A multifunctional antibacterial monomer and its preparation method, and an antibacterial elastomer and its preparation method

Abstract

The present invention provides a multifunctional antibacterial monomer and a preparation method thereof, and an antibacterial elastomer and a preparation method thereof, belonging to the field of antibacterial materials. The chemical formula of the multifunctional antibacterial monomer provided by the present invention is shown in Formula I; A-SO3 ‑ B + ‑R‑B + SO3 ‑ -A formula I; wherein A ‑ SO3 ‑ B is a sulfonate ion containing a dicarboxyl group; + The multifunctional antibacterial monomer provided by the present invention has a decomposition temperature of up to 320°C. When polymerized with a prepolymer obtained by depolymerization of waste polyamide and dicarboxylic acid, it produces a high-performance elastomer with a molecular weight of up to 22 kDa, a tensile strength of up to 51 MPa, and an elongation at break of up to 625%. It exhibits 100% antibacterial performance against Escherichia coli and Staphylococcus aureus, and exhibits excellent high-temperature resistance, antibacterial properties, and mechanical properties.

Description

Technical Field

[0001] The present invention relates to the field of antibacterial materials, and in particular to a multifunctional antibacterial monomer and a preparation method thereof, and an antibacterial elastomer and a preparation method thereof. Background Art

[0002] Polyamide is non-toxic, lightweight, and possesses excellent mechanical strength, wear resistance, and good corrosion resistance. Its most prominent advantage is its wear resistance, which surpasses all other fibers—10 times higher than cotton and 20 times higher than wool. However, large quantities of discarded polyamide are non-biodegradable, posing serious risks to the natural environment and human society. Traditional methods for recycling polyamide can be categorized into energy recovery, physical recovery, and chemical recovery. Energy recovery involves incineration of waste polyamide, which not only has the lowest utilization rate but also produces toxic gases that increase post-processing costs. Physical recovery involves sorting, cleaning, crushing, melting, and granulating waste polyamide for direct molding and reprocessing. However, during processing, polyamide undergoes degradation or oxidation, resulting in a decrease in molecular weight and deterioration in material properties. Furthermore, the recycling process is cumbersome and costly. Chemical recovery involves depolymerizing waste polyamide into oligomers or monomers, which are then reused and converted into products. Chemical depolymerization pathways include hydrolysis, aminolysis, alcoholysis, and hydrogenolysis. However, the recovered monomers require purification, increasing costs and lacking an economic competitive advantage over primary synthesis products. If waste polyamide products are given antibacterial properties, it will not only enable the upgrading and recycling of waste polyamide materials, but also make the recycled products antibacterial and able to be used in the antibacterial field.

[0003] However, pure polyamide products themselves do not have antibacterial function. Generally, they are made antibacterial by physical blending with antibacterial agents or chemical modification. However, physical blending has many disadvantages. For example, its bactericidal function lies in the release of antibacterial agents. Once the antibacterial agents are completely released, the material will lose its antibacterial ability, and the antibacterial ability is not long-lasting. Chemical modification is to graft the antibacterial agent onto the polymer molecular chain through chemical reaction to achieve the antibacterial purpose, but this method has cumbersome and complicated synthesis steps, which greatly increases production costs.

[0004] The most economically viable and market-demanded method for producing antimicrobial elastomers from waste polyamide is a one-pot melt polycondensation process. However, the melting temperature of polyamide is generally above 200°C, while the decomposition temperature of common antimicrobial monomers on the market is generally below 200°C, thus limiting the promotion and application of this method. Furthermore, since common antimicrobial monomers on the market only provide antimicrobial properties, the introduction of these monomers disrupts the molecular chain sequence, thereby affecting the mechanical properties of the material and negatively impacting the mechanical properties of the antimicrobial elastomer. Summary of the Invention

[0005] The present invention provides a multifunctional antimicrobial monomer and a method for preparing the same, as well as an antimicrobial elastomer and a method for preparing the same. The multifunctional antimicrobial monomer provided by the present invention has a high decomposition temperature, and the antimicrobial elastomer prepared using the multifunctional antimicrobial monomer exhibits excellent antimicrobial properties and good mechanical properties.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] A multifunctional antibacterial monomer, the chemical formula of the multifunctional antibacterial monomer is shown in Formula I:

[0008] A-SO3 - B + -RB + SO3 - -A formula I;

[0009] In the formula I, A-SO3 - It is a sulfonate ion containing a dicarboxyl group;

[0010] B + is an imidazolium quaternary ammonium salt cation;

[0011] R is o-dibenzyl, m-dibenzyl or p-dibenzyl.

[0012] Preferably, the dicarboxyl-containing sulfonate ion is 5-isophthalic acid sulfonate ion, 5-dimethyl terephthalate sulfonate ion or dimethyl succinate sulfonate ion.

[0013] The present invention provides a method for preparing the multifunctional antibacterial monomer described in the above technical solution, comprising the following steps:

[0014] (1) mixing a compound containing an imidazole group, a xylene halide, and methanol to carry out a substitution reaction to obtain a benzyl compound containing a bisimidazole group;

[0015] (2) mixing the benzyl compound containing a bisimidazole group obtained in step (1), a halogenated alkane and anhydrous ethanol to carry out a quaternization reaction to obtain an intermediate; the number of carbon atoms of the alkane in the halogenated alkane is ≥6;

[0016] (3) The intermediate obtained in step (2), the dicarboxyl-containing sulfonate and deionized water are mixed to carry out an ion exchange reaction to obtain a multifunctional antibacterial monomer.

[0017] The present invention also provides a method for preparing an antibacterial elastomer, comprising:

[0018] The multifunctional antibacterial monomer according to claim 1 or the multifunctional antibacterial monomer prepared by the preparation method according to claim 2, polyamide, dicarboxylic acid and a catalyst are mixed and then subjected to depolymerization reaction and polymerization reaction in sequence to obtain an antibacterial elastomer; the depolymerization reaction is carried out in an inert atmosphere; and the polymerization reaction is carried out under vacuum conditions.

[0019] Preferably, the polyamide includes one or more of polybutyrolactam, polycaprolactam, polyheptamide, polyoctylamide, polynonanamide, polyundecalactam, polydodecamide, polytridecanamide, polyhexamethylenediamine adipamide, polyglutamamide, polybutylene adipamide, polybutylene adipamide, polypentamethylenediamine, polyhexamethylenediamine, polydodecanoyldiamine, polydodecanoyldiamine, polyhexamethylenediamine, polydodecanoyldiamine, polyhexamethylenediamine terephthalamide, polynonamethylenediamine, polydecane terephthalamide, polytrimethylhexamethylenediamine, polyparaphenylene terephthalamide, polymethyleneisophthalamide or polymethyleneisophthalamide.

[0020] Preferably, the mass ratio of the multifunctional antibacterial monomer, polyamide and dicarboxylic acid is (0.5-0.6): (5-12): (10-18).

[0021] Preferably, the added amount of the catalyst is 0.01 to 5% of the total mass of the multifunctional antibacterial monomer, polyamide and dicarboxylic acid.

[0022] Preferably, the temperature of the depolymerization reaction is 100 to 280° C., and the time of the depolymerization reaction is 0.5 to 24 hours.

[0023] Preferably, the polymerization reaction temperature is 100 to 280° C., and the polymerization reaction time is 0.5 to 24 hours.

[0024] The present invention also provides an antibacterial elastomer prepared by the preparation method described in the above technical solution.

[0025] The present invention provides a multifunctional antibacterial monomer, the chemical formula of which is shown in Formula I: A-SO3 - B + -RB + SO3 - -A formula I; wherein A-SO3 - B is a sulfonate ion containing a dicarboxyl group; + is an imidazolium quaternary ammonium salt cation; R is o-dibenzyl, m-dibenzyl or p-dibenzyl. In the chemical structure of the multifunctional antibacterial monomer provided by the present invention, the imidazole group and the benzene ring structure can improve the high temperature resistance of the monomer; the quaternary ammonium ion can provide the monomer with good antibacterial properties; A-SO3 -The dicarboxyl groups contained in the group allow the multifunctional antimicrobial monomer to be a tetracarboxylic acid, providing crosslinking sites. This allows waste polyamide, dicarboxylic acid, and the multifunctional antimicrobial monomer to form a high-performance elastomer, thereby improving the mechanical properties of the elastomer. Experimental results show that the multifunctional antimicrobial monomer provided by the present invention has a decomposition temperature of up to 320°C, and the prepolymer obtained by depolymerization with waste polyamide and dicarboxylic acid produces a high-performance elastomer with a molecular weight of up to 22kDa, a tensile strength of up to 51MPa, and an elongation at break of up to 625%. It also exhibits 100% antimicrobial performance against Escherichia coli and Staphylococcus aureus, and exhibits excellent high-temperature resistance, antimicrobial properties, and mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a tensile curve diagram of the antibacterial elastomer obtained in Example 2 of the present invention. DETAILED DESCRIPTION

[0027] The present invention provides a multifunctional antibacterial monomer, the chemical formula of which is shown in Formula I:

[0028] A-SO3 - B + -RB + SO3 - -A formula I;

[0029] In the formula I, A-SO3 - It is a sulfonate ion containing a dicarboxyl group;

[0030] B + is an imidazolium quaternary ammonium salt cation;

[0031] R is o-dibenzyl, m-dibenzyl or p-dibenzyl.

[0032] In the present invention, the dicarboxyl-containing sulfonate ion is preferably 5-isophthalic acid sulfonate ion, 5-dimethyl terephthalate sulfonate ion or dimethyl succinate sulfonate ion. The present invention limits the dicarboxyl-containing sulfonate ion to the above range to ensure that the multifunctional antibacterial monomer has better high temperature resistance.

[0033] The multifunctional antibacterial monomer of the present invention has a symmetrical structure centered on a benzene ring; wherein the benzene ring structure in the imidazole group and the benzyl group can improve the high temperature resistance of the monomer; the quaternary ammonium ion can provide the monomer with good antibacterial properties; A-SO3 - The dicarboxyl structure contained in the group makes the multifunctional antibacterial monomer a tetracarboxylic acid, which can provide a cross-linking site, promote the polyamide, dicarboxylic acid and the multifunctional antibacterial monomer to form a high-performance elastomer, and improve the mechanical properties of the elastomer.

[0034] The present invention provides a method for preparing the multifunctional antibacterial monomer described in the above technical solution, comprising the following steps:

[0035] (1) mixing a compound containing an imidazole group, a xylene halide, and methanol to carry out a substitution reaction to obtain a benzyl compound containing a bisimidazole group;

[0036] (2) mixing the benzyl compound containing a bisimidazole group obtained in step (1), a halogenated alkane and anhydrous ethanol to carry out a quaternization reaction to obtain an intermediate; the number of carbon atoms of the alkane in the halogenated alkane is ≥6;

[0037] (3) The intermediate obtained in step (2), the dicarboxyl-containing sulfonate and deionized water are mixed to carry out an ion exchange reaction to obtain a multifunctional antibacterial monomer.

[0038] The invention mixes a compound containing an imidazole group, a xylene halide and methanol to carry out a substitution reaction to obtain a benzyl compound containing a biimidazole group.

[0039] In the present invention, the compound containing an imidazole group preferably includes imidazole, 2-phenylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-butylimidazole, 2-nonylimidazole, 2-isopropylimidazole, 2-cyclopropylimidazole, 2-benzylimidazole, 2-phenylimidazole, 2-propylbenzimidazole, benzimidazole, 4-methylimidazole, 4(5)-ethylimidazole or 4-phenylimidazole. The present invention limits the type of compound containing an imidazole group to the above range, which can ensure that the multifunctional antibacterial monomer has good high temperature resistance.

[0040] In the present invention, the ratio of the mass of the compound containing an imidazole group, the mass of the xylene halide, and the volume of methanol is preferably (3-4) g: (0.5-1) g: (45-55) mL, more preferably (3.1-3.5) g: (0.6-0.8) g: (47-52) mL, and even more preferably 3.16 g: 0.8 g: 50 mL. In the present invention, limiting the ratio of the mass of the compound containing an imidazole group, the mass of the xylene halide, and the volume of methanol to the above range can ensure that the substitution reaction proceeds sufficiently, thereby obtaining a high-purity bisimidazole-containing compound.

[0041] The present invention has no special limitation on the mixing of the compound containing an imidazole group, the xylene halide and the methanol, and the mixing can be carried out in a mixing manner commonly used by those skilled in the art.

[0042] In the present invention, the temperature of the substitution reaction is preferably 70-90°C; the time of the substitution reaction is preferably 5-24 hours, more preferably 10-20 hours, and even more preferably 18 hours. Limiting the temperature and time of the substitution reaction to the above ranges can facilitate the reaction.

[0043] After the substitution reaction is completed, the present invention preferably adds the product of the substitution reaction to a salt solution after rotary evaporation, allows it to stand for precipitation, and then dries it to obtain a benzyl compound containing a bisimidazole group.

[0044] In the present invention, the structural formula of the benzyl compound containing a bisimidazole group is preferably as shown in Formula II-1 to II-3.

[0045]

[0046] In an embodiment of the present invention, the salt solution is preferably a K 2 CO 3 solution. The present invention has no particular limitation on the concentration of the salt solution, and any concentration commonly used by those skilled in the art may be used.

[0047] The present invention has no special requirements for the standing time, as long as the benzyl compound containing the bisimidazole group can be fully precipitated.

[0048] The present invention has no particular limitation on the drying temperature and time, and the drying temperature and time commonly used by those skilled in the art may be adopted.

[0049] After obtaining the benyl compound containing a biimidazole group, the present invention mixes the benyl compound containing a biimidazole group, a halogenated alkane and anhydrous ethanol to carry out a quaternization reaction to obtain an intermediate.

[0050] In the present invention, the mass ratio of the benyl compound containing a bisimidazole group, the alkyl halide, and the anhydrous ethanol is preferably (0.3-0.7): (1.2-1.6): (5-5.5), more preferably (0.4-0.6): (1.3-1.5): (5.1-5.3), and even more preferably 0.5:1.4:5.2. In the present invention, limiting the mass ratio of the benyl compound containing a bisimidazole group, the alkyl halide, and the anhydrous ethanol to the above range can ensure that the quaternization reaction proceeds sufficiently.

[0051] In the present invention, the carbon number of the alkane in the halogenated alkane is ≥ 6, and more preferably 8 to 14. The present invention limits the carbon number of the alkane in the halogenated alkane to the above range to ensure the best antibacterial effect.

[0052] In the present invention, the temperature of the quaternization reaction is preferably 80-100° C., more preferably 90° C.; the time of the quaternization reaction is preferably 24-72 hours, more preferably 48 hours. In the present invention, limiting the temperature and time of the quaternization reaction to the above ranges can ensure that the reaction proceeds fully.

[0053] In the present invention, the chemical reaction equation of the quaternization reaction is preferably as shown in Formula III:

[0054]

[0055] In the formula III, R is o-dibenzyl, m-dibenzyl or p-dibenzyl;

[0056] R1 is preferably imidazolyl, 2-phenylimidazolyl, 2-methylimidazolyl or 2-ethylimidazolyl;

[0057] R2 is preferably an alkane containing at least 6 carbon atoms;

[0058] X is preferably chlorine or bromine.

[0059] After the quaternization reaction is completed, the product of the quaternization reaction is preferably washed and dried in sequence to obtain an intermediate.

[0060] The present invention has no particular limitation on the washing and drying operations, and the washing and drying operations commonly used by those skilled in the art may be used.

[0061] After obtaining the intermediate, the present invention mixes the intermediate, a dicarboxyl-containing sulfonate and deionized water to carry out an ion exchange reaction to obtain a multifunctional antibacterial monomer.

[0062] In the present invention, the ratio of the mass of the intermediate, the mass of the dicarboxyl-containing sulfonate, and the volume of deionized water is preferably (1-4) g: (8-12) g: (180-220) mL, more preferably (1-3) g: (9-11) g: (190-210) mL, and even more preferably 2 g: 10 g: 200 mL. Limiting the ratio of the mass of the intermediate, the mass of the dicarboxyl-containing sulfonate, and the volume of deionized water to the above range ensures the smooth progress of the ion exchange reaction and produces a multifunctional antibacterial monomer with high purity.

[0063] In the present invention, the anion in the dicarboxyl-containing sulfonate is preferably an isophthalic acid 5-sulfonate ion, a dimethyl terephthalate 5-sulfonate ion, or a dimethyl succinate sulfonate ion. The cation in the dicarboxyl-containing sulfonate is preferably a sodium ion. By limiting the anions and cations in the dicarboxyl-containing sulfonate to the above ranges, the performance of the elastomer can be further improved.

[0064] In the present invention, the temperature of the ion exchange reaction is preferably room temperature. The present invention has no particular limitation on the time of the ion exchange reaction, as long as the reaction is complete.

[0065] In the present invention, the chemical reaction equation of the ion exchange reaction is preferably as shown in Formula IV:

[0066]

[0067] After the ion exchange reaction is completed, the present invention preferably sequentially washes and dries the product of the ion exchange reaction to obtain a multifunctional antibacterial monomer.

[0068] The present invention has no particular limitation on the washing and drying operations, and the washing and drying operations commonly used by those skilled in the art may be used.

[0069] The present invention also provides a method for preparing an antibacterial elastomer, comprising:

[0070] The multifunctional antibacterial monomer, polyamide, dicarboxylic acid and catalyst described in the above technical solution are mixed and then subjected to depolymerization reaction and polymerization reaction in sequence to obtain an antibacterial elastomer; the depolymerization reaction is carried out in an inert atmosphere; and the polymerization reaction is carried out under vacuum conditions.

[0071] The invention mixes a multifunctional antibacterial monomer, polyamide, dicarboxylic acid and a catalyst, and then sequentially performs depolymerization reaction and polymerization reaction to obtain an antibacterial elastomer.

[0072] In the present invention, the polyamide is preferably recycled waste polyamide. The preparation method provided by the present invention can be used to recycle and reuse waste polyamide.

[0073] In the present invention, the polyamide preferably includes polybutyrolactam, polycaprolactam, polyheptylamide, polyoctylamide, polynonylamide, polyundecalactam, polydodecylamide, polytridecanamide, polyhexamethylenediamine adipamide, polyglutamylamide, polybutylene adipamide, polybutylene adipamide, polypentamethylenediamine, polyhexamethylenediamine, polypentamethylenediamine, polydodecylamide, polydodecylamide, polyhexamethylenediamine, polydodecylamide, polyhexamethylenediamine, polynonamethylenediamine, polydecanediamine, polyterephthalamide, One or more of poly(trimethylhexamethylenediamine), poly(p-phenylene terephthalamide), poly(m-phenylene isophthalamide) or poly(m-phenylene adipamide), more preferably one or more of poly(hexamethylene adipamide), poly(hexamethylene glutaramide), poly(butylene adipamide), poly(butylene adipamide), poly(pentamethylene adipamide), poly(hexamethylene diamine), poly(dodecanoyl hexamethylenediamine), poly(dodecanoyl dodecanoyl dodecanoyl dodecylamine), further preferably one or more of poly(hexamethylene adipamide), poly(hexamethylene glutaramide) or poly(butylene adipamide). The present invention limits the type of polyamide to the above range to prepare a high-performance elastomer.

[0074] In the present invention, the dicarboxylic acid preferably includes malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, 120,000 decanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, methylmalonic acid, 2-butyl suberic acid, 2-propylmalonic acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-methyladipic acid, maleic acid, fumaric acid, itaconic acid, isopropylmalonic acid, 2,3-dibromosuccinic acid, terephthalic acid, isophthalic acid, phthalic acid, 5-methylisophthalic acid, phenylsuccinic acid, benzylmalonic acid, cyclohexanedicarboxylic acid, 1,2-dimethyl-1,3-dimethyl-2-propanediol ... One or more of formic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, dimer acid, hydrogenated dimer acid, hydrogenated dimer oleic acid, dimer linoleic acid, dimer linolenic acid, dimer myristic acid, polyethylene glycol terminated with carboxyl groups at both ends, or polytetrahydrofuran terminated with carboxyl groups at both ends, more preferably one or more of dimer acid, hydrogenated dimer acid, hydrogenated dimer oleic acid, dimer linoleic acid, dimer linolenic acid, dimer myristic acid, polyethylene glycol terminated with carboxyl groups at both ends, or polytetrahydrofuran terminated with carboxyl groups at both ends, further preferably one or more of dimer acid, hydrogenated dimer acid, hydrogenated dimer oleic acid, dimer linoleic acid, or dimer linolenic acid. In the present invention, limiting the type of dicarboxylic acid to the above range can further improve the performance of the elastomer.

[0075] In the present invention, the mass ratio of the multifunctional antimicrobial monomer, polyamide, and dicarboxylic acid is preferably (0.5-0.6):(5-12):(10-18), more preferably (0.54-0.58):(6-10):(12-16), and even more preferably 0.56:8:14. Limiting the mass ratio of the multifunctional antimicrobial monomer, polyamide, and dicarboxylic acid to the above range ensures that the elastomer has good performance.

[0076] In the present invention, the catalyst is preferably p-toluenesulfonic acid. The catalyst is preferably added in an amount of 0.01-5% by weight, more preferably 2-4%, and even more preferably 3%, of the total mass of the multifunctional antimicrobial monomer, polyamide, and dicarboxylic acid. Limiting the catalyst content to this range ensures a smooth and rapid reaction.

[0077] In the present invention, the depolymerization reaction temperature is preferably 100-280°C, more preferably 150-250°C, and even more preferably 180-240°C; the depolymerization reaction time is preferably 0.5-24 hours, more preferably 8 hours. Limiting the depolymerization reaction temperature and time to the above ranges ensures that the long-chain structures in the waste polyamide and dicarboxylic acid are decomposed into low-molecular-weight prepolymers.

[0078] In the present invention, the depolymerization reaction is carried out in an inert atmosphere; preferably, argon. The flow rate of the introduced argon is not particularly limited, and a flow rate commonly used by those skilled in the art can be used. The introduction of argon can prevent the introduction of impurities into the reaction and can also remove the adipic acid produced during the reaction, thereby promoting the reaction.

[0079] In the present invention, the depolymerization reaction is preferably carried out under stirring conditions; the stirring speed is preferably greater than 100 rpm, more preferably 150 to 500 rpm. The present invention can promote the reaction by stirring.

[0080] In the present invention, the polymerization reaction is carried out under vacuum conditions; the vacuum degree of the vacuum conditions is preferably less than 150 Pa, more preferably less than 30 Pa. The present invention limits the vacuum degree to the above range to ensure that the polymerization reaction proceeds sufficiently while preventing small molecular prepolymers from being vacuumed away.

[0081] In the present invention, the polymerization reaction temperature is preferably 100-280°C, more preferably 200-260°C; and the polymerization reaction time is preferably 0.5-24 hours, more preferably 10-15 hours. Limiting the polymerization reaction temperature and time within these ranges ensures sufficient reaction progress and produces a high-performance antimicrobial elastomer.

[0082] In the present invention, the polymerization reaction is preferably carried out under stirring conditions; the stirring speed is preferably >100 rpm, more preferably 150 to 500 rpm. The present invention can promote the polymerization reaction by stirring.

[0083] The present invention also provides an antibacterial elastomer prepared by the preparation method described in the above technical solution. The antibacterial elastomer provided by the present invention has good high temperature resistance and antibacterial properties.

[0084] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0085] Example 1

[0086] A multifunctional antibacterial monomer, the chemical formula of the multifunctional antibacterial monomer is shown in Formula I:

[0087]

[0088] The preparation method of the multifunctional antibacterial monomer comprises the following steps:

[0089] (1) Imidazole, α,α'-dichloro-p-xylene, and methanol were refluxed and subjected to substitution reaction at 70°C for 18 hours, followed by distillation. The mixture was then added to a K2CO3 aqueous solution and allowed to stand to precipitate white bisimidazole-p-dibenzyl. The ratio of the mass of the imidazole, the mass of the α,α'-dichloro-p-xylene, and the volume of the methanol was 3.16 g:0.8 g:50 mL.

[0090] (2) The diimidazole-p-dibenzyl and anhydrous ethanol obtained in step (1) are slowly added dropwise with tetradecane bromide under reflux condensation and argon flow to carry out a quaternization reaction to obtain an intermediate; the mass ratio of the diimidazole-p-dibenzyl, tetradecane bromide and anhydrous ethanol is 0.5:1.4:5.2; the temperature of the quaternization polymerization reaction is 90° C., and the time of the quaternization polymerization reaction is 48 hours;

[0091] (3) The intermediate obtained in step (2), sodium 5-sulfoisophthalate and deionized water are mixed to perform an ion exchange reaction to obtain a multifunctional antibacterial monomer; the ratio of the mass of the intermediate, the mass of sodium 5-sulfoisophthalate and the volume of deionized water is 2g:10g:200mL.

[0092] The high temperature resistance test of the intermediate and the multifunctional antibacterial monomer in Example 1 was performed using a thermogravimetric analyzer (TG). The decomposition temperature of the intermediate obtained after the quaternization reaction was 280°C, and the decomposition temperature of the multifunctional antibacterial monomer was 320°C.

[0093] Example 2

[0094] An antibacterial elastomer prepared from polyhexamethylene adipamide (recycled waste polyhexamethylene adipamide film), hydrogenated dimer acid and the multifunctional antibacterial monomer described in Example 1;

[0095] The preparation method of the antibacterial elastomer comprises the following steps:

[0096] (a) A multifunctional antibacterial monomer, polyhexamethylene adipamide (recycled waste polyhexamethylene adipamide film), hydrogenated dimer acid, and p-toluenesulfonic acid are placed in a 250 mL three-necked flask, purged with argon gas to discharge air from a device, and gradually heated to 220° C. under stirring at 150 rpm for depolymerization to obtain a prepolymer; the mass ratio of the polyhexamethylene adipamide, hydrogenated dimer acid, and multifunctional antibacterial monomer is 8:14:0.56; the amount of the p-toluenesulfonic acid added is 0.5% of the total mass of the multifunctional antibacterial monomer, polyhexamethylene adipamide, and hydrogenated dimer acid;

[0097] (b) The prepolymer obtained in step (a) was subjected to polymerization reaction at 250° C. for 10 h under vacuum conditions (pressure less than 100 Pa) with stirring at 150 rpm to obtain an antibacterial elastomer.

[0098] The viscosity-average molecular weight of the antibacterial elastomer obtained in Example 2 is 22 kDa.

[0099] The antibacterial properties of the antibacterial elastomer were tested using an antibacterial experiment. The operation of the antibacterial experiment was as follows: S. aureus and E. coli suspensions were inoculated onto the surface of the antibacterial elastomer, respectively, and cultured at a constant temperature of 37.5°C. After culturing for 24 hours, the bacterial survival rate was determined using the drop plate counting method.

[0100] Through antibacterial experiments, the antibacterial elastomer obtained in Example 2 has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0101] Example 3

[0102] The only difference between Example 3 and Example 1 is that α,α'-dichloro-p-xylene in step (1) is replaced by α,α'-dichloro-o-xylene, and the rest is the same as Example 1.

[0103] Example 4

[0104] The only difference between Example 4 and Example 2 is that the multifunctional antibacterial monomer of Example 3 is used, and the rest is the same as Example 2.

[0105] The viscosity-average molecular weight of the antibacterial elastomer obtained in Example 4 is 21 kDa.

[0106] The antibacterial properties of the antibacterial elastomer were tested using an antibacterial experiment. The operation of the antibacterial experiment was as follows: S. aureus and E. coli suspensions were inoculated onto the surface of the antibacterial elastomer, respectively, and cultured at a constant temperature of 37.5°C. After culturing for 24 hours, the bacterial survival rate was determined using the drop plate counting method.

[0107] Through antibacterial experiments, the antibacterial elastomer obtained in Example 4 has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0108] Example 5

[0109] The only difference between Example 5 and Example 1 is that α,α'-dichloro-p-xylene in step (1) is replaced by α,α'-dichloro-m-xylene, and the rest is the same as Example 1.

[0110] Example 6

[0111] The only difference between Example 6 and Example 2 is that the multifunctional antibacterial monomer of Example 5 is used, and the rest is the same as Example 2.

[0112] The viscosity-average molecular weight of the antibacterial elastomer obtained in Example 6 is 20 kDa.

[0113] The antibacterial properties of the antibacterial elastomer were tested using an antibacterial experiment. The operation of the antibacterial experiment was as follows: S. aureus and E. coli suspensions were inoculated onto the surface of the antibacterial elastomer, respectively, and cultured at a constant temperature of 37.5°C. After culturing for 24 hours, the bacterial survival rate was determined using the drop plate counting method.

[0114] Through antibacterial experiments, the antibacterial elastomer obtained in Example 6 has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0115] Example 7

[0116] The only difference between Example 7 and Example 2 is that the polyhexamethylene adipamide (recycled waste polyhexamethylene adipamide film) in step (a) is replaced by polyhexamethylene glutaramide (recycled waste polyhexamethylene glutaramide film), and the rest is the same as Example 2.

[0117] The viscosity-average molecular weight of the antibacterial elastomer obtained in Example 7 is 20 kDa.

[0118] The antibacterial properties of the antibacterial elastomer were tested using an antibacterial experiment. The operation of the antibacterial experiment was as follows: S. aureus and E. coli suspensions were inoculated onto the surface of the antibacterial elastomer, respectively, and cultured at a constant temperature of 37.5°C. After culturing for 24 hours, the bacterial survival rate was determined using the drop plate counting method.

[0119] Through antibacterial experiments, the antibacterial elastomer obtained in Example 7 has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0120] Example 8

[0121] The only difference between Example 8 and Example 2 is that the polyhexamethylene adipamide (recycled waste polyhexamethylene adipamide film) in step (a) is replaced by polybutylene adipamide (recycled waste polybutylene adipamide film), and the rest is the same as Example 2.

[0122] The viscosity-average molecular weight of the antibacterial elastomer obtained in Example 8 is 20 kDa.

[0123] The antibacterial properties of the antibacterial elastomer were tested using an antibacterial experiment. The operation of the antibacterial experiment was as follows: S. aureus and E. coli suspensions were inoculated onto the surface of the antibacterial elastomer, respectively, and cultured at a constant temperature of 37.5°C. After culturing for 24 hours, the bacterial survival rate was determined using the drop plate counting method.

[0124] Through antibacterial experiments, the antibacterial elastomer obtained in Example 8 has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0125] Example 9

[0126] The only difference between Example 9 and Example 3 is that the polyhexamethylene adipamide (recycling waste polyhexamethylene adipamide film) in step (a) is replaced by polyhexamethylene adipamide (recycling waste polyhexamethylene adipamide film), and the rest is the same as Example 3.

[0127] The viscosity-average molecular weight of the antibacterial elastomer obtained in Example 9 is 15 kDa.

[0128] The antibacterial properties of the antibacterial elastomer were tested using an antibacterial experiment. The operation of the antibacterial experiment was as follows: S. aureus and E. coli suspensions were inoculated onto the surface of the antibacterial elastomer, respectively, and cultured at a constant temperature of 37.5°C. After culturing for 24 hours, the bacterial survival rate was determined using the drop plate counting method.

[0129] Through antibacterial experiments, the antibacterial elastomer obtained in Example 9 has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0130] Example 10

[0131] The only difference between Example 10 and Example 2 is that the polyhexamethylene adipamide (recycling waste polyhexamethylene adipamide film) in step (a) is replaced by polyhexamethylene adipamide (recycling waste polyhexamethylene adipamide film), and the rest is the same as Example 2.

[0132] The viscosity-average molecular weight of the antibacterial elastomer obtained in Example 10 is 18 kDa.

[0133] The antibacterial properties of the antibacterial elastomer were tested using an antibacterial experiment. The operation of the antibacterial experiment was as follows: S. aureus and E. coli suspensions were inoculated onto the surface of the antibacterial elastomer, respectively, and cultured at a constant temperature of 37.5°C. After culturing for 24 hours, the bacterial survival rate was determined using the drop plate counting method.

[0134] Through antibacterial experiments, the antibacterial elastomer obtained in Example 10 has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0135] Example 11

[0136] The only difference between Example 11 and Example 2 is that the hydrogenated dimer acid in step (a) is replaced by hydrogenated dimer oleic acid, and the rest is the same as Example 2.

[0137] The viscosity-average molecular weight of the antibacterial elastomer obtained in Example 11 is 20 kDa.

[0138] The antibacterial properties of the antibacterial elastomer were tested using an antibacterial experiment. The operation of the antibacterial experiment was as follows: S. aureus and E. coli suspensions were inoculated onto the surface of the antibacterial elastomer, respectively, and cultured at a constant temperature of 37.5°C. After culturing for 24 hours, the bacterial survival rate was determined using the drop plate counting method.

[0139] Through antibacterial experiments, the antibacterial elastomer obtained in Example 11 has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0140] Example 12

[0141] The only difference between Example 12 and Example 2 is that the hydrogenated dimer acid in step (a) is replaced by dimer linoleic acid, and the rest is the same as Example 2.

[0142] The viscosity-average molecular weight of the antibacterial elastomer obtained in Example 12 is 20 kDa.

[0143] The antibacterial properties of the antibacterial elastomer were tested using an antibacterial experiment. The operation of the antibacterial experiment was as follows: S. aureus and E. coli suspensions were inoculated onto the surface of the antibacterial elastomer, respectively, and cultured at a constant temperature of 37.5°C. After culturing for 24 hours, the bacterial survival rate was determined using the drop plate counting method.

[0144] Through antibacterial experiments, the antibacterial elastomer obtained in Example 12 has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0145] Example 13

[0146] The only difference between Example 13 and Example 2 is that the hydrogenated dimer acid in step (a) is replaced by dimer linolenic acid, and the rest is the same as Example 2.

[0147] The viscosity-average molecular weight of the antibacterial elastomer obtained in Example 13 is 19 kDa.

[0148] The antibacterial properties of the antibacterial elastomer were tested using an antibacterial experiment. The operation of the antibacterial experiment was as follows: S. aureus and E. coli suspensions were inoculated onto the surface of the antibacterial elastomer, respectively, and cultured at a constant temperature of 37.5°C. After culturing for 24 hours, the bacterial survival rate was determined using the drop plate counting method.

[0149] Through antibacterial experiments, the antibacterial elastomer obtained in Example 13 has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.

[0150] The mechanical properties of the antibacterial elastomer obtained in Example 2 were tested using a universal testing machine. The tensile curve obtained from the test is shown in FIG. Figure 1 As shown, from Figure 1 It can be seen that the tensile strength of the antibacterial elastomer can reach 51MPa and the elongation at break can reach 625%.

[0151] It can be seen from the above examples that the multifunctional antibacterial monomer provided by the present invention has a decomposition temperature of up to 320°C, and reacts with waste polyamide and dicarboxylic acid to generate a high-performance elastomer with a molecular weight of up to 22 kDa, a tensile strength of up to 51 MPa, and an elongation at break of up to 625%. It has an antibacterial property of up to 100% against Escherichia coli and Staphylococcus aureus, and has good high temperature resistance, antibacterial properties and mechanical properties.

[0152] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A multifunctional antibacterial monomer, the chemical formula of which is shown in Formula I: A-SO3 - B + -R-B + SO3 - -Formula I; In the formula I, A-SO3 - It is a sulfonate ion containing a dicarboxyl group; B + is an imidazolium quaternary ammonium salt cation; R is o-dibenzyl, m-dibenzyl or p-dibenzyl; The dicarboxyl-containing sulfonate ion is an isophthalic acid-5-sulfonate ion or a dimethyl terephthalate-5-sulfonate ion; The preparation method of the multifunctional antibacterial monomer comprises the following steps: (1) A compound containing an imidazole group, a xylene halide, and methanol are mixed to undergo a substitution reaction to obtain a benzyl compound containing a bisimidazole group; (2) mixing the benzyl compound containing a bisimidazole group obtained in step (1), a halogenated alkane and anhydrous ethanol to carry out a quaternization reaction to obtain an intermediate; the number of carbon atoms of the alkane in the halogenated alkane is ≥6; (3) The intermediate obtained in step (2), the dicarboxyl-containing sulfonate and deionized water are mixed to carry out an ion exchange reaction to obtain a multifunctional antibacterial monomer.

2. The method for preparing the multifunctional antibacterial monomer according to claim 1, comprising the following steps: (1) A compound containing an imidazole group, a xylene halide, and methanol are mixed to undergo a substitution reaction to obtain a benzyl compound containing a bisimidazole group; (2) mixing the benzyl compound containing a bisimidazole group obtained in step (1), a halogenated alkane and anhydrous ethanol to carry out a quaternization reaction to obtain an intermediate; the number of carbon atoms of the alkane in the halogenated alkane is ≥6; (3) The intermediate obtained in step (2), the dicarboxyl-containing sulfonate and deionized water are mixed to carry out an ion exchange reaction to obtain a multifunctional antibacterial monomer.

3. A method for preparing an antibacterial elastomer, comprising: The multifunctional antibacterial monomer according to claim 1, polyamide, dicarboxylic acid and catalyst are mixed and then subjected to depolymerization reaction and polymerization reaction in sequence to obtain an antibacterial elastomer; the depolymerization reaction is carried out in an inert atmosphere; and the polymerization reaction is carried out under vacuum conditions.

4. The preparation method according to claim 3, characterized in that The polyamide includes one or more of polybutyrolactam, polycaprolactam, polyheptamide, polyoctylamide, polynonanamide, polyundecalactam, polydodecamide, polytridecanamide, polyhexamethylenediamine adipamide, polyhexamethylenediamine glutaramide, polybutylene adipamide, polybutylene adipamide, polypentamethylenediamine, polyhexamethylenediamine, polydodecanoyldiamine, polydodecanoyldiamine, polyhexamethylenediamine terephthalamide, polynonamethylenediamine, polydecane terephthalamide, polytrimethylhexamethylenediamine, polyparaphenylene terephthalamide, polymethyleneisophthalamide or polymethyleneisophthalamide.

5. The preparation method according to claim 3, characterized in that The mass ratio of the multifunctional antibacterial monomer, polyamide and dicarboxylic acid is (0.5-0.6): (5-12): (10-18).

6. The preparation method according to claim 3, characterized in that The added amount of the catalyst is 0.01-5% of the total mass of the multifunctional antibacterial monomer, polyamide and dicarboxylic acid.

7. The preparation method according to claim 3, characterized in that The temperature of the depolymerization reaction is 100-280° C., and the time of the depolymerization reaction is 0.5-24 hours.

8. The preparation method according to claim 3, characterized in that The polymerization reaction temperature is 100-280° C., and the polymerization reaction time is 0.5-24 hours.

9. The antibacterial elastomer prepared by the preparation method according to any one of claims 3 to 8.

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