CN108314934B - Preparation method of rainbow effect water-soluble polyacrylic acid coating - Google Patents
Preparation method of rainbow effect water-soluble polyacrylic acid coating Download PDFInfo
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- CN108314934B CN108314934B CN201810131351.4A CN201810131351A CN108314934B CN 108314934 B CN108314934 B CN 108314934B CN 201810131351 A CN201810131351 A CN 201810131351A CN 108314934 B CN108314934 B CN 108314934B
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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
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/02—Cellulose; Modified cellulose
- C09D101/04—Oxycellulose; Hydrocellulose
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
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Abstract
The invention discloses a preparation method of a rainbow effect water-soluble polyacrylic acid coating, belonging to the field of polyacrylic acid coatings. The preparation method of the rainbow effect water-soluble polyacrylic acid coating comprises the steps of carrying out sulfuric acid hydrolysis and ultrasonic crushing on microcrystalline cellulose to prepare a nano crystalline cellulose colloid, and then adding the water-soluble polyacrylic acid coating into the nano crystalline cellulose colloid for reaction to prepare the rainbow effect water-soluble polyacrylic acid coating. Compared with the common water-soluble polyacrylic acid coating, the rainbow effect water-soluble polyacrylic acid coating copies the chiral nematic liquid crystal structure of the nanocrystalline cellulose colloid in the coating, so that the prepared coating has rich colors and spans the whole visible region.
Description
Technical Field
The invention relates to the application field of polyacrylic acid coating, in particular to a preparation method of rainbow effect water-soluble polyacrylic acid coating.
Background
The water-soluble polyacrylic acid coating has the characteristics of low price, safety, environmental protection, excellent weather resistance, good film forming property, good color retention, simple synthesis and processing and the like. In addition, the formula of the water-soluble polyacrylic acid coating is flexible, and the water-soluble polyacrylic acid coating product meeting different functionalization requirements can be prepared by adding fillers with different performances or copolymerizing with functional monomers and the like. At present, water-soluble polyacrylic acid coatings are widely applied in the functional directions of water resistance, fire resistance, corrosion resistance, marine antifouling, heat insulation and preservation coatings and the like, but the functional modification of the color of the water-soluble polyacrylic acid coatings is only reported.
Nanocrystalline cellulose (NCC) is a rigid rod-shaped body with the size of tens to hundreds of nanometers, has excellent characteristics of high crystallinity, high young modulus, high strength, high specific surface area and the like, and also has a hierarchical pore channel structure, and the surface of the nanometer crystalline cellulose has a template structure containing a plurality of reactive hydroxyl groups. Due to the presence of sulfonic acid groups in the NCC colloid, at a certain concentration, NCC can form an ordered liquid crystal phase structure, called chiral nematic liquid crystal phase. In the drying process of the NCC colloid, the ordered liquid crystal phase structure is remained in the NCC film, so that the NCC film realizes selective reflection on different wavelengths in a visible light region, and the color of the NCC film is changed from red orange to blue purple, namely, the NCC film shows a rainbow effect. At present, the NCC/polyethylene glycol rainbow film is prepared by copying the ordered liquid crystal phase structure of NCC into polyethylene glycol by using an NCC template. The ordered liquid crystal phase structure of the NCC is copied into the water-soluble polyacrylic acid coating to prepare the water-soluble polyacrylic acid coating with the rainbow effect, so that the water-soluble polyacrylic acid coating is endowed with color functionality, the application field of the water-soluble polyacrylic acid coating is expanded, and the application of the NCC is expanded.
Disclosure of Invention
The purpose of the invention is as follows: provides a preparation method of a rainbow effect water-soluble polyacrylic acid coating.
The technical solution of the invention is as follows: a rainbow effect water-soluble polyacrylic acid paint is prepared through acidolysis of microcrystalline cellulose with sulfuric acid, ultrasonic breaking to obtain crystalline cellulose colloid, and adding it to said crystalline cellulose colloid for reaction. The preparation method comprises the following steps:
(1) dispersing microcrystalline cellulose in 58-64% sulfuric acid aqueous solution by mass, fully mixing the microcrystalline cellulose and the sulfuric acid aqueous solution at a mass ratio of 1: 8-12, stirring at 45-60 ℃ for 1-2 h to obtain a blend of the microcrystalline cellulose and the sulfuric acid aqueous solution, diluting, centrifuging and dialyzing the blend until the pH value is neutral, and then carrying out ultrasonic treatment for 25-50 min at an ultrasonic power of 600-900W to obtain a nano crystalline cellulose colloid with a mass fraction of 0.8-2.3%;
(2) and (2) weighing the water-soluble polyacrylic acid coating in the nano crystalline cellulose colloid in the step (1) according to the mass ratio of the nano crystalline cellulose colloid to the water-soluble polyacrylic acid coating of 100: 6-30, adding the water-soluble polyacrylic acid coating into the nano crystalline cellulose colloid, fully mixing, carrying out ultrasonic treatment for 20-40 min, carrying out ultrasonic treatment at the power of 120-150W, and stirring for 2-4 h at the temperature of 20-25 ℃ to form the rainbow effect water-soluble polyacrylic acid coating.
The invention has the advantages that:
(1) the method utilizes the chiral nematic liquid crystal structure of the nano crystalline cellulose colloid and good template effect to copy the chiral nematic liquid crystal structure of the nano crystalline cellulose colloid into the water-soluble polyacrylic acid coating, and the stability is good.
(2) Compared with the common water-soluble polyacrylic acid coating, the rainbow effect water-soluble polyacrylic acid coating has the advantages that the color of a coating film of the water-soluble polyacrylic acid coating changes from initial white semi-transparency to red orange in the drying process, and the coating film presents different colors after the drying is finished.
(3) In the coating film after the drying is finished, the color of the coating film is changed from red orange to blue under natural light along with the gradual increase of the content of the nano crystalline cellulose colloid.
Drawings
FIG. 1 shows a bluish water-soluble polyacrylic acid coating film obtained in example 1.
FIG. 2 is a coating film of a water-soluble polyacrylic acid having a yellowish green color obtained in example 2.
FIG. 3 is a red-orange water-soluble polyacrylic acid coating film obtained in example 3.
Detailed Description
In the case of the example 1, the following examples are given,
(1) dispersing microcrystalline cellulose in 58-64% sulfuric acid aqueous solution by mass, fully mixing the microcrystalline cellulose and the sulfuric acid aqueous solution at a mass ratio of 1: 8, stirring at 45 ℃ for 1-2 h to obtain a blend of the microcrystalline cellulose and the sulfuric acid aqueous solution, diluting, centrifuging and dialyzing the blend until the pH value is neutral, and then carrying out ultrasonic treatment for 25-50 min at an ultrasonic power of 600-900W to obtain a nano crystalline cellulose colloid with a mass fraction of 0.8%;
(2) and (2) weighing the water-soluble polyacrylic acid coating in the nano crystalline cellulose colloid in the step (1) according to the mass ratio of the nano crystalline cellulose colloid to the water-soluble polyacrylic acid coating of 100: 6, adding the water-soluble polyacrylic acid coating into the nano crystalline cellulose colloid, fully mixing, carrying out ultrasonic treatment for 20-40 min at the ultrasonic power of 120-150W, and stirring for 2-4 h at the temperature of 20-25 ℃ to form the rainbow effect water-soluble polyacrylic acid coating.
Measuring 3mL of the rainbow effect water-soluble polyacrylic acid coating, coating the rainbow effect water-soluble polyacrylic acid coating in a polyethylene culture dish with the diameter of 3.5cm, observing that the rainbow effect water-soluble polyacrylic acid coating is gradually changed into red orange from initial white translucence in the drying process, and changing into a bluish coating after the drying is finished.
In the case of the example 2, the following examples are given,
(1) dispersing microcrystalline cellulose in 58-64% sulfuric acid aqueous solution by mass, fully mixing the microcrystalline cellulose and the sulfuric acid aqueous solution at a mass ratio of 1: 10, stirring at 45 ℃ for 1-2 h to obtain a blend of the microcrystalline cellulose and the sulfuric acid aqueous solution, diluting, centrifuging and dialyzing the blend until the pH value is neutral, and then carrying out ultrasonic treatment for 25-50 min at an ultrasonic power of 600-900W to obtain a nanocrystalline cellulose colloid with a mass fraction of 1.5%;
(2) and (2) weighing the water-soluble polyacrylic acid coating in the nano crystalline cellulose colloid in the step (1) according to the mass ratio of the nano crystalline cellulose colloid to the water-soluble polyacrylic acid coating of 100: 13, adding the water-soluble polyacrylic acid coating into the nano crystalline cellulose colloid, fully mixing, carrying out ultrasonic treatment for 20-40 min at the ultrasonic power of 120-150W, and stirring for 2-4 h at the temperature of 20-25 ℃ to form the rainbow effect water-soluble polyacrylic acid coating.
Measuring 3mL of the rainbow effect water-soluble polyacrylic acid coating, coating the rainbow effect water-soluble polyacrylic acid coating in a polyethylene culture dish with the diameter of 3.5cm, observing that the rainbow effect water-soluble polyacrylic acid coating is gradually changed into red orange from initial white translucence in the drying process, and changing into a yellow-green coating after the drying is finished.
In the case of the example 3, the following examples are given,
(1) dispersing microcrystalline cellulose in 58-64% sulfuric acid aqueous solution by mass, fully mixing, stirring at 45 ℃ for 1-2 h to obtain a blend of microcrystalline cellulose and sulfuric acid aqueous solution, diluting, centrifuging and dialyzing the blend until the pH value is neutral, and then carrying out ultrasonic treatment for 25-50 min at the ultrasonic power of 600-900W to obtain a nanocrystalline cellulose colloid with the mass fraction of 2.3%;
(2) and (2) weighing the water-soluble polyacrylic acid coating in the nano crystalline cellulose colloid in the step (1) according to the mass ratio of the nano crystalline cellulose colloid to the water-soluble polyacrylic acid coating of 100: 30, adding the water-soluble polyacrylic acid coating into the nano crystalline cellulose colloid, fully mixing, carrying out ultrasonic treatment for 20-40 min at the ultrasonic power of 120-150W, and stirring for 2-4 h at the temperature of 20-25 ℃ to form the rainbow effect water-soluble polyacrylic acid coating.
Measuring 3mL of the rainbow effect water-soluble polyacrylic acid coating, coating the rainbow effect water-soluble polyacrylic acid coating in a polyethylene culture dish with the diameter of 3.5cm, observing that the rainbow effect water-soluble polyacrylic acid coating is gradually changed into red orange from initial white translucence in the drying process, and changing into a red orange coating after the drying is finished.
Claims (1)
1. A rainbow effect water-soluble polyacrylic acid coating is prepared by preparing microcrystalline cellulose into a nano crystalline cellulose colloid through sulfuric acid hydrolysis and ultrasonic crushing, and then adding the water-soluble polyacrylic acid coating into the nano crystalline cellulose colloid for reaction to prepare the rainbow effect water-soluble polyacrylic acid coating, wherein the preparation method comprises the following steps:
(1) dispersing microcrystalline cellulose in 58-64% sulfuric acid aqueous solution by mass, fully mixing the microcrystalline cellulose and the sulfuric acid aqueous solution at a mass ratio of 1: 8-12, stirring at 45-60 ℃ for 1-2 h to obtain a blend of the microcrystalline cellulose and the sulfuric acid aqueous solution, diluting, centrifuging and dialyzing the blend until the pH value is neutral, and then carrying out ultrasonic treatment for 25-50 min at an ultrasonic power of 600-900W to obtain a nano crystalline cellulose colloid with a mass fraction of 0.8-2.3%;
(2) and (2) weighing the water-soluble polyacrylic acid coating in the nano crystalline cellulose colloid in the step (1) according to the mass ratio of the nano crystalline cellulose colloid to the water-soluble polyacrylic acid coating of 100: 6-30, adding the water-soluble polyacrylic acid coating into the nano crystalline cellulose colloid, fully mixing, carrying out ultrasonic treatment for 20-40 min, carrying out ultrasonic treatment at the power of 120-150W, and stirring for 2-4 h at the temperature of 20-25 ℃ to form the rainbow effect water-soluble polyacrylic acid coating.
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| CN103174046B (en) * | 2013-04-11 | 2015-08-26 | 浙江理工大学 | A kind of acid hydrolysis and ultrasonic process coordinate system are for the method for nano micro crystal cellulose |
| CN103183987A (en) * | 2013-04-26 | 2013-07-03 | 深圳市宝仕杰塑胶制品有限公司 | Novel color cholesteric liquid crystal coating as well as preparation method and application thereof |
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