Abstract
This research aims to design and develop a novel polyurethane elastomer (PUE) material with potential for biomedical optical applications. The study investigates the influence of hard segment (HS) content on transparency and tensile strength to optimize optical and mechanical properties. A one-step polymerization method is employed to synthesize a series of PUEs based on polyester, poly (3-methyl-1,5-pentandioladipate) (PMPA), diisocyanate (4,4-methylene bis (phenyl isocyanate) (MDI)), and the chain extender 1,4 butanediol (BD). By varying the ratios of PMPA/BD/MDI, PUE samples with different HS concentrations are synthesized. Analytical techniques including infrared spectroscopy, refractometer, UV/visible spectrophotometer, and tensile tests confirm the chemical structure of the synthesized PMPAPUE materials and investigate refractive indices (n), transmission spectra, and Young's modulus (YM), respectively. Films (PUE-1, PUE-2, and PUE-3) prepared using solvent-casting techniques exhibit varying optical and mechanical properties. PUE-1, with low HS content, demonstrates excellent transparency, with n = 1.59 and 89.63% of total transmitted light, and possesses excellent elastic properties with a YM of 10.654 MPa and a high strain value of S = 303.7%, meeting lens material requirements, promising for biomedical optical applications. Conversely, PUE-2 and PUE-3, with high HS content, are translucent and stiffer materials exhibiting higher YM, suitable for polymer processing, and tissue engineering applications. The optimization of the material's properties was achieved by carefully tailoring the composition of HS and soft segments, raw material ratios, and optimizing reaction conditions.
References
1.
Deodhar
, T.
,
Nugay
, N.
,
Nugay
, T.
,
Patel
, R.
,
Moggridge
, G.
, and
Kennedy
, J. P.
, 2022
, “Synthesis of High‐Molecular‐Weight and Strength Polyisobutylene‐Based Polyurethane and Its Use for the Development of a Synthetic Heart Valve
,” Macromol. Rapid Commun.
, 44
(1
), p. 2200147
.10.1002/marc.2022001472.
Kianpour
, G.
,
Bagheri
, R.
,
Pourjavadi
, A.
, and
Ghanbar
, H.
, 2022
, “Synergy of Titanium Dioxide Nanotubes and Polyurethane Properties for Bypass Graft Application: Excellent Flexibility and Biocompatibility
,” Mater. Des.
, 215
, p. 110523
.10.1016/j.matdes.2022.1105233.
Zeng
, Y.
,
Fan
, L.
,
Deng
, M.
,
Sun
, P.
,
Zhang
, B.
,
Zhang
, Q.
,
Li
, L.
, and
Xu
, Z.
, 2019
, “Development of High Refractive and High Water Content Polythiourethane/AA Hydrogels for Potential Artificial Cornea Implants
,” Int. J. Polym. Mater. Polym. Biomater.
, 69
(9
), pp. 580
–591
.10.1080/00914037.2019.15969084.
Soleimanifar
, F.
,
Mortazavi
, Y.
,
Nadri
, S.
, and
Soleimani
, M.
, 2017
, “Conjunctiva Derived Mesenchymal Stem Cell (CJMSCs) as a Potential Platform for Differentiation Into Corneal Epithelial Cells on Bioengineered Electrospun Scaffolds
,” J. Biomed. Mater. Res., Part A
, 105
(10
), pp. 2703
–2711
.10.1002/jbm.a.361235.
Riehle
, N.
,
Thude
, S.
,
Kandelbauer
, A.
,
Tovar
, G.
, and
Lorenz
, G.
, 2019
, “Synthesis of Soft Polysiloxane-Urea Elastomers for Intraocular Lens Application
,” J. Visualized Exp.
, 8
(145
), p. e58590
.10.3791/585906.
Jalie
, M.
, 1994
, The Principles of Ophthalmic Lenses
, The Association of British Dispensing Opticians
, London, UK
.7.
Sankar
, V.
,
Suresh Kumar
, T.
, and
Panduranga Rao
, K.
, 2004
, “Preparation, Characterisation and Fabrication of Intraocular Lens From Photo Initiated Polymerised Poly (Methyl Methacrylate)
,” Trends Biomater. Artif. Organs
, 17
(2
), pp. 24
–31
.https://go.gale.com/ps/i.do?p=HRCA&id=GALE%7CA165431689&v=2.1&it=r&userGroupName=anon%7E4688d116&aty=open-web-entry8.
Gacek
, M.
,
Wyslocki
, J.
,
Gondro
, J.
,
Badura
, F.
, and
Letkiewicz
, S.
, 2019
, “Structure and Selected Properties of Intraocular Implants (PMMA, Acrylic)
,” Mater. Plast.
, 56
(3
), pp. 621
–624
.10.37358/MP.19.3.52419.
Fannin
, T. E.
, and
Grosvenor
, T.
, 2013
, Clinical Optics
, Butterworth-Heinemann
, Waltham, MA.10.
Migahed
, M. D.
, and
Zidan
, H. M.
, 2006
, “Influence of UV-Irradiation on the Structure and Optical Properties of Polycarbonate Films
,” Curr. Appl. Phys.
, 6
(1
), pp. 91
–96
.10.1016/j.cap.2004.12.00911.
Grytsenko
, K.
,
Kolomzarov
, Y.
,
Lytvyn
, P.
,
Kondratenko
, O.
,
Sopinskyy
, M.
,
Lebedyeva
, I.
,
Niemczyk
, A.
,
Baranovska
, J.
,
Moszyński
, D.
,
Villringer
, C.
, and
Schrader
, S.
, 2023
, “Optical and Mechanical Properties of Thin PTFE Films, Deposited From a Gas Phase
,” Macromol. Mater. Eng.
, 308
(6
), p. 2200617
.10.1002/mame.20220061712.
Myung
, D.
,
Duhamel
, P.-E.
,
Cochran
, J. R.
,
Noolandi
, J.
,
Ta
, C. N.
, and
Frank
, C. W.
, 2008
, “Development of Hydrogel-Based Keratoprostheses: A Materials Perspective
,” Biotechnol. Prog.
, 24
(3
), pp. 735
–741
.10.1021/bp070476n13.
Riehle
, N.
,
Thude
, S.
,
Götz
, T.
,
Kandelbauer
, A.
,
Thanos
, S.
,
Tovar
, G. E.
, and
Lorenz
, G.
, 2018
, “Influence of PDMS Molecular Weight on Transparency and Mechanical Properties of Soft Polysiloxane-Urea-Elastomers for Intraocular Lens Application
,” Eur. Polym. J.
, 101
, pp. 190
–201
.10.1016/j.eurpolymj.2018.02.02914.
MasterEyeAssociates, Austin, TX, 2024, “
Comparing Lens Materials
,” MasterEyeAssociates, Austin, TX, accessed Aug. 7, 2024, https://www.mastereyeassociates.com/eyeglass-lens-materials15.
Bozukova
, D.
,
Pagnoulle
, C.
,
Jérôme
, R.
, and
Jérôme
, C.
, 2010
, “Polymers in Modern Ophthalmic Implants-Historical Background and Recent Advances
,” Mater. Sci. Eng.: R: Rep.
, 69
(6
), pp. 63
–83
.10.1016/j.mser.2010.05.00216.
Ren
, C.
,
Su
, Z.
,
Su
, Y.
, and
Wang
, L.
, 2022
, “Polyurethane Elastomer Layered Nanocomposite Material for Sports Grounds and the Preparation Method Thereof
,” BioMed Res. Int.
, 2022
(1
), p. 5152911
.10.1155/2022/515291117.
Lamba
, M. K.
,
Woodhouse
, A. K.
, and
Cooper
, L. S.
, 1997
, Polyurethanes in Biomedical Applications
, CRC Press LLC
, Boca Raton, FL.18.
Oh
, J.
,
Kim
, Y. K.
,
Hwang
, S. H.
,
Kim
, H. C.
,
Jung
, J. H.
,
Jeon
, C. H.
,
Kim
, J.
, and
Lim
, S. K.
, 2022
, “Synthesis of Thermoplastic Polyurethanes Containing Bio-Based Polyester Polyol and Their Fiber Property
,” Polymers
, 14
(10
), p. 2033.10.3390/polym1410203319.
Pavličević
, J.
,
Špírková
, M.
,
Jovičić
, M.
,
Bera
, O.
,
Poręba
, R.
, and
Budinski-Simendić
, J.
, 2013
, “The Structure and Thermal Properties of Novel Polyurethane/Organoclay Nanocomposites Obtained by Pre-Polymerization
,” Composites, Part B
, 45
(1
), pp. 232
–238
.10.1016/j.compositesb.2012.09.01820.
Pattanayak
, A.
, and
Jana
, S. C.
, 2005
, “Properties of Bulk-Polymerized Thermoplastic Polyurethane Nanocomposites
,” Polymer
, 46
(10
), pp. 3394
–3406
.10.1016/j.polymer.2005.03.02121.
Delebecq
, E.
,
Pascault
, J. P.
,
Boutevin
, B.
, and
Ganachaud
, F.
, 2013
, “On the Versatility of Urethane/Urea Bonds: Reversibility, Blocked Isocyanate, and Non-Isocyanate Polyurethane
,” Chem. Rev.
, 113
(1
), pp. 80
–118
.10.1021/cr300195n22.
Santerre
, J. P.
,
Woodhouse
, K.
,
Laroche
, G.
, and
Labow
, R. S.
, 2005
, “Understanding the Biodegradation of Polyurethanes: From Classical Implants to Tissue Engineering Materials
,” Biomaterials
, 26
(35
), pp. 7457
–7470
.10.1016/j.biomaterials.2005.05.07923.
Kavlock
, K.
D.,
Pechar
, T.
W.,
Hollinger
, J.
O.,
Guelcher
, S.
A., and
Goldstein
, A. S.
, 2007
, “Synthesis and Characterization of Segmented Poly(Esterurethane Urea) Elastomers for Bone Tissue Engineering
,” Acta Biomater.
, 3
(4
), pp. 475
–484
.10.1016/j.actbio.2007.02.00124.
Bueno‐Ferrer
, C.
,
Hablot
, E.
,
Perrin‐Sarazin
, F.
,
Garrigós
, M. C.
,
Jiménez
, A.
, and
Averous
, L.
, 2012
, “Structure and Morphology of New Bio‐Based Thermoplastic Polyurethanes Obtained From Dimeric Fatty Acids
,” Macromol. Mater. Eng.
, 297
(8
), pp. 777
–784
.10.1002/mame.20110027825.
Hepburn
, C.
, and
Hepburn
, C.
, 1992
, “Property-Structure Relationships in Polyurethanes
,” Polyurethane Elastomers
, Springer
, Dordrecht
, The Netherlands, pp. 51
–106
.26.
Adhikari
, R.
,
Gunatillake
, P. A.
,
Meijs
, G. F.
, and
McCarthy
, S. J.
, 1999
, “The Effect of Diisocyanate Isomer Composition on Properties and Morphology of Polyurethanes Based on 4,4′-Dicyclohexyl Methane Diisocyanate and Mixed Macrodiols (PDMS–PHMO
),” J. Appl. Polym. Sci.
, 73
(4
), pp. 573
–582
.10.1002/(SICI)1097-4628(19990725)73:4<573::AID-APP13>3.0.CO;2-N27.
Saralegi
, A.
,
Etxeberria
, A.
,
Fernández-d'Arlas
, B.
,
Mondragon
, I.
,
Eceiza
, A.
, and
Corcuera
, M. A.
, 2013
, “Effect of H12MDI Isomer Composition on Mechanical and Physico-Chemical Properties of Polyurethanes Based on Amorphous and Semicrystalline Soft Segments
,” Polym. Bull.
, 70
(8
), pp. 2193
–2210
.10.1007/s00289-013-0930-328.
Hundiwale
, D. G.
,
Kapadi
, U. R.
, and
Pandya
, M. V.
, 1995
, “Effect of Macroglycol Structure and Its Molecular Weight on Physicomechanical Properties of Polyurethanes
,” J. Appl. Polym. Sci.
, 55
(9
), pp. 1329
–1333
.10.1002/app.1995.07055090629.
Riehle
, N.
,
Athanasopulu
, K.
,
Kutuzova
, L.
,
Götz
, T.
,
Kandelbauer
, A.
,
Tovar
, G. E. M.
, and
Lorenz
, G.
, 2021
, “Influence of Hard Segment Content and Diisocyanate Structure on the Transparency and Mechanical Properties of Poly(Dimethylsiloxane)-Based Urea Elastomers for Biomedical Applications
,” Polymers
, 13
(2
), p. 212
.10.3390/polym1302021230.
Kim
, S. G.
, and
Lee
, D. S.
, 2002
, “Effect of Polymerization Procedure on Thermal and Mechanical Properties of Polyether Based Thermoplastic Polyurethanes
,” Macromol. Res.
, 10
(6
), pp. 365
–368
.10.1007/BF0321833131.
Ahn
, T. O.
,
Choi
, L. S.
,
Jeong
, H. M.
, and
Cho
, K.
, 1993
, “Thermal and Mechanical Properties of Thermoplastic Polyurethane Elastomers From Different Polymerization Methods
,” Polym. Int.
, 31
(4
), pp. 329
–333
.10.1002/pi.499031040432.
Harrell
, L. L.
, Jr., 1969
, “Segmented Polyurethans. Properties as a Function of Segment Size and Distribution
,” Macromolecules
, 2
(6
), pp. 607
–612
.10.1021/ma60012a00833.
Pattamaprom
, C.
,
Wu
, C.-H.
,
Chen
, P.-H.
,
Huang
, Y.-L.
,
Ranganathan
, P.
,
Rwei
, S.-P.
, and
Chuan
, F.-S.
, 2020
, “Solvent-Free One-Shot Synthesis of Thermoplastic Polyurethane Based on Bio-Poly(1,3-Propylene Succinate) Glycol With Temperature-Sensitive Shape Memory Behavior
,” ACS Omega
, 5
(8
), pp. 4058
–4066
.10.1021/acsomega.9b0366334.
Abbas
, I.
,
Al-Jumaily
, A. M.
, and
Ramos
, M.
, 2004
, “An Improved Electroactive Polymer for Optical Applications
,” Proc. SPIE
5385
, pp. 449
–453
.10.1117/12.53872235.
Al-Jumaily
, A. M.
,
Abbas
, I.
, and
Ramos
, M.
, 2009
, “Transparent Electroactive Films for Optical Applications
,” J. Mater. Sci. Eng.
, 3
(12
), pp. 11
–16
.https://science24.com/paper/18804#gsc.tab=036.
Charlon
, M.
,
Heinrich
, B.
,
Matter
, Y.
,
Couzigné
, E.
,
Donnio
, B.
, and
Avérous
, L.
, 2014
, “Synthesis, Structure and Properties of Fully Biobased Thermoplastic Polyurethanes, Obtained From a Diisocyanate Based on Modified Dimer Fatty Acids, and Different Renewable Diols
,” Eur. Polym. J.
, 61
, pp. 197
–205
.10.1016/j.eurpolymj.2014.10.01237.
Garcia
, D. M. G.
,
Jurado
, L. T.
,
Gallegos
, J. R.
, and
Rodríguez-Lorenzo
, M. L.
, 2017
, “Novel Non-Cytotoxic, Bioactive and Biodegradable Hybrid Materials Based on Polyurethanes/TiO2 for Biomedical Applications
,” Mater. Sci. Eng.: C
, 75
, pp. 375
–384
.10.1016/j.msec.2017.02.04138.
Su
, J.
,
Zhang
, Q.
,
Wang
, P.-C.
,
MacDiarmid
, A. G.
, and
Wynne
, K. J.
, 1998
, “Preparation and Characterization of Electrostrictive Polyurethane Films With Conductive Polymer Electrodes
,” Polym. Adv. Technol.
, 9
(6
), pp. 317
–321
.10.1002/(SICI)1099-1581(199806)9:6<317::AID-PAT758>3.0.CO;2-Y39.
Guan
, S.
, 2003
, “Common Questions on 100% Solids Polyurethane Coatings
,” Coatings World, Montvale, NJ, accessed Aug. 7, 2024, http:/www.gltechnologiescorp.com/gltech/uploads/2015/10/tech_coatingsworld2003.pdf40.
Fried
, J. R.
, 2014
, Polymer Science and Technology
, Prentice Hall
, Upper Saddle River, NJ.41.
Saunders
, J. H.
, and
Frisch
, K. C.
, 1962
, Polyurethanes. Chemistry and Technology
, Interscience Publishers
, John Wiley & Sons, New York.42.
Adnan
, S.
,
Tuan Ismail
, T. N. M.
,
Mohd Noor
, N.
,
Nek Mat Din
, N. S. M.
,
Hanzah
, N. A.
,
Shoot Kian
, Y.
, and
Abu Hassan
, H.
, 2016
, “Development of Flexible Polyurethane Nanostructured Biocomposite Foams Derived From Palm Olein-Based Polyol
,” Adv. Mater. Sci. Eng.
, 2016
(1
), p. 4316424
.10.1155/2016/431642443.
Liu
, Z.
,
Wu
, B.
,
Jiang
, Y.
,
Lei
, J.
,
Zhou
, C.
,
Zhang
, J.
, and
Wang
, J.
, 2018
, “Solvent-Free and Self-Catalysis Synthesis and Properties of Waterborne Polyurethane
,” Polymer
, 143
, pp. 129
–136
.10.1016/j.polymer.2018.04.01044.
Nanaki
, S.
,
Viziridou
, A.
,
Zamboulis
, A.
,
Kostoglou
, M.
,
Papageorgiou
, G. Z.
, and
Bikiaris
, D. N.
, 2020
, “New Biodegradable Poly(l-Lactide)-Block-Poly(Propylene Adipate) Copolymer Microparticles for Long-Acting Injectables of Naltrexone Drug
,” Polymers
, 12
(4
), p. 852
.10.3390/polym1204085245.
Asefnejad
, A.
,
Khorasani
, M. T.
,
Behnamghader
, A.
,
Farsadzadeh
, B.
, and
Bonakdar
, S.
, 2011
, “Manufacturing of Biodegradable Polyurethane Scaffolds Based on Polycaprolactone Using a Phase Separation Method: Physical Properties and In Vitro Assay
,” Int. J. Nanomed.
, 6
, pp. 2375
–2384
.10.2147/IJN.S1558646.
Chen
, T.-K.
,
Tien
, Y. I.
, and
Wei
, K. H.
, 2000
, “Synthesis and Characterization of Novel Segmented Polyurethane/Clay Nanocomposites
,” Polymer
, 41
(4
), pp. 1345
–1353
.10.1016/S0032-3861(99)00280-347.
Lee
, H. S.
,
Lee
, N. W.
,
Ihm
, D. W.
, and
Paik
, K. H.
, 1994
, “Segmental Orientation Behavior of Poly(Butyleneterephthalate-Co-Tetramethylene Oxide) Upon Uniaxial Deformation
,” Macromolecules
, 27
(15
), pp. 4364
–4370
.10.1021/ma00093a04348.
Briber
, R. M.
, and
Thomas
, E. L.
, 1985
, “The Structure of MDI/BDO-Based Polyurethanes: Diffraction Studies on Model Compounds and Oriented Thin Films
,” J. Polym. Sci., Polym. Phys. Ed.
, 23
(9
), pp. 1915
–1932
.10.1002/pol.1985.18023091349.
Buckwalter
, J. D.
,
Zhang
, M.
,
Inglefield
, D. L.
,
Moore
, R. B.
, and
Long
, T. E.
, 2013
, “Synthesis and Characterization of Siloxane-Containing Poly(Urea Oxamide) Segmented Copolymers
,” Polymer
, 54
(18
), pp. 4849
–4857
.10.1016/j.polymer.2013.07.02550.
Lin
, S. B.
,
Hwang
, K. S.
,
Tsay
, S. Y.
, and
Cooper
, S. L.
, 1985
, “Segmental Orientation Studies of Polyether Polyurethane Block Copolymers With Different Hard Segment Lengths and Distributions
,” Colloid Polym. Sci.
, 263
(2
), pp. 128
–140
.10.1007/BF01412787
