全文获取类型
收费全文 | 711篇 |
免费 | 51篇 |
国内免费 | 69篇 |
专业分类
化学 | 812篇 |
晶体学 | 2篇 |
力学 | 2篇 |
综合类 | 1篇 |
物理学 | 14篇 |
出版年
2024年 | 2篇 |
2023年 | 4篇 |
2022年 | 10篇 |
2021年 | 7篇 |
2020年 | 19篇 |
2019年 | 16篇 |
2018年 | 24篇 |
2017年 | 33篇 |
2016年 | 31篇 |
2015年 | 34篇 |
2014年 | 17篇 |
2013年 | 67篇 |
2012年 | 54篇 |
2011年 | 54篇 |
2010年 | 49篇 |
2009年 | 49篇 |
2008年 | 57篇 |
2007年 | 55篇 |
2006年 | 44篇 |
2005年 | 42篇 |
2004年 | 49篇 |
2003年 | 37篇 |
2002年 | 27篇 |
2001年 | 17篇 |
2000年 | 13篇 |
1999年 | 4篇 |
1998年 | 6篇 |
1997年 | 5篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
排序方式: 共有831条查询结果,搜索用时 15 毫秒
1.
Hans R. Kricheldorf Lali Vakhtangishvili Gert Schwarz 《Journal of polymer science. Part A, Polymer chemistry》2004,42(22):5725-5735
Poly(pyridine ether)s were prepared in two ways: the polycondensation of silylated 1,1,1‐tris(4‐hydroxyphenyl)ethane (THPE) with 2,6‐difluoropyridine (method A) and the polycondensation of free THPE with 2,6‐dichloropyridine (method B). With method A, the THPE/difluoropyridine feed ratio was varied from 1.0:1.0 to 1.0:1.6. Cycles, bicycles, and multicycles were the main reaction products, and crosslinking was never observed. When ideal stoichiometry was used exclusively, multicycles free of functional groups were obtained. These multicycles were detectable in matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) mass spectra up to B38C76 with a mass of approximately 32,000 Da. With method B, the reaction conditions were varied at a fixed feed ratio to achieve an optimum for the preparation of multicyclic polyethers, but because of the lower reactivity of 2,6‐dichloropyridine, a quantitative conversion was not achieved. The reaction products were characterized with MALDI‐TOF mass spectrometry, viscosity measurements, and size exclusion chromatography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5725–5735, 2004 相似文献
2.
Compared with linear polymers, more factors may affect the glass‐transition temperature (Tg) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. Tg's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of Tg to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. Tg's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. Tg values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. Tg values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of Tg versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that Tg increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004 相似文献
3.
Xiaohui Yang Xiaoying Sun Jiajia Shao Yunhang Liu Xinling Wang 《Journal of Polymer Science.Polymer Physics》2004,42(22):4195-4198
A series of polymer electrolytes based on multiarm polymers and lithium salt complexes were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and impedance measurement. The relationships of conductivity with salt concentration, temperature, and arm numbers are discussed. It is suggested that the star polymer has a higher solvency and ion transfer ability on lithium salts than on linear polymers. The conductivity maximum appeared at a higher salt concentration ([EO]/[Li] = 4). Impedance measurement suggested that the optimum conductivity was 2 × 10?4 s · cm?1. The conductivity increased with temperature and the dependence of ionic conductivity on temperature fits the Arrhenius equation. Among the studied systems, the star polymer with a five arm number performs better than other structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4195–4198, 2004 相似文献
4.
Andr Luciani Christopher J. G. Plummer Tuan Nguyen Lszl Garamszegi Jan‐Anders E. Mnson 《Journal of Polymer Science.Polymer Physics》2004,42(7):1218-1225
The effects of the size (pseudo‐generation number) and nature of end groups on physical and rheological properties were investigated for a series of hyperbranched polyesters based on an ethoxylated pentaerythritol core and 2,2‐bis‐(hydroxymethyl)propionic acid repeat units. The observed linear dependence of the melt viscosity on the molar mass in the high pseudo‐generation‐number limit indicated that entanglement effects were substantially absent. Moreover, the marked influence of end capping of the end groups on the physical and rheological properties suggested that intermolecular interactions were dominated by contacts between the outer shells of the molecules, in which the end groups were assumed to be concentrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1218–1225, 2004 相似文献
5.
6.
7.
Nicolas Meyer Mohamad Nasser Eddine Christelle Delaite Guy Hurtrez Philippe Dumas 《Journal of polymer science. Part A, Polymer chemistry》2003,41(21):3329-3335
The reactions of polystyryllithium and potassium on dimethoxymethyl 1,1‐diphenylethylene derivatives were studied in different solvents. In a polar medium, A3 and A6 star types were formed according to the stoichiometry, whereas in a nonpolar medium, hyperbranched structures were synthesized. Extensions of an already proposed mechanism in polar and nonpolar media were examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3329–3335, 2003 相似文献
8.
Ye Lin Feng Zeng‐Guo Zhao Yu‐Mei Wu Feng Chen Shi Wang Guo‐Qing 《Journal of polymer science. Part A, Polymer chemistry》2006,44(11):3650-3665
A novel cyclic ether monomer 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxy‐methyl}‐3′‐methyloxetane (HEMO) was prepared from the reaction of 3‐hydroxymethyl‐3′‐methyloxetane tosylate with triethylene glycol. The corresponding hyperbranched polyether (PHEMO) was synthesized using BF3·Et2O as initiator through cationic ring‐opening polymerization. The evidence from 1H and 13C NMR analyses revealed that the hyperbranched structure is constructed by the competition between two chain propagation mechanisms, i.e. active chain end and activated monomer mechanism. The terminal structure of PHEMO with a cyclic fragment was definitely detected by MALDI‐TOF measurement. A DSC test implied that the resulting polyether has excellent segment motion performance potentially beneficial for the ion transport of polymer electrolytes. Moreover, a TGA assay showed that this hyperbranched polymer possesses high thermostability as compared to its liquid counterpart. The ion conductivity was measured to reach 5.6 × 10?5 S/cm at room temperature and 6.3 × 10?4 S/cm at 80 °C after doped with LiTFSI at a ratio of Li:O = 0.05, presenting the promise to meet the practical requirement of lithium ion batteries for polymer electrolytes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3650–3665, 2006 相似文献
9.
Suzanne J. Dilly Steven J. Carlisle Andrew J. Clark Andrew R. Shepherd Stephen C. Smith Paul C. Taylor Andrew Marsh 《Journal of polymer science. Part A, Polymer chemistry》2006,44(7):2248-2259
A practical and divergent synthesis of supported [1,3,5]‐triazine dendritic molecules on Wang resin, PEGA resin, SynPhase? Lanterns, and silica gel is described. The alkylamine linkers used allow derivatization with functionality for both synthetic (e.g., supported reagent and scavenger activity) and chemical biology applications. The use of supported intermediates allows differentiation of symmetric linkers without the need for protecting group chemistry. The synthetic route uses inexpensive, readily available starting materials in a straightforward and scaleable strategy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2248–2259, 2006 相似文献
10.