Synthesis and Application of a Cationic Polyamine as Yankee Dryer Coating Agent for the Tissue Paper-Making Process
Tissue paper is of high importance worldwide and, continuously, research is focused on improvements of the softening and durability properties of the paper which depend specifically on the production process. Polyamide-amine-epichlorohydrin (PAE) resins along with release agents are widely used to a...
- Autores:
-
Valencia, Cesar
- Tipo de recurso:
- Fecha de publicación:
- 2019
- Institución:
- Universidad del Atlántico
- Repositorio:
- Repositorio Uniatlantico
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.uniatlantico.edu.co:20.500.12834/781
- Acceso en línea:
- https://hdl.handle.net/20.500.12834/781
- Palabra clave:
- coating agent; paper creping; polyamine-epichlorohydrin resin; release agent; yankee dryer
- Rights
- openAccess
- License
- http://creativecommons.org/licenses/by-nc/4.0/
| id |
UNIATLANT2_3da9c9526c3c0fdb4c22ea735d42f89e |
|---|---|
| oai_identifier_str |
oai:repositorio.uniatlantico.edu.co:20.500.12834/781 |
| network_acronym_str |
UNIATLANT2 |
| network_name_str |
Repositorio Uniatlantico |
| repository_id_str |
|
| dc.title.spa.fl_str_mv |
Synthesis and Application of a Cationic Polyamine as Yankee Dryer Coating Agent for the Tissue Paper-Making Process |
| title |
Synthesis and Application of a Cationic Polyamine as Yankee Dryer Coating Agent for the Tissue Paper-Making Process |
| spellingShingle |
Synthesis and Application of a Cationic Polyamine as Yankee Dryer Coating Agent for the Tissue Paper-Making Process coating agent; paper creping; polyamine-epichlorohydrin resin; release agent; yankee dryer |
| title_short |
Synthesis and Application of a Cationic Polyamine as Yankee Dryer Coating Agent for the Tissue Paper-Making Process |
| title_full |
Synthesis and Application of a Cationic Polyamine as Yankee Dryer Coating Agent for the Tissue Paper-Making Process |
| title_fullStr |
Synthesis and Application of a Cationic Polyamine as Yankee Dryer Coating Agent for the Tissue Paper-Making Process |
| title_full_unstemmed |
Synthesis and Application of a Cationic Polyamine as Yankee Dryer Coating Agent for the Tissue Paper-Making Process |
| title_sort |
Synthesis and Application of a Cationic Polyamine as Yankee Dryer Coating Agent for the Tissue Paper-Making Process |
| dc.creator.fl_str_mv |
Valencia, Cesar |
| dc.contributor.author.none.fl_str_mv |
Valencia, Cesar |
| dc.contributor.other.none.fl_str_mv |
Valencia, Yamid Grande Tovar, Carlos David |
| dc.subject.keywords.spa.fl_str_mv |
coating agent; paper creping; polyamine-epichlorohydrin resin; release agent; yankee dryer |
| topic |
coating agent; paper creping; polyamine-epichlorohydrin resin; release agent; yankee dryer |
| description |
Tissue paper is of high importance worldwide and, continuously, research is focused on improvements of the softening and durability properties of the paper which depend specifically on the production process. Polyamide-amine-epichlorohydrin (PAE) resins along with release agents are widely used to adhere the paper to the yankee dryer (creping cylinder) in paper manufacture. Nevertheless, these resins are highly cationic and they normally adhere in excess to the paper which negatively a ects the creping process and the quality of the paper. For this reason, a low cationic polyamine-epichlorohydrin coating (Polycoat 38®) was synthesized from a diamine supplied by Disproquin S.A.S. and epichlorohydrin. The analysis of the synthesized polymer was carried out by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (1H-NMR). The molecular weight of the polymer was obtained by gel permeation chromatography (GPC), physical-chemical properties such as kinematic viscosity, percentage of solids, density, charge density were measured and compared with a commercial PAE resin (Dispro620®) Thermal stability of the Polycoat 38® and glass transition temperature in presence of a release agent (Disprosol 17®) were also evaluated by thermogravimetric analysis (TGA) and di erential scanning calorimetry (DSC), respectively. Finally, a peel adhesion test and an absorption durability assessment were carried out together with the evaluation of the creeping e ciency of the paper by caliber and tensile measurements in a tissue (towel paper) production plant, demonstrating a superior performance in the paper creping process as compared to some commercially available products. |
| publishDate |
2019 |
| dc.date.submitted.none.fl_str_mv |
2019-11-25 |
| dc.date.issued.none.fl_str_mv |
2020-01-09 |
| dc.date.accessioned.none.fl_str_mv |
2022-11-15T19:15:28Z |
| dc.date.available.none.fl_str_mv |
2022-11-15T19:15:28Z |
| dc.type.coarversion.fl_str_mv |
http://purl.org/coar/version/c_970fb48d4fbd8a85 |
| dc.type.coar.fl_str_mv |
http://purl.org/coar/resource_type/c_2df8fbb1 |
| dc.type.driver.spa.fl_str_mv |
info:eu-repo/semantics/article |
| dc.type.hasVersion.spa.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
| dc.type.spa.spa.fl_str_mv |
Artículo |
| status_str |
publishedVersion |
| dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/20.500.12834/781 |
| dc.identifier.doi.none.fl_str_mv |
10.3390/polym12010173 |
| dc.identifier.instname.spa.fl_str_mv |
Universidad del Atlántico |
| dc.identifier.reponame.spa.fl_str_mv |
Repositorio Universidad del Atlántico |
| url |
https://hdl.handle.net/20.500.12834/781 |
| identifier_str_mv |
10.3390/polym12010173 Universidad del Atlántico Repositorio Universidad del Atlántico |
| dc.language.iso.spa.fl_str_mv |
eng |
| language |
eng |
| dc.rights.coar.fl_str_mv |
http://purl.org/coar/access_right/c_abf2 |
| dc.rights.uri.*.fl_str_mv |
http://creativecommons.org/licenses/by-nc/4.0/ |
| dc.rights.cc.*.fl_str_mv |
Attribution-NonCommercial 4.0 International |
| dc.rights.accessRights.spa.fl_str_mv |
info:eu-repo/semantics/openAccess |
| rights_invalid_str_mv |
http://creativecommons.org/licenses/by-nc/4.0/ Attribution-NonCommercial 4.0 International http://purl.org/coar/access_right/c_abf2 |
| eu_rights_str_mv |
openAccess |
| dc.format.mimetype.spa.fl_str_mv |
application/pdf |
| dc.publisher.place.spa.fl_str_mv |
Barranquilla |
| dc.publisher.sede.spa.fl_str_mv |
Sede Norte |
| dc.source.spa.fl_str_mv |
polymers |
| institution |
Universidad del Atlántico |
| bitstream.url.fl_str_mv |
https://repositorio.uniatlantico.edu.co/bitstream/20.500.12834/781/1/polymers_12_00173_pdf.pdf https://repositorio.uniatlantico.edu.co/bitstream/20.500.12834/781/2/license_rdf https://repositorio.uniatlantico.edu.co/bitstream/20.500.12834/781/3/license.txt |
| bitstream.checksum.fl_str_mv |
5e1b44d0189b74a9fed6583f66b31019 24013099e9e6abb1575dc6ce0855efd5 67e239713705720ef0b79c50b2ececca |
| bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 MD5 |
| repository.name.fl_str_mv |
DSpace de la Universidad de Atlántico |
| repository.mail.fl_str_mv |
sysadmin@mail.uniatlantico.edu.co |
| _version_ |
1808413937827315712 |
| spelling |
Valencia, Cesar5ea2dcc3-88cf-4548-b38e-aaa8453a2d53Valencia, YamidGrande Tovar, Carlos David2022-11-15T19:15:28Z2022-11-15T19:15:28Z2020-01-092019-11-25https://hdl.handle.net/20.500.12834/78110.3390/polym12010173Universidad del AtlánticoRepositorio Universidad del AtlánticoTissue paper is of high importance worldwide and, continuously, research is focused on improvements of the softening and durability properties of the paper which depend specifically on the production process. Polyamide-amine-epichlorohydrin (PAE) resins along with release agents are widely used to adhere the paper to the yankee dryer (creping cylinder) in paper manufacture. Nevertheless, these resins are highly cationic and they normally adhere in excess to the paper which negatively a ects the creping process and the quality of the paper. For this reason, a low cationic polyamine-epichlorohydrin coating (Polycoat 38®) was synthesized from a diamine supplied by Disproquin S.A.S. and epichlorohydrin. The analysis of the synthesized polymer was carried out by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (1H-NMR). The molecular weight of the polymer was obtained by gel permeation chromatography (GPC), physical-chemical properties such as kinematic viscosity, percentage of solids, density, charge density were measured and compared with a commercial PAE resin (Dispro620®) Thermal stability of the Polycoat 38® and glass transition temperature in presence of a release agent (Disprosol 17®) were also evaluated by thermogravimetric analysis (TGA) and di erential scanning calorimetry (DSC), respectively. Finally, a peel adhesion test and an absorption durability assessment were carried out together with the evaluation of the creeping e ciency of the paper by caliber and tensile measurements in a tissue (towel paper) production plant, demonstrating a superior performance in the paper creping process as compared to some commercially available products.application/pdfenghttp://creativecommons.org/licenses/by-nc/4.0/Attribution-NonCommercial 4.0 Internationalinfo:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2polymersSynthesis and Application of a Cationic Polyamine as Yankee Dryer Coating Agent for the Tissue Paper-Making Processcoating agent; paper creping; polyamine-epichlorohydrin resin; release agent; yankee dryerinfo:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArtículohttp://purl.org/coar/version/c_970fb48d4fbd8a85http://purl.org/coar/resource_type/c_2df8fbb1BarranquillaSede NorteThe Basics of Creping in the Tissuemaking Process. Available online: https://www.tissuestory.com/2018/09/ 26/the-basics-of-creping/ (accessed on 25 September 2019).Michl PE, R.; Robert, A. Polyvinyl Alcohols in Combination With Glyoxlated-Vinyl Amide Polymers as Yankee Dryer Adhesive Compositions. U.S. Patent 5179150, 12 January 1993.Simpson, J.T.; Us, T.N. Thermosetting Adhesives Comprising a Resin Having Azetidinium Functional Groups. U.S. Patent 7781501B2, 24 August 2019.Gui, C.; Wang, G.; Wu, D.; Zhu, J.; Liu, X. Synthesis of a Bio-Based Polyamidoamine-Epichlorohydrin Resin and Its Application for Soy-Based Adhesives. Int. J. Adhes. Adhes. 2013, 44, 237–242.Archer, B.S.; Furman, G. Coating Space TM A 3-D View of Creping Cylinder Coatings. In Associação Brasileira Técnica de Celulose E Papel Conference; Nalco Company: Sao Paulo, Brazil, 2005; pp. 1–8.Wang, S.; Zhang, F.; Chen, F.; Pang, Z. Preparation of a Crosslinking Cassava Starch Adhesive and Its Application in Coating Paper. Bioresour 2013, 8, 3574–3589.Furman, G.; Archer, S. Yankee Coating Systems—The Functional Interface. In TissueWorld Americas Conference 2014; UBM Asia Trade Fairs Pte. Ltd.: Barcelona, Spain, 2014; pp. 34–53.Furman, G.S.; Harry, X.; Su,W.; Griegoriev, V.A. Modifying Agent for Yankee Coatings. U.S. Patent 8101045B2, 24 January 2012.van Beek, T.A.; Kuster, B.; Claassen, F.W.; Tienvieri, T.; Bertaud, F.; Lenon, G.; Petit-Conil, M.; Sierra-Alvarez, R. Fungal Bio-Treatment of SpruceWood with Trametes Versicolor for Pitch Control: Influence on Extractive Contents, Pulping Process Parameters, Paper Quality and E uent Toxicity. Bioresour. Technol. 2007, 98, 302–311.Obokata, T.; Isogai, A. The Mechanism of Wet-Strength Development of Cellulose Sheets Prepared with Polyamideamine-Epichlorohydrin (PAE) Resin. Colloids Surf. A Physicochem. Eng. Asp. 2007, 302, 525–531.Wågberg, L.; Mirjam, B. On the Mechanism behindWet Strength Development in Papers ContainingWet Strength Resins. Nord. Pulp Pap. Res. J. 2018, 8, 53–58.Kang, M.; Myung, S.J.; Jin, H.-J. Nylon 610 and Carbon Nanotube Composite by in Situ Interfacial Polymerization. Polymer 2006, 47, 3961–3966.Hagiopol, C.; Johnston, J. Chemistry of Modern Papermaking, 1st ed.; B/W Illustrations: Boca Raton, FL, USA, 2011.Sharoyan, D.E.; Tunell, J.A. Method of Producing a Creping Paper and the Creping Paper Thereof. U.S. Patent 20160168798A1, 16 June 2016.Allen, A. Methods of Making and Using Creping Adhesives Comprised of Polyamine-Epihalohydrin Resin/Poly (Vinylalcohol) Mixtures. U.S. Patent 2002/0173580A1, 21 November 2002.Brady, R.L.; Us, D.E.; Allen, A.J.; Mary, J.; Rossi, F. Adhesive Composition of Low Molecular Weight Polyaminopolyamide—Epichlorohydrin (Pae) Resin and Protein. U.S. Patent 2008/0050602A1, 28 February 2008.Häger, M.; Ese, M.; Sjöblom, J. Emulsion Inversion in an Oil-Surfactant-Water System Based on Model Naphthenic Acids under Alkaline Conditions. J. Dispers. Sci. Technol. 2005, 26, 673–682.Ese, M.; Kilpatrick, P.K. Stabilization of Water-in-Oil Emulsions by Naphthenic Acids and Their Salts: Model Compounds, Role of PH, and Soap:Acid Ratio. J. Dispers. Sci. Technol. 2004, 25, 253–261.Gao, D.; Fan, B.; Zhang, B.; Mi, Y.; Zhang, Y.; Gao, Z. Storage Stability of Polyamidoamine-Epichlorohydrin Resin and Its E ect on the Properties of Defatted Soybean Flour-Based Adhesives. Int. J. Adhes. Adhes. 2019, 91, 92–101.Kowalczyk, I. Synthesis, Molecular Structure and Spectral Properties of Quaternary Ammonium Derivatives of 1,1-Dimethyl-1,3-Propylenediamine. Molecules 2008, 13, 379–390. [CrossRef] 21. Huang, Z.; Gengenbach, T.; Tian, J.; Shen, W.; Garnier, G. The Role of Polyaminoamide-Epichlorohydrin (PAE) on Antibody Longevity in Bioactive Paper. Colloids Surf. B Biointerfaces 2017, 158, 197–202.Valencia, C.; Valencia, C.H.; Zuluaga, F.; Valencia, M.E.; Mina, J.H.; Grande-Tovar, C.D. Synthesis and Application of Sca olds of Chitosan-Graphene Oxide by the Freeze-Drying Method for Tissue Regeneration. Molecules 2018, 23, 2651.Obokata, T.; Isogai, A. 1H- and 13C-NMR Analyses of Aqueous Polyamideamine—Epichlorohydrin Resin Solutions. J. Aplp. Polym. Sci. 2004, 92, 1847–1854.Carr, M.E.; Doane, W.M.; Hamerstrand, G.E.; Hofreiter, B.T. Interpolymer from Starch Xanthate and Polyamide–Polyamine–Epichlorohydrin Resin: Structure and Papermaking Application. J. Appl. Polym. Sci. 1973, 17, 721–735.Devi, G.N.; Saranya, J.; Manjubaashini, N.; Thangadurai, T.D.; Roopan, S.M.; Chitra, S. Polyamidoaminoepichlorohydrin Resin a Novel Synthetic Anti-Corrosive Water Soluble Polymer for Mild Steel. Prog. Org. Coat. 2017, 109, 117–125.Zuluaga, F.; Gómez, F. Introducción a La Química de Polímeros, 3rd ed.; Programa Editorial Universidad del Valle: Cali, Colombia, 2015.Schmied, F.J.; Teichert, C.; Kappel, L.; Hirn, U.; Bauer, W.; Schennach, R. What Holds Paper Together: Nanometre Scale Exploration of Bonding between Paper Fibres. Sci. Rep. 2013, 3, 2432–2437.Pei, L.; Lucy, C.A. Insight into the Stability of Poly(Diallydimethylammoniumchloride) and Polybrene Poly Cationic Coatings in Capillary Electrophoresis. J. Chromatogr. A 2014, 1365, 226–233.Valencia Junca, M.A.; Valencia, C.; Flórez López, E.; Delgado-Ospina, J.; Zapata, P.A.; Solano, M.; Grande Tovar, C.D. Chitosan Beads Incorporated with Essential Oil of Thymus Capitatus: Stability Studies on Red Tilapia Fillets. Biomolecules 2019, 9, 458.Obokata, T.; Yanagisawa, M.; Isogai, A. Characterization of Polyamideamine-Epichlorohydrin (PAE) Resin: Roles of Azetidinium Groups and Molecular Mass of PAE in Wet Strength Development of Paper Prepared with PAE. J. Appl. Polym. Sci. 2005, 97, 2249–2255.Rieger, E.; Manhart, A.;Wurm, F.R. Multihydroxy Polyamines by Living Anionic Polymerization of Aziridines. ACS Macro Lett. 2016, 5, 195–198.Huang, K.; Xia, J.; Yang, X.; Li, M.; Ding, H. Properties and curing kinetics of C21-based reactive polyamides as epoxy-curing agents derived frpm tung oil. Polym. J. 2010, 42, 51–57.Thirtha, V.; Lehman, R.; Nosker, T. E ect of Additives on the Composition Dependent Glass Transition Variation in PS/PP Blends. J. Appl. Polym. Sci. 2008, 107, 3987–3992.McLeay, D.J.; Walden, C.C.; Munro, J.R. E ect of PH on Toxicity of Kraft Pulp and Paper Mill E uent to Salmonid Fish in Fresh and Seawater. Water Res. 1979, 13, 249–254.Shah, N.; Mewada, R.K.; Mehta, T. Crosslinking of Starch and Its E ect on Viscosity Behaviour. Rev. Chem. Eng. 2016, 32, 265–270.Neal, C.W.; Forde-Kohler, L.J. Method for Creping Paper. U.S. Patent 6187138B1, 13 February 2019.Scott,W. Principles of Wet End Chemistry, 1st ed.; Tappi Press: Atlanta, GA, USA, 1996.Carson, C.G.; Popil, R.E. Examining Interrelationships between Caliper, Bending, and Tensile Sti ness of Paper in Testing Validation. TAPPI J. 2008, 7, 17–24.Tissue Sheet Softness—Theory, Measurement, and Chemical Applications Which Can Improve It. Available online: https://www.tissuestory.com/2017/08/31/tissue-sheet-softness-theory-measurement-and-chemicalapplications- which-can-improve-it/ (accessed on 18 October 2019).TAPPI. Tensile Properties Of Paper And Paperboard (Using Constant Rate Of Elongation Apparatus); Technical Association of the Pulp and Paper Industry: Peachtree Corners, GA, USA, 2006; pp. 1–28.Kneller, J.F.; Park, L.G. Cross-Linked Poly(Aminoamides) as Yankee Dryer Adhesiver. U.S. Patent 5382323A, 17 January 1995.http://purl.org/coar/resource_type/c_6501ORIGINALpolymers_12_00173_pdf.pdfpolymers_12_00173_pdf.pdfapplication/pdf3913260https://repositorio.uniatlantico.edu.co/bitstream/20.500.12834/781/1/polymers_12_00173_pdf.pdf5e1b44d0189b74a9fed6583f66b31019MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8914https://repositorio.uniatlantico.edu.co/bitstream/20.500.12834/781/2/license_rdf24013099e9e6abb1575dc6ce0855efd5MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-81306https://repositorio.uniatlantico.edu.co/bitstream/20.500.12834/781/3/license.txt67e239713705720ef0b79c50b2ececcaMD5320.500.12834/781oai:repositorio.uniatlantico.edu.co:20.500.12834/7812022-11-15 14:15:29.745DSpace de la Universidad de Atlánticosysadmin@mail.uniatlantico.edu.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 |