阅读说明：本技术 一种用于制备抗菌聚合物的链转移剂及其制备方法 (Chain transfer agent for preparing antibacterial polymer and preparation method thereof ) 是由 吴张峰 陈继云 于 2020-07-27 设计创作，主要内容包括：本发明公开一种用于制备抗菌聚合物的链转移剂及其制备方法；用于制备抗菌聚合物的链转移剂具有以下所示结构：<Image he="287" wi="700" file="DDA0002604419640000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>式中R为<Image he="153" wi="700" file="DDA0002604419640000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>本发明制备用于制备抗菌聚合物的链转移剂的合成工艺操作简单,没有产生有毒副产物,合成原料价格低廉；将该链转移剂用于制备得到的聚合物具有良好的杀菌作用,且该链转移剂可作为润滑油添加剂,具有良好的抗磨减摩作用。(The invention discloses a chain transfer agent for preparing an antibacterial polymer and a preparation method thereof; the chain transfer agent used to prepare the antimicrobial polymer has the structure shown below: wherein R is The synthesis process for preparing the chain transfer agent for preparing the antibacterial polymer is simple to operate, no toxic by-product is generated, and the synthesis raw material is low in price; the chain transfer agent has good bactericidal effect on the polymer prepared by using the chain transfer agent, and can be used as a lubricating oil additive, so that the chain transfer agent has good anti-wear and anti-friction effects.)

1. A chain transfer agent for preparing an antibacterial polymer, wherein the chain transfer agent for preparing the antibacterial polymer has a structural formula shown as the following formula (I):

wherein R is

2. The method of preparing a chain transfer agent for use in preparing an antimicrobial polymer according to claim 1, comprising the steps of:

(1) adding a chain transfer agent and carbon tetrachloride into the mouth-branched bottle, fully and uniformly mixing, then adding an acyl chlorination reagent thionyl chloride, and continuously stirring until the mixture is clear; and (3) heating the mixed solution to 77 ℃, after the reaction is finished, rotationally evaporating the solvent in vacuum to obtain yellow oily liquid, and drying in vacuum at room temperature to obtain the chain transfer agent acyl chlorination product.

(2)N₂Under protection, adding 2 '-bromo-2, 6-difluoro-4-hydroxyacetophenone, freshly distilled pyridine and tetrahydrofuran into a flask with a branch mouth until the 2' -bromo-2, 6-difluoro-4-hydroxyacetophenone is completely dissolved; dissolving the chain transfer agent acyl chloride product prepared in the step in tetrahydrofuran, dropwise adding the tetrahydrofuran into a 2' -bromo-2, 6-difluoro-4-hydroxyacetophenone solution at 0 ℃, stirring the solution at room temperature for 1h, then adding chloroform, reacting at 65 ℃ for 10h, washing the mixed solution with saturated sodium bicarbonate, deionized water and dilute hydrochloric acid, and performing reduced pressure evaporation to dryness on the obtained crude product, and performing column purification to obtain a chain transfer agent esterification product A.

(3)N₂Under protection, adding a thioacetamide and chain transfer agent esterification product A into a branched flask, adding a reaction solvent N, N-dimethylformamide, reacting at 140 ℃ for 20 hours, monitoring the reaction process by TLC, extracting with ethyl acetate/water after the reaction is finished, washing the combined organic phase with water and brine, drying, filtering, concentrating, and purifying by a column to obtain a product B.

(4)N₂Under protection, the products B and NBS are dissolved in the reaction solvent CCl₄And (3) reacting at 80 ℃ for 4h, monitoring the reaction process by TLC, after the reaction is finished, evaporating the reaction crude product to dryness under reduced pressure, and purifying by a column to obtain a product C.

(5)N₂And under protection, dissolving the product C in N, N-dimethylformamide, adding 2, 6-difluoro-3-hydroxy-benzamide and alkali, reacting at room temperature for 18h, after the reaction is finished, evaporating the crude reaction product under reduced pressure to dryness, and purifying by a column to obtain a product D.

(6) Dissolving the product D in acetic acid, adding Zn powder, reacting at 120 ℃ for 2h, monitoring the reaction process by TLC, adding alkali to adjust the pH to 8-9, extracting with ethyl acetate/water, washing the combined organic phase with water and brine, drying, filtering, concentrating, and purifying by a column to obtain the antibacterial chain transfer agent product E.

3. The method of preparing a chain transfer agent for use in preparing an antibacterial polymer according to claim 2, wherein, in the step (1), the chain transfer agent is benzyltrithiocarbonate-based propionic acid and 2- (ethylmercaptothiocarbonylthio) -2-methylpropionic acid; the dosage of the chain transfer agent is 0.1-0.5 g of the chain transfer agent per milliliter of carbon tetrachloride; the volume ratio of the acyl chlorination reagent to the carbon tetrachloride is 0.1-0.5: 1.

4. The method for preparing a chain transfer agent for preparing an antibacterial polymer according to claim 2, wherein in the step (2), the molar ratio of the chain transfer agent acyl chlorination product, 2' -bromo-2, 6-difluoro-4-hydroxyacetophenone and pyridine is 1:1: 2-5.

5. The method for preparing the chain transfer agent for preparing the antibacterial polymer according to claim 2, wherein in the step (3), the molar ratio of thioacetamide to the chain transfer agent esterification product A is 5-10: 1.

6. The method of preparing a chain transfer agent for an antibacterial polymer according to claim 2, wherein in the step (4), the molar ratio of the product B to NBS is 1:1.2 to 2.0.

7. The method for preparing a chain transfer agent for antibacterial polymer according to claim 2, wherein in the step (5), the molar ratio of the product C, 2, 6-difluoro-3-hydroxy-benzamide to the base is 1:1: 3-5; the alkali is sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, etc.

8. The method for preparing a chain transfer agent for preparing an antibacterial polymer according to claim 2, wherein in the step (6), the molar ratio of the product D, acetic acid and Zn powder is 1: 1.2-1.5; the alkali is sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, etc.

9. The chain transfer agent for preparing an antibacterial polymer according to claim 1 or 2 can be applied to the preparation of antibacterial polymer materials such as antibacterial polyethylene, antibacterial polypropylene, antibacterial polystyrene, antibacterial polyvinyl chloride, antibacterial poly-N-isopropylacrylamide and the like.

Technical Field

The invention belongs to the field of chemical synthesis, and particularly relates to a chain transfer agent for preparing an antibacterial polymer and a preparation method thereof.

Background

RAFT polymerization is based on living propagation of a polymer chain by introducing a reversible chain transfer reaction through cleavage of an S — C bond after addition of a propagating radical to a double bond of a compound having an — S — C ═ S structure, and is called reversible addition-fragmentation chain transfer radical polymerization; the RAFT has the greatest advantage that the range of applicable monomers is wide, besides common monomers, protonic monomers such as acrylic acid, sodium p-vinylbenzene sulfonate, hydroxyethyl methacrylate, aminoethyl methacrylate and the like or acid and alkaline monomers can be smoothly polymerized, and the method is very favorable for the polymerization reaction of alkene monomers containing special functional groups; does not require the use of expensive reagents (such as TEMPO) and does not cause impurities or residual reagents (such as transition metal ions in ATRP, bipyridine, etc.) to be difficult to remove from the polymer product; the molecular design ability is strong, and the copolymer can be used for preparing block, graft and star copolymers, mainly comprising dithioester and trithioester compounds.

The invention discloses a RAFT chain transfer agent with antibacterial effect, which is prepared by using a RAFT chain transfer agent to initiate monomer copolymerization, so that a copolymerization material has antibacterial property without adding an antibacterial agent into a polymer material; in addition, the prepared chain transfer agent can be used as a lubricating oil additive and has good anti-wear and anti-friction effects.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides the chain transfer agent for preparing the antibacterial polymer, the synthesis process of the chain transfer agent for preparing the antibacterial polymer is simple to operate, no toxic by-product is generated, and the synthesis raw material is low in price; the chain transfer agent has good bactericidal effect on the polymer prepared by using the chain transfer agent, and can be used as a lubricating oil additive, so that the chain transfer agent has good anti-wear and anti-friction effects.

The invention aims to provide a chain transfer agent for preparing an antibacterial polymer.

It is another object of the present invention to provide a method for preparing the above chain transfer agent for preparing an antibacterial polymer.

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

a chain transfer agent for use in the preparation of an antimicrobial polymer having the formula (I):

wherein R is

The reaction flow and preparation method of the chain transfer agent for preparing the antibacterial polymer are as follows:

1. adding a chain transfer agent and carbon tetrachloride into the mouth-branched bottle, fully and uniformly mixing, then adding an acyl chlorination reagent thionyl chloride, and continuously stirring until the mixture is clear; and (3) heating the mixed solution to 77 ℃, after the reaction is finished, rotationally evaporating the solvent in vacuum to obtain yellow oily liquid, and drying in vacuum at room temperature to obtain the chain transfer agent acyl chlorination product.

Wherein the chain transfer agent is benzyl trithiocarbonate-based propionic acid and 2- (ethylmercapto-thiocarbonylthio) -2-methylpropionic acid.

Wherein the amount of the chain transfer agent is 0.1-0.5 g per milliliter of carbon tetrachloride.

Wherein the volume ratio of the acyl chlorination reagent to the carbon tetrachloride is 0.1-0.5: 1.

2.N₂Under protection, adding 2 '-bromo-2, 6-difluoro-4-hydroxyacetophenone, freshly distilled pyridine and tetrahydrofuran into a flask with a branch mouth until the 2' -bromo-2, 6-difluoro-4-hydroxyacetophenone is completely dissolved; the chain transfer prepared by the steps isDissolving the transfer agent acyl chloride product in tetrahydrofuran, dropwise adding the solution into a 2' -bromo-2, 6-difluoro-4-hydroxyacetophenone solution at 0 ℃, stirring for 1h at room temperature, adding chloroform, reacting for 10h at 65 ℃, washing the mixed solution with saturated sodium bicarbonate, deionized water and diluted hydrochloric acid, decompressing and evaporating the obtained crude product to dryness, and purifying by a column to obtain a chain transfer agent esterification product A.

Wherein the molar ratio of the chain transfer agent acyl chlorination product to the 2' -bromo-2, 6-difluoro-4-hydroxyacetophenone to the pyridine is 1:1: 2-5.

3.N₂Under protection, adding a thioacetamide and chain transfer agent esterification product A into a branched flask, adding a reaction solvent N, N-dimethylformamide, reacting at 140 ℃ for 20 hours, monitoring the reaction process by TLC, extracting with ethyl acetate/water after the reaction is finished, washing the combined organic phase with water and brine, drying, filtering, concentrating, and purifying by a column to obtain a product B.

Wherein the molar ratio of thioacetamide to chain transfer agent esterification product A is 5-10: 1.

4.N₂Under protection, the products B and NBS are dissolved in the reaction solvent CCl₄And (3) reacting at 80 ℃ for 4h, monitoring the reaction process by TLC, after the reaction is finished, evaporating the reaction crude product to dryness under reduced pressure, and purifying by a column to obtain a product C.

Wherein the molar ratio of the product B to NBS is 1: 1.2-2.0.

5.N₂And under protection, dissolving the product C in N, N-dimethylformamide, adding 2, 6-difluoro-3-hydroxy-benzamide and alkali, reacting at room temperature for 18h, after the reaction is finished, evaporating the crude reaction product under reduced pressure to dryness, and purifying by a column to obtain a product D.

Wherein the molar ratio of the product C, 2, 6-difluoro-3-hydroxy-benzamide to the base is 1:1: 3-5.

Wherein the alkali is sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate or potassium bicarbonate.

6. Dissolving the product D in acetic acid, adding Zn powder, reacting at 120 ℃ for 2h, monitoring the reaction process by TLC, adding alkali to adjust the pH to 8-9, extracting with ethyl acetate/water, washing the combined organic phase with water and brine, drying, filtering, concentrating, and purifying by a column to obtain the antibacterial chain transfer agent product E.

Wherein the molar ratio of the product D, acetic acid and Zn powder is 1: 1.2-1.5.

Wherein the alkali is sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate or potassium bicarbonate.

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

(1) the chain transfer agent synthesis process for preparing the antibacterial polymer, which is prepared by the invention, is simple to operate, does not generate toxic by-products, and the synthesis raw materials are low in price.

(2) The chain transfer agent prepared by the invention for preparing the antibacterial polymer has activity on gram-positive bacteria such as staphylococcus, clostridium and listeria and bacillus, such as staphylococcus aureus, staphylococcus epidermidis, hemolytic staphylococcus and saprophytic staphylococcus, bacillus subtilis, bacillus anthracis and bacillus cereus.

(3) The chain transfer agent for preparing the antibacterial polymer is used for preparing the polymer material, so that the polymer has antibacterial property, and the problems that the added antibacterial agent is poor in compatibility and dispersibility with the polymer material and the antibacterial agent is easy to lose when the antibacterial agent is added into the polymer through physical mixing are solved.

(4) The chain transfer agent for preparing the antibacterial polymer prepared by the invention can be used as a lubricating oil additive, and can be decomposed in the friction process to generate a layer of organic sulfide compact protective film, so that the abrasion and wear of the surface of a steel ball friction pair are effectively reduced, and the anti-wear effect is achieved.

Drawings

FIG. 1 Effect of mass fraction of antimicrobial chain transfer agent additive on scrub spot diameter.

Detailed Description

The invention is further illustrated by the following examples. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like.