Preparation and surface properties of core‐shell polyacrylate latex containing fluorine and silicon in the shell

The core‐shell polyacrylate latex particles containing fluorine and silicon in the shell were successfully synthesized by a seed emulsion polymerization, using methyl methacrylate (MMA) and butyl acrylate (BA) as main monomers, dodecafluoroheptyl methacrylate (DFMA), and γ‐(methacryloxy) propyltrimethoxy silane (KH‐570) as functional monomers. The influence of the amount of fluorine and silicon monomers on the emulsion polymerization process and the surface properties of the latex films were discussed, and the surface free energy of latex films were estimated using two different theoretical models. The emulsion and its films were characterized by particle size distribution (PSD) analysis, transmission electron microscopy (TEM), Fourier transform infrared spectrum (FTIR), nuclear magnetic resonance (¹H‐NMR and ¹⁹F‐NMR) spectrometry, contact angle (CA) and X‐ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and thermogravimetry (TG) analysis. The results indicate that the average particle size of the latex particles is about 160 nm and the PSD is narrow, the synthesized latex particles exist with core‐shell structure, and a gradient distribution of fluorine and silicon exist in the latex films. In addition, both the hydrophobicity and thermal stability of the latex films are greatly improved because of the enrichment of fluorine and silicon at the film‐air interface, and the surface free energy is as low as 15.4 mN/m, which is comparable to that of polytetrafluoroethylene (PTFE). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of fluorine‐containing polyurethane–acrylate core–shell emulsion

Fluorinated polyurethane–acrylate (FPUA) hybrid emulsion was prepared by copolymerization of polyurethane, methyl methacrylate, and 1H,1H,2H,2H‐heptadecafluorooctyl acrylate (FA) via emulsion polymerization in the presence of a perfluoronated reactive surfactant. The polyurethane was synthesized from isophorone diisocyanate, poly(propylene glycol)‐1000, dimethylolpropionic acid, 1,4‐butanediol, and 2‐hydroxyethyl methylacrylate. The influence of the monomer on the surface properties, wetting behaviors, particle size, and viscosity of the emulsion was investigated. The mechanical properties of FPUA latex films were improved, and water absorption and contact angle were improved with the addition of methyl methacrylate and FA. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43357.     

The effect of octamethylcyclotetrasiloxane (D4) addition on the structure and properties of film‐forming polyacrylate/silica core–shell composite particles

The film‐forming polyacrylate/silica core–shell nanocomposite particles with octamethylcyclotetrasiloxane (D₄) were successfully synthesized via aqueous emulsion polymerization in the presence of a glycerol‐functionalized nano silica sol. The ring‐opening polymerization of D₄ and the reaction with the glycerol‐functionalized nano silica particles before emulsion polymerization was the key procedure in this process. Transmission electron microscopy results showed that more nano silica particles tended to coat on the polyacrylate particles surface after the nano silica sols were modified with D₄. The silica aggregation efficiency was increased from 90.9 to 98.6% when the amount of D₄ used in the system was varied from 0 to 8.0 wt %. The transparency of the nanocomposite films was not compromised after D₄ was incorporated into the system. The films of the nanocomposite particles with or without D₄ both exhibited superior abrasive resistance. Furthermore, the water resistance and hydrophobicity of the films of these particles with D₄ were also improved significantly. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42003.     

Effect of 2‐ethylhexyl acrylate and N‐acryloylmorpholine on the properties of polyurethane/acrylic hybrid materials

A hybrid synthesis technology was used to prepare waterborne polyurethane/acrylic hybrid emulsions by polymerization of methyl methacrylate, butyl acrylate, 2‐ethylhexyl acrylate(EHA), and N‐acryloylmorpholine (AMCO) in presence of acrylic‐terminated PU dispersion. Various characterization methods were used to investigate the effect of EHA and ACMO content on the properties of the hybrid emulsions and their resultant films. The research results show that the introduction of EHA can enhance the elasticity of their films, meanwhile, ACMO endows the film with high gloss, adhesion on substrate, toughness, and hardness. Mixing the two monomers leads to yield the hybrid materials with moderate properties. While increasing the weight ratio of ACMO/EHA, the average particle size of the hybrid emulsions increases and their viscosity decreases. For the resultant films, their surface water contact angle, adhesion on substrates, tensile strength, and hardness increase, but the water resistance and elasticity decrease. It has been found that EHA and ACMO have a synergistic effect on gloss of the hybrid films and the hydrogen bond interaction increases with an increase in the ACMO content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41463.     

Synthesis and characterization of crosslinking waterborne fluorinated polyurethane‐acrylate with core‐shell structure

Crosslinking core‐shell emulsions of waterborne fluorinated polyurethane‐acrylate (WFPUA) were successfully synthesized using a solvent‐free method. The crosslinkers of diacetone acrylamide and adipic dihydrazide were introduced into the WFPUA emulsions. The physical properties of hybrid emulsions such as the average particle size, stability, and viscosity were characterized. The core‐shell of crosslinking WFPUA emulsion synthesized in this study was observed by transmission electron microscopy. Then, the results of Fourier transform infrared spectroscopy, atomic force microscopy, and X‐ray photoelectron spectroscopy indicated that the fluorinated monomer (FA) had been polymerized into the crosslinking waterborne polyurethane‐acrylate polymer, and the fluorinated groups have evident enrichment on the film‐air surface with the increase of FA content. At the same time, the thermal properties, water repellent/antifouling properties, and mechanical properties were measured. Moreover, the thermal properties and the elongation are raised but tensile stress and shore hardness are decreased with the increase of FA content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40970.     

Core‐shell latex synthesized by emulsion polymerization using an alkali‐soluble resin as sole surfactant

A series of alkali‐soluble resins were prepared from esterification reaction of styrene‐maleic anhydride copolymer (SMA) and four fatty alcohols having different alkyl chains. The critical aggregates concentration of the prepared hemiester was lower than SMA, indicating that modification of SMA resin with long alkyl chains could improve their emulsification efficiency. The detailed experiments of emulsion polymerization of methyl methacrylate and butyl acrylate using these hemiesters as sole surfactants showed that SMA‐C12‐75, SMA‐C14‐70, and SMA‐C16‐65 were good surfactants. In the end, we successfully prepared stable latexes using above three good surfactants with relatively low surfactant concentration and high solid content. Characterization of latexes by Zetasizer and transmission electron microscopy revealed that particles of these latexes have core‐shell nanostructure with average particle size below 60 nm. Compared with SMA, the improvement of emulsification efficiency of its hemiesters may come from the better hydrophilic‐lipophilic balance and steric stabilization after incorporation of long alkyl chain. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Simple method of related sensitivity range to predict the thermodynamic equilibrium morphology of a core–shell latex particle

The equilibrium morphologies of different core–shell latices are predicted, and a related sensitivity analysis is given for the predictions. This article proposes a related sensitivity range for estimating the accuracy of predictions, made with the simple method, of the thermodynamically preferred morphology of a core–shell latex particle in two‐stage seeded emulsion polymerization. The related sensitivity range of the predictions is defined and calculated, and the results show that different core–shell latices have different sensitivity ranges. The wider the sensitivity range is, the more reliable the prediction is of the morphology of the core–shell latex. The simple method of related sensitivity range has been verified in the literature and with experiments. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3144–3152, 2004     

Synthesis and properties of fluorine–silicon modified polyacrylate hybrid latex particles with core–shell structure obtained via emulsifier‐free emulsion polymerization

A core–shell fluorine–silicon modified polyacrylate hybrid latex was successfully prepared via emulsifier‐free emulsion polymerization. The chemical composition and core–shell morphology of the resultant hybrid particles were investigated using ¹H NMR and Fourier transform infrared spectroscopies and transmission electron microscopy (TEM), respectively. TEM analysis indicated that the core–shell hybrid particles were uniform with narrow size distributions. The particle size and zeta potential decreased with an increase of alkylvinylsulfonate surfactant from 2.5 to 6.0 wt%. X‐ray photoelectron spectroscopy revealed that fluorine concentrated preferentially at the film surface during a film‐formation process. The film formed from the fluorine–silicon modified polyacrylate showed much higher thermal stability than a film formed from polyacrylate and fluorine‐modified polyacrylate. Contact angle results showed that a finished fabric had remarkable water repellency. © 2015 Society of Chemical Industry     

Poly(methyl methacrylate) copolymer nanocapsules containing phase‐change material (n‐dodecanol) prepared via miniemulsion polymerization

Poly(methyl methacrylate) copolymer nanocapsules containing the phase‐change material n‐dodecanol, which could be used for energy storage, were prepared with different comonomers via miniemulsion polymerization. The thermal properties, morphology, and composition of nanocapsules were characterized with differential scanning calorimetry, thermogravimetric analysis, transmission electron microscopy, and Fourier transform infrared spectroscopy. The results show that the thermal properties and morphology of the nanocapsules were influenced greatly by the type and amount of comonomers. Under the same dosage of 4 wt %, the nanocapsules prepared with the comonomer acrylamine and which had a moderate hydrophilicity showed the highest phase‐change latent heat of 109.3 J/g; the acrylamine that had a moderate hydrophilicity and the highest encapsulation efficiency of 91.3%. The size of the nanocapsules ranged from 50 to 100 nm with a uniform spherical shape and apparent core–shell structure. We also found that when the amount of the soft comonomer butyl acrylate was increased, the phase‐change latent heat of the nanocapsules first decreased slightly, then increased to the maximum value with deformed spherical and conglutinated morphology, and finally decreased continuously. The thermal stability of the nanocapsules became weaker with higher contents of core material. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42334.     

Structure and property characterization of nanograde core‐shell polyurethane/polyacrylate composite emulsion

Anionic aqueous polyurethane dispersion was synthesized through self‐emulsifing method from cycloaliphatic isophorone diisocyanate (IPDI) and dimethylolpropionic acid (DMPA). The carboxyl acid group in DMPA was used to make the polyurethane dispersible. The polyurethane/polyacrylate (PU/PA) composite particles were also prepared by seeded surfactant‐free emulsion polymerization; the cycloaliphatic polyurethane aqueous dispersion was used as seed particles. The structures and properties of the composite emulsion as well as the physical mixture of polyurethane dispersion and polyacrylate emulsion were characterized by FTIR, DSC, dynamic light scattering, TEM, X‐ray photoelectron spectroscopy (ESCA), and electronic tensile machine. The results showed that the synthesized PU/PA composite emulsion was found to form inverted core‐shell structure with polyacrylate as the core and with polyurethane as the shell, and its diameter of particles is in the range of nanograde, the crosslinking reaction was existed in composite emulsion. The intimate molecular mixing of crosslinking polymers are also claims to result in a superior balance of properties compared to physical blends of polyurethane dispersion and acrylate emulsion. The crosslinking mechanism of PU/PA composite emulsion was also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Solvent diffusion in silica/poly[styrene‐co‐(acrylic acid)] core‐shell microspheres by pulsed field gradient NMR techniques

Polymer‐coated SiO₂ particles are prepared by precipitation of poly[styrene‐co‐(acrylic acid)] on SiO₂ microspheres through an improved phase inversion method. The diffusion resistance of the polymer membrane was considered to be the critical reason for producing tailor‐made polyethylene by catalysts supported on these polymer‐coated particles. This paper employs pulsed field gradient NMR (PFG‐NMR) to distinguish diffusion of n‐hexane in different regimes, i.e., in the space between each particle, the pores in SiO₂ and the polymer shell, by their respective diffusion coefficients. By varying the observation time, the time scale of the molecular exchange is discussed. A three‐region ansatz was used to interpret the exchange and diffusion in polymer‐coated SiO₂ system, and was compared with results acquired with noncoated particles. At long diffusion times, the mean‐squared displacement, and thus the averaged self‐diffusion coefficient, of hexane in the system of polymer‐coated SiO₂ particles is significantly reduced. The PSA membrane is identified as an efficient barrier against molecular exchange between the pores in SiO₂ and the intraparticle space. Consistently, the relaxation measurements indicated that the mobility of n‐hexane molecules, especially the rotation of n‐hexane, was limited by the PSA membrane. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40160.     

The diacetone acrylamide crosslinking reaction and its control of core‐shell polyacrylate latices at ambient temperature

Self crosslinkable core‐shell polyacrylate latices (PAs) cured at ambient temperature were synthesized by semicontinuous‐seeded emulsion polymerization with diacetone acrylamide (DAAM) and adipic dihydrazide (ADH) as crosslinkable monomers. The influences of DAAM monomer mass content, neutralizer, and curing temperature on the properties of self crosslinkable core‐shell latices and the keto‐hydrazide crosslinking were discussed. The spectroscopic techniques such as Fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), atomic force microscopy (AFM), transmission electron microscopy (TEM), and contact angle instruments were used to determine the structure and properties of PAs. The water evaporating rate during the film‐forming process of self crosslinkable core‐shell latices was also investigated. FTIR analyses demonstrate that the keto‐hydrazide crosslinking reaction does not occur in the latex environment but occurs at ambient temperature with the evaporation of water during the film‐forming process. The results of DSC show that the core‐shell crosslinkable PAs have two glass transition temperatures (T_g), and T_gs of crosslinked film are higher than that of non crosslinked fim. Moreover, the keto‐hydrazide reaction is found to be acid catalyzed and favored by the loss of water and the simultaneous decrease in pH arising from the evaporation of ammonia or amines during film‐forming process. Hence, in the volatile ammonia or amines neutralized latices, the latex pH value adjusted to 7–8, which not only ensure the crosslinkable latex with good storage stability but also obtain a coating film with excellent performances by introducing the keto‐hydrazine crosslinking reaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of novel self cross‐linking fluorinated acrylic latex

Self crosslinking fluorinated acrylic latex (SCLFAL) has been successfully prepared via starved seeded semibatch emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA), 2‐(perfluoro‐(1,1‐bisisopropyl)‐2‐propenyl)oxyethyl methacrylate (POMA), and N‐methylolacrylamide (NMA). The resultant SCLFAL is characterized by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance (NMR). Influences of the added amount of NMA on the crosslinking degree, contact angle, particle size, and glass transition temperature (T_g) of the film are investigated. Results show that the crosslinking degree, contact angle, and T_g of the film can be improved when the moderate amount of NMA is introduced into the mixed monomers. However, the added amount of NMA has no marked effect on the particle size of SCLFAL. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

Polyurethane‐acrylic hybrid emulsions with high acrylic/polyurethane ratios: Synthesis,characterization, and properties

Allyl polyoxyethylene ether (APEE) was used as coupling agent between polyurethane (PU) and acrylic polymer (AC) to synthesize stable waterborne polyurethane‐acrylic (PU‐AC) hybrid emulsions with high AC/PU weight ratio ranged from 45/55 to 70/30. The effect of the AC/PU weight ratio and the acrylate type including methyl methacrylate (MMA), butyl acrylate (BA) and mixture of them on the properties of the synthesized emulsions and resultant films were investigated. The research results showed that the colloidal particle of the emulsions behaved core‐shell structure, and the copolymers were not crosslinked. An increase in the AC/PU weight ratio led to an increase in the average particles size and the particle size distribution, but decrease in the viscosity of the emulsions. Meanwhile, the molecular weight distribution of the copolymers became wide, and the tensile stress, shore A hardness, storage modulus, glass transfer temperature, water resistance, and water contact angle of the resultant films increased, except that the films of PU‐BA were too soft to determine their mechanical properties. MMA and BA can provide the PU‐AC hybrid emulsions with very different properties, and which can be adjusted according to the special application. It was suggested that APEE can not only built up chemical bonds between PU and AC, but also increase the self‐emulsifying ability in the emulsion polymerization due to its hydrophilic ethylene oxide and carboxylic groups, resulting in that PU‐AC hybrid emulsions with high AC/PU ratio can be obtained by this method. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44488.     

Investigation of fluorinated polyacrylate latex with core–shell structure

Fluorinated polyacrylate latices with core–shell structure were prepared by semi‐continuous emulsion polymerization, using a mixed emulsifier system composed of a reactive emulsifier and a small amount of anionic emulsifier. The conversion and chemical components of the final latices were studied by gravimetric methods and Fourier‐transform infrared (FTIR) spectrometry, respectively. The structure of the latex particles was determined by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and particle size analysis. The latex films exhibited a low surface energy and high water‐contact angles. The surface analysis from X‐ray photoelectron spectroscopy (XPS) revealed that the fluorinated components preferentially self‐organized at the film–air interface. From XPS depth profiling of the film, it was found that a gradient concentration of fluorine existed in the structure of the latex film from the film–air interface to the film–glass interface. Compared with the core–shell structure with a fluorinated core, the core–shell structure with a fluorinated shell was more effective for modifying the properties of the latex films. Copyright © 2005 Society of Chemical Industry     

Synthesis of polystyrene/poly(butyl acrylate) core–shell latex and its surface morphology

A polystyrene (PS)/poly(butyl acrylate) (PBA) composite emulsion was produced by seeded emulsion polymerization of butyl acrylate (BA) with PS seed particles which were prepared by emulsifier‐free polymerization of styrene with potassium persulfate (KPS) under a nitrogen atmosphere at 70°C for 24 h with stirring at 60 rpm and swelled with the BA monomer in an ethanol/water medium. The structure of the PS/PBA composite particles was confirmed by the presence of the characteristic absorption band attributed to PS and PBA from FTIR spectra. The particles for pure PS and PS/PBA with a low content of the BA monomer were almost spherical and regular. As the BA monomer content was increased, the particle size of the PS/PBA composite particles became larger, and more golf ball‐like particles were produced. The surface morphology of the PS/PBA composite particles was investigated by AFM and SEM. The T_g's attributed to PS and PBA in the PS/PBA composite particles were found at 110 and ?49°C, respectively. The thermal degradation of the pure PS and PS/PBA composite particles occurred in one and two steps, respectively. With an increasing amount of PBA, the initial thermal decomposition temperature increased. On the contrary the residual weight at 450°C decreased with an increasing amount of PBA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 595–601, 2003     

Strategies for the production of high solids acrylic/methacrylic core‐shell latices

Well‐defined poly(butyl acrylate)/poly(methyl methacrylate) (PBA/PMMA) core shell particles with a moderately high solid content (49%) and particle diameters of less than 200 nm were prepared via seeded emulsion polymerization with a redox initiator and an anionic surfactant. Low‐viscosity (less than 150 cps at 20 s^?1) latex products were obtained by controlling the particle size distribution to within certain limits. Polymerization conversion and kinetics were followed gravimetrically and were adjusted so as to obtain recipes that could be scaled‐up for industrial production. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Cationic fluorinated polyacrylate core‐shell latex with pendant long chain alkyl: Synthesis,film morphology,and its performance on cotton substrates

We synthesized a novel cationic fluorinated polyacrylate latex (FLDH) with pendant long chain alkyl by copolymerization of perfluoroalkyl ethyl acrylate, lauryl methacrylate, dimethylaminoethyl methacrylate, and 2‐hydroxypropyl acrylate. FTIR, ¹H‐NMR, TEM, DSC, and TGA were used to characterize the as‐prepared FLDH. Then fine morphology, components, and hydrophobicity of films on silicon wafer and cotton substrates were investigated by scanning electron microscope, field emission scanning electronic microscope, atomic force microscope, X‐ray photoelectron spectroscopy (XPS), contact angle meter, etc. Results showed that the FLDH particles had quasi‐spherical core‐shell structure with an average diameter of 144 nm. The core‐shell FLDH film thus had two T_g and its thermal property was improved compared to fluorine‐free acrylate latex. FLDH could form a film on both the cotton fiber and silicon wafer substrate. At an amplification of <60,000 (of the original fiber) and the observation rule (working distance) of >100 nm, FLDH showed a smooth resin film on the treated fabric/fiber surface. However, as the observation rule decreased to 2 nm‐almost a molecular lever‐the FLDH film mostly exhibited an inhomogeneous structure and uneven morphology in its atomic force microscope images. There were many low or high peaks in FLDH topography. Consequently, in 5 μm² scanning field, the root mean square roughness of FLDH film reached to 0.506 nm. XPS analysis indicated the perfluoroalkyl groups had the tendency to enrich at the surface. In addition, water contact angle of the treated fabric could attain 146.2°. FLDH do not influence whiteness of the treated fabric but will make it slightly stiff at high doses. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci., 2013