A method for separating resin components in complex PPE alloy systems and its applications.

Abstract

This invention discloses a method for separating resin components in a complex PPE alloy system. The method includes the following steps: S1, qualitative analysis of the resin components in the complex PPE alloy system is performed using testing methods to identify the resin components contained in the complex PPE alloy system; the complex PPE alloy system includes PPE resin, and at least one resin selected from PP, SEBS, and PS; S2, a first good solvent is mixed and dissolved with the complex PPE alloy to obtain a solution; S3, based on the qualitative analysis results of step S1, the corresponding resin components in the complex PPE alloy system are sequentially separated and precipitated using a continuous solvent method with the solution from step S2. This method can effectively separate different resin components in a complex PPE alloy system, thereby achieving qualitative and quantitative analysis of multiple resin components, and the resin components have a high recovery rate.

Description

Technical Field

[0001] This invention belongs to the technical field of detection technology, and more specifically, relates to a method for separating resin components in a complex PPE alloy system and its application. Background Technology

[0002] Polyphenylene ether (PPE), chemically known as poly(2,6-dimethyl-1,4-phenylene ether), is a high-strength engineering plastic developed in the 1960s. It possesses excellent physical and mechanical properties, heat resistance, and insulation. However, due to its poor flowability, it is typically blended with other plastics to form engineering plastic alloys, which are currently the most typical and widely used engineering plastic alloys.

[0003] Common complex modified polyphenylene ether (PP) alloy materials include PS-modified PP alloy materials, SEBS-modified PP alloy materials, PP-modified PP alloy materials, or three-phase or four-phase alloy materials formed by any of the above resins. Due to their low density, good dimensional stability, excellent insulation, good heat resistance, low dielectric constant, and high heat distortion temperature, complex modified PP alloy materials are widely used in structural components (such as fans in computers) in the electronics and electrical industries.

[0004] Currently, there are few reports on methods for separating and quantitatively analyzing resin components in complex modified polyphenylene ether alloy systems. Traditional methods include infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and solvent separation. Infrared spectroscopy provides qualitative analysis based on the proportion of different wavenumbers, but accurate qualitative analysis is challenging when multiple components interfere with each other, making quantitative analysis difficult. Proton nuclear magnetic resonance spectroscopy analyzes based on characteristic chemical shifts, but requires resolution when the components are relatively defined. Solvent separation utilizes the differences in solubility of different components in the same solvent; however, it cannot completely separate the various resin components in complex modified polyphenylene ether three-phase or four-phase alloys based on various resin components (such as PS, SEBS, or PP). The separated precipitate still contains a mixture of resin components, making further quantitative analysis impossible. The reason solvent separation cannot achieve this is that the solubility parameters of different resin components in the same solvent are similar, and their molecular weight distributions overlap, making accurate quantitative analysis impossible.

[0005] Patent CN104744686A discloses a method for precipitating polyphenylene ether (PPE) from a PPE solution. This method involves continuously passing water vapor into a mixture of PPE solution and water to remove the solvent, causing the PPE to precipitate in the water. While this method utilizes a solvent, it is suitable for PPE synthesis but not for the quantitative analysis of resin components in complex PPE alloy systems used in the electronics and electrical industries. Furthermore, this method does not address how to separate different resin components within complex PPE alloy systems. Patent CN101423604B discloses a method for filtering PPE precipitates within a PPE solvent recovery system. This method uses a tubular filter to remove the solvent mixture after the initial PPE precipitation separation, along with a mixture of poorly washed solvents. The PPE particles and precipitates remain on the filter cloth surface. This method focuses on recovering PPE but does not address the separation or qualitative / quantitative analysis of other resin components within the PPE system. Summary of the Invention

[0006] To address the aforementioned technical problems, the primary objective of this invention is to provide a method for separating resin components in complex PPE alloy systems. This method effectively separates different resin components within a complex PPE alloy system, enabling qualitative and quantitative analysis of multiple resin components, and achieving a high recovery rate for the resin components.

[0007] The second objective of this invention is to provide a method for separating resin components in a complex PPE alloy system, which can be used for the quantitative and qualitative analysis of different resin components in the complex PPE alloy system.

[0008] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0009] A method for separating resin components in a complex PPE alloy system, comprising the following steps:

[0010] S1. Qualitative analysis of the resin components in the complex PPE alloy system is performed using testing methods to identify the resin components contained in the complex PPE alloy system; the complex PPE alloy system includes PPE resin, and at least one resin selected from PP, SEBS, and PS.

[0011] S2. Mix and dissolve the first good solvent and the complex PPE alloy to obtain a solution;

[0012] S3. Based on the qualitative analysis results of step S1, the solution obtained in step S2 is subjected to at least two of the following steps to separate and precipitate the corresponding resin components in the complex PPE alloy system:

[0013] (1) The solution and the second good solvent are mixed to precipitate the PP component in the complex PPE alloy system. The mixture is filtered to obtain the PP component precipitate and the first filtrate.

[0014] (2) The first filtrate and the third good solvent are mixed to precipitate the PPE component and / or SEBS component in the complex PPE alloy system. The mixture is filtered to obtain the PPE component precipitate and / or SEBS component precipitate, as well as the second filtrate.

[0015] (3) The second filtrate and the fourth good solvent are mixed to precipitate the PS component in the complex PPE alloy system. The mixture is then filtered to obtain the PS component precipitate and the third filtrate.

[0016] This invention first employs testing methods (such as infrared spectroscopy and / or differential scanning calorimetry) to qualitatively analyze the resin components in a complex PPE alloy system, thereby identifying which resin components are present in the complex PPE alloy system. Based on this qualitative analysis result, in the subsequent step S3, the precipitation and separation of different resin components, a suitable good solvent is selected to separate and precipitate the resin components contained in the complex PPE alloy system.

[0017] Furthermore, the applicant's research revealed that for complex PPE alloy systems and their different resin components, it is necessary to dissolve and extract the different resin components in a specific order to effectively and completely separate them. Failure to follow this specific order results in incomplete separation (or residue) of the resin components.

[0018] This invention utilizes the property differences between different resins and employs a continuous solvent method to sequentially separate different resin components in a complex PPE alloy system. This method enables accurate and effective separation and quantitative analysis of each resin component in the complex alloy system, with high resin component recovery rates. Furthermore, this invention uses relatively few chemical reagents, has simple testing procedures, and offers advantages such as low carbon footprint and environmental friendliness.

[0019] In this invention, the first, second, third, and fourth good solvents refer to solvents in which the corresponding resin components (e.g., the second good solvent corresponds to the PP resin component, and the fourth good solvent corresponds to the PS resin component) have good solubility. More specifically, in each of the above-mentioned good solvents, the solubility of the corresponding resin component is ≥0.5 g / L, ≥1 g / L, ≥2 g / L, ≥3 g / L, ≥4 g / L, ≥5 g / L, ≥6 g / L, ≥7 g / L, ≥8 g / L, ≥9 g / L, ≥10 g / L, ≥15 g / L, ≥20 g / L, ≥30 g / L, ≥40 g / L, ≥50 g / L, ≥60 g / L, ≥70 g / L, ≥80 g / L, ≥90 g / L, or ≥100 g / L. The first, second, third, and fourth good solvents can be selected from solvents already disclosed in the art that have good solubility for each resin component (PP, PPE, SEBS, PS).

[0020] In some embodiments, in step S2, the first good solvent and the complex PPE alloy can be mixed and then heated to dissolve them, and the heating temperature is 120-260°C.

[0021] In some embodiments, the first good solvent is selected from one or more of toluene, xylene, trichlorobenzene, and limonene.

[0022] In some embodiments, the second good solvent is selected from one or more of dichloromethane, chloroform, and 1,2-tetrachloroethane.

[0023] In some embodiments, the third good solvent is selected from one or more of acetone, tetrahydrofuran, and N-methylpyrrolidone.

[0024] In some embodiments, the fourth good solvent is selected from one or more of methanol, ethanol, and isopropanol.

[0025] In some embodiments, in step (2), the first filtrate is concentrated and then a third good solvent is added; and / or in step (3), the second filtrate is concentrated and then a fourth good solvent is added.

[0026] This invention increases the concentration of the resin components to be separated in the filtrate through concentration, which can effectively improve the separation degree of the resin components in subsequent separation steps and obtain resin component precipitates with higher content.

[0027] In some implementations, the first and second filtrates can be concentrated to 1 / 3 to 3 / 4 of their original volume.

[0028] In some implementations, complex PPE alloy materials undergo shearing during polymer processing, resulting in the breakage of some molecular chains and the formation of oligomers. When complex PPE alloy systems contain oligomers, the third filtrate and the fifth good solvent can be mixed to allow the oligomer groups in the complex PPE alloy system to be extracted.

[0029] Preferably, the fifth good solvent is selected from one or more of diethyl ether, petroleum ether, n-hexane, and ethyl acetate.

[0030] In some implementation schemes, qualitative analysis is performed on the PP component precipitation, PPE component precipitation and / or SEBS component precipitation, and PS component precipitation using test methods to determine whether they are still complex components; precipitates that are still complex components are dissolved using deuterated reagents, and the complex components are qualitatively and quantitatively analyzed using 1H NMR spectroscopy.

[0031] In addition, qualitative and quantitative analysis of molecular weight differences and characteristic carbon chemical shift differences of complex components can also be performed by gel permeation chromatography / carbon nuclear magnetic resonance spectroscopy.

[0032] Specifically, the aforementioned complex component refers to a component formed from at least two resins selected from PP, PPE, SEBS, and PS. More specifically, in the complex component, the content of the less abundant resin component is >2%.

[0033] In some embodiments, the deuterated reagent may be a deuterated reagent conventionally used in the art, including but not limited to deuterated chloroform, deuterated dichloromethane, etc.

[0034] Furthermore, this invention claims protection for the use of a method for separating resin components in a complex PPE alloy system in the qualitative and quantitative analysis of different resin components in the complex PPE alloy system.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] This invention utilizes the property differences between different resins and employs a continuous solvent method to sequentially separate different resin components in a complex PPE alloy system. This method enables accurate and effective separation and quantitative analysis of each resin component in the complex alloy system, with high resin component recovery rates. Furthermore, this invention uses relatively few chemical reagents, has simple testing procedures, and offers advantages such as low carbon footprint and environmental friendliness. Attached Figure Description

[0037] Figure 1 The image shows the infrared spectrum of the modified polyphenylene ether alloy material-1 in Example 1.

[0038] Figure 2 The image shows the DSC diagram of the modified polyphenylene ether alloy material-1 in Example 1.

[0039] Figure 3 The image shows the infrared spectrum of the PP component precipitate in Example 1.

[0040] Figure 4 The image shows the infrared spectrum of the PPE and SEBS components precipitated in Example 1.

[0041] Figure 5 The image shows the infrared spectrum of the PS component precipitate in Example 1.

[0042] Figure 6 The image shows the 1H NMR spectrum of the PPE and SEBS components precipitated in Example 1.

[0043] Figure 7 The image shows the infrared spectrum of the modified polyphenylene ether alloy material-2 in Example 2.

[0044] Figure 8 The image shows the infrared spectrum of the PPE component precipitate in Example 2.

[0045] Figure 9 The image shows the infrared spectrum of the modified polyphenylene ether alloy material-3 in Example 3.

[0046] Figure 10 The image shows the infrared spectrum of the modified polyphenylene ether alloy material-4 in Example 4.

[0047] Figure 11 The image shows the infrared spectrum of the first precipitate in Comparative Example 1.

[0048] Figure 12 The image shows the infrared spectrum of the first precipitate in Comparative Example 2. Detailed Implementation

[0049] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0050] The testing methods and conditions used in this invention are as follows:

[0051] Infrared spectroscopy: The temperature is raised to 260°C using a hot-pressing mold and heating device. The sample is placed in the middle of the polytetrafluoroethylene (PTFE) film as a carrier. The sample is heated and melted at the melting temperature and then pressed into a thin film. Infrared spectroscopy is performed using the transmission mode of an infrared spectrometer. The composition of the sample is qualitatively analyzed based on the obtained infrared spectrum.

[0052] Differential scanning calorimetry (DSC): Nitrogen was used as both the purge and protective gas at a flow rate of 50 mL / min. Before starting the heating process, the system was pre-cleaned with nitrogen for 5 min. The temperature was increased from 40 °C to 300 °C at a rate of 20 °C / min and held for 5 min. The temperature was then decreased from 300 °C to 40 °C at a rate of 20 °C / min and held for 5 min. A second heating was performed, increasing the temperature from 40 °C to 300 °C at a rate of 20 °C / min. The results from the second heating curve were used. Qualitative analysis of the components, including glass transition temperature, melting temperature, and crystallization temperature, was performed using data processing software on the tested DSC curves.

[0053] 1H NMR spectroscopy: The sample is dissolved in deuterated chloroform to form a homogeneous solution, and then the 1H NMR spectrum is scanned using an NMR spectrometer to obtain the sample's 1H NMR spectrum. The obtained spectrum is then analyzed using NMR processing software, and qualitative and quantitative analysis is performed based on the characteristic chemical shifts of different components.

[0054] The raw material information used in this invention is as follows:

[0055] Modified polyphenylene ether alloy material-1, by weight percentage, comprises: PPE 47wt%, PP 33wt%, PS 14wt%, SEBS 6wt%, and its preparation method is as follows:

[0056] (1) Weigh each component according to the above weight percentage and mix them evenly;

[0057] (2) The mixture obtained in step (1) is melt-extruded and granulated using a twin-screw extruder at a processing temperature of 280℃ to prepare modified polyphenylene ether alloy material-1. The granulation process parameters are as follows: the feed rate is controlled at 450kg / h, and the temperature of each zone is controlled as follows: zone 1 temperature 140±10℃, zone 2 temperature 280±10℃, zone 3 temperature 280±10℃, zone 4 temperature 280±10℃, zone 5 temperature 280±10℃, zone 6 temperature 280±10℃, zone 7 temperature 280±10℃, zone 8 temperature 280±10℃, and zone 9 temperature 280±10℃.

[0058] Modified polyphenylene ether alloy material-2, by weight percentage, comprises: 50 wt% PPE and 50 wt% PS. The preparation method of modified polyphenylene ether alloy material-2 is the same as that of modified polyphenylene ether alloy material-1.

[0059] Modified polyphenylene ether alloy material-3, by weight percentage, comprises: 40 wt% PPE, 40 wt% PP, and 20 wt% PS. The preparation method of modified polyphenylene ether alloy material-3 is the same as that of modified polyphenylene ether alloy material-1.

[0060] Modified polyphenylene ether alloy material-4, by weight percentage, comprises: 50 wt% PPE and 50 wt% PP. The preparation method of modified polyphenylene ether alloy material-4 is the same as that of modified polyphenylene ether alloy material-1.

[0061] Example 1

[0062] (1) The infrared spectrum of the modified polyphenylene ether alloy material-1 sample was tested by infrared spectroscopy; the DSC of the modified polyphenylene ether alloy material-1 sample was tested by differential scanning calorimetry (DSC) to obtain the DSC pattern and analysis results.

[0063] Figure 1 The image shows the infrared spectrum of the modified polyphenylene ether alloy material-1 in Example 1. Figure 2 This is the DSC chart of the modified polyphenylene ether alloy material-1 in Example 1. (From...) Figure 1 It can be seen that the modified polyphenylene ether alloy material-1 contains resin components PP, PPE, SEBS and PS.

[0064] (2) Add the sample modified polyphenylene ether alloy material-1 to toluene, heat to 140℃ and reflux until completely dissolved to obtain a solution;

[0065] (3) Dichloromethane was added to the solution to precipitate the PP component. The PP component was filtered under reduced pressure to obtain the PP component precipitate and the first filtrate. The PP component precipitate was dried and weighed using an electronic analytical balance (recovery rate 94.6%).

[0066] (4) The first filtrate is concentrated to 1 / 2 of the total volume, and then acetone is added to precipitate the PPE and SEBS components. The PPE and SEBS components are filtered under reduced pressure to obtain the precipitate of PPE and SEBS components and the second filtrate. The PPE and SEBS components are dried and weighed using an electronic analytical balance.

[0067] (5) The third filtrate is concentrated to 1 / 2 of the total volume, and methanol is added to precipitate the PS component. The PS component is filtered under reduced pressure to obtain the PS component precipitate and the fourth filtrate. The PS component precipitate is dried and weighed using an electronic analytical balance (recovery rate 93.5%).

[0068] (6) The component precipitates after drying in steps (3), (4), and (5) were qualitatively analyzed using infrared spectroscopy and differential scanning calorimetry.

[0069] Figure 3 The image shows the infrared spectrum of the PP component precipitate in Example 1. Figure 4 The image shows the infrared spectrum of the PPE and SEBS components precipitated in Example 1. Figure 5The image shows the infrared spectrum of the PS component precipitate in Example 1.

[0070] Depend on Figure 3 It can be seen that, Figure 3 Infrared spectral characteristic absorption wavenumbers of PP: at 2920 cm⁻¹ -1 2850cm -1 Stretching vibrations attributed to methyl and methylene groups, 1475 (1460) cm -1 1377cm -1 Attributable to the C-H deformation vibration and methyl bending vibration in the methylene group, l160 cm -1 970cm -1 The characteristic peak of [CH2CH(CH3)]n and 841 cm⁻¹ -1 The absorption peak is attributed to the isotactic crystalline state.

[0071] according to Figure 3 The characteristic absorption peaks in the infrared spectrum show that there are no absorption signals of PPE, PS, or SEBS in the PP component precipitate. Combined with the melting temperature of the DSC, it can be proved that the purity of the sample is above 98%.

[0072] Depend on Figure 4 It can be seen that, Figure 4 Characteristic absorption wavenumbers of infrared spectra containing PPE and SEBS: 2800–3200 cm⁻¹ -1 The absorption peaks between these values ​​are all absorption peaks of the stretching vibration of the C-H bond in PPE and SEBS, while those between 1300 and 1700 cm⁻¹ are absorption peaks of the stretching vibration of the C-H bond in PPE and SEBS. -1 The absorption peak between these two points is the rocking vibration absorption peak of the C-H bond in PPE (1600 cm⁻¹). -1 1605cm -1 1471cm -1 1452cm -1 1 305cm -1 The absorption peak of the rocking vibration of the benzene ring skeleton in SEBS (1493 cm⁻¹) -1 PPE and SEBS at 1350 cm -1 ~3200cm -1 The absorption peaks overlap significantly within the wavenumber range, with the absorption peak at 1190 cm⁻¹. -1 The vibrational absorption peak of the COC bond in PPE at this location is observed. Furthermore, SEBS is present at 1150 cm⁻¹. -1 The nearby peaks are due to CH bending vibrations. Based on the above analysis, it can be inferred that PPE and SEBS precipitate simultaneously after the addition of acetone.

[0073] according to Figure 4The characteristic absorption peaks in the infrared spectrum show that the PPE and SEBS components are precipitated as a two-component system with no other resin components. Further quantitative analysis using 1H NMR spectroscopy is required.

[0074] Depend on Figure 5 It can be seen that, Figure 5 Infrared spectral characteristic absorption wavenumber containing PS: 3100 cm⁻¹ -1 -3000cm -1 Peaks within this range indicate CH tensile vibrations on the base ring; 3050 cm⁻¹ -1 The nearby peak is the stretching vibration of the adjacent C-H bond on the benzene ring, 2920 cm⁻¹. -1 -2850cm -1 The peaks within the range represent symmetrical stretching of 4.1600 cm^2. -1 The nearby peak is due to the C=C vibration of the benzene ring, 1500 cm⁻¹. -1 -1480cm- 1 The peaks within this range represent symmetrical deformation vibrations of the benzene ring. (1150 cm⁻¹) -1 The peaks that appear nearby are due to the CH bending vibration.

[0075] according to Figure 5 The characteristic absorption peaks in the infrared spectrum show that there are no characteristic absorption signals of PPE, SEBS, and PP, proving that the purity of the sample is above 98%.

[0076] Based on the results of step (5), the next step is to use deuterated chloroform as a solvent to dissolve the PPE and SEBS components precipitate, and to perform a proton NMR spectroscopy scan and integrate the area to analyze the proton NMR spectrum (e.g., ...). Figure 6 Quantitative analysis (as in formula (1)) was performed to determine the content of PPE and SEBS components.

[0077] (1)N PPE / N SEBS =S 2.08 / (S 0.81 *2)=6 / (0.38*2)=7.89

[0078] According to the three-step precipitation method, the proportions of PP and PS are 32.5% and 13.8%, respectively, and the remaining proportions of PPE and SEBS are 1 - 39.8% - 13.8% = 46.7%. Based on the total mass fraction of PPE and SEBS precipitation of 46.7%, the proportion of SEBS can be calculated to be 6.04%, which is close to the theoretical value of 6%.

[0079] In addition, the PPE and SEBS component precipitates generated in step (4) above can be separated by conventional gel permeation chromatography or solvent separation methods in the art.

[0080] Example 2

[0081] (1) The infrared spectrum of the modified polyphenylene ether alloy material-2 sample was obtained by infrared spectroscopy.

[0082] Figure 7 The image shows the infrared spectrum of the modified polyphenylene ether alloy material-2 in Example 2. Figure 7 It can be seen that the modified polyphenylene ether alloy material-2 contains PPE and PS.

[0083] (2) Add the sample modified polyphenylene ether alloy material-2 to toluene and heat under reflux until it is completely dissolved to obtain a solution;

[0084] (3) Add acetone to the solution to precipitate the PPE component. Filter under reduced pressure to obtain the PPE component precipitate and the first filtrate. Dry the PPE component precipitate and weigh it (recovery rate 95.1%).

[0085] (4) The first filtrate was concentrated to 1 / 2 of the total volume, and then methanol was added to precipitate the PS component. The PS component was filtered under reduced pressure, dried, and weighed (recovery rate 93.8%).

[0086] The precipitates dried in steps (3) and (4) were qualitatively analyzed using infrared spectroscopy and differential scanning calorimetry.

[0087] Figure 8 The image shows the infrared spectrum of the PPE component precipitate in Example 2.

[0088] Depend on Figure 8 It can be seen that, Figure 8 Characteristic absorption wavenumbers of infrared spectra containing PPE: 2800–3200 cm⁻¹ -1 The absorption peaks between these values ​​are all absorption peaks of the stretching vibration of the C-H bond in PPE, while those between 1300 and 1700 cm⁻¹ are absorption peaks of the stretching vibration of the C-H bond in PPE. -1 The absorption peak between these two points is the rocking vibration absorption peak of the C-H bond in PPE (1600 cm⁻¹). -1 1605cm -1 1471cm -1 1452cm -1 1 305cm -1 ) and absorption peak at 1190 cm⁻¹ -1 The vibrational absorption peak of the COC bond in PPE at that location.

[0089] according to Figure 8 The characteristic absorption peaks in the infrared spectrum show that there is no characteristic absorption signal of PS, which proves that the purity of the sample is above 98%.

[0090] The infrared spectrum of the PS component precipitate in Example 2 is basically as follows: Figure 5 As shown, its infrared characteristic absorption wavenumber including PS is 3100 cm⁻¹. -1 -3000cm -1 Peaks within this range indicate CH tensile vibrations on the base ring; 3050 cm⁻¹ -1 The nearby peak is the stretching vibration of the adjacent C-H bond on the benzene ring, 2920 cm⁻¹. -1 -2850cm -1 The peaks within the range represent symmetrical stretching of 4.1600 cm^2. -1 The nearby peak is due to the C=C vibration of the benzene ring, 1500 cm⁻¹. -1 -1480cm- 1 The peaks within this range represent symmetrical deformation vibrations of the benzene ring. (1150 cm⁻¹) -1 The peaks that appear nearby are due to the CH bending vibration.

[0091] The data above shows that there is no characteristic absorption signal of PPE in the PS component precipitate, proving that the purity of the sample is above 98%.

[0092] Example 3

[0093] (1) The infrared spectrum of the modified polyphenylene ether alloy material-3 sample was obtained by infrared spectroscopy.

[0094] Figure 9 The image shows the infrared spectrum of the modified polyphenylene ether alloy material-3 in Example 3. Figure 9 It can be seen that the modified polyphenylene ether alloy material-3 contains PP, PPE and PS.

[0095] (2) Add the sample modified polyphenylene ether alloy material-3 to xylene and heat under reflux until completely dissolved to obtain a solution;

[0096] (3) Dichloromethane was added to the solution to precipitate the PP component. The solution was filtered under reduced pressure to obtain the PP component precipitate and the first filtrate. The PP component precipitate was dried and weighed (recovery rate 95.8%).

[0097] (4) The first filtrate is concentrated to 1 / 2 of the total volume, and then acetone is added to cause the PPE component to precipitate. The PPE component is filtered under reduced pressure to obtain the PPE component precipitate and the second filtrate. The PPE component precipitate is dried and weighed (recovery rate 94.5%).

[0098] (5) The second filtrate is concentrated to 1 / 2 of the total volume, and then methanol is added to precipitate the PS component. The PS component is filtered under reduced pressure, dried, and weighed (recovery rate 93.9%).

[0099] The precipitates dried in steps (3), (4), and (5) were qualitatively analyzed using infrared spectroscopy and differential scanning calorimetry.

[0100] The infrared spectrum of the PP component precipitation in Example 3 is basically as follows: Figure 3 As shown, the characteristic absorption wavenumber of the infrared spectrum containing PP is at 2920 cm⁻¹. -1 2850cm -1 Stretching vibrations attributed to methyl and methylene groups, 1475 (1460) cm -1 1377cm -1 Attributable to the C-H deformation vibration and methyl bending vibration in the methylene group, l160 cm -1 970cm -1 The characteristic peak of [CH2CH(CH3)]n and 841 cm⁻¹ -1 The absorption peak is attributed to the isotactic crystalline state.

[0101] The data above shows that there are no absorption signals of PPE or PS in the PP component precipitate. Combined with the melting temperature of the DSC, it can be proved that the purity of the sample is above 98%.

[0102] The infrared spectrum of the PPE component precipitation in Example 3 is basically as follows: Figure 8 As shown, the characteristic absorption wavenumbers of the infrared spectrum containing PPE are: absorption wavenumbers in the range of 2800–3200 cm⁻¹. -1 The absorption peaks between these values ​​are all absorption peaks of the stretching vibration of the C-H bond in PPE, while those between 1300 and 1700 cm⁻¹ are absorption peaks of the stretching vibration of the C-H bond in PPE. -1 The absorption peak between these two points is the rocking vibration absorption peak of the C-H bond in PPE (1600 cm⁻¹). -1 1605cm -1 1471cm -1 1452cm -1 1 305cm -1 ) and absorption peak at 1190 cm⁻¹ -1 The vibrational absorption peak of the COC bond in PPE at that location.

[0103] The data above shows that there are no absorption signals of PP or PS in the PPE component precipitate, which proves that the sample purity is above 98%.

[0104] The infrared spectrum of the PS component precipitate in Example 3 is basically as follows: Figure 5 As shown, the characteristic absorption wavenumber of the infrared spectrum containing PS is 3100 cm⁻¹. -1 -3000cm -1 Peaks within this range indicate CH tensile vibrations on the base ring; 3050 cm⁻¹ -1The nearby peak is the stretching vibration of the adjacent C-H bond on the benzene ring, 2920 cm⁻¹. -1 -2850cm -1 The peaks within the range represent symmetrical stretching of 4.1600 cm^2. -1 The nearby peak is due to the C=C vibration of the benzene ring, 1500 cm⁻¹. -1 -1480cm- 1 The peaks within this range represent symmetrical deformation vibrations of the benzene ring. (1150 cm⁻¹) -1 The peaks that appear nearby are due to the CH bending vibration.

[0105] The data above shows that there are no characteristic absorption signals of PPE and PP in the PS component precipitate, proving that the purity of the sample is above 98%.

[0106] Example 4

[0107] (1) The infrared spectrum of the modified polyphenylene ether alloy material-4 was obtained by infrared spectroscopy.

[0108] Figure 10 The image shows the infrared spectrum of the modified polyphenylene ether alloy material-4 in Example 4. Figure 10 It can be seen that the modified polyphenylene ether alloy material-4 sample contains PP and PPE.

[0109] (2) Add the sample modified polyphenylene ether alloy material-4 to xylene and heat under reflux until completely dissolved to obtain a solution;

[0110] (3) Add chloroform to the solution to precipitate the PP component. Filter under reduced pressure to obtain the PP component precipitate and the first filtrate. Dry the PP component precipitate and weigh it (recovery rate 95.8%).

[0111] (4) The first filtrate was concentrated to 1 / 2 of the total volume, and then acetone was added to cause the PPE component to precipitate. The PPE component was filtered under reduced pressure, dried, and weighed (recovery rate 96.4%).

[0112] The precipitates dried in steps (3) and (4) were qualitatively analyzed using infrared spectroscopy and differential scanning calorimetry.

[0113] The infrared spectrum of the PP component precipitation in Example 4 is basically as follows: Figure 3 As shown, the characteristic absorption wavenumber of the infrared spectrum containing PP is at 2920 cm⁻¹. -1 2850cm -1 Stretching vibrations attributed to methyl and methylene, 1475 (1460) cm -1 1377cm -1 Attributable to the deformation vibration of C—H in the methylene group, the bending vibration of the methyl group, and l160 cm.-1 970cm -1 The characteristic peak of [CH2CH(CH3)]n and 841 cm⁻¹ -1 The absorption peak is attributed to the isotactic crystalline state.

[0114] The data above shows that there is no PPE absorption signal in the PP component precipitate, and combined with the melting temperature of the DSC, it can be proved that the sample purity is above 98%.

[0115] The infrared spectrum of the PPE component precipitation in Example 4 is basically as follows: Figure 8 As shown, the characteristic absorption wavenumbers of the infrared spectrum containing PPE are: absorption wavenumbers in the range of 2800–3200 cm⁻¹. -1 The absorption peaks between these values ​​are all absorption peaks of the stretching vibration of the C-H bond in PPE, while those between 1300 and 1700 cm⁻¹ are absorption peaks of the stretching vibration of the C-H bond in PPE. -1 The absorption peak between these two points is the rocking vibration absorption peak of the C-H bond in PPE (1600 cm⁻¹). -1 1605cm -1 1471cm -1 1452cm -1 1 305cm -1 ) and absorption peak at 1190 cm⁻¹ -1 The vibrational absorption peak of the COC bond in PPE at that location.

[0116] The data above shows that there is no absorption signal of PP in the PPE component precipitate, which proves that the sample purity is above 98%.

[0117] Comparative Example 1

[0118] (1) The modified polyphenylene ether alloy material-1 sample was tested by infrared spectroscopy to obtain the infrared spectrum of the sample; the modified polyphenylene ether alloy material-1 sample was tested by differential scanning calorimetry (DSC) to obtain the DSC pattern and analysis results of the sample;

[0119] (2) Add the sample modified polyphenylene ether alloy material-1 to xylene and heat under reflux until completely dissolved to obtain a solution;

[0120] (3) Add acetone to the solution to cause the precipitate to precipitate, filter under reduced pressure to obtain the first precipitate and the first filtrate, dry the first precipitate and weigh it;

[0121] (4) The first filtrate is concentrated to 1 / 2 of the total volume, and then methanol is added to cause the precipitate to precipitate. The precipitate is filtered under reduced pressure to obtain the second precipitate, which is then dried and weighed.

[0122] The precipitates dried in steps (3) and (4) were qualitatively analyzed using infrared spectroscopy and differential scanning calorimetry.

[0123] Figure 11 The image shows the infrared spectrum of the first precipitate in Comparative Example 1.

[0124] Depend on Figure 11 It can be seen that, Figure 11 Infrared spectral characteristic absorption wavenumbers of PP: at 2920 cm⁻¹ -1 2850cm -1 Stretching vibrations attributed to methyl and methylene groups, 1475 (1460) cm -1 1377cm -1 Attributable to the C-H deformation vibration and methyl bending vibration in the methylene group, l160 cm -1 970cm -1 The characteristic peak of [CH2CH(CH3)]n and 841 cm⁻¹ -1 The absorption peak is attributed to the isotactic crystalline state.

[0125] Figure 11 Characteristic absorption wavenumbers of infrared spectra containing PPE and SEBS: 2800–3200 cm⁻¹ -1 The absorption peaks between these values ​​are all absorption peaks of the stretching vibration of the C-H bond in PPE and SEBS, while those between 1300 and 1700 cm⁻¹ are absorption peaks of the stretching vibration of the C-H bond in PPE and SEBS. -1 The absorption peak between these two points is the rocking vibration absorption peak of the C-H bond in PPE (1600 cm⁻¹). -1 1605cm -1 1471cm -1 1452cm -1 1 305cm -1 The absorption peak of the rocking vibration of the benzene ring skeleton in SEBS (1493 cm⁻¹) -1 PPE and SEBS at 1350 cm -1 ~3200cm -1 The absorption peaks overlap significantly within the wavenumber range, with the absorption peak at 1190 cm⁻¹. -1 The vibrational absorption peak of the COC bond in PPE at this location is observed. Furthermore, SEBS is present at 1150 cm⁻¹. -1 The nearby peaks are due to CH bending vibrations. Based on the above analysis, it can be inferred that both precipitate simultaneously when acetone precipitant is added.

[0126] The presence of characteristic peaks indicates that the first precipitate contains components of PP, PPE, and SEBS. These three components precipitate together in acetone solvent, making effective separation impossible.

[0127] The infrared spectrum of the second precipitate in Comparative Example 1 is basically as follows: Figure 5 As shown in the figure, the absorption wavenumber of the infrared characteristic absorption peak of PS is 3100 cm⁻¹.-1 -3000cm -1 Peaks within this range indicate CH tensile vibrations on the base ring; 3050 cm⁻¹ -1 The nearby peak is the stretching vibration of the adjacent C-H bond on the benzene ring, 2920 cm⁻¹. -1 -2850cm -1 Peaks within the range indicate symmetrical stretching; the peak near 1600 cm⁻¹ represents the C=C vibration of the benzene ring; and the peak at 1500 cm⁻¹ represents the C=C vibration of the benzene ring. -1 -1480cm- 1 The peaks within this range represent symmetrical deformation vibrations of the benzene ring. (1150 cm⁻¹) -1 The peaks that appear nearby are due to the CH bending vibration.

[0128] Comparative Example 2

[0129] (1) The modified polyphenylene ether alloy material-1 sample was tested by infrared spectroscopy to obtain the infrared spectrum of the sample; the modified polyphenylene ether alloy material-1 sample was tested by differential scanning calorimetry (DSC) to obtain the DSC pattern and analysis results of the sample;

[0130] (2) Add the sample modified polyphenylene ether alloy material-1 to xylene and heat under reflux until completely dissolved to obtain a solution;

[0131] (3) Add methanol to the solution to cause precipitation, filter under reduced pressure to obtain the first precipitate and the first filtrate, dry the first precipitate and weigh it;

[0132] The precipitate after drying in step (3) was qualitatively analyzed using infrared spectroscopy and differential scanning calorimetry.

[0133] Figure 12 The image shows the infrared spectrum of the first precipitate in Comparative Example 2.

[0134] Depend on Figure 12 It can be seen that, Figure 12 Infrared spectral characteristic absorption wavenumber of PP: at 2920 cm⁻¹ -1 2850cm -1 Stretching vibrations attributed to methyl and methylene groups, 1475 (1460) cm -1 1377cm -1 Attributable to the C-H deformation vibration and methyl bending vibration in the methylene group, l160 cm -1 970cm -1 The characteristic peak of [CH2CH(CH3)]n and 841 cm⁻¹ -1 The absorption peak is attributed to the isotactic crystalline state.

[0135] Figure 12Characteristic absorption wavenumbers of infrared spectra of PPE, SEBS, and PS: 2800–3200 cm⁻¹ -1 The absorption peaks between these values ​​are all absorption peaks of the stretching vibration of the C-H bonds in PPE, SEBS, and PS, while the absorption peaks between 1300 and 1700 cm⁻¹ are all absorption peaks of the C-H bond stretching vibration in PPE, SEBS, and PS. -1 The absorption peak between these two points is the rocking vibration absorption peak of the C-H bond in PPE (1600 cm⁻¹). -1 1605cm -1 1471cm -1 1452cm -1 1 305cm -1 The absorption peak of the rocking vibration of the benzene ring skeleton in SEBS and PS (1493 cm⁻¹) -1 PPE and SEBS at 1350 cm -1 ~3200cm -1 The absorption peaks overlap significantly within the wavenumber range, with the absorption peak at 1190 cm⁻¹. -1 The vibrational absorption peak of the COC bond in PPE is observed at 1150 cm⁻¹. SEBS and PS are also present at this peak. -1 The nearby peaks are due to CH bending vibrations. Based on the above analysis, it can be inferred that the four components precipitated simultaneously after the methanol solvent was added.

[0136] The foregoing examples are merely illustrative, used to explain some features of the method described in this invention. The appended claims are intended to claim the broadest possible scope, and the embodiments presented herein are demonstrated by the applicant's actual experimental results. Therefore, the applicant intends that the appended claims are not limited by the selection of examples illustrating the features of the invention. Some resin ranges used in the claims also include sub-ranges within them, and variations within these ranges should also be interpreted as being covered by the appended claims where possible.

Claims

1. A method for separating resin components in a complex PPE alloy system, characterized in that, Includes the following steps: S1. Qualitative analysis of the resin components in the complex PPE alloy system is performed using testing methods to identify the resin components contained in the complex PPE alloy system; the complex PPE alloy system includes PPE resin, and at least one resin selected from PP, SEBS, and PS. S2. Mix and dissolve the first good solvent and the complex PPE alloy to obtain a solution; S3. Based on the qualitative analysis results of step S1, the solution obtained in step S2 is subjected to at least two of the following steps to separate and precipitate the corresponding resin components in the complex PPE alloy system: (1) The solution and the second good solvent are mixed to precipitate the PP component in the complex PPE alloy system. The mixture is filtered to obtain the PP component precipitate and the first filtrate. (2) The first filtrate and the third good solvent are mixed to precipitate the PPE component and / or SEBS component in the complex PPE alloy system, and filtered to obtain the PPE component precipitate and / or SEBS component precipitate, as well as the second filtrate. (3) The second filtrate and the fourth good solvent are mixed to precipitate the PS component in the complex PPE alloy system. The mixture is then filtered to obtain the PS component precipitate and the third filtrate.

2. The separation method according to claim 1, characterized in that, The first good solvent is selected from one or more of toluene, xylene, trichlorobenzene, and limonene.

3. The separation method according to claim 1, characterized in that, The second good solvent is selected from one or more of dichloromethane, chloroform, and 1,2-tetrachloroethane.

4. The separation method according to claim 1, characterized in that, The third good solvent is selected from one or more of acetone, tetrahydrofuran, and N-methylpyrrolidone.

5. The separation method according to claim 1, characterized in that, The fourth good solvent is selected from one or more of methanol, ethanol, and isopropanol.

6. The separation method according to claim 1, characterized in that, In step (2), the first filtrate is concentrated and then a third good solvent is added; and / or In step (3), the second filtrate is concentrated and then a fourth good solvent is added.

7. The separation method according to claim 1, characterized in that, In step S1, the testing method is selected from one or more of infrared spectroscopy, differential scanning calorimetry, Raman spectroscopy, and near-infrared spectroscopy.

8. The separation method according to claim 1, characterized in that, The third filtrate and the fifth good solvent are mixed to extract the oligomer components in the complex PPE alloy system.

9. The separation method according to claim 1, characterized in that, Qualitative analysis was performed on the PP component precipitation, PPE component precipitation and / or SEBS component precipitation, and PS component precipitation using test methods to determine whether they were still complex components. For precipitates of complex components, deuterated reagents were used for dissolution, and 1H NMR spectroscopy was used for qualitative and quantitative analysis of the complex components.

10. The method for separating resin components in a complex PPE alloy system according to any one of claims 1 to 9 is used for the qualitative and quantitative analysis of different resin components in a complex PPE alloy system.

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