甲基丙烯酸二甲氨基乙酯溴代烷季铵盐与苯乙烯共聚合的研究

以甲基丙烯酸二甲氨基乙酯溴代乙烷（ Ｍ Ａ Ｅ Ｂ） 或丁烷（ Ｍ Ａ Ｂ Ｂ） 季胺盐与苯乙烯（ Ｓｔ）为单体,采用溶液自由基共聚合方法,合成了一类新型阳离子两亲共聚物．详细地研究了聚合条件及共聚物的溶解性．共聚物“亲油”和“亲水”单元的无规结构被 Ｉ Ｒ、１ Ｈ Ｎ Ｍ Ｒ 及１３ Ｃ Ｎ Ｍ Ｒ所证实．最后,用线性化（ Ｙ Ｂ Ｒ） 法分别求得 Ｍ Ａ Ｅ Ｂ／ Ｓｔ 和 Ｍ Ａ Ｂ Ｂ／ Ｓｔ 的单体竞聚率,ｒ Ｍ Ａ Ｂ Ｂ ＝０４４ ,ｒ Ｓｔ ＝ ０１５ ,ｒ Ｍ Ａ Ｅ Ｂ＝ ０６６ ,ｒ Ｓｔ＝ ０３６ ．     

尼龙6/多单体接枝聚丙烯共混物的形态结构及力学性能的研究

用多组分熔融接枝的方法将甲基丙烯酸缩水甘油酯（ Ｇ Ｍ Ａ） 和苯乙烯（ Ｓｔ） 共同接枝于聚丙烯（ Ｐ Ｐ） 上,制得多单体接枝聚丙烯 Ｐ Ｐ ｇ （ Ｇ Ｍ Ａ ｃｏ Ｓｔ） ．该接枝物具有高的 Ｇ Ｍ Ａ 接枝率．本研究利用 Ｆ Ｔ Ｉ Ｒ、 Ｓ Ｅ Ｍ、 Ｔ Ｅ Ｍ、 Ｄ Ｓ Ｃ 和力学性能测试等分析方法,研究了多组分熔融接枝聚丙烯（ Ｐ Ｐ ｇ （ Ｇ Ｍ Ａ ｃｏ Ｓｔ）） 对尼龙６／ Ｐ Ｐ 共混物的形态结构, Ｔｇ 和力学性能的影响．结果表明, Ｐ Ｐ ｇ （ Ｇ Ｍ Ａ ｃｏ Ｓｔ） 中的环氧基团与尼龙６（ Ｐ Ａ６） 末端的胺基发生化学反应,原位形成的 Ｐ Ｐ Ｐ Ａ６ 共聚物能有效的改善 Ｐ Ａ６ 与 Ｐ Ｐ 的相容性,可以使 Ｐ Ｐ 均匀的分散在 Ｐ Ａ６ 基体中,相区尺寸明显减小,提高了拉伸强度．由于两相的相容性较好,从而共混物的 Ｔｇ 有明显的变化．此外,通过透射电镜观察,发现 Ｐ Ａ６／ Ｐ Ｐ ｇ （ Ｇ Ｍ Ａ ｃｏ Ｓｔ）（７０／３０） 合金中存在着特殊的微相分离结构．     

甲基丙烯酸丁酯和苯乙烯的原子转移自由基共聚

研究了甲基丙烯酸丁酯（ＢＭＡ）和苯乙烯（Ｓ）这两种不同极性单体的原子转移自由基嵌段共聚和无规共聚,得到了实测分子量与理论分子量相近,分子量分布较窄的嵌段共聚物和无规共聚物．聚合过程中分子量和单体转化率成比例增加,多分散性指数变化不大．用１Ｈ ＮＭＲ法测定共聚组成,Ｋｅｌｅｎ Ｔｕｄｏｓ法计算竞聚率．得到ｒＳｔ＝０９１,ｒＢＭＡ＝０３２．     

α-氯乙酰氧基大分子引发剂的合成及其引发原子转移自由基聚合

通过阴离子聚合制备了α－氯乙酰氧端基大分子引发剂。并用于引发（甲基）丙烯酸酯类单体进行“活性”／可控的原子转移自由基聚合（ＡＴＲＰ）。结果表明：酰化反应温度为６０℃,氯乙酰氯过量５倍和反应２４ｈ,酰化效率达到９９．８％,产物经红外和核磁共振表征,证明α－氯乙酰氧端基的结构。用此引发剂引发乙烯基单位进行ＡＴＲＰ,合成了ＰＳｔ－ｂ－ＰＭＡ和ＰＳｔ－ｂ－ＰＢＡ嵌段共聚物,其结构通过＾１Ｈ ＮＭＲ得到确证     

N,N—二乙基二硫代氨基甲酸聚氯乙烯酯引发甲基丙烯酸甲…

用铜试剂（Ｎ，Ｎ－二乙基二硫代氨基甲酸钠）取代聚氯乙烯中的部分氯原子制备了Ｎ，Ｎ－二乙基二硫代氨基甲酸聚氯乙烯酯（ＰＶＣ－ＳＲ），研究了紫外光照下ＰＶＣ－ＳＲ引发甲基丙烯酸甲酯（ＭＭＡ）的聚合反应，考察了光照时间、单体浓度、ＰＶＣ－ＳＲ用量及官能度的影响。结果表明，ＰＶＣ－ＳＲ能有效地引发ＭＭＡ聚合，其产物是交联型接枝聚合物，且具有高接枝率和接枝效率。     

PP—g—MAZn离聚物的固相法合成与表征

以ＤＣＰＯ为引发剂，将ＰＰ粉末通过固相法与马为酸锌发生接枝反应，合成不同接枝率的ＰＰ－ｇ－ＭＡＺｎ离聚物。考察反应温度，引发剂浓度，单体的用量对接枝率的影响，研究表明，（１）ＰＰ－ｇ－ＭＡＺｎ离聚物的ＦＴＩＲ图中，１５４０ｃｍ＾－１－１６４３ｃｍ＾－１之间出现宽的峰，说明ＭＡＺｎ与ＰＰ发生了接枝反应；（２）ＰＰ－ｇ－ＭＡＺｎ的ＷＡＸＤ谱中在２θ＝１０．６°，３１．２°，３３．２°，处有衍射峰，表明     

聚环氧乙烷为支链的两亲共聚物的表征及性能

用端基带有甲基丙烯酸酯的聚环氧乙烷大分子单体（ＰＥＯ—ＭＡ）分别与小分子单体苯乙烯（Ｓ）、甲基丙烯酸甲酯（ＭＭＡ）、丙烯酸甲酯（ＭＡ）溶液自由基共聚合得到了三种具有不同主链结构的以聚环氧乙烷（ＰＥＯ）为支链的两亲接枝嵌段共聚物（分别简写为：ＰＳ─ｇ─ＰＥＯ，ＰＭＭＡ─ｇ─ＰＥＯ，ＰＭＡ─ｇ─ＰＥＯ）．用ＧＰＣ、ＩＲ、１Ｈ─ＮＭＲ、ＷＡＸＤ和ＤＳＣ对其结构进行了表征．研究了接校共聚物的结晶性能、乳化性能以及在Ｗｉｌｌｉａｍｓｏｎ反应中相转移催化作用．结果表明，不同主链结构有不同的结晶度，并随支链ＰＥＯ含量的增加，分子量的增大而提高；其乳化体积和相转移催化反应的转化率均随着共聚物浓度的增加、支链ＰＥＯ含量的增人而增大，随支链ＰＥＯ分子量的提高而减小．     

N，N－二乙基二硫代氨基甲酸聚氯乙烯酯引发甲基丙烯酸甲酯的光接枝交联聚合反应

用铜试剂（Ｎ，Ｎ－二乙基二硫代氨基甲酸钠）取代聚氯乙烯中的部分氯原子制备了Ｎ，Ｎ－二乙基二硫代氨基甲酸聚氯乙烯酯（ＰＶＣ－ＳＲ），研究了紫外光照下ＰＶＣ－ＳＲ引发甲基丙烯酸甲酯（ＭＭＡ）的聚合反应，考察了光照时间、单体浓度、ＰＶＣ－ＳＲ用量及官能度的影响．结果表明，ＰＶＣ－ＳＲ能有效地引发ＭＭＡ聚合，其产物是交联型接枝聚合物，且具有高接枝率和接枝效率。     

GMA熔融接枝EPDM的研究

以甲基丙烯酸缩水甘油酯（ＧＭＡ）为接枝单体，过氧化二异丙苯（ＤＣＰ）为引发剂，对三元乙丙胶（ＥＰＤＭ）进行了熔融接枝，在烃链上引入极性基团，以改善ＥＰＤＭ与极性聚合物的相容性。用差示扫描量热计（ＤＳＣ）研究了ＧＭＡ的聚合温度，用富里叶红外（ＦＴ－ＩＲ）、凝胶渗透色谱（ＧＰＣ）对接枝产物进行了表征。实验结果表明，产物的接枝率和凝胶量可以通过反应条件（温度、时间、反应物组成及加料方式）来控制。     

元素分析法测定苯乙烯和丙烯酸－β－羟乙酯竞聚率的误差分析

一对单体，可查到非常多数值不同的竞聚率文献值，说明无论从精度和准确性来说，竞聚率的测定和求算都可能产生很大误差。本文在单体敏感点组成进行实验，用元素分析法测定共聚物组成，用Ｅｒｒｏｒ－ｉｎ－ＶａｒｉａｂｌｅＭｅｔｈｏｄ（ＥＶＭ）［１］法计算苯乙烯（Ｓｔ，Ｍ１）和丙烯酸－β－羟乙酯（ＨＥＡ，Ｍ２）竞聚率，分析全过程的误差来源和大小。     

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.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

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。     

化学计量中不确定度评定研究进展

测量不确定度是表征合理地赋予被测量之值的分散性的参数。本文针对化学计量不确定度评定基础模型仅适用于线性模型、概率分布为正态分布或缩放位移t分布等局限,介绍了近年来不确定度评定的研究热点:蒙特卡罗方法(Monte Carlo Method,MCM),不确定度评定的来源、评定概念、评估方法及其发展过程,扩大了测量不确定度评定与表示的适用范围。     

微量钙的测定方法研究进展

介绍了1995-2006年期间测定微量和痕量钙的方法,如电感耦合等离子体-原子发射光谱法、原子吸收光谱法以及离子色谱法等的工作原理和特点,并说明了其测定微量钙的应用领域。并对微量钙的测定技术进行了展望(引用文献55篇)。     

Stages of thermal decomposition of sodium oxo-salts of sulphur

Thermal behaviour of sodium oxo-salts of sulphur: Na₂SO₄, Na₂S₂O₇, Na₂S₂O₆, Na₂SO₃, Na₂S₂O₅, Na₂S₂O₄, Na₂S₂O₃, Na₂S₃O₆ and of sulphides Na₂S and Na₂S₂ was studied on heating up to 1000°C. The experiments were performed with anhydrous compounds obtained from commercial products by recrystallisation and dehydration. The stage mechanisms of decomposition of anionic sub-lattices of the salts have been proposed basing on the Górski’s morphological classification of simple species. The thermal stability and the stage decomposition mechanisms were correlated with the structure and the potential chemical properties of the salt anions. The thermal decomposition processes were studied by means of thermal analysis, and the decomposition products were identified by means of X-ray phase analysis.     

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.     

过渡金属配合物的合成、表征及纳米胶束自组装

以异烟酸和溴代十二烷为原料合成液晶基元异烟酸十二烷基酯,以水杨醛和邻氨基苯酚为原料来制各希夫碱,将希夫碱与异烟酸酯同时与过渡金属配位,透射电镜形态观测到10～60m左右的线状形态的纳米胶束。并利用红外光谱,紫外可见吸收光谱等手段对其结构和性质进行了表征。