Synthesis of silver (nano)particle under hyperbranched poly(amido amine)s

Ag colloidal particles stabilized by poly (N,N′‐methylene bis‐acrylamide N‐aminoethyl piperazine) (MBA‐AEPZ) were prepared. The Ag⁺ ion concentration and reaction temperature were studied on the size and size distribution of Ag colloidal particles, which were determined from the ultraviolet (UV) plasmon absorption band and transmission electron microscopic (TEM) analyses. The data show that poly(MBA‐AEPZ) behaves like lower molecular mass stabilizers; some polymers surround the surface of the Ag colloidal particles and the particle size can be controlled by a change in the Ag⁺ ion concentration and reaction temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3701–3705, 2007     

Photopolymerization of hyperbranched aliphatic acrylated poly(amide ester). I. Synthesis and properties

The hyperbranched aliphatic poly(amide ester) (HAPAE) was synthesized based on 4‐N,N‐di(2‐hydroxy ethyl)‐4‐ketobutyric acid prepared by the reaction of succinic anhydride with diethanol amine, as an AB₂ monomer (repeating unit), and with 2‐ethyl‐2‐(hydroxymethyl)‐1,3‐propanediol, as a core molecule, using acid catalysis. The second generation of the product was characterized by measuring dynamic viscosity, which decreased sharply with the increase in frequency. The product exhibits relative thermal stability as analyzed by thermogravimetry in a nitrogen atmosphere. The glass transition temperature, determined by differential scanning calorimetry, is ?27 °C. The molar mass was measured by vapor pressure osmometry. The polydispersity, measured by size exclusion chromatography, is 2.16. Dynamic mechanical thermal analyses were performed to characterize the thermal properties of the ultraviolet‐cured films of the acrylate‐modified HAPAE. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1630–1636, 2001     

Synthesis, optical and electrochemical properties of new hyperbranched poly(triphenylamine amide)s

A new triphenylamine-containing AB₂ type monomer with one carboxylic acid and two amino groups, 4-(bis(4-aminophenyl)amino)benzoic acid (3), was synthesized and used for the preparation of hyperbranched poly(triphenylamine amide)s. The self-polycondensation of the AB₂ monomer (3) afforded hyperbranched poly(triphenylamine amide) with amino end groups. The molecular weight of the hyperbranched poly(triphenylamine amide) was 21,000 Da determined by light scattering. End-capped hyperbranched polyamides were isolated by the chemical modification of unreacted amino groups with various acid chlorides. All the hyperbranched poly(triphenylamine amide)s exhibit excellent solubility in organic solvents such as NMP, DMF, DMSO, and DMAc at room temperature. The viscosities of hyperbranched poly(triphenylamine amide)s are as low as about 0.15 dL/g due to their dendritic structures. Poly(triphenylamine amide)s end-capped with rigid benzene ring have higher thermal stability than those with amino or aliphatic end groups. The photoluminescence of the hyperbranched polyamides is blue-yellow emissions around 430-510 nm. The energy gaps of the hyperbranched poly(triphenylamine amide)s with different end groups are about 2.93 eV and are independent on the end groups, but the HOMO and LUMO energy levels are dependent on the end groups.     

Preparation and thermal stability of new cellulose‐based poly(propylene imine) and poly(amido amine) hyperbranched derivatives

New cellulose‐based hyperbranched derivatives having different degrees of branching were prepared via reaction of cellulose with acrylonitrile followed by reduction of nitrile groups and successive reaction with acrylonitrile or methylacrylate. First‐ (G = 1) and half‐ (G = 0.5) generation cellulose‐based hyperbranched poly(propylene imine) or poly(amido amine) derivatives have been prepared with high reaction yield. The structure of the prepared derivatives was confirmed by Fourier transform infrared and ¹³C nuclear magnetic resonance (¹³C NMR). Thermal stability of the different cellulose‐based hyperbranched derivatives were examined using thermogravimetric analysis to study the effect of branching on the thermal decomposition parameters. The onset degradation temperature and the activation energy of the thermal degradation decreased with increasing the branching of the cellulose‐based hyperbranched derivatives. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2079–2087, 2006     

Synthesis and photoluminescence properties of heterocycle-containing poly(disubstituted acetylene)s

The metathesis polymerizations of disubstituted acetylenes containing heterocycles such as thiophene, furan, benzo[b]thiophene, and benzothiazole were examined using NbCl₅, TaCl₅, and WCl₆. Thiophene-containing monomers polymerized to afford relatively high-molecular-weight polymers in moderate yields. Benzo[b]thiophene-containing monomers also polymerized to give polymers with relatively high molecular weights. On the other hand, furan- and benzothiazole-containing monomers exhibited low metathesis polymerizability, and the polymerizations did not provide high-molecular-weight polymers. Poly(1-hexyl-2-arylacetylene)s having heterocycles [poly(1a) and poly(3a), Scheme 1] emitted blue-colored lights, and the emission maxima were around 480 nm. Heterocycle-containing poly(1-phenyl-2-arylacetylene) [poly(1b)] and poly(1-fluorenyl-2-arylacetylene) [poly(3d)] showed green-colored and yellow-colored emissions, and the emission maxima were 520 and 540 nm, respectively. The emission wavelengths of poly(disubstituted acetylene)s having heterocycles were almost the same as those of the corresponding poly(disubstituted acetylene)s without heterocycles. However, heterocycle-containing polymers showed high fluorescence quantum yields compared to the corresponding polymers without heterocycles. Diarylacetylene polymers showed emission red-shifts between the solution and cast film, while the emission maximum of poly(1-hexyl-2-phenylacetylene) [poly(1a)] in the cast film was almost the same as that in the solution. Benzo[b]thiophene-containing poly(1-(4-trimethylsilylphenyl)-2-phenylacetylene) [poly(3b)] and poly(1-(9,9-dimethyl-2-fluorenyl)-2-phenylacetylene) [poly(3d)] afforded the free-standing membranes because of their high molecular weights. The oxygen permeability coefficient (PO₂) of poly(3b) was as large as 1400 barrers. Poly(3d) showed higher gas permeability, and its PO₂ was 5300 barrers.     

脂肪族聚丁二酸丁二醇-聚乙二醇嵌段共聚物的制备及性能研究

采用熔融缩聚法以钛酸四丁酯为催化剂,使单体发生酯交换反应,成功制备了一系列以聚乙二醇(PEG)为亲水软段,以聚丁二酸丁二醇酯(PBS)为硬段的嵌段共聚物,采用1H-NMR确定了共聚物的结构组成;采用DSC、吸水性测试及水解降解试验对嵌段共聚物性能表征,结果表明共聚物中两种链段的含量与原料投料比一致,具有可调控性。由于PEG的引入,使共聚物结晶性下降,亲水性和降解性得到显著改善。     

Synthesis of hyperbranched P poly(glycerol-diacid) oligomers

Novel oligomeric prepolymers were synthesized by acid-catalyzed condensation of glycerol with iminodiacetic, azelaic, or succinic acid. The prepolymers were obtained, on average, in 62% yield and were characterized by ¹³C NMR, ¹H NMR, matrix-assisted laser desorption ionization-time of flight-mass spectrometry, and gel permeation chromatography. The synthesized oligomers had an average M.W. of 1543 Daltons (average polydispersity (PD)=1.34, average degree of polymerization (DOP)=5.5). Hyperbranching was evident in the oligomers produced when using azelaic acid and succinic acid as co-monomers with glycerol, whereas the reaction between iminodiacetic acid and glycerol resulted in linear products bearing cyclic urethane structures.     

两亲性超支化聚酯-酰胺的制备及其性能

引言 在同一分子中,既含有亲水性链段,又含有疏水性链段的聚合物称为两亲性聚合物,这种聚合物的凝聚态常具有多相结构,并对不同极性的化合物都具有一定的亲和力,这种独特的性质就使其既不同于低分子表面活性剂也异于一般的离子聚合物.带有亲水性支链的两亲性聚合物具有很大的应用潜能.可以用作乳液和分散体的稳定剂,颜料及塑料的表面改性剂,高分子材料的助剂及改性剂等[1-2].     

Synthesis and characterization of new hyperbranched poly(ether ketones) with various number of phenylene units

A new series of AB₂ type monomers with aromatic thio and various number of phenylene units were prepared. Three series of AB₂ type monomers, 4-thio-3′,5′-bis(4-fluorobenzal)biphenyl 1, 4-thio-3′′,5′′-bis(4-fluorobenzal)-p-terphenyl 2 and 4-thio-3′′′,5′′′-bis(4-fluorobenzal)-p-quarterphenyl 3 were synthesized in a stepwise manner starting from 3,5-bis(4-fluorobenzoyl)phenol 4 by repeating a series of conversions of the hydroxy group to the triflate, cross-coupling reaction of the triflate with (p-methoxythiophenyl)boronic acid, reduction of carbonyl groups followed by conversion of methylthio to thio group. Three kinds of hyperbranched poly(ether ketones) were prepared by the polymerization of the these three AB₂ type monomers. All compounds were characterized by elemental analysis, thermal analysis, ¹H and ¹³C NMR spectrometry.     

Synthesis and properties of poly(ferrocenylsilane) high polymers

Ring-opening polymerization of strained, ring-tilted cyclic ferrocenylsilanes has recently provided access to the first examples of high molecular weight poly(ferrocenylsilanes) [1], which possess backbones of alternating ferrocenyl groups and silicon atoms. In this paper we provide an overview of the progress to date on the synthesis and properties of these unusual polymers.Presented at the XXVIth Silicon Symposium, Indiana University-Purdue University at Indianapolis, March 26–27, 1993.     

Aliphatic poly(amido acids) and polyimides with cyclobutane ring in the main chain

New aliphatic polyimides with cyclobutane ring in the main chain have been synthesized successfully from cyclobutane tetracarboxylic dianhydride and diamine. In order to establish the reaction path poly(amido acids), intermediates to polyimides, were isolated and characterized. All poly(amido acids) are hygroscopic and were found to be converted into polymides through dicarboacetoxy intermediate by heating in dimethylformamide at 100°C in the presence of acetic anhydride. Thermal study by means of thermal gravimetric analysis and differential scanning calorimetry revealed that conversion of poly(amido acid) to polyimide also occurred by thermal cyclocondensation reaction at around 180°C. These reactions were confirmed by parallel reaction of the model compounds. Properties of polyimides thus obtained were characterized and are discussed in comparison with known polymers with polyimide or cyclobutane ring structures.     

Synthesis,characterization, and properties of PCDL aliphatic hyperbranched polyurethane coatings

The isocyanate‐terminated polyurethane pre‐polymer (PPU) was synthesized via the step‐growth polymerization approach by using polycarbonate diol (PCDL, Mn = 2000) and isophorone disocyanate (IPDI) as monomers, dibutyltin dilaurate (DBTDL) as the catalyst. Subsequently, the hyperbranched polyurethane (HBPU) was synthesized by graft copolymerization using PPU, hyperbranched poly(amide–ester) polyol (HPAE) and 1,4‐butanediol (BDO). The molecular structure of HBPU was characterized by means of FTIR, ¹H‐NMR, and ¹³C‐NMR. It was observed that HBPU was synthesized as anticipated. The thermal and mechanical properties, the microstructure, and morphologies of the filmed HBPU and LPU (linear polyurethane) were tested, respectively. The filmed HBPU, revealed better thermal stability, and higher T_g accompanied with lower viscosity than those of filmed LPU. Additionally, the mechanical experiment showed that the filmed HBPU exhibited enhanced mechanical properties because it contained certain amounts of HPAE. Compared with its linear analog (LPU) specimen, the tensile strength of the filmed HBPU containing 10 wt % HPAE increased by 1.9 times (up to 28.15 MPa), and its elongation at break increased by 1.5 times (up to 543.8%), resulting from the dual effects of the hydrogen bonding and the crosslinking density in the HBPU system. The morphologies of filmed HBPU were characterized by means of WAXD and SEM, which indicated that increasing the content of HPAE lowers the crystallinity of HBPU. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2671–2679, 2013     

Demulsification of oil-in-water emulsions using hyperbranched poly(amido amine) demulsifiers with 4,4-diaminodiphenyl methane as initial cores

Hyperbranched poly(amido amine) demulsifier (PDDM) was synthesized by a modified “one-pot” method with 4,4-diaminodiphenyl methane as the central core and ethylenediamine as the interior branches. The structure of the demulsifier was confirmed by proton nuclear magnetic resonance and Fourier transform infrared. The effects of the temperature and PDDM concentration on the demulsification performance were investigated, and PDDM performance was compared to that of the hyperbranched demulsifier with 1,3-propanediamine as the central core. When the emulsions were treated with the demulsifier concentration of 50 mg L⁻¹ at 60 °C for 120 min, the light transmittance and removed total organic content of the aqueous phase reached 87.4 and 99.72%, respectively. At the optimal demulsification temperature of 60 °C, the surface tension reduction and the critical micelle concentration were 27.38 mN m⁻¹ and 1.30 × 10⁻³ mol L⁻¹, respectively. The combination of surface tension and interfacial tension measurements and the analysis of micrographs and particles sizes provide evidence for the possible demulsification mechanism. The excellent demulsification performance of the hyperbranched demulsifier indicates that it has great potential for use in the demulsification of oil-in-water emulsions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48846.     

Synthesis and photoluminescence properties of fluorine-containing poly(phenylene vinylene) bearing hexafluorocyclopentene-fused phenanthrene unit

The intramolecular oxidative photocyclization of 1,2-diarylhexafluorocyclopentene ( 1 ) under light irradiation (λ = 365 nm) provided hexafluorocyclopentene-fused phenanthrene with formyl groups ( 2 ) in moderate yield. The copolymerization of 2 with tetraethyl(2,5-bis(dodecyloxy)-1,4-phenylene)bis(methylene)diphosphonate by the Horner–Wadsworth–Emmons reaction gave a fluorine-containing poly(phenylene vinylene), Polymer-2, in 41% yield. For comparison, a diphenylethene-type copolymer, Polymer-1, was also prepared analogously. The number-average molecular weights of Polymer-1 and Polymer-2 were 8900 and 3300 g mol^?1, respectively. The copolymers showed high thermal stability, as revealed by their thermogravimetric analysis. UV–visible spectra of the copolymers in CHCl₃ showed π–π* transition peaks at around 420 nm, and the peaks shifted to longer wavelengths by ca 10 nm for samples in film form. The photoluminescence spectra of Polymer-1 and Polymer-2 exhibited peaks at 542 and 560 nm in CHCl₃, respectively, whereas the photoluminescence intensity of Polymer-2 was very low in the solid state, presumably owing to the partial aggregation of the polymer molecules. © 2021 Society of Industrial Chemistry.     

Synthesis and characterization of hyperbranched aromatic poly(ester-imide)s

The synthesis and characterization of hyperbranched aromatic poly(ester-imide)s are described. A variety of AB₂ monomers, N-[3- or 4-bis(4-acetoxyphenyl)toluoyl]-4-carboxyl-phthalimide and N-{3- or 4-[1,1-bis(4-acetooxyphenyl)]ethylphenyl}-4-carboxy phthalimides were prepared starting from condensation of nitrobenzaldehydes or nitroacetophenones with phenol and used for synthesis of hyperbranched poly(ester-imide)s containing terminal acetyl groups by transesterification reaction. These hyperbranched poly(ester-imide)s were produced with weight-average molecular weight of up to 6.87 g/mol. Analysis of ¹H NMR and ¹³C NMR spectroscopy revealed the structure of the four hyperbranched poly(ester-imide)s. These hyperbranched poly(ester-imide)s exhibited excellent solubility in a variety of solvents such as N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran and showed glass-transition temperatures between 217 and 255 °C. The thermogravimetric analytic measurement revealed the decomposition temperature at 10% weight-loss temperature (T_d¹⁰) ranging from 365 to 416 °C in nitrogen.     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006     

Synthesis and aqueous solution properties of aliphatic double chain end-capped poly(ethylene glycol)

Summary A PEG-based amphiphilic polymer bearing two aliphatic double chain moieties was prepared. Its diluted aqueous solution properties were studied by viscometry, dye solubilization and rheology. At concentrations lower than (6–8)×10⁻³ g/mL ring-shaped macromolecules were formed due to intrachain hydrophobic interactions. At concentrations about (6–8)×10⁻³ g/mL a formation of "flower" type aggregates took place. 1,6-Diphenyl-1,3,5-hexatriene solubilization was used to prove the existence of hydrophobic domains and a critical aggregation concentration of 7×10⁻³ g/mL was determined. The peculiar viscosity profile and the rheopectic behavior of the amphiphilic polymer were attributed to the existence of aggregates and to a temporary network formation during deformation, respectively. Received: 13 February 2001/Revised version: 15 June 2001/Accepted: 15 June 2001     

Synthesis and solution properties of a new poly(electrolyte-zwitterion)

A novel electrolytic-zwitterionic (EZ) monomer, Sodium N-(3-sulfopropyl)-3-(N,N-diallylamino)propanesulfonate, on homopolymerization in aqueous solution using tert-butylhydroperoxide, afforded the poly(electrolyte-zwitterions) (PEZ). The copolymer of the above monomer and sulfur dioxide was also synthesized in excellent yield. The EZ monomer as well as the PEZs contains structural features common to both polyzwitterions and conventional polyelectrolytes. The solution properties of these polymers were studied in detail. The PEZ, as the name implies, possess dual type of structural character and it is the electrolytic portion of the structure that dictates the solubility and viscosity behavior of the polymers.     

White‐light‐emitting hybrid film from fluorescent hyperbranched poly(amido amine)

The flexible, strong, and tough white‐light‐emitting (WLE) hybrid films are highly demanded in large‐scale displays, including TV sets, monitors, and electronic interactive devices. In this work, a kind of WLE hybrid film was fabricated from hyperbranched poly(amido amine) (HPAMAM) and nanoclay with the incorporation of riboflavin (VB₂) and rhodamine B (RhB). The fluorescence emission of HPAMAM was partially absorbed and effectively transferred into green and red color, which combined into a bright white light with the residue blue fluorescence. Due to the alignment of nanoclay inside the HPAMAM matrix, in addition to the strong interaction among the HPAMAM molecules and that between HPAMAM and nanoclay, this hybrid film shows to be strong and tough. The mechanical strength is about 20 MPa and the elongation is about 30%. It is convinced that this hybrid film is promising in flexible large‐scale displays. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46015.     

Synthesis and characterization of poly(pyridinium salt)s with oxyalkylene units exhibiting amphotropic liquid-crystalline and photoluminescence properties

Several novel poly(pyridinium salt)s with oxyalkylene moieties in the main chain with bulky organic counterions (tosylate and triflimide) were prepared by either the ring-transmutation polymerization of phenylated bis(pyrylium tosylate) salt with a series of oxyalkylene containing diamines in dimethyl sulfoxide on heating for 48 h or the metathesis reaction of the corresponding tosylate polymers with lithium triflimide in methanol. Their chemical structures were determined by elemental analysis and ¹H and ¹³C NMR spectroscopies, and their polyelectrolyte behavior in dimethyl sulfoxide was determined by solution viscosity measurements. Their weight average molecular weights were in the range 14,000-22,000 and polydispersity indices were in the range 1.20-1.70 as determined by gel permeation chromatography. They were characterized both for their thermotropic and lyotropic liquid-crystalline properties by using differential scanning calorimetry and polarizing optical microscopy. Since these polymers exhibited liquid-crystalline phase both in the melt and in solution, they can be appropriately classified as amphotropic class of ionic polymers. Their light-emitting properties were also determined by using spectrofluorometry.