Synthesis of a thioether modified hyperbranched polyglycerol and its template effect on fabrication of CdS and CdSe nanoparticles

A thioether‐containing hyperbranched polyglycerol (PG) was synthesized by a simple and effective two‐step reaction; first a part of the hydroxyls of PG was transformed to carbamates by the reaction with the highly reactive 2‐chloroethyl isocyanate, and then the chlorine group was S‐alkylated with HS(CH₂)_nOH (n = 2, 6, 11). The resulting PGs with various molecular weights were successfully used as template for synthesis of nanoscale cadmium chalcogenide quantum dots (QDs). It was found that the size of these QDs was dependent on the polymer template. Moreover, after solvent evaporation, the polymer was assembled into large cluster, and a variety of morphologies were formed by the cluster inside the QDs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3679–3684, 2006     

Synthesis of gold nanoparticles in hyperbranched polyol dispersions

In this study, a series of different generation hyperbranched poly(amine‐ester) with hydroxyl as terminal group were synthesized and used as protectants to synthesize gold nanoparticles with a facile and highly reproducible method. The effect of hyperbranched poly(amine‐ester) generation on size and their distribution of gold nanopartciels were discussed. The results of ultraviolet visible absorption spectroscopy, Transmission electron microscopy and scanning electron microscopy showed that the mean diameter were 24.3 ± 2.6 nm, 18.2 ± 2.1 nm, and 13.6 ± 1.5 nm corresponding to the different generation hyperbranched poly(amine‐ester), and the synthesized gold nanoparticles were almost monodisperse with a narrow size distribution. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Solution properties of hyperbranched polymers and synthetic application for amphiphilic star‐hyperbranched copolymers by grafting from hyperbranched macroinitiator

Hyperbranched polystyrenes (PS) were prepared by living radical photopolymerization of N,N‐diethyldithiocarbamoylmethylstyrene (DTCS) as an inimer under UV irradiation. Branched PS with an average chain length between branching points of four styrene units was also prepared by living radical copolymerization of DTCS with styrene. The ratio of radius of gyration to hydrodynamic radius R_G/R_H for these hyperbranched polymers was in the range 0.82–0.89 in toluene. The translational diffusion coefficient D(C) showed a constant value in the range of 0–14 × 10^?3 g ml^?1 in toluene. It was found from these dilute solution properties that hyperbranched PSs formed a unimolecular structure even in a good solvent because of their compact nature. These hyperbranched PSs exhibited large amounts of photofunctional carbamate (DC) groups on their outside surfaces. Subsequently, we derived amphiphilic star‐hyperbranched copolymers by grafting from hyperbranched macroinitiator with 1‐vinyl‐2‐pyrrolidinone. These star‐hyperbranched copolymers were soluble in water and methanol. © 2001 Society of Chemical Industry     

Nano‐scaled ordering of hyperbranched and star‐hyperbranched polymers

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 R_g/R_h 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     

Synthesis of hyperbranched polyester‐amides and their application as crosslinkers for polyurethane curing systems

A series of hyperbranched polyester‐amides (S1, S2, S3) with trimethylolpropane as a core molecule were synthesized using core‐dilution/slow monomer addition strategy. The products were characterized by FTIR, ¹³C NMR, GPC, TGA, hydroxyl value measurement, and viscosity measurement. The result showed that the hyperbranched polyester‐amides synthesized had narrow molecular weight distribution and high degree of branching (DB). The hyperbranched polyester‐amides synthesized were used as crosslinkers for polyurethane curing systems and the mechanical properties of the polyurethane curing systems were investigated. It was found that the best tensile property and tear strength were obtained when the S2 were used as crosslinkers and the molar ratio of  OH and  NCO was 1 : 1. It was also found that the polyurethane curing systems had the highest hardness and T_g when the S3 were used as crosslinkers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Xanthate‐mediated polymerization of styrene on hyperbranched polyethylenimine: Synthesis,characterization, and guest‐encapsulating property

Hyperbranched polyethylenimine (HPEI) is a highly polar, multifunctional polymer bearing active amines throughout its globular structure. In this article, the amino protons, which were incompatible with living radical polymerization techniques, were alkylated with propylene oxide, leading to tertiary amines and hydroxyls, and part of the hydroxyl groups were further transformed into xanthate groups. The HPEI‐xanthate could mediate the polymerization of styrene, leading to a star‐like, multiarm amphiphilic polymer. It was found that the polymerization was a hybrid of living and conventional radical processes. The resulting amphiphilic, core‐shell‐structured polymer existed as a unimolecular micelle (UIM) in apolar solvent and could irreversibly encapsulate water‐soluble anionic dyes. At high pH, the encapsulated dyes could be partly released. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of the environmental‐sensitive hyperbranched polymers as novel carriers for controlled drug release

Novel hyperbranched polymers, which contain a hydrophobic branched poly(p‐(chloromethy)styrene) (PCMS) core and poly(N,N‐dimethylaminoethyl methacrylate) (PDMA) shell that exhibited environmental sensitivity, have been synthesized by atom transfer radical polymerization (ATRP). At first, a hyperbranched polymer (PCMS) core is obtained via ATRP of p‐(chloromethy)styrene (CMS), which may act as an “inimer”‐monomer and initiator. Then the modified hyperbranched polymers having different average arm length consisting of PCMS and PDMA are synthesized by ATRP using anterior PCMS as macroinitiators. Their macromolecular structures are characterized by FTIR and ¹H NMR. Using chlorambucil as a model drug, the behaviors of the controlled drug release from the environmental‐sensitive hyperbranched polymers with different average chain length of PDMA and degree of branching are studied. The data demonstrate that the rate of the drug release can be effectively controlled by pH value, and these environmental‐sensitive hyperbranched polymers have the potential to be used as novel carriers in some controlled drug release systems in the future. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 311–316, 2006     

Size control of gold nanoparticles synthesized in a DNA hydrogel

A DNA crosslinked hydrogel, which efficiently absorbs Au³⁺, was used as a ‘reactor’ for in‐gel synthesis of gold nanoparticles. Chemical reduction of Au³⁺ absorbed by the DNA hydrogel proceeds inside the hydrogel volume and yields well‐dispersed gold nanoparticles with a narrow size distribution. The average diameter of the nanoparticles varies from 1 to 2 to 5 nm on changing the pH during the reduction. The electrostatic properties of DNA hydrogels containing gold nanoparticles are discussed. © 2014 Society of Chemical Industry     

有机-无机杂化核壳型乳胶粒的制备及其粒径控制

以苯乙烯乳液聚合合成种子,再在种子外生成苯乙烯与甲基丙烯酸-3-三甲氧基硅丙酯（MPS）的共聚物,利用MPS中硅氧烷基的水解-缩合反应,形成交联的壳,得到有机-无机杂化型核壳乳胶粒.然后用溶剂将聚苯乙烯模板溶解,可得到空心微胶囊.通过透射电镜（TEM）和动态光散射粒径仪（DLS）观测乳胶粒及微胶囊的形态.并研究了乳化剂种类、介质pH值、MPS用量和加入方式对粒径、粒子数和体系稳定性的影响.发现非离子型乳化剂、酸性或碱性介质、MPS用量过多均促进乳胶粒子数减少,减弱了乳液稳定性.而采取连续滴加MPS的方法则可提高乳液的稳定性,且粒径可控.     

Synthesis and properties of partially conjugated hyperbranched light‐emitting polymers

Via A₂ + B₄ and A₂ + B₃ [where A₂ is 1,4‐distyrylol‐2,5‐butoxybenzene, B₃ is 1,1,1‐tris‐(p‐tosyloxymethyl)‐propane, and B₄ is pentaerythritol tetra(methyl benzene sulfonate)] approaches, we synthesized two kinds of partially conjugated hyperbranched polymers, hyperbranched polymer with 3 arms (HP1) and hyperbranched polymer with 4 arms (HP2), which had rigid conjugated segments [oligo‐poly(phenylene vinylene)] and flexible, nonconjugated spacers arranged alternately through ether bonds in the skeleton. The conjugated segments were modified by pendant butoxy groups, which imparted the resulting polymers with excellent solubility in common organic solvents and excellent film‐forming abilities. Fourier transform infrared and nuclear magnetic resonance spectroscopy were used to identify the structure of the monomers and polymers. Thermal property investigations showed that two polymers both had good thermal stability with their decomposition temperatures in the range 396–405°C and high glass‐transition temperatures, which are of benefit to the fabrication of high‐performance light‐emitting devices. The photophysical properties were studied, and the relative photoluminescence quantum efficiencies of HP1 and HP2 in dilute chloroform solution amounted to 56.8 and 49.3%, respectively. A brief light‐emitting diode device with a configuration of indium tin oxide/HP1/Ca/Al was fabricated, and its electroluminescence performance was studied. The brightness of the device reached an optimistic maximum of 190 cd/m² at 8.2 V. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of a novel hyperbranched polyether

A hyperbranched polyether has been synthesized by a single‐step nucleophilic displacement polymerization technique between cyanuric chloride and the sodium salt of bisphenol‐A. The effects of various reaction parameters on the yield, and molecular weight, as measured by the intrinsic viscosity of the polymer, have been studied. The synthesized polymer has been characterized by FT‐IR, UV and ¹H NMR spectroscopies, elemental analysis, solubility and viscosity measurements. The polymer is soluble in highly polar solvents such as N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide, partially soluble in dilute aqueous NaOH solution, methanol, ethanol, chloroform, etc., but insoluble in water and non‐polar hydrocarbon solvents. The solubility parameter of the hyperbranched polymer has also been measured experimentally. Copyright © 2004 Society of Chemical Industry     

Filled polymers with high nanoparticles concentration—Synthesis and properties

High refractive index optical compositions based on polymer matrices filled with high concentrations of ZnS nanoparticles were developed. These materials have good optical properties and processability like usual polymers, and they are suitable for factory scale use. At 25 vol % ZnS nanoparticles concentration an increase in refractive index up to 0.25 in 150 um transparent film was obtained. A process was develope for formation of polymeric compositions consisting of polymer filled with high concentrations of inorganic crystalline nanoparticles. Effects connected to high concentration of nanoparticles in the polymer were discussed. Optical properties of these materials were investigated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of well‐defined dendritic hyperbranched polymers by iterative methodologies using living/controlled polymerizations

This review presents firstly the synthesis of various dendritic hyperbranched polymers with well‐defined structures by generation‐based growth methodologies using living/controlled polymerization. Secondly, the synthesis of dendritic hyperbranched poly(methyl methacrylate)s (PMMAs) and their functionalized block copolymers using a novel iterative methodology is described. The methodology involves a two‐reaction sequence in each iterative process: (a) a linking reaction of α‐functionalized living anionic PMMA with tert‐butyldimethylsilyloxymethylphenyl (SMP) groups with benzyl bromide (BnBr)‐chain‐end‐functionalized polymer and (b) a transformation reaction of the SMP groups into BnBr functions. This reaction sequence is repeated several times to construct high‐generation (maximum seventh generation) dendritic hyperbranched polymers. Similar branched architectural block copolymers have also been synthesized by the same iterative methodology using other α‐functionalized living anionic polymers. Surface structures of the resulting dendritic hyperbranched block copolymers composed of PMMA and poly(2‐(perfluorobutyl)ethyl methacrylate) segments have been characterized using X‐ray photoelectron spectroscopy and contact angle measurements. Solution behaviors of dendritic hyperbranched PMMAs with different generations and branch densities are discussed based on their intrinsic viscosities, g′ values and R_h values. Copyright © 2007 Society of Chemical Industry     

Synthesis and self‐assembly of hyperbranched polyethers peripherally modified with adenosine 5′‐monophosphate

The chloride functionalized hyperbranched poly(3‐ethyl‐3‐oxetanemethanol) (HBPO) was prepared via reaction of thionyl chloride with hydroxyl groups. Adenosine 5′‐monophosphate (AMP) groups were attached to HBPO in CH₂Cl₂ in the presence of triethylamine (TEA) as an acceptor of HCl. The self‐assembly of resultant hyperbranched molecules bearing self‐complementary hydrogen‐bonding patterns would allow the generation of a highly organized supramolecular architecture in a selected solvent. The morphologies of self‐assembly structures were depended on the level of AMP in polymer and the concentration in solvent. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1147–1152, 2006     

Initiator‐fragment incorporation radical polymerization of ethylene glycol dimethacrylate in the presence of 1,1‐diphenylethylene: synthesis and characterization of soluble hyperbranched polymer nanoparticles

The polymerization of ethylene glycol dimethacrylate (EGDMA) as crosslinker was carried out at 70 and 80 °C in benzene using dimethyl 2,2′‐azobisisobutyrate (MAIB) as initiator at concentrations as high as 0.50–0.70 mol l^?1 in the presence of 1,1‐diphenylethylene (DPE), where the concentrations of EGDMA and DPE were 0.50–0.70 and 0.25–0.50 mol l^?1, respectively. The polymerization proceeded homogeneously, without gelation, to give soluble polymers. The yield and molecular weight of the resulting polymers increased with time. The homogeneous polymerization system involved ESR‐observable DPE‐derived radicals of considerably high concentration (3.6–5.3 × 10^?5 mol l^?1). The methoxycarbonylpropyl groups as MAIB‐fragments were incorporated as a main constituent (35–50 mol%) into the polymers (initiator‐fragment incorporation radical polymerization). The polymers also contained DPE units (15 mol%) and EGDMA units with double bonds (10–25 mol%) and without double bonds (20 mol%). Results from gel permeation chromatography (GPC)–multiangle laser light scattering (MALLS), transmission electron microscopy (TEM) and viscometric measurements revealed that the individual polymer molecules were formed as hyperbranched nanoparticles. Copyright © 2004 Society of Chemical Industry     

以均苯四甲酰四二乙醇胺为核的水溶性超支化聚酰胺-酯的合成与表征

超支化聚酰胺-酯(HPAE)含有类似于球形状的分子结构和大量活性端基,因而在胶粘剂、涂料、流变改性剂及染料等领域中具有潜在的应用前景。以均苯四甲酸酐(PMDA)和二乙醇胺(DEA)为原料,合成出一种中心核(By);然后以2,2-二羟甲基丙酸(DMPA)为AB2单体,将其与By进行熔融缩聚反应,制成水溶性的HPAE。结果表明:By的数均相对分子质量(Mn)、重均相对分子质量(Mw)分别为1 697、1 889 g/mol,Mw/Mn=1.11,说明其相对分子质量分布较窄;HPAE分子骨架中含有强极性酰胺键、弱极性酯键和大量强极性羟基,易溶于水;水溶性HPAE的支化度为0.47,其Mn、Mw分别为2 195、3 676 g/mol,Mw/Mn=1.67。合成原料易得、工艺简单,适合大量制备超支化聚合物。     

Formation of a soluble hyperbranched polymer via initiator–fragment incorporation radical copolymerization of divinyl adipate and isobutyl vinyl ether

The copolymerization of divinyl adipate (DVA) with isobutyl vinyl ether (IBVE) was conducted at 70 and 80 °C in benzene using azobisisobutyronitrile (AIBN), at a concentration as high as 0.50 mol l^?1 as the initiator, where the concentrations of DVA and IBVE were 0.40 and 0.60 mol l^?1, respectively. The copolymerization proceeded homogeneously, without any gelation, to yield soluble copolymers in spite of the high molar ratio of DVA as an excellent cross‐linker for IBVE. The copolymer yield increased with time, and the number‐average molecular weight (M_n = 0.9–2.4 × 10⁴ g mol^?1) from gel permeation chromatography (GPC) and molecular weight distribution (M_w/M_n = 1.5–7.6) of the resulting copolymer increased with copolymer yield. The cyanopropyl group, as a fragment of AIBN, was incorporated as a main constituent in the copolymer, the fraction of which increased from ca 10 to ca 20 % with copolymer yield, hence indicating that the copolymerization is an initiator–fragment incorporation radical polymerization. The copolymers also contained IBVE units (10–30 %) and DVA units with intact double bond (8–36 %) and without double bond (45 %). The intrinsic viscosity of the copolymer was very low (0.1 dl g^?1) at 30 °C in tetrahydrofuran. The results from GPC–multi‐angle laser light scattering (MALLS), transmission electron microscopy (TEM) and MALLS revealed that individual copolymer molecules were formed as hyperbranched nanoparticles. Copyright © 2004 Society of Chemical Industry     

A novel method for the preparation of core‐shell nanoparticles and hollow polymer nanospheres

A one‐step method to prepare core‐shell nanoparticles and thus hollow nanospheres is reported. The process for the formation of core and shell took place during reaction. Once the core formed, it was covered with the shell substance produced in situ, and thus, the shell hindered the continued growth of the core. Based on this method, we readily obtained core‐shell nanoparticles by choosing AgCl, CuS, or Fe(III) diethyldithiocarbamate (FeDEC)₃ as model core substances and the cogel from gelatin and gum arabic as the shell substance. High‐resolution transmission electron microscopy (HRTEM) directly revealed the core‐shell structure. TEM results showed the average particle sizes were under 100 nm, depending on the core substance and the concentration of substances producing cores. After removal of the core materials, hollow nanospheres resulted, which were directly observed by TEM. The observation further verified the core‐shell structure. UV spectrophotometry also gave signals of coated structure and revealed high core content (51.1%) and nearly perfect coating (91.6%). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2594–2600, 2004     

Effect of particle size on the mechanical properties of polystyrene and poly(butyl acrylate) core/shell polymers

The effects of particle size and polymer location (core or shell) on the mechanical properties of core/shell materials composed of polystyrene (PST) and poly(butyl acrylate) (PBA) made by a two-stage emulsion or microemulsion polymerization process are reported. Low-seed content (LSC) latexes were made by batch polymerization in microemulsions stabilized with DTAB in the presence of an organic salt (dibutyl phosphite). High-seed content (HSC) latexes were produced by microemulsion or emulsion polymerization in semi-continuous process. These latexes were subsequently used to form core/shell particles of PST/PBA or PBA/PST and their mechanical properties were examined and compared. Our results indicate that core/shell particle size and the location of the polymers have important effects on the mechanical properties.     

Synthesis of cyclodextrin‐based polymers and their use as debittering agents

Cyclodextrins (CDs) and their derivatives are used to suppress unpleasant tastes and odors or to achieve a controlled release of certain food constituents. This article describes the synthesis by nonconventional methods of (1) crosslinked, insoluble CD polymers and (2) water‐soluble, CD‐grafted carboxymethylchitosan and carboxymethylcellulose. The CD polymers were obtained by the reaction of β‐CD with one of the following crosslinking agents: epichlorohydrin, diphenyl carbonate, or hexamethylene diisocyanate. Their preparations were usually carried out under high‐intensity ultrasound, which resulted in much shorter reaction times and narrower distributions of particle size (as determined by scanning electron microscopy measurements). A novel, insoluble CD polymer was obtained by reticulation under microwaves of propargyl‐β‐CD with 1,3‐bis(azidomethyl)benzene through Huisgen 1,3‐dipolar cycloaddition. Short columns packed with the insoluble polymers were found to efficiently sequester naringin from aqueous solutions; successively, they could be easily regenerated by a counter‐current ethanol wash that also achieved an excellent recovery of the flavonoid. Differential scanning calorimetry thermograms showed that the crosslinked CD polymers formed inclusion complexes with naringin. The soluble polymers also interacted with bitter flavonoids of citrus fruits (naringin and limonin), as shown by the results of sensorial panel tests, in which they behaved as bitter‐masking agents. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008