CN113956767A - Wear-resistant floor paint and preparation method thereof - Google Patents
Wear-resistant floor paint and preparation method thereof Download PDFInfo
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- CN113956767A CN113956767A CN202111327052.6A CN202111327052A CN113956767A CN 113956767 A CN113956767 A CN 113956767A CN 202111327052 A CN202111327052 A CN 202111327052A CN 113956767 A CN113956767 A CN 113956767A
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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
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
The invention discloses a wear-resistant floor paint and a preparation method thereof, and the wear-resistant floor paint comprises the following components: the component A comprises: the coating comprises disulfide bond-containing polyurethane, chitosan acrylate polymer, high-functionality inorganic nanoparticles, a dispersing agent, pigment, deionized water and an auxiliary agent; and B component: carboxymethyl cellulose modified epoxy resin, filler and deionized water. The wear-resistant floor paint disclosed by the invention has better mechanical properties and can withstand long-time friction. The high-functionality inorganic nano-particles are added to enhance the adhesion between the floor paint and the base material made of silicate materials, so that the floor paint is not easy to fall off; the self-repairing function of hydrogen bonds formed between disulfide bonds in the polymer and chitosan and carboxymethyl cellulose enables the floor paint to be capable of repairing damaged parts to a certain extent when being damaged, self-repairing is achieved, and the wear resistance of the floor paint is enhanced. According to the preparation method of the wear-resistant floor paint, the raw materials are uniformly mixed to form a hydrogen bond or a cross-linking structure, so that the wear resistance of the floor paint is enhanced.
Description
Technical Field
The invention belongs to the technical field of floor paint preparation, and particularly relates to wear-resistant floor paint and a preparation method thereof.
Background
The floor paint is different from common paint in use and is usually applied to the ground, the common paint is poor in wear resistance, and a painted floor can be worn and fall off at most in half a year, so that the floor paint has higher wear resistance than the common paint and also has better ground adhesion, is resistant to wear and cannot fall off after long-time use.
And the floor paint is often used on a certain area as a whole, and the abrasion caused by long-time friction often occurs at the position with frequent movement, and the abrasion degree of the floor paint at the position is high, so that the abraded floor paint needs to be repaired or replaced after long-term use. If the overall replacement cost is too high, and if the repair is only partial, the overall aesthetic appearance is often damaged, and even the overall performance is locally reduced due to the segmentation. Meanwhile, for some areas which are not frequently used, the wear caused by the occasional use is attractive if the repair and replacement are not carried out, and the wear is possibly further expanded, and the repair and replacement are too high in cost.
There is therefore a need to provide more abrasion resistant floor finishes with self-healing functionality.
Disclosure of Invention
In order to overcome the defects of the prior art, the first object of the invention is to provide a wear-resistant floor paint which has better mechanical properties, can withstand long-time friction, has good adhesiveness to a base material made of silicate materials so as to be difficult to fall off, has a certain repair function on a damaged part, realizes self-repair, and enhances the wear resistance of the floor paint.
The second purpose of the invention is to provide a preparation method of the wear-resistant floor paint.
The first purpose of the invention can be achieved by adopting the following technical scheme:
the wear-resistant floor paint is characterized by comprising the following raw materials in parts by weight:
the component A comprises: 50-60 parts of disulfide bond-containing polyurethane, 10-15 parts of chitosan acrylate polymer, 0.5-2 parts of high-functionality inorganic nanoparticles, 1-5 parts of dispersing agent, 2-5 parts of pigment, 10-15 parts of deionized water and 5-10 parts of auxiliary agent; and B component: 40-60 parts of carboxymethyl cellulose modified epoxy resin, 8-15 parts of filler and 10-25 parts of water.
Preferably, the disulfide bond-containing polyurethane is obtained by polymerizing diisocyanate and 2, 2' -dithiodiethanol, wherein the diisocyanate is one or a combination of two or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
Preferably, the chitosan acrylic polymer is prepared according to the following steps:
s21, dissolving chitosan with the deacetylation degree of 80-90% and the molecular weight of 30w in an acid solution, and adding an acrylic compound for reaction to obtain chitosan acrylate;
s22, carrying out emulsion polymerization on the chitosan acrylate obtained in the step S21 by using sodium persulfate as an initiator to obtain the chitosan acrylic polymer;
the acrylic compound is one or a composition of more than two of acrylic acid, methacrylic acid, 2-ethacrylic acid and 3-methoxyacrylic acid.
Preferably, the carboxymethyl cellulose-modified epoxy resin is obtained by grafting carboxymethyl cellulose with bisphenol A epoxy resin in the presence of sodium hydroxide.
Preferably, the bisphenol A epoxy resin is E-44 type, the carboxymethyl cellulose has an average molecular weight of 250000, a DS of 0.7 and a viscosity of 200-500 mPa.s.
Preferably, the highly functional inorganic nanoparticles are inorganic nanoparticles having formula I (a)1Na2O·a2K2O·a3Li2O)·bSiO2·cH2O formula I wherein a1,a2,a3≥0，a1+a2+a3＞0；b≥a1+a2+a3The inorganic nano-particles pass through 400-600 meshesAnd (4) screening.
Preferably, the inorganic nanoparticles of formula I are prepared by:
s31, mixing sodium silicate, potassium silicate, lithium silicate and silicon dioxide according to the metering number to obtain a first composition;
s32, dissolving inorganic acid in water, and then mixing with the first composition obtained in the step S31 to obtain the inorganic nanoparticles of the formula I; the inorganic acid is phosphoric acid or boric acid.
Preferably, the auxiliary agent is one or a composition of more than two of a leveling agent, a toughening agent, a thickening agent, a defoaming agent, a wetting agent, an antibacterial agent and a mildew preventive.
Preferably, the filler is one or a composition of more than two of heavy calcium carbonate powder, kaolin, talcum powder, mica powder, silicon micropowder and quartz powder, and the filler is sieved by a 400-mesh and 600-mesh sieve.
The second purpose of the invention can be achieved by adopting the following technical scheme:
a preparation method of wear-resistant floor paint comprises the following steps: preparing a component A mixed solution: adding the other component A substances except the disulfide bond-containing polyurethane and the chitosan acrylate polymer and deionized water into a dispersion kettle in proportion, dispersing for 30-60min in the reaction kettle at the rotation speed of 700-1200 r/min, then adding the disulfide bond-containing polyurethane and the chitosan acrylate polymer, and continuing to disperse for 30-60min at the rotation speed of 1000-1200r/min to obtain a component A mixed solution;
preparing a component B mixed solution: adding the carboxymethyl cellulose modified epoxy resin of the component B and the filler into deionized water according to a proportion, and dispersing for 30-60min under the condition of the rotating speed of 700-900r/min to obtain a component B mixed solution;
mixing: and mixing the component A mixed solution and the component B mixed solution, and uniformly stirring at the rotation speed of 1000-1200r/min to obtain the wear-resistant floor paint.
Compared with the prior art, the invention has the beneficial effects that:
1. the wear-resistant floor paint disclosed by the invention takes disulfide bond-containing polyurethane, chitosan acrylate polymer, high-functionality inorganic nanoparticles and carboxymethyl cellulose modified epoxy resin as main components, wherein the polyurethane contains disulfide bonds which are groups with a self-repairing function, so that the polyurethane also has a self-repairing function; and the chitosan contained in the acrylate polymer contains abundant amino groups, acetamide groups and other groups, the carboxymethyl cellulose contained in the epoxy resin contains abundant carboxyl groups and hydroxyl groups, and the groups interact with each other to form diversified hydrogen bond networks. The hydrogen bonds can also break along with the damaged interface, however, the carboxyl cellulose contains abundant crosslinking sites, so the hydrogen bonds in the interface can be quickly superposed, and the quick healing behavior of the material can realize the self-repairing of the floor paint together with a single disulfide bond with slower healing capacity. In addition, the three components of polyurethane, acrylate and epoxy resin are crosslinked to form a film, so that good mechanical properties are provided for the floor paint, and the wear resistance is improved.
2. The wear-resistant floor paint disclosed by the invention is also added with high-functionality inorganic nano particles, wherein Si replaces central metal atoms, so that single metal atoms are changed into double bonds, a net structure is formed, the silicon-containing wear-resistant floor paint can perform condensation reaction with silicate, the adhesion or adhesion with a substrate is improved, the silicon-containing wear-resistant floor paint is not easy to fall off, and the wear resistance of the floor paint is enhanced.
3. According to the preparation method of the wear-resistant floor paint, the raw materials are divided into the component A and the component B, the component A and the component B are respectively and uniformly mixed, and then the components A and the component B are mixed to prepare the wear-resistant floor paint, so that the raw materials can be uniformly mixed in water to form a hydrogen bond or a cross-linking structure, the performance of the floor paint is enhanced, and the wear resistance is improved.
Detailed Description
The invention will be further described with reference to specific embodiments:
the wear resistance is an important characteristic of the floor paint, the wear resistance refers to the resistance of a paint film to a friction effect after being dried, and the traditional method generally increases the thickness of the paint layer or finishes coating the epoxy floor paint and then coats a layer of polyurethane varnish on the surface of the epoxy floor paint in a rolling way, so that the glossiness and the wear resistance of the epoxy floor paint are improved. But none of these can fundamentally improve the abrasion resistance of floor paints. The invention provides a wear-resistant floor paint which has excellent wear resistance.
The wear-resistant floor paint comprises the following raw materials in parts by weight:
the component A comprises: 50-60 parts of disulfide bond-containing polyurethane, 10-15 parts of chitosan acrylate polymer, 0.5-2 parts of high-functionality inorganic nanoparticles, 1-5 parts of dispersing agent, 2-5 parts of pigment, 10-15 parts of deionized water and 5-10 parts of auxiliary agent; and B component: 40-60 parts of carboxymethyl cellulose modified epoxy resin, 8-15 parts of filler and 10-25 parts of water.
The disulfide bond-containing polyurethane, the chitosan acrylate polymer and the carboxymethyl cellulose modified epoxy resin are used as main components, the three polymers can be crosslinked into a net shape, and a polymer blend is formed through mutual penetration and entanglement, so that the floor paint has excellent mechanical properties and physicochemical properties, and can withstand the long-time action of friction force.
The disulfide bond is introduced into the main chain of the polyurethane, when the polyurethane is damaged, the disulfide bond can be broken under the conditions of stress and the like to form a sulfur free radical, and further a sulfydryl group is formed, and the external energy can be released in the change process to prevent the coating from being further damaged; meanwhile, the broken polyurethane chains are reconnected and form disulfide bonds again, and the self-repairing function is achieved.
And chitosan contained in the acrylate polymer contains abundant amino groups, acetamide groups and other groups, carboxymethyl cellulose contained in the epoxy resin contains abundant carboxyl groups and hydroxyl groups, and the amino groups, the acetamide groups and other groups in the chitosan interact with the carboxyl groups and the hydroxyl groups in the carboxymethyl cellulose to form diversified hydrogen bond networks. At a damaged interface, hydrogen bonds can break, however, because carboxyl cellulose and chitosan contain abundant cross-linking sites, the hydrogen bonds in the interface can be rapidly superposed, the material can realize rapid repair behavior, and the repair of the hydrogen bond action and the covalent repair of a single disulfide bond with slower repair capability can jointly realize the self-repair of the floor paint. Through the restoration function, the floor paint can withstand the action of friction force and can be quickly restored under the dual actions of hydrogen bonds and disulfide bond covalent bonds after being subjected to friction damage.
As a further embodiment, the disulfide bond-containing polyurethane is obtained by polymerizing diisocyanate with 2, 2' -dithiodiethanol. The polyurethane is prepared by the polymerization reaction of diisocyanate and polyol or micromolecular diol. The 2, 2' -dithiodiethanol is used as the small molecular polyol, and the disulfide bonds are introduced into the main chain of the polyurethane through polymerization reaction, so that the disulfide bonds can be uniformly distributed in the polyurethane, and the polyurethane has a self-repairing function. Therefore, when the floor paint is worn or damaged, the disulfide bonds in the polyurethane main chain are damaged, on one hand, the damage can be prevented from being aggravated, and on the other hand, the material can be repaired through the reformation of the disulfide bonds.
The diisocyanate is one or a composition of more than two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate. The diisocyanate is selected from nonionic diisocyanate, and can easily react with 2, 2' -dithiodiethanol, so that the obtained polyurethane has better wear resistance. In addition, the diisocyanate is slightly excessive, so that the tail end of the polymer contains a large amount of-NCO groups, and the polymer can react with epoxy groups or other hydroxyl-containing groups of the epoxy resin to be crosslinked and modified.
As a further embodiment, the chitosan acrylic polymer is prepared according to the following steps:
s21, dissolving chitosan in an acid solution, and adding an acrylic compound for reaction to obtain chitosan acrylate;
s22, carrying out emulsion polymerization on the chitosan acrylate obtained in the step S21 by using sodium persulfate as an initiator to obtain the chitosan acrylic polymer;
as a further embodiment, after the reaction in step S21 is completed, the chitosan methacrylate is precipitated with ethanol, and then freeze-dried to obtain pure chitosan methacrylate for the subsequent polymerization.
As a further embodiment, the chitosan has a degree of deacetylation of 80 to 90% and a molecular weight of 30 ten thousand. The chitosan with deacetylation degree of 80-90% is adopted, not only partial acetamide is retained, but also a large amount of amino groups are contained in the chitosan, and hydrogen bonds can be formed between the chitosan and carboxyl or hydroxyl. Further, the degree of deacetylation is not limited to 80-90%, and any degree of deacetylation can achieve the purpose of the present invention. The chitosan with the molecular weight of 30 ten thousand is used for ensuring that the synthesized chitosan polyacrylate has controllable molecular weight, viscosity and the like, and the chitosan with the molecular weight of 20 ten thousand to 40 ten thousand can achieve the aim of the invention. The emulsion polymerization may be carried out according to conventional reaction procedures, the initiator is sodium persulfate, and other conventional initiators capable of initiating emulsion polymerization of acrylates may be selected. The polymerization can be carried out at a temperature of from 30 to 120 ℃.
As a further embodiment, the acid solution in step S21 may be acetic acid, which not only helps to dissolve chitosan, but also can be used as a catalyst to promote the esterification reaction between chitosan and acrylic acid.
In a further embodiment, the acrylic compound is one or a combination of two or more of acrylic acid, methacrylic acid, 2-ethacrylic acid, and 3-methoxyacrylic acid.
In a further embodiment, the carboxymethyl cellulose-modified epoxy resin is obtained by grafting carboxymethyl cellulose with a bisphenol a epoxy resin in the presence of sodium hydroxide.
As a further embodiment, the bisphenol A type epoxy resin is E-44 type, the carboxymethyl cellulose has an average molecular weight of 25 ten thousand, a DS of 0.7 and a viscosity of 200-500 mPa.s. The bisphenol A type epoxy resin is a common epoxy resin, the epoxy value of the E-44 type epoxy resin is 0.41-0.47, the softening point is 12-20 ℃, and the reaction with carboxymethyl cellulose is facilitated, so that the carboxymethyl cellulose is introduced into an epoxy resin chain.
Therefore, in the formed floor paint, chitosan acrylic acid polymer and epoxy resin containing disulfide bond polyurethane and carboxymethyl cellulose are mutually penetrated and entangled to form a cross-linked network polymer blend, wherein amino groups, acetamide groups and other groups contained in chitosan interact with carboxyl groups and hydroxyl groups contained in carboxymethyl cellulose to form diversified hydrogen bond networks. At the damaged interface, rapid repair behavior is achieved by rapid coincidence following hydrogen bond cleavage.
As a further embodiment, the highly functional inorganic nanoparticles are inorganic nanoparticles having formula I (a)1Na2O·a2K2O·a3Li2O)·bSiO2·cH2O (formula I) wherein a1,a2,a3≥0，a1+a2+a3＞0；b≥a1+a2+a3(ii) a The Si replaces central metal atoms, so that single metal atoms are changed into double bonds, a net structure is formed, condensation reaction can be carried out on the net structure and silicate, the bonding strength of the net structure and the silicate to a base material is improved, and the net structure is not easy to fall off. In addition, after Si is substituted, the compatibility with an organic reagent is increased, so that the high-functionality inorganic nano-particles have better dispersibility and stability, and meanwhile, the mechanical property is provided for the floor paint. Preferably, the inorganic nanoparticles are sieved through a 400-600 mesh sieve.
As a further embodiment, the inorganic nanoparticles of formula I are prepared by:
s31, mixing sodium silicate, potassium silicate, lithium silicate and silicon dioxide according to the metering number to obtain a first composition;
s32, dissolving inorganic acid in water, and then mixing with the first composition obtained in the step S31 to obtain the inorganic nanoparticles of the formula I; the inorganic acid is phosphoric acid or boric acid.
The high-functionality inorganic nano-particles can be obtained by adding the sodium silicate, the potassium silicate, the lithium silicate and the silicon dioxide according to the measured amount and mixing under the condition of phosphoric acid or boric acid, does not need a complex treatment process and is suitable for production.
In a further embodiment, the auxiliary agent is one or a combination of more than two of a leveling agent, a toughening agent, a thickening agent, a defoaming agent, a wetting agent, an antibacterial agent and a mildew preventive. The auxiliaries are conventional agents, and the auxiliaries of the conventional kind in the art can be added to the floor paint of the present invention.
As a further embodiment, the filler is one or a composition of more than two of heavy calcium carbonate powder, kaolin, talcum powder, mica powder, silicon powder and quartz powder, and the filler is sieved by a 400-sand 600-mesh sieve.
A preparation method of wear-resistant floor paint comprises the following steps: preparing a component A mixed solution: adding the other component A substances except the disulfide bond-containing polyurethane and the chitosan acrylate polymer and deionized water into a dispersion kettle according to the parts by weight, dispersing for 30-60min in the reaction kettle at the rotating speed of 700-1200 r/min, then adding the disulfide bond-containing polyurethane and the chitosan acrylate polymer, and continuously dispersing for 30-60min at the rotating speed of 1000-1200r/min to obtain a component A mixed solution;
preparing a component B mixed solution: adding the carboxymethyl cellulose modified epoxy resin and the filler of the component B into deionized water according to parts by weight, and dispersing for 30-60min under the condition of the rotating speed of 700-900r/min to obtain a component B mixed solution;
mixing: and mixing the component A mixed solution and the component B mixed solution, and uniformly stirring at the rotation speed of 1000-1200r/min to obtain the wear-resistant floor paint.
The raw materials are divided into a component A and a component B, wherein the component A is polyurethane containing disulfide bonds, chitosan acrylate polymer, high-functionality inorganic nanoparticles, a dispersing agent, pigment, deionized water and an auxiliary agent substance, and can be fully mixed through the dispersing agent; the component B is carboxymethyl cellulose modified epoxy resin, filler and deionized water, and organic and inorganic components can be dissolved and mixed in the aqueous solution better. Wherein the carboxymethyl cellulose and chitosan hydrophilic groups on the polymer can help the polymer to disperse in water to form stable emulsion. The components A and B are respectively and uniformly mixed and then are mixed to prepare the wear-resistant floor paint, so that the raw materials can be uniformly mixed in water to form a hydrogen bond or a cross-linked structure, the performance of the floor paint is enhanced, and the wear resistance is improved.
Example 1 preparation of disulfide bond-containing polyurethane
Adding 2, 2' -dithiodiethanol into a reactor, adding 1.05 equivalent of toluene diisocyanate, controlling the reaction to react for a period of time in stages at 65 ℃, 70 ℃ and 75 ℃, respectively, adjusting the temperature of the system to the next temperature stage after the temperature of the system is stable, and finally reacting for 2 hours at 80 ℃ to obtain the polyurethane containing disulfide bonds.
Example 2 preparation of Chitosan methacrylate Polymer
25g of chitosan with deacetylation degree of 85% and molecular weight of 30w are dissolved in 1.5% acetic acid at room temperature to prepare a 3% solution. Adding methacrylic acid to the solution at a concentration of 0.5 ml/g chitosan; after being mixed evenly, the mixture is stirred at 60 ℃ and 160rpm for substitution reaction; the reaction time is lh, chitosan methacrylate with a degree of substitution of 20% is generated, the product is precipitated with ethanol, frozen and air-dried. Chitosan methacrylate was dissolved in PBS (phosphate buffered saline) having pH 6, 3ml of 0.06mol/L sodium persulfate was added thereto, and the mixture was reacted at 40 ℃ for 20min to polymerize chitosan methacrylate.
Example 3 preparation of highly functional inorganic nanoparticles
In a 14mmol mixture of 33.8% sodium silicate, 33.8% potassium silicate and 26.5% lithium silicate, 53mmol of SiO were added2After being mixed evenly, the mixture is stirred, mixed and reacted with 95g of water and 0.6g of boric acid for 1 hour to obtain the high-functionality inorganic nano-particles.
EXAMPLE 4 preparation of carboxymethyl cellulose-modified epoxy resin
Dissolving E-44 type bisphenol A epoxy resin in a sodium hydroxide aqueous solution, dissolving and diluting carboxymethyl cellulose with the average molecular weight of 25 ten thousand, the DS of 0.7 and the viscosity of 200-500mPa.s in water, adding the solution into the sodium hydroxide aqueous solution containing the epoxy resin in batches, stirring and reacting at normal temperature until the carboxymethyl cellulose aqueous solution is completely dripped, continuing to react for 1h to obtain the carboxymethyl cellulose modified epoxy resin,
example 5
Preparing a component A mixed solution: adding the component A except the disulfide bond-containing polyurethane and the chitosan acrylate polymer and deionized water into a dispersion kettle according to parts by weight, dispersing for 60min in a reaction kettle at the rotating speed of 700r/min, then adding the disulfide bond-containing polyurethane prepared in the example 1 and the chitosan methacrylate polymer prepared in the example 2, and continuously dispersing for 30 at the rotating speed of 1200r/min to obtain a component A mixed solution; preparing a component B mixed solution: adding the carboxymethyl cellulose modified epoxy resin prepared in the embodiment 4 of the component B and the filler into deionized water according to parts by weight, and dispersing for 30min at the rotating speed of 700r/min to obtain a component B mixed solution; mixing: and mixing the component A mixed solution and the component B mixed solution, and uniformly stirring at the rotating speed of 1200r/min to obtain the wear-resistant floor paint.
Comparative example 1
Comparative example 1 differs from example 5 in that the chitosan methacrylate polymer was replaced with the chitosan and methacrylate in the reactive amounts of example 2, the carboxymethyl cellulose and epoxy resin were replaced with the carboxymethyl cellulose and epoxy resin in the reactive amounts of example 4, and the other ingredient steps were the same.
Comparative example 2
Comparative example 2 differs from comparative example 1 in that the procedure was the same for the other ingredients without the addition of chitosan and carboxymethyl cellulose.
Comparative example 3
Comparative example 3 is different from example 5 in that the procedure of other ingredients is the same without adding the highly functional inorganic nanoparticles.
Floor paint performance test
The terrace paints of examples 1-3 and comparative examples 1-3 were tested according to the method of GB/T1768-:
TABLE 1 abrasion resistance of floor paints
| Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Abrasion resistance 750g/500R | 0.0001 | 0.012 | 0.017 | 0.0009 |
As can be seen from Table 1, comparative example 2 is slightly higher than 750g/500R of comparative example 1, which shows that the wear resistance of the floor paint can be slightly improved by using chitosan core carboxymethyl cellulose alone, but compared with the floor paint of example 5, the wear resistance of the floor paint can be improved by introducing chitosan into acrylate polymer, introducing carboxymethyl cellulose into epoxy resin, and then crosslinking with disulfide bond-containing polyurethane, and hydrogen bonds formed by chitosan and carboxymethyl cellulose. Comparison of comparative example 3 with 750g/500R of example 5 and comparative examples 1-2 shows that the added high-functionality inorganic nanoparticles of the present invention cooperate with the self-healing ability to enhance the abrasion resistance of floor paints.
The floor paints of example 5 and comparative examples 1 to 3 were roller coated on the glass surface to form a coating of the same thickness, and after the coating was dried, the coating was scratched with a scratch having a width of 30 to 70 μm, then exposed to light at a temperature of 37 c, and the recovered width and percentage value were observed under an optical microscope. The self-healing rate (%) (width of scratch-width of scratch after self-healing)/× 100 width of scratch) was calculated and the time until 80% self-healing rate was reached was recorded. The results are given in table 2 below.
TABLE 2 self-repair Rate of floor finish
| Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Time/h | 1.5 | 4.3 | 4.5 | 1.5 |
As can be seen from table 2, the disulfide bond-containing polyurethane can achieve self-repair of the floor paint, but the self-repair speed can be slightly increased after the chitosan and the carboxymethyl cellulose are added, but as can be seen from example 5 and comparative example 3, if the chitosan and the carboxymethyl cellulose are introduced into the polymer chain, after the polymer is crosslinked, the self-repair capability of the floor paint can be significantly improved by using the hydrogen bond formed by the chitosan and the carboxymethyl cellulose.
In conclusion, the terrace paint disclosed by the invention adopts the terrace paint self-repairing function and the method for improving the adhesion force between the terrace paint and the substrate by increasing the high-functionality inorganic nanoparticles, so that the wear resistance of the terrace paint can be increased, the damaged paint layer can be self-repaired, the problems that the paint layer needs to be repaired and replaced due to the aggravated damage are solved, the appearance of the terrace paint is attractive, the overall performance is poor, and the cost is saved.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. The wear-resistant floor paint is characterized by comprising the following raw materials in parts by weight:
the component A comprises: 50-60 parts of disulfide bond-containing polyurethane, 10-15 parts of chitosan acrylate polymer, 0.5-2 parts of high-functionality inorganic nanoparticles, 1-5 parts of dispersing agent, 2-5 parts of pigment, 10-15 parts of deionized water and 5-10 parts of auxiliary agent; and B component: 40-60 parts of carboxymethyl cellulose modified epoxy resin, 8-15 parts of filler and 10-25 parts of deionized water.
2. The wear-resistant floor paint according to claim 1, wherein the polyurethane containing disulfide bonds is prepared by polymerization reaction of diisocyanate and 2, 2' -dithiodiethanol, and the diisocyanate is one or a combination of more than two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
3. The wear-resistant floor paint according to claim 1, wherein the chitosan acrylic polymer is prepared by the following steps:
s21, dissolving chitosan with the deacetylation degree of 80-90% and the molecular weight of 30w in an acid solution, and adding an acrylic compound for reaction to obtain chitosan acrylate;
s22, carrying out emulsion polymerization on the chitosan acrylate obtained in the step S21 by using sodium persulfate as an initiator to obtain the chitosan acrylic polymer;
the acrylic compound is one or a composition of more than two of acrylic acid, methacrylic acid, 2-ethacrylic acid and 3-methoxyacrylic acid.
4. The wear-resistant floor paint of claim 1, wherein the carboxymethyl cellulose modified epoxy resin is obtained by grafting carboxymethyl cellulose with bisphenol A epoxy resin in the presence of sodium hydroxide.
5. The wear-resistant floor paint as claimed in claim 4, wherein the bisphenol A epoxy resin is E-44 type, the carboxymethyl cellulose has an average molecular weight of 250000, a DS of 0.7 and a viscosity of 200-500 mPa.s.
6. The wear-resistant floor paint as claimed in claim 1, wherein the high-functionality inorganic nanoparticles are (a)1Na2O·a2K2O·a3Li2O)·bSiO2·cH2O, wherein a1,a2,a3≥0，a1+a2+a3＞0；b≥a1+a2+a3Inorganic nanoparticles, said inorganic nanoparticles passing through a 400-pass 600-mesh screen.
7. The wear-resistant floor paint according to claim 6, wherein the inorganic nanoparticles are prepared by the following steps:
s31, mixing sodium silicate, potassium silicate, lithium silicate and silicon dioxide to obtain a first composition;
s32, dissolving inorganic acid in water, and then mixing the inorganic acid with the first composition obtained in the step S31 to obtain the high-functionality inorganic nano-particles; the inorganic acid is phosphoric acid or boric acid.
8. The wear-resistant floor paint as claimed in claim 1, wherein the auxiliary agent is one or a combination of more than two of leveling agent, toughening agent, thickening agent, defoaming agent, wetting agent, antibacterial agent and mildew preventive.
9. The wear-resistant floor paint of claim 1, wherein the filler is one or a composition of more than two of heavy calcium carbonate powder, kaolin, talcum powder, mica powder, silica powder and quartz powder; the filler is sieved by a 400-mesh and 600-mesh sieve.
10. A method of making a wear resistant floor finish according to any one of claims 1-9, comprising the steps of:
preparing a component A mixed solution: adding the other component A substances except the disulfide bond-containing polyurethane and the chitosan acrylate polymer and deionized water into a dispersion kettle in proportion, dispersing for 30-60min in the reaction kettle at the rotation speed of 700-1200 r/min, then adding the disulfide bond-containing polyurethane and the chitosan acrylate polymer, and continuing to disperse for 30-60min at the rotation speed of 1000-1200r/min to obtain a component A mixed solution;
preparing a component B mixed solution: adding the carboxymethyl cellulose modified epoxy resin of the component B and the filler into deionized water according to a proportion, and dispersing for 30-60min under the condition of the rotating speed of 700-900r/min to obtain a component B mixed solution;
mixing: and mixing the component A mixed solution and the component B mixed solution, and uniformly stirring at the rotation speed of 1000-1200r/min to obtain the wear-resistant floor paint.
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