Synthesis and Thermoresponsive Behaviors of Thermo-, pH-, CO<sub>2</sub>-, and Oxidation-Responsive Linear and Cyclic Graft Copolymers

Zhang, Hongcan; Wu, Wentao; Zhao, Xiaoqi; Zhao, Youliang

doi:10.1021/acs.macromol.7b00220

Cited by 69 publications

(75 citation statements)

References 81 publications

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“…Hence, the obtained polymers are integrated to be triply responsive (thermo‐, oxidation‐, and pH/CO 2 ‐responsive). The behavioral change of a macromolecule in biological system is often a result of a combination of environmental changes, and therefore multistimuli‐responsive polymer, which can provide better spatiotemporal control, offers an ideal platform to mimic the biological processes and has received much attention in the past decade . Owing to the commercially available starting materials, our work provides a convenient strategy for the synthesis of applicable multifunctional polymers in a large scale.…”

Section: Methodsmentioning

confidence: 99%

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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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Section: Methodsmentioning

confidence: 99%

“…Besides thermo‐responsiveness, these kinds of functional polymers containing thioether groups are expected to be oxidation‐responsive as well . For this study, PEG200DA‐EDT‐PA was adopted for the oxidation testing.…”

Section: Methodsmentioning

confidence: 99%

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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“…As is known, most of the covalent bonds linked polymers tend to be either soft or brittle, not capable of exhibiting performance for self‐healing and responses to external stimuli . Relatively, polymers with dynamic supramolecular interactions show great potential in providing materials with better functions such as stretchability, durability, self‐recovery, and stimuli‐responsiveness, thus can find more applications in drug delivery, artificial implants, tissue engineering, etc …”

Section: Introductionmentioning

confidence: 99%

Photoregulating of Stretchability and Toughness of a Self‐Healable Polymer Hydrogel

Xiong

Zhang

Xie

et al. 2018

Macromol. Rapid Commun.

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Supramolecular hydrogels that are assembled through dynamic host-guest interactions have presented apparent potential in the construction of materials with promising performance. Herein, a photoregulated hydrogel cross-linked by host-guest interactions with multifunctions of high stretchability, strong toughness, and rapid self-healing property is reported. The hydrogel exhibits unique light-responsive property due to the introduction of two photoisomerized groups. For example, the stress-strain curve of the original hydrogel indicates 1020% rupture strain with the maximum tensile strain value of 214 kPa. Upon 365 nm light irradiation for an hour, its tensile strain increases to 15 times with lower tensile stress indicating a better stretchability. Moreover, the hydrogel is photochromic and surface patternable, where it can reversibly switch color between luminous yellow and brown while exposed to 365 and 440 nm light irradiation. It holds great promise for applying in self-recovering optically controlled and labeled elastic mechanical materials.

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“…Azide‐alkyne click chemistry is often coupled with controlled radical polymerization methods such as atom transfer radical polymerization (ATRP), nitroxide‐mediated polymerization (NMP), and ring‐opening metathesis polymerization (ROMP) for the purpose of synthesizing diverse structured polymers. The introduction of alternating linear polymer allows to create functional materials usually exhibiting diverse features . Sumerlin et al coupled azido terminal polymers and azido functional charge transfer agents with various propargyl‐terminated molecules and obtained a range of functional telechelics and charge transfer agents .…”

Section: Introductionmentioning

confidence: 99%

Azide telechelics chain extended by click reaction: Synthesis, characterization, and cross‐linking

Sunitha

Unnikrishnan

Nair

2018

Polymers for Advanced Techs

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Azide telechelics of poly(dimethylsiloxane) (PDMS), polypropylene oxide (PPO), and polyethylene oxide (PEO) were synthesized from the corresponding epoxy telechelics and characterized. These oligomeric azides were chain extended by reaction with bispropargyl ether of bisphenol A (BPEBA) through a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. PDMS manifested a faster reaction in contrast to PPO or PEO. The chain-extended polymers underwent cross-linking above 170°C through thermal cleavage of residual (terminal) azide groups. This was manifested in their rheograms and was further substantiated by FTIR and NMR spectroscopic analyses. Dynamic mechanical analyses of the cross-linked polymers exhibited characteristic transitions of hard and soft segments, implying microphase separation in the system. Microscopic evaluation of the thermally cross-linked sample revealed a porous morphology with microsized to nanosized pores. KEYWORDS azide telechelics, propargyl ether, thermal cross-linking, triazole, click reaction 1 | INTRODUCTION Telechelic polymers evince a lot of interest because of their various applications such as precursors for the synthesis of multiblock copolymers and synthesis aid for a large number of branched and complex polymeric structures. 1,2 For example, hydroxyl-terminated polybutadiene (HTPB) is a well-known telechelic system used as a propellant binder and as adhesive, sealant, elastomer, 3 etc. End-functional poly(dimethylsiloxane) (PDMS) is another example of a very useful synthesis intermediate widely used in adhesives, sealants, and coatings formulations 4 in space research. The possibility to externally steer the morphology and the associated physical properties of telechelic polymers renders them important and versatile building blocks for modern materials science. 2,3Diverse methods such as anionic, cationic, ring opening, group transfer, free radical, step-growth polymerization, and chain scission processes are adopted for the syntheses of these telechelic polymers. [5][6][7][8] The criticality in synthesis of telechelic polymers lies in the quantitative introduction and subsequent conversion of the functional group at the chain ends. Living polymerization technique is a good technique for getting telechelic polymers with narrow molecular weight distribution. 9,10 However, the properties of polymers obtained by end-linking of telechelic oligomers depend strongly on stoichiometry, side reactions, extent of conversion, etc. The relative reactivities of the groups, substitution effects, side groups, etc play a major role 11,12 in deciding the success factor. Different types of synthesis strategies such as Diels-Alder, [13][14][15] thiol-ene, [16][17][18][19] and azide-alkyne 20,21 figure under the title of "click chemistry." Of these, the Diels-Alder belongs to a class of thermoreversible reactions. 22 Copper-catalyzed azide-alkyne cyclo addition (CuAAC) is shown to be the most effective and versatile, since it is highly specific and efficient, requires mild conditions, 23 has ...

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Synthesis and Thermoresponsive Behaviors of Thermo-, pH-, CO₂-, and Oxidation-Responsive Linear and Cyclic Graft Copolymers

Cited by 69 publications

References 81 publications

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

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

Photoregulating of Stretchability and Toughness of a Self‐Healable Polymer Hydrogel

Azide telechelics chain extended by click reaction: Synthesis, characterization, and cross‐linking

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Synthesis and Thermoresponsive Behaviors of Thermo-, pH-, CO2-, and Oxidation-Responsive Linear and Cyclic Graft Copolymers

Cited by 69 publications

References 81 publications

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

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

Photoregulating of Stretchability and Toughness of a Self‐Healable Polymer Hydrogel

Azide telechelics chain extended by click reaction: Synthesis, characterization, and cross‐linking

Contact Info

Product

Resources

About

Synthesis and Thermoresponsive Behaviors of Thermo-, pH-, CO₂-, and Oxidation-Responsive Linear and Cyclic Graft Copolymers

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

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