乙丙共聚物的过氧化氢基化反应及其与烯类单体的接枝共聚合

本文研究了乙丙共聚物在含臭氧的氧气流中的过氧化氢基化反应,考察了温度、时间、浓度以及添加剂等对过氧化氢基化物(EPHP)中过氧化氢基含量的影响;研究了EPHP与苯乙烯类单体进行接枝共聚反应以及接枝产物的共混增韧作用。     

新洁尔灭与过氧化氢酶的微观作用机理

模拟生理条件下,利用多种光谱技术和酶活性测定法研究了新洁尔灭与过氧化氢酶的相互作用过程,探讨了二者的结合特性,过氧化氢酶空间结构和酶活性的变化.结果表明新洁尔灭对过氧化氢酶无荧光猝灭作用,其使过氧化氢酶骨架结构变松散,部分氨基酸残基微环境和蛋白二级结构发生改变,说明新洁尔灭对过氧化氢酶活性具有显著的抑制作用.从分子水平上证明了新洁尔灭可改变过氧化氢酶的结构和功能.     

TS-1/尿素/过氧化氢体系中的丙烯环氧化反应

 研究了TS-1/尿素/过氧化氢体系中的丙烯环氧化反应,考察了尿素用量和过氧化氢浓度对反应的影响. 结果表明,加入适量尿素可以显著提高环氧丙烷选择性和过氧化氢的利用率,而提高过氧化氢浓度不利于丙烯环氧化反应. 在尿素用量为31.2 g/L和过氧化氢浓度为0.09 mol/L时,过氧化氢转化率可达90.00%,环氧丙烷选择性可达96.12%,过氧化氢利用率可达98.46%.     

半干法烟气脱硫中过氧化氢溶液强化吸收二氧化硫的研究

在半干法烟气脱硫的基础上,提出了利用过氧化氢的强氧化性,在喷水增湿脱硫剂过程中添加少量的过氧化氢溶液进一步提高其脱硫效率的方法,并重点研究了过氧化氢水溶液浓度以及各种因素(Ca/S摩尔比、近绝热饱和温度等)对脱硫效率的影响.结果表明,采用1.0%～2.0%过氧化氢水溶液增湿脱硫剂,其脱硫效率可提高20%～30%;随着过氧化氢溶液浓度的增加,脱硫效率及吸收剂利用率更高.     

水溶性金属卟啉类过氧化氢酶的催化活性研究

过氧化氢酶与血红蛋白、肌红蛋白一样,统属于血红蛋白质,具有相同的活性部位——铁卟啉,因此金属卟啉作为生物酶模拟的研究有着重要意义和广阔的应用前景。我们曾报道水溶性金属卟啉修饰的阴离子交换树脂类过氧化氢酶的催化活性。本文应用光谱法,通过测量反应(1)生成的醌型染料,进一步研究了Fe—TPPS作为类过氧化氢酶的均相催化活性,得到了较满意的结果。     

氯化血红素的催化显色反应及分析应用

本文研究了以氯化血红素替代辣根过氧化物酶催化过氧化氢与4-氨基安替比林和苯酚的催化显色反应条件,拟订了测定过氧化氢的高灵敏催化分光光度法,做了多种离子对测定过氧化氢的干扰实验。并通过与葡萄糖氧化酶联用,拟订了水介质和血清中葡萄糖的分光光度测定方法,试用于测定血清样品中的葡萄糖含量得到了较满意的结果。     

有机过氧化氢物与芳叔胺体系引发甲基丙烯酸甲酯聚合的研究

以有机过氧化氢物叔丁基过氧化氢(TBH)或异丙苯过氧化氢(CHP)与芳叔胺N,N-二甲基苯胺(DMA)或其衍生物组成的体系引发甲基丙烯酸甲酯(MMA)聚合。研究有机过氧化氢物与芳叔胺结构对聚合的影响,测定了TBH-胺与CHP-胺体系引发MMA聚合的总活化能分别为50-57KJ/mol与39-62KJ/mol,并对CHP-DMT(N,N-二甲基对甲苯胺)引发MMA聚合动力学以及有关引发聚合机理进行了研究。     

过氧化氢水溶液催化氧化环戊烯制备戊二醛

用过氧化氢水溶液氧化环戊烯制得戊二醛。对多种催化剂-溶剂体系进行了试验, 在钨酸-叔丁醇体系中得到了最高的戊二醛得率: 近60%(30%过氧化氢水溶液为氧化剂)或80%(50%过氧化氢水溶液为氧化剂)。同时, 对该反应的机理进行了初步研究, 提出环戊烯被过氧化氢氧化为戊二醛是经过环氧化物中间产物的观点。     

荧光光谱法研究喹诺酮抗菌素与过氧化氢酶的相互作用

应用荧光光谱法研究了水溶液中喹诺酮抗菌素氧氟沙星、环丙沙星与过氧化氢酶分子间的结合反应。结果表明：药物对过氧化氢酶的内源荧光有较强的猝灭作用,形成复合物所产生的静态猝灭是引起过氧化氢酶荧光猝灭的主要原因。进一步依据荧光猝灭结果确定了药物－酶复合物的形成常数和结合位点数。     

双金属催化剂体系催化过氧化氢分解反应

研究了双金属催化剂体系催化过氧化氢分解反应,测量了不同催化剂体系的活化能.结果表明,双金属催化剂对过氧化氢分解反应具有良好的催化性能,且双金属催化剂存在协同催化作用;而酸性环境对过氧化氢催化分解有明显的抑制作用.     

Polymerization of Acrylonitrile Initiated by 1,4-Dimethyl-1,4-bis(p-nitrophenyl)-2-tetrazene

The polymerization of acrylonitrile (AN) initiated by 1,4-dimethyl-1,4-bis(p-nitrophenyl)-2-tetrazene (Ie) was studied in dimethylformamide (DMF) at high temperature. The polymerization proceeds by a radical mechanism. The rate of polymerization is proportional to [Ie]^0.64 and [AN]^1.36. The overall activation energy for the polymerization is 21.5 kcal/mole within the temperature range of 115-130°C. The chain transfer of Ie was also undertaken over the temperature range of 120-135°C. The activation parameters for the decomposition of Ie at 120°C are k_d = 2.78 × 10^?6 sec^?1, ΔH^? = 40.8 kcal/mole, and ΔS^? = 19.5 cal/mole-deg, respectively.     

A Kinetic Study of Free-Radical Styrene-Acrylonitrile Copolymerization by Differential Scanning Calorimeter

Abstract

The isothermal free-radical copolymerization of styrene and acrylonitrile was examined in the temperature range of 333-373 °K. Initial rate studies of styrene homopolymerization were conducted and agreed favorably with values in the literature. Initial rate studies for acrylonitrile solution polymerization in DMF were also performed. Initiator decomposition rate constants measured in the presence of AN and styrene monomer are reported for AIBN, BP, and DTBP. Rate functions for the full spectrum of comonomer compositions initiated by AIBN and benzoyl peroxide are reported. Several copolymerization kinetic models were tested and found to be inadequate. Conversion histories were found to be consistent with observed initial rates and follow a simple pseudohomopolymerization kinetic model. Autoacceleration was observed and found to increase in severity with increased AN feed compositions and decreased reaction temperatures.     

芳氧基钇在DMF中引发丙烯腈聚合的动力学研究

用单组分三(2,6-二叔丁基4甲基苯氧基)钇配合物[Y(OAr)3]引发丙烯腈聚合,发现介质对聚合反应的影响很大,在介电常数较大的极性溶剂N,N-二甲基甲酰胺(DMF)中,AN聚合反应的活性较高,在50℃下聚合3h,丙烯腈聚合反应转化率达到94%,所得聚丙烯腈(PAN)含52%间规结构.在DMF中聚合反应速率与单体、引发剂的浓度分别呈一级关系,丙烯腈聚合反应的表观活化能为22.1kJ·mol-1.     

Polymerization of Acrylonitrile Initiated by the System Tetramethyl-2-tetrazene and p-Toluenesulfonic Acid

The polymerization of acrylonitrile (AN) initiated by tetramethyl-2-tetrazene (TMT) and p-toluenesulfonic acid (TSA) in dimethylformamide (DMF) was studied. The polymerization was confirmed to proceed through a radical mechanism. The initial rate of polymerization R was expressed by the equation: R_p = k[TMT]^0.6 [TSA]^0.46 [AN]^1.35. The overall activation energy for the polymerization was estimated as 20.7 kcal/mole. In the absence of monomer, the reaction of TMT with TSA was also studied kinetically by measuring the evolution of nitrogen. From these results and ESR measurement of the TMT/TSA system, a possible initiation mechanism is proposed.     

Copolymerisation radiochimique du styrene avec l'acrylonitrile en solution

The radiation-initiated copolymerization of styrene and acrylonitrile was investigated at 20° in dimethylformamide (DMF) and in benzylalcohol solutions. The compositions of the copolymers were only slightly affected by these polar solvents. The influence of temperature on the copolymerization in DMF solutions was studied in greater detail. It was found that the acrylonitrile content in the copolymer obtained at -78° drastically increased as a result of an anionic polymerization of acrylonitrile. Fractional precipitation of the products obtained at -78° showed that they were not mixtures of polymers but were block copolymers containing long sequences of acrylonitrile units. This copolymer is assumed to arise as a result of the simultaneous growing of the two ends of a primary radical-ion, acrylonitrile adding to one end by an anionic mechanism while the free radical end initiates a random copolymerization of styrene and acrylonitrile. The anionic contribution to the over-all process was established. The anionic homopolymerization of acrylonitrile was studied in DMF, toluene and their mixtures. The rate was found to exhibit a maximum for 20% acrylonitrile in DMF. It was further noticed that significant amounts of DMF could be replaced by toluene or styrene without affecting the rate. The reduction in rate in more concentrated monomer solutions was attributed to an autoinhibition of acrylonitrile in its anionic polymerization.     

Vinyl polymerization. Part 268. Polymerization of acrylonitrile initiated by the system of tetramethyl tetrazene and bromoacetic acid

The polymerization of acrylonitrile (AN) initiated by the system of tetramethyl tetrazene (TMT) and bromoacetic acid (BA) in dimethylformamide (DMF) was studied. The TMT–BA system could initiate the polymerization of AN more easily than TMT alone. The polymerization was confirmed to proceed through a radical mechanism. The initial rate of polymerization R_p was expressed by the equation: R_p = [TMT]^0.62-[BA]^0.5[AN]^1.5. The overall activation energy for the polymerization was estimated as 9.4 kcal/mole. In the absence of monomer, the reaction of TMT with BA in DMF was also studied kinetically by measuring the evolution of nitrogen gas. The reaction was first-order in TMT and first-order in BA; the rate data at 49°C were k₂ = 9.1 × 10^?2l./mole-sec., ΔH? = 17.0 kcal/mole, and ΔS? = ? 6.6 eu. In addition, the treatment of TMT with BA in benzene led to the formation of tetramethylhydrazine radical cation, which was identified by its ESR spectrum. On the other hand, the relatively strong interaction between TMT and DMF was observed by absorption spectrophotometry.     

Photopolymerization of Acrylonitrile: Benzophenone-Isopropanol System as Initiator

Abstract

Irradiation of benzophenone in the presence of a suitable hydrogen donor like alcohol leads to benzpinacol and the ketone as sole products. This reaction proceeds through ketyl radical intermediates. This photoredox system may be used for photopolymerization. Photopolymerization of acrylonitrile using isopropanol and benzophenone combination as initiator has been studied. The formation of the polymer is directly proportional to irradiation time, [acrylonitrile] and [isopropanol]. The rate of polymerization increases with an increase in concentration of benzophenone to an optimum and a further increase in benzophenone concentration decreases the polymerization rate. A suitable mechanism is suggested.     

Polymerization of methyl methacrylate with the use of cetyl trimethyl ammonium bromide-benzoyl peroxide combination as the initiating system

Methyl methacrylate (MMA) was polymerized at 40 in the presence of dimethyl formamide (DMF), using cetyl trimethyl ammonium bromide with benzoyl peroxide (CTABBZ₂O₂) as the initiating system. At high dilutions the rate of polymerization was proportional to (initiator)^1–2. In near-bulk conditions using low [DMF], the rate was practically independent of [BZ₂O₂], while the kinetic order with respect to CTAB was about 0.16. The polymerization was inhibited by hydroquinone. A radical mechanism is suggested for the polymerization with primary radical termination significant in near-bulk systems and bimolecular termination significant for high dilution with DMF. Effects of various other solvents or additives on the polymerization were examined. DMF, acetonitrile and pyridine act as rate accelerating diluents; benzene, methanol, chloroform and acetone as inert diluents; formamide and acetamide cause pronounced retardation.     

Fe(III) complexes of 1,4,8,11-tetraaza[14]annulenes as catalase mimics

The development of enzyme mimics of catalase which decompose hydrogen peroxide to water and molecular oxygen according to the 2:1 stoichiometry of native catalase and in aqueous solution at pH 7 and at micromolar concentrations of the enzyme model and hydrogen peroxide is reported. For this purpose, iron(III) complexes of 1,4,8,11-tetraaza[14]annulenes are prepared by various procedures. Efficacious preparations utilize reaction of the [N4] macrocyles with FeII salts in the presence of triphenylamine, followed by gentle oxidation of the FeII complexes by molecular oxygen or by tris(4-bromophenyl)aminium hexachloroantimonate. The complexes are characterized by SQUID magnetometry and by M?ssbauer, EPR, and UV/vis spectrometry. In the solid state, the iron(III) center of the catalytically active complexes exists in the intermediate (quartet, S = 3/2) spin state. Several of these complexes decompose hydrogen peroxide in aqueous buffer solution at pH 7.2 at room temperature with turnover numbers between 40 and 80. The apparent second-order rate constant for hydrogen peroxide decomposition is in the range of 1400-2400 M(-1) s(-1), about 3 orders of magnitude lower than the value for native catalase. Besides oxygen production, a non-oxygen releasing pathway of hydrogen peroxide decomposition is unveiled.     

新型含联萘基团的旋光聚氨酯的制备与性能表征

以旋光联萘二酚(BINOL)和甲苯-2,4-二异氰酸酯(TDI)为原料, 采用氢转移加成聚合法制备了含联萘基团的新型旋光聚氨酯(S-BPU和R-BPU), 并用FTIR, 1H NMR, UV-Vis, CD和DSC/TGA等手段对该聚氨酯进行了结构和性能表征. 结果表明, 当BINOL的光学纯度逐渐增加时, BPU的旋光度和特性粘度逐渐增大, S-BPU和R-BPU的旋光度最高可分别达到-78°和＋54.6°, 具有较高的旋光能力; S-BPU和R-BPU的玻璃化转变温度(Tg)分别达到258.4和286.6 ℃, 热分解温度(Td)分别为305.6和323.6 ℃, 热分解温度比通常的PU材料提高了100 ℃ 左右, 显示了较好的热稳定性; R-BPU和S-BPU的红外发射率分别为0.682和0.618, 显示了较低的红外发射率.