界面粘接对填充复合材料力学性能的影响

利用原位聚合的方法将聚甲基丙烯酸甲酯（PMMA）包覆在滑石粉的表面,制得了含PMMA粘接层的滑石粉／PVC复合材料。聚合物粘接层类似于粘接材料的粘接剂的作用,它很好地改善了复合材料的界面粘附性,提高了复合材料的机械强度,由于聚合物粘和基体聚合物的相互扩散以及界面内应力的存在,和昨合材料中存在一个最佳的聚合物粘接层。     

以PVC为外壳层的ACR抗冲改性剂的合成及其对PVC的增韧作用

以聚丙烯酸丁酯(PBA)为内核,通过种子乳液聚合制备了分别以聚甲基丙烯酸甲酯(PMMA)、聚氯乙烯(PVC)、PMMA/PVC为壳层的纯丙烯酸酯(ACR)和PVC改性ACR乳液.扫描电镜观察发现,纯ACR乳胶粒子具有明显的核-壳结构,进一步包覆PVC后形成疏松外层.考察了不同结构ACR与PVC共混物的相态结构、抗冲性能和断面形貌,发现用PVC部分或完全替代PMMA壳层的改性ACR在PVC基体分散良好,具有与纯ACR相当的增韧PVC作用,冲击断面呈现典型的韧性断裂特征.     

纳米CaCO_3的接枝改性及其填充PVC复合材料的性能

采用表面原位接枝聚合在纳米CaCO3颗粒表面引入聚甲基丙烯酸甲酯(PMMA)或聚丙烯酸丁酯(PBA),用共混法制备了纳米CaC03/PVC复合材料,研究了不同界面特性时纳米CaCO,/PVC复合材料的力学性能.研究结果表明:通过表面原位接枝聚合反应可以在纳米CaCO3颗粒表面接枝PMMA和PBA;表面接枝聚合改性大大促进了纳米CaCO3粒子在PVC基体中的分散行为,增加了复合材料的拉伸强度以及与聚合物的界面粘接强度,但复合材料的冲击强度有所下降.     

Effect of the core/shell latex particle interphase on the mechanical behavior of rubber-toughened poly(methyl methacrylate)

Two- and three-layer composite latex particles were used to prepare rubber-toughened poly(methyl methacrylate) (RT-PMMA). The interfacial thicknesses of the multi-layered particles were varied by using different emulsion polymerization synthesis techniques. The resulting interphases were previously characterized by ¹³C nuclear magnetic resonance techniques. The poly(divinyl benzene)/poly(butyl acrylate) (PDVB/PBA) interphase thickness was found to be in the range of 5–7 nm. It was also found that the PBA/PMMA interphase thickness could be varied from 5 to 7 nm (batch addition of MMA) to 15 to 17 nm (interphase compatibilized with PMMA macromonomer). The interphase thickness was expected to play an important role in the mechanical behavior of PMMA. The effect of the interphase of two- and three-layer particles on the tensile and fracture behavior of PMMA composites was evaluated. The fracture surfaces were examined by scanning electron microscopy. The two-layer PBA/PMMA particles with a thicker interphase (15–17 nm) exhibited higher K_IC values with the PMMA composites compared with PBA/PMMA particles with a thinner interphase (5–7 nm). The three-layer particles were found to be more effective in toughening PMMA compared with the two-layer particles. The differences in toughening behavior are speculated to arise from the morphological effects caused by a thicker interphase, which in turn results in better coverage by the PMMA shell and a more uniform distribution of the toughening particles in the PMMA matrix. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:581–593, 1997     

Evaluation of polymethacrylic ionomer as compatibilizers for MCPA6/clay composites

The compatibilization effects provided by polymethacrylic ionomer (PMMA ionomer) on monomer‐casting polyamide6 (MCPA6)/clay (pristine sodium montmorillonite) composites were studied in this work. The PMMA ionomer used in this study was sodium polymethacrylate ionomer (PMMA Na⁺‐ionomer), which is a copolymer of methyl methacrylate and sodium methacrylate, prepared using emulsion polymerization. MCPA6/clay/PMMA Na⁺‐ionomer composites were prepared by in situ anionic ring‐opening polymerization (AROP) of ε‐caprolactam (CLA). X‐ray diffraction (XRD) and transmission electron microscopy (TEM) plus rheological measurement were used to characterize those composites. The results indicated that PMMA Na⁺‐ionomer is a good compatibilizer for this system. With increasing PMMA Na⁺‐ionomer content, a better dispersion of clay layers was successfully achieved in the MCPA6 matrix. Furthermore, differential scanning calorimetry (DSC) and XRD results indicated that well dispersed silicate layers limit the mobility of the MCPA6 molecule chains to crystallize, reduce the degree crystalline, and favor the formation of the γ‐crystalline form of the MCPA6 matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Improving mechanical properties of poly(vinyl chloride) by doping with organically functionalized reactive nanosilica

Nanosilica particles are functionalized by in situ surface‐modification with trimethyl silane and vinyl silane. Resultant reactive nanosilica (coded as RNS) contains double bonds and possesses good compatibility with vinyl chloride (VC) and polyvinyl chloride (PVC). This makes it feasible for RNS to copolymerize with VC generating RNS/PVC composites via in situ suspension polymerization. As‐prepared RNS/PVC composite resins are analyzed by means of FTIR. The tensile strength and impact strength of compression‐molded RNS/PVC composites are measured and compared with that of compression‐molded PVC composites doped with dispersible nano‐SiO₂ particles (abridged as DNS) surface‐modified with trimethyl silane alone. Moreover, the thermal stability of compression‐molded RNS/PVC and DNS/PVC composites is evaluated by thermogravimetric analysis. It has been found that RNS/PVC composites possess greatly increased impact strength and tensile strength than PVC matrix, while DNS/PVC composites possess higher impact strength than PVC matrix but almost the same tensile strength as the PVC matrix. This implies that DNS is less effective than RNS in improving the mechanical strength of PVC matrix. Particularly, RNS/PVC composites prepared by in situ suspension polymerization have much higher mechanical strength than RNS/PVC composites prepared by melt‐blending, even when their nanosilica content is only 1/10 of that of the melt‐blended ones. Besides, in situ polymerized RNS/PVC and DNS/PVC composites have better thermal stability than melt‐blended nanosilica/PVC composites. Hopefully, this strategy, may be extended to fabricating various novel high‐performance polymer‐matrix composites doped with organically functionalized nanoparticles like RNS. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of PMMA composites activated with starch for immobilization of L‐asparaginase

Poly (methyl methacrylate) (PMMA)–starch composites were prepared by emulsion polymerization technique for L‐asparaginase (L‐ASNase) immobilization as highly activated support. The hydroxide groups on the prepared composites offer a very simple, mild and firm combination for enzyme immobilization. The pure PMMA and PMMA‐starch composites were characterized as structural, thermal and morphological. PMMA‐starch composites were found to have better thermal stability and more hydrophilic character than pure PMMA. L‐ASNase was immobilized onto PMMA‐starch composites contained the different ratio of starch (1, 3, 5, and 10 wt %). Immobilized L‐ASNase showed better performance as compared to the native enzyme in terms of thermal stability and pH. K_m value of immobilized enzyme decreased approximately eightfold compared with the native enzyme. In addition to, immobilized L‐ASNase was found to retain 60% of activity after 1‐month storage period at 4 °C. Therefore, PMMA‐starch composites can be provided more advantageous in terms of enzymatic affinity, thermal, pH and storage stability as L‐ASNase immobilization matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43421.     

The inverse emulsion polymerization of acrylamide using poly(methyl methacrylate)‐graft‐polyoxyethylene as the stabilizer

Inverse emulsion polymerization of an aqueous solution of acrylamide (AM) in toluene is carried out using poly(methyl methacrylate)‐graft‐polyoxyethylene (PMMA‐g‐PEO) as an emulsifier. The kinetics of polymerization, morphology of the particle, and particle size of the inverse emulsion have been investigated. The rates of polymerization are found to be proportional to the initiator concentration, the monomer concentration, and the emulsifier concentration. The morphology of particles shows a spherical structure. The mechanism of inverse emulsion polymerization using amphipathic graft copolymer as the emulsifier is proposed. The resulting molecular weights of polyacrylamide are extremely high, and relate to the amphipathic graft copolymer structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 528–534, 2001     

Intercalated structure of polypropylene/in situ polymerization-modified talc composites via melt compounding

Talc was modified with methyl methacrylate (MMA) or butyl acrylate (BA) via in situ polymerization. The talc/isotactic polypropylene (PP) composites with nano-sized intercalated structure were formed by melt compounding of PP with the modified talc. The results showed that the talc layers were partially delaminated, aligned along the flow direction, and uniformly dispersed in the PP matrix. The thickness of the PMMA-modified talc layers in the PP matrix was in the range 80-240 nm, while the PBA-modified talc was even thinner. PMMA or PBA macromolecules attached on the surface of talc layers hindered the crystallization of the PP component. Moreover, the aligned pristine talc layers promoted the orientation of the PP crystals. However, the extent of PP crystal orientation decreased in the presence of PMMA or PBA-modified talc.     

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。     

Preparation and morphological characterization of two- and three-component natural rubber-based latex particles

Different emulsion polymerization processes allowed variation in the microstructure of composite natural rubber (NR)-based latex particles. A prevulcanized and a not-crosslinked natural rubber latex were coated with a shell of crosslinked poly(methyl methacrylate) (PMMA) or polystyrene (PS). The bipolar redox initiating system tert-butyl hydroperoxide/tetraethylene pentamine promoted a core–shell arrangement. Furthermore, PS subinclusions were introduced into the NR core. The initiators used for the subinclusion synthesis were azobisisobutyronitrile at high temperature and a redox initiation system consisting of tert-butyl hydroperoxide/dimethylaniline at low temperature. The morphology of the resulting latex interpenetrating networks (IPN) was characterized by transmission electron micros-copy (TEM) and scanning electron microscopy (SEM). Different staining methods allowed us to increase the contrast between the NR phase and the secondary polymers in the composite latex particles. A semicontinuous feeding process decreased the PS subinclusions size by a factor of 6 in comparison with a batch reaction. Depending on the NR/styrene swelling ratio, the crosslinking degree, and the polymerization temperature used, distinct differences of the phase arrangement of polymers in the latex particles were revealed. © 1996 John Wiley & Sons, Inc.     

Modification of porous suspension‐PVC particles by stabilizer‐free aqueous dispersion polymerization of absorbed monomers

The modification of porous PVC particles by an in‐situ stabilizer‐free polymerization/crosslinking of a monomer/crosslinker/peroxide solution absorbed within the PVC particles is presented. The modifying crosslinked polymers are polystyrene (PS) crosslinked with DVB (divinyl benzene), polymethyl methacrylate (PMMA) crosslinked with ethylene glycol dimethacrylate (EGDMA), and styrene‐MMA copolymer crosslinked with DVB. The modified PVC particles characterization includes polymerization yield, non‐extractables, ¹³C solid‐state CPMAS NMR, porosity measurements and also morphology and dynamic mechanical behavior (DMTA). The levels of nonextractable fractions found and ¹³C solid‐state CPMAS NMR results are indicative of low chemical interaction in the semi‐IPN PVC particles. Particle porosity levels and SEM observations indicate that styrene and MMA mainly polymerize within the PVC particles' bulk and just small amounts in the pores. MMA polymerization in the PVC pores is as crusts covering the PVC pore surfaces, whereas styrene polymerization in the PVC pores is by filling the pores. Dynamic mechanical studies show that tanδ and the storage modulus curves are influenced by the incorporation of PS and XPS but not by the incorporation of PMMA and XPMMA.     

Particle morphology and NMR structure of polymethylmethacrylate/polystyrene emulsifier‐free core–shell cationic latices in the presence of DBMEA

In the absence of emulsifier, we prepared stable emulsifier‐free polymethylmethacrylate/polystyrene (PMMA/PSt) copolymer latex by batch method with comonomer N,N‐dimethyl, N‐butyl, N‐methacryloloxylethyl ammonium bromide (DBMEA) by using A1BN as initiator. The size distribution of the latex particles was very narrow and the copolymer particles were spherical and very uniform. Under the same recipe and polymerization conditions, PMMA/PSt and PSt/PMMA composite polymer particle latices were prepared by a semicontinuous emulsifier‐free seeded emulsion polymerization method. The sizes and size distributions of composite latex particles were determined both by quasi‐elastic light scattering and transmission electron microscopy (TEM). The effects of feeding manner and staining agents on the morphologies of the composite particles were studied. The results were as follows: the latex particles were dyed with pH 2.0 phosphotungestic acid solution and with uranyl acetate solution, respectively, revealing that the morphologies of the composite latex particles were obviously core–shell structures. The core–shell polymer structure of PMMA/PSt was also studied by ¹H, ¹³C, 2D NMR, and distortionless enhancement by polarization transfer, or DEPT, spectroscopy. Results showed that PMMA/PSt polymers are composed of PSt homopolymer, PMMA homopolymer, and PMMA‐g‐PSt graft copolymers; results by NMR are consistent with TEM results. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1681–1687, 2005     

Batch and semicontinuous emulsion copolymerization of vinylidene chloride and butyl methacrylate. I. Kinetics in VDC–BMA emulsion polymerization and surface and colloidal properties of VDC–BMA latexes

Vinylidene chloride (VDC)—butyl methacrylate (BMA) comonomer mixtures with various composition (83 : 17, 60 : 40, 33 : 67 in mol %) were polymerized at 25°C using redox catalyst by batch and seeded semicontinuous emulsion copolymerization. The reactivity ratios determined in VDC (M₁)—BMA (M₂) emulsion copolymerization system were r₁ = 0.22 and r₂ = 2.41. Seven 35% solids (83 : 17 mol %) VDC–BMA copolymer latexes were prepared: one batch (G), one seeded batch (F), and 5 seeded semicontinuous polymerizations of 5 different monomer feed rates ranging from 0.27 (A) to 1.10 wt %/min (E). The kinetic studies of seeded semicontinuous polymerizations A-E showed that the rates of polymerizations (R_p) were controlled by the monomer addition rates (R_a). The conversion versus time curves for the polymerizations of 0 : 100–100 : 0 VDC–BMA mixtures by batch polymerization showed that the rate of polymerization (R_p) was a function of the number of particles, and that the rate of polymerization in a latex particle (R_pp) increased with increasing proportions of butyl methacrylate in the monomer mixture. All of the latexes had narrow particle size distributions. The greater particle number density in VDC polymerization and the greater water solubility of VDC suggest that the homogeneous nucleation mechanism is operative in VDC–BMA copolymerizations. The latex copolymers prepared by semicontinuous polymerization had lower number-and weight-average molecular weights than those of the corresponding batch copolymers, resulting from the monomer starvation occurring during the semicontinuous polymerization. The surface characterization study of the cleaned latexes showed that for the latexes by batch process, the surface charge density derived from strong-acid groups decreased with increasing proportion of VDC in the monomer mixture. On the other hand, for the latexes prepared by semicontinuous polymerization, the surface charge density derived from strong-acid groups did not depend on the monomer composition of the copolymers.     

Effects of mesoporous silica particles on the emulsion polymerization of methyl methacrylate

Rod‐like and spherical mesoporous SBA‐15 silica particles were synthesized as pure silicas and surface modified by organosilane coupling agents firstly, and then the effects of these mesoporous materials on the critical micelle concentration (CMC) of sodium dodecylsulfate (SDS), the stabilities of batch and semi‐continuous MMA emulsion polymerizations, and the molecular weights and molecular weight distributions of the polymer products were studied. The incorporation of both unmodified and silane‐modified forms of the mesoporous silica particles in the polymerization reaction increased the CMC of SDS. The presence of the unmodified mesoporous silica in the polymerization process led to instability in the batch emulsion polymerization process, as indicated by the formation of increased amounts of coagulum, and a decrease in the molecular weight of the polymer product. However, in comparison to the polymer formed in the absence of particle additives the molecular weight of the PMMA polymer increased with the amount of emulsifier and the addition of silane‐modified SBA‐15 particles, suggesting the growth of the polymer chains is facilitated at least in part by reaction in the pores of the particles. The improvement in molecular weight indicates that semi‐continuous MMA emulsion polymerization is best suited for the preparation of PMMA–mesoporous silica composites. POLYM. ENG. SCI., 54:2746–2752, 2014. © 2013 Society of Plastics Engineers     

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 conducting polymer composites: effects of porosity on electrical conductivity

To prepare conducting polymer composites, porous polymethyl methacrylate (PMMA) particles with different specific surface areas were prepared by seeded emulsion polymerization and solvent extraction. The dried porous particles were imbibed with the oxidant solution and adsorbed pyrrole from a solution. The incorporation of pyrrole into the porous particles was achieved by chemical oxidative polymerization. The effects of various polymerization parameters on the electrical conductivity were systematically investigated. The important factors affecting conductivity were the porosity of the host polymer particles and the solvent polarizability. © 1998 SCI.     

Effects of preparation methods on the property of PMMA/SBA-15 mesoporous silica composites

In the paper, poly(methyl methacrylate)(PMMA)/SBA-15 composite materials were prepared by four different methods, that is, in-situ batch emulsion polymerization in the presence of mesoporous SBA-15, PMMA emulsion mixed with SBA-15 powder or dispersion in water, PMMA powder mixed with SBA-15 powder, and the properties of the composite materials were determined and compared. The composites were characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanics analysis (DMA) and scanning electron microscope (SEM). The results showed that the glass transition temperatures (Tg), the storage modulus and tensile strength of the PMMA/SBA-15 composites were all improved obviously, while the thermal decomposition temperature did not influenced apparently. The composite made by in-situ batch polymerization exhibited the most improvement in the mechanical properties and Tg while the composite prepared by mixing PMMA emulsion and SBA-15 dispersion gave rise to the least improvement in the mechanical properties and Tg. These results were contributed to introducing different amount of voids into polymer matrix which were demonstrated by dielectric constant measurement and SEM morphology observation.     

Double‐miniemulsion preparation of Fe3O4/poly(methyl methacrylate) magnetic latex

Magnetic poly(methyl methacrylate) (PMMA) microspheres were prepared by double‐miniemulsion polymerization. First, oleic acid coated magnetite particles synthesized by means of coprecipitation were dispersed into octane to obtain a ferrofluid. The ferrofluid and MMA were emulsified to form O/W emulsion, respectively. Subsequently two miniemulsions were mixed together for polymerization. The obtained magnetic polymer particles were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, X‐ray powder diffraction, and thermogravimetry. The results showed that oleic acid coated magnetite particles were well encapsulated in PMMA. The effects of initiator dosage and monomer concentration on the conversion of MMA were also investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚甲基丙烯酸甲酯包覆纳米CaCO3改性聚氯乙烯研究

研究了聚甲基丙烯酸甲酯(PMMA)包覆纳米CaCO3复合粒子填充聚氯乙烯(PVC)复合材料的加工塑化和力学性能，并与未改性纳米CaCO3的改性效果进行比较。结果发现，填充纳米CaCO3使PVC平衡扭矩和平衡熔融温度均会有所提高，填充未改性碳酸钙增加更大，填充PMMA包覆CaCO3使材料冲击性能提高的幅度大于填充未改性纳米CaCO3，而拉伸强度下降幅度较小。当PMMA包覆CaCO3填充量为8％时缺口冲击强度增加到未改性PVC的194％。冲击缺口断面形态分析表明，采用PMMA包覆CaCO3时，纳米CaCO3在PVC基体中分散均匀、团聚少。