Antibacterial composite organic guanidine polymer and preparation method thereof

Abstract

The present application relates to the technical field of antibacterial agents, and aims at the problem that the existing antibacterial composite organic guanidine polymer antibacterial agent is easy to be lost in washing after treating pure cotton fabric, resulting in poor long-acting antibacterial performance, and provides an antibacterial composite organic guanidine polymer and a preparation method thereof.The antibacterial composite organic guanidine polymer comprises an antibacterial active component, a crosslinking agent polyethylene glycol diglycidyl ether and an anchor connecting agent silane coupling agent, takes polyhexamethylene monoguanidine as an antibacterial core, and is connected through a single carboxyl polyethylene glycol as a flexible connecting arm;the double covalent bond anchoring of ether bond formed by the crosslinking agent and siloxane ether bond formed by the silane coupling agent is used to improve the combination stability with the fabric and realize long-acting antibacterial performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of antibacterial agents, in particular to an antibacterial composite organic guanidine polymer and a preparation method thereof. BACKGROUND

[0002] Antibacterial agents for fabric antibacterial are the key barrier to block the breeding of microorganisms and prevent cross infection. They not only can prolong the service life of fabrics and reduce the generation of odor, but also can meet the rigid demand for health and safety in special environments, and are one of the core supports for the upgrading of modern textile functions. Among the commonly used antibacterial agents, natural antibacterial agents such as chitosan and plant extracts have biocompatibility and environmental friendliness, and can improve washability after microencapsulation treatment; inorganic antibacterial agents mainly include silver ions, copper ions and graphene, silver ions have broad-spectrum antibacterial property but are high in cost, copper ions are safer and can be metabolized and excreted, and graphene is suitable for direct contact with the skin due to its low toxicity and high stability; organic antibacterial agents such as quaternary ammonium salts achieve antibacterial property by destroying cell membranes, and have softness and washability, and halamine compounds kill bacteria by releasing active chlorine and have strong stability. Antibacterial composite organic guanidine polymers in the field of fabric antibacterial are mainly developed by high polymer-based composite materials, combined with nano-composite, graft copolymerization and microcapsule encapsulation technologies, to realize efficient combination of antibacterial components and fabrics. However, the antibacterial composite organic guanidine polymer still has the problems of insufficient stability of antibacterial agents and easy loss in washing, and long-acting antibacterial performance becomes a research focus. SUMMARY

[0003] In view of the deficiencies of the prior art, the present application provides an antibacterial composite organic guanidine polymer and a preparation method thereof. The antibacterial composite organic guanidine polymer comprises an antibacterial active component, a crosslinking agent polyethylene glycol diglycidyl ether and an anchoring linker silane coupling agent, takes polyhexamethylene monoguanidine as the antibacterial core and connects through single carboxyl polyethylene glycol as a flexible connecting arm; the double covalent bond anchoring of ether bond formed by the crosslinking agent and siloxane bond formed by the silane coupling agent is used to improve the combination stability with fabrics and realize long-acting antibacterial property.

[0004] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0005] In a first aspect, the present application provides an antibacterial composite organic guanidine polymer, comprising an antibacterial active component, a crosslinking agent and an anchoring linker; the antibacterial active component is obtained by reaction of polyhexamethylene monoguanidine, single carboxyl polyethylene glycol and condensation coupling agent; the single carboxyl polyethylene glycol is obtained by reaction of polyethylene glycol monomethyl ether and succinic anhydride; the crosslinking agent is polyethylene glycol diglycidyl ether; and the anchoring linker is a silane coupling agent.

[0006] In a possible implementation, the mass ratio of the antibacterial active component, the crosslinking agent and the anchoring linker is (32-35):(15-18):7; the mass ratio of the polyhexamethylene monoguanidine, the moncarboxyl polyethylene glycol and the condensation coupling agent is (90-110):(80-90):25; and the mass ratio of the polyethylene glycol monomethyl ether and the succinic anhydride is 10:(2.5-3).

[0007] In a possible implementation, the silane coupling agent is 3-glycidyloxypropyltrimethoxysilane; and the condensation coupling agent is N,N'-dicyclohexyl carbodiimide.

[0008] In a possible implementation, the polyethylene glycol monomethyl ether comprises at least one of MPEG-200, MPEG-400 and MPEG-600, the molecular weight of the polyethylene glycol diglycidyl ether is 800-1000 Da, and the molecular weight of the polyhexamethylene monoguanidine is 8000-10000 Da.

[0009] In a second aspect, the application provides a preparation method of the antibacterial composite organic guanidine polymer.

[0010] S1, mixing the polyethylene glycol monomethyl ether with pyridine, heating to a first set temperature, adding succinic anhydride, and performing a first holding reaction; after the reaction is completed, cooling to room temperature to obtain a crude reaction liquid; adding diethyl ether to the crude reaction liquid, stirring and then standing to separate the layers, centrifuging the lower layer of the precipitate, and drying to obtain moncarboxyl polyethylene glycol.

[0011] S2, dissolving the polyhexamethylene monoguanidine in a mixed solvent of ethanol and water to prepare a polyhexamethylene monoguanidine solution, adding the moncarboxyl polyethylene glycol and the condensation coupling agent, heating to a second set temperature, performing a second holding reaction, filtering, collecting the filtrate, and obtaining the antibacterial active component.

[0012] S3, heating the antibacterial active component to a third set temperature, adding the polyethylene glycol diglycidyl ether and the silane coupling agent, performing a third holding reaction, and performing vacuum distillation to obtain the antibacterial composite organic guanidine polymer.

[0013] In a possible implementation, the mass ratio of the polyethylene glycol monomethyl ether and pyridine is (1.9-2.1):1, and the amount of diethyl ether is 5-5.5 times the volume of the crude reaction liquid.

[0014] In a possible implementation, the first set temperature is 80-85°C, the first holding reaction time is 3.5-4.5h, and the stirring time is 30-60min. The terminal hydroxyl group of polyethylene glycol monomethyl ether attacks the anhydride bond of succinic anhydride, resulting in the breaking of the anhydride bond to form an ester bond, while the other end of succinic anhydride retains a carboxyl group, and finally a monocarboxyl polyethylene glycol is generated, which provides an active site for subsequent amidation reaction with the amino group of polyhexamethylene monoguanidine, and the polyethylene glycol segment serves as a flexible connecting arm to balance the interfacial force between the antibacterial agent and the fabric and reduce the degree of hardening of the fabric caused by the rigid structure.

[0015] Pyridine is a basic catalyst that neutralizes the trace amount of carboxylic acid generated in the reaction as a proton acceptor, promotes the equilibrium to move in the direction of the product, and improves the esterification efficiency; ethyl ether is a precipitant that uses the high polarity of monocarboxyl polyethylene glycol and the difference in solubility in ethyl ether between the unreacted raw material (such as succinic anhydride, which has lower polarity) to realize purification through centrifugal separation, with the monocarboxyl polyethylene glycol being precipitated and the impurities remaining in the ethyl ether phase.

[0016] In a possible implementation, the volume ratio of ethanol to water in the mixed solvent is 7:3, and the concentration of the polyhexamethylene monoguanidine solution is 8wt%-12wt%.

[0017] In a possible implementation, the second set temperature is 45-55°C, and the second holding reaction time is 3-5h.

[0018] Polyhexamethylene monoguanidine and monocarboxyl polyethylene glycol undergo condensation reaction (amidation reaction) of carboxyl and amino groups, and under the action of condensation coupling agent N,N'-dicyclohexyl carbodiimide (DCC), the carboxyl group of monocarboxyl polyethylene glycol first reacts with DCC to generate active ester intermediate -O-CO-N(C6H 11 )2, which is then attacked by the primary amino group (-NH2) of polyhexamethylene monoguanidine to form an amide bond (-CONH-), thereby connecting polyhexamethylene monoguanidine and polyethylene glycol segments through the amide bond, retaining the biguanide group antibacterial active site of polyhexamethylene monoguanidine, which can subsequently destroy the bacterial cell membrane through hydrogen bonding and hydrophobic interaction to achieve antibacterial effect, and meanwhile DCC is converted into byproduct dicyclohexyl urea (DCU, which can be removed by filtration). The ethanol / water mixed solvent (7:3) not only dissolves polyhexamethylene monoguanidine (containing a polar group), but also ensures the dispersibility of monocarboxyl polyethylene glycol (hydrophilic), avoiding phase separation; 40-50°C is a suitable temperature for the amidation reaction, which can accelerate the formation of active ester intermediate.

[0019] In a possible implementation, the third set temperature is 50-55°C, and the third holding reaction time is 2-3h.

[0020] The ring-opening reaction of the epoxy groups at both ends of the cross-linking agent (polyethylene glycol diglycidyl ether) with the hydroxyl groups of the polyethylene glycol segments in the antibacterial active component occurs at 50-55℃, forming ether bonds, realizing intermolecular cross-linking, constructing a cross-linked network structure, and being able to improve the molecular weight and structural stability of the polymer, avoiding the antibacterial agent from falling off due to molecular chain rupture during the washing process; the ring-opening reaction of the epoxy groups of 3-glycidyloxypropyltrimethoxysilane with the hydroxyl groups or the imino groups (-NH-) beside the amide bonds of the antibacterial active component introduces the siloxane group -Si(OCH3)3 into the molecular chain; the hydrolysis of the siloxane group into silicon hydroxyl groups -Si(OH)3 in the subsequent pure cotton fabric treatment and the condensation reaction of the silicon hydroxyl groups with the hydroxyl groups of the cellulose of the pure cotton fabric form siloxane ether bonds (-Si-O-C-), anchor the antibacterial agent on the surface of the pure cotton fabric, provide chemical stability, and further enhance the binding strength of the antibacterial agent and the surface of the pure cotton fabric; the flexible polyethylene glycol segments buffer the stress generated by fabric friction, and reduce the risk of physical falling off of the antibacterial agent due to excessive rigidity.

[0021] Beneficial technical effects:

[0022] The antibacterial composite organic guanidine polymer prepared by the method has polyhexamethylene monoguanidine as the antibacterial active component, introduces monovalent carboxyl polyethylene glycol (generated by the reaction of polyethylene glycol monomethyl ether and succinic anhydride) as a flexible connecting arm, and connects the antibacterial active component and the anchoring functional group through an amidation reaction, balances the interfacial force between the antibacterial agent and the fabric, maintains the flexibility of the fabric, and promotes the uniform distribution of the antibacterial sites; at the same time, the ring-opening reaction of the epoxy groups of the cross-linking agent polyethylene glycol diglycidyl ether with the surface hydroxyl groups of the pure cotton fabric forms ether bonds, constructs a cross-linked network, improves the binding stability of the polymer and the fabric, and reduces the risk of molecular chain rupture and falling off during washing; on the other hand, the silane coupling agent is combined with the antibacterial component, and the siloxane group is hydrolyzed and condensed to form a siloxane ether bond with the hydroxyl groups of the fabric cellulose, which cooperates with the ether bond to form a double bond with the fabric, improves the long-acting antibacterial effect, and finally maintains an antibacterial rate of more than 99% after 100 times of washing. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The figure is a schematic diagram of the preparation method of the antibacterial composite organic guanidine polymer. DETAILED DESCRIPTION

[0024] In order to make the technical problems, technical solutions and beneficial effects of the present application clearer, the present application will be further described in detail below in conjunction with the embodiments. However, it should not be understood as limiting the scope of the present application to the following examples. Without departing from the method idea of the present application, all other embodiments obtained by those skilled in the art without making creative efforts shall fall within the scope of protection of the present application.

[0025] In this application, the terms used in this application are merely for the purpose of describing specific embodiments, and are not intended to limit the application.

[0026] The singular forms "is", "are", "one", "any", and "the" used in this application are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0027] In addition, if the terms "first", "second" appear, they are only for the purpose of description, and cannot be understood as indicating or implying relative importance.

[0028] The following will be described in detail in combination with different embodiments, a kind of antibacterial composite organic guanidine polymer and preparation method thereof provided by the application.

[0029] Example 1

[0030] As shown in the preparation method of a kind of antibacterial composite organic guanidine polymer, comprising the following steps: Figure 1

[0031] 1.MPEG-400 and pyridine are mixed in a mass ratio of 2:1, heated to 80 DEG C, succinic anhydride is added, the mass ratio of MPEG-400 and succinic anhydride is 10:2.8, after 4h reaction, cooling to room temperature to obtain crude reaction liquid, pour 5 times volume of ether into the crude reaction liquid, stir for 45min, then stand to separate, centrifugal separation of the lower layer precipitate, dry to obtain moncarboxyl polyethylene glycol;

[0032] 2.polyhexamethylene monoguanidine with molecular weight of 8000Da is dissolved in mixed solvent of ethanol and water with volume ratio of 7:3, 10wt% polyhexamethylene monoguanidine solution is prepared, moncarboxyl polyethylene glycol and N,N'-dicyclohexyl carbonyl imidazole are added, the mass ratio of polyhexamethylene monoguanidine, moncarboxyl polyethylene glycol and N,N'-dicyclohexyl carbonyl imidazole is 100:85:25, 50 DEG C reaction for 4h, filtration, collect the filtrate, obtain antibacterial active component;

[0033] 3.the antibacterial active component is heated to 50 DEG C, polyethylene glycol diglycidyl ether with molecular weight of 800Da and 3-glycidyl ether oxypropyl trimethoxysilane are added, the mass ratio of antibacterial active component, polyethylene glycol diglycidyl ether and 3-glycidyl ether oxypropyl trimethoxysilane is 34:17:7, keep warm for 2.5h, vacuum distillation to obtain antibacterial composite organic guanidine polymer.

[0034] Antibacterial performance test:

[0035] ​The antibacterial composite organic guanidine polymer of Example 1 was configured into a 5wt% antibacterial agent solution, padded onto pure cotton fabric (pick-up rate 60%), and air-dried at 80°C for 30min to obtain antibacterial fabric A. The antibacterial performance of the antibacterial fabric after 100 washes was tested in accordance with GB / T 20944.3-2008 "Evaluation of the antibacterial properties of textiles Part 3: shaking method". A 30g sample of the antibacterial fabric A was washed 100 times using a household double-barrel washing machine under the following conditions: 40°C±3°C, bath ratio 1:30, AATCC 1993 WOB non-phosphorus standard detergent concentration 0.2%. After washing, the sample was cut into pieces of about 5mm x 5mm in size, and 0.75g±0.05g was weighed out as the antibacterial fabric sample A and placed in a flask. Inoculum was added, and the viable bacterial concentration after 18h of shaking was measured and recorded as Q. The inoculum was Staphylococcus aureus, ATCC6538; Candida albicans, ATCC10231; Klebsiella pneumonia, ATCC4352. A flask without the addition of the antibacterial fabric sample A was used as a standard blank sample, and the viable bacterial concentration of the standard blank sample at "0" contact time was measured and recorded as W0. The viable bacterial concentration of the standard blank sample after 18h of shaking was measured and recorded as W t , and the antibacterial rate Y was calculated as Y=[(W t -Q) / W t ]x100%, and the results are shown in Table 1.

[0036] Table 1. Antibacterial performance test results of the antibacterial composite organic guanidine polymer prepared in Example 1

[0037]

[0038] Example 2

[0039] As shown in Figure 1 , a method for preparing an antibacterial composite organic guanidine polymer includes the following steps:

[0040] 1. Mix MPEG-200 and pyridine at a mass ratio of 1.9:1, heat to 85°C, and add succinic anhydride at a mass ratio of MPEG-200 to succinic anhydride of 10:2.5. After 3.5h of reaction, cool to room temperature to obtain a crude reaction solution. Pour 5.5 times the volume of diethyl ether into the crude reaction solution, stir for 30min, and then separate the layers by standing. Centrifuge the lower layer of precipitate, and dry to obtain a moncarboxyl polyethylene glycol;

[0041] 2. The polyhexamethylene monoguanide with a molecular weight of 9000 Da was dissolved in a mixed solvent of ethanol and water with a volume ratio of 7:3 to prepare a 8 wt% polyhexamethylene monoguanide solution. Carboxymethyl polyethylene glycol and N,N'-dicyclohexyl carbodiimide were added, and the mass ratio of polyhexamethylene monoguanide, carboxymethyl polyethylene glycol and N,N'-dicyclohexyl carbodiimide was 90:80:25. The mixture was reacted at 45°C for 5h, filtered, and the filtrate was collected to obtain an antibacterial active component;

[0042] 3. The antibacterial active component was warmed to 55°C, and polyethylene glycol diglycidyl ether with a molecular weight of 900 Da and 3-glycidyloxypropyl trimethoxysilane were added. The mass ratio of the antibacterial active component, polyethylene glycol diglycidyl ether and 3-glycidyloxypropyl trimethoxysilane was 32:18:7. The mixture was reacted for 2h, and an antibacterial composite organic guanidine polymer was obtained by distillation under reduced pressure.

[0043] Antibacterial performance test:

[0044] An antibacterial agent solution of 5 wt% of the antibacterial composite organic guanidine polymer prepared in Example 2 was prepared, and pure cotton fabric was padded (pick-up rate 60%) and dried at 80°C for 30min to obtain antibacterial fabric B. The antibacterial performance of the antibacterial fabric after 100 washes was tested according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: shaking method". A 30g sample of the antibacterial fabric B was taken, and the test conditions were 40°C±3°C, bath ratio 1:30, and AATCC 1993 WOB non-phosphorus standard detergent concentration 0.2%. After 100 washes using a household double-barrel washing machine, the sample was cut into pieces of about 5mm x 5mm, and 0.75g±0.05g was taken as the antibacterial fabric sample B and placed in a flask. Inoculated bacteria solution was added, and the viable bacteria concentration after 18h of shaking contact was recorded as Q. The inoculated bacteria solution was Staphylococcus aureus with preservation number ATCC6538, Candida albicans with preservation number ATCC10231, and Klebsiella pneumonia with preservation number ATCC4352. The inoculated bacteria solution was added to a flask without the antibacterial fabric sample B as a standard blank sample. The viable bacteria concentration of the standard blank sample after 0 contact time was recorded as W0, and the viable bacteria concentration after 18h of shaking was recorded as W t t t The results are shown in Table 2.

[0045] Table 2. Antibacterial performance test results of the antibacterial composite organic guanidine polymer prepared in Example 2

[0046] ​​

[0047] Example 3

[0048] As Figure 1 shown, a preparation method of an antibacterial composite organic guanidine polymer, comprising the following steps:

[0049] 1. Mix MPEG-600 and pyridine at a mass ratio of 2.1:1, heat to 85℃, add succinic anhydride, the mass ratio of MPEG-600 to succinic anhydride is 10:3, after 4.5h of reaction and cooling to room temperature, a crude reaction solution is obtained, pour 5 times volume of ethyl ether into the crude reaction solution, stir for 60min, then stand and separate the layers, centrifuge the lower layer precipitate, and dry to obtain monocarboxyl polyethylene glycol;

[0050] 2. Dissolve polyhexamethylene monoguanidine with a molecular weight of 10000Da in a mixed solvent of ethanol and water at a volume ratio of 7:3, prepare a 12wt% polyhexamethylene monoguanidine solution, add monocarboxyl polyethylene glycol and N,N'-dicyclohexyl carbodiimide, the mass ratio of polyhexamethylene monoguanidine, monocarboxyl polyethylene glycol and N,N'-dicyclohexyl carbodiimide is 110:90:25, react at 55℃ for 3h, filter, collect the filtrate, and obtain an antibacterial active component;

[0051] 3. Heat the antibacterial active component to 55℃, add polyethylene glycol diglycidyl ether with a molecular weight of 1000Da and 3-glycidyl ether oxypropyl trimethoxysilane, the mass ratio of the antibacterial active component, polyethylene glycol diglycidyl ether and 3-glycidyl ether oxypropyl trimethoxysilane is 35:15:7, react for 3h, and distill under reduced pressure to obtain an antibacterial composite organic guanidine polymer.

[0052] Antibacterial performance test:

[0053] The antibacterial composite organic guanidine polymer of Example 3 was configured into a 5wt% antibacterial agent solution, padded onto pure cotton fabric (pick-up rate 60%), and dried at 80℃ for 30min to obtain antibacterial fabric C. The antibacterial performance of the antibacterial fabric after 100 washes was tested according to GB / T 20944.3-2008 "Evaluation of the antibacterial properties of textiles Part 3: shaking method". A 30g sample of the antibacterial fabric C was taken, and the test conditions were 40℃±3℃, bath ratio 1:30, AATCC 1993 WOB non-phosphorus standard detergent concentration 0.2%, and after 100 washes using a household double-barrel washing machine, the sample was cut into pieces of about 5mm x 5mm, 0.75g±0.05g was weighed as the antibacterial fabric sample C, placed in a flask, and inoculated with bacteria solution, and the viable bacteria concentration after 18h of shaking contact was tested, recorded as Q. The bacteria in the inoculated bacteria solution were Staphylococcus aureus, preservation number ATCC6538; Candida albicans, preservation number ATCC10231; Klebsiella pneumonia, preservation number ATCC4352. A flask without the addition of the antibacterial fabric sample C was added with the inoculated bacteria solution as a standard blank sample, and the viable bacteria concentration of the standard blank sample at "0" contact time was tested, recorded as W0; the viable bacteria concentration of the standard blank sample after 18h of shaking was tested, recorded as W t , and the bacteriostatic rate Y was calculated, Y=[(W t -Q) / W t ]x100%, and the results are shown in Table 3.

[0054] Table 3 Test results of the antibacterial performance of the antibacterial composite organic guanidine polymer prepared in Example 3

[0055]

[0056] Comparative Example 1

[0057] A method for preparing an antibacterial composite organic guanidine polymer, the implementation steps and parameters were the same as in Example 1, except that no silane coupling agent was added.

[0058] Antibacterial performance test:

[0059] The antibacterial composite organic guanidine polymer of Comparative Example 1 was configured into a 5wt% antibacterial agent solution, padded onto pure cotton fabric (pick-up rate 60%), and dried at 80°C for 30min to obtain antibacterial fabric D. The antibacterial performance of the antibacterial fabric after 100 washes was tested according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: shaking method". A 30g sample of the antibacterial fabric D was taken, and the test conditions were 40°C±3°C, bath ratio 1:30, AATCC 1993 WOB non-phosphorus standard detergent concentration 0.2%, and after 100 washes using a household double-barrel washing machine, the sample was cut into pieces of about 5mm x 5mm in size, 0.75g±0.05g was weighed as the antibacterial fabric sample D, placed in a flask, and inoculated with bacteria solution, and the viable bacteria concentration after 18h of shaking contact was tested, denoted as Q. The bacteria in the inoculated bacteria solution were Staphylococcus aureus, preservation number ATCC6538; Candida albicans, preservation number ATCC10231; Klebsiella pneumonia, preservation number ATCC4352. A flask without the addition of the antibacterial fabric sample D was inoculated with bacteria solution as a standard blank sample, and the viable bacteria concentration of the standard blank sample at "0" contact time was tested, denoted as W0; the viable bacteria concentration of the standard blank sample after 18h of shaking was tested, denoted as W t , and the bacteriostatic rate Y was calculated, Y=[(W t -Q) / W t ]x100%, and the results are shown in Table 4.

[0060] Table 4 Test results of the antibacterial performance of the antibacterial composite organic guanidine polymer prepared in Comparative Example 1

[0061]

[0062] Comparative Example 2

[0063] A method for preparing an antibacterial composite organic guanidine polymer, the implementation steps and parameters being the same as those of Example 1, except that polypropylene glycol monomethyl ether PPG-400 was used instead of MPEG-400.

[0064] Antibacterial performance test:

[0065] The antibacterial composite organic guanidine polymer of Comparative Example 2 was configured into a 5wt% antibacterial agent solution, padded onto pure cotton fabric (pick-up rate 60%), and dried at 80°C for 30min to obtain antibacterial fabric E. The antibacterial performance of the antibacterial fabric after 100 washes was tested according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: shaking method". A 30g sample of the antibacterial fabric E was taken, and the test conditions were 40°C±3°C, bath ratio 1:30, AATCC 1993 WOB non-phosphorus standard detergent concentration 0.2%, and after 100 washes using a household double-barrel washing machine, the sample was cut into pieces of about 5mm x 5mm in size, 0.75g±0.05g was weighed as the antibacterial fabric sample E, placed in a flask, inoculated with bacterial solution, and the viable bacterial concentration after 18h of shaking contact was tested, denoted as Q. The bacterial species of the inoculated bacterial solution were Staphylococcus aureus, preservation number ATCC6538; Candida albicans, preservation number ATCC10231; Klebsiella pneumonia, preservation number ATCC4352. A flask without the addition of the antibacterial fabric sample E was inoculated with bacterial solution as a standard blank sample, and the viable bacterial concentration of the standard blank sample at "0" contact time was tested, denoted as W0; the viable bacterial concentration of the standard blank sample after 18h of shaking was tested, denoted as W t , and the antibacterial rate Y was calculated, Y=[(W t -Q) / W t ]x100%, and the results are shown in Table 5.

[0066] Table 5. Antibacterial performance test results of the antibacterial composite organic guanidine polymer prepared in Comparative Example 2

[0067]

[0068] As can be seen from Table 1, the antibacterial composite organic guanidine polymer prepared in Examples 1-3 of the present application still has an antibacterial rate of 99% against Staphylococcus aureus, Candida albicans and Klebsiella pneumonia after treating pure cotton fabric and 100 washes, exhibiting excellent long-acting antibacterial performance.

[0069] The antibacterial rate of the antibacterial fabric against S. aureus was reduced to 78%, against C. albicans to 72%, and against K. pneumoniae to 70% after 100 times of washing. The siloxane groups of the silane coupling agent can form siloxane ether bonds with the hydroxyl groups of the cellulose of the pure cotton fabric after hydrolysis, which can resist mechanical friction and chemical erosion during washing. The ether bond formed with the crosslinking agent synergistically binds the antibacterial composite organic guanidine polymer to the pure cotton fabric. However, Comparative Example 1 lacks siloxane ether bonds and only relies on ether bonds, which have low bond energy and are prone to hydrolysis and rupture in alkaline detergents. The antibacterial composite organic guanidine polymer is largely detached from the fabric surface during 100 times of washing due to the rupture of the ether bond, resulting in a significant decrease in the number of active antibacterial sites on the fabric surface and a significant decrease in antibacterial performance.

[0070] In Comparative Example 2, PPG-400 was used instead of MPEG-400, and after 100 times of washing, the antibacterial fabric had an antibacterial rate of 88% against S. aureus, 85% against C. albicans, and 82% against K. pneumoniae, which met the standard but was significantly lower than that of the examples. The oxygen ethyl segment of MPEG has high flexibility, which can buffer the frictional stress of the fabric during washing and reduce mechanical damage to the binding sites of the antibacterial agent and the fabric. The methylene rigid segment of PPG-40 cannot absorb frictional energy, which disrupts the balance of interfacial forces and causes the covalent bond between the antibacterial agent and the fabric to easily break due to stress concentration. Meanwhile, the flexible segment of MPEG can uniformly distribute the antibacterial groups (guanidine groups) on the fabric surface through molecular chain movement. The rigid segment of PPG limits molecular movement, causing the antibacterial groups to aggregate, and the concentration of the antibacterial agent in some areas is insufficient to effectively kill the contacted microorganisms, resulting in a decrease in the antibacterial rate after 100 times of washing.

[0071] The above results show and describe the basic principles and main features of the present application and the advantages of the present application.

[0072] Those skilled in the art should understand that the present application is not limited to the above examples, and the above examples and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection claimed by the present application is defined by the equivalents of the appended claims.

Claims

1. An antibacterial composite organic guanidine polymer, characterized in that, The product comprises an antibacterial active component, a crosslinking agent, and an anchoring binder; the antibacterial active component is obtained by reacting polyhexamethylene monoguanidine, monocarboxylated polyethylene glycol, and a condensation coupling agent; the monocarboxylated polyethylene glycol is obtained by reacting polyethylene glycol monomethyl ether with succinic anhydride; the crosslinking agent is polyethylene glycol diglycidyl ether; the anchoring binder is a silane coupling agent; the silane coupling agent is 3-glycidyl etheroxypropyltrimethoxysilane; and the condensation coupling agent is N,N'-dicyclohexylcarboimide.

2. The antibacterial composite organic guanidine polymer according to claim 1, characterized in that, The mass ratio of the antibacterial active component, crosslinking agent, and anchoring agent is (32-35):(15-18):7; the mass ratio of the polyhexamethylene monoguanidine, monocarboxylated polyethylene glycol, and condensation coupling agent is (90-110):(80-90):25; and the mass ratio of polyethylene glycol monomethyl ether to succinic anhydride is 10:(2.5-3).

3. The antibacterial composite organic guanidine polymer according to claim 1, characterized in that, The polyethylene glycol monomethyl ether includes at least one of MPEG-200, MPEG-400 and MPEG-600, the polyethylene glycol diglycidyl ether has a molecular weight of 800-1000 Da, and the polyhexamethylene monoguanidine has a molecular weight of 8000-10000 Da.

4. A method for preparing an antibacterial composite organic guanidine polymer as described in any one of claims 1-3, characterized in that, Includes the following steps: S1. After mixing polyethylene glycol monomethyl ether and pyridine, the mixture is heated to the first set temperature. Succinic anhydride is added to carry out the first heat preservation reaction. After the reaction is completed, the mixture is cooled to room temperature to obtain a crude reaction solution. Diethyl ether is added to the crude reaction solution, and the mixture is stirred and allowed to stand to separate into layers. The lower precipitate is separated by centrifugation and dried to obtain monocarboxylated polyethylene glycol. S2. Dissolve polyhexamethylene monoguanidine in a mixed solvent of ethanol and water to prepare a polyhexamethylene monoguanidine solution. Add monocarboxylated polyethylene glycol and a condensation coupling agent. Heat to a second set temperature, carry out a second heat preservation reaction, filter, collect the filtrate, and obtain the antibacterial active component. S3. Heat the antibacterial active component to the third set temperature, add polyethylene glycol diglycidyl ether and silane coupling agent, carry out the third heat preservation reaction, and obtain the antibacterial composite organic guanidine polymer by vacuum distillation.

5. The method for preparing an antibacterial composite organic guanidine polymer according to claim 4, characterized in that, The mass ratio of polyethylene glycol monomethyl ether to pyridine is (1.9-2.1):1, and the amount of diethyl ether used is 5-5.5 times the volume of the crude reaction liquid.

6. The method for preparing an antibacterial composite organic guanidine polymer according to claim 4, characterized in that, The first set temperature is 80-85℃, the first heat preservation reaction time is 3.5-4.5h, and the stirring time is 30-60min.

7. The method for preparing an antibacterial composite organic guanidine polymer according to claim 4, characterized in that, The volume ratio of ethanol to water in the mixed solvent is 7:3, and the concentration of the polyhexamethylene monoguanidine solution is 8wt%-12wt%.

8. The method for preparing an antibacterial composite organic guanidine polymer according to claim 4, characterized in that, The second set temperature is 45-55℃, and the second heat preservation reaction time is 3-5h.

9. The method for preparing an antibacterial composite organic guanidine polymer according to claim 4, characterized in that, The third set temperature is 50-55℃, and the third heat preservation reaction time is 2-3h.

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