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Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis
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Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis

A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (31 August 2019) | Viewed by 117622

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editors

Prof. Dr. Sándor Kéki

E-Mail Website
Guest Editor
Department of Applied Chemistry, Faculty of Sciences and Technology, University of Debrecen, Egyetem tér 1, H-4032 Debrecen, Hungary
Interests: polymers; polyurethanes; shape-memory polymers; cationic polymerization; light emitting materials; fluorescent dyes; mass spectrometry
Special Issues, Collections and Topics in MDPI journals
Prof. József Karger-Kocsis (4 March 1950 -- 13 December 2018)

E-Mail Website
Guest Editor
Department of Polymer Engineering, Faculty of Mechanical Engineering, Budapest University of Technology and Economics, Műegyetem rkp. 3., H-1111 Budapest, Hungary
Interests: polymers from renewable resources; functional polymers; structure–property relationships; rubbers

Special Issue Information

Dear Colleagues,

Polyurethanes (PUs) are the most versatile polymeric materials, produced both in linear and crosslinked forms, via the chemical reactions between isocyanates and polyols. Depending on the chemical formulation (e.g., type, structure and reactivity of the monomers, type and amount of the catalysts) the physico-chemical, mechanical and biological properties can be made unique for a particular PU system. The potential application of PUs is further broadened by the incorporation of various polymer segments in the main chains, pendant groups onto the polymer backbone, and the like. The attribute “functional” covers not only chemical functionalization possibilities but also the creation of functional (i.e., non-mechanical) properties with different working principles. Using variants of the ‘click’ chemistry, such as the Diels-Alder coupling, chemical functionalization and generation of functional properties (e.g., self-healing, shape memory) can even be combined. Such “functional” PUs have gained significant attention in both the polymer industry and academic research because of their manifold application possibilities.

The aim of this Special Issue of Polymers, entitled “Functional Polyurethanes”, is to cover the most recent progress in the rapidly growing field of polyurethane “functionalization”. This Special Issue will address novel design strategies, synthesis and characterization of functional monomers/polymers (also from renewable resources), as well as the applications of functional PUs (protective coatings, polymer modifiers, nanocomposites, high performance elastomers, ionomers, waterborne PUs, tissue engineering, shape memory and self-healing effects). Both original and review papers are welcome.

Special Statement: It is our sad duty to announce that Professor József Karger-Kocsis, one of the Guest Editors of this Special Issue has passed away, at the age of 68, on 13 December, 2018. Professor Karger-Kocsis served as a full professor at the Budapest University of Technology and Economics and was the Editor-in-Chief of the internationally respected polymer journal Express Polymer Letters. Professor Karger-Kocsis’s research interest covered a wide range of scientific and practical areas including the improvement of the mechanical properties of synthetic and natural polymers and their composites, development of new techniques and methodologies for the investigation of polymer composites, and studying the interaction between polymer matrices and reinforcing materials. Professor Karger-Kocsis also acted with great enthusiasm to the challenges of various environmental issues by focusing on the recycling of plastic and rubber wastes, as well as on the application of renewable raw materials in the synthesis of polymers. Furthermore, he obtained excellent seminal results in the field of smart and functional materials. His outstanding scientific achievements are marked by his 4 books, 50 book chapters, approximately 500 scientific papers published in peer-reviewed journals, and more than 20,000 citations with a Hirsh-index of 72. As a tribute to his lifelong work, this Special Issue of Polymers is dedicated to the memory of Professor József Karger-Kocsis and the deadline for submission of manuscripts to this Special Issue is extended to 31 August, 2019. We hope that this extension will be appropriate to allow for manuscript submissions by the scientists who want to salute Professor Karger-Kocsis’s scientific work.

Prof. Sándor Kéki
Prof. József Karger-Kocsis
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Polyurethanes
  • Synthesis, mechanisms
  • Characterization
  • Physical properties
  • ‘Click’ chemistry
  • Shape memory polyurethanes
  • Self-healing polyurethanes
  • Tissue engineering
  • Ionomers, waterborne PUs
  • Nanocomposites

Published Papers (23 papers)

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Editorial

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5 pages, 364 KiB  
Editorial
Functional Polyurethanes—In Memory of Prof. József Karger-Kocsis
by Sándor Kéki
Polymers 2020, 12(2), 434; https://doi.org/10.3390/polym12020434 - 13 Feb 2020
Viewed by 2177
Abstract
In the era of our “plastic age”, polyurethanes (PUs) represent one of the most versatile polymers that are produced by the nucleophilic addition reaction between isocyanates and various polyols [...] Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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Research

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15 pages, 8228 KiB  
Article
Thermoplastic Dynamic Vulcanizates with In Situ Synthesized Segmented Polyurethane Matrix
by Andrea Kohári, István Zoltán Halász and Tamás Bárány
Polymers 2019, 11(10), 1663; https://doi.org/10.3390/polym11101663 - 12 Oct 2019
Cited by 6 | Viewed by 3324
Abstract
The aim of this paper was the detailed investigation of the properties of one-shot bulk polymerized thermoplastic polyurethanes (TPUs) produced with different processing temperatures and the properties of thermoplastic dynamic vulcanizates (TDVs) made by utilizing such in situ synthetized TPUs as their matrix [...] Read more.
The aim of this paper was the detailed investigation of the properties of one-shot bulk polymerized thermoplastic polyurethanes (TPUs) produced with different processing temperatures and the properties of thermoplastic dynamic vulcanizates (TDVs) made by utilizing such in situ synthetized TPUs as their matrix polymer. We combined TPUs and conventional crosslinked rubbers in order to create TDVs by dynamic vulcanization in an internal mixer. The rubber phase was based on three different rubber types: acrylonitrile butadiene rubber (NBR), carboxylated acrylonitrile butadiene rubber (XNBR), and epoxidized natural rubber (ENR). Our goal was to investigate the effect of different processing conditions and material combinations on the properties of the resulting TDVs with the opportunity of improving the interfacial connection between the two phases by chemically bonding the crosslinked rubber phase to the TPU matrix. Therefore, the matrix TPU was synthesized in situ during compounding from diisocyanate, diol, and polyol in parallel with the dynamic vulcanization of the rubber mixture. The mechanical properties were examined by tensile and dynamical mechanical analysis (DMTA) tests. The morphology of the resulting TDVs was studied by atomic force microscopy (AFM) and scanning electron microscopy (SEM) and the thermal properties by differential scanning calorimetry (DSC). Based on these results, the initial temperature of 125 °C is the most suitable for the production of TDVs. Based on the atomic force micrographs, it can be assumed that phase separation occurred in the TPU matrix and we managed to evenly distribute the rubber phase in the TDVs. However, based on the SEM images, these dispersed rubber particles tended to agglomerate and form a quasi-continuous secondary phase where rubber particles were held together by secondary forces (dipole–dipole and hydrogen bonding) and can be broken up reversibly by heat and/or shear. In terms of mechanical properties, the TDVs we produced are on a par with commercially available TDVs with similar hardness. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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11 pages, 2114 KiB  
Article
Urethane Formation with an Excess of Isocyanate or Alcohol: Experimental and Ab Initio Study
by Wafaa Cheikh, Zsófia Borbála Rózsa, Christian Orlando Camacho López, Péter Mizsey, Béla Viskolcz, Milán Szőri and Zsolt Fejes
Polymers 2019, 11(10), 1543; https://doi.org/10.3390/polym11101543 - 22 Sep 2019
Cited by 16 | Viewed by 10764
Abstract
A kinetic and mechanistic investigation of the alcoholysis of phenyl isocyanate using 1-propanol as the alcohol was undertaken. A molecular mechanism of urethane formation in both alcohol and isocyanate excess is explored using a combination of an accurate fourth generation Gaussian thermochemistry (G4MP2) [...] Read more.
A kinetic and mechanistic investigation of the alcoholysis of phenyl isocyanate using 1-propanol as the alcohol was undertaken. A molecular mechanism of urethane formation in both alcohol and isocyanate excess is explored using a combination of an accurate fourth generation Gaussian thermochemistry (G4MP2) with the Solvent Model Density (SMD) implicit solvent model. These mechanisms were analyzed from an energetic point of view. According to the newly proposed two-step mechanism for isocyanate excess, allophanate is an intermediate towards urethane formation via six-centered transition state (TS) with a reaction barrier of 62.6 kJ/mol in the THF model. In the next step, synchronous 1,3-H shift between the nitrogens of allophanate and the cleavage of the C–N bond resulted in the release of the isocyanate and the formation of a urethane bond via a low-lying TS with 49.0 kJ/mol energy relative to the reactants. Arrhenius activation energies of the stoichiometric, alcohol excess and the isocyanate excess reactions were experimentally determined by means of HPLC technique. The activation energies for both the alcohol (measured in our recent work) and the isocyanate excess reactions were lower compared to that of the stoichiometric ratio, in agreement with the theoretical calculations. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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14 pages, 4454 KiB  
Article
Synthetic Environmentally Friendly Castor Oil Based-Polyurethane with Carbon Black as a Microphase Separation Promoter
by Jia-Wun Li, Wen-Chin Tsen, Chi-Hui Tsou, Maw-Cherng Suen and Chih-Wei Chiu
Polymers 2019, 11(8), 1333; https://doi.org/10.3390/polym11081333 - 12 Aug 2019
Cited by 23 | Viewed by 4926
Abstract
This study created water polyurethane (WPU) prepolymer by using isophorone diisocyanate, castor oil, dimethylolpropionic acid, and triethanolamine (TEA) as the hard segment, soft segment, hydrophilic group, and neutralizer, respectively. TEA, deionized water, and carbon black (CB) were added to the prepolymer under high-speed [...] Read more.
This study created water polyurethane (WPU) prepolymer by using isophorone diisocyanate, castor oil, dimethylolpropionic acid, and triethanolamine (TEA) as the hard segment, soft segment, hydrophilic group, and neutralizer, respectively. TEA, deionized water, and carbon black (CB) were added to the prepolymer under high-speed rotation to create an environmentally friendly vegetable-oil-based polyurethane. CB served as the fortifier and promoter of microphase separation. Fourier transform infrared spectroscopy was performed to elucidate the role of H-bond interactions within the CB/WPUs. Additionally, atomic force microscopy was conducted to determine the influence of H-bond interactions on the degree of microphase separation in the WPU. Furthermore, this study used four-point probe observation to discover the materials’ conductivity of CB in the WPU. Thermogravimetric analysis and dynamic mechanical analysis were performed to measure the thermal properties of the CB/WPUs. The mechanical properties of CB/WPUs were measured using a tensile testing machine. The CB/WPUs were also soaked in 1 wt.% NaOH solution for different amounts of time to determine the degradation properties of the CB/WPUs. Finally, scanning electron microscopy was performed to observe the topography of the CB/WPUs after degradation. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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15 pages, 5048 KiB  
Communication
Sequential Recovery of Heavy and Noble Metals by Mussel-Inspired Polydopamine-Polyethyleneimine Conjugated Polyurethane Composite Bearing Dithiocarbamate Moieties
by Dingshuai Xue, Ting Li, Guoju Chen, Yanhong Liu, Danping Zhang, Qian Guo, Jujie Guo, Yueheng Yang, Jiefang Sun, Benxun Su, Lei Sun and Bing Shao
Polymers 2019, 11(7), 1125; https://doi.org/10.3390/polym11071125 - 02 Jul 2019
Cited by 19 | Viewed by 3989
Abstract
Dithiocarbamate-grafted polyurethane (PU) composites were synthesized by anchoring dithiocarbamate (DTC) as a chelating agent to the polyethyleneimine-polydopamine (PE-DA)-functionalized graphene-based PU matrix (PE-DA@GB@PU), as a new adsorbent material for the recovery of Cu2+, Pb2+, and Cd2+ from industrial effluents. [...] Read more.
Dithiocarbamate-grafted polyurethane (PU) composites were synthesized by anchoring dithiocarbamate (DTC) as a chelating agent to the polyethyleneimine-polydopamine (PE-DA)-functionalized graphene-based PU matrix (PE-DA@GB@PU), as a new adsorbent material for the recovery of Cu2+, Pb2+, and Cd2+ from industrial effluents. After leaching with acidic media to recover Cu2+, Pb2+, and Cd2+, dithiocarbamate-grafted PE-DA@GB@PU (DTC-g-PE-DA@GB@PU) was decomposed and PE-DA@GP was regenerated. The latter was used to recover Pd2+, Pt4+, and Au3+ from the copper leaching residue and anode slime. The present DTC-g-PE-DA@GB@PU and PE-DA@GB@PU composites show high adsorption performance, effective separation, and quick adsorption of the target ions. The morphologies of the composites were studied by scanning electron microscopy and their structures were investigated by Fourier transform infrared (FT-IR) spectroscopy and Raman spectroscopy. The effects of pH values, contact time, and initial metal ion concentration conditions were also studied. An adsorption mechanism was proposed and discussed in terms of the FT-IR results. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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20 pages, 7728 KiB  
Article
POSS Compounds as Modifiers for Rigid Polyurethane Foams (Composites)
by Anna Strąkowska, Sylwia Członka and Krzysztof Strzelec
Polymers 2019, 11(7), 1092; https://doi.org/10.3390/polym11071092 - 27 Jun 2019
Cited by 23 | Viewed by 5019
Abstract
Three types of polyhedral oligomeric silsesquioxanes (POSSs) with different functional active groups were used to modify rigid polyurethane foams (RPUFs). Aminopropylisobutyl-POSS (AP-POSS), trisilanoisobutyl-POSS (TS-POSS) and octa(3-hydroxy-3-methylbutyldimethylsiloxy-POSS (OH-POSS) were added in an amount of 0.5 wt.% of the polyol weight. The characteristics of fillers [...] Read more.
Three types of polyhedral oligomeric silsesquioxanes (POSSs) with different functional active groups were used to modify rigid polyurethane foams (RPUFs). Aminopropylisobutyl-POSS (AP-POSS), trisilanoisobutyl-POSS (TS-POSS) and octa(3-hydroxy-3-methylbutyldimethylsiloxy-POSS (OH-POSS) were added in an amount of 0.5 wt.% of the polyol weight. The characteristics of fillers including the size of particles, evaluation of the dispersion of particles and their effect on the viscosity of the polyol premixes were performed. Next, the obtained foams were evaluated by their processing parameters, morphology (Scanning Electron Microscopy analysis, SEM), mechanical properties (compressive test, three-point bending test, impact strength), viscoelastic behavior (Dynamic Mechanical Analysis, DMA), thermal properties (Thermogravimetric Analysis, TGA, thermal conductivity) and application properties (contact angle, water absorption). The results showed that the morphology of modified foams is significantly affected by the fillers typology, which resulted in inhomogeneous, irregular, large cell shapes and further affected the physical and mechanical properties of the resulting materials. RPUFs modified with AP-POSS represent better mechanical properties compared to the RPUFs modified with other POSS. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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9 pages, 2285 KiB  
Article
An In Vitro Evaluation, on Polyurethane Foam Sheets, of the Insertion Torque (IT) Values, Pull-Out Torque Values, and Resonance Frequency Analysis (RFA) of NanoShort Dental Implants
by Luca Comuzzi, Giovanna Iezzi, Adriano Piattelli and Margherita Tumedei
Polymers 2019, 11(6), 1020; https://doi.org/10.3390/polym11061020 - 10 Jun 2019
Cited by 29 | Viewed by 3375
Abstract
Objectives: The aim of this study was to investigate, in polyurethane foam sheets, the primary implant stability of a NanoShort implant compared to a self-condenser implant and to a standard, conventional implant. Materials and Methods: Three implant designs were evaluated in the present [...] Read more.
Objectives: The aim of this study was to investigate, in polyurethane foam sheets, the primary implant stability of a NanoShort implant compared to a self-condenser implant and to a standard, conventional implant. Materials and Methods: Three implant designs were evaluated in the present in vitro investigation: The Test implant (NanoShort), the Control A implant (self-condenser), and the Control B implant (standard design). The study was conducted by comparing the insertion torque values, the pull-out strength values, and the resonance frequency analysis (RFA) values of the Test and Control A and B implants inserted in polyurethane foam models of different thicknesses and densities. The foam densities were 10, 20, and 30 pounds per cubic foot (pcf). Three thicknesses of polyurethane foams (1, 2, 3 mm) were evaluated for a total of 640 experimental sites. Results: The Pearson correlation showed a moderate/strong correlation between all study groups (r > 0.3) for insertion torque and pull-out strength levels. Increased stability of the Test implants was obtained in 3 mm polyurethane sheets. The 2.5 and 3.5 mm Test implants presented good stability in 3 mm polyurethane sheets of 20–30 pcf densities. The Control implants showed better results compared to the Test implants in 1, 2, and 3 mm polyurethane sheets with densities of 10, 20, and 30 pcf. Conclusions: The NanoShort dental implant evaluated in this in vitro study showed a high level of stability in some experimental conditions, and could represent a useful tool, especially in the posterior mandible, as an alternative to vertical augmentation procedures. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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17 pages, 2841 KiB  
Article
Degradable Poly(ether-ester-urethane)s Based on Well-Defined Aliphatic Diurethane Diisocyanate with Excellent Shape Recovery Properties at Body Temperature for Biomedical Application
by Minghui Xiao, Na Zhang, Jie Zhuang, Yuchen Sun, Fang Ren, Wenwen Zhang and Zhaosheng Hou
Polymers 2019, 11(6), 1002; https://doi.org/10.3390/polym11061002 - 05 Jun 2019
Cited by 16 | Viewed by 4659
Abstract
The aim of this study is to offer a new class of degradable shape-memory poly(ether-ester-urethane)s (SMPEEUs) based on poly(ether-ester) (PECL) and well-defined aliphatic diurethane diisocyanate (HBH) for further biomedical application. The prepolymers of PECLs were synthesized through bulk ring-opening polymerization using ε-caprolactone as [...] Read more.
The aim of this study is to offer a new class of degradable shape-memory poly(ether-ester-urethane)s (SMPEEUs) based on poly(ether-ester) (PECL) and well-defined aliphatic diurethane diisocyanate (HBH) for further biomedical application. The prepolymers of PECLs were synthesized through bulk ring-opening polymerization using ε-caprolactone as the monomer and poly(ethylene glycol) as the initiator. By chain extension of PECL with HBH, SMPEEUs with varying PEG content were prepared. The chemical structures of the prepolymers and products were characterized by GPC, 1H NMR, and FT-IR, and the effect of PEG content on the physicochemical properties (especially the shape recovery properties) of SMPEEUs was studied. The microsphase-separated structures of the SMPEEUs were demonstrated by DSC and XRD. The SMPEEU films exhibited good tensile properties with the strain at a break of 483%–956% and an ultimate stress of 23.1–9.0 MPa. Hydrolytic degradation in vitro studies indicated that the time of the SMPEEU films becoming fragments was 4–12 weeks and the introduction of PEG facilitates the degradation rate of the films. The shape memory properties studies found that SMPEEU films with a PEG content of 23.4 wt % displayed excellent recovery properties with a recovery ratio of 99.8% and a recovery time of 3.9 s at body temperature. In addition, the relative growth rates of the SMPEEU films were greater than 75% after incubation for 72 h, indicating good cytocompatibility in vitro. The SMPEEUs, which possess not only satisfactory tensile properties, degradability, nontoxic degradation products, and cytocompatibility, but also excellent shape recovery properties at body temperature, promised to be an excellent candidate for medical device applications. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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20 pages, 6786 KiB  
Article
Polyhexamethylene Biguanide:Polyurethane Blend Nanofibrous Membranes for Wound Infection Control
by Anna Worsley, Kristin Vassileva, Janice Tsui, Wenhui Song and Liam Good
Polymers 2019, 11(5), 915; https://doi.org/10.3390/polym11050915 - 22 May 2019
Cited by 22 | Viewed by 5795
Abstract
Polyhexamethylene biguanide (PHMB) is a broad-spectrum antiseptic which avoids many efficacy and toxicity problems associated with antimicrobials, in particular, it has a low risk of loss of susceptibility due to acquired antimicrobial resistance. Despite such advantages, PHMB is not widely used in wound [...] Read more.
Polyhexamethylene biguanide (PHMB) is a broad-spectrum antiseptic which avoids many efficacy and toxicity problems associated with antimicrobials, in particular, it has a low risk of loss of susceptibility due to acquired antimicrobial resistance. Despite such advantages, PHMB is not widely used in wound care, suggesting more research is required to take full advantage of PHMB’s properties. We hypothesised that a nanofibre morphology would provide a gradual release of PHMB, prolonging the antimicrobial effects within the therapeutic window. PHMB:polyurethane (PU) electrospun nanofibre membranes were prepared with increasing PHMB concentrations, and the effects on antimicrobial activities, mechanical properties and host cell toxicity were compared. Overall, PHMB:PU membranes displayed a burst release of PHMB during the first hour following PBS immersion (50.5–95.9% of total released), followed by a gradual release over 120 h (≤25 wt % PHMB). The membranes were hydrophilic (83.7–53.3°), gradually gaining hydrophobicity as PHMB was released. They displayed superior antimicrobial activity, which extended past the initial release period, retained PU hyperelasticity regardless of PHMB concentration (collective tensile modulus of 5–35% PHMB:PU membranes, 3.56 ± 0.97 MPa; ultimate strain, >200%) and displayed minimal human cell toxicity (<25 wt % PHMB). With further development, PHMB:PU electrospun membranes may provide improved wound dressings. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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13 pages, 4826 KiB  
Article
Preparation, Physicochemical Properties, and Hemocompatibility of the Composites Based on Biodegradable Poly(Ether-Ester-Urethane) and Phosphorylcholine-Containing Copolymer
by Jun Zhang, Bing Yang, Qi Jia, Minghui Xiao and Zhaosheng Hou
Polymers 2019, 11(5), 860; https://doi.org/10.3390/polym11050860 - 11 May 2019
Cited by 10 | Viewed by 3324
Abstract
To improve the hemocompatibility of the biodegradable medical poly(ether-ester-urethane) (PEEU), containing uniform-size aliphatic hard segments that was prepared in our lab, a copolymer containing phosphorylcholine (PC) groups was blended with the PEEU. The PC-copolymer of poly(MPC-co-EHMA) (PMEH) was first obtained by copolymerization of [...] Read more.
To improve the hemocompatibility of the biodegradable medical poly(ether-ester-urethane) (PEEU), containing uniform-size aliphatic hard segments that was prepared in our lab, a copolymer containing phosphorylcholine (PC) groups was blended with the PEEU. The PC-copolymer of poly(MPC-co-EHMA) (PMEH) was first obtained by copolymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) and 2-ethylhexyl methacrylate (EHMA), and then dissolved in mixed solvent of ethanol/chloroform to obtain a homogeneous solution. The composite films (PMPU) with varying PMEH content were prepared by solvent evaporation method. The physicochemical properties of the composite films with varying PMEH content were researched. The PMPU films exhibited higher thermal stability than that of the pure PEEU film. With the PMEH content increasing from 5 to 20 wt%, the PMPU films also possessed satisfied tensile properties with ultimate stress of 22.9–15.8 MPa and strain at break of 925–820%. The surface and bulk hydrophilicity of the films were improved after incorporation of PMEH. In vitro degradation studies indicated that the degradation rate increased with PMEH content, and it took 12–24 days for composite films to become fragments. The protein adsorption and platelet-rich plasma contact tests were adapted to evaluate the surface hemocompatibility of the composite films. It was found that the amount of adsorbed protein and adherent platelet on the surface decreased significantly, and almost no activated platelets were observed when PMEH content was above 5 wt%, which manifested good surface hemocompatibility. Due to the biodegradability, acceptable tensile properties and good surface hemocompatibility, the composites can be expected to be applied in blood-contacting implant materials. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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19 pages, 7357 KiB  
Article
Designed Polyurethanes for Potential Biomedical and Pharmaceutical Applications: Novel Synthetic Strategy for Preparing Sucrose Containing Biocompatible and Biodegradable Polyurethane Networks
by Lajos Nagy, Miklós Nagy, Bence Vadkerti, Lajos Daróczi, György Deák, Miklós Zsuga and Sándor Kéki
Polymers 2019, 11(5), 825; https://doi.org/10.3390/polym11050825 - 07 May 2019
Cited by 13 | Viewed by 2873
Abstract
In this paper the preparation and detailed characterization of designed polyurethanes (SPURs) are reported for potential biological, biomedical and/or pharmaceutical applications. Importantly, in order to fulfill these goals all reactants and solvents used were selected according to the proposal of EUR-8 Pharmacopoeia. For [...] Read more.
In this paper the preparation and detailed characterization of designed polyurethanes (SPURs) are reported for potential biological, biomedical and/or pharmaceutical applications. Importantly, in order to fulfill these goals all reactants and solvents used were selected according to the proposal of EUR-8 Pharmacopoeia. For the synthesis, a novel strategy was introduced and elaborated. A series of SPUR samples was prepared from poly(ε-caprolactone)-diol, 1,6-hexamethylene diisocyanate and sucrose as a chain extender/crosslinking agent to obtain sucrose containing polyurethanes. In addition, the mol ratios of the sucrose were varied within an order of magnitude. The prepolymers and the products of the syntheses were investigated by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and infrared spectroscopy (IR), respectively. It was found that the reactivity of the eight free hydroxyl groups of sucrose are different, and after curing the SPUR samples at 60 °C no free isocyanate groups can be observed. Furthermore, swelling experiments performed with various solvents of different polarities revealed that the highest degree of swelling took place in dimethyl-sulfoxide. However, low degrees of swelling were recognized in water and hexane. It is important to note that the gel contents were around 90% in all cases, which demonstrate that the crosslinking was almost complete. In addition, the kinetics of swelling were also evaluated and successfully modeled. The crosslink densities were calculated from the data of the swelling experiments by means of the Flory-Rehner equation. Unexpectedly, it was found that the crosslink density decreased with the increasing sucrose content also in line with the results obtained by relaxation modulus experiments and dynamic mechanical analysis (DMA). The Tg and Tm of SPUR samples, determined from DSC and DMA measurements, were around −57 °C and 27 °C, respectively. According to the mechanical tests the SPUR samples showed high elongation at break values, i.e., high flexibilities. Furthermore, the stress-strain curves were also modeled and discussed. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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14 pages, 3254 KiB  
Article
An Ab Initio Investigation of the 4,4′-Methlylene Diphenyl Diamine (4,4′-MDA) Formation from the Reaction of Aniline with Formaldehyde
by R. Zsanett Boros, László Farkas, Károly Nehéz, Béla Viskolcz and Milán Szőri
Polymers 2019, 11(3), 398; https://doi.org/10.3390/polym11030398 - 01 Mar 2019
Cited by 7 | Viewed by 10395
Abstract
The most commonly applied industrial synthesis of 4,4′-methylene diphenyl diamine (4,4′-MDA), an important polyurethane intermediate, is the reaction of aniline and formaldehyde. Molecular understanding of the 4,4′-MDA formation can provide strategy to prevent from side reactions. In this work, a molecular mechanism consisted [...] Read more.
The most commonly applied industrial synthesis of 4,4′-methylene diphenyl diamine (4,4′-MDA), an important polyurethane intermediate, is the reaction of aniline and formaldehyde. Molecular understanding of the 4,4′-MDA formation can provide strategy to prevent from side reactions. In this work, a molecular mechanism consisted of eight consecutive, elementary reaction steps from anilines and formaldehyde to the formation of 4,4′-MDA in acidic media is proposed using accurate G3MP2B3 composite quantum chemical method. Then G3MP2B3-SMD results in aqueous and aniline solutions were compared to the gas phase mechanism. Based on the gas phase calculations standard enthalpy of formation, entropy and heat capacity values were evaluated using G3MP2B3 results for intermediates The proposed mechanism was critically evaluated and important side reactions are considered: the competition of formation of protonated p-aminobenzylaniline (PABAH+), protonated aminal (AMH+) and o-aminobenzylaniline (OABAH+). Competing reactions of the 4,4′-MDA formation is also thermodynamically analyzed such as the formation of 2,4-MDAH+, 3,4-MDAH+. AMH+ can be formed through loose transition state, but it becomes kinetic dead-end, while formation of significant amount of 2,4-MDA is plausible through low-lying transition state. The acid strength of the key intermediates such as N-methylenebenzeneanilium, PABAH+, 4-methylidenecyclohexa-2,5-diene-1-iminium, and AMH+ was estimated by relative pKa calculation. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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17 pages, 4658 KiB  
Article
Comparison of Adhesive Properties of Polyurethane Adhesive System and Wood-plastic Composites with Different Polymers after Mechanical, Chemical and Physical Surface Treatment
by Barbora Nečasová, Pavel Liška, Jakub Kelar and Jiří Šlanhof
Polymers 2019, 11(3), 397; https://doi.org/10.3390/polym11030397 - 01 Mar 2019
Cited by 21 | Viewed by 4937
Abstract
The cost of most primary materials is increasing, therefore, finding innovative solutions for the re-use of residual waste has become a topic discussed more intensely in recent years. WPCs certainly meet some of these demands. The presented study is focused on an experimental [...] Read more.
The cost of most primary materials is increasing, therefore, finding innovative solutions for the re-use of residual waste has become a topic discussed more intensely in recent years. WPCs certainly meet some of these demands. The presented study is focused on an experimental analysis of the effect of surface treatment on the adhesive properties of selected WPCs. Bonding of polymer-based materials is a rather complicated phenomenon and modification of the bonded area in order to improve the adhesive properties is required. Two traditional types of surface treatments and one entirely new approach have been used: mechanical with sandpaper, chemical with 10 wt % NaOH solution and physical modification of the surface by means of a MHSDBD plasma source. For comparison purposes, two high-density polyethylene based products and one polyvinyl-chloride based product with different component ratios were tested. A bonded joint was made using a moisture-curing permanently elastic one-component polyurethane pre-polymer adhesive. Standardized tensile and shear test methods were performed after surface treatment. All tested surface treatments resulted in an improvement of adhesive properties and an increase in bond strength, however, the MHSDBD plasma treatment was proven to be a more suitable surface modification for all selected WPCs. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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13 pages, 4527 KiB  
Article
One-Pot Processing of Regenerated Cellulose Nanoparticles/Waterborne Polyurethane Nanocomposite for Eco-friendly Polyurethane Matrix
by Soon Mo Choi, Min Woong Lee and Eun Joo Shin
Polymers 2019, 11(2), 356; https://doi.org/10.3390/polym11020356 - 18 Feb 2019
Cited by 19 | Viewed by 4316
Abstract
Regenerated cellulose nanoparticles (RCNs) reinforced waterborne polyurethanes (WPU) were developed to improve mechanical properties as well as biodegradability by using a facile, eco-friendly approach, and introducing much stronger chemical bonding than common physical bonding between RCNs and WPU. Firstly, RCNs which have an [...] Read more.
Regenerated cellulose nanoparticles (RCNs) reinforced waterborne polyurethanes (WPU) were developed to improve mechanical properties as well as biodegradability by using a facile, eco-friendly approach, and introducing much stronger chemical bonding than common physical bonding between RCNs and WPU. Firstly, RCNs which have an effect on improving the solubility and stability of a solution, thereby resulting in lower crystallinity, were fabricated by using a NaOH/urea solution. In addition, the stronger chemical bond between RCNs and WPU was here introduced by regarding at which stage in particular added RCNs worked best on strengthening their bond in the process of WPU synthesis. The chemical structure, mechanical, particle size and distribution, viscosity, and thermal properties of the resultant RCNs/WPU nanocomposites were investigated by Fourier transform infrared analysis (FTIR), Zeta-potential analysis, viscometer, thermogravimetric analysis (TGA), Instron, and dynamic mechanical analysis (DMA). The results of all characterizations indicated that the RCNs/WPU-DMF associated with the addition of RCNs in DMF-dispersed step resulted in more effectively crosslinked between WPU and nano-fillers of nanocellulose particles in the dispersion than Acetone and Water-dispersed steps, thereby attributing to novel interactions formed between RCNs and WPU. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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17 pages, 9444 KiB  
Article
Synthesis and Morphological Control of Biocompatible Fluorescent/Magnetic Janus Nanoparticles Based on the Self-Assembly of Fluorescent Polyurethane and Fe3O4 Nanoparticles
by Botian Li, Wei Shao, Yanzan Wang, Da Xiao, Yi Xiong, Haimu Ye, Qiong Zhou and Qingjun Jin
Polymers 2019, 11(2), 272; https://doi.org/10.3390/polym11020272 - 05 Feb 2019
Cited by 9 | Viewed by 4116
Abstract
Functionalized Janus nanoparticles have received increasing interest due to their anisotropic shape and the particular utility in biomedicine areas. In this work, a simple and efficient method was developed to prepare fluorescent/magnetic composite Janus nanoparticles constituted of fluorescent polyurethane and hydrophobic nano Fe [...] Read more.
Functionalized Janus nanoparticles have received increasing interest due to their anisotropic shape and the particular utility in biomedicine areas. In this work, a simple and efficient method was developed to prepare fluorescent/magnetic composite Janus nanoparticles constituted of fluorescent polyurethane and hydrophobic nano Fe3O4. Two kinds of fluorescent polyurethane prepolymers were synthesized by the copolymerization of fluorescent dye monomers, and the fluorescent/magnetic nanoparticles were fabricated in one-pot via the process of mini-emulsification and self-assembly. The nanostructures of the resulting composite nanoparticles, including core/shell and Janus structure, could be controlled by the phase separation in assembly process according to the result of transmission electron microscopy, whereas the amount of the nonpolar segments of polyurethane played an important role in the particle morphology. The prominent magnetic and fluorescent properties of the Janus nanoparticles were also confirmed by vibrating magnetometer and confocal laser scanning microscope. Furthermore, the Janus nanoparticles featured excellent dispersity, storage stability, and cytocompatibility, which might benefit their potential application in biomedical areas. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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17 pages, 1980 KiB  
Article
Computational Analysis of Nonuniform Expansion in Polyurethane Foams
by D. Niedziela, I. E. Ireka and K. Steiner
Polymers 2019, 11(1), 100; https://doi.org/10.3390/polym11010100 - 09 Jan 2019
Cited by 24 | Viewed by 5420
Abstract
This paper computationally investigates heterogeneity in the distribution of foam fraction in chemically expanding blown polyurethane foam. The experimentally observed disparity in the volumes of expanded foam when an equal mass of the foaming mixture was injected into tubes of different dimensions motivated [...] Read more.
This paper computationally investigates heterogeneity in the distribution of foam fraction in chemically expanding blown polyurethane foam. The experimentally observed disparity in the volumes of expanded foam when an equal mass of the foaming mixture was injected into tubes of different dimensions motivated this study. To understand this phenomenon, attributed to local variations in the thermal and rheological properties of the expanding system, we explore available data from free-rise foam-expansion experiments in different geometries. Inspired by the mathematical framework for the microstructure modelling of bubble growth in viscous liquids, we study the reacting mixture as a continuum and formulate appropriate mathematical models that account for spatial inhomogeneity in the foam-expansion process. The nonlinear coupled system of partial differential equations governing flow was numerically solved using finite-volume techniques, and the associated results are presented and discussed with graphical illustrations. The proximity of the foaming-mixture core to the external environment and the thickness of a thermal-diffusion layer formed near the bounding geometry was seen to influence the distribution of the foam fraction. Our simulations showed an average spatial variation of about 1.1% in the distribution of solid foam fraction from the walls to the core, as verified with data from μ CT scan analysis of the expanded foam. This also reflects the distribution of void fraction in the foam matrix. The models were validated with experimental data, and our results favourably compared with the experiment observations. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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17 pages, 9092 KiB  
Article
Effects of Tung Oil-Based Polyols on the Thermal Stability, Flame Retardancy, and Mechanical Properties of Rigid Polyurethane Foam
by Wei Zhou, Caiying Bo, Puyou Jia, Yonghong Zhou and Meng Zhang
Polymers 2019, 11(1), 45; https://doi.org/10.3390/polym11010045 - 30 Dec 2018
Cited by 27 | Viewed by 4425
Abstract
A phosphorus-containing tung oil-based polyol (PTOP) and a silicon-containing tung oil-based polyol (PTOSi) were each efficiently prepared by attaching 9,10-dihydro-9-oxa-10-phosphaphenanthrene (DOPO) and dihydroxydiphenylsilane (DPSD) directly, respectively, to the epoxidized monoglyceride of tung oil (EGTO) through a ring-opening reaction. The two new polyols were [...] Read more.
A phosphorus-containing tung oil-based polyol (PTOP) and a silicon-containing tung oil-based polyol (PTOSi) were each efficiently prepared by attaching 9,10-dihydro-9-oxa-10-phosphaphenanthrene (DOPO) and dihydroxydiphenylsilane (DPSD) directly, respectively, to the epoxidized monoglyceride of tung oil (EGTO) through a ring-opening reaction. The two new polyols were used in the formation of rigid polyurethane foam (RPUF), which displayed great thermal stability and excellent flame retardancy performance. The limiting oxygen index (LOI) value of RPUF containing 80 wt % PTOP and 80 wt % PTOSi was 24.0% and 23.4%, respectively. Fourier transfer infrared (FTIR), Nuclear Magnetic Resonance (NMR) and thermogravimetric (TG) analysis revealed that DOPO and DPSD are linked to EGTO by a covalent bond. Interestingly, PTOP and PTOSi had opposite effects on Tg and the compressive strength of RPUF, where, with the appropriate loading, the compressive strengths were 0.82 MPa and 0.25 MPa, respectively. At a higher loading of PTOP and PTOSi, the thermal conductivity of RPUF increased while the RPUF density decreased. The scanning electron microscope (SEM) micrographs showed that the size and closed areas of the RPUF cells were regular. SEM micrographs of the char after combustion showed that the char layer was compact and dense. The enhanced flame retardancy of RPUF resulted from the barrier effect of the char layer, which was covered with incombustible substance. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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20 pages, 16048 KiB  
Article
Effect of Evening Primrose Oil-Based Polyol on the Properties of Rigid Polyurethane–Polyisocyanurate Foams for Thermal Insulation
by Joanna Paciorek-Sadowska, Marcin Borowicz, Bogusław Czupryński and Marek Isbrandt
Polymers 2018, 10(12), 1334; https://doi.org/10.3390/polym10121334 - 03 Dec 2018
Cited by 35 | Viewed by 4573
Abstract
The article presents the results of research on the synthesis of a new biopolyol based on evening primrose oil, and its use in the production of rigid polyurethane–polyisocyanurate foams intended for thermal insulation. The obtained biopolyol was subjected to analytical, physicochemical, and spectroscopic [...] Read more.
The article presents the results of research on the synthesis of a new biopolyol based on evening primrose oil, and its use in the production of rigid polyurethane–polyisocyanurate foams intended for thermal insulation. The obtained biopolyol was subjected to analytical, physicochemical, and spectroscopic tests (Fourier transform infrared (FTIR), 1H NMR, 13C NMR) to confirm its suitability for the synthesis of polyurethane materials. Then, it was used for the partial replacement of the petrochemical polyol in the polyurethane formulation. Obtained rigid polyurethane–polyisocyanurate foams are characterized by a lower apparent density, brittleness, water absorption, and thermal conductivity coefficient λ. In addition, foams modified by biopolyols had a higher content of closed cells and higher aging resistance. The results of the conducted research showed that the use of the biopolyol based on evening primrose oil may be an alternative to petrochemical polyols. The research presented herein is perfectly consistent with the trends of sustainable development and the philosophy of green chemistry. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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21 pages, 7537 KiB  
Article
Synthesis and Properties of Novel Polyurethanes Containing Long-Segment Fluorinated Chain Extenders
by Jia-Wun Li, Hsun-Tsing Lee, Hui-An Tsai, Maw-Cherng Suen and Chih-Wei Chiu
Polymers 2018, 10(11), 1292; https://doi.org/10.3390/polym10111292 - 21 Nov 2018
Cited by 38 | Viewed by 8514
Abstract
In this study, novel biodegradable long-segment fluorine-containing polyurethane (PU) was synthesized using 4,4′-diphenylmethane diisocyanate (MDI) and 1H,1H,10H,10H-perfluor-1,10-decanediol (PFD) as hard segment, and polycaprolactone diol (PCL) as a biodegradable soft segment. Nuclear magnetic resonance (NMR) was used to perform 1H NMR, 19F [...] Read more.
In this study, novel biodegradable long-segment fluorine-containing polyurethane (PU) was synthesized using 4,4′-diphenylmethane diisocyanate (MDI) and 1H,1H,10H,10H-perfluor-1,10-decanediol (PFD) as hard segment, and polycaprolactone diol (PCL) as a biodegradable soft segment. Nuclear magnetic resonance (NMR) was used to perform 1H NMR, 19F NMR, 19F–19F COSY, 1H–19F COSY, and HMBC analyses on the PFD/PU structures. The results, together with those from Fourier transform infrared spectroscopy (FTIR), verified that the PFD/PUs had been successfully synthesized. Additionally, the soft segment and PFD were changed, after which FTIR and XPS peak-differentiation-imitating analyses were employed to examine the relationship of the hydrogen bonding reaction between the PFD chain extender and PU. Subsequently, atomic force microscopy was used to investigate the changes in the microphase structure between the PFD chain extender and PU, after which the effects of the thermal properties between them were investigated through thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Finally, the effects of the PFD chain extender on the mechanical properties of the PU were investigated through a tensile strength test. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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11 pages, 3325 KiB  
Article
Investigation on the Short-Term Aging-Resistance of Thermoplastic Polyurethane-Modified Asphalt Binders
by Ruien Yu, Xijing Zhu, Maorong Zhang and Changqing Fang
Polymers 2018, 10(11), 1189; https://doi.org/10.3390/polym10111189 - 25 Oct 2018
Cited by 41 | Viewed by 3842
Abstract
In this reported work, thermoplastic polyurethane (TPU) was used as a reactive polymer modifying agent to prepare a modified-asphalt, using a high-speed shearing method. Physical performance tests of the TPU-modified asphalt were conducted before and after short-term aging, and the aging resistance was [...] Read more.
In this reported work, thermoplastic polyurethane (TPU) was used as a reactive polymer modifying agent to prepare a modified-asphalt, using a high-speed shearing method. Physical performance tests of the TPU-modified asphalt were conducted before and after short-term aging, and the aging resistance was examined by the change in materials properties. In addition, low-temperature rheological properties, thermal properties, the high-temperature storage stability, and the aging mechanism of TPU-modified asphalt were also investigated. The results showed that the addition of TPU improved the aging resistance of base asphalt, which was evidenced by the increased penetration ratio and decreased softening point of the asphalt, after aging. Similarly, Fourier Transform infrared (FTIR) spectroscopy results verified that TPU improved the asphalt aging resistance. It was found that the TPU functional groups played a role in improving thermal properties, high-temperature storage stability, and in the dispersion of modified asphalt. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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16 pages, 5308 KiB  
Article
Synthesis and Characterization of Isosorbide-Based Polyurethanes Exhibiting Low Cytotoxicity Towards HaCaT Human Skin Cells
by Barbara S. Gregorí Valdés, Clara S. B. Gomes, Pedro T. Gomes, José R. Ascenso, Hermínio P. Diogo, Lídia M. Gonçalves, Rui Galhano dos Santos, Helena M. Ribeiro and João C. Bordado
Polymers 2018, 10(10), 1170; https://doi.org/10.3390/polym10101170 - 20 Oct 2018
Cited by 16 | Viewed by 6873
Abstract
The synthesis of four samples of new polyurethanes was evaluated by changing the ratio of the diol monomers used, poly(propylene glycol) (PPG) and D-isosorbide, in the presence of aliphatic isocyanates such as the isophorone diisocyanate (IPDI) and 4,4′-methylenebis(cyclohexyl isocyanate) (HMDI). The thermal properties [...] Read more.
The synthesis of four samples of new polyurethanes was evaluated by changing the ratio of the diol monomers used, poly(propylene glycol) (PPG) and D-isosorbide, in the presence of aliphatic isocyanates such as the isophorone diisocyanate (IPDI) and 4,4′-methylenebis(cyclohexyl isocyanate) (HMDI). The thermal properties of the four polymers obtained were determined by DSC, exhibiting Tg values in the range 55–70 °C, and their molecular structure characterized by FTIR, 1H, and 13C NMR spectroscopies. The diffusion coefficients of these polymers in solution were measured by the Pulse Gradient Spin Echo (PGSE) NMR method, enabling the calculation of the corresponding hydrodynamic radii in diluted solution (1.62–2.65 nm). The molecular weights were determined by GPC/SEC and compared with the values determined by a quantitative 13C NMR analysis. Finally, the biocompatibility of the polyurethanes was assessed using the HaCaT keratinocyte cell line by the MTT reduction assay method showing values superior to 70% cell viability. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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13 pages, 2747 KiB  
Article
A Mild Method for Surface-Grafting PEG Onto Segmented Poly(Ester-Urethane) Film with High Grafting Density for Biomedical Purpose
by Lulu Liu, Yuanyuan Gao, Juan Zhao, Litong Yuan, Chenglin Li, Zhaojun Liu and Zhaosheng Hou
Polymers 2018, 10(10), 1125; https://doi.org/10.3390/polym10101125 - 10 Oct 2018
Cited by 24 | Viewed by 4201
Abstract
In the paper, poly(ethylene glycol) (PEG) was grafted on the surface of poly(ester-urethane) (SPEU) film with high grafting density for biomedical purposes. The PEG-surface-grafted SPEU (SPEU-PEG) was prepared by a three-step chemical treatment under mild-reaction conditions. Firstly, the SPEU film surface was treated [...] Read more.
In the paper, poly(ethylene glycol) (PEG) was grafted on the surface of poly(ester-urethane) (SPEU) film with high grafting density for biomedical purposes. The PEG-surface-grafted SPEU (SPEU-PEG) was prepared by a three-step chemical treatment under mild-reaction conditions. Firstly, the SPEU film surface was treated with 1,6-hexanediisocyanate to introduce -NCO groups on the surface with high density (5.28 × 10−7 mol/cm2) by allophanate reaction; subsequently, the -NCO groups attached to SPEU surface were coupled with one of -NH2 groups of tris(2-aminoethyl)amine via condensation reaction to immobilize -NH2 on the surface; finally, PEG with different molecular weight was grafted on the SPEU surface through Michael addition between terminal C = C bond of monoallyloxy PEG and -NH2 group on the film surface. The chemical structure and modified surface were characterized by FT-IR, 1H NMR, X-ray photoelectron spectroscopy (XPS), and water contact angle. The SPEU-PEGs displaying much lower water contact angles (23.9–21.8°) than SPEU (80.5°) indicated that the hydrophilic PEG chains improved the surface hydrophilicity significantly. The SPEU-PEG films possessed outstanding mechanical properties with strain at break of 866–884% and ultimate stress of 35.5–36.4 MPa, which were slightly lower than those of parent film, verifying that the chemical treatments had minimum deterioration on the mechanical properties of the substrate. The bovine serum albumin adsorption and platelet adhesion tests revealed that SPEU-PEGs had improved resistance to protein adsorption (3.02–2.78 μg/cm2) and possessed good resistance to platelet adhesion (781–697 per mm2), indicating good surface hemocompatibility. In addition, due to the high grafting density, the molecular weight of surface-grafted PEG had marginal effect on the surface hydrophilicity and hemocompatibility. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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12 pages, 3004 KiB  
Article
Branched Polyurethanes Based on Synthetic Polyhydroxybutyrate with Tunable Structure and Properties
by Joanna Brzeska, Anna Maria Elert, Magda Morawska, Wanda Sikorska, Marek Kowalczuk and Maria Rutkowska
Polymers 2018, 10(8), 826; https://doi.org/10.3390/polym10080826 - 26 Jul 2018
Cited by 25 | Viewed by 4050
Abstract
Branched, aliphatic polyurethanes (PURs) were synthesized and compared to linear analogues. The influence of polycaprolactonetriol and synthetic poly([R,S]-3-hydroxybutyrate) (R,S-PHB) in soft segments on structure, thermal and sorptive properties of PURs was determined. Using FTIR and Raman spectroscopies it was found that increasing the [...] Read more.
Branched, aliphatic polyurethanes (PURs) were synthesized and compared to linear analogues. The influence of polycaprolactonetriol and synthetic poly([R,S]-3-hydroxybutyrate) (R,S-PHB) in soft segments on structure, thermal and sorptive properties of PURs was determined. Using FTIR and Raman spectroscopies it was found that increasing the R,S-PHB amount in the structure of branched PURs reduced a tendency of urethane groups to hydrogen bonding. Melting enthalpies (on DSC thermograms) of both soft and hard segments of linear PURs were higher than branched PURs, suggesting that linear PURs were more crystalline. Oil sorption by samples of linear and branched PURs, containing only polycaprolactone chains in soft segments, was higher than in the case of samples with R,S-PHB in their structure. Branched PUR without R,S-PHB absorbed the highest amount of oil. Introducing R,S-PHB into the PUR structure increased water sorption. Thus, by operating the number of branching and the amount of poly([R,S]-3-hydroxybutyrate) in soft segments thermal and sorptive properties of aliphatic PURs could be controlled. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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