Synthesis of Diverse Asymmetric α,ω‐Dienes Via the Passerini Three‐Component Reaction for Head‐to‐Tail ADMET Polymerization

Abstract

The Passerini three‐component reaction is applied to synthesize, in a one‐step procedure, diverse asymmetric α,ω‐dienes containing an acrylate and a terminal olefin. Such monomers are well known to undergo head‐to‐tail acyclic diene metathesis (ADMET) polymerization due to the high cross‐metathesis selectivity between acrylates and terminal olefins. Additionally, amphiphilic block copolymers are synthesized using a monofunctional PEG480 monoacrylate, which acts as a selective chain‐transfer agent during the polymerization process. Thus, control over the molecular weight of the amphiphilic ADMET polymers is shown by using different ratios of mono­mer and chain‐transfer agent. All the polymers are thoroughly characterized, and their ability to form nanoparticles in aqueous solution is studied.

Precisely designed perylene bisimide-substituted polyethylene with a high glass transition temperature and an ordered architecture

“…7b, P1d exhibited an obvious glass transition according to the DSC curve, with a T g value of 80.4 C. For HP1d, the glass transition was detected at a T g value of 75.8 C, which is slightly lower than that of its precursor P1d, but beyond what was expected and much higher than those of PE polymers with well-dened short or long alkyl branches and even large pyrene branches, 22,23 as well as of ADMET polyesters with amide branches. 24 More importantly, the change in the T g value that occurred upon saturation of P1d to form HP1d is also different from such changes of previously reported well-dened poly-olens, where the T g of the saturated polymer increased slightly compared to the unsaturated analogue; these observations for polyolens were indicative of the segmented motion of the branches being restricted by the crystallinity of the PE backbone. 23c The shi of T g to a much higher temperature relative to previous perfectly sequenced EP or EO copolymers with methyl or hexyl branches 22,23 is attributed to the polymer chain exibility being inhibited by the bulky rigid PBI branches, and the backbone crystallization being impeded by strong p-p stacking interactions and aggregation of PBI.…”

Covalent Tethering of Temperature Responsive pNIPAm onto TEMPO-Oxidized Cellulose Nanofibrils via Three-Component Passerini Reaction

“…The three-component Passerini reaction (Passerini 3-CR) has captured the special attention of both academic and industrial scientists due to the carbenic reactivity of isocyanides leading to the quick and easy synthesis of a larger variety of multifunctional products with excellent yields, at or below room temperature . For instance, Meier and co-workers reported the divergent synthesis of a variety of functional monomers such as tunable acrylate monomers, AB-type monomers bearing carboxylic acid and aldehyde moieties, as well as asymmetric α,ω-dienes containing an acrylate and a terminal olefin . Such monomers were then directly polymerized in a polyaddition approach applying the Passerini 3-CR for the formation of sequence-controlled and high-molecular-weight polymers with different side chains. − In other studies, it was described that the Passerini 3-CR was successfully used as an efficient approach for the divergent and convergent synthesis of well-designed dendrimers.…”

“…For instance, Meier and co-workers reported the divergent synthesis of a variety of functional monomers such as tunable acrylate monomers, AB-type monomers bearing carboxylic acid and aldehyde moieties, as well as asymmetric α,ω-dienes containing an acrylate and a terminal olefin . Such monomers were then directly polymerized in a polyaddition approach applying the Passerini 3-CR for the formation of sequence-controlled and high-molecular-weight polymers with different side chains. − In other studies, it was described that the Passerini 3-CR was successfully used as an efficient approach for the divergent and convergent synthesis of well-designed dendrimers. In addition, Söyler et al has recently reported the successful surface modification of succinylated cellulose by employing small molecular model of Passerini components under mild conditions …”

Concurrent Oxidation of Alcohols and the Passerini Three‐Component Polymerization for the Synthesis of Functional Poly(ester amide)s

“…It has many advantages, such as high efficiency, mild reaction conditions, and good tolerance to many functional groups . Despite all these advantages, Ugi‐4CR and Passerini‐3CR have been applied in polymer synthesis only until recently . It is thus becoming a simple multicomponent polymerization (MCP) method for the synthesis of functional polyesters, poly(ester amide)s, polyamides, graft copolymers, and hyperbranched polymers .…”

“…It is thus becoming a simple multicomponent polymerization (MCP) method for the synthesis of functional polyesters, poly(ester amide)s, polyamides, graft copolymers, and hyperbranched polymers . Owing to the high efficiency, Passerini‐3CR has also been used for the synthesis of monomers, sequence‐regulated polymers, and dendrimers, and for post‐modification of polymers . Passerini MCP of a dicarboxylic acid with an aldehyde and a diisocyanide has been reported to be a facile method to prepare poly(ester amide)s .…”