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1996 Volume 14 Issue 4
1996, 14(4): 289-294
Abstract:
A new type of selenious polymer, silica-bound polybispropoxyethyl-selenidesilsesquioxane,and its platinum complex were synthesized from bis-allyloxyethyl selenide via hydrosily-lation with triethoxysilane, followed by immobilized on fumed silica, and then reactingwith potassium chloroplatinite under nitrogen atmosphere in acetone. It was found thatthe platinum complex can catalyze the hydrosilylation of olefins with triethoxysilane effec-tively The effects of the nature of the substrate, the amount of complex used,and the reaction temperature on the catalytic activity were investigated.
A new type of selenious polymer, silica-bound polybispropoxyethyl-selenidesilsesquioxane,and its platinum complex were synthesized from bis-allyloxyethyl selenide via hydrosily-lation with triethoxysilane, followed by immobilized on fumed silica, and then reactingwith potassium chloroplatinite under nitrogen atmosphere in acetone. It was found thatthe platinum complex can catalyze the hydrosilylation of olefins with triethoxysilane effec-tively The effects of the nature of the substrate, the amount of complex used,and the reaction temperature on the catalytic activity were investigated.
1996, 14(4): 295-303
Abstract:
A series of novel polysiloxane polyurea-urethane blockcopolymers based on methy-lene bis (p-phenylisocyanate (MDI), sodium-s-1, 2-dihydroxy propyl sulphonate (SDPS) andaminopropyl-terminated polydimethylsiloxane (ATPS) was synthesized with varying lengthof soft segments and neutralizing cation. The effect of the chemical composition and thecation on the morphology and mechanical properties of the samples were studied.It was found that the SDPS chain extender based samples have definite chemical struc-ture (-MDI-SDPS-MDI-ATPS-).As the length of the soft segment increases,an improvement of phase separation was observed.In addition,when SO3Na was translated into SO3H or the sulphonic acid groups were neutralized with different charge cations(Na+,Zn2+and Al3+),the morphology and mechanical properties changed greatly.
A series of novel polysiloxane polyurea-urethane blockcopolymers based on methy-lene bis (p-phenylisocyanate (MDI), sodium-s-1, 2-dihydroxy propyl sulphonate (SDPS) andaminopropyl-terminated polydimethylsiloxane (ATPS) was synthesized with varying lengthof soft segments and neutralizing cation. The effect of the chemical composition and thecation on the morphology and mechanical properties of the samples were studied.It was found that the SDPS chain extender based samples have definite chemical struc-ture (-MDI-SDPS-MDI-ATPS-).As the length of the soft segment increases,an improvement of phase separation was observed.In addition,when SO3Na was translated into SO3H or the sulphonic acid groups were neutralized with different charge cations(Na+,Zn2+and Al3+),the morphology and mechanical properties changed greatly.
1996, 14(4): 304-310
Abstract:
The selective water plugging agent was prepared by heating the blends of the polyacry-lamide inverse latex, modified urea formaldehyde resin, crosslinking agent and catalysts.The results show that using different types of polymers and additives or changing in theirproportion of the blends, the gelling viscosity, starting point of gelling and other propertiesof the IPN can be controlled.
The selective water plugging agent was prepared by heating the blends of the polyacry-lamide inverse latex, modified urea formaldehyde resin, crosslinking agent and catalysts.The results show that using different types of polymers and additives or changing in theirproportion of the blends, the gelling viscosity, starting point of gelling and other propertiesof the IPN can be controlled.
1996, 14(4): 311-317
Abstract:
In this paper, the effects of shear rate on the intrinsic viscosity measurement of partiallyHydrolysed Polyacrylamide (HPAM) in salt solution were studied with homemade multi-bulb viscometer and low shear rate rheometer. The critical shear rate of HPAM in saltsolution for high molecular weight HPAM was determined. A low shear rate capillaryviscometer was designed in which the [η] approached to value at zero shear rate can beobtained for HPAM-salt system. The effect of molecular weight on shear rate dependence of viscosity was also studied.
In this paper, the effects of shear rate on the intrinsic viscosity measurement of partiallyHydrolysed Polyacrylamide (HPAM) in salt solution were studied with homemade multi-bulb viscometer and low shear rate rheometer. The critical shear rate of HPAM in saltsolution for high molecular weight HPAM was determined. A low shear rate capillaryviscometer was designed in which the [η] approached to value at zero shear rate can beobtained for HPAM-salt system. The effect of molecular weight on shear rate dependence of viscosity was also studied.
1996, 14(4): 318-323
Abstract:
The structural parameters of the aggregated state of polyamide (PA)-1010 annealedat various temperatures were computed by means of the desmearing intensity from SmallAngle X-ray Scattering (SAXS) measurements and by using the concept of the distance dis-tribution function. The results indicated that the structural parameters of the aggregatedstate were strongly dependent upon heat treatment conditions and the maximum valuesof the structural parameters were obtained for the samples annealed at T = 175℃. The particle size Z annealed at different temperature was ranged between 8.1-12.8nm,and the values of the distance distribution function Pmax(Z)were obtained when Z=4.0-6.8nm.Using one dimension electron density correlation function (ID EDCF) method long period (L) and thickness of the lamellar(do)were estimated and were found to increase with the increase of the degree of crystallinity.
The structural parameters of the aggregated state of polyamide (PA)-1010 annealedat various temperatures were computed by means of the desmearing intensity from SmallAngle X-ray Scattering (SAXS) measurements and by using the concept of the distance dis-tribution function. The results indicated that the structural parameters of the aggregatedstate were strongly dependent upon heat treatment conditions and the maximum valuesof the structural parameters were obtained for the samples annealed at T = 175℃. The particle size Z annealed at different temperature was ranged between 8.1-12.8nm,and the values of the distance distribution function Pmax(Z)were obtained when Z=4.0-6.8nm.Using one dimension electron density correlation function (ID EDCF) method long period (L) and thickness of the lamellar(do)were estimated and were found to increase with the increase of the degree of crystallinity.
1996, 14(4): 324-329
Abstract:
D, L)-Lactide (LA) was first polymerized with one component of rare earth cata-lysts [Nd(naph)3, Nd(oct)3, Nd(O-iPr)3, Nd(AcAc)3, Y(AcAc)3, Sm(AcAc)3, Er(AcAc)3)]respectively in solution and in melt state. The effects of [Cat]/[LA] molar ratio, solvents,polymerization time, temperature, various rare earth elements and ligands were investi-gated in detail. The results showed that both the conversion of polymerization and themolecular weight (MW) of poly (D, L-Lactide) (PLA) in melt polymerization are higher than that in solution polymerization,but the polymerization rate in melt was lower than in solution.The molecular weight distribution (MWD)of PLA is broader with increasing temperature.X-ray study indicated that PLA obtained by Nd(AcAc)3 in melt polymerization is an amorphous polymer.
D, L)-Lactide (LA) was first polymerized with one component of rare earth cata-lysts [Nd(naph)3, Nd(oct)3, Nd(O-iPr)3, Nd(AcAc)3, Y(AcAc)3, Sm(AcAc)3, Er(AcAc)3)]respectively in solution and in melt state. The effects of [Cat]/[LA] molar ratio, solvents,polymerization time, temperature, various rare earth elements and ligands were investi-gated in detail. The results showed that both the conversion of polymerization and themolecular weight (MW) of poly (D, L-Lactide) (PLA) in melt polymerization are higher than that in solution polymerization,but the polymerization rate in melt was lower than in solution.The molecular weight distribution (MWD)of PLA is broader with increasing temperature.X-ray study indicated that PLA obtained by Nd(AcAc)3 in melt polymerization is an amorphous polymer.
STRUCTURAL ANALYSIS AND ENVIRONMENTAL STABILITY OF POLYFLUORINATED GROUP SUBSTITUTED POLYTHIOPHENES*
1996, 14(4): 330-337
Abstract:
Electrochemical polymerization of 3-fluoroalkoxy and 3-fluoroether thiophenes givespolymers with relatively high molecular weights and good processibility. Investigationof these polymers by means of GPC indicates that an increase in the number of fluorineatoms in the fluorinated group results in a decrease in degree of polymerization of thepolymers in the same polythiophene series. As shown by NMR and FTIR, the polyfluo-rinated group substituted polythiophenes have regular 2, 5-coupling in their main chains.The SEM micrographs of the polymer films exhibit that polymer (1)-poly [3-2,2,3,3-tetrafluoro-propoxy) thiophene] possesses more regular structure than the other polymers do.Substitution of polythiophenes by fluorinated groups leads to the polymers with high electric,electrochemical and thermal stability.
Electrochemical polymerization of 3-fluoroalkoxy and 3-fluoroether thiophenes givespolymers with relatively high molecular weights and good processibility. Investigationof these polymers by means of GPC indicates that an increase in the number of fluorineatoms in the fluorinated group results in a decrease in degree of polymerization of thepolymers in the same polythiophene series. As shown by NMR and FTIR, the polyfluo-rinated group substituted polythiophenes have regular 2, 5-coupling in their main chains.The SEM micrographs of the polymer films exhibit that polymer (1)-poly [3-2,2,3,3-tetrafluoro-propoxy) thiophene] possesses more regular structure than the other polymers do.Substitution of polythiophenes by fluorinated groups leads to the polymers with high electric,electrochemical and thermal stability.
1996, 14(4): 338-345
Abstract:
The biodegradability of Aspergillus niger (A. niger), Mucor (M-305) and Trichoderma(T-311) strains on regenerated cellulose films in media was investigated. The results showedthat T-311 strain isolated from soil adhered on the cellulose film fragments has strongerdegradation effect on the cellulose film than A. niger strain. The weights, molecular weightsand tensile strengths of the cellulose films in both shake culture and solid media decreasedwith incubation time, accompanied by producing CO2 and saccharides.HPLC,IR and released CO2 analysis indicated that the biodegradation products of the regenerated cellulose films mainly contain oligosacharides,cellobiose,glucose,arabinose,erythrose,glycerose,glycerol,ethanal,formaldehyde and organic acid,the end products were CO2 and water.After a month,the films were completely decomposed by fungi in the media at 30℃.
The biodegradability of Aspergillus niger (A. niger), Mucor (M-305) and Trichoderma(T-311) strains on regenerated cellulose films in media was investigated. The results showedthat T-311 strain isolated from soil adhered on the cellulose film fragments has strongerdegradation effect on the cellulose film than A. niger strain. The weights, molecular weightsand tensile strengths of the cellulose films in both shake culture and solid media decreasedwith incubation time, accompanied by producing CO2 and saccharides.HPLC,IR and released CO2 analysis indicated that the biodegradation products of the regenerated cellulose films mainly contain oligosacharides,cellobiose,glucose,arabinose,erythrose,glycerose,glycerol,ethanal,formaldehyde and organic acid,the end products were CO2 and water.After a month,the films were completely decomposed by fungi in the media at 30℃.
1996, 14(4): 346-354
Abstract:
Films were prepared from mixtures of copolymers of 4-nitro-4'- [N- methylacryloyloxyethyl,N'-ethyl] amino azobenzene with glycidyl methacrylate (chromophore content: 6 mol%) andcopolymers containing anhydride units, which was obtained by the reaction of 4-nitro-4'-[N-hydroxyethyl, N'-ethyl] amino azobenzene with polymethacryloyl chloride (chromophorecontent: 25 mol %). During thermal poling process the anhydride reacts with the epoxygroup and the resulting crosslinked network structure will stabilize the second harmonic generation in the poled film.The second harmonic generation of the poled film shows a maximum with the variation of composition,this is presumed to be due to the effects of the increasing of concentration,orientation order as well as orientation stability of chromophore groups during crosslinking.
Films were prepared from mixtures of copolymers of 4-nitro-4'- [N- methylacryloyloxyethyl,N'-ethyl] amino azobenzene with glycidyl methacrylate (chromophore content: 6 mol%) andcopolymers containing anhydride units, which was obtained by the reaction of 4-nitro-4'-[N-hydroxyethyl, N'-ethyl] amino azobenzene with polymethacryloyl chloride (chromophorecontent: 25 mol %). During thermal poling process the anhydride reacts with the epoxygroup and the resulting crosslinked network structure will stabilize the second harmonic generation in the poled film.The second harmonic generation of the poled film shows a maximum with the variation of composition,this is presumed to be due to the effects of the increasing of concentration,orientation order as well as orientation stability of chromophore groups during crosslinking.
1996, 14(4): 355-361
Abstract:
A silica-supported cross-linked poly(maleic acid -co- styrene)-platinum complex (PMS-Pt) has been prepared and found to be active in the hydrogenation of p-cresol undermild conditions (303-323K, 1.01×10~5Pa). In this hydrogenation system water servesas a solvent and p-cresol can be converted to 4-methylcyclohexanol quantitatively via4-methylcyclohexanone as intermediate.
A silica-supported cross-linked poly(maleic acid -co- styrene)-platinum complex (PMS-Pt) has been prepared and found to be active in the hydrogenation of p-cresol undermild conditions (303-323K, 1.01×10~5Pa). In this hydrogenation system water servesas a solvent and p-cresol can be converted to 4-methylcyclohexanol quantitatively via4-methylcyclohexanone as intermediate.
1996, 14(4): 362-367
Abstract:
Three A-shaped nitropyrimidine derivatives with benzyl or furfuryl as bridge havebeen synthesized. They possess shorter absorption wavelengths (λcut-off))-46 esu). The second order nonlinear optical coefficient d33 ofpoled BNPMOPMDA/PMMA doped film is 1.2-2.0×10-9 esu obtained by in-situ SHGmeasurements. It can be expected that the chromophore-functionalized polymer containinghigher number density of synthesized chromophore as side chain will be the potential blue-light transparent frequency doubling materials.
Three A-shaped nitropyrimidine derivatives with benzyl or furfuryl as bridge havebeen synthesized. They possess shorter absorption wavelengths (λcut-off))-46 esu). The second order nonlinear optical coefficient d33 ofpoled BNPMOPMDA/PMMA doped film is 1.2-2.0×10-9 esu obtained by in-situ SHGmeasurements. It can be expected that the chromophore-functionalized polymer containinghigher number density of synthesized chromophore as side chain will be the potential blue-light transparent frequency doubling materials.
1996, 14(4): 368-375
Abstract:
The polysiloxane containing propylene carbonate side group and several lithium poly-meric salts were synthesized. The structure were confirmed by IR, NMR and XPS. Theblending systems of polysiloxane containing propylene carbonate group with different lithiumpolymeric salts were studied by ion conductivity XPS and DSC. Different lithium poly-meric salts in the blending system lead to conductivity arranged in the following sequence:poly(lithium ethylenebenzene sulfonate methylsiloxane)>poly(lithium propionate methylsiloxane)>poly(lithium propylsulfonate methylsiloxane)>poly(lithium styrenesulfonate).In the blending system the best single ion conductivity was close to 10-5 Scm -1 at room temperature.XPS showed that at low lithium salt concentration the conductivity increased with the increasing content of lithium salt,in consequence of the increase of free ion and solvent separated ion pair.At high lithium salt concentration the free ion was absent and the solvent-separated ion pair functioned carrier.
The polysiloxane containing propylene carbonate side group and several lithium poly-meric salts were synthesized. The structure were confirmed by IR, NMR and XPS. Theblending systems of polysiloxane containing propylene carbonate group with different lithiumpolymeric salts were studied by ion conductivity XPS and DSC. Different lithium poly-meric salts in the blending system lead to conductivity arranged in the following sequence:poly(lithium ethylenebenzene sulfonate methylsiloxane)>poly(lithium propionate methylsiloxane)>poly(lithium propylsulfonate methylsiloxane)>poly(lithium styrenesulfonate).In the blending system the best single ion conductivity was close to 10-5 Scm -1 at room temperature.XPS showed that at low lithium salt concentration the conductivity increased with the increasing content of lithium salt,in consequence of the increase of free ion and solvent separated ion pair.At high lithium salt concentration the free ion was absent and the solvent-separated ion pair functioned carrier.
1996, 14(4): 376-379
Abstract:
Polypropylene (PP) microporous film prepared by biaxial stretching of isotactic PPis treated with non-solvent liquid at room temperature. The dimension of the film maychange after the treatment. The degree of area contraction of PP film is dependent on thematch between PP and liquid in solubility parameter and polarity. The fact indicates thatsome interactions do exist between liquid and isotactic PP, and a shrinkable porous film isa sensitive probe to detect the weak interactions.
Polypropylene (PP) microporous film prepared by biaxial stretching of isotactic PPis treated with non-solvent liquid at room temperature. The dimension of the film maychange after the treatment. The degree of area contraction of PP film is dependent on thematch between PP and liquid in solubility parameter and polarity. The fact indicates thatsome interactions do exist between liquid and isotactic PP, and a shrinkable porous film isa sensitive probe to detect the weak interactions.
1996, 14(4): 380-384
Abstract:
The organic salts as initiators [A+B-:Ph3C+ClO4-, Ph3C+SbCl6-, (-)Sp+ClO4- and(-)(Sp)2+3(ClO4)3] and catalysts [A+B-:(+)CSA, A+B-:Ph3C+(+)CSA- and(-)Sp+(+)CSA] are prepared and characterized by specific rotation. The asymme-trically stereoselective induction of the initiators and catalysts in the polymerization ofN-vinylcarbazole is in an order of A+B->A+B->A+B-. The specific rotations ofobtained poly (N-vinylcarbazole ) (PVCZ) generally are in accordance with mentioned order.
The organic salts as initiators [A+B-:Ph3C+ClO4-, Ph3C+SbCl6-, (-)Sp+ClO4- and(-)(Sp)2+3(ClO4)3] and catalysts [A+B-:(+)CSA, A+B-:Ph3C+(+)CSA- and(-)Sp+(+)CSA] are prepared and characterized by specific rotation. The asymme-trically stereoselective induction of the initiators and catalysts in the polymerization ofN-vinylcarbazole is in an order of A+B->A+B->A+B-. The specific rotations ofobtained poly (N-vinylcarbazole ) (PVCZ) generally are in accordance with mentioned order.
