CN113444197A - Halamine antibacterial agent and preparation method and application thereof - Google Patents
Halamine antibacterial agent and preparation method and application thereof Download PDFInfo
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- CN113444197A CN113444197A CN202010214759.5A CN202010214759A CN113444197A CN 113444197 A CN113444197 A CN 113444197A CN 202010214759 A CN202010214759 A CN 202010214759A CN 113444197 A CN113444197 A CN 113444197A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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Abstract
The invention discloses a halamine antibacterial agent and a preparation method thereof, wherein the preparation method comprises the following steps: (1) adding methacrylic acid into a solvent, adding N-hydroxymethyl acrylamide and dibenzoyl peroxide under the stirring condition, and reacting to obtain a product A; (2) adding the product A, deionized water and potassium hypochlorite into a reaction vessel, and stirring and reacting for 8-10h at 60-80 ℃ to obtain a solution B; (3) and (3) dropwise adding an acid solution into the solution B to adjust the pH value of the solution to be neutral, filtering, washing, drying and grinding to obtain the halamine antibacterial agent. The invention also discloses application of the halamine antibacterial agent in the nylon composite material. The halogen amine antibacterial agent prepared by the invention has simple synthesis process and strong antibacterial effect, and can well improve the antibacterial property of the nylon composite material. The antibacterial agent prepared by the invention has good compatibility with polyamide, is more uniformly dispersed during processing, and can be slowly released in a product, so that the antibacterial agent has better safety and durability.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a halamine antibacterial agent, and a preparation method and application thereof.
Background
The antibacterial material is a novel functional material with the function of killing or inhibiting microorganisms. The application of the antibacterial material can create a healthy living environment, and the probability of bacterial infection is reduced through prevention in advance; effectively reduces or eliminates the bacterial cross infection between people and objects. The common antibacterial plastic can be processed by adding organic antibacterial agent and natural antibacterial agent into resin. The organic antibacterial agent and the natural antibacterial agent comprise various antibiotic drugs, chitosan and the like, and have the advantages of good antibacterial effect and strong killing power to various bacteria; but has poor heat resistance, is easily decomposed at high temperature, and has a short life. The invention creatively synthesizes a novel halamine antibacterial agent, which can well improve the antibacterial performance of the polyamide composite material and has good heat resistance and durability.
Disclosure of Invention
The invention aims to provide a halamine antibacterial agent, and a preparation method and application thereof, so as to solve the problems in the prior art.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a halamine antibacterial agent comprises the following steps:
(1) adding methacrylic acid (MAA) into a solvent, adding N-Hydroxymethyl Acrylamide (HAM) and dibenzoyl peroxide (BPO) under the stirring condition, reacting for 6-8h at 70-90 ℃, filtering and drying to obtain a product A; the chemical equation of the reaction is shown as follows:
(2) adding the product A, deionized water and potassium hypochlorite (KClO) into a reaction vessel, and stirring and reacting at 60-80 ℃ for 8-10h to obtain a solution B; the chemical equation of the reaction is shown as follows:
(3) and (3) dropwise adding concentrated hydrochloric acid into the solution B to adjust the pH value of the solution to be neutral, filtering, washing, drying and grinding to obtain the halamine antibacterial agent with the particle size not more than 23 mu m.
In a further scheme, in the step (1), the solvent is acetone; the mass ratio of the methacrylic acid to the acetone to the dibenzoyl peroxide to the N-hydroxymethyl acrylamide is (30-40): (180-240): (0.8-1): (20-24).
In the step (1), the drying temperature is 60-80 ℃, and the drying time is 4-6 h.
Further, in the step (2), the mass ratio of the product A, the deionized water and the potassium hypochlorite is (60-80): (200-280): (50-70).
The second object of the present invention is to provide a halamine-type antibacterial agent obtained by the above-mentioned preparation method.
The third purpose of the invention is to provide the application of the halamine antibacterial agent in the nylon composite material, wherein the nylon composite material is prepared from the halamine antibacterial agent and nylon by the following method:
adding the halamine antibacterial agent and the nylon into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, and performing blending extrusion to obtain the nylon composite material.
In a further scheme, the nylon is one of polycaprolactam (PA6), polyhexamethylene adipamide (PA66) and polypentylene adipamide (PA56)
Compared with the prior art, the invention has the beneficial effects that:
(1) the synthesis of the halamine antibacterial agent is innovative, the synthesis process is simple, the antibacterial effect of the antibacterial agent is strong, and the antibacterial property of the nylon composite material can be well improved.
(2) Compared with other antibacterial agents, the antibacterial agent is prepared by substituting hydrogen atoms of amino groups on amide groups with chlorine, has a chemical structure similar to that of the amide groups, has good compatibility, is more uniformly dispersed during processing, can be slowly released in products, cannot be quickly separated out, and has better safety and durability.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The types and suppliers of reagents used in this example were as follows: methacrylic acid, denna century, chemical ltd; acetone solution, Shandong Xu Chen chemical science and technology Co., Ltd; dibenzoyl peroxide, tanzhou haixiang chemical ltd; n-methylolacrylamide, Vietnam chemical Limited; deionized water, xianmen australian spring environmental protection technology ltd; potassium hypochlorite, Cangzhou gold lion chemical Co., Ltd; PA6 (model IM), russian gutobov nitrogen; PA66 (model U4800), Invitrogen; PA56 (model 1200G), Kaiser bio.
The reagents are provided only for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not indicate that the present invention cannot be realized by using other reagents of the same type or other reagents supplied by other suppliers.
The test instrument used in the present invention is as follows:
model ZSK30 twin-screw extruder, W & P, Germany; JL-1000 type tensile testing machine, produced by Guangzhou Youcai laboratory instruments; HTL900-T-5B injection molding machine, manufactured by Haita plastics machinery, Inc.; XCJ-500 impact tester, manufactured by Chengde tester; QT-1196 tensile tester, Gaotai detection instruments, Inc. of Dongguan; QD-GJS-B12K model high-speed mixer, HengOde instruments, Beijing.
Unless otherwise specified, the parts in the following embodiments are parts by weight. The antibacterial rate of the present invention was measured in accordance with JIS Z2801, and the test was carried out using a test piece of the specification (50 mm. + -. 2 mm. + -. 6 mm. + -. 0.1mm) and after 24 hours of inoculation.
Example 1
(1) 300g of methacrylic acid (MAA), 1.8kg of acetone solution, 8g of dibenzoyl peroxide (BPO) and 200g of N-methylolacrylamide (HAM) are weighed out.
(2) Adding MAA into a three-neck flask filled with acetone solution, adding MAA and BPO under rapid stirring, reacting at 70 ℃ for 6h, filtering the product obtained by the reaction, and drying in an oven at 60 ℃ for 4h to obtain the product A.
(3) 600g of the product A, 2.0kg of deionized water and 500g of potassium hypochlorite (KClO) are weighed and added into a reaction vessel, and the mixture is stirred and reacted for 8 hours at the temperature of 60 ℃ to obtain a solution B.
(4) Dropwise adding a certain amount of concentrated hydrochloric acid into the solution B until the pH value of the solution is 7, filtering, washing, drying, grinding, and sieving with a 600-mesh sieve to obtain the antibacterial agent P1 with the particle size of no more than 23 μm.
Application example 1
Adding 1 part of P1 into 99 parts of PA66, stirring for 10min by a high-speed mixer, and then adding into a double-screw extruder for blending and extruding to obtain the PA66 composite material X1.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first temperature zone is 210 ℃, the temperature of the second temperature zone is 220 ℃, the temperature of the third temperature zone is 240 ℃, the temperature of the fourth temperature zone is 260 ℃, the temperature of the fifth temperature zone is 265 ℃, the temperature of the sixth temperature zone is 265 ℃, the head temperature of the double-screw extruder is 265 ℃, and the screw rotating speed is 200 r/min.
Comparative example 1
And (3) taking 99 parts of PA66, stirring for 10min by a high-speed mixer, and then adding the PA66 into a double-screw extruder for blending and extruding to obtain the PA66 composite material D1.
The antibacterial performance data of the PA66 composite materials prepared in application example 1 and comparative example 1 are shown in table 1 below:
TABLE 1 antimicrobial Performance data for the products
As can be seen from the above table, X1 has better antibacterial property than D1, which indicates that the antibacterial property of the PA66 composite material is better after the antibacterial agent of the present invention is added.
Example 2
(1) 400g of methacrylic acid (MAA), 2.4kg of acetone solution, 10g of dibenzoyl peroxide (BPO) and 240g of N-methylolacrylamide (HAM) are weighed out.
(2) Adding MAA into a three-neck flask filled with acetone solution, adding MAA and BPO under rapid stirring, reacting for 8h at 90 ℃, filtering the product obtained by the reaction, and drying in an oven at 80 ℃ for 6h to obtain the product A.
(3) 800g of the product A, 2.8kg of deionized water and 700g of potassium hypochlorite (KClO) are weighed and added into a reaction vessel, and the mixture is stirred and reacted for 10 hours at 80 ℃ to obtain a solution B.
(4) Dropwise adding a certain amount of concentrated hydrochloric acid into the solution B until the pH value of the solution is 7, filtering, washing, drying, grinding, and sieving with a 600-mesh sieve to obtain the antibacterial agent P2 with the particle size of no more than 23 μm.
Application example 2
Adding 1 part of P2 into 99 parts of PA56, stirring for 10min by a high-speed mixer, and then adding into a double-screw extruder for blending and extruding to obtain the PA56 composite material X2.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first temperature zone is 210 ℃, the temperature of the second temperature zone is 220 ℃, the temperature of the third temperature zone is 235 ℃, the temperature of the fourth temperature zone is 255 ℃, the temperature of the fifth temperature zone is 260 ℃, the temperature of the sixth temperature zone is 260 ℃, the head temperature of the double-screw extruder is 260 ℃, and the screw rotating speed is 300 r/min.
Comparative example 2
And (3) taking 99 parts of PA56, stirring for 10min by a high-speed mixer, and then adding the PA56 into a double-screw extruder for blending and extruding to obtain the PA56 composite material D2.
The antibacterial performance data of the PA56 composite materials prepared in application example 2 and comparative example 2 are shown in table 2 below:
TABLE 2 antimicrobial Performance data of the products
As can be seen from the above table, X2 has better antibacterial property than D2, which indicates that the antibacterial property of the PA56 composite material is better after the antibacterial agent of the present invention is added.
Example 3
(1) 350g of methacrylic acid (MAA), 2.1kg of acetone solution, 9g of dibenzoyl peroxide (BPO) and 220g of N-methylolacrylamide (HAM) are weighed out.
(2) Adding MAA into a three-neck flask filled with acetone solution, adding MAA and BPO under rapid stirring, reacting at 80 ℃ for 7h, filtering the product obtained by the reaction, and drying in a 70 ℃ oven for 5h to obtain the product A.
(3) 700g of the product A, 2.4kg of deionized water and 600g of potassium hypochlorite (KClO) are weighed and added into a reaction vessel, and the mixture is stirred and reacted for 9 hours at 70 ℃ to obtain a solution B.
(4) Dropwise adding a certain amount of concentrated hydrochloric acid into the solution B until the pH value of the solution is 7, filtering, washing, drying, grinding, and sieving with a 600-mesh sieve to obtain the antibacterial agent P3 with the particle size of no more than 23 μm.
Application example 3
Adding 1 part of P3 into 99 parts of PA6, stirring for 10min by a high-speed mixer, and then adding into a double-screw extruder for blending and extruding to obtain the PA6 composite material X3.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first temperature zone is 200 ℃, the temperature of the second temperature zone is 210 ℃, the temperature of the third temperature zone is 220 ℃, the temperature of the fourth temperature zone is 225 ℃, the temperature of the fifth temperature zone is 225 ℃, the temperature of the sixth temperature zone is 225 ℃, the head temperature of the double-screw extruder is 225 ℃, and the screw rotating speed is 300 r/min.
Comparative example 3
And (3) taking 99 parts of PA6, stirring for 10min by a high-speed mixer, and then adding the PA6 into a double-screw extruder for blending and extruding to obtain the PA6 composite material D3.
Example 4
(1) 360g of methacrylic acid (MAA), 2.1kg of acetone solution, 8g of dibenzoyl peroxide (BPO) and 230g of N-methylolacrylamide (HAM) are weighed out.
(2) Adding MAA into a three-neck flask filled with acetone solution, adding MAA and BPO under rapid stirring, reacting at 75 ℃ for 6h, filtering the product obtained by the reaction, and drying in a 65 ℃ oven for 6h to obtain the product A.
(3) 750g of the product A, 2.5kg of deionized water and 650g of potassium hypochlorite (KClO) are weighed and added into a reaction vessel, and the mixture is stirred and reacted for 10 hours at 65 ℃ to obtain a solution B.
(4) Dropwise adding a certain amount of concentrated hydrochloric acid into the solution B until the pH value of the solution is 7, filtering, washing, drying, grinding, and sieving with a 600-mesh sieve to obtain the antibacterial agent P4 with the particle size of no more than 23 μm.
Application example 4
Adding 1 part of P4 into 99 parts of polyamide 6(PA6), stirring for 10min by a high-speed mixer, and then adding into a double-screw extruder for blending and extruding to obtain the PA6 composite material X4.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first temperature zone is 200 ℃, the temperature of the second temperature zone is 210 ℃, the temperature of the third temperature zone is 220 ℃, the temperature of the fourth temperature zone is 225 ℃, the temperature of the fifth temperature zone is 225 ℃, the temperature of the sixth temperature zone is 225 ℃, the head temperature of the double-screw extruder is 225 ℃, and the screw rotating speed is 320 r/min.
Comparative example 4
And (2) taking 1 part of antibacterial agent chitosan micro powder and 99 parts of PA6, stirring for 10min by using a high-speed mixer, and then adding the materials into a double-screw extruder for blending and extruding to obtain the PA6 composite material D4.
Example 5
(1) 410g of methacrylic acid (MAA), 2.1kg of acetone solution, 8g of dibenzoyl peroxide (BPO) and 230g of N-methylolacrylamide (HAM) are weighed out.
(2) Adding MAA into a three-neck flask filled with acetone solution, adding MAA and BPO under rapid stirring, reacting at 75 ℃ for 6h, filtering the product obtained by the reaction, and drying in a 65 ℃ oven for 6h to obtain the product A.
(3) 750g of the product A, 2.5kg of deionized water and 650g of potassium hypochlorite (KClO) are weighed and added into a reaction vessel, and the mixture is stirred and reacted for 10 hours at 65 ℃ to obtain a solution B.
(4) Dropwise adding a certain amount of concentrated hydrochloric acid into the solution B until the pH value of the solution is 7, filtering, washing, drying, grinding, and sieving with a 600-mesh sieve to obtain the antibacterial agent P5 with the particle size of no more than 23 μm.
Application example 5
Adding 1 part of P5 into 99 parts of polyamide 6(PA6), stirring for 10min by a high-speed mixer, and then adding into a double-screw extruder for blending and extruding to obtain the PA6 composite material X5.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first temperature zone is 200 ℃, the temperature of the second temperature zone is 210 ℃, the temperature of the third temperature zone is 220 ℃, the temperature of the fourth temperature zone is 225 ℃, the temperature of the fifth temperature zone is 225 ℃, the temperature of the sixth temperature zone is 225 ℃, the head temperature of the double-screw extruder is 225 ℃, and the screw rotating speed is 320 r/min.
The antibacterial performance data of the PA6 composites prepared in application example 3, comparative example 3, application example 4, comparative example 4, and application example 5 described above are shown in table 3 below:
TABLE 3 antimicrobial Performance data for the products
As can be seen from the above table, X3 has better antibacterial property than D3, and X4 has better antibacterial property than D4, which shows that the antibacterial performance of the PA6 composite material is better after the antibacterial agent of the present invention is added. And as further seen from the table, the antibacterial performance of X4 is better than that of X5, which indicates that the antibacterial performance can be optimized by optimizing the proportion of the raw materials.
The PA6 composite materials prepared in application example 3, comparative example 3, application example 4, comparative example 4, and application example 5 were used as antibacterial test specimens, and the specimens were placed in a drying oven at a constant temperature of 150 ℃ for 400 hours to perform a heat aging test. After the test is finished, the plate is taken out to test the antibacterial performance and is respectively marked as X3-LH, D3-LH, X4-LH, D4-LH and X5-LH, and the data are shown in the following table 4:
TABLE 4 antimicrobial Performance data of the aged product
The nylon material is decomposed after long-term aging, and the antibacterial effect is reduced; meanwhile, if the compatibility of the antibacterial agent and nylon is poor, the antibacterial agent is easy to precipitate and decompose at high temperature. As can be seen from Table 4, the antibacterial rates of X3-LH and X4-LH are still high after aging, while the antibacterial rates of D3-LH and D4-LH are greatly reduced. This shows that the antibacterial agent of the present invention has good compatibility, good temperature resistance and good durability in the nylon system.
The patent describes a preparation method of a novel antibacterial agent, and nylon composite materials prepared by the novel antibacterial agent have improved antibacterial performance, expand the types and application fields of the antibacterial agent and have very important significance.
The above disclosure is only for the purpose of describing several embodiments of the present application, but the present application is not limited thereto, and any variations that can be considered by those skilled in the art are intended to fall within the scope of the present application.
Claims (8)
1. A preparation method of a halamine antibacterial agent is characterized by comprising the following steps: the method comprises the following steps:
(1) adding methacrylic acid into a solvent, adding N-hydroxymethyl acrylamide and dibenzoyl peroxide under the stirring condition, reacting for 6-8h at 70-90 ℃, filtering and drying to obtain a product A;
(2) adding the product A, deionized water and potassium hypochlorite into a reaction vessel, and stirring and reacting for 8-10h at 60-80 ℃ to obtain a solution B;
(3) and (3) dropwise adding an acid solution into the solution B to adjust the pH value of the solution to be neutral, filtering, washing, drying and grinding to obtain the halamine antibacterial agent.
2. The method of claim 1, wherein: in the step (1), the solvent is acetone; the mass ratio of the methacrylic acid to the acetone to the dibenzoyl peroxide to the N-hydroxymethyl acrylamide is (30-40): (180-240): (0.8-1): (20-24).
3. The method of claim 1, wherein: in the step (1), the drying temperature is 60-80 ℃, and the drying time is 4-6 h.
4. The method of claim 1, wherein: in the step (2), the mass ratio of the product A, the deionized water and the potassium hypochlorite is (60-80): (200-280): (50-70).
5. The method of claim 1, wherein: in the step (3), the acid solution is concentrated hydrochloric acid; the particle size of the halamine antibacterial agent is not more than 23 μm.
6. The halogen amine-based antibacterial agent obtained by the production method according to any one of claims 1 to 5.
7. Use of a halamine-based antibacterial agent in a nylon composite according to claim 6, characterized in that: the nylon composite material is prepared from the halamine antibacterial agent and nylon by the following method:
adding the halamine antibacterial agent and the nylon into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, and performing blending extrusion to obtain the nylon composite material.
8. Use according to claim 7, characterized in that: the nylon is one of polycaprolactam, polyhexamethylene adipamide and polypentylene adipamide.
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Cited By (1)
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