β-胡萝卜素和α-生育酚协同抗氧化作用的微环境效应

分别用水溶性和脂溶性的偶氮引发剂2，2＇－偶氮二（2－眯基丙烷）二盐酸盐（AAPH）和连二次硝酸二叔丁酯（DBHN）引发亚油酸的过氧化，用氧气吸收法研究了β-胡萝卜素（β－C）和α-生育酚（VE）在负离子胶束十二烷基硫酸钠（SDS）、非离子胶束辛基苯基聚氧乙烯醚（TritonX－100）和正离子胶束十六烷基三甲基溴化铵（CTAB）中对亚油酸自动氧化的抗氧化和协同抗氧化作用．发现它们的抗氧化活性强烈地依赖于介质的微观环境及引发剂的亲脂性．β-C仅在SDS胶束中对DBHN引发的亚油酸过氧化有明显的抗氧化作用，但在SDS和TritonX－100中β-C可以和VE协同作用，显著加强VE对AAPH和DBHN引发的亚油酸过氧化的抑制作用．讨论了抗氧化活性与介质微环境的关系．     

丙烯酸与丙烯酰胺共聚制备高吸水性树脂

采用溶液聚合法,以N,N’-亚甲基双丙烯酰胺（NMBA）为交联剂,过硫酸钾（KPS）为引发剂合成了高吸水性树脂聚（丙烯酸-丙烯酰胺）（P（AA—AM））,研究了单体配比、丙烯酸中和度、引发剂及交联剂用量、反应温度对树脂在去离子水和0．9％盐水中吸水率的影响．最佳条件下制备的树脂在去离子水中吸水率为750g·g^-1,在0．9％盐水中吸水率为85g·g^-1．     

速吸油型高吸油性树脂的研究

以丙烯酸－２乙基己酯与甲基丙烯酸异丁酯为单体，采用加入一种惰性溶剂的悬浮聚合法合成了多孔性高吸油性树脂。在单体中基丙烯酸异丁酯含量为２７％以及引发剂为１％和交联剂为０．５％的条件，制得的树脂吸油速度在１小时内达最大值；可以吸其自身重量１０倍的煤油、１８．２倍的苯。     

双官能度引发剂引发苯乙烯聚合微观动力学

采用 2 ,5 二甲基 2 ,5 二己酰基过氧化己烷 (DMDEHPH)为引发剂 ,在 5 5～ 80℃下引发苯乙烯聚合 .通过研究影响聚合速率的各种因素 ,得出了聚合速率对单体浓度和引发剂浓度的级数分别为 1 0和 0 5次、聚合活化能为 92 0kJ mol、引发效率为 0 5 5± 0 0 3.温度一定 ,引发效率随引发剂浓度的增加而减小 .求得 6 0和70℃下DMDEHPH向引发剂的链转移常数分别为 0 0 37和 0 0 4 8、向单体的链转移常数分别为 0 5 9× 10 - 4和0 75× 10 - 4.     

反相悬浮聚合法合成超强吸水剂

以两性高分子作悬浮稳定剂，用反相悬浮聚合法合成了聚（丙烯酸盐－丙烯酰胺）类超强吸水剂．研究了交联剂、稳定剂、引发剂等用量、中和程度、单体组成及链转移剂等聚合条件对吸水剂吸水性能的影响．得到了吸蒸馏水１０５０ｍＬ／ｇ及吸０．９％ＮａＣｌ溶液８６ｍＬ／ｇ的超强吸水剂．此外，还比较了含不同反离子的聚丙烯酸类吸水剂的吸水性能     

芳香PET树脂母粒的研制

通过丙烯酸和丙烯酸正丁酯溶液共聚合，得到丙烯酸－丙烯酸正丁酯共聚物，该树脂与环氧氯丙烷反应后再与PET树脂切片继续反应，可使PET树脂切片表面形成聚丙烯酸酯自膨润型吸油网络结构，将表面具有聚丙烯酸酯自身膨润型吸油网络结构的PET树脂切片（简称为留香剂）在油溶性香精中浸泡，香精就被吸附在留香剂表面，即得到芳香PET树脂母粒。用SEM观察了母粒的表面结构形态。     

用多官能链转移剂通过普通自由基聚合制备两亲性杂臂星形聚合物

以偶氮二异丁腈为引发剂,四(3-巯基丙酸季戊四醇四酯)(PETMP)为链转移剂进行甲基丙烯酸甲酯(MMA)的自由基聚合,得到了含有残余巯基的聚甲基丙烯酸甲酯大分子链转移剂(HS-PMMA).然后,以HS-PMMA作为大分子链转移剂进行甲基丙烯酸叔丁酯(tBMA)的自由基聚合,合成了杂臂星形聚合物.最后,将所得杂臂星形聚合物的PtBMA链段水解得到了两亲性杂臂星形聚合物.     

新型引发剂引发苯乙烯聚合的动力学

采用过氧化2-乙基己基碳酸叔丁酯为引发剂,研究了苯乙烯自由基本体聚合的动力学过程,考察了引发剂浓度、温度、乙苯质量分数对聚合反应速率和聚苯乙烯分子量的影响.结果表明:在117℃下,聚合速率(Rp)对引发剂浓度的反应级数为0.42,对苯乙烯浓度的反应级数为1,聚合反应的表观活化能为54.8 kJ/mol.引发剂浓度、温度、乙苯质量分数的提高导致聚苯乙烯数均分子量分别下降了约30％、20％和15％,其中引发剂浓度的影响最为显著.     

原子转移自由基聚合合成(甲基)丙烯酸酯类模型聚合物及其动力学研究

本文采用一种新颖的活性自由基聚合—原子转移自由基聚合（ＡＴＲＰ）的方法，以１－溴代苯乙烷作为引发剂，过渡金属卤化物与配位剂络合物（ＣｕＢｒ／２，２’－联吡啶）为催化体系，环己酮为溶剂，进行了甲基丙烯酸正丁酯（ＢＭＡ）和丙烯酸正丁酯（ＢＡ）的活性聚合。得到具有指定分子量和窄分子量分布（１．２＜Ｍｗ／Ｍｎ＜１．５）的模型聚合物。计算并讨论了两聚合体系的ＡＴＲＰ的动力学数据     

TBPB-TBPO引发不饱和聚酯树脂固化的动力学

采用差示扫描量热法(DSC)对不饱和聚酯(UP)树脂复配引发体系进行固化动力学研究,复配引发剂为过氧化苯甲酸叔丁酯(TBPB)-过氧化辛酸酯(TBPO)。采用高斯(Gaussian)分峰法对DSC曲线上的固化放热峰进行双峰拟合,并通过Ozawa方程对拟合结果进行固化动力学参数分析。研究表明:Gaussian双峰拟合后得到的结果与实验数据非常吻合,固化动力学参数更贴近实际固化过程。     

采用重复互贯聚合用废弃白球末合成凝胶型阳离子交换树脂的研究

采用重复互贯聚合工艺将废弃白球末加入单体－交联剂－引发剂体系中充分溶胀，再按照常规悬浮聚合和磺化反应工艺合成凝胶型阳离子交换树脂，结果显示，细粒度白球的交联度在4％－7％，单体吸收比为100％，采用盐水滴加工艺保证单体在白球中的均匀扩散和吸收，所合成的阳树脂的各项性能指标均国家标准，这种重复互贯聚合白球与相同交联度的普通白球比较，具有较高的磺化反应活性，较高的交联度，湿真密度，湿视密度和较高的交换容量。     

Solid-state storage of Ag nanoparticles in anion exchange resin beads and their recovery

This paper reports the idea and describes a method of reversible storage and recovery of silver nanoparticles (NPs) in anion exchange resin beads based on the principle of ion exchange. We also report that similar exchange of NPs was not possible with cation exchange resins. The Ag NPs were stored by simple exchange of anions of the resins, which were activated with OH- and NO3- ions. FTIR spectroscopic measurements support that the Ag NPs were exchanged with NO3- ions in the resins. The so-stored NPs could be regenerated by addition of NaBH4 solution to the resins. These NPs were recovered and subsequently utilized for catalytic reduction of an organic dye (eosin). Powder X-ray diffraction (XRD) pattern indicated storage of the NPs in the form of various oxides of silver in the resin, with the peak value of intensity corresponding to XRD of the NPs not changing with time. Scanning electron microscopic measurements show that the NPs in the beads were stable for over a month without the formation of any apparent agglomeration.     

The preparation of poly(aryl ether ketones) by the use of trifluoromethanesulfonic acid

Two synthetic routes were used for the preparation of aromatic poly(ether ketones): Friedel-Crafts acylation and aromatic nucleophilic substitution. The first route involved the reaction of diphenyl ether and terephthalic acid dichloride in trifluoromethane-sulfonic acid. The addition of trifluoromethanesulfonic anhydride or phosphorus pentoxide resulted in increased molecular weights. The second synthetic route involved the synthesis of an amorphous tert -butyl-substituted poly(ether ketone) prepolymer. Subsequently, the tert -butyl groups were removed by a reversed Friedel-Crafts alkylation reaction yielding the crystalline polymer PEEK. The dealkylation reaction was performed in trifluoromethanesulfonic acid. The addition of a tert -butyl group acceptor resulted in high dealkylation conversions.     

Non-aqueous capillary electrophoretic enantioseparation of N-derivatized amino acids using cinchona alkaloids and derivatives as chiral counter-ions

A non-aqueous capillary electrophoretic method developed with quinine and tert.-butyl carbamoylated quinine as chiral selectors for the enantioseparation of N-protected amino acids was applied to the investigation of other quinine derivatives as chiral additives. The optimum composition of the background electrolyte was found to be 12.5 mM ammonia, 100 mM octanoic acid and 10 mM chiral selector in an ethanol-methanol (60:40, v/v) mixture. Under these conditions, a series of chiral acids, as various benzoyl, 3,5-dinitrobenzoyl and 3,5-dinitrobenzyloxycarbonyl amino acid derivatives were investigated with regards to selectand-selector relationships and enantioselectivity employing quinine, quinidine, cinchonine, cinchonidine, tert.-butyl carbamoylated quinine, tert.-butyl carbamoylated quinidine, dinitrophenyl carbamoylated quinine and cyclohexyl carbamoylated quinine as chiral selector.     

表面亲水性粒度单分散交联PMMA树脂的合成及表征

用种子溶胀聚合方法 ,合成出了粒度单分散的交联聚甲基丙烯酸甲酯微球 .将微球通过水解 ,使其转化为表面带羧基的树脂 .分别用多糖化合物Dextran和DEAE Dextran对水解树脂表面进行包覆涂层 ,然后用n 丁二醇双环氧丙醚分别进行交联 ,制备出两种表面带高交联多糖覆盖层的树脂 .以两种改性树脂为填料 ,以人血清蛋白为试样 ,用HPLC方法对树脂的亲水性能进行了表征 .研究表明 ,两种改性树脂均有很好的亲水性 ,蛋白质的回收率分别在 97%和 99%以上 ,并有良好的机械强度和化学稳定性     

烷基十八胺在离子交换树脂上的吸附及影响研究

研究发现，各种离子交换树脂对烷基十八胺均有较强的吸附作用，阳树脂吸附作用最强，可以近似100％吸附，吸附烷基十八胺后的树脂强度降低，沉降速度改变。常用的无机复苏液无法将吸附的十八胺洗脱出来。     

Simultaneous determination of methyl tert.-butyl ether and its degradation products,other gasoline oxygenates and benzene,toluene, ethylbenzene and xylenes in Catalonian groundwater by purge-and-trap-gas chromatography-mass spectrometry

In Catalonia (northeast Spain), a monitoring program was carried out to determine methyl tert.-butyl ether (MTBE), its main degradation products, tert.-butyl alcohol (TBA), tert.-butyl formate (TBF), and other gasoline additives, the oxygenate dialkyl ethers ethyl tert.-butyl ether, tert.-amyl methyl ether and diisopropyl ether and the aromatic compounds benzene, toluene, ethylbenzene and xylene (BTEX) in 21 groundwater wells that were located near different gasoline point sources (a gasoline spill and underground storage tank leakage). Purge-and-trap coupled to gas chromatography-mass spectrometry was optimised for the simultaneous determination of the above mentioned compounds and enabled to detect concentrations at ng/l or sub-microg/l concentrations. Special attention was given to the determination of polar MTBE degradation products, TBA and TBF, since not much data on method performance and environmental levels are given on these compounds in groundwater. All samples analysed contained MTBE at levels between 0.3 and 70 microg/l. Seven contaminated hot spots were identified with levels up to US Environmental Protection Agency drinking water advisory (20-40 microg/l) and a maximum concentration of 670 microg/l (doubling the Danish suggested toxicity level of 350 microg/l). Samples with high levels of MTBE contained 0.1-60 microg/l of TBA, indicating (but not proving) in situ degradation of parent compound. In all cases, BTEX was at low concentrations or not detected showing less solubility and persistence than MTBE. This fact confirms the suitability of MTBE as a tracer or indicator of long-term gasoline contamination than the historically used BTEX.     

氯甲基化苯乙烯-二乙烯苯共聚物的Friedel-Craft反应

氯甲基化苯乙烯-二乙烯苯共聚物在傅氏催化剂存在下与取代酚(芳香胺)反应可以得到一些含取代酚基的离子交换树脂。它们的物理化学性质和红外光谱分析证实了该类树脂的结构。溶剂的性质、催化剂的种类、用量、反应温度、时间、取代酚(芳香胺)的取代基位置、聚合物的含氯量和孔结构都对反应和副反应有明显的影响。这类离子交换树脂在重金属分离、脱色,特别在维生素和抗菌素的选择吸附等方面,都有十分重要的意义。     

The carboxyl derivatives of 6,8-di-(tert.-butyl)phenoxazine: Synthesis,oxidation reactions and fluorescence

New carboxyl-containing o-aminophenols and phenoxazines were synthesized by condensation of 3,5-di-(tert.-butyl)-quinone with p-aminobenzoic and anthranilic acids. Oxidative transformations of the o-aminophenols and intermediate o-iminoquinones occur with the formation of the ESR detected phenoxazinyl radicals, which furthermore transform to phenoxazines or the dimeric products emerged through the radical attack at the C1 carbon of a formed phenoxazine. Molecular structure of the dimer obtained by oxidation of methyl ester of 4-[3,5-di-(tert.-butyl)-1-(2′-hydroxyphenyl)amino]benzoic acid was X-ray determined. Reaction of 4-[3,5-di-(tert.-butyl)-1-(2′-hydroxyphenyl)amino]benzoic acid with thionyl chloride gives rise to the formation of a derivative of 2-oxido-3H-benzo[d,j][1,2,3]oxathiazol system, the structure of which was established using X-ray crystallography. Solutions of methyl-6,8-di-(tert.-butyl)-10H-phenoxazine-3-carboxylate solvents display intense fluorescence covering a broad spectral region in the range of 400–600?nm.     

含有多甘醇、多甘醇单醚功能基的树脂的合成及其对贵金属离子的吸附性

合成了六种含有乙二醇、多甘醇及多甘醇单醚功能基的树脂。树脂的功能基转化率达93.4—97.5％。树脂2—6对Au(Ⅲ)的吸附率达90—100％,对Pt(Ⅳ)为40—50％,但对共存的Pd(Ⅱ)、Cu~(2+)、Ni(2+)、Cd(2+)等离子甚少吸附。六种树脂的吸金容量在226.3—93.8mg Au(Ⅲ)/g树脂之间。被吸附的金可用3％。硫脲-1N盐酸容液洗脱。洗脱率达95.8％以上。