CN110306340B - Antibacterial natural textile material with surface modified borneol and preparation method and application thereof - Google Patents
Antibacterial natural textile material with surface modified borneol and preparation method and application thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
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Abstract
The invention relates to an antibacterial natural textile material with surface modified borneol, which is prepared from a natural textile material coupled by aminosiloxane and a 4-aldehyde benzoic acid borneol derivative by utilizing a new antibacterial strategy of surface stereochemistry, and has the advantages of mild reaction conditions and simple preparation process in the preparation process. The antibacterial natural textile material is a non-release antibacterial textile material, does not release a bactericide to kill microorganisms, but influences the adhesion of the microorganisms through the surface stereochemical structure of the material, can ensure the use safety, does not cause skin irritation and sensitization, and does not damage the self flora of the skin; meanwhile, the material has good anti-adhesion effect on bacteria and fungi, can effectively inhibit the adhesion of the bacteria and the fungi for a long time, and has a stable structure and water washing resistance. The antibacterial natural textile material is a novel safe, stable and environment-friendly antibacterial natural textile, and can be widely applied to medical, sanitary, environment-friendly and clothing industries and the like.
Description
Technical Field
The invention belongs to the field of biological antibacterial materials, and relates to an antibacterial natural textile material with a surface modified borneol, and a preparation method and application thereof.
Background
The natural textile is widely applied to daily life of people, such as clothes, bed sheets, masks, white clothes, medical gauze and the like, but simultaneously provides hotbeds and media for the growth, the propagation and the spread of harmful microorganisms, and seriously threatens the health of human beings in the using process. With the improvement of science and technology and the improvement of health and safety consciousness of people, people also put higher requirements on the antibacterial performance of textiles. Therefore, how to satisfy the requirement of endowing the textile with efficient and durable antibacterial function without affecting the appearance and safe use of the textile becomes a research hotspot of common attention in academia and industry nowadays.
The existing preparation methods of the antibacterial textile mainly comprise two methods: one is to add antibacterial agent into textile raw material to make antibacterial fiber, then to weave into various antibacterial fabric products. The method has more lasting antibacterial effect and good washing fastness, but has large processing difficulty and high requirement on antibacterial agent; the other method is to add an antibacterial agent in the finishing process after the textile is printed and dyed to prepare various antibacterial textiles. The method is simpler than the processing technology, but also has the problems of poor durability of the antibacterial effect and poor washability. The existing antibacterial agents mainly comprise antibiotics, metals and salts thereof, quaternary ammonium salts, halogen amines and the like. But also has the problems of weak antibacterial effect and poor washing fastness, and also has the risks of toxicity, skin irritation and drug resistance caused by the release of the antibacterial agent. Therefore, the development of a novel, more stable, efficient and safe preparation method of the antibacterial textile has important significance.
Disclosure of Invention
The invention aims to solve the technical problem in the prior art and provides an antibacterial natural textile material with a surface modified with borneol, which can effectively inhibit the adhesion of bacteria and fungi for a long time, has a stable structure, is washable, has no irritation and toxicity to skin and can not cause drug resistance.
The invention also provides a preparation method of the antibacterial natural textile material, which utilizes a new antibacterial strategy of surface stereochemistry, has mild reaction conditions and simple preparation method, and can be widely applied to industries of medical treatment, sanitation, environmental protection, clothing and the like.
To this end, the present invention provides, in a first aspect, an antibacterial natural textile material surface-modified with borneol, which is composed of an aminosiloxane-coupled natural textile material and a 4-aldehyde benzoic acid borneol derivative.
According to the invention, the configuration of the 4-aldehyde benzoic acid borneol derivative comprises D-borneol, L-borneol and Iso-one or more of borneol.
In some embodiments of the present invention, the molecular structural formula of the 4-aldehyde benzoic acid borneol derivative is shown as formula (I):
in the invention, the aminosiloxane comprises one or more of 3-aminopropyl triethoxy siloxane, 3-aminopropyl trimethoxy siloxane and 4-aminobutyl triethoxy siloxane; optionally, in the antibacterial natural textile material with the surface modified borneol, the 4-aldehyde benzoic acid borneol derivative is modified on the surface of the natural textile material coupled with the aminosiloxane through Schiff base reaction.
According to the present invention, the antibacterial natural textile material is capable of inhibiting or preventing adhesion of microorganisms to the surface thereof.
In some embodiments of the invention, the microorganism comprises a bacterium and/or a fungus.
In some embodiments of the invention, the natural textile material comprises one or more of a cotton fiber material, a cotton fiber textile material, a hemp fiber textile material, a bamboo fiber material and a bamboo fiber textile material.
The second aspect of the present invention provides a method for preparing an antibacterial natural textile material with surface modified borneol, comprising:
step B, placing the natural textile material in amino siloxane finishing liquid for soaking treatment, then taking out, heating, washing and airing to obtain the natural textile material with the surface modified with amino silane groups;
and step C, placing the natural textile material with the surface modified with the aminosilane group into 4-aldehyde benzoic acid borneol derivative finishing liquid for soaking treatment, and then washing and airing to prepare the antibacterial natural textile material with the surface modified with the borneol.
According to the method of the invention, the aminosiloxane finishing liquor is formed by dissolving aminosiloxane in I organic solvent.
In some embodiments of the invention, the I organic solvent comprises toluene and/or acetone.
In the invention, the aminosilicone comprises one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and 4-aminobutyltriethoxysilane.
In some embodiments of the invention, the aminosiloxane content of the aminosiloxane finishing liquid is from 5 to 15 vol%.
According to the method, the 4-aldehyde benzoic acid borneol derivative finishing liquid is formed by dissolving 4-aldehyde benzoic acid borneol derivative in a II organic solvent.
In some embodiments of the present invention, the 1I organic solvent comprises one or more of ethanol, methanol and acetone.
In the invention, the configuration of the 4-aldehyde benzoic acid borneol derivative comprises D-borneol, L-borneol and Iso-one or more of borneol.
In some embodiments of the invention, the content of the 4-aldehyde benzoic acid borneol derivative in the 4-aldehyde benzoic acid borneol derivative finishing liquid is 0.01-0.05 g/mL.
According to the method of the invention, in step B, the temperature of the soaking treatment is room temperature.
In some embodiments of the present invention, in step B, the soaking time is 10-60 min.
In some embodiments of the invention, in step B, the temperature of the heating is 50 to 100 ℃.
In some embodiments of the invention, in step B, the heating time is 0.5 to 3 hours.
According to the method of the invention, in step C, the temperature of the soaking treatment is room temperature.
In some embodiments of the present invention, in step C, the soaking treatment time is 1 to 3 hours.
In a third aspect, the present invention provides the use of an antibacterial natural textile material surface-modified borneol according to the first aspect of the present invention or an antibacterial natural textile material surface-modified borneol prepared according to the method of the second aspect of the present invention in the preparation of an antibacterial natural textile product.
In some embodiments of the invention, the natural textile material comprises one or more of a cotton fiber material, a cotton fiber textile material, a hemp fiber textile material, a bamboo fiber material and a bamboo fiber textile material.
The antibacterial natural textile material with the surface modified with the borneol is prepared by modifying a natural textile material by amino siloxane to expose active amino on the surface, and then modifying the 4-aldehyde benzoic acid borneol derivative by reacting with Schiff base of the amino on the surface. The 4-aldehyde benzoic acid borneol derivative is modified on the surface of the natural textile material modified by amino silane, so that the natural textile material can effectively inhibit the adhesion of bacteria and fungi, and the aim of antibacterial protection of the natural textile material is fulfilled.
The antibacterial natural textile material with the surface modified borneol provided by the invention is a novel antibacterial natural textile material prepared by utilizing a new antibacterial strategy of surface stereochemistry, and the Schiff base reaction condition in the preparation method is mild, and the preparation process is simple.
The antibacterial natural textile material with the surface modified borneol provided by the invention is a non-release antibacterial textile material, does not release a bactericide to kill microorganisms, but influences the adhesion of the microorganisms through the surface stereochemical structure of the material, can ensure the use safety, does not cause skin irritation and sensitization, and does not damage the self-existing flora of the skin; meanwhile, the material has good anti-adhesion effect on bacteria and fungi, can effectively inhibit the adhesion of the bacteria and the fungi for a long time, has a stable structure and is resistant to water washing, the anti-bacterial adhesion rate is more than 95 percent, the anti-fungus durability is longer than 30 days, and the material is resistant to 50 times of mechanical water washing. Therefore, the antibacterial natural textile material with the surface modified borneol provided by the invention is a novel safe, stable and environment-friendly antibacterial natural textile, and can be widely applied to industries such as medical treatment, sanitation, environmental protection and clothes.
Drawings
The invention is described in further detail below with reference to the attached drawing figures:
FIG. 1 is a schematic diagram of a reaction process for preparing a natural textile material modified with aminosilane groups on the surface.
FIG. 2 is a reaction process diagram of preparing the antibacterial natural textile material with surface modified borneol as shown in formula (II).
FIG. 3 is a schematic diagram of a reaction process for preparing the 4-aldehyde benzoic acid borneol derivative.
Fig. 4 is a control group: blank cotton fabric and experimental group: and comparing the plate counting results of the number of bacteria adhered to the surface of the cotton fabric after the borneol modification with the plate counting results.
Fig. 5 is a control group: blank cotton fabric and aminosilicone modified cotton fabric, experimental group: and (5) a macroscopic antifungal adhesion effect graph of the modified cotton fabric by the borneol (cultured for 30 days).
Fig. 6 shows the control group: blank cotton fabric and experimental group: and (5) making a rabbit back skin picture after the borneol is used for modifying the cotton fabric.
FIG. 7 is a graph showing the antifungal adhesion effect of borneol modified cotton fabric after 50 times of circulating water washing (30 days of culture).
Detailed Description
In order that the invention may be readily understood, a detailed description of the invention is provided below. However, before the invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Where a range of values is provided, it is understood that each intervening value, to the extent that there is no stated or intervening value in that stated range, to the extent that there is no such intervening value, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where a specified range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.
Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
I. Term(s) for
The term "textile material" as used herein refers to fibers and fibrous articles, including fibers, yarns, fabrics, composites thereof, and the like.
The term "textile" as used herein refers to a fibrous product, a product made by processing and weaving textile fibers, including fabrics (e.g., cloth, knit, etc.) and composites thereof with fibers and/or yarns.
The term "scouring" in the present invention is to remove impurities from the fabric by using caustic soda and other scouring aids to perform chemical degradation reaction or emulsification, swelling and the like with pectin, waxy substances, nitrogen-containing substances, cottonseed hulls and the like, and washing with water.
The term "water" as used herein means deionized water, ultrapure water or distilled water unless otherwise specified.
The term "optional" or "optionally" as used herein means that an optional ingredient may or may not be added.
Embodiments of
As mentioned above, some of the existing methods for preparing antibacterial textiles are to add antibacterial agents into textile raw materials to prepare antibacterial fibers, and then to weave various antibacterial fabric products, and the method has high processing difficulty and high requirement on antibacterial agents; some antibacterial agents are added in the finishing process after the textile is printed and dyed to prepare various antibacterial textiles. The method has the problems of poor durability of the antibacterial effect and poor washability. The existing antibacterial agents have the problems of non-lasting antibacterial effect and poor washability, and also have the risks of toxicity, skin irritation and drug resistance caused by the release of the antibacterial agents. In view of this, the present inventors have conducted extensive studies on antibacterial natural textile materials.
The inventor researches and discovers that an antibacterial natural textile material can be prepared by a novel antibacterial strategy of surface stereochemistry through an aminosiloxane-coupled natural textile material and a 4-aldehyde benzoic acid borneol derivative, the material is a non-release antibacterial textile material, a bactericide cannot be released to kill microorganisms, the adhesion of the microorganisms is influenced through the surface stereochemistry structure of the material, the skin irritation and sensitization cannot be caused, and the self flora of the skin cannot be damaged; the material can effectively inhibit the adhesion of bacteria and fungi for a long time, has a stable structure, is washable, has no toxicity, and can not cause drug resistance. The present invention has been made based on the above findings.
Therefore, the antibacterial natural textile material with the surface modified borneol according to the first aspect of the invention is formed by coupling the natural textile material with aminosiloxane and the 4-aldehyde benzoic acid borneol derivative.
In the invention, the 4-aldehyde benzoic acid borneol derivative is 4-aldehyde benzoic acid borneol ester formed by combining 4-aldehyde benzoic acid and borneol through ester bond, and the molecular structural formula is shown as the formula (I):
the structure of the borneol for forming the 4-aldehyde bornyl benzoate comprises D-borneol, L-borneol and Iso-borneol.
It should be understood by those skilled in the art that the antibacterial natural textile material with surface modified borneol in the invention is prepared by using aminosiloxane as a coupling agent, grafting the aminosiloxane to the surface of the natural textile material with hydroxyl on the surface through hydrolysis condensation to endow the surface with amino, and modifying the 4-aldehyde benzoic acid borneol derivative to the surface of the textile material with amino through Schiff base reaction, and the prepared antibacterial natural textile material also has the following characteristics:
(1) the configuration of the 4-aldehyde benzoic acid borneol derivative used for forming the antibacterial natural textile material comprises D-borneol, L-borneol and Iso-one or more of borneol.
(2) The aminosilicone used for constituting the antibacterial natural textile material in the present invention includes one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and 4-aminobutyltriethoxysilane.
(3) In the antibacterial natural textile material with the surface modified with the borneol, the 4-aldehyde benzoic acid borneol derivative is modified on the surface of the natural textile material coupled with the aminosiloxane through Schiff base reaction.
In some embodiments of the present invention, for example, the molecular structure of the antibacterial natural textile material is represented by formula (II):
it should be understood by those skilled in the art that the antibacterial natural textile material represented by the formula (II) is only one specific example provided for easy understanding, and the structural formula of the antibacterial natural textile material of the present invention is not limited thereto.
In the present invention, the antibacterial natural textile material is capable of inhibiting or preventing microorganisms from adhering to its surface; the microorganism includes bacteria and/or fungi, including but not limited to Escherichia coli, Staphylococcus aureus, Aspergillus and Mucor one or more.
In some embodiments of the invention, the natural textile material comprises one or more of a cotton fiber material, a cotton fiber textile material, a hemp fiber textile material, a bamboo fiber material and a bamboo fiber textile material.
The preparation method of the antibacterial natural textile material with the surface modified with the borneol comprises the steps of exposing active amino on the surface of the natural textile material modified with the aminosiloxane, and then modifying the 4-aldehyde benzoic acid borneol derivative through the Schiff base reaction with the surface amino to obtain the antibacterial natural textile material with the surface modified with the borneol, wherein the preparation method comprises the following specific steps:
step B, placing the natural textile material in amino siloxane finishing liquid for soaking treatment, then taking out, heating, washing and airing to obtain the natural textile material with the surface modified with amino silane groups;
and step C, placing the natural textile material with the surface modified with the aminosilane group into 4-aldehyde benzoic acid borneol derivative finishing liquid for soaking treatment, and then washing and airing to prepare the antibacterial natural textile material with the surface modified with the borneol.
In the step B:
(1) the amino siloxane finishing liquid is formed by dissolving amino siloxane in an organic solvent I. Wherein the I organic solvent comprises toluene and/or acetone; the aminosilicone comprises one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and 4-aminobutyltriethoxysilane.
(2) In some embodiments of the invention, the aminosiloxane content of the aminosiloxane finishing liquid is from 5 to 15 vol%.
(3) The temperature of the soaking treatment is room temperature; the soaking time is 10-60 min.
(4) The heating temperature is 50-100 ℃; the heating time is 0.5-3 h.
In the step C:
(1) the finishing liquid of the 4-aldehyde benzoic acid borneol derivative is formed by dissolving the 4-aldehyde benzoic acid borneol derivative in a II organic solvent. Wherein, the II organic solvent comprises one or more of ethanol, methanol and acetone; the 4-aldehyde benzoic acid borneol derivative has the configuration comprising D-borneol, L-borneol and Iso-one or more of borneol.
(2) The content of the 4-aldehyde benzoic acid borneol derivative in the 4-aldehyde benzoic acid borneol derivative finishing liquid is 0.01-0.05 g/mL.
(3) The temperature of the soaking treatment is room temperature; the soaking time is 1-3 h.
In some preferred embodiments of the present invention, in step B, the pretreated natural textile material is placed in an aminosiloxane finishing solution for soaking treatment, and then taken out, heated, washed, and dried to obtain a natural textile material with a surface modified with aminosilane groups;
in some further preferred embodiments of the present invention, the method for preparing the antibacterial natural textile material with surface modified borneol according to the present invention further comprises a step of pre-treating the natural textile material. The method for pretreating a natural textile material in the present invention is not particularly limited, and a method for pretreating a natural textile material, which is conventional in the art, may be employed. For example, by a high temperature scouring pre-treatment.
In some embodiments of the present invention, for example, the reaction scheme for preparing a natural textile material modified with aminosilane groups on the surface in step B is shown in fig. 1.
In other embodiments of the present invention, for example, step C, a reaction scheme for preparing the antibacterial natural textile material of the surface-modified borneol of the present invention is shown in fig. 2.
It should be understood by those skilled in the art that the reaction process for preparing the natural textile material having the surface-modified aminosilane group in step B shown in fig. 1, the reaction process for preparing the antibacterial natural textile material having the surface-modified borneol shown in formula (II) shown in fig. 2, and the antibacterial natural textile material having the surface-modified borneol shown in formula (II) are only one specific example provided by the present inventors for easy understanding, and the structural formula of the antibacterial natural textile material having the surface-modified borneol and the reaction process thereof in the present invention are not limited thereto.
In some further specific embodiments of the present invention, the antibacterial natural textile material of the present invention is prepared by the following typical processes:
(1) preparing a natural textile material modified with an aminosilane group on the surface: firstly, soaking a pretreated natural textile material in amino siloxane finishing liquid with the concentration of 5-15 vol% for 10-60min, then taking out the natural textile material, heating the natural textile material for 0.5-2h at the temperature of 50-100 ℃ to promote the formation of covalent bonds, finally thoroughly washing off excessive amino siloxane, and airing to obtain the natural textile material with the surface modified with amino silane groups.
(2) Preparing an antibacterial natural textile material with surface modified borneol: and (2) soaking the natural textile material modified with the aminosilane group on the surface, obtained in the step (1), in 4-aldehyde benzoic acid borneol derivative finishing liquid with the concentration of 0.01-0.05g/mL for 1-3h at room temperature. And finally, thoroughly washing off excessive unbound 4-aldehyde benzoic acid borneol derivatives, and airing to obtain the antibacterial natural textile material with the surface modified with borneol.
The aminosilicones described in the preferred method of carrying out the invention include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and 4-aminobutyltriethoxysilane.
The solvents used for the aminosiloxane finishing liquor described in the preferred method of carrying out the invention include toluene and acetone.
The solvents used in the finishing liquor of the 4-aldehyde bornyl benzoate derivative in the preferred method of the invention include ethanol, methanol and acetone.
The reaction scheme for preparing the 4-aldehyde bornyl benzoate in the invention is shown in figure 3. The preparation method comprises the following steps:
in some examples, 1.6mmol 4-aldehyde benzoic acid was weighed into a reaction flask and added to a solvent environment provided by 30mL methylene chloride. Then, 0.2mmol of 4-Dimethylaminopyridine (DMAP) and 2.0mmol of Dicyclohexylcarbodiimide (DCC) are sequentially added into the mixture, after complete dissolution, 1mmol of borneol is added into the system, reaction is continuously carried out for 12 hours at room temperature, a crude product is collected after the reaction is stopped, the crude product is sequentially subjected to vacuum filtration and petroleum ether sedimentation under reduced pressure, and finally, a target product, namely the 4-aldehyde bornyl benzoate is obtained through post-treatment steps of column chromatography, vacuum drying and the like, wherein the yield is 95%. The reaction has the advantages of mild conditions and simple operation.
In the reaction shown in FIG. 3, the borneol comprises D-borneol, L-borneol and Iso-one or more of borneol.
The use of a surface modified borneol antimicrobial natural textile material according to the first aspect of the invention or prepared according to the second aspect of the invention in the preparation of an antimicrobial natural textile product according to the third aspect of the invention.
In some embodiments of the invention, the natural textile material comprises one or more of a cotton fiber material, a cotton fiber textile material, a hemp fiber textile material, a bamboo fiber material and a bamboo fiber textile material.
In the present invention, the antibacterial natural textile material is capable of inhibiting or preventing microorganisms from adhering to its surface; the microorganism includes bacteria and/or fungi, including but not limited to Escherichia coli, Staphylococcus aureus, Aspergillus and Mucor one or more.
The bacteriostasis or antibiosis test method of the invention is as follows:
antifungal experiments: blank natural textile materials (e.g., cotton fabric), aminosilicone-modified natural textile materials (e.g., cotton fabric) and borneol-modified natural textile materials (e.g., cotton fabric) were cut into circular samples with a diameter of 15.0 + -0.1 mm, sterilized by ultraviolet irradiation for 20min, and then flatly attached on malt extract agar medium. Then, 10. mu.L of the fungal solution was dropped on the center, incubated at a constant temperature of 30 ℃ and the growth of the fungus around the material was observed and recorded by a camera at different times.
Antibacterial experiments: immersing a blank natural textile material (e.g., cotton fabric) and a modified natural textile material (e.g., cotton fabric) in 107CFU·mL-1The bacterial suspension of (2) was allowed to act at 37 ℃ for 4 hours. Then, the material is washed three times with sterile physiological saline, after physically adsorbed bacteria are washed away, the bacteria firmly adhered to the surface of the material are washed away by ultrasonic waves and dispersed in the sterile physiological saline. Finally, 100. mu.L of the dispersion was applied to nutrient agar medium, incubated at 37 ℃ for 24 hours, and plated colonies were counted to calculate the anti-bacterial adhesion rate according to formula (III):
R(％)＝(A-B)/A×100％ (III)
in the formula (III):
r-antibacterial adhesion rate of the sample;
a-surface bacteria adhesion quantity (CFU/mL) after a blank natural textile material (such as cotton fabric) is acted with a bacterium solution for 4 hours;
and B, allowing the modified natural textile material (such as cotton fabric) of the borneol to act on the bacteria liquid for 4 hours, and then, allowing the bacteria on the surface to adhere to the surface (CFU/mL).
Example III
The present invention will be specifically described below with reference to specific examples. The experimental methods described below are, unless otherwise specified, all routine laboratory procedures. The experimental materials described below, unless otherwise specified, are commercially available.
Example 1:
soaking the pretreated cotton textile in 10 vol% acetone solution of 3-aminopropyltriethoxysilane for 10min, taking out, heating at 50 deg.C for 2h to promote formation of covalent bond, thoroughly washing off excess aminosilane with acetone, and air drying to obtain aminosilane-modified cotton textile. Then soaking the mixture in 0.02g/mL ethanol solution of D-borneol derivative at room temperature for 1 h. And finally, completely washing excessive unbound borneol derivatives with ethanol, and airing to obtain the borneol modified cotton textile. The antibacterial adhesion rate is more than 90%, and the antifungal effect is more than 25 days (adopting experimental strains such as escherichia coli, staphylococcus aureus, aspergillus, mucor and the like).
Example 2:
soaking the pretreated cotton textile in 10 vol% acetone solution of 3-aminopropyltrimethoxysilane for 10min, taking out, heating at 60 ℃ for 2h to promote formation of covalent bonds, finally thoroughly washing off excess aminosilane with acetone, and airing to obtain the aminosilane-modified cotton textile. Then soaking the mixture in 0.02g/mL ethanol solution of L-borneol derivative at room temperature for 2 h. And finally, completely washing excessive unbound borneol derivatives with ethanol, and airing to obtain the borneol modified cotton textile. The antibacterial adhesion rate is more than 90%, and the antifungal effect is more than 25 days (adopting experimental strains such as escherichia coli, staphylococcus aureus, aspergillus, mucor and the like).
Example 3:
soaking the pretreated cotton textile in 5 vol% 3-aminopropyltriethoxysilane toluene solution for 20min, taking out, heating at 70 ℃ for 1h to promote formation of covalent bonds, thoroughly washing off excess aminosilane with toluene, and air drying to obtain the aminosilane-modified cotton textile. Then soaking the mixture in a methanol solution of a D-borneol derivative with the concentration of 0.01g/mL for 2 hours at room temperature. And finally, thoroughly washing excessive unbound borneol derivatives with methanol, and airing to obtain the borneol modified cotton textile. The antibacterial adhesion rate is more than 90%, and the antifungal effect is more than 25 days (adopting experimental strains such as escherichia coli, staphylococcus aureus, aspergillus, mucor and the like).
Example 4:
soaking the pretreated cotton textile in 5 vol% 3-aminopropyltrimethoxysilane toluene solution for 20min, taking out, heating at 80 ℃ for 1h to promote formation of covalent bonds, finally thoroughly washing off excessive aminosilane by toluene, and airing to obtain the aminosilane-modified cotton textile. Then soaking the mixture in 0.01g/mL methanol solution of L-borneol derivative at room temperature for 2 h. And finally, thoroughly washing excessive unbound borneol derivatives with methanol, and airing to obtain the borneol modified cotton textile. The antibacterial adhesion rate is more than 90%, and the antifungal effect is more than 25 days (adopting experimental strains such as escherichia coli, staphylococcus aureus, aspergillus, mucor and the like).
Example 5:
soaking the pretreated cotton textile in an acetone solution of 4-aminobutyltriethoxysilane with the concentration of 15 vol% for 30min, taking out, heating for 0.5h at 100 ℃ to promote the formation of covalent bonds, finally thoroughly washing off excessive aminosilane by acetone, and airing to obtain the aminosilane-modified cotton textile. Then, the mixture was soaked in an acetone solution of the Iso-borneol derivative with a concentration of 0.05g/mL for 3 hours at room temperature. And finally, thoroughly washing excess unbound borneol derivatives with acetone, and airing to obtain the borneol modified cotton textile. The antibacterial adhesion rate is more than 95% (figure 4), and the antifungal effect is more than 30 days (figure 5) (experimental strains are adopted, such as escherichia coli, staphylococcus aureus, aspergillus, mucor, and the like).
Example 6:
soaking the pretreated cotton textile in acetone solution of 3-aminopropyltrimethoxysilane with the concentration of 15 vol% for 30min, then taking out and heating for 1h at 100 ℃ to promote the formation of covalent bonds, finally thoroughly washing off excessive aminosilane by acetone, and airing to obtain the aminosilane-modified cotton textile. Then soaking the mixture in an acetone solution of a D-borneol derivative with the concentration of 0.05g/mL for 3 hours at room temperature. And finally, thoroughly washing excess unbound borneol derivatives with acetone, and airing to obtain the borneol modified cotton textile. The antibacterial adhesion rate is more than 95%, and the antifungal effect is more than 30 days (experimental strains are adopted, such as escherichia coli, staphylococcus aureus, aspergillus, mucor and the like).
Example 7:
soaking the pretreated cotton textile in acetone solution of 3-aminopropyltriethoxysilane with the concentration of 15 vol% for 40min, taking out, heating for 0.5h at 80 ℃ to promote the formation of covalent bonds, finally thoroughly washing off excessive aminosilane by acetone, and airing to obtain the aminosilane-modified cotton textile. Then soaking the mixture in 0.05g/mL methanol solution of L-borneol derivative at room temperature for 3 h. And finally, thoroughly washing excessive unbound borneol derivatives with methanol, and airing to obtain the borneol modified cotton textile. The antibacterial adhesion rate is more than 95%, and the antifungal effect is more than 30 days (experimental strains are adopted, such as escherichia coli, staphylococcus aureus, aspergillus, mucor and the like).
Example 8:
soaking the pretreated cotton textile in a toluene solution of 4-aminobutyltriethoxysilane with the concentration of 15 vol% for 40min, taking out, heating for 1h at 90 ℃ to promote the formation of covalent bonds, finally thoroughly washing off excessive aminosilane by toluene, and airing to obtain the aminosilane-modified cotton textile. Then, the mixture was soaked in a methanol solution of the Iso-borneol derivative with a concentration of 0.05g/mL for 3 hours at room temperature. And finally, thoroughly washing excessive unbound borneol derivatives with methanol, and airing to obtain the borneol modified cotton textile. The antibacterial adhesion rate is more than 95%, and the antifungal effect is more than 30 days (experimental strains are adopted, such as escherichia coli, staphylococcus aureus, aspergillus, mucor and the like).
Example 9:
soaking the pretreated cotton textile in a toluene solution of 4-aminobutyltriethoxysilane with the concentration of 15 vol% for 60min, taking out, heating for 1h at 100 ℃ to promote the formation of covalent bonds, finally thoroughly washing off excessive aminosilane by toluene, and airing to obtain the aminosilane-modified cotton textile. Then soaking the mixture in 0.05g/mL ethanol solution of L-borneol derivative at room temperature for 3 h. And finally, completely washing excessive unbound borneol derivatives with ethanol, and airing to obtain the borneol modified cotton textile. The antibacterial adhesion rate is more than 95%, and the antifungal effect is more than 30 days (experimental strains are adopted, such as escherichia coli, staphylococcus aureus, aspergillus, mucor and the like).
Example 10:
soaking the pretreated cotton textile in 10 vol% acetone solution of 4-aminobutyltriethoxysilane for 60min, taking out, heating at 100 deg.C for 3h to promote formation of covalent bond, thoroughly washing off excess aminosilane with acetone, and air drying to obtain the final product. Then soaking the mixture in 0.05g/mL ethanol solution of D-borneol derivative at room temperature for 3 h. And finally, completely washing excessive unbound borneol derivatives with ethanol, and airing to obtain the borneol modified cotton textile. The antibacterial adhesion rate is more than 95%, and the antifungal effect is more than 30 days (experimental strains are adopted, such as escherichia coli, staphylococcus aureus, aspergillus, mucor and the like). After the blank cotton fabric and the borneol modified cotton fabric are acted on the back skin of the shaved rabbit for 6h, the back skin is observed for 24h, and then a picture is taken, as shown in figure 6, the skin surface has no skin irritation and sensitization phenomena such as scabbing, red swelling and the like. Meanwhile, after the cotton fabric modified by the borneol is washed by 50 times of circulating water, the antifungal adhesion can still be maintained for 30 days (figure 7).
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (14)
1. An antibacterial natural textile material with surface modified borneol is composed of an aminosiloxane coupled natural textile material and a 4-aldehyde benzoic acid borneol derivative; the configuration of the 4-aldehyde benzoic acid borneol derivative comprises one or more of D-borneol, L-borneol and Iso-borneol; the molecular structural formula of the 4-aldehyde benzoic acid borneol derivative is shown as the formula (I):
2. the antibacterial natural textile material according to claim 1, wherein the aminosilicone comprises one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and 4-aminobutyltriethoxysilane.
3. The antibacterial natural textile material according to claim 2, wherein in the antibacterial natural textile material surface-modified with borneol, the 4-aldehyde benzoic acid borneol derivative is modified to the surface of the aminosiloxane-coupled natural textile material by schiff base reaction.
4. The antimicrobial natural textile material of any one of claims 1-3, wherein the antimicrobial natural textile material is capable of inhibiting or preventing the adhesion of microorganisms to its surface, wherein the microorganisms comprise bacteria and/or fungi; and/or the natural textile material comprises one or more of a cotton fiber material, a cotton fiber textile material, a hemp fiber textile material, a bamboo fiber material and a bamboo fiber textile material.
5. A method for preparing the antibacterial natural textile material of surface-modified borneol according to any one of claims 1 to 4, which comprises:
step B, placing the natural textile material in amino siloxane finishing liquid for soaking treatment, then taking out, heating, washing and airing to obtain the natural textile material with the surface modified with amino silane groups;
and step C, placing the natural textile material with the surface modified with the aminosilane group into 4-aldehyde benzoic acid borneol derivative finishing liquid for soaking treatment, and then washing and airing to prepare the antibacterial natural textile material with the surface modified with the borneol.
6. The preparation method according to claim 5, wherein the aminosiloxane finishing liquid is formed by dissolving aminosiloxane in I organic solvent; wherein the I organic solvent comprises toluene and/or acetone; and/or the aminosilicone comprises one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and 4-aminobutyltriethoxysilane.
7. A method of producing as claimed in claim 6 wherein the aminosiloxane finishing liquor has an aminosiloxane content of 5-15vo 1%.
8. The preparation method of claim 5, wherein the 4-aldehyde bornyl benzoate derivative finishing liquid is formed by dissolving a 4-aldehyde bornyl benzoate derivative in a II organic solvent; wherein, the II organic solvent comprises one or more of ethanol, methanol and acetone; and/or the configuration of the 4-aldehyde benzoic acid borneol derivative comprises one or more of D-borneol, L-borneol and Iso-borneol.
9. The production method according to claim 8, wherein the content of the 4-aldehyde benzoic acid borneol derivative in the 4-aldehyde benzoic acid borneol derivative finishing liquid is 0.01-0.05 g/mL.
10. The method according to any one of claims 5 to 9, wherein in step B, the temperature of the soaking treatment is room temperature, the time of the soaking treatment is 10 to 60min, the temperature of heating is 50 to 100 ℃, and the time of heating is 0.5 to 3 h.
11. The method according to any one of claims 5 to 9, wherein in step C, the temperature of the soaking treatment is room temperature, and the time of the soaking treatment is 1 to 3 hours.
12. The method according to claim 10, wherein in the step C, the temperature of the soaking treatment is room temperature, and the time of the soaking treatment is 1 to 3 hours.
13. Use of the antibacterial natural textile material of surface-modified borneol according to any one of claims 1 to 4 or the antibacterial natural textile material of surface-modified borneol prepared by the method according to any one of claims 5 to 12 for the preparation of antibacterial natural textile products.
14. The use according to claim 13, wherein the natural textile material comprises one or more of a cotton fiber material, a cotton fiber textile material, a hemp fiber textile material, a bamboo fiber material and a bamboo fiber textile material.
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| CN111041828A (en) * | 2019-11-29 | 2020-04-21 | 曾艳清 | Lasting antibacterial polypropylene non-woven fabric and preparation method thereof |
| CN113881086B (en) * | 2020-06-17 | 2023-01-24 | 北京化工大学 | Application of non-release antimicrobial adhesion coating in antibacterial building material |
| CN113817198B (en) * | 2020-06-17 | 2023-05-02 | 湖南宝升塑业科技开发有限公司 | Use of non-releasing antimicrobial adhesive coating in antimicrobial feeding bottles |
| CN113979894B (en) * | 2021-11-16 | 2023-06-23 | 北京工商大学 | Safe durable antibacterial natural textile material and preparation method thereof |
| CN115821588A (en) * | 2022-12-13 | 2023-03-21 | 周权有 | Fabric finishing agent for modal fabric and finishing method |
| CN115975242A (en) * | 2023-01-19 | 2023-04-18 | 北京化工大学 | Biocompatible sterilization anti-adhesion PET material and preparation method and application thereof |
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| CN103255543A (en) * | 2013-05-06 | 2013-08-21 | 浙江大学 | Method for preparing borneol synthetic fiber anti-mosquito functional fabric |
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