CN113789122A - Polyvinyl alcohol resin organic silicon modified water-soluble equipment protective film solution and preparation method thereof - Google Patents
Polyvinyl alcohol resin organic silicon modified water-soluble equipment protective film solution and preparation method thereof Download PDFInfo
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- CN113789122A CN113789122A CN202111194777.2A CN202111194777A CN113789122A CN 113789122 A CN113789122 A CN 113789122A CN 202111194777 A CN202111194777 A CN 202111194777A CN 113789122 A CN113789122 A CN 113789122A
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- polyvinyl alcohol
- alcohol resin
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a protective film solution of a polyvinyl alcohol resin organic silicon modified water-soluble device, which comprises the following raw materials: phthalic acid mono-esterified polyvinyl alcohol resin, phthalic anhydride, p-toluenesulfonic acid, dimethylformamide, octamethylcyclotetrasiloxane, an alkali catalyst, dimethyldichlorosilane, an acid-binding agent and an acid neutralizing agent. The base catalyst can be potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide. In the scheme, dimethyl siloxane synthesized by taking octamethylcyclotetrasiloxane as a raw material is connected to a molecular chain of polyvinyl alcohol by taking dimethyl dichlorosilane as a bridging agent, so that the purposes of reducing surface tension, reducing adhesion of pollutants and improving water resistance are achieved.
Description
Technical Field
The invention relates to a novel technology for preventing pollutants from polluting equipment or accumulating and attaching to the surface of the equipment to cause the damage of the outer surface of the equipment during cleaning, which is used on easily-polluted equipment, 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 in order to achieve the purposes of attractiveness, warning, easiness in distinguishing and the like, however, in the using process of the equipment, the phenomenon that the surface of the equipment is attached and covered by pollutants due to the fact that the pollutants are easy to leak is avoided, part of the pollutants are difficult to clean in the cleaning process or difficult to clean quickly, even the paint on the surface 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 white pollution is generated in post treatment. 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 protective film solution of a polyvinyl alcohol resin organic silicon modified water-soluble device and a preparation method thereof, and aims to provide a protective film solution of a polyvinyl alcohol resin organic silicon modified water-soluble device and a preparation method thereof, wherein the protective film solution comprises the following components in parts by weight:
according to the invention, a layer of film with high strength and certain water solubility can be formed on the surface of a treated object by spraying, so that dirt is prevented from directly contacting the surface of the object, the pollutant can be easily removed by only washing the dissolved protective film with water in the later stage, the production efficiency is improved, and the biodegradable raw material has little pollution.
In order to achieve the above object, the present invention provides the following technical solutions.
A protection film solution of polyvinyl alcohol resin organic silicon modified water-soluble equipment comprises the following raw materials: phthalic acid mono-esterified polyvinyl alcohol resin, phthalic anhydride, p-toluenesulfonic acid, dimethylformamide, octamethylcyclotetrasiloxane, an alkali catalyst, dimethyldichlorosilane, an acid-binding agent and an acid neutralizing agent. The base catalyst can be potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide.
Optionally, the acid-binding agent is sodium carbonate, potassium carbonate, calcium carbonate, or triethylamine.
Optionally, the acid neutralizer is potassium hydroxide or sodium hydroxide.
According to the technical content, the preparation method of the polyvinyl alcohol resin organic silicon modified water-soluble equipment protective film solution comprises the following steps:
step 1: adding octamethylcyclotetrasiloxane into a reaction kettle, adding an alkali catalyst, reacting for 1-5h at 90-130 ℃, then cooling to 40-80 ℃, adding an acid-binding agent and dimethyldichlorosilane, and continuing to react for 2-5h to obtain a first-step product, namely, end-chloro-silicone oil;
step 2: under the condition of stirring, adding phthalic acid mono-esterified polyvinyl alcohol resin and dimethylformamide, raising the temperature of a reaction kettle to 70-100 ℃, adding the product obtained in the step (1) into the reaction kettle for reaction, starting nitrogen in the reaction process, keeping the reaction kettle at a weak negative pressure, keeping dry, absorbing tail gas alkali liquor for 1-5h, cooling to 40-60 ℃ after the reaction is finished, adding ethanol for crystallization, filtering, and washing with ethanol for 2 times to obtain a product, namely the organic silicon modified polyvinyl alcohol resin;
wherein the mass ratio of the product obtained in the step 1 to the phthalic acid mono-esterified polyvinyl alcohol resin is (3-10): 100, respectively; the mass ratio of the phthalic acid mono-esterified polyvinyl alcohol resin to the dimethylformamide is 1: (3-8).
And step 3: and (3) adding the product obtained in the step (3) into a reaction kettle for reaction, adding deionized water, dropwise adding an acid neutralizing agent until the resin is dissolved, and then adjusting the pH to be neutral to obtain a target product, namely a polyvinyl alcohol resin organic silicon modified water-soluble equipment protective film solution.
Further, the mass ratio of the octamethylcyclotetrasiloxane salt to the base catalyst is (100- & 1000): 1; the mass ratio of the octamethylcyclotetrasiloxane salt to the dimethyldichlorosilane is (100-2000): 1; the molar ratio of the dimethyldichlorosilane to the acid-binding agent is 1: (0.9-1).
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. In addition, the spraying treatment has high speed, does not need to invest special equipment, has low technical requirement, can be finished by ordinary people, reduces the cost, improves the production efficiency, is biodegradable and has little pollution.
(2) In the scheme, dimethyl siloxane synthesized by taking octamethylcyclotetrasiloxane as a raw material is connected to a molecular chain of polyvinyl alcohol by taking dimethyl dichlorosilane as a bridging agent, so that the purposes of reducing surface tension, reducing adhesion of pollutants and improving water resistance are achieved.
Detailed Description
In order to make the objects, technical solutions, advantages and significant progress of the embodiments of the present invention clearer and more obvious, the technical solutions in the embodiments of the present invention will be described below clearly and completely in conjunction with the embodiments of the present invention, and it is obvious that all the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
It should be noted that:
the terms "first," "second," and "third" (if present) and the like in the description and claims of the invention and in the embodiments of the invention, are used solely to distinguish one from another object and not necessarily to describe a particular sequence;
furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to the listed steps or elements, but may alternatively include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
It is to be understood that:
in the description of the embodiments of the present invention, the terms "upper", "lower", "top", "bottom", and other indicative orientations or positions are only used for describing the orientation or position relationship based on the embodiments of the present invention, and are used for facilitating the description of the embodiments of the present invention and simplifying the description, but do not indicate or imply that the device or the element must have a specific orientation, a specific orientation configuration and operation, and therefore, the present invention should not be construed as being limited thereto.
In the present invention, unless otherwise specifically stated or limited, the terms "mounted," "connected," "fixed," and the like are to be understood broadly, and for example, may be fixedly connected, detachably connected, movably connected, or integrated; the term "a" or "an" refers to a compound that can be directly connected or indirectly connected through an intermediate, and can be used in combination with or without other elements, unless otherwise specifically limited, and the specific meaning of the term in the present invention can be understood by those skilled in the art according to specific situations.
It should also be noted that:
the following embodiments may be combined with each other, and the same or similar concepts or processes may not be described in detail in some embodiments.
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.
A protection film solution of polyvinyl alcohol resin organic silicon modified water-soluble equipment comprises the following raw materials: phthalic acid mono-esterified polyvinyl alcohol resin, phthalic anhydride, p-toluenesulfonic acid, dimethylformamide, octamethylcyclotetrasiloxane, an alkali catalyst, dimethyldichlorosilane, an acid-binding agent and an acid neutralizing agent. The base catalyst can be potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide.
In a further improvement, the acid-binding agent is sodium carbonate, potassium carbonate, calcium carbonate and triethylamine; the acid neutralizer is potassium hydroxide or sodium hydroxide.
Example 1
Step 1: adding 1kg of octamethylcyclotetrasiloxane into a reaction kettle, adding 1g of tetramethylammonium hydroxide, reacting for 3 hours at 95 ℃, then cooling to 50 ℃, adding 7.8g of triethylamine and 10g of dimethyldichlorosilane, and continuing to react for 5 hours to obtain a first-step product, namely, the chlorine-terminated organic silicone oil;
step 2: under the condition of stirring, adding 20kg of phthalic acid mono-esterified polyvinyl alcohol resin and 80kg of dimethylformamide, heating the temperature of a reaction kettle to 85 ℃, adding the product obtained in the step 1 into the reaction kettle for reaction, starting nitrogen in the reaction process, keeping the reaction kettle at a weak negative pressure, keeping the reaction kettle dry, absorbing tail gas alkali liquor, and reacting for 3 hours; after the reaction is finished, cooling to 60 ℃, adding 120kg of ethanol for crystallization, filtering, and washing a filter cake for 2 times by 10kg of ethanol to obtain a product: organic silicon modified polyvinyl alcohol resin;
and step 3: adding the product obtained in the step 2 into a reaction kettle for reaction, adding 40kg of deionized water, slowly dropwise adding a strong sodium oxide aqueous solution with the mass fraction of 50% until the resin is dissolved, stirring for 1h, adjusting the pH to be neutral, and filtering to obtain the target product of the invention: a polyvinyl alcohol resin organic silicon modified water-soluble equipment protective film solution.
Example 2
Step 1: adding 1kg of octamethylcyclotetrasiloxane into a reaction kettle, adding 5g of potassium hydroxide, reacting for 3 hours at 130 ℃, then cooling to 50 ℃, adding 7.7g of calcium carbonate and 10g of dimethyldichlorosilane, and continuing to react for 5 hours to obtain the first-step product, namely, the chloro-terminated silicone oil;
step 2: under the condition of stirring, adding 20kg of phthalic acid mono-esterified polyvinyl alcohol resin and 60kg of dimethylformamide, heating the temperature of a reaction kettle to 95 ℃, adding the product obtained in the step 1 into the reaction kettle for reaction, starting nitrogen in the reaction process, keeping the reaction kettle at a weak negative pressure, keeping the reaction kettle dry, absorbing tail gas alkali liquor, and reacting for 4 hours; after the reaction is finished, cooling to 60 ℃, adding 100kg of ethanol for crystallization, filtering, and washing a filter cake for 2 times by 10kg of ethanol to obtain a product: organic silicon modified polyvinyl alcohol resin;
and step 3: and (3) adding the product obtained in the step (2) into a reaction kettle for reaction, adding 50kg of deionized water, slowly dropwise adding a strong sodium oxide aqueous solution with the mass fraction of 50% until the resin is dissolved, stirring for 1h, and then adjusting the pH to be neutral. The target product of the invention is obtained: a polyvinyl alcohol resin organic silicon modified water-soluble equipment protective film solution.
In both the above examples 1 and 2, dimethyl siloxane synthesized from octamethylcyclotetrasiloxane as a raw material is linked to the molecular chain of polyvinyl alcohol by using dimethyldichlorosilane as a bridging agent, so as to reduce surface tension, reduce adhesion of pollutants, and improve 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 (5)
1. A protection film solution of polyvinyl alcohol resin organic silicon modified water-soluble equipment is characterized in that: the raw materials comprise: phthalic acid mono-esterified polyvinyl alcohol resin, phthalic anhydride, p-toluenesulfonic acid, dimethylformamide, octamethylcyclotetrasiloxane, an alkali catalyst, dimethyldichlorosilane, an acid-binding agent and an acid neutralizing agent. The base catalyst can be potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide.
2. The protective film solution of polyvinyl alcohol resin organic silicon modified water-soluble equipment according to claim 1, characterized in that: the acid-binding agent is sodium carbonate, potassium carbonate, calcium carbonate and triethylamine.
3. The protective film solution of polyvinyl alcohol resin organic silicon modified water-soluble equipment according to claim 1, characterized in that: the acid neutralizer is potassium hydroxide or sodium hydroxide.
4. The method for preparing the protective film solution of the polyvinyl alcohol resin organic silicon modified water-soluble device according to claims 1 to 3, wherein the method comprises the following steps: the preparation method comprises the following steps:
step 1: adding octamethylcyclotetrasiloxane into a reaction kettle, adding an alkali catalyst, reacting for 1-5h at 90-130 ℃, then cooling to 40-80 ℃, adding an acid-binding agent and dimethyldichlorosilane, and continuing to react for 2-5h to obtain a first-step product, namely, end-chloro-silicone oil;
step 2: under the condition of stirring, adding phthalic acid mono-esterified polyvinyl alcohol resin and dimethylformamide, raising the temperature of a reaction kettle to 70-100 ℃, adding the product obtained in the step (1) into the reaction kettle for reaction, starting nitrogen in the reaction process, keeping the reaction kettle at a weak negative pressure, keeping dry, absorbing tail gas alkali liquor for 1-5h, cooling to 40-60 ℃ after the reaction is finished, adding ethanol for crystallization, filtering, and washing with ethanol for 2 times to obtain a product, namely the organic silicon modified polyvinyl alcohol resin;
wherein the mass ratio of the product obtained in the step 1 to the phthalic acid mono-esterified polyvinyl alcohol resin is (3-10): 100, respectively; the mass ratio of the phthalic acid mono-esterified polyvinyl alcohol resin to the dimethylformamide is 1: (3-8).
And step 3: and (3) adding the product obtained in the step (3) into a reaction kettle for reaction, adding deionized water, dropwise adding an acid neutralizing agent until the resin is dissolved, and then adjusting the pH to be neutral to obtain a target product, namely a polyvinyl alcohol resin organic silicon modified water-soluble equipment protective film solution.
5. The method for preparing the protective film solution of the polyvinyl alcohol resin organic silicon modified water-soluble device according to claim 4, wherein the method comprises the following steps: the mass ratio of the octamethylcyclotetrasiloxane salt to the base catalyst is (100-1000): 1; the mass ratio of the octamethylcyclotetrasiloxane salt to the dimethyldichlorosilane is (100-2000): 1; the molar ratio of the dimethyldichlorosilane to the acid-binding agent is 1: (0.9-1).
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Application publication date: 20211214 |