CN114409553A - Biquaternary ammonium salt-containing diol, preparation method thereof and application thereof in antibacterial self-extinction aqueous polyurethane coating - Google Patents

Biquaternary ammonium salt-containing diol, preparation method thereof and application thereof in antibacterial self-extinction aqueous polyurethane coating Download PDF

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CN114409553A
CN114409553A CN202210109360.XA CN202210109360A CN114409553A CN 114409553 A CN114409553 A CN 114409553A CN 202210109360 A CN202210109360 A CN 202210109360A CN 114409553 A CN114409553 A CN 114409553A
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ammonium salt
diol
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aqueous polyurethane
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CN114409553B (en
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彭晓宏
潘玮辰
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South China University of Technology SCUT
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    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/14—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to a carbon atom of a six-membered aromatic ring
    • C07C217/16—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to a carbon atom of a six-membered aromatic ring the six-membered aromatic ring or condensed ring system containing that ring not being further substituted
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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    • 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
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    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/3275—Hydroxyamines containing two hydroxy groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C08G18/6633—Compounds of group C08G18/42
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract

The invention discloses a biquaternary ammonium salt-containing diol, a preparation method thereof and application thereof in an antibacterial self-extinction aqueous polyurethane coating. The preparation method of the antibacterial self-extinction waterborne polyurethane coating comprises the steps of mixing dehydrated polymer dihydric alcohol and a monomer containing biquaternary ammonium salt glycol, adding isocyanate and a catalyst for prepolymerization, and reacting to generate a block copolymer; adding deionized water under high-speed stirring to emulsify to form emulsion by depending on the hydrophilicity of the diquaternary ammonium salt-containing diol monomer; and adding an amine or hydrazine chain extender with higher reactivity to completely react the residual isocyanate, and finally mixing a proper amount of an auxiliary agent to obtain the waterborne polyurethane coating. The coating adhesive film has good antibacterial property, and can achieve excellent self-extinction effect without additional addition of auxiliary agents or surface treatment.

Description

Biquaternary ammonium salt-containing diol, preparation method thereof and application thereof in antibacterial self-extinction aqueous polyurethane coating
Technical Field
The invention relates to a polyurethane coating, in particular to a self-extinction water-based polyurethane coating with an antibacterial function and a preparation method thereof.
Background
Gloss is an indication of the ability of a surface material to reflect light and can be divided into high gloss surfaces and low gloss surfaces depending on the appearance. High gloss surfaces result from the specular reflection of light at the surface of the material. Strong specular reflection can not only amplify the defects on the surface of the material, but also influence the appearance; and more seriously, light pollution and harm to human health. The low-gloss surface can make the surface of the material show a delustering effect through diffuse reflection and scattering of light, so that the light pollution can be greatly reduced, and the material is widely applied.
Matting materials can be divided into two types: physical extinction and self-extinction. The physical extinction material is obtained by adding an extinction agent into resin to achieve extinction. The addition of the matting agent has a remarkable effect, but has problems such as precipitation of the matting agent, non-uniformity of film formation, and high brittleness. The self-matting material forms a rough surface by the accumulation of resin particles themselves, and thus can effectively avoid problems caused by physical matting. The waterborne polyurethane material has been widely applied to the fields of medical treatment, sanitation, food and other industries due to strong molecular designability, excellent mechanical properties and biocompatibility and environmental friendliness. CN113105815A describes a self-matting waterborne polyurethane coating, the self-matting effect of the surface of the coating is completely generated by a film-forming resin body, and the excellent matting effect is achieved without an additional auxiliary agent or subsequent surface treatment, and meanwhile, the coating also has good abrasion resistance, folding fastness and blocking resistance.
Common polyurethane does not have antibacterial effect, and can achieve multiple effects by introducing special functional groups, such as quaternary ammonium salt. CN112831266A discloses an antibacterial and mildewproof polyurethane paint film and a preparation method thereof, in the method, dihydroxyl quaternary ammonium salt obtained by quaternizing N-alkyl diol amine is introduced to a polyurethane molecular chain, and the obtained polyurethane has good antibacterial property. CN113444222A also discloses a preparation method of the antibacterial polyurethane, which adopts dihydric alcohol or diamine containing quaternary ammonium-furan or quaternary ammonium-maleic anhydride structure as a chain extender for polyurethane preparation, not only introduces quaternary ammonium groups, but also enhances the creep resistance of the material. Although the prior art endows polyurethane with certain antibacterial effect, the introduced quaternary ammonium salt is a single-season ammonium salt, and the antibacterial effect has great promotion space. In addition, the antibacterial systems are mainly prepared based on solvent type polyurethane, which neither meets the requirement of environmental protection, nor inevitably brings biological toxicity.
Chinese invention patent CN103420868A discloses a method for preparing antibacterial aqueous polyurethane emulsion by using biquaternary ammonium salt diamine or diol monomer as chain extender, which is to copolymerize polyol and diisocyanate, introduce biquaternary ammonium salt and hydrophilic chain extender, then add alkaline substance for neutralization, finally prepare emulsion. However, the diquaternary ammonium salt monomer used in the method contains a secondary amine structure, which is not beneficial to the growth of a polyurethane molecular chain in the polymerization process, and the obtained emulsion does not have self-extinction performance after film forming. And the biquaternary ammonium salt monomer is added after the copolymerization of the polyalcohol and the diisocyanate, the viscosity of the system is higher, the biquaternary ammonium salt monomer has the phenomenon of uneven polymerization, and the problem of poor local antibacterial property can occur in use. In addition, the diquaternary ammonium salt monomer has no hydrophilicity, and a hydrophilic chain extender is required to provide self-emulsifying property for a molecular chain, so that the complexity of the preparation process is increased.
Disclosure of Invention
In view of the above, the primary object of the present invention is to provide a diquaternary ammonium salt diol-containing monomer, which not only has good antibacterial property and reaction controllability, but also can enhance the rigidity of the polyurethane molecular chain.
The invention also provides a preparation method of the di-quaternary ammonium salt-containing diol monomer.
The invention also aims to provide a method for preparing the waterborne polyurethane coating with the antibacterial self-extinction function by using the monomer containing the biquaternary ammonium salt diol.
The purpose of the invention is realized by the following technical scheme:
the di-quaternary ammonium salt-containing diol is characterized by having a structural general formula as follows:
Figure BDA0003494622000000021
wherein R is1An alkyl group having 1 to 10 carbon atoms; x is a chlorine atom or a bromine atom; m is an integer of 0-5, n is an integer of 0-20, and k is an integer of 1-20; r2Is hydrogen atom, methyl, sulfonic group or benzyl.
Preferably R in the general structural formula1Represents an alkyl group having 1 to 4 carbon atoms; x is chlorine or bromine atom; m is 0 or 1, n is an integer of 1-14, and k is an integer of 1-5; r2Represents a hydrogen atom, a methyl group or a sulfonic acid group.
The preparation method of the di-quaternary ammonium salt-containing diol comprises the following steps and process conditions:
1) under the protection of inert gas, dissolving a raw material I, a raw material II and an alkaline substance in a solvent A, reacting for 48-96 hours at 50-120 ℃, filtering to remove precipitates, and dissolving a purified product in water;
2) mixing the aqueous solution of the product obtained in the step 1), a formaldehyde solution and concentrated hydrochloric acid in an acidic atmosphere, reacting at room temperature for 12-24 hours, and removing water out of the system; adding a mixed solvent of methanol and ethyl acetate into the product, filtering and collecting filter residues, and hydrolyzing the filter residues under an alkaline condition to obtain a diol monomer containing the ditertiary amine;
3) dissolving the di-tertiary amine diol-containing monomer obtained in the step 2) and a raw material III in a solvent B, reacting for 72-120 hours at 50-90 ℃, and purifying to obtain a di-quaternary ammonium salt diol-containing monomer;
the structural formulas of the raw material I, the raw material II and the raw material III are as follows:
Figure BDA0003494622000000031
wherein m is an integer of 0-5; k is an integer of 1 to 20, Y is a halogen element, R1An alkyl group having 1 to 10 carbon atoms; x is a chlorine atom or a bromine atom; m is an integer of 0 to 5, n isAn integer of 0 to 20, R2Is hydrogen atom, methyl, sulfonic group or benzyl.
Preferably, in the general formula structural raw materials I, II and III, m is 0 or 1; k is an integer of 1 to 5, Y is a chlorine, bromine or iodine atom, R1Represents an alkyl group having 1 to 4 carbon atoms; x represents a chlorine or bromine atom, n is an integer of 1 to 14, R2Represents a hydrogen atom, a methyl group or a sulfonic acid group.
To further achieve the object of the present invention, preferably, the solvent a is any one of acetonitrile, acetone, tetrahydrofuran, dimethyl sulfoxide, 1, 4-dioxane, N-dimethylformamide and N, N-dimethylacetamide; the solvent B is any one of acetonitrile, acetone, isopropanol, tetrahydrofuran and dioxane.
Preferably, the raw material I, the raw material II and the alkaline substance are mixed according to a molar ratio of 1: 2-4: 4-50 of the compound is dissolved in a solvent A; the water solution, the formaldehyde solution and the concentrated hydrochloric acid are mixed according to the mol ratio of 1: 2-3: 2-20 mixing; the di-tertiary amine containing diol monomer and the raw material III are mixed according to a molar ratio of 1: 2-3 are dissolved in the solvent B.
Preferably, the volume ratio of methanol to ethyl acetate in the mixed solvent is 1: 50-100 parts; the alkaline substance is at least one of sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
The method for preparing the antibacterial self-extinction waterborne polyurethane coating by using the glycol containing the biquaternary ammonium salt as the chain extender comprises the following process steps and conditions:
1) dehydrating the polymer dihydric alcohol, and cooling to 40-50 ℃; under the protection of inert gas, adding a glycol monomer containing biquaternary ammonium salt for mixing;
2) adding diisocyanate and a catalyst into the mixture obtained in the step 1), heating to 60-90 ℃, and reacting for 2-5 hours to obtain a polyurethane prepolymer; when the residual isocyanate value reaches 85-95% of a theoretical value, controlling the temperature to be room temperature;
3) adding deionized water into the product obtained in the step 2) for emulsification under strong stirring (the stirring speed is more than or equal to 600 rpm);
4) dropwise adding hydrazine or aliphatic diamine chain extenders into the product obtained in the step 3) under the condition of 0-room temperature, and continuing emulsifying and chain extending for 15-50 minutes until isocyanate in the emulsion is completely reacted;
5) filtering the product obtained in the step 4) to obtain an antibacterial self-extinction polyurethane emulsion with the solid content of 20-50%;
6) adding an auxiliary agent into the antibacterial self-extinction aqueous polyurethane emulsion obtained in the step 5) at room temperature, and uniformly mixing to obtain an antibacterial self-extinction aqueous polyurethane coating; the auxiliary agent comprises a defoaming agent, a leveling agent, a thickening agent and a curing agent.
Preferably, the polymer diol is one or more of polycaprolactone diol, polycarbonate diol, polyethylene adipate diol, polytetrahydrofuran ether glycol, polypropylene adipate diol and polybutylene adipate diol; the molecular weight of the polymer dihydric alcohol is 1000-2000;
the diisocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and dicyclohexylmethane diisocyanate;
the catalyst is any one of dibutyltin dilaurate, stannous octoate and zinc octoate;
the hydrazine chain extender is one or more of hydrazine hydrate, dimethylhydrazine, carbohydrazide, adipic dihydrazide and oxalic dihydrazide;
the aliphatic diamine chain extender is one or more of KH-792, ethylenediamine, di-o-chlorodiphenylamine methane and N, N-dihydroxy (diisopropyl) aniline; the amount of the catalyst is 0.001-0.010% of the mass of the diisocyanate.
Preferably, the time for adding the diquaternary ammonium salt-containing glycol monomer for mixing is 20-40 minutes;
the molar ratio of the polymer diol to the biquaternary ammonium salt diol to the diisocyanate is 1: 0.05-0.6: 1.4-2.5;
the emulsifying time in the step 3) is 20-40 minutes; the mass ratio of the deionized water to the prepolymer is 1-4: 1;
the molar ratio of the chain extender I to the diisocyanate in the step 4) is 0.2-0.4: 1.
preferably, the filtering screen is 80-400 meshes; the step of uniformly mixing is to stir for 30-90 min under the condition of 400-1000 r/min;
the raw materials in the step 5) comprise, by mass, 70-95% of the aqueous polyurethane emulsion, 0.5-3% of the defoaming agent, 0.1-1% of the leveling agent, 0.5-3% of the thickening agent, 0.1-1.5% of the curing agent, and the balance of deionized water.
Preferably, the defoaming agent is one or more of Foamex 843, BYK-019 and GSK 716;
the leveling agent is one or more of BYK333, Tego 450, FSN1 and Tego 482;
the thickening agent is Gel LW44, and the curing agent is one or more of Coat0Sil1770 or Bayhydur 305.
Compared with the prior art, the invention has the following advantages:
1) the monomer with the antibacterial function provided by the invention is a monomer containing biquaternary ammonium salt glycol, only two hydroxyl groups are used as active sites, and the monomer reacts with isocyanate, so that the reaction controllability is high; the biquaternary ammonium salt has excellent hydrophilicity and antibacterial property, and endows the polyurethane with self-emulsifying property and antibacterial property.
2) The diquaternary ammonium salt-containing diol monomer with the antibacterial function is introduced into a polyurethane main chain as a chain extender, so that the precipitation of an antibacterial agent can be effectively avoided, and the diquaternary ammonium salt-containing diol monomer can be quantitatively introduced according to needs to meet different antibacterial requirements.
3) The self-extinction waterborne polyurethane coating with the antibacterial function provided by the invention has the advantages that the rigidity of polyurethane latex particles is improved through the benzene ring and the carbamido group under the condition of completely not adding additional auxiliary agents or carrying out surface treatment on the adhesive film, so that the polyurethane latex particles are accumulated on the surface of the adhesive film to form an uneven structure, and an extinction effect is obtained.
Drawings
FIG. 1 is a structural formula and NMR spectrum of a diquaternary diol monomer prepared in example 1;
FIG. 2 is a structural formula and NMR spectrum of a diquaternary diol monomer prepared in example 2;
FIG. 3 is an infrared spectrum of a diquaternary ammonium salt diol monomer prepared in example 1 and a solid solute of an antibacterial self-extinction aqueous polyurethane coating prepared in example 8.
Detailed Description
The present invention is further described with reference to the following drawings and examples, which should be construed as being merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever, and which will enable those skilled in the art to make various changes and modifications within the spirit and scope of the present invention without making any creative effort.
Example 1
(1) Under the protection of nitrogen gas, 10g of hydroquinone, 38.5g of 2-diethylaminochloroethane hydrochloride and 130g of K2CO3Dissolving in 500ml acetone, reacting at 58 deg.C for 72 hr, filtering to remove precipitate, removing acetone by rotary evaporation, and dissolving the product in 50ml water;
(2) mixing the aqueous solution obtained in the step (2), 260ml of formaldehyde solution and 190ml of concentrated hydrochloric acid under hydrogen chloride atmosphere, reacting at room temperature for 16 hours, removing water out of the system, adding 600ml of mixed solvent of methanol and ethyl acetate (1: 75), filtering and collecting filter residue. Hydrolyzing the filter residue in 800ml of 20 percent NaOH ethanol solution to obtain a diol monomer containing the di-tertiary amine;
(3) the di-tertiary amine diol monomer containing the di-tertiary amine obtained in step (2) was dissolved in 200ml of acetone with 9.5g of n-butyl bromide and reacted at 58 ℃ for 72 hours. Drying to remove acetone, and washing with excessive n-hexane to obtain the monomer containing biquaternary ammonium salt diol.
The monomer structural formula and the NMR spectrum obtained in this example are shown in FIG. 1. Nuclear magnetic resonance hydrogen spectrum (600MHz, DMSO): δ 6.98(s,2H),4.34(s,4H), 4.28-4.25 (m,4H), 3.67-3.65 (m,4H),3.28(dtd,16H),1.94(s,2H),1.08(t, 22H); wherein the peak at 6.98ppm is hydrogen on the benzene ring of the obtained monomer, the peak at 4.34ppm is hydrogen on the carbon bonded to the benzene ring, and the peaks at 4.28-4.25 and 3.67-3.65ppm are subgeneric between N and OHydrogen on the methyl group, multiplet at 3.28ppm with N+Hydrogen on the attached methylene, the peak at 1.94ppm is hydrogen on the hydroxyl group, the peak at 1.08ppm is the methyl group and hydrogen on the adjacent 1 methylene group.
Example 2
(1) Under the protection of nitrogen gas, 10g of hydroquinone, 38.5g of 2-diethylaminochloroethane hydrochloride and 130g of K2CO3Dissolving in 500ml acetone, reacting at 58 deg.C for 72 hr, filtering to remove precipitate, removing acetone by rotary evaporation, and dissolving the product in 50ml water;
(2) mixing the aqueous solution obtained in the step (2), 260ml of formaldehyde solution and 190ml of concentrated hydrochloric acid under hydrogen chloride atmosphere, reacting at room temperature for 16 hours, removing water out of the system, adding 600ml of mixed solvent of methanol and ethyl acetate (1: 75), filtering and collecting filter residue. Hydrolyzing the filter residue in 800ml of 20 percent NaOH ethanol solution to obtain a diol monomer containing the di-tertiary amine;
(3) dissolving the diol monomer containing the di-tertiary amine obtained in the step (2) and 12.5g of bromo-n-hexane in 200ml of acetone, and reacting at 58 ℃ for 72 hours. Drying to remove acetone, and washing with excessive ethyl acetate to obtain the monomer containing biquaternary ammonium salt diol.
The structural formula and the NMR spectrum of the monomer obtained in example 2 are shown in FIG. 2. Hydrogen nuclear magnetic resonance spectrum (600MHz, DMSO) < delta > 6.97(s,2H),4.46(s,4H), 3.96-3.86 (m,4H),3.35(dtd,16H), 2.75-2.63 (m,4H),1.98(s,2H),0.97(t,30H) < delta > wherein the peak at 6.97ppm is hydrogen on the resulting monomeric benzene ring, the peak at 4.46ppm is hydrogen on the carbon attached to the benzene ring, the peaks at 3.96-3.86ppm and 2.75-2.63ppm are hydrogen on the methylene between N and O, the multiplet at 3.35ppm is hydrogen on the methylene connected to N+The hydrogen on the attached methylene group, the peak at 1.98ppm was the hydrogen on the hydroxyl group, and the peak at 0.97ppm was the methyl group and the hydrogen on the adjacent three methylene groups.
Example 3
(1) Dehydrating 100g of polycarbonate diol (PCDL, 1000g/mol), and cooling to 50 ℃; under the protection of nitrogen, 4.1g of the diquaternary ammonium salt-containing diol monomer obtained in example 1 is added and mixed for 30 minutes;
(2) adding 33.4g of isophorone diisocyanate (IPDI) and 0.01g of catalyst into the mixture obtained in the step (1), heating to 60-90 ℃, reacting for 3 hours, extracting a sample every 30 minutes, judging the reaction end point by using an n-butylamine titration method, and controlling the temperature to room temperature when the residual isocyanate value reaches 2.3 percent (the theoretical value is 2.8 percent);
(3) adding 317.2g of deionized water into the product obtained in the step (2) for emulsification for 30 minutes under strong stirring (the stirring speed is more than or equal to 600 rpm);
(4) dropwise adding 4.7g of hydrazine hydrate (with the hydrazine content of 80%) into the product obtained in the step (3) at 10 ℃, and continuing emulsifying and chain extending for 40 minutes;
(5) filtering the product obtained in the step (4) by using a 300-mesh filter screen to obtain an antibacterial self-extinction aqueous polyurethane emulsion with the solid content of 30 percent;
(6) at room temperature, 2.8g of a defoaming agent (Foamex 843, Evanik Degussa), 0.4g of a BYK333 leveling agent, 2.6g of a thickening agent (Gel LW44, Borchers Borchi) and 0.3g of a curing agent (Coat0Sil1770, motion Performance Materials Inc) are added into the antibacterial self-extinction aqueous polyurethane emulsion obtained in the step (5), and the mixture is dispersed for 30 minutes at 600rpm, so that the antibacterial self-extinction aqueous polyurethane coating is obtained, and the test results of the antibacterial self-extinction aqueous polyurethane coating are shown in Table 1.
Example 4
(1) Dehydrating 100g polytetrahydrofuran ether glycol (PTMG, 1000g/mol), and cooling to 50 deg.C; under the protection of nitrogen, 8.6g of the diquaternary ammonium salt-containing diol monomer obtained in example 1 is added and mixed for 30 minutes;
(2) adding 35.9g of isophorone diisocyanate (IPDI) and 0.01g of catalyst into the mixture obtained in the step (1), heating to 60-90 ℃, reacting for 3 hours, extracting a sample every 30 minutes, judging the reaction end point by using an n-butylamine titration method, and controlling the temperature to room temperature when the residual isocyanate value reaches 2.3 percent (the theoretical value is 2.8 percent);
(3) adding 329.4g of deionized water into the product obtained in the step (2) for emulsification for 30 minutes under strong stirring (the stirring speed is more than or equal to 600 rpm);
(4) dropwise adding 4.8g of hydrazine hydrate (with the hydrazine content of 80%) into the product obtained in the step (3) at 10 ℃, and continuing emulsifying and chain extending for 40 minutes;
(5) filtering the product obtained in the step (4) by using a 300-mesh filter screen to obtain an antibacterial self-extinction aqueous polyurethane emulsion with the solid content of 30 percent;
(6) and (3) adding 2.9g of a defoaming agent (Foamex 843, Evanik Degussa), 0.3g of a BYK333 leveling agent, 2.6g of a thickening agent (Gel LW44, Borchers Borchi) and 0.3g of a curing agent (Coat0Sil1770, motion Performance Materials Inc) into the antibacterial self-extinction aqueous polyurethane emulsion obtained in the step (5) at room temperature, and dispersing for 30 minutes at 600rpm to obtain the antibacterial self-extinction aqueous polyurethane coating.
Example 5
(1) Dehydrating 100g of polycarbonate diol (PCDL, 1000g/mol), and cooling to 50 ℃; under the protection of nitrogen, 13.2g of the diquaternary ammonium salt-containing diol monomer obtained in example 1 is added and mixed for 30 minutes;
(2) adding 45.5g of dicyclohexyl methane diisocyanate (HMDI) and 0.01g of catalyst into the mixture obtained in the step (1), heating to 60-90 ℃, reacting for 3 hours, extracting a sample every 30 minutes, judging the reaction end point by using an n-butylamine titration method, and controlling the temperature to room temperature when the residual isocyanate value reaches 2.3 percent (the theoretical value is 2.8 percent);
(3) adding 342.6g of deionized water into the product obtained in the step (2) for emulsification for 30 minutes under strong stirring (the stirring speed is more than or equal to 600 rpm);
(4) dropwise adding 4.9g of hydrazine hydrate (with the hydrazine content of 80%) into the product obtained in the step (3) at 10 ℃, and continuing emulsifying and chain extending for 40 minutes;
(5) filtering the product obtained in the step (4) by using a 300-mesh filter screen to obtain an antibacterial self-extinction aqueous polyurethane emulsion with the solid content of 30 percent;
(6) and (3) adding 3g of a defoaming agent (Foamex 843, Evonik Degussa), 0.4g of a BYK333 leveling agent, 2.3g of a thickening agent (Gel LW44, Borchers Borchi) and 0.3g of a curing agent (Coat0Sil1770, Momentive Performance Materials Inc) into the antibacterial self-extinction aqueous polyurethane emulsion obtained in the step (5) at room temperature, and dispersing for 30 minutes at 600rpm to obtain the antibacterial self-extinction aqueous polyurethane coating.
Example 6
(1) Dehydrating 100g of polycarbonate diol (PCDL, 1000g/mol), and cooling to 50 ℃; under the protection of nitrogen, 4.1g of the diquaternary ammonium salt-containing diol monomer obtained in the example 2 is added and mixed for 30 minutes;
(2) adding 33.4g of isophorone diisocyanate (IPDI) and 0.01g of catalyst into the mixture obtained in the step (1), heating to 60-90 ℃, reacting for 3 hours, extracting a sample every 30 minutes, judging the reaction end point by using an n-butylamine titration method, and controlling the temperature to room temperature when the residual isocyanate value reaches 2.3 percent (the theoretical value is 2.8 percent);
(3) adding 317.2g of deionized water into the product obtained in the step (2) for emulsification for 30 minutes under strong stirring (the stirring speed is more than or equal to 600 rpm);
(4) at 10 ℃, 8.5g of carbohydrazide is dripped into the product of the step (3), and the emulsification and chain extension are continued for 40 minutes;
(5) filtering the product obtained in the step (4) by using a 300-mesh filter screen to obtain an antibacterial self-extinction aqueous polyurethane emulsion with the solid content of 30 percent;
(6) and (3) adding 2.8g of a defoaming agent (Foamex 843, Evonik Degussa), 0.4g of a BYK333 leveling agent, 2.6g of a thickening agent (Gel LW44, Borchers Borchi) and 0.3g of a curing agent (Coat0Sil1770, motion Performance Materials Inc) into the antibacterial self-extinction aqueous polyurethane emulsion obtained in the step (5) at room temperature, and dispersing for 30 minutes at 600rpm to obtain the antibacterial self-extinction aqueous polyurethane coating.
Example 7
(1) Dehydrating 100g of polycarbonate diol (PCDL, 1000g/mol), and cooling to 50 ℃; under the protection of nitrogen, 8.6g of the diquaternary ammonium salt-containing diol monomer obtained in example 2 is added and mixed for 30 minutes;
(2) adding 45.5g of dicyclohexyl methane diisocyanate (HMDI) and 0.01g of catalyst into the mixture obtained in the step (1), heating to 60-90 ℃, reacting for 3 hours, extracting a sample every 30 minutes, judging the reaction end point by using an n-butylamine titration method, and controlling the temperature to room temperature when the residual isocyanate value reaches 2.3 percent (the theoretical value is 2.8 percent);
(3) adding 329.4g of deionized water into the product obtained in the step (2) for emulsification for 30 minutes under strong stirring (the stirring speed is more than or equal to 600 rpm);
(4) dropwise adding 4.8g of hydrazine hydrate (with the hydrazine content of 80%) into the product obtained in the step (3) at 10 ℃, and continuing emulsifying and chain extending for 40 minutes;
(5) filtering the product obtained in the step (4) by using a 300-mesh filter screen to obtain an antibacterial self-extinction aqueous polyurethane emulsion with the solid content of 30 percent;
(6) and (3) adding 2.9g of a defoaming agent (Foamex 843, Evanik Degussa), 0.3g of a BYK333 leveling agent, 2.6g of a thickening agent (Gel LW44, Borchers Borchi) and 0.3g of a curing agent (Coat0Sil1770, motion Performance Materials Inc) into the antibacterial self-extinction aqueous polyurethane emulsion obtained in the step (5) at room temperature, and dispersing for 30 minutes at 600rpm to obtain the antibacterial self-extinction aqueous polyurethane coating.
Example 8
(1) Dehydrating 100g polytetrahydrofuran ether glycol (PTMG, 1000g/mol), and cooling to 50 deg.C; under the protection of nitrogen, 8.6g of the diquaternary ammonium salt-containing diol monomer obtained in example 1 is added and mixed for 30 minutes;
(2) adding 35.9g of isophorone diisocyanate (IPDI) and 0.01g of catalyst into the mixture obtained in the step (1), heating to 60-90 ℃, reacting for 3 hours, extracting a sample every 30 minutes, judging the reaction end point by using an n-butylamine titration method, and controlling the temperature to room temperature when the residual isocyanate value reaches 2.3 percent (the theoretical value is 2.8 percent);
(3) adding 329.4g of deionized water into the product obtained in the step (2) for emulsification for 30 minutes under strong stirring (the stirring speed is more than or equal to 600 rpm);
(4) at 10 ℃, dropwise adding 5.8g of ethylenediamine into the product obtained in the step (3), and continuing emulsifying and chain extending for 40 minutes;
(5) filtering the product obtained in the step (4) by using a 300-mesh filter screen to obtain an antibacterial self-extinction aqueous polyurethane emulsion with the solid content of 30 percent;
(6) and (3) adding 2.9g of a defoaming agent (Foamex 843, Evanik Degussa), 0.3g of a BYK333 leveling agent, 2.6g of a thickening agent (Gel LW44, Borchers Borchi) and 0.3g of a curing agent (Coat0Sil1770, motion Performance Materials Inc) into the antibacterial self-extinction aqueous polyurethane emulsion obtained in the step (5) at room temperature, and dispersing for 30 minutes at 600rpm to obtain the antibacterial self-extinction aqueous polyurethane coating.
The monomer obtained in example 1 was subjected to Fourier infrared transmission test by KBr pellet method. As shown in FIG. 3, in the infrared spectrum of example 1, 3200-3300cm-1The peak is the vibration peak of hydroxyl; at 2800 and 3000cm-1The peak appeared here is the characteristic peak of methyl methylene; in particular, at 2940cm-1The subsidiary peaks at (A) are the peaks of C-H on the benzene ring at 1496 and 1467cm-1Is located at 1229cm from the vibration peak of benzene ring skeleton-1Is at the vibration peak of C-O at 1394cm-1The C-H bond is deformed by vibration, which is similar to N+It is related. In conclusion, the hydroxyl quaternary ammonium salt with a benzene ring structure has been successfully prepared.
The coating prepared in example 8 was poured into a tetrafluoroethylene mold with a film thickness of (0.5. + -. 0.1) mm, and then baked in an oven at 60 ℃ for 12 hours until dry, and the dried film was subjected to a Fourier transform infrared spectroscopy total reflection test. As shown in FIG. 3, in the infrared spectrum of example 8, 2260cm-1There is no absorption peak, which is a characteristic absorption peak of-NCO, indicating that the-NCO group has reacted to completion. At 2940 and 2760cm-1Absorption peaks observed in the range due to stretching vibrations of methyl and methylene groups. 3321cm-1、1701cm-1And 1041cm-1The peaks appearing there are N-H vibration, C ═ O vibration and C-O-C vibration in the carbamate group, respectively. Likewise, the C-H bond is at 1394cm-1The peak at (a) exhibited vibrational distortion, demonstrating that the bis-quaternary glycol had been incorporated into the molecular backbone. The infrared characteristic peaks indicate that the polyurethane is successfully synthesized.
Comparative example 1
(1) Dehydrating 100g of polycarbonate diol (PCDL, 1000g/mol), and cooling to 50 ℃; under the protection of nitrogen, 4.1g of the diquaternary ammonium salt-containing diol monomer obtained in example 1 is added and mixed for 30 minutes;
(2) adding 33.4g of isophorone diisocyanate (IPDI) and 0.01g of catalyst into the mixture obtained in the step (1), heating to 60-90 ℃, reacting for 3 hours, extracting a sample every 30 minutes, judging the reaction end point by using an n-butylamine titration method, and controlling the temperature to room temperature when the residual isocyanate value reaches 2.3 percent (the theoretical value is 2.8 percent);
(3) adding 317.2g of deionized water into the product obtained in the step (2) for emulsification for 30 minutes under strong stirring (the stirring speed is more than or equal to 600 rpm);
(4) filtering the product obtained in the step (3) by using a 300-mesh filter screen to obtain a water-based polyurethane emulsion with the solid content of 30%;
(5) and (3) adding 2.8g of a defoaming agent (Foamex 843, Evonik Degussa), 0.4g of a BYK333 leveling agent, 2.6g of a thickening agent (Gel LW44, Borchers Borchi) and 0.3g of a curing agent (Coat0Sil1770, Momentive Performance Materials Inc) into the aqueous polyurethane emulsion obtained in the step (4) at room temperature, and dispersing for 30 minutes at 600rpm to obtain the aqueous polyurethane coating.
Comparative example 2
(1) Dehydrating 100g of polycarbonate diol (PCDL, 1000g/mol), and cooling to 50 ℃; under the protection of nitrogen, 6.4g of DMPA is added and mixed for 30 minutes;
(2) adding 52.4g of isophorone diisocyanate (IPDI) and 0.01g of catalyst into the mixture obtained in the step (1), heating to 60-90 ℃, reacting for 3 hours, extracting a sample every 30 minutes, judging the reaction end point by using an n-butylamine titration method, and controlling the temperature to room temperature when the residual isocyanate value reaches 2.3 percent (the theoretical value is 2.8 percent);
(3) adding 4.8g of triethylamine to the product of the step (2) to adjust the pH value to 8, wherein the neutralization time is 30 minutes, and the neutralization temperature is 50 ℃; adding 367.6g of deionized water for emulsification under strong stirring (the stirring speed is more than or equal to 600rpm), wherein the emulsification time is 30 minutes;
(4) dropwise adding 4.7g of hydrazine hydrate (with the hydrazine content of 80%) into the product obtained in the step (3) at 10 ℃, and continuing emulsifying and chain extending for 40 minutes;
(5) filtering the product obtained in the step (4) by using a 300-mesh filter screen to obtain a water-based polyurethane emulsion with the solid content of 30%;
(6) and (3) adding 2.8g of a defoaming agent (Foamex 843, Evonik Degussa), 0.4g of a BYK333 leveling agent, 2.6g of a thickening agent (Gel LW44, Borchers Borchi) and 0.3g of a curing agent (Coat0Sil1770, Momentive Performance Materials Inc) into the aqueous polyurethane emulsion obtained in the step (5) at room temperature, and dispersing for 30 minutes at 600rpm to obtain the aqueous polyurethane coating.
In order to investigate the extinction and antibacterial properties of the prepared antibacterial self-extinction aqueous polyurethane coating, the following tests are carried out: the coatings obtained in examples 3 to 8, comparative example 1 and comparative example 2 were applied by roller coating to clean glass plates to a film thickness of (35. + -.5) μm, then baked in an oven at 60 ℃ for 15 minutes to dryness and measured for 60 ℃ gloss by a gloss meter according to ISO/2813, the results being shown in Table 1. The self-extinction index of paper made by Bachuan of Japan K.K. is considered to be an ideal self-extinction effect when the 60 ℃ gloss is 0 to 20. The paint obtained by the embodiment of the invention has 60-degree glossiness less than 20 without additional auxiliary agents or surface treatment, and achieves excellent self-extinction effect. It should be noted that step 4) in the technical solution of the present invention is one of the key points for imparting self-extinction property, and the lack of step 4) leads to rapid increase of glossiness. Comparative example 1 is an antibacterial coating in the prior art, lacks step 4) in the technical scheme, and has no self-extinction function; example 3, example 4 and example 5 have a self-extinction effect, and the gloss can be controlled by controlling the content of the diquaternary ammonium salt diol therein. This is because such a diquaternary ammonium salt diol is introduced into polyurethane as a chain extender having hydrophilicity, and as the content thereof increases, the hydrophilicity of polyurethane increases, smaller latex particles tend to be formed at the time of emulsification, the surface roughness formed by stacking decreases, and the gloss macroscopically increases.
TABLE 1
Figure BDA0003494622000000111
The coatings obtained in examples 3 to 8 and comparative examples 1 to 2 were poured into tetrafluoroethylene molds with a film thickness of (1. + -. 0.2) mm, and then baked in an oven at 60 ℃ for 12 hours to dry. Cutting the dried adhesive film into 2cm × 2cm sample pieces, and dripping 100 μ l of 10-concentration solution onto the surface6CFU/mL of bacterial suspension (E.coli or S.aureus) was spread evenly on the slide surface by covering the surface with a 2cm by 2cm coverslip. After the sample is incubated at 37 ℃ for 12 hours, the antibacterial rate of the sample is determined by using ultrasonic desorption bacteria and a flat plate bacteria culture method, and the results are shown in the specificationTable 1 shows. Comparative example 2 is waterborne polyurethane prepared without adding a diquaternary ammonium salt-containing diol monomer, and has no antibacterial property; examples 3-8 showed good antibacterial activity against both Escherichia coli and Staphylococcus aureus, which indicates that the antibacterial activity of the antibacterial self-extinction aqueous polyurethane coating prepared by the present invention is derived from the diquaternary ammonium salt diol monomer. The biquaternary ammonium salt content in examples 3-5 and examples 6-8 increased, and the antibacterial activity of the samples against escherichia coli and staphylococcus aureus increased. This is because, when the film is dried to form a film, the quaternary ammonium salt tends to be distributed on the outer side of the polyurethane latex microsphere due to its hydrophilicity, and the quaternary ammonium salt group having an antibacterial effect is concentrated on the surface, so that the antibacterial property is increased. The diquaternary ammonium salt diol monomer provided by the invention has certain hydrophilicity, and can endow the polyurethane molecular chain with self-emulsifying property when being introduced as a chain extender, so that other hydrophilic chain extenders and neutralizing agents are not required to be added, the preparation process is simplified, and the diquaternary ammonium salt diol only takes hydroxyl as a reaction active site for being connected to a polyurethane main chain, so that the reaction controllability is stronger, and the antibacterial and self-extinction properties can be obtained simultaneously.

Claims (10)

1. The di-quaternary ammonium salt-containing diol is characterized by having a structural general formula as follows:
Figure FDA0003494621990000011
wherein R is1An alkyl group having 1 to 10 carbon atoms; x is a chlorine atom or a bromine atom; m is an integer of 0-5, n is an integer of 0-20, and k is an integer of 1-20; r2Is hydrogen atom, methyl, sulfonic group or benzyl.
2. The method for preparing di-quaternary ammonium salt-containing diol according to claim 1, characterized by comprising the following steps and process conditions:
1) under the protection of inert gas, dissolving a raw material I, a raw material II and an alkaline substance in a solvent A, reacting for 48-96 hours at 50-120 ℃, filtering to remove precipitates, and dissolving a purified product in water;
2) mixing the aqueous solution of the product obtained in the step 1), a formaldehyde solution and concentrated hydrochloric acid in an acidic atmosphere, reacting at room temperature for 12-24 hours, and removing water out of the system; adding a mixed solvent of methanol and ethyl acetate into the product, filtering and collecting filter residues, and hydrolyzing the filter residues under an alkaline condition to obtain a diol monomer containing the ditertiary amine;
3) dissolving the di-tertiary amine diol-containing monomer obtained in the step 2) and a raw material III in a solvent B, reacting for 72-120 hours at 50-90 ℃, and purifying to obtain a di-quaternary ammonium salt diol-containing monomer;
the structural formulas of the raw material I, the raw material II and the raw material III are as follows:
Figure FDA0003494621990000012
wherein m is an integer of 0-5; k is an integer of 1 to 20, Y is a halogen element, R1An alkyl group having 1 to 10 carbon atoms; x is a chlorine atom or a bromine atom; m is an integer of 0 to 5, n is an integer of 0 to 20, R2Is hydrogen atom, methyl, sulfonic group or benzyl.
3. The method for preparing glycol containing diquaternary ammonium salt according to claim 2, wherein the solvent A is any one of acetonitrile, acetone, tetrahydrofuran, dimethyl sulfoxide, 1, 4-dioxane, N-dimethylformamide and N, N-dimethylacetamide; the solvent B is any one of acetonitrile, acetone, isopropanol, tetrahydrofuran and dioxane.
4. The method for preparing di-quaternary ammonium salt-containing diol according to claim 2 or 3, wherein the molar ratio of the raw material I to the raw material II to the alkaline substance is 1: 2-4: 4-50 of the compound is dissolved in a solvent A; the water solution, the formaldehyde solution and the concentrated hydrochloric acid are mixed according to the mol ratio of 1: 2-3: 2-20 mixing; the di-tertiary amine containing diol monomer and the raw material III are mixed according to a molar ratio of 1: 2-3 are dissolved in the solvent B.
5. The method for preparing glycol containing diquaternary ammonium salt according to claim 2, wherein the volume ratio of methanol to ethyl acetate in the mixed solvent is 1: 50-100 parts; the alkaline substance is at least one of sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
6. The method for preparing the antibacterial self-extinction aqueous polyurethane coating by using the diquaternary ammonium salt-containing glycol as the chain extender in claim 1 is characterized by comprising the following process steps and conditions:
1) dehydrating the polymer dihydric alcohol, and cooling to 40-50 ℃; under the protection of inert gas, adding a glycol monomer containing biquaternary ammonium salt for mixing;
2) adding diisocyanate and a catalyst into the mixture obtained in the step 1), heating to 60-90 ℃, and reacting for 2-5 hours to obtain a polyurethane prepolymer; when the residual isocyanate value reaches 85-95% of a theoretical value, controlling the temperature to be room temperature;
3) adding deionized water into the product obtained in the step 2) for emulsification under strong stirring (the stirring speed is more than or equal to 600 rpm);
4) dropwise adding hydrazine or aliphatic diamine chain extenders into the product obtained in the step 3) under the condition of 0-room temperature, and continuing emulsifying and chain extending for 15-50 minutes until isocyanate in the emulsion is completely reacted;
5) filtering the product obtained in the step 4) to obtain an antibacterial self-extinction polyurethane emulsion with the solid content of 20-50%;
6) adding an auxiliary agent into the antibacterial self-extinction aqueous polyurethane emulsion obtained in the step 5) at room temperature, and uniformly mixing to obtain an antibacterial self-extinction aqueous polyurethane coating; the auxiliary agent comprises a defoaming agent, a leveling agent, a thickening agent and a curing agent.
7. The method for preparing the antibacterial self-extinction aqueous polyurethane coating according to claim 6, wherein the polymer diol is one or more of polycaprolactone diol, polycarbonate diol, polyethylene adipate diol, polytetrahydrofuran ether glycol, polypropylene adipate diol, and polybutylene adipate diol; the molecular weight of the polymer dihydric alcohol is 1000-2000;
the diisocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and dicyclohexylmethane diisocyanate;
the catalyst is any one of dibutyltin dilaurate, stannous octoate and zinc octoate;
the hydrazine chain extender is one or more of hydrazine hydrate, dimethylhydrazine, carbohydrazide, adipic dihydrazide and oxalic dihydrazide;
the aliphatic diamine chain extender is one or more of KH-792, ethylenediamine, di-o-chlorodiphenylamine methane and N, N-dihydroxy (diisopropyl) aniline; the amount of the catalyst is 0.001-0.010% of the mass of the diisocyanate.
8. The method for preparing the antibacterial self-extinction aqueous polyurethane coating according to claim 6, wherein the time for adding the diquaternary ammonium salt-containing diol monomer for mixing is 20-40 minutes;
the molar ratio of the polymer diol to the biquaternary ammonium salt diol to the diisocyanate is 1: 0.05-0.6: 1.4-2.5;
the emulsifying time in the step 3) is 20-40 minutes; the mass ratio of the deionized water to the prepolymer is 1-4: 1;
the molar ratio of the chain extender I to the diisocyanate in the step 4) is 0.2-0.4: 1.
9. the method for preparing the antibacterial self-extinction waterborne polyurethane coating according to claim 6, wherein the filtering mesh is 80-400 meshes; the step of uniformly mixing is to stir for 30-90 min under the condition of 400-1000 r/min;
the raw materials in the step 5) comprise, by mass, 70-95% of the aqueous polyurethane emulsion, 0.5-3% of the defoaming agent, 0.1-1% of the leveling agent, 0.5-3% of the thickening agent, 0.1-1.5% of the curing agent, and the balance of deionized water.
10. The method for preparing the antibacterial self-extinction aqueous polyurethane coating according to claim 6 or 9, wherein the defoaming agent is one or more of Foamex 843, BYK-019 and GSK 716;
the leveling agent is one or more of BYK333, Tego 450, FSN1 and Tego 482;
the thickening agent is Gel LW44, and the curing agent is one or more of Coat0Sil1770 or Bayhydur 305.
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