全文获取类型
收费全文 | 209篇 |
免费 | 4篇 |
国内免费 | 25篇 |
专业分类
化学 | 215篇 |
力学 | 13篇 |
综合类 | 1篇 |
物理学 | 9篇 |
出版年
2023年 | 1篇 |
2020年 | 5篇 |
2019年 | 3篇 |
2018年 | 3篇 |
2017年 | 7篇 |
2016年 | 7篇 |
2015年 | 4篇 |
2014年 | 5篇 |
2013年 | 18篇 |
2012年 | 2篇 |
2011年 | 9篇 |
2010年 | 6篇 |
2009年 | 12篇 |
2008年 | 7篇 |
2007年 | 8篇 |
2006年 | 8篇 |
2005年 | 17篇 |
2004年 | 17篇 |
2003年 | 5篇 |
2002年 | 7篇 |
2001年 | 12篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 7篇 |
1995年 | 9篇 |
1994年 | 11篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 1篇 |
1989年 | 4篇 |
1988年 | 1篇 |
1985年 | 1篇 |
1981年 | 2篇 |
排序方式: 共有238条查询结果,搜索用时 359 毫秒
71.
通过稀土催化丁二烯配位聚合制备了一系列不同分子量、分子量分布及顺-1,4结构含量的稀土高顺式聚丁二烯(cis-PB),采用扫描示差量热仪法(DSC)研究了cis-PB在-18~-27℃范围内等温结晶过程,采用配有在线冷热台的偏光显微镜(POM)观测结晶形态.结果表明,在cis-PB等温结晶过程中,Avrami指数(n)在2.0~3.0之间,呈现三维球晶的生长方式,与微观结构参数及结晶温度无关,但其球晶尺寸与微观结构有关,并随着顺-1,4结构含量升高而增大;当顺-1,4结构含量小于98.4%时,半结晶期(t1/2)随其含量增加而缩短,结晶速率加快,但若其含量继续增加至99.0%左右时,结晶速率反而有所降低;若同时提高聚合物分子量及顺-1,4结构含量或者在分子量及顺-1,4结构含量相近的前提下使分子量分布变窄,均有利于提高结晶速率;随顺-1,4结构含量增加,过冷度(ΔT)增加,结晶驱动力增大;结晶活化能(ΔE)为负值,降低结晶温度有利于提高结晶速率,当顺-1,4结构含量大于98.2%时,ΔE值接近(~-137 k J/mol),结晶速率对温度的依赖程度相近. 相似文献
72.
合成了一系列吡唑亚胺二齿Ni(Ⅱ)配合物(4a~4e), 并通过红外光谱、元素分析及单晶衍射等对配合物进行了表征。 配合物4b属于单斜晶系, 以Ni原子为中心形成扭曲的三角双锥构型。 该系列配合物在倍半乙基氯化铝(EASC)的活化下, 对1, 3-丁二烯聚合表现出较高的顺-1, 4选择性, 得到了相对分子质量为4500~9000、顺-1, 4含量在91%左右的液体聚丁二烯。 随着取代基空间位阻的增大, 催化活性逐渐减低。 进一步详细研究了Al/Ni摩尔比和温度对聚合的影响。 在20~60 ℃范围内, 催化活性随着聚合温度的升高而提高, 聚合温度为80 ℃时, 聚合物收率仅略有降低, 表明该系列催化剂产生的活性中心具有良好的高温稳定性。 相似文献
73.
74.
Several types of the chiral thiols with two aromatic rings have been synthesised and grafted on polybutadiene diols backbone. The resulting functional polymers possess the OH end groups for the possible preparation of liquid crystal ordered networks. The thermal and mesomorphic properties of the synthesised side-chain units and resulting polymers have been studied by polarising optical microscopy, differential scanning calorimetry and X-ray scattering. Some of the resulting polymers possess a mesomorphic behaviour. The effects of the side-chain structure, number of the chiral groups and density of grafting on the polybutadiene diols have been studied. 相似文献
75.
Yonghong Wang Xingrong Zeng Hongqiang Li Jianhua Guo 《Journal of Macromolecular Science: Physics》2013,52(10):1904-1920
A novel polymeric antioxidant, hydroxyl-terminated polybutadiene-bound 2,2-thiobis(4-methyl-6-tert-butylphenol) (HTPB-IPDI-TPH), was prepared by binding 2, 2-thiobis(4-methyl-6-tert-butylphenol) (TPH) onto hydroxyl-terminated polybutadiene (HTPB) with isophorone diisocyanate (IPDI). Fourier-transform infrared spectroscopy (FTIR), 13C nuclear magnetic resonance spectroscopy (13C NMR), and gel permeation chromatography (GPC) were used to characterize the structure of HTPB-IPDI-TPH. The thermal stability of HTPB-IPDI-TPH was studied by thermogravimetry analysis (TGA). The effect of HTPB-IPDI-TPH on thermo-oxidative aging resistance of NR vulcanizates was investigated, and the mechanism of thermo-oxidative aging resistance was preliminarily discussed. The results showed that HTPB-IPDI-TPH contributed better thermal stability and thermo-oxidative aging resistance to NR vulcanizates than TPH. The thermo-oxidative aging resistance of HTPB-IPDI-TPH was more remarkable in the later stage of aging. Attenuated total-reflectance Fourier-transform infrared spectroscopy (FTIR-ATR) analysis showed that the relative content of carbonyl groups of NR vulcanizate with HTPB-IPDI-TPH was obviously lower than that with TPH after thermo-oxidative aging. It is suggested that ?NHCOO? groups in HTPB-IPDI-TPH enhanced the ability of trapping alkyl peroxide radicals. 相似文献
76.
端羟基聚丁二烯/增塑剂共混物相容性的分子动力学模拟 总被引:10,自引:0,他引:10
固体推进剂和炸药的力学性能在很大程度上依赖于配方中高分子粘结剂与增塑剂的相容性. 本文对相容和非相容两种体系进行了分子动力学(MD)模拟, 以考察分子模拟方法的实用性. 为预测固体推进剂中端羟基聚丁二烯(HTPB)与增塑剂癸二酸二辛酯(DOS)、硝化甘油(NG)的相容性, 采用MD模拟方法在COMPASS力场下, 对HTPB、DOS、NG和共混物HTPB/DOS、HTPB/NG的密度、内聚能密度及溶度参数等进行了模拟计算. 通过比较溶度参数差值(△δ)的大小、分子间径向分布函数和模拟前后体系密度变化情况均可以预测HTPB/DOS属于相容体系,而HTPB/NG属于不相容体系, 与实验结果一致. 径向分布函数分析同时揭示了HTPB/增塑剂组分之间的相互作用及本质. 本文的模拟方法可以作为预测聚合物与增塑剂相容性的有利工具, 也可以为固体推进剂和炸药的配方设计提供理论指导. 相似文献
77.
China is rich in rare earth resources. Rare earth elements, also named lanthanides, are number 58 to number 81 elements in the elemental periodic table. They have unique electronic structures and may form various coordination compounds. In the early 1960s, researchers at the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (CIAC) found the catalytic activities of lanthanide compounds in stereospecific polymerization of conjugated dienes, and published the first paper on this topic in 19... 相似文献
78.
Liezhong Gong Richard P. Wool Anthony D. Friend Konstantin Goranov 《Journal of polymer science. Part A, Polymer chemistry》1999,37(16):3129-3138
High molecular weight carboxylated polybutadienes (cPBDs) with number-average molecular weight (Mn) from 98,000 to 200,000 and carboxylic acid (COOH) contents of 0.5–10 mol % were successfully synthesized through hydrocarboxylation of polybutadienes (PBDs) at temperatures of 140–150°C using PdCl2(PPh3)2 and SnCl2 · 2H2O catalysts. At low extents of hydrocarboxylation (COOH < 6 mol %), glass transition temperatures (Tg's) of the resulting cPBDs did not change considerably (<10°C). Significant chain scission and crosslinking was not detected during the chemical modification process. Characterization of the microstructures of cPBDs by FTIR, 13C-NMR, and Raman spectroscopy showed that the carboxylic groups were incorporated on the pendant (1,2) PBD double bonds as well as the backbone (1,4) double bonds, indicating the hydrocarboxylation reaction did not solely occur at the terminal carbons of the pendant double bonds. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3129–3138, 1999 相似文献
79.
Roderic P. Quirk Jianxin Kuang 《Journal of polymer science. Part A, Polymer chemistry》1999,37(8):1143-1156
Attempted preparation of ω‐formyl‐functionalized polydienes by termination of poly(butadienyl)lithium and poly(isoprenyl)lithium with 4‐morpholinecarboaldehyde resulted in 73 and 38% dimer formation (SEC), respectively, under conditions that quantitativey produced ω‐formyl‐functionalized polystyrene. Dimer formation was attributed to postfunctionalization, base‐catalyzed, aldol‐type condensation based on FTIR and 1H‐NMR analysis of the dimer products. High yields (>97%) of ω‐formyl‐functionalized polydienes were formed by workup using acidic methanol; quantitative functionalization resulted from end capping the polymeric organolithium chain ends with 1,1‐diphenylethylene prior to the functionalization reaction. The ω‐formylpolydienes were characterized by hydroxylamine end‐group titration, FTIR, and both 1H‐ and 13C‐NMR spectroscopy. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1143–1156, 1999 相似文献
80.
A. Sultan Nasar S. Subramani Ganga Radhakrishnan 《Journal of polymer science. Part A, Polymer chemistry》1999,37(12):1815-1821
N-Methylaniline-, diphenylamine-, and N-phenylnaphthylamine-blocked toluene diisocyanates (TDI) were prepared and characterized by IR, NMR spectroscopy, and nitrogen content analyses. The structure–property relationship of these adducts was established by reacting with hydroxyl-terminated polybutadiene (HTPB). The cure rate of the adduct increases from the N-phenylnaphthylamine- to diphenylamine- and to N-methylaniline-blocked TDI adduct. Simultaneous TGA/DTA results also confirm this trend, and the thermal stability of the adduct decreases in the following order: N-phenylnaphthylamine–TDI > diphenylamine–TDI > N-methylaniline–TDI. The gas chromatogram of the amine-blocked isocyanate confirms that the thermolysis products are the blocking agent and isocyanate. The solubilities of the adducts were carried out in polyether, polyester, and hydrocarbon polyols, and it was found that the N-methylaniline–TDI adduct shows higher solubility than the rest and also found that the polyester polyol shows higher solvating power against the adducts than the polyether and hydrocarbon polyols. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1815–1821, 1999 相似文献