Development of self-healing coatings based on urea-formaldehyde/polyurethane microcapsules containing epoxy resin

In this study, the synthesis of urea-formaldehyde/polyurethane (UF/PU) microcapsules containing epoxy resin for self-healing and anti-corrosion coatings with good stability has been reported. Spherical microcapsules were prepared with a diameter of about 50–720 μm and a shell thickness of 0.6–0.7 μm via in situ polymerization in an oil-in-water emulsion using 2,4-toluene diisocyanate-based pre-polymer along with the urea-formaldehyde. Scanning electron microscopy (SEM) and optical microscopy (OM) were employed to evaluate the shape and morphology of the microcapsules. Fourier transform infrared (FTIR) spectroscopy showed the absence of free isocyanate groups within the microcapsule shell confirming the completion of shell formation reactions. OM illustrated that the microcapsules were stable over a period of 30-days in toluene and xylene. Increasing microcapsule loading improved crack repairing and anti-corrosion performance of the coating layer. Low-carbon steel coupons coated with an epoxy resin containing 10 wt% microcapsules and scribed using a scalpel blade showed no visible sign of corrosion after up to 5 weeks of exposure in a standard salt spray test chamber.     

原位聚合法制备脲醛树脂包覆环氧树脂微胶囊

以脲醛树脂为囊壁、环氧树脂E-51的乙酸乙酯溶液为囊芯,采用原位聚合法成功制备了脲醛树脂包覆环氧树脂溶液的微胶囊。通过改变尿素、甲醛、芯材用量等研究了脲醛树脂生成速率和沉积速率对微胶囊形貌和结构的影响。利用扫描电子显微镜、光学显微镜、傅里叶变换红外光谱仪和热重分析仪对微胶囊进行表征。结果表明:成功制备了外表面粗糙和光滑的两种微胶囊,且这两种微胶囊的芯材都具有良好的流动性;外表面粗糙的微胶囊力学性能较好,热稳定性优良。     

Particle features of a poly(methyl methacrylate) resin prepared by a new emulsion polymerization process

A new emulsion polymerization process, in which water acted as the dispersed phase and a mixture of methyl methacrylate (MMA) and cyclohexane acted as the continuous phase, was applied to the preparation of a poly(methyl methacrylate) (PMMA) resin. The primary (latex) particles were formed in the early stage of polymerization and coagulated as the polymerization conversion increased. Scanning electron micrographs showed that the final PMMA particles were porous and composed of loosely aggregated primary particles. The porosity characterized by cold di(2‐ethylhexyl) phthalate absorption increased as the water/oil and cyclohexane/MMA mass ratios increased. The PMMA primary particles were smaller than the primary particles in the PMMA resin prepared by suspension polymerization in the presence of cyclohexane. Because of the phase composition of the reaction system, the solubility of PMMA in a mixture of cyclohexane and MMA, and the particle morphology of PMMA, a particle formation mechanism, including the formation, growth, and coagulation of primary particles in dispersed water droplets, was proposed. The primary particles formed mainly through a homogeneous nucleation mechanism and increased in size as MMA diffused from the oil phase to the water phase to the primary particles. The coagulation of the primary particles occurred because of the lower colloidal stability and the space limitations of the primary particles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1905–1911, 2004     

Transparent antifouling coatings via nanoencapsulation of a biocide

Transparent coatings releasing an antifouling agent (AF) can be used to reduce the marine fouling of optical lenses. A variety of water‐borne coatings based on poly(methyl methacrylate‐co‐butyl acrylate) (PMMA‐co‐PBA) were synthesized using a two‐stage miniemulsion process. During this process, the AF, SeaNine 211, was nanoencapsulated in domains small enough not to scatter light. The release rate of SeaNine 211 was studied for the polymers of different T_g, and found to be sufficient to impart AF properties. However, over time, the coatings were found to develop a whitish aspect (blushing) due to water retrodiffusion. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Polymeric coatings based on acrylic resin latexes from miniemulsion polymerization using hydrocarbon resins as osmotic agents

Waterborne acrylic resins with a solid content higher than 40 wt % were obtained by miniemulsion polymerization of methyl methacrylate, butyl acrylate, and acrylic acid using a hydrocarbon coumarone–indene resin (HCR) as osmotic agent. HCR is a cheap polymer widely used for coatings and pressure‐sensitive adhesives. The resin leads to a higher hydrophobicity for the acrylic latex film and acts as osmotic agent in miniemulsion polymerization preventing Ostwald ripening, leading to latexes with particle sizes, size distributions, and stability comparable to those obtained using n‐hexadecane as osmotic agent. However, the monomer conversion and molecular weight were lower, indicating the occurrence of a chain‐transfer reaction. Atomic force microscopy analysis demonstrated that a smooth film surface with phase‐separated morphology was formed when using HCR. Faster film hardness development was achieved with HCR comparing with hexadecane. Compared with market standard in a paint formulation, a similar performance was achieved. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40569.     

Effect of nanoparticles on the morphology and thermal properties of self-healing poly(urea-formaldehyde) microcapsules

The preparation of microcapsules with adequate performance is required for the fabrication of self-healing composites. Self-healing microcapsules with improved morphology as well as thermal and water resistance were prepared by introducing either single-walled carbon nanotubes (SWCNTs) or aluminum oxide nanoparticles (nano-alumina) into a urea–formaldehyde resin (which acts as the wall material). The prepared microcapsules were studied using various characterization techniques, including Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), optical microscopy (OM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and contact-angle measurements. Based on comparisons with traditional poly(urea–formaldehyde) microcapsules, the modified microcapsules exhibited a smoother surface. Our results indicate that the presence of the nanoparticles did not affect the core content of the microcapsules, which was approximately 78 wt.%. The average size of the traditional microcapsules was reduced from 168 μm to 115 and 95 μm for the SWCNT- and nano-alumina-modified microcapsules, respectively. In addition, the thermal resistance of the microcapsules was improved after modifying the capsule walls. After the microcapsules had been modified with SWCNTs, the water resistance of the capsules improved, and the contact angle increased from 44° to 50°.     

Dispersion of nanoparticles in poly(vinyl chloride) grains during In situ polymerization

Inorganic nanoparticles such as calcium carbonate, silica, or hydrotalcite were dispersed in vinyl chloride prior to suspension polymerization. That led to the production of poly(vinyl chloride) (PVC) composite grains with higher porosity and different internal morphology from those of commercial PVC. The PVC/composite grain sizes and their distribution were also influenced by the presence of nanofillers. The distribution of filler nanoparticles (either calcium carbonate or silica) was not uniform throughout the PVC grains. Regions of high and low filler concentration were observed. Regions of pure polymer were also observed. Reasons for that are suggested. Hydrotalcite did not remain in the PVC grains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Properties of poly(n‐butyl methacrylate) prepared by reverse atom transfer radical polymerization in an aqueous dispersed system

Reverse atom transfer radical polymerization (ATRP) of n‐butyl methacrylate (BMA) in waterborne media using Cu(II) complexes with azo initiators (i.e., reverse ATRP) was conducted. The influence of several factors, such as surfactant, catalyst, and reaction time, on the stability of the emulsion, the particle size, the morphology of the emulsion particles, and the control of the polymerization was investigated. The results showed great differences between ATRP and conventional emulsion polymerization, especially the nucleation mechanism and the kinetics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1542–1547, 2003     

Self film‐forming and opaque hollow latexes fabricated via seeded emulsion polymerization followed by alkali post‐treatment

In order to obtain novel hollow latexes with both opaque and self film‐forming properties, the four‐layer core/shell latex particles—sequentially consisting of a high carboxyl‐containing soft core, a transition layer, a rigid supporting layer, and an outermost film‐forming layer—are first designed and prepared by emulsion polymerization, and then treated with alkali to fabricate self film‐forming hollow latexes. On the basis of the previous research on the three‐layer core/shell latex, influences of the composition and thickness of the film‐forming layer on the properties and morphologies of the four‐layer core/shell and the final hollow latexes are investigated. Results show that under optimized conditions with butyl acrylate/styrene (BA/St) mass ratio of 2/1, divinyl benzene (DVB) content of 1 wt %, and core/film‐forming layer mass ratio of 1/6 in the film‐forming layer preparation, the final hollow latex particles exhibit best morphology considering both light scattering efficiency and film‐forming capability at room temperature. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42541.     

Preparation of poly(methyl methacrylate)/titanium oxide composite particles via in‐situ emulsion polymerization

Poly(methyl methacrylate) (PMMA)/Titanium oxide (TiO₂) composite particles were prepared via in‐situ emulsion polymerization of MMA in the presence of TiO₂ particles. Before polymerization, the TiO₂ particles was modified by the silane coupling agent, which is crucial to ensure that PMMA reacts with TiO₂ via covalent bond bindings. The structure of the obtained PMMA/TiO₂ composite particles was characterized using Fourier transform infrared spectra (FTIR) and thermogravimetric analysis (TGA). The results indicate that there are covalent bond bindings between PMMA macromolecules and TiO₂ particles. Based on these facts, several factors affecting the resulting PMMA/TiO₂ composite system, such as the type of coupling agents, the mass ratio of the MMA to the modified TiO₂, the emulsifier concentration, and the initiator concentration, etc., were examined by the measurement of conversion of monomers, the gel content of polymers, the percentage of grafting, and the grafting efficiency, using gravity method or TGA method. As a result, the optimized recipe was achieved, and the percentage of grafting and the grafting efficiency could reach 216.86 and 96.64%, respectively. In addition, the obtained PMMA/TiO₂ composite particles were found to a stable colloidal dispersion in good solvent for PMMA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4056–4063, 2006     

Morphology of poly(butyl acrylate)/poly(styrene‐co‐methyl methacrylate) latex prepared by starved emulsion polymerization: II. Development of particle morphology

Heterogeneous latexes were prepared by a two‐stage seeded emulsion polymerization process under monomer starved conditions at 80 °C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(butyl acrylate) latexes were used as seeds. The second‐stage polymer was poly(styrene‐co‐methyl methacrylate). By varying the amount of methyl methacrylate (MMA) in the second‐stage copolymer, the polarity of the copolymer phase could be controlled. It was found that the latex particles displayed different morphologies depending on the monomer ratio. The amount of MMA had a significant effect on the evolution of morphology. The morphologies were observed by transmission electron microscopy. In addition, the evolution of the particle morphology was predicted by the mathmatical model for cluster migration. The model gave the same trends as the experimental results. © 2002 Society of Chemical Industry     

Modification of halloysite nanotubes with poly(styrene–butyl acrylate–acrylic acid) via in situ soap‐free graft polymerization

Halloysite nanotubes (HNTs) were grafted with poly(styrene–butyl acrylate–acrylic acid) (P‐SBA) via an in situ soap‐free emulsion polymerization. To introduce double bonds into the HNTs, N‐(β‐aminoethyl)‐γ‐aminopropyl trimethoxysilane was first used to modify the HNTs and render amino groups, and then, the double bonds were anchored through an amidation reaction between acryloyl chloride and amino groups. P‐SBA chains were grafted onto HNTs because of participating of double bonds in the copolymerization of styrene, butyl acrylate, and acrylic acid. Fourier transforms infrared spectroscopy, transmission electron microscopy, specific surface area measurements, and thermogravimetric analysis were used to characterize the HNTs grafted with P‐SBA. The results indicate that 25.21% of P‐SBA was grafted onto the outer walls of the HNTs and filled into the inner spaces of the HNTs. The modification dramatically decreased the surface area of the HNTs. The property study of the HNTs grafted with P‐SBA focused on the dispersion behavior in the biphase system. The results show that the grafted HNTs dispersed stably in the water/cyclohexane biphase system and were a potential emulsifier. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Doxorubicin‐loaded poly(butylcyanoacrylate) nanoparticles produced by emulsifier‐free emulsion polymerization

ABSTRACT: Doxorubicin‐loaded poly(butylcyanoacrylate) (PBCA) nanoparticles (NPs) were prepared by an emulsifier‐free emulsion polymerization technique. The pH values of the polymerization medium and the weight ratios of doxorubicin to butylcyanoacrylate had a significant effect on the mean particle size. The particle diameter determined by transmission electron microscopy showed that the nanoparticles were predominantly less than 50 nm. Drug loading and entrapment efficiency increased with increasing pH of the medium. The surface tension of the polymerization media increased with increasing polymerization time and reached a plateau after 4 h. Doxorubicin‐loaded PBCA NPs carried a positive charge, and the zeta potential of drug‐loaded nanoparticles increased with the increase of the polymerization pH. Molecular weight, analyzed by gel permeation chromatography, showed that the nanoparticles mainly consisted of oligomers of PBCA. The release rate of doxorubicin from nanoparticles in biological phosphate buffer was very slow, with a half‐life of 111.43 h. The results indicate that drug‐loaded nanoparticles can be prepared by an emulsifier‐free emulsion polymerization technique and that the resulting nanoparticles might be suitable for targeting drug delivery vehicles for clinical application. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 517–526, 2000     

Synthesis of poly(butyl acrylate)‐poly(methyl methacrylate) core–shell nanomaterials of anti‐crease‐whitening properties

Core–shell nanomaterials of poly(butyl acrylate)‐poly(methyl methacrylate) were synthesized using a differential microemulsion polymerization method for being used as polyacrylate‐based optical materials, which meet the requirement of anti‐crease‐whitening and proper mechanical strength. The effects of reaction temperature and surfactant amount on the particle sizes, as well as the effect of reaction temperature on the conversion and solid content were investigated to reveal the dependence of the application properties on the reaction conditions. The spherical morphology of core–shell nanoparticles was also studied via transmission electron microscopy. The resulting polymers with a core–shell monomer ratio of butyl acrylate/methyl methacrylate at 32/10 (vol/vol) demonstrated the optimal balanced properties in the anti‐crease‐whitening and mechanical property, confirmed by the visible light transmittance measurement and the dynamic analysis of the viscoelastic properties of the synthesized core–shell nanomaterials. The smaller the particle size, the better the transparency of the resulting polymer films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39991.     

Complexation of poly(dimethylsiloxane)/poly(methyl methacrylate‐co‐butyl acrylate‐co‐methacrylic acid) latex with poly(dimethylsiloxane)/poly(vinyl acetate‐co‐butyl acrylate) latex

Two latices—the poly(dimethylsiloxane) (PDMS)/poly(methyl methacrylate‐co‐butyl acrylate‐co‐methacrylic acid) system (PA latex) and the PDMS/poly(vinyl acetate‐co‐butyl acrylate) system (PB latex)—were prepared by seeded emulsion polymerization, and PA/PB complex latices were obtained through the interparticle complexation of the PA latex with the PB latex. In addition, for the further study of the interparticle complexation of the PA latex with the PB latex, copolymer latices [PDMS/methyl methacrylate‐co‐butyl acrylate‐co‐vinyl acetate‐co‐methacrylic acid) (PC)] were prepared according to the monomer recipe of the complex latices and the polymerization process of the component latices. The properties of the obtained polymer latices and complex latices were investigated with surface‐tension, contact‐angle, and viscosity measurements. The mechanical properties of the coatings obtained from the latices were investigated with tensile‐strength measurements. The results showed that, in comparison with the two component latices (PA latex and PB latex) and the corresponding copolymer latices (PC latices), the PA/PB complex latices had lower surface tension, lower viscosities, and better wettability to different substrates. The tensile strengths of the coatings obtained from the complex latices were higher than the tensile strengths of the coatings from the two component latices and copolymer latices. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2522–2527, 2004     

一步法制备聚脲甲醛包覆反应性乙烯基硅油微胶囊

以聚脲甲醛(PUF)为囊壁,乙烯基硅油为囊芯,采用原位聚合"一步法"成功制备出具有自修复功能且粒径均匀的新型PUF包覆乙烯基硅油微胶囊。研究了分散剂/表面活性剂种类及用量、m(囊芯)∶m(囊壁)比例对微胶囊物理性能的影响,并通过扫描电镜(SEM)、金相显微镜、激光粒度分析仪和红外光谱(FT-IR)法等对微胶囊的形貌、粒径大小等进行了研究。结果表明:选用较高浓度的聚乙烯醇(PVA1799)作为分散剂时,有利于微胶囊的形成;当w(PVA1799)=3.00%(相对于体系总质量而言)、m(囊芯)∶m(囊壁)=2.8∶1.0时,在1500r/min条件下,可制备出平均粒径小于20μm且粒径分布较均匀的理想微胶囊。     

Influences of the polymerization ingredients on the porous morphology of soap‐free poly(methyl methacrylate/ethyl acrylate/methacrylic acid) seeded latex particles

Monodispersed soap‐free poly(methyl methacrylate/ethyl acrylate/methacrylic acid) latex particles were synthesized by the seeded emulsion polymerization of methyl methacrylate, ethyl acrylate, and methacrylic acid (MAA), and particles with a porous morphology were obtained after an alkali posttreatment. The effects of the unsaturated acid and crosslinking agent on the properties and morphology of the latex particles were investigated. The results showed that the particle size decreased and its distribution widened when the concentration of MAA was greater than 10.0 mol % or the concentration of ethylene glycol dimethacrylate (EGDMA) was greater than 1.5%. When more than 4.0 mol % MAA was used, a porous structure could be detected clearly under a transmission electron microscope, and the particle volume and pore size first gradually increased to a maximum and then decreased rapidly with an increase in the MAA concentration. The porous morphology disappeared completely as the MAA concentration reached 16.0 mol %. A multihollow morphology was generated when the EGDMA concentration exceeded 1.0%, and the particle volume decreased monotonously with the concentration of EGDMA increased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1934–1939, 2006     

Synthesis of chitosan‐modified poly(methyl methacrylate) by emulsion polymerization

Emulsion polymerization of methyl methacrylate (MMA) in the presence of chitosan was studied and a reaction mechanism was proposed. It was proved in the companion article that potassium persulfate (KPS) free radicals can degrade chitosan chains into chain free radicals. Therefore, it is possible to produce a chitosan copolymer when the monomer and the KPS initiator are added into the chitosan solution. According to the proposed mechanism, concentrations of different species such as the initiator, total free radicals, and degraded chitosan chain were calculated with the reaction time. All the results agreed with the experimental observation. The results showed that the polymerization rate varied with 0.83‐ and 0.82‐order of the total free‐radical concentration and chitosan repeating unit concentration, respectively. It was also verified that chitosan played multiple roles in the reaction system. If the monomer was added into the chitosan solution before the addition of KPS, chitosan served mainly as a surfactant. Consequently, the polymer particle number was increased with the chitosan addition and so was the polymerization rate. However, if the monomer was added into the solution where the chitosan was already degraded by KPS, the polymerization rate was decreased with the predegradation time of chitosan. In both cases, the final polymer particles consisted of the poly(methyl methacrylate) (PMMA) homopolymer and the chitosan‐PMMA copolymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3047–3056, 2002     

Preparation of hemispherical poly(4‐vinylpyridine‐co‐butyl acrylate)/poly(styrene‐co‐butyl acrylate) composite microspheres by seeded preswelling emulsion polymerization

Seeded preswelling emulsion polymerization was carried out by using monodispersed poly(4‐vinylpyridine‐co‐butyl acrylate) [P(4VP‐BA)] particles as the seed, and styrene and butyl acrylate as the second‐stage monomers under different polymerization conditions, to obtain hemispherical polystyrene (PST)‐rich–P4VP‐rich microspheres. Prior to polymerization, toluene was added into the preswelling system together with the second‐stage monomers. It was found that, with the increase of the amount of toluene, the particle morphology showed a tendency toward desirable hemispherical structure, and the colloidal stability of composite latex was improved. When the weight ratio of toluene/seed latex was increased up to 7.5/40 (g/g), the stable hemispherical latex could be obtained. However, when toluene was not added, the coagulum formed on the wall of the reactor during polymerization, and the composite particles with multiple surface domains (such as sandwich‐like, popcorn‐like) were formed. In addition, the final morphology of composite particles was influenced by the polarity of the seed crosslinker and the hydrophilicity of the second‐stage initiator, which could affect the mobility of poly(styrene‐co‐butyl acrylate) [P(ST‐BA)] chains. The morphology development during the polymerization was investigated in detail, and a schematic model was derived to depict the formation mechanism of hemispherical P(4VP‐BA)/P(ST‐BA) composite microspheres. The results revealed that the mobility of the P(ST‐BA) chains influenced the diffusion of the P(ST‐BA) domains on the surface of the P(4VP‐BA) matrix. When the mobility of the P(ST‐BA) chains allowed small‐size P(ST‐BA) domains to coalesce into one larger domain, complete phase‐separated morphology (hemisphere) could be achieved. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3811–3821, 2003