Thermosetting resins bismaleimide

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). 

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. 

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... 

Thermosetting resins Unsaturated polyesters phenol formaldehyde urea formaldehyde melamine formaldehyde epoxies vinyl ester resins cyanate ester resins bismaleimides certain polyimides... 

Table 3.2 also includes data for the advanced thermoplastic resins (PEEK) and for a thermosetting resin, an end-capped bismaleimide (BMI) called PMR-15. Moisture contents tend to be lower for these advanced materials [12,13]. One way to overcome the environmental sensitivity of epoxide resins is to employ these advanced resins, as demonstrated in Table 3.2. However, changing to other resin systems brings with it other concerns. For example, PEEK relies on crystallinity for its higher temperature performance. Its glass transition temperature is only 143°C and a change in modulus can be observed at that temperature. In addition, higher process temperatures are required both for high performance thermosets and thermoplastics. The consequent higher residual thermal stresses can off-set some of the advantages of a higher service temperature, in comparison with advanced epoxy resins.

Hirayama, K.-I, Irie, T, Teramoto, N. and Shibata, M. (2009) High-performance bio-based thermosetting resins composed of dehydrated castor oil and bismaleimide. Journal of Applied Polymer Science, 114(2), 1033-1039. 

Bismaleimides and polyimides have good thermal stability, extending the working temperature range of epoxides from about 200°C to 280°C. In the UK, polyimide is not widely used due to the high cost and difficulty in processing. However, bismaleimides are now becoming an important class of thermoset resins. 

The global thermoset resins market is expected to reach as high as 95 million metric tons by 2016 (Axis Research Mind report 2012). Excluding the alkyd resins, which are used primarily in the coatings, commercially important major types of thermoset resins, altuig with their relative % market share, estimated from literature (Fosdyke and Starr 2002), can be categorized as follows Polyurethanes (31 %), PhenoUcs (18 %), Amino resins (18 %), Unsaturated polyesters (12 %), Epoxies and other specialty/high performance thermosets (12 %), such as silicones, polyimides, bismaleimides (BMl), cyanate ester thermosets, etc. 

Commercial bismaleimide thermoset resins are based on aromatic bismaleimides such as 4,4 -bismaleimidodiphenylmethane (Compimid MDAB, Evraiik). Compimid MDAB, also known in literature as MDA-BMT is derived from the condensation reaction between 4,4 -methylene dianiline (MDA) and maleic anhydride, both relatively low-cost monomers. The MDA-BMI is often used as a eutectic mixture with other BMIs such as TDA-BMI, to reduce its melting point for improved impregnation and tackiness in the glass and carbon-fiber-based composite prepregs. 

Many matrix choices are available, and each type has an impact on the processing techniques, physical and mechanical properties, and enviromnental resistance of the finished part. Thermoplastic and thermoset materials can be resin matrices. Thermoplastic matrices have been developed to increase hot/wet use temperature and the fracture toughness of composites. Thermosetting resins, however, are more common. The common thermoset matrices for composites include polyester and vinyl esters, epoxy, bismaleimide, polyimide, and cyanate ester and phenolic triazine resins. 

Addition-type polyimides, which are thermosetting resins, were developed to improve the processability of polyimides, but their thermal stability is severely degraded by the presence of aliphatic bonds in place of the aromatic nuclei. However, the adhesive strength has been evaluated for the bismaleimide- (Section 4.3.4.1), bisnadimide- (Section 4.3.4.2) and acetylene-terminated (Section 4.3.4.3) imide oligomers. 

Other thermosetting resins used as matrices for structural composites are phenolics [89], aromatic polyimides [90], and other special high-temperature, high-strength resins Uke bismaleimides and cyanate esters [91]. Typical properties of these resins are reported in Table 8.3. 

Table 8.3. Typical properties of phenolics, polyimide, bismaleimide and cyanate ester thermoset resins...

Shibata Mitsuhiro, Teramoto Naozumi, and Nakamura Yu. High performance bio-based thermosetting resins composed of tung oil and bismaleimide. J. Appl. Polym. Sci. 119 no. 2 (2011a) 896-901. 

Yao Yuan, Zhao Tong, and Yu Yunzhao. Novel thermosetting resin with a very high glass-transition temperature based on bismaleimide and allylated novolac. J. Appl. Polym. Sci. 97 no. 2 (2005) 443-448. 

In fact all these properties were unavailable in conventional materials but may be covered by aromatic and heterocyclic Unear and thermosetting resins such as acetylene terminated resins, bismaleimides, polyetherimides, polyamide-imides, polybenzimidazoles, pol3dmides, polyetherketones, pol3qjhenylquinoxalines, polyphenylensulfides, polysulfones derivatives, polyst5nylp3nidines, fluoropol3mers, silicones, etc. 

The principal thermosetting resins used are phenolics, vinyl esters, polyesters (especially w ith glass fibres), and epoxies, bismaleimides, polyimides and polystyryl pyridine — all used with carbon fibres. Low or lower temperature curing systems must be employed with organic fibres to avoid damaging these by excessive heating during fabrication. 

Bismaleimides or BMI resins are a family of thermosetting resins with an upper working temperature higher than that of an epoxy, i.e. 180— 200°C compared with 150°C. Some data, including an entry from Table 5.14, are shown in Table 5.18. 

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. 

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... 

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