TPU (thermoplastic polyurethane) floor mat for ball field and preparation method of TPU floor mat

Abstract

The invention relates to a TPU (thermoplastic polyurethane) floor mat for a ball field and a preparation method of the TPU floor mat, and belongs to the technical field of preparation of TPU floor mats. The TPU ground mat comprises the following raw materials in parts by weight: 100 parts of TPU base material, 1-10 parts of modified porous microspheres and 1-5 parts of auxiliary agent. The modified porous microspheres are introduced into the TPU, the porous characteristic of the modified porous microspheres is utilized, the mixed melt is endowed with the uniform porous characteristic, the injected supercritical gas is promoted to enter the mixed melt, the supercritical gas and the mixed melt are more easily blended into a homogeneous phase, the pressure process parameters of the injected supercritical gas are reduced, and in addition, the pressure of the injected supercritical gas is reduced. The introduction of the modified porous microspheres improves the resilience of the obtained TPU floor mat, so that the TPU floor mat can meet the requirement of a Pick ball on the resilience force of the floor mat.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of TPU floor mats, and in particular, relates to a TPU floor mat for a ball field and a preparation method thereof. Background Art

[0002] The existing ball court mats in the market are generally made of polyvinyl chloride (PVC) material or highly foamed polyethylene (PE) material or acrylic acid. These mats have average elasticity and can meet the elasticity requirements of ordinary balls (such as basketball and football), but cannot meet the requirements of pickleball for the rebound force of the mat. Therefore, it is necessary to provide a TPU ball court mat and a preparation method thereof to meet the requirements of the pickleball court for the rebound force of the mat. Summary of the invention

[0003] The object of the present invention is to provide a TPU floor mat for ball games and a preparation method thereof.

[0004] The technical problem to be solved by the present invention is to solve the problem of insufficient resilience of existing floor mats.

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

[0006] A TPU floor mat for ball games comprises the following raw materials in parts by weight: 100 parts of TPU base material, 1-10 parts of modified porous microspheres, and 1-5 parts of auxiliary agents.

[0007] Furthermore, the modified porous microspheres are prepared by suspension polymerization of porous silica particles with double bonds grafted on the surface and polyborosiloxane monomers;

[0008] The porous silica particles with double bonds grafted on the surface are prepared by surface grafting reaction of porous silica particles and double-bond silane coupling agent.

[0009] Furthermore, the particle size of the porous silica particles is 1-20 μm.

[0010] Preferably, the porous silica particles have a particle size of 5-10 μm.

[0011] Furthermore, in the porous silica particles with double bonds grafted on the surface, the mass ratio of the porous silica particles to the double bond silane coupling agent is 10:1-3; and the molar ratio of the double bond silane coupling agent to the polyborosiloxane monomer is 1:1-3.

[0012] Furthermore, the porous silica particles with double bonds grafted on the surface are obtained by:

[0013] The porous silica particles are ultra-dispersed in a mixed solvent (water and ethanol in a volume ratio of 1:9), heated to 50-70°C, and a double-bond silane coupling agent is added under stirring. After the addition, the reaction is continued with stirring for 1-24 hours, the reaction is stopped, aged, filtered, washed, and dried to obtain porous silica particles with double bonds grafted on the surface.

[0014] Furthermore, the suspension polymerization reaction occurs in the presence of an initiator, the reaction temperature of the suspension polymerization reaction is 60-75° C., and the reaction time is 6-24 hours.

[0015] Preferably, the suspension polymerization reaction comprises:

[0016] The porous silica particles with double bonds grafted on the surface are ultra-dispersed in an organic solvent (one or a mixture of benzene, N,N-dimethylformamide, tetrahydrofuran) to obtain a suspension, and then the suspension is heated to 60-75°C under stirring, and an initiator and a polyborosiloxane monomer are added. After the addition, the reaction is continued with stirring for 6-24 hours, and the reaction is stopped, aged, filtered, washed, and dried to obtain modified porous microspheres.

[0017] Furthermore, the initiator is one of the azo initiators, such as azobisisobutyronitrile.

[0018] Further, the polyborosiloxane monomer is prepared by reacting phenylboronic acid and dimethylvinylchlorosilane in a first organic solvent;

[0019] The molar ratio of phenylboronic acid to dimethylvinylchlorosilane is 1:2-2.5, and a substitution reaction is performed between the chloro group in dimethylvinylchlorosilane and the boron-connected hydroxyl group in phenylboronic acid, so that two boron-connected hydroxyl groups in phenylboronic acid are replaced by dimethylvinylsilyl groups, thereby obtaining a polyborosiloxane monomer, that is, one mole of the polyborosiloxane monomer contains two moles of dimethylvinylsilyl groups.

[0020] Preferably, the polyborosiloxane monomer is obtained by:

[0021] After phenylboric acid, ether (as the first organic solvent) and triethylamine (acid binding agent) are evenly mixed, ether solution containing dimethylvinylchlorosilane is added at 20-40°C with stirring. After the addition is completed, stirring and reacting is continued for 3-24 hours, the reaction is stopped, rotary evaporated, washed and dried to obtain polyborosiloxane monomer.

[0022] Furthermore, the auxiliary agent is an antioxidant, a weathering agent, or a mixture of both.

[0023] The second object of the present invention can be achieved by the following technical solutions:

[0024] A method for preparing a TPU floor mat for a ball field, characterized by comprising:

[0025] The thermoplastic TPU, modified porous microspheres and auxiliary agents are mixed and added into an extruder, and melt-blended to obtain a mixed melt;

[0026] Injecting supercritical gas into the middle section of the extruder, and mixing and cooling the injected supercritical gas and the mixed melt in the subsequent temperature zone of the extruder to obtain a cooled homogeneous phase;

[0027] The homogeneous phase is extruded through an extruder and pelletized underwater to obtain foamed particles;

[0028] The foamed particles are molded by steam molding to obtain a TPU floor mat.

[0029] Furthermore, the temperature of the melt blending temperature zone is 150-190°C.

[0030] Furthermore, the temperature of the temperature zone into which the supercritical gas is injected is set to 190-210°C.

[0031] Furthermore, the supercritical gas is supercritical carbon dioxide or supercritical nitrogen.

[0032] Furthermore, the injection pressure of the supercritical gas is 8-25Mpa.

[0033] Furthermore, the injection amount of the supercritical gas is 3-15% of the mass of the melt.

[0034] Furthermore, the temperature of the temperature zone for mixing and cooling the injected supercritical gas and the mixed melt is set to 150-190°C.

[0035] Furthermore, the extrusion temperature is 150-190°C.

[0036] Furthermore, the temperature of the underwater pelletizing is 40-80°C.

[0037] The third object of the present invention can be achieved by the following technical solutions:

[0038] The TPU floor mat for ball games is used to prepare the floor mat for pickleball courts.

[0039] Beneficial effects of the present invention:

[0040] The present invention discloses a TPU floor mat for ball games and a preparation method thereof. The TPU floor mat is made by a "supercritical" foaming extrusion process of TPU. Modified porous microspheres are introduced into TPU and the porous characteristics of the modified porous microspheres are utilized. When the modified porous microspheres are blended with raw materials into a mixed melt, the mixed melt is endowed with uniform porous characteristics, and the injected supercritical gas is promoted to enter the mixed melt and fill the pre-pores, so that the supercritical gas is easier to blend with the mixed melt into a homogeneous phase, and the pressure process parameters of the supercritical gas injection are reduced. In addition, the surface of the modified porous microspheres is a polymer chain (polyborosiloxane), and the inside is rigid porous silica. The introduction of the modified porous microspheres improves the resilience of the obtained TPU floor mat, so that the modified microspheres can meet the requirements of pickle ball for the resilience of the floor mat. DETAILED DESCRIPTION

[0041] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0042] Example 1

[0043] Preparation of modified porous microspheres:

[0044] 1. After 0.1 mol of phenylboric acid, 100 mL of ether and 0.21 mol of triethylamine were mixed evenly, 0.2 mol of dimethylvinylchlorosilane solution was added at 30°C under stirring. After the addition, the reaction was continued under stirring for 12 hours, the reaction was stopped, rotary evaporated, washed and dried to obtain polyborosiloxane monomer.

[0045] 2. Disperse 100 g of porous silica particles (particle size of 5-10 μm) in 250 mL of a mixed solvent (water and ethanol in a volume ratio of 1:9), heat to 50°C, add 24.83 g (0.1 mol) of a double bond silane coupling agent (KH570) under stirring, continue stirring and react for 8 h, stop the reaction, age, filter, wash, and dry to obtain porous silica particles with double bonds grafted on the surface.

[0046] 3. Ultra-disperse 100 g of porous silica particles with double bonds grafted on the surface in 800 mL of benzene to obtain a suspension, then heat to 60°C under stirring, add 0.6 g of azobisisobutyronitrile and 25.83 g (0.1 mol) of polyborosiloxane monomer, and continue to stir and react for 8 h after addition. Stop the reaction, age, filter, wash, and dry to obtain modified porous microspheres.

[0047] Example 2

[0048] Preparation of modified porous microspheres:

[0049] 1. After 0.1 mol of phenylboric acid, 100 mL of ether and 0.23 mol of triethylamine were mixed evenly, 0.25 mol of dimethylvinylchlorosilane ether solution was added at 40°C under stirring. After the addition was completed, the reaction was continued with stirring for 3 hours, the reaction was stopped, rotary evaporated, washed and dried to obtain polyborosiloxane monomer.

[0050] 2. Disperse 250 g of porous silica particles (particle size of 5-10 μm) in 500 ml of a mixed solvent (water and ethanol in a volume ratio of 1:9), heat to 50-70 ° C, add 24.83 g (0.1 mol) of a double bond silane coupling agent (KH570) under stirring, continue stirring and react for 1-24 hours, stop the reaction, age, filter, wash, and dry to obtain porous silica particles with double bonds grafted on the surface.

[0051] 3. Ultra-disperse 200 g of porous silica particles with double bonds grafted on the surface in 600 mL of benzene to obtain a suspension, then heat to 60°C under stirring, add azobisisobutyronitrile and 77.49 g (0.3 mol) of polyborosiloxane monomer, and continue to stir and react for 12 hours after addition. Stop the reaction, age, filter, wash, and dry to obtain modified porous microspheres.

[0052] Example 3

[0053] Preparation of TPU floor mats:

[0054] The first step is to prepare the following raw materials by weight: 100 parts of TPU base material (brand BASF1170A, BASF, Germany), 3 parts of modified porous microspheres prepared in Example 1, and 1 part of auxiliary agent (antioxidant 1010);

[0055] Step 2: Mix the thermoplastic TPU, modified porous microspheres and auxiliary agent and add them into an extruder for melt blending to obtain a mixed melt;

[0056] The third step is to inject supercritical gas into the middle section (fourth zone) of the extruder, and the injected supercritical gas and the mixed melt are mixed and cooled in the subsequent temperature zones (fifth zone and sixth zone) of the extruder to obtain a cooled homogeneous phase; the homogeneous phase is extruded by the extruder and pelletized underwater to obtain foamed particles; wherein the temperature of the melt blending temperature zone is 150-190°C; the temperature of the temperature zone where the supercritical gas is injected is set to 190-200°C (i.e., the temperature of the fourth zone is 190-200°C ), the injection pressure of the supercritical gas is 20Mpa, and the injection amount of the supercritical gas is 6% of the mass of the melt; the temperature of the mixing and cooling temperature zones of the injected supercritical gas and the mixed melt is set to 150-190°C (170-180°C for zone five and 150-160°C for zone six), the extrusion temperature is 150±5°C, the temperature of the underwater pelletizing is 40±5°C, and the pressure is 100-150 kPa (the extruder has a total of six temperature zones);

[0057] Step 4: The foamed particles are molded by steam molding to obtain a TPU floor mat.

[0058] Example 4

[0059] Preparation of TPU floor mats:

[0060] The first step is to prepare the following raw materials in parts by weight: 100 parts of TPU base material (brand BASF1170A, BASF, Germany), 6 parts of modified porous microspheres prepared in Example 1, and 1.5 parts of auxiliary agent (antioxidant 1010);

[0061] Step 2: Mix the thermoplastic TPU, modified porous microspheres and auxiliary agent and add them into an extruder for melt blending to obtain a mixed melt;

[0062] The second step is to inject supercritical gas into the middle section (fourth zone) of the extruder, and the injected supercritical gas and the mixed melt are mixed and cooled in the subsequent temperature zones (fifth zone and sixth zone) of the extruder to obtain a cooled homogeneous phase; the homogeneous phase is extruded by the extruder and pelletized underwater to obtain foamed particles; the foamed particles are subjected to steam molding to obtain a TPU floor mat, wherein the temperature of the melt blending temperature zone is 150-190°C; the temperature of the temperature zone (fourth zone) for injecting supercritical gas is set to 200 -210℃, the injection pressure of the supercritical gas is 15Mpa, and the injection amount of the supercritical gas is 10% of the mass of the melt; the temperature of the mixing and cooling temperature zones of the injected supercritical gas and the mixed melt is set to 150-190℃ (170-180℃ for zone five and 150-160℃ for zone six), the extrusion temperature is 160±5℃, the temperature of the underwater pelletizing is 60±5℃, and the pressure is 100-150 kPa (the extruder has a total of six temperature zones).

[0063] Step 4: The foamed particles are molded by steam molding to obtain a TPU floor mat.

[0064] Example 5

[0065] Preparation of TPU floor mats:

[0066] The first step is to prepare the following raw materials in parts by weight: 100 parts of TPU base material (brand BASF1170A, BASF, Germany), 10 parts of modified porous microspheres prepared in Example 1, and 1 part of auxiliary agent (antioxidant 1010);

[0067] Step 2: Mix the thermoplastic TPU, modified porous microspheres and auxiliary agent and add them into an extruder for melt blending to obtain a mixed melt;

[0068] The third step is to inject supercritical gas into the middle section (fifth zone) of the extruder, and the injected supercritical gas and the mixed melt are mixed and cooled in the subsequent temperature zones (sixth and seventh zones) of the extruder to obtain a cooled homogeneous phase; the homogeneous phase is extruded by the extruder and pelletized underwater to obtain foamed particles; the foamed particles are subjected to steam molding to obtain a TPU floor mat, wherein the temperature of the melt blending temperature zone is 150-190°C; the temperature of the temperature zone where the supercritical gas is injected is set to 200-21 0℃, the injection pressure of the supercritical gas is 8Mpa, and the injection amount of the supercritical gas is 15% of the mass of the melt; the temperature of the mixing and cooling temperature zones of the injected supercritical gas and the mixed melt is set to 150-190℃ (170-180℃ for the sixth zone and 150-160℃ for the seventh zone), the extrusion temperature is 170±5℃, the temperature of the underwater pelletizing is 70±5℃, and the pressure is 100-150 kPa (the extruder is provided with 7 temperature zones in total).

[0069] Step 4: The foamed particles are molded by steam molding to obtain a TPU floor mat.

[0070] Comparative Example 1

[0071] Compared with Example 3, the modified porous microspheres in the raw material are replaced with spherical silica with a particle size of 5-10 μm, and the rest are the same.

[0072] Comparative Example 2

[0073] Compared with Example 3, the modified porous microspheres in the raw material were replaced with spherical porous silica particles with a particle size of 5-10 μm, and the rest were the same.

[0074] The physical properties of the TPU floor mats of Examples 3-5 and Comparative Examples 1-2 were tested, and the test results are shown in Table 1. In the ball rebound test: a free fall test of a pickle ball was performed at the same fixed height, and the ratio of the rebound height of the pickle ball to the fixed height (i.e., the rebound rate of the ball) was tested. The free fall test of the pickle ball was repeated 5 times, and the rebound rate of the ball was averaged.

[0075] Table 1

[0076]

[0077] It can be seen from the data in Table 1 that the TPU floor mats obtained in Examples 3-5 of the present invention have good tensile properties and rebound performance, meeting the rebound force requirements of pickle ball on the floor mats.

[0078] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0079] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A TPU floor mat for ball games, characterized in that: The invention comprises the following raw materials in parts by weight: 100 parts of TPU base material, 1-10 parts of modified porous microspheres and 1-5 parts of auxiliary agent.

2. A TPU floor mat for ball games according to claim 1, characterized in that: The modified porous microspheres are prepared by suspension polymerization of porous silica particles with double bonds grafted on the surface and polyborosiloxane monomers; The porous silica particles with double bonds grafted on the surface are prepared by surface grafting reaction of porous silica particles and double-bond silane coupling agent.

3. A TPU floor mat for ball games according to claim 2, characterized in that: In the porous silica particles with double bonds grafted on the surface, the mass ratio of the porous silica particles to the double-bond silane coupling agent is 10:1-3; and the molar ratio of the double-bond silane coupling agent to the polyborosiloxane monomer is 1:1-3.

4. The TPU floor mat for ball games according to claim 2, characterized in that: The suspension polymerization reaction occurs in the presence of an initiator, the reaction temperature of the suspension polymerization reaction is 60-75° C., and the reaction time is 6-24 hours.

5. The TPU floor mat for ball games according to claim 2, characterized in that: The polyborosiloxane monomer is prepared by reacting phenylboronic acid and dimethylvinylchlorosilane in a first organic solvent.

6. The TPU floor mat for ball games according to claim 5, characterized in that: The molar ratio of the phenylboric acid to dimethylvinylchlorosilane is 1:2-2.

5.

7. The TPU floor mat for ball games according to claim 1, characterized in that: The auxiliary agent is one of an antioxidant and a weathering agent or a mixture of the two.

8. A method for preparing a TPU floor mat for a ball field according to any one of claims 1 to 7, characterized in that: include: The thermoplastic TPU, modified porous microspheres and auxiliary agents are mixed and added into an extruder, and melt-blended to obtain a mixed melt; Injecting supercritical gas into the middle section of the extruder, and mixing and cooling the injected supercritical gas and the mixed melt in the subsequent temperature zone of the extruder to obtain a cooled homogeneous phase; The homogeneous phase is extruded through an extruder and pelletized underwater to obtain foamed particles; The foamed particles are molded by steam molding to obtain a TPU floor mat.

9. The method for preparing a TPU floor mat for a ball field according to claim 8, characterized in that: The supercritical gas is supercritical carbon dioxide or supercritical nitrogen, and the injection amount of the supercritical gas is 3-15% of the mass of the melt.

10. The TPU floor mat for ball games according to any one of claims 1 to 7 is used to prepare a floor mat for a pickleball court.

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