Abstract:The ability to prepare block, multiblock and segmented polymers is an essential and established tool in polymer chemistry to tailor the properties of materials and steer the formation of complex...
“…This Diels-Alder polymerization proved to be a highly versatile route to the preparation of novel polyimides, with broad possibilities and considerable potency.Figure 28.Synthesis of the polymer via Diels-Alder polymerization. 159 …”
Section: Pericyclic Reactionsmentioning
confidence: 99%
“…151 Taking advantage of the fact that the D-A and the opposite retro-Diels-Alder (RDA) reactions can be controlled by temperature, the D-A reaction, especially with the furan/ maleimide couple, has been applied in the production of novel polymer materials bearing recyclable, 152 mendable, [153][154][155] and thermo-responsive features. [156][157][158] In recent years, the progress around the DA reaction to synthesize polymers has been ingeniously developed by Ian Teasdale et al 159 Diels-Alder reaction by phenylethynyl endfunctionalized oligomers containing preformed ring-closed imides (Figure 28). The reaction of alkynes with bistetraphenylcyclopentadienone chain extender occurs chemically with CO gas at high temperature, forming phenylene segments and polymerizing chains in the process.…”
With the development of polymer science, more and more named reactions have been applied to synthesizing polymers. Introducing new reactions into polymer synthesis is undoubtedly an excellent expansion for monomer and polymer libraries. In this review, the named reactions employed in polymer-chain synthesis were divided into seven types: electrophilic reactions, nucleophilic reactions, transition metal-mediated cross-coupling reactions, free radical reactions, pericyclic reactions, multi-component reactions and rearrangement reactions. The discussion was mainly focused on the progress in the utilization of these named reactions in polymer synthesis, which could be a valuable reference for researchers in the polymer field.
“…This Diels-Alder polymerization proved to be a highly versatile route to the preparation of novel polyimides, with broad possibilities and considerable potency.Figure 28.Synthesis of the polymer via Diels-Alder polymerization. 159 …”
Section: Pericyclic Reactionsmentioning
confidence: 99%
“…151 Taking advantage of the fact that the D-A and the opposite retro-Diels-Alder (RDA) reactions can be controlled by temperature, the D-A reaction, especially with the furan/ maleimide couple, has been applied in the production of novel polymer materials bearing recyclable, 152 mendable, [153][154][155] and thermo-responsive features. [156][157][158] In recent years, the progress around the DA reaction to synthesize polymers has been ingeniously developed by Ian Teasdale et al 159 Diels-Alder reaction by phenylethynyl endfunctionalized oligomers containing preformed ring-closed imides (Figure 28). The reaction of alkynes with bistetraphenylcyclopentadienone chain extender occurs chemically with CO gas at high temperature, forming phenylene segments and polymerizing chains in the process.…”
With the development of polymer science, more and more named reactions have been applied to synthesizing polymers. Introducing new reactions into polymer synthesis is undoubtedly an excellent expansion for monomer and polymer libraries. In this review, the named reactions employed in polymer-chain synthesis were divided into seven types: electrophilic reactions, nucleophilic reactions, transition metal-mediated cross-coupling reactions, free radical reactions, pericyclic reactions, multi-component reactions and rearrangement reactions. The discussion was mainly focused on the progress in the utilization of these named reactions in polymer synthesis, which could be a valuable reference for researchers in the polymer field.
“…Copolymerization between polyimide and poly-(phenylene) has been reported by utilizing a Diels−Alder reaction on phenylethynyl end-functionalized oligomers containing preformed, ring-closed imides. 31 Unfortunately, further investigation regarding the copolymers' physical properties as well as gas transport phenomena is lacking.…”
Section: ■ Introductionmentioning
confidence: 99%
“…Good architectural control over a block copolymer consisting of highly selective polyimide and highly permeable poly(phenylene) provides an opportunity for gas separation tunability. Copolymerization between polyimide and poly(phenylene) has been reported by utilizing a Diels–Alder reaction on phenylethynyl end-functionalized oligomers containing preformed, ring-closed imides . Unfortunately, further investigation regarding the copolymers’ physical properties as well as gas transport phenomena is lacking.…”
A series of 6FDA-DABA (6FD) polyimide
and branched poly(phenylene)
(PP) block copolymers and homopolymers were successfully synthesized
using Diels–Alder and polycondensation reactions. PP and 6FD
homopolymer blends in tetrahydrofuran were immiscible. The result
coincides with their large chemical dissimilarity and theoretical
solubility parameter differences of 25.47 and 33.17 (MJ/m3)1/2. However, 6FD-PP block copolymer solutions were clear,
and thin films were robust and creasable. Densities and fractional
free volumes (FFV) (0.162–0.346) largely obeyed the rule of
mixing, suggesting a “blend-like” morphology. At moderate
PP block lengths, two distinct glass transition temperatures (340
and 420 °C) were evident, while large PP block lengths suppressed
first-order polyimide transitions entirely. A small-angle X-ray scattering
and atomic force microscopy morphological analysis revealed two distinct
domains, with separation lengths increasing with the PP block length.
Their gas permeation, diffusion, sorption, and separation properties
were thoroughly investigated and exhibited a strong correlation with
polymer chemistry, block length, and FFV. A block copolymer had an
O2 permeability roughly between 6FD and PP, resulting in
a 30% increase in O2/N2 selectivity. The N2/CH4 selectivities ranged from 4.2 to 0.58, suggesting
that this 6FD-PP system could be efficiently tuned from highly N2-selective to CH4-selective performance. Five structural
models, rule-of-mixture, Maxwell, equivalent box model, laminate,
and blend, were used to predict gas transport properties. Compared
with experimental data, the miscible blend model provided the best
results for the 6FD-PP block copolymer system. Block copolymerization
by combining highly selective polyimide and highly permeable branched
poly(phenylene) provides an opportunity for gas separation tunability
and improvement in selected gas pairs.
“…15 They have also been employed in polymer science, and numerous polymers containing cyclic segments have been produced. 16,17 For instance, a chaingrowth cycloaddition polymerization via a catalytic alkyne [2 + 2 + 2] cyclotrimerization reaction (Scheme 1a), 18 [2 + 2] photopolymerization (Scheme 1b), 19,20 and Diels-Alder cycloaddition polymerization 21,22 have been developed toward the construction of novel polymer structures. However, the versatility of cycloaddition polymerization has not been fully employed to enrich the diversity of thiacyclic polymers.…”
An organocatalytic cycloaddition polymerization approach for the facile synthesis of thiacyclic polymers is established in this work. Bis(N-sulfonyl aziridine)s and diisocyanates are employed as the monomers, and they undergo cycloaddition...
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