INTUMESCENT UNSATURATED POLYESTER RESIN WITH LEATHER POLISHING POWDER AND AMMONIUM POLYPHOSPHATE.

Abstract

Unsaturated polyester resin is commonly used in the production of molded parts, composite materials, nanocomposites, and materials with natural and glass fibers, as well as in the production of polymer concrete, etc. However, its major drawbacks are its rapid combustion and the burning droplets that detach from the material, causing secondary fires. Therefore, the present invention aims to describe the composition of a mixture of unsaturated polyester resin with ammonium polyphosphate and powdered residue from the leather polishing process. These additives exhibit a synergistic chemical reaction, giving the composition intumescent flame-retardant properties that meet the V0 classification, according to the UL94 flammability evaluation method in a vertical position. This thermosetting resin possesses sufficient physical and mechanical properties to also be used in the construction and roadway industries.

Description

Intumescent unsaturated polyester resin with leather polishing powder and ammonium polyphosphate OBJECT OF THE INVENTION The present invention aims to describe the composition of a mixture of unsaturated polyester resin with ammonium polyphosphate and the powder residue from the leather polishing process, with flame-retardant intumescent properties, which complies with the V0 classification, according to the UL94 evaluation method in a vertical position. The thermosetting resin produced has flame-retardant properties and sufficient physical and mechanical properties to be used in the construction and road industry, composite materials, nanocomposite materials, fiberglass composites, polymer concrete for the manufacture of streets, sidewalks, walkways, runways, etc. BACKGROUND The current economy, based on a linear flow of materials and energy (the take-make-throw-away concept), contributes to the rapid consumption of raw materials and the generation of waste, whose inappropriate management degrades the ecosystem. Hence the need for solutions that allow industry to reduce its negative impact on the environment and simultaneously meet consumer expectations. The circular economy involves a cyclical flow of materials and energy that focuses on the remanufacturing, repair, and upgrading of components; that is, the use of renewable resources and the reuse of waste as secondary raw materials. The circular economy model is, by far, more economical than the traditional economy (lower consumption of energy and non-renewable resources) and more beneficial to the environment (reuse of waste, lower emissions of pollutants). This model drives business development by introducing innovative technologies and improving their performance.As an example, the industry of. QQQRnn / ZZnZ / B / YIAI Leather is one of the most polluting and resource-intensive industries. Approximately 250 kg of leather is produced from 1,000 kg of virgin leather, requiring 15 to 120 m3 of water. The process generates 15,000 to 50,000 liters of wastewater and 400-700 kg of waste, not to mention odors, greenhouse gases (CO2, H2S, NH3), and volatile organic compounds (amines, aldehydes, and hydrocarbons). The amount of chemicals emitted depends on the type of treatment and the technology used to process the leather. Global production capacity is estimated at approximately 15 metric tons of leather per year, demonstrating the scale of the problem. Until now, landfilling and partial disposal of waste were the only practices used in waste management. Tannery waste is a renewable resource of valuable substances, and its reuse could be an important step toward sustainable development.For example, 2 to 6 kilograms of polishing dust are produced per 1000 kg of processed leather, which is practically collagen. Katarzina Chojnacka, Dawid Skrzypczak, Katarzina Mikula, Anna Witek-Krowiak, Grzegorz Izydorczyk, Ksawery Kuligowski, Paulina Bandrów, Marek Kulazynski. Progress in sustainable technologies of leather waste valorization as Solutions for the circular economy. Journal of Cleaner Production, 313, 2021, 127902. This waste has also been studied to manufacture activated carbon, as exemplified by R. Gila, B. Ruiza, M.S. Lozanob, E. Fuentea. Influence of the pyrolysis step and the tanning process on KOH-activated carbons from biocollagenic wastes. Prospects as adsorbent for CO2 capture. Journal of Analytical and Applied Pyrolysis 110 (2014) 194–204. They use a mixture of leather waste, treated with vegetable tanning, and treat it with KOH for activation, and then carry it to pyrolysis.The activated carbons prepared are essentially microporous, with a certain degree of mesoporosity, and contain a significant amount of nitrogen. The activated carbons obtained showed high adsorption capacities for CO2, low to moderate for CH4, and very low adsorption capacities for H2 at high pressures. To study the effect of vegetable tanning, defatted, dehydrated hide and a mixture of commercial tannins were used as reference materials. The data obtained by thermogravimetry indicated that the... QQQRnn / ZZnZ / B / YIAI interactions between tannin and collagen increased the thermal stability of leather waste and H2O, CO, CO2, H2, CH4, CxHy, NxOy, SO2 and toluene were the main gases produced during pyrolysis. The resulting sorbent materials showed high specific surface area and total pore volume up to 1602 m2g-1 and VTOT of 0.695 cm3g'1, respectively. Direct chemical activation of the materials increased the median micropore volume and micropore size. Also, Alba Cabrera-Codony, B. Ruiz b, R.R. Gil, Lucia Alexandra Poparían, Eric Santos-Clotas, María J. Martín, E. Fuente. From biocollagenic waste to efficient biogas purification. Applying circular economy in the leather industry. Environmental Technology & Innovation 21 (2021) 101229, studied industrial biocollagenic waste with vegetable tanning.They treat them by chemical activation (KOH, NaOH, K2CO3), with and without prior pyrolysis, the results present low-cost, sustainable activated carbons, and the obtained materials proved to be efficient for gaseous pollutant reduction applications. They exhibit good chemical and textural properties, with BET specific surface area and total pore volume of up to 1600 m2g1 and 0.76 cm3g1, respectively. These efficient activated carbons also showed a siloxane adsorption capacity of up to 500 mg g-1, higher than that of commercial steam-activated carbons supplied by adsorbent producers that reach values ​​of up to 349 mg g-1. Waseem Hittini, AbdelHamid I. Mourad, Basim Abu-Jdayil. Cleaner production of thermal insulation boards utilizing buffing dust Waste. Journal of Cleaner Production 236 (2019) 117603, developed an insulating composite of polystyrene and skin dust residue. .The prepared insulation composites show better performance than pure polystyrene insulation panels. This study shows that adding 10% by weight of powder to polystyrene composites reduces the thermal conductivity of the board by 13%. All the prepared composites showed higher thermal conductivity (0.044–0.056 W / mK), compressive strength (11.55–8.23 MPa), and flexural strength (29.51–10.53 MPa) compared to the conventional thermal combination. Polishing powder (from 5% by weight to 25% by weight) was used. The blends were mixed using an extruder and a. QQQRnn / ZZnZ / B / YIAI hot pressing machine. The thermal, physical and mechanical properties. On the other hand, H. Lakrafli , S. Tahiri, A. Albizane, M.E. El Otmani. Effect of wet blue chrome shaving and buffing dust of leather industry on the thermal conductivity of cement and plaster based materials. Construction and Building Materials 30 (2012) 590-596, present an experimental study of the effect of the addition of leather waste and polishing powder (BD), on the mechanical and thermal properties of specimens composed of cement and plaster. The results obtained show a significant decrease in density, mechanical strength and thermal conductivity. The use as a separating or filling material considerably increases the thermal insulation capacity. To avoid a decrease in mechanical strength, leather waste can be used to fill hollow samples or to separate panels with an increased content of tannery waste.The determination of the thermal conductivity of all samples showed that the incorporation of tanned waste into the formulation of cement or plaster significantly increases the thermal insulation capacity. K. Chronska, A. Przepiorkowska. Buffing dust as a filler of carboxylated butadiene-acrylonitrile rubber and butadiene-acrylonitrile rubber. Journal of Hazardous Materials 151 (2008) 348-355, describe that buffering dust from chrome-tanned leather is one of the most difficult tannery wastes to manage. It is also hazardous to both human health and the environment. Mixtures with rubber improved mechanical properties and increased resistance to thermal aging, as well as electrical conductivity and crosslink density of vulcanizates. Sylwia Cztonkaa, Massimo F. ​​Bertinob, Krzysztof Strzeleca, Anna Strqkowskaa, Marcin Maslowskia. Rigid polyurethane foams reinforced with solid waste generated in leather.Industry Polymer Testing 69 (2018) 225–237. This study presents the results of adding leather powder residues to rigid polyurethane foams. It was found that the addition of leather powder leads to notable changes in several properties, mainly in foam morphology, bulk density, thermal conductivity, and mechanical strength. The results show that compared to the reference foam, the composition modified with 0.1 wt% of powder provides higher density. QQQRnn / ZZnZ / B / YIAI (36.9 kg / m3), higher compressive strength (216 kPa), lower water absorption (9% after 24 h) and thermal conductivity (0.026 W / m K). However, the addition of tannery waste powder was also found to have a negative effect on the cell morphology, leading to the deterioration of the physical-mechanical properties of the modified foams. Qilin Wen, Xintao Wu, Weixing Xu, B¡ Shi. Effects of dispersion and fixation of collagen fiber network on its fiber retardancy. Polymer Degradation and Stability 175 (2020), 109122. In this study, the results of using collagen fibers as a flame retardant agent are presented. It was found that since collagen fibers have a nitrogen content, they have the potential to be transformed into an effective flame retardant filler. Due to these properties, these collagen fibers can be considered as a valuable flame retardant modifier for polymeric materials. With zirconium tanning agent, they showed the best performance. The results showed that flame retardancy improved with an increase in the degree of dispersion of collagen fibers and removal of interfibrillar substance. Its LOI, total heat release, char yield at 800 °C, and thermal conductivity were 62.3%, 15.51 MJ m2, 18.33%, and 0.1362 W ητ1K1, respectively. Katarzyna Chojnacka, Dawid Skrzypczak, Katarzyna Mikula, Anna Witek-Krowiak, Grzegorz Izydorczyk, Ksawery Kuligowski, Paulina Bandr'ow, Marek Kulazynski.Progress in sustainable technologies of leather waste valorization as solutions for the circular economy. Journal of Cleaner Production 313 (2021) 127902. This study considers the circular economy of the tanning industry. It is estimated that leather processing produces 200 times more waste than the total leather product. A review of methods that offer recycling of tannery materials is presented, including chemical, thermal, and biological techniques to recover chromium, nutrients, collagen hydrolysate, fats, biogas, and anaerobic digestate, which can be used in other industrial processes. Rethinam Senthil, Thiagarajan Hemalatha,. QQQRnn / zznz / e / Yi Ramasamy Manikandan, Bhabendra Nath Das, Thotapalli Parvathaleswara Sastry. Leather boards from buffing dust: a novel perspective. Olean Techn Environ Policy (2015) 17:571–576. This study investigates the potential of manufacturing synthetic leathers from leather sanding dust bonded with natural rubber. They found that leathers can be made with good appearance for use in shoes, linings, etc. The material was prepared from leather polishing dust using rubber latex as a binder. Rethinam Senthil, Sundaramurthy Inbasekaran, Nallathambi Gobi, Bhabendra Nath Das, Thotapalli Parvathaleswara Sastry. Utilization of finished leather wastes for the production of blended fabrics. Olean Tech Environ Policy (2015) 17:1535–1546. This study presents the conversion of waste leather residue into useful resources. Leather fibers were extracted from tannery waste and blended with cotton and polyester.The mechanical properties displayed by these fibers make them suitable for use in the textile industry, solving two problems: waste management and the generation of sustainable profits. DETAILED DESCRIPTION OF THE INVENTION This invention describes the product of unsaturated polyester resin mixtures that are specifically modified by the addition of the product of leather sanding (leather dust or scraping) and ammonium polyphosphate, which results in a self-extinguishing, flame-retardant intumescent material (production of an insulating carbon layer upon contact with high temperatures). The intumescent effect is a result of the synergy between the rasp and the ammonium polyphosphate. It was determined that polyester resin with rasp does not produce a flame retardant effect, nor does polyester resin with ammonium polyphosphate. However, the combination of both, at certain concentrations, produces a synergistic effect, and the intumescent effect occurs. QQQRnn / ZZnZ / B / YIAI To obtain the compound, it is essential, as a first step, to dehumidify the scrape (which has an approximate humidity concentration of 6%) to levels of 0.5%. Unsaturated polyester resin, raspberry, and ammonium polyphosphate are physically mixed in a ratio of 10 to 40% by weight of ammonium polyphosphate and 1 to 20% raspberry. Mixing is carried out in a container with vigorous stirring at room temperature until both additives are completely dispersed and distributed, for 5 to 10 minutes of stirring. The mixture is then allowed to stand for 20 to 30 minutes to allow the bubbles caused by stirring to disappear, or the mixture is vacuum-packed for 5 minutes. Between 2 and 6% methyl ethyl ketone peroxide is added to the mixture obtained by the previous procedure as a catalyst, and between 1 and 3% cobalt octoate is added as an accelerator of the cross-linking reaction. The ratio of catalyst to accelerator determines the reaction set time. A set time of 15 minutes is sufficient for manufacturing castings or distributing the material in molds. The self-extinguishing, intumescent, and flame-retardant unsaturated polyester resin formulated with ammonium polyphosphate and rasp can be used in the production of profiles, plates, molded objects, car and truck bodies, polymer concrete, streets, sidewalks, fire walkways, etc. EXAMPLES The following examples are intended to illustrate the invention but in no way limit it. Table 1 shows the results of combustibility testing of different formulations under the Underwriters Laboratories (UL94) standard. Compliance means the test tube is held upright, the flame is extinguished within 10 seconds when removed from the test tube, and there is no dripping. QQQRnn / ZZnZ / B / YIAI Table 1 Polyester resin XXXX Styrene monomer XXXX Cobalt octoate XXXX Methyl ethyl ketone peroxide XXXX Scrape (skin powder) XX Ammonium polyphosphate XX VO fail fail fail comply QQQRnn / ZZnZ / B / YIAI Table 2 presents the composition (formulation) of self-extinguishing and intumescent unsaturated polyester resin that complies with the VO classification. Parts Polyester resin 20 Styrene monomer 7 Cobalt octoate 0.4 Methyl ethyl ketone peroxide 0.8 Rasp (skin powder) 1 Ammonium polyphosphate 4

Claims

1. A polymeric material characterized in that it is a mixture formed from the following elements: a) Unsaturated polyester resin, b) Styrene monomer in a concentration between 10 and 40% by weight, with respect to the weight of the resin; c) Methyl ethyl ketone peroxide in a concentration between 2 and 6% by weight, with respect to the weight of the resin; d) Cobalt octoate in a concentration between 1 and 3% with respect to the weight of the resin; e) Skin powder (rasp) in a concentration between 1 and 20% by weight, with respect to the weight of the resin; f) Ammonium polyphosphate in a concentration between 10 and 40% by weight, with respect to the weight of the resin.

2. The polymeric material according to claim 1; characterized in that the unsaturated polyester resin can be orthophthalic, isophthalic, and isophthalic / neopentyl glycol.

3. The polymeric material according to claim 1, characterized in that in the physical mixture of unsaturated polyester resin and styrene monomer, the concentration of styrene monomer with respect to the weight of the resin is preferably 35% by weight.

4. The polymeric material according to claim 1, characterized in that in the physical mixture of unsaturated polyester resin and methyl ethyl ketone peroxide (MECK), the concentration of MECK with respect to the weight of the resin is preferably 4% by weight.

5. The polymeric material according to claim 1, characterized in that in the physical mixture of unsaturated polyester resin and cobalt octoate, the concentration of cobalt octoate with respect to the weight of the resin is preferably 2% by weight. QQQRnn / ZZnZ / B / YIAI 6. The polymeric material according to claim 1, characterized in that in the physical mixture of unsaturated polyester resin and skin powder (rasp), the concentration of rasp with respect to the weight of the resin is preferably 5% by weight.

7. The polymeric material according to claim 1, characterized in that in the physical mixture of unsaturated polyester resin and ammonium polyphosphate, the concentration of ammonium polyphosphate with respect to the weight of the resin is preferably 20% by weight.

8. Use of polymeric nanocomposite materials according to claims 1 to 7, for the production of profiles, plates, molded objects, car and truck bodies, polymeric concrete, streets, sidewalks, firebreak walkways, etc.