Free radical copolymerization of N,N‐dimethylaminoethyl methacrylate with styrene and methyl methacrylate: monomer reactivity ratios and glass transition temperatures

BACKGROUND: The properties of copolymers depend strongly on their composition; therefore in order to tailor some for specific applications, it is necessary to control their synthesis, and, in particular, to know the reactivity ratios of their constituent monomers. Free radical copolymerizations of N,N‐dimethylaminoethyl methacrylate (DMAEM) with styrene (ST) and methyl methacrylate (MMA) in toluene solution using 1‐di(tert‐butylperoxy)‐3,3,5‐trimethylcyclohexane as initiator at 70 °C were investigated. Monomer reactivity ratios were determined for low conversions using both linear and nonlinear methods. RESULTS: For the DMAEM/ST system the average values are r₁ = 0.43 and r₂ = 1.74; for the DMAEM/MMA system the average values are r₁ = 0.85 and r₂ = 0.86. The initial copolymerization rate, R_p, for DMAEM/ST sharply decreases as the content of ST in the monomer mixture increases up to 30 mol% and then attains a steady value. For the DMAEM/MMA copolymerization system the composition of the feed does not have a significant influence on R_p. The glass transition temperatures (T_g) of the copolymers were determined calorimetrically and calculated using Johnston's sequence length method. A linear dependence of T_g on copolymer composition for both systems is observed: T_g increases with increasing ST or MMA content. CONCLUSION: Copolymerization reactivity ratios enable the design of high‐conversion processes for the production of copolymers of well‐defined properties for particular applications, such as the improvement of rheological properties of lubricating mineral oils. Copyright © 2009 Society of Chemical Industry     

Thermal Stability of Lubricating Oil Additives Based on Styrene and n-Alkyl Methacrylate Terpolymers

In this work the thermal stability of polymeric additives for the improvement of rheological behavior of mineral lubricating oils was investigated. The systems studied comprised methyl methacrylate (MMA)/dodecyl methacrylate (DDMA)/octadecyl methacrylate (ODMA) and styrene (Sty)/DDMA/ODMA terpolymers. The composition of the terpolymers was determined by the ¹H nuclear magnetic resonance spectroscopy and molar mass distribution by the size exclusion chromatography. The thermal degradation of terpolymers was studied by the thermogravimetric analysis. Sty/DDMA/ODMA terpolymers exhibited an improved thermal stability in comparison with MMA/DDMA/ODMA terpolymers of the corresponding compositions. Thus, the temperatures of 50% weight loss were found to be 313°C and 363°C for MMA terpolymer and Sty terpolymer, respectively, where x (MMA) = x (Sty) = 30 mol%.     

Synthesis and characterization of suspension terpolymer of N‐cyclohexylmaleimide,methyl methacrylate,and styrene

N‐cyclohexylmaleimide (ChMI) and styrene (St) were polymerized with methyl methacrylate (MMA) at different St feed content by suspension polymerization method. The glass transition temperatures (T_g) of the terpolymers were detected by torsional braid analysis (TBA). Two transition peaks in TBA curves of the terpolymers with a high St content illustrated that these terpolymers have a heterogeneous chain structure and the phase separation occurred. The lower transition temperature, T_g1, was assigned to the random St‐MMA components, and the higher transition temperature, T_g2, was assigned to the St‐ChMI units‐rich segments. Thermogravimetric analyses (TGA) revealed that all the terpolymers showed a two‐step degradation process. The tensile strength of the terpolymers decrease with increasing St content while the impact strength tended to increase slightly. The rheological behavior of the terpolymers was also detected. The result illustrated that the terpolymers showed rheological behavior similar to that of pseudoplastic liquid. The apparent shear viscosity decreased with the increasing of St content. All terpolymers have a higher value of flow n than the poly(MMA‐co‐ChMI). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 918–922, 2006     

Synthesis of methacrylate copolymers and their effects as pour point depressants for lubricant oil

In this study, polymethacrylate polymers were synthesized by free‐radical polymerization for use as pour point depressants in lubricant oil, and their low‐temperature properties were investigated. Four methacrylate monomers were synthesized by the esterification of methyl methacrylate (MMA) with four kinds of fatty alcohols. The purification step was performed to prepare the pure monomers. Two polymerization experiments were carried out with four kinds of methacrylate monomers obtained previously and MMA. Copolymers, which were made from one kind of monomer and MMA, and terpolymers, which were made from two kinds of monomers and MMA, were prepared. The molecular structures of the synthesized methacrylate monomers and polymethacrylate polymers were verified by ¹H‐NMR, and the molecular weight data were obtained by gel permeation chromatography. The pour points of the base oils containing 0.1 wt % polymethacrylate polymers were measured according to ASTM D 97‐93. The pour points of most base oils containing each polymer decreased compared to that of the pure base oil. Particularly, poly(dodecyl methacrylate‐co‐hexadecyl methacrylate‐co‐methyl methacrylate), made of dodecyl methacrylate, hexadecyl methacrylate, and MMA at a molar ratio of 3.5 : 3.5 : 3, showed the best low‐temperature properties. This terpolymer dropped the pour point of the base oil by as much as 23°C, and its yield was 93.5%. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improvement of the physical properties of poly(methyl methacrylate) by copolymerization with pentafluorophenyl methacrylate

Copolymers of methyl methacrylate (MMA) and pentafluorophenyl methacrylate (PFPMA) of various compositions were prepared with a free‐radical initiator. When PFPMA was included in the copolymers, the glass‐transition temperatures increased and showed a positive deviation from the Gordon–Taylor equation. A copolymer containing 20 wt % PFPMA exhibited almost zero orientational birefringence, and the photoelastic birefringence became zero when the copolymer contained 13 wt % PFPMA. When 20 wt % PFPMA was incorporated into the MMA copolymer, its water absorption decreased to 0.4 wt % versus 1.8 wt % for poly(methyl methacrylate) (PMMA) under the same condition. The flammability of the PFPMA/MMA copolymer was reduced in comparison with that of the MMA homopolymer. The refractive indices of the PFPMA/MMA copolymers were very close to that of PMMA, and the transmittances of the copolymers were slightly better than that of PMMA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

Synthesis and thermal analysis of emulsion terpolymers of N‐phenylmaleimide,methyl methacrylate,and acrylonitrile

Terpolymers of N‐phenylmaleimide (PMI), methyl methacrylate (MMA), and acrylonitrile (AN) were synthesized by emulsion polymerization. The thermal properties of the terpolymers, at different PMI and AN feed contents, were investigated by TBA, TGA, and the Vicat softening point test. The results show that the glass transition temperature (T_g) and decomposition temperature of the terpolymers increase with increasing PMI feed content. Furthermore, the Vicat softening points of the terpolymers increase with the PMI feed content. The M?_w and M?_n of the terpolymers were also determined by GPC. The results show that the M?_w and M?_n of the terpolymers have a maximum value in the range of 0–30% PMI feed content and decrease with an increasing AN feed content. The mechanical properties (tensile strength and impact strength) of the terpolymers decrease with an increasing PMI feed content and increase with an increasing AN feed content. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2455–2462, 2001     

Reactivity ratios and copolymer properties of 2‐(diisopropylamino)ethyl methacrylate with methyl methacrylate and styrene

Free radical copolymerization kinetics of 2‐(diisopropylamino)ethyl methacrylate (DPA) with styrene (ST) or methyl methacrylate (MMA) was investigated and the corresponding copolymers obtained were characterized. Polymerization was performed using tert‐butylperoxy‐2‐ethylhexanoate (0.01 mol dm^?3) as initiator, isothermally (70 °C) to low conversions (<10 wt%) in a wide range of copolymer compositions (10 mol% steps). The reactivity ratios of the monomers were calculated using linear Kelen–Tüd?s (KT) and nonlinear Tidwell–Mortimer (TM) methods. The reactivity ratios for MMA/DPA were found to be r₁ = 0.99 and r₂ = 1.00 (KT), r₁ = 0.99 and r₂ = 1.03 (TM); for the ST/DPA system r₁ = 2.74, r₂ = 0.54 (KT) and r₁ = 2.48, r₂ = 0.49 (TM). It can be concluded that copolymerization of MMA with DPA is ideal while copolymerization of ST with DPA has a small but noticeable tendency for block copolymer building. The probabilities for formations of dyad and triad monomer sequences dependent on monomer compositions were calculated from the obtained reactivity ratios. The molar mass distribution, thermal stability and glass transition temperatures of synthesized copolymers were determined. Hydrophobicity of copolymers depending on the composition was determined using contact angle measurements, decreasing from hydrophobic polystyrene and poly(methyl methacrylate) to hydrophilic DPA. Copolymerization reactivity ratios are crucial for the control of copolymer structural properties and conversion heterogeneity that greatly influence the applications of copolymers as rheology modifiers of lubricating oils or in drug delivery systems. © 2015 Society of Chemical Industry     

Synthesis and characterization of side-chain poly(methacrylate)s bearing new azo-moieties

New side-chain poly(methacrylate)s with azo moieties were prepared by free radical copolymerization, starting from methyl methacrylate (MMA) and some original azo-monomers. The chromophore content was evaluated from ¹H-NMR spectroscopy and elemental analyses; all structures exhibited a high content of azobenzene units. UV–Vis measurements have also supported this fact. Reactivity ratios for the methacrylate systems and their corresponding Q–e values were calculated based on several initial feed compositions (MMA and the newly synthesized azo-monomers) using an integral method with its appropriate software. The polymers were also characterized by FTIR, SEC and DSC-TGA techniques. The coloured poly(methacrylate)s exhibited glass transition temperatures between 141 and 168 °C and thermal stabilities up to 306 °C.     

Synthesis of defined polyhedral oligosilsesquioxane‐containing diblock and triblock methacrylate copolymers by atom transfer radical polymerization

Defined diblock and triblock copolymers composed of methyl methacrylate‐co‐glycidyl methacrylate block and 3‐{3,5,7,9,11,13,15‐hepta(2‐methylpropyl)‐pentacyclo[9.5.1.1^3,9.1^5,15.1^7,13]‐octasiloxan‐1‐yl}propyl methacrylate block(s), i.e., P(MMA‐co‐GMA)‐b‐PiBuPOSSMA and PiBuPOSSMA‐b‐P(MMA‐co‐GMA)‐b‐PiBuPOSSMA, were synthesized by atom transfer radical polymerization (ATRP). First, monofunctional and bifunctional P(MMA‐co‐GMA) copolymers were synthesized by ATRP. Subsequently, these copolymers were successfully used as macroinitiators for ATRP of POSS‐containing methacrylate monomer. The process showed high initiation efficiency of macroinitiators and led to products with low dispersity. The synthesized block copolymers were characterized by size exclusion chromatography, ¹H‐NMR spectroscopy and their glass transition temperatures were determined by differential scanning calorimetry. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

Effects of poly(methyl methacrylate)‐based low‐profile additives on the properties of cured unsaturated polyester resins. I. Miscibility,curing behavior,and glass‐transition temperatures

The effects of three series of self‐synthesized poly(methyl methacrylate) (PMMA)‐based low‐profile additives (LPAs), including PMMA, poly(methyl methacrylate‐co‐butyl acrylate), and poly(methyl methacrylate‐co‐butyl acrylate‐co‐maleic anhydride), with different chemical structures and MWs on the miscibility, cured‐sample morphology, curing kinetics, and glass‐transition temperatures for styrene (ST)/unsaturated polyester (UP) resin/LPA ternary systems were investigated by group contribution methods, scanning electron microscopy, differential scanning calorimetry (DSC), and dynamic mechanical analysis, respectively. Before curing at room temperature, the degree of phase separation for the ST/UP/LPA systems was generally explainable by the calculated polarity difference per unit volume between the UP resin and LPA. During curing at 110°C, the compatibility of the ST/UP/LPA systems, as revealed by cured‐sample morphology, was judged from the relative magnitude of the DSC peak reaction rate and the broadness of the peak. On the basis of Takayanagi's mechanical models, the effects of LPA on the final cure conversion and the glass‐transition temperature in the major continuous phase of ST‐crosslinked polyester for the ST/UP/LPA systems was also examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3369–3387, 2004     

Synthesis,characterizations and thermal behavior of methyl methacrylate and N‐(p‐carboxyphenyl) methacrylamide/acrylamide copolymers

The synthesis, characterization, and thermal properties of copolymers of methyl methacrylate (MMA) and N‐(p‐carboxyphenyl) methacrylamide/acrylamide (CPMA/CPA) are described. The copolymerization was carried out in solution by taking different mole fractions (0.1–0.5) of CPMA/CPA in the initial feed using azobisisobutyronitrile as an initiator and dimethylformamide as a solvent at 60°C. The copolymer composition was determined from ¹H‐NMR spectra by taking the ratio of the proton resonance signal due to the  OCH₃ of MMA (δ = 3.59 ppm) and the aromatic protons (δ = 7.6–7.8 ppm) of CPMA/CPA. The monomer reactivity ratios of MMA:CPMA and MMA:CPA were determined using the Fineman Ross and Kelen Tudos methods and were found to be 1.32 ± 0.01 [MMA], 1.11 ± 0.02 [CPMA], 2.60 ± 0.01 [MMA], and 0.20 ± 0.01 [CPA]. Incorporation of these comonomers in the MMA backbone resulted in an improvement in the glass‐transition temperature and thermal stability. The percent char also increased with the increase of CPMA/CPA content in the copolymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 259–267, 2000     

Atom transfer radical copolymerization of glycidyl methacrylate and methyl methacrylate

Glycidyl methacrylate (GMA) and methyl methacrylate (MMA) copolymers were synthesized by atom transfer radical polymerization (ATRP). The effect of different molar fractions of GMA, ranging from 0.28 to 1.0, on the polymer polydispersity index (weight‐average molecular weight/number‐average molecular weight) as the indicator of a controlled process was investigated at 70°C, with ethyl 2‐bromoisobutyrate as an initiator and 4,4′‐dinonyl‐2,2′‐bipyridyne (dNbpy)/CuBr as a catalyst system in anisole. The monomer reactivity ratios (r values) were obtained by the application of the conventional linearization Fineman–Ross method (r_GMA = 1.24 ± 0.02 and r_MMA = 0.85 ± 0.03) and by the Mayo–Lewis method (r_GMA = 1.19 ± 0.04 and r_MMA = 0.86 ± 0.03). The molecular weights and polydispersities of the copolymers exhibited a linear increase with GMA content. The copolymer compositions were determined by ¹H‐NMR and showed a domination of syndiotactic structures. The glass‐transition temperatures (T_g) of the copolymers analyzed by differential scanning calorimetry (DSC) decreased in the range 105–65°C with increasing GMA units. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of acrylic‐based processing aids on processibility,rheology, thermal and structural stability,and mechanical properties of PVC/wood–sawdust composites

Methyl methacrylate and ethylacrylate (MMA‐co‐EA) and methyl methacrylate and butylacrylate (MMA‐co‐BA) copolymeric processing aids were introduced into poly(vinyl chloride) (PVC)/33.3 wt % wood–sawdust composites containing 0.6 and 2.4 phr of calcium stearate lubricant. The properties of the composites were monitored in terms of processibility, rheology, thermal and structural stability, and mechanical properties. It was found that the mixing torque, wall shear stress, and extrudate swell ratio increased with increasing processing aid content because of increased PVC entanglement. MMA‐co‐BA (PA20) was found to be more effective than MMA‐co‐EA (K120 and K130), this being associated with the flexibility of the processing aids, and the dipole–dipole interactions between sawdust particles and polymeric processing aids. The sharkskin characteristic of the composite extrudate at high extrusion rate was moderated by the presence of processing aids. Adding the acrylic‐based processing aids and lubricant into PVC/sawdust composites improved the thermal and structural stability of the composites, which were evidenced by an increase in glass transition and decomposition temperatures and a decrease in polyene sequences, respectively. The changes in the mechanical properties of the composites involved a composite homogeneity, which was varied by degree of entanglement and the presence of wood sawdust, and un‐reacted processing aids left in the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 782–790, 2004     

THERMOANALYSIS AND MECHANICAL PROPERTIES OF EMULSION COPOLYMER POLY(MMA-PMI-ST)

Terpolymers of methyl methacrylate (MMA), N-phenylmaleimide (PMI) and styrene (St) were synthesized by emulsion copolymerization. The glass transition temperatures (T_g) and the thermostability of copolymers were determined by differential scanning calorimetry (DSC) and programmed thermogravimetric analysis (TGA), respectively. The terpolymers show a considerable increase in decomposition temperature, activation energy of decomposition and T_g with increasing content of PMI. Furthermore, the Vicat softening points of the terpolymers rise with PMI content. The mechanical properties (tensile strength and impact strength) of the terpolymers decrease with increasing PMI content and increase insignificantly with increasing St content.     

Synthesis of methyl methacrylate and N‐aryl itaconimide block copolymers via atom‐transfer radical polymerization

The paper describes the synthesis of block copolymers of methyl methacrylate (MMA) and N‐aryl itaconimides using atom‐transfer radical polymerization (ATRP) via a poly(methyl methacrylate)–Cl/CuBr/bipyridine initiating system or a reverse ATRP AIBN/FeCl₃·6H₂O/PPh₃ initiating system. Poly(methyl methacrylate) (PMMA) macroinitiator, ie with a chlorine chain‐end (PMMA‐Cl), having a predetermined molecular weight (M_n = 1.27 × 10⁴ g mol^?1) and narrow polydispersity index (PDI = 1.29) was prepared using AIBN/FeCl₃·6H₂O/PPh₃, which was then used to polymerize N‐aryl itaconimides. Increase in molecular weight with little effect on polydispersity was observed on polymerization of N‐aryl itaconimides using the PMMA‐Cl/CuBr/Bpy initiating system. Only oligomeric blocks of N‐aryl itaconimides could be incorporated in the PMMA backbone. High molecular weight copolymer with a narrow PDI (1.43) could be prepared using tosyl chloride (TsCl) as an initiator and CuBr/bipyridine as catalyst when a mixture of MMA and N‐(p‐chlorophenyl) itaconimide in the molar ratio of 0.83:0.17 was used. Thermal characterization was performed using differential scanning calorimetry (DSC) and dynamic thermogravimetry. DSC traces of the block copolymers showed two shifts in base‐line in some of the block copolymers; the first transition corresponds to the glass transition temperature of PMMA and second transition corresponds to the glass transition temperature of poly(N‐aryl itaconimides). A copolymer obtained by taking a mixture of monomers ie MMA:N‐(p‐chlorophenyl) itaconimide in the molar ratio of 0.83:0.17 showed a single glass transition temperature. Copyright © 2005 Society of Chemical Industry     

Three‐component terpolymers of glycidyl methacrylate with good swelling characteristics

Highly swellable glycidyl methacrylate terpolymers with styrene and a series of crosslinkers (divinyl benzene and ethylene, diethylene, and triethylene glycol dimethacrylates) were obtained by suspension polymerization. The loading capacities of the resins, their glass‐transition temperatures, and their swelling characteristics in 20 solvents were examined with respect to the monomer composition. A selected resin was modified for a cobalt–imine complex and tested as a catalyst in a model ring‐opening reaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Copolymers of methyl methacrylate with cinnamic acid

Methyl methacrylate (MMA) and cinnamic acid (CA) have been copolymerized radically at 60°C; the amounts of CA incorporated in copolymers are surprisingly low. The CA units sensitize the MMA units towards alkaline hydrolysis. The copolymers are less soluble than the homopolymer of MMA in toluene; their thermal stabilities are significantly higher and their glass transition temperatures are slightly lower.