Nano-SiO2 was modified using silane coupling agent （KH-550） and hyperbranched poly（amine-ester） respectively, and Poly（vinyl chloride） （PVC）/modified nano-SiO2 composites were made by melt-blending. The compos...Nano-SiO2 was modified using silane coupling agent （KH-550） and hyperbranched poly（amine-ester） respectively, and Poly（vinyl chloride） （PVC）/modified nano-SiO2 composites were made by melt-blending. The composites＇ structures andmechanical properties were characterized by transmission electron microscopy（TEM）, sanning electronic microscopy（SEM） and electronic universal testing machine. The results. show that nano-SiO2 grafted by hyperbranched poly （amine-ester） increases obviously in dispersion in PVC matrix, and mechanical properties of PVC are effectively improved. Moreover, it was found that mechanical properties of PVC/nano-SiO2 composites reach the best when weight percent of nano-SiO2 in PVC matrix is 1%. Compared with crude PVC, the tensile strength of hyperbranched poly （amine-ester） grafted nano-SiO2/ PVC composite increases by 24.68 % and its break elongation, flexural strength and impact strength increase by 15.73%, 4.07% and 1 841.84%, respectively. Moreover, the processing of the composites is improved.展开更多
Hydrophilic hyperbranched poly(ester-amine) (HPEA) synthesized from diethanolamine and methyl acrylate was used as phase transfer agent for the first time to transfer methyl orange (MO) from water into chloroform. Thi...Hydrophilic hyperbranched poly(ester-amine) (HPEA) synthesized from diethanolamine and methyl acrylate was used as phase transfer agent for the first time to transfer methyl orange (MO) from water into chloroform. This process was quantified by UV-Vis spectra. A possible mechanism was put forward based on the formation of amphiphilic aggregates.展开更多
The aromatic hyperbranched poly（ester amines）（AHPEAs） were successfully synthesized via the mild condensation of N-4-cyanobenzyl diethanolamine hydrogenchloride as an AB2 monomer in concentrated HCI. The polymeriz...The aromatic hyperbranched poly（ester amines）（AHPEAs） were successfully synthesized via the mild condensation of N-4-cyanobenzyl diethanolamine hydrogenchloride as an AB2 monomer in concentrated HCI. The polymerization was monitored by FTIR to suppose the reasonable reaction mechanism. The degree of branching was determined to be 0.55 by 1H NMR with an increased conversion of up to 96%. The glass transition temperature was measured by differential scanning calorimetry to range from -19 to 15℃ The molecular weights and polydispersities were investigated by gel permeation chromatography.展开更多
Crosslinked film of hyperbranched poly（amine-ester） （HPAE） was prepared by crosslinking its terminal hydroxyl groups with glutaraldehyde （GA）. Atom force microscope （AFM） and scanning electron microscope （SEM...Crosslinked film of hyperbranched poly（amine-ester） （HPAE） was prepared by crosslinking its terminal hydroxyl groups with glutaraldehyde （GA）. Atom force microscope （AFM） and scanning electron microscope （SEM） reveals that they have smooth surfaces, dense and homogenous matrices. It was found that the water static contact angle is smaller than 41.7°, the tensile strength is higher than 8.9 MPa, the elongation at break is higher than 5.1%, the swelling degree is higher than 42% in water, and the Bovine hemoglobin （Hb） adsorption is relatively low. These results indicate that the crosslinked HPAE films might have some potential applications in many areas.展开更多
Three secondary amine terminated hyperbranched poly（ester-amine）s （defined as HPEA1, HPEA2 and HPEA3） were synthesized from piperazine （A2） and trimethylolpropane triacrylate （TMPTA, B3） at their molar ratios ...Three secondary amine terminated hyperbranched poly（ester-amine）s （defined as HPEA1, HPEA2 and HPEA3） were synthesized from piperazine （A2） and trimethylolpropane triacrylate （TMPTA, B3） at their molar ratios of 2.5：1, 2.25：1 and 2.0：1, respectively. The polymers were analyzed by 1H NMR, GPC, DSC and TGA. The results indicated that the ratio of secondary amine to tertiary amine and the content of secondary amine decreased, while the molecular weight, molecular weight distribution and glass transition temperature （Tg） increased from HPEA1 to HPEA3. Due to their reactive terminal groups and flexible chains, these polymers further reacted with an epoxy resin （E51） to form cured films under ambient conditions. With increasing the ratio between secondary amine groups and epoxy groups from 1：2 to 2：1, the gel content, film hardness and onset decomposing temperature of the cured samples increased. The good film performances should make the polymers as the components of non-solvent coating materials.展开更多
Hyperbranched poly(amine-ester) (HBPAE) was synthesized via pseudo-one-step process between trimethylolpropane as a core molecule and N, N-diethylol-3-amine methylpropionate as the AB2 branched monomer. The prepared p...Hyperbranched poly(amine-ester) (HBPAE) was synthesized via pseudo-one-step process between trimethylolpropane as a core molecule and N, N-diethylol-3-amine methylpropionate as the AB2 branched monomer. The prepared polymer was analyzed by IR, GPC, 1H-NMR and thermal analysis (TGA and DSC). The performance of the polymer in cement was tested by measuring the effect of 1, 3 and 5 wt% of HBPAE solutions on the properties of Ordinary Portland Cement. Water of consistency, setting times, bulk density, apparent porosity, compressive strength and combined water content of the polymer/cement pastes were studied. The results showed that water of consistency and apparent porosity decreased while setting times, compressive strength, combined water and bulk density increased with the polymer addition.展开更多
The new approach for synthesis of hyperbranched polymers from commercially available A2 and BB'2 type monomers was extended to synthesize hyperbranched copolymers. In this work, hyperbranched copoly(sulfone-amine)...The new approach for synthesis of hyperbranched polymers from commercially available A2 and BB'2 type monomers was extended to synthesize hyperbranched copolymers. In this work, hyperbranched copoly(sulfone-amine) was prepared by copolymerization of divinyl sulfone (A2) with 4,4'-trimethylenedipiperidine (B2) and N-ethylethylenediamine (BB'2). During the reaction,secondary-amino groups of B2 and BB'2 monomers react rapidly with vinyl groups of A2 monomers within 35 s, generating a type of intermediate containing one vinyl group and two reactive hydrogen atoms. Now the intermediates can be regarded as a new BB2 type monomer, whichfurther polymerizes to form hyperbranched copoly(sulfone-amine). The polymerization mechanism was investigated with FTIR and LC-MSD. The degree of branching (DB) of hyperbranched copolymers increased with decreasing the ratio of 4, 4'-trimethylenedipiperidine to N-ethylethylenediamine, so DB can be controlled. When the initial mole ratio of B2 to BB2 was equal to or higher than four, r≥4, resulted copolymers were semi-crystalline, while copolymers with r<3 were amorphous.展开更多
Aliphatic hyperbranched poly(ester amine)s with terminal acrylate groups were synthesized by Michael addition reaction between pizine and trimethylol propanetriacrylate (TMPTA) under various molar ratios, and their st...Aliphatic hyperbranched poly(ester amine)s with terminal acrylate groups were synthesized by Michael addition reaction between pizine and trimethylol propanetriacrylate (TMPTA) under various molar ratios, and their structures were characterized by 1H NMR,GPC and DSC analysis.The multi peaks within δ 4.04～4.18 (RCH 2OCOR′) in the 1H NMR spectra were analyzed and the peaks at δ 4.15, δ 4 06～4 07 and δ 4.04 can be assigned to terminal ( T ),linear ( L ) and dendritic units ( D ),respectively.Based on 1H NMR spectra,the degree of branching ( DB) for these polymers were calculated by using both the Fréchet method and the Frey method.With the molar ratio between pizine and TMPTA increased to 1/1,the terminate units decreased,both of the dendritic and linear units increased,while M n and M w/ M n became large and the T g value became high,accordingly.Moreover,cured films were obtained through UV radiation of the polymers.The gel contents for the films decreased with increasing the molar ratio between pizine and TMPTA,which may account for the changes of their mechanical properties.展开更多
Hyperbranched poly(ester-amine) with terminal amine groups was synthesized by Michael addition reaction between trimethylolpropanetriacrylate (B 3 monomer) and pizine (A 2 monomer) under molar ratio of 6∶13 via a one...Hyperbranched poly(ester-amine) with terminal amine groups was synthesized by Michael addition reaction between trimethylolpropanetriacrylate (B 3 monomer) and pizine (A 2 monomer) under molar ratio of 6∶13 via a one-step procedure.It was further modified by stearyl chloride to form an amphiphilic hyperbranched polymer.The structures of these polymers were characterized by FT-IR,{}+1H-NMR,DSC and GPC analyses.Due to the existence of interior secondary amines,the modified polymer can be used as phase transferring agent to extract methylic orange from water layer to CHCl-3 layer.Both higher transferring capability and higher transferring rate were achieved at lower pH of the water phase.The extracted dye in the organic layer can be further released to the water layer under a basic condition.A possible mechanism for extracting dye by amphiphilic hyperbranched polymer was suggested.展开更多
Water\|soluble hyperbranched copoly(ester\|amine)s with various degree of branching (DB) were prepared \%via\% the "A\-2+B\-2+BB′\-2" approach. Due to the faster reaction between A and B functional groups, ...Water\|soluble hyperbranched copoly(ester\|amine)s with various degree of branching (DB) were prepared \%via\% the "A\-2+B\-2+BB′\-2" approach. Due to the faster reaction between A and B functional groups, the intermediate containing one A group and two B′ groups was generated\% in situ\%. Further self\|polyaddition of the AB′\-2 intermediate gave hyperbranched polymer. In this communication, A\-2 is ethylene diacrylate (EDA), B\-2 is piperazine (PZ), and BB′\-2 is 1\|(2\|aminoethyl)piperazine (AP). The combination of mass spectrum and \%in situ\% FTIR determined the reaction mechanism and propagating paths predicted. DB of the resulting branched poly(ester\|amine)s decreases with increasing the feed ratio of PZ to AP. In the same molecular weight, the inherent viscosity of the polymers presented here increases with decreasing DB. The simplicity of the reaction process, the controllability of the architecture, and the commercially availability of the raw materials would make this approach attractive in the large scale manufacture and application of hyperbranched polymer materials.展开更多
基金Sponsored by the Ministerial Level Advanced Research Foundation (120701BQ0126)
文摘Nano-SiO2 was modified using silane coupling agent （KH-550） and hyperbranched poly（amine-ester） respectively, and Poly（vinyl chloride） （PVC）/modified nano-SiO2 composites were made by melt-blending. The composites＇ structures andmechanical properties were characterized by transmission electron microscopy（TEM）, sanning electronic microscopy（SEM） and electronic universal testing machine. The results. show that nano-SiO2 grafted by hyperbranched poly （amine-ester） increases obviously in dispersion in PVC matrix, and mechanical properties of PVC are effectively improved. Moreover, it was found that mechanical properties of PVC/nano-SiO2 composites reach the best when weight percent of nano-SiO2 in PVC matrix is 1%. Compared with crude PVC, the tensile strength of hyperbranched poly （amine-ester） grafted nano-SiO2/ PVC composite increases by 24.68 % and its break elongation, flexural strength and impact strength increase by 15.73%, 4.07% and 1 841.84%, respectively. Moreover, the processing of the composites is improved.
文摘Hydrophilic hyperbranched poly(ester-amine) (HPEA) synthesized from diethanolamine and methyl acrylate was used as phase transfer agent for the first time to transfer methyl orange (MO) from water into chloroform. This process was quantified by UV-Vis spectra. A possible mechanism was put forward based on the formation of amphiphilic aggregates.
基金Supported by the National Natural Science Foundation of China(No.50633010)
文摘The aromatic hyperbranched poly（ester amines）（AHPEAs） were successfully synthesized via the mild condensation of N-4-cyanobenzyl diethanolamine hydrogenchloride as an AB2 monomer in concentrated HCI. The polymerization was monitored by FTIR to suppose the reasonable reaction mechanism. The degree of branching was determined to be 0.55 by 1H NMR with an increased conversion of up to 96%. The glass transition temperature was measured by differential scanning calorimetry to range from -19 to 15℃ The molecular weights and polydispersities were investigated by gel permeation chromatography.
基金This work was supported by the National Natural Science Foundation of China (No. 50103010)the "973" Program (No. 2003. CB615705)
文摘Crosslinked film of hyperbranched poly（amine-ester） （HPAE） was prepared by crosslinking its terminal hydroxyl groups with glutaraldehyde （GA）. Atom force microscope （AFM） and scanning electron microscope （SEM） reveals that they have smooth surfaces, dense and homogenous matrices. It was found that the water static contact angle is smaller than 41.7°, the tensile strength is higher than 8.9 MPa, the elongation at break is higher than 5.1%, the swelling degree is higher than 42% in water, and the Bovine hemoglobin （Hb） adsorption is relatively low. These results indicate that the crosslinked HPAE films might have some potential applications in many areas.
文摘Three secondary amine terminated hyperbranched poly（ester-amine）s （defined as HPEA1, HPEA2 and HPEA3） were synthesized from piperazine （A2） and trimethylolpropane triacrylate （TMPTA, B3） at their molar ratios of 2.5：1, 2.25：1 and 2.0：1, respectively. The polymers were analyzed by 1H NMR, GPC, DSC and TGA. The results indicated that the ratio of secondary amine to tertiary amine and the content of secondary amine decreased, while the molecular weight, molecular weight distribution and glass transition temperature （Tg） increased from HPEA1 to HPEA3. Due to their reactive terminal groups and flexible chains, these polymers further reacted with an epoxy resin （E51） to form cured films under ambient conditions. With increasing the ratio between secondary amine groups and epoxy groups from 1：2 to 2：1, the gel content, film hardness and onset decomposing temperature of the cured samples increased. The good film performances should make the polymers as the components of non-solvent coating materials.
文摘Hyperbranched poly(amine-ester) (HBPAE) was synthesized via pseudo-one-step process between trimethylolpropane as a core molecule and N, N-diethylol-3-amine methylpropionate as the AB2 branched monomer. The prepared polymer was analyzed by IR, GPC, 1H-NMR and thermal analysis (TGA and DSC). The performance of the polymer in cement was tested by measuring the effect of 1, 3 and 5 wt% of HBPAE solutions on the properties of Ordinary Portland Cement. Water of consistency, setting times, bulk density, apparent porosity, compressive strength and combined water content of the polymer/cement pastes were studied. The results showed that water of consistency and apparent porosity decreased while setting times, compressive strength, combined water and bulk density increased with the polymer addition.
基金the National Natural Science Foundation of China (Grant No. 29974017).
文摘The new approach for synthesis of hyperbranched polymers from commercially available A2 and BB'2 type monomers was extended to synthesize hyperbranched copolymers. In this work, hyperbranched copoly(sulfone-amine) was prepared by copolymerization of divinyl sulfone (A2) with 4,4'-trimethylenedipiperidine (B2) and N-ethylethylenediamine (BB'2). During the reaction,secondary-amino groups of B2 and BB'2 monomers react rapidly with vinyl groups of A2 monomers within 35 s, generating a type of intermediate containing one vinyl group and two reactive hydrogen atoms. Now the intermediates can be regarded as a new BB2 type monomer, whichfurther polymerizes to form hyperbranched copoly(sulfone-amine). The polymerization mechanism was investigated with FTIR and LC-MSD. The degree of branching (DB) of hyperbranched copolymers increased with decreasing the ratio of 4, 4'-trimethylenedipiperidine to N-ethylethylenediamine, so DB can be controlled. When the initial mole ratio of B2 to BB2 was equal to or higher than four, r≥4, resulted copolymers were semi-crystalline, while copolymers with r<3 were amorphous.
文摘Aliphatic hyperbranched poly(ester amine)s with terminal acrylate groups were synthesized by Michael addition reaction between pizine and trimethylol propanetriacrylate (TMPTA) under various molar ratios, and their structures were characterized by 1H NMR,GPC and DSC analysis.The multi peaks within δ 4.04～4.18 (RCH 2OCOR′) in the 1H NMR spectra were analyzed and the peaks at δ 4.15, δ 4 06～4 07 and δ 4.04 can be assigned to terminal ( T ),linear ( L ) and dendritic units ( D ),respectively.Based on 1H NMR spectra,the degree of branching ( DB) for these polymers were calculated by using both the Fréchet method and the Frey method.With the molar ratio between pizine and TMPTA increased to 1/1,the terminate units decreased,both of the dendritic and linear units increased,while M n and M w/ M n became large and the T g value became high,accordingly.Moreover,cured films were obtained through UV radiation of the polymers.The gel contents for the films decreased with increasing the molar ratio between pizine and TMPTA,which may account for the changes of their mechanical properties.
文摘Hyperbranched poly(ester-amine) with terminal amine groups was synthesized by Michael addition reaction between trimethylolpropanetriacrylate (B 3 monomer) and pizine (A 2 monomer) under molar ratio of 6∶13 via a one-step procedure.It was further modified by stearyl chloride to form an amphiphilic hyperbranched polymer.The structures of these polymers were characterized by FT-IR,{}+1H-NMR,DSC and GPC analyses.Due to the existence of interior secondary amines,the modified polymer can be used as phase transferring agent to extract methylic orange from water layer to CHCl-3 layer.Both higher transferring capability and higher transferring rate were achieved at lower pH of the water phase.The extracted dye in the organic layer can be further released to the water layer under a basic condition.A possible mechanism for extracting dye by amphiphilic hyperbranched polymer was suggested.
文摘Water\|soluble hyperbranched copoly(ester\|amine)s with various degree of branching (DB) were prepared \%via\% the "A\-2+B\-2+BB′\-2" approach. Due to the faster reaction between A and B functional groups, the intermediate containing one A group and two B′ groups was generated\% in situ\%. Further self\|polyaddition of the AB′\-2 intermediate gave hyperbranched polymer. In this communication, A\-2 is ethylene diacrylate (EDA), B\-2 is piperazine (PZ), and BB′\-2 is 1\|(2\|aminoethyl)piperazine (AP). The combination of mass spectrum and \%in situ\% FTIR determined the reaction mechanism and propagating paths predicted. DB of the resulting branched poly(ester\|amine)s decreases with increasing the feed ratio of PZ to AP. In the same molecular weight, the inherent viscosity of the polymers presented here increases with decreasing DB. The simplicity of the reaction process, the controllability of the architecture, and the commercially availability of the raw materials would make this approach attractive in the large scale manufacture and application of hyperbranched polymer materials.
