Microwave synthesis and thermal properties of polyacrylate derivatives containing itaconic anhydride moieties
- Sameh M Osman†1,
- Mohamed H El-Newehy†1, 2Email author,
- Salem S Al-Deyab†1 and
- Ayman El-Faham†1, 3Email author
© Osman et al.; licensee Chemistry Central Ltd. 2012
Received: 10 April 2012
Accepted: 30 July 2012
Published: 8 August 2012
Microwave irradiation as an alternative heat source is now a well-known method in synthetic chemistry. Microwave heating has emerged as a powerful technique to promote a variety of chemical reactions, offering reduced pollution, low cost and offer high yields together with simplicity in processing and handling. On the other hand, copolymers containing both hydrophilic and hydrophobic segments are drawing considerable attention because of their possible use in biological systems. Various copolymer compositions can produce a very large number of different arrangements, producing materials of varying chemical and physical properties. Thus, the hydrophilicity of copolymers can be modified by changing the amount of incorporated itaconic anhydride.
A series of methyl methacrylate (MMA) and acrylamide (AA) copolymers containing itaconic anhydride (ITA) were synthesized by microwave irradiation employing a multimode reactor (Synthos 3000 Aton Paar, GmbH, 1400 W maximum magnetron) as well as conventional method. The thermal properties of the copolymers were evaluated by different techniques. Structure-thermal property correlation based on changing the itaconic anhydride ratio was demonstrated. Results revealed that the incorporation of itaconic anhydride into the polymeric backbone of all series affect the thermal stability of copolymers. In addition, the use of the microwave method offers high molecular weight copolymers which lead eventually to an increase in thermal stability.
Microwave irradiation method showed advantages for the produced copolymers compared to that prepared by conventional method, where it can offer a copolymer in short time, high yield, more pure compounds and more thermally stable copolymers, rather than conventional method. Also, microwave irradiation method gives higher molecular weight due to prevention of the chain transfer. Moreover, as the itaconic anhydride content increases the thermal stability and T g increase due to the decrease in the crystallinity.
Microwave-assisted organic synthesis has been recognized as one of the most interesting areas of current chemical research [1–5]. Microwave heating has emerged as a powerful technique to promote a variety of chemical reactions, offering reduced pollution, low cost and offer high yields together with simplicity in processing and handling [1, 6–11]. The application of microwave irradiation to organic synthesis has been the focus of considerable attention in recent years and is becoming an increasingly popular technology [12–19]. Recently, there has been growing interest in applying microwave irradiation to polymer synthesis [20–23] as it can accelerate many syntheses providing selective activation with short start-up phase and can allow fast optimization of reactions.
Itaconic anhydride (ITA) is an unsaturated dicarbonic organic anhydride with one carbonyl group conjugated to the methylene group. It can be regarded as a substituted acrylic or methacrylic derivatives. In addition, it can be obtained from renewable resources [24, 25]. Also, it can be polymerized [26, 27] or copolymerized with various other monomers by free radical reactions [28–33].
As a result of increasing studies of acrylate derivatives and itaconic acid polymers or copolymers, various methods for the synthesis of these polymers and their copolymers with the monomers such as acrylonitrile, styrene and acrylic esters have been reported, in most cases radical polymerizations [34–42]. Various copolymer compositions can produce a very large number of different arrangements, producing materials of varying chemical and physical properties. Thus, the hydrophilicity of copolymers can be modified by changing the amount of incorporated itaconic anhydride .
The present work described copolymerization of acrylic monomers such as methyl methacrylate (MMA) and acrylamide (AA) with different ratios of itaconic anhydride (ITA) through free radical copolymerization in the presence of α,α'-azobisisobutyro nitrile (AIBN). Copolymerizations were carried out in both conventional and microwave conditions. The chemical structure of the prepared copolymers was confirmed by FTIR and size exclusion chromatography (SEC) and the thermal stability were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).
Materials & Equipments
Itaconic anhydride (ITA) was purchased from Fluka. Acrylamide (AA) was purchased from LKB. Methyl methacrylate (MMA) was purchased from M & B. α,α`-Azobisisobutyronitrile (AIBN) was purchased from Aldrich and was recrystallized from absolute ethanol before use. All solvents were dried before use.
The microwave irradiation employing a multimode reactor (Synthos 3000, Aton Paar GmbH, 1400 W maximum magnetron) was used to prepare the copolymers. Fourier transform infrared spectroscopy (FTIR) Spectra was recorded on Nicolet 560 Magna spectrometer. Thermal properties of the copolymers were examined through using thermogravimetric analysis (TGA) under nitrogen, from room temperature to 800°C with heating rate of 10°C/min and differential scanning calorimetery (DSC) which was carried on TA-Q500 in which Specimens of (5–10 mg) were encapsulated in aluminum pans and were heated or cooled between -25°C and 400°C under dry nitrogen atmosphere with heating rate of 10°C /min. Number-average molecular weight (M n ) and molecular weight distribution (M w /M n ) were estimated by size exclusion chromatography (SEC) which was carried on Viscotek, HT-GPC. Polystyrene standards were employed for calibration. The analysis was performed at 35°C using high-performance liquid chromatography-grade THF as the eluent. Polystyrene standards were used to calibrate the molecular weight.
Synthesis of Copolymers
General Procedure for Conventional Method
Yield % of MMA/ITA and AA/ITA copolymers using microwave irradiation
General Procedure for Microwave-Assisted Synthesis
Employing a multimode reactor (Synthos 3000, Aton Paar GmbH, 1400 W maximum magnetron); the initial step was conducted with 4-Teflon vessels rotor (MF 100) that allow processing four reactions under the same conditions. Each vessel has itaconic anhydride (ITA) was mixed with methyl methacrylate (MMA) or acrylamide (AA) in specific ratio (10:1, 10:2, and 10:4), in the presence of (0.1 g) AIBN and 2-butanone as a solvent (Table 1). The individual vessels were purged with nitrogen gas for 10 min and then were placed in the corresponding rotor, fixed by screwing down the upper rotor place, and finally the rotor was closed with a protective hood. After heating the vessels for 5 min. at 140°C and hold at the same temperature for 5 min (~2 bar pressure, 400 W). Cooling was accomplished by a fan (5 min). The final product was washed with diethyl ether, and was dried in oven under vacuum at 40°C for 24 h.
Results and Discussion
Fourier Transform Infrared Spectroscopy (FT-IR)
The intensity of the anhydride peaks was increased as the ratio of ITA increased in the copolymer, Figures 1 and 2. Copolymers prepared by both conventional method and microwave irradiation showed the same spectral characterization.
Thermogravimetric Analysis (TGA)
For copolymers PMITA1 & PMITA5, the thermogram, Figure 3, showed that the prepared copolymers were degraded in four similar degradation steps. The first step with weight loss of 2.42% for conventional method at 70-115°C and 21.27% for microwave-assisted method at 130-225°C which is attributed to water evaporation and decarboxylation which is more clear in the prepared copolymers by microwave irradiation, respectively. The last stage exhibited subsequent major degradation process between 331-445°C (87.13%, wt loss) and between 331-445°C (80.71%, wt loss) for PMITA1 and PMITA5, respectively.
Information derived from TGA measurements of degradation of copolymers PMITA 1, 4-6 and PAITA 2, 7-9
T onset (°C)
T max (°C)
T 50 (°C)
The copolymerization using microwave irradiation led to an increased T onset of PMITA1 compared to PMITA5 which prepared by conventional method, however, T 50 and T max decreased. While on increasing the itaconic anhydride content (PMITA4-6), T onset and T 50 decreased and T max are too close.
Similarly, PAITA2, 7-9, T onset , T 50 and T max increased from PAITA2, which prepared by conventional method, to PAITA9, which prepared by microwave irradiation. The same conclusion was observed with increasing the itaconic anhydride content (PAITA7-9).
This could be explained by that microwave irradiation gave chance for increasing the itaconic anhydride content more than conventional method. As expected from the literature, the molecular weight of the copolymers decreased with increasing ITA concentration in the feed, which may be a consequence of the allylic hydrogen in ITA that can act as a chain transfer agent in radical polymerization [43, 44].
Differential Scanning Calorimetry (DSC)
Moreover, for the degradation process of the copolymer PAIT2, PAIT7-9 it is clear that the effect of the hydrogen bond so during the first degradation only dehydration followed by deamination process and this stage there is no differences between the prepared polymer by convention method and microwave irradiation while at higher temperature most of the hydrogen bond were broken and the difference in the thermal stabilities and the effect of the ITA was clear .
The molecular weight and Elemental microanalysis Determination
Elemental microanalysis of the prepared copolymers using microwave irradiation
Itaconic anhydride based copolymers with both methyl methacrylate and acrylamide with different ratios were successfully prepared using microwave irradiation technique. For comparison study, similar copolymers were prepared by conventional method. The obtained results showed the advantages of microwave irradiation method over conventional method. Microwave irradiation method offers the possibility of the preparation of copolymer in short time with high yield, high molecular weight and high thermal stability. Moreover, as the itaconic anhydride content increases the thermal stability and T g increase due to the decrease in the crystallinity.
This project was supported by King Saud University, Deanship of Scientific Research, College of Science Research Center.
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