CN113881304A - Nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution and preparation method thereof - Google Patents
Nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution and preparation method thereof Download PDFInfo
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- CN113881304A CN113881304A CN202111194371.4A CN202111194371A CN113881304A CN 113881304 A CN113881304 A CN 113881304A CN 202111194371 A CN202111194371 A CN 202111194371A CN 113881304 A CN113881304 A CN 113881304A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution, which comprises raw materials of a free radical initiator, methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, isooctyl methacrylate, glycidyl methacrylate, styrene, nano silicon dioxide, hexamethyldisiloxane, an acid neutralizer and an organic solvent. According to the scheme, the water solubility of the polymer is adjusted by adjusting the content of acrylic acid and hydroxyethyl methacrylate through free radical polymerization, and the antifouling property of the polymer and the toughness of the film are adjusted by adjusting the content of vinyl silicone oil, so that the surface tension is reduced, the adhesion of pollutants is reduced, and the water resistance is improved.
Description
Technical Field
The invention relates to a novel technology which is used on easily-polluted equipment to prevent pollutants from polluting the equipment or accumulating and attaching to the surface of the equipment to cause the damage of the outer surface of the equipment during cleaning, and belongs to the technical field of polymer coatings and preparation methods.
Background
Mechanical equipment is widely applied in the current social production, particularly in capital construction. Paint with different colors is often coated on the surface of mechanical equipment for the purposes of beauty, warning, easy distinguishing and the like, but the surface of the equipment is inevitably covered by pollutants due to easy pollutant leakage in the use process of the equipment. And part of pollutants are difficult to clean or difficult to clean quickly when being cleaned, even surface paint is damaged, and the operation cost and the maintenance cost are increased. At present, a plastic film is adhered to the outer surface of equipment in the market to prevent pollution, but the time and labor required for film adhering are high, and the acrylate resin has no self-cleaning property. For this reason, corresponding technical solutions need to be researched and solved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution and a preparation method thereof, aiming at:
can form the one deck at the treatment object surface through the spraying and have high strength and have certain water-soluble membrane, block filth direct contact object surface, the later stage only need with the water washing dissolve the protection film can easily get rid of the pollutant, and the spraying treatment spraying is fast, does not need investment professional equipment, requires lowly, and ordinary people can accomplish, and reduce cost improves production efficiency.
In order to achieve the above object, the present invention provides the following technical solutions.
The raw materials of the nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution comprise a free radical initiator, methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, isooctyl methacrylate, glycidyl methacrylate, styrene, nano silicon dioxide, hexamethyldisiloxane, an acid neutralizer and an organic solvent.
Optionally, the free radical initiator is AIBN, alkyl peroxide, alkyl hydroperoxide.
Optionally, the acid neutralizer is sodium carbonate, potassium carbonate, calcium carbonate, triethylamine, potassium hydroxide, sodium hydroxide, or tetramethylammonium hydroxide.
Optionally, the organic solvent is dichloroethane, dioxane, tetrahydrofuran.
According to the technical content, the preparation method of the nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution comprises the following steps:
step 1: adding methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, isooctyl methacrylate, styrene and an organic solvent into a reaction kettle, stirring, refluxing and condensing, adding a free radical initiator, reacting for 1 to 5 hours at 50 to 100 ℃, and then cooling to 40 to 80 ℃, wherein the obtained product is: an acrylic resin intermediate;
step 2: adding hexamethyldisiloxane, isopropanol and deionized water into a reaction kettle, adjusting the pH value to 4-5 in a dilute hydrochloric acid solution, stirring at 30-60 ℃ for 30-120min, adding nano silicon dioxide, stirring at 60-80 ℃, reacting for 2-5 h, cooling, neutralizing and filtering to obtain the organosilicon surface modified nano silicon dioxide;
and step 3: adding the acrylic resin intermediate product obtained in the step 1, the organic silicon surface modified nano-silica obtained in the step 2 and cyclohexanone into a reaction kettle, heating to 110-130 ℃, reacting for 1-5h, recovering the solvent at low pressure, adding deionized water, and stirring until the solvent is completely dissolved, thereby obtaining the product nano-silica modified polyacrylate water-soluble equipment protective film solution.
Further, in the step 1, the mass ratio of the free radical initiator to the acrylic acid is (1-10):1000, and the mass ratio of the methacrylic acid, the methyl methacrylate, the hydroxyethyl methacrylate, the glycidyl methacrylate, the isooctyl methacrylate and the styrene is (5-100): (0-100): (10-95): (2-10): (0-100): (0-100), wherein the ratio of the total mass of the organic solvent and the acrylic ester is (5-20): 10.
further, in the step 2, the mass ratio of the isopropanol to the nano silicon dioxide is (1-5): 1; the mass ratio of hexamethyldisiloxane to nano silicon dioxide is (1-5): 10; the concentration of the dilute hydrochloric acid solution is 1 to 20 percent; the molar ratio of the deionized water to the hexamethyldisiloxane is 1: 1.
further, in step 3, the mass ratio of the acrylic resin intermediate to the organosilicon surface modified nano-silica is 100: (1-5); the mass ratio of the cyclohexanone to the acrylic resin intermediate is (1-5): 1.
compared with the prior art, the invention has the beneficial effects and the progress that:
(1) according to the invention, a layer of film with high strength and certain water solubility can be formed on the surface of the treated object by spraying, so that the dirt is prevented from directly contacting the surface of the object, and the pollutant can be easily removed only by washing the dissolved protective film with water in the later stage.
(2) The invention adjusts the water solubility of the polymer by adjusting the content of acrylic acid and hydroxyethyl methacrylate through free radical polymerization, adjusts the antifouling property of the polymer and the toughness of the film by adjusting the content of vinyl silicone oil, and achieves the purposes of reducing surface tension, reducing pollutant adhesion and improving water resistance.
(3) The invention has the advantages of high spraying treatment speed, no need of investment on special equipment, low technical requirement, capability of being finished by ordinary people, cost reduction and production efficiency improvement.
Detailed Description
The technical means of the present invention will be described in detail below with specific examples.
Examples
The embodiment provides and is used in easy dirty equipment to reach and prevent that the pollutant from polluting equipment or piling up and attach to the equipment surface, cause the novel technique of equipment surface damage when clean.
The raw materials of the nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution comprise a free radical initiator, methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, isooctyl methacrylate, glycidyl methacrylate, styrene, nano silicon dioxide, hexamethyldisiloxane, an acid neutralizer and an organic solvent.
Further, the free radical initiator is AIBN, alkyl peroxide and alkyl hydroperoxide; the acid neutralizer is sodium carbonate, potassium carbonate, calcium carbonate, triethylamine, potassium hydroxide, sodium hydroxide and tetramethyl ammonium hydroxide; the organic solvent is dichloroethane, dioxane and tetrahydrofuran.
Example 1
(1) Adding 1kg of methacrylic acid, 20kg of methyl methacrylate, 10kg of hydroxyethyl methacrylate, 10kg of isooctyl methacrylate, 2kg of styrene, 6kg of glycidyl methacrylate and 50kg of dichloroethane into a reaction kettle, stirring, refluxing and condensing, adding 45g of free radical initiator AIBN, reacting for 3 hours at 70 ℃, and then evaporating the solvent to obtain a product, namely an acrylic resin intermediate;
(2) adding 300g of hexamethyldisiloxane, 3kg of isopropanol and 33g of deionized water into a reaction kettle, adjusting the pH value to 4-5 in a 15% dilute hydrochloric acid solution, stirring at 50 ℃ for 60min, adding 1kg of nano-silica, stirring at 80 ℃, reacting for 4 hours, cooling, neutralizing and evaporating to obtain the organosilicon surface modified nano-silica;
(3) adding the acrylic resin intermediate product in the step (1), the organic silicon surface modified nano silicon dioxide product in the step (2) and 90kg of cyclohexanone into a reaction kettle, heating to 130 ℃ for reaction for 3 hours, recovering the solvent at low pressure, adding 100kg of deionized water, and stirring until the deionized water is completely dissolved, thereby obtaining: the product of the invention is a nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution.
Example 2
(1) Adding 20kg of methyl methacrylate, 16kg of hydroxyethyl methacrylate, 10kg of isooctyl methacrylate, 2kg of styrene, 7kg of glycidyl methacrylate and 80kg of dichloroethane into a reaction kettle, stirring, refluxing and condensing, adding 55g of free radical initiator AIBN, reacting for 4 hours at 75 ℃, and then evaporating the solvent to dryness to obtain a product, namely an acrylic resin intermediate;
(2) adding 450g of hexamethyldisiloxane, 5kg of isopropanol and 50g of deionized water into a reaction kettle, adjusting the pH value to 4-5 in a 15% dilute hydrochloric acid solution, stirring at 60 ℃ for 60min, adding 1.5kg of nano-silica, stirring at 75 ℃, reacting for 5 hours, cooling, neutralizing, and evaporating to dryness to obtain the organosilicon surface modified nano-silica;
(3) adding the acrylic resin intermediate product in the step (1), the organosilicon surface modified nano-silica product in the step (2) and 100kg of cyclohexanone into a reaction kettle, heating to 120 ℃ for reaction for 5 hours, recovering the solvent at low pressure, adding 133kg of deionized water, and stirring until the deionized water is completely dissolved, thereby obtaining: the product of the invention is a nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution.
In both the above examples 1 and 2, the water solubility of the polymer is adjusted by adjusting the content of hydroxyethyl acrylate and hydroxyethyl methacrylate through radical polymerization, and the antifouling property of the polymer and the toughness of the film are adjusted by adjusting the content of vinyl silicone oil, so as to reduce the surface tension, reduce the adhesion of pollutants, and improve the water resistance.
Experimental demonstration of the Properties of the prepared device protective film solutions by the two examples
The liquid protective solution is a macromolecule polymerization elastic surface inert protective material, and is characterized by environmental protection, strong adhesive force, easy tearing off of the whole sheet, no residue, high transparency, fast curing, strong weather resistance, capability of being sprayed (or rolled or brushed) at normal temperature, simple and convenient construction and wide application. The adhesive film can be well attached to the body after 2-3 hours of operation, so that the whole body can be perfectly coated, the adhesive film can be integrally formed in one step particularly in case of irregular structures and side seams thereof, no leftover materials exist in the whole body, and no waste pollution and no harmful gas emission exist. Meanwhile, as a liquid protective material, the liquid protective material has extremely outstanding applicability, and can thoroughly solve the practical problems of paint pollution and the like of the aerial work platform.
Parameters associated with the equipment protection solution
The coating mode is flexible and diverse: the liquid protective agent can adopt a spraying mode, a roller coating mode or a brush coating mode, and is flexible, simple and convenient. The liquid protective agent can be constructed on the surface of a dry substrate, and the surface requirement of the substrate is simpler than that of the traditional coil protective material. So that the product can be used in any product processing.
The function is various: the liquid protective agent forms perfect coverage on the substrate, and can realize various effects of rust prevention, dust prevention, moisture prevention, scratch prevention, fingerprint removal and the like besides excellent protection.
Energy conservation and environmental protection: the consumption of traditional materials is reduced, resources are saved, and the generation of garbage during the later dismantling is reduced, so that the material saving is an important component for energy saving and environmental protection.
The water-based protective agent is coated on the surface of a product in a spraying mode and the like, a protective film is automatically generated, and the water-based protective agent has a good complementary effect on places which are difficult to protect conventionally.
The construction process flow of the equipment protective film solution comprises the following steps:
1. base surface treatment:
the base course should be cleaned thoroughly to loose, skinned, hollowly, powdered base course, then, remove pollutants such as dust, greasy dirt, etc.
2. Roller construction on the metal surface:
(1) tools and materials
Wool roller (roller)
(2) Before brushing, the base layer should be cleaned, floating dust should be cleaned, the brush should be kept clean, brushing is carried out for 1-2 times, brushing is even, and no brush leakage phenomenon exists. Water is forbidden during the construction of the water-based protective film.
3. Spraying a film on the metal surface of the spray gun:
(1) tools and materials
Spray gun and air compressor
(2) As with the base layer treatment of roller construction, the base layer needs to be clean and free of floating dust, and before spraying, the base layer needs to be fully dried and applied
The working temperature must be above-10 ℃, and the coating amount varies according to the coating effect, climate, base surface condition and construction method. The first construction needs to be guided by construction of professional personnel, and the product stored in a standing mode for a long time can be slightly stirred before being used after being uncovered, mechanical stirring is not needed, and water is not needed to be added for dilution.
During the description of the above description:
the description of the terms "present embodiment," "as shown at … …," "further improved technical solution," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention, and the schematic representation of the terms in this specification is not necessarily intended to refer to the same embodiment or example, and the particular feature, structure, material, or characteristic described, etc., may be combined or coupled in any suitable manner in any one or more embodiments or examples;
furthermore, those of ordinary skill in the art may combine or combine features of different embodiments or examples and features of different embodiments or examples described in this specification without undue conflict.
Finally, it should be noted that:
although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made on the technical solutions described in the foregoing embodiments, or some or all of the technical features of the embodiments can be equivalently replaced, and the corresponding technical solutions do not depart from the technical solutions of the embodiments of the present invention.
Claims (8)
1. A nanometer silicon dioxide modified polyacrylate water-soluble equipment protective film solution is characterized in that: the raw materials comprise a free radical initiator, methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, isooctyl methacrylate, glycidyl methacrylate, styrene, nano silicon dioxide, hexamethyldisiloxane, an acid neutralizer and an organic solvent.
2. The protective film solution for water-soluble equipment of nano-silica modified polyacrylate according to claim 1, wherein: the free radical initiator is AIBN, alkyl peroxide and alkyl hydroperoxide.
3. The protective film solution for water-soluble equipment of nano-silica modified polyacrylate according to claim 1, wherein: the acid neutralizer is sodium carbonate, potassium carbonate, calcium carbonate, triethylamine, potassium hydroxide, sodium hydroxide and tetramethyl ammonium hydroxide.
4. The protective film solution for water-soluble equipment of nano-silica modified polyacrylate according to claim 1, wherein: the organic solvent is dichloroethane, dioxane and tetrahydrofuran.
5. The method for preparing the protective film solution of the nano-silica modified polyacrylate water-soluble device according to claims 1 to 4, wherein the method comprises the following steps: the preparation method comprises the following steps:
step 1: adding methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, isooctyl methacrylate, styrene and an organic solvent into a reaction kettle, stirring, refluxing and condensing, adding a free radical initiator, reacting for 1 to 5 hours at 50 to 100 ℃, and then cooling to 40 to 80 ℃, wherein the obtained product is: an acrylic resin intermediate;
step 2: adding hexamethyldisiloxane, isopropanol and deionized water into a reaction kettle, adjusting the pH value to 4-5 in a dilute hydrochloric acid solution, stirring at 30-60 ℃ for 30-120min, adding nano silicon dioxide, stirring at 60-80 ℃, reacting for 2-5 h, cooling, neutralizing and filtering to obtain the organosilicon surface modified nano silicon dioxide;
and step 3: adding the acrylic resin intermediate product obtained in the step 1, the organic silicon surface modified nano-silica obtained in the step 2 and cyclohexanone into a reaction kettle, heating to 110-130 ℃, reacting for 1-5h, recovering the solvent at low pressure, adding deionized water, and stirring until the solvent is completely dissolved, thereby obtaining the product nano-silica modified polyacrylate water-soluble equipment protective film solution.
6. The method for preparing the protective film solution of the nano-silica modified polyacrylate water-soluble device according to claim 5, wherein the method comprises the following steps: in the step 1, the mass ratio of the free radical initiator to the acrylic acid is (1-10) to 1000, and the mass ratio of the methacrylic acid, the methyl methacrylate, the hydroxyethyl methacrylate, the glycidyl methacrylate, the isooctyl methacrylate and the styrene is (5-100): (0-100): (10-95): (2-10): (0-100): (0-100), wherein the ratio of the total mass of the organic solvent and the acrylic ester is (5-20): 10.
7. the method for preparing the protective film solution of the nano-silica modified polyacrylate water-soluble device according to claim 5, wherein the method comprises the following steps: in the step 2, the mass ratio of the isopropanol to the nano silicon dioxide is (1-5): 1; the mass ratio of hexamethyldisiloxane to nano silicon dioxide is (1-5): 10; the concentration of the dilute hydrochloric acid solution is 1 to 20 percent; the molar ratio of the deionized water to the hexamethyldisiloxane is 1: 1.
8. the method for preparing the protective film solution of the nano-silica modified polyacrylate water-soluble device according to claim 5, wherein the method comprises the following steps: in the step 3, the mass ratio of the acrylic resin intermediate to the organic silicon surface modified nano silicon dioxide is 100: (1-5); the mass ratio of the cyclohexanone to the acrylic resin intermediate is (1-5): 1.
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| CN116217834A (en) * | 2023-02-11 | 2023-06-06 | 江苏乐离新材料科技有限公司 | Preparation method of polyacrylate organosilicon modified water-soluble equipment protective film solution |
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Application publication date: 20220104 |