阅读说明：本技术 一种tpr鞋底及其制备方法 (TPR sole and preparation method thereof ) 是由 张昌其 于 2019-10-25 设计创作，主要内容包括：本发明公开了一种TPR鞋底及其制备方法,按重量份数计,其原料包括以下组分：SBS 100-120份；聚苯乙烯8-10份；顺丁橡胶6-8份；软化剂35-40份；填料5-7份；树脂6-8份；交联剂4-6份；抗老化剂1-2份；润滑剂4-5份。聚苯乙烯和SBS具有很好的相容性,可以改善SBS的硬度、耐磨性、抗撕裂性能和流动性能,增强剪切强度。顺丁橡胶分子链比较规整,滞后和生热量小,具有很大的高弹性、耐磨性和耐低温性,且顺丁橡胶和SBS的软段“B”极性相同,结构相似,顺丁橡胶和SBS具有很好的相容性。在SBS/PS胶中加入顺丁橡胶,能够有效提高TPR的耐磨性、耐屈挠性及耐低温性,使TPR鞋底在很冷的地方穿着也很舒服,不会因低温变硬,加入顺丁橡胶也减少了TPR鞋在苛刻条件下的生热量,延长其使用寿命。(The invention discloses a TPR sole and a preparation method thereof, wherein the TPR sole comprises the following raw materials in parts by weight: SBS 100-120 parts; 8-10 parts of polystyrene; 6-8 parts of butadiene rubber; 35-40 parts of a softener; 5-7 parts of a filler; 6-8 parts of resin; 4-6 parts of a cross-linking agent; 1-2 parts of an anti-aging agent; 4-5 parts of a lubricant. The polystyrene and the SBS have good compatibility, and can improve the hardness, the wear resistance, the tear resistance and the flow property of the SBS and enhance the shear strength. The butadiene rubber has regular molecular chains, small hysteresis and heat generation, high elasticity, wear resistance and low temperature resistance, the polarity of the soft segment B of the butadiene rubber and the SBS is the same, the structure is similar, and the butadiene rubber and the SBS have good compatibility. The addition of the butadiene rubber into the SBS/PS rubber can effectively improve the wear resistance, the flexing resistance and the low temperature resistance of the TPR, so that the TPR sole is comfortable to wear in a cold place and cannot be hardened due to low temperature, the heat generation quantity of the TPR shoe under severe conditions is reduced due to the addition of the butadiene rubber, and the service life of the TPR shoe is prolonged.)

1. A TPR sole, its characterized in that: the raw materials comprise the following components in parts by weight,

SBS 100-120 parts;

8-10 parts of polystyrene;

6-8 parts of butadiene rubber;

35-40 parts of a softener;

5-7 parts of a filler;

6-8 parts of resin;

4-6 parts of a cross-linking agent;

1-2 parts of an anti-aging agent;

4-5 parts of a lubricant.

2. The TPR shoe sole of claim 1, wherein: the softener is naphthenic oil.

3. The TPR shoe sole of claim 1, wherein: the filler is titanium dioxide.

4. The TPR shoe sole of claim 1, wherein: the resin is gum rosin.

5. The TPR shoe sole of claim 1, wherein: the cross-linking agent adopts dicumyl peroxide.

6. The TPR shoe sole of claim 1, wherein: the anti-aging agent is anti-aging agent SP.

7. The TPR shoe sole of claim 1, wherein: magnesium stearate is used as the lubricating agent.

8. The TPR shoe sole of claim 1, wherein: the raw materials comprise 3-5 parts of glycerol zinc by weight.

9. The method of preparing a TPR shoe sole according to any of claims 1-8, wherein: comprises the following steps of (a) carrying out,

s1, preparing master batch: plasticizing the butadiene rubber and the anti-aging agent SP through a double-roller plasticator at normal temperature, and taking out for later use; heating a double-roller plasticator to 150-160 ℃, melting polystyrene, adding the plasticized butadiene rubber, mixing uniformly, and then discharging to obtain master batch;

s2, mixing: continuously putting the masterbatch, SBS, titanium dioxide, gum rosin, dicumyl peroxide, magnesium stearate and zinc glycerolate into a double-roller plastic machine with the temperature of 150-;

s3, die pressing: performing compression molding on the mixed rubber material, wherein the pressure is 12-13Mpa, the temperature is 160 ℃, and preheating is performed for 5min, hot pressing is performed for 2min, and cold pressing is performed for 3 min;

s4, cutting: and cutting the rim charge of the pressed and formed sole to obtain the TPR sole.

Technical Field

The invention relates to the technical field of shoe materials, in particular to a TPR sole and a preparation method thereof.

Background

The TPR material is a thermoplastic rubber material, the TPR sole is generally a high polymer material modified by blending thermoplastic elastomer SBS and other functional additives, and the TPR sole is formed after processing by processes of extrusion, injection, mould pressing and the like, and has the advantages of skid resistance, strong bending property, good air permeability, firm bonding strength and the like.

The Chinese patent with publication number CNA discloses a preparation method of a high-bending-resistance SBS composite sole material, which comprises the following steps: (1) dissolving polypropylene reticular fiber in toluene, placing the dissolved polypropylene reticular fiber in an ultrasonic oscillator for oscillation to remove oil stains and impurities on the surface of the polypropylene reticular fiber, taking out the obtained product after 2 hours, washing the obtained product with deionized water, placing the obtained product in an oven for drying for 2 hours, moving the obtained product to a plasma treatment chamber, vacuumizing the obtained product, introducing argon gas, turning on a radio frequency power supply for plasma treatment, and taking out the obtained product after 3 minutes to obtain modified polypropylene reticular fiber for later use; (2) dissolving SBS and MAH in methyl ethyl ketone, stirring until the SBS and the MAH are completely dissolved, transferring the mixture to a constant-temperature water bath, introducing nitrogen to protect and dropwise adding BPO, wherein the weight ratio of SBS to MAH to BPO is 100:40:3, reacting for 1 hour, then carrying out reduced pressure distillation to remove methyl ethyl ketone, extracting with ketone to remove SBS and MAH which do not participate in the reaction, and placing the obtained product in a vacuum drying oven to dry the obtained product to constant weight to obtain SBS-g-MAH for later use; (3) adding SBS, PTFE and SBS-g-MAH obtained in the step (2) into a high-speed mixer to mix for 10 minutes to obtain a blend, mixing the blend with acetone, ultrasonically stirring until the blend is uniformly dispersed to obtain a prepreg, soaking the modified polypropylene reticular fiber obtained in the step (1) into the prepreg, taking out the prepreg after 20 hours, drying the prepreg, cutting the prepreg, flatly paving the prepreg in a mould, carrying out mould pressing by using a flat press, cooling and demoulding to obtain a high-bending-resistance SBS composite sole material; in the step (3), 52-63 parts of SBS, 10-14 parts of PTFE, 6-6 parts of SBS-g-MAH5 and 25-30 parts of modified polypropylene reticular fiber by weight.

In the above technical scheme, the direction of modifying the sole mainly focuses on the anti-bending performance, but the problem that the SBS material is relatively deficient in wear resistance is not solved, and the improvement is needed.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a TPR sole and a preparation method thereof, and the TPR sole has good wear resistance.

In order to achieve the purpose, the invention provides the following technical scheme:

the TPR sole comprises the following raw materials in parts by weight:

by adopting the technical scheme, the SBS is a triblock copolymer of A-B-A type styrene and butadiene, and structurally comprises a rubbery soft segment B and a plastic hard segment S, and the SBS has a linear or star-shaped structure, wherein the end part of a polybutadiene molecular chain of a central soft segment is inlaid by polystyrene of the hard segment. Because the polystyrene molecule has larger cohesive force and the association action leads the tail end of the polybutylene molecular chain at the central section to be fixed and not to be freely extended and curled, the polystyrene forms a physical crosslinking point, and the whole polymer forms a net structure. Polystyrene is associated and aggregated to form a micro-area which is in a glass state at normal temperature, and the self-reinforcing effect of the polymer is very obvious, which is equivalent to carbon black reinforced vulcanized rubber. When the temperature is raised above the glass transition temperature (100 ℃) of polystyrene, the network breaks and the plastic segments soften and can flow under force, and can therefore be freely shaped like plastic. When cooled, the micro-areas are re-formed and the network structure is restored. The reversibility of this network makes SBS thermoplastic.

Polystyrene (PS) and SBS have good compatibility, and can improve hardness, wear resistance, tear resistance and flow property of SBS and enhance shear strength.

The Butadiene Rubber (BR) has regular molecular chains, small hysteresis and heat generation, high elasticity, wear resistance and low temperature resistance, and the soft segment B of the butadiene rubber and the SBS have the same polarity and similar structure, so that the butadiene rubber and the SBS have good compatibility according to the principle of similar compatibility. The addition of the butadiene rubber into the SBS/PS rubber can effectively improve the wear resistance, the flexing resistance and the low temperature resistance of the TPR, so that the TPR sole is comfortable to wear in a cold place and cannot be hardened due to low temperature, the heat generation quantity of the TPR shoe under severe conditions is reduced due to the addition of the butadiene rubber, and the service life of the TPR shoe is prolonged.

Further, the softener is naphthenic oil.

By adopting the technical scheme, the naphthenic oil and SBS have good compatibility, and have little absorption to ultraviolet and other pipelines, and the fluidity of TPR is obviously improved along with the addition of the naphthenic oil so as to improve the processing performance. And the naphthenic oil weakens the acting force between polybutadiene molecular chain segments in SBS, the motion range of the chain segments is enlarged, the chain segments can be fully extended during stretching, and the external force is easily recovered after being eliminated, so that the bending resistance and the rebound resilience of the shoe material are obviously improved.

Further, the filler is titanium dioxide.

By adopting the technical scheme, as the elongation at break is increased along with the increase of the content of the softening agent, the melt flow rate is increased, the fluidity is improved, but the hardness is reduced. By adding titanium dioxide, the hardness and the wear resistance of TPR can be improved, so that the product performance can be adjusted. Meanwhile, the titanium dioxide can also absorb ultraviolet light to reduce the ultraviolet aging of the TPR, thereby prolonging the service life of the TPR.

Further, gum rosin is used as the resin.

By adopting the technical scheme, the polystyrene is added into the SBS, so that the fluidity and the hardness of a melt can be improved, the processability is improved, and the gum rosin can also play a role in improving the fluidity and the viscosity of a rubber material so as to improve the processability of the TPR. The polystyrene and the gum rosin have a synergistic interaction effect, and the processing performance of the TPR can be further improved by co-doping in the TPR according to a corresponding proportion.

Further, the crosslinking agent adopts dicumyl peroxide.

By adopting the technical scheme, the tensile strength and the bonding strength of the TPR can be effectively improved by adding the dicumyl peroxide.

Further, the anti-aging agent is an anti-aging agent SP.

By adopting the technical scheme, the anti-aging agent SP is also called styrenated phenol, can be used as an anti-aging agent for SBS and butadiene rubber, has good oxidation resistance and heat resistance, and can effectively improve the anti-aging performance of the system.

Further, magnesium stearate is used as the lubricant.

By adopting the technical scheme, the magnesium stearate can play a lubricating role on a system, the viscosity of the system is reduced, the self-adhesiveness is reduced, and the fluidity and the surface glossiness of a finished product are improved.

Further, the raw materials comprise 3-5 parts of glycerol zinc by weight.

By adopting the technical scheme, the zinc glycerolate has good ultraviolet light resistance and thermal stability, and can improve the aging resistance of a system by cooperating with the antioxidant SP. And the zinc glycerolate also has good lubricating effect, and can further reduce the viscosity of a system by being matched with magnesium stearate, and improve the fluidity and the surface gloss of a finished product. In addition, the zinc glycerolate and the magnesium stearate are compounded, so that good thermal stability can be achieved for a system, the thermal aging resistance of the TPR is effectively improved, and the service life of a product is prolonged.

The invention also aims to provide a preparation method of the TPR sole, which comprises the following steps:

s1, preparing master batch: plasticizing the butadiene rubber and the anti-aging agent SP through a double-roller plasticator at normal temperature, and taking out for later use; heating a double-roller plasticator to 150-160 ℃, melting polystyrene, adding the plasticized butadiene rubber, mixing uniformly, and then discharging to obtain master batch;

s2, mixing: continuously putting the masterbatch, SBS, titanium dioxide, gum rosin, dicumyl peroxide, magnesium stearate and zinc glycerolate into a double-roller plastic machine with the temperature of 150-;

s3, die pressing: performing compression molding on the mixed rubber material, wherein the pressure is 12-13Mpa, the temperature is 160 ℃, and preheating is performed for 5min, hot pressing is performed for 2min, and cold pressing is performed for 3 min;

s4, cutting: and cutting the rim charge of the pressed and formed sole to obtain the TPR sole.

By adopting the technical scheme, if the butadiene rubber is added into the SBS alone, the rubber content in the blend is increased, so that the melt elasticity effect is increased, the fluidity of an object is greatly reduced, and the processing is difficult. The master batch is prepared by blending polystyrene and butadiene rubber, so that the defect of SBS can be overcome, and the TPR thermoplastic elastomer material with excellent performance and convenient processing can be obtained.

In conclusion, the invention has the following beneficial effects:

1. polystyrene (PS) and SBS have good compatibility, and can improve hardness, wear resistance, tear resistance and flow property of SBS and enhance shear strength. The Butadiene Rubber (BR) has regular molecular chains, small hysteresis and heat generation, high elasticity, wear resistance and low temperature resistance, and the soft segment B of the butadiene rubber and the SBS have the same polarity and similar structure, so that the butadiene rubber and the SBS have good compatibility according to the principle of similar compatibility. The addition of the butadiene rubber into the SBS/PS rubber can effectively improve the wear resistance, the flexing resistance and the low temperature resistance of the TPR, so that the TPR sole is comfortable to wear in a cold place and cannot be hardened due to low temperature, the heat generation quantity of the TPR shoe under severe conditions is reduced due to the addition of the butadiene rubber, and the service life of the TPR shoe is prolonged.

2. The naphthenic oil and SBS have good compatibility, and less absorption to ultraviolet and other pipelines, and with the addition of the naphthenic oil, the fluidity of TPR is obviously improved, so as to improve the processing performance. And the naphthenic oil weakens the acting force between polybutadiene molecular chain segments in SBS, the motion range of the chain segments is enlarged, the chain segments can be fully extended during stretching, and the external force is easily recovered after being eliminated, so that the bending resistance and the rebound resilience of the shoe material are obviously improved.

The polystyrene is added into SBS to raise the flowability and hardness of the melt and improve the machining performance, and the gum rosin can improve the flowability and viscosity of the rubber material to improve the machining performance of TPR. The polystyrene and the gum rosin have a synergistic interaction effect, and the processing performance of the TPR can be further improved by co-doping in the TPR according to a corresponding proportion.

4. The anti-aging agent SP is also called styrenated phenol, can be used as an anti-aging agent for SBS and butadiene rubber, has good oxidation resistance and heat resistance, and can effectively improve the anti-aging performance of the system.

5. The magnesium stearate has a lubricating effect on a system, reduces the viscosity of the system, reduces the self-adhesiveness, and improves the fluidity and the surface gloss of a finished product.

6. The zinc glycerolate has good ultraviolet light resistance and thermal stability, and can improve the aging resistance of a system by cooperating with an antioxidant SP. And the zinc glycerolate also has good lubricating effect, and can further reduce the viscosity of a system by being matched with magnesium stearate, and improve the fluidity and the surface gloss of a finished product. In addition, the zinc glycerolate and the magnesium stearate are compounded, so that good thermal stability can be achieved for a system, the thermal aging resistance of the TPR is effectively improved, and the service life of a product is prolonged.

7. If butadiene rubber is added alone to SBS, the rubber content in the blend increases, leading to an increase in the melt elasticity effect, which greatly reduces the flowability of the object and makes processing difficult. The master batch is prepared by blending polystyrene and butadiene rubber, so that the defect of SBS can be overcome, and the TPR thermoplastic elastomer material with excellent performance and convenient processing can be obtained.

Drawings

FIG. 1 is a flow chart of a method provided by the present invention;

Detailed Description

The present invention will be described in further detail with reference to the following drawings and examples.