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21.
Lei Li Shihui Li Dongmei Cui 《Journal of polymer science. Part A, Polymer chemistry》2017,55(6):1031-1039
Here we report on the coordination polymerization of a vinyl‐functionalized butadiene monomer, 3‐methylenehepta‐1,6‐diene (MHD) with exclusive conjugated diene chemoselectivity, high 1,2‐regioselectivity and moderate isotacticity (1,2‐selectivity > 99%, mm triad = 93%). Random copolymers of MHD and other conjugated diene (isoprene or myrcene) are also synthesized. The pendent vinyl groups of MHD homo or copolymers could be quantitatively converted into various functional groups via thiol‐ene click reaction. The resulting functionalized polybutadiene‐based material display versatile thermal and surface properties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1031–1039 相似文献
22.
金属配合物中引入侧臂软电子给体膦或硫是提高配合物催化性能的有效途径。本文合成了一系列吡啶/喹啉单亚胺NNP三齿Ni(Ⅱ)配合物(2a~2d),采用傅里叶变换红外光谱、元素分析及单晶衍射对配合物进行了表征。配合物2a为方形锥体构型,配合物2d为三角双锥构型。该系列配合物在倍半乙基氯化铝(EASC)活化下,催化合成了数均相对分子质量为4200~7700、顺-1,4结构的摩尔分数在74.5%~79.9%的液体聚丁二烯。催化活性随着聚合温度的升高而提高。在90℃时,催化体系仍有很高的聚合活性,聚丁二烯的收率达到85.9%,表明其具有高的热稳定性。 相似文献
23.
Fanny Barbotin Roger Spitz Christophe Boisson 《Macromolecular rapid communications》2001,22(17):1411-1414
The synthesis of a series of neodymium complexes supported on modified silica is reported. In an initial step the silanol groups were masked by a Lewis acid (BCl3, AlCl3, TiCl4, ZrCl4, SnCl4, SbCl5, HfCl4), and then a soluble arene complex Nd(η6‐C6H5Me)(AlCl4)3 formed in situ was reacted with the modified silica. The supported complexes are active and highly stereospecific for butadiene polymerization; 1,4‐cis insertion is superior by 99%. The catalyst based on a treatment of silica with BCl3 is the most efficient. 相似文献
24.
Canan Atilgan Ibrahim Inanc Ali Rana Atilgan 《Journal of Polymer Science.Polymer Physics》2012,50(23):1653-1662
We study geometric and energetic factors that partake in modifying properties of polymeric melts via inserting well‐dispersed nanoscopic particles (NP). Model systems are cis‐1,4‐polybutadiene melts including a single atomic clusters of size varied in the range 10–150 atoms (3–7 Å in radius; 0.1–1.5% v/v). We modify the interactions between the chains and the particle by tuning attractive van der Waals interactions. Using molecular dynamics, we study equilibrium fluctuations and dynamical properties at the interface. The NPs move in the polymer matrix in two different regimes corresponding to trapped and free diffusion, depending on the NP size. Furthermore, degree of crowding around the NP by the polymer chains is quantified. Effect of NP size and interaction strength both on volume and volumetric fluctuations is manifested in mechanical properties, quantified here by bulk modulus, K. Tuning NP size and nonbonded interactions results in ~15% enhancement in K by addition of a maximum of 1.5% v/v NP. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012 相似文献
25.
A method is described for the preparation of functional polybutadiene (PB) with hydroxyl groups along the polymer chain. This material can be used directly or as the starting substrate for further polymerization in both academic and industrial processes. We have developed a convenient method to obtain a polymer with a narrow molecular weight distribution and with a known content of hydroxyl groups along the backbone. By controlling the hydroxylation reaction conditions, the appropriate molar ratios of THF, water and acid with the epoxide are 30, 15 and 1.5, respectively. By minimizing the crosslinking reaction, the desired PB was prepared and subsequently characterized. 相似文献
26.
反相气相色谱法表征聚丁二烯橡胶的表面性质 总被引:1,自引:0,他引:1
采用反相气相色谱技术测定了聚丁二烯橡胶的表面性质。以正己烷、正庚烷、正辛烷、正壬烷作为非极性探针测定其表面色散自由能,以二氯甲烷、三氯甲烷、丙酮、乙酸乙酯、乙醚和四氢呋喃作为极性探针测定其路易斯酸碱常数。经计算得出聚丁二烯橡胶在303、313、323、333和343 K的表面色散自由能分别为47.07、46.46、45.85、45.60和45.09 mJ/m2。结果表明,聚丁二烯橡胶表面色散自由能随着温度的升高呈线性降低,路易斯酸常数Ka为0.34,碱常数Kb为1.77,总酸碱作用能力2.11,该聚合物为弱碱性Lewis两性聚合物材料。此外还计算出聚丁二烯橡胶的酸碱作用吸附自由能(~ΔGsa)和吸附焓(~ΔHsa)。 相似文献
27.
Philip Dimitrov Pradeep Iyer Marcel Van Beylen Thieo E. Hogen‐Esch 《Journal of polymer science. Part A, Polymer chemistry》2009,47(8):2198-2206
The anionic polymerization of butadiene initiated with 1,4‐dilithio‐1,1,4,4‐tetraphenylbutane (LiTPB) in diethyl ether (DEE) gives polybutadiene (PBD) with high 1,2 content (>70%), narrow polydispersities (1.04 < Mw/Mn < 1.20), and predicted molecular weights. In THF, this polymerization does not work very well. After removal of DEE and addition of THF, the PBD dianion is end capped quantitatively by addition of 1,1‐diphenylethylene (DPE) to give the diphenylalkyl end capped PBD dianion. Subsequent addition of methyl methacrylate at low temperatures results in the formation of well‐defined PMMA‐b‐PBD‐b‐PMMA triblock copolymers. The results are accounted for by taking into account the effects of Li ion solvation on the BD initiation and end capping of the PBD anion by DPE. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2198–2206, 2009 相似文献
28.
Mustapha Bahani Francoise Lauprêtre Lucien Monnerie 《Journal of Polymer Science.Polymer Physics》1995,33(2):167-178
Differential scanning calorimetry and torsional braid analysis investigations of the phase diagram of cis-1,4-polyisoprene/polybutadiene blends as a function of the polybutadiene microstructure were reported by several authors. Polybutadienes containing a high vinyl content were shown to be miscible with cis-1,4-polyisoprene on the DSC spatial scale, whereas polybutadienes containing a low vinyl content were immiscible. In this article, we used variable-temperature determinations of 1H NMR free induction decays and low-temperature, high-resolution solid-state 13C NMR measurements of proton spin-lattice relaxation times in the rotating frame to probe the phase behavior of the cis-1,4-polyisoprene/polybutadiene blends at the smaller spatial scale of the NMR technique. Blends of cis-1,4-polyisoprene with a polybutadiene having a large number of vinyl 1,2 linkages appeared to be miscible on the molecular scale, in spite of small regions in which the polybutadiene component is not uniformily dispersed in the other polymer. On the contrary, blends in which the polybutadiene has a low content of vinyl 1,2 sequences were phase separated over the whole temperature range considered and no intermixed regions could be detected. The limiting case was observed with the polybutadiene containing 33 wt % vinyl 1,2 units, for which miscibility on a molecular scale is highly dependent on the blend composition. © 1995 John Wiley & Sons, Inc. 相似文献
29.
The dynamic mechanical properties of blends of diglycidyl ether of bisphenol-A-based epoxy resin and internally epoxidized polybutadiene rubber have been studied. It is shown that the influence of the composition of the continuous phase and of the dispersed phase can be studied not only from the variations of the glass transition temperature but also from the changes in the apparent enthalpy of activation associated with this transition. As the initial rubber content increases, the composition of the dispersed phase remains practically constant while more rubber is able to dissolve in the continuous phase. Analysis of the rubbery plateau region reveals that the shear modulus of the blends is not much affected by the presence of dissolved rubber in the continuous phase but strongly depends on the volume fraction of dispersed phase. This volume fraction can be obtained from the relative drop in shear modulus after modeling the results with the Kerner equation. The results compares well with independent measurements by scanning electron microscopy. © 1994 John Wiley & Sons, Inc. 相似文献
30.
酰化法测定端羟基聚丁二烯羟值的测量不确定度评定 总被引:4,自引:0,他引:4
评定了酰化法测定端羟基聚丁二烯羟值的测量不确定度。分析了测量重复性、称量过程及标准物质稳定性等因素所带来的不确定度分量,采用酰化法测定端羟基聚丁二烯羟值的扩展不确定度为0.01mmol/g。 相似文献