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Energetic Polymers and Plasticisers for Explosive Formulations A Review of Recent Advances Arthur Provatas DSTO-TR-0966

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Energetic Polymers and Plasticisers for Explosive Formulations - A Review of Recent Advances
Arthur Provatas
Weapons Systems Division Aeronautical and Maritime Research Laboratory DSTO-TR-0966

ABSTRACT In an effort to comply with Insensitive Munitions (IM) criteria, energetic binders comprising polymer and plasticiser(s) are finding use in cast-cured polymer bonded explosives and cast composite rocket propellants. Energetic binders can be considered as cross-linked polymers that provide a matrix to bind explosive ingredients together with a plasticiser. Once cured, the polymeric binder is a tough elastomeric rubber capable of absorbing and dissipating energy from hazardous stimuli, lending itself well to EM applications. This general document outlines the most promising energetic polymers and plasticisers being considered today. Attention is focussed on several energetic polymers including glycidyl azide polymer, GAP, poly(3-nitratomethyl-3-methyloxetane), polyNIMMO and poly(glycidyl nitrate), polyGLYN, although several other energetic polymers will also be reviewed. Energetic plasticisers including oligomers (low molecular weight) of the polymers mentioned above, as well as a variety of nitrate esters, nitroaromatics and azido plasticisers, will also be reviewed. Finally, the review will recommend binder systems for DSTO's future energetic binder programs.

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Published by DSTO Aeronautical and Maritime Research Laboratory PO Box 4331 Melbourne Victoria 3001 Australia Telephone: (03) 9626 7000 Fax: (03) 9626 7999 © Commonwealth of Australia 2000 AR-011-428 April 2000

Energetic Polymers and Plasticisers for Explosive Formulations - A Review of Recent Advances

Executive Summary
In an effort to comply with Insensitive Munitions (IM) criteria, energetic binders comprising polymer and plasticiser(s) are being used in cast-cured polymer bonded explosives and cast composite rocket propellants. These new energetic binder systems offer energy output increases over conventional 'inert' non-energetic binder systems and are thus of important consequence to the ADF. This report outlines the most promising energetic polymers and plasticisers being considered by Defence forces around the world. Energetic binders are polymers which crosslink explosive ingredients together with a plasticiser into a tough yet flexible three-dimensional network. Plasticisers are typically added both to facilitate processing and to improve mechanical properties of the final cured formulation. This review comprises two main sections. The first section examines the synthesis, properties, and polymerization chemistry of energetic polymers while the second section is concerned with the chemistry of energetic plasticisers and their role in energetic binder systems. This report reviews recent developments in energetic binder systems (both polymers and plasticisers) for use in advanced cast-cured explosive and propellant formulations, and recommends binder systems that might best address the future requirements of the ADF.

Tech. surface chemistry and organic synthesis.) from the 'k University of South Australia in 1997 in polymer chemistry. His multidisciplinary research has led him to publish research in inorganic chemistry. In 1998 he commenced work for the Explosives Group ofDSTO. US patents have been awarded to this research. The focus of his research at DSTO resides with energetic polymers as binders for military applications and polymer bonded explosives. chemical engineering. During 1995.Authors Arthur Provatas ■ Weapons Systems Division H Arthur Provatas graduated with a PhD (Chem. polymer science. he interrupted his PhD studies to travel to the USA. as part of a joint Dow Corning-UniSA visiting fellowship to investigate advanced copolymers made by interfacial polymerization. .

3.Contents GLOSSARY 1. PNP 2.3.1 GAP Properties 2..4..3 Nitramine Polyethers 2.1.1.2 Polynitrophenylene..7 ENERGETIC PLASTICISERS Nitrate Ester Plasticisers BDNPA/F Plasticisers Azido Plasticisers 3.2 PolyNIMMO Properties 2.4.1 PolyNIMMO 2.3 Oxirane Polymers 2. PVN 2..2 Properties of PolyGLYN Prepolymer 2.3.6.. INTRODUCTION 2.2 Oxetane Polymers 2.4 Miscellaneous Nitrogenous Polymers 2. 3.1 Fluorinated Copolymers 3.4 N...2 3.5 Nitration using Dinitrogen Pentoxide 2. CONCLUSIONS AND RECOMMENDATIONS 5.4 3.N'-Bonded Epoxy Binders 2.3 Stability of PolyGLYN Rubber 2.2 Branched GAP 2.5 3. ENERGETIC POLYMERS 2.1 3..4.2.2.1 Glycidyl Azide Polymers 2.1 Miscellaneous Azido Plasticisers K10 Plasticiser Nitrato Ethyl Nitramine Plasticisers (NENA) Oxetane Plasticisers GLYN Dimer Plasticiser .1 Polyvinylnitrate. 1 2 2 5 6 7 8 10 12 12 13 14 15 15 15 16 16 16 20 21 22 23 24 25 26 27 27 29 30 30 32 4.3.3 3.6 Fluorinated Polymers 2.6 3. REFERENCES .1 PolyGLYN 2.4..

2-dinitropropyl) formal Eutectic mixture of BDNPA and BDNPF Butyl-2-nitratoethyl nitramine 1.2-dinitropropyl) acetal Bis-(2.3-Bis(3-azidomethyl)oxetane Bis-(2.4-Butanetriol trinitrate Dibutyltin dilaurate Differential Scanning Calorimetry Epichlorohydrin Ethyl-2-nitratoethyl nitramine Glycidyl azide polymer Azido-terminated glycidyl azide polymer Glycidyl nitrate Hydroxyl terminated polybutadiene Cyclotetramethyleneterranitramine Insensitive Munitions Isophorone diisocyanate Specific impulse Low Vulnerability Ammunition Methyl-2-nitratoethyl nitramine Number average molecular weight Melting point Weight average molecular weight Nitrato ethyl nitramine Nitrated hydroxyl terminated polybutadiene 2-Nitratomethyl-3-methyloxetane Polymer Bonded Explosive Polyepichlorohydrin Polymer of 2-nitratomethyloxirane Polymer of 3-nitratomethyl-3-methyloxetane Cyclotrimemylenetrinitramine Glass transition temperature Melting temperature Trimethylolethane trinitrate Thermoplastic Elastomer .2.DSTO-TR-0966 GLOSSARY Abbreviations/ Acronyms BAMO BDNPA BDNPF BDNPA/F BuNENA BTTN DBTDL DSC ECH EtNENA GAP GAPA GLYN HTPB HMX IM IPDI Isp LOVA MeNENA Mn mp Mw NENA NHTPB NMMO PBX PECH polyGLYN polyNIMMO RDX Tg Tm TMETN TPE Name 3.

Introduction The design of future weapons systems requires the use of explosive and propellant formulations having enhanced performance (energy output) and reduced vulnerability during storage and transportation.DSTO-TR-0966 1. Another approach has . and containing a plasticiser such as dioctyl adipate (DOA). In particular. but 15-20% of binder is required to prepare a processable formulation. mitigation devices and packaging. the current practice is to encapsulate the explosive in a binder. reducing the overall energy output and the performance of the composition. For example. where the nitrocellulose was used to thicken the nitroglycerine and reduce impact and friction sensitivity [1]. Inert binder systems have been employed effectively in explosive compositions for underwater and air-blast application. One strategy is to change the fabrication method from cast-cure to extrusion or pressing. ordnance that fulfils performance expectations but in which the response to unplanned hazardous stimuli is reduced. as it is practical. HTPB requires a theoretical solids loading of 92% by weight of ammonium perchlorate for complete combustion. One approach to less sensitive explosives is the development of cast-cured polymer bonded explosives (PBX). Several important design considerations for such formulations include improved mechanical properties. Australia has a policy (DI(G) LOG 0-10) for introduction of IM into the ADF inventory. although perhaps the most obvious is the use of intrinsically less sensitive explosive and propellant formulations. . thereby reducing the quantity of inert binder required. extensive programmes have evolved worldwide for the development and introduction of Insensitive Munitions (IM). sensible and cost-effective to do so. One of the earliest binders used in energetic materials was a mixture of nitrocellulose and nitroglycerine. Several approaches are available to provide IM solutions. <ev\£ HTPB These binder systems have excellent physical properties and reduce the vulnerability of explosive charges. but it is difficult to formulate high performance cast-cured explosives for metal acceleration. composed of a polymer such as hydroxyterminated polybutadiene (HTPB) crosslinked with isocyanates. including weapon design.i. but they are inert. Binders are typically cross-linked polymers providing a matrix to bind the solids together with a plasticiser (usually not more than 50% of the total binder system) to ease processing of the uncured mix and to modify the mechanical properties of the final composition. in which the explosive ingredient is suspended in a polymeric binder. Other polymers include carboxy-terminated polybutadiene (CTPB) and hydroxy-terminated polyethers (HTPE) [2]. cured in-situ as a tough elastomeric rubber which absorbs and dissipates the energy from hazardous stimuli. use and disposal. decreased signature.e. the binder "dilutes" the explosive. extended service life and reduced environmental impact in manufacture. Nowadays.

2. polynitroaromatics. and poly(glycidyl ratiate) (polyGLYN). O-nitro (nitrate esters) and N-nitro (nitramines)) and difluoramine groups.N-bonded epoxy functional polymers. and nitrated polybutadienes Uke NHTPB. as well as a wide variety of nitrate esters. and recommends ingredients that might best address the future requirements of the ADR The report is split into 2 chapters. [Monomers are NIMMO. Other energetic binders discussed in this report include fluoropolymers. A more radical approach is inclusion of energetic functional groups.1 Glycidyl Azide Polymers Azido-functionalised polymers such as glycidyl azide polymer (GAP) were reported as heralding the next generation of energetic binders early in the 1980s [1]. The safety characteristics of GAP loaded with RDX (RDX/GAP 86. PECH-triol. Energetic Polymers 2. . riycidyl nitrate. N.4/13. Energetic plasticisers mclude oligomers of the polymers mentioned above. along the polymer backbone and in the plasticiser. respectively]. GAP may then be crosslinked by reaction with isocyanates to give an extended polymeric matrix. This report reviews recent advances in the development of energetic polymers and plasticisers for use in advanced cast-cured explosive and propellant formulations. Frankel and coworkers at Rocketdyne [5] synthesised PECH-triol by polymerization of epichlorohydrin (ECH) with glycerol as the initiator unit. nitro (C-nitro. the first chapter examines energetic polymers while the second chapter reviews the plasticisers before making any recommendations. polyvinylnitrates. as shown below in Figure 1. Incorporation of these explosophores increases the internal energy of the formulation.4/13.DSTO-TR-0966 been to use polymers and/or plasticisers which contribute to the overall energy of the composition This has been successful in the development of high performance explosives and advanced rocket propellants.6) are almost the same as those for RDX compositions made with the inert HTPB binder (RDX/HTPB 86. 3-nitrato-methyl-3-methyloxetane and GLYN. New energetic binders that appear to offer such promise include azide functional polymers like glycidyl azide polymer (GAP).6) [3]CH2N3 H0_|_CH2—C H O-j-H GAP GAP was first synthesised in 1972 by Vandenburg [4] by the reaction of sodium azide in dimethylformamide with the polyepichlorohydrin. nitroaromatics and azido plasticisers. such as azido. in addition to improving the overall oxygen balance. or the nitrato polyethers hke poly 3nitratomethyl-3-methyloxetane) (polyNTMMO).

and to achieve the desired level of crosslinking to produce a tough and elastomeric rubber it must be raised by the addition of triols or used with triisocyanate crosslinkers. by regiospecific epoxidation of linear PECH under basic conditions [9]. The first step of the process can actually be by-passed. Subsequent opening of the epoxides under different conditions leads to PECH polymers with different functionalities and structures depending on the reactants.—CHCH2CH2CI CH-CHCHaO -CH2CHO 'I H O CH2CI I -CH2CHOPECH-TRIOL CH2CI I NaN3 DMF HO+CHCH2CH2N3 -OCHpHCHfeO. Optimization of PECH production has led to the successful development of a process which yields GAP polymers having average molecular weights of 2100 and functionalities (the number of reactive hydroxyl groups per molecule) of 1.CH2CHOO CH2N3 I I GAP TRIOL -CH2CHOCH2N3 I Figure 1: Synthesis of GAP Triol This general process can also be used to produce linear GAP-diol and branched GAPdiol polymers [6]. The functionality of linear GAP is nearly 2. as commercial quantities of PECH-diol are available.6 to 3. depending on the catalyst.1. organic solvent [6] or in polyethylene oxide [8]. Ampleman conceived the novel idea of changing the functionality of PECH under mild basic conditions. The azidation step can now be carried out in aqueous solvent [7].DSTO-TR-0966 H2C—CH—CH2-CI + HOChfeCHCHgOH OH ECH Giycerol HO. Ampleman has patented a method of synthesising GAP with increased functionality. the initiator and the ratio of ECH/initiator. where PECH . Since the azidation step does not change the functionality of PECH (direct replacement of Cl by N3).

Frankel et al. respectively.ü>-Diisocyanate GAP and which was prepared by the reaction of GAP with hexamethylene diisocyanate. [10] has patented a process whereby linear GAP is terminated with isocyanate groups to give an a. azidation of these polymers yields GAP polymers with higher functionality and reactivity.G>-diisocyanate functionalised GAP with the general formula: Or OCN(CH2)6 -I j? C NH—(CH2)6NCO NH—C. only one end of the chain can be functionalised with isocyanate and the other end with trimethylene propane. a triol (trimethylolethane) or a tetrol (pentaerythritol) to give a polymer with a functionality of 2. R = ■0 CH—CH2fO CH2CI O. to give a trifunctional GAP isocyanate: .3 or 4.-CH2-CI CH2CI y The next stage of this three-step process is ring opening of the epoxy groups with acidic water. is also possible. Functionalisation of GAP with various other groups. and which then react with the chloride groups to give the epoxy functionalised PECH.OCH-CH2.DSTO-TR-0966 with terminal alcoholate groups are formed. Alternatively. Finally.O CH2N3 a. The mechanism for the epoxidation step can be shown as: Cl—CH2-CH-CH2-R-CH2—CH-CH2-CI ^ V l-Na« VO ONaV CH2-CH—CH2-R-CH2—CH—CH2 0 O where.

Certain organometallic catalysts such as triphenyl bismuth. Gas evolution on curing the liquid GAP with isocyanates is also a serious problem. AH{. Further. yellow liquid 280 >900 2.29 Lt. 280 cal/g M„ 1700+300 Functionality 2. structure and method of preparation. as well as promoting cure [13]. TPB and dibutyltin dilaurate have been found to suppress carbon dioxide formation. >3 200 h. Table 1: GAP Diol and Triol Polymers [11] GAP Diol Density.1 GAP Properties The physico-chemical properties of GAP depend on the degree of polymerization.29 Lt. 100 °C Tg.0 Vacuum stability. However at low temperatures GAP is hard and brittle as a consequence of the rigid.DSTO-TR-0966 CH3CH2C CH20—fCH2CHO—j-C \ r CHgNg' ll NH—(CH2)6NCO a-lsocyanate GAP 2. Isocyanates react with moisture to generate carbon dioxide.°C -45 GAP Triol 1.1. performance and safety of the explosive composition.5-3. g/cm3 1. the functionality of linear GAP is close to 2.0 >3 -45 GAP has a low glass transition temperature (-45°C) and a low weight percentage of polymer weight-bearing chain. mL/g. Gas generation can be readily expressed as: R—N=C=0 R—N=C=0 + + H20 RNH2 ► *► RNH2 + C02(g) RNH-CO-NH-R urea . yellow liquid Colour Heat of Formation. which remains trapped in the voids of the crosslinked binder and results in decreased mechanical properties. and must be raised by the addition of triol or crosslinked with triisocyanate to generate the desired extended polymeric matrix. see Table 1. which results in an energetically favourable binder system [12]. conjugated -N3 groups limiting the flexibility of the polymer backbone.

burning smoothly at elevated temperatures and pressure (>0. impact sensitivity and thermal stability. Table 2: GAP Explosive Classification Test Results [5] Test #8 Blasting cap . followed by a secondary weight loss without heat liberation. It is synthesised by the simultaneous degradation and azidation of high molecular weight solid polyepichlorohydrin (PECH) with sodium azide in the presence of a basic cleaving agent and polyol in a polar solvent (dimethyl sulfoxide.1.9°C Sayles [18] and Dhar [19] both found that GAP reduces the impact sensitivity of AP/RDX based composite propellants. . unconfined burning. Differential thermal analysis and thermogravimetric studies (DTA/TGA) of the decomposition of GAP under a helium atmosphere (0.2 Branched GAP Branched GAP consists of a long GAP backbone chain.DSTO-TR-0966 The energetic properties of GAP are not a consequence of its oxidation products.3 MPa) without explosion ri6i Thermal decomposition studies have been widely examined for GAP. and that subsequent decomposition of the resulting nitrile leads to carbonaceous by-products. 2. GAP also contains a relatively high concentration of carbon atoms. who observed initial decomposition at 240°C.)] [3].5% wt loss after 8 days at 73. Differential scanning calorimetry (DSC) studies on GAP have been carried out by Leu et al.1 MPa) revealed an exothermic decomposition at 202-277°C accompanied by a 40% weight loss. determined by standard explosive classification tests including initiation. [17]. followed by degradation at 260500°C GAP has a Hazard Classification of 1. GAP contributes an intrinsic energy content of 2500 kj kg-1 [AHexpl.Cotton soaked liquid Unconfined burning Impact sensitivity Thermal stability Result Did not detonate Did not detonate Burns smoothly and rapidly 200 kg-cm 0. (calc. Results are shown in Table 2. and therefore has a high "combustion potential" [15].Liquid . dimethylformamide or dimethylacetamide) [20]. to which shorter GAP chains have been grafted. which gives nitrogen gas with a heat of reaction of + 957 kj/kg at 5 MPa [14]. but rather are due to chain scission of the azide group. Kubota [15] has suggested that initial decomposition of GAP follows the reaction: R—CH2—N=N2 *R—C^^N+ N2 + H2 corresponding to the release of 685 kj/mole.3 (mass fire hazard).

9 2.3 1.1 2.6 2. 2.8 2.5 9. The synthesis of BAMO involves treating 3. All the samples possess narrow molecular weight distributions and low glass transition points. A pilot-plant for the manufacture of 5 kg/batch branched GAP has now been commisioned at DREV [22.4 1. Adjusting the catalyst/polymer weight ratio controls the molecular weight.2 a Hydroxyl functionality determined by gellation technique -15 -50 -50 -50 -55 -55 -55 [25].5 to 5. Solvents used in this process must solvate the high molecular weight polymer as well as the sodium azide and catalyst in order to accomplish the combined degradation and azidation step effectively.2 3. Table 3: Branched GAP Properties [24] Mw 90 000 22 000 9000 5600 4400 3600 3200 M» 36 000 10 000 4300 2800 2300 2000 1900 Mw/M„ Functionality3 Tg (°C) 2. cost and hazardous operations.2 Oxetane Polymers Energetic polyoxetanes were first synthesised by Manser from monomers such as 3nitratomethyl-3-methyl oxetane (NMMO or NIMMO). Typical degradation catalysts include lithium methanolate and sodium hydroxide. NTMMO is prepared by the acetyl nitrate nitration of 3-hydroxy-methyl-3-methyloxetane (HMMO). 77.0 x 105 by the degradation process was devised at DREV by Ahad [21]. The molecular weights all decrease with a corresponding reduction in the functionality of the polymer. with subsequent reductions in time.0 X 106) with an alkali metal azide in organic solvent with catalyst. The degradation process allows for the synthesis of branched GAP with a lower Tg than its corresponding linear analog (Tg = -55°C for branched GAP and -45°C for linear GAP).23]. .0 2. Some typical properties of branched GAP prepared by the degradation process are listed in Table 3.7 2.5 2.DSTO-TR-0966 The preparation of branched GAP with molecular weight ranges of 1000 to 2.25°C (cp) 500 000 70 000 39 000 28 000 22 000 19 000 16 000 (cal/g) -1995 -5025 -5000 -5010 - The large hydroxyl functionality of the higher molecular weight polymers is an indication that GAP obtained by the degradation process contains branches possessing terminal OH groups. 3. Ahad prepared branched hydroxyl-terminated GAP polymers via the reaction of a high molecular weight polyepichlorohydrin (0.3-bis(chloromethyl)oxetane (BCMO) with sodium azide in dimethylformamide at 85°C for 24h.7 2. The result of this innovative degradation process is that it is now possible to obtain branched hydroxyl-terminated polymers in a single step.3-bis-(azidomethyl)oxetane (BAMO) and 3-azidomethyl-3-methyl oxetane (AMMO) [26].3 1.

X + AcON02 'CH3 HMMO >v -' v CH2ON02 ^' CH3 N. The mechanism of polymerizing NTMMO with boron trifluoride etherate catalysts is shown below and gives pale yellow liquid elastomers. the mono-functional analog of BAMO. NIMMO is a low Tg monomer ideal in many munitions applications. dinitrogen pentoxide (N2O5) in a flow nitration system [29]. /vCH2R vs* R = Cl or OTs + NaN3 0 V<OH3 AMMO A more convenient synthesis of NIMMO can also be carried out using an alternative nitrating agent. This nitration process gives excellent yields and produces sufficiently pure NIMMO that requires no further purification [30]. ~80°C) ideal for use as the hard block in TPE manufacture. is synthesised by azidation with sodium azide of the chloro [27] or tosylate [28] product of 3-hydroxy-methyl-3methyloxetane. HMMO. 2. BAMO is a solid symmetric monomer (m. The energetic monomers described above are readily polymerized to liquid curable prepolymers by use of a boron trifluoride etherate/l.1 PolyNIMMO Traditionally.CH2CI 2NaN3 'CH2CI BCMO ^ ^ n/ «v /\ /CH2N3 \/ + 2 NaCI y\ ^ CH2N3 BAM0 AMMO.4-butanediol initiator. the polymerization of oxetanes to polyethers is achieved by cationic polymerization employing initiators (commonly diols) and catalyst (Lewis acid) [31].p. .MM0 + AcOH . while AMMO is an unsymmetrical monomer used to provide amorphous character.DSTO-TR-0966 yy CH2OH / \ / 0 .[32].2.

which then undergoes propagation with more oxetane monomers to generate the polymer chain. The molecular weight can be adjusted by changing monomer feed rates and the ratio of diol to Lewis acid co-initiator. including a lack of molecular weight control and product reproducibility. polymeric chains that terminate at both ends with primary hydroxyl groups possess an advantage over secondary or tertiary alcohols in that primary hydroxyl groups are more reactive towards isocyanate groups during cure. poor initiator incorporation and the failure to adequately form copolymers of the desired structure [33].e. The polymer is then terminated either with water or alcohol to give the hydroxyterminated polymer. Generally. at least one isocyanate equivalent must be used. aging and decomposition behaviour. End-modification of the primary hydroxyl groups must be carried out to ensure a stable energetic binder with respect to its vacuum stability. such primary hydroxyl reactivity can have an adverse effect in regards to the final cure stability of energetic binders. for crosslinking purposes. Use of an activated monomer polymerization method changes the underlying mechanism from a cationic polymerization process to the attack of a hydroxyl-terminated polymer on an activated monomer as follows: . The classical canonic polymerization of oxetanes described above suffers from several shortcomings. since 1. The polyNTMMO prepared above is difunctional.OEt2 BF3OROH ON02 BF3OROH ON02 V ONO. For chain elongation.-an isocyanate of higher functionality. i. However. or a separate crosslinking agent such as trimethylolethane or trimethylolpropane must be used.4-butanediol is the initiating alcohol (R = -(CH2)4-). each molecule contains two hydroxyl groups. ONO ON02 PolyNIMMO (n-2) Polymerization occurs by donation of proton from initiator to the oxetane.DSTO-TR-0966 \f + HOEt2 + O -Et20 ON02 HOROH + BF3.

primarily in avoiding the formation of unstable and highly active cationic propagating species. triethoxonium tetrafluoroborate. such as polyNIMMO. requires only catalytic quantities of a stable acid catalyst with an inexpensive alcohol initiator and is carried out at ambient temperatures. and are cured with conventional isocyanates upon heating. This is in complete contrast to the classical cationic polymerization route. This method has several advantages over the classical cationic polymerization of oxetanes.2 PolyNIMMO Properties Oxetane based polymers. fluoroboric acid [35] to the spirosiloxane developed by Sogah [36]. Table 4 highlights relevant properties of commercial polyNIMMO.DSTO-TR-0966 Activated Monomer Polymerization R . Catalysts employed for activated monomer polymerization range from boron trifluoride etherate. 10 .R' WVW\(V*OH + /$■ .)] [3] and is classified as a non-explosive (UK classification).•VWWi »■ R' •WWV*^*0. 2. both difunctional and trifunctional species.2. offer low glass transition temperatures and miscibility with similar plasticisers.OH + X Classical Cationic Polymerization -R' R' . £■ The salient feature of activated monomer polymerization is attack of an alcohol on an activated oxetane monomer. which comprises a marginally stable co-initiator (typically BF3 or AgSbFe) with biscumyl chloride (BCC) co-catalyst and is carried out at -90°C. thus ensuring rapid and complete initiator incorporation into the polymer chain [34]. The activated monomer polymerization yields copolymers with good molecular weight control and reproducibility. PolyNIMMO has an intrinsic energy content of 818 kj kg"1 [AHexpl (calc.

with atmospheric oxygen playing a greater part.DSTO-TR-0966 Table 4: Properties of Difunctional and Trifunctional PolyNIMMO [37] Properties Mwa M„b Mw/Mnc PolyNIMMO Difunctional 17 000 12 500 1. the initial process is rapid and anaerobic. although this can be reduced by the inclusion of stabilisers such as diphenylamine and 2-nitrophenylamine (1% wt/wt). The basic degradation mechanism involves homolytic scission of the CH2-O-NO2 bond to give CH2O. Aging and degradation studies on polyNIMMO have been carried out at DERA in the UK and showed that polyNIMMO exhibits gassing. radicals and N02« initiates auto-oxidation reactions involving peroxide formation. (DSC @ 5°C/min) Very stable Stability (Vacuum Stability Test) Insensitive Impact Sensitivity (Rotter Test) 1600 Viscosity.36 <2 -30°C 187°C PolyNIMMO Trifunctional 6500 4200 1. d as determined by JH NMR e commercial product (Bayer). 11 . The activation energy is in the range associated with the decomposition by nitrate ester bond cleavage [38]. and reaction with oxygen to give chain scission of the polyether backbone. alkoxy and alkyl reactions. at temperatures of around 60°C the reaction is slower. Kinetic data obtained on polyNIMMO decomposition follows first order rate laws with no autocatalysis observed. At temperatures greater than 120°C. 30°C 99%+ Purity Desmodur N-100e Recommended Cure Reagent a Mw is the weight average molecular weight b Mn is the number average molecular weight c Mw/Mn is the molecular weight distribution. radicals and N02» [39].55 <3 -35°C 184°C Very stable Insensitive 99%+ MDI Functionality4 Tg (DSC) Onset of decomp. yielding both chain scission and crosslinking. Production of the CtkO.

2. 12 .3 Oxirane Polymers Oxirane polymers possess similar physical and chemical properties to oxetane polymers. which adds to the polymer chain. regenerating a proton. as used in the synthesis of polyNIMMO) combined with a di-functional alcohol (glycol).DSTO-TR-0966 2. Urethane crosslinking with isocyanates leads to polyGLYN cured rubbers. and is polymerised to give a hydroxyl terminated prepolymer. ON02 . with the major difference being one fewer methylene group in the repeating unit. Slow addition of the monomer solution to the initiator solution generates an activated monomer unit. The proton activates a further monomer unit. to give a nominally di-functional polymer [40]. Polymerisation of the prepolymer employs a tetrafluoroboric acid etherate initiator (not boron trifluoride etherate initiator. is now prepared using N2O5 in a flow reactor to give dichloromethane solutions in high yields and high purity. like its oxetane counterpart NIMMO. which combines with the alcohol in a ring opening process.3. O 0 PolyGLYN Prepolymer PolyGLYN Rubber NHR GLYN.ON02 p*^o £±S GLYN X ON02 * pw*0 / \ OH /- . However some confusion results from the term 'polyGLYN' being used for both the prepolymer and the cured rubber.1 PolyGLYN Glycidyl nitrate (GLYN) is prepared by the nitration of glycidol. requiring no further purification before polymerisation. Reaction is terminated by quenching in excess water followed by neutralisation. .0.

g/cm Tg.DSTO-TR-0966 HBF4 + s\/\ ONO. of I. yellow liquid high in energy and density with a low Tg [Table 5].)]. GLYN Protonation z6.OH HOROH _ HORO + HBF4 / ON20 Ä ON02 BFV2n ON02 PolyGLYN Figure 2: Active Monomer Polymerization of GLYN 2. (calc. PolyGLYN has a calculated energy of 2661 kj kg-1 [AHexpl.5 170 13 .46 -35 -68 ~2 -37 -60.°C Heat of formation.2 Properties of PolyGLYN Prepolymer PolyGLYN prepolymer is a clear. Table 5: Typical Properties of Poly (GLYN) [41] PolyGLYN Density. its sensitiveness is classed as too low to require classification as a Class 1 explosive (UK classification). + ON02 BF4 . °C 3 1. comparatively higher than both GAP and polyNIMMO (2500 and 818 kj kg"1.3. respectively) [3]. kcal/mol Functionality Hydroxy value (mg KOH/g) O2 balance Temp. In addition.

when cured with isocyanates the resulting polyurethane rubbers show poor stability. Long term or accelerated aging results in degradation of the rubber. while the sulphuric acid/THF end-modified rubbers maintain their structural integrity with good resistance to tearing. Such dramatic aging was not observed in polyNIMMO rubbers (Fig.3. /~ <v—o y a ON02 yr s PolyGLYN X HN Further. 3) [1]. Such chain scission is not possible in the case of polyNIMMO. and Shore Hardness measurements on polyGLYN cured with Desmodur N100 and isophorone diisocyanate (IPDI) reveals that the cured rubbers from unmodified polyGLYN degrade rapidly./' PolyNIMMO (v/\^0 /" OH J .ON02 ISQCYANATE _ .DSTO-TR-0966 2. degradation is not prevented by the presence of stabilisers. 14 . which has no labile H atom available for transfer. or by the exclusion of oxygen. Accelerating aging tests at 60°C in a sealed tube. This decomposition of polyGLYN rubber is attributed to a low activation energy degradation associated with chain scission at the urethane linkage and has little to do with the normal nitrate ester degradation process. The problem has been overcome by modification of the chain ends to give a diol terminated polyGLYN prepolymer. ON02 p<vs^O O PolyGLYN NHR P»N/^0 ONO. and is not dependent on the isocyanate used.3 Stability of PolyGLYN Rubber Uncured polyGLYN prepolymer exhibits good chemical stability. Figure 3: Uncured and Cured PolyNIMMO and PolyGLYN CH3 >*/N^O ON02 ISQCYANATE CH3 ON02 /~ \ OH \ HN . /} +co2 + RNH2 This instability appears to be an inherent problem with polyGLYN prepolymer. However.

Modifications involve a 50% K2CO3 wash. nitramine polyethers and N.4 Miscellaneous Nitrogenous Polymers Miscellaneous nitrogen-containing polymers that have found use as energetic binders include polyvinylnitrate. Vacuum stability tests showed that sulphuric acid/THF endmodified rubber had stabilities of around 2mL/g. double-base composite propellants to improve mechanical properties. ON02 / pvs^Q OH PolyGLYN Prepolymer End Modification Route for PolyGLYN n OHW p^s^o A H30© p^~o ^s0H \H Diol-terminated PolyGLYN Prepolymer 2. PVN Polyvinylnitrate. Recently the inert poly(furfuryl glycidyl ether) has also been identified as a possible route to energetic binders [43]. It is expected that energetic polymers can be produced via incorporation of explosophoric groups onto the poly(furfuryl glycidyl ether) backbone. For comparison.5 mL/g [1]. [44] nitric acid in ether.N'-bonded epoxy binders.4. The polymer has a density of 1. [42]. Pure PVN has been found by vacuum stability tests to be more stable than nitrocellulose and has been added to cast-cured. amorphous polymer of relatively low molecular weight (-2000) and is manufactured by Dynamit Nobel [47].3-dichloro-2. polynitrophenylene. and a THF/H2O wash prior to isocyanate curing.4. 1 15 . 2.1 Polyvinylnitrate. and was first synthesised in 1929 [2] by nitration of polyvinyl alcohol with mixed acids.DSTO-TR-0966 Researchers then discovered that these end-modified polymers were exhibiting high gasssing rates.5 g/cm3 and molecular weight over 100 000. PNP PNP is a thermostable.6-trinitrobenzene with copper powder catalyst in The vacuum stability test measures the volume of gas evolved from a sample while it is heated at 100CC for 40 hours and is qouted in mL per grams. the energetic binder polyNIMMO has a vacuum stability of around 0.4. [45] or nitric acid in chlorinated solvents [46]. 2.2 Polynitrophenylene. followed by a 10% K2CO3 wash.' This problem has now been solved by effectively washing the diol terminated polyGLYN prepolymer. The polymer is obtained by Ullmann's reaction of l. -[CH2-CH(ON02)-]n-/ was devised to replace nitrocellulose binders.

Jain et al. Figure 4: General Structure ofN. and are largely synthesised by nitration [51]. 2.N(CH2)(7NCH2]y[ORO)] where R = -CH2CH2OCH2CH2-. The reaction of nitramine-containing monomer with a diol in the absence of solvent gives polymers of the type: N02 N02 N02 N02 N02 [CH2NCH2(CH2)mNCH2]JCH2N(CH2)/. These polymers show high specific impulse in propellant formulations. [49]. and a relatively low Tg (-18°C). They can be prepared in a molecular weight range from 500 to 10 000 by simply varying the stoichiometry of the diol and monomer. They exhibit good propellant characteristics (superior ignition rates and increased burn rate) over conventional polybutadiene binders. The classical nitration method using mixed acid (either 100% nitric acid or mixtures of nitric acid/sulphuric acid) is generally too severe for polyether 16 .3 Nitramine Polyethers A recent patent [48] detailed the synthesis of nitramine functionalised polyethers by a solvent free.[50] has synthesised such compounds by the epoxidation of bis dicarbonylhydrazones of adipic. 2. The polymer does not melt and is coated onto fillers by an acetone-ethanol solution and finds uses as a heat resistant binder for propellants.N'-Bonded Epoxy Binders These compounds are based on a.4 N. azelaic and sebacic dihydrazides (Fig. low viscosity properties and resistance to hydrolysis.N'-bonded Epoxy Binders OH .N'-bonded epoxy binder (16%). N.5 Nitration using Dinitrogen Pentoxide The C-nitro (C-NO2). Propellant samples were made by press-moulding together ammonium perchlorate (80%).DSTO-TR-0966 nitrobenzene at 150°C.co-epoxy functional compounds having N. nitramine (N-NO2) and nitrate ester (-ONQ2) functional groups are basic building blocks for energetic materials.4. melt polymerization reaction process to yield polymers with low Tg.4. a functionality close to 2.N'-bonds in the backbone. diaminodiphenylmethane curing agent (4%) and dimethyl sebacate as plasticiser. /Ox jCZ_CH -CH JN— L | L (CH 2)X—N—N—CH A N A N I 2-CH -CH 2J— CH 2-CH J n CH2 2. 4).

care must be observed with regards to the temperature and time of reaction. 30 min Glycidyl Nitrate ». or by anodic electrolysis of N2O4 in 100% nitric acid) are quantitative and rapid. N2O5 has differing nitrating behaviour according to the medium in which it is employed. 3-5 s Glycidol -CH2ONO2 N2Q 2^5 5°C. In 100% nitric acid there is a high degree of dissociation arising from the polarity of the solvent. nitration of polyNIMMO and polyGLYN takes place at low temperature and within a few seconds. leading to unselective nitration akin to that in mixed acids. then ring cleavage is the only reaction observed. and is not selective. However. For example. If an equimolar amount of N2O5 is used to nitrate the epoxy groups. N2O5 (produced by ozonation of N2O4. Glycidyl Nitrate ON02 I ON02 Nitroglycerine I ON02 I 17 . typically complete within minutes at ambient temperature. Furthermore. However. without attack at the olefin sites. whereas nitration reactions of over 30 mins and with excess N2O5 produces ring-opening. reactions with dinitrogen pentoxide. This feature can be observed in the partial nitration of polybutadiene in which only a portion of the double bonds have been converted to epoxy groups. wv-CH2-CH=CH— CH2-CH— CH— CH2vwv A N205 ON02 vv~CH2-CH=CH—CH2-CH— CH— CH2^^ ON02 I I When preparing energetic binders by nitration with N2O5. nitrations carried out in organic solvents (preferably chlorinated hydrocarbons) involve undissociated N2O5 [52]. as shown in the following GLYN example: -CH2OH ^ 7 CH2ON02 N205 -10°C.DSTO-TR-0966 backbones. A further feature of N2O5 nitrations is that reactive polymer backbones can be nitrated without chain scission of the backbone.

or alternatively. nitration of the hydroxyl group produces nitric acid which may also cause ring-opening to give a nitrate and another hydroxyl group [52]. 18 . the classical route which employs a nitromercuration-demercuration route. shown on opposite page. H3C. /CH2ON02 HN03 -*ÖNO2 ÖH H3CK /CH2ÜN02 -CH2ON02 I 1 ON02 HNO3 ** Oxirane I I ON02 OH The nitration of the hydroxyl group is exothermic.DSTO-TR-0966 Monomer purity is vital for the polymerization step and care must also be taken to control reaction conditions to minimise ring-opening nitration. This problem has been overcome by nitrating in a continuous flow reactor followed by quenching with aqueous sodium carbonate solution [52]. epoxidising hydroxy-terminated polybutadiene and then nitrating with dinitrogen pentoxide [53]. and long addition times are required to control the exotherm. The nitration of HTPB has been carried out by two reaction pathways. In addition.

low Tg and is readily cured by isocyanates.66 -58 150 Fairly stable Out of range 128 19 . poise 8000 3000 2. Thus a level of nitration corresponding to 10% nitration on the polymer backbone will give a good compromise between energy output. Some typical properties of nitrated hydroxy-terminated polybutadiene at 10% nitration levels are given in Table 6. mechanical properties and miscibility with energetic plasticisers.DSTO-TR-0966 orv^?H H Epoxidation CH3COOH / CH2CI2 rv^rK^M:0H Ho Nitration ON02 ON02 NHTPB It has been observed that the level of nitration in the final polymer affects the thermal stability and mechanical properties. Table 6: Properties of NHTPB [37] Mw Mn Mw/M„ Tg (DSC). °C Stability (Vacuum Stability Test) Impact Sensitivity (Rotter Test) Viscosity @ 30°C. NHTPB has low viscosity. °C Onset of decomposition (DSC @ 5°C/min). At this low level of nitration (10-15%) the glass transition temperature is kept low (<-50°C) with complete miscibility in most energetic plasticisers.

although information in the open literature is scarce. N02 F X N02 F C—CH2-0—CH2—C—CH2-0—CH2—C NO. I X I N02 I 20 .6 Fluorinated Polymers Fluorinated polymers offer intrinsic advantages over inert hydrocarbons such as HTPB. The application of these functional groupings is illustrated in the structurally related SYEP and FDNA molecules. In addition to fluorine itself. In an US Patent. Adolph [55] describes an energetic binder comprising: HO-CH2(CF2)nCH2[OCH2OCH2(CF2)nCH2]m-OH which is a hydroxy terminated polyfluoroformal prepolymer with molecular weight between 1. although the univalent fluorine is half as effective as divalent oxygen in providing a stoichiometric combustion balance [57]. HOCH2(CF2)nCH2OH H+ *HOCH2((CF2)nCH2OCH2o)nH + H20 Various chain lengths have been prepared to give polymers with low Tg and find use as copolymers with other low Tg monomers. several functional groups have been considered as explosophores.2-dinitroethyl)formal. One of the main types of fluorinated polymers are the polyformals. Molecules with a single difluoroamine group tend to be sensitive and unstable. The difluoroamine group is also a potent oxidizing functional group. The composition is cast-cured with polyisocyanates to give rubber-like polymers. and this has been attributed to lability of the a-hydrogens. again enhancing performance. including the fluorodinitroethyl and difluoramine groups. geminal bis(difluoramines) are typically less sensitive and more stable [56]. Fluorocarbons have higher densities which results in formulations with higher densities and inherently higher performance. Polyformals are synthesised by the reaction of dihydric alcohols with formaldehdye to yield hydroxyterminated polymers. A general reaction scheme for the production of polyformals is shown below [54]. The novelty of this patent lies in the use of fluorinated polymers/plasticisers to form HMX-containing PBXs of the same energy (detonation pressure) as conventional nitrated polymers/plasticisers with HMX.DSTO-TR-0966 2. both prepared by Fluorochem [58].[59]. The increased compatibility of the prepolymer with fluorinated plasticisers is due to the presence of the formal moieties in the polymer backbone. Furthermore.000 and 10. replacement of hydrogen (a fuel) on the polymer backbone with fluorine (an oxidant) increases the overall oxygen balance of the composition. and a compatible energetic plasticiser such as bis(2-fluoro2.000. Secondly. The fluorinated polymers are believed to possess greater chemical and thermal stability than the polynitro polymers. diflouroamine groups are relatively sensitive to impact.

05 158 Typically. The measured impact sensitivity of SYEP is slightly higher. which is prepared by direct fluorination of aqueous urea [61]. In addition.691 -2.75 141 FDNA (X = NO2) 1. kbar Impact Sensitivity.9 273. Copolymers are typically vinylidene fluoride and hexafluoropropylene.5 264. although caution must be exercised in any comparison of liquids with solids. fluorinated copolymers used in PBXs allow for processing methods such as ram extrusion and compression moulding without the loss of performance.N-difluorourea.640 21 254. Difluoramine is generated in-situ by acid hydrolysis of N. °C Specific Impulse. H F -ix «- CF.1 Fluorinated Copolymers Copolymers of fluorinated polymers have found uses as inert binders with high densities for energetic compositions for the last 30 years. known commercially as Viton A (DuPont).5 249. fluorinated polymers can be synthesized readily and incorporated into PBX systems to boost energy output. but has a slightly increased density and enhanced specific impulse and detonation pressure. g/cm3 Melting point. Absence of side 21 . SYEP has a lower melting point and a slightly lower oxygen balance than FDNA. A major disadvantage with these copolymers is the use of flammable solvents to process these copolymers with energetic ingredients. Recent advances made in the synthesis of dense. It is deemed an environmental and safety issue to remove such flammable solvents from energetic processing towards a solvent-free processing energetic system. cyclic energetic materials can also be applied to polymers. cm/2. In this manner. F -y Copolymer of vinylidene fluoride/hexafluoropropylene Such copolymers give high densities concomitant with high fluoride content and good thermal stability. Adolph and Cason-Smith [62] have prepared randomly distributed copolymers of polynitrofluoroformals via the polycondensation of nitraminediols and fluorodiols with formaldehyde in sulpholane/boron trifluoride etherate solvent.6. s Detonation Pressure.5 kg SYEP (X = NF2) 1.DSTO-TR-0966 Density. 2. The introduction of bis-(difluoramine) groups onto polymer backbones can now be made possible by the reaction of carbonyl compounds with difluoroamine in fuming sulphuric acid (difluorosulphamic acid) [60].

DSTO-TR-0966 reactions in the propagation and termination steps of the reaction results in polymers that are nearly 100% difunctional and terminated by fluorodiol monomer hydroxy groups (ideal for block copolymer synthesis and reproducible curing).e. A general scheme for the production of polynitrofluoroformals is given by [63]: RC(N02)2CH(R')OH CHoO H so » RC(N02)2CH(R')OCH2OCH(R')C(N02)2R R = F. toughness and softening point (Tg point). This is achieved by softening the polymer matrix and making it more flexible. These roles include a reduction of mix viscosity to ease processing. CH3. and in the case of propellants. bum rate modification to tailor ballistics. Manser at Thiokol has found that copolymers comprised of difluoroamino and AMMO or BAMO monomers. To fulfil these roles. R'= H or R = F. such as: • • • • a positive influence on safety and performance a positive influence on mechanical properties chemical and physical compatibility with all ingredients chemical stability and absence of toxicity 22 . modification of oxygen balance and energy content. In addition to improving properties such as tensile strength. elongation. which if present would cause the polymer to decompose to hydrofluoric acid. 3. and this is believed to be due to the presence of the difluoroamine group [56]. R' = CH3 The crude copolyformal product contains unstable terminal hemiformal groups (CH2OCH2OH) as well as labile cUnitramine-derived terminal hydroxy groups. Energetic Plasticisers The primary role of energetic plasticisers in energetic material formulations is to modify the mechanical properties of the charge to improve safety characteristics. the plasticiser can have secondary roles. have better thermal properties than the polymer (i. N02. lower Tg). thereby reducing the thermal stability of the copolymer. The carbon atom connected to the difluoroamino group does not contain a hydrogen atom. plasticisers require certain characteristics. Removal of these groups to leave only the stable fluorodiol-terminated groups is accomplished by treating the mixture with hydrogen peroxide (30%). OH' ► RCH2OH + CH20 HoOo RCH2OCH2OH » HCOOH Recent advances in oxetane polymers have focussed on difluoramino oxetane copolymers/ although the synthesis is rather cumbersome and costly at present [56].

1 Nitrate Ester Plasticisers The first energetic plasticiser for commercial explosives . 3. triethyleneglycol 23 . In addition. plasticisers are typically oligomeric materials that have number average molecular weights ranging from 200 to 2000. but they are highly volatile and tend to migrate out of a formulation readily (exudation). nitroglycerine is a sensitive explosive easily initiated by friction and impact. Those with molecular weights below 200 may be more effective in reducing Tg. with properties more akin to the polymer matrix. NG exhibits significant physiological effects. Plasticisers with molecular weights above 2000 tend to be viscous. nitroglycerine still remains an effective plasticiser for many applications. When heated above 200°C it will explode. The nitrate esters have proved to be a fertile source of energetic plasticisers and a complete review is beyond the scope of this report.acetyl triethyl citrate.DSTO-TR-0966 • • • absence of volatility and exudation (migration) low environmental impact availability and affordability. diethyl adipate. by using low molecular weight oligomers of the polymer matrix as the plasticiser. and hence miscibility. while upon storage it proves unstable at temperatures exceeding 70-80°C [65]. Similar improvements in mechanical properties are desired from energetic plasticisers. Nevertheless. but degrade the output of the formulation by reduction of the overall oxygen balance. Non-energetic plasticisers are effective in improving mechanical properties. Number average molecular weights of plasticisers between 400 to 1000 are considered to give optimum plasticising effect. causing dilation of the arteries and severe headaches.is a high performance nitrate ester having the following structure: CH2ON02 CHONOg CH2ON02 Nitroglycerine I First discovered in 1846. A promising recent approach has been to increase the structural similarity. but with a contribution to the oxygen balance and/or energy of the formulation. Some of the major nitrate esters in use today include trimethylol ethane trinitrate (MTN or TMETN). Examples of non-energetic plasticisers include the esters . By their own nature. Like their polymeric counterparts.nitroglycerine (NG) or glycerol trinitrate . however one of the most common problems has been exudation . Energetic plasticisers are typically nitro compounds or nitrate esters. plasticisers can be inert (non-energetic) or energetic [64]. diethyl sebacate and dioctyl adipate.migration of the volatile low molecular weight plasticiser to (and from) the surface of the formulation. Structural similarity with the energetic polymer should facilitate incorporation.

2-dinitropropyl)acetal (BDNPA) and bis(2. and butanetriol trinitrate (BTTN). US Army applications such as the M900 tank program. The formal is a solid. 3.1 explosives that possess low critical diameters.CHP CH2ON02 CH2ON02 CH2 CH2ON02 CH2ON02 < CH2 CH2ON02 CH. I MTN or TMETN is chemically stable. making them difficult to handle. ON02 i2 / MTNorTMETN CH2 CH2ON02 TEGDN EGDN BTTN . BDNPA/F plasticisers are typically 50/50 mixtures. slightly less energetic than the liquid acetal and is used to form an eutectic to lower the melting 24 . BDNPA/F NO. has more energy but is also sensitive to impact. It possesses a lower density and a greater volatility than NG. PBXN-106 used to fill the US Navy 5"54 gun also contains BDNPA/F [66]. most of these molecules possess some of NG's properties without the severe hazards of NG. they were developed to replace this material. EGDN is a more efficient plasticiser of NC than NG. ethyleneglycol dinitrate (EGDN or nitroglycol). / (CH3CCH20)2CH2 NO. CH2ON02 CH2ON02 H3C -uor 2ON02 CCH CH. high volatility and high sensitivity. Being structurally similar to NG. For example.DSTO-TR-0966 dinitrate (TEGDN). insoluble in water and has low volatility.2 BDNPA/F Plasticisers Plasticisers composed of bis(2.2dinitropropyl)formal (BDNPF) have found widespread application in energetic formulations. TEGDN is also chemically stable and has less impact sensitivity than NG and is less volatile than EGDN. BTTN is often used in propellants as a replacement for NG. Most of the energetic nitrate esters are HD 1. (CH3CCH20)2CHCH3 NO. LOVA gun propellant and the insensitive HMX-based explosive PAX-2A all use BDNPA/F as an energetic plasticiser. NO. It has a lower density than NG but offers improved stability.

5-3. By replacing chlorinated solvents with MTBE (methyl-terf-butyl ether). Table 7: Properties of GAP Plasticisers [11] Properties AHf. The nitration is also now carried out with inexpensive persulphate salts as the oxidant with a catalytic amount of potassium ferricyanide. The synthesis of low molecular weight azido polymers such as GAP plasticisers can be achieved in a single process involving azide displacement of chlorine from epichlorohydrin monomer. BDNPA/F was first developed by oxidative nitration of nitroethane to 2.0 >3 -45 25 . ECH.DSTO-TR-0966 point (making plasticiser useable at lower temperatures) [67]. 100°C (cm3). mg/L Tg.29 light yellow liquid >900 2. cal/g Density. BDNPA/F may become unstable under severe conditions.°C GAP Diol +280 1. Furthermore. the process has now been made environmentally friendly. 3.0 >3 -45 GAP Triol 1. TMETN. This nitration process was uneconomical because of problems with waste and loss of silver (-1%) and was modified further to include a selective chlorination step of nitroethane to 1-chloronitroethane. Properties of GAP diol and triol plasticisers are given in Table 7 below. as are nitrate esters such as butanetriol trinitrate. 200h. K3Fe(CN)6 Na2S208 -jq^JQ *" CH3CH(N02)2 NaOH/CH20 CH3CH2N02 CH3C(N02)2CH2OH DNPOH ^ BDNPA/F BDNPA/F exhibits poor plasticising properties in terms of lowering Tg and viscosity of uncured PBX formulations. followed by polymerisation without the need for a catalyst [70]. GAP plasticisers are compatible with GAP polymer.29 light yellow liquid 1700 ±300 2. Furthermore. g/cm3 Colour Mn Functionality Thermal Stability. such as a combination of elevated temperatures (>74°C) and high shock loading (#8 blasting cap with 33 g composition C-4 booster) [69]. BTTN and trimethylol ethane trinitrate.3 Azido Plasticisers The poor mechanical properties of azide functional polymers like GAP can be improved markedly by incorporation of energetic azido functional plasticisers. the synthesis of BDNPA/F is now automated and run continuously to give high output of product [68].2-dinitropropanol (DNPOH) with silver nitrate as catalyst [66].

200h.DSTO-TR-0966 As a general rule. Properties are given in Table 9. cal/g Density. namely ethylene glycol bis(azidoacetate) (EGBAA).1 Miscellaneous Azido Plasticisers A new class of energetic plasticisers based on azido-acetate esters have recently been reported as giving binders with low Tg.27 light yellow 700-900 <3 N3CH2CH20[CH5-CH—0-]nCH2CHN3 CH2N3 CH2N3 GAPA -56 3.°C + 550 1.N- X V \ TMNTA N3H2COCOH2C- -CH2OCOCH2N3 CH2OCOCH2N3 PETKAA 26 . Table 8: Properties of Azido-Terminated GAP Plasticiser (GAPA) [11] AHf. Ampleman [71] developed the synthesis of an azide terminated glycidyl azide plasticiser (GAPA). mg/L Tg. trimethylol nitromethane tris(azidoacetate) (TMNTA). With this in mind. good thermal stability and compatibility [72]. g/cm3 Colour M„ Thermal Stability 100°C (cm3). GAPA is a pale yellow liquid with low molecular weight. a plasticiser having no reactive terminal hydroxyl groups available for isocyanate cure. Four new compounds have been described. diethyleneglycol bis(azidoacetate) (DEGBAA). plasticising effect will be lost if terminal hydroxyl groups on the plasticiser react with the isocyanate crosslinking agent. /W\ EGBAA DEGBAA CH20COCH2N3 0. pentaerythritol tetrakis (azidoacetate) (PETKAA).3. effectively tying the plasticiser into the cross linked polymer matrix. low Tg and good stability.

25 16 192 PETKAA 1.4 K10 Plasticiser K10.39 88. yellow/orange liquid with an UK hazards classification of 6. Nm Friction sensitivity.5 165 DEGBAA 1.95 -230. °C. Deflagration point.2 2880 -35. mPas Tg. K10 is manufactured by Royal Ordnance in the UK.54 1288 -34.82 -215.9 5. . (5K/min) Weight loss.NOz 02N.°C Stab. (90°C @ ca. g/cm3 O2 balance. and finds use as an energetic plasticiser in polymer bonded explosives. Compatibility issues with K10 include sensitivity to lead azide and other primary explosives. Props. 3.4 234 60 360 The new plasticiser (EGBAA) has been combined with polyNIMMO at 50% plasticiser loading to give a rubber with a Tg of -66. NENAs contain both nitrate ester and nitramine functionalities. N02 K10 3. is a nitroaromatic plasticiser consisting of a mixture of 2.5 Nitrato Ethyl Nitramine Plasticisers (NENA) The rdtratoemylrdtramine family (NENAs) are effective plasticisers in energetic formulations.45 -71.00 -99.15 -167.4 -70.92 -328.4-dinitroethylbenzene and 2. K10 is a clear.3 235 0.8 232 0. . Prop. N EGBAA 1. also known as Rowanite 8001. particularly in nitrocellulosic systems. kj/mol Viscosity.4. %) Impact sensitivity.1 (toxic).48 >10 160 TMNTA 1. Density.7°C with good stability [72]. and have the following structure: RN(N02)CH2CH2ON02 27 .86 29.34 -84.DSTO-TR-0966 Table 9: Physical and Stability Properties ofAzido Plasticisers [72] Phys. % AHf.2 -63. 80 days.6-trinitroethylbenzene (65%/35%).1 214 0.36 23.

264 -2 -87. NENAs are readily manufactured by nitration of commercially available alkyl ethanolamines.1 1. butyl. While offering excellent initial plasticising effects. they are low molecular weight materials that are volatile and migrate readily from the polymeric binder system [77]. is often considered with the NENAs). °C AH.1 1. or DANPE. propellant formulations containing NENAs have difficulty achieving 10-year service life [78].1 1.. p. Consequently. in high yields (80%). propyl. It was not until the late 1970s where researchers at Eglin AFB used NENAs in gun propellants that required low flame temperatures and low molecular weight [75]. where DINA (dinitroxy ethyl nitramine) was scaled-up for use in Navy flashless gun propellants [73].211 -27 to -28 -104. Table 10: NENA Properties [77] MeNENA Molecular Wt.53 38-40 -43. NENAs possess good thermal stability. kj/mol 165.178 -8 to -5 -119.[75]. generate low molecular weight combustion gases.0 210 259 PentylNENA 221.0 210 503 BuNENA 207. g/cm3 m.0 210 784 PrNENA 193. NO 2 *RNCH2CH2ON02 RNHCH2CH2OH 98% HN03 -H20 The use of NENAs as plasticisers in gun and rocket propellants confer excellent properties such as high burning rates. Trifunctional polyNIMMO and BuNENA plasticiser in a 1:1 ratio gives 28 . Important properties are listed in Table 10. On the other hand.DSTO-TR-0966 Typical NENA derivatives in use include (R=) methyl.2 1.5-diazido-3-nitrazapentane. recent research on polyNIMMO and polyGLYN binders has shown that BuNENA significantly decreases glass transition temperature without plasticiser migration [79]. °C O2 balance DSC exotherm.p.[74]. and pentyl (the structurally related l. iso-propyl.1 47 One of the main disadvantages of NENAs as plasticisers is migration from compositions on standing or on long-term aging. The NENAs have been known since the 1940s.6 218 1113 EtNENA 179.2 1.32 1-5 -67. and give good impact sensitivity [77]. ethyl. readily plasticise nitrocellulose and other polymers. reductions in flame temperature and product gas molecular weight. and higher specific impulse (based on moderate loadings of 6070% RDX in a nitrocellulose/NENA binder) [76].

Melting point and glass transition temperature are clearly the most critical criteria.6 Oxetane Plasticisers Migration of the plasticiser is one of the major problems encountered with the use of energetic binder systems for explosive and propellant formulations. hopefully. but other important considerations include energy balance. A cyclic tetramer of NIMMO was prepared at DERA. [80] have shown that NENA plasticisers are better than BDNPA/F at reducing the viscosity and Tg of polyNIMMO cured rubbers. In order to remove the terminal hydroxy groups. 3. Linear NIMMO oligomers (polymers consisting of between 1-10 monomer units) were therefore prepared for use as plasticisers in polyNTMMO binder systems. Neither have proved as effective for NENAs. A recent approach has been to design plasticisers that resemble even more closely the polymer matrix. This compound. Nitration with excess N2O5 also converts residual NIMMO monomer into TMETN. Campbell et al. has a relatively high Tg and is not an effective plasticiser. oligomeric NIMMO has been further nitrated (nitration also increases the oxygen balance and enhances the energy of the binder system). which is also present in commercial polyNTMMO (5-10%). The authors suggest the use of alkyl ureas as effective stabilisers for NENAs when used in combination with AP [81]. Separation of the TMETN and isolation of purified nitrato oligomers is currently in progress at DERA [82]. One disadvantage of NENA plasticisers is a potential incompatibility with ammonium perchlorate [81]. 04—H /n >3molN2Q5 ^ CH2CI2 o2NO_(_/ \ 0-}-N02 ON02 ON02 ON02 TMETN 29 . minimising migration. and prevent unwanted reaction with the isocyanate crosslinking agent.DSTO-TR-0966 a binder system having a Tg of -61°C. Oligomeric NTMMO has a lower Tg than the cyclic tetramer but still contains NIMMO monomer. In the past such ammonium perchlorate and nitrate esters issues have been resolved by the inclusion of free radical scavengers (2-nitrodiphenylamine or alkaline additives such as sodium bicarbonate). enhancing physical and chemical compatibility and. ON02 QNO. Nitration with N2O5 for 30 minutes at -10°C gave clean conversion to nitrato terminated oligomers without sign of chain scission. energy content and safety.

g/cm3 1. As with the NIMMO oligomer. ON02 ON02 "GLYN Dimer" The linear "GLYN dimer" molecule is significantly smaller than polyGLYN. "GLYN dimer" is normally a mixture of oligomers and has a low Tg (-64.°C -64. The use of energetic binder systems is a promising means of enhancing the output of cast cured polymer-bonded explosives and cast composite rocket propellants.DSTO-TR-0966 3.38 %Hso. Table 11: "GLYN Dimer" Properties [83] Tg. Initial studies of polyGLYN with "GLYN dimer" as plasticiser have produced well-cured binders with good mechanical properties. then IM-compliant high performance explosives and propellants should be possible.9 Density. nitration both increases oxygen balance and energy content. and in advanced minimum smoke rocket propellants. and is prepared by end capping a 1. and prevents unwanted reaction of the plasticiser with the isocyanate crosslinking agent. BuNENA and BDNPA/F. This technology shows promise for use in high performance cast cured explosives for volume constrained and metal accelerating applications.m/s 6900 Pcj. Conversely. 4. a derivative of glycidyl nitrate described as "GLYN dimer" has been prepared at DERA for plasticisation of polyether binder systems such as polyGLYN and polyNIMMO. kcal/mol -188. and then nitrating the terminal hydroxy groups [83]. 2.1 TofI.7 AHf.7 GLYN Dimer Plasticiser In a similar fashion.GPa 17. Conclusions and Recommendations 1.4-butanediol spacer unit with GLYN. the use of energetic 30 . If energetic binders can be made to replicate the mechanical properties of inert binder systems such as those based on HTPB. °C 167 VoD.9°C).6 "GLYN dimer" also has a calculated explosive performance superior to K10. and impact sensitivity compared with nitrate esters such as BTTN and TMETN. Some important properties are listed in Table 11. It is anticipated that the "GLYN dimer" will be less susceptible to migration than the more conventional plasticisers. cm 18.

The mechanical properties of these compositions and their response on generic IM-tests must then be investigated. The cost of polyNIMMO and polyGLYN is currently high. The DSTO programme will therefore be based on these polymers. where the nitrato group contributes to both the energy and the oxygen balance of the formulation. PolyGLYN is currently the most energetic polymer available. The most practical short-term solution appears to be for DSTO to use the nitroaromatic plasticiser K10 manufactured by RO and employed by researchers at DERA. Following initial characterisation of successful binder systems.DSTO-TR-0966 binder systems may allow the performance of a composition to be maintained while the level of energetic (and sensitive) nitramine solid is reduced. DSTO research should address the explosive performance of PBX's composed of solid nitramines suspended in a matrix of energetic binder. although the polyNIMMO technology is more mature. AMMO and BAMO are effective as the polymer matrix in rocket propellants. it may be sensible to conduct initial research on RDX analogues. targeting Octol-like performance. It is therefore appropriate for DSTO to conduct research and development to explore this technology for future generations of energetic material compositions to address the evolving needs of the ADF. Likely candidates are high solids loading HMX-based PBX's. aiming at cast-cured PBX's with the performance of Composition B. it is appropriate at this point in time for DSTO to conduct its research using commercially available ingredients. While fluorocarbons find use as binders/desensitisers in pressed explosives. The most promising energetic plasticisers for use with nitrato substituted polyethers appear to be the NIMMO oligomers and "GLYN dimer". rather than developing its own. 31 . Most effective use of energetic polymers will be achieved by inclusion of energetic plasticisers to modify the mechanical properties. although these materials are not yet fully charaterised. Pragmatically. while ICI Explosives is supplying research quantities of polyNIMMO and polyGLYN. Given the available level of effort. and immediate application is likely to be restricted to high performance cast-cured metal accelerating explosives. nor are they commercially available. The US nitrato oxetanes are not currently available. and azido-substituted polymers such as GAP. the most promising polymers for application in explosives are isocyanate-cured nitrato-substituted polyethers. offering an alternative approach to the formulation of IM-compliant energetic materials.

Energetic Hydroxy Terminated Azide Polymer. 2.B. Explos. Yamamoto.E. T. A. Karlsruhe.C. Millar..R. Finck.A.686. M. Mishra. E. Prop. D. N. LA. 13. W. M. C. (1984). European Patent 0 296 310.E. D. US Patent 4 486 3351. D. E. Energetic Azido Curing Agents. New Orleans. 5.O. 8.H. 3.E. Conf. Woolery. Germany. Polymer. 8. (1996). Ampleman.... and Graindorge. Grant. JANNAF Propulsion Meeting. John Hopkins University Chemical Propulsion Information Agency. (1988).F..172. J..W. 32 . Kubota.L. Aqueous Process for the Quantitative Conversion of Polyepichlorohydrin to Glycidyl Azide Polymer. HJ. Conf.J. /. (1984). Rodgers.... H. Desai. GAP-TAGN-PEG Propellant-Part 1 . Germany. Witucki. Synthesis of a New Class of Glycidyl Azide Polymers.. Karlsruhe. (3). Shimizu. Use of Polymeric Ethylene Oxides in the Preparation of Glycidyl Azide Polymer.. 4. 560. Power. Ann. E. /. LB.. (15).K. H.. Power.O. pp 153-182. A.B. R.R... New Molecules for High Energy Materials. Frankel. (1981). Frauhofer Institut für Chemische Technologie. 27th Int.J. Kubota. Prop. (1983). R. (1983). Bull. US Patent 3 645 917. Burning Rate Characteristics of GAP Propellants. ICT.. Frankel. H.. E. and Hanagan. N. oflCT. 13. US Patent 4 379 903. Mehrotra-Dev. 12. 37. A. Paul. A. B. US Patent 5 256 804. Frankel. 7. 3471-3476. Amass. Historical Development of Glycidyl Azide Polymer. Propellant Binders Cure Catalyst. 6. 27th Int.II. Prop. I. (1996). M. Rickenbaugh. Vandenburg. References 1. US Patent 4 379 894.. US Patent 4 268 450. 10..J. Ann.. Marshall.J..J. G. (1992). 15. Sonobe. New York. An Investigation into PolyGLYN Cure Stability. (1972). Stewart. Vol. Woolery.DSTO-TR-0966 5. Pergamon Press.co-hydroxy telechelic poly(glycidyl nitrate) and estimation of theoretical heat of explosion. M. (1996). Fraunhofer Institut für Chemische Technologie. M.B. T.B. Wilson. Ashmore. N. Combustion Mechanism of Azide Polymer. (1990). Cunliffe..B. Frankel. Urbanski.V. J. 6. 99-1.. Reed. Pyro. (1984). Chemistry and Technology of Explosives. (1988). Earl. 9. Polymers Containing Azidomethyl Side Chains. Flanagan.. 14.Study of Ingredients Vol. R. Synthesis of narrow molecular weight cc.. Jr. (1990). M. 23-1. Leeming. IV. 11.

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554-560. Indian Chem. 40. pp 79-91. Goldwasser. Royal Society of Chemistry. Polymers for Adv. (1981). (1995). T. McGonigle.M. Redecker. S. Fraunhofer Institut für Chemische Technologie. R.V. Cunliffe.E. Desai. Pyro. (1993).. J.G. ]. Mat. (1991). Sei. (1994). Colclough. Desai. Polyvinylnitrat . Germany. 46.. Honey. (1976)...F. Cambridge. (1).. Nitramine Containing Polyether Polymers and a Process for the Preparation Thereof. Bunyan. Ann. 55. Nitrations by Dinitrogen Pentoxide (N205): A Versatile and Efficient Methodology for the Production of Energetic Materials. 5. (1993). P. and Hani. H. Paul. A. P.... J.H. 43. Millar. Hohn.H. 35 . Torry. Fawcett. 42.R... Sanderson... M.. Conf.A. (1997). H. Stewart. A Novel ThermoReversible Rubber.J.W. Russell.C. Explosives in the Service of Man. R.C. p 105-111. (1993). 45. S. M. Explos. Backof. 48. and Amanulla. Uth Int. R. Id. N.239.C.D. Symp. M.. (1996). Energetic Polymers as Binders in Composite Propellants and Explosives. 16. Day. (1999). Nitrated Hydroxy-Terminated Polybutadiene (NHTPB) a New Energetic Binder. Prepr. New Directions in Energetic Materials. Boileau. dimming. 418. Overview on Energetic Polymers. H. (1989). Dolan.. N. Colclough. R. S. Karlsruhe. J.E.DSTO-TR-0966 41. 319. and Hagel. B. Def. Conf. P..R.196. Res. (1996). 56. E. M. 6-9th October.. N. E.E.W. Soc.N'Aliphatic Dicarboxylbis(hydrazones). Synthesis and Chararcterisation of N. 5-1.A. 52. Proc. P. US Patent 5 319 068. Tech.. Orlando. Golding. Energetic Binders for Plastic Bonded Explosives. 67-84. 47. New Energetic Epoxy Binders. 44.. Polym.. 49. Paul... Karlsruhe. R. and Vanderame. F. A.W. Jain. R. S..A. G. 24th Int. 12th Int. K. S. Golding.. Stewart.. Modern Explosives and Nitration Techniques... W. Difluoramino Oxetanes and Polymers Formed therefrom for use in Energetic Formulations.S. 36B.. (3). Jain. Symp.. 50.. Millar. 54. and Paul.. US Patent 3 965 081. Soc. Res. Paul.. A. 687. Colclough. A. Prop. ICT. Proc. US Patent 4 988 397.. Manser. 232-233. H.. E. Clements..Eine Komponente fur Treib. Pyrotechnics Seminar...und Explosivstoff. Ann. l-3rd July. 12. (1997). and Amanulla. and Archibald. 51... (1997). Bull. Adolph. Mat. Strecker. Germany. US Patent 5 272 249. 53. S. p 91. Insensitive Munitions and Energetic Materials Technology Symposium. Lawrence. and Langer. E. FL. Stability Studies on End-Modified polyGLYN. 1. (1987). Fraunhofer Institut für Chemische Technologie.. N. NDIA. M.E. Materials Research Society. 418.

66. I. Grakauskas. Khosrowshahi.. Ann. Ampleman.R. (1991). Insensitive Munitions Technology Symposium. (1970). (1999).. Direct Fluorination of Ureas. Shipp. Messmer. Pyro. D. S. N. 63. (1986). Synthesis and Characterization of Azido Plasticizer. US Patent 5 124 463. Damavarapu. Am. Fluorochem Inc. Chem. V.. Vol.D. (1989). Azusa.. Energetic Materials. R. Hamilton. Chem. CA. High Explosives and Propellants. NWCTP6720. ONR9-1.G. S. 67. Conf ICT. Nair. M. Pergamon Press: Oxford.E. Schmid. R. T. Bis(2-Azido Ethyl) Adipate Plasticizer: Synthesis and Characterisation. David.. ONR-7-1 Contract No. 71. H. M. Fordham.. (1966). Direct Conversion of Epichlorohydrin to Glycidyl Azide Polymer. Drees. 64. H.853-56. R. 11. B.. Am.. Fraunhofer Institut für Chemsiche Technologie. Aerojet... Baum. Acetal Preparation in Sulfuric Acid. J. Federal Republic of Germany. 60. Soc. /.. K. T. 6-9th June. Adolph. /.. 92. 62.S. (1994). 70. US Patent 4 997 499. and Hill. (1993). (USA).. and Baum.K. K. 61. Reactions of Carbonyl Compounds with Difluoramine. Org.DSTO-TR-0966 57. 39-1.P.. Merrill. N00014-89-C-0215. Contract No. Karlsruhe. D. Research in Energetic Compounds.. Soc. K. 7083-89. A. Bis(dinitropropyl)formal/dinitrobutyl Dinitropropyl Formal Plasticizer. D. /.159-162. V. E. Mancini. Baum. Energetic Polymer. American Defense Preparedness Association. J. Agrawal. Bhongle.. K. 90. Handbook of Energetic Polymers and Plasticizers.A.. An Environmentally Favorable Continuous Process for the Synthesis of BDNPA/F. Technologie. Nguyen. Azusa. Novel Approaches to the Synthesis of Fluorodinitromethane and Fluorvdinitroethanol. Fluorochem Inc.. 2096-100. (1966). VA.. 58. Löffel. Expl. 72. Lovatob.... NWC.M. 65. 59. K. Chapman. (7). (1986).G. M. CA. US Patent 5 266 675. K.G. Ahad. G. J. US Patent 4 891 438.. Fraunhofer Institut für Chemsiche... J. 30th Int..67.. Fraunhofer Institut für Chemsiche(s): Technologie. 31. K. N00014-88-C-0536.. Archibald.. New Approach to BDNPA/F. Geslin. Baum.M.K. R. Archibald. (1999). M.. Chem. Adolph. Synthesis of a Diazido Teminated Energetic Plasticizer. (1990). Rhein. Baum. 69. and Cason-Smith. /. (1990).G. Prop. F. (1993). D.. 24. Mezger. 36 . Wardle. Material Safety Data Sheet. (1992). 68.G..

5-7 October.J. TTCP. A. M. 76. D.J. Characterisation of PolyNTMMO and PolyGLYN Energetic Binders. Stability and Performance Characteristics of NENA Materials and Formulations.. 10-1. Fraunhofer Institut für Chemische Technologie. and Chute. Joint International Symposium on Energetic Materials Technology. Conf. VA. (1994). Salisbury.. Johnson. Colclough. ICT. 78. R. NATO. (1994).L. 6-9fh June. Ann. Nitramines and Their Preparation.. NMIC-S-275-94. DSTO. Cunliffe.. Germany. (1997). Cumming. Mullay.F. N. Karlsruhe. Brussels. }.DSTO-TR-0966 73. New Orleans.. New Energetic Plasticizers. (1994). 74. SA. E. R. US Patent 2 462 052. (1999). Wright. and Garaty. G. Focus Area Report for Propellants and Explosives.. Johnson. Ann. 37 . 25th Int. Chauhan. Belgium. DSTO-TR-0884.. A. W. TTCP. PolyGLYN Binder Studies and PBX Formulation: Technical Achievements from a UTA to DERA Fort Halstead. Germany. US Patent 2 461 582. R. Norman. Campbell. Simmons. Tampa..J. Insensitive Munitions Symposium Technology. American Defense Preparedness Association. Insensitive Munitions & Energetic Materials Technology Symposium. Wright.. B. FL. (1997).E. 25th Int. 77. R. G. 70-1. (1992). NDIA. NDIA. 79. NENAs . and Mullay. P. International Symposium on Energetic Materials Technology. Conf. Energetic Materials and Propulsion Technology.. Karlsruhe. 81. 405411.L. (1994). 21-24th March. Cliff. A. Development of Insensitive Rocket Propellants Based on Ammonium Nitrate and PolyNIMMO.. W. Method of Converting Secondary Amines to Nitramines.. LA. 22nd meeting... 6-9th October. 83.A. 75. J.. 82. Marshall. (1949). Orlando.V. W-4.J. Flower.F. Simmons.S. Thermochemistry of NENA Plasticizers. (1994). American Defense Preparedness Association. (1949). Thermal Stability of Stabilized NENA/AP Mixtures. and Chute. FL.V. 229-239. Fraunhofer Institut für Chemische Technologie.New Energetic Plasticizers. p 112. ICT. J. Cumming. M.S. 80.

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will also be reviewed. NO. This general document outlines the most promising energetic polymers and plasticisers being considered today. polyGLYN. ABSTRACT In an effort to comply with Insensitive Munitions (IM) criteria. DSTO NUMBER DSTO-TR-0966 8. NO. AR NUMBER AR-011-428 9. TYPE OF REPORT Technical Report 10. plasticizers. the review will recommend binder systems for DSTO's future energetic binder programs. SECONDARY RELEASE STATEMENT OF THIS DOCUMENT 14.au/corporate/reports/DSTO-TR0966. poly(3nitratomethyl-3-methyloxetane). Once cured. energetic materials. as well as a variety of nitrate esters. rocket propellants. DOCUMENT DATE April 2000 12. URL on World Wide Web http://www. DELIBERATE ANNOUNCEMENT No Limitation 17. GAP. CORPORATE AUTHOR Aeronautical and Maritime Research Laboratory PO Box 4331 Melbourne Vic 3001 Australia (U) (U) (U) 4. polyNIMMO and poly(glycidyl nitrate). FO BOX 1500.gov.pdf 15. CASUAL ANNOUNCEMENT 18. AUTHOR(S) Arthur Provatas 6a. nitroaromatics and azido plasticisers. TITLE Energetic Polymers and Plasticisers for Explosive Formulations A Review of Recent Advances 1. PRIVACY MARKING/CAVEAT (OF DOCUMENT) 3. Page classification: UNCLASSIFIED . TASK SPONSOR DSTO 11. FILE NUMBER J9505/17/202 6b.Page classification: UNCLASSIFIED DEFENCE SCIENCE AND TECHNOLOGY ORGANISATION DOCUMENT CONTROL DATA 2. Weapons Systems Division Approved for Public Release OVERSEAS ENQUIRIES OUTSIDE STATED LIMITATIONS SHOULD BE REFERRED THROUGH DOCUMENT EXCHANGE. DEFTEST DESCRIPTORS Yes Energetic binders. Energetic binders can be considered as cross-linked polymers that provide a matrix to bind explosive ingredients together with a plasticiser. TASK NUMBER 98/077 6c. the polymeric binder is a tough elastomeric rubber capable of absorbing and dissipating energy from hazardous stimuli. lending itself well to IM applications. although several other energetic polymers will also be reviewed. RELEASE AUTHORITY Chief. Energetic plasticisers including oligomers (low molecular weight) of the polymers mentioned above. SA 5108 16.defence. SECURITY CLASSIFICATION (FOR UNCLASSIFIED REPORTS THAT ARE LIMITED RELEASE USE (L) NEXT TO DOCUMENT CLASSIFICATION) Document Title Abstract 5.dsto. polymer bonded explosives. OF PAGES 42 7. Finally. SALISBURY. Attention is focussed on several energetic polymers including glycidyl azide polymer. OF REFERENCES 83 13. insensitive munitions 19. energetic binders comprising polymer and plasticiser(s) are finding use in cast-cured polymer bonded explosives and cast composite rocket propellants.

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