交联密度对聚氨酯／聚苯乙烯互穿聚合物网络动态力学性能…

采用同步法合聚氨酯／聚苯乙烯互穿聚合物网络，通过改变ＮＣＯ／ＯＨ比、三元醇／二元醇比、异氰酸酯类型、多元醇分子量、二乙烯苛苯含量及丙烯酸β－羟乙酸的含量，研究了单网及网间交联密度对ＰＵ／ＰＳＩＰＮ动态力学性能影响的规律。结果表明：对相容性差的ＰＵ／ＰＳＩＮＰ体系，要用增加交联密度，加快网络固化速度导致“强迫互容”、能提高两网的互穿与缠结，增进组份的互容，但单网固化速度过快相容性反而下降。     

聚环氧氯丙烷聚氨酯／聚甲基丙烯酸甲酯互穿网络聚合物的相容性与力学性能

用同步法合成了聚环氧氯丙烷聚氨酯／聚甲基丙烯酸甲酯互穿网络聚合物［ＰＵ（ＰＥＣＨ）／ＰＭＭＡＩＰＮ］，调节ＩＰＮ中两组分组成比制备出由完全弹性体、增强弹性体、增韧塑料到脆性塑料多种高聚物合金材料．用ＤＳＣ、动态力学谱、ＴＥＭ对ＩＰＮ的研究结果表明，ＰＵ（ＰＥＣＨ）／ＰＭＭＡＩＰＮ的两组分是完全相容的；同时对各种组成比的ＩＰＮ材料进行力学性能测试，用相容性ＩＰＮ中互穿、缠结结构解释其力学行为，并用ＳＥＭ对断面形貌进行了观察解释．     

聚氨酯型互穿网络聚合物的研究

以甲苯二异氰酸酯和蓖麻油反应，合成了一系列室温固化的蓖麻油型聚氨酯。分别研究了蓖麻油聚氨酯（ＣＯＰＵ）／聚苯乙烯（ＰＳｔ）ＩＰＮｓ、ＣＯＰＵ／聚丙烯腈（ＰＡＮ）ＩＰＮｓ的结构和性能。结果表明：ＣＯＰＵ／ＰＡＮ的力学性能较ＣＯＰＵ／ＰＳｔ的力学性能为好。为进一步改善聚合物之间的相容性，在聚苯乙烯网络中引入极性较大的丙烯腈制备了ＣＯＰＵ／Ｐ（Ｓｔ－ＣＯ－ＡＮ）ＩＰＮｓ，并对它的力学性能、热分析、动态力学性能、热稳定性等作了系统的研究。结果表明：当聚氨酯浓度为６０％时，改变Ｓｔ、ＡＮ的比例，随ＡＮ含量的增加，体系的微相分离程度降低。改变ＣＯＰＵ／Ｐ（Ｓｔ－ＣＯ－ＡＮ）的比例，ｔａｎδ－Ｔ曲线上均呈现一个较宽的玻璃化转变温度；热重分析表明，其初始分解温度可达２４４℃。     

聚氨酯／聚（苯乙烯－甲基丙烯酸甲酯－甲基丙烯酸）互穿聚合物网络的研究

研究了（蓖麻油－聚乙二醇）聚氨酯／聚（苯乙烯－甲基丙烯酸甲酯－甲基丙烯酸）（ＰＵ／Ｐ（Ｓｔ－ＭＭＡ－ＭＡＡ））互穿聚合物网络（ＩＰＮ）．动态力学性能及透射电镜结果均表明该体系相分离较严重；ＩＰＮ具有两个玻璃化转变温度，它们有不同程度的内移，形成一定程度分子水平的混合，而ＩＰＮ（５０／５０）其分子混合水平较大，互穿缠结程度较高。形成ＩＰＮ后，其力学性能得以改善。透射电镜结果表明，聚氨酯网的交联密度直接影响ＩＰＮ的相区尺寸。形成ＩＰＮ后热稳定性提高，易于降解断链的Ｓｔ－ＭＭＡ－ＭＡＡ单体起到了自由基消除剂的作用。     

丁腈橡胶对聚甲醛树脂的增韧机理研究

研究了丁腈橡胶（ＮＢＲ） 对聚甲醛（ＰＯＭ） 树脂的增韧机理,并比较了ＰＯＭ／ＮＢＲ 体系和ＰＯＭ／ 热塑性聚氨酯（ＴＰＵ） 体系的异同．结果表明,高丙烯腈（ＡＮ） 含量的ＮＢＲ 有着和ＴＰＵ 相近的溶度积参数,且其分子上的氰（ＣＮ） 基或双键对ＰＯＭ 分解时产生的甲醛及大分子自由基的捕捉作用,有利于改善ＮＢＲ 和ＰＯＭ 之间相容性,因而可和ＰＯＭ 树脂形成良好的合金体系;当ＮＢＲ 含量达４０ｗｔ％ 时,ＰＯＭ／ＮＢＲ 体系出现脆 韧转变,从逾渗机制、剪切带机制、类互穿网络（ＩＰＮ） 作用机制等角度进行考察的结果证明,ＮＢＲ 对ＰＯＭ 树脂的增韧行为以及ＰＯＭ／ＮＢＲ 共混合金体系的脆 韧转变规律与ＰＯＭ／ＴＰＵ 体系相一致．     

不饱和聚酯／聚氨酯互穿网络聚合物的合成

以醋酸酐封端的不饱和聚酯（ＦＵＰＲ）与交联聚氨酯预聚物制备了具有互穿聚合物网络（ＩＰＮ）的不饱和聚酯／聚氨酯，通过红外，ＤＳＣ和扫描电镜等分析了ＦＵＰＲ／ＰＵＩＰＮ网络形成的动力学，微相分离行为及力学性能，结果表明，当ＦＵＰＲ／ＰＵ达到某一比值时，产生网络互穿效应，可改善聚氨酯的刚性，提高不饱和聚酯的抗冲性。     

聚丙烯酸酯/环氧树脂互穿网络聚合物的研究Ⅲ.橡胶态弹性模量和互穿缠结

采用一步法（Ｓｉｍｕｌｔａｎｅｏｕｓｌｙ）合成了双组分的聚丙烯酸酯／环氧树脂互穿网络聚合物（ＩＰＮｓ）．选择预溶胀方法制备了聚丙烯酸酯和环氧树脂两种组分网络．测定了各种组分比的ＩＰＮ和不同溶胀度下的组分网络的动态力学性能，从橡胶态弹性理论出发讨论了ＩＰＮ和预溶胀网络之间在橡胶态弹性模量上的关系，并据此指出互穿缠结增加了网络的有效“交联密度”，因此，它对ＩＰＮ的橡胶态弹性模量有较大的贡献．密度测量的结果也提供了另一方面的证据     

聚氨酯互穿聚合物网络阻尼性能研究进展

介绍了聚氨酯互穿聚合物网络（ＰＵ ＩＰＮ）作为阻尼材料的研究进展,分别讨论了聚氨酯（ＰＵ）／环氧树脂（ＥＰ）ＩＰＮ和ＰＵ／乙烯基聚合物ＩＰＮ的阻尼性,以及影响阻尼性能的因素,并比较了不同类型的ＰＵ ＩＰＮ的优缺点及新的可能的探讨方向。     

聚环氧氯丙烷聚氨酯／聚甲基丙烯酸甲酯IPN力学性能

利用改变组成比、聚氨酯ＰＵ软段的分子量、Ｒ值、异氰酸酯和两网络各自交联剂含量合成出５个系列的聚环氧丙烷聚氨酯／聚甲基丙烯酸甲酯互穿聚合物网络，利用ＩＰＮ中交联、互穿、缠结程度的不同，并结合ＤＣＳ、ＴＥＭ、动态粘弹谱讨论了ＩＰＮ力学性能。     

SYNTHESIS AND CHARACTERIZATION OF NEIV PICKET FENCE CROWN－PORPHYRIN AND ITS Zn（Ⅱ），Fe（Ⅲ） COMIPLEXES

ＳＹＮＴＨＥＳＩＳＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦＮＥＩＶＰＩＣＫＥＴＦＥＮＣＥＣＲＯＷＮ－ＰＯＲＰＨＹＲＩＮＡＮＤＩＴＳＺｎ（Ⅱ），Ｆｅ（Ⅲ）ＣＯＭＩＰＬＥＸＥＳ￥ＹａｎｇｄｅＷＵ，ＦａＣｈｅｎｇＱＩＡＮ，ＬｉａｎＦａｎｇＳＨＥＮａ（Ｄｅ...     

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.     

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.     

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^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

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。