Synthesis and thermal self-crosslinking reaction of copolymers from 2,3-epoxypropyl methacrylate and p-substituted phenyl methacrylates

Copolymers of 2,3-expoxypropyl (glycidyl) methacrylate (GMA) with various phenyl methacrylates such as 4-nitrophenyl methacrylate (NPMA), 4-chlorophenyl methacrylate (CPMA), or phenyl methacrylate (PMA), and other monomers such as methyl methacrylate (MMA), ethyl acrylate (EA), or styrene (ST) were synthesized by radical copolymerization, and then thermal self-crosslinking reactions of the obtained copolymers were carried out using various catalysts such as quarternary ammonium salts, tert-amines, or the crown ether/potassium salt systems at 100–150°C. Although the copolymer of GMA–NPMA–MMA does not produce any gel products without catalyst upon heating at 110°C for 5 h, this copolymer gives gel products in 82% yield using 10 mol% of tetrabutylammonium bromide as a catalyst under the same conditions. The rate of gel production of the copolymer of NPMA is faster than those of copolymers of CPMA and PMA. The rate of the gel production of the copolymer of GMA–NPMA–EA is also faster than those of copolymers of MMA and ST. Furthermore, it was found that the rate of gel production of the copolymer was strongly affected by the kind of catalyst, the catalyst concentration, and the reaction temperature.     

Surface Energy and Thermal Stability Studies of Poly(dimethyl siloxane)–Poly(alkyl(meth)acrylate) Copolymers

The correlation between the surface energy and thermal stability of polymers plays an important role in engineering of plastic materials. In this work, microstructural characteristics of copolymers of poly(dimethyl siloxane) with benzyl methacrylate, ethyl methacrylate, and methyl acrylate are correlated with their surface energy and thermal stability. The poly(dimethyl siloxane) segments in the copolymer chains affected the hydrophobic behavior. The surface energy of the synthesized copolymers decreased by increasing segments of alkyl methacrylates. The thermal stability of copolymers suggesting that heat resistance of poly(dimethyl siloxane) copolymers used in this correlation can be improved by adjusting the units of alkyl methacrylates in copolymers.     

Effect of cardinyl acrylate on thermal behavior of methyl methacrylate copolymers

Cardinyl acrylate (CA), prepared by the reaction of acryloyl chloride and cardinol, was copolymerized with methyl methacrylate (MMA) in bulk at 80°C using 2% benzoyl peroxide as an initiator. The copolymer composition was determined by ¹H-NMR spectroscopy. Three copolymer samples containing 0.0048–0.0838 mol fraction of cardinyl acrylate were obtained. A significant improvement in the thermal stability of MMA was observed by incorporating 0.0048–0.0838 mol fraction of CA in the backbone. The activation energy for decomposition in the temperature range 350–480°C for copolymers was higher than PMMA. © 1992 John Wiley & Sons, Inc.     

Study on the Copolymerization Kinetics of 8-Quinolinyl Methacrylate with Methyl Methacrylate,n-Butyl Methacrylate and Styrene

Abstract

The 8-quinolinyl methacrylate (8-QMA) monomer was prepared and characterized by the conventional methods of analysis. The 8-QMA monomer was copolymerized with methyl methacrylate (MMA), n-butyl methacrylate (BMA) and styrene under different monomer feed ratio using azobisisobutyronitrilic (AIBN) as an initiator by solution copolymerization. The polymerization reaction was allowed to proceed only upto sim; 10%. The composition of the resulting copolymers was determined by UV-visible spectrophotometry and reactivity ratio for each monomer pair was calculated. The relative reactivity of the monomers was discussed on the basis of the size of alkyl group in methacrylates and effect of resonance on the stability of the styryl radicals during the copolymerization.     

Copolymerization of γ-methacryloxy propyl trimethoxy silane and methyl methacrylate

Copolymerization of methyl methacrylate (MMA) with low mole fractions of γ-methacryloxypropyl trimethoxy silane (MTS) was investigated with an aim to synthesize copolymers which can be cross-linked by hydrolytic cleavage of methoxy groups. Several copolymer samples were prepared by changing the molar ratios of two monomers in the initial monomer feed. Rate of copolymerization depended on the concentration of monomers and increased with an increase in MTS concentration. The copolymers were characterized by infrared (IR) and ¹H nuclear magnetic resonance (NMR) spectroscopy, elemental analysis, and intrinsic viscosity determination. The effect of structure on thermal behavior was investigated by using dynamic thermogravimetry in nitrogen atmosphere. An attempt was made to identify products of degradation using mass spectrometry. Copolymers were also hydrolyzed in water and cross-linked. The effect of MTS in copolymers on percentage gel formation was determined.     

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%.     

Copolymerization of methyl methacrylate with N-(methoxyphenyl) itaconimides

This article describes the synthesis and characterization of N-(3-methoxyphenyl) itaconimide (MAI) and N-(4-methoxyphenyl) itaconimide (PAI) obtained by the reaction of itaconic anhydride with m-anisidine and p-anisidine, respectively. Structural and thermal characterization of MAI and PAI monomers was performed with Fourier transform infrared (FTIR), ¹H-NMR, differential scanning calorimetry (DSC), and thermogravimetric analysis. Copolymerization of methyl methacrylate (MMA) with various amounts of MAI or PAI ranging from 0.1 to 0.5 was performed in solution with azobisisobutyronitrile as an initiator. Structural and molecular characterization of copolymers was performed with FTIR, ¹H-NMR, elemental analysis, and gel permeation chromatography. The nitrogen percentage was used to calculate the copolymer composition. The monomer reactivity ratios for MMA–MAI copolymers were found to be 1.00 ± 0.01 for MMA and 0.99 ± 0.07 for MAI; those for MMA–PAI copolymers were 0.93 ± 0.02 for MMA and 1.11 ± 0.10 for PAI. The molecular weights of the copolymers were in the range of 0.94–9.7 × 10³ (number-average molecular weight) and 3.3–101.8 × 10³ (weight-average molecular weight), with polydispersity indices in the range of 1.5–4.1. The molecular weight decreased with the increasing molar fraction of imide in the polymer backbone. The glass-transition temperature, as determined from DSC scans, increased with increasing amounts of itaconimides in the copolymers. A significant improvement in the char yield, as determined by thermogravimetry, was observed upon copolymerization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal behavior of poly(dimethyl itaconate) and poly(di‐n‐butyl itaconate) copolymerized with methyl methacrylate

The thermal degradation behavior of random copolymers of dimethyl itaconate and di‐n‐butyl itaconate with methyl methacrylate was studied. The thennal stability of copolymers depends on the structure of the di‐n‐alkyl itaconate comonomer, and on the copolymer composition. The relative thermal stability increases with the methyl methacrylate copolymer molar fraction, following a trend similar to the glass transition temperature variation. The activation energy was obtained by using MacCallum and Tanner's approach. In addition, the thermal degradation of homopolymers was evaluated in inert atmosphere as well as in thermo‐oxidative conditions, presenting different behaviors.     

Copolymerization of 4-cyanophenyl methacrylate with methyl methacrylate: Synthesis,characterization and determination of monomer reactivity ratios

Summary A novel methacrylic monomer, 4-cyanophenyl methacrylate (CPM) was synthesized by reacting 4-cyanophenol dissolved in methyl ethyl ketone (MEK) with methacryloyl chloride in the presence of triethylamine as a catalyst. Copolymers of CPM with methyl methacrylate(MMA) at different composition was prepared by free radical solution polymerization at 70±1 °C using benzoyl peroxide as initiator. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The solubility of the polymers was tested in various polar and non polar solvents. The molecular weight and polydispersity indices of the copolymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in mole fraction of MMA content. The thermal stability of the copolymer increases with increases in mole fraction of CPM content in the copolymer. The copolymer composition was determined by using ¹H-NMR spectroscopy. The monomer reactivity ratios estimated by the application of linearization methods such as Fineman-Ross (r₁=2.524±0.038, r₂=0.502±0.015), Kelen-Tudos (r₁=2.562±0.173, r₂=0.487±0.005) and extended Kelen-Tudos methods (r₁=2.735±0.128, r₂=0.4915±0.007).     

Synthesis of well‐defined comb‐like amphiphilic copolymers with protonizable units in the pendent chains: 1. Preparation of narrow polydispersity copolymers of methyl methacrylate and 2‐hydroxyethyl methacrylate by atom‐transfer radical polymerization

Well‐defined methyl methacrylate (MMA) and 2‐(trimethylsiloxy)ethyl methacrylate (Pro‐HEMA) copolymers were prepared by atom‐transfer radical polymerization(ATRP), using CuCl/2,2′‐bipyridine as catalytic system and p‐toluenesulfonyl chloride as initiator. ATRP process of MMA and Pro‐HEMA was monitored by ¹H NMR, and the kinetic curves of the MMA/Pro‐HEMA copolymerization were plotted in terms of the ¹H NMR data. At low content of Pro‐HEMA in the feed composition, the copolymerization can be well controlled with the molecular weight, polydispersity and the monomer distribution in the copolymer chain. With the increase of Pro‐HEMA content in the feed mixture, the composition of the final copolymer deviates from the composition of the feed mixture gradually, and gradient copolymers of MMA/Pro‐HEMA can be obtained. Through the hydrolysis process, well‐defined copolymers of MMA/HEMA were obtained from poly(MMA/Pro‐HEMA). Copyright © 2003 Society of Chemical Industry     

Star‐shaped POSS–methacrylate copolymers with phenyl–triazole as terminal groups,synthesis, and the pyrolysis analysis

Star‐shaped polyhedral oligomeric silsesquioxane (POSS)–methacrylate hybrid copolymers with phenyl–triazole as terminal groups had been designed and synthesized via sequential atom transfer radical polymerization (ATRP), azidation, and phenylacetylene‐terminated procedures, and the hybrid copolymers here could be denoted as POSS–(PXMA‐Pytl)₈, where X can be M, B, L, and S, represented four different methacrylate monomers, such as methacrylate (MMA), butyl methacrylate (BMA), lauryl methacrylate (LMA), and stearyl methacrylate (SMA), respectively. Thermal gravimetric analysis (TGA) and in situ Fourier transform infrared spectroscopy (FTIR) were applied for studying the thermal stability and degradation mechanism, and it was found that all of the POSS–(PXMA‐Cl)₈ and POSS–(PXMA‐Pytl)₈ copolymers exhibited excellent thermal stabilities, which had great potential in heat‐resistant material application. Different tendencies of decomposition temperatures at 5% and 10% weight loss (T₅ and T₁₀) dependent on the side‐chain length and terminal group species were investigated respectively. The longer alkyl side chains of the monomers, the lower thermal stabilities, and enhanced T₅ and T₁₀ were also shown with the introduction of phenyl–triazole groups instead of chlorine groups. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40652.     

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     

Studies on the microstructure of vinyl/N‐phenylmaleimide copolymers by NMR and their applications

The micro‐ and stereostructures and sequence distribution of methyl methacrylate (MMA)/N‐phenylmaleimide (PMI) and styrene (St)–PMI copolymers were studied in detail with NMR spectroscopy. The MMA–PMI copolymer was in a random sequence distribution and the St–PMI copolymer was alternating in structure. Some micro‐ and stereoinformation of the MMA–PMI copolymers could be obtained from ¹H‐NMR spectra. The average number sequence length obtained from the copolymer triad by ¹³C‐NMR spectra was in agreement with that calculated from the reactivity ratios measured by an elemental analyzer. From the triad fraction of the copolymer measured by ¹³C‐NMR, the copolymer chain of MMA–PMI was proved to be a one‐order Markov chain. More suitable propagation reactions were proposed from the deviation of sequence distribution of the St–PMI copolymer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2581–2587, 2000     

Functionalized polyethylene on property enhancement of lubricating oil and their performance evaluation study

Methyl methacrylate (MMA) functionalized polyethylene additives for improving the properties of lubricating oil has been investigated in which poly(MMA-co-ethylene) were synthesized by using three different polymerization techniques such as miniemulsion, post polymerization and reverse atom transfer radical polymerization with 1.0 molL −1 of MMA and 20 bar of ethylene pressure. The copolymers are block in nature with the composition of 1:3 molar ratios of ethylene:MMA which is independent of polymerization techniques used. ¹H NMR analysis confirmed the successful incorporation of the copolymers in the lubricating oil. Thermogravimetric analysis reveals that the addition of poly(MMA-co-ethylene) increases thermal stability of the additive doped lubricating oil by approximately 40°C with a single stage decomposition pattern. Flash point measurements show an increasing flash point values for copolymer doped lubricating oil. From rheological study, the viscosity index of base lubricating oil has found significant increases from 102 to 129 with the addition of poly(MMA-co-ethylene) and the higher molecular weight (MW) of this copolymer provides better thickening efficiency. However, copolymer with higher MW seems to be more susceptible to mechanical degradation resulting in lower shear stability whereas copolymer with lower MW acts as a better pour point depressant.     

Phenyl acrylates and divinyl benzene cross-linked copolymers as basic novel supports: Synthesis and characterization

Suspension Copolymerization of glycidyl methacrylate (GMA), phenyl methacrylate (PhMA), 2,4,6-tribromophenyl acrylate (TBPA), and 4-acetylphenyl acrylate (APA) with divinyl benzene (DVB) was carried out at 80 ± 1°C in aqueous medium, as basic supports for possible applications in polymer-supported chemistry. The resulting copolymer heads were characterized with various techniques. The identification of monomers in the copolymer was attempted using FTIR and ¹³C-CP/MAS-NMR spectroscopic techniques. The optical and scanning electron microscopic methods were used to study the shape, size, and surface morphology of the beaded copolymers. The particle-size distribution was measured, and the average particle size of the particulate copolymers were carried out using a Malvern particle-size analyzer. The decomposition temperatures and energy of activation involved in the thermal degradation were studied with thermogravimetry. The solvent imbibition of the polymer supports in various solvents was carried out with a centrifuge method.     

Copolymerization of N‐aryl substituted itaconimide with methyl methacrylate: Effect of substituents on monomer reactivity ratio and thermal behavior

The article describes the synthesis and characterization of N‐(4‐methoxy‐3‐chlorophenyl) itaconimide (MCPI) and N‐(2‐methoxy‐5‐chlorophenyl) itaconimide (OMCPI) obtained by reacting itaconic anhydride with 4‐methoxy‐3‐chloroanisidine and 2‐methoxy‐5‐chloroanisidine, respectively. Structural and thermal characterization of MCPI and OMCPI monomers was done by using ¹H NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of MCPI or OMCPI with methyl methacrylate (MMA) in solution was carried out at 60°C using AIBN as an initiator and THF as solvent. Feed compositions having varying mole fractions of MCPI and OMCPI ranging from 0.1 to 0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by FTIR, ¹H NMR, and elemental analysis and percent nitrogen content was used to calculate the copolymer composition. The monomer reactivity ratios for MMA–MCPI copolymers were found to be r₁ (MMA) = 0.32 ± 0.03 and r₂ (MCPI) = 1.54 ± 0.05 and that for MMA–OMCPI copolymers were r₁ (MMA) = 0.15 ± 0.02 and r₂ (OMCPI) = 1.23 ± 0.18. The intrinsic viscosity [η] of the copolymers decreased with increasing mole fraction of MCPI/or OMCPI. The glass transition temperature as determined from DSC scans was found to increase with increasing amounts of OMPCI in copolymers. A significant improvement in the char yield as determined by thermogravimetry was observed upon copolymerization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2391–2398, 2006     

Synergistic effect of alkyl lactate functional groups on properties of methacrylate polymers

In this work, four novel different alkyl lactate methacrylate monomers were synthesized through azeotropic esterification method by reacting methyl, ethyl, propyl and butyl lactates with methacrylic acid. The prepared monomers were polymerized through solution polymerization technique and both monomers and polymers were analyzed by FTIR, ¹H NMR and ¹³C NMR spectroscopy techniques to elucidate the structure and to confirm their formation. Increasing the number of methylene units in alkyl lactate side chain decreases the glass transition temperature (T_g) of the polymers. Average molecular interchain spacing (〈R〉) of polymers was obtained from the wide-angle X-ray diffraction measurement and the values ranged from 6.26 to 7.18 Å based on the length of alkyl lactate group. The prepared polymers showed hygroscopic property and their moisture absorption was in the range of 10–24% (w/w) depending upon the length of alkyl lactate moiety, relative humidity and time. These polymers have the potential for hydrogel applications owing to their increased moisture absorption capacity. Both polymethyl and propyl lactate methacrylate showed two distinct and prominent thermal degradations whereas polyethyl and butyl lactate methacrylates showed only a single distinct and prominent thermal degradation step. An interesting result of as-synthesized polymers showed odd–even chain length effect in the properties of 〈R〉, moisture uptake and thermal stability.

     

Copolymerization and thermal behavior of methyl methacrylate with N‐(phenyl/p‐tolyl) itaconimides

This study describes the synthesis, characterization, and thermal behavior of copolymers of methyl methacrylate (MMA) and N‐p‐tolyl itaconimide (PTI)/N‐phenyl itaconimide (I). Homopolymerization and copolymerization of N‐(phenyl/p‐tolyl) itaconimide with MMA was carried out by use of various mole fractions of N‐aryl itaconimide in the initial feed from 0.1 to 0.5, using azobisisobutyronitrile as an initiator and tetrahydrofuran as the solvent. The copolymer composition was determined by ¹H‐NMR spectroscopy using the proton resonance signals attributed to –OCH₃ of MMA (δ = 3.5–3.8 ppm) and the aromatic protons (δ = 7.0–7.5 ppm) of N‐aryl itaconimide. The reactivity ratios of the monomers were found to be r₁ (PTI) = 1.33 ± 0.05/r₂ (MMA) = 0.24 ± 0.03 and r₁ (I) = 1.465 ± 0.035/r₂ (MMA) = 0.385 ± 0.005. The molecular weight of the copolymers decreased with increasing mole fraction of N‐aryl itaconimide in the copolymers. Glass‐transition temperature (T_g) and thermal stability of PMMA increased with increasing amounts of itaconimides in the polymer backbone. A significant increase in the percentage char yield at 700°C was observed on incorporation of a low mole fraction of N‐aryl itaconimides. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1195–1202, 2003     

Polymerization initiated with polymeric compounds,II

The polymerization of methyl methacrylate initiated by the copolymers methacrylaldehyde — styrene — divinylbenzene and acrylaldehyde — ethylene dimethacrylate in the absence of usual initiators was investigated. The polymerization was found to proceed fairly readily and fast. Acceleration can be achieved by adding glycerylaldehyde. An increase in the surface of the initiating copolymer favourably influences the reaction rate; at the same time, however, physical trapping of ungraft poly(methyl methacrylate) molecules in the macroporous initiator seems likely to occur. It was also found that only copolymers containing aldehyde groups could be used for initiation and that besides MMA some other monomers could be polymerized in this way, such as glycidyl methacrylate, acrylic and methacrylic acid, acrylonitrile, and alkyl acrylate.     

Flow behavior in a corotating twin‐screw extruder of pure polymers and blends: Characterization by fluorescence monitoring technique

The objective of this work was to investigate the flow behavior of pure polymers and blends, especially miscible polymer/polymer systems, in a corotating twin‐screw extruder (TSE) using an online fluorescence monitoring device. An immiscible blend was also studied for the sake of comparison. The fluorescence signal was obtained by using synthesized fluorescence tracers added to the melt at very low concentrations. These tracers consisted of two styrene‐maleic anhydride copolymers (SMA) labeled with anthracene. The investigated blends were SMA8 (8 wt % of MA in SMA)/polystyrene (PS), SMA14 (14 wt % of MA in SMA)/styrene acrylonitrile copolymer (SAN), and poly(methyl methacrylate) (PMMA)/ethyl acrylate‐methyl methacrylate copolymer (PMMAEA). The residence time distribution (RTD), the mean residence time (t ), the dimensionless variance (σ_θ²), the Peclet number (Pe) and the fluorescence peak intensity distribution of pure polymers and binary polymer systems were investigated and interpreted in terms of polymers rheological properties. It was observed that polymers presenting higher viscosity or higher pressure showed longer residence time. A difference in behavior was also observed for the RTD of miscible and immiscible blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011