CN110804386A - PU (polyurethane) paint with antique effect for foam sculpture and preparation method thereof - Google Patents
PU (polyurethane) paint with antique effect for foam sculpture and preparation method thereof Download PDFInfo
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- CN110804386A CN110804386A CN201911068540.2A CN201911068540A CN110804386A CN 110804386 A CN110804386 A CN 110804386A CN 201911068540 A CN201911068540 A CN 201911068540A CN 110804386 A CN110804386 A CN 110804386A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/833—Chemically modified polymers by nitrogen containing compounds
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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
- C09D5/08—Anti-corrosive paints
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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
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to PU paint with an antique effect for foam sculptures, which is prepared from the following raw materials in parts by mass: 30-40 parts of 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride, 10-15 parts of hyperbranched polyvinyl chloride acrylate, 10-15 parts of inorganic filler, 5-10 parts of 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride, 1-3 parts of initiator, 1-3 parts of defoamer, 1-2 parts of dispersant, 0.4-0.8 part of flatting agent and 15-20 parts of solvent. The invention also discloses a preparation method of the PU paint with the antique effect for the foam sculpture. The PU paint with the antique effect for the foam sculpture, disclosed by the invention, has the advantages of excellent comprehensive performance, moderate hardness and softness, good scratch resistance and falling injury resistance, difficulty in occurrence of phenomena of uneven color and blooming, good pollution resistance of a paint surface, good antique artistic effect after being applied to the foam sculpture, good weather resistance and excellent corrosion resistance.
Description
Technical Field
The invention relates to the technical field of architectural decoration, in particular to PU paint with an antique effect for foam sculpture and a preparation method thereof.
Background
The sculpture is an ornamental and monument which is carved and molded for beautifying the city or for commemorative significance and has certain meaning, symbol or pictograph, is one of modeling arts, also called as sculpture, and is a general name of three creating methods of carving, carving and molding, and means that various plastic materials (such as gypsum, resin, clay and the like) or carved and carved hard materials (such as wood, stone, metal, jade blocks, agate, aluminum, glass steel, sandstone, copper and the like) are used for creating a visible and tangible artistic image with a certain space so as to reflect social life and express the aesthetic feeling, emotion and ideal aesthetic art of artists. The carveable material is reduced through carving and engraving, and the plastic achieves the purpose of artistic creation through stacking the plastic material. In order to commemorate history and protect history deposition, people increasingly attach importance to archaizing sculptures. The development of the sculpture with the antique effect is particularly urgent.
The existing carving art materials comprise unsaturated polyester resin, GRC cement, special gypsum and various metal materials, and are used as new materials of carving art. The latest technology uses high-density foam to make sculpture carving, and sprays liquid PU paint on the surface of sculpture, and then makes the sculpture undergo the processes of solidification, polishing and colouring so as to obtain the invented sculpture, and its hardness not only can be up to that of glass fibre reinforced plastics, but also its corrosion resistance is excellent. The foam sculpture has the advantages that the performance of the PU paint on the surface is particularly important to achieve excellent comprehensive performance and better antique artistic effect. Therefore, it is imperative to develop a PU paint for foam sculptures which has an antique effect.
The PU paint is a general name of all the polyvinyl chloride coatings, the film forming mode is natural film forming, no special process is needed: the chemical drying is carried out according to the proportion, and the comprehensive performance is good; good hardness, fullness, adhesion, durability and hand feeling. The paint film is thin and not very hard; but the adhesive force is particularly good, the luster is uniform, the appearance is not very bright, and the texture and the color of the floor can be well displayed. Has a certain service life after being prepared. However, the paint is not soft enough, the hardness is still to be further improved, the paint cannot resist scratch and fall injury, the phenomena of uneven color and flowering are easy to occur, the anti-pollution performance of the paint surface is poor, and the defects that a paint film is easy to dye after stains are attached, a fingerprint is not easy to erase after being pressed, and the like exist.
The Chinese patent with application number 201510978658.4 discloses a PU paint, which is composed of the following substances in parts by weight: 15-25 parts of castor oil fatty acid, 15-20 parts of glycerol, 2-6 parts of benzoic acid, 35-45 parts of a diluting solvent, 0.8-1.2 parts of catalyst hypophosphorous acid, 15-25 parts of tertiary carboxylic acid glycidyl ester, 10-15 parts of butyl acrylate, 5-10 parts of acrylic acid, 5-15 parts of 2-hydroxypropyl acrylate, 2-8 parts of hydroxyethyl methacrylate, 9-15 parts of crude terephthalic acid, 5-15 parts of phthalic anhydride, 15-20 parts of methyl methacrylate, 5-10 parts of styrene, 0.1-0.3 part of a chain transfer agent, 0.05-0.08 part of an antioxidant, 3-8 parts of an organic silicon auxiliary agent, 0.8-1.2 parts of an initiator, 5-10 parts of a curing agent, 5-8 parts of a diluent and 40-50 parts of a solvent. The PU paint provided by the invention has the advantages of thick paint film hand feeling, soft luster, uniform chromaticity, good impact strength, good leveling property and chemical resistance corrosion, but the components are complex, the manufacturing cost is higher, the paint is still not soft enough, can not resist scratch and fall injury, the phenomena of uneven color tone and blooming are easy to occur, and the anti-pollution performance of the paint surface is poorer.
Therefore, the PU paint with good paint surface pollution resistance meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the foam sculpture industry.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the PU paint with the antique effect for the foam sculpture and the preparation method thereof, and the preparation method has the advantages of simple formula and process, convenient operation, easy material taking, low preparation cost, small dependence on equipment, suitability for continuous industrial production, and higher economic value, social value and ecological value; the prepared PU paint with the antique effect for the foam sculpture is excellent in comprehensive performance, moderate in hardness and softness, good in scratch resistance and falling injury resistance, not prone to causing uneven color and flowering, good in paint surface pollution resistance, good in antique artistic effect of the sculpture, good in weather resistance and excellent in corrosion resistance after being applied to the foam sculpture.
In order to achieve the purpose, the invention adopts the technical scheme that:
the PU paint with the antique effect for the foam sculpture is characterized by comprising the following raw materials in parts by mass: 30-40 parts of 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride, 10-15 parts of hyperbranched polyvinyl chloride acrylate, 10-15 parts of inorganic filler, 5-10 parts of 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride, 1-3 parts of initiator, 1-3 parts of defoamer, 1-2 parts of dispersant, 0.4-0.8 part of flatting agent and 15-20 parts of solvent.
Further, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Further, the leveling agent is one or more of a polyacrylate leveling agent, a cellulose acetate butyrate leveling agent and a polyvinyl butyral leveling agent.
Further, the dispersing agent is sodium hexametaphosphate and/or sodium polycarboxylate; the antifoaming agent is one or more of tributyl phosphate, antifoaming agent Demodex 3100 and antifoaming agent BYK 088.
Further, the solvent is at least one of butyl acetate, ethyl acetate, methyl isobutyl ketone and diisobutyl ketone.
Further, the inorganic filler is at least one of zeolite powder, silicon dioxide, lime powder and talcum powder.
Further, the preparation method of the 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride comprises the following steps: dissolving 5- (trifluoromethyl) pyrazine-2-carboxylic acid, hydroxyl-terminated hyperbranched polyvinyl chloride, dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in an organic solvent, stirring at room temperature for reaction for 12-18 hours, and performing rotary evaporation to obtain the 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride.
Preferably, the mass ratio of the 5- (trifluoromethyl) pyrazine-2-carboxylic acid to the hydroxyl-terminated hyperbranched polyvinyl chloride to the dicyclohexylcarbodiimide to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to the organic solvent is 0.5 to (3-5) to (0.4-0.7) to 0.3 to (20-30).
Preferably, the organic solvent is one of tetrahydrofuran, chloroform, acetonitrile and acetone.
Further, the preparation method of the 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride comprises the following steps: dissolving 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester, hydroxyl-terminated hyperbranched polyvinyl chloride, dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in tetrahydrofuran, stirring at room temperature for reaction for 12-18 hours, and performing rotary evaporation to obtain the 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride.
Preferably, the mass ratio of the 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester, the hydroxyl-terminated hyperbranched polyvinyl chloride, the dicyclohexylcarbodiimide, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the tetrahydrofuran is 0.5: 3-5: 0.4-0.6: 0.25: 20-30.
Another object of the present invention is to provide a method for preparing the PU paint for foam sculptures having an antique effect, comprising the steps of: the raw materials are mixed according to the proportion, stirred for 10 to 20 minutes at the temperature of between 30 and 50 ℃ and at the temperature of between 500 and 800rmp, and then stirred for 20 to 30 minutes at the high speed of between 1000 and 1500rmp to prepare the final product.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the PU paint with the antique effect for the foam sculpture, provided by the invention, has the advantages of simple preparation method formula and process, convenience in operation, easiness in material obtaining, low preparation cost, small dependence on equipment, suitability for continuous industrial production, and higher economic value, social value and ecological value; the prepared PU paint with the antique effect for the foam sculpture is excellent in comprehensive performance, moderate in hardness and softness, good in scratch resistance and falling injury resistance, not prone to causing uneven color and flowering, good in paint surface pollution resistance, good in antique artistic effect of the sculpture, good in weather resistance and excellent in corrosion resistance after being applied to the foam sculpture.
Detailed Description
The invention relates to PU paint with an antique effect for foam sculptures, which is characterized by being prepared from the following raw materials in parts by mass: 30-40 parts of 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride, 10-15 parts of hyperbranched polyvinyl chloride acrylate, 10-15 parts of inorganic filler, 5-10 parts of 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride, 1-3 parts of initiator, 1-3 parts of defoamer, 1-2 parts of dispersant, 0.4-0.8 part of flatting agent and 15-20 parts of solvent.
Further, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the flatting agent is one or more of a polyacrylate flatting agent, a cellulose acetate butyrate flatting agent and a polyvinyl butyral flatting agent; the dispersing agent is sodium hexametaphosphate and/or sodium polycarboxylate; the antifoaming agent is one or more of tributyl phosphate, antifoaming agent dele 3100 and antifoaming agent BYK088
Further, the solvent is at least one of butyl acetate, ethyl acetate, methyl isobutyl ketone and diisobutyl ketone; the inorganic filler is at least one of zeolite powder, silicon dioxide, lime powder and talcum powder.
Further, the preparation method of the 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride comprises the following steps: dissolving 5- (trifluoromethyl) pyrazine-2-carboxylic acid, hydroxyl-terminated hyperbranched polyvinyl chloride, dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in an organic solvent, stirring at room temperature for reaction for 12-18 hours, and performing rotary evaporation to obtain the 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride.
Preferably, the mass ratio of the 5- (trifluoromethyl) pyrazine-2-carboxylic acid to the hydroxyl-terminated hyperbranched polyvinyl chloride to the dicyclohexylcarbodiimide to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to the organic solvent is 0.5 to (3-5) to (0.4-0.7) to 0.3 to (20-30); the organic solvent is one of tetrahydrofuran, chloroform, acetonitrile and acetone.
Further, the preparation method of the 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride comprises the following steps: dissolving 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester, hydroxyl-terminated hyperbranched polyvinyl chloride, dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in tetrahydrofuran, stirring at room temperature for reaction for 12-18 hours, and performing rotary evaporation to obtain the 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride.
Preferably, the mass ratio of the 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester, the hydroxyl-terminated hyperbranched polyvinyl chloride, the dicyclohexylcarbodiimide, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the tetrahydrofuran is 0.5: 3-5: 0.4-0.6: 0.25: 20-30.
Preferably, the hydroxyl-terminated hyperbranched polyvinyl chloride is self-made, and the preparation method refers to: the first embodiment of the chinese patent with application number 201810401957.5; the hyperbranched polyvinyl chloride acrylate is self-made, and the preparation method refers to: water solubility properties of the hyperbranched poly (vinyl chloride) acrylate [ J ]. proceedings of the academy of agricultural engineering of sec-ca, 2010, 23 (2): 43-47.
Another object of the present invention is to provide a method for preparing the PU paint for foam sculptures having an antique effect, comprising the steps of: the raw materials are mixed according to the proportion, stirred for 10 to 20 minutes at the temperature of between 30 and 50 ℃ and at the temperature of between 500 and 800rmp, and then stirred for 20 to 30 minutes at the high speed of between 1000 and 1500rmp to prepare the final product.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the PU paint with the antique effect for the foam sculpture, provided by the invention, has the advantages of simple preparation method formula and process, convenience in operation, easiness in material obtaining, low preparation cost, small dependence on equipment, suitability for continuous industrial production, and higher economic value, social value and ecological value; the prepared PU paint with the antique effect for the foam sculpture is excellent in comprehensive performance, moderate in hardness and softness, good in scratch resistance and falling injury resistance, not prone to causing uneven color and flowering, good in paint surface pollution resistance, good in antique artistic effect of the sculpture, good in weather resistance and excellent in corrosion resistance after being applied to the foam sculpture.
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
Embodiment 1 provides a PU paint for a foam sculpture with an antique effect, which is characterized by comprising the following raw materials in parts by mass: 30 parts of 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride, 10 parts of hyperbranched polyvinyl chloride acrylate, 10 parts of zeolite powder, 5 parts of 1- (9-H-fluorene-9-methyl) piperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride, 1 part of azobisisobutyronitrile, 1 part of tributyl phosphate, 1 part of sodium hexametaphosphate, 0.4 part of polyacrylate leveling agent and 15 parts of butyl acetate.
The preparation method of the 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride comprises the following steps: 5g of 5- (trifluoromethyl) pyrazine-2-carboxylic acid, 30g of hydroxyl-terminated hyperbranched polyvinyl chloride, 4g of dicyclohexylcarbodiimide and 3g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride are dissolved in 200g of tetrahydrofuran, stirred and reacted for 12 hours at room temperature, and then subjected to rotary evaporation to obtain the 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride.
The preparation method of the 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride comprises the following steps: 5g of 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester, 30g of hydroxyl-terminated hyperbranched polyvinyl chloride, 4g of dicyclohexylcarbodiimide and 2.5g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride are dissolved in 200g of tetrahydrofuran, stirred and reacted for 12 hours at room temperature, and then subjected to rotary evaporation to obtain the 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride.
A preparation method of the PU paint with antique effect for foam sculpture is characterized by comprising the following steps: the raw materials are mixed in proportion, stirred at 30 ℃ for 10 minutes at 500rmp and then stirred at high speed for 20 minutes at 1000rmp to prepare the final product.
Example 2
Embodiment 2 provides a PU paint for a foam sculpture having an antique effect, which has a formulation and a preparation method substantially the same as those of embodiment 1, except that the PU paint is prepared from the following raw materials in parts by mass: 32 parts of 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride, 11 parts of hyperbranched polyvinyl chloride acrylate, 11 parts of zeolite powder, 6 parts of 1- (9-H-fluorene-9-methyl) piperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride, 1.5 parts of azodiisobutyronitrile, 1.5 parts of tributyl phosphate, 1.2 parts of sodium hexametaphosphate, 0.5 part of polyacrylate flatting agent and 16 parts of butyl acetate.
Example 3
Embodiment 3 provides a PU paint for a foam sculpture having an antique effect, which has a formulation and a preparation method substantially the same as those of embodiment 1, except that the PU paint is prepared from the following raw materials in parts by mass: 35 parts of 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride, 13 parts of hyperbranched polyvinyl chloride acrylate, 13 parts of zeolite powder, 8 parts of 1- (9-H-fluorene-9-methyl) piperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride, 2 parts of azodiisobutyronitrile, 2 parts of tributyl phosphate, 1.5 parts of sodium hexametaphosphate, 0.6 part of polyacrylate flatting agent and 18 parts of butyl acetate.
Example 4
Embodiment 4 provides a PU paint for a foam sculpture having an antique effect, which has a formulation and a preparation method substantially the same as those of embodiment 1, except that the PU paint is prepared from the following raw materials in parts by mass: 38 parts of 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride, 14 parts of hyperbranched polyvinyl chloride acrylate, 14 parts of zeolite powder, 9 parts of 1- (9-H-fluorene-9-methyl) piperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride, 2.8 parts of azobisisobutyronitrile, 2.7 parts of tributyl phosphate, 1.8 parts of sodium hexametaphosphate, 0.7 part of polyacrylate flatting agent and 19 parts of butyl acetate.
Example 5
Embodiment 5 provides a PU paint for a foam sculpture having an antique effect, which has a formulation and a preparation method substantially the same as those of embodiment 1, except that the PU paint is prepared from the following raw materials in parts by mass: 40 parts of 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride, 15 parts of hyperbranched polyvinyl chloride acrylate, 15 parts of zeolite powder, 10 parts of 1- (9-H-fluorene-9-methyl) piperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride, 3 parts of azodiisobutyronitrile, 3 parts of tributyl phosphate, 2 parts of sodium hexametaphosphate, 0.8 part of polyacrylate leveling agent and 20 parts of butyl acetate.
Comparative example 1
Comparative example 1 provides a PU paint for foam sculptures having antique effects, the formulation and preparation method of which are substantially the same as those of example 1, except that 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride is not added.
Comparative example 2
Comparative example 2 provides a PU paint for foam sculptures having antique effects, the formulation and preparation method of which are substantially the same as those of example 1, except that 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride was not added.
Comparative example 3
Comparative example 3 provides a PU paint for foam sculptures having antique effects, the formulation and preparation method of which are substantially the same as those of example 1, except that hyperbranched polyvinyl chloride acrylate is not added.
To further illustrate the technical effects of the embodiments of the present invention, the PU paints for foam sculptures having antique effects, prepared in the embodiments 1 to 5 of the present invention and the comparative examples 1 to 3, were tested, the test results are shown in table 1, and the test methods are as follows:
(1) the coating adhesion is tested according to GB/T9286-1998, after being scribed by a ruling knife, the coating is pasted by a 3M adhesive tape and then pulled, and the area of the coating which is not pulled is observed by naked eyes and is expressed by percentage;
(2) the hardness of the coating is tested according to GB/T6739-2006, after a paint film is cured, the sample plate is placed in a horizontal position, pencil hardness of the coating is measured by pushing a pencil with gradually increased hardness on the coating, and the pencil hardness when no defect appears on the surface of the coating is taken as the hardness of the coating;
(3) and (3) determining the wear resistance of the coating: flatly placing the prepared sample piece on glass, wiping the surface of the coating by using a cotton swab until the coating is just scratched, and recording the wiping times, wherein the more wiping times, the more wear resistance of the coating is shown;
as can be seen from table 1, the PU paint for foam sculptures with antique effects disclosed by the embodiments of the present invention has strong adhesion, high hardness, and good scrub resistance, which is a result of the synergistic effect of 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched poly (vinyl chloride), hyperbranched poly (vinyl chloride) acrylate, and 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched poly (vinyl chloride).
TABLE 1
| Detecting items | Coating layerAdhesion (%) | Hardness scale (grade) | Number of scrub resistant |
| Example 1 | 100 | 3H | 30 |
| Example 2 | 100 | 3H | 32 |
| Example 3 | 100 | 4H | 33 |
| Example 4 | 100 | 4H | 35 |
| Example 5 | 100 | 4H | 38 |
| Comparative example 1 | 96 | 2H | 22 |
| Comparative example 2 | 95 | 2H | 20 |
| Comparative example 3 | 93 | 2H | 19 |
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The PU paint with the antique effect for the foam sculpture is characterized by comprising the following raw materials in parts by mass: 30-40 parts of 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride, 10-15 parts of hyperbranched polyvinyl chloride acrylate, 10-15 parts of inorganic filler, 5-10 parts of 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride, 1-3 parts of initiator, 1-3 parts of defoamer, 1-2 parts of dispersant, 0.4-0.8 part of flatting agent and 15-20 parts of solvent.
2. The PU paint for foam sculptures having an antique effect according to claim 1, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
3. The PU paint for foam sculptures having antique effects according to claim 1, wherein the leveling agent is one or more of polyacrylate leveling agent, cellulose acetate leveling agent, polyvinyl butyral leveling agent.
4. The PU paint for foam sculptures having an antique effect according to claim 1, wherein the dispersant is sodium hexametaphosphate and/or sodium polycarboxylate; the antifoaming agent is one or more of tributyl phosphate, antifoaming agent Demodex 3100 and antifoaming agent BYK 088.
5. The PU paint for foam sculptures having an antique effect according to claim 1, wherein the solvent is at least one of butyl acetate, ethyl acetate, methyl isobutyl ketone, and diisobutyl ketone; the inorganic filler is at least one of zeolite powder, silicon dioxide, lime powder and talcum powder.
6. The PU paint with antique effect for foam sculptures according to claim 1, wherein the preparation method of the 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride comprises the following steps: dissolving 5- (trifluoromethyl) pyrazine-2-carboxylic acid, hydroxyl-terminated hyperbranched polyvinyl chloride, dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in an organic solvent, stirring at room temperature for reaction for 12-18 hours, and performing rotary evaporation to obtain the 5- (trifluoromethyl) pyrazine-2-carboxylic acid modified hydroxyl-terminated hyperbranched polyvinyl chloride.
7. The PU paint for foam sculptures having antique effects according to claim 6, wherein the mass ratio of the 5- (trifluoromethyl) pyrazine-2-carboxylic acid, the hydroxyl-terminated hyperbranched poly (vinyl chloride), the dicyclohexylcarbodiimide, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the organic solvent is 0.5: 3-5: 0.4-0.7: 0.3: 20-30; the organic solvent is one of tetrahydrofuran, chloroform, acetonitrile and acetone.
8. The antique-looking PU paint for foam sculptures according to claim 1, wherein the preparation method of the 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl terminated hyperbranched poly (vinyl chloride) comprises the following steps: dissolving 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester, hydroxyl-terminated hyperbranched polyvinyl chloride, dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in tetrahydrofuran, stirring at room temperature for reaction for 12-18 hours, and performing rotary evaporation to obtain the 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester modified hydroxyl-terminated hyperbranched polyvinyl chloride.
9. The antique-looking PU paint according to claim 8, wherein the mass ratio of 1- (9-H-fluorene-9-methyl) hydropiperazine-1, 2, 4-tricarboxylic acid-4-allyl ester, hydroxyl terminated hyperbranched poly (chloride), dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and tetrahydrofuran is 0.5: 3-5: 0.4-0.6: 0.25: (20-30).
10. The PU paint for foam sculptures having an antique effect according to any one of claims 1 to 9, wherein the preparation method of the PU paint for foam sculptures having an antique effect comprises the steps of: the raw materials are mixed according to the proportion, stirred for 10 to 20 minutes at the temperature of between 30 and 50 ℃ and at the temperature of between 500 and 800rmp, and then stirred for 20 to 30 minutes at the high speed of between 1000 and 1500rmp to prepare the final product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911068540.2A CN110804386A (en) | 2019-11-05 | 2019-11-05 | PU (polyurethane) paint with antique effect for foam sculpture and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911068540.2A CN110804386A (en) | 2019-11-05 | 2019-11-05 | PU (polyurethane) paint with antique effect for foam sculpture and preparation method thereof |
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| CN110804386A true CN110804386A (en) | 2020-02-18 |
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| CN201911068540.2A Pending CN110804386A (en) | 2019-11-05 | 2019-11-05 | PU (polyurethane) paint with antique effect for foam sculpture and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732844A (en) * | 2020-07-08 | 2020-10-02 | 高雪梅 | Household fireproof coating and preparation method thereof |
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