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1.
溶剂在丁腈基聚氨酯中的溶解和扩散   总被引:2,自引:0,他引:2  
用石英弹簧法和示差扫描量热法 (DSC)、红外分光光度计 (FTIR)研究了苯、乙醇、丙酮、醋酸乙酯和1,2 二氯乙烷五种溶剂在端羟基聚丁二烯 丙烯腈共聚物为软段的聚氨酯中的溶解和扩散行为 .结果表明所有溶剂在丁腈聚氨酯中的扩散均为非费克扩散 ,且随着溶剂蒸汽压增大偏离费克扩散的程度增大 .相同相对蒸汽压下 1,2 二氯乙烷和醋酸乙酯偏离费克 (Fickian)扩散的程度较大 ,而乙醇、丙酮和苯则较小 ,这主要与它们和丁腈软段溶解度参数的极性分量和氢键分量有关 .1,2 二氯乙烷和苯在HTBN PU中的溶解度较高 ,而乙醇 ,醋酸乙酯和丙酮较低 ,主要与它们和丁腈软段溶解度参数的色散分量有关 .所有溶剂均表现出近似Flory Huggins型等温吸收曲线 .红外表明吸收溶剂后 ,氨基甲酸酯基团的氢键化程度有不同程度的下降 ,和溶剂与之形成氢键的能力大小有关 .力学性能表明非极性溶剂苯对材料的力学性能影响较小 ,而乙醇 ,醋酸乙酯和丙酮由于可与氨酯基团形成氢键 ,对原HTBN PU中氨酯键氢键的破坏大 ,力学性能下降大  相似文献   

2.
利用非水溶剂快速挥发的方法,以三嵌段共聚物P123等作为结构导向剂,双三乙氧硅基乙烷作为硅源,合成出一系列大孔径(>4nm)、高有序度、具有二维六角结构并且墙壁中含双亚甲基的介孔有机氧化硅(PMO)材料,并通过XRD、TEM、N2吸附-脱附、29SiNMR和SEM等方法对材料进行了表征.  相似文献   

3.
采用核磁共振波谱(NMR)研究了二苯基甲烷二异氰酸酯(MDI)在稀溶液中的水解反应机理.将同一MDI样品分别溶解在氘代氯仿、氘代丙酮和加入少量水分的氘代二甲基亚砜溶剂(DMSO)中,进行核磁共振氢谱(1H NMR)、核磁共振碳谱(13C NMR)测试.结果显示,MDI在含水的DMSO溶剂中测得的谱图与氘代氯仿、氘代丙酮中的差别显著.对该溶液进行了13C-1H异核近程相关(HMQC)、13C-1H异核远程相关(HMBC)及碳原子级数(DEPT 135)测试,并利用经验公式对其进行了详细归属,确认了反应产物的结构.分析得知MDI在含水溶剂中迅速反应,异氰酸酯基转化为脲基和氨基基团.异氰酸酯与水反应生成氨基基团,其与异氰酸酯反应活性比水高,对位取代氨基与水的竞聚率比值为7.1,邻位为1.4,对位取代氨基活性约是邻位的5倍.  相似文献   

4.
一微有交联的聚甲基丙烯酸甲酯试样在甲苯-乙醇和丙酮-水混合溶剂中的平衡溶胀比用容量法作直接测量,当非溶剂的体积分数分别为γ=0.17(乙醇)和0.02(水)时,平衡溶胀比均出现极大,与在稀溶液中的粘度和渗透压行为完全一致.在θ溶剂中的平衡溶胀比Q_θ是与溶剂-非溶剂对无关的常数,因而溶胀数据可以用一维溶胀因子X_(溶胀)= (Q/Q_θ)~(1/3)表示.从实验结果得到聚甲基丙烯酸甲酯的溶度参数δ=10.0.  相似文献   

5.
采用金属醇酯一步水解法, 在不同含水有机溶剂反应介质中在常温条件下制备了具有特殊形貌及等级孔道结构的超高比表面积γ-Al2O3材料. X射线衍射(XRD)、 N2吸附-脱附、 扫描电子显微镜(SEM)和透射电子显微镜(TEM)等表征结果证明, 通过调节反应介质中水含量和溶剂类型可以精确控制仲丁醇铝的水解缩合反应过程和副产物醇分子的扩散行为, 进而优化产物的孔道结构. 研究结果表明, 在水/乙腈体系下制备的γ-Al2O3材料整体呈现出由大孔直孔道和三维介孔孔道构成的等级孔道结构, 且随着水含量的增加, 大孔孔壁依次出现光滑状、 片状和褶皱状的特定形貌; 在饱和水的丁醇溶液体系下制备的材料则展现出由厚度约为10 nm的片状γ-Al2O3堆积而成的三维介孔结构, 比表面积高达517 m 2/g. 选取水含量为3 mL的水/乙腈体系下的大孔-介孔γ-Al2O3材料作为载体制备负载型Pt基催化剂. 负载后载体等级孔结构基本保持完好, 金属Pt纳米颗粒均匀分散在载体上, 该催化剂在渣油脱金属催化反应中的脱金属性能比商用薄水铝石为载体制备Pt基催化剂更加优异. 脱Ni率和脱V率分别提高11.62%和10.83%.  相似文献   

6.
本文测定了 NaClO_4在水-丙酮,水-乙腈,水-乙醇以及 NaBPh_4在甲醇-DMF,甲醇-苯,甲醇-二氧六圜混合溶剂体系中~(23)Na~ 的化学位移随溶剂组成的变化规律。利用等溶剂化点比较了各溶剂对 Na~ 的溶剂化能力:H_2O>(CH_3)_2CO≥CH_3CN≥C_2H_5OH;DMF>CH_3OH。对于甲醇-DMF 和水-丙酮体系,估算出 DMF 对甲醇,丙酮对水的 Na~ 优先溶剂化自由能分别为-2.7kJmol~(-1)和 4.6kJmol~(-1)。在甲醇-苯混合溶剂体系中,~(23)Na~ 的化学位移独立于苯的含量。它支持了甲醇-惰性溶剂混合体系的单一溶剂化模型。而在甲醇-二氧六圜体系中~(23)Na~ 的化学位移随混合溶剂组成而发生变化。~(23)Na~ 磁共振的峰宽随二氧六圜的加入急剧增加,这表明二氧六圜分子可能进入了在甲醇中的 Na~ 原溶剂化层,导致了 Na~ 化学环境不对称。  相似文献   

7.
刘卫  宋树忠  奚祖威 《催化学报》1988,9(4):411-417
考察了铑、钌、钯络合物对4,5-环氧-2-戊烯醛加氢的催化作用,发现Pd(acac)_2是高效的催化剂,用这一催化体系研究的结果表明:与环氧基因相邻的双键对环氧环有一定的活化作用;溶剂及配体对反应影响很大,加氢速度分别按下列顺序降低:乙酸>乙醇>丙酮>苯>四氢呋喃>环己烷,Pd(tfac)_2≥Pd(hfac)_2>Pd(acac)_2, 此外还考察了压力、温度对反应的影响,提出了包括环氧基参与配位的4,5-环氧-2-戊烯配合醛加氢的可能反应机理。  相似文献   

8.
本文测定了NaClO_4在水-丙酮, 水-乙腈,水-乙醇以及NaBPh_4在甲醇-DMF, 甲醇-苯, 甲醇-二氧六圜混合溶剂体系中~(23)Na~+的化学位移随溶剂组成的变化规律。利用等溶剂化点比较了各溶剂对Na~+的溶剂化能力: H_2O>(CH_3)_2CO≥CH_3CN≥C_2H_5OH; DMF>CH_3OH。对于甲醇-DMF和水-丙酮体系, 估算出DMF对甲醇, 丙酮对水的Na~+优先溶剂化自由能分别为-2.7 kJmol~(-1)和+4.6 kJmol~(-1)。在甲醇-苯混合溶剂体系中, ~(23)Na~+的化学位移独立于苯的含量。它支持了甲醇-惰性溶剂混合体系的单一溶剂化模型。而在甲醇-二氧六圜体系中~(23)Na~+的化学位移随混合溶剂组成而发生变化。~(23)Na~+磁共振的峰宽随二氧六圜的加入急剧增加, 这表明二氧六圜分子可能进入了在甲醇中的Na~+原溶剂化层, 导致了Na~+化学环境不对称。  相似文献   

9.
筛选出两种孔径较大且孔结构规则的植物为大孔模板, 以嵌段共聚物为介孔相模板成功合成了两种具有连续的骨架和贯通的大孔孔道(大孔孔径大于40 μm, 其孔壁为介孔相)的高度有序多级复合孔材料. 对该复合孔材料进行了水热稳定性研究. 用扫描电子显微镜(SEM)、粉末X射线衍射仪(XRD)、高分辨率透射电镜(HRTEM)以及N2吸附-脱附等测试手段对合成的样品进行了表征. 结果表明, 合成的产物是孔道相互贯通的多级有序复合孔硅材料, 具有较好的水热稳定性. 采用此合成方法可精确地复制大孔植物模板.  相似文献   

10.
以正硅酸乙酯(TEOS)和甲基三乙氧基硅烷(MTES)为共同前驱体,羟丙基-β-环糊精(HPCD)为致孔剂,水和乙醇为溶剂,氨水为催化剂,采用溶胶-凝胶法制备了HPCD-Si O2溶胶.溶胶经过六甲基二硅氮烷(HMDS)改性后,制得疏水型超低折射率膜层,其最低折射率可达1.05,静态水接触角从66.4°上升至128.7°.以羟丙基-β-环糊精为致孔剂制得的膜层孔径约为4 nm,因而膜层不会因为孔径接近光波长的1/4而引起散射.与传统的致孔剂泊洛沙姆(F127)等相比,羟丙基-β-环糊精具有致孔效率高及折射率更低等优点,在模板剂领域具有广泛的应用前景.  相似文献   

11.
Germanium is electrodeposited in a template formed from a dried suspension of silica spheres. The germanium completely fills the pores of the silica matrix. The semiconductor, as deposited, is amorphous but can be crystallized by annealing. Selective dissolution of the silica template gives a macroporous germanium-air sphere matrix, which offers interesting possibilities for photonic applications.  相似文献   

12.
Silica particles containing immobilised peptidic templates have been used for the generation of hierarchically imprinted polymers. The pores of the silica mould were filled with a mixture of monomers/initiator and polymerised, followed by dissolution of the silica template. This method leaves behind imprinted polymers with binding sites located at the surface, which are capable of recognising larger molecules with the same immobilised epitope. All the products resulting from solid-phase synthesis of peptides were characterised by elemental analysis, FT-IR spectroscopy and fluorescence microscopy. The hierarchically imprinted polymers generated from these products were characterised by elemental analysis, FT-IR spectroscopy, fluorescence microscopy, scanning electron microscopy (SEM) and nitrogen adsorption, providing evidence concerning the reproducibility of each step. The chromatographic properties of the materials have been investigated and the advantages of the immobilisation method have been proven. The materials exhibit selectivity for their templates and other structurally related dipeptides. Furthermore, the polymers proved to be capable of recognising larger peptides containing the immobilised sequence.  相似文献   

13.
杨桃状ZnO纳米片微球的制备及气敏性能的研究   总被引:1,自引:0,他引:1  
以六水合硝酸锌和尿素为原料,水为反应介质,油酸作为表面活性剂,经水热过程合成了由纳米片组装的碱式碳酸锌微球前驱体,经煅烧后得到形貌一致的氧化锌(ZnO)纳米片组装的杨桃状微球。采用X射线衍射仪(XRD)和环境扫描电镜(SEM)对样品进行表征,结果表明产物为六方纤维矿结构的ZnO,微球尺寸比较均一,直径约为20μm,组装单元扇形ZnO纳米片均匀排列,单元之间存在均匀空隙,BET测试显示纳米片呈现多级介孔结孔结构,比表面积为18.9m2·g-1,室温下的光致发光性能表明其结构表面存在大量氧空位,对产物ZnO气敏元件进行了乙醇和丙酮气体敏感性测试。  相似文献   

14.
Summary: A novel, stabilizer‐free dispersion polymerization with alkyl esters as reaction media gives uniform alternating microspheres of maleic anhydride (MAn)/vinyl acetate (VAc) copolymer. The diameter of the copolymer microspheres could be precisely controlled from 80 to 750 nm by changing the monomer concentration or feed ratio. Moreover, this new type of copolymer microspheres with reactive anhydride groups on the surface has good solubility in common nontoxic solvents such as water and ethanol.

SEM image of the powder surface of copolymer microspheres formed at [MAn] = [VAc] = 1.5 M .  相似文献   


15.
By using acetone‐water as the medium and potassium persulfate (KFS) as the initiator, emulsifier‐free emulsion co‐polymerization of styrene with co‐monomers: MMA, BMA, EA and BDA under microwave irradiation has been investigated. The influence of the each co‐monomer content and hydrophilicity on the hydrodynamic radius Rh of the synthesized copolymer nanoparticles is discussed in detail. The results show mat the increase in ratio of hydrophilic copolymer causes an increase in consumption of the initiator in the initiation reaction, so an increase in the concentration of the surface ? OSO3 groups which cause the increase in the stability of the latex and gives rise to the formation of smaller micelles. The nano‐particle radius will increase again when the co‐monomer content increases to a certain degree. The curve of the particle hydrodynamic radius vs the co‐monomer content has a minimum point.  相似文献   

16.
Calorimetry was used to measure the enthalpies of solution of chloroform in various proton-acceptor solvents and, vice versa, proton-acceptors in chloroform. Based on a previously proposed equation, the enthalpies of specific interaction were calculated and compared with the published data on the enthalpy of hydrogen bonding of chloroform with various proton-acceptor solvents. The composition of the H-bonded complexes mainly formed during the dissolution of proton-acceptor solutes in chloroform was established. It was demonstrated that the dissolution of ethers in chloroform is predominantly accompanied by the formation of 1: 1 complexes, while the dissolution of acetone, dimethylformamide, and dimethyl sulfoxide in chloroform gives rise to more complex associates.  相似文献   

17.
Complex formation in the Cu(II)-dihydrazinomethanethione (H2NHN-CS-NHNH2)-acetone ternary system in an ethanol solution containing CuCl2, dihydrazinomethanethione, and acetone, as well as on contact of gelatin-immobilized copper(II) hecacyanoferrate(II) with alkaline (pH >10) aqueous solutions containing the above organic compounds was studied. It was found that template synthesis is realized in both cases but gives different products: in the first case, a heteroligand chelate of CuL1(OH) with 9-hydrazino-9-mercapto-4,6,6-trimethyl-2,3,7,8-tetraazanona-3,8-dienethiohydrazide and hydroxide ion is formed, while in the second, a chelate of CuL2 with 2,8,10,10,16-pentamethyl-3,4,6,7,11,12,14,15-octaazaheptadeca-2,5,7,12,15-pentaene-5,13-dithiol. In both cases, dihydrazinomethanethione and acetone function as ligsons. A scheme of involved processes is suggested.  相似文献   

18.
The electrodeposition of poly(3,4-ethylenedioxythiophene) (PEDOT) films from aqueous surfactant solution through a two-dimensional poly(styrene) (PS) template onto indium tin oxide (ITO) substrate has been investigated. The polymer grows in the interstitial spaces of the self-assembled PS spheres which were subsequently removed by dissolution in tetrahydrofuran (THF). Surface characterization by scanning electron microscopy (SEM) and atomic force microscopy (AFM) reveals that two-dimensional nanoporous honeycomb PEDOT structures can easily be obtained by using PS spheres of different sizes. Gold electrodeposition onto the nanostructured PEDOT electrode was investigated and SEM images show preferential formation of nanoparticles (NP) on the wall and the rim of the PEDOT film but metal clusters inside the pores are also observed.  相似文献   

19.
分别以过硫酸钾和偶氮二异丁基脒盐酸盐为引发剂,以聚乙烯吡咯烷酮(PVP)为分散剂,在水中引发苯乙烯聚合制备了2种表面分别带负电性和正电性基团的聚苯乙烯(PS)模板微球.在氨水催化下,利用正硅酸乙酯的水解缩合,形成PS/SiO_2复合微球,去除模板后得到中空SiO_2微球,并对其进行FTIR、电子显微镜、TGA以及氮气吸附等分析表征.结果表明,PS模板微球表面的电性决定了OH-的分布,从而导致PS模板微球表面SiO_2壳层不同的形成机制.当以表面带负电的PS微球为模板时,可得到树莓状的中空SiO_2微球;而以表面带正电的PS微球为模板时,得到是表面光滑的,具有介孔结构的中空SiO_2微球.  相似文献   

20.
氧化铁纳米线阵列的溶胶-凝胶模板法制备与表征   总被引:16,自引:0,他引:16  
0引言氧化铁在颜料、磁记录材料和催化剂等方面具有广泛的应用[1,2]。尤其是纳米氧化铁在纳米尺度具有良好的气敏特性[3]。纳米材料可以分为零维、一维、二维纳米材料,一维材料是纳米材料的重要组成部分,是纳米组装的基础。一维纳米材料的制备方法中氧化铝模板法占有极其重要的  相似文献   

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