Chao gao as his supervisor in the department of polymer science and engineering at zhejiang university. Multipleresponsive dendronized hyperbranched polymers acs. Hyperbranched polymers with high degrees of branching and low. Raft polymerisation allows the control over the polymer synthesis by the simple addition of raft agent 7, and potentially dangerous or toxic. They are based on aromatic polyester hyperbranched polymer, are carboxylend hyperbranched polymer with high molecular weight and high activity. Nevertheless, the functional group numbers coupled with lower purchasing costs make these materials extremely promising in future applications. Functional dendrimers, hyperbranched and star polymers k. The last two decades have seen a surge of interest in hyperbranched polymers due to their ease of synthesis on a large scale and their promising applications in diverse fields, from medicine to nanotechnology.
Hyperbranched polymers are a subclass of dendritic molecules characterised by a highly branched architecture. It is also useful for scientists in related fields who need a primer on the synthesis, theory, and. Hyperbranched bismpa polyester16hydroxyl, generation 2. Hyperbranched polymers hbps have attracted considerable attention during the past decade because of their intrinsic globular structures and unique properties, such as low viscosity, high. Hyperbranched polymers for biomedical applications springerlink. Chapter i provides a general introduction to the basic concepts of living.
Hyperbranched polymers are used in many applications due to their. How hyperbranched polymers compare with dendrimers as well as linear polymers. Hyperbranched polymers are unique in that their properties are easily tailored by changing the nature of the end groups. A linear polymer, hyperbranched polymers with various degrees of branching, and 100% hyperbranched polymers were successfully synthesized by selfpolycondensation of 2,2,2trifluoro144phenoxyphenoxyphenylethanone by using different amounts of trifluoromethanesulfonic acid from the same ab 2 monomer. The count includes downloads for all files if a work has more than one. Jun 21, 2015 bioapplications of hyperbranched polymers. Hyperbranched polymers, an important subset of dendritic macromolecules, are highly branched, and have 3d globular nanopolymeric architectures.
Physical properties of polymers from protocatechuic acid and vanillic acid. Hyperbranched polymers with multiple alkyl bromide peripheral groups were synthesized by the copolymerization of styrene with ethylene glycol dimethacrylate 2. In the perspective of obtaining regulatory approval, this can be seen as a disadvantage. From the thermodynamic point of view, the modelling of these phase diagrams is quite challenging, because the thermodynamic properties depend on the architecture of the.
A process for preparing a hyperbranched polymer having a weightaverage molar mass of at least 30,000, includes coupling a first prepolymer having at least three functional end groups with a second prepolymer having at least two functional end groups by a dehydration condensation reaction between the end groups in the prepolymers. Army research laboratory has discovered a polymer that boosts bacteria growth. A muchneeded overview of the state of the art of hyperbranched polymers. Hbps can be straightforwardly synthesized in onepot processes, possess globular structures determined by their architecture as opposed to folding in proteins, and have documented ligand binding and catalytic properties. Structure of hyperbranched polyglycerol and amphiphilic polyglycerol esters in dilute aqueous and nonaqueous solution. Synthesis, properties, and applications a muchneeded overview of the state of the art of hyperbranched polymers. Synthesis of structurally controlled hyperbranched polymers using a. 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. Applications contrast agents for mri preliminary tests show dendrimers are stronger also good for mra. A read is counted each time someone views a publication summary such as the title, abstract, and list of authors, clicks on a figure, or views or downloads the fulltext. Hyperbranched polymers are phenomenologically different from linear polymers. Rajendar reddy mallepally aus hyderabad, india erlangen 2009. 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. The surface groups of hyperbranched polyglycerol were modified from hydroxyl to amine groups and then covalently modified to contain rhodamine to image by microscopy.
Hyperbranched polymers are less perfect molecules but still possess the highly branched architecture with a multitude of endgroups. Synthesis and characterisation of hyperbranched polymers. Interestingly, the irregularity of branching increases the functionality of the polymers for applications as sensors, delivery devices, coatings, crosslinkers and catalysts. There are four kinds of carboxylend hyperbranched polymers hyper c10, c20, c30 and c40 according to their chemical structure. Hyperbranched polymers are highly branched macromolecules with threedimensional dentritic architecture. Thermoresponsive and reducible hyperbranched polymers. Hyperbranched polymers show an outstanding potential for applications ranging from chemistry over nanotechnology to pharmacy. Synthesis of structurally controlled hyperbranched.
Perfluoroalkylfunctionalized hyperbranched polyglycerol. Thermogravimetric analysis of the decomposition of both pa and vabased polymer. Multifunctional hyperbranched glycoconjugated polymers. Fluorescent hyperbranched conjugated polymers fhcps can be used in sensing applications, as their fluorescense and conjugated character allow for high sensitivity toward analytes. Hyperbranched polymers with high transparency and inherent high refractive index for application in organic light. It is also useful for scientists in related fields who need a primer on the synthesis, theory, and applications of hyperbranched polymers. Hyperbranched polymers hps are highly branched threedimensional 3d. Through the michaeladdition polymerization of gentamycin and n,n. The number of arms andor molar mass of the functionalized. For some areas, such as coating resins and tougheners in epoxyresins, hyperbranched polymers are foreseen to play an important role. Duetotheiruniquephysicalandchemical properties and potential applications in various.
Nov 06, 20 hyperbranched polymers coating applications 1. Hyperbranched polymer hydrogels formed from both physical or chemical. Growth click polymerization of ab2 monomers for the. Hyperbranched polymers with controlled degree of branching. At the same time, the crosslinking molecule can be used to introduce other properties or additional functional groups. Influence of salinity, ph, and concentration on dispersion effectiveness a thesis presented to the graduate school of clemson university in partial fulfillment of the requirements for the degree master of science environmental engineering and earth sciences by kristen mae carpenter. One of the properties of dendrimers is they can be made water soluble unlike most synthetic polymers. Our strategy will be to use excess cui1 to control gelation, so called enhanced deactivation atrp. Encapsulation and controlled release of pharmaceuticals with. The hydroxyl group can be modified to obtain other functional polymers. It was found that the hyperbranched polymers studied could enter cells and were of appropriate size to be excluded from the nucleus.
Hyperbranched polymers hps are highly branched threedimensional 3d macromolecules. The resultant hyperbranched polymer with carboxylic acid terminal groups was endcapped with panisidine in order to avoid the aggregation effect in the. Hyperbranched polymers wiley online books wiley online library. Linear and hyperbranched multifunctional fivemembered cyclic carbonate 5ccbased polymers with welldefined structures, high weightaverage molecular weights mw up to 42500, and versatile properties such as aggregationinduced emission as well as chiral and porous properties are successfully produced in excellent yields up to 96%. Hy p erbranched polyamide resin hyper hpn202 product description. Fluorescent polymers can be useful in sensing because they may change their signal when in contact with analytes. In order to take advantage of this potential, the underlying phase behaviour must be known. Hyperbranched polymers that catalyze bacterial growth. New approaches for energy storage with hyperbranched polymers.
Hyperbranched alkanes for lubes us department of energy. Inset left shows the publication contributions of the top ten states form 1990 to 30 2005. Yan college of chemistry and chemical engineering, shanghai jiao tong university, 800 dongchuan road, shanghai 200240, china. Functional dendrimers, hyperbranched and star polymers. Perfluoroalkylfunctionalized hyperbranched polyglycerol as. Hyperbranched polymers hbps have attracted great interest due to their characteristics such as low viscosity, high solubility, numerous terminal groups, globular architecture and good capacity of encapsulating guest molecules. We propose a versatile approach to the production of hyperbranched polymers with high degrees of branching and low dispersity values d, involving slow monomer addition of a thiolyne monomer to multifunctional core molecules in the presence of photoinitiator and under uv irradiation. Hyperbranched and highly branched polymer architecturesssynthetic strategies and major characterization aspects brigitte i. Targeted multimodal hyperbranched polymers for imaging and. Hbps can be straightforwardly synthesized in onepot processes, possess globular structures determined by their architecture as opposed to folding in proteins, and have documented ligand. In 1833, jons jacob berzelius coined the term polymer from the greek word. Companies that want to leverage the technology, using it to create new products and services, can apply for a patent license agreement.
The thermomechanical properties of hyperbranched polymerepoxy blends and their dependence on hyperbranched polymer shell chemistry were investigated. Dendrimers usually a product of noniterative polymerization dendrimers are highly ordered differentiated by structural perfection. Synthesis of hyperbranched polymers with controlled degree. The method of preparing hyperbranched polymers by sunlight is also applicable for the systems only based on thiolene reaction.
This book presents a comprehensive study on a new class of branched polymers, known as hyperbranched polymers hbps. Hyperbranched polyamide wuhan hyperbranched polymers. From the thermodynamic point of view, the modelling of these phase diagrams is quite challenging, because the thermodynamic. Geared to novices and experts alike, hyperbranched polymers is a musthave resource for anyone working in polymer architectures, polymer engineering, and functional materials. While the former was better performing in terms of toughness, the latter showed. As noted above illdefined stars were prepared from hyperbranched cores prepared by atrp of ab molecules, i. Growing hyperbranched polymers using natural sunlight. Influence of branching architecture on polymer properties pages. A linear polymer, hyperbranched polymers with various degrees of branching. This thesis describes the development of a novel route for preparation of hyperbranched polymers. Preparation of hyperbranched polymers by controlledliving. Jun 10, 2015 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.
Based on aromatic polyamide structure, hydroxylended hyperbranched polyamide hyper hpn202 owning some particular properties, such as high molecular weight and high activity. Pdf hyperbranched polymers for coating applications. Dendrimers are polymeric macromolecules composed of multiple perfectlybranched monomers radially emanating from a central core figure 1. The target of this body research is mainly focused on development of new methodologies for synthesis of hyperbranched polymers and hyperbranched star hyperstar polymers with controlled structures and sitespecific functionalities via controlled radical polymerization crp techniques. Mar 14, 2017 new hyperbranched polymers have been investigated to provide new structurefunction relationships necessary for electrical and optical applications. Recent progress on hyperbranched polymers synthesized via. Nowadays hbps have shown many applications in polymer science and engineering, owing to the merits of convenient. Their globular and dendritic architectures endow them with unique structures and properties such as abundant functional groups, intramolecular cavities, low viscosity, and high solubility. Hyperbranched polyester series wuhan hyperbranched.
After cleavage of the disulfide bridge, the authors confirm that the polymers chains. Hyperbranched polymers hbps have shown widespread academic and commercial success in the preparation of films and novel materials, and now are emerging into the biomedical research space as nanocarriers for use in drug delivery and diagnostics. Improved additives promote the growth of microorganisms. May 7, 2016 1 this presentation does not contain any proprietary, confidential, or otherwise restricted information june 8 th, 2016 project id. Synthesis of ligninbased phenol terminated hyperbranched. In this article, we demonstrate the need for developing high dielectric. Dendrimers and hyperbranched polymers for controlling nuclear. These polymers, with their multitude of branches, are created in a onepot synthesis without the necessity of multiple synthetic steps required for traditional dendrimer synthesis. Jul 28, 2010 a linear polymer, hyperbranched polymers with various degrees of branching, and 100% hyperbranched polymers were successfully synthesized by selfpolycondensation of 2,2,2trifluoro144phenoxyphenoxyphenylethanone by using different amounts of trifluoromethanesulfonic acid from the same ab2 monomer. The aim is to produce hyperbranched polymers via enhanced deactivation atrp without crosslinking even at high conversion. 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.
Phase diagrams for systems containing hyperbranched polymers. Hyperbranched polymers with high transparency and inherent. The glucosebased hyperbranched polymer obtained had a m w of 16200, db of 0. Thermomechanical properties of hyperbranched polymer. Hyperbranched polymers are used as polymeric additives in many linear commercial polymers as compatibilising agents, process and strength improvers. Maksimova, holger kautz, emilie barriau, holger frey, ulf schlotterbeck. Rearrange individual pages or entire files in the desired order.
The mixture of potc and glucosamine in dmf was irradiated by sunlight for 20 h. Unlike welldefined dendrimers, hbps have linear units in structures except dendritic and terminal units, and the degree of branching db of them are usually less than 0. Hyperbranched polymers with controlled degree of branching from. It discusses in detail the synthesis strategies for these particular classes of po.
This is accomplished by obtaining high dielectric constants. Hyperbranched polymers are used in many applications due to their advantageous properties such as low intrinsic viscosity, low glass transition temperature, and. 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. Nevertheless, there was less study on the preparation and performance of functionalized hyperbranched polyamidoamine based selfassembly supramolecular systems.
Other approaches led to polymers with topologies similar to that of comb or star shaped polymer architectures. Hyperbranched polymers were shown to be able to increase resin toughness by inducing both a heterogeneous and homogeneous morphology. Future trends in the synthesis and application of hyperbranched polymers. Structure of hyperbranched polyglycerol and amphiphilic polyglycerol esters in dilute aqueous and nonaqueous solution vasil m. Doublyresponsive hyperbranched polymers and core crosslinked star polymers with tunable reversibility sunirmal pal, megan r. The number of branch points increases upon moving from the. Hps can be facilely synthesized dendrimers and hyperbranched polymers. Fulltext downloads displays the total number of times this works files e. Voit and albena lederer leibniz institute of polymer research dresden, hohe strasse 6, 01069 dresden, germany received february 20, 2009 contents 1. As we all know, functionalization of hyperbranched polymers was a reliable way to expand their application fields and develop new functional materials 28,29. Hyperbranched polymers hbps as a polymer with a threedimensional and highly branched globular structure have emerged during the past twenty years 1,2,3,4. The target of this body research is mainly focused on development of new methodologies for synthesis of hyperbranched polymers and hyperbranchedstar hyperstar polymers with controlled structures and sitespecific functionalities via controlled radical polymerization crp techniques. Application of controlled radical polymerization in the. Hyperbranched polymer an overview sciencedirect topics.
Watersoluble, thermoresponsive, hyperbranched copolymers. Multifunctional linear and hyperbranched fivemembered. Files available from the acs website may be downloaded for. Their globular and dendritic architectures endow them with. Such polymers are usually prepared in an easy and affordable onepot synthesis and therefore are considered suitable for industrial largescale applications such as. Pdf chapter 2 hyperbranched polymers ahmad reza taheri. Inoue department of applied chemistry, faculty of engineering, ehime university, matsuyama 7908577, japan received 7 november 1999. Pei polymers and corexit was also determined for various aquatic environments. In order to stimulate different environments that could be exposed to oil spills, the salinity and ph of the artificial seawater used in the dispersion tests was altered. Pdf hyperbranched macromolecules hms, also called hyperbranched polymers are highly branched threedimensional 3d structures in.
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. Multifunctional gene vectors with high transfection, low cytotoxicity, and good antitumor and antibacterial activities were prepared from natural aminoglycosides. Hyperbranched alkanes for lubes lelia cosimbescu, joshua robinson, j. We can take advantage of longrange delocalization in these structures for energy storage applications. Polymers free fulltext selfassembly supramolecular.
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