Degradable / antibacterial ester ammonium-based epoxy thermosetting system with high thermal stability and preparation method of degradable / antibacterial ester ammonium-based epoxy thermosetting system

Abstract

The invention discloses a degradable / antibacterial ester ammonium epoxy thermosetting system with high thermal stability and a preparation method thereof. 2-(p-toluenesulfonyloxy) acetic acid, epoxy resin and an organic solvent are stirred to react for 1-48 hours at the temperature of 80-130 DEG C, and polyfunctional p-toluenesulfonic epoxy resin is obtained; and adding the prepared p-toluenesulfonic acid-based epoxy resin with double functionality and polyfunctionality into an amine curing agent, stirring at the temperature of 20-80 DEG C for 1-30 minutes until the mixture is slightly viscous, pouring the mixture into a mold, and curing at the temperature of 80-180 DEG C for 1-10 hours to obtain the degradable / antibacterial modified epoxy thermosetting system with high thermal stability. The obtained thermosetting epoxy resin has the advantages of high thermal stability, antibacterial property and degradability.

Description

Technical Field

[0001] The invention belongs to the field of antibacterial materials, and in particular relates to a highly thermally stable degradable / antibacterial ester ammonium-based epoxy thermosetting system and a preparation method thereof. Background Art

[0002] Epoxy resin composites are widely used in many high-end fields such as aerospace, wind power generation, and transportation due to their excellent performance. However, after the resin matrix is ​​cured, a 3D network structure is formed. This structure cannot be treated by heating or solvents, which is the so-called insoluble and infusible. This means that thermosetting resin-based composites and their waste can only be simply recycled and reused through physical methods such as incineration, landfill, crushing, and reuse. Unlike thermoplastic resin-based composites and their waste, they cannot be made into the required composite products and recycled through heating, granulation, and remolding processes. Although many of the currently reported synthesis schemes for degradable epoxy resins have prepared a series of new materials with excellent degradation properties and have made a lot of progress, their thermal properties, dimensional stability, and mechanical properties still need to be improved, which greatly limits their practical application.

[0003] In addition, in recent years, harmful microorganisms have had a bad impact on human life in textiles, food, water sources, medical devices, etc., and even caused great harm to human life. We live in a world where we coexist with bacteria, and sub-health has become a common phenomenon. The overall decline in people's physical fitness makes it easier for pathogenic bacteria and viruses to invade the human body. In addition, in recent decades, the abuse of antibiotics has led to the emergence of a large number of drug-resistant strains, which gradually threaten human health. Although bacteria and viruses are both microorganisms. However, the size, structure, source, and mechanism of bacteria and viruses are completely different, so the antiviral and antibacterial mechanisms are different. Antimicrobial agents are mainly divided into three categories: natural antimicrobial agents, inorganic antimicrobial agents, and organic antimicrobial agents. The most commonly used synthetic organic antimicrobial agent is a quaternary ammonium salt antimicrobial agent, which has a relatively stable nature, a large variety, low toxicity, and is easy to use, so it has received widespread attention in recent years.

[0004] Before this project, we have made a model compound to simulate the heat resistance of the leaving group cl- and p-toluenesulfonyl, which proves that p-toluenesulfonyl has high heat resistance.

[0005] The invention provides a highly thermally stable degradable / antibacterial ester ammonium epoxy thermosetting system. The synthesized thermally stable degradable / antibacterial modified epoxy thermosetting system is prepared by esterification reaction between epoxy resin and synthesized 2-(p-toluenesulfonyloxy)acetic acid, so that the system has good heat resistance and mechanical properties. At the same time, an amine curing agent is introduced to perform quaternary ammonium salt curing, so that the system has obvious antibacterial effect, thereby preparing a highly thermally stable degradable / antibacterial ester ammonium epoxy thermosetting system and a preparation method thereof. Summary of the invention

[0006] The object of the present invention is to provide a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system and a preparation method thereof in view of the deficiencies of the prior art.

[0007] The objective of the present invention is achieved through the following technical solutions:

[0008] In a first aspect, the present invention provides a method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system, comprising the following steps:

[0009] (1) Preparing a difunctional p-toluenesulfonic acid epoxy resin: adding 2.5-3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy groups in a reactor, stirring and reacting at 100-130° C. for 1-48 hours; after the reaction is completed, precipitating, collecting and drying to obtain a difunctional p-toluenesulfonic acid epoxy resin;

[0010] (2) dissolving the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) in 1-10 mol of an organic solution, then adding 1-1.5 mol of an amine curing agent, stirring at 20-80° C. for 1-30 min, pouring into a mold, and curing at 80-180° C. for 1-10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0011] In a second aspect, the present invention also provides a method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system, comprising the following steps:

[0012] (1) Preparing a difunctional p-toluenesulfonic acid epoxy resin: adding 2.5-3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy groups in a reactor, stirring and reacting at 100-130° C. for 1-48 hours; after the reaction is completed, precipitating, collecting and drying to obtain a difunctional p-toluenesulfonic acid epoxy resin;

[0013] (2) Preparing a multifunctional p-toluenesulfonic acid epoxy resin: Subsequently, 2.5 to 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) are added to a reactor in sequence, and stirred for reaction at 100 to 130° C. for 1 to 48 hours; after the reaction is completed, the multifunctional p-toluenesulfonic acid epoxy resin is obtained by precipitation, collection, and drying;

[0014] (3) dissolving the multifunctional p-toluenesulfonic acid epoxy resin prepared in step (2) in 1-10 mol of an organic solution, then adding 0.5-1.0 mol of an amine curing agent, stirring at 20-80° C. for 1-30 min, pouring into a mold, and curing at 80-180° C. for 1-10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0015] Furthermore, the organic solvent is acetone, dichloromethane, chloroform or dimethyl sulfoxide.

[0016] In a third aspect, the present invention also provides a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system.

[0017] The invention has the beneficial effects of introducing a leaving group into a quaternary ammonium salt epoxy resin system and improving the problem of heat resistance in the system. Meanwhile, the epoxy resin has a quaternary ammonium salt structure, which enables the epoxy resin to have antibacterial ability. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 is the structural formula of the multifunctional p-toluenesulfonic acid epoxy resin prepared in Example 5;

[0019] Figure 2 This is a thermogravimetric analysis diagram of the highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system prepared in Example 1;

[0020] Figure 3 This is the nuclear magnetic resonance wave pattern of the multifunctional p-toluenesulfonic acid epoxy resin prepared in Example 5;

[0021] Figure 4 This is a physical picture of the highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system prepared in Example 1. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical scheme and advantages of the present invention more clear, the present invention is further described in detail in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0023] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0024] The present invention provides a method for preparing a highly thermally stable degradable / antibacterial ester ammonium-based epoxy thermosetting system, comprising the following steps:

[0025] (1) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 2.5-3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy group are added to a reactor in sequence, and stirred at 100-130° C. for 1-48 hours. After the reaction is completed, the difunctional p-toluenesulfonic acid epoxy resin is obtained by precipitation, collection and drying.

[0026] (2) dissolving the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) in 1-10 mol of an organic solution, then adding 1-1.5 mol of an amine curing agent, stirring at 20-80° C. for 1-30 min, pouring into a mold, and curing at 80-180° C. for 1-10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0027] The organic solvent is acetone, dichloromethane, chloroform or dimethyl sulfoxide.

[0028] The present invention also provides a method for preparing a highly thermally stable degradable / antibacterial ester ammonium-based epoxy thermosetting system, comprising the following steps:

[0029] (1) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 2.5-3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy group are added to a reactor in sequence, and stirred at 100-130° C. for 1-48 hours. After the reaction is completed, the difunctional p-toluenesulfonic acid epoxy resin is obtained by precipitation, collection and drying.

[0030] (2) Preparation of a multifunctional p-toluenesulfonic acid epoxy resin: Subsequently, 2.5 to 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) are added to a reactor in sequence, and the mixture is stirred and reacted at 100 to 130° C. for 1 to 48 hours. After the reaction is completed, a multifunctional p-toluenesulfonic acid epoxy resin is obtained by precipitation, collection, and drying.

[0031] (3) dissolving the multifunctional p-toluenesulfonic acid epoxy resin prepared in step (2) in 1-10 mol of an organic solution, then adding 0.5-1.0 mol of an amine curing agent, stirring at 20-80° C. for 1-30 min, pouring into a mold, and curing at 80-180° C. for 1-10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0032] The organic solvent is acetone, dichloromethane, chloroform or dimethyl sulfoxide.

[0033] Example 1

[0034] A method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system comprises the following steps:

[0035] (1) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy group were added to a reactor in sequence, and stirred at 100° C. for 48 hours. After the reaction was completed, pure difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection and drying.

[0036] (2) The difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) is dissolved in 2 mol of acetone, and then 1 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine is added, stirred at 50°C for 10 min, poured into a mold, and cured at 100°C for 10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0037] Figure 2 This is the thermogravimetric analysis diagram of the highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system prepared in this example.

[0038] Figure 4 This is a physical picture of the highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system prepared in this example.

[0039] Example 2

[0040] A method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system comprises the following steps:

[0041] (1) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy group were added to a reactor in sequence, and stirred at 100° C. for 48 hours. After the reaction was completed, pure difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection and drying.

[0042] (2) The difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) is dissolved in 2 mol of acetone, and then 1 mol of N,N,N',N'-tetramethyl-1,3-propylenediamine is added, stirred at 50°C for 10 min, and poured into a mold, and cured at 100°C for 10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0043] Example 3

[0044] A method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system comprises the following steps:

[0045] (1) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy group were added to a reactor in sequence, and stirred at 100° C. for 48 hours. After the reaction was completed, pure difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection and drying.

[0046] (2) The difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) is dissolved in 2 mol of acetone, and then 1 mol of N,N,N',N'-tetramethyl-1,3-propylenediamine is added, stirred at 40°C for 10 min, and poured into a mold, and cured at 120°C for 10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0047] Example 4

[0048] A method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system comprises the following steps:

[0049] (1) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy group were added to a reactor in sequence, and stirred at 100° C. for 48 hours. After the reaction was completed, pure difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection and drying.

[0050] (2) dissolving the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) in 2 mol of acetone, then adding 1 mol of 2,4,6-tris(dimethylaminomethyl)phenol, stirring at 40°C for 10 min, pouring into a mold, and curing at 120°C for 10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0051] Example 5

[0052] A method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system comprises the following steps:

[0053] (1) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy group were added to a reactor in sequence, and stirred at 130° C. for 48 hours. After the reaction was completed, pure difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection and drying.

[0054] (2) Preparing a multifunctional p-toluenesulfonic acid epoxy resin: Subsequently, 2.5 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) were added to a reactor in sequence, and stirred for reaction at 130° C. for 24 hours; after the reaction was completed, a multifunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection, and drying;

[0055] (3) The multifunctional p-toluenesulfonic acid epoxy resin prepared in step (2) is dissolved in 2 mol of acetone, and then 1.0 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine is added, stirred at 50°C for 10 min, and poured into a mold, and cured at 130°C for 10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0056] Figure 1 is the structural formula of the multifunctional p-toluenesulfonic acid epoxy resin prepared in this example.

[0057] Figure 3 This is the nuclear magnetic resonance wave diagram of the multifunctional p-toluenesulfonic acid epoxy resin prepared in this example.

[0058] Example 6

[0059] A method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system comprises the following steps:

[0060] (1) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy group were added to the reactor in sequence, and stirred at 130° C. for 48 hours. After the reaction, pure difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection and drying.

[0061] (2) Preparation of a multifunctional p-toluenesulfonic acid epoxy resin: Subsequently, 2.6 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) were added to a reactor in sequence, and stirred for reaction at 130° C. for 24 hours; after the reaction was completed, a multifunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection, and drying;

[0062] (3) The multifunctional p-toluenesulfonic acid epoxy resin prepared in step (2) is dissolved in 2 mol of acetone, and then 1.0 mol of N,N,N',N'-tetramethyl-13-propylenediamine is added, stirred at 50°C for 10 min, and poured into a mold, and cured at 100°C for 10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0063] Example 7

[0064] A method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system comprises the following steps:

[0065] (1) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy group were added to the reactor in sequence, and stirred at 100° C. for 48 hours. After the reaction was completed, pure difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection and drying.

[0066] (2) Preparation of a multifunctional p-toluenesulfonic acid epoxy resin: Subsequently, 2.6 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) were added to a reactor in sequence, and stirred for reaction at 130° C. for 48 hours; after the reaction was completed, a multifunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection, and drying;

[0067] (3) The multifunctional p-toluenesulfonic acid epoxy resin prepared in step (2) is dissolved in 2 mol of acetone, and then 1.0 mol of pentamethyldipropylenetriamine is added, stirred at 60° C. for 10 min, and poured into a mold, and cured at 100° C. for 10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0068] Example 8

[0069] A method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium-based epoxy thermosetting system comprises the following steps:

[0070] (1) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy group were added to the reactor in sequence, and stirred at 100° C. for 48 hours. After the reaction was completed, pure difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection and drying.

[0071] 2) preparing a multifunctional p-toluenesulfonic acid epoxy resin: subsequently adding 2.6 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) into a reactor in sequence, and stirring the mixture at 130° C. for 48 hours; after the reaction is completed, precipitating, collecting, and drying to obtain a multifunctional p-toluenesulfonic acid epoxy resin;

[0072] (3) The multifunctional p-toluenesulfonic acid epoxy resin prepared in step (2) is dissolved in 2 mol of acetone, followed by adding 1.0 mol of 2,4,6-tris(dimethylaminomethyl)phenol, stirring at 60°C for 10 min, and then pouring into a mold, and curing at 130°C for 10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

[0073] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system, characterized in that: The following steps are involved: (1) Preparing a difunctional p-toluenesulfonic acid epoxy resin: adding 2.5-3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy groups in a reactor, stirring and reacting at 100-130° C. for 1-48 hours; after the reaction is completed, precipitating, collecting and drying to obtain a difunctional p-toluenesulfonic acid epoxy resin; (2) dissolving the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) in 1-10 mol of an organic solution, then adding 1-1.5 mol of an amine curing agent, stirring at 20-80° C. for 1-30 min, pouring into a mold, and curing at 80-180° C. for 1-10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

2. A method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system, characterized in that: The following steps are involved: (1) Preparing a difunctional p-toluenesulfonic acid epoxy resin: adding 2.5-3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin with epoxy groups in a reactor, stirring and reacting at 100-130° C. for 1-48 hours; after the reaction is completed, precipitating, collecting and drying to obtain a difunctional p-toluenesulfonic acid epoxy resin; (2) Preparing a multifunctional p-toluenesulfonic acid epoxy resin: Subsequently, 2.5 to 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) are added to a reactor in sequence, and stirred for reaction at 100 to 130° C. for 1 to 48 hours; after the reaction is completed, the multifunctional p-toluenesulfonic acid epoxy resin is obtained by precipitation, collection, and drying; (3) dissolving the multifunctional p-toluenesulfonic acid epoxy resin prepared in step (2) in 1-10 mol of an organic solution, then adding 0.5-1.0 mol of an amine curing agent, stirring at 20-80° C. for 1-30 min, pouring into a mold, and curing at 80-180° C. for 1-10 h to obtain a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system.

3. The method for preparing a highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system according to claim 1 or 2, characterized in that High thermal stability, antibacterial and biodegradable, the organic solvent is acetone, dichloromethane, chloroform or dimethyl sulfoxide.

4. A highly thermally stable biodegradable / antibacterial ester ammonium epoxy thermosetting system prepared according to any one of claims 1 to 3.

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