scholarly journals Biobased Waterborne Polyurethane-Ureas Modified with POSS-OH for Fluorine-Free Hydrophobic Textile Coatings

Polymers ◽  
2021 ◽  
Vol 13 (20) ◽  
pp. 3526
Author(s):  
Amado Lacruz ◽  
Mireia Salvador ◽  
Miren Blanco ◽  
Karmele Vidal ◽  
Amaia M. Goitandia ◽  
...  

Waterborne polyurethane-urea dispersions (WPUD), which are based on fully biobased amorphous polyester polyol and isophorone diisocyanate (IPDI), have been successfully synthesized obtaining a finishing agent that provides textiles with an enhanced hydrophobicity and water column. Grafting of trans-cyclohexanediol isobutyl POSS (POSS-OH) to the biobased polymer backbone has also been investigated for the first time and its properties compared to a standard chain extender, 1,3-propanediol (PDO). The chemical structure of WPUD has been characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The thermal properties have been evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Mechanical properties have been studied by tensile stress–strain analysis. Moreover, the particle size, particle size distribution (PSD), and stability of developed waterborne dispersions have been assessed by dynamic light scattering (DLS), Z-potential, storage aging tests, and accelerated aging tests by analytical centrifuge (LUM). Subsequently, selected fabrics have been face-coated by the WPUD using the knife coating method and their properties have been assessed by measuring the water contact angle (WCA), oil contact angle (OCA), water column, fabric stiffness, air permeability, and water vapor resistance (breathability). Finally, the surface morphology and elemental composition of uncoated and coated fabrics have been studied by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), respectively. All of the synthesized polyurethane-ureas provided the coated substrates with a remarkable hydrophobicity and water column, resulting in a more sustainable alternative to waterproof coatings based on fluoropolymers, such as PTFE. Grafting POSS-OH to the polymeric backbone has led to textile coatings with enhanced hydrophobicity, maintaining thermal, mechanical, and water column properties, giving rise to multifunctional coatings that are highly demanded in protective workwear and technical textiles.

Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1624
Author(s):  
Amado Lacruz ◽  
Mireia Salvador ◽  
Miren Blanco ◽  
Karmele Vidal ◽  
Amaia M. Goitandia ◽  
...  

Waterborne polyurethane-urea dispersions (WPUD), which are based on 100% bio-based semi-crystalline polyester polyol and isophorone diisocyanate, have been successfully synthesized and doped with single-walled carbon nanotubes (SWCNT) to obtain a finishing agent that provides textiles with multifunctional properties. The chemical structure of WPUD has been characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The thermal properties have been evaluated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). Mechanical properties have been studied by tensile stress–strain analysis. Moreover, the particle size, particle size distribution (PSD), and stability of developed waterborne dispersions have been assessed by dynamic light scattering (DLS), Z-potential, and accelerated aging tests (analytical centrifugation). Subsequently, selected fabrics have been face-coated by the WPUD using knife coating method and their properties have been assessed by measuring water contact angle (WCA), water column, fabric stiffness, and air permeability. The electrical conductivity of textiles coated with SWCNT-doped WPUD has been evaluated by EN 1149 standard. Finally, the surface morphologies of uncoated and coated fabrics have been studied by scanning electron microscopy (SEM). All of the synthesized polyurethane-ureas provide the coated substrates with remarkable water-repellency and water column, being therefore a more sustainable alternative to waterproof coatings based on fluoropolymers, such as PTFE. The additivation of the polymeric matrices with SWCNT has led to textile coatings with excellent electrical conductivity, maintaining water column properties, giving rise to multifunctional coatings that are highly demanded in protective workwear and technical textiles.


2021 ◽  
Vol 29 (9_suppl) ◽  
pp. S1361-S1370
Author(s):  
Xuwu Luo ◽  
Guancheng Jiang ◽  
Xinliang Li ◽  
Lili Yang

In this paper, sodium montmorillonite was modified with gelatin of different concentrations, and various colloidal characteristics of the gelatin-treated clays were measured and analyzed in detail. First, the influence of gelatin on the interlayer space of Mt layers was investigated by X-ray diffraction analysis. Moreover, the aggregation of Mt particles was examined using a combination of electron microscopy and particle size distribution experiments, while the variation of the electrical property of Mt was measured using ζ potential test. Gelatin of different concentrations can increase the particle size of Mt in different degrees. The addition of 4% gelatin could improve the ζ potential of Mt from −30.65 to −15.55 mV. The wettability change of modified Mt induced by the adsorption of gelatin was followed by measurements of water contact angle and observations of the morphology of Mt/gelatin membrane through SEM images. 4% gelatin could improve the water contact angle of Mt to 81.3°. Finally, the rheological properties of Mt/gelatin dispersion including shear viscosity and shear stress were measured using a stress-controlled rheometer. All of the results were consistent by showing that the overall colloidal characteristics and behavior of the gelatin-treated Mt strongly varied depending on the gelatin concentration used in the modification process. These results can provide a deep and comprehensive understanding of the colloidal properties of clay/gelatin systems and give important guidance for the performance design and improvement of Mt/gelatin composite materials. Furthermore, this study can also be expanded the application of gelatin and its composites to other fields.


2019 ◽  
Vol 10 (4) ◽  
pp. 77-94
Author(s):  
Sashivinay Kumar Gaddam ◽  
Aruna Palanisamy

A novel cottonseed oil-based ionizable polyol was introduced as ionic soft segment in waterborne polyurethane dispersion (PUD) synthesis. The ionizable polyol was synthesized by ring opening of epoxidized cottonseed oil (ECSO) with 4-aminobenzoic acid (PABA) and blended with hydroxylated cottonseed oil polyol (HCSO) in different weight ratios to develop a series of mixed polyols having different hydroxyl numbers viz., 146, 130 and 114 mg KOH/g. Three different PUDs were synthesized using the mixed polyols, isophorone diisocyanate, and 3-aminopropyltriethoxysilane. The chemical structure, thermo-mechanical properties, and surface properties of cured PUD films were examined using Fourier-transform infrared spectroscopy (FTIR), Dynamic mechanical thermal analysis (DMTA), universal testing machine (UTM) and contact angle measurements respectively. The effect of Si–O–Si cross-linking network density, which increases with an increase in OH values of the mixed polyol was also investigated. All the PUDs prepared in this study exhibited good storage stability (>4 months), and the average particle sizes of PUDs ranged from 18 to 124 nm. The highest hydroxyl mixed polyol derived PUD film (PUD-35 film) exhibited high thermal stability, mechanical strength; Tg value, water contact angle value, chemical, and abrasion resistance properties due to the extended siloxane cross-link network structure. The introduction of ionizable polyol into the soft segment led to an improvement in hard and soft segment phase mixing of PUDs, and this strategy could enrich the exploration of new synthetic methodologies in the field of bio-based PUD manufacturing.


2020 ◽  
Vol 49 (5) ◽  
pp. 401-408
Author(s):  
Haojia Su ◽  
Zhengchun Cai ◽  
Zhengwei lv ◽  
Yongkang Chen ◽  
Yongxin Ji

Purpose In this work, the authors used reversible addition-fragmentation transfer (RAFT) polymerization to develop a new cationic acrylate modified epoxy resin emulsion for water-borne inkjet which have the advantages of both polyacrylate and epoxy resin. The emulsion was successfully used in the canvas coating for inkjet printing. This paper aims to contribute to the development of novel cationic emulsions for inkjet printing industry. Design/methodology/approach In this work, the epoxy acrylate was synthesized from RAFT agent and epoxy resin firstly. Cationic macromolecular emulsifier was prepared by RAFT polymerization, using 2,2’-Azobisisobutyronitrile as initiator, 2-(dimethylamino)ethyl methacrylate and styrene as monomer, which was directly used to prepare the emulsion. The influences of the amount of 2-(dimethylamino)ethyl methacrylate on particle size, zeta potential and water contact angle were studied. Finally, the cationic emulsion was used to print images by inkjet printing. Findings The emulsion has the smallest particle size, the highest potential and the highest water contact angle when the DM content is 13 Wt.%. The transmission electron microscopy analysis reveals the latex particles is core-shell sphere with the diameters in the range 120–200 nm. The emulsion was successfully used in the canvas coating for inkjet printing. This work will contribute to the development of novel cationic emulsions for inkjet printing industry. Originality/value The emulsion was successfully used in the canvas coating for inkjet printing. This work will contribute to the development of novel cationic emulsions for inkjet printing industry.


2013 ◽  
Vol 690-693 ◽  
pp. 1620-1623 ◽  
Author(s):  
Chang Qing Fu ◽  
Meng Xu ◽  
Zheng Yang ◽  
Qing Gui Lv ◽  
Liang Shen

The core-shell polyurethane-acrylate(PUA) emulsion containing fluorine and silicon in the core was synthesized by “one-pot” emulsion polymerization in the presence of castor oil-based polyurethane without traditional emulsifier, using methyl methacrylate (MMA), butyl acrylate (BA) as the main monomers, dodecafluoroheptyl methacrylate (G04), γ-methacryloxy propyl trimethoxyl silane (KH-570) as the functional monomers. The structure and properties of the fluorinated-silicated PUA and their films were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectrum (FT-IR) and contact angle testing. The results showed that fluorine and silicon monomers had effectively copolymerized with acrylic monomers and a core-shell structure in the latex was formed. The water contact angle for film-air interface is 92.5o, and the cetane contact angle for film-air interface is 47.5 o.


Coatings ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 32
Author(s):  
Jie Liu ◽  
Feifei Zhang ◽  
Yinghu Song ◽  
Kun Lv ◽  
Ni Zhang ◽  
...  

In this research, the epoxy silicone oil and self-made hydroxyl-terminated hyperbranched polymer (HBP-OH) were used to synthesis the nonionic hyperbranched organosilicone surfactant (NHSi). The molar rate of hydroxyl groups of HBP-OH and epoxy groups of epoxy silicon oil (n-OH: n-epoxy) was adjusted from 5:1~60:1 to prepare a series of NHSi. The Gel Permeation Chromatography (GPC), Fourier Transform Infrared Spectroscopy (FT-IR), contact angle measuring instrument, surface tensiometer and Scanning Electron Microscope (SEM) were employed to characterize the structure and property of HBP-OH and NHSi. GPC analysis indicated that the Mn of HBP-OH was 340.5. FT-IR analysis showed that with the increase of molar rate of n-OH:n-epoxy, the peak intensity of –OH increased. The prepared NHSi was then used to prepare the water solution. The lowest surface tension of NHSi solution was 24.71 mN·m−1 when the n-OH:n-epoxy was 30:1 in the preparation process. The minimum water contact angle of waterborne polyurethane (WPU) emulsion by adding 2% of NHSi was 14.85° on the surface of glass. The wetting experiments showed that the NHSi has good wetting ability to fixed sea-island superfine fiber synthetic material.


2019 ◽  
Vol 9 (2) ◽  
pp. 267-277
Author(s):  
Gang Liu ◽  
Chunlin Liu ◽  
Yuyuan Chen ◽  
Shuai Qin ◽  
Suyuan Yang ◽  
...  

<P>Background: Stimuli-responsive microgels have attracted extensive investigations due to their potential applications in drug delivery, catalysis, and sensor technology. The self-assembled mcirogel films can contain different functional groups (e.g., -COOH, -NH2, -C=ONH2) to interact with specific molecules and ions in water, and their study is becoming increasingly important for developing both absorbent materials and sensor coatings. This paper is aimed to obtain a better understanding of the LbL multilayer formation of microgels and the branched PEI using the mass sensitive QCM. Additionally the influence of the temperature and pH on the formation of the microgel films can be achieved. </P><P> Methods: The temperature and pH sensitive P(NIPAM-co-AA-co-TMSPMA) microgels were prepared by surfactant-free emulsion polymerization and confirmed by FT-IR, laser particle size analysis, and SEM. The obtained microgel and PEI were further used to prepare multilayer thin films by the LbL self-assembly technique monitored by QCM, and their morphology and hydrophilic properties were determined by AFM and water contact angle measurements. </P><P> Results: The thermosensitive and pH sensitive P(NIPAM-co-AA-co-TMSPMA) microgels were prepared by surfactant-free emulsion polymerization. The size and swelling properties of the microgels prepared are highly dependent on the preparation conditions such as the AA and crosslinker content, and microgels showed good temperature and pH responsive properties. SEM images showed that microgels dispersed evenly on the substrate and had a uniform particle size distribution, which was consistent with the light particle size analysis results. Furthermore, multilayer films composed of the negatively charged microgels and the positively charged PEI have been built up by a facile LbL assembly method and the influence of the deposition conditions on their formation was monitored in real time by QCM. Compared to the temperature of 25 °C, the high temperature of 35°C above the phase transition temperature leads to the more adsorbed mass of microgels on the gold surface of QCM sensors. The absorbed mass values at the deposition pH 7 and 10 are 9.82 and 7.28 µg cm-2, respectively, which are much higher than 1.51 µg cm-2 of the layers deposited at pH 4. The water contact angle and AFM both confirmed the wettability properties and morphology of multilayers on the gold surface of QCM sensors. </P><P> Conclusion: The formation of the multilayer films on the gold surface by the layer-by-layer deposition technique of the negatively charged microgels and the oppositely charged PEI can be achieved. The controllable multilayer formation can be attributed to the size difference, changes in the hydrophilic property and surface charge density of microgels responsive to the external temperature and pH.</P>


2013 ◽  
Vol 395-396 ◽  
pp. 351-354
Author(s):  
Qin Huan Yang

Cationic polyfluoroacrylate has been synthesized in the dual presence of cationic and non-ionic emulsifiers. Optimization studies indicated that the optimal proportions of cationic emulsifier 1631 and non-ionic emulsifiers FSA and AEO-9 were 1.75%, 1.25%, and 0.08%, respectively. Under these conditions, the conversion to the polymer was 92.5%, the particle size was 142 nm, and the water contact angle on a polymer film surface was 94.0°. With increasing dosage of hydrocarbon emulsifier, the water contact angles of copolymer films decreased dramatically. The magnitude of this decrease for a polymer with low fluoride content was greater than that for a polymer with high fluoride content. The fluorinated emulsifier FSA behaved similarly to the hydrocarbon emulsifier.


Polymers ◽  
2020 ◽  
Vol 12 (6) ◽  
pp. 1284
Author(s):  
Elizabeth Vázquez ◽  
Claudia Muro ◽  
Javier Illescas ◽  
Guillermina Burillo ◽  
Omar Hernández ◽  
...  

Polysulfone (PSU) film and N-vinylimidazole (VIM) were used to obtain grafted membranes with high hydrophilic capacity. The grafting process was performed by gamma irradiation under two experiments: (1) different irradiation doses (100–400 kGy) and VIM 50% solution; (2) different concentration of grafted VIM (30–70%) and 300 kGy of irradiation dose. Characteristics of the grafted membranes were determined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), contact angle, swelling degree, desalination test, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Both experiments indicated that the absorbed dose 300 kGy and the VIM concentration, at 50% v/v, were effective to obtain PSU grafted membranes with 14.3% of grafting yield. Nevertheless, experimental conditions, 400 kGy, VIM 50% and 300 kGy, VIM 60–70% promoted possible membrane degradation and VIM homopolymerization on the membrane surface, which was observed by SEM images; meanwhile, 100–200 kGy and VIM 30–50% produced minimal grafting (2 ± 0.5%). Hydrophilic surface of the grafted PSU membranes by 300 kGy and VIM 50% v/v were corroborated by the water contact angle, swelling degree and desalination test, showing a decrease from 90.7° ± 0.3 (PSU film) to 64.3° ± 0.5; an increment of swelling degree of 25 ± 1%, and a rejection-permeation capacity of 75 ± 2%. In addition, the thermal behavior of grafted PSU membranes registered an increment in the degradation of 20%, due to the presence of VIM. However, the normal temperature of the membrane operation did not affect this result; meanwhile, the glass transition temperature (Tg) of the grafted PSU membrane was found at 185.4 ± 0.5 °C, which indicated an increment of 15 ± 1%.


Crystals ◽  
2020 ◽  
Vol 10 (3) ◽  
pp. 196 ◽  
Author(s):  
Hatem Abushammala ◽  
Jia Mao

The hydrophilicity of cellulose nanocrystals (CNCs) is a major challenge for their processing with hydrophobic polymers and matrices. As a result, many surface modifications have been proposed to hydrophobize CNCs. The authors showed in an earlier study that grafting alcohols of different chain lengths onto the surface of CNCs using toluene diisocyanate (TDI) as a linker can systematically hydrophobize CNCs to a water contact angle of up to 120° depending on the alcohol chain length. Then, the hydrophobized CNCs were used to mechanically reinforce poly(butylene succinate) (PBS), which is a hydrophobic polymer. As a result of hydrophobization, PBS/CNCs interfacial adhesion and the composite mechanical properties significantly improved with the increasing CNC contact angle. Continuing on these results, this paper investigates the impact of CNC surface properties on the crystallization behavior of PBS using differential scanning calorimetry (DSC). The results showed that the crystallization temperature of PBS increased from 74.7 °C to up to 86.6 °C as a result of CNC nucleation activity, and its value was proportionally dependent on the contact angle of the CNCs. In agreement, the nucleation activity factor (φ) estimated using Dobreva and Gutzow’s method decreased with the increasing CNC contact angle. Despite the nucleation action of CNCs, the rate constant of PBS crystallization as estimated using the Avrami model decreased in general as a result of a prevailing impeding effect. This decrease was minimized with increasing the contact angle of the CNCs. The impeding effect also increased the average activation energy of crystallization, which was estimated using the Kissinger method. Moreover, the Avrami exponent (n) decreased because of CNC addition, implying a heterogeneous crystallization, which was also apparent in the crystallization thermograms. Overall, the CNC addition facilitated PBS nucleation but retarded its crystallization, and both processes were significantly affected by the surface properties of the CNCs.


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