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.     

Synthesis of well‐defined,functionalized polymer latex particles through semicontinuous emulsion polymerization processes

The design of a semicontinuous emulsion polymerization process, primarily based on theoretical calculations, has been carried out with the objective of achieving overall independent control over the latex particle size, the monodispersity in the particle size distribution, the homogeneous copolymer composition, the concentration of functional groups (e.g., carboxyl groups), and the glass‐transition temperature with n‐butyl methacrylate/n‐butyl acrylate/methacrylic acid as a model system. The surfactant coverage on the latex particles is very important for maintaining a constant particle number throughout the feed process, and this results in the formation of monodisperse latex particles. A model has been set up to calculate the surfactant coverage from the monomer feed rate, surfactant feed rate, desired solid content, and particle size. This model also leads to an equation correlating the polymerization rate to the instantaneous conversion of the monomer or comonomer mixture. This equation can be used to determine the maximum polymerization rate, only below or at which monomer‐starved conditions can be achieved. The maximum polymerization rate provides guidance for selecting the monomer feed rate in the semicontinuous emulsion polymerization process. The glass‐transition temperature of the resulting carboxylated poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) copolymer can be adjusted through variations in the compositions of the copolymers with the linear Pochan equation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 30–41, 2003     

Seeded emulsion terpolymerization of dimethyl meta-isopropenyl benzyl isocyanate (TMI®) with acrylic monomers

Dimethyl meta-isopropenyl benzyl isocyanate (TMI®) is a novel bifunctional monomer. It has a double bond and an isocyanate group. The seeded emulsion terpolymerization of TMI with the acrylic monomers, methyl methacrylate and n-butyl acrylate, has been studied. A copolymer of methyl methacrylate and n-butyl acrylate was used as the seed latex. In order to minimize the risk of hydrolysis of TMI, polymerizations were carried out at 40°C using redox initiators. No additional surfactant was added during the second-stage polymerization in order to avoid the nucleation of secondary particles. TMI was found to retard the polymerization kinetics. The effect of variables, such as the total number of particles, initiator concentration, and the monomer feed rate on polymerization kinetics, was investigated. The composition of the second-stage polymer could be controlled by running the polymerization under monomer-starved conditions. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 685–694, 1998     

Polymer-leather composites. I. Process and location study for the deposition of selected acrylate monomers by polymerization into chrome-tanned cattlehide

Three acrylate monomer systems were deposited by redox emulsion polymerization at room temperature into the fibrous matrix of 2-mm-thick chrome-tanned cattlehide over a wide range of composition. Polymer not bound to the matrix was separated by hot benzene extractions. Monomers used were methyl methacrylate, a mixture of n-butyl acrylate and methyl methacrylate and n-butyl acrylate, each selected to produce composites having wide variation in glass-transition temperature. The same three systems were introduced into the free space of leather by bulk and solution polymerization. All conversions were close to 100%. When the emulsion technique was used, with feed composition variable, overall deposition efficiency depended on the characteristic rate of deposition for the individual acrylate monomers. Observed orders in deposition rate and overall efficiency were: methyl methacrylate > comonomer > n-butyl acrylate. However, specific deposition efficiencies declined roughly monotonically with feed or time increase, but maintained the same order. Microscopic examination of thin sections revealed polymer only in the outer region of the leather cross section. Information on polymer location and its influence on specimen thickness for composites prepared by both emulsion and solution methods of deposition were obtained by correlating experimental densities with theoretical density–composition curves for various assumed models. The foregoing, together with observations of greatly reduced grafting frequency, in view of the maximum theoretically attainable, made a dominant grafting mechanism unattractive. A mechanism involving diffusion controlled monomer transport to occluded radicals in localized polymer deposits was suggested as an alternative.     

Thermal and sonochemical degradation kinetics of poly(n‐butyl methacrylate‐co‐alkyl acrylates): Variation of chain strength and stability with copolymer composition

The thermal degradation of poly(n‐butyl methacrylate‐co‐alkyl acrylate) was compared with ultrasonic degradation. For this purpose, different compositions of poly (n‐butyl methacrylate‐co‐methyl acrylate) (PBMAMA) and a particular composition of poly(n‐butyl methacrylate‐co‐ethyl acrylate) (PBMAEA) and poly(n‐butyl methacrylate‐co‐butyl acrylate) (PBMABA) were synthesized and characterized. The thermal degradation of polymers shows that the poly(alkyl acrylates) degrade in a single stage by random chain scission and poly(n‐butyl methacrylate) degrades in two stages. The number of stages of thermal degradation of copolymers was same as the majority component of the copolymer. The activation energy corresponding to random chain scission increased and then decreased with an increase of n‐butyl methacrylate fraction in copolymer. The effect of methyl acrylate content, alkyl acrylate substituent, and solvents on the ultrasonic degradation of these copolymers was investigated. A continuous distribution kinetics model was used to determine the degradation rate coefficients. The degradation rate coefficient of PBMAMA varied nonlinearly with n‐butyl methacrylate content. The degradation of poly (n‐butyl methacrylate‐co‐alkyl acrylate) followed the order: PBMAMA < PBMAEA < PBMABA. The variation in the degradation rate constant with composition of the copolymer was discussed in relation to the competing effects of the stretching of the polymer in solution and the electron displacement in the main chain. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

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     

Mechanical property investigation of single polymer particles with the variation of molecular structure of crosslinking monomer

The effects of the swelling ratio (S/R), the existence of methyl side groups, the length and molecular structure of backbone chain of crosslinking monomer on the variation of mechanical properties of single polymer particle were investigated. For the study, monodisperse polymer particles were prepared via one‐step seeded polymerization using PMMA as seed particles and 1,n‐alkanediol di(meth)acrylate or (ethylene glycol)_n di(meth)acrylate as crosslinking monomer. Recovery rate, K‐values, breaking strength, and breaking displacement were measured as mechanical properties and they were performed by using microcompression test. The following observations were made: (1) only breaking strength was closely related to the swelling ratio; (2) the existence of methyl side groups increased the K‐values but decreased the recovery rate of the polymer particles; and (3) K‐values were the most sensitive to the variation of backbone chain length of crosslinking monomer, and they were decreased with the increase of the backbone chain length of crosslinking monomer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis,characterization, and thermal behavior study of methyl methacrylate polymers containing 4‐carbazole substitutes

A new polymerizable monomer, [4‐(9‐ethyl)carbazolyl]methyl methacrylate ( 2 ), was synthesized by reacting of methacrylic acid and 4‐hydroxymethyl‐9‐ethyl carbazole ( 1 ) by esterification procedure in the presence of N,N′‐dicyclohexylcarbodiimide. The resulting monomer was then polymerized free‐radically to form the poly(methyl methacrylate) containing 4‐(9‐ethyl)carbazolyl pend ent groups. Also, copolymerization of monomer 2 with various acrylic monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, and n‐butyl acrylate by azobisisobutyronitrile as a free radical polymerization initiator gave the related copolymers in high yields. The structure of all the resulted compounds was characterized and confirmed by FTIR and ¹H NMR spectroscopic techniques. The average molecular weight of the obtained polymers was determined by gel permeation chromatography using tetrahydrofurane as the solvent. The thermal gravimetric analysis and differential scanning calorimeter instruments were used for studying of thermal properties of polymers. It was found that, with the incorporation of bulky 4‐(9‐ethyl)carbazolyl substitutes in side chains of methyl methacrylate polymers, thermal stability and glass transition temperature of polymers are increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4989–4995, 2006     

Mathematical modeling of diffusion‐controlled free‐radical terpolymerization reactions

A comprehensive mathematical model is developed to describe the kinetics and molecular and compositional developments in a free‐radical terpolymerization batch reactor. This model is based on a fairly general kinetic mechanism, including chain‐transfer and terminal double‐bond reactions. We take into account the effects of diffusion‐controlled phenomena (i.e., gel, glass, and cage effects) on polymerization kinetics by extending our previous model on diffusion‐controlled reactions to terpolymerization systems. Triple moments for the live and dead trivariate chain‐length terpolymer composition distributions are introduced to describe the molecular and compositional developments in the terpolymerization system. The predictive capabilities of this model are demonstrated by simulation of the free‐radical, bulk terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate under different experimental conditions. It is shown that the model predictions are in good agreement with experimental data on monomer conversion, average molecular weights, and terpolymer composition, as reported by Dube and Penlidis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 161–176, 2003     

Synthesis and characterization of oil sorbers based on docosanyl acrylate and methacrylates copolymers

Docosanyl acrylate (DCA) monomer was copolymerized with different monomer feed ratios of cinnamoyloxy ethyl methacrylate (CEMA) or methyl methacrylate (MMA) monomer to produce different compositions for DCA/CEMA or DCA/MMA copolymer with low conversions.¹H NMR spectroscopy was used to confirm the copolymer structure. DCA was crosslinked with different mol % of CEMA or MMA using dibenzoyl peroxide as initiator and various weight percentages of either 1,1,1‐trimethylolpropane triacrylates or 1,1,1‐trimethylolpropane trimethacrylates crosslinkers. The effects of monomer feed composition, crosslinker concentration, and the hydrophobicity of the copolymer units on swelling properties of the crosslinked polymers were studied through the oil absorbency tests. The network parameters, such as polymer solvent interaction (χ), effective crosslink density (υ_e), equilibrium modulus of elasticity (G_T), and average molecular weight between crosslinks (M_c), were determined and correlated with the structure of the synthesized copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Using hydroxypropyl‐β‐cyclodextrin for the preparation of hydrophobic poly(ketoethyl methacrylate) in aqueous medium

This work was committed to the polymerization of hydrophobic ketoethyl methacrylate monomer in aqueous medium in the presence of cyclodextrin, instead of polymerizing the monomer in toxic and volatile organic solvents. For this purpose, a new ketoethyl methacrylate monomer, p‐methylphenacylmethacrylate (MPMA), was synthesized from the reaction of p‐methylphenacylbromide with sodium methacrylate in the presence of triethylbenzylammonium chloride. The monomer was identified with FTIR, ¹H and ¹³C‐NMR spectroscopies. Hydroxypropyl‐β‐cyclodextrin (HPCD) was used to form a water‐soluble host/guest inclusion complex (MPMA/HPCD) with the hydrophobic monomer. The complex was identified with FTIR and NMR techniques and polymerized in aqueous medium using potassium persulfate as initiator. During polymerization the resulting hydrophobic methacrylate polymer precipitated out with a majority of HPCD left in solution and a minority of HPCD bonded on the resulting polymer. The thus‐prepared polymer exhibited little difference from the counterparts obtained in organic solvent in number average molecular weight (M_n), polydispersity (M_w/M_n) and yield. The investigation provides a novel strategy for preparing hydrophobic ketoethyl methacrylate polymer in aqueous medium by using a monomer/HPCD inclusion complex. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

n‐Butyl acrylate based latex interpenetrating polymer networks used as processing modifiers and impact modifiers of poly(vinyl chloride)

A latex interpenetrating polymer network (LIPN), consisting of poly(n‐butyl acrylate), poly(n‐butyl acrylate‐co‐ethylhexyl acrylate), and poly(methyl methacrylate‐co‐ethyl acrylate) and labeled PBEM, with 1,4‐butanediol diacrylate as a crosslinking agent was synthesized by three‐stage emulsion polymerization. The initial poly(n‐butyl acrylate) latex was agglomerated by a polymer latex containing an acrylic acid residue and then was encapsulated by poly(n‐butyl acrylate‐co‐ethylhexyl acrylate) and poly(methyl methacrylate‐co‐ethyl acrylate). A polyblend of poly(vinyl chloride) (PVC) and PBEM was prepared through the blending of PVC and PBEM. The morphology and properties of the polyblend were studied. The experimental results showed that the processability and impact resistance of PVC could be enhanced considerably by the blending of 6–10 phr PBEM. This three‐stage LIPN PBEM is a promising modifier for manufacturing rigid PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1168–1173, 2004     

Kinetics of atom transfer radical polymerization of crosslinkable terpolymer P(MMA‐BA‐HEMA)

A crosslinkable terpolymer P(MMA‐BA‐HEMA) was prepared by atom transfer radical copolymerization of 2‐hydroxyethyl methacrylate, methyl methacrylate and butyl acrylate. The structure of the terpolymer was characterized by ¹H NMR and gel permeation chromatography. The effects on the polymerization of ligand, initiator, solvent, CuCl₂ added in the initial stage and reaction temperature were investigated. The optimal reaction conditions were ethyl 2‐bromopropionate as initiator, CuCl/PMDETA as catalyst, cyclohexanone as solvent, catalyst/ligand = 1:1.5, [M]₀:[I]₀ = 200:1 and temperature 70 °C. The reaction followed first‐order kinetics with respect to monomer concentration, indicating the best control over the polymerization process, a constant concentration of the propagating radical during the polymerization, efficient control over M_n of the polymer and low polydispersity (M_w/M_n < 1.3). © 2013 Society of Chemical Industry     

Synthesis and characterization of functionalized polymer latex particles through a designed semicontinuous emulsion polymerization process

Monodispersed noncarboxylated and carboxylated poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) latices were synthesized with a well‐defined semicontinuous emulsion polymerization process. A modified theory to correlate the polymerization rate to the instantaneous conversion of the monomer or comonomer mixture was developed. The resulting equation was used to determine the maximum polymerization rate only below or equal to which the polymerization could be operated in the highly monomer‐starved regime, which corresponded to an instantaneous conversion of 90% or greater. Experimental data from reaction calorimetry supported that the polymerization was under highly monomer‐starved conditions when the model latices were synthesized with the modified model. The estimation of the average number of free radicals per latex particle(n?) during the feeding stage revealed that n? was as high as 1.4 in the actual polymerization, which showed that the original selection of 0.5 as the n? value was not accurate in the developed model. From the conductimetric titration experiments, we found that most of the carboxyl groups from the methacrylic acid (MAA) were buried inside the latex particles, and the surface carboxyl group coverage increased as the MAA concentration in the comonomer feed increased. The glass‐transition temperatures of the synthesized polymers were close to the designed value from the Pochan equation, and only one glass transition was observed in the polymer samples in the differential scanning calorimetry measurements, indicating a homogeneous copolymer composition in the functionalized shell. Particle size characterization and transmission electron microscopy confirmed the uniformity in the latex particle size. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 248–256, 2005     

Synthesis and characterization of butyl acrylate/methyl methacrylate/glycidyl methacrylate latexes

The butyl acrylate (BA)/methyl methacrylate (MMA), and glycidyl methacrylate (GMA) composite copolymer latex was synthesized by seeded emulsion polymerization technique taking poly(methyl methacrylate) (PMMA) latex as the seed. Four series of experiments were carried out by varying the ratio of BA : MMA (w/w) (i.e. 3.1 : 1, 2.3 : 1, 1.8 : 1, and 1.5 : 1) and in each series GMA content was varied from 1 to 5% (w/w). The structural properties of the copolymer were analyzed by FTIR, ¹H‐, and ¹³C‐NMR. Morphological characterization was carried out using transmission electron microscopy (TEM). In all the experiments, monomer conversion was ～99% and final copolymer composition was similar to that of feed composition. The incorporation of GMA into the copolymer chain was confirmed by ¹³C‐NMR. The glass transition temperature (T_g) of the copolymer latex obtained from the differential scanning calorimetry (DSC) curve was comparable to the values calculated theoretically. With increase in GMA content, particles having core‐shell morphology were obtained, and there was a decrease in the particle size as we go from 2–5% (w/w) of GMA. The adhesive strength of the latexes was found to be dependent on the monomer composition. With increase in BA : MMA ratio, the tackiness of the film increased while with its decrease the hardness of the film increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

(Meth)acrylic Cross‐Linked Polymer Microparticles: Synthesis by Dispersion Polymerization and Particle Characterization

(Meth)acrylic cross‐linked polymer microparticles have been synthesized by dispersion polymerization in organic media. They were produced by radical copolymerization of mono(meth)acrylate monomers with a certain concentration of a diacrylate as cross‐linker, in a mixture of two organic solvents, heptane and propan‐2‐ol. The reactive surfactant (“surfmer”) was a low solubility parameter acrylate monomer, based on an aliphatic ester group (generally C₁₈) or an isobornyl cycle, which gave auto‐dispersing character to the microparticles. By using glycidyl methacrylate in the monomer mixture, oxirane groups were introduced in the particles. The influence of the major synthesis parameters such as solvent composition, monomer composition and concentration, and initiator concentration has been investigated regarding the size and the molar mass of the cross‐linked polymer microparticles. The study was completed with the influence of the nature and the concentration of the surfmer, the concentration of cross‐linking agent and the composition of monomers feed. Stable cross‐linked microparticles ranging from z‐average radius of gyration, R_z = 20 nm to R_z > 60 nm were obtained by varying the synthesis conditions. The smallest microparticles were prepared with a blend of heptane and propan‐2‐ol in the 50/50 ratio by weight. Increasing the surfmer concentration or reducing the monomer concentration in the reaction mixture usually led to smaller microparticles. The longer the aliphatic chain of the surfmer, the smaller the microparticles. Minimum sizes were obtained for cross‐linking agent concentrations between 5 and 7.5 mol‐%, depending on monomers composition. For higher concentrations, macrogelation may occur during the synthesis.     

Morphologies of polybutylacrylate/poly(styrene‐co‐methyl methacrylate) latex prepared by starved emulsion polymerization Part I. Thermodynamics equilibrium morphology

Heterogeneous latexes were prepared by a semicontinuous seeded emulsion polymerization process under monomer starved conditions at 80 °C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(butyl acrylate) latexes were used as seeds. The second‐stage polymer was poly(styrene‐co‐methyl methacrylate). By varying the amounts of methyl methacrylate (MMA) in the second‐stage copolymer, the polarity of the copolymer phase could be controlled. Phase separation towards the thermodynamic equilibrium morphology was accelerated either by ageing the composite latex at 80 °C or by adding a chain‐transfer agent during polymerization. The morphologies of the latex particles were examined by transmission electron microscopy (TEM). The morphology distributions of latex particles were described by a statistical method. It was found that the latex particles displayed different equilibrium morphologies depending on the composition of the second‐stage copolymers. This series of equilibrium morphologies of [poly(butyl acrylate)/poly(styrene‐co‐methyl methacrylate)] (PBA/P(St‐co‐MMA)) system provides experimental verification for quantitative simulation. Under limiting conditions, the equilibrium morphologies of PBA/P(St‐co‐MMA) were predicted according to the minimum surface free energy change principle. The particle morphology observed by TEM was in good agreement with the predictions of the thermodynamic model. Therefore, the morphology theory for homopolymer/homopolymer composite systems was extended to homopolymer/copolymer systems. © 2002 Society of Chemical Industry     

Modeling of the Emulsion Terpolymerization of Styrene, α‐Methylstyrene and Methyl Methacrylate

Summary: This work deals with modeling the terpolymerization of styrene, α‐methylstyrene and methyl methacrylate in the presence of an inhibitor. The model used is a “tendency model” based on the kinetics of the complex elementary chemical reactions both in the aqueous phase and in the particles. It considers the reversible propagation of α‐methylstyrene and the main physical phenomena occurring during the process, i.e., (i) partitioning of monomers, surfactant and inhibitor between the aqueous phase, polymer particles, monomer droplets and micelles; (ii) homogeneous and micellar nucleation; (iii) radical absorption and desorption; (iv) gel and glass effects. The main kinetic parameters of the model are estimated on the basis of batch experimental data in order to be able to describe the complete picture of this complex process. The model can be used to predict (with good precision) the global monomer conversion, number and weight‐average molecular weight, the average diameter and number of polymer particles and the glass transition temperature, and consequently to study the effects of AMS on conversion and terpolymer and latex characteristics.

Comparison of experimental and simulated results of the weight‐average molecular weight versus conversion for the emulsion terpolymerization of styrene, alpha methylstyrene and methyl methacrylate at 60 °C.     

Azeotropy in terpolymerization of 2-pyrimidyl acrylamide with different alkyl acrylates and acrylonitrile

2-Pyrimidyl acrylamide monomer (2PA) has been prepared by the reaction of 2-amino pyrimidine with acrylolyl chloride in the presence of triethylamine as catalyst. Its structure was confirmed by IR and ¹H NMR spectroscopy. Ternary copolymerizations of 2-pyrimidyl acrylamide monomer (2PA) with methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), butyl acrylate (BuA) and acrylonitrile (AN) were carried out in THF at 65°C in the presence of a free radical initiator. Experimental terpolymerization data agree well with calculations based on the Alfrey–Goldfinger equation. The determination of unitary, binary and ternary azeotropies of the various systems studied were easily handled by a computer. The ternary azeotropic compositions for 2PA–MA–AN and 2PA–MMA–AN were 32.20:17.5:50.30 and 13.54:52.64:33.82mol%, respectively. Pseudo-azeotropic regions were identified where the deviation between feed and polymer composition is very small.