全文获取类型
收费全文 | 2963篇 |
免费 | 145篇 |
国内免费 | 963篇 |
专业分类
化学 | 3829篇 |
晶体学 | 28篇 |
力学 | 8篇 |
综合类 | 27篇 |
数学 | 9篇 |
物理学 | 170篇 |
出版年
2024年 | 1篇 |
2023年 | 23篇 |
2022年 | 29篇 |
2021年 | 52篇 |
2020年 | 47篇 |
2019年 | 82篇 |
2018年 | 49篇 |
2017年 | 74篇 |
2016年 | 91篇 |
2015年 | 74篇 |
2014年 | 106篇 |
2013年 | 268篇 |
2012年 | 153篇 |
2011年 | 183篇 |
2010年 | 156篇 |
2009年 | 179篇 |
2008年 | 217篇 |
2007年 | 201篇 |
2006年 | 191篇 |
2005年 | 213篇 |
2004年 | 204篇 |
2003年 | 160篇 |
2002年 | 147篇 |
2001年 | 126篇 |
2000年 | 81篇 |
1999年 | 73篇 |
1998年 | 107篇 |
1997年 | 70篇 |
1996年 | 77篇 |
1995年 | 118篇 |
1994年 | 117篇 |
1993年 | 85篇 |
1992年 | 70篇 |
1991年 | 73篇 |
1990年 | 37篇 |
1989年 | 47篇 |
1988年 | 17篇 |
1987年 | 21篇 |
1986年 | 17篇 |
1985年 | 7篇 |
1984年 | 13篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1972年 | 1篇 |
排序方式: 共有4071条查询结果,搜索用时 15 毫秒
31.
Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage 下载免费PDF全文
Ze‐Kun Yang Dong‐Yu Wang Hiroki Minami Hiroyuki Ogawa Takashi Ozaki Dr. Tatsuo Saito Dr. Kazunori Miyamoto Dr. Chao Wang Prof. Dr. Masanobu Uchiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15693-15699
Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod)2] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh3)2Cl2] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot. 相似文献
32.
In this paper,an axial dispersion mathematical model is developed to simulate a three-phase slurry bubble column reactor for direct synthesis of dimethyl ether(DME) from syngas.This large-scale reactor is modeled using mass and energy balances,catalyst sedimentation andsingle-bubble as well as two-bubbles class flow hydrodynamics.A comparison between the two hydrodynamic models through pilot plantexperimental data from the literature shows that heterogeneous two-bubbles flow model is in better agreement with the experimental data thanhomogeneous single-bubble gas flow model.Also,by investigating the heterogeneous gas flow and axial dispersion model for small bubblesas well as the large bubbles and slurry(i.e.including paraffins and the catalyst) phase,the temperature profile along the reactor is obtained.Acomparison between isothermal and non-isothermal reactors reveals no obvious performance difference between them.The optimum values ofreactor diameter and height were obtained at 7 m and 50 m,respectively.The effects of operating variables on the axial catalyst distribution,DME productivity and CO conversion are also investigated in this research. 相似文献
33.
Sarah Crotty Felix H. Schacher Ulrich S. Schubert 《Journal of polymer science. Part A, Polymer chemistry》2012,50(23):4958-4965
We report the synthesis and characterization of well‐defined homo‐ and diblock copolymers containing poly(furfuryl glycidyl ether) (PFGE) via living anionic ring‐opening polymerization using different initiators. The obtained materials were characterized by SEC, MALDI‐TOF MS, and 1H NMR spectroscopy and molar masses of up to 9400 g/mol were obtained for PFGE homopolymers. If the amphiphilic diblock copolymer PEG‐block‐PFGE was dissolved in water, micelles with a PFGE core and a PEG corona were formed. Hereby, the hydrophobic PFGE core domains were used for the incorporation of a suitable bismaleimide and heating to 60 °C induced the crosslinking of the micellar core via Diels‐Alder chemistry. This process was further shown to be reversible. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
34.
Mitsutoshi Jikei Daisuke Uchida Yuuki Haruta Yuuki Takahashi Kazuya Matsumoto 《Journal of polymer science. Part A, Polymer chemistry》2012,50(18):3830-3839
Hyperbranched poly(ether sulfone)s were prepared by the self‐polycondensation of the novel AB2 monomer, 4‐(3,5‐hydroxyphenoxy)‐4′‐fluorodiphenylsulfone. The high‐molecular‐weight polymers were isolated in good yields. The degree of branching (DB) of the resulting polymers was investigated by the preparation of dendritic and linear model compounds. The DB determined by gated decoupling 13C NMR measurements was in the range 0.17–0.41 and was dependent on the base used for the self‐polycondensation. It was found that cesium fluoride was an effective base to form the polymer having the DB of 0.41. The resulting hyperbranched poly(ether sulfone)s showed good solubility in organic solvents. The solubility and the glass transition temperature of the polymers were influenced by the terminal functional groups. The unique thermal crosslinking phenomenon was observed during the DSC measurements of the hydroxyl‐terminated hyperbranched poly(ether sulfone) under air condition. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
35.
Hou Chien Chang Ching Hsuan Lin Hung Tse Lin Shenghong A. Dai 《Journal of polymer science. Part A, Polymer chemistry》2012,50(5):1008-1017
Generally, protection and deprotection procedures of amino groups are required in preparing propargyl ether‐containing benzoxazines. In this study, we report a facile, deprotection‐free preparation of a propargyl ether‐containing phosphinated benzoxazine (2) from the nucleophilic substitution of a phenolic OH‐containing phosphinated benzoxazine (1) and propargyl bromide in the catalysis of potassium carbonate. The structure of (2) was characterized and confirmed by a high‐resolution mass spectrum, 1H, 13C, 1H‐1H, 1H‐13C nuclear magnetic resonance (NMR) spectra, and X‐ray single crystal diffractogram. infrared (IR) and differential scanning calorimetry were used to monitor the ring‐opening of benzoxazine and crosslinking of propargyl ether. The microstructure and the structure–property relationship of the resulting homopolymers and copolymers are discussed. The Tg of homopolymer of (2) is 208 °C by dynamic mechanical analysis, the coefficient of thermal expansion is 43 ppm/°C, and Td 5% (N2) is 393 °C, respectively, which are higher than those of the homopolymer of (1) . Similar trends were observed in the copolymerization system. The results demonstrate the beneficial effect of crosslinking afforded by the propargyl ether group is higher than that by the phenolic OH group. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
36.
A new monomer, (2,5‐dimethoxy)phenylhydroquinone (DMPH), was prepared in a two‐step synthetic procedure. One aromatic poly(ether ether ketone)s with 2,5‐dimethoxy phenyl side group (DMP‐PEEK) was synthesized via an aromatic nucleophilic substitution reaction with 4,4′‐difluorobenzophenone (DFB). Poly(ether ether ketone)s with 2,5‐dihydroxy phenyl side group (DHP‐PEEK) was obtained via hydrolysis of methoxy group on the DMP‐PEEK. Both of the high molecular weight polymers could be obtained despite the steric effect of the bulky pendant groups. The two polymers have good solubility at room temperature. 相似文献
37.
《高分子科学杂志,A辑:纯化学与应用化学》2013,50(11):1199-1211
Abstract A high temperature thermosetting bisphenol‐A dicyanate (BADCy) was blended with a novel thermoplastic poly(ether imide) (PEI) at various composition. The phase separation behavior during isothermal curing was studied by differential scanning calorimeter (DSC), time‐resolved light scattering (TRLS), scanning electron microscopy (SEM), and rheological measurements. The results suggested that the phase structure changed from separated phase, via co‐continuous phase, to phase inversion with the increase of the PEI content. The curing conversion of BADCy was slightly affected by the composition in the blend and the curing rate was decreased with the increase of PEI content. The co‐continuous phase morphology was attributed to a spinodal decomposition. The initial concentration of PEI had an effect on the rheological behavior during phase separation. It was found by tensile test that the blend with 15 wt.% PEI had higher tensile strength and elongation at break than that without PEI. 相似文献
38.
Atomic levels population measurements constitute an essential contribution to various aspects of plasma research: balance and cross-section of inelastic processes, admixtures effects on level excitation mechanism, purposeful optimisation of plasma parameters etc. Atomic level populations in the negative glow of a hollow cathode discharge are of utmost interest in view of the peculiarities of the spectral source: a rich spectrum consisting of gas lines, lines of the cathode material and also lines of the substances introduced in the discharge; intensive atomic and ionic lines of high excitation potentials; small spectral linewidth, convenient for analytical purposes. 相似文献
39.
Rongyi Zhang Qigang Li Dr. Qiqiang Xie Prof. Dr. Chuanfa Ni Prof. Dr. Jinbo Hu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(71):17773-17779
The ring-opening difluoromethylation-halogenation of cyclic (thio)ethers is reported through a simple strategy relying on carbon-chalcogen bond activation with difluorocarbene. The reaction proceeds through in situ protonation of the previously little-known difluoromethylene oxonium or sulfonium ylide intermediate followed by ring-opening with halide ion to afford halogenated acyclic difluoromethyl (thio)ethers that can then be employed for further elaboration. TMSCF2X (X=Br, Cl) are unique reagents to achieve this synthetic purpose, which serve as both the difluorocarbene source and the halide ion source. 相似文献
40.
Uwe Emmerling Jurgen Lindau Siegmar Diele Johannes Werner Horst Kresse 《Liquid crystals》2013,40(8):1069-1073
A tin-containing liquid crystalline side group polymer was synthesized and characterized. Two glass transitions were detected by calorimetric investigations. The X-ray pattern corresponds to a smectic C order of the side groups and a disordered isotropic main chain. Dielectric measurements show two relaxation ranges which are influenced by the glass transitions and a fast local process. The low frequency mechanism can be related to the reorientation of the side groups and the higher glass transition temperature. The second is connected with the α-relaxation of the main chain and freezes in at lower temperatures. 相似文献