Dendrimers and hyperbranched polymers are hot topics with broad and persistent interest for both academic and industrial researchers due to their unique threedimensional highlybranched topology, multifunctionality, special chemical and physical properties, and potential applications. Hyperbranched polymers are highly branched macromolecules with threedimensional dentritic architecture. Hyperbranchedpolymer functionalization of graphene sheets. Dendritic polymers such as dendrimers, hyperbranched polymers, and dendronized polymers are highly branched polymers with complex, secondary architectures and wellde.
Roomtemperature autonomous selfhealing glassy polymers. Doublyresponsive hyperbranched polymers and core crosslinked star polymers with tunable reversibility sunirmal pal, megan r. Geared to novices and experts alike, hyperbranched polymers is a musthave resource for anyone working in polymer architectures, polymer engineering, and functional materials. Design and synthesis of hyperbranched aromatic polymers.
The hyperbranchedtype crosslinker hbpac, which is a hyperbranched polymer with an acryloyl group at the periphery, was obtained as viscous oils in 75% yield by the reaction of the low molecular weight hbpoh mn 3000 with an excess of. A new strategy for synthesis of hyperbranched polymers from commercially available a2 type and bb2 type monomers has been developed. Synthesis, characterization, and lcst behavior mario luzon,1,2 cyrille boyer,2 carmen peinado, 1teresa corrales, michael whittaker, 2lei tao, thomas p. Star and hyperbranched polymers crc press book synthesizing the raw data needed for a wide variety of industrial applications, this work supplies uptodate advanced in research on star, hyperbranched and dendritic polymers. Based on a brief description of the synthesis and properties of hyperbranched polymers, a detailed overview of the research regarding the phase behavior of hyper branched polymers is given, followed by a discussion of new potential chemical engineering applications of hyperbranched.
In 1833, jons jacob berzelius coined the term polymer from the greek word poly, meaning. Wateralcoholsoluble hyperbranched polyelectrolytes and. Encapsulation and controlled release of pharmaceuticals with. Possembedded supramolecular hyperbranched polymers constructed from a 17 branching monomer with controllable morphology transitions. The thermal properties of hyperbranched polymers have been shown to depend on the nature of the chain ends. For larger hyperbranched polymers based on ab 2 monomers the fraction of terminal.
Kulkarni, gregory beaucage introduction hyperbranched polymers hbps constitute a special class of macromolecules characterized by their randomly branched topology obtained in a singlestep synthesis as opposed to the controlled branching of dendrimers which. Silica aerogels and hyperbranched polymers as drug delivery. Hyperbranched polymersall problems solved after 15 years of. Growth click polymerization of ab2 monomers for the. During the past four decades, significant advances in polymer chemistry have been reported including, but not limited to, various controlled polymerization methods atom transfer radical polymerization, reversible additionfragmentation polymerization, ringopening metathesis polymerization, etc. Degree of branching of the hyperbranched polymers resulted. Synthesis and applications of hyperbranched polymers. Hyperbranched polymers 10 years after wiley online library. Hyperbranched polymers for functional surfaces technology portfolio overview joshua a. Hyperbranched polymers and haag type dendrimers for the molecular imprinting of polymers by brandon s lange thesis submitted in partial fulfillment of the requirements for the degree of master of science in chemistry in the graduate college of the university of illinois at urbanachampaign, 2009 urbana, illinois adviser. Recent progress on hyperbranched polymers synthesized via. Hps can be facilely synthesized via a onepot polymerization of traditional small molecular monomers. Hyperbranched polymers with multiple alkyl bromide peripheral groups were synthesized by the copolymerization of styrene with ethylene glycol dimethacrylate 2.
Hyperbranched polymer an overview sciencedirect topics. Maksimova, holger kautz, emilie barriau, holger frey, ulf schlotterbeck. Impact of butyl glycidyl ether comonomer on polyglycerol. For the calculation of the sle the temperature of fusion and the heat of fusion of the hyperbranched polymer have to be known. Future trends in the synthesis and application of hyperbranched polymers. In particular, the influence of uv intensity and reactive blend composition on structural transitions, such as gelation and vitrification, and on the dynamics of internal stress was considered. Watersoluble, thermoresponsive, hyperbranched copolymers. Highly branched polymers that are comprised of dendrimers and hyperbranched polymers represent an intriguing class of macromolecules with compact structure, high density of branching linkers, threedimensional globular shape and multiple chainend groups 16. In the present era, hyperbranched polymers hbps has been received much progress in the structural understanding and their unique chemical and physical properties as well as their potential applications in coatings. Furthermore, hyperbranched polymer has more advantages compared with the twoblock or threeblock polymers, such as the ability to form a small single molecule micelle, lower viscosity, reduce the molecular chain tangles, etc. Structural properties of hyperbranched polymers in the melt under shear via nonequilibrium molecular dynamics simulation tu c. Hyperbranched polymers are often easier to produce since the synthesis strategy is more straightforward.
Watersoluble, thermoresponsive, hyperbranched copolymers based on pegmethacrylates. Thus, hyperbranched pcl could be prepared by using ectvp as the raft agent through scvp route. Jul 01, 2002 hyperbranched polymers are based on the same monomers but contain linear segments and are polydisperse. How hyperbranched polymers compare with dendrimers as well as linear polymers. Synthesis and characterization of hyperbranched polymer. Due to their unique physical and chemical properties and potential applications in various fields from drugdelivery to coatings, interest in hyperbranched polymers is growing rapidly, as confirmed by the increasing number of publications. However, the development of high performance gsbased composites is difficult because of the easy aggregation of gss in a polymer matrix as well as the weak interfacial adhesion between gss and the host polymer. Using 2d nmr to determine the degree of branching of. This approach has been extended recently by combining the ab2. Hyperbranched polymers for functional surfaces technology. The properties of hyperbranched polymers have been shown to depend on several parameters, the most important ones ate. Degree of branching in hyperbranched polymers request pdf. Additionally, the broad peak, due to the merge of multi peaks in gpc traces, further verified such hyperbranched structures.
Oct 24, 2008 degree of branching db is a crucial structure parameter of hyperbranched polymers, which can be determined by 1 h nmr, quantitative c nmr, degradative method, etc. Hyperbranched and highly branched polymer architecturesssynthetic strategies and major characterization aspects brigitte i. May 04, 2011 how hyperbranched polymers compare with dendrimers as well as linear polymers. Pdf hyperbranched polymers 10 years after zhaofeng. Based on the property of the solvents, polymers exhibit variable hydrodynamic radii.
Here, we fabricate a series of randomly hyperbranched polymers rhp with high density of multiple hydrogen bonds, which show t g up to 49 c and storage modulus up to 2. Topological considerations concerning the ratio of linear, imperfectly branched, dendritic and terminal units in hyperbranched polymers based on ab2, ab3 and abm m. Cyclodextrinbased hyperbranched polymers by acyclic diene metathesis polymerization of an abn monomer. The molecular weight of hyperbranched polymers as well as dendrimers determined by sec using linear polymers such as polystyrene, polyethyleneoxide and. Synthesis and property study of bismuth based macronanomaterials 092003072007.
Hyperbranched polymers are phenomenologically different from linear polymers. Hyperbranched polymers have a controllable size of 215 nm yan et al 2010. The crosslinking reaction was continued in a forcedraft oven at 80 c for 45 h and at 110 c for 1 h, and finally 10 h at 50 c in a vacuum oven. Hyperbranched polymer based coatings are with low voc, high solid content ecofriendly because they show lower viscosities at high molecular weights. Hps can be facilely synthesized dendrimers and hyperbranched polymers. We reveal that the hyperbranched structure not only allows the external branch. The synthesis and characterisation of hyperbranched polyesters abstract a new route to the ab2 monomer dimethyl 52hydroxyethoxy isophthalate and its subsequent polymerisation is reported. The incorporation of graphene sheets gss into polymer matrices affords engineers an opportunity to synthesize polymer composites with excellent physical performances. Abstract fifteen years of research on hyperbranched polymers in the group of.
Topological considerations concerning the ratio of linear, imperfectly branched, dendritic and terminal units in hyperbranched polymers based on ab 2, ab 3 and ab m m. Investigating the molecular architecture of hyperbranched. The paper aims to give a brief historical background and to give a survey of hyperbranched polymers in the literature. Hyperbranched polymers developed by our research group 18. The resulted hyperbranched polymer vesicles, defined as branchedpolymersomes bps, have shown unique properties, such as giant and easilytuned. Over the past 15 years, hyperbranched polymers have received much attention due to their unique chemical and physical properties as well as their potential applications in coatings, additives, drug and gene delivery, macromolecular building blocks, nanotechnology, and supramolecular science. Polyurethane networks based on hyperbranched polymer hem. Multipleresponsive dendronized hyperbranched polymers. Especially, hyperbranched polymer was thought to have wide industry prospects due to its simple synthesis method.
Nov 06, 20 hyperbranched polymers developed by our research group 18. Hyperbranched polyesters were prepared by melt condensation polymerisation of the ab2 monomer and also by copolymerisation with suitable core molecules. In sharp contrast, the polyacetalization of the nonprotected homologue, namely, hydroxymethylbenzaldehyde 2. Today it is known that this is true for many aspects, for example, both types. Wo2008068180a1 binder mixture comprising hyperbranched. Possembedded supramolecular hyperbranched polymers. The present invention provides a binder comprising a 0. However, for complicated hyperbranched polymers, intricate structure and severe overlap of spectral signals hinder the determination of db using traditional methods. Inoue department of applied chemistry, faculty of engineering, ehime university, matsuyama 7908577, japan received 7 november 1999. Furthermore, the triazole group in a linear l monomer unit complexed cu i, which catalyzed a faster reaction of the second azide group to quickly convert the l unit into a dendritic unit, producing hyperbranched polymers with db0. Supakij suttiruengwong aus bangkok, thailand erlangen 2005. Controlled synthesis of hyperbranched polymers by slow monomer addition to a core p. Their globular and dendritic architectures endow them with unique structures and properties such as abundant functional groups, intramolecular cavities, low viscosity, and high solubility. How hyperbranched polymers compare with dendrimers as well as linear polymers future trends in the synthesis and application of hyperbranched polymers geared to novices and experts alike, hyperbranched polymers is a musthave resource for anyone working in polymer architectures, polymer engineering, and functional materials.
Hyperbranched polymers are polymers based on axbmonomers, ie, monomers having one bfunctionality and two or more agroups resulting in polymers with a potential branching point in each repeat unit. The reactivity difference between the b group in linear unit and that in terminal group has great effect on the molecular parameters of the products obtained. Jun 21, 2015 hyperbranched polymers hbps, an important subclass of dendritic macromolecules, are highly branched, threedimensional globular nanopolymeric architectures. In photocatalysis, these hyperbranched polyelectrolytes show good water dispersity and provide good interface contact between polyelectrolytes and water, resulting in e.
Rajendar reddy mallepally aus hyderabad, india erlangen 2009. Polymerization for advanced applications sigmaaldrich. The reaction of ab 2 monomers with a core molecule of the structure b f is also treated. Functional dendrimers, hyperbranched and star polymers. The present invention further provides the preparation of the binder mixture, the woodbase. Structure of hyperbranched polyglycerol and amphiphilic polyglycerol esters in dilute aqueous and nonaqueous solution vasil m. Investigating the molecular architecture of hyperbranched polymers amit s. Leibniz institute of polymer research dresden, hohe strasse 6, 01069 dresden, germany.
Pdf chapter 2 hyperbranched polymers ahmad reza taheri. The development of hyperbranched polymers is a rapidly expanding field in the area of macromolecular science. Controlled synthesis of hyperbranched polymers by slow. New paper describes firstever synthesis of hyperbranched.
Tuneable extraction systems based on hyperbranched polymers. Attractive features like highly branched topological structures, adequate spatial cavities, numerous terminal functional groups and convenient synthetic procedures distinguish them from. History of hyperbranched polymers as shown in table 1, showing the development of hyperbranched polymers, highly branched arti. Chao gao as his supervisor in the department of polymer science and. Jul 28, 2011 the analytical expressions of the various structural units and the average degree of branching for the hyperbranched polymers resulted from ab2 polycondensation with substitution effect were derived by the kinetic mechanism. The conformation of hyperbranched polymers from one pot polymerization with abn n 2, 4 type monomers, applying the reactive 3d bond fluctuation lattice model, are.
Polymers free fulltext hyperbranched polycaprolactone. Hyperbranched polymers are used as polymeric additives in many linear commercial polymers as compatibilising agents, process and strength improvers. Dsc showed that the hyperbranched resins decomposed between 315345c. Uhlherr3 1centre for molecular simulation, swinburne university of technology. The properties of hyperbranched polymers to a large extent depend on the endgroup structure and this can be used to tailor their properties. Voit and albena lederer leibniz institute of polymer research dresden, hohe strasse 6, 01069 dresden, germany received february 20, 2009 contents 1. Fluorocarbon polymers, like smallmolecule fluorocarbons, exhibit increased thermal stability, hydrophobicity, lipophobicity, improved chemical resistance, and decreased intermolecular attractive forces in comparison to their hydrocarbon analogs. In many cases, the hyperbranched polymers are discussed as a more rapidly prepared and more economical replacement for perfect dendrimers in special applications. Selfassembly of phospholipidanalogous hyperbranched polymers nanomicelles for drug delivery. Durham etheses the synthesis and characterisation of.
The synthesis of a hyperbranched polymer is easier than that of dendrimers as hyperbranched polymers can be synthesized in a onestep process from ab x. Polymer plastics technology and engineering 2016, 55 1, 92117. Glassy polymers are extremely difficult to selfheal below their glass transition temperature t g due to the frozen molecules. Functional dendrimers, hyperbranched and star polymers k. Quickly, the potential of aromatic hb polyesters as blend components was. For coatings applications, the hyperbranched fluorinated polymer has to be crosslinked to make it less brittle fluorocarbon polymers have not only reduced adhesion, but also reduced cohesion. Domanska and zolektryznowska estimated the temperature of fusion and heat of fusion of boltorn w3000 using differential scanning calorimetry dsc. Hyperbranched polymers made from a2 and bb2 type monomers. Pdf hyperbranched polymers for coating applications. Hyperbranched polymers have a dendritic structure with a large number of endgroups 1,2,3.
One group of polymers which has the potential to merge the approaches of utilizing high molar mass and complex molecular architecture is hyperbranched hb polymers. Hyperbranched polymers are used as polymeric additives in many linear commercial. Structural properties of hyperbranched polymers in the. Hyperbranched polymers hps are highly branched threedimensional 3d macromolecules. Polymers obtained from the statistical polymerization of axb monomers by means of condensation or addition procedures are referred to as hyperbranched polymers. Jul 16, 2015 hyperbranched polymers with treelike nanostructures and multiple chainend functionalities represent an important type of soft nanomaterials that can be used in a variety of applications, ranging. In the first part of this series, hyperbranched polysulfone. Hyperbranched polymersilica nanocomposites which are very important in. Direct growth of hyperbranched polymers on both ends of a linear polymer was reported recently by wan and pan.
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