CN109096692B - Antistatic PEEK resin material and preparation method thereof - Google Patents
Antistatic PEEK resin material and preparation method thereof Download PDFInfo
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- CN109096692B CN109096692B CN201810537808.1A CN201810537808A CN109096692B CN 109096692 B CN109096692 B CN 109096692B CN 201810537808 A CN201810537808 A CN 201810537808A CN 109096692 B CN109096692 B CN 109096692B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
Abstract
The invention discloses an antistatic PEEK resin material and a preparation method thereof. The antistatic PEEK resin material consists of 70-90 parts of PEEK and 10-30 parts of modified carbon black in parts by mass, wherein the modified carbon black is obtained by performing surface treatment on the carbon black through N- (benzocyclobutene-4-yl) maleimide (or N-phenylmaleimide). According to the method, N- (benzocyclobutene-4-yl) maleimide (or N-phenylmaleimide) is adopted to carry out surface treatment on carbon black, so that the lipophilicity and the dispersibility of the carbon black are improved, the carbon black can be uniformly dispersed in PEEK, and the PEEK resin material has excellent elongation at break and surface resistivity; the benzocyclobutene groups have excellent thermal stability, so that the decomposition temperature of the modified carbon black reaches more than 450 ℃, and the thermal decomposition cannot occur at the PEEK processing temperature of 370-390 ℃.
Description
Technical Field
The invention belongs to the field of resin materials, and particularly relates to an anti-static PEEK resin material and a preparation method thereof.
Background
Polyetheretherketone, also known by the english name Polyetheretherketone (PEEK), is a linear aromatic polymer compound having chain segments in the main chain of the molecule. The PEEK resin is a special engineering plastic with excellent performance, and has more remarkable advantages compared with other special engineering plastics, such as high temperature resistance of 260 ℃, excellent mechanical properties, good self-lubricating property, chemical corrosion resistance, flame retardance, peeling resistance, wear resistance, poor resistance to strong nitric acid and concentrated sulfuric acid, radiation resistance and super-strong mechanical properties, and the PEEK is widely applied to the fields of aerospace, automobile manufacturing, electronics and electrical, medical treatment, food processing and the like.
The PEEK resin material has excellent electrical insulation, and in order to meet the requirement of special fields on antistatic performance of PEEK products, PEEK antistatic bars or plates are developed. In the traditional process, a carbon fiber or carbon black and other conductive materials are usually blended with a PEEK material to prepare the antistatic PEEK material, but due to the agglomeration of the carbon fiber, the direct blending of the carbon fiber or the carbon black and the PEEK can cause the toughness of the whole material to be poor, and the agglomeration can cause the carbon fiber to be uniformly distributed in a PEEK matrix, so that the surface resistance of the whole material can be influenced, and the antistatic performance of the PEEK material can be reduced.
Modifying carbon fiber materials such as carbon black before blending with PEEK is a breakthrough to solve the above problems. For example, chinese patent application No. CN 201510738521.1 discloses an antistatic PEEK resin material, which is made of 68-84 parts of PEEK, 15-30 parts of chopped carbon fibers, and 1-2 parts of carbon nanotubes, wherein the carbon nanotubes are surface-treated with sulfonated PEEK, the sulfonation degree of the sulfonated PEEK is 70-80, and the chopped carbon fibers are surface-oxidized (at 500 ℃ for 6-8 hours).
The PEEK resin material also has the following defects: (1) the carbon nano tube is modified by the highly sulfonated PEEK, but the heat stability of the highly sulfonated PEEK is lower, the weight loss at 400 ℃ can reach 35 percent, the processing temperature of the PEEK is usually between 370 and 390 ℃, and the highly sulfonated PEEK can be decomposed during the PEEK processing, so that the highly sulfonated PEEK can lose the effect on the surface modification of the carbon black; (2) the chopped carbon fiber needs to be treated at 500 ℃ for 6-8 hours to realize surface modification, the modification condition is harsh, and the requirement on equipment is high; (3) the elongation at break of the finally obtained PEEK resin material is only 8.4-11.7%, the lower toughness of the material indicates that the agglomeration problem of the carbon fibers is not completely solved, and the distribution of the carbon fibers in the material is still uneven.
Disclosure of Invention
The invention aims to provide an antistatic PEEK resin material which is uniform in carbon fiber distribution, free of carbon fiber agglomeration and high in thermal stability.
The above object is not achieved, and the technical scheme of the application is as follows:
an antistatic PEEK resin material comprises, by mass, 70-90 parts of PEEK and 10-30 parts of modified carbon black, wherein the modified carbon black is obtained by subjecting carbon black to surface treatment of N- (benzocyclobutene-4-yl) maleimide.
This application adopts N- (benzocyclobutene-4-yl) maleimide to carry out surface treatment to carbon black, and N- (benzocyclobutene-4-yl) maleimide can improve the lipophilicity and the dispersibility of carbon black to carbon black can evenly disperse in PEEK, the carbon black aggregate can not appear, makes antistatic PEEK resin material have good elongation at break and antistatic properties.
And the benzocyclobutene group and the imide five-membered ring structure of the N- (benzocyclobutene-4-yl) maleimide have excellent thermal stability, and the decomposition temperature of the modified carbon black modified by the N- (benzocyclobutene-4-yl) maleimide reaches more than 450 ℃, so that the modified carbon black still has excellent thermal stability and cannot be thermally decomposed at the PEEK processing temperature of 370-390 ℃.
Moreover, the N- (benzocyclobutene-4-yl) maleimide has good mechanical and electrical properties, and can further improve the antistatic performance and tensile strength of the antistatic PEEK resin material.
Preferably, the modified carbon black is obtained by subjecting carbon black to surface treatment with N- (benzocyclobutene-4-yl) maleimide and N-phenylmaleimide.
After the carbon black is modified by adopting the N-phenylmaleimide and the N- (benzocyclobutene-4-yl) maleimide simultaneously, the performance of the PEEK bar can be further improved, probably because the strength of particles formed by grafting or covering a polymer formed by the Diels-Alder reaction between the N-phenylmaleimide and the N- (benzocyclobutene-4-yl) maleimide on the surface of the carbon black is higher, the dispersity is further improved, and the PEEK bar can obtain good elongation at break and surface resistivity.
Preferably, the antistatic PEEK resin material consists of 80-85 parts of PEEK and 15-20 parts of modified carbon black in parts by mass.
The application also provides a preparation method of the antistatic PEEK resin material, which sequentially comprises the following steps:
(1) preparing modified carbon black;
the application provides two preparation methods of modified carbon black: a and B, wherein the A method comprises: mixing carbon black with N- (benzocyclobutene-4-yl) maleimide, and carrying out Diels-Alder reaction to obtain modified carbon black subjected to surface treatment by the N- (benzocyclobutene-4-yl) maleimide;
the method B comprises the following steps: mixing carbon black, N- (benzocyclobutene-4-yl) maleimide and N-phenylmaleimide, and carrying out Diels-Alder reaction to obtain the modified carbon black subjected to surface treatment by the N- (benzocyclobutene-4-yl) maleimide and the N-phenylmaleimide.
When the method A is adopted for modifying the carbon black, not only can the N- (benzocyclobutene-4-yl) maleimide and the conjugated diene structure on the surface of the carbon black generate Diels-Alder reaction, but also the N- (benzocyclobutene-4-yl) maleimide is grafted on the surface of the carbon black (grafting is realized by polymerizing an imide five-membered ring and the conjugated diene into a six-membered ring), so that the dispersibility, the lipophilicity and the thermal stability of the carbon black are improved; and a Diels-Alder reaction between N- (benzocyclobuten-4-yl) maleimide monomers occurs (benzocyclobutene of the N- (benzocyclobuten-4-yl) maleimide monomer is ring-opened at high heat and an imide five-membered ring on another N- (benzocyclobuten-4-yl) maleimide is polymerized into a six-membered ring), so that the N- (benzocyclobutene-4-yl) maleimide can aggregate the carbon black particles into chain-shaped or grape-shaped or net-shaped aggregates, wherein the aggregates contain a plurality of repeating units of 'N- (benzocyclobutene-4-yl) maleimide + carbon black + N- (benzocyclobutene-4-yl) maleimide', and the two repeating units are connected through respective N- (benzocyclobutene-4-yl) maleimide; and because the imide five-membered ring of the N- (benzocyclobutene-4-yl) maleimide has steric hindrance effect, the long polymer chain can not rotate and agglomerate; more N- (benzocyclobutene-4-yl) maleimide can be grafted on the same carbon black particle, so that the aggregate is grape-shaped or net-shaped; the modified carbon black has extremely high structurability, a space network which is not easy to damage is formed, and N- (benzocyclobutene-4-yl) maleimide has good mechanical and electrical properties, so that an infinite chain type conductive structure can be formed in the space network, and the PEEK is endowed with excellent conductivity.
Similarly, when the carbon black is modified by the method B, not only can N- (benzocyclobutene-4-yl) maleimide and N-phenylmaleimide be grafted on the surface of the carbon black, but also Diels-Alder reactions can occur among N- (benzocyclobutene-4-yl) maleimide monomers, N- (benzocyclobutene-4-yl) maleimide monomers and N-phenylmaleimide monomers, so that chain type conductive structures are more closely stacked and the network degree is higher in a space network of formed aggregates, the conductivity of the antistatic PEEK resin material can be further enhanced while the dispersibility, lipophilicity and thermal stability of the carbon black are further improved, and the excellent antistatic performance is endowed.
In both the method A and the method B, before Diels-Alder reaction, the carbon black needs to be dried at 110 ℃ for more than 25h and then used after cooling. Carbon black has some water absorption, but water molecules adsorbed on carbon black affect subsequent reactions of carbon black with N- (benzocyclobutene-4-yl) maleimide or N- (benzocyclobutene-4-yl) maleimide and N-phenylmaleimide, affecting surface modification of carbon black.
When the method A is used for modifying the carbon black, the mass ratio of the N- (benzocyclobutene-4-yl) maleimide to the carbon black is (0.01-30): 100; preferably, the mass ratio of the N- (benzocyclobutene-4-yl) maleimide to the carbon black is (3-7): 100; more preferably, the mass ratio of N- (benzocyclobutene-4-yl) maleimide to carbon black is 6: 100; at the above mixing ratio, N- (benzocyclobutene-4-yl) maleimide is most effective in improving the thermal stability of carbon black.
When the carbon black is modified by the method B, the mass ratio of the N- (benzocyclobutene-4-yl) maleimide to the N-phenylmaleimide to the carbon black is (2-4): (2-4): 100. Compared with the surface modification by simply using the N- (benzocyclobutene-4-yl) maleimide, after the surface modification is carried out by adopting the N- (benzocyclobutene-4-yl) maleimide and the N-phenyl maleimide together, the use amount of the N- (benzocyclobutene-4-yl) maleimide can be reduced while the effect which can be achieved by independently modifying the N- (benzocyclobutene-4-yl) maleimide is achieved, and the carbon black modification cost is greatly saved.
In the above preparation method of modified carbon black, the reaction conditions of the Diels-Alder reaction are as follows: reacting at 150 ℃ and 200 ℃ for 1-7 h. Preferably, the reaction conditions of the Diels-Alder reaction in method a are: reacting for 4-5h at 170 ℃; the reaction conditions of the Diels-Alder reaction in the method B are as follows: reacting for 3-4h at 200 ℃.
(2) Uniformly mixing the modified carbon black and the PEEK according to the preset weight part, drying at the temperature of 100-200 ℃ for 4-12h, and cooling;
(3) and injecting the cooled mixed material into a molding material at the temperature of 370-390 ℃.
The injection molding process adopts the conventional PEEK injection molding process and injection molding machine in the prior art, and the section obtained by injection molding can be a bar, a plate, a sheet or a film as required.
Compared with the prior art, the invention has the beneficial effects that:
(1) this application adopts N- (benzocyclobutene-4-yl) maleimide to carry out surface treatment to carbon black to improve the lipophilicity and the dispersibility of carbon black, make carbon black can the homodisperse in PEEK, the carbon black aggregate can not appear, make antistatic PEEK resin material have good elongation at break and antistatic properties.
(2) The N- (benzocyclobutene-4-yl) maleimide adopted by the application has benzocyclobutene groups and imide five-membered rings, the two groups have excellent thermal stability, and the decomposition temperature of the modified carbon black modified by the N- (benzocyclobutene-4-yl) maleimide reaches more than 450 ℃, so that the modified carbon black still has excellent thermal stability and cannot be thermally decomposed at the PEEK processing temperature of 370-390 ℃; moreover, the N- (benzocyclobutene-4-yl) maleimide has good mechanical and electrical properties, and can further improve the antistatic performance and tensile strength of the antistatic PEEK resin material.
(3) According to the method, after the carbon black is modified by replacing part of N- (benzocyclobutene-4-yl) maleimide with N-phenylmaleimide, the performance of the PEEK bar can be further improved, probably because the strength of particles formed by grafting or covering a polymer formed by the Diels-Alder reaction between the N-phenylmaleimide and the N- (benzocyclobutene-4-yl) maleimide on the surface of the carbon black is higher, the dispersity is further improved, and the PEEK bar can obtain good elongation at break and antistatic performance.
(4) The method adopts a dry method to modify the carbon black, omits the post-treatment process of wet modification, and has simple and convenient process.
Detailed Description
The technical means of the present invention will be described in further detail below with reference to specific embodiments.
The following examples used PEEK, carbon black, N- (benzocyclobutene-4-yl) maleimide and N-phenylmaleimide, which were commercially available, and reference was also made to the literature for N- (benzocyclobutene-4-yl) maleimide: TanL.S., Arnlod F.E., Resin systems derived from benzocyclobutene-maleimidocopouns, US,4916235[ P]The method described in 1990-04-10. The prepared PEEK bars are all in the same type
In the meantime.
Example 1
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) preparing modified carbon black;
drying the carbon black at the temperature of 100-110 ℃ for more than 25h, cooling, mixing with N- (benzocyclobutene-4-yl) maleimide in a mass ratio of 100:0.01, uniformly dispersing in a high-speed mixer, transferring into a reaction kettle at the temperature of 150 ℃ for Diels-Alder reaction for 7h to obtain the modified carbon black.
(2) Taking 70 parts of PEEK and 30 parts of modified carbon black, putting the PEEK and the modified carbon black into a high-speed mixer, uniformly mixing, putting the mixture into a 100 ℃ oven to remove water, and cooling for later use after the mixture is completely dried;
(3) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
Example 2
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) preparing modified carbon black;
drying the carbon black at the temperature of 100-110 ℃ for more than 25h, cooling, mixing the carbon black with N- (benzocyclobutene-4-yl) maleimide in a mass ratio of 100:3, uniformly dispersing in a high-speed mixer, transferring into a reaction kettle at the temperature of 170 ℃ for Diels-Alder reaction for 4h to obtain the modified carbon black.
(2) Taking 80 parts of PEEK and 20 parts of modified carbon black, putting the PEEK and the modified carbon black into a high-speed mixer, uniformly mixing, putting the mixture into a 150 ℃ oven to remove water, and cooling for later use after the mixture is completely dried;
(3) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
Example 3
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) preparing modified carbon black;
drying the carbon black at the temperature of 100-110 ℃ for more than 25h, cooling, mixing with N- (benzocyclobutene-4-yl) maleimide in a mass ratio of 100:5, uniformly dispersing in a high-speed mixer, transferring into a reaction kettle at the temperature of 170 ℃ for Diels-Alder reaction for 4h to obtain the modified carbon black.
(2) Taking 80 parts of PEEK and 20 parts of modified carbon black, putting the PEEK and the modified carbon black into a high-speed mixer, uniformly mixing, putting the mixture into a 150 ℃ oven to remove water, and cooling for later use after the mixture is completely dried;
(3) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
Example 4
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) preparing modified carbon black;
drying the carbon black at the temperature of 100-110 ℃ for more than 25h, cooling, mixing with N- (benzocyclobutene-4-yl) maleimide in a mass ratio of 100:7, uniformly dispersing in a high-speed mixer, transferring into a reaction kettle at the temperature of 170 ℃ for Diels-Alder reaction for 5h to obtain the modified carbon black.
(2) Taking 85 parts of PEEK and 15 parts of modified carbon black, putting the PEEK and the 15 parts of modified carbon black into a high-speed mixer, uniformly mixing, putting the mixture into a 200 ℃ oven to remove water, and cooling the mixture for later use after the mixture is completely dried;
(3) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
Example 5
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) preparing modified carbon black;
drying the carbon black at the temperature of 100-110 ℃ for more than 25h, cooling, mixing with N- (benzocyclobutene-4-yl) maleimide in a mass ratio of 100:15, uniformly dispersing in a high-speed mixer, transferring into a reaction kettle at the temperature of 200 ℃ for Diels-Alder reaction for 5h to obtain the modified carbon black.
(2) Taking 85 parts of PEEK and 15 parts of modified carbon black, putting the PEEK and the 15 parts of modified carbon black into a high-speed mixer, uniformly mixing, putting the mixture into a 200 ℃ oven to remove water, and cooling the mixture for later use after the mixture is completely dried;
(3) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
Example 6
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) preparing modified carbon black;
drying the carbon black at the temperature of 100-110 ℃ for more than 25h, cooling, mixing with N- (benzocyclobutene-4-yl) maleimide in a mass ratio of 100:30, uniformly dispersing in a high-speed mixer, transferring into a reaction kettle at the temperature of 200 ℃ for Diels-Alder reaction for 7h to obtain the modified carbon black.
(2) Taking 90 parts of PEEK and 10 parts of modified carbon black, putting the mixture into a high-speed mixer, uniformly mixing, putting the mixture into a 200 ℃ oven to remove water, and cooling the mixture for later use after the mixture is completely dried;
(3) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
Example 7
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) preparing modified carbon black;
drying the carbon black at the temperature of 100-110 ℃ for more than 25h, cooling, mixing with N- (benzocyclobutene-4-yl) maleimide and N-phenylmaleimide in a mass ratio of 100:2:4, uniformly dispersing in a high-speed mixer, transferring into a reaction kettle at the temperature of 170 ℃ for Diels-Alder reaction for 5h to obtain the modified carbon black.
(2) Taking 85 parts of PEEK and 15 parts of modified carbon black, putting the PEEK and the 15 parts of modified carbon black into a high-speed mixer, uniformly mixing, putting the mixture into a 200 ℃ oven to remove water, and cooling the mixture for later use after the mixture is completely dried;
(3) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
Example 8
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) preparing modified carbon black;
drying the carbon black at the temperature of 100-110 ℃ for more than 25h, cooling, mixing with N- (benzocyclobutene-4-yl) maleimide and N-phenylmaleimide in a mass ratio of 100:3:3, uniformly dispersing in a high-speed mixer, transferring into a reaction kettle at the temperature of 170 ℃ for Diels-Alder reaction for 5h to obtain the modified carbon black.
(2) Taking 85 parts of PEEK and 15 parts of modified carbon black, putting the PEEK and the 15 parts of modified carbon black into a high-speed mixer, uniformly mixing, putting the mixture into a 200 ℃ oven to remove water, and cooling the mixture for later use after the mixture is completely dried;
(3) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
Example 9
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) preparing modified carbon black;
drying the carbon black at the temperature of 100-110 ℃ for more than 25h, cooling, mixing with N- (benzocyclobutene-4-yl) maleimide and N-phenylmaleimide in a mass ratio of 100:4:2, uniformly dispersing in a high-speed mixer, transferring into a reaction kettle at the temperature of 170 ℃ for Diels-Alder reaction for 5h to obtain the modified carbon black.
(2) Taking 85 parts of PEEK and 15 parts of modified carbon black, putting the PEEK and the 15 parts of modified carbon black into a high-speed mixer, uniformly mixing, putting the mixture into a 200 ℃ oven to remove water, and cooling the mixture for later use after the mixture is completely dried;
(3) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
Example 10
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) preparing modified carbon black;
drying the carbon black at the temperature of 100-110 ℃ for more than 25h, cooling, mixing with N- (benzocyclobutene-4-yl) maleimide and N-phenylmaleimide in a mass ratio of 100:4:2, uniformly dispersing in a high-speed mixer, transferring into a reaction kettle at the temperature of 200 ℃ for Diels-Alder reaction for 3 h to obtain the modified carbon black.
(2) Taking 85 parts of PEEK and 15 parts of modified carbon black, putting the PEEK and the 15 parts of modified carbon black into a high-speed mixer, uniformly mixing, putting the mixture into a 200 ℃ oven to remove water, and cooling the mixture for later use after the mixture is completely dried;
(3) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
Comparative example 1
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) taking 85 parts of PEEK, 15 parts of carbon black, 5 parts of lubricant and 5 parts of dispersant, putting the mixture into a high-speed mixer, uniformly mixing the mixture, putting the mixture into a 200 ℃ oven to remove water, and cooling the mixture for later use after the mixture is completely dried;
(2) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
Comparative example 2
The preparation method of the antistatic PEEK resin material comprises the following steps:
(1) preparing modified carbon black;
drying the carbon black at the temperature of 100-110 ℃ for more than 25h, cooling, mixing with N-phenylmaleimide in a mass ratio of 100:6, uniformly dispersing in a high-speed mixer, transferring into a reaction kettle at the temperature of 200 ℃ for Diels-Alder reaction for 3 h to obtain the modified carbon black.
(2) Taking 85 parts of PEEK and 15 parts of modified carbon black, putting the PEEK and the 15 parts of modified carbon black into a high-speed mixer, uniformly mixing, putting the mixture into a 200 ℃ oven to remove water, and cooling the mixture for later use after the mixture is completely dried;
(3) transferring the cooled mixed material into an injection molding machine, and injecting at 370-390 ℃ to mold into a bar.
The PEEK bars prepared in the above examples were subjected to performance tests, and the test results are shown in Table 1.
TABLE 1
| Examples | Tensile strength/MPa | Elongation at break/% | Surface resistivity/omega |
| Example 1 | 88 | 50％ | 8×106 |
| Example 2 | 105 | 68％ | 2×106 |
| Example 3 | 117 | 75％ | 1.4×106 |
| Example 4 | 109 | 70％ | 1.8×106 |
| Example 5 | 94 | 57％ | 6×106 |
| Example 6 | 92 | 55％ | 6×106 |
| Example 7 | 105 | 72％ | 2×106 |
| Example 8 | 108 | 71％ | 1.7×106 |
| Example 9 | 112 | 74％ | 1.5×106 |
| Example 10 | 119 | 77％ | 1×106 |
| Comparative example 1 | 48 | 10％ | 4×1010 |
| Comparative example 2 | 60 | 47％ | 7×1012 |
As shown in Table 1, when the carbon black is graft-modified by N- (benzocyclobutene-4-yl) maleimide with a proper proportion (examples 2-4), the tensile strength and the elongation at break of the obtained PEEK bar are effectively improved, and the surface resistivity is as low as 1.4 × 106Omega; while examples 5 and 6 have good tensile strength but relatively low elongation at break, excessive poly-N-phenylmaleimide is probably formed during modification to wrap the surface of carbon black, resulting in insufficient toughness of the modified carbon black.
In the modification of carbon black, if only N-phenylmaleimide was used for the modification (comparative example 2), the properties of the obtained PEEK bar were not satisfactory, but when N-phenylmaleimide was used in place of part of N- (benzocyclobuten-4-yl) maleimide (examples 7 to 10), the properties of the obtained PEEK bar were not only similar to those of examples 2 to 4, but also improved by adjusting the ratio of N-phenylmaleimide to N- (benzocyclobuten-4-yl) maleimide, possibly because the polymer formed by Diels-Alder reaction of N-phenylmaleimide and N- (benzocyclobuten-4-yl) maleimide could form a chain-type conductive structure more densely packed after grafting or covering the surface of carbon black, The spatial network with higher network degree further enhances the conductivity of the antistatic PEEK resin material and endows the antistatic PEEK resin material with excellent antistatic performance.
Claims (5)
1. An antistatic PEEK resin material is characterized by comprising 70-90 parts of PEEK and 10-30 parts of modified carbon black in parts by mass, wherein the modified carbon black is obtained by performing surface treatment on the carbon black through N- (benzocyclobutene-4-yl) maleimide;
the preparation method of the modified carbon black comprises the following steps: mixing carbon black with N- (benzocyclobutene-4-yl) maleimide, and carrying out Diels-Alder reaction to obtain modified carbon black subjected to surface treatment by the N- (benzocyclobutene-4-yl) maleimide;
the mass ratio of the N- (benzocyclobutene-4-yl) maleimide to the carbon black is (0.01-30) to 100;
the reaction conditions of the Diels-Alder reaction are as follows: reacting at 150 ℃ and 200 ℃ for 1-7 h.
2. An antistatic PEEK resin material is characterized by comprising 70-90 parts of PEEK and 10-30 parts of modified carbon black in parts by mass, wherein the modified carbon black is obtained by performing surface treatment on the carbon black through N- (benzocyclobutene-4-yl) maleimide and N-phenylmaleimide;
the preparation method of the modified carbon black comprises the following steps: mixing carbon black, N- (benzocyclobutene-4-yl) maleimide and N-phenylmaleimide, and carrying out Diels-Alder reaction to obtain modified carbon black subjected to surface treatment by the N- (benzocyclobutene-4-yl) maleimide and the N-phenylmaleimide;
the mass ratio of the N- (benzocyclobutene-4-yl) maleimide to the N-phenylmaleimide to the carbon black is (2-4) to 100;
the reaction conditions of the Diels-Alder reaction are as follows: reacting at 150 ℃ and 200 ℃ for 1-7 h.
3. The antistatic PEEK resin material of claim 1 or 2, wherein the carbon black is dried at 100-110 ℃ for more than 25 hours before Diels-Alder reaction, and then cooled for use.
4. The antistatic PEEK resin material as claimed in claim 1 or 2, which consists of 80 to 85 parts by mass of PEEK and 15 to 20 parts by mass of modified carbon black.
5. The method for preparing an antistatic PEEK resin material as claimed in any one of claims 1 to 4, comprising the following steps in sequence:
(1) preparing modified carbon black;
(2) uniformly mixing the modified carbon black and the PEEK according to the preset weight part, drying at the temperature of 100-200 ℃ for 4-12h, and cooling;
(3) and injecting the cooled mixed material into a molding material at the temperature of 370-390 ℃.
Priority Applications (1)
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Address after: No. 313200, Guangming Lake Economic Development Zone, Zhejiang Province Patentee after: Zhejiang Kesai New Material Technology Co.,Ltd. Address before: No. 313200, Guangming Lake Economic Development Zone, Zhejiang Province Patentee before: ZHEJIANG DEQING CONCEPTFE PLASTIC PRODUCTS Co.,Ltd. |