Login In
1983 Volume 1 Issue 2
1983, 1(2): 101-107
Abstract:
The chain structure of 1,2-polybutadienes prepared with molybdenum catalyst systems has been studied by IR,13C-NMR and Tg method, and the method to regulate the chain structure investigated. It was found that some polar additives, e. g., allyl halides, are able to regulate not only the content of 1,2-units in the polymer, but also its configuration and sequence distribution. Attempt has been made to estimate the sequence length of stereo-isomers of 1,2-units by statistical theory.
The chain structure of 1,2-polybutadienes prepared with molybdenum catalyst systems has been studied by IR,13C-NMR and Tg method, and the method to regulate the chain structure investigated. It was found that some polar additives, e. g., allyl halides, are able to regulate not only the content of 1,2-units in the polymer, but also its configuration and sequence distribution. Attempt has been made to estimate the sequence length of stereo-isomers of 1,2-units by statistical theory.
1983, 1(2): 108-114
Abstract:
The interatomic distance function of rareearth catalyzed cis-1,4-polybutadiene was studied by" radial distribution function (RDF) derived from electron diffraction. Two intramolecular peaks and three interrnolecular peaks have been found on the RDF. The appearance of such a number of intermolecular maxima on the RDF can be explained by the local parallel packing of long molecular chains of the amorphous polymers.
The interatomic distance function of rareearth catalyzed cis-1,4-polybutadiene was studied by" radial distribution function (RDF) derived from electron diffraction. Two intramolecular peaks and three interrnolecular peaks have been found on the RDF. The appearance of such a number of intermolecular maxima on the RDF can be explained by the local parallel packing of long molecular chains of the amorphous polymers.
1983, 1(2): 115-124
Abstract:
This article reports the polymerization kinetics of acrylonitrile initiated by metallic magnesiumnitric acid system. The rate of polymerization is independent of the amount of magnesium used; when the concentration of nitric acid is higher than acrylonitrile, the equation of polymerization kinetics may be expressed asRp =1.91×105e-15000/RT[Mg]0[AN]2.2 [HNO3]0.45 The result of copolymerization of acyrlonitrile and methyl acrylate supports a free-radical mechanism.
This article reports the polymerization kinetics of acrylonitrile initiated by metallic magnesiumnitric acid system. The rate of polymerization is independent of the amount of magnesium used; when the concentration of nitric acid is higher than acrylonitrile, the equation of polymerization kinetics may be expressed asRp =1.91×105e-15000/RT[Mg]0[AN]2.2 [HNO3]0.45 The result of copolymerization of acyrlonitrile and methyl acrylate supports a free-radical mechanism.
1983, 1(2): 125-131
Abstract:
With the aid of the theoretical relationship between the calibration relation of a SEC column for the monodisperse polymer species under ideal working condition and the effective relations between the molecular weight and the elution volume for characterized polymer samples, a computational procedure for simultaneous calibration of molecular weight separation and column dispersion is proposed. From the experimental chromatograms of narrow MWD polystyrene standards and broad MWD 1,2-polybutadiene fractions the spreading factor with the elution volume is independent upon the polymer sample used.
With the aid of the theoretical relationship between the calibration relation of a SEC column for the monodisperse polymer species under ideal working condition and the effective relations between the molecular weight and the elution volume for characterized polymer samples, a computational procedure for simultaneous calibration of molecular weight separation and column dispersion is proposed. From the experimental chromatograms of narrow MWD polystyrene standards and broad MWD 1,2-polybutadiene fractions the spreading factor with the elution volume is independent upon the polymer sample used.
1983, 1(2): 132-137
Abstract:
The nature of the transition in molten FEP copolymer was examined in relation to the enthalpy change, mechanical damping and melt viscosity. For a pre-heat-treated FEP copolymer sample a small endothermic peak appeared at 309—312 ℃ in DSC trace with enthalpy change 0.03—0.05 cal/g. A peak was also detected in damping versus temperature curve at the same temperature range. The theological property of FEP copolymer melt was similar to that of liquid crystal, but no birefrigence was viewed in the melt. Therefore the transition was explained as the melting of small crystallites which persist in typical copolymer beyond its melting temperature.These crystallites can act as nuclei for crystallization upon cooling.
The nature of the transition in molten FEP copolymer was examined in relation to the enthalpy change, mechanical damping and melt viscosity. For a pre-heat-treated FEP copolymer sample a small endothermic peak appeared at 309—312 ℃ in DSC trace with enthalpy change 0.03—0.05 cal/g. A peak was also detected in damping versus temperature curve at the same temperature range. The theological property of FEP copolymer melt was similar to that of liquid crystal, but no birefrigence was viewed in the melt. Therefore the transition was explained as the melting of small crystallites which persist in typical copolymer beyond its melting temperature.These crystallites can act as nuclei for crystallization upon cooling.
1983, 1(2): 138-145
Abstract:
Styrene-co-maleic anhydride, vinyl acetate-co-maleic anhydride, methyl methacrylate-co-maleic anhydride copolymers were deposited on the surface of carbon fibers by an electrodcposition technique. The anion-free radical mechanism of this process and the physical adhesion to the surface were preliminarily confirmed. The adhesion at fiber-resin matrix interface in carbon fiber reinforced plastics was improved by the electrodeposited polymer interlayer and the shear failure occurred mainly in the matrix. Interlaminar shear strength of the unidirectional carbon fiber reinforced epoxy composite is increased Interlaminar shear strength of the unidirectional carbon fiber reinforced epoxy composite is increased from about 600 kg/cm2 by electrodeposition of polymers and the strength loss of the composite which has been immersed in boiling water for 100 hrs is decreased.
Styrene-co-maleic anhydride, vinyl acetate-co-maleic anhydride, methyl methacrylate-co-maleic anhydride copolymers were deposited on the surface of carbon fibers by an electrodcposition technique. The anion-free radical mechanism of this process and the physical adhesion to the surface were preliminarily confirmed. The adhesion at fiber-resin matrix interface in carbon fiber reinforced plastics was improved by the electrodeposited polymer interlayer and the shear failure occurred mainly in the matrix. Interlaminar shear strength of the unidirectional carbon fiber reinforced epoxy composite is increased Interlaminar shear strength of the unidirectional carbon fiber reinforced epoxy composite is increased from about 600 kg/cm2 by electrodeposition of polymers and the strength loss of the composite which has been immersed in boiling water for 100 hrs is decreased.
1983, 1(2): 145-151
Abstract:
Multiple melting behavior of nylon 1010 has been investigated by using DSC instrument. Effects of partial scanning, partial scanning and annealing, heating rate, cooling rate and stepwise annealing on the melting curve were studied. Experimental results indicate that the sample undergoes a process of continuous melting and recrystallization during DSC scanning. Nylon 1010 contains a distribution of crystallites of different degrees of perfection which is strongly dependent on its previous thermal history. From the structural reorganization point of view,the origin of double and multiple peaks of the melting curve is explained.
Multiple melting behavior of nylon 1010 has been investigated by using DSC instrument. Effects of partial scanning, partial scanning and annealing, heating rate, cooling rate and stepwise annealing on the melting curve were studied. Experimental results indicate that the sample undergoes a process of continuous melting and recrystallization during DSC scanning. Nylon 1010 contains a distribution of crystallites of different degrees of perfection which is strongly dependent on its previous thermal history. From the structural reorganization point of view,the origin of double and multiple peaks of the melting curve is explained.
1983, 1(2): 152-160
Abstract:
The title resins (DTC resins) with high adsorption capacity were prepared. The influences of various reaction conditions of amination and dithiocarboxylation were examined. The adsorption capacities of the produced DTC resin for Hg2+, Cu2+, Zn2+ and Cd2+ are 4.40, 2.44, 1.77 and 1.36 mmol/g, respectively. It is highly effective in collecting traces of heavy metal ions in water over a wide pH range. The conversion of the functional groups were confirmed by the IR-spectra and elementary. analysis.
The title resins (DTC resins) with high adsorption capacity were prepared. The influences of various reaction conditions of amination and dithiocarboxylation were examined. The adsorption capacities of the produced DTC resin for Hg2+, Cu2+, Zn2+ and Cd2+ are 4.40, 2.44, 1.77 and 1.36 mmol/g, respectively. It is highly effective in collecting traces of heavy metal ions in water over a wide pH range. The conversion of the functional groups were confirmed by the IR-spectra and elementary. analysis.
1983, 1(2): 161-167
Abstract:
The relations between polymerization conditions of vinylidene fluoride and contents of head-tohead chain in the polymer have been studied. It shows that the contents of head-to-head chain of the polymer are related to its polymerization temperature, but are not related with the kinds of initiators used. Therefore, poly(vinylidene fluoride) with low contents of head-to-head chain (ca. 3%) can be prepared under lower polymerization temperature. Plot of the contents of A chains against melting points of the polymer is linear,which can be expressed by an equation:A=24.8+0.362 Tm(%).
The relations between polymerization conditions of vinylidene fluoride and contents of head-tohead chain in the polymer have been studied. It shows that the contents of head-to-head chain of the polymer are related to its polymerization temperature, but are not related with the kinds of initiators used. Therefore, poly(vinylidene fluoride) with low contents of head-to-head chain (ca. 3%) can be prepared under lower polymerization temperature. Plot of the contents of A chains against melting points of the polymer is linear,which can be expressed by an equation:A=24.8+0.362 Tm(%).
1983, 1(2): 168-175
Abstract:
Acoustic emission has been studied for a wide range of polymers including amorphous glasses, semi-crystalline polymers, copolymers, polymer blends and a crosslinked rubber during the course of uni-axial stretching at room temperature. For non-crystalline polymers acoustic emission occurred in rather small number of events accompanied by crazing and micro-crack formation. Strong acoustic activity appeared during yielding and necking of crystalline polymers. Rather small number or none of acoustic bursts occurred during the initial stage of neck drawing but numerous strong bursts appeared when drawing proceeded approaching specimen break.Specimens of the same polymer but of different fabrication history may be reflected in their acoustic emission behavior.Acoustic emission during stretching crosslinked polybutadiene rubber was very weak but observable when the force-elongation curve started to deviate from the linear region.No Kaiser effect was observed for the rubber.Very strong and numerous acoustic emission was observed during stretching specimens of polymer blends.High impact resistant polymer modifications showed no sharp increase of acoustic activity before specimen break.So long as the polymer and conditions of specimen fabrication are the same quite reproducible acoustic behavior could be observed.
Acoustic emission has been studied for a wide range of polymers including amorphous glasses, semi-crystalline polymers, copolymers, polymer blends and a crosslinked rubber during the course of uni-axial stretching at room temperature. For non-crystalline polymers acoustic emission occurred in rather small number of events accompanied by crazing and micro-crack formation. Strong acoustic activity appeared during yielding and necking of crystalline polymers. Rather small number or none of acoustic bursts occurred during the initial stage of neck drawing but numerous strong bursts appeared when drawing proceeded approaching specimen break.Specimens of the same polymer but of different fabrication history may be reflected in their acoustic emission behavior.Acoustic emission during stretching crosslinked polybutadiene rubber was very weak but observable when the force-elongation curve started to deviate from the linear region.No Kaiser effect was observed for the rubber.Very strong and numerous acoustic emission was observed during stretching specimens of polymer blends.High impact resistant polymer modifications showed no sharp increase of acoustic activity before specimen break.So long as the polymer and conditions of specimen fabrication are the same quite reproducible acoustic behavior could be observed.
1983, 1(2): 176-182
Abstract:
Carboxyl terminated polyethers, the adducts of hydroxyl terminated polytetrahydrofuran and maleic anhydride, were used as toughener for epoxy resins. The morphology of the toughened resins was investigated by means of turbidity measurement, dynamic mechanical testing and scanning electron microscope observation. It turned out that the molecular weight and the carboxyl content of the polyether and the cure conditions are important factors, which affect the particle size of the polyether-rich domains and, in turn,the mechanical properties of the cured resin.Carboxyl terminated polytetrahydrofurans have a low glass transition temperature,and in appropriate amount they do not affect the thermal resistance of the resin.These advantages make them preferable as toughener for epoxy resins.
Carboxyl terminated polyethers, the adducts of hydroxyl terminated polytetrahydrofuran and maleic anhydride, were used as toughener for epoxy resins. The morphology of the toughened resins was investigated by means of turbidity measurement, dynamic mechanical testing and scanning electron microscope observation. It turned out that the molecular weight and the carboxyl content of the polyether and the cure conditions are important factors, which affect the particle size of the polyether-rich domains and, in turn,the mechanical properties of the cured resin.Carboxyl terminated polytetrahydrofurans have a low glass transition temperature,and in appropriate amount they do not affect the thermal resistance of the resin.These advantages make them preferable as toughener for epoxy resins.
1983, 1(2): 182-188
Abstract:
A new method of graft copolymerization of acrylamide (AAM) on poly(ether-urethane) (PEU) which was prepared from poly(tetramethylene ether) glycol (PTMG), 4,4'-diphenylmethane diisocyanate (MDI) and ethylene diamine or butanediol extender was investigated. Hydroperoxide group was first introduced onto the surface of PEU through photo-oxidation in the presence of hydrogen peroxide, then it was reacted with ferrous ion or N,N-dimethyl toluidine (DMT) to initiate AAM graft copolymerization on PEU surface. The graft reaction could be carried out effectively at low temperature.The formation of graft copolymer has been verified by its water absorption % and the scanning electron microscopy photographs.Some model compounds of PEU soft segment and hard segment were synthesized in order to clarify the site of graft reaction. The results of oxidation and graft copolymerization of model compounds showed that this graft copolymerization possesses higher selectivity,and it takes place predominately at the polyether segments,because the ether linkage in soft segment is very sensitive to oxidation and can form hydroperoxide easily.Thus,the grafting site appears to be at α-carbon of the ether linkage.
A new method of graft copolymerization of acrylamide (AAM) on poly(ether-urethane) (PEU) which was prepared from poly(tetramethylene ether) glycol (PTMG), 4,4'-diphenylmethane diisocyanate (MDI) and ethylene diamine or butanediol extender was investigated. Hydroperoxide group was first introduced onto the surface of PEU through photo-oxidation in the presence of hydrogen peroxide, then it was reacted with ferrous ion or N,N-dimethyl toluidine (DMT) to initiate AAM graft copolymerization on PEU surface. The graft reaction could be carried out effectively at low temperature.The formation of graft copolymer has been verified by its water absorption % and the scanning electron microscopy photographs.Some model compounds of PEU soft segment and hard segment were synthesized in order to clarify the site of graft reaction. The results of oxidation and graft copolymerization of model compounds showed that this graft copolymerization possesses higher selectivity,and it takes place predominately at the polyether segments,because the ether linkage in soft segment is very sensitive to oxidation and can form hydroperoxide easily.Thus,the grafting site appears to be at α-carbon of the ether linkage.
1983, 1(2): 189-195
Abstract:
The photopolymerization of acrylonitrile (AN) initiated with phenyl hydrazine (PHZ) and its derivatives has been studied. The initiator exponent and monomer exponent were determined from the kinetic investigation to be 0.66th and 2.1th respectively and the overall activation energy was 33.4KJ/mol for the PHZ-AN system. Spectral analysis and other data indicate that a charge transfer complex between PHZ as a donor and AN as an aceeptor is formed. The initiation mechanism was proposed.
The photopolymerization of acrylonitrile (AN) initiated with phenyl hydrazine (PHZ) and its derivatives has been studied. The initiator exponent and monomer exponent were determined from the kinetic investigation to be 0.66th and 2.1th respectively and the overall activation energy was 33.4KJ/mol for the PHZ-AN system. Spectral analysis and other data indicate that a charge transfer complex between PHZ as a donor and AN as an aceeptor is formed. The initiation mechanism was proposed.
1983, 1(2): 196-199
Abstract:
The condensation oligomers of 5-fluorouracil were prepared by reaction of 2,4-bis-(trimethyl-silyloxy)-5-fluoropyrimidine) with various dicarboxylic chlorides, e.g.The structures of obtained oligomers were characterized by IR and the oligomers were then hydrolyzed in acid, alkaline and neutral media at room temperature respectively. The amount of 5-fluorouracil released was quantitated by measuring its UV absorbance at 265.5nm. However in the case of oligomers containing phenylene moiety, 5-fluorouracil was not detected when the hydrolysis was conducted in acid or neutral medium,while in the case of oligomers containing methylene moiety,hydrolysis proceeded easily in acid,alkaline and neutral media.
The condensation oligomers of 5-fluorouracil were prepared by reaction of 2,4-bis-(trimethyl-silyloxy)-5-fluoropyrimidine) with various dicarboxylic chlorides, e.g.The structures of obtained oligomers were characterized by IR and the oligomers were then hydrolyzed in acid, alkaline and neutral media at room temperature respectively. The amount of 5-fluorouracil released was quantitated by measuring its UV absorbance at 265.5nm. However in the case of oligomers containing phenylene moiety, 5-fluorouracil was not detected when the hydrolysis was conducted in acid or neutral medium,while in the case of oligomers containing methylene moiety,hydrolysis proceeded easily in acid,alkaline and neutral media.
1983, 1(2): 200-204
Abstract:
l-(Acetylsalicylyl)-benzotriazole, a new active amide of acetylsalicylic acid has been synthesized either from acetylsalicylic acid and benzotriazole using DCCI as condensation agent or via acetylsalicylyl chloride and benzotriazole in the presence of triethylamine. The obtained active amide reacted readily with the hydroxyl group of PVA to produce the acetylsalicylyl ester of PVA.
l-(Acetylsalicylyl)-benzotriazole, a new active amide of acetylsalicylic acid has been synthesized either from acetylsalicylic acid and benzotriazole using DCCI as condensation agent or via acetylsalicylyl chloride and benzotriazole in the presence of triethylamine. The obtained active amide reacted readily with the hydroxyl group of PVA to produce the acetylsalicylyl ester of PVA.
