Silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic resin, and preparation method and application thereof

Abstract

The application discloses a kind of silicon-free fluorine-free hydrophobic sterilization water-based polyacrylic resin and its preparation method and application, belong to water-based functional polymer coating material technical field.The resin of the present application is prepared from deionized water, non-special acrylic functional monomer component, special acrylic functional monomer component, polyvinyl alcohol modified nano zinc oxide component, emulsifier component and initiator component.The present application is based on "molecular bridge crosslinking-nano structure coupling" strategy, introduces 1,6 hexanediol diacrylate of hydrophobic long alkyl chain in tertiary butyl chain polyacrylic acid resin to construct crosslinking molecular bridge, promotes tertiary butyl and long chain alkyl synergistic hydrophobic, and polyvinyl alcohol modified nano zinc oxide component is designed to be introduced, synergistically realizes the efficient integration of hydrophobic barrier and antibacterial site function, provides more environmentally friendly multifunctional solution for the field of medical protection, outdoor sports and household textiles and other textile functional finishing protection, and has wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of water-based functional polymer coating materials, and particularly relates to a silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic resin, a preparation method and application thereof. BACKGROUND

[0002] With the improvement of global environmental awareness and the demand for green transformation of the textile industry, traditional fluorine / silicon fabric finishing agents are strictly limited due to their environmental persistence, bioaccumulation and potential toxicity (such as PFOA, PFOS, etc.) (such as the EU REACH regulation). Cotton fabric, as the most widely used natural fiber material, has excellent air permeability and skin-friendliness, but its inherent hydrophilicity leads to problems such as easy staining, microbial breeding and insufficient UV protection, limiting its application in high-value-added fields such as medical protection and outdoor sports. Existing fluorine-free hydrophobic coating technologies mainly focus on polyurethane, silicone and polyacrylate systems, but all have significant defects: polyurethane systems rely on highly toxic isocyanate monomers, have high costs and low crosslinking density; silicone systems require a high proportion of siloxane (≥30%), which leads to hardening of the fabric and a 30%-50% decrease in air permeability; water-based polyacrylate is environmentally friendly and low-cost, but its hydrophobic groups (such as long-chain alkyl groups) are randomly distributed, the surface energy is not sufficiently reduced, the water contact angle is usually less than 100°, and it lacks effective antibacterial and anti-UV functions.

[0003] In terms of antibacterial and anti-UV functions, inorganic antibacterial agents are widely used due to their high stability and good durability, including silver-based, copper-based and zinc-based types. Among them, silver-based antibacterial agents (such as nano-Ag2O) have the advantages of high-efficiency broad-spectrum antibacterial, rapid action and strong stability, but the continuously released silver ions pose a biological safety risk, have high costs and may induce bacterial resistance; copper-based antibacterial agents (nano-CuO) have moderate costs, diverse antibacterial mechanisms and relatively high environmental friendliness, but have limited antibacterial efficiency, slow release rate and insufficient stability; zinc-based antibacterial agents (such as nano-ZnO) have the advantages of excellent biological safety, broad-spectrum antibacterial, anti-UV and hydrophobic enhancement effects, and low cost, but the nano-particles are prone to agglomeration, resulting in poor dispersibility. In addition, other inorganic antibacterial agents such as titanium dioxide (TiO2) and silicon dioxide (SiO2) composite systems have the characteristics of safety and low cost, but they have limitations such as dependence on light activation or introduction of toxic metal ions. Moreover, coatings with single hydrophobic or antibacterial function cannot meet the needs of complex scenarios, and the development of fluorine-free and silicon-free coatings with multiple functions such as hydrophobicity, antibacterial property and anti-UV property and environmental friendliness has become an industry bottleneck.

[0004] To solve the above problems, the prior art attempts to improve the performance by introducing crosslinking agents or nanomaterials, but the problem of the synergistic balance of "performance-safety-durability" has not been solved. For example, traditional crosslinking agents cannot induce the arrangement of hydrophobic groups in a targeted manner, and the poor dispersibility of nanomaterials leads to weak interfacial bonding force, and the function decays significantly after washing. Therefore, there is an urgent need for a synergistic strategy that couples molecular-level design with nanotechnology to construct a fluorine-free and silicon-free multifunctional coating that can improve hydrophobicity, antibacterial property, and ultraviolet resistance while ensuring the durability of the coating and the air permeability of the fabric. SUMMARY

[0005] To solve the problems of the prior art, the primary purpose of the present application is to provide a silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin. The present application also provides a method for preparing a silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin.

[0006] Another purpose of the present application is to provide an application of a silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin, which is particularly applicable to the functional finishing and protection of textiles such as medical protection, outdoor sports, and household textiles.

[0007] To achieve the above technical purposes, based on the "molecular bridge crosslinking-nano structure coupling" strategy, the present application constructs a molecular bridge to drive the directional arrangement of hydrophobic groups in the water-based polyacrylic acid resin, and combines polyvinyl alcohol (PVA) modified nano zinc oxide (ZnO), i.e., polyvinyl alcohol modified nano zinc oxide component (PNZ), which not only improves its dispersibility but also enhances the mechanical stability of ZnO through hydrogen bonding and the formation of an interpenetrating network structure between PVA molecular chains and the polyacrylic ester matrix. Together, they build a micro-nano rough structure, achieving efficient integration of hydrophobic barriers and antibacterial sites, and breaking through the performance limitations of traditional fluorine-free systems. Specifically, the technical scheme adopted by the present application is as follows:

[0008] A silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin is prepared from the following raw materials in the following amounts by weight: deionized water 60.0-100.0 parts, non-special acrylic functional monomer component 40.0-80.0 parts, special acrylic functional monomer component 10.0-30.0 parts, polyvinyl alcohol modified nano zinc oxide component 1.0-10.0 parts, emulsifier component 0.2-2.0 parts, and initiator component 0.1-2.0 parts.

[0009] Preferably, a silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin is prepared from the following raw materials in the following amounts by weight: deionized water 60.0-100.0 parts, non-special acrylic functional monomer component 60.0-80.0 parts, special acrylic functional monomer component 13.0-25.0 parts, polyvinyl alcohol modified nano zinc oxide component 1.0-5.0 parts, emulsifier component 1.0-2.0 parts, and initiator component 0.2-1.2 parts.

[0010] Preferably, a kind of silicon-free fluorine-free hydrophobic bactericidal aqueous polyacrylic acid resin is prepared from the following raw materials by weight: 100 parts of deionized water, 75 parts of non-special acrylic functional monomer component, 15 parts of special acrylic functional monomer component, 1.0 parts of polyvinyl alcohol modified nano zinc oxide component, 1.5 parts of emulsifier component and 0.5 parts of initiator component.

[0011] Preferably, the non-special acrylic functional monomer component is a combination of butyl acrylate, isooctyl acrylate and methyl methacrylate.

[0012] Preferably, the special acrylic functional monomer component is a combination of acrylic acid, hydroxypropyl acrylate, tertiary carbon acid vinyl ester and 1,6-hexanediol diacrylate.

[0013] Preferably, the preparation method of the polyvinyl alcohol modified nano zinc oxide component is as follows: nano zinc oxide is dispersed in anhydrous ethanol to prepare a dispersion liquid with a mass fraction of 5.0%, then pre-dispersed at a speed of 17000 rpm for 15 min, and then ultrasonically treated for 1 h to obtain a nano zinc oxide dispersion liquid (1.0 kg), then the above nano zinc oxide dispersion liquid is added to an 80℃ polyvinyl alcohol aqueous solution (2.0 kg) with a mass concentration of 8.0% at a constant rate of 2 mL / min, the mass ratio of nano zinc oxide dispersion liquid to polyvinyl alcohol aqueous solution is 1:2, after the addition is completed, the reaction is continued for 24 h, then cooled to room temperature, then centrifuged, washed with anhydrous ethanol and vacuum dried to obtain the polyvinyl alcohol modified nano zinc oxide component.

[0014] Preferably, the emulsifier component is one or a combination of several of allyloxy isomerol ether sulfate ammonium salt SR-10 (Adeka, Japan), sodium vinyl sulfonate SVS (Solvay, Belgium), castor oil polyoxyethylene ether EL-10 (Hai'an Petrochemical, China) and 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate DNS86 (Hank Chemistry, China).

[0015] More preferably, the emulsifier component is allyloxy isomerol ether sulfate ammonium salt SR-10 (Adeka, Japan).

[0016] Preferably, the initiator component is one or a combination of several of ammonium persulfate, potassium persulfate and sodium persulfate.

[0017] More preferably, the initiator component is potassium persulfate, specifically a 25% potassium persulfate aqueous solution.

[0018] The application discloses a preparation method of a silicon-free and fluorine-free hydrophobic and sterilizing water-based polyacrylic acid resin, and the method comprises the following steps: adding 80% of an emulsifier component and 40% of deionized water into a pre-emulsification reaction kettle, uniformly stirring, then adding 80% of an initiator and stirring for 10 minutes, then sequentially adding a non-special acrylic functional monomer component and a special acrylic functional monomer component, and pre-emulsifying for 60 minutes to obtain a pre-emulsified liquid; then adding the remaining 60% of deionized water and 20% of the emulsifier component into a polymerization reaction kettle, stirring for 10 minutes, then adding a polyvinyl alcohol modified nano zinc oxide component, stirring and heating to 83 DEG C, then taking 10% of the pre-emulsified liquid and the remaining 20% of the initiator and adding them into the polymerization reaction kettle, when the emulsion turns blue and does not backflow (about 30 minutes), uniformly dropping the remaining whole pre-emulsified liquid into the polymerization reaction kettle at a dropping time of 3 hours; after the dropping is completed, heating to 88 DEG C and performing heat preservation reaction for 2 hours, then cooling to 50 DEG C, adjusting the pH value to 7-8 by using ammonia water, filtering impurities through a 180-mesh filter screen, and thus the silicon-free and fluorine-free hydrophobic and sterilizing water-based polyacrylic acid resin is obtained.

[0019] The silicon-free and fluorine-free hydrophobic and sterilizing water-based polyacrylic acid resin prepared by the method has the structure of formula (I).

[0020] (I).

[0021] The silicon-free and fluorine-free hydrophobic and sterilizing water-based polyacrylic acid resin can be applied to medical, outdoor and household related protective textiles, and is specifically applied to medical health (medical protective textiles, hospital infection control textiles), outdoor and sports equipment (jacket, sun protection clothes, tent cloth), daily consumer goods (stain-resistant curtains, children's clothing, work clothes), industrial and special protection (dust-proof clothes, filter cloth) and environmental protection and sustainable fields (organic cotton products, degradable fabrics), and has the characteristics of hydrophobicity, antibacterial property, ultraviolet resistance, air permeability and washing resistance, and is suitable for medical protection, outdoor sports and household textile functional finishing protection fields.

[0022] Beneficial effects:

[0023] (1) The present application is based on the strategy of "molecular bridge crosslinking-nano structure coupling", introduces 1,6 hexanediol diacrylate with hydrophobic long alkyl chain into the tertiary butyl chain polyacrylic acid resin to construct a molecular bridge, promotes the synergistic hydrophobicity of tertiary butyl and long chain alkyl, and designs to introduce polyvinyl alcohol modified nano zinc oxide component, the long chain of polyvinyl alcohol not only effectively improves the dispersion stability of nano zinc oxide, but also the hydrogen bond effect of the long chain of polyvinyl alcohol not only plays a role in protecting the colloidal stable emulsion polymerization, but also together with nano zinc oxide and polymer main chain constructs micro-nano rough structure, further realizes the efficient integration of hydrophobic barrier and antibacterial site function, breaks through the performance limitation of traditional fluorine-free system, and provides more environmentally friendly multifunctional solution for the functional finishing protection field of medical protection, outdoor sports and household textiles.

[0024] (2) The present application relates to a silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin, which can meet the needs of different application fields by optimizing the ratio and composition of raw materials.

[0025] (3) The present application relates to a silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin, which does not involve organic solvents such as acetone and xylene, and does not release other small organic molecules during curing, is green and environmentally friendly, and has wide application prospects. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The synthesis route of the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid ester of the present application;

[0027] Figure 2 The contact angle of the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid ester of the present application and the comparative example;

[0028] Figure 3 The antibacterial performance (Escherichia coli) of the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid ester of the present application Example 2, wherein (a) is Escherichia coli cultured normally for 12h, and (b) is Escherichia coli cultured for 12h after adding 1x1cm fabric loaded with coating and oscillating;

[0029] Figure 4 The antibacterial performance (Staphylococcus aureus) of the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid ester of the present application Example 2, wherein (a) is Staphylococcus aureus cultured normally for 12h, and (b) is Staphylococcus aureus cultured for 12h after adding 1x1cm fabric loaded with coating and oscillating;

[0030] Figure 5 The contact angle of the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid ester of the present application Example 2 changes with time;

[0031] Figure 6The morphology (SEM) and energy spectrum analysis (EDS) results of the cotton fabric coated with the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylate of Embodiment 2;

[0032] Figure 7 The mechanism diagram of the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylate of the present application. DETAILED DESCRIPTION

[0033] The technical solutions of the present application are further described below in combination with specific embodiments, but are not limited thereto.

[0034] Embodiment 1

[0035] A silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylate resin, the preparation method thereof comprising the following steps: 1.0 kg of allyloxy isomeric alcohol ether sulfate SR-10 (Adeka, Japan) and 40.0 kg of deionized water are added to a pre-emulsification kettle, stirred uniformly, and then 0.4 kg of 25% potassium persulfate aqueous solution is added, stirred for 10 min, and then 15 kg of methyl methacrylate, 50 kg of butyl acrylate, 10.0 kg of isooctyl acrylate, 2.0 kg of acrylic acid, 2.0 kg of hydroxypropyl acrylate, 10.0 kg of vinyl versatate, and 1.0 kg of 1, 6 hexanediol diacrylate are sequentially added, and pre-emulsification is carried out for 60 min to obtain a pre-emulsion. At the same time, 60.0 kg of deionized water and 0.5 kg of allyloxy isomeric alcohol ether sulfate SR-10 (Adeka, Japan) are added to a polymerization kettle and stirred for 10 min, then 1.0 kg of PNZ component is added, stirred and heated to 83℃, and then 10% of the above pre-emulsion (13.0 kg) and 0.1 kg of 25% potassium persulfate aqueous solution are added to the polymerization kettle, and when the emulsion turns blue and does not backflow (about 30 min), the remaining pre-emulsion is uniformly added to the polymerization kettle at a constant speed, and the dropping time is controlled for 3 h. After the dropping is completed, the temperature is raised to 88℃ for 2 h, and then the temperature is lowered to 50℃, the pH value is adjusted to 7-8 with ammonia water, and the impurities are removed by filtering through a 180 mesh filter screen to obtain a silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylate resin.

[0036] Embodiment 2

[0037] A kind of silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin, its preparation method includes the following steps: 1.0kg allyloxy isomerol ether sulfate ammonium salt SR-10 (Adeka, Japan), 40.0kg deionized water is added to pre-emulsification kettle, after stirring uniformly, then 0.4kg 25% potassium persulfate aqueous solution is added, stirring 10min, then 15.0kg methyl methacrylate, 50.0kg butyl acrylate, 10.0kg isooctyl acrylate, 2.0kg acrylic acid, 2.0kg hydroxypropyl acrylate, 10.0kg vinyl versatate, 2.0kg 1, 6 hexanediol diacrylate are added in turn, pre-emulsification 60min to obtain pre-emulsion.Liaison, 60.0kg deionized water and 0.5kg allyloxy isomerol ether sulfate ammonium salt SR-10 (Adeka, Japan) are added to polymerization reactor kettle and stirred for 10min, then 1.0kg PNZ component is added, stirring and heating to 83℃, then the above 10% pre-emulsion (13.0kg) and 0.1kg 25% potassium persulfate aqueous solution are added to polymerization reactor kettle, when emulsion is blue, not reflux (about 30min), the remaining whole pre-emulsion is added to polymerization reactor kettle at a constant speed, control drop time is 3h. After drop, heating to 88℃ and reacting for 2h, then cooling to 50℃, adjust pH value to 7-8 with ammonia water, filter with 180 mesh filter screen to remove impurities, to obtain silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin.

[0038] Example 3

[0039] A kind of silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin, its preparation method includes the following steps: 1.0kg allyloxy isomerol ether sulfate ammonium salt SR-10 (Adeka, Japan), 40.0kg deionized water is added to pre-emulsification kettle, after stirring uniformly, then 0.4kg 25% potassium persulfate aqueous solution is added, stirring 10min, then 15.0kg methyl methacrylate, 50kg butyl acrylate, 10.0kg isooctyl acrylate, 2.0kg acrylic acid, 2.0kg hydroxypropyl acrylate, 10.0kg vinyl versatate, 3.0kg 1, 6 hexanediol diacrylate are added in sequence, pre-emulsification 60min to obtain pre-emulsion.Liaison, in polymerization reactor kettle 60.0kg deionized water and 0.5kg allyloxy isomerol ether sulfate ammonium salt SR-10 (Adeka, Japan) are added and stirred 10min, then 1.0kg PNZ component is added, stirring and heating to 83℃, then the above 10% pre-emulsion (13.0kg) and 0.1kg 25% potassium persulfate aqueous solution are added to polymerization reactor kettle, when emulsion is blue, not reflux (about 30min), the remaining whole pre-emulsion is added to polymerization reactor kettle at uniform speed, control drop time to be 3h. After drop, heating to 88℃ and reacting 2h, then cooling to 50℃, adjust pH value to 7-8 with ammonia water, 180 mesh filter screen is filtered to remove impurities, to obtain silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin.

[0040] Example 4

[0041] A kind of silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin.The preparation method includes the following steps: 1.0kg allyloxy isomerol ether sulfate ester ammonium salt SR-10 (Aidiko, Japan), 40.0kg deionized water is added to pre-emulsification kettle, after stirring evenly, then 0.4kg 25% potassium persulfate aqueous solution is added, stirring 10min, then 15.0kg methyl methacrylate, 50.0kg butyl acrylate, 10.0kg isooctyl acrylate, 2.0kg acrylic acid, 2.0kg hydroxypropyl acrylate, 10.0kg vinyl versatate, 4.0kg 1, 6 hexanediol diacrylate is added in turn, pre-emulsification 60min to obtain pre-emulsion.At the same time, 60.0kg deionized water and 0.5kg allyloxy isomerol ether sulfate ester ammonium salt SR-10 (Aidiko, Japan) are added to polymerization kettle and stirred for 10min, then 1.0kg PNZ component is added, stirring and heating to 83℃, then 10% of the above pre-emulsion (13.0kg) and 0.1kg 25% potassium persulfate aqueous solution are added to the polymerization kettle, when the emulsion turns blue and does not reflux (about 30min), the remaining whole pre-emulsion is added to the polymerization kettle at a constant speed, and the dropping time is controlled for 3h.After dropping, heat to 88℃ and keep for 2h, then cool to 50℃, adjust pH to 7-8 with ammonia water, filter with 180 mesh screen to remove impurities, and then a silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin is obtained.

[0042] Comparative example 1

[0043] A kind of silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin, the preparation method includes the following steps: 1.0kg allyloxy isomerol ether sulfate ester ammonium salt SR-10 (Aidiko, Japan), 40.0kg deionized water is added to pre-emulsification kettle, after stirring evenly, then 0.4kg 25% potassium persulfate aqueous solution is added, stirring 10min, then 15.0kg methyl methacrylate, 50.0kg butyl acrylate, 10.0kg isooctyl acrylate, 7.5.0kg acrylic acid, 7.5kg hydroxypropyl acrylate is added in turn, pre-emulsification 60min to obtain pre-emulsion.At the same time, 60.0kg deionized water and 0.5kg allyloxy isomerol ether sulfate ester ammonium salt SR-10 (Aidiko, Japan) are added to polymerization kettle and stirred for 10min, then 1.0kg PNZ component is added, stirring and heating to 83℃, then 10% of the above pre-emulsion (13.0kg) and 0.1kg 25% potassium persulfate aqueous solution are added to the polymerization kettle, when the emulsion turns blue and does not reflux (about 30min), the remaining whole pre-emulsion is added to the polymerization kettle at a constant speed, and the dropping time is controlled for 3h.After dropping, heat to 88℃ and keep for 2h, then cool to 50℃, adjust pH to 7-8 with ammonia water, filter with 180 mesh screen to remove impurities, and then a silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin is obtained.

[0044] The comparative example, relative to example 1, only changed the monomer type of the special acrylic functional monomer component, that is, no vinyl versatate, 1, 6 hexanediol diacrylate was used, and the rest of the raw material type and dosage and process steps were the same as example 1.

[0045] Comparative example 2

[0046] A silicon-free and fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin, its preparation method comprises the following steps: 1.0 kg of allyloxy isomeric alcohol ether sulfate ammonium salt SR-10 (Adeka, Japan) and 40.0 kg of deionized water are added to a pre-emulsification kettle, after stirring uniformly, 0.4 kg of 25% potassium persulfate aqueous solution is added, stirring for 10 min, then 15.0 kg of methyl methacrylate, 50.0 kg of butyl acrylate, 10.0 kg of isooctyl acrylate, 2.5 kg of acrylic acid, 2.5 kg of hydroxypropyl acrylate and 10.0 kg of vinyl versatate are added in turn, and pre-emulsification is carried out for 60 min to obtain a pre-emulsion. At the same time, 60.0 kg of deionized water and 0.5 kg of allyloxy isomeric alcohol ether sulfate ammonium salt SR-10 (Adeka, Japan) are added to a polymerization kettle and stirred for 10 min, then 1.0 kg of PNZ component is added, stirring and heating to 83℃, then 10% of the above pre-emulsion (13.0 kg) and 0.1 kg of 25% potassium persulfate aqueous solution are added to the polymerization kettle, when the emulsion turns blue and does not backflow (about 30 min), the remaining whole pre-emulsion is added to the polymerization kettle at a constant speed, and the dropping time is controlled for 3 h. After dropping, the temperature is raised to 88℃ for 2 h, then the temperature is lowered to 50℃, the pH value is adjusted to 7-8 with ammonia water, and the impurities are removed by filtering through a 180 mesh filter screen, to obtain a silicon-free and fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin.

[0047] The comparative example, relative to example 1, only changed the monomer type of the special acrylic functional monomer component, that is, no 1, 6 hexanediol diacrylate was used, and the rest of the raw material type and dosage and process steps were the same as example 1.

[0048] Comparative example 3

[0049] A kind of silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin, its preparation method includes the following steps: 1.0kg allyloxy isomerol ether sulfate ammonium salt SR-10 (Adeka, Japan), 40.0kg deionized water is added to pre-emulsification kettle, after stirring uniformly, 0.4kg 25% potassium persulfate aqueous solution is added, stirring 10min, then 15.0kg methyl methacrylate, 50.0kg butyl acrylate, 10.0kg isooctyl acrylate, 7.0kg acrylic acid, 7.0kg hydroxypropyl acrylate, 1.0kg 1, 6 hexanediol diacrylate are sequentially added, pre-emulsification 60min to obtain pre-emulsion.Liaison, in polymerization reactor kettle 60.0kg deionized water and 0.5kg allyloxy isomerol ether sulfate ammonium salt SR-10 (Adeka, Japan) are stirred 10min, then 1.0kg PNZ component is added, stirring and heating to 83℃, then the above 10% pre-emulsion (13.0kg) and 0.1kg 25% potassium persulfate aqueous solution are added to polymerization reactor kettle, when emulsion is blue, not reflux (about 30min), the remaining whole pre-emulsion is added to polymerization reactor kettle at a constant speed, control drop time is 3h. After drop, heating 88℃ is carried out for 2h, then cooling 50℃ is carried out, and pH value is adjusted to 7-8 with ammonia water, 180 mesh filter screen is filtered to remove impurities, to obtain silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin.

[0050] In the present comparative example, only the monomer type of special acrylic functional monomer component is changed, i.e. no vinyl versatate is used, and the rest of the raw material types and dosages and process steps are the same as those of example 1.

[0051] Comparative example 4

[0052] A kind of silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin. Its preparation method includes the following steps: 1.0kg allyloxy isomerol ether sulfate SR-10 (Adeka, Japan), 40.0kg deionized water is added to pre-emulsification kettle, after stirring evenly, 0.4kg 25% potassium persulfate aqueous solution is added, stirring 10min, then 15.0kg methyl methacrylate, 50.0kg butyl acrylate, 10.0kg isooctyl acrylate, 2.0kg acrylic acid, 2.0kg hydroxypropyl acrylate, 10.0kg vinyl versatate, 1.0kg 1, 6 hexanediol diacrylate are sequentially added, pre-emulsification 60min to obtain pre-emulsified liquid. At the same time, 60.0kg deionized water and 0.5kg allyloxy isomerol ether sulfate SR-10 (Adeka, Japan) are added to polymerization reactor kettle and stirred for 10min, then 1.0kg nano zinc oxide component is added, stirring and heating to 83℃, then 10% of the above pre-emulsified liquid (13.0kg) and 0.1kg 25% potassium persulfate aqueous solution are added to the polymerization reactor kettle, when the emulsion turns blue and does not reflux (about 30min), the remaining whole pre-emulsified liquid is added to the polymerization kettle at a constant speed, and the dropwise adding time is controlled to be 3h. After dropwise adding, the temperature is increased to 88℃ and the reaction is kept for 2h, then the temperature is decreased to 50℃, the pH value is adjusted to 7-8 with ammonia water, and the impurities are removed by 180 mesh filter screen filtration, to obtain silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin.

[0053] In the present comparative example, compared with example 1, only nano zinc oxide is directly used, and the rest of the raw material types and process steps are the same as those of example 1.

[0054] Performance test

[0055] The synthetic route of the silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin prepared in the present application is shown in Figure 1 The performance test indexes of the silicon-free fluorine-free hydrophobic bactericidal water-based polyacrylic acid resin mainly include appearance, particle size and distribution, contact angle, water absorption rate and antibacterial performance.

[0056] Firstly, the present application uses dynamic light scattering instrument (DLS) to measure (Brookhaven ZetaPlus) to prepare the particle size and distribution test of the silicon-free and fluorine-free hydrophobic sterilization water-based polyacrylic acid resin layer. The appearance, stability, particle size and distribution of the silicon-free and fluorine-free hydrophobic sterilization water-based polyacrylic acid resin prepared by the present application are shown in Table 1. As can be seen from the table, the silicon-free and fluorine-free hydrophobic sterilization water-based polyacrylic acid resin prepared by the present application is a milky white uniform liquid, which does not separate after standing for six months. At the same time, the particle size is uniform, the average particle size is between 100-150 nm, and the particle size distribution (PDI) is also narrow. It is very beneficial to subsequent coating and protection use. While the comparative example 4 only uses unmodified nano zinc oxide to prepare the silicon-free and fluorine-free hydrophobic sterilization water-based polyacrylic acid resin, the emulsion is unstable and easy to separate, and the particle size distribution is wide, which is very unfavorable for subsequent application. At the same time, the emulsion particle size of comparative examples 1-3 without ethylene carbonate and 1, 6-hexanediol diacrylate functional monomers will decrease, but the PNZ dispersibility is not as good as example 1, so the overall particle size is large, and the particle size distribution (PDI) is also wide.

[0057] Table 1 Appearance, stability, particle size and distribution of silicon-free and fluorine-free hydrophobic sterilization water-based polyacrylic acid resin of the present application and comparative examples

[0058]

[0059] Secondly, in order to evaluate the hydrophobic and water resistance of the silicon-free and fluorine-free hydrophobic sterilization water-based polyacrylic acid resin, the contact angle (JY-82B, Chengde Dingsheng Test Equipment Co., Ltd.) of the film coated with the silicon-free and fluorine-free hydrophobic sterilization water-based polyacrylic acid resin is determined, and the water absorption rate of the film is determined according to the JC / T 1017-2006 "Polymer Emulsion for Building Waterproof Coatings" industry standard. The contact angle and water absorption rate of the film coated with the silicon-free and fluorine-free hydrophobic sterilization water-based polyacrylic acid resin prepared by the present application are shown in Table 2. As can be seen from the table, the film coated with the fluorosilicon polyacrylate emulsion prepared by the present application has excellent hydrophobic performance, and the contact angles of examples 1-4 are all greater than 90 o , while in the comparative examples, with the selective addition of ethylene carbonate and 1, 6-hexanediol diacrylate, the hydrophobic effect decreases obviously, and the contact angles of comparative examples 1-3 are all less than 90 oThis also fully illustrates that the present application is based on the "molecular bridge crosslinking-nanostructure coupling" strategy, and 1,6 hexanediol diacrylate with a hydrophobic long alkyl chain is introduced into the tertiary butyl chain-containing polyacrylic acid resin to construct a molecular bridge, so as to promote the hydrophobicity of the tertiary butyl group and the long alkyl group, and to jointly give the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin designed by the present application excellent hydrophobicity. At the same time, the coating film of the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin designed by the present application also has low water absorption, and the 72h coating film water absorption is less than 8.0%. Therefore, the fluorosilicon polyacrylate emulsion coating film prepared by the present application not only has excellent hydrophobicity, but also has low water absorption, which provides a solid foundation for the subsequent application of the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin.

[0060] Table 2 Contact angle and water absorption of the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin of the present application and the comparative examples

[0061]

[0062] Finally, in the antibacterial performance test, the present application uses representative escherichia coli and staphylococcus aureus as test bacteria, uniformly coats the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin prepared by the present application on cotton cloth, then cuts it according to 1cm*1cm, and quantitatively tests its bactericidal performance according to GB / T 20944.3-200 Textiles-Determination of antibacterial activity of an antibacterial agent added in the textile-Part 3: Shake flask method. Specifically, escherichia coli and staphylococcus aureus are selected as test bacteria, cultured and diluted to an appropriate concentration of about 1x10 4 CFU / mL. A certain volume of bacterial solution is accurately measured and inoculated into the triangular flask of the sample. After 12h of culture, it is observed that the colonies grow. The bactericidal rate is calculated by colony counting. The results of the bactericidal rate of the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin prepared by the present application are shown in Table 3, Figure 3 and Figure 4 As compared with Comparative Example 4, the present application introduces a polyvinyl alcohol modified nano zinc oxide component, the long chain of polyvinyl alcohol not only effectively improves the dispersion stability of nano zinc oxide, but also the hydrogen bonding of the long chain of polyvinyl alcohol plays a role in protecting the colloidal stability of emulsion polymerization; and the special molecular bridge structure of the present application further promotes the full and uniform dispersion of the PNZ component, which jointly gives the coating excellent antibacterial performance. At the same time, the present application uniformly coats the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin prepared in Example 2 on cotton cloth, and characterizes the contact angle (JY-82B, Chengde Dingsheng Test Machine Detection Equipment Co., Ltd.) and the morphology (scanning electron microscope, SEM5000, CIQYEK, CHN and EDX energy spectrum analysis) of the cotton cloth. The contact angle and surface morphology of the cotton cloth coated with the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin prepared in Example 2 are shown in Table 4 and Figure 1, Figure 5and Figure 6 It can be seen that the cotton fabric coated with the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin prepared in Example 2 exhibits excellent hydrophobic performance, and the cotton fabric coated with the silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin prepared in Comparative Example 1 exhibits poor hydrophobic performance. Figure 5 It can be seen that the cotton fabric has a micro-nano rough structure, and is also silicon-free and fluorine-free, and the polyethylene modified nano zinc oxide is also very uniformly distributed in the coating. Figure 6

[0063] Table 1: Antibacterial performance of silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resins of the present application and comparative examples

[0064]

[0065] In summary, the present application is based on the "molecular bridge crosslinking-nano structure coupling" strategy (as shown in the figure), Figure 7 ), a 1,6-hexanediol diacrylate with a hydrophobic long alkyl chain is introduced into a t-butyl chain-containing polyacrylic acid resin to construct a molecular bridge, which promotes the synergistic hydrophobicity of the t-butyl group and the long alkyl chain. At the same time, a polyvinyl alcohol modified nano zinc oxide component is designed to be introduced, the polyvinyl alcohol long chain not only effectively improves the dispersion stability of the nano zinc oxide, but also the hydrogen bonding of the polyvinyl alcohol long chain not only plays a role in protecting the colloidal stability of the emulsion polymerization, but also together with the nano zinc oxide and the polymer main chain, it constructs a micro-nano rough structure, further realizing the efficient integration of the hydrophobic barrier and the antibacterial site function, breaking through the performance limitations of traditional fluorine-free systems, and providing a more environmentally friendly multifunctional solution for the functional finishing and protection of medical protection, outdoor sports and household textiles.

[0066] It should be noted that the above examples are only part of the preferred modes of implementing the present application, not all. Obviously, based on the above examples of the present application, all other examples obtained by those of ordinary skill in the art without creative labor should fall within the scope of the present application.​

Claims

1. A silicon-free, fluorine-free, hydrophobic, bactericidal, aqueous polyacrylic acid resin, characterized in that, It is prepared from the following raw materials by weight: deionized water 60.0-100.0 parts, non-special acrylic functional monomer component 40.0-80.0 parts, special acrylic functional monomer component 10.0-30.0 parts, polyvinyl alcohol modified nano zinc oxide component 1.0-10.0 parts, emulsifier component 0.2-2.0 parts, initiator component 0.1-2.0 parts; the special acrylic functional monomer component is a combination of acrylic acid, hydroxypropyl acrylate, vinyl carbonate and 1,6-hexanediol diacrylate; the structure of the vinyl carbonate is: 。 2. The silicon-free, fluorine-free, hydrophobic, bactericidal aqueous polyacrylic acid resin according to claim 1, characterized in that, It is prepared from the following raw materials by weight: deionized water 60.0-100.0 parts, non-special acrylic functional monomer component 40.0-80.0 parts, special acrylic functional monomer component 10.0-30.0 parts, polyvinyl alcohol modified nano zinc oxide component 1.0-10.0 parts, emulsifier component 0.2-2.0 parts, initiator component 0.1-2.0 parts; the special acrylic functional monomer component is a combination of acrylic acid, hydroxypropyl acrylate, vinyl carbonate and 1,6-hexanediol diacrylate; the structure of the vinyl carbonate is:

3. The silicon and fluorine-free hydrophobic and antimicrobial aqueous polyacrylic acid resin according to claim 1, characterized by It is prepared from the following raw materials by weight: deionized water 60.0-100.0 parts, non-special acrylic functional monomer component 40.0-80.0 parts, special acrylic functional monomer component 10.0-30.0 parts, polyvinyl alcohol modified nano zinc oxide component 1.0-10.0 parts, emulsifier component 0.2-2.0 parts, initiator component 0.1-2.0 parts; the special acrylic functional monomer component is a combination of acrylic acid, hydroxypropyl acrylate, vinyl carbonate and 1,6-hexanediol diacrylate; the structure of the vinyl carbonate is:

4. The silicon-free, fluorine-free, hydrophobic, bactericidal aqueous polyacrylic acid resin according to any one of claims 1 to 3, characterized in that The non-special acrylic functional monomer component is a combination of butyl acrylate, isooctyl acrylate and methyl methacrylate.

5. The silicon-free, fluorine-free, hydrophobic, bactericidal aqueous polyacrylic acid resin according to any one of claims 1 to 3, characterized in that The preparation method of the polyvinyl alcohol modified nano zinc oxide component is: dispersing nano zinc oxide in anhydrous ethanol to prepare a dispersion liquid with a mass fraction of 5.0%, then pre-dispersing at a speed of 17000 rpm for 15 min, then ultrasonic treatment for 1 h to obtain a nano zinc oxide dispersion liquid, then adding the above nano zinc oxide dispersion liquid to an 80℃ polyvinyl alcohol aqueous solution with a mass concentration of 8.0% at a constant rate of 2 mL / min, the mass ratio of nano zinc oxide dispersion liquid to polyvinyl alcohol aqueous solution is 1:2, after the addition is completed, continue to react for 24 h, end the reaction and cool to room temperature, then centrifuge, wash with anhydrous ethanol and vacuum dry to obtain the polyvinyl alcohol modified nano zinc oxide component.

6. The silicon-free, fluorine-free, hydrophobic, bactericidal aqueous polyacrylic acid resin according to any one of claims 1 to 3, characterized in that The emulsifier component is one or more combinations of allyloxy isomerol ether sulfate ammonium salt SR-10, sodium vinyl sulfonate SVS, castor oil polyoxyethylene ether EL-10 and 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate DNS86.

7. The silicon-free, fluorine-free, hydrophobic, bactericidal aqueous polyacrylic acid resin according to any one of claims 1 to 3, characterized in that The initiator component is one or more combinations of ammonium persulfate, potassium persulfate and sodium persulfate.

8. A method for preparing the silicon-free and fluorine-free hydrophobic and bactericidal aqueous polyacrylic acid resin according to any one of claims 1 to 3, characterized in that, The preparation steps include: adding 80% of emulsifier component and 40% of deionized water into a pre-emulsification reaction kettle, stirring uniformly, then adding 80% of initiator and stirring for 10 min, then adding non-special acrylic functional monomer component and special acrylic functional monomer component in sequence, pre-emulsifying for 60 min to obtain a pre-emulsified liquid; then adding the remaining 60% of deionized water and 20% of emulsifier component into a polymerization reaction kettle, stirring for 10 min, then adding polyvinyl alcohol modified nano zinc oxide component, stirring and heating to 83 DEG C, then taking 10% of the pre-emulsified liquid and the remaining 20% of initiator and adding into the polymerization reaction kettle, when the emulsion turns blue and does not backflow, adding the remaining whole pre-emulsified liquid into the polymerization reaction kettle at a uniform speed, controlling the dropping time to be 3 h; after the dropping is completed, heating to 88 DEG C and reacting for 2 h, then cooling to 50 DEG C, adjusting the pH value to 7-8 by using ammonia water, filtering impurities by using a 180 mesh filter screen, thereby obtaining a silicon-free and fluorine-free hydrophobic and bactericidal water-based polyacrylic acid resin.

9. Use of the silicon-free and fluorine-free hydrophobic and bactericidal aqueous polyacrylic resin according to any one of claims 1 to 3, characterized in that, The application in medical, outdoor and household related protective textiles.

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