Synthesis and characterization of methyl methacrylate - glycerol hydrogels by polymerization in acid medium

Laura Trujillo-Vargas

doi:10.36561/ING.27.5

Authors

Laura Trujillo-Vargas Tecnológico de Antioquía, Colombia https://orcid.org/0000-0002-9998-5916

DOI:

https://doi.org/10.36561/ING.27.5

Keywords:

Poly (methyl methacrylate), Glycerol, Sulfuric acid, Citric acid, Cross Linking

Abstract

Hydrogels were prepared from methyl methacrylate, glycerol, and sulfuric or citric acid. A novel route for the synthesis of crosslinked materials using unconventional initiators was evaluated using a 23 factorial experimental design. Effects of independent variables (polymerization time, type, and acid concentration) were statistically analyzed through ANOVA. The synthesis route includes condensation, free-radical and transesterification reactions with modifications of the polymer chemical properties such as the formation of a crosslinking polyester with polymethylmethacrylate (PMMA) and improvement of the mechanical and thermal properties of the hydrogel. A polymerization time of 4-hour produced the highest amount of material when 1.37 g sulfuric acid was used and 3.46 g when citric acid was added. The polymer synthesized with citric acid has a swelling rate up to 214.6%, compared with the materials produced with sulfuric acid that reach up to 31.3% of water absorption.

Downloads

Download data is not yet available.

References

N. N. Ferreira, L. M. B. Ferreira, V. M. O. Cardoso, F. I. Boni, A. L. R. Souza, y M. P. D. Gremião, «Recent advances in smart hydrogels for biomedical applications: From self-assembly to functional approaches», European Polymer Journal, vol. 99, pp. 117-133, feb. 2018, doi: 10.1016/j.eurpolymj.2017.12.004.

T. R. Hoare y D. S. Kohane, «Hydrogels in drug delivery: Progress and challenges», Polymer, vol. 49, n.o 8, pp. 1993-2007, abr. 2008, doi: 10.1016/j.polymer.2008.01.027.

S. Ma, B. Yu, X. Pei, y F. Zhou, «Structural hydrogels», Polymer, vol. 98, pp. 516-535, ago. 2016, doi: 10.1016/j.polymer.2016.06.053.

C. Bilici, D. Karaarslan, S. Ide, y O. Okay, «Toughness improvement and anisotropy in semicrystalline physical hydrogels», Polymer, vol. 151, pp. 208-217, ago. 2018, doi: 10.1016/j.polymer.2018.07.077.

J. L. Gadea, L. C. Cesteros, y I. Katime, «Chemical–physical behavior of hydrogels of poly(vinyl alcohol) and poly(ethylene glycol)», European Polymer Journal, vol. 49, n.o 11, pp. 3582-3589, nov. 2013, doi: 10.1016/j.eurpolymj.2013.07.027.

H. H. Kim, J. W. Kim, J. Choi, Y. H. Park, y C. S. Ki, «Characterization of silk hydrogel formed with hydrolyzed silk fibroin-methacrylate via photopolymerization», Polymer, ago. 2018, doi: 10.1016/j.polymer.2018.08.019.

L. A. G. Sala, K. M. A. Villanueva, M. T. Chua, y S. Chakraborty, «Novel glycerol crosslinked poly(methyl methacrylate) synthesized by chemo-enzymatic method for controlled release application», Materials Science and Engineering: C, vol. 32, n.o 8, pp. 2205-2211, dic. 2012, doi: 10.1016/j.msec.2012.06.001.

H.-T. Hsieh, H.-M. Chang, W.-J. Lin, Y.-T. Hsu, y F.-D. Mai, «Poly-Methyl Methacrylate/Polyvinyl Alcohol Copolymer Agents Applied on Diabetic Wound Dressing», Scientific Reports, vol. 7, n.o 1, dic. 2017, doi: 10.1038/s41598-017-10193-5.

L. Yu, L. Yao, J. You, Y. Guo, y L. Yang, «Poly(methyl methacrylate)/poly(ethylene glycol)/poly(ethylene glycol dimethacrylate) micelles: Preparation, characterization, and application as doxorubicin carriers: Article», Journal of Applied Polymer Science, vol. 131, n.o 1, p. n/a-n/a, ene. 2014, doi: 10.1002/app.39623.

N. D. Sachinvala, R. F. (Redford) Ju, M. H. Litt, y W. P. Niemczura, «Preparation of poly(methyl methacrylate) and copolymers having enhanced thermal stabilities using sucrose-based comonomers and additives», Journal of Polymer Science Part A: Polymer Chemistry, vol. 33, n.o 1, pp. 15-29, ene. 1995, doi: 10.1002/pola.1995.080330103.

H. Zhang y M. W. Grinstaff, «Recent Advances in Glycerol Polymers: Chemistry and Biomedical Applications», Macromolecular Rapid Communications, vol. 35, n.o 22, pp. 1906-1924, nov. 2014, doi: 10.1002/marc.201400389.

F. Camara, S. Caillol, y B. Boutevin, «Free radical polymerization study of glycerin carbonate methacrylate for the synthesis of cyclic carbonate functionalized polymers», European Polymer Journal, vol. 61, pp. 133-144, dic. 2014, doi: 10.1016/j.eurpolymj.2014.10.001.

B. S. Fernandes, J. Carlos Pinto, E. C. M. Cabral-Albuquerque, y R. L. Fialho, «Free-radical polymerization of urea, acrylic acid, and glycerol in aqueous solutions», Polymer Engineering & Science, vol. 55, n.o 6, pp. 1219-1229, jun. 2015, doi: 10.1002/pen.24081.

S. Shi, X. Peng, T. Liu, Y.-N. Chen, C. He, y H. Wang, «Facile preparation of hydrogen-bonded supramolecular polyvinyl alcohol-glycerol gels with excellent thermoplasticity and mechanical properties», Polymer, vol. 111, pp. 168-176, feb. 2017, doi: 10.1016/j.polymer.2017.01.051.

M. Pagliaro y M. Rossi, The Future of Glycerol: New Usages for a Versatile Raw Material. en Green Chemistry Series. Cambridge: Royal Society of Chemistry, 2008. doi: 10.1039/9781847558305.

G. Pistoia, A. Ricci, y M. A. Voso, «Electroinitiated polymerization of methyl methacrylate in aqueous sulfuric acid», Journal of Applied Polymer Science, vol. 20, n.o 9, pp. 2441-2450, sep. 1976, doi: 10.1002/app.1976.070200913.

M.-M. Wang, H.-F. Wang, D.-Q. Jiang, S.-W. Wang, y X.-P. Yan, «A strong inorganic acid-initiated methacrylate polymerization strategy for room temperature preparation of monolithic columns for capillary electrochromatography», ELECTROPHORESIS, vol. 31, n.o 10, pp. 1666-1673, abr. 2010, doi: 10.1002/elps.200900756.

C. E. Barnes, «Mechanism of Vinyl Polymerization. I. Role of Oxygen», Journal of the American Chemical Society, vol. 67, n.o 2, pp. 217-220, feb. 1945, doi: 10.1021/ja01218a023.

C. E. Barnes, R. M. Elofson, y G. D. Jones, «Role of Oxygen in Vinyl Polymerization. II. Isolation and Structure of the Peroxides of Vinyl Compounds», Journal of the American Chemical Society, vol. 72, n.o 1, pp. 210-215, ene. 1950, doi: 10.1021/ja01157a059.

C. C. Price, «Mechanism of vinyl polymerizations. IX. Some factors affecting copolymerization», Journal of Polymer Science, vol. 1, n.o 2, pp. 83-89, mar. 1946, doi: 10.1002/pol.1946.120010203.

A. B. Martins, A. K. Cattelan, y R. M. C. Santana, «How the compatibility between polyethylene and thermoplastic starch can be improved by adding organic acids?», Polymer Bulletin, vol. 75, n.o 5, pp. 2197-2212, may 2018, doi: 10.1007/s00289-017-2147-3.

J. B. Olivato, M. V. E. Grossmann, F. Yamashita, D. Eiras, y L. A. Pessan, «Citric acid and maleic anhydride as compatibilizers in starch/poly(butylene adipate-co-terephthalate) blends by one-step reactive extrusion», Carbohydrate Polymers, vol. 87, n.o 4, pp. 2614-2618, mar. 2012, doi: 10.1016/j.carbpol.2011.11.035.

E. A. Bugni, M. G. Lachtermacher, E. E. C. Monteiro, E. B. Mano, y C. G. Overberger, «An unusual reaction polymerization in nitric acid medium», Journal of Polymer Science Part A: Polymer Chemistry, vol. 24, n.o 7, pp. 1463-1486, jul. 1986, doi: 10.1002/pola.1986.080240705.

E. B. Mano, E. E. C. Monteiro, y L. C. Mendes, «Preparation of alkyl acrylate-acrylic acid copolymers by simultaneous hydrolysis and polymerization», Polymer Bulletin, vol. 23, n.o 5, pp. 497-504, may 1990, doi: 10.1007/BF00419968.

R. Zuluaga, J. L. Putaux, J. Cruz, J. Vélez, I. Mondragon, y P. Gañán, «Cellulose microfibrils from banana rachis: Effect of alkaline treatments on structural and morphological features», Carbohydrate Polymers, vol. 76, n.o 1, pp. 51-59, mar. 2009, doi: 10.1016/j.carbpol.2008.09.024.

N. V. Kozhevnikov, A. V. Trubnikov, y A. D. Stepukhovich, «Polymerization of acrylic monomers in presence of sulphuric acid.», Polymer Science U.S.S.R, vol. 26, n.o 4, pp. 761-769, 1984.

J. Jose y M. A. Al-Harthi, «Citric acid crosslinking of poly(vinyl alcohol)/starch/graphene nanocomposites for superior properties», Iranian Polymer Journal, vol. 26, n.o 8, pp. 579-587, ago. 2017, doi: 10.1007/s13726-017-0542-0.

M. Lazár, L. Hrčková, A. Fiedlerová, y E. Borsig, «Crosslinking during radical polymerization of dodecyl methacrylate», Macromolecular Materials and Engineering, vol. 283, n.o 1, pp. 88-92, nov. 2000, doi: 10.1002/1439-2054(20001101)283:1<88::AID-MAME88>3.0.CO;2-N.

K. Sykam y S. Donempudi, «Novel multifunctional hybrid diallyl ether monomer via azide alkyne click reaction as crosslinking agent in protective coatings», Polymer, vol. 62, pp. 60-69, abr. 2015, doi: 10.1016/j.polymer.2015.02.017.

E. M. Abdelrazek, A. M. Hezma, A. El-khodary, y A. M. Elzayat, «Spectroscopic studies and thermal properties of PCL/PMMA biopolymer blend», Egyptian Journal of Basic and Applied Sciences, vol. 3, n.o 1, pp. 10-15, mar. 2016, doi: 10.1016/j.ejbas.2015.06.001.

S. Mori, «Compositional analysis and infrared spectra of styrene–methyl methacrylate random copolymers», Journal of Applied Polymer Science, vol. 38, n.o 3, pp. 547-555, ago. 1989, doi: 10.1002/app.1989.070380314.

S. Sengupta, T. Das, U. K. Ghorai, y A. Bandyopadhyay, «Copolymers from methyl methacrylate and butyl acrylate with hyperbranched architecture», Journal of Applied Polymer Science, vol. 134, n.o 42, p. 45356, nov. 2017, doi: 10.1002/app.45356.

Y.-H. Hu y C.-Y. Chen, «Study of the thermal behaviour of poly(methyl methacrylate) initiated by lactams and thiols», Polymer Degradation and Stability, vol. 80, n.o 1, pp. 1-10, ene. 2003, doi: 10.1016/S0141-3910(02)00375-0.

M. Ferriol, A. Gentilhomme, M. Cochez, N. Oget, y J. L. Mieloszynski, «Thermal degradation of poly(methyl methacrylate) (PMMA): modelling of DTG and TG curves», Polymer Degradation and Stability, vol. 79, n.o 2, pp. 271-281, ene. 2003, doi: 10.1016/S0141-3910(02)00291-4.

D. R. Paul, «Polymer Blends: Phase Behavior and Property Relationships», en Multicomponent Polymer Materials, vol. 211, D. R. Paul y L. H. Sperling, Eds., Washington, DC: American Chemical Society, 1985, pp. 3-19. doi: 10.1021/ba-1986-0211.ch001.

A. E. Rydholm, N. L. Held, C. N. Bowman, y K. S. Anseth, «Gel Permeation Chromatography Characterization of the Chain Length Distributions in Thiol−Acrylate Photopolymer Networks», Macromolecules, vol. 39, n.o 23, pp. 7882-7888, nov. 2006, doi: 10.1021/ma060858u.

A. Wang, G. Li, y H. Meng, «Strain rate effect on the thermomechanical behavior of a thermoset shape memory polymer», Smart Materials and Structures, vol. 22, n.o 8, p. 085033, ago. 2013, doi: 10.1088/0964-1726/22/8/085033.

K. P. Menard, Dynamic mechanical analysis: a practical introduction. Boca Raton, Fla: CRC Press c/o Taylor & Francis, 2008.