Accelerated controlled radical polymerization of methacrylates

BACKGROUND: Nitroxide adducts 1,1‐ditertbutyl‐1‐(1‐methyl‐1‐cyanoethoxy)‐amine (AIBN/DBN), 1,1‐ditertbutyl‐1‐(benzoylperoxy)‐amine (BPO/DBN) and 2,2,6,6,‐tetramethyl‐4‐oxo‐1‐(1‐methyl‐1‐cyanoethoxy)‐piperidine (AIBN/4‐OXO‐TEMPO) were prepared and evaluated as stabilized unimolecular initiators for controlled radical polymerization of methacrylate monomers using sulfuric acid as an accelerating additive. Their effectiveness was evaluated from polymerization rates, molecular weight control and dispersity (D) of the polymers. Thermal stabilities of the polymers were also examined. The monomers used were methyl methacrylate, triethylene glycol dimethacrylate (TEGDMA) and ethoxylated bisphenol A dimethacrylate (EBPADMA). RESULTS: Polymerization was accomplished at 70 and 130 °C in 5 min to 144 h. The value of D of poly(methyl methacrylate) (PMMA) was 1.05–1.22. The glass transition temperature (T_g) for PMMA was 122–127 °C. The activity of the chain ends was established by chain extension and controlled polymerization was established by plotting M_n versus monomer conversion. First‐order kinetics in monomer consumption was established and an electron paramagnetic resonance study was conducted. Decomposition temperature (T_d) for PMMA was 360–380 °C, for poly(TEGDMA) was 300–380 °C and for poly(EBPADMA) was 360–440 °C. Photoinitiation without additive yielded no polymer. Thermal initiation by AIBN/4‐OXO‐TEMPO was the fastest. CONCLUSIONS: The initiators are applicable in low‐temperature additive‐enhanced controlled polymerization of methacylates and dimethacrylates, producing polymers with excellent attributes and a low value of D. Copyright © 2008 Society of Chemical Industry     

Synthesis of PMMA‐PTHF‐PMMA and PMMA‐PTHF‐PST linear and star block copolymers

Combination of cationic, redox free radical, and thermal free radical polymerizations was performed to obtain linear and star polytetramethylene oxide (poly‐THF)‐polymethyl methacrylate (PMMA)/polystyrene (PSt) multiblock copolymers. Cationic polymerization of THF was initiated by the mixture of AgSbF₆ and bis(4,4′ bromo‐methyl benzoyl) peroxide (BBP) or bis (3,5,3′,5′ dibromomethyl benzoyl) peroxide (BDBP) at 20°C to obtain linear and star poly‐THF initiators with M_w varying from 7,500 to 59,000 Da. Poly‐THF samples with hydroxyl ends were used in the methyl methacrylate (MMA) polymerization in the presence of Ce(IV) salt at 40°C to obtain poly(THF‐b‐MMA) block copolymers containing the peroxide group in the middle. Poly(MMA‐b‐THF) linear and star block copolymers having the peroxide group in the chain were used in the polymerization of methyl methacrylate (MMA) and styrene (St) at 80°C to obtain PMMA‐b‐PTHF‐b‐PMMA and PMMA‐b‐PTHF‐b‐PSt linear and star multiblock copolymers. Polymers obtained were characterizated by GPC, FT‐IR, DSC, TGA, ¹H‐NMR, and ¹³C‐NMR techniques and the fractional precipitation method. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 219–226, 2004     

Investigation of thermal behavior of poly(2‐hydroxyethyl methacrylate‐co‐itaconic acid) networks

The thermal behavior of poly(2‐hydroxyethyl methacrylate) [PHEMA] homopolymer and poly(2‐hydroxyethyl methacrylate‐co‐itaconic acid) [P(HEMA/IA)] copolymeric networks synthesized using a radiation‐induced polymerization technique was investigated by differential scanning calorimetry, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The glass‐transition temperature (T_g) of the PHEMA homopolymer was found to be 87°C. On the other hand, the T_g of the P(HEMA/IA) networks increased from 88°C to 117°C with an increasing amount of IA in the network system. The thermal degradation reaction mechanism of the P(HEMA/IA) networks was determined to be different from the PHEMA homopolymer, as confirmed by thermogravimetric analysis. It was observed that the initial thermal degradation temperature of these copolymeric networks increased from 271°C to 300°C with IA content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1602–1607, 2007     

Methyl methacrylate based copolymers and terpolymers: Preparation,identification, and plasticizing capability for a poly(methyl methacrylate) used in aviation

In this study, we first synthesized transparent poly(methyl methacrylate–maleic anhydride) [P(MMA–MAH)] and poly(methyl methacrylate–maleic anhydride–N‐2‐methyl‐4‐nitrophenyl maleimide) [P(MMA–MAH–MI)] via free‐radical polymerization at different monomer ratios. The synthesized polymers were characterized by titration, viscometric, spectroscopy, and thermal analyses. Higher contents of maleic anhydride (MAH) resulted in increases in the viscosity, glass‐transition temperature (T_g), and transparency. The synthesized polymers were then blended with a commercial‐grade poly(methyl methacrylate) (PMMA) used in aviation in the presence of CHCl₃. According to the free volume theory, the incorporation of 5 wt % P(MMA–MAH)s or P(MMA–MAH–MI)s into the commercial PMMA resulted in a plasticizing impact on this thermoplastic, which was confirmed by the decrease in the T_g values of the blends with almost the same transparency as the initial PMMA. In fact, the higher the content of MAH was, the lower the T_g of the blends was. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46603.     

The influence of oxide nanoparticles on the kinetics of free radical methyl methacrylate polymerization in bulk

A series of poly(methyl methacrylate) (PMMA) nanocomposites were synthesized using free radical polymerization in bulk, by addition of 1 vol% of oxide nanoparticles (silica, alumina, and titania), differing in the nature and type. The influence of nanofiller presence on the kinetics of methyl methacrylate (MMA) free radical polymerization was investigated. For this purpose, the kinetic model that includes the contribution from the first‐order reaction and the autoacceleration was applied on data obtained following the isothermal polymerization at 70°C by differential scanning calorimetry (DSC). The effect of the size and the surface nature of nanofillers on the interfacial layer thickness (d), as well as the influence of d on the glass transition temperature (T_g) of PMMA hybrid materials was studied. It was found that hydrophilic particles accelerated the initiator decomposition and affected the monomer polymerization on the surface, which caused the formation of thicker interfacial layer compared to the one around hydrophobic fillers. The addition of smaller nanoparticles size decreased the glass transition temperature of pure poly(methyl metacrylate). The linear increase of PMMA T_g value with increasing the polymeric interfacial layer was determined. The T_g values of pure PMMA and PMMA nanocomposite with d of 1.4 nm were estimated to be the same. POLYM. COMPOS. 34:1342–1348, 2013. © 2013 Society of Plastics Engineers     

Mechanical and thermal properties of epoxypolymethyl methacrylate blends synthesizedin supercritical carbon dioxide

A series of epoxy/polymethyl methacrylate (E/PMMA) blends was synthesized through impregnation polymerization of methyl methacrylate at concentrations ranging (0–1.5 phr) into diglycidyl ether of bisphenol‐A (0.1 mol) in presence of 2,2‐azobisisobutyronitrile (2 × 10^?2 mol) at 3000 psi, (60–90 ± 1)°C for 3 h in supercritical carbon dioxide, followed by curing of treated epoxy with triethylene tetramine (10 phr) at (40 ± 1)°C. The progress of all such impregnation polymerization reactions was monitored rheoviscometrically. Formation of E/PMMA blends was ascertained through of PMMA mass uptake (%) into epoxy, UV–vis and FTIR spectra, and TEM. With PMMA mass uptake (%), compression strength and resistance against wear of E/PMMA blends were increased with simultaneous decrease in their Rockwell hardness (R scale), charpy impact, and tensile strength, respectively. All E/PMMA blends have shown nonuniform photoelastic behavior at applied load ranging 4–20 kgf and significant stability against thermooxidation with T_g/T_m and char yield (%) ranging 0.53–0.59, 29.31–31.66, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1303–1310, 2007     

Fast transient fluorescence technique for studying swelling of gels made at various crosslinker contents and exposed to organic vapour

Fast transient fluorescence technique (FTRF) was employed for studying swelling of disc‐shaped poly(methyl methacrylate) (PMMA) gels, which were prepared by free radical copolymerization of methyl methacrylate (MMA) using various ethylene glycol dimethacrylate (EGDM) contents at 60 °C. Pyrene (P) was introduced as a fluorescence probe during polymerization. Swelling experiments were performed by using P‐doped PMMA gels under chloroform vapor. Decay curves of P were measured during in situ swelling experiments. Exponential fits were performed to measure pyrene lifetimes, τ, inside the PMMA gels. It was observed that τ values decreased as swelling proceeded. An equation is derived for low quenching efficiencies to interpret the behaviour of P lifetimes during swelling. The Li–Tanaka equation was used to determine the cooperative diffusion coefficients, D_c, for the gels made at various crosslinker contents. It is observed that D_c values decrease as the crosslinker content is increased. © 2002 Society of Chemical Industry     

Surface‐initiated atom transfer radical polymerization from Mg(OH)2 nanoparticles to prepare the well‐defined polymer‐Mg(OH)2 nanocomposites

Well‐defined polymer‐Mg(OH)₂ nanocomposites were prepared by atom transfer radical polymerization (ATRP). The ATRP initiators were covalently attached to the Mg(OH)₂ by esterification of 2‐chloropropionyl chloride with hydroxyl group. The amount of polymer grafted from Mg(OH)₂ can be controlled using a different catalyst system and adding a small amount of polar solvent. The well‐defined diblock copolymer, consisting of poly(styrene) (PS) and poly(methyl methacrylate) (PMMA) were synthesized. The products were characterized by nuclear magnetic resonance, Fourier transform infrared, differential scanning calorimetry, and thermal gravimetric analysis. The morphologies of PS/PMMA and PS/PMMA/Mg(OH)₂‐g‐PS‐b‐PMMA blends are compared by using a scanning electron microscope. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3680–3687, 2007     

Synthesis and characterization of diblock,triblock, and multiblock copolymers containing poly(3‐hydroxy butyrate) units

A poly[(R,S)‐3‐hydroxybutyrate] macroinitiator (PHB‐MI) was obtained through the condensation reaction of poly[(R,S)‐3‐hydroxybutyrate] (PHB) oligomers containing dihydroxyl end functionalities with 4,4′‐azobis(4‐cyanopentanoyl chloride). The PHB‐MI obtained in this way had hydroxyl groups at two end of the polymer chain and an internal azo group. The synthesis of ABA‐type PHB‐b‐PMMA block copolymers [where A is poly(methyl methacrylate) (PMMA) and B is PHB] via PHB‐MI was accomplished in two steps. First, multiblock active copolymers with azo groups (PMMA‐PHB‐MI) were prepared through the redox free‐radical polymerization of methyl methacrylate (MMA) with a PHB‐MI/Ce(IV) redox system in aqueous nitric acid at 40°C. Second, PMMA‐PHB‐MI was used in the thermal polymerization of MMA at 60°C to obtain PHB‐b‐PMMA. When styrene (S) was used instead of MMA in the second step, ABCBA‐type PMMA‐b‐PHB‐b‐PS multiblock copolymers [where C is polystyrene (PS)] were obtained. In addition, the direct thermal polymerization of the monomers (MMA or S) via PHB‐MI provided AB‐type diblocks copolymers with MMA and BCB‐type triblock copolymers with S. The macroinitiators and block copolymers were characterized with ultraviolet–visible spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, cryoscopic measurements, and thermogravimetric analysis. The increases in the intrinsic viscosity and fractional precipitation confirmed that a block copolymer had been obtained. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1789–1796, 2004     

Studies on synthesis and characterization of poly(methyl methacrylate)‐bentonite clay composite by emulsion polymerization and simultaneous in situ clay incorporation

Well‐dispersed poly(methyl methacrylate) (PMMA)–bentonite clay composite was synthesized by emulsion polymerization using methyl methacrylate (MMA) monomer and 3% sodium carbonate treated bentonite clay. The composite lost its transparency normally encountered with the neat PMMA. The composite was characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), vicat softening point (VSP), dynamic mechanical thermal analysis (DMTA), and tensile studies. The morphology was investigated by scanning electron microscopy (SEM) and atomic forced microscopy (AFM) as well. The crystallography was studied to estimate the changes in crystallographic planes by X‐ray diffraction (XRD) analysis. The particle size distribution was compared amongst neat bentonite clay, neat PMMA and the composite. The FTIR spectra reveal the fact that no new primary valence bond is formed between the clay and PMMA. The thermal stability of the composite is significantly improved, as indicated by the TGA and VSP studies. A substantial increase in glass transition temperature (T_g) approximately, 10°C was recorded from the DMTA as both the storage modulus and tan δ values underwent inflexion at higher temperatures in case of the composite compared with the pristine PMMA. The XRD pattern indicates increase in basal “d” spacing for the composite. The morphology from both the SEM and AFM is quite supportive to well‐dispersed exfoliation. The incorporation of nanosized activated clay particles in PMMA during its in situ polymerization from MMA led to the formation of nanocomposites. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Thermal and gas permeation properties of copolymers derived from 3‐methacryloxypropyltris(trimethylsiloxy)silane and adamantyl group‐containing methacrylate derivatives

Novel copolymer membranes derived from three types of adamantyl group‐containing methacrylate derivatives and 3‐methacryloxypropyltris(trimethylsiloxy)silane (SiMA) were synthesized via free radical polymerization. The thermal and permeation properties of these copolymer membranes were investigated. Copolymer membranes with less than 11.9 mol % adamantane content exhibited good membrane forming abilities that are suitable for permeation measurement. The decomposition temperature of all copolymers increased up to approximately 40–80°C with increasing adamantane content compared with poly(SiMA). Moreover, the glass transition temperature (T_g) of all copolymers increased up to approximately 46–60°C with increasing adamantane content compared with the theoretical value, which was estimated from Fox equation. 1‐Adamantyl methacrylate copolymer had the highest fractional free volume among the three types of adamantly group‐containing methacrylate derivatives. The gas permeability coefficient of this copolymer increased by 22–45% with increasing adamantane content compared with that of poly(SiMA). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43129.     

Use of short isobornyl methacrylate building blocks to improve the heat and oil resistance of thermoplastic elastomers via RAFT emulsion polymerization

Triblock copolymer (TCP)‐based thermoplastic elastomers (TPEs) were designed via reversible addition–fragmentation chain‐transfer emulsion polymerization. Short isobornyl methacrylate (IM) building blocks in the two ends of molecular chain were incorporated to guarantee the mechanical properties of the TPEs at high temperature (i.e., heat resistance) because of the high glass‐transition temperature (T_g) of poly(isobornyl methacrylate) (PIM; ～180 °C). The microphase separation, tensile properties at different temperatures, dynamic mechanical properties, oil resistance, and thermal stability of the TPEs were extensively characterized. The TPEs had distinct microphase separation with a wide inter‐T_g interval (150–185 °C). The tensile strength and elongation at break of the TPEs decreased with increasing temperature from 25 to 100 °C because of the reduced interactions in the phase domain. Even so, the TPEs had a high elongation at break beyond 200% and little change in the tensile strength even at 100 °C together with a wide quasi‐platform stage between the T_g values in dynamic mechanical analysis; this indicated good heat resistance. Meanwhile, the TPEs had an enhanced oil resistance and a thermal stability higher than 300 °C. These TCP‐based TPEs with heat and oil resistance broaden the application potential in practical fields. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45379.     

Effect of layered hydroxide salts,produced by two different methods,on the mechanical and thermal properties of poly(methyl methacrylate)

In this study, eight different layered hydroxide salts (LHSs) based on copper and zinc, intercalated with stearate, myristate, azelate, and poly(ethylene glycol) (PEG) monolaurate, were prepared. All the LHSs were produced according two different methods: co‐precipitation (direct method) and synthesis of zinc hydroxide nitrate (ZHN) and copper hydroxide nitrate (CHN) followed by exchange reaction (indirect method). The synthetic layered compounds were characterized by X‐ray diffraction (XRD) and thermogravimetric analysis (TGA). TGA results revealed that higher thermal stability was observed for the LHSs synthesized by direct method. The effects of all these LHSs on the thermal and mechanical properties of poly(methyl methacrylate) (PMMA) nanocomposites were investigated. The LHSs percentage (wt%) in the PMMA was fixed at 1%. PMMA and PMMA nanocomposites were produced by in situ bulk polymerization. Compared to PMMA, all the nanocomposites exhibited higher thermal stability. The nanocomposite containing ZHN(stearate) by indirect method revealed both T₅₀ (temperature at which a 50% loss of mass occurs) and T₉₀ (temperature at which a 90% loss of mass occurs) 71°C higher than PMMA. Compared to PMMA, the nanocomposite with ZHN(PEG monolaurate) exhibited an increase of 14% in the elastic modulus, at 30°C. POLYM. ENG. SCI., 59:1065–1074, 2019. © 2019 Society of Plastics Engineers     

Living functionalization of polymethacrylates by group transfer polymerization (GTP) using low ceiling temperature monomers

A living functionalization method for group transfer polymerization (GTP) has been developed for poly(alkyl methacrylates) using the sterically hindered monomer, methyl-2-phenylpropenoate (MPHA). The end-capping reactions of MPHA with living trimethylsilyl ketene acetal-ended poly(methyl methacrylate) (PMMA) chain ends have been systematically studied and characterized by size exclusion chromatography, vapor pressure osmometry, ultraviolet-visible, ¹H and ¹³C nuclear magnetic resonance spectroscopy. Although oligomerization of MPHA is observed at - 78° C, this is reversible and only monoaddition is observed at room temperature. In principle, various functional groups can be introduced into poly(alkyl methacrylates) via substituents on the aromatic ring of MPHA and related monomers. Amino-functionalized PMMA was prepared by end-capping reactions of living trimethylsilyl ketene acetal-ended PMMA with methyl E-3-(2-dimethylaminophenyl)-2-phenylacrylate.     

Highly reversible and repeatable PTCR characteristics of PMMA/Ag‐coated glass bead composites based on CTE mismatch phenomena

Positive temperature coefficient of resistivity (PTCR) behavior of poly(methyl methacrylate) PMMA/silver (Ag)‐coated glass bead composites has been investigated with reference to the conventional PMMA/carbon black (CB) composites. The PMMA/CB composites showed a sudden rise in resistivity (PTC trip) at 115°C, close to the glass transition temperature (T _g, 113°C) of the PMMA. However, the PTC trip temperature (92°C) of PMMA/Ag‐coated glass bead composites was appeared well below the T _g of PMMA. The room temperature resistivity and PTC trip temperature of the composites were also very much stable upon thermal cycling. Addition of 1 phr of nanoclay increased the PTC trip temperature of PMMA/CB composites to 120°C, close to the T _g (118°C) of PMMA/clay nanocomposites, while PMMA/clay/Ag‐coated glass bead nanocomposites showed the PTC trip at 98°C. We proposed that the mismatch in coefficient of thermal expansion (CTE) between PMMA and glass beads played a key role that led to a disruption in continuous network structure of Ag‐coated glass beads even at a temperature well below the T _g of PMMA. The decrease in dielectric permittivity of PMMA/Ag‐coated glass bead composites on increasing frequency indicated possible use of the PTC composites as dielectric material. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Synthesis and characterization of poly(methyl methacrylate)/montmorillonite nanocomposites by in situ bulk polymerization

Poly(methyl methacrylate)/montmorillonite (MMT) nanocomposites were prepared by in situ bulk polymerization. The results showed that the silicone coupling agent affected the structure and properties of hybrid materials. XRD analysis showed that the dispersion of clay in nanocomposites with silicone‐modified organophilic MMT was more ordered than that in nanocomposites with unmodified organophilic MMT. The glass transition temperature (T_g) of the nanocomposites was 6–15°C higher and the thermal decomposition temperature (T_d) was 100–120°C higher than those of pure PMMA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2256–2260, 2003     

Synthesis of polyglutarimides from p(methyl methacrylate) and cyclohexylamine. I. Influence of working conditions on imidization reaction

Over the last 50 years methacrylic polymers, especially poly(methyl methacrylate) (PMMA), have reached a noteworthy place in world polymer production. However, for special applications that require thermal properties, polycarbonates take the place of PMMA because of the latter's low glass transition temperature (T_g) of 105°C. The aminolysis reaction of PMMA with cyclohexylamine in xylene was studied to obtain a polyglutarimide exhibiting higher T_g values. The mechanism involving aminolysis and further amidization of ester groups was correlated with the experimental characterization of all the species created during the reaction. Poly(N‐cyclohexylacrylamide) and polyglutarimide (prepared from this precursor) were prepared in order to determine the special characteristics of these model compounds by FTIR. This method abled the quantification of ester, amide, acid, and imide groups. This aminolysis reaction was optimized (190–250°C; ratio of constituents, 0.5: 3) by spectroscopically following the different groups and monitoring the increase of the T_g. Poly(N‐cyclohexyl glutarimide) (65%) containing amide groups (25%) and acid groups (10%) presents a T_g value of 195°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1876–1888, 2000     

Thermal decomposition behavior of γ‐irradiated poly(vinyl acetate)/poly(methyl methacrylate) miscible blends

Miscible polymer blends based on various ratios of poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) were prepared in film form by the solution casting technique using benzene as a common solvent. The thermal decomposition behavior of these blends and their individual homopolymers before and after γ‐irradiation at various doses (50–250 kGy) was investigated. The thermogravimetric analysis technique was utilized to determine the temperatures at which the maximum value of the rate of reaction (T_max) occurs and the kinetic parameters of the thermal decomposition. The rate of reaction curves of the individual homopolymers or their blends before or after γ‐ irradiation displayed similar trends in which the T_max corresponding to all polymers was found to exist in the same position but with different values. These findings and the visual observations of the blend solutions and the transparency of the films gave support to the complete miscibility of these blends. Three transitions were observed along the reaction rate versus temperature curves; the first was around 100–200°C with no defined T_max, which may arise from the evaporation of the solvent. The second T_max was in the 340–380°C range, which depended on the polymer blend and the γ‐irradiation condition. A third transition was seen in the rate of reaction curves only for pure PVAc and its blends with PMMA with ratios up to 50%, regardless of γ‐ irradiation. We concluded that γ‐irradiation improved the thermal stability of PVAc/PMMA blends, even though the PMMA polymer was degradable by γ irradiation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1773–1780, 2006     

Synthesis,characterization, and thermal degradation of novel poly(2‐(5‐bromo benzofuran‐2‐yl)‐2‐oxoethyl methacrylate)

A novel methacrylate monomer containing benzofuran side group, 2‐(5‐bromo benzofuran‐2‐yl)‐2‐oxoethyl methacrylate (BOEMA), was synthesized from esterification reaction of 2‐bromo‐1‐(5‐bromo benzofuran‐2‐yl) ethanone with sodium methacrylate at 85°C in the presence of 1,4‐dioxane solvent. After characterization with Fourier transform infrared spectrophotometer, nuclear magnetic resonance (¹H‐NMR and ¹³C‐NMR), its homopolymerization was carried out by free radical polymerization at 60°C in the presence of benzoyl peroxide initiator and 1,4‐dioxane solvent. The glass transition temperature (T_g) of the synthesized novel polymer, poly(2‐(5‐bromo benzofuran‐2‐yl)‐2‐oxoethyl methacrylate) [poly(BOEMA)], was determined to be 137°C with differential scanning calorimetry technique. Thermal degradation kinetics of poly(BOEMA) was investigated by thermogravimetric analysis method at different heating rates with 5°C/min intervals between measurements. From dynamic measurements, the analysis of each process mechanism of Coats–Redfern and Van Krevelen methods showed that the most probable model for the decomposition process of poly(BOEMA) homopolymer agrees with the random nucleation, F₁ mechanism. The apparent decomposition activation energies of poly(BOEMA) by Kissinger's and Flynn–Wall–Ozawa methods in the studied conversion range were 188.47 and 180.13 kJ/mol, respectively. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Blends containing core–shell impact modifiers. Part 3 – Effects of temperature on tensile impact behaviour

Abstract

The performances of two contrasting core–shell impact modifiers, in blends with polycarbonate (PC), poly (methyl methacrylate) (PMMA), and poly (styrene-co-acrylonitrile) (PSAN), have been evaluated using tensile impact tests at temperatures between -80 and +50°C. In both modifiers, each individual particle has a 10 nm thick outer shell of PMMA, which is grafted to the rubber phase. In the case of modifier PB, the core of the particle is a 200 nm diameter homogeneous sphere of polybutadiene, with a T _g of -86°C. Modifier PBA has a 260 nm core of PMMA, surrounded by a 20 nm inner shell of poly (butyl acrylate-co-styrene), which has a T _g of -17°C. Tensile impact tests show that the T _g of the rubber does not necessarily control the brittle–ductile transition temperature T _BD. Both the PC–PB and PC–PBA blends exhibit some ductility at -80°C, although neither blend is as tough as plain PC at any temperature. The blend of PB with PMMA shows a modest increase in toughness above -40°C and there is a similar but rather larger increase in the toughness of the PMMA–PBA above -20°C. In PSAN blends, the PBA modifier is the more effective toughening agent ahove 0°C. It is concluded that these differences originate from differences in the balance between shear yielding and crazing in the matrix polymer, and in the ability of cavitated rubber particles to prevent crazes from turning into cracks. In PMMA and PSAN blends, the PBA modifier is the more effective toughening agent at 23°C because of its rigid core, which enables stable rubber fibrils both to form and to contribute to local strain hardening, thereby stabilising the yield zone.