CN114672215A - Preparation method of nano ZnO modified polyacrylate emulsion composite coating - Google Patents

Preparation method of nano ZnO modified polyacrylate emulsion composite coating Download PDF

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CN114672215A
CN114672215A CN202210316566.XA CN202210316566A CN114672215A CN 114672215 A CN114672215 A CN 114672215A CN 202210316566 A CN202210316566 A CN 202210316566A CN 114672215 A CN114672215 A CN 114672215A
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nano zno
composite coating
emulsion
modified polyacrylate
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尚磊
张友志
张董寅
张欣
方慎之
吴迪
庄斯宇
杜沄飞
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Jiangsu University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a preparation method of a nano ZnO modified polyacrylate emulsion composite coating, which adopts nano ZnO, acrylic soft and hard monomers and functional monomers as raw materials, and prepares the polyacrylate nano ZnO composite coating through Pickering emulsion polymerization, the process is simple, a surfactant is not required, and the environment can be effectively protected; the introduction of the nano particles improves various performances of the coating after film forming, the water resistance of the coating exceeds 5 days, and the antibacterial property reaches 80%, so that the nano particles can be widely applied to the fields of building wall coatings, adhesives and the like.

Description

Preparation method of nano ZnO modified polyacrylate emulsion composite coating
Technical Field
The invention relates to the technical field of composite coatings, in particular to a preparation method of a nano ZnO modified polyacrylate emulsion composite coating.
Background
As a polymer material with wide application prospect, polyacrylate has good light resistance, ultraviolet resistance and acid and alkali resistance, and a coating film formed by a polymer of the polyacrylate also has high toughness and high corrosion resistance, so that the polyacrylate is widely applied to the fields of building wall coatings, adhesives, leather appliances and the like.
However, the modified material still has other defects, such as poor water resistance, easy viscosity loss at high temperature, easy brittleness at low temperature and the like, so that the application prospect is limited, and the polyacrylate cannot be further developed.
In recent years, there are many methods for compounding polyacrylate emulsions, for example, Pickering emulsion polymerization, which is a polymerization method for preparing stable emulsion by replacing emulsifier with nanoparticles, so as to reduce the use of surfactant reagents and reduce environmental pollution.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a nano ZnO modified polyacrylate emulsion composite coating, which can effectively improve the water resistance, acid resistance and antibacterial property of the coating.
The technical scheme is as follows: the preparation method of the nano ZnO modified polyacrylate emulsion composite coating comprises the following steps:
(1) preparation of pre-emulsion: adding nano ZnO and deionized water into a beaker together for ultrasonic emulsification, then adding methyl methacrylate, butyl acrylate, acrylic acid and hydroxyethyl acrylate, mixing, carrying out ultrasonic crushing treatment, and finally mechanically stirring at the rotating speed of 1000r/min to obtain Pickering emulsion;
(2) preparing a modified acrylate emulsion: transferring the Pickering emulsion obtained in the step (1) into a four-neck flask, introducing nitrogen into the flask, heating to 75-80 ℃ while stirring, dropwise adding 1/3 initiator into the flask at a constant speed for 1h, dropwise adding the rest 1/3 initiator after 1h, wherein the dropwise adding time is 1h, dropwise adding the initiator 1/3 initiator after one hour interval, wherein the time is also 1h, and finally cooling, discharging and filtering for later use, wherein the initiator is 0.48-0.96 g of potassium persulfate dissolved in 34.29-68.57 g of KPS aqueous solution;
(3) preparing the composite coating: and (3) adding a dispersing agent and a wetting agent into deionized water, stirring uniformly, adding titanium dioxide, weighing the composite emulsion obtained in the step (2) according to requirements, adding a thickening agent and a film-forming auxiliary agent, stirring uniformly by using a mixing magnetic force, and finally adding a defoaming agent to obtain the polyacrylate nano ZnO composite coating.
Preferably, in the step (1), the amount of the deionized water is 81.2-83.6 g.
Preferably, in the step (1), the nano ZnO accounts for 2-6% of the total mass of the monomer.
Preferably, in the step (1), the time of ultrasonic emulsification is 5-30 min.
Preferably, in the step (1), 15.92 to 27.84g of methyl methacrylate, 27.84 to 31.84g of butyl acrylate, 0.24 to 0.48g of acrylic acid and 2.4 to 7.2g of hydroxyethyl acrylate are added.
Preferably, in the step (1), the time of the ultrasonic disruption treatment is 15-30 min.
Preferably, in step (1), the time for mechanical stirring is 10 min.
Preferably, in the step (2), the four-necked flask is equipped with a thermostatic heating device, a digital display stirrer, a reflux condenser and a thermometer.
Has the advantages that: compared with the prior art, the invention has the advantages that: in the scheme, nano ZnO, acrylic soft and hard monomers and functional monomers are adopted as raw materials, and the polyacrylate nano ZnO composite coating is prepared through Pickering emulsion polymerization, so that the process is simple, a surfactant is not required, and the environment can be effectively protected; the introduction of the nano particles improves various performances of the coating after film forming, the water resistance of the coating exceeds 5 days, and the antibacterial property reaches 80 percent, so that the coating can be widely applied to the fields of building wall coatings, adhesives and the like.
Drawings
FIG. 1 is a flow chart of the steps of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
As shown in fig. 1, example 1: the preparation method of the nano ZnO modified polyacrylate emulsion composite coating comprises the following steps:
adding 81.2g of nano ZnO and 80g of deionized water into a beaker, wherein the nano ZnO accounts for 2 percent of the total mass of the monomers, and then carrying out ultrasonic emulsification for 5 min. After completion of the emulsification, 27.84g of methyl methacrylate, 27.84g of butyl acrylate, 0.24g of acrylic acid and 2.4g of hydroxyethyl acrylate were added thereto, and the mixture was sonicated for 30min using a sonicator.
Transferring the ultrasonic emulsion into a four-neck flask provided with a thermometer, a reflux condenser and a boosting electric stirrer, stirring for 10min at the speed of 1000r/min, then dropwise adding 1/3 of potassium persulfate aqueous solution (0.48g of potassium persulfate dissolved in 34.29g of water) at a slower speed, controlling the temperature at 80 ℃, adding the rest 1/3 at one hour intervals, reacting for 5h in total, finally cooling, filtering and discharging.
Example 2: adding 81.8g of nano ZnO and 80g of deionized water into a beaker, wherein the nano ZnO accounts for 2 percent of the total mass of the monomers, and then carrying out ultrasonic emulsification for 5 min. After completion of the emulsification, 27.87g of methyl methacrylate, 29.83g of butyl acrylate, 0.3g of acrylic acid and 3.6g of hydroxyethyl acrylate were added thereto, and the mixture was sonicated for 15min using a sonicator.
Transferring the ultrasonic emulsion into a four-neck flask provided with a thermometer, a reflux condenser and a boosting electric stirrer, stirring for 10min at the speed of 1000r/min, then dropwise adding 1/3 of potassium persulfate aqueous solution (0.6g of potassium persulfate dissolved in 42.86g of water) at a slower speed, controlling the temperature at 78 ℃, adding the rest 1/3 at one hour intervals, reacting for 5h in total, finally cooling, filtering and discharging.
Example 3: adding 82.4g of nano ZnO and 80g of deionized water into a beaker, wherein the nano ZnO accounts for 4% of the total mass of the monomers, and then carrying out ultrasonic emulsification for 15 min. After completion of the emulsification, 20.69g of methyl methacrylate, 31.03g of butyl acrylate, 0.36g of acrylic acid and 4.8g of hydroxyethyl acrylate were added thereto, and the mixture was sonicated for 10min using a sonicator.
Transferring the ultrasonic emulsion into a four-neck flask provided with a thermometer, a reflux condenser and a boosting electric stirrer, stirring for 10min at the speed of 1000r/min, then dropwise adding 1/3 of potassium persulfate aqueous solution (0.72g of potassium persulfate dissolved in 51.43g of water) at a slower speed, controlling the temperature at 78 ℃, adding the rest 1/3 at one hour intervals, reacting for 5h in total, finally cooling, filtering and discharging.
Example 4: adding 83g of nano ZnO and 80g of deionized water into a beaker, wherein the nano ZnO accounts for 5 percent of the total mass of the monomers, and then carrying out ultrasonic emulsification for 15 min. After completion of the emulsification, 18.09g of methyl methacrylate, 31.65g of butyl acrylate, 0.42g of acrylic acid and 6g of hydroxyethyl acrylate were added thereto, and the mixture was sonicated for 30min using a sonicator.
Transferring the ultrasonic emulsion into a four-neck flask provided with a thermometer, a reflux condenser and a boosting electric stirrer, stirring for 10min at the speed of 1000r/min, then dropwise adding 1/3 of potassium persulfate aqueous solution (0.84g of potassium persulfate dissolved in 60g of water) at a slower speed, controlling the temperature at 80 ℃, adding the rest 1/3 at one-hour intervals, reacting for 5h in total, finally cooling, filtering and discharging.
Example 5: adding 83.6g of nano ZnO and 80g of deionized water into a beaker, wherein the nano ZnO accounts for 6 percent of the total mass of the monomers, and then carrying out ultrasonic emulsification for 25 min. After completion of the emulsification, 15.92g of methyl methacrylate, 31.84g of butyl acrylate, 0.48g of acrylic acid, and 7.2g of hydroxyethyl acrylate were added thereto, and the mixture was sonicated for 30min using a sonicator.
Transferring the ultrasonic emulsion into a four-neck flask provided with a thermometer, a reflux condenser and a boosting electric stirrer, stirring for 10min at the speed of 1000r/min, then dropwise adding 1/3 of potassium persulfate aqueous solution (0.96g of potassium persulfate dissolved in 68.571g of water) at a slower speed, controlling the temperature at 75 ℃, adding the rest 1/3 at intervals of one hour, reacting for 5h in total, finally cooling, filtering and discharging.
The coating is prepared by taking the composite emulsion in the five embodiments as a main film forming substance, firstly taking a proper amount of deionized water, adding the dispersing agent and the wetting agent, stirring, adding the titanium dioxide after uniformly stirring, and accelerating the speed of dispersion. Weighing the qualified emulsion according to the requirements, adding the thickening agent and the film-forming auxiliary agent, mixing and magnetically stirring uniformly, and finally adding the defoaming agent to prepare the polyacrylate nano ZnO composite coating.
The components in the formula are as follows:
Figure BDA0003569970630000031
Figure BDA0003569970630000041
and (3) performance determination of the composite coating:
1. hardness test
According to the GB/T6739-2006 standard test, a manual method is adopted, a hardness range d [ 6B, 5B, 4B, 3B, 2B, B, HB, H, 2H, 3H, 4H, 5H, 6H ] is selected as a determination standard, so that the hardness of the coated pencil is determined, and the operation procedure is as follows:
(1) a tin plate (120mm by 50mm by 0.28mm) of fixed dimensions was taken as a standard sample plate, and then the surface thereof was treated: firstly, polishing by using sand paper, then drying in the air, and finally wiping by using ethanol;
(2) spraying the base material surface by a spray gun air spraying mode, and drying for 7 days at normal temperature.
The five panel experiments were repeated and scratches were observed, whereby the pencil hardness was recorded as the pencil hardness of the coating.
2. Water resistance test
Reference is made to the GB/T1733-1993 standard test. The panels were prepared according to the method used and were edge-sealed with tape. The sample was immersed under distilled water for a length of 2/3 parts, and the cotton condition of the sample was observed every 24 hours, and the time for the sample to change (e.g., foam and fall) was recorded.
3. Salt water resistance test
The test is carried out according to the GB1763-79 standard A method. After the edge sealing treatment of the sample plate, most of the sample plate is soaked in a sodium chloride solution with the concentration of 5%, the change condition of the sample plate is observed, and the time for the sample plate to change is recorded.
4. Acid/base resistance test of coatings
Reference is made to the GB/T9274-1988 standard test. After the sample plate is prepared, edge sealing treatment is carried out on the sample plate, the sample plate is soaked in a 5% NaOH solution, and the change condition of the sample plate is observed every 8 hours.
5. Antibacterial property test
According to a general preparation method of a paint film GB1727-79, the composite paint film is prepared by a dip coating method, cultured for 24 hours in an incubator at a constant temperature of 37 ℃, the number of colony monomers of a culture dish is observed, and the bacteriostasis rate is calculated, which is shown as a formula (1).
Figure BDA0003569970630000042
In the formula, R*And H is the number of colony controls on a blank culture dish and K is the colony on a single culture dish for bacteriostasis rate.
The specific evaluations are shown in the following table:
table 1: measurement of coating hardness
Test specimen Hardness of coating
Composite emulsion 3H
Pure acrylic emulsion 2H
Table 2: water and acid resistance measurement
Test specimen Water resistance/h Salt water resistance per hour
Composite emulsion >120 >72
Pure acrylic emulsion >96 >48
Table 3: alkali resistance measurement
Test specimen Alkali resistance
Composite emulsion 4d later strippable
Pure acrylic emulsion Peelable after 3d
Table 4: measurement of antibacterial Properties
Test specimen Antibacterial property
Composite emulsion 80.23％
Pure acrylic emulsion 40.67％

Claims (8)

1. A preparation method of a nano ZnO modified polyacrylate emulsion composite coating is characterized by comprising the following steps:
(1) preparation of pre-emulsion: adding nano ZnO and deionized water into a beaker together for ultrasonic emulsification, then adding methyl methacrylate, butyl acrylate, acrylic acid and hydroxyethyl acrylate, mixing, carrying out ultrasonic crushing treatment, and finally mechanically stirring at the rotating speed of 1000r/min to obtain Pickering emulsion;
(2) preparing a modified acrylate emulsion: transferring the Pickering emulsion obtained in the step (1) into a four-neck flask, introducing nitrogen into the flask, heating to 75-80 ℃ while stirring, dropwise adding 1/3 initiator into the flask at a constant speed for 1h, dropwise adding the rest 1/3 initiator after 1h, wherein the dropwise adding time is 1h, dropwise adding the initiator 1/3 initiator after one hour interval, wherein the time is also 1h, and finally cooling, discharging and filtering for later use, wherein the initiator is 0.48-0.96 g of potassium persulfate dissolved in 34.29-68.57 g of KPS aqueous solution;
(3) preparing the composite coating: and (3) adding a dispersing agent and a wetting agent into deionized water, stirring uniformly, adding titanium dioxide, weighing the composite emulsion obtained in the step (2) according to requirements, adding a thickening agent and a film-forming auxiliary agent, stirring uniformly by using a mixing magnetic force, and finally adding a defoaming agent to obtain the polyacrylate nano ZnO composite coating.
2. The method for preparing the nano ZnO modified polyacrylate emulsion composite coating according to claim 1, wherein in the step (1), the total amount of nano ZnO and deionized water is 81.2-83.6 g.
3. The method for preparing nano ZnO modified polyacrylate emulsion composite coating according to claim 1, wherein in the step (1), nano ZnO accounts for 2-6% of the total mass of the monomers.
4. The preparation method of the nano ZnO modified polyacrylate emulsion composite coating according to claim 1, wherein in the step (1), the time of ultrasonic emulsification is 5-30 min.
5. The preparation method of the nano ZnO modified polyacrylate emulsion composite coating according to claim 1, wherein in the step (1), 15.92-27.84 g of methyl methacrylate, 27.84-31.84 g of butyl acrylate, 0.24-0.48 g of acrylic acid and 2.4-7.2 g of hydroxyethyl acrylate are added.
6. The preparation method of the nano ZnO modified polyacrylate emulsion composite coating according to claim 1, wherein in the step (1), the time of ultrasonic crushing treatment is 15-30 min.
7. The method for preparing nano ZnO modified polyacrylate emulsion composite coating according to claim 1, wherein in the step (1), the time of mechanical stirring is 10 min.
8. The method for preparing nano ZnO modified polyacrylate emulsion composite paint according to claim 1, wherein in the step (2), a constant-temperature heating device, a digital display stirrer, a reflux condenser tube and a thermometer are arranged in the four-neck flask.
CN202210316566.XA 2022-03-29 2022-03-29 Preparation method of nano ZnO modified polyacrylate emulsion composite coating Pending CN114672215A (en)

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