Enhanced, antibacterial and hydrophobic high polymer material, preparation method thereof and application of enhanced, antibacterial and hydrophobic high polymer material in paper protection

Abstract

The invention belongs to the field of polymer antibacterial materials, and particularly relates to a reinforced, antibacterial and hydrophobic polymer material, a preparation method and application in paper protection. The preparation method comprises the following steps: taking acryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate and hydroxyethyl methylacrylate as monomers, and carrying out water phase polymerization to prepare the polyacryloyloxyethyl trimethyl ammonium chloride-methyl methacrylate-hydroxyethyl methylacrylate high polymer material. The synthesis method is simple, the use of an organic solvent is avoided, and the obtained high polymer material is used for paper protection, has reinforcing, antibacterial and hydrophobic effects on paper, and has important significance in promoting the anti-aging protection process of the paper.

Description

Technical Field

[0001] The invention belongs to the field of polymer antibacterial materials, and in particular relates to a polymer material with enhanced antibacterial and hydrophobic properties, a preparation method thereof, and application in paper protection. Background Art

[0002] Bacterial infection has had a profound impact on human production and life, causing many serious problems. In terms of cultural heritage protection, paper cultural relics are subject to microbial erosion, and precious historical and cultural heritage is at risk of damage. In this context, the use of antibacterial materials to inhibit the growth of microorganisms on the surface of materials has become a research direction with great scientific value and practical significance. Due to historical conditions, geographical restrictions and imperfect cultural relics preservation technology, the problem of paper being corroded by bacteria and reduced mechanical strength has always been a difficult problem in the field of its protection. Over time, paper is corroded by bacteria, the appearance and form of cultural relics change, the mechanical strength decreases, and the original physical and chemical properties also change. Therefore, solving the problem of paper damage has become an important issue that needs to be overcome in paper protection work.

[0003] Among the numerous antibacterial materials, amphiphilic cationic polymers stand out for their unique performance advantages and have been widely used in fields such as biomedicine and materials science. Among them, quaternary ammonium salt compounds are favored for their low toxicity, low price, and broad antibacterial spectrum. Quaternary ammonium salt molecules are composed of a positively charged hydrophilic head group and a lipophilic tail chain. This special structure gives them good surface activity and antibacterial properties. Studies have shown that the antibacterial activity of quaternary ammonium salts is closely related to the structure of the substituents on their nitrogen atoms and the type of paired anions. By rationally designing the molecular structure, its antibacterial properties can be further optimized. However, the current synthesis process of quaternary ammonium salt polymers has problems such as harsh reaction conditions, solvent and environmental pollution. In the future, it is necessary to overcome these shortcomings through green synthesis technology, development of efficient catalysts, process optimization, etc., in order to improve synthesis efficiency and reduce costs.

[0004] In the prior art, paper reinforcement, antibacterial and hydrophobicity are all carried out in steps. The increase of reagents and operating procedures not only increases costs, but also causes harm to the surrounding environment. More importantly, as the use of chemical agents increases, the harm to paper also increases. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention aims to provide a polymer material which has a simple synthesis method, is green and safe, and has the advantages of strengthening paper cultural relics, antibacterial and hydrophobic. The polymer material is prepared by aqueous polymerization using acryloyloxyethyltrimethylammonium chloride (DAC), methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) as monomers.

[0006] The preparation method of polyacryloyloxyethyl trimethyl ammonium chloride-methyl methacrylate-2-hydroxyethyl methacrylate (P(DAC-MMA-HEMA)) provided by the present invention comprises the following steps:

[0007] (1) Acryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, and 2-hydroxyethyl methacrylate are dispersed in water and dissolved by ultrasonic treatment. Then, nitrogen is introduced at room temperature to remove oxygen, obtaining a mixed solution.

[0008] (2) The mixed solution in step (1) is heated to 60 °C, and an aqueous solution of a mixture of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (AIBA) and ammonium persulfate as an oxidant is added dropwise within 30 min. Then, an aqueous solution of sodium bisulfite as a reducing agent is added dropwise within 30 min. After the addition is completed, the temperature is raised to 50-80 °C and the reaction is carried out for 5-10 h.

[0009] Among them, the mass ratio of the reaction raw materials acryloyloxyethyl trimethyl ammonium chloride, 2-hydroxyethyl methacrylate, and methyl methacrylate is 3:(4-5):1.5. The dosage of the initiator (the total mass of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, ammonium persulfate, and sodium bisulfite) accounts for 0.6-1.5% of the total mass of the monomers. Among them, the content of 2,2'-azobis(2-methylpropionamidine) dihydrochloride accounts for 25% of the total mass of the initiator. The molar ratio of the oxidant to the reducing agent is 1:1, and the monomer mass concentration is 30-35%.

[0010] After the reaction, acetone is added for precipitation. The precipitated substance is left for 12 h and then vacuum dried at room temperature for 24 h to obtain polyacryloyloxyethyl trimethyl ammonium chloride-methyl methacrylate-2-hydroxyethyl methacrylate. The intrinsic viscosity of the polymer and its minimum inhibitory concentration against Escherichia coli and Staphylococcus aureus are detected by GB / T31246-2014 and WS / T 639-2018 respectively.

[0011] The high molecular material of the present invention is used for the strengthening, antibacterial, and hydrophobic properties of paper. The specific application method is as follows: The prepared high molecular material is dissolved in a 30% ethanol solution (volume ratio) to prepare a dispersion liquid, and then the dispersion liquid is evenly sprayed on a 26 cm × 18 cm paper in four times. After drying at room temperature, it is placed in a blast drying oven at 105 °C for 30-40 s. The dosage of the high molecular material is 0.1-0.4 g / m 2 paper.

[0012] The tensile strength and tear degree of the paper are measured by GB / T 12914-2018 and GB / T 455-2002 respectively. The antibacterial performance of the polymer on the paper is measured by GB / T 42702-2023.

[0013] For the application of the above paper protective agent, the paper used is the paper of "Popular Cinema" magazine published in 1980, and its basis weight is 53.0 ± 1.0 g / m 2 .

[0014] Compared with the prior art, the beneficial effects of the technical solution provided by the present invention are as follows:

[0015] (1) The water-phase polymerization of the polymer material avoids the use of organic solvents and improves safety.

[0016] (2) The polymer material contains acryloyloxyethyl trimethyl ammonium chloride cations, which can play an obvious antibacterial effect when applied to paper. The combination of methyl methacrylate and 2-hydroxyethyl acrylate can endow the paper with certain strengthening and hydrophobic effects.

[0017] (3) The polymer material of the present invention has multiple functions such as strengthening, antibacterial, and hydrophobic. It is not only green and safe, simple to operate, with fewer steps, but also reduces the damage to the paper performance caused by multiple uses of drugs. Description of the Drawings

[0018] Figure 1 Infrared spectrum of P(DAC-MMA-HEMA) prepared in Example 1;

[0019] Figure 2 1H nuclear magnetic resonance spectrum of P(DAC-MMA-HEMA) prepared in Example 1;

[0020] Figure 3 Transmission electron microscope image of Escherichia coli after being treated with P(DAC-MMA-HEMA) prepared in Example 1;

[0021] Figure 4 Transmission electron microscope image of Staphylococcus aureus after being treated with P(DAC-MMA-HEMA) prepared in Example 1;

[0022] Figure 5 Effect of the dosage of P(DAC-MMA-HEMA) on the tearing strength of the paper sample;

[0023] Figure 6 Effect of the dosage of P(DAC-MMA-HEMA) on the tensile strength of the paper sample;

[0024] Figure 7 Water contact angle of the P(DAC-MMA-HEMA) obtained in Example 1 applied on the paper. Detailed Embodiments

[0025] The present invention will be further described in detail below with reference to specific embodiments. These embodiments are only for illustrative purposes of the present invention and do not limit the scope of the present invention in any way.

[0026] Example 1

[0027] At room temperature, 3.75 g of DAC (mass percentage of monomer: 80%), 4.04 g of HEMA (mass percentage of monomer: 99%), 1.53 g of MMA (mass percentage of monomer: 98%), and 5 mL of H2O were successively added into a three-necked flask. After ultrasonic treatment for 5 min, N2 was introduced to remove oxygen for 30 min. Stirring was started. When the reaction temperature reached 60 °C, an aqueous solution mixture containing 0.0263 g of (NH4)2S2O8 and 0.0127 g of AIBA in 8 mL was added dropwise within 30 min. After stirring for 5 min, an aqueous solution containing 0.0120 g of NaHSO3 in 7 mL was added dropwise within 30 min. After the addition was completed, the reaction solution was raised to 65 °C and reacted for 8 h. After the reaction was completed, precipitation was carried out using acetone to obtain P(DAC-MMA-HEMA). The total amount of initiator accounted for 0.6% of the monomer mass, and the monomer mass concentration was 30%. The intrinsic viscosity of P(DAC-MMA-HEMA) was measured to be 47.51 mL / g. The minimum inhibitory concentration of P(DAC-MMA-HEMA) against Escherichia coli was 1.40 mg / mL, and the minimum inhibitory concentration against Staphylococcus aureus was 2.81 mg / mL.

[0028] Example 2

[0029] At room temperature, 3.75 g of an aqueous solution of DAC (mass percentage of monomer: 80%), 5.05 g of HEMA (mass percentage of monomer: 99%), 1.53 g of MMA (mass percentage of monomer: 98%), and 5 mL of H2O were successively added into a three-necked flask and ultrasonicated for 5 min, then N2 was introduced to remove oxygen for 30 min. Stirring was started. When the reaction temperature reached 60 °C, an aqueous solution mixture containing 0.0294 g of (NH4)2S2O8 and 0.0143 g of AIBA in 8 mL was added dropwise within 30 min. After stirring for 5 min, an aqueous solution containing 0.0134 g of NaHSO3 in 7 mL was added dropwise within 30 min. After the addition was completed, the reaction was carried out at 65 °C for 8 h. After the reaction was completed, precipitation was carried out using acetone. The total amount of initiator accounted for 0.6% of the monomer mass, and the monomer mass concentration was 30%. The intrinsic viscosity of P(DAC-MMA-HEMA) was measured to be 42 mL / g. P(DAC-MMA-HEMA) had no obvious antibacterial effect against Escherichia coli, and the minimum inhibitory concentration against Staphylococcus aureus was 5.63 mg / mL.

[0030] Example 3

[0031] At room temperature, 3.75 g of DAC (mass percentage of monomer is 80%), 4.04 g of HEMA (mass percentage of monomer is 99%), 1.53 g of MMA (mass percentage of monomer is 98%), and 5 mL of H2O were successively added to a three-necked flask. After ultrasonic treatment for 5 min, N2 was introduced, and deoxygenation was carried out for 30 min. Stirring was started, and when the reaction temperature reached 60 °C, 5 mL of an aqueous solution containing 0.0263 g of (NH4)2S2O8 and 0.0127 g of AIBA was added dropwise within 30 min. After stirring for 5 min, 5 mL of an aqueous solution containing 0.0120 g of NaHSO3 was added dropwise within 30 min. After the addition was completed, the reaction was carried out at 65 °C for 8 h. After the reaction was completed, precipitation was carried out using acetone. The total amount of initiator accounted for 0.6% of the monomer mass, and the monomer mass concentration was 35%. The intrinsic viscosity of P(DAC-MMA-HEMA) was measured to be 64.88 mL / g. The minimum inhibitory concentration of P(DAC-MMA-HEMA) against Escherichia coli was 5.63 mg / mL, and the minimum inhibitory concentration against Staphylococcus aureus was 5.63 mg / mL.

[0032] Example 4

[0033] At room temperature, 3.75 g of DAC (mass percentage of monomer is 80%), 4.04 g of HEMA (mass percentage of monomer is 99%), 1.53 g of MMA (mass percentage of monomer is 98%), and 5 mL of H2O were successively added to a three-necked flask. After ultrasonic treatment for 5 min, N2 was introduced, and deoxygenation was carried out for 30 min. Stirring was started, and when the reaction temperature reached 60 °C, the amount of initiator was changed, accounting for 0.4%, 1%, and 1.5% of the total monomer mass respectively. The proportion of each initiator remained unchanged, and the addition method remained unchanged. After the addition was completed, the reaction was carried out at 65 °C for 8 h. After the reaction was completed, precipitation was carried out using acetone. The total amount of initiator accounted for 0.6% of the monomer mass, and the monomer mass concentration was 30%. The polymers obtained with initiator dosages of 0.4%, 1%, and 1.5% were denoted as 1, 2, and 3 respectively.

[0034] The intrinsic viscosities of samples 1, 2, and 3 were measured to be 72.65 mL / g, 35.45 mL / g, and 20.25 mL / g respectively.

[0035] The minimum inhibitory concentrations of samples 1, 2, and 3 against Escherichia coli were measured to be 11.25 mg / mL, 5.63 mg / mL, and 5.63 mg / mL respectively.

[0036] The minimum inhibitory concentrations of samples 1, 2, and 3 against Staphylococcus aureus were measured to be 5.63 mg / mL, 2.81 mg / mL, and 5.63 mg / mL respectively.

[0037] Example 5

[0038] Apply the P(DAC-MMA-HEMA) prepared in Example 1 to the paper of the magazine *Popular Cinema* published in 1980, and test its antibacterial, hydrophobic, and paper strengthening properties. The steps are as follows: Dissolve 9.4 mg of P(DAC-MMA-HEMA) in a 30% ethanol solution (by volume ratio) to prepare a 20 mL dispersion, and then evenly spray the dispersion on the front and back of a 26 cm × 18 cm magazine paper in four times. After drying at room temperature, place it in a forced-air drying oven at 105 °C for 30 - 40 s. The spraying amount of P(DAC-MMA-HEMA) is 0.1 g / cm 2 paper, and the water contact angle of the paper is increased from the original 79° to 117.1°.

[0039] When the dosages of P(DAC-MMA-HEMA) are 0.1, 0.2, 0.3, and 0.4 g / cm 2 paper, after drying, the paper samples are left standing in an environment of 23 ± 1 °C and 50 ± 2% RH for 24 h, and then the tearing strength and tensile strength of the treated paper samples are measured.

[0040] Comparative Example 1

[0041] At room temperature, add 3.75 g of DAC (mass percentage of monomer 80%), 4.04 g of HEMA (mass percentage of monomer 99%), and 5 mL of H2O to a three-necked flask in sequence. After ultrasonic treatment for 5 min, introduce N2, deoxygenate for 30 min, start stirring. When the reaction temperature reaches 60 °C, dropwise add an aqueous solution mixture containing 0.0220 g of (NH4)2S2O8 and 0.0105 g of AIBA in 8 mL within 30 min. After stirring for 5 min, dropwise add an aqueous solution containing 0.0095 g of NaHSO3 in 7 mL within 30 min. After the addition is completed, react at 65 °C for 8 h. After the reaction ends, the mixed solution is thin and there is no obvious polymerization.

[0042] Comparative Example 2

[0043] At room temperature, add 3.75 g of DAC (mass percentage of monomer 80%), 4.04 g of HEMA (mass percentage of monomer 99%), 1.53 g of MMA (mass percentage of monomer 98%), and 5 mL of H2O to a three-necked flask in sequence. After ultrasonic treatment for 5 min, introduce N2, deoxygenate for 30 min, start stirring. When the reaction temperature reaches 60 °C, dropwise add an aqueous solution mixture containing 0.0263 g of (NH4)2S2O8 and 0.0127 g of AIBA in 6 mL within 30 min. After stirring for 5 min, dropwise add an aqueous solution containing 0.0120 g of NaHSO3 in 6 mL within 30 min. After the addition is completed, react at 65 °C for 8 h. After the reaction ends, the mixed solution is thin and there is no obvious polymerization. The total amount of initiator accounts for 0.6% of the monomer mass, and the monomer mass concentration is 40%.

[0044] Comparative Example 3

[0045] At room temperature, 5 g of DAC (mass percentage of monomer: 80%), 4.04 g of HEMA (mass percentage of monomer: 99%), 1.53 g of MMA (mass percentage of monomer: 98%), and 6 mL of H2O were successively added to a three-necked flask. After ultrasonic treatment for 5 min, N2 was introduced, and the oxygen was removed for 30 min. Stirring was started, and when the reaction temperature reached 60 °C, an aqueous solution mixture containing 0.0294 g of (NH4)2S2O8 and 0.0143 g of AIBA in 8 mL was added dropwise within 30 min. After stirring for 5 min, an aqueous solution containing 0.0134 g of NaHSO3 in 7 mL was added dropwise within 30 min. After the addition was completed, the reaction was carried out at 65 °C for 8 h. After the reaction was completed, the mixed solution was thin and there was no obvious polymerization. The total amount of initiator accounted for 0.6% of the monomer mass, and the monomer mass concentration was 30%.

[0046] Comparative Example 4

[0047] At room temperature, 3.75 g of DAC (mass percentage of monomer: 80%), 4.04 g of HEMA (mass percentage of monomer: 99%), 1.51 g of butyl methacrylate (BMC, mass percentage of monomer: 99%), and 5 mL of H2O were successively added to a three-necked flask. After ultrasonic treatment for 5 min, N2 was introduced to remove oxygen for 30 min. Stirring was started, and when the reaction temperature reached 60 °C, an aqueous solution mixture containing 0.0263 g of (NH4)2S2O8 and 0.0127 g of AIBA in 8 mL was added dropwise within 30 min. After stirring for 5 min, an aqueous solution containing 0.0120 g of NaHSO3 in 7 mL was added dropwise within 30 min. After the addition was completed, the reaction solution was heated to 65 °C and reacted for 8 h. After the reaction was completed, the mixed solution was thin and there was no obvious polymerization. The total amount of initiator accounted for 0.6% of the monomer mass, and the monomer mass concentration was 30%.

Claims

1. A polymer material with enhanced antibacterial hydrophobicity, characterized in that, The polymer material is prepared by aqueous phase polymerization from acryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, and 2-hydroxyethyl methacrylate.

2. The enhanced, antibacterial and hydrophobic polymer material according to claim 1, characterized in that, The mass ratio of acryloyloxyethyl trimethyl ammonium chloride, 2-hydroxyethyl methacrylate, and methyl methacrylate is 3:4 - 5:1.5, and the monomer concentration is 30 - 35%.

3. A method for preparing a polymer material with enhanced antibacterial hydrophobicity according to claim 1, characterized in that, The preparation method is as follows: acryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, and 2-hydroxyethyl methacrylate are mixed and dissolved in deionized water, heated and stirred, then an initiator is added for reaction, followed by precipitation filtration with acetone to remove unreacted monomers, and vacuum drying to obtain the polymer material.

4. The preparation method of the polymer material with enhanced antibacterial hydrophobicity according to claim 3, characterized in that, The initiator consists of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, sodium bisulfite, and ammonium persulfate. The dosage of the initiator is 0.6 - 1.5% of the total mass of the monomers. The content of 2,2'-azobis(2-methylpropionamidine) dihydrochloride accounts for 25% of the total mass of the initiator, and the molar ratio of sodium bisulfite to ammonium persulfate is 1:

1.

5. The preparation method of the polymer material with enhanced antibacterial and hydrophobic properties according to claim 3, characterized in that, The reaction temperature is 50 - 80 °C, and the reaction time is 5 - 10 h.

6. Use of the polymer material with enhanced antibacterial hydrophobicity according to claim 1, characterized in that, The polymer material is used as an antibacterial, strengthening, and hydrophobic protective agent for paper.

7. Use of the polymer material with enhanced antibacterial hydrophobicity according to claim 6, characterized in that The application method is as follows: the polymer material is dissolved in a 30% ethanol solution to prepare a dispersion, and then the dispersion is evenly sprayed on a 26 cm × 18 cm piece of paper in four portions. After drying at room temperature, it is placed in a forced-air drying oven at 105 °C for 30 - 40 s.

8. The application of the polymer material according to claim 7, wherein The dosage of the polymer material is 0.1 - 0.4 g / m 2 paper.

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