Synthesis and Characterization of Lignin Grafting Modification-based Aliphatic Superplasticizer

Abstract

Lignin as the main component of black liquor is generally employed to modify aliphatic superplasticizer (AFS). However, the modification effect is hard to evaluate correctly due to the uncertain molecular structure of lignin and the disturbance from the complexity of black liquor compositions. In this paper, the purified lignin via acid precipitation from straw black liquor is used to modify AFS. The modified AFS named as LAFS for short presents lower molecular mass than AFS. It is assumed that it is due to the single active site of guaiacol segments in lignin by which lignin graft modifies AFS in virtue of methylolation reaction. In order to verify this assumption, guaiacol and dihydro eugenol as the typical segments of lignin macromolecule were selected, respectively, as the simplified model compounds of lignin to modify AFS, and corresponding products are abbreviated in GAFS and DAFS. Both GAFS and DAFS show the lower molecular mass than unmodified AFS. FTIR and TG-DTG analyses prove that lignin is successfully grafted onto AFS. The graft modification of lignin results in a decrease in electrostatic epulsion, but an enhanced steric hindrance. Therefore, although the replacement rate of lignin in LAFS was about 23.3%, the dispersion performance was only slightly affected.

Keywords

grafting modification / lignin / aliphatic superplasticizer / model compound / dispersion performance

References

[1] Bennett S J. Using Past Transitions to Inform Scenarios for the Future of Renewable Raw Materials in UK[J]. Energy Policy, 2012, 50: 95-108.

[2] Owusu P A, Asumadu-Sarkodie S. A Review of Renewable Energy Sources, Sustainability Issues and Climate Change Mitigation[J]. Cogent Engineering, 2016, 3(1): 1167990

[3] Tripathi L, Mishra A K, Dubey A K, et al. Renewable Energy: An Overview on Its Contribution in Current Energy Scenario of India[J]. Renewable and Sustainable Energy Reviews, 2016, 60: 226-233.

[4] Dey P, Saggi S K. An Innovative Approach towards Economic Bio-ethanol Production from Starchy and Ligno-Cellulosic Biomass through Simultaneous Saccharification and Fermentation (SSF)[J]. International Journal of Current Microbiology and Applied Sciences, 2016, 5(5): 870-877.

[5] Vourdoubas J, Skoulou V K. Possibilities of Upgrading Solid Underutilized Lingo-cellulosic Feedstock (Carob Pods) to Liquid Bio-fuel: Bio-ethanol Production and Electricity Generation in Fuel Cells-A Critical Appraisal of the Required Processes[J]. Studies in Engineering and Technology, 2017, 4(1): 25-34.

[6] Gosselink R J A D, Jong E, Guran B, et al. Co-ordination Network for Lignin-standardisation, Production and Applications Adapted to Market Requirements (EUROLIGNIN)[J]. Industrial Crops and Products, 2004, 20(2): 121-129.

[7] Kamali M, Gameiro T, Costa M E V, et al. Anaerobic Digestion of Pulp and Paper Mill Wastes-An Overview of the Developments and Improvement Opportunities[J]. Chemical Engineering Journal, 2016, 298: 162-182.

[8] Mahmood N, Yuan Z, Schmidt J, et al. Depolymerization of Lignins and Their Applications for the Preparation of Polyols and Rigid Polyurethane Foams: A Review[J]. Renewable and Sustainable Energy Reviews, 2016, 60: 317-329.

[9] Zou F, Tan H, Guo Y, et al. Effect of Sodium Gluconate on Dispersion of Polycarboxylate Superplasticizer with Different Grafting Density in Side Chain[J]. Journal of Industrial and Engineering Chem-istry, 2017, 55: 91-1000.

[10] Gupta C, Perkins K M, Rios R T, et al. Poly (Ethylene oxide)-Grafted Lignosulfonate Superplasticisers: Improving Performance by Increasing Steric Interactions[J]. Advances in Cement Research, 2017, 29(1): 2-10.

[11] Kim G M, Nam I W, Yoon H N, et al. Effect of Superplasticizer Type and Siliceous Materials on the Dispersion of Carbon Nanotube in Cementitious Composites[J]. Composite Structures, 2018, 185: 264-272.

[12] Malhotra V M. Innovative Applications of Superplasticizers in Concrete: a Review[C]. Proceeding of the International Symposuim ‘The Role of Admixtures in High Performance Concrete, 1999, 5: 421-460.

[13] Lei Lei. A Comprehensive Study of Interaction Occurring Between Superplasticizers and Clays, and Superplasticizers and Cement, 2016 München: Technische Universität München.

[14] Aignesberger A, Plank J. Use of Acid Groups Containing Thermostable Hydrophilic Condensation Products of Aldehydes and Ketones as Surface Active Agents[P]. Germany: DE3144673, 1983.5.26

[15] Plank J, Aignesberger A. Dispersion Agent for Saliferous Systems[P]. Germany: DE3344291, 1985.6.13

[16] Zhou M, Kong Q, Pan B, et al. Evaluation of Treated Black Liquor Used as Dispersant of Concentrated Coal-water Slurry[J]. Fuel, 2010, 89(3): 716-723.

[17] Mohan K K, Fangong K, Pedram Fatehi. Production of Car-Boxymethylated Lignin and Its Application as a Dispersant[J]. European Polymer Journal, 2015, 70: 371-383.

[18] Zhor J G, Bremner T W. Influence of New Environmentally Beneficial Lignin-Based Superplasticizer on Concrete Performance[C]. Ravindra K Dhir, Peter C Hewlett. Concrete in the Service of Mankind: Radical Concrete Technology, London: E & FN Spon, 2003

[19] De Z Y, Li J, Chao M, et al. The Graft Polymers from Different Species of Lignin and Acrylic Acid: Synthesis and Mechanism Study[J]. International Journal of Biological Macromolecules, 2014, 63: 43-48.

[20] Zhang T, Gao J, Deng X, et al. Graft Copolymerization of Black Liquor and Sulfonated Acetone Formaldehyde and Research on Concrete Performance[J]. Construction and Building Materials, 2015, 83: 308-313.

[21] Lou H, Lai H, Wang M, et al. Preparation of Lignin-based Superplasticizer by Graft Sulfonation and Investigation of the Dispersive Performance and Mechanism in a Cementitious System[J]. Industrial & Engineering Chemistry Research, 2013, 52(46): 16101-16109.

[22] Plank J, Pöllmann K, Zouaoui N, et al. Synthesis and Performance of Methacrylic Ester Based Polycarboxylate Superplasticizers Possessing Hydroxy Terminated Poly (Ethylene Glycol) Side Chains[J]. Cement and Concrete Research, 2008, 38: 1210-1216.

[23] Sjöström E. Lignin. Wood Chemistry: Fundamentals and Applications, Second Edition, 1993 San Diego: Harcourt Brace Jovanovich Academic Press Inc..

[24] Magnus N, Håkan Edlund. Lignin: Recent Advances and Emerging Applications[J]. Current Opinion in Colloid & Interface Science, 2014, 19(5): 409-416.

[25] Stéphanie L, Luc Avérous. Chemical Modification of Lignins: Towards Biobased Polymers[J]. Progress in Polymer Science, 2014, 39(7): 1266-1290.

[26] Yang H, Yan R, Chen H, et al. Characteristics of Hemicellulose, Cellulose and Lignin Pyrolysis[J]. Fuel, 2007, 86: 1781-1788.

[27] Kim J-Y, Hwang H, Oh S, et al. Investigation of Struc-tural Modification and Thermal Characteristics of Lignin after Heat Treatment[J]. International Journal of Biological Macromolecules, 2014, 66: 57-65.

[28] Kim J-Y, Hwang H, Park J, et al. Predicting Structural Change of Lignin Macromolecules Before and After Heat Treatment Using the Pyrolysis-GC/MS Technique[J]. Journal of Analytical and Applied Pyrolysis, 2014, 110: 305-312.

[29] Kazuo Yamada. Basics of Analytical Methods Used for the Investigation of Interaction Mechanism Between Cements and Superplasticizer[J]. Cement and Concrete Reseach, 2011, 41: 793-798.

[30] Rath S, Puthipad N, Attachaiyawuth A, et al. Critical Size of Entrained Air to Stability of Air Volume in Mortar of Self-Compacting Concrete at Fresh Stage[J]. Jounal of Advanced Concrete Technology, 2017, 15(1): 29-37.