全文获取类型
收费全文 | 875篇 |
免费 | 35篇 |
国内免费 | 84篇 |
专业分类
化学 | 917篇 |
晶体学 | 3篇 |
力学 | 9篇 |
综合类 | 2篇 |
数学 | 9篇 |
物理学 | 54篇 |
出版年
2023年 | 5篇 |
2022年 | 17篇 |
2021年 | 17篇 |
2020年 | 12篇 |
2019年 | 8篇 |
2018年 | 19篇 |
2017年 | 19篇 |
2016年 | 15篇 |
2015年 | 22篇 |
2014年 | 22篇 |
2013年 | 56篇 |
2012年 | 41篇 |
2011年 | 51篇 |
2010年 | 53篇 |
2009年 | 62篇 |
2008年 | 74篇 |
2007年 | 65篇 |
2006年 | 60篇 |
2005年 | 51篇 |
2004年 | 40篇 |
2003年 | 35篇 |
2002年 | 24篇 |
2001年 | 19篇 |
2000年 | 29篇 |
1999年 | 21篇 |
1998年 | 12篇 |
1997年 | 14篇 |
1996年 | 19篇 |
1995年 | 25篇 |
1994年 | 13篇 |
1993年 | 21篇 |
1992年 | 13篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 6篇 |
1988年 | 7篇 |
1987年 | 9篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1979年 | 1篇 |
排序方式: 共有994条查询结果,搜索用时 15 毫秒
81.
The free radical copolymerization of (5-bromo-1-Benzofuran-2-yl)(phenyl)-O-methacrylketoxime (BPMKO) with 2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate(AOEMA) has been carried out in 1, 4-dioxane at 65°C ± 1 and was analyzed by Fourier transform infrared, 1H-NMR, 13C-NMR and gel permeation chromatography. Elemental analysis was used to determine the molar fractions of BPMKO and AOEMA in the copolymers. The monomer–reactivity ratios were calculated according to the general copolymerization equation using Kelen-Tüdõs and Finemann-Ross linearization methods. The reactivity ratios indicated a tendency toward random copolymerization. The polydispersity indices of the polymers were determined by gel permeation chromatography and suggested a strong tendency for chain termination by disproportionation. The thermal behaviors of copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The glass-transition temperature of the copolymers increased with increasing BPMKO content in the copolymers. All the products showed moderate activity against different strains of bacteria and fungi. 相似文献
82.
The oxygen permeability of films is relevant for packaging related and technical applications. An increasingly used test method for the measurement of oxygen permeability is the optical test method, because it allows a simple and cost-efficient measurement setup. This method is based on optical chemical sensors. However, not much is known about its validity. Therefore, method validation is necessary which is subject of this study. The optical method is compared with the carrier gas method for a variety of film samples. In the tested permeability range of 0.5–2500 cm3 (STP)·(m2 d bar)−1 both methods deviated less than 20% for zero and 50% relative humidity. 相似文献
83.
Huali Yu Zhengbiao Zhang Zhenping Cheng Jian Zhu Nianchen Zhou Wei Zhang Xiulin Zhu 《Journal of polymer science. Part A, Polymer chemistry》2012,50(11):2182-2187
In this work, zero‐valent iron (Fe(0)) (powder or wire) and elemental bromine (Br2) were used as the catalysts for atom transfer radical polymerization (ATRP) of styrene (St) without any additional initiator at 110 °C. The polymerizations happened with controlled evidence at appropriate molar ratio of Fe(0) to Br2: a remarkable increase of molecular weights with St conversions, the narrow molecular weight distributions and living polymer chains end‐capped by Br. More Br2 or less Fe(0) led to a slow polymerization rate but an improved control over molecular weights. After examining the polymer chain ends by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, it was concluded that the polymerization was initiated by thermal self‐initiation, and regulated by the in situ generated FeIIIBr3. The results suggested that the Fe(0)/Br2 catalyzing polymerization was a classical ATRP process with easier operation and more economical components. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
84.
The temperature dependence of gas sorption and transport properties is examined for two polyimide isomers. The permeabilities and solubilities of five gases in these materials are reported over an extensive temperature range from 35 to 325°C. Also, the activation energies for permeation, the heats of sorption, and the activation energies for diffusion obtained for both polyimides are compared and correlated with physical properties of the polymers and penetrants. The influence of temperature on the selective properties of these membrane materials is discussed for three gas separations; He/N2, CO2/CH4, and O2/N2. Thorough analysis of these data provides insight into the influence of the subtle difference in chain structure of the two isomers. The performance of the 6FDA-6Fp DA as a separation membrane at high temperatures suggests that it is an outstanding candidate for use in novel elevated temperature applications. ©1995 John Wiley & Sons, Inc. 相似文献
85.
Dan He Seok Kyun Noh Won Seok Lyoo 《Journal of polymer science. Part A, Polymer chemistry》2011,49(21):4594-4602
Past research has examined the atom transfer radical polymerization (ATRP) with high oxidation state metal complexes and without the need for any additives such as reducing agent or free radical initiator. To extend this research, half‐metallocene ruthenium(III) (Ru(III)) catalysts were used for the polymerization of methyl methacrylate (MMA) for the first time. These catalysts were generated in situ simply by mixing phosphorus‐containing ligand and pentamethylcyclopentadienyl (Cp*) Ru(III) polymer ((Cp*RuCl2)n). The complexes in their higher oxidation state such as Cp*RuCl2(PPh3) were air‐stable, highly active, and removable catalysts for the ATRPs of MMA with both precision control of molecular weight and narrow polydispersity index. The addition of ppm amount of metal catalyst contributed to the formation of very well‐defined homopolymers and copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
86.
Kannapiran Rajendrakumar R. Dhamodharan 《Journal of polymer science. Part A, Polymer chemistry》2011,49(10):2165-2172
Isobornyl methacrylate (IBMA), a bulky hydrophobic methacrylate, undergoes very fast polymerization, in bulk, with Cu(I)Br/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA)/ethyl‐2‐bromoisobutyrate system, at ambient temperature. IBMA also undergoes a spontaneous initiator‐free polymerization, at ambient temperature, with Cu(I)Br/PMDETA catalytic system in dimethyl sulfoxide–water mixtures. The rate of the polymerization is seen to increase with the water content up to 80 mol % of water. A possible intervention of air in initiation is proposed. The active Cu(0) formed by the disproportionation of Cu(I) species in aqueous medium probably plays a vital role for a possible air‐initiation of IBMA via single electron transfer‐living radical polymerization (SET‐LRP) mechanism. A high tolerance level to water under SET‐LRP conditions is demonstrated. The poly(IBMA) samples obtained exhibit low molecular weight distributions (1.1–1.3). Similar behavior was not observed with other common methacrylates such as methyl methacrylate, t‐butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
87.
Ravi Aggarwal Durairaj Baskaran 《Journal of polymer science. Part A, Polymer chemistry》2011,49(23):5049-5056
Hydrated sodium montmorillonite (Na‐clay) has been used as a catalyst support for the heterogeneous atom transfer radical polymerization of benzyl methacrylate in the presence of various concentrations of water, reducing agent, and CuBr2 in anisole at ambient temperature. The polymerization was promoted via reduction of CuII to CuI through the addition of sodium ascorbate (NaAsc) as a reducing agent in aqueous solution. The polymerizaton proceeded in a controlled manner and produced poly(benzyl methacylate) with moderately narrow molecular weight distribution (MWD) when performed under optimum conditions of hydration (10 wt % ≤ H2O/Na‐clay ≤ 21 wt %) and reducing agent (0.15 ≤ [NaAsc]/[I] ≤ 0.23). The polymerization was uncontrolled if hydration and NaAsc exceed above their optimum range of concentrations. Apparent rate of the polymerization (kapp) increased in the presence of decane–anisole (1/3, v/v) mixture solvent. Selective adsorption of decane at the interfaces of the hydrated clay was attributed for the rate enhancement due to increased polymer and hydrophobic interface interaction. The polymerization progressed in a controlled manner as confirmed by the first‐order time‐conversion plot, linear increase in molecular weights, and moderately narrow MWDs over conversion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
88.
Benchuan Zhu Guannan Qian Yuli Xiao Sheng Deng Meng Wang Aiguo Hu 《Journal of polymer science. Part A, Polymer chemistry》2011,49(24):5330-5338
Employing enediynes as crosslinking precursors, a novel yet efficient strategy, namely photo‐triggered Bergman cyclization, was integrated with intramolecular chain collapse to yield polymeric nanoparticles with the size regime below 20 nm. Enediyne motif was designed delicately to possess a high photo‐reactivity, with the double bond locked in a methyl benzoate ring while triple bonds substituted with phenyls. Single electron transfer‐living radical polymerization was conducted to provide linear acrylate copolymers with controlled molecular weights and narrow polydispersities. Poly(butylarylate‐co‐ 5 ) went through UV‐irradiation with a concurrent Bergman cyclization, resulting in well‐defined ultrafine polymeric nanoparticles. Results from NMR, Raman scattering, photoluminescence and UV‐vis spectra corroborated the presence of conjugative structures in the polymeric nanoparticles, indicating the occurrence of photo‐induced Bergman cyclization. A series of other acrylate‐based nanoparticles were investigated to confirm the applicability of such a unique strategy in thermal sensitive but UV‐stable polymeric structures, making photo‐Bergman cyclization a promising tool towards polymeric nanoparticles. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
89.
Qifeng Chen Zhengbiao Zhang Nianchen Zhou Zhenping Cheng Yingfeng Tu Xiulin Zhu 《Journal of polymer science. Part A, Polymer chemistry》2011,49(5):1183-1189
The copper(0)‐catalyzed living radical polymerization of acrylonitrile (AN) was investigated using ethyl 2‐bromoisobutyrate as an initiator and 2,2′‐bipyridine as a ligand. The polymerization proceeded smoothly in dimethyl sulphoxide with higher than 90% conversion in 13 h at 25 °C. The polymerization kept the features of controlled radical polymerization. 1H NMR spectra proved that the resultant polymer was end‐capped by ethyl 2‐bromoisobutyrate species. Such polymerization technique was also successfully introduced to conduct the copolymerization of styrene (St) and AN to obtain well‐controlled copolymers of St and AN at 25 °C, in which the monomer conversion of St could reach to higher than 90%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
90.
Hidetaka Tobita 《Journal of Polymer Science.Polymer Physics》2001,39(23):2960-2968
In free‐radical olefin polymerizations, the polymer‐transfer reactions could lead to chain scission as well as the formation of long‐chain branches. The Monte Carlo simulation for free‐radical polymerization that involves simultaneous long‐chain branching and random scission is used to investigate detailed branched structure. The relationship between the mean‐square radius of gyration 〈s2〉 and degree of polymerization P as well as that between the branching density and P is the same for both with and without random scission reactions—at least for smaller frequencies of scission reactions. The 〈s2〉 values were larger than those calculated from the Zimm–Stockmayer (Z‐S) equation in which random distribution of branch points is assumed, and therefore, the Z‐S equation may not be applied for low‐density polyethylenes. The elution curves of size exclusion chromatography were also simulated. The molecular weight distribution (MWD) calibrated relative to standard linear polymers is much narrower than the true MWD, and high molecular weight tails are clearly underestimated. A simplified method to estimate the true MWD from the calibrated MWD data is proposed. The MWD obtained with a light scattering photometer in which the absolute weight‐average molecular weight of polymers at each retention volume is determined directly is considered a reasonable estimate of the true MWD. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2960–2968, 2001 相似文献