纳米SiO_2表面接枝甲基丙烯酸甲酯的研究

为了提高纳米二氧化硅(SiO2)粒子在阻燃型聚合物基纳米复合材料中的有效利用,需要对粒子的表面进行改性。此实验采用溶液聚合法,使甲基丙烯酸甲酯单体(MMA)在烷基化预处理的纳米SiO2粒子的表面进行接枝聚合,得到以纳米SiO2粒子为核、接枝聚甲基丙烯酸甲酯为壳的复合颗粒(SiO2-g-PMMA)。结果表明,PMMA以化学键成功地接到纳米SiO2的表面,并可通过改变接枝聚合的条件来调节粒子上所接聚甲基丙烯酸甲酯的结构,改性后的纳米SiO2粒子具有良好的热稳定性及分散性。     

无皂乳液聚合制备SiO_2/PMMA纳米复合胶体微球

采用半连续无皂乳液聚合方法在未经硅烷偶联剂改性的230 nm亲水性SiO2微球表面聚合甲基丙烯酸甲酯(PMMA)壳层,制备以SiO2粒子为核、PMMA为壳层的复合胶体微球。研究微球表面形貌、组成、粒径变化规律,探索聚合反应的成核过程和PMMA进料流量对复合微球粒径的影响。结果表明,在未经硅烷偶联剂改性的纳米SiO2表面可形成稳定规整的PMMA壳层,SiO2/PMMA复合胶体微球球型度接近1.0,单分散性较好,多分散度指数(PDI)小于0.04。聚合反应受甲基丙烯酸甲酯(PMMA)单体含量控制,随着PMMA进料流量增加,乳胶粒子成核过程由均相成核过渡为胶束成核,复合微球粒径加速增大,多分散性增强,其粒径可通过调节PMMA进料流量控制。     

纳米SiO_2表面接枝聚合改性及在PP中的分散

纳米SiO2粒子经硅烷偶联剂表面处理后,采用乳液聚合方法在纳米SiO2粒子表面接枝苯乙烯单体,实现了纳米SiO2表面的高分子包覆改性,制备了具有核壳结构的聚苯乙烯接枝SiO2复合纳米粒子.采用傅里叶变换红外光谱、透射电子显微镜对纳米SiO2粒子的表面结构及其在聚丙烯(PP)中的分散状况进行了表征.结果表明,接枝改性后纳米SiO2粒子能够在PP基体中均匀分散,明显改善了PP复合材料的力学性能.     

PMMA/PAN核壳复合粒子的制备与表征

用无皂乳液聚合法制备粒径分布较窄的单分散聚甲基丙烯酸甲酯(PMMA)乳液粒子后,以此乳液粒子为种子,以丙烯腈为壳层单体,用种子乳液聚合法制备了粒径分布更窄、具有核壳结构形态的PMMA／聚丙烯腈(PAN)复合粒子,测定了核及核壳粒子粒径及其分布,并用透射电镜表征了其核壳形态特征。结果表明,PMMA／PAN核壳粒子的壳层厚度约为20nm,粒径分布要比PMMA粒子的窄。     

悬浮-乳液耦合聚合制备大粒径核-壳结构PS/PMMA复合粒子

采用在苯乙烯(St)悬浮聚合不同时期滴加甲基丙烯酸甲酯(MMA)乳液聚合组分的悬浮-乳液耦合聚合方法,制备大粒径核-壳结构复合粒子。研究发现：在St悬浮聚合初期和宏观成粒基本完成的聚合后期滴加MMA乳液聚合组分,分别得到由初级粒子凝并的非核-壳结构粒子和核-壳结构不完整的复合粒子,粒径分布较宽;在St悬浮聚合中期滴加MMA乳液聚合组分,MMA和PMMA乳胶粒子易于向PS粒子扩散或粘并,制备得到平均粒径大于100gm、粒径分布窄和核-壳结构良好的PS／PMMA复合粒子。     

PMMA/PAN核-壳粒子制备工艺研究

加入适量的引发剂,通过无皂乳液聚合,以聚甲基丙烯酸甲酯( PMMA)核体为种子乳液,制备了PMMA/PAN核-壳乳液.实验中分别对引发剂量、丙稀腈( AN)滴加量对PMMA/PAN壳层厚度及其粒径和粒径分布的影响进行了较详细的研究,确定了种子乳液聚合法制备PMMA/PAN核-壳结构聚合物粒子的实验方法及条件.通过激光粒度仪、扫描电镜和透射电镜对核-壳粒子的形态结构进行了表征,证明了PMMA/PAN复合粒子的核-壳结构.     

纳米SiO2粒子静电吸附引发剂及引发甲基丙烯酸甲酯乳液聚合

对纳米SiO2粒子静电吸附2,2′-偶氮(2-脒基丙烷)二氯化氢(AIBA)引发剂,进而在其表面引发甲基丙烯酸甲酯乳液聚合而制备聚甲基丙烯酸甲酯(PMMA)/纳米SiO2复合粒子进行了研究.发现当介质pH值高于SiO2粒子等电势点时,纳米SiO2能与AIBA发生静电吸附而锚固上引发剂.使用高速离心分离/紫外分光光度计分析,证明引发剂吸附存在一个稳定上限,在pH=10时为0.067g·(g·SiO2)-1.随着纳米SiO2粒子锚固AIBA量的增加,聚合速率增加,PMMA/纳米SiO2复合粒子的平均粒径变小;乳化剂OP-10用量过大时,复合粒子的胶体稳定性降低.原位乳液聚合得到的PMMA/纳米SiO2复合粒子的典型形态为"草莓"型核壳结构.     

核壳PBA/PMMA乳液粒径分布规律与壳层聚合研究

通过半连续饥饿态法合成了核壳型PBA/PMMA乳液,并利用激光粒度仪时实监控壳层聚合阶段粒子粒径变化,结合理论数学计算模型,研究了壳层单体加料速度与补加乳化剂的量对平均数均粒径及其分布与总粒子数的影响.理论计算乳液中的总粒子数的变化规律和对比反应前后粒径大小,并通过傅立叶红外光谱证实了核壳结构的存在.核壳聚合中壳层聚合机理为单体在加入种子核乳液过程中大部分先在水相中均相成核形成PMMA低聚物,随后由于表面吸附作用而迁移到PBA核表面成为活性中心继续聚合成为壳层.     

聚甲基丙烯酸甲酯／纳米SiO2复合粒子的制备与表征

采用甲基丙烯酸-3-甲氧基硅丙酯（MPs）对分散于甲基丙烯酸甲酯（MMA）中的纳米SiO2粒子进行偶联改性，得到了表面改性的纳米SiO2单体分散液，用原位悬浮聚合方法制备了不同SiO2含量的PMMA／纳米SiO2复合粒子。通过红外光谱、透射电镜、差示扫描量热分析和热重分析等方法对制备的纳米复合粒子进行了表征，结果表明，纳米SiO2粒子在PMMA中分散良好；MMA可通过与MPS的共聚而有效地接枝到SiO2粒子表面，当SiO2含量为6．6％（质量分数，下同）、MPS用量为0．06g／gSiO2时，其接枝率可达73．8％；同时，纳米SiO2的引入可提高PMMA的耐热性能，当Si02含量为14.7％时，其玻璃化转变温度和最大热分解速率时的温度分别提高了11．8℃和18．8℃。     

二氧化硅球的制备及其功能化

以正硅酸四乙酯为硅源,分别在碱性和酸性条件下制备了二氧化硅(SiO2)球状粒子;在碱性条件下制备了具有荧光功能的SiO2-FITC复合纳米球;以Sn2+作为敏化剂,在SiO2球表面沉积Ag纳米颗粒,制备了SiO2/Ag核-壳结构纳米粒子。通过透射电子显微镜(TEM)、紫外-可见近红外(UV-vis-NIR)分光光度计,荧光分光光度计对SiO2球,SiO2-FITC荧光纳米球,SiO2/Ag核-壳结构纳米粒子的形貌和光学吸收、荧光发射特性进行了表征。结果表明,碱性环境下制备的SiO2球粒径大小为纳米级,酸性环境下制备的SiO2球粒径大小为微米级,酸性环境下制备的SiO2球比碱性环境下制备的硅球致密。掺入FITC的SiO2球具有荧光发射特性,且发光强度可以控制。Ag纳米颗粒修饰的SiO2/Ag核-壳结构纳米粒子具有等表面等离子体共振吸收特性。     

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     

烷基化纳米SiO2/MMA乳液聚合物及其对PC的改性研究

用乳液聚合方法制备了烷基化纳米SiO2/MMA乳液聚合物，用TEM、FTIR分析研究了乳液聚合物的结构。结果表明，该乳液聚合物的粒子基本呈球形，由核、壳组成，中心为SiO2核，外围为PMMA壳，核壳之间存在化学键，在适量第三组分配合下，烷基化纳米SiO2/MMA乳液聚合物能大幅度提高PC的韧性，加工流动性及耐热性。同时对其增韧机理也进行了研究。     

核壳结构SiO_2/SnO_2纳米复合微粒的合成与表征

文章从TEOS出发,先水解制备了纳米二氧化硅微粒,再以五水四氯化锡为锡源,碳酸铵为沉淀剂,通过控制反应条件,用共沉淀法在二氧化硅表面包覆上一层锡化物层,经600℃煅烧2 h后形成了具有核壳结构的SiO2/SnO2纳米复合微粒,并用透射电镜、激光粒度仪、FTIR等手段对其形貌、结构、组成进行了表征。结果表明：形成的核壳结构SiO2/SnO2纳米复合微粒是以二氧化硅为核,氧化锡为壳,内核直径约为120 nm,壳层厚度为8～18 nm;氧化锡基本以成膜包覆为主,伴有部分氧化锡自身成核团聚。     

PMMA/SiO2复合微球在常规乳液体系中的制备及其形态研究

以4-乙烯基吡啶(4-VP)为辅助单体,分别使用十二烷基硫酸钠(SDS)和OP-40(CA897)作乳化剂,在SiO2存在下用常规乳液聚合合成了PMMA/SiO2复合微球.在阴离子乳化剂体系中,通过改变聚合物乳胶粒大小可以得到不同形态的复合微球,在非离子乳化剂体系中,可以得到草莓型或核-壳形态的SiO2/PMMA复合微球,取决于单体滴加速度、乳化剂的浓度和单体/SiO2比.复合微球的形态通过透射电镜及扫描电镜进行表征.     

Synthesis of poly(butyl acrylate)—laponite nanocomposite nanoparticles for improving the impact strength of poly(lactic acid)

This work aims at preparing and characterizing poly(butyl acrylate) (PBA)—laponite (LRD) nanocomposite nanoparticles and nanocomposite core (PBA‐LRD)‐shell poly(methyl methacrylate) (PMMA) nanoparticles, on the one hand, and the morphology and properties of poly(lactic acid) (PLA)‐based blends containing PBA‐LRD nanocomposite nanoparticles or (PBA‐LRD)/PMMA core–shell nanoparticles as the dispersed phase, on the other hand. The PBA and (PBA‐LRD)/PMMA nanoparticles were synthesized by miniemulsion or emulsion polymerization using LRD platelets modified by 3‐methacryloxypropyltrimethoxysilane (MPTMS). The grafting of MPTMS onto the LRD surfaces was characterized qualitatively using FTIR and quantitatively using thermogravimetric analysis (TGA). The amounts of LRD in the PBA‐LRD nanocomposites were characterized by TGA. The PBA/PMMA core–shell particles were analyzed by ¹H‐NMR. Their morphology was confirmed by SEM and TEM. Mechanical properties of (PBA‐LRD)/PLA blends and (PBA‐LRD)/PMMA/PLA ones were tested and compared with those of the pure PLA, showing that core–shell particles allowed increasing impact strength of the PLA while minimizing loss in Young modulus and tensile strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Controlling Shell Thickness of PS/SiO2 Core-Shell Particles and Their Crystallization into 3-D Ordered Thin Film

PS/SiO2 particles with core-shell structure were synthesized by coating silica on surface of polystyrene (PS)colloidal particles. The reaction parameters, such as initial tetraethyl orthosilicate (TEOS) concentration, water concentration and reaction temperature, have been investigated to control the thickness of silica shells. The shell thickness was prepositional to the square root of the initial concentration of TEOS and first increased with increasing water concentration, reached a maximum at about 2.0 mol/L and then started decreasing beyond that concentration. It was also found that the shell thickness decreased firstly with the reaction temperature added, then tended to a constant. The so-synthesized PS/SiO2 core-shell particles were directly crystallized into 3-D ordered thin film, then sintered at 570 ℃ into the ordered macroporous thin film.Compared with the conditional method, the present approach avoids repeatedly filling the precursor in the templetes and save time more.     

Preparation of toughened PMMA through PEG-modified urethane acrylate/PMMA core–shell composite particles

Poly(urethane acrylate) (PUA)/poly(methylmethacrylate) (PMMA) core–shell composite particles were prepared by two-stage emulsion polymerization. The sizes of composite particles could be varied from 25 to 210 nm by introducing polyoxyethylene (POE) groups to the urethane acrylate molecular backbone. Core–shell morphology was identified by investigating the polarity of the surface of the core and shell polymer particles and by measuring the contact angle of the composite particles. A composite particle prepared with relatively small particles (about 20 nm) did not show the core/shell morphology, because the high polar surface of the core polymer particle and the low-stage ratio of the core to the shell cause the formation of a core/shell two-stage latex to be more thermodynamically unstable. The fracture toughness of rubber-toughened PMMA containing PUA/PMMA composite particles increased as the particle sizes decreased and the shell thickness of the composite particles increased. In particular, when the average size of the composite particle was about 43 nm and the stage ratio was 50/50, the fracture toughness of the rubber-toughened PMMA increased more than three times compared with that of pure PMMA. Furthermore, the transparency of toughened PMMA could be maintained up to 91% in the visible spectra range. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2291–2302, 1998     

Preparation of polystyrene/poly(methyl methacrylate) core‐shell composite particles by suspension‐emulsion combined polymerization

Suspension‐emulsion combined polymerization process, in which methyl methacrylate (MMA) emulsion polymerization constituents (EPC) were drop wise added to styrene (St) suspension polymerization system, was applied to prepare polystyrene/poly(methyl methacrylate) (PS/PMMA) composite particles. The influences of the feeding condition and the composition of EPC on the particle feature of the resulting composite polymer particles were investigated. It was found that PS/PMMA core‐shell composite particles with a narrow particle size distribution and a great size would be formed when the EPC was added at the viscous energy dominated particle formation stage of St suspension polymerization with a suitable feeding rate, whereas St‐MMA copolymer particles or PS/PMMA composite particles with imperfect core‐shell structure would be formed when the EPC was added at the earlier or later stage of St suspension polymerization, respectively. It was also showed that the EPC composition affected the composite particles formation process. The individual latex particles would exist in the final product when the concentrations of MMA monomer, sodium dodecyl sulfate emulsifier, and potassium persulfate initiator were great in the EPC. Considering the feature of St suspension polymerization and the morphology of PS/PMMA composite particles, the formation mechanism of PS/PMMA particles with core‐shell structure was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of poly(methyl methacrylate)‐Silica nanoparticles via differential microemulsion polymerization and physical properties of NR/PMMA‐SiO2 hybrid membranes

Poly(methy methacrylate) (PMMA)‐SiO₂ nanoparticles were prepared via differential microemulsion polymerization. The effects of silica loading, surfactant concentration, and initiator concentration on monomer conversion, particle size, particle size distribution, grafting efficiency, and silica encapsulation efficiency were investigated. A high monomer conversion of 99.9% and PMMA‐SiO₂ nanoparticles with a size range of 30 to 50 nm were obtained at a low surfactant concentration of 5.34 wt% based on monomer. PMMA‐SiO₂ nanoparticles showed spherical particles with a core‐shell morphology by TEM micrographs. A nanocomposite membrane from natural rubber (NR) and PMMA‐SiO₂ emulsion was studied for mechanical and thermal properties and pervaporation of water‐ethanol mixtures. PMMA‐SiO₂ nanoparticles which were uniformly dispersed in NR matrix, significantly enhanced mechanical properties and showed high water selectivity in permeate flux. Thus, the NR/PMMA‐SiO₂ hybrid membranes have great potential for pervaporation process in membrane applications. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers