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

Mu, Bin; Liu, Tingting; Tian, Wei

doi:10.1002/marc.201800471

Cited by 43 publications

(40 citation statements)

References 168 publications

(961 reference statements)

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“…[31,32] As branched analogs of HBPs, longchain hyperbranched polymers (LCHBPs) have attracted considerable attention in the past decades. [33] The linear subchains between branching points endow LCHBPs with virtues of both HBPs and linear polymers, and by altering the subchain length, fine tuned LCHBP materials can be obtained conveniently. How ever, the introducing of cyclic segment between branching points of HBPs is rarely reported, and the combination of cyclic and branched topologies may produce a much more compact conformation, which would cause lower viscosity that may have potential application value in polymer processing or synthetic lubricants, etc.…”

Section: Uv-vis Spectrophotometry and Triple-detection Size-exclusiomentioning

confidence: 99%

“…Nevertheless, gelation is an intrinsic issue in this system, and various strategies have been developed to avoid gelation, including optimization of polymerization conditions and utilizing of couple‐monomer methodology . As branched analogs of HBPs, long‐chain hyperbranched polymers (LCHBPs) have attracted considerable attention in the past decades . The linear subchains between branching points endow LCHBPs with virtues of both HBPs and linear polymers, and by altering the subchain length, fine‐tuned LCHBP materials can be obtained conveniently.…”

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confidence: 99%

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Hyperbranched Multicyclic Polymer Built from Tailored Multifunctional Monocyclic Prepolymer

Liu

Zhang

et al. 2019

Macromol. Rapid Commun.

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A simple and efficient method to construct a hyperbranched multicyclic polymer is introduced. First, a tailored trithiocarbonate with two terminal anthracene units and three azide groups is successfully synthesized, and this multifunctional trithiocarbonate is used as chain transfer agent (CTA) to afford anthracene‐telechelic polystyrene (PS) via reversible addition‐fragmentation chain transfer (RAFT) polymerization. After that, linear PS is irradiated under 365 nm UV light to achieve the cyclization process. The monocyclic polymer further reacts with sym‐dibenzo‐1,5‐cyclooctadiene‐3,7‐diyne via “A2+B3” strategy based on a self‐accelerating click reaction to produce hyperbranched multicyclic polymer. The structures and properties of the polymers are characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), UV–vis spectrophotometry, and triple‐detection size‐exclusion chromatography (TD‐SEC). The number of monocyclic units of the resultant hyperbranched multicyclic polymer reaches about 21 based on multi‐angle laser light scattering (MALLS) measurements. The plot of intrinsic viscosity versus molecular weight reveals that the α value of the unique hyperbranched multicyclic polymer is lower than both hyperbranched polymers and cyclic polymers.

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Section: Uv-vis Spectrophotometry and Triple-detection Size-exclusiomentioning

confidence: 99%

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confidence: 99%

Hyperbranched Multicyclic Polymer Built from Tailored Multifunctional Monocyclic Prepolymer

Liu

Zhang

et al. 2019

Macromol. Rapid Commun.

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“…The introduction of, normally, randomly dispersed dendritic units with multi-functionalities along the polymeric backbone is key to the unique physiochemical properties they possess [4,5]. In comparison with their linear counterparts, highly branched materials exhibit low viscosity and enhanced solubility, and the higher density branches can optionally possess functional groups to allow further modification [6]. The relative simplicity of the synthetic routes to dendritic branches differentiates them from the perfectly structured dendrimers that require laborious synthesis and work-up procedures; the higher the generation number, the more likely defects are to be generated.…”

Section: Introductionmentioning

confidence: 99%

Spatially Controlled Highly Branched Vinylsilicones

2021

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Branched silicones possess interesting properties as oils, including their viscoelastic behavior, or as precursors to controlled networks. However, highly branched silicone polymers are difficult to form reliably using a “grafting to” strategy because functional groups may be bunched together preventing complete conversion for steric reasons. We report the synthesis of vinyl-functional highly branched silicone polymers based, at their core, on the ability to spatially locate functional vinyl groups along a silicone backbone at the desired frequency. Macromonomers were created and then polymerized using the Piers–Rubinsztajn reaction with dialkoxyvinylsilanes and telechelic HSi-silicones; molecular weights of the polymerized macromonomers were controlled by the ratio of the two reagents. The vinyl groups were subjected to iterative (two steps, one pot) hydrosilylation with alkoxysilane and Piers–Rubinsztajn reactions, leading to high molecular weight, highly branched silicones after one or two iterations. The vinyl-functional products can optionally be converted to phenyl/methyl-modified branched oils or elastomers.

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“…Hyperbranched polymers have many unique physical and chemical properties and have shown great application value in many fields such as coatings, catalysts, biomedicine, etc., which are attributed to their unique structure. [1][2][3][4][5][6] At present, many synthesis methods of the hyperbranched polymers have been developed. For example, AB g type polycondensation, [7][8][9] self-condensation vinyl polymerization (SCVP), [10] ring opening polymerization, [11] multimonomer methods, [12] and so on.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Methods of the Size Distribution Function for the Products of Hyperbranched Polymerization

Hao

Zhou

Nie

2020

Macro Theory & Simulations

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wide application of the hyperbranched polymers. To solve this problem, people first need to understand the relationship between monomer type, reaction conditions, and product structure parameters.In fact, the theoretical development of hyperbranched polymers has been in step with the experimental work, and guides the experimental development. At first, the resin with highly free branched structure was prepared mainly based on A a , and A a +B b type approaches. [13,14] This kind of polymerization is easy to gel. Flory carried out the theoretical research on hyperbranched polymers in 1940s. [15][16][17] He first demonstrated the possibility of preparing highly branched polymers from polyfunctional monomers, and calculated the critical gel conditions and relative molecular weight distribution of three functional and four functional branched monomers by means of probability statistics. In 1952, he further predicted the possibility that AB g type monomers could form highly branched polymers via condensation polymerization and derived the molecular weight distribution function for the products obtained by the probability method. [18] From another point of view, Stockmayer thinks that polymerization is similar to that of gas liquefaction. By using statistical mechanics methods of non-ideal gases, he derived the gelation conditions and size distribution functions of products for the A a , A 2 +A a , and A 2 +A a +B 2 (a > 2) type branching reactions. [19][20][21] Like the experiment of hyperbranched polymer synthesis, a new round of theoretical research climax also originated from the work of Kim et al. in the 1980s, [7][8][9] when they first synthesized highly branched polyphenylene with AB 2 monomer, and named this kind of product hyperbranched polymer. Because of its unique structure and characteristics, it is expected that it will be widely used in many fields, which has attracted the general attention of academia and industry. Hawker et al. [22] and Kim et al. [7][8][9] proposed the definition of the degree of branching (DB) of hyperbranched polymers by comparing them with perfectly branched dendrimers, Frey et al. [23,24] derived the formula of degree of branching for AB g hyperbranched polymers by kinetic and statistical methods respectively. Müller and Yan et al. developed the kinetic theory for AB 2 polycondensation and SCVP, and derived the analytical expressions of branching degree, polymerization degree distribution function, and other molecular parameters for the products. [25,26] Then Yan and Zhou [27][28][29][30][31] extended the kinetic method to the polycondensation of more general AB g type monomers and the reaction system in the presence of the In the theory of hyperbranched polymerization, due to the difficulty of deriving isomers of conformations, the early Flory's probability method and Stockmayer's statistical mechanics method have been rarely used. In this work, a new and easy way to derive the total number of configurations is developed, which can extend the application of the two theoretical me...

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

Cited by 43 publications

References 168 publications

Hyperbranched Multicyclic Polymer Built from Tailored Multifunctional Monocyclic Prepolymer

Hyperbranched Multicyclic Polymer Built from Tailored Multifunctional Monocyclic Prepolymer

Spatially Controlled Highly Branched Vinylsilicones

Theoretical Methods of the Size Distribution Function for the Products of Hyperbranched Polymerization

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