Nitrate polymers

B. Kosowski, C. Meyersand, D. Robitelle, A. Ruebner and G. Station, Cyclodextrin Polymer Nitrate , Proc. 31st International Annual Conference of ICT, Karlsruhe, Germany, 2000, V12-1. 

Ethyleneglycol Polymers Nitrated. Propellants contg nitrated polyglycols are described in Ref. Tranchant prepd slabs of 60/40 CPSj SD... 

Glycol Polymers or Polyglycols. See Ethyleneglycol Polymers, Nitrated in this vol, p E279-R... 

Polymer-based rocket propellants are generally referred to as composite propellants, and often identified by the elastomer used, eg, urethane propellants or carboxy- (CTPB) or hydroxy- (HTPB) terrninated polybutadiene propellants. The cross-linked polymers act as a viscoelastic matrix to provide mechanical strength, and as a fuel to react with the oxidizers present. Ammonium perchlorate and ammonium nitrate are the most common oxidizers used nitramines such as HMX or RDX may be added to react with the fuels and increase the impulse produced. Many other substances may be added including metallic fuels, plasticizers, stabilizers, catalysts, ballistic modifiers, and bonding agents. Typical components are Hsted in Table 1. 

Propellants cast into rockets are commonly case-bonded to the motors to achieve maximum volumetric loading density. The interior of the motor is thoroughly cleaned, coated using an insulating material, and then lined with a composition to which the propellant binder adheres under the environmental stresses of the system. The insulation material is generally a mbber-type composition, filled with siUca, titanium dioxide, or potassium titanate. SiUca-filled nitrate mbber and vulcanizable ethylene—propylene mbber have been used. The liner generally consists of the same base polymer as is used in the propellant. It is usually appHed in a thin layer, and may be partially or fully cured before the propellant is poured into the rocket. 

MDA reacts similarly to other aromatic amines under the proper conditions. For example, nitration, bromination, acetylation, and dia2oti2ation (1 3) all give the expected products. Much of the chemistry carried out on MDA takes advantage of the diftmctionality of the molecule in reacting with multiftmctional substrates to produce low and high molecular weight polymers. 

Catalysts. Silver and silver compounds are widely used in research and industry as catalysts for oxidation, reduction, and polymerization reactions. Silver nitrate has been reported as a catalyst for the preparation of propylene oxide (qv) from propylene (qv) (58), and silver acetate has been reported as being a suitable catalyst for the production of ethylene oxide (qv) from ethylene (qv) (59). The solubiUty of silver perchlorate in organic solvents makes it a possible catalyst for polymerization reactions, such as the production of butyl acrylate polymers in dimethylformamide (60) or the polymerization of methacrylamide (61). Similarly, the solubiUty of silver tetrafiuoroborate in organic solvents has enhanced its use in the synthesis of 3-pyrrolines by the cyclization of aHenic amines (62). 

Cellulose Deriva.tives, Cellulose can be derivatized to make both water-soluble gums and hydrophobic polymers. The preparation of the hydrophobic cellulose esters (qv), cellulose acetates and cellulose nitrates, has already been mentioned. The water-soluble cellulose derivatives are cellulose ethers (qv). 

There are a variety of reaction systems that allow the formation of cellulose trinitrate [9046-47-3]. HNO in methylene chloride, CH2CI2, yields a trinitrate with essentially no degradation of the cellulose chain (53). The HNO /acetic acid/acetic anhydride system is also used to obtain the trinitrate product with the fiber stmcture largely intact (51,52). Another polymer analogous reaction utilises a 1 1 mixture of HNO and H PO with 2.5% P2O5 to achieve an almost completely nitrated product (54). 

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