ANDERSON BENJAMIN J (US)
FUKUSHI TATSUO (US)
MCBRIDE JUSTIN P (US)
SUZUKI YUTA (JP)
WO2010151610A2 | 2010-12-29 | |||
WO2020245683A1 | 2020-12-10 |
EP2070982A1 | 2009-06-17 | |||
US8906821B2 | 2014-12-09 |
What is claimed is: 1. A composition comprising (i) an uncured highly fluorinated amorphous polymer comprising nitrile groups, wherein at least 80 mole% of the hydrogen atoms of the polymer backbone of the highly fluorinated amorphous polymer have been replaced with fluorine atoms; (ii) a catalyst comprising an organo onium cation and an anion of Formula I: (I) wherein each R and R’ is independently is H, halo, alkyl, aryl, aralkyl, or cycloalkyl, and which also may be halogenated, fluorinated, or perfluorinated, optionally wherein each R or R’ group independently may contain one or more heteroatom(s); wherein two or more of R and R' groups may together form a ring with the proviso that R' cannot be halo; and (iii) an additive comprising a compound of Formula II wherein X1 and X2 are independently selected from O or S, and L comprises at least one multivalent six-membered arene group. 2. The composition of claim 1 wherein each R is F and R ' is selected from H, phenyl, methoxyphenyl, toluyl, phenoxy, fluorophenyl, trifluoromethylphenyl, and CF3. 3. The composition of any one of the previous claims, wherein Formula I comprises at least one of tetra-alkylammonium 2-phenyl-1,1,1,3,3,3 hexafluoroisopropanoate, tetra-alkylammonium 1,1,1,3,3,3 hexafluoroisopropanoate, tetrabutylphosphonium 2-phenyl-1,1,1,3,3,3 hexafluoroisopropanoate, tetrabutylphosphonium 1,1,1,3,3,3 hexafluoroisopropanoate, tetrabutylphosphonium 2-methoxyphenyl-1,1,1,3,3,3 hexafluoroisopropanoate, or tetrabutylphosphonium 2-p-toluyl-1,1,1,3,3,3 hexafluoroisopropanoate. 4. The composition of any one of the preceding claims, wherein at least 95 mole % of the hydrogen atoms of the polymer backbone of the uncured highly fluorinated amorphous polymer have been replaced with fluorine atoms. 5. The composition of any one of the preceding claims, wherein the uncured highly fluorinated amorphous polymer comprises repeating units derived from a perfluorinated monomer comprising a nitrile group, tetrafluoroethylene (TFE), and at least one comonomer selected from the group consisting of a perfluoroalkyl vinyl ether (PAVE) and a perfluoroalkyl allyl ether (PAAE). 6. The composition of any one of the preceding claims, wherein the uncured highly fluorinated amorphous polymer comprises at least 1 mole % and no greater than 5 mole % of nitrile groups. 7. The composition of any one of the preceding claims, wherein the composition comprises at least 0.05 to at most 5 weight % of the catalyst. 8. The composition of any one of the preceding claims, wherein the composition comprises at least 0.05 to at most 9 weight % of the compound according to Formula (II). 9. The composition of any one of the preceding claims, wherein L is a divalent, trivalent or tetravalent group. 10. The composition of any one of the preceding claims, wherein L is wherein R1 is selected from the group consisting of a methyl, methoxy, ethyl, and ethoxy group and R2 is selected from the group consisting of a methyl, methoxy, ethyl, and ethoxy group. 11. The composition of any one of claims 1-10, wherein L is wherein R4 is selected from the group consisting of: bond, -S-, -O-, -C(CF3)2-, -C(CH3)2-, - CH2-, -SO2-, -C(=O)-, and -C(CH3)2-C6H4-C(CH3)2-; each R1 is independently selected the group consisting of a methyl, methoxy, ethyl, and ethoxy group and each R2 is independently selected from the group consisting of a methyl, methoxy, ethyl, and ethoxy group. 12. The composition of any one of the preceding claims, wherein the composition further comprises a filler, wherein the filler is at least one of carbon black, or polytetrafluoroethylene. 13. An article comprising a cured elastomer derived from the composition according to any one of claims 1 to 12. 14. The article of according to claim 13, wherein the article has a compression set of no greater than 80% after 70 hours at 335 °C. 15. A method of make a highly fluorinated elastomer, the method comprising: (a) combining (i) a highly fluorinated amorphous polymer comprising nitrile groups, wherein at least 80 mole% of the hydrogen atoms of the polymer backbone of the highly fluorinated amorphous polymer have been replaced with fluorine atoms; (ii) a catalyst comprising an organo onium cation and an anion of Formula I: (I) wherein each R and R’ is independently is H, halo, alkyl, aryl, aralkyl, or cycloalkyl, and which also may be halogenated, fluorinated, or perfluorinated, optionally wherein each R or R’ group independently may contain one or more heteroatom(s); wherein two or more of R and R' groups may together form a ring with the proviso that R' cannot be halo; and (iii) an additive comprising a compound of Formula II (II) wherein X1 and X2 are independently selected from O or S, and L comprises at least one multivalent six-membered arene group to form a mixture. 16. The method of claim 15, further comprising (b) molding an article at a temperature suitable for press cure to form a molded article; and (c) contacting the molded article with a non-isothermic heat cycle. 17. The method of claim 16, wherein the non-isothermic heat cycle includes a final ramp of less than 1 hour to a temperature of at least 300°C. 18. The use of a catalyst and an additive to cure a highly fluorinated amorphous polymer comprising nitrile groups, wherein at least 80 mole% of the hydrogen atoms of the polymer backbone of the highly fluorinated amorphous polymer have been replaced with fluorine atoms; the catalyst comprises an organo onium cation and an anion of Formula I: (I) wherein each R and R’ is independently is H, halo, alkyl, aryl, aralkyl, or cycloalkyl, and which also may be halogenated, fluorinated, or perfluorinated, optionally wherein each R or R’ group independently may contain one or more heteroatom(s); wherein two or more of R and R' groups may together form a ring with the proviso that R' cannot be halo; and the additive comprises a compound of Formula II (II) wherein X1 and X2 are independently selected from O or S, and L comprises at least one multivalent six-membered arene group. |
[0037] Curable Composition [0038] The organo onium catalyst according to formula (I) and the bis phthalonitrile-containing compound of Formula (II) can be used to cure highly fluorinated, nitrile-group containing amorphous fluoropolymers. [0039] In one embodiment, at least 0.05, 0.1 or even 1 part by weight; and at most 2, 4, 6, or even 10 parts by weight of the organo onium catalyst is used per 100 grams of amorphous highly fluorinated polymer. In one embodiment, at least 0.05, 0.1 or even 1 part by weight; and at most 2, 2.5, 3, 4, 5, 6, 8 or even 10 parts by weight of amount of the bis phthalonitrile-containing compound according to Formula (II) is used per 100 grams of amorphous highly fluorinated polymer. [0040] In some embodiments, the curable compositions comprising the highly fluorinated, nitrile- group containing amorphous fluoropolymer, the organo onium catalyst according to formula (I) and the bis phthalonitrile-containing compound of Formula (II) can also contain a wide variety of additives of the type normally used in the preparation of elastomeric compositions, such as acid acceptors, process aides, pigments, fillers, pore-forming agents, and those known in the art. [0041] Such fillers include: an organic or inorganic filler such as clay, silica (SiO 2 ), alumina, iron red, talc, diatomaceous earth, barium sulfate, wollastonite (CaSiO 3 ), calcium carbonate (CaCO 3 ), calcium fluoride, titanium oxide, iron oxide and carbon black fillers, a polytetrafluoroethylene powder, PFA (TFE/perfluorovinyl ether copolymer) powder, an electrically conductive filler, a heat-dissipating filler, and the like may be added as an optional component to the composition. Those skilled in the art are capable of selecting specific fillers at required amounts to achieve desired physical characteristics in the vulcanized compound. The filler components may result in a compound that is capable of retaining a preferred elasticity and physical tensile, as indicated by an elongation and tensile strength value, while retaining desired properties such as retraction at lower temperature (TR-10). [0042] In one embodiment, the composition comprises less than 50, 40, 30, 20, 15, or even 10% by weight of the inorganic filler. [0043] Conventional adjuvants may also be incorporated into the composition of the present disclosure to enhance the properties of the resulting composition. For example, acid acceptors may be employed to facilitate the cure and thermal stability of the compound. Suitable acid acceptors may include magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphite, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, hydrotalcite, alkali stearates, magnesium oxalate, or combinations thereof. The acid acceptors are preferably used in amounts ranging from about 1 to about 20 parts per 100 parts by weight of the polymer. [0044] Generally, the organo onium catalyst, the bis phthalonitrile-containing compound, and optional additives can be blended with the highly fluorinated amorphous fluoropolymer and formed into articles such as sheets and O-rings using commonly known equipment and methods. For example, the compounded composition can be press cured at temperatures of at least 175 °C, e.g., at least 185 °C. In some embodiments, the press curing temperature is no greater than 225 °C, or even no greater than 200 °C. The extent of cure can be determined according to the cure rheology test described in the Examples. The press cure time is selected to achieve a desired level of cure, which can be indicated by the Tan δ at M H . Generally, adequate cure is indicated by a Tan δ at M H of no greater than 0.5, e.g., no greater than 0.2, or even no greater than 0.1, as determined according to the cure rheology test described below. For most applications, t’90 (as determined according to the cure rheology test) should be less than 20 minutes, for example no greater than 10 minutes. To minimize the risk of scorching, t’90 should be at least 2 minutes. In some embodiments, longer cure times, e.g., a t’90 value of at least 4 minutes may be beneficial. [0045] Ideally, the molded mixture or press-cured article is post-cured (e.g., in an oven) at a temperature and for a time sufficient to complete the curing. Post curing is usually between about 150 ºC and about 300ºC, typically at about 230 ºC, for a period of from about 2 hours to 50 hours or more, generally increasing with the cross-sectional thickness of the article. For thick sections, the temperature during the post cure is usually raised gradually from the lower limit of the range to the desired maximum temperature. The maximum temperature used is typically about 300 ºC, and this temperature is held for about 4 hours or more. The post-cure step generally completes the cross-linking and may also release residual volatiles from the cured compositions. In one embodiment, the post-cure involves exposing molded parts to non-isothermic heat cycle. For example, the temperature is increased from room temperature to 150 °C over 2 hours with a 7 hour hold at 150 °C followed by a ramp to 300 ° C over 2 hours with a hold at 300°C for 2 hours. Finally, the part was ramped to 320 °C over 15 min with a hold for 15 min before returning to ambient temperature (e.g., by shutting off the oven heat). Another example of a suitable post-cure cycle involves exposing molded parts to heat under nitrogen using six stages of conditions. First, the temperature is increased from 25 ºC to 200 ºC over 6 hours, then the parts are held at 200 ºC for 16 hours, after which the temperature is increased from 200 ºC to 250 ºC over 2 hours. Then the parts are held at 250 ºC for 8 hours, after which the temperature is increased from 250 ºC to 300 ºC over 2 hours. Then the parts are held at 300 ºC for 16 hours. Finally, the parts are returned to ambient temperature such as by shutting off the oven heat. [0046] In some applications, for examples, O-rings and seals, the compression set is a critical property. In some embodiments, the cured compositions of the present disclosure have improved compression set, especially at higher temperatures, e.g., at 300, 325, 335, or even 350 °C. In some embodiments, the cured compositions have a compression set of no greater than 60, 55, 50, 40, 35, 30, or even 25% after 70 hours at 300 °C, as measured in accordance with ASTM D 395-03 Method B and ASTM D 1414-94 with an initial deflection of 25 percent. In some embodiments, the cured compositions have a compression set of no greater than 80, 70, 60, 55, 50, or even 45%, after 70 hours at 335 °C, as measured in accordance with ASTM D 395-03 Method B and ASTM D 1414-94 with an initial deflection of 25 percent. In some embodiments, the compositions of the present disclosure maintain article integrity upon exposure to high temperatures, for example, the cured article does not melt. Although not wanting to be limited by theory, it is believed that the presence of the additive according to Formula II aids in maintaining the crosslinks of the cured article upon exposure to high temperatures. EXAMPLES [0047] Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, and all materials are commercially available, for example from Sigma-Aldrich Chemical Company, Milwaukee, WI, USA, or known to those skilled in the art, unless otherwise stated or apparent. [0048] The following abbreviations are used in this section: g=grams, lb=pounds, cm=centimeters, min=minutes, h=hours, N=newtons, dNm=decinewton meters, MV=Mooney viscosity, °C=degrees Celsius, °F=degrees Fahrenheit, PSI=pounds per square inch, MPa=megapascals, mol=moles. Abbreviations for materials used in this section, as well as descriptions of the materials, are provided in Table 1. Table 1. [0049] Preparative Example 1: BF6 Phth [0050] To a three necked 500 mL reaction flask was added 50.0 g (0.289 mol) of 4- nitrophthalonitrile, 48.55 g (0.144 mol) of 4,4'- (hexafluoroisopropylidene)diphenol, 49.9 g (0.361 mol) of anhydrous K 2 CO 3 and 225 g of dry DMSO. The reaction solution was heated to 70° C and mechanically stirred with sparging nitrogen for 3.5 h. Stirring was ceased, and the reaction salts settled to the bottom of the vessel. Some of the reaction product had begun to crystalize from the reaction liquid. The reaction solution liquid and product were decanted from the reaction salts into a stirring chilled mixture of 250 g of 80/20 methanol/water by mass. Additional product crystallized from the DMSO/methanol/water solution. The reaction salts were washed with 25 g of DMSO, and the wash DMSO decanted into the stirring DMSO/methanol/water solution. The product solids were collected on a Büchner funnel and washed with methanol, water, and methanol. The solids were collected in an aluminum pan and were dried of methanol and water in a convection oven at 140 °C for 2 h. The solids were further heated to 250 °C for 15 min which melted the solids and drove off residual DMSO. The product melt was removed from the oven and allowed to cool to ambient temperature. The product, 79.0 g (92.9% yield), had a melt temperature of 231-232 °C by differential scanning calorimetry measurement (DSC Q 2000, TA Instruments, New Castle, DE). The product was identified as bis(3,4-dicyanophenyl) ether of 4,4'- (hexafluoroisopropylidene)diphenol by infrared analysis and NMR and had a purity of >99%. [0051] Preparative Example 2: Diphenyl Phth [0052] 4-nitrophthalonitrile (48.8 g) and 4,4’-biphenol (26.24 g) were added to a two neck 500 mL round bottom flask.200 g of DMF was added to the flask. The 4-nitrophthalonitrile and the 4,4’-biphenol were dissolved in the DMF by stirring with an egg-shaped stir bar on a magnetic stir plate. DBU (53.6 g) was added in one addition. The flask necks were sealed with rubber septums with a thermoprobe inserted through one rubber septum. The solution was stirred with an egg- shaped stir bar and heated to 70 °C with a heating mantle. The flask solution was held at 70 o C for 2 h. The solution was allowed to cool to ambient temperature. The product was precipitated by addition to 500 mL of stirring methanol. The precipitate was collected on a Büchner funnel with #4 Whatman filter paper with suction and washed with 200 mL of methanol, 200 mL of water, and 200 mL of methanol. The collected solids were air dried overnight, and further dried in a vacuum oven at 180 °C the next day for 1 hour. The solids, 59.1g (95.6% yield), had a melt temperature of 236°C as measured by differential scanning calorimetry, and were identified as 4,4′-bis(3,4- dicyanophenoxy)biphenyl by infrared and NMR analysis. [0053] Preparative Example 3: Resorc Phth [0054] To a three necked 500 mL reaction flask was added 50.0 g (0.289 mol) of 4- nitrophthalonitrile, 15.90 g (0.144 mol) of resorcinol, 49.9 g (0.361 mol) of anhydrous K 2 CO 3 , and 175 g of dry DMSO. The reaction solution was heated to 70 °C and mechanically stirred with sparging nitrogen for 3.5 h. Stirring was ceased, and the reaction salts settled to the bottom of the vessel. The reaction solution liquid and product were decanted from the reaction salts into a stirring chilled mixture of 200 g of 80/20 methanol/water by mass. The product crystallized from the DMSO/methanol/water solution. The reaction salts were washed with 25 g of DMSO, and the wash DMSO decanted into the stirring DMSO/methanol/water solution. The product solids were collected on a Büchner funnel and washed with methanol, water and methanol. The solids were collected in an aluminum pan and were dried of methanol and water in a convection oven at 140 °C for 2 h. The solids were further heated in a vacuum oven to 200 °C for 1 h which melted the solids and stripped off residual DMSO. The product melt was removed from the oven and allowed to cool to ambient temperature. The product, 47.3 g (90.4% yield), had a melt temperature of 185 °C by differential scanning calorimetry measurement on a TA Instruments DSC Q 2000. The product was identified as bis(3,4-dicyanophenyl) ether of resorcinol infrared analysis and NMR and had a purity of >99%. [0055] Preparative Example 4: BPT Phth [0056] To a three necked 500 mL reaction flask was added 50.0 g (0.289 mol) of 4- nitrophthalonitrile, 31.52 g (0.144 mol) of bisphenol T, 49.9 g (0.361 mol) of anhydrous K 2 CO 3 , and 225 g of dry DMSO. The reaction solution was heated to 70 °C and mechanically stirred with sparging nitrogen for 3.5 h. Stirring was ceased, and the reaction salts settled to the bottom of the vessel. The reaction solution liquid and product were decanted from the reaction salts into a stirring chilled mixture of 250 g of 80/20 methanol/water by mass. The product crystallized from the DMSO/methanol/water solution. The reaction salts were washed with 25 g of DMSO, and the wash DMSO decanted into the stirring DMSO/methanol/water solution. The product solids were collected on a Büchner funnel and washed with methanol, water and methanol. The solids were collected in an aluminum pan and were dried of methanol and water in a convection oven at 140 °C for 2 h. The solids were further heated in a vacuum oven to 200 °C for 1 h which melted the solids and stripped off residual DMSO. The product melt was removed from the oven and allowed to cool to ambient. The product, 60.6 g (89.2% yield), had a melt temperature of 178 °C by differential scanning calorimetry measurement on a TA Instruments DSC Q 2000. The product was identified as bis(3,4-dicyanophenyl) ether of bisphenol T by infrared analysis and NMR and had a purity of >99%. [0057] Samples were made in 100 g polymer batches by compounding the amounts of materials as listed in Table 1 on a two-roll mill. For example, 0.7 g of Catalyst was added to 100 g of Fluoropolymer A in CE-1. [0058] Cure rheology tests were carried out using uncured, compounded samples using a rheometer marketed under the trade designation PPA 2000 by Alpha technologies, Akron, OH, in accordance with ASTM D 5289-93a at 177 ºC, no pre-heat, 15 minute elapsed time, and a 0.5 degree arc. Both the minimum torque (M L ) and highest torque attained during a specified period of time when no plateau or maximum torque (M H ) was obtained were measured. Also measured were the time for the torque to reach a value equal to M L + 0.5(M H - M L ), (t '50), the time for the torque to reach M L + 0.9(M H - M L ), and the value of the tan d curve at the maximum torque, (tan δ M H ). Results are reported in Tables 3. [0059] O-rings (214, AMS AS568) were molded at 177 °C for 15 min. The press cured O-rings were post-cured at one of two conditions: (A) 250 °C for 16 h or (B) a ramp from room temperature to 150 °C over 2 h with a 7 h hold at 150 °C followed by a ramp to 300 ° C over 2 h with a hold at 300°C for 2 h, and finally a ramp to 320 °C over 15 min with a hold for 15 min. The post cured O-rings were tested for compression set resistance for 70 h at 300 °C, 325 °C, and 335 °C in accordance with ASTM D 395-03 Method B and ASTM D 1414-94 with 25 % initial deflection. Results are reported as percentages in Table 4. Table 2. Table 3. Table 4. [0060] FT-IR Analysis [0061] CE-1 and EX-2 were analyzed by Fourier Transform-Infrared (FT-IR) spectroscopy (Perkin Elmer FT-IR Frontier spectrometer, Waltham, MA) in transmission. A sample of uncured compound (6 to 8g) was placed into the PPA 2000 rheometer and cured for 15 minutes a 177°C to form a press cured disk. The disk was then post cured following condition (B) as described above for the O-rings. An initial IR spectrum was obtained for the post cured disk. Then the disk was placed on a stainless-steel plate and subjected to heat aging at 335°C for 70 hours. The heat-aged sample was allowed to cool for 30 minutes, then an IR spectrum was obtained. [0062] Data analysis of the absorbance spectra was performed using Perkin Elmer Spectrum IR software. For the peaks of interest, a baseline was first established. For the C-F overtone, the baseline was established from 2210-2750 cm -1 , and the area of this peak was determined by using endpoints of 2210 cm -1 and 2700 cm -1 . Baseline from the triazine peak was determined by endpoints of 1525 cm -1 and 1575 cm -1 and the area of this peak was determined by using endpoints of 1525 cm -1 and 1575 cm -1 . Results are listed in Table 5. Table 5. [0063] CE-1 and EX-2 were prepared at the same thickness and as observed in Table 5, they have a similar initial integrated peak area for the C-F overtone. CE-1 and EX-2 also have a similar initial integrated peak area for the triazine peak. However, upon heat aging, CE-1 appears to show a decrease in both the C-F overtone and the triazine peak areas whereas the integrated peak areas for EX-2 appear relatively unchanged, indicating retention of crosslinking sites which may explain the unexpectedly good compression set data for the o-ring samples of the present disclosure. [0064] Foreseeable modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention. This invention should not be restricted to the embodiments that are set forth in this application for illustrative purposes. To the extent that there is any conflict or discrepancy between this specification as written and the disclosure in any document mentioned or incorporated by reference herein, this specification as written will prevail.