Effect of storage on film-formation property of vinylidene chloride-acrylonitrile-methyl acrylate terpolymer latex

Latex prepared from 91 : 5 : 4 wt % vinylidene chloride-acrylonitrile-methyl acrylate monomer mixture by seeded semicontinuous emulsion polymerization was investigated for a change in minimum film-formation temperature (MFFT) during storage, with focus placed on polymer crystallinity in the dispersed state. MFFT rose from 20°C to 32°C, with storage at 20°C for 49 weeks. Infrared absorption of fresh and stored latexes in the dispersed state indicated an increase in absorbance at 1048 cm⁻¹, which is characteristic of a crystalline vinylidene chloride polymer, that correlated with the MFFT rise with storage. This suggested that the MFFT rise with storage was caused by increasing crystallinity of the polymer in the dispersed state. X-ray wide-angle diffraction and infrared absorption of powder polymers obtained by lyophilization of fresh and stored latexes also indicated increasing crystallinity with latex storage. Oxygen gas permeabilities of films coated with fresh and stored latexes were measured. Latex stored for long periods exhibited poor barrier property, indicating that such latex is unsuitable as an industrial barrier coating material for films and papers. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 573–579, 1998     

Emulsion copolymerization of vinylidene chloride and butyl methacrylate, 83:17 in mol %

Seven 35% solids, (83 : 17 in mol %), vinylidene chloride (VDC)–butyl methacrylate (BMA) copolymer latexes were prepared at 25°C using redox catalyst by batch and seeded semicontinuous emulsion copolymerization processes: one batch (G), one seeded batch (F), and five seeded semicontinuous polymerizations of five different monomer feed rates ranging from 0.27 (A) to 1.10 (E) wt %/min. All of the emulsion polymerizations gave stable latexes of almost 100% conversion with negligible coagulum and narrow particle size distributions. The kinetic studies of seeded semicontinuous polymerization A–E showed that the rates of polymerization (R_p) were controlled by the monomer addition rates (R_a), and polymerizations A–D (0.27–0.79 wt %/min) were under monomer-starved conditions; polymerization E (1.10 wt %/min) was in near-flooded condition. Significant differences were found in the physical and mechanical properties of the latex films, depending on the mode of monomer addition. Infrared spectroscopy, ¹³C solid-state NMR spectroscopy, X-ray diffraction, the T_g and T_m values by DSC, dynamic mechanical spectroscopy, and tensile strength measurement of the latex films post-heat-treated for 30 min at 70°C or aged for several months at room temperature demonstrated that batch polymerizations F and G gave copolymers of heterogeneous composition and a crystalline character. In contrast, semicontinuous polymerizations A–E gave copolymers of more uniform composition and an amorphous character.     

聚偏氯乙烯乳液最低成膜温度对涂层阻隔性能的影响

通过对连续乳液聚合的偏氯乙烯-丙烯酸甲酯（VDC—MA）共聚乳液最低成膜温度（MFFT）的测量和涂覆膜阻隔性能的测试,研究了VDC含量和PVDC胶乳的存放时间对乳液MFFT的影响。结果表明,当单体中w（VDC）〉92％时。MFFT剧增,阻隔性能急剧下降;当w（VDC）〈92％时,MFFT随VDC的质量分数上升而缓慢下降,但表观质量下降;当w（VDC）约为92％时,MFFT最低,涂层阻隔性能最佳。     

Particle size and shell composition as effective parameters on MFFT for acrylic core–shell particles prepared via seeded emulsion polymerization

In this study, acrylic-based copolymer particles were prepared with core–shell morphology and the effect of T_g of the shell, particle size and their bimodal size distribution on minimum film formation temperature (MFFT) were investigated. The main goal was to optimize conditions to obtain latexes with low MFFT and appropriate mechanical properties. These will develop the applicability of such water-borne binders as paints and coatings at ambient conditions. A series of latexes with core–shell morphology with variable T_g of the shell from −56 to 30 °C were prepared and the MFFT, hardness and thermal behavior of the obtained films were studied. Then a series of latexes with particle sizes ranging from 46 to 960 nm were prepared and the effect of particle size on MFFT was studied too. By inducing the formation of secondary nucleation during emulsion polymerization, latexes with bimodal size distribution were obtained and the effect of presence of such particles on film formation was investigated. Results indicate that latexes with appropriate composition and bimodal particle size distribution lead to optimized performance in both mechanical and film formation properties as a proper choice for water-borne coatings.     

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.     

Viscoelastic properties and film morphology of heterogeneous styrene–butadiene latexes

Heterogeneous carboxylated styrene–butadiene (S/Bu) latexes were prepared by a twostage emulsion polymerization process, using three PS seeds with different molecular weights. The second-stage polymer was a copolymer with a fixed S/Bu ratio of 1 : 1 and a methacrylic acid (MAA) content of either 1 or 10 wt %. Morphological studies by transmission electron microscopy (TEM) as well as studies of the viscoelastic properties by mechanical spectroscopy have been performed on films prepared from the latexes. The studies showed that the glass transition temperature, T_g, of the second-stage polymer was considerably affected by copolymerization with MAA. An increase in the MAA content in the second-stage polymer increased the T_g of this phase significantly. Addition of DVB as a crosslinking agent in the preparation of the PS seed phase substantially increased the rubbery moduli of the films, whereas the glass transition temperature of the second-stage polymer was unaffected. On the other hand, the presence of a chain transfer agent reduced the glass transition of the second-stage copolymer containing 1 wt % MAA dramatically, whereas the rubbery modulus was unaffected. When the MAA content was increased to 10 wt % the influence of the MAA monomer had a dominating effect on T_g. Latexes containing 10 wt % MAA had T_g values close to each other, regardless of chain transfer agent present in the second-stage polymerization. It was found that the morphology of the latex particles influenced the rubbery modulus of the films. The presence of irregularly shaped seed particles in samples prepared from a crosslinked PS seed had a considerable reinforcing effect on the films, whereas spherical seed particles originating from core–shell particles had a less reinforcing effect. © 1996 John Wiley & Sons, Inc.     

A simple approach to fabricate morphological gradient on polymer surfaces

This paper presents a novel and feasible approach for fabrication of morphological gradient surfaces based on the film-formation of nanocomposite polymer latex. In this method, when the polymer latex with relatively low glass transition temperature (T_g) was blended with colloidal silica and then dried at certain temperatures, a morphological evolution with deeper pores from the center to the edge could be directly obtained on polymer surface. Neither careful control of experimental conditions nor any complex processes are needed. The T_g of polymer, the silica content, the solvent and the drying temperature have significant influences on this surface morphology. The film-formation mechanisms at different drying temperatures are also discussed.     

Development of VOC-free, high-T g latex binders by a high-temperature water-extended latex technology

The potentiometric titration of carboxylated methyl methacrylate latexes prepared with varying amounts of methacrylic acid showed that only very small amounts of their total acids copolymerized were neutralized at room temperature until the acid level was well above 10%. However, it was found that all the acids copolymerized were completely titrated either in a 50/50 water/ethanol mixture at room temperature or in water at high temperatures near their backbone polymer T _gs, regardless of their acid contents, as predicted from the existing theories on the alkali-swelling of carboxylated latexes. It was also found that these high-temperature alkali-swollen latex particles remained in the swollen state even after they were cooled down to room temperature and became film-forming at much lower temperatures. This discovery led to a new technology coined as a high-temperature water-extended latex technology. This new technology enabled us to develop VOC-free water-extended latexes of high-T _g polymers that would exhibit good film formation at ambient temperature and turn into hard and non-blocking latex films and latex-bound pigmented coatings upon drying. Particularly, when fugitive bases were used for neutralization at high temperatures, the resulting water-extended latexes became hard, non-blocking, and water-resistant binders upon drying.     

Improvement of film properties of vinyl acetate based emulsion polymers by using different types of maleic acid diesters

Two types of maleic acid diesters, dibutyl maleate (DBM) and dioctyl maleate (DOM) were used as comonomers in semicontinuous emulsion copolymerization of vinyl acetate (VAc) in order to improve the film properties of poly(vinyl acetate), PVAc emulsion polymer. The effects of the comonomer type and comonomer ratio on minimum film forming temperature (MFFT), glass transition temperature (T_g), polymer structure, molecular weights, water contact angle and water resistance of PVAc latex films were examined. It was found that MFFT and T_g of the PVAc emulsion polymer decreased by the presence of the maleic acid disters in copolymer composition. This decrease was more affected by the increasing content and alkyl chain length of the comonomers. The molecular weights of the emulsion polymers were also affected by the comonomers and their ratios. Moreover, hydrophobicity and water resistance of the PVAc latex films were increased by using DBM and DOM as comonomer.     

Mechanism of alkali thickening of acid-containing emulsion polymers. I. Examination of latexes by means of viscosity

Viscosity-versus-pH relationships for a large number of methacrylic acid-containing emulsion polymers have been measured. The monomers chosen for this study were so selected because they represent synthesized latexes of high and low T_g and comparative hydrophilicity. These were styrene, methyl methacrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. The postulated mechanism involved in the transition from an unneutralized latex particle to the neutralized species is accounted for in terms of varying degrees of particle swelling. In the limiting case, particle swelling is followed by complete solution of the polymer. The most important variables are the per cent methacrylic acid and the polymer T_g and hydrophilicity as determined by the comonomers present. The degree of particle swelling ranges from none for high styrene-containing latexes to high degrees of swelling followed by polymer solubilization for high ethyl acrylate-containing latexes.     

Effect of acrylic acid on water-whitening resistance of polyacrylate latex films and its mechanism

Two groups of polyacrylate latexes with higher (21 ~ 35 °C) or lower (−33 ~ −43 °C) glass transition temperatures (T_g) were prepared by adjusting the monomer ratio of butyl acrylate (BA) and styrene (St), and the effect of acrylic acid (AA) on water-whitening resistance of these latex films was investigated. It was found that the water-whitening resistance of the two groups of latex films was different. With the increase of AA content, the water whitening resistance of the latex films with higher T_g continued to improve, while that of the latex films with lower T_g increased first and then decreased. A series of characterizations, such as light transmittance, water whitening, water absorption, static water contact angle, surface morphology, and optical microscope test of the latex film, and so forth, showed that the reason for this difference was that under higher AA content (≥5%), compared with the polyacrylate latex films with lower T_g, the latex films with higher T_g could reach the saturation state of water absorption quickly, and water in these latex films exhibited continuous and large area distribution, rather than formation of many so-called micro- or nano-scale water sacs that can scatter light as found in the latex films with lower T_g.     

Batch and semicontinuous emulsion copolymerization of vinylidene chloride and butyl methacrylate. II. Physical and mechanical properties of copolymer latex films

Vinylidene chloride (VDC)–butyl methacrylate (BMA) copolymer latex films of various compositions (83 : 17, 60 : 40, 33 : 67 in mol %), prepared by batch and semicontinuous processes, were investigated for their physical properties by infrared spectroscopy, ¹³C solidstate NMR spectroscopy, X-ray diffraction, solubility in various solvents, differential scanning calorimetry (DSC), and water vapor transmission rates (WVTR), and for their mechanical properties by dynamic mechanical spectroscopy (DMS), and tensile strength measurements. Semicontinuous latex films were found to be homogeneous in composition and amorphous in character. On the other hand, batch latex films containing high VDC monomer content were heterogeneous in composition and crystalline in character. These differences were found to reflect the effect of mode of monomer addition during the emulsion polymerization process, and correlated well to the results on kinetics, colloidal, and surface properties of the VDC-BMA copolymer latexes, as described in the first part of this study.     

Effect of colophony emulsion on the adhesive properties of vinyl acetate/n‐butyl acrylate copolymeric latex

We prepared a novel copolymeric latex of vinyl acetate and n‐butyl acrylate (V‐B) using a semibatch emulsion polymerization process. The glass‐transition temperature (T_g), steady viscosity, flow activation energy (E_f), dynamic moduli, and amphiphilic properties of the V‐B latex in the presence of colophony were systematically investigated. The experimental results demonstrate that excellent adhesive behaviors were achieved for the V‐B latex blended with 20 wt % colophony, whereas good adhesive performance was related to the moderate T_g, viscosity, E_f, storage modulus, and low contact angle on the adherent. The debonding mechanisms for V‐B and its colophony‐modified latexes were analyzed. A possible mechanism for the V‐B latex blended with colophony emulsion was determined. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphologies and dynamic mechanical properties of core‐shell emulsifier‐free latexes and their copolymers for P(BA/MMA)/P(MMA/BA) and P(BA/MMA)/PSt systems in the presence of AHPS

Different poly(methyl methacrylate/n‐butyl acrylate)/poly(n‐butyl acrylate/methyl methacrylate) [P(BA/MMA)/P(MMA/BA)] and poly(n‐butyl acrylate/methyl methacrylate)/polystyrene [P(BA/MMA)/PSt] core‐shell structured latexes were prepared by emulsifier‐free emulsion polymerization in the presence of hydrophilic monomer 3‐allyloxy‐2‐hydroxyl‐propanesulfonic salt (AHPS). The particle morphologies of the final latexes and dynamic mechanical properties of the copolymers from final latexes were investigated in detail. With the addition of AHPS, a latex of stable and high‐solid content (60 wt %) was prepared. The diameters of the latex particles are ～0.26 μm for the P(BA/MMA)/P(MMA/BA) system and 0.22–0.24 μm for the P(BA/MMA)/PSt system. All copolymers from the final latexes are two‐phase structure polymers, shown as two glass transition temperatures (T_gs) on dynamic mechanical analysis spectra. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3078–3084, 2002     

偏氯乙烯共聚物/纳米水滑石复合材料及多孔炭的制备与表征

采用原位悬浮聚合和熔融加工制备了不同纳米水滑石含量的偏氯乙烯-丙烯酸甲酯(VDC-MA)共聚物/纳米水滑石复合材料,并通过高温炭化和模板消除得到多孔炭材料。采用电镜、X射线衍射、N₂吸脱附法表征了复合材料和多孔炭的结构。结果表明,纳米水滑石含量≤6.25%（质量）时,纳米水滑石基本以初级粒子均匀分散在VDC-MA共聚物基体中,并在炭化过程中转化为金属氧化物;金属氧化物可经酸洗去除,起到模板致孔作用;同时VDC-MA共聚物炭化过程形成大量微孔,因此得到的多孔炭具有微孔和中孔分布。当炭化温度较低时(600～700℃)相似文献   

Effect of polymer latexes with varied glass transition temperature on cement hydration

Influence of styrene‐acrylate latexes with varied glass transition temperature (T_g) on cement hydration was studied and the mechanism was analyzed. Results show that polymer latexes with varied T_g retard cement hydration to different extents. Specifically, low T_g polymer shows stronger retardation effect than the high T_g polymer. Despite similar surface charges, colloidal particles with lower T_g exhibit higher affinity to surface of cement grains than the high T_g polymer, indicated by the higher adsorption amount and denser covering layer. The low T_g polymer experiences particle packing, deforming, and film forming processes along with the consumption of water during cement hydration, which eventually produces a covering layer of polymer surrounding cement grains. However, for the high T_g polymer, film forming process is absent. Consequently, the higher adsorption amount and the film‐formation process along with cement hydration are the two reasons for the stronger retardation effect of the low T_g polymer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45264.     

Mechanism of alkali-thickening of acid-containing emulsion polymers. II. Examination of latexes with the light microscope

The mechanism of alkali thickening of acid-containing emulsion polymers has been confirmed by visual examination of the swelling and disappearance of latex particles with the light microscope. Specially prepared large particle-sized latexes were used in this study. Each latex was examined from 0%–200% neutralization with base. The particle swelling and dissolution behavior correlated with viscosity measurements, high viscosity being present for swollen particle systems and low viscosity for true solutions. The neutralized state of all acid-containing latexes can be pictured in a cube with the important variables being per cent acid, hydrophilicity of the comonomers, and T_g. At the bottom will be latexes only slightly affected by neutralization, above this will be a swollen particle zone, and the largest area will be a true solution zone. The true solution zone will be enlarged by lowering the molecular weight of the latex polymer.     

Role of particle size on latex deformation during film formation

The ability of latex particles to deform and coalesce to form an integral film upon drying is an important property in many latex coating applications. Many theories have been proposed to account for the origin of the deformation forces. The capillary forces which depend inversely on particle size have been accepted as important for latex deformation and film formation. The minimum film forming temperature (MFFT) has been found to be a function of the particle size of latexes and has been used as evidence that the capillary forces are responsible for film formation. In this study, the deforming force at MFFT has been determined from the moduli of water-equilibrated latex polymers. No particle size dependence was observed. The magnitude of the deforming forces was at least an order of magnitude lower than that predicted by the capillary force theory. Electron microscopy of film formed below the MFFT, a condition that corresponds to early stage film formation, showed significant deformation, indicating that at the beginning of film formation, forces of magnitude predicted by the capillary force theory are present. However, the magnitude of the forces decreases rapidly as film formation progresses. The MFFT particle size dependency can be explained by the difference in the degree of water plasticization. Evidence that latexes of different particle size were plasticized by water to different extents was determined from the T_gs of the latex emulsions. Presented at the 76th Annual Meeting of the Federation of Societies for Coalings Technology, on October 15, 1998, in New Orleans, LA. Emusion Polymers Research 1604 Building, Midland, MI 48674.     

Composite latex production with high solid content

Poly(methyl methacrylate-co-butyl acrylate) (PMMA-co-PBA) and poly(sytrene-co-butyl acrylate) (PSt-co-PBA) latexes in which solid content (SC) varied from 20% up to 40 wt % armored with laponite clay have been successfully synthesized using a simple method, which does not require modification of the clay particles prior to polymerization. Incorporation of quite high amounts of laponite nanoparticles into PMMA-co-PBA and PSt-co-PBA latexes with a certain amount of solids content was achieved. The nanocomposite latexes and polymer samples were characterized using Fourier transform infrared (FTIR) spectroscopy in attenuated total reflectance (ATR) mode, dynamic light scattering (DLS), X-ray diffraction (XRD), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), contact angle, zeta potential, viscosimetry and analytical ultracentrifuge (AUC). Zeta potential values showed that stable latex was obtained and precipitation problem of the nanoparticles in the latex was not seen during the storage. Obtained nanocomposite latex showed fine particle size between 88 and 160 nm. TEM images and XRD results pointed out that the exfoliated nanocomposite structure for latexes was obtained. DSC analyzes showed that the glass-transition temperature (T _g) values of nanocomposite films decreased slightly compared with those of pure (PMMA-co-PBA) films. Mechanical properties of laponite clay armored PMMA-co-PBA were tested and compared with those of pure PMMA-co-PBA, indicating that incorporated the Young's modulus and tensile strength are also improved to a noticeable extent after the incorporation of laponite. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47423.     

Preparation and structure control of hollow polymer particles: Influence of seeded emulsion polymerization and alkalization treatment process

Hollow polymer latex particles containing a hydrophilic core were prepared by seeded emulsion polymerization with MAA/BA/MMA/St as comonomers, followed by stepwise alkalization treatment with ammonia. The size and morphology of composite latex particles was determined by TEM. The effects of the seeded emulsion polymerization conditions and alkalization treatment on the size and hollow structure of latex were investigated. The results showed that the optimum content of crosslinking agent in the shell polymers was about 0.5–1.0 wt %, emulsifier was about 0.8–1.1 wt %, and the core/shell weight ratio was 1/7. To obtain uniform hollow latex particles with large size, the starved feeding technique should be adopted in seeded emulsion polymerization, and the neutralization temperature should equal to the T_g of the shell polymer. Then, the obtained polymer particles under this condition had an excellent hollow structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009