聚甲基丙烯酸甲酯预聚物作为助稳定剂的细乳液聚合速率研究

以聚甲基丙烯酸甲酯(PMMA)预聚物为助稳定剂、十二烷基硫酸钠为乳化剂、十六醇为助乳化剂和过硫酸钾为引发剂,研究甲基丙烯酸甲酯(MMA)的细乳液聚合反应速率.考察乳化剂浓度、助乳化剂浓度、引发剂浓度、预聚物浓度、预聚物分子量以及反应温度对聚合速率的影响.结果表明:聚合速率RP随着乳化剂浓度或反应温度的提高而增加,随着助乳化剂浓度的提高而减小,引发剂浓度对RP影响不明显.在相同条件下,加入预聚物的细乳液体系聚合速率RP在聚合反应前期比常规细乳液有明显提高:PMMA(MH=520000)浓度为2×10-3mmol·L-1时,RP的最大峰值为1.84×10-2mol·L-1·min-1.预聚物PMMA在MMA细乳液聚合体系中,可以提高聚合速率和增加体系稳定性.     

反光布用聚丙烯酸酯无皂乳液的研制及应用

以过硫酸铵（APS）为引发剂,甲基丙烯酸甲酯 MMA 为硬单体,丙烯酸丁酯 BA 和丙烯酸乙酯（EA）为软单体,丙烯酸 AA 为功能单体,阴-非复合可聚合乳化剂（WE-9）为乳化剂,采用预乳化法合成了一种聚丙烯酸酯无皂乳液。讨论了各单体用量和乳化剂用量对其性能的影响。结果表明,当w（BA+EA）=80%、w（MMA）=15%、w（AA）=5%和w（WE-9）=1.2%时,该无皂乳液有优良的综合性能,可满足反光布生产要求。（）（）（）     

活化溶胀法大粒径聚甲基丙烯酸甲酯微球的制备

探讨了活化溶胀法制备大粒径聚甲基丙烯酸甲酯（PMMA）微球的方法。首先用无皂乳液聚合法制备了中位径为0．21μm的PMMA种子微球。然后以正庚烷为活化剂、以十二烷基硫酸钠（SDS）为乳化剂进行活化溶胀,再以单体甲基丙烯酸甲酯（MMA）和引发剂偶氮二异丁腈（AIBN）对活化微球进行溶胀,溶胀平衡后升温进行聚合反应,制得了中位径为0．77μm的PMMA微球。     

甲基丙烯酸甲酯的电化学乳液聚合

采用可编程的线性直流电源电解铁阳极产生Fe2+,以此引发过硫酸铵（APS）产生自由基,催化甲基丙烯酸甲酯（MMA）单体进行乳液聚合。在优化的聚合时间和引发剂浓度条件下,重点研究了电流强度对聚合物相对分子质量及分布的调控作用。结果表明：在0.10~0.18 A的电流范围内,随着电流强度的增大,聚合物的平均相对分子质量也有所增加。通过调节电流的大小,可以对聚合物的相对分子质量分布进行调控,当电流从0.10 A增大至0.12 A时,聚甲基丙烯酸甲酯（PMMA）相对分子质量分布指数（Mw/Mn）减小为1.461。     

基于细乳液聚合法TiO2/PMMA纳米复合粒子的制备及其性能

采用细乳液聚合法制备了二氧化钛/聚甲基丙烯酸甲酯（TiO2/PMMA）纳米复合粒子,考察了引发剂、助乳化剂、乳化剂、单体结构和种类对TiO2/PMMA纳米复合粒子性能的影响。结果表明与十二醇和十六醇相比,十六烷（HD）更能抑制甲基丙烯酸甲酯（MMA）液滴的Ostwald熟化效应,当MMA占TiO2质量分数的60%,HD对单体质量分数的6%,可聚合乳化剂1-烯丙氧基-3-(4-壬基苯酚)-2-丙醇聚氧乙烯(10)醚硫酸铵（DNS-86）占整个体系的质量分数为2%时,制备TiO2/PMMA纳米复合粒子分散体的粒径为185nm,此时TiO2/PMMA纳米复合粒子与细乳液粒径差距较小;采用TiO2/PMMA纳米复合粒子制备白色涂料墨水的稳定性和遮盖力明显优于同等条件下TiO2所制备的涂料墨水。     

高固含量无皂丙烯酸酯共聚乳液的合成研究

以烯丙氧基壬基酚乙基聚氧乙烯硫酸钠（DNS-86）为反应性乳化剂,甲基丙烯酸甲酯（MMA）为硬单体,丙烯酸丁酯（BA）为软单体,甲基丙烯酸（MAA）为功能性单体,采用预乳化种子半连续聚合方式,合成了固含量65％的无皂丙烯酸酯乳液。讨论了软硬单体配比、乳化剂用量、聚合温度等反应条件对高固含量乳液的合成及性能的影响。     

可聚合乳化剂合成含氟丙烯酸酯无皂乳液及其性能

以甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）、甲基丙烯酸六氟丁酯（HFMA）等为主要原料,采用预乳化种子乳液聚合法合成了含氟丙烯酸酯无皂乳液,考察了可聚合乳化剂烯丙氧基壬基酚聚氧乙烯（10）醚硫酸铵（DNS-86）和HFMA的用量对无皂乳液的电解质稳定性和涂膜耐水性的影响。利用傅里叶红外光谱、差示量热扫描仪及热重分析对氟丙乳液涂膜进行了表征。结果表明：与传统乳液聚合得到的乳液及相应的涂膜相比,无皂乳液的耐电解质性能和涂膜的耐水性都有一定的提高,含氟单体有效地参与了聚合,涂膜的疏水性大大增强,耐热性显著提高。     

超声引发乳液聚合同步原位合成纳米Ag/聚合物复合粒子的研究

超声辐射不含引发剂、还原剂而仅含有银盐的甲基丙烯酸甲酯乳液,原位合成了纳米Ag/PMMA复合粒子。这种复合粒子的IR、HRTEM和TEM表征结果显示,以纳米银为核的复合粒子具有很好的分散性,且纳米银为多晶体,纳米银粒子与聚合物间存在化学作用。通过考查反应过程中各因素对单体转化率的影响发现：不存在AgNO3时MMA几乎不聚合,而加入AgNO3时MMA不但能聚合,而且在一定浓度范围内,转化率随AgNO3浓度增加而增大说明银离子的存在能够促进单体的聚合。纳米Ag/PMMA复合物的热分析实验结果表明,银粒子的存在可能催化复合材料中PMMA的分解,导致分解温度提前。     

苯乙烯-甲基丙烯酸甲酯悬浮-乳液耦合聚合动力学

采用苯乙烯(St)悬浮聚合过程滴加甲基丙烯酸甲酯(MMA)乳液聚合组分,进行悬浮-乳液耦合聚合(SECP), 制备大粒径聚苯乙烯-聚甲基丙烯酸甲酯(PS-PMMA)复合粒子.采用¹H NMR分析方法,讨论了SECP动力学特征.St的SECP聚合速率和转化率与悬浮聚合一致;MMA聚合速率决定于乳胶粒子聚合速度和凝并在悬浮粒子表面的速度,聚合速率比常规乳液聚合速率低.由于凝并在悬浮粒子表面的PMMA乳胶粒子不再有乳液聚合特征,MMA在SECP中转化率低于同条件常规乳液聚合.分别得到乳化剂和引发剂浓度与SECP和普通乳液聚合恒速段聚合速率的关系.     

含氟丙烯酸酯共聚物膜的制备及其表面性能研究

以甲基丙烯酸甲酯(MMA)、丙烯酸六氟丁酯(HFBA)为单体,聚乙二醇甲醚甲基丙烯酸酯(MPEGMA)为可聚合乳化剂,采用无皂反相微乳液聚合法制备了新型含氟丙烯酸酯三元共聚物疏水膜。利用傅立叶红外光谱(FTIR)、扫描电镜(SEM)、X射线衍射(XRD)、接触角测量仪对聚合物膜性能进行表征分析,主要考查了含氟量、乳化剂浓度、成膜方式以及含水量对聚合物膜表面性能及其亲疏水性的影响。结果表明,增加含氟量在一定程度可提高聚合物膜表面的疏水性,MPEGMA侧链结晶有利于含氟基团的表面离析,不同成膜方式影响分子基团的排列、分布及表面粗糙度。     

Poly(methyl methacrylate)/clay nanocomposites by photoinitiated free radical polymerization using intercalated monomer

A series of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposite were prepared by successfully dispersing the inorganic nanolayers of MMT clay in an organic PMMA matrix via in situ photoinitiated free radical polymerization. Methyl methacrylate monomer was first intercalated into the interlayer regions of organophilic clay hosts by “click” chemistry followed by a typical photoinitiated free radical polymerization. The intercalated monomer was characterized by FT-IR spectroscopy, elemental analysis and thermogravimetric analysis methods. The intercalation ability of the modified monomer and exfoliated nanocomposite structure were confirmed by X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Thermal stability of PMMA/MMT nanocomposites was also studied by both differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).     

PMMA/BA无皂乳液聚合

以过硫酸铵为引发剂,用超声波引发PMMA/BA无皂乳液聚合;探讨了单体和引发剂的质量分数对单体转化率的影响,并对聚合物进行了FT-IR和TEM的表征。结果表明:PMMA/BA乳胶粒直径大约在100nm左右。     

Montmorillonite clay/poly(methyl methacrylate) hybrid resin and its barrier property to the plasticizer within poly(vinyl chloride) composite

A poly(methyl methacrylate) (PMMA)‐clay hybrid resin was prepared via bulk polymerization methyl methacrylate monomer in the presence of montmorillonite intercalated with an ammonium salt of dctadecylamine. The products were characterized by infrared spectroscopy, X‐ray diffraction, pyrolysis gas chromatography, and transmission electron microscopy. Results confirm that the resin is intercalated with PMMA molecules. The layer spacing of montmorillonite are enlarged, whereas the silicate layers are homogeneously dispersed individually. When the PMMA‐clay hybrid was blended with plasticized poly(vinyl chloride), the resulting composite exhibited excellent barrier property in preventing the plastizer's migration from the inner matrix to the surface of the product. This is presumably caused by barrier property of the silicate layers dispersed in the composite. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 425–430, 1999     

Study on bulk polymerization of methyl methacrylate initiated by low intensity ultrasonic irradiation

Methyl methacrylate (MMA) was polymerized in bulk solutions using low intensity ultrasonic radiation of 0.25 W/cm². The polymerization occurred after 1 h of irradiation time was applied. The polymerization rate was greatly accelerated either by increasing the amount of poly (methyl methacrylate) (PMMA) granular added into the system or by elongating the irradiation time. However, it was found that the reaction rate increased with the decreasing of the ultrasonic frequencies when the exposure time of the polymerization under the irradiation was less than 3 h. Experimental results verified that the polymerization was initiated by free radicals, which were mainly generated from the degradation of PMMA macromolecular chains, the friction between the polymer macromolecular chains and the solvent monomer. These findings were obviously different from those obtained when high intensity ultrasonic irradiation was used. The polymers fabricated in this study by using ultrasound irradiation have a narrower molecular weight distribution compared to those obtained from the polymerizations induced by the conventional initiators. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation,characterization, and thermal properties of poly (methyl methacrylate)/boron nitride composites by bulk polymerization

Poly (methyl methacrylate)/boron nitride (PMMA/BN) composites were prepared by dispersing BN particles into methyl methacrylate monomer phase by bulk polymerization method. BN particles modified with silane coupling agent, γ‐methacryloxypropyl trimethoxy silane, were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Effects of modified BN particle content on thermal conductivity were investigated, and the experimental values were compared with those of theoretical and empirical models. With 16 wt% of BN particles, the thermal conductivity of the composite was 0.53 W/(m·K), 1.8 times higher than that of pure PMMA. The microstructures of the PMMA/BN composites were examined by scanning electron microscopy, energy‐dispersive X‐ray analysis, and transmission electron microscopy. Dynamic mechanical analysis and thermogravimetric analysis traces also corroborated the confinement of the polymer in an inorganic layer by exhibiting an increase in glass‐transition temperatures and weight loss temperatures in the thermogram. Mechanical properties and electrical insulation property of the PMMA/BN composites were also determined. These results showed that PMMA/BN composites may offer new technology and business opportunities. POLYM. COMPOS., 36:1675–1684, 2015. © 2014 Society of Plastics Engineers     

Preparation and characterization of a PMMA/Ce(OH)3, Pr2O3/graphite nanosheet composite

An easy process for the synthesis of poly(methyl methacrylate)/Ce(OH)₃, Pr₂O₃/graphite nanosheet (PMMA/Ce(OH)₃, Pr₂O₃/NanoG) composite was developed. Graphite nanosheets (NanoG) were prepared by treating the expanded graphite with sonication in aqueous alcohol solution. The PMMA/Ce(OH)₃, Pr₂O₃/NanoG composites were prepared via in situ polymerization of MMA monomer in the presence of graphite nanosheets and Ce(OH)₃, Pr₂O₃ through reverse micelle template, in which the methyl methacrylate was designated as the oily phase. The composites were then dispersed with chloroform and coated on glass slides to form films. Scanning and transmission electron microscopy were used to characterize the structure and dispersion of the graphite nanosheets and the composites. The results showed that the high-aspect-ratio structure of the nanosheets played an important role in forming a conducting network in the PMMA matrix. From thermogravimetric analysis, the introduction of graphite nanosheets and inorganic nanopartices exhibited a beneficial effect on the thermal stability of PMMA.     

粒径可控的聚丙烯酸丁酯/聚甲基丙烯酸甲酯核壳乳液的制备及表征

采用种子乳液聚合法制备了聚丙烯酸丁酯(PBA)乳液,然后通过第二单体甲基丙烯酸甲酯的预溶胀法聚合制备了PBA/聚甲基丙烯酸甲酯(PMMA)乳液,用激光散射粒度仪和透射电子显微镜对乳液粒径和结构进行了表征.结果表明,当乳化剂十二烷基硫酸钠质量分数为丙烯酸丁酯的1.5%时,可制备粒径为53.6 nm且分布窄的PBA种子乳液;通过调整补加乳化剂、单体与种子乳液的用量,可制得粒径为53.6～443.8 nm的一系列单分散PBA乳液;PBA/PMMA乳液具有完善的核壳结构,且在核壳两相间存在着一个过渡层.     

Ag/PMMA复合粒子的制备及表征

纳米银/聚甲基丙烯酸甲酯(Ag/PMMA)复合粒子是一种新型的功能粒子,可以有效利用昂贵金属纳米粒子组元的独特性能,是高表面能金属纳米粒子稳定化的有效途径.本文首先在超声波场中用表面活性剂SDS对纳米Ag粒子进行亲油化处理,然后在N<,2>保护下利用超声波的分散、粉碎、活化、引发等多重作用,在实现纳米Ag粒子在反应介质...     

Natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) blends

The grafting of the methyl methacrylate (MMA) monomer onto natural rubber using potassium persulfate as an initiator was carried out by emulsion polymerization. The rubber macroradicals reacted with MMA to form graft copolymers. The morphology of grafted natural rubber (GNR) was determined by transmission electron microscopy and it was confirmed that the graft copolymerization was a surface‐controlled process. The effects of the initiator concentration, reaction temperature, monomer concentration, and reaction time on the monomer conversion and grafting efficiency were investigated. The grafting efficiency of the GNR was determined by a solvent‐extraction technique. The natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) (NR‐g‐MMA/PMMA) blends were prepared by a melt‐mixing system. The mechanical properties and the fracture behavior of GNR/PMMA blends were evaluated as a function of the graft copolymer composition and the blend ratio. The tensile strength, tear strength, and hardness increased with an increase in PMMA content. The tensile fracture surface examined by scanning electron microscopy disclosed that the graft copolymer acted as an interfacial agent and gave a good adhesion between the two phases of the compatibilized blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 428–439, 2001