EVALUATION OF POLYISOCYANURATE WASTES IN OIL-BASED SYSTEMS

Abstract

The invention relates to the utilization of polyisocyanurate (PIR)-based insulation material waste in oil-based bio-based thermoset systems. Within the scope of this invention, PIR waste generated after production or use is ground into a powder with a size range of 200–400 mesh. The resulting PIR powders are modified with epoxy silane compounds via their surface hydroxyl groups, thus becoming epoxy-functionalized. The modified PIR powders are dispersed in specific ratios within a bio-based epoxy system containing oils and bio-based carboxylic acids. The resulting mixture is cured using a stepwise heating protocol to transform it into a bio-based thermoset composite material. Thanks to this invention, costly and environmentally harmful PIR waste is recovered, resulting in bio-based, environmentally friendly, and recyclable thermoset systems.These systems contribute to waste management in line with sustainability principles and enable the production of high-performance new materials.

Description

POLYISOCYANURATE WASTES IN OIL-BASED SYSTEMS EVALUATION Technical Area The invention relates to the utilization of insulation waste in oil-based systems. The invention specifically concerns polyisocyanurate (PIR) waste powder used as insulation material. thermoset systems made from renewable chemicals It is related to the evaluation. State of the Art One of the biggest problems of today's developing society is waste production. Waste disposal is not at the desired levels due to inadequate waste management. This is not the case. Due to the diversity of waste types, the recycling rates of all wastes are not sufficient. Globally, this figure is around 19%, and recycling rates vary by country. It increases in direct proportion to the level of development. The remaining very large A significant amount of waste is released into nature in various ways. One of these ways is... They are buried in landfills. However, landfills have limited capacity and lifespan. It is necessary to open new landfill sites, and therefore new landfill sites are needed. While opening up is starting to be abandoned in developed countries, this situation is more prevalent here. This is common in underdeveloped countries. Furthermore, these materials are often thrown into landfills. It is also seen as a loss of value. One of the recovery methods is incineration. Energy is recovered, but even though flue gases can be filtered, in the final step... The inevitable release of carbon dioxide into the atmosphere contributes to global warming. Therefore, waste should be recycled instead of being buried or burned in landfills. Transformation always presents itself as the preferred option. PIR The abbreviation stands for polyisocyanurate (in English, polyisocyanurate It is referred to as PIR in the literature. In the PIR production processes, normal isocyanate / polyol ratio is much higher compared to obtaining polyurethane (PUR). This ratio is maintained. This ratio is called the isocyanate index. In normal PUR production, this ratio is maintained. While the index is around 100-110 in other countries, in PIR production this index reaches values ​​of 350. This is observed (Kurańska et al., 2015). The reaction with polyol in a high isocyanate ratio occurs. isocyanate when started (at a higher temperature than normal polyurethane production) 2 The molecules first react with each other to form trifunctional isocyanurate. It forms its molecule. Subsequently, isocyanurate and kala isocyanate groups are combined with the diol. They react to form a mixture of polyisocyanurate (PIR) and polyurethane (PUR) and a complex structure. A thermoset polymer is obtained. The PIR / PUR ratio is changed by altering the index. It can be modified. Although this material is a PIR-PUR mixture, it is PIR material. This is how it is described. Waste from such materials is ground up again or After being compressed, it is mixed again with polyurethane resin or suitable adhesives. They are cured to obtain new materials. Or these wastes are gasified or incinerated. It is disposed of via this method (Scheirs, 1988; Rossignolo et al., 2024). Polyurethane 2020 The production volume was approximately 24 million tons (Rakov, 2020). Approximately one-third of the polyurethane materials are burned, while another third is... It is sent to landfills. The remaining one-third is only recycled. It can be converted (Gomez et al., 2019; Gadhave et al., 2019). PIR material offers better insulation compared to other materials such as XPS and glass wool. It can deliver high performance. Furthermore, it is more suitable for different applications. It has flexible application areas. For example, with XPS. In comparison, XPS melts and drips while burning during any combustion event, whereas PIR... It maintains its integrity only by carbonization. Furthermore, XPS has a maximum operating temperature. While PIR material melts at around 90°C and is safe at around 75°C, it can be safely used at around 120°C. It somehow continues to work (https: / / www.rmax.com / polyiso-vs-xps). This is hot. It is very effective in pipe insulation. Along with rock wool, another popular insulation material. It provides better performance when compared. For example, the same R The rock wool used to achieve this value is 7 times heavier and 2.5 times thicker than PIR. This is necessary because this issue causes difficulties in flooring and also increases costs. It increases (https: / / www.rmax.com / polyiso-vs-mineral-wool). PIR can be produced in the form of laminated sheets with protective layers, as well as... In the future, they will also be produced in large, single-cast masses (slabs) and then applied. It can be processed on the surface in a suitable way. For example, complex pipelines can be processed with PIR. CNC and similar machines are used to process these large, cast pieces in order to apply insulation. Suitable parts can be produced with it. During this production process, a large amount of powdered material is used. The crushed PIR powder, which has no application, is produced as waste. This Dust and end-of-service-life PIR waste pose a problem in terms of disposal. As previously mentioned, the preferred method for disposing of these wastes is burial. If this is done, in addition to environmental impacts, transportation and other costs will arise. 3 This results in the following: When the incineration disposal method is preferred, the final result is... Carbon dioxide is causing a problem, which in turn is increasing carbon emissions. Therefore, exploring ways to recycle this material is important. The amount of waste collected from this material is sufficient for a sustainable chemical transformation. This is not the case. Therefore, mechanical recycling is becoming more prominent. Mechanical recycling involves pulverizing the PIR material and placing it into a suitable system. This involves the integration of the particle sizes of the resulting PIR powders, PIR Regardless of the dimensions in which the materials are prepared, they are processed on a CNC machine. Therefore, it remains largely constant. In the current technique / practice, a patent originating from the Netherlands, WO2012091557A1 (NL2005946C2) PIR powders and / or other thermoset powders, especially for use in toothed boards instead of particleboard. along with other thermoset polymers such as PET, PVC, PP, and PS for the purpose of making facade claddings. It is being mixed up. In another German patent, DE102006021263A1, powdered PIR particles are different. quantities of wood dust, wood fiber, volcanic ash, and thermoplastic polyester, thermoplastic polyester + polyacrylate or thermoplastic polyester + epoxy resin mixed together It is used in the production of panels. In another invention, CN108484127A, PIR powders are combined with other inorganic materials. It is used in the production of high-temperature resistant bricks. The PIR powders here are high-temperature resistant. It decomposes at high temperatures, causing the brick to have a porous structure. Polish patent number PL193835B1 (PL341548A1) describes a heat insulator at 130-150°C. The manufacture of polyisocyanurate type header foams that can be used as such has a moisture content of 5.5% and 5-30% (oligomeric) based on dried distillation waste with particle size <0.1 mm It consists of fillers (based on the total of polyols and polyisocyanates). In conclusion, the solutions in the inventions described above all involve PIR powders. It has been observed that it has not been evaluated in a holistic, bio-based system, and the existing Due to the inadequacy of the solutions on the subject, an improvement is needed in the relevant technical field. It has been deemed necessary to do so. Purpose of the Invention The invention was created by drawing inspiration from existing situations and overcoming the aforementioned drawbacks. It aims to solve the problem. 4 The main objective of the invention is to find a holistic way to dispose of PIR waste, which is costly to dispose of. It is an evaluation within a bio-based system. Another purpose of the invention is to prevent environmental pollution and loss of value by treating these wastes. It is an evaluation. Another aim of the invention is to obtain a material that is biodegradable. It is the process of obtaining it. Another objective of the invention is to integrate PIR waste into a bio-based thermoset structure. by being preferred, PIR waste is then recycled in subsequent processes that affect nature. The goal is to keep the impact level to a minimum. Another aim of the invention is to utilize commercially readily available epoxidized materials as a bio-based system. This involves using oils and plant-derived acids. For the purposes stated above, the invention is a thermoset composite system, in a matrix consisting of bio-based epoxy oils and bio-based carboxylic acids homogeneously dispersed silane-modified polyisocyanurate (PIR) waste dusts It includes. The preferred configurations of the invention are ground PIR in the 200–400 mesh size range. It contains powders. The preferred formulations of the invention are 3-Glycidoxypropyltrimethoxysilane (GPTMS), 3- With glycidoxypropyltriethoxysilane (GPTES) or other epoxy functional silanes It contains modified PIR powders. The preferred formulations for the invention are soybean oil, linseed oil in epoxy, and cotton in epoxy. The oil contains at least one bio-based epoxy oil selected from among castor oils in epoxy. The preferred formulations of the invention are succinic acid, adipic acid, itaconic acid, tartaric acid, It contains at least one bio-based carboxylic acid selected from among citric acid. The preferred formulations of the invention are 1–30% by weight, preferably 5–20% by weight. It contains PIR powder. The preferred configurations of the invention involve a stepped heating protocol in the range of 60–150 °C. It contains a composite structure that has been cured using a special process. Detailed Description of the Invention The PIR particles / powders used in the invention were first subjected to maximum particle size reduction. Therefore, it is ground in order to achieve maximum surface area. PIR particles preferably in a shredding mill at 25,000 rpm, with a mesh size of 20 to 500 mesh, preferably 200 to It is ground to a size that passes through a sieve between 400 mesh and especially 200 mesh. The ground PIR particles are then modified with epoxy silane. PIR Hydroxyl groups located on the outer surface of the particles are silane molecules of epoxy silane. It reacts with the groups at one end but does not react with the epoxy group at the other end. Thus, the PIR particles are surrounded by epoxy groups from epoxy silane molecules. It is modified and becomes functionally epoxy. Epoxy silane molecules are used. 3-Glycidoxypropyltrimethoxysilane (GPTMS or GLYMO, CAS 2530-83-8), 3- Glycidoxypropyltriethoxysilane (GPTES, CAS 2602-34-8), β-(3,4- Epoxycyclohexyl)ethyltrimethoxysilane (CAS 3388-04-3), γ-(Glycidoxy) propylmethyldiethoxysilane (CAS 2897-60-1) and other epoxy-terminated ethoxy and / or These may be methoxysilane molecules. Epoxy silanization process involves aqueous alcohol containing epoxysilane. using the solution, by dipping, washing or spraying This is done. Preferably, a washing process is used. Bio-based systems in which epoxy-modified PIR powders will be evaluated are bio-based. They are obtained from biodegradable materials. These materials are bio-based carboxylic acids. It consists of oils in bio-based epoxy. Epoxy modified PIR powders. The bio-based carboxylic acids to be used in the system in which they will be evaluated must be at least two or These are more multifunctional carboxylic acids. Bifunctional carboxylic acids are found in corn. Succinic acid, obtained from the fermentation of organic biomass such as syrup, is bio-based. The adipic acid that has begun to be obtained is derived from malonic acid and oleic acid found in natural fruits. Azeclic acid is obtained by ozonation, sebakic acid is obtained from castor oil, and corn oil... itaconic acid and oxalic acid, obtained from sugar through fermentation. Fumaric acid, maleic acid, muconic acid, and dicarboxyfurfural, which can be produced through fermentation, These are terephthalic acid and other difunctional carboxylic acids produced from dicarboxyfurfural. In addition to these bifunctional carboxylic acids, there are also hydroxyl and dicarboxylic acids. It can be used in bio-based carboxylic acids containing a group. Such acids are obtained from grapes. These could be tartaric acid, malic acid derived from apples, or 2,3-dihydroxysuccinic acid. Also... 6 Bio-based products containing or lacking three carboxylic acids and hydroxyl groups, such as citric acid. It can be used in polycarboxylic acids. Bio-based solutions will be used in the system where epoxy-modified PIR powders will be evaluated. Carboxylic epoxy oils, on the other hand, have at least two or more functional unsaturations. These are oils that contain and can be epoxidized. Epoxy oils are obtained from these oils. epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxidized sunflower oil, epoxidized safflower oil, epoxidized canola oil, epoxidized corn oil, epoxidized sesame oil, epoxy hazelnut oil, epoxy peanut oil, epoxy olive oil, epoxy palm oil epoxidized castor oil, hydrogenated epoxidized castor oil, epoxidized castor oil mono- or diglyceride form, with glycidyl ether containing the hydroxyl group of castor oil. The modified form is animal-based epoxy fish oil, obtained directly from plants. a minimum of two or more derived from vernonia oil and other oil-based chemicals They are oils in epoxy that have more epoxy functionality. The fatty acid / epoxy ratio in the selected bio-based carboxylic acid and bio-based epoxy is 0.5 to 1. The ratio is mixed, preferably 0.7. Epoxy-modified PIR is added to this mixture. The powders should constitute between 1 and 30 percent of the total resin by weight, preferably between 5 and 20 percent. The mixture is stirred until it is evenly distributed, preferably at a concentration of 10%. Homogeneous Once the mixture is obtained, it is first heated, preferably at 50 to 70 °C, for 30 minutes to two hours. between, then preferably between 90 and 120 °C for two to six hours, and finally preferably... A heating protocol is applied overnight at temperatures between 130 and 150 °C. Heating protocol preferably at 60°C for 1 hour, then at 105°C for 4 hours, and finally at 140°C overnight. It is of a certain size. In alternative applications, a catalyst can be added to the system.

Claims

ALSO EVALUATION The invention relates to the conversion of polyisocyanurate (PIR) based insulation material waste into oil-based bio-based products. It relates to the evaluation in thermoset systems. Within the scope of the invention, production or PIR waste generated after use is ground into powder with a size range of 200–400 mesh. They are converted into this form. The resulting PIR powders, through the hydroxyl groups on their surface Epoxy is modified with silane compounds and epoxy is made functional. Modified PIR powders, bio-based epoxy oils and bio-based carboxylic acids. It is distributed in specific proportions within a system containing [the other ingredients]. The resulting mixture is then gradually... It is cured using a heating protocol to become a bio-based thermoset composite material. PIR waste, which is costly and environmentally harmful to dispose of, is being transformed. Thanks to this invention, They are being recovered; bio-based, environmentally friendly and recyclable thermoset systems are being obtained. These systems contribute to waste management in line with sustainability principles. It provides and enables the production of new high-performance materials. 7 REQUESTS 1. It is a thermoset composite system characterized by its composition of bio-based epoxy with oils and bio-based components. silane homogeneously dispersed in a matrix of carboxylic acids It contains modified polyisocyanurate (PIR) waste dust.

2. It is a thermoset composite system according to Claim 1, with a size of 200–400 mesh. It contains ground PIR powder within a certain range.

3. Thermoset composite system according to claim 1 or 2, having the following characteristic: 3- Glycidoxypropyltrimethoxysilane (GPTMS), 3-Glycidoxypropyltriethoxysilane PIR powders modified with (GPTES) or other epoxy functional silanes It includes.

4. It is a thermoset composite system according to Claim 1, and its characteristic is; soybean oil in epoxy, epoxy in... at least one of the following must be selected: linseed oil, epoxidized cottonseed oil, or epoxidized castor oil. It is a bio-based epoxy containing oil.

5. It is a thermoset composite system according to Claim 1, and its properties are; succinic acid, adipic acid, At least one bio-based carboxylic acid selected from itaconic acid, tartaric acid, and citric acid. It contains acid.

6. Thermoset composite system according to claims 1-3, with the characteristic of being; 1–30% by weight, preferably It contains 5–20% PIR powders by weight.

7. According to Claim 1, the subject of the invention is a thermoset composite system with the characteristic of being able to withstand temperatures between 60–150 °C. composite structure cured by applying a gradual heating protocol within a certain range. It includes.