全文获取类型
收费全文 | 890篇 |
免费 | 53篇 |
国内免费 | 22篇 |
专业分类
化学 | 928篇 |
晶体学 | 1篇 |
力学 | 7篇 |
综合类 | 2篇 |
数学 | 4篇 |
物理学 | 23篇 |
出版年
2024年 | 1篇 |
2023年 | 6篇 |
2022年 | 17篇 |
2021年 | 22篇 |
2020年 | 14篇 |
2019年 | 30篇 |
2018年 | 18篇 |
2017年 | 24篇 |
2016年 | 38篇 |
2015年 | 33篇 |
2014年 | 37篇 |
2013年 | 61篇 |
2012年 | 46篇 |
2011年 | 40篇 |
2010年 | 54篇 |
2009年 | 52篇 |
2008年 | 74篇 |
2007年 | 57篇 |
2006年 | 51篇 |
2005年 | 70篇 |
2004年 | 59篇 |
2003年 | 53篇 |
2002年 | 42篇 |
2001年 | 20篇 |
2000年 | 7篇 |
1999年 | 13篇 |
1998年 | 5篇 |
1997年 | 6篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1994年 | 5篇 |
1993年 | 4篇 |
1992年 | 1篇 |
1984年 | 1篇 |
排序方式: 共有965条查询结果,搜索用时 15 毫秒
831.
Yu‐En Tai Chen‐Yu Li Chia‐Her Lin Yi‐Chang Liu Bao‐Tsan Ko Ya‐Sen Sun 《Journal of polymer science. Part A, Polymer chemistry》2011,49(18):4027-4036
A series of efficient zinc catalysts supported by sterically bulky benzotriazole phenoxide ( BTP ) ligands are synthesized and structurally characterized. The reactions of diethyl zinc (ZnEt2) with CMe2PhBTP ‐H, t‐BuBTP ‐H, and TMClBTP ‐H yield monoadduct [(μ‐ BTP )ZnEt]2 ( 1 – 3 ), respectively. Bisadduct complex [( t‐BuBTP )2Zn] ( 4 ) results from treatment of ZnEt2 with t‐BuBTP ‐H (2 equiv.) in toluene, but treatment of TMClBTP ‐H with ZnEt2 in the same stoichiometric proportion in Et2O produces five‐coordinated monomeric complex [( TMClBTP )2Zn(Et2O)] ( 5 ). The molecular structures of compounds 1 , 4 , and 5 are characterized by X‐ray crystal structure determinations. All complexes 1 – 5 are efficient catalysts for the ring‐opening polymerization of ε‐caprolactone (ε‐CL) in the presence of 9‐anthracenemethanol. Experimental results indicate that complex 3 exhibits the greatest activity with well‐controlled character among these complexes. The polymerizations of ε‐CL and β‐butyrolactone catalyzed by 3 are demonstrated in a “living” character with narrow polydispersity indices (monomer‐to‐initiator ratio in the range of 25–200, PDIs ≤ 1.10). The “immortal” character of 3 provides a way to synthesize as much as 16‐fold polymer chains of poly(ε‐CL) (PCL) with narrow PDI in the presence of a catalyst in a small proportion. The controlled fashion of complex 3 also enabled preparation of the PCL‐b‐poly(3‐hydroxybutyrate) copolymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
832.
Weipu Zhu Shuai Sun Ning Xu Zhiquan Shen 《Journal of polymer science. Part A, Polymer chemistry》2011,49(23):4987-4992
The ring‐opening copolymerization of methyl ethylene phosphate (MEP, 2‐methoxy‐2‐oxo‐1,3,2‐dioxaphospholane) and ε‐caprolactone (CL) was performed in bulk with lanthanum tris(2,6‐di‐tert‐butyl‐4‐methylphenolate)s as single‐component catalyst, resulting in poly(ester‐phosphoester) random copolymers with high molecular weight and moderate molecular weight distribution. The properties of the copolymers were characterized by differential scanning calorimetry, X‐ray diffractometer, dynamic mechanical analysis, and static water contact angle measurement. The crystallinities of the copolymers were reduced with the increase of MEP molar fraction in the products. Moreover, copolymers with enhanced hydrophilicity and lower glass transition temperature could be obtained with higher MEP content, which may provide potential applications in biomedical field. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011. 相似文献
833.
Li Zhang Yakai Feng Hong Tian Miao Zhao Musammir Khan Jintang Guo 《Journal of polymer science. Part A, Polymer chemistry》2013,51(15):3213-3226
Well‐defined amphiphilic multiblock copolymers PDMAEMA‐b‐P(IBMD‐co‐PDO)‐b‐PEG‐b‐P(IBMD‐co‐PDO)‐b‐PDMAEMA [PDMAEMA‐PIBMD‐PPDO‐PEG], based on poly(2‐(dimethylamino)ethyl methacrylate) block (PDMAEMA), poly(3(S)‐isobutyl‐morpholine‐2,5‐dione‐co‐p‐dioxanone) block (P(IBMD‐co‐PDO)), and poly(ethylene glycol) block (PEG) were successfully synthesized by combination of ring‐opening polymerization (using 3(S)‐isobutyl‐morpholine‐2,5‐dione and p‐dioxanone initiated by hydroxyl end of PEG) and atom transfer radical polymerization (ATRP). Furthermore, all these copolymers were characterized by 1H NMR, 13C NMR, Fourier transformed‐infrared, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis measurements. The degradation experiments showed that the molecular weight of PDMAEMA‐PIBMD‐PPDO‐PEG decreased along with degradation time. In addition, these copolymers could readily self‐assemble into nanosized microspheres in phosphate buffered solution. Ibuprofen (IBU) and doxorubicin (DOX) as a kind of combined model drugs were loaded into these microspheres by the combination of ionic interaction and hydrophobic effect. These copolymer microspheres exhibited high loading capacity (LC, up to 26.88%), encapsulation efficiency (EE, up to 61.29%), and sustained release behavior of IBU–DOX in phosphate buffered solution. The results of transmission electron microscopy and dynamic light scattering showed that the microspheres were well‐defined uniform spherical particles with average diameter less than 120 nm. Therefore, it can be envisaged that these copolymer systems are promising candidates for controlled release application. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3213–3226 相似文献
834.
835.
Soliman Mehawed Abdellatif Soliman Cécile Nouvel Jérôme Babin Jean‐Luc Six 《Journal of polymer science. Part A, Polymer chemistry》2014,52(15):2192-2201
Polymers containing o‐nitrobenzyl esters are promising for preparation of light sensitive materials. o‐Nitrobenzyl methacrylate has already been polymerized by controlled ATRP or RAFT. Unfortunately, the radical polymerization of o‐nitrobenzyl acrylate (NBA) was not controlled until now due to inhibition and retardation effects coming from the nitro‐aromatic groups. Recent developments in the Single Electron Transfer–Living Radical Polymerization (SET–LRP) provide us an access to control this NBA polymerization and living character of this NBA SET–LRP is demonstrated. Effects of CuBr2 and ligand concentrations, as well as Cu(0) wire length on SET–LRP kinetics are shown presently. A first‐order kinetics with respect to the NBA concentration is observed after one induction period. SET–LRP proceeds with a linear evolution of molecular weight and a narrow distribution. High initiation efficiency close to 1 and high chain‐end functionality (~93%) are reached. Chain extension of poly(o‐nitrobenzyl acrylate) is realized with methyl acrylate (MA) to obtain well defined poly(o‐nitrobenzyl acrylate)‐b‐poly(methyl acrylate) (PNBA‐b‐PMA). Finally, light‐sensitive properties of PNBA are checked upon UV irradiation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2192–2201 相似文献
836.
Yuushou Nakayama Takamichi Inaba Yosuke Toda Ryo Tanaka Zhengguo Cai Takeshi Shiono Hiroyuki Shirahama Chikara Tsutsumi 《Journal of polymer science. Part A, Polymer chemistry》2013,51(20):4423-4428
l ‐Lactide (l ‐LA) was polymerized in the presence of N‐methyldiethanolamine as an initiator and Sn(Oct)2 as a catalyst to give hydroxy‐telechelic poly(l ‐lactide) (PLLA‐diol) bearing a tertiary amine group at the center of the polymer chain. Successive chain extension of the PLLA‐diol with hexamethylene diisocyanate afforded PLLA‐based poly(ester‐urethane)s (PEU) with equally spaced tertiary amine groups. Treatment of the PEU with iodomethane converted tertiary amine groups to quaternary ammonium groups to give cationic ionomers (PEU‐MeI). The thermal, mechanical, hydrophilic, and biodegradation properties of the obtained polymers were investigated. The thermal properties of the PEUs and the PEU‐MeIs were similar each other. The PEU‐MeIs exhibited higher tensile modulus than those of the starting PEUs. The contact angles of water on the PEU‐MeIs were lower than those of the PEUs with similar NMDA content indicating their higher hydrophilicity. In compost degradation tests, the PEU‐MeIs showed slower degradation than those of the PEUs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4423–4428 相似文献
837.
Simone F. Medeiros Amilton M. Santos Hatem Fessi Abdelhamid Elaissari 《Journal of polymer science. Part A, Polymer chemistry》2010,48(18):3932-3941
The goal of this study was to develop a new route to prepare thermally responsive polymer nanogels. Poly(N‐vinylcaprolactam) nanogels were prepared via inverse miniemulsion polymerization (W/O) at 70 °C using n‐hexadecane as a nonpolar continuous phase, potassium persulfate as an initiator, and N,N′‐methylenebisacrylamide as a crosslinker. Sorbitan monooleate (Span 80) was used as surfactant and its influence on the polymerization kinetics and on the colloidal characteristics of the nanogels were principally investigated. It was observed that the addition of a strong “lipophobe” is required to stabilize the resulting miniemulsion. The nanogels were characterized in terms of morphology, size, zeta potential, and thermoproperties using transmission electron microscopy and dynamic light scattering. It was observed that all the nanogels obtained collapsed when the lower critical solution temperature (LCST) was raised. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3932–3941, 2010 相似文献
838.
Anu Stella Mathews Suresh Narine 《Journal of polymer science. Part A, Polymer chemistry》2010,48(15):3236-3243
A novel block copolymer of poly[N‐isopropyl acrylamide]‐co‐polyurethane was designed, synthesized, and applied as controlled release fertilizer coating. Structural confirmation of the copolymer was performed using FTIR and 1H‐NMR spectra and elemental analysis. The coating process consists essentially of immersing urea granules in molten polymer and removing the coated urea from the melt by centrifugal action. The morphology of the coated urea was studied using scanning electron microscope (SEM). The polymer coat of the urea granules was found to swell in water forming pores and enabling the release of urea. The urea released from the granule, monitored using a mass spectroscopy technique, was found to be governed by pH of the aqueous medium. The study anticipates development of a beneficiary fertilizer coat in terms of improving controlled release over a period of time which can be tailored by soil temperature, pH and moisture. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3236–3243, 2010 相似文献
839.
The effects of crystallinity and temperature on enzymatic degradation of poly‐ε‐caprolactone (PCL) films and structural changes after degradation have been studied using weight loss, differential scanning calorimetry, and optical microscopy. The weight loss during the enzymatic degradation of PCL suggested that the extent of biodegradation and the rate of degradation strongly depend on the initial crystallinity. PCL films of lower crystallinity (24%) degraded much faster than films of higher crystallinity (45%). The crystallinity of low‐crystalline PCL films increased with increasing degradation time, whereas the crystallinity of high‐crystalline PCL films decreased with time. The spherulite size increased with increasing degradation time for low‐crystalline samples but decreased with time for high‐crystalline samples. These results revealed that degradation occurs first in the amorphous region where the degradation rate is much higher, and the crystalline region of the PCL film started to degrade simultaneously for those PCL with higher crystallinity. The enzymatic degradation of PCL proceeded from the free amorphous to restricted amorphous followed by lamellar edges, where PCL chains have higher mobility irrespective of hydrolysis temperature. Caproic acid was identified as the primary product formed after degradation and confirmed by proton nuclear magnetic resonance spectroscopy, suggesting that degradation occurs through the depolymerization mechanism. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 202–211, 2010 相似文献
840.
Chen‐Yu Li Shi‐Jie Hsu Chin‐lung Lin Chen‐Yen Tsai Jun‐Han Wang Bao‐Tsan Ko Chia‐Her Lin Hsi‐Ya Huang 《Journal of polymer science. Part A, Polymer chemistry》2013,51(18):3840-3849
Air‐stable copper catalysts supported by bis‐ BTP ligands ( BTP = N,O‐bidentate benzotriazole phenoxide) were synthesized and structurally characterized. The reactions of Cu(OAc)2·H2O with 2.0 molar equivalents of sterically bulky 2‐(2H‐benzotriazol‐2‐yl)‐4,6‐bis(1‐methyl‐1‐phenylethyl)phenol ( CMe2PhBTP ‐H) and 2‐(2H‐benzotriazol‐2‐yl)‐4,6‐di‐tert‐butylphenol ( t‐BuBTP ‐H) in refluxing ethanol solution afforded monomeric copper complexes [(CMe2PhBTP)2Cu] ( 1 ) and [(t‐BuBTP)2Cu] ( 2 ), respectively. The four‐coordinated copper analogue [(TMClBTP)2Cu] (3 ) resulted from treatment of 2‐tert‐butyl‐6‐(5‐chloro‐2H‐benzotriazol‐2‐yl)‐4‐methylphenol ( TMClBTP ‐H) as the ligand under the same synthetic method with ligand to metal precursor ratio of 2:1, but treatment of complex 3 in acetone gave five‐coordinated monomeric complex [(TMClBTP)2Cu(Me2CO)] (4 ). X‐ray diffraction of single crystals indicates that Cu complex 4 assumes a distorted square pyramidal geometry, penta‐coordinated by two BTP ligands, and one Me2CO molecule. Catalysis for lactide (LA) polymerization of BTP ‐containing Cu complexes in the presence of various alcohol initiators was investigated. Complex 3 initiated by 9‐anthracenemethanol catalyzes the ring‐opening polymerization effectively not only in a “living” fashion but also in an “immortal” manner, yielding polymers with the predictable molecular weights and narrow molecular weight distributions. Initiations from multifunctional alcohols were able to produce PLLAs with two‐arm linear and three‐arm star‐shaped molecular architectures. The controlled character of Cu complex 3 also enabled us to synthesize the PEG‐b‐PLLA copolymer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3840–3849 相似文献