Impact modification of thermoplastics by methyl methacrylate and styrene-grafted natural rubber latexes

The preparation and characterization of polymer blends with structured natural rubber (NR)-based latex particles are presented. By a semicontinuous emulsion polymerization process, a natural rubber latex (prevulcanized or not) was coated with a shell of crosslinked polymethylmethacrylate (PMMA) or polystyrene (PS). Furthermore, core–shell latexes based on a natural rubber/crosslinked PS latex semi-interpenetrating network were synthesized in a batch process. These structured particles were incorporated as impact modifiers into a brittle polymer matrix using a Werner & Pfleiderer twin screw extruder. The mechanical properties of PS and PMMA blends with a series of the prepared latexes were investigated. In the case of PMMA blends, relatively simple core (NR)–shell (crosslinked PMMA) particles improved the mechanical properties of PMMA most effectively. An intermediate PS layer between the core and the shell or a natural rubber core with PS subinclusions allowed the E-modulus to be adjusted. The situation was different with the PS blends. Only core–shell particles based on NR-crosslinked PS latex semi-interpenetrating networks could effectively toughen PS. It appears that microdomains in the rubber phase allowed a modification of the crazing behavior. These inclusions were observed inside the NR particles by transmission electron microscopy. Transmission electron photomicrographs of PS and PMMA blends also revealed intact and well-dispersed particles. Scanning electron microscopy of fracture surfaces allowed us to distinguish PS blends reinforced with latex semi-interpenetrating network-based particles from blends with all other types of particles.     

Radiation-induced grafting polymerization of MMA onto polybutadiene rubber latex

The grafting of methyl methacrylate (MMA) onto polybutadiene rubber latex by the direct radiation method was carried out. The effects of monomer concentration, absorbed dose and dose rate of gamma rays on the grafting yield were investigated. The graft copolymers were characterized by transmission electron microscopy (TEM), FTIR spectroscopy, and differential scanning calorimetry. TEM photographs revealed that the core–shell structures of latex particles are formed at low MMA content, and with the increasing of MMA content, the semi-IPN-like structure with core–shell could be developed due to the high gel fraction of polybutadiene (PBD) seed particles. In addition, infrared analysis confirmed that MMA could be grafted onto PBD molecular chains effectively under appropriate irradiation conditions. The interfacial adhesion between PBD rubber (core) and PMMA (shell) phases could be enhanced with the increase of MMA concentration.     

Effects of methyl methacrylate grafting and in situ silica particle formation on the morphology and mechanical properties of natural rubber composite films

The effects of methyl methacrylate (MMA) grafting and in situ formation of silica particles on the morphology and mechanical properties of natural rubber latex (NRL) were investigated. MMA grafting on NRL was carried out using cumyl hydroxy peroxide/tetraethylene pentamine (CHPO/TEPA) as a redox initiator couple. The grafting efficiency of the grafted NR was determined by solvent extractions and the grafted NRL was then mixed with tetraethoxysilane (TEOS), a precursor of silica, coated by adherence to a glass surface to form a film and cured at 80°C. The resultant products were characterized by FT‐IR and transmission electron microscopy. The influence of varying the MMA monomer weight ratio on the surface morphology of the composites was investigated by scanning electron and atomic force microscopy. The PMMA (poly MMA) grafted NRL particles were obtained as a core/shell structure from which the NR particles were the core seed and PMMA was a shell layer. The silane was converted into silica particles by a sol–gel process which was induced during film drying at 80°C. The silica particles were fairly evenly distributed in the ungrafted NR matrix but were agglomerated in the grafted NR matrix. The root‐mean‐square roughness increased with an increasing weight ratio of MMA in the rubber. The in situ silica particles in the grafted NR matrix slightly increased both the modulus and the tear strength of the composite film. Copyright © 2008 John Wiley & Sons, Ltd.     

Imaging of block copolymer vesicles in solvated state by wet scanning transmission electron microscopy

Morphology of polystyrene-block-poly(acrylic acid) vesicles was imaged by various modes of scanning electron microscopy (SEM), including recently developed wet scanning transmission electron microscopy (wet-STEM) by means of which we were able to follow the decrease in the thickness of a liquid solvent layer around the vesicles during controlled evaporation of water from the sample. Results show that wet-STEM allows for imaging of nanosized polymeric particles in the presence of the solvent.     

Studies on radiation grafting of methyl methacrylate onto natural rubber for improving modulus of latex film

Methyl methacrylate (MMA) can be grafted onto natural rubber (NR) in latex by gamma irradiation for improving the mechanical properties of the dry films. Physical blending of MMA-grafted NR latex with radiation vulcanized natural rubber latex (RVNRL) or simultaneous radiation grafting and crosslinking are found to be useful techniques for improving the properties of latex films. Moduli of the films are improved with increasing MMA content; however, tensile strength is reduced. High modulus without much reduction in tensile strength can be achieved if the MMA content is 50–60 parts per hundred rubber.     

Modification of natural rubber: A study by H NMR to assess the degree of graftization of polyDMAEMA or polyMMA onto rubber particles under latex form in the presence of a redox couple initiator

On the basis of the proposal that cumene hydroperoxide (CHP) in the presence of the base tetraethylenepentamine (TEPA) can form radicals by the abstraction reaction over addition to allylic double bonds, the efficiency of grafting monomers of methyl methacrylate (MMA) and dimethylaminoethylmethacrylate (DMAEMA) on to natural rubber (NR) has been studied. Seeded emulsion polymerization was used to graft such monomers. Different concentrations of each monomer have been examined. The effects of the concentrations of the monomers were evaluated by ¹H NMR spectroscopy and Transmission Electron Microscopy (TEM). There is good evidence for the formation of graft copolymers of modified NR under the core-shell morphology as well as satisfactory efficiency of grafting in the presence of high concentrations of both monomers. At lower concentrations the grafting were not significant. The images of the morphology was obtained by Transmission Electron Microscopy after the preparation of the samples by cryo-sectioning and chemical fixation techniques.     

Preparation of HPMC–EA–DMAEMA nanosized latex

Nanosized copolymer latex of hydroxypropylmethylcellulose (HPMC) grafted with ethyl acrylate (EA) and dimethylaminoethyl methacrylate (DMAEMA) has been prepared by acidifying submicron-sized latex particles synthesized by soap-free emulsion graft copolymerization using potassium persulfate (KPS) as initiator. The effects on the diameter of the latex particles of different conditions, for example concentration of DMAEMA, amount of HPMC, and ratio of HCl to DMAEMA for acidification, were investigated. It was found that increasing the mole ratio of HCl to DMAEMA to 1.0 and increasing the DMAEMA content both resulted in a decrease in particle diameter, whereas increasing the amount of HPMC resulted in larger particle sizes. Measurement by dynamic light scattering (DLS) revealed the diameter of the latex particles was >200 nm before acidification and <100 nm after acidification. Evidence of grafting was obtained by use of Fourier transform infrared (FTIR) spectroscopy. Transmission electron microscopy (TEM) was used to characterize the morphology of the copolymer particles before and after acidification.     

Skim and cream natural rubber particles: colloidal properties, coalescence and film formation

Cream and skim fractions of freshly tapped natural rubber latex have been studied using atomic force microscopy and scanning electric potential microscopy to elucidate the topology and charge properties in film formation. Elemental distribution maps of the particles have also been obtained using electron energy-loss imaging in a low-energy transmission electron microscope. The two rubber fractions are obtained by centrifugation. The cream fraction is stable while rapid coagulation occurs in the skim fraction. After removal of the coagulum, no further coagulation occurs and the remaining skim rubber particles are stable. The rubber particles from the cream rubber particles contain higher amount of adsorbed protein-phospholipid materials compared to those in the "self-cleaned" skim fraction. This difference in membrane property has a significant impact on the spreading of the cis-1,4-polyisoprene cores, their coalescence and film formation behavior. Coalescence of cream particles appears to be hindered by the membrane materials, forming a rough film that retains the topology of individual particles. Skim particles coalesce more readily, forming relatively smooth films.     

Modification of epoxidised natural rubber film surface by polymerisation of methyl methacrylate

Epoxidised natural rubber (ENR) latex, having 25% of epoxide content, was prepared by in situ epoxidation reaction using performic acid. The ENR latex film surface was modified by immersing into methyl methacrylate (MMA) emulsion and then alkaline aqueous solution of ferrous ion/fructose for redox-initiated polymerisation. Increasing polymerisation time caused an increase in percent conversion of MMA swelled in ENR sheet. The presence of poly(methyl methacrylate) on the ENR surface was examined by attenuated total reflection-Fourier transform infrared spectroscopy. The nano-scale indentation experiment performed on the cross-section of the modified ENR sheet indicated that MMA polymerisation occurred mainly near the rubber’s surface. The surface morphology observed under scanning electron microscopy and atomic force microscopy revealed a pronounced roughness which, consequently, decreased the friction coefficient of ENR surface.     

Investigation of Cationic Soapless P(St-co-DMAEMA) Latex and Its Electrostatic Adsorption of Laponite

Cationic poly(styrene-co-N,N-dimethylaminoethyl methacrylate)(P(St-co-DMAEMA)) latexes were prepared in the absence of surfactant by using 2,2'-azobis(2-methylpropionamidine) dihydrochloride(AIBA) as the initiator. The effects of the AIBA concentration, HCl/DMAEMA molar ratio and DMAEMA amount on the emulsion polymerization and the latex properties were investigated. The particle morphology and size, the zeta potential and the amino distribution of the P(Stco-DMAEMA) latexes were characterized by transmission electron microscope(TEM), dynamic light scattering(DLS) and conductometric titration, respectively. Results showed that the emulsion polymerization performed smoothly with high monomer conversion and narrow particle size distribution under the optimized conditions with AIBA concentration of1 wt%, HCl/DMAEMA molar ratio of 1.2 and DMAEMA content of 5 wt%. The diameter of the dried latex particles decreased and the density of amino groups on the particle surfaces increased with increasing the DMAEMA content. The zeta potential of the P(St-co-DMAEMA) latexes was p H-dependent and the zero point was around at p H 7.2. A facile method was developed to fabricate P(St-co-DMAEMA)/laponite hybrid nanoparticles via electrostatic adsorption, in which the loading capacity of laponite platelets reached 17.7 wt%, and the resultant hybrid nanoparticles showed good thermal stability.     

Investigation of cationic soapless P(St-<Emphasis Type="Italic">co</Emphasis>-DMAEMA) latex and its electrostatic adsorption of laponite

Cationic poly(styrene-co-N,N-dimethylaminoethyl methacrylate) (P(St-co-DMAEMA)) latexes were prepared in the absence of surfactant by using 2,2’ -azobis (2-methylpropionamidine) dihydrochloride (AIBA) as the initiator. The effects of the AIBA concentration, HCl/DMAEMA molar ratio and DMAEMA amount on the emulsion polymerization and the latex properties were investigated. The particle morphology and size, the zeta potential and the amino distribution of the P(St-co-DMAEMA) latexes were characterized by transmission electron microscope (TEM), dynamic light scattering (DLS) and conductometric titration, respectively. Results showed that the emulsion polymerization performed smoothly with high monomer conversion and narrow particle size distribution under the optimized conditions with AIBA concentration of 1 wt%, HCl/DMAEMA molar ratio of 1.2 and DMAEMA content of 5 wt%. The diameter of the dried latex particles decreased and the density of amino groups on the particle surfaces increased with increasing the DMAEMA content. The zeta potential of the P(St-co-DMAEMA) latexes was pH-dependent and the zero point was around at pH 7.2. A facile method was developed to fabricate P(St-co-DMAEMA)/laponite hybrid nanoparticles via electrostatic adsorption, in which the loading capacity of laponite platelets reached 17.7 wt%, and the resultant hybrid nanoparticles showed good thermal stability.     

SBA/PVC复合树脂的制备与表征

采用聚丙烯酸正丁酯(PBA)改性的丁苯(SBR)胶乳为种子乳液(SBA),通过乳液接枝共聚氯乙烯制备了SBA/PVC复合树脂.通过粒径分析仪、动态力学分析仪(DMA)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)等测试手段,表征了复合胶乳粒的粒径与形态,以及材料的形态结构.粒径分析表明PVC确实包覆在SBA上;TEM研究结果显示SBA/PVC胶乳粒子呈现明显的核壳结构,PBA加入可提高SBR在复合材料中的分散性;DMA分析表明SBA/PVC复合树脂在低温区呈现了一个宽而弱的转变峰,揭示了接枝过渡层的微观结构特征;研究了交联剂和PBA用量对材料性能的影响,结果表明在PBA含量较低时,SBA/PVC复合树脂就显示了优良的冲击性能,且SEM照片显示材料断面形貌为特征性韧性断裂.     

AFM imaging and characterization of latex particles formed by copolymerization of styrene and poly(ethylene oxide) macromonomer

A new type of latex particle was prepared by copolymerization of styrene and poly(ethylene oxide) macromonomer. By controlling the concentration of styrene in reaction mixtures, several latexes with different grain sizes were obtained. The packing patterns of the latex films as well as shapes and sizes of the latex particles were measured with atomic force microscopy (AFM). AFM images revealed that the grain sizes of the latexes increase with increasing concentration of styrene. At a higher styrene concentration (10 wt%), the latex showed a rather homogenous distribution of grain sizes. Lateral force microscopy (LFM) was used to reveal frictional features of latex particles. Contact and non-contact mode AFM were employed to image the same sample of the latex films. The results show that AFM working in non-contact mode can be used to effectively eliminate the horizontal-line-like artifacts, which may obscure AFM images.     

种子乳液聚合法制备多孔乳胶粒

用批量乳液聚合法制备了苯乙烯（Ｓｔ）———甲基丙烯酸甲酯（ＭＭＡ）二元共聚种子乳液Ｓ１以及Ｓｔ ＭＭＡ 丙烯酸（ＡＡ）三元共聚种子乳液Ｓ２,通过连续法无皂种子乳液聚合合成了一系列不同ＡＡ或ＭＡＡ（甲基丙烯酸）含量的Ｓｔ、ＭＭＡ三元共聚乳液．将所得复合胶乳进行碱／酸分步处理,得到具有多孔结构的乳胶粒．用透射电镜对胶粒形态进行了表征,考察了不饱和酸种类和用量、碱处理初始ｐＨ值及溶胀剂对胶粒成孔的影响．     

Influence of hydrophobic monomers on secondary nucleation of hydroxyl‐functionalized latexes

The influence of butyl acrylate (BA) and methyl methacrylate (MMA) on hydroxyl functionalized latexes was investigated. The hydrophobicity of the monomer feed was varied via the BA/MMA ratio. In addition to monitoring the effect of hydrophobic monomer feed on secondary nucleation, the polymerization kinetics and final latex properties were also obtained for comparison. Five different BA to MMA molar ratios were combined with five 2‐hydroxyethyl methacrylate (HEMA) concentrations (0, 10, 20, 30 and 40 mol% in monomer composition). All latexes were synthesized through seeded semibatch emulsion polymerization process. Particle size distributions and average particle sizes of the latexes were determined by dynamic light scattering (DLS) and qualitatively compared with transmission electron microscope (TEM) images. The BA to MMA ratio significantly influences the boundary HEMA concentration at which homogeneous secondary nucleation occurs. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2190–2202     

The characterization of latex particles prepared by pulsed electron beam induced emulsion polymerization

The emulsion polymerization of styrene (St) and methyl methacrylate (MMA) induced by 10 MeV pulsed electron beams (PEB) was investigated. The monomer conversion of MMA and St was found to be very low so that the final prepared poly(methyl methacrylate) (P(MMA)) and polystyrene (PS) latex particles exhibit porous structures, as verified by TEM and SEM observations. The results of dynamic light scattering (DLS) and gel permeation chromatography (GPC) showed that both the particle size and the molecular weight of PS and PMMA latexes decrease with the increase of the absorbed dose. However, the molecular weights and the particle sizes of the PS and PMMA latexes change differently with the irradiation time. This work indicated that emulsion polymerization induced by high energy electron beam has an advantage over that induced by γ-ray or chemical initiators in the preparation of latex with a low molecular weight and porous structure.     

Study on grafting of different types of acrylic monomers onto natural rubber by γ-rays

 A comparative study of various acrylic monomers for grafting onto natural rubber was done. The stability of natural rubber latex (NRL) against coagulum with monomer, mechanical properties of grafted rubbers and percent of grafting were investigated. The NRL with monomers, methylacrylate (MA), ethylacrylate (EA) and n-butylacrylate (n-BA), is unstable but it is stable with methyl methacrylate (MMA), n-butyl methacrylate (BMA) and cyclohexyl methacrylate (CHMA). The mechanical properties and degree of grafting attained a maximum at a total radiation dose of 4 kGy. The values of tensile properties of MMA and CHMA grafted rubbers are almost similar, and higher than those of BMA grafted rubbers. On the other hand, the degree of grafting for CHMA is higher than those of MMA and BMA grafted rubbers. The infrared (IR) spectra of monomer grafted natural rubber were also studied.     

Nano-matrix structure formed by graft-copolymerization of styrene onto natural rubber

Nano-matrix structure was formed by graft-copolymerization of styrene onto urea-deproteinized natural rubber (U-DPNR) latex. The grafted U-DPNR was characterized by FT-IR spectroscopy, ¹H NMR spectroscopy and transmission electron microscopy. Conversion and grafting efficiency of styrene were more than 90% under the best condition of the graft-copolymerization. In transmission electron micrograph of film specimen stained by OsO₄, it was found that natural rubber particle of about 0.5 μm in diameter was dispersed in polystyrene matrix of about 15 nm in thickness. The conversion and grafting efficiency for the grafted U-DPNR were compared with those for a control sample prepared from enzymatic deproteinized natural rubber (E-DPNR) with styrene.     

The effect of electrolyte on the colloidal properties of poly(N-isopropylacrylamide-co-dimethylaminoethylmethacrylate) microgel latexes

Monodisperse cationic thermosensitive latex microgels prepared by radical-initiated precipitation copolymerization of N-isopropylacrylamide (NIPAM), methylenebisacrylamide, and dimethylaminoethylmethacrylate (DMAEMA) have been reported (Zha LS, Hu JH, Wang CC, Fu SK, Elaissari A, Zhang Y 2002 Colloid Polym Sci 280:1) and we suggested (Zhang Y, Zha LS, Fu SK J Appl Polym Sci) that the polyelectrolyte chains are rich in their expanded shell layers. The effect of a range of electrolytes on several colloidal properties of these cationic latexes (such as particle size, zeta potential and colloidal stability) has been investigated. The ability of the anions to induce the particle deswelling and flocculation is related to their position in the Hofmeister series. Owing to the DMAEMA-rich layer on the latex particles, the ionic-strength dependence of the particle hydrodynamic size and the zeta potential become more profound with increasing amount of DMAEMA incorporated into the microgel. It is suggested that the effect of electrolytes on the colloidal properties of the copolymer microgel latexes is attributed to the dehydration of the poly(NIPAM) segment and the screening of the electrostatic interaction between the charged DMAEMA units induced by electrolytes.     

MORPHOLOGY EVOLUTION OF POLY（St-co-BuA）/SILICA NANOCOMPOSITE PARTICLES SYNTHESIZED BY EMULSION POLYMERIZATION

Poly（St-co-BuA）/silica nanocomposite latexes were synthesized via conventional emulsion polymerization in the presence of 3-（trimethoxysilyl）propyl methacrylate modified colloidal nano-silica. The effects of surface property, particle size and content of colloidal nano-silica as well as the concentrations of monomer and surfactant on the morphology of nanocomposite latex particles were investigated by transmission electron microscope （TEM） and scanning electron microscope （SEM） in detail. Various interesting morphologies such as grape-like, Chinese gooseberry-like, pomegranate-like and normal core-shell structures were observed. Droplet nucleation mechanism competing with micelle nucleation mechanism was proposed to explain the morphological evolution of the nanocomposite particles.