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The synthesis of hyperbranched poly(methyl methacrylate) (PMMA) via reversible addition fragmentation chain transfer (RAFT) polymerization was investigated by varying the ratio chain transfer agent (CTA): monomer (methyl methacrylate, MMA): brancher (ethylene glycol dimethyl methacrylate, EGDMA): free radical initiator (AIBN) at various temperatures (50, 55, 60, 65, 70 °C). The rate of polymerization was observed to increase with temperature and concentration in brancher, whilst it was lowered by an increase in chain transfer agent concentration. The molecular weight of the samples increased with the ratios brancher: CTA and monomer: CTA. The polydispersity of the samples increase with conversion, as the level of branching increases. At fixed concentration in brancher, an increase of CTA concentration led to polymers with lower PDI. The variation of enthalpy and entropy relative to the monomer reaction were calculated, and it was observed that an increase in the brancher concentration induced an increase in both and , whilst lower CTA concentrations led to an increase in . The variation in Gibbs energy for the monomer reaction was calculated at 60 °C, and results confirmed the presence of a retardation effect when increasing CTA concentration generally observed in RAFT polymerization. 相似文献
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Multiblock copolymers (mBCPs) could offer new opportunities to design new nanomaterials with multifunctions or enhanced properties in a cost-effective way. However, it is still very challenging to obtain high degree of polymerization in each block of mBCPs with large block number using one-pot synthesis via controlled radical polymerizations. This is due to the accumulation of the dead chains throughout the many step polymerization. In this work, we developed a new highly efficient strategy for preparing mBCPs with large block number using one-pot reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization, where every polymer block was formed by sequential addition of monomers. We achieved high block degree of polymerizations (~100 per block) for a model system of “octablock” polystyrene (PS) in just 2 hr per block. Experimentally measured molecular weights are in excellent agreement with theoretical predictions. The dead chains generated through the polymerization are negligible due to the low initiator concentration. Yet the polymerization rates are still very fast due to the heterogeneous advantages of emulsion polymerization. We have also applied this strategy to a series of mBCPs from diblock (PS176-PnBA286)1 to octablock (PS176-PnBA286)4 (PnBA for poly(n-butyl acrylate)). The high degree of polymerization in our mBCPs ensures microphase separation even though PS/PnBA system is known for small χ values. We have also found that the tensile properties of our mBCPs increase significantly with increased number of blocks. Our work reveals that the number of blocks is an important molecular variable for tuning the mechanical properties of block copolymers. 相似文献
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Hyperbranched polyethers and hyperbranched poly(amino ester)s were synthesized through one-pot method, and characterized by fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance and thermogravimetry analysis (TGA). The as-obtained hyperbranched polyols with different molecular structure and sizes were used to crosslink hydroxyl-terminated polybutadiene-based polyurethane (PU). The PU was characterized by tensile test, dynamic mechanical analysis, TGA, and swelling properties. It was found that the crosslinker structure and size have great effects on the properties of the PU. Hyperbranched polyether cross-linked PU showed the best mechanical properties, which reached mechanical strength of 1.45 MPa with elongation at break of 617 % for the third generation with hard segment content of 26.8 % at 25 °C. 相似文献
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In this paper, the morphology of thermotropic systems with fixed domains (TSFD) was evaluated applying high resolution Atomic Force Microscopy (AFM) also upon heating and cooling. Furthermore nano-mechanical characteristics of the samples were determined by means of Force/Distance spectrometry. TSFD formulated with additive types exhibiting a short chain length displayed roughly spherical scattering particles with dimensions between 0.6???m and 4???m. By means of Force Distance spectroscopy stiffness values of 0.6?N/m and 7.8?N/m were determined for the scattering domains and the matrix, respectively. Upon heating, melting and deliquescence of the additive along with migration was ascertained. After cooling to ambient temperature the formation and growth of terrace-like additive domains on the surface was recorded. Additive types with long-chain molecules developed anisotropic scattering domains resembling distorted disks without predominating orientation. Diameters up to 50???m and a thickness between 200?nm and 600?nm were ascertained. Determination of stiffness yielded values of 0.9?N/m and 13.1?N/m of the scattering domains and the matrix, respectively. Upon heating, swelling and deliquescence of the additive were detected. After cooling to ambient temperature a partial recovery of swelling was observed. Force-Distance spectroscopy yielded a 5 to 10?nm thick additive layer which coated wide areas of the surface after the heating cycle for all samples investigated. 相似文献
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Biocompatible poly(ε-caprolactone)-b-poly(vinyl alcohol) (PCL-b-PVA), poly(δ-valerolactone)-b-PVA, and poly(trimethylene carbonate)-b-PVA block copolymers were synthesized at 30 °C using a hydroxyl-functionalized xanthate reversible addition-fragmentation chain transfer (RAFT) agent, 2-hydroxyethyl 2-(ethoxycarbonothioylthio)propanoate, as a dual initiator for ring-opening polymerization (ROP) and RAFT polymerization in a one-pot procedure. The ROP of ε-caprolactone, δ-valerolactone, and trimethylene carbonate was first performed using diphenyl phosphate as the ROP catalyst followed by the RAFT polymerization of vinyl chloroacetate after quenching the ROP with 4-dimethyamino pyridine. The resulting block copolymers were aminolyzed directly to the PVA-based biocompatible block copolymers by adding hexylamine to the reaction mixture. To the best of our knowledge, this is the most convenient method for synthesizing PVA-based biocompatible block copolymers. 相似文献
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Thermosensitive, biocompatible poly(ε-caprolactone)-b-poly(N-vinylcaprolactam) (PCL-b-PVCL), poly(δ-valerolactone)-b-PVCL, and poly(trimethylene carbonate)-b-PVCL block copolymers were synthesized at 30 °C using a hydroxyl-functionalized xanthate reversible addition-fragmentation chain transfer (RAFT) agent, 2-hydroxyethyl 2-(ethoxycarbonothioylthio)propanoate (HECP), as a dual initiator for ring-opening polymerization (ROP) and RAFT polymerization in a one-pot procedure. The hydrophobic blocks were first synthesized by the ROP of cyclic monomers using diphenyl phosphate (DPP) as a catalyst and the RAFT polymerization of the PVCL block was followed by adding N-vinylcaprolactam (VCL) and 2,2′-azobis(4-methoxy-2,4-dimethyl valeronitrile) (V-70) as an initiator to the reaction mixture. This novel one-pot process is convenient and powerful method for the synthesis of the PVCL-based biocompatible block copolymers. The lower critical solution temperature (LCST) of the PVCL-based biocompatible block copolymer can be readily tuned by controlling the hydrophobicity of the block copolymers. By copolymerizing a hydrophilic N-vinylpyrrolidone moiety to the PVCL blocks by RAFT copolymerization, the LCST of the copolymer was matched with the body temperature for its future biomedical applications. 相似文献
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This paper provides an overview and discusses some recent developments in radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization). Guidelines for the selection of RAFT agents are presented. The utility of the RAFT process is then illustrated with several examples of the synthesis of polymers with reactive end-groups. Thus, RAFT polymerization with appropriately designed trithiocarbonate RAFT agents is successfully applied to the synthesis of narrow polydispersity carboxy-functional poly(methyl methacrylate) and primary amino-functional polystyrene. Methods for removing the thiocarbonylthio end-group by aminolysis, reduction and thermal elimination are discussed. It is shown that the thiocarbonylthio end-group can be cleanly cleaved by radical induced reduction with tri-n-butylstannane, to leave a saturated chain end, or by thermolysis, to leave an unsaturated chain end. 相似文献
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Benefiting from their responsiveness and adaptability, the stimuli-responsive polymers have been widely investigated and exploited in the various fields, such as environmental monitoring, electronics, photonics, controlled drug delivery, medical imaging and diagnostics. These potential applications have greatly promoted the development of advanced functional materials, and meanwhile set higher requirements for the smart materials in the aspects of the spatial structures, diverse linkages and variable functions. However, the linear functional polymers can not satisfy all the requirements of the multi-dimensional molecular design and acute sensitiveness due to the architectural limitation. Accordingly, stimuli-responsive hyperbranched polymers (HBPs) have been drawing more and more attention in recent years owing to their unique globular void-containing topological structure featured with a large number of terminal functional groups and branches, lower solution or melt viscosity, and better solubility. Therefore, design and synthesis of stimuli-responsive HBPs provide a robust tool for controlling the structure transition and creating the hierarchical sensitivity driven by different triggers. In this review, the developments and recent advances of preparation procedures, performance control and promising applications of various stimuli-responsive HBPs have been comprehensively summarized. Besides, the developing trend of stimuli-responsive HBPs is also discussed. It can be found that stimuli-responsive HBPs with different synthetic strategies and diverse performances have manifested more and more versatile applications. 相似文献
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A. P. Filippov E. V. Belyaeva E. B. Tarabukina A. I. Amirova 《Polymer Science Series C》2011,53(1):107-117
Hyperbranched polycarbosilanes are investigated by the methods of molecular hydrodynamics and optics. Dependences of the hydrodynamic
and conformational properties of these polymers on their molecular mass, the length of linear chains between branching points,
and the chemical structure of end groups are analyzed. The hydrodynamic behavior of hyperbranched polycarbosilanes is explained
by the fact that the dimensions of their macromolecules are compact and their shape is close to spherical. The convolution
of chains between branching points becomes more pronounced with an increase in their length and a decrease in the molecular
mass of the polymer. When end fluorinated groups are incorporated into the hyperbranched polycarbosilane, in thermodynamically
good solvents and θ solvents, hydrodynamic characteristics change apparently owing to a change in the density of macromolecules
in solution. In a poor solvent, the compaction of fluorinated macromolecules and a reduction in their shape asymmetry are
observed. At a fixed branching degree, the hydrodynamic properties of hyperbranched polymers depend on the structural regularity
of their macromolecules: In terms of hydrodynamic properties, the hyperbranched polycarbosilane with a degree of branching
of 1 and a random distribution of branching points within the volume of a macro-molecule is appreciably different from a dendrimer
of the same chemical nature and is close to polycarbosilanes with a degree of branching of 0.5. 相似文献
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Hyperbranched polystyrenes (HPS) were prepared by living radical polymerization of 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC) as an inimer under UV irradiation. These HPS exhibited large amounts of photofunctional diethyldithiocarbamate (DC) groups on their outside surfaces. We derived star‐HPS (SHPS) by grafting from such HPS macroinitiator with methyl methacrylate (MMA) or ethyl methacrylate (EMA). The ratios of radius of gyration to hydrodynamic radius Rg/Rh for HPS and SHPS in tetrahydrofuran (THF) were in the range of 0.74–0.90 and 1.05–1.12, respectively. HPS and SHPS behaved in a good solvent as hard and soft spheres, respectively. We demonstrated the structural ordering of both branched polymers in THF through small‐angle X‐ray scattering (SAXS), by varying the polymer concentration. As a result, HPS and SHPS formed face‐centered‐cubic (fcc) and body‐centered‐cubic (bcc) structures, respectively, near the overlap threshold (C*). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3340–3345, 2006 相似文献
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Yunfeng Shi Zhimin Ma Ningning Cui Yanli Liu Xiaoyu Hou Weimin Du Lin Liu Tong Gangsheng 《Nanoscale research letters》2014,9(1):121
A new strategy for in situ preparation of highly fluorescent CdTe quantum dots (QDs) with 3-mercaptopropionic acid (MPA) and hyperbranched poly(amidoamine)s (HPAMAM) as co-stabilizers was proposed in this paper. MPA and HPAMAM were added in turn to coordinate Cd2+. After adding NaHTe and further microwave irradiation, fluorescent CdTe QDs stabilized by MPA and HPAMAM were obtained. Such a strategy avoids the aftertreatment of thiol-stabilized QDs in their bioapplication and provides an opportunity for direct biomedical use of QDs due to the existence of biocompatible HPAMAM. The resulting CdTe QDs combine the mechanical, biocompatibility properties of HPAMAM and the optical, electrical properties of CdTe QDs together. 相似文献
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Polyethylene is one of the largest volume commodity polymers, with excellent physical and chemical properties. Polyethylene-based functionalized hyperbranched polymers are newly developed materials with unique structures and properties. Their architecturally complex structure – topology, composition and functionality – may be designed for different applications, with reduction of complexity and cost in preparation. This review focuses on the synthesis strategies and applications of polyethylene-based functionalized hyperbranched polymers. 相似文献
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Carbazole-based novel hyperbranched conjugated polymers linked with triphenylamine and benzene moieties were synthesized by Sonogashira coupling polycondensation of N-octadecyl- and N-octyl-3,6-diethynylcarbazoles with tris(4-iodophenyl)amine and 1,3,5-tribromobenzene. Solvent-soluble polymers with number-average molecular weights in the range of 3500-21,000 were obtained in 48-66% yields. The UV-vis absorption bands of the polymers were red-shifted compared to that of carbazole, indicating the extension of conjugation length. The polymers emitted blue-green fluorescence with high quantum yields up to 67% in CHCl3. Poly(1/3) containing triphenylamine units emits visible light and shows unique solvatochromism. The polymers were electrochemically redox-active. 相似文献
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Nikolay V Tsvetkov Alexander S Gubarev Elena V Lebedeva Alexey A Lezov Mariya E Mikhailova Igor P Kolomiets Nina G Mikusheva Lilija I Akhmadeeva Nina V Kuchkina Elena S Serkova Zinaida B Shifrina 《Polymer International》2017,66(4):583-592
Hydrodynamic and optical methods were applied to study conformational and physical properties of hyperbranched pyridylphenylene polymers in dilute solutions. The samples were synthesized using Diels–Alder polycyclocondensation. It was demonstrated that hydrodynamic properties of the studied macromolecules were typical for compact non‐percolated spheres. Optical and electro‐optical methods revealed information regarding the shape and asymmetry of the macromolecules (p ≈ 1.4). The contributions of optical shape effect to the observed flow birefringence of polypyridylphenylene solutions and intrinsic anisotropy of polarizability were evaluated and analysed. It was shown that varying the polymer composition (i.e. the degree of branching) caused considerable changes in the anisotropy of optical polarizability of the polymers. Dramatic difference of the electro‐optical properties in non‐polar (toluene) and polar (tetrachloroethane) solvents was found; this difference was related to the orientational correlation of polar solvent molecules with respect to the macromolecules. Dynamic properties were studied by non‐equilibrium electric birefringence which had a reasonable agreement with the dimensions estimated from hydrodynamic data. © 2016 Society of Chemical Industry 相似文献
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Surfacing hydroxyl groups of hyperbranched polyglycerol (PG) were transformed into trithiocarbonates (TTC), an efficient multi radical addition‐fragmentation transfer (RAFT) agent, to mediate the polymerization of ethyl acrylate (EA) under controllable conditions, and PG with multiarm PEA was obtained. In this system, PG was a part of Z groups, and trithiolcarbonates were bonded directly to the PG, whereas the growing PEA macroradical was detached. The molecular weight and the molecular weight distribution of the products were in the range of 1.05–3.24 × 104 g/mol and 1.28–1.42, respectively, when the concentration ratio of EA to PG‐TTC was 39.8. The number of the PEA arms was about 16. It was found that the measured molecular weights of the products were deviated from the theoretical value, and the molecular weight distribution was broadened with the conversion due to the termination between the leaving macroradicals. The final and the intermediate products were characterized by NMR in detail. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2203–2209, 2006 相似文献
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In this paper, we designed and synthesized five novel reversible addition–fragmentation chain transfer (RAFT) agents bearing naphthyl moieties in the Z or R groups, including 3,4,5-trimethoxy-benzyl dithio-2-naphthalenoate (TOBDN), 4-nitrobenzyl dithio-2-naphthalenoate (NBDN), 1-menaphthyl 4-cyanodithiobenzoate (NCDB), 1-menaphthyl dithiobenzoate (NDB) and 1-menaphthyl dithio-2-naphthalenoate (NDN). The RAFT polymerizations of styrene mediated by these RAFT agents with AIBN as the initiator at 80 °C were conducted and evaluated. Except for NCDB, the RAFT agents showed good control over the polymerization at different RAFT agent concentrations: the Mn,GPC increased linearly with the monomer conversion, and the PDIs of the polymers were relatively low (PDI = 1.20–1.50). The structure of RAFT agents bearing three different R groups with naphthyl as the Z group showed less effects on the polymerization rate, while those bearing different Z groups with 1-menaphthyl as the R group presented significant effects on the polymerization rates. The polymerization rate with phenyl as the Z group was higher than that with 2-naphthyl as the Z group, and it decreased significantly when using 4-cycno phenyl as the Z group. Retardation effects were observed with all the RAFT agents. 1H NMR spectra and chain extension results confirmed that most of the polymer chains were “living”. Ultraviolet (UV) absorption of naphthyl moieties at the R group showed blue shifts compared with those of naphthyl at the Z group. The UV absorption intensity of PS was uniformly lower than that of the corresponding RAFT agent, while the fluorescence intensity of PS was higher than that of the corresponding RAFT agent. 相似文献