Reactive compatibilization of polyamide‐6 (PA 6)/polybutylene terephthalate (PBT) blends by a multifunctional epoxy resin

A multifunctional epoxy resin has been demonstrated to be an efficient reactive compatibilizer for the incompatible and immiscible blends of polyamide‐6 (PA 6) and polybutylene terephthalate (PBT). The torque measurements give indirect evidence that the reaction between PA and PBT with epoxy has an opportunity to produce an in situ formed copolymer, which can be as an effective compatibilizer to reduce and suppress the size of the disperse phase, and to greatly enhance mechanical properties of PA/PBT blends. The mechanical property improvement is more pronounced in the PA‐rich blends than that in the PBT‐rich blends. The fracture behavior of the blend with less than 0.3 phr compatibilizer is governed by a particle pullout mechanism, whereas shear yielding is dominant in the fracture behavior of the blend with more than 0.3 phr compatibilizer. As the melt and crystallization temperatures of the base polymers are so close, either PA or PBT can be regarded as a mutual nucleating agent to enhance the crystallization on the other component. The presence of compatibilizer and in situ formed copolymer in the compatibilized blends tends to interfere with the crystallization of the base polymers in various blends. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 23–33, 2000     

Synthesis and characterization of poly(fluorene)‐based copolymer containing triphenylamine group

The copolymers that are composed of poly(fluorene) (PF), poly(p‐phenylene), and Poly(p‐phenylenevinylene) as backbone and a large 4′‐(N,N′‐diphenylamino)diphenyl or 4′‐(N,N′‐diphenylamino)phenyl as pendent group were synthesized by the nickel(0)‐mediated polycoupling. The composition of the obtained copolymers was confirmed by H NMR. All the copolymers possessed a high weight‐average molecular weight and good solubility in common organic solvents. As the content of triphenyl amine pendants increases, the copolymers showed increased thermal stability due to increased glass transition temperature and increased hole injection ability because of decreased onset of the oxidation potential. In the photoluminescence spectra of copolymers, poly (BDAV₃₀‐co‐DHF₇₀) and poly(BDAPV₃₀‐co‐DHF₇₀) showed efficient energy transfer. indium tin oxide/poly(styrene sulfonate)‐doped poly(3,4‐ethylene dioxythiophene)/poly (BDAV₃₀‐co‐DHF₇₀)/LiF/Al device showed maximum brightness of 2267 cd/m² and efficiency of 0.80 cd/A, with turn‐on voltage at 9.1 V. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 172–182, 2006     

Morphology development of immiscible polymer blends during melt blending: Effects of interfacial agents on the liquid-solid interfacial heat transfer

This article reports on a new phenomenon: The presence of a compatibilizer accelerates the melting/plastification of an immiscible polymer blend during melt blending. The increase in the rate of melting as a result of the addition of a compatibilizer is believed to be one of the important factors responsible for the fact that the morphology of compatibilized blends develops much faster than that of their uncompatibilized counterparts. To substantiate the above statement, blends based on polypropylene (PP) and polyamide 6 (PA6) were used as model systems. The compatibilizer was a graft copolymer (PP-g-PA6) with PP as the backbone and PA6 as grafts. Its presence in a PP/PA6 blend accelerated the rate of melting of the PA6. This effect was observed only when the compatibilizer itself was molten and migrated to the interfacial layer between the PA6 and PP phases. It is likely that the presence of the compatibilizer increased the chain entanglements at the PP and PA6 interface and consequently reduced the thermal resistance of the interfacial layer. Detailed mechanisms are discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3368–3384, 1999     

Thiol-ene Reaction: An Efficient Tool to Design Lipophilic Polyphosphoesters for Drug Delivery Systems

Poly(ethylene glycol)-b-polyphosphoester (PEG-b-PPE) block copolymer nanoparticles are promising carriers for poorly water soluble drugs. To enhance the drug loading capacity and efficiency of such micelles, a strategy was investigated for increasing the lipophilicity of the PPE block of these PEG-b-PPE amphiphilic copolymers. A PEG-b-PPE copolymer bearing pendant vinyl groups along the PPE block was synthesized and then modified by thiol-ene click reaction with thiols bearing either a long linear alkyl chain (dodecyl) or a tocopherol moiety. Ketoconazole was used as model for hydrophobic drugs. Comparison of the drug loading with PEG-b-PPE bearing shorter pendant groups is reported evidencing the key role of the structure of the pendant group on the PPE backbone. Finally, a first evidence of the biocompatibility of these novel PEG-b-PPE copolymers was achieved by performing cytotoxicity tests. The PEG-b-PPE derived by tocopherol was evidenced as particularly promising as delivery system of poorly water-soluble drugs.     

Foaming behavior of polypropylene/polystyrene blends enhanced by improved interfacial compatibility

A series of polypropylene (PP)/polystyrene (PS) blends were prepared by solvent blending with PS‐grafted PP copolymers (PP‐g‐PS) having different PS graft chain length as compatibilizers. The interfacial compatibility was significantly improved with increasing PS graft chain length until the interface was saturated at PS graft chain length being 3.29 × 10³ g/mol. The blends were foamed by using pressure‐quenching process and supercritical CO₂ as the blowing agent. The cell preferentially formed at compatibilized interface because of low energy barrier for nucleation. Combining with the increased interfacial area, the compatibilized interface lead to the foams with increased cell density compared to the uncompatibilized one. The increase in interfacial compatibility also decreased the escape of gas, held more gas for cell growth, and facilitated the increase in expansion ratio of PP/PS blend foams. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1641–1651, 2008     

Reactively and physically compatibilized immiscible polymer blends: stability of the copolymer at the interface

This paper reports on the interfacial behaviour of block and graft copolymers used as compatibilizers in immiscible polymer blends. A limited residence time of the copolymer at the interface has been shown in both reactive blending and blend compatibilization by preformed copolymers. Polystyrene (PS)/polyamide6 (PA6), polyphenylene oxide (PPO)/PA6 and polymethylmethacrylate (PMMA)/PA6 blends have been reactively compatibilized by a styrene-maleic anhydride copolymer SMA. The extent of miscibility of SMA with PS, PPO and PMMA is a key criterion for the stability of the graft copolymer at the interface. For the first 10 to 15 minutes of mixing, the in situ formed copolymer is able to decrease the particle size of the dispersed phase and to prevent it from coalescencing. However, upon increasing mixing time, the copolymer leaves the interface which results in phase coalescence. In PS/LDPE blends compatibilized by preformed PS/hydrogenated polybutadiene (hPB) block copolymers, a tapered diblock stabilizes efficiently a co-continuous two-phase morphology, in contrast to a triblock copolymer that was unable to prevent phase coarsening during annealing at 180°C for 150 minutes.     

ABA-type amphiphilic triblock copolymers containing p-ethoxy azobenzene via atom transfer radical polymerization: Synthesis,characterization, and properties

ABA-type amphiphilic triblock copolymers composed of poly(ethylene glycol)s (PEGs) with different number-average molecular weights as the hydrophilic blocks (B) and poly{6-[4-(4-ethoxyphenylazo)phenoxy]hexyl methacrylate} (PA6C) as the hydrophobic blocks (A) were prepared via atom transfer radical polymerization. These copolymers were prepared from bromo-terminated macroinitiators based on PEG6000, PEG2000, and PEG600, with CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine as the catalytic system, at 85 °C in anisole. The block copolymers were characterized with ¹H NMR spectroscopy and gel permeation chromatography. Differential scanning calorimetry measurements were performed to reveal the phase segregation. In contrast to those polymers with similar compositions and structures in previous reports, these amphiphilic copolymers exhibited unusual liquid-crystalline properties over a wide temperature range, being stable even at room temperature. These copolymers showed photoresponsive isomerization under the irradiation of UV–vis light both in THF solutions and in solid films. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2225–2234, 2007     

Effect of PBT molecular weight and reactive compatibilization on the dispersed‐phase coalescence of PBT/SAN blends

Poly(butylene terephthalate) (PBT)/styrene‐acrylonitrile copolymer (SAN) blends were investigated with respect to their phase morphology. The SAN component was kept as dispersed phase and PBT as matrix phase and the PBT/SAN viscosity ratio was changed by using different PBT molecular weights. PBT/SAN blends were also compatibilized by adding methyl methacrylate‐co‐glycidyl methacrylate‐co‐ethyl acrylate terpolymer, MGE, which is an in situ reactive compatibilizer for melt blending. In noncompatibilized blends, the dispersed phase particle size increased with SAN concentration due to coalescence effects. Static coalescence experiments showed evidence of greater coalescence in blends with higher viscosity ratios. For noncompatibilized PBT/SAN/MGE blends with high molecular weight PBT as matrix phase, the average particle size of SAN phase does not depend on the SAN concentration in the blends. However noncompatibilized blends with low molecular weight PBT showed a significant increase in SAN particle size with the SAN concentration. The effect of MGE epoxy content and MGE molecular weight on the morphology of the PBT/SAN blend was also investigated. As the MGE epoxy content increased, the average particle size of SAN initially decreased with both high and low molecular weight PBT phase, thereafter leveling off with a critical content of epoxy groups in the blend. This critical content was higher in the blends containing low molecular weight PBT than in those with high molecular weight PBT. At a fixed MGE epoxy content, a decrease in MGE molecular weight yielded PBT/SAN blends with dispersed nanoparticles with an average size of about 40 nm. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

The effect of in situ-formed copolymers on the morphology of reactive poly(phenylene ether)/poly(amide-6) blends

Poly(phenylene ether) (PPE)/poly(amide-6) (PA6) blends are examined in light of the information provided by two-dimensional chromatography and chemorheology. Chromatography provides a snapshot of the blend composition in the finished material, while rheology presents us with a direct insight into the reactions taking place in the melt. Block copolymer formation is chromatographically confirmed for the blends prepared with a coupling agent, but also for the blend prepared without any coupling agent. No co-continuous morphology is observed by scanning electron microscope. Instead, a coarse structure of PPE droplets in the PA6 matrix is obtained for the blend prepared without coupling agent. This is explained by the combined effects of the low viscosity of PA6 and the inherently formed copolymers. The PPE domains are smaller in the blends prepared with the coupling agents. Their size is correlated with the copolymer formation, surface tension, and interphase relaxation time. The data evidence a complex system where reactions resulting in the formation of copolymer via coupling or grafting take place together with the extension of the PPE and condensation growth of the PA6 polymers.     

Helix-sense-selective copolymerization of phenyl[bis(2-pyridyl)]methyl methacrylate,diphenyl(2-pyridyl)methyl methacrylate and triphenylmethyl methacrylate with chiral anionic initiators

Optically active poly[triphenylmethyl methacrylate-co-phenyl[bis(2-pyridyl)]methyl methacrylate] (poly[TrMA-co-PB2PyMA], poly[diphenyl(2-pyridyl)methyl methacrylate-co-phenyl[bis(2-pyridyl)]methyl methacrylate] (poly[D2PyMA-co-PB2PyMA]), and poly[triphenylmethyl methacrylate-co-diphenyl(2-pyridyl)-methyl methacrylate] (poly[TrMA-co-D2PyMA]) were prepared by helix-sense-selective copolymerization with complexes of organolithium with (−)-sparteine [(−)Sp],(S, S)-(+)- and (R, R)-(−)-2,3-dimethoxy-1,4-bis(dimethylamino)butane [(+)- and (−)DDB], and (S)-(+)-2-(1-pyrrolidinylmethyl)pyridine [(+)PMP] as anionic initiators in toluene at low temperature. The copolymers obtained with (−)Sp and (+)DDB or (−)DDB complexes of organolithium showed low optical activity, but to [(+)PMP] complex with N,N′-diphenyleneamine monolithium amide [(+)PMP–DPEDA–Li)] was effective in synthesizing copolymers of high optical rotation ([α] about +320 to + 370°) which were comparable to those of corresponding homopolymers with one-handed helical structure. The optical rotations of poly[TrMA-co-PB2PyMA] and poly[TrMA-co-D2PyMA] were much more stable than that of poly(D2PyMA) or poly(PB2PyMA) in a solution of CHCl₃–2,2,2-trifluoroethanol (10 : 1, v/v) at 25°C, but optical rotation of poly[D2PyMA-co-PB2PyMA] slowly decreased with time in the same conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2127–2133, 1998     

SYNTHESIS OF POLY(METHYL METHACRYLATE)-SILICA NANO-COMPOSITE

ABSTRACT

Transparent organic/pre-ceramic composite films of poly(methyl methacrylate) [PMMA] and perhydropolysilazane [PHPS] were synthesized by blending poly(methyl methacrylate-co-2-hydroxyethyl methacrylate) [P(MMA-co-HEMA)] random copolymers and PHPS. In the blend films, P(MMA-graft-PHPS) graft copolymers were formed, PMMA and PHPS were microscopically phase-separated in the solid state. Morphology of the microphase separation was investigated by transmission electron microscopy by changing HEMA content of the random copolymers and blend ratio of PHPS to HEMA. To convert PHPS to silica glass, the blend films were calcinated at 100°C. The morphology of the microphase separation of the films was not changed by the calcinations; the calcinated films were transparent. When the molar content of HEMA of P(MMA-co-HEMA) and the molar content of PHPS to HEMA in feed were 14.5% and 150%, respectively, the morphology was well ordered lamellae of PMMA and silica.     

Influence of microstructure and deformation behavior on toughening of reactively compatibilized polyamide 6 and poly(ethylene-co-butyl acrylate) blends

Influence of microstructure on impact toughness and fracture behavior of PA6 and EBA blends reactively compatibilized by EBA-g-MAH was quantitatively studied. The reactively compatibilized blends showed better distribution of elastomeric EBA particles in the PA6 matrix and the presence of EBA-g-MAH resulted in considerable reduction of interfacial tension between the component polymers. The interfacial adhesion between the PA6 and EBA phase in the compatibilized blends was enhanced by the interfacial reaction between the amide end-groups of PA6 and maleic anhydride group of EBA-g-MAH compared to uncompatibilized blends. The matrix ligament thickness and particle diameter values were lower than the predicted critical values and were responsible for the ductile behavior of the compatibilized blends. Stress whitening around the notch occurred in all the compatibilized blends which was the major energy dissipation zone in the blends. Matrix shear yielding or plastic flow without crazing was the dominant deformation mechanism in the tough compatibilized blends. There was no sign of shear yielding during impact fracture of the uncompatibilized blends where the elastomeric particles were completely dislodged from the matrix.     

Synthesis of aromatic polyesters and polyamides by alternating copolymerizations of 1,4-dicarbonyl-1,4-dihydronaphthalene with bezoquinones and benzoquinone diimines

1,4-Dicarbonyl-1,4-dihydronaphthalene ( 1 ) was synthesized by the dehydrochlorination reaction of 1,4-dihydronaphthalene-1,4-dicarbonyl chloride with triethylamine and obtained as its very dilute solution, but it easily polymerized in the concentration as high as 0.1 mol/L to give its polymer. 1 generated in situ by the dehydrochlorination reaction of 1,4-dihydronaphthalene-1,4-dicarbonyl chloride in a deoxygenated toluene polymerized alternatingly with benzoquinones such as 2-dodecylthio-p-benzoquinone, 2,5-di(tert-butyl)-p-benzoquinone, p-benzoquinone, and 2,3-dichloro-5,6-dicyano-p-benzoquinone, and with benzoquinone diimines such as N,N′-diethoxycarbonyl-p-benzoquinone diimine, N,N′-dibenzoyl-p-benzoquinone diimine, and N,N′-diphenyl-p-benzoquinone diimine to give aromatic polyesters and polyamides, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1929–1936, 1998     

Effect of Structure of Functionalizing Molecules on the Inter‐Macromolecular Reactions and Blending of Poly(ethylene‐co‐propylene) (EPM) with Poly(6‐aminohexanoic Acid) (PA6)

Two different functionalizing systems, i.e., monohexadecyl maleate (= hexadecyl hydrogen (2Z)‐but‐2‐enedioate) in the presence of dicumyl peroxide (= bis(1‐methyl‐1‐phenylethyl) peroxide) or 4‐carboxybenzenesulfonazide (= 4‐(azidosulfonyl)benzoic acid), were used in distinct experiments to perform in a one‐step procedure the formation of a EPM–PA6 graft copolymer, necessary to obtain a compatibilized blend, from a molten mixture of ethylene–propylene copolymer (EPM) and polyamide 6 (PA6). The characterization of the graft polymer by selective solvent extraction of the blends and the subsequent IR and NMR analysis of the various fractions established the occurrence of functionalization reactions preferentially onto the polyolefin with both reagents. Also the formation in good yield of graft copolymers at the phases interface was observed. Moreover, the morphology and thermal characterizations of the blends by means of SEM and DSC analyses were used to evaluate the compatibilization extent in comparison with blends obtained by the conventional two‐step procedure or by the one‐step procedure with commercial maleic acid derivatives.     

Specific properties of in situ ruthenium‐catalyzed polyamide 12/polydimethylsiloxane compatibilized blend

The main objective of this work focused on the chemical modification of polyamide 12 (PA12) properties through the reaction with a hydride‐terminated polydimethylsiloxane (PDMS‐SiH). The investigated PA12/PDMS‐SiH blend was compatibilized by ruthenium derivative catalyzed hydrosilylation reaction in molten state. This original route enhanced interfacial adhesion and avoid PDMS‐SiH leaching phenomenon between the two immiscible phases. More specifically, the size of PDMS‐SiH domains in the blend decreased from around 4 μm to 800 nm and from 30 to 1 μm after compatibilization with 10 and 20 wt % PDMS‐SiH, respectively. For the best compatibilized PA12/PDMS‐SiH blend, the introduction of PDMS lowered the surface free energy and the PA12‐based blend turned from hydrophilic to hydrophobic behavior, as evidenced by the water contact angle measurements. Gas permeability and CO₂/H₂ and CO₂/He gas selectivity were also improved with the increase in PDMS content. Besides, the mechanical properties were enhanced with 13% increase in Young's modulus after in situ compatibilization with 15 wt % PDMS‐SiH. Thermal stability was also improved after compatibilization as the initial degradation temperature of reactive blends obviously increased compared with nonreactive ones. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 978–988     

Graft formation and chain scission in blends of polyamide-6 and -6.6 with maleic anhydride containing polymers

The in situ formation of a compatibilizer, consisting of a copolymer of PA grafted onto a maleic anhydride (MA) containing polymer, is essential for the morphology and properties of the corresponding PA blends. In this study four blends, containing PA-6 or PA-6.6 and EPDM-g-MA or poly(styrene-co-maleic anhydride) (SMA; 28 wt % MA), were prepared and characterized. Chemical analyses showed that the amount of PA graft is independent of the blend composition. Going from EPDM-g-MA to SMA the MA content of the original MA-containing polymer increases, which in the corresponding blends results in an increase in the number of PA grafts and a decrease in the length of the PA grafts. In the SMA blends the number averaged molecular weight of the grafted PA is only about 200 g/mol. It is postulated that the water molecule, released upon imide formation at the PA/(MA-containing polymer) interface, hydrolyses a PA amide group, resulting in a new amine end group, which in its turn reacts with the MA-containing polymer, etc. Differential scanning calorimetry shows that the degree of crystallinity of the PA phase is decreased only when the size of the PA phase between the MA-containing polymer domains approaches the PA crystalline lamellar thickness. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 179–188, 1998     

Synthesis of triblock copolymers—(polyA-poly butadiene-polyA)—via metathesis polymerization

A series of triblock copolymers of the type A-B-A were synthesized using tungsten chloride-anchored hydroxyl-terminated polybutadiene (HTPBD) catalyst. Monomers like phenylacetylene (PA), norbornene (NBE), cyclooctadiene (COD), and cyclopentene (CP) were polymerized via metathesis pathway using this catalyst. The efficiency of this anchored catalyst in producing A-B-A triblock copolymers was explored and compared under the same experimental conditions like solvent system and reaction temperature. This anchored catalyst upon reaction with PA produced polyPA-block-polyBD-block-polyPA in high yield and with low polydispersity (pdi) compared to HTPBD. The formation of the triblock copolymers by this method was evinced by NMR, TGA, and GPC data as well as by delinking and inverse addition studies. All the cycloalkenes polymerized via ring-opening metathesis polymerization (ROMP) with the catalyst and yielded triblock copolymers. The mode of synthesis of triblocks could be construed as switching the mechanism of polymerization from radical to olefin metathesis. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2601–2610, 1998     

Stress–strain behavior of low‐density polyethylene/poly(methyl methacrylate) blends with modulated interfaces with a hydrogenated polybutadiene‐block‐poly(methyl methacrylate) diblock copolymer

The stress–strain diagrams and ultimate tensile properties of uncompatibilized and compatibilized hydrogenated polybutadiene‐block‐poly(methyl methacrylate) (HPB‐b‐PMMA) blends with 20 wt % poly(methyl methacrylate) (PMMA) droplets dispersed in a low‐density polyethylene (LDPE) matrix were studied. The HPB‐b‐PMMA pure diblock copolymer was prepared via controlled living anionic polymerization. Four copolymers, in terms of the molecular weights of the hydrogenated polybutadiene (HPB) and PMMA sequences (22,000–12,000, 63,300–31,700, 49,500–53,500, and 27,700–67,800), were used. We demonstrated with the stress–strain diagrams, in combination with scanning electron microscopy observations of deformed specimens, that the interfacial adhesion had a predominant role in determining the mechanism and extent of blend deformation. The debonding of PMMA particles from the LDPE matrix was clearly observed in the compatibilized blends in which the copolymer was not efficiently located at the interface. The best HPB‐b‐PMMA copolymer, resulting in the maximum improvement of the tensile properties of the compatibilized blend, had a PMMA sequence that was approximately half that of the HPB block. Because of the much higher interactions encountered in the PMMA phase in comparison with those in HPB (LDPE), a shorter sequence of PMMA (with respect to HPB but longer than the critical molecular weight for entanglement) was sufficient to favor a quantitative location of the copolymer at the LDPE/PMMA interface. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 22–34, 2005     

Thermal crosslinking of poly(methyl methacrylate) by reaction of methyl ester and quaternary ammonium salt and application to (meth)acrylate-based TPEs

Copolymers of N-vinylbenzyl N-methyl pyrrolidinium chloride (VBMPC) and methyl methacrylate, PVBMPC-co-poly(methyl methacrylate) (PMMA), were synthesized by free-radical copolymerization and proved to be prone to crosslinking as a result of the reaction of methyl ester groups with benzyl methyl pyrrolidinium chloride (BMPC) moieties at temperatures higher than 110 °C. When the VBMPC content was lower than 20 wt %, these copolymers were miscible with homo-PMMA. Blends of homo-PMMA and PVBMPC-co-PMMA fully could be cured above 150 °C, when the molecular weight of PMMA exceeded 10,000 and the VBMPC content of the copolymer was higher than 5 wt %. This reaction was carried out to crosslink selectively the PMMA microdomains of PMMA-b-poly(isooctyl acrylate) (PIOA)-b-PMMA (MIM) triblock copolymers to explain the mechanism for the mechanical failure of fully (meth)acrylic thermoplastic elastomers. Comparison of the ultimate tensile properties of MIM block copolymers, when the dispersed PMMA phases and PIOA matrix were crosslinked, led to the conclusion that the ductile failure of the hard PMMA microdomains rather than the elastic failure of the PIOA matrix was the reason for the mechanical failure of MIM triblocks. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4402–4411, 1999     

Controlled copolymerization of 1‐octene and butyl methacrylate via RAFT and their nonisothermal model‐free thermokinetic decomposition study

Reversible addition fragmentation chain transfer (RAFT) copolymerization of 1‐octene and butyl methacrylate (BMA) was carried out for the first time using 4‐cyano‐4‐(phenylcarbonothioylthio)pentanoic acid as RAFT agent in N,N′‐dimethyl formamide. Poly(1‐octene‐co‐BMA) copolymers with well‐controlled molecular weights and narrow molecular weight distribution were obtained throughout the polymerization. The copolymers have been well characterized by different analytical techniques such as SEC, FT‐IR, NMR, SEM, AFM, XRD, and TG analyses. FT‐IR and NMR analyses confirmed the synthesis of poly(1‐octene‐co‐BMA) copolymers. SEM and AFM analyses demonstrated the wavy‐lamellar morphological structure of the copolymers. Thermogravimetric analysis revealed good thermal stability of poly(1‐octene‐co‐BMA) copolymers synthesized via RAFT mediated polymerization. The thermokinetic parameters were evaluated by adopting model‐free methods of Friedman and Flynn–Wall–Ozawa using the nonisothermal thermogravimetric data. The multivariate nonlinear regression analysis established the most appropriate kinetic model and the corresponding kinetic parameters of thermal decomposition of poly(1‐octene‐co‐BMA) copolymers were also calculated. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2093–2103