Synthesis and Characterization of Quaternary Polymers as Superplasticizer and Assessing Their Effectiveness on Micronized Cement Particles

Document Type : Research Paper

Author

Department of Polymerization Engineering, Iran Polymer and Petrochemical Institute, P.O. Box: 14975/112, Tehran, Iran

Abstract

Different macromonomers having polyethylene glycol branches were synthesized via esterification reactions in various conditions. Quaternary polymers were prepared using synthesized macromonomers of polyoxyethylene acrylate and methacrylate with a PEG molecular weight of 600-3000 g/mol, and sodium acrylate, sodium methacrylate and sodium maleate. The superplasticizers were synthesized by free radical polymerization in water medium at 65-80oC. The recipe and polymerization conditions have a direct effect on the structure of superplasticizers. The structures of the synthesized quaternary polymers were characterized by 1H NMR, Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) analyses. The efficiency of a superplasticizer depends on the size of main chain, the chemical structure of repeating unit, molar ratio of monomers, chain-to-ion molar ratio (B/I) and size of the branches. These structural parameters affect the geometrical restriction, adsorption and the interaction between the superplasticizer chains and cement particles. FTIR, thermal gravimetric analysis (TGA) and X-ray powder diffraction (XRD) methods were also used to characterize the effect of superplasticizer structure on the hydration reaction of the cement pastes. FTIR spectroscopy was used to explore the effect of superplasticizer structure such as branch length and chain-to-ion molar ratios on the structure of the hydrated calcium silicate gels, polysilicate (SiO4-2) and calcium hydroxide generated during 7 days hydration. The results of XRD indicated that the structure of superplasticizer affects the content of anhydrous phase and hydrated products during hydration. The increase of PEG branch length slightly increased the decomposition temperatures of the hydrated calcium silicate gels and calcium hydroxide crystals. Furthermore, the size of calcium hydroxide crystals changed with the superplasticizer branch size.

Keywords


Fiat D., Lazar M., Baciu V., and Hubca Gh., Superplasticizer Polymeric Additives Used in Concrete, Mater. Plast., 49, 62-67, 2012.
Habbaba A., Lange A., and Plank J., Synthesis and Performance of a Modified Polycarboxylate Dispersant for Concrete Possessing Enhanced Cement Compatibility, J. Appl. Polym. Sci., 129, 346-353, 2013.
Sakai E., Kawakami A., and Daimon M., Dispersion Mechanisms of Comb-type Superplasticizers Containing Grafted Poly(ethylene oxide) Chains, Macromol. Symp., 175, 367-376, 2001.
Puertas F., Santos H., Palacios M., and Martı´nez-Ramı´rez S., Polycarboxylate Superplasticiser Admixtures: Effect on Hydration, Microstructure and Rheological Behavior in Cement Pastes, Adv. Cem. Res., 17, 77-89, 2005.
Lu S.H., Liu G., Ma Y.F., and Li F., Synthesis and Application of a New Vinyl Copolymer Superplasticizer, J. Appl. Polym. Sci., 117, 273–280, 2010.
Lv Sh., Ju H., Qiu C., Ma Y., and Zhou Q., Effects of Connection Mode Between Carboxyl Groups and Main Chains on Polycarboxylate Superplasticizer Properties, J. Appl. Polym. Sci., 128, 3925-3932, 2013.
Liu X., Wang Z., Zheng Y., Cui S., Lan M., Li H., Zhu J., and Liang X., Preparation, Characterization and Performances of Powdered Polycarboxylate Superplasticizer with Bulk Polymerization, Materials, 7, 6169-6183, 2014.
Yamada K., Takahashi T., Henahara S., and Matsuhira M., Effects of the Chemical Structure on the Properties of Polycarboxylate Type Superplasticizer, Cem. Conr. Res., 30, 197-207, 2000.
Cho H.Y. and Sun J.M., Effects of the Synthetic Conditions of Poly{carboxylate-g-(ethylene glycol) methyl ether} on the Dispersibility in Cement Paste, Cem. Conr. Res., 35, 891-899, 2005.
Winnefeld F., Becker S., Pakusch J., and Götz T., Effects of the Molecular Architecture of Comb-shaped Superplasticizers on Their Performance in Cementitious Systems, Cem. Conr. Compos., 29,251-262, 2007.
Plank J., Pöllmann K., Zouaoui N., Andres P.R., and Schaefer C., Synthesis and Performance of Methacrylic Ester Based Polycarboxylate Superplasticizers Possessing Hydroxy Terminated Poly(ethylene glycol) Side Chains, Cem. Conr. Res., 38, 1210-1216, 2008.
Dalas F., Pourchet S., Nonat A., Rinaldi D., Sabio S., and Mosquet M., Fluidizing Efficiency of Comb-like Superplasticizers: The Effect of the Anionic Function, the Side Chain Length and the Grafting Degree, Cem. Conr. Res., 71, 115-123, 2015.
Liu X.,Wang Z., Zhu J., Zheng Y., Cui S., Lan M., and Li H., Synthesis, Characterization and Performance of a Polycarboxylate superplasticizer with Amide Structure, Coll. Sur. A: Phys. Eng. Asp., 448, 119-129, 2014.
Alonso M., Palacios M., and Puertas F., Effect of Polycarboxylate–Ether Admixtures on Calcium Aluminate Cement Pastes. Part 2: Hydration Studies, Ind. Eng. Chem. Res., 52, 17330-17340, 2013.
de Reese J., Lenz P., Zilch K., and Plank J., Influence of Type of Superplasticizer and Cement Composition on the Adhesive Bonding Between Aged and Fresh Concrete, Const. Build. Mater., 48, 717-724, 2013.
Li Y., Yang Ch., Zhang Y., Zheng J., Guo H., and Lu M., Study on Dispersion, Adsorption and Flow Retaining Behaviors of Cement Mortars with TPEG-type Polyether Kind Polycarboxylate Superplasticizers, Const. Build. Mater., 64, 324-332, 2014.
Lva Sh., Gaob R., and Duan J., Effects of Chemical Structure on Adsorption of Polycarboxylate Superplasticizers on Cement Particles, Appl. Mech. Mater., 80-81, 185-189, 2011.
Pourchet S., Liautaud S., Rinaldi D., and Pochard I., Effect of the Repartition of the PEG Side Chains on the Adsorption and Dispersion Behaviors of PCP in Presence of Sulfate, Cem. Conr. Res., 42, 431-439, 2012.
Nawa T., Effect of Chemical Structure on Steric Stabilization of Polycarboxylate-Based Superplasticizer, J. Adv. Conr. Tech., 4, 225-232, 2006.
Liu M., Lei J., Guo L., Du X., and Li J., The Application of Thermal Analysis, XRD and SEM to Study the Hydration Behavior of Tricalcium Silicate in the Presence of a Polycarboxylate Superplasticizer, Therm. Acta, 613, 54-60, 2015.
Felekog˘lu B. and Sarıkahya H., Effect of Chemical Structure of Polycarboxylate-Based Superplasticizers on Workability Rretention of Self-Compacting Concrete, Const. Buil. Mater., 22, 1972-1980, 2008.
Lei J.H., Li H., Du X.-D., and Zhang A.F., Effect of Diester in Esterification Product of Polyethylene Glycol and Acrylic Acid on the Performance of Polycarboxylate Superplasticizer, Iran. Polym. J., 2, 117-122, 2013.
Ran Q., Qiao M., and Liu J., Influence of Ca2+ on the Performance of Poly(acrylic acid)-g-poly(ethylene glycol) Comb-Like Copolymers in Cement Suspensions, Iran. Polym. J., 9, 663-669, 2014.
Zhang R., Li Q., Zhang A., Liu Y., and Lei J., The Synthesis Technique of Polyacrylic Acid Superplasticizer, J. Wu. Un. Tech.-Mater. Sci. Ed., 6, 830-833, 2008.
Rostami Daronkola M.R., Synthesis of Acrylic Aacid, Maleic Anhydride, Methacrylic Acid Sodium Salts and Hydroxy Polyethylene Glycol Methacrylate Branched Four Polymers by Free Radical Polymerization as Concrete Additives, IR Pat., 86195, 2015.
Rostami Daronkola M.R., Synthesis of Multi Component Superplasticiser to Improve Interaction with Various Active Species in Concrete, IR Pat., 89368, 2016.
Zhang Zh., Wang Z., Ren J., and Pei J., Polycarboxylate Superplasticizers of Acrylic Acid–Isobutylene Polyethylene Glycol Copolymers: Monomer Reactivity Ratios, Copolymerization Behavior and Performance, Iran. Polym. J., 25, 549-557, 2016
Rostami Daronkola M.R., Structural Effect of Various Superplasticizer on Interaction with Concrete Active Particles and Their Properties, Besparesh, 7, 38-49, 2017.
Krˇı´zˇ J., Masarˇ B., Plesˇtil J., Tuzar Z., Pospı´sˇil H., and  Doskocˇilova D., Three-Layer Micelles of an ABC Block Copolymer: NMR, SANS, and LS Study of a Poly(2-ethylhexyl acrylate)-block-Poly(methyl methacrylate)-block-Poly(acrylic acid) Copolymer in D2O, Macromolecules, 31, 41-51, 1998.
Choi Ch., Chae S.Y., Kim T.H., Jang M.K., Cho C.S., and Nah J.W., Preparation and Characterizations of Poly(ethylene glycol)-Poly(Ɛ-caprolactone) Block Copolymer Nanoparticles, Bull. Korean Chem. Soc., 4, 523-528, 2005.
Krieg A., Pietsch Ch., Baumgaertel A., Hager M.D., Becer R. and Schubert U.S., Dual Hydrophilic Polymers Based on (meth)Acrylic Acid and Poly(ethylene glycol)–Synthesis and Water Uptake Behavior, Polym. Chem., 1, 1669-1676, 2010.
Perdih P., Čebašek S., Možir A., and Žagar E., Post-Polymerization Modification of Poly(L-glutamic acid) with D-(+)-Glucosamine, Molecules, 19, 19751-19768, 2014.
Imani M., Sharifi Sh., Mirzadeh H., and Ziaee F., Monitoring of Polyethylene Glycoldiacrylate-based Hydrogel Formation by Real Time NMR Spectroscopy, Iran. Polym. J., 1, 13-20, 2007.
Kim B. and Peppas N.A., Analysis of Molecular Interactions in Poly(methacrylic acid-g-ethylene glycol) Hydrogels, Polymer, 44, 3701-3707, 2003.
Fan W., Stoffelbach F., Rieger J., Regnaud L., Vichot A., Bresson B., and Lequeux N., A New Class of Organosilane-Modified Polycarboxylate Superplasticizers with Low Sulfate Sensitivity, Cem. Conr. Res., 42, 166-172, 2012.
Liu X., Wang Z., Zhu J., Zheng Y., Cui S., Lan M., and Li H., Synthesis, Characterization and Performance of a Polycarboxylate Superplasticizer with Amide Structure, Coll. Sur. A: Phys. Chem. Eng. Asp., 448, 119-129, 2014.
 Zhang Y. and Kong X., Correlations of the Dispersing Capability of NSF and PCE Types of Superplasticizer and Their Impacts on Cement Hydration with the Adsorption in Fresh Cement Pastes, Cem. Conr. Res., 69, 1-9, 2015.
Plank J., Zhimin D., Keller H., Hössle F., and Seid W., Fundamental Mechanisms for Polycarboxylate Intercalation into C3A Hydrate Phases and the Role of Sulfate Present in Cement, Cem. Conr. Res., 40, 45-57, 2010.
Schröf Ch., Gruber M., and Plank J., Preferential Adsorption of Polycarboxylate Superplasticizers on Cement and Silica Fume in Ultra-high Performance Concrete (UHPC), Cem. Conr. Res., 42, 1401-1408, 2012.
Snellings R., Salze A., and Scrivener K.L., Use of X-Ray Diffraction to Quantify Amorphous Supplementary Cementitious Materials in Anhydrous and Hydrated Blended Cements, Cem. Conr. Res., 64, 89-98, 2014.