Maleimide – Platform function for innovative materials

Article Maleimide

DATE

January 2022

Maleimide-containing polymers are gaining a great deal of attention in both scientific and industrial communities since they can be used in high performance macromolecular systems such as self-healing materials, biological materials, high temperature thermoset materials or UV-curable materials.[1], [2]. SPECIFIC POLYMERS is developing building-blocks, monomers and polymers containing maleimide functionalities for more than 15 years because it can bring outstanding properties in very different application fields.

 

Indeed, due to an high electron deficient double bond, the maleimide functional groups can be involved in a large range of chemical reactions such as, Michael additions with various nucleophiles, Diels-Alder (DA) reactions due to its dienophilic character, radical co-polymerization reactions with electron donor compounds (vinyl ether or styrene derivatives) or anionic or radical homo-polymerization.[3]

Maleimide-based Self-Healing Materials

The healing capacity of maleimide-containing polymeric materials is coming from the Diels Alder (DA) reactions between a diene (furan) and a dienophile (maleimide) leading to thermoreversible bonds in the polymer network.

As for example, PEG-PPG polyethers bearing maleimides groups were used for various robotic applications. Indeed, by combining PEG-PPG with different chain lengths, an entire range of mechanical properties between flexible and brittle networks can be reached. Low molecular weight PEG-PPG maleimide polymers were used to construct a self-healing mechanical fuse that can protect a robotic actuator. High molecular weight ones were more dedicated to build-up soft robots.[4] Based on the same reversible chemistry, self-healable polyurethanes were designed based on diols bearing thermo-reversible furfuryl and maleimide moieties and, tuning the content of thermo-reversible moieties into the materials allowed to observe the influence of the cross-linking density on the healing properties.[5]  It was shown that the glass transition temperature of the materials also impact the DA cycloaddition kinetic, i.e. higher Tg correspond to mobility-restricted conditions and imply slower healing process.[6]  The relevance of maleimide moieties for the design of Covalent Adaptable Networks is one of SPECIFIC POLYMER’s lever of innovation in the research toward more sustainable thermoset materials, notably targeting longer life-time of recyclability, reprocessability and repairability properties.

Related R&D products

Poly(propylene glycol), α,ω-bis(maleimide)
PPG-block-PEG-block-PPG, α,ω-bis(maleimide)
Poly(propylene glycol)
tris(maleimide)
Alkyl(C10) maleimide
Allyl maleimide

Maleimide for Biomedical applications

The highly selective nature of the Michael addition of thiols to maleimides has led to maleimide-containing polymers being widely used in biological applications, mostly to conjugate biomolecules via thiol-containing cysteine residues.

Such covalent attachment of polymers, most commonly poly(ethylene oxide), to biomolecules increases the in vivo effectiveness of protein-based drugs. As a consequence the hydrodynamic volume of the protein increase and hence (i) reducing renal filtration, (ii) preventing the approach of antibodies or antigen processing cells by masking the protein surface  and (iii) increasing the solubility and reducing the degradation of the protein by proteolytic enzymes. These superior properties to unmodified proteins make the materials of particular interest for applications in the fields of medicine, biotechnology and nanotechnology. Indeed PEGylation has become a field of interest in its own right.[7]

Photopolymerization of maleimides

Maleimides functional molecules or macromolecules can also be polymerized by photopolymerization. Fast polymerization kinetics can be obtained with such monomers but the main singularity of this moiety is linked to its ability to self-photopolymerized without photoinitiators. Indeed, maleimides can initiate the polymerization on their own and the mechanism of initiation was demonstrated to be linked to an electron transfer which provides a radical anion that can initiate the polymerization.[8] More, it can also initiate the polymerization of other types of unsaturated resins such as acrylate, vinyl ether or epoxies.

This feature of maleimides is of high interest in the development of multi-functional and UV-curable coatings, especially due to the sustainability of the UV curing process which is fast and can be achieved at ambient temperature,without any solvents.

In this field of research, SPECIFIC POLYMERS offers a large range of R&D products. Furthermore, we have the ability to custom design maleimide-containing monomers, polymers and building-blocks that are consistent with your need.

Do not hesitate to contact us!

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