不饱和聚酯树脂低温固化收缩影响因素

通过正交试验设计,探究了固化温度、固化剂和促进剂含量、低收缩剂(LPA)种类、含量五种因素对邻苯型不饱和聚酯(UPR)固化线收缩率的影响.方差分析的结果表明:当显著水平为95％时,LPA含量对UPR的线收缩率影响最大,所对应的F值高达8.362,超过了分位数.体系的线收缩率随LPA含量的增加而降低.然而,LPA也会同时影响树脂的力学强度.与未改性UPR相比,当LPA-4含量为6％时,体系的线收缩率由2.148％大幅下降至0.531％,弯曲强度保持率达到80％,冲击强度提高了95％,综合性能较好.     

改性不饱和聚酯树脂的形态和性能

不饱和聚酯树脂(UPR)由于固化收缩率大和固化物韧性差而影响了它的广泛应用,继合成了同时具有增韧和降收缩效果的添加剂PMB后,本文研究了添加剂的分子量和用量、添加改性后UPR体系的固化工艺及不同UPR基体树脂等因素对固化物的微现形态和性能的影响。结果表明,PMB在多种UPR中都可以产生明显的第二相结构,PMB的分子量和用量都存在一个增韧效果的最佳值,较高的固化温度有利于第二相结构的产生。     

液体聚硫聚脲增韧环氧树脂形态结构的研究

以液体聚硫聚脲齐聚物来增韧环氧-聚酰胺体系,用DMTA和SEM研究了固化后环氧树脂的形态结构、相分离程度和增韧效果．结果表明,液体聚硫聚脲齐聚物的用量、齐聚物中聚脲含量对固化后的环氧树脂玻璃化温度、模量及形态有较大影响。随增韧剂中聚脲含量的提高,固化物的玻璃化温度、相分离程度及模量增加,同时固化物韧性增加。     

PA6/PS双连续相的临界组分比及相形态研究

在哈克转矩流变仪中,研究了操作温度、螺杆转速、共混时间和相容剂苯乙烯马来酸酐共聚物(SMA)对尼龙6/聚苯乙烯(PA6/PS)共混物形成双连续相组分比例范围的影响.结果表明:操作温度、螺杆转速、共混时间对共混物形成双连续相组分比例范围的影响不大,SMA的加入使形成双连续相的比例范围大大减小,SMA阻碍分散相间的碰撞、降低其凝聚是产生这种现象的主要原因.对双连续相PA6/PS(50/50,质量分数/%)共混物进行静态热处理,用扫描电镜(SEM)观察形态发现:在一定温度下双连续相相尺寸随热处理时间增加而增大;温度越高,相尺寸随时间增大的速度也大大加快,但仍能够保持双连续相态.在一定温度下,连续相经过破裂、凝聚,使两组分的界面面积降低是相态粗化的主要原因.     

聚合温度对聚磷酸钙聚合度及结构的影响

聚合度作为一个重要影响因素对聚磷酸钙的性能必然产生影响. 采用磷酸二氢钙作为原料, 在不同聚合温度下制备了聚磷酸钙. 采用³¹P核磁共振波谱测定聚磷酸钙的聚合度, 评价聚合温度对聚合度及结构的影响, 结合磷酸二氢钙差示扫描量热-热失重分析结果, 提出了磷酸二氢钙缩聚反应的机理. 结果表明, 磷酸二氢钙缩聚产物以聚磷酸钙为主, 当聚合温度低于1000℃时, 升高聚合温度有利于聚合度的增大, 1000℃以上则反之; 此外, 升高聚合温度促进环状结构(偏磷酸钙)的生成, 其含量随聚合温度的升高而增大且1000℃以上增幅较大.     

聚醋酸乙烯酯(PVAc)/聚离子液体(PILs)半互穿聚合物网络膜的制备及气体分离性能

利用紫外光固化法,制备了聚醋酸乙烯酯(PVAc)/聚离子液体(PILs)半互穿聚合物网络膜,用于CO2/N2的分离,并对其化学结构、形貌及热稳定性进行了表征.结果表明,加入PILs后,半互穿膜的热稳定性增加,并且PILs与PVAc的相容性较好,随着PILs含量的增加,PVAc/PILs半互穿膜的CO2和N2渗透系数和溶解度系数均提高,渗透选择性先增后减,当PILs含量为50%时达到最大值64.20.     

嵌入式电容器用钛酸钡/环氧复合材料性能的研究

将颗粒尺寸分布较宽的钛酸钡(BT)粉末与环氧树脂采用溶液共混旋涂工艺制备了嵌入式电容器材料,并对该复合材料的显微结构、晶相、热稳定性及介电性能进行了分析.研究表明,该复合材料的介电常数及介电损耗与陶瓷相含量和陶瓷粉末的分散有关;在20～150kHz频率范围内,复合材料介电常数的变化较为稳定,而介电损耗值均在0.036～0.039之间,随频率增大略有增大;受BT粒子的影响,复合材料基体聚合物的有序排列分子结构被破坏,环氧树脂分子链的排列密度降低;BT粉末的加入及BT含量的增加均导致材料体系的固化温度和热分解温度提高.     

双马来酰亚胺-聚醚砜复相树脂固化与相行为

采用非等温DSC研究了双马来酰亚胺-聚醚砜（BMI-PES）复相树脂体系的固化行为和固化动力学,根据Kissinger方程计算BMI-PES复相树脂固化的表观活化能和指前因子,利用Crane方程计算反应级数,得到反应动力学方程,进行了实验固化度与理论固化度对比验证,通过SEM研究BMI-PES复相树脂微观相结构随固化温度和时间的演化规律。树脂固化行为显示:BMI-PES复相树脂固化反应存在自催化现象,PES参与了BMI固化;随着升温速率增大,BMI-PES复相树脂固化特征温度均向高温移动,但固化热焓基本不变;随着PES添加量增多,反应速率增大,BMI-PES复相树脂固化热焓降低,而峰值固化温度无变化。固化动力学研究表明:随着PES添加量增多,BMI-PES复相树脂固化表观活化能增大,但指前因子和反应级数无变化,固化为一级反应;BMI-PES树脂在200℃固化时,反应前期固化度实验数据与理论值吻合度很高。SEM结果表明,BMI-PES树脂经180℃固化处理后产生了相反转结构。      

两性星形嵌段共聚物的某些特殊性质

研究了两性聚合物(聚苯乙烯-聚环氧乙烷星形嵌段共聚物)的乳化性质,相转移催化作用及高分子共混时的增容作用。结果指出,对水-苯体系的乳化效果而言,四臂共聚物>三臂>二臂。乳化效果还随共聚物浓度增加、分子量减小及聚环氧乙烷嵌段含量的增大而增大。对于Williamson固液相反应,嵌段共聚物的相转移催化效果较纯聚环氧乙烷为好,星形的较二嵌段的为好。随分子量增大,反应物浓度及温度增加,苯酚钾的转化率增加。加2％星形嵌段共聚物有利于聚苯乙烯与氯醇橡-胶的共混,使产物的物理机械性能有所提高。     

端羟基丁二烯型聚氨酯/聚苯乙烯互穿聚合物网络的研究

研究了同步法合成的端羟基聚丁二烯型聚氨酯/聚苯乙烯互穿聚合物网络〔PU(HTPB)/PS_t-IPN〕的形态结构、热转变行为和力学性能。电镜结果表明:该类 IPN 形成既二相分离又各自连续的相结构,当 PU(HTPB)/PS_t 组成比为25/75时,体系发生相转变;组成比为50/50左右时,形成的聚苯乙烯分散相区域尺寸较小。增加每一相的交联程度,均可提高二相的互穿能力,所有 IPN 都呈现出独特的细胞状结构形态,文中根据聚氨酯首先形成的事实,提出了该结构的形成机理。T_(?)研究结果表明:玻璃化转变温度的移动将受到 IPN 自身诸因素的制约。力学性能结果表明:随 IPN 中 PU(HTPB)含量增加,材料的刚性下降,而断裂伸长则出现由增加到下降的过程,在组成比为60/40左右时,达最大值。     

Kinetically trapped co-continuous polymer morphologies through intraphase gelation of nanoparticles

We describe an approach to prepare co-continuous microstructured blends of polymers and nanoparticles by formation of a percolating network of particles within one phase of a polymer mixture undergoing spinodal decomposition. Nanorods or nanospheres of CdSe were added to near-critical blends of polystyrene and poly(vinyl methyl ether) quenched to above their lower critical solution temperature. Beyond a critical loading of nanoparticles, phase separation is arrested due to the aggregation of particles into a network (or colloidal gel) within the poly(vinyl methyl ether) phase, yielding a co-continuous spinodal-like structure with a characteristic length scale of several micrometers. The critical concentration of nanorods to achieve kinetic arrest is found to be smaller than for nanospheres, which is in qualitative agreement with the expected dependence of the nanoparticle percolation threshold on aspect ratio. Compared to structural arrest by interfacial jamming, our approach avoids the necessity for neutral wetting of particles by the two phases, providing a general pathway to co-continuous micro- and nanoscopic structures.     

Morphology and rheology of poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide)/polystyrene blends filled with silica nanoparticles

The successful development of co-continuous structure from poly(l-lactide) (PLLA) blends by melt mixing with lower PLLA content is highly desired in preparing macroporous biomaterials. However, the low viscosity of PLLA makes it difficult to prepare co-continuous PLLA blends at low PLLA concentration. In this study, hydrophilic silica nanoparticle is adopted to control the morphology of co-continuous polystyrene (PS)/PLLA blends. The influence of nanoparticle concentration on the co-continuity intervals and rheological properties of PS/PLLA blends are examined. The morphological stability of blends against melt annealing is also determined and discussed with a conceptual coarsening model for co-continuous structure. The results demonstrate that the incorporation of silica nanoparticles into PS/PLLA blends can be used to prepare macroporous PLLA structure with controllable pore size at lower PLLA content.     

聚醋酸乙烯酯/二氧化硅杂化材料的制备与性能研究

以硅酸钠在HCl溶液中的水解,经四氢呋喃(THF)萃取,制备聚硅酸溶胶,再与聚醋酸乙烯酯(PVAC)的THF溶液混合,经溶胶-凝胶过程制备了PVAC/SiO2有机/无机杂化材料.用扫描电镜(SEM),红外光谱(IR),X射线衍射,热失重及透光率等的分析测试,对制备的PVAC/SiO2杂化材料进行了结构与性能的研究.结果表明:本法制备的杂化材料中SiO2在PVAC的基体中分布均匀,SiO2在非晶态的PVAC中亦呈无定形态,杂化材料的硬度、软化温度和热分解温度都比纯PVAC有较大的提高;SiO2含量少于40%的杂化材料其断裂伸长率、屈服强度和断裂强度也比纯PVAC提高;另外,还发现在制备过程中加入少许偶联剂KH-570后,杂化材料中的有机-无机相间的相容性增加,不易发生相分离,材料的透光性能也大为改善.     

Preparation and characterization of chitosan/poly(vinyl alcohol)/poly(vinyl pyrrolidone) electrospun fibers

Ultrafine fibers of chitosan/poly(vinyl alcohol)/poly(vinyl pyrrolidone) (CS/PVA/PVP) were prepared via electrospinning. The structure and morphology of CS/PVA/PVP ultrafine fibers was characterized by the Fourier transform infrared (FT-IR) spectroscope and scanning electron microscope (SEM). Furthermore, the effects of the concentration of PVA, PVP and the electrospinning voltage on the morphology of ultrafine fibers were investigated the the SEM. When the concentration of PVA was at the range of 30wt%–40wt%, ultrafine fibers could be obtained. The diameter distributions of ultrafine fibers decreased when the electrospinning voltage increased from 20 to 30 kV. The rough surface fibers could be obtained after etching with CHCl₃.     

Sorption and diffusion of aromatic solvents through linear low density polyethylene–ethylene vinyl acetate blend membranes

An investigation has been made for understanding the transport behaviour of organic solvents through linear low-density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blend membranes with special reference to the effects of blend ratio, concentration of cross-linking agent, penetrant size and temperature. Attempts have been made to relate the transport parameter with the morphology of the blend. The various transport parameters such as diffusion coefficient (D), permeation coefficient (P) and sorption coefficients (S) were evaluated at different diffusion conditions. The results were compared with theoretical predictions and found that the diffusion process follows anomolous type behaviour. The blends show dispersed/matrix and co-continuous phase morphologies depending on the composition. Dynamic vulcanization leads to fine and uniform distribution of the dispersed domains with a stable morphology. Among the blends E₇₀ sample shows the maximum solvent uptake and E₃₀ the minimum. The solvent uptake of blend varies with concentration of cross-linking agent. Molecular size of the solvent is a decisive factor in the solvent uptake. The rate of sorption and maximum solvent uptake increase with increase of temperature. Irrespective of the solvents used, the maximum solvent uptake increases with increase of temperature. The observed sorptivity, diffusivity and permeability are associated with cross-link densities of different samples. The D, S and P values increase with increase of EVA content in the blend.     

Photoluminescence of 2,4,6-tris[4-(phenylethynyl)phenyl]-1,3,5-triazines dispersed in polymer films

Photoluminescence of three types of 1,3,5-triazine derivatives with three kinds of diphenylacetylene side chains was investigated. They showed quantum yields higher than 46% in chloroform, and the Stokes shift (66–114 nm) in chloroform depended on the kind of the diphenylacetylene side chain. In cast films, the three compounds gave a larger Stokes shift of 132–211 nm, suggesting formation of an excimer in the solid. The 1,3,5-triazine derivatives were dispersed in films of polymers such as polystyrene and poly(vinyl acetate), and photoluminescence of the films containing the 1,3,5-triazine derivatives was investigated. Dispersion of the compound in a poly(vinyl acetate) film still gave a rather larger Stokes shift of 128–203 nm. In contrast, dispersion in polystyrene reduced the Stokes shift to about 60 nm, revealing an excellent dispersing effect of polystyrene for the compounds.     

Properties of pressure sensitive adhesive made of acrylic quaternary copolymers and their blends with vinyl chloride copolymers

Acrylic quaternary copolymers (AQC) were synthesized from copolymerization reaction of 2-ethylhexyl acrylate (2-EHA), n-butyl acrylate (BA), ethyl acrylate (EA) and vinyl acetate (VAc). The blends of AQC with poly(vinyl chloride-co-vinyl acetate) (PVCVAc) and with poly(vinyl chloride-co-vinyl propionate) (PVCVP) were prepared by solution blending. Pressure sensitive adhesive (PSA) properties of AQC and their blends were investigated. Glass transition temperature T _g and holding power of AQC decreases with increasing contents of 2-EHA and BA. Tackiness, however, increases with increasing the contents of 2-EHA and BA. Peel strength shows maximum value for the sample with 15 wt% of those monomers. Tackiness of blend systems is similar, but holding power begins to decrease at 15 wt% or higher PVCVAc contents in AQC+PVCVAc blends. On the other hand, holding power of AQC+PVCVP blends increases as the contents of PVCVP increases. Failure modes of the blend are adhesive except for blends with 5 wt% of PVCVP.     

High-performance conductive materials based on the selective location of carbon black in poly(ether ether ketone)/polyimide matrix

A novel high performance conductive material with excellent comprehensive properties was prepared by melt-blending, and its performances were adjusted by controlling the selective location of carbon black (CB) in poly(ether ether ketone) (PEEK)/thermoplastic polyimide (TPI) matrix. With increasing the CB loadings, the morphology of PEEK/TPI blends changed from sea-island to co-continuous structure, which was owing to the selective location of CB in TPI phase. Notably, with the selective location of CB in the induced co-continuous PEEK/TPI matrix, the electrical percolation threshold was reduced to 5 wt%, which was significantly lower than that of binary PEEK/CB (9 wt%) and TPI/CB (10 wt%) composites. And the electrical conductivity of ternary PEEK/TPI/CB composites was 10⁴ to 10⁶ times higher than that of binary composites at identical 7.5 wt% CB loading, which was attributed to the double percolation effect. Moreover, the incorporation of CB could improve the thermal and mechanical properties effectively.     

同轴共纺技术制备聚苯乙烯中空亚微米纤维

利用同轴静电纺丝技术制备出壳层为聚苯乙烯(PS),芯层为聚乙烯吡咯烷酮(PVP)的壳-芯结构复合纤维,通过除去芯层PVP,成功地制备出了PS中空亚微米纤维。并对其进行了TEM、SEM测试。结果表明,纺丝过程中内、外液流速比值K直接影响着复合泰勒锥的形成及复合纤维的微观形态,且复合纤维平均直径随K值的增大而减小。     

聚L-乳酸/聚丁二烯基聚氨酯的合成与表征

以乙二醇和L-乳酸熔融直接缩聚制备双端羟基聚L-乳酸预聚物(PLLA),并用1H、13C-NMR、DSC、XRD对PLLA结构和性能分析表征.以液化二苯基甲烷二异氰酸酯(MDI)为偶联剂,端羟基聚L-乳酸和端羟基聚丁二烯(HTPB)偶联反应制备橡胶改性聚乳酸基聚氨酯弹性体,并用FT-IR,1H、13C-NMR对聚合产物进行结构表征确认.DSC测试结果表明聚氨酯有聚丁二烯段和聚乳酸段两个玻璃化转变温度,熔融温度基本在130℃.随着聚丁二烯含量的增加,结晶衍射峰逐渐消失,聚氨酯的拉伸强度降低,断裂伸长率增加.断面扫描电镜结果显示聚氨酯呈微相分离结构和弹性断裂.