CN113956792B - Preparation method of water-based paint of organic siloxane composite hectorite - Google Patents

Preparation method of water-based paint of organic siloxane composite hectorite Download PDF

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CN113956792B
CN113956792B CN202110542816.7A CN202110542816A CN113956792B CN 113956792 B CN113956792 B CN 113956792B CN 202110542816 A CN202110542816 A CN 202110542816A CN 113956792 B CN113956792 B CN 113956792B
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hectorite
water
siloxane
coupling agent
stirring
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CN113956792A (en
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陈晋阳
洪梦寒
杨云凡
马国丽
洪晓敏
杨丁卿
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University of Shanghai for Science and Technology
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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
    • C09D183/04—Polysiloxanes
    • 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
    • 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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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a preparation method of water paint of organic siloxane complex hectorite, belonging to the preparation field of organic siloxane paint, under the temperature range of 30-60 ℃, siloxane coupling agent containing vinyl and hectorite powder are selected to be added into stirred water, AMP-95 is used for adjusting the pH value to 7.5-9.5, the mixed system is stirred uniformly for a period of time, in the process, the siloxane coupling agent can be hydrolyzed to generate silanol, the silanol can be compounded with the edge hydroxyl of dispersed flaky hectorite, then redox free radical initiator for initiating free radical reaction is slowly dropped into the system, the initiator can generate free radical at low temperature to initiate siloxane vinyl polymerization, thereby obtaining siloxane polymer of complex hectorite, as the flaky hectorite surface has negative electricity, the edge has positive electricity, organic siloxane is combined at the edge of hectorite, the hydrophilic surface of the hectorite is stably dispersible in solution due to its negative electrical repulsion, thereby forming a coating of organosiloxane that is stably dispersible in water.

Description

Preparation method of water-based paint of organic siloxane composite hectorite
Technical Field
The invention relates to the field of preparation of organic siloxane coatings, in particular to a preparation method of an organic siloxane hectorite composite water-based coating.
Background
The organic silicon resin is a high molecular weight, three-dimensionally crosslinked polymer compound whose basic structure is a main chain composed of silicon atoms and oxygen atoms. The paint prepared by the organic silicon resin has excellent weather resistance, heat resistance, water resistance, stable chemical property, electric insulation property and the like.
The water-based organic silicon coating is prepared by adopting organic siloxane monomer to carry out hydrolytic polymerization in a surfactant system, and the obtained organic silicon coating contains the surfactant system, so that the water resistance of the obtained coating is influenced.
Disclosure of Invention
The invention provides a method for preparing water-based paint of organic siloxane composite hectorite, which is characterized in that a surfactant is not needed, the positively charged edge of the hectorite is combined with organic silicon, and the surface of the hectorite is still negatively charged, so that the formed organic silicon can be stably dispersed in water, and the water-based paint is green and environment-friendly and has a long shelf life.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an organic siloxane laponite composite water-based paint comprises the following steps:
s1, weighing a certain proportion of double bond-containing organosilane coupling agent and hectorite;
s2, adding an organosilane coupling agent and hectorite into water under stirring at the temperature of 30-60 ℃, and adjusting the pH of the mixed system to 7.5-9.5 by AMP-95;
s3, continuously stirring the mixed system in the S2 to uniformly mix the mixed system, and continuously stirring for a certain time after the mixed system is uniformly mixed;
s4, after stirring for a certain time in S3, slowly dripping a redox free radical initiator into the system to initiate the double bond polymerization of the silane coupling agent in the system;
and S5, after the initiator is added dropwise, continuously stirring and reacting for a certain time, and stopping the reaction to obtain the water-based organic silicon resin coating.
Preferably, the organosilicon coupling agent in S1 can be selected from vinyltrimethoxysilane, vinylmethyldimethoxysiloxane, vinyltriethoxysilane, vinylmethyldiethoxysiloxane, and other silane coupling agents containing vinyl group.
Preferably, the redox radical initiator in S4 can be selected from hydrogen peroxide/tartaric acid, tert-butyl hydroperoxide/sodium metabisulfite, hydrogen peroxide// rongalite, tert-butyl hydroperoxide/rongalite or potassium persulfate/sodium bisulfite.
Preferably, the weight ratio of the silane coupling agent to the hectorite in S1 is 10: (1-3).
Preferably, the ratio of the total weight of the silane coupling agent and the hectorite in S2 to water is (1-3): 10.
preferably, the weight ratio of the redox radical initiator to the silane coupling agent in S4 is (0.1-0.8): 100.
compared with the prior art, the invention provides a preparation method of the water-based paint of organic siloxane composite hectorite, which has the following beneficial effects:
1. the invention has the beneficial effects that:
the object of the present invention is to solve the above-mentioned problems by proposing the use of a water-dispersible hectorite as a dispersion medium without using a surfactant. The general chemical structure formula of the hectorite is Mx[LixMg6-xSi8O20(OH)yF4-y](M ═ Na, Li, etc.), which is an inorganic silicate layered nano mineral material. It consists of silicon-oxygen tetrahedra and magnesium-oxygen octahedra in a vertical direction in a ratio of 2: 1, and the molecular structure thereof is shown in figure 1. The silicon-oxygen tetrahedron is formed by connecting a Si atom and four O atoms, wherein the Si atom is at the center of the tetrahedron, and the four O atoms are at four top corners of the tetrahedron; in magnesium-oxygen octahedrons, the magnesium atom is located in the center of the octahedron, and the oxygen atoms at the vertices of the octahedron also form additional octahedrons with adjacent magnesium atoms. Wherein the magnesium ions in the positive two valences in the magnesium-oxygen octahedron sheet are replaced by the lithium ions in the positive one valences, resulting in the layer surface being negatively charged, and the corresponding number of cations such as sodium ions are adsorbed between the layers to maintain the electrical neutrality.
And (3) under the stirring action in the aqueous solution, cations are adsorbed among layers of the hectorite lamellar structure to generate hydration, the volume is increased, and the exfoliation dissolution is generated. The edges of the lamellae carry a small positive charge due to protonation of the Mg-OH groups. In water, when the laponite reaches a certain concentration, the positive electricity edge and the negative electricity surface of the nanosheet layer attract each other to form a structure of 'card house', so that thixotropic gel containing a large amount of water network structures is formed, and the whole process is shown in fig. 2.
By utilizing a lamellar structure formed by dispersing hectorite in water and having negative electricity on the surface and positive electricity on the edge, and adding an organosilane coupling agent containing vinyl, silanol is formed by hydrolyzing siloxane of the organosilane coupling agent, and can be combined with the positive electricity edge of the flaky hectorite, as shown in figure 3. The surface of the flaky hectorite still has negative charges, so that a condensation structure of 'clamping houses' formed by the flaky pure hectorite is avoided, and the surface still has the negative charges, so that the precipitation is avoided. Vinyl polymerization is then initiated to give a high molecular silicone resin coating. In the polymer, as the flaky hectorite surface still has negative electricity, the formed polymerized organosilicon can be stably dispersed in water, and the polymer is green and environment-friendly and has a longer quality guarantee period.
Drawings
FIG. 1 is a schematic view showing a layered structure of hectorite in a method for preparing an aqueous coating material of organic siloxane complex hectorite according to the present invention;
FIG. 2 is a diagram showing a process of dispersing hectorite in water according to a method for preparing an aqueous coating of an organosiloxane complex hectorite according to the present invention;
FIG. 3 is a schematic representation of the combination of silicone and hectorite for a method of preparing an aqueous coating of organosiloxane laponite in accordance with the present invention;
FIG. 4 is a water drop diagram of a cured coating according to an embodiment of the present invention;
FIG. 5 is a water drop diagram of a cured coating of a conventional silicone-acrylic emulsion for a method of preparing an aqueous coating of an organosiloxane laponite in accordance with the present invention;
FIG. 6 is a water drop diagram of a second cured coating according to an example of a method of preparing an aqueous coating of an organosiloxane laponite in accordance with the present invention;
FIG. 7 is a water drop pattern of a three-cure coating according to an example of a method of preparing an aqueous coating of an organosiloxane laponite in accordance with the present invention;
FIG. 8 is a water drop pattern of a four-cure coating according to an example of a method of preparing an aqueous coating of an organosiloxane laponite in accordance with the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
The first embodiment is as follows:
the invention provides a preparation method of an organic siloxane hectorite composite water-based paint, which comprises the following steps:
10g of vinyltrimethoxysilane and 1.5g of hectorite were weighed.
② under the condition of 50 ℃, adding the two into 100g of water while stirring, setting the stirring speed at 300r/min, stirring evenly, dripping AMP-95 to adjust the pH value to about 9, and continuing stirring for 5 hours.
③ 0.009g of tert-butyl hydroperoxide and 0.006g of rongalite are weighed, dissolved by a small amount of water respectively, and are slowly dripped into the mixed system respectively, and the stirring reaction is continued for 3 hours after the dripping is finished.
And fourthly, after the reaction is finished, pouring out the product to obtain a homogeneous mixture, namely the water-based organic silicon resin coating.
The organic silicon resin coating is directly smeared on a clean stainless steel sheet and cured for 12 hours at room temperature, the obtained coating has good transparency, the hardness is about 3H, the adhesive force is about 2 grades, and no appearance appears after being soaked in water for 18 hours.
Compared with the common silicone-acrylate emulsion, the hydrophobicity of the silicone-acrylate emulsion is obviously enhanced, the dropping photo of the cured coating is shown in fig. 4, and the dropping photo of the cured layer of the common silicone-acrylate emulsion is shown in fig. 5. The water drop on the coating is difficult to spread, the contact angle is about 126 degrees, and the coating belongs to a non-wetting state, while the contact angle of the water drop on the solidified layer of the common silicone acrylic emulsion is about 69 degrees, and the coating belongs to a wetting state.
Example two:
the invention provides a preparation method of an organic siloxane hectorite composite water-based paint, which comprises the following steps:
15g of vinylmethyldimethoxysilane and 1.5g of hectorite were weighed out.
② at the temperature of 60 ℃, adding the two into 100g of water while stirring, setting the stirring speed at 300r/min, stirring evenly, dripping AMP-95 to adjust the pH value to about 8.5, and continuing stirring for 5 hours.
③ 0.009g of tert-butyl hydroperoxide and 0.006g of rongalite are weighed, dissolved by a small amount of water respectively, and are slowly dripped into the mixed system respectively, and the stirring reaction is continued for 3 hours after the dripping is finished.
And fourthly, after the reaction is finished, pouring out the product to obtain a homogeneous mixture, namely the water-based organic silicon resin coating.
The organic silicon resin coating is directly smeared on a clean stainless steel sheet and cured for 12 hours at room temperature, the obtained coating has good transparency, the hardness is about 3H, the adhesive force is about 3 grades, and no appearance appears after being soaked in water for 24 hours. Fig. 6 is a photograph of a drop of water from the cured coating, where the drop of water is difficult to spread and the contact angle is about 136 deg., which is in a non-wetting state.
Example three:
the invention provides a preparation method of an organic siloxane hectorite composite water-based paint, which comprises the following steps:
10g of vinyltrimethoxysilane and 2g of hectorite were weighed.
② at the temperature of 45 ℃, adding the two into 100g of water while stirring, setting the stirring speed at 300r/min, stirring evenly, dripping AMP-95 to adjust the pH value to about 9, and continuing stirring for 5 hours.
③ 0.009g of tert-butyl hydroperoxide and 0.006g of rongalite are weighed, dissolved by a small amount of water respectively, and are slowly dripped into the mixed system respectively, and the stirring reaction is continued for 3 hours after the dripping is finished.
And fourthly, after the reaction is finished, pouring out the product to obtain a homogeneous mixture, namely the water-based organic silicon resin coating.
The organic silicon resin coating is directly smeared on a clean stainless steel sheet and cured for 12 hours at room temperature, the obtained coating has good transparency, the hardness is about 4H, the adhesive force is about 2 grades, and no appearance appears after being soaked in water for 18 hours. FIG. 7 is a photograph of a drop of the cured coating, on which the drop of water is difficult to spread and has a contact angle of about 118 degrees, which is in a non-wetting state.
Example four:
the invention provides a preparation method of an organic siloxane hectorite composite water-based paint, which comprises the following steps:
10g of vinylmethyldimethoxysilane and 2.5g of hectorite were weighed out.
② at the temperature of 50 ℃, adding the two into 100g of water while stirring, setting the stirring speed at 300r/min, stirring evenly, dripping AMP-95 to adjust the pH value to about 8.5, and continuing stirring for 5 hours.
③ 0.009g of tert-butyl hydroperoxide and 0.006g of rongalite are weighed, dissolved by a small amount of water respectively, and are slowly dripped into the mixed system respectively, and the stirring reaction is continued for 3 hours after the dripping is finished.
And fourthly, after the reaction is finished, pouring out the product to obtain a homogeneous mixture, namely the water-based organic silicon resin coating.
The organic silicon resin coating is directly smeared on a clean stainless steel sheet and cured for 12 hours at room temperature, the obtained coating has good transparency, the hardness is about 4H, the adhesive force is about 2 grades, and no appearance appears after being soaked in water for 18 hours. Fig. 8 is a photograph of a drop of water from the cured coating, where the drop of water is difficult to spread and the contact angle is around 115 deg., which is in a non-wetting state.
Example 5:
a preparation method of an organic siloxane laponite composite water-based paint comprises the following steps:
s1, weighing a certain proportion of double bond-containing organosilane coupling agent and hectorite;
s2, adding an organosilane coupling agent and hectorite into water under stirring at the temperature of 30-60 ℃, and adjusting the pH of the mixed system to 7.5-9.5 by AMP-95;
s3, continuously stirring the mixed system in the S2 to uniformly mix the mixed system, and continuously stirring for a certain time after the mixed system is uniformly mixed;
s4, after stirring for a certain time in S3, slowly dripping a redox free radical initiator into the system to initiate the double bond polymerization of the silane coupling agent in the system;
and S5, after the initiator is added dropwise, continuously stirring and reacting for a certain time, and stopping the reaction to obtain the water-based organic silicon resin coating.
Further, preferably, the organosilicon coupling agent in S1 can be selected from vinyltrimethoxysilane, vinylmethyldimethoxysiloxane, vinyltriethoxysilane, vinylmethyldiethoxysiloxane, and other silane coupling agents containing vinyl.
Further, preferably, the redox radical initiator in S4 may be selected from hydrogen peroxide/tartaric acid, tert-butyl hydroperoxide/sodium metabisulfite, hydrogen peroxide// rongalite, tert-butyl hydroperoxide/rongalite or potassium persulfate/sodium bisulfite.
Further, preferably, the weight ratio of the silane coupling agent to the hectorite in S1 is 10: (1-3).
Further, it is preferable that the ratio of the total weight of the silane coupling agent and the hectorite to water in S2 is (1-3): 10.
further, preferably, the weight ratio of the redox radical initiator to the silane coupling agent in S4 is (0.1-0.8): 100.
the invention discloses a preparation method of a water-based organic silicon resin coating for compounding hectorite by a double-bond-containing silane coupling agent. Firstly, the siloxane coupling agent is hydrolyzed to generate silanol which is compounded with the dispersed hydroxyl at the edge of the flaky hectorite. And then slowly dropping a redox initiator for initiating a free radical reaction into the system to initiate siloxane vinyl polymerization, thereby obtaining the hectorite-compounded siloxane polymer resin coating.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (4)

1. A preparation method of an organic siloxane laponite composite water-based paint is characterized by comprising the following steps:
s1, weighing a certain proportion of double bond-containing organosilane coupling agent and hectorite;
s2, adding an organosilane coupling agent and hectorite into water under stirring at the temperature of 30-60 ℃, and adjusting the pH of the mixed system to 7.5-9.5 by AMP-95;
s3, continuously stirring the mixed system in the S2 to uniformly mix the mixed system, and continuously stirring for a certain time after the mixed system is uniformly mixed;
s4, after stirring for a certain time in S3, slowly dripping a redox free radical initiator into the system to initiate the double bond polymerization of the organosilane coupling agent in the system;
s5, after the initiator is added dropwise, continuing stirring to react for a certain time, and stopping the reaction, wherein the mixed system is the water-based organic silicon resin coating;
the organosilane coupling agent in the S1 is one of vinyl trimethoxy siloxane, vinyl methyl dimethoxy siloxane, vinyl triethoxy siloxane and vinyl methyl diethoxy siloxane;
the weight ratio of the organosilane coupling agent to the hectorite in the S1 is 10: (1-3).
2. The method of claim 1, wherein the redox radical initiator of S4 is selected from hydrogen peroxide/tartaric acid, tert-butyl hydroperoxide/sodium metabisulfite, hydrogen peroxide// rongalite, tert-butyl hydroperoxide/rongalite or potassium persulfate/sodium bisulfite.
3. The method for preparing an aqueous coating of organosilicone laponite according to claim 1 or 2, wherein the weight ratio of the total weight of the organosilane coupling agent and the laponite to the water in S2 is (1-3): 10.
4. the method for preparing an aqueous coating of organosilicone laponite according to claim 1 or 2, wherein the weight ratio of the redox radical initiator to the organosilane coupling agent in S4 is (0.1-0.8): 100.
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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN111333792A (en) * 2020-04-07 2020-06-26 中国石油大学(华东) Modified nano hectorite and preparation method and application thereof

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JPWO2008156032A1 (en) * 2007-06-20 2010-08-26 昭和電工株式会社 Organized clay, method for producing the same, and resin composite containing organized clay
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CN111333792A (en) * 2020-04-07 2020-06-26 中国石油大学(华东) Modified nano hectorite and preparation method and application thereof

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