CN117127409A - Preparation method of multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent - Google Patents

Preparation method of multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent Download PDF

Info

Publication number
CN117127409A
CN117127409A CN202310931522.2A CN202310931522A CN117127409A CN 117127409 A CN117127409 A CN 117127409A CN 202310931522 A CN202310931522 A CN 202310931522A CN 117127409 A CN117127409 A CN 117127409A
Authority
CN
China
Prior art keywords
fabric
antibacterial
durable
self
polyurethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310931522.2A
Other languages
Chinese (zh)
Inventor
张庆华
张甜丽
刘权
詹晓力
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Quzhou Research Institute of Zhejiang University
Original Assignee
Quzhou Research Institute of Zhejiang University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Quzhou Research Institute of Zhejiang University filed Critical Quzhou Research Institute of Zhejiang University
Priority to CN202310931522.2A priority Critical patent/CN117127409A/en
Publication of CN117127409A publication Critical patent/CN117127409A/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
    • D06M11/65—Salts of oxyacids of nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/252—Mercaptans, thiophenols, sulfides or polysulfides, e.g. mercapto acetic acid; Sulfonium compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/01—Stain or soil resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Biochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a preparation method of a multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent. The method is an organosilicon aqueous polyurethane fabric coating material modified by isocyanate, polysiloxane, polyether, an antibacterial agent and a self-healing agent, and the preparation method is simple and environment-friendly and accords with the theme of green development. The invention provides application of the antibacterial self-repairing durable fabric, and the invention achieves the technical effects: the modified fabric has excellent hydrophobic static contact angle which can reach 143 degrees, can restore the surface hydrophobicity after being worn and placed for 2 hours at room temperature, can bear multiple washing environments while being efficient and antibacterial, can meet the daily application requirements of the fabric, widens the application scene, and is a fabric coating material with wide application prospect.

Description

Preparation method of multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent
Technical Field
The invention belongs to the technical field of fabric coating materials, and particularly relates to a preparation method of a multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent.
Background
In practical application, the fabric is endowed with various functions such as hydrophobic, antifouling, self-cleaning, self-repairing, antibacterial, durable and the like, and more importantly, the environment-friendly and nontoxic coating material prepared by a simple process meets the production requirements of the modern textile industry. Water-based paints have become a promising alternative to traditional solvent-based paints due to their environmental protection and ease of application.
Because the fabric is inevitably worn or scratched in the daily use process, the wear of the fabric is mainly characterized by breakage, quality loss, appearance discoloration, pilling and fuzzing and the like on the aspect of morphological change, and the service life of the fabric is affected to different degrees. Therefore, the preparation of the fabric coating material with the self-repairing function can effectively solve the problem and realize the long-term durability of the hydrophobic surface. There are two main methods of self-repair: the first is external repair, a special medicament is embedded as a self-healing agent to repair the material part damaged by external force, and the second is internal self-repair, namely the material stimulated by external factors is self-repaired by utilizing the self structural characteristics of the material. Although various methods for realizing the self-repairing function have been designed at present, the problems of long self-repairing time and low efficiency often occur, and the realization of the self-repairing needs a certain temperature or other external stimulus, which is very inconvenient for daily use of the fabric.
Antibacterial fabrics are attracting attention due to their importance and indispensable nature in many fields of medicine, hygiene, hospitals, etc. Antibacterial fabrics can inhibit the growth of bacteria and microorganisms and even kill them to reduce the spread of infectious diseases. At present, various antibacterial agents such as metal and oxide nanoparticles, nano composite particles, antibacterial cationic polymers, chitosan and other natural antibacterial agents are approved to be applied to fabrics to eliminate the threat of bacterial microorganisms and the like to human health, and can damage the membrane structure of the microorganisms, so that the internal components of cells leak to kill the microorganisms. Despite considerable progress in the development of antimicrobial fabrics in recent years, one challenge facing this field is that the antimicrobial ability of the antimicrobial agent on the fabric may gradually decrease after a period of use, wherein living and killed dead bacteria may adhere to the fabric to form a biofilm that is difficult to remove.
Most of the functional fabrics in the current market are single in function, and cannot meet the increasing demands of the modern textile industry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method of a multifunctional water-repellent antibacterial durable organic silicon polyurethane fabric treating agent, and the preparation scheme of the fabric coating is simple, convenient, environment-friendly and universal. The problem of the function singleization of the existing fabric can be solved, the self-repairing efficiency based on dynamic reversible covalent bonds is high, the service life of the fabric is prolonged, the antibacterial component is grafted into the polymer, the leaching of the antibacterial agent can be avoided, and the antibacterial capability can be maintained for a long time and efficiently. The preparation method comprises the following specific steps:
(1) Pre-preparing prepolymer aqueous polyurethane: mixing polysiloxane, polyether and isocyanate in solvent, T 1 Cooling reflux stirring time at temperature is h 1 ；
(2) Preparation of organosilicon aqueous polyurethane emulsion: adding an antibacterial agent and a self-healing agent into the organosilicon polyurethane prepolymer in the solution prepared in the step (1) to continue T 1 Cooling and refluxing at the temperature, and stirring for h 2 Spin-evaporating to remove solvent, and cooling to T 2 Adding water to emulsify and disperse to obtain emulsion;
(3) Curing of silicone aqueous polyurethane emulsion on fabric: treating the clean fabric with the solution prepared in step (2) at a high temperature T 3 Lower drying and curing time is h 3 Obtaining the hydrophobic antibacterial durable organosilicon polyurethane modified fabric.
Further, the polysiloxane compound in the step (1) is specifically a symmetrical alcohol hydroxyl double-end-capped polydimethylsiloxane compound.
Further, the polyether compound in the step (1) is at least one of polytetrahydrofuran glycol and polycarbonate glycol.
Further, the isocyanate in the step (1) is at least one of hexamethylene diisocyanate, isophorone diisocyanate and xylylene diisocyanate.
Further, the solvent in the step (1) is acetone or tetrahydrofuran.
Further, the temperature T in the step (1) 1 Cooling to 70-80deg.C to T 2 Stirring at 40-60deg.C for a period of time h 1 2-3h.
Further, the antibacterial agent in the step (2) is one of an antibacterial cationic compound, metal and oxide nanoparticles and a natural antibacterial agent.
Further, the self-healing agent in the step (2) is one of other reversible dynamic covalent bond compounds containing hydrogen bonds or disulfide bonds, diels-Alder bonds and the like.
Further, the stirring time h in the step (2) 2 The solid content of the emulsion is 20% -30% after 1-2 h.
Further, the treatment method in the step (3) is to soak or uniformly spray the fabric, and the high temperature T is adopted 3 Drying and curing for a time h of 100-120 DEG C 3 The antibacterial self-repairing durable multifunctional fabric is obtained after 10-30 min.
Further, the fabric is one of cotton cloth, nylon or terylene.
In order to achieve the aim, the invention also provides an application of the antibacterial self-repairing durable organic silicon aqueous polyurethane fabric coating material.
The invention has the beneficial effects that:
(1) The water-based polyurethane fabric coating material adopts water as a solvent, is green and pollution-free in the whole preparation process, avoids using any fluorine-containing compound and higher preparation temperature, reduces the emission of an organic solvent harmful to the environment, and meets the requirement of green development.
(2) The fabric coating material prepared by the invention can be quickly self-repaired at room temperature without external stimulation, and has short healing time and high efficiency.
(3) The addition of the organosilicon to the fabric coating material of the invention exhibits excellent hydrophobic properties and enhances the stain resistance of the fabric without compromising the original breathability and softness of the fabric.
(4) According to the invention, the antibacterial material is grafted in the polymer to avoid leaching of the antibacterial agent, so that the fabric can exert long-term and efficient antibacterial capability.
(5) The antibacterial self-repairing durable organic silicon aqueous polyurethane fabric coating material prepared by the invention can realize a plurality of functional synergistic effects, and can effectively prolong the service life of the fabric and widen the application scene compared with a single functional fabric.
(6) The preparation process does not need an organic solvent, the preparation temperature is lower, the operation is simple, and the cost is low, so that the industrial production is easy.
Drawings
FIG. 1 is a schematic diagram showing the growth of bacteria according to the present invention;
fig. 2 is a picture before and after scratch self-repair according to the present invention.
Detailed Description
The preparation method and the technical scheme of the invention are further described below by combining specific examples. Wherein these are meant to illustrate embodiments of the invention only, and not all embodiments of the invention. Furthermore, those skilled in the art will appreciate that many variations and modifications may be made in the solutions and other matters set forth in the present invention, and that such matters are considered to fall within the scope of the present invention.
The invention relates to an organosilicon aqueous polyurethane fabric coating material modified by isocyanate, polysiloxane, polyether, an antibacterial agent and a self-healing agent, and the preparation method is simple and environment-friendly and accords with the theme of green development. The invention provides application of the antibacterial self-repairing durable fabric, and the invention achieves the technical effects: the modified fabric has excellent hydrophobic static contact angle which can reach 143 degrees, can restore the surface hydrophobicity after being worn and placed for 2 hours at room temperature, can bear multiple washing environments while being efficient and antibacterial, can meet the daily application requirements of the fabric, widens the application scene, and is a fabric coating material with wide application prospect.
Example 1
The preparation method of the antibacterial self-repairing durable organic silicon water-based polyurethane fabric coating material comprises the following specific steps:
step 1 is the preparation of prepolymer organosilicon waterborne polyurethane: the symmetrical alcohol hydroxyl double-end-capped polydimethylsiloxane, polycarbonate diol, hexamethylene diisocyanate and diisobutyltin dilaurate are taken as catalysts to be dissolved in tetrahydrofuran, and are condensed, refluxed and stirred for 3 hours at 8 ℃ with the stirring speed of 250r/min.
Step 2 is preparation of organosilicon aqueous polyurethane emulsion: and (2) adding chitosan serving as an antibacterial substance and 2-hydroxyethyl disulfide into the solution obtained in the step (1) to realize self-repairing, continuously stirring at 75 ℃ for 2 hours, cooling to 50 ℃, and adding water to emulsify to form emulsion with 20% of solid content.
Step 3 is curing of the organosilicon aqueous polyurethane coating on the fabric: selecting clean cotton cloth as a treated fabric, diluting 2g of the organosilicon aqueous polyurethane emulsion prepared in the step 2 by 20 times, soaking the cotton cloth in the diluted solution, and drying and curing for 20min at 100 ℃ to obtain the functional fabric with antibacterial self-repairing durability.
Example 2
The preparation method of the antibacterial self-repairing durable organic silicon water-based polyurethane fabric coating material comprises the following specific steps:
step 1 is the preparation of prepolymer organosilicon waterborne polyurethane: symmetrical alcohol hydroxyl double-end-capped polydimethylsiloxane, polytetrahydrofuran glycol, hexamethylene diisocyanate and diisobutyltin dilaurate are taken as catalysts to be dissolved in tetrahydrofuran, and are condensed, refluxed and stirred for 3 hours at 80 ℃ with the stirring speed of 250r/min.
Step 2 is preparation of organosilicon aqueous polyurethane emulsion: the above-mentionedAgNO is added into the solution in the step 1 3 Self-repairing is realized by the nano particles and the 2-hydroxyethyl disulfide, stirring is continued for 2 hours at 70 ℃, then the temperature is reduced to 50 ℃, and water is added for emulsification to form emulsion with 20 percent of solid content.
Step 3 is curing of the organosilicon aqueous polyurethane coating on the fabric: selecting clean cotton cloth as a treated fabric, diluting 2g of the organosilicon aqueous polyurethane emulsion prepared in the step 2 by 20 times, soaking the cotton cloth in the diluted solution, and drying and curing for 20min at 100 ℃ to obtain the functional fabric with antibacterial self-repairing durability.
Example 3
The preparation method of the antibacterial self-repairing durable organic silicon water-based polyurethane fabric coating material comprises the following specific steps:
step 1 is the preparation of prepolymer organosilicon waterborne polyurethane: symmetrical alcohol hydroxyl double-end-capped polydimethylsiloxane, polytetrahydrofuran glycol, hexamethylene diisocyanate and diisobutyltin dilaurate are taken as catalysts to be dissolved in tetrahydrofuran, and are condensed, refluxed and stirred for 3 hours at 80 ℃ with the stirring speed of 250r/min.
Step 2 is preparation of organosilicon aqueous polyurethane emulsion: 3-dimethylamino-1, 2-propanediol is added into the solution in the step 1 to serve as a cationic chain extender to play an antibacterial role and the 2-hydroxyethyl disulfide is used for realizing self-repairing, stirring is continued at 70 ℃ for 2 hours, then the temperature is reduced to 50 ℃, and water is added to emulsify to form emulsion with 20% of solid content.
Step 3 is curing of the organosilicon aqueous polyurethane coating on the fabric: selecting clean cotton cloth as a treated fabric, diluting 2g of the organosilicon aqueous polyurethane emulsion prepared in the step 2 by 20 times, soaking the cotton cloth in the diluted solution, and drying and curing for 20min at 100 ℃ to obtain the functional fabric with antibacterial self-repairing durability.
Example 4
The preparation method of the antibacterial self-repairing durable organic silicon water-based polyurethane fabric coating material comprises the following specific steps:
step 1 is the preparation of prepolymer organosilicon waterborne polyurethane: symmetrical alcohol hydroxyl double-end-capped polydimethylsiloxane, polytetrahydrofuran glycol, hexamethylene diisocyanate and diisobutyltin dilaurate are taken as catalysts to be dissolved in tetrahydrofuran, and are condensed, refluxed and stirred for 3 hours at 65 ℃ with the stirring speed of 250r/min.
Step 2 is preparation of organosilicon aqueous polyurethane emulsion: 3-dimethylamino-1, 2-propanediol is added into the solution in the step 1 to serve as a cationic chain extender to play an antibacterial role and the 2-hydroxyethyl disulfide is used for realizing self-repairing, stirring is continued at 60 ℃ for 2 hours, then the temperature is reduced to 50 ℃, and water is added to emulsify to form emulsion with 20% of solid content.
Step 3 is curing of the organosilicon aqueous polyurethane coating on the fabric: selecting clean cotton cloth as a treated fabric, diluting 2g of the organosilicon aqueous polyurethane emulsion prepared in the step 2 by 20 times, soaking the cotton cloth in the diluted solution, and drying and curing for 20min at 100 ℃ to obtain the functional fabric with antibacterial self-repairing durability.
Example 5
The preparation method of the antibacterial self-repairing durable organic silicon water-based polyurethane fabric coating material comprises the following specific steps:
step 1 is the preparation of prepolymer organosilicon waterborne polyurethane: symmetrical alcohol hydroxyl double-end-capped polydimethylsiloxane, polytetrahydrofuran glycol, hexamethylene diisocyanate and diisobutyltin dilaurate are taken as catalysts to be dissolved in tetrahydrofuran, and are condensed, refluxed and stirred for 3 hours at 80 ℃ with the stirring speed of 250r/min.
Step 2 is preparation of organosilicon aqueous polyurethane emulsion: 3-dimethylamino-1, 2-propanediol is added into the solution in the step 1 to serve as a cationic chain extender to play an antibacterial role and the self-repairing of the polyethyleneimine is realized, the stirring is continued at 70 ℃ for 2 hours, then the temperature is reduced to 50 ℃, and water is added to emulsify to form emulsion with 20% of solid content.
Step 3 is curing of the organosilicon aqueous polyurethane coating on the fabric: selecting clean cotton cloth as a treated fabric, diluting 2g of the organosilicon aqueous polyurethane emulsion prepared in the step 2 by 20 times, soaking the cotton cloth in the diluted solution, and drying and curing for 20min at 100 ℃ to obtain the functional fabric with antibacterial self-repairing durability.
Comparative example:
the comparative example was clean cotton cloth without any treatment.
The performance test method and the result of the functionalized fabric are as follows:
the antibacterial self-repairing durable organosilicon aqueous polyurethane fabric coating material prepared by the invention is tested for emulsion stability, and the emulsion appearance of examples 1-5 is changed from milky white, opaque to blue light and semitransparent from table 1, so that the prepared emulsion can be stably placed on the basis of not damaging the color of the fabric.
The antibacterial self-repairing durable organic silicon aqueous polyurethane fabric coating material prepared by the invention is tested for antibacterial capability, and escherichia coli and staphylococcus aureus are selected as gram-negative bacteria and gram-positive bacteria representatives to evaluate the antibacterial capability of examples 1-5 and comparative examples. The bacterial suspension was first incubated in a constant temperature shaking incubator at 37℃for 12h, after which the glass sheet coated with the emulsion cured into a gel film was placed in a petri dish containing 20ml of bacterial suspension and incubated at 37℃for 12h. Then 1mL of co-cultured bacterial suspension per sample was aspirated, diluted 1000-fold with sterile water, finally 20uL of diluted bacterial suspension was aspirated and spread evenly on solid medium, and incubated for a further 12h at 37 ℃. The growth of the bacteria was recorded with a camera after incubation as shown in fig. 1 below, indicating that the prepared textile coating material has excellent antibacterial ability against escherichia coli and staphylococcus aureus. The E.coli resistance of example 3 was improved by 96% or more than that of the comparative example, and the Staphylococcus aureus resistance of example 3 was improved by 94% or more than that of the comparative example.
The antibacterial self-repairing durable organosilicon aqueous polyurethane fabric coating material prepared by the invention is tested for hydrophobic capacity, 5 points at different positions are selected on the surface of each fabric to measure water contact angles for reducing errors, then an average value is obtained, the measurement results are shown in table 2, and all examples 1-5 show excellent hydrophobic performance.
The antibacterial self-repairing durable organosilicon aqueous polyurethane fabric coating material prepared by the invention tests the self-repairing capability, and is used for performing abrasion test on the surface of the fabric and observing the change of a contact angle. The fabric was placed on sandpaper and then pulled with a 100g weight at a constant speed over the length of sandpaper (15 cm) with an applied force, and then moved back the same distance back to the start point for a wear cycle. The contact angle values were measured once every 10 wear cycles and the wear test was performed for 50 cycles. After the abrasion test is finished, the fabric is placed in a room temperature environment, the contact angle is measured again after 2 hours, and the obtained data are shown in the following table 3, so that the hydrophobic property of the surface of the fabric can be recovered after the fabric is placed for a period of time at room temperature, and the whole process is free from external stimulation, so that self-repairing is simply and rapidly realized.
The antibacterial self-repairing durable organosilicon aqueous polyurethane fabric coating material prepared by the invention tests the self-repairing capability, and can be used for curing the prepared modified organosilicon polyurethane emulsion on a glass sheet to form a film and carrying out scratch-repairing experiments on the surfaces of different films. A scratch was made on the surface of the coating layer by a blade, and then left at room temperature, and the scratch was observed for self-repair by an optical microscope at intervals, and the healing was as shown in fig. 2.
Table 1 appearance of fabric finishing coating material emulsion
Table 2 hydrophobic ability test data
TABLE 3 New measurement of contact Angle data
Contact angle Example 1 Example 2 Example 3 Example 4 Example 5
Initial initiation 138.983° 139.593° 142.951° 125.035 141.333°
After abrasion 132.378 129.944 129.218 100.766 127.132
After 2 hours at room temperature 140.147 141.74 141.015 124.912 136.342
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the present invention is not limited thereto, but is intended to be covered by any person skilled in the art without inventive changes or substitutions within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope defined by the claims.

Claims (10)

1. The preparation method of the multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent is characterized in that isocyanate, polysiloxane, polyether, antibacterial agent and self-healing agent are used for modifying aqueous polyurethane, and the aqueous polyurethane is coated on fabric to enable the fabric to have the functions of hydrophobicity, antibacterial property, self-repairing and durability.
2. The method for preparing the multifunctional water-repellent antibacterial durable organic silicon polyurethane fabric treating agent as claimed in claim 1, which is characterized by comprising the following steps:
step 1, pre-preparing prepolymer aqueous polyurethane: mixing polysiloxane, polyether and isocyanate in solvent, T 1 Cooling reflux stirring time at temperature is h 1 ；
Step 2, preparing organic silicon aqueous polyurethane emulsion: adding an antibacterial agent and a self-healing agent into the organosilicon polyurethane prepolymer prepared in the step 1 to continue T 1 Cooling and refluxing at the temperature, and stirring for h 2 Spin-evaporating to remove solvent, and cooling to T 2 Adding water after the temperature, emulsifying and dispersing to obtain emulsion;
step 3, curing the organosilicon aqueous polyurethane emulsion on the fabric: treating the clean fabric with the emulsion prepared in step 2 at an elevated temperature T 3 Lower drying and curing time is h 3 Obtaining the hydrophobic antibacterial durable organosilicon polyurethane modified fabric.
3. The method for preparing the multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treatment agent according to claim 2, which is characterized in that the polysiloxane in the step 1 is specifically a symmetrical alcohol hydroxyl double-end-blocked polydimethylsiloxane compound; the polyether is at least one of polytetrahydrofuran glycol and polycarbonate glycol; the isocyanate is at least hexamethylene diisocyanate or isophorone diisocyanateOne of isocyanate and xylylene diisocyanate; the solvent is acetone or tetrahydrofuran; said temperature T 1 Cooling to 70-80deg.C to T 2 Stirring at 40-60deg.C for a period of time h 1 2-3h.
4. The method for preparing a multifunctional water-repellent antimicrobial durable organosilicon polyurethane fabric treatment agent according to claim 2 or 3, wherein the antimicrobial agent in the step 2 is one of an antimicrobial cationic compound, metal and oxide nanoparticles and a natural antimicrobial agent.
5. A method for preparing a multifunctional water repellent antimicrobial durable silicone polyurethane fabric treating agent according to claim 2 or 3, wherein the antimicrobial agent of step 2 is an antimicrobial cationic compound.
6. The method for preparing the multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treatment agent according to claim 4, wherein the self-healing agent in the step 2 is a reversible dynamic covalent bond compound comprising hydrogen bond or disulfide bond and Diels-Alder bond; the stirring time h 2 The solid content of the emulsion is 20% -30% after 1-2 h.
7. The method for preparing the multifunctional water-repellent antibacterial durable organic silicon polyurethane fabric treating agent according to claim 4, wherein the self-healing agent in the step 2 is hydrogen bond or disulfide bond; the stirring time h 2 The solid content of the emulsion is 20% -30% after 1-2 h.
8. The method for preparing the multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent according to claim 2, 6 or 7, wherein the treating method in the step 3 is soaking or uniformly spraying on the fabric, and the method is high-temperature T 3 Drying and curing at 80-110 deg.c for a period of time h 3 The antibacterial self-repairing durable multifunctional fabric is obtained after 10-30 min.
9. The method for preparing the multifunctional water-repellent antibacterial durable organic silicon polyurethane fabric treating agent according to claim 1 or 2, wherein the fabric is one of cotton cloth, nylon or terylene.
10. Use of a multifunctional water repellent antimicrobial durable silicone polyurethane fabric treatment prepared according to the method of any one of claims 1-9, characterized in that: is used for preparing multifunctional clothing fabrics.
CN202310931522.2A 2023-07-27 2023-07-27 Preparation method of multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent Pending CN117127409A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310931522.2A CN117127409A (en) 2023-07-27 2023-07-27 Preparation method of multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310931522.2A CN117127409A (en) 2023-07-27 2023-07-27 Preparation method of multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent

Publications (1)

Publication Number Publication Date
CN117127409A true CN117127409A (en) 2023-11-28

Family

ID=88855557

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310931522.2A Pending CN117127409A (en) 2023-07-27 2023-07-27 Preparation method of multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent

Country Status (1)

Country Link
CN (1) CN117127409A (en)

Similar Documents

Publication Publication Date Title
Cao et al. Guanidine-functionalized cotton fabrics for achieving permanent antibacterial activity without compromising their physicochemical properties and cytocompatibility
KR102179352B1 (en) Eco-friendly antibacterial fabric with waterproof and water-repellent coating and method for manufacturing the same
Gu et al. Non-leaching bactericidal cotton fabrics with well-preserved physical properties, no skin irritation and no toxicity
CN107987570B (en) Nano TiO (titanium dioxide)2In-situ hybridization antibacterial waterproof coating treating agent and preparation method thereof
CN107815871B (en) Preparation method of durable antibacterial fabric
CN108385375A (en) A kind of preparation method of super-hydrophobic antibiotic fabric
CN110306340B (en) Antibacterial natural textile material with surface modified borneol and preparation method and application thereof
Abdelghaffar et al. Functional antibacterial finishing of woolen fabrics using ultrasound technology
WO2012146917A1 (en) Biocide-coated substrate
CN103835124A (en) Silver-carried cotton fabric antibacterial material and preparation method thereof
Muzaffar et al. Study of the UV protective and antibacterial properties of aqueous polyurethane dispersions extended with low molecular weight chitosan
CN111411512B (en) Preparation method of super-hydrophobic fabric and super-hydrophobic fabric
CN111534650A (en) Durable antibacterial soft leather for leather bags and preparation method thereof
CN117127409A (en) Preparation method of multifunctional water-repellent antibacterial durable organosilicon polyurethane fabric treating agent
CN113881005A (en) Polymer, preparation method and application thereof, and substrate coated with polymer on surface
CN111704856B (en) Gamma-polyglutamic acid-polycation compound and preparation method and application thereof
CN112920376A (en) Moisture-absorbing quick-drying water-based antibacterial polyurethane finishing agent and preparation method and application thereof
CN1169488A (en) Anti-bacterial odour-proof and easy-to-remove-dirt fabric, preparation method and products thereof
CN109468847B (en) Super-amphiphobic textile finishing agent and preparation method and application thereof
CN115160485B (en) Preparation method of double-active-center thiazole acrylate copolymer nano microsphere
KR101903896B1 (en) Polyurethane-based UV Absorber
CN115814141A (en) Medical dressing with antibacterial and anti-adhesion functions and preparation method thereof
Zhang et al. Highly Antibacterial and Self-Healing Janus Fabric for Effective Body Moisture/Thermal Management and Durable Waterproof
JPH01197557A (en) Composition for antibacterial treatment
CN1508354A (en) Modified treating agent for fiber and processing and treating method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination