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91.
Yongtang Jia Xinyuan Shen Xiaohua Gu Jiong Dong Chunxiao Mu Yuqing Zhang 《先进技术聚合物》2008,19(2):159-166
A series of tri‐components copolymers with different molar ratios were synthesized via bulk ring‐opening copolymerization of trimethylene carbonate (TMC), L ‐lactide (LLA), and ε‐caprolactone (ε‐CL), using stannous octoate as catalyst. The sequence structure of the tercopolymer chain was characterized by 1H and 13C nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), and gel permeation chromatography (GPC). The results showed that although block sequence of the corresponding monomers still existed in the tercopolymer chain, the random tercopolymers were ultimately obtained due to the transesterification during polymerization. For the samples TP1 and TP2, longer sequence of LLA existed in the molecular chains. The thermal properties of tercopolymers were investigated by differential scanning calorimetry (DSC) and the mechanical properties of the resulting copolymers were studied by using a tensile tester. The results indicated that the properties of these copolymers could be adjusted by changing the compositions of the copolymers. The resulting tercopolymers are expected to have potential uses as nerve regeneration and other biomedicine materials. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
92.
93.
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
94.
Summary: The effect of poly(ε‐caprolactone) (PCL) molecular weight on the orientation of crystalline PCL in miscible poly(ε‐caprolactone)/poly(vinyl chloride) (PCL/PVC) blends, melt crystallized under strain, has been studied by a combination of wide angle X‐ray diffraction (WAXD) and small angle X‐ray scattering (SAXS) studies. An unusual crystal orientation with the b‐axis parallel to the stretching direction was observed in miscible PCL/PVC blends with PCL of high molecular weight (>21 000). SAXS showed the presence of nanosize confined PCL in the PCL/PVC blends, which could be preserved at temperatures higher than the Tm of PCL but lower than the Tg of PVC. A mechanism based on the confinement of PCL crystal growth was proposed, which can explain the formation of b‐axis orientation in PCL/PVC blends crystallized under strain.
95.
Nobuhiro Kawatsuki Michael Drr Hans-Werner Schmidt 《Journal of polymer science. Part A, Polymer chemistry》1993,31(4):1013-1021
The synthesis, characterization, and structure—property relations of aromatic polyesters with dicyanovinyl substituents is presented. Two comparable series of polyesters based on 3,4-dihydroxybenzylidenemalononitrile and 3,4-dihydroxy-5-methoxybenzylidenemalononitrile were prepared. As aromatic diacid components, terephthalic acid, phenylterephthalic acid, isophthalic acid, and 2-phenylisophthalic acid were used. The polyesters were prepared by solution polycondensation. GPC investigations revealed the existence of substantial amounts of defined cyclic products. These cycles could be isolated by preparative GPC. The polyesters are soluble in common low boiling organic solvents, particularly the phenyl-substituted ones. The polyesters are amorphous and have glass transition temperatures between 140 and 170°C. The absorption maxima are in the 306–322 nm range. The cut-off wavelength is between 400 and 428 nm. The polyesters with methoxy substitutent have generally the absorptions at longer wavelength. The refractive index of thin films of these polyesters were between 1.61 and 1.63 at 632.8 nm. © 1993 John Wiley & Sons, Inc. 相似文献
96.
Biodegradable elastomeric network polyesters were prepared from multifunctional aliphatic carboxylic acids such as tricarballylic acid (Yt) or meso-1,2,3,4-butanetetracarboxylic acid (Xb) and poly(epsilon-caprolactone) (PCL) diols with molecular weights of 530, 1,250 and 2,000 g.mol-1. Prepolymers prepared by a melt polycondensation were cast from DMF solution and postpolymerized at 280 degrees C for various periods of times to form a network. The resultant films were transparent, flexible and insoluble in organic solvents. The network polyesters obtained were characterized by IR absorption spectra, WAXS, density measurement, DSC, and tensile test. YtPCL1250, and XbPCL1250 network polyester films showed good elastomeric properties with high ultimate elongation (540-590%), and low Young's modulus (2.5-3.3 MPa). The enzymatic degradation was estimated by the weight loss of network films in a buffer solution with Rhizopus delemar lipase at 37 degrees C. The degree and rate of degradation were significantly affected by the molecular weight of PCL diol, chemical structures of multifunctional aliphatic carboxylic acids and the morphology of network films. The changes in the solid states of network films during the degradation were also estimated by the results of DSC and WAXS. [see text] 相似文献
97.
Masahiro Kihara Shin‐Ichiro Kohama Shota Umezono Kanji Wakabayashi Shinichi Yamazaki Kunio Kimura 《Journal of polymer science. Part A, Polymer chemistry》2011,49(5):1088-1096
Poly(p‐oxybenzoyl) (POB) crystals were prepared by reaction‐induced crystallization during direct polymerization of p‐hydroxybenzoic acid in the presence of boronic anhydrides. Polymerizations were carried out at 300 °C in dibenzyltoluene at a concentration of 1% with three kinds of anhydrides of boronic acid such as 3,4,5‐trifluorophenylboronic acid (TFB), 4‐methoxyphenylboronic acid (MPB) and 4‐biphenylboronic acid (BPB). The POB crystals were formed as precipitates in the solution and the morphology was considerably influenced by both the structure of the boronic anhydride and its concentration (cB). Needle‐like crystals were firmed in the presence of TFB anhydride (TFBA) at cBs of 5 and 10 mol % by the spiral growth of lamellae. Spherical aggregates of slab‐like crystals were formed at cBs from 50 to 100 mol %. The polymerization with MPB anhydride and BPB anhydride (BPBA) also yielded the needle‐like crystals at cBs of 50 and 5 mol %, respectively. The polymerization with TFBA at lower cB was favorable to prepare the needle‐like crystal. Molecular weight was also influenced by the structure of the boronic anhydride and cB. Mn increased generally with cB and BPBA gave the highest Mn of 14.7 × 103 at cB of 100 mol %. The loose packing of the molecules in the crystal caused by the bulkiness of the end‐groups made the polymerization in the crystals more efficiently. Morphology and molecular weight of the POB crystals could be controlled by the chemical structure and the content of boronic anhydride. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011. 相似文献
98.
Ryan M. Weiss Evan M. Jones David E. Shafer Ryan M. Stayshich Tara Y. Meyer 《Journal of polymer science. Part A, Polymer chemistry》2011,49(8):1847-1855
Repeating sequence copolymers of poly(lactic‐co‐caprolactic acid) (PLCA), poly(glycolic‐co‐caprolactic acid) (PGCA), and poly(lactic‐co‐glycolic‐co‐caprolactic acid) (PLGCA) have been synthesized by polymerizing segmers with a known sequence in yields of 50–85% with Mns ranging from 18–49 kDa. The copolymers exhibited well‐resolved NMR resonances indicating that the sequence encoded in the segmers used in their preparation is retained and that transesterification is minimal. The exact sequences allowed for unambiguous assignment of the NMR spectra, and these standards were compared with the data previously reported for random copolymers. The glass transition temperatures (Tgs) of the PLCA and PGCA copolymers were found to depend primarily on monomer ratio rather than sequence. Sequence dependent Tgs were, however, noted for the PLGCA polymers with 1:1:1 L:G:C ratios; poly LGC and poly GLC exhibited Tgs that differed by nearly 8 °C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
99.
Toshimitsu Ichimori Shinichi Yamazaki Kunio Kimura 《Journal of polymer science. Part A, Polymer chemistry》2011,49(21):4613-4617
The influence of shear flow, especially the timing for the application of shearing, was examined to enhance the selectivity for the preparation of poly(p‐oxybenzoyl) (Pp‐OB) by using hydrodynamically induced phase separation during polymerization of 4‐(4‐acetoxybenzoyloxy)benzoic acid (p‐ABAD) and m‐acetoxybenzoic acid (m‐ABA). The polymers containing few m‐oxybenzoyl (m‐OB) moieties were obtained as precipitates even at high content of m‐OB moiety in feed (χf) under shear flow. The content of m‐OB moiety in the precipitates (χp) prepared under shearing throughout the polymerization at the shear rate (γ) of 489 s?1 was 6.3 mol % even at χf of 60 mol %. Especially, the Pp‐OB was obtained as the precipitates at χf of less than 50 mol %. The timing of the application of the shearing influenced the selectivity significantly, and the shearing just after the precipitation of the oligomers started was quite efficient to enhance the selectivity more. The χp of the precipitates prepared with shearing at γ of 489 s?1 just after the precipitation was only 3.9 mol % even at χf of 60 mol %. The shear flow reduced the difference in the reactivity between p‐ABAD and m‐ABA, resulting in the decrease in the selectivity with regard to the formation of p‐oxybenzoyl homo‐oligomer. However, the shear flow enhanced the difference in the miscibility between homo‐oligomers and co‐oligomers. This change in the miscibility by shear flow brought about the more rapid precipitation of homo‐oligomers, leading to the enhancement of the selectivity. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
100.
Kosuke Makiguchi Seiya Kikuchi Toshifumi Satoh Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2013,51(11):2455-2463
The ring‐opening polymerization (ROP) of cyclic esters, such as ε‐caprolactone, 1,5‐dioxepan‐2‐one, and racemic lactide using the combination of 3‐phenyl‐1‐propanol as the initiator and triflimide (HNTf2) as the catalyst at room temperature with the [monomer]0/[initiator]0 ratio of 50/1 was investigated. The polymerizations homogeneously proceeded to afford poly(ε‐caprolactone) (PCL), poly(1,5‐dioxepan‐2‐one) (PDXO), and polylactide (PLA) with controlled molecular weights and narrow polydispersity indices. The molecular weight determined from an 1H NMR analysis (PCL, Mn,NMR = 5380; PDXO, Mn,NMR = 5820; PLA, Mn,NMR = 6490) showed good agreement with the calculated values. The 1H NMR and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry analyses strongly indicated that the obtained compounds were the desired polyesters. The kinetic measurements confirmed the controlled/living nature for the HNTf2‐catalyzed ROP of cyclic esters. A series of functional alcohols, such as propargyl alcohol, 6‐azido‐1‐hexanol, N‐(2‐hydroxyethyl)maleimide, 5‐hexen‐1‐ol, and 2‐hydroxyethyl methacrylate, successfully produced end‐functionalized polyesters. In addition, poly(ethylene glycol)‐block‐polyester, poly(δ‐valerolactone)‐block‐poly(ε‐caprolactone), and poly(ε‐caprolactone)‐block‐polylactide were synthesized using the HNTf2‐catalyzed ROP. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2455–2463 相似文献