A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and C...A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and C_n types of monomers by one-pot polymerization via the couple-monomer methodology(CMM). The AB type monomer used in this paper was methyl acrylate, and C_n monomers were multi-amino compounds such as ethylenediamine(EDA), diethylenetriamine(DETA), triethylenetetraamine(TETA), tetraethylenepentaamine(TEPA) and pentaethylenehexamine(PEHA). The reaction mechanism was investigated by means of the mass spectra of the reaction intermediates. Adjusting the feed ratio of AB to C_n, hyperbranched polymers with different terminal groups and properties were obtained. FTIR, NMR, DSC, and TGA were used to characterize the polymers. It was found that the polymers′ properties such as solubility, thermal behaviour and encapsulation capability varied with changing the feed ratio of AB to C_n. Benzoyl and palmitoyl groups were introduced into these macromolecules by acidylation to form amphiphilic hyperbranched polymers which have a high capability to encapsulate water soluble dyes such as Congo red. It is expected that the hyperbranched PAMAMs can play an important role in the industrial applications, such as coatings, cross-linking and phase-transferring agents because of their versatility and availability.展开更多
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
This paper reports the production of glycopolymers via a simple and flexible method.A novel glycopolymer with a hyperbranched poly(amido amine) core and a sugar shell (HPAA-GLc) was synthesized by using thiol-ene clic...This paper reports the production of glycopolymers via a simple and flexible method.A novel glycopolymer with a hyperbranched poly(amido amine) core and a sugar shell (HPAA-GLc) was synthesized by using thiol-ene click reaction via facile one-pot method.Hyperbranched poly(amido amine) with vinyl terminals was first synthesized by Michael addition polymerization of N,N'-methylene bisacrylamide (MBA) with 1-(2-aminoethyl) piperazine (AEPZ).Subsequently,thiol-ene click reaction between vinyl units of hyperbranched poly(amido amine) and thio-glucose was performed in situ.Based on the NMR result,all the vinyl groups reacted with thiol-glucose in 120 min.Strong photoluminescence emission was observed from the aqueous solution of HPAA-GLc.展开更多
To make photoinitiators （PI） to be polymeric and water-soluble is an effective approach to develop the high efficient photoinitiator systems with low-migration, low-toxic and environment-friend. We developed a serie...To make photoinitiators （PI） to be polymeric and water-soluble is an effective approach to develop the high efficient photoinitiator systems with low-migration, low-toxic and environment-friend. We developed a series of novel amphiphilic hyperhranched polymeric photoinitiators （hPEA-TXs, and hPEA- BPs） by introducing thioxanthone （TX） or benzophenone （BP） moieties into the periphery of the hyperbranched poly（ether amine） （hPEA） comprised of the hydrophilic poly（ethylene oxide） （PEO） short chain and coinitiator amine moieties in the backbone. Compared with their water-soluble low-molecular weight analogues, the resulting hyperbranched polymeric photoinitiators hPEA101-TX, hPEA211-TX, hPEA101-BP and hPEA211-BP could be dissolved very well not only in many organic systems including acrylate monomers, but also in water with high solubility of 10 wt~. The photopolymerization kinetics of water-soluble monomer acrylamide （AM） and three hydrophobic multifunctional acrylate monomers initiated by these hyperbranched photoinitiators were investigated in detail by photo-differential scanning calorimetric （photo-DSC）. Both hPEA-TXs and hPEA-BPs can initiate photopolymerization of AM as efficiently as their low-molecular weight analogues MGA-TX and MGA-BP, respectively. The final double bond conversion （DBC） of oil-soluble monomer hexanediol diacrylate （HDDA） photoinitiated by these hyperbranched photoinitiators can reach as high as 99%. Especially for photopolymerization of multifunctional monomers initiated by these hyperbranched polymeric photoinitiators, the final DBC of trimethylolpropane triacrylate （TMPTA） and pentaerythritol tetraacrylate （PETTA） can reach 80% and 60%, respectively, which is much higher than that of low-molecular weight photoinitiators.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
文摘A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and C_n types of monomers by one-pot polymerization via the couple-monomer methodology(CMM). The AB type monomer used in this paper was methyl acrylate, and C_n monomers were multi-amino compounds such as ethylenediamine(EDA), diethylenetriamine(DETA), triethylenetetraamine(TETA), tetraethylenepentaamine(TEPA) and pentaethylenehexamine(PEHA). The reaction mechanism was investigated by means of the mass spectra of the reaction intermediates. Adjusting the feed ratio of AB to C_n, hyperbranched polymers with different terminal groups and properties were obtained. FTIR, NMR, DSC, and TGA were used to characterize the polymers. It was found that the polymers′ properties such as solubility, thermal behaviour and encapsulation capability varied with changing the feed ratio of AB to C_n. Benzoyl and palmitoyl groups were introduced into these macromolecules by acidylation to form amphiphilic hyperbranched polymers which have a high capability to encapsulate water soluble dyes such as Congo red. It is expected that the hyperbranched PAMAMs can play an important role in the industrial applications, such as coatings, cross-linking and phase-transferring agents because of their versatility and availability.
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supported by the National Natural Science Foundation of China (20874093,50973102)
文摘This paper reports the production of glycopolymers via a simple and flexible method.A novel glycopolymer with a hyperbranched poly(amido amine) core and a sugar shell (HPAA-GLc) was synthesized by using thiol-ene click reaction via facile one-pot method.Hyperbranched poly(amido amine) with vinyl terminals was first synthesized by Michael addition polymerization of N,N'-methylene bisacrylamide (MBA) with 1-(2-aminoethyl) piperazine (AEPZ).Subsequently,thiol-ene click reaction between vinyl units of hyperbranched poly(amido amine) and thio-glucose was performed in situ.Based on the NMR result,all the vinyl groups reacted with thiol-glucose in 120 min.Strong photoluminescence emission was observed from the aqueous solution of HPAA-GLc.
基金the National Natural Science Foundation of China(Nos. 21522403,51373098)Education Commission of Shanghai Municipal Government(No.15SG13)IFPM2016B002 of Shanghai jiao Tong University & Affiliated Sixth People's Hospital South Campus for their financial support
文摘To make photoinitiators （PI） to be polymeric and water-soluble is an effective approach to develop the high efficient photoinitiator systems with low-migration, low-toxic and environment-friend. We developed a series of novel amphiphilic hyperhranched polymeric photoinitiators （hPEA-TXs, and hPEA- BPs） by introducing thioxanthone （TX） or benzophenone （BP） moieties into the periphery of the hyperbranched poly（ether amine） （hPEA） comprised of the hydrophilic poly（ethylene oxide） （PEO） short chain and coinitiator amine moieties in the backbone. Compared with their water-soluble low-molecular weight analogues, the resulting hyperbranched polymeric photoinitiators hPEA101-TX, hPEA211-TX, hPEA101-BP and hPEA211-BP could be dissolved very well not only in many organic systems including acrylate monomers, but also in water with high solubility of 10 wt~. The photopolymerization kinetics of water-soluble monomer acrylamide （AM） and three hydrophobic multifunctional acrylate monomers initiated by these hyperbranched photoinitiators were investigated in detail by photo-differential scanning calorimetric （photo-DSC）. Both hPEA-TXs and hPEA-BPs can initiate photopolymerization of AM as efficiently as their low-molecular weight analogues MGA-TX and MGA-BP, respectively. The final double bond conversion （DBC） of oil-soluble monomer hexanediol diacrylate （HDDA） photoinitiated by these hyperbranched photoinitiators can reach as high as 99%. Especially for photopolymerization of multifunctional monomers initiated by these hyperbranched polymeric photoinitiators, the final DBC of trimethylolpropane triacrylate （TMPTA） and pentaerythritol tetraacrylate （PETTA） can reach 80% and 60%, respectively, which is much higher than that of low-molecular weight photoinitiators.
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.
