A novel calcium-containing sulfonic acid-type ionomer flame retardant and its preparation method and application

Abstract

The present invention discloses a novel calcium-sulfonic acid ionomer flame retardant, a preparation method thereof, and an application thereof, and belongs to the technical field of flame retardant synthesis. The preparation method of the calcium-sulfonic acid ionomer flame retardant of the present invention comprises the following steps: mixing polycarbonate and a sulfonating reagent, performing a sulfonation reaction to obtain a sulfonated polycarbonate, mixing with a metal source modification component, and performing an ion exchange reaction to obtain the calcium-sulfonic acid ionomer flame retardant. The chemical structure of the calcium-sulfonic acid ionomer flame retardant of the present invention is similar to that of polycarbonate, and the synthesis process is simple and easy to operate. After being added to PC, it has little effect on the compatibility of the product system, is non-toxic, heat-insulating and oxygen-isolating, can achieve a high flame retardant effect at a relatively low addition amount, and maintains the high mechanical properties of the composite material, and is suitable for promotion and application.

Description

Technical Field

[0001] The present invention relates to the technical field of flame retardant synthesis, in particular to a novel calcium-containing sulfonic acid type ionomer flame retardant and a preparation method and application thereof. Background Art

[0002] Bisphenol A-based polycarbonate (PC) boasts excellent transparency, high mechanical strength, good stability, a high glass transition temperature, and electrical insulation properties, making it a popular alternative to glass and other plastics in many demanding environments. However, PC's tendency to produce dripping and toxic fumes during combustion limits its use in safety-critical applications, such as medical devices, electronic appliances, and automotive parts. These applications typically require the material to be self-extinguishing, produce minimal smoke and toxic gases, and minimize dripping, thereby minimizing fire risk and injury.

[0003] Currently, commonly used polycarbonate flame retardants can be divided into two categories based on the elements they contain: inorganic flame retardants and organic flame retardants. Inorganic and organic flame retardants can be further categorized based on the primary elements that contribute to their flame retardancy into organic / inorganic halogen flame retardants, organic / inorganic phosphorus flame retardants, organic / inorganic boron flame retardants, organic / inorganic silicon flame retardants, and organic / inorganic sulfonate flame retardants.

[0004] Sulfonate flame retardants can rapidly release large amounts of stable gases at high temperatures, forming a protective layer that effectively isolates the combustion source and slows the spread of fire. They also exhibit excellent antioxidant properties, remain stable at high temperatures, and are less susceptible to decomposition and failure. They also exhibit good weather resistance in open environments, are less susceptible to UV rays, moisture, and other factors, maintain a long-term flame retardant effect, and can effectively delay the release of smoke generated during combustion. However, the molecular structure of sulfonate flame retardants in existing technologies differs significantly from that of polycarbonate, which can lead to poor compatibility and reduced mechanical properties of the composite material. For example, when a commercially available KSS sulfonate flame retardant is added at a 0.2 wt.% concentration, the notched impact strength of the composite material drops to 19.27 MPa, a nearly 70% decrease from the 63.35 MPa of pure PC. Therefore, further improvement is needed. Summary of the Invention

[0005] The present invention aims to provide a novel calcium-sulfonic acid-based ionomer flame retardant, its preparation method, and its application, to address the aforementioned problems in the background art. The calcium-sulfonic acid-based ionomer flame retardant of the present invention has a chemical structure similar to that of polycarbonate, a simple and easy-to-operate synthesis process, and has minimal impact on the compatibility of the product system after addition to PC. It is non-toxic, heat-insulating, and oxygen-insulating, and can achieve a high flame retardant effect at a relatively low addition amount while maintaining the high mechanical properties of the composite material, making it suitable for widespread application.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] One of the technical solutions of the present invention is to provide a calcium-containing sulfonic acid-type ionomer flame retardant, the structural formula of the flame retardant is as follows:

[0008]

[0009] The second technical solution of the present invention is to provide a method for preparing the above-mentioned calcium-containing sulfonic acid type ionomer flame retardant, comprising the following steps:

[0010] The polycarbonate and the sulfonation reagent are mixed and subjected to a sulfonation reaction to obtain the sulfonated polycarbonate, which is then mixed with a metal source modification component and subjected to an ion exchange reaction to obtain the calcium-containing sulfonic acid type ionomer flame retardant.

[0011] Preferably, the sulfonating agent is diethyl sulfate.

[0012] Preferably, the preparation method of diethyl sulfate is: 98 wt.% concentrated sulfuric acid and acetic anhydride are mixed in a solvent 1,2-dichloroethane, and an esterification reaction is carried out to obtain a solution of intermediate compound II, wherein the intermediate compound II is diethyl sulfate. The relevant reaction formula is shown in Formula (1):

[0013]

[0014] More preferably, the temperature of the esterification reaction is 0-5° C., and the volume ratio of concentrated sulfuric acid to acetic anhydride is 1:2.5.

[0015] Because the reaction between concentrated sulfuric acid and acetic anhydride is vigorous, the reaction must be performed in an ice bath at 0-5°C. After the esterification reaction is complete, the solution becomes a yellow oil. However, when too much acetic anhydride is added, the product solution becomes colorless and transparent, indicating incomplete reaction.

[0016] More preferably, the mass ratio of the polycarbonate to the sulfonated reagent is 1-100:0-10, and is not 0.

[0017] More preferably, the sulfonation reaction is as follows: dissolving polycarbonate in 1,2-dichloroethane, adding diethyl sulfate, and reacting at 60° C. for 2 hours to obtain sulfonated polycarbonate.

[0018] More preferably, the sulfonation reaction is as follows: dissolving polycarbonate in 1,2-dichloroethane, adding diethyl sulfate, reacting at 60°C for 2 hours, then slowly adding the reaction system dropwise to boiling distilled water, filtering the precipitate, washing, and drying to obtain a white solid sulfonated polycarbonate (intermediate compound III). The relevant reaction formula is shown in Formula (II):

[0019]

[0020] More preferably, the ratio of 1,2-dichloroethane to polycarbonate is 10 mL:1 g.

[0021] When the reaction temperature exceeds 65°C, the reaction solution turns black-yellow and the thermal stability of the product decreases.

[0022] During the reaction, the reaction solution was tested with pH test paper, and the reaction was completed when the solution reached neutrality.

[0023] Since the boiling point of 1,2-dichloroethane is 83° C., boiling distilled water is used to remove excess solvent, and then the sulfonated polycarbonate is obtained by filtration.

[0024] More preferably, the drying temperature is less than 60°C.

[0025] Preferably, the metal source modifying component is calcium chloride.

[0026] Preferably, the ion exchange reaction is as follows: dissolving sulfonated polycarbonate in 1,2-dichloroethane, adding calcium chloride, reacting for 48 hours, then slowly adding the reaction system dropwise to boiling distilled water, filtering the precipitate, washing, and drying to obtain the calcium-containing sulfonic acid ionomer flame retardant (Compound I). The relevant reaction formula is shown in Formula (III):

[0027]

[0028] More preferably, the ratio of 1,2-dichloroethane to sulfonated polycarbonate is 10 mL:1 g.

[0029] More preferably, the drying temperature is less than 60°C.

[0030] More preferably, the added amount of the metal source modification component is 120 wt% of the theoretical required amount; the theoretical required amount is obtained by measuring the sulfonation degree of the sulfonated polycarbonate.

[0031] Preferably, the ion exchange reaction time is 48 hours.

[0032] Preferably, the sulfonation degree of the sulfonated polycarbonate is measured by dissolving the sulfonated polycarbonate in 1,2-dichloroethane, adding an excess of 0.1 mol / L KOH standard solution, and adding anhydrous ethanol to completely dissolve the KOH standard solution and the 1,2-dichloroethane solution of the sulfonated polycarbonate. After standing for 30 minutes, 0.1 mol / L HCl standard solution is added dropwise to the solution, and phenolphthalein is used as an indicator. The color change point is used as the titration endpoint, and the sulfonation degree of the sulfonated polycarbonate is calculated by detecting the volume of the consumed HCl standard solution.

[0033] More preferably, the ratio of the volume of 1,2-dichloroethane to the mass of the sulfonated polycarbonate is 5 mL:1 g.

[0034] The third technical solution of the present invention is to provide an application of the above-mentioned calcium-containing sulfonic acid type ionomer flame retardant in the field of polycarbonate flame retardants.

[0035] The fourth technical solution of the present invention: provides a polycarbonate composite material, wherein the raw materials of the polycarbonate composite material include the above-mentioned calcium-containing sulfonic acid type ionomer flame retardant; the addition amount of the calcium-containing sulfonic acid type ionomer flame retardant is 0-2wt.%, and is not 0.

[0036] The beneficial technical effects of the present invention are as follows:

[0037] The calcium-sulfonic acid-based ionomer flame retardant of this invention has a chemical structure similar to that of polycarbonate, and its synthesis process is simple and easy to operate. When added to PC, it has minimal impact on the compatibility of the resulting system. It is non-toxic, provides thermal insulation, and is oxygen-insulating. It can achieve high flame retardancy at relatively low addition levels while maintaining the high mechanical properties of the composite material, making it suitable for widespread application. When a 2 wt.% sulfonated flame retardant with a 5 wt.% degree of sulfonation is added, the resulting composite material exhibits a LOI value of 36% and passes UL-94 V-0.

[0038] The flame retardant system designed in this invention not only improves the flame retardancy of polycarbonate composites but also enhances mechanical properties such as impact strength and flexural strength. The calcium-sulfonic acid-based ionomer flame retardant designed in this invention has minimal impact on the mechanical properties and transparency of polycarbonate. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0040] Figure 1 Flow chart of the preparation method of Examples 1-3 of the present invention.

[0041] Figure 2 This is a Fourier transform infrared spectrum of the product of Example 3 of the present invention. DETAILED DESCRIPTION

[0042] Various exemplary embodiments of the present invention are now described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention.

[0043] In addition, for numerical ranges in the present invention, it is understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any stated value or stated range, and any other stated value or intervening value in the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention.

[0045] The terms “include,” “including,” “have,” “contain,” etc. used in the present invention are open-ended terms, meaning including but not limited to.

[0046] The present invention provides a method for preparing a calcium-containing sulfonic acid type ionomer flame retardant, comprising the following steps:

[0047] The polycarbonate and the sulfonation reagent are mixed and subjected to a sulfonation reaction to obtain the sulfonated polycarbonate, which is then mixed with a metal source modification component and subjected to an ion exchange reaction to obtain the calcium-containing sulfonic acid type ionomer flame retardant.

[0048] Preferably, the preparation method of diethyl sulfate is: mixing 98 wt.% concentrated sulfuric acid with acetic anhydride, and performing an esterification reaction to obtain a solution of intermediate compound II, wherein the intermediate compound II is diethyl sulfate. The relevant reaction formula is shown in formula (1):

[0049]

[0050]

[0051] More preferably, the temperature of the esterification reaction is 0-5° C., and the volume ratio of concentrated sulfuric acid to acetic anhydride is 1:2.5.

[0052] Because the reaction between concentrated sulfuric acid and acetic anhydride is vigorous, the reaction must be performed in an ice bath at 0-5°C. After the esterification reaction is complete, the solution becomes a yellow oil. However, when too much acetic anhydride is added, the product solution becomes colorless and transparent, indicating incomplete reaction.

[0053] More preferably, the sulfonation reaction is as follows: dissolving polycarbonate in 1,2-dichloroethane, adding diethyl sulfate, reacting at 60°C for 2 hours, then slowly adding the reaction system dropwise to boiling distilled water, filtering the precipitate, washing, and drying to obtain a white solid sulfonated polycarbonate (intermediate compound III). The relevant reaction formula is shown in Formula (II):

[0054]

[0055] More preferably, the ratio of 1,2-dichloroethane to polycarbonate is 10 mL:1 g.

[0056] When the reaction temperature exceeds 65°C, the reaction solution turns black-yellow and the thermal stability of the product decreases.

[0057] During the reaction, the reaction solution was tested with pH test paper, and the reaction was completed when the solution reached neutrality.

[0058] Since the boiling point of 1,2-dichloroethane is 83° C., boiling distilled water is used to remove excess solvent, and then the sulfonated polycarbonate is obtained by filtration.

[0059] More preferably, the drying temperature is less than 60°C.

[0060] Preferably, the sulfonation degree of the sulfonated polycarbonate is measured by dissolving the sulfonated polycarbonate in 1,2-dichloroethane, adding an excess of 0.1 mol / L KOH standard solution, and adding anhydrous ethanol to completely dissolve the KOH standard solution and the 1,2-dichloroethane solution of the sulfonated polycarbonate. After standing for 30 minutes, 0.1 mol / L HCl standard solution is added dropwise to the solution, and phenolphthalein is used as an indicator. The color change point is used as the titration endpoint, and the sulfonation degree of the sulfonated polycarbonate is calculated by detecting the volume of the consumed HCl standard solution.

[0061] More preferably, the ratio of 1,2-dichloroethane to sulfonated polycarbonate is 5 mL:1 g.

[0062] Preferably, the ion exchange reaction is as follows: dissolving sulfonated polycarbonate in 1,2-dichloroethane, adding calcium chloride, reacting for 48 hours, then slowly adding the reaction system dropwise to boiling distilled water, filtering the precipitate, washing, and drying to obtain the calcium-containing sulfonic acid ionomer flame retardant (Compound I). The relevant reaction formula is shown in Formula (III):

[0063]

[0064] More preferably, the ratio of 1,2-dichloroethane to sulfonated polycarbonate is 10 mL:1 g.

[0065] More preferably, the drying temperature is less than 60°C.

[0066] The method for measuring the sulfonation degree of the sulfonated polycarbonate in the following embodiments of the present invention is as follows: the sulfonated polycarbonate is dissolved in 1,2-dichloroethane (the ratio of 1,2-dichloroethane to sulfonated polycarbonate is 5 mL:1 g), an excess of 0.1 mol / L KOH standard solution is added, and anhydrous ethanol is added to completely dissolve the KOH standard solution and the 1,2-dichloroethane solution of the sulfonated polycarbonate. After standing for 30 minutes, a 0.1 mol / L HCl standard solution is added dropwise to the solution, and phenolphthalein is used as an indicator. The color change point is used as the titration endpoint, and the sulfonation degree of the sulfonated polycarbonate is calculated by detecting the volume of the consumed HCl standard solution.

[0067] The concentration of concentrated sulfuric acid used in the following examples of the present invention is 98 wt.%.

[0068] The temperature of the boiling distilled water used in the following embodiments of the present invention is 100°C.

[0069] The raw materials used in the following examples of the present invention are all commercially available products.

[0070] Example 1

[0071] A preparation method of a calcium-containing sulfonic acid type ionomer flame retardant:

[0072] First, 1 mL of concentrated sulfuric acid and 2.5 mL of acetic anhydride were dissolved in 1,2-dichloroethane and subjected to an esterification reaction at 0°C to produce diethyl sulfate. 100 g of polycarbonate was dissolved in 1 L of 1,2-dichloroethane and the diethyl sulfate produced in the first step was added with stirring at 60°C. The reaction was allowed to react for 2 hours. The reaction system was then slowly added dropwise to boiling distilled water. The precipitate was filtered, washed, and dried (drying temperature < 60°C) to obtain a white solid sulfonated polycarbonate (the degree of sulfonation of this sulfonated polycarbonate was determined to be 1 wt.%).

[0073] 10 g of sulfonated polycarbonate was dissolved in 100 mL of 1,2-dichloroethane, 0.15 g of calcium chloride (20 wt% excess) was added to distilled water, dissolved, and then poured into the solution system. The mixture was stirred for 48 h to carry out an ion exchange reaction. The reaction system was then slowly added dropwise to boiling distilled water. The precipitate was filtered, washed, and dried (drying temperature <60°C) to obtain a calcium-containing sulfonic acid ionomer flame retardant (denoted as SPC-Ca).

[0074] Example 2

[0075] A preparation method of a calcium-containing sulfonic acid-type ionomer flame retardant:

[0076] First, 2 mL of concentrated sulfuric acid and 5 mL of acetic anhydride were dissolved in 1,2-dichloroethane and subjected to an esterification reaction at 0°C to produce diethyl sulfate. Then, 100 g of polycarbonate was dissolved in 1 L of 1,2-dichloroethane and the diethyl sulfate produced in the first step was added with stirring at 60°C. The reaction was allowed to react for 2 hours. The reaction system was then slowly added dropwise to boiling distilled water. The precipitate was filtered, washed, and dried (drying temperature < 60°C) to obtain a white solid sulfonated polycarbonate (the degree of sulfonation of this sulfonated polycarbonate was determined to be 3 wt.%).

[0077] 5 g of sulfonated polycarbonate was dissolved in 50 mL of 1,2-dichloroethane, 0.24 g of calcium chloride was added to distilled water and dissolved, and then poured into the solution system and stirred for 48 hours to carry out ion exchange reaction. Then, the reaction system was slowly added dropwise to boiling distilled water, the precipitate was filtered, washed and dried (drying temperature <60°C) to obtain a calcium-containing sulfonic acid type ionomer flame retardant (denoted as SPC-Ca).

[0078] Example 3

[0079] A preparation method of a calcium-containing sulfonic acid-type ionomer flame retardant:

[0080] First, 5 mL of concentrated sulfuric acid and 12.5 mL of acetic anhydride were dissolved in 1,2-dichloroethane and subjected to an esterification reaction at 0°C to produce diethyl sulfate. Then, 100 g of polycarbonate was dissolved in 1 L of 1,2-dichloroethane and the diethyl sulfate produced in the first step was added with stirring at 60°C. The reaction was allowed to react for 2 hours. The reaction system was then slowly added dropwise to boiling distilled water. The precipitate was filtered, washed, and dried (drying temperature < 60°C) to obtain a white solid sulfonated polycarbonate (the degree of sulfonation of this sulfonated polycarbonate was determined to be 1 wt.%).

[0081] 20 g of sulfonated polycarbonate was dissolved in 200 mL of 1,2-dichloroethane, 5 g of calcium chloride was added to distilled water and dissolved, and then poured into the solution system, stirred for 48 hours to carry out ion exchange reaction, and then the reaction system was slowly added dropwise to boiling distilled water. The precipitate was filtered, washed and dried (drying temperature <60°C) to obtain a calcium-containing sulfonic acid type ionomer flame retardant (denoted as SPC-Ca).

[0082] Figure 1 Flow chart of the preparation method of Examples 1-3 of the present invention.

[0083] Figure 2 This is a Fourier transform infrared spectrum of the product of Example 3 of the present invention.

[0084] Figure 2 Medium, 3455cm -1Nearby is the OH stretching vibration peak. Since there is no OH stretching vibration peak in the infrared characteristic peak of polycarbonate, it can be proved that it comes from the sulfonic acid group introduced by the sulfonation reaction; 2919cm -1 The peak near 1619cm is the CH stretching vibration peak, which comes from the isopropylidene group in the sulfonated polycarbonate, proving that it does not break during the sulfonation reaction; -1 The C=O stretching vibration absorption peak is located at 1285cm, which proves that the two bonds with the smallest dissociation energy are not destroyed in the sulfonation reaction. -1 The absorption peak between is caused by the stretching vibration of the sulfonic acid group S=O. The sulfonated product is at 1072 cm -1 The stretching vibration absorption peak representing the sulfonic acid group on the benzene ring is difficult to distinguish. -1 Nearby, an absorption peak representing the in-plane bending vibration of the sulfonic acid group-substituted benzene ring appears.

[0085] Effect verification

[0086] The polycarbonate composite material was prepared as follows:

[0087] (1) The PC masterbatch was dried in a forced air drying oven at 100°C for 10 h. The products of each example and a commercial KSS flame retardant were then mixed with the PC masterbatch in different proportions. The mixture was then extruded, cooled, and pelletized using a twin-screw extruder to obtain pellets. The screw speed was 100 r / min. The temperature settings for each temperature zone of the twin-screw extruder are shown in Table 1.

[0088] Table 1 Temperature of each temperature section of twin-screw extruder

[0089]

[0090] (2) The pellets were dried in a forced air drying oven at 100°C for 10 h, and then an injection molding machine was used to produce experimental standard specimens (polycarbonate composite materials) in accordance with GB / T 25156-2010. The LOI values ​​(limiting oxygen index) of the experimental standard specimens were obtained using the ISO4589-1996 standard test, and the specimen specifications were 120 mm × 10 mm × 4 mm. The vertical combustion test was conducted using the UL-94 standard, and the specimen specifications were 120 mm × 13 mm × 3.2 mm. Injection molding pressure: 50 MPa for the first and second sections, respectively. The temperatures of each temperature section of the injection molding machine are shown in Table 2. The results of the limiting oxygen index and vertical combustion tests are shown in Table 3. The results of the mechanical properties tests are shown in Table 4.

[0091] Table 2 Temperature of each temperature range of injection molding machine

[0092]

[0093] Table 3 Flame retardant performance test at different flame retardant additions

[0094]

[0095] As shown in Table 3, the LOI value of the experimental standard specimen prepared from pure PC was 26.8%, and the UL-94 vertical combustion rating was UL-94 V-2. The LOI value of the composite material gradually increased with increasing flame retardant addition. When 1 wt.% of a 1 wt.% sulfonated flame retardant was added, the composite material's LOI value was 33.5%, passing the UL-94 V-0 rating. When 2 wt.% of a 5 wt.% sulfonated flame retardant was added, the composite material's LOI value was 36.5%, also passing the UL-94 V-0 rating. This demonstrates that the calcium-sulfonic acid-based ionomer flame retardant prepared in this invention can significantly improve the LOI value of composite materials, exhibiting excellent flame retardancy, surpassing commercial KSS flame retardants.

[0096] In summary, the calcium sulfonic acid ionomer flame retardant effectively enhances the flame retardancy of the substrate. This is likely due to its ability to prematurely decompose and rearrange PC, leading to cross-linking reactions that increase the stability and density of the carbon layer and act as an oxygen barrier.

[0097] Table 4 Mechanical properties test at different addition amounts of SPC-Ca

[0098]

[0099]

[0100] As shown in Table 4, the composite material to which the novel calcium-containing sulfonic acid ionomer flame retardant of the present invention is added has enhanced flexural strength and elongation at break while maintaining the tensile strength and slightly reducing the notched impact strength.

[0101] The flame retardant designed in the present invention has a novel structure, is non-toxic, and is heat-insulating and oxygen-insulating. It can achieve a high flame retardant effect even at a low addition amount without affecting the mechanical properties. At the same time, the synthesis process is simple, easy to operate, and suitable for promotion and application.

[0102] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A calcium-containing sulfonic acid type ionomer flame retardant, characterized in that: The structural formula of the flame retardant is as follows:

2. A method for preparing the calcium-containing sulfonic acid type ionomer flame retardant according to claim 1, characterized in that: The following steps are involved: The polycarbonate and the sulfonating agent are mixed and subjected to a sulfonation reaction to obtain the sulfonated polycarbonate, which is then mixed with a metal source modification component and subjected to an ion exchange reaction to obtain the calcium-containing sulfonic acid type ionomer flame retardant.

3. The preparation method according to claim 2, characterized in that The sulfonating agent is diethyl sulfate.

4. The preparation method according to claim 3, characterized in that The sulfonation reaction is as follows: polycarbonate is dissolved in 1,2-dichloroethane, diethyl sulfate is added, and the mixture is reacted at 60° C. for 1-5 hours to obtain sulfonated polycarbonate.

5. The preparation method according to claim 3, characterized in that The mass ratio of the polycarbonate to the sulfonated reagent is 1-100:0-10, and is not 0.

6. The preparation method according to claim 2, characterized in that The metal source modification component is calcium chloride.

7. The preparation method according to claim 6, characterized in that The added amount of the metal source modification component is 120 wt% of the theoretical required amount; the theoretical required amount is obtained by measuring the sulfonation degree of the sulfonated polycarbonate.

8. The preparation method according to claim 2, characterized in that The ion exchange reaction time is 48 hours.

9. Use of the calcium-containing sulfonic acid ionomer flame retardant according to claim 1 in the field of polycarbonate flame retardants.

10. A polycarbonate composite material, characterized in that: The raw materials of the polycarbonate composite material include the calcium-containing sulfonic acid type ionomer flame retardant according to claim 1; the addition amount of the calcium-containing sulfonic acid type ionomer flame retardant is 0-2wt.%, and is not 0.

Images