CN-122013591-A - Preparation method of durable antibacterial hydrophobic paper based on combination of intramammary self-assembly and surface photopolymerization

CN122013591ACN 122013591 ACN122013591 ACN 122013591ACN-122013591-A

Abstract

The invention discloses a preparation method of durable antibacterial hydrophobic paper based on combination of intramammary self-assembly and surface photopolymerization. The method comprises the steps of firstly adding nanocellulose into a dispersible solvent and stirring for a period of time to obtain nanocellulose suspension, then dissolving quaternary ammonium salt monomer, organosilane monomer, cross-linking agent and photoinitiator into the polymerizable solvent to obtain quaternary ammonium salt-organosilane solution, then mixing the obtained nanocellulose suspension and the quaternary ammonium salt-organosilane solution, then adding the mixture into paper pulp to obtain special spraying liquid, finally spraying the special spraying liquid on the surface of a substrate, simultaneously irradiating a spraying area with ultraviolet light under a nitrogen atmosphere simultaneously, forming a coating on the surface of the substrate to obtain the substrate with the coating, and finally carrying out specific drying treatment on the substrate with the coating to obtain the durable antibacterial hydrophobic paper. The hydrophobic paper prepared by the method has extremely durable performance and high integration level of the production process.

Inventors

WU MINGBANG
SUN JUNJUN
YANG JING
ZHAO YUTING
CHEN JIAYOU
YAO JUMING

Assignees

浙江理工大学
浙江大胜达包装股份有限公司
现代纺织技术创新中心(鉴湖实验室)

Dates

Publication Date: 20260512
Application Date: 20260409

Claims (10)

1. The preparation method of the durable antibacterial hydrophobic paper based on the combination of intra-pulp self-assembly and surface photopolymerization is characterized by comprising the following steps of: (1) Adding a certain amount of nanocellulose into a dispersible solvent at a certain temperature, and stirring for a period of time to obtain a nanocellulose suspension; (2) Dissolving a certain amount of quaternary ammonium salt monomer, organosilane monomer, cross-linking agent and photoinitiator in a polymerizable solvent to obtain a quaternary ammonium salt-organosilane solution; (3) Mixing the nanocellulose suspension obtained in the step (1) and the quaternary ammonium salt-organosilane solution obtained in the step (2), and then adding the mixture into paper pulp according to a certain proportion to prepare special spraying liquid; (4) Spraying the special spraying liquid prepared in the step (3) on the surface of a substrate, simultaneously irradiating the spraying area with ultraviolet light under the nitrogen atmosphere so as to enable the spraying liquid to carry out photopolymerization on the surface of the substrate, forming a coating on the surface of the substrate to obtain a coated substrate, and finally carrying out specific drying treatment on the coated substrate to obtain the durable antibacterial hydrophobic paper.
2. The method for preparing durable antimicrobial hydrophobic paper based on combination of intramammary self-assembly and surface photopolymerization according to claim 1, wherein the step (1) is specifically: adding a certain amount of nanocellulose into a dispersible solvent at a temperature of between 0 and 90 ℃, and stirring to obtain a nanocellulose suspension.
3. The method for preparing durable antibacterial hydrophobic paper based on combination of intramammary self-assembly and surface photopolymerization according to claim 1, which is characterized in that: in the step (1), the nanocellulose is at least one of cellulose nanocrystals, cellulose nanofibrils, regenerated nanocellulose, bacterial cellulose and other high molecular polymers, the dispersible solvent is at least one of water, dimethyl sulfoxide, N-dimethylformamide and other solvents, and in the step (1), the nanocellulose accounts for 1 wt% -15% wt% of the dispersible solvent by mass.
4. The method for preparing durable antibacterial hydrophobic paper based on combination of intramammary self-assembly and surface photopolymerization according to claim 1, which is characterized in that: The quaternary ammonium salt monomer in the step (2) is quaternary ammonium salt containing at least one long-chain alkyl group; the organic silane monomer is one of hexadecyl trimethoxy silane, (methyl) acryloxypropyl trimethoxy silane, vinyl trimethoxy silane, (3-glycidoxypropyl) trimethoxy silane and N-octyl triethoxy silane, the cross-linking agent is at least one of N, N '-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, pentaerythritol tetraacrylate and trimethylolpropane triacrylate, the photoinitiator is at least one of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-dimethoxy-2-phenyl acetophenone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and benzotriazole, the polymerizable solvent is at least one of water, dimethyl sulfoxide, N-dimethylformamide, methanol, ethanol, isopropanol, acetone, ethyl acetate and toluene, the quaternary ammonium salt monomer accounts for 15wt% of the quaternary ammonium salt-organic silane solution, the cross-linking agent accounts for 5wt% of the quaternary ammonium salt-organic silane monomer solution, the quaternary ammonium salt monomer accounts for 15wt% of the organic silane solution, the organic silane monomer accounts for 5wt% to 5wt% of the organic silane solution, the photoinitiator accounts for 0.1-5wt% of the quaternary ammonium salt-organosilane solution, and the quaternary ammonium salt of the long-chain alkyl is the quaternary ammonium salt with the carbon chain length being longer than C8.
5. The method for preparing durable antimicrobial hydrophobic paper based on combination of intramammary self-assembly and surface photopolymerization according to claim 1, wherein the step (3) is specifically: mixing the nanocellulose suspension obtained in the step (1) and the quaternary ammonium salt-organosilane solution obtained in the step (2) in a mass ratio of 4:1 to 8:1 to obtain quaternary ammonium silanized nanocellulose, and adding the quaternary ammonium silanized nanocellulose into paper pulp according to 2-10wt% to obtain special spraying liquid.
6. The method for preparing durable antibacterial hydrophobic paper based on combination of intramammary self-assembly and surface photopolymerization according to claim 1, wherein the step (4) is specifically: And (3) spraying the special spraying liquid and nitrogen prepared in the step (3) onto a substrate simultaneously by using a coaxial spray gun, irradiating a spraying area with ultraviolet light during spraying, enabling the spraying solution to carry out photopolymerization reaction on the surface of the substrate to form a coating, obtaining the substrate with the coating, and finally carrying out specific drying treatment to obtain the durable antibacterial hydrophobic paper.
7. The method for preparing durable antibacterial hydrophobic paper based on combination of intramammary self-assembly and surface photopolymerization according to claim 6, wherein the method comprises the following steps: the pressure of the outer layer channel of the coaxial spray gun is in the range of 0.1-8 Mpa, the dominant wavelength of ultraviolet light is 365-nm, and the ultraviolet light intensity is in the range of 100-400mW/cm <2 >.
8. The method for preparing durable antibacterial hydrophobic paper based on combination of intramammary self-assembly and surface photopolymerization according to claim 6, wherein the method comprises the following steps: In the step (4), the specific drying is at least one of vacuum oven drying, normal pressure oven drying, normal temperature drying, freeze drying, supercritical drying, and the like.
9. A durable antibacterial hydrophobic paper based on combination of intra-pulp self-assembly and surface photopolymerization is characterized in that: Is prepared by the preparation method of any one of claims 1-8.
10. Use of durable antimicrobial hydrophobic paper obtained by the process according to any one of claims 1 to 8, characterized in that: The application in high-end packaging materials, medical protection articles, file preservation materials and the like.

Description

Preparation method of durable antibacterial hydrophobic paper based on combination of intramammary self-assembly and surface photopolymerization Technical Field The invention belongs to the technical field of functional paper product manufacture and surface modification, in particular to antibacterial hydrophobic paper with quaternary ammonium salt and organosilane difunctional groups prepared by photoinitiated spray polymerization technology and a preparation method thereof. Background The inherent hydrophilicity and organic matter characteristics of paper also have two significant defects that firstly, the paper is extremely easy to be wetted and permeated by liquid water, so that the mechanical strength of the paper is drastically reduced, the application of the paper in the fields of moistureproof packaging, outdoor identification and the like is limited, and secondly, cellulose fibers and the water on the surfaces of the cellulose fibers are turned into a warm bed for the growth and propagation of microorganisms (such as bacteria and mold). To overcome these drawbacks, researchers have developed a variety of paper modification techniques. The currently prevailing methods include surface coating and dipping treatments. For example, certain water repellency can be imparted to paper by coating hydrophobic agents (e.g., paraffin, fluorocarbon), but such coatings tend to be mechanically weak, wear and tear, and can affect the breathability and feel of the paper. In terms of antimicrobial, impregnation or addition of inorganic antimicrobial agents (e.g., silver nanoparticles) or organic antimicrobial agents (e.g., quaternary ammonium salts) is often employed. However, these methods have obvious disadvantages in that the inorganic antibacterial agent has high cost and may have biotoxicity, while the small molecular organic antibacterial agent, particularly quaternary ammonium salt, has a weak binding force with paper fiber although having high antibacterial efficiency, is easy to run off during washing or use, and causes rapid attenuation of antibacterial performance and poor durability. The prior art generally solves the problem of hydrophobicity or antibacterial property only singly, and has difficulty in integrating two functions into a whole in an efficient and durable way. If the hydrophobing agent and the antibacterial agent are simply physically mixed and then coated, the effect is often poor due to poor compatibility or interference of functions. In addition, the conventional thermosetting process is energy intensive and unsuitable for use with heat sensitive paper substrates. Disclosure of Invention In order to solve the limitations of the prior art, the invention provides a preparation method of durable antibacterial hydrophobic paper based on combination of internal self-assembly and surface photopolymerization. The composition and technological parameters of the functional spraying liquid are precisely controlled, molecular pre-assembly is realized by utilizing hydrogen bonding, a stable cross-linked network is constructed by photoinitiated polymerization, and finally interface combination is strengthened by heat treatment. The obtained product has excellent antibacterial property (the antibacterial rate is more than or equal to 99.0%) and hydrophobicity (the contact angle is more than or equal to 140 degrees), and the performance is durable. The process is environment-friendly and efficient, and is suitable for large-scale production. The invention successfully prepares the functional paper with the advantages of high-efficiency antibacterial property, strong hydrophobicity, high durability, environmental protection, energy conservation and the like by combining ingenious molecular design (hydrogen bond pre-assembly) with advanced process technology (photoinitiated polymerization and spraying), and the comprehensive performance is far superior to that of the prior art, thus having extremely high market application value and popularization prospect. The technical scheme adopted by the invention is as follows: 1. Preparation method of durable antibacterial hydrophobic paper based on combination of intramammary self-assembly and surface photopolymerization The preparation method of the invention comprises the following steps: (1) Adding a certain amount of nano cellulose into a dispersible solvent at a certain temperature and stirring for a period of time to obtain a nano cellulose suspension, specifically adding a certain amount of nano cellulose into the dispersible solvent at a temperature of between 0 and 90 ℃, and stirring for 1 to 48 hours at a rotating speed of between 200 and 1000rpm to obtain the nano cellulose suspension. The nanocellulose is nanocellulose and derivatives thereof, specifically at least one of high molecular polymers such as Cellulose Nanocrystals (CNCs), cellulose Nanofibrils (CNFs), regenerated Nanocellulose (RNC), bacterial Cellulose (BC) and the like, the dispersible so