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SYNTHESIS AND CHARACTERIZATION OF A NOVEL BLUE LIGHT EMITTING ROD-COIL DIBLOCK OLIGOMER

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Chinese Journal of polymer science 2002年第5期20卷 401-407页

作者： Lifang Yang Haifeng He Hongqing Cao Xinhua Wan qi-feng zhou department of polymer science & engineering college of chemistry & Molecular engineering peking {13. beijing 100871, china peking Univ Coll Chem & Mol Engn Dept Polymer Sci & Engn Beijing 100871 Peoples R China

Four new rod-coil diblock molecules, which had well-defined para-phenylene oligomers (PPP, from biphenyl to quinquephenyl) as rigid segments and poly(ethylene oxide) (PEO, M-w ca. 750) as flexible segments, were synthesized. The chemical structure and the number of repeating unit in PEO coil and PPP rod were characterized by H-1-NMR and MALDI-TOF mass spectrometry. The diblock oligomers showed good solubility in common organic solvents and aggregated in water as characterized by a blue shift in UV-vis absorption spectra, a red shift in emission spectra, quenching of the fluorescence and formation of the microfibrilla and fractal-like structures. The formation of different supramolecular structures meant that this effort might lead to commercial important highly organized functional materials.

关键词： rod-coil diblock oligomer MALDI-TOF mass spectrometry microfibrilla aggregate fractal-like pattern

“LIVING”/CONTROLLED RADICAL polymerIZATION OF ETHYL METHYLACRYLATE WITH 2,2’-AZOBISISOBUTYRONITRILE/FERRIC CHLORIDE/TRIPHENYLPHOSPHINE INITIATION SYSTEM

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Chinese Journal of polymer science 2000年第2期18卷 149-153页

作者： Xiao-ping Chen Kun-yuan qiu department of polymer {3. and engineering, college of chemistry, peking university, beijing 100871, china peking Univ Coll Chem Dept Polymer Sci & Engn Beijing 100871 Peoples R China

'Living'/controlled radical polymerization of ethyl methacrylate (EMA) was carried out with a 2,2'-azobisisobutyronitrile (AIBN)/ferric chloride (FeCl_3./triphenylphosphine (PPh_3. initiation system at 85℃. Thc numberaverage molecular weight (M_n) increases linearly with monomer conversion and the rate of polymerization is first order withrespect to monomer concentration. The M_w of PEMA ranges from 3.00 to 17600 and the polydispersity indices are quitenarrow (1.09～1.22). The conversion can reach up to～100% and M_w of the polymers obtained is close to that designed. Thepolymerization mechanism belongs to the reverse atom transfer radical polymerization (ATRP). The polymer was end-functionalized by chlorine atom, which acts as a macroinitiator to proceed extension polymerization in the presence ofCuBr/bipy catalyst system via an ATRP process. The presence of ω-chlorine in the PEMA obtained was identified by ~1H-NMR spectrum.

关键词： 'Living'/controlled radical polymerization Reverse ATRP Ethyl methacrylate AIBN/FeCl_3.PPh_3 Bulk polymerization

A NOVEL PHOTO-INITIATING SYSTEM FOR ATOM TRANSFER RADICAL polymerIZATION OF STYRENE

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Chinese Journal of polymer science 2001年第5期19卷 441-445页

作者： Shu-hui qin Dong-qi qin Kun-yuan qiu department of polymer science and engineering college of chemistry and Molecular engineering peking university{13., china beijing Univ Dept Polymer Sci & Engn Coll Chem & Mol Engn Beijing 100871 Peoples R China

A novel photo-induced initiating system, 2,2-dimethoxy-2-phenylacetophenone (DMPA)/ferric tri(NN-diethyldithiocarbamate) [Fe(DC)(3.], was developed and used for the atom transfer radical polymerization (ATRP) of styrene in toluene. The polymerization proceeds with DMPA as photo-initiator, Fe(DC)(3. as catalyst and DC as a reversible transfer group, while the halogen and ligands are free. Well-defined PSt was prepared and the polymerization mechanism revealed by end group analysis belongs to a reverse ATRP. Block copolymer was prepared by using thus obtained PSt as macroinitiator and Fe(DC)(2) as catalyst under UV light irradiation via a conventional ATRP process.

关键词： photo atom transfer radical polymerization living radical polymerization well-defined polystyrene block copolymer

SYNTHESIS OF NOVEL LIQUID CRYSTALLINE POLY(METH)ACRYLATES CONTAINING SILOXANE SPACER AND TERPHENYLENE MESOGENIC UNIT

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Chinese Journal of polymer science 2000年第2期18卷 101-107页

作者： Zhi-qian Zang Yu-fei Luo Dong Zhang Xin-hua Wan qi-feng {3. department of polymer science & engineering, college of chemistry, peking university, beijing 100871,{13. peking Univ Coll Chem Dept Polymer Sci & Engn Beijing 100871 Peoples R China

Novel side-chain liquid-crystalline poly(meth)acrylates were synthesized using 1-(3.hydroxyl-propyl)-3.[(4 '-cyano-p-terphenyloxycarbonyl)alkyl]-1,1,3.3.tetramethyldisiloxane as the key intermediate. The polymers used a disiloxane moiety as decoupling spacer with cyano-p-terphenyl as mesogenic unit. The products were characterized by NMR, GPC, DSC and polarizing optical microscopy. All the polymers with cyano-p-terphenyl mesogens formed a stable mesophase. However, if the mesogenic unit is replaced by cyano-p-biphenyl, the liquid crystalline character will be lost. The results also showed that the decoupling is incomplete even if a complex and very flexible decoupling spacer is deliberately incorporated to obtain the highest possible decoupling effect.

关键词： liquid crystalline polymers polyacrylates 4 ''-cyano-p-terphenyl

A DSC STUDY OF PHOTOpolymerIZATION OF POLYESTERS CONTAINING CONJUGATED DIACETYLENES

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Chinese Journal of polymer science 2000年第4期18卷 351-356页

作者： Yao-wen Bai Xiao-fang Chen Dong Zhang Xin-hua Wan qi-feng zhou {3. of polymer science and engineering, college of chemistry, peking university, beijing 100871, china peking Univ Coll Chem Dept Polymer Sci & Engn Beijing 100871 Peoples R China

The photopolymerization of two kinds of prepolyesters containing conjugated diacetylene (PDA-6 and PDA-12) was investigated using DSC. By measuring the endothermic enthalpy of the prepolymers after different UV-irradiation times, the polymerizations were found to follow the first-order rate law which agreed with the results of other investigators using a different method. The endothermic enthalpy measurements of PDA-6 and PDA-12 before UV-irradiation precluded the possibility that the decrease of endothermic enthalpy was caused by thermal polymerization.

关键词： diacetylene-containing polyesters DSC enthalpy

PROPERTIES OF POLYURETHANE ELASTOMERS BASED ON POLY (OXYETHYLENE-co-OXYTETRAMETHYLENE) DIOL

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Chinese Journal of polymer science 2001年第4期19卷 371-376页

作者： Chen-yu Su Guang-li Zhang Hong-zhi Zhang department of polymer science and {3. college of chemistry and Molecular {3. peking university beijing 100871, china peking Univ Dept Polymer Sci & Engn Coll Chem & Mol Engn Beijing 100871 Peoples R China

Polyurethane elastomers derived from 4,4 ' -methylene bis(phenyl isocyanate), butylene glycol and the low oxyethylene moiety content copolyether of tetrahydrofuran and ethylene oxide, obtained by copolymerization using heteropolyacid-ethylene oxide initiator system, were prepared. The polyurethanes exhibited an increased water absorption and much better low temperature resilience, which remained high even at a temperature of -3.degreesC, while that of polyurethane based upon poly(tetramethylene ether) glycol of the 'same molecular weight, i.e. being 2000, and molecular weight distribution, i.e, in the range of 1.4-1.5, starts to decrease dramatically at 5 degreesC.

关键词： polyurethane poly(oxyethylene-co-oxytetramethylene) diol low temperature resilience heteropolyacid-ethylene oxide initiator system

SYNTHESIS AND PROPERTIES OF LIQUID CRYSTAL POLYSILOXANES WITH MESOGENIC STILBENE SIDE GROUPS

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Chinese Journal of polymer science 2000年第2期18卷 95-99页

作者： Dong Zhang Yan-tao Zhu Da-hui Zhao Xin-hua Wan qi-feng zhou {3. of polymer science & engineering, college of chemistry, peking university, beijing 100871, china peking Univ Coll Chem Dept Polymer Sci & Engn Beijing 100871 Peoples R China

A variety of mesomorphic side-chain polysiloxanes were synthesized by using hydrosilylation reaction with dicyclopentadienylplatinum(II) (DPPC) as the catalyst. The mesogenic groups are derivatives of stilbene with cyano or nitro tail groups. The products were characterized by DSC, X-ray diffraction and polarizing optical microscopy (POM). All the polymers were found to have relatively low T-g and can form a smectic liquid crystal phase.

关键词： liquid crystal polymer polysiloxane

SYNTHESIS AND PROPERTIES OF A NEW AZOBENZENE SIDE-CHAIN polymer CONTAINING A TEMPO RADICAL

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Chinese Journal of polymer science 2002年第4期20卷 285-290页

作者： Yong Zhang Ze-da Xu Xing-he Fan Xiao-fang Chen Xin-hua Wan qi-feng zhou {3. of polymer science and engineering college of chemistry and Molecular engineering peking university, beijing 100871,{13. peking Univ Coll Chem & Mol Engn Dept Polymer Sci & Engn Beijing 100871 Peoples R China

To allow anisotropies of optical properties in a magnetic field, nitroxide radical is introduced into the ortho-position of the phenylene ring in the side chain. A new azobenzene side-chain polymer (TEMPO-PAZ) containing TEMPO radical was synthesized. The polymer has a good solubility in organic solvents. The ESR spectrum of the polymer indicated three absorption lines characteristic of TEMPO radical. The optical phase conjugated responses (I-4) of the polymer films were investigated by degenerate four-wave mixing (DFWM). The experimental results showed that optical phase conjugated response of the TEMPO-PAZ could be easily controlled by choosing the appropriate direction of magnetic field presumably due to the nitroxide radical in the TEMPO-PAZ molecular structure. For the polymer investigated here, the nitroxide radical was introduced to increase optical phase conjugated response intensity in a magnetic field, aiming originally at searching for a new photo-active organic magnetic multifunctional materials.

关键词： azobenzene nitroxide radical polymer photo-active organic magnetic materials optical phase conjugated responses

IMPACT PROPERTIES OF METALLOCENE - CATALYZED ETHYLENE-α-OLEFIN COpolymerS

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Chinese Journal of polymer science 2002年第5期20卷 473-480页

作者： Xu-rong Xu Jun-ting Xu Lin-xian feng department of polymer {3. and engineering Zhejiang university Hangzhou 3.0027,china department of polymer {3. and engineering college of {13. & Molecular engineering peking university beijing 100871, china Zhejiang Univ Dept Polymer Sci & Engn Hangzhou 310027 Peoples R China peking Univ Coll Chem & Mol Engn Dept Polymer Sci & Engn Beijing 100871 Peoples R China

The impact properties of two selected metallocene-catalyzed ethylene-butene copolymers and one conventionalcopolymer were evaluated using Izod impact test. It is found that the metallocene-catalyzed copolymer shows superior impactproperties. This result was explained on the basis of the more homogeneous inter-molecular composition distribution andnarrower molecular weight distribution, which leads to more homogeneous morphology with fewer defects. Stepwisecrystallization improves the impact properties, especially in the crack propagation process, to a large extent. This is due to thedecrease of entanglements by stepwise crystallization, which is advantageous for the chain slip and shear. The polymer withheterogeneous intra-molecular composition distribution exhibits a more evident improvement of impact properties understepwise crystallization.

关键词： Metallocene-catalyzed ethylene-butene copolymer Impact properties Molecular heterogeneities Thermal treatment