Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/62—Halogen-containing esters
  • C07C69/63—Halogen-containing esters of saturated acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/36—Oxalic acid esters
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Definitions

• Useful oxalate blocked compounds used as crosslinking agents in accordance with the present invention have the formula:
• A is a difunctional aliphatic, cycloaliphatic, or aromatic radical of 1 to 13 carbon atoms, or a thio, oxy, carbonyl, sulfonyl, or sulfonyl radical, A is optionally substituted with at least one chlorine or fluorine atom, x is 0 or 1 ; R is an aryl group or an alkyl group; and n and n' each is independently selected as 0 or 1 with the proviso that when either n or n' is 0, its corresponding portion of the Z moiety is terminated by hydrogen (that is, its corresponding terminal portion is -Z-OH) or is terminated by a metal or nonmetal cation.
• A is a difunctional aliphatic radical or a difunctional perfluoroaliphatic radical.
• x is a number between 1 and 4 inclusive and where R' is hydrogen, a halogen atom, or is an acyl, aryl, polyaryl (fused to or separated from the aromatic ring) or alkyl radical substituent (or any combination thereof), the latter three of which may be fluorinated but are preferably non-fluorinated and may be straight-chained, branched, cyclic.
• the -R' group may optionally contain one or more catenary heteroatoms, that is, a non-carbon atom such as nitrogen or oxygen. It will be understood from the above formula that the constituent -R group can be attached in any position in the ring relative to the bond attaching it to the oxalate group depicted in Formula V.
• Useful alkyl groups include alkyl groups having from 2 to
• the alkyl groups may be cyclic or acyclic, linear or branched, fluorinated or non-fluorinated, may be un-substituted or may be substituted with an aryl or one or more functional groups, and may contain one or more catenary heteroatoms.
• Preferred alkyl and substituted alkyl groups include ethyl, propyl, and isopropyl. It will be understood that the oxalate-blocked compounds may be oligomerized oxalates. Oligomeric oxalates, so formed, are also useful in the practice of the invention and are considered within the scope thereof.
• compositions of the invention may contain one or more oxalate blocked compounds or may contain a mixture of one or more oxalate-blocked compounds and one or more other crosslinking agents.
• One type of conventional crosslinking agent for a fluorocarbon elastomer gum which may be used in combination with an oxalate-blocked crosslinking agent of the invention is a polyhydroxy compound.
• the polyhydroxy compound may be used in its free or non-salt form or as the anionic portion of the chosen organo-onium accelerator.
• the crosslinking agent may be any of those polyhydroxy compounds known in the art to function as a crosslinking agent or co-curative for fluoropolymers, such as those polyhydroxy compounds disclosed in U.S. Pat. Nos. 3,876,654 (Pattison) and 4,233,421
• Fillers can be mixed with the fluoropolymer gum to improve molding characteristics and other properties. When a filler is employed, it can be added to the vulcanization recipe in amounts of up to about 100 parts per hundred parts by weight of gum, preferably between about 15 to 50 parts per hundred parts by weight of the gum. Examples of fillers which may be used are reinforcing thermal or furnace grade carbon blacks or non-black pigments of relatively low reinforcement characteristics such as clays and barytes.
• the relative amounts of the crosslinking agent or agents that is, the chosen total amount of aryl, alkyl, or allyl oxalate along with conventional crosslinking agents, if any) and 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
• Pressing of the compounded mixture is usually conducted at a temperature between about 95 °C and about 230 °C, preferably between about 150 °C and about 205 °C, for a period of from 1 minute to 15 hours, typically from 5 minutes to 30 minutes.
• a pressure of between about 700 kPa and about 20,600 kPa is usually imposed on the compounded mixture in the mold.
• the molds first may be coated with a release agent and prebaked.
• Cure Rheology Tests were run on uncured, compounded admixture using a Monsanto Moving Die Rheometer (MDR) Model 2000 in accordance with ASTM D 5289- 93a at 150 °C, 177 °C, and 200 °C, no preheat, for the indicated time (60, 12, or 6 minutes), and a 0.5° arc.
• Mf Monsanto Moving Die Rheometer
• M Maximum torque
• Elongation were determined using ASTM D 412-92 ⁇ on samples cut from the press-cure or post-cure sheet with ASTM Die D. Units reported in Mega Pascals (MPa).
• a glass round bottom flask was assembled with a stirring bar, a refluxing condenser, and a thermometer.
• the flask was charged with 17 grams of 4,4'- hexafluoroisopropylidene-diphenol (bisphenol AF), 100 mL of methyl ene chloride, and 14 mL of triethylamine.
• bisphenol AF 4,4'- hexafluoroisopropylidene-diphenol
• the reaction solution was stirred at room temperature until the bisphenol-AF was dissolved.
• Fifteen grams of ethyl oxaly chloride was slowly added to the reaction mixture under stirring. Some white precipitate appeared in the solution, which was believed to be hydrochloric ammonia salt.
• the solution was stirred for 2 - 3 hours.
• the white solid was filtered and then washed with a small amount of methyl ene chloride.
• the filterate and the washed methylene chloride were combined and washed with cold water (4 x 150 mL) and 150 mL 0.3 N HCl and the washed filtrate was dried over MgSO4 overnight.
• the MgSO4 salt was filtered and washed with about 30 mL of methylene chloride.
• the solvent was removed on a rotary evaporator and the resulting white solid was further dried under vacuum to give 24.9 grams (92 percent yield) of the expected product.
• iHNMR 400 MHz, CDCI3
• 7.45 (d, J 36 Hz, 4 H)
• 7.26 (d, J 36 Hz, 4 H)
• Cl-C-C-O-Z-O-C-C-Cl Z Bisphenol AF Radical Bisphenol AF (50 grams, 148.8 mmole) and dichloroethane (625 grams) were charged to a flask fitted with a fractionation column and a still head attached to a NaOH bubbler. Nitrogen was bubbled through the reaction vessel. To this was added oxalyl chloride (145 grams, 1.141 mole). The mixture was heated to reflux ( ⁇ 90 °C) and all components were dissolved. The reaction was run at this temperature for 6 hours with the
• a glass round bottom flask was assembled with a stirring bar, a refluxing condenser and a thermometer.
• Bisphenol AF bisoxalyl chloride (10.0 grams, 19.3 mmol)
• 80 mL of methylene chloride 80 mL
• the solution was cooled to -35 °C with a dry ice/isopropanol/water bath.
• To the solution was slowly added dry n-propanol (2.4 grams, 40 mmol) in 25 mL CH2CI2. After the completion of the addition, the reaction was further carried out for 1 hour at -35 °C and for 2 hours at room temperature.
• Bisphenol AF bisoxalyl chloride (10.2 grams, 19.72 mmole) was dissolved in dichloroethane (23 grams).
• n-Octanol (5.14 grams, 39.53 mmole) was mixed with dichloroethane (40 grams).
• the alcohol solution was added slowly to the dichloroethane with stirring and cooling. The temperature was maintained at 10 - 15 °C for 2 hours. The reaction was allowed to proceed at room temperature overnight.
• the product was obtained by rotary evaporation and further under vacuum to give 13.8 grams (100 percent yield) of a light straw colored viscous liquid.
• Gum A was a copolymer which, except as otherwise indicated, has a Mooney Viscosity of 38 and nominal weight percents of interpolymerized units derived from 60 weight percent vinylidene fluoride and 40 weight percent hexafluoropropene.
• Gum B was a terpolymer having nominal weight percents of interpolymerized units derived from 44.5 weight percent vinylidene fluoride, 31.2 weight percent hexafluoropropene, and 24.3 weight percent tetrafluoroethylene and had a nominal Mooney Viscosity of 75.
• Some additives, such as curatives for example, are listed in quantities of millimoles per hundred parts of gum (mmhr). Other additives are listed in grams. Percentages are in weight percent unless otherwise specified.
• Comparative Example 1 shows the kinetics at 150 °C of a composition using bisphenol AF as the crosslinking agent. The cure is essentially complete after 3.2 minutes
• Examples 15 and 16 and Comparative Examples 2 and 3 show that similar results to those described above can be obtained using a different catalyst and different fluoropolymer gum.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=23646160

Family Applications (1)

Country Status (7)

Cited By (2)

Families Citing this family (2)

Citations (5)

Family Cites Families (13)

• 1999
  • 1999-10-08 US US09/415,552 patent/US6359166B1/en not_active Expired - Lifetime
• 2000
  • 2000-02-01 CA CA002384809A patent/CA2384809A1/en not_active Abandoned
  • 2000-02-01 DE DE60016453T patent/DE60016453T2/de not_active Expired - Lifetime
  • 2000-02-01 EP EP04027111A patent/EP1512674B1/en not_active Expired - Lifetime
  • 2000-02-01 AU AU27486/00A patent/AU2748600A/en not_active Abandoned
  • 2000-02-01 JP JP2001530408A patent/JP4615804B2/ja not_active Expired - Fee Related
  • 2000-02-01 WO PCT/US2000/002454 patent/WO2001027195A1/en not_active Ceased
  • 2000-02-01 DE DE60028426T patent/DE60028426T2/de not_active Expired - Lifetime
  • 2000-02-01 EP EP00905879A patent/EP1235875B1/en not_active Expired - Lifetime
• 2001
  • 2001-12-28 US US10/033,483 patent/US6566455B2/en not_active Expired - Lifetime
  • 2001-12-28 US US10/033,485 patent/US6562911B2/en not_active Expired - Lifetime

Patent Citations (5)

Also Published As

Similar Documents

Legal Events