超声波辐照作用下部分水解聚丙烯酰胺与甲基丙烯酸酯共聚反应的研究

研究了部分水解聚丙烯酰胺（ＨＰＡＭ）和一系列甲基丙烯酸酯在超声波辐照作用下的共聚反应。研究结果表明，共聚反应前期，单体的转化率随单体水溶性增大而增大，共聚反应动力学决定于单体的水溶性。通过红外光谱、核磁共振及质谱研究了共聚物的结构．证实共聚物为嵌段体。     

Preparation and characterization of molecularly imprinted poly(hydroxyethyl methacrylate) microspheres for sustained release of gatifloxacin

Molecularly imprinted poly(hydroxyethyl methacrylate) microspheres (PHEMA MIPMs) were prepared via precipitation polymerization in this article, using gatifloxacin (GFLX), hydroxyethyl methacrylate (HEMA), and ethylene glycol dimethacrylate (EGDMA) as template molecule, functional monomer and cross-linker, respectively. The effects of reaction medium, initial total monomers, cross-linker and molecular imprinting on the polymerization were investigated systematically. The interaction between GFLX and HEMA in pre-solution was studied by UV–Visible spectrophotometer, both size and morphology of products were characterized by a scanning electron microscope. When the total initial monomer concentration was 1 vol%, EGDMA content was 70 mol%, a group of uniform PHEMA MIPMs were prepared at different GFLX/MAA molar ratios, with diameter range from 2.06 ± 0.07 to 2.82 ± 0.20 μm. The results of drug loading and in vitro release experiments demonstrated that PHEMA MIPMs could achieve a higher GFLX loading content and a more acceptable sustained release than non-imprinted ones.     

核壳型PBA/P(St-co-MMA)乳胶粒子热力学平衡形态分布

采用饥饿态加料的半连续乳液聚合法,制备了系列PBA/P（St-co-MMA）复合乳液,通过改变St/MMA配比调节第Ⅱ阶段无规共聚物极性,利用透射电子显微镜观测到从反向核壳向正向核壳形态变化的复合乳胶体系,发现同一乳液样品在相同处理条件下存在着粒子形态的多样性,提出采用数学统计的方法来描述这种形态分布,对粒子形态分布的量化,可使核壳型乳胶粒子形态的表述更为直观、准确.根据不同温度处理方式下所得粒子形态分布结果的对比,判定了核壳型乳胶粒子热力学平衡形态的趋向。     

高聚物增强木质基复合材料的结构与性能

为探索性能优异的高聚物增强木质基复合材料的制备方法, 以大青杨木材为研究对象, 选用双功能性单体甲基丙烯酸缩水甘油酯(GMA)和丙烯酸类单体甲基丙烯酸甲酯(MMA), 通过加热引发聚合的方式制得P(GMAcoMMA)/木材复合材料。利用SEM、 FTIR和XRD表征其结构, 并测试其相关性能。结果表明: GMA的加入, 使高聚物与木材细胞壁紧密接触, 界面相互作用力增强; GMA一端的环氧基团, 与木材细胞壁上的羟基充分发生了化学反应, 其双键与MMA单体发生自由基共聚合反应, 从而使P(GMAcoMMA)接枝在木材细胞壁上, 并且主要以无定形态存在。与未改性的木材相比, P(GMAcoMMA)/木材复合材料的静曲强度(MOR)、 尺寸稳定性、 防腐性能和热稳定性依次提高90.53%、 54.05%、 92.85%和31℃。      

Preparation and properties of close-packed composite materials

Monodisperse silica particles of about 0.3m diameter are suspended in methacrylate monomer using a carefully selected dispersant. Many steric dispersants are hydrocarbon chains with a reactive end-group. These are not effective as dispersants for silica in moderately polar solvents, such as esters and the methacrylate monomers. Good dispersion was obtained with a methacrylate polymer terminated by a chlorosilane end group. Settling or centrifugation of these unagglomerated dispersions gives well-packed particle beds. Polymerization of the surrounding monomer produces composite materials with high packing fractions and a high degree of regularity. Moduli and strengths of these composites are reported.     

Effect of composition on the mechanical properties and water sorption of a butadiene/styrene copolymer-methacrylate monomer soft lining material

A series of experimental soft lining materials has been produced using a butadiene/styrene copolymer with methacrylate monomers, and assessed in terms of their tensile properties. Three different methacrylate monomers, n-hexyl (HMA), ethyl hexyl (EHMA) and 1-tridecyl (TDMA), and two different initiators, benzoyl peroxide (BP) and lauryl peroxide (LP), were used. Other variables were copolymer/monomer ratio and level of cross-linking. Water sorption studies were also carried out on some of the materials, selected in terms of strength, on the pure copolymer (with and without partitioning agent) and on homopolymers of HMA and EHMA. Generally, the EHMA-based materials had the highest strengths and the TDMA the lowest. The highest tensile strength at 11.36±1.80 MPa was produced by the 50/50, LP initiated EHMA material with 1% cross-linking agent, which also had the lowest water uptake. There appeared to be a relationship between tensile strength and water uptake. Water uptake was found to be governed by the partitioning agent in the copolymer powder.     

带有环氧基的反应型聚丙烯酸酯乳液的合成及表征

以甲基丙烯酸甲酯、丙烯酸-2-乙基己酯和甲基丙烯酸缩水甘油酯等为单体,制备了以PMMA-BA为"核"、PEHA-GMA为"壳"的微相复合乳液.利用透射电镜和激光动态光散射对乳胶粒子的形态和粒径分布进行了表征.研究了乳液聚合物和乳液与水溶性脲醛树脂共混物经不同温度热处理后的物理性能.结果表明,合成乳液的乳胶粒子具有预期的核-壳结构,粒度分布窄,平均粒径为132 nm;乳液聚合物和乳液与脲醛树脂共混物均随着热处理温度的升高,玻璃化转变温度升高,拉伸强度增大,断裂伸长率变小,吸水率降低.     

Surface-initiated atom transfer radical polymerization of methyl methacrylate from magnetite nanoparticles at ambient temperature

The synthesis of methyl methacrylate (MMA) brush from the surface of magnetite nanoparticles (core-shell structure), from initiator moieties anchored covalently to the nanoparticles, via room temperature atom transfer radical polymerization (ATRP) is described. The surface-initiated polymerization was carried out from a surface-confined initiator containing a 2-bromoisobutyrate moiety with Cu(I)Br/PMDETA catalytic system. The initiator moiety was covalently anchored to the nanoparticles via a two step modification reaction scheme. Controlled polymerization was observed if ethyl-2-bromoisobutyrate (2-EiBrB) was added as a free/sacrificial initiator. A linear increase of molecular weight and a narrow molecular weight distribution of the PMMA formed in solution, provide evidence for a controlled surface-initiated polymerization, leading to surface-attached polymer brushes under mild conditions. The grafted PMMA provides good stability and dispersibility for the nanoparticles in organic solvents.     

含氟丙烯酸酯复合乳液的制备及性能

含氟丙烯酸酯性能优异,目前以丙烯酸六氟丁酯(HFBM)单体合成水性含氟丙烯酸酯乳液的报道较少。以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)为主要单体,HFBM为功能单体,采用预乳化工艺合成了含氟丙烯酸酯复合乳液,优化了乳液合成条件(复合乳化剂配比、引发剂用量、含氟单体用量),并用红外光谱和热重分析研究了优化条件合成乳液的结构和其所成乳胶膜的热稳定性。结果表明:复合乳化剂中m(十二烷基硫酸钠)∶m(曲拉通X-100)=3∶2,引发剂(过硫酸钾)用量为1.0%,含氟单体用量为9%时,合成的含氟丙烯酸酯复合乳液性能最好,具有较大的单体转化率和较小的凝胶率,乳胶膜有较大的拉伸强度;HFBM被成功地引入聚合物链段结构中,并使聚合物的热稳定性大幅提高。     

相反转界面细乳液聚合法制备石蜡纳胶囊与表征

采用相反转乳化的界面细乳液聚合法制备了以交联聚甲基丙烯酯甲酯为壁材,以石蜡为芯材的纳胶囊。利用光学显微镜、激光粒度分析仪、透射电镜、红外光谱仪、差示扫描量热分析仪等研究了含氟助乳化剂FC-4430、丙烯酸十八酯(SA)及芯材投料量对聚合过程、产品表面形貌、粒径、化学结构、储热性能和包覆率的影响。结果表明,FC-4430对相反转有促进作用,可降低胶囊粒子尺寸且利于包封;SA能提高纳胶囊的包覆率和热稳定性;当FC-4430用量为0.4%,SA用量为2%,m(core)∶m(shell)为2∶1时,纳胶囊的相变潜热为91.7 J/g,包覆率为63.3%,包覆效率为95.0%,胶囊粒子为球形,表面光滑,粒径为0.6~1μm,呈明显的核壳结构,芯材直径为300~500 nm。     

Preparation of poly(methyl methacrylate)/lanthanum hydroxide nanowire nanocomposites with improvement in thermal stability

Poly(methyl methacrylate) (PMMA)/lanthanum hydroxide (La(OH)₃) nanowire nanocomposites were prepared by in-situ polymerization of methyl methacrylate (MMA) in the DMF solution. The improvement in thermal stability of the nanocomposites is remarkable with low inorganic nanowires content. The experimental results indicate ultimate network formation for the nanocomposites is possibly through interaction between La³⁺ and MMA monomer during polymerization. The network induces the mobility restriction of polymer chains and greatly prevents polymer chains from decomposition. The characteristic of one-dimensional nanowires used here may play a key role in the formation of the “cross-link” network and decision of the low content of nanowires addition in the polymer matrix.     

Flower-like silicon dioxide/polymer composite particles synthesized by dispersion polymerization route

A vital issue for the manufacture of multifunctional thin films is to synthesize polymer/ceramic hybrid particles. Silicon dioxide (SiO₂)/polymer composite particles were synthesized through dispersion copolymerization of methyl methacrylate (MMA) in the presence of SiO₂ bullet-like particles, using a “grafting-through” approach. The SiO₂ particles were previously modified with the silane-coupling agent 3-(trimethoxysilyl)propyl methacrylate (MPTS). Scanning electron microscopy and transmission electron microscopy analyses confirmed the formation of particles with a rough surface and flower-like morphology. Fourier transform infrared spectroscopy, thermogravimetric analysis, and energy-dispersive X-ray investigations indicated that a nucleation and aggregation process of the growing copolymer MPTS/poly(methyl methacrylate) (PMMA) occurred on the surface of the modified SiO₂ particles. As a result, the SiO₂ core became embedded in a PMMA shell. The influence of MPTS and the concentration of polyvinylpyrrolidone as a steric stabilizer on the flower-like morphology was demonstrated. Dispersion polymerizations have been proven to be simple and effective ways to synthesize composite particles with a high surface area. By using homogeneous systems (i.e., the monomer was soluble in the reaction solvent), no emulsification process was required, and copious amounts of well-dispersed particles were produced. These characteristics open many application possibilities for the use of the synthesized particles in functional coatings and optical devices, for mechanical reinforcement in polymeric materials, and as biomaterials.     

细乳液聚合法制备双相核材料的电子墨水纳胶囊

摘要：利用细乳液法制备包含炭黑纳米颗粒／TiO2纳米颗粒和分散剂[四氯乙烯（TEC）和SPAN-80的混合液]的双相核材料的电子墨水纳米胶囊。以苯乙烯（SM）-甲基丙烯酸甲酯（MMA）为反应单体,十六烷（HD）为疏水剂,偶氮二异丁腈（AIBN）为引发剂,聚乙烯醇（PVA）为表面活性剂,乙醇为溶剂。把分别包含TiO2有机...     

Improving the thermal and mechanical properties of silicone polymer by incorporating functionalized graphene oxide

Functionalized graphene oxide (FGO) was produced by reacting graphene oxide nanosheets with vinyl trimethoxy silane (VTMS). The results confirmed the attachment of VTMS molecules to the surface of GO sheets by Si–O–C bonding. The introduction of VTMS molecules led to an excellent dispersibility in tetrahydrofuran and to the complete exfoliation of FGO with a thickness of about 1.19 nm. Meanwhile, FGO/silicone polymer composites were prepared by solution blending method. The incorporation of 0.5 wt% of FGO in silicone polymer improved remarkably the thermal stability, tensile strength, and thermal conductivity of the silicone polymer composite, due to the homogeneous dispersion of FGO in the composites as well as to the strong interfacial adhesion with silicone polymer matrix. Tensile strength and thermal conductivity of the FGO/silicone polymer composite were increased by 95.6 and 78.3 %, respectively, with the addition of 0.5 wt% FGO. The 5 % weight loss temperature of the composite at 0.5 wt% FGO loading was detected 26.1 °C higher than that of silicone polymer.     

Influence of Ultrasonic on the Dispersibility of ZrB2 Particles

To obtain the better ZrB₂/Al(OH)₃-Y(OH)₃ core-shell composite particles, ZrB₂ particles must be adequately dispersed during the coating process. In this article, the dispersibility of ZrB₂ particles in the ZrB₂ suspension is investigated via the sedimentation method. Through test and analysis, the dispersibility is rapidly increased with prolonging the ultrasonic dispersion time before 10 minutes. After 30 minutes, the sedimentation grads using ultrasonic dispersion basically reach the sedimentation balance, but the grads using mechanical agitating dispersion does not basically change after 5 minutes. The ultrasonic dispersion is one of more effective ways between ultrasonic and mechanical agitating dispersion, the dispersion time for 10 minutes is chosen in the dispersibility of ZrB₂ particles via ultrasonic dispersion.     

Preparation of hydrophobic organic-silicanano composites

In this paper, we use silica nanoparticles modified by methacryloxy propyl trimethoxylsilane (KH570) as the core material, and employ polymers including hexafluorobutyl methacrylate (HFMA), dodecafluoroheptyl methacrylate (DFMA) and acrylic ester as the shell materials to prepare the hydrophobic inorganic–organic hybrid nanocomposites with a seed emulsion polymerization strategy. The size, morphologyandproperties of the core-shell structured nanoparticles are investigated by TEM and SEM. The results showthat the polymer nanocomposite has three concentric layers with silica nanoparticles in the center, acrylic polymer as the internal shell and fluorosilicone polymer as the outmost shell. By controlling the ratio of the silica nanoparticles and monomers, we can achieve each composite particle has the core-shell structure with silica nanoparticles as the core and the thin layer of fluorosilicone polymer as the shell. Compared with the traditional polymer film, the nanocomposite film shows a hydrophobic property with a contact angle of up to 100 degree. Therefore, it is feasible to prepare hydrophobic organic–inorganic nanocomposites using the method proposed here.     

A new route of emulsifier-free emulsion polymerization for the preparation of polymer coated magnetite nanoparticles

A new route of emulsifier-free emulsion polymerization based on the homogenous mechanism was investigated to prepare magnetic nanoparticles coated by poly (methyl methacrylate) (PMMA). The experimental results confirm the formation of PMMA thin and unique layers covering magnetite cores. The polymer layer thickness, determined from transmission electron microscopy (TEM) images, increases from 4.3 nm to 6.8 nm with increasing mass ratio of MMA to magnetite from 3:1 to 11:1. The increase of the polymer thickness results in the decrease in magnetization saturation of polymeric coated magnetic particles. However, this reduction, no more than 13 emu g^?1, is much lower compared to that in other studies with the presence of surfactants or emulsifiers. Besides, the dispersion stability of the prepared particles is significantly improved.     

含氟丙烯酸树脂的合成及性能研究

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为主要单体,甲基丙烯酸全氟烷基酯(FMA)为合氟单体,甲基丙烯酸羟基乙酯(HEMA)为交联单体,采用溶液聚合法合成含氟丙烯酸树脂,并与固化剂六甲撑二异氰酸酯(HDI)三聚体固化成膜.研究了软硬单体配比、羟值、聚合温度、氟单体含量及添加方式等因素对树脂粘度、分子量及其分布以及涂膜的疏水性、硬度、附着力和耐热性的影响.结果表明,在m(BA):m(MMA)=6:4、羟值为64.8mg/g、氟单体用量为3%且采用后期添加、反应温度为85℃的条件下制得了含氟丙烯酸树脂,其分子量Mn=26980,分布窄(D=1.391),涂膜与水的静态接触角达到110°,硬度为1H,附着力为0级,分解温度为310℃.     

Modification in Surface Chemistry of the Polyetrafluoroethylene Through Chemical Graft Copolymerization for Potential Oil Contamination Control

In the present study, an attempt has been made to design an oleophobic surface through chemical graft copolymerization of methyl methacrylate (MMA) onto polytetrafluroethylene (PTFE) film. The PTFE films were grafted with MMA resulting in PTFE-g-MMA grafts using benzoyl peroxide (BPO) as initiator in aqueous media. Optimum conditions pertaining to maximum percentage of grafting were evaluated by varying time, temperature, initiator, and monomer concentration. The maximum graft yield 9.47% was obtained at [BPO] = 0.03 M, [MMA] = 10%V/V, [reaction temperature] = 50°C and [reaction time] = 120 min. Methyl iodide was used to measure the contact angle, which revealed the oleophobic nature of grafted PTFE-g-MMA film. Maximum contact angle 95.5° of PTFE-g-MMA film was observed at optimum grafting conditions. The surface morphology of PTFE-g-MMA films was studied by Field emission scanning electron microscopy (FE-SEM) and x-ray diffraction (XRD) analysis confirmed the change in structure of PTFE after MMA grafting.     

新型室温酯化法制备纳米SiO2引发剂和原位引发聚合

提出了一种在室温、潮湿和大气环境等温和条件下,通过酯化反应在纳米SiO2微球表面接枝偶氮分子,合成纳米SiO2引发剂的新方法.使用这种纳米SiO2引发剂原位引发单体苯乙烯和甲基丙烯酸甲酯进行自由基聚合,在SiO2表面接枝聚苯乙烯或聚甲基丙烯酸甲酯.结果表明:用合成的纳米SiO2引发剂原位引发单体聚合后,在纳米SiO2表...