Abstract
Living oligomers of methyl methacrylate (MMA) were synthesized photochemically with iron(III) tris(oxalato) ferrate(III) tetrahydrate (Fe[Fe(C2O4)3]·4H2O) as photoinitiator under UV irradiation of 254 nm at 40 °C in dimethyl sulfoxide in the presence of triethylamine as coinitiator. The synthesized oligomers were incorporated in the ethylene chain by reverse atom transfer radical polymerization in N,N′-dimethylformamide using 2,2′-azobisisobutyronitrile as initiator with FeCl3/2,2′-bipyridine (bpy) catalyst system. FT-IR and 1H NMR analysis confirms the incorporation of pre-synthesized poly(MMA) in the ethylene chain. Thermogravimetric analysis of the copolymer shows a three step decomposition process with the major decomposition at approximately 380 °C. Apparent activation energy (E a) of each step was calculated using non-isothermal methods of Kissinger, Friedeman, Flynn–Wall–Ozawa (FWO) and modified Coats-Redfern (MCR). The E a value obtained from FWO and MCR methods shows good agreement and the value for the final step of decomposition was calculated to be 235 kJ mol−1. The conversion dependency of decompositions on the process rate can be best explained by Sestak-Berggren model which can be established as \(\begin{aligned} f(\alpha ) = 3.67 \times 10^{2} \exp \left( {\frac{-199.28}{RT}} \right)(1 - \alpha )^{2.03} \alpha^{3.03} \hfill \\ \hfill \\ \end{aligned}\) with pre-exponential factor (A) = 3.67 × 102 min−1.
Similar content being viewed by others
References
Boaen NK, Hillmyer MA (2005) Postpolymerization functionalization of polyolefins. Chem Soc Rev 34:267–275
Clark HC, Jablonski CR (1974) Insertion of ethylene into a cationic hydrido(acetone)platinum(II) complex. Kinetics and mechanism. Inorg Chem 13:2213–2218
Duan G, Zhang C, Li A, Yang X, Lu L, Wang X (2008) Preparation and characterization of mesoporous zirconia made by using a poly (methyl methacrylate) template. Nanoscale Res Lett 3:118–122
Passaglia E, Coiai S, Cicogna F, Ciardelli F (2014) Some recent advances in polyolefin functionalization. Polym Int 63:12–21
Wiles DM, Scott G (2006) Polyolefins with controlled environmental degradability. Polym Degrade Stabil 91:1581–1592
Lee TY, Roper TM, Jonsson ES, Kudyakov I, Viswanathan K, Nason C, Guymon CA, Hoyle CE (2003) The kinetics of vinyl acrylate photopolymerization. Polymer 44:2859–2865
Younkin TR, Connor EF, Henderson JI, Friedrich SK, Grubbs RH, Bansleben DA (2000) Neutral single-component Nickel(II) polyolefin catalysts that tolerate heteroatoms. Science 287:460–462
Moineau G, Dubois Ph, Jerome R, Senninger T, Tessie Ph (1998) Alternative atom transfer radical polymerization for MMA using FeCl3 and AIBN in the presence of triphenylphosphine: an easy way to well-controlled PMMA. Macromolecules 31:545–547
Wang G, Zhu X, Cheng Z, Zhu J (2006) New ligands for the Fe(III)-mediated reverse atom transfer radical polymerization of methyl methacrylate. J Polym Sc 44:2912–2921
Ozturk T, Cakmak I (2008) Synthesis of poly(ethylene glycol-b-styrene) block copolymers by reverse atom transfer radical polymerization. J Polym Res 15:241–247
Yagci Y, Schnabel W (1990) Light-induced synthesis of block and graft copolymers. Prog Polym Sci 15:551–601
Ruzette AV, Leibler L (2005) Block copolymers in tomorrow’s plastics. Nat Mater 4:19–31
Shipp DA, Wang J, Matyjaszewski K (1998) Synthesis of acrylate and methacrylate block copolymers using atom transfer radical polymerization. Macromolecules 31:8005–8008
Bates FM, Fredrickson GH (1990) Block copolymer thermodynamics: theory and experiment. Ann Rev Phys Chem 41:525–557
Bilalis P, Pitsikalis M, Hadjichristidis N (2006) Controlled nitroxide mediated and reversible addition-fragmentation chain transfer polymerization of N-vinylpyrrolidone: synthesis of block copolymers with styrene and 2-vinylpyridine. J Polym Sci Part A Polym Chem 44:659–665
Noshay A, Mcgrath JE (1977) Block copolymers, overview and critical survey. Academic Press, New York
Makarova LI, Filimonova LV, Dubrovina LV, Buzin MI, Nikiforova GG, Zavin BG, Papkov VS (2010) Synthesis and properties of siloxane(ethylene oxide) urethane block copolymers. Polym Sci Ser B 52:346–352
Vinchon Y, Reeb R, Riess G (1976) Preparation of macromolecular azo initiators by anionic polymerization: application to synthesis of block copolymers. Eur Polym J 12:317–321
Peng ZP, Wang D, Liu X, Tong Z (2007) RAFT synthesis of a water-soluble triblock copolymer of poly(styrenesulfonate)-b-poly(ethylene glycol)-b-poly(styrenesulfonate) using a macromolecular chain transfer agent in aqueous solution. J Polym Sci Part A Polym Chem 45:3698–3706
Yoshikawa C, Goto A, Tsujii Y, Fukuda T, Yamamoto K, Kishida A (2005) Fabrication of high density polymer brush on polymer substrate by surface-initiated living radical polymerization. Macromolecules 38:4604–4610
Benarbia A, Elidrissi A, Ganetri I, Touzani R (2014) Synthesis, characterization and thermal degradation kinetics of copolyesters. J Mater Environ Sci 5:1262–1279
Sanyal TK, Das NN (1980) Synthesis and the thermal decomposition of iron(III) tris(oxalato) ferrate(III) tetrahydrate. J Inorg Nucl Chem 42:811–813
Malek J, Criado JM (1994) A simple method of kinetic-model discrimination. 1. Analysis of differential nonisothermal data. Thermochim Acta 236:187–197
Atkins P, Paula J (2010) Physical chemistry, 9th edn. WH Freeman, New York
Brown ME (2001) Introduction to thermal analysis, 2nd edn. Kluwer, Dodrecht
Kissinger HE (1957) Reaction kinetics in differential thermal analysis. Anal Chem 29:1702–1706
Friedeman HL (1964) Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. J Polym Sci 6:183–195
Ozawa T (2000) Thermal analysis-review and prospect. Thermochim Acta 355:35–42
Flynn JH (1991) General differential technique for the determination of parameters for d(α)/dt = f(α)A exp (−E/RT). Energy of activation, pre exponential factor and order of reaction (when applicable). J Therm Anal 37:293–305
Jankovic B, Kolar-Anic L, Smiciklas I, Dimovic S, Arandelovic D (2009) The non-isothermal thermogravimetric tests of animal bones combustion. Part 1: kinetic analysis. Thermochim Acta 495:129–138
Akahira T, Sunose T (1971) Joint convention of four electrical institutes. Res Rep Chiba Inst Technol 16:22–23
Coats AW, Redfern JP (1964) Kinetic parameters from thermogravimetric data. Nature 201:68–69
Jankovic B, Mentus S, Jankovic M (2008) A kinetic study of the thermal decomposition process of potassium metabisulfite: estimation of distributed reactivity model. J Phys Chem Solids 69:1923–1933
Ozturk T, Goktas M, Hazer B (2010) One-step synthesis of triarm block copolymers via simultaneous reversible-addition fragmentation chain transfer and ring-opening polymerization. J Appl Polym Sci 117:1638–1645
Ozturk T, Goktas M, Hazer B (2011) Synthesis and characterization of poly(methyl methacrylate-block-ethyleneglycol-block-methyl methacrylate) block copolymers by reversible addition fragmentation chain transfer polymerization. J Macromol Sci Part A Pure Appl Chem 48:265–272
Ozturk T, Yavuz M, Goktas M, Hazer B (2016) One-step synthesis of triarm block copolymers by simultaneous atom transfer radical and ring-opening polymerization. Polym Bull 73:1497–1513
Cowie JMG (1985) Alternating copolymers. Plenum Press, New York
Moayed SH, Fatemi S, Pourmahdian S (2007) Synthesis of a latex with bimodal particle size distribution for coating applications using acrylic monomers. Prog Org Coat 60:312–319
Biros J, Larina T, Trekoval J, Pouchly J (1982) Dependence of the glass transition temperature of poly(methyl methacrylates) on their tacticity. Colloid Polym Sci 260:27–30
Kermagoret A, Debuigne A, Jerome C, Detrembleur C (2014) Precision design of ethylene- and polar-monomer-based copolymers by organometallic-mediated radical polymerization. Nature Chem 6:179–187
Kashiwagi T, Inaba A, Brown JE, Hatada K, Kitayama T, Masuda E (1986) Effects of weak linkages on the thermal and oxidative degradation of Poly(methyl methacrylates). Macromolecules 19:2160–2168
Beyler CL, Hirschler MM (2002) Thermal decomposition of polymers, sect 1, chap 7. In: DiNenno PJ (ed) SFPE handbook of fire protection engineering, 3rd edn. National Fire Protection Association Inc, Quincy, Massachusetts
Vyazovkin S, Burnham AK, Criado JM, Maqueda LAP, Popescu C, Sbirrazzuoli N (2011) ICTAC kinetics committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta 520:1–19
Assanvo EF, Konwar D, Baruah SD (2015) Thermal behavior of Ricinodendron heudelotii oil polymer. J Therm Anal Calorim 119:1995–2003
Malek J (1992) The kinetic analysis of non isothermal data. Thermochim Acta 200:257–269
Malek J (2000) Kinetic analysis of crystallization processes in amorphous materials. Thermochim Acta 355:239–253
Svoboda R, Malek J (2011) Interpretation of crystallization kinetics results provided by DSC. Thermochim Acta 526:237–251
Acknowledgments
The authors wish to thank Dr. D. Ramaiah, Director, CSIR-North East Institute of Science and Technology, Jorhat for his permission to publish the results. Financial support from CSIR-network Project CSC-0206 is also acknowledged.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Baruah, U., Saikia, M., Assanvo, E.F. et al. Synthesis and thermal analysis of poly(methyl methacrylate) oligomer functionalized polyethylene block copolymer. Polym. Bull. 74, 2137–2158 (2017). https://doi.org/10.1007/s00289-016-1828-7
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00289-016-1828-7