CN116410506B - Anti-skid dirt-resistant thermoplastic plastic runway and preparation method thereof - Google Patents

Abstract

The invention discloses an anti-skid and dirt-resistant thermoplastic plastic runway and a preparation method thereof, which includes a thermoplastic elastic base layer and a coating covering the surface of the thermoplastic elastic base layer; the thermoplastic elastic base layer includes thermoplastic elastomer, oily filler, reinforced resin, inorganic Filled with powder, antioxidants and surface modification additives, the coating includes hydroxyl-terminated polybutadiene, isophorone diisocyanate, catalyst, hydroxyethyl acrylate and UV photoinitiator. The prefabricated plastic track of the present invention uses surface modifiers to build chemical bonds between the UV cured coating and the plastic track to improve the interface compatibility and adhesion between the UV cured coating and the SEBS-based track. With the help of UV curing The surface coating improves the anti-skid and dirt-resistant performance of the plastic runway, and has the advantages of good elasticity, high durability, anti-skid and dirt-resistant surface.

Description

An anti-skid and dirt-resistant thermoplastic plastic runway and its preparation method

Technical field

The invention relates to the technical field of track preparation, and in particular to an anti-skid and dirt-resistant thermoplastic plastic track and a preparation method thereof.

Background technique

Plastic track, also known as all-weather track and field track, is usually composed of polyurethane prepolymer, mixed polyether, waste tire rubber particles or PU particles, pigments, additives and fillers. This kind of track roll is made of vulcanized rubber, and the raw materials are mostly Thermoset materials are difficult to recycle and can easily cause environmental pollution. At present, the thermoplastic plastic runway industry is developing rapidly. Thermoplastic plastic runways based on SEBS are widely used in urban stadiums, campuses and other scenes. SEBS-based plastic track has good environmental weather resistance and aging resistance, excellent mechanical properties, and is a thermoplastic material that is environmentally friendly and recyclable. However, SEBS is a non-polar material with low surface polarity and is easy to absorb stains. Plastic tracks made with SEBS as the base material often have problems such as poor stain resistance and insufficient anti-skid ability.

Patent CN202010189713.2 provides a prefabricated plastic track roll, which uses SEBS as the base material, adds calcium carbonate to improve the strength and toughness of the track, and adds EPDM rubber to provide corrosion resistance and electrical insulation properties. However, the patent provides Modification technology has not solved the problem of poor surface polarity of track materials. This type of track is prone to wear and tear during actual use. At the same time, it has strong adsorption to non-polar stains and is difficult to remove by washing. At the same time, the addition of polyurethane to the track leads to its recycling. Difficult and easy to cause pollution.

Contents of the invention

In view of the above problems, the present invention provides an anti-skid and dirt-resistant thermoplastic plastic track and a preparation method thereof to solve the problems existing in the prior art such as poor polarity of track materials, insufficient interface affinity with polar materials, material polarity and anti-skid properties, etc. It is difficult to achieve simultaneous improvement of mechanical properties. The present invention uses a surface modifier to improve the interface compatibility and adhesion between the UV cured coating and the SEBS-based track by building a chemical bond between the UV cured coating and the plastic track. The anti-skid and dirt-resistant performance of the runway improves the overall performance.

In order to achieve the above objects, the specific technical solutions of the present invention are as follows:

An anti-skid and dirt-resistant thermoplastic plastic runway, including a thermoplastic elastic base layer and a coating covering the surface of the thermoplastic elastic base layer;

The thermoplastic elastic base layer includes the following components by weight: 100 parts of thermoplastic elastomer, 50-100 parts of oily filler, 10-30 parts of reinforcing resin, 20-60 parts of inorganic filling powder, 1-3 parts of antioxidant and 5 to 10 parts of surface modification additive;

The coating includes the following components by weight: 100 parts of hydroxyl-terminated polybutadiene, 11.1-22.2 parts of isophorone diisocyanate, 0.01-0.2 parts of catalyst, 5-10 parts of hydroxyethyl acrylate and UV light initiation 0.5~3.0 parts.

Preferably, the thermoplastic elastomer is SEBS.

Preferably, the oily filler is one of naphthenic oil, paraffin oil or epoxidized soybean oil.

Preferably, the reinforcing resin is one of polypropylene, high-density polyethylene or low-density polyethylene.

Preferably, the inorganic filling powder is one of calcium carbonate, quartz powder or talc powder.

Preferably, the antioxidant is one of antioxidants 1010 or 168.

Preferably, the surface modification assistant is a combination of 1,2-epoxy-4-vinylcyclohexane and hydroxyl-terminated polydimethylsiloxane. More preferably, the mass ratio of 1,2-epoxy-4-vinylcyclohexane and hydroxyl-terminated polydimethylsiloxane is 2:1 to 1:1.

Preferably, the molecular weight of the hydroxyl-terminated polybutadiene is 2000-4000.

Preferably, the catalyst is one of stannous octoate or dibutyltin dilaurate.

Preferably, the UV photoinitiator is one of benzophenone or 2,4-dihydroxybenzophenone.

The invention also provides a method for preparing the above-mentioned anti-skid and dirt-resistant thermoplastic plastic track, which specifically includes the following steps:

(1) Preparation of UV curable surface coating: stir and react hydroxyl-terminated polybutadiene, isophorone diisocyanate and catalyst under anhydrous conditions, control the molar ratio of hydroxyl group to isocyanate group to 1:2, and the reaction temperature 60~80℃ for 3~6 hours, then add hydroxyethyl acrylate and continue the reaction for 5~7 hours. After cooling, add UV photoinitiator to obtain a coating liquid;

(2) Preparation of anti-skid and stain-resistant prefabricated plastic track: Mix the raw materials evenly, then melt, blend and extrude, and then roll to obtain a thermoplastic elastic base layer with rough patterns on the surface;

(3) Apply the coating liquid obtained in step (1) to the surface of the thermoplastic elastic base layer, dry and mold it, and then irradiate it with ultraviolet light to obtain the anti-skid and dirt-resistant thermoplastic plastic track.

Preferably, the mixing temperature in step (2) is 25°C, and the mixing time is 5 to 15 minutes.

Preferably, the extrusion temperature in step (2) is 170-200°C.

Preferably, the extrusion described in step (2) is performed using a twin-screw extruder.

Preferably, the dose of irradiation described in step (3) is 10-15M rad.

The beneficial effects of the present invention are:

The anti-skid and dirt-resistant thermoplastic plastic track provided by the invention can improve the interface affinity between the plastic track surface and the UV cured coating, which not only ensures that the original mechanical properties of the track are not affected, but also solves the problem of the thermoplastic elastomer-based prefabricated plastic track. The problem of being stain-resistant and not slip-resistant.

The present invention uses a polyurethane type UV cured coating as the surface structure of the track. The coating has a polar structure and has excellent wear resistance and anti-fouling properties. However, the SEBS-based thermoplastic plastic track is a non-polar material because the SEBS material is added. The main auxiliary materials of oily fillers and reinforced resins also have very small polarity, and there are problems such as low surface polarity and difficulty in adhesion of surface coatings. The present invention uses the composition of 1,2-epoxy-4-vinylcyclohexane and hydroxyl-terminated polydimethylsiloxane as a surface modifier to improve the adhesion between the track base and the surface coating. The peeling strength is significantly improved, while the contact angle of the track surface is reduced, and the anti-skid value and anti-fouling effect are simultaneously improved.

The polyurethane soft segment structure of the UV curing coating designed in this invention is a polybutadiene polymer segment, which contains a large amount of butadiene-based structure, and the track base material SEBS is styrene-butadiene-benzene. Ethylene block copolymer also contains butadiene structure, so that both the base layer and the surface coating contain the same segment structure, ensuring good compatibility and adhesion between the two.

The surface modifier used in the present invention is a composition of 1,2-epoxy-4-vinylcyclohexane and hydroxyl-terminated polydimethylsiloxane. Under preferred conditions, the mass ratio of the two is 2: 1～1:1. First, both 1,2-epoxy-4-vinylcyclohexane and hydroxyl-terminated polydimethylsiloxane have good compatibility with oily fillers in the runway matrix; second, 1,2-epoxy- 4-Vinylcyclohexane contains unsaturated double bonds. Under the action of UV light and UV photoinitiator, it can be co-cured at the interface with the polyurethane acrylate prepolymer (acrylic functional group) in the UV curable coating. Reaction improves the compatibility and adhesion between the UV cured coating and the SEBS substrate; thirdly, the hydroxyl groups in the hydroxyl-terminated polydimethylsiloxane can react with a small amount of residual isocyanate groups in the UV cured coating (controlling hydroxyl acrylic acid The amount of ester used causes the cross-linking reaction of the isocyanate group (with a small amount of residual isocyanate group), which can also improve the compatibility and adhesion between the UV cured coating and the SEBS substrate; finally, by regulating 1,2-epoxy-4-vinyl The dosage ratio of cyclohexane and hydroxyl-terminated polydimethylsiloxane can control the interface bonding effect.

Description of drawings

Figure 1 is a photo of the antifouling performance test of the sheet made in Example 1 and Comparative Example 1, where a is the initial state of the sheet in Example 1 and Comparative Example 1, and b is the process of the sheet in Example 1 and Comparative Example 1. The state of cleaning with water after contamination.

Detailed ways

The technical solution of the present invention is clearly and completely described below. The following examples are used to illustrate the present invention without limiting the scope of the present invention.

Example 1

(1) Preparation of UV curable surface coating: 100g hydroxyl-terminated polybutadiene (molecular weight 4000), 11.1g isophorone diisocyanate and 0.01g stannous octoate are stirred and reacted under anhydrous conditions, and the hydroxyl group and isocyanate are controlled. The molar ratio of the base is 1:2, the reaction temperature is 60°C, and the time is 6 hours. Finally, 5g hydroxyethyl acrylate is added, and the reaction is continued for 5 hours. After cooling, 1.5g benzophenone is added to obtain UV curing polybutadiene polyurethane. Coating fluid.

(2) Preparation of anti-skid and dirt-resistant prefabricated plastic track:

Combine 100g thermoplastic elastomer SEBS, 50g naphthenic oil, 10g low density polyethylene, 20g calcium carbonate, 1g antioxidant 1010, 5g 1,2-epoxy-4-vinylcyclohexane, 5g hydroxyl-terminated polydimethyl The silicone-based silicone is mixed evenly in a mixer, the mixing temperature is 25°C, and the mixing time is 5 minutes.

The above uniformly mixed materials are melted and blended through a twin-screw extruder, and the extrusion temperature is controlled to 170°C.

The above-mentioned melt-extruded thermoplastic elastomer track roll is introduced from the die head into a double-roller extrusion. One roller extrudes rough patterns on the surface of the track, and the other roller extrudes the bottom of the track into a hollow shape. Finally, it is cooled and formed to obtain Prefabricated plastic track.

(3) The surface of the prefabricated plastic track obtained by cooling and shaping is coated with a coating liquid, and after it is dried and formed, it is irradiated with ultraviolet light at a dose of 10M rad to obtain the anti-skid and dirt-resistant prefabricated plastic track.

Example 2

(1) Preparation of UV curable surface coating: 100g hydroxyl-terminated polybutadiene (molecular weight 2000), 22.2g isophorone diisocyanate and 0.2g dibutyltin dilaurate are stirred and reacted under anhydrous conditions, and controlled The molar ratio of hydroxyl group to isocyanate group is 1:2, the reaction temperature is 80°C, the time is 3 hours, then 10g hydroxyethyl acrylate is added, the reaction continues for 7 hours, after cooling, 3g 2,4-dihydroxybenzophenone is added to obtain UV curable polybutadiene polyurethane coating liquid.

(2) Preparation of anti-skid and dirt-resistant prefabricated plastic track:

Combine 100g thermoplastic elastomer SEBS, 100g naphthenic oil, 30g polypropylene, 60g calcium carbonate, 3g antioxidant 1010, 6g 1,2-epoxy-4-vinylcyclohexane, 3g hydroxyl-terminated polydimethylsiloxane The alkane is mixed evenly in a mixer, the mixing temperature is 25°C, and the mixing time is 15 minutes.

The above uniformly mixed materials were melted and blended through a twin-screw extruder, and the extrusion temperature was controlled to 200°C.

The above-mentioned melt-extruded thermoplastic elastomer track roll is introduced from the die head into a double-roller extrusion. One roller extrudes rough patterns on the surface of the track, and the other roller extrudes the bottom of the track into a hollow shape. Finally, it is cooled and formed to obtain Prefabricated plastic track.

(3) The surface of the prefabricated plastic track obtained by cooling and shaping is coated with a coating liquid, and after it is dried and formed, it is irradiated with ultraviolet light at a dose of 15M rad to obtain the anti-skid and dirt-resistant prefabricated plastic track.

Example 3

(1) Preparation of UV curable surface coating: 100g hydroxyl-terminated polybutadiene (molecular weight 4000), 11.1g isophorone diisocyanate and 0.05g stannous octoate are stirred and reacted under anhydrous conditions, and the hydroxyl group and isocyanate are controlled. The molar ratio of the base is 1:2, the reaction temperature is 70°C, and the time is 5 hours. Finally, 5g hydroxyethyl acrylate is added, and the reaction is continued for 5 hours. After cooling, 0.5g benzophenone is added to obtain UV curing polybutadiene polyurethane. Coating fluid.

(2) Preparation of anti-skid and dirt-resistant prefabricated plastic track:

Combine 100g thermoplastic elastomer SEBS, 75g paraffin oil, 20g high-density polyethylene, 40g talc, 2g antioxidant 1010, 2.5g 1,2-epoxy-4-vinylcyclohexane, 2.5g hydroxyl-terminated polydiethylene The methylsiloxane is mixed evenly in a mixer, the mixing temperature is 25°C, and the mixing time is 10 minutes.

The above uniformly mixed materials are melted and blended through a twin-screw extruder, and the extrusion temperature is controlled to 180°C.

The above-mentioned melt-extruded thermoplastic elastomer track roll is introduced from the die head into a double-roller extrusion. One roller extrudes rough patterns on the surface of the track, and the other roller extrudes the bottom of the track into a hollow shape. Finally, it is cooled and formed to obtain Prefabricated plastic track.

(4) The surface of the prefabricated plastic track obtained by cooling and shaping is coated with a coating liquid, and after it is dried and formed, it is irradiated with ultraviolet light at a dose of 12M rad to obtain the anti-skid and dirt-resistant prefabricated plastic track.

Example 4

(1) Preparation of UV curable surface coating: 100g hydroxyl-terminated polybutadiene (molecular weight 2000), 22.2g isophorone diisocyanate and 0.1g dibutyltin dilaurate are stirred and reacted under anhydrous conditions, and controlled The molar ratio of hydroxyl group to isocyanate group is 1:2, the reaction temperature is 70℃, the time is 4 hours, then 10g hydroxyethyl acrylate is added, the reaction continues for 7 hours, after cooling, 2g 2,4-dihydroxybenzophenone is added to obtain UV Cured polybutadiene-based polyurethane coating fluid.

(2) Preparation of anti-skid and dirt-resistant prefabricated plastic track:

Combine 100g thermoplastic elastomer SEBS, 80g epoxy soybean oil, 30g polypropylene, 50g quartz powder, 2g antioxidant 168, 5g 1,2-epoxy-4-vinylcyclohexane, 2.5g hydroxyl-terminated polydimethyl The siloxane is mixed evenly in a mixer, the mixing temperature is 25°C, and the mixing time is 12 minutes.

The above uniformly mixed materials were melted and blended through a twin-screw extruder, and the extrusion temperature was controlled to 200°C.

The above-mentioned melt-extruded thermoplastic elastomer track roll is introduced from the die head into a double-roller extrusion. One roller extrudes rough patterns on the surface of the track, and the other roller extrudes the bottom of the track into a hollow shape. Finally, it is cooled and formed to obtain Prefabricated plastic track.

(3) The surface of the prefabricated plastic track obtained by cooling and shaping is coated with a coating liquid, and after it is dried and formed, it is irradiated with ultraviolet light at a dose of 15M rad to obtain the anti-skid and dirt-resistant prefabricated plastic track.

Comparative example 1

Preparation of anti-skid and dirt-resistant prefabricated plastic runway:

(1) Mix 100g of thermoplastic elastomer SEBS, 50g of naphthenic oil, 10g of low-density polyethylene, 20g of calcium carbonate, and 1g of antioxidant 1010 in a mixing mixer. The mixing temperature is 25°C and the mixing time is 5 minutes.

(2) Melt and blend the above uniformly mixed materials through a twin-screw extruder, and control the extrusion temperature to 170°C.

(3) The above-mentioned melt-extruded thermoplastic elastomer track roll is introduced from the die head into a double-roller extrusion. One roller extrudes a rough pattern on the surface of the track, and the other roller extrudes a hollow shape on the bottom of the track, and finally cools it. After molding, a prefabricated plastic runway is obtained.

Comparative example 2

(1) Preparation of UV curable surface coating: 100g hydroxyl-terminated polybutadiene (molecular weight 4000), 11.1g isophorone diisocyanate and 0.01g stannous octoate are stirred and reacted under anhydrous conditions, and the hydroxyl group and isocyanate are controlled. The molar ratio of the base is 1:2, the reaction temperature is 60°C, and the time is 6 hours. Finally, 5g hydroxyethyl acrylate is added, and the reaction is continued for 5 hours. After cooling, 1.5g benzophenone is added to obtain UV curing polybutadiene polyurethane. Coating fluid.

(2) Preparation of anti-skid and dirt-resistant prefabricated plastic track:

Mix 100g of thermoplastic elastomer SEBS, 50g of naphthenic oil, 10g of low-density polyethylene, 20g of calcium carbonate, and 1g of antioxidant 1010 in a mixer. The mixing temperature is 25°C and the mixing time is 5 minutes.

The above uniformly mixed materials are melted and blended through a twin-screw extruder, and the extrusion temperature is controlled to 170°C.

The above-mentioned melt-extruded thermoplastic elastomer track roll is introduced from the die head into a double-roller extrusion. One roller extrudes rough patterns on the surface of the track, and the other roller extrudes the bottom of the track into a hollow shape. Finally, it is cooled and formed to obtain Prefabricated plastic track.

(3) The surface of the prefabricated plastic track obtained by cooling and shaping is coated with a coating liquid, and after it is dried and formed, it is irradiated with ultraviolet light at a dose of 10M rad to obtain the anti-skid and dirt-resistant prefabricated plastic track.

Performance tests were performed on the runway samples prepared in each embodiment to demonstrate the performance of the runway. The testing basis is the Track and Field Facilities Standard Manual. The test results are shown in Table 1:

Table 1 Runway instance performance test

test track 180° peel strength (N/m) Surface contact angle (°) Anti-skid value (BPN20℃) Example 1 278 78.6 52 Example 2 297 76.4 54 Example 3 231 78.9 50 Example 4 254 76.2 55 Comparative example 1 / 94.3 40 Comparative example 2 85 82.6 45

As can be seen from Table 1, the anti-skid and dirt-resistant prefabricated plastic track added with surface modification additives 1,2-epoxy-4-vinylcyclohexane and hydroxyl-terminated polydimethylsiloxane is better than Plastic tracks without UV-cured surface coating, or with UV-cured surface coating without surface modification additives, have higher 180° peel strength, surface polarity and anti-skid performance. This is due to surface modification. The additive and the polyurethane acrylate prepolymer in the UV-cured coating undergo a co-curing reaction at the interface, improving the compatibility and adhesion between the UV-cured coating and the SEBS substrate, thereby improving the material's anti-skid and stain-resistant properties.

Although the present invention has been illustrated and described with specific embodiments, it should be realized that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit it; those of ordinary skill in the art should understand that: Without departing from the spirit and scope of the present invention, the technical solutions described in the foregoing embodiments may be modified, or some or all of the technical features thereof may be equivalently substituted; however, these modifications or substitutions shall not make the corresponding technical solutions Essentially departing from the scope of the technical solutions of the various embodiments of the present invention, this means that all such substitutions and modifications falling within the scope of the present invention are included in the appended claims.

Claims (11)

1. An anti-skid dirt-resistant thermoplastic plastic track is characterized by comprising a thermoplastic elastic base layer and a coating layer coated on the surface of the thermoplastic elastic base layer;

the thermoplastic elastic base layer comprises the following components in parts by weight: 100 parts of thermoplastic elastomer, 50-100 parts of oily filler, 10-30 parts of reinforcing resin, 20-60 parts of inorganic filling powder, 1-3 parts of antioxidant and 5-10 parts of surface modification auxiliary agent; the thermoplastic elastomer is SEBS; the surface modification auxiliary agent is a composition of 1, 2-epoxy-4-vinylcyclohexane and hydroxyl-terminated polydimethylsiloxane, and the mass ratio of the 1, 2-epoxy-4-vinylcyclohexane to the hydroxyl-terminated polydimethylsiloxane is 2:1-1:1;

the coating comprises the following components in parts by weight: 100 parts of hydroxyl-terminated polybutadiene, 11.1-22.2 parts of isophorone diisocyanate, 0.01-0.2 part of catalyst, 5-10 parts of hydroxyethyl acrylate and 0.5-3.0 parts of UV photoinitiator.

2. The anti-skid and dirt-resistant thermoplastic racetrack of claim 1, wherein the antioxidant is one of antioxidants 1010 or 168.

3. The non-slip dirt-resistant thermoplastic racetrack of claim 1, wherein the oily filler is one of naphthenic oil, paraffinic oil, or epoxidized soybean oil.

4. The non-slip dirt-resistant thermoplastic racetrack of claim 1, wherein the reinforcement resin is one of polypropylene, high density polyethylene, or low density polyethylene.

5. The non-slip dirt-resistant thermoplastic racetrack of claim 1, wherein the inorganic filler powder is one of calcium carbonate, quartz powder, or talc.

6. The anti-slip and dirt-resistant thermoplastic racetrack of claim 1, wherein the hydroxyl-terminated polybutadiene has a molecular weight of 2000-4000.

7. The non-slip, dirt-resistant thermoplastic racetrack of claim 1, wherein the catalyst is one of stannous octoate or dibutyltin dilaurate.

8. The non-slip dirt-resistant thermoplastic racetrack of claim 1, wherein the UV photoinitiator is one of benzophenone or 2, 4-dihydroxybenzophenone.

9. A method of making an anti-slip and dirt-resistant thermoplastic racetrack as claimed in any one of claims 1 to 8, comprising the steps of:

(1) Preparation of UV-cured surface coating: stirring hydroxyl-terminated polybutadiene, isophorone diisocyanate and a catalyst under anhydrous condition for reaction, controlling the molar ratio of hydroxyl to isocyanate groups to be 1:2, reacting at 60-80 ℃ for 3-6 hours, adding hydroxyethyl acrylate, continuously reacting for 5-7 hours, cooling, and adding a UV photoinitiator to obtain a coating liquid;

(2) Preparing an anti-slip and dirt-resistant prefabricated plastic track: uniformly mixing the raw materials, then melting, blending and extruding, and then rolling to obtain a thermoplastic elastic base layer with a rough pattern on the surface;

(3) And (3) coating the surface of the thermoplastic elastic base layer with the coating liquid obtained in the step (1), and carrying out ultraviolet irradiation after drying and forming to obtain the anti-slip dirt-resistant thermoplastic runway.

10. The method according to claim 9, wherein the extrusion temperature in step (2) is 170 to 200 ℃.

11. The method of claim 9, wherein the irradiation in step (3) is at a dose of 10 to 15 mrad.