Copolymerized polyether-ether-ketone composite material, preparation method thereof and preparation method of pipe

Abstract

The invention provides a copolymerized polyether-ether-ketone composite material, a preparation method thereof and a preparation method of a pipe, and belongs to the field of high polymer material manufacturing. The invention provides a copolymerized polyether-ether-ketone composite material. The copolymerized polyether-ether-ketone composite material comprises copolymerized polyether-ether-ketone resin, hydroxylated carbon nanotubes and silane coupling agent modified wollastonite, wherein the hydroxylated carbon nanotubes and the silane coupling agent modified wollastonite are dispersed in the copolymerized polyether-ether-ketone resin; the melt index of the copolymerized polyether-ether-ketone resin is 23 to 80g / 10min at 400 DEG C and 500N. The copolymerized polyether-ether-ketone composite material disclosed by the invention is excellent in antistatic property and mechanical property.

Description

Technical Field

[0001] The present invention relates to the field of polymer material manufacturing, and in particular to a copolymerized polyetheretherketone composite material and a preparation method thereof, and a pipe preparation method. Background Art

[0002] With the continuous development of chemical, petroleum, pharmaceutical and other industrial fields, many equipment and products in industrial production processes are very sensitive to static electricity. The production process will cause static electricity accumulation and discharge. Static electricity discharge may cause fires and explosions of flammable gases, liquids and dust. In order to fundamentally solve the problem of static electricity accumulation and discharge and improve production safety, antistatic materials are used.

[0003] Polyetheretherketone (PEEK) is a semi-crystalline, ultra-high-performance special engineering plastic. With its excellent mechanical properties, high temperature resistance, and chemical corrosion resistance, the films, pipes, and components made from it are widely used in aerospace, electronics, medical machinery, and other fields. However, pure PEEK resin is an electrical insulating material with a volume resistivity of up to 10 15 ~10 16 Ω·cm, which can easily lead to static electricity accumulation. Traditional solutions to PEEK's antistatic issues rely primarily on adding conductive fillers, such as carbon nanotubes, carbon fibers, graphene, and metal powders. While these can reduce the volume resistivity of PEEK to a certain extent, they often face two major issues: First, high levels of conductive fillers, while improving antistatic properties, can also reduce toughness; second, conductive fillers tend to agglomerate, resulting in uneven dispersion and reduced antistatic and mechanical properties. Summary of the Invention

[0004] The present invention provides a copolymerized polyetheretherketone composite material, a preparation method thereof, and a pipe preparation method. The copolymerized polyetheretherketone composite material has excellent antistatic properties and mechanical properties.

[0005] The present invention provides a copolymerized polyetheretherketone composite material, comprising a copolymerized polyetheretherketone resin, hydroxylated carbon nanotubes dispersed in the copolymerized polyetheretherketone resin, and wollastonite modified by a silane coupling agent;

[0006] At 400° C. and 500N, the melt index of the copolymerized polyetheretherketone resin is 23 to 80 g / 10 min.

[0007] Preferably, in terms of mass fraction, the mass fraction of the copolymerized polyetheretherketone resin in the copolymerized polyetheretherketone composite material is 80-95%, the mass fraction of the hydroxylated carbon nanotubes is 3-10%, and the mass fraction of the silane coupling agent-modified wollastonite is 2-10%; the sum of the mass fractions of the copolymerized polyetheretherketone resin, the hydroxylated carbon nanotubes and the silane coupling agent-modified wollastonite is 100%.

[0008] Preferably, the method for preparing the hydroxylated carbon nanotubes comprises the following steps:

[0009] Mixing concentrated sulfuric acid, concentrated nitric acid and carbon nanotubes and performing a hydroxylation treatment, then performing solid-liquid separation on the obtained product, washing, drying and vacuum annealing the obtained solid to obtain the hydroxylated carbon nanotubes;

[0010] The total volume ratio of the concentrated sulfuric acid and concentrated nitric acid to the carbon nanotubes is 100 mL:1 g; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1; the mass concentration of the concentrated sulfuric acid is 98%; and the mass concentration of the concentrated nitric acid is 60-68%.

[0011] Preferably, the aspect ratio of the carbon nanotubes is 200 to 1500:1;

[0012] The carbon nanotubes include array carbon nanotubes.

[0013] Preferably, the temperature of the hydroxylation treatment is 50-70° C., and the time is 60-120 min.

[0014] Preferably, the preparation method of the silane coupling agent-modified wollastonite comprises the following steps:

[0015] Wollastonite and a silane coupling agent are mixed and then modified to obtain the silane coupling agent-modified wollastonite.

[0016] Preferably, the silane coupling agent includes one or more of KH-550, KH-560 and KH-570; and the mass ratio of the wollastonite to the silane coupling agent is 100:1.

[0017] Preferably, the modification temperature is 60-90° C. and the modification time is 60-90 min.

[0018] The present invention also provides a method for preparing the copolymerized polyetheretherketone composite material described in the above technical solution, comprising the following steps:

[0019] The copolymerized polyetheretherketone resin, hydroxylated carbon nanotubes and silane coupling agent-modified wollastonite are mixed and then melt-extruded and granulated;

[0020] The temperature of the melt extrusion is 240-350°C.

[0021] The present invention also provides a method for preparing a pipe, comprising the following steps:

[0022] The copolymerized polyetheretherketone composite material described in the above technical solution of the claim or the copolymerized polyetheretherketone composite material prepared by the preparation method described in the above technical solution is melt-extruded, and then the extruded tube blank is annealed to obtain the tube.

[0023] Because carbon nanotubes have excellent electrical conductivity, when incorporated into a copolymerized PEEK matrix, they form a conductive network structure within the matrix, enabling rapid charge transfer and preventing static electricity accumulation. Adding silane-coupling-modified wollastonite can reduce carbon nanotube aggregation, thereby forming an excellent interface between the carbon nanotubes and the PEEK matrix. Furthermore, as nanoscale reinforcements, the uniform dispersion of carbon nanotubes can effectively improve the strength and modulus of the composite material. Furthermore, as heterogeneous nucleating agents, carbon nanotubes can promote crystallization of the copolymerized PEEK, thereby optimizing the rigidity and strength of the composite material. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is the TGA characterization of the composite material of Example 3 of the present invention;

[0025] Figure 2 DSC characterization of the composite material of Example 8 of the present invention;

[0026] Figure 3 This is a characterization of the mechanical properties of the composite material of Example 2 of the present invention. DETAILED DESCRIPTION

[0027] The present invention provides a copolymerized polyetheretherketone composite material, comprising a copolymerized polyetheretherketone resin, hydroxylated carbon nanotubes dispersed in the copolymerized polyetheretherketone resin, and wollastonite modified by a silane coupling agent;

[0028] At 400° C. and 500N, the melt index of the copolymerized polyetheretherketone resin is 23 to 80 g / 10 min.

[0029] The copolymerized polyetheretherketone composite material provided by the present invention comprises a copolymerized polyetheretherketone resin; at 400°C and 500N, the melt index of the copolymerized polyetheretherketone resin is 23 to 80 g / 10min. In a specific embodiment of the present invention, the melt index of the copolymerized polyetheretherketone resin can be 30 g / 10min, 40 g / 10min, 50 g / 10min, 60 g / 10min or 70 g / 10min, and the melting point is preferably ≤310°C; the copolymerized polyetheretherketone resin The resin preferably includes one or more of CN114805789A, CN113736044A, CN116515101A, CN106146771A, and 202111140603; in terms of mass fraction, the mass fraction of the copolymerized polyetheretherketone resin in the copolymerized polyetheretherketone composite material is preferably 80-95%. In a specific embodiment of the present invention, the mass fraction of the copolymerized polyetheretherketone resin in the copolymerized polyetheretherketone composite material can be 85% or 95%.

[0030] The copolymerized polyetheretherketone composite material provided by the present invention includes hydroxylated carbon nanotubes dispersed in the copolymerized polyetheretherketone resin. Calculated by mass fraction, the mass fraction of the hydroxylated carbon nanotubes in the copolymerized polyetheretherketone composite material is preferably 3 to 10%. In a specific embodiment of the present invention, the mass fraction of the hydroxylated carbon nanotubes in the copolymerized polyetheretherketone composite material can be 4%, 5%, 6%, 7%, 8% or 9%.

[0031] In the present invention, the method for preparing the hydroxylated carbon nanotubes preferably comprises the following steps:

[0032] Concentrated sulfuric acid, concentrated nitric acid and carbon nanotubes are mixed and then subjected to hydroxylation treatment. The obtained product is then subjected to solid-liquid separation. The obtained solid is washed, dried and vacuum annealed to obtain the hydroxylated carbon nanotubes.

[0033] In the present invention, the total volume ratio of the concentrated sulfuric acid and concentrated nitric acid to the carbon nanotubes is preferably 100 mL:1 g; the aspect ratio of the carbon nanotubes is preferably 200 to 1500:1, and the model of the arrayed carbon nanotubes preferably includes GT-300 or GT210; the carbon nanotubes preferably include arrayed carbon nanotubes; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is preferably 3:1; the mass concentration of the concentrated sulfuric acid is preferably 98%; and the mass concentration of the concentrated nitric acid is preferably 60 to 68%.

[0034] In the present invention, the temperature of the hydroxylation treatment is preferably 50 to 70° C., the time is preferably 60 to 120 min, and the hydroxylation treatment is preferably performed under ultrasonic conditions.

[0035] In the present invention, the vacuum annealing treatment is preferably performed at a temperature of 220° C., a time of 2.5 h, and a vacuum degree of 0.1 Pa. The vacuum annealing treatment can remove amorphous carbon impurities and catalyst residues, and can also repair defects in the carbon nanotubes into a complete network structure as much as possible.

[0036] The copolymerized polyetheretherketone composite material provided by the present invention includes silane coupling agent-modified wollastonite dispersed in the copolymerized polyetheretherketone resin. Calculated by mass fraction, the mass fraction of the hydroxylated silane coupling agent-modified wollastonite in the copolymerized polyetheretherketone composite material is preferably 2 to 10%. In a specific embodiment of the present invention, the mass fraction of the hydroxylated silane coupling agent-modified wollastonite in the copolymerized polyetheretherketone composite material can be 3%, 4%, 5%, 6%, 7%, 8% or 9%.

[0037] In the present invention, the preparation method of the silane coupling agent-modified wollastonite preferably comprises the following steps:

[0038] Wollastonite and a solution of a silane coupling agent are mixed and then modified to obtain the silane coupling agent-modified wollastonite.

[0039] Before the mixing, the wollastonite is preferably dried and then washed with dilute hydrochloric acid (pH between 5-6) for 60 minutes and then dried.

[0040] In the present invention, the method for preparing the solution of the silane coupling agent preferably comprises the following steps:

[0041] After the silane coupling agent and the solvent are mixed, the pH value of the resulting solution is adjusted to 4-5 with hydrochloric acid.

[0042] The dosage ratio of the silane coupling agent to the solvent is preferably 10 g:100 mL, and the silane coupling agent preferably includes one or more of KH-550, KH-560 and KH-570; the solvent preferably includes ethanol and water, and the volume ratio of ethanol and water is preferably 1:1. The mass ratio of wollastonite to silane coupling agent is preferably 100:1.

[0043] In the present invention, the mass concentration of the hydrochloric acid is preferably 36%.

[0044] In the present invention, the modification temperature is preferably 60-90°C, and the modification time is preferably 60-90 min. In a specific embodiment of the present invention, the modification temperature can be 75°C, 80°C or 85°C, and the modification time can be 70 min or 80 min.

[0045] The present invention also provides a method for preparing the copolymerized polyetheretherketone composite material described in the above technical solution, comprising the following steps:

[0046] The copolymerized polyetheretherketone resin, hydroxylated carbon nanotubes and silane coupling agent-modified wollastonite are mixed and then melt-extruded and granulated.

[0047] In the present invention, the temperature of the melt extrusion is 240-350°C.

[0048] The present invention also provides a method for preparing a pipe, comprising the following steps:

[0049] The copolymerized polyetheretherketone composite material described in the above scheme or the copolymerized polyetheretherketone composite material prepared by the preparation method described in the above scheme is melt-extruded, and then the extruded tube blank is annealed to obtain the tube.

[0050] In the present invention, the annealing temperature is preferably 200° C., and the annealing time is preferably 2 hours.

[0051] The copolymerized polyetheretherketone composite material, its preparation method and the pipe preparation method provided by the present invention are described in detail below with reference to the embodiments, but they should not be understood as limiting the scope of protection of the present invention.

[0052] In this embodiment, the modified carbon nanotubes are prepared by mixing mixed acid with carbon nanotubes (model (GT210)), ultrasonically treating them at 70°C for 60 minutes, performing solid-liquid separation, and then washing, drying, and vacuum annealing the resulting solid. The volume ratio of the mixed acid to the carbon nanotubes is 100 mL:1 g; the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid is 3:1; the mass concentration of the concentrated sulfuric acid is 98%; the mass concentration of the concentrated nitric acid is 68%; and the vacuum annealing temperature is 220°C, the time is 2.5 hours, and the vacuum degree is 0.1 Pa.

[0053] The preparation method of silane-coupled wollastonite is as follows: drying wollastonite powder, washing with dilute hydrochloric acid (pH between 5-6) for 60 minutes and then drying;

[0054] 10g of silane coupling agents KH-550, KH560, and KH-570 (the mass ratio of the three coupling agents is 1:1:1) are added to 100mL of ethanol solution (the volume ratio of ethanol to water is 1:1) and dissolved. The pH is adjusted to between 4-5 with 36% hydrochloric acid and stirred for 90 minutes until it becomes slightly turbid. The treated wollastonite powder (the mass ratio of wollastonite to silane coupling agent is 100:1) is then added to the silane coupling agent hydrolyzate and stirred at 80°C for 60 minutes for a dehydration condensation reaction. The resulting product is then separated, and the resulting solid is washed and dried.

[0055] Example 1

[0056] (1) 90 wt% of the 3D printed polyetheretherketone interlayer reinforcement material prepared in Example 1 of CN114805789A, 5 wt% of modified carbon nanotubes and 5 wt% of silane-coupled wollastonite were blended in a grinder to prepare a mixed material, and the mixed material was melt-extruded (twin-screw extrusion speed 300 r / min, feeding temperature 240°C, extrusion section temperature 350°C, extrusion die temperature 330°C) and granulated.

[0057] (2) The prepared antistatic composite material was injection molded into tensile specimens using an injection molding machine, and samples were prepared and tested according to the national standard GB / T1040.2-2022. The prepared antistatic composite material was placed in a mold and pressed into a sheet using a hot press to obtain a volume resistivity specimen, which was prepared and tested according to the national standard GB / T 31838.1-2015. The prepared specimens, sheets, and extruded tubes were placed in an oven and annealed at 200°C for 2 hours.

[0058] Example 2

[0059] The difference between Example 2 and Example 1 is that the material ratios are 95 wt% of 3D printed polyetheretherketone interlayer reinforcement material, 3 wt% of modified carbon nanotubes, and 2 wt% of silane-coupled wollastonite.

[0060] Example 3

[0061] The difference between Example 3 and Example 1 is that the material ratios are 90 wt % of 3D printed polyetheretherketone interlayer reinforcement material, 7 wt % of modified carbon nanotubes, and 3 wt % of silane-coupled wollastonite.

[0062] Example 4

[0063] The difference between Example 4 and Example 1 is that the material ratios are 90 wt % of 3D printed polyetheretherketone interlayer reinforcement material, 8 wt % of modified carbon nanotubes, and 2 wt % of silane-coupled wollastonite.

[0064] Example 5

[0065] The difference between Example 5 and Example 1 is that the material ratios are 90 wt % of 3D printed polyetheretherketone interlayer reinforcement material, 6 wt % of modified carbon nanotubes, and 4 wt % of silane-coupled wollastonite.

[0066] Example 6

[0067] The difference between Example 6 and Example 1 is that the material ratios are 86 wt % of 3D printed polyetheretherketone interlayer reinforcement material, 8 wt % of modified carbon nanotubes, and 6 wt % of silane-coupled wollastonite.

[0068] Example 7

[0069] The difference between Example 7 and Example 1 is that the material ratios are 88 wt % of 3D printed polyetheretherketone interlayer reinforcement material, 6 wt % of modified carbon nanotubes, and 6 wt % of silane-coupled wollastonite.

[0070] Example 8

[0071] The difference between Example 8 and Example 1 is that the material ratios are 80 wt% of 3D printed polyetheretherketone interlayer reinforcement material, 10 wt% of modified carbon nanotubes, and 10 wt% of silane-coupled wollastonite.

[0072] The properties of the low melting point copolymerized polyetheretherketone antistatic composite materials prepared according to Examples 1 to 8 are shown in Table 1

[0073] Table 1 Characterization of tensile strength, elongation at break and volume resistivity of Examples 1 to 8

[0074]

[0075]

[0076] Table 2 Impact performance characterization of copolymerized polyetheretherketone antistatic materials of Examples 1 to 4

[0077] Test items Example 1 Example 2 Example 3 Example 4 <![CDATA[冲击强度(KJ / m 2 )]]> 109 102 105 107

[0078] As shown in Table 1, the volume resistivity of the material is in the range of 102 to 109 Ω·cm, and while maintaining high mechanical properties, it has excellent antistatic properties.

[0079] It can be seen from Table 2 that the material has a very high elongation at break, and the impact toughness of the material is also characterized.

[0080] Figure 1 This is the TGA characterization of the composite material of Example 3 of the present invention.

[0081] Depend on Figure 1 It can be seen that the 5% thermal decomposition temperature of the material of Example 3 reaches 560°C, which means that the material has excellent thermal stability.

[0082] Figure 2 This is the DSC characterization of the composite material of Example 8 of the present invention.

[0083] Depend on Figure 2 It can be seen that the melting point of the material is around 290°C, which is significantly lower than the melting point of polyetheretherketone, making it more conducive to melt processing.

[0084] Figure 3 This is a characterization of the mechanical properties of the composite material of Example 2 of the present invention.

[0085] Depend on Figure 3It can be seen that while maintaining antistatic properties, the material has a tensile strength of 94 MPa and an elongation at break of 120%.

[0086] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A copolymerized polyetheretherketone composite material, characterized in that: The invention comprises a copolymerized polyetheretherketone resin, hydroxylated carbon nanotubes dispersed in the copolymerized polyetheretherketone resin, and wollastonite modified by a silane coupling agent; At 400° C. and 500N, the melt index of the copolymerized polyetheretherketone resin is 23 to 80 g / 10 min.

2. The copolymerized polyetheretherketone composite material according to claim 1, characterized in that Calculated by mass fraction, the mass fraction of the copolymerized polyetheretherketone resin in the copolymerized polyetheretherketone composite material is 80-95%, the mass fraction of the hydroxylated carbon nanotubes is 3-10%, and the mass fraction of the silane coupling agent-modified wollastonite is 2-10%; the sum of the mass fractions of the copolymerized polyetheretherketone resin, the hydroxylated carbon nanotubes and the silane coupling agent-modified wollastonite is 100%.

3. The copolymerized polyetheretherketone composite material according to claim 1 or 2, characterized in that: The method for preparing the hydroxylated carbon nanotubes comprises the following steps: Mixing concentrated sulfuric acid, concentrated nitric acid and carbon nanotubes and performing a hydroxylation treatment, then performing solid-liquid separation on the obtained product, washing, drying and vacuum annealing the obtained solid to obtain the hydroxylated carbon nanotubes; The total volume ratio of the concentrated sulfuric acid and concentrated nitric acid to the carbon nanotubes is 100 mL:1 g; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1; the mass concentration of the concentrated sulfuric acid is 98%; and the mass concentration of the concentrated nitric acid is 60-68%.

4. The copolymerized polyetheretherketone composite material according to claim 3, characterized in that The aspect ratio of the carbon nanotubes is 200 to 1500:1; The carbon nanotubes include array carbon nanotubes.

5. The copolymerized polyetheretherketone composite material according to claim 3, characterized in that: The temperature of the hydroxylation treatment is 50-70° C., and the time is 60-120 minutes.

6. The copolymerized polyetheretherketone composite material according to claim 1, characterized in that The preparation method of the silane coupling agent-modified wollastonite comprises the following steps: Wollastonite and a solution of a silane coupling agent are mixed and then modified to obtain the silane coupling agent-modified wollastonite.

7. The copolymerized polyetheretherketone composite material according to claim 6, characterized in that: The silane coupling agent includes one or more of KH-550, KH-560 and KH-570; the mass ratio of the wollastonite to the silane coupling agent is 100:

1.

8. The copolymerized polyetheretherketone composite material according to claim 6 or 7, characterized in that: The modification temperature is 60-90° C. and the modification time is 60-90 minutes.

9. The method for preparing the copolymerized polyetheretherketone composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: The copolymerized polyetheretherketone resin, hydroxylated carbon nanotubes and silane coupling agent-modified wollastonite are mixed and then melt-extruded and granulated; The temperature of the melt extrusion is 240-350°C.

10. A method for preparing a pipe, characterized in that: The following steps are involved: The copolymerized polyetheretherketone composite material according to any one of claims 1 to 8 or the copolymerized polyetheretherketone composite material prepared by the preparation method according to claim 9 is melt-extruded, and then the extruded tube blank is annealed to obtain the tube.

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