PBA/SiO_2杂化弹性体材料的性能及表征

以含羟基的乙烯基单体为共聚单体,合成了功能化的聚丙烯酸丁酯（PBA）乳液,以硅溶胶为无机相,用溶胶-凝胶法制备了PBA/SiO2杂化弹性体材料,进行了力学性能研究和结构表征。结果表明,PBA/SiO2杂化材料热压后成为一种力学性能优良的弹性体。扫描电镜和透射电镜分析表明,SiO2粒子均匀分散于PBA基体中,两相结合紧密,无脱落现象发生;结合橡胶分析结果表明,杂化材料热压后,无机相与有机相之间发生缩合反应,形成了共价键,使得两相间的界面结合力增强;TG表明,杂化材料的热稳定性有显著提高。     

聚丙烯／弹性体／纳米SiO2复合材料性能研究

以聚丙烯（PP）为基体,以弹性体（POE、TPU）和纳米SiO2为改性剂,采用熔融共混法制备了PP／弹性体／纳米SiO2复合材料,研究了材料的力学性能、动态力学性能、结晶性能与流变性能。结果表明,弹性体和纳米粒子的加入具有明显的协同增韧效应;弹性体和纳米SiO2促进PP的结晶,TPU和纳米SiO2有更好的结晶成核作用;弹性体和纳米粒子使复合材料的模量、复合粘度增大。     

聚酰亚胺/二氧化钛杂化材料的制备及性能研究

采用超声分散-原位聚合工艺制备了聚酰亚胺(PI)/二氧化钛(TiO2)杂化膜。通过傅里叶转换红外光谱、紫外-可见光谱、扫描电子显微镜等对杂化膜进行了表征,探讨了杂化膜中TiO2含量对杂化膜的热性能、吸湿性能和力学性能的影响。结果表明,纳米TiO2粒子均匀分散在PI基体中,TiO2的掺入及与有机基体的杂化提高了材料的热分解温度与玻璃化转变温度,降低了材料的吸湿性能,改善了材料的力学性能。当TiO2含量为6%时,杂化膜的拉伸弹性模量和断裂强度达到最大值,分别为纯PI膜的2.17倍和1.63倍。     

PMDA-6FHP-DR1／SiO2杂化纳米材料的结构设计和合成

以含氟的二胺5，5′—(六氟异丙基)—二—(2—氨基苯酚)及均苯四甲酸酐(PMDA)为单体，首先合成了经酰胺化的主链上带有活性羟基的含氟聚酰亚胺，再通过Mitsunobu反应将活性生色分子分散红1(DR1)共价链接到聚酰亚胺的侧链骨架上，合成了含氟聚酰亚胺．采用溶胶—凝胶(SOl—Gel)技术，并利用偶联剂γ—氨丙基三乙氧基硅烷(AFTES)制备带有发色团的和含有硅氧烷端分子的聚酰胺酸，其中的Si(OR)3基经水解、缩合后，与正硅酸乙酯(TEOS)在催化剂作用下反应，经杂化、凝胶后，得到光学透明且热稳定性高的有机／无机杂化材料．将制得的含氟聚酰亚胺／SiO2杂化材料，采用红外光谱(FT—IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、示差扫描量热法(DSC)，对材料的结构、表面形貌、热性能进行了表征．     

纳米二氧化硅杂化粒子的结构设计及可控合成

采用分步原子转移自由基聚合(ATRP)法合成接枝了聚丙烯酸羟乙酯(PHEA)和聚苯乙烯(PS)链段的纳米SiO2杂化粒子,PHEA具有丰富的活性羟基官能团,可以与碳纤维形成化学键结合,PHEA和PS可分别与不同性质的基体形成良好的缠结和扩散,实现碳纤维与不同性质基体自适应构建强相互作用,改善界面粘结性能。用元素分析、傅立叶变换红外光谱、动态热机械分析、热重分析等手段对合成的纳米SiO2杂化粒子进行表征,确保合成的目标产物与设计的分子结构相吻合。     

无机粒子的有机高分子化及其对PVC填充改性的研究

本文研究了几种无机 有机复合粒子与聚氯乙烯共混复合材料力学性能的变化规律。结果表明 :SiO2 /HPMC PMMA(SiO2 经SDS预处理 )和HPMC g PMMA使材料力学性能下降 ,而SiO2 /HPMC PMMA(未经SDS处理 )、TiO2 /HPMC PMMA、ZnO/HPMC PMMA复合粒子使材料的力学性能有所提高。经柔性设计后的SiO2 /HPMC PBA/PMMA和ZnO/HPMC PBA/PMMA使材料的冲击强度提高的幅度更大。SEM提供的证据也表明 :ZnO复合粒子使材料出现较好的塑性变形 ;经柔性设计的SiO2 复合粒子比未经柔性设计的SiO2 复合粒子使材料的塑性变形也更加显著     

聚二甲基硅氧烷/SiO2杂化材料的结构与性能

采用Sol-Gel法,以正硅酸乙酯(TEOS)为无机组分前驱物,以含端羟基的聚二甲基硅氧烷(PDMS)为有机组分,合成出了块状的PDMS/SiO2杂化材料.考察了TEOS与PDMS的质量比对杂化材料的硬度、动态力学性能及微观结构的影响.结果表明:随着PDMS/SiO2杂化材料中无机组分含量的增加,其硬度增大,玻璃化转变温度升高,储能模量增大,阻尼因子下降;XPS分析表明:有机组分与无机组分之间存在化学键连接.     

纳米粒子链的弹性及其填料网络的补强机理

介绍了纳米SiO2粒子表面微细结构对聚硅氧烷分子吸附和缠结的影响.探讨纳米SiO2粒子链形成的填料网络补强硅橡胶的机理纳米SiO2粒子链与聚硅氧烷分子链进行的复合,SiO2粒子链形成的填料网络能随着基体形变而通过自身的屈服变形过程吸收大量的能量,从而补强硅橡胶.     

有机-无机同步聚合法制备水溶性酚醛树脂/SiO2杂化材料及其应用

采用有机-无机同步聚合法使酚醛树脂(PF)的单体聚合和正硅酸乙酯(TEOS)的水解缩合反应同步进行制备了水溶性PF/SiO2杂化材料。红外光谱分析和扫描电镜分析表明,在有机-无机同步聚合过程中,SiO2粒子与PF基体间形成有机、无机互穿网络结构,并且实现了有机、无机两相间的强界面结合。采用差示扫描量热仪对杂化材料的固化行为进行了研究。热失重分析表明,杂化材料的耐热性能明显提高,大大拓宽了其应用范围。     

镁碳砖用纳米SiO_2改性酚醛树脂的研究

采用有机硅溶胶-凝胶法原位生成纳米SiO2粒子合成了改性酚醛树脂,并利用IR和TG-DTA对纳米SiO2改性酚醛树脂进行结构和热分析.结果表明,有机硅改性剂与酚醛树脂间发生了相互作用,降低了酚羟基的相对含量,并在酚醛树脂分子链上引入了杂原子Si,改善了酚醛树脂的抗氧化性和热稳定性.采用纳米SiO2改性酚醛树脂替代传统的酚醛树脂作为镁碳砖的结合剂,可以有效地降低镁碳砖显气孔率,提高体积密度,明显增加常温耐压强度.     

Design and Synthesis of Mechano‐Responsive Color‐Changing Thermoplastic Elastomer Based on Poly(n‐Butyl Acrylate)–Spiropyran‐Polystyrene Comb‐Structured Graft Copolymers

Colorimetric mechanophores like spiropyran (SP) represent an emerging type of interesting signal molecule that can be incorporated into polymers or other materials as a stress transducer. In this work, a new type of spiropyran‐containing inimer molecule MA‐SP‐Br are designed and synthesized, which is incorporated into polybutylacrylate (PBA) chains through reversible addition‐fragmentation chain transfer (RAFT) copolymerization with n‐butyl acrylate (BA). PBA‐SP‐Br is then used as a macro‐initiator to graft polystyrene (PS) side chains from the PBA backbone through atom transfer radical polymerization (ATRP) of styrene. The resulting comb‐structured graft copolymer PBA‐SP‐PS contains 0.15–0.34% SP and exhibits a characteristic feature of thermoplastic elastomers. Under uniaxial stretch, the materials possess an excellent mechano‐responsivity and change color at strains as low as about 14%.     

Synthesis and characterization of poly(butyl acrylate)/silica and poly(butyl acrylate)/silica/poly(methyl methacrylate) composite particles

Poly(butyl acrylate)/poly(methyl methacrylate) (PBA/PMMA) core–shell particles embedded with nanometer‐sized silica particles were prepared by emulsion polymerization of butyl acrylate (BA) in the presence of silica particles preabsorbed with 2,2′‐azobis(2‐amidinopropane)dihydrochloride (AIBA) initiator and subsequent MMA emulsion polymerization in the presence of PBA/silica composite particles. The morphologies of the resulting PBA/silica and PBA/silica/PMMA composite particles were characterized, which showed that AIBA could be absorbed effectively onto silica particles when the pH of the dispersion medium was greater than the isoelectric potential point of silica. The critical amount of AIBA added to have stable dispersion of silica particles increased as the pH of the dispersion medium increased. PBA/silica composite particles prepared by in situ emulsion polymerization using silica preabsorbed with AIBA showed higher silica absorption efficiency than did the PBA/silica composite particles prepared by direct mixing of PBA latex and silica dispersion or by emulsion polymerization in which AIBA was added after the mixing of BA and silica. The PBA/silica composite particles exhibited a raspberrylike morphology, with silica particles “adhered” to the surfaces of the PBA particles, whereas the PBA/silica/PMMA composite latex particles exhibited a sandwich morphology, with silica particles mainly at the interface between the PBA core and the PMMA shell. Subsequently, the PBA/silica/PMMA composite latex obtained had a narrow particle size distribution and good dispersion stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3425–3432, 2006     

Phase rearrangement in two-stage emulsion polymers of butyl acrylate and styrene: Mechanical properties

The mechanical and thermal properties of films from a series of two-stage emulsion polymers were investigated. The emulsion polymers were made by polymerizng styrene in the presence of a preformed poly(butyl acrylate-co-divinyl benzene) seed latex. The effects of seed particle size, seed particle crosslinking via the amount of divinyl benzene, styrene/butyl acrylate ratio, and thermal history on the film properties were studied. Latex particles were characterized by light scattering and film formation behavior. Dried films were characterized by differential scanning calorimetry, dynamic mechanical analysis, and stress-strain behavior. Although evidence was obtained for nearly complete phase separation between the polystyrene (PS) and poly(butyl acrylate) (PBA) phases, the site of styrene polymerization and thus the PS phase morphology is influenced by seed particle size, seed crosslinking, and S/BA ratio. The morphology of as-dried films consists of finely dispersed PS domains in a continuous PBA matrix. Thermal annealing above the PS T_g causes coalescence of the PS domains, resulting in significantly improved mechanical properties. The extent of PS phase coalescence is also influenced by the level of seed crosslinking.     

Morphology,thermal property,and mechanical property of core–shell latex polymers. I. Effect of heating and pressuring on PBA/PS linear composite polymer

In this work, butyl acrylate and styrene were used as monomers in the first stage and second stage of polymerization, respectively, and potassium persulfate (K₂S₂O₈) was used as the initiator to synthesize the poly(butyl acrylate)–polystyrene (PBA/PS) composite latex by the method of two-stage soapless emulsion polymerization. The morphology of the latex particles was observed by transmission electron microscopy (TEM), which showed that the composite latex particles had a core–shell structure. The particle-size distribution of the composite latex was very uniform. A thin layer of a PBA-graft-PS copolymer was formed in between the core (PBA) and shell (PS) regions, which thus increased the compatibility between the PBA and PS phases. The process of heating and pressuring influenced the morphology, mechanical properties, and thermal properties of the PBA/PS composite polymer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 13–23, 1998     

Synthesis and characterization of nanosilica/polyacrylate composite latex

The nanosilica/polyacrylate organic–inorganic composite latex was synthesized by in‐situ emulsion polymerization of methyl methacrylate (MMA) and butyl acrylate (BA) in the presence of silica nanoparticles, which were modified by silane coupling agent. The surface properties and dispersibility of silica nanoparticles modification, chemical structure, Zeta potential, diameter distribution of the composite latex prepared, surface roughness, and thermal stability of the hybrid film formed by the composite latex were investigated by fourier transform infrared spectrometer (FTIR), transmission electron microscopy (TEM), Zeta meter, ZetaPlus apparatus (dynamic light scattering method), atomic force microscopy (AFM), and thermogravimetric analysis (TGA), respectively. After modification with silane coupling agent, silane was grafted onto the surface of silica nanoparticles to form the organic layers, which was able to efficiently prevent the silica nanoparticles from aggregating to individually homogeneous disperse in the in‐situ emulsion polymerization system and improve the compatibility of silica nanoparticles with the acrylate monomers. The nanosilica/polyacrylate organic–inorganic composite latex prepared had the properties of silica nanoparticles and pure polyacrylate latex but was not simply a combination. Strong chemical bonding tethered the silica and acrylate chains to form the core/shell structural composite latex. Consequently, the hybrid film formed by nanosilica/polyacrylate composite latex exhibited a smooth surface and better thermal properties than the pure polyacrylate film. POLYM. COMPOS. 27:282–288, 2006. © 2006 Society of Plastics Engineers     

Toughening of polylactide with natural rubber grafted with poly(butyl acrylate)

Natural rubber grafted with poly(butyl acrylate) (NR‐g‐PBA) in an attempt to toughen polylactide (PLA) was prepared by grafting butyl acrylate onto natural rubber (NR) through emulsion polymerization. The purified NR‐g‐PBA was confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. NR‐g‐PBA/PLA blend and NR/PLA blend were prepared with a Haake internal melt mixer. The morphology and mechanical properties of the blends were investigated as a function of rubber content. Observations by scanning electron microscopy showed that the spherical‐particle‐dispersed phase appearing in the NR/PLA blend was not found in the NR‐g‐PBA/PLA blend, which showed that NR grafted with PBA is compatible with PLA, and accounted for the efficient toughening effect on PLA. The elongation at break and the impact strength were significantly improved with an increase in NR‐g‐PBA content. The thermal stability of PLA decreased when blended with NR but was retained with NR‐g‐PBA. Copyright © 2011 Society of Chemical Industry     

聚氨酯-丙烯酸酯细乳液聚合及其压敏胶应用

以十八烷基丙烯酸酯为助稳定剂（ODA）,Dowfax2A1（80%）为乳化剂,十二烷基硫醇为链转移剂,采用细乳液聚合的方法制备了聚氨酯-丙烯酸酯杂化乳液。系统的研究了聚合温度、链转移剂的量、2-羟乙基甲基丙烯酸酯（HEMA）和羟乙基化双酚A的比例、PU含量以及丙烯酸丁酯（BA）与甲基丙烯酸甲酯（MMA）的质量比等因素对乳液聚合及其膜的机械性、粘合性的影响。结果表明,当n（HEMA）/n（NCO）=1∶5,链转移剂对单体的量为0.2%,PU含量为20%,m（BA）/m（MMA）=3∶1时,在70℃下制备的乳胶膜的机械性能和粘合性能最佳。     

纳米SiO2/聚氨酯-含氟丙烯酸酯杂化乳液的合成与表征

采用种子乳液聚合法,以聚氨酯（PU）乳液为种子（在聚合过程中为壳相）,甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）、甲基丙烯酸十二氟庚酯（DFMA）和γ-甲基丙烯酰氧丙基三甲氧基硅烷（KH-570）改性的纳米SiO₂组成的混合物为核相,合成了具有核壳结构的纳米SiO₂/聚氨酯-含氟丙烯酸酯（SiO₂/FPUA）复合乳液。考察了纳米SiO₂和DFMA用量对乳液聚合过程及乳胶膜性能的影响。通过傅里叶红外光谱（FT-IR）、接触角（CA）、透射电子显微镜（TEM）、热重（TG）、差示扫描量热仪（DSC）和力学性能测试（MPT）等表征乳液的结构形态、乳胶膜的表面性能和综合性能。结果表明：乳胶粒子呈现“反相核壳”结构,以聚丙烯酸酯（PA）相为核,PU相为壳;由于纳米SiO₂和DFMA的协同作用,涂膜的疏水性和综合性能得到了较大的提高。     

Effect of particle size on the mechanical properties of polystyrene and poly(butyl acrylate) core/shell polymers

The effects of particle size and polymer location (core or shell) on the mechanical properties of core/shell materials composed of polystyrene (PST) and poly(butyl acrylate) (PBA) made by a two-stage emulsion or microemulsion polymerization process are reported. Low-seed content (LSC) latexes were made by batch polymerization in microemulsions stabilized with DTAB in the presence of an organic salt (dibutyl phosphite). High-seed content (HSC) latexes were produced by microemulsion or emulsion polymerization in semi-continuous process. These latexes were subsequently used to form core/shell particles of PST/PBA or PBA/PST and their mechanical properties were examined and compared. Our results indicate that core/shell particle size and the location of the polymers have important effects on the mechanical properties.