CN116427168A - Poly (p-aminophenol) -modified ultra-high molecular weight polyethylene fiber and preparation method of composite material thereof - Google Patents
Poly (p-aminophenol) -modified ultra-high molecular weight polyethylene fiber and preparation method of composite material thereof Download PDFInfo
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- CN116427168A CN116427168A CN202310210076.6A CN202310210076A CN116427168A CN 116427168 A CN116427168 A CN 116427168A CN 202310210076 A CN202310210076 A CN 202310210076A CN 116427168 A CN116427168 A CN 116427168A
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- 239000000835 fiber Substances 0.000 title claims abstract description 137
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 105
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 105
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 239000003822 epoxy resin Substances 0.000 claims abstract description 63
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 63
- 230000004048 modification Effects 0.000 claims abstract description 57
- 238000012986 modification Methods 0.000 claims abstract description 57
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 108010001336 Horseradish Peroxidase Proteins 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002715 modification method Methods 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 3
- 239000010452 phosphate Substances 0.000 claims 3
- 239000008055 phosphate buffer solution Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 24
- 125000003277 amino group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/335—Amines having an amino group bound to a carbon atom of a six-membered aromatic ring
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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Abstract
The invention discloses a preparation method of a poly-p-aminophenol modified ultra-high molecular weight polyethylene fiber and a composite material thereof. The invention takes ultra-high molecular weight polyethylene fiber as a raw material, horseradish peroxidase as a catalyst, hydrogen peroxide as an oxidant, p-aminophenol as a monomer and phosphate buffer solution as a reaction medium. The ultra-high molecular weight polyethylene fiber is soaked in phosphate buffer solution containing horseradish peroxidase and para-aminophenol, after hydrogen peroxide is added, the para-aminophenol forms free radicals, and a poly-para-aminophenol coating is formed on the surface of the ultra-high molecular weight polyethylene through covalent bond and non-covalent bond. The modification steps are repeated, and the polymer content on the surface of the fiber can be further improved after the 3 rd modification, so that the bonding capability of the ultra-high molecular weight polyethylene fiber and the epoxy resin is enhanced, and the performance of the composite material is improved.
Description
Technical Field
The invention belongs to the technical field of fiber/epoxy resin composite materials, and particularly relates to a polyaminophenol modified ultra-high molecular weight polyethylene fiber and a preparation method of the composite material.
Background
The ultra-high molecular weight polyethylene fiber is spun from polyethylene with molecular weight of 100-500 ten thousand, has smooth surface, luster, white color and minimum density, and has high strength, good impact resistance, wear resistance, corrosion resistance and the like. In ultra-high molecular weight polyethylene fiber applications, compounding with a resin matrix is most desirable. However, the ultra-high molecular weight polyethylene fiber is a linear polymer, only contains hydrocarbon two elements, has a smooth surface, does not contain active groups, and is difficult to chemically graft with other compounds, so that chemical bond combination is difficult to generate between the fiber and a resin matrix, and stronger interaction force is difficult to generate between fiber molecules and resin matrix molecules, so that the cohesiveness of the fiber and the resin matrix is poor. Therefore, the ultra-high molecular weight polyethylene fiber reinforced composite material is easy to deglue, crack a resin matrix and the like in the use process, and the application of the ultra-high molecular weight polyethylene fiber in the field of composite materials is greatly limited. Therefore, surface modification of the ultra-high molecular weight polyethylene fiber is necessary.
Currently, the means for modifying ultra-high molecular weight polyethylene fibers can be broadly divided into dry modification and wet modification, the former is further divided into gas phase oxidation, radiation grafting, plasma treatment and the like; conventional wet modification is more widely used than dry modification, and includes chemical etching, polymer coating, and the like.
The invention aims to provide a novel method for modifying ultra-high molecular weight polyethylene fibers by poly (p-aminophenol), which solves the problems in the prior art.
Disclosure of Invention
The invention aims to provide a method which is simple to operate and environment-friendly, adopts a means of catalyzing polymerization of para-aminophenol by biological enzyme, and ensures that the poly-para-aminophenol is adhered to the surface of the ultra-high molecular weight polyethylene through covalent bond and non-covalent bond, thereby not only increasing the surface roughness of fibers, but also providing rich amino groups to enable the poly-para-aminophenol to react with epoxy groups in epoxy resin prepolymer to form chemical bonds, thereby improving the bonding force between the ultra-high molecular weight polyethylene and the epoxy resin and improving the mechanical property of the composite material.
The invention provides a preparation method of a poly-p-aminophenol modified ultra-high molecular weight polyethylene fiber and a composite material thereof, which comprises the following steps:
(1) Cleaning of ultra-high molecular weight polyethylene fibers
Soaking ultra-high molecular weight polyethylene fibers into deionized water, performing ultrasonic treatment for 2-3h, removing impurities such as dust on the surfaces of the fibers, taking out, and drying in a blast drying oven at 50-60 ℃.
(2) Modification 1: poly (p-aminophenol) coated ultra-high molecular weight polyethylene fiber
Adding 3-15mg of horseradish peroxidase into about 1L of phosphate buffer solution, soaking ultra-high molecular weight polyethylene fiber in the solution, and placing on a shaking table for shaking. 400mL of an aqueous solution containing 2-6g of p-aminophenol was prepared and added to the above solution in 3-4 portions. Preparing 12-36mL of 5% hydrogen peroxide, and adding the solution 13-15 times. And continuing shaking for 30-50min after the dripping is finished. Taking out the fiber, washing with water and ethanol for 2-3 times, and drying in a forced air drying oven at 50-60deg.C. Under the catalysis of horseradish peroxidase and the oxidation of hydrogen peroxide, the para-aminophenol can form para-aminophenol free radicals, and the free radicals can react with ultra-high molecular weight polyethylene or interact with the ultra-high molecular weight polyethylene to generate poly-para-aminophenol which is coated on the surface of the fiber. In addition, although a phenol oxygen radical is first generated in p-aminophenol, this radical can be converted into a carbon radical on the benzene ring by resonance, and thus the poly-p-aminophenol on the fiber surface contains not only a large amount of amino groups but also a large amount of phenolic hydroxyl groups.
(3) Modification 2: poly (p-aminophenol) coated ultra-high molecular weight polyethylene fiber
The step is identical to the step (2). Under the action of horseradish peroxidase and hydrogen peroxide, the phenolic hydroxyl groups on the surface of the fiber can still form free radicals to be coupled with the para-aminophenol in the solution, so that the content of the polymer on the surface of the fiber is greatly improved by repeated modification.
(4) 3 rd modification: poly (p-aminophenol) coated ultra-high molecular weight polyethylene fiber
The step is identical to the step (2). The modification is performed for a plurality of times, because the excessive concentration of hydrogen peroxide in the reaction solution can lead to the inactivation of horseradish peroxidase, so that the grafting is performed for a plurality of times. The fiber surface after 3 times of modification is rich in amino groups, can react with epoxy groups in the epoxy resin prepolymer to form chemical bonds, and greatly improves the binding force between the fiber and the resin, thereby obviously improving the mechanical property of the composite material.
(5) Preparation of a monofilament pull-out strength test sample: the method comprises the steps of passing ultra-high molecular weight polyethylene fiber monofilaments before and after modification through a self-made cylindrical mold, injecting an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:40-50) into the mold, placing the prepared sample in a vacuum oven at 20-30 ℃, curing for 7.5-8.5 hours under vacuum conditions to remove bubbles, taking out, placing in the oven, heating to 115-125 ℃ to cure for 14-16 hours, and demolding and testing.
(6) Preparation of transverse fiber bundle test samples: pre-soaking the ultra-high molecular weight polyethylene chopped fiber bundles before and after modification in resin, transversely fixing the resin in the middle part of a columnar mould, pouring an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:40-50) into the mould, placing the prepared sample in a vacuum oven at 20-30 ℃, curing for 7.5-8.5 hours under the vacuum condition to remove bubbles, taking out the sample, placing the sample in the oven, heating to 115-125 ℃ to cure for 14-16 hours, and demoulding and testing.
(7) Preparation of a longitudinal reinforced tensile test sample: pre-soaking the ultra-high molecular weight polyethylene long fiber bundles before and after modification in resin, then longitudinally placing the resin in a dumbbell-shaped mold, pouring an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:40-50) into the mold, wherein the ultra-high molecular weight polyethylene fibers account for 1.5-2.5% of the mass ratio of the epoxy resin. And (3) placing the prepared sample in a vacuum oven at 20-30 ℃, curing for 7.5-8.5 hours under vacuum conditions to remove bubbles, taking out, placing in the oven, heating to 115-125 ℃ for curing for 14-16 hours, demolding and testing.
The beneficial effects of this application lie in:
1. the invention provides a new modification method, which is characterized in that ultra-high molecular weight polyethylene fibers are immersed in para-aminophenol/horseradish peroxidase/hydrogen peroxide solution, para-aminophenol and para-aminophenol free radicals are generated under the catalysis of horseradish peroxidase and the action of hydrogen peroxide, then poly-para-aminophenol is firmly adsorbed on the surfaces of the ultra-high molecular weight polyethylene fibers through covalent bond or non-covalent bond action, and the para-aminophenol contains phenolic hydroxyl groups and amino groups. And the poly-p-aminophenol contains a large amount of amino units, so that the poly-p-aminophenol can form chemical bonds with epoxy groups in the epoxy resin prepolymer, and the binding force between the modified material and the epoxy resin is greatly improved.
2. In the modification process, hydrogen peroxide is added for multiple times, and the fiber surface modified for 3 times is rich in amino groups, so that the fiber surface modified for 3 times can react with epoxy groups in the epoxy resin prepolymer to form chemical bonds, the binding force between the fiber and the resin is greatly improved, and the mechanical property of the composite material is remarkably improved.
3. Compared with the traditional modification, the method has simple reaction conditions, is easy to operate and is suitable for industrial production.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
In the drawings:
FIG. 1 is a schematic diagram of the modification process of ultra-high molecular weight polyethylene fibers.
Figure 2 ultra high molecular weight polyethylene fiber surface infrared spectrum after 3 modifications (ATR mode test) of example 2.
FIG. 3 tensile breaking strength of ultra high molecular weight polyethylene fibers after various modifications of example 2.
FIG. 4 interfacial shear strength of ultra high molecular weight polyethylene fibers and epoxy after various modifications of example 2.
FIG. 5 tensile breaking strength of transverse cellulose prepared from ultra high molecular weight polyethylene fibers and epoxy resin after various modifications of example 2.
FIG. 6 tensile break strength of ultra high molecular weight polyethylene fiber reinforced epoxy resin composites after various modifications of example 2.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that, the azimuth or positional relationship indicated by the terms "inner", "outer", etc. are based on the azimuth or positional relationship shown in the drawings, or the azimuth or positional relationship in which the inventive product is conventionally put in use, are merely for convenience of describing the present invention and simplifying the description, and are not indicative or implying that the apparatus or element to be referred to must have a specific azimuth, be configured and operated in a specific azimuth, and therefore, should not be construed as limiting the present invention.
Example 1:
(1) Washing the ultra-high molecular weight polyethylene fiber, immersing the ultra-high molecular weight polyethylene fiber into deionized water, performing ultrasonic treatment for 2 hours to remove impurities such as dust on the surface of the fiber, taking out, and drying in a blast drying oven at 50 ℃.
(2) Modification 1: the ultra-high molecular weight polyethylene fiber is soaked in about 1L of phosphate buffer solution, 3mg of horseradish peroxidase is added, and the ultra-high molecular weight polyethylene fiber is placed on a shaking table for shaking. 400mL of an aqueous solution containing 2g of p-aminophenol was prepared and added to the above solution in 4 portions of 100mL each. Preparing 12mL of 5% hydrogen peroxide, adding the solution into the solution for 14 times, wherein the dripping amount is the same every time, and the interval is 5 min. After the end of the dropwise addition, the shaking was continued for 30 min. The fibers were removed and rinsed 3 times with water and ethanol each, and dried in a forced air oven at 50 ℃.
(3) Modification 2: the step of wrapping the ultra-high molecular weight polyethylene fiber by the poly-p-aminophenol is completely the same as the step (2).
(4) 3 rd modification: the step of wrapping the ultra-high molecular weight polyethylene fiber by the poly-p-aminophenol is completely the same as the step (2).
(5) Preparation of a monofilament pull-out strength test sample: the ultra-high molecular weight polyethylene fiber monofilaments before and after modification were passed through a self-made cylindrical mold, and an epoxy resin/hardener system (epoxy resin:
the mass ratio of the curing agent is 100:45 Placing the prepared sample in a vacuum oven at 25 ℃, curing for 8 hours under vacuum conditions to remove bubbles, then taking out, placing in the oven, heating to 120 ℃ for curing for 15 hours, demolding and testing.
(6) Preparation of transverse fiber bundle test samples: pre-soaking the ultra-high molecular weight polyethylene chopped fiber bundles before and after modification in resin, transversely fixing the resin in the middle part of a columnar mould, pouring an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:45) into the mould, placing the prepared sample in a vacuum oven at 25 ℃, curing for 8 hours under the vacuum condition to remove bubbles, taking out the sample, placing the sample in the oven, heating to 120 ℃ for curing for 15 hours, demoulding and testing.
(7) Preparation of a longitudinal reinforced tensile test sample: pre-soaking the ultra-high molecular weight polyethylene long fiber bundles before and after modification in resin, longitudinally placing the resin in a dumbbell-shaped mold, pouring an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:45) into the mold, wherein the ultra-high molecular weight polyethylene fibers account for 2% of the mass ratio of the epoxy resin. And (3) placing the prepared sample in a vacuum oven at 25 ℃, curing for 8 hours under vacuum conditions to remove bubbles, taking out, placing in the oven, heating to 120 ℃ for curing for 15 hours, demoulding and testing.
The results are shown in Table 1: after the third modification, the tensile breaking strength of the ultra-high molecular weight polyethylene fiber, the interfacial shear strength of the ultra-high molecular weight polyethylene fiber and the epoxy resin, the tensile breaking strength of the transverse cellulose prepared by the ultra-high molecular weight polyethylene fiber and the epoxy resin and the tensile breaking strength of the ultra-high molecular weight polyethylene fiber reinforced epoxy resin composite material are respectively as follows: 3.09GPa, 0.93MPa, 19.16MPa and 153MPa. According to analysis, the addition of p-aminophenol is less, so that the amino content of the surface of the ultra-high molecular weight polyethylene fiber is lower, and the bonding force of the fiber and the epoxy resin interface is greatly affected by the number of chemical bonds between the amino group and the epoxy resin, so that the mechanical strength of the prepared sample of the embodiment is obviously lower than that of the prepared samples of the embodiments 2 and 3.
Example 2:
(1) Washing the ultra-high molecular weight polyethylene fiber, immersing the ultra-high molecular weight polyethylene fiber into deionized water, performing ultrasonic treatment for 2-3 hours to remove impurities such as dust on the surface of the fiber, taking out, and drying in a blast drying oven at 50-60 ℃.
(2) Modification 1: the ultra-high molecular weight polyethylene fiber is soaked in about 1L of phosphate buffer solution, 9mg of horseradish peroxidase is added, and the ultra-high molecular weight polyethylene fiber is placed on a shaking table for shaking. 400mL of an aqueous solution containing 4g of p-aminophenol was prepared and added to the above solution in 4 portions of 100mL each. Preparing 24mL of 5% hydrogen peroxide, adding the solution into the solution for 14 times, wherein the dripping amount is the same each time, and the interval is 4-5 min. After the end of the dropwise addition, the shaking was continued for 30 min. Taking out the fiber, washing with water and ethanol for 2-3 times, and drying in a forced air drying oven at 50-60deg.C.
(3) Modification 2: the step of wrapping the ultra-high molecular weight polyethylene fiber by the poly-p-aminophenol is completely the same as the step (2).
(4) 3 rd modification: the step of wrapping the ultra-high molecular weight polyethylene fiber by the poly-p-aminophenol is completely the same as the step (2).
(5) Preparation of a monofilament pull-out strength test sample: and (3) passing the ultra-high molecular weight polyethylene fiber monofilaments before and after modification through a self-made cylindrical mold, injecting an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:45) into the mold, placing the prepared sample in a vacuum oven at 25 ℃, curing for 8 hours under vacuum conditions to remove bubbles, taking out, placing in the oven, heating to 120 ℃, curing for 15 hours, and demolding and testing.
(6) Preparation of transverse fiber bundle test samples: pre-soaking the ultra-high molecular weight polyethylene chopped fiber bundles before and after modification in resin, transversely fixing the resin in the middle part of a columnar mould, pouring an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:45) into the mould, placing the prepared sample in a vacuum oven at 25 ℃, curing for 8 hours under the vacuum condition to remove bubbles, taking out the sample, placing the sample in the oven, heating to 120 ℃ for curing for 15 hours, demoulding and testing.
(7) Preparation of a longitudinal reinforced tensile test sample: pre-soaking the ultra-high molecular weight polyethylene long fiber bundles before and after modification in resin, longitudinally placing the resin in a dumbbell-shaped mold, pouring an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:45) into the mold, wherein the ultra-high molecular weight polyethylene fibers account for 2% of the mass ratio of the epoxy resin. And (3) placing the prepared sample in a vacuum oven at 25 ℃, curing for 8 hours under vacuum conditions to remove bubbles, taking out, placing in the oven, heating to 120 ℃ for curing for 15 hours, demoulding and testing.
The results are shown in Table 1: after the third modification, the tensile breaking strength of the ultra-high molecular weight polyethylene fiber, the interfacial shear strength of the ultra-high molecular weight polyethylene fiber and the epoxy resin, the tensile breaking strength of the transverse cellulose prepared by the ultra-high molecular weight polyethylene fiber and the epoxy resin and the tensile breaking strength of the ultra-high molecular weight polyethylene fiber reinforced epoxy resin composite material are respectively as follows: 3.29GPa, 1.26MPa, 25.16MPa and 193MPa.
Example 3:
(1) Washing the ultra-high molecular weight polyethylene fiber, immersing the ultra-high molecular weight polyethylene fiber into deionized water, performing ultrasonic treatment for 2-3 hours to remove impurities such as dust on the surface of the fiber, taking out, and drying in a blast drying oven at 50-60 ℃.
(2) Modification 1: the ultra-high molecular weight polyethylene fiber is soaked in about 1L of phosphate buffer solution, 15mg of horseradish peroxidase is added, and the ultra-high molecular weight polyethylene fiber is placed on a shaking table for shaking. 400mL of an aqueous solution containing 6g of p-aminophenol was prepared and added to the above solution in 4 portions of 100mL each. Preparing 36mL of 5% hydrogen peroxide, adding the solution into the solution for 14 times, wherein the dripping amount is the same each time, and the interval is 4-5 min. After the end of the dropwise addition, the shaking was continued for 30 min. Taking out the fiber, washing with water and ethanol for 2-3 times, and drying in a forced air drying oven at 50-60deg.C.
(3) Modification 2: the step of wrapping the ultra-high molecular weight polyethylene fiber by the poly-p-aminophenol is completely the same as the step (2).
(4) 3 rd modification: the step of wrapping the ultra-high molecular weight polyethylene fiber by the poly-p-aminophenol is completely the same as the step (2).
(5) Preparation of a monofilament pull-out strength test sample: and (3) passing the ultra-high molecular weight polyethylene fiber monofilaments before and after modification through a self-made cylindrical mold, injecting an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:45) into the mold, placing the prepared sample in a vacuum oven at 25 ℃, curing for 8 hours under vacuum conditions to remove bubbles, taking out, placing in the oven, heating to 120 ℃, curing for 15 hours, and demolding and testing.
(6) Preparation of transverse fiber bundle test samples: pre-soaking the ultra-high molecular weight polyethylene chopped fiber bundles before and after modification in resin, transversely fixing the resin in the middle part of a columnar mould, pouring an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:45) into the mould, placing the prepared sample in a vacuum oven at 25 ℃, curing for 8 hours under the vacuum condition to remove bubbles, taking out the sample, placing the sample in the oven, heating to 120 ℃ for curing for 15 hours, demoulding and testing.
(7) Preparation of a longitudinal reinforced tensile test sample: pre-soaking the ultra-high molecular weight polyethylene long fiber bundles before and after modification in resin, longitudinally placing the resin in a dumbbell-shaped mold, pouring an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:45) into the mold, wherein the ultra-high molecular weight polyethylene fibers account for 2% of the mass ratio of the epoxy resin. And (3) placing the prepared sample in a vacuum oven at 25 ℃, curing for 8 hours under vacuum conditions to remove bubbles, taking out, placing in the oven, heating to 120 ℃ for curing for 15 hours, demoulding and testing.
The results are shown in Table 1: after the third modification, the tensile breaking strength of the ultra-high molecular weight polyethylene fiber, the interfacial shear strength of the ultra-high molecular weight polyethylene fiber and the epoxy resin, the tensile breaking strength of the transverse cellulose prepared by the ultra-high molecular weight polyethylene fiber and the epoxy resin and the tensile breaking strength of the ultra-high molecular weight polyethylene fiber reinforced epoxy resin composite material are respectively as follows: 3.30GPa, 1.29MPa, 26.15MPa and 195MPa.
Example 4:
the difference between the embodiment and the embodiment 1 is that in the modification step, the hydrogen peroxide with the mass fraction of 5% is added into the reaction system at one time, and the influence of the hydrogen peroxide addition step on the modification of the high molecular weight polyethylene fiber is explored. The results of the mechanical properties of the samples are shown in Table 1. The result shows that the mechanical property of the sample is obviously reduced, because the hydrogen peroxide is added at one time to cause the concentration of the hydrogen peroxide in the reaction system to be excessively high instantaneously, the horseradish peroxidase is partially deactivated, the polymerization efficiency of the para-aminophenol is reduced, the content of amino on the surface of the fiber is finally lower, and the binding force between the fiber and the epoxy resin is deteriorated.
Example 5:
this example differs from example 1 in that in the modification step, an aqueous solution of para-aminophenol was added at one time, and the effect of the para-aminophenol addition step on the modification of the high molecular weight polyethylene fiber was investigated. The results of the mechanical properties of the samples are shown in Table 1. The results show that the mechanical properties of the sample are poor, because the concentration of the para-aminophenol in the system is instantaneously overlarge due to the fact that the para-aminophenol is added at one time, the capability of the poly-para-aminophenol for coating the ultra-high molecular weight polyethylene fiber is reduced, the amino content on the surface of the fiber is reduced, and the bonding force between the fiber and the epoxy resin is small.
Experimental example 1:
the modified high molecular weight polyethylene fibers prepared by the method of examples 1-5 are used for detecting the interfacial shear strength of the ultra-high molecular weight polyethylene fibers and the epoxy resin. Sample preparation: and (3) passing the ultra-high molecular weight polyethylene fiber monofilaments before and after modification through a self-made cylindrical mold, injecting an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:45) into the mold, placing the prepared sample in a vacuum oven at 25 ℃, curing for 8 hours under vacuum conditions to remove bubbles, taking out, placing in the oven, heating to 120 ℃, curing for 15 hours, and demolding to obtain a test sample. The experimental results are shown in table 1.
Experimental example 2:
the high molecular weight polyethylene fibers prepared as described in examples 1-5 were used to prepare epoxy resin composites. Sample preparation process: pre-soaking the ultra-high molecular weight polyethylene chopped fiber bundles before and after modification in resin, transversely fixing the resin in the middle of a columnar mould, pouring an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:45) into the mould, placing the prepared sample in a vacuum oven at 25 ℃, curing for 8 hours under the vacuum condition to remove bubbles, taking out the sample, placing the sample in the oven, heating to 120 ℃ for curing for 15 hours, and demoulding to obtain a test sample. The experimental results are shown in table 1.
Experimental example 3:
the high molecular weight polyethylene fibers prepared according to the methods of examples 1-5 were used to prepare epoxy resin composites for longitudinal reinforcement tensile testing. Sample preparation process: pre-soaking the ultra-high molecular weight polyethylene long fiber bundles before and after modification in resin, longitudinally placing the resin in a dumbbell-shaped mold, pouring an epoxy resin/curing agent system (the mass ratio of the epoxy resin to the curing agent is 100:45) into the mold, wherein the ultra-high molecular weight polyethylene fibers account for 2% of the mass ratio of the epoxy resin. And (3) placing the prepared sample in a vacuum oven, curing for 8 hours at 25 ℃ under vacuum conditions to remove bubbles, taking out, placing in the oven, heating to 120 ℃ for curing for 15 hours, and demolding to obtain the test sample. The experimental results are shown in table 1.
TABLE 1
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A modification method of ultra-high molecular weight polyethylene fiber is characterized in that: pre-treating, namely cleaning and drying the ultra-high molecular weight polyethylene fiber for later use; the modification treatment, namely adding horseradish peroxidase into a phosphate solution for multiple times, soaking the ultra-high molecular weight polyethylene fibers into the solution, adding pre-prepared para-aminophenol into the solution for multiple times, and adding pre-prepared hydrogen peroxide solution into the solution for multiple times and fully reacting; taking out the ultra-high molecular weight polyethylene fiber after the modification treatment is finished, washing and drying; the modification treatment step is carried out at least 3 times.
2. The method for modifying an ultra-high molecular weight polyethylene fiber according to claim 1, wherein: the pretreatment steps specifically include: soaking the ultra-high molecular weight polyethylene fibers in deionized water, performing ultrasonic treatment for 2-3h, removing impurities such as dust on the surfaces of the fibers, taking out, and drying in a blast drying oven at 50-60 ℃.
3. The method for modifying an ultra-high molecular weight polyethylene fiber according to claim 1, wherein: in the modification treatment step, 1L of the phosphate solution with the pH of 6.5-7.5 is prepared, and the addition amount of the horseradish peroxidase is 3-15mg.
4. The method for modifying an ultra-high molecular weight polyethylene fiber according to claim 1, wherein: the ultra-high molecular weight polyethylene fiber is soaked in phosphate solution containing the horseradish peroxidase and then is placed on a shaking table for shaking treatment.
5. The method for modifying an ultra-high molecular weight polyethylene fiber according to claim 1, wherein: in the step of preparing the aqueous solution of para-aminophenol, 2-6g of para-aminophenol is taken and added to 400mL of water.
6. The method for modifying an ultra-high molecular weight polyethylene fiber according to claim 1, wherein: the aqueous solution of the para-aminophenol is added into the reaction system for 3 to 4 times.
7. The method for modifying an ultra-high molecular weight polyethylene fiber according to claim 1, wherein: in the step of preparing the hydrogen peroxide solution, 12-36mL of 5% hydrogen peroxide is prepared, and the hydrogen peroxide solution is added into a reaction system for 13-15 times.
8. The method for modifying an ultra-high molecular weight polyethylene fiber according to claim 1, wherein: and continuing vibrating for 30-50min after the hydrogen peroxide solution is added.
9. The method for modifying an ultra-high molecular weight polyethylene fiber according to claim 1, wherein: in the washing and drying step, the ultra-high molecular weight polyethylene fibers are respectively washed 2-3 times by water and ethanol, and are put into a blast drying oven for drying at 50-60 ℃.
10. A preparation method of an ultra-high molecular weight polyethylene fiber composite material is characterized by comprising the following steps: preparing modified ultra-high molecular weight polyethylene fiber according to the method of claims 1-9, injecting epoxy resin and curing agent into a mold, wherein the mass ratio of the epoxy resin to the curing agent is 100:40-50, placing the prepared sample in a vacuum oven at 20-30 ℃, curing for 7.5-8.5 hours under vacuum condition to remove bubbles, then taking out, placing in the oven, heating to 115-125 ℃ to cure for 14-16 hours, and demoulding to obtain the composite material.
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| CN113667154A (en) * | 2021-09-22 | 2021-11-19 | 天津工业大学 | Preparation method for constructing hydrogen bond modified ultra-high molecular weight polyethylene fiber by using tannic acid and polyaniline |
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