Bio-based polyurethane adhesive with enhanced thermal resistance.

Abstract

The invention relates to a bio-based polyurethane adhesive composition and production method that is resistant to heat and hydrolytic effects.

Description

Bio-based polyurethane adhesive with enhanced thermal resistance. TECHNICAL FIELD The invention provides applications in the construction, automotive, furniture, and textile industries that can withstand high temperatures and hydrolytic degradation. durable bio-based polyurethane adhesives for environments exposed to adverse effects It is related to its development and production method. PREVIOUS TECHNIQUE Traditional adhesive technologies generally use solvent-based adhesives, hot melt adhesives. It consists of formulations and epoxy-based materials. Solvent-based Adhesives have a wide range of uses due to their low cost and ease of application. However, these types of adhesives have low thermal resistance and the solvents are harmful to the environment. They have limitations due to their effects. Hot melt adhesives, on the other hand, have fast curing and certain advantages. Although they can provide high adhesion to surfaces, they are sensitive to temperature and humidity changes. They are not resistant to corrosion. Epoxy-based adhesives, on the other hand, offer high mechanical strength and hardness. They are frequently preferred in structural applications by providing this; however, these types of adhesives, In applications requiring flexibility, performance is lost, and in some cases... Problems such as cracking are encountered. Polyurethane adhesives offer flexibility and superiority compared to traditional adhesive technologies. It offers significant advantages in terms of mechanical strength. Polyurethane is soft. Its flexible structure, gained thanks to the segment, allows it to withstand mechanical impacts and lateral displacements. It provides superior performance against stresses. However, the current Significant improvements in thermal and hydrolytic resistance in polyurethane adhesive technologies. There are shortcomings. The structural integrity of polyurethane when exposed to high temperatures... Its integrity is compromised and its adhesive function is lost. Similarly, hydrolytic effects occur. Underneath, especially in humid or water-exposed environments, the chemical properties of adhesives... The structure deteriorates and the bonds between substrates break. This situation affects polyurethane. Adhesives have a limited range of applications requiring long-lasting performance in demanding settings. This leads to it having a field of use. 1 In addition, traditional polyurethane adhesives also have some drawbacks in terms of environmental sustainability. They have disadvantages. Most polyurethane adhesives are based on fossil fuels. It is produced with raw materials, and this situation both increases environmental impact and Compliance with modern environmental standards due to the lack of bio-based alternatives This makes things more difficult. Growing environmental awareness and sustainability requirements necessitate environmentally friendly and sustainable solutions. This has made the development of bio-based adhesives a necessity. The following documents were encountered during the preliminary patent search. Document number US11345776B2 concerns carbodiimide compounds and water-based polyurethanes. focusing on the development of resins with improved water resistance, storage stability, and viscosity. It provides features such as control. However, because it does not contain bio-based components... It lacks the advantage of environmental sustainability. Furthermore, it is resistant to high temperatures. It does not offer solutions to increase thermal resistance and mechanical strength. It does not address these issues. Document number DE19958843A1 concerns water-based polyurethane dispersions. By focusing on its production, carbodiimide groups can disperse in water with hydrophilic structures. while aiming to make it suitable for properties such as high temperature and hydrolytic resistance It has not focused on its development. Document number US20080021176A1, low temperature tolerance and long service life Method for producing stable uretonium modified isocyanate compounds This explains polyisocyanate compounds such as 4,4'-diphenylmethane diisocyanate (MDI). the formation of carbodiimides using and the incorporation of these carbodiimides into uretonin structures The aim was to transform it, but thermal and hydrolytic resistance or mechanical It does not mention improving the features. Literature studies have investigated the thermal and hydrolytic resistance of polyurethane adhesives. Research on bio-based polyols with additives such as carbodiimide aimed at increasing their effectiveness. Research has shown that by combining these materials, both bio-based and... describing a high-strength adhesive composition and its application in different industries. No comprehensive studies on these applications could be found. These shortcomings seen in current adhesive technologies affect the construction, automotive, furniture, and other industries. in industries such as textiles under high temperature, humidity and mechanical stress the need for a durable, long-lasting and environmentally friendly adhesive that can be used 2 This clearly demonstrates. In this context, a new polyurethane adhesive composition... its development and the fact that this composition both increases thermal and hydrolytic resistance Producing it with raw materials that meet environmental sustainability standards is a major advantage. It has become a necessity. In conclusion, all the problems mentioned above necessitate innovation in the relevant field. It has brought it to this state. THE PURPOSE OF THE INVENTION The present invention aims to eliminate the aforementioned problems and to provide technical solutions in the relevant field. It aims to create an innovation. The main purpose of the invention is to create an environmentally friendly, bio-based solution that provides thermal and hydrolytic resistance. The aim is to reveal the structure of polyurethane adhesive. Another aim of the invention is to investigate the cycloaddition reaction of isocyanates and carbodiimides. By forming urethane structures, the internal strength of the structure is increased, making it more durable and long-lasting. The goal is to create a long-lasting adhesive. Another aim of the invention is environmental sustainability through the use of bio-based components. to comply with standards. One aim of the invention is to increase the mechanical strength of the adhesive, thereby making it suitable for a wide range of industrial applications. The goal is to make it available for use across a wide range of applications. A BRIEF DESCRIPTION OF THE INVENTION All the purposes mentioned above and those that will emerge from the detailed explanation below. The present invention is designed to be used in the construction, automotive, furniture, and textile industries. ceramics, wood, concrete in environments that will be exposed to high temperatures and hydrolytic effects. for bonding substrates such as wood, concrete, fiber cement board, and ceramic tile covering materials. It is an improved adhesive composition. Accordingly, component A must be formed.  To provide adhesive performance as a result of reaction with isocyanate 20-40% polyol by weight,  Filling to control viscosity and increase mechanical strength as a material, 30-70% by weight of CaCO3, 3  To increase thermal and hydrolytic resistance, 0.02-1% by weight Carbodiimide,  Zeolite at a concentration of 1-5% by weight as a moisture and carbon dioxide absorber,  Hydrogenated at a rate of 1-5% by weight to improve rheological properties Castor oil, To create component B  Increasing mechanical strength by creating rigid segments and with polyol To ensure adhesion performance as a result of the reaction, 7.8% by weight. 15.52% Methylene Diphenyl Diisocyanate (MDI), It includes. A preferred configuration of the invention is a polyol structure with an OH number of 120-200. It is a trifunctional polyester polyol with a KOH concentration between mg*g. Another preferred configuration of the invention is a polyol-structured material;  Castor oil derivatives with increased degree of cross-linking,  polyether,  polyester,  polycarbonate,  polycaprolactone polyols,  soy,  palm, • Corn  Sunflower oil-based biopolyol It consists of one of the individuals or combinations selected from the group containing it. A preferred configuration of the invention is that of the filler material.  silicon dioxide,  barium sulfate,  aluminum hydroxide,  feldspar,  titanium dioxide,  talk,  basalt, 4  bentonite,  kaolin,  mica It consists of one of the individuals or combinations selected from the group containing it. Another preferred configuration of the invention is a moisture and carbon dioxide absorbing material.  Monomeric isocyanate,  Ca(OH)2,  Bentonite It consists of one of the individuals or combinations selected from the group containing it. A preferred configuration of the invention is bentonite, organophilic, as the viscosity-enhancing material. phyllosilicate, modified urea, polyamide, polyhydroxycarboxylic acid ester derivative rheological additives It consists of one of the individuals or combinations selected from the group containing it. Another preferred configuration of the invention is to create rigid segments. diisocyanate structure of the material  Containing 2,4, 2,2 and 4,4 isomers and mixtures with different functionalities diphenylmethane diisocyanate (MDI),  Toluene diisocyanate (TDI) including 2,4, 2,6 isomers and their mixtures,  hexamethylene diisocyanate (HDI),  isophorone diisocyanate (IPDI),  tetramethylxylene diisocyanate (TMXDI), It is one of the individuals or combinations selected from the group containing. Another preferred configuration of the invention is; a) to form soft segments of the polyurethane structure and cross-linking mixing polyol and carbodiimide to provide, b) zeolite as a moisture and carbon dioxide absorber and as a viscosity regulator Addition of hydrogenated castor oil, c) Mechanical strength and viscosity of the mixture obtained in process step b Adding CaCO3 as a filler material to optimize, d) To ensure that the mixture obtained in step c becomes homogeneous. mixing at a speed of 500-2000 revolutions per minute and the temperature of the mixture Stop stirring when the temperature reaches 55°C. e) Packaging of the resulting component A, f) To increase mechanical strength by creating rigid segments in the polyurethane structure and To ensure adhesion performance, a concentration of 7.8-15.52% by weight. Packaging of methylene diphenyl diisocyanate (MDI) under nitrogen gas, g) component A obtained in step e and component B obtained in step f initiating the polyurethane reaction by mixing the components, h) Application of the resulting mixture to substrates and chemical reaction completed and the adhesive cured, It is characterized by including the process steps. Another preferred design feature of the invention is flexibility and adhesion in process step a. Castor oil derivatives with an increased degree of cross-linking to ensure their performance, polyester, polyether, polycarbonate, polycaprolactone polyols, soy, palm, corn, sunflower oil It involves the use of bio-polyol based on biopolyol. Another preferred configuration of the invention involves moisture and carbon dioxide in process step b. The monomeric isocyanate, Ca(OH)₂, and bentonite are used as binders. 2 Another preferred configuration of the invention is the viscosity regulator in process step b. The materials used include bentonite, organophilic phyllosilicate, modified urea, and polyamide. Another preferred configuration of the invention is as a filler material in process step c. silicon dioxide, barium sulfate, aluminum hydroxide, feldspar, titanium dioxide, talc, The materials used include basalt, bentonite, kaolin, and mica. Another preferred configuration of the invention involves the formation of a rigid polyurethane structure in the f processing step. to create segments  Containing 2,4, 2,2 and 4,4 isomers and mixtures with different functionalities diphenylmethane diisocyanate (MDI),  Toluene diisocyanate (TDI) including 2,4, 2,6 isomers and their mixtures,  hexamethylene diisocyanate (HDI),  isophorone diisocyanate (IPDI), tetramethylxylene diisocyanate (TMXDI), It is the use of. 6 DETAILED DESCRIPTION OF THE INVENTION This detailed description defines the invention as Thermally Resistance Enhanced Bio-Based Polyurethane. The adhesive is used solely to facilitate a better understanding of the subject matter, without any limiting effects. This is explained with examples that will not create a problem. The invention deals with a bio-based, environmentally friendly material resistant to high temperatures and hydrolytic effects. It relates to the development and production method of polyurethane adhesives. Traditional polyurethane adhesives have certain limitations in terms of flexibility and mechanical strength. Although they have advantages, they have significant shortcomings in terms of thermal and hydrolytic resistance. This shows that they lose their structural stability when exposed to high temperatures. These adhesives undergo chemical degradation when exposed to moisture and water, damaging the substrates. This leads to the weakening or breaking of ties between them. Furthermore, traditional Additives used in polyurethane formulations are generally based on fossil fuel derivatives. Therefore, it has limitations in terms of environmental sustainability. This This situation requires polyurethane adhesives to withstand high temperature and humidity conditions. application areas in industries such as construction, automotive, furniture and textiles that require limiting existing technologies from offering long-lasting and durable solutions. This prevents the use of traditional polyurethane adhesives. Developing innovative contributions and production methods has become essential. The invention relates to the cycloaddition of carbodiimide with isocyanate during the reaction of polyurethane. This reaction leads to the formation of cyclic structures with higher bond energy. This results in the formation of covalent bonds with higher decomposition energy in the final product. It increases the internal strength, thereby improving the material's performance compared to traditional solutions. It takes it beyond. To create component A; Polyols react with isocyanates to improve the flexibility and adhesion of the adhesive. It creates structures that ensure its performance. The soft segments of the polyurethane structure It forms and provides impact resistance and elasticity to the adhesive. Calcium carbonate (CaCO3) is used as a filler material. It regulates viscosity. It increases mechanical strength and optimizes cost. It also improves the processability of the mixture. It improves. 7 Carbodiimide undergoes a cycloaddition reaction with isocyanate, resulting in decomposition and loss of bond energy. the formation of higher cyclic structures, thereby increasing the internal strength in the structure. It improves the thermal and hydrolytic resistance of the adhesive by promoting cross-linking. It enhances the formation of cyclic structures during the polyurethane reaction. Zeolite acts as a moisture and carbon dioxide absorber. This improves the stability of the adhesive. It enhances and prevents degradation caused by environmental factors. Hydrogenated castor oil improves the rheological properties of adhesives. Component B contains 7.8-15.52% by weight of methylene diphenyl diisocyanate (MDI). This component forms the rigid segments of the polyurethane structure and provides mechanical strength. It increases MDI, between the isocyanate groups and the hydroxyl groups of the polyol in component A. The reaction that takes place causes the adhesive to transform into a strong polymer network. This The structure is resistant to mechanical stresses such as tension, compression and impact caused by the adhesive. while strengthening its durability, it also provides stability under high temperature conditions. Furthermore, packaging MDI under nitrogen gas preserves the reactivity of the component. This ensures protection against other side reactions and moisture effects. In this way, B The component plays a critical role in enhancing the thermal, mechanical, and environmental resistance of the adhesive. The adhesive is produced using the following method: Step A: Mixing Polyol and Carbodiimide: To create soft segments of the polyurethane structure and to enable cross-linking. with 20-40% polyol by weight and 0.02-1% carbodiimide by weight. This mixture is used to increase the thermal and hydrolytic resistance of the structure. It initiates the reactions after contact with isocyanate. Step B: Addition of Zeolite and Hydrogenated Castor Oil: In step A, the resulting mixture should be mixed with 1-5% moisture and carbon dioxide by weight. Zeolite as a binder, and 1-5% by weight of hydrogenated oil as a viscosity regulator. Castor oil is added. Step C: Adding Filler Material: The aim is to increase the mechanical strength of the mixture and control its viscosity using fillers. Calcium carbonate (CaCO₃) is added as an ingredient at a rate of 30-70% by weight. 3 8 Step D: Mixing and Temperature Control: The mixture is stirred at a speed of 500-2000 rpm until it becomes completely homogeneous. Temperature Stirring is stopped when the temperature reaches 55°C. Step E - Packaging of Component A: The prepared component A is packaged under appropriate conditions to maintain its reactivity. Step F: Preparation and Packaging of Component B: Methylene diphenyl diisocyanate (MDI) at a concentration of 7.8-15.52% by weight, under nitrogen gas It is packaged to protect it from adverse reactions. Step G: Mixing Components A and B: The resulting components A and B are used to initiate the polyurethane reaction. They are mixed in proportions. As a result of the reaction between isocyanate and polyol, the adhesive's chemical composition is formed. its structure is created. Step H: Application and Curing of Substrates: The prepared mixture is applied to the substrates. Through the curing process, the polyurethane adhesive becomes the final product. It gains thermal, mechanical and hydrolytic resistance. Reference Carbodiimide Additive Product Product Sample Code - S1-0.1 S1-0.2 S1-0.3 Rate (%) - 0.1 0.2 0.3 Slip (mm) 0.82 0.36 0.35 0.8 Tensile Strength (N / mm^2) >2 >2 >2 >2 Initial Shear Adhesion Strength 3.06 3.57 3.37 3.44 (N / mm²) Cutting Adhesion After Immersion in Water 2.51 2.78 3.17 3.21 Strength (N / mm²) Post-Thermal Shock Shear Adhesion 0 3.26 3.24 3.41 Strength (N / mm²) Table 1 Table 1 shows the specifications of polyurethane adhesives containing carbodiimide additives according to TS EN 12004. The performance results of the tests conducted are presented by comparing them with the reference product. The effects of different carbodiimide addition rates (0.1%, 0.2%, 0.3%) were evaluated. In the slip (mm) test results, the slip in the reference product was measured as 0.82 mm. With the addition of carbodiimide, shear values ​​were significantly reduced, and at 0.1% and 0.2%. The lowest levels were recorded in these percentages, 0.36 mm and 0.35 mm, representing 0.3%. 9 The shear value (0.8 mm) increased. This indicates that the low proportion of carbodiimide additive... It increases shear strength, but high ratios may limit this effect. It shows. According to the tensile strength (N / mm²) results, both the reference product and carbodiimide The tensile strength of the additive products was measured as >2 N / mm². This indicates that carbodiimide The study shows that the additive has no negative effect on tensile strength. When looking at the Initial Shear Adhesion Strength (N / mm²) results, the reference product It was measured as 3.06 N / mm². Carbodiimide-added products are better compared to the reference product. It showed high initial shear adhesion strength (%0.1: 3.57, %0.2: 3.37, 0.3%: 3.44). This shows that the carbodiimide additive increased the shear adhesion strength. It shows. When looking at the shear adhesion strength (N / mm²) results after immersion in water... The reference product was measured at 2.51 N / mm². Carbodiimide-modified products, immersion in water. Afterwards, a significant increase in adhesion strength was observed (%0.1: 2.78, %0.2: 3.17, 0.3%: 3.21). This clearly shows that the addition of carbodiimide increased water resistance. It shows. Looking at the Shear Adhesion Strength (N / mm²) results after Thermal Shock The value of the reference product was measured as 0 N / mm². The reference product conforms to TS EN 12004-1. According to the report, the shear adhesion strength test after thermal shock consisted of 4 cycles. Carbodiimide showed no resistance after exposure to water at 100°C and water at 23°C. The additive products exhibited high resistance after thermal shock (%0.1: 3.26, %0.2: 3.24, (0.3%: 3.41). This indicates that a low amount of carbodiimide additive is resistant to high-temperature water. It has been shown to significantly increase durability. The scope of protection of the invention is specified in the claims attached hereto, and these details are strictly adhered to. The explanation cannot be limited to those given for illustrative purposes. Because a technically skilled person... the person, without deviating from the main theme of the invention, in light of what has been described above, similar It is clear that these structures can emerge.

Claims

1. The invention relates to applications in the construction, automotive, furniture, and textile industries that can withstand high temperatures and conditions. ceramic, wood, and concrete substrates in environments that will be exposed to hydrolytic effects For bonding to wood, concrete, fiber cement board, and ceramic tile covering materials. It is an improved adhesive composition, the characteristic of which is; To create component A  To form and bond the soft segments of the polyurethane structure. its performance is achieved by weight of the reaction result with isocyanate 20-40% Polyol,  To increase thermal and hydrolytic resistance, 0.02-1% by weight Carbodiimide,  Filling to control viscosity and increase mechanical strength as a material, 30-70% by weight of CaCO3,  Zeolite at a concentration of 1-5% by weight as a moisture and carbon dioxide absorber,  Hydrogenated at a rate of 1-5% by weight to improve rheological properties Castor oil, To create component B  Increasing mechanical strength and adhesion by forming rigid segments To ensure its performance, it contains 7.8% - 15.52% Methylene Diphenyl by weight. Diisocyanant (MDI), It is characterized by its inclusion.

2. Composition according to claim 1, its characteristic is; the number of OH groups of the material in the polyol structure. It is a trifunctional polyester polyol with a KOH concentration between 120-200 mg*KOH / g.

3. Composition according to Claim 1, its characteristic is that the material has a polyol structure;  Castor oil derivatives with increased degree of cross-linking,  polyether,  polyester,  polycarbonate,  polycaprolactone polyols,  soy, 11  palm, • Corn  from sunflower oil-based biopolyols It consists of one of the individuals or combinations selected from the group containing it.

4. Composition according to Claim 1, its characteristic feature is; the filler material  silicon dioxide,  barium sulfate,  aluminum hydroxide,  feldspar,  titanium dioxide,  talk,  basalt,  bentonite,  kaolin,  mica It consists of one of the individuals or combinations selected from the group containing it.

5. Composition according to Claim 1, its characteristic is; moisture and carbon dioxide absorbing material.  Monomeric isocyanate,  Ca(OH)2,  Bentonite It consists of one of the individuals or combinations selected from the group containing it.

6. Composition according to Claim 1, its characteristic is that the material regulates the viscosity. bentonite, organophilic phyllosilicate, modified urea, polyamide, polyhydroxycarboxylic acid from individuals or combinations selected from a group containing ester-derived rheological additives It consists of one of them.

7. Composition to Claim 1, its characteristic is to form rigid segments. diisocyanate structure of the material 12  Including 2,4, 2,2 and 4,4 isomers and mixtures with different functionalities diphenylmethane diisocyanate (MDI),  Toluene diisocyanate (TDI) including 2,4, 2,6 isomers and their mixtures,  hexamethylene diisocyanate (HDI),  isophorone diisocyanate (IPDI),  tetramethylxylene diisocyanate (TMXDI), It is one of the individuals or combinations selected from the group containing.

8. The invention relates to applications in the construction, automotive, furniture, and textile industries that can withstand high temperatures and conditions. ceramic, wood, and concrete substrates in environments that will be exposed to hydrolytic effects For bonding to wood, concrete, fiber cement board, and ceramic tile covering materials. It is an improved adhesive composition production method, the characteristic of which is; i) to form soft segments of the polyurethane structure and cross-linking mixing polyol and carbodiimide to provide, j) zeolite as a moisture and carbon dioxide absorber and as a viscosity regulator Addition of hydrogenated castor oil, k) Mechanical strength and viscosity of the mixture obtained in process step b Adding CaCO3 as a filler material to optimize, l) To ensure that the mixture obtained in step c becomes homogeneous. the mixture should be mixed at a speed of 500-2000 rpm and the temperature of the mixture should be raised to 55°C. Stopping the mixing process when it reaches this point. m) Packaging of the resulting component A, n) to increase mechanical strength by creating rigid segments in the polyurethane structure and To ensure adhesion performance, a concentration of 7.8-15.52% by weight. Packaging of methylene diphenyl diisocyanate (MDI) under nitrogen gas, o) component A obtained in step e and component B obtained in step f initiating the polyurethane reaction by mixing the components, p) Application of the resulting mixture to substrates and chemical reaction completed and the adhesive cured, It is characterized by including the process steps.

9. The method conforming to claim 8 is characterized by: flexibility and adhesion in process step a. Castor oil with an increased degree of cross-linking to ensure its performance. 13 derivatives, polyether, polyester, polycarbonate, polycaprolactone, polyols, soy, palm, The method involves using corn or sunflower oil-based biopolyols.

10. This method complies with claim 8 and its characteristic is that moisture and carbon dioxide are removed in process step b. The use of monomeric isocyanate, Ca(OH)₂, and bentonite as binders. 2 11. This method complies with claim 8 and its characteristic is that a viscosity regulator is added in process step b. This involves using hydrogenated castor oil.

12. This method complies with claim 8 and its characteristic is that it is used as a filler material in process step c. silicon dioxide, barium sulfate, aluminum hydroxide, feldspar, titanium dioxide, The materials used include talc, basalt, bentonite, kaolin, and mica.

13. The method conforming to claim 8 is characterized by the formation of a rigid polyurethane structure in process step f. to create segments  Including 2,4, 2,2 and 4,4 isomers and mixtures with different functionalities diphenylmethane diisocyanate (MDI),  Toluene diisocyanate (TDI) including 2,4, 2,6 isomers and their mixtures,  hexamethylene diisocyanate (HDI),  isophorone diisocyanate (IPDI), tetramethylxylene diisocyanate (TMXDI), It is the use of. 14