全文获取类型
收费全文 | 1093篇 |
免费 | 46篇 |
国内免费 | 94篇 |
专业分类
化学 | 1127篇 |
晶体学 | 7篇 |
力学 | 22篇 |
综合类 | 4篇 |
数学 | 5篇 |
物理学 | 68篇 |
出版年
2023年 | 4篇 |
2022年 | 5篇 |
2021年 | 10篇 |
2020年 | 17篇 |
2019年 | 18篇 |
2018年 | 18篇 |
2017年 | 26篇 |
2016年 | 39篇 |
2015年 | 36篇 |
2014年 | 28篇 |
2013年 | 89篇 |
2012年 | 44篇 |
2011年 | 50篇 |
2010年 | 47篇 |
2009年 | 47篇 |
2008年 | 72篇 |
2007年 | 76篇 |
2006年 | 55篇 |
2005年 | 62篇 |
2004年 | 66篇 |
2003年 | 62篇 |
2002年 | 55篇 |
2001年 | 37篇 |
2000年 | 39篇 |
1999年 | 34篇 |
1998年 | 27篇 |
1997年 | 32篇 |
1996年 | 29篇 |
1995年 | 21篇 |
1994年 | 29篇 |
1993年 | 18篇 |
1992年 | 17篇 |
1991年 | 5篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 2篇 |
排序方式: 共有1233条查询结果,搜索用时 890 毫秒
1.
Naoto Takase Junpei Kuwabara Seong Jib Choi Takeshi Yasuda Liyuan Han Takaki Kanbara 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):536-542
The Pd‐catalyzed polycondensation of 4‐octylaniline with various dibromoarylenes was carried out under microwave heating. Microwave heating led to a decrease in the reaction time and an increase in the molecular weight of the polymers as compared to conventional heating. Microwave heating also allowed the catalyst loading to be reduced to 1 mol %, yielding polymerization results that were comparable to those under conventional heating and 5 mol % catalyst. Investigations regarding field‐effect transistors and organic photovoltaic cells using the obtained poly(arylamine) with azobenzene units revealed that increasing the molecular weight of the polymer led to improved device performance, including hole mobility and power conversion efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 536–542 相似文献
2.
Haitao Qian Edith Mathiowitz 《Journal of polymer science. Part A, Polymer chemistry》2007,45(24):5899-5915
We succeeded in developing the acyl chloride‐facilitated condensation polymerization method for the synthesis of new poly(anhydride‐ester)s with aromatic side groups, which cannot be polymerized by the classic melt condensation polymerization method. Using chlorinated and acylated carboxylic acids as the intermediates, the polymerization was carried out at low temperatures of 120 or 135 °C to yield pure poly(anhydride‐ester)s of molecular weights as high as 1.55 × 105 with minimal side‐reactions. A homogeneous route of preparation was developed and optimized, using butyric anhydride as the acylating reagent and oxalyl chloride as the chlorinating reagent. A comparison of the mechanisms of the classic method and the new method indicates that the effects of transacylation—cyclization and oligomer formation—were greatly reduced due to the high reactivity of carboxylic acid chloride and the steric effect of bulky acyl groups. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5899–5915, 2007 相似文献
3.
Peixiang Xing Gilles P. Robertson Michael D. Guiver Serguei D. Mikhailenko Serge Kaliaguine 《Journal of polymer science. Part A, Polymer chemistry》2004,42(12):2866-2876
A series of sulfonated poly(aryl ether ketone)s (SPAEKs) were prepared by aromatic nucleophilic polycondensation of 2,6‐dihydroxynaphthalene with 5,5′‐carbonyl‐bis(2‐fluorobenzenesulfonate) and 4,4′‐difluorobenzophenone. The structure and degree of sulfonation (DS) of the SPAEKs were characterized using 1H NMR spectroscopy. The experimentally observed DS values were close to the expected values derived from the starting material ratios. The thermal stabilities of the SPAEKs were characterized by thermogravimetric analysis, which showed that in acid and sodium salt forms they were thermally stable in air up to about 240 and 380 °C, respectively. Transparent membranes cast from the directly polymerized SPAEKs exhibited good mechanical properties in both dry and hydrated states. The dependence of water uptake and of membrane swelling on the DS at different temperatures was studied. SPAEK membranes with a DS from 0.72 to 1.60 maintained adequate mechanical properties after immersion in water at 80 °C for 24 h. The proton conductivity of SPAEK membranes with different degrees of sulfonation was measured as a function of temperature. The proton conductivity of the SPAEK films increased with increased DS, and the highest room temperature conductivity (4.2 × 10?2 S/cm) was recorded for a SPAEK membrane with a DS of 1.60, which further increased to 1.1 × 10?1 S/cm at 80 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2866–2876, 2004 相似文献
4.
Fukuji Higashi Kanako Sugishita 《Journal of polymer science. Part A, Polymer chemistry》2004,42(1):44-51
A two‐stage co‐oligomerization of the oligomers initially formed from an equimolar mixture of isophthalic acid (IPA) and terephthalic acid (TPA) and 2,2‐bis(4‐hydroxyphenyl)propane (BPA, 50 mol %) with bisphenols (BPs, 20 mol %) was carried out using a tosyl chloride/dimethylformamide/pyridine condensing agent. The distributions of the resulting oligomers (nx‐mers), which were quenched with methanol, were determined by a combination of gel permeation chromatography (GPC) and NMR. These distributions (presented by molar percentage) were conveniently calculated with the equation nx (mol %) = nx (% mol by GPC) × n0 (mol % by NMR)/n0 (% mol by GPC), where nx (% mol) = nx (wt % by GPC)/its molecular weight. The results showed the distributions of the preformed IPA/TPA‐BPA oligomers to be in fairly good accord with those obtained directly from GPC and to be supported by the NMR results. The calculation was applied to the co‐oligomers prepared up to a reaction of 0.7, at which there was an increase in the number of higher oligomers indivisible by GPC and the distributions could no longer be determined by molar percentage. The calculated distributions are discussed in relation to the results of copolycondensation. The sequence distributions in the resulting co‐oligomers, which were also examined by NMR, are compared with those in the copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 44–51, 2004 相似文献
5.
Zhaoqiang Lu Lin Cheng Jun Li Kai Zhang Song Yi Jingui Qin 《Journal of polymer science. Part A, Polymer chemistry》2004,42(4):925-932
The synthesis and structural characterization of a series of novel, fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties are described. The monomers, 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a – 2d ), were conveniently and efficiently synthesized from phenols and phthalic anhydride in two steps via 2‐(4′‐hydroxybenzoyl)benzoic acids, which were first obtained by the Friedel–Crafts reaction in good yields and with high stereoselectivity and were then converted into 2a – 2d by fusion with hydrazine. All the polymers were prepared by nucleophilic aromatic substitution (SNAr) polycondensation between the compounds perfluorobiphenyl and 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a ‐ 2d ). The resulting fluorinated polymers were readily soluble in common organic solvents (e.g., CHCl3, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, N‐methylpyrrolidone, etc.) at room temperature. Their weight‐average molecular weights and the polydispersities ranged from (7.96–18.25) × 103 to 1.31–2.71, respectively. Their glass‐transition temperatures varied from 213 to 263 °C. They were all stable up to 390 °C both in air and in argon. The 5% weight‐loss temperatures of these polymers in air and argon ranged from 393–487 to 437–509 °C, respectively. Wide‐angle X‐ray diffraction studies indicated they were all amorphous and could be attributed to the presence of kink nonplanar moiety, phenyl phthalazinone along the polymer backbone. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 925–932, 2004 相似文献
6.
Thomas Pautzsch Elisabeth Klemm 《Journal of polymer science. Part A, Polymer chemistry》2004,42(12):2911-2919
Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by 1H and 13C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004 相似文献
7.
Thomas Pautzsch Lars Blankenburg Elisabeth Klemm 《Journal of polymer science. Part A, Polymer chemistry》2004,42(3):722-732
A series of novel π-conjugated polymers containing ruthenium bipyridine complexes was synthesized by a cross-coupling reaction and characterized. These polymers exhibit absorption maxima around 330–350 nm (π-π*) and 460–500 nm metal-to-ligand charge transfer (MLCT), respectively. They are soluble in common organic solvents, and all polymers can be converted into transparent films. We investigated the influence of different donating and acceptor diethynylarenes of the ultraviolet-visible spectra. The oxidation potential, which was measured by cyclic- and square-wave voltametry, showed a typical Ru2+/3+ exhibited at 1.25 V versus the saturated calomel electrode. The polymers were further characterized with photoluminescence measurements. When excited at 442 nm ( 11a ), the polymer exhibited an emission peak at 690 nm. This peak was attributed to the MLCT states. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 722–732, 2004 相似文献
8.
Hans R. Kricheldorf Lali Vakhtangishvili Gert Schwarz 《Journal of polymer science. Part A, Polymer chemistry》2004,42(22):5725-5735
Poly(pyridine ether)s were prepared in two ways: the polycondensation of silylated 1,1,1‐tris(4‐hydroxyphenyl)ethane (THPE) with 2,6‐difluoropyridine (method A) and the polycondensation of free THPE with 2,6‐dichloropyridine (method B). With method A, the THPE/difluoropyridine feed ratio was varied from 1.0:1.0 to 1.0:1.6. Cycles, bicycles, and multicycles were the main reaction products, and crosslinking was never observed. When ideal stoichiometry was used exclusively, multicycles free of functional groups were obtained. These multicycles were detectable in matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) mass spectra up to B38C76 with a mass of approximately 32,000 Da. With method B, the reaction conditions were varied at a fixed feed ratio to achieve an optimum for the preparation of multicyclic polyethers, but because of the lower reactivity of 2,6‐dichloropyridine, a quantitative conversion was not achieved. The reaction products were characterized with MALDI‐TOF mass spectrometry, viscosity measurements, and size exclusion chromatography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5725–5735, 2004 相似文献
9.
Fukuji Higashi Kaori Kira 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2725-2733
The solution polyesterification of dicarboxylic acids in pyridine, the activated intermediates of which were difficult to dissolve in tosyl chloride/dimethylformamide/pyridine, was investigated in the presence of lithium chloride. The solubility of the activated dicarboxylic acids was largely improved by the presence of the salt, and the polycondensation with bisphenols was greatly facilitated. The salt was more effectively added to a pyridine solution of dicarboxylic acids than to the activated dicarboxylic acids in pyridine. The favorable additive effect on the improved solubility was attributed to a lowered degree of association of the activated dicarboxylic acids, which led to distributions of the resulting oligomers from bisphenols at an earlier stage closer to the theoretical ones and yielded better polycondensation results. The reaction, which proceeded through favorable distributions of the co‐oligomers, produced copolymers of higher inherent viscosities and slightly block sequence distributions determined by NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2725–2733, 2004 相似文献
10.
A two-dimensional model for the simulation of a binary dendritic growth with convection has been developed in order to investigate the effects of convection on dendritic morphologies. The model is based on a cellular automaton (CA) technique for the calculation of the evolution of solid/liquid (s/l) interface. The dynamics of the interface controlled by temperature, solute diffusion and Gibbs–Thomson effects, is coupled with the continuum model for energy, solute and momentum transfer with liquid convection. The solid fraction is calculated by a governing equation, instead of some approximate methods such as lever rule method [A. Jacot, M. Rappaz, Acta Mater. 50 (2002) 1909–1926.] or interface velocity method [L. Nastac, Acta Mater. 47 (1999) 4253; L. Beltran-Sanchez, D.M. Stefanescu, Mat. and Mat. Trans. A 26 (2003) 367.]. For the dendritic growth without convection, mesh independency of simulation results is achieved. The simulated steady-state tip velocity are compared with the predicted values of LGK theory [Lipton, M.E. Glicksmanm, W. Kurz, Metall. Trans. 18(A) (1987) 341.] as a function of melt undercooling, which shows good agreement. The growth of dendrite arms in a forced convection has been investigated. It was found that the dendritic growth in the upstream direction was amplified, due to larger solute gradient in the liquid ahead of the s/l interface caused by melt convection. In the isothermal environment, the calculated results under very fine mesh are in good agreement with the Oseen–Ivanstov solution for the concentration-driven growth in a forced flow. 相似文献