卟啉降冰片烯聚合物的合成、表征及性质研究

本文设计合成了卟啉的降冰片烯单体,采用Grubbs催化剂与长链烷基的降冰片烯单体开环易位聚合,直接得到了卟啉降冰片烯聚合物,通过紫外-可见吸收光谱、荧光光谱、电化学等手段研究了卟啉降冰片烯聚合物的性质,与小分子单体相比,所得卟啉高分子共聚物相当好地保持了卟啉应有的光物理、电化学等特性.     

降冰片烯开环易位聚合反应的分子量及分子量分布控制

使用Grubbs催化剂催化降冰片烯单体进行开环易位聚合反应, 研究了催化剂搅拌溶解时间、聚合反应的溶剂极性和三苯基膦的加入等反应条件对降冰片烯单体ROMP反应分子量及分子量分布的影响, 从而得到降冰片烯ROMP反应的最佳条件.     

钌催化降冰片烯开环移位聚合的研究

CpRuCl(PPh~3)~2/O~2和CH~3OCH~2CH~2CpRuCl(PPh~3)~2/O~2体系对降冰片(NBE)开环移位聚合(ROMP)有活性,降冰片烯的转化率和聚降冰片烯主链双键顺反比与气氛催化剂摩尔比及催化剂本身性质有关。在实验的基础上提出了钌催化降冰片烯开环移位聚合的可能机理。     

后过渡金属催化降冰片烯加成聚合

综述了后过渡金属催化剂催化降冰片烯加成聚合的研究进展。主要介绍了Ni、Pd、Co三种金属催化剂各自的结构以及其催化降冰片烯聚合的特点,同时也阐述了Ni、Pd催化剂催化降冰片烯聚合的机理。     

5-丁氧基亚甲基-2-降冰片烯的合成及其加成聚合反应

采用降冰片烯-5-甲醇和溴丁烷在氢化钠作用下合成了5-丁氧基亚甲基-2-降冰片烯,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系使之聚合。 考察了聚合时间对其均聚合的影响以及5-丁氧基亚甲基-2-降冰片烯和降冰片烯不同摩尔投料比对其共聚行为的影响。 采用1H NMR、FTIR和TGA测试技术对所得的聚合物进行了结构表征和性能测试。 结果表明,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系对5-丁氧基亚甲基-2-降冰片烯均聚和共聚具有较高的催化活性。 得到的均聚物和共聚物为加成型聚合物,料液中5-丁氧基亚甲基-2-降冰片烯的摩尔分数为10%~90%时,其在共聚物中的插入率为22.1%~76.9%,所得聚合物具有较好的热稳定性（Td＞360 ℃）,在THF和CHCl3等许多普通溶剂中有很好的溶解性能。     

茂钛/MAO催化体系进行降冰片烯聚合的研究

以降冰片烯为例的环状烯烃的聚合方式主要有两种 :( A) Vinyl-type polymerization;( B) Ring-Opening Polymerization　　 80年代中期以前 ,环烯烃聚合研究主要集中在开环易位聚合 (ROMP)反应 [1] .Kaminsky[2 ] 首次以[En(Ind) 2 Zr Cl2 ]/MAO等为催化剂进行降冰片烯的聚合 ,获得了熔点极高 (高于其 40 0℃的分解温度 )的大分子量加成结构的聚合物 .研究结果表明 ,具有 C2 和 Cs对称性的茂锆催化体系能高活性地得到降冰片烯加成聚合物 [3,4 ] ,但是这些由茂锆催化体系合成的降冰片烯聚合物不溶于有机溶剂 ,难以进行精确定量的结…     

大位阻α-二亚胺钯配合物催化降冰片烯与5-降冰片烯-2-乙酸酯的共聚研究

采用大位阻9,10-二氢-9,10-乙醇蒽~(-1)1,12-二亚胺钯配合物为主催化剂,三五氟苯基硼B(C6F5)3为助催化剂,在甲苯中对降冰片烯与极性降冰片烯衍生物5-降冰片烯-2-乙酸酯进行加成共聚合研究,呈现出高催化活性(1.1×10~4~1.6×10~6g_(polymer)/molPd·h)。当5-降冰片烯-2-乙酸酯加入摩尔比为10~50%时,其插入率为5.53~8.45%。聚合反应产率随着5-降冰片烯-2-乙酸酯加入摩尔比的增大而减小。共聚物的热分解温度T_d、玻璃化转变温度T_g和分子量Mw分别为332.4~432.5℃、259.9~306.6℃和2.3×104~8.6×104g·mol~(-1)。     

双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3/AlEt3体系催化醋酸降冰片烯酯的聚合

采用双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3/AlEt3体系可在20～90 ℃范围内在甲苯溶剂中催化醋酸降冰片烯酯聚合,得到中等分子量(Mw＝7.0×103～3.1×104 g/mol)和分子量分布较窄(Mw/Mn为1.8～2.0)的醋酸降冰片烯酯聚合物.采用1H NMR、13C NMR、FT-IR、DSC、TGA及广角X射线衍射(WAXD)等技术对所得聚合物进行了结构表征和性能测试.结果表明,所得的聚醋酸降冰片烯酯为加成型产物,证明此催化体系催化醋酸降冰片烯酯聚合是按乙烯基加成模式进行的;所得聚合产物为非晶态,具有短程有序长程无序的特征,分子链间的距离为1.24 nm;聚合产物具有较好的热稳定性(Td＞330 ℃),并能够溶解在大部分普通有机溶剂中.     

手性降冰片烯衍生物的制备及应用

手性降冰片烯类衍生物是C5主馏分之一的(双)环戊二烯中一类重要的高附加值衍生产品,主要由环戊二烯和非对称的亲双烯体通过Diels-Alder反应制得。本文从合成手性降冰片烯衍生物的机理出发,重点介绍了在有/无催化剂条件下制备手性降冰片烯酯类、醛类、酮类和酰基口恶唑烷酮类衍生物时的收率和立体选择性等。由手性二醇、二酚或口恶唑啉与配位较强的铝、硼、铜、钛或镧系金属络合物等配位而成的手性催化剂有利于提高手性降冰片烯衍生物合成速度及其立体选择性。同时,本文针对近年来手性降冰片烯衍生物在光致变色的光学材料和阴离子、阳离子及复合离子交换膜领域中的应用进行了简要概述。最后,对其研究方向和应用前景进行了展望。     

8-苯胺-1-萘磺酸钛配合物的合成及催化乙烯与降冰片烯共聚合反应

合成了新型催化剂8-苯胺-1-萘磺酸钛配合物, 并应用于乙烯与降冰片烯的共聚合反应中. 分别考察了助催化剂种类[甲基铝氧烷(MAO)和三乙基铝(TEA)]、 降冰片烯浓度、 Al/Ti摩尔比、 聚合温度和聚合压力对催化活性与共聚性能的影响. 通过核磁共振、示差扫描量热和凝胶渗透色谱等对所制备的共聚物进行了表征. 结果表明, 在相同条件下, 以MAO为助催化剂时, 共聚催化活性更高, 催化剂为单活性中心, 可得到分子量分布较窄(PDI≈3)的共聚产物, 其共聚反应机理为加成聚合. 另外, 随着降冰片烯浓度的升高, 共聚物中降冰片烯单元的摩尔比呈线性上升趋势, 所得共聚物的熔点随之降低.     

PREPARATION AND CHARACTERIZATION OF SCHIFF BASE POLYMERS DERIVED FROM 4,4′-METHYLENEBIS(CINNAMALDEHYDE)

New Schiff base polymers poly[4,4＇-methylenebis（cinnamaldehyde）ethylenediimine] （PMBCen）, poly[4,4＇- methylenebis（cinnamaldehyde）1,2-propylenediimine] （PMBCPn）, poly[4,4＇-methylenebis（cinnamaldehyde）1,3-propylenediimine] （PMBCPR）, poly[4,4＇-methylenebis（cinnamaldehyde） 1,2-phenylenediimine] （PMBCPh）, poly[4,4＇-methylenebis（cinnamaldehyde）meso-stilbenediimine] （PMBCS）, poly[4,4＇-methylenebis（cinnamaldehyde）urea] （PMBCUR）, poly[4,4＇- methylenebis（cinnamaldehyde）semicarbazone] （PMBCSc）, poly[4,4＇-methylenebis（cinnamaldehyde）thiosemicarbazone] （PMBCTSc） and poly[4,4＇-methylenebis（cinnamaldehyde）hydrazone] （PMBCH） were formed by polycondensation of 4,4＇- methylenebis（cinnamaldehyde） with ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-phenylenediamine, meso-stilbenediamine, urea, semicarbazide, thiosemicarbazide and hydrazine, respectively. The dialdehyde and polymers have been characterized through elemental micro-analysis, IR, UV-Vis and ^1H-NMR spectroscopic techniques. Thermoanalytical studies and viscous flow of dilute solutions of dialdehyde and its polymers have been examined and compared.     

Bridged bis-pyridinylimino dinickel(II) complexes: Syntheses, characterization, ethylene oligomerization and polymerization

A series of bridged bis(pyridinylimino) ligands were efficiently synthesized through the condensation reaction of 4,4′-methylene-bis(2,6-disubstituted aniline) with 2-pyridinecarboxaldehyde or 2-benzoylpyridine. They reacted with (DME)NiBr₂ to form dinuclear Ni(II) complexes. All resultant compounds were characterized by elemental analysis, IR spectra as well as the single-crystal X-ray diffraction to confirm the structures of ligands and complexes. Activated with methylaluminoxane (MAO), these nickel complexes showed considerably good activities for ethylene oligomerization and polymerization. Their catalytic activities and the properties of PEs obtained were depended on the arched environment of ligand and reaction conditions.     

Molten salt ionic liquid-assisted synthesis of nano-structured poly(amide imide)s based on 4,4′-methylenebis(3-chloro-2,6-diethyl trimellit imidobenzene) via microwave process as an environmentally friendly methodology

In this paper, for the first time, 4,4′-methylene-bis(3-chloro-2,6-diethyl trimellit imidobenzene) was prepared by the condensation reaction of 4,4′-methylene-bis(3-chloro-2,6-diethylaniline) and trimellitic anhydride. A series of novel poly(amide imide)s was prepared by the direct polycondensation of the synthesized diimide diacid and various commercial diamines using tetra-n-butylammonium bromide and triphenyl phosphite as a condensing agent under microwave irradiation. Tetra-n-butylammonium bromide acts both as a solvent and a catalyst to mediate clean polymerization reactions to yield the desired polymers. The obtained polymers were characterized with FTIR, ¹H NMR, X-ray diffraction, field emission scanning electron microscopy, elemental and thermogravimetric analysis. The poly(amide imide)s were generally soluble in polar organic solvents, such as N,N′-dimethyl acetamide, N,N′-dimethylformamide, N-methyl-2-pyrrolidone and sulfuric acid at room temperature, and are insoluble in methylene chloride, cyclohexane and water. Morphology probes showed these macromolecules were non-crystalline and nano-structured polymers. The effect of ultrasonic irradiation on the surface morphology of polymers was studied and the results demonstrated that the morphology of macromolecules after ultrasonication became more homogenous than it is before ultrasonic radiation. On the basis of thermogravimetric analysis data, such polymers are thermally stable and can be classified as self-extinguishing polymers.     

Blends of an epoxy thermosetting polymer with aromatic liquid-crystalline polyesters

A series of aromatic liquid-crystalline polyesters with different composition have been synthesized to adjust transition temperatures and molecular weight. Miscibility of polyesters with bisphenol-A-diglycidyl ether (DEGBA), 4,4′-methylene-bis(3-chloro-2,6-dimethylaniline) (MCDEA) and the influence on transition temperatures has been studied. Miscibility of binary and ternary mixtures was found over the whole range of composition depending on the temperature. Thermoset formation by curing of LC-polyester / DEGBA / MCDEA mixtures containing different amounts of polyester resulted in reaction-induced phase separation with polyester content from 30 to 50 wt.%. Cloud point techniques, scanning electron microscopy (SEM) and dynamic mechanical thermal analysis (DMTA) have been applied.     

Polyethers from 5,5′-methylene-bis (8-hydroxyquinoline)

Polyethers have been prepared by condensing the disodium salt of 5,5′-methylene-bis(8-hydroxyquinoline) (MBQ) with p-xylylene dichloride and dibromide, 4,4′-dichloromethyldiphenyl ether, 4,4′-dichloroacetyldiphenyl, 4,4′-dichloroacetyldiphenyl ether and methylene and ethylene dichlorides. All the polycondensations except those with the two aliphatic dihalides could be effected in dioxane and in DMF. The polycondensation of the disodium salt of MBQ with the two aliphatic dihalides could be effected in the absence of solvent in a sealed tube using Ullman catalysts. All the polyethers are insoluble in common organic solvents. I.R. spectra of the polyethers have been measured in KBr. The thermal and electrical properties of these polyethers have been studied.     

Segmented poly(ether urethane) films containing ferrocene units in the hard segments

Segmented poly(ether urethanes) were synthesized from polypropylene glycol (PPG) and 4,4′-methylene-bis(phenyl-isocyanate) (MDI), using 1,1′-bis(β-aminoethyl)ferrocene (BAF) and 1,1′-bis(β-hydroxyethyl)ferrocene (BHF) as chain extenders. These polymers were characterized by infrared and ¹³C-NMR spectroscopy. Mass spectrometry was also utilized to determine the linkage of BAF and BHF in these polymers.     

Supramolecular helical architecture assembled by double-helical [Ag2L2] units

A series of new sterically hindered bridged ligand 4,4^′-methylene-N,N^′-bis(phenyl-2-pyridylmethylene)-bis(2,6-dialkylanil)s was efficiently synthesized by the condensation reaction of 4,4^′-methylene-bis(2,6-disubstituted aniline) and benzoyl pyridine. They easily coordinated with Ag(I) to form Ag(I) complexes. The structure of complex [Ag₂L⁴₂][ClO₄]₂ was determined by the single X-ray crystallographic analysis, and the double-helical asymmetric unit containing two [Ag₂L⁴₂] moieties was interconnected with the adjacent unit through hydrogen bonds to form a helical supramolecular architecture.     

Catalysis of copper(II) chelate-amine complexes in the oxidative coupling of 2,6-dialkylphenols

The oxidative coupling reaction of 2,6-dimethylphenol and 2,6-di-tert-butylphenol with molecular oxygen was performed by using a series of copper(II) chelate complexes as a catalyst, derived from copper(II), β-diketone, and some Shiff bases. Under the applied reaction conditions, the reaction products of 2,6-dimethylphenol were poly(2,6-dimethyl-1,4-phenylene oxide) (C? O coupling product) and 3,3′,5-5′-tetramethyl-4,4′-diphenoquinone (C? C coupling product), and that of 2,6-di-tert-butylphenol oxidation was only 3,3′,5-5′-tetra-tert-butyl-4,4′-diphenoquinone (C? C coupling product). The catalytic activity has been shown to be dependent on the properties of the copper(II) chelates used as catalysts and the mole ratios of amine ligand to copper(II) chelate (ligand ratio). The basicity and the steric bulkiness of the amine used as a ligand for copper(II) β-diketonato catalysts were found to be two of the main factors that govern the oxidative coupling mode (C? O and/or C? C coupling) of 2,6-dimethylphenol. The oxidative coupling activity of 2,6-dialkylphenol is discussed in terms of both the stabilities of the copper(II) chelates and of the copper(II) chelate-amine adducts. The rate of oxygen absorption for 2,6-dimethylphenol catalyzed by the copper(II) acetylacetonato-piperidine system is first order in oxygen partial pressure and zero order in 2,6-dimethylphenol concentration, respectively. A Cu(II)-oxygen, as an intermediate is suggested on the basis of the results obtained.     

Synthesis and coordination properties of the zinc complex of dimeric porphyrin in reactions with imidazole, 2-methylimidazole, and the pyridine in benzene

Dimeric porphyrin(2,6-bis[15′-(3″,5″-di-tert-butylphenol)-3′,7′,13′,17′-tetramethyl-2′,8′,12′,18-tetraethylporphin-5′-yl]-4-tert-buthylphenol) and its binuclear zinc complex were obtained from 4,4′-dimethyl-3,3′-diethyldipyrrolylmethane, 2,6-diformyl-4-tert-butylphenol and 3,5-di-tert-buthylbenzaldehyde. Coordina-tion properties of dimeric zincporphyrin in the intermolecular reaction with nitrogen-containing bases (imidazole, 2-methylimidazole, and pyridine) in benzene were studied. Geometry and electronic structure of the zincporphyrin and its molecular complexes were calculated by a quantum-chemical method. Energy characteristics of the intermolecular reaction of the dimeric zincporphyrin with bases were determined. The calculated energies of the central metal atom interaction with the nitrogen atom of an extra-ligand agree well with the stability of the Zn-porphyrin molecular complexes. The influence of the deformation distortions of the porphyrin ligand on the strength of the metal-extra-ligand σ-bond was established.     

Polyamides from 2,6,(7)-diamino-9,10-dihydro-9,10-ethanoanthracene and 2,6,(7)-diaminoanthracene

High-molecular-weight, film-forming, amorphous polyamides have been prepared from 2,6(7)-diamino-9,10-dihydro-9,10-ethanoantracene with adipic, sebacic, dodecanoic, isophthalic, 4,4′-oxybibenzoic, 2,6-naphthoic, 4,4′-bibenzoic, and terephthalic acid. Thermal elimination of ethylene from these polymers has yielded the corresponding polyamides from 2,6(7)-diaminoanthracene which were of high molecular weight, film forming, and crystalline.