POLYMER NETWORK-POLY(ETHYLENE GLYCOL)COMPLEXES WITH SHAPE MEMORY EFFECT

The complexes of poly(methacrylic acid-co-methyl methacrylate) network with poly(ethylene glycol) stabilized byhydrogen bonds were prepared. By introducing the poly(ethylene glycol), a large difference in storage modulus below andabove the glass transition temperature occurred and the complexes exhibited shape memory behaviors. The morphology ofcomplexes was studied by using DSC, WAXD, and DMA. The results indicate that the fixed phase of this kind of novelshape memory materials is the network, and the reversible phase is the amorphous state of PEG:PMAA complex phase. Theshape recoverability almost reaches 100%. This type of complexes can be regarded as a novel shape memory network.     

苯乙烯基形状记忆聚合物热力学行为的有限元分析

对苯乙烯基形状记忆聚合物进行了拉伸实验研究,测定了该材料在25℃、30℃、40℃和50℃时的弹性模量和屈服极限.根据实验结果,建立了苯乙烯基形状记忆聚合物的材料参数方程,描述了苯乙烯基形状记忆聚合物在玻璃体转化过程中,材料参数和温度的关系.在假设形状记忆聚合物为各向同性材料的基础上,将Tobushi等建立的热力学本构方程从一维扩展到三维.基于有限元分析软件ABAQUS的二次开发功能,针对上述本构方程和材料参数方程,编写了可供ABAQUS调用的UMAT函数,并对苯乙烯基形状记忆聚合物实现形状记忆效应的高温变形、应力冻结和形状恢复等热力学过程,进行了有限元数值模拟分析.     

液化MDI/PHMA体系形状记忆聚氨酯结构与性能的研究

用聚已二酸已二酯(PHMA)为软段,液化MDI和BDO为硬段,采用两步溶液法合成了具有形状记忆功能的多嵌段聚氨酯,利用DSC,WAXD等测试手段分析了该体系的形态结构,同时讨论了该体系的形状记忆行为、拉伸力学性能及动态力学性能.结果发现,该体系SMPU的硬段以无定形存在,软段具有很好的结晶性能;具有很好的形状记忆性能,形状固定率可达100%,形状回复率在97%以上,回复温度在35~45℃;同时它兼有较高的拉伸强度(约为28~50 MPa)和断裂伸长率(约为900%~1400%);动态力学性能卓越,其室温模量可达279.8 MPa,软段熔融前后模量比可达140.     

气相生长碳纤维/形状记忆聚氨酯复合薄膜的力学及形状记忆性能研究

采用溶液混合法制备了不同含量的气相生长碳纤维(VGCF)增强形状记忆聚氨酯(SMPU)的复合材料薄膜,测试分析了纯SMPU及VGCF/SMPU复合材料薄膜的力学性能及形状记忆性能.结果表明,制得的复合材料薄膜在VGCF含量达到9 wt%时,VGCF在SMPU基体中仍具有较好的分散性;SMPU与VGCF复合后,得到的复合材料薄膜的拉伸强度和刚度有较大程度的提高,含量达到9 wt%时复合材料薄膜的拉伸强度比纯SMPU提高66%,弹性模量提高300%,储能模量也有较大程度提高;SMPU与VGCF复合后,形状记忆性能有一定的下降,但经过适当预处理后,其形状记忆性能可以基本接近纯SMPU.     

SHAPE MEMORY EFFECT OF SLIGHTLY-CROSSLINKED POLYETHYLENE

A series of slightly crosslinked polyethylenes (SXLPE) was prepared by aone-step method using dicumyl peroxide as crosslinking agent in a Haake Mixer. The gelcontents G (Soxhlet extracted) of the samples are in the range from 5% to 20% by weight.Their shear viscosity, crystallization and melting behavior, dynamic mechanical propertiesand shape recovery effect were systematically investigated in terms of the content of thecrosslinking agent. It shows that under certain experimental conditions the SXLPE's mayexhibit good shape fixation ability and shape memory properties, which are similar to thoseof the commercially available shape memory polyethylenes prepared by gamma-irradiationtechnique. However the shape memory behavior of these samples is not very stable due totheir low crosslinking degree, or gel content. Thus their application is limited in specialcases with fast strain fixing procedures.     

具有热致形状记忆功能的热塑性多嵌段聚氨酯

以ＰＣＬ为软段、ＴＤＩ－ＢＤＯ为硬段，采用溶液聚合的方法合成了具有形状记忆功能的线性多嵌段聚氨酯．利用ＤＳＣ、ＤＭＴＡ、ＷＡＸＤ等测试手段对体系的结晶性、微相分离行为进行了研究．结果发现：聚氨酯中硬段的存在对软段的结晶有着很大的影响，当软段序列的平均分子量达到３０００以上时，软段才可以很好地结晶；并且，硬段含量也必须高于一定值才能形成较为完善的物理交联点．符合这些条件的试样能显示很好的形状记忆特征．此外还就拉伸比、多次形变以及组成等对材料的形状回复性能的影响进行了详细的研究．     

THERMALLY STIMULATED SHAPE MEMORY BEHAVIOR OF POLYMERS WITH PHYSICAL CROSSLINKS*

The shape memory effect of polymers was investigated for the purpose of improving the processingconditions of their preparation and broadening the list of polymers for shape memory applications. Emphasiswas put on the possibility of using polymers with physical crosslinks as shape memory materials and theirstructure-function relationships. Segmented block polyurethanes and polyethylene/nylon 6 graft copolymerswere used as examples of polymers with physical crosslinks. It was found that these copolymers can really beused as thermally stimulated shape memory materials with large recoverable strain and high final recoveryrate. The main advantage of using copolymers is their improved processing conditions as compared withpolymers with chemical crosslinks. As only physical crosslinks are introduced, all conventional processingtechniques for thermal plastics can be used, and the materials become easily reusable. The results indicatethat the high crystallinity of these copolymers at room temperature and the formation of stable physicalcrosslinks are the two prerequisites for these polymers to exhibit shape memory effect. The successful use ofblock and graft copolymers imply the possibility of using polymers of various structure and properties asshape memory materials.     

形状记忆聚合物热力学本构方程

借鉴聚合物结晶学相关理论,建立了一个针对该类材料的新的热力学本构关系,通过与已有实验结果相比较,发现理论预测值与实验吻合较好.     

Poly(urethane-oxazolidone): Synthesis, characterisation and shape memory properties

Poly(urethane-oxazolidone) were synthesized by reacting isocyanate-terminated oxazolidone with hydroxy-telechelic poly(tetramethylene oxide) (PTMO). The molar ratios of the reactants were varied to get polymers of varying oxazolidone and urethane compositons. The polymers were characterized by DSC, FTIR, XRD, dynamic mechanical thermal analysis and chemical analyses. An increase in the concentration of urethane and oxazolidone groups caused a decrease in tensile strength and elongation of the poly(urethane-oxazolidone). The polymers possessed crystallites of PTMO whose melting transition temperature decreased on enhancing the oxazolidone concentration. The polymers exhibited thermo-responsive shape memory properties, which was confirmed and quantified by cyclic tensile tests. The influence of oxazolidone modification and the consequent soft/hard segment variation on the thermal, mechanical, dynamic-mechanical and shape recovery properties of the resultant polymers was investigated. The oxazolidone moities conferred enhanced shape recovery and shape fixity to the polyurethane.     

THERMALLY STIMULATED SHAPE MEMORY BEHAVIOR OF(ETHYLENE OXIDE-BUTYLENE TEREPHTHALATE)SEGMENTED COPOLYMER

The thermally stimulated shape memory behavior of ethylene oxide-butylene terephthalate (EOBT) segmentedcopolymers with different soft segment molecular weight and hard segment content was investigated. The deformationrecovery ratio R_f of the EOBT samples increases with the soft segment molecular weight and the hard segment weightcontent, while the average overall deformation recovery speed V_r increases with the hard segment content. The temperatureof maximum deformation recovery speed (T_M) is determined by the melting temperature of the soft segment crystals and thestability of the crystallized hard segment domains.     

可生物降解多嵌段聚(酯-氨酯)的合成及其热致形状记忆性质

以端羟基L-丙交酯/乙交酯共聚物(PLLG-diol)和端羟基ε-己内酯/乙交酯共聚物(PCG-diol)为硬段和软段,通过与二异氰酸酯反应制得了软、硬分子量和组成均可调的多嵌段聚(酯-氨酯),表征了它们的形状记忆行为.多嵌段聚(酯-氨酯)具有良好的形状记忆性质,应变固定率达98%~99.5%,应变恢复率达93%~98.5%;通过转变温度的调节,可使多嵌段聚(酯-氨酯)在37℃体温下不发生形状变化,而在稍高于体温的温度(40~50℃)下恢复原始形状,其形状恢复速率可通过温度和升温速率来调节.     

甲壳型液晶聚合物纤维的形状记忆效应

采用TA-Q800动态热机械分析仪(DMA)研究了聚乙烯基对苯二甲酸二(对丁氧基苯)酯(PBPCS)纤维的形变回复性能,发现PBPCS纤维具有非常好的形状记忆效应,在145℃及以上温度,形状回复速率最好,9min左右可以从400%的伸长回复到原来的尺寸,于145℃,重复实验5次,结果说明形变回复重复性好.二维X衍射(2DX-Ray)研究显示形变前后PBPCS柱状分子直径d由2.54nm变为2.42nm,表明拉伸后PBPCS螺旋状的大分子主链处于更为伸直的构象,因此分子主链产生一定的内应力,即形变回复应力.由此可见,PBPCS相对柔性的聚乙烯主链使纤维具有良好的形变回复性能,而侧基的甲壳效应使得纤维能够保持初始尺寸,即PBPCS所具有的类似弹簧的特殊螺旋状分子结构是其纤维具有形状记忆效应的内在原因.     

2-溴丙酰基末端对于PLLA成核行为影响的研究

通过研究2-溴丙酰基单封端的PLLA结晶行为,来探讨聚合物结晶过程中的端基效应.首先通过开环聚合的方法(ROP),以苯甲醇为引发剂,合成了聚(L-乳酸)(PLLA).再将PLLA自由末端的羟基转化为2-溴丙酰基,得到2-溴丙酰基单封端的PLLA-Br.研究表明,2-溴丙酰基末端引入后,聚合物链段运动能力受到抑制,PLL...     

POLYMERIC IONIC CONDUCTORS MODIFIED WITH POLAR GROUPS:PART Ⅰ. IONIC CONDUCTION AND MECHANICAL PROPERTY OF LI-COMPLEX BASED ON ACRYLAM ID E-COPOLYMERIZED METHACRYLATES

Acrylamide was introduced onto the chain of poly[oligo(oxyethylene) methacrylate] as a polar constituent, and the effect of its presence on the mechanical strength and ionic conduction properties of Li-salt complex based on the resultant copolymer was investigated. The introduction of the polar constituent raises chain rigidity, retards crystallization of oligo(oxyethylene) domain and promotes the dissociation of lithium salt. The factors work on the mechanical and conduction properties synergistically, therefore both of the properties are improved simultaneously as the consequence of acrylamide-introduction.     

流动注射分光光度法研究离子强度对活性炭吸附阴离子染料的影响

利用流动注射分光光度法技术，考察了不同离子强度（NaCl)下，在水溶液中表面带负电的活性炭分别吸附3种阴离子染料的动力学行为．利用固-液相互作用方程，求取了活性炭-染料相互作用能．比较了无机盐中阳离子的种类对吸附影响的差异．结果表明：对于3种阴离子染料，离子强度的增大都起到加速吸附的作用：表现吸附速率常数、活性炭-染料相互作用能与离子强度三者之间存在密切的内在联系：在相同离子强度下，二价阳离子对吸附的加速作用要比一价阳离子的显著，但在同价阳离子之间这种作用的差别较小．     

聚甲基丙烯酸-对-甲氧基偶氮苯烷氧基酯的合成及柔性间隔基对液晶行为的影响

通过甲基丙烯酸钾盐与溴化物的反应合成了一系列柔性间隔基长度不同的甲基丙烯酸 对 甲氧基偶氮苯烷氧基酯（ＰＭＡＡＺＯｎ,ｎ＝２,３,４,５,６）,然后聚合成相应的聚合物．用１Ｈ ＮＭＲ和ＩＲ表征了聚合物的结构,ＧＰＣ测定了分子量,ＤＳＣ和偏光显微镜观测了液晶高分子的相行为和织构．研究了间隔基长度对织构、相变和热力学性质的影响,观测到聚合物的ＴＮＩ随间隔基的长度变化表现出的奇偶效应．     

铜(Ⅱ)离子对人血清γ球蛋白热变性的影响

观察对人血清y球蛋白热变性的抑制作用是筛选抗炎药物的一种体外实验方法。测定蛋白变性率的方法有两种,一种是测定加热后凝聚的蛋白,另一种是测定凝聚蛋白在醋酸中的不溶物。这两种方法在检验一般的抗炎药物时得到的结论基本上是一致的,但是在检验铜(Ⅱ)离子及其配合物时。两种方法得到相反的结论。本文旨在探讨铜(Ⅱ)离子在人血清r球蛋白热变性过程中,对形成外观凝聚物和醋酸不溶物的作用,并对两者的差异进行比较。     

ACID DISSOCIATION BEHAVIOR OF 2, 3- AND 2, 3, 9,lO-METHYL- OR CYCLOHEXYL-SUBSTITUTED CYCLAMS,THEIR COMPLEXATION BEHAVIOR WITH COPPER@) AND THE AXIAL SOLVENT SPECTRUM OF THEIR COMPLEXESINTERACTION EFFECT ON THE LIGAND-FIELD

Abstract

Stability constants of Cu(Il)-complexes for 1, 4, 8, 11-tetra-azacyclotetradecane (cyclam) analogs with periphery substituted [14]aneN₄-ring, 2, 3-tetramethyl-, 2, 3, 9, 10-octamethyl-, 2, 3-cyclohexyl, and 2, 3, 9, 10-dicyclohexyl-cyclams have been determined at 25°C in aqueous solution. The UV-Vis absorption spectra of their complexes, ([Cu(L)] (C1O₄)₂), were measured in water and some typical organic solvents (methanol, acetone, propylene carbonate, formamide, N, N-dimethylformamide, and dimethylsulfoxide). A good linear relationship was found between the stability constant logK_CuL) and the difference between the wavenumber of maximum absorption in water and in the organic solvents (δλ_max ^?1 (W-S)). The value of logK_CuL at δλ_max ^?1(W-S) = 0 not only shows a linear relation to solvent parameters, donor number and dielectric constant, but also to the enthalpy of transfer of ClO₄ ^? from water to the organic solvents. The value is proposed as a new solvent parameter ‘Kλlue’ to be used as an index for solvent-effects on Cu(II)-complexes of cyclam analogs. The increasing order of the new parameter (log scale) is as follows; DMF(27.24)>DMSO(27.14)>FA(26.82)>MeOH(26.27)>PC(25.75)>AC(24.71). Another meaning of the new parameter is assumed from connection of the potentiometric data with spectrometric data. The solvent effects on stability and the UV-Vis spectra are assumed to be caused by perturbation of the D_{4 h} or axially-elongated ligand field through axial approach of solvent to the Cu(II)-complexes and by formation of a solvent-separated ion pair between a solvated Cu(lI)-complex cation and counter anion (ClO₄)