Polymer Blend for Electrolyte and Electrode Coatings

Summary: The thermal and morphological properties of PEO/copolyether electrolyte and carbon black composite have been studied. A copolyether poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) was used at 20 wt.-% in relation to PEO in order the improve the carbon black dispersion through interaction with the amino end capped function. The polymer matrix presented semicrystalline structure and the addition of LiClO₄ and carbon black decreases significantly the crystallinity of the system. Sub-micrometric dispersion of carbon black was observed. The conductivity results as a function of temperature exhibited a typical VTF behaviour for the electrolyte. Almost constant conductivities of 2 × 10⁻⁴ S · cm⁻¹ were observed for the composite with 5 wt.-% of carbon black, in the range of temperature between 35 and 95 °C, which indicates a significantly contribution of electronic conduction.     

One-step synthesis of amine-functionalized thermo-responsive magnetite nanoparticles and single-crystal hollow structures

A high-temperature solution phase hydrolysis has been developed for the synthesis of amine-functionalized Fe₃O₄ nanostructures. The concentrations of the reagents and the reaction time have great influence on the morphologies of the products. Increasing the amounts of poly (propylene glycol) bis (2-aminopropyl ether) transformed the product morphology from hollow nanostructures to magnetite nanoparticles. Single-crystal solid spherical aggregates, hollow spheres, loose nanoclusters and polyhedral-like magnetite particles can be selectively synthesized by varying the synthesis parameters, including the reaction time or the weight ratio of iron precursors to polyetheramine. The morphological transformation could be attributed to the cooperation of oriented aggregation and Ostwald ripening mechanisms. By using poly (propylene glycol) bis (2-aminopropyl ether) as the capping agent, the amine-functionalized nanoparticles show high water dispersibility and thermo-responsive. In addition, the Pickering emulsion stabilized by amine-functionalized nanoparticles was fabricated. One of the most promising applications of the as-prepared single-crystal hollow structures is as support materials for biological testing, catalysis and targeted drug delivery.     

Synthesis and properties of hyperbranched polyurethanes,hyperbranched polyurethane copolymers with and without ether and ester groups using blocked isocyanate monomers

Starting from 3,5‐diamino benzoic acid, 2‐hydroxy propyl[3,5‐bis{(benzoxycarbonyl)imino}]benzyl ether, an AB₂‐type blocked isocyanate monomer with flexible ether group, and 2‐hydroxy propyl[3,5‐bis{(benzoxycarbonyl)imino}]benzoate, an AB₂‐type blocked isocyanate monomer with ester group, were synthesized for the first time. Using the same starting compound, 3,5‐bis{(benzoxycarbonyl)imino}benzylalcohol, an AB₂‐type blocked isocyanate monomer, was synthesized through a highly efficient short‐cut route. Step‐growth polymerization of these monomers at individually optimized experimental conditions results in the formation of hyperbranched polyurethanes with and without ether and ester groups. Copolymerizations of these monomers with functionally similar AB monomers were also carried out. The molecular weights of the polymers were determined using GPC and the values (M_w) were found to vary from 1.5 × 10⁴ to 1.2 × 10⁶. While hyperbranched polyurethanes having no ether or ester group were found to be thermally stable up to 217 °C, hyperbranched poly(ether–urethane)s and poly(ester–urethane)s were found to be thermally stable up to 245 and 300 °C, respectively. Glass transition temperature (T_g) of polyurethane was reduced significantly when introducing ether groups into the polymer chain, whereas T_g was not observed even up to 250 °C in the case of poly(ester–urethane). Hyperbranched polyurethanes derived from all the three different AB₂ monomers were soluble in highly polar solvents and the copolymers showed improved solubility. Polyethylene glycol monomethyl ether of molecular weight 550 and decanol were used as end‐capping groups, which were seen to affect the thermal, solution, and solubility properties of polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3877–3893, 2007     

STUDIES ON METAL-CONTAINING POLYURETHANES BASED ON DIVALENT METAL SALTS OF MONO(HYDROXYETHOXYETHYL)PHTHALATE

By reacting phthalic anhydride with excess of diethylene glycol and metal acetate, the metal salts of mono(hydroxyethoxyethyl)phthalate were prepared (metal = Cu²⁺, Mn²⁺ and Zn²⁺). Polyurethanes containing metal ions in the main chain were synthesized by reacting hexamethylene diisocyanate (HMDI) or tolulylene 2,4-diisocyanate (TDI) with Cu²⁺, Mn²⁺ and Zn²⁺ salts of mono(hydroxyethoxyethyl)phthalate using di-n-butyltin dilaurate (DBTDL) as catalyst. The prepared monomers and polyurethanes were characterized by FT-IR, ¹H-NMR, ¹³C-NMR, UV spectra, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), elemental analysis, solubility and viscosity studies. The antibacterial activity of these polyurethanes have also been investigated using agar diffusion method.     

Calcium‐containing poly(urethane‐urea)s: Synthesis,spectral, and thermal studies

A calcium salt of mono(hydroxypentyl)phthalate [Ca(HPP)₂] was synthesized by the reaction of 1,5‐pentanediol, phthalic anhydride, and calcium acetate. Four different bisureas such as hexamethylene bis(ω,N‐hydroxyethylurea), tolylene 2,4‐bis(ω,N‐hydroxyethylurea), hexamethylene bis(ω,N‐hydroxypropylurea), and tolylene 2,4‐bis(ω,N‐hydroxypropylurea) were prepared by reacting ethanolamine or propanolamine with hexamethylene diisocyanate (HMDI) or tolylene 2,4‐diisocyanate (TDI). Calcium‐containing poly(urethane‐urea)s (PUUs) were synthesized by reacting HMDI or TDI with 1:1 mixtures of Ca(HPP)₂ and each of the bisureas with di‐n‐butyltin dilaurate as a catalyst. The PUUs were well characterized by Fourier transform infrared spectroscopy, ¹H and ¹³C NMR, solid‐state ¹³C–cross‐polarization/magic‐angle spinning NMR, viscosity, solubility, elemental analysis, and X‐ray diffraction studies. Thermal properties of the polymers were also examined with thermogravimetric analyses and differential scanning calorimetry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1809–1819, 2004     

由聚丙二醇二缩水甘油醚和甘油制备温敏性超支化聚合物

由聚丙二醇二缩水甘油醚和甘油通过质子转移聚合(proton transfer polymerization)一步法制备了端羟基的温敏性超支化聚醚.聚合产物的分子量(Mn)在1.76×104~2.43×104之间,玻璃化转变温度(Tg)在-31.5~-26.7℃之间,热分解温度(Td)在367~376℃之间.通过控制聚丙二醇二缩水甘油醚和甘油的投料比,实现了对温敏性超支化聚醚最低临界溶解温度(LCST)的调节,LCST可控制在28.3~39.6℃之间.     

Gel formation in cationic polymerization of divinyl ethers. III. Effect of oligooxyethylene chain versus oligomethylene chain as central spacer units

Cationic polymerizations of two series of divinyl ethers were carried out to clarify the effects of their central spacer chain structure on their crosslinking polymerization behavior. One series of the monomers involves divinyl ethers with an oligooxyethylene central spacer chain: diethylene glycol divinyl ether ( O‐3 ), triethylene glycol divinyl ether ( O‐4 ), tetraethylene glycol divinyl ether ( O‐5 ), pentaethylene glycol divinyl ether ( O‐6 ), and heptaethylene glycol divinyl ether ( O‐8 ) (see Scheme 1 ). The other series includes divinyl ethers with an oligomethylene central spacer chain: 1,4‐butanediol divinyl ether ( C‐4 ), 1,6‐hexanediol divinyl ether ( C‐6 ), and 1,8‐octanediol divinyl ether ( C‐8 ). Cationic polymerizations of these monomers were carried out with the hydrogen chloride/zinc chloride (HCl/ZnCl₂) initiating system in methylene chloride (CH₂Cl₂) at ?30 °C ([Monomer]₀ = 0.15 M; [HCl]₀ = 5.0 mM; [ZnCl₂]₀ = 0.5 mM). The polymerizations of the oligomethylene‐based divinyl ethers C‐6 and C‐8 caused gel formation at high monomer conversions (～90%), whereas C‐4 formed soluble polymers even at almost 100% monomer conversion. The oligooxyethylene‐based divinyl ethers O‐3 , O‐4 , O‐5 , and O‐6 underwent gel‐free polymerizations up to 100% monomer conversion and O‐8 did so at least up to ～80% conversion. The content of unreacted pendant vinyl groups of the obtained soluble polymers was measured by ¹H NMR spectroscopy. In the polymerizations of the oligomethylene‐based divinyl ethers ( C‐4 , C‐6 , and C‐8 ), the vinyl contents of the polymers decreased monotonously with increasing monomer conversion, and their number‐average molecular weights (M_n's) and polydispersity ratios (M_w/M_n's) increased considerably just before the gelation occurred. On the contrary, the vinyl contents of the polymers obtained from the oligooxyethylene‐based divinyl ethers ( O‐3 , O‐4 , O‐5 , O‐6 , and O‐8 ) decreased steeply even in the early stage of the polymerizations and almost all the pendant vinyl ether groups were consumed in the soluble polymers at the final stage of the polymerizations. The oligooxyethylene spacer units adjacent to the pendant unreacted vinyl ether groups may solvate intramolecularly with the carbocationic active center to accelerate frequent occurrence of intramolecular crosslinking reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3729–3738, 2004     

Excess Molar Volumes and Viscosities for Binary Mixtures of 1-Alkoxypropan-2-ols with 1-Butanol, and 2-Butanol at 298.15 K and Atmospheric Pressure

Excess molar volumes Vm^E and kinematic viscosities v have been measured as a function of composition for binary mixtures of propylene glycol monomethyl ether （1-methoxy-2-propanol）, MeOCH2CH（OH）Me, propylene glycol monoethyl ether （1-ethoxy-2-propanol）, EtOCH2CH（OH）Me, propylene glycol monopropyl ether （1-propoxy-2-propanol）, PrOCH2CH（OH）Me, propylene glycol monobutyl ether （1-butoxy-2-propanol）, BuOCH2CH（OH）Me, and propylene glycol tert-butyl ether （1-tert-butoxy-2-propanol）, t-BuOCH2CH（OH）Me with 1-butanol, and 2-butanol, at 298.15 K and atmospheric pressure. The excess molar volumes are negative across the entire range of composition for all the systems with 1-butanol, and positive for the systems 2-butanol＋ 1-methoxy-2-propanol, and ＋1-propoxy-2-propanol, negative for the systems 2-butanol＋1-butoxy-2-propanol, and change sign for the systems 2-butanol＋ 1-ethoxy-2-propanol, and ＋ 1-tert-butoxy-2-propanol. From the experimental data, the deviation in dynamic viscosity η from ∑χiηi has been calculated. Both excess molar volumes and viscosity deviations have been correlated using a Redlich-Kister type polynomial equation by the method of least-squares for the estimation of the binary coefficients and the standard errors.     

Studies on calcium‐containing poly(urethane ether)s

The calcium salt of mono(hydroxyethoxyethyl)phthalate [Ca(HEEP)₂] was synthesized by the reaction of diethylene glycol, phthalic anhydride, and calcium acetate. Calcium‐containing poly(urethane ether)s (PUEs) were synthesized by the reaction of hexamethylene diisocyanate (HMDI) or tolylene 2,4‐diisocyanate (TDI) with a mixture of Ca(HEEP)₂ and poly(ethylene glycol) (PEG₃₀₀ or PEG₄₀₀) with di‐n‐butyltin dilaurate as a catalyst. A series of calcium‐containing PUEs of different compositions were synthesized with Ca(HEEP)₂/PEG₃₀₀ (or PEG₄₀₀)/diisocyanate (HMDI or TDI) molar ratios of 2:2:4, 3:1:4, and 1:3:4 so that the coating properties of the PUEs could be studied. Blank PUEs without calcium‐containing ionic diols were also prepared by the reaction of PEG₃₀₀ or PEG₄₀₀ with HMDI or TDI. The PUEs were well characterized by Fourier transform infrared, ¹H and ¹³C NMR, solid‐state cross‐polarity/magic‐angle‐spinning ¹³C NMR, viscosity, solubility, and X‐ray diffraction studies. The thermal properties of the polymers were also studied with thermogravimetric analysis and differential scanning calorimetry. The PUEs were applied as top coats on acrylic‐coated leather, and their physicomechanical properties were also studied. The coating properties of PUEs, such as the tensile strength, elongation at break, tear strength, water vapor permeability, flexing endurance, cold crack resistance, abrasion resistance, color fastness, and adhesive strength, were better than the standard values. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2865–2878, 2003     

Free-radical synthesis of poly(urethane-g-N-vinyl pyrrolidone)

Relatively high-molecular-weight segmented polyurethanes based on methylene bis(4-phenyl-iso-cyanate), poly(propylene glycol), butane-1,4 diol, and cis-2-butene-1,4 diol have been synthesized and characterized. These unsaturated polyurethanes were successfully grafted using N-vinyl pyrrolidone as monomer and 2,2′-azobisisobutyronitrile as free-radical initiator. However, grafting experiments involving benzoyl peroxide as initiator were unsuccessful. The graft copolymers were isolated from the ungrafted polyurethane and poly(N-vinyl pyrrolidone) by selective solvent extraction. Elemental microanalysis, IR, NMR, thermogravimetric analysis, and equilibrium water sorption measurements were used to characterize the graft copolymers.     

新型三硅氧烷表面活性剂的合成与界面性能

低聚乙二醇单甲醚和环氧氯丙烷在相转移催化剂(P.T.C)存在下合成出低聚乙二醇甲醚缩水甘油醚, 然后与氨丙基三硅氧烷进行开环反应, 合成出了新型的三硅氧烷表面活性剂Me₃SiOSiMeROSiMe₃ [R＝(CH₂)₃N(CH₂CH(OH)CH₂- (OCH₂CH₂)_xOCH₃)₂, x＝1, 2]. 通过¹H NMR确证了这些目标产物的结构, 并且通过测定其水溶液的平衡表面张力研究了其表面活性. 在浓度约为10^－4 mol•L^－1时可以将水的表面张力降低至约21～22 mN•m^－1.     

Segmented poly(ether urethane) films containing ferrocene units in the hard segments

Segmented poly(ether urethanes) were synthesized from polypropylene glycol (PPG) and 4,4′-methylene-bis(phenyl-isocyanate) (MDI), using 1,1′-bis(β-aminoethyl)ferrocene (BAF) and 1,1′-bis(β-hydroxyethyl)ferrocene (BHF) as chain extenders. These polymers were characterized by infrared and ¹³C-NMR spectroscopy. Mass spectrometry was also utilized to determine the linkage of BAF and BHF in these polymers.     

Hyperbranched poly(ether–urea)s using AB2‐type blocked isocyanate monomer and azide monomer: Synthesis,characterization, reactive end functionalization,and copolymerization with AB monomer

3,5‐bis(4‐aminophenoxy)phenyl phenylcarbamate—a novel AB₂‐type blocked isocyanate monomer and 3,5‐bis{ethyleneoxy(4‐aminophenoxy)}phenyl carbonyl azide—a novel AB₂‐type azide monomer were synthesized in high yield. Step‐growth polymerization of these monomers were found to give a first example of hyperbranched poly (aryl‐ether‐urea) and poly(aryl‐alkyl‐ether‐urea). Molecular weights (M_w) of the polymer were found to vary from 1,858 to 52,432 depending upon the monomer and experimental conditions used. The polydispersity indexes were relatively narrow due to the controlled regeneration of isocyanate functional groups for the polymerization reaction. The degree of branching (DB) was determined using ¹H‐NMR spectroscopy and the values ranged from 87 to 54%. All the polymers underwent two‐stage decomposition and were stable up to 300 °C. Functionalized end‐capping of poly(aryl‐ether‐urea) using phenylchloroformate and di‐t‐butyl dicarbonate (Boc)₂O changed the thermal properties and solubility of the polymers. Copolymerization of AB₂‐type blocked isocyante monomer with functionally similar AB monomer were also carried out. The molecular weights of copolymers were found to be in the order of 6 × 10⁵ with narrow dispersity. It was found that the T_g's of poly(aryl‐alkyl‐ether‐urea)s were significantly less (46–49 °C) compared to poly(aryl‐ether‐urea)s. Moreover the former showed melting transition at 154 °C, which was not observed in the latter case. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2959–2977, 2007     

Post Polymerization of Saturated and Unsaturated Poly(3-hydroxy alkanoate)s

Summary : Chemical modification is useful to diversify poly(3-hydroxyalkanoate)s, for medical and industrial applications. In this manner, transesterification reactions of poly(3-hydroxy butyrate) were carried out under reflux condition of 1,2-dichlorobenzene in the presence of 1,4-butane diol, poly(ethylene glycol) bis(2-aminopropyl ether) with molecular weights of 1000 and 2000, poly(ethylene glycol)methacrylate or glycerol at 180 °C. Addition reactions of bromine and –SH groups of 3-mercaptopropionic acid to the double bond of poly(3-hydroxy-10-undecenoate) were also carried out. Functionalized poly(3-hydroxyalkanoate)s were characterized using ¹H NMR, FTIR, GPC and thermal analysis techniques.     

Sucrose-Branched Polymer Synthesized by Protease from Bacillus Subtilis

Summary: Vinyl sugar ester, 1′-O-vinyladipoyl-sucrose, was synthesized using sucrose and DVA (divinyl adipate) in organic medium (dimethylformamide), catalyzed by protease from Bacillus subtilis. Several reaction conditions were examined by means of qualitative analysis (TLC). The monomer obtained has undergone chemical polymerization with potassium persulfate and hydrogen peroxide to produce an amphiphilic polymer having sugar branches. The monomer was characterized by ¹³C-NMR and FTIR spectra. The IR analysis confirmed the synthesis of the poly (1′-O-vinyladipoyl-sucrose).     

Sequence distribution of poly(ether)urethane elastomer

Poly(ether)urethane elastomers (PEUE) having different sequence distributions can be synthesized by the reaction of p-phenylene diisocyanate, poly(oxytetramethylene glycol), and hydrazine by four different routes. The degree of the sequence distribution of PEUE was determined by high-resolution NMR spectroscopy. The sequence distribution of PEUE synthesized by the prepolymer method in solvent (method 1) was found to coincide with the sequence distribution calculated from the reactivity ratio of two isocyanate groups in p-phenylene diisocyanate. On the other hand, the sequence distribution of PEUE obtained by the prepolymer method without solvent (method 2) was found to deviate from that expected from the reactivity ratio. The degree of the distribution of monomers in PEUE having the same composition ratio corresponded to the infrared absorbance ratio at 1720 and 1700 cm^?1.     

Synthesis and characterization of polyurethanes containing cholesterol and phosphatidylcholine analogous moieties

Several new polyurethanes containing cholesterol and phosphatidylcholine analogous moieties were synthesized by addition polymerization of 2-[bis(2-hydroxyethyl)methylammonio]ethyl 5-cholesten-3β-yl phosphate ( 2 ) with diisocyanates such as hexamethylene diisocyanate (HDI), 2,4-tolylene diisocyanate (TDI), 4,4′-methylenediphenyl diisocyanate (MDI) and m-xylylene diisocyanate (XDI), respectively. They were characterized by their IR and ¹H NMR spectral data and elemental analyses. Preliminary studies suggest that these polyurethanes show the viscosity behavior of common polyelectrolytes.     

Synthesis of networked polymers with lithium counter cations from a difunctional epoxide containing poly(ethylene glycol) and an epoxide monomer carrying a lithium sulfonate salt moiety

Poly(ethylene glycol)‐based networked polymers that had lithium sulfonate salt structures on the network were prepared by heating a mixture of poly(ethylene glycol) diglycidyl ether (PEGGE), poly(ethylene glycol) bis(3‐aminopropyl) terminated (PEGBA), and an ionic epoxy monomer, lithium 3‐glycidyloxypropanesulfonate (LiGPS). Flexible self‐standing networked polymer films showed high thermal stability, low crystallinity, low glass transition temperature, and good mechanical strength. The materials were ion conductive at room temperature even under a dry condition, although the ionic conductivity was rather low (10^?6 to 10^?5 S/m). The ionic conductivity increased with the increase in temperature to above 1 × 10^?4 S/m at 90 °C. The film samples became swollen by immersing in propylene carbonate (PC) or PC solution of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The samples swollen in PC showed higher ionic conductivity (ca.1 × 10^?3 S/m at room temperature), and the samples swollen in LiTFSI/PC showed much higher ionic conductivity (nearly 1 S/m at room temperature). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3113–3118, 2010     

Electroninitiated polymerization of bis(trichlorophenoxo)-tetramethylethylene diamine copper(II)

Electroninitiated polymerization of bis(trichlorophenoxo)-N,N,N′,N′-tetramethylethylene diamine copper(II) was achieved in acetonitrile at various peak potentials of the monomer. A constant potential approach was selected in polymerization reactions. Electrolyses were carried out under air, nitrogen, and oxygen atmospheres. Structural analyses of the polymers were done by ¹H-NMR and ¹³C-NMR FT–IR spectroscopy. Molecular weights of the polymers were determined by vapor pressure (isopiestic) method.     

Thermoresponsive hyperbranched polymers via In Situ RAFT copolymerization of peg‐based monomethacrylate and dimethacrylate monomers

Here we report the preparation of PEG‐based thermoresponsive hyperbranched polymers via a facile in situ reversible addition‐fragmentation chain transfer (RAFT) copolymerization using bis(thiobenzoyl) disulphide to form 2‐cyanoprop‐2‐yl dithiobenzoate in situ. This novel one‐pot in situ RAFT approach was studied firstly using methyl methacrylate (MMA) monomer, then was used to prepare thermoresponsive hyperbranched polymers by copolymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMEMA, M_n = 475), poly(propylene glycol) methacrylate (PPGMA, M_n = 375) and up to 30 % of ethylene glycol dimethacrylate (EGDMA) as the branching agent. The resultant PEGMEMA‐PPGMA‐EGDMA copolymers from in situ RAFT were characterized by Gel Permeation Chromatography (GPC) and ¹H‐NMR analysis. The results confirmed the copolymers with multiple methacrylate groups and hyperbranched structure as well as RAFT functional residues. These water‐soluble copolymers with tailored compositions demonstrated tuneable lower critical solution temperature (LCST) from 22 °C to 32 °C. The phase transition temperature can be further altered by post functionalization via aminolysis of RAFT agent residues in polymer chains. Moreover, it was demonstrated by rheological studies and particle size measurements that these copolymers can form either micro‐ or macro photocrosslinked gels at suitable concentrations due to the presence of multiple methacrylate groups. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3751–3761