Modified metal organic framework material as well as preparation method and application thereof

Abstract

The invention provides a modified metal organic framework material as well as a preparation method and application thereof. The preparation method comprises the following steps: (1) reacting acrylamide with dopamine acrylamide to obtain PND nanogel; (2) mixing the metal organic framework with an organic solution and hydrochloric acid, and heating and activating to obtain an activated metal organic framework; and (3) mixing the PND nanogel prepared in the step (1) and the activated metal organic framework prepared in the step (2), and reacting to obtain the modified metal organic framework material. The modified metal organic framework material provided by the invention can improve the mechanical property and antibacterial property of a polymer matrix, and the antibacterial composite material prepared by adding the modified metal organic framework material has excellent mechanical property and marine organism resistance; the material can be used as a main body material of a marine organism prevention device for removing marine organisms by utilizing marine driving force, and can be used in a marine environment for a long time.

Description

Technical Field

[0001] The invention belongs to the technical field of marine antifouling materials, and specifically relates to a modified metal organic framework material and a preparation method and application thereof. Background Art

[0002] The development of marine engineering, marine resources and energy, such as offshore wind power and offshore oil platforms, has become an important pillar industry of my country's national economy. However, sub-water structures, such as pile foundations of offshore wind power and jackets of offshore oil platforms, are often seriously affected by the complex biological communities in the ocean, especially the reproduction of barnacles and mussels. In addition to affecting the mechanical properties of the structure, these marine organisms may also affect the normal operation and maintenance of the equipment. At present, the removal of marine organisms on wind power pile foundations or jackets mainly relies on mechanical cleaning, such as underwater cleaning by divers carrying high-pressure water guns, or underwater cleaning using remotely controlled unmanned submersibles (ROVs). However, in addition to the high cost of removal, these two methods also have problems such as high construction risks.

[0003] In recent years, new methods for preventing marine growth have gradually attracted attention. For example, CN218085969U discloses a device for preventing marine growth from attaching and an offshore support foundation. The device for preventing marine growth from attaching is used to form a polygonal ring around the outer wall of the protected body, and comprises: at least one impact roller and at least one connecting device, wherein the at least one impact roller has at least one connecting female part; the at least one connecting device has at least one connecting male part, at least one flexible part and / or at least one arc-shaped part; the at least one connecting male part is rotatably clamped in the at least one connecting female part; the at least one impact roller and the at least one connecting device are sequentially connected through at least one connecting female part and at least one connecting male part to form a polygonal ring structure; CN21 8537052U discloses a marine growth prevention ring, pile and offshore support foundation, wherein the marine growth prevention ring comprises at least one collision roller and at least one serial connection body, wherein the middle part of the at least one collision roller has at least one first serial connection hole; the at least one serial connection body is configured to serially connect the at least one collision roller through the at least one first serial connection hole and construct a closed ring structure; at least one spacer assembly is arranged between adjacent at least one collision roller, and the at least one serial connection body is also configured to pass through the at least one spacer assembly; the at least one collision roller and / or at least one spacer assembly are configured to be rotatable on the at least one serial connection body; and CN220598313U and CN220598312U.

[0004] The above technical solutions all use the driving force of the ocean and adopt anti-marine biological devices to remove marine organisms using purely physical methods. The driving force of this method comes from seawater and tides, which is energy-saving and environmentally friendly and has good application prospects. However, the anti-marine biological devices used are used in seawater for a long time, and the mechanical properties of the impact materials are required to be high. In addition, the anti-marine biological devices themselves are required to have the ability to prevent the growth of marine organisms. Therefore, it is necessary to develop a high-strength material with anti-marine biological function to meet the use requirements of this new anti-fouling device. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention aims to provide a modified metal organic framework material and a preparation method and application thereof. The modified metal organic framework material can improve the mechanical properties of the polymer matrix and the protection against marine organisms.

[0006] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a method for preparing a modified metal organic framework material, the preparation method comprising the following steps:

[0008] (1) acrylamide and dopamine acrylamide react to obtain PND nanogel;

[0009] (2) mixing the metal organic framework with an organic solution and hydrochloric acid, and heating and activating the mixture to obtain an activated metal organic framework;

[0010] (3) mixing the PND nanogel prepared in step (1) and the activated metal organic framework prepared in step (2), and reacting them to obtain the modified metal organic framework material.

[0011] In the present invention, the metal organic framework is modified by using PND nanogel, and a large number of hydroxyl groups on the surface of the PND nanogel can react with the hydroxyl groups on the surface of the metal organic framework to generate ether bonds, so that the PND nanogel and the metal organic framework are tightly combined to form a modified metal organic framework material. The modified metal organic framework material can have a reinforcing effect on the polymer matrix, can improve the mechanical strength in the amorphous region, and can provide antibacterial properties to play a role in preventing marine organisms.

[0012] In the present invention, the PND nanogel refers to acrylamide-dopamine acrylamide copolymer nanogel.

[0013] Preferably, the acrylamide comprises N-isopropylacrylamide.

[0014] Preferably, the reaction in step (1) further comprises adding aminosiloxane for reaction.

[0015] Preferably, the aminosilicone comprises 3-aminopropyltriethoxysilane (APS).

[0016] Preferably, the mass ratio of acrylamide to dopamine acrylamide is 9:(1-3), for example, 9:1.2, 9:1.4, 9:1.6, 9:1.8, 9:2.0, 9:2.2, 9:2.4, 9:2.6 or 9:2.8, etc.

[0017] Preferably, the mass ratio of acrylamide to aminosilicone is (5-18):1, for example, 7:1, 9:1, 11:1, 13:1, 15:1 or 17:1.

[0018] Preferably, step (1) specifically comprises the following steps: under nitrogen protection, acrylamide and water are mixed to form an acrylamide aqueous solution, and then an aminosiloxane aqueous solution and a dopamine acrylamide aqueous solution are added to react to obtain the PND nanogel.

[0019] In the present invention, acrylamide, dopamine acrylamide and aminosiloxane are mixed, and the self-polymerization of dopamine acrylamide and the free radical reaction of dopamine acrylamide with acrylamide under the induction of aminosiloxane are utilized to prepare acrylamide-dopamine acrylamide copolymer nanogel, referred to as PND nanogel. The dopamine acrylamide has a structure shown in the following formula a.

[0020]

[0021] In the present invention, the acrylamide is preferably N-isopropyl acrylamide, and the reaction formula of N-isopropyl acrylamide and dopamine acrylamide in step (1) is shown in the following formula b. In the formula, APS refers to 3-aminopropyl triethoxysilane, which can induce copolymerization of N-isopropyl acrylamide and dopamine acrylamide.

[0022]

[0023] Preferably, the concentration of the aqueous acrylamide solution is 4-8 g / L, for example, 4.5 g / L, 5 g / L, 5.5 g / L, 6 g / L, 6.5 g / L, 7 g / L or 7.5 g / L.

[0024] Preferably, the concentration of the aminosilicone aqueous solution is 15-20 g / L, for example, 15.5 g / L, 16 g / L, 16.5 g / L, 17 g / L, 17.5 g / L, 18 g / L, 18.5 g / L, 19 g / L or 19.5 g / L.

[0025] Preferably, the concentration of the dopamine acrylamide aqueous solution is 2 to 6 g / L, for example, 2.5 g / L, 3 g / L, 3.5 g / L, 4 g / L, 4.5 g / L, 5 g / L or 5.5 g / L.

[0026] Preferably, the adding of the aminosilicone aqueous solution is dropwise addition of the aminosilicone aqueous solution.

[0027] Preferably, the reaction temperature in step (1) is 60-80°C (e.g., 62°C, 64°C, 66°C, 68°C, 70°C, 72°C, 74°C, 76°C or 78°C, etc.), and the reaction time is 6-12h (e.g., 7h, 8h, 9h, 10h or 11h, etc.).

[0028] Preferably, the reaction in step (1) further includes dialysis and freeze-drying steps.

[0029] Preferably, the metal organic framework comprises NU-1000 or UiO-66(Zr).

[0030] Preferably, the preparation method of NU-1000 comprises the following steps:

[0031] (I) Dissolve zirconium oxychloride octahydrate (ZrOCl2·8H2O) and benzoic acid in an organic solvent to obtain solution A.

[0032] (II) 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene (H4TBAPy) is dissolved in an organic solvent to obtain solution B.

[0033] (III) The solution A obtained in step (I) and the solution B obtained in step (II) are mixed and reacted to obtain NU-1000.

[0034] Preferably, the organic solvent in step (I) and step (II) comprises dimethylformamide.

[0035] Preferably, the concentration of zirconium oxychloride octahydrate in the solution A is 0.05-0.15 mol / L, for example, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, 0.10 mol / L, 0.11 mol / L, 0.12 mol / L, 0.13 mol / L or 0.14 mol / L, etc.

[0036] Preferably, the concentration of benzoic acid in the solution A is 0.5-1.5 mol / L, for example, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1.0 mol / L, 1.1 mol / L, 1.2 mol / L, 1.3 mol / L or 1.4 mol / L.

[0037] Preferably, the concentration of 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene in the B solution is 0.005-0.015 mol / L, for example, 0.006 mol / L, 0.007 mol / L, 0.008 mol / L, 0.009 mol / L, 0.010 mol / L, 0.011 mol / L, 0.012 mol / L, 0.013 mol / L or 0.014 mol / L, etc.

[0038] Preferably, in step (III), the molar ratio of zirconium dichloride octahydrate in solution A to 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene in solution B is (5-15):1, for example 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1 or 14:1.

[0039] Preferably, the reaction temperature in step (III) is 120-140°C (e.g., 122°C, 124°C, 126°C, 128°C, 130°C, 132°C, 134°C, 136°C or 138°C, etc.), and the reaction time is 10-12h (e.g., 10.2h, 10.4h, 10.6h, 10.8h, 11.0h, 11.2h, 11.4h, 11.6h or 11.8h, etc.).

[0040] Preferably, the reaction in step (III) further includes filtering and washing steps.

[0041] Preferably, the organic solvent in step (2) comprises dimethylformamide.

[0042] Preferably, the mass ratio of the metal organic framework to hydrochloric acid in step (2) is 1:(25-75), for example, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65 or 1:70, etc.

[0043] Preferably, the concentration of the hydrochloric acid in step (2) is 1 to 2 mol / L, for example, 1.1 mol / L, 1.2 mol / L, 1.3 mol / L, 1.4 mol / L, 1.5 mol / L, 1.6 mol / L, 1.7 mol / L, 1.8 mol / L or 1.9 mol / L.

[0044] Preferably, the temperature of the heating activation in step (2) is 120-140°C (for example, 122°C, 124°C, 126°C, 128°C, 130°C, 132°C, 134°C, 136°C or 138°C, etc.), and the time is 12-24h (for example, 14h, 16h, 18h, 20h or 22h, etc.).

[0045] Preferably, the heating activation in step (2) further comprises the steps of filtering, washing and vacuum drying.

[0046] Preferably, the mass ratio of the PND nanogel to the activated metal organic framework in step (3) is 1.5:1 to 1:1.5, for example, 1.4:1, 1.3:1, 1.2:1, 1.1:1, 1:1, 1:1.1, 1:1.2, 1:1.3 or 1:1.4, etc.

[0047] Preferably, the mixing in step (3) also includes mixing with water.

[0048] Preferably, the volume of water in step (3) is 50-300 mL, for example, 80 mL, 110 mL, 140 mL, 170 mL, 200 mL, 230 mL, 260 mL or 290 mL.

[0049] Preferably, the water in step (3) is deionized water.

[0050] Preferably, the reaction temperature in step (3) is 25-40°C (e.g., 27°C, 29°C, 31°C, 33°C, 35°C, 37°C or 39°C, etc.), and the reaction time is 2-4h (e.g., 2.2h, 2.4h, 2.6h, 2.8h, 3.0h, 3.2h, 3.4h, 3.6h or 3.8h, etc.).

[0051] Preferably, the reaction in step (3) further includes dialysis and freeze-drying steps.

[0052] In a second aspect, the present invention provides a modified metal organic framework material, wherein the modified metal organic framework material is prepared by the preparation method described in the first aspect.

[0053] In a third aspect, the present invention provides an antibacterial composite material, comprising the following components in parts by weight: 100 parts of polyethylene and 3 to 15 parts of the modified metal organic framework material as described in the second aspect, for example 4 parts, 6 parts, 8 parts, 10 parts, 12 parts or 14 parts.

[0054] In the present invention, the composite of polyethylene and modified metal organic framework material can improve mechanical properties; in terms of preventing marine organisms, PND nanogel and polyethylene are thermodynamically incompatible. When seawater infiltrates, part of the PND nanogel will automatically seep out to the surface of the material to form a layer of hydrogel on the surface. At the same time, the self-oxidation of the PND nanogel will also produce active free radicals, thereby producing an antibacterial effect under the dual action of the hydrogel and the active free radicals, thereby achieving protection against marine organisms.

[0055] Preferably, the polyethylene comprises high density polyethylene.

[0056] Preferably, the density of the high-density polyethylene is 0.94-0.96 g / cm3 , for example 0.962 g / cm 3 , 0.964g / cm 3 , 0.966g / cm 3 、0.968g / cm 3 , 0.970g / cm 3 , 0.972g / cm 3 , 0.974g / cm 3 , 0.976g / cm 3 or 0.978 g / cm 3 wait.

[0057] Preferably, the antibacterial composite material further comprises a compatibilizer.

[0058] Preferably, the weight proportion of the compatibilizer in the antibacterial composite material is 4 to 6 parts, for example, 4.2 parts, 4.4 parts, 4.6 parts, 4.8 parts, 5.0 parts, 5.2 parts, 5.4 parts, 5.6 parts or 5.8 parts.

[0059] Preferably, the compatibilizer comprises polyethylene grafted maleic anhydride (HDPE-g-MAH).

[0060] In the present invention, the surface of the modified metal organic framework material contains olefin oligomers and secondary amino groups. A large number of secondary amino groups on the surface of the modified metal organic framework material can be connected to the anhydride groups in the polyethylene grafted maleic anhydride through amide chemical bonds, and the polyethylene chains in the polyethylene grafted maleic anhydride have good compatibility with the polyethylene matrix, thereby increasing the compatibility between the components.

[0061] Preferably, the antibacterial composite material further comprises an antioxidant.

[0062] Preferably, the weight portion of the antioxidant in the antibacterial composite material is 0.1 to 0.2 parts, for example, 0.11 parts, 0.12 parts, 0.13 parts, 0.14 parts, 0.15 parts, 0.16 parts, 0.17 parts, 0.18 parts or 0.19 parts.

[0063] In a fourth aspect, the present invention provides a use of the antibacterial composite material as described in the third aspect in the preparation of a marine organism prevention device.

[0064] Compared with the prior art, the present invention has the following beneficial effects:

[0065] The modified metal organic framework material of the present invention can improve the mechanical properties and antibacterial properties of a polymer matrix. The antibacterial composite material prepared by adding the modified metal organic framework material has excellent mechanical properties and anti-marine biomass properties. It can be used as the main material of an anti-marine biomass device that utilizes ocean driving force to remove marine biomass, and can be used in a marine environment for a long time. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 This is a scanning electron microscope image of the modified metal organic framework material prepared in Example 1;

[0067] Figure 2 This is the XRD pattern of the modified metal organic framework material obtained in Example 1;

[0068] Figure 3 The infrared spectra of the PND nanogel and modified metal organic framework material prepared in Example 1 are shown. DETAILED DESCRIPTION

[0069] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0070] The sources of some components in the following examples and comparative examples are as follows:

[0071] Zirconium dichloride octahydrate, benzoic acid, N,N-dimethylformamide, 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene, acetone, N-isopropylacrylamide, 3-aminopropyltriethoxysilane, dopamineacrylamide, antioxidant 1010, all of the above products are analytically pure and commercially available;

[0072] High-density polyethylene, grade 5000S;

[0073] Polyethylene grafted with maleic anhydride, brand name CMG5804.

[0074] Example 1

[0075] This embodiment provides a modified metal organic framework material and an antibacterial composite material, wherein the modified metal organic framework material is prepared by the following method:

[0076] (1) 0.9 g of N-isopropylacrylamide was added to 150 mL of deionized water under magnetic stirring to form an N-isopropylacrylamide aqueous solution, and nitrogen was used for protection. Then, 5 mL of 3-aminopropyltriethoxysilane aqueous solution (concentration of 20 g / L) was added dropwise to the above N-isopropylacrylamide aqueous solution within 30 min. During this process, the system temperature was raised to 70°C, and then 50 mL of dopamine acrylamide aqueous solution (concentration of dopamine acrylamide was 5 g / L) was added thereto. The reaction lasted for 6 h, and then the obtained solution was dialyzed through a dialysis membrane (pore size 10 nm) (water was replaced every 3 h for 7 days). After freeze-drying at -40°C for 12 h, 0.60 g of white PND nanogel was obtained, which was recorded as PND.

[0077] (2) Dissolve 0.03 mol of zirconium oxychloride octahydrate and 0.3 mol of benzoic acid in 300 mL of dimethylformamide, and continue stirring until the solution is clear to obtain solution A; dissolve 0.003 mol of 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene in 300 mL of dimethylformamide, and stir to obtain solution B; heat solution A and solution B to 50° C. respectively, and then slowly add solution B to solution A under stirring, wherein the molar ratio of zirconium oxychloride octahydrate in solution A to 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene in solution B is 10:1; then react the mixed solution at 120° C. for 10 h, filter, wash with dimethylformamide solvent, and vacuum dry to obtain NU-1000 in the form of a yellow powder;

[0078] 0.2 g of the above NU-1000 was dispersed in 10 mL of dimethylformamide, and then 10 g of hydrochloric acid (concentration of 2 mol / L) was added, and hydrothermally heated to 120° C. for activation for 12 h, and then filtered, washed with dimethylformamide and acetone three times respectively, and vacuum dried to obtain an activated metal organic framework.

[0079] (3) 0.2 g of the PND nanogel prepared in step (1) and 0.2 g of the activated metal organic framework prepared in step (2) were dispersed in 50 mL of deionized water and mixed, stirred at 25° C. for 2 h, dialyzed through a dialysis membrane (pore size 10 nm) (water was replaced every 3 h for 7 days), and freeze-dried at -40° C. for 12 h to obtain the modified metal organic framework material, recorded as NU-1000@PND.

[0080] The antibacterial composite material includes the following components by weight: 100 parts of polyethylene (high-density polyethylene, 5000S), 10 parts of the above-mentioned modified metal organic framework material, 5 parts of a compatibilizer (polyethylene grafted maleic anhydride, CMG5804) and 0.1 parts of an antioxidant (antioxidant 1010).

[0081] The antibacterial composite material is prepared by the following method: polyethylene, the modified metal organic framework material, a compatibilizer and an antioxidant are mixed, and injection molding is performed by an injection molding machine at an injection molding temperature of 175° C. to obtain the antibacterial composite material.

[0082] Example 2

[0083] This embodiment provides a modified metal organic framework material and an antibacterial composite material. The difference between this embodiment and embodiment 1 is that the weight proportion of the modified metal organic framework material in the antibacterial composite material is adjusted to 4 parts, and other conditions are the same as those in embodiment 1.

[0084] Example 3

[0085] This embodiment provides a modified metal organic framework material and an antibacterial composite material. The difference between this embodiment and embodiment 1 is that the weight proportion of the modified metal organic framework material in the antibacterial composite material is adjusted to 6 parts, and other conditions are the same as those in embodiment 1.

[0086] Example 4

[0087] This embodiment provides a modified metal organic framework material and an antibacterial composite material. The difference between this embodiment and embodiment 1 is that the weight proportion of the modified metal organic framework material in the antibacterial composite material is adjusted to 8 parts, and other conditions are the same as those in embodiment 1.

[0088] Example 5

[0089] This embodiment provides a modified metal organic framework material and an antibacterial composite material. The difference between this embodiment and embodiment 1 is that the weight proportion of the modified metal organic framework material in the antibacterial composite material is adjusted to 12 parts, and other conditions are the same as those in embodiment 1.

[0090] Example 6

[0091] The present embodiment provides a modified metal organic framework material and an antibacterial composite material, which differs from the embodiment 1 in that step (2) is adjusted to disperse 0.2 g UiO-66 (Zr) in 10 mL dimethylformamide, then add 10 g hydrochloric acid (concentration is 2 mol / L), hydrothermally heat to 120° C. for activation for 12 h, then filter, wash with dimethylformamide and acetone for 3 times respectively, and vacuum dry to obtain an activated metal organic framework. The other conditions are the same as those in the embodiment 1.

[0092] Example 7

[0093] This embodiment provides a modified metal organic framework material and an antibacterial composite material, wherein the modified metal organic framework material is prepared by the following method:

[0094] (1) 0.9 g of N-isopropylacrylamide was added to 150 mL of deionized water under magnetic stirring to form an N-isopropylacrylamide aqueous solution, and nitrogen was used for protection. Then, 5 mL of 3-aminopropyltriethoxysilane aqueous solution (concentration of 10 g / L) was added dropwise to the above N-isopropylacrylamide aqueous solution within 30 min. During this process, the system temperature was raised to 70°C, and then 50 mL of dopamine acrylamide aqueous solution (concentration of dopamine acrylamide was 2 g / L) was added thereto. The reaction lasted for 6 h, and then the obtained solution was dialyzed through a dialysis membrane (pore size 10 nm) (water was replaced every 3 h for 7 days). After freeze-drying at -40°C for 12 h, 0.45 g of white PND nanogel was obtained.

[0095] (2) Dissolve 0.015 mol of zirconium oxychloride octahydrate and 0.15 mol of benzoic acid in 300 mL of dimethylformamide, and continue stirring until the solution is clear to obtain solution A; dissolve 0.015 mol of 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene in 300 mL of dimethylformamide, and stir to obtain solution B; heat solution A and solution B to 50° C. respectively, and then slowly add solution B to solution A under stirring, wherein the molar ratio of zirconium oxychloride octahydrate in solution A to 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene in solution B is 10:1; then react the mixed solution at 120° C. for 10 h, filter, wash with dimethylformamide solvent, and vacuum dry to obtain NU-1000 in the form of a yellow powder;

[0096] 0.2 g of the above NU-1000 was dispersed in 10 mL of dimethylformamide, and then 5 g of hydrochloric acid (concentration of 2 mol / L) was added, and hydrothermally heated to 120° C. for activation for 12 h, and then filtered, washed with dimethylformamide and acetone three times respectively, and vacuum dried to obtain an activated metal organic framework.

[0097] (3) Disperse 0.15 g of the PND nanogel prepared in step (1) and 0.1 g of the activated metal organic framework prepared in step (2) into 50 mL of deionized water, stir at 25° C. for 2 h, dialyze through a dialysis membrane (pore size 10 nm) (replace water every 3 h for 7 days), and freeze-dry at -40° C. for 12 h to obtain the modified metal organic framework material.

[0098] The antibacterial composite material includes the following components by weight: 100 parts of polyethylene (high-density polyethylene, 5000S), 10 parts of the above-mentioned modified metal organic framework material, 4 parts of a compatibilizer (polyethylene grafted maleic anhydride, CMG5804) and 0.1 parts of an antioxidant (antioxidant 1010).

[0099] The antibacterial composite material is prepared by the following method: polyethylene, the modified metal organic framework material, a compatibilizer and an antioxidant are mixed, and injection molding is performed by an injection molding machine at an injection molding temperature of 175° C. to obtain the antibacterial composite material.

[0100] Example 8

[0101] This embodiment provides a modified metal organic framework material and an antibacterial composite material, wherein the modified metal organic framework material is prepared by the following method:

[0102] (1) 0.9 g of N-isopropylacrylamide was added to 150 mL of deionized water under magnetic stirring to form an N-isopropylacrylamide aqueous solution, and nitrogen was used for protection. Then, 5 mL of 3-aminopropyltriethoxysilane aqueous solution (concentration of 30 g / L) was added dropwise to the above N-isopropylacrylamide aqueous solution within 30 min. During this process, the system temperature was raised to 70°C, and then 50 mL of dopamine acrylamide aqueous solution (concentration of dopamine acrylamide was 6 g / L) was added thereto. The reaction was continued for 12 h, and then the obtained solution was dialyzed through a dialysis membrane (pore size 10 nm) (water was replaced every 3 h for 7 days). After freeze-drying at -40°C for 12 h, 0.72 g of white PND nanogel was obtained.

[0103] (2) Dissolve 0.045 mol of zirconium oxychloride octahydrate and 0.45 mol of benzoic acid in 300 mL of dimethylformamide, and continue stirring until the solution is clear to obtain solution A; dissolve 0.045 mol of 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene in 300 mL of dimethylformamide, and stir to obtain solution B; then heat solution A and solution B to 50° C. respectively, and then slowly add solution B to solution A under stirring, wherein the molar ratio of zirconium oxychloride octahydrate in solution A to 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene in solution B is 10:1; then react the mixed solution at 140° C. for 12 h, filter, wash with dimethylformamide solvent, and vacuum dry to obtain NU-1000 in the form of a yellow powder;

[0104] 0.2 g of the above NU-1000 was dispersed in 10 mL of dimethylformamide, and then 15 g of hydrochloric acid (concentration of 2 mol / L) was added, and hydrothermally heated to 140° C. for activation for 24 h, and then filtered, washed with dimethylformamide and acetone three times respectively, and vacuum dried to obtain an activated metal organic framework.

[0105] (3) Disperse 0.10 g of the PND nanogel prepared in step (1) and 0.15 g of the activated metal organic framework prepared in step (2) into 50 mL of deionized water, stir at 40° C. for 4 h, dialyze through a dialysis membrane (pore size 10 nm) (replace water every 3 h for 7 days), and freeze-dry at -40° C. for 12 h to obtain the modified metal organic framework material.

[0106] The antibacterial composite material includes the following components by weight: 100 parts of polyethylene (high-density polyethylene, 5000S), 10 parts of the above-mentioned modified metal organic framework material, 6 parts of a compatibilizer (polyethylene grafted maleic anhydride, CMG5804) and 0.2 parts of an antioxidant (antioxidant 1010).

[0107] The antibacterial composite material is prepared by the following method: polyethylene, the modified metal organic framework material, a compatibilizer and an antioxidant are mixed, and injection molding is performed by an injection molding machine at an injection molding temperature of 175° C. to obtain the antibacterial composite material.

[0108] Comparative Example 1

[0109] This comparative example provides a modified metal organic framework material and an antibacterial composite material. The difference between this comparative example and Example 1 is that the weight portion of the modified metal organic framework material in the antibacterial composite material is adjusted to 2 parts, and other conditions are the same as those in Example 1.

[0110] Comparative Example 2

[0111] This comparative example provides a composite material, which includes the following components in parts by weight: 100 parts of polyethylene (high-density polyethylene, 5000S), 5 parts of a compatibilizer (polyethylene grafted maleic anhydride, CMG5804) and 0.1 parts of an antioxidant (antioxidant 1010).

[0112] The composite material is prepared by the following method: polyethylene, a compatibilizer and an antioxidant are mixed, and injection molding is performed by an injection molding machine at an injection molding temperature of 175° C. to obtain the composite material.

[0113] Comparative Example 3

[0114] This comparative example provides an antibacterial composite material, which differs from Example 1 in that the modified metal organic framework material in the antibacterial composite material is replaced by an activated metal organic framework obtained in step (2) of the same mass, and other conditions are the same as those in Example 1.

[0115] Comparative Example 4

[0116] This comparative example provides an antibacterial composite material, which differs from Example 1 in that the modified metal organic framework material in the antibacterial composite material is replaced by the PND nanogel prepared in step (1) of the same mass, and other conditions are the same as those in Example 1.

[0117] The antibacterial composite materials provided in the above-mentioned Examples 1-8 and Comparative Examples 1, 3, 4 and the composite material provided in Comparative Example 2 were subjected to the following performance tests:

[0118] Tensile strength: tested in accordance with GB / T1040.1-2006 standard, the test results are shown in Table 1;

[0119] Elongation at break: tested in accordance with GB / T1040.1-2006 standard, the test results are shown in Table 1;

[0120] Bending strength: tested in accordance with GB / T9341-2008 standard, the test results are shown in Table 1;

[0121] Antibacterial properties: Shewanella (S. oneidensis MR -1 ) as the representative, verify the antibacterial results, and test by plate colony counting method. Different samples were placed in 30mL of 10 5 CFU / mL of bacterial solution and cultured at 37°C for 24 hours. The bacterial solution after soaking was spread on nutrient agar plates and cultured at 37°C for 24 hours. The number of colonies was observed to determine the antibacterial effect of the sample. The fewer the number of colonies, the better the antibacterial effect. The test results are shown in Table 1.

[0122] Table 1

[0123]

[0124] In Table 1, “ / ” means that the test was not conducted.

[0125] From the contents of Table 1, it can be seen that the antibacterial composite materials provided by Examples 1 to 8 have a tensile strength of ≥31.69 MPa, an elongation at break of ≥663.8%, a bending strength of ≥24.0 MPa, and a colony count of ≤15, and have both high mechanical properties and antibacterial effects.

[0126] The morphology of the modified metal organic framework material obtained in Example 1 is as follows: Figure 1 As shown, it is a rod-like structure, and its XRD pattern is as follows Figure 2 As shown, the infrared spectra of PND nanogel and modified metal organic framework materials are shown in Figure 3 As shown, located at 1621cm -1 The characteristic peak of νC=C at π confirms the occurrence and completion of the free radical copolymerization reaction.

[0127] It can be seen from Comparative Example 1 and Examples 1-5 that under the condition of fixed addition of 5 parts of compatibilizer and 0.1 parts of antioxidant, after adding 2, 4, 6, 8, 10 and 12 parts of modified metal organic framework materials respectively, the antibacterial composite materials are prepared, and the tensile strength, elongation at break and flexural strength first increase and then decrease, and the antibacterial property increases; as the weight portion of the modified metal organic framework material increases from 2 to 10 parts, the tensile strength and flexural strength are significantly improved, and the elongation at break increases by a greater margin. This is because a large number of hydroxyl groups on the surface of PND nanogel can react with hydroxyl groups on the surface of NU-1000 nanoparticles to form ether bonds, so that PND and NU-1000 nanoparticles are closely combined, and the effect of the polyethylene grafted maleic anhydride compatibilizer enhances the bonding between NU-1000 and polyethylene. The interface compatibility between the bodies is improved, the mechanical properties are improved, and the antibacterial effect is also significantly improved; when the weight portion of the modified metal organic framework material is greater than 10 parts, the tensile strength, elongation at break and flexural strength are reduced. This is because when the content of the modified metal organic framework material is too high, agglomeration will occur, thereby affecting the mechanical properties, but the surface of the antibacterial performance test culture dish can still remain free of any bacterial growth (Example 5); when the weight portion of the modified metal organic framework material is 10 parts, the various performance indicators are optimal. Compared with the composite material prepared without adding the modified metal organic framework material, the tensile strength increases from 30.99Mpa to 34.38Mpa, and the flexural strength increases from 23Mpa to 26.8MPa, indicating that the addition of the modified metal organic framework material has significantly improved both the mechanical properties and the antibacterial properties.

[0128] Compared with Example 1, if NU-1000 is replaced with UiO-66(Zr) of the same mass (Example 6), the tensile strength, elongation at break and flexural strength of the prepared antibacterial composite material are slightly reduced. It can be seen that the metal organic framework is preferably NU-1000, and the mechanical properties of the prepared antibacterial composite material are better.

[0129] Compared with Example 1, if the modified metal organic framework material is not added (Comparative Example 2), the mechanical properties and antibacterial properties of the prepared antibacterial composite material are relatively low.

[0130] Compared with Example 1, if the modified metal-organic framework material is replaced with the same mass of activated metal-organic framework (Comparative Example 3) or the modified metal-organic framework material is replaced with the same mass of PND nanogel (Comparative Example 4), the mechanical properties and antibacterial properties of the prepared antibacterial composite material are reduced. It can be seen that the mechanical properties and antibacterial properties of the antibacterial composite material prepared using the modified metal-organic framework material are better.

[0131] In summary, the addition of modified metal-organic framework materials in the present invention can improve the bending strength, tensile strength and anti-marine biological performance of the material, and the raw material cost is low. The antibacterial composite material prepared by modified metal-organic framework materials, polyethylene, compatibilizers and antioxidants has the advantages of high mechanical strength, good anti-marine biological performance, etc., is economical and convenient, and has no pollution emissions.

[0132] The applicant declares that the present invention illustrates the process method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned process steps, that is, it does not mean that the present invention must rely on the above-mentioned process steps to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a modified metal organic framework material, characterized in that: The preparation method comprises the following steps: (1) acrylamide and dopamine acrylamide react to obtain PND nanogel; (2) mixing the metal organic framework with an organic solution and hydrochloric acid, and heating and activating the mixture to obtain an activated metal organic framework; (3) mixing the PND nanogel prepared in step (1) and the activated metal organic framework prepared in step (2), and reacting them to obtain the modified metal organic framework material.

2. The preparation method according to claim 1, characterized in that: The acrylamide includes N-isopropylacrylamide; Preferably, the reaction in step (1) further comprises adding aminosiloxane for reaction; Preferably, the aminosilicone comprises 3-aminopropyltriethoxysilane; Preferably, the mass ratio of acrylamide to dopamine acrylamide is 9:(1-3); Preferably, the mass ratio of acrylamide to aminosiloxane is (5-18):1; Preferably, step (1) specifically comprises the following steps: under nitrogen protection conditions, mixing acrylamide and water to form an acrylamide aqueous solution, and then adding an aminosiloxane aqueous solution and a dopamine acrylamide aqueous solution to react to obtain a PND nanogel; Preferably, the concentration of the acrylamide aqueous solution is 4 to 8 g / L; Preferably, the concentration of the aminosilicone aqueous solution is 15 to 20 g / L; Preferably, the concentration of the dopamine acrylamide aqueous solution is 2 to 6 g / L; Preferably, the adding of the aminosilicone aqueous solution is dropwise addition of the aminosilicone aqueous solution; Preferably, the reaction temperature in step (1) is 60-80° C., and the reaction time is 6-12 h; Preferably, the reaction in step (1) further includes dialysis and freeze-drying steps.

3. The preparation method according to claim 1 or 2, characterized in that: The metal organic framework comprises NU-1000 or UiO-66(Zr); Preferably, the preparation method of NU-1000 comprises the following steps: (I) dissolving zirconium dichloride octahydrate and benzoic acid in an organic solvent to obtain a solution A; (II) dissolving 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene in an organic solvent to obtain a solution B; (III) mixing the solution A obtained in step (I) and the solution B obtained in step (II), reacting them to obtain NU-1000; Preferably, the organic solvent in step (I) and step (II) comprises dimethylformamide; Preferably, the concentration of zirconium oxychloride octahydrate in the A solution is 0.05 to 0.15 mol / L; Preferably, the concentration of benzoic acid in the solution A is 0.5 to 1.5 mol / L; Preferably, the concentration of 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene in the B solution is 0.005 to 0.015 mol / L; Preferably, in step (III), the molar ratio of zirconium oxychloride octahydrate in solution A to 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene in solution B is (5-15):1; Preferably, the reaction temperature in step (III) is 120-140°C, and the reaction time is 10-12h; Preferably, the reaction in step (III) further comprises filtering and washing steps.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The organic solvent in step (2) comprises dimethylformamide; Preferably, the mass ratio of the metal organic framework to hydrochloric acid in step (2) is 1:(25-75); Preferably, the concentration of the hydrochloric acid in step (2) is 1 to 2 mol / L; Preferably, the temperature of the heating activation in step (2) is 120-140° C. and the time is 12-24 hours; Preferably, the heating activation in step (2) further comprises the steps of filtering, washing and vacuum drying.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The mass ratio of the PND nanogel to the activated metal organic framework in step (3) is 1.5:1 to 1:1.5; Preferably, the mixing in step (3) further comprises mixing with water; Preferably, the volume of water in step (3) is 50 to 300 mL; Preferably, the water in step (3) is deionized water; Preferably, the reaction temperature in step (3) is 25-40°C and the reaction time is 2-4h; Preferably, the reaction in step (3) further includes dialysis and freeze-drying steps.

6. A modified metal organic framework material, characterized in that: The modified metal organic framework material is prepared by the preparation method according to any one of claims 1 to 5.

7. An antibacterial composite material, characterized in that: The antibacterial composite material comprises the following components by weight: 100 parts of polyethylene and 3 to 15 parts of the modified metal organic framework material according to claim 6.

8. The antibacterial composite material according to claim 7, characterized in that: The polyethylene includes high-density polyethylene; Preferably, the density of the high-density polyethylene is 0.94-0.96 g / cm 3 ; Preferably, the antibacterial composite material further comprises a compatibilizer; Preferably, the weight proportion of the compatibilizer in the antibacterial composite material is 4 to 6 parts; Preferably, the compatibilizer comprises polyethylene grafted with maleic anhydride.

9. The antibacterial composite material according to claim 7 or 8, characterized in that: The antibacterial composite material also includes an antioxidant; Preferably, the weight portion of the antioxidant in the antibacterial composite material is 0.1 to 0.2 parts.

10. Use of the antibacterial composite material according to any one of claims 7 to 9 in the preparation of a marine organism prevention device.

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