A facile synthesis of branched graft copolymers via combination of RAFT self-condensing vinyl polymerization and aldehyde–aminooxy reaction

Huang, Jianbing; Lin, Lvhuan; Liang, Hui; Lu, Jiang

doi:10.1039/c5py00436e

Cited by 17 publications

(17 citation statements)

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“…presented a kind of HBP with thermally‐labile branching points prepared from designed inimer incorporated with a reversible‐covalent linkage between the propagating and initiating groups via SCVP, thus the degradation and reconstruction of thus obtained HBPs were examined, allowing the investigation of the mechanism of SCVP . The SCVP‐based copolymerization process was further widely used to prepare various LCHBPs based on poly(vinyl acetate)s and poly(2‐(dimethylamino)ethyl methacrylate)s …”

Section: Synthetic Methodologies Of Lchbpsmentioning

confidence: 99%

“…[119] Therefore, only the specific methods that will result in LCHBPs are included herein, and are primarily categorized into two different methods (Figure 1). The one is copolymerization of a small molecular inimer with comonomers, [80][81][82][83][84][85][86][87][88][89][90][91][92][93][94][95][96][97][98][99] where the additional comonomers are utilized for producing linear polymeric subchains. The other is direct homopolymerization of a macromolecular inimer or abbreviated macroinimer.…”

Section: Lchbps Based On Self-condensing Vinyl Polymerization (Scvp)mentioning

confidence: 99%

“…Although the original SCVP of simple inimers usually produce conventional HBPs with short subchains, [79,116,119,[131][132][133][134][135][136][137][138] through copolymerization with a conventional comonomer that is only capable of propagation, a LCHBP structure could be created through both the linear propagation of additional comonomer and branching process of inimer ( Figure 1). [80][81][82][83][84][85][86][87][88][89][90][91][92][93][94][95][96][97][98][99] Furthermore, the DB value during SCVP process may also allow to be tuned by the introduced conventional comonomer. Through RAFT copolymerization of monomer DMAEMA and inimer ACDT (Figure 12), Gao et al successfully prepared regular poly(tertiarl amino methacrylate) LCHBPs of uniform linear subchains hung with tertiary amino group.…”

Section: Copolymerization Of Small Molecular Inimers and Comonomersmentioning

confidence: 99%

“…[84,85] Sumerlin et al presented a kind of HBP with thermally-labile branching points prepared from designed inimer incorporated with a reversible-covalent linkage between the propagating and initiating groups via SCVP, thus the degradation and reconstruction of thus obtained HBPs were examined, allowing the investigation of the mechanism of SCVP. [86] The SCVP-based copolymerization process was further widely used to prepare various LCHBPs based on poly(vinyl acetate)s [87] and poly(2-(dimethylamino)ethyl methacrylate)s. [88] In addition, copolymerization of monovinylic monomer with divinylic comonomer has also showed the potential to afford LCHBP structures, which should essentially follow the process of generalized SCVP since the vinylic group may be easily converted into initiating group after activation by free radicals. [89][90][91][92] For instance, very recently, Sumerlin et al prepared iminecross-linked LCHBPs by RAFT copolymerization of novel divinyl compounds containing dynamic-covalent moieties, which could degrade into well-defined polymers when subjected to aqueous acidic conditions.…”

Section: Copolymerization Of Small Molecular Inimers and Comonomersmentioning

confidence: 99%

“…[1,5,7,8,10,15] This synthetic simplicity along with the fact that many of their physical and mechanical properties of both HBPs and dendrimers are evidenced to be similar make HBPs attractive alternatives to dendrimers and thus the investigation of HBPs encourages considerable attention. The results in a large number of contributions have shown HBPs to be good candidates for a wide range of applications including been adjusted for the preparation of LCHBPs through copolymerization of the traditional small molecular inimer with an additional comonomer, [80][81][82][83][84][85][86][87][88][89][90][91][92][93][94][95][96][97][98][99] or direct homopolymerization of a macroinimer. [100][101][102] Besides their unique synthetic strategies and novel structural features or topologies, LCHBPs have displayed some novel properties in both bulk and solution states.…”

Section: Introductionmentioning

confidence: 99%

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Long‐Chain Hyperbranched Polymers: Synthesis, Properties, and Applications

Liu

Tian

2018

Macromol. Rapid Commun.

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By combining the virtues of conventional linear and hyperbranched polymers, long‐chain hyperbranched polymers (LCHBPs) have attracted great attention. Therefore, a comprehensive summary of the research progress of LCHBPs is presented, with a particular focus on their synthetic strategies, unique properties, and potential applications. The synthetic methodologies are rationalized into four main classes according to their construction process or mechanism, namely ABx (x ≥ 2), A2 + Bx (x ≥ 3), AB + ABx (x ≥ 2), and self‐condensing vinyl polymerization. Some of their rheological properties, self‐assembly behavior, and stimuli‐response features are then discussed. Finally, the emergent applications including biomedicine, electrical conductivity, chemical sensing, and catalyst carrier, are outlined. It is anticipated that this review will stimulate more inspiration for advancing the development of this novel kind of LCHBP.

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Section: Synthetic Methodologies Of Lchbpsmentioning

confidence: 99%

Section: Lchbps Based On Self-condensing Vinyl Polymerization (Scvp)mentioning

confidence: 99%

Section: Copolymerization Of Small Molecular Inimers and Comonomersmentioning

confidence: 99%

Section: Copolymerization Of Small Molecular Inimers and Comonomersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Long‐Chain Hyperbranched Polymers: Synthesis, Properties, and Applications

Liu

Tian

2018

Macromol. Rapid Commun.

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Synthesis of Highly Branched Copolymers in Microemulsion

Cuneo

Graff

Gao

2019

Macro Chemistry & Physics

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NMP) [20][21][22][23][24] and reversible addition-fragmentation chain transfer (RAFT) polymerization have been intensively applied in the (co)polymerization of inimers and transmers, primarily in solution, for synthesis of branched polymers with various compositions. For instance, those synthesized by ATRP possess high density of chain-end initiating groups and are easy to extend with vinyl monomers using the same technique. [4,48] However, all the solution (co)polymerizations have been shown to result in broad molecular weight distributions due to the random bimolecular (monomer-monomer, monomer-polymer, and polymer-polymer) reactions. [48] Meanwhile, biphasic dispersed systems, such as microemulsion [49][50][51] emulsion, and miniemulsion, [52] have long been employed in conventional radical polymerization and were recently applied in RDRP techniques, [50,51,53] exhibiting intriguing compartmentalization effects on regulating polymerization kinetics and polymer structures. Previous work by our group established a one-pot method for SCVP of inimer in microemulsion through Activators Generated by Electron Transfer [54] (AGET) ATRP. The key feature in this method was that micelles functioned as confined space to segregate the polymerization of inimers into each discrete nanoparticle, which effectively regulated the polymer-polymer reaction and defined the dispersity of the hyperbranched polymers based on the uniformity of the latexes. [4] Further investigation verified the versatility of the method by using a variety of inimer species carrying different reactive and degradable groups. [5] The utility of these hyperbranched polymers was expanded to the synthesis of seeded two-step one-pot polymerization and produce core-shell structured branched polymers. [6] Herein, we present the first, to the best of our knowledge, one-pot copolymerization of inimer and monomer in confined space, that is, microemulsion, providing a simple framework for producing branched polymers with varied compositions and branching densities, while retaining the same extent of polymer molecular weight. To explore the suitability of copolymerization of monomers with inimers in AGET ATRP microemulsion, a model system was developed, consisting of a monomer and inimer with similar structures and vinyl reactivity. The ratio of monomer to inimer was varied to alter the structural composition while holding constant all other formulation parameters, Branched PolymersAtom transfer radical copolymerization of monomer and inimer (containing initiating and monomer fragments in one molecule) is carried out in a micro emulsion to produce branched copolymers with similar molecular weights but varied branching densities. The monomer 2-(isobutyryloxy) ethyl methacrlyate (IEM) shares a similar structure as the selected inimer 2-(2-bromoisobutylryloxy) ethyl methacrylate (BIEM) and provides microemulsification with little change of micelle size upon varying the molar ratio of monomer to inimer (γ ) from 2 to 50. The copolymerization of IEM and BIEM in the disc...

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Synthesis of Thermo‐, Oxidation‐, pH‐, and CO₂‐Responsive Polymers via the Combination of Aza‐Michael and Thiol‐Michael Reactions in One Pot

Qin

Luo

et al. 2019

Macromol. Rapid Commun.

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additional base since amines can act as both nucleophiles and bases, which means that the adducts can be accessed via easily mixing amines with activated olefins. Derived from the step-growth aza-Michael addition polymerization, the amine-containing polymers are generally pH-responsive and CO 2 -responsive, and they can usually be protonated and electropositive so as to interact electrostatically with negatively charged materials. [2,3,[10][11][12][13][14][15][16][17][18] In the case of thiol-Michael reactions, the thiols are the Michael donors. However, bases or nucleophiles as the catalyst are usually indispensable to make the addition smoothly occur. Thiol-Michael reaction has been used to form polymers from simple, ideal step-growth reactions of dithiol and divinyl monomers. The resulting thioether linkages in the backbone endow the polymers with unique characters such as a high degree of flexibility, oxidation-responsiveness, and a relatively high refractive index. [8,9,[19][20][21][22] Owing to the dual role of the amine in which it can directly add to activated olefins (nucleophile) and meanwhile catalyze the thiol-Michael reaction (base), the aza-and thiol-Michael reactions are anticipated to be carried out in a one-pot fashion and no additional catalyst is needed. This may be an effective polymer synthesis strategy because of the distinct advantages as mentioned above. Furthermore, due to the availability of appropriate amine and thiol derivatives, diverse functionalities from the monomers can be facilely incorporated into the polymer backbones, allowing the production of sophisticated macromolecular systems and offering the flexibility to tune their properties, which can largely enrich the functions and diversities of the polymers. Therefore, this strategy can serve as a powerful tool for the design and synthesis of multifunctional polymers. Surprisingly, to the best of our knowledge, even though tremendous efforts have been devoted to apply single type of Michael reaction for polymer synthesis, no example has been focused on the combination of them for synthesis of multifunctional polymers.Herein, we report for the first time the robust synthesis of multifunctional polymers via the combination of efficient azaand thiol-Michael reaction using the commercial diamine, dithiol, and diacrylate in one pot. Specifically, as shown in Scheme 1, the secondary amine undergoes an aza-Michael addition to poly(ethylene glycol) diacrylate (PEGDA) from Multifunctional PolymersThe combination of efficient and harmonious aza-Michael and thiol-Michael reactions in one pot is first reported for the convenient synthesis of thermo-, oxidation-, pH-, and CO 2 -responsive polymers. The simultaneous two-type Michael reactions are proved to proceed smoothly without additional catalyst. The dithiol and diamine are involved in the copolymerization competitively and thus in a random distribution. A wide range of commercially available starting materials are utilized for the simultaneous two-type Michael reactions in one pot to obt...

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A facile synthesis of branched graft copolymers via combination of RAFT self-condensing vinyl polymerization and aldehyde–aminooxy reaction

Abstract: A facile synthetic route to the branched graft copolymer BPDEM-g-PEO has been developed by combination of the RAFT-SCVP technique and aldehyde–aminooxy reaction.

Cited by 17 publications

References 35 publications

Long‐Chain Hyperbranched Polymers: Synthesis, Properties, and Applications

Long‐Chain Hyperbranched Polymers: Synthesis, Properties, and Applications

Synthesis of Highly Branched Copolymers in Microemulsion

Synthesis of Thermo‐, Oxidation‐, pH‐, and CO₂‐Responsive Polymers via the Combination of Aza‐Michael and Thiol‐Michael Reactions in One Pot

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A facile synthesis of branched graft copolymers via combination of RAFT self-condensing vinyl polymerization and aldehyde–aminooxy reaction

Abstract: A facile synthetic route to the branched graft copolymer BPDEM-g-PEO has been developed by combination of the RAFT-SCVP technique and aldehyde–aminooxy reaction.

Cited by 17 publications

References 35 publications

Long‐Chain Hyperbranched Polymers: Synthesis, Properties, and Applications

Long‐Chain Hyperbranched Polymers: Synthesis, Properties, and Applications

Synthesis of Highly Branched Copolymers in Microemulsion

Synthesis of Thermo‐, Oxidation‐, pH‐, and CO2‐Responsive Polymers via the Combination of Aza‐Michael and Thiol‐Michael Reactions in One Pot

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Product

Resources

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Synthesis of Thermo‐, Oxidation‐, pH‐, and CO₂‐Responsive Polymers via the Combination of Aza‐Michael and Thiol‐Michael Reactions in One Pot