Bonding prepolymer

For all three diallyl phthalate isomers, gelation occurs at nearly the same conversion DAP prepolymer contains fewer reactive allyl groups than the other isomeric prepolymers (36). More double bonds are lost by cyclisation in DAP polymerisation, but this does not affect gelation. The heat-distortion temperature of cross-linked DAP polymer is influenced by the initiator chosen and its concentration (37). Heat resistance is increased by electron beam irradiation. 

Additive Polyimides. Rhc ne-Poulenc s Kin el molding compound and Kerimid impregnating resin (115), Mitsubishi s BT Resins (116), and Toshiba s Imidaloy Resin (117) are based on bismaleimide (4) technology. Maleic anhydride reacts with a diamine to produce a diimide oligomer (7). Eurther reaction with additional diamine (Michael addition) yields polyaminohismaleimide prepolymer with terminal maleic anhydride double bonds. Cure is achieved by free-radical polymerization through the terminal double bonds. 

The reaction of water with isocyanate is shown in the third item of Fig. 1 [5]. The water/isocyanate reaction is the major curing mechanism for the one-component urethane adhesives. Most one-component urethanes are based on an isocyanate-terminated prepolymer (I). Usually, the moisture in the air is used to cure the adhesive, but in some instances, a fine mist of water may be introduced on top of the adhesive before the bond is closed, in order to facilitate cure ... 

A variety of applications exist for liquid, 100% solid adhesives, (An adhesive is considered 100% solid if there is no solvent in the adhesive.) Some of the largest uses include structural wood adhesives and adhesives used for the transportation industry, such as windshield adhesives and those used for bonding composite sidewalls of a recreational vehicle (RV). Structural wood adhesives are often made of a polymeric MDI with functionality of approximately 2.7 or higher. Rigid assemblies often utilize polymeric MDI, whereas flexible adhesive assemblies will more often utilize pure MDI, a solid waxy material that melts at around 37°C, or a modified MDI , i.e., MDI that has been modified to make it a liquid at room temperature. Prepolymers are made with ratios of anywhere from NCO/OH = 1.6 to 3.0 or higher. 

Furthermore, photochemically induced homolytical bond cleavage can also be applied when the prepolymer itself does not contain suitable chromophoric groups [113-115]. Upon thermolysis of ACPA in the presence of styrene, a carboxyl-terminated polystyrene is formed. This styrene-based prepolymer was reacted with lead tetraacetate and irradiated with UV light yielding free radicals capable of initiating the polymerization of a second monomer (Scheme 33) [113]. 

Because the ketene acetal-terminated prepolymer is a viscous Liquid at room temperature, therapeutic agents and the triol can be mixed into the prepolymer at room temperature and the mixture crosslink id at temperatures as low as 40°C. This allows incorporation of heat-sensitive therapeutic agents into a solid polymer under very mild conditions of thermal stress. However, because the prepolymer con-tedns reactive ketene acetal groups, any hydroxyl groups present in the therapeutic agent will result in the covalent attachment of the therapeutic agent to the matrix via ortho ester bonds (16). 

Hydroxy-terminated polyester (HTPS) is made from diethylene glycol and adipic acid, and hydroxy-terminated polyether (HTPE) is made from propylene glycol. Hydroxy-terminated polyacetylene (HTPA) is synthesized from butynediol and paraformaldehyde and is characterized by acetylenic triple bonds. The terminal OH groups of these polymers are cured with isophorone diisocyanate. Table 4.3 shows the chemical properties of typical polymers and prepolymers used in composite propellants and explosives.E4 All of these polymers are inert, but, with the exception of HTPB, contain relatively high oxygen contents in their molecular structures. 

GAP is synthesized by replacing C-Cl bonds of polyepichlorohydrin with C-N3 bonds.The three nitrogen atoms of the N3 moiety are attached linearly with ionic and covalent bonds in every GAP monomer unit, as shown in Fig. 4.6. The bond energy of N3 is reported to be 378 kj mol per azide group. Since GAP is a liquid at room temperature, it is polymerized by allowing the terminal -OH groups to react with hexamethylene diisocyanate (HMDl) so as to formulate GAP copolymer, as shown in Fig. 4.7, and crosslinked with trimethylolpropane (TMP) as shown in Fig. 4.8. The physicochemical properhes of GAP prepolymer and GAP copolymer are shown in Table 4.4 and Table 4.5, respectively.I ]... 

The heat of decomposition, Qj, of BAMO copolymer containing different levels of N3 bond density, KN3), is shown as a function of KN3) in Fig. 5.21. BAMO prepolymer is copolymerized with THF. The N3 bond density is varied by adjusting the mass fraction ratio of BAMO prepolymer and THF. 

As described in Sections 4.2.4.1 and 5.2.2, GAP is a unique energetic material that burns very rapidly without any oxidation reaction. When the azide bond is cleaved to produce nitrogen gas, a significant amount of heat is released by the thermal decomposition. Glycidyl azide prepolymer is polymerized with HMDI to form GAP copolymer, which is crosslinked with TMP. The physicochemical properties of the GAP pyrolants used in VFDR are shown in Table 15.3.PI The major fuel components are H2, GO, and G(g), which are combustible fragments when mixed with air in the ramburner. The remaining products consist mainly of Nj with minor amounts of GOj and HjO. 

Fumaric and itaconic acids are also used as the diacid component. Most reaction formulations involve a mixture of a saturated diacid (iso- and terephthalic, adipic) with the unsaturated diacid or anhydride in appropriate proportions to control the density of crosslinking (which depends on the carbon-carbon double-bond content of the prepolymer) for specific applications [Parker and Peffer, 1977 Selley, 1988], Propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, and bisphenol A are also used in place of ethylene glycol as the diol component. Aromatic reactants are used in the formulation to improve the hardness, rigidity, and heat resistance of the crosslinked product. Halogenated reactants are used to impart flame resistance. 

The prepolymers described above are one type of telechelic polymer. A telechelic polymer is one containing one or more functional end groups that have the capacity for selective reaction to form bonds with another molecule. The functionality of a telechelic polymer or prepolymer is equal to the number of such end groups. The macrodiol and macrodiisocyanate telechelic prepolymers have functionalities of 2. Many other telechelic prepolymers were discussed in Sec. 2-12. (The term functional polymer has also been used to describe a polymer with one or more functional end groups.)... 

Typical liquid systems require doses between 10 and 50 kGy. They consist of binders (prepolymers) with acrylic (H2C=CH-CO-0-) double bonds in the main chain (polymaleates and polyfumarates) and of monomers, usually acrylates used as reactive thinners. Other ingredients added to the formulation may be pigments, dyes, fillers, flatting agents, and additives to improve film and surface properties and attain the required performance criferia. ... 

---