Hydroxy terminated polybutadiene

CTPB = carboxy-terminated polybutadiene HTPB = hydroxy-terminated polybutadiene PBAN = polybutadiene-acrylic acid-acrylonitrile and PBAA = polybutadiene-acrylic acid. 

Predominantly di-end-functional polymers may be prepared by conducting polymerizations with high concentrations of a functional initiator. Some of the first commercial products of this class, carboxy and hydroxy-terminated polybutadienes, were produced by this route.194... 

For example, using hydroxy-terminated polybutadiene as the binder, RDX as the expl, toluenediisocyanate as a co-polymer, sym-di-(2-naphthyl)-p-phenylenediamine as an antioxidant, and poly butene as the plasticizer in a wt % ratio of 12.1/42.7/5/0.2/40, a castable expl is produced. 

Synthesis and Characterisation of Hydroxy-Terminated Polybutadienes , Report No 6/R/66, ERDE, Waltham Abbey, Essex (Engl) (1967)... 

Composite proplnts, which are used almost entirely in rocket propulsion, normally contain a solid phase oxidizer combined with a polymeric fuel binder with a -CH2—CH2— structure. Practically speaking AP is the only oxidizer which has achieved high volume production, although ammonium nitrate (AN) has limited special uses such as in gas generators. Other oxidizers which have been studied more or less as curiosities include hydrazinium nitrate, nitronium perchlorate, lithium perchlorate, lithium nitrate, potassium perchlorate and others. Among binders, the most used are polyurethanes, polybutadiene/acrylonitrile/acrylic acid terpolymers and hydroxy-terminated polybutadienes... 

Another class of hydrocarbon binders used in propints are the carboxy-terminated polybutadiene polymers which are cross-linked with either tris[l-(2-methyl)aziridinyl] phosphine oxide (MAPO) or combinations with phenyl bis [l -(2-methyl)aziridinyl] phosphine oxide (Phenyl MAPO). Phenyl MAPO is a difunctional counterpart of MAPO which makes possible chain extension of polymers with two carboxylic acid groups. A typical propint formulation with ballistic properties is in Table 11 (Ref 83) Another class of composites includes those using hydroxy-terminated polybutadienes cross-linked with toluene diisocyanate as binders. The following simplified equations illustrate typical reactions involved in binder formation... 

The influence of ambient aging at 70°F and accelerated aging at 160°F on the stress-strain behavior of carboxy-terminated polybutadiene, polybutadiene-acrylic acid, polybutadiene-acrylic acid-acrylonitrile, and hydroxy-terminated polybutadiene composite propints is shown in Figures 10 and 11. The elastomers and curative agents for these formulations are listed below... 

The first SANS experiments on end-linked elastomers with a well-defined functionality were carried out by Hinkley et al, (22). Hydroxy-terminated polybutadiene was crosslinked by a trifunctional isocyanate, and the resultant polymer was uniaxially stretched. 

Hydroxy-terminated polybutadiene (8) (HTPB) has been treated with dinitrogen pentoxide in methylene chloride. The product (9) is an energetic oligomer but is unlikely to find application because of the inherent instability of /3-nitronitrates." Initial peroxyacid epoxidation of some of the double bonds of HTPB followed by reaction with dinitrogen pentoxide yields a product containing vtc-dinitrate ester groups and this product (NHTPB) is of much more interest as an energetic binder (see Section 3.10)." ... 

Research efforts are ongoing into the use of dinitrogen pentoxide for the industrial synthesis of nitrated hydroxy-terminated polybutadiene (NHTPB) from epoxidated HTPB (Section 3.10). The reaction of aziridines with dinitrogen pentoxide is an important route to 1,2-nitramine-niU ates and these reactions are discussed in Section 5.8.1. ... 

The synthesis of nitrated hydroxy-terminated polybutadiene (NHTPB) (44) from the reaction of partially epoxidized hydroxy-terminated polybutadiene with dinitrogen pentoxide... 

The polymeric hydrocarbon also acts as a binder of the particles, holding them together so as to formulate a propellant grain. Ammonium perchlorate (AP) is a typical crystalline oxidizer and hydroxy-terminated polybutadiene (HTPB) is a typical polymeric fuel. When AP and HTPB are decomposed thermally on the propellant surface, oxidizer and fuel gases are produced, which diffuse into each other and react to produce high-temperature combustion gases. 

Hydroxy-terminated polybutadiene (HTPB) is considered to be the best binder for obtaining high combustion performance, superior elongation properties at low temperatures, and superior mechanical strength properties at high temperatures. This combination of properties is difficult to achieve in double-base propellants. HTPB is characterized by terminal -OH groups on a butadiene polymer. The other type of butadiene polymer used is carboxy-terminated polybutadiene (CTPB), which is cured with an imine or an epoxy resin. It should be noted that CTPB is somewhat sensitive to humidity, which has an adverse effect on its ageing charac-... 

Typical examples of HCP are hydroxy-terminated polybutadiene (HTPB), car-boxy-terminated polybutadiene (CTPB), hydroxy-terminated polyether (HTPE), hydroxy-terminated polyester (HTPS), and hydroxy-terminated polyacetylene (HTPA). The physicochemical properties of various types of HCP are described in Section 4.2.3. 

There are a number of inert binders such as polyester, epoxy, polysulfide, polyurethane which have been reported as binders for composite propellants and plastic bonded explosives (PBXs). At present, hydroxy-terminated polybutadiene (HTPB) is regarded as the state-of-the-art workhorse binder for such applications. However, the recent trend is to use energetic binders such as poly [3,3-bis(azidomethyl oxetane)] [poly(BAMO)], poly (3-azidomethyl-3-methyl oxetane) [poly(AMMO)], PNP, GAP diol and triol, nitrated HTPB(NHTPB), poly(NiMMO), poly(GlyN) and nitrated cyclodextrin polymers poly(CDN) for PBXs and composite propellants in order to get better performance. 

N. (1989) Nitrated hydroxy-terminated polybutadiene (NHTPB) a new energetic binder. Proc. 14th Inti. Pyrotech. Seminar, Henry ling Press, Dorset, UK, pp. 105-111. 

Inert binders Polybutadiene and cellulose derivatives are used as binders for LOVA formulations [24]. The commonly used polybutadiene-based binders are hydroxy-terminated polybutadiene (HTPB) and carboxy-terminated polybutadiene (CTPB)/poly(butadiene-acrylonitrile) (PBAN) while the most commonly used cellulose derivatives are ethyl cellulose (EC), cellulose acetate (CA), cellulose acetate butyrate (CAB) and cellulose... 

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