Ultra-high molecular weight polyethylene fiber resin composite material interface regulation and control composition, interface regulation and control method and fiber resin composite material prepared by using interface regulation and control composition and interface regulation and control method

Abstract

The invention provides an ultra-high molecular weight polyethylene fiber resin composite material interface regulation composition which comprises the following components in parts by weight: 100 parts of ultra-high molecular weight polyethylene fiber, 12 parts of polyethylene, 0.6 part of a compatilizer, 0.03 part of an initiator, 2.5 parts of gallic acid, 1 part of tetraethylenepentamine and 5 parts of nano silicon dioxide. The compatilizer is used for melt grafting with polyethylene, and the initiator is used for initiating melt grafting of the compatilizer and polyethylene. The invention also provides a method for carrying out interface regulation and control by adopting the interface regulation and control composition and an ultra-high molecular weight polyethylene fiber resin composite material prepared by the method. The ultra-high molecular weight polyethylene fiber resin composite material obtained by carrying out interface regulation and control treatment on the ultra-high molecular weight polyethylene fiber resin composite material interface regulation and control composition has a good interface state, excellent mechanical properties and good impact resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of fiber resin composite materials, in particular to the technical field of ultra-high molecular weight polyethylene fiber resin composite materials, specifically to an ultra-high molecular weight polyethylene fiber resin composite material interface control composition, an interface control method and a fiber resin composite material prepared thereby. Background Art

[0002] Ultra-high molecular weight polyethylene (UHMWPE) fibers have attracted widespread attention from researchers and the manufacturing industry in recent years. They feature ultra-low density, excellent mechanical properties, and outstanding environmental resistance and durability, making them widely used in personal protection, aerospace, construction, and other fields. Although UHMWPE fibers possess significant mechanical advantages that far surpass other fibers, their molecular chains lack polar groups and have a high degree of crystallinity (up to 95%), resulting in poor adhesion to the fiber surface and difficulty forming a good bond with the resin matrix. This limits their widespread application in various fields.

[0003] Therefore, improving the interfacial adhesion between UHMWPE fibers and the resin matrix has always been a technical challenge in the preparation of UHMWPE fiber-resin composites. The search for new methods for regulating the interface of UHMWPE fiber-resin composites, which can result in UHMWPE fiber-resin composites with a good interfacial state, excellent mechanical properties, and good impact resistance, has important practical application value.

[0004] Therefore, it is hoped to provide a method for controlling the interface of an ultra-high molecular weight polyethylene fiber resin composite material, wherein the ultra-high molecular weight polyethylene fiber resin composite material prepared by the method has a good interface state, excellent mechanical properties and good impact resistance. Summary of the Invention

[0005] In order to overcome the shortcomings of the above-mentioned prior art, one object of the present invention is to provide an ultra-high molecular weight polyethylene fiber resin composite interface control composition. The ultra-high molecular weight polyethylene fiber resin composite material prepared using the composition has a good interface state, excellent mechanical properties and good impact resistance, and is suitable for large-scale promotion and application.

[0006] Another object of the present invention is to provide a method for controlling the interface of ultra-high molecular weight polyethylene fiber resin composite materials. The ultra-high molecular weight polyethylene fiber resin composite materials prepared by this method have good interface state, excellent mechanical properties and good impact resistance, and are suitable for large-scale promotion and application.

[0007] Another object of the present invention is to provide an ultra-high molecular weight polyethylene fiber resin composite material, which has a good interface state, excellent mechanical properties and good impact resistance, and is suitable for large-scale promotion and application.

[0008] To achieve the above objectives, in a first aspect of the present invention, there is provided an ultra-high molecular weight polyethylene fiber resin composite interface control composition, comprising ultra-high molecular weight polyethylene fiber, characterized in that the ultra-high molecular weight polyethylene fiber resin composite interface control composition further comprises polyethylene, a compatibilizer, an initiator, gallic acid, tetraethylene pentamine and nano-silica, wherein:

[0009] The ultra-high molecular weight polyethylene fiber comprises 100 parts by weight, the polyethylene comprises 12 parts by weight, the compatibilizer comprises 0.6 parts by weight, the initiator comprises 0.03 parts by weight, the gallic acid comprises 2.5 parts by weight, the tetraethylene pentamine comprises 1 part by weight, and the nano-silica comprises 5 parts by weight. The compatibilizer is used for melt grafting with the polyethylene, and the initiator is used for initiating melt grafting of the compatibilizer with the polyethylene.

[0010] Preferably, the ultra-high molecular weight polyethylene fiber is an ultra-high molecular weight polyethylene fiber plain weave cloth.

[0011] Preferably, the polyethylene is linear low density polyethylene.

[0012] Preferably, the compatibilizer is a maleic anhydride compatibilizer.

[0013] Preferably, the initiator is dicumyl peroxide initiator.

[0014] In a second aspect of the present invention, a method for controlling the interface of an ultra-high molecular weight polyethylene fiber resin composite material is provided, which is characterized by using the above-mentioned ultra-high molecular weight polyethylene fiber resin composite material interface control composition and comprising the following steps:

[0015] (1) preparing a gallic acid-tetraethylpentamine solution with the gallic acid and the tetraethylpentamine;

[0016] (2) preparing the nano-silica into an amino-silica solution;

[0017] (3) uniformly mixing the gallic acid-tetraethylenepentamine solution and the amino-modified nano-silica solution to obtain a composite modified solution;

[0018] (4) immersing the ultra-high molecular weight polyethylene fiber in the composite modification solution, shaking at a constant temperature, rinsing with water and drying to obtain a modified ultra-high molecular weight polyethylene fiber;

[0019] (5) uniformly mixing the polyethylene, the compatibilizer, and the initiator, and repeatedly extruding the mixture to form a film to obtain a grafted polyethylene film;

[0020] (6) The grafted polyethylene film and the modified ultra-high molecular weight polyethylene fiber are stacked and cured to form an ultra-high molecular weight polyethylene fiber resin composite material.

[0021] Preferably, the specific steps of step (1) are: adding the gallic acid and the tetraethylene pentamine to a Tris hydrochloric acid buffer solution with a pH of 8.5, stirring and mixing, to obtain the gallic acid-tetraethylene pentamine solution.

[0022] Preferably, the specific steps of step (2) are: dissolving the nano-silica in ethanol and ultrasonically dispersing it to form solution A; mixing other ethanol, deionized water, glacial acetic acid and silane coupling agent, stirring and ultrasonically treating it to form solution B; slowly adding solution B dropwise to solution A, stirring evenly and then heating it to obtain the amino-treated nano-silica solution.

[0023] Preferably, in step (4), the temperature of the constant temperature oscillation is room temperature, the frequency of the constant temperature oscillation is 80 rpm, and the time of the constant temperature oscillation is 6 hours to 18 hours.

[0024] In a third aspect of the present invention, an ultra-high molecular weight polyethylene fiber resin composite material is provided, which is characterized in that it is prepared by the above-mentioned interface control method of the ultra-high molecular weight polyethylene fiber resin composite material.

[0025] The beneficial effects of the present invention are mainly:

[0026] 1. The ultra-high molecular weight polyethylene fiber resin composite interface control composition of the present invention comprises ultra-high molecular weight polyethylene fiber, polyethylene, a compatibilizer, an initiator, gallic acid, tetraethylene pentamine and nano-silica, comprising 100 parts by weight of ultra-high molecular weight polyethylene fiber, 12 parts by weight of polyethylene, 0.6 parts by weight of a compatibilizer, 0.03 parts by weight of an initiator, 2.5 parts by weight of gallic acid, 1 part by weight of tetraethylene pentamine and 5 parts by weight of nano-silica. The compatibilizer is used for melt grafting with the polyethylene, and the initiator is used for initiating the melt grafting of the compatibilizer with the polyethylene. The ultra-high molecular weight polyethylene fiber resin composite prepared using the composition has a good interface state, excellent mechanical properties and good impact resistance, and is suitable for large-scale promotion and application.

[0027] 2. The interface control method of the ultra-high molecular weight polyethylene fiber resin composite material of the present invention adopts the above-mentioned ultra-high molecular weight polyethylene fiber resin composite material interface control composition and comprises the following steps: (1) preparing gallic acid and tetraethylpentamine into a gallic acid-tetraethylpentamine solution; (2) preparing nano-silica into an amino-type nano-silica solution; (3) uniformly mixing the gallic acid-tetraethylpentamine solution and the amino-type nano-silica solution to obtain a composite modified solution; (4) immersing the ultra-high molecular weight polyethylene fiber in the composite modified solution, oscillating at a constant temperature, rinsing with water and drying to obtain a modified ultra-high molecular weight polyethylene fiber; (5) uniformly mixing polyethylene, a compatibilizer and an initiator, and repeatedly extruding to form a film to obtain a grafted polyethylene film; (6) stacking the grafted polyethylene film and the modified ultra-high molecular weight polyethylene fiber and curing and forming them to obtain an ultra-high molecular weight polyethylene fiber resin composite material. The ultra-high molecular weight polyethylene fiber resin composite material prepared by this method has a good interface state, excellent mechanical properties and good impact resistance, and is suitable for large-scale promotion and application.

[0028] 3. The ultra-high molecular weight polyethylene fiber resin composite material of the present invention is prepared by the above-mentioned ultra-high molecular weight polyethylene fiber resin composite material interface control method, has a good interface state, excellent mechanical properties and good impact resistance, and is suitable for large-scale promotion and application.

[0029] These and other objects, features and advantages of the present invention are fully reflected in the following detailed description and drawings, and can be achieved by the means, devices and their combinations particularly pointed out in the summary of the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is an SEM photograph of the surface of the UHMWPE fiber of Comparative Example 1 that has not undergone interface regulation.

[0031] Figure 2 This is an SEM photograph of the UHMWPE fiber surface after 12 hours of GA-TEPA “flexible” coating surface treatment in Comparative Example 3.

[0032] Figure 3 This is a SEM photograph of the UHMWPE fiber surface after being surface treated with a "rigid and flexible" coating composed of a GA-TEPA and amino-treated nano-N-SiO2 composite solution for 12 hours in Example 3.

[0033] Figure 4 It is a graph showing the variation of peel strength and interlaminar shear strength of the ultra-high molecular weight polyethylene (UHMWPE) fiber resin composite materials obtained in Comparative Examples 1 to 4 and Examples 1 to 3.

[0034] Figure 5It is a curve diagram of the change of tensile strength, flexural strength and low-speed impact toughness of the ultra-high molecular polyethylene (UHMWPE) fiber resin composite material obtained from Comparative Examples 1 to Comparative Examples 4 and Examples 1 to Example 3. DETAILED DESCRIPTION

[0035] In response to the problem that ultra-high molecular weight polyethylene (UHMWPE) fibers lack polar groups and have a high degree of crystallinity, resulting in poor adhesion performance on the fiber surface and difficulty in forming a good bond with the resin matrix, which limits its wide application in multiple fields, the inventors have conducted sufficient and extensive research on the interface regulation treatment of ultra-high molecular weight polyethylene fibers, and thus proposed a method for interface regulation of ultra-high molecular weight polyethylene fiber-resin composite materials to improve the interfacial compatibility between ultra-high molecular weight polyethylene fibers and the resin matrix, enhance the mechanical properties and impact resistance of ultra-high molecular weight polyethylene fiber-resin composite materials, and improve the practical application value of ultra-high molecular weight polyethylene fiber-resin composite materials.

[0036] The present invention first provides an ultra-high molecular weight polyethylene fiber resin composite interface control composition, comprising ultra-high molecular weight polyethylene fiber, polyethylene, a compatibilizer, an initiator, gallic acid (GA), tetraethylenepentamine (TEPA) and nano-silicon dioxide (SiO2), wherein:

[0037] The ultra-high molecular weight polyethylene fiber comprises 100 parts by weight, the polyethylene comprises 12 parts by weight, the compatibilizer comprises 0.6 parts by weight, the initiator comprises 0.03 parts by weight, the gallic acid comprises 2.5 parts by weight, the tetraethylene pentamine comprises 1 part by weight, and the nano-silica comprises 5 parts by weight. The compatibilizer is used for melt grafting with the polyethylene, and the initiator is used for initiating melt grafting of the compatibilizer with the polyethylene.

[0038] The ultra-high molecular weight polyethylene fiber can be any suitable form of ultra-high molecular weight polyethylene fiber. Preferably, the ultra-high molecular weight polyethylene fiber is an ultra-high molecular weight polyethylene fiber plain weave cloth.

[0039] The polyethylene may be any suitable type of polyethylene, preferably, the polyethylene is a linear low density polyethylene.

[0040] The compatibilizer can be any suitable compatibilizer. Preferably, the compatibilizer is a maleic anhydride compatibilizer.

[0041] The initiator may be any suitable initiator. Preferably, the initiator is dicumyl peroxide initiator.

[0042] The gallic acid and the tetraethylene pentamine can be used in any suitable form. Preferably, the gallic acid and the tetraethylene pentamine are used in the form of a gallic acid-tetraethylene pentamine solution.

[0043] The solvent of the gallic acid-tetraethylenepentamine solution can be any suitable solvent. More preferably, the solvent of the gallic acid-tetraethylenepentamine solution is a Tris hydrochloric acid buffer solution (tris(hydroxymethyl)aminomethane hydrochloric acid buffer solution) with a pH of 8.5.

[0044] The nano-silica can be used in any suitable form. Preferably, the nano-silica is used in the form of an amino-treated nano-silica solution.

[0045] The amino-modified nano-silica solution can be prepared by any suitable method. More preferably, the amino-modified nano-silica solution is prepared by the following method: dissolving the nano-silica in ethanol and ultrasonically dispersing it to form solution A; mixing additional ethanol, deionized water, glacial acetic acid and a silane coupling agent, stirring and ultrasonically treating it to form solution B; slowly adding solution B dropwise to solution A, stirring evenly, and then heating it to obtain the amino-modified nano-silica solution.

[0046] The present invention also provides a method for controlling the interface of an ultra-high molecular weight polyethylene fiber resin composite material, which uses the above-mentioned ultra-high molecular weight polyethylene fiber resin composite material interface control composition and comprises the following steps:

[0047] (1) preparing a gallic acid-tetraethylpentamine solution with the gallic acid and the tetraethylpentamine;

[0048] (2) preparing the nano-silica into an amino-silica solution;

[0049] (3) uniformly mixing the gallic acid-tetraethylenepentamine solution and the amino-modified nano-silica solution to obtain a composite modified solution;

[0050] (4) immersing the ultra-high molecular weight polyethylene fiber in the composite modification solution, shaking at a constant temperature, rinsing with water and drying to obtain a modified ultra-high molecular weight polyethylene fiber;

[0051] (5) uniformly mixing the polyethylene, the compatibilizer, and the initiator, and repeatedly extruding the mixture to form a film to obtain a grafted polyethylene film;

[0052] (6) The grafted polyethylene film and the modified ultra-high molecular weight polyethylene fiber are stacked and cured to form an ultra-high molecular weight polyethylene fiber resin composite material.

[0053] The step (1) can adopt any appropriate specific steps. Preferably, the specific steps of the step (1) are: adding the gallic acid and the tetraethylene pentamine to a Tris hydrochloric acid buffer solution with a pH of 8.5, stirring and mixing, to obtain the gallic acid-tetraethylene pentamine solution.

[0054] The step (2) can adopt any appropriate specific steps. Preferably, the specific steps of the step (2) are: dissolving the nano-silica in ethanol and ultrasonically dispersing it to form a solution A; mixing other ethanol, deionized water, glacial acetic acid and a silane coupling agent, stirring and ultrasonically treating it to form a solution B; slowly adding the solution B dropwise to the solution A, stirring evenly and then heating it to obtain the amino-treated nano-silica solution.

[0055] The heat treatment may be performed by any suitable method. More preferably, the heat treatment is performed in a 75° C. oil bath.

[0056] The silane coupling agent can be any suitable silane coupling agent. More preferably, the silane coupling agent is silane coupling agent KH550.

[0057] In step (4), the temperature, speed and time of the constant temperature oscillation can be determined as needed. Preferably, in step (4), the temperature of the constant temperature oscillation is room temperature, the frequency of the constant temperature oscillation is 80 rpm, and the time of the constant temperature oscillation is 6 hours to 18 hours.

[0058] In step (4), the drying treatment can be carried out using any suitable equipment, and the temperature and time of the drying treatment can be determined as needed. Preferably, in step (4), the drying treatment is carried out using a blast oven, the drying treatment temperature is 60°C, and the drying treatment time is 8 hours.

[0059] In the step (5), the mixing can be carried out by any suitable equipment, and the repeated extrusion film-making can be carried out by any suitable equipment. Preferably, in the step (5), the mixing is carried out in a high-speed mixer, the mixing temperature is 160°C, the mixing speed is 1200rpm, and the mixing time is 5min; the repeated extrusion film-making is carried out by a twin-screw extruder, and the screw speed of the twin-screw extruder is 50rpm~60rpm.

[0060] In the step (6), the curing molding can be carried out by any suitable method. Preferably, in the step (6), the curing molding is carried out by hot pressing molding, the temperature of the hot pressing molding is 130°C, the pressure of the hot pressing molding is 5MPa, and the time of the hot pressing molding is 20min.

[0061] The present invention also provides an ultra-high molecular weight polyethylene fiber resin composite material, which is prepared by adopting the above-mentioned ultra-high molecular weight polyethylene fiber resin composite material interface control method.

[0062] In order to more clearly understand the technical content of the present invention, the following examples are specifically described in detail. It should be understood that the specific examples described herein are merely illustrative of the present invention and are not intended to limit the present invention. Unless otherwise stated, the instruments, drugs, reagents, etc. used in the following examples can be obtained by conventional commercial means.

[0063] Example 1

[0064] Ultra-high molecular weight polyethylene fiber 100g, polyethylene 12g, compatibilizer 0.6g, initiator 0.03g, gallic acid 2.5g, tetraethylene pentamine 1g, nano-silica 5g.

[0065] A 0.01 mol / L Tris solution was prepared in deionized water, and dilute hydrochloric acid was added dropwise to adjust the pH of the solution to 8.5 to obtain a Tris-HCl buffer solution. 2.5 g of gallic acid (GA) and 1 g of tetraethylenepentamine (TEPA) were added to 1 L of the Tris-HCl buffer solution, and mechanical stirring was used until completely dissolved to obtain a GA-TEPA solution (i.e., gallic acid-tetraethylenepentamine solution).

[0066] 5g of nano-SiO2 was dissolved in 50ml of ethanol and ultrasonically dispersed for 10min to obtain a milky white uniform liquid. 50ml of ethanol and 25ml of deionized water were then added, and mechanical stirring was performed for 1h and ultrasonic continuous dispersion was performed for 30min to form a uniform solution A. 100ml of ethanol, 2ml of deionized water, 5ml of glacial acetic acid, and 500mg of silane coupling agent KH550 (Aladdin Biochemical Technology Co., Ltd.) were added to another beaker in sequence. Magnetic stirring was performed for 10min at room temperature and ultrasonication was performed for 20min until the silane coupling agent was fully hydrolyzed to obtain solution B. Solution B was slowly added dropwise to solution A, stirred evenly, and reacted in a 75°C oil bath for 4h to obtain an amino-type nano-SiO2 (N-SiO2) solution, i.e., an amino-type nano-silica solution. Finally, low-speed centrifugation was used for 10min to remove large particles and precipitates, the supernatant was diluted to 1g / L, and mixed with the above-mentioned GA-TEPA solution to form a composite modified solution.

[0067] The UHMWPE fiber plain woven fabric was immersed in the composite modification solution, oscillated in a constant temperature oscillator at 80 rpm at room temperature for 18 hours, then taken out, rinsed with deionized water and dried in a blast oven at 60°C for 8 hours to obtain a UHMWPE plain woven fabric with a "rigid and flexible" coating surface treatment.

[0068] Polyethylene, maleic anhydride (MAH) and dicumyl peroxide (DCP) were added to a high-speed mixer (wherein the mass fraction of polyethylene was 95% and the MAH / DCP ratio was 2:0.1), mixed uniformly at 160°C and 1200 rpm for 5 min, and then added to a twin-screw extruder for repeated extrusion to form a film at a screw speed of 50 rpm to obtain a melt-grafted polyethylene resin film, which was recorded as PO resin film.

[0069] The PO resin film and the surface-modified UHMWPE plain fabric were laid alternately up and down, and the UHMWPE / PO composite material was prepared by hot pressing using a flat-plate vulcanizer. The hot pressing temperature of the flat-plate vulcanizer was 130°C, the pressure was 5 MPa, and the time was 20 min.

[0070] Example 2

[0071] Ultra-high molecular weight polyethylene fiber 100g, polyethylene 12g, compatibilizer 0.6g, initiator 0.03g, gallic acid 2.5g, tetraethylene pentamine 1g, nano-silica 5g.

[0072] A 0.01 mol / L Tris solution was prepared in deionized water, and dilute hydrochloric acid was added dropwise to adjust the pH of the solution to 8.5 to obtain a Tris-HCl buffer solution. 2.5 g of gallic acid (GA) and 1 g of tetraethylenepentamine (TEPA) were added to 1 L of the Tris-HCl buffer solution, and mechanical stirring was used until completely dissolved to obtain a GA-TEPA solution (i.e., gallic acid-tetraethylenepentamine solution).

[0073] 5g of nano-SiO2 was dissolved in 50ml of ethanol and ultrasonically dispersed for 10min to obtain a milky white uniform liquid. 50ml of ethanol and 25ml of deionized water were then added, and mechanical stirring was performed for 1h and ultrasonic continuous dispersion was performed for 30min to form a uniform solution A. 100ml of ethanol, 2ml of deionized water, 5ml of glacial acetic acid, and 500mg of silane coupling agent KH550 (Aladdin Biochemical Technology Co., Ltd.) were added to another beaker in sequence. Magnetic stirring was performed for 10min at room temperature and ultrasonication was performed for 20min until the silane coupling agent was fully hydrolyzed to obtain solution B. Solution B was slowly added dropwise to solution A, stirred evenly, and reacted in a 75°C oil bath for 4h to obtain an amino-type nano-SiO2 (N-SiO2) solution, i.e., an amino-type nano-silica solution. Finally, low-speed centrifugation was used for 10min to remove large particles and precipitates, the supernatant was diluted to 1g / L, and mixed with the above-mentioned GA-TEPA solution to form a composite modified solution.

[0074] The UHMWPE fiber plain woven fabric was immersed in the composite modification solution, oscillated in a constant temperature oscillator at 80 rpm for 6 hours at room temperature, taken out, rinsed with deionized water and dried in a blast oven at 60°C for 8 hours to obtain a UHMWPE plain woven fabric with a "rigid and flexible" coating surface treatment.

[0075] Polyethylene, maleic anhydride (MAH) and dicumyl peroxide (DCP) were added to a high-speed mixer (wherein the mass fraction of polyethylene was 95% and the MAH / DCP ratio was 2:0.1), mixed uniformly at 160°C and 1200 rpm for 5 min, and then added to a twin-screw extruder for repeated extrusion to form a film at a screw speed of 60 rpm to obtain a melt-grafted polyethylene resin film, which was recorded as PO resin film.

[0076] The PO resin film and the surface-modified UHMWPE plain fabric were laid alternately up and down, and the UHMWPE / PO composite material was prepared by hot pressing using a flat-plate vulcanizer. The hot pressing temperature of the flat-plate vulcanizer was 130°C, the pressure was 5 MPa, and the time was 20 min.

[0077] Example 3

[0078] Ultra-high molecular weight polyethylene fiber 100g, polyethylene 12g, compatibilizer 0.6g, initiator 0.03g, gallic acid 2.5g, tetraethylene pentamine 1g, nano-silica 5g.

[0079] A 0.01 mol / L Tris solution was prepared in deionized water, and dilute hydrochloric acid was added dropwise to adjust the pH of the solution to 8.5 to obtain a Tris-HCl buffer solution. 2.5 g of gallic acid (GA) and 1 g of tetraethylenepentamine (TEPA) were added to 1 L of the Tris-HCl buffer solution, and mechanical stirring was used until completely dissolved to obtain a GA-TEPA solution (i.e., gallic acid-tetraethylenepentamine solution).

[0080] 5g of nano-SiO2 was dissolved in 50ml of ethanol and ultrasonically dispersed for 10min to obtain a milky white uniform liquid. 50ml of ethanol and 25ml of deionized water were then added, and mechanical stirring was performed for 1h and ultrasonic continuous dispersion was performed for 30min to form a uniform solution A. 100ml of ethanol, 2ml of deionized water, 5ml of glacial acetic acid, and 500mg of silane coupling agent KH550 (Aladdin Biochemical Technology Co., Ltd.) were added to another beaker in sequence. Magnetic stirring was performed for 10min at room temperature and ultrasonication was performed for 20min until the silane coupling agent was fully hydrolyzed to obtain solution B. Solution B was slowly added dropwise to solution A, stirred evenly, and reacted in a 75°C oil bath for 4h to obtain an amino-type nano-SiO2 (N-SiO2) solution, i.e., an amino-type nano-silica solution. Finally, low-speed centrifugation was used for 10min to remove large particles and precipitates, the supernatant was diluted to 1g / L, and mixed with the above-mentioned GA-TEPA solution to form a composite modified solution.

[0081] The UHMWPE fiber plain woven fabric was immersed in the composite modification solution, oscillated in a constant temperature oscillator at 80 rpm for 12 hours at room temperature, taken out, rinsed with deionized water and dried in a blast oven at 60°C for 8 hours to obtain a UHMWPE plain woven fabric with a "rigid and flexible" coating surface treatment.

[0082] Polyethylene, maleic anhydride (MAH) and dicumyl peroxide (DCP) were added to a high-speed mixer (wherein the mass fraction of polyethylene was 95% and the MAH / DCP ratio was 2:0.1), mixed uniformly at 160°C and 1200 rpm for 5 min, and then added to a twin-screw extruder for repeated extrusion to form a film at a screw speed of 55 rpm to obtain a melt-grafted polyethylene resin film, which was recorded as PO resin film.

[0083] The PO resin film and the surface-modified UHMWPE plain fabric were laid alternately up and down, and the UHMWPE / PO composite material was prepared by hot pressing using a flat-plate vulcanizer. The hot pressing temperature of the flat-plate vulcanizer was 130°C, the pressure was 5 MPa, and the time was 20 min.

[0084] Comparative Example 1

[0085] 100g ultra-high molecular weight polyethylene fiber, 12g polyethylene, 0.6g compatibilizer, 0.03g initiator.

[0086] Polyethylene, maleic anhydride (MAH) and dicumyl peroxide (DCP) were added to a high-speed mixer (wherein the mass fraction of polyethylene was 95% and the MAH / DCP ratio was 2:0.1), mixed uniformly at 160°C and 1200 rpm for 5 minutes, and then added to a twin-screw extruder for repeated extrusion to form a film. The screw speed was controlled within the range of 50 rpm to 60 rpm to obtain a melt-grafted polyethylene resin film, which was recorded as PO resin film.

[0087] The PO resin film and the UHMWPE plain woven fabric were laid alternately up and down, and the UHMWPE / PO composite material was prepared by hot pressing using a flat vulcanizer. The hot pressing temperature of the flat vulcanizer was 130°C, the pressure was 5 MPa, and the time was 20 min.

[0088] Comparative Example 2

[0089] Ultra-high molecular weight polyethylene fiber 100g, polyethylene 12g, compatibilizer 0.6g, initiator 0.03g, gallic acid 2.5g, tetraethylene pentamine 1g.

[0090] A 0.01 mol / L Tris solution was prepared in deionized water, and dilute hydrochloric acid was added dropwise to adjust the pH of the solution to 8.5 to obtain a Tris-HCl buffer solution. 2.5 g of gallic acid (GA) and 1 g of tetraethylenepentamine (TEPA) were added to 1 L of the Tris-HCl buffer solution, and mechanical stirring was used until completely dissolved to obtain a GA-TEPA solution (i.e., gallic acid-tetraethylenepentamine solution).

[0091] The UHMWPE fiber plain woven fabric was immersed in the GA-TEPA solution, oscillated at 80 rpm in a constant temperature oscillator at room temperature for 6 hours, then taken out, rinsed with deionized water and dried in a forced air oven at 60°C for 8 hours to obtain a UHMWPE plain woven fabric with a "flexible" coating surface treatment.

[0092] Polyethylene, maleic anhydride (MAH) and dicumyl peroxide (DCP) were added to a high-speed mixer (wherein the mass fraction of polyethylene was 95% and the MAH / DCP ratio was 2:0.1), mixed uniformly at 160°C and 1200 rpm for 5 minutes, and then added to a twin-screw extruder for repeated extrusion to form a film. The screw speed was controlled within the range of 50 rpm to 60 rpm to obtain a melt-grafted polyethylene resin film, which was recorded as PO resin film.

[0093] The PO resin film and the surface-modified UHMWPE plain fabric were laid alternately up and down, and the UHMWPE / PO composite material was prepared by hot pressing using a flat-plate vulcanizer. The hot pressing temperature of the flat-plate vulcanizer was 130°C, the pressure was 5 MPa, and the time was 20 min.

[0094] Comparative Example 3

[0095] Ultra-high molecular weight polyethylene fiber 100g, polyethylene 12g, compatibilizer 0.6g, initiator 0.03g, gallic acid 2.5g, tetraethylene pentamine 1g.

[0096] A 0.01 mol / L Tris solution was prepared in deionized water, and dilute hydrochloric acid was added dropwise to adjust the pH of the solution to 8.5 to obtain a Tris-HCl buffer solution. 2.5 g of gallic acid (GA) and 1 g of tetraethylenepentamine (TEPA) were added to 1 L of the Tris-HCl buffer solution, and mechanical stirring was used until completely dissolved to obtain a GA-TEPA solution (i.e., gallic acid-tetraethylenepentamine solution).

[0097] The UHMWPE fiber plain woven fabric was immersed in the GA-TEPA solution, oscillated in a constant temperature oscillator at 80 rpm at room temperature for 12 hours, then taken out, rinsed with deionized water and dried in a forced air oven at 60°C for 8 hours to obtain a UHMWPE plain woven fabric with a "flexible" coating surface treatment.

[0098] Polyethylene, maleic anhydride (MAH) and dicumyl peroxide (DCP) were added to a high-speed mixer (wherein the mass fraction of polyethylene was 95% and the MAH / DCP ratio was 2:0.1), mixed uniformly at 160°C and 1200 rpm for 5 minutes, and then added to a twin-screw extruder for repeated extrusion to form a film. The screw speed was controlled within the range of 50 rpm to 60 rpm to obtain a melt-grafted polyethylene resin film, which was recorded as PO resin film.

[0099] The PO resin film and the surface-modified UHMWPE plain fabric were laid alternately up and down, and the UHMWPE / PO composite material was prepared by hot pressing using a flat-plate vulcanizer. The hot pressing temperature of the flat-plate vulcanizer was 130°C, the pressure was 5 MPa, and the time was 20 min.

[0100] Comparative Example 4

[0101] Ultra-high molecular weight polyethylene fiber 100g, polyethylene 12g, compatibilizer 0.6g, initiator 0.03g, gallic acid 2.5g, tetraethylene pentamine 1g.

[0102] A 0.01 mol / L Tris solution was prepared in deionized water, and dilute hydrochloric acid was added dropwise to adjust the pH of the solution to 8.5 to obtain a Tris-HCl buffer solution. 2.5 g of gallic acid (GA) and 1 g of tetraethylenepentamine (TEPA) were added to 1 L of the Tris-HCl buffer solution, and mechanical stirring was used until completely dissolved to obtain a GA-TEPA solution (i.e., gallic acid-tetraethylenepentamine solution).

[0103] The UHMWPE fiber plain woven fabric was immersed in the GA-TEPA solution, oscillated in a constant temperature oscillator at 80 rpm at room temperature for 18 hours, then taken out, rinsed with deionized water and dried in a blast oven at 60°C for 8 hours to obtain a UHMWPE plain woven fabric with a "flexible" coating surface treatment.

[0104] Polyethylene, maleic anhydride (MAH) and dicumyl peroxide (DCP) were added to a high-speed mixer (wherein the mass fraction of polyethylene was 95% and the MAH / DCP ratio was 2:0.1), mixed uniformly at 160°C and 1200 rpm for 5 minutes, and then added to a twin-screw extruder for repeated extrusion to form a film. The screw speed was controlled within the range of 50 rpm to 60 rpm to obtain a melt-grafted polyethylene resin film, which was recorded as PO resin film.

[0105] The PO resin film and the surface-modified UHMWPE plain fabric were laid alternately up and down, and the UHMWPE / PO composite material was prepared by hot pressing using a flat-plate vulcanizer. The hot pressing temperature of the flat-plate vulcanizer was 130°C, the pressure was 5 MPa, and the time was 20 min.

[0106] Example 4

[0107] The ultrahigh molecular weight polyethylene (UHMWPE) fiber-resin composites obtained in Comparative Examples 1 to 4 and Examples 1 to 3 were tested for tensile strength, flexural strength, interlaminar shear strength, peel strength, and low-velocity impact toughness. The test results are shown in the following table. The interlaminar shear strength test was conducted in accordance with ASTM D2344, the tensile strength test was conducted in accordance with GB / T 1040-2006, the flexural strength test was conducted in accordance with GB / T 1449-2005, the peel strength test was conducted in accordance with GB / T 2791-1995, "Adhesives - T-Peel Strength Test Method - Flexible Material to Flexible Material," and the low-velocity impact toughness test was conducted in accordance with GB / T 1043-2008.

[0108]

[0109]

[0110] As shown in the table above, the tensile strength, flexural strength and interlaminar shear strength of the ultra-high molecular polyethylene (UHMWPE) fiber resin composite material (Comparative Example 1) prepared by compounding the UHMWPE plain fabric without interface regulation treatment and the PO resin film all showed low values; the various properties of the ultra-high molecular polyethylene (UHMWPE) fiber resin composite material (Comparative Example 2) prepared by compounding the PPTA plain fabric with the PO resin film after the GA-TEPA (2.5:1) solution was subjected to interface regulation treatment for 6 hours were improved compared with the comparative example 1; the various properties of the ultra-high molecular polyethylene (UHMWPE) fiber resin composite material prepared by compounding the PPTA plain fabric with the PO resin film after the GA-TEPA (2.5:1) solution was subjected to interface regulation treatment for 12 hours (Comparative Example 3) were further improved; however, the various properties of the ultra-high molecular polyethylene (UHMWPE) fiber resin composite material (Comparative Example 4) prepared by compounding the PPTA plain fabric with the PO resin film after the GA-TEPA (2.5:1) solution was subjected to interface regulation treatment for 18 hours were significantly improved. Reduce; After GA-TEPA and N-SiO2 are mixed into a composite modification solution, the interface of the PPTA plain fabric is subjected to 18-hour control treatment and then the ultra-high molecular polyethylene (UHMWPE) fiber resin composite material (Example 1) is prepared, and its tensile strength, flexural strength and interlaminar shear strength are significantly improved compared with the use of GA-TEPA solution; After GA-TEPA and N-SiO2 are mixed into a composite modification solution, the interface of the PPTA plain fabric is subjected to 6-hour control treatment and then the ultra-high molecular polyethylene (UHMWPE) fiber resin composite material (Example 2) is prepared, and its tensile strength, flexural strength and interlaminar shear strength are improved compared with 18 hours; Finally, after GA-TEPA and N-SiO2 are mixed into a composite modification solution, the interface of the PPTA plain fabric is subjected to 12-hour control treatment and then the ultra-high molecular polyethylene (UHMWPE) fiber resin composite material (Example 3) is prepared, and its overall performance is the best, indicating that the "rigid and flexible" coating modification treatment can significantly improve the performance of the composite material; Combined with the accompanying drawings, Figure 1 SEM photos of the UHMWPE fiber surface without interface regulation, Figure 2 SEM photos of the UHMWPE fiber surface after 12 hours of GA-TEPA "flexible" coating treatment and Figure 3Comparison of SEM photographs of the UHMWPE fiber surface after 12 hours of surface treatment with a "rigid and flexible" coating composed of GA-TEPA and amino-containing nano-N-SiO2 composite solution shows that the surface coating of the UHMWPE fiber after the "flexible" coating treatment is uniform and continuous, and the surface roughness is significantly increased; after the "rigid and flexible" coating treatment, the N-SiO2 distribution on the UHMWPE fiber surface is more uniform, showing a dense and uniform interface coating structure, which is beneficial to the optimization and improvement of the interface performance and mechanical properties of the composite material.

[0111] Therefore, the present invention provides an ultra-high molecular weight polyethylene fiber resin composite interface control composition, which is used to carry out interface control treatment of the ultra-high molecular weight polyethylene fiber resin composite to prepare an ultra-high molecular weight polyethylene fiber resin composite material. The ultra-high molecular weight polyethylene fiber resin composite material has a good interface state, excellent mechanical properties and good impact resistance, and the interface control treatment equipment requirements are low, the operation is simple, the cost is low, and it is suitable for large-scale promotion and application in engineering.

[0112] In summary, the ultra-high molecular weight polyethylene fiber resin composite material obtained by interface regulation treatment using the ultra-high molecular weight polyethylene fiber resin composite material interface regulation composition in the present invention has a good interface state, excellent mechanical properties and good impact resistance, and is suitable for large-scale promotion and application.

[0113] It can be seen that the objectives of the present invention have been fully and effectively achieved. The functional and structural principles of the present invention have been demonstrated and illustrated in the embodiments. The embodiments may be modified as desired without departing from the principles described. Therefore, the present invention includes all variations within the spirit and scope of the claims.

Claims

1. An ultra-high molecular weight polyethylene fiber resin composite interface control composition, comprising ultra-high molecular weight polyethylene fiber, characterized in that: The ultra-high molecular weight polyethylene fiber resin composite material interface control composition further comprises polyethylene, a compatibilizer, an initiator, gallic acid, tetraethylene pentamine and nano-silicon dioxide, wherein: The ultra-high molecular weight polyethylene fiber comprises 100 parts by weight, the polyethylene comprises 12 parts by weight, the compatibilizer comprises 0.6 parts by weight, the initiator comprises 0.03 parts by weight, the gallic acid comprises 2.5 parts by weight, the tetraethylene pentamine comprises 1 part by weight, and the nano-silica comprises 5 parts by weight. The compatibilizer is used for melt grafting with the polyethylene, and the initiator is used for initiating melt grafting of the compatibilizer with the polyethylene.

2. The ultra-high molecular weight polyethylene fiber resin composite material interface control composition according to claim 1, characterized in that: The ultra-high molecular weight polyethylene fiber is an ultra-high molecular weight polyethylene fiber plain weave cloth.

3. The ultra-high molecular weight polyethylene fiber resin composite material interface control composition according to claim 1, characterized in that: The polyethylene is linear low density polyethylene.

4. The ultra-high molecular weight polyethylene fiber resin composite material interface control composition according to claim 1, characterized in that: The compatibilizer is a maleic anhydride compatibilizer.

5. The ultra-high molecular weight polyethylene fiber resin composite material interface control composition according to claim 1, characterized in that: The initiator is dicumyl peroxide initiator.

6. A method for controlling the interface of an ultra-high molecular weight polyethylene fiber resin composite material, characterized in that: The ultra-high molecular weight polyethylene fiber resin composite material interface control composition according to claim 1 is used and includes the following steps: (1) preparing a gallic acid-tetraethylpentamine solution with the gallic acid and the tetraethylpentamine; (2) preparing the nano-silica into an amino-silica solution; (3) uniformly mixing the gallic acid-tetraethylenepentamine solution and the amino-modified nano-silica solution to obtain a composite modified solution; (4) immersing the ultra-high molecular weight polyethylene fiber in the composite modification solution, shaking at a constant temperature, rinsing with water and drying to obtain a modified ultra-high molecular weight polyethylene fiber; (5) uniformly mixing the polyethylene, the compatibilizer, and the initiator and repeatedly extruding the mixture to form a film to obtain a grafted polyethylene film; (6) The grafted polyethylene film and the modified ultra-high molecular weight polyethylene fiber are stacked and cured to form an ultra-high molecular weight polyethylene fiber resin composite material.

7. The method for controlling the interface of an ultra-high molecular weight polyethylene fiber resin composite material according to claim 6, wherein: The specific steps of step (1) are: adding the gallic acid and the tetraethylpentamine into a Tris hydrochloric acid buffer solution with a pH of 8.5, stirring and mixing, and obtaining the gallic acid-tetraethylpentamine solution.

8. The method for controlling the interface of an ultra-high molecular weight polyethylene fiber resin composite material according to claim 6, wherein: The specific steps of step (2) are: dissolving the nano-silica in ethanol and ultrasonically dispersing it to form solution A; mixing other ethanol, deionized water, glacial acetic acid and a silane coupling agent, stirring and ultrasonically treating it to form solution B; slowly adding solution B dropwise to solution A, stirring evenly and then heating it to obtain the amino-treated nano-silica solution.

9. The method for controlling the interface of an ultra-high molecular weight polyethylene fiber resin composite material according to claim 6, wherein: In the step (4), the temperature of the constant temperature oscillation is room temperature, the frequency of the constant temperature oscillation is 80 rpm, and the time of the constant temperature oscillation is 6 hours to 18 hours.

10. An ultra-high molecular weight polyethylene fiber resin composite material, characterized in that: The ultra-high molecular weight polyethylene fiber resin composite material is prepared by the interface control method according to any one of claims 6 to 9.

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