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2006 Volume 24 Issue 3
2006, 24(3): 221-227
Abstract:
Two novel polyacetylenes bearing nonlinear optical chromophoric group poly(3-(4-[4-(n-butyloxy) phenylazophenyl]carbonyl)oxy-1-propyne) (poly(1a)) and poly(3-(4-[4-(n-heptyloxy)phenylazophenyl]carbonyl)-oxy-1-propyne) (poly(1b)) were synthesized with [Rh(nbd)Cl]2-Et3N as catalysts. These polyacetylenes are soluble by using an alkyl spacer and an alkyloxyl group as a substituent. They were characterized by FTIR, NMR, GPC and UV-Vis and their optical limiting and nonlinear optical properties were investigated using 8 ns pulse at 532 nm wavenumber. The results show that these soluble functional polyacetylenes possess optical limiting properties and large nonlinear optical properties and poly(1b) possesses better optical limiting and nonlinear optical properties than poly(1a).
Two novel polyacetylenes bearing nonlinear optical chromophoric group poly(3-(4-[4-(n-butyloxy) phenylazophenyl]carbonyl)oxy-1-propyne) (poly(1a)) and poly(3-(4-[4-(n-heptyloxy)phenylazophenyl]carbonyl)-oxy-1-propyne) (poly(1b)) were synthesized with [Rh(nbd)Cl]2-Et3N as catalysts. These polyacetylenes are soluble by using an alkyl spacer and an alkyloxyl group as a substituent. They were characterized by FTIR, NMR, GPC and UV-Vis and their optical limiting and nonlinear optical properties were investigated using 8 ns pulse at 532 nm wavenumber. The results show that these soluble functional polyacetylenes possess optical limiting properties and large nonlinear optical properties and poly(1b) possesses better optical limiting and nonlinear optical properties than poly(1a).
2006, 24(3): 229-236
Abstract:
We have theoretically resolved phonon excitations in quasi-two-dimensional organic crystals of polyacenic semiconductor material which may be obtained by the pyrolytic treatment of phenol-formaldehyde resin. A model for studying the dynamical properties using three polyacene chains is proposed with the aim to present the vibrational properties of this structure. It employs the formalism of solid states in two dimensions which admit phonons. A simulation process of the two-dimensional lattice structure shows that elastic waves may explain the existence of vibrational modes in the frequency range 100400 cm1. The presence of acoustic and optical like phonons is discussed in terms of the elastic force constants. A hyperfine resonance structure is obtained. It allows the analysis of the dynamical evolution in thin films of polyacene. It is found that the behavior of the phonon density of states exhibits resonance between modes in the structure.
We have theoretically resolved phonon excitations in quasi-two-dimensional organic crystals of polyacenic semiconductor material which may be obtained by the pyrolytic treatment of phenol-formaldehyde resin. A model for studying the dynamical properties using three polyacene chains is proposed with the aim to present the vibrational properties of this structure. It employs the formalism of solid states in two dimensions which admit phonons. A simulation process of the two-dimensional lattice structure shows that elastic waves may explain the existence of vibrational modes in the frequency range 100400 cm1. The presence of acoustic and optical like phonons is discussed in terms of the elastic force constants. A hyperfine resonance structure is obtained. It allows the analysis of the dynamical evolution in thin films of polyacene. It is found that the behavior of the phonon density of states exhibits resonance between modes in the structure.
2006, 24(3): 237-244
Abstract:
Short two-dimensional compact chains adsorbed on the attractive surface at different temperatures were investigated by using the enumeration calculation method. First we investigate the chain size and shape of adsorbed chains, such as characteristic ratios of mean-square radii of gyration x /N and y /N, shape factor , and the orientation of chain bonds to illuminate how the size and shape of adsorbed compact chains change with increasing temperatures. There are some special behaviors for the chain size and shape at low temperature, especially for strong attraction interaction. In the meantime, adsorbed compact chains have different behaviors from general adsorbed polymer chains. Some thermodynamics properties are also discussed here. Heat capacity changes non-monotonously, first increases and then reduces. The transition temperature Tc is nearly 1.0, 1.4, 2.0 and 4.2 （in the unit of T0）for the case of e = 0, -1, -2 and –4 (in the unit of kT0), respectively. Average energy per bond increases while average Helmholtz free energy per bond decreases with increasing temperatures. From these two thermodynamics parameters we can also get another transition temperature Tc′, and it is close to 0.7, 1.1, 1.5 and 3.4 for e = 0, -1, -2, and -4, respectively. Therefore, Tc is greater than Tc′ under the same condition. These investigations may provide some insights into the thermodynamics behaviors of adsorbed protein-like chains.
Short two-dimensional compact chains adsorbed on the attractive surface at different temperatures were investigated by using the enumeration calculation method. First we investigate the chain size and shape of adsorbed chains, such as characteristic ratios of mean-square radii of gyration x /N and y /N, shape factor , and the orientation of chain bonds to illuminate how the size and shape of adsorbed compact chains change with increasing temperatures. There are some special behaviors for the chain size and shape at low temperature, especially for strong attraction interaction. In the meantime, adsorbed compact chains have different behaviors from general adsorbed polymer chains. Some thermodynamics properties are also discussed here. Heat capacity changes non-monotonously, first increases and then reduces. The transition temperature Tc is nearly 1.0, 1.4, 2.0 and 4.2 （in the unit of T0）for the case of e = 0, -1, -2 and –4 (in the unit of kT0), respectively. Average energy per bond increases while average Helmholtz free energy per bond decreases with increasing temperatures. From these two thermodynamics parameters we can also get another transition temperature Tc′, and it is close to 0.7, 1.1, 1.5 and 3.4 for e = 0, -1, -2, and -4, respectively. Therefore, Tc is greater than Tc′ under the same condition. These investigations may provide some insights into the thermodynamics behaviors of adsorbed protein-like chains.
2006, 24(3): 245-252
Abstract:
Both four-arm star-shaped poly(-caprolactone) (4sPCL) and two-arm linear PCL (2LPCL) were synthesized and their inclusion complexation with a-cyclodextrin (a-CD) were studied. The inclusion complexes (ICs) formed between the PCL polymers and a-CD were characterized by 1H-NMR, DSC, TGA, WAXD, and FT-IR, respectively. Both branch arm number and molecular weight of the PCL polymers have apparent effect on the stoichiometry (CL:CD, mol:mol) of these ICs. All these analytical results indicate that the branch arms of the PCL polymers are incorporated into the hydrophobic a-CD cavities and their original crystalline properties are completely suppressed. Moreover, the inclusion complexation between two-arm linear or four-arm star-shaped PCL polymers and a-CD not only enhances the thermal stability of the guest PCL polymers but also improves that of a-CD.
Both four-arm star-shaped poly(-caprolactone) (4sPCL) and two-arm linear PCL (2LPCL) were synthesized and their inclusion complexation with a-cyclodextrin (a-CD) were studied. The inclusion complexes (ICs) formed between the PCL polymers and a-CD were characterized by 1H-NMR, DSC, TGA, WAXD, and FT-IR, respectively. Both branch arm number and molecular weight of the PCL polymers have apparent effect on the stoichiometry (CL:CD, mol:mol) of these ICs. All these analytical results indicate that the branch arms of the PCL polymers are incorporated into the hydrophobic a-CD cavities and their original crystalline properties are completely suppressed. Moreover, the inclusion complexation between two-arm linear or four-arm star-shaped PCL polymers and a-CD not only enhances the thermal stability of the guest PCL polymers but also improves that of a-CD.
2006, 24(3): 253-263
Abstract:
The copolymer poly(3-(4-fluorophenyl)thiophene-co-3-methylthiophene) was successfully prepared from mixtures of 3-(4-fluorophenyl)thiophene (FPT) and 3-methylthiophene (MeT) via electrochemical oxidation in boron trifluoride diethyl etherate (BFEE) and its mixed electrolytes with acetonitrile (ACN). The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy (SEM), respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT:MeT = 1:2, was about 1.08:1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.
The copolymer poly(3-(4-fluorophenyl)thiophene-co-3-methylthiophene) was successfully prepared from mixtures of 3-(4-fluorophenyl)thiophene (FPT) and 3-methylthiophene (MeT) via electrochemical oxidation in boron trifluoride diethyl etherate (BFEE) and its mixed electrolytes with acetonitrile (ACN). The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy (SEM), respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT:MeT = 1:2, was about 1.08:1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.
2006, 24(3): 265-271
Abstract:
The novel shish-kebab-type liquid crystalline poly(p-phenylene)s were synthesized through Suzuki coupling reaction from 2,5-bis[(4-n-alkoxyl)benzoyloxy]1,4-dibromobenzene (monomer 1) and 1,4-benzenediboronic acid bistrimethylene cyclic ester (monomer 2). Their structure and properties were characterized by GPC, DSC, X-ray diffraction and polarizing optical microscope (POM). It was found that the polymers turned to liquid crystalline phase above their melting point. The melting point (Tm) of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The mesophase was identified by X-ray diffraction method. The polymers could dissolve in common organic solvents and show strong blue fluorescence. The maximum absorption bands of polymers prepared from annealed films have large red-shift due to the spontaneous orientation of the liquid crystalline side chains. The same phenomena were also observed in the fluorescence spectra.
The novel shish-kebab-type liquid crystalline poly(p-phenylene)s were synthesized through Suzuki coupling reaction from 2,5-bis[(4-n-alkoxyl)benzoyloxy]1,4-dibromobenzene (monomer 1) and 1,4-benzenediboronic acid bistrimethylene cyclic ester (monomer 2). Their structure and properties were characterized by GPC, DSC, X-ray diffraction and polarizing optical microscope (POM). It was found that the polymers turned to liquid crystalline phase above their melting point. The melting point (Tm) of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The mesophase was identified by X-ray diffraction method. The polymers could dissolve in common organic solvents and show strong blue fluorescence. The maximum absorption bands of polymers prepared from annealed films have large red-shift due to the spontaneous orientation of the liquid crystalline side chains. The same phenomena were also observed in the fluorescence spectra.
2006, 24(3): 273-279
Abstract:
Chiral polymers P-1 and P-2 were synthesized by the polymerization of (R)-3,3-diiodo-2,2-bisbutoxy-1,1-binaphthyl (M-1) with 2,5-di(4-ethynylphenyl)-1,3,4-oxadiazole (M-3) and (R)-3,3-diethylnyl-2,2-bisbutoxy-1,1-binaph- thyl (M-2) with 1,2-di(4-bromophenyl)acetylene (M-4) under Sonogashira reaction, respectively. Both monomers and polymers were analyzed by NMR, MS, FT-IR, UV-Vis spectroscopy, DSC-TGA, fluorescence spectroscopy, GPC and CD spectroscopy. CD spectra of P-1 and P-2 are similar due to the same chiral center units and main chain structure. The long wavelengths CD effect of P-1 and P-2 can be regarded as the more extended conjugated structure and a highly rigid backbone in the polymer chain. Polymers have strong blue fluorescence due to the efficient energy migration from the extended π-electronic structure of the polymers to the chiral binaphthyl core and are expected to provide understanding of the relationship between molecular structure and fluorescent property of the chiral polymers.
Chiral polymers P-1 and P-2 were synthesized by the polymerization of (R)-3,3-diiodo-2,2-bisbutoxy-1,1-binaphthyl (M-1) with 2,5-di(4-ethynylphenyl)-1,3,4-oxadiazole (M-3) and (R)-3,3-diethylnyl-2,2-bisbutoxy-1,1-binaph- thyl (M-2) with 1,2-di(4-bromophenyl)acetylene (M-4) under Sonogashira reaction, respectively. Both monomers and polymers were analyzed by NMR, MS, FT-IR, UV-Vis spectroscopy, DSC-TGA, fluorescence spectroscopy, GPC and CD spectroscopy. CD spectra of P-1 and P-2 are similar due to the same chiral center units and main chain structure. The long wavelengths CD effect of P-1 and P-2 can be regarded as the more extended conjugated structure and a highly rigid backbone in the polymer chain. Polymers have strong blue fluorescence due to the efficient energy migration from the extended π-electronic structure of the polymers to the chiral binaphthyl core and are expected to provide understanding of the relationship between molecular structure and fluorescent property of the chiral polymers.
2006, 24(3): 281-289
Abstract:
Through the preparation of PVDF membranes using various nonsolvent coagulation baths following the phase inversion process, the influence of alcohol-based nonsolvents on the formation and structure of PVDF membranes were investigated. The light scattering and light transmission measurements were used to characterize the equilibrium phase diagram and the gelation speed, respectively. The locations of the crystallization-induced gelation boundaries for various systems and precipitation processes were explained from the corresponding thermodynamic and kinetic parameters. It was found that the better affinity between alcohol-based nonsolvents and DMAc solvent caused the gelation boundaries further away from the PVDF-DMAc axis with the coagulation bath varying from water, methanol, ethanol to iso-propanol. Due to the lower exchange rate of DMAc and alcohols, the delayed demixing took place for the membrane-forming using alcohols as baths, and the delayed time became longer when the coagulation bath was changed from methanol, ethanol to iso-propanol. The characterization results of membranes indicate that the influence of nonsolvents on the phase diagram and the precipitation process are in agreement with those on the membrane morphology. The better thermodynamic stability and a low exchange diffusion rate of PVDF/DMAc/alcohols favor the liquid-solid phase separation in gelation process, and therefore yield the membranes with a porous upper surface, a particular bottom surface and symmetrical structure.
Through the preparation of PVDF membranes using various nonsolvent coagulation baths following the phase inversion process, the influence of alcohol-based nonsolvents on the formation and structure of PVDF membranes were investigated. The light scattering and light transmission measurements were used to characterize the equilibrium phase diagram and the gelation speed, respectively. The locations of the crystallization-induced gelation boundaries for various systems and precipitation processes were explained from the corresponding thermodynamic and kinetic parameters. It was found that the better affinity between alcohol-based nonsolvents and DMAc solvent caused the gelation boundaries further away from the PVDF-DMAc axis with the coagulation bath varying from water, methanol, ethanol to iso-propanol. Due to the lower exchange rate of DMAc and alcohols, the delayed demixing took place for the membrane-forming using alcohols as baths, and the delayed time became longer when the coagulation bath was changed from methanol, ethanol to iso-propanol. The characterization results of membranes indicate that the influence of nonsolvents on the phase diagram and the precipitation process are in agreement with those on the membrane morphology. The better thermodynamic stability and a low exchange diffusion rate of PVDF/DMAc/alcohols favor the liquid-solid phase separation in gelation process, and therefore yield the membranes with a porous upper surface, a particular bottom surface and symmetrical structure.
2006, 24(3): 291-297
Abstract:
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.
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.
2006, 24(3): 299-306
Abstract:
Melt extrusion was used to prepare binary nanocomposites of ethylene copolymers and organoclay and trinary nanocomposites of low-density polyethylene (LDPE), ethylene copolymer and organoclay. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to analyze the structure of the clay phase and the morphology of the nanocomposites. Influences of the comonomer in the copolymer and the content of the copolymer on the morphology of the resulting nanocomposites were discussed. The binary and the trinary composites may form intercalated or exfoliated structures depending on the interaction between the copolymer and the clay layers and the content of the copolymer.
Melt extrusion was used to prepare binary nanocomposites of ethylene copolymers and organoclay and trinary nanocomposites of low-density polyethylene (LDPE), ethylene copolymer and organoclay. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to analyze the structure of the clay phase and the morphology of the nanocomposites. Influences of the comonomer in the copolymer and the content of the copolymer on the morphology of the resulting nanocomposites were discussed. The binary and the trinary composites may form intercalated or exfoliated structures depending on the interaction between the copolymer and the clay layers and the content of the copolymer.
2006, 24(3): 307-313
Abstract:
PVC disulfide (2SPVC) was synthesized by solution crosslink and its molecular structure was confirmed by infrared spectrum. 2SPVC’s specific area is 36.1 m2•g-1 tested by stand BET method, and granularity experiment gives out the particle size of d0.5 = 11.3 m. With SEM (Scanning Electron Microscope) experiment the surface morphology and particle shape of 2SPVC were observed. Cyclic voltammetry (scan rate: 0.5 mV•s-1) shows that 2SPVC experience an obvious S―S redox reaction in charge-discharge process. When 2SPVC was used as cathode material for secondary lithium battery in a 1 mol•L-1 solution of lithium bis(trifluoromethylsulfonyl) imide (Li(CF3SO2)2N) in a 5:45:50 volume ratio mixture of o-xylene (oxy), diglyme (DG) and dimethoxymethane (DME) at 30℃, the first discharge capacity of 2SPVC is about 400.3 mAh•g-1 which is very close to its theoretical value (410.5 mAh•g-1) at a constant discharge current of 15 mA•g-1. It can retain at about 346.1 mAh•g-1 of discharge capacity after 30 charge-discharge cycles. So 2SPVC is a very promising cathode candidate for rechargeable lithium batteries.
PVC disulfide (2SPVC) was synthesized by solution crosslink and its molecular structure was confirmed by infrared spectrum. 2SPVC’s specific area is 36.1 m2•g-1 tested by stand BET method, and granularity experiment gives out the particle size of d0.5 = 11.3 m. With SEM (Scanning Electron Microscope) experiment the surface morphology and particle shape of 2SPVC were observed. Cyclic voltammetry (scan rate: 0.5 mV•s-1) shows that 2SPVC experience an obvious S―S redox reaction in charge-discharge process. When 2SPVC was used as cathode material for secondary lithium battery in a 1 mol•L-1 solution of lithium bis(trifluoromethylsulfonyl) imide (Li(CF3SO2)2N) in a 5:45:50 volume ratio mixture of o-xylene (oxy), diglyme (DG) and dimethoxymethane (DME) at 30℃, the first discharge capacity of 2SPVC is about 400.3 mAh•g-1 which is very close to its theoretical value (410.5 mAh•g-1) at a constant discharge current of 15 mA•g-1. It can retain at about 346.1 mAh•g-1 of discharge capacity after 30 charge-discharge cycles. So 2SPVC is a very promising cathode candidate for rechargeable lithium batteries.
2006, 24(3): 315-321
Abstract:
Novel amphiphilic fluorescent graft copolymer (PVP-PyAHy) was successfully synthesized by the free radical copolymerization of hydrophobic monomer N-(1-pyrenebutyryl)-N-acryloyl hydrazide (PyAHy) with hydrophilic precursor polymers of vinyl-functionalized poly(N-vinylpyrrolidone) (PVP) in DMF. The copolymer is amphiphilic and has intrinsic fluorescence. FT-IR, 1H-NMR, TEM, gel permeation chromatography-multi-angle laser light scattering, UV-Vis spectroscopy and fluorescence spectroscopy were used to characterize this copolymer. The TEM observation shows that the copolymer PVP-PyAHy forms micelles in aqueous solution. Results of fluorometric measurements illustrate that the critical micelle concentration (CMC) value of PVP-PyAHy in aqueous solution is about 0.90 mg/mL. To examine the encapsulation ability of the copolymer in aqueous media, methyl yellow was employed as a model hydrophobic agent. The loading level of the polymer to methyl yellow is 8.8 mg/g. The cytotoxicity assays for Madin Darby Canine Kidney (MDCK) cells shows good biocompatibility of PVP-PyAHy in vitro. These results suggest the potential of this copolymer PVP-PyAHy as drugs delivery carrier and fluorescent tracer.
Novel amphiphilic fluorescent graft copolymer (PVP-PyAHy) was successfully synthesized by the free radical copolymerization of hydrophobic monomer N-(1-pyrenebutyryl)-N-acryloyl hydrazide (PyAHy) with hydrophilic precursor polymers of vinyl-functionalized poly(N-vinylpyrrolidone) (PVP) in DMF. The copolymer is amphiphilic and has intrinsic fluorescence. FT-IR, 1H-NMR, TEM, gel permeation chromatography-multi-angle laser light scattering, UV-Vis spectroscopy and fluorescence spectroscopy were used to characterize this copolymer. The TEM observation shows that the copolymer PVP-PyAHy forms micelles in aqueous solution. Results of fluorometric measurements illustrate that the critical micelle concentration (CMC) value of PVP-PyAHy in aqueous solution is about 0.90 mg/mL. To examine the encapsulation ability of the copolymer in aqueous media, methyl yellow was employed as a model hydrophobic agent. The loading level of the polymer to methyl yellow is 8.8 mg/g. The cytotoxicity assays for Madin Darby Canine Kidney (MDCK) cells shows good biocompatibility of PVP-PyAHy in vitro. These results suggest the potential of this copolymer PVP-PyAHy as drugs delivery carrier and fluorescent tracer.
2006, 24(3): 323-331
Abstract:
Poly(St-co-BuA)/silica nanocomposite latexes were synthesized via conventional emulsion polymerization in the presence of 3-(trimethoxysilyl)propyl methacrylate modified colloidal nano-silica. The effects of surface property, particle size and content of colloidal nano-silica as well as the concentrations of monomer and surfactant on the morphology of nanocomposite latex particles were investigated by transmission electron microscope (TEM) and scanning electron microscope (SEM) in detail. Various interesting morphologies such as grape-like, Chinese gooseberry-like, pomegranate-like and normal core-shell structures were observed. Droplet nucleation mechanism competing with micelle nucleation mechanism was proposed to explain the morphological evolution of the nanocomposite particles.
Poly(St-co-BuA)/silica nanocomposite latexes were synthesized via conventional emulsion polymerization in the presence of 3-(trimethoxysilyl)propyl methacrylate modified colloidal nano-silica. The effects of surface property, particle size and content of colloidal nano-silica as well as the concentrations of monomer and surfactant on the morphology of nanocomposite latex particles were investigated by transmission electron microscope (TEM) and scanning electron microscope (SEM) in detail. Various interesting morphologies such as grape-like, Chinese gooseberry-like, pomegranate-like and normal core-shell structures were observed. Droplet nucleation mechanism competing with micelle nucleation mechanism was proposed to explain the morphological evolution of the nanocomposite particles.
