A highly wear-resistant semi-precast polyurethane runway and its preparation method

Abstract

The present invention discloses a highly wear-resistant semi-preformed polyurethane runway and a preparation method thereof, including a base layer and a surface layer. The base layer is formed by baking a mixture of material A and material B in a mold, and the surface layer is obtained by pouring and baking and curing a mixture of material A and material B on the surface of the base layer. The material A includes the following raw materials in parts by weight: 45-55 parts of polyether polyol, 2-2.5 parts of chain extender, 5-6 parts of azobisisobutyronitrile, 2.5-3.0 parts of foam stabilizer, 2-3 parts of plasticizer, 25-35 parts of reinforcing filler, 4-6 parts of pigment, 0.8-1.0 part of catalyst, 0.6-1 part of water, and 3-3.5 parts of water absorbent. The material B includes the following raw materials in parts by weight: 18-22 parts of diphenylmethane diisocyanate, and 8-12 parts of ethylene propylene diene monomer (EPDM) raw rubber particles. The addition of the synthesized plasticizer and reinforcing filler comprehensively enhances the flame retardancy, wear resistance, yellowing resistance, waterproofness and mechanical properties of the runway.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane materials, and particularly relates to a highly wear-resistant semi-precast polyurethane runway and a preparation method thereof. Background Art

[0002] Polyurethane is a block copolymer formed by alternating soft segments composed of oligomeric polyols and hard segments composed of diisocyanates and chain extenders, and is a high-performance polymer material. In order to ensure that the raw materials used in the synthesis of polyurethane have sufficient fluidity before gelation and achieve the effect of a smooth surface of the finished product, it is necessary to add a suitable plasticizer to reduce the viscosity of the raw materials. In order to meet the requirements of environmental protection concepts, the development of plant-based environmentally friendly plasticizers is an important research topic at present. Polyurethane rubber with good overall elasticity and high wear resistance is commonly used in the production of plastic runways. The high elasticity of polyurethane rubber is mainly due to the hydrogen bond force in its molecular main chain. The plastic runways commonly seen on campus are exposed to the outdoor environment and are affected by high temperatures and various thrown combustibles, which puts higher requirements on the flame retardancy of polyurethane runways in actual use; after being irradiated by sunlight for a long time, polyurethane will turn yellow, which has an adverse impact on the color and service performance of the runway, and it is necessary to improve the yellowing resistance of polyurethane runways.

[0003] In summary, with the improvement of the living standards of human society, schools pay more and more attention to the development of students' physical education disciplines, and higher requirements are also put forward for the comprehensive performance of polyurethane runways, which are closely related to the physical fitness of students. Appropriate modifiers are needed to solve the problems encountered in the actual use of polyurethane runways. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a highly wear-resistant semi-precast polyurethane runway and a preparation method thereof.

[0005] The object of the present invention can be achieved by the following technical solutions:

[0006] A highly wear-resistant semi-precast polyurethane runway, comprising a base layer and a surface layer. The base layer is formed by baking a mixture of material A and material B in a mold, and the surface layer is obtained by pouring and baking and curing a mixture of material A and material B on the surface of the base layer; Material A comprises the following raw materials in parts by weight: 45-55 parts of polyether polyol, 2-2.5 parts of chain extender, 5-6 parts of azobisisobutyronitrile, 2.5-3.0 parts of foam stabilizer, 2-3 parts of plasticizer, 25-35 parts of reinforcing filler, 4-6 parts of pigment, 0.8-1.0 part of catalyst, 0.6-1 part of water, and 3-3.5 parts of water absorbent; Material B comprises the following raw materials in parts by weight: 18-22 parts of diphenylmethane diisocyanate, 8-12 parts of ethylene propylene diene monomer (EPDM) raw rubber particles;

[0007] The polyether polyol is polyether polyol 220;

[0008] The chain extender is hydroquinone di (2-hydroxyethyl) ether;

[0009] The foam stabilizer is prepared from lauroyl diethanolamine and diethanolamine in a ratio of 1:1;

[0010] The pigment is iron oxide red;

[0011] The catalyst is zinc isooctanoate;

[0012] The water absorbent is zeolite powder;

[0013] The preparation of the plasticizer comprises the following steps:

[0014] Step A1: Add castor oil and diethyl chlorophosphate into chloroform, start stirring, heat up to 60 °C, stir and react for 4 - 5 h, and carry out vacuum distillation to obtain reaction product 1;

[0015] Furthermore, the dosage ratio of castor oil, diethyl chlorophosphate and chloroform is 0.1 mol: 0.3 mol: 300 - 350 mL;

[0016] During the reaction process of Step A1, the hydroxyl group in castor oil reacts with diethyl chlorophosphate to remove hydrogen chloride, generating reaction product 1 containing a phosphate ester structure; the structure of reaction product 1 is as follows:

[0017]

[0018] Step A2: Add reaction product 1, glacial acetic acid and phosphoric acid into a round-bottom flask, start stirring, and drop hydrogen peroxide into the round-bottom flask within 30 min at room temperature, heat up to 60 °C, and continue stirring and reacting for 8 - 8.5 h, and carry out vacuum distillation at 60 °C to obtain reaction product 2;

[0019] Furthermore, the dosage ratio of reaction product 1, glacial acetic acid, phosphoric acid and hydrogen peroxide is 110 - 120 g: 10 g: 0.5 g: 60 mL, and the mass fraction of hydrogen peroxide is 30%;

[0020] During the reaction process of Step A2, the unsaturated double bond in reaction product 1 is oxidized to an epoxy group to obtain reaction product 2; the structure of reaction product 2 is as follows:

[0021]

[0022] Step A3: Add reaction product 2 and tri (2-hydroxyethyl) isocyanurate into methanol, start stirring, then add trimethylamine, and reflux and stir and react at 110 - 120 °C for 6 - 7 h to obtain the plasticizer;

[0023] Furthermore, the dosage ratio of reaction product 2, tris(2-hydroxyethyl) isocyanurate, methanol and trimethylamine is 0.1 mol: 0.1 mol: 280 - 320 mL: 0.012 - 0.018 mol;

[0024] During the reaction process of step A3, the epoxy group of reaction product 2 reacts with the hydroxyl group of tris(2-hydroxyethyl) isocyanurate to generate a plasticizer with a hyperbranched macromolecular network structure.

[0025] The preparation of the reinforcing filler includes the following steps:

[0026] Step B1: Add 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylcinnamic acid to DMF, start stirring, slowly add thionyl chloride, and reflux and stir at 50 °C for 4 - 5 h to obtain acyl chloride product a;

[0027] Furthermore, the dosage ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylcinnamic acid, DMF and thionyl chloride is 0.1 mol: 150 mL: 0.1 - 0.15 mol;

[0028] During the reaction process of step B1, 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylcinnamic acid reacts with thionyl chloride to generate acyl chloride product a; the structure of acyl chloride product a is as follows:

[0029]

[0030] Step B2: Add N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, potassium carbonate and dimethyl sulfoxide to a flask to obtain mixture 1; then add acyl chloride product a to dimethyl sulfoxide to obtain mixture 2. Under an ice-water bath, slowly add mixture 2 to mixture 1 drop by drop. After the addition is complete, raise the temperature to 40 °C and react at a constant temperature for 6 - 7 h, and then perform vacuum distillation to obtain reaction product b;

[0031] Furthermore, the dosage ratio of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.012 - 0.015 mol: 80 - 90 mL; the dosage ratio of acyl chloride product a and dimethyl sulfoxide is 0.1 mol: 10 - 20 mL;

[0032] During the reaction process of step B2, the amino group of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine reacts with the acyl chloride of acyl chloride product a to generate reaction product b; the structure of reaction product b is as follows:

[0033]

[0034] Step B3: At room temperature, add cetyltrimethylammonium bromide to deionized water, stir for 10 min, then add ammonia water under stirring, continue stirring for 2 - 2.5 h, slowly dropwise add tetraethyl orthosilicate, then continue stirring for 24 h, filter, add the filter cake to absolute ethanol, then add 3-aminopropyltrimethoxysilane under stirring, and stir and react at room temperature for 12 h, centrifuge, remove the supernatant, and obtain mesoporous silica after vacuum drying; then add the dried mesoporous silica and reaction product b to acetone, stir at room temperature for 2 - 3 h, repeat the operations of evacuating for 30 min and then introducing air for 15 min three times, then wash with ethanol and deionized water, dry and grind to obtain the reinforcing filler;

[0035] Further, the dosage ratio of cetyltrimethylammonium bromide, deionized water, ammonia water, tetraethyl orthosilicate, absolute ethanol and 3-aminopropyltrimethoxysilane is 0.0096 mol : 800 mL : 24 - 25 mL : 15 mL : 200 mL : 7.4 - 7.5 mL; the dosage ratio of mesoporous silica, reaction product b and acetone is 2 g : 10 g : 100 mL;

[0036] During the reaction process of Step B3, using cetyltrimethylammonium bromide as the template and tetraethyl orthosilicate as the silicon source, mesoporous silica nanorods were synthesized. Through the repeated steps of evacuating and introducing air, the mesoporous silica is equivalent to multiple small "capillaries". The reaction product b can wet it in the acetone solution. The reaction product b overcomes the "barrier" at the pore orifice of the mesoporous silica through the action of van der Waals forces in a vacuum environment and enters the interior of the mesoporous silica to obtain mesoporous silica loaded with the reaction product b, that is, the reinforcing filler.

[0037] Advantages of the present invention: The present invention discloses a highly wear-resistant semi-preformed polyurethane runway. During its preparation process, raw materials such as plasticizers and reinforcing fillers are used in the synthesis of the A material. The synthesized plasticizer is a substance with a hyperbranched macromolecular network structure formed by introducing a phosphate ester structure and an isocyanuric acid structure into a plant-based castor oil skeleton through chemical reactions. The phosphate ester structure can effectively reduce the viscosity of the A material system, maintain the fluidity of the raw materials used in the synthesis of the A material, play a good plasticizing role, and can also generate phosphorus-containing compounds during the combustion of the polymer, promoting the formation of a carbon layer, covering the surface of the polymer. The carbon layer is incombustible, oxygen-insulating and has poor thermal conductivity, preventing heat from being transferred from the flame zone to the substrate; the isocyanuric acid structure is similar to the polyurethane structure, enhancing the dispersibility of the plasticizer in the matrix, and the isocyanuric acid structure contains a large amount of nitrogen elements. During the combustion of the polymer, non-combustible gases are formed to dilute the combustible gases, enabling the plasticizer to have a coordinated effect of phosphorus-nitrogen-based flame retardancy and improving the flame retardancy of the runway; the active hydroxyl groups contained in the plasticizer can form hydrogen bonds with the main chain of the polyurethane molecule, enhancing the elasticity and hardness of the polyurethane, thereby improving the wear resistance of the runway.

[0038] The synthesized reinforcing filler is obtained by loading the reaction product b on mesoporous silica with an amino-modified surface. The triazine structure and the hindered amine structure are introduced through the reaction product b. The triazine structure and the ortho-hydroxy groups on the benzene ring connected to the nitrogen atom in it jointly play the role of absorbing ultraviolet rays. The hindered amine structure inhibits the photo-oxidative degradation of the matrix. The triazine structure and the hindered amine structure work together coordinately to enhance the light stability of the matrix and improve the yellowing resistance of the runway. The amino groups on the surface of mesoporous silica can form hydrogen bond cross-linked networks with the hydroxyl groups in the plasticizer and the main chain of the polyurethane molecule, further enhancing the elasticity and hardness of the polyurethane, making the matrix more dense, and improving the wear resistance and waterproofness of the runway. The reaction product b is loaded on mesoporous silica, which can also effectively avoid the migration of small molecule reaction product b. Mesoporous silica has a small size effect and active chemical properties, making it easy to disperse into the voids of the polyurethane molecular segments. The reinforcing filler has good dispersion in the matrix, and the mechanical properties of the runway are effectively improved. Specific Embodiments

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0040] Example 1

[0041] A plasticizer, the preparation of which includes the following steps:

[0042] Step A1: Castor oil and diethyl chlorophosphate are added to chloroform, stirring is started, the temperature is raised to 60 °C, and the reaction is stirred for 4 h, followed by vacuum distillation to obtain reaction product 1; the dosage ratio of castor oil, diethyl chlorophosphate and chloroform is 0.1 mol: 0.3 mol: 300 mL;

[0043] Step A2: Reaction product 1, glacial acetic acid and phosphoric acid are added to a round-bottom flask, stirring is started, and hydrogen peroxide is dropped into the round-bottom flask within 30 min at room temperature, the temperature is raised to 60 °C, and the reaction is continued to stir for 8 h, followed by vacuum distillation at 60 °C to obtain reaction product 2; the dosage ratio of reaction product 1, glacial acetic acid, phosphoric acid and hydrogen peroxide is 110 g: 10 g: 0.5 g: 60 mL, and the mass fraction of hydrogen peroxide is 30%;

[0044] Step A3: Add reaction product 2 and tri(2-hydroxyethyl)isocyanurate into methanol, start stirring, then add trimethylamine, and reflux and stir for reaction at 110 °C for 6 h to obtain the plasticizer; the dosage ratio of reaction product 2, tri(2-hydroxyethyl)isocyanurate, methanol and trimethylamine is 0.1 mol: 0.1 mol: 280 mL: 0.012 mol.

[0045] Example 2

[0046] A plasticizer, the preparation of which comprises the following steps:

[0047] Step A1: Add castor oil and diethyl chlorophosphate into chloroform, start stirring, heat up to 60 °C, stir and react for 4.5 h, and perform reduced pressure distillation to obtain reaction product 1; the dosage ratio of castor oil, diethyl chlorophosphate and chloroform is 0.1 mol: 0.3 mol: 320 mL;

[0048] Step A2: Add reaction product 1, glacial acetic acid and phosphoric acid into a round-bottom flask, start stirring, drop hydrogen peroxide into the round-bottom flask within 30 min at room temperature, heat up to 60 °C, continue stirring and reacting for 8.2 h, and perform reduced pressure distillation at 60 °C to obtain reaction product 2; the dosage ratio of reaction product 1, glacial acetic acid, phosphoric acid and hydrogen peroxide is 115 g: 10 g: 0.5 g: 60 mL, and the mass fraction of hydrogen peroxide is 30%;

[0049] Step A3: Add reaction product 2 and tri(2-hydroxyethyl)isocyanurate into methanol, start stirring, then add trimethylamine, and reflux and stir for reaction at 115 °C for 6.5 h to obtain the plasticizer; the dosage ratio of reaction product 2, tri(2-hydroxyethyl)isocyanurate, methanol and trimethylamine is 0.1 mol: 0.1 mol: 300 mL: 0.015 mol.

[0050] Example 3

[0051] A plasticizer, the preparation of which comprises the following steps:

[0052] Step A1: Add castor oil and diethyl chlorophosphate into chloroform, start stirring, heat up to 60 °C, stir and react for 5 h, and perform reduced pressure distillation to obtain reaction product 1; the dosage ratio of castor oil, diethyl chlorophosphate and chloroform is 0.1 mol: 0.3 mol: 350 mL;

[0053] Step A2: Add reaction product 1, glacial acetic acid and phosphoric acid into a round-bottom flask, start stirring, drop hydrogen peroxide into the round-bottom flask within 30 min at room temperature, heat up to 60 °C, continue stirring and reacting for 8.5 h, and perform reduced pressure distillation at 60 °C to obtain reaction product 2; the dosage ratio of reaction product 1, glacial acetic acid, phosphoric acid and hydrogen peroxide is 120 g: 10 g: 0.5 g: 60 mL, and the mass fraction of hydrogen peroxide is 30%;

[0054] Step A3: Add reaction product 2 and tris(2-hydroxyethyl)isocyanurate into methanol, start stirring, then add trimethylamine, and reflux and stir the reaction at 120 °C for 7 h to obtain the plasticizer; the dosage ratio of reaction product 2, tris(2-hydroxyethyl)isocyanurate, methanol and trimethylamine is 0.1 mol: 0.1 mol: 320 mL: 0.018 mol.

[0055] Example 4

[0056] A reinforcing filler, the preparation of which comprises the following steps:

[0057] Step B1: Add 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylcinnamic acid into DMF, start stirring, slowly add thionyl chloride, and reflux and stir the reaction at 50 °C for 4 h to obtain acyl chloride product a; the dosage ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylcinnamic acid, DMF and thionyl chloride is 0.1 mol: 150 mL: 0.1 mol;

[0058] Step B2: Add N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, potassium carbonate and dimethyl sulfoxide into a flask to obtain mixture 1; then add acyl chloride product a into dimethyl sulfoxide to obtain mixture 2. Under an ice-water bath, slowly dropwise add mixture 2 into mixture 1. After the addition is completed, raise the temperature to 40 °C and keep the reaction at a constant temperature for 6 h, then carry out reduced pressure distillation to obtain reaction product b; the dosage ratio of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.012 mol: 80 mL; the dosage ratio of acyl chloride product a and dimethyl sulfoxide is 0.1 mol: 10 mL;

[0059] Step B3: At room temperature, add cetyltrimethylammonium bromide to deionized water, stir for 10 min, then add ammonia water under stirring, continue to stir for 2 h, slowly dropwise add tetraethyl orthosilicate, then continue to stir for 24 h, filter, add the filter cake to absolute ethanol, then add 3-aminopropyltrimethoxysilane under stirring, and stir and react at room temperature for 12 h, centrifuge, remove the supernatant, and obtain mesoporous silica after vacuum drying; then add the dried mesoporous silica and reaction product b to acetone, stir at room temperature for 2 h, repeat the operations of pumping to vacuum for 30 min and then introducing air for 15 min three times, then wash with ethanol and deionized water, dry and grind to obtain the reinforcing filler; the dosage ratio of cetyltrimethylammonium bromide, deionized water, ammonia water, tetraethyl orthosilicate, absolute ethanol and 3-aminopropyltrimethoxysilane is 0.0096 mol: 800 mL: 24 mL: 15 mL: 200 mL: 7.4 mL; the dosage ratio of mesoporous silica, reaction product b and acetone is 2 g: 10 g: 100 mL.

[0060] Example 5

[0061] An enhanced filler, the preparation of which comprises the following steps:

[0062] Step B1: Add 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylcinnamic acid to DMF, start stirring, slowly add thionyl chloride, and reflux and stir for reaction at 50 °C for 4.5 h to obtain an acyl chloride product a; the dosage ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylcinnamic acid, DMF and thionyl chloride is 0.1 mol: 150 mL: 0.12 mol;

[0063] Step B2: Add N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, potassium carbonate and dimethyl sulfoxide to a flask to obtain a mixture 1; then add the acyl chloride product a to dimethyl sulfoxide to obtain a mixture 2. Under an ice-water bath, slowly drop the mixture 2 into the mixture 1. After dropping, raise the temperature to 40 °C and react at a constant temperature for 6.5 h, then carry out vacuum distillation to obtain a reaction product b; the dosage ratio of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.013 mol: 85 mL; the dosage ratio of the acyl chloride product a and dimethyl sulfoxide is 0.1 mol: 15 mL;

[0064] Step B3: At room temperature, add cetyltrimethylammonium bromide to deionized water, stir for 10 min, then add ammonia water under stirring, continue stirring for 2.2 h, slowly dropwise add tetraethyl orthosilicate, then continue stirring for 24 h, filter, add the filter cake to absolute ethanol, then add 3-aminopropyltrimethoxysilane under stirring, and stir and react at room temperature for 12 h, centrifuge, remove the supernatant, and obtain mesoporous silica after vacuum drying; then add the dried mesoporous silica and the reaction product b to acetone, stir at room temperature for 2.5 h, repeat the operations of evacuating for 30 min and then introducing air for 15 min three times, and then wash with ethanol and deionized water, dry and grind to obtain the enhanced filler; the dosage ratio of cetyltrimethylammonium bromide, deionized water, ammonia water, tetraethyl orthosilicate, absolute ethanol and 3-aminopropyltrimethoxysilane is 0.0096 mol: 800 mL: 24 mL: 15 mL: 200 mL: 7.4 mL; the dosage ratio of mesoporous silica, the reaction product b and acetone is 2 g: 10 g: 100 mL.

[0065] Example 6

[0066] An enhanced filler, the preparation of which comprises the following steps:

[0067] Step B1: Add 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid into DMF, start stirring, slowly add thionyl chloride, and reflux and stir for reaction at 50 °C for 5 h to obtain acyl chloride product a; the dosage ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylphenylpropionic acid, DMF and thionyl chloride is 0.1 mol: 150 mL: 0.15 mol;

[0068] Step B2: Add N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, potassium carbonate and dimethyl sulfoxide into a flask to obtain mixture 1; then add acyl chloride product a into dimethyl sulfoxide to obtain mixture 2. Under an ice-water bath, slowly dropwise add mixture 2 into mixture 1. After the addition is completed, raise the temperature to 40 °C and react at a constant temperature for 7 h, then perform vacuum distillation to obtain reaction product b; the dosage ratio of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 90 mL; the dosage ratio of acyl chloride product a and dimethyl sulfoxide is 0.1 mol: 20 mL;

[0069] Step B3: At room temperature, add cetyltrimethylammonium bromide to deionized water, stir for 10 min, then add ammonia water while stirring, continue to stir for 2.5 h, slowly dropwise add tetraethyl orthosilicate, then continue to stir for 24 h, filter, add the filter cake to absolute ethanol, and then add 3-aminopropyltrimethoxysilane while stirring, stir and react at room temperature for 12 h, centrifuge, remove the supernatant, and obtain mesoporous silica after vacuum drying; then add the dried mesoporous silica and reaction product b to acetone, stir at room temperature for 3 h, repeat the operations of evacuating for 30 min and then introducing air for 15 min three times, and then wash with ethanol and deionized water, dry and grind to obtain the reinforcing filler; the dosage ratio of cetyltrimethylammonium bromide, deionized water, ammonia water, tetraethyl orthosilicate, absolute ethanol and 3-aminopropyltrimethoxysilane is 0.0096 mol: 800 mL: 25 mL: 15 mL: 200 mL: 7.5 mL; the dosage ratio of mesoporous silica, reaction product b and acetone is 2 g: 10 g: 100 mL.

[0070] Example 7

[0071] A highly wear-resistant semi-precast polyurethane runway, comprising a base layer and a surface layer. The base layer is formed by baking a mixture of Material A and Material B in a mold. The surface layer is obtained by pouring and baking and curing a mixture of Material A and Material B on the surface of the base layer. Material A comprises the following raw materials in parts by weight: 45 parts of polyether polyol, 2 parts of chain extender, 5 parts of azobisisobutyronitrile, 2.5 parts of foam stabilizer, 2 parts of plasticizer, 25 parts of reinforcing filler, 4 parts of pigment, 0.8 part of catalyst, 0.6 part of water and 3 parts of water absorbent. Material B comprises the following raw materials in parts by weight: 18 parts of diphenylmethane diisocyanate and 8 parts of ethylene propylene diene monomer (EPDM) raw rubber particles. The polyether polyol is polyether polyol 220. The chain extender is hydroquinone bis(2-hydroxyethyl) ether. The foam stabilizer is prepared from lauroyl diethanolamine and diethanolamine in a ratio of 1:1. The pigment is iron oxide red. The catalyst is zinc isooctanoate. The water absorbent is zeolite powder.

[0072] The preparation of the highly wear-resistant semi-precast polyurethane runway comprises the following steps:

[0073] Step S1: Add polyether polyol, chain extender, azobisisobutyronitrile, foam stabilizer, plasticizer, reinforcing filler, pigment, catalyst, water and water absorbent to a reaction kettle, stir for 40 min to obtain Material A; mix and stir diphenylmethane diisocyanate and EPDM raw rubber particles for 15 min to obtain Material B; add Material A and Material B to the reaction kettle, and stir at 65 °C for 2 h to obtain polyurethane slurry.

[0074] Step S2: Pour the polyurethane slurry into a mold, with an average pouring thickness of 6 mm, bake and cure at 75 °C for 25 min, un-mold and wind up to obtain the base layer, then pour polyurethane slurry on the surface of the base layer, with an average pouring thickness of 2 mm, and bake and cure at 75 °C to form the surface layer, thus obtaining the highly wear-resistant semi-precast polyurethane runway.

[0075] Example 8

[0076] A highly wear-resistant semi-precast polyurethane runway, comprising a base layer and a surface layer. The base layer is formed by baking a mixture of material A and material B in a mold. The surface layer is obtained by pouring and baking and curing a mixture of material A and material B on the surface of the base layer. The material A comprises the following raw materials in parts by weight: 50 parts of polyether polyol, 2.2 parts of chain extender, 5.5 parts of azobisisobutyronitrile, 2.7 parts of foam stabilizer, 2.5 parts of plasticizer, 30 parts of reinforcing filler, 5 parts of pigment, 0.9 part of catalyst, 0.8 part of water, and 3.2 parts of water absorbent. The material B comprises the following raw materials in parts by weight: 20 parts of diphenylmethane diisocyanate, 10 parts of ethylene propylene diene monomer (EPDM) raw rubber particles. The polyether polyol is polyether polyol 220. The chain extender is hydroquinone bis(2-hydroxyethyl) ether. The foam stabilizer is prepared from lauroyl diethanolamine and diethanolamine in a ratio of 1:1. The pigment is iron oxide red. The catalyst is zinc isooctanoate. The water absorbent is zeolite powder.

[0077] The preparation of the highly wear-resistant semi-precast polyurethane runway comprises the following steps:

[0078] Step S1: Add the polyether polyol, chain extender, azobisisobutyronitrile, foam stabilizer, plasticizer, reinforcing filler, pigment, catalyst, water, and water absorbent to a reaction kettle, and stir for 45 min to obtain material A; mix and stir diphenylmethane diisocyanate and EPDM raw rubber particles for 20 min to obtain material B; add material A and material B to the reaction kettle, and stir at 70 °C for 2.5 h to obtain polyurethane slurry.

[0079] Step S2: Pour the polyurethane slurry into a mold, with an average pouring thickness of 7 mm, bake and cure at 75 °C for 28 min, and after demolding, wind it up to obtain the base layer. Then pour polyurethane slurry on the surface of the base layer, with an average pouring thickness of 3 mm, and bake and cure at 75 °C to form the surface layer, thus obtaining the highly wear-resistant semi-precast polyurethane runway.

[0080] Example 9

[0081] A highly wear-resistant semi-precast polyurethane runway, comprising a base layer and a surface layer. The base layer is formed by baking a mixture of material A and material B in a mold. The surface layer is obtained by pouring and baking and curing a mixture of material A and material B on the surface of the base layer. Material A comprises the following raw materials in parts by weight: 55 parts of polyether polyol, 2.5 parts of chain extender, 6 parts of azobisisobutyronitrile, 3.0 parts of foam stabilizer, 3 parts of plasticizer, 35 parts of reinforcing filler, 6 parts of pigment, 1.0 part of catalyst, 1 part of water, and 3.5 parts of water absorbent. Material B comprises the following raw materials in parts by weight: 22 parts of diphenylmethane diisocyanate, 12 parts of ethylene propylene diene monomer (EPDM) raw rubber particles. The polyether polyol is polyether polyol 220. The chain extender is hydroquinone bis(2-hydroxyethyl) ether. The foam stabilizer is prepared from lauroyl diethanolamine and diethanolamine in a ratio of 1:1. The pigment is iron oxide red. The catalyst is zinc isooctanoate. The water absorbent is zeolite powder.

[0082] The preparation of the highly wear-resistant semi-precast polyurethane runway comprises the following steps:

[0083] Step S1: Add polyether polyol, chain extender, azobisisobutyronitrile, foam stabilizer, plasticizer, reinforcing filler, pigment, catalyst, water, and water absorbent to a reaction kettle, stir for 50 min to obtain material A; mix diphenylmethane diisocyanate and EPDM raw rubber particles and stir for 25 min to obtain material B; add material A and material B to the reaction kettle, and stir at 75 °C for 3 h to obtain polyurethane slurry.

[0084] Step S2: Pour the polyurethane slurry into a mold, with an average pouring thickness of 8 mm, bake and cure at 75 °C for 30 min, un-mold and wind up to obtain the base layer, then pour polyurethane slurry on the surface of the base layer, with an average pouring thickness of 4 mm, and bake and cure at 75 °C to form the surface layer, thus obtaining the highly wear-resistant semi-precast polyurethane runway.

[0085] Comparative Example 1

[0086] This comparative example is a commercially available semi-precast polyurethane runway.

[0087] Comparative Example 2

[0088] Compared with Example 9, replace the plasticizer with triethyl phosphate, and the others are exactly the same as Example 9 to prepare a highly wear-resistant semi-precast polyurethane runway.

[0089] Comparative Example 3

[0090] Compared with Example 9, replace the reinforcing filler with nano-silica, and the others are exactly the same as Example 9 to prepare a highly wear-resistant semi-precast polyurethane runway.

[0091] The following is a further effect detection of the highly wear-resistant semi-precast polyurethane runway prepared by the present invention, and the detection results are as follows.

[0092] To test the high-wear-resistant semi-preformed polyurethane runway prepared by the present invention, the hardness was tested according to the method of GB / T 14833-2020; the tensile strength and elongation at break were tested according to the method of GB / 36246-2018; the abrasion loss was tested according to the method of GB / T 1689-1998; the limiting oxygen index was determined according to the method of GB10707-2008; the waterproof performance test method was to immerse the semi-preformed polyurethane runway samples obtained from Examples 7-9 and Comparative Examples 1-3 with a weight of 150.0 g in water (water temperature 15°C). After soaking for one week, the weight after soaking was measured and recorded in Table 1;

[0093] Table 1:

[0094]

[0095] According to the data in Table 1, by comparing Examples 7, 8 and 9 with Comparative Example 1, it can be seen that compared with the commercially available semi-preformed polyurethane runway, the high-wear-resistant semi-preformed polyurethane runway prepared by the present invention has excellent flame retardancy, wear resistance, yellowing resistance, waterproofness and mechanical properties; by comparing Example 9 with Comparative Example 2, it can be seen that the use of plasticizers, containing phosphate ester structures, isocyanuric acid structures and hydroxyl groups improves the flame retardancy and wear resistance of the runway; by comparing Example 9 with Comparative Example 3, it can be seen that the use of reinforcing fillers, containing triazine structures, hindered phenol structures, mesoporous silica and amino groups on its surface, improves the yellowing resistance, mechanical properties, wear resistance and waterproofness of the runway.

[0096] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

Claims

1. A highly wear-resistant semi-prefabricated polyurethane runway, characterized in that: The invention comprises a base layer and a surface layer, wherein the base layer is formed by mixing material A and material B and then baking in a mold, and the surface layer is formed by mixing material A and material B and then pouring and baking on the surface of the base layer; the material A comprises the following raw materials in parts by weight: 45-55 parts of polyether polyol, 2-2.5 parts of chain extender, 5-6 parts of azobisisobutyronitrile, 2.5-3.0 parts of foam stabilizer, 2-3 parts of plasticizer, 25-35 parts of reinforcing filler, 4-6 parts of pigment, 0.8-1.0 parts of catalyst, 0.6-1 parts of water and 3-3.5 parts of water absorbent; the material B comprises the following raw materials in parts by weight: 18-22 parts of diphenylmethane diisocyanate and 8-12 parts of EPDM rubber raw rubber particles; The preparation of the plasticizer comprises the following steps: Step A1: Add castor oil and diethyl chlorophosphate into chloroform, start stirring, raise the temperature to 60° C., stir and react for 4-5 hours, and perform distillation under reduced pressure to obtain reaction product 1; Step A2: Add the reaction product 1, glacial acetic acid and phosphoric acid into a round-bottom flask, start stirring, and at room temperature, drop hydrogen peroxide into the round-bottom flask within 30 minutes, raise the temperature to 60°C, continue stirring and reacting for 8-8.5 hours, and distill under reduced pressure at 60°C to obtain the reaction product 2; Step A3: Add the reaction product 2 and trihydroxyethyl isocyanurate into methanol, start stirring, then add trimethylamine, and reflux and stir at 110-120° C. for 6-7 hours to obtain a plasticizer; The preparation of the reinforcing filler comprises the following steps: Step B1: Add 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid to DMF, start stirring, slowly add thionyl chloride, reflux and stir at 50° C. for 4-5 hours to obtain an acyl chloride product a; Step B2: Add N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution 1; then add the acyl chloride product a into dimethyl sulfoxide to obtain a mixed solution 2, slowly dropwise add the mixed solution 2 into the mixed solution 1 under an ice-water bath, after the dropwise addition is completed, heat to 40°C, react at a constant temperature for 6-7 hours, and distill under reduced pressure to obtain a reaction product b; Step B3: At room temperature, add hexadecyltrimethylammonium bromide to deionized water, stir for 10 minutes, then add ammonia water under stirring, continue stirring for 2-2.5 hours, slowly add tetraethyl orthosilicate dropwise, and then continue stirring for 24 hours, filter, add the filter cake to anhydrous ethanol, and then add 3-aminopropyltrimethoxysilane under stirring, stir and react at room temperature for 12 hours, centrifuge, remove the supernatant, and vacuum dry to obtain mesoporous silica; then add the dried mesoporous silica and reaction product b to acetone, stir at room temperature for 2-3 hours, repeat the operation of vacuuming for 30 minutes and then opening the atmosphere for 15 minutes three times, then wash with ethanol and deionized water, dry and grind to obtain reinforcing filler.

2. A highly wear-resistant semi-prefabricated polyurethane runway according to claim 1, characterized in that: The polyether polyol is polyether polyol 220; the chain extender is hydroquinone dihydroxyethyl ether; the foam stabilizer is prepared by mixing lauroyl diethanolamine and diethanolamine in a ratio of 1:1; the pigment is red iron oxide; the catalyst is zinc isooctanoate; and the water absorbent is zeolite powder.

3. The highly wear-resistant semi-prefabricated polyurethane runway according to claim 1, characterized in that: In step A1, the usage ratio of castor oil, diethyl chlorophosphate and chloroform is 0.1 mol:0.3 mol:300-350 mL.

4. The highly wear-resistant semi-prefabricated polyurethane runway according to claim 1, characterized in that: In step A2, the usage ratio of reaction product 1, glacial acetic acid, phosphoric acid and hydrogen peroxide is 110-120 g: 10 g: 0.5 g: 60 mL, and the mass fraction of hydrogen peroxide is 30%.

5. The highly wear-resistant semi-prefabricated polyurethane runway according to claim 1, characterized in that: In step A3, the amount ratio of reaction product 2, trishydroxyethyl isocyanurate, methanol and trimethylamine is 0.1 mol: 0.1 mol: 280-320 mL: 0.012-0.018 mol.

6. The highly wear-resistant semi-prefabricated polyurethane runway according to claim 1, characterized in that: In step B1, the usage ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid, DMF and dithionyl chloride is 0.1 mol:150 mL:0.1-0.15 mol.

7. The highly wear-resistant semi-prefabricated polyurethane runway according to claim 1, characterized in that: In step B2, the usage ratio of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.012-0.015 mol: 80-90 mL; the usage ratio of acyl chloride product a and dimethyl sulfoxide is 0.1 mol: 10-20 mL.

8. The highly wear-resistant semi-prefabricated polyurethane runway according to claim 1, characterized in that: In step B3, the usage ratio of hexadecyltrimethylammonium bromide, deionized water, ammonia water, ethyl orthosilicate, anhydrous ethanol and 3-aminopropyltrimethoxysilane is 0.0096 mol: 800 mL: 24-25 mL: 15 mL: 200 mL: 7.4-7.5 mL; the usage ratio of mesoporous silica, reaction product b and acetone is 2 g: 10 g: 100 mL.

9. The method for preparing a highly wear-resistant semi-prefabricated polyurethane runway according to claim 1, characterized in that: The steps include: Step S1: adding polyether polyol, chain extender, azobisisobutyronitrile, foam stabilizer, plasticizer, reinforcing filler, pigment, catalyst, water and water absorbent to a reactor, stirring for 40-50 minutes to obtain material A; mixing diphenylmethane diisocyanate and EPDM rubber raw rubber particles and stirring for 15-25 minutes to obtain material B; adding material A and material B to a reactor, stirring at 65-75° C. for 2-3 hours to obtain polyurethane slurry; Step S2: Pour the polyurethane slurry into the mould with an average pouring thickness of 6-8mm, bake and cure at 75°C for 25-30min, roll up after opening the mould to obtain the base layer, and then pour the polyurethane slurry on the surface of the base layer with an average pouring thickness of 2-4mm, bake and cure at 75°C to form the surface layer, thus obtaining a highly wear-resistant semi-prefabricated polyurethane runway.

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