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2005 Volume 23 Issue 5
2005, 23(5): 453-462
Abstract:
A new coupled finite element formulation is proposed to calculate a conformation tensor model in two complex flows: a planar contraction flow and a planar flow around a symmetrically placed cylinder. The components of conformation tensor are first computed together with the velocity and pressure to describe the change of morphology of polymer chain coils in flow fields. Macroscopic quantities of viscoelastic flow are then calculated based on the conformation tensor. Comparisons between the numerical simulations and experiments for stress patterns and velocity profiles are carried out to prove the validity of the method.
A new coupled finite element formulation is proposed to calculate a conformation tensor model in two complex flows: a planar contraction flow and a planar flow around a symmetrically placed cylinder. The components of conformation tensor are first computed together with the velocity and pressure to describe the change of morphology of polymer chain coils in flow fields. Macroscopic quantities of viscoelastic flow are then calculated based on the conformation tensor. Comparisons between the numerical simulations and experiments for stress patterns and velocity profiles are carried out to prove the validity of the method.
2005, 23(5): 463-469
Abstract:
A series of acrylic-based superabsorbent resins were synthesized by inverse suspension polymerization, using potassium persulfate as the initiator, N, N-methylene bisacrylamide (BIS) and divinylbenzene (DVB) as the multiple crosslinking agents. The morphology of the resulting superabsorbent resins revealed by SEM demonstrated that a hard shell layer was indeed formed due to surface crosslinking. The swelling and deswelling properties, and the mechanical strength of superabsorbents were investigated. The results indicated that the adding time of DVB and the amount of DVB participated in the crosslinking show a significant influence on the properties of superabsorbents. When DVB was added in polymerization later, the amount of DVB participated in reaction decreases and the surface crosslinked shell becomes thinner. It is suitable for DVB to be introduced in the later stage of the polymerization process, because the absorption rate of resin is efficiently improved in conjunction with higher water absorption. Furthermore, it was found that the mechanical strength of swollen superabsorbent with surface crosslinking was indeed enhanced in comparison with that of the conventional one.
A series of acrylic-based superabsorbent resins were synthesized by inverse suspension polymerization, using potassium persulfate as the initiator, N, N-methylene bisacrylamide (BIS) and divinylbenzene (DVB) as the multiple crosslinking agents. The morphology of the resulting superabsorbent resins revealed by SEM demonstrated that a hard shell layer was indeed formed due to surface crosslinking. The swelling and deswelling properties, and the mechanical strength of superabsorbents were investigated. The results indicated that the adding time of DVB and the amount of DVB participated in the crosslinking show a significant influence on the properties of superabsorbents. When DVB was added in polymerization later, the amount of DVB participated in reaction decreases and the surface crosslinked shell becomes thinner. It is suitable for DVB to be introduced in the later stage of the polymerization process, because the absorption rate of resin is efficiently improved in conjunction with higher water absorption. Furthermore, it was found that the mechanical strength of swollen superabsorbent with surface crosslinking was indeed enhanced in comparison with that of the conventional one.
2005, 23(5): 471-478
Abstract:
Unsaturated polyester resin (UPR)/acrylate-terminated polyurethane (ATPU)/organo-modified montmorillonite (OMMT) nanocomposites were prepared by the in situ intercalative polymerization method. Samples were prepared by the sequential mixing, i.e. mixture of the ATPU and styrene (S) and OMMT were prepared in the first step; UPR was then added to the pre-intercalates of ATPU/S/OMMT. Results indicate that the mechanical properties and thermal properties of UPR/ATPU/OMMT nanocomposites greatly depend on the amount of ATPU and OMMT. Results show that the addition of ATPU could increase the impact strength of UPR/ATPU composites, but the tensile strength, flexural strength and heat resistance of the materials are obviously decreased. When the weight ratio between UPR, ATPU and OMMT were 82:15:3, the impact strength and heat distortion-temperature of nanocomposite were greatly improved, meanwhile there was little change for other properties of the nanocomposites. The synergistic enhancement effects of ATPU and OMMT on the composites were observed. The structures and morphology of the composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.
Unsaturated polyester resin (UPR)/acrylate-terminated polyurethane (ATPU)/organo-modified montmorillonite (OMMT) nanocomposites were prepared by the in situ intercalative polymerization method. Samples were prepared by the sequential mixing, i.e. mixture of the ATPU and styrene (S) and OMMT were prepared in the first step; UPR was then added to the pre-intercalates of ATPU/S/OMMT. Results indicate that the mechanical properties and thermal properties of UPR/ATPU/OMMT nanocomposites greatly depend on the amount of ATPU and OMMT. Results show that the addition of ATPU could increase the impact strength of UPR/ATPU composites, but the tensile strength, flexural strength and heat resistance of the materials are obviously decreased. When the weight ratio between UPR, ATPU and OMMT were 82:15:3, the impact strength and heat distortion-temperature of nanocomposite were greatly improved, meanwhile there was little change for other properties of the nanocomposites. The synergistic enhancement effects of ATPU and OMMT on the composites were observed. The structures and morphology of the composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.
2005, 23(5): 479-485
Abstract:
Soap-free poly(methyl methacrylate-ethyl acrylate-methacrylic acid) latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwise alkali/acid treatment method. Effects of acid treatment conditions on the particle morphology were investigated. Results show that one to three pores were formed inside most of particles after post-treatment. At pH 7.0, when the treatment temperature was lower than 70℃, the size of particles and the volume of pores remained almost unchanged, and these two values increased significantly when the temperature was higher than 70℃. Both the particle size and the pore volume decreased with the increase in initial pH value and treatment time in the acid treatment. As the pH was below 4.0 and the treatment time was longer than 180 min, the particles shrunk in size.
Soap-free poly(methyl methacrylate-ethyl acrylate-methacrylic acid) latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwise alkali/acid treatment method. Effects of acid treatment conditions on the particle morphology were investigated. Results show that one to three pores were formed inside most of particles after post-treatment. At pH 7.0, when the treatment temperature was lower than 70℃, the size of particles and the volume of pores remained almost unchanged, and these two values increased significantly when the temperature was higher than 70℃. Both the particle size and the pore volume decreased with the increase in initial pH value and treatment time in the acid treatment. As the pH was below 4.0 and the treatment time was longer than 180 min, the particles shrunk in size.
2005, 23(5): 487-495
Abstract:
Polymer-stabilized platinum/ruthenium bimetallic colloids (Pt/Ru) were synthesized by polyol reduction with microwave irradiation and characterized by TEM and XPS. The colloidal nanoparticles have small and narrow size distributions. Catalytic performance of the Pt/Ru colloidal catalysts was investigated on the selective hydrogenation of crontonaldehyde (CRAL). A suitable amount of the added metal ions and base can improve the selectivity of CRAL to crotylalcohol (CROL) remarkably. The catalytic activity and the selectivity are dependent on the compositions of bimetallic colloids. Thereinto, PVP-stabilized 9Pt/1Ru colloid with a molar ratio of metals Pt:Ru = 9:1 shows the highest catalytic selectivity 77.3% to CROL at 333 K under 4.0 MPa of hydrogen.
Polymer-stabilized platinum/ruthenium bimetallic colloids (Pt/Ru) were synthesized by polyol reduction with microwave irradiation and characterized by TEM and XPS. The colloidal nanoparticles have small and narrow size distributions. Catalytic performance of the Pt/Ru colloidal catalysts was investigated on the selective hydrogenation of crontonaldehyde (CRAL). A suitable amount of the added metal ions and base can improve the selectivity of CRAL to crotylalcohol (CROL) remarkably. The catalytic activity and the selectivity are dependent on the compositions of bimetallic colloids. Thereinto, PVP-stabilized 9Pt/1Ru colloid with a molar ratio of metals Pt:Ru = 9:1 shows the highest catalytic selectivity 77.3% to CROL at 333 K under 4.0 MPa of hydrogen.
2005, 23(5): 497-501
Abstract:
The effect of storage on physico-chemical properties of non-irradiated natural rubber and radiation vulcanized natural rubber (RVNR) were evaluated. The rubber films were stored under two different conditions, namely in open air and sealed polyethylene bags. The antioxidant, tris(nonylated phenyl) phosphite (TNPP) was used for preventing degradation of RVNR films. Gel content, cross-link density, tensile strength at break and 500% elongation of rubber films were measured. The results show that the retention (%) of tensile properties of rubber films with TNPP is higher than that of rubber films without antioxidants. The rubber films stored in polyethylene bags also show better retention of tensile properties than those of rubber films stored in open air.
The effect of storage on physico-chemical properties of non-irradiated natural rubber and radiation vulcanized natural rubber (RVNR) were evaluated. The rubber films were stored under two different conditions, namely in open air and sealed polyethylene bags. The antioxidant, tris(nonylated phenyl) phosphite (TNPP) was used for preventing degradation of RVNR films. Gel content, cross-link density, tensile strength at break and 500% elongation of rubber films were measured. The results show that the retention (%) of tensile properties of rubber films with TNPP is higher than that of rubber films without antioxidants. The rubber films stored in polyethylene bags also show better retention of tensile properties than those of rubber films stored in open air.
2005, 23(5): 503-511
Abstract:
The adsorption behaviors of 2-naphthalenesulfonic acid and aniline on a conventional macroporous resin Amberlite XAD4 and the other two newly-developed hypercrosslinked resins NDA101 and NDA100 were investigated in a single or binary batch system at 293 K and 313 K, respectively. All the adsorption isotherms of 2-naphthalenesulfonic acid and aniline on the test resins in both systems can fit well with the Langmuir equation, indicating that the adsorption is a favorable process. At the identical equilibrium concentration, the amount of aniline adsorbed on polymeric resins in the single system is higher than that in the binary system because of the competitive adsorption between 2-naphthalenesulfonic acid and aniline on the resin surface. However, the uptake amount of 2-naphthalenesulfonic acid in the binary system is markedly larger than that in the single system, which is presumably due to the cooperative effect arisen from the electrostatic interaction between 2-naphthalenesulfonic acid and aniline adsorbed on the resin surface. The simultaneous adsorption system was proven to be helpful for the selective adsorption toward 2-naphthalenesulfonic acid due to its larger selective index.
The adsorption behaviors of 2-naphthalenesulfonic acid and aniline on a conventional macroporous resin Amberlite XAD4 and the other two newly-developed hypercrosslinked resins NDA101 and NDA100 were investigated in a single or binary batch system at 293 K and 313 K, respectively. All the adsorption isotherms of 2-naphthalenesulfonic acid and aniline on the test resins in both systems can fit well with the Langmuir equation, indicating that the adsorption is a favorable process. At the identical equilibrium concentration, the amount of aniline adsorbed on polymeric resins in the single system is higher than that in the binary system because of the competitive adsorption between 2-naphthalenesulfonic acid and aniline on the resin surface. However, the uptake amount of 2-naphthalenesulfonic acid in the binary system is markedly larger than that in the single system, which is presumably due to the cooperative effect arisen from the electrostatic interaction between 2-naphthalenesulfonic acid and aniline adsorbed on the resin surface. The simultaneous adsorption system was proven to be helpful for the selective adsorption toward 2-naphthalenesulfonic acid due to its larger selective index.
2005, 23(5): 513-519
Abstract:
A series of novel p(N-isopropylacrylamide) (PNIPAM) hydrogels were synthesized by radical copolymerization of N-isopropylacrylamide (NIPAM) and 3-methacryloxypropyltrimethoxysilane (MPTMS). The copolymers were then crosslinked through hydrolysis of the siloxane in acetic acid/water mixed solvent. Beta-cyclodextrin (Beta-CD) was introduced into the polymeric networks by condensation of 3-glycidoxypropyltrimethoxysilane derived beta-cyclodextrin (KH560-beta-CD) with MPTMS under acidic condition. These gels were heterogeneous, porous and exhibited fast deswelling kinetics when the temperature was elevated to above lower critical solution temperature (LCST). The swelling ratios of the gels containing beta-CD at room temperature were higher than that of the normal PNIPAM hydrogel, which was caused by the lower crosslinking density in beta-CD contained gels. In comparison to that of the normal PNIPAM gel, the amount of loaded-drug in the hydrogel containing beta-CD was higher, and the release time of 5-fluorouracil (5-Fu) was prolonged, which was attributed to the formation of inclusion compounds between 5-Fu and beta-CD in gel network.
A series of novel p(N-isopropylacrylamide) (PNIPAM) hydrogels were synthesized by radical copolymerization of N-isopropylacrylamide (NIPAM) and 3-methacryloxypropyltrimethoxysilane (MPTMS). The copolymers were then crosslinked through hydrolysis of the siloxane in acetic acid/water mixed solvent. Beta-cyclodextrin (Beta-CD) was introduced into the polymeric networks by condensation of 3-glycidoxypropyltrimethoxysilane derived beta-cyclodextrin (KH560-beta-CD) with MPTMS under acidic condition. These gels were heterogeneous, porous and exhibited fast deswelling kinetics when the temperature was elevated to above lower critical solution temperature (LCST). The swelling ratios of the gels containing beta-CD at room temperature were higher than that of the normal PNIPAM hydrogel, which was caused by the lower crosslinking density in beta-CD contained gels. In comparison to that of the normal PNIPAM gel, the amount of loaded-drug in the hydrogel containing beta-CD was higher, and the release time of 5-fluorouracil (5-Fu) was prolonged, which was attributed to the formation of inclusion compounds between 5-Fu and beta-CD in gel network.
2005, 23(5): 521-529
Abstract:
A new type of aromatic tetraamine containing biphenyl moiety in the side chain was synthesized via a modified Chichibabin’s reaction. 3-Nitro-4-acetamidoacetophenone was reacted with 4-phenyl benzaldehyde in the presence of ammonium acetate to obtain 2,6-bis(3,4-diaminophenyl)-4-biphenyl pyridine (DPPA). A series of polypyrrolones (PPys) were prepared using tetraamine and various aromatic dianhydrides via a two-step cyclization procedure. All the PPys show excellent high temperature stabilities with the initial decomposition temperatures of 530-549℃ and residual weight ratio of 49%-80% at 750℃ in nitrogen. The polymers exhibit no apparent glass transition temperatures (Tgs) except PPy-1 (Tg = 327℃), which is derived from tetraamine DPPA and 2,2-bis[4-(3,4-dicarboxyphenoxy)-phenyl]propane dianhydride (BPADA). In addition, the polymers have acceptable mechanical properties with the tensile strength of 65-94 MPa. The PPy films show excellent hydrolysis-resistance in alkaline aqueous medium and could maintain most of the properties even after boiling in 10% aqueous sodium hydroxide solution for a week.
A new type of aromatic tetraamine containing biphenyl moiety in the side chain was synthesized via a modified Chichibabin’s reaction. 3-Nitro-4-acetamidoacetophenone was reacted with 4-phenyl benzaldehyde in the presence of ammonium acetate to obtain 2,6-bis(3,4-diaminophenyl)-4-biphenyl pyridine (DPPA). A series of polypyrrolones (PPys) were prepared using tetraamine and various aromatic dianhydrides via a two-step cyclization procedure. All the PPys show excellent high temperature stabilities with the initial decomposition temperatures of 530-549℃ and residual weight ratio of 49%-80% at 750℃ in nitrogen. The polymers exhibit no apparent glass transition temperatures (Tgs) except PPy-1 (Tg = 327℃), which is derived from tetraamine DPPA and 2,2-bis[4-(3,4-dicarboxyphenoxy)-phenyl]propane dianhydride (BPADA). In addition, the polymers have acceptable mechanical properties with the tensile strength of 65-94 MPa. The PPy films show excellent hydrolysis-resistance in alkaline aqueous medium and could maintain most of the properties even after boiling in 10% aqueous sodium hydroxide solution for a week.
2005, 23(5): 531-537
Abstract:
Polyoxymethylene (POM)/elastomer/filler ternary composites were prepared, in which thermoplastic polyurethane (TPU) and inorganic filler, namely, CaCO3, were used to achieve balanced mechanical properties of POM. The dispersion and phase morphology of POM/elastomer/filler composites were found to depend largely on processing method, CaCO3 content in masterbatch and the filler size. Two processing methods were employed to prepare POM/elastomer/filler ternary composites. One is called the one-step method, in which elastomer and the filler directly melt blended with POM matrix. The other is called the two-step method, in which the elastomer and the filler were mixed to get masterbatch first, which was then melt blended with pure POM of different content. The effect of phase morphology and processing method on impact strength was investigated. It was found that the two-step method results in an increase in impact strength but not for the one-step method. Additionally, the impact strength of POM ternary composites decreases with the increase in the size of CaCO3 particles.
Polyoxymethylene (POM)/elastomer/filler ternary composites were prepared, in which thermoplastic polyurethane (TPU) and inorganic filler, namely, CaCO3, were used to achieve balanced mechanical properties of POM. The dispersion and phase morphology of POM/elastomer/filler composites were found to depend largely on processing method, CaCO3 content in masterbatch and the filler size. Two processing methods were employed to prepare POM/elastomer/filler ternary composites. One is called the one-step method, in which elastomer and the filler directly melt blended with POM matrix. The other is called the two-step method, in which the elastomer and the filler were mixed to get masterbatch first, which was then melt blended with pure POM of different content. The effect of phase morphology and processing method on impact strength was investigated. It was found that the two-step method results in an increase in impact strength but not for the one-step method. Additionally, the impact strength of POM ternary composites decreases with the increase in the size of CaCO3 particles.
2005, 23(5): 539-548
Abstract:
Polyethersulfone membranes were prepared from quaternary systems containing N,N-dimethylacetamide (DMAc) as solvent, polyvinylpyrrolidone (PVP) as constant additive and acetic acid, acetone and water as variable additives. Phase inversion via immersion precipitation was employed for manufacturing of membranes. The prepared films were immersed in the mixture of pure water and 2-propanol (30/70 vol%) as the non-solvent. Acetic acid caused an increment in the flux at high polymer concentration (16 wt%) and a decline in the flux at low polymer concentrations (10 wt% and 13 wt%). Acetone and water as the solvent in the casting solution declined the flux at any polymer concentration tested. The morphology and performance of the prepared membranes were investigated by scanning electron microscopy and separation experiments using milk as the feed.
Polyethersulfone membranes were prepared from quaternary systems containing N,N-dimethylacetamide (DMAc) as solvent, polyvinylpyrrolidone (PVP) as constant additive and acetic acid, acetone and water as variable additives. Phase inversion via immersion precipitation was employed for manufacturing of membranes. The prepared films were immersed in the mixture of pure water and 2-propanol (30/70 vol%) as the non-solvent. Acetic acid caused an increment in the flux at high polymer concentration (16 wt%) and a decline in the flux at low polymer concentrations (10 wt% and 13 wt%). Acetone and water as the solvent in the casting solution declined the flux at any polymer concentration tested. The morphology and performance of the prepared membranes were investigated by scanning electron microscopy and separation experiments using milk as the feed.
2005, 23(5): 549-556
Abstract:
A novel series of main chain liquid crystalline copolyesters with X-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4-bis(4-hydroxyphenylazo) dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4-(a,w-hexanedioyloxy) dibenzoyl dichloride (M1), 2,5-bis(p-octyloxybenzoyloxy) hydro-quinone (M2) and cis-4,4-bis(4-hydroxyphenylazo) dibenzo-18-crown-6 (M3). Monomer M1 was synthesized by esterification and substitution of adipoyl chloride with p-hydroxybenzoic acid, monomer M2 was synthesized by esterfication and reduction reaction of 2,5-dihydroxybenzoquinone and p-octanoxybenzoyl chloride and monomer M3 was synthesized by diazotization and coupling reaction of cis-diaminodibenzo-18-crown-6 with phenol. The molecular weights of copolyesters are not high, and the intrinsic viscosity [h] of copolyesters ranges from 0.25-0.35. The monomers’ structures were identified by using elemental analysis, IR, UV, 1H-NMR, MS, etc. All the copolyesters are yellowish powders and insoluble in THF and CHCl3 at room temperature except CP9. The properties of copolyesters were investigated by using GPC, [h] , DSC, TG, WAXD and POM. It was found that all the copolyesters entered into liquid crystal phase when they were heated to above their melting temperature (Tm). The typical smectic and nematic phase texture can be observed on POM. Their mesophase transition temperature and thermal stability change regularly with varying the content of cis-4,4-bis(4-hydroxyphenylazo) dibenzo-18-crown-6 unit in the copolyesters.
A novel series of main chain liquid crystalline copolyesters with X-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4-bis(4-hydroxyphenylazo) dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4-(a,w-hexanedioyloxy) dibenzoyl dichloride (M1), 2,5-bis(p-octyloxybenzoyloxy) hydro-quinone (M2) and cis-4,4-bis(4-hydroxyphenylazo) dibenzo-18-crown-6 (M3). Monomer M1 was synthesized by esterification and substitution of adipoyl chloride with p-hydroxybenzoic acid, monomer M2 was synthesized by esterfication and reduction reaction of 2,5-dihydroxybenzoquinone and p-octanoxybenzoyl chloride and monomer M3 was synthesized by diazotization and coupling reaction of cis-diaminodibenzo-18-crown-6 with phenol. The molecular weights of copolyesters are not high, and the intrinsic viscosity [h] of copolyesters ranges from 0.25-0.35. The monomers’ structures were identified by using elemental analysis, IR, UV, 1H-NMR, MS, etc. All the copolyesters are yellowish powders and insoluble in THF and CHCl3 at room temperature except CP9. The properties of copolyesters were investigated by using GPC, [h] , DSC, TG, WAXD and POM. It was found that all the copolyesters entered into liquid crystal phase when they were heated to above their melting temperature (Tm). The typical smectic and nematic phase texture can be observed on POM. Their mesophase transition temperature and thermal stability change regularly with varying the content of cis-4,4-bis(4-hydroxyphenylazo) dibenzo-18-crown-6 unit in the copolyesters.
2005, 23(5): 557-559
Abstract:
The tetrahedral borate ion can crosslink with polymer guar gum in aqueous solutions. If the concentration of guar gum is less than 0.045 g/dL, the intramolecular interaction between guar gum and borate ion increases due to the formation of crosslinks. As a result, the polymer chains of guar gum in solution shrink in size and the reduced viscosity of polymer solution decreases accordingly. On the other hand, if the concentration of guar gum is greater than 0.045 g/dL, the intermolecular interaction becomes apparent due to the same reason. The polymer chains, therefore, associate together and the reduced viscosity of polymer solution increases considerably. According to this technique, the critical concentration c*, presented by de-Gennes[1], is determined successfully.
The tetrahedral borate ion can crosslink with polymer guar gum in aqueous solutions. If the concentration of guar gum is less than 0.045 g/dL, the intramolecular interaction between guar gum and borate ion increases due to the formation of crosslinks. As a result, the polymer chains of guar gum in solution shrink in size and the reduced viscosity of polymer solution decreases accordingly. On the other hand, if the concentration of guar gum is greater than 0.045 g/dL, the intermolecular interaction becomes apparent due to the same reason. The polymer chains, therefore, associate together and the reduced viscosity of polymer solution increases considerably. According to this technique, the critical concentration c*, presented by de-Gennes[1], is determined successfully.
2005, 23(5): 561-566
Abstract:
Sub-micron sized phenolic epoxy resin waterborne particles were prepared by phase inversion emulsification. Micro-phase separation occurred during the curing process at high temperature. The as-prepared samples possessed one glass transition temperature (Tg) and two exothermal processes during DSC heating scannings. After being thermally treated above the exothermal peak temperature, they possessed two glass transition temperatures with the disappearance of exothermal peaks, whilst a core/shell structure was formed. This was likely related with the outward diffusion of reactive oligomers to the outer layer of particles.
Sub-micron sized phenolic epoxy resin waterborne particles were prepared by phase inversion emulsification. Micro-phase separation occurred during the curing process at high temperature. The as-prepared samples possessed one glass transition temperature (Tg) and two exothermal processes during DSC heating scannings. After being thermally treated above the exothermal peak temperature, they possessed two glass transition temperatures with the disappearance of exothermal peaks, whilst a core/shell structure was formed. This was likely related with the outward diffusion of reactive oligomers to the outer layer of particles.
