Login In
1998 Volume 16 Issue 4
1998, 16(4): 289-291
Abstract:
1998, 16(4): 292-296
Abstract:
Silica-bound mercaptoselenaether-containing silsesquioxane and its plat-inum or rhodium complex were synthesized from γ-(2,3-epithiopropyl) propyltrimethoxysi-lane via ring-opening reaction with bis(2-hydroxyethyl) sclenide, followed by hydrolysisand immobilization on fumed silica, and then reacting with potassium chloroplatinite orrhodium chloride in acetone under nitrogen atmosphere. It was found that two noble metalcomplexes can catalyze the hydrosilylation of olefins with triethoxysilane effectively. The influences of temperature,the amount of complex used,the nature of olefin on catalytic activity were investigated.
Silica-bound mercaptoselenaether-containing silsesquioxane and its plat-inum or rhodium complex were synthesized from γ-(2,3-epithiopropyl) propyltrimethoxysi-lane via ring-opening reaction with bis(2-hydroxyethyl) sclenide, followed by hydrolysisand immobilization on fumed silica, and then reacting with potassium chloroplatinite orrhodium chloride in acetone under nitrogen atmosphere. It was found that two noble metalcomplexes can catalyze the hydrosilylation of olefins with triethoxysilane effectively. The influences of temperature,the amount of complex used,the nature of olefin on catalytic activity were investigated.
1998, 16(4): 297-303
Abstract:
Ring-opening polymerization of ε-caprolactone (CL) catalyzed bylanthanocenes, O(C2H4C5H3CH3)22YCl (Cat-YCl) and Me2Si[(CH3)3SiC5H3]2NdCl(Cat-NdCl) has been carried out for the first time. It has been found that both yttroceneand neodymocene are very efficient to catalyze the polymerization of CL, giving high molec-ular weight poly (ε-caprolactone) (PCL ). The effects of [cat] / [ε- CL] molar ratio, polymeriza-tion temperature and time, as well as solvents were investigated and polymerization temperature is found to be the most important factor affecting the polymerization.The bulk polymerization gives higher molecular weight PCL and higher conversion than that in solution polymerization.NaBPh4 was found to promote the polymerization of ε-caprolactone,and thus yo increase both the polymerization conversion and MW of poly(ε-caprolactone).
Ring-opening polymerization of ε-caprolactone (CL) catalyzed bylanthanocenes, O(C2H4C5H3CH3)22YCl (Cat-YCl) and Me2Si[(CH3)3SiC5H3]2NdCl(Cat-NdCl) has been carried out for the first time. It has been found that both yttroceneand neodymocene are very efficient to catalyze the polymerization of CL, giving high molec-ular weight poly (ε-caprolactone) (PCL ). The effects of [cat] / [ε- CL] molar ratio, polymeriza-tion temperature and time, as well as solvents were investigated and polymerization temperature is found to be the most important factor affecting the polymerization.The bulk polymerization gives higher molecular weight PCL and higher conversion than that in solution polymerization.NaBPh4 was found to promote the polymerization of ε-caprolactone,and thus yo increase both the polymerization conversion and MW of poly(ε-caprolactone).
1998, 16(4): 304-309
Abstract:
The copolymers of chloroethyl methacrylate (CMA), glycidyl methacry-late (GMA), and methyl methacrylate (MMA) were synthesized in benzene solution. Theirbreadths of the molecular weight distributions are 2.1 and 2.3, respectively The ther-mal stability of P(GMA-CMA) is superior to that of P(CMA-MMA). The resolutionsof P(CMA-MMA) and P(GMA-CMA) photoresists were found to be 0.1～0.16μm and0.17 ～0.2μm, respectively.
The copolymers of chloroethyl methacrylate (CMA), glycidyl methacry-late (GMA), and methyl methacrylate (MMA) were synthesized in benzene solution. Theirbreadths of the molecular weight distributions are 2.1 and 2.3, respectively The ther-mal stability of P(GMA-CMA) is superior to that of P(CMA-MMA). The resolutionsof P(CMA-MMA) and P(GMA-CMA) photoresists were found to be 0.1～0.16μm and0.17 ～0.2μm, respectively.
1998, 16(4): 310-315
Abstract:
The photoinitiating system composed of 1-ethyl-3'-methylthiacyanine bro-mide (C-I), 2-chlorohexaarylbiimidazole (o-Cl-HABI) and 3-mercapto-4-methyl-4H-1, 2, 4-triazole (MTA), which act as sensitizer, initiator and hydrogen-donor respectively, can beused to initiate the polymerization of methyl methacrylate (MMA). The kinetic study wascarried out in trichloromathane solution at 30℃ by using dilatometry. The relation be-tween the polymerization rate and the concentrations of C-I, o-Cl-HABI, MTA and MMA was studied.
The photoinitiating system composed of 1-ethyl-3'-methylthiacyanine bro-mide (C-I), 2-chlorohexaarylbiimidazole (o-Cl-HABI) and 3-mercapto-4-methyl-4H-1, 2, 4-triazole (MTA), which act as sensitizer, initiator and hydrogen-donor respectively, can beused to initiate the polymerization of methyl methacrylate (MMA). The kinetic study wascarried out in trichloromathane solution at 30℃ by using dilatometry. The relation be-tween the polymerization rate and the concentrations of C-I, o-Cl-HABI, MTA and MMA was studied.
1998, 16(4): 316-326
Abstract:
Poly(arylene ether diketone)s were prepared by the aromatic nucleophilicdisplacement reaction of 4,4'-difluorobenzil with different bisphenols in the presence of an-hydrous potassium carbonate in diphenylsulfone at elevated temperature. The polymersobtained had inherent viscosity of 0.51 ～ 0.63 dL/g, and exhibited glass transition temper-ature ranging from 136 ～217℃ mainly depending on the bisphenols used in the polymersynthesis. Thermogravimetry of these polymers showed excellent thermal stability, indi-cating that 10% weight losses of the polymers were observed in the range above 428℃ and 438℃ in air and nitrogen,respectively.The mechanical properties of these polymers were also described and the permeability of five polymers for H2,O2and N2 was determined at 30℃.
Poly(arylene ether diketone)s were prepared by the aromatic nucleophilicdisplacement reaction of 4,4'-difluorobenzil with different bisphenols in the presence of an-hydrous potassium carbonate in diphenylsulfone at elevated temperature. The polymersobtained had inherent viscosity of 0.51 ～ 0.63 dL/g, and exhibited glass transition temper-ature ranging from 136 ～217℃ mainly depending on the bisphenols used in the polymersynthesis. Thermogravimetry of these polymers showed excellent thermal stability, indi-cating that 10% weight losses of the polymers were observed in the range above 428℃ and 438℃ in air and nitrogen,respectively.The mechanical properties of these polymers were also described and the permeability of five polymers for H2,O2and N2 was determined at 30℃.
1998, 16(4): 327-331
Abstract:
Association behavior of ethylene vinyl acetate (EVA) copolymer in foursolvents 1, 2-dichloroethane (DCE), cyclohexane (CYH), xylene (XYL) and chloroform(CF) has been investigated by dilute solution viscometry The critical association concen-tration (CA) was determined at which the incipient decrease in slope of the ηsp/C～ Ccurve in solutions at the dilute regime. Our results showed that whether the CA couldexist depends on solvent property. The values of CA in DCE increase with increasing, of temperature and vinyl acetate(VA) content in EVA and decreasing of molecular weight of EVA.
Association behavior of ethylene vinyl acetate (EVA) copolymer in foursolvents 1, 2-dichloroethane (DCE), cyclohexane (CYH), xylene (XYL) and chloroform(CF) has been investigated by dilute solution viscometry The critical association concen-tration (CA) was determined at which the incipient decrease in slope of the ηsp/C～ Ccurve in solutions at the dilute regime. Our results showed that whether the CA couldexist depends on solvent property. The values of CA in DCE increase with increasing, of temperature and vinyl acetate(VA) content in EVA and decreasing of molecular weight of EVA.
1998, 16(4): 332-338
Abstract:
The glassy transition of the polyethylene terephthalate (PET) sampleswhich have been subjected to solvent induced crystallization (SINC) was investigated bymodulated differential scanning calorimetry (MDSC) and density measurement. The dif-ferential of heat capacity signal, d Cp/dT from MDSC, was used to monitor the SINCprocess. It reveals that the Tg temperature shifts to higher value with the advancement ofSINC. When the toluene-immersing time was longer (168h), the detection of T_g becomemore difficult,because some smaller peaks emerged at the lower temperatures and these are explained as the movement of small segments in the amorphous region.These observed results are due to the morphology and structure introduced by the SINC process.
The glassy transition of the polyethylene terephthalate (PET) sampleswhich have been subjected to solvent induced crystallization (SINC) was investigated bymodulated differential scanning calorimetry (MDSC) and density measurement. The dif-ferential of heat capacity signal, d Cp/dT from MDSC, was used to monitor the SINCprocess. It reveals that the Tg temperature shifts to higher value with the advancement ofSINC. When the toluene-immersing time was longer (168h), the detection of T_g becomemore difficult,because some smaller peaks emerged at the lower temperatures and these are explained as the movement of small segments in the amorphous region.These observed results are due to the morphology and structure introduced by the SINC process.
1998, 16(4): 339-344
Abstract:
The effect of γ-ray irradiation on the mechanical properties of high densitypolyethylene(HDPE) filled with sericite-tridymite-cristobalite(STC) was studied. The ex-perimental results show that γ-ray irradiation can improve the affinity between HDPE andSTC, and the dispersion of STC in HDPE matrix. Compared with HDPE/STC (80/20)blend, the yield stress and impact strength of irradiated HDPE (10kGy)/STC (80/20) blendare increased from 22.8 MPa and 70J/m to 28.5 MPa and 144J/m. The yield stress andimpact strength of HDPE/irradiated HDPE/STC (48/32/20) are 27.8MPa and 210J/m,respectively.
The effect of γ-ray irradiation on the mechanical properties of high densitypolyethylene(HDPE) filled with sericite-tridymite-cristobalite(STC) was studied. The ex-perimental results show that γ-ray irradiation can improve the affinity between HDPE andSTC, and the dispersion of STC in HDPE matrix. Compared with HDPE/STC (80/20)blend, the yield stress and impact strength of irradiated HDPE (10kGy)/STC (80/20) blendare increased from 22.8 MPa and 70J/m to 28.5 MPa and 144J/m. The yield stress andimpact strength of HDPE/irradiated HDPE/STC (48/32/20) are 27.8MPa and 210J/m,respectively.
1998, 16(4): 345-350
Abstract:
Water swelling rubber (WSR) was prepared by reaction blending SBR andsodium polyacrylate (PAANa). The existing states of water in the WSR was studied bymeans of DSC and TG. It was found that water exists in three states: nonfreezing water,bound freezable water and free water. The relationships between water states and structureof PAANa were investigated. The results showed that the amount of non-freezing waterwas related to total water content, and the ratio of non-freezing water versus -COONa groups on PAANa(mol/mol) was about 4.However,total water content slightly affected the content of bound freezable water and remarkably affected the amount of free waer.
Water swelling rubber (WSR) was prepared by reaction blending SBR andsodium polyacrylate (PAANa). The existing states of water in the WSR was studied bymeans of DSC and TG. It was found that water exists in three states: nonfreezing water,bound freezable water and free water. The relationships between water states and structureof PAANa were investigated. The results showed that the amount of non-freezing waterwas related to total water content, and the ratio of non-freezing water versus -COONa groups on PAANa(mol/mol) was about 4.However,total water content slightly affected the content of bound freezable water and remarkably affected the amount of free waer.
1998, 16(4): 351-355
Abstract:
Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl chloride as the reaction termi-nating agent. The polymer was characterized by FTIR and SEC. The emulsifier-free emul-sion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containingvarious concentrations of PEO-A was studied. In all cases stable emulsion coplymerizations of MMA and BA were obtained.The stabilizing effect was found to be dependent on the molecular weight and the feed amount of the macromonomer.
Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl chloride as the reaction termi-nating agent. The polymer was characterized by FTIR and SEC. The emulsifier-free emul-sion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containingvarious concentrations of PEO-A was studied. In all cases stable emulsion coplymerizations of MMA and BA were obtained.The stabilizing effect was found to be dependent on the molecular weight and the feed amount of the macromonomer.
1998, 16(4): 356-361
Abstract:
The optical α-amino acids were synthesized under room temperature byalkylation of N-(diphenyl methylene) glycine t-butyl ester under polymer-supported phasetransfer conditions using polymer-supported cinchonine (or quinine) alkaloids as chiralphase transfer catalysts and dichloromethane as solvent, followed by hydrolysis of theabove intermediates introduced to the final products-optical α-amino acids. This is anew method for the asymmetric synthesis of α-amino acids. The influences of catalyst,temperature,substrates,and organic solvents on the chemical yield and optical purities of products were stydied.
The optical α-amino acids were synthesized under room temperature byalkylation of N-(diphenyl methylene) glycine t-butyl ester under polymer-supported phasetransfer conditions using polymer-supported cinchonine (or quinine) alkaloids as chiralphase transfer catalysts and dichloromethane as solvent, followed by hydrolysis of theabove intermediates introduced to the final products-optical α-amino acids. This is anew method for the asymmetric synthesis of α-amino acids. The influences of catalyst,temperature,substrates,and organic solvents on the chemical yield and optical purities of products were stydied.
1998, 16(4): 362-369
Abstract:
In the course of investigating the catalytic behavior of metal complexes forring opening metathesis polymerization of cycloolefins, metathesis, hydroformylation andselective hydrogenation of olefins experimental results time and again indicate the pres-ence of effects of macromolecular supports -the utilization of macromolecular supportsincreases obviously the activity, selectivity, and stability of the catalysts and so as to in-crease the conversion of substrates, yields of reactions, properties of formed polymers and so on.Discussed these effects on the basis of the sythors'experiments.
In the course of investigating the catalytic behavior of metal complexes forring opening metathesis polymerization of cycloolefins, metathesis, hydroformylation andselective hydrogenation of olefins experimental results time and again indicate the pres-ence of effects of macromolecular supports -the utilization of macromolecular supportsincreases obviously the activity, selectivity, and stability of the catalysts and so as to in-crease the conversion of substrates, yields of reactions, properties of formed polymers and so on.Discussed these effects on the basis of the sythors'experiments.
1998, 16(4): 370-376
Abstract:
Seven new binuclear titanocenes with different linking bridges, unsubsti-tuted or substituted on the Cp rings, were synthesized and tested for their effect on ethylenepolymerization in the presence of MAO. The polyethylenes thus obtained had broad MWDor even bimodal GPC curves, as compared with that from two reference mononuclear ti-tanocenes. This is explained by the difference in degree of steric hindrance around the activecenter sites imposed by the bulky substituted ligands assuming different configurations in the rotation of the catalyst molecules.Lower polymerization temperatures alleviate the effect of these configuration differnces,as reflected in change in MW and Mw/Mn.This effect is not caused by decomposition or disproportionation of the binuclear titanocenes as evidenced by the stability of the catalyst.
Seven new binuclear titanocenes with different linking bridges, unsubsti-tuted or substituted on the Cp rings, were synthesized and tested for their effect on ethylenepolymerization in the presence of MAO. The polyethylenes thus obtained had broad MWDor even bimodal GPC curves, as compared with that from two reference mononuclear ti-tanocenes. This is explained by the difference in degree of steric hindrance around the activecenter sites imposed by the bulky substituted ligands assuming different configurations in the rotation of the catalyst molecules.Lower polymerization temperatures alleviate the effect of these configuration differnces,as reflected in change in MW and Mw/Mn.This effect is not caused by decomposition or disproportionation of the binuclear titanocenes as evidenced by the stability of the catalyst.
1998, 16(4): 377-380
Abstract:
The synthesis of rod-coil diblock copolymers was achieved for the firsttime by TEMPO-mediated "living" free radical polymerization of styrene and 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene(MPCS). The block architecture of the two diblockcopolymers thus prepared, MPCS-b-St(5400/2400) and MPCS-b-St(10800/8700), was con-firmed by GPC, DSC studies and the formation of multimolecular micelles.
The synthesis of rod-coil diblock copolymers was achieved for the firsttime by TEMPO-mediated "living" free radical polymerization of styrene and 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene(MPCS). The block architecture of the two diblockcopolymers thus prepared, MPCS-b-St(5400/2400) and MPCS-b-St(10800/8700), was con-firmed by GPC, DSC studies and the formation of multimolecular micelles.
