全文获取类型
收费全文 | 836篇 |
免费 | 39篇 |
国内免费 | 177篇 |
专业分类
化学 | 941篇 |
晶体学 | 7篇 |
力学 | 20篇 |
综合类 | 12篇 |
数学 | 11篇 |
物理学 | 61篇 |
出版年
2023年 | 2篇 |
2022年 | 5篇 |
2021年 | 11篇 |
2020年 | 15篇 |
2019年 | 19篇 |
2018年 | 21篇 |
2017年 | 19篇 |
2016年 | 30篇 |
2015年 | 18篇 |
2014年 | 29篇 |
2013年 | 72篇 |
2012年 | 54篇 |
2011年 | 46篇 |
2010年 | 48篇 |
2009年 | 49篇 |
2008年 | 48篇 |
2007年 | 50篇 |
2006年 | 51篇 |
2005年 | 55篇 |
2004年 | 51篇 |
2003年 | 40篇 |
2002年 | 54篇 |
2001年 | 34篇 |
2000年 | 44篇 |
1999年 | 26篇 |
1998年 | 24篇 |
1997年 | 27篇 |
1996年 | 14篇 |
1995年 | 19篇 |
1994年 | 18篇 |
1993年 | 12篇 |
1992年 | 9篇 |
1991年 | 7篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1987年 | 1篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1977年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有1052条查询结果,搜索用时 31 毫秒
1.
Synthesis of diisocyanides with phenolic groups and their polymerization to helically chiral poly(quinoxaline‐2,3‐diyl)s 下载免费PDF全文
Johannes Scholz Michael Reggelin 《Journal of polymer science. Part A, Polymer chemistry》2015,53(11):1320-1329
The development of synthetic routes which lead to five new diisocyanide monomers with one or two phenolic groups is described. Their polymerization behavior is studied with Pd‐ and Ni‐based initiators, as well as under microwave irradiation. The polymerizability is mainly dominated by steric effects as is concluded from experiments using different protecting groups. Chiroptical properties of these new polymers are studied by CD‐spectroscopy. After deprotection, helically chiral poly(quinoxalin‐2,3‐diyl)s are obtained which display a Brønsted function attached to a stereolabile biaryl axis whose configuration should be influenced by the chiral polymer backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1320–1329 相似文献
2.
Chin‐Ping Yang Ruei‐Shin Chen Kuei‐Hung Chen 《Journal of polymer science. Part A, Polymer chemistry》2003,41(7):922-938
To investigate the position and amount of the CF3 group affecting the coloration of polyimides (PIs), we prepared 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]hexafluoropropane ( 2 ) with four CF3 groups with 2‐chloro‐5‐nitrobenzotrifluoride and 2,2‐bis(4‐hydroxyphenol)hexafluoropropane. A series of soluble and light‐colored fluorinated PIs ( 5 ) were synthesized from 2 and various aromatic dianhydrides ( 3a – 3f ). 5a – 5f had inherent viscosities ranging from 0.80 to 1.19 dL/g and were soluble in amide polar solvents and even in less polar solvents. The glass‐transition temperatures of 5 were 221–265 °C, and the 10% weight‐loss temperatures were above 493 °C. Their films had cutoff wavelengths between 343 and 390 nm, b* values (a yellowness index) ranging from 5 to 41, dielectric constants of 2.68–3.01 (1 MHz), and moisture absorptions of 0.03–0.29 wt %. In a comparison of the PI series 6 – 8 based on 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane, we found that the CF3 group close to the imide group was more effective in lowering the color; this means that CF3 of 5 , 7 , and 8f was more effective than that of 6c . The color intensity of the four PI series was lowered in the following order: 5 > 7 > 6 > 8 . The PI 5f , synthesized from diamine 2 and 4,4′‐hexafluoroisopropylidenediphthalic anhydride, had six CF3 groups in a repeated segment, so it exhibited the lightest color among the four series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 922–938, 2003 相似文献
3.
R. Jayakumar Y.‐S. Lee S. Nanjundan 《Journal of polymer science. Part A, Polymer chemistry》2003,41(18):2865-2878
The calcium salt of mono(hydroxyethoxyethyl)phthalate [Ca(HEEP)2] was synthesized by the reaction of diethylene glycol, phthalic anhydride, and calcium acetate. Calcium‐containing poly(urethane ether)s (PUEs) were synthesized by the reaction of hexamethylene diisocyanate (HMDI) or tolylene 2,4‐diisocyanate (TDI) with a mixture of Ca(HEEP)2 and poly(ethylene glycol) (PEG300 or PEG400) with di‐n‐butyltin dilaurate as a catalyst. A series of calcium‐containing PUEs of different compositions were synthesized with Ca(HEEP)2/PEG300 (or PEG400)/diisocyanate (HMDI or TDI) molar ratios of 2:2:4, 3:1:4, and 1:3:4 so that the coating properties of the PUEs could be studied. Blank PUEs without calcium‐containing ionic diols were also prepared by the reaction of PEG300 or PEG400 with HMDI or TDI. The PUEs were well characterized by Fourier transform infrared, 1H and 13C NMR, solid‐state cross‐polarity/magic‐angle‐spinning 13C NMR, viscosity, solubility, and X‐ray diffraction studies. The thermal properties of the polymers were also studied with thermogravimetric analysis and differential scanning calorimetry. The PUEs were applied as top coats on acrylic‐coated leather, and their physicomechanical properties were also studied. The coating properties of PUEs, such as the tensile strength, elongation at break, tear strength, water vapor permeability, flexing endurance, cold crack resistance, abrasion resistance, color fastness, and adhesive strength, were better than the standard values. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2865–2878, 2003 相似文献
4.
KunHuaLIN MaoPingSONG ChenXiaDU QiaoHongZHANG YangJieWU 《中国化学快报》2003,14(7):673-676
The cyclomercurated ferrocenylimines containing heterocyclic ring were prepared by the condensation of cyclomercuration of acylferrocene with the appropriate heterocyclic amine.This procedure provides an efficient method for the synthesis of cyclomerucurated ferrocenylimines containing heterocyclic ring which are difficultly synthesized by the conventional method.The reaction mechanism is proposed. 相似文献
5.
A novel copolymer, poly(N‐hexyl‐3,7‐phenothiazylene‐1,2‐ethenylene‐2,6‐pyridylene‐1,2‐ethenylene) ( P3 ), containing N‐hexyl‐3,7‐phenothiazylene and 2,6‐pyridylene chromophores was synthesized to investigate the effect of protonation, metal complexation, and chemical oxidation on its absorption and photoluminescence (PL). Poly(N‐hexyl‐3,8‐iminodibenzyl‐1,2‐ethenylene‐1,3‐phenylene‐1,2‐ethenylene) and poly(N‐hexyl‐3,7‐phenothiazylene‐1,2‐ethenylene‐1,3‐phenylene‐1,2‐ethenylene) ( P2 ), consisting of 1,3‐divinylbenzene alternated with N‐hexyl‐3,8‐iminodibenzyl and N‐hexyl‐3,7‐phenothiazylene, respectively, were also prepared for comparison. Electrochemical investigations revealed that P3 exhibited lower band gaps (2.34 eV) due to alternating donor and acceptor conjugated units (push–pull structure). The absorption and PL spectral variations of P3 were easily manipulated by protonation, metal chelation, and chemical oxidation. P3 displayed significant bathochromic shifts when protonated with trifluoroacetic acid in chloroform. The complexation of P3 with Fe3+ led to a significant absorption change and fluorescence quenching, and this implied the coordination of ferric ions with the 2,6‐pyridylene groups in the backbone. Moreover, both phenothiazylene‐containing P2 and P3 showed conspicuous PL quenching with a slight redshift when oxidized with NOBF4. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1272–1284, 2004 相似文献
6.
New Schiff bases of 2,4‐dihydroxybenzaldehyde with siloxane‐α,ω‐diamines having different numbers of siloxane units in the chain have been synthesized and characterized by spectroscopy, elemental and thermal analyses. These azomethines were found to form complexes readily with copper(II), nickel(II), cobalt(II), cadmium(II) and zinc(II). From IR and UV–Vis studies, the phenolic oxygen and imine nitrogen of the ligand were found to be the coordination sites. Thermogravimetric analysis (TGA) data indicate the chelates to be more stable than the corresponding ligands. The melting points increase with shortening of the siloxane segment from azomethine, as well as the result of complexation. The chelates obtained were covalently inserted in polymeric linear structures by polycondensation through the OH‐difunctionalized ligand with 1,3‐bis(carboxypropyl)tetramethyldisiloxane. Direct polycondensation, assisted either by acetic anhydride or N,N′‐dicyclohexylcarbodiimide as dehydrating agent and the complex 4‐(dimethylamino)pyridinium 4‐toluenesulfonate as catalyst, was used for the synthesis of these compound types. The structures of the polymers obtained were confirmed by IR, UV and 1H NMR. Characterization was undertaken by TGA, solubility tests and viscosity measurements. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
7.
Michelina Soccio Lara Finelli Nadia Lotti Valentina Siracusa Tiberio A. Ezquerra Andrea Munari 《Journal of Polymer Science.Polymer Physics》2007,45(13):1694-1703
Poly(butylene naphthalate) (PBN), poly(diethylene naphthalate) (PDEN), and poly(thiodiethylene naphthalate) (PTDEN) were synthesized and characterized in terms of chemical structure and molecular weight. The polyesters were examined by TGA, DSC, and DMTA. All the polymers showed a good thermal stability, even though depending on chemical structure. At room temperature they appeared as semicrystalline materials; the effect of the introduction along the PBN polymer chain of ether oxygen atoms or sulfur ones was a lowering in the Tg value, a decrement of Tm, and a decrease of the crystallization rate. Changing in chemical structure also affects the main α absorption associated with the glass transition which moves to lower temperature and whose energetic requirements decrease. The results were explained as due to the presence of highly flexible C? S? C or C? O? C bonds in the polymeric chain. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1694–1703, 2007 相似文献
8.
Huricha Baigude Kaname Katsuraya Kohsaku Okuyama Kenichi Hatanaka Emi Ikeda Naokazu Shibata Toshiyuki Uryu 《Journal of polymer science. Part A, Polymer chemistry》2004,42(6):1400-1414
A novel sugar‐containing poly(ornithine) dendrimer is synthesized for possible antigen delivery and related applications. The dendrimer contains an ornithine dendron as interior scaffolding and oligosaccharides on the periphery, which provide an attachment site for a peptide antigen. Maltose or lactose is bound to both hemispherical and spherical poly(ornithine) dendrimer generation 3 (G3) by reductive amination between its reducing end and the peripheral amino group of the dendrimer using a borane‐pyridine complex in a buffer solution at 50 °C. The degree of substitution of sugar is changed by varying the molar ratio of sugar to dendrimer. When the surface of spherical poly(ornithine) dendrimer G3 is modified by binding β‐alanine to the 16 amino groups, highly substituted maltose‐ or lactose‐β‐alanine‐poly(ornithine) dendrimer G3 is obtained in high yield after 7 days of reaction. The structures of these sugar‐containing dendrimers are characterized by NMR and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analyses. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1400–1414, 2004 相似文献
9.
A method for direct sulfenylation of aldehydes and ketones, catalyzed by a novel pyrrolidine trifluoromethanesulfonamide organocatalyst, has been developed. This process serves as an efficient and mild approach to the preparation of α-phenylthio-ketones and -aldehydes. 相似文献
10.
Mitsunori Oda Yosuke Fukuchi Satoshi Ito Nguyen Chung Thanh Shigeyasu Kuroda 《Tetrahedron letters》2007,48(52):9159-9162
Reactions of pyrrolidine with 2 equiv of aldehydes without any catalyst in a pressurized vessel at 140–200 °C yielded 1,3-disubstituted pyrroles. -Branched aldehydes gave fairly good yields of the corresponding products by this method, which provides a facile non-oxidative procedure for synthesizing 1,3-dialkylpyrroles from inexpensive pyrrolidine and aldehydes. 相似文献