Thermosets bismaleimides

Pascal et al. [49-50] studied semi-2-IPN derived from linear thermoplastic polyimides and thermosetting bismaleimides from the same type of starting... 

Kerimid 60 P Thermosetting bismaleimide 39 + diamine 34 (Fig. 17) Solid powder... 

Shibata Mitsuhiro, Teramoto Naozumi, Imada Ayumi, Neda Makiyo, and Sugimoto Shimon. Bio-based thermosetting bismaleimide resins using eugenol, bieugenol and eugenol novolac. React. Funct. Polym. 73 no. 8 (2013) 1086-1095. 

Currendy, epoxy resins (qv) constitute over 90% of the matrix resin material used in advanced composites. The total usage of advanced composites is expected to grow to around 45,500 t by the year 2000, with the total resin usage around 18,000 t in 2000. Epoxy resins are expected to stiH constitute about 80% of the total matrix-resin-systems market in 2000. The largest share of the remaining market will be divided between bismaleimides and polyimide systems (12 to 15%) and what are classified as other polymers, including thermoplastics and thermoset resins other than epoxies, bismaleimides, cyanate esters, and polyimide systems (see Composites,polymer-matrix-thermoplastics). 

A number of BMI resias based on this chemistry became commercially available through Rhc ne Poulenc for appHcation ia priated circuit boards and mol ding compounds and Rhc ne Poulenc recognized the potential of bismaleimides as building blocks for temperature-resistant thermoset systems. The basic chemistry, however, was not new, because the Michael addition reaction had been employed by Du Pont to obtain elastomeric reaction products from bismaleimides and Hquid polymeric organic diamines (15). 

The Michael addition of nucleophiles to the carbon—carbon double bond of maleimide has been exploited ia the synthesis of a variety of linear polymers through reaction of bismaleimide with bisthiols (39). This method has been used to synthesize ethynyl-terminated imidothioether from the reaction of 4,4 -dimercaptodiphenyl ether [17527-79-6] and A/-(3-ethynylphenyl)maleimide (40). The chemical stmcture of this Michael addition imide thermoset is as follows ... 

Diels-AIder Copolymers. The Diels-Alder reaction can also be employed to obtain thermosetting polyimides. If bismaleimide (the bisdienophile) and the bisdiene react nonstoichiometricaHy, with bismaleimide in excess, a prepolymer carrying maleimide terminations is formed as an intermediate, which can then be cross-linked to yield a temperature-resistant network. 

Modified Bismaleimides. Bismaleknide resins may be further modified and blended with other thermoset resins or reactive diluents to achieve either specific end-use properties or processibiUty. Thermoset resins that can be used for modification are unsaturated polyesters, vinylesters, cyanate esters, and epoxies. 

A great variety of resia formulations is possible because other thermosets, such as epoxies or acrylates, and reactive diluents, such as o-diaUyl phthalate [131-17-9] triaUyl cyanurate [101-37-17, or triaUyl isocyanurate [1023-13-6J, can be used to further modify the BT resias. The concept is very flexible because bismaleimide and biscyanate can be blended and copolymerized ia almost every ratio. If bismaleimide is used as a major constituent, then homopolymerization of the excess bismaleimide takes place ia addition to the copolymerization. Catalysts such as ziac octoate or tertiary amines are recommended for cure. BT resias are mainly used ia ptinted circuit and multilayer boards (58). 

If the bismaleimide-amine reaction is carried out with a deficiency of amine the polymer will have terminal double bonds which allows a cure site to give a thermosetting polymer via a double bond polymerisation mechanism. This approach was developed by Ciba-Geigy with their product P13N (Figure 18.42). 

Stenzenberger H. D. Thermosetting Polyimides from Bismaleimides via Diels-Alder Reaction in Polyimides Other High-Temp. Polym., Proc. Eur. Tech. Symp., 2nd" 1991 215, Eds. Abadie M. J. M. and Sillion B., Pb. Elsevier Amsterdam... 

The typical resin systems include thermoset polyesters, vinyl esters, epoxies, polymi-dies, bismaleimide, and phenolics. Thermoplastics are also finding their way into filament winding. Wet thermoset filament winding requires a resin with viscosity in the range of 1000-3000 cpoise. Resin components are chosen on the basis of pot life, winding temperature, viscosity, gel time, and cure time. 

Several researchers have modeled the cure kinetics of thermosetting resins in the past, including an unsaturated polyester resin [8], epoxies [9-11], and bismaleimide [5], As an example, a graphite/BMI material, IM6/3100, was modeled in [5] using... 

Matrix materials for commercial composites are mainly liquid thermosetting resins such as polyesters, vinyl esters, epoxy resins, and bismaleimide resins. Thermoplastic composites are made from polyamides, polyether ether ketone (PEEK), polyphenylene sulfide (PPS), polysulfone, polyetherim-ide (PEI), and polyamide-imide (PAI). 

The most common advanced composites are made of thermosetting resins, such as epoxy polymers (the most popular singlematrix material), polyesters, vinyl esters, polyurethanes, polyimids, cianamids, bismaleimides, silicones, and melamine. Some of the most widely used thermoplastic polymers are polyvinyl chloride (PVC), PPE (poly[phenylene ether]), polypropylene, PEEK (poly [etheretherketone]), and ABS (acrylonitrile-butadiene-styrene). The precise matrix selected for any given product depends primarily on the physical properties desired for that product. Each type of resin has its own characteristic thermal properties (such as melting point... 

Structural modifications were envisioned early to overcome these limitations. A first improvement was outlined by preparing copolymers, which were soluble in the state of full imidation, mainly poly(ester-imide)s and poly(amide-imide)s [2,4, 5]. As an alternative to these conventional copolymers, addition polyimides were developed in the 1970s as a new class of thermosetting materials. Thus, bismaleimides, bisnadimides, and end-capped thermocurable polyimides were successfully developed and marketed [6,7]. These resins were the precursors of the modern PMR (polymeric monomer reactants) formulations [8]. 

FRP materials are made up of the polymer and reinforcing fibers. The polymer is typically a thermoset polymer thermoplastics can be used as well. Some typical thermoset polymers used are epoxy resins, unsaturated polyester resins, epoxy vinyl ester resins, phenolic resins, and high performance aerospace resins such as cyanate esters, polyimides, and bismaleimides. These resins... 

Within the past several years, improvements in the toughening of high-temperature epoxies and other reactive thermosets, such as cyanate esters and bismaleimides, have been accomplished through the incorporation of engineering thermoplastics. Additions of poly(arylene ether ketone) or PEK and poly(aryl ether sulfone) or PES have been found to improve fracture toughness. Direct addition of these thermoplastics generally improves fracture toughness but results in decreased tensile properties and reduced chemical resistance. 

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