CN116052805A - Calculation method for analyzing thermal performance of PET flame-retardant master batch - Google Patents
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 141
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 59
- 238000004364 calculation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 78
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 47
- 230000004913 activation Effects 0.000 claims description 30
- 230000004580 weight loss Effects 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 17
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- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 238000002411 thermogravimetry Methods 0.000 claims description 9
- 238000009499 grossing Methods 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
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- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 101
- 239000005020 polyethylene terephthalate Substances 0.000 description 101
- 230000000694 effects Effects 0.000 description 9
- -1 Polyethylene terephthalate Polymers 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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Abstract
The invention relates to a calculation method for analyzing the thermal performance of PET flame-retardant master batch, which is characterized in that a large bright PET slice and a halogen-free flame retardant are processed to prepare the PET flame-retardant master batch, then a Scipy library of a Python tool is used for calling a cut_fit function, a fit function command of a Gnurlot tool and relevant experimental data for calculation are processed by a smooths csprines function, and then the thermal performance of the PET flame-retardant master batch is analyzed by a Flynn-Wall-Ozawa method and a Kissinger method. The data fitting degree obtained by calculation through the method is high, the calculation time of researchers is greatly shortened, and the working efficiency and the reliability are improved.
Description
Technical Field
The invention relates to the technical field of PET flame-retardant master batches, in particular to a calculation method for analyzing the thermal performance of PET flame-retardant master batches.
Background
Polyethylene terephthalate (PET) is a synthetic polymer and is widely applied to industries such as textile, automobiles, electric appliances and the like, however, strict requirements are placed on flame retardance and safety performance of materials in the application scene. However, PET is a flammable material, and the limiting oxygen index is only 20.8%, which is far lower than the flame retardant standard required in flame retardant occasions. In addition, PET has a molten drop phenomenon in the combustion process, so that the dangerous degree of fire is increased, and the PET has great potential safety hazard in practical application, so that the difficulty is increased in escaping for personnel and rescuing firefighters. Therefore, the development of PET with flame retardant function has profound significance for protecting public property and life safety. PET is a class of organic polymers, and combustion is a reaction process of exothermic decomposition. The pyrolysis dynamics and the thermal stability and the thermal performance parameters reflected in the pyrolysis are closely related to the functional effect of the high polymer material, so that the research on the thermal performance parameters of the high polymer material is very significant for designing the flame-retardant PET. In order to solve the inflammability problem of the polymer material, adding the flame retardant master batch rich in the flame retardant is one of effective methods, wherein the selection of the flame retardant plays a vital role in the flame retardant modification effect of the flame retardant master batch. As the melting point of PET is about 255 ℃, the decomposition temperature of the added flame retardant is higher, and the matching degree of the flame retardant and the PET thermal performance directly influences the flame retardant effect, so that the research of the thermal performance related parameters of the flame retardant master batch is greatly helpful for understanding the flame retardant effect.
In order to reveal and deeply analyze the flame retardant effect of flame retardants on PET, it is an effective approach to recognize thermal behavior changes from thermodynamic processes. In practical applications, a thermogravimetric analyzer and a differential scanning calorimeter are often used for analyzing physical properties related to thermodynamics in materials, and performing mathematical analysis according to a related thermodynamic classical equation. However, the traditional calculation mode is often manual calculation, takes a long time to calculate, is low in efficiency, and brings great inconvenience to research and development work. The present invention is innovatively improved in view of the above problems.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a calculation method for analyzing the thermal performance of PET flame retardant master batch with high calculation efficiency.
The specific embodiments of the present invention are as follows:
a calculation method for analyzing thermal performance of PET flame-retardant master batch is characterized by comprising the following steps: the method comprises the following steps:
s1: respectively taking 10mg of big bright PET slices and 10mg of halogen-free flame retardant as raw materials, placing the raw materials in a crucible, and performing thermogravimetric analysis to obtain a thermogravimetric TG-DTG curve at multiple heating rates;
s2: taking 50-80% of large bright PET slices and 20-50% of halogen-free flame retardant, drying at 120 ℃ for 4-6 hours, uniformly mixing the dried raw materials by a high-speed mixer, extruding the mixed raw materials by a double-screw extruder to prepare PET flame-retardant master batches, placing 10mgPET flame-retardant master batches into a crucible, and performing thermogravimetric analysis to obtain a thermogravimetric TG-DTG curve at multiple heating rates;
s3: acquiring peak temperature and final char formation data corresponding to the maximum initial decomposition temperature and the maximum weight loss rate, qualitatively evaluating the thermal stability of the large bright PET slices, the halogen-free flame retardant and the PET flame retardant master batch, analyzing the temperature difference between the initial decomposition temperature and the peak temperature of the PET flame retardant master batch and the temperature corresponding to the large bright PET slices, deducing the stage that the halogen-free flame retardant plays a flame retardant role by combining the final char formation, and if the numerical value of the final char formation of the PET flame retardant master batch is obviously larger than the numerical value of the char formation of the large bright PET slices, representing the flame retardance of the PET flame retardant master batch;
s4: the related experimental data for calculation is processed by adopting a Scipy library of a Python tool to call a cut_fit function and a fit function command of Gnupplot and a Smooth csprines function, and noise interference existing in the data is eliminated by utilizing a command line in the application process;
s5: the activation energy and the logarithmic pre-finger factor were calculated by using the Flynn-Wall-Ozawa method and the Kissinger method to quantitatively evaluate the performance of the halogen-free flame retardant.
Preferably, it is: and when the Flynn-Wall-Ozawa method in the S5 is applied, sequentially calling thermal weight data of large bright PET slices, halogen-free flame retardant and PET flame retardant master batches in a local document at different heating rates through a Python tool, substituting the temperature data at the selected weight loss rate into a compiled Flynn-Wall-Ozawa method formula, and fitting the selected data by using a curve_fit.
Preferably, it is: and (3) smoothing the DTG data by utilizing the Gnupplot' S Smooth cspline when the Kissinger method is applied in the S5, searching out the peak temperature when the weightlessness rate is maximum, and substituting the peak temperature into a Kissinger method formula for operation.
Preferably, it is: the loss rate of the Flynn-Wall-Ozawa method in the S5 is 5-70%.
Preferably, it is: the thermogravimetric analysis was performed under the following conditions: the temperature range is 25-800 ℃, the temperature rising rate is 10-25 ℃/min, and the nitrogen atmosphere condition is 30ml/min.
Preferably, it is: the temperature of each zone of the double-screw extruder is 250-280 ℃.
Preferably, it is: the halogen-free flame retardant is one or more of aluminum alkyl phosphate, zinc alkyl phosphate and magnesium alkyl phosphate.
Compared with the prior art, the invention has the beneficial effects that:
thermal performance parameters are calculated by means of a Python tool and a Gnurlot implementation Flynn-Wall-Ozawa method and a Kissinger method, and activation energy and logarithmic finger front factors of the large bright PET slices, the halogen-free flame retardant and the PET flame retardant master batch are calculated, so that flame retardant modification effects of the halogen-free flame retardant on the large bright PET slices are analyzed. The results show that the prepared PET flame-retardant master batch is mainly because the activation energy is improved, and the halogen-free flame retardant is decomposed into carbon to protect the PET matrix so as to improve the flame retardance.
The method greatly reduces the inconvenience and error of manual calculation and improves the working efficiency and accuracy by automatically acquiring experimental data by using a calculation tool (Python and Gnumulot) and substituting the experimental data into a compiled formula for calculation.
In addition, the calculation model related to the invention can be generally applied to application analysis of other modified matrixes, flame retardants and formulas. The method is beneficial to researchers to analyze the influences of different types and proportions on the flame retardant effect of the material and quickly screen out the optimal proportion.
The beneficial effects of the present invention will be described in detail in the examples, thereby making the beneficial effects more apparent.
Drawings
FIG. 1 is a flowchart illustrating the operation steps for analyzing the calculation of thermal performance parameters of PET flame retardant masterbatch in an embodiment of the invention;
FIG. 2 is a graph showing the comparison of activation energy of large bright PET slices calculated by the Flynn-Wall-Ozawa method under different weightlessness rates in an embodiment of the invention;
FIG. 3 is a graph showing the comparison of activation energy of halogen-free flame retardant calculated by Flynn-Wall-Ozawa method under different weight loss rates in an embodiment of the invention;
FIG. 4 is a graph showing the comparison of activation energy of PET flame retardant master batches calculated by the Flynn-Wall-Ozawa method under different weightlessness rates in the specific embodiment of the invention;
FIG. 5 is a schematic diagram showing the Kissinger method of large bright PET slices in accordance with an embodiment of the present invention;
FIG. 6 is a schematic diagram showing the Kissinger normal relationship of a halogen-free flame retardant in an embodiment of the invention;
FIG. 7 is a schematic drawing showing the Kissinger normal relationship of PET flame retardant masterbatch in an embodiment of the invention.
Detailed Description
Technical solutions in the embodiments of the present application will be clearly described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application are within the scope of the protection of the present application.
The terms first, second and the like in the description and in the claims, are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged, as appropriate, such that embodiments of the present application may be implemented in sequences other than those illustrated or described herein, and that the objects identified by "first," "second," etc. are generally of a type and not limited to the number of objects, e.g., the first object may be one or more. Furthermore, in the description and claims, "and/or" means at least one of the connected objects, and the character "/", generally means that the associated object is an "or" relationship.
Example 1
A calculation method for analyzing thermal performance of PET flame-retardant master batch is provided, in the specific embodiment of the invention: the method comprises the following steps:
s1: respectively taking 10mg of big bright PET slices and 10mg of halogen-free flame retardant as raw materials, placing the raw materials in a crucible, and performing thermogravimetric analysis to obtain a thermogravimetric TG-DTG curve at multiple heating rates;
s2: taking 50-80% of large bright PET slices and 20-50% of halogen-free flame retardant, drying at 120 ℃ for 4-6 hours, uniformly mixing the dried raw materials by a high-speed mixer, extruding the mixed raw materials by a double-screw extruder to prepare PET flame-retardant master batches, placing 10mgPET flame-retardant master batches into a crucible, and carrying out thermogravimetric analysis to obtain a thermogravimetric TG-DTG curve at multiple heating rates, wherein the thermogravimetric analysis conditions are as follows: the temperature range is 25-800 ℃, the temperature rising rate is 10-25 ℃/min, and the nitrogen atmosphere condition is 30ml/min. The halogen-free flame retardant is one or more of aluminum alkyl phosphate, zinc alkyl phosphate and magnesium alkyl phosphate, and has excellent flame retardant effect. The temperature of each zone is 250-280 ℃.
S3: acquiring peak temperature and final char formation data corresponding to the maximum initial decomposition temperature and the maximum weight loss rate, qualitatively evaluating the thermal stability of the large bright PET slices, the halogen-free flame retardant and the PET flame retardant master batch, analyzing the temperature difference between the initial decomposition temperature and the peak temperature of the PET flame retardant master batch and the temperature corresponding to the large bright PET slices, deducing the stage that the halogen-free flame retardant plays a flame retardant role by combining the final char formation, and if the numerical value of the final char formation of the PET flame retardant master batch is obviously larger than the numerical value of the char formation of the large bright PET slices, representing the flame retardance of the PET flame retardant master batch;
s4: the related experimental data for calculation is processed by adopting a Scipy library of a Python tool to call a cut_fit function and a fit function command of Gnupplot and a Smooth csprines function, and noise interference existing in the data is eliminated by utilizing a command line in the application process;
s5: the activation energy and the logarithmic pre-finger factor were calculated by using the Flynn-Wall-Ozawa method and the Kissinger method to quantitatively evaluate the performance of the halogen-free flame retardant.
And when the Flynn-Wall-Ozawa method is applied, sequentially calling thermal weight data of the large bright PET slices, the halogen-free flame retardant and the PET flame retardant master batch in the local document at different heating rates through a Python tool, substituting temperature data at a selected weightlessness rate into a compiled Flynn-Wall-Ozawa method formula, and fitting the selected data by using curvefit.
The loss rate of the Flynn-Wall-Ozawa method is 5-70%. The standard of the Flynn-Wall-Ozawa method for selecting a feasible interval of the weight loss rate is that the difference between the maximum value and the minimum value of the activation energy in the interval is 10-20% of the average activation energy value, and the calculation reliability of the selected method is high.
In general, the thermal degradation rate equation for the thermal degradation process can be expressed as
In formula (1): f (α) is a reaction rate function, α is a weight loss rate, and T is absolute temperature.
Substituting the Arrhenius formula into formula (1) can obtain:
in formula (2): e is the activation energy (kJ/mol) and R is the gas constant (8.314J/mol.K).
Let the temperature rise rate
Substituting the formula (2) and obtaining the modified product by variation: />
In formula (3): f (α) is a function related to the weight loss rate α.
The integral of the method is obtained:
order the
Substitution into equation (4) is obtained by derivative algorithm: />
Let y be more than or equal to 20 and less than or equal to 100, and the change can be obtained: lg ρ (y) ≡ 2.315-0.4567y (6)
In the formula (7), F (α) is an integral function of the mechanism function F (α).
Thus obtaining the formula of Flynn-Wall-Ozawa method:
when α is a constant, it is known from equation 9 that an equation relationship is established with lgβ to 1000/T, and a slope d (lgβ)/d (1/T) is obtained, so as to calculate the activation energy corresponding to each weight loss rate of the material in the pyrolysis process, i.e., e= - (R/0.4567) x d (lgβ)/d (1/T).
The method comprises the following steps: as shown in tables 1-4 and FIGS. 2-4, the activation energy E of the bright PET chips, halogen-free flame retardant and PET flame retardant master batch with weight loss rates of 5%, 20%, 40% and 70% was calculated by plotting the graph with 1000/T as the abscissa and lgβ as the ordinate and β as the heating rate (values of 10, 15, 20 and 25 ℃/min).
Table 1: flynn-Wall-Ozawa method is used for calculating activation energy of large-sized bright PET (polyethylene terephthalate) slice, halogen-free flame retardant and PET flame retardant master batch when weight loss rate is 5%
Table 2: flynn-Wall-Ozawa method is used for calculating activation energy of large-sized bright PET (polyethylene terephthalate) slice, halogen-free flame retardant and PET flame retardant master batch when weight loss rate is 20 percent
Table 3: flynn-Wall-Ozawa method is used for calculating activation energy of large-sized bright PET (polyethylene terephthalate) slice, halogen-free flame retardant and PET flame retardant master batch when weight loss rate is 40 percent
Table 4: flynn-Wall-Ozawa method is used for calculating activation energy of large-sized bright PET (polyethylene terephthalate) slice, halogen-free flame retardant and PET flame retardant master batch when weight loss rate is 70 percent
In order to further analyze the thermal performance and simultaneously provide activation energy at the weight loss rates of 10%, 15%, 30%, 50% and 60%, as shown in table 5, the activation energy and the correlation coefficient of the large bright PET chips, the halogen-free flame retardant and the PET flame retardant master batch are obtained according to the fitting curves of fig. 2-4 at different weight loss rates, the lgβ and 1000/T are all good in linear correlation, and the correlation coefficient r is larger than 0.98, so that the reliability and the accuracy of the calculation method are proved to be high.
Meanwhile, compared with the thermal degradation activation energy in Table 5, the activation energy of the halogen-free flame retardant and the PET flame retardant master batch is higher than that of the PET slice with large light. The addition of the halogen-free flame retardant proves that the degradation of the PET flame retardant master batch is relieved to a certain extent, and the carbon residue is produced mainly because the PET flame retardant master batch is heated, and the carbon layer plays roles of isolating air and protecting a matrix.
Table 5: activation energy of large-gloss PET (polyethylene terephthalate) slice, halogen-free flame retardant and PET flame retardant master batch calculated by Flynn-Wall-Ozawa method under different weight loss rates
And deducing the stage of the halogen-free flame retardant playing a flame retardant role by combining the final char formation amount, wherein if the numerical value of the final char formation amount of the PET flame retardant master batch is obviously larger than the numerical value of the char formation amount of the large-sized bright PET slice, the flame retardance of the PET flame retardant master batch can be represented, as shown in Table 6.
Table 6: t of large bright PET slice, halogen-free flame retardant and PET flame retardant master batch at heating rate of 10 ℃/min 5％ 、T max Final char formation data
As is clear from Table 6, the initial decomposition temperature (temperature at which the weight loss is 5%, T) of the halogen-free flame retardant was found at a temperature rise rate of 10℃per minute 5％ ) And peak temperature (T) corresponding to the maximum rate of weight loss max ) The temperature is higher than the corresponding temperature of the big bright PET slice by more than 30 ℃, which indicates that the PET flame-retardant master batch can be used for preparing PET flame-retardant master batch, is favorable for processing, wherein T is max Is found by smoothing the data of the DTG by gnuppot application smoothcsplines. Combined with the final char formationAs a result, after the halogen-free flame retardant is added, the char yield of the PET flame retardant master batch is improved by 41 percent compared with that of the pure large bright PET slices. This shows that the halogen-free flame retardant forms a carbon layer in the decomposition process to play a role in blocking, slows down the decomposition of PET, and plays a role in flame retardance, thereby increasing the carbon formation amount.
When the Kissinger method is applied, smoothing is carried out on the DTG data by utilizing the Smooth cspline of Gnupplot, and peak temperature when the weightlessness rate is maximum is searched out and substituted into a formula of the Kissinger method for operation. Linear solution to obtain slope
And intercept->
The activation energy E and the logarithmic pre-finger factor lnA were thus determined. The activation energy obtained by the method is the activation energy and the logarithmic pre-finger factor when the weight loss rate is maximum. />
The Kissinger method formula is:
the method comprises the following steps: in the pyrolysis process, finding out the temperature T corresponding to the maximum weight loss rate of the large bright PET slice, the halogen-free flame retardant and the PET flame retardant master batch in the pyrolysis process at the heating rate of 10-25 ℃/min max (T at a heating rate of 10 ℃ C./min as shown in Table 6) max ) And substituting the obtained product into a Kissinger formula to calculate and fit to obtain a Kissinger normal relation diagram of the large bright PET slice, the halogen-free flame retardant and the PET flame retardant master batch, wherein the Kissinger normal relation diagram is shown in figures 5-7, and specific activation energy, logarithmic pre-finger factor and other data are shown in table 7. The absolute values of the correlation coefficients r of the schematic diagrams of the normal relation of the Kissinger are all larger than 0.99, which indicates that the graph drawn by using the Gnupilot and using the Kissinger method has higher fitting degree, and proves that the Kissinger method has higher reliability of activation energy when the calculated weightlessness rate is maximum.
Table 7: big bright PET slice, halogen-free flame retardant and PET flame retardant master batch calculated by Kissinger method are in T max Activation energy at time and logarithmic pre-finger factor
As can be seen from Table 7, after the halogen-free flame retardant is added into PET, the activation energy and the factor before logarithmic finger of the PET flame-retardant master batch at the maximum weight loss rate are higher than those of the large-light PET slice, and the analysis results are consistent with the Flynn-Wall-Ozawa method.
The Kissinger normal linear relation schematic diagrams of the large bright PET slice, the halogen-free flame retardant and the PET flame retardant master batch are shown in figures 5-7, and the absolute value of the correlation coefficient is larger than 0.99. From the results, the graph drawn by using the Kissinger method by Gnupplot has higher fitting degree, and the Kissinger method has higher reliability on the activation energy when the weight loss rate is calculated to be maximum.
From experimental results, the invention can effectively and accurately help researchers analyze the thermal performance of PET flame retardant master batch, the flame retardant effect of flame retardant and potential influencing factors. According to the two methods, the thermal stability of the PET flame-retardant master batch is qualitatively and quantitatively analyzed by analyzing the thermal performance parameters of the large-gloss PET slice, the halogen-free flame retardant and the PET flame-retardant master batch. Compared with the traditional manual calculation, the time and the labor for analyzing the test data are greatly shortened, and the efficiency of developing PET flame-retardant master batches and other flame-retardant materials is obviously improved.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. Furthermore, it should be noted that the scope of the methods and apparatus in the embodiments of the present application is not limited to performing the functions in the order shown or discussed, but may also include performing the functions in a substantially simultaneous manner or in an opposite order depending on the functions involved, e.g., the described methods may be performed in an order different from that described, and individual steps may also be added, omitted, or combined. Additionally, features described with reference to certain examples may be combined in other examples.
The embodiments of the present application have been described above with reference to the accompanying drawings, but the present application is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and many forms may be made by those of ordinary skill in the art without departing from the spirit of the present application and the scope of the claims, which are also within the protection of the present application.
Claims (7)
1. A calculation method for analyzing thermal performance of PET flame-retardant master batch is characterized by comprising the following steps: the method comprises the following steps:
s1: respectively taking 10mg of big bright PET slices and 10mg of halogen-free flame retardant as raw materials, placing the raw materials in a crucible, and performing thermogravimetric analysis to obtain a thermogravimetric TG-DTG curve at multiple heating rates;
s2: taking 50-80% of large bright PET slices and 20-50% of halogen-free flame retardant, drying at 120 ℃ for 4-6 hours, uniformly mixing the dried raw materials by a high-speed mixer, extruding the mixed raw materials by a double-screw extruder to prepare PET flame-retardant master batches, placing 10mgPET flame-retardant master batches into a crucible, and performing thermogravimetric analysis to obtain a thermogravimetric TG-DTG curve at multiple heating rates;
s3: acquiring peak temperature and final char formation data corresponding to the maximum initial decomposition temperature and the maximum weight loss rate, qualitatively evaluating the thermal stability of the large bright PET slices, the halogen-free flame retardant and the PET flame retardant master batch, analyzing the temperature difference between the initial decomposition temperature and the peak temperature of the PET flame retardant master batch and the temperature corresponding to the large bright PET slices, deducing the stage that the halogen-free flame retardant plays a flame retardant role by combining the final char formation, and if the numerical value of the final char formation of the PET flame retardant master batch is obviously larger than the numerical value of the char formation of the large bright PET slices, representing the flame retardance of the PET flame retardant master batch;
s4: the related experimental data for calculation is processed by adopting a Scipy library of a Python tool to call a cut_fit function and a fit function command of Gnupplot and a Smooth csprines function, and noise interference existing in the data is eliminated by utilizing a command line in the application process;
s5: the activation energy and the logarithmic pre-finger factor were calculated by using the Flynn-Wall-Ozawa method and the Kissinger method to quantitatively evaluate the performance of the halogen-free flame retardant.
2. The method for calculating the thermal performance of the PET flame-retardant master batch according to claim 1, which is characterized in that: and when the Flynn-Wall-Ozawa method in the S5 is applied, sequentially calling thermal weight data of large bright PET slices, halogen-free flame retardant and PET flame retardant master batches in a local document at different heating rates through a Python tool, substituting the temperature data at the selected weight loss rate into a compiled Flynn-Wall-Ozawa method formula, and fitting the selected data by using a curve_fit.
3. The method for calculating the thermal performance of the PET flame-retardant master batch according to claim 1, which is characterized in that: and (3) smoothing the DTG data by utilizing the Gnupplot' S Smooth cspline when the Kissinger method is applied in the S5, searching out the peak temperature when the weightlessness rate is maximum, and substituting the peak temperature into a Kissinger method formula for operation.
4. The method for calculating the thermal performance of the PET flame-retardant master batch according to claim 2, which is characterized in that: the loss rate of the Flynn-Wall-Ozawa method in the S5 is 5-70%.
5. A method of calculating thermal performance of a profiled PET flame retardant masterbatch according to any one of claims 1-4, characterized by: the thermogravimetric analysis in S1 and S2 was performed under the following conditions: the temperature range is 25-800 ℃, the temperature rising rate is 10-25 ℃/min, and the nitrogen atmosphere condition is 30ml/min.
6. The method for calculating the thermal performance of the PET flame-retardant master batch according to claim 5, which is characterized in that: the temperature of each zone of the twin-screw extruder in the step S2 is 250-280 ℃.
7. The method for calculating the thermal performance of the PET flame-retardant master batch according to claim 6, which is characterized in that: the halogen-free flame retardant is one or more of aluminum alkyl phosphate, zinc alkyl phosphate and magnesium alkyl phosphate.
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