全文获取类型
收费全文 | 6973篇 |
免费 | 437篇 |
国内免费 | 871篇 |
专业分类
化学 | 6883篇 |
晶体学 | 79篇 |
力学 | 96篇 |
综合类 | 35篇 |
数学 | 47篇 |
物理学 | 1141篇 |
出版年
2024年 | 16篇 |
2023年 | 55篇 |
2022年 | 137篇 |
2021年 | 166篇 |
2020年 | 189篇 |
2019年 | 174篇 |
2018年 | 112篇 |
2017年 | 122篇 |
2016年 | 230篇 |
2015年 | 214篇 |
2014年 | 217篇 |
2013年 | 599篇 |
2012年 | 283篇 |
2011年 | 319篇 |
2010年 | 273篇 |
2009年 | 338篇 |
2008年 | 433篇 |
2007年 | 500篇 |
2006年 | 428篇 |
2005年 | 387篇 |
2004年 | 392篇 |
2003年 | 331篇 |
2002年 | 266篇 |
2001年 | 218篇 |
2000年 | 242篇 |
1999年 | 223篇 |
1998年 | 171篇 |
1997年 | 206篇 |
1996年 | 171篇 |
1995年 | 168篇 |
1994年 | 151篇 |
1993年 | 123篇 |
1992年 | 142篇 |
1991年 | 61篇 |
1990年 | 36篇 |
1989年 | 32篇 |
1988年 | 36篇 |
1987年 | 16篇 |
1986年 | 18篇 |
1985年 | 17篇 |
1984年 | 12篇 |
1983年 | 4篇 |
1982年 | 12篇 |
1981年 | 10篇 |
1980年 | 8篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1974年 | 3篇 |
1973年 | 3篇 |
排序方式: 共有8281条查询结果,搜索用时 15 毫秒
11.
LI Shufeng LI Qian YANG Xinlin HUANG Wenqiang** State Key Laboratory of Functional Polymer Materials for Adsorption Separation Institute of Polymer Chemistry Nankai University Tianjin China 《Chinese Journal of Reactive Polymers》2004,(Z1)
1. INTRODUCTION The development of efficient polymer-supported catalysts has attracted much attention [1]. For obtaining polymeric catalysts, catalytically active groups were introduced onto polymers mostly by copolymerization of the appropriate monomers bearing the desired catalyticfunctionalities (e.g. imidazole, OH, and COOH) or by modification of preformed polymers.Another possibility involves the attachment of side chains, containing the desired arrangement of functional groups, o… 相似文献
12.
Daria E. Lonsdale Geoffrey Johnston‐Hall Amanda Fawcett Craig A. Bell Carl N. Urbani Michael R. Whittaker Michael J. Monteiro 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3620-3625
In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (Ctrs) determined using the Mayo method is equal to 3.8 × 10?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the Mn data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007 相似文献
13.
Jie Xue Liang Chen Li Zhou Zhifeng Jia Yanping Wang Xinyuan Zhu Deyue Yan 《Journal of Polymer Science.Polymer Physics》2006,44(15):2050-2057
α‐Cyclodextrin (α‐CD) has been complexed with various poly(ethylene glycol) (PEG) derivatives in aqueous solution. It has been found that the end groups of PEG derivatives affect the complexation kinetics greatly, but have only a little influence on the thermodynamic behavior. By increasing the hydrophobicity of end groups, the complexation speeds up rapidly. On the other hand, the bulky end groups slow down the threading of polymeric guests into the cavity of CD. By changing the hydrophobicity and the size of end groups, the complexation rate can be adjusted in the range of several orders of magnitudes, which should be quite useful in the design of new supramolecular systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2050–2057, 2006 相似文献
14.
Sung‐Fu Hsu Tzong‐Ming Wu Chien‐Shiun Liao 《Journal of Polymer Science.Polymer Physics》2006,44(23):3337-3347
Poly(3‐hydroxybutyrate) (PHB)/layered double hydroxides (LDHs) nanocomposites were prepared by mixing PHB and poly(ethylene glycol) phosphonates (PEOPAs)‐modified LDH (PMLDH) in chloroform solution. Both X‐ray diffraction data and TEM micrographs of PHB/PMLDH nanocomposites indicate that the PMLDHs are randomly dispersed and exfoliated into the PHB matrix. In this study, the effect of PMLDH on the isothermal crystallization behavior of PHB was investigated using a differential scanning calorimeter (DSC) and polarized optical microscopy. Isothermal crystallization results of PHB/PMLDH nanocomposites show that the addition of 2 wt % PMLDH into PHB induced more heterogeneous nucleation in the crystallization significantly increasing the crystallization rate and reducing their activation energy. By adding more PMLDH into the PHB probably causes more steric hindrance of the diffusion of PHB, reducing the transportation ability of polymer chains during crystallization, thus increasing the activation energy. The correlation among crystallization kinetics, melting behavior and crystalline structure of PHB/PMLDH nanocomposites can also be discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3337–3347, 2006 相似文献
15.
Leong‐Huat Gan Palaniswamy Ravi Bao Wei Mao Kam‐Chiu Tam 《Journal of polymer science. Part A, Polymer chemistry》2003,41(17):2688-2695
Polymerization of 2‐(diethylamino)ethyl methacrylate (DEAEMA) via homogeneous atom transfer radical polymerization under various reaction conditions is described. The effects of the initiators and solvents were examined. With 1,1,4,7,10,10‐hexamethyl triethylenetetramine/copper(I) chloride/p‐toluenesulfonyl chloride as the ligand/catalyst/initiator system in methanol, poly(DEAEMA) with a polydispersity index as low as 1.07 was synthesized. Kinetic studies demonstrated the polymerization was very well controlled and exhibited the living characteristic of the process. Well‐defined block copolymers of DEAEMA and tert‐butyl methacrylate (tBMA) were successfully synthesized. The copolymers could be synthesized with equally good results by starting with either p(DEAEMA) or p(tBMA) as the macroinitiators. However, only the macroinitiators terminated with chlorine should be used. The corresponding macroinitiators with bromine as a transferable group did not yield well‐defined copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2688–2695, 2003 相似文献
16.
Md. Nur Alam Per B. Zetterlund Masayoshi Okubo 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4995-5004
Bimolecular termination in nitroxide‐mediated radical polymerization in miniemulsion has been investigated through the heating of a polystyrene–2,2,6,6‐tetramethylpiperidinyl‐1‐oxy macroinitiator and its 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy analogue in an aqueous toluene dispersion with sodium dodecyl benzenesulfonate as a surfactant at 125 °C. The level of bimolecular termination by combination, evaluated from the high‐molecular‐weight shoulder, was higher in miniemulsion than in solution and increased with decreasing particle size. Quantitative analysis revealed that these results cannot be rationalized solely by nitroxide partitioning to the aqueous phase. The results are explained by an interface effect, by which nitroxide is adsorbed or located at the aqueous–organic interface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4995–5004, 2007 相似文献
17.
Govindarajan Sankar A. Sultan Nasar 《Journal of polymer science. Part A, Polymer chemistry》2007,45(8):1557-1570
A series of substituted N‐methylaniline‐blocked polyisocyanates based on 4,4′‐methylenebis(phenyl isocyanate) and poly(tetrahydrofuran) were prepared and characterized thoroughly with FTIR, 1H NMR, and 13C NMR spectroscopy methods. Compared with unsubstituted N‐methylaniline, a blocking agent with an electron‐releasing substituent at the para position took a shorter time, whereas those with an electron‐releasing substituent at the ortho position or an electron‐withdrawing substituent at the ortho and para positions took longer times for the blocking reaction. The thermal dissociation reactions of blocked polyisocyanates were carried out with an FTIR spectrophotometer attached to hot‐stage accessories under dynamic and isothermal conditions. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate the deblocking kinetics and activation parameters. The cure times of blocked polyisocyanates with hydroxyl‐terminated polybutadiene were also determined. The deblocking temperatures, the results of cure‐time studies, and the kinetic parameters revealed that the thermal dissociation of the N‐methylaniline‐blocked polyisocyanates was retarded by electron‐donating substituents and facilitated by electron‐withdrawing substituents. The action of N‐methylanilines as blocking agents for isocyanate was explained by the formation of a four‐center, intramolecularly hydrogen‐bonded ring structure during the thermal dissociation of the blocked polyisocyanates. The formation of such a hydrogen‐bonded ring structure was confirmed and supported by variable‐temperature 1H NMR studies and entropy parameters, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1557–1570, 2007 相似文献
18.
V. V. AntiĆ M. P. AntiĆ M. N. Govedarica P. R. DvorniĆ 《Journal of polymer science. Part A, Polymer chemistry》2007,45(11):2246-2258
The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10−6 to 3.1 × 10−5 mol Pt/mol CHCH2. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10−6 mol of Pt per mol of CHCH2, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH2 groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007 相似文献
19.
Hiroshi Ito Masaki Okazaki Dolores C. Miller 《Journal of polymer science. Part A, Polymer chemistry》2004,42(6):1478-1505
Radical copolymerizations of electron‐deficient 2‐trifluoromethylacrylic (TFMA) monomers, such as 2‐trifluoromethylacrylic acid and t‐butyl 2‐trifluoromethylacrylate (TBTFMA), with electron‐rich norbornene derivatives and vinyl ethers with 2,2′‐azobisisobutyronitrile as the initiator were investigated in detail through the analysis of the kinetics in situ with 1H NMR and through the determination of the monomer reactivity ratios. The norbornene derivatives used in this study included bicyclo[2.2.1]hept‐2‐ene (norbornene) and 5‐(2‐trifluoromethyl‐1,1,1‐trifluoro‐2‐hydroxylpropyl)‐2‐norbornene. The vinyl ether monomers were ethyl vinyl ether, t‐butyl vinyl ether, and 3,4‐dihydro‐2‐H‐pyran. Vinylene carbonate was found to copolymerize with TBTFMA. Although none of the monomers underwent radical homopolymerization under normal conditions, they copolymerized readily, producing a copolymer containing 60–70 mol % TFMA. The copolymerization of the TFMA monomer with norbornenes and vinyl ethers deviated from the terminal model and could be described by the penultimate model. The copolymers of TFMA reported in this article were evaluated as chemical amplification resist polymers for the emerging field of 157‐nm lithography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1478–1505, 2004 相似文献
20.
Tatiana B. Mikenas Vladimir A. Zakharov Lyudmila G. Echevskaya Mikhail A. Matsko 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5057-5066
The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl2/MgCl2‐Al(i‐Bu)3 (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl2/MgCl2‐Al(i‐Bu)3 has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl2/MgCl2‐Al(i‐Bu)3 has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007 相似文献