WO1997023556A1 - Fluorinated onium salts, curable compositions containing same, and method of curing using same - Google Patents
Fluorinated onium salts, curable compositions containing same, and method of curing using same Download PDFInfo
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- WO1997023556A1 WO1997023556A1 PCT/US1996/018936 US9618936W WO9723556A1 WO 1997023556 A1 WO1997023556 A1 WO 1997023556A1 US 9618936 W US9618936 W US 9618936W WO 9723556 A1 WO9723556 A1 WO 9723556A1
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- group
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- onium
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- 0 [*-]**(**=N)N*N=O Chemical compound [*-]**(**=N)N*N=O 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
Definitions
- This invention relates to curing vinylidene fluoride-containing fluoropolymer compositions.
- Fluoropolymers containing vinylidene fluoride units have particular utility in high temperature applications, including seals, gaskets, and linings, as described, for example, in Brullo, R.A., "Fluoroelastomer Rubber for Automotive Applications,” Automotive Elastomer & Design, June 1985, “Fluoroelastomer Seal Up Automotive Future," Materials
- organo-onium compounds have been proposed for this purpose.
- the cured polymers generally adhere to the surface of the mold.
- a shaped article prepared from the fluoropolymer is frequently torn or damaged when removed from the mold.
- the incorporation of a mold release agent into the polymer can have serious adverse effects on the physical properties of the cured composition (e.g., Mooney Scorch, shrinkage, and compression set) which can limit the successful commercial use of the cured composition.
- Mold fouling deposits of polymer on the mold cavity surface ("mold fouling") and poor release of the shaped, cured article from the mold are major reasons for defects, resulting in rejection of the article (which then adds to the expense of manufacturing such articles).
- mold release problem is proposed in Kolb et al., U.S. Pat. No. 5,262,490 (which is hereby inco ⁇ orated by reference).
- Kolb describes compositions containing a phosphonium or ammonium salt, a sulfonium compound, and (optionally) a polyhydroxy compound that are designed to perform the dual functions of accelerating fluoropolymer cure and providing mold release properties.
- the invention features a class of compounds useful, e.g., as cure accelerators for vinylidene fluoride-containing polymers having the formula:
- R 1 , R 2 , R 3 , and R 4 independently, comprise (a) a non-fluorinated alkyl (e.g., a branched or straight chain alkyl group such as methyl, ethyl, propyl, butyl, or iso-butyl), cycloalkyl (e.g., cyclohexyl), allyl, aryl (e.g., phenyl), or aralkyl (e.g., benzyl) group; (b) an onium- containing group; or (c) a group having the formula -(CH 2 ) ceremoni-Y-R 5 in which n is at least two; Y is a spacer arm comprising a -CH 2 -, -O-, -OCH 2 -, -S-, -SO -, or -Z- S0 2 - group; Z
- At least one of the R 1 , R 2 , R 3 , and R 4 groups comprises (1) an alkyl group having at least four carbon atoms; (2) a group having the formula -(CH 2 ) n -O-R 5 ; or (3) a group having the formula -(CH 2 ) n -Ph-O-SO 2 -R 5 where Ph is a phenyl group.
- the R 5 group preferably is (1) a perfluorinated alkyl group; (2) a perfluorinated ether group having the formula:
- Rf is a perfluoroalkyl group (e.g., a Ci-Ce perfluorinated alkyl group such as a perfluorinated methyl group), and R f • is F or a perfluoroalkyl group (e.g., a Ci-C ⁇ perfluorinated alkyl group such as a perfluorinated methyl group); or (3) a fluorinated alkyl group having the formula -CH 2 -(CF 2 ) X -H in which x is at least four.
- Preferred onium ions include phosphonium, ammonium, and sulfonium ion, as well as combinations thereof, with phosphonium ions being particularly preferred.
- One example of a preferred compound has the formula
- a second example of a preferred compound has the formula:
- a third example of a preferred compound has the formula:
- a fourth example of a preferred compound has the formula:
- a fifth example of a preferred compound has the formula
- a sixth example of a preferred compound has the formula.
- the invention also features a method of curing a polymer comprising vinylidene fluoride units using the above-described cure accelerators, as well as curable compositions comprising such polymers and the above-described cure accelerators.
- cure is conducted in the absence of mold release agents.
- Mold release agent refers to a material other than the cure accelerator that aids in removing the final cured composition from the mold in which cure takes place. Mold release agents include materials applied to the surface of the mold, as well as materials mixed together with the curable composition.
- Ph refers to a phenyl group.
- t-Bu refers to an isobutyl group
- the invention provides curable compositions with rapid cure times in which cure time is decreased by means of a fluorinated onium cure accelerator.
- the fluorinated onium cure accelerator itself also provides good mold release properties, thereby dispensing with the need for separate mold release agents.
- the resulting cured articles exhibit good physical properties.
- Curable vinylidene fluoride-containing fluoropolymer compositions according to the invention contain a fluorinated onium salt as a cure accelerator.
- a fluorinated onium salt as a cure accelerator.
- the counterion A ' may be an organic or inorganic anion, e.g., halide, thiosulfate, formate, cyanate, thiocyanate, tetraphenylborate, perchlorate, nitrate, tetrafluoroborate, hexafluorophosphate, oxalate, stearate, haloacetate, para-toluenesulphonate, ZnCl 4 2 ⁇ CdCl 2" , NiBr 4 2' , Hgl 3 " , sulfate, acetate, phosphate, phosphonate, hydroxide, alkoxide, phenoxide, trifluorome
- R 1 to R 4 and R 6 groups are preferably selected from the group of radicals consisting of alkyl, aryl, allyl, and alkenyl radicals, or combinations thereof.
- the R groups may be unsubstituted or substituted with one or more neutral, nonfunctional substituents that are non-ionizable under conditions of compounding or cure.
- substituents include, e.g., halogen atoms, cyano, - OR', and -COOR' moieties where R* is selected from the group of radicals consisting of C ⁇ -C 20 alkyl, aryl, aralkyl, and alkenyl radicals.
- R* is selected from the group of radicals consisting of C ⁇ -C 20 alkyl, aryl, aralkyl, and alkenyl radicals.
- any pair of R groups can be connected with each other and the onium ion to form a heterocyclic ring.
- the R 5 group is a fluorinated group, perfluorinated group, or combination thereof.
- preferred groups include fluorinated and perfluorinated alkyl and alkoxy groups.
- the fluorinated onium salts are generally prepared by reacting, e.g., a phosphine, amine, or sulfide with an alkylating agent, resulting in the expansion of the valence of the electron donating phosphorous, nitrogen, or sulfur atom and a positive charge on the organo-onium.
- curable vinylidene fluoride-containing polymers are described in the aforementioned Kolb patent; Worm, U.S. Pat. No. 4,233,421 ; and Grootaert et al., U.S. Pat. No. 4,882,390, all of which are hereby incorporated by reference.
- Fluorine-free terminally unsaturated monoolefin monomers e.g., ethylene or propylene, may also be used as co-monomers.
- Fillers are often added to the polymers discussed above to improve the physical properties of the cured composition or vulcanizate.
- a filler When a filler is employed, it is added to the vulcanization recipe in amounts of up to about 100 parts per hundred parts by weight of polymer, preferably between about 1 and 50 parts per hundred parts by weight of the polymer.
- fillers which may be used are reinforcing thermal grade carbon blacks or non-black pigments of relatively low reinforcement characteristics such as clays, barytes, etc.
- the curable composition preferably contains a crosslinking agent as well.
- a crosslinking agent is well known and are described in the art, e.g., in the aforementioned Kolb and Worm patents, and in U.S. Pat. Nos. 4,259,463 (Moggi et al.), 3,876,654 (Pattison), and 5,384,374 (Guerra et al ), all of which are hereby inco ⁇ orated by reference, and can include aromatic polyhydroxy compounds, aliphatic polyhydroxy compounds, and derivatives thereof. Blends may be used as well.
- Preferred polyhydroxy compounds are aromatic polyhydroxy compounds such as isopropylidene-bis(4-hydroxy-benzene) (“bisphenol A”) and hexafluoro- isopropylidenebis(4-hydroxybenzene) (“bisphenol AF").
- Fluoroaliphatic sulfonamides can also be added, including those of the formula RfSO 2 NHR", where R" is a hydrogen atom or alkyl radical having, for example, from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, R f is a fluoroaliphatic radical such as a perfluoroalkyl, e.g., C n F2n+ ⁇ where n is 1 to 20, or perfluorocycloalkyl, e.g , C n F 2n . ⁇ where n is 3 to 20, such compounds being described, for example, in U.S.
- the fluoroaliphatic sulfonamide is preferably a perfluoroalkylsulfonamide and may be added as a separate compound, or as the anion of the organo-onium compound
- the fluorinated cure accelerators and crosslinking agent can be added to the uncured polymer gum in the form of finely divided solids or as solutions in alcohol or ketone solvents by mixing the materials into the polymer gum stock
- the gum stock can generally be stored at room temperature for extended periods, e.g., up to two years or more
- an acid acceptor is mixed into the gum stock, after which storage life of the stock is more limited
- Acid acceptors can be inorganic or organic Organic acceptors include epoxies, sodium stearate, and magnesium oxalate
- inorganic acceptors include magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphite, zinc oxide, barium carbonate,
- the relative amounts of the crosslinking agent and fluorinated onium salt are present in the composition in such amounts as to provide the desired cure and/or mold release of the composition when mixed with acid acceptor
- Representative proportions of components of the curing system are as follows Acid acceptor 0.5 to 40 phr
- Onium salt 0.2 to 5 mmhr Crosslinker . 0.3 to 10 mmhr All amounts are given in parts per 100 parts polymer (abbreviated “phr”) or in millimoles per hundred grams polymer (abbreviated “mmhr”) These proportions are general ranges. The particular amount for each particular cure time and temperature will be apparent to one of ordinary skill in the art.
- the desired amount of acid acceptor, fluorinated onium salt, crosslinking agent, diorgano sulfur oxide compounds (if any), and other conventional adjuvants or ingredients are added to the unvulcanized polymer (i.e. gum stock) and intimately admixed therewith or compounded by employing any of the usual rubber mixing devices such as Banbury mixers, roll mills, or any other convenient mixing device.
- the temperature of the composition during mixing should not rise above about 120°C. During mixing it is necessary to distribute the components and adjuvants uniformly throughout the curable polymer.
- the curing process typically comprises molding the resulting composition under pressure at a temperature ranging from about 95°C to about 230°C, followed by curing.
- the composition of this invention is particularly useful for injection molding.
- the molded product is then usually post cured (e.g., oven cured) at a temperature between about 150°C and about 315°C, usually at about 232°C, for a period of from about 2 hours to 50 hours or more depending on the cross-sectional thickness of the sample.
- Structural characterization data were obtained by NMR, IR spectroscopic techniques.
- the precursor fluoroalkyl phosphines used for the preparation of cure accelerators according to the invention were prepared via free radical hydrophosphorylation reaction between diisobutylphosphine (DIBP) and a fluoroalkyl allyl ether or an allyl fluorosulfonamide
- DIBP diisobutylphosphine
- Such hydrophosphorylation reactions are well-known in the art The teachings of Rahut, M. M et al J. Org. Chem., 1961, 26, 5138; Pellon, j, J. Am Chem .Soc, 1961, 83, 1915, Buckler, S.A , et al, J. Am Chem .Soc, 1961, 83, 168; Langhans, K.P , et al Z.
- Cure and rheological properties of curable compositions and physical properties of cured sheets were evaluated using the following test methods Cure Rheology Tests were run on uncured, compounded admixtures using a Monsanto Moving Die Rheometer (MDR) Model 2000E at 177°C on an 8 0 g quantity of the admixture in accordance with ASTM D 5289-93a for a rotorless rheometer, no preheat, an oscillator frequency of 100 cpm and a 0.5° arc Minimum torque (M L ), maximum torque (M H ), and delta torque ( ⁇ T), the difference between M H and M L , were reported.
- MDR Monsanto Moving Die Rheometer
- ts2 the time to a 2 unit rise in torque from M L
- t'50 the time to increase torque above ML by 50% of delta torque
- t'90 the time to increase torque above M by 90% of delta torque
- a l " (25.4 mm) gage section was used to follow the cross head displacement. All tests were run at a constant crosshead displacement rate of 20"/minute (508 mm/min.) in triplicate. The values reported were averages of the three tests. Stress at 100% elongation, elongation at break, and tensile strength at break were reported in units of mega Pascals (MPa), %, and MPa, respectively.
- O-rings was a 4 cavity mold with O-ring internal diameter of 48 mm, O-ring cross- section of 2.90 mm, a runner length of 13 mm, sprue base diameter of 5.2 mm, sprue length of 29 mm, and each cavity had a vacuum canal.
- the mold steel was STAVAX ESR with a surface finish EDM.
- the mold was conditioned before each experiment (change of formulation) by blasting the mold surface with 50-150 micron glass beads under 0.2 MPa pressure for 10 minutes. The mold was then conditioned for 30 minutes in a water-based caustic solution at 80°C and then ultrasonically cleaned in the solution for 10 minutes. After cleaning, the mold was rinsed with deionized water, dried and stored overnight before use Multiple molding cycles were made of each formulation
- the steady state O-ring injection molding conditions were 1 0°C mold temperature, 95°C injection barrel temperature, 60°C screw barrel temperature, injection speed 60% of maximum, after-injection pressure of 5 5 MPa for 2 seconds, screw RPM 35% of maximum, backpressure of 0 5 MPa, plastication delay of 2 seconds after end holding time and a vacuum time of 2 5 seconds
- the holding time and heating time were both dependent upon vulcanization speed and were adjusted to obtain cured O-rings
- the shot size was adjusted to give similar flash to the parts molded
- Precursor fluoroalkyl phosphines or amides used in the preparation of the fluorinated onium cure accelerators of the invention were prepared as described below.
- Phosphine A 3-(l, l-dihydroperfluorooctyloxy)propyl diisobutylphosphine
- DIBP DIBP
- Cytec Industries, Inc. available from Cytec Industries, Inc.
- the flask assembly was placed on an adjustable lab jack so that either external heating or cooling of the reaction flask could be done. Additional toluene was added to dilute the DIBP solution to about 50% solids. The reaction flask was purged with nitrogen for fifteen minutes and a positive stream of nitrogen was maintained through the reaction flask to minimize the oxidation of the DIBP.
- the toluene solution of DIBP was warmed to about 80°C and the allyl ether solution in the second flask was added to the warm DIBP at about 2.5 mL/min. via a syringe pump. After about 20 min., a noticeable exotherm was detected and the rate of allyl ether addition and external heating was adjusted so that a temperature of 80 to 95°C could be maintained. After complete addition of the allyl ether solution, the reaction mixture was heated to 85°C for an additional 2 hrs to ensure complete consumption of the DIBP had occurred.
- Phosphine B 3-(l,l-dihydroperfluoropropoxy) propyl diisobutylphosphine (Phosphine)
- the 3-(l,l-dihydroperfluoropropoxy) propyl diisobutylphosphine was then prepared in a manner similar to the preparation described for Phosphine A except that 3-( 1 , 1 -dihydropentafluoropropyl) allyl ether was used in the hydrophosphorylation reaction.
- Phosphine C Bis(3-(l,l-dihydroperfluoropropoxy)propyl) isobutyl phosphine
- Phosphine D N-ethyl, N-(3-diisobutyl phosphino)propyl perfluoro octane sulfonamide
- Phosphine D was prepared in a manner similar to Phosphine A except N-ethyl, N-allyl perfluorooctane sulfonamide, prepared according to Example 7 of U.S. Pat. No. 3,442,664 (Heine), was used.
- the starting allyl sulfonamide was not completely consumed by the DIBP after 60 hrs at 100 °C.
- a 31 P NMR spectrum of the reaction mixture after 60 hrs of reaction time showed that approximately 35% of the desired phosphine formed.
- the flask was charged with 38 g (0.26 mol) of DBP.
- the reaction mixture was heated at this temperature for an additional 60 hrs. The progress of the reaction was monitored by gas chromatography and 31 P NMR spectroscopy. After this time period, the toluene solvent and unreacted DIBP were removed by simple distillation under reduced pressure (40 to 80°C @ 1 mmHg). The remaining mixture of the desired product and unreacted transferred to a 200 mL, one neck, round bottomed flask.
- the allyl sulfonamide starting material was removed by Kugelrohr distillation at 140 to 150°C at 1 mm
- Example 1 a fluorinated phosphonium cure accelerator of the present invention was prepared in a 200 ml airless flask equipped with a nitrogen purge inlet and a magnetic stir bar by charging 50 g (0.085 mol) of Phosphine A
- fluorinated phosphonium cure accelerators of the invention were made in a manner similar to Example 1 except Phosphine B was used in Example 2 instead of Phosphine A, Phosphine C was used in Example 3, and Phosphine D was used in Example 4.
- 2-((3-diisobutyl benzyl phosphonium chloride)propyl)phenyl perfluorooctane sulfonate was made by first preparing 3-(2-hydroxyl phenyl)propyl diisobutyl phosphine in a manner similar to Phosphine A except using 2-allyl phenol and DIBP.
- a 3 -neck reaction vessel equipped with condenser, mechanical stirrer and an addition funnel was then charged with 3.6 g (0.09 mol) of NaH, 60% dispersion in mineral oil, and 350 mL of dry THF.
- the resulting mixture was then heated to reflux (about 45°C) for 16 hrs.
- the reaction was followed by l9 F NMR spectroscopy and was considered complete when the sulfonyl fluoride signal at +40 ppm downfield from CFC1 3 was no longer detected in the NMR spectrum.
- the reaction mixture was worked up by extraction of the product mixture with water and methylene chloride. The organic layers were combined and dried with MgSO 4 and the solvent was removed under reduced pressure. The product was isolated as a viscous, light brown oil, 61.6 g (88% yield). Characterization by 1H, 3I P, l9 F NMR spectroscopy confirmed the proper structure of the product.
- the phosphonium product was isolated by removal of the solvent by rotoevaporation followed by further drying under vacuum at room temperature.
- Example 7 a curable composition of the invention was prepared by mixing the following ingredients together on a conventional two-roll mill using standard methods: 100 g of a fluorine-containing copolymer of vinylidene fluoride (60 wt%) and hexafluoropropylene (40 wt%), available from 3M Co. as FluorelTM
- Fluoroelastomer FC-2145 2.1 g (6.1 mmol) of bisphenol- AF and a methanol solution (about 50% solids) of 0.92 g (1.29 mmhr) of the fluorinated onium cure accelerator prepared above as Example 1.
- 6 g of Ca(OH) 2 , 3g of MgO and 30 g of carbon black were added to the composition being milled.
- the cure properties of the resulting curable composition were analyzed using a Monsanto Moving Die Rheometer at 177°C for 12 minutes. The results are reported in Table 1.
- a press-cured sheet was prepared by pressing a quantity of the curable composition at about 6.9 MPa at 177°C for 10 minutes. The resulting press-cured sheet was evaluated for physical properties. A sample of the press-cured sheet was further treated or cured for 16 hours at 232°C, resulting in a post-cured sheet which was also evaluated for physical properties. The press-cured and post-cured sheet test results are reported in Tables 2 and 3.
- Examples 8-1 curable compositions of the invention were prepared and evaluated in a manner similar to Example 7 except the fluorinated onium cure accelerator used was varied as follows: Example 8 used the compound prepared above as Example 2, Example 9 was prepared using the compound prepared above as Example 3, Example 10 was prepared using the compound prepared above as
- Example 4 was prepared using the compound prepared above as Example 5. Data are reported in Tables 1-4.
- Example 12 The curable fluoroelastomer composition of Example 12 was prepared and evaluated in a manner similar to Example 7 except the fluorinated onium cure accelerator used was varied as follows: the phosphonium compound described in Example 6 was used and 0.662 phr (1 mmhr) of onium was used instead of 1.29 mmhr. Data are reported in Tables 1-5.
- Example Cl a curable composition was prepared and evaluated as in Example 7 except the onium cure accelerator used was benzyltriphenyl phosphonium chloride, a commonly used cure accelerator commercially available from Aldrich Chemical Company, Inc.
- a curable composition was prepared and evaluated as in Example 7 except the onium cure accelerator used, N-3 -(diisobutyl benzyl phosphonium chloride) propyl perfluorooctanoic acid amide, was prepared in a one neck, airless flask, equipped with a magnetic stir bar, a nitrogen inlet adapter and a rubber septum into which was charged 28.5 g (0.067 mol) of methyl perfluorooctanoate, available from PCR Corp.
- the onium cure accelerator used N-3 -(diisobutyl benzyl phosphonium chloride) propyl perfluorooctanoic acid amide
- reaction mixture was warmed to about 45°C, diluted to about 50% solids with methanol and then 7.9 g (0.063 mol) of benzyl chloride was added and the reaction was continued for 12 hrs.
- a 31 P NMR spectrum of the reaction mixture consisted of only a singlet at +30 ppm suggesting that complete consumption of the phosphine had occurred.
- the product a highly viscous, light brown oil, was isolated by solvent removal and drying the product under vacuum. The product was characterized by P, 1H and 19 F NMR spectroscopy.
- Comparative Example C3 a curable composition was prepared and evaluated as in Example 7 except the onium cure accelerator used was prepared in a manner similar to the onium cure accelerator in Comparative Example C2 except methyl perfluoro butoxy ethoxy ethanoate was used instead of methyl perfluorooctanoate.
- Compression set data were obtained using ASTM method D-395-89. O-rings were press cured for 12 min. at 177°C and post cured for 16 hrs at 232°C. O-rings were compressed 25% for 70 hrs at 200°C. Data (shown in Table 4) are reported as percent of the compression remaining after the tests.
- Example 13 a curable composition of the invention was made in a manner similar to Example 7 except that the fluorine-containing copolymer used was prepared as described by Example 3 of U.S. Pat. No. 5,285,002 (Grootaert).
- Comparative Example C4 a curable composition was made in a manner similar to Comparative Example C 1 except that the fluorine-containing copolymer used was prepared as described by Example 3 of U.S. Pat. No. 5,285,002
- Table 5 show an improved mold release rating when using a fluorinated onium cure accelerator of the invention compared to a currently used commercial onium cure accelerator.
- fluorinated onium cure accelerators of the invention show a combination of rapid cure rates, no loss in physical properties, and improved injection molding release properties and generally improved compression set properties relative to the Comparative Examples evaluated.
- Example 14 a curable composition of the invention was made and evaluated as in Example 7 except 100 g of a fluorine-containing terpolymer was used instead of FluorelTM fluoroelastomer FC-2145.
- the specific terpolymer used was made as described in Example 5 of U.S. Pat. No. 5,285,002 (Grootaert).
- 0.42 g (1.25 mmhr) of bisphenol- AF was reacted with the fluorinated onium cure accelerator by reacting the fluorinated phosphonium chloride (prepared as Example 1) with the sodium salt of bisphenol AF (prepared as described in Example 22 of U.S. Pat. No.
- Comparative Example C5 a curable composition was made and evaluated in a manner similar to Example 1 except the onium cure accelerator used was tributyl methoxy propyl phosphonium chloride, prepared as described in Example 16 of U.S. Pat. No. 4,912,171 (Grootaert et al).
- Comparative Example C6 a curable composition was made and evaluated in a manner similar to Example 14 except the onium cure accelerator used was the fluoroalkyl amide onium described in comparative example C2.
- Comparative Example C7 a curable composition was made and evaluated in a manner similar to Example 14 except the onium cure accelerator used was the fluoroalkyl amide onium described in comparative example C3
- Compression set data were obtained using ASTM method D-395-89. O-rings were press cured for 12 min. at 177°C and post cured for 16 hrs at 232°C. O-rings were compressed 25% for 70 hrs at 200°C. Data (shown in Table 10) are reported as percent of the compression remaining after the tests.
- Table 10 show the curable compositions of this invention provide cured articles with improved compression set properties.
- the mold release performance of compositions prepared according to Examples 14-18 and C5-C7 was evaluated as well. The results are reported in Table 11.
- Table 11 show an improved mold release rating when using a fluorinated onium cure accelerator of the invention compared to other onium cure accelerators.
- fluorinated onium cure accelerators of the invention show a combination of rapid cure rates, no loss in physical properties, and improved injection molding release properties and generally improved compression set properties relative to the Comparative Examples evaluated.
Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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JP52364697A JP3723221B2 (en) | 1995-12-21 | 1996-11-26 | Fluorinated onium salts, fluorinated onium-containing curable composition, and curing method using fluorinated onium |
DE69633135T DE69633135T2 (en) | 1995-12-21 | 1996-11-26 | FLUORINATED ONIUM SALES, HARDENABLE COMPOSITIONS CONTAINING ITSELES AND CURING PROCESSES USING THEM |
AU10617/97A AU1061797A (en) | 1995-12-21 | 1996-11-26 | Fluorinated onium salts, curable compositions containing same, and method of curing using same |
CA002238941A CA2238941C (en) | 1995-12-21 | 1996-11-26 | Fluorinated onium salts, curable compositions containing same, and method of curing using same |
EP96941490A EP0868477B1 (en) | 1995-12-21 | 1996-11-26 | Fluorinated onium salts, curable compositions containing same, and method of curing using same |
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US08/576,097 | 1995-12-21 | ||
US08/576,097 US5591804A (en) | 1995-12-21 | 1995-12-21 | Fluorinated onium salts, curable compositions containing same, and method of curing using same |
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EP (1) | EP0868477B1 (en) |
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US6096428A (en) * | 1998-04-09 | 2000-08-01 | 3M Innovative Properties Company | Multi-layer compositions comprising a fluoropolymer |
JP5079187B2 (en) | 1998-08-21 | 2012-11-21 | デュポン パフォーマンス エラストマーズ エルエルシー | Fluoroelastomer composition having good processability and low temperature properties |
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EP1194462A1 (en) | 1999-07-02 | 2002-04-10 | Dyneon LLC | Fluoroelastomer compositions and articles made therefrom |
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US6767948B1 (en) | 1999-12-22 | 2004-07-27 | 3M Innovative Properties Company | Polyolefin polymer and catalyst blend for bonding fluoropolymers |
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US6593416B2 (en) | 2000-02-01 | 2003-07-15 | 3M Innovative Properties Company | Fluoropolymers |
IT1318488B1 (en) * | 2000-04-21 | 2003-08-25 | Ausimont Spa | FLUOROVINYLETERS AND POLYMERS THAT CAN BE OBTAINED. |
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- 1996-11-26 WO PCT/US1996/018936 patent/WO1997023556A1/en active IP Right Grant
- 1996-11-26 DE DE69633135T patent/DE69633135T2/en not_active Expired - Fee Related
- 1996-11-26 EP EP96941490A patent/EP0868477B1/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
AU1061797A (en) | 1997-07-17 |
JP2000502389A (en) | 2000-02-29 |
EP0868477B1 (en) | 2004-08-11 |
DE69633135D1 (en) | 2004-09-16 |
CA2238941A1 (en) | 1997-07-03 |
EP0868477A1 (en) | 1998-10-07 |
US5591804A (en) | 1997-01-07 |
CA2238941C (en) | 2006-10-03 |
JP3723221B2 (en) | 2005-12-07 |
DE69633135T2 (en) | 2005-09-08 |
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