Electrospraying: an in-situ polymerisation route for fabricating high macroporous scaffolds

This paper reports a direct jet-based polymerisation by polycondensation approach to forming a self-supporting scaffold structure. The processing technique is electrospraying, which is also known as electrohydrodynamic atomization. A specially formulated ethanolic siloxane sol derived from alkoxysilanes was synthesised and electrosprayed using a ring-shaped ground electrode configuration. The medium was seen to electrospray in the stable cone-jet mode, which later gave rise to the growing or forming of “fir-tree” like structures. The materials were characterised using microscopy, solid state NMR, FTIR, XRD and DSC. Hence this paper explains the direct controlled polycondensation from the siloxane sol and further presents the basis by which these scaffolds take shape.     

Fluorine containing poly(amide-imide)s: synthesis and formation of Langmuir-Blodgett monolayers

Soluble fluorine containing poly(amide-imide)s, PAI(1-4), were synthesized from diimide-dicarboxylic acid, 2,2-bis[N-(4-carboxyphenyl)-phthalimide-1,4-yl]hexafluoropropane with various diamines by direct polycondensation in N-methyl-2-pyrrolidone (NMP) containing CaCl₂ and using triphenyl phosphite and pyridine as condensing agents. The polymers were readily soluble in aprotic polar solvents such as NMP, N,N-dimethylacetamide, dimethyl sulfoxide and tetrahydrofuran. Their Langmuir monolayers were studied at the air/water interface. The monolayers were generally stable at the water surface and could be reproducibly transferred onto solid substrates to build up Langmuir-Blodgett (LB) multilayers. The LB mono- and multilayers were characterized by ultra-violet/visible spectroscopy (UV-Vis), surface plasmon resonance, atomic force microscopy.     

Novel conjugated polymer poly(benzobisoxazole-2,6-diylvinylene): synthesis and evidence of aggregate formation in methanesulfonic acid

A new conjugated polymer poly(benzobisoxazole-2,6-diylvinylene) (PBOV) has been synthesized as an analogue of poly(p-phenylene benzobisoxazole) (PBO). The comparison between PBOV and PBO has been carried out by Fourier transform infrared spectroscopy, thermogravimetric analysis, UV, and photoluminescence (PL) spectroscopy. The UV absorption peaks, PL excitation and emission wavelengths of PBOV have a significant red-shift due to the better electronic delocalization. Similar to PBO, it can be observed in the PL spectra of PBOV at various concentrations in methanesulfonic acid (MSA) that the intensity of emission was depressed and the highly structured emission spectra gradually changed to featureless, red-shifted, and broad spectra with increasing concentration. The change in emission spectra can be attributed to the existence of the interchain aggregates, although PBOV does not show highly ordered structure as PBO does.     

Synthesis and characterization of novel heat resistant poly(amide imide)s

A series of new poly(amide imide)s was prepared from new diacid containing sulfone, ether, amide and imide groups with various aromatic diamines. The diacid was synthesized via four steps, starting from reaction of 4-aminophenol with 4-nitrobenzoyl chloride in the presence of propylene oxide afforded N-(4-hydroxy phenyl)-4-nitrobenzamide. In the second step, reduction of nitro group resulted in preparation of 4-amino-N-(4-hydroxy phenyl) benzamide. In the next step for the preparation of diamine, the reaction of 4-amino-N-(4-hydroxy phenyl) benzamide with bis-(4-chlorophenyl) sulfone in the presence of K₂CO₃ was achieved. The prepared sulfone ether amide diamine was reacted with two moles of trimellitic anhydride to synthesize related sulfone ether amide imide diacid. The precursors and final monomer were characterized by FT-IR, H-NMR and elemental analysis. Direct polycondensation reaction of the sulfone ether amide imide diacid with different diamines in the presence of triphenyl phosphite afforded five different poly (sulfone ether amide imide amide)s. The obtained polymers were fully characterized and their physical properties including thermal behavior, thermal stability, solubility, and inherent viscosity were studied.     

Novel aromatic polyimides derived from benzofuro[2,3-b]benzofuran-2,3,8,9-tetracarboxylic dianhydride (BBTDA)

Benzofuro[2,3-b]benzofuran-2,3,8,9-tetracarboxylic dianhydride (BBTDA) is introduced as a monomer for the synthesis of a series of novel polyimides with enhanced high thermal stability. Polyimides derived from BBTDA and aromatic diamines showed high glass transition (T_g>296 °C) and degradation (T₅>455 °C) temperatures, and were soluble in organic solvents (i.e. N-methyl pyrrolidone (NMP), N,N^′-dimethylformamide (DMF), N,N^′-dimethylacetamide (DMAc)). The polymerization yielded high-molecular-weight polyimides with inherent viscosities ranging from 1.75 to 2.14 dl/g. The polymers were characterized by IR and elemental analysis.     

酚酞型聚芳醚砜(Ⅶ):K_2C0_3存在下PP/DCDPS体系聚合反应机理的研究

利用~(13)C-NMR方法研究了弱碱K_2CO_3存在下酚酞成盐反应及其与活性双卤砜亲核缩聚反应过程中的结构特征。对一系列碱性条件下酚酞(PP)与4,4'-二氯二苯砜(DCDPS)的缩聚反应的研究表明任何影响内酯结构酚酞盐生成的因素都会严重阻碍聚合反应的进行。对模型化合物存在下K_2CO_3在极性非质子溶剂中的溶解/解离行为的研究结果表明酚酞类Card。双酚与固体K_2CO_3之间可能存在着一种特殊的络合作用。基于我们系列研究结果,本文中总结提出了弱碱K_2CO_3存在下酚酞的反应机理。     

Synthesis and characterization of new polyamides derived from di(4-cyanophenyl)isosorbide

New optically active polyamides were synthesized according to two ways: using a microwave-assisted polycondensation of an optically active isosorbide-derived diacylchloride with different aromatic diamines in NMP and using interfacial polymerization from an isosorbide-derived diamine with different diacylchlorides. The polymers are obtained with inherent viscosities in the range from 0.11 to 1.05 dL/g. The DSC and TGA measurements clearly demonstrate the high thermal stability of these polymers when considering the range of the melting points from 200 °C to 300 °C and the absence of decomposition till 350 °C.     

PAMAM体型缩聚物的制备及其性能研究

以分子末端带有多官能度活泼端基的PAMAM等为原料 ,通过缩聚反应制备了一类新型体型缩聚物 .借助X射线光电子能谱仪 (XPS)对制备的体型缩聚物进行分析 ,利用其化学分析电子光谱 (ESCA)中碳元素价态的拟合数据判断体型缩聚反应进行的程度 ,数据表明酯基碳 (—COO)拟合峰已基本消失 ,说明其与氨基缩合反应转化为酰胺基 (—CON) ,且反应进行的比较彻底 .通过体型缩聚物在乙醇、正己烷、甲苯、氯仿、异丙醇、乙酸、甲酸、去离子水中进行溶胀试验 ,发现其在甲酸作为溶剂体系中的溶胀比出现最大值 ,根据溶度参数的意义估测体型缩聚物的溶度参数约为δ2 =2 7 6 (MJ m3) 1 2 (即甲酸的溶度参数 ) .对原料PAMAM以及制备的体型缩聚物进行DSC分析 ,发现制备体型缩聚物的玻璃化转变温度 (Tg)有了较大提高 ,从初始原料PAMAM的负值提高到 4 8℃左右 .     

Soluble, thermally stable poly(ester amide)s derived from terephthalic acid bis(carboxydiphenyl methyl)ester and different diamines

Terephthalic acid bis(carboxydiphenyl methyl)ester (TBE) as a new monomer for the preparation of polyamides was synthesized through the nucleophilic substitution reaction of benzilic acid with terephthaloyl chloride. This diester-diacid (TBE) was characterized using conventional spectroscopic methods. Polycondensation reactions of TBE with different aromatic and semi-aromatic diamines via Yamazaki method resulted different poly(ester amide)s. All the polymers were characterized and their physical and thermal properties were studied.     

逐步增长聚合的研究进展

逐步增长聚合应用面广,且聚合物分子量是逐步增加的,近来利用逐步增长聚合可以合成新型高分子材料日益引人注目。按照逐步增长聚合的不同类型,对近年来逐步增长聚合研究的新进展,特别是对合成聚酯等的缩聚反应,以及利用二异氰酸酯和Click反应的逐步加成聚合等进行了综述。为了进一步获得性能优良、分子量可控、结构理想且制备方法简便的高分子材料,加强逐步增长聚合理论研究、开发新型结构的单体,并充分开发相应的聚合新技术,是今后逐步增长聚合研究的重点。