Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C247/00—Compounds containing azido groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
  • C07C243/02—N-nitro compounds
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
  • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/6856—Dicarboxylic acids and dihydroxy compounds

Definitions

• This invention relates generally to energetic binders, and, more specifically, to a class of nitramine-containing polymers characterized by enhanced energy, as well as favorable viscosity, glass transition 5 temperature, and resistance to hydrolysis.
• P-DEND ⁇ oly(diethylene glycol-4,7- nitrazadecanedioate) designated as P-DEND.
• P-DEND ⁇ oly(diethylene glycol-4,7- nitrazadecanedioate)
• U.S. Patent 3,808,276 discloses polyether polymer binders for propellant compositions prepared by reacting 1,6-dichloro-2,5-dinitrahexane (DCDNH) with a polyhydroxy alcohol, such as ethylene glycol. No polyester polymer binders are disclosed in this patent.
• DCDNH 1,6-dichloro-2,5-dinitrahexane
• New polymer binders exhibiting enhanced energy during use and characterized by an advantageous viscosity and glass transition temperature, as well as a resistance to hydrolysis, would be highly desirable to the propellants and explosives community.
• the present invention relates to a nitramine-containing polymer prepared by reacting a nitramine-containing diol with a nitramine-containing diacid or a nitramine-containing, dihalogen-containing compound.
• the resulting polymer is characterized by high energy as measured by a high specific impulse.
• the present invention relates to a nitramine-containing polymer characterized by an advantageous combination of a low viscosity and a low glass transition temperature, as well as resists ⁇ ce to ydrol sis; represent-. ⁇ . b th ⁇ "nllowing e*> ;*iri» structural formula:
• ⁇ . and g. have a value 0 or 1, and & have values of 1 to 3 (preferably 1 or 2), a has a value of 2 or 3, f has a value of 0 to 3 (preferably 0 and 1) , z. has a value of 1, y has a value of from .10 to 1, and z. has a value of from 0 to 0.9, with the proviso that the sum of y plus a. is equal to 1, and wherein R is a linear or branched chain alkylene or alkylene ether radical having between 2 and 12 carbon atoms and having primary or secondary carbon atoms at points of attachment of said radical in said polymer, and n has a value between 2 and 50.
• the present invention relates to a process for producing a nitramine-containing polymer which comprises the steps of reacting a nitramine-containing diol with a nitramine-containing diacid or a nitramine-containing, dihalogen-containing compound in the presence of an acid catalyst by a melt polymerization reaction to form said nitramine- containing polymer while removing by-product water during the course of said reaction.
• the present invention relates to a process for producing a nitramine- containing diol which comprises the steps of:
• the present invention relates to novel nitramine- plus nitro- and/or fluoro-containing polymers characterized by an advantageous combination of high energy, low viscosity, and low glass transition temperature made by a solution polymerization reaction of a nitramine-containing diacid chloride with a nitro- or fluoro-containing diol.
• These polymers have a weight average molecular weight of between about 1,500 and about 5,000, and are characterized by the following empirical structural formula:
• R 1 and R3 are independently selected from the following formula:
• R is independently selected from the following formula:
• anhydrous organic solvent preferably tetrahydrofuran (THF), acetonitrile, or diethylether, although other organic solvents can be employed such as pentane, hexane, heptane, methylene chloride, dichloroethane, toluene, benzene, and the
• a tertiary amine base in the presence of a tertiary amine base at a reaction temperature of between about 0°C and about 50 ⁇ C (preferably between about 20°C and about 40°C) .
• the melt polymerization process of the present invention after the reaction has begun and particularly during the later stage of the reaction, it is preferred that hydrogen chloride be removed by vacuum 10 as the reaction progresses in order to expedite formation of the desired nitramine-containing polymer product.
• Another possibility for the removal of the by-product hydrogen chloride is the addition of an acid acceptor which is non-reactive with the bischloromethyl 15 monomer in the reaction mixture.
• the polymer product be purified in a purification step, suitably by precipitation in a solvent/non-solvent mixture or by using gel permeation chromatography.
• the nitramine-containing 20 polymer is end-capped with a functional moiety to impart a desired terminal functionality to the polymer. In the absence of such end-capping, the polymer is generally chloro- or hydroxyl-terminated.
• Certain polymers described in this invention are 2. of the class described by the general ⁇ -; ⁇ pirical formula g-' * • * *----j bc o'v.
• a. and s. have a value 0 or 1
• b and fl. have values 0 of 1 to 3 (preferably 1 or 2)
• c. has a value of 2 or 3
• f has a value of 0 to 3 (preferably 0 and 1)
• x has a value of 1
• y has a value of from .10 to 1
• z. has a value of from 0 to 0.9, with the proviso that the sum of y plus z. is equal to 1
• R is a linear or branched chain alkylene or alkylene ether radical having between 2 and 12 carbon atoms and having primary or secondary carbon atoms at points of attachment of said radical in said polymer
• n has a value between 2 and 50.
• the polyether polymers are suitably prepared by reacting a nitramine-containing bischloromethyl monomer with a diol under melt polymerization reaction conditions (i.e. in the absence of a solvent).
• Table I summarizes the polymers that were prepared based on the above polymerization method.
• Monomers useful in the present invention include the following bischloromethyl derivatives: 2,5-dinitraza-l,6- dichlorohexane; 2,5,8-trinitraza-l,9-dichlorononane; 2,4,6- trinitraza-l,7-dichloroheptane, and 2,6-dinitraza-l,7- dichloroheptane and other bischloromethyl derivatives of similar structure.
• Useful nitramine-containing diols include the following: 3-nitraza-l,5-pentanediol and 5 3,6-dinitraza-l,8-octanediol.
• Useful diol monomers include a wide variety of diols, such as, for example, ethylene glycol, propylene glycol, 1,4- butanediol, 1,6-hexanediol, diethylene glycol and various other diols of similar structure. 10
• the polymers identified in Table I above as Polymer 1-8 are preferred due to their relatively low glass transition temperature which provides superior process ability into formulated products, such as propellants or explosives.
• these polymers 15 were found to have relatively low viscosity which gives superior performance during processing of the formulated propellent or explosive product.
• the polymers and co-polymers of the present invention combine the advantages cited above with high 20 calculated (by the Naval Weapons Center PEP method) impetus in propellent formulations, a desired functionality of very near two, primarily hydroxyl termination (if desired) of the polymer chains, and a molecular weight which can readily be controlled to many :.i desired values over a wide range.
• the preferred polymer mn ⁇ i ⁇ s uz' ' - r. weig is between about F90 and ab ut 10,000, more preferably between about 1,500 and about 5,000.
• These molecular weights are weight average molecular weights as measured by gel permeation chromatography 0 (GPC) using a polystyrene standard.
• the molecular weight of the polymers can be controlled by varying the stoichiometry of the diol and bischloromethyl monomers.
• the molar ratio of diol to bischloromethyl monomer ranges between about 1:0.5 and about 0.5:1.
• the polymers are prepared using an excess of the diol monomer relative to the bischloromethyl monomer, thereby providing a hydroxy-terminated polymer, preferably a molar ratio of diol to bischloromethyl monomer of between about 1:0.99 and about 1:0.6.
• the polymer may be terminated by chloride groups by the simple technique of adjusting the stoichiometric ratio of monomers such that the bischloromethyl (i.e. the bischloromethyl monomer) is present in excess relative to the diol monomer.
• other functional moieties can be used to end-cap the polymer molecules to impart a desired terminal functionality to the polymer.
• the hydroxy-terminated polymer can be reacted with an excess of diisocyanate to yield an isocyanate-terrainated polymer.
• a diacid chloride such as adipoyl chloride, phosgene, or other similar compounds can be reacted with the hydroxy-terminated polymer to give polymers terminated with acid chloride or chloroformate groups.
• the chloride end groups of the chloride-terminated polymer can be chemically modified to yield any of a variety of functional groups as terminal groups for these polymers. This flexibility in designing the end group or terminal group on the polymer molecule is important because ic allows a great renge of possibilities in terms of the curing of these materials with other components to fabricate the desired final product, namely the propellant or explosive product.
• the reaction time useful for the melt polymerization process of the present invention is not narrowly critical and can vary over a wide range. It is preferred that the reaction time be between about 2 and about 8 hours, more preferably between about 3 and about 5 hours.
• the reaction temperature is not narrowly critical and can vary over a wide range. Preferably the reaction temperature is between about 0 C C and about 120°C, more preferably between about 25°C and about 95°, and most preferably between about 45°C and about 65°C, desireably using a melt polymerization.
• the melt polymerization reaction in accordance with the present invention is preferably suitably conducted, for the most part, at subatmospheric pressure, most preferably at a pressure of between about 0.001 mm of Hg and about 600 mm of Hg.
• the subatmospheric pressure makes it possible for easy removal of the hydrogen chloride by-product from the reaction mixture, thereby driving the polycondensation reaction to completion as desired. Because of the volatility of some of the monomers employed, however, subatmospheric pressure is preferably not applied during the initial stage of the reaction.
• Alternative or additional methods can be used to remove by-product hydrogen chloride from the reaction mixture, such as bases which do not react with the bischloromethyl monomer.
• the optional polymer purification step is preferably conducted by precipitation in a mixture of a paired solvent/non-solvent.
• Suitable solven-t/ui-n-'-solvsnt pairs can be chosen £ ⁇ om tlis following solvents: methylene chloride, chloroform, tetrahydrofuran, or any other organic solvent capable of dissolving the polymers; and the following non-solvents: methanol, ethanol, water, hexane, cyclohexane, benzene or any other organic medium which is not a solvent for polymers.
• other purification methods can be employed such as gel permeation chromatography.
• the polymers produced in accordance with the process of the present invention generally have a weight average molecular weight of between about 500 and about 10,000, preferably between about 1000 and about 5000.
• the glass transition temperature of the polymer (T ) is generally less than 0°C, preferably less than -10°C, and more preferably less than -15°C.
• the viscosity of the polymer is generally less than 50,000 centipoise, preferably less than 20,000 centipoise, and more preferably less than 10,000 centipoise.
• the solution polymerization process used in the present invention is carried out under mild reaction conditions by reacting an energetic diacid chloride monomer with an energetic diol monomer which are unstable and starts decomposing under the (hot) melt polymerization condition.
• concentration of each monomer reactant in the solvent generally ranges between 0.05 and about 1 molar concentration (M.).
• the molar ratio of diacid chloride monomer relative to the diol monomer is generally between about 0.8:1.2 and about 1.2:0.8.
• the amine base acts as a catalyst for the polymerization reaction as well as an acid scavenger for HC1 released during the reaction.
• the amount of amine base employed in the process of this invention generally ranges between 0.5 to 2.5 molar equivalents per mole of diacid c'ilori ⁇ icnom ⁇ r.
• the amine base " rve,* as both a catalyst and an acid scavenger in order to facilitate completion of the polymerization reaction.
• the by-products, hydrochloride amine salt and free hydrochloride are removed by means of aqueous and brine washes.
• the polymer is either recovered from the solution by stripping off the solvent or isolated as a precipitate by decanting the solvent.
• the polymers could be purified in a purification step, suitably by precipitation in a solvent/non-solvent mixture or by using gel-permeation chromatography.
• the polymers thus prepared are either acid or a hydroxyl terminated, depending upon whether an excess of the diacid chloride or the diol is employed in the polymerization reaction.
• the terminal acid groups can be further extended or modified, typically before the aqueous work-up, as an acid chloride, with another nucleophile such as a diol, an alcohol, an amine, a thiol and a water molecule.
• the terminal hydroxyl groups could also be further extended, before the aqueous work-up, with another electrophile such as a diacid chloride, an acid chloride, an isocyanate, an diisocyanate, an acid, a diacid, an ester, a diester, and an active organic halide.
• the diol monomers suitably employed in this invention include 2-fluoro-2-nitro-l, 3-pro ⁇ ane-diol, 2,2-dinitro-l,3- ⁇ ro ⁇ ane-diol, 2,5- dinitraza-l,6-hexanediol and 2,2,5,5-tetranitro-l, 6-hexanediol.
• fluoro-containing monomers such as 2-fluoro-2-nitro-l,3-pro ⁇ ane-diol or 2,2-dinitro-l,3-propane-diol
• the resulting polymers exhibit enhanced e ergy (impetus) as compared to conventional energetic binders.
• 2,5-Dinitraza-l,6-hexanediol is one of the nitramine diols with very good energy, but unfortunately it is subject to thermal degradation using melt processing, and therefore the process of the present invention is particularly useful since thermal degradation of the monomers does not occur during processing.
• diacid chlorides include 4,7-dinitrazadecanoic-l,10-diacid chloride and 4,8- dinitrazaundecanoic-l,ll-diacid chloride which are prepared readily from their diacid precursors and thionyl chloride.
• the amine base is necessary to add to the reaction in order to achieve desirable molecular weights, 1,000 to 5,000. Without the amine base, we found in our investigation, only low molecular weight polymers, ⁇ 1,000, were obtained.
• We are also able to control the molecular weights of the polymers by appropriately adjusting the equivalents of amine base : in general, the higher equivalent of the amine base, the higher molecular weight of the polymer.
• the polymers prepared by solution polymerization in accordance with this invention are any of a variety described by the general empirical formula given above.
• the polymers are prepared by reacting at least one nitramine-containing diacid chloride monomer with at least one nitramine- and/or nitro- and/or fluoro- and/or other energetic and non- energetic-containing diol monomer in an anhydrous solvent.
• the addition of an appropriate amount, for example 0.5-2.5 equivalents, of an amine base serves as both a catalyst and an acid scavenger to complete the reaction.
• the by-products, hydrochloride amine salt and free hydrochloride are suitably removed by repeatedly aqueous and brine washes.
• the polymer is either recovered from the solution by stripping off the solvent or isolated as a precipitate by decanting the solvent. If desirable, the polymers could be purified in a purification step, suitably by precipitation in a solvent/non-solvent mixture or by using gel-permeation chromatography.
• the diol monomers are generally nitro- or fluoro-containing monomers, although, if desired, nitramine-containing diol monomers are suitably employed as the diol monomer in the p.ocess of the present invention, and the process is particularly useful in polymerizing monomers whose decomposition temperature is at (or below) the melting point of the monomer, such as 2,5-dinitraza-l,6-hexanediol, since melt polymerization methodology would not be suitable for processing such degradable monomers.
• the sequence of addition is not critical.
• the diacid chloride monomer, the diol monomer, and the amine base can be added neat or in solution either simultaneously or sequentially.
• One exception is with 2,5-dinitraza-l,6-hexanediol which is incompatible with amine base and monodehydroxylated in the presence of amine base, and amine base must be added after the additions of the diacid chloride and the diol monomers are completed.
• the concentration of the diacid chloride is generally between about 0.05 to about 1 molar, preferably between about 0.1 to about 0.8 molar, and more preferred between about 0.2 to 0.4 molar.
• the molar equivalents of the diol is generally between about 0.8 to about 1.2, preferably between about 0.9 to about 1.1, and more preferably between about 0.95 to about 1.05.
• the molar equivalents of the amine base is generally between about 0.5 to about 2.5, preferably between about 1 to about 2, and more preferrably between about 1.3 to about 1.7.
• the preferable reaction time is between about 10 min. to about 24 hrs., more preferably between about 1 to about 20 hrs., and most preferably between about 3 to about 18 hrs.
• the preferable reaction temperature is between about 0 to about 50°C, more preferably between about 10 to about 40°C, and most preferably between about 20 to about 30°C.
• Useful amine bases include aromatic amines such as pyridine and lutidine, aliphatic 3° amines such as triethyl amine, tributyl amine, and amines with similar structure.
• Useful solvents include anhydrous nonprotonic solvents, such as, for example, tetrahydrofuran (THF), acetonitrile, diethyl ether, pentane, hexane, heptane, methylene chloride, chloroform, dichloroethane, toluene, benzene, N,N-dimethylformamide and solvents with similar structure.
• THF tetrahydrofuran
• acetonitrile such as, for example, tetrahydrofuran (THF), acetonitrile, diethyl ether, pentane, hexane, heptane, methylene chloride, chloroform, dichloroethane, tol
• the polymers prepared in accordance with the solution polymerization of the present invention have a weight average molecular weight by gpc between about 1,000 to about 5,000, a glass transition temperature (Tg) between about -30 to about 10°C, in general ⁇ 0°C, and a decomposition temperature (Td) between about 200 to about 250°C.
• percent designates weight percent and the term “fraction” designates mole fraction unless otherwise specified.
• the intermediate product (A) was mixed with 900 ml of hot (50-60°C) water in a covered beaker and heated to boiling while stirring for 20 minutes. The solution was cooled, with slow stirring, to 15°C for 15 minutes, the product filtered off, washed with 100 ml of ice water and dried under vacuum at room temperature. Ethylenedinitramine, EDNA (21 g), (B) was produced in a 69.9% yield. The EDNA (21 g), 1,3,5-trioxane (21 g) and acetic acid (71 ml) were charged to a stirred 200 ml flask. Anhydrous HC1 was bubbled at 50-55° in via a dip tube for 1.5 hours.
• 1,3-Diaminopropane (8.30 g, 0.1120 mole) and 170 ml of methanol were charged to a stirred 300 ml 3-neck flask with reflux condenser and under a nitrogen cover.
• Acrylonitrile (12.5 ml) was added dropwise while keeping the temperature below 45°C.
• the reaction mixture was stirred for 30 minutes at 45°C, then heated to reflux for another 30 minutes.
• the reactor was cooled to 10°C and a solution of 70% HN0 3 (22.4 ml) and water (11.2 ml) added and the reactor cooled to 5°C for 1 hour.
• the product was filtered, washed with 40 ml of cold methanol and dried - ider vacuum at room temperature to give 22.0 g of (B), a 64% yield.
• Acetic anhydride (94 ml) was charged to a stirred 300 ml 3- neck flask under N 2 ⁇ The reactor was cooled to 10°C, 98% HN0 3 (1.7 ml) and 37% HCl (1.1 ml) were added. 19.9 g of (B) was added in small portions over a period of 4 hour at 30-35°C. Extra portions of HCl, totaling 54 ml were added dropwise as needed to keep the reaction mixture a dark yellow color. After the addition was complete the reaction mixture was held for 30 minutes at 35°C, then warmed to. 50-55°C for another 30 minutes. The reactor was cooled to 10°C and 120 ml of ice/water added. The product was removed by filtration, washed with 100 ml of cold water and allowed to dry for about 15 minutes on the filter.
• Acetic anhydride (19.0 g) and acetyl chloride (0.2 g) were charged to a stirred 50 ml, 3-neck flask under N_. At 35°C the nitration mixture (A) was added dropwise at 35°C, and held at that temperature for 2 hours. The reaction mixture was then poured into 135 ml of stirred ice-water. The precipitated product was filtered off, washed with 10 ml of ice water and then dissolved in 21 ml of acetone. The pH was adjusted to 7.0 with 0.5M a 2 C0 3 and the solution poured into 120 ml of stirred ice- water. The mixture was allowed to stand in a refrigerator for 3 hours, the product filtered off and washed with 50 ml of ice water.
• HN0 3 HN0 3 HN0 3 ( ⁇ ) N0 2 OCH 2 CH 2 NHCH 2 CH HHCH 2 CH 2 ON0 2 >
• Nitric acid 120 ml 98%) was charged to a stirred 200 ml, 3-neck flask under N 2 and cooled to 5°C.
• N,N'-Bis(2- hydroxyethyl)ethylenediamine 25.64 g, 0.20 mole was added in small portions over a 1.75 hours at 5°C. Stirring was continued for 30 minutes at 5°C after completing the addition, then for another hour at 23°C.
• the reaction mixture was poured into 350 ml of stirred ice-water, the product filtered off, washed with 200 ml of ice water and dried under vacuum at 50°C to leave 59.22 g. of product (A) (decomposed at 149°C) for a 81.3% yield.
• Acetic anhydride (210 ml) was charged to a stirred 500 ml flask under N 2 and cooled to 10°C. HN0 3 (3.72 m. , 98%) and HCl (2.43 ml, 37%) were added.
• Product A (59.22 g, 0.1626 mole) was added in small portions over 3.5 hours at 33°. An additional 6.31 g of 37% HCl was added a few drops at the time as needed to keep the reaction mixture a dark yellow color. After completing the addition, the reaction mixture was held for 30 minutes at 35°C and 30 minutes at 50-55°C. The reactor was cooled to 10°C and its contents poured into 1 liter of stirred ice-water.
• the reaction mixture was cooled to room temperature and then poured dropwise into 100 ml of rapidly stirred methanol.
• the methanol solubles were decanted off, the polymer washed twice with 25 ml of methanol and dried under high vacuum at 60°C. 3.83 g of polymer was produced for a 93% yield.
• the polymer had a weight averaged molecular weight of 836, as determined by Gel Permeation Chromatography, a glass transition temperature of -18°C and a decomposition temperature of 188°C, as determined by Differential Scanning Calorimetry.
• the estimated heat of formation using the values according to Benson is -49.8 kcal/mole.
• 1,6-Dichloro-2,5-dinitrazahexane (2.4705g, 0.0100 mole), 3- Nitraza-l,5-pentanediol (1,6637 g, 95%, 0.0105 mole), and dry tetrahydrofuran (5 ml) were charged to a dry, stirred 50 ml, 3- neck flask fitted with an inlet tube and a reflux condenser. A slow N, flow was maintained through the solution to remove HCl.
• the reactor was heated at reflux with an oil bath for 12 hours. About 1.5 ml per hour of THF was added to make up for evaporative losses.
• the reaction mixture was cooled to room temperature and poured dropwise into 100 ml of rapidly stirring methanol.
• the bath temperature was lowered to 60°C and 5 ml. THF was added to dissolve the polymer.
• the resulting solution was cooled to room temperature and poured dropwise into 100 ml of rapidly stirring methanol. The methanol solubles were decanted away from the polymer which was then washed twice with 25 ml of fresh methanol and dried under vacuum at 55°C 2.98 g of polymer was recovered for a 81.0% yield.
• the weight-average molecular weight of the polymer was 1144, the T G was -29°C and the T, was 226°C. E ⁇ ample 10
• the bath temperature was lowered to 60°C and 5 ml THF was added to dissolve the polymer.
• the resulting solution was cooled to room temperature and poured dropwise into 100 ml of rapidly stirring methanol.
• the methanol solubles were decanted away from the polymer which was then washed twice with 25 ml of fresh methanol and dried under vacuum at 55 C C. 2.64 g of polymer was recovered for a 81.6% yield.
• the weight-average molecular weight of the polymer was 1214, the T Q was -28°C and the T Q was 228°C. E ⁇ ample 11
• the reactor was heated to reflux with a 110°C oil bath for 6 hrs.
• Wet EDC was removed as needed and replaced with an equal volume of dry solvent.
• the EDC was stripped off and the product was dissolved in 5 ml tetrahydrofuran.
• the solution was poured dropwise into 100 ml of rapidly stirring methanol, the methanol solubles were decanted away, the polymer washed two times with 25 ml of methanol and dried under high vacuum at 60°C 3.82 g of polymer was recovered for a 82% yield.
• the weight-average molecular weight of the polymer was 1220, the T Q was 24°C, and the T D was 250°C. E ⁇ a ple 12
• the reaction mixture was stirred for about 5 minutes until the solids were dissolved.
• the THF layer was separated, washed with 4 x 0.4 ml of brine, dried over anhydrous MgS04, filtered, and stripped off the solvent. 91 mg of a gummy material were recovered.
• the polymer was determined to have a Tg of 1.31°C, a Td of 238.7 ⁇ C and a Mw of 3763 by gpc.
• Example 2 was repeated except the pyridine use level was reduced from about 2 equivalents (51 ul, 0.63 mmol) to about 1.5 equivalents (38 ul, 0.47 mmol). 136 mg of a clear viscous polymer were obtained.
• the polymer has a Tg of 21°C, a Td of 257°C, and a Mw of 2534 by gpc.
• the solution was decanted, and the polymer was repeatedly washed with 3 x 25 ml of methanol and dried under vacuum at 60°C. 3.03 g (77.3% yield) of polymer was obtained.
• the polymer has a Tg of 20°C, a Td of 239°C, and a Mw of 5441 by gpc.
• Example 3 was repeated except two diols, 2- fluoro-2-nitro-l,3-propane-diol(30 mg, 0.22 mmol) and diethylene glycol (9 ul, 0.095 mmol) were used. 117 mg of a clear viscous polymer were obtained.
• the polymer has a Tg of -23.3°C, a Td of 252°C, and a Mw of 2016.
• the remaining solids were repeatedly washed with 3 x 0.4 ml of brine and 2 x 0.4 ml of water, and dried under high vacuum and heat. 140 mg of lightly yellow solids were obtained.
• the polymer has a Tg of 8°C, and a Td of 221°C, and a Mw of 4322 by gpc using DMF as the eluting solvent.
• the THF layer was separated, repeatedly washed with 4 x 0.4 ml brine, dried over anhydrous MgS04, filtered, and stripped off the solvent. 141 mg of a viscous polymer were obtained.
• the polymer has a Tg of -27, a Td of 244, and a Mw of 1863 by gpc.
• the reaction mixture was stirred for another several hrs., and then added 1 ml of THF and few drops of water. 0.4 ml of brine were added after all the precipitates were dissolved.
• the THF layer was separated, washed with 4 x 0.4 ml of brine, dried over with anhydrous MgS04, filtered, and stripped off the solvent. 137 mg of a yellowish viscous polymer were obtained.
• the polymer has a Tg of -13 °C, a Td of 218.71, and a Mw of 3056.
• This example is similar to example 7 except the post reaction time was reduced from 18 hrs. to 6.5 hrs. 122 mg of a slightly brown and viscous polymer were obtained.
• the polymer has a Mw of 4082.
• the polymer After drying under high vacuum and heat at about 55°C, 4.35 g (about 100% yield) of polymer were obtained.
• the polymer has a Tg of 18.5°C, a Td of 216°C and a Mw of 3940 by gpc.
• the polymer has a Tg of -22°C, a Td of 213°C, and a Mw of 1038 by gpc.
• the THF layer was decanted from the remaining undissolved small amount of a gummy material, washed with 0.4 ml of water and 2 x 0.4 ml of brine, dried over anhydrous MgS04, filtered, and stripped off the solvent. 192 mg of a viscous polymer were obtained.
• the polymer has a Tg of -28°C, and a Td of 230°C, and a Mw of 1026.
• reaction mixture was heated at 65 °C for additional 3.25 hrs., cooled and added 5 ml of THF, and poured in 100 ml of methanol. After standing overnight, the liquid solution was decanted, and the residue was dried under high vacuum to give 0.25 g ( about 4.4% yield) of a brown oil.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Polyamides (AREA)
• Polyesters Or Polycarbonates (AREA)

Applications Claiming Priority (5)

Publications (2)

Family

ID=27123591

Family Applications (1)

Country Status (4)

Families Citing this family (4)

Citations (3)

Family Cites Families (12)

• 1992
  • 1992-12-07 JP JP5511677A patent/JPH08500325A/ja active Pending
  • 1992-12-07 AU AU32400/93A patent/AU3240093A/en not_active Abandoned
  • 1992-12-07 WO PCT/US1992/010499 patent/WO1993013051A1/en not_active Application Discontinuation
  • 1992-12-07 EP EP93900885A patent/EP0618893A4/de not_active Withdrawn

Patent Citations (3)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events