阅读说明：本技术 塑料抗菌剂及抗菌塑料 (Plastic antibacterial agent and antibacterial plastic ) 是由 朱金娥 于 2020-05-27 设计创作，主要内容包括：本发明公开了一种塑料抗菌剂及抗菌塑料,本发明的塑料抗菌剂通过季鏻盐与聚乙二醇接枝,增加抗菌剂稳定性,避免小分子季鏻盐易分解产生毒性；另一方面,抗菌剂与塑料混合体系的相容性增强,分散性更好,界面结合作用也更强,季鏻盐分子链与细胞膜所带电性相反,通过异性相吸作用,更多地聚集在细菌表面,阻止细菌从外界获取营养物质进入胞内,从而杀死细菌。本发明的抗菌塑料具有良好的抗菌性能。(The invention discloses a plastic antibacterial agent and antibacterial plastic, wherein the plastic antibacterial agent is grafted by quaternary phosphonium salt and polyethylene glycol, so that the stability of the antibacterial agent is improved, and the toxicity generated by easy decomposition of small molecular quaternary phosphonium salt is avoided; on the other hand, the compatibility of the antibacterial agent and a plastic mixed system is enhanced, the dispersibility is better, the interface combination effect is stronger, the quaternary phosphonium salt molecular chain and the cell membrane are opposite in electric property, more quaternary phosphonium salt molecular chains are gathered on the surface of bacteria through the opposite attraction effect, and the bacteria are prevented from getting nutrient substances from the outside and entering the cells, so that the bacteria are killed. The antibacterial plastic disclosed by the invention has good antibacterial performance.)

1. The preparation method of the plastic antibacterial agent is characterized by comprising the following steps:

adding an organic phosphine reagent and 2-chloro-1, 1-dimethoxyethane into an organic solvent, wherein the mass ratio of the organic phosphine reagent to the 2-chloro-1, 1-dimethoxyethane is (1-1.5): (2-3), wherein the mass ratio of the organic phosphine reagent to the organic solvent is (3.5-5.5): (60-70), reacting for 2.0-3.5h at 50-60 ℃; and then sequentially adding acetaldehyde and a 92-99 wt% sulfuric acid solution, wherein the mass ratio of the acetaldehyde to the 2-chloro-1, 1-dimethoxyethane is (1-5): (1-1.5), wherein the mass ratio of the 92-99 wt% sulfuric acid solution to the organic solvent is (0.1-1.0): (60-70), reacting for 3.0-5.0h at 50-60 ℃; cooling, extracting with water, and collecting a water phase to obtain a reaction solution A;

mixing a polyethylene glycol solution with a reaction solution A, wherein the volume ratio of the polyethylene glycol solution to the reaction solution A is (1-10) to (1.0-1.5), reacting at 50-55 ℃ for 10-25min, and heating to 90-100 ℃ for 2.5-3.5 h; cooling, adding sodium sulfate to separate out solid, wherein the mass ratio of the sodium sulfate to the reaction solution A is (1.0-1.5): (5.0-6.5), washing with water for 1-3 times, and drying at 65-75 ℃ for 10-15 h.

2. The method for preparing the plastic antibacterial agent according to claim 1, wherein the organic solvent is a mixture of dichloromethane and trichloromethane according to a mass ratio of 1 (1-3).

3. The method of claim 1, wherein the polyethylene glycol solution is prepared by the following steps: adding polyethylene glycol into water, stirring for 5-15min at a stirring speed of 120-.

4. The method of claim 1 wherein the organophosphine reagent is at least one of triisopropylphosphine, tri-tert-butylphosphine, and tricyclopentylphosphine.

5. An antimicrobial agent for plastics, which is obtainable by the process of any one of claims 1 to 4.

6. An antibacterial plastic characterized in that the raw material contains the plastic antibacterial agent of claim 5.

7. The antibacterial plastic of claim 6, wherein the mass ratio of the resin in the raw material to the plastic antibacterial agent is (80-120): (2-8).

8. The antibacterial plastic according to claim 7, wherein the resin is at least one of ABS resin, PVC resin, PET resin, PBT resin and polycarbonate resin.

Technical Field

The invention belongs to the technical field of plastics, and particularly relates to a plastic antibacterial agent and antibacterial plastic.

Background

With the higher requirements of people on living environment, the demand of high-performance antibacterial materials is also increasing. The antibacterial plastic is prepared by adding an antibacterial agent into plastic, so that the plastic has antibacterial property, and can kill or inhibit bacteria on the plastic in a long time.

The selection of an antimicrobial agent that has broad spectrum, long-lasting efficacy, good compatibility, and high safety for plastics is an urgent problem to be solved.

According to the difference of the internal components of chemical substances, the antibacterial agent can be divided into a natural antibacterial agent, an inorganic antibacterial agent, an organic antibacterial agent and other antibacterial agents, wherein the organic antibacterial agent has the advantages of small molecular weight, strong action effect, quick sterilization effect and the like; in addition, a large number of resistant bacteria are produced.

Disclosure of Invention

In view of the defects of the prior art, one of the technical problems to be solved by the invention is to provide a preparation method of a plastic antibacterial agent; secondly, providing the plastic antibacterial agent prepared by the method; thirdly, an antibacterial plastic is provided, which contains the plastic antibacterial agent.

The invention conception of the invention is as follows:

starch and polyvinyl alcohol can be used as a carbon source and an energy source of bacteria, and the polyvinyl alcohol is the only vinyl polymer which can be used as the carbon source and the energy source by the bacteria; compared with starch, polyvinyl alcohol, silica gel and the like which are used as high molecular materials for grafting, the polyethylene glycol has the advantages of better compatibility with plastics, difficult growth of bacteria on the polyethylene glycol and the like; according to the invention, polyethylene glycol is grafted and copolymerized to prepare the plastic antibacterial agent, on one hand, the stability of the antibacterial agent is increased by grafting the quaternary phosphonium salt and the polyethylene glycol, and the toxicity generated by easy decomposition of the micromolecular quaternary phosphonium salt is avoided; on the other hand, the compatibility of the antibacterial agent and a plastic such as polycarbonate mixed system is enhanced, the dispersibility is better, the interface combination effect is stronger, the quaternary phosphonium salt molecular chain and the cell membrane are opposite in electric charge, more quaternary phosphonium salt molecular chains are gathered on the surface of bacteria through the opposite attraction effect, and the bacteria are prevented from getting nutrient substances from the outside and entering the cells, so that the bacteria are killed.

Based on the above conception, the technical scheme of the invention is as follows:

the invention provides a preparation method of a plastic antibacterial agent, which comprises the following steps:

adding an organic phosphine reagent and 2-chloro-1, 1-dimethoxyethane into an organic solvent, wherein the mass ratio of the organic phosphine reagent to the 2-chloro-1, 1-dimethoxyethane is (1-1.5): (2-3), wherein the mass ratio of the organic phosphine reagent to the organic solvent is (3.5-5.5): (60-70), reacting for 2.0-3.5h at 50-60 ℃; and then sequentially adding acetaldehyde and a 92-99 wt% sulfuric acid solution, wherein the mass ratio of the acetaldehyde to the 2-chloro-1, 1-dimethoxyethane is (1-5): (1-1.5), wherein the mass ratio of the 92-99 wt% sulfuric acid solution to the organic solvent is (0.1-1.0): (60-70), reacting for 3.0-5.0h at 50-60 ℃; cooling, extracting with water, and collecting a water phase to obtain a reaction solution A;

mixing a polyethylene glycol solution with a reaction solution A, wherein the volume ratio of the polyethylene glycol solution to the reaction solution A is (1-10) to (1.0-1.5), reacting at 50-55 ℃ for 10-25min, and heating to 90-100 ℃ for 2.5-3.5 h; cooling, adding sodium sulfate to separate out a solid, wherein the mass ratio of the sodium sulfate to the reaction solution A is (1.0-1.5) to (5.0-6.5), washing with water for 1-3 times, and drying at 65-75 ℃ for 10-15h to obtain the sodium sulfate/sodium hydrogen phosphate solid;

firstly, reacting an organic phosphine reagent with 2-chloro-1, 1-dimethoxyethane and acetaldehyde in an organic solvent system, thereby introducing aldehyde groups into organic phosphine molecules; and secondly, grafting and copolymerizing aldehyde groups in the organic phosphine molecules and hydroxyl groups in polyethylene glycol molecules to generate the plastic antibacterial agent.

Preferably, the organic solvent is at least one of tetrahydrofuran, acetone, dichloromethane and chloroform; further preferably, the organic solvent is a mixture of dichloromethane and trichloromethane according to a mass ratio of 1 (1-3);

preferably, the preparation method of the polyethylene glycol solution is as follows: adding polyethylene glycol into water, stirring for 5-15min at a stirring speed of 120-.

Preferably, the organic phosphine reagent is at least one of triisopropylphosphine, tri-tert-butylphosphine and tricyclopentylphosphine; further preferably, the organic phosphine reagent is a mixture of tri-tert-butylphosphine and tricyclopentylphosphine according to a mass ratio of 1 (0.5-5).

The organic phosphine reagent is compounded by tri-tert-butylphosphine and tricyclopentylphosphine, so that the synergistic effect is achieved, and the antibacterial performance of the plastic is further improved; the plastic antibacterial agent, namely the polyethylene glycol-quaternary phosphonium salt antibacterial agent, which is formed by respectively taking tri-tert-butylphosphine and tricyclopentylphosphine as centers and carrying out graft copolymerization with polyethylene glycol has more stable structure, better dispersibility in a plastic system and higher antibacterial performance of plastics.

The invention also provides a plastic antibacterial agent prepared by the method.

The invention also provides an antibacterial plastic, and the raw materials of the antibacterial plastic comprise the plastic antibacterial agent.

Preferably, the mass ratio of the resin to the plastic antibacterial agent in the raw materials of the antibacterial plastic is (80-120): 2-8. The resin in the antibacterial plastic can be: at least one of ABS resin, PVC resin, PET resin, PBT resin and polycarbonate resin.

Preferably, the antibacterial plastic is prepared from the following raw materials: 80-120 parts of polycarbonate resin, 2-8 parts of plastic antibacterial agent, 3-12 parts of triphenyl phosphite and 6-20 parts of N, N' -ethylene bis stearamide.

The invention also discloses the antibacterial plastic prepared by the following method:

the method comprises the following steps: adding the raw materials into a mixer according to the formula, and mixing for 5-20min, wherein the set rotating speed is 300-600 rpm;

step two: adding the mixed materials into a double-screw extruder for extrusion granulation, wherein the temperature of a feeding section is set to be 250-plus-270 ℃, the temperature of a melting section is set to be 260-plus-280 ℃, the temperature of a homogenizing section is set to be 270-plus-290 ℃, and the temperature of a machine head is set to be 280-plus-300 ℃;

step three: drying the extruded granules, setting the drying temperature to be 80-100 ℃, the drying time to be 5-20h, and carrying out injection molding to obtain the composite material.

The invention has the beneficial effects that: the invention adopts a plastic antibacterial agent prepared by a specific method; on one hand, the stability of the antibacterial agent is improved by grafting the quaternary phosphonium salt and the polyethylene glycol, and the toxicity generated by the easy decomposition of the micromolecular quaternary phosphonium salt is avoided; on the other hand, the compatibility of the antibacterial agent and a plastic such as polycarbonate mixed system is enhanced, the dispersibility is better, the interface combination effect is stronger, the quaternary phosphonium salt molecular chain and the cell membrane are opposite in electric charge, more quaternary phosphonium salt molecular chains are gathered on the surface of bacteria through the opposite attraction effect, and the bacteria are prevented from getting nutrient substances from the outside and entering the cells, so that the bacteria are killed. Furthermore, the organic phosphine reagent is compounded by tri-tert-butylphosphine and tricyclopentylphosphine, so that the synergistic effect is achieved, and the antibacterial performance of the plastic is further improved; the plastic antibacterial agent formed by respectively taking tri-tert-butylphosphine and tricyclopentylphosphine as centers and carrying out graft copolymerization with polyethylene glycol has more stable structure, better dispersibility in a plastic system and higher antibacterial performance of plastics.

Detailed Description

The specific parameters of some substances in the embodiment of the invention are as follows:

polycarbonate resin, designation LXTY1609T-11, available from Luxi chemical group, Inc.

Polyethylene glycol, CAS: 25322-68-3, PEG8000, purity: 99% of the total weight of the product, purchased from Nantong sea Tianyuan chemical Co.

Triphenyl phosphite, CAS: 101-02-0, purity: 99% of the total amount of the product obtained from Yarui chemical Co., Ltd.

N, N' -ethylene bis stearamide, CAS: 110-30-5, purity: 98% of the total weight of the composition, which is purchased from Shanghai-derived leaf Biotech Co.

Triphenylphosphine, CAS: 603-35-0, purity: 98% of the total amount of the compound, available from Beijing coupled technology, Inc.

Tri-tert-butylphosphine, CAS: 13716-12-6, purity: 98% of the total weight of the composition, purchased from Beijing national Dingsheng science and technology Limited.

Tricyclopentylphosphine, CAS: 7650-88-6, purity: 95% of the total amount of.

Acetaldehyde, CAS: 75-07-0, purity: 40 wt% aqueous solution, purchased from Shanghai Teita chemical science and technology Limited.

2-chloro-1, 1-dimethoxyethane, purity: 98% of the total weight of the product, purchased from Shijiazhuang Dongcheng chemical Co.