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用基团转移聚合法(GTP)合成嵌段共聚物是近年来国际上高分子研究的热门之一.在室温下制备嵌段共聚物是GTP的一大特点.本文利用三类不同GTP单体的活性差别[1,2],控制适当的加料顺序及聚合条件,首次用GTP法合成含丙烯腈嵌段的A-B型共聚物并进行表征. 相似文献
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在最近召开的美国化学会会议上,以Webster为首的Du Pont公司的研究工作者报道了一种催化合成聚合物的新方法。到目前为止,这种称之为“基团转移聚合”(GTP)的新方法,只应用于丙烯型聚合物,但它具有用于其它类型单体的可能性。Wisconsin州立大学的Trost与Du Pont小组进行了讨论后,认为GTP是“近几十年来有关合成聚合物的第一个新方法”。该法的主要优点是能对聚合过程和所生成的聚合物的大小进行较为准确的控制。在GTP过程中,聚合的引发剂之一是methyltrim(?)thylsilyl dimethylketene acetal(MTDA),也可 相似文献
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合成了一种基团转移聚合(GTP)的新引发剂:3-乙氧基-3-三甲基硅氧基丙烯腈(ETSAN),合成在室温下进行且原料简单.用IR、MS、1HNMR及13CNMR方法对新引发剂进行了测定.ETSAN可引发丙烯腈发生暴聚反应,也能使丙烯酸酯类单体快速聚合.此外,分析了GTP引发剂及活性链遇水易分解的特性,解释了GTP反应速度快与试剂纯度要求高的内在联系,给出了用ETSAN引发丙烯腈和丙烯酸酯的GTP过程反应式。 相似文献
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研究了丙烯酸铈(Ⅲ)配合物的合成及其与明胶的配位反应,以(NH4)2S2O8-NaHSO3作引发剂,用丙烯酸乙酯(EA)对明胶进行聚合鞣制改性。考察了温度、时间、引发主单体浓度及铈离子含量等因素对聚合鞣制过程的影响,并讨论了反应机理。 相似文献
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Cr(Ⅱ)与过氧化莰烷酮酰体系引发的活性自由基聚合反应研究 总被引:1,自引:1,他引:0
合成了过氧化茨烷酮酰 (KPO) ,用它和Cr(Ac) 2 组成的氧化还原体系经陈化后 ,引发甲基丙烯酸甲酯 ,甲基丙烯酸 β 羟乙酯和丙烯酸进行了聚合反应 .其中甲基丙烯酸甲酯具有活性聚合特征 .并有效引发含羟基单体如甲基丙烯酸 β羟乙酯和丙烯酸进行聚合 .实验表明 ,引发剂利用效率随陈化温度的升高而降低 . 相似文献
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Cengiz Soykan Ramazan Coskun Ali Delibas Ertan Sahin 《高分子科学》2007,(5):491-500
2-Acrylamido-2-methy1-1-propanesulfonic acid(AMPS),and maleic acid(MA)copolymerized with different feed ratios using N,N-dimethylformamide as a solvent and benzoyl peroxide(Bz_2O_2)as an initiator at 70℃.Structure and composition of copolymers for a wide range of monomer feed were determined by elemental analysis(content of N for AMPS-units).Monomer reactivity ratios for AMPS(M_1)-MA(M_2)pair were determined by the application of conventional linearization methods such as Fineman-Ross(F-R),Kelen-Tüd(?)s(KT)and Extended Kelen-Tüds(EKT)and a nonlinear error invariable model method using a computer program RREVM.The characterizations were done by Fourier transform infrared spectroscopy(FTIR),differential scanning calorimetry(DSC)thermal gravimetry analysis(TGA),and and X-ray diffraction.The antimicrobial effects of polymers were also tested on various bacteria,and yeast. 相似文献
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Yu J Huang W Wang L Redshaw C Sun WH 《Dalton transactions (Cambridge, England : 2003)》2011,40(39):10209-10214
A series of unsymmetrical 2,6-bis(imino)pyridylcobalt(II) complexes, {2-[2,6-(CH(C(6)H(5))(2))(2)-4-Me-C(6)H(2)N==C(CH(3))]-6-(2,6-R(1)(2)-4-R(2)-C(6)H(2)N==CCH(3))-C(5)H(3)NCoCl(2)} where R(1) = Me, Et or (i)Pr, R(2) = H or Me, together with the new symmetrical complex 2,6-[2,6-(CH(C(6)H(5))(2))(2)-4-Me-C(6)H(2)N==C(CH(3))](2)-C(5)H(3)NCoCl(2), were synthesized. All of the compounds were fully characterized by (1)H NMR and IR spectroscopy, as well as by elemental analysis. The molecular structures of Co1 (R(1) = Me, R(2) = H) and Co5 (R(1) = Et, R(2) = Me) were further confirmed by single crystal X-ray diffraction, which indicated that the cobalt centres were penta-coordinate with a pseudo square-pyramidal geometry. Upon treatment with MAO or MMAO, these cobalt pre-catalysts exhibited higher activities than any previously reported cobalt pre-catalysts, with values as high as 4.64 × 10(6) g PE mol(-1)(Co) h(-1) for ethylene polymerization at atmospheric pressure. The polyethylenes obtained were of high molecular weight and narrow molecular weight distribution. 相似文献
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Two novel heterotetranuclear complexes [V(2)O(2)(μ-MeO)(2)(μ-WO(4))(2)(4,4'-(t)Bubpy)(2)] (1) and [V(2)O(2)(μ-MeO)(2)(μ-MoO(4))(2)(4,4'-(t)Bubpy)(2)] (2) were synthesized, and the solid state structures of these complexes were revealed by single crystal X-ray crystallography. The heterotetranuclear complexes 1 and 2 are centrosymmetric building blocks, considered as consisting of two [VO(4,4'-(t)Bubpy)](3+) units bridged by μ-MO(4)(2-) (M = W or Mo) anions connected with methoxy groups. Furthermore, catalytic activities of 1 and 2 in the alcohol oxidation with hydrogen peroxide as terminal oxidants in water as solvent were investigated. 相似文献
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Cheng X Li S Jia H Zhong A Zhong C Feng J Qin J Li Z 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(6):1691-1699
A new series of intramolecular-charge-transfer (ICT) molecules (compounds 1, 2, and 3) were synthesized by attaching various electron-donating thiophenes groups to a triphenylamine backbone with an aldehyde group as the electron acceptor. Based on the protection reaction between ethanethiol and aldehyde, the corresponding dithioacetals (compounds S1, S2, and S3) were prepared to serve as novel colorimetric and fluorescent chemosensors for Hg(2+) ions. Also, compound S1 was further utilized to construct the chemical-reaction-based conjugated polymer probe (PS1) towards Hg(2+) ions. In the presence of as little as 10 nM Hg(2+), compound PS1 displayed an apparent change in the fluorescent intensity. The sensing processes were revealed to be mediated by ICT, as confirmed by time-dependent DFT calculations. Furthermore, compound S1 was successfully applied to microscopic imaging for the detection of Hg(2+) in HeLa cells with ratiometric fluorescent methods. 相似文献
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Gandelman M Naing KM Rybtchinski B Poverenov E Ben-David Y Ashkenazi N Gauvin RM Milstein D 《Journal of the American Chemical Society》2005,127(43):15265-15272
A new general, synthetically simple, and safe method for the preparation of metal carbene complexes, which is based on diphenyl sulfonium salts as carbenoid precursors, has been developed, and its scope and applications were studied. In general, deprotonation of a sulfonium salt with a base results in a sulfur ylide, which, in turn, reacts with an appropriate metal precursor to give the corresponding metal carbene complex. Thus, starting from benzyldiphenylsulfonium salt, the complexes (PCX)Rh=CHPh (X = P, N) were prepared in quantitative yield. Syntheses of Grubbs' catalyst, (PCy(3))(2)Cl(2)Ru=CHPh, and of Werner's carbene, [Os(=CHPh)HCl(CO)(P(i)Pr(3))(2)], were achieved by this method. Novel trans-bisphosphine Rh and Ir carbenes, ((i)Pr(3)P)(2)(Cl)M=CHPh, which could not be prepared by other known methods, were synthesized by the sulfur ylide approach. The method is not limited to metal benzylidenes, as demonstrated by the preparation of the Ru vinyl-alkylidene, (PCy(3))(2)Cl(2)Ru=CH-CH=CH(2), methoxycarbonyl-alkylidene, (PCy(3))(2)Cl(2)Ru=CH(CO(2)Me), and alkylidene (PCy(3))(2)Cl(2)Ru=CH(CH(3)), (PCy(3))(2)Cl(2)Ru=CH(2) compounds. The problem of recycling of starting materials as well as the issue of facile purification of the product metal carbene complex were addressed by the synthesis of a polymer-supported diarylsulfide, the carrier of the carbenoid unit in the process. Based on the sulfur ylide route, a methodology for the synthesis of metallocarbenes anchored to a polymer via the carbene ligand, using a commercial Merrifield resin, was developed. 相似文献
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Ke J Bartlett PN Cook D Easun TL George MW Levason W Reid G Smith D Su W Zhang W 《Physical chemistry chemical physics : PCCP》2012,14(4):1517-1528
Several Ge(II) and Ge(IV) compounds were investigated as possible reagents for the electrodeposition of Ge from liquid CH(3)CN and CH(2)F(2) and supercritical CO(2) containing as a co-solvent CH(3)CN (scCO(2)) and supercritical CH(2)F(2) (scCH(2)F(2)). For Ge(II) reagents the most promising results were obtained using [NBu(n)(4)][GeCl(3)]. However the reproducibility was poor and the reduction currents were significantly less than the estimated mass transport limited values. Deposition of Ge containing films was possible at high cathodic potential from [NBu(n)(4)][GeCl(3)] in liquid CH(3)CN and supercritical CO(2) containing CH(3)CN but in all cases they were heavily contaminated by C, O, F and Cl. Much more promising results were obtained using GeCl(4) in liquid CH(2)F(2) and supercritical CH(2)F(2). In this case the reduction currents were consistent with mass transport limited reduction and bulk electrodeposition produced amorphous films of Ge. Characterisation by XPS showed the presence of low levels of O, F and C, XPS confirmed the presence of Ge together with germanium oxides, and Raman spectroscopy showed that the as deposited amorphous Ge could be crystallised by the laser used in obtaining the Raman measurements. 相似文献
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Four chelating nitrogen ligands 2-5 derived from N,N-bis(2-picolyl)amine (bpa, 1) were synthesized, namely, (PyCH(2))(2)N-CH(2)-p-C(6)H(4)-CO(2)R (R = Me, 2, and R = H, 3) and (PyCH(2))(2)N-(CH(2))(n)-CO(2)H (n = 2, 4, and n = 5, 5). Amino acid conjugates 6 and 7 were formed by condensation of 3 with H-Phe-OMe and H-betaAla-OMe, respectively. Cu(II) and Zn(II) complexes of 1-7 were prepared and fully characterized. The X-ray structures of 1(Zn), 2(Zn), 4(Cu), and 7(Cu) were determined. The Zn complexes 1(Zn) and 2(Zn) as well as 7(Cu) show a distorted trigonal bipyramidal coordination environment in the solid state. An octahedral complex is observed for 4(Cu) which forms chains along the crystallographic b axis by intermolecular coordination of the carboxylic acid to the metal ion of a neighboring complex. Ligand 3 was used to prepare the peptide bioconjugate 8 (3-Ahx-Pro-Lys-Lys-Lys-Arg-Lys-Phe-NH(2)) with a nuclear localization signal (nls) heptapeptide by solid phase synthesis. Cu(II) and Zn(II) complexes of 8 were synthesized in situ and studied by FAB-MS, ESI-MS, UV/vis, and EPR (for 8(Cu)), and FAB-MS, ESI-MS, and NMR (for 8(Zn)). All spectroscopic results clearly support metal coordination to the bpa ligand in the bioconjugates 8(M), even in the presence of other potential ligands from amino acid side chains of the peptide. We suggest metal-peptide conjugates like 8(M) as artificial metallochaperones because they have the potential to deliver metal ions to specific compartments in the cell as determined by the peptide moieties. 相似文献
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The title compound,2,6-bis(2-pyridinylmethyl)-3,5-bis(2-hydroxyl-5-chlorophe nyl)-pyrazine(C26H12Cl2N4O2C2H8O2,Mr=551.41),has been synthesized and characterized by LC-ESIMS,NMR,UV and IR spectroscopy as well as by X-ray single-crystal diffraction.The compound behaves as a substituted pyrazine.The hydrogen atoms on C(2) and C(3) are substituted by 2-pyridinyl,whereas those on C(1) and C(4) are substituted by 2-hydroxyl-5-chlorophenyl.It crystallizes in the monoclinic system,space group P21/c with a=8.9433(12),b=32.003(4),c=10.5209(18),β=111.199(2)°,V=2807.5(7)3,Z=4,Dc=1.305 mg/m3,F(000)=1144 and μ=0.094 mm-1.A total of 13235 reflections were collected in the range of 2.17~25.01o by using a phi and omega scan mode,of which 4923 were unique(Rint=0.0692) and 2872 observed reflections with Ⅰ > 2σ(Ⅰ) were used in the structure solution and refinement. 相似文献
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