全文获取类型
收费全文 | 34800篇 |
免费 | 3815篇 |
国内免费 | 6475篇 |
专业分类
化学 | 31344篇 |
晶体学 | 1345篇 |
力学 | 798篇 |
综合类 | 248篇 |
数学 | 2079篇 |
物理学 | 9276篇 |
出版年
2024年 | 73篇 |
2023年 | 389篇 |
2022年 | 982篇 |
2021年 | 923篇 |
2020年 | 1154篇 |
2019年 | 1142篇 |
2018年 | 962篇 |
2017年 | 1319篇 |
2016年 | 1350篇 |
2015年 | 1215篇 |
2014年 | 1646篇 |
2013年 | 3047篇 |
2012年 | 2036篇 |
2011年 | 2462篇 |
2010年 | 2093篇 |
2009年 | 2367篇 |
2008年 | 2415篇 |
2007年 | 2402篇 |
2006年 | 2237篇 |
2005年 | 2113篇 |
2004年 | 1873篇 |
2003年 | 1540篇 |
2002年 | 1303篇 |
2001年 | 1110篇 |
2000年 | 1049篇 |
1999年 | 874篇 |
1998年 | 726篇 |
1997年 | 649篇 |
1996年 | 557篇 |
1995年 | 571篇 |
1994年 | 491篇 |
1993年 | 429篇 |
1992年 | 325篇 |
1991年 | 233篇 |
1990年 | 144篇 |
1989年 | 142篇 |
1988年 | 126篇 |
1987年 | 76篇 |
1986年 | 78篇 |
1985年 | 72篇 |
1984年 | 57篇 |
1983年 | 34篇 |
1982年 | 47篇 |
1981年 | 47篇 |
1980年 | 54篇 |
1979年 | 43篇 |
1978年 | 32篇 |
1977年 | 27篇 |
1976年 | 14篇 |
1973年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
111.
The reaction of O-methyl tetramethyldiamidophosphite with 3-bromopropanol or 3-bromo-2-butanol occurs with the liberation of dimethylamine and results in mixed phosphites. The reaction of O-methyl tetramethyldiamidophosphite with 3-thiocyano-2-butanol proceeds with the participation of the sulfur atom of the thiocyano group and formation ofS-(3-hydroxybutyl) tetramethyldiamidothiophosphate.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 167–169, January, 1994. 相似文献
112.
Electrolysis of dimethyl malonate or methyl cyanoacetate in methanol in the presence of LiCl in an undivided cell leads to formation of 1,1,2,2-cyclopropanetetracarboxylic derivatives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1835–1836, October, 1994.This work was supported by the International Science Foundation (Grant No MHY 000). 相似文献
113.
114.
R. Souzy B. Ameduri B. Boutevin 《Journal of polymer science. Part A, Polymer chemistry》2004,42(20):5077-5097
The radical co‐ and terpolymerization of 4‐[(α,β,β‐trifluorovinyl)oxy]bromo benzene (TFVOBB) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF, or VF2), hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), and chlorotrifluroroethylene (CTFE) is presented. Although TFVOBB could be thermocyclodimerized, it could not homopolymerize under radical initiation. TFVOBB could be copolymerized in solution under a radical initiator with VDF or CTFE comonomers, while its copolymerization with HFP or PMVE were unsuccessful. The terpolymerization of TFVOBB with VDF and HFP, or VDF and PMVE, or VDF and CTFE also led to original fluorinated terpolymers bearing bromoaromatic side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature of the radical initiators, and of the nature of solvents (fluorinated or nonhalogenated). Various monomer concentrations in the co‐ and terpolymers were assessed by 19F and 1H‐NMR spectroscopy. The thermal and physico chemical properties were also studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5077–5097, 2004 相似文献
115.
A. S. Peregudov L. N. Usatova E. I. Smyslova E. I. Fedin D. N. Kravtsov 《Russian Chemical Bulletin》1995,44(8):1513-1519
It has been shown by the19F NMR method that the relative polarities of nitrogenelement bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and PPh3Au derivatives increase in the order N-H19F NMR. It has been found that these reactions occur by a bimolecular associative mechanism and that the N-H bond is substantially less reactive than the N-Hg and N-Au bonds, which have identical reactivities within the limits of sensitivity of the method used.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1574–1580, August, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 93-03-5528). 相似文献
116.
A general class of Fuller modified maximum likelihood estimators are considered. It is shown that this class possesses finite moments. Asymptotic bias and asymptotic mean squared error are derived using small-σ expansions. A simulation study is carried out to compare different estimators in this class with standard estimators. 相似文献
117.
Michael-Addition Reaction of Malononitrile with a,β-Unsaturated Cycloketones Catalyzed by KF/Al_2O_3
The utility of fluoride salts as potential base in a va-riety of synthetic reactions has been recognized in re-cent years.1 However, low solubility of fluoride salts in ordinary solvents hampers their wide applications in organic synthesis. On the other hand, there has been increasing use of inorganic solid supports as catalysts for many years2 resulting in higher selectivity, milder reaction conditions and easier work-up. Especially po-tassium fluoride-coated alumina (KF-alumina) has been a … 相似文献
118.
Duygu Avci Aylin Ziylan Albayrak 《Journal of polymer science. Part A, Polymer chemistry》2003,41(14):2207-2217
Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003 相似文献
119.
Yonggang Shangguan Li Zhao Liyang Tao Qiang Zheng 《Journal of Polymer Science.Polymer Physics》2007,45(13):1704-1712
The effects of preparation method, composition, and thermal condition on formation of β‐iPP in isotactic polypropylene/ethylene–propylene rubber (iPP/EPR) blends were studied using modulated differential scanning calorimeter (MDSC), wide angle X‐ray diffraction (WAXD), and phase contrast microscopy (PCM). It was found that the α‐iPP and β‐iPP can simultaneity form in the melt‐blended samples, whereas only α‐iPP exists in the solution‐blended samples. The results show that the formation of β‐iPP in the melt‐blended samples is related to the crystallization temperature and the β‐iPP generally diminishes and finally vanishes when the crystallization temperature moves far from 125 °C. The phenomena that the lower critical temperature of β‐iPP in iPP/EPR obviously increases to 114 °C and the upper critical temperature decreases to 134 °C indicate the narrowing of temperature interval, facilitating the formation of β‐iPP in iPP/EPR. Furthermore, it was found that the amount of β‐iPP in melt‐blended iPP/EPR samples is dependent on the composition and the maximum amount of β‐iPP formed when the composition of iPP/EPR blends is 85:15 in weight. The results through examining the effect of annealing for iPP/EPR samples at melt state indicate that this annealing may eliminate the susceptibility to β‐crystallization of iPP. However, only α‐iPP can be observed in solution‐blended samples subjected to annealing for different time. The PCM images demonstrate that an obvious phase‐separation happens in both melt‐blended and solution‐blended iPP/EPR samples, implying that compared with the disperse degree of EPR in iPP, the preparation method plays a dominant role in formation of β‐iPP. It is suggested that the origin of formation of β‐iPP results from the thermomechanical history of the EPR component in iPP/EPR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1704–1712, 2007 相似文献
120.
Peng Ping Wenshou Wang Xuesi Chen Xiabin Jing 《Journal of Polymer Science.Polymer Physics》2007,45(5):557-570
Poly(ε‐caprolactone)‐based segmented polyurethanes (PCLUs) were prepared from poly(ε‐caprolactone) diol, diisocyanates (DI), and 1,4‐butanediol. The DIs used were 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluenediisocyanate (TDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI). Differential scanning calorimetry, small‐angle X‐ray scattering, and dynamic mechanical analysis were employed to characterize the two‐phase structures of all PCLUs. It was found that HDI‐ and MDI‐based PCLUs had higher degree of microphase separation than did IPDI‐ and TDI‐based PCLUs, which was primarily due to the crystallization of HDI‐ and MDI‐based hard‐segments. As a result, the HDI‐based PCLU exhibited the highest recovery force up to 6 MPa and slowest stress relaxation with increasing temperature. Besides, it was found that the partial damage in hard‐segment domains during the sample deformation was responsible for the incomplete shape‐recovery of PCLUs after the first deformation, but the damage did not develop during the subsequent deformation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 557–570, 2007 相似文献