阅读说明：本技术 一种持久抗菌聚丙烯牙刷毛及其制备方法 (Lasting antibacterial polypropylene toothbrush bristles and preparation method thereof ) 是由 张洪胜 于 2020-06-17 设计创作，主要内容包括：本发明公开一种持久抗菌聚丙烯牙刷毛及其制备方法；该持久抗菌聚丙烯牙刷毛由含有端羟基聚丙烯与含有硅烷的RAFT链转移试剂反应制备的得到大分子链转移剂,然后通过可逆加成-断裂链转移反应将具有抗菌作用的季铵盐引入聚合物分子链中,制备得到的持久抗菌聚丙烯牙刷毛克服了聚合物和抗菌剂共混时分散的不均匀性和避免抗菌成分的流失问题,使牙刷毛具有长久的抗菌性。(The invention discloses a polypropylene toothbrush hair with lasting antibacterial property and a preparation method thereof; the durable antibacterial polypropylene toothbrush hair is prepared by reacting hydroxyl-terminated polypropylene with a silane-containing RAFT chain transfer reagent to obtain a macromolecular chain transfer agent, and then introducing quaternary ammonium salt with an antibacterial effect into a polymer molecular chain through a reversible addition-fragmentation chain transfer reaction.)

1. A durable antibacterial polypropylene toothbrush bristle having a structure of formula (I):

wherein R is ═ CH₂)₁₅CH₃The value of n is 50-2000, and the value of m is 15-220.

2. The method for preparing durable antibacterial polypropylene toothbrush bristles according to claim 1, comprising the steps of:

(1) dissolving mercaptoacetic acid and potassium carbonate in dichloromethane, and reacting for 60 minutes at 40 ℃; then adding carbon disulfide into the system drop by drop, and continuing to react for 60 minutes at 40 ℃; adding 4- (chloromethyl) phenyltrimethoxysilane into the system, and continuing to react for 12 hours at the temperature of 40 ℃ to obtain a RAFT chain transfer reagent containing silane;

(2) dissolving a RAFT chain transfer reagent containing silane in dichloromethane, slowly dropwise adding thionyl chloride, reacting at 40 ℃ for 60 minutes, and removing low-boiling-point residues under reduced pressure; further preparing the obtained acyl-chlorinated silane-containing RAFT chain transfer reagent into a toluene solution, dropwise adding the toluene solution into a monohydroxy terminal-substituted polypropylene toluene solution, heating to 80 ℃, adding pyridine and the acyl-chlorinated silane-containing RAFT chain transfer reagent toluene solution, and reacting for 2 hours at 80 ℃ to obtain a polypropylene macromolecular RAFT chain transfer reagent;

(3) mixing Azodiisobutyronitrile (AIBN), a polypropylene macromolecule RAFT chain transfer reagent and a double-branched cationic hydrophobic monomer N, N' -bis (hexadecyldimethyl) -1, 2-dichloro-2-butylene-ammonium salt in dioxane, and reacting for 30 minutes at 80 ℃ to obtain a polypropylene block quaternary ammonium salt copolymer;

(4) dissolving the polypropylene block quaternary ammonium salt copolymer and the graphene oxide in ethanol, N₂Protecting, and reacting at 80 ℃ for 12h to obtain a graphene oxide loaded polypropylene block quaternary ammonium salt copolymer;

(5) and (3) putting the dried solid graphene oxide loaded polypropylene block quaternary ammonium salt copolymer into a melt spinning machine for spinning at 250 ℃, and finally cooling and forming at 0 ℃ for 2.5 hours to prepare the antibacterial bristles.

3. The method for preparing durable antibacterial polypropylene toothbrush bristles according to claim 2, wherein the molar ratio of thioglycolic acid to potassium carbonate, carbon disulfide and 4- (chloromethyl) phenyltrimethoxysilane in the step (1) is 1:1:2: 1.

4. The method for preparing polypropylene toothbrush bristles having lasting antibacterial effect as claimed in claim 2, wherein the molar ratio of the monohydroxy-terminally substituted polypropylene to the silane-containing RAFT chain transfer agent and thionyl chloride in step (2) is 1:4: 20.

5. The method of preparing durable antibacterial polypropylene toothbrush bristles according to claim 2, wherein the molar ratio of azobisisobutyronitrile to polypropylene macro-molecule RAFT chain transfer agent, the double-branched cationic hydrophobic monomer N, N '-bis (hexadecyldimethyl) -1, 2-dichloro-2-butene-ammonium salt in step (3) is 1:8:800, and the molar concentration of the double-branched cationic hydrophobic monomer N, N' -bis (hexadecyldimethyl) -1, 2-dichloro-2-butene-ammonium salt in the polymerization reaction system is 1 mol/L.

Technical Field

The invention belongs to a high polymer material, and particularly relates to a durable antibacterial polypropylene toothbrush bristle and a preparation method thereof.

Background

The toothbrush belongs to daily necessities, and has the functions of brushing residues in the oral cavity and cleaning teeth and gums so as to keep the oral cavity clean and sanitary. However, the material for manufacturing the toothbrush is generally plastic, and the plastic is easy to breed bacteria due to the nature of the plastic, and the toothbrush is polluted every day, so that thorough sanitation, hygiene and health and safety are difficult to realize. Especially, the combination part of the toothbrush bristle bottom and the toothbrush handle and the toothbrush bristles can store dirty and dirty, is very difficult to clean, can breed a large amount of bacteria after being used for a long time, and will certainly cause adverse effects on human health.

In order to improve the antibacterial performance of toothbrushes, there are many researches in the prior art, some of which change the working mode of toothbrushes, change manual toothbrushes into electric-driven rotary and high-frequency sound wave vibration toothbrushes, and some of which change the materials of toothbrushes, and improve the antibacterial performance of toothbrushes by improving the materials of toothbrushes. CN1107-31610A discloses an antibacterial toothbrush and a preparation method thereof, the bristles of the antibacterial toothbrush are made from 96-97.5% of plant fiber, cellulose, polyethylene terephthalate mixture, 0.5-1% of coupling agent and 2-3% of antibacterial agent through physical mixing, stirring concentration, extrusion, granulation and melt spinning, wherein the antibacterial agent is the extract of tea, common andrographis herb, horseradish and garden balsam stem. The obtained antibacterial toothbrush bristles have a good antibacterial effect, and are simple to prepare and low in cost. The invention patent adds the antibacterial agent into the polymer base material by a physical mixing method, and because the inorganic antibacterial molecules and the polymer base material do not have chemical bond action, the uniformity of the dispersion of the antibacterial agent is not easy to ensure, and in addition, the loss problem of the antibacterial component is difficult to avoid, thus directly influencing the long-term antibacterial performance of the product.

The polypropylene fiber has the advantages of rich raw materials, low production cost, light weight, high strength, good wear resistance and elasticity, good hot melt property, excellent ultrasonic welding property, low price and the like, the polypropylene also has the advantage of relatively stable chemical property, the moisture absorption rate of the fiber material is zero, and the prepared melt-blown non-woven fabric has the characteristics of acid and alkali resistance, organic chemical solvent resistance, worm damage resistance, mildew and rot resistance, no toxicity and the like, and is suitable for environments under various conditions. Based on the polypropylene toothbrush bristles, the polypropylene toothbrush bristles have good and lasting antibacterial stability.

Disclosure of Invention

In order to solve the defects of the prior art, the invention provides the lasting antibacterial polypropylene toothbrush hair and the preparation method thereof, the lasting antibacterial polypropylene toothbrush hair is prepared by reacting hydroxyl-terminated polypropylene with a silane-containing RAFT chain transfer reagent to obtain a macromolecular chain transfer agent, and then introducing quaternary ammonium salt with antibacterial effect into a polymer molecular chain through reversible addition-fragmentation chain transfer reaction, so that the prepared lasting antibacterial polypropylene toothbrush hair overcomes the problems of dispersion nonuniformity and antibacterial component loss during blending of a polymer and an antibacterial agent.

The invention aims to provide a durable antibacterial polypropylene toothbrush bristle.

The invention also aims to provide a preparation method of the durable antibacterial polypropylene toothbrush hair.

The above purpose of the invention is realized by the following technical scheme:

the durable antibacterial polypropylene toothbrush bristle has a structural formula shown as the following formula (I):

wherein R is ═ CH₂)₁₅CH₃The value of n is 50-2000, and the value of m is 15-220.

The reaction process and the preparation method of the lasting antibacterial polypropylene toothbrush bristles are as follows:

1. preparation of RAFT chain transfer reagents containing silane.

Dissolving mercaptoacetic acid and potassium carbonate in dichloromethane, and reacting for 60 minutes at 40 ℃; then adding carbon disulfide into the system drop by drop, and continuing to react for 60 minutes at 40 ℃; and adding 4- (chloromethyl) phenyltrimethoxysilane into the system, and continuing to react for 12 hours at the temperature of 40 ℃ to obtain the RAFT chain transfer reagent containing silane. Wherein the molar ratio of the thioglycolic acid to the potassium carbonate to the carbon disulfide to the p-chloro 4-phenyltrimethoxysilane is 1:1:2: 1.

2. Preparing a polypropylene macromolecule RAFT chain transfer reagent.

Dissolving a RAFT chain transfer reagent containing silane in dichloromethane, slowly dropwise adding thionyl chloride, reacting at 40 ℃ for 60 minutes, and removing low-boiling-point residues under reduced pressure; and (3) further preparing the obtained acyl-chlorinated silane-containing RAFT chain transfer reagent into a toluene solution, dropwise adding the toluene solution into a monohydroxy terminal-substituted polypropylene toluene solution, heating to 80 ℃, adding pyridine and the acyl-chlorinated silane-containing RAFT chain transfer reagent into the toluene solution, and reacting for 2 hours at 80 ℃ to obtain the polypropylene macromolecular RAFT chain transfer reagent. Wherein the molar ratio of the monohydroxy terminal substituted polypropylene to the silane-containing RAFT chain transfer agent to the thionyl chloride is 1:4: 20.

3. And (3) preparing a polypropylene block quaternary ammonium salt copolymer.

Azodiisobutyronitrile (AIBN), a polypropylene macromolecule RAFT chain transfer reagent and a double-branched cationic hydrophobic monomer N, N' -bis (hexadecyldimethyl) -1, 2-dichloro-2-butylene-ammonium salt are mixed in dioxane and react for 30 minutes at 80 ℃ to obtain the polypropylene block quaternary ammonium salt copolymer. Wherein the molar ratio of the azodiisobutyronitrile to the polypropylene macromolecule RAFT chain transfer reagent to the double-branched cationic hydrophobic monomer N, N '-bis (hexadecyldimethyl) -1, 2-dichloro-2-butene-ammonium salt is 1:8:800, and the molar concentration of the double-branched cationic hydrophobic monomer N, N' -bis (hexadecyldimethyl) -1, 2-dichloro-2-butene-ammonium salt in a polymerization reaction system is 1 mol/L.

4. And (3) preparing the graphene oxide loaded polypropylene block quaternary ammonium salt copolymer.

Dissolving the polypropylene block quaternary ammonium salt copolymer and the graphene oxide in ethanol, N₂And (4) protecting, and reacting for 12h at 80 ℃ to obtain the graphene oxide loaded polypropylene block quaternary ammonium salt copolymer.

5. And (3) preparing the durable antibacterial polypropylene toothbrush bristles.

And (3) putting the dried solid graphene oxide loaded polypropylene block quaternary ammonium salt copolymer into a melt spinning machine for spinning at 250 ℃, and finally cooling and forming at 0 ℃ for 2.5 hours to prepare the antibacterial bristles.

Compared with the prior art, the invention has the following advantages and beneficial effects:

the durable antibacterial polypropylene toothbrush hair with antibacterial effect is prepared through reversible addition-fragmentation chain transfer reaction, and the prepared durable antibacterial polypropylene toothbrush hair overcomes the problems of non-uniformity of dispersion and avoidance of loss of antibacterial components when the polymer and the antibacterial agent are blended.

Detailed Description

The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.