全文获取类型
收费全文 | 2477篇 |
免费 | 113篇 |
国内免费 | 698篇 |
专业分类
化学 | 2998篇 |
晶体学 | 11篇 |
力学 | 7篇 |
综合类 | 21篇 |
数学 | 9篇 |
物理学 | 242篇 |
出版年
2024年 | 2篇 |
2023年 | 27篇 |
2022年 | 46篇 |
2021年 | 82篇 |
2020年 | 90篇 |
2019年 | 91篇 |
2018年 | 71篇 |
2017年 | 88篇 |
2016年 | 93篇 |
2015年 | 84篇 |
2014年 | 120篇 |
2013年 | 239篇 |
2012年 | 170篇 |
2011年 | 141篇 |
2010年 | 134篇 |
2009年 | 142篇 |
2008年 | 162篇 |
2007年 | 157篇 |
2006年 | 150篇 |
2005年 | 123篇 |
2004年 | 141篇 |
2003年 | 130篇 |
2002年 | 110篇 |
2001年 | 77篇 |
2000年 | 77篇 |
1999年 | 78篇 |
1998年 | 61篇 |
1997年 | 58篇 |
1996年 | 52篇 |
1995年 | 45篇 |
1994年 | 43篇 |
1993年 | 43篇 |
1992年 | 31篇 |
1991年 | 26篇 |
1990年 | 16篇 |
1989年 | 9篇 |
1988年 | 13篇 |
1987年 | 10篇 |
1986年 | 14篇 |
1985年 | 2篇 |
1984年 | 8篇 |
1983年 | 5篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 5篇 |
1973年 | 1篇 |
排序方式: 共有3288条查询结果,搜索用时 46 毫秒
71.
Dense membranes were prepared from poly(vinyl alcohol)–poly(N-vinyl pyrrolidone) (PVA–PVP) blends of different compositions and studied in swelling and dehydration by pervaporation of three organic solvents contaminated by 5 wt% water. The swelling generally increases with the PVP content. No extraction occurs in water–tetrahydrofuran (THF) and water–methyl ethyl ketone (MEK) mixtures. In ethanol containing 10 wt% of water, there is no extraction for blends containing less than 40 wt% PVP and an increasing extraction beyond this PVP content. The pervaporation flux of the water–ethanol mixture increases drastically at the same threshold whereas the water permselectivity falls to a low level. The values of the diffusion and permeability coefficients determined from transient permeation of the test water–ethanol mixture exhibit a similar sudden increase at the same PVP content threshold. This singular behavior of the blend membranes is interpreted by a strong affinity of the PVP component to ethanol, combined with a disappearance of crystallites in the blend at this threshold. Consequently the amorphous membrane can swell freely according to the affinity of the PVP component, leading to the observed behavior. 相似文献
72.
73.
顺丁烯二酸二异辛酯的合成 总被引:4,自引:0,他引:4
以顺丁烯二酸酐和异辛酯为原料,用对甲苯磺酸作催化剂合成顺丁烯二酸二异辛酯。用正交试验确定了酯化反应的优化条件,酯化率达97.96%. 相似文献
74.
An efficient and mild one‐pot synthesis of bis(oxazoline) (BOX) ligands is developed from reactions of dicarboxy dichlorides with β‐amino alcohols in the presence of 11.0 equiv. NEt3 followed by the addition of 3.6 equiv. methanesulfonyl chloride (MsCl). Nine different BOX ligands were prepared in excellent yields of ≥ 80%. Advantages of this improved synthesis are mild reaction conditions, short total reaction time of 9 h, and high isolated yields. 相似文献
75.
Cycloheptatrienes were obtained by the reaction of 2-substituted allylic alcohols with alkynes in the presence of catalytic amounts of palladium complexes and p-toluenesulfonic acid. 相似文献
76.
77.
Cu-Zn/γ-Al2O3催化剂的制备及其在选择加氢反应中的催化性能 总被引:4,自引:0,他引:4
通过浸渍法制备了不同Cu/Zn比的γ-Al2O3和改性γ-Al2O3负载的Cu-Zn催化剂,并用XRD,XPS和SEM等手段对催化剂进行了表征.XRD表征结果表明,还原活化前催化剂中的Cu和Zn分别以CuO和ZnO的形式存在;还原活化后Cu以单质的形式存在;催化剂失活后,单质Cu又转变成CuO.XPS和SEM分析结果表明,催化剂中金属的价态及颗粒的形貌在反应前后发生了变化.所制备的催化剂在糠醛加氢制糠醇反应中表现出较高的选择性.用Co改性的γ-Al2O3负载的Cu-Zn催化剂不仅具有较高的催化活性和选择性,而且还呈现出较长的寿命.催化剂中的Cu晶相是催化活性中心;催化剂中的Cu晶相转变成CuO和烧结是催化剂失活
的主要原因. 相似文献
78.
Ken-ichi Ogu 《Journal of fluorine chemistry》2003,124(1):69-80
Treatment of allylic alcohols with hexafluoropropene-diethylamine adduct (PPDA) afforded N,N-diethyl-2-fluoro-2-trifluoromethyl-4-alkenamides which were formed by the Claisen rearrangement of intermediary 2-alkenyl-1-diethylamino-2,3,3,3-tetrafluoro-1-propenyl ethers. Although (E)-allylic alcohols gave two diastereomeric products in about 1:1 ratio, (Z)-allylic alcohols gave the corresponding product as a single diastereomer. 相似文献
79.
To make clear the reason of unsuitability of poly(vinyl alcohol) (PVA) protective colloid for the emulsion polymerization
of conjugated monomers, a model experiment of emulsion polymerization of methyl methacrylate (MMA) was carried out with ammonium
persulfate (APS) or azobis(isobutyronitrile) (AIBN) initiators, where a small amount of MMA (1/100th of the concentration
compared with ordinary emulsion polymerization) was employed. This corresponds to the initial stage of the emulsion polymerization.
Grafting of MMA onto PVA took place remarkably irrespective of the kind of the initiators. Formation of homo-poly(MMA) was
observed to a small extent. The formation of new emulsion particles smaller than 100 nm continued to increase to almost the
end of the polymerization. PVA molecules in the grafted polymer are supposed to act as stabilizers of newly formed particles.
From kinetic treatment using the experimental data, the important issues were derived as follows. Firstly, the sulfate anion
radical from APS is much more reactive than the isobutyronitrile radical from AIBN in terms of hydrogen abstraction from PVA.
Secondly, high grafting ability of the latter initiator system, notwithstanding the much lower reactivity in the hydrogen
abstraction compared with the APS system, is attributed to the relative reactivity of the primary radicals, i.e., hydrogen
abstraction reaction from PVA to initiation reaction with MMA. The much slower rate of addition of the isobutyronitrile radical
to the monomer compared with that of hydrogen abstraction from PVA facilitates the grafting, although the rate constant of
hydrogen abstraction is far smaller than that with the sulfate anion radical by 10−4 times.
Received: 26 April 2001 Accepted: 6 September 2001 相似文献
80.
锌和锡参与下末端环氧化物的选择性烯丙基化反应 总被引:1,自引:0,他引:1
烯丙基溴和金属辛或锡成功地将末端环氧化合物1一锅法合成高烯丙基醇2和双高烯丙基醇3. 还研究了环氧化合物取代基的影响, 并提出了此烯丙基化的反应途径 . 相似文献