Epoxy resin alcoholysis model-based degradation conversion rate calculation method and system

Abstract

The invention discloses a degradation conversion rate calculation method and system based on an epoxy resin alcoholysis model, and belongs to the technical field of thermosetting epoxy resin degradation and recovery. The method comprises the following steps: pouring epoxy resin to cure and mold, carrying out an epoxy resin alcoholysis degradation experiment at different temperatures, and recording degradation conversion rates at different moments; constructing an epoxy resin geometric model, and analyzing to obtain a degradation conversion rate differential expression containing reaction rate constants and geometric parameters; solving the differential equation to obtain a reaction rate constant, and fitting by using an Arrhenius formula to obtain degradation activation energy; analyzing a transesterification process of the epoxy resin and the alcohol solvent and a diffusion process of the alcohol solvent in the epoxy resin, and establishing a degradation conversion rate expression which does not contain geometric dimension parameters; and substituting degradation reaction activation energy, and fitting to determine a degradation conversion rate expression which does not contain geometric dimension parameters. The invention aims to provide a reference for the degradation process analysis of the large-size epoxy resin with a complex shape.

Description

Background Art

[0002] The polymer formed by compounding anhydride-cured epoxy resin with fillers such as fibers or powders has the advantages of excellent insulation properties, high mechanical strength and good heat resistance stability. It is also resistant to chemical corrosion and easy to process. Therefore, it is widely used in the field of electrical equipment, such as transmission line insulators, dry-type transformers and insulating pull rods. Although the performance of epoxy resins prepared by different anhydride curing agents is different, the cross-linking bonds in their three-dimensional networks are all ester bonds, and they show the unified characteristics of being difficult to dissolve and melt. This results in the inability to mold and process again after the product fails and expires, and it is difficult to degrade and recycle. Therefore, it is listed in the list of high-pollution products in the "Comprehensive List of Environmental Protection". Although some scholars have conducted research and development on recyclable and self-healing epoxy resins, the epoxy resins in service will occupy a large amount of land after retirement, and the problem of solid waste treatment cannot be avoided. With the increase in the number of years of operation, the number of retired epoxy resins has increased, and the environmental problems caused have become increasingly significant. However, the traditional methods of plastic waste disposal (incineration and landfill) have brought great pressure to the environment, so it is urgent to develop green and efficient degradation and recycling methods.

[0003] Existing studies have shown that for electrical epoxy resins, that is, anhydride-cured epoxy systems, alcohol solvents can undergo ester exchange reactions (alcoholysis) with polymer cross-linked ester bonds, and epoxy resin degradation can be achieved under mild conditions and in a short time. Moreover, the alcoholysis process only destroys the cross-linked bonds, retains the integrity of the main chain of the molecule, and the degradation products still have use value. Since the degradation products are polyols, they can be mixed with isocyanates for curing to prepare polyurethanes. The whole process is green and economical, and the difficulty of handling waste solid epoxy resins is reduced (patent CN113956428A). In addition to preparing polyurethanes, some studies have considered reusing them to prepare new epoxy resins. Patent CN118652472A uses ethylene glycol alcoholysis to recover epoxy resin degradation products, and adds them to new epoxy resins at an addition amount of 5-20% for curing. In addition, the catalyst used in the alcoholysis process can also be recycled and reused multiple times, which further reduces the economic cost and improves the use value of the degradation products (patents CN116063738A and CN116554024A).

[0004] The above results show that alcoholysis has become an important way for the degradation and recovery of anhydride-cured epoxy resins. However, there is a lack of a clear mathematical model between the degradation rate, geometric size, time and temperature of epoxy resins during the alcoholysis process. Therefore, a method for establishing an epoxy resin alcoholysis model is proposed, in order to provide a reference for the degradation process of large-sized and complex-shaped epoxy resins. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a degradation conversion rate calculation method and system based on the epoxy resin alcoholysis model in view of the deficiencies in the above-mentioned prior art, so as to obtain the relationship between time, temperature, geometric dimensions and degradation rate in the epoxy resin alcoholysis process, so as to solve the technical problem of the current lack of epoxy resin alcoholysis process.

[0006] The present invention adopts the following technical solutions: A method for calculating the degradation conversion rate based on an epoxy resin alcoholysis model comprises the following steps: Pour epoxy resin to solidify it, perform alcoholysis degradation experiment on epoxy resin at different temperatures, and record the degradation conversion rate at different times; The geometric model of epoxy resin was constructed based on the degradation conversion rate at different times, and the degradation conversion rate differential equation containing reaction rate constant and geometric parameters was obtained through analysis. The reaction rate constant is obtained by solving the differential equation and the degradation activation energy is obtained by fitting; The transesterification process between epoxy resin and alcohol solvent and the diffusion process of alcohol solvent in epoxy resin were analyzed, and the degradation conversion rate expression without geometric size parameters was established based on the degradation activation energy. Substituting the activation energy of the degradation reaction, the degradation conversion rate without geometric size parameters was determined by fitting.

[0007] Preferably, the epoxy resin is an anhydride-cured resin and a composite material thereof, the anhydride includes a combination of one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and maleic anhydride, and the composite filler includes a combination of one or more of silica powder, alumina powder, glass fiber and carbon fiber.

[0008] Preferably, the volume of the epoxy resin is less than or equal to 125 cm 3 .

[0009] Preferably, the degradation conversion rate for:

[0010] in, m 1 is the initial mass of epoxy resin, m t for t Always check the quality of epoxy resin.

[0011] Preferably, the alcohol solvent used in the degradation reaction is in excess, and the alcohol solvent includes one or more combinations of ethanol, ethylene glycol and trifluoroethanol.

[0012] Preferably, the degradation conversion rate differential equation containing the reaction rate constant and geometric parameters is as follows:

[0013] in, k T for T The reaction rate constant at temperature, f ( a ) is a geometric parameter function.

[0014] Preferably, the degradation activation energy obtained by fitting is specifically: Solve the differential equation to get the reaction rate constant k T , substitute into the Arrhenius formula to get the degradation activation energy, the Arrhenius formula is as follows:

[0015] in, k 0 is the pre-exponential factor, ΔE For the degradation activation energy, R is the gas constant.

[0016] Preferably, the degradation conversion rate expression is as follows:

[0017] in, d (-COO-) / dt is the transesterification reaction rate, D is the diffusion coefficient.

[0018] Preferably, the transesterification reaction rate d (-COO-) / dt for:

[0019] in, k 1 is the transesterification reaction rate, φ 1 is the volume fraction of the solvent in the epoxy resin inner swelling layer, V 1 is the molar volume of alcohol solvent, V 2 is the molar volume of epoxy resin.

[0020] In a second aspect, an embodiment of the present invention provides a degradation conversion rate calculation system based on an epoxy resin alcoholysis model, comprising: Experimental module: pouring epoxy resin to solidify it, carrying out alcoholysis degradation experiment of epoxy resin at different temperatures, and recording the degradation conversion rate at different times; The analysis module builds the geometric model of epoxy resin based on the degradation conversion rate at different times, and obtains the degradation conversion rate differential equation containing the reaction rate constant and geometric parameters; The fitting module solves the differential equation to obtain the reaction rate constant and fits it to obtain the degradation activation energy; Construct a module to analyze the transesterification process between epoxy resin and alcohol solvent and the diffusion process of alcohol solvent in epoxy resin, and establish a degradation conversion rate expression without geometric size parameters based on degradation activation energy; The calculation module substitutes the activation energy of the degradation reaction and determines the degradation conversion rate without geometric size parameters through fitting.

[0021] In a third aspect, a computer device comprises a memory, a processor, and a computer program stored in the memory and executable on the processor, wherein the processor implements the steps of the above-mentioned method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model when executing the computer program.

[0022] In a fourth aspect, an embodiment of the present invention provides a computer-readable storage medium, comprising a computer program, which, when executed by a processor, implements the steps of the above-mentioned method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model.

[0023] In a fifth aspect, a chip comprises a memory, a processor, and a computer program stored in the memory and executable on the processor, wherein when the processor executes the computer program, the steps of the above-mentioned method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model are implemented.

[0024] In a sixth aspect, an embodiment of the present invention provides an electronic device, including a computer program, which, when executed by the electronic device, implements the steps of the above-mentioned method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model.

[0025] Compared with the prior art, the present invention has at least the following beneficial effects: A method for calculating the degradation conversion rate based on the alcoholysis model of epoxy resin. A mathematical model of the epoxy resin degradation process can be established by performing a preliminary degradation experiment on the cured epoxy resin, recording the data and executing the process according to the process. The model can provide data reference for the degradation of the same epoxy resin material, and provide method experience for the degradation of large-sized epoxy resins.

[0026] Furthermore, when the alcohol solvent is in excess, the alcoholysis transesterification reaction can be ensured to proceed in the forward direction. At the same time, the combination of one or more alcohol solvents can achieve the degradation of anhydride-cured epoxy resin, which is to increase the scope of use of the alcohol solvent.

[0027] Furthermore, the degradation activation energy is fitted in order to substitute it into the differential expression of the degradation conversion rate in order to solve the differential equation, so that the relationship between time, temperature, geometric dimensions and degradation rate can be calculated.

[0028] It can be understood that the beneficial effects of the second to sixth aspects mentioned above can be found in the relevant description of the first aspect mentioned above, and will not be repeated here.

[0029] In summary, the present invention provides an accurate and efficient calculation method by creating a mathematical model of epoxy resin degradation, which is applicable to anhydride-cured epoxy resin and its composite materials; it not only simplifies the calculation of degradation conversion rate, but also realizes the integration of experiment and calculation through the automation system, which helps to solve the recycling problem of epoxy resin, reduce environmental pollution, and improve the economic value of degradation products. In addition, this method provides an important reference for the degradation analysis of large-sized epoxy resins, opening up a new way for industrial application and environmental protection.

[0030] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 is a flow chart of the method of the present invention; Figure 2 The graphs are the results of degradation conversion rate at different temperatures; Figure 3 It is the graph of model fitting value and experimental result; Figure 4 A schematic diagram of a computer device provided by an embodiment of the present invention; Figure 5 The block diagram of a chip provided according to an embodiment of the present invention. DETAILED DESCRIPTION

[0032] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the 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.

[0033] In the description of the present invention, it should be understood that the terms “include” and “comprises” indicate the presence of described features, wholes, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, components and / or collections thereof.

[0034] It should also be understood that the terms used in the present specification are only for the purpose of describing specific embodiments and are not intended to limit the present invention. As used in the present specification and the appended claims, unless the context clearly indicates otherwise, the singular forms "a", "an" and "the" are intended to include plural forms.

[0035] It should be further understood that the term "and / or" used in the present specification and the appended claims refers to any combination of one or more of the associated listed items and all possible combinations, and includes these combinations. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in the present invention generally indicates that the associated objects are in an "or" relationship.

[0036] It should be understood that, although the terms first, second, third, etc. may be used to describe preset ranges, etc. in the embodiments of the present invention, these preset ranges should not be limited to these terms. These terms are only used to distinguish preset ranges from each other. For example, without departing from the scope of the embodiments of the present invention, the first preset range may also be referred to as the second preset range, and similarly, the second preset range may also be referred to as the first preset range.

[0037] The word "if" as used herein may be interpreted as "at the time of" or "when" or "in response to determining" or "in response to detecting", depending on the context. Similarly, the phrases "if it is determined" or "if (stated condition or event) is detected" may be interpreted as "when it is determined" or "in response to determining" or "when detecting (stated condition or event)" or "in response to detecting (stated condition or event)", depending on the context.

[0038] Various structural schematic diagrams of the embodiments disclosed in the present invention are shown in the accompanying drawings. These figures are not drawn to scale, and some details are magnified and some details may be omitted for the purpose of clear expression. The shapes of various regions and layers shown in the figures and the relative sizes and positional relationships therebetween are only exemplary, and may deviate in practice due to manufacturing tolerances or technical limitations, and those skilled in the art may additionally design regions / layers with different shapes, sizes, and relative positions according to actual needs.

[0039] The invention provides a degradation conversion rate calculation method based on an epoxy resin alcoholysis model. The method comprises the following steps: firstly, pouring an epoxy resin to solidify it into a shape, performing an epoxy resin alcoholysis degradation experiment at different temperatures, and recording the degradation conversion rates at different times; constructing an epoxy resin geometric model, analyzing and obtaining a degradation conversion rate differential expression containing a reaction rate constant and geometric parameters; solving a differential equation to obtain a reaction rate constant, and fitting the degradation activation energy using an Arrhenius formula; analyzing an ester exchange process between the epoxy resin and an alcohol solvent and a diffusion process of the alcohol solvent in the epoxy resin, and establishing a degradation conversion rate expression without geometric size parameters; finally, substituting the degradation reaction activation energy, and fitting and determining the degradation conversion rate expression without geometric size parameters; establishing an epoxy resin alcoholysis model according to the above steps, and aiming to provide a reference for the degradation process analysis of large-sized epoxy resins with complex shapes.

[0040] See also Figure 1 The present invention provides a method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model, comprising the following steps: S1. pouring epoxy resin to solidify it into shape, performing alcoholysis degradation experiment of epoxy resin at different temperatures, and recording the degradation conversion rate at different times; Epoxy resins are anhydride-cured resins and their composite materials, with a volume not exceeding 125 cm 3 The acid anhydride includes one or more combinations of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and maleic anhydride, and the composite filler includes one or more combinations of silicon micropowder, alumina powder, glass fiber and carbon fiber.

[0041] The alcohol solvent used in the degradation reaction is excessive to ensure the forward progress of the degradation reaction, and the alcohol solvent includes one or more combinations of ethanol, ethylene glycol and trifluoroethanol.

[0042] Degradation conversion rate The calculation is as follows: (1) in, m 1 is the initial mass of epoxy resin, m t for t Always check the quality of epoxy resin.

[0043] S2. Constructing a geometric model of epoxy resin based on the degradation conversion rate at different times, and analyzing and obtaining a differential expression of the degradation conversion rate containing a reaction rate constant and geometric parameters; Assuming that the density of the epoxy resin remaining after degradation is the same as that before degradation, it is convenient to obtain the relationship between the degradation conversion rate and the geometric parameters.

[0044] The differential form of the epoxy resin degradation conversion rate is expressed as the reaction rate constant and geometric parameters as follows: (2) in, k T for T The reaction rate constant at temperature, A is the epoxy resin surface area.

[0045] S3, solving the differential equation to obtain the reaction rate constant, and using the Arrhenius formula to fit the degradation activation energy; Solve the differential equation to get the reaction rate constant k T , substitute into the Arrhenius formula to get the degradation activation energy, the Arrhenius formula is as follows: (3) in, k 0 is the pre-exponential factor, ΔE For the degradation activation energy, R is the gas constant.

[0046] S4. Analyze the transesterification process between epoxy resin and alcohol solvent and the diffusion process of alcohol solvent in epoxy resin, and establish a degradation conversion rate expression without geometric size parameters based on degradation activation energy; The degradation process of epoxy resin is determined by two parts, one is the transesterification reaction rate, and the other is the diffusion of alcohol solvent. The differential form of the degradation conversion rate is proportional to the transesterification reaction rate. According to Fick's diffusion law, the diffusion distance is proportional to the power of half of the time. The differential form of the degradation conversion rate is as follows: (4) in, d (-COO-) / dt is the transesterification reaction rate, D is the diffusion coefficient.

[0047] The transesterification reaction rate is written as the product of the transesterification reaction rate constant and the substance concentration, and the expression is as follows: (5) in, k 1 is the transesterification reaction rate, φ 1 is the volume fraction of the solvent in the epoxy resin inner swelling layer, V 1 is the molar volume of alcohol solvent, V 2 is the molar volume of epoxy resin.

[0048] S5. Substitute the activation energy of the degradation reaction and determine the degradation conversion rate without geometric size parameters by fitting.

[0049] It will be appreciated by those skilled in the art that various aspects of the present invention may be implemented as systems, methods or program products. Therefore, various aspects of the present invention may be specifically implemented in the following forms, namely: complete hardware implementation, complete software implementation (including firmware, microcode, etc.), or a combination of hardware and software implementations, which may be collectively referred to herein as "circuits", "modules" or "platforms".

[0050] In another embodiment of the present invention, a degradation conversion rate calculation system based on the epoxy resin alcoholysis model is provided, which can be used to implement the above-mentioned degradation conversion rate calculation method based on the epoxy resin alcoholysis model. Specifically, the degradation conversion rate calculation system based on the epoxy resin alcoholysis model includes an experimental module, an analysis module, a fitting module, a construction module and a calculation module.

[0051] Among them, in the experimental module, epoxy resin is poured to solidify and shape it, and the alcoholysis degradation experiment of epoxy resin is carried out at different temperatures, and the degradation conversion rate at different times is recorded; The analysis module builds the geometric model of epoxy resin based on the degradation conversion rate at different times, and obtains the degradation conversion rate differential equation containing the reaction rate constant and geometric parameters; The fitting module solves the differential equation to obtain the reaction rate constant and fits it to obtain the degradation activation energy; Construct a module to analyze the transesterification process between epoxy resin and alcohol solvent and the diffusion process of alcohol solvent in epoxy resin, and establish a degradation conversion rate expression without geometric size parameters based on degradation activation energy; The calculation module substitutes the activation energy of the degradation reaction and determines the degradation conversion rate without geometric size parameters through fitting.

[0052] In another embodiment of the present invention, a terminal device is provided, the terminal device includes a processor and a memory, the memory is used to store a computer program, the computer program includes program instructions, and the processor is used to execute the program instructions stored in the computer storage medium. The processor may be a central processing unit (CPU), or other general-purpose processors, digital signal processors (DSP), application-specific integrated circuits (ASIC), field-programmable gate arrays (FPGA) or other programmable logic devices, discrete gates or transistor logic devices, discrete hardware components, etc., which are the computing core and control core of the terminal, which are suitable for implementing one or more instructions, and are specifically suitable for loading and executing one or more instructions to implement the corresponding method flow or corresponding function; the processor described in the embodiment of the present invention can be used for the operation of the degradation conversion rate calculation method based on the epoxy resin alcoholysis model, including: Epoxy resin is poured to solidify and form, and epoxy resin alcoholysis degradation experiments are carried out at different temperatures, and the degradation conversion rates at different times are recorded; a geometric model of epoxy resin is constructed based on the degradation conversion rates at different times, and a degradation conversion rate differential equation containing reaction rate constants and geometric parameters is obtained by analysis; the reaction rate constant is obtained by solving the differential equation, and the degradation activation energy is obtained by fitting; the ester exchange process between epoxy resin and alcohol solvent and the diffusion process of alcohol solvent in epoxy resin are analyzed, and a degradation conversion rate expression without geometric size parameters is established based on the degradation activation energy; the degradation reaction activation energy is substituted and the degradation conversion rate without geometric size parameters is determined by fitting.

[0053] See also Figure 4 , the terminal device is a computer device, and the computer device 60 of this embodiment includes: a processor 61, a memory 62, and a computer program 63 stored in the memory 62 and executable on the processor 61. When the computer program 63 is executed by the processor 61, the degradation conversion rate calculation method based on the epoxy resin alcoholysis model in the embodiment is implemented. To avoid repetition, it is not described one by one here. Alternatively, when the computer program 63 is executed by the processor 61, the functions of each model / unit in the degradation conversion rate calculation system based on the epoxy resin alcoholysis model in the embodiment are implemented. To avoid repetition, it is not described one by one here.

[0054] The computer device 60 may be a computing device such as a desktop computer, a notebook, a PDA, or a cloud server. The computer device 60 may include, but is not limited to, a processor 61 and a memory 62. Those skilled in the art will appreciate that Figure 4 This is only an example of the computer device 60 and does not constitute a limitation of the computer device 60. It may include more or fewer components than shown in the figure, or a combination of certain components, or different components. For example, the computer device may also include input and output devices, network access devices, buses, etc.

[0055] The processor 61 may be a central processing unit (CPU), or other general-purpose processors, digital signal processors (DSP), application-specific integrated circuits (ASIC), field-programmable gate arrays (FPGA) or other programmable logic devices, discrete gate or transistor logic devices, discrete hardware components, etc. A general-purpose processor may be a microprocessor or any conventional processor, etc.

[0056] The memory 62 may be an internal storage unit of the computer device 60, such as a hard disk or memory of the computer device 60. The memory 62 may also be an external storage device of the computer device 60, such as a plug-in hard disk, a smart media card (SMC), a secure digital (SD) card, a flash card, etc., equipped on the computer device 60.

[0057] Furthermore, the memory 62 may include both an internal storage unit of the computer device 60 and an external storage device. The memory 62 is used to store computer programs and other programs and data required by the computer device. The memory 62 may also be used to temporarily store data that has been output or is to be output.

[0058] See also Figure 5 , the terminal device is a chip, and the chip 600 of this embodiment includes a processor 622, which may be one or more, and a memory 632 for storing a computer program executable by the processor 622. The computer program stored in the memory 632 may include one or more modules, each corresponding to a set of instructions. In addition, the processor 622 may be configured to execute the computer program to execute the above-mentioned degradation conversion rate calculation method based on the epoxy resin alcoholysis model.

[0059] In addition, the chip 600 may further include a power supply component 626 and a communication component 650, wherein the power supply component 626 may be configured to perform power management of the chip 600, and the communication component 650 may be configured to implement communication, for example, wired or wireless communication, of the chip 600. In addition, the chip 600 may further include an input / output interface 658. The chip 600 may operate based on an operating system stored in the memory 632.

[0060] In another embodiment of the present invention, the present invention also provides a storage medium, specifically a computer-readable storage medium, which is a memory device in a terminal device for storing programs and data. It can be understood that the computer-readable storage medium here can include both the built-in storage medium in the terminal device and the extended storage medium supported by the terminal device. The computer-readable storage medium provides a storage space, which stores the operating system of the terminal. In addition, one or more instructions suitable for being loaded and executed by the processor are also stored in the storage space, and these instructions can be one or more computer programs. It should be noted that the computer-readable storage medium here can be a high-speed RAM memory, or a non-volatile memory (Non-VolatileMemory), such as at least one disk memory.

[0061] The processor may load and execute one or more instructions stored in a computer-readable storage medium to implement the corresponding steps of the method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model in the above embodiment; the processor may load and execute the following steps: Epoxy resin is poured to solidify and form, and epoxy resin alcoholysis degradation experiments are carried out at different temperatures, and the degradation conversion rates at different times are recorded; a geometric model of epoxy resin is constructed based on the degradation conversion rates at different times, and a degradation conversion rate differential equation containing reaction rate constants and geometric parameters is obtained by analysis; the reaction rate constant is obtained by solving the differential equation, and the degradation activation energy is obtained by fitting; the ester exchange process between epoxy resin and alcohol solvent and the diffusion process of alcohol solvent in epoxy resin are analyzed, and a degradation conversion rate expression without geometric size parameters is established based on the degradation activation energy; the degradation reaction activation energy is substituted and the degradation conversion rate without geometric size parameters is determined by fitting.

[0062] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. The components of the embodiments of the present invention described and shown in the drawings here can usually be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the drawings is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0063] Example By side length a =10 mm epoxy resin / silica powder composite cube as an example.

[0064] 1) The sample was cured at 120 ℃ / 2 h+150 ℃ / 6 h, and then mixed with trifluoroethanol and potassium phosphate for alcoholysis degradation at 105 ℃, 120 ℃ and 135 ℃. The degradation conversion rate at different times was recorded. The results are shown in the figure. Figure 2 shown.

[0065] 2) Construct a a The cube geometry model, when the dissolution erosion distance is x When the residual epoxy resin side length is a -2 x , assuming that the density of the residual epoxy resin is the same as before dissolution, the degradation conversion rate becomes: (6) The surface area of ​​the epoxy resin cube is: (7) in, A is the surface area of ​​the cube.

[0066] The differential expression of degradation rate is: (8) in, k T for T The reaction rate constant at temperature.

[0067] 3) Substitution t =0, w = 0, solve the differential equation to get the reaction rate constant k T , substitute k T and T The fitting result is Δ E ; (9) 4) Substituting the differential form of the degradation conversion rate into the epoxy resin cubic parameters yields: (10) 5) Finally, the relationship between degradation conversion rate, temperature and time is solved.

[0068] (11) Taking 120 °C as an example, substituting the activation energy of the degradation reaction, the fitting is determined C 0, the degradation conversion rate expression without geometric size parameters is obtained, the model fitting value and experimental results are shown in Figure 3 shown.

[0069] In summary, the present invention provides a method and system for calculating the degradation conversion rate based on the epoxy resin alcoholysis model, and calculates the reaction rate constant k T The effects of transesterification and alcohol solvent diffusion on the degradation process are considered at the same time. During the analysis, a degradation conversion rate expression without geometric parameters can be established through degradation experiments on small-sized samples. This method lays the foundation for the degradation model of large-sized epoxy resins with complex shapes, which is of great significance for subsequent large-scale industrial production applications.

[0070] The technicians in the relevant field can clearly understand that for the convenience and simplicity of description, only the division of the above-mentioned functional units and modules is used as an example for illustration. In practical applications, the above-mentioned function allocation can be completed by different functional units and modules as needed, that is, the internal structure of the device can be divided into different functional units or modules to complete all or part of the functions described above. The functional units and modules in the embodiment can be integrated in a processing unit, or each unit can exist physically separately, or two or more units can be integrated in one unit. The above-mentioned integrated unit can be implemented in the form of hardware or in the form of software functional units. In addition, the specific names of the functional units and modules are only for the convenience of distinguishing each other, and are not used to limit the scope of protection of this application. The specific working process of the units and modules in the above-mentioned system can refer to the corresponding process in the aforementioned method embodiment, which will not be repeated here.

[0071] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described or recorded in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0072] Those skilled in the art will appreciate that the units and algorithm steps of each example described in conjunction with the embodiments disclosed in the present invention can be implemented in electronic hardware, or a combination of computer software and electronic hardware. Whether these functions are performed in hardware or software depends on the specific application and design constraints of the technical solution. Professional and technical personnel can use different methods to implement the described functions for each specific application, but such implementation should not be considered to be beyond the scope of the present invention.

[0073] In the embodiments provided by the present invention, it should be understood that the disclosed devices / terminals and methods can be implemented in other ways. For example, the device / terminal embodiments described above are only schematic. For example, the division of the modules or units is only a logical function division. There may be other division methods in actual implementation, such as multiple units or components can be combined or integrated into another system, or some features can be ignored or not executed. Another point is that the mutual coupling or direct coupling or communication connection shown or discussed can be through some interfaces, indirect coupling or communication connection of devices or units, which can be electrical, mechanical or other forms.

[0074] The units described as separate components may or may not be physically separated, and the components shown as units may or may not be physical units, that is, they may be located in one place or distributed on multiple network units. Some or all of the units may be selected according to actual needs to achieve the purpose of the solution of this embodiment.

[0075] In addition, each functional unit in each embodiment of the present invention may be integrated into one processing unit, or each unit may exist physically separately, or two or more units may be integrated into one unit. The above-mentioned integrated unit may be implemented in the form of hardware or in the form of software functional units.

[0076] If the integrated module / unit is implemented in the form of a software functional unit and sold or used as an independent product, it can be stored in a computer-readable storage medium. Based on this understanding, the present invention implements all or part of the processes in the above-mentioned embodiment method, and can also be completed by instructing the relevant hardware through a computer program. The computer program can be stored in a computer-readable storage medium, and the computer program can implement the steps of the above-mentioned various method embodiments when executed by the processor. Among them, the computer program includes computer program code, and the computer program code can be in source code form, object code form, executable file or some intermediate form. The computer-readable medium may include: any entity or device capable of carrying the computer program code, recording medium, U disk, mobile hard disk, disk, optical disk, computer memory, read-only memory (ROM), random access memory (RAM), electric carrier signal, telecommunication signal and software distribution medium, etc. It should be noted that the content contained in the computer-readable medium can be appropriately increased or decreased according to the requirements of legislation and patent practice in the jurisdiction. For example, in some jurisdictions, according to legislation and patent practice, computer-readable media do not include electric carrier signals and telecommunication signals.

[0077] The present application is described with reference to the flowcharts and / or block diagrams of the methods, devices, and computer program products according to the embodiments of the present application. It should be understood that each process and / or block in the flowchart and / or block diagram, as well as the combination of the processes and / or blocks in the flowchart and / or block diagram, can be implemented by computer program instructions. These computer program instructions can be provided to a processor of a general-purpose computer, a special-purpose computer, an embedded processor, or other programmable data processing device to generate a machine, so that the instructions executed by the processor of the computer or other programmable data processing device generate instructions for implementing the processes in the flowchart and / or block diagram. Figure 1 A process or multiple processes and / or boxes Figure 1 A device that provides the functions specified in a block or multiple blocks.

[0078] These computer program instructions may also be stored in a computer readable memory capable of directing a computer or other programmable data processing device to operate in a specific manner, so that the instructions stored in the computer readable memory produce an article of manufacture including an instruction device, which implements the process Figure 1A process or multiple processes and / or boxes Figure 1 A function specified in one or more boxes.

[0079] These computer program instructions can also be loaded onto a computer or other programmable data processing device so that a series of operating steps are executed on the computer or other programmable device to produce a computer-implemented process, thereby providing instructions for implementing the process in the computer or other programmable device. Figure 1 A process or multiple processes and / or boxes Figure 1 The steps for the functions specified in one or more boxes.

[0080] The above contents are only for explaining the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A method for calculating the degradation conversion rate based on an epoxy resin alcoholysis model, characterized in that: The following steps are involved: Pour epoxy resin to solidify it, perform alcoholysis degradation experiment on epoxy resin at different temperatures, and record the degradation conversion rate at different times; The geometric model of epoxy resin was constructed based on the degradation conversion rate at different times, and the degradation conversion rate differential equation containing reaction rate constant and geometric parameters was obtained through analysis. The reaction rate constant is obtained by solving the differential equation and the degradation activation energy is obtained by fitting; The transesterification process between epoxy resin and alcohol solvent and the diffusion process of alcohol solvent in epoxy resin were analyzed, and the degradation conversion rate expression without geometric size parameters was established based on the degradation activation energy. Substituting the activation energy of the degradation reaction, the degradation conversion rate without geometric size parameters was determined by fitting.

2. The method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model according to claim 1, wherein: The epoxy resin is an anhydride-cured resin and a composite material thereof, wherein the anhydride comprises a combination of one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and maleic anhydride, and the composite filler comprises a combination of one or more of silicon micropowder, alumina powder, glass fiber and carbon fiber.

3. The method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model according to claim 2, wherein: The volume of epoxy resin is less than or equal to 125 cm 3 .

4. The method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model according to claim 1, wherein: Degradation conversion rate for: in, m 1 is the initial mass of epoxy resin, m t for t Always check the quality of epoxy resin.

5. The method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model according to claim 4, characterized in that: The alcohol solvent used in the degradation reaction is excessive, and the alcohol solvent includes one or more combinations of ethanol, ethylene glycol and trifluoroethanol.

6. The method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model according to claim 1, characterized in that: The degradation conversion rate differential equation containing the reaction rate constant and geometric parameters is as follows: in, k T for T The reaction rate constant at temperature, f ( a ) is a geometric parameter function.

7. The method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model according to claim 1, characterized in that: The degradation activation energy obtained by fitting is: Solve the differential equation to get the reaction rate constant k T , substitute into the Arrhenius formula to get the degradation activation energy, the Arrhenius formula is as follows: in, k 0 is the pre-exponential factor, ΔE For the degradation activation energy, R is the gas constant.

8. The method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model according to claim 1, characterized in that: The degradation conversion rate expression is as follows: in, d (-COO-) / dt is the transesterification reaction rate, D is the diffusion coefficient.

9. The method for calculating the degradation conversion rate based on the epoxy resin alcoholysis model according to claim 8, characterized in that: Transesterification reaction rate d (-COO-) / dt for: in, k 1 is the transesterification reaction rate, φ 1 is the volume fraction of the solvent in the epoxy resin inner swelling layer, V 1 is the molar volume of alcohol solvent, V 2 is the molar volume of epoxy resin.

10. A degradation conversion rate calculation system based on epoxy resin alcoholysis model, characterized in that: include: Experimental module: pouring epoxy resin to solidify it, carrying out alcoholysis degradation experiment of epoxy resin at different temperatures, and recording the degradation conversion rate at different times; The analysis module builds the geometric model of epoxy resin based on the degradation conversion rate at different times, and obtains the degradation conversion rate differential equation containing the reaction rate constant and geometric parameters; The fitting module solves the differential equation to obtain the reaction rate constant and fits it to obtain the degradation activation energy; Construct a module to analyze the transesterification process between epoxy resin and alcohol solvent and the diffusion process of alcohol solvent in epoxy resin, and establish a degradation conversion rate expression without geometric size parameters based on degradation activation energy; The calculation module substitutes the activation energy of the degradation reaction and determines the degradation conversion rate without geometric size parameters through fitting.

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