A thermosetting polyaryletherketone, a composite material, and a preparation method and application of the thermosetting polyaryletherketone
A crosslinkable thermosetting polyarylether ketone containing amino groups was synthesized through nucleophilic condensation reaction. The in-situ crosslinking reaction between amino and carbonyl groups solved the problem of uneven dispersion of diamine monomers, achieving high stability and excellent ablation resistance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2023-12-06
- Publication Date
- 2026-06-26
AI Technical Summary
In the prior art, diamine monomers are difficult to disperse evenly in polyaryletherketone matrix, resulting in defects in the crosslinking network and making it impossible to obtain stable products.
Thermosetting polyaryletherketones containing amino groups are synthesized by nucleophilic condensation reaction. The in-situ crosslinking reaction between amino and carbonyl groups avoids the addition of crosslinking agents and adopts a rigid and stable crosslinking structure to prepare thermosetting polyaryletherketones.
It improves the product's stability and ablation resistance, with a carbon residue rate of up to 87% at 600℃ and 78% at 800℃, and avoids defects caused by uneven distribution of crosslinking agent.
Smart Images
Figure CN117645717B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of special polymer materials, specifically to a thermosetting polyaryletherketone, a composite material, and a method for preparing and applying the thermosetting polyaryletherketone. Background Technology
[0002] Polyaryletherketone (PAGE) is a thermoplastic engineering plastic with excellent comprehensive properties, and it has important applications in key components in special fields such as aerospace and military. However, PAGE has inherent limitations in terms of high-temperature resistance. By cross-linking PAGE molecules to form a three-dimensional network structure, its high-temperature resistance, mechanical properties, dimensional stability, and ablation resistance can be improved, enabling it to meet more demanding service environments.
[0003] In existing technologies, diamine monomers are used as crosslinking agents to react with the carbonyl groups in polyaryletherketones (PAKs) to form imine bonds, thereby achieving crosslinking. The resulting crosslinked PAKs exhibit high thermal stability, as reported in patent application CN112566960A. However, the diamine monomers are difficult to disperse uniformly in the PAK matrix, leading to defects in the crosslinked network formed after curing, and consequently, a stable product cannot be obtained. Summary of the Invention
[0004] To address the aforementioned shortcomings, this invention provides a thermosetting polyaryletherketone (PAE), a composite material, a method for preparing the PAE, and its applications. The PAE exhibits a stable crosslinking network, effectively yielding a stable product.
[0005] The first aspect of this invention protects a thermosetting polyaryletherketone having a molecular structure as shown in Formula I:
[0006]
[0007] Where m and n are the mole percentages of repeating units, m+n=1, 0.6≤n≤1, 0≤m≤0.4.
[0008] Ar is selected from one of formulas 1-8:
[0009]
[0010] The second aspect of this invention protects a method for preparing thermosetting polyaryletherketones, comprising the following steps:
[0011] 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene, the second bisphenol monomer, 4,4-dihalobenzophenone, solvent, catalyst and dehydrating agent were mixed and subjected to a first heating reflux. After the reflux was completed, the dehydrating agent was removed and the temperature was raised to the second heating temperature to obtain the crude product liquid.
[0012] The second bisphenol monomer is selected from one of the following formulas 1'-8':
[0013]
[0014] The crude product liquid was post-treated to obtain thermosetting polyaryletherketone.
[0015] Furthermore, the amount of the catalyst is 1.15-1.5 times that of the 4,4-dihalobenzophenone.
[0016] The molar ratio of 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene to the second bisphenol monomer is 3:2-1:0;
[0017] The total number of moles of 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene and the second bisphenol monomer is equal to the number of moles of 4,4-dihalobenzophenone.
[0018] Furthermore, the temperature of the first heating is 130-180℃, and the reflux time is 1-3h.
[0019] The second heating temperature is 180-230℃, and the reaction time is 2-5 hours.
[0020] Furthermore, the 4,4-dihalobenzophenone is one or both of 4,4-difluorobenzophenone and 4,4-dichlorobenzophenone.
[0021] The solvent is one or more of sulfolane (TMS), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).
[0022] The dehydrating agent is toluene or xylene, and the mass of the dehydrating agent is 5%-70% of the mass of the solvent.
[0023] The catalyst is one or more of potassium carbonate, sodium carbonate, and calcium carbonate.
[0024] Furthermore, the post-processing steps are as follows:
[0025] The crude product solution was diluted with N,N-dimethylacetamide, then precipitated in an ethanol-water mixture, pulverized, and boiled with deionized water 5-6 times, each time for 40-90 minutes, and dried to obtain thermosetting polyarylether ketone.
[0026] Furthermore, the mass of the N,N-dimethylacetamide is 0.5-8 times the theoretical mass yield of the obtained thermosetting polyaryletherketone.
[0027] The volume ratio of ethanol to water in the ethanol-water mixture is 4-9:1-6.
[0028] The third aspect of this invention protects the use of thermosetting polyaryletherketones in thermosetting products.
[0029] A fourth aspect of this invention protects a composite material comprising a thermosetting polyaryletherketone, a filler, and a silane coupling agent.
[0030] The thermosetting polyaryletherketone has a mass percentage of 57-99.8%, the filler has a mass percentage of 0-40%, and the silane coupling agent has a mass percentage of 0.2-3%.
[0031] The composite material is made by mixing the thermosetting polyaryletherketone, the filler and the silane coupling agent, first molding at a temperature of 300-380℃ for 1-5 hours, and then post-curing at a temperature of 320-360℃ for 2-48 hours.
[0032] Furthermore, the filler is selected from one or more of chopped glass fiber, chopped carbon fiber, and chopped basalt fiber. The silane coupling agent is KH550.
[0033] Beneficial effects: This invention synthesizes an amino-containing crosslinkable thermosetting polyaryletherketone through nucleophilic condensation reaction. This thermosetting polyaryletherketone does not require the addition of crosslinking agents such as diamine monomers, thus completely avoiding the impact of uneven distribution of crosslinking agents on thermosetting polyaryletherketone products.
[0034] This invention prepares thermosetting polyaryletherketones through an in-situ crosslinking reaction of amino and carbonyl groups, avoiding the defects caused by uneven distribution of crosslinking agents that may exist in the prior art, and improving product stability; in addition, this invention selects a rigid and stable crosslinking structure, which improves the ablation resistance of thermosetting polyaryletherketone products.
[0035] This invention further heats thermosetting polyaryletherketones (PAEs), enabling them to cure in situ through self-crosslinking, thus obtaining the PAE product without the addition of any crosslinking agent. The resulting PAE product exhibits a carbon residue rate of 87% at 600°C and 78% at 800°C in a nitrogen atmosphere.
[0036] Attached Description
[0037] Figure 1 The TGA test curves are for the thermosetting polyaryletherketones in Examples 1 and 2.
[0038] Figure 2 The image shows the infrared spectrum of the polyaryletherketone powder from Example 1. Detailed Implementation
[0039] Example 1
[0040] 0.08 mol of 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene, 0.02 mol of biphenyl hydroquinone, 0.1 mol of 4,4-difluorobenzophenone, 100 ml of sulfolane, 0.12 mol of sodium carbonate, and 30 ml of toluene were added sequentially to a reaction vessel. Under nitrogen protection, the mixture was refluxed at 150 °C for 2.5 h. The toluene and the resulting water were then removed, and the temperature was raised to 210 °C for another 2.5 h. The reaction was then terminated, and N,N-dimethylacetamide (DMA) was added. c) Dilute, and finally precipitate in a 1:1 ethanol-water mixture, pulverize, and boil and wash with deionized water 5-6 times, each time for 40-90 minutes, and dry to obtain polyaryletherketone powder with amino side groups of formula (II); mold by hot press at 360℃ for 3 hours to obtain cross-linked polyaryletherketone molded parts, and then heat treat at 320℃ for 24 hours to obtain the final thermosetting polyaryletherketone product, with a carbon residue rate of 84% at 600℃.
[0041]
[0042] Figure 2 The image shows the infrared spectrum of the polyaryletherketone product prepared in this embodiment. In the image, 3461 cm⁻¹... -1 and 3357cm -1 The peak represents the asymmetric and symmetric stretching vibrations of amino groups, at 1652 cm⁻¹. -1 The peak of C=O stretching vibration on the side base is 1585 cm⁻¹. -1 The peak for C-C stretching vibration is 1228 cm⁻¹. -1 The characteristic absorption peak of Ar-O-Ar in the polymer backbone is 1103 cm⁻¹. -1 The peak of CN asymmetric vibration stretching vibration.
[0043] Take 5g of chopped glass fiber and 0.1g of silane coupling agent KH550 and mix them evenly in a high-speed mixer. Then add 45g of polyaryletherketone powder and continue stirring. The resulting mixture is then molded at 360℃ for 3 hours. The molded part is then heat-treated at 320℃ for 24 hours to obtain the final thermosetting polyaryletherketone composite material. The mass ablation rate of oxyacetylene at 2700℃ for 20 seconds reaches 0.040g / s, which shows excellent ablation resistance.
[0044] Example 2
[0045] Take 0.07 mol of 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene, 0.03 mol of 2,7-dihydroxy-9-fluorenone, 0.1 mol of 4,4-difluorobenzophenone, 110 ml of sulfolane, and 0.12 mol of sodium carbonate. 1. 30 ml of toluene was added sequentially to the reaction vessel. Under nitrogen protection, the mixture was refluxed at 150 °C for 2.5 h. Then, the toluene and the generated water were discharged, and the temperature was raised to 210 °C for 2.5 h to stop the reaction. The mixture was then diluted with N,N-dimethylacetamide (DMAc) and finally precipitated in a 1:1 ethanol-water mixture. The precipitate was crushed and boiled with deionized water 5-6 times for 40-90 min each time. The precipitate was dried to obtain polyaryletherketone powder with amino side groups of formula (III). The powder was then molded by hot pressing at 360 °C for 3 h to obtain cross-linked polyaryletherketone molded parts. Finally, the parts were heat-treated at 330 °C for 36 h to obtain the final thermosetting polyaryletherketone product. The carbon residue rate reached 87% at 600 °C.
[0046]
[0047] Take 10g of chopped glass fiber and 0.1g of silane coupling agent KH550 and mix them evenly in a high-speed mixer. Then add 40g of polyaryletherketone powder and continue stirring. The resulting mixture is then molded at 360℃ for 3 hours. The molded part is then heat-treated at 330℃ for 36 hours to obtain the final thermosetting polyaryletherketone composite material. The mass ablation rate of oxyacetylene at 2700℃ for 20 seconds reaches 0.032g / s, which shows excellent ablation resistance.
[0048] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.
Claims
1. A thermosetting polyaryletherketone, characterized in that, It has a molecular structure as shown in Formula I: Where m and n are the molar percentages of repeating units, m+n=1, 0.6≤n≤1, 0≤m≤0.4; Ar is selected from one of formulas 1-8:
2. A method for preparing the thermosetting polyaryletherketone as described in claim 1, characterized in that, Includes the following steps: 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene, the second bisphenol monomer, 4,4-dihalobenzophenone, solvent, catalyst and dehydrating agent were mixed and subjected to a first heating reflux. After the reflux was completed, the dehydrating agent was removed and the temperature was raised to the second heating temperature to obtain the crude product liquid. The second bisphenol monomer is selected from one of the following formulas 1'-8': The crude product liquid was post-treated to obtain thermosetting polyaryletherketone.
3. The method for preparing thermosetting polyaryletherketone according to claim 2, characterized in that, The amount of the catalyst is 1.15-1.5 times that of the 4,4-dihalobenzophenone; The molar ratio of 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene to the second bisphenol monomer is 3:2-1:0; The total number of moles of 9,9-bis(4-aminophenyl)-2,7-dihydroxyfluorene and the second bisphenol monomer is equal to the number of moles of 4,4-dihalobenzophenone.
4. The method for preparing thermosetting polyaryletherketone according to claim 2, characterized in that, The temperature of the first heating is 130-180℃, and the reflux time is 1-3 hours; The second heating temperature is 180-230℃, and the reaction time is 2-5 hours.
5. The method for preparing thermosetting polyaryletherketone according to claim 2, characterized in that, The 4,4-dihalobenzophenone is one or both of 4,4-difluorobenzophenone and 4,4-dichlorobenzophenone; The solvent is one or more of sulfolane, dimethyl sulfoxide and N-methylpyrrolidone; The dehydrating agent is toluene or xylene, and the mass of the dehydrating agent is 5%-70% of the mass of the solvent; The catalyst is one or more of potassium carbonate, sodium carbonate, and calcium carbonate.
6. The method for preparing thermosetting polyaryletherketone according to claim 2, characterized in that, The post-processing steps are as follows: The crude product solution was diluted with N,N-dimethylacetamide, then precipitated in an ethanol-water mixture, crushed, and boiled with deionized water for 40-90 minutes each time. The product was then dried to obtain thermosetting polyarylether ketone.
7. The method for preparing thermosetting polyaryletherketone according to claim 6, characterized in that, The mass of the N,N-dimethylacetamide is 0.5-8 times the theoretical mass yield of the obtained thermosetting polyaryletherketone. The volume ratio of ethanol to water in the ethanol-water mixture is 4-9:1-6.
8. The application of a thermosetting polyaryletherketone as described in claim 1 or a thermosetting polyaryletherketone prepared by any one of claims 2 to 7 in thermosetting products.
9. A composite material, characterized in that, Includes the thermosetting polyaryletherketone as described in claim 1 or the thermosetting polyaryletherketone prepared by the preparation method described in any one of claims 2 to 7, fillers, and silane coupling agents; The thermosetting polyaryletherketone has a mass percentage of 57-99.8%, the filler has a mass percentage of 0-40%, and the silane coupling agent has a mass percentage of 0.2-3%. The composite material is made by mixing the thermosetting polyaryletherketone, the filler and the silane coupling agent, first molding at a temperature of 300-380℃ for 1-5 hours, and then post-curing at a temperature of 320-360℃ for 2-48 hours.
10. The composite material according to claim 9, characterized in that, The filler includes one or more of chopped glass fiber, chopped carbon fiber and chopped basalt fiber; The silane coupling agent is KH550.