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.

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.

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.

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.

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.

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。

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。

Chloromethyl pivalate based electrolyte for non-aqueous lithium oxygen batteries

A novel electrolyte with chloromethyl pivalate （CP） used as solvent was first reported for non-aqueous lithium-oxygen （Li-O2） batteries. Since there are no α-H atoms in the structure of CP, the CP based electrolyte in both superoxide radical solution and real LifO2 battery environment showed good chemical stability against superoxide radicals, which was confirmed by ^1H NMR and ^13C NMR measurements. Without a catalyst in the cathode of Li-O2 batteries, the batteries showed high specific capacity and cycling stability.

Graft polymerization of 2-hydroxyethyl methacrylate via ATRP with poly(acrylonitrile-co-p-chloromethyl styrene) as a macroinitiator

Amphiphilic graft copolymers are excellent additives for the development of antifouling membranes by nonsolvent induced phase separation. We report a convenient approach to the synthesis of novel graft copolymers with hydrophobic polyacrylonitrile (PAN) backbones and hydrophilic poly(2-hydroxyethyl methacrylate) (PHEMA) side chains. Atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate was carried out with poly(acrylonitrile-co-p-chloromethyl styrene) (PAN-co-PCMS) as a macroinitiator in the presence of CuCl/2,2'-bipyridine at 50 °C in dimethyl sulfoxide. Kinetics of the graft polymerization was also evaluated. The synthesis of poly(acrylonitrile-co-p-chloromethyl styrene-g-2-hydroxyethyl methacrylate) (PAN-co-(PCMS-g-PHEMA)) can be relatively controlled when CMS (the ATRP sites) unit in the macroinitiator is around 5 mol%. Both the macroinitiators and graft copolymers were characterized by FTIR, NMR and GPC. The surface morphology and wettability of the copolymer films were studied by AFM and water contact angle measurement, respectively. We demonstrate that phase segregation between the PAN-co-PCMS backbones and the PHEMA side chains takes place and the surface hydrophilicity of the graft copolymers increases with the length of the PHEMA side chains. Because these amphiphilic graft copolymers can be synthesized in mass, they will be useful as latent additives for the fabrication of advanced PAN separation membranes.

氯甲基化杂萘联苯聚芳醚酮的热交联及性能

对杂萘联苯聚芳醚酮(PPEK)进行氯甲基化改性,得到一系列不同氯甲基化程度(DCM)的氯甲基化杂萘联苯聚芳醚酮(CMPPEK),以三氯化铝为催化剂,采用热交联的方式制备得到TMPPEK耐溶剂膜,考察了热处理温度和DCM对TMPPEK膜结构和性能的影响。结果表明,随着热处理温度和DCM的增加,膜交联程度增加,耐溶剂性能逐渐增强,同时热稳定性也有所提高;当热处理温度为120℃时,膜在N-甲基吡咯烷酮、乙醇和四氢呋喃等有机溶剂中的凝胶含量介于90%~99%;当DCM在2.34 mmol/g以上时,膜在N,N-二甲基乙酰胺等有机溶剂中的凝胶含量高于90%,表明TMPPEK膜具有优异的耐溶剂性。

P(NVP-DVB)的改性及其检测水中双酚A的应用

为提高水中双酚A(BPA)检测的准确性,采用两步法制备胺功能化聚(N-乙烯吡咯烷酮-二乙烯苯)[P(NVP-DVB)]吸附剂。采用SEM、FTIR、BET、TGA和水接触角测试对两步反应中的样品进行表征,并将胺功能化P(NVP-DVB)用于水中BPA检测。通过优化实验得到氯甲基化反应的最佳条件为:以多聚甲醛[(CH_(2)O)n]和盐酸为氯化试剂,Zn Cl_(2)为催化剂,n(HCl)∶n[(CH_(2)O)n]∶n(Zn Cl_(2))=1∶1∶1,反应温度为80℃,氯化时间为3 h,在该条件下制得中间体[P(NVP-DVB-CH2Cl)]氯含量可达11.14%;以苯胺为胺化试剂对P(NVP-DVB-CH2Cl)进行接枝改性制得的P(NVP-DVB-苯胺),其平均孔径为8.59 nm,比表面积为590.36 m^(2)/g,热失重率为70.66%,其对水中BPA的回收效果最好,回收率为99.65%,相对标准偏差为1.96%,其在模拟水样和实际水样中应用效果均较好,且回收率比商业吸附剂提高了近32%。