Two new functional polyacetylenes bearing different azobenzene group, -{ HC=C[azo-N （CH3）CH2CH2OH] } n-, [poly（EHAB）; azo = 4,4＇-azobenzene] and - { HC=C[azo-N（CH3）CH2CH2O COC3H7]},-, [poly（EEAB）]} were prepa...Two new functional polyacetylenes bearing different azobenzene group, -{ HC=C[azo-N （CH3）CH2CH2OH] } n-, [poly（EHAB）; azo = 4,4＇-azobenzene] and - { HC=C[azo-N（CH3）CH2CH2O COC3H7]},-, [poly（EEAB）]} were prepared by [Rh（nbd）Cl]2-Et3N catalysts. Poly（EHAB） has poor solubility while poly（EEAB） can be dissolved in common solvent. The polymers were characterized by FHR, ^1H NMR, UV and GPC. The nonlinear optical property of the soluble poly（EEAB） was investigated with 8 ns width pulse at 532 nm by Z-scan technique. The results show that poly（EEAB） is endowed with the larger third-order nonlinear optical property.展开更多
Novel 9-proparylcarbazole monomers containing amino acid moieties,2-N(tert-butoxycarbonyl)-L-alanine- 9-proparylcarbazole ester(1),2-N-(tert-butoxycarbonyl)-L-O-cyclohexyl-L-glutamic acid-9-proparylcarbazole ester(2) ...Novel 9-proparylcarbazole monomers containing amino acid moieties,2-N(tert-butoxycarbonyl)-L-alanine- 9-proparylcarbazole ester(1),2-N-(tert-butoxycarbonyl)-L-O-cyclohexyl-L-glutamic acid-9-proparylcarbazole ester(2) and 2-N-(tert-butoxycarbonyl)-L-phenylalanine-9-proparylcarbazole ester(3) were synthesized and polymerized with (nbd)Rh^+[η~6-C_6H_5B^-(C_6H_5)_3]to give the corresponding polymers with number-average molecular weights ranging from 7050 to 10500 in 70%-86%yields.The polymers were completely so...展开更多
Two acetylene polymers containing cyanobiphenyl-based mesogens, poly{10-[((4'-cyano-4-biphenylyl)oxy)carbonyl]-1-decyne} (PA8CN), which has a relatively flexible polyalkyne backbone, and poly {[4-(((12-((4'-cy...Two acetylene polymers containing cyanobiphenyl-based mesogens, poly{10-[((4'-cyano-4-biphenylyl)oxy)carbonyl]-1-decyne} (PA8CN), which has a relatively flexible polyalkyne backbone, and poly {[4-(((12-((4'-cyano-4-biphenylyl)oxy)dodecyl)oxy) carbonyl) phenyl]-acetylene} (PB12CN), which has a fairly rigid poly(phenylacetylene) backbone, were synthesized using respectively WCl6 and [Rh(nbd)Cl](2) as the catalysts. PA8CN exhibits enantiotropic interdigitated smectic A phase (S-Ad) over a temperature range as wide as ca. 100 degrees C, whereas PB12CN is non-mesomorphic, demonstrating that the backbone rigidity plays an important role in determining the liquid crystallinity of the polyacetylenes.展开更多
A substituted polyacetylene bearing a furan ring, poly(2-propynyl 2-furoate) (PPF), was synthesized for the first time with palladium acetylide complex catalysts in CHCl3 at 60°C to give a soluble and stable poly...A substituted polyacetylene bearing a furan ring, poly(2-propynyl 2-furoate) (PPF), was synthesized for the first time with palladium acetylide complex catalysts in CHCl3 at 60°C to give a soluble and stable polymer with a yield of ca. 75%. Some features for polymerization of 2-propynyl 2-furoate are described and discussed. The resulting polymer was characterized by IR, GPC and 1H-NMR analysis.展开更多
While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410× 10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are ca...While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410× 10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are carried out in the presence of C_(60) using the W catalyst under the same conditions.The polymers are soluble in common organic solvents such as THF, chloroform, and toluene. Molecularstructures of the polymers are characterized by FT-IR, UV, NMR, GPC and XRD, and it is found that C_(60) iscopolymerized with PP. Thus C_(60) plays the dual roles of comonomer and cocatalyst in the polymerizationreaction. C_(60) contents of the copolymers can be easily changed by varying the C_(60) amounts in the feedmixtures. The copolymers effectively limit strong 532 nm laser pulses, whose limiting performance issuperior to that of parent C_(60).展开更多
A novel functional polyacetylene containing fluorene group as a pendant,poly（2-（p-methylstyrene）-7-acetylene-9,9-dioctyl-fluorene）, was synthesized in moderate yield by[Rh（nbd）Cl]_2-Et_3N catalyst.The structures...A novel functional polyacetylene containing fluorene group as a pendant,poly（2-（p-methylstyrene）-7-acetylene-9,9-dioctyl-fluorene）, was synthesized in moderate yield by[Rh（nbd）Cl]_2-Et_3N catalyst.The structures and properties of monomer and polymer were characterized and evaluated with FTIR,NMR,UV-vis,GPC and Z-scan,respectively.The results show that the incorporation of fluorene into polyacetylene has endowed the resultant polymer with well optical limiting properties for laser at wavelength 780 nm based on two-photon absorption mechanism.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.50073001 and 90206014)Program for New Century Excellent Talents in University(NCET-04-0588)+1 种基金the Outstanding Youth Fund of Anhui Province(Grant No.04044060)the Award for High Level Intellectuals(Grant No.2004Z027)from Anhui Province.
文摘Two new functional polyacetylenes bearing different azobenzene group, -{ HC=C[azo-N （CH3）CH2CH2OH] } n-, [poly（EHAB）; azo = 4,4＇-azobenzene] and - { HC=C[azo-N（CH3）CH2CH2O COC3H7]},-, [poly（EEAB）]} were prepared by [Rh（nbd）Cl]2-Et3N catalysts. Poly（EHAB） has poor solubility while poly（EEAB） can be dissolved in common solvent. The polymers were characterized by FHR, ^1H NMR, UV and GPC. The nonlinear optical property of the soluble poly（EEAB） was investigated with 8 ns width pulse at 532 nm by Z-scan technique. The results show that poly（EEAB） is endowed with the larger third-order nonlinear optical property.
基金supported by the"Program for New Century Excellent Talents in University"(NCET-08-0204)"The Project Sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry(China)"
文摘Novel 9-proparylcarbazole monomers containing amino acid moieties,2-N(tert-butoxycarbonyl)-L-alanine- 9-proparylcarbazole ester(1),2-N-(tert-butoxycarbonyl)-L-O-cyclohexyl-L-glutamic acid-9-proparylcarbazole ester(2) and 2-N-(tert-butoxycarbonyl)-L-phenylalanine-9-proparylcarbazole ester(3) were synthesized and polymerized with (nbd)Rh^+[η~6-C_6H_5B^-(C_6H_5)_3]to give the corresponding polymers with number-average molecular weights ranging from 7050 to 10500 in 70%-86%yields.The polymers were completely so...
基金This work was in part supported by the Hong Kong RGC grants HKUST597/95P and HKUST6149/97P.
文摘Two acetylene polymers containing cyanobiphenyl-based mesogens, poly{10-[((4'-cyano-4-biphenylyl)oxy)carbonyl]-1-decyne} (PA8CN), which has a relatively flexible polyalkyne backbone, and poly {[4-(((12-((4'-cyano-4-biphenylyl)oxy)dodecyl)oxy) carbonyl) phenyl]-acetylene} (PB12CN), which has a fairly rigid poly(phenylacetylene) backbone, were synthesized using respectively WCl6 and [Rh(nbd)Cl](2) as the catalysts. PA8CN exhibits enantiotropic interdigitated smectic A phase (S-Ad) over a temperature range as wide as ca. 100 degrees C, whereas PB12CN is non-mesomorphic, demonstrating that the backbone rigidity plays an important role in determining the liquid crystallinity of the polyacetylenes.
基金This work was supported by the Scientific and Technological Agreement, China-France.
文摘A substituted polyacetylene bearing a furan ring, poly(2-propynyl 2-furoate) (PPF), was synthesized for the first time with palladium acetylide complex catalysts in CHCl3 at 60°C to give a soluble and stable polymer with a yield of ca. 75%. Some features for polymerization of 2-propynyl 2-furoate are described and discussed. The resulting polymer was characterized by IR, GPC and 1H-NMR analysis.
基金This work was in part supported by the Hong Kong Research Grants Council(HKUST6062/98P and DAG96/97 SC11).
文摘While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410× 10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are carried out in the presence of C_(60) using the W catalyst under the same conditions.The polymers are soluble in common organic solvents such as THF, chloroform, and toluene. Molecularstructures of the polymers are characterized by FT-IR, UV, NMR, GPC and XRD, and it is found that C_(60) iscopolymerized with PP. Thus C_(60) plays the dual roles of comonomer and cocatalyst in the polymerizationreaction. C_(60) contents of the copolymers can be easily changed by varying the C_(60) amounts in the feedmixtures. The copolymers effectively limit strong 532 nm laser pulses, whose limiting performance issuperior to that of parent C_(60).
基金financially supported by the National Natural Science Fund of China(Nos.20971021,51073031 and 20974018)the National Oversea Scholar Cooperation Research Found of China(No.50928301)
文摘A novel functional polyacetylene containing fluorene group as a pendant,poly（2-（p-methylstyrene）-7-acetylene-9,9-dioctyl-fluorene）, was synthesized in moderate yield by[Rh（nbd）Cl]_2-Et_3N catalyst.The structures and properties of monomer and polymer were characterized and evaluated with FTIR,NMR,UV-vis,GPC and Z-scan,respectively.The results show that the incorporation of fluorene into polyacetylene has endowed the resultant polymer with well optical limiting properties for laser at wavelength 780 nm based on two-photon absorption mechanism.
