An epoxy-terminated hyperbranched aromatic polyester (P3) was synthesized from a hyperbranched aromatic polyester containing carboxylic acid end groups (P1), which was derived from the condensation polymerization of t...An epoxy-terminated hyperbranched aromatic polyester (P3) was synthesized from a hyperbranched aromatic polyester containing carboxylic acid end groups (P1), which was derived from the condensation polymerization of the AB(2) monomer, 5-acetoxyisophthalic acid. Polymer P1 was converted into the polymeric acid chloride by reaction with thionyl chloride. The acid chloride was reacted with ethanol and glycidol to form a poly(ethyl ester) (P2) and an epoxy terminated material (P3), respectively. The reaction conditions in each step of these processes had to be controlled very carefully to avoid unwanted cross-linking reactions. The characterization of products and intermediates, including molecular weight distributions and thermal properties, are reported.展开更多
The synthesis and characterization of hyperbranched polyester （HBP） with different molecular weight are studied. The effect of HBP on the modification of epoxy resins cured with anhydride is mainly discussed. The ch...The synthesis and characterization of hyperbranched polyester （HBP） with different molecular weight are studied. The effect of HBP on the modification of epoxy resins cured with anhydride is mainly discussed. The characteristics of HBP and the morphologies of cured system are determined by nuclear magnetic resonance spectroscopy （NMR）, gel permeation chromatography （GPC） and scanning electron microscope （SEM）. The impact strength of cured system is detected and Fourier transform infrared （FTIR） measurements were used to pursue the curing process. The investigation shows that HBP can improve the toughness by forming copolymer networks between epoxy resins, HBP and anhydride. Moreover, when the molecular weight of HBP is 1342g/mol the toughening effect is the best, and the changes of toughness are small with the increase of molecular weight of HBP to 3500 g/mol.展开更多
The viscosity, the shrinkage degree and the photopolymerization rate of the epoxy acrylate (EB600) blended with hyperbranched acrylated aromatic polyester (HAAPE) were investigated. The addition of HAAPE into EB600 la...The viscosity, the shrinkage degree and the photopolymerization rate of the epoxy acrylate (EB600) blended with hyperbranched acrylated aromatic polyester (HAAPE) were investigated. The addition of HAAPE into EB600 largely reduces the viscosity of the blend formulation and the shrinkage degree. For example, EB600 resin with 50% weight fraction of HAAPE has the 1250 cps of the viscosity and 2.0% of shrinkage degree, while the pure EB600 resin has 3000 cps of the viscosity and 10.5% of shrinkage degree. The photopolymerization rate of the resin is also promoted by HAAPE addition. The good miscibility between HAAPE and EB600 was also observed from the dynamic mechanical analysis. The tensile, flexural and compressive strength, and the thermal properties of the UV cured films are greatly improved.展开更多
Recently, hyperbranched polymers(HBPs), which differ significantly in structure and properties from linear, cross-linked and branched analogs, have become increasingly important. HBP have a spatial unloaded core and a...Recently, hyperbranched polymers(HBPs), which differ significantly in structure and properties from linear, cross-linked and branched analogs, have become increasingly important. HBP have a spatial unloaded core and a shell of branched monomer units(dendrons), in which functional groups are predominantly located in the surface layer. The size of macromolecules ranges from 2 nm to 100 nm. Currently, there are a fairly large number of publications in the literature devoted to the modification of hyperbranched polyester polyols with various functional groups and the assessment of the potential for their use. However, there are no review articles on this topic in recent years. In this regard, it is relevant to generalize the latest achievements in the field of synthesis, properties and application of hyperbranched polyester polyols with terminal oxygen, nitrogen, silicon, sulfur and organophosphorus fragments. The advantage of hyperbranched polyester polyols of the Boltorn H series is their industrial availability, biodegradability, nanoscale, non-toxicity and high solubility in various polar solvents due to short monomer units, as well as the presence of reactive terminal hydroxyl groups. Functionalization of hyperbranched polyester polyols at hydroxyl groups is mainly carried out by addition of acid anhydrides, iso(thio)cyanates, alkenes, lactides, lactones, lactams, epoxy compounds or reactions with halogenated compounds(alkyl halides, acid chlorides). In some cases, for the functionalization of polyester polyols special linkers are used, such as acid chlorides of unsaturated or dicarboxylic acids, diisocyanates, etc., which provide covalent bonding of the hyperbranched polymer with the target functional group. The obtained derivatives of hyperbranched polyesters are widely used in such areas as biomedicine, pharmacy, paints and varnishes, they are also used as catalysts, membranes, multifunctional coatings, plasticizers and polymer stabilizers.展开更多
The amphiphilic multiarm copolymers were synthesized through the modification of commercially available hyperbranched polyesters（Boltorn H40） with N-ε-carbobenzoxy-L-Lysine N-carboxyanhydride（ZLys-NCA）.After bein...The amphiphilic multiarm copolymers were synthesized through the modification of commercially available hyperbranched polyesters（Boltorn H40） with N-ε-carbobenzoxy-L-Lysine N-carboxyanhydride（ZLys-NCA）.After being condensed with N-Boc-phenylalanine（Boc-^NPhe） and deprotected the Boc-groups in trifluoroacetic acid（TFA）,the original terminal hydroxyl groups were transformed into the amino groups and then initiated the ring-opening polymerization of ZLys-NCA.The hydrophilic poly（L-lysine） was grafted to the surface of Boltorn H40 successfully after the protecting benzyl groups were removed by the HBr solution in glacial acetic acid（33 wt%）.The resulting multiarm copolymers were characterized by the ^1H-NMR,GPC and FTIR.The arm length calculated by NMR and GPC analysis was about 3 and 13 lysine-units for H40-Phe-PLysl and H40-Phe-PLys2 respectively.Due to the amphiphilic molecular structure,they displayed ability to self-assemble into spherical micelles in aqueous solution with the average diameter in the range from 70 nm to 250 nm.The CMC of H40-Phe-PLysl and H40-Phe-PLys2 was 0.013 mg/mL and 0.028 mg/mL,respectively, indicating that H40-Phe-PLysl with shorter arm length is easier to self-assemble than H40-Phe-PLys2 with longer arm length.展开更多
Hyperbranched polymers possess special architectures and have potential applications in various areas. In this study, two AB 2 monomers, dipropyl 5 (hydroxyethoxy) isophthalate (I) and 5 hydroxyethoxyisophthaic a...Hyperbranched polymers possess special architectures and have potential applications in various areas. In this study, two AB 2 monomers, dipropyl 5 (hydroxyethoxy) isophthalate (I) and 5 hydroxyethoxyisophthaic acid (II), were prepared. By bulk polycondensation of each monomer, two aliphatic aromatic hyperbranched polyesters were prepared and characterized by 1H nuclear magnetic resonance ( 1H NMR), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), and scanning electron microscopy (SEM). Compared with all aromatic hyperbranched polyesters, the prepared polymers showed lower glass transition temperatures in connection with the moderate decrease in their decomposition temperatures.展开更多
基金The project is supported by the EPSRC and the Youth Science Foundation of Shanghai Higher Education.
文摘An epoxy-terminated hyperbranched aromatic polyester (P3) was synthesized from a hyperbranched aromatic polyester containing carboxylic acid end groups (P1), which was derived from the condensation polymerization of the AB(2) monomer, 5-acetoxyisophthalic acid. Polymer P1 was converted into the polymeric acid chloride by reaction with thionyl chloride. The acid chloride was reacted with ethanol and glycidol to form a poly(ethyl ester) (P2) and an epoxy terminated material (P3), respectively. The reaction conditions in each step of these processes had to be controlled very carefully to avoid unwanted cross-linking reactions. The characterization of products and intermediates, including molecular weight distributions and thermal properties, are reported.
文摘The synthesis and characterization of hyperbranched polyester （HBP） with different molecular weight are studied. The effect of HBP on the modification of epoxy resins cured with anhydride is mainly discussed. The characteristics of HBP and the morphologies of cured system are determined by nuclear magnetic resonance spectroscopy （NMR）, gel permeation chromatography （GPC） and scanning electron microscope （SEM）. The impact strength of cured system is detected and Fourier transform infrared （FTIR） measurements were used to pursue the curing process. The investigation shows that HBP can improve the toughness by forming copolymer networks between epoxy resins, HBP and anhydride. Moreover, when the molecular weight of HBP is 1342g/mol the toughening effect is the best, and the changes of toughness are small with the increase of molecular weight of HBP to 3500 g/mol.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .5 0 2 330 30 )
文摘The viscosity, the shrinkage degree and the photopolymerization rate of the epoxy acrylate (EB600) blended with hyperbranched acrylated aromatic polyester (HAAPE) were investigated. The addition of HAAPE into EB600 largely reduces the viscosity of the blend formulation and the shrinkage degree. For example, EB600 resin with 50% weight fraction of HAAPE has the 1250 cps of the viscosity and 2.0% of shrinkage degree, while the pure EB600 resin has 3000 cps of the viscosity and 10.5% of shrinkage degree. The photopolymerization rate of the resin is also promoted by HAAPE addition. The good miscibility between HAAPE and EB600 was also observed from the dynamic mechanical analysis. The tensile, flexural and compressive strength, and the thermal properties of the UV cured films are greatly improved.
文摘Recently, hyperbranched polymers(HBPs), which differ significantly in structure and properties from linear, cross-linked and branched analogs, have become increasingly important. HBP have a spatial unloaded core and a shell of branched monomer units(dendrons), in which functional groups are predominantly located in the surface layer. The size of macromolecules ranges from 2 nm to 100 nm. Currently, there are a fairly large number of publications in the literature devoted to the modification of hyperbranched polyester polyols with various functional groups and the assessment of the potential for their use. However, there are no review articles on this topic in recent years. In this regard, it is relevant to generalize the latest achievements in the field of synthesis, properties and application of hyperbranched polyester polyols with terminal oxygen, nitrogen, silicon, sulfur and organophosphorus fragments. The advantage of hyperbranched polyester polyols of the Boltorn H series is their industrial availability, biodegradability, nanoscale, non-toxicity and high solubility in various polar solvents due to short monomer units, as well as the presence of reactive terminal hydroxyl groups. Functionalization of hyperbranched polyester polyols at hydroxyl groups is mainly carried out by addition of acid anhydrides, iso(thio)cyanates, alkenes, lactides, lactones, lactams, epoxy compounds or reactions with halogenated compounds(alkyl halides, acid chlorides). In some cases, for the functionalization of polyester polyols special linkers are used, such as acid chlorides of unsaturated or dicarboxylic acids, diisocyanates, etc., which provide covalent bonding of the hyperbranched polymer with the target functional group. The obtained derivatives of hyperbranched polyesters are widely used in such areas as biomedicine, pharmacy, paints and varnishes, they are also used as catalysts, membranes, multifunctional coatings, plasticizers and polymer stabilizers.
基金supported by the National Basic Research Program(Nos.2007CB808000,2009CB930400)the National Natural Science Foundation of China(Nos.50873058,20874060,50633010)+1 种基金Shanghai Leading Academic Discipline Project(No.B202)the Zhejiang Provincial Natural Science Foundation of China(No.Y405411)
文摘The amphiphilic multiarm copolymers were synthesized through the modification of commercially available hyperbranched polyesters（Boltorn H40） with N-ε-carbobenzoxy-L-Lysine N-carboxyanhydride（ZLys-NCA）.After being condensed with N-Boc-phenylalanine（Boc-^NPhe） and deprotected the Boc-groups in trifluoroacetic acid（TFA）,the original terminal hydroxyl groups were transformed into the amino groups and then initiated the ring-opening polymerization of ZLys-NCA.The hydrophilic poly（L-lysine） was grafted to the surface of Boltorn H40 successfully after the protecting benzyl groups were removed by the HBr solution in glacial acetic acid（33 wt%）.The resulting multiarm copolymers were characterized by the ^1H-NMR,GPC and FTIR.The arm length calculated by NMR and GPC analysis was about 3 and 13 lysine-units for H40-Phe-PLysl and H40-Phe-PLys2 respectively.Due to the amphiphilic molecular structure,they displayed ability to self-assemble into spherical micelles in aqueous solution with the average diameter in the range from 70 nm to 250 nm.The CMC of H40-Phe-PLysl and H40-Phe-PLys2 was 0.013 mg/mL and 0.028 mg/mL,respectively, indicating that H40-Phe-PLysl with shorter arm length is easier to self-assemble than H40-Phe-PLys2 with longer arm length.
文摘Hyperbranched polymers possess special architectures and have potential applications in various areas. In this study, two AB 2 monomers, dipropyl 5 (hydroxyethoxy) isophthalate (I) and 5 hydroxyethoxyisophthaic acid (II), were prepared. By bulk polycondensation of each monomer, two aliphatic aromatic hyperbranched polyesters were prepared and characterized by 1H nuclear magnetic resonance ( 1H NMR), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), and scanning electron microscopy (SEM). Compared with all aromatic hyperbranched polyesters, the prepared polymers showed lower glass transition temperatures in connection with the moderate decrease in their decomposition temperatures.
