几种聚醚酰亚胺的气体透过性能

本文研究了一系列芳环聚醚酰亚胺(PEI)对H_2、CO_2、O_2和N_2的透过性能与分子结构之间的关系。单醚酐型聚醚酰亚胺具有较高的透氢系数和H_2/N_2分离系数。由半刚性的4,4′-二氨基二苯酮(DABP)与柔性的三苯二醚四酸二酐(HQDPA)、二苯醚四酸二酐(ODPA)缩聚得到的聚醚酰亚胺具有很高的H_2/N_2、CO_2/N_2和O_2/N_2分离系数。     

有机硅类共聚物的合成,成膜及其透气性能

本文对聚二甲基硅氧烷(PDMS)进行了改性研究。研究了α,ω-双端羟基聚二甲基硅氧烷(Ⅱ)和乙二醇(Ⅲ)与二甲胺苄基丙二酸二乙酯(Ⅰ)共缩聚物的合成方法,成膜方法,并从电子给体-受体的观点讨论了此类膜对氧,氮气体的透过性能。结果表明,改变原料的摩尔比,用共缩聚反应可得到不同含量的(Ⅱ)和(Ⅰ)的共聚物,它们具有良好的成膜性。其氧气透过系数P_(O_2)值通常在10~(-8)[cc(STP)·cm/cm~2·s·cmHg]数量级,氧、氮气体透过系数比P_(O_2)/P_(N_2)可达2.54,并且随着电子给体化合物(Ⅰ)在共聚物中含量的增加,P_(O_2)/P_(N_2)值也随着增高。     

PDMS/EPDM二元聚合物网络杂化膜的制备及性能研究

根据氧气的促进输送机制,使用乙丙三元橡胶磺酸钴离聚体(Co(Ⅱ)-S-EPDM)与硅橡胶PDMS进行了共混交联改性,制备出PDMS/Co(Ⅱ)-S-EPDM互穿网络杂化交联膜。Co(Ⅱ)-S-EPDM中双键、PDMS的乙烯基与含氢硅油在氯铂酸的催化下发生加成反应,形成了有机硅分子链与碳链的杂化交联互穿网络。共价键交联可使两种化学结构明显不同的分子链实现"强迫互容"。新的制备方法不仅改善了成膜性能,还使得在低压差下透氧性能P_(O_2)、和分离性能α_(O_2/N_2)同时增大。试验结果表明,在20℃和0.025 MPa压差条件下,当PDMS/Co(Ⅱ)-S-EPDM质量比为80/20时,P_(O_2)为729 Barrer,α_(O_2/N_2)则高达6.52,富氧性能超越了Robeson上限。     

含有机硅多嵌段共聚物的研究Ⅳ.含有机硅多嵌段共聚物的富氧功能

研究了几种新型含有机硅二元和三元多嵌段共聚物的氧、氮选择透过性能。其中双酚A聚羟基醚-聚二甲基硅氧烷二元多嵌段共聚物-(PHE-PDMS)_n的透氧系数Po_2=510Barrer、氧氮分离系数a o_2/N_2=2.2,聚苯醚-聚二甲基硅氧烷-聚对羟基苯乙烯三元多嵌段共聚物-(PPO-PDMS-pHS)_n的Po_2=156 Barrer、do_2/N_2=2.4,两者都具有良好的力学性能。此外,含有机硅三元多嵌段共聚物与聚三甲硅基丙炔(PTMSP)起薄复合后,改善了PTMSP超薄膜的透气稳定性。其JO_2≈1.0×10~(-3)cm~2/cm~2·s·cmHg,do_2/N_2≥2.0。     

TMSP—PMDSP共聚物膜的氧,氮透过性

研究了三甲基硅丙炔(TMSP) 和五甲基二硅丙炔(PMDSP) 的共聚物膜对O_2、N_2气体的透过行为。发现 TMSP-PMDSP共聚物膜对O_2、N_2气体的透过活化能为负值,透过系数随温度升高而下降;受热历程不同,气体在膜中的透过行为也不相同。膜两侧气体压差不同时,气体在膜中的透过系数亦发生变化。用氟化物HFBM对共聚物膜表面进行了化学改性,改性膜的P_(O_2)/PN_2值达到3.52。     

H_8[P_2Mo_(17)Co(OH_2)O_(61)]和H_8[P_2Mo_(17)Ni(OH_2)O_(61)]的抑酶活性研究

合成了2种过渡金属取代的多酸H_8[P_2Mo_(17)Co(OH_2)O_(61)]和H_8[P_2Mo_(17)Ni(OH_2)O_(61)],并对其抑酶活性进行了研究.结果表明,这2种化合物对酪氨酸酶均有有效的抑制效果.抑制机理表明2种化合物均是可逆竞争型抑制剂.H_8[P_2Mo_(17)Co(OH_2)O_(61)]和H_8[P_2Mo_(17)Ni(OH_2)O_(61)]的半抑制率IC_(50)值分别为(0.434 0±0.000 4)和(0.466 5±0.012 0)mmol/L,抑制常数K_Ⅰ分别为0.216 7和0.220 4mmol/L.该研究能够扩大多金属氧酸盐的应用范围.     

CF4等离子体表面氟化PTMSP膜

本文对聚三甲基硅基丙炔(PTMSP)膜进行CF_4等离子体表面氟化研究。改性的PTMSP膜氧氮选择性显著提高(P_(O_2)/P_(N_2)=4-5,P_(O_2)=10~2-10~3barrer)。等离子体改性条件,如处理时间、单体压力、放电功率对PTMSP膜透气性的影响进行了研究。XPS谱分析表明改性后,膜表层化学组成发生了显著变化、碳硅含量大幅度减小,氟含量随着处理程度的增加而增加,氟碳比与膜的选择性有着密切的关系,当 F/C>1时,膜的P_(O_2)/P_(N_2)可达4以上。     

土壤反硝化培养气体中N_2和O_2的气相色谱测定方法

为测定土壤反硝化培养气体中的N_2和O_2的浓度,利用厌氧箱制备样品,建立了自动进样器阀进样、填充柱分离,气相色谱-热导检测器测定的方法。N_2和O_2在2min内达到基线分离。对于低浓度的样品(N2≤1.0%,O2≤0.254%),使用厌氧箱后N_2和O_2测定的峰面积比未使用时相比降低约20.0%。目标分析物的保留时间和峰面积的相对标准偏差(RSD)分别小于0.1%和1.0%。N_2和O_2的线性范围分别为780~60 100μmol/mol和290~20 000μmol/mol,线性相关系数均在0.999以上,检出限分别为232.7μmol/mol和87.5μmol/mol。厌氧箱的使用很大程度上避免了空气中的N_2和O_2进入,使培养气体中低含量N_2和O_2的测定更加准确。     

聚三甲硅基丙炔膜表面改性的XPS研究——Ⅰ.用N-溴代丁二酰亚胺的表面改性

用N-溴代丁二酰亚胺的丙酮溶液在回流温度下对三甲硅基丙炔的均聚物和共聚物作了表面改性。XPS的研究表明,试样表面层中Br原子含量随溴化时间的增长而增加,C_(IS)谱变宽且产生来自C-O和C-Br结构的新谱线。红外光谱证明溴化反应产生CH_2Br结构。溴化使膜的气透性发生相应的变化,即α_(O_2/N_2)值增高,P_(O_2)值降低。     

一种可溶性聚酰亚胺的合成与性能研究

选用三苯二醚四酸二酐 (HQDPA)和二甲基二苯甲烷二胺 (DMMDA)为单体 ,在NMP中通过低温溶液缩聚 化学亚胺化法合成了高分子量可溶性聚醚酰亚胺PI(HQDPA DMMDA) .通过FT IR、WAXD、TG DTG以及DSC等手段对聚酰亚胺的结构和性能进行了表征 .结果表明 ,合成的PI为无规高分子结构 ,平均分子链间距为 0 5 16 3nm ;易溶于N 甲基吡咯烷酮、N ,N 二甲基乙酰胺和四氢呋喃等极性溶剂中 ;其 10 %的分解温度为5 2 8℃ ,玻璃化转变温度Tg 为 2 5 1℃ ;断裂伸长率为 2 4 % ,断裂强度为 10 7MPa ;2 5℃时 ,PI均质膜的透H2 系数为 3 80 9Barrer ,H2 N2 、H2 CH4 的理想分离系数为 16 6 9、2 14 0 ;其透N2 、O2 、CO2 和CH4 系数均在 0 0 18～0 5 76Barrer之间     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

解决能源问题的新途径--光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。