Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
  • C08G64/0208—Aliphatic polycarbonates saturated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates

Definitions

• This invention is directed to processes for making a poly(trimethylene carbonate) glycol by the polymerization of a trimethylene carbonate employing one or more acidic ion exchange resin catalysts in the presence of a solvent.
• the products formed are substantially free of the catalysts.
• Poly(thmethylene carbonate) diols find use in a variety of materials. These diols have been prepared by the polymerization of trimethylene carbonate (TMC, 1 ,3-dioxan-2-one), generally using catalysts containing organometallic compounds such as zinc, tin and alkali metal compounds, as described in Hyun, H.; et. al. J. Polym. Sci. Part A: Polym. Chem.: Vol.44 (2006). Also, it has been reported that TMC can be polymerized via various alcohol and HCI initiator systems, as described in Shibasaki, Y.; et al., Macromol. Rapid Commun. 20, 532 (1999) and Macromolecules 2000, 33, 4316. These methods necessitate the removal of the catalyst used, especially when the resulting diols are to be used in biomedical applications.
• the initiating agent becomes incorporated into the polymer ends.
• One aspect of the present invention is a process for producing poly(trimethylene carbonate) glycols, comprising contacting an unsubstituted or substituted thmethylene carbonate with an acidic ion exchange resin as a catalyst, in the presence of one or more solvents at a temperature within the range from the freezing point of the solvent to about 30 degrees Celsius, to form a reaction mixture comprising a poly(trimethylene carbonate) diol.
• the present invention relates to a process to make an unsubstituted or R-substituted poly(thmethylene carbonate) glycol (PTMC) from an unsubstituted or R-substituted thmethylene carbonate (TMC, 1 ,3-dioxan-2-one) via polymerization in the presence of a solvent utilizing an acidic ion exchange resin catalyst and at temperatures between the freezing point of the solvent used to room temperature (generally about 20 to 30 degrees Celsius, typically around 25 degrees Celsius) .
• PTMC poly(thmethylene carbonate) glycol
• TMC unsubstituted or R-substituted thmethylene carbonate
• TMC unsubstituted or R-substituted thmethylene carbonate
• each R substituent is independently H, C1-C20 alkyl, particularly Ci-C 6 alkyl; C 3 -C 2 O cyclic alkyl, particularly C 3 -C 6 cyclic alkyl; C 6 -C 2S aryl, particularly C 6 -Cn aryl; C 6 -C 20 alkaryl, particularly C 6 -Cn alkaryl; C 6 -C 2 O arylalkyl, particularly C 6 -Cn arylalkyl; and wherein each R substituent may form a cyclic structural group with adjacent R substituents; and each n is independently 2 to 100, and particularly 2 to 50.
• each R substituent may form a cyclic structure with adjacent R substituents
• the resulting cyclic structural group can be selected from C 3 -C 8 ; for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane.
• the trimethylene carbonate can be derived from 1 ,3- propanediol.
• TMC can be prepared by any of the various chemical or biochemical methods known to those skilled in the art. Chemical methods for the preparation of TMC include, but are not limited to, a) reacting 1 ,3-propanediol with diethylcarbonate in the presence of zinc powder, zinc oxide, tin powder, tin halide or an organotin compound at elevated temperature, b) reacting 1 ,3-propanediol and phosgene or bis-chloroformates to produce a polycarbonate intermediate that is subsequently depolymerized using heat and, optionally, a catalyst, c) depolymehzing poly(trimethylene carbonate) in a wiped film evaporator under vacuum, d) reacting 1 ,3-propanediol and urea in the presence of metal oxides, e) dropwise addition of triethylamine to a solution
• Biochemical methods for the preparation of TMC include, but are not limited to, a) lipase catalyzed condensation of diethylcarbonate or dimethylcarbonate with 1 ,3-propanediol in an organic solvent, and b) lipase-catalyzed depolymehzation of poly(trimethylene carbonate) to produce TMC.
• the 1 ,3-propanediol and/or TMC can be obtained biochemically from a renewable source ("biologically-derived" 1 ,3-propanediol).
• the 1 ,3-propanediol used as the reactant or as a component of the reactant has a purity of greater than about 99%, and more preferably greater than about 99.9%, by weight as determined by gas chromatographic analysis.
• the 1 ,3-propanediol preferably has the following characteristics:
• a concentration of total organic impurities (organic compounds other than 1 ,3-propanediol) of less than about 400 ppm, more preferably less than about 300 ppm, and still more preferably less than about 150 ppm, as measured by gas chromatography.
• the PTMCG can be isolated using known methods.
• the processes disclosed herein employ an acidic ion exchange resin as a catalyst.
• Ion exchange resins suitable for use in the processes are available from a number of sources.
• the catalysts are generally added to the reactants to form a reaction mixture. As shown in the examples below, conveniently small amounts of these catalysts afford high conversion within about 25 hours.
• acidic ion exchange resin catalysts suitable for use in the processes herein include sulfonated tetrafluoroethylene copolymers, for example, Nafion® SAC-13 or NAFION® NR50 (tetrafluoroethylene/perfluoro(4-methyl-3,6-dioxa-7-octene-1 -sulfonic acid) copolymer, an ionomer available from E.I.
• sulfonated tetrafluoroethylene copolymers for example, Nafion® SAC-13 or NAFION® NR50 (tetrafluoroethylene/perfluoro(4-methyl-3,6-dioxa-7-octene-1 -sulfonic acid) copolymer, an ionomer available from E.I.
• sulfonated tetrafluoroethylene copolymers for example NAFION® NR50 (tetrafluoroethylene/perfluoro(4-methyl-3,6- dioxa-7-octene-1 -sulfonic acid) copolymer, an ionomer available from E.I. DuPont de Nemours and Company, Wilmington, DE, and DOWEX® 50WX8-200 ion-exchange resin available from Acros Organics N.V., Fair Lawn, NJ.
• NAFION® NR50 tetrafluoroethylene/perfluoro(4-methyl-3,6- dioxa-7-octene-1 -sulfonic acid copolymer
• DOWEX® 50WX8-200 ion-exchange resin available from Acros Organics N.V., Fair Lawn, NJ.
• the process uses one or more solvents.
• any solvent can be used, as long as it is substantially non-reactive (i.e., does not react with the ingredients to form moieties that interfere with the reaction) with the reactants and/or catalyst.
• solvents useful in the process disclosed herein include but are not limited to methylene chloride, toluene and dioxane. As shown in the examples below, lower amounts of solvent generally provide for higher conversion rates.
• the processes disclosed herein are carried out at ambient temperature, generally between about 20 and 30 degrees Celsius, but can be carried out as low as the freezing points of the solvents used.
• the reactants Once the reactants are added together, they may be mixed by any convenient method.
• the process can be done in batch, semi-batch or continuous mode, and generally are carried out in an inert atmosphere (i.e., under nitrogen).
• the reaction is allowed to continue for the desired time.
• at least 6 percent of the TMC polymerizes to give the desired poly(trimethylene carbonate) glycol after about 6 hours, with greater than about 75 percent conversion achieved within about 25 hours.
• 100 percent conversion can be achieved by the selection of solvent and catalyst, and amounts thereof. Selection of solvent and catalyst and amounts thereof is within the purview of one skilled in the art.
• the desired degree of polymerization, n can be achieved by selection of solvent and catalyst, and amounts thereof.
• n is 2 to 100, and more specifically 2 to 50 in the present invention.
• the resulting poly(trimethylene carbonate) glycol can be separated from the unreacted starting materials and catalyst by any convenient means, such as filtration, including filtration after concentration.
• the catalyst used can also be recycled a number of times (i.e., at least 12 cycles for NAFION® NR50 copolymer) and still provide for approximately 100 percent conversion of the reactants to the desired product.
• the process disclosed herein allows for the degree of polymerization to be selected based on the solvent and/or catalyst chosen, and the amount of those materials used. This is advantageous as the materials resulting from the process can vary in properties including viscosity.
• the diols can find wide use in products including biomaterials, engineered polymers, personal care materials, coatings, lubricants and polycarbonate/polyurethanes (TPUs).
• This example demonstrates the production of poly(trimethylene carbonate) glycol using Nafion® NR50 copolymer as catalyst.
• TMC (10.00 g, 0.098 mol) and Nafion® NR50 copolymer (2.5 g) were placed in three round bottomed flasks equipped with stirrer and under nitrogen.
• the reaction mixture was stirred at room temperature. Aliquots were withdrawn after 17 hours and 25 hours, concentrated at reduced pressure and analyzed via Proton NMR. The following table tabulates the results:
• This example demonstrates the production of poly(trimethylene carbonate) glycol using Dowex® 50x8-200 (Dowex ®50W-Hydrogen) ion-exchange resin as catalyst.
• TMC (10.00 g, 0.098 mol) and Dowex® 50x8-200 ion-exchange resin (Dowex® 50W-Hydrogen) (2.5 g) were placed in three round bottomed flasks equipped with stirrer and under nitrogen. To the first flask 25 ml_ of methylene chloride was added, to the second flask 50 ml_ of methylene chloride was added and to the third flask 100 ml_ of methylene chloride. The reaction mixture was stirred at room temperature. Aliquots were withdrawn after 17 hours, concentrated at reduced pressure and analyzed via Proton NMR. The following table tabulates the results:
• TMC (10.00 g, 0.098 mol) and toluene (25 ml_) were placed in three round bottomed flasks equipped with stirrer and under nitrogen.
• To the first flask 0.5 g of Nafion® copolymer was added, to the second flask 1.0 g of Nafion® copolymer was added and to the third flask 2.00 g of Nafion® copolymer was added.
• the reaction mixture was stirred at room temperature. Aliquots were withdrawn after ⁇ 4 hours and -20 hours, concentrated at reduced pressure and analyzed via Proton NMR. The following table tabulates the results:
• a stock solution containing trimethylene chloride (136.Og) and diluted to 400 ml_ with methylene chloride was prepared, this representing a 3.33M solution.
• the above stock solution (Example 20, 30 ml_) was added, via syringe, to an oven dried 100 ml_ round bottomed flask equipped with a stirrer and under nitrogen, containing Nafion® NR50 (2.0 g).
• the reaction mixture was stirred at room temperature.
• An aliquots were withdrawn after 3.5 and 22 hrs, concentrated at reduced pressure and analyzed via NMR. After 22 hours the reaction mixture was filtered and the recovered Nafion® catalyst was washed with methylene chloride (2 x -50 ml_). The filtrate was concentrated at reduced pressure and dried under nitrogen.
• the recovered catalyst was placed in an oven dried 100 ml_ RB flask equipped with a stirrer and under nitrogen. To this material was added the above stock solution (30 ml_), via syringe. The reaction mixture was stirred at room temperature. An aliquots were withdrawn after 6 and 22 hrs., concentrated at reduced pressure and analyzed via

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• 2008
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