Compatibilization of polystyrene/poly(butyl methacrylate)/poly[(ethylene glycol) dimethacrylate] blends via concentrated emulsion polymerization

Two concentrated emulsions in water containing styrene and butyl methacrylate (BMA) as dispersed phases were prepared. Each of them contained a small amount of an amphiphilic macromonomer, poly[(ethylene glycol) dimethacrylate] (PEGD), in the continuous phase. The two concentrated emulsions were partially polymerized at 50 °C until conversions of about 22.5 % were reached. They were then mixed mechanically and the mixture was subjected to complete polymerization. During the latter polymerization, homopolymers of styrene and BMA and copolymers of the two were generated. The copolymers, particularly the crosslinked structures, which were formed through copolymerization of PEGD with styrene and BMA at the interface of the latexes, provided compatibilizers for the homopolymers. This blend of homopolymers, copolymers and crosslinked structures possessed excellent toughness and processability. The blends were characterized by their gel content, and by X‐ray photoelectron spectroscopy, rheometric testing, dynamic mechanical thermal analysis, transmission electron microscopy and impact strength measurements. Copyright © 2005 Society of Chemical Industry     

Preparation and properties of poly(butyl methacrylate/lauryl methacrylate) and its blend fiber

The functionalized copolymers, based on butyl methacrylate (BMA), and lauryl methacrylate (LMA) with crosslinking agent HEMA (hydroxyethyl methacrylate) or DVB (divinyl benzene), have been innovatively synthesized by suspension polymerization for oil absorption. Further, the copolymers and polypropylene (PP) blend fiber were attained via melt spinning. Swelling behaviors were evaluated by equilibrium swelling experiment, oil absorbency test, gel fraction measurement, and optical observations in toluene. The thermal properties and morphologies of the blend fibers were analyzed by thermogravimetry (TGA) and a field-emission scanning electron microscope, respectively. The results show that the copolymers and their blend fibers have an impressive absorbency. PBMA/LMA/HEMA can be up to 35.18?g/g, showing the highest absorption in trichloroethylene. Optical images of swollen polymers in toluene depicted a colloidal translucence with gel structure. Thermogravimetric measurement demonstrates that the copolymer and PP are incompatible and PBMA/LMA/DVB component possesses more thermal stability. The micrographs of the blend fibers exhibit coarse surface and porous cross-section, which leads to the fibers being much more readily wetted by oil and provides a huge space for oil storage.     

DPE法合成双亲性丙烯酸酯嵌段共聚物及用于颜料分散剂的研究

以1,1-二苯基乙烯（DPE）为分子量调节剂,偶氮二异丁腈（AIBN）为引发剂进行甲基丙烯酸丁酯（BMA）的可控自由基聚合（DPE法）。研究了溶剂、DPE用量及反应温度对于聚合的影响,得到分子量分布较窄（PDI=1.43）的含有DPE半醌式休眠种结构的聚甲基丙烯酸丁酯（PBMA）。以PBMA为引发剂引发甲基丙烯酸二甲氨基乙酯（DMAEMA）聚合,得到分子量分布较窄的（PDI=2.0）双亲性嵌段共聚物（PBMA-b-PDMAEMA）。核磁共振氢谱（¹H NMR）测得共聚物组成与GPC测试结果相近。差示扫描量热分析（DSC）测试表明嵌段共聚物在11℃和35℃处有两个玻璃化转变温度。色浆的流变和粒径测试及漆膜性能测试表明,将所得双亲性嵌段共聚物作为酞菁蓝颜料分散剂,可以明显提高酞菁蓝颜料在丙烯酸酯树脂中的分散效率。     

Modified emulsifier‐free emulsion polymerization of butyl methacrylate with ionic or/and nonionic comonomers

A modified emulsifier‐free emulsion polymerization of butyl methacrylate (BMA) with ionic or/and nonionic comonomers was successfully used to prepare nanosized poly(butyl methacrylate) (PBMA) latices with high polymer contents. After seeding particles were generated in an initial emulsion system, consisting of a portion of BMA, water, ionic comonomer [sodium styrenesulfonate (NaSS)] or nonionic comonomer [2‐hydroxyethyl methacrylate (HEMA)] and potassium persulfate, most of the BMA monomer or the mixture of BMA and HEMA was added dropwise to the polymerizing emulsion over a period of 6–12 h. Stable latices with high PBMA contents up to 27% were obtained. It was found that the latex particle sizes (2R_h) were largely reduced (34 nm) by the continuous addition of monomer(s) compared to those (107 nm) obtained by the batch polymerization method. The effect of comonomer concentration on the particle size, the number of PBMA particles/mL of latex (N_d), and the molar mass (M_w) of copolymer during the polymerization were discussed. The surface compositions of latex particles were analyzed by X‐ray photoelectron spectroscopy, indicating that the surface of latex particles was significantly enriched in NaSS or/and HEMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3080–3087, 2004     

Self-compatibilization of polymer blends via concentrated emulsions

Summary A novel approach to the formation and compatibilization of polymeric blends is suggested, namely the self-compatibilization via concentrated emulsions. In this method, two concentrated emulsions are prepared from different monomers and subjected to partial polymerization; at least one concentrated emulsion contains also some di-vinyl-terminated macro-monomers. A blend is formed by mixing the partially polymerized latexes and subjecting the mixture to complete polymerization. Some AB networks, with the macro-monomers as chains A and the homo- and co-polymers generated from the other monomers as chains B, are formed, which ensure the self-compatibilization of the resulting blend. Blends of styrene-co-methyl methacrylate and poly (vinyl acetate) were prepared and investigated as a model system.     

Preparation of poly(butyl methacrylate)/γ‐Al2O3 nanocomposites via ultrasonic irradiation

A new technique (ultrasonic irradiation) has been employed to prepare poly(n‐butyl methacrylate) PBMA/γ‐Al₂O₃ nanocomposites, taking advantages of the multiple effects of ultrasonic irradiation, such as dispersion, pulverization and activation. When subjected to ultrasonic irradiation, n‐butyl methacrylate (BMA) is polymerized to form poly(n‐butyl methacrylate) (PBMA) latex without any chemical initiators, and the monomer conversion reaches 72.5% in 25 min. At an appropriate pH, surfactant bilayers are formed through electrostatic interactions between γ‐Al₂O₃ nanoparticles and the anionic surfactant sodium dodecyl sulfate (SDS), which adsorb BMA. After ultrasonic induced polymerization of BMA in the presence of nanoparticles of γ‐Al₂O₃, the γ‐Al₂O₃ nanoparticles are encapsulated by PBMA shells formed. The influence of factors such as pH, surfactant concentration and the nanoparticle content is investigated. The FTIR spectra show that there are still polymers tightly adsorbed by nanoparticles even after extraction by acetone for 72 h. The difference observed in the XPS spectra of nanocomposite residues and the pure γ‐Al₂O₃ nanoparticles may indicate some interactions between γ‐Al₂O₃ nanoparticles and the PBMA matrix. Furthermore, the feasibility of SDS bilayer formation and encapsulating polymerization is proven by XPS characterization. © 2001 Society of Chemical Industry     

Synthesis and characterization of PBMA‐b‐PSt‐b‐PBMA triblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate)‐b‐polystyrene‐b‐poly(n‐butyl methacrylate) (PBMA‐b‐PSt‐b‐PBMA) triblock copolymers were successfully synthesized by emulsion atom transfer radical polymerization (ATRP). Difunctional polystyrene (PSt) macroinitiators that contained alkyl chloride end‐groups were prepared by ATRP of styrene (St) with CCl₄ as initiator and were used to initiate the ATRP of butyl methacrylate (BMA). The latter procedure was carried out at 85°C with CuCl/4,4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as catalyst and polyoxyethylene (23) lauryl ether (Brij35) as surfactant. Using this technique, triblock copolymers consisting of a PSt center block and PBMA terminal blocks were synthesized. The polymerization was nearly controlled, ATRP of St from those macroinitiators showed linear increases in the number average molecular weight (Mn) with conversion. The block copolymers were characterized with infrared (IR) spectroscopy, hydrogen‐1 nuclear magnetic resonance (¹HNMR), and differential scanning calorimetry (DSC). The effects of the molecular weight of macroinitiators, concentration of macroinitiator, catalyst, emulsion, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP were also reported. POLYM. ENG. SCI., 45:1508–1514, 2005. © 2005 Society of Plastics Engineers     

Synthesis, characterization, and energy transfer studies of dye-labeled poly(butyl methacrylate) latex particles prepared by miniemulsion polymerization

Poly(butyl methacrylate) (PBMA) latex particles have been copolymerized with new fluorescent naphthalimide dyes by miniemulsion polymerization. A new pair of naphthalimide dye monomers was synthesized and copolymerized with butyl methacrylate (BMA) via miniemulsion polymerization, producing approximately 80 nm diameter particles with a narrow size distribution. We were able to prepare polymers with molecular weights in excess of 100,000 g/mol. We also prepared 30,000 g/mol polymers using 1-dodecanethiol as a chain transfer agent. GPC and UV characterization suggest that nearly all of the dye monomers were incorporated into the PBMA polymer chains. The polymerized naphthalimide dyes can be used as a donor-acceptor pair for fluorescence resonance energy transfer (FRET) experiments. The analysis of FRET experiments is complicated by the slightly non-exponential decay of the donor naphthalimide dye. We propose a simple method to deal with this non-exponential behavior in the data analysis. Using our approach, we find that the Förster radius (R_o) between the donor and the acceptor dyes incorporated in the PBMA latex is 3.8 nm. This value is similar to the 3.6 nm Förster radius of a comparable model dye pair in ethyl acetate obtained by a different method.     

Properties of n‐butyl methacrylate copolymer latex films derived from crosslinked latex particles

Films obtained from copolymer latexes of n‐butyl methacrylate (BMA) with a series of crosslinking monomers [i.e., a macromonomer crosslinker (Mac), ethylene glycol dimethacrylate (EGDMA), and aliphatic urethane acrylate] exhibited differences in their tensile properties and swelling behaviors. For P(BMA‐co‐EGDMA) copolymer, a dependence on the initiator type was obtained. It is postulated that the network microstructures for the various copolymers evolved as the result of the copolymerization reactions between the monomer pairs during the synthesis in the miniemulsion free‐radical copolymerization. These network microstructures are, therefore, hypothesized to influence the mechanical properties of the resultant films. Copolymers prepared with Mac were tough in comparison with copolymers made with EGDMA. The presence of longer linear or lightly crosslinked poly(n‐butyl methacrylate) (PBMA) chains and the looseness of the crosslinked network structures in the PBMA‐co‐Mac copolymers appear to be the factors responsible for the differences. All of the copolymer films disintegrated into swollen individual microgels when they were immersed in tetrahydrofuran. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 42–49, 2003     

Morphology of micron‐sized,monodisperse, nonspherical polystyrene/poly(n‐butyl methacrylate) composite particles produced by seeded dispersion polymerization

Nonspherical polystyrene (PS)/poly(n‐butyl methacrylate) (PBMA) composite particles with uneven surfaces were produced by seeded dispersion polymerization of BMA with 1.65‐μm, monodisperse, spherical PS seed particles. The composite particles consisted of a PS core and an incomplete PBMA shell. The formation mechanism of such nonspherical particles was discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2013–2021, 2002     

Study of compartmentalization in the polymerization of miniemulsions of styrene and butyl methacrylate

Different surfactant and costabilization systems were studied for the miniemulsion polymerizations of styrene (St) and of butyl methacrylate (BMA). It was found that the combination of sodium dodecyl sulfate, Triton X‐405, and octadecyl acrylate yielded excellent results. With this system all of the droplets initially present in the reactor polymerized. This stabilization system was then used in the study of compartmentalization of the monomer droplets in miniemulsion polymerization. Blends of BMA and St miniemulsions were prepared separately and polymerized together to study mass transfer in this system. It was observed that no matter is exchanged between the different phases. This compartmentalization was also demonstrated and exploited by producing a bimodal molecular weight distributions latex, achieved with a semicontinuous process. The lower MWD was created by adding a second miniemulsion containing a transfer agent. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 115–124, 2004     

Synthesis of ABA triblock copolymers of N-substituted maleimides and methacrylates by group transfer polymerization

Summary ABA type block copolymerization of N-phenylmaleimide (NPM), N-hexyl maleimide (NHM), methyl methacrylate (MMA), and butyl methacrylate (BMA) was investigated by group transfer polymerization (GTP) with [1,5-bis (trimethylsilyloxy)-1,5-dimethoxy-1,4-pentadiene] (1) as difunctional initiator. A novel block copolymers (2) of NPM and MMA (or BMA) could be prepared by sequential addition of NPM to the living PMMA (or PBMA) produced with 1. The reaction did not exhibit the characteristics of living polymerization when NPM was added. The resulting copolymers showed good thermal stability. On the other hand, gelation occurred in GTP of NHM.     

Preparation of asymmetric film by blending two kinds of polymer emulsions having greatly different storage stabilities

Two kinds of anionic polymer emulsions with different particle sizes were blended and cast on a release-paper at 30°C. One was poly(butyl acrylate) emulsion, and the other was ethyl acrylate–methyl methacrylate (1 : 1, weight ratio) copolymer emulsion. They were produced by emulsifier-free emulsion polymerization. The blend films prepared in an appropriate range of the blend ratio had a great difference in tackiness between both surfaces: The air-side surface exhibited tackiness and the release-paper side showed nontackiness. The forming mechanism is discussed.     

Compatibility studies with blends based on poly(n‐butyl methacrylate) and polyacrylonitrile

In this study, poly(n‐butyl methacrylate) (PBMA) was prepared by a suspension polymerization process, and blending with polyacrylonitrile (PAN) in N,N‐dimethyl acetamide to prepare PAN/PBMA blends in various proportions. Hansen's three dimensional solubility parameters of PAN and PBMA were calculated approximately through the contributions of the structural groups. The compatibility in these blend systems was studied with theoretical calculations as well as experimental measurements. Viscometric methods, Fourier transform infrared spectroscopy, dynamic mechanical analysis, scanning electron microscopy, and thermogravimetric analysis were used for this investigation. All the results showed that a partial compatibility existed in PAN/PBMA blend system, which may be due to the intermolecular interactions between the two polymers. And, the adsorption experiment results showed that the addition of PBMA contributed to the enhancing adsorptive properties of blend fibers, which lays the foundation for further studying PAN/PBMA blend fibers with adsorptive function. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The effects of acrylate monomers and polystyrene addition on the morphology of DOP‐plasticized styrene–acrylate polymer particles prepared by SPG emulsification and suspension polymerization

Fairly uniform copolymer particles of methyl acrylate (MA), butyl acrylate (BA), or butyl methacrylate (BMA) were synthesized via Shirasu porous glass (SPG) membrane and followed by suspension polymerization. After a single‐step SPG emulsification, the emulsion composed mainly of the monomers. Hydrophobic additives of dioctyl phthalate (DOP), polystyrene molecules, and an oil‐soluble initiator, suspended in an aqueous phase containing poly(vinyl alcohol) (PVA) stabilizer and sodium nitrite inhibitor (NaNO₂), were subsequently subjected to suspension polymerization. Two‐phase copolymers with a soft phase and a hard phase were obtained. The composite particles of poly(St‐co‐MA)/PSt were prepared by varying the St/PSt ratios or the DOP amount. The addition of PSt induced a high viscosity at the dispersion phase. The molecular weight slightly increased with increasing St/PSt concentration. The multiple‐phase separation of the St‐rich phase and PMA domains, observed by transmission electron microscopy, was caused by composition drift because the MA reactivity ratio is greater than that of St. The addition of DOP revealed the greater compatibility between the hard‐St and soft‐MA moieties than that without DOP. The phase morphologies of poly(St‐co‐MA), poly(St‐co‐BMA), and their composites with PSt were revealed under the influence of DOP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1195–1206, 2006     

Electrospun polyvinyl chloride/poly (butyl methacrylate-<Emphasis Type="Italic">co</Emphasis>-butyl acrylate) fibrous mat for absorption of organic matters

Polyvinyl chloride (PVC) is a hydrophobic and lipophilic polymer, and its electrospun mat has plenty of micro- and nanopores. However, the PVC electrospun mat cannot absorb organic substances due to its weak fiber-web structure. The copolymer of butyl methacrylate (BMA) and butyl acrylate (BA) has very good electrospinnability, and its electrospun fibers can construct a firm fiber-web structure through many bonded nodes. However, there are few micro- and nanopores in the fiber-web of the copolymer of BMA and BA since the electrospun fibers of the copolymer of BMA and BA can cohere with each other. Therefore, the copolymer of BMA and BA was blended with PVC in N,N-dimethylformamide to provide their electrospun fibrous mat with good fiber-web structure and many micro- and nanopores, and their electrospun fibrous mat was then used as an absorbent of organic substances in this work. We first discovered the electrospinnable concentrations for PVC solution, the solution of the copolymer of BMA and BA, and the blend solution of PVC and the copolymer of BMA and BA by researching the characteristics of these solutions, and we analyzed the effect of the electrospinnability of PVC in the blend solution on the formation of fiber-web structure. Then, the blend solution with an electrospinnable concentration was electrospun into fibrous mat, and its surface characteristics and absorption capability to organic matters were subsequently investigated. The correlation between absorption capability and fiber-web structure was analyzed through field emission scanning electron microscope. The result showed that the blend solution of PVC and the copolymer of BMA and BA had better electrospinnability in comparison with PVC solution, and the corresponding fibrous mat had a great potential application in removing organic matters since it owned better hydrophobic and lipophilic properties than the fibrous mat electrospun from PVC solution or the solution of the copolymer of BMA and BA.     

Synthesis and properties of a ternary polyacrylate copolymer resin for the absorption of oil spills

A high‐oil‐absorption resin of a ternary copolymer for the absorption of oil spills was successfully prepared by suspension polymerization, and characterizations of the oil‐absorption resin were also examined in this study. The high‐oil‐absorption resin, a ternary copolymerized long‐chain polyacrylate with styrene (St), butyl methacrylate (BMA), and stearyl methacrylate (SMA) as the monomers and synthesized by suspension polymerization, was introduced. The oil‐absorption resin of St/BMA/SMA was characterized by Fourier transform infrared spectrometry. The particle morphology of the resin was observed by scanning electron microscopy. The effects of different polymerization technological parameters, such as the mass ratios of the monomer, the benzoyl peroxide initiator, and the crosslinking agent of divinylbenzene; the sort and concentrations of the dispersing agent of hydroxyl ethyl cellulose, sodium dodecyl benzene sulfonate, and gelatin, and the polymerization temperature, on the oil absorbency of St/BMA/SMA are discussed in detail. The optimum polymerization conditions of the St/BMA/SMA copolymer were obtained as follows: m_St/m_monomer = 50 wt %, m_BMA/m_{soft monomer} = 60 wt %, m_water/m_oil = 3:1, m_DVB/m_monomer = 1.0 wt %, m_BPO/m_monomer = 1.5 wt %, m_HEC/m_monomer = 0.07 wt %, m_SDBS/m_monomer = 0.03 wt %, m_gelatin/m_monomer = 0.14 wt % (where m is the mass), temperature = 85°C. With increasing content of these factors, the oil absorbency increased at first and then decreased. Compared with binary copolymer St/BMA prepared in previous research, the highest oil absorbencies to dichloromethane were 12.80 and 23.00 g/g in the St/BMA and St/BMA/SMA copolymers, respectively. St/BMA/SMA had a higher oil absorbency and faster oil‐adsorbing rate than St/BMA. The oil absorption in the oil–water mixture and the recovery of the resin were also studied in detail. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40180.     

Rheology of poly(n‐butyl methacrylate) and its composites with calcium carbonate

Poly(n‐butyl methacrylate) (PBMA) composites with calcium carbonate (CaCO₃) were prepared by in situ radical copolymerization of butyl methacrylate (BMA) and methacrylic acid (MA) with precipitated calcium carbonate. To compare the different rheological behaviors of the monomer mixtures with CaCO₃ and the composites, the steady and dynamic viscosities of BMA/MA/CaCO₃ and poly(BMA/MA/CaCO₃) were measured by means of steady and oscillatory shear flows. The viscosity of the mixture BMA/MA/CaCO₃ was found to increase evidently with the increasing of CaCO₃%. The influence of MA% on viscosity of BMA/MA/CaCO₃ was slight. During the in situ polymerization, the viscosity of the reacting system was measured to be enhanced by a factor of about 10⁴ from the monomer/CaCO₃ mixture to composites. The dependency of zero‐shear viscosity on molar mass of PBMA was also investigated. The relation between the zero‐shear viscosity and molar mass is η₀ = 10^?15 M_w^3.5. The evolution of the viscosity with the temperature for both PBMA and its composites was obtained and time–temperature superposition was used to build master curves for the dynamic moduli. The flow activation energies were found to be 115.0, 148.6, and 178.7 kJ/mol for PBMA, composite PBMA/CaCO₃ (90/10), and PBMA/MA/CaCO₃ (89/1/10), respectively. The viscosity of the composites containing less than 10% CaCO₃ was lower than that of pure PBMA with the same molar mass. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1376–1383, 2003     

含3nm硅溶胶的苯丙杂化乳液的制备与性能研究

在单一乳化剂存在下 ,用原位分散聚合方法制备了含 3 nm硅溶胶的苯丙杂化乳液。通过 FTIR、粒径分析、ζ电位和流变性能测试 ,表征了杂化乳液中的杂化效应、微粒形态及乳液稳定性 ,并与分别由 3 nm和 1 0 nm硅溶胶与苯丙乳液直接共混形成的杂化乳液进行了比较。与直接共混的杂化乳液成膜后的力学性能相比 ,由原位分散聚合形成的 3 nm硅溶胶杂化乳液成膜后 ,显示出较高的拉伸强度、拉伸模量和断裂伸长率。     

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.