variety of non-black fillers:
Fluoroelastomer Composition Polymerl 100 100 100 100 K2AF3 4-5 4-5 3.0 3.0 10 18-Crown-6 ~ ~ 3-0 3-0 Hydrated alumina 11.2 11.2 Zr2 ~ - 26 26 C.I. Red-206 - 5 - 2 1. Copolymer of tetrafluoroethylene (67.5 mole %), perfluoromethyl perfluorovinyl ether (32 mole ~), and perfluoro(2-phenoxypropyl vinyl ether) (0.5 mole %) 2. 1,4,7,10,13,16-hexaoxacyclooctadecane 3. Dipotassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene) 5. 2,5,8,15,18,21-hexaoxatricyclo~20-4--9'1 ]~
hexacosane P~57~89 Physical Properties Stress/Strain (Post Cure - 2 days) Initial Mloo, MPa 7.3 9.2 6.5 7.7 TB, MPa 11.3 13.2 12.3 15.7 EB, % 140 160 170 180 Heat Aged (2 days) Mloo, MPA 2.4 4.5 3.2 4.8 TB, MPa 5.5 8.2 7.7 15.1 EB, % 400 290 330 280 Heat Aged (4 days) Mloo, MPa - - Not 3.3 TB, MPa - - Test- 8.0 EB~ % able 390 Compression Set (70 h/204C) Pellets, ~
Initial 39 56 41 36 Heat Aged (2 days1 - - n.t. n.t.
Heat Aged (4 days) - - n.t. n.t.
O-Rings, %
Initial n.t. 62 62 56 Heat Aged (2 days) - - 100+ 76 Heat Aged (4 days~ - - n.t. n.t.
:
~5789 EX~MPLES 35-36 These examples demonstrate the superior stability, upon heat aging, of compositions treated with a small quantity of quinacridone pigment (Example 36) as comPared with untreated compositions ~Example 35), wherein the monomer concentrations differ from that exemplified above.
Fluoroelastomer Composition Polymer7 100 100 18-Crown-62 4.0 4.0 TiO2 20 20 C.I. Red-202 0 4,0 15 2. 1~4~7~lo~l3~l6-hexaoxacyclooctadecane 3. Dipotassium salt of hexafluoroisopropylidenebis(4-hydroxybenzene)
7. Copolymer of tetrafluoroethylene (71.5 mole %), perfluoromethyl perfluorovinyl ether (28 mole %), and perfluoro(2-phenoxypropylvinyl ether) (0.5 mole ~) 1~57~89 Physical Properties Stress/Strain (Post Cure - 5 days~
Initial MlOO,MPa 11.6 13.5 TB,MPa 17.2 16.6 EB' % 150 130 Heat Aged (2 days) M10O,MPa 5-.9 6.8 TB,~Pa 9.2 10.3 B' ~ 330 280 Heat Aged (4 days~
M10O,MPa Not 5.2 TB,MPa Test- 4.0 EB, % able 340 Compression Set (70 h/204C) Pellets, %
Initial 40 44 Heat Aged (4 days) 100+ 96 O-Rings, %
Initial 79 77 ~eat Aged (4 days) Not Testable 100+
These examples demonstrate the superior stability, upon heat aging, of compositions treated with a small quantity of quinacridone pigment (Example 38) as compared with compositions treated with other type pigments (Examples 39-41), as well as with un-treated compositions (Example 37):
-~57~89 Fluoroelastomer Composition 37 38 39 ~ 41 Polymerl 100 100 100 100 100 18-Crown-62 3 3 3 3 3 g2AF3 4.5 ~.5 4.5 4.~ 4 5 TiO2 20 17 18 18 18 C.I. Orange-48 - 3 - - -C.I. Green-75 - - 2 C.I. Blue-155 - - - 2 10 Black SAF6 _ _ _ 2 1. Copolymer of tetrafluoroethylene (67.5 mole %), perfluoromethyl perfluorovinyl ether (32 mole %3 and perfluoro(2-phenoxypropyl vinyl ether) (0.5 mole %) 2. 1,4,7~10,13,16-hexaoxacyclooctadec-ane 3. Dipotassium salt of hexafluoroisopropylidene-bis(4-hydroxybenzene) 5. Copper phthalocyanine pigment 6. Carbon black ~3 57189 Physical Properties Stress/Strain (Post Cure - 2 days) Initial Mloo, Pa 10.5 12.8 9.8 10.211.2 TB, MPa 15.8 16.7 15.5 13.215.4 EB, % 140 130 140 120130 PS, % 4 7 5 3 3 Heat Aged (2 days) Mloo, MPa 5.7 7.2 Not Not5.0 TB, MPa 11.5 14.7 - 8.1 EB, % 250 210 test- test-280 P`S, % 15 11 able able 17 15 Heat Aged (4 days) Mloo~ MPa 3.85.0 Not Not Not TB, MPa 6.0 11.0 EB, ~ 360 290~ Run RunRun PS, ~ 34 19 Compression Set (70 h/204C) Pellets, %
Initial 27 28 30 27 24 Heat Aged Surface (2 days)76 68 Degraded Melted 75 Heat Aged (4 aays)92 72 89 O-Rings, %
Initial 67 71 78 75 77 Heat Aged (2 days)90 82.~lted Melted100 Heat Aged (4 days)100+ 100+
Hardness, Shore A 76 78 75 78 79 ~57189 ~6 Industrial Applicability The fluoroelastomer compositions of the present invention are useful in the manufacture of finished parts such as O-rings, flange seals, gasket 5 stock, pump diaphragms and liners. The extraordinary physical properties and resistance to environmental attack of such parts made from these compositions make them particularly well suited for applications in process streams subject to severe fluid service at in-10 line temperatures as high as 700F (371C) or in streamscarrying highly corrosive fluids, such as hydrogen sulfide.
Best Mode Although the best mode of the present inven-15 tion, i.e., the single best fluoroelastomer compositionof the present invention, will depend upon the partic-ular desired end use and the specific re~uisite combination of properties for that use, the single most preferred composition of the present invention 20 is that described in detail in Example 24.
Initial MlOO,MPa 11.6 13.5 TB,MPa 17.2 16.6 EB' % 150 130 Heat Aged (2 days) M10O,MPa 5-.9 6.8 TB,~Pa 9.2 10.3 B' ~ 330 280 Heat Aged (4 days~
M10O,MPa Not 5.2 TB,MPa Test- 4.0 EB, % able 340 Compression Set (70 h/204C) Pellets, %
Initial 40 44 Heat Aged (4 days) 100+ 96 O-Rings, %
Initial 79 77 ~eat Aged (4 days) Not Testable 100+
These examples demonstrate the superior stability, upon heat aging, of compositions treated with a small quantity of quinacridone pigment (Example 38) as compared with compositions treated with other type pigments (Examples 39-41), as well as with un-treated compositions (Example 37):
-~57~89 Fluoroelastomer Composition 37 38 39 ~ 41 Polymerl 100 100 100 100 100 18-Crown-62 3 3 3 3 3 g2AF3 4.5 ~.5 4.5 4.~ 4 5 TiO2 20 17 18 18 18 C.I. Orange-48 - 3 - - -C.I. Green-75 - - 2 C.I. Blue-155 - - - 2 10 Black SAF6 _ _ _ 2 1. Copolymer of tetrafluoroethylene (67.5 mole %), perfluoromethyl perfluorovinyl ether (32 mole %3 and perfluoro(2-phenoxypropyl vinyl ether) (0.5 mole %) 2. 1,4,7~10,13,16-hexaoxacyclooctadec-ane 3. Dipotassium salt of hexafluoroisopropylidene-bis(4-hydroxybenzene) 5. Copper phthalocyanine pigment 6. Carbon black ~3 57189 Physical Properties Stress/Strain (Post Cure - 2 days) Initial Mloo, Pa 10.5 12.8 9.8 10.211.2 TB, MPa 15.8 16.7 15.5 13.215.4 EB, % 140 130 140 120130 PS, % 4 7 5 3 3 Heat Aged (2 days) Mloo, MPa 5.7 7.2 Not Not5.0 TB, MPa 11.5 14.7 - 8.1 EB, % 250 210 test- test-280 P`S, % 15 11 able able 17 15 Heat Aged (4 days) Mloo~ MPa 3.85.0 Not Not Not TB, MPa 6.0 11.0 EB, ~ 360 290~ Run RunRun PS, ~ 34 19 Compression Set (70 h/204C) Pellets, %
Initial 27 28 30 27 24 Heat Aged Surface (2 days)76 68 Degraded Melted 75 Heat Aged (4 aays)92 72 89 O-Rings, %
Initial 67 71 78 75 77 Heat Aged (2 days)90 82.~lted Melted100 Heat Aged (4 days)100+ 100+
Hardness, Shore A 76 78 75 78 79 ~57189 ~6 Industrial Applicability The fluoroelastomer compositions of the present invention are useful in the manufacture of finished parts such as O-rings, flange seals, gasket 5 stock, pump diaphragms and liners. The extraordinary physical properties and resistance to environmental attack of such parts made from these compositions make them particularly well suited for applications in process streams subject to severe fluid service at in-10 line temperatures as high as 700F (371C) or in streamscarrying highly corrosive fluids, such as hydrogen sulfide.
Best Mode Although the best mode of the present inven-15 tion, i.e., the single best fluoroelastomer compositionof the present invention, will depend upon the partic-ular desired end use and the specific re~uisite combination of properties for that use, the single most preferred composition of the present invention 20 is that described in detail in Example 24.
Claims (9)
1. A vulcanizable composition comprising a fluoroelastomer which is a terpolymer consisting essentially of 53-79.8 mole percent of tetrafluoro-ethylene, 20-45 mole percent of perfluoromethyl per-fluorovinyl ether and 0.2-2 mole percent of a cure-site monomer, at least one non-black filler, and a small quantity of at least one quinacridone-type pig-ment selected from the group consisting of quinacri-done, quinacridone quinone, substituted quinacridone, substituted quinacridone quinone, and mixtures and solid solutions of such substituted and unsubstituted quinacridones and quinacridone quinones.
2. A composition of Claim 1 wherein the cure-site monomer is selected from the group con-sisting of:
(a) perfluoro(4-cyanobutyl vinyl ether), (b) perfluoro(4-carbomethoxybutyl vinyl ether), (c) perfluoro(2-phenoxypropyl vinyl ether), (d) perfluoro(3-phenoxypropyl vinyl ether), and (e) perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene).
(a) perfluoro(4-cyanobutyl vinyl ether), (b) perfluoro(4-carbomethoxybutyl vinyl ether), (c) perfluoro(2-phenoxypropyl vinyl ether), (d) perfluoro(3-phenoxypropyl vinyl ether), and (e) perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene).
3. A composition of Claim 2 wherein the cure-site monomer is perfluoro(2-phenoxypropyl vinyl ether).
4. A composition of Claim 3 wherein the terpolymer consists essentially of 65.4-73.6 mole percent of tetrafluoroethylene, 26-34 mole percent of perfluoromethyl perfluorovinyl ether and 0.5 mole percent of perfluoro(2-phenoxypropyl vinyl ether).
5. A composition of Claim 1 wherein the non-black filler is selected from the group consisting of titanium dioxide, zirconium dioxide, silica, clay asbestos and hydrated aluminum oxide.
6. A composition of Claim 5 wherein the non-black filler is titanium dioxide.
7. A composition of Claim 1 wherein the quinacridone-type pigment is a solid solution con-taining quinacridone.
8. A composition of Claim 1 wherein quinacridone-type pigment is present in the composi-tion in an amount of 0.1-10 phr.
9. A composition of Claim 1 wherein the quinacridone-type pigment is selected from the group consisting of Colour Index Orange-48, Colour Index Violet-l9, Colour Index Red-206, Colour Index Orange-49, Monastral? transparent Red B pigment and Colour Index Red-202.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/143,817 US4316836A (en) | 1980-04-23 | 1980-04-23 | Stabilized fluoroelastomer compositions |
| US143,817 | 1980-04-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1157189A true CA1157189A (en) | 1983-11-15 |
Family
ID=22505782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000375773A Expired CA1157189A (en) | 1980-04-23 | 1981-04-21 | Stabilized fluoroelastomer compositions |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4316836A (en) |
| EP (1) | EP0038535B1 (en) |
| JP (1) | JPS56166251A (en) |
| AT (1) | ATE9482T1 (en) |
| AU (1) | AU541036B2 (en) |
| BR (1) | BR8102324A (en) |
| CA (1) | CA1157189A (en) |
| DE (1) | DE3166123D1 (en) |
| MX (1) | MX158928A (en) |
| NO (1) | NO155809B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS594473A (en) * | 1982-06-28 | 1984-01-11 | Asahi Glass Co Ltd | Painting and finishing method of cement base material |
| US4525539A (en) * | 1982-12-02 | 1985-06-25 | E. I. Du Pont De Nemours And Company | Vulcanizable nitrile-containing perfluoroelastomer |
| JPS59152914A (en) * | 1983-02-18 | 1984-08-31 | Asahi Glass Co Ltd | Curable resin composition |
| JPS61254A (en) * | 1984-06-13 | 1986-01-06 | Hitachi Cable Ltd | Fluoroelastomer composition |
| US5256747A (en) * | 1991-05-20 | 1993-10-26 | Leo Ojakaar | Soluble perfluoroelastomers |
| US5696189A (en) * | 1995-12-01 | 1997-12-09 | E. I. Du Pont De Nemours And Company | Perfluoroelastomer compositions |
| US6239223B1 (en) | 1997-09-05 | 2001-05-29 | Chemfab Corporation | Fluoropolymeric composition |
| JP4550954B2 (en) * | 1998-05-29 | 2010-09-22 | デュポン パフォーマンス エラストマーズ エルエルシー | White elastomer sealing material and method for producing the same |
| US7049380B1 (en) * | 1999-01-19 | 2006-05-23 | Gore Enterprise Holdings, Inc. | Thermoplastic copolymer of tetrafluoroethylene and perfluoromethyl vinyl ether and medical devices employing the copolymer |
| US6730760B2 (en) * | 2001-01-31 | 2004-05-04 | 3M Innovative Properties Company | Perfluoroelastomers having a low glass transition temperature and method of making them |
| CN1256355C (en) * | 2001-05-02 | 2006-05-17 | 3M创新有限公司 | Emulsifier free aqueous emulsion polymerization process for making fluoropolymers |
| US6833418B2 (en) * | 2002-04-05 | 2004-12-21 | 3M Innovative Properties Company | Dispersions containing perfluorovinyl ether homopolymers and use thereof |
| US6822059B2 (en) * | 2002-04-05 | 2004-11-23 | 3M Innovative Properties Company | Dispersions containing bicomponent fluoropolymer particles and use thereof |
| US20040024448A1 (en) | 2002-08-05 | 2004-02-05 | Chang James W. | Thermoplastic fluoropolymer-coated medical devices |
| US7892600B2 (en) * | 2002-12-06 | 2011-02-22 | E. I. Du Pont De Nemours And Company | Rotolining process |
| JP2008001894A (en) * | 2006-05-26 | 2008-01-10 | Daikin Ind Ltd | Fluorine-containing elastomer composition excellent in plasma resistance property and sealing material comprising the same |
| WO2009126708A1 (en) * | 2008-04-08 | 2009-10-15 | Greene, Tweed Of Delaware, Inc. | Oxygen plasma-resistant composition characterized by low sticking and related mothods |
| US8523503B2 (en) * | 2010-07-30 | 2013-09-03 | Nuovo Pignone, S.P.A. | Threaded joint and method of sealing a threaded joint |
| JP5354051B2 (en) * | 2012-04-09 | 2013-11-27 | ユニマテック株式会社 | Perfluoroelastomer composition |
| JP6166577B2 (en) * | 2013-04-16 | 2017-07-19 | 三井・デュポンフロロケミカル株式会社 | Fluororesin composition and molded product thereof |
| EP3156448B1 (en) * | 2014-09-16 | 2020-11-11 | Daikin Industries, Ltd. | Fluoroelastomer composition and molded article |
| WO2023042510A1 (en) * | 2021-09-14 | 2023-03-23 | ユニマテック株式会社 | Fluorine-containing elastomer composition |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL136331C (en) * | 1961-04-11 | |||
| US3244720A (en) * | 1965-01-21 | 1966-04-05 | Mcneilab Inc | Octahydro-9-acridanones |
| GB1145445A (en) * | 1966-02-16 | 1969-03-12 | Du Pont | Fluorinated perfluorovinylethers, their preparation and copolymers thereof |
| US3467638A (en) * | 1967-03-07 | 1969-09-16 | Du Pont | Fluorinated cure-site monomers and vulcanizable fluorocarbon polymers made therewith |
| US3580889A (en) * | 1967-08-17 | 1971-05-25 | Du Pont | Vulcanization accelerators of polycyclic ethers for fluorinated polymers |
| US3579474A (en) * | 1968-12-16 | 1971-05-18 | Du Pont | Elastomeric copolymers of tetrafluoroethylene containing phenoxyethyl groups,and their vulcanization |
| US3642742A (en) * | 1969-04-22 | 1972-02-15 | Du Pont | Tough stable tetrafluoroethylene-fluoroalkyl perfluorovinyl ether copolymers |
| US3682872A (en) * | 1970-03-18 | 1972-08-08 | Du Pont | Perfluoro(3-phenoxypropyl vinyl ether) monomer and copolymers made therefrom |
| US3707469A (en) * | 1970-09-22 | 1972-12-26 | Du Pont | 2,9-bis-trifluoromethylquinacridone and intermediate therefor |
| US3686154A (en) * | 1971-03-29 | 1972-08-22 | Du Pont | Composition and process for preparing cross-linked fluoro-polymer products |
| CA950923A (en) * | 1971-03-29 | 1974-07-09 | E. I. Du Pont De Nemours And Company | Polymers of perfluorovinyl ethers |
| US3819594A (en) * | 1972-05-17 | 1974-06-25 | Du Pont | Tetrafluoroethylene fine powder resin of a copolymer of tetrafluoroethylene and perfluoro(alkyl vinyl ether) |
| US3933767A (en) * | 1972-06-14 | 1976-01-20 | E. I. Du Pont De Nemours And Company | Cyanoperfluoroether acid fluorides and copolymers derived therefrom |
| US3852237A (en) * | 1972-09-08 | 1974-12-03 | Phillips Petroleum Co | Clearer polyefins by combination of aryl carboxlic acid phthalocyanine, and quinacridone |
| DE2311096C3 (en) * | 1973-03-06 | 1981-08-20 | Hoechst Ag, 6000 Frankfurt | Process for connecting molded articles containing polytetrafluoroethylene |
| US3855191A (en) * | 1973-04-04 | 1974-12-17 | Du Pont | Polytetrafluoroethylene molding powders of tetrafluoroethylene and perfluoro (alkyl vinyl ether) copolymer |
| DE2457102C3 (en) | 1974-01-31 | 1981-07-02 | E.I. Du Pont De Nemours And Co., Wilmington, Del. | Vulcanizable fluoroelastomer copolymer |
| JPS5334145B2 (en) * | 1975-03-07 | 1978-09-19 | ||
| US4015998A (en) * | 1975-09-24 | 1977-04-05 | E. I. Du Pont De Nemours And Company | 2,9-Dichloroquinacridone pigment compositions |
-
1980
- 1980-04-23 US US06/143,817 patent/US4316836A/en not_active Expired - Lifetime
-
1981
- 1981-04-15 BR BR8102324A patent/BR8102324A/en unknown
- 1981-04-16 DE DE8181102931T patent/DE3166123D1/en not_active Expired
- 1981-04-16 AT AT81102931T patent/ATE9482T1/en not_active IP Right Cessation
- 1981-04-16 EP EP81102931A patent/EP0038535B1/en not_active Expired
- 1981-04-21 JP JP5933281A patent/JPS56166251A/en active Granted
- 1981-04-21 CA CA000375773A patent/CA1157189A/en not_active Expired
- 1981-04-21 AU AU69674/81A patent/AU541036B2/en not_active Ceased
- 1981-04-22 NO NO811361A patent/NO155809B/en unknown
- 1981-04-22 MX MX186964A patent/MX158928A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6360785B2 (en) | 1988-11-25 |
| BR8102324A (en) | 1981-12-08 |
| DE3166123D1 (en) | 1984-10-25 |
| NO811361L (en) | 1981-10-26 |
| NO155809B (en) | 1987-02-23 |
| JPS56166251A (en) | 1981-12-21 |
| EP0038535A3 (en) | 1982-02-03 |
| ATE9482T1 (en) | 1984-10-15 |
| EP0038535A2 (en) | 1981-10-28 |
| MX158928A (en) | 1989-03-31 |
| US4316836A (en) | 1982-02-23 |
| AU6967481A (en) | 1981-10-29 |
| AU541036B2 (en) | 1984-12-13 |
| EP0038535B1 (en) | 1984-09-19 |
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