CN112852028B - Thermoplastic elastomer composition for sports floor and preparation method thereof - Google Patents

Abstract

The invention provides a thermoplastic elastomer composition for a sports floor and a preparation method thereof, wherein the thermoplastic elastomer composition for the sports floor comprises the following raw materials in parts by weight: 90-110 parts of butadiene rubber powder, 60-80 parts of natural rubber powder, 40-60 parts of polyvinyl chloride resin, 40-50 parts of epoxy resin, 60-70 parts of polystyrene, 20-30 parts of talcum powder, 20-30 parts of white carbon black, 40-60 parts of benzene glycol, 40-60 parts of benzene, 20-30 parts of vulcanization activator, 15-25 parts of vulcanization accelerator, 15-25 parts of rubber auxiliary agent, 10-20 parts of silane coupling agent, 10-20 parts of stabilizer, 10-20 parts of plasticizer, 15-25 parts of cross-linking agent and 15-25 parts of vulcanizing agent. In the invention, the thermoplastic elastomer composition for the sports floor has the advantages of good elasticity, crack resistance, shock absorption, elasticity, oil control, shrinkage resistance and the like, and long service life.

Description

A kind of thermoplastic elastomer composition for sports floor and preparation method thereof

technical field

The invention relates to the technical field of sports field floors, in particular to a thermoplastic elastomer composition for sports floors and a preparation method thereof.

Background technique

Sports flooring is a floor specially developed for sports venues using polyvinyl chloride materials. Specifically, it uses polyvinyl chloride and its copolymer resin as the main raw material, adding fillers, plasticizers, stabilizers, colorants and other auxiliary materials. A floor covering produced by coating or calendering, extrusion or extrusion on a sheet-like continuous substrate.

A thermoplastic elastomer composition and its preparation method and application are disclosed in the Chinese invention patent with the publication number CN107974024B. The composition includes the following raw material components in parts by weight: SEPS and/or SEEPS, 75-120 parts; ethylene - Octene block copolymer olefin, 65-102 parts; Paraffin oil, 80-150 parts; Maleic anhydride grafted butadiene, 66-120 parts; Maleic anhydride grafted polypropylene, 66-135 parts; Rubber powder , 120-175 parts; silicone powder, 45-66 parts; calcium carbonate, 25-58 parts; PP particles 30-50 parts; DCP masterbatches accounting for 3%-8% of the total weight of the thermoplastic elastomer composition; and TMPTMA accounting for 1.9%-10% of the total weight of the thermoplastic elastomer composition. The floor prepared by adopting the thermoplastic elastomer has the advantages of high wet slip resistance, abrasion resistance and weather resistance.

However, the inventor believes that the sports field floor prepared from the above thermoplastic elastomer composition has defects such as poor deformation resistance and poor cracking resistance, which greatly shortens the service life of the sports field floor.

Contents of the invention

Aiming at the problems existing in the prior art, the present invention provides a thermoplastic elastomer composition for sports flooring and a preparation method thereof. The sports flooring has excellent performances such as deformation resistance, crack resistance, elasticity, and shock absorption.

To achieve the above object, the present invention is achieved through the following technical solutions:

A thermoplastic elastomer composition for sports flooring, the composition of the elastomer composition includes the following raw materials in parts by weight:

Butadiene rubber powder 90-110 parts, natural rubber powder 60-80 parts, polyvinyl chloride resin 40-60 parts, epoxy resin 40-50 parts, polystyrene 60-70 parts, talcum powder 20-30 parts, white 20-30 parts of carbon black, 40-60 parts of benzene glycol, 40-60 parts of benzene, 20-30 parts of vulcanization activator, 15-25 parts of vulcanization accelerator, 15-25 parts of rubber additives, 10 parts of silane coupling agent -20 parts, stabilizer 10-20 parts, plasticizer 10-20 parts, crosslinking agent 15-25 parts, vulcanizing agent 15-25 parts.

Preferably, the constituents of the elastomer composition include the following raw materials in parts by weight:

100 parts of butadiene rubber powder, 70 parts of natural rubber powder, 50 parts of polyvinyl chloride resin, 45 parts of epoxy resin, 65 parts of polystyrene, 25 parts of talcum powder, 25 parts of white carbon black, 50 parts of benzene glycol, benzene 50 parts, 25 parts of vulcanization activator, 20 parts of vulcanization accelerator, 20 parts of rubber additives, 15 parts of silane coupling agent, 15 parts of stabilizer, 15 parts of plasticizer, 20 parts of crosslinking agent, 20 parts of vulcanizing agent.

Preferably, the vulcanization activator is stearic acid.

Preferably, the vulcanization accelerator is zinc oxide.

Preferably, the rubber additive is one of sulfur phenolic compounds, alkylphenol disulfides or aromatic hydrocarbon disulfides.

A preparation method of a thermoplastic elastomer composition for sports flooring comprises the following steps:

(1) Weigh benzenediol, benzene and butadiene rubber powder in proportion, mix them evenly, extract until the solution is colorless, dry the solution at 80°C, and after microwave radiation treatment, keep it sealed to obtain microwave-modified Butadiene rubber powder;

(2) Take natural rubber powder, vulcanization activator, vulcanization accelerator, talcum powder and vulcanization agent in proportion, put them into an open mill after mixing, at a temperature of 140-150°C, and a pressure of 10MPa, knead 1-2h to get the mixed glue A, set aside;

(3) Weigh rubber additives and crosslinking agents in proportion, mix them evenly with microwave-modified butadiene rubber powder, and then put them into an open mill. At a temperature of 45-50 ° C and a pressure of 5 MPa, mix for 45 -55min to get the mixed glue B, set aside;

(4) Weigh polyvinyl chloride resin, epoxy resin, polystyrene, white carbon black, silane coupling agent, stabilizer and plasticizer in proportion, mix them with mixed rubber A and mixed rubber B evenly, and put them into refining machine, kneading to obtain a blend sheet, which is the result.

Preferably, the microwave radiation treatment time in the step (1) is 30-300s.

Preferably, the mixing temperature in the step (4) is 170-180°C, and the mixing time is 1-2h.

The beneficial effects of the present invention are:

Microwave radiation breaks some of the crosslinks in the butadiene rubber powder, and the surface oxidizes to increase the oxygen-containing groups, thereby activating the surface of the butadiene rubber powder and strengthening the bond between polystyrene and the butadiene rubber powder after microwave radiation. Compatibility, thereby enhancing the bonding force between polystyrene and butadiene rubber powder after microwave radiation, so that the particle distance between the two components is reduced, resulting in short and dense silver streaks, so that silver The probability of meeting between grains and silver grains or particles is increased, and it is used to prepare a thermoplastic elastomer composition for sports flooring, so that the toughness of the elastomer composition is enhanced, and the probability of tile deformation on the surface of the sports floor is reduced.

After natural rubber powder and talcum powder are mixed, the barrier effect of talc powder limits the mobility of natural rubber powder. The effect of talc powder on the mechanical properties of natural rubber powder is to make its molecular chain orientate, thereby improving the thermoplasticity of sports flooring. The tensile strength, tearing breaking strength and mechanical stability of the elastomer composition are beneficial to prolonging the service life of the sports floor.

The molecular chain of butadiene rubber powder has a high degree of linearity and a narrow molecular weight distribution, and the molecular chain structure is relatively regular, so that its molecular chain can enter the nano-pores of silica to form an "interlocking structure". Butadiene rubber powder and white carbon black are used in combination to prepare a thermoplastic elastomer composition for sports floors, thereby enhancing the mechanical properties of the elastomer composition such as elasticity, shock absorption, wear resistance, and shrinkage resistance.

Under the combined effect of vulcanization activator and crosslinking agent, butadiene rubber molecules and natural rubber molecules gradually form a three-dimensional molecular network, which is used to prepare thermoplastic elastomer compositions for sports floors, and reduces the viscosity of elastomer compositions in oils. The dissolved amount, the cross-linked molecular chain is longer and stretches well, and the oil absorption ratio gradually increases, thereby improving the oil absorption performance of the elastomer composition and reducing the oil yield of the sports floor.

The use of stearic acid as a vulcanization activator can reduce the friction between other molecules in the system between resin and rubber and processing equipment, improve its fluidity and mold release during molding, and promote the progress of the reaction.

The rubber additive is one of sulfur phenolic compounds, alkylphenol disulfides, and aromatic hydrocarbon disulfides, which can improve the plasticity of raw rubber and shorten the plasticating time. Vulcanization accelerator, also known as rubber accelerator or accelerator, can reduce the vulcanization temperature, reduce the amount of vulcanizing agent, shorten the vulcanization time and improve the performance of vulcanized rubber.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the present invention Examples, not all examples. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

Example 1:

A thermoplastic elastomer composition for sports flooring, the composition of the elastomer composition includes the following raw materials in parts by weight:

Butadiene rubber powder 90 parts, natural rubber powder 60 parts, polyvinyl chloride resin 40 parts, epoxy resin 40 parts, polystyrene 60 parts, talcum powder 20 parts, white carbon black 20 parts, benzene glycol 40 parts, benzene 40 parts, 20 parts of stearic acid, 15 parts of zinc oxide, 15 parts of thiophenolic compound, 10 parts of silane coupling agent, 10 parts of stabilizer, 10 parts of plasticizer, 15 parts of crosslinking agent, and 15 parts of vulcanizing agent.

A preparation method for a thermoplastic elastomer composition for sports floors, comprising the following steps:

(1) Weigh benzene glycol, benzene and cis-butadiene rubber powder in proportion, mix them evenly, extract until the solution is colorless, dry the solution at 80°C, treat it with microwave radiation for 30s, and keep it sealed to obtain microwave modified butadiene rubber powder;

(2) Take natural rubber powder, stearic acid, zinc oxide, talcum powder and vulcanizing agent in proportion, put them into an open mill after mixing evenly, and mix for 1 hour at a temperature of 140° C. and a pressure of 10 MPa to obtain a mixture Glue A, spare;

(3) Weigh the sulfur phenolic compound and cross-linking agent in proportion, mix them evenly with microwave-modified butadiene rubber powder, and then put them into an open mill. At a temperature of 45°C and a pressure of 5 MPa, knead for 45 minutes to obtain Mixed glue B, spare;

(4) Weigh polyvinyl chloride resin, epoxy resin, polystyrene, white carbon black, silane coupling agent, stabilizer and plasticizer in proportion, mix them with mixed rubber A and mixed rubber B evenly, and put them into refining machine, kneading at 170°C for 1 hour to obtain a blend sheet, which is the obtained product.

Example 2:

A thermoplastic elastomer composition for sports flooring, the composition of the elastomer composition includes the following raw materials in parts by weight:

110 parts of butadiene rubber powder, 80 parts of natural rubber powder, 60 parts of polyvinyl chloride resin, 50 parts of epoxy resin, 70 parts of polystyrene, 30 parts of talcum powder, 30 parts of white carbon black, 60 parts of benzene glycol, benzene 60 parts, 30 parts of stearic acid, 25 parts of zinc oxide, 25 parts of alkylphenol disulfide, 20 parts of silane coupling agent, 20 parts of stabilizer, 20 parts of plasticizer, 25 parts of crosslinking agent, 25 parts of vulcanizing agent share.

A preparation method for a thermoplastic elastomer composition for sports floors, comprising the following steps:

(1) Weigh benzenediol, benzene and butadiene rubber powder in proportion, mix them evenly, extract until the solution is colorless, dry the solution at 80°C, treat it with microwave radiation for 300s, and keep it sealed to obtain microwave modified butadiene rubber powder;

(2) Take natural rubber powder, stearic acid, zinc oxide, talcum powder and vulcanizing agent in proportion, put them into an open mill after mixing evenly, and mix for 2 hours at a temperature of 150 ° C and a pressure of 10 MPa to obtain a mixture Glue A, spare;

(3) Weigh the alkylphenol disulfide and cross-linking agent in proportion, mix them evenly with the microwave-modified butadiene rubber powder, put them into the open mill, and mix them at a temperature of 50°C and a pressure of 5MPa 55 minutes to get the mixed glue B, set aside;

(4) Weigh polyvinyl chloride resin, epoxy resin, polystyrene, white carbon black, silane coupling agent, stabilizer and plasticizer in proportion, mix them with mixed rubber A and mixed rubber B evenly, and put them into refining machine, kneading at 180°C for 2 hours to obtain a blend sheet, which is the obtained.

Example 3:

A thermoplastic elastomer composition for sports flooring, the composition of the elastomer composition includes the following raw materials in parts by weight:

100 parts of butadiene rubber powder, 70 parts of natural rubber powder, 50 parts of polyvinyl chloride resin, 45 parts of epoxy resin, 65 parts of polystyrene, 25 parts of talcum powder, 25 parts of white carbon black, 50 parts of benzene glycol, benzene 50 parts, 25 parts of stearic acid, 20 parts of zinc oxide, 20 parts of alkylphenol disulfide, 15 parts of silane coupling agent, 15 parts of stabilizer, 15 parts of plasticizer, 20 parts of crosslinking agent, 20 parts of vulcanizing agent share.

A preparation method for a thermoplastic elastomer composition for sports floors, comprising the following steps:

(1) Weigh benzenediol, benzene and butadiene rubber powder in proportion, mix them evenly, extract until the solution is colorless, dry the solution at 80°C, treat it with microwave radiation for 50s, and keep it sealed to obtain microwave modified butadiene rubber powder;

(2) Weigh natural rubber powder, stearic acid, zinc oxide, talcum powder and vulcanizing agent in proportion, put them into an open mill after mixing evenly, and mix for 1.5h at a temperature of 145°C and a pressure of 10MPa to obtain Mixed glue A, spare;

(3) Weigh the alkylphenol disulfide and cross-linking agent in proportion, mix them evenly with the microwave-modified butadiene rubber powder, put them into the open mill, and mix them under the conditions of temperature 47.5 °C and pressure 5 MPa Mixed glue B was obtained in 50 minutes and set aside;

(4) Weigh polyvinyl chloride resin, epoxy resin, polystyrene, white carbon black, silane coupling agent, stabilizer and plasticizer in proportion, mix them with mixed rubber A and mixed rubber B evenly, and put them into refining machine, kneading at 175°C for 1.5h to obtain a blend sheet, which is the obtained.

Example 4:

A thermoplastic elastomer composition for sports flooring, the composition of the elastomer composition includes the following raw materials in parts by weight:

Butadiene rubber powder 95 parts, natural rubber powder 65 parts, polyvinyl chloride resin 45 parts, epoxy resin 45 parts, polystyrene 65 parts, talcum powder 25 parts, white carbon black 25 parts, benzene glycol 45 parts, benzene 45 parts, 25 parts of stearic acid, 18 parts of zinc oxide, 20 parts of aromatic disulfide, 17 parts of silane coupling agent, 17 parts of stabilizer, 17 parts of plasticizer, 20 parts of crosslinking agent, and 20 parts of vulcanizing agent.

A preparation method for a thermoplastic elastomer composition for sports floors, comprising the following steps:

(1) Weigh benzene glycol, benzene and cis-butadiene rubber powder in proportion, mix them evenly, extract until the solution is colorless, dry the solution at 80°C, treat it with microwave radiation for 100s, and keep it sealed to obtain microwave modified butadiene rubber powder;

(2) Take natural rubber powder, stearic acid, zinc oxide, talcum powder and vulcanizing agent in proportion, put them into an open mill after mixing evenly, and mix for 1 hour at a temperature of 142 ° C and a pressure of 10 MPa to obtain a mixture Glue A, spare;

(3) Weigh aromatic hydrocarbon disulfide and crosslinking agent in proportion, mix them evenly with microwave-modified butadiene rubber powder, and then put them into an open mill. At a temperature of 47°C and a pressure of 5 MPa, knead for 52 minutes to obtain Mixed glue B, spare;

(4) Weigh polyvinyl chloride resin, epoxy resin, polystyrene, white carbon black, silane coupling agent, stabilizer and plasticizer in proportion, mix them with mixed rubber A and mixed rubber B evenly, and put them into refining machine, kneading at 174°C for 2 hours to obtain a blend sheet, which is the obtained.

Example 5:

A thermoplastic elastomer composition for sports flooring, the composition of the elastomer composition includes the following raw materials in parts by weight:

Butadiene rubber powder 105 parts, natural rubber powder 75 parts, polyvinyl chloride resin 55 parts, epoxy resin 48 parts, polystyrene 68 parts, talcum powder 26 parts, white carbon black 26 parts, benzene glycol 57 parts, benzene 50 parts, 27 parts of stearic acid, 22 parts of zinc oxide, 22 parts of aromatic disulfide, 17 parts of silane coupling agent, 17 parts of stabilizer, 17 parts of plasticizer, 22 parts of crosslinking agent, and 22 parts of vulcanizing agent.

A preparation method for a thermoplastic elastomer composition for sports floors, comprising the following steps:

(1) Weigh benzene glycol, benzene and cis-butadiene rubber powder in proportion, mix them evenly, extract until the solution is colorless, dry the solution at 80°C, treat it with microwave radiation for 200s, and keep it sealed to obtain microwave-modified butadiene rubber powder;

(2) Take natural rubber powder, stearic acid, zinc oxide, talcum powder and vulcanizing agent in proportion, put them into an open mill after mixing evenly, and mix for 1 hour at a temperature of 148 °C and a pressure of 10 MPa to obtain a mixture Glue A, spare;

(3) Weigh aromatic hydrocarbon disulfide and crosslinking agent in proportion, mix them evenly with microwave-modified butadiene rubber powder, and put them into an open mill. At a temperature of 48 ° C and a pressure of 5 MPa, knead for 50 minutes to obtain Mixed glue B, spare;

(4) Weigh polyvinyl chloride resin, epoxy resin, polystyrene, white carbon black, silane coupling agent, stabilizer and plasticizer in proportion, mix them with mixed rubber A and mixed rubber B evenly, and put them into refining machine, kneading at 172°C for 1 hour to obtain a blend sheet, which is the obtained product.

Comparative example 1:

The only difference between this comparative example and Example 3 is that no polystyrene is added.

Comparative example 2:

The only difference between this comparative example and Example 3 is that no talcum powder is added.

Comparative example 3:

The only difference between this comparative example and Example 3 is that no white carbon black is added.

Comparative example 4:

The only difference between this comparative example and Example 3 is that no benzenediol and benzene were added.

Comparative example 5:

The only difference between this comparative example and Example 3 is that no stearic acid is added.

Comparative example 6:

The only difference between this comparative example and Example 3 is that no zinc oxide is added.

Comparative example 7:

The only difference between this comparative example and Example 3 is that no alkylphenol disulfide is added.

Comparative example 8:

The only difference between this comparative example and Example 3 is that no butadiene rubber powder is added.

Comparative example 9:

The only difference between this comparative example and Example 3 is that no microwave radiation treatment was performed in step (1).

The elastomer composition obtained in the above-mentioned examples 1-5 and comparative examples 1-9 is subjected to a performance test,

The total phenol content, viscosity, and free fatty acid ratio of the elastomer composition in the elastomer composition were measured, and the results are shown in Table 1.

Table 1 embodiment 1-3, the performance parameter of comparative example 1-9 gained elastomer composition

As can be seen from Table 1, the hardness, elasticity, tensile strength and fracture resistance of the thermoplastic elastomer compositions for sports floors obtained in Examples 1-5 are all better than those obtained in Comparative Examples 1-9. things.

In the present invention, microwave radiation breaks part of the cross-linking bonds in the butadiene rubber powder, and the surface oxidizes to increase the oxygen-containing groups, thereby activating the surface of the butadiene rubber powder and strengthening the polystyrene and butadiene rubber after microwave radiation. Compatibility between rubber powders, thereby enhancing the bonding force between polystyrene and butadiene rubber powder after microwave radiation, so that the particle distance between the two components is reduced, resulting in short and dense silver streaks In this way, the probability of silver crazes and silver crazes or particles meeting increases, which is used to prepare thermoplastic elastomer compositions for sports floors, so that the toughness of the elastomer compositions is enhanced, and the probability of tile deformation on the surface of sports floors is reduced.

The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it can still be described in the foregoing embodiments Modifications are made to the recorded technical solutions, or equivalent replacements are made to some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. The thermoplastic elastomer composition for the sports floor is characterized by comprising the following raw materials in parts by weight:

90-110 parts of butadiene rubber powder, 60-80 parts of natural rubber powder, 40-60 parts of polyvinyl chloride resin, 40-50 parts of epoxy resin, 60-70 parts of polystyrene, 20-30 parts of talcum powder, 20-30 parts of white carbon black, 40-60 parts of benzene glycol, 40-60 parts of benzene, 20-30 parts of vulcanization activator, 15-25 parts of vulcanization accelerator, 15-25 parts of rubber auxiliary agent, 10-20 parts of silane coupling agent, 10-20 parts of stabilizer, 10-20 parts of plasticizer, 15-25 parts of cross-linking agent and 15-25 parts of vulcanizing agent;

the preparation method of the thermoplastic elastomer composition for the sports floor comprises the following steps:

(1) Weighing benzene glycol, benzene and butadiene rubber powder according to a proportion, uniformly mixing, extracting until the solution is colorless, drying the solution at 80 ℃, carrying out microwave radiation treatment, and sealing and preserving to obtain microwave modified butadiene rubber powder;

(2) Weighing natural rubber powder, a vulcanization activator, a vulcanization accelerator, talcum powder and a vulcanizing agent according to a proportion, uniformly mixing, and then putting into an open mill, and mixing for 1-2 hours under the conditions of 140-150 ℃ and 10MPa of pressure to obtain mixed rubber A for later use;

(3) Weighing a rubber auxiliary agent and a cross-linking agent according to a proportion, uniformly mixing the rubber auxiliary agent and the microwave modified butadiene rubber powder, and then putting the mixture into an open mill, and mixing the mixture for 45-55min under the conditions of the temperature of 45-50 ℃ and the pressure of 5MPa to obtain a mixed rubber B for later use;

(4) And (3) weighing polyvinyl chloride resin, epoxy resin, polystyrene, white carbon black, a silane coupling agent, a stabilizer and a plasticizer according to a proportion, uniformly mixing the polyvinyl chloride resin, the epoxy resin, the polystyrene, the white carbon black, the silane coupling agent, the stabilizer and the plasticizer with the mixed glue A and the mixed glue B, and then putting the mixture into an open mill for mixing to obtain a blend sheet.

2. The thermoplastic elastomer composition for sports floors as claimed in claim 1, wherein the composition components of the elastomer composition comprise the following raw materials in parts by weight:

100 parts of butadiene rubber powder, 70 parts of natural rubber powder, 50 parts of polyvinyl chloride resin, 45 parts of epoxy resin, 65 parts of polystyrene, 25 parts of talcum powder, 25 parts of white carbon black, 50 parts of benzene, 25 parts of vulcanization activator, 20 parts of vulcanization accelerator, 20 parts of rubber auxiliary agent, 15 parts of silane coupling agent, 15 parts of stabilizer, 15 parts of plasticizer, 20 parts of cross-linking agent and 20 parts of vulcanizing agent.

3. The thermoplastic elastomer composition for sports flooring according to claim 1, wherein the vulcanization activator is stearic acid.

4. The thermoplastic elastomer composition for sports floors according to claim 1, characterized in that the vulcanization accelerator is zinc oxide.

5. The thermoplastic elastomer composition for sports floors according to claim 1, wherein the rubber auxiliary is one of a thiophenol compound, an alkylphenol disulfide or an aromatic hydrocarbon disulfide.

6. The thermoplastic elastomer composition for sports flooring according to claim 1, wherein the microwave irradiation treatment time in step (1) is 30 to 300 seconds in the preparation method of the thermoplastic elastomer composition for sports flooring.

7. The thermoplastic elastomer composition for sports flooring according to claim 1, wherein the kneading temperature in step (4) is 170 to 180℃and the kneading time is 1 to 2 hours.