Environment-friendly foaming polyurethane coiled material as well as preparation process and application thereof

Abstract

The invention discloses an environment-friendly foaming polyurethane coiled material as well as a preparation process and application thereof. The environment-friendly foaming polyurethane coiled material comprises the following preparation raw materials in parts by weight: 100 parts of thermoplastic polyurethane; 5 parts to 15 parts of glass fiber gridding cloth; 3 to 10 parts of chopped fiber; 8 parts to 20 parts of inorganic filler; 0 to 10 parts of pigment; 5-15 parts of an inorganic foaming agent; 0.5 to 2 parts of a silane coupling agent; 3 to 10 parts of an antioxidant; and 0.5 to 3.5 parts of an ultraviolet light absorber. The environment-friendly foaming polyurethane coiled material has the advantages of high elasticity, high mechanical strength, excellent wear resistance, good aging resistance, good skid resistance, safety, environmental protection, no odor, long service life, simple preparation method and low production cost, and is suitable for large-scale industrial production and application.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyurethane floor, in particular to an environment-friendly foamed polyurethane coiled material and its preparation process and application. BACKGROUND

[0002] The polyurethane coiled material is a high-performance polymer material product, which has the advantages of good waterproofness, large elasticity, good flexibility, good wear resistance, good weather resistance and the like, and flexible construction mode (various processes such as cold bonding, hot melting and welding can be adopted, which can adapt to different engineering requirements), and is widely used in industrial, commercial and civil fields. The polyurethane coiled material has large elasticity, can effectively absorb the impact force generated by the runner on the ground during the movement, and has a good buffering effect, which not only can reduce the damage to the joints and muscles of the runner, but also can effectively reduce the physical injury caused by accidental falling of the runner, so as to provide a comfortable and safe movement experience for the runner, and is deeply loved by the runner, and is widely used in the fields of running track, sports field and playground. However, the existing polyurethane coiled material generally has the problems of low elasticity, low mechanical strength (weak anti-puncture and anti-tear ability), low wear resistance, contains toxic and harmful components (part of the polyurethane coiled material contains harmful substances such as free TDI, which will release irritating gas during construction, which will endanger the health of the construction personnel), short service life and the like, which is difficult to completely meet the actual application requirements.

[0003] Therefore, it is of great significance to develop a polyurethane coiled material with high elasticity, high mechanical strength, excellent wear resistance, safety, environmental protection, no odor and long service life.

[0004] The above statements only provide background information related to the present application, and do not necessarily constitute the prior art. SUMMARY

[0005] The purpose of the present application is to provide an environment-friendly foamed polyurethane coiled material and its preparation process and application.

[0006] The technical scheme adopted by the present application is:

[0007] An environment-friendly foamed polyurethane coiled material comprises the following preparation raw materials by weight:

[0008] Thermoplastic polyurethane: 100 parts;

[0009] Glass fiber mesh cloth: 5-15 parts;

[0010] Short cut fiber: 3-10 parts;

[0011] Inorganic filler: 8-20 parts;

[0012] Pigment: 0-10 parts;

[0013] Inorganic foaming agent: 5-15 parts;

[0014] Silane coupling agent: 0.5-2 parts;

[0015] Antioxidant: 3-10 parts;

[0016] UV absorber: 0.5-3.5 parts.

[0017] Preferably, the mesh size of the glass fiber mesh is 4-8 mm.

[0018] Preferably, the chopped fiber is at least one of cotton fiber, silk fiber, aramid fiber.

[0019] Preferably, the length of the chopped fiber is 1-3 mm, and the diameter is 100-500 μm.

[0020] Preferably, the inorganic filler is at least one of talc powder, alumina powder, montmorillonite, kaolin, heavy calcium carbonate powder, and precipitated barium sulfate powder.

[0021] Preferably, the inorganic foaming agent is at least one of sodium bicarbonate and ammonium sulfate.

[0022] 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-glycidyl ether propyltrimethoxysilane (silane coupling agent KH-560).

[0023] Preferably, the antioxidant is at least one of antioxidant 1010 (tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester), antioxidant 1076 (β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester), 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).

[0024] Preferably, the UV absorber is at least one of 2-hydroxy-4-methylbenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,4-dihydroxybenzophenone.

[0025] Preferably, the cells in the environmentally friendly foamed polyurethane coiled material are closed cells with a pore size of 50-150 μm.

[0026] Preferably, the environmentally friendly foamed polyurethane coil comprises at least one layer of glass fiber mesh cloth.

[0027] A preparation process of the above-mentioned environmentally friendly foamed polyurethane coil comprises the following steps:

[0028] 1) dispersing a silane coupling agent with a solvent and spraying the dispersed silane coupling agent on the surface of a glass fiber mesh, followed by drying to obtain a silane coupling agent-modified glass fiber mesh;

[0029] 2) Laying a glass fiber mesh cloth modified with a silane coupling agent in a mold, then uniformly mixing thermoplastic polyurethane, chopped fibers, inorganic fillers, pigments, inorganic foaming agents, antioxidants, and ultraviolet absorbers, injecting the mixture into the mold, and then foaming the mixture to obtain an environmentally friendly foamed polyurethane coil.

[0030] Preferably, the solvent in step 1) is at least one of water and ethanol.

[0031] Preferably, the drying in step 1) is carried out at a temperature of 80° C. to 100° C., and the drying time is 20 min to 40 min.

[0032] Preferably, the mixing method in step 2) is melt blending, and the melt blending temperature is controlled at 160° C. to 190° C. (to avoid decomposition of the inorganic foaming agent).

[0033] Preferably, the equipment used for mixing in step 2) is a twin-screw extruder or an internal mixer.

[0034] Preferably, the foaming molding in step 2) is carried out at a temperature of 200° C. to 230° C., and the foaming molding time is 20 min to 40 min.

[0035] An elastic floor, the surface of which is paved with the above-mentioned environmentally friendly foamed polyurethane coiled material.

[0036] The beneficial effects of the present invention are: the environmentally friendly foamed polyurethane coil of the present invention has high elasticity and high mechanical strength, and has excellent wear resistance, good aging resistance, good anti-slip properties, safety, environmental protection, odorlessness, long service life, simple preparation method, low production cost, and is suitable for large-scale industrial production and application.

[0037] Specifically:

[0038] 1) The interior of the environmentally friendly foamed polyurethane coil of the present invention contains a large number of closed micropores, which are evenly distributed and have a uniform pore size (pore size is 50μm to 150μm), giving the polyurethane coil high elasticity;

[0039] 2) The glass fiber mesh cloth modified by the silane coupling agent added in the environment-friendly foamed polyurethane coiled material of the present application has good compatibility with the thermoplastic polyurethane system, can greatly improve the mechanical strength (strong puncture resistance and tear resistance) and wear resistance of the polyurethane coiled material, effectively reduces the damage of the polyurethane coiled material caused by external force, and prolongs the service life of the polyurethane coiled material;

[0040] 3) The chopped fibers added in the environment-friendly foamed polyurethane coiled material of the present application can further improve the mechanical strength and wear resistance of the polyurethane coiled material;

[0041] 4) The glass fiber mesh cloth modified by the silane coupling agent, the chopped fibers and the inorganic filler added in the environment-friendly foamed polyurethane coiled material of the present application have a synergistic effect, which can significantly improve the mechanical strength and wear resistance of the polyurethane coiled material;

[0042] 5) The antioxidants and ultraviolet absorbers added in the environment-friendly foamed polyurethane coiled material of the present application can significantly improve the aging resistance of the polyurethane coiled material, and prolong the service life of the polyurethane coiled material;

[0043] 6) The environment-friendly foamed polyurethane coiled material of the present application has good aging resistance, good anti-skid property, safety, environmental protection and no odor, long service life and low maintenance cost;

[0044] 7) The preparation method of the environment-friendly foamed polyurethane coiled material of the present application is simple, the raw materials are widely available, the production cost is low, and it is suitable for large-scale industrial production and application. DETAILED DESCRIPTION

[0045] The present application will be further explained and described below in combination with specific examples.

[0046] Example 1:

[0047] An environment-friendly foamed polyurethane coiled material, the raw material composition of which is shown in the following table:

[0048] Table 1 Raw material composition table of an environment-friendly foamed polyurethane coiled material

[0049]

[0050] The preparation process of the above-mentioned environment-friendly foamed polyurethane coiled material is as follows:

[0051] 1) The silane coupling agent KH-570 is dispersed in water and then sprayed on the surface of the glass fiber mesh cloth, and then dried at a temperature of 90℃ for 20min, and naturally cooled to room temperature to obtain the glass fiber mesh cloth modified by the silane coupling agent;

[0052] 2) The silane coupling agent modified glass fiber mesh is laid (single layer laying) in the mold, and then the thermoplastic polyurethane, cotton fiber, precipitated barium sulfate powder, iron oxide red, sodium bicarbonate, antioxidant 1010 and 2-hydroxy-4-methyl benzophenone are added into a double screw extruder for melt blending, and then injected into the mold, the temperature of melt blending is controlled at 160°C, and then foamed and formed at a temperature of 220°C for 30 min, and naturally cooled to room temperature to obtain the environment-friendly foamed polyurethane coiled material.

[0053] Example 2:

[0054] An environment-friendly foamed polyurethane coiled material, the raw material composition of which is shown in the following table:

[0055] Table 2 Raw material composition table of an environment-friendly foamed polyurethane coiled material

[0056]

[0057]

[0058] The preparation process of the above-mentioned environment-friendly foamed polyurethane coiled material is as follows:

[0059] 1) The silane coupling agent KH-570 is dispersed with water and then sprayed on the surface of the glass fiber mesh, and then dried at a temperature of 90°C for 20 min, and naturally cooled to room temperature to obtain the silane coupling agent modified glass fiber mesh;

[0060] 2) The silane coupling agent modified glass fiber mesh is laid (single layer laying) in the mold, and then the thermoplastic polyurethane, aramid fiber, talc powder, iron oxide yellow, ammonium sulfate, antioxidant 1010 and 2-hydroxy-4-methyl benzophenone are added into a double screw extruder for melt blending, and then injected into the mold, the temperature of melt blending is controlled at 180°C, and then foamed and formed at a temperature of 230°C for 40 min, and naturally cooled to room temperature to obtain the environment-friendly foamed polyurethane coiled material.

[0061] Example 3:

[0062] An environment-friendly foamed polyurethane coiled material, the raw material composition of which is shown in the following table:

[0063] Table 3 Raw material composition table of an environment-friendly foamed polyurethane coiled material

[0064]

[0065]

[0066] The preparation process of the above-mentioned environment-friendly foamed polyurethane coiled material is as follows:

[0067] 1) The silane coupling agent KH-570 is dispersed in water and then sprayed on the surface of the glass fiber mesh, and then dried at a temperature of 90°C for 20 min, and naturally cooled to room temperature to obtain a silane coupling agent modified glass fiber mesh;

[0068] 2) The silane coupling agent modified glass fiber mesh is laid (double layer interval) in the mold, and then the thermoplastic polyurethane, cotton fiber, precipitated barium sulfate powder, ultramarine blue, sodium bicarbonate, antioxidant 1010, antioxidant 168 and 2-hydroxy-4-methyl benzophenone are added to the twin-screw extruder for melt blending, and then injected into the mold, and the temperature of melt blending is controlled at 160°C, and then foamed and molded at a temperature of 220°C for 30 min, and naturally cooled to room temperature to obtain an environmentally friendly foamed polyurethane coiled material.

[0069] Example 4:

[0070] An environmentally friendly foamed polyurethane coiled material, the raw material composition of which is shown in the following table:

[0071] Table 4 Raw material composition table of an environmentally friendly foamed polyurethane coiled material

[0072]

[0073] The preparation process of the above environmentally friendly foamed polyurethane coiled material is as follows:

[0074] 1) The silane coupling agent KH-560 is dispersed in water and then sprayed on the surface of the glass fiber mesh, and then dried at a temperature of 90°C for 20 min, and naturally cooled to room temperature to obtain a silane coupling agent modified glass fiber mesh;

[0075] 2) The silane coupling agent modified glass fiber mesh is laid (double layer interval) in the mold, and then the thermoplastic polyurethane, silk fiber, heavy calcium carbonate powder, red iron oxide, ammonium sulfate, antioxidant 1010 and 2-hydroxy-4-n-octyloxy benzophenone are added to the twin-screw extruder for melt blending, and then injected into the mold, and the temperature of melt blending is controlled at 180°C, and then foamed and molded at a temperature of 230°C for 40 min, and naturally cooled to room temperature to obtain an environmentally friendly foamed polyurethane coiled material.

[0076] Comparative Example 1:

[0077] An environmentally friendly foamed polyurethane coiled material, except that it does not contain silane coupling agent modified glass fiber mesh, and the rest is exactly the same as the environmentally friendly foamed polyurethane coiled material of Example 3.

[0078] Comparative Example 2:

[0079] An environment-friendly foamed polyurethane coiled material, which is completely same as the environment-friendly foamed polyurethane coiled material of Example 3 except that the preparation raw material does not contain silane coupling agent KH-570 (i.e. the glass fiber mesh is not surface modified by silane coupling agent KH-570).

[0080] Comparative Example 3:

[0081] An environment-friendly foamed polyurethane coiled material, which is completely same as the environment-friendly foamed polyurethane coiled material of Example 3 except that the preparation raw material does not contain cotton fiber.

[0082] Comparative Example 4:

[0083] An environment-friendly foamed polyurethane coiled material, which is completely same as the environment-friendly foamed polyurethane coiled material of Example 3 except that the preparation raw material does not contain precipitated barium sulfate powder.

[0084] Performance test:

[0085] The performance test data of the environment-friendly foamed polyurethane coiled materials of Examples 1-4 and Comparative Examples 1-4 are shown in the following table:

[0086] Table 5 Performance test data of environment-friendly foamed polyurethane coiled materials

[0087]

[0088]

[0089] Note:

[0090] Micropore aperture: The environment-friendly foamed polyurethane coiled material is cut open, and then the cross section is observed and photographed by using a microscope, and the micropore aperture range is measured and counted.

[0091] Tensile strength: tested according to "GB / T 10654-2001 Determination of tensile strength and elongation at break of cellular polymeric elastic materials".

[0092] Impact absorption: tested according to "GB / T 14833-2011 Synthetic materials for runway surfacing".

[0093] Rebound rate: tested according to "GB / T 14833-2011 Synthetic materials for runway surfacing".

[0094] Wear resistance: tested according to "GB / T 1768-2006 Determination of abrasion resistance of pigmented and clear coatings - Rotary rubber wheel method".

[0095] From Table 5, it can be seen that:

[0096] 1) The micro-porous polyurethane foam roll of the environment-friendly type of Examples 1-4 has uniform micro-porous pore size, high tensile strength, good impact absorption performance, good resilience, good wear resistance, is safe, environmentally friendly and odorless, and has very excellent comprehensive performance, and is suitable for use in fields such as runways, sports fields, and ball courts;

[0097] 2) The environment-friendly polyurethane foam roll of Comparative Example 1 (not containing the glass fiber mesh cloth modified by the silane coupling agent) has a significantly decreased tensile strength and wear resistance compared with the environment-friendly polyurethane foam roll of Example 3, indicating that the glass fiber mesh cloth modified by the silane coupling agent can significantly improve the mechanical strength and wear resistance of the polyurethane roll;

[0098] 3) The environment-friendly polyurethane foam roll of Comparative Example 2 (not containing the silane coupling agent KH-570) has a significantly decreased tensile strength and wear resistance compared with the environment-friendly polyurethane foam roll of Example 3, indicating that the surface modification of the glass fiber mesh cloth by the silane coupling agent is a necessary operation, and this modification operation can significantly improve the compatibility of the glass fiber mesh cloth with the thermoplastic polyurethane system, thereby significantly improving the mechanical strength and wear resistance of the polyurethane roll;

[0099] 4) The environment-friendly polyurethane foam roll of Comparative Example 3 (not containing the cotton fiber) has a significantly decreased tensile strength and wear resistance compared with the environment-friendly polyurethane foam roll of Example 3, indicating that the short fibers can significantly improve the mechanical strength of the polyurethane foam roll, and thereby improve the wear resistance of the polyurethane foam roll;

[0100] 5) The environment-friendly polyurethane foam roll of Comparative Example 4 (not containing the precipitated barium sulfate powder) has not only a decreased tensile strength, but also a significantly decreased wear resistance compared with the environment-friendly polyurethane foam roll of Example 3, indicating that the inorganic filler can significantly improve the mechanical strength and wear resistance of the polyurethane roll;

[0101] From the above, it can be seen that the synergistic effect of the glass fiber mesh cloth modified by the silane coupling agent, the short fibers and the inorganic filler can significantly improve the wear resistance of the polyurethane roll.

[0102] The above examples are preferred embodiments of the present application, but the embodiments of the present application are not limited by the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application should be equivalent replacement methods, and are all included in the protection scope of the present application.

Claims

1. An environmentally friendly foamed polyurethane coil, characterized in that: The preparation comprises the following raw materials in parts by weight: Thermoplastic polyurethane: 100 parts; Glass fiber mesh: 5 to 15 parts; Chopped fiber: 3 to 10 parts; Inorganic filler: 8 to 20 parts; Pigment: 0 to 10 parts; Inorganic foaming agent: 5 to 15 parts; Silane coupling agent: 0.5 to 2 parts; Antioxidant: 3 to 10 parts; Ultraviolet absorber: 0.5 to 3.5 parts.

2. The environmentally friendly foamed polyurethane coil according to claim 1, characterized in that: The mesh side length of the glass fiber mesh cloth is 4 mm to 8 mm.

3. The environmentally friendly foamed polyurethane coil according to claim 1, characterized in that: The chopped fibers are at least one of cotton fibers, silk fibers, and aramid fibers; the chopped fibers have a length of 1 mm to 3 mm and a diameter of 100 μm to 500 μm.

4. The environmentally friendly foamed polyurethane coil according to any one of claims 1 to 3, characterized in that: The inorganic filler is at least one of talc powder, alumina powder, montmorillonite, kaolin, heavy calcium carbonate powder, and precipitated barium sulfate powder.

5. The environmentally friendly foamed polyurethane coil according to any one of claims 1 to 3, characterized in that: The inorganic foaming agent is at least one of sodium bicarbonate and ammonium sulfate.

6. The environmentally friendly foamed polyurethane coil according to any one of claims 1 to 3, characterized in that: The silane coupling agent is at least one of γ-methacryloxypropyltrimethoxysilane and γ-glycidyloxypropyltrimethoxysilane.

7. The environmentally friendly foamed polyurethane coil according to any one of claims 1 to 3, 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.

8. The environmentally friendly polyurethane foam coil according to any one of claims 1 to 3, characterized in that: The cells in the environmentally friendly foamed polyurethane coil are closed micropores with a pore diameter of 50 μm to 150 μm.

9. A process for preparing the environmentally friendly foamed polyurethane coil according to any one of claims 1 to 8, characterized in that: The following steps are involved: 1) dispersing a silane coupling agent with a solvent and spraying the dispersed silane coupling agent on the surface of a glass fiber mesh, followed by drying to obtain a silane coupling agent-modified glass fiber mesh; 2) Laying a glass fiber mesh cloth modified with a silane coupling agent in a mold, then uniformly mixing thermoplastic polyurethane, chopped fibers, inorganic fillers, pigments, inorganic foaming agents, antioxidants, and ultraviolet absorbers, injecting the mixture into the mold, and then foaming the mixture to obtain an environmentally friendly foamed polyurethane coil.

10. An elastic floor, characterized in that: The surface is paved with the environmentally friendly foamed polyurethane coiled material according to any one of claims 1 to 8.

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