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1.
1965年Allcock等[1 ] 首次报道六氯三聚膦腈 (HCCP)热开环聚合制备聚二氯膦腈 (PDCP)以来 ,大量的研究工作集中在引入不同的侧链以合成具有各种性能的无机有机高分子。迄今为止 ,聚膦腈已经广泛地被研究用做阻燃材料[2 ] 、生物高分子[3] 、液晶[4,5] 、非线性光学材料[6] 、分离膜[7] 以及固体聚合物电解质[8,9] 。目前的研究热点主要在通过活性聚合合成相对分子量和结构可控的有新型功能性的均聚或者共聚膦腈聚合物。HCCP的亲核取代反应的难易程度取决于反应介质的选择和离去基团的性质。目前采用较多的是用金属钠或者…  相似文献   

2.
茂钛催化剂聚1-丁烯的合成   总被引:8,自引:0,他引:8  
茂金属催化烯烃聚合以其高活性、定向性等特点受到广泛重视.Kaminsky[1~4]等用二茂基(Cp、Ind和Flu)过渡金属(Ti、Zr和Hf)化合物/MAO催化剂催化1丁烯聚合,可得到间规(sPB)、无规(aPB)或等规(iPB)聚1丁烯.Lin[5]和Wu[6]分别用单茂基的CpTi(OPr)3/MAO和CpTi(OBz)3/MAO催化剂进行丙烯聚合,都得到无规聚丙烯(aPP),并研究了催化体系中Ti氧化态分布,认为Ti+4有利于α烯烃聚合.有关用单茂钛化合物/MAO催化体系催化1丁烯聚合的研究目前较少文献报道.本文用新型茂钛催化剂—…  相似文献   

3.
一种新型双亚胺吡啶铁系催化剂的乙烯低聚研究   总被引:1,自引:0,他引:1  
线性α 烯烃广泛地应用于洗涤剂、增塑剂、润滑油等精细化学品的合成以及作为共单体制备线性低密度聚乙烯 (LLDPE) .目前工业上主要是应用SHOP法[1] 、Chevron工艺和Amoco工艺[2 ] 通过乙烯低聚制备 .近些年发展起来的新型高活性后过渡金属乙烯低聚催化剂能够高选择性地制备线性α 烯烃[3 ,4] .Brookhart等[4] 的研究表明 ,对于双亚胺吡啶铁系乙烯聚合催化剂而言 ,配体上苯基的邻位取代基位阻减小可以实现乙烯低聚 ,并具有高活性、高选择性以及理想的低聚产物分布 .本文的工作是从配体的空间位阻效应对催化剂…  相似文献   

4.
具有RAFT链转移过程的活性自由基聚合的Monte Carlo模拟   总被引:1,自引:0,他引:1  
活性自由基聚合是近年来高分子合成领域中研究的热点之一 .目前主要有两种体系 ,其一是TEMPO调控的自由基聚合[1],但单体选择面窄 ,聚合速率慢 ;其二是原子转移聚合 ,单体适用面较广 ,但产物中常含有难以除去的金属离子[2 ].因此寻找单体适用性广 ,产物纯净的聚合体系 ,具有十分重要的意义 .近两年来 ,Thang等[36 ]发现用双硫酯调聚的自由基聚合具有活性特征 ,并指出其原因是这类体系中的链转移具有可逆性 ,称为可逆加成 裂解链转移过程 (RAFT) ,可示意如下 :Ri·+ CSZSRj(DSE)kaddkdisC·SRiZSRj…  相似文献   

5.
沸石是天然和合成水合钠 (钾、钙、钡 )铝硅酸盐矿物的通称。合成沸石基于铝硅酸盐外配位层和沸石分子中碱 (碱土 )金属、铝、硅之间摩尔比的不同以及合成条件的差异 ,而有多种型号。其中常用的Na Al Si结构框架的就有 4A、 13X、Y、丝光沸石等类型[1] ,而 4A沸石经KCl或CaCl2 部分交换处理后 ,生成 3A (K Na Al Si)或 5A (Ca Na Al Si)沸石 ;13X型 (Na Al Si)经CaCl2 交换后生成10X (Ca Na Al Si)沸石。因此 ,Na Al Si型合成沸石是制取其它合成沸石的基础。本文介绍的合成沸…  相似文献   

6.
自从Matyjaszewski等[1,2 ] 发现原子转移自由基聚合 (ATRP)以来 ,寻求新的双多官能引发剂是该领域的重要研究方向之一[3~ 7] .2 0 0 0年 ,我们[8]曾报道了α ,α 二溴乙酸乙酯可作为丙烯酸酯ATRP的双官能引发剂 ,并基于其两端增长的活性聚合性质合成了PS b PBA b PS和PMMA b PBA b PMMA两种三嵌段共聚物 .与此同时 ,Hocker等[9] 通过比较氯化苄与α ,α 二氯甲苯引发的苯乙烯ATRP的聚合速度 ,认为α ,α 二氯甲苯是苯乙烯ATRP的双官能引发剂 .当我们参照上述结果 ,用α ,α 二…  相似文献   

7.
聚氯乙烯-g-聚甲基丙烯酸-2-羟乙酯共聚物的合成和表征   总被引:4,自引:0,他引:4  
聚氯乙烯 (PVC)是常用医用高分子材料之一 ,可以制作储血袋、导液管、人工尿道等 .PVC亲水性差 ,影响其生物相容性 .采用亲水性单体与PVC接枝共聚是提高PVC亲水性的重要方法[1] .Krishnan等[2 ] 对Co60 辐照下PVC接枝N 乙烯基吡咯烷酮进行了研究 .Singh等[3~ 5] 采用辐照引发甲基丙烯酸在PVC薄膜的接枝反应 ,对接枝动力学、接枝后薄膜表面形态、溶胀和抗凝血性等进行了研究 .Goldberg等[6] 采用辐照引发甲基丙烯酸2 羟乙酯 (HEMA)在PVC薄膜上的接枝 .Lee等[7]采用溶液接枝共聚制备了…  相似文献   

8.
稀土掺杂PMMA包裹硅铝氧烷凝胶的ER效应   总被引:3,自引:2,他引:1  
以二氧化硅微粒制备电流变液是研究者使用较多的一种方法[1] ,但由于二氧化硅的密度相对于分散相硅油来说太大 ,所以制成的电流变液稳定性较差。而用导电高分子微粒制成的电流变液则有在高电场时漏电流密度较大的问题[2 ] 。有研究者用直接聚合法在二氧化硅纳米微粒外包裹一层有机共聚物 ,生成一种微囊复合颗粒 ,可以使其相对密度减小 ,提高了电流变液的稳定性[3] 。我们以廉价水玻璃为原料制取硅铝氧烷溶胶 ,在其表面包裹聚甲基丙烯酸甲酯 (PMMA)后 ,得到PMMA包裹的硅铝氧烷凝胶具有相当的稳定性和易极化性 ,易形成较稳定的悬浮液 …  相似文献   

9.
乙烯 (E) /乙烯醇 (V)共聚物 (EVOH)为结晶性高聚物 ,作为膜材料有着广泛的用途 .在该体系中 ,不仅存在复杂的化学和物理结构 ,如序列分布、立构规整性和共晶结构 ,还存在复杂的氢键相互作用 ,是研究化学结构、聚集态结构和氢键相互作用之间关系的代表性体系 .通过DSC[1 ] 、X 射线衍射[2 ] 、固体高分辨核磁共振碳谱 (1 3C CP/MAS NMR) [3~ 7] 等不同的研究方法 ,前人对EVOH体系及与之直接相关的乙烯醇均聚物(PVA)的熔融温度、结晶度以及结晶结构等问题进行了大量研究 .1 984年Terao等[6] 首先报道了在固…  相似文献   

10.
羟基磷灰石合成工艺研究   总被引:1,自引:0,他引:1  
羟基磷灰石 [Ca10 (PO4 ) 6(OH) 2 ,简称HAP]是80年代发展起来的新型牙科、骨科材料 ,其成份接近生物体骨质的无机成份 ,能诱发新骨生长 ,具有良好的生物相容性。HAP的制备方法较多 ,有溶胶 凝胶法[1,2 ] 、沉淀法、电化学合成法[3 ,4 ] 等。1 实验1 1 试剂与仪器所用试剂除磷酸三丁酯为化学纯外 ,其它都是分析纯。美国尼高力公司 (NICOLET)傅里叶变换红外光谱仪 (MAGNA 5 5 0 (Ⅱ ) )。1 2 HAP的制备1 2 1 溶胶 凝胶法合成HAP 我们以不同原料制备了HAP。第一种方法是以Ca(NO3)2 与磷酸三丁…  相似文献   

11.
在Al_2O_3-P_2O_5-六次甲基四胺-H_2O体系中,水热合成出新型磷酸铝分子筛(AlPO_4-CJ_2),培养了单晶,经多晶X射线衍射、四圆单晶结构测定及红外光谱研究证明,AlPO_4-CJ_2具有空旷的骨架结构,沿(100)和(001)方向具有8元环孔道,骨架中Al原子以AlO_5(三角双锥)和AlO_5F(扭曲八面体)形式存在,水分子氧的桥联产生Al—O—Al连接模式。  相似文献   

12.
The Cuban chromites with a spinel structure, FeCr2O4 have been studied using optical absorption and EPR spectroscopy. The spectral features in the electronic spectra are used to map the octahedral and tetrahedral co-ordinated cations. Bands due Cr3+ and Fe3+ ions could be distinguished from UV-vis spectrum. Chromite spectrum shows two spin allowed bands at 17,390 and 23,810 cm(-1) due to Cr3+ in octahedral field and they are assigned to 4A2g(F) --> 4T2g(F) and 4A2g(F) --> 4T1g(F) transitions. This is in conformity with the broad resonance of Cr3+ observed from EPR spectrum at g = 1.903 and a weak signal at g = 3.861 confirms Fe3+ impurity in the mineral. Bands of Fe3+ ion in the optical spectrum at 13,700, 18,870 and 28,570 cm(-1) are attributed to 6A1g(S) --> 4T1g(G), 6A1g(S) --> 4T2g(G) and 6A1g(S) --> 4T2g(P) transitions, respectively. Near-IR reflectance spectroscopy has been used effectively to show intense absorption bands caused by electronic spin allowed d-d transitions of Fe2+ in tetrahedral symmetry, in the region 5000-4000 cm(-1). The high frequency region (7500-6500 cm(-1)) is attributed to the overtones of hydroxyl stretching modes. Correlation between Raman spectral features and mineral chemistry are used to interpret the Raman data. The Raman spectrum of chromite shows three bands in the CrO stretching region at 730, 560 and 445 cm(-1). The most intense peak at 730 cm(-1) is identified as symmetric stretching vibrational mode, A1g(nu1) and the other two minor peaks at 560 and 445 cm(-1) are assigned to F2g(nu4) and E(g)(nu2) modes, respectively. Cation substitution in chromite results various changes both in Raman and IR spectra. In the low-wavenumber region of Raman spectrum a significant band at 250 cm(-1) with a component at 218 cm(-1) is attributed F2g(nu3) mode. The minor peaks at 195, 175, 160 cm(-1) might be due to E(g) and F2g symmetries. Broadening of the peak of A1g mode and shifting of the peak to higher wavenumber observed as a result of increasing the proportion of Al3+O6. The presence of water in the mineral shows bands in the IR spectrum at 3550, 3425, 3295, 1630 and 1455 cm(-1). The vibrational spectrum of chromite gives raise to four frequencies at 985, 770, 710 and 650 cm(-1). The first two frequencies nu1 and nu2 are related to the lattice vibrations of octahedral groups. Due to the influence of tetrahedral bivalent cation, vibrational interactions occur between nu3 and nu4 and hence the low frequency bands, nu3 and nu4 correspond to complex vibrations involving both octahedral and tetrahedral cations simultaneously. Cr3+ in Cuban natural chromites has highest CFSE (20,868 cm(-1)) when compared to other oxide minerals.  相似文献   

13.
The crystal structure of NH(4)(+)OOH(-) is determined from single-crystal x-ray data obtained at 150 K. The crystal belongs to the space group P2(1)/c and has four molecules in a unit cell. The structure consists of discrete NH(4)(+) and OOH(-) ions. The OOH(-) ions are linked by short hydrogen bonds (2.533 A?) to form parallel infinite chains. The ammonium ions form links between these chains (the N?O distances vary from 2.714 to 2.855 A?) giving a three-dimensional network. The harmonic IR spectrum and H-bond energies are computed at the Perdew-Burke-Ernzerhof (PBE)/6-31G(??) level with periodic boundary conditions. A detailed analysis of the shared (bridging) protons' dynamics is obtained from the CPMD simulations at different temperatures. PBE functional with plane-wave basis set (110 Ry) is used. At 10 K the shared proton sits near the oxygen atom, only a few proton jumps along the chain are detected at 70 K while at 270 K numerous proton jumps exist in the trajectory. The local-minimum structure of the space group Cc is localized. It appears as a result of proton transfer along a chain. This process is endothermic (~2?kJ/mol) and is described as P2(1)/c?2Cc. The computed IR spectrum at 10 K is close to the harmonic one, the numerous bands appear at 70 K while at 270 K it shows a very broad absorption band that covers frequencies from about 1000 to 3000?cm(-1). The advantages of the NH(4)(+)OOH(-) crystal as a promising model for the experimental and DFT based molecular dynamics simulation studies of proton transfer along the chain are discussed.  相似文献   

14.
用原位合成的方法制备不同物质的量配比的CoPc(β-OC6Cl5)4/SnO2复合材料,利用UV,IR和XRD对产物进行表征,并在可见光条件下测定其对罗丹明B光催化降解反应产率.结果表明:复合材料在紫外光谱中出现红移现象,红外光谱中出现了M—O的振动吸收峰,XRD谱图中显现出SnO2晶粒变小,说明CoPc(β-OC6Cl5)4与SnO2之间形成部分化学键,负载量物质的量分数为4%的CoPc(β-OC6Cl54)/SnO2复合材料对罗丹明B的光催化降解产率最高.  相似文献   

15.
Single crystal X-ray diffraction and IR spectroscopy have been used to study the conformation of 2-hydroxyphenyl 2-hydroxy-2-(-naphthyl)vinyl ketone in solid state. It was found that one of the two possible enol tautomeric forms is stabilized in the crystal. The 1-hydroxy-3-oxo-1,3-propenylene moiety, O=C—CH=C—OH, shows a strong intramolecular H bond with a definite character of reasonance-assisted hydrogen bond in spite of being in competition with ring intermolecular hydrogen bonds. The comparison of the present results with solution NMR data indicates that the molecular geometry in solid state and in solution are similar.  相似文献   

16.
IntroductionAllsB.O,, is a refractory compound with the melting point of 1 713 K. It has a low density of 2. 94 g/cm' and tends to form a needle--shaped crystal. These characteristics lead to itspotential application in reinforced plastics or metal alloys['j. The investigationL'] in the crystalstructure Of Al,SB,O,, by X-ray study has reve.aled that the material has a 10Al,O,. BZO3type structure. This structure contains AIO.--tetrahedra, AIO,-octahedra, five-oxygen-coordinated Al ato…  相似文献   

17.
Rh/Al2O3上H2的化学吸附   总被引:1,自引:0,他引:1  
  相似文献   

18.
The title coordination compound has been synthesized by the reaction of HLaEDTA.7H2O with (formula; see text) in ethanol aqueous solution. The single crystal has grown from aqueous solution and has been characterized by IR, TG-DTA, X-ray powder diffraction, molar conductance, UV and 1H-NMR. The determination of its crystal and molecular structure shows that it crystallizes in space group P21/n with lattice parameters: a = 14.735A, b = 29.335A, c = 16.409A, beta = 99.24 degrees, v = 7009.30A3, z = 4, F(000) = 3488, molecular weight M = 1756.90, Dc = 1.665g/cm3. It has been refined by the full matrix least squares method to final discrepancy factor R = 0.096. The anion [La2(EDTA)2(H2O)4]2- turns out to be a dimer, in which each of the two EDTA4- ions is coordinated to a La3+ ion with five of its six coordinating sites and the remaining sixth one--the oxygen atom of carboxylis bridged to two La3+ ions, thus forming a parallelogrammic four-membered ring La2O2. The nine coordinations about each metal are completed by two water molecules. The average bond length is 2.560 A for La-O and 2.833A for La-N. Approximately, the dimer belongs to point group Ci with the centre of inversion at the centre of La2O2 parallelogram. The antitumor activity of the coordination compound was studied by observing its effect on the incorporation of 3H-TdR into DNA of leukemia (L7712) cells in vitro. The degree of inhibition reached 83.9% after exposing 2 X 10(5) cells per millilitre to 4 X 10(-5) mol/L of the compound for 24 h, being higher than those of its precursors.  相似文献   

19.
UV-visible, infrared (IR), and resonance Raman (RR) spectra were measured and analyzed for a high-valent molybdenum(V)-oxo complex of 5,10,15-tris[3,5-bis(trifluoromethyl)phenyl]corrole (1) at room temperature. The strength of the metal-oxo bond in 1 was found to be strongly solvent-dependent. Solid-state IR and RR spectra of 1 exhibited the MoVO stretching vibration at nu(MoVO)=969 cm(-1). It shifted up by 6 cm(-1) to 975 cm(-1) in n-hexane and then gradually shifted to lower frequencies in more polar solvents, down to 960 cm(-1) in dimethyl sulfoxide. The results imply that stronger acceptor solvents weaken the MoVO bond. The 45-cm(-1) frequency downshifts displayed by 1 containing an 18O label in the molybdenum(V)-oxo unit confirmed the assignments for the observed IR and RR nu(MoVO) bands. The solvent-induced frequency shift for the nu(MoVO) RR band, measured in a series of 25 organic solvents ranging from n-hexane (AN=0.0) to N-methylformamide (AN=32.1), did not decrease in direct proportion to Gutmann's solvent acceptor numbers (ANs). However, a good linear correlation of the nu(MoVO) frequency was found against an empirical "solvent polarity" scale (A+B) of Swain et al. J. Am. Chem. Soc. 1983, 105, 502-513. A molecular association was observed between chloroform and oxomolybdenum(V) corrole 1 through MoO...H/CCl3 hydrogen-bonding interactions. This association manifested itself as a shift of the nu(MoVO) RR band of 1 in CDCl3 to a higher frequency compared to that in CHCl3.  相似文献   

20.
Raman spectroscopy complimented with infrared ATR spectroscopy has been used to characterise a halotrichite FeSO(4) x Al(2)(SO(4))(3) x 22 H(2)O from The Jaroso Ravine, Aquilas, Spain. Halotrichites form a continuous solid solution series with pickingerite and chemical analysis shows that the jarosite contains 6% Mg(2+). Halotrichite is characterised by four infrared bands at 3569.5, 3485.7, 3371.4 and 3239.0 cm(-1). Using Libowitsky type relationships, hydrogen bond distances of 3.08, 2.876, 2.780 and 2.718 Angstrom were determined. Two intense Raman bands are observed at 987.7 and 984.4 cm(-1) and are assigned to the nu(1) symmetric stretching vibrations of the sulphate bonded to the Fe(2+) and the water units in the structure. Three sulphate bands are observed at 77K at 1000.0, 991.3 and 985.0 cm(-1) suggesting further differentiation of the sulphate units. Raman spectrum of the nu(2) and nu(4) region of halotrichite at 298 K shows two bands at 445.1 and 466.9 cm(-1), and 624.2 and 605.5 cm(-1), respectively, confirming the reduction of symmetry of the sulphate in halotrichite.  相似文献   

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