Cationic ring-opening polymerization of 3,3-bis(chloromethyl)oxacyclobutane in ionic liquids

Cationic ring-opening polymerization of 3,3-bis（chloromethyl）oxacyclobutane catalyzed by BF3.OEt2 was carded out in ionic liquids [bmim]BF4 and [bmim]PF6. The influences of BCMO concentration and molar ratio of BCMO/BF3.OEt2 on the molecular weights and yield of PBCMO were investigated. The polymerization in ionic liquids proceed to high conversions, although molecular weights are limited, similar to polymerization in organic solvent such as CH2Cl2. Follow a viewpoint of green chemistry, we feel ionic liquid [bmim]BF4 is superior to [bmim]PF6. Extracting [bmim]PF6 from the product using organic solvent as extractant limits its advantage as a green reaction media.

CHLOROMETHYLATION OF POLYMERS MADE FROM TECHNICAL DIVINYLBENZENE AND PROPERTY OF THE CHLOROMETHYLATED POLYMERS

The goal of this paper was to reveal the feasibility of chloromethylation of polymers made from technical divinylbenzene so as to introduce functional groups into polymeric adsorbents. For this study, the factors that effect the chloromethylation reaction, such as the pore structure of the polymer, the ratio of the reactants to catalyst, the reaction temperature and reaction time and so on were investigated, and the pore structure and property of the chloromethylated polymers were studied. The results showed that polymers of technical divinylbenzene could be chloromethylated successfully, and the adsorptive property of the chloromethylated resin was different from that of the initial resin.

The Chloromethylation Reaction of Substituted Titanocenes(η~5-C_5H_5)(η~5-C_5H_4CRR'C_6H_4X)TiCl_2

The chloromethylation reaction of substituted titanocenes (η~5-C_5H_5)(η~5-C_5H_4CRR'C_6H_4X)TiCl2 1 in the presence of polyformaldehyde and dry hydrogen chloride isreported.

RING OPENING POLYMERIZATION OF （CHLOROMETHYL）THIIRANE BY RARE EARTH COORDINATION CATALYSTS Ⅲ．HOMOPOLYMERIZATION OF （CHLOROMETHYL）THIIRANE AND ITS POLYMERIZATION KINETICS

Ring opening polymerization of (chloromethyl) thiirane (CMT) usingrare earth coordination catalysts has been investigated for the first time: Ithas been found that binary rare earth coordination catalyst composed of rareof phosphonate and trialkyl aluminum are effective catalysts for the polymerization of (chloromethyl)thiirane with high yield. Kinetic studies showed that the polymerization rate is of first order with respect to both monomer concentration and catalyst concentration. The antivation energy of the polyimerization reaction is 28.4kJ/mol.

2-FURFURYLKETONES FROM 2-(CHLOROMETHYL)FURAN AND LITHIUM TRIALKYLALKYNYLBORATES

2-(Chloromethyl)furan as an electrophile attacks lithium trialkylalkynylborates,followed by the oxidation with H_2O_2 under basic conditions to afford 2-furfurylketones in good yields.

IMMOBILIZATION OF AMINOACYLASE FROM ASPERGILLUS ORYZAE ON CHLOROMETHYLATED CROSS-LINKED POLYSTYRENES

A number of chlorumethylated polystyrenes were synthesized and tried to immobilize aminoacylase from Aspergillus oryzae and many factors which affected immobilized enzyme activity were studied in detail. The results indicated that the immobilized enzyme on support(IAR-1) possessed high enzymatic activity and high stability.

FLUORESCENCE STUDIES ON MORPHOLOGICAL CHANGE OF ST/DVB CROSSLINKED GELS DURING CHLOROMETHYLATION

The morphological change of St/DVB crosslinked gels during chloromethylation wasstudied by fluorescence spectroscopy using St/DVB crosslinked and hypercrosslinked gels as controlsamples. It has been found that with increase of chlorine content, the excimer emission band (~325nm)approaches to vanish, while the intensity of multi-ring aggregate emission band (~420nm) quicklyreaches a maximum, and then decreases sharply accompanied by appearance ofa new broad bandcentred at ca 488nm which roughly coincides with the typical emission band of hypercrossllinkedSt/DVB gels. Mearwhile, the result of IR measurement suggests that methylene bridge between phenylrings forms and increases with chloromethylation process. These results are explained in terms ofaside reaction of post-crosslinking, which densifies the loosely crosslinked networks and undoes thedensely entangled microgel nuclei. As a result, the morphology of the crosslinked gels becom es morehomogeneous with chloromethylation.

Ring-opening Polymerization of Chloromethyl Thiirane with Catalytic Systems Composed of Lanthanide Compound and Ethyl Aluminum Sesquichloride

The Ziegler-Natta type catalytic systems composed of lanthanide compound and ethyl aluminum sesquichloride are effective to convert chloromethyl thiirane to polymer of molecular weight ca. 10,000. The effects of rare earth element and ligand were studied.

氯球嫁接L-脯氨酸绿色催化合成香豆素-3-羧酸酯

将L-脯氨酸嫁接在树脂氯球上,催化水杨醛及其衍生物和丙二酸酯直接合成香豆素-3-羧酸酯类物质,反应具有选择性强、产率高、成本低、三废少、后处理简单、催化剂可以多次重复使用等优点,符合绿色催化的特性。实验表明:反应在100℃下,醛和酯的摩尔比为1:1.2,催化剂的用量1 g,10 mL DMF中反应5h,反应的选择性≥98%,产率高达92%;催化剂循环使用6次反应的产率仍在85%以上。在此优化的反应条件下,高效合成了一系列其他香豆素-3-羧酸酯类物质,产品的结构和纯度通过了NMR、IR和熔点等手段进行了鉴定。

固有荧光聚合物纳米球的制备及性能表征

设计了固有荧光聚合物纳米球作为荧光涂层和Fe^(3+)荧光探针的综合实验。采用12-冠醚-4辅助的无皂乳液聚合法制备了平均粒径55 nm的单分散聚氯甲基苯乙烯(PCMSt)荧光纳米球,并对其性能进行了表征,包括纳米球的形貌和荧光性能、纳米荧光涂层制备、对Fe^(3+)的选择性、抗干扰性和高灵敏度检测。实验结果表明,该纳米球具有良好的荧光稳定性和固体荧光性能,对Fe^(3+)表现出高灵敏度和选择性,在纳米荧光涂层和Fe^(3+)荧光纳米探针方面具有很大的应用潜力。

乙二胺螯合树脂对Cu(Ⅱ)和Cd(Ⅱ)的吸附性能研究

采用表面引发原子转移自由基聚合(SI-ATRP)将甲基丙烯酸缩水甘油酯(GMA)接枝到氯甲基化聚苯乙烯树脂(PS-CH2Cl)表面,再经环氧基和氨基的开环反应,制备了一种乙二胺螯合树脂(PEDA-g-PS)。采用红外光谱、扫描电镜和元素分析对树脂进行了表征,考查了树脂对Cu(Ⅱ)和Cd(Ⅱ)的吸附性能。通过分析溶液pH对吸附容量的影响、吸附等温线和吸附动力学曲线,证明Cu(Ⅱ)和Cd(Ⅱ)在PEDA-g-PS树脂上的吸附属于Langmuir单层吸附模型,符合准二级动力学方程。pH3.0时,树脂对Cu(Ⅱ)和Cd(Ⅱ)的最大吸附量可达1.19和1.95 mmol/g,经过10次吸附-解吸循环实验,树脂的吸附容量无显著变化,表明树脂对重金属离子具有优异的吸附性能以及优良的重复使用性能。

含苯氧甲基、氯甲基的十元、十二元及十六元氮杂内酯化合物的合成及抑菌活性

大环内酯类化合物已被广泛应用于药物中,为发现新型高活性抑菌化合物,以课题组之前研究的大环内酯化合物WLD、D16-19等为先导化合物,设计、合成一系列新型含苯氧甲基、氯甲基的十元、十二元及十六元氮杂内酯化合物C和E,并进行离体抑真菌活性测定。结果表明:在50 mg/L质量浓度下,大部分化合物C和E对供试的5种病原真菌均有一定的抑菌活性,其中C5和C6对马铃薯早疫病菌Alternaria solani的抑制率分别为88%和90%,化合物C6对小麦赤霉病菌Fusarium graminearum的抑制率为94%。对比C和E对5种真菌的抑制率,加入氨基甲酸酯和脲结构片段对化合物活性没有明显提高;十六元氮杂内酯化合物C5、C6的抑菌活性高于十元和十二元氮杂内酯化合物C1~C4,说明化合物的主体结构氮杂内酯环对化合物的活性影响较大。C5对马铃薯早疫病菌的EC_(50)值为2.95 mg/L,与对照药剂吡唑醚菌酯活性相近,优于先导化合物D16-19对番茄早疫病菌A. solani的活性(EC50值为4.76 mg/L),表明在十六元氮杂内酯中加入苯氧甲基可提高化合物对早疫病菌的活性,C5可作为新型抑菌活性先导化合物进一步研究。

2-氯-5-氯甲基吡啶的合成及应用研究进展

综述了近年来2-氯-5-氯甲基吡啶(CCMP)的合成及应用的研究进展,包括各种底物的合成路径,并对各种工艺路线及应用领域进行了阐述,最后对其在农药中的应用研究进行了综述,并对未来合成2-氯-5-氯甲基吡啶及新烟碱类杀虫剂的合成进行了展望。

Chloromethylation and Quaternization of Poly(aryl ether ketone sulfone)s with Clustered Electron-rich Phenyl Groups for Anion Exchange Membranes

Ion segregation is critically important for achieving high ion conductivity for anion exchange membranes(AEMs).Herein,a new bisphenol monomer bearing ten electron-rich phenyl groups was designed and polymerized with various amounts of electron-deficient 4,4′-dihydroxydiphenylsulfone and 4,4′-difluorobenzophenone to yield dense and selective reaction sites for chloromethylation and quaternization.As the most challenging step,chloromethylation was optimized by tuning the reaction temperature,reaction time,and reactant ratios.Ion exchange capacity,water uptake,anion conductivity,mechanical stability,and alkaline stability of the resulting AEMs were characterized in detail.It is found that chloromethylation reaction needed to be carried out at low equivalent of chloromethylation agents to avoid undesirable crosslinking.The QA-PAEKS-20 sample with an IEC of 1.19 mmol·g^-1 exhibited a Cl^–conductivity of 11.2 mS·cm^-1 and a water uptake of 30.2%at80°C,which are promising for AEM applications.

Chloromethylation of 2-chloroethylbenzene catalyzed by micellar catalysis

The chloromethylation reaction of 2-chloroethylbenzene was performed successfully by micellar ca-talysis in the biphasic oil/water system. The effects of anionic, cationic and non-ionic surfactants on the reaction were compared. The mechanism of chloromethylation reaction and the mechanism of micellar catalysis were investigated. The results show that the micellar catalysis is an effective way to realize the chloromethylation of 2-chloroethylbenzene, and the cationic surfactant shows the most effectiveness. The longer the hydrophobic chain of the cationic surfactant is, the better the catalysis effect will be, and the addition of inorganic electrolyte into the aqueous phase can markedly promote the catalysis effect.

One-Pot Synthesis of Chloromethylated Mesoporous Silica Nanoparticles as Multifunctional Fillers in Hybrid Anion Exchange Membranes

Chloromethylated mesoporous silica nanoparticles （CM MSN） were synthesized through co-condensation of tetraethoxysilane and （chloro） phenyltrimethoxysilane precursors using hexadecyl trimethyl ammonium bromide as template.With the addition of the particles into chloromethylated poly （ether ether ketone） （PEEK）,the hybrid membranes were prepared by a solution-casting method after complete quatemization of the casting solution.The successful synthesis of the particles was verified by transmission electron microscopy,X-ray diffraction and Fourier transform infrared spectroscopy while the effect of CM MSN incorporation on membrane performance including thermal stability,mechanical strength and hydroxide conductivity was investigated by thermal gravimetric analysis,electronic stretching machine,alternating-current impedance and so on.Owing to the large pore volume and high surface area of the particles,the hybrid membranes exhibited enhanced hydroxide conductivity （88.7% increase at 60 ℃,100% RH with 5.0 wt% filling content） due to an increase in ion concentration and optimization of the channel morphology.Besides,higher mechanical strength,thermal and dimensional stability of hybrid membranes were obtained compared with those of the imidazolium PEEK membrane.

Li^＋ Ion Attachment to Chloromethyl and Chlorofluoromethyl Peroxyl Radicals： Structures and Properties, of CHnCl3-nO2-Li^＋ and CFnCl3-nO2-Li^＋ （n=0-3） Complexes

The structures and stabilities of these still experimentally unknown CHnCl3-nO2-Li^＋ and CFnCl3-nO2-Li^＋ ions have been theoretically investigated by ab initio molecular orbital theory and density functional theory （DFT） in conjunction with the 6-311G（d,p）, 6-311 ＋G（d,p）, 6-311 ＋G（2d,p） and 6-311 ＋G（2df,2p） basis sets. The optimized geometries, chemical bonding and NBO analysis indicate that these complexes of CHnCl3-nO2-Li^＋ and CFnCl3-nO2- Li^＋ exist as ion-dipole molecules. The calculated affinity energies of these species exceed 41.9 kJ/mol, which are large enough to suggest the possibility that these title complexes could be detected as stable species in gas phase by Li^＋ ion attachment mass spectrometry.

Studies on Ring-Opening Polymerization of Chloromethyl Thiirane with Rare Earth Catalysts and Functional Resins Synthesized therewith

Studies on ring-opening polymerization of chloromethyl thiirane with rareearth catalysts and functional resins synthesized therewith were reviewed.

Anion Exchange Membranes Based on Chloromethylation of Fluorinated Poly（arylene ether）s

This report details the properties of fluorine-containing anion exchange membranes（AEMs） synthesized by chloromethylation and quaternization of fluorinated poly（arylene ether）s（FPAEs） based on decafluorobiphenyl and bisphenol A. Meanwhile, we compared their properties with those of their non-fluorinated counterparts, Udel-based AEMs. The reactivity of the chloromethylation of fluorinated poly（arylene ether）s was lowered by the strong elec- tron-withdrawing group, per-fluorinated biphenyl residue. Therefore higher temperature, more chloromethylation reagent, and longer reaction time were needed in the chloromethylation of FPAEs. Because of the hydrophobicity of fluorine, the swelling of FPAEs was depressed. In the FPAE-based AEMs, the water uptake of FPAE-1 membrane（F-1） was just 30%. There is a strong correlation between water uptake and conductivity for both Udel- and FPAE-based AEMs. Among all the membranes, the water uptake and the conductivity of FPAE-3 membrane（F-3） could reach up to 100% and 13.47 mS/cm respectively at 30 ℃. The mechanical properties of FPAE-based AEMs at room tempera- ture were worse than those of Udel-based ones because of the weak intermolecular interaction caused by the low po- larizability of fluorine. However, their high temperature mechanical properties are better, which can be explained in terms of low swelling.

法莫替丁合成工艺改进

采用脒基硫脲和1,3-二氯丙酮环合反应制得2-(4-(氯甲基)噻唑-2-基)胍基盐酸盐,再与硫脲反应制得(S)-((2-胍基-4-噻唑基)甲基)异硫脲二盐酸盐,最后与N-硫酰胺基-3-氯丙脒盐酸盐反应生成法莫替丁。采用一锅法制备关键中间体2-(4-(氯甲基)噻唑-2-基)胍基盐酸盐,单步反应收率达到95%以上,合成法莫替丁的总收率达到60%,大大降低了法莫替丁的生产成本。