基于醛基化改性的交联聚苯乙烯微球制备席夫碱型螯合树脂的研究

在缚酸剂Na2CO3存在下,使溶胀的氯甲基化交联聚苯乙烯(CMCPS)微球表面的氯甲基与对羟基苯甲醛(HBA)发生亲核取代反应,制得了醛基(AL)化改性的交联聚苯乙烯(ALCPS)微球;利用所制得的ALCPS微球与甘氨酸(GL)发生缩合反应,制备了同时含有席夫碱配基与羧基的席夫碱型螯合树脂AGCPS微球。采用红外光谱法表征了微球功能基团的结构变化,重点研究了CMCPS微球醛基化改性反应,考察了影响亲核取代反应的主要因素,推测和探讨了反应的机理。研究表明,CMCPS微球表面的苄氯基团与HBA缩合反应的速率与HBA的浓度无关,属于典型的SN1反应;使用极性较强的溶剂DMF,在较高的反应温度(90℃)下,有利于亲核取代反应的进行。所得席夫碱型螯合树脂对铜离子具有较强的螯合吸附能力。     

交联聚苯乙烯微球的醛基化改性及卟啉的固载化

以二甲基亚砜(DMSO)为氧化剂,然后采用Kornblum氧化法,将氯甲基化的交联聚苯乙烯(CMCPS)微球表面的氯甲基氧化成醛基,制备了醛基化改性的交联聚苯乙烯(AL-CPS)微球,研究了主要反应条件对改性反应的影响规律。结果表明,在使用催化剂KI及缚酸剂NaHCO3并在110℃下,溶胀在DMSO中的CMCPS微球能被有效地转化为表面带有醛基的改性微球AL-CPS,成为同步合成与固载卟啉的前驱体。随后,以微球AL-CPS、溶液中的苯甲醛及吡咯为共反应物,通过固-液界面上的Alder反应,实现了四苯基卟啉(TPP)在交联聚苯乙烯(CPS)微球表面的同步合成与固载,制得了固载有卟啉的微球TPP-CPS。     

在氯甲基化交联聚苯乙烯微球表面合成与固载手性金属-Salen配合物及其表征

氯甲基化交联聚苯乙烯(CMCPS)微球的氯甲基与苯甲醛衍生物2-羟基-3-甲氧基苯甲醛(HMBA)发生傅克烷基化反应,形成改性微球HMBA-CPS;微球HMBA-CPS与环己二胺发生席夫碱反应,形成键合Salen配基的微球Salen-CPS;最后,使之与锰盐发生配位螯合反应,制得了固载有手性Mn(Ⅲ)-Salen配合物的固体催化剂Mn(Ⅲ)Salen-CPS,分别采用红外光谱、紫外/可见吸收光谱及扫描电子显微镜对固体催化剂的结构与形貌进行了表征和观察。 研究了微球CMCPS与HMBA之间傅克烷基化反应的规律。 结果表明,以AlCl3为Lewis酸催化剂,使用二氯甲烷与硝基苯混合溶剂,可有效地实施CMCPS与HMBA的傅克烷基化反应,制得固体催化剂Mn(Ⅲ)Salen-CPS。 在V(CH2Cl2)∶V(NB)=10∶1的混合溶剂中,40 ℃下反应10 h,可制得氯甲基转化率近于51%的改性微球HMBA-CPS。 该制备途径具有简便、高效与快捷的特点。     

在CPS微球表面固载氨基酚型双齿席夫碱氧钒(Ⅳ)配合物及其催化氧化性能

使乙醛酸(GA)与氯甲基化交联聚苯乙烯(CMCPS)微球发生酯化反应,将醛基(AG)引入交联聚苯乙烯(CPS)微球表面,得到改性微球CPS-AG;再以间氨基苯酚(MAP)为试剂,使微球CPS-AG表面的AG发生席夫碱反应,制得了表面键合有氨基酚型双齿席夫碱配基的功能微球CPS-AGAP;最后,使微球CPS-AGAP与硫酸氧钒发生配位螯合反应,获得了表面固载有氨基酚型双齿席夫碱氧钒(Ⅳ)配合物的固体催化剂微球CPS-[VO(AGAP)2]。重点考察了主要因素对GA与CMCPS微球的酯化反应的影响。采用红外光谱(FT-IR)、固体紫外(UV)及扫描电子显微镜(SEM)对催化剂微球进行了充分表征。分别将微球CPS-[VO(AGAP)2]用于环己醇和乙苯的分子氧氧化过程,考察其催化活性。实验结果表明,溶剂的极性有利于GA与CMCPS微球之间的酯化反应,极性较强的N,N-二甲基乙酰胺为适宜的反应溶剂,90℃为适宜的反应温度。在适宜的反应条件下,CMCPS微球的氯甲基转化率可以达到82%。在分子氧氧化环己醇和乙苯的过程中,非均相催化剂CPS-[VO(AGAP)2]微球均表现出良好的催化活性。     

在醛基化交联聚苯乙烯微球表面同步合成与固载卟啉及固载化金属卟啉的高效催化氧化性能

采用Kornblum氧化反应, 先将氯甲基交联聚苯乙烯(CMCPS)的氯甲基氧化为醛基, 制得醛基(AL)化改性微球ALCPS, 然后使改性微球ALCPS与溶液中的苯甲醛(或取代的苯甲醛)、吡咯之间发生固-液相之间的Adler反应, 成功地实现了卟啉在交联聚苯乙烯微球表面的同步合成与固载, 制得了固载有苯基卟啉(PP) 、对氯苯基卟啉(CPP)、对硝基苯基卟啉(NPP)的功能微球, 最后使功能微球与钴盐发生配合反应, 制备了固载有三种钴卟啉的固体催化剂. 研究重点有两方面: (1)考察主要因素对卟啉同步合成与固载过程的影响|(2)考察固载化钴卟啉在催化分子氧氧化环己烷羟基化过程中的催化特性. 实验结果表明, 以醛基化改性微球ALCPS与溶液中的吡咯及小分子苯甲醛(或取代的苯甲醛)为共反应物, 通过固-液之间的Adler反应, 可以顺利地实现卟啉在微球ALCPS表面的同步合成与固载, 这是制备固载化卟啉的新途径|苯甲醛的取代基结构、催化剂的酸性与溶剂的性质对卟啉的同步合成与固载都有较大的影响|所制备的固体催化剂对分子氧氧化环己烷羟基化的反应, 具有很高的催化活性(环己烷最高转化率约为40%)与选择性(环己醇的选择性在90%以上), 这是由固体催化剂特殊的化学结构所决定的.     

交联聚苯乙烯微球的表面化学改性及吡啶基卟啉的固载化

以无致癌毒性的1,4-二氯甲氧基丁烷为氯甲基化试剂,先将交联聚苯乙烯(CPS)微球氯甲基化,制得氯甲基化微球CMCPS。 然后使微球CMCPS与4-吡啶甲醛进行季铵化反应,将4-吡啶甲醛键合到CPS微球表面,制得键合吡啶甲醛(PyAL)的改性微球PyAL-CPS。 考察了主要反应条件对季铵化反应的影响,最终确定季铵化反应的优化条件:溶剂CCl4,反应温度60 ℃,最后使改性微球PyAL-CPS、4-吡啶甲醛及吡咯在固-液界面上进行Adler反应,形成固载吡啶基卟啉(PyP)的微球PyP-CPS。 用IR和UV-Vis以及Zn2+配合物生成法表征了微球PyP-CPS的形成及负载量。     

以氯代酰氯为试剂的交联聚苯乙烯微球的Friedel-Crafts酰基化反应

采用ω-氯代酰氯试剂氯乙酰氯和氯丁酰氯,在Lewis酸催化剂存在下,于室温下分别与交联聚苯乙烯(CPS)微球进行了Friedel-Crafts酰基化反应,制备了氯代酰基化(chloroacylation,CA)的交联聚苯乙烯微球(CACPS),用红外光谱与佛尔哈德分析法表征了产物的化学结构与组成,研究了各种因素对反应过程的影响。 结果表明,在Friedel-Crafts酰基化反应过程中,伴随的副反应─微球表面聚苯乙烯大分子之间的Friedel-Crafts烷基化附加交联反应,不但降低了在CPS微球表面引入氯代酰基的效率,还使微球变脆。 在室温(25 ℃)下,以CHCl3溶剂、催化剂SnCl4与白球中聚苯乙烯链节的摩尔比为1.2∶1、采用10 mL/g CPS微球的溶剂用量反应5 h,可以达到酰基化反应和烷基化交联副反应的最佳平衡点(此时的氯含量最高)。 结果还表明,采用氯丁酰氯对CPS微球进行氯代酰基化反应的效果明显好于氯乙酰氯。     

阳离子苯基卟啉在交联聚苯乙烯微球表面的同步合成与固载及其主-客体相互作用初探

以对羟基苯甲醛(HBA)与氯甲基化交联聚苯乙烯(CMCPS)微球表面的氯甲基发生取代反应,将醛基苯基键合在CPS微球表面,形成改性了的BA-CPS微球,然后以其与溶液中的对二甲氨基苯甲醛及吡咯在固-液界面上进行Adler反应,实现了含叔胺基苯基卟啉(TAPP)在交联微球CPS表面的同步合成与固载,再使叔胺基团发生季铵化反应,将TAPP转变为meso-三(p-三甲铵基)苯基卟啉(TMAPP),得到了固载有TMAPP的TMAPP-CPS微球。重点考察了主要因素对TAPP在微球表面的同步合成与固载的影响,并分别以牛血清白蛋白(BSA)与溶菌酶为模型蛋白质,探索了固载化TMAPP与生物大分子形成主-客体作用体系的特性。结果表明,通过固-液相之间的Alder反应及随后的季铵化反应,可以顺利地把TMAPP固载在CPS微球表面且其可与蛋白质分子之间产生强烈的主-客体相互作用。     

制备氯甲基化聚苯乙烯交联微球的新方法

使用Lewis酸催化剂, 用自制的氯甲基化试剂1,4-二氯甲氧基丁烷(BCMB), 在室温下对聚苯乙烯交联微球(白球)进行氯甲基化反应, 制得了氯含量接近17%的氯甲基化聚苯乙烯交联微球(氯球); 通过红外光谱法与佛尔哈德分析法表征了产物的化学结构与组成; 考察了各种因素对氯甲基化反应过程的影响规律. 结果表明, 各种因素对白球氯甲基化过程的影响表现在两个方面: (1) 影响白球的氯甲基化程度; (2) 抑制或促进分子链之间通过Friedel-Crafts反应进一步交联, 影响微球的强度.     

交联聚苯乙烯微球固载的双齿席夫碱型氧钒(Ⅳ)配合物催化分子氧氧化苯甲醇

利用水杨醛(SA)和氨甲基(MA)交联聚苯乙烯(CPS)微球反应,制得键合有双齿席夫碱配体SAAM的交联聚苯乙烯SAAM-CPS微球,再与硫酸氧钒发生螯合配位反应,制备了固载有席夫碱型氧钒(Ⅳ)配合物催化剂,采用红外光谱、扫描电镜及热失重等手段对催化剂进行了表征,并用于催化分子氧氧化苯甲醇反应,考察了催化剂用量、反应温...     

Effect of ligand structure of Schiff base oxovanadium(IV) complexes on their catalytic activity in aerobic oxidation of alcohols

Two kinds of immobilized bidentate Schiff base oxovanadium(IV) complexes are prepared via polymer reactions and coordination reactions with chloromethylated cross-linked polystyrene (CMCPS) microspheres as matrix. Benzaldehyde (BA)-functionalized CPS microspheres, BA-CPS microspheres, were prepared through nucleophilic substitution with CMCPS microsphere as precursor and p-hydroxy benzaldehyde as reagent, and then Schiff base reactions were carried out with 3-aminopyridine (AP) and glycine (GL) as reagents, respectively, obtaining two kinds of bidentate Schiff base ligand-bonded microspheres, BAAP-CPS microspheres and BAGL-CPS microspheres. Finally, through coordination reactions with vanadyl sulfate (VOSO₄) as reagent, the two kinds of immobilized bidentate Schiff base oxovanadium(IV) complex microspheres, CPS-[VO(BAAP)₂] and CPS-[VO(BAGL)₂], were obtained. The two immobilized complexes, VO(BAAP)₂ and VO(BAGL)₂, are N,N- and N,O-type bidentate Schiff base oxovanadium(IV) complexes and their ligands have different chemical structures. The two catalyst microspheres were used in oxidation of cyclohexanol and benzyl alcohol with molecular oxygen as oxidant and their catalytic activities are compared. The experimental results show that both solid catalysts can catalyze the transformation reactions of cyclohexanol and benzyl alcohol to their corresponding carbonyl compounds under mild conditions. However, CPS-[VO(BAAP)₂] microspheres have much higher catalytic activity and better stability than CPS-[VO(BAGL)₂] microspheres. For the immobilized bidentate Schiff base oxovanadium(IV) catalysts, the catalytic property is closely related to the chemical structures of the ligands, and for this, a theoretical explanation is given.     

Realizing porphyrin‐functionalization of crosslinked polystyrene microspheres via two special polymer reactions

A novel route to make crosslinked polystyrene (CPS) microspheres to be porphyrin‐functionalized via two special polymer reactions, Kornblum reaction and Adler reaction, was designed and founded. The chloromethyl groups of chloromethylated crosslinked polystyrene (CMCPS) microspheres were first oxidized to aldehyde groups by dimethyl sulfoxide as oxidant via Kornblum oxidation reaction, obtaining aldehyde group‐modified microspheres, ALCPS microspheres, in which, a great quantity of benzaldehyde groups suspend from the main chain, and the effects of the main factors including the reaction temperature, the addition of KI as catalyst and the used amount of NaHCO₃ as acid acceptor on the oxidation reaction were examined. Subsequently, the synchronic synthesizing and immobilizing of porphyrins on CPS microspheres were carried out via the Adler reaction between solid and liquid phases, in which, ALCPS microspheres, pyrrole and benzaldehyde or benzaldehyde analog in a solution were used as co‐reactants, resulting in porphyrin‐functionalized microspheres, and the influence of diverse factors including the acidity of the protonic acid catalyst, the substituent structure of benzaldehyde analog, and the polarity of the solvent as well as the swelling property of the solvent for CPS microspheres on the process of synchronously synthesizing and immobilizing porphyrins on CPS microspheres were investigated in depth. The experimental results indicate that via the designed route, the porphyrin‐functionalization of CPS microspheres can successfully be realized. For the Kornblum oxidation reaction, under the optimal reaction conditions, the conversion of chloromethyl groups can reach 90%. For the Adler reaction between solid and liquid phases, the fitting protonic acid catalyst is lactic acid, appropriate solvent is a mixture of dimethyl sulfoxide and xylene, and using 4‐chlorobenzaldehyde as a benzaldehyde analog reactant in the solution is in favor of the porphyrin‐functionalization of CPS microspheres. Under these specific conditions, the immobilized amount of porphyrin can get up to 23.33 mmol/100 g. Copyright © 2011 John Wiley & Sons, Ltd.     

在交联聚苯乙烯微球表面同步合成与固载吡啶基卟啉及固载化钴卟啉的催化氧化性能

先通过季铵化反应将吡啶甲醛(PyAL)基团键合于交联聚苯乙烯微球(CPS)表面,制得改性微球PyAL-CPS,再通过Adler反应,成功地实现了吡啶基卟啉(PyP)在CPS微球表面的同步合成与同载,制得功能微球PyP-CPS,它再与碘甲烷发生季铵化反应制成N-甲基吡啶基卟啉(MPyP)季铵盐,从而制得固载有阳离子卟啉的...     

水杨酸型螯合树脂对Fe(III)离子的螯合吸附行为

以5-氨基水杨酸(ASA)为胺化试剂, 使氯甲基化的交联聚苯乙烯(CMCPS)微球表面的苄氯基团发生亲核取代反应, 制得了水杨酸型螯合树脂ASA-CPS. 研究了该螯合树脂对金属离子的螯合吸附行为, 探讨了其吸附热力学与吸附机理, 考察了介质pH值对树脂螯合吸附性能的影响以及树脂对不同金属离子的螯合吸附能力. 实验结果表明, 水杨酸型螯合树脂ASA-CPS 对重金属离子具有强螯合吸附性能, 尤其对Fe3+离子表现出很强的螯合吸附能力, 常温下吸附容量可达21 g/100 g. 吸附过程属熵驱动的化学吸附过程, 升高温度, 吸附容量增高; 在可抑制金属离子水解的pH范围内, 介质的pH值越高, 螯合吸附能力越强; 对于性质不同的金属离子, ASA-CPS的吸附性能是有差别的, 吸附容量的顺序为Fe3+>Ni2+>Cu2+>Zn2+.     

Hydroxylation of cyclohexane with molecular oxygen catalyzed by highly efficient heterogeneous Mn(III) porphyrin catalysts prepared by special synthesis and immobilization method

A novel method to synthesize and immobilize porphyrins as well as manganese porphyrins on crosslinked polystyrene (CPS) microspheres was designed. The chloromethyl groups of chloromethylated CPS microspheres (CMCPS microspheres) were first oxidized to aldehyde groups via Kornblum oxidation reaction, obtaining aldehyde group-functionalized microspheres, and then, the synchronous synthesis and immobilization of porphyrins on CPS microspheres were carried out via the Adler reaction between solid–liquid phases, obtaining three kinds of functional microspheres, on which phenyl porphyrin (PP), p-chlorophenyl porphyrin (CPP) and p-nitrophenyl porphyrin (NPP) were immobilized. Finally, three manganese porphyrin-immobilized microspheres, MnPP–CPS, MnCPP–CPS and MnNPP–CPS, were prepared, these solid catalysts were used in the catalytic hydroxylation reaction of cyclohexane with molecular oxygen as oxidant, and their catalytic performances were mainly investigated in this work. Some surprising experimental results were obtained. The prepared immobilized manganese porphyrin catalysts display amazing catalytic activity and selectivity, and cyclohexane conversion can get up to 45?% and cyclohexanol selectivity in the reaction product can be up to 90–100?%.