全文获取类型
收费全文 | 5684篇 |
免费 | 211篇 |
国内免费 | 1046篇 |
专业分类
化学 | 6675篇 |
晶体学 | 13篇 |
力学 | 8篇 |
综合类 | 32篇 |
数学 | 1篇 |
物理学 | 212篇 |
出版年
2024年 | 4篇 |
2023年 | 17篇 |
2022年 | 37篇 |
2021年 | 51篇 |
2020年 | 99篇 |
2019年 | 89篇 |
2018年 | 100篇 |
2017年 | 150篇 |
2016年 | 197篇 |
2015年 | 137篇 |
2014年 | 190篇 |
2013年 | 532篇 |
2012年 | 230篇 |
2011年 | 246篇 |
2010年 | 232篇 |
2009年 | 263篇 |
2008年 | 328篇 |
2007年 | 327篇 |
2006年 | 292篇 |
2005年 | 324篇 |
2004年 | 321篇 |
2003年 | 265篇 |
2002年 | 785篇 |
2001年 | 257篇 |
2000年 | 221篇 |
1999年 | 193篇 |
1998年 | 153篇 |
1997年 | 153篇 |
1996年 | 112篇 |
1995年 | 107篇 |
1994年 | 112篇 |
1993年 | 127篇 |
1992年 | 97篇 |
1991年 | 41篇 |
1990年 | 33篇 |
1989年 | 31篇 |
1988年 | 18篇 |
1987年 | 11篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 9篇 |
1983年 | 5篇 |
1982年 | 3篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1971年 | 3篇 |
1967年 | 1篇 |
排序方式: 共有6941条查询结果,搜索用时 10 毫秒
61.
Gregory B. Kharas Matthew J. Lazzarotto Kara A. Ledin Michelle M. Mulvaney Jason R. Nazarof Jean E. Pineda 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(8):1127-1133
Electrophilic trisubstituted ethylene monomers, akyl and alkoxy ring‐trisubstituted methyl 2‐cyano‐3‐phenyl‐2‐propenoates, RC6H2CH[dbnd]C(CN)CO2CH3, (where R is 2,3‐dimethyl‐4‐methoxy, 2,5‐dimethyl‐4‐methoxy‐, 2,3,4‐trimethoxy‐, 2,4,5‐trimethoxy, 2,4,6‐trimethoxy, and 2,4‐dimethoxy‐3‐methyl), were synthesized by the piperidine catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and methyl cyanoacetate, and characterized by CHN elemental analysis, IR, 1H‐ and 13C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (AIBN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, 1H and 13C NMR, GPC, DSC, and TGA. High Tg of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 283–306°C range. 相似文献
62.
In part 1 of this series of two extensive overviews of multi-component polymerization case studies, we present mathematical modelling results with experimental confirmations. The case studies are from free-radical, bulk and/or solution polymerizations, covering the range from homo- to hexa-polymerization at both regular and elevated temperature levels, i.e., without and with possible depropagation steps. The model eventually tackles complex polymerization features, ranging from conversion-time histories to more esoteric multi-component composition and/or sequence length profiles. Part 2 of the series will describe more complicated situations with depropagation and composition control policies, all relying solely on a unique monomer/polymer database of physico-chemical properties and other characteristics, with no further parameter adjustment. These database items will be cited in tables in part 2 of the series. 相似文献
63.
K. Sugiyama 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(1):13-30
The polymerization of acrylonitrile (AN) initiated by tetramethyl-2-tetrazene (TMT) and p-toluenesulfonic acid (TSA) in dimethylformamide (DMF) was studied. The polymerization was confirmed to proceed through a radical mechanism. The initial rate of polymerization R was expressed by the equation: Rp = k[TMT]0.6 [TSA]0.46 [AN]1.35. The overall activation energy for the polymerization was estimated as 20.7 kcal/mole. In the absence of monomer, the reaction of TMT with TSA was also studied kinetically by measuring the evolution of nitrogen. From these results and ESR measurement of the TMT/TSA system, a possible initiation mechanism is proposed. 相似文献
64.
Microwave assisted free radical copolymerization of diisopropyl fumarate (DIPF) and benzyl acrylate (BzA) with different copolymer compositions was performed using benzoyl peroxide as initiator. The effect of the reaction conditions on the macromolecular characteristics, monomer reactivity ratio and copolymer properties were studied. The monomer conversion and average molecular weights increase with the content of BzA units in the copolymer. The copolymers were characterized by IR, 1H and 13C-NMR spectroscopies and the molecular weights were analyzed with size exclusion chromatography (SEC). The reactivity ratios obtained from an extended Kelen-Tüdös method under microwave irradiations are a factor which is double than those obtained by thermal copolymerization. The product r1r2 = 0.152 suggests a preference of both propagating macroradicals toward consecutive homopolymerization. The hydrodynamic and polydispersity size were measured in ethylacetate, tetrahydrofuran and methylethylketone with a quasi-elastic light scattering (QELS) technique showing that the quality of the solvents increases in the order: EA < THF < MEK. 相似文献
65.
Harry Adams Neil A. Bailey David E. Fenton Choki Fukuhara Masatoshi Kanesato 《Supramolecular chemistry》2013,25(4):325-330
Abstract The synthesis and crystal structure of the diprotonated cryptand derived from the reaction of tren and 2,6-diacetyl pyridine is reported. The imino nitrogens of the Schiff base linkages are directed so that the dicarbimine functions are in trans, trans geometry relative to the pyridine C-N bond. This configuration has not previously been reported in related pyridine-derived Schiff base macrocycles. 相似文献
66.
Feng Yu 《International journal of quantum chemistry》2013,113(21):2355-2360
The intermolecular interactions of formic acid (HCOOH) with benzene (C6H6) have been investigated using localized molecular orbital energy decomposition analyses (LMO‐EDA) with ab initio MP2 and several double‐hybrid density functionals. The molecular geometries of five HCOOH…C6H6 complexes and corresponding benchmark total interaction energies at the CCSD(T)/CBS level are taken from literature (Zhao et al., J. Chem. Theory Comput. 2009, 5, 2726). According to the results of LMO‐EDA with the MP2 method, the dispersion energies are found to be as important as the electrostatic energies for the total interaction energies of the five HCOOH…C6H6 complexes. Based on LMO‐EDA with the double‐hybrid density functionals of B2PLYP, B2K‐PLYP, B2T‐PLYP, and B2GP‐PLYP computations, two new parameters for the framework of B2PLYP are extrapolated. These two new parameters are tested with other 10 complexes involving C6H6 (Crittenden, J. Phys. Chem. A 2009, 113, 1663), and they perform well on predicting the corresponding total interaction energies. Interestingly, these two new parameters for the framework of B2PLYP also perform well on the noncovalent complexation energies database (NCCE31/05) developed by Truhlar's group (Zhao and Truhlar, J. Phys. Chem. A 2005, 109, 5656). Therefore, these two new parameters appear to be suitable for investigating the noncovalent interactions, and they are denoted as B2N‐PLYP, where N stands for the noncovalent interaction. This study is expected to provide new insight into the derivation of double‐hybrid density functionals for studying the noncovalent interactions. © 2013 Wiley Periodicals, Inc. 相似文献
67.
Fu-Qiang Jin Jian-Chun Zhang Min Li Xin-Min Hao Hua Zhang 《Journal of Dispersion Science and Technology》2013,34(8):1148-1151
NaOH/poly(sodium acrylate) composites were prepared by in situ polymerization of acrylic acid with an overneutralization level by adding excess NaOH. The composites were studied by XRD, IR and 23Na MAS NMR spectroscopy. The results showed that the high neutralization degree (>100%) may lead to a complete polymerization. Both XRD and 23Na MAS NMR spectra did not show any peaks of phase-separated NaOH or Na2CO3 until the neutralization degree was up to 217.5%. It can be presumed that the aggregates of Na+ ions can contain approximately two Na+ units for every carboxyl group before the phase separation. 相似文献
68.
Benjamin Prek Jure Bezenšek Marta Kasunič Uroš Grošelj Jurij Svete Branko Stanovnik 《Tetrahedron》2014
Herein a simple one-pot metal-free synthesis of alkyl-, aryl-, heteroaryl- and alkoxycarbonyl substituted 1,3-bis(dimethylamino)benzene derivatives is described. The products were prepared from the corresponding methyl ketones or compounds with an α-methylene group in regard to the carbonyl group, using N,N-dimethylacetamide dimethyl acetal (DMADMA) as the reagent. 相似文献
69.
《催化学报》2014,(12):1781-1792
Chin. J. Catal., 2014, 35: 1911–1916 doi: 10.1016/S1872‐2067(14)60208‐4 Dehydrogenation of primary aliphatic alcohols to aldehydes over Cu‐Ni bimetallic catalysts Tianliang Lu, Zhongtian Du, Junxia Liu, Chen Chen, Jie Xu * Dalian Institute of Chemical Physics, Chinese Academy of Sciences; University of Chinese Academy of Sciences 相似文献
70.
Mordenite (MOR) has demonstrated potential as a catalyst for alkylation due to high variability, intrinsic porosity, and outstanding stability. However, the contact probability of benzene and methanol has been limited by typical layered structures of MOR and there is no connection between layers. Here, we report the preparedness of H-MOR via a sequential post-treatment method based on a commercial MOR. H-MOR sample had appeared lattice imperfections inferred from characterization means. The samples were tested with benezene methylation reaction. Results show that the high conversion of benzene and the high selectivity of toluene were obtained from the miracle role of lattice imperfections in the H-MOR sample. Sequentially, based on the study of all catalyst structure and physical properties, a plausible reaction mechanism for the selectivity of the desired toluene was proposed. 相似文献