首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   53305篇
  免费   8510篇
  国内免费   5696篇
化学   37427篇
晶体学   643篇
力学   3075篇
综合类   328篇
数学   5983篇
物理学   20055篇
  2024年   183篇
  2023年   1122篇
  2022年   2078篇
  2021年   2191篇
  2020年   2272篇
  2019年   2141篇
  2018年   1831篇
  2017年   1780篇
  2016年   2608篇
  2015年   2640篇
  2014年   3101篇
  2013年   3961篇
  2012年   4856篇
  2011年   4790篇
  2010年   3324篇
  2009年   3115篇
  2008年   3338篇
  2007年   2964篇
  2006年   2662篇
  2005年   2289篇
  2004年   1743篇
  2003年   1389篇
  2002年   1275篇
  2001年   1020篇
  2000年   897篇
  1999年   1046篇
  1998年   859篇
  1997年   809篇
  1996年   797篇
  1995年   731篇
  1994年   615篇
  1993年   519篇
  1992年   431篇
  1991年   394篇
  1990年   341篇
  1989年   249篇
  1988年   180篇
  1987年   166篇
  1986年   160篇
  1985年   139篇
  1984年   87篇
  1983年   94篇
  1982年   55篇
  1981年   39篇
  1980年   29篇
  1979年   18篇
  1977年   18篇
  1976年   20篇
  1975年   21篇
  1972年   19篇
排序方式: 共有10000条查询结果,搜索用时 17 毫秒
991.
Self organization and redox behavior of a ferrocene containing triblock copolymer, poly(vinylferrocene)-block-poly(isobutylene)-block-poly(vinylferrocene), with narrow molecular weight distribution in solutions and in thin films were investigated. Dynamic light scattering studies of the block copolymer in dilute solutions indicated that the polymer chains aggregated at relatively low concentrations. The aggregations of polymer chains were observed in toluene, as well as in tetrahydrofuran at concentrations as low as 0.014 mg/mL and 0.0045 mg/mL, respectively. Thin films of the copolymer showed reversible single electron redox behavior, similar to that of ferrocene. Morphology and micro-phase separation of the copolymer was analyzed by transmission electron microscopy.  相似文献   
992.
(S)-6-Acrylyl-2,2’-dimethoxy-1,1’-binaphthyl (ADBN) was synthesized and anionically polymerized using n-BuLi as an initiator. The absolute value of specific optical rotation [α]25589 of poly-ADBN is ?118.0 and that is about 8 times that of the starting monomer ADBN. Poly-ADBN was confirmed to exist in the form of one-handed helical structure in solution by means of comparing the specific optical rotation, the CD and UV-Vis spectra with that of ADBN and the model compounds such as (S)-6-propionyl-2,2’-dimethoxy-1,1’-binaphthyl (PDBN) and (S)-6-heptanoyl-2,2’-dimethoxy-1,1’-binaphthyl (HDBN). This conclusion was also confirmed by the fact that the g-value of poly-ADBN is about 13 times as high as that of its monomer and model compounds  相似文献   
993.
The characterization of polymers by pyrolysis directly in the ion source of a double focusing magnetic sector mass spectrometer, operating in the chemical ionization mode, is described. Pyrolysis is achieved by two different probe techniques. A low temperature, slow heating rate direct insertion probe (DIP) is used at 400°C, and a specifically constructed high temperature, fast heating rate, high temperature pyrolysis (HTP) probe is used at 1000°C. This probe is capable of achieving pyrolysis temperatures of 1200°C at controlled heating rates up to 20,000°C/s. The mass spectrometric analysis of the pyrolysis products was achieved under chemical ionization (CI) conditions utilizing methane, isobutane, and ammonia as reagent gases. Under CI conditions the molecular ions formed in the mass spectrometer show little tendency to fragment. The CI mass pyrograms are very simple, with each peak in the spectra ascribable to a particular component in the pyrolysis product mixture. The results of the two probe pyrolysis techniques are compared and the utility of each technique for the characterization of polymers is demonstrated using the vinyl polymers polymethyl methacrylate, polyvinyl chloride, and polystyrene.  相似文献   
994.
Polystyrene-supported N-phenyl-N-acyl sulfonamide resin was prepared by reacting polystyrene sulfonyl chloride resin with aniline and acylating in pyridine with either acid chlorides or anhydrides. Then, this resin was utilized as a new type of acyl transfer reagent to synthesize the amide library. It was approved to be a more effective acyl transfer reagent with higher amide yields than the polystyrene-supported N-methyl-N-acyl sulfonamide resin and N-benzyl-N-acyl sulfonamide resin. When the phenyl group bonded to the N atom on N-phenyl-N-acyl sulfonamide resin was substituted by the electron withdrawing group or electron donating group, a decreasing amide yield was obtained. N-phenyl-N-acyl sulfonamide resin could be regenerated many times.  相似文献   
995.
The emulsifier-free emulsion copolymerization of α-methylstyrene (AMS) and methyl methacrylate (MMA) in the presence of functional monomer acrylic acid (AA) was carried out in batch process, giving birth to sub-100 nm nanoparticles. The kinetics of polymerization was investigated. The morphology and size of particles were monitored by TEM. The influences of the functional monomer AA concentration, initiator ammonium persulfate (APS) concentration, and polymerization temperature were studied. It was found that AMS caused a drastic decrease in both the rate of polymerization and the average degree of polymerization. The activation energy calculated from Arrhenius plot turned out to be 83.6 kJ/mol.  相似文献   
996.
The effect of reaction time and mechanical stirring on thermal degradation of high density polyethylene(HDPE) was studied at 350°C under nitrogen atomosphere in a batch pressure reactor. Changes in molecular weight(MW), molecular weight distribution (MWD), and crystalline behaviors of the degraded products were investigated by gel chromatography (GPC) and differential scanning calorimetry (DSC). It was found that MWD curves all shifted toward lower molecular weight with increasing reaction time, with both the extent of the movement and its showing a rapid initial drop and then leveling off. In a short period of reaction time, the MW, MWD and crystalline behaviors of the degraded products were affected notably by the mechanical stirring. The of the degraded products without stirring was lower than that of products with stirring in the same time, which should be related to the large difference of temperature distributions in the reactor. When the reaction time reached 4 h, the of the degraded products had dropped to about 5 × 103g/mol from about 3 × 105g/mol for the original , and the product did not show the melting and crystallization behaviors of high density polyethylene again.  相似文献   
997.
The development of methodology for synthesizing new materials in which metal atoms are linked by hydrocarbons whose electronic conjugation is unbroken is described. The fundamental idea is to twist the hydrocarbons into helices. By attaching bulky groups to their precursors, the helices can be made to twist mainly in one direction. The molecules synthesized are helicenes capped by five-membered rings to which metals are attached. If the size of the helix is chosen appropriately, a polymeric structure forms in which hydrocarbon rings and metal atoms alternate. An oligomer with Structure 22 is the first such material prepared. It and related structures might be precursors of molecular solenoids, examples of which are not yet known.  相似文献   
998.

Nanoscale poly(alkyl methacrylate)s including poly(methyl methacrylate), poly(ethyl methacrylate), poly(cyclohexyl methacrylate), poly(iso‐butyl methacrylate) and poly(benzyl methacrylate) were prepared by a modified microemulsion polymerization procedure. NMR analysis suggested that these poly(methacrylate)s samples were higher in syndiotactic content, lower in isotactic content and the glass transition temperatures (Tgs) of them were also higher than those reported in the literature. The tacticities of the poly(methacrylate)s, beside the restricted volume effect of nanoparticles during the modified microemulsion polymerization, were mainly influenced by the reaction temperature, the lower the reaction temperature, the higher the syndiotacticity of the products. The syndiotacticity of the product decreased obviously when the polymerization was carried out at a temperature far above the Tg of the resulting polymer. It was also shown that the tacticity of the polymer was affected by the monomer structure, a monomer with the bulkier alkyl side group would liable to result in a polymer with richer syndiotacticity. Possible mechanism of rich‐syndiotacticity was also discussed.  相似文献   
999.
A method is described for the preparation of functional polybutadiene (PB) with hydroxyl groups along the polymer chain. This material can be used directly or as the starting substrate for further polymerization in both academic and industrial processes. We have developed a convenient method to obtain a polymer with a narrow molecular weight distribution and with a known content of hydroxyl groups along the backbone. By controlling the hydroxylation reaction conditions, the appropriate molar ratios of THF, water and acid with the epoxide are 30, 15 and 1.5, respectively. By minimizing the crosslinking reaction, the desired PB was prepared and subsequently characterized.  相似文献   
1000.
The 2H NMR of uniaxially strained swollen chloroprene rubbers and butadiene-styrene copolymers with different crosslink densities is studied. the relative number of chain segments between cross-links of various samples is obtained. the results are in approximate agreement with those obtained from the Flory equilibrium-swelling method. It is found that the enhancement factor G depends not only on the lattice-walk model and swelling of rubber, such as Tanaka etc. expected, but also on the crosslink density and the structure of the rubber. the formula relating G to the number of chain segments between cross links is derived from theory. Moreover, we can also estimate the relation between the enhancement factor Gr of real rubber and G calculated from the theory of the lattice model. the 2H NMR results of these samples indicate that the interaction between chain segments decreases with increasing crosslink density.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号