柔性OLED显示用聚酰亚胺基板的合成与性能

合成了一种含吡啶结构的刚性二胺,2-(4-氨基苯基)-5-氨基吡啶(PD),将其与二氨基二苯醚(ODA)以及均苯四甲酸二酐(PMDA)共聚,调控分子链中刚性与柔性结构单元的比例,制备出一系列聚酰亚胺共聚物.结果表明:随着聚酰亚胺中含吡啶结构的刚性二胺PD含量增加,玻璃化转变温度显著提高(Tg>450℃),热膨胀系数逐渐降低(CTE<5×10^-6K^-1,50～400℃).同时,聚酰亚胺薄膜的拉伸强度提高(1.25倍),模量显著增加(4.53倍),但仍保持较高的断裂伸长率(>35%).利用广角X射线衍射(WAXD)分析聚合物聚集态结构表明,含吡啶结构刚性二胺(PD)的引入使聚酰亚胺分子链倾向于有序排列和紧密堆积,结晶度增加.因此,通过调控聚合物链中刚性二胺(PD)含量可使PI薄膜同时达到优异的尺寸稳定性、高耐热性、高强度以及较好的柔韧性,此类PI有望应用于柔性OLED显示领域.     

多嵌段高分子的溶解性和分子形状的蒙特卡罗研究

利用 Ｍｏｎｔｅ Ｃａｒｌｏ 方法模拟了两组分多嵌段高分子链在稀溶液中的行为,着重探讨了不同的嵌段长度对高分子性质的影响．研究中以自避的分子链为研究对象,分别考察了稀溶液中该分子链的溶解性、分子线团形状和嵌段单元的空间分布,与嵌段长度的关系．结果表明,在相同溶剂条件下,嵌段序列的长度对共聚高分子溶解性有较大影响,嵌段序列长度与溶解性能具有非单调的变化规律．该分子链在溶剂中的形状同样受到嵌段序列长度的影响．嵌段间的相互作用能的差别越大,则高分子的溶解性和形状对嵌段长度的依赖性就越显著     

可结晶共聚物的分子建模及其应用

共聚是调控高分子材料结晶性能的有效手段,因而共聚物链单元的序列结构对其结晶行为的影响机制是高分子结构与性能关系研究中的重要科学问题.本文从可结晶共聚物链单元序列化学结构的分子建模出发,围绕无规共聚物和嵌段共聚物序列结构对其结晶行为的调控机制,总结了近年来采用动态蒙特卡罗(Monte Carlo)分子模拟方法所开展的相关研究进展.以静态条件下温度调控结晶和动态条件下应变诱导结晶这两个方面为脉络,本文结合线型低密度聚乙烯结晶、两嵌段共聚物自组装受限结晶和热塑性弹性体取向诱导结晶等典型应用案例,旨在表明有效的分子建模有助于研究人员深入理解共聚物结晶的微观调控机制,从而更好地从事高分子材料的基础研究和应用开发.     

PDLA-PBS-PDLA三嵌段共聚物的合成及性能

合成了末端均为羟基的聚丁二酸丁二醇酯(PBS)预聚物,再以PBS的端羟基引发D-丙交酯(D-LA)开环聚合,得到聚右旋乳酸(PDLA)与PBS的三嵌段共聚物(PDLA-PBS-PDLA).通过凝胶渗透色谱和核磁共振氢谱进行了结构表征.随着m(D-LA)∶m(PBS)由0.51∶1逐渐增加至2.60∶1,PDLA-PDS-PDLA中PDLA链段的长度逐渐增加.随着PDLA嵌段长度的增加,PDLA嵌段对PBS嵌段的限制作用增强,并导致PBS嵌段结晶温度下降,结晶焓降低.当m(D-LA)∶m(PBS)=2.60∶1时,PBS嵌段不再能形成结晶.而m(D-LA)∶m(PBS)在0.51∶1~3.04∶1范围内,PDLA嵌段均可形成结晶,PDLA嵌段的熔点随其在嵌段共聚物中含量的增加而逐渐升高,但PDLA嵌段的熔融焓呈现先增加后降低的趋势.在部分嵌段共聚物中,PBS和PDLA嵌段可各自形成结晶,且PBS和PDLA的结晶结构不随组分的变化而发生改变,表明该嵌段共聚物中PDLA嵌段和PBS嵌段呈微相分离结构.     

聚谷氨酸苄酯-g-(聚四氢呋喃-b-聚异丁烯)共聚物的微观结构与形态

通过可控/活性离子聚合方法设计合成一系列不同共聚组成的聚谷氨酸苄酯-g-(聚四氢呋喃-b-聚异丁烯)的新型嵌段接枝共聚物,即PBLG-g-(PTHF-b-PIB),研究共聚物中支链(PTHF-b-PIB)长度及接枝密度对主链PBLG玻璃化转变温度、α-螺旋二级结构及其转变的影响,研究支链中PTHF链段长度对其双端受限的玻璃化转变及凝聚态结构的影响.结果表明:PBLG-g-(PTHF-b-PIB)共聚物中刚性主链保持α-螺旋二级结构;随着支链长度增加或接枝密度增加,主链PBLG的α-螺旋二级结构特征峰逐渐减弱,玻璃化转变温度逐渐提高,α-螺旋结构发生转变的焓值逐渐增大;在确定接枝密度的情况下,随着支链中PTHF链段长度增加,共聚物中双端受限的PTHF链段结晶逐渐增强,结晶熔融温度及熔融焓均增加;在确定支链中PTHF链段长度的情况下,随着接枝密度增大,支链间链段相互排斥,PTHF链段结晶逐渐减弱.     

二嵌段共聚物PCL-b-PB与PVME共混体系的结晶行为比较

用^1H—NMR对两种不同共聚组成的己内酯-丁二烯嵌段共聚物（PCL-b-PB）链结构进行了分析。尽管两种共聚物中丁二烯百分含量不N,但丁二烯链段的平均长度基本一致。用红外光谱、差示扫描量热法和偏光显微镜研究了在两种己内酯-丁二烯嵌段共聚物中加入非晶组分聚乙烯基甲基醚（PVME）所形成共混体系的混容性和结晶行为。结果表明具有较长己内酯链段的PCL1-b-PB和较短己内酯链段的PCL2-b-PB与PVME形成的共混体系中均存在着分子间相互作用,且都具有一定的混容性。然而由于嵌段共聚物中己内酯链段的长度不同,样品的结晶能力存在明显差异,PCL1-b—PB／PVME体系中PCL链段结晶能力明显较强。并且结晶形态具有一定的差异：形成清晰环带球晶的温度、组成范围不一致。     

聚苯乙烯-b-聚右旋乳酸二嵌段共聚物的热性能和结晶行为研究

合成了系列聚右旋乳酸(PDLA)嵌段重量分率(fw=0～0.61)的窄分子量分布聚苯乙烯-b-聚右旋乳酸二嵌段共聚物(PS-b-PDLA).运用温度调制示差扫描热分析仪(TMDSC)和热台偏振光显微镜(POM)等研究手段,对制备所得的结晶性二嵌段共聚物的热性能、结晶速率与结晶形貌等进行了研究.研究结果表明,与聚右旋乳酸均聚物相比,随着PS-b-PDLA中结晶性PDLA嵌段重量分率fw减少,无定形聚苯乙烯嵌段(PS)对PDLA嵌段链段的结晶抑制作用增强,PS-b-PDLA的热结晶性能与结晶形貌发生显著变化;相对于PDLA均聚物,PS-b-PDLA的冷结晶温度(Tcc)和结晶平衡熔点(Tm0)分别下降14℃和38℃,球晶生长速率明显降低.在无定形PS嵌段链段的玻璃化温度(Tg)附近,二嵌段PS-b-PDLA的结晶行为出现拐点,揭示PS嵌段由于相分离所形成纳米微相空间对PS-b-PDLA中PDLA链段的结晶产生影响,并且该影响作用程度与PDLA嵌段的重量分率fw和结晶温度(Tc)相关。     

呼吸图法制备聚亚甲基-b-聚甲基丙烯酸甲酯多孔薄膜

首先利用叶立德活性聚合和原子转移活性自由基聚合(ATRP)相结合制备了三个不同链段比的聚亚甲基-b-聚甲基丙烯酸甲酯(PM-b-PMMA)两嵌段聚合物. 接着以它们为原料, 利用静态呼吸图方法在四种不同溶剂中制备了一系列的具有蜂窝状表面的多孔薄膜, 用扫描电子显微镜(SEM)观察了多孔薄膜的形貌. 研究了溶剂、溶液浓度、聚合物链段长度及链段比等因素对多孔薄膜表面孔的大小和分布的影响. 结果表明: 当PM_2k-b-PMMA_2k嵌段聚合物浓度为3 wt%、溶剂为二硫化碳(CS₂)和二氯甲烷(CH₂Cl₂)时, 可以通过静态呼吸图方法制备出孔径为纳米级(520 nm)和微米级(1.1 μm)的较为规整的多孔薄膜. 多孔薄膜表面的孔径随PM-b-PMMA浓度的减小而增大|两嵌段聚合物中两个链段的长度及其链段比的变化对多孔膜表面孔径均产生较大的影响.     

长软链段对苯二甲酸乙二酯-环氧乙烷多嵌段共聚物的组成不均一性研究

合成了不同软链段长度和不同硬链段含量的系列对苯二甲酸乙二酯－环氧乙烷(PET-PEO)多嵌段共聚物,用NMR质子港测定了硬链段含量,对部分溶于氯仿的PET－PEO多嵌段共聚物进行了分离,并分别测定其氯仿可溶物和不溶物的硬链段含量、熔融热谱和热结晶谱.揭示了PET－PEO多嵌段共聚物的组成不均一性及其对软镇段长度和硬链段含量的依赖性,进而用DSC热谱证明了软链段和硬链段的结晶能力与PET－PEO多嵌段共聚物组成不均一性密切相关.     

表面活性单体NaAMC14S/丙烯酰胺共聚物的分子链微结构与疏水缔合性

在实施丙烯酰胺型阴离子表面活性单体2-丙烯酰胺基十四烷磺酸钠(NaAMC14S)与丙烯酰胺(AM)水溶液均相共聚合过程中,分别通过改变AM与NaAMC14S的投料比、改变外加电解质NaCl的加入量以及引发剂的用量,制备了分子链微结构系列变化的具有微嵌段结构的共聚物NaAMC14S/AM;采用荧光探针法与表观粘度法研究了共聚物分子链微结构与其疏水缔合性能之间关系,探索了共聚物分子链中疏水微嵌段含量、疏水微嵌段长度及共聚物分子量诸微结构因数对共聚物疏水缔合性的影响.结果表明,共聚物NaAMC14S/AM的疏水缔合性随着疏水微嵌段含量的增加而增强,随着疏水微嵌段长度的增长而增强,当疏水微嵌段含量和嵌段长度一定时,共聚物的疏水缔合性随分子量的增大而增强.     

Specific essential work of fracture of polyurethane thin films with different molecular structures

A series of polyurethane (PU) thin films with different hard-to-soft segment ratios were synthesized in our laboratory. The molecular and morphological structures of the PU films were characterized with Fourier transform infrared (FTIR), small-angle X-ray scattering (SAXS), wide-angle x-ray diffraction, dynamic mechanical analysis, and differential scanning calorimetry. The PU films showed a single glass transition when the hard-to-soft segment ratio varied from 1:2 to 1:8, suggesting no significant phase separation between the hard and soft segments. FTIR and SAXS results disclosed that the PU films had a network structure with the physical crosslinks formed via the intermolecular hydrogen bonds established between the hard segments. The fracture toughness of the ductile PU films was characterized with the essential work of fracture method under different conditions. It was found that the specific essential work of fracture was a function of the chain length between crosslinks and independent of the test temperature when fracture occurred at a temperature below the glass transition temperature. The physical meaning of this fracture parameter was proposed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1418–1424, 2007     

Studies on surface structures of poly(ethylene oxide)‐segmented nylon films

The surface structures of three kinds of poly(ethylene oxide)‐segmented nylon (PEO‐Ny) molten films were investigated using a scanning electron microscopy (SEM), an electron spectroscopy for a chemical analysis (ESCA), and a static secondary ion mass spectrometry (SSIMS). The PEO‐Ny's used were high semicrystalline PEO‐segmented poly(iminosebacoyliminohexamethylene) (PEO‐Ny610), low semicrystalline PEO‐segmented poly(iminosebacoylimino‐m‐xylene) (PEO‐NyM10), and amorphous PEO‐segmented poly(iminoisophthaloyliminomethylene‐1,3‐cyclohexylenemethylene) (PEO‐NyBI). SEM observations show that the surfaces of the PEO‐Ny610 and PEO‐NyM10 films are composed of spherulite, and that PEO‐NyBI film has a smooth surface. The results of ESCA and SSIMS exhibit the significant enrichments of PEO segment at the surfaces of all the films regardless of the crystallinity. The reason for the enrichment of PEO segment was discussed in terms of the surface tension of the corresponding homopolymers in the melting state. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1045–1056, 2000     

Microphase Separation of Bulk and Ultrathin Films of Polyurethane Elastomers

Surmmary: Polyurethane elastomers (PUEs) were synthesized with poly(oxytetramethylene) glycol (PTMG), 4,4′-diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD)/1,1,1-trimethylol propane (TMP) by a prepolymer method. The degree of microphase separation of bulk and ultrathin films for these PUEs was confirmed by Fourier transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC) and atomic force microscopy (AFM). In the bulk films, FT-IR and DSC measurements revealed that the degree of micro-phase separation strengthened with increasing BD content. AFM observation of the BD-PUE showed hard segment domains surrounded by a soft segment matrix. The domains ranged in size from 10-20 nm, while BD/TMP- and TMP PUEs did not have clear domains. On the other hand, AFM observation was carried out on thin films (200 mm in thickness) and ultrathin films (approximately 8-5 nm) prepared by spin-coating the different concentrations of PUE solutions. The microphase separated strucuture under 10 nm in thickness showed marked decreases in the size of the microphase-separated domain.     

Aqueous dispersion of polyurethane ionomers from hexamethylene diisocyanate and trimellitic anhydride

Polyurethane (PU) ionomers were prepared from trimellitic anhydride (TMA), poly(tetramethylene adipate) glycol (PTAd), and hexamethylene diisocyanate (HDI) in acetone. Upon neutralizing the carboxylic groups with a tertiary amine (TEA), and adding water to PU ionomer solution, followed by removing the acetone, stable aqueous PU dispersions were obtained.Effects of interionic molecular weight and nonionic hydrophilic segment, viz. monofunctional ethylene-propylene oxide ether on particle, size, emulsion viscosity, mechanical, and viscoelastic properties of the emulsion cast films were examined.     

Flow rates of polymer solutions through porous disks as a function of solute. II. Thickness and structure of adsorbed polymer films

The thickness of films of poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc), and polystyrene (PS) adsorbed on Pyrex glass was studied by measuring the flow rates of polymer solutions and the corresponding pure solvents through sintered filter disks. Adsorption isotherms were in agreement with those reported by other workers and showed saturation adsorption equivalent to 2–8 condensed monolayers of monomer units. Film thicknesses were of the order of magnitude of the free coil diameters in solution and were directly proportional to the intrinsic viscosity of the polymer, except for PS in benzene where the thicknesses leveled off as molecular weight increased. It was concluded that polymers adsorb from solution in monolayers of compressed or interpenetrating coils; that below some critical molecular weight which varies with polymer and solvent, a much larger fraction of the segments lies directly in the interface; that adsorbed films may consist of a dense layer immediately adjacent to the surface and a deep layer of loops extending into the solvent; and that it is the segment—solvent interaction rather than the segment—surface interaction which dominates the conformation of the adsorbed chain.     

具有明确硬段结构的水性聚氨酯脲的研究

通过逐步反应由4,4′-二苯基甲烷二异氰酸酯、2,2-二羟甲基丙酸和1,4-丁二醇,合成了结构明确的硬段模型化合物.通过13C NMR对其序列结构进行了表征,并通过FTIR、DSC和WAXD对其形态结构进行了研究.进一步制备了具有这类规整结构硬段的水性聚氨酯脲,初步考察了水分散液及其成膜后的性能.实验结果表明,这类聚氨酯脲水分散液的粒径小于110nm,在室温下贮存期大于一年,成膜后具有优异的耐水性能以及表面疏水性能.     

亲水改性PBS基共聚物的N435酶降解差异性及分子模拟

在水相体系中, 采用脂肪酶Novozym435对聚丁二酸丁二醇酯(PBS)分子主链中氧醚键在醇段和酸段的不同位置的共聚物聚(丁二酸丁二醇-co-丁二酸二甘醇酯)[P(BS-co-BDGA)]和聚(丁二酸丁二醇-co-二甘醇酸丁二醇酯)[P(BS-co-DEGS)]进行酶促降解研究. 以分子对接模拟探讨了酶对亲水性底物的识别及相互作用机制. 通过对降解前后不同摩尔比的共聚物薄膜的质量损失率、 亲水性、 热性能以及降解产物的分析, 研究了PBS改性共聚物的降解规律. 结果表明, 随着降解时间的推移, 所有共聚物薄膜的质量损失率升高, 亲水性增强, 热分解温度升高; 降解5 d后, P(BS-co-BDGA)降解产生的低聚物种类比P(BS-co-DEGS)的多. 分子对接结果表明, 醚键在酸段的P(BS-co-BDGA)型酯键与Novozym435酶活性位点的结合比醚键在醇段的P(BS-co-DEGS)型酯键更稳定, 因此, 在N435脂肪酶作用下, P(BS-co-BDGA)比P(BS-co-DEGS)的降解效果好. 实验结果表明, 当DGA摩尔分数为20%时, 降解效果最佳.     

Evaluation of physico-mechanical properties of precipitated polyurethane films in medium of free radical agents

Segmented poly(ester-urethanes) (PU) elastomers based on poly(ethylene diethylene adipate)diols as a soft segment and aromatic diisocyanates in the hard segment were synthesized by a conventional method. The precipitated PU elastomers films have been degraded after a limited exposure to free radical agents. An increase of the ratio of radical agents had an increase in the hard segment content which was associated with increased hard microdomain crystallinity, hardness and improvement in mechanical properties. It is suggested that the superior mechanical performance may be related to a interconnecting hard microdomain texture by a radical cross-linking process. The present study attempts to correlate the physical-mechanical properties of the precipitated PU films with the concentration of the free radical agents. In all cases, the effect of free radical cross-linking was to increase the ultimate tensile strain.     

Synthesis,characterization, and permeability evaluation of hybrid organic–inorganic films

The preparation and characterization of hybrid organic–inorganic films based on poly(dimethylsiloxane), PDMS, crosslinked with nanoclusters obtained from pentaerythrithol triacrylate (PETA) and 2‐aminoethyl‐3‐aminopropyltrimethoxysilane (AS), are reported. The introduction of silica nanoclusters, obtained from tetraethoxysilane as an additional crosslinker, improved the mechanical stability of the films and also produced a noticeable decrease in the solvent sorption and in the distance between the nodes of the polymeric networks. The performance of these films as membranes for gas separation processes was similar to those reported for commercial PDMS, although they presented polar organic PETA/AS crosslinker nuclei. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4281–4292, 2004     

Mechanical behavior during different weathering tests of the polyurethane elastomers films

Segmented poly(ester-urethane)elastomers (PU) based on poly(ethylene diethylene adipate) diols as a soft segment and aromatic diisocyanates in the hard segment were synthesized by a conventional method. The precipitated and compact polyurethane films have been degraded after a limited exposure to natural weathering. The effects on mechanical properties of precipitated and compact polyurethane films were found to be a measure of the degradation due to weathering. The present study attempts to correlate the physical-mechanical properties of the precipitated polyurethane and compact films with time of weathering. In all cases a certain amount of oxidative change had been initiated. This was probably associated with enzyme adsorption on surfaces. We compared natural weathering of PU films carried out in earth, seawater and exposure to sunlight with untreated samples. In common with other weathering tests, the effect was to decrease the ultimate tensile strain, except seawater. It was found that enzymatic degradation in the earth occurred only after, the ageing process was continuous and practically linear with a relatively short initial period of increase in degradation rate.