CN111760534A - Microwave curing reaction system and method for microwave curing and quantitative evaluation of microwave curing reaction non-thermal effect - Google Patents
Microwave curing reaction system and method for microwave curing and quantitative evaluation of microwave curing reaction non-thermal effect Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a microwave curing reaction system, a microwave curing reaction method and a method for quantitatively evaluating the non-thermal effect of the microwave curing reaction. The temperature control circulation unit, the infrared in-situ detection unit and the isothermal reactor unit are ingeniously combined, the influence of thermal effect on reaction in the microwave irradiation process is eliminated, the reaction degree of resin is tracked through real-time infrared, and the reaction activation energy change condition under the condition is further calculated, so that the non-thermal effect of microwave curing is quantitatively evaluated, and the key bottleneck problem in the research of microwave irradiation accelerated curing of the composite material is solved; moreover, the cured resin obtained by the microwave curing reaction system has better mechanical property.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a microwave curing reaction system, a microwave curing reaction method thereof and a method for quantitatively evaluating the non-thermal effect of the microwave curing reaction.
Background
Microwave irradiation is one of the important means for accelerating the curing of matrix resin in the field of composite material processing. The liquid resin is changed into a solid state by the action of microwaves, namely, the microwaves induce the resin to form a three-dimensional insoluble and infusible network structure. The microwave field can excite polar molecules to vibrate at fixed points, so that heat is generated, the temperature of a reaction system is increased, and compared with a conduction heating mode, the microwave irradiation can avoid the phenomenon of uneven solidification caused by local hot spots; the processing time can be further shortened by the characteristic of microwave irradiation instantaneous heating; the microwave penetration capability is strong, and the processing method has great advantages in the processing aspect of complex structural parts; meanwhile, with the development of the technology, the size of the microwave generating equipment is continuously reduced, the cost is continuously reduced, and the advantages in the aspect of industrial production are more obvious. In addition, the microwave irradiation can maintain the accelerating effect on the resin curing in extreme environments such as vacuum, low temperature and the like, so that the microwave irradiation becomes one of means for rapidly repairing the aerospace craft in orbit.
However, the research and evaluation of the resin curing acceleration mechanism still have a bottleneck on the basic method, and mainly focus on how to evaluate and quantitatively calculate the non-thermal effect of microwave irradiation. The microwave can not only increase the reaction temperature by resonating the polar groups and further accelerate the curing, but also increase the reaction speed by increasing the probability of mutual collision of the polar groups. This acceleration effect does not result from an increase in the temperature of the reaction system and is therefore referred to as "non-thermal effect". Although academia argues about the principle of microwave non-thermal effect, 32429is widely accepted under the support of a large amount of data, the method for quantitatively evaluating the non-thermal effect is unimportant, and the bottleneck is a method for separating the microwave thermal effect from the non-thermal effect in a lack of research.
There is currently no uniform and widely recognized method in the field. The difficulty is that microwave irradiation must cause polar molecule resonance, which leads to the increase of system temperature, but the reaction temperature has an influence on the non-thermal effect of the microwave. By accurately detecting the temperature of the reactant under microwave irradiation and simulating temperature rise, the reaction rate difference between a conduction heating sample and a microwave irradiation sample under the same temperature rise condition can be compared, and the non-thermal effect of the microwave irradiation under the temperature change condition can be quantitatively calculated. Boey1，Navabpour2([1]F.Y.C.Boey,B.H.Yap,Microwave curing ofan epoxy-amine system:effect ofcuring agent on the glass-transitiontemperature.Polym.Test.20(2001)837-845；[2]The research methods used by researchers such as P.Navabpour, A.Nesbit, T.Man, R.J.day, company soft sight peptides of a DGEBA/Acid Anhydride Epoxy resin system Using Differential Scanning and a Microwave-Heated calibration.J.appl.Polymer.Sci.104 (2007)2054-2063.) can prove the existence of Microwave irradiation non-thermal effect based on the above means, and obtain the overall change trend of activation energy for the specific reaction temperature interval of the specific resin. However, the above method can only be studied for the non-thermal effect in a certain temperature range, and the value of the non-thermal effect changes according to the temperature rise rate, so that the above result is not universal. In the actual microwave irradiation curing process of the composite material, the overall temperature of the resin is greatly changed and finally tends to be stable. The non-thermal effect dynamic data which are obtained by simulating temperature rise measurement and calculation and only aim at specific temperature rise rate and temperature range cannot be used in practical application scenes. How to accurately and quantitatively evaluate the non-thermal effect of microwave irradiation curing is one of hot bottleneck problems which are commonly concerned in the fields of composite material application and scientific research.
Disclosure of Invention
In order to eliminate the influence of microwave thermal effect on the non-thermal effect test process, the invention utilizes heat-conducting silicone oil which is less influenced by microwave as a heat-conducting system of a temperature control circulating unit, utilizes a microwave transmitting unit to adjust the microwave irradiation dose, utilizes an infrared in-situ detection unit to track the reaction degree in real time, designs, connects and calibrates the structure, obtains the reaction activation energy by analyzing the constant-temperature reaction kinetic parameters and calculating, realizes the quantitative calculation of the microwave irradiation non-thermal effect, and solves the bottleneck problem in the research and application of the microwave accelerated curing of the composite material. The invention designs and assembles the microwave-induced isothermal reactor, which can eliminate the influence of the thermal effect of the microwave on the curing reaction and can independently evaluate the non-thermal effect of the microwave curing reaction.
The invention aims to provide a microwave curing reaction system, which comprises an isothermal reaction unit and an infrared in-situ detection unit; the isothermal reaction unit comprises a microwave transmitting unit and an isothermal reactor which are positioned in a microwave resonant cavity, and a temperature control circulating unit connected with the microwave resonant cavity, and the infrared in-situ detection unit is connected with the isothermal reactor in the isothermal reaction unit.
The infrared in-situ detection unit adopts instruments which can perform infrared in-situ detection in the prior art, and comprises an infrared light source, a diaphragm, an interferometer, a detector, an infrared reflector and the like. When the resin to be solidified reacts in the isothermal reactor of the microwave resonant cavity for a certain time, infrared detection is carried out, light beams emitted by infrared spectrums enter the interferometer after passing through the diaphragm, the light beams pass through the resin to be solidified of the isothermal reactor and then are focused on the detector to obtain an infrared spectrogram of a sample, and the solidification degree of the sample is judged according to the obtained infrared spectrogram.
The temperature control circulating unit comprises a heat-conducting silicone oil circulating pipeline and a constant temperature control platform connected with the heat-conducting silicone oil circulating pipeline; the heat-conducting silicone oil which is less affected by microwaves is used as a heat-conducting medium, the silicone oil circulating pipeline is connected with the constant-temperature control platform to play a role in constant-temperature control, and the temperature of a sample can be ensured to be as close to a numerical value displayed by a constant-temperature display as possible due to the fact that the silicone oil in the system has a high heat-conducting coefficient;
the isothermal reaction unit also comprises a frequency converter, the frequency converter is connected with the microwave transmitting unit, the frequency converter converts 50Hz power frequency into 2450MHz +/-50 Hz microwave frequency, and a Micro Control Unit (MCU) in the frequency converter adjusts the self-adaptive controller according to the change conditions of mathematical models such as temperature change data, reaction substance polarity, heat capacity change, reaction time and the like detected by the thermal resistance sensor in real time, and automatically controls the microwave output power in a frequency conversion manner;
a mould is arranged in the isothermal reactor; the mold is preferably a dynamic thermo-mechanical analysis (DMA) mold or a fourier infrared spectrometer test mold.
It is another object of the present invention to provide a method for microwave curing reactions using the above system, comprising the steps of:
(1) adding resin to be cured into an isothermal reactor;
(2) modulating and stabilizing the microwave frequency of the isothermal reactor through a frequency converter;
(3) carrying out constant-temperature microwave heating curing reaction;
(4) the reaction degree was monitored using an infrared in situ detection unit.
In the step (1), the resin to be cured is selected from at least one of epoxy resin and unsaturated polyester, preferably epoxy resin. During the curing reaction, the resin to be cured and the curing agent are mixed, and the mixture is obtained after uniform stirring, poured into a mold and added into an isothermal reactor; the mold is a dynamic thermomechanical analysis mold, and the dynamic thermomechanical analysis (DMA) mold is a mold matched with a dynamic thermomechanical analyzer in the prior art.
When the resin to be cured is epoxy resin, in the microwave curing reaction:
the epoxy value range of the epoxy resin is 0.44-0.67; the epoxy resin is a multifunctional epoxy resin, is selected from at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin and alicyclic epoxy resin, is preferably selected from glycidyl ether epoxy resin, and is more preferably selected from bisphenol A epoxy resin;
the curing agent is selected from linear polyether amine, preferably the molecular weight of the linear polyether amine is 230-2000 g/mol, the amine value is 0.95-8.1 mmol/g, the active hydrogen equivalent is 60-514 g/eq, more preferably the molecular weight of the linear polyether amine is 230g/mol, the amine value is 7.5-8.1 mmol/g, and the active hydrogen equivalent is 60 g/eq;
the amount of the curing agent is 20 to 60 parts by weight, preferably 30 to 50 parts by weight, based on 100 parts by weight of the epoxy resin;
an accelerator is also added in the epoxy resin curing reaction, and the accelerator is an amine accelerator, preferably selected from 2,4, 6-tris (dimethylaminomethyl) phenol; the amount of the accelerator is 0.1 to 2 parts by weight, preferably 0.2 to 1.5 parts by weight, based on 100 parts by weight of the epoxy resin;
removing bubbles from the mixture of the resin to be cured and the curing agent under vacuum;
during curing reaction, the microwave frequency is 2400-2500 Hz, the constant-temperature heating temperature is 10-250 ℃, and the curing reaction time is 2-5 h.
The epoxy resin can be cured by adopting the reaction system, and the obtained epoxy resin cured product has excellent thermodynamic property, glass transition temperature and thermal stability.
The invention also aims to provide a method for quantitatively evaluating the non-thermal effect of the microwave curing reaction by adopting the microwave curing reaction system, which comprises the following steps:
(1) adding resin to be cured into an isothermal reactor;
(2) modulating and stabilizing the microwave frequency of the isothermal reactor through a frequency converter;
(3) carrying out constant-temperature microwave heating curing reaction;
(4) monitoring the reaction degree by using an infrared spectrogram obtained by an infrared in-situ detection unit;
(5) and (4) calculating the infrared spectrogram obtained in the step (4) by combining a formula to obtain the activation energy and the pre-exponential factor of the microwave curing reaction so as to quantitatively evaluate the non-thermal effect of the microwave curing reaction.
The resin to be cured for quantitatively evaluating the non-thermal effect of the microwave curing reaction is selected from at least one of epoxy resin and unsaturated polyester, preferably epoxy resin, the resin to be cured and a curing agent are mixed in the step (1), the uniformly stirred mixture is coated on a potassium bromide tablet, a double-layer potassium bromide tablet is formed by a tablet pressing method, and the double-layer potassium bromide tablet is added into an isothermal reactor.
When the resin to be cured is epoxy resin, the method for quantitatively evaluating the non-thermal effect of the microwave curing reaction comprises the following steps:
the epoxy value range of the epoxy resin is 0.44-0.67; the epoxy resin is a multifunctional epoxy resin, is selected from at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin and alicyclic epoxy resin, is preferably selected from glycidyl ether epoxy resin, and is more preferably selected from bisphenol A epoxy resin;
the curing agent is selected from linear polyether amine, preferably the molecular weight of the linear polyether amine is 230-2000 g/mol, the amine value is 0.95-8.1 mmol/g, the active hydrogen equivalent is 60-514 g/eq, more preferably the molecular weight of the linear polyether amine is 230g/mol, the amine value is 7.5-8.1 mmol/g, and the active hydrogen equivalent is 60 g/eq;
the amount of the curing agent is 20 to 60 parts by weight, preferably 30 to 50 parts by weight, based on 100 parts by weight of the epoxy resin;
an accelerator is also added in the epoxy resin curing reaction, and the accelerator is an amine accelerator, preferably selected from 2,4, 6-tris (dimethylaminomethyl) phenol; the amount of the accelerator is 0.1 to 2 parts by weight, preferably 0.2 to 1.5 parts by weight, based on 100 parts by weight of the epoxy resin;
removing bubbles from the mixture of the resin to be cured and the curing agent under vacuum;
in the method for quantitatively evaluating the microwave curing non-thermal effect, the microwave frequency is 2400-2500 Hz; heating at a constant temperature of 10-250 ℃; the curing reaction time is 2-5 h; the thickness of the potassium bromide tablet is 0.7-0.8 mm, and the diameter is 13-15 mm; the smear thickness of the uniformly stirred mixture is 0.8-0.9 mm.
The method comprises the steps of placing a double-layer KBr sheet coated with a mixture in a microwave-induced isothermal reactor, tracking the reaction degree through a Fourier transform infrared spectrum of an infrared in-situ detector, obtaining characteristic peaks (such as a characteristic peak of an epoxy structure and a characteristic peak of a benzene ring) of a characteristic structure from the obtained infrared spectrum, performing integral treatment on the characteristic peaks, and performing isothermal dynamics calculation and analysis by utilizing a secondary autocatalytic reaction and an Arrhenius equation to obtain the activation energy and pre-exponential factor of the isothermal microwave reaction.
Taking the curing of epoxy resin as an example, the curing of epoxy resin conforms to the two-stage autocatalytic reaction, and the kinetic equation is as follows:
where a represents the degree of cure and k represents the rate constant.
The expression of the Arrhenius equation is as follows:
integrating the epoxy peak and benzene ring peak with the measured infrared spectrogram, wherein a is conversion rate, A is915Is the area of the epoxy peak, A1508Is the area of the benzene ring peak, wherein the value of the conversion a is the area of the epoxy peak/the area of the benzene ring peak. Under the microwave and thermal curing conditions, obtaining a curve of an a-t isothermal curing system of the epoxy resin, and performing straight line fitting by taking (da/dt)/(1-a) as an ordinate and a as an abscissa, wherein the slope is k2Intercept of k1Linear value of ordinate ln (60 × k)1) And ln (60 × k)2) The abscissa is 1000/T (1/K) and the slope value is-Eathe/R and intercept are calculated as ln (A) by Arrhenius equation, and kinetic parameters obtained by isothermal kinetic calculation analysis are pre-exponential factor A and activation energy Ea。
Compared with the traditional thermal effect, the microwave non-thermal effect causes the kinetic energy distribution in a molecular chain to be uneven, for example, an epoxy group and an amino group are both reaction groups and strong-polarity functional groups, and are easily excited under the microwave effect to improve the self kinetic energy, so that the reaction activity is improved, the molecular main chain has weaker microwave absorption capacity, so that the kinetic energy of the molecular chain under the constant temperature condition is reduced, the macro expression is that the molecular average kinetic energy distribution is uneven, and although the polar groups contain more kinetic energy, the apparent activation energy is low.
The microwave reactor utilizes heat-conducting silicone oil which is slightly influenced by microwaves as a heat-conducting medium in the temperature control circulating unit; the heat conduction silicone oil circulating pipeline is connected with the constant temperature control platform to play a role in constant temperature control, and silicone oil and potassium bromide in the system have higher heat conductivity coefficients, so that the temperature of a sample can be ensured to be as close to a numerical value displayed by the constant temperature display as possible. The microwave irradiation dose is adjusted through a microwave reaction control box in a microwave emission unit, the temperature of a cured object under microwave irradiation is accurately detected and temperature rise simulation is carried out, the difference of reaction rates between conduction heating and microwave irradiation samples under the same temperature rise condition is compared, heat of reaction temperature rise caused by the fact that microwaves act on resonant polar groups is removed, and the activation energy of the microwave effect reduction after the heat effect is removed can be attributed to the microwave non-heat effect. Therefore, the non-thermal effect under the action of the constant-temperature microwave reactor means that the microwave curing reaction system designed in the invention can utilize the heat-conducting silicone oil to timely remove excessive heat, reduce the heat conduction outside the reactant, control the temperature of the curing system to be constant, enable the macroscopic molecular average kinetic energy in the system to be the same, and better evaluate the non-thermal effect of the microwave curing reaction.
In the microwave curing technology, the heat effect and the non-heat effect of the microwave reaction cannot be distinguished in the existing technical equipment, and the influence of the microwave action on the activation energy of the resin cannot be quantitatively calculated; the application of microwaves to various resins cannot be accurately guided; the microwave effect cannot be properly utilized to improve the resin properties. The invention can compare the reaction rate difference between the conduction heating and the microwave irradiation sample under the same temperature rise condition by accurately detecting the temperature of the reactant under the microwave irradiation and simulating the temperature rise, and can quantitatively calculate the non-thermal effect of the microwave irradiation by calculating the reaction activation energy. The temperature control circulating unit of the microwave reactor replaces a high-voltage transformer used by the traditional microwave reactor, the temperature of the heat-conducting silicone oil in the reactor is monitored in real time by using a thermocouple, the accurate detection and the temperature rise simulation are carried out, and the technical defect that the high-voltage transformer is impacted by spike pulse to cause frequent damage of the transformer when the temperature of the traditional microwave reactor is accurately controlled is perfectly overcome. And on the basis, the epoxy resin is cured by the constant-temperature microwave reactor, so that the mechanical property, the glass transition temperature and the thermal stability of the cured epoxy resin are improved. Compared with other microwave reactors, the microwave curing reaction system has more stable and accurate control on temperature; the improvement of the resin performance is controllable.
In addition, on the basis of the existing constant-temperature microwave reactor, the invention further controls and optimizes various reaction condition parameters, such as power adjustment of the microwave reactor, thickness of a KBr sheet structure, epoxy value of epoxy resin and the like. The embodiment proves that the energy consumption can be reduced while the product performance is improved, and the curing reaction process is green and environment-friendly.
Drawings
Fig. 1 is a schematic structural diagram of a microwave curing reaction system, in which a microwave emitting unit 101, a microwave resonant cavity 102, a thermostatic control platform 103, a heat-conducting silicone oil circulation pipeline 104, an isothermal reactor 105, and an infrared in-situ detection unit 106 are shown;
FIG. 2 is a schematic view of a constant temperature microwave reaction double-layer potassium bromide tablet, in which a metal fixing ring 201, a potassium bromide tablet 202 and an object tablet 203 to be measured are provided;
FIG. 3 is an infrared spectrum of an epoxy resin measured under microwave conditions of example 1 and heat curing conditions of comparative example 1 at different times, FIG. 3-a is an infrared spectrum of an epoxy resin at 60 ℃ at different times, FIG. 3-b is an infrared spectrum of an epoxy resin at 60 ℃ at different times, FIG. 3-c is a conversion of an epoxy resin under microwave and heat curing conditions, c1Conversion of epoxy resin upon microwave curing at 60 ℃, c2Is the conversion of the epoxy resin upon thermal curing at 60 ℃;
FIG. 4 is an analysis of fitted kinetics of infrared spectrum measured at different times for epoxy resins under microwave conditions of example 1 and under heat curing conditions of comparative example 1, FIG. 4-a is a fitted curve of epoxy resin when heat cured at 60 ℃ and FIG. 4-b is a fitted curve of epoxy resin when microwave cured at 60 ℃ with (da/dt)/(1-a) as ordinateThe standard, a is a straight line fitting with abscissa and the slope is k2(solid line) intercept k1(dotted line);
FIG. 5 is a DMA curve of an epoxy resin under microwave conditions of example 1 and under heat curing conditions of comparative example 1, FIG. 5-a is a storage modulus (G') curve, and FIG. 5-b is a loss angle factor (Tan) curve, wherein a solid line is a DMA curve of a heat-cured epoxy resin and a dotted line is a DMA curve of a microwave-cured epoxy resin;
FIG. 6 is a TGA curve of an epoxy resin under microwave conditions of example 1 and under thermal curing conditions of comparative example 1, FIG. 6-a is a TG curve of an epoxy resin under different conditions of microwave and thermal curing, and FIG. 6-b is a DTG curve of an epoxy resin under different conditions of microwave and thermal curing, wherein a solid line is a thermal weight loss curve of the epoxy resin during thermal curing, and a dotted line is a thermal weight loss curve of the microwave-cured epoxy resin;
FIG. 7 shows the cross-sectional morphology of the epoxy resin under the microwave condition of example 1 and the thermosetting condition of comparative example 1, FIG. 7-a shows the cross-sectional morphology of the epoxy resin during thermosetting, and FIG. 7-b shows the cross-sectional morphology of the epoxy resin during microwave curing, which shows that the epoxy resin obtained by microwave irradiation is cured more uniformly, has dense silver streaks at fracture, and has good fracture toughness.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The sources of the compounds used in the examples are as follows:
epoxy resin DGEBA (E51, E44) was from yueyang barlinghuaxing petrochemical limited (china); the curing agent polyetheramine D230 is from Beijing YinuoKai science and technology Co., Ltd (China); accelerator 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) was obtained from Beijing chemical plant (China).
The test instruments and test conditions used in the examples were as follows:
thermo-mechanical properties: adopting a TAInstrucnt Q800 dynamic thermomechanical analyzer (DMA analyzer), adopting a tensile mode for testing, wherein the heating rate is 5 ℃/min, the frequency is 1Hz, and the temperature range is-50-200 ℃;
thermogravimetric analysis: the type of a thermogravimetric analyzer (TGA) is TG209, the temperature is raised at a rate of 10 ℃/min in a nitrogen atmosphere, and the weight of a test sample is about 5mg from 40 ℃ to 600 ℃;
transmission electron microscopy: characterizing the epoxy fracture morphology with a scanning electron microscope (SEM, JEOL, JSM-6700M) at an accelerating voltage of 5kV, and sputtering all surfaces of the sample with gold to improve conductivity;
infrared characterization: potassium bromide tablets in the thermostated microwave reactor were detected by Alpha-T infrared spectroscopy (Bruker, Germany) with a resolution of 4cm-1In the range of 4000-400 cm-1。
The microwave curing reaction system comprises an isothermal reaction unit and an infrared in-situ detection unit, wherein the isothermal reaction unit comprises a microwave emitting unit 101 and an isothermal reactor 105 which are positioned in a microwave resonant cavity 102, and a temperature control circulation unit connected with the microwave resonant cavity 102, the infrared in-situ detection unit 106 is connected with the isothermal reactor 105, and the temperature control circulation unit comprises a heat-conducting silicone oil circulation pipeline 104 and a constant temperature control platform 103 connected with the heat-conducting silicone oil circulation pipeline. The isothermal reaction unit further comprises a frequency converter, and the frequency converter is connected with the microwave transmitting unit 101.
The constant temperature microwave curing system parameters are as follows:
table 1: constant temperature microwave curing system parameters
| Power supply: | AC220V±10％50Hz |
| input power: | 1350W |
| microwave power: | less than or equal to 900W (0-900 continuous automatic frequency conversion adjustment) |
| Microwave frequency: | 2450MHz±50Hz |
| temperature control: | constant temperature mode (Room temperature-250 degree) |
| Resolution ratio: | 0.1℃ |
| temperature control precision: | ±1℃ |
| number of program segments: | |
| The working time is as follows: | not limited for a long time |
| Interface: | reaction system |
| Communication interface: | is free of |
| The working size is as follows: | 325 x 202 (length, width, height) mm |
| The external dimension is as follows: | 500 x 420 x 400 (length, width, height) mm |
Comparative example 1
E51 and D230 were mixed in a 1:0.31 weight ratio and 0.5 wt% DMP-30 was added as an accelerator. The mixture was stirred uniformly and the bubbles were removed under vacuum, then cast in a DMA mould of size 40mm x 6mm x 1mm, cured in an oven at 60 ℃ for 3h and the cured product at different times during curing was tested by infrared spectroscopy.
After the reaction is finished, performing DMA, TGA and TEM characterization on the cured product, and calculating to obtain E by combining the obtained infrared spectrogram with a formulaa1、Ea220.0kJ/mol and 55.6kJ/mol respectively, and a glass transition temperature TgAt 78.2 ℃ and an initial decomposition temperature of 376.8 ℃.
Example 1
E51 and D230 were mixed in a 1:0.31 weight ratio and 0.5 wt% DMP-30 was added as an accelerator. The mixture was stirred uniformly and the bubbles were removed under vacuum, then poured into a DMA mould of size 40mm x 6mm x 1mm, placed in a microwave induced isothermal reactor and cured in a constant temperature microwave reactor at 60 ℃ for 3h, and the cured product at different times during curing was subjected to infrared spectroscopy.
After the reaction is finished, performing DMA, TGA and TEM characterization on the cured product, and calculating to obtain E by combining the obtained infrared spectrogram with a formulaa1、Ea2Respectively 18.2kJ/mol and 52.2kJ/mol, and a glass transition temperature Tg84.6 ℃ and an initial decomposition temperature of 383.2 ℃.
Example 2
E51 and D230 were mixed in a 1:0.45 weight ratio and 0.2 wt% DMP-30 was added as an accelerator. The mixture was stirred uniformly and the bubbles were removed under vacuum, and 1mg of the mixture was applied between two KBr plates, 0.7mm thick, 13mm diameter and 0.8mm reactant thickness, and sealed with PTFE tape. Placing the double-layer KBr sheet in a microwave-induced isothermal reactor, curing for 3h in a constant-temperature microwave reactor at 60 ℃, performing infrared spectrum test on cured products at different times in the curing process, and calculating to obtain E by combining the obtained infrared spectrogram with a formulaa1、Ea2Are respectively 19.1kJ/mol、53.5kJ/mol。
Example 3
E51 and D230 were mixed in a 1:0.31 weight ratio and 0.5 wt% DMP-30 was added as an accelerator. The mixture was stirred uniformly and the bubbles were removed under vacuum, and 1mg of the mixture was applied between two KBr plates, 0.7mm thick, 13mm diameter and 0.8mm reactant thickness, and sealed with PTFE tape. Placing the double-layer KBr sheet in a microwave-induced isothermal reactor, curing for 3h in a 80 ℃ isothermal microwave reactor, performing infrared spectrum test on cured products at different times in the curing process, and calculating to obtain E by combining the obtained infrared spectrogram with a formulaa1、Ea2Respectively 17.8kJ/mol and 51.6 kJ/mol.
Example 4
E44 and D230 were mixed in a 1:0.31 weight ratio and 0.5 wt% DMP-30 was added as an accelerator. The mixture was stirred uniformly and the bubbles were removed under vacuum, and 1mg of the mixture was applied between two KBr plates, 0.7mm thick, 13mm diameter and 0.8mm reactant thickness, and sealed with PTFE tape. Placing the double-layer KBr sheet in a microwave-induced isothermal reactor, curing for 3h in a constant-temperature microwave reactor at 60 ℃, performing infrared spectrum test on cured products at different times in the curing process, and calculating to obtain E by combining the obtained infrared spectrogram with a formulaa1、Ea2Respectively 19.6kJ/mol and 55.2 kJ/mol.
As can be seen from the data of examples and comparative examples, the reaction activation energy of the epoxy resin prepared in the examples of the present invention is significantly lower than that of the comparative example, and in comparison of example 1 with comparative example 1, E in example 1 caused by microwave non-thermal effecta1、Ea2Respectively 18.2kJ/mol and 52.2kJ/mol, and respectively reduced by 9.0 percent and 6.4 percent compared with the value of the comparative example 1 without microwave irradiation, and the comparison shows that the glass transition temperature, the initial decomposition temperature, the room temperature modulus, the carbon residue rate and the curing uniformity of the epoxy resin cured by the constant-temperature microwave reaction system provided by the invention in the example 1 are all higher than those of the epoxy resin cured by the conventional heat in the comparative example 1, which shows that the non-thermal action of the microwave promotes the curing of the epoxy resin, and can improve the curing effect of the epoxy resinProperties of the cured epoxy resin.
Compared with a comparative example, the types of reactors, the addition amount of the accelerator, the curing temperature and epoxy resins with different epoxy values are respectively adjusted in examples 1-4, and comparison shows that the microwave curing reaction system can effectively reduce activation energy and improve reaction rate and mechanical property; the activation energy can be increased and the reaction rate can be reduced by reducing the addition amount of the accelerator, the curing temperature and the epoxy value of the epoxy resin, and the reaction conditions can be effectively regulated and controlled according to actual needs. The constant-temperature microwave reactor can reduce energy loss, improve the reaction rate of epoxy resin, improve the performance of the epoxy resin, improve the curing depth and meet the requirements of green chemical industry.
Claims (10)
1. A microwave solidification reaction system comprises an isothermal reaction unit and an infrared in-situ detection unit, and is characterized in that: the isothermal reaction unit comprises a microwave transmitting unit and an isothermal reactor which are positioned in a microwave resonant cavity, and a temperature control circulating unit connected with the microwave resonant cavity; the infrared in-situ detection unit is connected with the isothermal reactor in the isothermal reaction unit.
2. The system of claim 1, wherein:
the temperature control circulating unit comprises a heat-conducting silicone oil circulating pipeline and a constant temperature control platform connected with the heat-conducting silicone oil circulating pipeline; and/or the presence of a gas in the gas,
the isothermal reaction unit also comprises a frequency converter, and the frequency converter is connected with the microwave transmitting unit; and/or the presence of a gas in the gas,
a mould is arranged in the isothermal reactor; the mold is preferably a dynamic thermo-mechanical analysis mold or a fourier infrared spectrometer test mold.
3. A method of microwave curing reactions according to the system of claim 1 or 2, comprising the steps of:
(1) adding resin to be cured into an isothermal reactor;
(2) modulating and stabilizing the microwave frequency of the isothermal reactor through a frequency converter;
(3) carrying out constant-temperature microwave heating curing reaction;
(4) and monitoring the reaction degree by using an infrared spectrogram obtained by an infrared in-situ detection unit.
4. The method according to claim 3, wherein the resin to be cured in step (1) is at least one selected from epoxy resin and unsaturated polyester, preferably epoxy resin.
5. The method according to claim 4, wherein the step (1) comprises mixing the resin to be cured and the curing agent, stirring uniformly to obtain a mixture, pouring the mixture into a mold, and adding the mixture into an isothermal reactor; the mold is a dynamic thermomechanical analysis mold.
6. The method according to claim 5, wherein when the resin to be cured is an epoxy resin:
the epoxy value range of the epoxy resin is 0.44-0.67; and/or the presence of a gas in the gas,
the epoxy resin is multifunctional epoxy resin, is selected from at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin and alicyclic epoxy resin, is preferably selected from glycidyl ether epoxy resin, and is more preferably selected from bisphenol A epoxy resin; and/or the presence of a gas in the gas,
the curing agent is selected from linear polyether amine, preferably selected from linear polyether amine with the molecular weight of 230-2000 g/mol, the amine value of 0.95-8.1 mmol/g and the active hydrogen equivalent of 60-514 g/eq, more preferably selected from polyether amine with the molecular weight of 230g/mol, the amine value of 7.5-8.1 mmol/g and the active hydrogen equivalent of 60 g/eq; and/or the presence of a gas in the gas,
the amount of the curing agent is 20-60 parts by weight, preferably 30-50 parts by weight, based on 100 parts by weight of the epoxy resin; and/or the presence of a gas in the gas,
an accelerator is also added in the epoxy resin curing reaction, and the accelerator is an amine accelerator, preferably selected from 2,4, 6-tri (dimethylaminomethyl) phenol; the amount of the accelerator is 0.1-2 parts by weight, preferably 0.2-1.5 parts by weight, based on 100 parts by weight of the epoxy resin; and/or the presence of a gas in the gas,
the mixture is also subjected to bubble removal under vacuum conditions; and/or the presence of a gas in the gas,
the microwave frequency is 2400-2500 Hz; and/or the presence of a gas in the gas,
the constant-temperature heating temperature is 10-250 ℃; and or (b) a,
the curing reaction time is 2-5 h.
7. A method for quantitatively evaluating the non-thermal effect of a microwave curing reaction according to the system of claim 1 or 2, comprising the steps of:
(1) adding resin to be cured into an isothermal reactor;
(2) modulating and stabilizing the microwave frequency of the isothermal reactor through a frequency converter;
(3) carrying out constant-temperature microwave heating curing reaction;
(4) monitoring the reaction degree by using an infrared spectrogram obtained by an infrared in-situ detection unit;
(5) and (4) calculating the infrared spectrogram obtained in the step (4) by combining a formula to obtain the activation energy and the pre-exponential factor of the microwave curing reaction so as to quantitatively evaluate the non-thermal effect of the microwave curing reaction.
8. The method according to claim 7, wherein the resin to be cured for quantitatively evaluating the non-thermal effect of the microwave curing reaction is at least one selected from epoxy resin and unsaturated polyester, preferably epoxy resin.
9. The method according to claim 8, wherein the step (1) comprises mixing the resin to be cured and the curing agent, smearing the uniformly stirred mixture on a potassium bromide tablet, forming a double-layer potassium bromide tablet by a tablet forming method, and adding the double-layer potassium bromide tablet into an isothermal reactor.
10. The method of claim 9, wherein when the resin to be cured is an epoxy resin:
the epoxy value range of the epoxy resin is 0.44-0.67; and/or the presence of a gas in the gas,
the epoxy resin is multifunctional epoxy resin, is selected from at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin and alicyclic epoxy resin, is preferably selected from glycidyl ether epoxy resin, and is more preferably selected from bisphenol A epoxy resin; and/or the presence of a gas in the gas,
the curing agent is selected from linear polyether amine, preferably the molecular weight of the selected linear polyether amine is 230-2000 g/mol, the amine value is 0.95-8.1 mmol/g, the active hydrogen equivalent is 60-514 g/eq, more preferably the molecular weight of the selected linear polyether amine is 230g/mol, the amine value is 7.5-8.1 mmol/g, and the active hydrogen equivalent is 60 g/eq; and/or the presence of a gas in the gas,
the amount of the curing agent is 20-60 parts by weight, preferably 30-50 parts by weight, based on 100 parts by weight of the epoxy resin; and/or the presence of a gas in the gas,
an accelerator is also added in the epoxy resin curing reaction, and the accelerator is an amine accelerator, preferably selected from 2,4, 6-tri (dimethylaminomethyl) phenol; the amount of the accelerator is 0.1-2 parts by weight, preferably 0.2-1.5 parts by weight, based on 100 parts by weight of the epoxy resin; and/or the presence of a gas in the gas,
the mixture is also subjected to bubble removal under vacuum conditions; and/or the presence of a gas in the gas,
the microwave frequency is 2400-2500 Hz; and/or the presence of a gas in the gas,
the constant-temperature heating temperature is 10-250 ℃; and or (b) a,
the curing reaction time is 2-5 h; and/or the presence of a gas in the gas,
the thickness of the potassium bromide tablet is 0.7-0.8 mm, and the diameter of the potassium bromide tablet is 13-15 mm; and/or the presence of a gas in the gas,
the smear thickness of the uniformly stirred mixture is 0.8-0.9 mm.
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