A graphene-based water-resistant additive suitable for water-based coatings and its preparation process

Abstract

The present invention belongs to the technical field of water-based coating water-resistant additives, and specifically relates to a graphene-based water-resistant additive suitable for water-based coatings and a preparation process thereof. The additive is composed of a main material and an auxiliary material. The main material is graphene oxide, and the auxiliary materials are glycidyl methacrylate, peroxide, polyethylene glycol, and deionized water. The additive has the characteristic of improving the water resistance of water-based coatings, and the water resistance time is increased from 180 hours to 500 hours or more.

Description

Technical Field

[0001] The present invention belongs to the technical field of water-based coating water-resistant additives, and specifically relates to a graphene-based water-resistant additive suitable for water-based coatings and a preparation process thereof. Background Art

[0002] Waterproof coatings are divided into water-based waterproof coatings and oil-based waterproof coatings; among them, oil-based waterproof coatings are insoluble in water and need to be dissolved with chemical liquids, which is also the reason why they are not environmentally friendly; water-based waterproof coatings do not have this hazard and are environmentally friendly and non-toxic; therefore, the research and development of water-based coatings has received more and more attention.

[0003] Due to problems such as poor water resistance, water-based coatings in my country are still unable to completely replace traditional non-environmentally friendly solvent-based coating materials.

[0004] Therefore, it is urgent to solve the water resistance problem of water-based coatings. Summary of the invention

[0005] In view of the above-mentioned technical problems, the present invention provides a graphene-based water-resistant additive suitable for water-based coatings and a preparation process thereof. The additive can coat and shield the water-based part of the resin in the water-based coating, weaken the hydrophilicity of the resin, and thus improve the water resistance of the water-based coating.

[0006] The technical solution of the present invention is:

[0007] A graphene-based water-resistant additive suitable for water-based coatings, the additive comprising a main ingredient of graphene oxide and auxiliary materials; in parts by mass, the main ingredients include 100 parts of graphene oxide, 10-25 parts of glycidyl methacrylate, 5-20 parts of peroxide, 20-50 parts of polyethylene glycol, and 1000-5000 parts of deionized water.

[0008] Furthermore, graphene oxide is an oxide of graphene, the purity of glycidyl methacrylate is greater than 95%, the peroxide is a compound with a peroxy group -OO-, the molecular weight range of polyethylene glycol is 200-6000, and the conductivity of deionized water is less than 0.5 mS / cm.

[0009] A preparation process of a graphene-based water-resistant additive suitable for water-based coatings comprises the following preparation steps: step 1, initial preparation of the graphene-based water-resistant additive; step 2, preparation of the graphene-based water-resistant additive; step 3, canning of the graphene-based water-resistant additive.

[0010] Furthermore, step 1 is specifically as follows: deionized water is added into a clean reactor with stirring and heating functions, graphene oxide is added while stirring, and after the graphene oxide is evenly dispersed, ultrasonic treatment is performed, and then peroxide is added and stirred for 30 minutes, and then glycidyl methacrylate and polyethylene glycol are added and stirred for 30 minutes, heated to a certain temperature and stirred, and cooled to room temperature to obtain an initial graphene-based water-resistant additive.

[0011] Furthermore, the ultrasonic treatment is treatment with an ultrasonic vibration rod for 0.5-2 hours.

[0012] Furthermore, the heating temperature is 60-90° C., and the stirring is performed for 3-6 hours.

[0013] Furthermore, step 2 is specifically as follows: the initial graphene-based water-resistant additive is filtered through a 100-300 mesh sieve to remove substances that cannot be filtered, and the filtered additive is collected to obtain a graphene-based water-resistant additive.

[0014] Furthermore, step 3 specifically includes: injecting the graphene-based water-resistant additive into a clean and water-free storage tank and sealing it for storage.

[0015] The design idea of ​​the present invention is:

[0016] The suspension of graphene oxide dispersed in deionized water is used as a carrier to ensure that the main ingredient graphene oxide in the additive is fully mixed with auxiliary ingredients such as glycidyl methacrylate, peroxide, polyethylene glycol, and deionized water, thereby giving full play to the synergistic effect of the main ingredient and the auxiliary ingredients. The free radicals generated by peroxide in water form a chemical bond between the main ingredient and the auxiliary ingredient; the carbon-carbon double bonds on the glycidyl methacrylate molecule establish a stable interface bonding force with graphene oxide through the free radicals generated by peroxide; polyethylene glycol improves the compatibility of the additive with the water-based coating resin; and deionized water provides a carrier for uniform and stable dispersion of the additive. Based on the above characteristics, a water-resistant additive for water-based coatings is finally obtained.

[0017] Compared with the prior art, the invention has the following beneficial effects.

[0018] 1. The auxiliary agent prepared by the present invention has a simple preparation process, and the raw materials required in the formula can be directly purchased in the market. The coating is suitable for various water-based coating substrates such as water-based acrylic coatings, water-based alkyd coatings, water-based epoxy coatings, water-based polyurethane coatings, and water-based amino coatings.

[0019] 2. The additive prepared by the present invention can coat and shield the aqueous part of the resin, weaken the hydrophilicity of the resin, thereby improving the water resistance of the water-based coating, and the water resistance time is increased from 180 hours to 500 hours or more. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1This is the macroscopic state of the graphene-based water-resistant additive of Example 1.

[0021] Figure 2 This is the microscopic morphology of the graphene-based water-resistant additive of Example 1.

[0022] Figure 3 The effect of the graphene-based water-resistant additive of Example 1 on the water resistance of water-based epoxy coating (a, water resistance of coating without adding graphene-based water-resistant additive, b, water resistance of coating with adding graphene-based water-resistant additive). DETAILED DESCRIPTION

[0023] The following examples are further detailed descriptions of the present invention. It should be understood that these examples are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0024] A graphene-based water-resistant additive suitable for water-based coatings, the additive comprising a main ingredient of graphene oxide and auxiliary materials; in parts by mass, the main ingredients include 100 parts of graphene oxide, 10-25 parts of glycidyl methacrylate, 5-20 parts of peroxide, 20-50 parts of polyethylene glycol, and 1000-5000 parts of deionized water.

[0025] Furthermore, graphene oxide is an oxide of graphene, the purity of glycidyl methacrylate is greater than 95%, the peroxide is a compound with a peroxy group -OO-, the molecular weight range of polyethylene glycol is 200-6000, and the conductivity of deionized water is less than 0.5 mS / cm.

[0026] A preparation process of a graphene-based water-resistant additive suitable for water-based coatings, comprising the following preparation steps:

[0027] Step 1, preparation of initial graphene-based water-resistant additive: add deionized water into a clean reactor with stirring and heating functions, start stirring and add graphene oxide, after the graphene oxide is evenly dispersed, treat with an ultrasonic vibration rod for 0.5-2 hours, then add peroxide and stir for 30 minutes, then add glycidyl methacrylate and polyethylene glycol and stir for 30 minutes, heat to 60-90° C. and stir for 3-6 hours, and cool to room temperature to obtain an initial graphene-based water-resistant additive;

[0028] Step 2, preparation of graphene-based water-resistant additive: the initial graphene-based water-resistant additive is filtered through a 100-300 mesh screen to remove substances that cannot be filtered, and the filtered additive is collected to obtain a graphene-based water-resistant additive;

[0029] Step 3: Canning the graphene-based water-resistant additive: inject the graphene-based water-resistant additive into a clean, water-free storage tank and seal it for storage. The storage tank can be made of stainless steel, fluoroplastics, glass, ceramics, etc.

[0030] Example 1

[0031] Step 1: Add 5000 grams of deionized water into a clean reactor with stirring and heating functions, start stirring and add 100 grams of graphene oxide. After the graphene oxide is evenly dispersed, add an ultrasonic vibrator for treatment for 2 hours, then add 20 grams of 30% hydrogen peroxide and stir for 30 minutes, then add 25 grams of 97% pure glycidyl methacrylate and 20 grams of polyethylene glycol with a molecular weight of 6000 and stir for 30 minutes, heat to 90°C and stir for 6 hours, and cool to room temperature to obtain the initial graphene-based water-resistant additive.

[0032] Step 2: The initial graphene-based water-resistant additive is filtered through a 300-mesh sieve to remove substances that cannot be filtered, and the filtered slurry is collected to obtain a graphene-based water-resistant additive.

[0033] Step 3: Inject the graphene-based water-resistant additive into a clean, water-free stainless steel storage tank and seal it for storage.

[0034] The additive obtained in Example 1 was added to the waterborne epoxy coating, and the waterborne epoxy coating without the additive of Example 1 was used as a blank sample. The water resistance of the waterborne epoxy coating sample was tested according to GB / T1733 "Determination of water resistance of paint film".

[0035] like Figure 1 As shown, the macroscopic morphology of the prepared graphene-based water-resistant additive suitable for water-based coatings is a black-gray dispersion.

[0036] like Figure 2 As shown, the microscopic morphology of the prepared graphene-based water-resistant additive suitable for water-based coatings, with auxiliary materials distributed on the main material graphene oxide.

[0037] like Figure 3 As shown, the water resistance time of water-based epoxy coatings is increased from 180 hours to 500 hours by adding a graphene-based water-resistant additive suitable for water-based coatings.

[0038] Example 2

[0039] Step 1: Add 1000 grams of deionized water into a clean reactor with stirring and heating functions, start stirring and add 100 grams of graphene oxide. After the graphene oxide is evenly dispersed, add an ultrasonic vibrator for treatment for 0.5 hours, then add 5 grams of chemically pure sodium persulfate and stir for 30 minutes, then add 10 grams of 95% pure glycidyl methacrylate and 50 grams of polyethylene glycol with a molecular weight of 200 and stir for 30 minutes, heat to 60°C and stir for 3 hours, and cool to room temperature to obtain the initial graphene-based water-resistant additive.

[0040] Step 2: The initial graphene-based water-resistant additive is filtered through a 100-mesh sieve to remove substances that cannot be filtered, and the filtered slurry is collected to obtain a graphene-based water-resistant additive.

[0041] Step 3: Inject the graphene-based water-resistant additive into a clean, water-free fluoroplastic storage tank and seal it for storage.

[0042] The additive obtained in Example 2 was added to the waterborne epoxy coating. The waterborne epoxy coating without the additive of Example 2 was used as a blank sample. The water resistance of the waterborne epoxy coating sample was tested according to GB / T1733 "Determination of water resistance of paint film".

[0043] The water-resistant time of water-based epoxy coatings added with graphene-based water-resistant additives suitable for water-based coatings is 500 hours.

[0044] Example 3

[0045] Step 1: Add 2000 grams of deionized water into a clean reactor with stirring and heating functions, start stirring and add 100 grams of graphene oxide. After the graphene oxide is evenly dispersed, add an ultrasonic vibrator for treatment for 1 hour, then add 7 grams of chemically pure potassium persulfate and stir for 30 minutes, then add 10 grams of 95% pure glycidyl methacrylate and 30 grams of polyethylene glycol with a molecular weight of 800 and stir for 30 minutes, heat to 60°C and stir for 3 hours, and cool to room temperature to obtain the initial graphene-based water-resistant additive.

[0046] Step 2: The initial graphene-based water-resistant additive is filtered through a 180-mesh sieve to remove substances that cannot be filtered, and the filtered slurry is collected to obtain a graphene-based water-resistant additive.

[0047] Step 3: Inject the graphene-based water-resistant additive into a clean, water-free fluoroplastic storage tank and seal it for storage.

[0048] The additive obtained in Example 3 was added to the waterborne epoxy coating. The waterborne epoxy coating without the additive of Example 3 was used as a blank sample. The water resistance of the waterborne epoxy coating sample was tested according to GB / T1733 "Determination of water resistance of paint film".

[0049] The water-resistant time of water-based epoxy coatings added with graphene-based water-resistant additives suitable for water-based coatings is 500 hours.

[0050] Example 4

[0051] Step 1: Add 3000 grams of deionized water into a clean reactor with stirring and heating functions, start stirring and add 100 grams of graphene oxide. After the graphene oxide is evenly dispersed, add an ultrasonic vibrator to treat for 1.5 hours, then add 20 grams of 20% peracetic acid and stir for 30 minutes, then add 15 grams of 95% pure glycidyl methacrylate and 38 grams of polyethylene glycol with a molecular weight of 2000 and stir for 30 minutes, heat to 70°C and stir for 2.5 hours, and cool to room temperature to obtain the initial graphene-based water-resistant additive.

[0052] Step 2: The initial graphene-based water-resistant additive is filtered through a 180-mesh sieve to remove substances that cannot be filtered, and the filtered slurry is collected to obtain a graphene-based water-resistant additive.

[0053] Step 3: Inject the graphene-based water-resistant additive into a clean, water-free glass storage jar and seal it for storage.

[0054] The additive obtained in Example 4 was added to the waterborne epoxy coating. The waterborne epoxy coating without the additive of Example 4 was used as a blank sample. The water resistance of the waterborne epoxy coating sample was tested according to GB / T1733 "Determination of water resistance of paint film".

[0055] The water-resistant time of water-based epoxy coatings added with graphene-based water-resistant additives suitable for water-based coatings is 500 hours.

[0056] Example 5

[0057] Step 1: Add 3000 grams of deionized water into a clean reactor with stirring and heating functions, start stirring and add 100 grams of graphene oxide. After the graphene oxide is evenly dispersed, add an ultrasonic vibrator to treat for 1.5 hours, then add 12 grams of chemically pure calcium peroxide and stir for 30 minutes, then add 12 grams of 97% pure glycidyl methacrylate and 25 grams of polyethylene glycol with a molecular weight of 4000 and stir for 30 minutes, heat to 80°C and stir for 1 hour, and cool to room temperature to obtain the initial graphene-based water-resistant additive.

[0058] Step 2: The initial graphene-based water-resistant additive is filtered through a 250-mesh sieve to remove substances that cannot be filtered, and the filtered slurry is collected to obtain a graphene-based water-resistant additive.

[0059] Step 3: Inject the graphene-based water-resistant additive into a clean, water-free ceramic storage tank and seal it for storage.

[0060] The additive obtained in Example 5 was added to the waterborne epoxy coating. The waterborne epoxy coating without the additive of Example 5 was used as a blank sample. The water resistance of the waterborne epoxy coating sample was tested according to GB / T1733 "Determination of water resistance of paint film".

[0061] The water-resistant time of water-based epoxy coatings added with graphene-based water-resistant additives suitable for water-based coatings is 500 hours.

[0062] Example 6

[0063] Step 1: Add 2500 grams of deionized water into a clean reactor with stirring and heating functions, start stirring and add 100 grams of graphene oxide. After the graphene oxide is evenly dispersed, add an ultrasonic vibrator for treatment for 1 hour, then add 18 grams of 30% hydrogen peroxide and stir for 30 minutes, then add 17 grams of 95% pure glycidyl methacrylate and 16 grams of polyethylene glycol with a molecular weight of 2000 and stir for 30 minutes, heat to 70°C and stir for 2 hours, and cool to room temperature to obtain the initial graphene-based water-resistant additive.

[0064] Step 2: The initial graphene-based water-resistant additive is filtered through a 200-mesh sieve to remove substances that cannot be filtered, and the filtered slurry is collected to obtain a graphene-based water-resistant additive.

[0065] Step 3: Inject the graphene-based water-resistant additive into a clean, water-free stainless steel storage tank and seal it for storage.

[0066] The additive obtained in Example 6 was added to the waterborne epoxy coating. The waterborne epoxy coating without the additive in Example 6 was used as a blank sample. The water resistance of the waterborne epoxy coating sample was tested according to GB / T1733 "Determination of water resistance of paint film".

[0067] The water-resistant time of water-based epoxy coatings added with graphene-based water-resistant additives suitable for water-based coatings is 500 hours.

Claims

1. A graphene-based water-resistant additive suitable for water-based coatings, characterized in that: The auxiliary agent comprises a main material of graphene oxide and auxiliary materials; by weight, the graphene oxide comprises 100 parts, glycidyl methacrylate comprises 10-25 parts, peroxide comprises 5-20 parts, polyethylene glycol comprises 20-50 parts, and deionized water comprises 1000-5000 parts; The preparation process of the graphene-based water-resistant additive suitable for water-based coatings comprises the following preparation steps: step 1, preparation of initial graphene-based water-resistant additive: adding deionized water into a clean reactor with stirring and heating functions, stirring and adding graphene oxide, performing ultrasonic treatment after the graphene oxide is evenly dispersed, then adding peroxide and stirring for 30 minutes, then adding glycidyl methacrylate and polyethylene glycol and stirring for 30 minutes, heating to a certain temperature and stirring, and cooling to room temperature to obtain the initial graphene-based water-resistant additive; step 2, preparation of graphene-based water-resistant additive; step 3, canning the graphene-based water-resistant additive.

2. A graphene-based water-resistant additive suitable for water-based coatings according to claim 1, characterized in that: Graphene oxide is an oxide of graphene, the purity of glycidyl methacrylate is greater than 95%, the peroxide is a compound with a peroxy group -OO-, the molecular weight range of polyethylene glycol is 200-6000, and the conductivity of deionized water is less than 0.5 mS / cm.

3. A graphene-based water-resistant additive suitable for water-based coatings according to claim 1, characterized in that: The ultrasonic treatment is carried out with an ultrasonic vibration rod for 0.5-2 hours.

4. A graphene-based water-resistant additive suitable for water-based coatings according to claim 1, characterized in that: The heating temperature is 60-90° C. and the stirring is performed for 3-6 hours.

5. A graphene-based water-resistant additive suitable for water-based coatings according to claim 1, characterized in that: Step 2 is specifically as follows: the initial graphene-based water-resistant additive is filtered through a 100-300 mesh screen to remove substances that cannot be filtered, and the filtered additive is collected to obtain a graphene-based water-resistant additive.

6. A graphene-based water-resistant additive suitable for water-based coatings according to claim 1, characterized in that: Step 3 is specifically as follows: injecting the graphene-based water-resistant additive into a clean, water-free storage tank and sealing it for storage.

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