A pps-based chlorine-containing standard substance and a preparation method thereof

Abstract

The application discloses a PPS-based chlorine-containing standard substance and a preparation method thereof, and belongs to the technical field of high polymer materials. The product is prepared by taking bis(hexachlorocyclopentadiene) cyclooctane or a derivative thereof as a chlorine-containing component in PPS resin and introducing a specific dispersant for compounding. When the product is used as a standard substance, the calibration of the chlorine content of the product can realize the uniformity and stability required by a standard, and the product is suitable for calibration and effective quantitative analysis of PPS products in XRF test of chlorine element content. In addition, the product can also be used as a solid standard substance and applied to common quantitative test analysis and instrument calibration of chlorine elements.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a PPS-based chlorine-containing standard substance and its preparation method. Background Technology

[0002] PPS (polyphenylene sulfide) is a high-performance engineering plastic that can be used in many fields. However, chlorine impurities may be introduced during the preparation of PPS. The amount of these impurities directly affects the performance and stability of the product. Therefore, the amount of chlorine in PPS is often used to measure its purity and quality.

[0003] Among the methods for detecting chlorine content in PPS, the traditional oxygen bomb combustion-ion chromatography method, while highly accurate, has a long testing cycle, cumbersome operation steps, involves the use of corrosive gases during the testing process, has a high equipment wear rate, and low safety. Therefore, people have begun to use XRF (X-ray fluorescence spectrometry) as an alternative. XRF has simple operation steps, a short testing cycle, and can achieve rapid sample screening. However, during the testing process, after baseline calibration and standard curve establishment using conventional liquid or solid chlorine-containing standards (such as polyethylene plastic matrix standard materials), when testing PPS products, the sulfur element contained in PPS will interfere with the Ka line of chlorine, resulting in an artificially high chlorine detection intensity. This will directly lead to the chlorine content obtained by the standard curve test being much higher than the actual content. At the same time, chlorine has poor stability in PPS and is highly sensitive to external factors. If solid chlorine-containing standards are prepared using PPS resin, the homogeneity and stability requirements of the standard material cannot be met. Summary of the Invention

[0004] Based on the deficiencies of existing technologies, the purpose of this invention is to provide a PPS-based chlorine-containing standard material. This product uses bis(hexachlorocyclopentadiene)cyclooctane or its derivatives as the chlorine-containing component in PPS resin and introduces a specific dispersant for compounding. When used as a standard material, its chlorine content calibration can achieve the uniformity and stability required by the standard. It is suitable for calibration and effective quantitative analysis of chlorine content in PPS products during XRF testing. It can also be used as a solid standard material in various quantitative testing and analysis of chlorine elements and instrument calibration.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A PPS-based chlorine-containing standard material, comprising bis(hexachlorocyclopentadiene)cyclooctane or a derivative thereof, and further comprising the following components in parts by weight: 90-100 parts PPS resin, 0.5-1 part dispersant, and 0.5-3 parts compatibilizer; The chlorine content in the PPS-based chlorine-containing standard material is 40~3000 mg / kg; The thiol content of the PPS resin is 600~1500 mg / kg; The dispersant includes at least one of polyethylene wax and organosilicone.

[0006] In the process of rapid XRF quantification of chlorine content in PPS materials, sulfur in PPS interferes with the Ka curve. Therefore, it is necessary to use a standard or reference material with similar properties for baseline calibration and standard curve establishment to eliminate the interference of sulfur in the curve background, thereby quantifying the true chlorine content. This type of material is also required for instrument calibration during routine maintenance. However, existing chlorine standards are mainly divided into liquid-phase standards and solid-phase standards. Although liquid-phase standards have high homogeneity and stability, they are not suitable for XRF testing of solid samples, especially PPS-based materials, for chlorine content determination. Solid standards are mainly made of plastic. While these non-PPS-based standards can be used for routine instrument calibration and other testing scenarios, the significant difference in sulfur content between them and PPS resin makes them unsuitable for XRF testing of chlorine content in PPS-based materials. Furthermore, the poor and uncontrollable stability of chlorine in PPS-based chlorine-containing materials fails to meet the homogeneity and stability requirements of a standard, making them unsuitable as effective reference materials.

[0007] Therefore, in this invention, the inventors have developed a standard substance that can be used for routine instrument maintenance and quantitative testing, especially suitable for XRF rapid quantitative analysis of chlorine content in PPS materials. This product uses PPS resin as a matrix and can be effectively used for baseline calibration and standard curve establishment when testing solid PPS-based materials with sulfur interference. To meet the homogeneity and stability requirements of the standard substance, bis(hexachlorocyclopentadiene)cyclooctane or its derivatives are introduced into the matrix as a chlorine-containing positive ion, and the thiol content of the PPS resin is controlled within a specific range. Finally, at least one of polyethylene wax and organosilicone is used as a dispersant. Bis(hexachlorocyclopentadiene)cyclooctane or its derivatives, due to their high thermal stability and highly compatible multi-ring structure, exhibit higher compatibility and stability compared to inorganic or other organic molecules when combined with PPS resin. When applied as a standard substance, it can exhibit ideal chlorine content. Content stability; Furthermore, due to the high controllability of its chlorine content, this substance can precisely match the actual chlorine content requirements of the product during application. When combined with polyethylene wax and / or silicone, which also have high compatibility, the small molecular weight of these two substances provides compatibility and internal lubrication between bis(hexachlorocyclopentadiene)cyclooctane or its derivatives and the matrix resin during preparation (the molecular chains of polyethylene wax and silicone interweave between the molecular chains of PPS resin), significantly improving the dispersion uniformity of each component. On the other hand, by controlling the mercapto content of PPS resin, the interaction force between PPS resin and bis(hexachlorocyclopentadiene)cyclooctane or its derivatives can be optimized, further reducing the probability of bis(hexachlorocyclopentadiene)cyclooctane or its derivatives precipitating, migrating, or agglomerating from the product, and improving the thermal stability of PPS resin itself, enabling the product to effectively meet the high uniformity and high stability requirements of standard substances.

[0008] When the PPS-based chlorine-containing standard material with uniformity and stability described in this invention is used for XRF testing of the chlorine content of PPS-based materials, the standard curve established by this standard material, which is also a PPS-based material, can effectively offset the interference of sulfur element in the sample during the test compared with other types of solid standard materials, and the accuracy of the test results is significantly improved.

[0009] Preferably, the PPS resin is in the range of any one or both of the following weight parts: 90 parts, 91 parts, 92 parts, 93 parts, 95 parts, 97 parts, 97.5 parts, 98 parts, 98.5 parts, 99 parts, and 100 parts; the dispersant is in the range of any one or both of the following weight parts: 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, and 1 part; and the compatibilizer is in the range of any one or both of the following weight parts: 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 2 parts, and 3 parts.

[0010] Preferably, the chlorine content in the PPS-based chlorine-containing standard substance is one or any two of the following values: 40 mg / kg, 80 mg / kg, 100 mg / kg, 200 mg / kg, 500 mg / kg, 800 mg / kg, 1000 mg / kg, 1500 mg / kg, 2000 mg / kg, 2500 mg / kg, and 3000 mg / kg.

[0011] It should be noted that the chlorine content in the PPS-based chlorine-containing standard material described in this application was confirmed in the following manner: Weigh 0.1 g of sample (accurate to 0.0001 g) and place it in a metal crucible for oxygen bomb combustion. Add 20 mL of ultrapure water as the absorption solution and seal the crucible. Inflate the crucible with oxygen at 1.2 MPa and ignite it using an ignition device. After the sample has fully burned, shake it 2-3 times and allow it to stand for absorption for 2 hours. After complete absorption, rinse the electrode and crucible with ultrapure water and transfer the solution to a 50 mL plastic volumetric flask. Make up to volume and quantitatively determine the chlorine content using an ion chromatograph.

[0012] Preferably, the PPS-based chlorine-containing standard substance contains PPS resin at a mass percentage of ≥80wt%.

[0013] Preferably, the PPS resin has a melt index of 400~800 cm⁻¹ at 316°C and 5.0 kg load according to ISO 1133-1-2022. 3 / 10min.

[0014] Preferably, the mass percentage of chlorine in the PPS resin is ≤30 mg / kg.

[0015] Preferably, the thiol content of the PPS resin is one or any two of the following: 600 mg / kg, 800 mg / kg, 900 mg / kg, 1000 mg / kg, 1100 mg / kg, 1200 mg / kg, 1300 mg / kg, 1400 mg / kg, and 1500 mg / kg.

[0016] Preferably, the thiol content of the PPS resin is 700~1200 mg / kg.

[0017] It should be noted that the thiol content of the PPS resin can be confirmed in the following way: Referring to Liu Lin's "The Influence of End-Group Control and Post-treatment on the Structure and Properties of Polyphenylene Sulfide", section 2.2.4.3, the method for testing mercapto content is as follows: Dissolve an appropriate amount of sample in 1-chloronaphthalene, add excess 2,4-dinitrochlorobenzene and anhydrous potassium carbonate, heat to 220℃ and react for 2 hours. After cooling, extract with water, take the supernatant, and determine the chloride ion content by mercuric nitrate solution titration or ion chromatography to indirectly calculate the mercapto content of the sample.

[0018] Preferably, the PPS-based chlorine-containing standard substance contains 0.01 to 1 part by weight of bis(hexachlorocyclopentadiene)cyclooctane or its derivatives.

[0019] Preferably, the bis(hexachlorocyclopentadiene)cyclooctane derivative includes dodecachlorooctahydro-methylene-cyclobutane.

[0020] More preferably, the bis(hexachlorocyclopentadiene)cyclooctane or its derivative is added in the form of a masterbatch, wherein the masterbatch is 0.1 to 10 parts by weight.

[0021] To avoid corrosion of processing equipment by chlorine during the processing of bis(hexachlorocyclopentadiene)cyclooctane or its derivatives, those skilled in the art can preprocess bis(hexachlorocyclopentadiene)cyclooctane or its derivatives in masterbatch form based on the actual processing scenario, and then compound them with PPS resin to prepare the product. At the same time, based on the processing effect requirements, the PPS resin in the final product can be used as the matrix resin in the masterbatch, and some or all of the polyethylene wax can be compounded as a dispersant. In addition, other processing aids that do not degrade the uniformity and stability of the product, such as antioxidants and compatibilizers, can be introduced.

[0022] Preferably, the masterbatch contains 1% to 20% by mass of bis(hexachlorocyclopentadiene)cyclooctane or its derivatives.

[0023] Preferably, the polyethylene wax is oxidized polyethylene wax, and the density of the oxidized polyethylene wax is 0.9~1.3 g / cm³. 3 .

[0024] It should be noted that in the PPS-based chlorine-containing standard material of the present invention, in addition to polyethylene wax and organosilicone, other common PPS dispersant components can be introduced in combination as long as the function of polyethylene wax is not affected. For example, pentaerythritol stearic acid, which has both dispersing and lubricating effects, can be used in combination with polyethylene wax to further improve the dispersion effect of the product components. However, at least one of polyethylene wax and organosilicone must be a necessary component; otherwise, the resulting product will be difficult to achieve the uniformity and stability required by the standard material.

[0025] Preferably, the organosilicone includes at least one of polysiloxane, polydimethylsiloxane, and epoxy-modified siloxane.

[0026] More preferably, the silicone exists in the form of a masterbatch, wherein the mass percentage of silicone in the masterbatch is 40-60%.

[0027] More preferably, the masterbatch is at least one of GT-300 and MB50-002.

[0028] Preferably, the compatibilizer comprises maleic anhydride grafts, which include at least one of maleic anhydride-grafted polyolefins and maleic anhydride-grafted elastomers.

[0029] More preferably, the maleic anhydride graft includes at least one of maleic anhydride-grafted POE, maleic anhydride-grafted polypropylene, maleic anhydride-grafted polyethylene, maleic anhydride-grafted SEBS (styrene-ethylene-butene-styrene copolymer), and maleic anhydride-grafted EPDM (ethylene propylene diene monomer rubber).

[0030] Preferably, the grafting rate of the maleic anhydride graft is 0.5% to 2%.

[0031] More preferably, the grafting rate of the maleic anhydride graft is 1% to 1.2%.

[0032] The grafting rate of the maleic anhydride graft was confirmed by titration. Weigh 0.5g of the analyte and dissolve it completely in 50mL of hot xylene. Add V1mL of C1mol / L NaOH-ethanol solution. Reflux at 140℃ for 10min to allow the maleic anhydride groups in the analyte to react fully with the alkali. Add an appropriate amount of deionized water to promote the hydrolysis of the anhydride to carboxylic acid. Simultaneously add 3 drops of phenolphthalein indicator solution. Titrate with hydrochloric acid / isopropanol solution to the endpoint. The concentration of hydrochloric acid / isopropanol is C2 (mol / L). Titrate m (g) of sample, consuming V2 (mL) of solution. The grafting rate G is calculated using the following formula: ; As mentioned above, V1 is the volume of excess NaOH-ethanol solution, V2 is the volume of HCl-isopropanol solution in the back titration, C1 is the concentration of NaOH-ethanol standard solution, C2 is the concentration of HCl-isopropanol solution, and m is the mass of the analyte, i.e., 0.5g.

[0033] When bis(hexachlorocyclopentadiene)cyclooctane or its derivatives and polyethylene wax and / or organosilicone are selected as positive substances and dispersants, compatibilizers can be further introduced into the product of the present invention to improve the uniformity and stability required when the product is used as a standard substance, so that the product has better performance. On this basis, maleic anhydride grafted polyethylene is used for compounding. Under the condition of high compatibility of components, the entanglement effect of maleic anhydride can further improve the tightness of the connection between components, especially the tightness of the connection between bis(hexachlorocyclopentadiene)cyclooctane or its derivatives. This makes the chemical stability of the component better during product preparation and storage, and the uniformity and stability of the product are improved more significantly.

[0034] Preferably, the PPS-based chlorine-containing standard substance further comprises 0.1 to 1 part of processing aids.

[0035] More preferably, the processing aid includes at least one of antioxidants, antistatic agents, antibacterial agents, and UV stabilizers.

[0036] Those skilled in the art can add various functional additives as needed, without affecting the homogeneity and stability of the PPS-based chlorine-containing standard material described in this invention. For example, in order to prevent the product from being affected by static electricity during transportation and storage, those skilled in the art can add antistatic agents to the product; in order to reduce the oxidation probability of the product during processing, those skilled in the art can add antioxidants to the product.

[0037] Another object of the present invention is to provide a method for preparing the PPS-based chlorine-containing standard substance, comprising the following steps: The components are added to a screw extruder for melt extrusion and granulation to obtain the PPS-based chlorine-containing standard substance.

[0038] Preferably, the temperature range of the screw extruder is set to 180~320℃, the screw speed is 300~500rpm, and the screw length-to-diameter ratio is (20~40):1.

[0039] The preparation method of the PPS-based chlorine-containing standard substance described in this invention has simple operation steps and can be industrialized on a large scale.

[0040] Preferably, when preparing the PPS-based chlorine-containing standard substance, the components are compounded in the following weight parts: 90-100 parts of PPS resin, 0.1-10 parts of bis(hexachlorocyclopentadiene)cyclooctane or its derivatives, 0.5-1 parts of dispersant, and 0.5-3 parts of compatibilizer.

[0041] More preferably, in the components of the PPS-based chlorine-containing standard material, bis(hexachlorocyclopentadiene)cyclooctane or its derivatives are added in the form of masterbatch when fed into the screw extruder.

[0042] More preferably, the bis(hexachlorocyclopentadiene)cyclooctane or its derivative is mixed with a portion of PPS resin and a dispersant and melt-extruded to prepare a masterbatch.

[0043] Another object of the present invention is to provide the application of the PPS-based chlorine-containing standard material in the detection of solid chlorine content and in the evaluation and calibration of equipment for testing the chlorine content of samples.

[0044] Another object of the present invention is to provide the application of the PPS-based chlorine-containing standard material in the rapid XRF quantification of chlorine content in PPS-based materials.

[0045] The PPS-based chlorine-containing standard material described in this invention exhibits high stability and uniformity. Based on the controllability of positive substances, it has a wide range of chlorine element detection intervals. In addition to being used as a conventional solid chlorine element standard material, it can be specifically used as a standard material for XRF testing of chlorine content in PPS-based materials. It overcomes the interference phenomenon of sulfur element in PPS resin and can be applied to baseline calibration and standard curve establishment. It has high adaptability to various application scenarios and its overall performance is superior to existing products.

[0046] The beneficial effects of this invention are that it provides a PPS-based chlorine-containing standard material. This product uses bis(hexachlorocyclopentadiene)cyclooctane or its derivatives as the chlorine-containing component in PPS resin and introduces a specific dispersant for compounding. When used as a standard material, its chlorine content calibration can achieve the uniformity and stability required by the standard. It is suitable for calibration and effective quantitative analysis of chlorine content in PPS products during XRF testing. It can also be used as a solid standard material in various common applications of chlorine quantitative testing and analysis and instrument calibration. Attached Figure Description

[0047] Figure 1 The standard curves were constructed using the PPS-based chlorine-containing standard substances obtained in Experiments 1-5. Detailed Implementation

[0048] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments and comparative examples. The purpose of this description is to provide a detailed understanding of the invention, not to limit its scope. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this invention. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this invention are commonly used reagents and instruments.

[0049] Examples 1-11 An embodiment of the PPS-based chlorine-containing standard substance and its preparation method described in this invention is shown in Table 1.

[0050] The preparation method of the PPS-based chlorine-containing standard substance includes the following steps: The components are mixed evenly, then melt-extruded and granulated in a screw extruder, and then injection molded and pressed at 280°C for 30 seconds to form a sheet, thus obtaining the 3mm thick sheet of PPS-based chlorine-containing standard material.

[0051] The temperature zones of the screw extruder are set as follows: Zone 1 185℃, Zone 2 190℃, Zone 3 200℃, Zone 4 260℃, Zone 5 280℃, Zone 6 300℃, Zone 7 300℃, Zone 8 320℃, and Zone 9 320℃. The screw speed is 400 rpm, and the screw length-to-diameter ratio is 30:1.

[0052] Comparative Examples 1-6 The only difference between each comparative example and the embodiment is the type and ratio of components, as shown in Table 2.

[0053] In the components described in each embodiment and comparative example, The PPS resin 1 is J200 produced by HDC Polymer Co., Ltd. of South Korea, with a mercapto content of 853 mg / kg; The PPS resin 2 is PPS 3418 HA produced by Zhejiang Xinhecheng, with a thiol content of 1050 mg / kg; The PPS resin 3 is PPS 3418 produced by Zhejiang Xinhecheng, with a thiol content of 2200 mg / kg; The PPS resin 4 is X200 produced by HDC Polymer Co., Ltd. of South Korea, with a mercapto content of 502 mg / kg; The bis(hexachlorocyclopentadiene)cyclooctane 1 is added in the form of a masterbatch, which contains 5% by mass of bis(hexachlorocyclopentadiene)cyclooctane, with the remainder being 94.5% PPS resin 1 and 0.5% dispersant 1. The bis(hexachlorocyclopentadiene)cyclooctane derivative 2, dodecachlorooctahydro-methylene-cyclobutadiene, is added in the form of a masterbatch containing 5% by mass of bis(hexachlorocyclopentadiene)cyclooctane, with the remainder being 94.5% PPS resin 1 and 0.5% dispersant 1. The bis(hexachlorocyclopentadiene)cyclooctane 3 has a chlorine content of 65.08 wt%; it is added directly by mixing with the components and is not introduced in the form of masterbatch.

[0054] The chlorine-containing substance 1 is sodium chloride produced by Guangzhou Chemical Reagent Factory; it is added in the form of masterbatch, which contains 5% sodium chloride by mass, and the remainder is 94.5% PPS resin 1 and 0.5% dispersant 1. The chlorine-containing substance 2 is CPE-132C produced by Hangzhou Keli Chemical Co., Ltd., with a chlorine content of 32wt%. It is added in the form of masterbatch, which contains 10% by mass of chlorinated polyethylene, and the remainder is 89.5% PPS resin 1 and 0.5% dispersant 1. The dispersant 1 is Honeywell's A-C6A oxidized polyethylene wax; The dispersant 2 is Honeywell AC-617A, an oxidized polyethylene wax; The dispersant 3 is GT-300 silicone masterbatch produced by Zhejiang Jiahua, a polysiloxane masterbatch with a silicone content of 50% by mass. The dispersant 4 is PETS produced by Lonza in the United States, pentaerythritol stearic acid; The dispersant 5 is EBS, ethylene bis-stearamide, produced by Shandong Xuchen Chemical Technology Co., Ltd. The compatibilizer 1 is PE-G-MAH G-6 produced by Nanjing Sutai, which is maleic anhydride grafted polyethylene with a grafting rate of 1.18%.

[0055] The compatibilizer 2 is GR209 produced by Dow Chemical in the United States, which is maleic anhydride grafted polyethylene with a grafting rate of 1.2%.

[0056] The compatibilizer 3 is Orevac 18302N produced by Arkema, France, which is maleic anhydride grafted polyethylene with a grafting rate of 0.5%.

[0057] The compatibilizer 4 is MH5020 produced by Mitsui Chemicals, which is maleic anhydride grafted with POE at a grafting rate of 2.0%.

[0058] The compatibilizer 5 is FH1012 produced by Ningbo Nengzhiguang New Material Technology Co., Ltd., which is maleic anhydride grafted polypropylene with a grafting rate of 0.95%.

[0059] The antioxidant is a mixture of commercially available hindered phenolic antioxidants and commercially available phosphite antioxidants: antioxidant 1010 and antioxidant 168 are compounded in a mass ratio of 1:1.

[0060] Unless otherwise specified, all components and raw materials used in the embodiments and comparative examples of this invention are commercially available, and the same type of components and raw materials are used in each parallel experiment.

[0061] Table 1 Note: The weight parts of bis(hexachlorocyclopentadiene)cyclooctane or its derivatives in Table 1 are their respective effective parts. For example, bis(hexachlorocyclopentadiene)cyclooctane 1 in Example 1 was added in the form of masterbatch. The actual number of parts of masterbatch added was 1.5 parts. The mass content of bis(hexachlorocyclopentadiene)cyclooctane in the masterbatch was 5%, so its effective part was 0.075 parts, which is as recorded in Example 1 of Table 1.

[0062] Table 2 Note: The weight percentages of chlorine-containing substances in Table 2 are their respective effective percentages, which are the same as in Table 1, and will not be repeated here.

[0063] To verify the performance of the product described in this invention, the products prepared in each embodiment and comparative example were subjected to the following performance tests, the specific steps of which are as follows: Chlorine content analysis: Chloride ion aqueous solutions of different concentrations were prepared using liquid chlorine standard solution, and a series of concentration standard solutions were tested using ion chromatography to establish a standard curve for chlorine quantification.

[0064] Homogeneity test: Ten samples (one bag per group, 200 tablets per bag) were randomly selected from the packaged standard substances for homogeneity verification. Pretreatment and quantitative analysis were performed according to standard IEC 62321-3-2:2020 "Determination of certain substances in electrical and electronic products - Part 3-2: Combustion-ion chromatography (C-IC) for screening fluorine, chlorine and bromine in polymers and electronic components"; each sample was tested twice. One-way ANOVA (F-test) was used to analyze the test results. If the F-value was less than the specified limit (F... 0.05 (9,10)=3.02), indicating that there were no significant differences within and between samples.

[0065] Stability testing: After storing the standard substance in a sealed incubator at 25°C and 50% relative humidity for 6 months, 10 groups of samples were randomly selected from the standard samples. Pretreatment and quantitative analysis were performed according to standard IEC 62321-3-2:2020 "Determination of certain substances in electrical and electronic products – Part 3-2: Combustion-ion chromatography (C-IC) – Screening for fluorine, chlorine and bromine in polymers and electronic components". Each group of samples was tested twice. The test results were analyzed using the t-test. If the t-value is less than the specified limit (t... 0 .05 (20+20-2)=2.024), proving that the standard substance did not undergo significant changes.

[0066] The test results are shown in Tables 3 and 4. Table 3 Table 4 As can be seen from the table, the PPS-based chlorine-containing standard material of the present invention can effectively achieve the uniformity standard of chlorine content in the case of PPS-based resin matrix solid, and can effectively replace existing liquid chlorine standard solution or other types of standard materials, with good convenience.

[0067] Furthermore, following the preparation method of the product obtained in Example 1, PPS-based chlorine-containing standard substances with gradient chlorine content were prepared according to the component ratios in Table 5. The component composition of each product is shown in Table 5.

[0068] Table 5 A standard curve was established using the XRF test results of each test case product as the theoretical value, such as... Figure 1 As shown, this standard curve was then used to test the chlorine content of three commercially available PPS resins. Simultaneously, a commercially available PE-based solid chlorine-containing standard substance was used as a standard sample to construct the same standard curve, and the same sample tests were performed. PPS-A, manufactured by Zhejiang Xinhecheng, is a PPS 1350C product. PPS-B, manufactured by Zhejiang Xinhecheng (PPS 20030C); PPS-C, manufactured by Zhejiang Xinhecheng (PPS 11100C); Meanwhile, the chlorine content of these three test samples was detected using an ion chromatograph, and the results were used for comparison. The results are shown in Table 6.

[0069] Table 6 It can be seen that the standard curve constructed by the existing PE-based solid standard material cannot effectively eliminate the influence of sulfur in the PPS sample on the chlorine test results, and the test results are much higher than the actual results. However, the standard curve constructed using the test example product as the standard material for XRF testing has good consistency with the product test results using ion chromatography (error not exceeding 10%, referring to the relative error standard of bromine content in polymers in GB / T 39560.301-2020, this comparison result meets the relative accuracy requirement), indicating that the standard material can be effectively used in XRF testing methods.

[0070] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A PPS-based chlorine-containing reference material, characterized in that, It includes bis(hexachlorocyclopentadiene)cyclooctane or its derivatives, and also includes the following components in parts by weight: 90-100 parts PPS resin, 0.5-1 part dispersant, and 0.5-3 parts compatibilizer; The chlorine content in the PPS-based chlorine-containing standard material is 40~3000 mg / kg; The thiol content of the PPS resin is 600~1500 mg / kg; The dispersant includes at least one of polyethylene wax and organosilicone.

2. The PPS-based chlorine-containing standard substance as described in claim 1, characterized in that, The PPS resin has a melt index of 400 to 800 cm 3 / 10 min.

3. The PPS-based chlorine-containing standard substance as described in claim 1, characterized in that, The polyethylene wax is an oxidized polyethylene wax having a density of 0.9 to 1.3 g / cm 3 .

4. The PPS-based chlorine-containing standard substance as described in claim 1, characterized in that, The compatibilizer includes maleic anhydride grafts, which include at least one of maleic anhydride-grafted polyolefins and maleic anhydride-grafted elastomers.

5. The PPS-based chlorine-containing standard substance as described in claim 4, characterized in that, The maleic anhydride graft includes at least one of maleic anhydride-grafted polypropylene, maleic anhydride-grafted polyethylene, maleic anhydride-grafted SEBS, maleic anhydride-grafted EPDM, and maleic anhydride-grafted POE; preferably, the grafting rate of the maleic anhydride graft is 0.5% to 2%.

6. The PPS-based chlorine-containing standard substance as described in claim 4, characterized in that, The PPS-based chlorine-containing standard material contains 0.01 to 1 part by weight of bis(hexachlorocyclopentadiene)cyclooctane or its derivatives.

7. The PPS-based chlorine-containing standard substance as described in claim 1, characterized in that, The PPS-based chlorine-containing standard substance also includes 0.1 to 1 part of processing aids, which include at least one of antioxidants, antistatic agents, antibacterial agents, and UV stabilizers.

8. The method for preparing the PPS-based chlorine-containing standard substance according to any one of claims 1 to 7, characterized in that, Includes the following steps: The components are added to a screw extruder for melt extrusion and granulation to obtain the PPS-based chlorine-containing standard substance.

9. The application of the PPS-based chlorine-containing standard material as described in any one of claims 1 to 7 in the detection of solid chlorine content and the evaluation and calibration of equipment for testing the chlorine content of samples.

10. The application of the PPS-based chlorine-containing standard material as described in any one of claims 1 to 7 in the rapid quantitative determination of chlorine content in PPS-based materials using XRF.

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