Antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of being degraded to original resin in weak base mode

Abstract

The invention discloses an antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of being degraded to original resin in a weak base mode, which is prepared by the following steps: dissolving phenoxy resin and haloacetic acid in a water-carrying agent, reacting at 80-130 DEG C for 1-12 hours, continuously separating generated water in the process, and after the reaction is finished, evaporating and precipitating to obtain the antibacterial thermosetting coating / plastic system. The halogenated acetic acid esterified phenoxy resin is obtained; mixing the obtained halogenated acetic acid esterified phenoxy resin with a poly-tertiary amine compound, and curing in a mold at 40-100 DEG C for 1-10 hours to obtain a thermosetting polymer; compared with the traditional phenoxy resin, the material prepared by the invention has the characteristics of organic solvent resistance, intrinsic antibiosis, degradability and the like, and the composite characteristic can enrich the application scene and the application range of the phenoxy resin.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of green cyclic polymer materials, and particularly relates to an antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin. BACKGROUND

[0002] Traditional thermosetting plastics are covalently cross-linked polymers that are insoluble and infusible, and are difficult to recycle and reuse when discarded. In recent years, the development of closed-loop recycling of new thermosetting materials and their application in composite materials, 3D printing materials, etc. have been witnessed through the innovation of degradation technology and reversible chemistry (or dynamic chemistry). The methods for realizing closed-loop recycling of new thermosetting materials and their downstream materials are divided into two categories. One is to hydrolyze thermosetting materials in acidic, alkaline or catalyst solutions, and then recover monomers or oligomers, which can be reused to prepare thermosetting materials or functional materials thereof. The other is to de-cross-link and re-cross-link thermosetting materials through exchange reactions of dynamic bonds. By adopting the strategy of hydrolytic closed-loop recycling, the recovered thermosetting resin has the same structure and performance as the original resin.

[0003] Quaternary ammonium salts (QASs) are a class of cationic compounds with simple structural composition, consisting of two main parts: a positively charged quaternary ammonium nitrogen ion (N+) as the main head, and a long hydrophobic tail composed of alkyl chains. R can represent methyl, saturated or unsaturated long-chain alkyl, benzyl or other organic groups, where the four hydrocarbon groups of R can be the same or different. X represents the counterion, which is usually a halide anion (such as F-, Cl-, Br-, I-, etc.), or an acid (such as HSO4-, RCOO-, etc.).

[0004] The antibacterial performance of quaternary ammonium salt structure is derived from its positively charged center, and its antibacterial mechanism is generally believed to be: positively charged quaternary ammonium salt molecules are adsorbed to negatively charged bacteria under the action of Coulomb force, and then their alkyl chains are combined with the hydrophobic interaction of the cell membrane phospholipid bilayer, inserting and cutting into the cell membrane, causing the leakage of intracellular proteins, DNA, RNA, etc., thereby leading to bacterial death. Therefore, combining quaternary ammonium salt compounds with materials can endow these materials with antibacterial properties. These antibacterial materials can be used to manufacture medical devices, food packaging, medical supplies, household supplies, etc. to reduce the growth and spread of microorganisms, helping to maintain a clean and sanitary environment. The use of antibacterial materials can effectively prevent cross-infection and disease transmission, which is of great significance for protecting public health.

[0005] The cationic charge close to the ester linkage makes ordinary ester quats unusually stable in acidic conditions and susceptible to hydrolysis in basic conditions. The pH dependence of hydrolysis of ester quats has been studied in detail. It was found that the rate of hydrolysis reaches a minimum at pH 3-4 and accelerates significantly above pH 5-6. Such esters hydrolyze more rapidly in base than esters lacking a nearby charge, but the difference is not large. However, if the charge is on the other side of the ester linkage, the rate increase is much more dramatic, and such esters are extremely unstable in basic conditions. The rate of base hydrolysis is increased 200-fold, and the rate of acid hydrolysis is decreased 2000-fold, compared to esters lacking a cationic charge. In Europe, dialkyl ester quats have largely replaced the stable dialkyl quats as rinse cycle softeners. The shift from stable dialkyl quats to dialkyl ester quats represents the second largest product type change in surfactant history.

[0006] The application provides an antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin, which is prepared by the following steps: firstly, dissolving phenoxy resin and halogenated acetic acid in a water-carrying agent and reacting at 80-130 DEG C for 1-12 hours, continuously removing the generated water in the process, and after the reaction is completed, evaporating and precipitating to obtain phenoxy resin esterified with halogenated acetic acid; and secondly, mixing the obtained phenoxy resin esterified with halogenated acetic acid with a polytertiary amine compound, curing in a mold at 40-100 DEG C for 1-10 hours to obtain a thermosetting polymer. SUMMARY

[0007] The application aims at overcoming the defects of the prior art and provides an antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin.

[0008] The application is achieved by the following technical scheme: an antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin, which is prepared by the following steps: (1) dissolving phenoxy resin and halogenated acetic acid in a water-carrying agent and reacting at 80-130 DEG C for 1-12 hours, continuously removing the generated water in the process, and after the reaction is completed, evaporating and precipitating to obtain phenoxy resin esterified with halogenated acetic acid; The molar ratio of the hydroxyl group of the phenoxy resin to the halogenated acetic acid is 1:0.1-1; (2) mixing the obtained phenoxy resin esterified with halogenated acetic acid with a polytertiary amine compound, curing in a mold at 40-100 DEG C for 1-10 hours to obtain an antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin; The feed molar ratio of the haloacetic ester groups in the haloacetic esterified phenoxy resin to the tertiary amine groups in the polytertiary amine compound is 1:0.5-1.5.

[0009] Further, the haloacetic acid is chloroacetic acid, bromoacetic acid or iodoacetic acid.

[0010] Further, the water-carrying agent is benzene, toluene, cyclohexane or dichloromethane.

[0011] Further, the polytertiary amine compound is N,N,N',N'-tetramethyl-1,2-ethanediamine, N'-[(dimethylamino)methyl]-N,N-dimethylmethanediamine, tetramethyl-1,3-propanediamine, N,N,N',N'-tetramethylethylenediamine, N-ethyl-N,N',N'-trimethyl-1,2-ethanediamine, tetramethylpropanediamine or 4,4'-methylenebis(N,N-dimethylaniline).

[0012] The present application has the following advantages: by introducing a quaternary amine ester structure into the system, intrinsic antibacterial properties are imparted to the material, and the resistance to organic solvents (toluene, ethyl acetate, etc.) is also greatly improved, and the cured product can be hydrolyzed back to the original phenoxy resin by weak base. BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 is the nuclear magnetic resonance hydrogen spectrum of the phenoxy resin; Figure 2 is the nuclear magnetic resonance hydrogen spectrum of the antibacterial thermosetting coating / plastic body derived from the phenoxy resin and capable of being weakly alkaline degraded to the original resin prepared in Example 1; Figure 3 is the actual picture of the antibacterial thermosetting coating / plastic body derived from the phenoxy resin and capable of being weakly alkaline degraded to the original resin prepared in Example 1. DETAILED DESCRIPTION

[0014] 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 the examples. Based on the examples in the present application, all the other examples obtained by those skilled in the art without making creative efforts are within the protection scope of the present application.

[0015] In the following examples, the experimental methods are conventional methods unless otherwise specified, and the reagents and materials can be obtained from commercial channels unless otherwise specified.

[0016] The present application provides a preparation method of an antibacterial thermosetting coating / plastic system derived from a phenoxy resin and capable of being weakly alkaline degraded to the original resin, comprising the following steps: (1) The phenoxy resin and the haloacetic acid are dissolved in a water-carrying agent, and reacted at 80-130°C for 1-12 hours, in the process, the generated water is continuously removed, after the reaction is completed, the haloacetic acid esterified phenoxy resin is obtained by evaporation and precipitation.

[0017] The chemical formula of the phenoxy resin is: .

[0018] The molar ratio of the hydroxyl group of the phenoxy resin to the haloacetic acid is 1:0.1-1.

[0019] The haloacetic acid is chloroacetic acid, bromoacetic acid or iodoacetic acid.

[0020] The water-carrying agent is benzene, toluene, cyclohexane or dichloromethane.

[0021] (2) The obtained haloacetic acid esterified phenoxy resin is mixed with a poly tertiary amine compound, and cured in a mold at 40-100°C for 1-10 hours to obtain a thermosetting polymer, that is, an antibacterial thermosetting coating / plastic system derived from a phenoxy resin and capable of weakly alkaline degradation to the original resin.

[0022] The molar ratio of the haloacetic acid ester group in the haloacetic acid esterified phenoxy resin to the tertiary amine group in the poly tertiary amine compound is 1:0.5-1.5.

[0023] The poly tertiary amine compound is N,N,N',N'-tetramethyl-1,2-ethanediamine, N'-[(dimethylamino)methyl]-N,N-dimethylmethanediamine, tetramethyl-1,3-propanediamine, N,N,N',N'-tetramethylethylenediamine, N-ethyl-N,N',N'-trimethyl-1,2-ethanediamine, tetramethylpropanediamine or 4,4'-methylenebis(N,N-dimethylaniline).

[0024] The chemical formula of the antibacterial thermosetting coating / plastic system derived from a phenoxy resin and capable of weakly alkaline degradation to the original resin is: .

[0025] Example 1: (1) The phenoxy resin and the chloroacetic acid are dissolved in toluene, and reacted at 130°C for 1 hour, in the process, the generated water is continuously removed, after the reaction is completed, the chloroacetic acid esterified phenoxy resin is obtained by evaporation and precipitation.

[0026] The molar ratio of the hydroxyl group of the phenoxy resin to the chloroacetic acid is 1:0.1, 1g of phenoxy resin is put in, and 0.0337g of chloroacetic acid is put in.

[0027] (2) The obtained chloroacetic acid-esterified phenoxy resin is mixed with N,N,N',N'-tetramethyl-1,2-ethylenediamine and cured in a mold at 40°C for 10 hours to obtain a thermosetting polymer, that is, an antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin.

[0028] The molar ratio of the chloroacetic acid ester group in the chloroacetic acid esterified phenoxy resin to the tertiary amine group in N,N,N',N'-tetramethyl-1,2-ethylenediamine is 1:0.5, with 1g of phenoxy resin and 0.2g of N,N,N',N'-tetramethyl-1,2-ethylenediamine added.

[0029] Example 2: (1) Phenoxy resin and bromoacetic acid are dissolved in cyclohexane and reacted at 80°C for 10 hours. During the reaction, the generated water is continuously removed. After the reaction is completed, the phenol esterified by bromoacetic acid is obtained by evaporation and precipitation.

[0030] The molar ratio of the hydroxyl groups of the phenoxy resin to bromoacetic acid is 1:1, with 1g of phenoxy resin and 0.50g of bromoacetic acid added.

[0031] (2) The obtained bromoacetic acid-esterified phenoxy resin is mixed with N,N,N',N'-tetramethyl-1,2-ethylenediamine and cured in a mold at 100°C for 1 hour to obtain a thermosetting polymer, that is, an antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin.

[0032] The molar ratio of the bromoacetic acid ester group in the bromoacetic acid esterified phenoxy resin to the tertiary amine group in N,N,N',N'-tetramethyl-1,2-ethylenediamine is 1:1.5, with 1g of phenoxy resin and 0.62g of N,N,N',N'-tetramethyl-1,2-ethylenediamine added.

[0033] Example 3: (1) Phenoxy resin and iodoacetic acid are dissolved in toluene and reacted at 90°C for 8 hours. During the reaction, the generated water is continuously removed. After the reaction is completed, the iodoacetic acid-esterified phenoxy resin is obtained by evaporation and precipitation.

[0034] The molar ratio of the hydroxyl groups of the phenoxy resin to iodoacetic acid is 1:0.8, with 1g of phenoxy resin and 0.53g of iodoacetic acid added.

[0035] (2) The obtained iodoacetic acid-esterified phenoxy resin is mixed with N'-[(dimethylamino)methyl]-N,N-dimethylmethanediamine and cured in a mold at 50°C for 8 hours to obtain a thermosetting polymer, that is, an antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin.

[0036] The molar ratio of the iodacetoxy groups in the iodacetoxy-esterified phenoxy resin to the tertiary amine groups in N'-[(dimethylamino)methyl]-N,N-dimethylmethanediamine is 1 :0.7, 1 g of phenoxy resin is put in, and 0.32 g of N'-[(dimethylamino)methyl]-N,N-dimethylmethanediamine is put in.

[0037] Example 4: (1) The phenoxy resin is dissolved in cyclohexane with chloroacetic acid, and reacted at 100°C for 5 hours, during which the generated water is continuously removed, after the reaction is completed, evaporation and precipitation are carried out to obtain the chloroacetoxy-esterified phenoxy resin.

[0038] The molar ratio of the hydroxyl groups in the phenoxy resin to the chloroacetic acid is 1 :0.7, 1 g of phenoxy resin is put in, and 0.46 g of chloroacetic acid is put in.

[0039] (2) The obtained chloroacetoxy-esterified phenoxy resin is mixed with N-ethyl-N,N',N'-trimethyl-1,2-ethanediamine, and cured in a mold at 60°C for 7 hours to obtain a thermosetting polymer, that is, an antibacterial thermosetting coating / plastic system derived from the phenoxy resin and capable of weakly alkaline degradation to the original resin.

[0040] The molar ratio of the chloroacetoxy groups in the chloroacetoxy-esterified phenoxy resin to the tertiary amine groups in N-ethyl-N,N',N'-trimethyl-1,2-ethanediamine is 1 :0.6, 1 g of phenoxy resin is put in, and 0.28 g of N-ethyl-N,N',N'-trimethyl-1,2-ethanediamine is put in.

[0041] Example 5: (1) The phenoxy resin is dissolved in toluene with bromoacetic acid, and reacted at 110°C for 6 hours, during which the generated water is continuously removed, after the reaction is completed, evaporation and precipitation are carried out to obtain the bromoacetoxy-esterified phenoxy resin.

[0042] The molar ratio of the hydroxyl groups in the phenoxy resin to the bromoacetic acid is 1 :0.6, 1 g of phenoxy resin is put in, and 0.30 g of bromoacetic acid is put in.

[0043] (2) The obtained bromoacetoxy-esterified phenoxy resin is mixed with tetramethyl-1,3-propanediamine, and cured in a mold at 70°C for 6 hours to obtain a thermosetting polymer, that is, an antibacterial thermosetting coating / plastic system derived from the phenoxy resin and capable of weakly alkaline degradation to the original resin.

[0044] The bromoacetate groups in the bromoacetate-esterified phenoxy resin and the tertiary amine groups in tetramethyl-1,3-propanediamine are in a molar ratio of 1 :0.5, 1 g of phenoxy resin is used, and 0.23 g of tetramethyl-1,3-propanediamine is used.

[0045] Example 6: (1 ) The phenoxy resin is dissolved in dichloromethane with iodine acetate, and reacted at 115°C for 7 hours, during which the generated water is continuously removed, after the reaction is completed, evaporation and precipitation are performed to obtain the iodine acetate-esterified phenoxy resin.

[0046] The hydroxyl groups in the phenoxy resin and the iodine acetate are in a molar ratio of 1 :0.5, 1 g of phenoxy resin is used, and 0.331 g of iodine acetate is used.

[0047] (2) The obtained iodine acetate-esterified phenoxy resin is mixed with N'-[(dimethylamino)methyl]-N,N-dimethylmethanediamine, and cured in a mold at 80°C for 5 hours to obtain a thermosetting polymer, i.e. to obtain an antibacterial thermosetting coating / plastic system derived from the phenoxy resin and capable of weakly alkaline degradation to the original resin.

[0048] The iodine acetate groups in the iodine acetate-esterified phenoxy resin and the tertiary amine groups in N'-[(dimethylamino)methyl]-N,N-dimethylmethanediamine are in a molar ratio of 1 :0.4, 1 g of phenoxy resin is used, and 0.23 g of N'-[(dimethylamino)methyl]-N,N-dimethylmethanediamine is used.

[0049] Example 7: (1 ) The phenoxy resin is dissolved in cyclohexane with chloroacetate, and reacted at 120°C for 8 hours, during which the generated water is continuously removed, after the reaction is completed, evaporation and precipitation are performed to obtain the chloroacetate-esterified phenoxy resin.

[0050] The hydroxyl groups in the phenoxy resin and the chloroacetate are in a molar ratio of 1 :0.7, 1 g of phenoxy resin is used, and 0.235 g of chloroacetate is used.

[0051] (2) The obtained chloroacetate-esterified phenoxy resin is mixed with 4,4'-methylenebis(N,N-dimethylaniline), and cured in a mold at 90°C for 4 hours to obtain a thermosetting polymer, i.e. to obtain an antibacterial thermosetting coating / plastic system derived from the phenoxy resin and capable of weakly alkaline degradation to the original resin.

[0052] The chloroacetate groups in the chloroacetate-esterified phenoxy resin and the tertiary amine groups in 4,4'-methylenebis(N,N-dimethylaniline) are in a molar ratio of 1 :0.3, 1 g of phenoxy resin is used, and 0.27 g of 4,4'-methylenebis(N,N-dimethylaniline) is used.

[0053] Example 8: (1) The phenoxy resin was dissolved in dichloromethane with chloroacetic acid at 110°C for 6 hours, during which the generated water was removed, and after the reaction was completed, the chloroacetic esterified phenoxy resin was obtained by evaporation and precipitation.

[0054] The molar ratio of the hydroxyl groups of the phenoxy resin to the chloroacetic acid was 1:0.6, 1 g of the phenoxy resin was added, and 0.202 g of chloroacetic acid was added.

[0055] (2) The obtained chloroacetic esterified phenoxy resin was mixed with tetramethylpropylenediamine, and cured in a mold at 70°C for 6 hours to obtain a thermosetting polymer, i.e. an antibacterial thermosetting coating / plastic system derived from the phenoxy resin and capable of being degraded to the original resin by weak alkaline.

[0056] The molar ratio of the chloroacetic ester groups in the chloroacetic esterified phenoxy resin to the tertiary amine groups in the tetramethylpropylenediamine was 1:0.5, 1 g of the phenoxy resin was added, and 0.28 g of tetramethylpropylenediamine was added.

[0057] Figure 1 It is the nuclear magnetic resonance hydrogen spectrum of the phenoxy resin. δ 6.5-8.0: the hydrogen on the benzene ring is shifted to a high field due to the ring current effect, and the peak shape is multiple. δ 4.0: the methylene hydrogen connected to oxygen is shifted to a low field due to the electronegativity of oxygen. δ 3.0-4.0: the hydroxyl hydrogen, the peak is wide due to hydrogen bonding. δ 1.0-2.0: the alkyl chain hydrogen is shielded and shifted to a high field.

[0058] Figure 2 It is the nuclear magnetic resonance hydrogen spectrum of the antibacterial thermosetting coating / plastic system derived from the phenoxy resin and capable of being degraded to the original resin by weak alkaline prepared in Example 1. δ 6.5-8.0: the 8 hydrogens on the two benzene rings are shifted to a high field due to the ring current deshielding effect, and the peak shape is multiple, reflecting the ortho-para coupling. δ 4.0: the methylene hydrogen connected to oxygen (2n) is shifted to a low field due to the electronegativity of oxygen, and the peak shape is single or double. δ 3.0-4.0: the hydroxyl hydrogen (2n) is affected by hydrogen bonding, and the peak shape is wide, and the chemical shift fluctuates with conditions. δ 1.0-2.0: the alkyl chain hydrogen (2n) is shielded and shifted to a high field, and the peak shape is single or multiple.

[0059] Figure 3 It is the actual picture of the antibacterial thermosetting coating / plastic system derived from the phenoxy resin and capable of being degraded to the original resin by weak alkaline prepared in Example 1.

[0060] 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 thermosetting antibacterial coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin, characterized in that, The antibacterial thermosetting coating / plastic system, derived from phenoxy resin and capable of weakly alkaline degradation to the original resin, is prepared through the following steps: (1) Phenoxy resin and haloacetic acid are dissolved in a dehydrating agent and reacted at 80~130℃ for 1~12 hours. During the process, the generated water is continuously removed. After the reaction is completed, the phenoxy resin esterified with haloacetic acid is obtained by evaporation and precipitation. The molar ratio of the hydroxyl groups of the phenoxy resin to the haloacetic acid is 1:0.1~1; (2) The obtained halogenated acetic acid esterified phenoxy resin is mixed with a polytert-amine compound and cured in a mold at 40~100℃ for 1~10 hours to obtain an antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly basic degradation to the original resin. The molar ratio of the haloacetic acid ester group in the halogenated phenoxy resin to the tertiary amine group in the polytertiary amine compound is 1:0.5~1.

5.

2. The antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin according to claim 1, characterized in that, The haloacetic acid is chloroacetic acid, bromoacetic acid, or iodoacetic acid.

3. The antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin according to claim 1, characterized in that, The water-removing agent is benzene, toluene, cyclohexane, or dichloromethane.

4. The antibacterial thermosetting coating / plastic system derived from phenoxy resin and capable of weakly alkaline degradation to the original resin according to claim 1, characterized in that, The polytert-amine compound is N,N,N',N'-tetramethyl-1,2-ethylenediamine, N'-[(dimethylamino)methyl]-N,N-dimethylmethanediamine, tetramethyl-1,3-propanediamine, N,N,N',N'-tetramethylethylenediamine, N-ethyl-N,N',N'-trimethyl-1,2-ethylenediamine, tetramethylpropanediamine, or 4,4'-methylenebis(N,N-dimethylaniline).

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