阅读说明：本技术 一种双胍衍生物抗菌型环氧树脂固化剂及其制备方法 (Biguanide derivative antibacterial epoxy resin curing agent and preparation method thereof ) 是由 王玉丹 袁璇 刘立佳 董红星 白建伟 于 2019-09-05 设计创作，主要内容包括：本发明提供的是一种双胍衍生物抗菌型环氧树脂固化剂及其制备方法。以甲基苯基双胍盐酸盐和伯胺为原料,反应得到双胍衍生物抗菌型环氧树脂固化剂。本发明制备的双胍衍生物抗菌型环氧树脂固化剂为粘稠液体,其自身可作为抗菌剂使用,其对革兰式阴性菌及革兰氏阳性菌均表现出有良好的抗菌活性,具有广谱抗菌性和良好的水溶性。该双胍衍生物可作为抗菌型固化剂用于环氧树脂的固化,制备抗菌型环氧树脂。可与环氧树脂均匀混合,并在固化温度下使环氧树脂固化。所固化环氧树脂,在保持树脂优良的力学性能的同时,具有较好的抗菌能力。该双胍衍生物抗菌型固化剂合成简单、成本低,可广泛用于抗菌材料、医疗卫生、化工、建筑、农林园艺和环境保护等领域。(The invention provides a biguanide derivative antibacterial epoxy resin curing agent and a preparation method thereof. Methyl phenyl biguanide hydrochloride and primary amine are used as raw materials to react to obtain the biguanide derivative antibacterial epoxy resin curing agent. The biguanide derivative antibacterial epoxy resin curing agent prepared by the invention is viscous liquid, can be used as an antibacterial agent, has good antibacterial activity on gram-negative bacteria and gram-positive bacteria, and has broad-spectrum antibacterial property and good water solubility. The biguanide derivative can be used as an antibacterial curing agent for curing epoxy resin to prepare antibacterial epoxy resin. Can be mixed homogeneously with the epoxy resin and the epoxy resin cured at the curing temperature. The cured epoxy resin has good antibacterial ability while maintaining excellent mechanical properties of the resin. The biguanide derivative antibacterial curing agent has simple synthesis and low cost, and can be widely used in the fields of antibacterial materials, medical treatment and sanitation, chemical industry, construction, agriculture, forestry, gardening, environmental protection and the like.)

1. A biguanide derivative antibacterial epoxy resin curing agent is characterized in that the structural formula is as follows:

wherein R is₁Is o-methylphenyl, m-methylphenyl or p-methylphenyl; r₂Is an aliphatic chain having 6 to 18 carbon atoms in length.

2. A process for preparing a biguanide derivative antibacterial epoxy resin curing agent according to claim 1, which comprises:

dissolving methyl phenyl biguanide in ethanol, adjusting the solution to be neutral by using 1 mol/L hydrochloric acid, concentrating to remove the solvent, and drying to constant weight to obtain methyl phenyl biguanide hydrochloride;

and step two, under the protection of nitrogen, dissolving methyl phenyl biguanide hydrochloride in N, N-dimethylacetamide, heating to the reaction temperature, adding primary amine, stirring for reaction for 20-28 hours, cooling to room temperature after the reaction is finished, concentrating, separating and purifying to obtain the biguanide derivative antibacterial epoxy resin curing agent.

3. The method for preparing a biguanide derivative antibacterial epoxy resin curing agent according to claim 2, comprising: the methyl phenyl biguanide is one of o-methyl phenyl biguanide, m-methyl phenyl biguanide or p-methyl phenyl biguanide.

4. The method for preparing a biguanide derivative antibacterial epoxy resin curing agent according to claim 3, wherein: the primary amine is one of aliphatic primary amine, oleyl primary amine, stearyl primary amine and lauryl primary amine.

5. The method for preparing a biguanide derivative antibacterial epoxy resin curing agent according to claim 2, comprising: the aliphatic primary amine is hexylamine, heptylamine, dodecylamine or hexadecylamine.

6. The method for preparing a biguanide derivative antibacterial epoxy resin curing agent according to claim 2, comprising: the reaction temperature is 80-150 ℃.

7. The method for preparing a biguanide derivative antibacterial epoxy resin curing agent according to claim 2, comprising: the molar ratio of the methyl phenyl biguanide hydrochloride to the primary amine is 1: 1-1: 2, and the concentration of the methyl phenyl biguanide hydrochloride is 30-80 g/L.

8. The method for preparing a biguanide derivative antibacterial epoxy resin curing agent according to claim 2, comprising: the separation and purification is to use a silica gel chromatographic column to carry out column chromatography separation and purification.

Technical Field

The invention relates to a bacteriostatic and antibacterial material and a preparation method thereof. In particular to an antibacterial epoxy resin curing agent and a preparation method thereof.

Background

Epoxy resin is a kind of thermosetting material, and has been the research hotspot of people. The epoxy resin has excellent mechanical property, chemical corrosion resistance, electrical insulation property, processing property and bonding property, and is widely applied to the fields of coatings, adhesives, printed circuit boards, electronic packaging materials, composite materials, aerospace, automobiles and the like. When the epoxy resin reacts with the curing agent to form a three-dimensional network structure, the performance characteristics of the epoxy resin can be fully exerted. The structure and performance of the curing agent directly affect the final performance and use effect of the epoxy resin, and therefore, the development of the curing agent has an important influence on the performance and application of the epoxy resin.

Under certain special conditions, epoxy resin used on the surface of pipelines, the bottom of ships, the aerospace field and the like needs to have specific antibacterial property and corrosion resistance to deal with the corrosion of microorganisms to materials. Traditional antibacterial agents act to kill bacteria primarily through their specific targets in the antibacterial mechanism, which inevitably renders the bacteria resistant. Guanidine compounds can be ionized in a solvent so as to be positively charged, and are combined with bacteria through the electrostatic action of positive and negative charges to simultaneously generate a plane with a hydrogen bond donor, guanidine positive ions and negative ions in phospholipid are close to each other through the action force between ions, and then form stable double hydrogen bonds with carboxylate radicals, phosphate radicals and sulfate radicals in the phospholipid, so that the charge balance on cell walls or cell membranes is broken, the phospholipid is locally concentrated, the cell membranes are broken, internal nutrients flow out, and finally the bacteria die. Meanwhile, compared with amino, the guanidine compound has a wider pH range for ionization and higher applicability. The double hydrogen bond combination mode has larger bond energy, firmer bond and stronger acting force, and can be combined with bacteria more stably, thereby having stronger antibacterial property; in addition, the antibacterial mechanism of the guanidine antibacterial agent is that the cell membrane structure of bacteria is destroyed through the electrostatic action of positive and negative charges, so that the guanidine antibacterial agent has lower possibility of causing the bacteria to generate drug resistance.

Disclosure of Invention

The invention aims to provide a biguanide derivative antibacterial epoxy resin curing agent which has curing performance, antibacterial performance and lower drug resistance. The invention also aims to provide a method for simply and quickly preparing the biguanide derivative antibacterial epoxy resin curing agent through one-step reaction.

The purpose of the invention is realized as follows:

the structural formula of the biguanide derivative antibacterial epoxy resin curing agent is as follows:

wherein R is₁Is o-methylphenyl, m-methylphenyl or p-methylphenyl; r₂Is an aliphatic chain having 6 to 18 carbon atoms in length.

The preparation method of the biguanide derivative antibacterial epoxy resin curing agent comprises the following steps:

dissolving methyl phenyl biguanide in ethanol, adjusting the solution to be neutral by using 1 mol/L hydrochloric acid, concentrating to remove the solvent, and drying to constant weight to obtain methyl phenyl biguanide hydrochloride;

and step two, under the protection of nitrogen, dissolving methyl phenyl biguanide hydrochloride in N, N-dimethylacetamide, heating to the reaction temperature, adding primary amine, stirring for reaction for 20-28 hours, cooling to room temperature after the reaction is finished, concentrating, separating and purifying to obtain the biguanide derivative antibacterial epoxy resin curing agent.

The preparation method of the biguanide derivative antibacterial epoxy resin curing agent of the present invention may further comprise:

1. the methyl phenyl biguanide is one of o-methyl phenyl biguanide, m-methyl phenyl biguanide or p-methyl phenyl biguanide.

2. The primary amine is one of aliphatic primary amine, oleyl primary amine, stearyl primary amine and lauryl primary amine.

3. The aliphatic primary amine is hexylamine, heptylamine, dodecylamine or hexadecylamine.

4. The reaction temperature is 80-150 ℃.

5. The molar ratio of the methyl phenyl biguanide hydrochloride to the primary amine is 1: 1-1: 2, and the concentration of the methyl phenyl biguanide hydrochloride is 30-80 g/L.

6. The separation and purification is to use a silica gel chromatographic column to carry out column chromatography separation and purification.

The invention provides a biguanide derivative antibacterial epoxy resin curing agent and a preparation method thereof. Methyl phenyl biguanide hydrochloride and primary amine with different chain lengths are used as raw materials to react to synthesize the biguanide derivative antibacterial epoxy resin curing agent. The biguanide derivative antibacterial epoxy resin curing agent prepared by the invention is viscous liquid, can be used as an antibacterial agent, has good antibacterial activity on gram-negative bacteria and gram-positive bacteria, and has broad-spectrum antibacterial property and good water solubility. Meanwhile, the biguanide derivative can be used as an antibacterial curing agent for curing epoxy resin to prepare antibacterial epoxy resin. It can be mixed homogeneously with the epoxy resin and the epoxy resin cured at the curing temperature. The obtained cured epoxy resin has good antibacterial ability while maintaining excellent mechanical properties of the resin. The biguanide derivative antibacterial epoxy resin curing agent has simple synthesis and low cost, and can be widely applied to the fields of antibacterial materials, medical treatment and health, petrochemical industry, civil construction, agriculture, forestry, gardening, environmental protection and the like.

The biguanide derivative antibacterial epoxy resin curing agent can be simply and quickly synthesized through one-step reaction, and has good antibacterial effect on gram-positive staphylococcus aureus standard strains and gram-negative escherichia coli standard strains. The minimum inhibitory concentration of the above strains of the synthesized derivatives is in the range of 2.5-312 micrograms/ml (TTC method). Meanwhile, the biguanide derivative is used as a curing agent to cure epoxy resin, so that an epoxy resin material with antibacterial performance can be prepared, and the prepared epoxy resin material has obvious antibacterial performance. Therefore, the biguanide derivative antibacterial epoxy resin curing agent provided by the invention has wide antibacterial spectrum and good antibacterial effect, and has important significance for preparing novel antibacterial resin materials.

The main advantages of the invention include:

1. the biguanide derivative antibacterial epoxy resin curing agent is synthesized by taking commercially available methyl phenyl biguanide hydrochloride and common primary amine as raw materials, and has the characteristics of simple synthesis and low cost.

2. The biguanide derivative antibacterial epoxy resin curing agent has the advantages of good water solubility, broad-spectrum antibacterial property, strong permeability, low toxicity and the like. The epoxy resin curing agent can be used as an antibacterial agent and an epoxy resin curing agent, and has double functions of antibacterial and resin curing.

3. The biguanide derivative antibacterial epoxy resin curing agent is viscous liquid and can be uniformly mixed with epoxy resin; the biguanide group and the epoxy resin form a three-dimensional curing network in the structure, and the biguanide group with antibacterial property is introduced into the resin structure, so that the epoxy resin has excellent mechanical property and good antibacterial property, and the preparation of the antibacterial epoxy resin material can be realized.

Drawings

FIG. 1 is an infrared spectrum (KBr pellet) of m-methylheptylbididynobenzene (m-HTB).

FIG. 2 is a test of minimum inhibitory concentration of m-methylhexadecyl biguanidinobenzene (m-HdTB) against Escherichia coli and Staphylococcus aureus (TTC method).

FIG. 3 shows the growth curves (OD test) of Staphylococcus aureus in 1-8 hours with different antibacterial E51 resins.

Detailed Description

The invention is described in more detail below by way of example.