Natural alcohol modified polyacrylate as well as preparation method and application thereof

Abstract

The invention provides natural alcohol modified polyacrylate as well as a preparation method and application thereof. The preparation method comprises the following steps: firstly, dissolving acrylic anhydride and 4-dimethylaminopyridine in tetrahydrofuran; adding menthol into the solution to carry out esterification reaction; sequentially adding acrylic acid and ammonium persulfate to carry out polymerization reaction; after the reaction liquid is cooled, sequentially adding N, N-dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and then adding geraniol to carry out esterification reaction; and finally, carrying out filtration, rotary evaporation, extraction and dialysis to obtain the natural alcohol modified polyacrylate. The natural alcohol modified polyacrylate disclosed by the invention has high antibacterial activity and excellent bacterial adhesion resistance; the preparation method is simple, convenient to operate, good in controllability, low in treatment equipment requirement and beneficial to industrial production; the natural fiber fabric can be endowed with good antibacterial property, bacterial adhesion resistance and durability, and has a wide application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of printing and dyeing auxiliaries, and particularly relates to a natural alcohol-modified polyacrylate and a preparation method and application thereof. Background Art

[0002] With the impact of the pandemic and evolving consumer preferences, consumers are increasingly concerned about the hygiene, health, and antimicrobial properties of textiles. Natural fibers, derived from natural sources such as plants, animals, or minerals, possess excellent properties such as skin-friendly softness, moisture wicking, and antistatic properties. However, the rough surface structure and texture of natural fibers can easily harbor dirt. Microorganisms such as bacteria easily attach and thrive on textile surfaces, forming plaque and even biofilms, which can cause discoloration, mold, and brittle degradation. Furthermore, textiles harboring large numbers of microorganisms can also induce skin diseases in humans, seriously impacting human health and hygiene. Antimicrobial finishing is an important way to enhance the comfort of natural fiber textiles.

[0003] At present, textile antimicrobial agents on the market are mainly divided into three categories: organic, inorganic and natural antimicrobial agents. Antimicrobial agents for textiles should not only kill harmful microorganisms and prevent the spread of diseases, but also have low toxicity to humans and the environment. Compared with organic and inorganic antimicrobial agents, natural antimicrobial agents are completely extracted from animals and plants, are environmentally friendly, have good biocompatibility, are highly safe and easily biodegraded, and have less impact on humans and the environment. However, natural antimicrobial agents have some shortcomings: high-molecular-weight antimicrobial activity is insufficient (such as chitosan), and low-molecular-weight antimicrobial agents are volatile, water-soluble and have poor stability. Improving the antimicrobial activity and stability of natural antimicrobial agents is a current research hotspot.

[0004] Typically, after a period of use, antimicrobial textiles can become susceptible to the adhesion of live and dead bacteria to their surfaces, covering or blocking the antimicrobial active sites and compromising their long-term antimicrobial properties. Ideal textile antimicrobial agents should not only kill harmful microorganisms and prevent the spread of disease, but also prevent bacteria from adhering to the textile surface, ensuring that the textile surface remains clean and sterile. To effectively prevent bacterial adhesion on material surfaces, strategies such as superhydrophobic surfaces, hydration, and stereochemistry are currently being employed. However, superhydrophobic surfaces and hydration are easily damaged by changes in the external environment, resulting in a decrease in the antibacterial adhesion properties of textiles. Stereochemistry is a ubiquitous phenomenon in nature, and the chiral structure of organic compounds plays a key role in various biological and physiological processes. Menthol is a naturally occurring chiral terpene small molecule compound with eight stereochemical structures. L-menthol ((-)-menthol) is the most common of these eight structures, and its stereochemical structure effectively prevents bacterial adhesion on material surfaces.

[0005] To combine the antimicrobial activity of natural extracts with their chiral antibacterial properties, while also addressing the stability and poor water solubility of low-molecular-weight natural extracts, a combination of esterification and free radical polymerization can be used to prepare natural alcohol-modified acrylates with high antimicrobial and antibacterial properties through chemical modification and structural manipulation. Currently, there are no reports on the use of natural menthol and geraniol to modify acrylates for textile finishing. Summary of the Invention

[0006] To address the problems existing in the prior art, the present invention provides a natural alcohol-modified polyacrylate, its preparation method, and its application. The natural alcohol-modified polyacrylate of the present invention exhibits excellent antibacterial and anti-bacterial adhesion properties. Furthermore, the preparation method is simple, easy to operate, highly controllable, requires minimal processing equipment, and is amenable to industrial production.

[0007] The present invention also provides an application of a natural alcohol-modified polyacrylate as an antibacterial adhesion agent, and applies it to the post-finishing of natural fiber textiles. The natural fiber textiles after this finishing have good antibacterial properties, antibacterial adhesion and durability, and have broad application prospects in the antibacterial finishing of natural fiber fabrics.

[0008] A natural alcohol modified polyacrylate, the structural formula of the natural alcohol modified polyacrylate is as follows:

[0009]

[0010] Where R is OH or

[0011] The preparation method of the natural alcohol modified polyacrylate comprises the following steps:

[0012] 1) dissolving acrylic anhydride and 4-dimethylaminopyridine in tetrahydrofuran to obtain an acrylic anhydride solution;

[0013] 2) adding menthol to the above solution and carrying out esterification reaction at 60-80°C for 3-7 hours;

[0014] 3) adding acrylic acid and ammonium persulfate in sequence, and polymerizing at 60-80° C. for 3-5 hours to obtain menthol-modified polyacrylate;

[0015] 4) After the reaction solution is cooled, N,N-dicyclohexylcarbodiimide and 4-dimethylaminopyridine are added in sequence, and then geraniol is added, and the esterification reaction is carried out at 20-40°C for 9-15 hours;

[0016] 5) After filtering, rotary evaporation, extraction and dialysis, natural alcohol modified polyacrylate is obtained.

[0017] In the above preparation method, preferably, in step 1), the concentration of the acrylic anhydride solution is 0.5 to 1.5 mol / L; and the amount of 4-dimethylaminopyridine added is 1 to 3 wt% of the amount of acrylic anhydride added.

[0018] In the above preparation method, preferably, in step 2), the molar ratio of menthol to acrylic anhydride is 1.5-2.5:1.

[0019] In the above preparation method, preferably, in step 3), the molar ratio of acrylic acid to acrylic anhydride is 1.5-2.5:1; and the amount of ammonium persulfate added is 0.5-1.5 wt% of the amount of acrylic anhydride added.

[0020] In the above preparation method, preferably, in step 4), the molar ratio of N,N-dicyclohexylcarbodiimide to acrylic anhydride is 0.5-1.5:1; the amount of 4-dimethylaminopyridine added is 1-3wt% of the amount of acrylic anhydride added; and the molar ratio of geraniol to acrylic anhydride is 0.75-1.25:1.

[0021] In the above preparation method, preferably, in step 5), the rotary evaporation temperature is 40-60° C., the rotary evaporation time is 30-50 min; the extraction solvent is water and dichloromethane; a dialysis bag with a molecular weight of 2000-5000 is selected, and the dialysis time is 40-50 h.

[0022] Application of the natural alcohol modified polyacrylate in the preparation of antibacterial adhesion agents.

[0023] A method for finishing natural fiber textiles, comprising padding the natural fiber textiles with a natural alcohol-modified polyacrylate solution, drying, and baking to obtain bacterial-resistant natural fiber textiles. The structure of the natural alcohol-modified polyacrylate is as follows:

[0024]

[0025] Where R is OH or

[0026] In the above technical solution, preferably, the natural alcohol-modified polyacrylate solution is a solution with water / ethanol in a volume ratio of 8 to 10:1 as solvent, 30 to 50 g / L of natural alcohol-modified polyacrylate and 0.1 to 0.3 g / L of 4-dimethylaminopyridine as solute.

[0027] The present invention first esterifies acrylic anhydride with menthol, then adds the water-soluble monomer acrylic acid for free radical polymerization to produce a stable and water-soluble menthol-modified polyacrylate. Geraniol is then used to esterify this polymer to produce a natural alcohol-modified polyacrylate. This natural alcohol-modified polyacrylate combines the high antimicrobial activity of geraniol, the stereochiral antibacterial properties of menthol, and the water solubility and high stability of the carboxyl groups of the polyacrylate. Through a durable finishing process, it can impart excellent antimicrobial properties, antibacterial adhesion, and durability to natural fiber textiles.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) Natural alcohol-modified polyacrylates contain multiple terpene geraniol segments with high antibacterial activity, which can impart high antibacterial properties to textiles. Compared with the minimum inhibitory concentration (MIC) values ​​of geraniol against Staphylococcus aureus and Escherichia coli of 64 μg / mL and 128 μg / mL, the MIC values ​​of natural alcohol-modified polyacrylates are 16 μg / mL and 32 μg / mL, respectively. The antibacterial rate of cotton fabrics treated with natural alcohol-modified polyacrylates against Staphylococcus aureus and Escherichia coli is as high as 99.9%, which is 9.78% and 17.1% higher than that of cotton fabrics treated with geraniol alone.

[0030] (2) Natural alcohol-modified polyacrylates also contain multiple stereochiral menthol segments that inhibit bacterial adhesion, which affect bacterial recognition on the fabric surface and impart excellent antibacterial adhesion properties to the textile. This invention effectively alleviates the problem of live / dead bacteria adhering to the surface of antibacterial textiles after a period of use, causing secondary bacterial infection or biofilm formation. Natural alcohol-modified polyacrylate-treated cotton fabrics exhibited an antibacterial adhesion rate of 99.9% against Staphylococcus aureus and Escherichia coli, respectively, which is 28.2% and 33.2% higher than cotton fabrics treated with menthol alone.

[0031] (3) The carboxyl groups in the natural alcohol-modified polyacrylate structure are esterified and grafted onto the hydroxyl groups on the surface of natural fiber textiles, making the finished textiles highly washable. After 20 home washes, the antibacterial rate and anti-bacterial adhesion rate of the finished textiles can still retain more than 80% of their original levels.

[0032] In summary, the natural alcohol-modified polyacrylate of the present invention combines the advantages of geraniol, menthol, and polyacrylate, exhibiting highly effective and stable antimicrobial properties and bacterial adhesion resistance. When applied to the post-finishing of natural fiber textiles, the finished natural fiber textiles exhibit excellent antimicrobial properties, bacterial adhesion resistance, and durability, showing broad application prospects in the antimicrobial finishing of natural fiber textiles. Furthermore, the preparation method is simple, easy to operate, highly controllable, requires minimal processing equipment, and is amenable to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The infrared spectra of geraniol (GE), menthol (MT), menthol-modified polyacrylate (PEA) and natural alcohol-modified polyacrylate (PMAG);

[0034] Figure 2 The effect of the molar ratio of geraniol (GE) to acrylic anhydride on the growth of Staphylococcus aureus (S.Auteus) and Escherichia coli (S.Coli) on cotton fabrics treated with different methods is shown;

[0035] Figure 3 is the effect of the molar ratio of menthol (MT) to acrylic anhydride on the adhesion of Staphylococcus aureus (S.Aureus) and Escherichia coli (S.Coli) on cotton fabrics with different treatments; DETAILED DESCRIPTION

[0036] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.After reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0037] Examples 1-5: Changing the molar ratio of menthol to acrylic anhydride.

[0038] 1) First, 30 mmol of acrylic anhydride and 2 wt% of 4-dimethylaminopyridine added with acrylic anhydride were dissolved in 30 mL of tetrahydrofuran and stirred to fully dissolve.

[0039] 2) Menthol was added to the above solution, and the molar ratio of menthol to acrylic anhydride was controlled to be 0.5:1, 1:1, 1.5:1, 2:1, and 2.5:1, respectively, and the esterification reaction was carried out at 70° C. for 5 h.

[0040] 3) 60 mmol of acrylic acid and 1 wt% of ammonium persulfate of acrylic anhydride were added in sequence, and the polymerization reaction was carried out at 70° C. for 4 hours.

[0041] 4) After the reaction solution was cooled, 30 mmol of N,N-dicyclohexylcarbodiimide and 2 wt% of 4-dimethylaminopyridine with acrylic anhydride were added in sequence, and then 30 mmol of geraniol was added, and the reaction was carried out at 30° C. for 12 h.

[0042] 5) Finally, the product was filtered, rotary evaporated at 50°C for 40 minutes, extracted with water and dichloromethane, and dialyzed for 48 hours using a 3500 molecular weight dialysis bag to obtain five natural alcohol-modified polyacrylates (PMAGs) with different menthol segment contents.

[0043] The reaction process of the above preparation method is as follows:

[0044]

[0045] In the above reaction formula, 4-dimethylaminopyridine is abbreviated as DMAP; ammonium persulfate is abbreviated as APS; N,N-dicyclohexylcarbodiimide (DCC); menthol-modified polyacrylate is abbreviated as PEA; and natural alcohol-modified polyacrylate is abbreviated as PMAG.

[0046] 6) Finishing of natural fiber textiles: Prepare a finishing solution containing 30 g / L PAMG and 0.1 g / L 4-dimethylaminopyridine using a water / ethanol ratio of 8:1 by volume. Use a bath ratio of 1:30. Immerse cotton fabric in this finishing solution for 5 minutes, then double-dip and double-pad (pad yield 90%). Dry at 80°C for 3 minutes, and bake at 140°C for 3 minutes.

[0047] Referring to GB / T 20944.3-2008, "Evaluation of Antimicrobial Properties of Textiles," the antibacterial efficiency of PMAG-treated cotton fabrics was tested by varying the molar ratio of menthol to acrylic anhydride. The antibacterial adhesion rate was also tested with reference to the literature (Wu J D, Zhang C, Xu S T, et al. Preparation of zwitterionic polymer-functionalized cotton fabrics and the performance of anti-biofouling and long-term biofilm resistance [J]. Colloid and Interface Science Communications, 2018, 24: 98-104). The experimental results are shown in Table 1.

[0048] Table 1 Effect of the molar ratio of menthol to acrylic anhydride on the antibacterial rate and anti-bacterial adhesion rate of PMAG-treated cotton fabrics

[0049]

[0050] Depend on Figure 3 As the molar ratio of menthol to acrylic anhydride increases, the number of E. coli and S. aureus attached to PMAG-treated cotton fabric decreases, indicating improved anti-adhesion properties. When the molar ratio of menthol to acrylic anhydride is 2:1, the anti-adhesion rate against E. coli and S. aureus reaches a maximum of 99.9%. However, further increasing the molar ratio maintains the same anti-adhesion rate.

[0051] Figure 1The infrared spectra of menthol (MT), geraniol (GE), menthol modified polyacrylate (PEA) and natural alcohol modified polyacrylate (PMAG) are shown in Figure 1. -1 The range shows the characteristic stretching vibration absorption peaks of -CH2 and -CH3 groups, and at 3500cm -1 The stretching vibration peak of hydroxyl (-OH) was observed near 1650 cm -1 The typical stretching vibration peak of C=O in the ester group appears at 1170 cm -1 The appearance of the characteristic absorption peak of COC bond at 1730 cm-1 confirmed that MT was successfully grafted onto the polyacrylate backbone through esterification reaction. In addition, compared with natural alcohol modified polyacrylate (PMAG), PEA has a -1 The newly added C=C double bond stretching vibration absorption peak further confirms the structural difference between the two modified products.

[0052] Example 5-10: Changing the molar ratio of geraniol to acrylic anhydride.

[0053] 1) First, 30 mmol of acrylic anhydride and 2 wt% of 4-dimethylaminopyridine added with acrylic anhydride were dissolved in 30 mL of tetrahydrofuran and stirred to fully dissolve.

[0054] 2) Menthol was added to the above solution, and the molar ratio of menthol to acrylic anhydride was controlled to be 2:1, and the esterification reaction was carried out at 70° C. for 5 hours.

[0055] 3) 60 mmol of acrylic acid and 1 wt% of ammonium persulfate of acrylic anhydride were added in sequence, and the polymerization reaction was carried out at 70° C. for 4 hours.

[0056] 4) After the reaction solution is cooled, 30 mmol of N,N-dicyclohexylcarbodiimide and 2 wt% of 4-dimethylaminopyridine with acrylic anhydride added were added in sequence, and then geraniol was added, with the molar ratio of geraniol to acrylic anhydride being controlled at 0.5:1, 1:1, 1.5:1, 2:1, and 2.5:1, respectively. The esterification reaction was carried out at 30°C for 12 h.

[0057] 5) Finally, the product was filtered, rotary evaporated at 50°C for 40 minutes, extracted with water and dichloromethane, and dialyzed for 48 hours using a 3500 molecular weight dialysis bag to obtain five natural alcohol-modified polyacrylates (PMAGs) with different menthol segment contents.

[0058] The reaction process of the above preparation method is as follows:

[0059]

[0060] In the above reaction formula, 4-dimethylaminopyridine is abbreviated as DMAP; ammonium persulfate is abbreviated as APS; N,N-dicyclohexylcarbodiimide (DCC); menthol-modified polyacrylate is abbreviated as PEA; and natural alcohol-modified polyacrylate is abbreviated as PMAG.

[0061] 6) Finishing process for natural fiber textiles: A finishing solution containing 50 g / L PAMG and 0.3 g / L 4-dimethylaminopyridine was prepared using a water / ethanol ratio of 10:1 by volume. A bath ratio of 1:40 was selected. Cotton fabric was immersed in the finishing solution for 5 minutes, followed by a double dip and double padding (padding yield of 90%), drying at 80°C for 3 minutes, and baking at 150°C for 1 minute.

[0062] According to GB / T20944.3-2008 “Evaluation of Antibacterial Properties of Textiles”, under the above conditions, the molar ratio of menthol to acrylic anhydride was changed to investigate the antibacterial rate and anti-bacterial adhesion rate of the finished cotton fabric. The results are shown in Table 2.

[0063] Table 2 Effect of the molar ratio of geraniol to acrylic anhydride on the MIC value of PMAG and the antibacterial rate and antibacterial adhesion rate of the treated cotton fabric

[0064]

[0065] Table 2 shows that as the molar ratio of geraniol to acrylic anhydride increases, the MIC value of PMAG decreases before remaining constant. When the molar ratio of geraniol to acrylic anhydride is 1:1, the MIC values ​​of PMAG against Staphylococcus aureus and Escherichia coli are 32 μg / mL and 64 μg / mL, respectively. However, further increases in the molar ratio do not change the MIC values. Furthermore, as the MIC value of PMAG decreases, the antibacterial efficiency of the PAMG-treated cotton fabric increases. When the molar ratio of geraniol to acrylic anhydride is 1:1, the antibacterial efficiency of the PAMG-treated cotton fabric against both Escherichia coli and Staphylococcus aureus reaches 99.9%.

[0066] Example 11: Comparison of the effects of menthol, acrylic anhydride and PMAG on the antibacterial rate and antibacterial adhesion rate of finished cotton fabrics.

[0067] 1) First, 30 mmol of acrylic anhydride and 2 wt% of 4-dimethylaminopyridine added with acrylic anhydride were dissolved in 30 mL of tetrahydrofuran and stirred to fully dissolve.

[0068] 2) Menthol was added to the above solution, and the molar ratio of menthol to acrylic anhydride was controlled to be 2:1, and the esterification reaction was carried out at 70° C. for 5 hours.

[0069] 3) 60 mmol of acrylic acid and 1 wt% of ammonium persulfate of acrylic anhydride were added in sequence, and the polymerization reaction was carried out at 70° C. for 4 hours.

[0070] 4) After the reaction solution is cooled, 30 mmol of N,N-dicyclohexylcarbodiimide and 2 wt% of 4-dimethylaminopyridine with acrylic anhydride added were added in sequence, and then geraniol was added to control the molar ratio of geraniol to acrylic anhydride to be 1:1. The esterification reaction was carried out at 30°C for 12 hours.

[0071] 5) Finally, the product was filtered, rotary evaporated at 50° C. for 40 minutes, extracted with water and dichloromethane, and dialyzed for 48 hours using a 3500 molecular weight dialysis bag to obtain a natural alcohol-modified polyacrylate (PMAG) containing menthol segments.

[0072] The reaction process of the above preparation method is as follows:

[0073]

[0074] In the above reaction formula, 4-dimethylaminopyridine is abbreviated as DMAP; ammonium persulfate is abbreviated as APS; N,N-dicyclohexylcarbodiimide (DCC); menthol-modified polyacrylate is abbreviated as PEA; and natural alcohol-modified polyacrylate is abbreviated as PMAG.

[0075] 6) Finishing of natural fiber textiles: Prepare a finishing solution containing 40 g / L PAMG and 0.2 g / L 4-dimethylaminopyridine using a 9:1 volume ratio of water to ethanol. Use a bath ratio of 1:40. Immerse cotton fabric in this finishing solution for 5 minutes, then double-dip and double-pad (pad yield 90%). Dry at 80°C for 3 minutes and bake at 140°C for 2 minutes.

[0076] Finishing process for natural fiber cotton fabrics treated with natural alcohol alone: ​​Use ethanol as the solvent, prepare a finishing solution of 40g / L geraniol and menthol, respectively, at a bath ratio of 1:40. Immerse the cotton fabric in the finishing solution for 5 minutes, perform a double dip and double padding (padding yield 90%), and dry at 80°C for 3 minutes.

[0077] According to GB / T20944.3-2008, under the above conditions, the molar ratio of menthol to acrylic anhydride was changed to study the antibacterial rate and anti-bacterial adhesion rate of PMAG-treated cotton fabrics. The results are shown in Table 3.

[0078] Table 3 MIC values ​​of polyacrylate modified with geraniol, menthol and natural alcohol and the antibacterial rate and antibacterial adhesion rate of the three types of treated cotton fabrics.

[0079]

[0080] As shown in Table 3, menthol exhibits some antibacterial adhesion properties but lacks antibacterial properties. Geraniol exhibits good antibacterial properties but lacks antibacterial adhesion properties. Compared to cotton fabric treated with geraniol alone, PMAG-treated cotton fabric exhibited higher antibacterial and antibacterial adhesion properties against Staphylococcus aureus and Escherichia coli by 9.78% and 17.1%, respectively. Compared to cotton fabric treated with menthol alone, PMAG-treated cotton fabric exhibited higher antibacterial and anti-adhesion properties by 28.2% and 33.2%, respectively. This demonstrates that the modified menthol and geraniol enhance their stability, thereby imparting enhanced antibacterial and anti-adhesion properties to cotton fabrics.

[0081] Example 12: Washing durability test of cotton fabric finished with natural alcohol modified polyacrylate.

[0082] 1) First, 30 mmol of acrylic anhydride and 2 wt% of 4-dimethylaminopyridine added with acrylic anhydride were dissolved in 30 mL of tetrahydrofuran and stirred to fully dissolve.

[0083] 2) Menthol was added to the above solution, and the molar ratio of menthol to acrylic anhydride was controlled to be 2:1, and the esterification reaction was carried out at 70° C. for 5 hours.

[0084] 3) 60 mmol of acrylic acid and 1 wt% of ammonium persulfate of acrylic anhydride were added in sequence, and the polymerization reaction was carried out at 70° C. for 4 hours.

[0085] 4) After the reaction solution is cooled, 30 mmol of N,N-dicyclohexylcarbodiimide and 2 wt% of 4-dimethylaminopyridine with acrylic anhydride added were added in sequence, and then geraniol was added to control the molar ratio of geraniol to acrylic anhydride to be 1:1. The esterification reaction was carried out at 30°C for 12 hours.

[0086] 5) Finally, the mixture was filtered, rotary evaporated at 50° C. for 40 minutes, extracted with water and dichloromethane, and dialyzed for 48 hours using a 3500 molecular weight dialysis bag to obtain a natural alcohol-modified polyacrylate (PAMG) containing menthol segments.

[0087] The reaction process of the above preparation method is as follows:

[0088]

[0089] In the above reaction formula, 4-dimethylaminopyridine is abbreviated as DMAP; ammonium persulfate is abbreviated as APS; N,N-dicyclohexylcarbodiimide (DCC); menthol-modified polyacrylate is abbreviated as PEA; and natural alcohol-modified polyacrylate is abbreviated as PMAG.

[0090] 6) Finishing of natural fiber textiles: Prepare a finishing solution containing 40 g / L PAMG and 0.2 g / L 4-dimethylaminopyridine using a 9:1 volume ratio of water to ethanol. Use a bath ratio of 1:40. Immerse cotton fabric in this finishing solution for 5 minutes, then double-dip and double-pad (pad yield 90%). Dry at 80°C for 3 minutes and bake at 140°C for 2 minutes.

[0091] According to AATCC 61-2013 "Color Fastness to Laundering of Household and Commercial Textiles: Accelerated Method", the antibacterial rate and anti-bacterial adhesion rate of the dual-functional cotton fabric prepared in this example were measured at 40°C after 5, 10, 15, and 20 washes to evaluate its durability.

[0092] According to GB / T20944.3-2008, under the above conditions, the antibacterial rate and anti-bacterial adhesion rate of PMAG-treated cotton fabrics were tested by changing the number of washings. The results are shown in Table 4.

[0093] Table 4 Effect of washing times on the antibacterial rate and anti-bacterial adhesion rate of PMAG-treated cotton fabrics

[0094]

[0095] The antibacterial and anti-adhesion rates of PMAG-treated cotton fabric against Staphylococcus aureus and Escherichia coli decreased slightly with increasing wash cycles. However, after 20 washes, these rates remained above 80%, indicating that the antibacterial and anti-adhesion properties of PMAG-treated cotton fabric are durable.

Claims

1. A natural alcohol modified polyacrylate, characterized in that: The structural formula of the natural alcohol modified polyacrylate is as follows: Where R is OH or 2. A method for preparing the natural alcohol modified polyacrylate according to claim 1, characterized in that: The following steps are involved: 1) dissolving acrylic anhydride and 4-dimethylaminopyridine in tetrahydrofuran to obtain an acrylic anhydride solution; 2) adding menthol to the above solution and carrying out esterification reaction at 60-80°C for 3-7 hours; 3) Subsequently, acrylic acid and ammonium persulfate are added in sequence, and polymerization reaction is carried out at 60-80° C. for 3-5 hours to obtain menthol-modified polyacrylate; 4) After the reaction solution is cooled, N,N-dicyclohexylcarbodiimide and 4-dimethylaminopyridine are added in sequence, and then geraniol is added, and the esterification reaction is carried out at 20-40°C for 9-15 hours; 5) After filtering, rotary evaporation, extraction and dialysis, natural alcohol modified polyacrylate is obtained.

3. The preparation method according to claim 2, characterized in that In step 1), the concentration of the acrylic anhydride solution is 0.5 to 1.5 mol / L; and the amount of 4-dimethylaminopyridine added is 1 to 3 wt% of the amount of acrylic anhydride added.

4. The preparation method according to claim 2, characterized in that In step 2), the molar ratio of menthol to acrylic anhydride is 1.5-2.5:

1.

5. The preparation method according to claim 2, characterized in that In step 3), the molar ratio of acrylic acid to acrylic anhydride is 1.5-2.5:1; and the amount of ammonium persulfate added is 0.5-1.5 wt % of the amount of acrylic anhydride added.

6. The preparation method according to claim 2, characterized in that In step 4), the molar ratio of N,N-dicyclohexylcarbodiimide to acrylic anhydride is 0.5-1.5:1; the amount of 4-dimethylaminopyridine added is 1-3 wt% of the amount of acrylic anhydride added; and the molar ratio of geraniol to acrylic anhydride is 0.75-1.25:

1.

7. The preparation method according to claim 2, characterized in that In step 5), the rotary evaporation temperature is 40-60° C., the rotary evaporation time is 30-50 min; the extraction solvents are water and dichloromethane; a dialysis bag with a molecular weight of 2000-5000 is selected, and the dialysis time is 40-50 h.

8. Use of the natural alcohol modified polyacrylate according to claim 1 in the preparation of an antibacterial adhesion agent.

9. A method for finishing natural fiber textiles, characterized in that: Natural fiber textiles are padded with a natural alcohol-modified polyacrylate solution, dried, and baked to obtain anti-bacterial adhesion natural fiber textiles. The structure of the natural alcohol-modified polyacrylate is as follows: Where R is OH or 10. The natural fiber textile finishing method according to claim 9, characterized in that: The natural alcohol modified polyacrylate solution is a solution using water / ethanol with a volume ratio of 8-10:1 as solvent, 30-50 g / L natural alcohol modified polyacrylate and 0.1-0.3 g / L 4-dimethylaminopyridine as solute.

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