CN112992282B - Method for verifying dissolution curve of double-component polyurethane high polymer physical foaming agent - Google Patents
Method for verifying dissolution curve of double-component polyurethane high polymer physical foaming agent Download PDFInfo
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Abstract
The invention provides a method for verifying a dissolution curve of a double-component polyurethane high polymer physical foaming agent, which comprises the following steps of: heating and dissolving a high polymer B component mixed solution containing a physical foaming agent, recording temperature values and liquid level height values of the high polymer B component mixed solution at different moments, calculating a volume value of the mixed solution at the corresponding moment according to the liquid level height value, then calculating the solubility of the physical foaming agent at different temperatures according to the temperature and the volume of the high polymer B component mixed solution to obtain a curve of the solubility of the physical foaming agent along with the change of the temperature, and finally verifying the applicability of the measured curve of the solubility of the physical foaming agent through the comparison of a high polymer slurry foaming test and a numerical simulation result. The invention compares the analog value with the test value by using temperature and density, and then is more consistent, thereby proving the accuracy and the rationality of the solubility curve.
Description
Technical Field
The invention belongs to the field of chemical grouting, and particularly relates to a method for verifying a dissolution curve of a double-component polyurethane high polymer physical foaming agent.
Background
The high polymer grouting material has the advantages of fast expansion, early strength, water resistance, durability, environmental protection and the like. In recent years, high polymer grouting is widely applied to infrastructure repair engineering as a novel engineering repair technology. Especially, in recent years, with the progress of modern polymer industry, the bi-component polyurethane polymer grouting material with self-expansion characteristic and the high-pressure injection technology thereof are developed very rapidly internationally, are applied more and more widely, become one of the more active development directions in the chemical grouting field, have been widely applied to the aspects of water damage prevention, foundation reinforcement, road maintenance and the like of underground engineering such as mines, tunnels and the like, become a development direction with obvious characteristics in the geotechnical engineering field, and have important guiding significance for grouting design and construction in research on the diffusion mechanism of the polymer grout.
The main components of the polymer mixture include isocyanate, polyol, foaming agent, catalyst, and the like. The components mainly comprise two raw materials, namely a material A and a material B, wherein the material A is mainly isocyanate, and the material B contains polyol, a catalyst, a physical foaming agent, a chemical foaming agent and the like.
Simulating the expansion diffusion process of the high polymer by means of simulation is an important way for researching the diffusion mechanism of the high polymer slurry. After the high polymer is injected, chemical reaction is rapidly carried out, a large amount of heat energy is released, the temperature of the slurry is continuously increased, the physical foaming agent is gradually gasified to form a large amount of micro closed-cell bubbles and the micro closed-cell bubbles are suspended in the slurry, so that the volume of the slurry is continuously expanded, and the slurry is driven to flow. Therefore, in order to research the diffusion mechanism of the high polymer, the expansion process of the high polymer slurry needs to be accurately solved, and the key point is to master a solubility model of the physical foaming agent in the high polymer slurry. At present, a quick and efficient method for calculating the solubility curve of the physical foaming agent is lacked.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a method for verifying the dissolution curve of a double-component polyurethane high polymer physical foaming agent, which comprises the steps of heating a high polymer B component mixed solution in which a physical foaming agent is dissolved, recording temperature values and liquid level height values of the high polymer B component mixed solution at different moments, calculating the volume value of the mixed solution at the corresponding moment according to the liquid level height value, calculating the solubility of the physical foaming agent at different temperatures according to the temperature and the volume of the high polymer B component mixed solution to obtain a curve of the solubility of the physical foaming agent along with the temperature change, and finally verifying the applicability of the measured solubility curve of the physical foaming agent through the comparison of a high polymer slurry foaming test and a numerical simulation result.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the invention provides a method for verifying a dissolution curve of a double-component polyurethane high polymer physical foaming agent, which comprises the following steps of:
s1, heating and dissolving a B component high polymer mixed solution containing a physical foaming agent, reading and recording temperature values and liquid level height values of the B component high polymer mixed solution at different moments, and calculating the volume V (t) of the mixed solution at the moment t according to the liquid level height values;
s2, according to the volume V of the mixed liquid at the initial moment 0 And the volume V (t) of the mixed liquid obtained in the step S1, and calculating the mass m of the gasified partial physical foaming agent at the time t by using an ideal gas equation and a molar mass formula BG ；
S3, utilizing the mass m of the partial physical foaming agent gasified at the time t obtained in the step S2 BG Calculating the mass fraction r of the physical foaming agent in the component B mixed solution at the time t according to a solubility formula BL ；
S4, repeating the steps S1-S3, calculating the solubility of the physical foaming agent at the corresponding temperature at different moments, and performing data fitting in an exponential function mode to obtain a curve of the solubility of the physical foaming agent along with the change of the temperature;
and S5, verifying the applicability of the curve of the solubility along with the temperature change obtained in the step S4 through a foaming test of the A and B double-component polymer mixed solution.
In a preferred embodiment, the step S1 specifically includes:
s11: injecting the B component high polymer mixed solution containing the physical foaming agent into a graduated measuring cylinder;
s12: placing the temperature sensor in a measuring cylinder, and immersing a probe of the temperature sensor in the mixed solution;
s13: placing the measuring cylinder in the step S12 on a heating device for heating;
s14: reading and recording temperature values T of the mixed liquid at different moments in the heating process;
s15: reading the height value of the highest point of the mixed liquid level on the measuring cylinder and the corresponding height value of the regular liquid level according to
Calculating the volume V (t) of the mixed liquid at the time t,
in the above formula, R is the radius, h (t) is the height from the bottom to the highest point of the liquid level at the moment t, h 1 And (t) is the height from the bottom to the lowest point of the liquid level at the time t.
In a preferred embodiment, the step S2 specifically includes:
s21, volume V (t) of the mixed liquid at time t and volume V of the mixed liquid at initial time 0 Determining the volume Δ V of the physical blowing agent vaporized at time t,. DELTA.V = V (t) -V 0 ；
S22, calculating the mole number n of the gasified physical foaming agent according to the delta V and an ideal gas equation p delta V = nRT, wherein p is the atmospheric pressure, R is a Prov gas constant and is 8.31J/(mol · k), and T is the temperature of the mixed liquid at the moment T;
s23, according to the mole number n and the molar mass formula m BG ＝n×M B Calculating to obtain the mass m of the physical foaming agent of the gasified part at the time t BG Wherein M is B Is the physical blowing agent molar mass.
In a preferred embodiment, the step S3 is specifically:
according to m BG And formula of solubility
Calculating to obtain the mass fraction r of the physical foaming agent in the mixed solution BL Wherein m is the total mass of the mixed liquid of the component B and m B Is the total mass of the physical blowing agent.
In a preferred embodiment, said step S5 comprises the steps of:
a. heating and dissolving A and B double-component high polymer mixed liquor containing a physical foaming agent, reading and recording temperature values and liquid level height values of the A and B double-component high polymer mixed liquor at different moments, calculating the volume V (t) of the A and B double-component high polymer mixed liquor at t moment according to the liquid level height values, and further calculating density values of the A and B double-component high polymer mixed liquor at t moment;
b. calculating the solubility of the A and B double-component high polymer mixed liquor at the t moment by using the obtained curve of the solubility changing along with the temperature and the measured temperature value, and then calculating the temperature and the density of the A and B double-component high polymer mixed liquor at the t moment according to the solubility;
c. and (c) comparing the temperature and the density of the double-component high polymer mixed liquid obtained by the calculation in the step (B) at the time (t) with the temperature value and the density value obtained in the step (a), and judging the applicability of the solubility curve of the measured physical foaming agent according to the deviation of the two values.
In a preferred embodiment, the temperature of the two-component polymer mixed solution at time t in step B is calculated by the expressions of a gelation reaction rate equation, a chemical foaming reaction and an energy balance equation, wherein the expression of the gelation reaction rate equation is as follows:
the foaming reaction expression is as follows:
the energy balance equation expression is as follows:
wherein, A OH Indicative of the gel reaction, E OH Indicates the activation energy of the gel reaction, A W A pre-exponential factor for the foaming reaction, E W Activation energy for the foaming reaction, c i,0 Denotes the initial concentration of the component, c i Denotes the current concentration of the component, X i As a result of the conversion rate of the components,
r is the Prussian gas constant, T is the slurry temperature, R i The mass fraction of each component is expressed,
r BG ＝r BL,0 -r BL ，ρ i denotes the density of each component, C i Showing specific heat of each component, (. DELTA.H) i Denotes the heat of reaction, and λ is the heat of vaporization.
In a preferred embodiment, the density of the two-component high polymer mixed solution at time a and B in step B is calculated by a density formula, and the expression of the density formula is as follows:
wherein ρ P Is the density of the polyurethane mixture, rho BL Density of physical blowing agent dissolved in liquid, r BL,0 Is the initial mass fraction, r, of the liquid physical blowing agent at the initial moment BL Is the mass fraction of the liquid physical blowing agent at the present moment, r BG Is the mass fraction of the gaseous physical blowing agent at the present moment, r BG ＝r BL,0 -r BL ，r W Is the mass fraction of water, r W,0 Is the initial mass fraction of water, p W Is the density of water, M i The molar mass of the components, R, is the Peyer's disease constant, and T is the slurry temperature.
In a preferred embodiment, the component B high polymer mixed solution comprises polyol, a chemical foaming agent, a physical foaming agent and a catalyst.
In a preferred embodiment, the polymer of component A is an isocyanate.
In a preferred embodiment, the physical blowing agent comprises one of monofluorotrichloromethane, monofluorotrichloroethane, trifluoromonochloromethane, monofluorodichloroethane, cyclopentane.
In the expression, OH represents polyol, NCO represents isocyanate, P represents polyurethane, the high polymer generated by the reaction of the two components A and B after mixing is called polyurethane high polymer, BL represents a physical foaming agent, BG represents a gaseous physical foaming agent, W represents water, namely X OH Denotes the conversion of the polyol, c OH.0 Indicating the initial solubility of the polyol, and so on.
In the application, two raw materials, namely a material A and a material B are mainly formed, wherein the material A is mainly isocyanate, the material B contains polyol, a catalyst, a physical foaming agent and a chemical foaming agent, two parts of gas exist simultaneously in the reaction process of a high polymer mixture, one part of gas is gas formed by gasifying the liquid physical foaming agent, and the other part of gas is carbon dioxide generated by reacting isocyanate and water, so that if the gas change value of the mixed liquid of the component A and the component B is tested, the gasified amount of the physical foaming agent cannot be obtained. The physical foaming agent only exists in the material B at the initial moment, so that the solubility model of the physical foaming agent can be obtained by analyzing the amount of the gasified physical foaming agent in a mode of physically heating a single material B, and the interference of carbon dioxide gas is avoided. Numerical simulation of the chemical reaction process of the high polymer slurry is an important way to study the expansion and diffusion mechanism of the high polymer slurry, and the expansion mechanism can be characterized by the temperature and the density of the slurry in the expansion process. The control of the solubility model of the physical foaming agent is one of the preconditions for numerical solution of the expansion process of the polymer slurry.
The invention has the following beneficial effects:
(1) The invention provides a method for calculating a dissolution curve of a double-component high polymer physical foaming agent, which comprises the steps of heating a high polymer B component mixed solution in which a physical foaming agent is dissolved, recording temperature values and liquid level height values of the high polymer B component mixed solution at different moments, calculating a volume value of the mixed solution at the corresponding moment according to the liquid level height values, calculating the solubility of the physical foaming agent at different temperatures according to the temperature and the volume of the high polymer B component mixed solution, and performing data fitting in an exponential function mode to obtain a curve of the change of the solubility of the physical foaming agent along with the temperature, thereby providing an important way for researching the diffusion mechanism of the high polymer.
(2) The invention provides a method for verifying a dissolution curve of a double-component high polymer physical foaming agent, which comprises the steps of calculating the temperature and the density of A and B double-component polyurethane high polymer mixed liquid containing the physical foaming agent at different moments, then utilizing the obtained dissolution curve to carry out solution calculation to obtain the temperature and the density of high polymer slurry at different moments, comparing the results, judging the applicability of the measured solubility curve of the physical foaming agent according to the deviation of the two, and verifying the accuracy of the solubility curve.
Drawings
FIG. 1 is a solubility model of a physical blowing agent of example 1 of the present invention;
FIG. 2 is a graph showing the temperature values of the A and B two-component polymer mixtures according to the present invention in comparison with the temperature values obtained from the solubility curve over time;
FIG. 3 is a graph of density values of the provided A, B bicomponent polymer blends of the present invention example 1 compared to density values solved from solubility curves over time;
FIG. 4 is a solubility model of a physical blowing agent of example 2 in the present invention;
FIG. 5 is a graph showing the temperature values of the A and B two-component polymer mixtures according to example 2 of the present invention compared with the temperature values obtained by solving the solubility curve;
FIG. 6 is a graph comparing the density values of the A and B bicomponent polymer blends according to the invention as provided in example 2 with the density values over time as calculated from the solubility curves.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description of the present specification, reference to the description of "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
A method for calculating a dissolution curve of a double-component high polymer physical foaming agent comprises the following steps:
s1, heating and dissolving a B component high polymer mixed solution containing a physical foaming agent, reading and recording temperature values and liquid level height values of the B component high polymer mixed solution at different moments, and calculating the volume V (t) of the mixed solution at the moment t according to the liquid level height values.
The specific method comprises the following steps:
s11: injecting the B component high polymer mixed solution containing the physical foaming agent into a graduated measuring cylinder;
s12: placing the temperature sensor in a measuring cylinder, and immersing a probe of the temperature sensor in the mixed solution;
s13: placing the measuring cylinder in the step S12 on a heating device for heating;
s14: reading and recording temperature values T of the mixed solution at different moments in the heating process;
s15: reading the highest point of the mixing level on the cylinderHeight value and corresponding height value at regular liquid level according to
Calculating the volume V (t) of the mixed solution at the time t,
in the above formula, R is the radius, h (t) is the height from the bottom to the highest point of the liquid level at the moment t, h 1 (t) is the height from the bottom to the lowest point of the liquid surface at time t.
S2, according to the volume V of the mixed liquid at the initial moment 0 And the volume V (t) of the mixed liquid obtained in the step S1, and calculating the mass m of the gasified partial physical foaming agent at the time t by using an ideal gas equation and a molar mass formula BG 。
The specific method comprises the following steps:
volume V (t) of mixed liquid at time t and volume V of mixed liquid at initial time 0 Determining the volume Δ V of the physical blowing agent vaporized at time t,. DELTA.V = V (t) -V 0 ；
Calculating the mole number n of the gasified physical foaming agent according to the delta V and an ideal gas equation p delta V = nRT, wherein p is atmospheric pressure, R is a Poisson's gas constant and is 8.31J/(mol · k), and T is the temperature of the mixed liquid at the moment T;
according to the molar number n and the molar mass formula m BG ＝n×M B Calculating to obtain the mass m of the physical foaming agent of the gasified part at the time t BG Wherein M is B Is the physical blowing agent molar mass.
S3, utilizing the mass m of the partial physical foaming agent gasified at the time t obtained in the step S2 BG Calculating the mass fraction r of the physical foaming agent in the component B mixed liquid at the time t according to a solubility formula BL 。
The specific method comprises the following steps: according to m BG And solubility formula
Calculating to obtain the mass fraction r of the physical foaming agent in the mixed solution BL Wherein m is the total mass of the mixed liquid of the component B and m B Is the total mass of the physical blowing agent.
And S4, repeating the steps S1-S3, calculating the solubility of the physical foaming agent at the corresponding temperature at different moments, and performing data fitting in an exponential function mode to obtain a curve of the solubility of the physical foaming agent along with the change of the temperature.
A verification method for a dissolution curve of a two-component high polymer physical foaming agent is used for verifying the applicability of a physical foaming agent solubility change curve along with temperature, which is calculated by the calculation method for the dissolution curve of the two-component high polymer physical foaming agent, and comprises the following steps:
a. heating and dissolving A and B double-component high polymer mixed liquor containing a physical foaming agent, reading and recording temperature values and liquid level height values of the A and B double-component high polymer mixed liquor at different moments, calculating the volume V (t) of the t-moment high polymer mixed liquor according to the liquid level height values, further calculating the density value of the t-moment high polymer mixed liquor,
wherein according to
The volume V (t) of the mixed liquor at time t is calculated, and then the density value of the high polymer mixed liquor at time t is calculated by using density = mass/volume.
b. And calculating the solubility of the A and B double-component high polymer mixed liquor at the t moment by using the obtained curve of the solubility changing along with the temperature and the measured temperature value, and then calculating the temperature and the density of the A and B double-component high polymer mixed liquor at the t moment according to the solubility.
the temperature of the A and B two-component high polymer mixed liquid at the t moment is calculated by a gelation reaction rate equation, a chemical foaming reaction and an energy balance equation expression, wherein the gelation reaction rate equation expression is as follows:
the foaming reaction expression is as follows:
the energy balance equation expression is as follows:
wherein A is OH Indicative of the gel reaction, E OH Indicates the activation energy of the gel reaction, A W A pre-exponential factor for the foaming reaction, E W Activation energy for the foaming reaction, c i,0 Denotes the initial concentration of the component, c i Denotes the current concentration of the component, X i As a result of the conversion rate of the components,
r is the Peyer's gas constant, T is the slurry temperature, R i The mass fraction of each component is expressed,
r BG ＝r BL,0 -r BL ，ρ i denotes the density of each component, C i Showing specific heat of each component, (. DELTA.H) i Denotes the heat of reaction, and λ is the heat of vaporization.
In this expression, OH represents a polyol, NCO represents an isocyanate, P represents a polyurethane, BL represents a physical blowing agent, BG represents a gaseous physical blowing agent, W represents water, i.e., X OH Denotes the conversion of the polyol, c OH.0 Indicating the initial solubility of the polyol, and so on.
the density of the A and B double-component high polymer mixed liquid at the time t is calculated by a density formula, and the expression of the density formula is as follows:
where ρ is P Density of polyurethane mixture, ρ BL For dissolving in liquidDensity of physical blowing agent of (2), r BL,0 Is the initial mass fraction, r, of the liquid physical blowing agent at the initial moment BL Is the mass fraction of the liquid physical foaming agent at the current moment, r BG Is the mass fraction of the gaseous physical blowing agent at the present moment, r BG ＝r BL,0 -r BL ，r W Is the mass fraction of water, r W,0 Is the initial mass fraction of water, p W Is the density of water, M i R is the Poisson's gas constant and T is the slurry temperature.
c. And (c) comparing the temperature and the density of the double-component high polymer mixed liquid obtained by the calculation in the step (B) at the time (t) with the temperature value and the density value obtained in the step (a), and judging the applicability of the solubility curve of the measured physical foaming agent according to the deviation of the two values.
Example 1
In the embodiment, the isocyanate in the component A high polymer is polymethylene polyphenyl isocyanate, the polyol in the component B high polymer mixed solution is polytetrahydrofuran ether glycol, the chemical foaming agent is water, the catalyst is triethylene diamine, and the physical foaming agent is trichloromonofluoro ethane. Mass m of physical blowing agent in polymer slurry at initial time B 7.20g, the initial polymer slurry mass m was 372g, the initial temperature was 26.5 ℃ and the initial polymer slurry volume was 150cm 3 The standard atmospheric pressure p is 1.01325X 10 5 Pa。
The solubility model of the physical blowing agent in the polymer slurry obtained according to this example is:
wherein, a =0.00211, b =0.03665, c =341.79292, d =5.14675.
FIG. 1 is a solubility model curve for a physical blowing agent.
The relevant parameters involved in the formula in the verification method are shown in table 1:
TABLE 1
According to the method, the inverse calculation results of the temperatures of the A and B two-component high polymer mixed liquid at different times are calculated through expressions of a gelling reaction rate equation, a foaming reaction and an energy balance equation and relevant parameters in the table 1, and are compared with temperature values at different times obtained through experiments, as can be known from the graph 2, the temperature of the high polymer is rapidly increased at the initial stage of the reaction and then tends to be stable, the calculation value (analog value) of a dissolution curve is consistent with a test value, and the accuracy and the reasonability of the dissolution curve are proved.
Using p F According to the formula and the relevant parameters in the table 1, the back calculation result of the density of the two-component polymer mixed solution A and B at different times is calculated and compared with the density value obtained by the experiment at different times, and it can be known from fig. 3 that the density of the polymer is sharply reduced before about 20s and tends to be stable after 20 s. It can be seen that the results of the numerical analysis are closer to the test results, further illustrating the accuracy of the solubility curve.
Example 2
In the embodiment, the isocyanate in the component A high polymer is polyaryl polyisocyanate, the polyol in the component B high polymer mixed solution is polytetramethylene ether glycol, the chemical foaming agent is water, the catalyst is triethylene diamine, and the physical foaming agent is cyclopentane. Mass m of physical blowing agent in polymer slurry at initial time B 8.40g, the initial mass m of the polymer slurry was 369g, the initial temperature was 31.5 ℃ and the initial volume of the polymer slurry was 150cm 3 The standard atmospheric pressure p is 1.01325X 10 5 Pa。
The solubility model of the physical blowing agent in the polymer slurry obtained according to this example is:
wherein, a =0.008707, b =0.5617, c =0.7043, d =0.2785.
FIG. 4 is a solubility model curve for a physical blowing agent.
The relevant parameters in the formulas of step b and step c in the verification method are shown in table 2:
TABLE 2
According to the method, the inverse calculation results of the temperatures of the A and B two-component high polymer mixed liquid at different times are calculated through expressions of a gelling reaction rate equation, a foaming reaction and an energy balance equation and relevant parameters in the table 1, and are compared with temperature values at different times obtained through experiments, as can be known from the graph 4, the temperature of the high polymer is rapidly increased at the initial stage of the reaction and then tends to be stable, the calculation value (analog value) of a dissolution curve is consistent with the test value, and the accuracy and the reasonability of the dissolution curve are proved.
Using p F According to the formula and the relevant parameters in the table 1, the back calculation result of the density of the two-component polymer mixed solution A and B at different times is calculated and compared with the density value obtained by the experiment at different times, and it can be known from fig. 5 that the density of the polymer is sharply reduced before about 20s and tends to be stable after 20 s. It can be seen that the results of the numerical analysis are closer to the test results, further illustrating the accuracy of the solubility curve.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and is not intended to limit the practice of the invention to these embodiments. For those skilled in the art to which the invention pertains, numerous simple deductions or substitutions may be made without departing from the spirit of the invention, which shall be deemed to belong to the scope of the invention.
Claims (6)
1. A method for verifying a dissolution curve of a double-component polyurethane high polymer physical foaming agent is characterized by comprising the following steps of:
s1, heating and dissolving a B component high polymer mixed solution containing a physical foaming agent, reading and recording temperature values and liquid level height values of the B component mixed solution of the high polymer at different moments, and calculating the volume V (t) of the mixed solution at the moment t according to the liquid level height values;
s2, according to the volume V of the mixed liquid at the initial moment 0 And the volume V (t) of the mixed liquid obtained in the step S1, and calculating the mass m of the gasified partial physical foaming agent at the time t by using an ideal gas equation and a molar mass formula BG ；
S3, utilizing the mass m of the partial physical foaming agent gasified at the time t obtained in the step S2 BG Calculating the mass fraction r of the physical foaming agent in the component B mixed liquid at the time t according to a formula BL ；
The method specifically comprises the following steps:
according to m BG And formula
Calculating to obtain the mass fraction r of the physical foaming agent in the mixed solution BL Wherein m is the total mass of the mixed liquid of the component B and m B Is the total mass of the physical blowing agent;
s4, repeating the steps S1-S3, calculating the mass fraction of the physical foaming agent at the corresponding temperature at different moments, and performing data fitting in an exponential function mode to obtain a curve of the mass fraction of the physical foaming agent changing along with the temperature;
s5, verifying the applicability of the mass fraction of the physical foaming agent obtained in the step S4 along with a temperature change curve through a foaming test of the A and B double-component high polymer mixed solution;
the component B high polymer mixed solution comprises polyol, a chemical foaming agent, a physical foaming agent and a catalyst;
the component A is isocyanate;
step S5 includes the steps of:
a. heating and dissolving A and B double-component high polymer mixed liquor containing a physical foaming agent, reading and recording temperature values and liquid level height values of the A and B double-component high polymer mixed liquor at different moments, calculating the volume V (t) of the A and B double-component high polymer mixed liquor at t moment according to the liquid level height values, and further solving the density value of the A and B double-component high polymer mixed liquor at t moment;
b. calculating the mass fraction of the physical foaming agent of the two-component high polymer mixed liquid at the time t by using the obtained mass fraction of the physical foaming agent along with the temperature change curve and the measured temperature value, and then calculating the temperature and the density of the two-component high polymer mixed liquid at the time t according to the mass fraction of the physical foaming agent;
c. and (c) comparing the temperature and the density of the double-component high polymer mixed solution of the component A and the component B obtained in the step (B) at the time t with the temperature value and the density value obtained in the step (a), and judging the applicability of the dissolution curve of the measured physical foaming agent according to the deviation of the two.
2. The method for verifying the dissolution curve of the physical blowing agent for two-component polyurethane polymer according to claim 1, wherein the step S1 comprises:
s11: injecting the B component high polymer mixed solution containing the physical foaming agent into a graduated measuring cylinder;
s12: placing the temperature sensor in a measuring cylinder, and immersing a probe of the temperature sensor in the mixed solution;
s13: placing the measuring cylinder in the step S12 on a heating device for heating;
s14: reading and recording temperature values T of the mixed liquid at different moments in the heating process;
s15: reading the height value of the highest point of the mixed liquid level on the measuring cylinder and the corresponding height value of the regular liquid level according to
Calculating the volume V (t) of the mixed liquid at the time t,
in the above formula, R is the radius, h (t) is the height from the bottom to the highest point of the liquid level at the moment t, h 1 And (t) is the height from the bottom to the lowest point of the liquid level at the time t.
3. The method for verifying the dissolution curve of the two-component polyurethane polymer physical foaming agent according to claim 1, wherein the step S2 specifically comprises:
s21, volume V (t) of the mixed liquid at time t and volume V of the mixed liquid at initial time 0 Determining the volume Δ V, Δ V = V (t) -V of the physical blowing agent vaporized at time t 0 ；
S22, calculating the mole number n of the gasified physical foaming agent according to the delta V and an ideal gas equation p delta V = nRT, wherein p is atmospheric pressure, R is a Poisson' S gas constant and is 8.31J/(mol · k), and T is the temperature of the mixed liquid at the moment T;
s23, according to the mole number n and the molar mass formula m BG ＝n×M B Calculating to obtain the mass m of the physical foaming agent of the gasified part at the time t BG Wherein M is B Is the physical blowing agent molar mass.
4. The method for verifying the dissolution curve of the physical foaming agent for two-component polyurethane polymers as claimed in claim 1, wherein the temperature of the mixed solution of the two-component polyurethane polymers at the time point A and the time point B in the step B is calculated by the expressions of a gelation reaction rate equation, a chemical foaming reaction and an energy balance equation, wherein the expression of the gelation reaction rate equation is as follows:
the foaming reaction expression is as follows:
the energy balance equation expression is as follows:
wherein A is OH Indicative of the gel reaction, E OH Indicates the activation energy of the gel reaction, A W A pre-exponential factor for the foaming reaction, E W Activation energy for foaming reaction, c i,0 Denotes the initial concentration of the component, c i Denotes the current concentration of the component, X i As a result of the conversion rate of the components,
r is the Prussian gas constant, T is the slurry temperature, R i The mass fraction of each component is expressed,
r BG ＝r BL,0 -r BL ，ρ i denotes the density of each component, C i Represents the specific heat of each component, (. DELTA.H) i Denotes the heat of reaction, and λ is the heat of vaporization.
5. The method for verifying the dissolution curve of the two-component polyurethane polymer physical foaming agent as claimed in claim 1, wherein the density of the two-component polymer mixture at time a and B in step B is calculated by a density formula, wherein the expression of the density formula is as follows:
where ρ is P Is the density of the polyurethane mixture, rho BL Density of physical blowing agent dissolved in liquid, r BL,0 Is the initial mass fraction, r, of the liquid physical blowing agent at the initial moment BL Is the mass fraction of the liquid physical blowing agent at the present moment, r BG Is the mass fraction of the gaseous physical blowing agent at the present moment, r BG ＝r BL,0 -r BL ，r W Is the mass fraction of water, r W,0 Is the initial mass fraction of water, p W Is the density of water, M i R is the Poisson's gas constant and T is the slurry temperature.
6. The method for verifying the dissolution curve of the physical blowing agent for two-component polyurethane polymers as claimed in any one of claims 1 to 5, wherein the physical blowing agent comprises one of fluorotrichloromethane, fluorotrichloroethane, trifluoromonochloromethane, fluorodichloroethane, and cyclopentane.
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