CN120384421A - Preparation method of fluorine-free waterproofing agent based on polyurethane-nanosilica composite - Google Patents
Preparation method of fluorine-free waterproofing agent based on polyurethane-nanosilica compositeInfo
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- CN120384421A CN120384421A CN202510508329.7A CN202510508329A CN120384421A CN 120384421 A CN120384421 A CN 120384421A CN 202510508329 A CN202510508329 A CN 202510508329A CN 120384421 A CN120384421 A CN 120384421A
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Abstract
The invention belongs to the technical field of waterproofing agents, and particularly relates to a preparation method of a fluorine-free waterproofing agent based on polyurethane-nano silicon dioxide composite. Aiming at the problems of unsatisfactory waterproof performance and poor durability of polyurethane fluoride-free waterproof agents in the prior art, the invention provides a preparation method of a fluoride-free waterproof agent based on polyurethane-nano silicon dioxide compounding, which comprises the steps of reacting bio-based polyol with isocyanate to obtain isocyanate-terminated polyurethane prepolymer; the preparation method comprises the steps of taking a silane coupling agent as a surface modifier to carry out surface modification on nano silicon dioxide to obtain modified hydrophobic nano silicon dioxide, mixing the prepared polyurethane prepolymer with the modified hydrophobic nano silicon dioxide, adding an emulsifying agent, a dispersing agent and deionized water, shearing and emulsifying to form stable emulsion, and regulating the pH value to obtain the fluorine-free waterproof agent. According to the invention, the modified hydrophobic nano silicon dioxide is added into the polyurethane fluorine-free waterproof agent system, so that the waterproof performance of the system is better improved.
Description
Technical Field
The invention belongs to the technical field of waterproofing agents, and particularly relates to a preparation method of a fluorine-free waterproofing agent based on polyurethane-nano silicon dioxide composite.
Background
With the rise of outdoor exercises, demands of people on outdoor articles are greatly increased, and especially demands and demands of textiles such as outdoor tents, backpacks and outdoor jackets are synchronously increased. Such as imparting excellent water and oil repellency to outdoor tents, backpacks, outdoor jacket, etc., while also requiring durability of the water repellency. The waterproof agents are classified into fluorine-containing waterproof agents and fluorine-free waterproof agents, wherein the fluorine-containing waterproof agents can endow fabrics with excellent waterproof effects due to the characteristic of fluorine atoms, but the waterproof agents are limited or even forbidden due to biodegradation and harm caused by substances containing perfluorooctanoic acid (PFOA) or perfluorooctyl sulfonic acid (PFOS). Compared with fluorine-containing waterproofing agents, fluorine-free waterproofing agents have the advantages of safety and environmental protection, and are widely paid attention to.
The present market is mainly divided into three major categories of fluorine-free waterproofing agents of acrylic ester, polyurethane and organosilicon. The traditional fluorine-free waterproofing agent has the defects of reduced waterproof performance, poor washing fastness and insufficient mechanical performance after washing fabrics such as organic silicon and acrylic ester. The polyurethane structural material has good elasticity and good ductility, but the polyurethane fluorine-free waterproof agent has the problems of unsatisfactory waterproof performance and poor durability.
For example, chinese patent application discloses a two-component polyurethane waterproof coating [ application number: 202210945186.2], wherein the two-component polyurethane waterproof coating comprises a component A and a component B, the component A comprises, by weight, 55-75 parts of polyether polyol, 0.3-0.7 part of glycerol, 20-30 parts of diphenylmethane diisocyanate and 0.007-0.01 part of organotin catalyst based on the total weight of the component A, and the component B comprises, by weight, 5-10 parts of polyether polyol, 35-45 parts of liquid filler, 25-55 parts of solid filler, 0.15-0.3 part of dispersing agent, 0.01-0.05 part of anti-settling agent, 0.8-1.3 parts of weather-resistant toner, 0.5-1.5 parts of antioxidant, 0.3-1.0 part of ultraviolet absorber and 3-8 parts of cross-linking agent based on the total weight of the component B.
The bi-component polyurethane waterproof paint provided by the patent application has the advantages of excellent physical properties, good ageing resistance and capability of being directly used in an exposed environment, but the waterproof performance of the polyurethane fluorine-free waterproof agent is still not improved, and the problems of poor durability and the like are solved.
Disclosure of Invention
The invention aims at providing a preparation method of a fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite comprises the following steps:
Reacting bio-based polyol with isocyanate to obtain isocyanate-terminated polyurethane prepolymer;
Step two, surface modification is carried out on the nano silicon dioxide by taking a silane coupling agent as a surface modifier to prepare modified hydrophobic nano silicon dioxide;
And step three, mixing the polyurethane prepolymer prepared in the step one with the modified hydrophobic nano silicon dioxide prepared in the step two, adding an emulsifying agent, a dispersing agent and deionized water, shearing and emulsifying to form stable emulsion, and regulating the pH value to 6-7 to prepare the fluorine-free waterproof agent.
In the preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, the bio-based polyol comprises at least one of castor oil and hydrogenated castor oil.
In the preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, the isocyanate comprises at least one of isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate.
In the preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, the reaction step of the bio-based polyol and isocyanate in the step one is that the bio-based polyol is heated to more than 100 ℃ under the negative pressure condition, then cooled to 50-60 ℃ and isocyanate is added, an organic bismuth catalyst is added under the protection of inert gas atmosphere, and the temperature is raised to 85-90 ℃ for reaction.
In the preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, the molar ratio of the bio-based polyol to the isocyanate is 0.95-1.0:2.0-2.1.
In the preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, the addition amount of the organic bismuth catalyst is 0.05-0.4% of the mass of the bio-based polyol.
The preparation method of the modified hydrophobic nano-silica comprises the following steps of uniformly stirring and dispersing nano-silica and absolute ethyl alcohol at normal temperature, dissolving a silane coupling agent into water to enable the silane coupling agent to be fully hydrolyzed until the silane coupling agent is cooled to the room temperature, stopping stirring, pouring a mixed solution of the silane coupling agent and the water into a mixed solution of the nano-silica and the absolute ethyl alcohol, heating to 60-80 ℃ under the condition of magnetic stirring, condensing and refluxing for 2-4 hours, washing with absolute ethyl alcohol, filtering for several times after the reaction is completed, vacuum drying, grinding and crushing to obtain the modified hydrophobic nano-silica.
In the preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, the particle size of the nano silicon dioxide is 20-50nm.
In the preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, the silane coupling agent is gamma-aminopropyl triethoxysilane.
In the preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, the emulsifying agent comprises at least one of straight-chain dodecanol polyoxyethylene ether and isomeric tridecanol polyoxyethylene ether, and the dispersing agent comprises epoxidized soybean oil.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the modified hydrophobic nano silicon dioxide is added into the polyurethane fluorine-free waterproof agent system, so that the waterproof performance of the system is better improved, and meanwhile, the rough surface of the modified hydrophobic nano silicon dioxide is complementary with the flexibility of polyurethane, so that the problem that the hydrophobicity and durability of the traditional fluorine-free material are difficult to achieve is solved.
2. The fluorine-free waterproof agent disclosed by the invention accords with green chemical standards from raw materials to processes, accords with the green chemical industry and the renewable concept, and actively promotes the sustainable development of green textiles.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
Example 1
The embodiment provides a preparation method of a fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, which comprises the following steps:
Taking 46.65g of castor oil, heating to 100 ℃ under the negative pressure condition, cooling to 55 ℃ and adding 22.23g of isophorone diisocyanate, adding 0.02g of organic bismuth catalyst under the protection of inert gas atmosphere, heating to 88 ℃ and reacting for 2.5 hours to obtain isocyanate-terminated polyurethane prepolymer;
step two, 10g of nano silicon dioxide with the particle size of 20-50nm is added into 30g of absolute ethyl alcohol, the mixture is stirred and dispersed uniformly at normal temperature, gamma-aminopropyl triethoxysilane and water are mixed according to the mass ratio of 1:2, the silane coupling agent is fully hydrolyzed until the mixture is cooled to the room temperature, stirring is stopped, then the mixed solution of gamma-aminopropyl triethoxysilane and water is poured into the mixed solution of nano silicon dioxide and absolute ethyl alcohol, the mixed solution is heated to 70 ℃ under the condition of magnetic stirring, the condensation reflux reaction is carried out for 3 hours, after the reaction is completed, the mixture is washed and filtered for a plurality of times by absolute ethyl alcohol, and the modified hydrophobic nano silicon dioxide is obtained after vacuum drying and grinding and crushing;
And step three, mixing the polyurethane prepolymer prepared in the step one with the modified hydrophobic nano silicon dioxide prepared in the step two, adding 2g of isomeric tridecanol polyoxyethylene ether, 5g of epoxy soybean oil and 200g of deionized water, shearing and emulsifying to form stable emulsion, and regulating the pH value to 6-7 by using acetic acid to prepare the fluorine-free waterproof agent.
Example 2
The embodiment provides a preparation method of a fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, which comprises the following steps:
Taking 46.65g of castor oil, heating to 100 ℃ under the negative pressure condition, cooling to 55 ℃ and adding 26.35g of dicyclohexylmethane-4, 4' -diisocyanate, adding 0.02g of organic bismuth catalyst under the protection of inert gas atmosphere, heating to 88 ℃ and reacting for 2.5 hours to obtain isocyanate-terminated polyurethane prepolymer;
step two, 10g of nano silicon dioxide with the particle size of 20-50nm is added into 30g of absolute ethyl alcohol, the mixture is stirred and dispersed uniformly at normal temperature, gamma-aminopropyl triethoxysilane and water are mixed according to the mass ratio of 1:2, the silane coupling agent is fully hydrolyzed until the mixture is cooled to the room temperature, stirring is stopped, then the mixed solution of gamma-aminopropyl triethoxysilane and water is poured into the mixed solution of nano silicon dioxide and absolute ethyl alcohol, the mixed solution is heated to 70 ℃ under the condition of magnetic stirring, the condensation reflux reaction is carried out for 3 hours, after the reaction is completed, the mixture is washed and filtered for a plurality of times by absolute ethyl alcohol, and the modified hydrophobic nano silicon dioxide is obtained after vacuum drying and grinding and crushing;
And step three, mixing the polyurethane prepolymer prepared in the step one with the modified hydrophobic nano silicon dioxide prepared in the step two, adding 2g of isomeric tridecanol polyoxyethylene ether, 5g of epoxy soybean oil and 200g of deionized water, shearing and emulsifying to form stable emulsion, and regulating the pH value to 6-7 by using acetic acid to prepare the fluorine-free waterproof agent.
Example 3
The embodiment provides a preparation method of a fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, which comprises the following steps:
Taking 46.65g of castor oil, heating to 100 ℃ under the negative pressure condition, cooling to 55 ℃ and adding 16.82g of hexamethylene diisocyanate, adding 0.02g of organic bismuth catalyst under the protection of inert gas atmosphere, and heating to 88 ℃ for reacting for 2.5 hours to obtain isocyanate-terminated polyurethane prepolymer;
step two, 10g of nano silicon dioxide with the particle size of 20-50nm is added into 30g of absolute ethyl alcohol, the mixture is stirred and dispersed uniformly at normal temperature, gamma-aminopropyl triethoxysilane and water are mixed according to the mass ratio of 1:2, the silane coupling agent is fully hydrolyzed until the mixture is cooled to the room temperature, stirring is stopped, then the mixed solution of gamma-aminopropyl triethoxysilane and water is poured into the mixed solution of nano silicon dioxide and absolute ethyl alcohol, the mixed solution is heated to 70 ℃ under the condition of magnetic stirring, the condensation reflux reaction is carried out for 3 hours, after the reaction is completed, the mixture is washed and filtered for a plurality of times by absolute ethyl alcohol, and the modified hydrophobic nano silicon dioxide is obtained after vacuum drying and grinding and crushing;
And step three, mixing the polyurethane prepolymer prepared in the step one with the modified hydrophobic nano silicon dioxide prepared in the step two, adding 2g of isomeric tridecanol polyoxyethylene ether, 5g of epoxy soybean oil and 200g of deionized water, shearing and emulsifying to form stable emulsion, and regulating the pH value to 6-7 by using acetic acid to prepare the fluorine-free waterproof agent.
Example 4
The embodiment provides a preparation method of a fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, which comprises the following steps:
Taking 46.65g of castor oil, heating to 100 ℃ under the negative pressure condition, cooling to 50 ℃ and adding 22.23g of isophorone diisocyanate, adding 0.02g of organic bismuth catalyst under the protection of inert gas atmosphere, heating to 85 ℃ and reacting for 2 hours to obtain isocyanate-terminated polyurethane prepolymer;
Step two, 10g of nano silicon dioxide with the particle size of 20-50nm is added into 30g of absolute ethyl alcohol, the mixture is stirred and dispersed uniformly at normal temperature, gamma-aminopropyl triethoxysilane and water are mixed according to the mass ratio of 1:2, the silane coupling agent is fully hydrolyzed until the mixture is cooled to the room temperature, stirring is stopped, then the mixed solution of gamma-aminopropyl triethoxysilane and water is poured into the mixed solution of nano silicon dioxide and absolute ethyl alcohol, the mixture is heated to 60 ℃ under the condition of magnetic stirring, the condensation reflux reaction is carried out for 2 hours, after the reaction is completed, the mixture is washed and filtered for a plurality of times by absolute ethyl alcohol, and the modified hydrophobic nano silicon dioxide is obtained after vacuum drying and grinding and crushing;
And step three, mixing the polyurethane prepolymer prepared in the step one with the modified hydrophobic nano silicon dioxide prepared in the step two, adding 2g of isomeric tridecanol polyoxyethylene ether, 5g of epoxy soybean oil and 200g of deionized water, shearing and emulsifying to form stable emulsion, and regulating the pH value to 6-7 by using acetic acid to prepare the fluorine-free waterproof agent.
Example 5
The embodiment provides a preparation method of a fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite, which comprises the following steps:
taking 46.65g of castor oil, heating to 100 ℃ under the negative pressure condition, cooling to 60 ℃ and adding 22.23g of isophorone diisocyanate, adding 0.02g of organic bismuth catalyst under the protection of inert gas atmosphere, heating to 90 ℃ and reacting for 3 hours to obtain isocyanate-terminated polyurethane prepolymer;
Step two, 10g of nano silicon dioxide with the particle size of 20-50nm is added into 30g of absolute ethyl alcohol, the mixture is stirred and dispersed uniformly at normal temperature, gamma-aminopropyl triethoxysilane and water are mixed according to the mass ratio of 1:2, the silane coupling agent is fully hydrolyzed until the mixture is cooled to the room temperature, stirring is stopped, then the mixed solution of gamma-aminopropyl triethoxysilane and water is poured into the mixed solution of nano silicon dioxide and absolute ethyl alcohol, the mixed solution is heated to 80 ℃ under the condition of magnetic stirring, the condensation reflux reaction is carried out for 4 hours, after the reaction is completed, the mixture is washed and filtered for a plurality of times by absolute ethyl alcohol, and the modified hydrophobic nano silicon dioxide is obtained after vacuum drying and grinding and crushing;
And step three, mixing the polyurethane prepolymer prepared in the step one with the modified hydrophobic nano silicon dioxide prepared in the step two, adding 2g of isomeric tridecanol polyoxyethylene ether, 5g of epoxy soybean oil and 200g of deionized water, shearing and emulsifying to form stable emulsion, and regulating the pH value to 6-7 by using acetic acid to prepare the fluorine-free waterproof agent.
Comparative example 1
The comparative example provides a preparation method of a fluorine-free waterproof agent, which comprises the following steps:
Taking 46.65g of castor oil, heating to 100 ℃ under the negative pressure condition, cooling to 55 ℃ and adding 22.23g of isophorone diisocyanate, adding 0.02g of organic bismuth catalyst under the protection of inert gas atmosphere, heating to 88 ℃ and reacting for 2.5 hours to obtain isocyanate-terminated polyurethane prepolymer;
Step two, 10g of nano silicon dioxide with the particle size of 20-50nm is taken and added into 30g of absolute ethyl alcohol, the mixture is stirred and dispersed uniformly at normal temperature, the mixture is washed by the absolute ethyl alcohol and filtered for a plurality of times, and the mixture is dried in vacuum and ground and crushed to obtain nano silicon dioxide raw materials;
And step three, mixing the polyurethane prepolymer prepared in the step one and the nano silicon dioxide raw material prepared in the step two, adding 2g of isomeric tridecanol polyoxyethylene ether, 5g of epoxy soybean oil and 200g of deionized water, shearing and emulsifying to form stable emulsion, and regulating the pH value to 6-7 by using acetic acid to prepare the fluorine-free waterproof agent.
Comparative example 2
The comparative example provides a preparation method of a fluorine-free waterproof agent, which comprises the following steps:
Taking 46.65g of castor oil, heating to 100 ℃ under the negative pressure condition, cooling to 55 ℃ and adding 22.23g of isophorone diisocyanate, adding 0.02g of organic bismuth catalyst under the protection of inert gas atmosphere, heating to 88 ℃ and reacting for 2.5 hours to obtain isocyanate-terminated polyurethane prepolymer;
And step two, adding 2g of isomeric tridecanol polyoxyethylene ether, 5g of epoxidized soybean oil and 200g of deionized water into the polyurethane prepolymer prepared in the step one, shearing and emulsifying to form stable emulsion, and regulating the pH value to 6-7 by using acetic acid to prepare the fluorine-free waterproof agent.
Application example 1
The fluorine-free waterproofing agents prepared in examples 1-3 and comparative examples 1-2 were prepared into working solutions with mass fractions of 70g/L, the natural cotton fabrics (20 cm. Times.20 cm) were subjected to waterproof finishing with the working solutions, a padding-padding process was adopted, the padding surplus was 90%, and the materials were baked at 160 ℃ for 2min for setting, thereby obtaining waterproof finished cotton fabrics.
The fluorine-free waterproofing agents prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to contact angle detection corresponding to the obtained waterproof finished cotton fabrics. The spray water test was performed according to AATCC22-2017, the waterproof grade was rated, and after 10 times of water washing, the waterproof finishing cotton fabric was rated again. The results are shown in the following table:
As is clear from the above table, the fluorine-free waterproofing agents in examples 1 to 3 of the present invention all have excellent waterproofing performance and good durability. From the comparison of example 1 and comparative example 1, it is understood that the nano silica is not modified and is combined with the polyurethane component by non-chemical bond force, so that the washing fastness is lowered. As can be seen from the comparison of the example 1 and the comparative example 2, the addition of the modified nano-silica into the fluorine-free waterproofing agent system can improve the waterproofing performance of the system. Comprehensive comparison shows that the polyurethane-nano SiO 2 composite system combines bio-based polyurethane with hydrophobic nano particles, and improves the waterproof performance through the double functions of chemical bond and physical adsorption. The rough surface of the nano SiO 2 is complementary with the flexibility of polyurethane, so that the problem that the hydrophobicity and durability of the traditional fluorine-free material are difficult to be achieved. The fluorine-free waterproof agent provided by the invention accords with the green chemical standard from raw materials (bio-based polyether) to processes (solvent-free emulsification), accords with the green chemical industry and the renewable concept, and actively promotes the sustainable development of green textiles.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (10)
1. The preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite is characterized by comprising the following steps of:
Reacting bio-based polyol with isocyanate to obtain isocyanate-terminated polyurethane prepolymer;
Step two, surface modification is carried out on the nano silicon dioxide by taking a silane coupling agent as a surface modifier to prepare modified hydrophobic nano silicon dioxide;
And step three, mixing the polyurethane prepolymer prepared in the step one with the modified hydrophobic nano silicon dioxide prepared in the step two, adding an emulsifying agent, a dispersing agent and deionized water, shearing and emulsifying to form stable emulsion, and regulating the pH value to 6-7 to prepare the fluorine-free waterproof agent.
2. The method for preparing a fluorine-free waterproofing agent based on polyurethane-nano silica composite according to claim 1, wherein the bio-based polyol comprises at least one of castor oil and hydrogenated castor oil.
3. The method for preparing a fluorine-free waterproofing agent based on polyurethane-nano silica composite according to claim 1, wherein the isocyanate comprises at least one of isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate.
4. The preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite according to claim 1, wherein the reaction step of the bio-based polyol and isocyanate in the first step is that the bio-based polyol is heated to more than 100 ℃ under the negative pressure condition, then cooled to 50-60 ℃ and isocyanate is added, and under the protection of inert gas atmosphere, an organic bismuth catalyst is added and the temperature is raised to 85-90 ℃ for reaction.
5. The method for preparing a fluorine-free waterproof agent based on polyurethane-nano silica composite according to claim 4, wherein the molar ratio of the bio-based polyol to the isocyanate is 0.95-1.0:2.0-2.1.
6. The preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite according to claim 4, wherein the addition amount of the organobismuth catalyst is 0.05-0.4% of the mass of the bio-based polyol.
7. The preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite of claim 1, wherein the preparation method of the modified hydrophobic nano silicon dioxide in the second step is characterized in that nano silicon dioxide and absolute ethyl alcohol are uniformly stirred and dispersed at normal temperature, a silane coupling agent is dissolved into water to enable the silane coupling agent to be fully hydrolyzed until the silane coupling agent is cooled to room temperature, stirring is stopped, then a mixed solution of the silane coupling agent and water is poured into a mixed solution of nano silicon dioxide and absolute ethyl alcohol, heating is carried out to 60-80 ℃ under the condition of magnetic stirring, condensation reflux reaction is carried out for 2-4 hours, and after the reaction is completed, the modified hydrophobic nano silicon dioxide is obtained after washing and suction filtration for a plurality of times by absolute ethyl alcohol, vacuum drying and grinding and crushing.
8. The method for preparing a fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite according to claim 7, wherein the particle size of the nano silicon dioxide is 20-50nm.
9. The method for preparing a fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite according to claim 7, wherein the silane coupling agent is gamma-aminopropyl triethoxysilane.
10. The preparation method of the fluorine-free waterproof agent based on polyurethane-nano silicon dioxide composite of claim 1, wherein the emulsifier comprises at least one of straight-chain dodecanol polyoxyethylene ether and isomeric tridecanol polyoxyethylene ether, and the dispersant comprises epoxidized soybean oil.
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| CN121065961A (en) * | 2025-11-10 | 2025-12-05 | 石狮市宝益织造印染有限公司 | Fluorine-free waterproof composite fabric and preparation method thereof |
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| CN121065961A (en) * | 2025-11-10 | 2025-12-05 | 石狮市宝益织造印染有限公司 | Fluorine-free waterproof composite fabric and preparation method thereof |
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