New hybrid polyhydroxyurethane networks were quantitatively synthesized by radical polymerization of new hydroxyurethane methacrylate (HUMA) prepolymers. These HUMAs were synthesized in several steps. First, bis(cyclic carbonate) poly(propylene oxide) was reacted with two different diamines (ethylene diamine and 2,2 0 -(ethylenedioxy)diethylamine) in excess. Then, these end-functionalized hydroxyurethane prepolymers were converted into end-functionalized hydroxyl prepolymers by ring opening of ethylene carbonate. Finally, a methacrylate function was grafted to the hydroxyl functions. All these steps were performed at room temperature. These prepolymers were thermally either homopolymerized or copolymerized using benzylmethacrylate or poly(ethylene oxide) bisphenol A dimethacrylate as comonomers, leading to new hybrid nonisocyanate polyurethane networks with various properties.Polyurethane acrylates are currently widely used for coating applications and are notably obtained by ultraviolet (UV)-light processes. They exhibit excellent mechanical and chemical properties such as high abrasion resistance, toughness, or tear strength. [18][19][20][21][22] Moreover, thanks to various reactive diluents, their properties can be easily adjusted depending on the desired requests. Furthermore, the microphase separation of the urethane segments, mainly governed by the soft segment, enables the control of the mechanical properties of the thermosets. 23 Additionally, polyurethane methacrylates were also developed in order to obtain high glass transition temperatures and to improve the stability of the prepolymers. 24 Polyurethane methacrylates are major curing agents providing solvent-resistance, mechanical strength, and UV or thermal curing ability. 22,25,26 When moving to NIPU, few literature is provided for hydroxyurethane methacrylate (HUMA) monomers having only one HU unit. They are synthesized from the ring-opening reaction of ethylene carbonate by an amine followed by the grafting of methacrylic moiety. For example, these methacrylate monomers were investigated for their ability to react under UV Additional supporting information may be found in the online version of this article.M. Decostanzi and C. Bonneaud contributed equally to this article.
Perfluoropolyalkylethers (PFPAEs) are a class of fluorinated polymers having −OCF2–, −OCF2CF2–, and −OCF2CF(CF3)– as common chain units. The ether linkages distinguish them from other famous fluorinated polymers such as poly(tetrafluoroethylene). Their higher mobility highlighted by below zero glass transition temperatures permit them to be noncrystalline, which makes them easy to use for many applications. They possess interesting tribological properties, combined with an excellent thermal and chemical stability, make them very useful as lubricants. However, after chemical modifications, they also demonstrated to be very useful in numerous applications as surfactants, electrolytes, high performance coatings, vitrimers, or microfluidic devices, to give a few examples. This Perspective aims to summarize all the chemical modifications reported on these PFPAEs to provide a new insight into their potential utility in emerging fields. Indeed, the end group can modulate the properties of PFPAE-based materials such as lubricity, superhydrophobicity, biofouling, antibacterial activity, amphiphilicity, and the ability to react further with comonomers under photochemical and thermal processes. It can also modulate their intrinsic properties such as viscosity and solubility in common organic solvents. The chemical modifications are sorted in five main parts: the condensation reactions, the nucleophilic reactions, the click chemistry reactions, the radical reactions, and finally reactions going through other mechanisms or requiring a multistep process. They can be employed as such or for further polymerization processes depending on the targeted application. Examples of applications are thoroughly described to demonstrate their current usefulness and to help provide direction for their future use.
Hydrophobic macromonomers synthesized by Steglich esterification to generate UV-curable materials.
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