Synthesis and Properties of Photodegradable Poly(furan-amine)s by a Catalyst-free Multicomponent Cyclopolymerization

Fu, Weiqiang; Zhu, Guinan; Shi, Jianbing; Tong, Bin; Cai, Zhengxu; Dong, Yuping

doi:10.1007/s10118-019-2281-5

Cited by 17 publications

(21 citation statements)

References 39 publications

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“…The MCCP mechanism of diisocyanate, activated alkyne and various third components was discovered and discussed in detail in our previous reports. [ 48–51 ] Therefore, the polymerization mechanism of PIFs based on diisocyanate, activated alkynes and 1,4‐dibromo‐2,3‐butanedione is not shown here. However, their structural verification follows in the next section.…”

Section: Resultsmentioning

confidence: 99%

“…Over the years, our group has been committed to the development of catalyst‐free MCCP based on diisocyanides, activated alkynes and various third monomers, and have prepared a series of functional heterocyclic polymers with good solubility and thermal stability, such as polyfurans, [ 48,49 ] poly(iminofuran‐arylene)s, [ 50 ] and spiropolymers. [ 51,52 ] In particular, the poly(iminofuran‐arylene)s have attracted much attention due to their cluster‐triggered emission properties, meanwhile the bromomethyl groups in the side chains provide the possibility for further post functionalization.…”

Section: Introductionmentioning

confidence: 99%

“…Additionally, the photodegradation of PIFs is almost nonresidual under ultraviolet irradiation, which is similar with our previous report. [ 49 ] Moreover, a large number of carboxylates and bromomethyl groups on the side chains can be easily post modified to prepare multifunctional PIFs materials.…”

Section: Introductionmentioning

confidence: 99%

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Catalyst‐Free Multicomponent Cyclopolymerizations of Diisocyanides, Activated Alkynes, and 1,4‐Dibromo‐2,3‐Butanedione: a Facile Strategy toward Functional Polyiminofurans Containing Bromomethyl Groups

Zhu

Han

et al. 2020

Macromol. Rapid Commun.

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Polymers containing iminofuran (PIFs) are rarely reported due to the lack of simple and effective synthesis methods. In this work, a novel multicomponent cyclopolymerization (MCCP) of diisocyanides, activated alkynes, and 1,4‐dibromo‐2,3‐butanedione using catalyst‐free one‐pot reactions under mild conditions to prepare PIFs containing bromomethyl groups is reported. PIFs with good solubility and thermal stability are obtained with high Mws (up to 19 600) and good yields (up to 89.5%) under optimized polymerization conditions. The structure of the PIFs is characterized by nuclear magnetic resonance, Fourier transform infrared spectroscopy, and gel permeation chromatography. The photophysical properties indicate that polymers P1a2b3 and P1c2b3 have cluster‐triggered emission characteristics. Thin films made from PIFs quickly degrade under UV irradiation. Moreover, the obtained polymers are decorated with bromomethyl and carboxylate groups in the side chain, which can be postfunctionalized to prepare multifunctional materials, such as star branched polymers and biomedical carrier materials. Thus, this work not only enriches the field of polymerization based on isocyanates and activated alkynes but also provides a facile strategy toward functional iminofuran polymers.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Catalyst‐Free Multicomponent Cyclopolymerizations of Diisocyanides, Activated Alkynes, and 1,4‐Dibromo‐2,3‐Butanedione: a Facile Strategy toward Functional Polyiminofurans Containing Bromomethyl Groups

Zhu

Han

et al. 2020

Macromol. Rapid Commun.

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“…P8a and P8d containing bromine, nitrogen, and oxygen elements have high RI values in the spectral region of 400−900 nm. Poly(furan−amine)s containing pyrimidine (P7m) show an RI value of n = 1.680 at 632.8 nm (Figure 2), 47,48 which is much higher than those of commercial optical polymeric materials, such as polystyrene (n = 1.587 at 632.8 nm) and polycarbonate (n = 1.581 at 632.8 nm).…”

Section: Refractive Indexmentioning

confidence: 94%

Functional Isocyanide-Based Polymers

Cai

Ren

et al. 2020

Acc. Chem. Res.

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Conspectus Research interest in the isocyanide-based reaction can be traced back to 1921 when the Passerini reaction was first reported. However, most of these research efforts did not lead to important progress in the synthesis of isocyanide-based polymers (IBPs). The major challenge resides in the lack of highly efficient polymerization methods, which limits large-scale preparation and applications. Modern organic chemistry provides efficient access to develop functional IBPs on the basis of isocyanide chemistry. However, it is still challenging to prepare the IBPs with small molecular isocyanide reaction. Our investigations into catalyst exploration and polymerization methodology have prompted the synthesis of a series of IBPs. Two classes of isocyanide monomers can be used for the construction of IBPs. The first class includes monomers with a single isocyanide. Novel catalysts for the synthetic chemistry of isocyanide allow the introduction of functional pendants into the linear polymer chains. This molecular functionalization endows the polymers with an array of new functional properties. For example, the incorporation of a chromophore on the polymeric side chain provides novel functional properties, such as aggregation-induced emission and optical activity. Diisocyanide monomers can be also utilized for the construction of heterocyclic, spiro-heterocyclic, and bispiro-heterocyclic polymers in the polymeric backbones. A new concept of “multi-component spiropolymerization” has been developed for the preparation of spiropolymers using the catalysis-free one-pot reaction. Proper structural design allows for the preparation of a heterocyclic polymeric chain with natural bioactivity and biological compatibility, generating new IBPs with biofunctionalities. In this Account, we discuss progress mainly made in our lab and related fields for the design of isocyanide monomers, exploration of new catalysts, and optimization of reaction conditions. The subsequent section discusses the characteristic properties and applications of selected examples of these functional polymers, mainly focusing on their optical applications. We have investigated the UV-sensitive IBPs that could potentially be used for lithography applications. One-pot highly efficient polymerization of diisocyanides and CO2 under mild conditions can provide a new method for realizing the reuse of CO2 and reducing the greenhouse effect. Through a combination of structural modifications, IBPs bearing dimethylbenzene moieties exhibit characteristics of black materials that can be potentially utilized as pyroelectric sensors, thermal detectors, and optical instruments. Most recently, our group synthesized a spiro-heterocyclic IBP with clusterization-triggered emission properties that can be used to discriminate cancer cells from normal cells and provides a new method for the treatment of cancer. The studies reviewed in this Account suggest that polymerization with isocyanide chemistry can be implemented in diverse functional macromolecules and materials.

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“…Therefore, this MCC process can yield useful photodegradable materials, which may offer a new platform for the design of multifunctional PAFs. 123 Second, a catalyst-free MCS route for the facile construction of heteroatom-containing spiropolymers has been developed by Dong et al (Fig. 14, Route 3).…”

Section: Mcp Based On Triple-bond Building Blocksmentioning

confidence: 99%