Amino POSS (polyhedral oligomeric silsesquioxane) modified polyaryletherketone as well as preparation method and application thereof
By modifying PAEK resin with amino POSS, the problems of high melting temperature and high viscosity of polyaryletherketone resin have been solved, enabling low-temperature processing and high-performance resin modification, thus improving the application performance of aerospace, electronics and automotive devices.
Patent Information
- Application Number
- CN202610002703.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-04
- Publication Date
- 2026-03-17
AI Technical Summary
Existing polyaryletherketone resins have limited processing performance due to their high melting temperature and high viscosity, and their poor interfacial properties with fibers affect their application in aerospace, electronics and automotive fields.
By introducing amino POSS to modify PAEK resin, the cage-like structure of POSS is used for cross-linking modification, which reduces the resin melt viscosity, improves processing performance, and enhances the interfacial compatibility with fibers.
This technology enables low-temperature processing of PAEK resin, improving its mechanical strength and thermal properties, while also enhancing its interfacial properties with fibers, reducing the melting temperature, and improving processing performance.
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Figure CN121673554A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of high polymer materials, and particularly relates to an amino-POSS modified polyaryletherketone as well as a preparation method and application thereof. BACKGROUND
[0002] High-performance engineering plastic polyaryletherketone (PAEK) has been widely used in various applications such as aerospace, electronics and automobiles due to its high mechanical properties, excellent thermal stability and chemical resistance. However, due to its semi-crystalline characteristics, such polymers are insoluble in organic solvents at ambient temperature, except for strong acids. Therefore, they cannot be processed by casting methods, and require high molding temperatures due to the high melting temperature (about 340℃). The high melting temperature and high viscosity of such resins limit their processability and manufacturing costs. At present, PAEK resins can be blended with some oligomers to improve their processability, but these oligomers can cause a certain degree of reduction in the thermal properties and mechanical properties of PAEK. Therefore, it is necessary to modify PAEK to improve its processability without losing its thermal properties and mechanical properties. SUMMARY
[0003] The application aims to provide an amino-POSS modified polyaryletherketone as well as a preparation method and application thereof. The amino-POSS modified PAEK resin optimizes the processing temperature of the PAEK resin, improves the interfacial properties of the PAEK resin and fiber, and is beneficial to maintaining the mechanical strength and thermal properties of the PAEK resin.
[0004] In order to achieve the object of the application, the application provides the following technical solutions: A preparation method of an amino-POSS modified polyaryletherketone, comprising the following steps: Step 1: mixing polyaryletherketone polymer, oxalyl chloride and tetrahydrofuran to perform nucleophilic substitution reaction to obtain intermediate 1; Step 2: mixing the intermediate 1, amino-POSS and tetrahydrofuran to perform polymerization reaction to obtain the amino-POSS modified polyaryletherketone; The number of amino groups in the amino-POSS is greater than or equal to 2.
[0005] Preferably, the amino-POSS is one or more of diaminoposs, tetraaminoposs, hexaaminoposs and octaaminoposs.
[0006] Preferably, the preparation method of the polyaryletherketone polymer comprises the following steps: Mixing aromatic difluoromonomer, phenothalin, diphenol monomer, inorganic alkaline catalyst, water-carrying agent and organic solvent to perform polymerization reaction to obtain the polyaryletherketone polymer.
[0007] Preferably, the aromatic group bifiuorine monomer is 4,4'-difluorobenzophenone. The diphenol monomer is one or more of diphenylol, hydroquinone and resorcinol. The inorganic alkaline catalyst is potassium carbonate or sodium carbonate; and the water-carrying agent is toluene or xylene.
[0008] Preferably, the molar ratio of the polyaryletherketone polymer and oxalyl chloride is 2:1-1.5.
[0009] Preferably, the molar ratio of the amino POSS and the diphenol polymerization unit in the polyaryletherketone polymer is 0.5-1:2.
[0010] Preferably, the temperature of the nucleophilic substitution reaction is 25-40 DEG C, and the time is 12-48 h.
[0011] Preferably, the temperature of the polymerization reaction is 25-40 DEG C, and the time is 12-48 h.
[0012] The application also provides the amino POSS modified polyaryletherketone prepared by the preparation method.
[0013] The application also provides the application of the amino POSS modified polyaryletherketone in aerospace, electronic or automobile devices.
[0014] The application provides a preparation method of amino POSS modified polyaryletherketone, comprising the following steps: mixing polyaryletherketone polymer, oxalyl chloride and tetrahydrofuran, and performing nucleophilic substitution reaction to obtain intermediate 1; mixing the intermediate 1, amino POSS and tetrahydrofuran, and performing polymerization reaction to obtain the amino POSS modified polyaryletherketone; and the substitution number of amino in the amino POSS is greater than or equal to 2.
[0015] Further, the polyhedral oligomeric silsesquioxane (POSS) of the present application is a kind of organic-inorganic hybrid with cage structure, the skeleton is inorganic siloxane structure with nanometer size, and the skeleton is surrounded by organic substituent group.The nanometer size inorganic siloxane skeleton will bring excellent thermal stability and oxidation resistance to the material, and modify polyaryletherketone at molecular level.The organic component will make the combination between POSS macromolecule and polyaryletherketone better, which can be used to enhance the compatibility of polymer matrix and promote the dispersion at molecular level.The amino POSS modification of the present application can reduce the melt viscosity of PAEK resin, improve the processing performance, and at the same time maintain the thermal performance and mechanical performance of PAEK pure polymer.The number of amino group substitution in the amino POSS of the present application is greater than or equal to 2, and the POSS monomer with multiple active functional groups can act as a crosslinking point to prepare a polymer with crosslinked structure. BRIEF DESCRIPTION OF DRAWINGS
[0016] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the drawings needed in the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative effort on the basis of these drawings.
[0017] Figure 1 The infrared spectrum of the octaamino POSS modified PAEK resin obtained in Example 1. DETAILED DESCRIPTION
[0018] The present application provides a preparation method of amino POSS modified polyaryletherketone, comprising the following steps: Step 1: mixing polyaryletherketone polymer, oxalyl chloride and tetrahydrofuran to carry out nucleophilic substitution reaction to obtain intermediate 1; Step 2: mixing the intermediate 1, amino POSS and tetrahydrofuran to carry out polymerization reaction to obtain the amino POSS modified polyaryletherketone; The number of amino group substitution in the amino POSS is greater than or equal to 2.
[0019] In the present application, all raw materials are commercially available products or prepared by methods well known to those skilled in the art, unless otherwise specified.
[0020] In the present application, the polyaryletherketone polymer is mixed with oxalyl chloride and tetrahydrofuran to carry out nucleophilic substitution reaction to obtain intermediate 1.In the present application, the preparation method of the polyaryletherketone polymer comprises the following steps: Mixing aromatic difluoromonomer, phenothalin, diphenol monomer, inorganic alkaline catalyst, water-carrying agent and organic solvent to carry out polymerization reaction to obtain the polyaryletherketone polymer.
[0021] In the present application, the aromatic group difluoro monomer is 4,4'-difluorobenzophenone; the diphenol monomer is one or more of diphenylolpropane, hydroquinone and resorcinol, and in specific embodiments can be hydroquinone and diphenylolpropane; the inorganic alkaline catalyst is potassium carbonate or sodium carbonate; the water-carrying agent is toluene or xylene; the polymerization reaction is carried out under the condition of nitrogen atmosphere, 160-220℃ for 6-8h; after the polymerization reaction, the obtained product is washed and dried; the washing is water washing 5-8 times and ethanol washing 3-5 times; the drying is vacuum oven drying for 12-24h.
[0022] In the present application, the molar ratio of the polyaryletherketone polymer and oxalyl chloride is 2:1-1.5; the solid content of the polyaryletherketone polymer in tetrahydrofuran during the nucleophilic substitution reaction is 10-15%; the temperature of the nucleophilic substitution reaction is 25-40℃, and the time is 12-48h; after the nucleophilic substitution reaction, the obtained product is washed and dried; the washing is ethanol washing 3-5 times; the drying is vacuum oven drying for 24-48h.
[0023] After obtaining the intermediate 1, the present application mixes the intermediate 1, amino POSS and tetrahydrofuran to carry out polymerization reaction to obtain the amino POSS modified polyaryletherketone.
[0024] In the present application, the amino POSS is one or more of diaminoposs, tetraaminoposs, hexaaminoposs and octaaminoposs; the molar ratio of the amino POSS and the diphenol polymerization unit in the polyaryletherketone polymer is 0.5-1:2, and in specific embodiments can be 0.7 or 0.8:2; the temperature of the polymerization reaction is 25-40℃, and the time is 12-48h; the total solid content of the intermediate 1 and the amino POSS in tetrahydrofuran during the polymerization reaction is 10-15%; the temperature of the polymerization reaction is 25-40℃, and the time is 12-48h; after the substitution reaction, the obtained product is washed and dried; the washing is acetone washing 3-5 times; the drying is vacuum oven drying for 24-48h.
[0025] The present application also provides the amino POSS modified polyaryletherketone prepared by the preparation method.
[0026] The present application also provides the application of the amino POSS modified polyaryletherketone in aerospace, electronics or automotive devices.
[0027] In order to further illustrate the present application, the amino POSS modified polyaryletherketone, the preparation method and the application thereof provided by the present application are described in detail below in combination with the drawings and examples, but they cannot be understood as limiting the protection scope of the present application.
[0028] Example 1 0.2 mol of 4,4'-difluorobenzophenone, 0.04 mol of resorcinol, 0.15 mol of hydroquinone, 0.01 mol of phenolphthalein, 0.21 mol of potassium carbonate, 20 mL of xylene and 0.75 mol of diphenyl sulfone were mixed and reacted at 160°C for 2 h under a nitrogen atmosphere, then the temperature was increased to 180°C for 2 h, then the temperature was increased to 200°C for 2 h, and then the temperature was increased to 220°C for 2 h. The obtained product was washed with deionized water for 5 times and with ethanol for 5 times, and then dried in a vacuum oven at 80°C for 24 h to obtain a PAEK resin. The PAEK resin and 0.008 mol of oxalyl chloride were dissolved in tetrahydrofuran, and the solid content of the PAEK resin was controlled to be 15 wt%. The mixture was reacted at room temperature for 48 h. The obtained product was washed with ethanol for 5 times, and then dried in a vacuum oven at 80°C for 48 h to obtain intermediate 1. Intermediate 1 and octaamino-POSS were dissolved in tetrahydrofuran, and the molar ratio of octaamino-POSS to phenolphthalein was 0.5:2. The total solid content of intermediate 1 and octaamino-POSS was controlled to be 15 wt% when they were reacted. The mixture was reacted at room temperature for 48 h. The obtained product was washed with acetone for 5 times, and then dried in a vacuum oven at 80°C for 48 h to obtain a POSS-modified PAEK resin.
[0029] Figure 1 The infrared spectrum of the obtained POSS-modified PAEK resin of Example 1 is shown in FIG. 1. Figure 1 As can be seen from the results, the infrared characteristic peaks of the PAEK are: 1225 cm −1 (Ar-O-Ar in the main chain); 1497 cm −1 and 1598 cm −1 (benzene ring); 1654 cm −1 (C=O bond of aromatic ketone in the main chain); and the characteristic peaks representing the successful crosslinking of octaamino-POSS are: 1100 cm -1 (stretching vibration peak of Si-O-Si); and 587 cm -1 (bending vibration peak of Si-O-Si, which is the fingerprint peak of the inorganic framework of POSS).
[0030] Example 2 0.2 mol of 4,4'-difluorobenzophenone, 0.04 mol of resorcinol, 0.15 mol of hydroquinone, 0.01 mol of phenolphthalein, 0.21 mol of potassium carbonate, 20 mL of xylene, and 0.75 mol of diphenyl sulfone were mixed, reacted at 160°C for 2 h under a nitrogen atmosphere, continued to be heated to 180°C for 2 h, continued to be heated to 200°C for 2 h, continued to be heated to 220°C for 2 h, and the obtained product was sequentially washed with deionized water for 5 times and ethanol for 5 times, and dried in a vacuum oven at 80°C for 24 h to obtain a PAEK resin; The PAEK resin and oxalyl chloride were dissolved in tetrahydrofuran, the solid content of the PAEK resin was controlled to be 15 wt%, and the obtained product was washed with ethanol for 5 times and dried in a vacuum oven at 80°C for 48 h to obtain an intermediate 1. The intermediate 1 and octaamino POSS were dissolved in tetrahydrofuran, the molar ratio of octaamino POSS to resorcinol was 0.8:2, the total solid content of the intermediate 1 and octaamino POSS was controlled to be 15 wt% when reacting, and the obtained product was washed with acetone for 5 times and dried in a vacuum oven at 80°C for 48 h to obtain a POSS modified PAEK resin.
[0031] Example 3 0.2 mol of 4,4'-difluorobenzophenone, 0.04 mol of resorcinol, 0.15 mol of hydroquinone, 0.01 mol of phenolphthalein, 0.21 mol of potassium carbonate, 20 mL of xylene, and 0.75 mol of diphenyl sulfone were mixed, reacted at 160°C for 2 h under a nitrogen atmosphere, continued to be heated to 180°C for 2 h, continued to be heated to 200°C for 2 h, continued to be heated to 220°C for 2 h, and the obtained product was sequentially washed with deionized water for 5 times and ethanol for 5 times, and dried in a vacuum oven at 80°C for 24 h to obtain a PAEK resin; The PAEK resin and oxalyl chloride were dissolved in tetrahydrofuran, the solid content of the PAEK resin was controlled to be 15 wt%, and the obtained product was washed with ethanol for 5 times and dried in a vacuum oven at 80°C for 48 h to obtain an intermediate 1. The intermediate 1 and octaamino POSS were dissolved in tetrahydrofuran, the molar ratio of octaamino POSS to resorcinol was 0.8:2, the total solid content of the intermediate 1 and octaamino POSS was controlled to be 15 wt% when reacting, and the obtained product was washed with acetone for 5 times and dried in a vacuum oven at 80°C for 48 h to obtain a POSS modified PAEK resin.
[0032] Example 4 The 0.2 mol 4,4'-difluorobenzophenone, 0.04 mol resorcinol, 0.15 mol hydroquinone, 0.01 mol phenolphthalein, 0.21 mol potassium carbonate, 20 mL xylene and 0.75 mol diphenyl sulfone were mixed, reacted under the condition of nitrogen atmosphere and 160℃ for 2h, continued to heat to 180℃ for 2h, continued to heat to 200℃ for 2h, continued to heat to 220℃ for 2h, the obtained product was washed with deionized water for 5 times and ethanol for 5 times in turn, dried in a vacuum oven at 80℃ for 24h, and a PAEK resin was obtained. The PAEK resin and oxalyl chloride were dissolved in tetrahydrofuran, the solid content of the PAEK resin was controlled to be 15wt%, and the reaction was carried out at room temperature for 48h, the obtained product was washed with ethanol for 5 times, and dried in a vacuum oven at 80℃ for 48h, and an intermediate 1 was obtained. The intermediate 1 and tetraamino POSS were dissolved in tetrahydrofuran, the molar ratio of tetraamino POSS to resorcinol was 0.5:2, the total solid content of the intermediate 1 and tetraamino POSS was controlled to be 15wt% when reacting, the reaction was carried out at room temperature for 48h, the obtained product was washed with acetone for 5 times, and dried in a vacuum oven at 80℃ for 48h, and a POSS modified PAEK resin was obtained.
[0033] Example 5 The 0.2 mol 4,4'-difluorobenzophenone, 0.04 mol resorcinol, 0.15 mol hydroquinone, 0.01 mol phenolphthalein, 0.21 mol potassium carbonate, 20 mL xylene and 0.75 mol diphenyl sulfone were mixed, reacted under the condition of nitrogen atmosphere and 160℃ for 2h, continued to heat to 180℃ for 2h, continued to heat to 200℃ for 2h, continued to heat to 220℃ for 2h, the obtained product was washed with deionized water for 5 times and ethanol for 5 times in turn, dried in a vacuum oven at 80℃ for 24h, and a PAEK resin was obtained. The PAEK resin and oxalyl chloride were dissolved in tetrahydrofuran, the solid content of the PAEK resin was controlled to be 15wt%, and the reaction was carried out at room temperature for 48h, the obtained product was washed with ethanol for 5 times, and dried in a vacuum oven at 80℃ for 48h, and an intermediate 1 was obtained. The intermediate 1 and tetraamino POSS were dissolved in tetrahydrofuran, the molar ratio of tetraamino POSS to resorcinol was 0.5:2, the total solid content of the intermediate 1 and tetraamino POSS was controlled to be 15wt% when reacting, the reaction was carried out at room temperature for 48h, the obtained product was washed with acetone for 5 times, and dried in a vacuum oven at 80℃ for 48h, and a POSS modified PAEK resin was obtained.
[0034] Comparative Example 1 The 0.2 mol 4,4'-difluorobenzophenone, 0.04 mol resorcinol, 0.15 mol hydroquinone, 0.01 mol phenolphthalein, 0.21 mol potassium carbonate, 20 mL xylene and 0.75 mol diphenyl sulfone were mixed and reacted at 160°C for 2 h under a nitrogen atmosphere, then heated to 180°C for 2 h, then heated to 200°C for 2 h, then heated to 220°C for 2 h, then heated to 280°C for 2 h, and the obtained product was washed with deionized water for 5 times and washed with ethanol for 5 times, and dried in a vacuum oven at 80°C for 24 h to obtain a PAEK resin.
[0035] Comparative Example 2 The 0.2 mol 4,4'-difluorobenzophenone, 0.04 mol resorcinol, 0.15 mol hydroquinone, 0.01 mol phenolphthalein, 0.21 mol potassium carbonate, 20 mL xylene and 0.75 mol diphenyl sulfone were mixed and reacted at 160°C for 2 h under a nitrogen atmosphere, then heated to 180°C for 2 h, then heated to 200°C for 2 h, then heated to 220°C for 2 h, and the obtained product was washed with deionized water for 5 times and washed with ethanol for 5 times, and dried in a vacuum oven at 80°C for 24 h to obtain a PAEK resin; The PAEK resin and oxalyl chloride were dissolved in tetrahydrofuran, and the solid content of the PAEK resin was controlled to be 15 wt%, and the obtained product was washed with ethanol for 5 times and dried in a vacuum oven at 80°C for 48 h to obtain an intermediate 1. The intermediate 1 and monoamino POSS were dissolved in tetrahydrofuran, and the molar ratio of monoamino POSS to phenolphthalein was 1:2, and the total solid content of the intermediate 1 and monoamino POSS was controlled to be 15 wt% when reacting, and the obtained product was washed with acetone for 5 times and dried in a vacuum oven at 80°C for 48 h to obtain a POSS modified PAEK resin.
[0036] Test Example The POSS modified PAEK resins obtained in Examples 1-5 and Comparative Examples 1-2 were respectively tested for melting temperature, glass transition temperature, tensile strength and notched impact strength according to test standards GB / T 19466.2, GB / T 1040.2 and GB / T 1043.1.
[0037] Table 1 Test performance of the POSS modified PAEK resins obtained in Examples 1-5 and Comparative Examples 1-2
[0038] From the data in Table 1, it can be seen that the impact resistance of the PAEK resin modified by POSS is improved by using the cage structure of POSS and the flexibility of the PAEK chain, and under the action of POSS, the PAEK is crosslinked to improve the crosslinking density of the resin, and the glass transition temperature of the resin is also improved, the melting temperature of the resin is reduced, the processing performance of the resin is improved, and the improvement of the interfacial shear strength shows that the crosslinked resin has more excellent fiber matching performance.
[0039] In summary, the POSS modified PAEK resin is popularized in the manufacture of high polymer materials, the molding time can be reduced, the toughness of the PAEK resin is improved, the product has excellent heat resistance and mechanical properties, and the process is convenient, efficient and high-performance.
[0040] Although the above embodiment describes the present application in detail, it is only a part of the embodiment of the present application, not all the embodiments, and other embodiments can be obtained under the premise of no creativity according to the embodiment, which belongs to the protection scope of the present application.
Claims
1. A method for preparing an amino-POSS modified polyarylene ether ketone, characterized in that, The method comprises the following steps: Step 1: mixing polyaryletherketone polymer, oxalyl chloride and tetrahydrofuran to perform a nucleophilic substitution reaction to obtain intermediate 1; Step 2: mixing intermediate 1, amino-POSS and tetrahydrofuran to perform a polymerization reaction to obtain the amino-POSS modified polyaryletherketone; The number of amino groups in the amino-POSS is greater than or equal to 2.
2. The production method according to claim 1, characterized by, The amino-POSS is one or more of diamin-POSS, tetraamino-POSS, hexaamino-POSS and octaamino-POSS.
3. The production method according to claim 1, characterized by, The method for preparing the polyaryletherketone polymer comprises the following steps: Mixing aromatic difluoromonomer, phenothalin, diphenol monomer, inorganic alkaline catalyst, water-carrying agent and organic solvent to perform a polymerization reaction to obtain the polyaryletherketone polymer.
4. The production method according to claim 3, characterized by, The aromatic difluoromonomer is 4,4'-difluorobenzophenone; The diphenol monomer is one or more of biphenylol, hydroquinone and resorcinol; The inorganic alkaline catalyst is potassium carbonate or sodium carbonate; and the water-carrying agent is toluene or xylene.
5. The preparation method according to claim 1, characterized in that, The molar ratio of the polyaryletherketone polymer to oxalyl chloride is 2:1-1.
5.
6. The method of claim 1, wherein, The molar ratio of the amino-POSS to the diphenol polymerization unit in the polyaryletherketone polymer is 0.5-1:
2.
7. The preparation method according to claim 1, characterized in that, The temperature of the nucleophilic substitution reaction is 25-40℃, and the time is 12-48h.
8. The production method according to claim 1 or 6, characterized by, The temperature of the polymerization reaction is 25-40℃, and the time is 12-48h.
9. The amino-POSS modified polyaryletherketone prepared by the method of any one of claims 1-8.
10. The amino-POSS modified polyaryletherketone of claim 9 is used in aerospace, electronic or automotive devices.