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Itaru Natori Kimio Imaizumi Hideyuki Yamagishi Miyuki Kazunori 《Journal of Polymer Science.Polymer Physics》1998,36(10):1657-1668
The relationship between the microstructure and the properties of poly(1,3-cyclohexadiene)s, obtained by living anionic polymerization with an alkyllithium/amine system, and their hydrogenated derivatives are reported. The 1,2-bond/1,4-bond molar ratio of poly(1,3-cyclohexadiene) was determined by measuring 2D-NMR with the H H COSY method. The glass transition temperature of poly(1,3-cyclohexadiene) was found to rise with an increase in the ratio of 1,2-bonds to 1,4-bonds or with an increase of the number average molecular weight. The 1,2-bond of the polymer chain gives a high flexural strength and heat distortion temperature. Hydrogenated poly(1,3-cyclohexadiene) has the highest Tg (231°C) among all hydrocarbon polymers ever reported. 1,3-Cyclohexadiene–butadiene–1,3-cyclohexadiene triblock copolymer and 1,3-cyclohexadiene–styrene–1,3-cyclohexadiene triblock copolymer have high heat resistance and high mechanical strength. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1657–1668, 1998 相似文献
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Jian Ming Yu Philippe Dubois Robert Jerome 《Journal of polymer science. Part A, Polymer chemistry》1997,35(16):3507-3515
New block copolymers of the ABA type, where B stands for polybutadiene (PBD) and A for polyglycidylmethacrylate(PGMA), poly(methylmethacrylate(MMA)-co-GMA) and PMMA-b-PGMA, respectively, have been successfully synthesized by using the diadduct of tert-butyllithium (tert-BuLi) to meta-diisopropenylbenzene (m-DIB) as a difunctional initiator. The PBD midblock has been synthesized in a cyclohexane/diethylether (100/6, v/v) mixture at room temperature, whereas the methacrylate outer blocks have been synthesized in a cyclohexane/diethylether/THF (100/6/150, v/v/v) mixture at −78°C. Block copolymers of a very narrow molecular weight distribution (1.10) have been analyzed by differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and tensile testing. These materials are phase separated and can exhibit tensile strength up to 22 MPa together with very high elongation at break (1500%). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3507–3515, 1997 相似文献
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V. Panchalingam John R. Reynolds 《Journal of polymer science. Part A, Polymer chemistry》1992,30(6):967-976
Poly(1,3-cyclohexadiene-alt-α-fluoroacrylonitrile) [poly(1,3-CHD/α-FAN)], an alternating copolymer of α-fluoroacrylonitrile and 1,3-cyclohexadiene has been prepared in bulk using varied monomer feed ratios and AIBN as initiator at 65°C. Elemental and 1H-NMR analyses indicate that the copolymer contains an equimolar composition of α-FAN and 1,3-CHD as observed for alternating copolymers with donor-acceptor polymerizations. A 2-D 1H-COSY NMR experiment indicates that the copolymer contains 1,4-linkages across the cyclohexene unit while more reliable 13C-NMR spectra suggests the copolymer to contain both 1,2- and 1,4-linkages. Poly(1,3-CHD/α-FAN) exhibits improved thermal stability relative to the alternating copolymer of 1,3-CHD and α-chloroacrylonitrile due to a higher resistance to HF elimination relative to HCl elimination. 相似文献
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采用温控原子力显微镜方法,在线跟踪了远离临界组成聚甲基丙烯酸甲酯/苯乙烯-丙烯腈无规共聚物(PMMA/SAN)共混薄膜的表面相分离行为,并研究了其动力学规律。 结果表明,在SAN含量为70%的样品中观察到了表面相分离行为,其过程可分为早期、中期和晚期3个阶段,分别对应特征化的标度指数:早期结果验证了Cahn线性理论,即标度指数为零;中期相行为主要受“碰撞-扩散”机理控制,因此表现出1/3的标度指数;在相分离后期,流体动力学主导了相区的生长和归并行为,此时标度指数变为2/3。 我们的研究结果对于深刻理解高分子相行为具有积极作用,并将对高分子薄膜加工提供必要的指导。 相似文献
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Itaru Natori Shizue Natori 《Journal of polymer science. Part A, Polymer chemistry》2008,46(10):3282-3293
The grafting reaction of poly(1,3‐cyclohexadienyl)lithium onto fullerene‐C60 (C60) was strongly affected by the nucleophilicity of poly(1,3‐cyclohexadiene) (PCHD) carbanions and the polymer chain microstructure, and progressed via step‐by‐step reactions. A star‐shaped PCHD, having a maximum of four arms, was obtained from poly(1,3‐cyclohexadienyl)lithium composed of all 1,4‐cyclohexadiene (1,4‐CHD) units. The rate of the grafting reaction was accelerated by the addition of amine. The grafting density of PCHD arms onto C60 decreased with an increase in the molar ratio of 1,2‐cyclohexadiene (1,2‐CHD) units. The electron‐transfer reaction from PCHD carbanions to C60 did not occur in either a nonpolar solvent or a polar solvent. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3282–3293, 2008. 相似文献
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Tsuguto Imaeda Tamotsu Hashimoto Satoshi Irie Michio Urushisaki Toshikazu Sakaguchi 《Journal of polymer science. Part A, Polymer chemistry》2013,51(8):1796-1807
ABA‐type triblock copolymers and AB‐type star diblock copolymers with poly(2‐adamantyl vinyl ether) [poly(2‐AdVE)] hard outer segments and poly(n‐butyl vinyl ether) [poly(NBVE)] soft inner segments were synthesized by sequential living cationic copolymerization. Although both the two polymer segments were composed solely of poly(vinyl ether) backbones and hydrocarbon side chains, they were segregated into microphase‐separated structure, so that the block copolymers formed thermoplastic elastomers. Both the ABA‐type triblock copolymers and the AB‐type star diblock copolymers exhibited rubber elasticity over wide temperature range. For example, the ABA‐type triblock copolymers showed rubber elasticity from about ?53 °C to about 165 °C and the AB‐type star diblock copolymer did from about ?47 °C to 183 °C with a similar composition of poly(2‐AdVE) and poly(NBVE) segments in the dynamic mechanical analysis. The AB‐type star diblock copolymers exhibited higher tensile strength and elongation at break than the ABA‐type triblock copolymers. The thermal decomposition temperatures of both the block copolymers were as high as 321–331 °C, indicating their high thermal stability. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
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Y. S. Yu Ph. Dubois R. Jrme Ph. Teyssi 《Journal of polymer science. Part A, Polymer chemistry》1996,34(11):2221-2228
MSBSM five-block copolymers where B stands for butadiene, S for styrene, and M for either methyl methacrylate (MMA) or tert-butyl methacrylate (tBMA) have been synthesized by sequential anionic polymerization in an apolar solvent by using a difunctional anionic initiator derived from 1,3-diisopropenylbenzene. These block copolymers show improved mechanical properties and an extended service temperature compared to traditional SBS thermoplastic elastomers. Upon hydrolysis and further neutralization of the PolytBMA end-blocks, the upper glass transition temperature (Tg) of the five-block copolymers has been raised up to about 150°C. A further increase in this service temperature (up to ca. 160°C) has resulted from the blending of sPMMA-SBS-sPMMA five-block copolymers with isotactic poly(methacrylate) (iPMMA), due to the formation of a stereocomplex. The tensile properties of these modified five-block copolymers have remained essentially unchanged. © 1996 John Wiley & Sons, Inc. 相似文献
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Lei Ren Feng Xu Wei Jian Xu 《Journal of polymer science. Part A, Polymer chemistry》2016,54(15):2291-2301
The anionic polymerization of (E)‐1,3‐pentadiene (EP) and (Z)‐1,3‐pentadiene (ZP) together with mixture of the E/Z isomers are investigated, respectively. The kinetic analysis shows that the activation energy for EP (86.17 kJ/mol) is much higher than that for ZP (59.03 kJ/mol). GPC shows that it is the EP rather than the ZP isomer that undergoes anionic living polymerization affording quantitative products of the polymers with well‐controlled molecular weights and narrow molecular weight distributions (1.05 ≤? ≤ 1.09). In addition, THF as polar additive has proved its validity to reduce the molecular weight distribution of poly(ZP) from 1.38 to as low as 1.19. The microstructure and sequence distributions of polypentadiene are characterized by 1H NMR and quantitative 13C NMR. Finally, the distinctive reaction activity of two isomers can be elucidated by two different mechanisms which involve the presence of four forms of zwitterions for EP and the typical [1,5]‐sigmatropic hydrogen‐shift phenomenon for ZP. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2291–2301 相似文献
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用化学聚合方法合成了聚丁基噻吩导电材料,并研究了不同的聚合条件对聚合物性能的影响。聚丁基噻吩导电材料具有较好的稳定性和加工性,其掺杂态的导电率可达到10s/cm。 相似文献
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以聚碳酸1,6-已二醇酯(PC)、聚己二酸-1,4-丁二醇酯(PBAG)、4,4-二苯基甲烷二异氰酸酯(MDI)和1,4-丁二醇(BDO)为原料,合成线型聚碳酸酯改性聚酯型热塑性聚氨酯弹性体(TPCZE).对其玻璃化转变温度Tg、力学性能、耐水解性能和流变特性进行了研究。实验结果表明:随PC二醇含量的增加,弹性体的贮能模量下降,Tg则向高温方向(从-7.8℃到+2.6℃)移动。水解后的强度保持率从85.4%提高到99,7%和117%,熔体的表现粘度降低,加工性能得到改善。 相似文献
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Itaru Natori Shizue Natori 《Journal of polymer science. Part A, Polymer chemistry》2012,50(17):3682-3689
The first‐ever grafting of poly(1,3‐cyclohexadiene) (PCHD) onto single‐walled carbon nanotubes (SWNTs) was accomplished by reaction with poly(1,3‐cyclohexadienyl)lithium. The rate of this reaction was especially slow due to the heterogeneous nature of the reaction system. The concentration of active carbons available for reaction with PCHDLi on the solid surface of the SWNTs was found to be approximately 2.0 mol %. The mass of PCHD attached to the SWNTs was effectively controlled by varying the molecular weight of the PCHD. The resulting PCHD‐grafted SWNTs exhibited excellent solubility in organic solvent, maintaining a highly stable homogeneous dispersion even after 3 months. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
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The crystal structure of the title complex, [K2(5-nbdc)2Cd(Ⅱ)·imH·H2O]∞ (5-nbdc=5-nitro-1,3-benzenedicarbonate, imH=imidazole) has been determined by X-ray diffraction analysis. The crystal data are: tetragonal, space group P41, Mr=694.93 for CdC19H12N4O13K2, a=1.018 6(10) nm, b=1.018 6(10) nm, c=2.436 7(5) nm; Z=4, V=2.528 2(6) nm3, F(000)=1 376, Dc=1.826 Mg·m-3, μ=1.267 mm-1. The title polymeric complex exhibits a two-dimensional framework, in which adjacent Cd(Ⅱ) ions are bridged by μ-O4-5-nitro-1,3-benzenedicarbonate groups forming one-dimensional chains that are further linked by μ-O3-5-nitro-1,3-benzenedicarbonate groups into two-dimensional anion rectangle sheets with large 32-membered rings. The strong π-π stacks of the benzene rings link these adjacent sheets into a three-dimensional van der Waals network. CCDC: 245527. 相似文献
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Christoph H. Braun Benjamin Schpf Chheng Ngov Cyril Brochon Georges Hadziioannou Edward J. W. Crossland Sabine Ludwigs 《Macromolecular rapid communications》2011,32(11):813-819
We report the synthesis of a series of block copolymers consisting of a rod‐like semiconducting poly(2,5‐di(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene) (DEH‐PPV) block and a flexible poly(lactic acid) (PLA) block that can be selectively degraded under mild conditions. Such selectively degradable block copolymers are designed as self‐assembling templates for bulk heterojunction donor–acceptor layers in organic solar cells. A lamellar microphase‐separated domain structure was identified for block copolymers with PLA volume fractions between 29 and 79% in bulk and thin films using SAXS, TEM, and AFM. Depending on the ratio of the two blocks we find either lamellae oriented parallel or perpendicular to the substrate in thin films.
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Molecular mechanics and MNDO calculations showed that the six-membered ring in the molecule of 5-oxo-1,3-cyclohexadiene possesses high conformational mobility. The transition from a planar equilibrium conformation to a distorted sofa conformation in which the C(sp2)-C(=O)-C(sp3)-C(sp2) torsion angle is equal to ±30° increases the energy of the molecule by less than 1 kcal mol–1. The influence of steric (R = Me, Et, Pri, But) and electronic (R = NH2, NO2) effects of substituents R on the equilibrium conformation and mobility of the carbocycle has been analyzed. Both types of substituents at unsaturated C atoms do not change the equlibrium conformation or flexibility of the six-membered ring. Substituents at saturated C atoms cause the transition of the carbocycle to the distorted sofa conformation and significantly restrict its mobility. The electronic structures of 5-oxo-1,3-cyclohexadiene and its amino and nitro derivatives have been analyzed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 849–854, May, 1995. 相似文献
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Adem Zengin Ertan Yildirim Tuncer Caykara 《Journal of polymer science. Part A, Polymer chemistry》2013,51(4):954-962
Well‐defined, high‐density poly(2‐(2‐methoxyethoxy)ethyl methacrylate) [poly(MEO2MA)] brushes were fabricated through a reliable strategy by the combination of self‐assembly of a monolayer of 3‐aminopropyltrimethoxy silane on silicon surface to immobilize 4‐cyano‐4‐(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid chain transfer agent and reversible addition‐fragmentation chain transfer‐mediated polymerization of MEO2MA. The whole fabrication process of the poly(MEO2MA) brushes was followed by water contact angle, grazing angle‐Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and atomic force microscopy. Characterization of the poly(MEO2MA) brushes, such as molecular weight and thickness determination, were measured by gel permeation chromatography and ellipsometry, and the grafting density was estimated. The temperature‐responsive property of the poly(MEO2MA) brushes was further investigated and the result verified the brush‐to‐mushroom phase transition of the poly(MEO2MA) chains from low to high temperature. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
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An atomic force microscope in the compression mode was used to probe the nanomechanical response of single dendrimeric molecules, as well as dendrimer aggregates adsorbed on silicon surface. The force‐compression behaviour of individual, generation 5 poly(amido amine) (PAMAM) dendrimers was described by a Hertzian model for the deformation of elastic bodies. The modulus values obtained ranged between 700 MPa (single dendrimers) and 150 MPa (dendrimer aggregates).