A waterproof and oil-proof composition, emulsified slurry, and preparation method and application thereof

Abstract

The present application discloses a waterproof and oil-proof composition, an emulsified slurry, and a preparation method and application thereof. The waterproof and oil-proof composition of the present application is formed by dispersing paraffin in a polymeric cross-linked network containing silicon dioxide; wherein the polymeric cross-linked network containing silicon dioxide is generated by a condensation reaction of tetraethyl orthosilicate hydrolyzed and polyvinyl alcohol. The waterproof and oil-proof composition of the present application utilizes paraffin and a polymeric cross-linked network containing silicon dioxide generated by a condensation reaction of tetraethyl orthosilicate hydrolyzed and polyvinyl alcohol to obtain excellent waterproof and oil-proof properties; and all raw materials are non-toxic and harmless, and have the advantages of safety and environmental protection, and will not cause harm to the human body and the environment. The preparation method of the waterproof and oil-proof composition of the present application is simple and has broad application prospects.

Description

Technical Field

[0001] The present application relates to the technical field of waterproof and oil-proof materials, and in particular to a waterproof and oil-proof composition, an emulsified slurry, and a preparation method and application thereof. Background Art

[0002] Traditional disposable plastic food tableware has caused huge environmental pollution problems because it is difficult to degrade. With the increasing attention paid to environmental protection, degradable tableware has developed rapidly, including routes based on degradable polylactic acid and biomass cellulose. Among them, cellulose is widely used in degradable tableware because of its wide biomass source, fast degradation rate, and high environmental friendliness. However, after hot pressing, cellulose tableware has a porous structure inside, which has the disadvantages of easy water absorption and high air permeability, affecting the barrier properties of cellulose tableware. Therefore, it is necessary to add waterproof and oil-proof agents to prevent water and oil from seeping out of food and beverages. The main ingredients of the most commonly used waterproof and oil-proof agents contain perfluorooctanoic acid (PFOA) and / or perfluorooctane sulfonic acid (PFOS). However, perfluoro oil-proof agents not only produce toxic substances when heated, such as perfluorooctane sulfonamide, which cause great harm to the human body and can cause diseases such as liver cancer and fat metabolism disorders in the body; and the use of perfluoro oil-proof agents will also bring serious land pollution problems.

[0003] The patent application with application number 202010675496.8 discloses a waterproof and oil-proof agent, a preparation method and an application. The waterproof and oil-proof agent coating includes raw materials styrene acrylic polymer, beeswax emulsion, polyvinyl alcohol, modified starch, plasticizer, and deionized water. The styrene acrylic polymer used is difficult to degrade, and the phenyl groups therein can cause harm to the human body and the environment.

[0004] The patent application with application number 202011066406.1 discloses a fluorine-free waterproof and oil-proof agent and its preparation method. The waterproof and oil-proof coating includes raw materials of fluorine-free acrylic polymer particles, bio-wax, natural adhesive components, inorganic nanoparticles, anti-settling agents, and solvents. The preparation process of the waterproof and oil-proof coating requires a nitrogen atmosphere, which is costly, and requires the use of organic solvents such as n-pentane, isopentane, n-hexane, and cyclohexane, which still has environmental problems.

[0005] The patent application with application number 202111503080.9 discloses a fluorine-free waterproof and oil-proof agent and its preparation method and application. The main raw material components of the waterproof and oil-proof agent are sodium alginate and polyethylene glycol cross-linked to prepare the oil-proof agent, and polydimethylsiloxane derivatives are condensed to prepare the waterproof agent; the waterproof agent and the oil-proof agent are compounded to obtain the fluorine-free waterproof and oil-proof agent. The preparation process of the waterproof agent requires the use of organic solvents such as anhydrous ethanol, propanol, methanol, and acetone, which increases the risk of environmental problems.

[0006] In addition, paraffin wax, as a product of petrochemical industry, has large reserves and low price, and does not produce carcinogens. Many scholars at home and abroad use paraffin wax as an additive for paper, but the effect of using paraffin wax alone as a waterproofing agent is not good.

[0007] Therefore, how to develop a waterproof and oil-proof agent that has excellent waterproof and oil-proof properties and is non-toxic and harmless to the human body and the environment remains a research focus and difficulty in this field. Summary of the invention

[0008] The purpose of the present application is to provide a new waterproof and oil-proof composition, an emulsified slurry, and a preparation method and application thereof.

[0009] This application adopts the following technical solutions:

[0010] The first aspect of the present application discloses a waterproof and oil-proof composition, which is formed by dispersing paraffin in a polymeric cross-linked network containing silicon dioxide; wherein the polymeric cross-linked network containing silicon dioxide is generated by the condensation reaction of polyvinyl alcohol and hydrolyzed ethyl orthosilicate.

[0011] It should be noted that the waterproof and oil-proof composition of the present application produces waterproof and oil-proof properties through paraffin wax, and produces excellent oil-proof ability through a polymer cross-linked network containing silicon dioxide generated by the hydrolysis of tetraethyl orthosilicate and the condensation reaction of polyvinyl alcohol; paraffin wax and the polymer cross-linked network containing silicon dioxide are mixed to obtain a waterproof and oil-proof agent with further improved performance; and the raw materials are non-toxic and will not cause harm to the human body and the environment.

[0012] It should also be noted that in the present application, paraffin wax provides the main water and oil resistance properties; the silicon dioxide generated by the hydrolysis of tetraethyl orthosilicate can enhance the oil resistance; polyvinyl alcohol can enhance the oil resistance and adhesion to paper, and condense with the hydrolysis product of tetraethyl orthosilicate to generate a cross-linked network, further enhancing the oil resistance.

[0013] In one implementation of the present application, the paraffin wax is food grade microcrystalline wax.

[0014] It should be noted that in one implementation of the present application, food-grade microcrystalline wax, tetraethyl orthosilicate and polyvinyl alcohol are uniformly mixed in water to prepare a waterproof and oil-proofing agent having more excellent waterproof and oil-proofing properties.

[0015] In one implementation of the present application, the waterproof and oil-proof composition contains 100-150 parts by weight of paraffin wax, and the polymerized cross-linked network containing silicon dioxide is generated by the condensation reaction of 20-60 parts by weight of tetraethyl orthosilicate hydrolyzed and 15-30 parts by weight of polyvinyl alcohol.

[0016] Preferably, the waterproof and oil-proof composition contains 120 parts by weight of paraffin wax, and the polymerized cross-linked network containing silicon dioxide is produced by the condensation reaction of 50 parts by weight of ethyl orthosilicate hydrolyzed and 20 parts by weight of polyvinyl alcohol.

[0017] It should be noted that the above specific dosage is only specifically adopted in one implementation of the present application, and can prepare a formula and dosage with better waterproof and oil-proof performance. It can be understood that on this basis, appropriate adjustments can be made according to needs.

[0018] The second aspect of the present application discloses a waterproof and oil-proof emulsified slurry, which comprises 100-150 parts by weight of paraffin, 30-45 parts by weight of emulsifier, 20-60 parts by weight of tetraethyl orthosilicate and 15-30 parts by weight of polyvinyl alcohol dispersed in 600-800 parts by weight of deionized water to form an emulsified slurry.

[0019] In one implementation of the present application, the waterproof and oil-proof emulsified slurry includes dispersing 120 parts by weight of paraffin, 36 parts by weight of emulsifier, 50 parts by weight of tetraethyl orthosilicate and 20 parts by weight of polyvinyl alcohol in 680 parts by weight of deionized water to form an emulsified slurry.

[0020] In one implementation of the present application, the paraffin wax used in the waterproof and oil-proof emulsified slurry is food-grade microcrystalline wax.

[0021] Preferably, the emulsifier used in the waterproof and oil-proof emulsified slurry is 58# emulsifier.

[0022] It should be noted that the waterproof and oil-proof emulsified slurry of the present application is actually a waterproof and oil-proof agent prepared by dispersing the waterproof and oil-proof composition of the present application in water; the component that mainly plays a role in waterproof and oil-proof properties in the waterproof and oil-proof emulsified slurry of the present application is the waterproof and oil-proof composition of the present application; the emulsifier is only used to make paraffin, tetraethyl orthosilicate and polyvinyl alcohol better dispersed in deionized water, and emulsified to obtain the waterproof and oil-proof emulsified slurry of the present application.

[0023] It should also be noted that in one implementation of the present application, the waterproof and oil-proof emulsified slurry is directly added to the cellulose pulp during use, and after mixing evenly, the paper-based disposable degradable tableware is obtained by film pressing. In principle, the waterproof and oil-proof composition of the present application can also be directly added to the cellulose pulp, but this requires a good guarantee that the waterproof and oil-proof composition is evenly dispersed in the cellulose pulp; therefore, it is relatively more convenient to add the waterproof and oil-proof emulsified slurry of the present application to the cellulose pulp for even mixing, so that the final paper tableware has better and more uniform waterproof and oil-proof properties. It can be understood that the waterproof and oil-proof composition of the present application can be directly used in the form of solid powder for easy transportation, and then the waterproof and oil-proof emulsified slurry of this application is prepared before use; this is convenient for transportation, convenient for use, and ensures the use effect.

[0024] The third aspect of the present application discloses a method for preparing the waterproof and oil-proof emulsified slurry of the present application, comprising heating a portion of deionized water, adding paraffin wax to melt it, adding an emulsifier and tetraethyl orthosilicate, and mixing them evenly to obtain a first solution; heating the remaining portion of deionized water, adding polyvinyl alcohol, and mixing them evenly to obtain a second solution; and mixing the first solution and the second solution evenly to obtain the waterproof and oil-proof emulsified slurry of the present application. Among them, the portion of deionized water is usually calculated according to the proportion of the total amount of deionized water required, and the total deionized water is evenly divided into two parts, one part is used to prepare the first solution, that is, the paraffin solution; and the other part is used to prepare the second solution, that is, the polyvinyl alcohol solution.

[0025] It should be noted that in the preparation method of the present application, the deionized water is heated mainly to facilitate the melting of paraffin or polyvinyl alcohol, and the heating temperature is usually 85°C-95°C. In one implementation of the present application, the deionized water of the first solution is heated to 85°C-95°C, and the deionized water of the second solution is heated to 90°C-95°C; and the time for mixing the first solution and the second solution evenly is at least 20 minutes, so that the cross-linking reaction can proceed fully, and the heating is continued to maintain the temperature at 85°C-95°C during the process.

[0026] The fourth aspect of the present application discloses the use of the waterproof and oil-proof composition of the present application or the waterproof and oil-proof emulsified slurry of the present application in the preparation of waterproof and oil-proof paper or waterproof and oil-proof plastic.

[0027] It should be noted that the key to the present application is to form a waterproof and oil-proof agent with better waterproof and oil-proof properties through the combination of paraffin, tetraethyl orthosilicate and polyvinyl alcohol; therefore, in principle, the existing waterproof and oil-proof agents can be replaced by the waterproof and oil-proof composition of the present application or the waterproof and oil-proof emulsified slurry of the present application, including but not limited to waterproof and oil-proof paper and waterproof and oil-proof plastics.

[0028] The fifth aspect of the present application discloses a waterproof and oil-proof paper or waterproof and oil-proof plastic, which contains the waterproof and oil-proof composition of the present application, or the raw materials for preparing the waterproof and oil-proof paper or waterproof and oil-proof plastic are added with the waterproof and oil-proof emulsified slurry of the present application.

[0029] It should be noted that the waterproof and oil-proof paper or waterproof and oil-proof plastic of the present application has better waterproof and oil-proof performance because it contains the waterproof and oil-proof composition of the present application, or is added with the waterproof and oil-proof emulsified slurry of the present application; and the waterproof and oil-proof composition or waterproof and oil-proof emulsified slurry of the present application is non-toxic and will not cause harm to the human body and the environment.

[0030] The beneficial effects of this application are:

[0031] The waterproof and oil-proof composition of the present application utilizes a cross-linked polymer network containing silicon dioxide generated by the polycondensation reaction of paraffin and ethyl orthosilicate after hydrolysis and polyvinyl alcohol to obtain excellent waterproof and oil-proof performance; in addition, all raw materials are non-toxic and harmless, have the advantages of safety and environmental protection, and will not cause harm to the human body and the environment. The preparation method of the waterproof and oil-proof composition of the present application is simple and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 1 is a statistical result diagram of the particle size of the water-proof and oil-proof agent in the embodiment of the present application;

[0033] Figure 2 This is a test result diagram of the waterproof performance of paper tableware prepared by adding a waterproof and oil-proof agent in an embodiment of the present application;

[0034] Figure 3 This is a graph showing the oil-proof performance test results of paper tableware prepared by adding a waterproof and oil-proof agent in an embodiment of the present application. DETAILED DESCRIPTION

[0035] The present application is further described in detail below through specific examples. The following examples are only used to further illustrate the present application and should not be construed as limiting the present application.

[0036] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources, and the experimental methods used in the following examples are conventional methods unless otherwise specified.

[0037] Embodiment 1

[0038] The preparation method of the waterproof and oil-proofing agent of this example comprises:

[0039] 1. Weigh 120 kg of food-grade microcrystalline wax (purchased from Jingmen Weijia Industrial Co., Ltd.), 36 kg of 58# emulsifier (purchased from Hai'an Petrochemical Plant in Jiangsu Province), 50 kg of ethyl orthosilicate (purchased from Chongqing Huanghui Co., Ltd.), 20 kg of polyvinyl alcohol (purchased from Aladdin), and 680 kg of deionized water.

[0040] 2. First, heat 340kg of water to 85-95 degrees Celsius, then add food-grade microcrystalline wax and stir until it is completely melted, then add 58# emulsifier to mix evenly, then add ethyl orthosilicate and stir for 20 minutes to obtain the first solution.

[0041] 3. Add polyvinyl alcohol to 340 kg of water, heat to 90-95 degrees Celsius, and stir until the polyvinyl alcohol is completely melted to obtain a second solution.

[0042] 4. Add the second solution into the first solution and stir at 85-95 degrees Celsius for 20 minutes.

[0043] 5. Cooling can obtain the silicone-based fluorine-free oil-proof agent, that is, the water-proof and oil-proof agent in this example.

[0044] Embodiment 2

[0045] The raw materials used in this example are the same as those in Example 1. The specific formula and preparation method of the waterproof and oil-proofing agent in this example include:

[0046] 1. Weigh 150kg of food-grade microcrystalline wax, 45kg of 58# emulsifier, 60kg of ethyl orthosilicate, 30kg of polyvinyl alcohol, and 800kg of deionized water.

[0047] 2. First heat 400kg of water to 85-95 degrees Celsius, then add food-grade microcrystalline wax and stir until it is completely melted, then add 58# emulsifier to mix evenly, then add ethyl orthosilicate and stir for 20 minutes to obtain the first solution.

[0048] 3. Add polyvinyl alcohol into 400 kg of water, heat to 90-95 degrees Celsius, and stir until the polyvinyl alcohol is completely melted to obtain a second solution.

[0049] 4. Add the second solution into the first solution and stir at 85-95 degrees Celsius for 20 minutes.

[0050] 5. Cooling can obtain the silicone-based fluorine-free oil-proof agent, that is, the water-proof and oil-proof agent in this example.

[0051] Embodiment 3

[0052] The raw materials used in this example are the same as those in Example 1. The specific formula and preparation method of the waterproof and oil-proofing agent in this example include:

[0053] 1. Weigh 100kg of food-grade microcrystalline wax, 30kg of 58# emulsifier, 20kg of ethyl orthosilicate, 15kg of polyvinyl alcohol, and 600kg of deionized water.

[0054] 2. First, heat 300 kg of water to 85-95 degrees Celsius, then add food-grade microcrystalline wax and stir until it is completely melted, then add emulsifier to mix evenly, then add ethyl orthosilicate and stir for 20 minutes to obtain the first solution.

[0055] 3. Add polyvinyl alcohol to 300 kg of water, heat to 90-95 degrees Celsius, and stir until the polyvinyl alcohol is completely melted to obtain a second solution.

[0056] 4. Add the second solution into the first solution and stir at 85-95 degrees Celsius for 20 minutes.

[0057] 5. Cooling can obtain the silicone-based fluorine-free oil-proof agent, that is, the water-proof and oil-proof agent in this example.

[0058] The three water-proof and oil-proofing agents prepared in Examples 1 to 3 were respectively subjected to particle size test, water-proof performance test and oil-proof performance test, as follows:

[0059] Particle size test of water-proof and oil-proof agent: In this example, a dynamic light scattering instrument was used to measure the particle size of the water-proof and oil-proof agent. The test results showed that the particle sizes of the three water-proof and oil-proof agents prepared in Examples 1 to 3 were mainly distributed between 700-955 nm, which could meet the use requirements. Among them, the particle size distribution of the water-proof and oil-proof agent in Example 1 is as follows: Figure 1 shown.

[0060] Waterproof performance test: Cellulose pulp, generally sugarcane fiber, bamboo fiber and / or wood fiber, is made by removing impurities from the raw materials, separating the fibers mechanically or chemically, and then washing, bleaching, drying and pressing them into pulp boards for use. In this case, sugarcane fiber is used, and the waterproof and oil-proof agent is added at a ratio of 9 parts by weight to 100 parts by weight of fiber. The molding is performed by hot pressing using Zhiben's Aichuang 12510 equipment. According to the functional requirements of the product, the thickness of paper tableware is generally greater than 0.6mm. The specific thickness in this case is 0.8mm. A contact angle meter is used to test the waterproof performance of paper tableware.

[0061] The test results show that the water contact angle of the paper tableware added with the waterproof and oil-proofing agent of Example 1 is 125°, the water contact angle of the paper tableware added with the waterproof and oil-proofing agent of Example 2 is 121°, and the water contact angle of the paper tableware added with the waterproof and oil-proofing agent of Example 3 is 123°; it can be seen that the water contact angle of the paper tableware prepared by adding the waterproof and oil-proofing agent can reach more than 120°, indicating that the waterproof and oil-proofing agent has very excellent waterproof performance. Among them, the test results of the paper tableware added with the waterproof and oil-proofing agent of Example 2 are as follows: Figure 2 shown.

[0062] Oil-proof performance test: Use the same method as the "waterproof performance test" to prepare waterproof and oil-proof paper tableware, pour 45° hot oil into the paper tableware. In this example, conventional household rapeseed oil, peanut oil, blended oil, soybean oil, olive oil, and chili oil were used for the test. After pouring the hot oil for 30 minutes, observe whether there is oil leakage.

[0063] The test results show that the paper tableware added with the water-proof and oil-proof agent of Example 1, Example 2, and Example 3 respectively, poured with 45°C hot oil and left for 30 minutes without leakage, indicating that the water-proof and oil-proof agent prepared in the three examples has very excellent oil-proof performance. Some of the photographic results are shown in FIG. Figure 3 shown.

[0064] The above contents are further detailed descriptions of the present application in combination with specific implementation methods, and it cannot be determined that the specific implementation of the present application is limited to these descriptions. For ordinary technicians in the technical field to which the present application belongs, several simple deductions or substitutions can be made without departing from the concept of the present application.

Claims

1. A waterproof and oil-proof composition, characterized in that: It is formed by paraffin wax dispersed in a polymeric cross-linked network containing silica; The polymeric cross-linked network containing silicon dioxide is generated by the condensation reaction of tetraethyl orthosilicate and polyvinyl alcohol; The waterproof and oil-proof composition contains 100-150 parts by weight of paraffin wax, and the polymer cross-linked network containing silicon dioxide is generated by the condensation reaction of 20-60 parts by weight of ethyl orthosilicate hydrolyzed and 15-30 parts by weight of polyvinyl alcohol.

2. The waterproof and oil-proof composition according to claim 1, characterized in that: The paraffin wax is food grade microcrystalline wax.

3. The waterproof and oil-proof composition according to claim 1 or 2, characterized in that: The waterproof and oil-proof composition contains 120 parts by weight of paraffin wax, and the polymerized cross-linked network containing silicon dioxide is generated by the condensation reaction of 50 parts by weight of ethyl orthosilicate hydrolyzed and 20 parts by weight of polyvinyl alcohol.

4. A waterproof and oil-proof emulsified slurry, characterized in that: The method comprises dispersing 100-150 parts by weight of paraffin wax, 30-45 parts by weight of emulsifier, 20-60 parts by weight of tetraethyl orthosilicate and 15-30 parts by weight of polyvinyl alcohol in 600-800 parts by weight of deionized water to form an emulsified slurry; The preparation method of the waterproof and oil-proof emulsified slurry comprises heating part of the deionized water, adding paraffin to melt it, adding an emulsifier and tetraethyl orthosilicate, mixing them evenly, and obtaining a first solution; heating the remaining part of the deionized water, adding polyvinyl alcohol, mixing them evenly, and obtaining a second solution; and mixing the first solution and the second solution evenly, thus obtaining the waterproof and oil-proof emulsified slurry; The heating temperature is 85°C-95°C; The first solution and the second solution are mixed evenly for at least 20 minutes to facilitate the cross-linking reaction to proceed fully. During this process, heating is continued to maintain the temperature at 85° C.-95° C.

5. The waterproof and oil-proof emulsified slurry according to claim 4, characterized in that: The method comprises dispersing 120 parts by weight of paraffin wax, 36 parts by weight of emulsifier, 50 parts by weight of tetraethyl orthosilicate and 20 parts by weight of polyvinyl alcohol in 680 parts by weight of deionized water to form an emulsified slurry.

6. The waterproof and oil-proof emulsified slurry according to claim 4 or 5, characterized in that: The paraffin wax is food grade microcrystalline wax.

7. The waterproof and oil-proof emulsified slurry according to claim 4 or 5, characterized in that: The emulsifier is 58# emulsifier.

8. Use of the waterproof and oil-proof composition according to any one of claims 1 to 3 or the waterproof and oil-proof emulsified slurry according to any one of claims 4 to 7 in the preparation of waterproof and oil-proof paper or waterproof and oil-proof plastic.

9. A waterproof and oil-proof paper or waterproof and oil-proof plastic, characterized in that: The invention relates to a waterproof and oil-proof composition comprising the waterproof and oil-proof composition according to any one of claims 1 to 3, or is prepared from raw materials to which the waterproof and oil-proof emulsified slurry according to any one of claims 4 to 7 is added.

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