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2018 Volume 36 Issue 11
2018, 36(11):
Abstract:
2018, 36(11): 1207-1216
doi: 10.1007/s10118-018-2146-3
Abstract:
In this study, a series of aryloxy-aluminoxanes originated directly from the hydrolysis of reaction products of AlMe3 and phenols were synthesized, which could serve as effective polymer-retarding activators for the iron-catalyzed ethylene oligomerization. The molar ratios of [PhOH]/[AlMe3] and [H2O]/[Al] during the preparation were explored and their impacts on the oligomerization activity and product distribution were discussed. To obtain the effective activators with good polymer-retarding effect and relatively high activity, the optimized conditions were proposed to be [PhOH]/[AlMe3] = 0.5 and [H2O]/[Al] = 0.7. Various aluminoxanes with different [―OH] sources confirmed the importance of using phenols in preparing the effective polymer-retarding activators. By utilizing these aryloxy-aluminoxanes, the mass fraction of polymers in the total products could be reduced to lower than 1.0 wt%, which is much lower than that of the MAO-activated systems (> 30 wt%). This is a potential benefit for the industrial application of the iron-catalyzed oligomerization process.
In this study, a series of aryloxy-aluminoxanes originated directly from the hydrolysis of reaction products of AlMe3 and phenols were synthesized, which could serve as effective polymer-retarding activators for the iron-catalyzed ethylene oligomerization. The molar ratios of [PhOH]/[AlMe3] and [H2O]/[Al] during the preparation were explored and their impacts on the oligomerization activity and product distribution were discussed. To obtain the effective activators with good polymer-retarding effect and relatively high activity, the optimized conditions were proposed to be [PhOH]/[AlMe3] = 0.5 and [H2O]/[Al] = 0.7. Various aluminoxanes with different [―OH] sources confirmed the importance of using phenols in preparing the effective polymer-retarding activators. By utilizing these aryloxy-aluminoxanes, the mass fraction of polymers in the total products could be reduced to lower than 1.0 wt%, which is much lower than that of the MAO-activated systems (> 30 wt%). This is a potential benefit for the industrial application of the iron-catalyzed oligomerization process.
Effect of Halogen Chain End Fidelity on the Synthesis of Poly(methyl methacrylate-b-styrene) by ATRP
2018, 36(11): 1217-1224
doi: 10.1007/s10118-018-2139-2
Abstract:
Poly(methyl methacrylate-b-styrene) (PMMA-b-PS) block copolymers are synthesized by two consecutive ATRPs and fractionated into four fractions. The halogen chain end fidelity (CEF) in PMMA-b-PS is quantified based on the analysis of each fraction. Compared to ethyl 2-phenyl-2-bromoacetate/CuBr/2,2′-bipyridine (EPBA/CuBr/bpy) and CuBr/N,N,N′,N″,N″-pentamethyldiethylene-triamine (CuBr/PMDETA) catalysts, PMMA-b-PS synthesized using p-toluenesulfonyl chloride/CuCl/bpy (TsCl/CuCl/bpy) and CuCl/PMDETA catalysts has a higher halogen CEF and a better control on molecular weight.
Poly(methyl methacrylate-b-styrene) (PMMA-b-PS) block copolymers are synthesized by two consecutive ATRPs and fractionated into four fractions. The halogen chain end fidelity (CEF) in PMMA-b-PS is quantified based on the analysis of each fraction. Compared to ethyl 2-phenyl-2-bromoacetate/CuBr/2,2′-bipyridine (EPBA/CuBr/bpy) and CuBr/N,N,N′,N″,N″-pentamethyldiethylene-triamine (CuBr/PMDETA) catalysts, PMMA-b-PS synthesized using p-toluenesulfonyl chloride/CuCl/bpy (TsCl/CuCl/bpy) and CuCl/PMDETA catalysts has a higher halogen CEF and a better control on molecular weight.
2018, 36(11): 1225-1238
doi: 10.1007/s10118-018-2159-y
Abstract:
The synthesis and structure-property correlation of poly(N-(2-hydroxypropyl) methacrylamide) (PHPMA) conjugates with various architectures including random, block, branched or star-like structures and compositions have been thoroughly explored. However, related synthesis and structure-property data are still lacking for comb-like PHPMA. In this work, we report the synthesis of comb-like PHPMA copolymer-doxorubicin (DOX) conjugates with different backbone/side-chain lengths and location of drug moieties. Well-defined comb-like PHPMA-DOX conjugates are obtained via the combination of controlled radical polymerization and fractional precipitation techniques. The influences of structural factors on the biological properties such as cellular uptake, blood circulation and tumor accumulation have been investigated. Long blood circulation and efficient tumor accumulation can be achieved by proper control of the comb number, length and location of drug moieties. These facile comb-like structures possess great potentials in future theranostics for brachytherapy or surgical navigation.
The synthesis and structure-property correlation of poly(N-(2-hydroxypropyl) methacrylamide) (PHPMA) conjugates with various architectures including random, block, branched or star-like structures and compositions have been thoroughly explored. However, related synthesis and structure-property data are still lacking for comb-like PHPMA. In this work, we report the synthesis of comb-like PHPMA copolymer-doxorubicin (DOX) conjugates with different backbone/side-chain lengths and location of drug moieties. Well-defined comb-like PHPMA-DOX conjugates are obtained via the combination of controlled radical polymerization and fractional precipitation techniques. The influences of structural factors on the biological properties such as cellular uptake, blood circulation and tumor accumulation have been investigated. Long blood circulation and efficient tumor accumulation can be achieved by proper control of the comb number, length and location of drug moieties. These facile comb-like structures possess great potentials in future theranostics for brachytherapy or surgical navigation.
2018, 36(11): 1239-1250
doi: 10.1007/s10118-018-2156-1
Abstract:
Bacterial infections and the associated morbidity and mortality due to bacterial pathogens in wounds and medical implants have been increasing as most of current coatings cannot fulfill all the requirements including excellent intrinsically antibacterial activity, low cytotoxicity, and favorable physical properties. Herein, we present a kind of antibacterial hydrogel based on ε-poly(L-lysine) (EPL) grafted carboxymethyl chitosan (CMC-g-EPL) as the inherently antibacterial matrix and the surplus EPL as highly efficient antimicrobial agent. Such hydrogels possess tunable swelling abilities with water absorption percentages of 800%–2000% and modulus varying from 10 kPa to 100 kPa, and exhibit two-stage excellent antibacterial behavior. First, the free EPL can be released from the hydrogel network for quick and highly efficient bacteria killing with 99.99% of efficacy; second, the grafted EPL endows hydrogel matrix with prolonged intrinsically antibacterial activity, especially when most of free EPL is released from the hydrogel. Overall, we provide a new insight for preparing highly effective antibacterial hydrogels.
Bacterial infections and the associated morbidity and mortality due to bacterial pathogens in wounds and medical implants have been increasing as most of current coatings cannot fulfill all the requirements including excellent intrinsically antibacterial activity, low cytotoxicity, and favorable physical properties. Herein, we present a kind of antibacterial hydrogel based on ε-poly(L-lysine) (EPL) grafted carboxymethyl chitosan (CMC-g-EPL) as the inherently antibacterial matrix and the surplus EPL as highly efficient antimicrobial agent. Such hydrogels possess tunable swelling abilities with water absorption percentages of 800%–2000% and modulus varying from 10 kPa to 100 kPa, and exhibit two-stage excellent antibacterial behavior. First, the free EPL can be released from the hydrogel network for quick and highly efficient bacteria killing with 99.99% of efficacy; second, the grafted EPL endows hydrogel matrix with prolonged intrinsically antibacterial activity, especially when most of free EPL is released from the hydrogel. Overall, we provide a new insight for preparing highly effective antibacterial hydrogels.
2018, 36(11): 1251-1261
doi: 10.1007/s10118-018-2163-2
Abstract:
Developing a low-cost and well-recyclable adsorbent with high adsorption capacity is greatly desirable in dye wastewater treatment. Here, we demonstrate a kind of novel tough and reusable hydrogel beads with quite high capacity of dye adsorption via incorporating mussel-bioinspired poly(L-DOPA) (PDOPA) into alginate/poly(acrylamide) double network (DN) hydrogels. The synthesized PDOPA nanoaggregates were introduced into the DN hydrogels by simple one-pot mixing with the monomers prior to polymerization. The fabricated hydrogel beads exhibited high mechanical strength and good elastic recovery due to the interpenetrating Ca2+-alginate and poly(acrylamide) networks. It was shown that the beads exhibited relatively high dye adsorption capacity compared to other adsorbents reported in literature, and the introduction of PDOPA with an appropriate amount raised the adsorption capacity. It is believed that the addition of PDOPA and the matrix of double network architecture contributed synergistically to the high adsorption capacity of hydrogel beads. Moreover, the desorption of dyes could be easily realized via rinsing in acidic water and ethanol solution. The hydrogel beads remained the high adsorption capacity even after 5 times of adsorption and desorption cycles. This tough and stable hydrogel with high adsorption capacity may have potential in treatment of dye wastewater released by textile dyeing industry.
Developing a low-cost and well-recyclable adsorbent with high adsorption capacity is greatly desirable in dye wastewater treatment. Here, we demonstrate a kind of novel tough and reusable hydrogel beads with quite high capacity of dye adsorption via incorporating mussel-bioinspired poly(L-DOPA) (PDOPA) into alginate/poly(acrylamide) double network (DN) hydrogels. The synthesized PDOPA nanoaggregates were introduced into the DN hydrogels by simple one-pot mixing with the monomers prior to polymerization. The fabricated hydrogel beads exhibited high mechanical strength and good elastic recovery due to the interpenetrating Ca2+-alginate and poly(acrylamide) networks. It was shown that the beads exhibited relatively high dye adsorption capacity compared to other adsorbents reported in literature, and the introduction of PDOPA with an appropriate amount raised the adsorption capacity. It is believed that the addition of PDOPA and the matrix of double network architecture contributed synergistically to the high adsorption capacity of hydrogel beads. Moreover, the desorption of dyes could be easily realized via rinsing in acidic water and ethanol solution. The hydrogel beads remained the high adsorption capacity even after 5 times of adsorption and desorption cycles. This tough and stable hydrogel with high adsorption capacity may have potential in treatment of dye wastewater released by textile dyeing industry.
2018, 36(11): 1262-1268
doi: 10.1007/s10118-018-2149-0
Abstract:
pH-responsive micelles with a biodegradable PLA core and a mixed PEG/PDPA shell were prepared by self-assembly of poly(ethylene glycol)-b-poly(lactic acid) (PEG-b-PLA) and poly(2-(diisopropylamino)ethyl methacrylate)-b-poly(lactic acid) (PDPA-b-PLA). The micellization status with different pH and the enzyme degradation behavior were characterized by 1H-NMR spectroscopy, dynamic light scattering measurement and zeta potential test. The pH turning point of PDPA block was determined to be in the range of 5.5−7.0. While the pH was above 7.0, the PDPA block collapsed onto the PLA core and could protect the PLA core from invasion of enzyme, as a result, the micelle exhibited a resistance to the enzymatic degradation.
pH-responsive micelles with a biodegradable PLA core and a mixed PEG/PDPA shell were prepared by self-assembly of poly(ethylene glycol)-b-poly(lactic acid) (PEG-b-PLA) and poly(2-(diisopropylamino)ethyl methacrylate)-b-poly(lactic acid) (PDPA-b-PLA). The micellization status with different pH and the enzyme degradation behavior were characterized by 1H-NMR spectroscopy, dynamic light scattering measurement and zeta potential test. The pH turning point of PDPA block was determined to be in the range of 5.5−7.0. While the pH was above 7.0, the PDPA block collapsed onto the PLA core and could protect the PLA core from invasion of enzyme, as a result, the micelle exhibited a resistance to the enzymatic degradation.
2018, 36(11): 1269-1276
doi: 10.1007/s10118-018-2135-6
Abstract:
The phase transition from tetragonal form II to hexagonal form I was studied for the butene-1/ethylene and butene-1/1,5-hexadiene random copolymers, which have comparable molecular weight but distinct linear ethylene and ringlike methylene-1,3-cyclopentane (MCP) structural co-units, respectively. It is known that this solid phase transition follows the nucleation-growth mechanism, so the stepwise annealing protocol was utilized to investigate the influences of co-units on the optimal nucleation and growth temperatures. Compared with optimal nucleation and growth temperatures of −10 and 35 °C, respectively, in polybutene-1 homopolymer, two butene-1/ethylene copolymers with 1.5 mol% and 4.3 mol% co-units have the slightly lower optimal nucleation temperature of −15 °C but much higher optimal growth temperature of 50 °C. Clearly, the effect of ethylene co-unit is more significant on varying optimal temperature for growth than for nucleation. Furthermore, when the incorporated co-unit is ringlike MCP, the optimal nucleation temperature is −15 °C for 2.15 mol% co-units, the same with above BE copolymers, but −13 °C for a very low concentration of 0.65 mol%. Interestingly, the optimal growth temperature of butene-1/1,5-hexadiene copolymers with 0.65 mol%−2.15 mol% MCP co-units increases to 55 °C, which is also independent on co-unit concentration. These obtained values of optimal temperatures provide crucial parameters for rapid II-I phase transition.
The phase transition from tetragonal form II to hexagonal form I was studied for the butene-1/ethylene and butene-1/1,5-hexadiene random copolymers, which have comparable molecular weight but distinct linear ethylene and ringlike methylene-1,3-cyclopentane (MCP) structural co-units, respectively. It is known that this solid phase transition follows the nucleation-growth mechanism, so the stepwise annealing protocol was utilized to investigate the influences of co-units on the optimal nucleation and growth temperatures. Compared with optimal nucleation and growth temperatures of −10 and 35 °C, respectively, in polybutene-1 homopolymer, two butene-1/ethylene copolymers with 1.5 mol% and 4.3 mol% co-units have the slightly lower optimal nucleation temperature of −15 °C but much higher optimal growth temperature of 50 °C. Clearly, the effect of ethylene co-unit is more significant on varying optimal temperature for growth than for nucleation. Furthermore, when the incorporated co-unit is ringlike MCP, the optimal nucleation temperature is −15 °C for 2.15 mol% co-units, the same with above BE copolymers, but −13 °C for a very low concentration of 0.65 mol%. Interestingly, the optimal growth temperature of butene-1/1,5-hexadiene copolymers with 0.65 mol%−2.15 mol% MCP co-units increases to 55 °C, which is also independent on co-unit concentration. These obtained values of optimal temperatures provide crucial parameters for rapid II-I phase transition.
2018, 36(11): 1277-1285
doi: 10.1007/s10118-018-2134-7
Abstract:
In this study, we attempt to prepare a new blending system of poly(vinylidene fluoride) (PVDF) and aliphatic polyketone (POK) by melt compounding. The latter is a promising engineering plastic with comprehensive mechanical performances. When POK acted as minor phase to homogeneously disperse in and intimately contact with PVDF matrix, the brittle tensile behavior of neat PVDF transferred into a remarkably flexible manner (the elongation at break increased for 20 times), and more interestingly, the room-temperature durability of β-form PVDF in the uniaxially drawn blend film was obviously better than that in the neat PVDF film. Fourier transform infrared spectroscopy revealed that specific dipole interaction existed between CF2 group of PVDF and C＝O group of POK. The intermolecular dipolar interaction induced good compatibility in the PVDF/POK blends, as evidently proved by fine two-phase morphology and decreased melting points of POK crystals. Therefore, the good compatibility and interfacial enhancement are responsible for the improvement of the stretch ductility and β-form room-temperature durability of the PVDF/POK blends.
In this study, we attempt to prepare a new blending system of poly(vinylidene fluoride) (PVDF) and aliphatic polyketone (POK) by melt compounding. The latter is a promising engineering plastic with comprehensive mechanical performances. When POK acted as minor phase to homogeneously disperse in and intimately contact with PVDF matrix, the brittle tensile behavior of neat PVDF transferred into a remarkably flexible manner (the elongation at break increased for 20 times), and more interestingly, the room-temperature durability of β-form PVDF in the uniaxially drawn blend film was obviously better than that in the neat PVDF film. Fourier transform infrared spectroscopy revealed that specific dipole interaction existed between CF2 group of PVDF and C＝O group of POK. The intermolecular dipolar interaction induced good compatibility in the PVDF/POK blends, as evidently proved by fine two-phase morphology and decreased melting points of POK crystals. Therefore, the good compatibility and interfacial enhancement are responsible for the improvement of the stretch ductility and β-form room-temperature durability of the PVDF/POK blends.
2018, 36(11): 1286-1296
doi: 10.1007/s10118-018-2148-1
Abstract:
In this study, the effects of halloysite nanotubes (HNTs) reinforcement in expandable graphite based intumescent fire retardant coatings (IFRCs) developed using a polydimethylsiloxane (PDMS)/phenol BA epoxy system were investigated. Intumescent coating formulations were developed by incorporating different weight percentages of HNTs and PDMS in basic intumescent ingredients (ammonium polyphosphate/melamine/boric acid/expandable graphite, APP/MEL/BA/EG). The performance of intumescent formulations was investigated by furnace fire test, Bunsen burner fire test, field emission electron microscopy (FESEM), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and Fourier transform infrared analysis (FTIR). The Bunsen burner fire test results indicated that the fire performance of HNTs and PDMS reinforced intumescent formulation has improved due to the development of silicate network over the char residue. Improved expansion in char residue was also noticed in the formulation, SH(3), due to the minimum decomposition of char carbon. FESEM and TEM results validated the development of silicate network over char layer of coating formulations. A considerable mass loss difference was noticed during thermal gravimetric analysis (TGA) of intumescent coating formulations. Reference formulation, SH(0) with no filler, degraded at 300 °C and lost 50% of its total mass but SH(3), due to synergistic effects between PDMS and HNTs, degraded above 400 °C and showed the maximum thermal stability. XRD analysis showed the development of thermally stable compound mulltie, due to the synergism of HNTs and siloxane during intumescent reactions, which enhanced fire performance. FTIR analysis showed the presence of incorporated siloxane and silicates bonds in char residue, which endorsed the toughness of intumescent char layer produced. Moreover, the synergistic effect of HNTs, PDMS, and other basic intumescent ingredients enhanced the polymer cross-linking in binder system and improved fire resistive performance of coatings.
In this study, the effects of halloysite nanotubes (HNTs) reinforcement in expandable graphite based intumescent fire retardant coatings (IFRCs) developed using a polydimethylsiloxane (PDMS)/phenol BA epoxy system were investigated. Intumescent coating formulations were developed by incorporating different weight percentages of HNTs and PDMS in basic intumescent ingredients (ammonium polyphosphate/melamine/boric acid/expandable graphite, APP/MEL/BA/EG). The performance of intumescent formulations was investigated by furnace fire test, Bunsen burner fire test, field emission electron microscopy (FESEM), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and Fourier transform infrared analysis (FTIR). The Bunsen burner fire test results indicated that the fire performance of HNTs and PDMS reinforced intumescent formulation has improved due to the development of silicate network over the char residue. Improved expansion in char residue was also noticed in the formulation, SH(3), due to the minimum decomposition of char carbon. FESEM and TEM results validated the development of silicate network over char layer of coating formulations. A considerable mass loss difference was noticed during thermal gravimetric analysis (TGA) of intumescent coating formulations. Reference formulation, SH(0) with no filler, degraded at 300 °C and lost 50% of its total mass but SH(3), due to synergistic effects between PDMS and HNTs, degraded above 400 °C and showed the maximum thermal stability. XRD analysis showed the development of thermally stable compound mulltie, due to the synergism of HNTs and siloxane during intumescent reactions, which enhanced fire performance. FTIR analysis showed the presence of incorporated siloxane and silicates bonds in char residue, which endorsed the toughness of intumescent char layer produced. Moreover, the synergistic effect of HNTs, PDMS, and other basic intumescent ingredients enhanced the polymer cross-linking in binder system and improved fire resistive performance of coatings.
2018, 36(11): 1297-1302
doi: 10.1007/s10118-018-2145-4
Abstract:
Modified castor oil-based epoxy resin (EP)/polyurethane (PU) grafted copolymer by glycidyl polyhedral oligomeric silsesquioxane (glycidyl POSS) was synthesized. The damping properties, thermal stability, mechanical properties and morphology of the grafted copolymer modified by glycidyl POSS were studied systematically. The results revealed that the incorporation of glycidyl POSS improved the damping performance evidently and broadened damping temperature range, especially when the glycidyl POSS content was 0.2%–1%. At the same time, there was a slight increase in thermal stability with the increase of POSS content. The tensile properties changed with the change of the copolymer’sTg, decreased at low POSS contents and increased at high POSS contents. This modified copolymer has the potential to be used as film damping material or constrained damping layer.
Modified castor oil-based epoxy resin (EP)/polyurethane (PU) grafted copolymer by glycidyl polyhedral oligomeric silsesquioxane (glycidyl POSS) was synthesized. The damping properties, thermal stability, mechanical properties and morphology of the grafted copolymer modified by glycidyl POSS were studied systematically. The results revealed that the incorporation of glycidyl POSS improved the damping performance evidently and broadened damping temperature range, especially when the glycidyl POSS content was 0.2%–1%. At the same time, there was a slight increase in thermal stability with the increase of POSS content. The tensile properties changed with the change of the copolymer’sTg, decreased at low POSS contents and increased at high POSS contents. This modified copolymer has the potential to be used as film damping material or constrained damping layer.
