Elastic wear-resistant polyurethane floor material and preparation method thereof

Abstract

The invention discloses an elastic wear-resistant polyurethane floor material and a preparation method thereof. The elastic wear-resistant polyurethane floor material is prepared from the following raw materials: isocyanate, polymer polyol, chopped fibers, silane coupling agent modified nano silicon dioxide, inorganic filler, pigment, a chemical foaming agent, a physical foaming agent, an antioxidant and an ultraviolet light absorber. The preparation method of the elastic wear-resistant polyurethane floor material comprises the following steps: uniformly mixing isocyanate, chopped fiber, silane coupling agent modified nano silicon dioxide, inorganic filler, pigment, antioxidant and ultraviolet light absorber, adding polymer polyol, chemical foaming agent and physical foaming agent, and reacting. The elastic wear-resistant polyurethane floor material disclosed by the invention has high elasticity and excellent wear resistance, and is good in aging resistance, good in skid resistance, environment-friendly, odorless, long in service life, simple in preparation method, relatively low in production cost and suitable for large-scale industrial production and application.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane flooring, and in particular to an elastic wear-resistant polyurethane flooring material and a preparation method thereof. Background Art

[0002] Polyurethane flooring is a ground coating system with polyurethane (PU) resin as the main component, combined with fillers, pigments, additives and other components. It has the advantages of convenient construction, seamless beauty, good wear resistance, and good chemical corrosion resistance. It is widely used in industrial, commercial and civil fields.

[0003] Elastic polyurethane flooring has a certain elastic rebound ability, which can well absorb the impact force generated by athletes during exercise. It can not only reduce the damage to the joints and muscles of athletes, but also effectively reduce the damage caused by athletes' accidental falls, thereby providing athletes with a comfortable and safe exercise experience. It is deeply loved by athletes and is widely used in runways, stadiums, courts and other fields. At present, elastic polyurethane flooring is mainly given elastic rebound ability by adding highly elastic particles (for example: rubber particles, SPPR elastic particles, etc.). However, although polyurethane floors with added highly elastic particles have high elasticity, they generally have problems such as poor wear resistance, short service life, high production cost, and high maintenance cost, making it difficult to fully meet the requirements of actual applications.

[0004] Therefore, it is of great significance to develop a polyurethane floor material with high elasticity, excellent wear resistance and long service life.

[0005] The above statements merely provide background information related to the present invention and do not necessarily constitute prior art. Summary of the Invention

[0006] The purpose of the present invention is to provide an elastic wear-resistant polyurethane floor material and a preparation method thereof.

[0007] The technical solution adopted by the present invention is:

[0008] An elastic wear-resistant polyurethane floor material comprises the following raw materials in parts by weight:

[0009] Isocyanate: 25 to 40 parts;

[0010] Polymer polyol: 90 to 130 parts;

[0011] Chopped fiber: 5 to 15 parts;

[0012] Silane coupling agent modified nano-silica: 5 to 15 parts;

[0013] Inorganic filler: 10 to 30 parts;

[0014] Pigment: 0 to 10 parts;

[0015] Chemical foaming agent: 2 to 6 parts;

[0016] Physical foaming agent: 3 to 10 parts;

[0017] Antioxidant: 1 to 5 parts;

[0018] Ultraviolet absorber: 0.5 to 3.5 parts.

[0019] Preferably, the isocyanate is at least one of toluene diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and diphenylmethane diisocyanate (MDI).

[0020] Preferably, the polymer polyol is at least one of polyethylene glycol, polypropylene glycol, polyethylene adipate, polytetrahydrofuran, and polybutylene adipate-1,4-diol.

[0021] Preferably, the number average molecular weight of the polymer polyol is 400 g / mol to 1500 g / mol.

[0022] Preferably, the chopped fibers are at least one of aramid fibers, silk fibers, and cotton fibers.

[0023] Preferably, the length of the chopped fibers is 1 mm to 3 mm, and the diameter is 100 μm to 500 μm.

[0024] Preferably, the mass ratio of nano-silica to silane coupling agent in the nano-silica modified with silane coupling agent is 1:0.05-0.25.

[0025] Preferably, the silane coupling agent in the silane coupling agent-modified nano-silica is at least one of γ-methacryloxypropyltrimethoxysilane (silane coupling agent KH-570) and γ-glycidyloxypropyltrimethoxysilane (silane coupling agent KH-560).

[0026] Preferably, the particle size of the nano-silica modified with the silane coupling agent is 20 nm to 200 nm.

[0027] Preferably, the silane coupling agent-modified nano-silica is prepared by a preparation method comprising the following steps: dispersing nano-silica in a solvent to prepare a dispersion, adding a silane coupling agent for modification, and then separating, purifying and drying the product to obtain the silane coupling agent-modified nano-silica.

[0028] Further preferably, the silane coupling agent-modified nano-silica is prepared by a preparation method comprising the following steps: adding nano-silica to a solvent, stirring, and ultrasonically dispersing for 20 to 30 minutes to prepare a dispersion, then slowly adding the silane coupling agent, ultrasonically dispersing for 10 to 20 minutes after the addition, heating to 50° C. to 80° C. and stirring for 5 to 10 hours, naturally cooling to room temperature, centrifuging, washing the solid, and drying to obtain the silane coupling agent-modified nano-silica.

[0029] Preferably, the solvent is ethanol and water.

[0030] Preferably, the volume ratio of ethanol to water is 4 to 8:1.

[0031] Preferably, the drying is carried out at a temperature of 80° C. to 100° C., and the drying time is 5 h to 10 h.

[0032] Preferably, the inorganic filler is at least one of talc powder, montmorillonite, kaolin, alumina powder, heavy calcium carbonate powder, and precipitated barium sulfate powder.

[0033] Preferably, the pigment is at least one of iron oxide red, iron oxide yellow, carbon black, and ultramarine.

[0034] Preferably, the chemical foaming agent is at least one of sodium bicarbonate, N,N′-dinitrosopentamethylenetetramine, N,N′-dimethyl-N,N′-dinitrosoterephthalamide, azobisisobutyronitrile, 4,4′-disulfonylhydrazide diphenyl ether, p-phenylsulfonylhydrazide, 3,3′-disulfonylhydrazide diphenyl sulfone, and 4,4′-diphenyldisulfonylhydrazide.

[0035] Preferably, the physical foaming agent is at least one of n-pentane, isopentane, cyclopentane, n-hexane, n-butane, petroleum ether, and trichlorofluoromethane.

[0036] Preferably, the antioxidant is at least one of antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), antioxidant 1076 (n-octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), antioxidant 168 (tris[2,4-di-tert-butylphenyl]phosphite), antioxidant 264 (2,6-di-tert-butyl-p-cresol), antioxidant 1098 (N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine), and antioxidant 1024 (N,N'-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine).

[0037] Preferably, the ultraviolet absorber is at least one of 2-hydroxy-4-methylbenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,4-dihydroxybenzophenone.

[0038] A method for preparing the elastic wear-resistant polyurethane floor material as described above comprises the following steps:

[0039] Isocyanate, chopped fibers, nano-silica modified by a silane coupling agent, inorganic fillers, pigments, antioxidants and ultraviolet absorbers are evenly mixed, and then polymer polyols, chemical foaming agents and physical foaming agents are added and reacted to obtain an elastic and wear-resistant polyurethane floor material.

[0040] Preferably, the mixing is carried out at a temperature of 40° C. to 60° C., a stirring rate of 1000 rpm to 2000 rpm, and a mixing time of 20 min to 40 min.

[0041] Preferably, the reaction is carried out at a temperature of 70° C. to 90° C., and the reaction time is 1 h to 3 h.

[0042] An elastic floor comprises the elastic wear-resistant polyurethane floor material.

[0043] The beneficial effects of the present invention are: the elastic wear-resistant polyurethane floor material of the present invention has both high elasticity and excellent wear resistance, and has good aging resistance, good anti-slip properties, is environmentally friendly and odorless, has a long service life, a simple preparation method, and low production cost, and is suitable for large-scale industrial production and application.

[0044] Specifically:

[0045] 1) The elastic wear-resistant polyurethane floor material of the present invention has a large number of closed micropores inside, the micropores are evenly distributed and have a uniform pore size (pore size is 200μm to 800μm), which gives the polyurethane floor material high elasticity;

[0046] 2) The elastic wear-resistant polyurethane floor material of the present invention contains chopped fibers, which can significantly improve the mechanical strength of the polyurethane floor material, thereby effectively preventing the polyurethane floor material from being damaged or falling off due to external forces;

[0047] 3) The elastic wear-resistant polyurethane floor material of the present invention is added with chopped fibers, nano-silica modified with a silane coupling agent, and an inorganic filler. The synergistic effect of the three can significantly improve the wear resistance of the polyurethane floor material;

[0048] 4) The elastic wear-resistant polyurethane floor material of the present invention has good aging resistance and anti-slip properties, and has a long service life and low maintenance cost;

[0049] 5) The elastic wear-resistant polyurethane floor material of the present invention has a simple preparation method, a wide range of raw material sources, and a low production cost, and is suitable for large-scale industrial production and application. DETAILED DESCRIPTION

[0050] The present invention will be further explained and illustrated below with reference to specific embodiments.

[0051] Example 1:

[0052] An elastic wear-resistant polyurethane floor material, the raw material composition of which is shown in the following table:

[0053] Table 1 Raw material composition of elastic wear-resistant polyurethane floor material

[0054]

[0055] Note:

[0056] The preparation method of silane coupling agent modified nano-silica is as follows: nano-silica (particle size of 50nm to 100nm) is added to an ethanol-water mixed solvent (the volume ratio of ethanol to water is 5:1), the weight volume ratio of nano-silica to ethanol-water mixed solvent is 1g:30mL, and then stirred for 5min at a stirring rate of 500rpm, and then ultrasonically dispersed for 30min to prepare a dispersion liquid at an ultrasonic power of 600W, and then slowly added silane coupling agent KH-570, the mass ratio of nano-silica to silane coupling agent KH-570 is 1:0.15. After the addition, ultrasonic dispersion is continued for 15min, and then the temperature is raised to 70°C and stirred for 8h at a stirring rate of 500rpm. The mixture is naturally cooled to room temperature, centrifuged, and the solid is washed with water several times, and then placed in an oven at 90°C for 7h to obtain silane coupling agent modified nano-silica.

[0057] The preparation method of the above elastic wear-resistant polyurethane floor material is as follows:

[0058] Toluene diisocyanate, cotton fiber, silane coupling agent modified nano-silica, talcum powder, red iron oxide, antioxidant 1010 and 2-hydroxy-4-methylbenzophenone were mixed and stirred at 50°C for 30 minutes at a stirring rate of 1500 rpm, and then polyethylene glycol, sodium bicarbonate and n-pentane were added. The mixture was stirred for 5 minutes and then placed at 80°C for reaction and foaming for 2 hours to obtain an elastic and wear-resistant polyurethane floor material.

[0059] Example 2:

[0060] An elastic wear-resistant polyurethane floor material, the raw material composition of which is shown in the following table:

[0061] Table 2 Raw material composition of an elastic wear-resistant polyurethane floor material

[0062]

[0063] The preparation method of the above elastic wear-resistant polyurethane floor material is as follows:

[0064] Dicyclohexylmethane diisocyanate, aramid fiber, silane coupling agent modified nano-silica, heavy calcium carbonate powder, iron oxide yellow, antioxidant 1010 and 2-hydroxy-4-methylbenzophenone were mixed and stirred at 50°C for 30 minutes at a stirring rate of 1500 rpm, and then polyethylene glycol, sodium bicarbonate and n-hexane were added and stirred for 5 minutes. The mixture was then placed at 80°C for reaction and foaming for 2 hours to obtain an elastic and wear-resistant polyurethane floor material.

[0065] Example 3:

[0066] An elastic wear-resistant polyurethane floor material, the raw material composition of which is shown in the following table:

[0067] Table 3 Raw material composition of elastic wear-resistant polyurethane floor material

[0068]

[0069] The preparation method of the above elastic wear-resistant polyurethane floor material is as follows:

[0070] Isophorone diisocyanate, cotton fiber, silane coupling agent-modified nano-silica, precipitated barium sulfate powder, ultramarine, antioxidant 1010 and 2-hydroxy-4-n-octyloxybenzophenone were mixed and stirred at 50°C for 30 minutes at a stirring rate of 1500 rpm, and polyethylene adipate, sodium bicarbonate and n-hexane were added, and stirring was continued for 5 minutes. The mixture was then placed at 80°C for reaction and foaming for 2 hours to obtain an elastic and wear-resistant polyurethane floor material.

[0071] Example 4:

[0072] An elastic wear-resistant polyurethane floor material, the raw material composition of which is shown in the following table:

[0073] Table 4 Raw material composition of an elastic wear-resistant polyurethane floor material

[0074]

[0075]

[0076] The preparation method of the above elastic wear-resistant polyurethane floor material is as follows:

[0077] Hexamethylene diisocyanate, silk fiber, silane coupling agent-modified nano-silica, alumina powder, iron oxide yellow, antioxidant 1098 and 2,4-dihydroxybenzophenone were mixed and stirred at 50°C for 30 minutes at a stirring rate of 1500 rpm, and then polypropylene glycol, N,N′-dimethyl-N,N′-dinitrosoterephthalamide and n-hexane were added. The mixture was stirred for 5 minutes and then placed at 80°C for reaction and foaming for 2 hours to obtain an elastic and wear-resistant polyurethane floor material.

[0078] Comparative Example 1:

[0079] A polyurethane floor material is identical to the elastic wear-resistant polyurethane floor material of Example 3 except that the raw materials for its preparation do not contain cotton fibers.

[0080] Comparative Example 2:

[0081] A polyurethane floor material is identical to the elastic wear-resistant polyurethane floor material of Example 3 except that the raw materials for preparation do not contain nano-silica modified with a silane coupling agent.

[0082] Comparative Example 3:

[0083] A polyurethane floor material is identical to the elastic wear-resistant polyurethane floor material of Example 3 except that the raw materials for preparation do not contain precipitated barium sulfate powder.

[0084] Comparative Example 4:

[0085] A polyurethane floor material is identical to the elastic wear-resistant polyurethane floor material of Example 3 except that the weight of "nano-silica modified with a silane coupling agent" in the preparation raw material is replaced by "nano-silica (not modified with a silane coupling agent)".

[0086] Performance testing:

[0087] The performance test data of the elastic wear-resistant polyurethane floor materials of Examples 1 to 4 and the polyurethane floor materials of Comparative Examples 1 to 4 are shown in the following table:

[0088] Table 5 Performance test data of polyurethane floor materials

[0089]

[0090] Note:

[0091] Tensile strength: Tested in accordance with GB / T 10654-2001 Polymer porous elastic materials - Determination of tensile strength and elongation at break.

[0092] Elongation at break: Tested in accordance with GB / T 10654-2001 Polymer porous elastic materials - Determination of tensile strength and elongation at break.

[0093] Impact absorption: tested in accordance with GB / T 14833-2011 Synthetic material runway surface.

[0094] Rebound rate: tested in accordance with GB / T 14833-2011 Synthetic material runway surface.

[0095] Abrasion resistance: Tested with reference to GB / T 1768-2006 Paints and varnishes - Determination of abrasion resistance - Rotating rubber grinding wheel method.

[0096] From Table 5 we can see that:

[0097] 1) The elastic wear-resistant polyurethane floor materials of Examples 1 to 4 have high tensile strength, high elongation at break, good impact absorption, good resilience, and good wear resistance. They have excellent overall performance and are suitable for use in fields such as runways, sports fields, and courts.

[0098] 2) The tensile strength, elongation at break, and wear resistance of the polyurethane floor material of Comparative Example 1 (without cotton fiber) were significantly reduced compared to the elastic wear-resistant polyurethane floor material of Example 3, indicating that chopped fibers can significantly increase the strength of the polyurethane floor material and, in turn, improve the wear resistance of the polyurethane floor material to a certain extent.

[0099] 3) Compared with the elastic wear-resistant polyurethane floor material of Example 3, the polyurethane floor material of Comparative Example 2 (not containing nano-silica modified with a silane coupling agent) and the polyurethane floor material of Comparative Example 3 (not containing precipitated barium sulfate powder) have decreased tensile strength and elongation at break, and a significant decrease in wear resistance, indicating that the synergistic effect of chopped fibers, nano-silica modified with a silane coupling agent, and inorganic fillers can significantly improve the wear resistance of the polyurethane floor material.

[0100] 4) The tensile strength and elongation at break of the polyurethane floor material of Comparative Example 4 (nano-silica is not modified with a silane coupling agent) are reduced compared to the elastic wear-resistant polyurethane floor material of Example 3, and the wear resistance is also significantly reduced, indicating that it is crucial to modify the nano-silica with a silane coupling agent so that the nano-silica can be evenly dispersed in the polyurethane floor material system.

[0101] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. An elastic wear-resistant polyurethane floor material, characterized in that: The preparation comprises the following raw materials in parts by weight: Isocyanate: 25 to 40 parts; Polymer polyol: 90 to 130 parts; Chopped fiber: 5 to 15 parts; Silane coupling agent modified nano-silica: 5 to 15 parts; Inorganic filler: 10 to 30 parts; Pigment: 0 to 10 parts; Chemical foaming agent: 2 to 6 parts; Physical foaming agent: 3 to 10 parts; Antioxidant: 1 to 5 parts; Ultraviolet absorber: 0.5 to 3.5 parts.

2. The elastic wear-resistant polyurethane floor material according to claim 1, characterized in that: The isocyanate is at least one of toluene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate; the polymer polyol is at least one of polyethylene glycol, polypropylene glycol, polyethylene adipate, polytetrahydrofuran, and poly1,4-butylene adipate.

3. The elastic wear-resistant polyurethane floor material according to claim 1 or 2, characterized in that: The number average molecular weight of the polymer polyol is 400 g / mol to 1500 g / mol.

4. The elastic wear-resistant polyurethane floor material according to claim 1 or 2, characterized in that: The chopped fibers are at least one of aramid fibers, silk fibers, and cotton fibers; the chopped fibers have a length of 1 mm to 3 mm and a diameter of 100 μm to 500 μm.

5. The elastic wear-resistant polyurethane floor material according to claim 1 or 2, characterized in that: The mass ratio of nano-silica to silane coupling agent in the nano-silica modified by the silane coupling agent is 1:0.05-0.25; the silane coupling agent in the nano-silica modified by the silane coupling agent is at least one of γ-methacryloxypropyltrimethoxysilane and γ-glycidyloxypropyltrimethoxysilane; the particle size of the nano-silica modified by the silane coupling agent is 20nm-200nm.

6. The elastic wear-resistant polyurethane floor material according to claim 1 or 2, characterized in that: The inorganic filler is at least one of talc powder, montmorillonite, kaolin, alumina powder, heavy calcium carbonate powder, and precipitated barium sulfate powder.

7. The elastic wear-resistant polyurethane floor material according to claim 1 or 2, characterized in that: The chemical foaming agent is at least one of sodium bicarbonate, N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, azobisisobutyronitrile, 4,4'-disulfonylhydrazide diphenyl ether, p-phenylsulfonylhydrazide, 3,3'-disulfonylhydrazide diphenyl sulfone, and 4,4'-diphenyldisulfonylhydrazide; and the physical foaming agent is at least one of n-pentane, isopentane, cyclopentane, n-hexane, n-butane, petroleum ether, and trichlorofluoromethane.

8. The elastic wear-resistant polyurethane floor material according to claim 1 or 2, characterized in that: The antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 264, antioxidant 1098, and antioxidant 1024; the ultraviolet absorber is at least one of 2-hydroxy-4-methylbenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,4-dihydroxybenzophenone.

9. A method for preparing the elastic wear-resistant polyurethane floor material according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: uniformly mixing isocyanate, chopped fibers, nano-silica modified by a silane coupling agent, inorganic fillers, pigments, antioxidants and ultraviolet absorbers, and then adding polymer polyols, chemical foaming agents and physical foaming agents and reacting them to obtain elastic and wear-resistant polyurethane floor materials.

10. An elastic floor, characterized in that: The invention relates to a flexible and wear-resistant polyurethane floor material comprising the elastic and wear-resistant polyurethane floor material according to any one of claims 1 to 8.

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