A polytransesterification method of preparation of the high-molecular-weight poly(alkylene H-phosphonates) - polymers bearing a reactive -OP(O)(H)O-units, is described: Mechanism of transesterification involves mostly -OP(O)(H)O⊖, Mt⊕ “growing species”. The polyphosphonates were converted into a number of derivative polymers, like poly(alkylene phosphates), prepared by a direct oxidation, without decreasing of the DPn of the parent polymers. 相似文献
Twelve amphiphilic polymers were synthesized using poly(ethylene glycols) (PEGs) of different molecular weights, viz. 1000, 2000 and 4000 as hydrophilic block and linkers namely azelaic acid, sebacic acid, dimethyl isophthalate acid and dimethyl terephthalate as hydrophobic block in the presence of catalyst Conc. H2SO4. Synthesized polymers were characterized by using 1H-NMR, 13C-NMR and IR spectroscopy. Micellar sizes of the polymers were determined using Dynamic Light Scattering (DLS) which ranged from 51.6–174 nm for aliphatic polymers and 135.5–371 nm for aromatic polymers. Transmission Electron Microscope (TEM) results confirm the findings of DLS. Critical Micelle Concentrations (CMC) of the synthesized polymers were determined using electrical conductivity meter which ranged from 95 to 130 mg L?1 for aliphatic polymers and 420–1500 mg L?1 for aromatic polymers. 相似文献
Twelve amphiphilic polymers were synthesized using poly(ethylene glycols) (PEGs) of different molecular weights, viz. 300, 600 and1000 as hydrophilic block and aliphatic diacids namely glutaric acid, adipic acid, pimelic acid and suberic acid as hydrophobic block in presence of catalyst Conc. H2SO4. Synthesized polyesters were characterized by using 1H-NMR, 13C-NMR and IR spectroscopy. Micellar sizes of the polymers were determined using Dynamic Light Scattering (DLS) which ranged from 127.5–354 nm. Transmission Electron Microscope (TEM) results confirm the findings of DLS. Critical Micelle Concentrations (CMC) of the synthesized polymers were determined using electrical conductivity meter which ranged from 112 to 155 mg L?1. 相似文献
Organolithium compounds and other Group IA organometallics cleave high molecular weight poly(alkylene oxides) very rapidly at room temperature in dilute benzene solution. This reaction also works on a dimeric polyepoxide such as bis(2-n-butoxyethyl)ether and much less readily on a monomeric one as 1,2-dimethoxyethane. On the other hand, a simple aliphatic monoether such as di-n-butyl ether is not cleaved under conditions several orders of magnitude more drastic than were effective on the polyethers. The mechanism for this facile polyether cleavage is proposed as a β-elimination in which the organolithium is greatly activated by chelation with the main-chain oxygen atoms of the polyether. This cleavage method has been used broadly on high molecular weight polyethers to obtain quantitative yields of hydroxyl-ended, amorphous, and crystalline polyethers (Mn = 500–10,000), many of which cannot be made by direct polymerization. Aliphatic polysulfides and an N-substituted aliphatic polyamine cleave by this same method to, respectively, mercapto-ended and secondary amine-ended polymers. The mechanism aspects of these results are discussed. 相似文献
Polyurethanes and polyureas containing long methylene chain units have been prepared from the following six series of monomer combinations; aliphatic diisocyanates with aliphatic glycols or diamines, methylene bis(4-phenyl isocyanate) with aliphatic glycols or diamines, and p-xylylene diisocyanate with aliphatic glycols or diamines. A good linear relationship was noted between the polymer melting points of each series against the concentration of functional groups. Both polyurethanes and polyureas from p-xylylene diisocyanate showed higher melting points than those from methylene bis(4-phenyl isocyanate) with corresponding aliphatic monomers. The relations between the melting points of these polymers with long methylene chains, including polyamides which were previously reported, and the chain components were discussed. The higher melting points of polymers containing p-xylylene group are attributed to the high rigidity of this group. 相似文献
In this research, we developed a novel and facile strategy to prepare aliphatic tertiary amine chromophore hyperbranched poly(amino ether ester)s with pH and thermo responsiveness via phosphazene base (t-BuP2) catalyzed oxa-Michael addition polymerization of triethanolamine with ethylene glycol diacrylate at room temperature. UV–vis and fluorescence analyses results showed that the tertiary amine at branching point for hyperbranched poly(amino ether ester)s is very important to retain strong blue fluorescence of tertiary amine chromophore. Moreover, the hyperbranched poly(amino ether ester)s exhibit an aggregation caused quenching (ACQ) fluorescence, solvent induced red-shifted emission, molecular weight, and temperature dependent emission characters. More interestingly, the hyperbranched poly(amino ether ester)s show extreme acid induced quenching fluorescence phenomenon, and also display good water solubility, specific recognition of Fe3+ ion, low cytotoxicity, and bright cell imaging, which could serve as a microenvironment-responding fluorescent probe for application in chemical sensing, cell imaging, drug delivery, or disease diagnostics. This research provides a versatile method for the preparation of stimuli-responsive aliphatic tertiary amine chromophore polymers, and supplies ideas for researchers to explore other unconventional fluorescent polymers for application. 相似文献
The chemical synthesis of new electroconducting poly(2,5-thienylene)s containing alkylhydroxy and alkylester side-chains in the β-position of the thiophene rings is reported. The polymers were obtained by oxidative homopolymerization or copolymerization of 2-(3-thienyl)ethanol and 2-(3-thienyl)ethyl hexanoate by FeCl3 in nitromethane. Structural characterization using elemental analysis, FT-IR and NMR spectroscopy shows that a partial nucleophilic substitution of the hydroxy group by chlorine and a partial cleavage of the ester function take place during polymerization. The presence of the ester function with a long aliphatic chain makes the polymers soluble and allows them to be processed into films. The polymers can be doped using a solution of FeCl3 to the maximum electrical conductivity of 10−3 Ω−1 cm−1. 相似文献
Sixteen amphiphilic polymers were synthesized using poly(ethylene glycols) (PEGs) of different molecular weights, viz. 1000, 1500, 2000 and 4000 as hydrophilic block and linkers namely azelaic acid, suberic acid, terephthalic acid and glycolic acid as hydrophobic block in the presence of catalyst conc. H2SO4 out of which four with glycolic acid as linker are new. Synthesized polymers were characterized by using 1H-NMR, 13C-NMR and IR spectroscopy. Micellar sizes of the polymers were determined using Dynamic Light Scattering (DLS) technique which ranged from 32.1–262.0 nm and confirmed by Transmission Electron Microscope (TEM) analysis. Molecular weights were determined using HORIBA SZ-100 scientific and varied from 6.5?×?102 to 6.5?×?103 Kilo Daltons(kDa) by Debye plot. Critical Micelle Concentrations (CMC) of the synthesized polymers was determined using electrical conductivity meter and it ranged from 105 to 125 milligrams per litre (mg L?1). 相似文献
The pressure dependence of the melting temperature of six aliphatic polyesters belonging to two different homologous series, poly(x-succinate) and poly(x-adipate) having even number of methylene groups (2,4,6) in the alkylene segment (x) was investigated by high pressure differential thermal analysis (HP-DTA) up to 500 MPa. The phase diagrams of these polyesters were newly determined except for poly(ethylene adipate). The dTm/dpo at atmospheric pressure was obtained from the quadratic equation and the trend of dTm/dpo with respect to the number of methylene groups in the monomer unit in each homologous series is discussed. Amorphous densities at 25 °C, expansion and compressibility coefficients in the melt of these polyesters are also reported. The entropy of fusion (ΔSm), enthalpy of fusion (ΔHm), volume change on melting (ΔVm), conformational entropy (ΔSor) and volume entropy (ΔSv) were correlated with respect to the number of methylene groups in the alkylene segment. ΔVm and ΔSv displayed a similar trend as that of dTm/dpo while ΔSm, ΔSor and ΔHm showed an increasing trend. The influence of these parameters on dTm/dpo is discussed in the context of the Clapeyron equation. 相似文献
A novel degradable poly(alkylene carbonate anhydride) (PACA) was synthesized by the melt polycondensation reaction of the corresponding mixed anhydrides of the dicarboxylic acid derived from oligo(tetramethylene carbonate)diol (OTMCD) and oligo(hexamethylene carbonate)diol (OHMCD). The polymer's structure was confirmed by IR and 1H NMR spectroscopy. DSC analysis showed PACA had a low Tg (< –30°C). In vitro degradation tests indicated that the degradation rate of poly(alkylene carbonate) was more controlled with the incorporation of anhydride groups. 相似文献
Eight novel PEG-based amphiphilic block copolymers having self-assembling properties has been reported in the present study. The polymers have been synthesized by reacting Poly(ethylene glycols) (PEGs) of different molecular weights viz. 600, 1000, 1500 and 2000 and dimethyl-5-hydroxyisophthalate in presence of concentrated H2SO4 as catalyst in solventless condition at 80–90°C and further alkylating the resulting polymers by attaching octyl and hexadecanyl chains to phenolic hydroxyl group. The resulting functionalized amphiphilic polymers have been characterized by 1H and 13C-NMR spectroscopy. These polymers, when dissolved in water, aggregate to form micelles, giving sizes ranging from 13.00 to 87.24 nm as determined by Dynamic Light Scattering (DLS) instrument. The molecular weights have been also calculated from the DLS and are in the range 3.5×104 to 1.8×106 KDa (Kilo Daltons). Critical Micelle Concentrations (CMC) of the synthesized polymers was determined using electrical conductivity meter with values in the range of 105 to 138 mg L?1 (milligrams per litre). 相似文献
ABSTRACT The condensation copolymerization of Dimethyl 5-hydroxyisophthalate (1) with Polyethylene glycols (PEGs) (2a–2d) of varying molecular weights, catalyzed by Novozyme-435 (immobilized Candida antarctica lipase B) in bulk is reported. The structures of the resulting polymers, Poly[(poly(oxyethylene)-oxy-5-hydroxyisophthaloyl] (3a–3c) were characterized by 1H (1D and 2D) and 13C-NMR spectroscopic experiments. Further, these polymers have been derivatized by attaching decanyl and 12-hydroxydodecanyl chains to the phenolic hydroxyl group. The resulting amphiphilic polymeric systems were characterized by detailed spectroscopic analysis. Light Scattering Photometry as well as Gel Per meation Chromatography were used to evaluate the particle size and molecular weights of the polymers. In principle, the method developed is flexible so that it can be used to generate a wide array of functionalized amphiphilic polymers. In the absence of biocatalytic transformation, such structural control would be extremely difficult or currently impossible to obtain. 相似文献
The variation of refractive index increments with molecular weight has been studied using solutions of polystyrene (2.2 × 103 < Mw < 1.8 × 106), poly(ethylene glycol) (1.0 × 103 < Mw < 2.0 × 104), and poly(dichlorophenylene oxide) (3.3 × 103 < Mw < 4.8 × 105) in toluene and poly(propylene glycol) (1.2 × 103 < Mw < 4.0 × 103) in benzene. The refractive index increments of polyglycols containing aliphatic ether moieties are negative in these solvents. However, poly(dichlorophenylene oxide) polymers, which contain aromatic ether moieties, give positive values. Linear and branched halogenated poly(phenylene oxide)s show an asymptotic approach of the refractive index increment to the same limiting value, but the approach is more rapid for the branched polymer. 相似文献
Epichlorohydrin polymers cleave much more readily with organolithium compounds than do other poly(alkylene oxides). In dilute toluene solution (1–2%) at ?78°C, the cleavage of polyepichlorohydrin occurs as rapidly as BuLi is added. The end-groups formed are about equimolar amounts of hydroxyl and carbonyl with small amounts of acetylene ends. This same cleavage reaction but without acetylene ends can be obtained with NaOH or NaOCH3 in dimethyl sulfoxide at 65°C. The carbonyl groups can be reduced with LiAlH4 in tetrahydrofuran to give hydroxyl-ended polymers. A mechanism is presented for this unusual cleavage reaction. 相似文献