Free‐radical terpolymerization of n‐butyl acrylate/butyl methacrylate/d‐limonene

d ‐Limonene (Lim) is a renewable monoterpene derived from citrus fruit peels. We investigated it for use as part of a more sustainable polymer formulation. The bulk free‐radical terpolymerization of n‐butyl acrylate (BA)/butyl methacrylate (BMA)/Lim was carried out at 80°C with benzoyl peroxide as the initiator. The terpolymerization was studied at various initial BA/BMA/Lim molar ratios, and the products were characterized for conversion, terpolymer composition, molecular weight, and glass‐transition temperature. Lim was observed to undergo a significant degradative chain‐transfer reaction, which greatly influenced the polymerization kinetics. The rate of polymerization, final conversion, and polymer molecular weight were all significantly reduced because of the presence of Lim. Nonetheless, polymers with relatively high weight‐average molecular weights (20,000–120,000 Da) were produced. The terpolymer composition was well predicted with the reactivity ratios estimated for each of the three copolymer subsystems. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42821.     

Inline monitoring of styrene/butyl acrylate miniemulsion polymerization with attenuated total reflectance/Fourier transform infrared spectroscopy

The copolymerization of styrene/butyl acrylate in a miniemulsion was monitored inline with an attenuated total reflectance/Fourier transform infrared (ATR–FTIR) probe. ATR–FTIR spectroscopy was used to track the concentration of the monomers, thereby providing conversion and polymer composition data. Offline gravimetry and ¹H‐NMR spectroscopy were used to provide a comparison with the ATR–FTIR data. Because of inconsistent results with a univariate method, a multivariate or partial least squares calibration method using the full spectra of the reactions was selected and gave excellent results. No statistically significant differences were found between the offline and ATR–FTIR spectroscopy data coupled with multivariate statistics, and this confirmed that ATR–FTIR spectroscopy is a reliable tool for monitoring the conversion and polymer composition in miniemulsion polymerizations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 46–52, 2007     

Emulsion-based pressure sensitive adhesives from conjugated linoleic acid/styrene/butyl acrylate terpolymers

Free radical emulsion terpolymerizations of conjugated linoleic acid (CLA), styrene (Sty), and butyl acrylate (BA) were performed at 80 °C. Terpolymers were characterized for composition, conversion, molecular weight and glass transition temperature, latexes were characterized for viscosity and particle size while adhesives were characterized for tack, peel strength, shear strength, storage modulus, loss modulus and tan delta. One impurity commonly found in CLA, oleic acid, was shown to influence the reaction kinetics significantly. Adhesive performance was tuned using divinylbenzene (DVB) crosslinker to keep the terpolymer molecular weight in a desired range. By using a constrained mixture design, the influence of terpolymer composition, chain transfer agent (CTA) concentration, DVB concentration, molecular weights, viscosity and particle size on tack, peel strength and shear strength was investigated. The final forms of the resulting empirical models allowed the creation of 3D response surfaces for pressure sensitive adhesive (PSA) performance optimization.     

Agitation effects in the semicontinuous emulsion polymerization of styrene and butyl acrylate

The effect of agitation on the semicontinuous emulsion copolymerization of styrene and butyl acrylate was investigated. Both neat monomer addition and preemulsified feed were used. Experiments with and without a chain‐transfer agent were carried out. For neat monomer addition, a mild degree of agitation (≥ 0.1 kW/m³) was required to avoid monomer mass‐transfer limitations, but even a moderate degree of agitation (0.3 kW/m³) was not enough to overcome the CTA mass‐transfer limitations. Agitation was much less critical when preemulsified feeds were used. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 841–851, 2001     

Effect of freeze‐thaw pretreatment on thermal drying process and physicochemical properties of chitosan

The effect of freeze‐thaw pretreatment on the thermal drying process and physicochemical properties of chitosan was investigated in this study. Results showed that the freeze‐thaw treatment changed the form of chitosan paste and reduced 75.6–77.7% of the water content. The freeze‐thaw treatment decreased the drying time of chitosan from 16–19 h to 2.75–4 h and the dried product was loosely packed powder. After freeze‐thaw treatment, the molecular weight of chitosan was unchanged during the thermal drying. The heat‐induced browning effect of chitosan during drying was greatly alleviated by the pretreatment. Furthermore, the pretreatment increased the 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) radical‐scavenging activity of dried product by 40.4–59.8%. The molecular weight, color, and DPPH radical‐scavenging activity of the pretreated dried chitosan product were close to those of freeze‐dried product. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41017.     

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 styrene‐butyl acrylate polymers,varying feed composition in a semicontinuous emulsion process

Two‐stage polymerization has been used to improve properties of two‐component polymers. In this work, a semicontinuous emulsion process varying feed composition along the reaction is used to produce copolymer chains of different composition as conversion proceeds. Polymer composition and evidence of branching were determined by ¹H‐NMR. Polymer molecular weight values determined by GPC are beyond the range where mechanical properties depend on molecular weight. Mechanodynamic properties show a copolymer type behavior with a synergistic effect around the 50/50 styrene/butyl acrylate composition ratio. For such composition, mechanical performance superiority of variable composition copolymer with respect to two‐stage polymer was confirmed with stress–strain tests carried out at several temperatures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3964–3971, 2007     

醋酸乙烯酯/马来酸/丙烯酸丁酯无皂共聚乳液研究

采用无皂乳液聚合方法合成聚醋酸乙烯酯/马来酸/丙烯酸丁酯乳液。以透射电镜观察乳胶粒的表面形态并测量粒径,对乳胶粒的增长机理进行了分析。以转化率、吸水性、拉伸强度和乳液的稳定性为主要指标考查了共聚单体用量、pH等因素对乳液性能的影响。结果表明,马来酸占总单体量的3%,丙烯酸丁酯占8%,pH为6时共聚乳液具有良好的性能。     

苯乙烯/丙烯酸丁酯反向原子转移自由基乳液聚合的合成与表征

采用Tween 80为乳化剂,FeCl3.6H2O/EDTA/AIBN为催化引发体系,在乳液体系中对苯乙烯、丙烯酸丁酯进行反向原子转移自由基(RATRP)共聚合。考察了原料加入方式、过渡金属催化剂浓度及反应温度对RATRP乳液聚合影响。结果表明,得到聚合物的分子量与单体转化率呈线性增长,分子量分布较窄(PDI为1.40)的无规共聚物。借助于凝胶渗透色谱(GPC)和红外光谱仪(IR)对RATRP共聚乳液进行表征,表明加入催化体系进行RA-TRP乳液聚合是"活性"可控聚合。     

Toughness improvement of poly(lactic acid) with poly(vinyl propionate)-grafted natural rubber

Natural rubber (NR) grafted with poly(vinyl propionate) (NR-g-PVP) was prepared by emulsion polymerization. The monomer content was set at 5, 10, 20, and 30 wt%. The chemical structure of NR-g-PVP was confirmed by ¹H-NMR and FTIR techniques. The grafting parameters of purified NR-g-PVP were evaluated. Binary (PLA/NR and PLA/NR-g-PVP) and ternary (PLA/NR/NR-g-PVP) blends were prepared by melt blending using a twin-screw extruder. The percentage of grafted PVP on NR affected morphology, thermal and mechanical properties of the blends. In binary blends, 5% grafting showed the greatest improvement of toughness and ductility with PLA, whereas there was no improvement in the mechanical properties of PLA/NR blend from using NR-g-PVP as a compatibilizer. The mechanical properties of the blends are related to mutual compatibility of the components. Good interfacial adhesion and proper particle size of NR were the key factors contributing to mechanical properties.     

Molecular weight development in emulsion copolymerization of n‐butyl acrylate and styrene

The seeded emulsion copolymerization of n‐butyl acrylate and styrene in a weight ratio of 50/50 was investigated. The effect of the type of process (batch vs. semicontinuous) and the amounts of initiator and emulsifier charged into the reactor on the time evolution of the fractional conversion, number of polymer particles, and weight‐average molecular weight (M_w) was analyzed. It was found that the M_w depends to a slight extent on the type of process and the emulsifier concentration and to a larger extent on the initiator concentration. The molecular weight distributions (MWDs) and the gel content of the final latexes were also analyzed. In the absence of chain transfer agents (CTAs), the fraction of gel was higher in the semicontinuous processes. It was also found that the gel content increased with increasing initiator concentration in the recipe. The addition of 1 wt % CTA avoided gel formation and led to an important reduction of the M_w. Nevertheless, the MWDs presented a shoulder or even a second peak at high molecular weights that was due to reactions of chain transfer to the polymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1918–1926, 2003     

A novel flame retardant UV‐curable vinyl ester resin monomer based on industrial dipentene: Preparation,characterization, and properties

A novel bio‐based and flame‐retardant UV‐curable vinyl ester resin (VER) monomer named Diglycidyl ester of maleinized dipentene modified with dibutyphosphate and methacrylic anhydride (MDDMD) was synthesized from industrial dipentene via Diels‐Alder reaction, glycidylation, epoxy ring‐opening reaction, and esterification. Its chemical structures were characterized by Fourier transform infrared (FTIR) analysis and proton nuclear magnetic resonance (¹H‐NMR). In order to improve its flexibility, we prepared a series of copolymers under UV light radiation by mixing it with certain proportions of poly(ethylene glycol) dimethacrylate‐200 (PEGDMA‐200) which contained flexible groups. Their tensile property, curing degrees (CD), hardness, limiting oxygen index (LOI), dynamic mechanical thermal properties, and thermostability were all investigated. The cured mixed resins have a relatively high tensile strength of 10.05 MPa and curing degrees up to 92.5%. Both hardness (range: 50 to 23 HD) and LOI (range: 22.8% to 24.4%) of cured resins are improved with the increase of MDDMD content. Dynamic mechanical analysis (DMA) shows that their glass transition temperatures rise with the increase of MDDMD content. Thermogravimetric analysis (TGA) shows that the thermal stability of cured resins is enhanced with the increase of PEGDMA‐200 content, as the main thermal initial decomposition temperatures are all above 260 °C and char yield at 800 °C are above 18.10%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44084.     

Core–shell emulsion polymerization of styrene and butyl acrylate in the presence of polymerizable emulsifier

A series of core–shell polymeric particles of styrene butyl acrylate were successfully prepared in the presence of polymerizable emulsifier. The compositions of the emulsions obtained were confirmed by Fourier transformed infrared spectrometry. Latexes and emulsion films were characterized by transmission electron microscopy and scanning electron microscopy, respectively. The thermostability of emulsion films was characterized by thermogravimetric analysis. The results showed that the existence of polymerizable emulsifier could enhance the solid content of the emulsion and the monomer conversion. The optimum mass ratio of polymerizable emulsifier to traditional emulsifier was 1:1, and the polymerizable emulsifier can participate in the emulsion polymerization perfectly. An emulsion with reverse core–shell particles exhibited better hydrophobic properties and thermostability than one with traditional core–shell particles. The film formed by the emulsion with reverse core–shell particles had lower water absorption, and it could be used in the fields of coatings, surface sizing agents, and spinning. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43091.     

Synthesis and characterization of a soybean oil‐based macromonomer

An acrylate‐functional soybean oil‐based macromonomer (SoyAA‐1) was synthesized in high yields utilizing sequential amidation and acrylation processes to serve as an internal plasticizer in emulsion polymers. The structure and structure–property relationships of this unique macromonomer were validated with FTIR, NMR, and LC‐MS. The viability of SoyAA‐1 as a comonomer in emulsion polymerization was established via copolymerization with methyl methacrylate (MMA) at varying copolymer weight compositions. The effect of increasing SoyAA‐1 levels and concomitantly higher allylic functionality was measured through film coalescence, minimum film forming temperature, and initial and progressively increasing glass transition temperature(s). The results indicate that synthetic modification of a renewable resource, soybean oil, can yield a valuable monomer that can be copolymerized in high yields via emulsion polymerization to produce practical and mechanically stable latexes for a variety of coatings applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40249.     

Stability and copolymerization of concentrated emulsion of styrene and butyl acrylate in the presence of polyurethane macromonomer

A study has been made of the stability and copolymerization of concentrated emulsion of styrene (St) and butyl acrylate (BA) in the presence of polyurethane macromonomer (DPUA), which contains C?C at one end. First, the DPUA macromonomer was synthesized from the appropriate amount of 2,4‐diisocyanate (TDI), polypropylene glycol (PPG), 2‐hydroxyethyl methylacrylate (HEMA), dimethylolpropionic acid (DMPA), and triethylamine (TEA) by four steps. Then, the DPUA was dissolved in St‐BA monomer mixtures. The DPUA/St‐BA concentrated emulsion copolymerization using sodium dodecyl sulfate/cetyl alcohol (SDS/CA) as composite surfactant and polyvinyl alcohol (PVA) as liquid film reinforcer, and ammonium persulfate/sodium hydrogen sulfate (APS/SHS) as redox initiator system was carried out at 30°C. The effect of NCO/OH molar ratio, surfactants' concentration, mass ratio of DPUA/St‐BA, initiators' concentration, volume fraction of the monomer phase (Φ), and temperature on the stability or the copolymerization of the concentrated emulsion of DPUA/St‐BA were investigated. The average size and distribution of the latex particles obtained under different conditions were also analyzed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1992–1999, 2007     

Characterization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) biosynthesized by mixed microbial consortia fed fermented dairy manure

The bioplastic poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV), was isolated from a bioreactor using mixed microbial consortia fed volatile fatty acids (VFA), from fermented dairy manure, as the carbon source. The molar fraction of 3‐hydroxyvalerate (3HV) amounted to 0.33 mol mol^?1 for two isolated PHBV samples as determined by GC‐MS and ¹H‐NMR spectroscopy. The chemical, thermal, and mechanical properties were determined. The PHBVs had relatively high M_w (～790,000 g mol^?1). Only a single glass transition temperature (T_g) and melting point (T_m) were observed. Isolated PHBVs exhibited good flexibility and elongation to break as compared with commercial PHBVs with lower HV. The diad and triad sequence distributions of the monomeric units were determined by ¹³C‐NMR spectroscopy and followed Bernoullian statistics suggesting that the PHBVs were random. The PHBV sequence distribution was also characterized by electrospray ionization‐mass spectrometry (ESI‐MSⁿ) after partial alkaline hydrolysis to oligomers showing a random 3HV distribution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40333.     

Evaluation of the efficiency of copolymers of methyl methacrylate and vinyl acetate synthesized by emulsion polymerization for control of aqueous filtrate loss

One of the main problems faced while drilling oil wells is loss of fluid to the rock formation. This loss can be reduced with the use of chemical additives called filtrate controllers, which must be tailored to the specific characteristics of the rock formation and drilling conditions. In this study, copolymers made of methyl methacrylate‐co‐vinyl acetate were synthesized by the emulsion polymerization technique, the most efficient technique to obtain copolymers with widely differing reactivity ratios. The products were characterized and evaluated for filtrate reduction efficiency, in the form of an emulsion and a polymer suspended in water. The filtrate reduction percentage, on the order of 80%, increased with higher concentration of vinyl acetate. The use of the polymer suspended in water caused only a slightly greater reduction in filtrate loss than that produced by the respective emulsion. However, other important advantages are associated with the suspended formulation: lower optimal concentration (～ 8.5 g/mL), formation of extremely discrete filter cake particles and better logistical aspects, since in the case of emulsions, the volume of material that must be transported is much greater. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42191.     

聚合工艺对丙烯酸酯乳液胶粘剂性能的影响

主要研究了聚合工艺对丙烯酸酯乳液胶粘剂性能的影响 通过对乳液胶粘剂的各种性能测试,发现3种聚合方法中,种子乳液聚合法制备的乳液胶粘剂的综合性能较为理想 采用种子乳液聚合法,最佳聚合工艺为:单体的滴加时间4h、聚合温度50℃、搅拌速率80 r/min     

Thermal properties and crystallization behavior of fractionated blocky and random polyhydroxyalkanoate copolymers from mixed microbial cultures

This study represents the first detailed analysis of the thermal, morphological, and crystallization properties of the blend components within a range of mixed‐culture polyhydroxyalkanoates (PHAs), with 3‐hydroxyvalerate content in the as‐produced materials and in the fractions ranging from low (12 mol %) to high (91 mol %). Both coarse and fine fractionation of the as‐produced copolymers confirmed that they were blends of nominally blocky and/or random copolymers of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate), with very broad compositional distributions as governed by the PHA accumulation strategy. The crystallization kinetics and thermal properties of the fractions were found to be very significantly different from each other, consistent with the hypothesis that the overall mechanical properties were primarily controlled by the more rapidly crystallizing components. Two materials produced using an alternating feeding strategy demonstrated unique crystallization and thermal properties in their fractions, which are considered to have contributed to distinctly more elastic mechanical properties in these particular samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40836.     

Synthesis of poly(butyl acrylate)—laponite nanocomposite nanoparticles for improving the impact strength of poly(lactic acid)

This work aims at preparing and characterizing poly(butyl acrylate) (PBA)—laponite (LRD) nanocomposite nanoparticles and nanocomposite core (PBA‐LRD)‐shell poly(methyl methacrylate) (PMMA) nanoparticles, on the one hand, and the morphology and properties of poly(lactic acid) (PLA)‐based blends containing PBA‐LRD nanocomposite nanoparticles or (PBA‐LRD)/PMMA core–shell nanoparticles as the dispersed phase, on the other hand. The PBA and (PBA‐LRD)/PMMA nanoparticles were synthesized by miniemulsion or emulsion polymerization using LRD platelets modified by 3‐methacryloxypropyltrimethoxysilane (MPTMS). The grafting of MPTMS onto the LRD surfaces was characterized qualitatively using FTIR and quantitatively using thermogravimetric analysis (TGA). The amounts of LRD in the PBA‐LRD nanocomposites were characterized by TGA. The PBA/PMMA core–shell particles were analyzed by ¹H‐NMR. Their morphology was confirmed by SEM and TEM. Mechanical properties of (PBA‐LRD)/PLA blends and (PBA‐LRD)/PMMA/PLA ones were tested and compared with those of the pure PLA, showing that core–shell particles allowed increasing impact strength of the PLA while minimizing loss in Young modulus and tensile strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013