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WO1993013051A1 - Polymeres energetiques et leur procede de preparation - Google Patents

Polymeres energetiques et leur procede de preparation Download PDF

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Publication number
WO1993013051A1
WO1993013051A1 PCT/US1992/010499 US9210499W WO9313051A1 WO 1993013051 A1 WO1993013051 A1 WO 1993013051A1 US 9210499 W US9210499 W US 9210499W WO 9313051 A1 WO9313051 A1 WO 9313051A1
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WO
WIPO (PCT)
Prior art keywords
polymer
nitramine
fluoro
nitro
diol
Prior art date
Application number
PCT/US1992/010499
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English (en)
Inventor
Eugene F. Rothgery
Rahim Hani
Richard H. Dumas
Ming Shen
Original Assignee
Olin Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Olin Corporation filed Critical Olin Corporation
Priority to JP5511677A priority Critical patent/JPH08500325A/ja
Priority to EP93900885A priority patent/EP0618893A4/fr
Publication of WO1993013051A1 publication Critical patent/WO1993013051A1/fr

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    • 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 temperature, and resistance to hydrolysis.
  • Hercules Incorporated investigated a specific nitramine-containing polymer, poly(diethylene
  • P-DEND glycol-4,7- nitrazadecanedioate
  • ester-plasticide propellants This report states that attempts to fabricate P-DEND by an acid catalyzed esterification reaction of 4,7-dinitrazadecanedioic acid (DNDA) with diethylene glycol in a variety of organic solvents were unsuccessful. This failure is attributed in the report to the fact that a cyclization reaction rather than a polymerization reaction occurred. More recently, it has been found that P-DEND has a viscosity and a glass transition temperature that are higher than might be desired.
  • DNDA 4,7-dinitrazadecanedioic acid
  • solution polymerization generally known in the art is solution polymerization.
  • solution polymerization processes typically provide resulting polymers which do not have as high a molecular weight as might be desired.
  • 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
  • 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 resistance to hydrolysis, represented by the Following e*> ;*iri»
  • a and e have a value 0 or 1
  • b and d 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)
  • 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 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:
  • x and y are independently 0 or integers of from 1 to 100, and the sum of x plus y is at least 1;
  • R 1 and R 3 are independently selected from the following formula: -N(NO 2 )(CH 2 )zN(NO 2 )- wherein z is an integer from 1 to 6 and R 2 ,
  • R 4 is independently selected from the following
  • the present invention relates to a process for producing a polymer containing detramine- and/or nitro- and/or fluoro-groups which comprises reacting at least one nitramine-containing diacid chloride monomer with at least one nitro- or fluoro- containing diol monomer in an 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 like) 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).
  • anhydrous organic solvent preferably tetrahydrofuran (THF), acetonitrile, or diethylether, although other organic solvents can be employed such
  • the polymer product is purified in a purification step, suitably by precipitation in a solvent/non-solvent mixture or by using gel permeation chromatography.
  • the nitramine-containing 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 of the class described by the general empirical formula given below wherein a and e have a value 0 or 1, b and d have values 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, and z has a value of from 0 to 0.9, with the proviso that the sum of y plus z 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 polyether polymers are suitably prepared by reacting a nitramine-containing bischloromethyl monomer with a diol under melt polymerization reaction
  • 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:
  • Useful nitramine-containing diols include the following: 3-nitraza-1,5-pentanediol and
  • 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.
  • 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. In addition, these polymers 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 calculated (by the Naval Weapons Center PEP method) impetus in propellent formulations, a desired
  • the preferred polymer moleculer weight is between about 590 and about 10,000, more preferably between about 1,500 and about 5,000.
  • molecular weights are weight average molecular weights as measured by gel permeation chromatography (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
  • 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 it allows a great range of
  • 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. Likewise, the reaction temperature is not narrowly critical and can vary over a wide range.
  • the reaction temperature is between about 0°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.
  • melt polymerization reaction in accordance with the present invention is preferably suitably conducted, for the most part, at subatmospheric
  • 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
  • the optional polymer purification step is preferably conducted by precipitation in a mixture of a paired solvent/non-solvent.
  • Suitable solvent/non-solvent pairs can be chosen from the
  • 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 g ) 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
  • 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
  • the 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 HCl 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 chloride monomer.
  • 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. If desired, 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-1, 3-propane-diol, 2,2-dinitro-1,3-propane-diol, 2,5- dinitraza-1,6-hexanediol and 2,2,5,5-tetranitro-1,
  • 2,5-Dinitraza-1,6-hexanediol is one of the nitramine diols with very good energy, but
  • present invention is particularly useful since thermal degradation of the monomers does not occur during
  • 2,5-dinitraza-1,6-hexanediol in poly esters in our new process provides polyesters having higher energy than those prepared from 3,6-dinitraza-1,8- octanediol and 3-nitraza-1,5-pentanediol.
  • Preferred diacid chlorides include 4,7-dinitrazadecanoic-1,10-diacid chloride and 4,8- dinitrazaundecanoic-1,11-diacid chloride which are prepared readily from their diacid precursors and thionyl chloride.
  • a process of preparing the nitramine-, nitro-, and fluoro-containing polyesters under a mild anhydrous condition, generally at ambient temperature, in an nonprotonic solvent and the presence of a 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
  • 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 polymers could be purified in a
  • 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 process of the present
  • 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-1,6-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-1,6-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),
  • 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
  • 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 HCl 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.
  • 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.
  • reaction mixture was cooled to 5°C for 30 minutes.
  • the product was filtered off, washed with 50 ml of cold water and dried under vacuum at room temperature to give 10.0g. of (D) for a 50% yield.
  • the melting point of the diacid obtained was 144-146°C.
  • Acetic anhydride (19.0 g) and acetyl chloride (0.2 g) were charged to a stirred 50 ml, 3-neck flask under N 2 . 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 Na 2 CO 3 and the solution poured into
  • 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)ethylenedi amine 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.
  • 1,6-Dichloro-2,5-dinitrazahexane (2.4705 g, 0.0100 mole), 3, 6-dinitraza-1,8-octanediol (2.5074 g, 0.0105 mole), and dry tetrahydrofuran (5 ml) were charged to a dried 50 ml, 3- neck flask fitted with an inlet tube and a reflux condenser. A slow N 2 flow was maintained through the solution via the inlet tube in order to remove HCl. The reactor was heated at reflux for hours.
  • 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
  • 1,6-Dichloro-2,5-dinitrazahexane (2.4705g, 0.0100 mole), 3- Nitraza-1,5-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 2 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 EDC was stripped off and the product dissolved in 5 ml of tetrahydrofuran.
  • the solution was poured dropwise into 100 ml of rapidly stirred methanol, the solubles were decanted away, the polymer washed twice with 25 ml of methanol and dried under high vacuum at 60°C. 2.95g. of polymer was recovered for a 69.9% yield.
  • the weight averaged molecular weight of the polymer was 1000, the T G was -20°C and the T d was
  • the polymer has a Tg of -6°C, a Td of 235°C, and a Mw of 2419 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-1,3-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.
  • pyridine 51 ul. 0.63 mmol was added dropwise at ambient temperature. The addition of pyridine resulted in a brown gummy product. After stirring at ambient temperature for 18 hr., 1 ml of THF and 0.2 ml of water were added. The reaction mixture was stirred for 2 hrs, and the liquid phase was decanted. 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 MgSO4, 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 polymer has a Tg of -13 °C, a Td of
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyamides (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention se rapporte à des liants énergétiques, et plus spécifiquement à une classe de polymères de polyéther contenant de la nitramine et caractérisés par une viscosité et une température de transition vitreuse acceptables ainsi que par une résistance à l'hydrolyse. L'invention se rapporte également à un procédé de production d'un polymère contenant des groupes nitramine et/ou nitro et/ou fluoro et qui consiste à faire réagir au moins un monomère de chlorure diacide contenant de la nitramine avec au moins un monomère diol contenant nitro ou fluoro dans un solvant organique anhydre (de préférence du tétrahydrofurane (THF), de l'acétonitrile, ou du diéthyléther, bien que l'on puisse utiliser d'autres solvants organiques tels que le pentane, l'hexane, le chlorure de méthylène, le dichloroéthane, le toluène, le benzène, et analogues) en présence d'une base amine tertiaire à une température de réaction comprise entre environ 0 °C et environ 50 °C.
PCT/US1992/010499 1991-12-23 1992-12-07 Polymeres energetiques et leur procede de preparation WO1993013051A1 (fr)

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JP5511677A JPH08500325A (ja) 1991-12-23 1992-12-07 エネルギーのある重合体およびその製造方法
EP93900885A EP0618893A4 (fr) 1991-12-23 1992-12-07 Polymeres energetiques et leur procede de preparation.

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US81231191A 1991-12-23 1991-12-23
US812,311 1991-12-23
US81720392A 1992-01-06 1992-01-06
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000020382A1 (fr) * 1998-10-07 2000-04-13 Sri International Azoles energetiques liees a de la nitramine et sels d'hydroxylammonium utilises en tant qu'oxydants, amorces et generateurs de gaz
DE102011118462A1 (de) 2011-11-14 2013-05-16 Maximilian Born Energetische Polymere als reaktive Strukturmaterialien zur Verwendung für Waffensysteme
EP1773902B1 (fr) * 2004-08-04 2017-12-13 Foam Supplies, Inc. Derive de reactivite et degradation de catalyseur dans la mousse polyurethanne

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102386460B1 (ko) * 2020-10-30 2022-04-15 국방과학연구소 고체 추진제용 바인더에 사용되는 고에너지 프리폴리머 및 이의 제조방법

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WO2000020382A1 (fr) * 1998-10-07 2000-04-13 Sri International Azoles energetiques liees a de la nitramine et sels d'hydroxylammonium utilises en tant qu'oxydants, amorces et generateurs de gaz
US6255512B1 (en) 1998-10-07 2001-07-03 Sri International Energetic nitramine-linked azoles and hydroxylammonium salts as oxidizers, initiators and gas generators
US6552051B2 (en) 1998-10-07 2003-04-22 Sri International Energetic nitramine-linked azoles and related compounds as oxidizers, initiators and gas generators
EP1773902B1 (fr) * 2004-08-04 2017-12-13 Foam Supplies, Inc. Derive de reactivite et degradation de catalyseur dans la mousse polyurethanne
US10385177B2 (en) 2004-08-04 2019-08-20 Foam Supplies, Inc. Reactivity drift and catalyst degradation in polyurethane foam
DE102011118462A1 (de) 2011-11-14 2013-05-16 Maximilian Born Energetische Polymere als reaktive Strukturmaterialien zur Verwendung für Waffensysteme
DE102011118462B4 (de) 2011-11-14 2021-07-22 Maximilian Born Energetische Polymere als reaktive Strukturmaterialien zur Verwendung für Waffensysteme

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EP0618893A4 (fr) 1995-05-31
EP0618893A1 (fr) 1994-10-12
JPH08500325A (ja) 1996-01-16
AU3240093A (en) 1993-07-28

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