CN113403033B - Environment-friendly floor anti-slip agent and preparation method thereof - Google Patents

Environment-friendly floor anti-slip agent and preparation method thereof Download PDF

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CN113403033B
CN113403033B CN202110764324.2A CN202110764324A CN113403033B CN 113403033 B CN113403033 B CN 113403033B CN 202110764324 A CN202110764324 A CN 202110764324A CN 113403033 B CN113403033 B CN 113403033B
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CN113403033A (en
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王永生
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Shanghai Shiqing Anti Slip Protection Technology Co ltd
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K3/14Anti-slip materials; Abrasives
    • C09K3/149Antislip compositions

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Abstract

The invention belongs to the technical field of anti-skid products, and particularly relates to an environment-friendly floor anti-skid agent and a preparation method thereof, wherein the environment-friendly floor anti-skid agent at least comprises the following components in parts by weight: 5-7 parts of villiaumite; 2-5 parts of a surfactant; 0.2-2 parts of a humectant; 0.2-1 part of dispersion stabilizer; the balance being water. The anti-slip agent of this application preparation can form the protection film that has good flexibility and have small hole on floor surface, can the take place deformation of adaptability when receiving pressure, reduces the hard friction to the protection film, increase of service life, on the other hand this protection film can and the contact object between form the effect of similar sucking disc when receiving certain pressure, further improved anti-skidding effect.

Description

Environment-friendly floor anti-slip agent and preparation method thereof
Technical Field
The invention relates to the technical field of anti-skid products, in particular to an environment-friendly floor anti-skid agent and a preparation method thereof.
Background
The floor board as building decoration material has rich variety, has various decorative patterns, can obviously improve the decoration effect of decoration, and is popular. Because the surfaces of the products are very smooth, the products have beautifying and decorating effects, but also bring about the major potential safety hazard problem of smooth ground, and people usually only pay attention to the integral visual effect of decoration and ignore the ground anti-skidding problem in the decorating process. According to statistics, the casualties caused by slip accidents every year are only second to car accidents in daily life, wherein the ground slip prevention is the major problem of safety as children, old people, pregnant women and mobility-handicapped people are the most serious, and along with the improvement of safety consciousness and the popularization of people-oriented ideas, the requirements of people on floor products are certainly improved from the requirement of simply pursuing decorative effects to the requirement of having beautifying decorative effects and safer use.
At present, there are two main measures for preventing the floor from slipping: one is to make the surface of the brick into stripes with concave-convex grooves or other shapes to enhance the friction coefficient of the surface of the floor and realize the anti-skid function, but the floor tile prepared by the method has the concave-convex grooves on the surface, thus affecting the beauty to a certain extent, and on the other hand, being easy to hide dirt and being difficult to clean; the other is to paint an anti-slip agent on the surface of the floor, the anti-slip agent attached to the surface of the brick body is utilized to improve the friction coefficient, but the existing anti-slip agent on the market has weak seepage force and the painted anti-slip layer is easy to wear.
Patent application No. 201910780771.X provides a ceramic tile anti-slip agent and preparation method thereof, through regard hypochlorous acid and hydrochloric acid as the main raw materials who corrodes the ceramic tile brick face, fluoride salt and penetrant supplementary corruption, form a large amount of miniature recesses at the ceramic tile brick face, when the ceramic tile that anti-skidding was handled is stepped on to the foot, polymer expanded material pressurized will be extruded in polymer expanded material's gas, promote polymer expanded material adsorbs the instep, increase anti-skidding effect, improve the bright effect of ceramic tile with the help of the brightener.
The patent with the application number of 201710627403.2 provides a formula and a preparation method of an anti-slip agent for floor tiles, wherein the formula comprises octadecanol polyoxyethylene ether OP-10, ammonium fluosilicate, a surfactant A, a surfactant B, sodium chloride, tartaric acid and water, so that the anti-slip agent can effectively permeate and widen capillary channels of the floor tiles, pits cannot be seen by naked eyes are formed on the anti-slip agent, physical sucking disc action can be formed by contact with soles when water or oil stains are encountered, but the surface gloss of the floor is reduced after the floor is corroded.
Disclosure of Invention
The invention provides an environment-friendly floor anti-slip agent and a preparation method thereof, aiming at solving the problems that the glossiness of the floor surface is reduced and an anti-slip layer is easy to wear caused by the existing anti-slip agent.
The technical scheme for solving the problems is as follows:
the environment-friendly floor anti-slip agent at least comprises the following components in parts by weight:
5-7 parts of villiaumite;
2-5 parts of a surfactant;
0.2-2 parts of a humectant;
0.2-1 part of dispersion stabilizer;
the balance of water;
the general formula of the surfactant is as follows:
Figure BDA0003150447970000031
in the formula, R is C3~C5An alkyl group.
The invention has the following beneficial effects: nitrogen atoms carry positive charges in the synthesized surfactant and generate stronger adsorption force with the floor, the adhesive force between the synthesized surfactant and the floor is improved, and the synthesized surfactant has the property of carboxyl modified silicone oil, so that the synthesized surfactant has good flexibility, can be adaptively deformed when being subjected to certain pressure, reduces the hard friction of a protective film, prolongs the service life, improves the smooth property of the surface of the organic silicon, increases the surface friction, plays a role in skid resistance, can form the effect similar to a sucker with the sole by combining the protective film, and further improves the anti-skid effect.
Drawings
FIG. 1 is a SEM image of a coating layer formed by coating the anti-slip agent obtained in example 6 in the present invention.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Low hydrogen silicone oil CAS number 63148-57-2; trans-3-pentenoic acid CAS number 1617-32-9; triethanolamine CAS number 102-71-6; valeric acid CAS number 109-52-4; phosphorous acid CAS number 13598-36-2; copper sulfate CAS number 7758-99-8; n-butyric acid CAS number 107-92-6; caproic acid CAS number 142-62-1; ammonium acid fluoride CAS number 1341-49-7; propylene glycol CAS number 57-55-6; butanediol CAS number 107-88-0; ethylene glycol Ether CAS number 110-80-5. All chemicals were commercially available in a nitrogen purity of 99%.
Example 1
This example provides a method for preparing a surfactant:
the method comprises the following specific steps:
s1: adding 150ml of low-hydrogen silicone oil and 100ml of trans-3-pentenoic acid into a reaction bottle, simultaneously dropwise adding chloroplatinic acid-isopropanol into the reaction bottle to serve as a catalyst, starting stirring, heating to 100 ℃, and reacting for 6 hours to obtain transparent viscous liquid, namely an intermediate I, wherein the reaction equation is as follows:
Figure BDA0003150447970000041
s2: adding 60ml of triethanolamine and 100ml of valeric acid into a reaction bottle, adding 5g of phosphorous acid as a catalyst, introducing nitrogen, stirring, heating to 180 ℃, and reacting for 4 hours to obtain an oily substance, namely an intermediate II, wherein in the esterification reaction process, fatty acid reacts with the triethanolamine to generate a mixture of mono, di and tri fatty acid triethanolamine esters, wherein the main reaction equation is as follows:
Figure BDA0003150447970000042
s3: mixing the intermediate I obtained in the step S1 with the intermediate II obtained in the step II, adding 8g of copper sulfate, stirring, heating to 125 ℃, reacting for 4.5 hours, filtering to remove the copper sulfate, wherein the obtained oily matter is a target product, in the esterification reaction process, the inventor adopts the copper sulfate as a catalyst, on one hand, the copper sulfate is difficult to dissolve in alcohol, acid and ester, and after the reaction is finished, the copper sulfate can be separated only by filtering, so that the separation process is simplified, on the other hand, the copper sulfate has stable performance and good repeatability in the use process, and can be repeatedly used after the reaction, the filtration and the separation, so that the cost is saved, and the reaction equation is as follows:
Figure BDA0003150447970000051
the silicone oil is polyorganosiloxane with chain structure of different polymerization degrees, all organic groups of the polyorganosiloxane are methyl, the polyorganosiloxane has good hydrophobicity, excellent thermal oxidation stability and strong anti-foaming property, the low-hydrogen silicone oil has the characteristics of the silicone oil, and can generate addition reaction and crosslinking reaction due to the active hydrogen, the low-hydrogen silicone oil is modified to form carboxyl modified silicone oil, so that the carboxyl modified silicone oil has good flexibility, the smooth property of the surface of the silicone oil is reduced, the surface friction force is increased, a better anti-skid effect is achieved, meanwhile, triethanolamine is subjected to esterification reaction with fatty acid to generate a product mainly comprising fatty acid triethanolamine ester, the generated fatty acid triethanolamine ester is subjected to grafting reaction with the carboxyl modified silicone oil under the catalysis of copper sulfate, and the generated fatty acid triethanolamine ester is easy to interact with other atoms due to the existence of lone pair electrons on nitrogen atoms and has strong adsorption force on the surfaces of various solid substances and materials, the synthetic surfactant has the advantages that the adsorption performance on the floor surface is improved due to the existence of nitrogen atoms, the modified silicone oil has the property of flexibility, and meanwhile, the good glossiness of the surface of an object can be kept.
Example 2
This example provides a method for preparing a surfactant:
the method comprises the following specific steps:
s1: adding 150ml of low-hydrogen silicone oil and 100ml of trans-3-pentenoic acid into a reaction bottle, simultaneously dropwise adding chloroplatinic acid-isopropanol into the reaction bottle to serve as a catalyst, starting stirring, heating to 100 ℃, and reacting for 6 hours to obtain transparent viscous liquid, namely an intermediate I;
s2: adding 60ml of triethanolamine and 100ml of n-butyric acid into a reaction bottle, adding 5g of phosphorous acid as a catalyst, introducing nitrogen, stirring, heating to 180 ℃, and reacting for 4 hours to obtain an oily substance, namely an intermediate II, wherein in the esterification reaction process, fatty acid and triethanolamine react to generate a mixture of mono, di and tri fatty acid triethanolamine ester, wherein a diester product is mainly used;
s3: mixing the intermediate I obtained in the step S1 with the intermediate II obtained in the step II, adding 8g of copper sulfate, stirring, heating to 125 ℃, reacting for 4.5 hours, filtering to remove the copper sulfate, wherein the obtained oily matter is a target product.
Example 3
This example provides a method for preparing a surfactant:
the method comprises the following specific steps:
s1: adding 150ml of low-hydrogen silicone oil and 100ml of trans-3-pentenoic acid into a reaction bottle, simultaneously dropwise adding chloroplatinic acid-isopropanol into the reaction bottle to serve as a catalyst, starting stirring, heating to 100 ℃, and reacting for 6 hours to obtain transparent viscous liquid, namely an intermediate I;
s2: adding 60ml of triethanolamine and 100ml of caproic acid into a reaction bottle, adding 5g of phosphorous acid as a catalyst, introducing nitrogen, stirring, heating to 180 ℃, and reacting for 4 hours to obtain an oily substance, namely an intermediate II, wherein in the esterification reaction process, fatty acid reacts with the triethanolamine to generate a mixture of mono, bi and tri fatty acid triethanolamine ester, wherein a diester product is mainly used;
s3: mixing the intermediate I obtained in the step S1 with the intermediate II obtained in the step II, adding 8g of copper sulfate, stirring, heating to 125 ℃, reacting for 4.5 hours, filtering to remove the copper sulfate, wherein the obtained oily matter is a target product.
Example 4
The embodiment provides an environment-friendly floor anti-slip agent and a preparation method thereof:
the environment-friendly floor anti-slip agent at least comprises the following components in parts by weight:
5 parts of villiaumite, 2 parts of surfactant, 0.2 part of humectant, 0.2 part of dispersion stabilizer and the balance of water, wherein the villiaumite is ammonium bifluoride, the surfactant is the target product prepared in the embodiment 1, the humectant comprises propylene glycol and butanediol, and the dispersion stabilizer is ethylene glycol ethyl ether.
A preparation method of an environment-friendly floor anti-slip agent comprises the following steps: adding 5 parts of villiaumite into water, and stirring at the rotating speed of 800-1000 rpm for 20 min; and adding 2 parts of surfactant, stirring at the rotating speed of 1000-1100 rpm for 30min, adding 0.2 part of humectant and 0.2 part of dispersion stabilizer, and uniformly stirring to obtain the required environment-friendly floor anti-slip agent.
Example 5
The embodiment provides an environment-friendly floor anti-slip agent and a preparation method thereof:
the environment-friendly floor anti-slip agent at least comprises the following components in parts by weight:
7 parts of villiaumite, 5 parts of surfactant, 2 parts of humectant, 1 part of dispersion stabilizer and the balance of water, wherein the villiaumite is ammonium bifluoride, the surfactant is the target product prepared in the embodiment 1, the humectant comprises propylene glycol and butanediol, and the dispersion stabilizer is ethylene glycol ethyl ether.
A preparation method of an environment-friendly floor anti-slip agent comprises the following steps: adding 7 parts of villiaumite into water, and stirring at the rotating speed of 800-1000 rpm for 20 min; and adding 5 parts of surfactant, stirring at the rotating speed of 1000-1100 rpm for 30min, adding 2 parts of humectant and 1 part of dispersion stabilizer, and uniformly stirring to obtain the required environment-friendly floor anti-slip agent.
Example 6
The embodiment provides an environment-friendly floor anti-slip agent and a preparation method thereof:
the environment-friendly floor anti-slip agent at least comprises the following components in parts by weight:
6 parts of villiaumite, 3 parts of surfactant, 1.2 parts of humectant, 0.5 part of dispersion stabilizer and the balance of water, wherein the villiaumite is ammonium bifluoride, the surfactant is the target product prepared in the embodiment 1, the humectant comprises propylene glycol and butanediol, and the dispersion stabilizer is ethylene glycol ethyl ether.
A preparation method of an environment-friendly floor anti-slip agent comprises the following steps: adding 6 parts of villiaumite into water, stirring for 20min at the rotating speed of 800-1000 rpm, adding 3 parts of surfactant, stirring for 30min at the rotating speed of 1000-1100 rpm, adding 1.2 parts of humectant and 0.5 part of dispersion stabilizer, and uniformly stirring to obtain the required environment-friendly floor anti-slip agent.
Performance testing
The performance of the environment-friendly floor anti-slip agents prepared in examples 4 to 6 was tested, wherein the comparative example was a certain domestic product of the same type.
(1) And (3) testing the friction coefficient: the floor was tested for coefficient of friction slip in both dry and wet conditions.
Dry friction coefficient test: and (3) treating the surface of the floor by using an anti-slip agent, and drying the floor treated by using the anti-slip agent at 30 ℃ for 60 min.
Testing the wet friction coefficient: the anti-slip agent treated floor surface was wetted with distilled water and subjected to a coefficient of friction test.
(2) And (3) testing the glossiness: the gloss of the anti-slip agent treated floor was tested in the dry state using a gloss tester model WGG60-E4, manufactured by Coishika photoelectric instruments Inc.
The results data are shown in Table 1
TABLE 1
Figure BDA0003150447970000081
Figure BDA0003150447970000091
As can be seen from the analysis of Table 1, the environmentally-friendly floor anti-slip agent prepared by the invention improves the friction coefficient of the floor surface in the dry state and the wet state, can maintain better glossiness, and realizes the capability of maintaining good glossiness under the condition of no addition of a brightening agent, and comparative examples 4-6 find that the effect of example 6 is the best, probably because the addition amount of each effective component in example 4 is small, the effect is relatively poor, for example 5, the effect is relatively poor probably because the addition amount of each effective component is large, and the components are not uniformly dispersed, and the test effect of example 6 is the best.
The environmental-friendly floor anti-slip agent prepared in example 6 was tested by a field emission scanning electron microscope. The obtained result is shown in figure 1, and it can be seen from the figure that the environment-friendly floor anti-slip agent prepared by the invention forms a protective film on the surface of the floor, and a plurality of tiny holes are uniformly distributed on the formed protective film, because the protective film has flexibility, the protective film can be deformed adaptively when being pressed, when the protective film is contacted with the sole, the air in the holes is extruded and transferred to form the function similar to a sucker with the sole under the action of atmospheric pressure, the friction between the sole and the contact surface is increased, and a good anti-skid effect is achieved, when ground met water, downthehole by water full, when people passed through this ground this moment, the protection film received certain pressure, and deformation takes place thereupon, and the moisture pressurized of downthehole gathering is extruded from downthehole, forms similar sucking disc effect with the sole equally, consequently no matter all has good anti-skidding effect under the condition that dry or have water to exist.
When the anti-skid organic silicon protective film is used specifically, nitrogen atoms in the synthesized surfactant carry positive charges to generate stronger adsorption force with a floor, so that the adhesive force between the synthetic surfactant and the floor is improved, and the synthetic surfactant has the property of carboxyl modified silicone oil, so that the synthetic surfactant has good flexibility, can deform adaptively when being subjected to certain pressure, reduces the hard friction on the protective film, prolongs the service life, improves the smooth property of the surface of the organic silicon, increases the surface friction force, plays a role in skid resistance, and can form a function similar to a sucker with a sole by combining the protective film, thereby further improving the anti-skid effect.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present application have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.

Claims (2)

1. The environment-friendly floor anti-slip agent is characterized by at least comprising the following components in parts by weight:
5-7 parts of villiaumite;
2-5 parts of a surfactant;
0.2-2 parts of a humectant;
0.2-1 part of dispersion stabilizer;
the balance of water;
the fluorine salt is ammonium bifluoride;
the humectant is at least one of butanediol, propylene glycol, glycerol, polyethylene glycol and hexanediol;
the dispersion stabilizer is at least one of ethylene glycol ethyl ether, ethylene glycol butyl ether, diethanol amine, triethanol amine, dipropylene glycol methyl ether and propylene glycol phenyl ether;
the preparation method of the surfactant comprises the following steps:
s1: adding 150ml of low-hydrogen silicone oil and 100ml of trans-3-pentenoic acid into a reaction bottle, simultaneously dropwise adding chloroplatinic acid-isopropanol into the reaction bottle to serve as a catalyst, starting stirring, heating to 100 ℃, and reacting for 6 hours to obtain transparent viscous liquid, namely an intermediate I, wherein the reaction equation is as follows:
Figure FDA0003510414600000011
s2: adding 60ml of triethanolamine and 100ml of valeric acid into a reaction bottle, adding 5g of phosphorous acid as a catalyst, introducing nitrogen, stirring, heating to 180 ℃, and reacting for 4 hours to obtain an oily substance, namely an intermediate II, wherein in the esterification reaction process, fatty acid reacts with the triethanolamine to generate a mixture of mono, di and tri fatty acid triethanolamine esters, wherein the main reaction equation is as follows:
Figure FDA0003510414600000021
s3: mixing the intermediate I obtained in the step S1 with the intermediate II obtained in the step II, adding 8g of copper sulfate, stirring, heating to 125 ℃, reacting for 4.5 hours, filtering to remove the copper sulfate, wherein the obtained oily matter is the target product, and the reaction equation is as follows:
Figure FDA0003510414600000022
2. the method for preparing the environment-friendly floor anti-slip agent according to claim 1, wherein the method comprises the following steps: adding villiaumite into water, and stirring for 20min at the rotating speed of 800-1000 rpm; adding a surfactant, stirring for 30min at the rotating speed of 1000-1100 rpm, adding a humectant and a dispersion stabilizer, and uniformly stirring.
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