Synthesis and characterization of eugenol-based silicone modified waterborne polyurethane with excellent properties

A eugenol-based silicone-containing monomer 4,4′-(1,1,3,3-tetramethyldisiloxane-1,3-dipropyl)bis-2-methoxyphenol(EUSi) was synthesized from eugenol and 1,1,3,3-tetramethyldisiloxane via the hydrosilylation reaction. And waterborne polyurethane (WPU) with excellent properties was obtained by using EUSi as a type of diol chain extender. The unique combination of rigidity and flexibility in the chemical structure of EUSi greatly facilitated the mechanical properties, thermal properties, and water resistance of WPU. With only a 3% dosage of EUSi, the maximum tensile strength was increased from 6.2 to 22.4 MPa, while the water absorption was decreased from 31.3% to a surprisingly 7.6%. Our work provides a new convenient strategy for the preparation of organosilicon-modified WPU with improved performance.     

UV-shielding by a polyurethane/f-Oil fly ash-CeO2 protective coating

A waste material called oil fly ash (OFA) was acid-functionalized, yielding f-OFA-COOH, which was then reacted with cerium oxide (CeO₂) to make CeO₂-functionalized OFA, or f-OFA-CeO₂. Pristine OFA and f-OFA-CeO₂ were used to make waterborne polyurethane (WBPU) dispersions, referred to as WBPU/OFA and WBPU/f-OFA-CeO₂, respectively, with defined OFA and f-OFA-CeO₂ content. All the dispersions were applied to mild steel as organic coatings to evaluate their protective properties, such as their hydrophobicity, adhesive strength and UV-shielding resistance. These protective properties varied based on the OFA and f-OFA-CeO₂ content. The highest water contact angle, minimum water swelling and maximum adhesive strength were found using WBPU/f-OFA-CeO₂-20 coating (using 2.00 wt% f-OFA-CeO₂), which also showed the maximum ultraviolet (UV) absorption via UV–vis spectroscopy analysis. This UV shielding result also matched field test results, as that coating was found to exhibit the lowest UV degradation near a marine atmosphere, as shown by X-ray photoelectron spectroscopy (XPS) analysis. The least affected hydrophobicity was also recorded for the sample with the WBPU/f-OFA-CeO₂-20 coating.     

Enhancing flame retardant and antistatic properties of polyamide 6 by a grafted multiwall carbon nanotubes

In order to improve the flame retardancy and antistatic properties of polyamide 6 (PA6) at as low amount of additives as possible, an integrated-functional additive was synthesized by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and multiwalled carbon nanotubes (MWCNTs). The results showed 2 wt% of DOPO-MWCNTs distributed in PA6 formed an electric network and decreased volume resistivity sharply to 3.1 × 10⁸ Ω cm. In other words, it helped PA6 to get to the percolation threshold of semiconductor. By using of 3 wt% DOPO-MWCNTs, the severe dripping in burning of PA6 was almost controlled. The possible reason was also ascribed to the network formed by evenly dispersed DOPO-MWCNTs, which strengthened the char structure and held severe dripping of PA6. As a result, the heat and smoke release were also suppressed obviously. The most important is that CO release was about half cut in CONE test.     

Aramid pulp treated with imidazolium ionic liquids as a filler in rigid polyurethane bio-foams

This article reports an aramid pulp (AP) treated with two ionic liquids (IL), namely 1-n-butyl-3-methylimidazolium chloride (C₄.Cl) and 1-carboxymethyl-3-methylimidazolium chloride (HO₂C), and its use as a filler in reinforced rigid polyurethane foams (RPUF). The RPUF were incorporated with the treated AP at three weight fractions (c.a. 0.1, 0.5, and 1.0 wt%) and were produced by the free rising method. The results showed that the studied IL promoted a better interaction between the AP and the RPUF system, which increased the overall reactivity, imparting a higher cell anisotropy. This also yielded a positive effect in mechanical properties and thermal stability of the RPUF. Compared to the neat RPUF, outstanding increases of approximately 50 and 20% were achieved in compressive modulus and strength, respectively. In all, the use of IL promoted increased compatibility between matrix and reinforcement, especially that HO₂C IL.     

High-efficiency ammonium polyphosphate intumescent encapsulated polypropylene flame retardant

The flame retardant polypropylene containing the micro-envelope core-shell structure flame retardant, which encapsulated ammonium polyphosphate into melamine-formaldehyde resin and sodium silicate through in situ polymerization was prepared with polyamide 6, added as a carbon-forming agent. The composition of ammonium polyphosphate, encapsulated ammonium polyphosphate with melamine-formaldehyde resin and the micro-envelope core-shell structure flame retardant were characterized. The fire safety and thermal stability were investigated and showed an improvement including limiting oxygen index, thermogravimetric analysis, vertical burning tests, and microscale combustion calorimeter. The burned compounds were also studied to confirm the burning mechanism. The results showed the flame retardant performance had been greatly improved, while polyamide 6 had better char-forming effect. Besides, the water solubility of flame retardants and their influence on the mechanical properties of polypropylene were also investigated. The results on the effects of additives demonstrated a high efficiency flame retardant to polypropylene. A core-shell flame retardant that sodium silicate and melamine-formaldehyde resin-coated ammonium polyphosphate had been constructed. The effect of the built flame retardant system on the combustion performance of polypropylene was studied from the mechanism and performance. The LOI of the most flame retardant polypropylene reached 28.6%, and UL-94 reached the V-0 level.     

Tailoring new bisphenol a ethoxylated shape memory polyurethanes

Shape memory polyurethanes (SMPUs) have generated great attention because of their unique properties. These properties are result of a particular molecular structure consisting of flexible molecular chains with low glass transition temperatures alternating with hard urethane segments. In this field, bisphenol A (BA) has been used for a long time as chain extender due to the good properties of the obtained SPMU materials. Nevertheless, the high toxicity of this compound has caused a high decrease on its use. For this reason, it has been selected a lower toxicity compound, bisphenol A ethoxylate (BAE). In this work, it is described a new SMPUs based on BAE and the influence of the hard segment on the thermo-mechanical properties and shape memory capacity. For that, both the proportion of the components and the diisocyanate employed (2,4-toluene diisocyanate (TDI), 4,4′-methylene bis(phenylisocyanate) (MDI) or a TDI/MDI mixture) have been modified. Then, depending on the molecular architecture achieved, the polyurethanes present different properties, which were studied by different techniques, such as thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dynamic-mechanical thermal analysis (DMTA). It has been observed that glass transition temperature (T_g) increases as the hard phase content in the PU samples increases. In addition, T_g-MDI > T_g-MDI-TDI > T_g-TDI, so it is possible to control the T_g of the material, that is, shape memory transition temperature varying the diisocyanate. Finally, the shape memory capacity of the PUs was evaluated by thermo-mechanical analysis (TMA). All the synthesized PUs have shown good shape memory effect with fixation ratios up to 80% and recovery ratios close to 100%.     

Melt processing of nanocomposites of cellulose nanocrystals with biobased thermoplastic polyurethane

Nanocomposites of thermoplastic polyurethane (TPU) with cellulose nanocrystals (CNC) without and with surface treatment are obtained by melt processing. Nanocomposites are obtained with nanofiller weight content near of the theoretical percolation threshold (3.9 wt%). Visual observation of CNC agglomerates is sufficient to prove the inefficiency of the mixing in systems with untreated CNC. The crystallization kinetics of the TPU changes with the addition of CNC and this is confirmed by differential scanning calorimetry analysis. Thermogravimetric analysis prove that the addition of CNC increases the thermal stability of the TPU. From the rheological analysis it is possible to verify the absence of percolation and an intermediate state of sol–gel transition in the nanocomposites. CNC/TPU nanocomposites with 5 wt% of treated CNC present better mechanical performance than de neat TPU and the other processed nanocomposites and display around 130% increase in Young's modulus while retaining significant values of toughness, tensile strength and elongation at break.     

Effect of expandable graphite and ammonium polyphosphate on the thermal degradation and weathering of intumescent fire-retardant coating

This research aims to study the effect of ammonium polyphosphate and expandable graphite on the intumescent coating formulations (ICF). The coating presented in this research article is based on carbon source expandable graphite (EG), blowing agent melamine, acid source ammonium polyphosphate (APP), epoxy resin as a binder with polyamide amine. The stability of the developed coating was verified at 950°C for 1-hour fire test. The results showed that the coating is stable and well bond with the steel substrate. The char was characterized by using FESEM, XRD, FTIR, DTA, TGA, XPS, Py-GCMS and Weathering Test. The morphology of the char was studied by SEM of the coating after furnace fire test. XRD and FTIR show the presence of graphite, borophosphate; boron oxide and sassolite in the residual char. TGA and DTG disclosed that EG improved the residual mass of coating. XPS analysis showed the char residue of IF5-APP-EG contains carbon and oxygen contents 47.50 and 40.70, respectively. Py-GCMS analysis described that the IF5-APP-EG released less gaseous compounds. The weathering test illustrated that's the char expansion of coatings samples was decreased due to the presence of a humid environment and UV light. The IF5-APP-EG showed the maximum char expansion, lower substrate temperature and high residual weight among the studied formulations.     

Structure and properties of bio-based polyurethane coatings for controlled-release fertilizer

Two kinds of bio-based polyurethane coatings for controlled-release urea were prepared by in-situ polymerization used castor oil and liquefied starch as raw materials, respectively. Scanning electron microscopy (SEM) showed that the section morphology of castor oil based polyurethane (Castor-PU) coating was uniform and dense, and that of liquefied starch based polyurethane (Starch-PU) coating had certain proportion of microporous. Infrared spectroscopy (IR) showed that the two coatings had typical urethane characteristic structure, but the difference was that the Starch-PU had obvious unreacted isocyanate structure. Differential scanning calorimetry (DSC) showed that the glass transition temperature of the two coatings was around 58°C, but the Castor-PU had a crystallization domain with obvious crystallization melting peak at 130°C. Thermogravimetric analysis (TG) showed that the thermal stability of Castor-PU was significantly higher than that of Starch-PU. The controlled-release property test showed that when the coating ratio was 2.8%, the nutrient release longevity of urea coated with Castor-PU was 49 days and that of urea coated with Starch-PU was 14 days. The reasons for the poor controlled-release performance of Starch-PU were analyzed, which probably caused by concentrated sulfuric acid and hydrophilic dispersant added in the liquefied starch.     

Acrylic-based fire-retardant coatings for steel protection: Employing the concept of in situ ceramization

Traditional intumescent coatings are widely used as passive fire-protective coatings for steel structures as they are capable of expanding in the range of 20–50 times the original thickness thereby providing excellent insulation. However, the fragile nature of such residue and susceptibility to thermo-oxidation given their carbonaceous nature are key problematic issues. The concept of in situ ceramization is explored in this work as a means to form inorganic cohesive char with improved rigidity and thermo-oxidative stability. Coating samples were prepared by incorporating ammonium polyphosphate, talc, Mg(OH)₂, and polydimethylsiloxane as additives into acrylic resin at different weight fractions. Thermal analysis and x-ray diffraction have confirmed the reactions between the additives to form various crystalline magnesium phosphate phases, and to a small extent, silicon phosphate, thereby ensuring the thermo-oxidative stability of the residue. This is reiterated by the fire performance tests (by exposing the coatings to a temperature profile in a furnace similar to ISO 834 fire curve). Despite the advantages of rigid char and its thermo-oxidative stability as a result of formation of inorganic phosphates, the lack of swelling has resulted in relatively poor insulation capabilities of the char, and subsequently, compromised the fire protection times (that are in the range of 45–55 min). However, pyrolysis flow combustion calorimeter results of the coatings are promising and have shown a significant drop of up to 70% in the peak of heat release rate values as compared to neat resin.