CN109776754B - Preparation method of cationic waterborne UV polyurethane acrylate self-antibacterial resin - Google Patents
Preparation method of cationic waterborne UV polyurethane acrylate self-antibacterial resin Download PDFInfo
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Abstract
The invention discloses a preparation method of a cationic waterborne UV polyurethane acrylate self-antibacterial resin. Firstly, mixing and heating polyisocyanate, a polyol compound and a catalyst to prepare an intermediate product containing 3-4 isocyanic acid radical (-NCO) groups; then adding amine compound and hydroxyl-terminated vinyl compound for end capping, adding organic acid and photoinitiator to obtain hydrophilic resin, adding water, stirring at high speed to form dispersion, and finally adding auxiliary agent to obtain the cationic water-based UV self-antibacterial coating. Aiming at the problems of poor storage stability, need of additionally adding an antibacterial agent and weak antibacterial durability of the common cationic water-based UV coating, the prepared coating has high stability and excellent mechanical properties, tensile strength and thermal decomposition resistance of a coating film; the preparation method is novel, simple in steps and nontoxic and odorless; the self-killing rate of the bacteria exceeds 99 percent.
Description
Technical Field
The invention relates to a preparation method of cationic waterborne UV (ultraviolet) polyurethane acrylate self-antibacterial resin, belonging to the technical field of polyurethane acrylate resin materials.
Background
The polyurethane has excellent mechanical properties, adjustable molecular structure and good biocompatibility, and can be widely applied to the fields of mechanical equipment, transportation equipment, terrace venues, medical equipment and the like. The ministry of industry and informatization, issued "guidance on development of key common technology in industry (2017), in particular proposed aqueous polyurethane resin and downstream application technologies, including acrylate modified aqueous polyurethane technology, aqueous polyurethane coating technology, aqueous solvent-free high-solid-content foamed polyurethane technology and the like. In these emphatically advocated fields, UV waterborne polyurethanes are favored because of their non-toxicity, environmental protection, good biocompatibility, good flexibility and elasticity of the coating, high decorativeness, and the advantage of rapid curing. The traditional cationic UV waterborne polyurethane is prepared by adopting a method of prepolymerization of glycol and diisocyanate, chain extension by using diamine, end capping by using hydroxyl acrylate, and finally neutralizing by using organic acid and adding water for dispersion, wherein a resin chain segment is in a linear structure, amino is positioned at the main chain of a molecular chain, and part of amino can be hidden due to winding and folding of the molecular chain and can not completely react with acid in a neutralization stage, so that excessive amine is needed to obtain enough hydrophilicity of the resin, the amine value is high (generally more than 50 mgKOH/g), and the coating is easy to yellow.
Chinese patent CN100487014 discloses a preparation method of a polyurethane acrylate resin, which comprises reacting isocyanate tripolymer with hydroxyl acrylate in the presence of a catalyst, a solvent and a polymerization inhibitor, and the coating prepared by the method has high hardness and good wear resistance. However, this patent uses a large amount of organic solvent, and has high VOC; chinese patent CN101906192B discloses a preparation method of a waterborne polyurethane-acrylate composite dispersion. The method comprises the steps of synthesizing a waterborne polyurethane prepolymer from polymer dihydric alcohol, diisocyanate and a hydrophilic chain extender, then carrying out end capping on the prepolymer by using a vinyl compound, then neutralizing, dropwise adding water for self-emulsification to obtain a waterborne polyurethane dispersoid with a linear structure, and dropwise adding an acrylate monomer dissolved with an initiator for polymerization to obtain the waterborne polyurethane-acrylate composite dispersoid. When the equivalent effect of the invention is achieved, the steps are complicated, the product lacks antibacterial property, and the dispersion is unstable; U.S. Pat. No. 5,430,440 describes the preparation of aqueous resin dispersions by introducing hydrophilic groups by reaction of carboxyl-terminated polyethers with polyisocyanates, followed by addition of diluents and deionized water. The resin dispersion prepared by the method has poor stability, is easy to hydrolyze, and the product lacks antibacterial property. In conclusion, most of the existing aqueous polyurethane acrylate aqueous dispersions and coatings have the defects of large particle size of the aqueous dispersions, higher VOC, low solid content and instability; poor thermal stability of the coating and the like.
Along with the improvement of the living level of people and the requirement on environmental safety, higher antibacterial requirements are put forward on the coating, in particular to the water-based coating used on the surfaces of home medical treatment, public places, children products and books and paper. Most of the antibacterial coatings on the market realize functions by adding additional metal or organic antibacterial agents, such as nano silver particles, triclosan and the like, and Chinese patent CN101077077A discloses a nano silver antibacterial mixture which is sprayed on the surface of an object, wherein the antibacterial agent has high price, single antibacterial group and short action time; chinese patent CN101250344B discloses a paint with triclosan as an antibacterial agent, wherein triclosan is harmful to human body and is prohibited from being used in countries such as america and japan, and the durable antibacterial performance of the external antibacterial paint is also poor.
Disclosure of Invention
The invention solves the technical problems that the existing cationic water-based UV polyurethane acrylic resin has high amine value, unstable dispersion, poor coating tensile strength, poor self antibacterial property, poor high-temperature decomposition resistance and the like.
The technical scheme of the invention is to provide a preparation method of cationic waterborne UV polyurethane acrylate self-antibacterial resin, wherein the resin mainly comprises the following raw materials (except solvent) in percentage by mass:
3 to 5 percent of amine compound, 32 to 45 percent of diisocyanate, 35 to 50 percent of alcohol compound, 0.5 to 2.5 percent of catalyst, 2.5 to 10 percent of hydroxyl-terminated acrylate compound, 2 to 5 percent of organic acid and 2 to 6 percent of photoinitiator; the alcohol compounds comprise dihydric alcohol compounds and trihydric alcohol compounds; the preparation method of the resin comprises the following steps:
(1) adding diisocyanate, a triol compound and a catalyst into a reaction device, uniformly mixing, heating to 90-100 ℃, and reacting for 1-4 h to generate a prepolymer; dripping a dihydric alcohol compound into a reaction device containing the prepolymer, performing chain extension reaction with the prepolymer at the temperature of 60-90 ℃, and continuously reacting for 2-4 h after dripping to obtain an intermediate product with isocyanate groups;
(2) adding the intermediate product with the isocyanate group, the hydroxyl-terminated acrylate compound and the amine compound into a reaction device to react for 4 to 7 hours at the temperature of between 70 and 80 ℃, removing the redundant amine compound and reaction solvent, adding organic acid and a photoinitiator, mixing and stirring for 1 to 3 hours, and obtaining the cationic waterborne UV polyurethane acrylate self-antibacterial resin.
Preferably, the mass ratio of the dihydric alcohol compound to the trihydric alcohol compound is 1: 0.4-4.
Preferably, the diol compound is polyester diol and/or polyether diol.
Preferably, the diol compound is one or more of polycaprolactone diol, polycarbonate diol, polybutylene adipate, polyethylene glycol and polypropylene glycol; the triol compound is polycaprolactone triol and/or glycerol.
Preferably, the raw material of the resin also contains 0.1-0.5 mass percent of polyethylene glycol monomethyl ether.
Preferably, the diisocyanate is one or more of isophorone diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and toluene diisocyanate; the amine compound is one or more of N-methyldiethanolamine, N-dimethylethanolamine, triethanolamine, triethylamine and N-benzoyl phenylhydroxylamine.
The hydroxyl-terminated acrylate compound is acrylate with hydroxyl at the end. Preferably, the hydroxyl-terminated acrylate compound is one or more of hydroxyethyl acrylate, beta-hydroxyethyl methacrylate, hydroxypropyl acrylate and pentaerythritol triacrylate;
preferably, the catalyst is an organobismuth catalyst; preferably, the organic acid is one or more of acetic acid, lactic acid, glycocyamine and glycocyamine; preferably, the organic acid comprises a guanidino group-containing organic acid.
The invention also provides a resin dispersion which mainly comprises 20-50% of the resin obtained by the preparation method and 50-80% of water according to mass percentage.
The invention also provides a coating which comprises 99.0-99.8% of the resin dispersoid, 0.1-0.5% of a leveling agent and 0.1-0.5% of a wetting agent in percentage by mass.
The photoinitiator, the leveling agent and the wetting agent are all products sold in the market, and the specific models are the photoinitiator 1173, the wetting agent BYK-2000 and the leveling agent BYK-306.
The preparation of the coating is realized by the following four steps: (1) synthesizing an intermediate product with 3-4-NCO groups; (2) preparing ultraviolet curing resin; (3) dispersing deionized water and preparing a coating; (4) and (4) preparing the coating.
The concrete content of each step is as follows:
step one, preparing an intermediate product with 3-4-NCO isocyanate groups: adding diisocyanate, a triol compound and a catalyst into a reaction device, uniformly mixing, heating to 90-100 ℃ for reaction, and continuously reacting for 1-4 h at constant temperature to generate a prepolymer; dropwise adding a calculated amount of polyester or polyether diol into the device within 2h, further reacting with the prepolymer at 60-90 ℃ for chain extension, and continuously reacting for 2-4 h at constant temperature after dropwise adding to obtain an intermediate product with 3-4 isocyanate groups (preferably 4 isocyanate groups); the number of isocyanate groups in the intermediate product is the average number;
step two, preparing ultraviolet light curing polyurethane acrylic resin: adding the intermediate product with 3-4 isocyanate groups, the hydroxyl-terminated acrylate compound, the amine compound and the polyethylene glycol monomethyl ether in the proportion into a reaction device at the temperature of 70-80 ℃ for reaction for 4-7 h, removing redundant amines and organic solvents by reduced pressure distillation, adding organic acid and a photoinitiator, mixing and stirring for 1-3 h to obtain the cationic waterborne UV polyurethane acrylate self-antibacterial resin;
step three, deionized water dispersion and coating preparation: adding deionized water into dispersing equipment at one time, mixing the deionized water with the waterborne UV polyurethane acrylate self-antibacterial resin, adjusting the stirring speed to 1000-3000 r/min, dispersing for 10-30 min to obtain a transparent slightly blue-light-carrying dispersoid, adding a flatting agent and a wetting agent, and stirring for 1h to obtain the coating, wherein the solid content of the dispersoid is about 20-50%, the pH value is 4.7-6.9, and the viscosity is 300-1000 mPa.s;
step four, preparing a coating film by using the water-based UV coating: the coating is coated according to different coating modes such as spraying, rolling, spraying or wiping, the coating with the thickness of 10-50 microns can be obtained, the coating is firstly baked for 5-15 min at the temperature of 80 ℃, and then the coating is cured in ultraviolet curing equipment for 1-3 min, so that the coating is obtained.
The cationic waterborne UV polyurethane acrylate self-antibacterial resin belongs to a pendant ammonium salt waterborne UV polyurethane acrylate self-antibacterial resin, and the raw materials of the resin comprise, by mass, 3% -5% of an amine compound, 32% -45% of diisocyanate, 35% -50% of an alcohol compound, 0.5% -2.5% of a catalyst, 2.5% -10% of a hydroxyl-terminated acrylate compound, 2% -5% of an organic acid and 2% -6% of a photoinitiator. The above composition is a raw material composition of the resin, wherein water or an organic solvent (reaction solvent providing liquid phase conditions) is not counted as a raw material of the resin.
The cationic waterborne UV polyurethane acrylate self-antibacterial resin dispersion comprises the following components in percentage by mass: 20 to 50 percent of self-antibacterial resin and 50 to 80 percent of deionized water.
The cationic waterborne UV polyurethane acrylate self-antibacterial resin coating comprises the following components in percentage by mass: 99 percent of self-antibacterial resin dispersoid, 0.1 to 0.5 percent of flatting agent and 0.1 to 0.5 percent of wetting agent.
The diisocyanate is one or more of isophorone diisocyanate (IPDI), tetramethylxylene diisocyanate (TMXDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI), etc.; the amine compound is one or more of N-methyldiethanolamine, N-dimethylethanolamine, triethanolamine, triethylamine, N-benzoylphenylhydroxylamine and the like; the alcohol compound is diol and triol compound, and comprises one or more of polycaprolactone diol, polycaprolactone triol, polycarbonate diol, glycerol, polybutylene adipate, polyethylene glycol monomethyl ether, polypropylene glycol and the like; the weight average molecular weight (Mw) of the alcohol compound is 500-4000; the hydroxyl-terminated acrylate compound is hydroxyethyl acrylate, methacrylic acid-beta-hydroxyethyl ester, hydroxypropyl methacrylate, hydroxypropyl acrylate, pentaerythritol triacrylate, derivatives and the like; the catalyst is one or more of organic bismuth catalysts BICAT8118, 8108 and 8106; the organic solvent is one or more of ethyl acetate, butyl acetate, methyl isobutyl ketone, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate and acetone, and the using amount of the organic solvent during synthesis is 10-20% of the total mass of the raw materials; the organic acid is one or more of acetic acid, lactic acid, glycocyamine and glycocyamine, and the dosage of the organic acid is 2-5% of the total mass of the raw materials.
Firstly, mixing and heating diisocyanate, a polyol compound and a catalyst to prepare an intermediate product containing 3-4 isocyanic acid radical (-NCO) groups; then adding amine compounds and hydroxyl-terminated acrylate compounds for end capping, adding organic acid and a photoinitiator to obtain hydrophilic resin, adding water, stirring at a high speed to form a dispersion, and finally adding an auxiliary agent to obtain the cationic water-based UV self-antibacterial coating. Aiming at the problems of poor storage stability, need of additionally adding an antibacterial agent and weak antibacterial durability of the common cationic water-based UV coating, the prepared coating has high stability and excellent mechanical properties, tensile strength and thermal decomposition resistance of a coating film; the preparation method is novel, simple in steps and nontoxic and odorless; the self-killing rate of the bacteria exceeds 99 percent.
The invention designs and prepares an intermediate product with 3-4-NCO groups by a macromolecular synthesis principle, then adds hydroxyl polyester or polyether, utilizes the reaction of-NCO and-OH to carry out chain extension, and finally uses hydroxyl-terminated acrylate and amine compounds to carry out end capping, so that a chain segment with an amine group can be effectively controlled on the whole polymer side chain, thereby the resin can be endowed with hydrophilicity to the maximum extent, and the amine group exposed on the side chain can be more easily neutralized with acid to carry out salt forming reaction, so the resin obtained by the invention can reduce the usage amount of amine substances, and the amine value is relatively low; in addition, natural organic acids such as lactic acid, glycocyamine and the like are introduced to be matched as a neutralizing agent, so that the antibacterial capability and durability of the waterborne UV polyurethane acrylate self-antibacterial resin coating are further improved. The self-antibacterial coating disclosed by the invention contains antibacterial groups such as quaternary ammonium salt, guanidino, polyethylene glycol and the like, and can realize multi-effect long-term self-antibacterial without an additional bactericide. For example, the resin of the present invention has a killing rate of over 99% against gram-negative and positive bacteria.
Compared with the prior art, the invention has the following beneficial effects:
(1) the amino group of the waterborne UV-cured self-antibacterial coating is positioned on the side group of a molecular chain in the synthesis process, so that the coating can be fully exposed in the dispersion process, the needed amine is less, and the amine value is low and is about 20 mgKOH/g.
(2) The water-based UV self-antibacterial coating has good storage stability, does not have the phenomena of layering and sedimentation after being stored for 30 days at 50 ℃, and is convenient to store and transport.
(3) The water-based UV self-antibacterial coating has good biocompatibility, and the mechanical property, tensile strength and high-temperature decomposition resistance of the coating are obviously improved compared with those of common linear polyurethane acrylate.
(4) The organic bismuth catalyst used in the synthesis is an accelerator for curing reaction, so that the water-based UV self-antibacterial coating has short curing time and high curing speed (the water-based UV self-antibacterial coating has 1kW power and can be completely cured only by curing for 30-120 s at a rotating speed of 20 m/min).
(5) In the invention, guanidinoacetic acid, guanidinopropionic acid, guanidinophosphoric acid and other guanidino acids are introduced to neutralize the cationic resin, guanidino is connected to the molecular chain of the tertiary amino resin through neutralization reaction to form macromolecules of quaternary ammonium salt with guanidino, the coating can realize the antibacterial effect of the structure, and the antibacterial performance is greatly improved compared with that of the common antibacterial coating.
The invention can be directly applied to the technical field of coating, improves the appearance decoration and antibacterial property, and is particularly suitable for the fields of medical equipment, automotive interior, printing ink and the like.
Drawings
FIG. 1 is an infrared spectrum of the molecular structure of a cationic aqueous UV polyurethane acrylate self-antibacterial resin in example 1 provided by the invention.
FIG. 2 is a particle size distribution diagram of a cationic aqueous UV urethane acrylate self-antibacterial resin dispersion in example 1 provided by the present invention.
Fig. 3 is a schematic contact angle diagram of a cationic aqueous UV urethane acrylate self-antibacterial coating in example 2 provided by the present invention.
FIG. 4 is a differential thermal (DSC) comparison of a cationic waterborne UV urethane acrylate self-antimicrobial coating of example 2 provided by the present invention and a comparative example coating.
FIG. 5 is a graph showing the antibacterial results of a cationic aqueous UV urethane acrylate self-antibacterial coating in example 3 provided by the present invention (the left side is a comparative example coating, the right side is a coating of example 2 of the present invention; the upper side is a comparison of tannery-negative bacteria (E. coli) and the lower side is a comparison of tannery-positive bacteria (Bacillus subtilis)).
FIG. 6 is an atomic force microscope comparison of a cationic aqueous UV urethane acrylate self-antibacterial coating in example 3 provided by the present invention.
FIG. 7 is a comparative plot of the dispersions of examples 1, 2 and 3 provided by the present invention and the comparative dispersion (sample No. 1, 2, 3 is the dispersion of examples 1, 2, 3 of the present invention, sample No. 4 is the dispersion of the comparative example).
FIG. 8 is a comparison of the tensile strength of example 1 and comparative example coatings provided by the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Preparing the following raw materials in percentage by mass:
the mass percentage (wt.%) of the resin component is: 38.3% of isophorone diisocyanate, 7.2% of glycerol, 22% of polycarbonate diol, 8% of polycaprolactone diol, 3% of polycaprolactone triol, 1.5% of lactic acid, 1% of guanidinoacetic acid, 81180.9% of BICAT, 9.7% of pentaerythritol triacrylate, 0.3% of beta-hydroxyethyl methacrylate, 0.1% of polyethylene glycol monomethyl ether, 4% of N-methyldiethanolamine and 4% of photoinitiator.
Uniformly mixing the isophorone diisocyanate, the polycaprolactone triol, the glycerol, the BICAT8118 catalyst and the solvent in the proportion in a reactor provided with a reflux device, a heating device and a stirring device. Heating to 90-100 ℃ for mixing reaction, continuously reacting for 3h at constant temperature, adding the calculated polycarbonate diol and polycaprolactone diol into a device at 60-90 ℃, continuously reacting for 4h at constant temperature, adding pentaerythritol triacrylate, beta-hydroxyethyl methacrylate, polyethylene glycol monomethyl ether and N-methyldiethanolamine at the ratio for reacting for 4h at 70-80 ℃, removing redundant amines and organic solvents by reduced pressure distillation, dropwise adding guanidinoacetic acid, lactic acid and a photoinitiator into the reaction device, and reacting for 2h to obtain the cationic water-based UV polyurethane acrylate self-antibacterial resin, wherein the amine value is 17.1mgKOH/g, the dispersion is transparent with blue light, and the solid content is 31%.
The infrared spectrum of the cationic water-based UV polyurethane acrylate self-antibacterial resin of example 1 is shown in figure 1, wherein 3500cm-1No obvious stretching vibration of O-H is found, which indicates that most of-OH is completely reacted; 3387cm-12988cm, as a telescopic shock absorption peak of-NH-)-1、2843cm-1Are respectively-CH3、-CH2Characteristic absorption peak of functional group, 2267cm-1In order to find no obvious characteristic absorption peak of the-NCO group, the-NCO is completely reacted; 1714cm-1Is a C-O-C asymmetric stretching vibration characteristic absorption peak in an ester bond, and the formation of the urethane bond is shown above. 1638cm-1Characteristic absorption of stretching vibration of C ═ C skeleton at alkenyl group, and 814cm-1The peak appears in the position of expansion and contraction vibration of C-H on C ═ C double bond, which indicates that the end capping of HEMA is successful, 1469cm-1Is the stretching vibration of methoxyl group, 1090cm-1Is an absorption peak of ether bond C-O-C, which indicates that the capping of the polyethylene glycol monomethyl ether is successful, and 1169cm-1The stretching vibration of the C-N bond in N-methyldiethanolamine shows that the synthesis is successful.
Fig. 2 shows a particle size distribution diagram of a dispersion formed by emulsifying cationic aqueous UV polyurethane acrylate self-antibacterial resin according to the present invention, and it can be seen from the figure that the average particle size is 45.32nm, which illustrates that the cationic aqueous UV polyurethane acrylate self-antibacterial resin prepared according to the embodiment of the present invention has a good emulsifying ability. The coating dispersoid is coated on a galvanized iron test plate which is polished in advance, and a smooth transparent coating is formed by photocuring under an ultraviolet lamp after water is volatilized. The main performance criteria of the coating are shown in table 1:
table 1 comparison of coating properties of example 1 and comparative example
Example 2
Preparing the following raw materials in percentage by mass:
the mass percentage (wt.%) of the resin component is: 35% of tetramethylxylylene diisocyanate, 7.1% of glycerol, 20% of polycaprolactone diol, 10% of polycaprolactone triol, 7% of polyethylene glycol, 2.5% of acetic acid, 0.5% of guanidinopropionic acid, BICAT 81080.5%, 5.7% of pentaerythritol triacrylate, 3.5% of hydroxyethyl acrylate, 0.2% of polyethylene glycol monomethyl ether, 1% of diethanolamine, 2% of N-benzoylphenylhydroxylamine and 5% of photoinitiator.
Adding the tetramethyl xylylene diisocyanate, the polycaprolactone triol, the glycerol, the polycaprolactone triol, the BICAT8108 and the solvent in proportion into a reactor provided with a reflux device, a heating device and a stirring device, and uniformly mixing. Heating to 90-100 ℃ for mixing reaction, continuously reacting for 3h at constant temperature, adding the calculated amount of polycaprolactone diol and polyethylene glycol into a device at 60-90 ℃, continuously reacting for 4h at constant temperature, adding the pentaerythritol triacrylate, hydroxyethyl acrylate, polyethylene glycol monomethyl ether, N-benzoylphenylhydroxylamine and diethanolamine into the reaction device for reaction for 4h at 70-80 ℃, removing redundant amines and organic solvents by reduced pressure distillation, then adding guanidinopropionic acid, acetic acid and a photoinitiator into the reaction device, and stirring for 2h after the addition is finished, thus obtaining the cationic waterborne UV polyurethane acrylate self-antibacterial resin. The cationic resin is transparent viscous resin, has the solid content of 67 percent, the amine value of 18.3mgKOH/g and the solid content of 32 percent, and is transparent with blue light.
Compared with linear cationic resin, the amine value of the resin is about 60% lower when the molecular weight and the dispersion condition are the same, which means that the same dispersion effect is achieved, the amine needed by the resin is less, and the yellowing of a coating caused by the oxidation of the amine is avoided. The invention uses amine to seal the end, the amine loss is less, and the reaction degree is high.
Taking a proper amount of cationic resin, and adding a proper amount of deionized water to obtain the coating. The coating is transparent with blue light, has the solid content of 30 percent and the pH value of 5.77. As shown in fig. 3, the contact angle of the coating of example 2 with water was measured and found to be less than 90 °, and the prepared coating was hydrophilic, which indicates that the coating of the present invention has better biocompatibility.
The coating dispersion is coated on a polished tinplate test plate in advance, and after water is volatilized, the coating dispersion is photocured under a UV lamp to form a smooth transparent coating. As shown in FIG. 4, the heat absorption peak number of the coating of the invention is reduced and obviously shifted backwards by carrying out differential thermal analysis on the coating of the invention and the coating of the comparative example, the heat absorption decomposition temperature is improved by about 50 ℃ compared with the coating of the comparative example, and the high temperature decomposition resistance is greatly enhanced.
Example 3
Preparing the following raw materials in percentage by mass:
the mass percentage (wt.%) of the resin component is: 16.2% of isophorone diisocyanate, 8.5% of tetramethyl xylylene diisocyanate, 10.5% of diphenylmethane diisocyanate, 3.5% of N-methyldiethanolamine, 1.5% of N, N-dimethylethanolamine, 5% of polycarbonate diol, 23.6% of polypropylene glycol, 13% of polycaprolactone triol, 1.5% of acetic acid, 4.5% of guanidinoacetic acid, BICAT 81080.7%, 7% of pentaerythritol triacrylate, 0.5% of polyethylene glycol monomethyl ether and 4% of photoinitiator.
Uniformly mixing the diphenylmethane diisocyanate, the isophorone diisocyanate, the tetramethyl xylylene diisocyanate, the polycaprolactone triol, the BICAT8108 and the solvent in the proportion in a reactor provided with a reflux device, a heating device and a stirring device. Heating to 90-100 ℃ for mixing reaction, continuously reacting for 3h at constant temperature, adding the calculated polycarbonate diol and polypropylene glycol into a device at 60-90 ℃, continuously reacting for 4h at constant temperature, adding the pentaerythritol triacrylate, polyethylene glycol monomethyl ether, N-methyldiethanolamine and N, N-dimethylethanolamine in the proportion into the reaction device at 70-80 ℃ for reacting for 4h, removing redundant amines and organic solvents by reduced pressure distillation, dripping guanidino phosphoric acid, acetic acid and a photoinitiator into the reaction device, and stirring for 2h after dripping is finished to obtain the cationic aqueous UV polyurethane acrylate self-antibacterial resin. The cationic resin is transparent viscous resin, has the solid content of 72 percent, the amine value of 19.1mgKOH/g and the solid content of 32 percent, and is transparent with blue light.
Taking a proper amount of cationic resin, adding a proper amount of deionized water and an auxiliary agent to obtain the self-antibacterial coating. Bacterial experiments show that the example 3 of the invention has good killing or inhibiting effect on both leather-type negative bacteria and leather-type positive bacteria, and the killing rate is over 99 percent (figure 5). Atomic force microscope observation of the coating of example 3 of the present invention revealed that the coating of the present invention had smooth and flat surface and that the bactericidal groups were evenly distributed on the surface of the coating (fig. 6). Example 3 was subjected to accelerated storage stability tests at various temperatures and the results are shown in table 2:
table 2 comparison of the stability of example 3 and comparative dispersions at different temperatures in accelerated storage (30 days)
| |
0℃ | 25℃ | 50℃ | 65℃ |
| Example 3 | Not layering | Not layering | Not layering | Slightly layered |
| Comparative example | Slightly layered | Not layering | Layering | Layering |
According to GB/T6753.3-1986, samples can be stored for 6 months to 1 year under natural conditions if they pass the accelerated storage stability test at 50 ℃. By comparing accelerated tests at different temperatures, it can be shown that the emulsion of the invention has better stability than the comparative PUD.
As shown in FIG. 7, at the same 30% by weight solids content, the dispersions prepared according to the invention are clear in appearance, whereas the comparative dispersion appears milky, which represents the excellent dispersing properties of the dispersions according to the invention; fig. 8 clearly illustrates the better strength and toughness of the coating of the present invention.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (1)
1. The coating is characterized by comprising 99.0-99.8% of resin dispersoid, 0.1-0.5% of flatting agent and 0.1-0.5% of wetting agent by mass percent;
wherein, the resin dispersoid mainly comprises 20 to 50 percent of cationic water-based UV polyurethane acrylate self-antibacterial resin and 50 to 80 percent of water according to the mass percentage;
the cationic waterborne UV polyurethane acrylate self-antibacterial resin is mainly prepared from the following raw materials in percentage by mass:
16.2% of isophorone diisocyanate, 8.5% of tetramethylxylylene diisocyanate, 10.5% of diphenylmethane diisocyanate, 3.5% of N-methyldiethanolamine, 1.5% of N, N-dimethylethanolamine, 5% of polycarbonate diol, 23.6% of polypropylene glycol, 13% of polycaprolactone triol, 1.5% of acetic acid, 4.5% of guanidinium phosphate, BICAT 81080.7%, 7% of pentaerythritol triacrylate, 0.5% of polyethylene glycol monomethyl ether, and 4% of a photoinitiator;
the preparation method of the cationic waterborne UV polyurethane acrylate self-antibacterial resin comprises the following steps:
(1) adding diphenylmethane diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, polycaprolactone triol, BICAT8108 and a solvent into a reaction device, uniformly mixing, heating to 90-100 ℃, and reacting for 3 hours to generate a prepolymer; dripping polycarbonate diol and polypropylene glycol into a reaction device containing the prepolymer, performing chain extension reaction with the prepolymer at 60-90 ℃, and continuing to react for 4 hours after dripping is finished to obtain an intermediate product with isocyanate groups;
(2) adding the intermediate product with isocyanate groups, pentaerythritol triacrylate, polyethylene glycol monomethyl ether, N-methyldiethanolamine and N, N-dimethylethanolamine into a reaction device to react for 4 hours at the temperature of 70-80 ℃, removing redundant amine compounds and reaction solvents, adding guanidinophosphoric acid, acetic acid and a photoinitiator, mixing and stirring for 2 hours to obtain the cationic waterborne UV polyurethane acrylate self-antibacterial resin.
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| CN112574376B (en) * | 2020-11-16 | 2022-09-16 | 万华化学集团股份有限公司 | Antibacterial polyurethane resin and preparation method thereof |
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