全文获取类型
收费全文 | 804篇 |
免费 | 25篇 |
国内免费 | 14篇 |
专业分类
化学 | 831篇 |
晶体学 | 3篇 |
物理学 | 9篇 |
出版年
2024年 | 1篇 |
2023年 | 1篇 |
2022年 | 6篇 |
2021年 | 10篇 |
2020年 | 6篇 |
2019年 | 17篇 |
2018年 | 10篇 |
2017年 | 14篇 |
2016年 | 18篇 |
2015年 | 19篇 |
2014年 | 20篇 |
2013年 | 42篇 |
2012年 | 38篇 |
2011年 | 42篇 |
2010年 | 48篇 |
2009年 | 49篇 |
2008年 | 70篇 |
2007年 | 66篇 |
2006年 | 44篇 |
2005年 | 51篇 |
2004年 | 56篇 |
2003年 | 51篇 |
2002年 | 59篇 |
2001年 | 17篇 |
2000年 | 6篇 |
1999年 | 6篇 |
1998年 | 10篇 |
1997年 | 14篇 |
1996年 | 9篇 |
1995年 | 7篇 |
1994年 | 10篇 |
1993年 | 18篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1983年 | 1篇 |
排序方式: 共有843条查询结果,搜索用时 15 毫秒
51.
Sung-Jae Chung Seung-Moo Huh Jung-Il Jin 《Journal of polymer science. Part A, Polymer chemistry》1996,34(6):1105-1112
A series of new wholly aromatic polyesters was synthesized by melt polycondensation of 1-phenyl-2,6-naphthalenedicarboxylic acid (PNDA) and diacetates of various aromatic diols. The aromatic diols studied are hydroquinone (HQ), methylhydroquinone (MHQ), phenylhydroquinone (PHQ), (α-phenylisopropyl)hydroquinone (PIHQ), 2,6-naphthalenediol (2,6-ND), 1,4-naphthalenediol (1,4-ND), and 4,4′-biphenol (BP). These polyesters were characterized for their crystallinity, glass transition temperature (Tg), melting temperature (Tm), liquid crystallinity, and thermal stability. In general, crystallinity of the polyesters are very low and the Tg values of the polyesters range from 150 to 172°C depending on the structure of aromatic diols. All of the polymers formed nematic phases above their Tm or Tg. The polyesters derived from PHQ and PIHQ are soluble in chlorinated hydrocarbon solvents. The initial decomposition temperatures of the polyesters are above 400°C under N2 atmosphere. © 1996 John Wiley & Sons, Inc. 相似文献
52.
Melt or cold crystallization kinetics has a strong bearing on morphology and the extent of crystallization, which significantly affects the physical properties of polymeric materials. Nonisothermal crystallization kinetics are often analyzed by the classical Johnson–Mehl–Avrami–Kolmogorov (JMAK) model or one of its variants, even though they are based on an isothermal assumption. As a result, during the nonisothermal (e.g. constant heating or cooling rate) crystallization of polymeric material, different sets of model parameters are required to describe crystallization at different rates, thereby increasing the total number of model parameters. In addition, due to the uncorrelated nature of these model parameters with the cooling or heating rate, accurate modeling at any intermediate condition is not possible. In the present work, these two limitations of the conventional approach have been eliminated by exhibiting the existence of a functional relationship between cooling or heating rate and effective activation energy during nonisothermal melt or cold crystallization in three linear aromatic polyesters. Furthermore, it has been shown that when the JMAK model is used in conjunction with this functional relationship, it is possible to precisely predict the experimental nonisothermal melt or cold crystallization kinetics at any linear cooling or heating rate with a single set of model parameters. 相似文献
53.
Anna Kultys Wawrzyniec Podkocielny Stanisaw Pikus 《Journal of polymer science. Part A, Polymer chemistry》1998,36(13):2359-2369
Two series of new linear polyesters containing sulfur in the main chain were obtained by melt polycondensation of naphthalene-1,4-bis(methylthioacetic acid) (N-1,4-BMTAA) or naphthalene-1,5-bis(methylthioacetic acid) (N-1,5-BMTAA) with some aliphatic diols using a 0.05 molar excess of diol. Softening temperatures ranging from 55 to 130°C, reduced viscosities in the range of 0.15–0.39 dL/g, and low-molecular weights were their characteristic. The structure and thermal properties of all polyesters were examined by using elemental analysis, FT-IR and 1H-NMR spectroscopy, X-ray diffraction analysis, differential thermal analysis (DTA), thermogravimetric analysis (TGA), and differential scanning calorymetry (DSC). The kinetics of polyester formation by uncatalyzed melt polycondensation was studied in a model system: N-1,4-BMTAA or N-1,5-BMTAA and 2,2′-oxydiethanol (ODE) at 150, 160, and 170°C. Reaction rate constants (k3) and activation parameters (ΔG‡, ΔH‡, ΔS‡) from carboxyl group loss were determined using classical kinetic methods. Hydroxyl-terminated polyesters derived from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol were used for preparation of the polyurethanes by melt polyaddition with hexamethylene diisocyanate (HDI). They were characterized by reduced viscosity, FT-IR spectroscopy, X-ray diffraction analysis, TGA, DSC, polarizing microscope observation, and hardness and tensile properties. The resulting polyurethanes behave like high-elasticity thermoplastic elastomers, except the one derived from N-1,5-BMTAA and 1,6-hexanediol-based polyester. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2359–2369, 1998 相似文献
54.
Kontoyianni C Sideratou Z Theodossiou T Tziveleka LA Tsiourvas D Paleos CM 《Macromolecular bioscience》2008,8(9):871-881
A hyperbranched aliphatic polyester has been functionalized with PEG chains to afford a novel water-soluble BH40-PEG polymer which exhibits unimolecular micellar properties, and is therefore appropriate for application as a drug-delivery system. The solubility of the anticancer drug paclitaxel was enhanced by a factor of 35, 110, 230, and 355 in aqueous solutions of BH40-PEG of 10, 30, 60, and 90 mg x mL(-1), respectively. More than 50% of the drug is released at a steady rate and release is almost complete within 10 h. The toxicity of BH40-PEG was assessed in vitro with A549 human lung carcinoma cells and found to be nontoxic for 3 h incubation up to a 1.75 mg x mL(-1) concentration while LD50 was 3.5 mg x mL(-1). Finally, it was efficiently internalized in cells, primarily in the absence of foetal bovine serum, while confocal microscopy revealed the preferential localization of the compound in cell nuclei. [Figure: see text]. 相似文献
55.
Abraham J. Domb 《Journal of polymer science. Part A, Polymer chemistry》1993,31(8):1973-1981
Blends of biodegradable polymers having properties distinct from the individual polymer components, and that are suitable for use as carriers of pharmaceutically active agents, were prepared from two or more polyanhydrides, polyesters, and mixtures of polyanhydrides and low molecular weight polyesters. The blends have different properties than the original polymers, providing a mean for altering the characteristics of the polymeric matrix without altering the chemical structure of the component polymers. Aliphatic, aromatic, and copolymers of polyanhydrides were miscible in each other and formed less crystalline compositions with a single melting point which was lower than the melting point of the starting polymers. The polyesters: poly(lactide-glycolide), poly(caprolactone), and poly(hydroxybutyric acid) presented some miscibility in each other. However, the polyanhydrides were immiscible with the polyesters resulting in a complete phase separation both in solution or in melt mixing. Only low molecular weight polyesters (in the range of 2000) of lactide and glycolide, mandelic acid, propylenefumarate, and caprolactone presented some miscibility with polyanhydrides. Similarly, poly(orthoester) and hydroxybutyric acid polymers formed a uniform mixture with the anhydride polymers which had the two melting points of the original polymers. Drug release from polymer blends composed of poly(hydroxybutyric acid) or low molecular weight poly(lactic acid) with poly(sebacic anhydride) (PSA) showed a constant release of drug for periods from 2 weeks to several months as a function of the PSA content in the blend. Increasing the content of PSA, a fast degrading polymer, increases the release rate from the blend. © 1993 John Wiley & Sons, Inc. 相似文献
56.
海洋天然产物研究新进展 总被引:12,自引:0,他引:12
海洋天然产物化学是目前天然产物化学中最活跃的研究领域之一。近年来,从海洋生物中分离到非常多的化学结构和生理活性上令人注目的新化合物,引起了有机化学家和药物化学家的关注。本文按萜类、太环内酯、聚醚类、生物碱,环肽、含氰化合物、甾醇、聚丙酸酯类化合物等化学结构来概述海洋天然产物研究近年来的进展。 相似文献
57.
Sarah El Habnouni Vincent Darcos Jean Coudane 《Macromolecular rapid communications》2009,30(3):165-169
A new functional lactone, α‐iodo‐ε‐caprolactone (αIεCL), was synthesized from ε‐caprolactone by anionic activation using a non‐nucleophilic strong base (lithium diisopropylamide) followed by an electrophilic substitution with iodine chloride. Ring‐opening (co)polymerizations of the resulting monomer with ε‐caprolactone were carried out using tin 2‐ethylhexanoate as a catalyst in toluene at 100 °C. Homopolymerization of αIεCL was achieved, and poly(αIεCL) was fully characterized by SEC, 1H NMR and elemental analysis. Random copolymerizations of αIεCL with εCL were controlled with experimental molecular weights close to the theoretical values, narrow molecular weight distributions and a good agreement between experimental and theoretical molar compositions of αIεCL.
58.
Xin Li Yinghong Zhu Jun Ling Zhiquan Shen 《Macromolecular rapid communications》2012,33(11):1008-1013
Unmodified β‐cyclodextrin has been directly used to initiate ring‐opening polymerization of ϵ‐caprolactone in the presence of yttrium trisphenolate. Well‐defined cyclodextrin (CD)‐centered star‐shaped poly(ϵ‐caprolactone)s have been successfully synthesized containing definite average numbers of arms (Narm = 4–6) and narrow polydispersity indexes (below 1.10). The number‐average molecular weight ( ) and average molecular weight per arm ( ) are controlled by the feeding molar ratio of monomer to initiator. The prepared star‐PCL with of 2.7 × 103 is in fully amorphous and that with of 13.3 × 103 is crystallized. In addition, the obtained poly(e‐caprolactone) (PCL) stars with various molecular weights have different solubilities in methanol and tetrahydrofuran, which can be applied for further modifications. 相似文献
59.
60.
Comprehensive mathematical model based on the kinetics and thermodynamic equations is developed to examine a coesterification concept of biodegradable aliphatic‐aromatic copolyesters, poly(butylene succinate‐co‐butylene terephthalate) (PBST). The simulation results for batch process are validated with pilot experimental data. The continuous process is further studied to figure out the coesterification performance of succinic acid (SA) and terephthalic acid (TPA) with different reaction activities and thermodynamic properties in terms of reaction efficiency, small molecular evaporation and product quality. There is a compromise between the operating conditions of the two systems of SA/1,4‐butanediol (BDO) and TPA/BDO. Proper pressure reduction is beneficial to reaction efficiency and product quality. The way to increase reaction efficiency by raising temperature is limited due to the serious evaporation of reactants. Influenced by the solid–liquid equilibrium and the slow reaction rate of TPA, the esterification of acid needs sufficient residence time to complete. 相似文献