Highly thermally stable degradable / antibacterial ester ammonium-based epoxy thermoset systems and methods of making

Abstract

The application discloses a kind of high thermal stability degradable / antibacterial ester ammonium base epoxy thermosetting system and preparation method, 2-(p-toluenesulfonyloxy) acetic acid, epoxy resin and organic solvent are stirred in 80~130 ℃ under reaction 1~48 h, and the multifunctional p-toluenesulfonic acid base epoxy resin is obtained;The prepared double, multifunctional p-toluenesulfonic acid base epoxy resin is added to amine curing agent, and is stirred at 20~80 ℃ for 1~30 min to slightly sticky, the mixture is poured into mold, and is cured at 80~180 ℃ for 1~10 h, and the modified epoxy thermosetting system of high thermal stability degradable / antibacterial is obtained.The application obtains high thermal stability, antibacterial and degradable thermosetting epoxy resin.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of antibacterial materials, and particularly relates to a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system and a preparation method. BACKGROUND

[0002] Epoxy resin composites are widely used in aerospace, wind power, transportation and many other high-end fields due to their excellent performance. However, after the resin matrix is cured, a 3D network structure is formed, which cannot be treated by heating or solvent, that is, it is not soluble and not fusible. This makes the thermosetting resin matrix composite and its waste only be simply recycled and reused by incineration, burial, crushing, repeated use and other physical methods, and cannot be made into the required composite product and recycled like thermoplastic resin matrix composite and its waste, which can be heated, granulated, and reshaped. Although many reported synthesis schemes of degradable epoxy resins have prepared a series of new materials with excellent degradation performance, and have made a lot of progress, their thermal performance, dimensional stability and mechanical performance 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 coexisting with bacteria, and sub-health has become a common phenomenon. People's physical fitness has declined as a whole, making it easier for pathogenic bacteria and viruses to invade the human body. In recent decades, the abuse of antibiotics has led to the production of a large number of drug-resistant strains, gradually threatening human health. Bacteria and viruses are both microorganisms, but their size, structure, source and mechanism are completely different, so the mechanisms of antiviral and antibacterial are different. Antibacterial agents are mainly divided into three categories: natural antibacterial agents, inorganic antibacterial agents and organic antibacterial agents. The most commonly used synthetic organic antibacterial agent is quaternary ammonium salt antibacterial agent, which is relatively stable, has many types, low toxicity and is easy to use, so it has been widely concerned in recent years.

[0004] Before doing this project, model compounds have been simulated to simulate the ability of the leaving group Cl- and p-toluenesulfonyl in heat resistance. It is confirmed that p-toluenesulfonyl has high heat resistance.

[0005] The application provides a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system, and a preparation method thereof. SUMMARY

[0006] The application aims at the deficiencies of the prior art, and provides a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system and a preparation method thereof.

[0007] The application is achieved by the following technical scheme.

[0008] In a first aspect, the application provides a preparation method of a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system, which comprises the following steps.

[0009] (1) preparing a difunctional p-toluenesulfonic acid-based epoxy resin: 2.5-3 mol of 2-(p-toluenesulfonyloxy) acetic acid and 1 mol of an epoxy group-containing epoxy resin are sequentially added into a reactor, and stirring reaction is carried out at 100-130 DEG C for 1-48 h; after the reaction is completed, the difunctional p-toluenesulfonic acid-based epoxy resin is obtained through precipitation, collection and drying;

[0010] (2) the difunctional p-toluenesulfonic acid-based epoxy resin prepared in step (1) is dissolved in 1-10 mol of an organic solution, then 1-1.5 mol of an amine curing agent is added, stirring is carried out at 20-80 DEG C for 1-30 min, and then the mixture is poured into a mold, and curing is carried out at 80-180 DEG C for 1-10 h, so as to obtain the high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system.

[0011] In a second aspect, the application further provides a preparation method of a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system, which comprises the following steps.

[0012] (1) preparing a difunctional p-toluenesulfonic acid-based epoxy resin: 2.5-3 mol of 2-(p-toluenesulfonyloxy) acetic acid and 1 mol of an epoxy group-containing epoxy resin are sequentially added into a reactor, and stirring reaction is carried out at 100-130 DEG C for 1-48 h; after the reaction is completed, the difunctional p-toluenesulfonic acid-based epoxy resin is obtained through precipitation, collection and drying;

[0013] (2) The multifunctional p-toluenesulfonic acid group epoxy resin is prepared by sequentially adding 2.5-3 mol of 2-(p-toluenesulfonyloxy) acetic acid and 1 mol of the difunctional p-toluenesulfonic acid group epoxy resin prepared in step (1) into a reactor, and stirring and reacting at 100-130°C for 1-48 h; after the reaction is completed, the multifunctional p-toluenesulfonic acid group epoxy resin is obtained by precipitation, collection and drying;

[0014] (3) The multifunctional p-toluenesulfonic acid group epoxy resin prepared in step (2) is dissolved in 1-10 mol of an organic solvent, and then 0.5-1.0 mol of an amine curing agent is added, stirred at 20-80°C for 1-30 min, and then poured into a mold, and cured at 80-180°C for 1-10 h to obtain a high-thermal-stability degradable / antibacterial ester ammonium group epoxy thermosetting system.

[0015] Further, the organic solvent is acetone, dichloromethane, trichloromethane or dimethyl sulfoxide.

[0016] In a third aspect, the present application further provides a high-thermal-stability degradable / antibacterial ester ammonium group epoxy thermosetting system.

[0017] The present application has the advantages that a leaving group is introduced into a quaternary ammonium salt epoxy resin system, and the problem of poor heat resistance in the system can be improved, and the quaternary ammonium salt structure in the epoxy resin enables the epoxy resin to have antibacterial ability. BRIEF DESCRIPTION OF DRAWINGS

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

[0019] Figure 2 The nuclear magnetic resonance spectrum of the multifunctional p-toluenesulfonic acid group epoxy resin prepared for Example 5;

[0020] Figure 3 The thermogravimetric analysis graph of the high-thermal-stability degradable / antibacterial ester ammonium group epoxy thermosetting system prepared for Example 1;

[0021] Figure 4 The actual object graph of the high-thermal-stability degradable / antibacterial ester ammonium group epoxy thermosetting system prepared for Example 1. DETAILED DESCRIPTION

[0022] In order to make the objectives, technical solutions and advantages of the present application clearer, further detailed description will be given to the present application in combination with the drawings and examples, and it should be understood that the specific examples described herein are only used to explain the present application, rather than all examples. Based on the examples in the present application, all other examples obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0023] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials 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 containing epoxy group were added to the reactor in sequence, and stirred at 100-130°C for 1-48 hours. After the reaction, the difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection and drying.

[0026] (2) The difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) is dissolved in 1-10 mol of an organic solution, and then 1-1.5 mol of an amine curing agent is added. After stirring at 20-80°C for 1-30 min, the mixture is poured into a mold and cured 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 containing epoxy group were added to the reactor in sequence, and stirred at 100-130°C for 1-48 hours. After the reaction, the difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection and drying.

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

[0031] (3) The multifunctional p-toluenesulfonic acid-based epoxy resin prepared in step (2) is dissolved in 1-10 mol of an organic solvent, followed by the addition of 0.5-1.0 mol of an amine curing agent, and stirred at 20-80°C for 1-30 min, and then poured into a mold, and cured at 80-180°C for 1-10 h to obtain a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system.

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

[0033] Example 1

[0034] A method for preparing a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system, comprising the following steps:

[0035] (1) Preparation of a difunctional p-toluenesulfonic acid-based epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy) acetic acid and 1 mol of an epoxy group-containing epoxy resin are sequentially added to a reactor, and stirred at 100°C for 48 h. After the reaction is completed, the pure difunctional p-toluenesulfonic acid-based epoxy resin is obtained by precipitation, collection and drying.

[0036] (2) The difunctional p-toluenesulfonic acid-based epoxy resin prepared in step (1) is dissolved in 2 mol of acetone, followed by the addition of 1 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, and stirred at 50°C for 10 min. The mixture is uniformly poured into a mold and cured at 100°C for 10 h to obtain a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system.

[0037] Figure 3 A thermogravimetric analysis diagram of the high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system prepared in this example.

[0038] Figure 4 A physical diagram of the high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system prepared in this example.

[0039] Example 2

[0040] A method for preparing a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system, comprising the following steps:

[0041] (1) Preparation of a difunctional p-toluenesulfonic acid-based epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy) acetic acid and 1 mol of an epoxy group-containing epoxy resin are sequentially added to a reactor, and stirred at 100°C for 48 h. After the reaction is completed, the pure difunctional p-toluenesulfonic acid-based epoxy resin is obtained by precipitation, collection and drying.

[0042] (2) Dissolve the bifunctional p-toluenesulfonic acid-based epoxy resin prepared in step (1) in 2 mol of acetone, then add 1 mol of N,N,N',N'-tetramethyl-1,3-propanediamine, stir at 50°C for 10 min, pour into a mold after stirring uniformly, and cure at 100°C for 10 h to obtain a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system.

[0043] Example 3

[0044] A method for preparing a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system includes the following steps:

[0045] (1) Prepare a bifunctional p-toluenesulfonic acid-based epoxy resin: add 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of an epoxy group-containing epoxy resin into a reactor in sequence, and stir at 100°C for 48 h. After the reaction is completed, collect and dry the pure bifunctional p-toluenesulfonic acid-based epoxy resin after precipitation.

[0046] (2) Dissolve the bifunctional p-toluenesulfonic acid-based epoxy resin prepared in step (1) in 2 mol of acetone, then add 1 mol of N,N,N',N'-tetramethyl-1,3-propanediamine, stir at 40°C for 10 min, pour into a mold after stirring uniformly, and cure at 120°C for 10 h to obtain a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system.

[0047] Example 4

[0048] A method for preparing a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system includes the following steps:

[0049] (1) Prepare a bifunctional p-toluenesulfonic acid-based epoxy resin: add 3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of an epoxy group-containing epoxy resin into a reactor in sequence, and stir at 100°C for 48 h. After the reaction is completed, collect and dry the pure bifunctional p-toluenesulfonic acid-based epoxy resin after precipitation.

[0050] (2) Dissolve the bifunctional p-toluenesulfonic acid-based epoxy resin prepared in step (1) in 2 mol of acetone, then add 1 mol of 2,4,6-tris(dimethylaminomethyl)phenol, stir at 40°C for 10 min, pour into a mold after stirring uniformly, and cure at 120°C for 10 h to obtain a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system.

[0051] Example 5

[0052] A method for preparing a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system includes the following steps:

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

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

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

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

[0057] Figure 2 The nuclear magnetic resonance spectrum of the multifunctional p-toluenesulfonic acid based epoxy resin prepared in this example.

[0058] Example 6

[0059] A method for preparing a high-thermal-stability degradable / antibacterial ester ammonium based epoxy thermosetting system, comprising the following steps:

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

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

[0062] (3) The multifunctional p-toluenesulfonic acid-based epoxy resin prepared in step (2) is dissolved in 2 mol of acetone, then 1.0 mol of N,N,N',N'-tetramethyl-1,3-propanediamine is added, and stirred at 50°C for 10 min. After uniform stirring, it is poured into a mold and cured at 100°C for 10 h to obtain a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system.

[0063] Example 7

[0064] A method for preparing a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system, comprising the following steps:

[0065] (1) Preparation of a difunctional p-toluenesulfonic acid-based epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy) acetic acid and 1 mol of an epoxy group-containing epoxy resin are sequentially added to a reactor, and stirred at 100°C for 48 h. After the reaction is completed, the pure difunctional p-toluenesulfonic acid-based epoxy resin is obtained by precipitation, collection, and drying.

[0066] (2) Preparation of a multifunctional p-toluenesulfonic acid-based epoxy resin: 2.6 mol of 2-(p-toluenesulfonyloxy) acetic acid and 1 mol of the difunctional p-toluenesulfonic acid-based epoxy resin prepared in step (1) are sequentially added to a reactor, and stirred at 130°C for 48 h. After the reaction is completed, the multifunctional p-toluenesulfonic acid-based epoxy resin is obtained by precipitation, collection, and drying.

[0067] (3) The multifunctional p-toluenesulfonic acid-based epoxy resin prepared in step (2) is dissolved in 2 mol of acetone, then 1.0 mol of N,N,N',N'-tetramethyl-1,3-propanediamine is added, and stirred at 50°C for 10 min. After uniform stirring, it is poured into a mold and cured at 100°C for 10 h to obtain a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system.

[0068] Example 8

[0069] A method for preparing a high-thermal-stability degradable / antibacterial ester ammonium-based epoxy thermosetting system, comprising the following steps:

[0070] (1) Preparation of a difunctional p-toluenesulfonic acid-based epoxy resin: 3 mol of 2-(p-toluenesulfonyloxy) acetic acid and 1 mol of an epoxy group-containing epoxy resin are sequentially added to a reactor, and stirred at 100°C for 48 h. After the reaction is completed, the pure difunctional p-toluenesulfonic acid-based epoxy resin is obtained by precipitation, collection, and drying.

[0071] 2) Preparation of multifunctional p-toluenesulfonic acid based epoxy resin: 2.6 mol 2-(p-toluenesulfonyloxy) acetic acid and 1 mol of the bifunctional p-toluenesulfonic acid based epoxy resin prepared in step (1) were sequentially added in a reactor, and stirred at 130°C for 48 h. After the reaction was completed, the multifunctional p-toluenesulfonic acid based epoxy resin was obtained by precipitation, collection and drying.

[0072] (3) The multifunctional p-toluenesulfonic acid based epoxy resin prepared in step (2) was dissolved in 2 mol of acetone, and then 1.0 mol of 2,4,6-tris(dimethylaminomethyl) phenol was added, stirred at 60°C for 10 min, poured into a mold, and cured at 130°C for 10 h to obtain a high-heat-stable degradable / antibacterial ester ammonium based epoxy thermosetting system.

[0073] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the scope of protection of the present application.

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) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 2.5-3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin containing epoxy groups were added to a reactor in sequence, and stirred at 100-130°C for 1-48 hours. After the reaction, the difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection, and drying. (2) dissolving the difunctional p-toluenesulfonic acid epoxy resin prepared in step (1) in 1-10 mol of an organic solvent, 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; The amine curing agent is N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N'-tetramethyl-1,3-propylenediamine or 2,4,6-tris(dimethylaminomethyl)phenol.

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) Preparation of difunctional p-toluenesulfonic acid epoxy resin: 2.5-3 mol of 2-(p-toluenesulfonyloxy)acetic acid and 1 mol of epoxy resin containing epoxy groups were added to a reactor in sequence, and stirred at 100-130°C for 1-48 hours. After the reaction, the difunctional p-toluenesulfonic acid epoxy resin was obtained by precipitation, collection, and drying. (2) Preparation of a multifunctional p-toluenesulfonic acid epoxy resin: Subsequently, 2.5-3 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 at 100-130° C. for 1-48 hours; after the reaction, the multifunctional p-toluenesulfonic acid epoxy resin was 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 solvent, 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; The amine curing agent is N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N'-tetramethyl-1,3-propylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol or pentamethyldipropylenetriamine.

3. The method for preparing a highly thermally stable degradable / antibacterial ester ammonium epoxy thermosetting system according to claim 1 or 2, characterized in that 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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