CN106893419B - Preparation method of polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen resistance aqueous coating liquid - Google Patents
Preparation method of polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen resistance aqueous coating liquid Download PDFInfo
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Abstract
The invention discloses a preparation method of polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen resistance aqueous coating liquid, which comprises the following components in percentage by weight: 2.4-4.1% of polyvinyl alcohol, 0.5-1.6% of sigma-zirconium phosphate, 95-95.6% of deionized water, 0.05-0.1% of cross-linking agent and 0.16-0.27% of defoaming agent, wherein the preparation method of the polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen resistance coating liquid comprises the following steps: the preparation method comprises the steps of taking water as a dispersing agent, stripping crystalline layered sigma-zirconium phosphate by using a stripping agent, removing the stripping agent to obtain a sigma-zirconium phosphate nanoparticle dispersion liquid which is dispersed in water in a single piece, blending the dispersion liquid with a polyvinyl alcohol aqueous solution, adding a cross-linking agent, a defoaming agent and the like, performing ultrasonic treatment, stirring, sieving by a sieve of 250-400 and the like to obtain a polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen barrier water-based coating liquid, wherein the coating liquid can have excellent barrier property to oxygen in a high humidity environment, and the problem of low oxygen barrier property of the polyvinyl alcohol coating liquid in the prior art at 60-90% RH is solved.
Description
Technical Field
The invention relates to the field of packaging film coating liquid, in particular to a preparation method of polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen resistance aqueous coating liquid.
Background
Polyvinyl alcohol is a white powdery resin and has good water solubility and film forming property, but because polyvinyl alcohol easily absorbs water, the barrier property of a polyvinyl alcohol barrier coating to oxygen is deteriorated under high humidity (60-90% RH). In the prior art, the barrier property of a polyvinyl alcohol barrier coating to oxygen under high humidity is improved by blending melamine resin, nano silicon dioxide and polyvinyl alcohol, but the barrier coating has the problems of unstable quality, poor compatibility of different components in the coating and the like.
Sigma-zirconium phosphate is a layered multifunctional material used as an ion exchanger, a catalyst, an adsorbent, and the like. The layered zirconium phosphate has the advantages of easy preparation, good crystal form, high thermal stability, stable layered structure, large specific surface area, high ion exchange capacity and the like, meanwhile, the surface of the sigma-zirconium phosphate layer contains a large number of-OH groups which can generate hydrogen bond action with hydroxyl of polyvinyl alcohol, and the sigma-zirconium phosphate layer and the polyvinyl alcohol have good compatibility and bonding force, and the barrier property of the polyvinyl alcohol coating to oxygen under high humidity can be improved by compounding the sigma-zirconium phosphate and the polyvinyl alcohol.
Disclosure of Invention
In order to solve the problem that the polyvinyl alcohol in the existing coating liquid has low oxygen barrier performance under the condition of high humidity (60-90% RH), the invention aims to provide a preparation method of a polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen barrier aqueous coating liquid which can keep good oxygen barrier performance under the condition of high humidity.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
the polyvinyl alcohol/sigma-zirconium phosphate composite high-oxygen-resistance water-based coating liquid comprises the following raw materials in percentage by weight:
2.4 to 4.1 percent of polyvinyl alcohol;
0.5 to 1.6 percent of sigma-zirconium phosphate;
95% -95.6% of deionized water;
0.05 to 0.1 percent of cross-linking agent;
0.16 to 0.27 percent of defoaming agent.
Furthermore, the alcoholysis degree of the polyvinyl alcohol is 50-99.9%, and the polymerization degree is 1000-2000.
Furthermore, the sigma-zirconium phosphate is single-layer dispersed sigma-zirconium phosphate which is obtained by peeling lamellar crystal sigma-zirconium phosphate nano particles and then dispersing the peeled particles in water.
Preferably, the preparation method of the monolayer dispersion sigma-zirconium phosphate comprises the following steps:
(1) mixing lamellar crystal sigma-zirconium phosphate with an X-ray diffraction angle 2 theta value of 9.6-13.6 with deionized water, mechanically stirring for 28-32 min, and then performing ultrasonic dispersion for 28-32 min by using ultrasonic equipment to obtain a 3% mass concentration sigma-zirconium phosphate water dispersion;
(2) adding a stripping agent with the same molar mass as sigma-zirconium phosphate into the prepared sigma-zirconium phosphate aqueous dispersion, stripping for 28-32 min under the ultrasonic action of ultrasonic equipment to obtain a transparent sigma-zirconium phosphate stripping solution, then dropwise adding a hydrochloric acid solution into the sigma-zirconium phosphate stripping solution until the pH value of the sigma-zirconium phosphate stripping solution is 1.5-3.0, wherein gel sigma-zirconium phosphate precipitates appear in the sigma-zirconium phosphate stripping solution, and separating the gel sigma-zirconium phosphate precipitates in the sigma-zirconium phosphate stripping solution by a centrifugal separation method;
(3) deionized water is added into the gel-like sigma-zirconium phosphate obtained by centrifugal separation, and ultrasonic dispersion is carried out by ultrasonic equipment, so as to obtain the single-layer dispersion sigma-zirconium phosphate stripping solution.
Preferably, the stripping agent is at least one of n-propylamine, n-butylamine, isobutylamine, allylamine and tetrabutylammonium hydroxide.
The preparation method of the polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen resistance aqueous coating liquid comprises the steps of adding a polyvinyl alcohol solution with the mass concentration of 5%, a cross-linking agent and a defoaming agent into a single-layer dispersion sigma-zirconium phosphate stripping liquid prepared by dispersing sigma-zirconium phosphate in deionized water, stirring, carrying out ultrasonic treatment, and removing large particles by using a 250-400-mesh screen to obtain the polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen resistance aqueous coating liquid.
Further, the cross-linking agent is formed by mixing at least one of glyoxal, glutaraldehyde, boric acid and sodium borate.
Further, the defoaming agent is formed by mixing at least one of isopropanol and ethanol.
By adopting the technical scheme, the invention has the beneficial effects that: the polyvinyl alcohol/sigma-zirconium phosphate aqueous coating liquid prepared by compounding sigma-zirconium phosphate and polyvinyl alcohol can have excellent barrier property to oxygen in a high humidity environment by utilizing the advantages that the sigma-zirconium phosphate has easy preparation, good crystal form, high thermal stability, stable layered structure, large specific surface area and high ion exchange capacity, and a large number of-OH groups contained on the surface of the sigma-zirconium phosphate can generate hydrogen bonding action with carboxyl of the polyvinyl alcohol, so that the good compatibility and bonding force can be realized between the sigma-zirconium phosphate and the polyvinyl alcohol, and the problem that the oxygen barrier property of the polyvinyl alcohol coating liquid is low under 60-90% RH in the prior art is solved.
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The invention will be further elucidated with reference to the drawings and the detailed description:
FIG. 1 is a schematic view showing the preparation process of a polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen barrier aqueous coating liquid of the present invention.
Detailed Description
The polyvinyl alcohol/sigma-zirconium phosphate composite high-oxygen-resistance water-based coating liquid comprises the following raw materials in percentage by weight:
2.4 to 4.1 percent of polyvinyl alcohol;
0.5 to 1.6 percent of sigma-zirconium phosphate;
95% -95.6% of deionized water;
0.05 to 0.1 percent of cross-linking agent;
0.16 to 0.27 percent of defoaming agent.
Furthermore, the alcoholysis degree of the polyvinyl alcohol is 50-99.9%, and the polymerization degree is 1000-2000.
Furthermore, the sigma-zirconium phosphate is single-layer dispersed sigma-zirconium phosphate which is obtained by peeling lamellar crystal sigma-zirconium phosphate nano particles and then dispersing the peeled particles in water.
Preferably, the preparation method of the monolayer dispersion sigma-zirconium phosphate comprises the following steps:
(1) mixing lamellar crystal sigma-zirconium phosphate with an X-ray diffraction angle 2 theta value of 9.6-13.6 with deionized water, mechanically stirring for 28-32 min, and then performing ultrasonic dispersion for 28-32 min by using ultrasonic equipment to obtain a 3% mass concentration sigma-zirconium phosphate water dispersion;
(2) adding a stripping agent with the same molar mass as sigma-zirconium phosphate into the prepared sigma-zirconium phosphate aqueous dispersion, stripping for 28-32 min under the ultrasonic action of ultrasonic equipment to obtain a transparent sigma-zirconium phosphate stripping solution, then dropwise adding a hydrochloric acid solution into the sigma-zirconium phosphate stripping solution until the pH value of the sigma-zirconium phosphate stripping solution is 1.5-3.0, wherein gel sigma-zirconium phosphate precipitates appear in the sigma-zirconium phosphate stripping solution, and separating the gel sigma-zirconium phosphate precipitates in the sigma-zirconium phosphate stripping solution by a centrifugal separation method;
(3) deionized water is added into the gel-like sigma-zirconium phosphate obtained by centrifugal separation, and ultrasonic dispersion is carried out by ultrasonic equipment, so as to obtain the single-layer dispersion sigma-zirconium phosphate stripping solution.
Preferably, the stripping agent is at least one of n-propylamine, n-butylamine, isobutylamine, allylamine and tetrabutylammonium hydroxide.
As shown in figure 1, according to the preparation method of the polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen resistance aqueous coating liquid, a polyvinyl alcohol solution with the mass concentration of 5%, a cross-linking agent and a defoaming agent are added into a single-layer dispersion sigma-zirconium phosphate stripping liquid in which sigma-zirconium phosphate is dispersed in deionized water, and after stirring and ultrasonic treatment, large particles are removed by using a 250-400-mesh screen, so that the polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen resistance aqueous coating liquid can be obtained.
Further, the cross-linking agent is formed by mixing at least one of glyoxal, glutaraldehyde, boric acid and sodium borate.
Further, the defoaming agent is formed by mixing at least one of isopropanol and ethanol.
Example 1
(1) Mixing 200g of laminar crystalline sigma-zirconium phosphate with an X-ray diffraction angle 2 theta value of 13.6 with 6Kg of deionized water, mechanically stirring for 30min, and then performing ultrasonic dispersion for 30min by using ultrasonic equipment to obtain a 3% mass concentration sigma-zirconium phosphate aqueous dispersion;
(2) adding 10g of n-propylamine stripping agent into the prepared sigma-zirconium phosphate aqueous dispersion, stripping for 30min under the ultrasonic action of ultrasonic equipment to obtain a transparent sigma-zirconium phosphate stripping solution, then dropwise adding a hydrochloric acid solution into the sigma-zirconium phosphate stripping solution until the pH value of the sigma-zirconium phosphate stripping solution is 1.5, wherein gel sigma-zirconium phosphate precipitates appear in the sigma-zirconium phosphate stripping solution, and separating the gel sigma-zirconium phosphate precipitates in the sigma-zirconium phosphate stripping solution by a centrifugal separation method;
(3) adding deionized water into the gel sigma-zirconium phosphate obtained by centrifugal separation, performing ultrasonic dispersion by ultrasonic equipment, and adjusting the adding amount of the deionized water to obtain a monolayer dispersion sigma-zirconium phosphate stripping solution with the mass concentration of 3%;
(4) and (3) adding 30Kg of polyvinyl alcohol aqueous solution with the mass concentration of 5%, the alcoholysis degree of 99.9% and the polymerization degree of 2000 diluted by deionized water, 20g of glyoxal cross-linking agent and 100g of ethanol defoaming agent into the single-layer dispersion sigma-zirconium phosphate stripping solution prepared in the step (3), stirring for 30min by using mechanical stirring equipment and ultrasonic stirring equipment respectively, and sieving and discharging through a 400-mesh screen to obtain the polyvinyl alcohol/sigma-zirconium phosphate composite aqueous coating solution.
The prepared polyvinyl alcohol/sigma-zirconium phosphate composite aqueous coating liquid is coated on a 20 mu m biaxial stretching polypropylene film substrate on a machine, and the coating amount is 1g/m2After curing for 30h at 50 ℃, carrying out oxygen permeability test on the coating film, wherein the oxygen permeability of the coating film is 5.2cc/m under the conditions that the temperature is 23 ℃ and the humidity is 70 percent2•24 hr。
Example 2
(1) 500g of lamellar crystal sigma-zirconium phosphate with the X-ray diffraction angle 2 theta value of 11.6 is mixed with 15Kg of deionized water, and after mechanical stirring is carried out for 28min, ultrasonic dispersion is carried out for 32min by utilizing ultrasonic equipment, so as to obtain the water dispersion of the sigma-zirconium phosphate with the mass concentration of 3%;
(2) adding 20g of n-propylamine stripping agent into the prepared sigma-zirconium phosphate aqueous dispersion, stripping for 32min under the ultrasonic action of ultrasonic equipment to obtain a transparent sigma-zirconium phosphate stripping solution, then dropwise adding a hydrochloric acid solution into the sigma-zirconium phosphate stripping solution until the pH value of the sigma-zirconium phosphate stripping solution is 2.5, wherein gel-like sigma-zirconium phosphate precipitates appear in the sigma-zirconium phosphate stripping solution, and separating the gel-like sigma-zirconium phosphate precipitates in the sigma-zirconium phosphate stripping solution by a centrifugal separation method;
(3) adding 15Kg of deionized water into the gel-like sigma-zirconium phosphate obtained by centrifugal separation, and performing ultrasonic dispersion by ultrasonic equipment to obtain a single-layer dispersion sigma-zirconium phosphate stripping solution with the mass concentration of 3%;
(4) and (3) adding 30Kg of polyvinyl alcohol aqueous solution with the mass concentration of 5%, the alcoholysis degree of 75%, the polymerization degree of 1500, 30g of boric acid crosslinking agent and 100g of isopropanol defoaming agent which are diluted by deionized water into the single-layer dispersion sigma-zirconium phosphate stripping solution prepared in the step (3), stirring for 30min by using mechanical stirring equipment and ultrasonic stirring equipment respectively, and sieving and discharging through a 300-mesh screen to obtain the polyvinyl alcohol/sigma-zirconium phosphate composite aqueous coating solution.
The prepared polyvinyl alcohol/sigma-zirconium phosphate composite aqueous coating liquid is coated on a 20 mu m biaxial stretching polypropylene film substrate on a machine, and the coating amount is 1g/m2After curing for 30h at 50 ℃, the oxygen permeability of the coating film is tested, and the oxygen permeability of the coating film is 1.2cc/m under the conditions that the temperature is 23 ℃ and the humidity is 70 percent2•24 hr。
Example 3
(1) Mixing 1000g of laminar crystalline sigma-zirconium phosphate with an X-ray diffraction angle 2 theta value of 9.6 with 30Kg of deionized water, mechanically stirring for 32min, and then performing ultrasonic dispersion for 28min by using ultrasonic equipment to obtain a 3% mass concentration sigma-zirconium phosphate aqueous dispersion;
(2) adding 40g of n-propylamine stripping agent into the prepared sigma-zirconium phosphate aqueous dispersion, stripping for 28min under the ultrasonic action of ultrasonic equipment to obtain a transparent sigma-zirconium phosphate stripping solution, then dropwise adding a hydrochloric acid solution into the sigma-zirconium phosphate stripping solution until the pH value of the sigma-zirconium phosphate stripping solution is 3.0, wherein gel sigma-zirconium phosphate precipitates appear in the sigma-zirconium phosphate stripping solution, and separating the gel sigma-zirconium phosphate precipitates in the sigma-zirconium phosphate stripping solution by a centrifugal separation method;
(3) adding 30Kg of deionized water into the gel-like sigma-zirconium phosphate obtained by centrifugal separation, and performing ultrasonic dispersion by ultrasonic equipment to obtain a single-layer dispersion sigma-zirconium phosphate stripping solution with the mass concentration of 3%;
(4) and (3) adding 30Kg of polyvinyl alcohol aqueous solution with the mass concentration of 5%, the alcoholysis degree of 50% and the polymerization degree of 1000, which is diluted by deionized water, 60g of sodium borate cross-linking agent and 100g of isopropanol defoaming agent into the single-layer dispersed sigma-zirconium phosphate stripping solution prepared in the step (3), stirring for 30min by using mechanical stirring equipment and ultrasonic stirring equipment respectively, and sieving and discharging through a 300-mesh screen to obtain the polyvinyl alcohol/sigma-zirconium phosphate composite aqueous coating solution.
The prepared polyvinyl alcohol/sigma-zirconium phosphate composite aqueous coating liquid is coated on a 20 mu m biaxial stretching polypropylene film substrate on a machine, and the coating amount is 1g/m2After curing for 30h at 50 ℃, carrying out oxygen permeability test on the coating film, wherein the oxygen permeability of the coating film is 0.5cc/m under the conditions that the temperature is 23 ℃ and the humidity is 70 percent2•24 hr。
The foregoing is directed to embodiments of the present invention, and equivalents, modifications, substitutions and variations such as will occur to those skilled in the art, which fall within the scope and spirit of the appended claims.
Claims (6)
1. A polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen resistant water-based coating liquid is characterized in that: the coating liquid comprises the following raw materials in percentage by weight:
2.4 to 4.1 percent of polyvinyl alcohol;
0.5 to 1.6 percent of sigma-zirconium phosphate;
95% -95.6% of deionized water;
0.05 to 0.1 percent of cross-linking agent;
0.16 to 0.27 percent of defoaming agent;
the cumulative composition content of the polyvinyl alcohol, the sigma-zirconium phosphate, the deionized water, the cross-linking agent and the defoaming agent is 100 percent;
the sigma-zirconium phosphate is single-layer dispersed sigma-zirconium phosphate which is obtained by peeling lamellar crystal sigma-zirconium phosphate nano particles and dispersing the peeled particles in water;
the preparation method of the single-layer dispersion sigma-zirconium phosphate comprises the following steps:
(1) mixing lamellar crystal sigma-zirconium phosphate with an X-ray diffraction angle 2 theta value of 9.6-13.6 with deionized water, mechanically stirring for 28-32 min, and then performing ultrasonic dispersion for 28-32 min by using ultrasonic equipment to obtain a 3% mass concentration sigma-zirconium phosphate water dispersion;
(2) adding a stripping agent with the same molar mass as sigma-zirconium phosphate into the prepared sigma-zirconium phosphate aqueous dispersion, stripping for 28-32 min under the ultrasonic action of ultrasonic equipment to obtain a transparent sigma-zirconium phosphate stripping solution, then dropwise adding a hydrochloric acid solution into the sigma-zirconium phosphate stripping solution until the pH value of the sigma-zirconium phosphate stripping solution is 1.5-3.0, wherein gel sigma-zirconium phosphate precipitates appear in the sigma-zirconium phosphate stripping solution, and separating the gel sigma-zirconium phosphate precipitates in the sigma-zirconium phosphate stripping solution by a centrifugal separation method;
(3) deionized water is added into the gel-like sigma-zirconium phosphate obtained by centrifugal separation, and ultrasonic dispersion is carried out by ultrasonic equipment, so as to obtain the single-layer dispersion sigma-zirconium phosphate stripping solution.
2. The coating liquid according to claim 1, wherein the coating liquid comprises a polyvinyl alcohol/σ -zirconium phosphate composite, and is characterized in that: the alcoholysis degree of the polyvinyl alcohol is 50-99.9%, and the polymerization degree is 1000-2000.
3. The coating liquid according to claim 1, wherein the coating liquid comprises a polyvinyl alcohol/σ -zirconium phosphate composite, and is characterized in that: the stripping agent is formed by mixing at least one of n-propylamine, n-butylamine, isobutylamine, allylamine and tetrabutylammonium hydroxide.
4. The method for preparing a polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen barrier aqueous coating liquid according to any one of claims 1 to 3, characterized in that: adding a polyvinyl alcohol solution with the mass concentration of 5%, a cross-linking agent and a defoaming agent into a single-layer dispersion sigma-zirconium phosphate stripping solution prepared by dispersing sigma-zirconium phosphate in deionized water, stirring, performing ultrasonic treatment, and removing large particles by using a 250-400-mesh screen to obtain the polyvinyl alcohol/sigma-zirconium phosphate composite high-oxygen-resistance water-based coating liquid.
5. The method for preparing a polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen barrier aqueous coating liquid according to claim 4, wherein: the cross-linking agent is formed by mixing at least one of glyoxal, glutaraldehyde, boric acid and sodium borate.
6. The method for preparing a polyvinyl alcohol/sigma-zirconium phosphate composite high oxygen barrier aqueous coating liquid according to claim 4, wherein: the defoaming agent is formed by mixing at least one of isopropanol and ethanol.
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