CN106866915B - Bio-based water-based nano emulsion for canvas coating and preparation method thereof - Google Patents

Bio-based water-based nano emulsion for canvas coating and preparation method thereof Download PDF

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CN106866915B
CN106866915B CN201710118543.7A CN201710118543A CN106866915B CN 106866915 B CN106866915 B CN 106866915B CN 201710118543 A CN201710118543 A CN 201710118543A CN 106866915 B CN106866915 B CN 106866915B
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chain extender
dihydric alcohol
water
mixture
parts
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CN106866915A (en
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杜娟
顾洪溪
田梅娟
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Baoji University of Arts and Sciences
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    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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

Abstract

A biobased water-based nano emulsion for canvas paint and a preparation method thereof are disclosed, wherein oligomer dihydric alcohol and natural vegetable oil containing hydroxyl are added into a reactor, after vacuum dehydration, isocyanate compound, chain extender, solvent and catalyst are added, after reaction for 1-4 hours at 60-90 ℃, neutralizing agent is added, after stirring for 15-60 minutes at room temperature, deionized water is added, after standing, the solvent is removed in vacuum, and water-based resin a is obtained; adding the water-based resin a into a reactor, dropwise adding an acrylate monomer and an initiator at 40-50 ℃, keeping the temperature at 45-55 ℃ for reaction for 2-3 hours after dropwise adding, and finally concentrating.

Description

Bio-based water-based nano emulsion for canvas coating and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a bio-based water-based nano emulsion for canvas coating and a preparation method thereof.
Background
The emulsion acts as the "heart" of the coating and plays a crucial role in the coating performance. The canvas paint is not exceptional, the quality of the canvas paint is a key for determining the expressive force and the quality of the painting, and the service life of the painting is also influenced.
At present, a lot of work is carried out in the field of emulsion polymerization by workers in scientific research institutes, but the research on the field of aqueous emulsion for canvas coatings is less, no special enterprise exists in China, an emulsion which is suitable for canvas coatings and has perfect comprehensive performance is researched and developed aiming at the characteristics of canvas, most canvas factories in China can only use the emulsion in the construction industry to temporarily replace the emulsion for canvas coatings, and the comprehensive performance is unsatisfactory and the price is high.
The invention patent with the publication number of CN201010278991.1 and the name of 'styrene-acrylic emulsion for canvas paint and a preparation method thereof' discloses a styrene-acrylic emulsion for canvas paint and a preparation method thereof, which adopts the emulsion that styrene, a (methyl) acrylic acid monomer and a (methyl) acrylate monomer are polymerized and styrene-acrylic acid-acrylate copolymer (namely the styrene-acrylic emulsion) is partially crosslinked under the action of a crosslinking agent, and has the characteristics of excellent elasticity, strong adhesive force, good tensile strength, strong oil penetration resistance, good durability, aging resistance and the like.
The invention discloses a high gloss styrene-acrylic emulsion for canvas paint and a preparation method thereof with the publication number of CN201310175127.9, and the patent is based on the patent CN201010278991.1 and discloses the high gloss styrene-acrylic emulsion for canvas paint and the preparation method thereof, wherein the emulsion system is added with diacetone acrylamide and sorbitan oleate polyoxyethylene ether disodium sulfosuccinate, so that the high gloss of the emulsion is highlighted.
However, when the styrene-acrylic emulsion is used as the emulsion for canvas coating, the crosslinking degree is not high, the emulsion is easy to be thermally bonded and cold-brittle, the heat resistance is not good, the residual emulsifier can not be completely removed, and the stability is not good, so that the water-based emulsion for canvas coating is urgently needed to be provided at present.
Disclosure of Invention
In order to overcome the problems, the invention aims to provide the bio-based water-based nano emulsion for the canvas coating and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of bio-based water-based nano emulsion for canvas paint comprises the following steps:
1) weighing the following components in parts by weight: 10-20 parts of oligomer dihydric alcohol, 3-5 parts of hydroxyl-containing natural vegetable oil, 12-24 parts of isocyanate compound, 2-8 parts of chain extender, 1-5 parts of neutralizer, 40-60 parts of deionized water, 10-20 parts of acrylate monomer and 0.1-0.2 part of initiator;
adding oligomer dihydric alcohol and natural vegetable oil containing hydroxyl into a reactor, dehydrating in vacuum, adding an isocyanate compound, a chain extender, a solvent and a catalyst, reacting at 60-90 ℃ for 1-4 hours, adding a neutralizing agent, stirring at room temperature for 15-60 minutes, adding deionized water, standing, and removing the solvent in vacuum to obtain water-based resin a;
2) adding the water-based resin a into a reactor, dropwise adding an acrylate monomer and an initiator at 40-50 ℃, and after dropwise adding, keeping the temperature at 45-55 ℃ for 2-3 hours to obtain water-based resin b;
3) and (3) concentrating the water-based resin b under vacuum to obtain the bio-based water-based nano emulsion for the canvas paint.
The invention further improves that the molecular weight of the oligomer dihydric alcohol is 500-2000.
The further improvement of the invention is that the oligomer dihydric alcohol is one or a mixture of two of polycaprolactone dihydric alcohol, polytetrahydrofuran dihydric alcohol, polycarbonate dihydric alcohol, poly adipic acid glycol ester dihydric alcohol and poly adipic acid butanediol ester glycol in any proportion.
The further improvement of the invention is that the natural vegetable oil containing hydroxyl is one or a mixture of two of olive oil, castor oil, palm oil, rapeseed oil, coconut oil and peanut oil in any proportion;
the diisocyanate compound is one or a mixture of two of toluene diisocyanate, 4' -diphenylmethane diisocyanate and cyclohexyl diisocyanate in any proportion.
The invention is further improved in that the chain extender is a mixture of a dihydric alcohol hydrophilic chain extender and a trihydric alcohol chain extender.
The invention has the further improvement that the mass ratio of the dihydric alcohol hydrophilic chain extender to the trihydric alcohol chain extender is 1: 2;
the dihydric alcohol hydrophilic chain extender is one or a mixture of two of dimethylolpropionic acid, dimethylolbutyric acid, dihydroxy propane sodium sulfonate, 2-aminoethyl amino ethane sodium sulfonate, diaminobenzene sodium sulfonate and N-methyldiethanolamine in any proportion;
the trihydric alcohol chain extender is one or a mixture of two of trimethylolpropane and 1, 2, 4-butanetriol in any proportion.
The further improvement of the invention is that the neutralizing agent is one or a mixture of two of triethylamine, diethylenetriamine, N-dimethylethanolamine, hydrochloric acid and acetic acid in any proportion;
the acrylate monomer is one or a mixture of two of methyl methacrylate, methyl acrylate and butyl acrylate in any proportion;
the initiator is one or a mixture of two of potassium persulfate, ammonium persulfate, azobisisobutyronitrile and tert-butyl hydroperoxide in any proportion.
The further improvement of the invention is that the catalyst is one or more of dibutyltin dilaurate, tin naphthenate and bismuth naphthenate;
the adding amount of the catalyst is 1 percent of the total mass of the oligomer dihydric alcohol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator;
the solvent is acetone or butanone;
the adding amount of the solvent is 40 percent of the total mass of the oligomer dihydric alcohol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator.
The further improvement of the invention is that the temperature of the vacuum dehydration in the step 1) is 110-120 ℃, and the time is 1-2 hours;
the stirring speed in the step 1) is 750-850 rmp.
A bio-based water-based nano emulsion for canvas paint.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention takes the natural vegetable oil containing hydroxyl of the biological material as the raw material, replaces part of polyalcohol to prepare the aqueous nano emulsion as the canvas film forming substance, takes water as the solvent, does not contain toxic organic solvent, has no pungent smell, and is green and environment-friendly.
(2) The preparation process of the invention is divided into two steps, wherein in the first step, the raw materials of low polymer dihydric alcohol, natural vegetable oil containing hydroxyl, isocyanate compound, chain extender, neutralizer and the like are subjected to stepwise polymerization to prepare the water-based polyurethane emulsion, and in the second step, the acrylate monomer and the initiator are added to prepare the bio-based water-based nano emulsion for the canvas coating compounded by the water-based polyurethane and the acrylic resin through free radical polymerization, so that the coating has higher crosslinking degree than a styrene-acrylate emulsion which is polymerized by simply using free radicals of styrene and acrylate monomers, has good heat resistance, can not be thermally adhered and cold-brittle, has better performance than the styrene-acrylate emulsion with low crosslinking degree, and has the advantages of both the water-based polyurethane and the water.
(3) The invention prepares the aqueous polyurethane emulsion first, and then compounds the aqueous polyurethane emulsion and the acrylic emulsion to obtain the aqueous nano-emulsion, overcomes the defect of low solid content of common canvas coatings, has the characteristics of strong adhesive force, no cracking, no needle holes, aging resistance, weather resistance and the like, and meets the requirements of the canvas emulsion. The preparation method of the invention is simple and easy to implement,
furthermore, in the preparation process of the invention, an emulsifier is not needed, only the hydrophilic chain extender containing carboxyl is added, and after the preparation is finished, the amine neutralizer is added for neutralization and salt formation, and the obtained product is dispersed in water, so that the problem of emulsifier residue does not exist.
The bio-based water-based nano emulsion for the canvas coating, prepared by the invention, has good emulsion stability, weather resistance and aging resistance, and the solid content is more than 40%. High cross-linking degree to canvas, strong adhesive force and no cracking.
Drawings
FIG. 1 is a scanning electron micrograph of a cotton canvas, wherein (a) is a magnification of 600 times; (b) is magnified 1200 times;
FIG. 2 is a scanning electron micrograph of the canvas of example 1 coated with an aqueous nanoemulsion and wherein (a) is a magnification of 600; (b) is magnified 1200 times;
FIG. 3 is a scanning electron micrograph of the canvas of example 2 coated with an aqueous nanoemulsion and wherein (a) is a magnification of 600; (b) is a 1200 fold magnification.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
The canvas is made of a long fiber fabric layer or a non-woven fabric layer. The long-fiber fabric layer is a fabric layer formed by one or more of terylene, nylon, polyacrylonitrile fiber, polyvinyl formal fiber, polypropylene fiber, spandex, cotton, wool and flax. The molecular weight of the oligomer dihydric alcohol is 500-2000.
The following description will be made by way of specific examples.
Example 1 (the formulation is the optimal formulation, scanning electron microscopy does not have any pinholes)
1) Weighing the following components in parts by weight: 10 parts of oligomer dihydric alcohol, 3 parts of hydroxyl-containing natural vegetable oil, 15 parts of isocyanate compound, 2 parts of chain extender, 5 parts of neutralizer, 40 parts of deionized water, 15 parts of acrylate monomer and 0.1 part of initiator;
adding oligomer dihydric alcohol and natural vegetable oil containing hydroxyl into a reactor, dehydrating for 2 hours in vacuum at 110 ℃, adding an isocyanate compound, a chain extender, a solvent and a catalyst, reacting for 4 hours at 60 ℃, adding a neutralizer, stirring for 60 minutes at 750rmp at room temperature, adding deionized water, standing, and removing the solvent in vacuum to obtain water-based resin a;
2) adding the water-based resin a into a reactor, dropwise adding an acrylate monomer and an initiator at 40 ℃, and after dropwise adding, keeping the temperature at 45 ℃ for reacting for 3 hours to obtain water-based resin b;
3) and (3) removing the monomers of the water-based resin b for 1 hour under vacuum to remove trace residual monomers, thus obtaining the bio-based water-based nano emulsion for the canvas coating.
The oligomer dihydric alcohol is polycaprolactone dihydric alcohol.
The natural vegetable oil containing hydroxyl is olive oil;
the diisocyanate compound is toluene diisocyanate.
The chain extender is a mixture of a dihydric alcohol hydrophilic chain extender and a trihydric alcohol chain extender.
The mass ratio of the dihydric alcohol hydrophilic chain extender to the trihydric alcohol chain extender is 1: 2;
the dihydric alcohol hydrophilic chain extender is dimethylolpropionic acid;
the trihydric alcohol chain extender is trimethylolpropane;
the acrylate monomer is;
the initiator is potassium persulfate.
The catalyst is dibutyltin dilaurate;
the addition amount of the catalyst is 1 percent of the total mass of the oligomer dihydric alcohol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator;
the solvent is acetone;
the addition amount of the solvent is 40% of the total mass of the oligomer dihydric alcohol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator.
Example 2
1) Weighing the following components in parts by weight: 15 parts of oligomer dihydric alcohol, 5 parts of hydroxyl-containing natural vegetable oil, 12 parts of isocyanate compound, 5 parts of chain extender, 4 parts of neutralizer, 50 parts of deionized water, 10 parts of acrylate monomer and 0.2 part of initiator;
adding oligomer dihydric alcohol and natural vegetable oil containing hydroxyl into a reactor, dehydrating for 1 hour at 120 ℃ in vacuum, adding an isocyanate compound, a chain extender, a solvent and a catalyst, reacting for 1 hour at 90 ℃, adding a neutralizer, stirring for 15 minutes at room temperature of 850rmp, adding deionized water, standing, and removing the solvent in vacuum to obtain water-based resin a;
2) adding the water-based resin a into a reactor, dropwise adding an acrylate monomer and an initiator at 50 ℃, and after dropwise adding, keeping the temperature at 55 ℃ for 2 hours to react to obtain water-based resin b;
3) and (3) removing the monomers of the water-based resin b for 1 hour under vacuum to remove trace residual monomers, thus obtaining the bio-based water-based nano emulsion for the canvas coating.
The oligomer dihydric alcohol is a mixture of polytetrahydrofuran dihydric alcohol and polycarbonate dihydric alcohol.
The natural vegetable oil containing hydroxyl is a mixture of castor oil and palm oil;
the diisocyanate compound is a mixture of 4, 4' -diphenylmethane diisocyanate and cyclohexyl diisocyanate.
The chain extender is a mixture of a dihydric alcohol hydrophilic chain extender and a trihydric alcohol chain extender.
The mass ratio of the dihydric alcohol hydrophilic chain extender to the trihydric alcohol chain extender is 1: 2;
the dihydric alcohol hydrophilic chain extender is a mixture of dimethylolbutyric acid and dihydroxy propane sodium sulfonate;
the trihydric alcohol chain extender is a mixture of trimethylolpropane and 1, 2, 4-butanetriol.
The neutralizing agent is a mixture of diethylenetriamine and N, N-dimethylethanolamine;
the acrylate monomer is a mixture of methyl acrylate and butyl acrylate;
the initiator is a mixture of ammonium persulfate and azobisisobutyronitrile.
The catalyst is a mixture of tin naphthenate and bismuth naphthenate;
the adding amount of the catalyst is 1 percent of the total mass of the oligomer dihydric alcohol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator;
the solvent is butanone;
the adding amount of the solvent is 40 percent of the total mass of the oligomer dihydric alcohol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator.
Example 3
1) Weighing the following components in parts by weight: 20 parts of oligomer dihydric alcohol, 4 parts of hydroxyl-containing natural vegetable oil, 20 parts of isocyanate compound, 7 parts of chain extender, 3 parts of neutralizer, 60 parts of deionized water, 20 parts of acrylate monomer and 0.1 part of initiator;
adding oligomer dihydric alcohol and natural vegetable oil containing hydroxyl into a reactor, dehydrating for 1.5 hours in vacuum at 115 ℃, adding an isocyanate compound, a chain extender, a solvent and a catalyst, reacting for 3 hours at 70 ℃, adding a neutralizer, stirring for 20 minutes at 800rmp at room temperature, adding deionized water, standing, and removing the solvent in vacuum to obtain water-based resin a;
2) adding the water-based resin a into a reactor, dropwise adding an acrylate monomer and an initiator at 45 ℃, and after dropwise adding, keeping the temperature at 50 ℃ for 2 hours to react to obtain water-based resin b;
3) and (3) removing the monomers of the water-based resin b for 1 hour under vacuum to remove trace residual monomers, thus obtaining the bio-based water-based nano emulsion for the canvas coating.
The oligomer diol is a mixture of polyhexamethylene adipate diol and polybutylene adipate diol.
The natural vegetable oil containing hydroxyl is a mixture of rapeseed oil and coconut oil;
the diisocyanate compound is a mixture of toluene diisocyanate and cyclohexyl diisocyanate.
The chain extender is a mixture of a dihydric alcohol hydrophilic chain extender and a trihydric alcohol chain extender.
The mass ratio of the dihydric alcohol hydrophilic chain extender to the trihydric alcohol chain extender is 1: 2;
the dihydric alcohol hydrophilic chain extender is a mixture of 2-aminoethyl amino ethyl sodium sulfonate and diaminobenzene sodium sulfonate;
the trihydric alcohol chain extender is 1, 2, 4-butanetriol.
The neutralizing agent is a mixture of hydrochloric acid and acetic acid;
the acrylate monomer is butyl acrylate;
the initiator is tert-butyl hydroperoxide.
The catalyst is tin naphthenate;
the adding amount of the catalyst is 1 percent of the total mass of the oligomer dihydric alcohol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator;
the solvent is acetone;
the adding amount of the solvent is 40 percent of the total mass of the oligomer dihydric alcohol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator.
Example 4
1) Weighing the following components in parts by weight: 12 parts of oligomer dihydric alcohol, 3 parts of hydroxyl-containing natural vegetable oil, 24 parts of isocyanate compound, 8 parts of chain extender, 1 part of neutralizer, 45 parts of deionized water, 18 parts of acrylate monomer and 0.2 part of initiator;
adding oligomer dihydric alcohol and natural vegetable oil containing hydroxyl into a reactor, dehydrating for 1.5 hours in vacuum at 110 ℃, adding an isocyanate compound, a chain extender, a solvent and a catalyst, reacting for 2 hours at 80 ℃, adding a neutralizer, stirring for 40 minutes at room temperature of 820rmp, adding deionized water, standing, and removing the solvent in vacuum to obtain water-based resin a;
2) adding the water-based resin a into a reactor, dropwise adding an acrylate monomer and an initiator at 50 ℃, and after dropwise adding, keeping the temperature at 55 ℃ for 2 hours to react to obtain water-based resin b;
3) and (3) removing the monomers of the water-based resin b for 1 hour under vacuum to remove trace residual monomers, thus obtaining the bio-based water-based nano emulsion for the canvas coating.
The oligomer dihydric alcohol is a mixture of polycaprolactone dihydric alcohol and polybutylene adipate glycol.
The natural vegetable oil containing hydroxyl is a mixture of olive oil and peanut oil;
the diisocyanate compound is a mixture of toluene diisocyanate and cyclohexyl diisocyanate.
The chain extender is a mixture of a dihydric alcohol hydrophilic chain extender and a trihydric alcohol chain extender.
The mass ratio of the dihydric alcohol hydrophilic chain extender to the trihydric alcohol chain extender is 1: 2;
the dihydric alcohol hydrophilic chain extender is a mixture of sodium diaminobenzene sulfonate and N-methyldiethanolamine;
the trihydric alcohol chain extender is 1, 2, 4-butanetriol.
The neutralizing agent is a mixture of triethylamine and N, N-dimethylethanolamine;
the acrylate monomer is methyl acrylate;
the initiator is azobisisobutyronitrile.
The catalyst is a mixture of dibutyltin dilaurate, tin naphthenate and bismuth naphthenate;
the adding amount of the catalyst is 1 percent of the total mass of the oligomer dihydric alcohol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator;
the solvent is acetone;
the adding amount of the solvent is 40 percent of the total mass of the oligomer dihydric alcohol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator.
As can be seen from fig. 1, the uncoated cotton canvas had loose surface fiber bundles and many voids between them.
As can be seen in FIG. 2, the surface of the cotton canvas coated with the canvas paint optimum formulation was relatively flat, the fiber bundles were substantially tightly adhered together by the coating, and the voids between the fiber bundles disappeared, indicating that the canvas paint optimum formulation coating penetrated the fiber fabrics and bonded them together.
As can be seen in fig. 3, the cotton fabric canvas coated with the canvas paint in a non-optimal formulation had an uneven surface with a small amount of voids between the fiber bundles.
The performance of the bio-based water-based nano emulsion for canvas paint prepared by the invention is tested as follows:
the canvas suitable for the invention is made of a long fiber fabric layer or a non-woven fabric layer. The long-fiber fabric layer is a fabric layer formed by one or more of terylene, nylon, polyacrylonitrile fiber, polyvinyl formal fiber, polypropylene fiber, spandex, cotton, wool and flax.
1. Weather resistance
The emulsion prepared by the invention is put into a test box with the temperature ranging from 20 ℃ to 40 ℃ for 24 hours, and then the coagulation condition is observed.
2. Aging resistance
By means of an ultraviolet accelerated aging tester, referring to test standard GB/T4522-2008, the performance values before and after the sample exposure are compared by promoting the adhesive film deterioration under specific standard test conditions, and the sample is judged to be qualified if the critical performance values (such as whiteness, transparency, elasticity and the like) after the exposure are more than 80% before the exposure.
3. Emulsion stability
Visual inspection with naked eyes is adopted to determine whether the phenomena of demulsification, delamination, flocculation and precipitation exist or not, and if not, the phenomena are good.
4. Film appearance test
The presence or absence of cracks in the coating film was observed by naked eyes, and the presence or absence of pinholes in the coating film was observed by a scanning electron microscope.
5. Differential scanning calorimetry
The method is characterized by adopting a Japanese NETZSOH-DSC204 type differential scanning calorimeter for testing, wherein the testing range is-40-100 ℃, the weight of a test sample is 8-12 mg, the sample is cooled to-40 ℃ under the protection of liquid nitrogen, then the sample is heated at the heating rate of 10 ℃/min, the glass transition temperature of the sample is tested, the crosslinking degree is increased when the glass transition temperature is high, and the crosslinking degree is decreased when the glass transition temperature is not high. The results of the performance tests are shown in Table 1.
TABLE 1 Properties of Bio-based aqueous nanoemulsions for canvas coatings prepared in examples 1-4
Figure BDA0001236333840000111
The invention takes oligomer dihydric alcohol, natural vegetable oil containing hydroxyl, isocyanate compound, chain extender, neutralizer, deionized water, acrylate monomer and initiator as raw materials, and the raw materials are reacted to prepare the bio-based water-based nano emulsion for canvas paint. The bio-based water-based nano emulsion has excellent adhesive force, good durability and aging resistance, and is suitable for water-based emulsion for canvas coating.

Claims (5)

1. A preparation method of bio-based water-based nano emulsion for canvas paint is characterized by comprising the following steps:
1) weighing the following components in parts by weight: 10 parts of oligomer dihydric alcohol, 3 parts of hydroxyl-containing natural vegetable oil, 15 parts of isocyanate compound, 2 parts of chain extender, 5 parts of neutralizer, 40 parts of deionized water, 15 parts of acrylate monomer and 0.1 part of initiator;
adding oligomer dihydric alcohol and natural vegetable oil containing hydroxyl into a reactor, dehydrating in vacuum, adding an isocyanate compound, a chain extender, a solvent and a catalyst, reacting at 60-90 ℃ for 1-4 hours, adding a neutralizing agent, stirring at room temperature for 15-60 minutes, adding deionized water, standing, and removing the solvent in vacuum to obtain water-based resin a;
2) adding the water-based resin a into a reactor, dropwise adding an acrylate monomer and an initiator at 40-50 ℃, and after dropwise adding, keeping the temperature at 45-55 ℃ for 2-3 hours to obtain water-based resin b;
3) concentrating the water-based resin b under vacuum to obtain the bio-based water-based nano emulsion for the canvas coating;
the molecular weight of the oligomer dihydric alcohol is 500-2000;
the chain extender is a mixture of a dihydric alcohol hydrophilic chain extender and a trihydric alcohol chain extender, and the mass ratio of the dihydric alcohol hydrophilic chain extender to the trihydric alcohol chain extender is 1: 2;
the adding amount of the solvent is 40 percent of the total mass of the oligomer dihydric alcohol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator; the solvent is acetone or butanone;
the oligomer dihydric alcohol is one or a mixture of two of polycaprolactone dihydric alcohol, polytetrahydrofuran dihydric alcohol, polycarbonate dihydric alcohol, polyhexamethylene adipate dihydric alcohol and polybutanediol adipate glycol in any proportion;
the natural vegetable oil containing hydroxyl is one or a mixture of two of olive oil, castor oil, palm oil, rapeseed oil, coconut oil and peanut oil in any proportion;
the isocyanate compound is one or a mixture of two of toluene diisocyanate, 4' -diphenylmethane diisocyanate and cyclohexyl diisocyanate in any proportion;
the dihydric alcohol hydrophilic chain extender is one or a mixture of two of dimethylolpropionic acid and dimethylolbutyric acid in any proportion;
the trihydric alcohol chain extender is one or a mixture of two of trimethylolpropane and 1, 2, 4-butanetriol in any proportion;
the catalyst is one or more of dibutyltin dilaurate, tin naphthenate and bismuth naphthenate.
2. The method for preparing the bio-based aqueous nano emulsion for canvas coatings according to claim 1, wherein the neutralizer is one or a mixture of two of triethylamine, diethylenetriamine and N, N-dimethylethanolamine in any ratio;
the acrylate monomer is one or a mixture of two of methyl methacrylate, methyl acrylate and butyl acrylate in any proportion;
the initiator is one or a mixture of two of potassium persulfate, ammonium persulfate, azobisisobutyronitrile and tert-butyl hydroperoxide in any proportion.
3. The method for preparing the bio-based aqueous nano emulsion for canvas coating according to claim 1, wherein the amount of the catalyst added is 1% of the total mass of the oligomer diol, the natural vegetable oil containing hydroxyl, the isocyanate compound, the chain extender, the neutralizer, the deionized water, the acrylate monomer and the initiator.
4. The method for preparing the bio-based aqueous nano emulsion for canvas coating according to claim 1, wherein the temperature of vacuum dehydration in step 1) is 110-120 ℃ and the time is 1-2 hours;
the stirring speed in the step 1) is 750-850 rmp.
5. A biobased aqueous nanoemulsion for canvas coatings prepared according to the method of any one of claims 1 to 4.
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