Method for synthesizing epoxy resin material through resource utilization of nylon acid
Direct synthesis of epoxy resin materials from nylon acid waste liquid addresses the resource utilization challenge, producing high-performance products with adjustable properties for engineering and adhesive applications.
Patent Information
- Application Number
- CN202411303557.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-19
- Publication Date
- 2024-12-31
AI Technical Summary
Nylon acid, a byproduct of adipic acid production, is often discarded as industrial waste due to the lack of efficient and cost-effective methods for its resource utilization, particularly in synthesizing high-performance polymers like epoxy resin materials.
A method is developed to directly utilize nylon acid waste liquid as a raw material to synthesize epoxy resin materials without separation and purification, using additives and controlled heating and curing processes to achieve high-performance products.
The method enables the production of high-performance epoxy resin materials with adjustable properties, offering broad application prospects in engineering materials and adhesives, while reducing waste and lowering production costs.
Smart Images
Figure CN119219894A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of polymer materials, and particularly relates to a method for synthesizing epoxy resin materials by resource utilization of nylon acid. Background Art
[0002] Nylon acid is a byproduct produced during the production of adipic acid by nylon chemicals. It contains a variety of dibasic acids (i.e., mixed acids), metal ions such as copper, nitrogen-containing compounds such as ammonia, and a small amount of impurities such as sediment. Due to cost issues, early nylon acid was buried or incinerated as industrial waste, wasting resources and polluting the environment. In recent years, with the rapid growth of adipic acid production, the production of nylon acid has also continued to increase. On average, 50 to 60 kilograms of nylon acid byproducts are produced for every ton of adipic acid produced. Whether from an economic or environmental perspective, the resource utilization of nylon acid is an inevitable route.
[0003] The comprehensive utilization of nylon acid at home and abroad mainly includes separation and purification and the development of downstream products using nylon acid as raw materials. The separation and purification technologies of mixed dibasic acids mainly include crystallization, extraction, distillation, adsorption and chemical methods. The above separation and purification technologies all have certain limiting factors, such as low separation efficiency, low product purity, high technical difficulty, high energy consumption, etc., so it is impossible to achieve low-cost and high-efficiency separation of nylon acid. Therefore, it is still necessary to continuously improve the process to improve the separation efficiency of nylon acid and reduce costs. On the other hand, a series of downstream products can be directly developed without separation using nylon acid (mixed acid) as raw materials, including mixed acid ester high boiling point solvents, mixed acid ester plasticizers, mixed acid polyester polyols, synthetic waxes, etc. Among them, the manufacturer of nylon acid dimethyl ester is currently the largest product user of nylon acid.
[0004] Although there are studies on using nylon acid as a raw material to synthesize polyester polyols and then synthesize polyurethane elastomers, there are few reports in the literature on using it directly as a mixed monomer to synthesize high-performance polymers.
[0005] Epoxy resin refers to a polymer compound containing two or more epoxy groups in the molecule. Due to the active epoxy groups in the molecular structure, they can undergo cross-linking reactions with various types of curing agents to form insoluble, infusible polymers with a three-dimensional cross-linked network structure, which have excellent mechanical properties, chemical corrosion resistance, good thermal properties, adhesive properties and electrical insulation properties. In addition, the cured epoxy resin products have low shrinkage and excellent dimensional stability.
[0006] Seeking resource utilization of nylon acid can improve the use value of nylon acid and reduce resource waste. However, there are few reports in the literature on using nylon acid as a monomer to synthesize epoxy resin materials. Summary of the invention
[0007] The purpose of the present invention is to solve the problem of treating nylon acid, a byproduct of the existing nylon chemical industry in producing adipic acid, and to provide a method for synthesizing epoxy resin materials by resource utilization of nylon acid. Nylon acid waste liquid is used as a raw material, and the nylon acid is resource-utilized to synthesize high-performance epoxy resin without separation and purification. Products with different performances can be obtained by adjusting the amount of nylon acid used. The method has broad application prospects in the fields of engineering materials, adhesives, packaging materials, etc.
[0008] The present invention is specifically achieved through the following technical scheme. According to a method for synthesizing epoxy resin materials by resource utilization of nylon acid proposed by the present invention, the method comprises the following steps: nylon acid waste liquid, epoxy compound and additive are fully mixed and then heated and cured or heated and then extruded and molded, and cooled to obtain epoxy resin material. The additive comprises one or more of primary amine, secondary amine, tertiary amine, ammonium salt compound, nitrogen heterocyclic organic base, phosphine compound, zinc compound and tin compound. The mass ratio of nylon acid waste liquid, epoxy compound and additive is (0.1~5):1:(0.01~0.2).
[0009] The aforementioned method for recycling nylon acid to synthesize epoxy resin material can be performed by mixing nylon acid waste liquid, epoxy compound and additives, removing water and drying, mixing again and then heating and curing or heating and then extruding and cooling to obtain epoxy resin material; Alternatively, the nylon acid waste liquid is mixed with the additive, dehydrated, dried, and then the epoxy compound is added, mixed evenly, heated and cured or heated and then extruded, and cooled to obtain the epoxy resin material; Alternatively, the nylon acid waste liquid is dehydrated and dried, and then the epoxy compound and the additive are added, mixed evenly, and then heated and cured or heated and then extruded and cooled to obtain the epoxy resin material; Alternatively, nylon acid waste liquid, epoxy compound and additive are mixed evenly and dehydrated, and then heated and extruded to obtain epoxy resin material; Alternatively, the product after dehydration of nylon acid waste liquid is recrystallized, water and additives are added to the recrystallized product, mixed and stirred, and water is removed, and the obtained product is added with epoxy compound, mixed evenly, and then heated and cured or heated and then extruded to obtain epoxy resin material.
[0010] Further, the nitrogen heterocyclic organic base includes one or more of 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene; the phosphine compound includes one or more of triphenylphosphine, tri-n-butylphosphine, triisopropylphosphine, and tri(2-methylphenyl)phosphine; the zinc compound includes one or more of zinc borate, zinc oxide, zinc hydroxide, zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc oxalate, and zinc acetylacetonate; and the tin compound includes one or more of tin tetrachloride, tin acetate, stannous octoate, stannous oxalate, and dibutyltin dilaurate.
[0011] Furthermore, the epoxy compound includes one or more of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, linear phenol polyglycidyl ether, aliphatic glycidyl ether, phthalic acid glycidyl ester, N,N,N',N'-tetracyclyl-4,4'-diaminodiphenylmethane, etc.
[0012] Furthermore, the water removal process includes but is not limited to natural volatilization, heating evaporation, and reduced pressure distillation. The temperature during heating evaporation does not exceed 100°C, preferably 60 to 80°C.
[0013] Furthermore, the drying process is carried out in a vacuum drying oven at 60 to 90 °C for 2 to 4 h.
[0014] Furthermore, the temperature of heating and curing is 90 to 220°C, preferably 140 to 180°C, and the extruder temperature is set to 150 to 200°C during extrusion molding.
[0015] The aforementioned method for resource utilization of nylon acid to synthesize epoxy resin materials, the material mixing methods include but are not limited to crushing mixing, stirring mixing, grinding mixing, ball milling mixing, sand milling mixing, and the mixing equipment includes but is not limited to crushers, stirrers, grinders, ball mills, sand mills, and material mixers.
[0016] The epoxy resin material obtained by the aforementioned method of recycling nylon acid resources to synthesize epoxy resin materials can also be molded, and the molding method includes placing the epoxy resin material in a mold for hot pressing molding, and the hot pressing conditions are a temperature of 160 ~ 220 ° C and a pressure of 0.1 ~ 10 MPa.
[0017] Compared with the prior art, the present invention has obvious advantages and beneficial effects. By means of the above technical solution, the present invention can achieve considerable technical progress and practicality, and has a wide range of utilization value, and has at least the following advantages: The present invention develops a method for directly synthesizing a high-performance epoxy resin material using nylon acid waste liquid as a raw material without separation and purification. The nylon acid and the epoxy compound directly react to obtain the epoxy resin material. By adjusting the amount of nylon acid, products with different performances can be obtained. The present invention has broad application prospects in the fields of engineering materials, adhesives, packaging materials, etc. The preparation method of the present invention is simple, the experimental equipment is simple, the operation is easy, the preparation is efficient, the raw materials are easy to obtain, the production technology requirements and the cost are low, and the synthesized epoxy resin material has excellent repeated processing performance, which provides a new direction for the resource utilization of nylon acid waste liquid. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 It is the thermal gravimetric curve of the epoxy resin material 1 prepared in Example 1.
[0020] Figure 2 It is a dynamic mechanical curve diagram of the epoxy resin material 1 prepared in Example 1.
[0021] Figure 3 This is a photo of a circular sample obtained by injection molding the viscous fluid obtained during the curing process of Example 1.
[0022] Figure 4 This is a sample photo of the epoxy resin material 5 prepared in Example 5 obtained by hot pressing in a mold.
[0023] Figure 5 yes Figure 4 Stress-strain curves obtained from tensile tests on dumbbell-shaped samples. DETAILED DESCRIPTION
[0025] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0026] In the following examples, if no specific conditions are specified, all the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The raw materials and reagents used, if no manufacturer is specified, are all conventional products that can be purchased from the market.
[0027] In the method for synthesizing epoxy resin materials by recycling nylon acid resources of the present invention, the solute content and components in the selected nylon acid waste liquid are not specifically limited. Due to certain changes in process conditions, treatment processes, etc., the composition and content of each batch of nylon acid waste liquid may be different, but the solvent of the nylon acid waste liquid is water, and the main solute is the carboxyl compound impurities generated in the process of producing adipic acid from nylon. The solute mass fraction of the batch of nylon acid waste liquid used in the following examples is 21 wt%, and the total carboxyl content after drying is 1.54 mol / 100 g.
[0028] Example 1 100 g of nylon acid waste liquid, 63.41 g of bisphenol A diglycidyl ether, and 4.45 g of zinc acetylacetonate were weighed and added to a polytetrafluoroethylene evaporating dish, the polytetrafluoroethylene evaporating dish was placed in an 80 °C forced air drying oven to evaporate and dry to remove most of the water, and then placed in a vacuum drying oven at 80 °C for vacuum drying for 2 h. After taking it out, a polytetrafluoroethylene rod was used to fully stir and mix the mixture in the polytetrafluoroethylene evaporating dish, and then the polytetrafluoroethylene evaporating dish was placed in a 160 °C oven for curing for 1 h, then taken out while hot, and the product was cut into small particles with scissors and cooled naturally to obtain a hard solid polymer, which was recorded as epoxy resin material 1.
[0029] The epoxy resin material 1 obtained in Example 1 was subjected to a thermogravimetric analysis. Before the test, the test sample (epoxy resin material 1) was placed in a vacuum drying oven and dried at 160°C for 2 h. 7 mg of the dried epoxy resin material 1 was weighed and placed in a crucible for thermogravimetric analysis. The N2 flow rate was 50 mL / min, the temperature range was 30 ~ 800°C, and the heating rate was 20°C / min. The thermogravimetric curve of the epoxy resin material 1 was obtained as shown in FIG. Figure 1 As shown, it can be known that the thermal weight loss temperature of the epoxy resin material 1 is about 380° C., indicating that the epoxy resin material prepared using nylon acid waste liquid as raw material has good thermal stability.
[0030] The epoxy resin material 1 obtained in Example 1 was subjected to rheological property test in an oscillating mode, with a test temperature range of 50-120°C and a heating rate of 5°C / min. The results are as follows: Figure 2 As shown, it can be seen that the glass transition temperature of the epoxy resin material 1 is around 65°C.
[0031] The viscous fluid obtained during the curing process of Example 1 was added to the cavity of the injection molding machine, the cavity temperature was maintained at 100 °C, the injection pressure was 2 MPa, the initial temperature of the mold was 180 °C, the sample was kept in the mold (pre-treated with a release agent) for 20 minutes, then cooled to room temperature and the sample was taken out. Using molds of different shapes, sizes or thicknesses can obtain samples of various forms, such as Figure 3 Circular sample shown.
[0032] Example 2 100 g of nylon acid waste liquid was weighed and added to a polytetrafluoroethylene evaporating dish, 5 g of zinc borate was added thereto, the polytetrafluoroethylene evaporating dish was placed in an 80 °C forced air drying oven to evaporate and dry to remove most of the water, and then placed in a vacuum drying oven at 80 °C for vacuum drying for 2 h, and then 63.00 g of hydrogenated bisphenol A diglycidyl ether was added to the polytetrafluoroethylene evaporating dish, and the mixture in the polytetrafluoroethylene evaporating dish was fully stirred and mixed using a polytetrafluoroethylene rod, and then the polytetrafluoroethylene evaporating dish was placed in a 160 °C oven for curing for 2 h, and then taken out while hot, and the product was cut into small particles with scissors and naturally cooled to obtain a hard solid polymer, which was recorded as epoxy resin material 2.
[0033] Example 3 100 g of nylon acid waste liquid was weighed and added to a polytetrafluoroethylene evaporating dish. The polytetrafluoroethylene evaporating dish was placed in an 80 °C forced air drying oven to evaporate and dry to remove most of the water, and then placed in a vacuum drying oven at 80 °C for vacuum drying for 2 h. Subsequently, 58.20 g of bisphenol F diglycidyl ether and 4.8 g of 1,8-diazabicyclo[5.4.0]undec-7-ene were added to the polytetrafluoroethylene evaporating dish. The mixture in the polytetrafluoroethylene evaporating dish was fully stirred and mixed using a polytetrafluoroethylene rod. The polytetrafluoroethylene evaporating dish was then placed in a 160 °C oven to react for 30 min. The obtained viscous fluid was poured into a twin-screw extruder preheated to 160 °C, the speed of the twin-screw extruder was adjusted to control the residence time of the material in the screw to be 15 min, and extruded to obtain a material with uniform coarseness and fineness, which was recorded as epoxy resin material 3.
[0034] Example 4 Weigh 200 g of nylon acid waste liquid and add it to a 50 mL polytetrafluoroethylene beaker, add 8 g of zinc oxide, 136.21 g of linear phenolic polyglycidyl ether and 12.31 g of tri-n-butylphosphine, stir and mix thoroughly, place in an 80°C forced air drying oven for evaporation to remove most of the water to obtain a viscous liquid, pour the obtained viscous liquid into a single-screw extruder preheated to 150°C, adjust the speed of the single-screw extruder to control the residence time of the material in the screw to 30 min, extrude, cool, and obtain a hard solid polymer, recorded as epoxy resin material 4.
[0035] Example 5 Weigh 200 g of nylon acid waste liquid and add it to a polytetrafluoroethylene evaporating dish. Place the polytetrafluoroethylene evaporating dish in an 80°C forced air drying oven for 2 h to remove water, precipitate a yellow solid, and use ethanol to recrystallize the yellow solid to obtain colorless crystalline particles. Weigh 20 g of colorless crystalline particles, add water to dissolve and add 2 g of zinc hydroxide. Stir the mixture and place it in an 80°C forced air drying oven again for 2 h to remove water to obtain a white solid. Add 77.27 g of E44 epoxy monomer to the white solid, stir evenly, heat to 200 °C and cure for 10 min, then take it out while hot, cut the product into small particles with scissors, and cool it naturally to obtain epoxy resin material 5.
[0036] The epoxy resin material 5 obtained in Example 5 was broken into small particles and then placed in a mold for hot pressing. After the mold was sealed, it was heated and cured according to a predetermined temperature and time program. Specifically, the processing temperature was 160 °C, the mold was preheated at 160 °C for 15 min before use, and the material was preheated for 10 min after adding the epoxy resin small particle material, and then pressurized to 4 MPa for 10 min. Samples of different shapes can be obtained by using molds of different shapes, sizes or thicknesses, such as Figure 4 As shown, including circular samples ( Figure 4 Left) and dumbbell-shaped samples ( Figure 4 on the right).
[0037] Will Figure 4 The obtained dumbbell-shaped samples were subjected to tensile tests using a 2 kN sensor and a clamp-type grip, and stretched at a rate of 1 mm / min at room temperature until the specimen broke. The load-elongation curve was then converted into a stress-strain curve, as shown in Figure 5 As shown, it shows that the epoxy resin material prepared with nylon acid waste liquid as raw material has good mechanical properties.
[0038] The above is only an embodiment of the present invention, and does not limit the present invention in any form. The present invention can also have other forms of embodiments according to the above structures and functions, which are not listed one by one. Therefore, any simple modification, equivalent change and modification made by any technician familiar with the profession to the above embodiment according to the technical essence of the present invention without departing from the scope of the technical solution of the present invention still falls within the scope of the technical solution of the present invention.
Claims
1. A method for synthesizing epoxy resin materials by recycling nylon acid, characterized in that The following steps are involved: The nylon acid waste liquid, epoxy compound and additive are fully mixed and then heated for curing or extrusion molding after heating, and cooled to obtain an epoxy resin material. The additive includes one or more of primary amines, secondary amines, tertiary amines, ammonium salt compounds, nitrogen heterocyclic organic bases, phosphine compounds, zinc compounds, and tin compounds. The mass ratio of nylon acid waste liquid, epoxy compound and additive is (0.1~5):1:(0.01~0.2).
2. The method for synthesizing epoxy resin material by resource utilization of nylon acid as claimed in claim 1, characterized in that The nylon acid waste liquid, epoxy compound and additive are mixed, dehydrated and dried, mixed evenly again, heated and cured or heated and then extruded and cooled to obtain an epoxy resin material; Alternatively, the nylon acid waste liquid is mixed with the additive, dehydrated, dried, and then the epoxy compound is added, mixed evenly, heated and cured or heated and then extruded, and cooled to obtain the epoxy resin material; Alternatively, the nylon acid waste liquid is dehydrated and dried, and then the epoxy compound and the additive are added, mixed evenly, and then heated and cured or heated and then extruded and cooled to obtain the epoxy resin material; Alternatively, nylon acid waste liquid, epoxy compound and additive are mixed evenly and dehydrated, and then heated and extruded to obtain epoxy resin material; Alternatively, the product after dehydration of nylon acid waste liquid is recrystallized, water and additives are added to the recrystallized product, mixed and stirred, and water is removed, and the obtained product is added with epoxy compound, mixed evenly, and then heated and cured or heated and then extruded to obtain epoxy resin material.
3. The method for synthesizing epoxy resin material by resource utilization of nylon acid as claimed in claim 1 or 2, characterized in that The nitrogen heterocyclic organic base includes one or more of 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene; the phosphine compound includes one or more of triphenylphosphine, tri-n-butylphosphine, triisopropylphosphine, and tri(2-methylphenyl)phosphine; the zinc compound includes one or more of zinc borate, zinc oxide, zinc hydroxide, zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc oxalate, and zinc acetylacetonate; and the tin compound includes one or more of tin tetrachloride, tin acetate, stannous octoate, stannous oxalate, and dibutyltin dilaurate.
4. The method for synthesizing epoxy resin material by resource utilization of nylon acid as claimed in claim 1 or 2, characterized in that The epoxy compound includes one or more of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, linear phenol polyglycidyl ether, aliphatic glycidyl ether, phthalic acid glycidyl ester, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, etc.
5. The method for synthesizing epoxy resin material by resource utilization of nylon acid as claimed in claim 2, characterized in that The water removal process is natural volatilization or heating evaporation or reduced pressure distillation, and the temperature during heating evaporation does not exceed 100 °C.
6. The method for synthesizing epoxy resin material by resource utilization of nylon acid as claimed in claim 2, characterized in that The drying process is to dry in a vacuum drying oven at 60~90 ℃ for 2~4 h.
7. The method for synthesizing epoxy resin material by resource utilization of nylon acid as claimed in claim 2, characterized in that The temperature of heating and curing is 90 ~ 220 °C, and the extruder temperature is set to 150 ~ 200 °C during extrusion molding.
8. The method for synthesizing epoxy resin material by resource utilization of nylon acid as claimed in claim 1 or 2, characterized in that The mixing methods include crushing mixing, stirring mixing, grinding mixing, ball milling mixing, and sand milling mixing. The mixing equipment includes a crusher, a stirrer, a grinder, a ball mill, a sand mill, and a material mixer.
9. The method for synthesizing epoxy resin material by resource utilization of nylon acid as claimed in claim 1, characterized in that The obtained epoxy resin material is further subjected to a molding process, wherein the molding process includes placing the epoxy resin material in a mold for hot pressing molding, and the hot pressing conditions are a temperature of 160 to 220 °C and a pressure of 0.1 to 10 MPa.