阅读说明：本技术 一种耐磨增韧橡胶地板革的制备方法 (Preparation method of wear-resistant toughened rubber floor leather ) 是由 肖殿业 饶保东 于 2019-10-09 设计创作，主要内容包括：本发明公开了一种耐磨增韧橡胶地板革的制备方法,制备方法如下：1)对长石粉进行改性处理；2)对碳纳米管进行改性处理；3)将双马来酰亚铵树脂熔融后加入改性长石粉,得到树脂预聚体,然后加入改性碳纳米管、二乙胺和硬脂酸钙,得到增韧双马来酰亚铵树脂；4)将苯乙烯和环烷油、古马隆树脂和增韧双马来酰亚铵树脂以及马隆树脂和丁苯橡胶组成的三组共混物混合,加入过氧化二异丙苯,得到增韧丁苯橡胶；5)将增韧丁苯橡胶与剩余原料经密炼、挤出、定型和硫化后即可制得橡胶地板革。本发明通过对原料中的合成橡胶进行改性处理,增强其韧性和耐磨性,从而使得橡胶地板革的表面具有良好的耐磨性和韧性,从而提高了橡胶地板革的脚感和使用寿命。(The invention discloses a preparation method of wear-resistant toughened rubber floor leather, which comprises the following steps: 1) modifying feldspar powder; 2) carrying out modification treatment on the carbon nano tube; 3) melting bismaleimide resin, adding modified feldspar powder to obtain a resin prepolymer, and adding a modified carbon nanotube, diethylamine and calcium stearate to obtain toughened bismaleimide resin; 4) mixing three groups of blends consisting of styrene, naphthenic oil, coumarone resin, toughened bismaleimide resin and the coumarone resin and styrene butadiene rubber, and adding dicumyl peroxide to obtain toughened styrene butadiene rubber; 5) the toughened styrene-butadiene rubber and the rest raw materials are banburied, extruded, shaped and vulcanized to obtain the rubber floor leather. According to the invention, the synthetic rubber in the raw materials is modified to enhance the toughness and wear resistance, so that the surface of the rubber floor leather has good wear resistance and toughness, the foot feel of the rubber floor leather is improved and the service life of the rubber floor leather is prolonged.)

1. The preparation method of the wear-resistant toughened rubber floor leather is characterized by comprising the following steps of:

1) adding feldspar powder into an excessive solution composed of hydrogen peroxide and concentrated sulfuric acid, stirring at the normal temperature at the rotation speed of 100-150r/min for 30-40min, washing the feldspar powder to be neutral after the reaction is finished, filtering and drying, slowly adding the feldspar powder into a coupling agent ethanol solution, reacting for 2-3h at the normal temperature, washing with distilled water after the reaction is finished, filtering for 4-5 times, and drying at the temperature of 50-60 ℃ to constant weight to obtain modified feldspar powder;

2) mixing hexamethylene diamine and N, N-dimethylformamide, oscillating and dispersing for 1-2h under 300-400W ultrasonic wave, adding N, N-dicyclohexylcarbodiimide and acidified carbon nano tubes, continuing to ultrasonically disperse for 20-30min, refluxing in an oil bath under magnetic stirring at 130-140 ℃ for 25-30h, naturally cooling to room temperature after the reaction is finished, filtering and washing, and vacuum drying the filtrate at 80-90 ℃ for 10-15h to obtain modified carbon nano tubes;

3) heating and melting bismaleimide resin, magnetically stirring at 175 ℃ of 160-plus materials for 30-40min, cooling to 110-plus materials, adding modified feldspar powder, continuing to stir for 20-30min, adding acetone as a solvent to obtain a resin prepolymer, adding a modified carbon nanotube into the resin prepolymer, stirring at 500r/min of 400-plus materials for 1-2h, adding diethylamine and calcium stearate, continuing to stir for 20-30min, placing in an oven, curing at 250 ℃ of 230-plus materials for 6-8h, cooling, and crushing to obtain toughened bismaleimide resin;

4) uniformly mixing styrene and naphthenic oil, then preserving heat for 2-3h at 165 ℃ of 155-plus-material, blending and heating liquid coumarone resin and toughened bismaleimide resin to 170 ℃ of 160-plus-material, preserving heat for 1-2h, blending and heating liquid coumarone resin and styrene butadiene rubber to 140 ℃ of 130-plus-material, preserving heat for 1-2h, then blending the pre-mixed three groups of blends, adding a small amount of dicumyl peroxide, heating to 180 ℃ of 170-plus-material, preserving heat for 3-4h, then cooling to 110 ℃ of 100-plus-material, and continuing preserving heat for 1-2h to obtain toughened styrene butadiene rubber;

5) the toughened styrene-butadiene rubber, the natural rubber, the anti-heat-aging agent and the colorant are sequentially put into an internal mixer for internal mixing, the internally mixed rubber material is cooled and then put into the internal mixer with the di-tert-butylperoxyisopropyl benzene for secondary internal mixing, the internally mixed rubber material is extruded into sheets by a rubber extruder, the sheets are vulcanized by a vulcanizer after hot press forming, and the rubber floor leather can be prepared after the vulcanized rubber sheets are completely cooled.

2. The preparation method of the wear-resistant toughened rubber flooring according to claim 1, wherein in the step 1), the particle size of the feldspar powder is 15-30 um; the mass volume ratio of the feldspar powder to the solution is 1:80-120g/ml, the volume ratio of hydrogen peroxide to concentrated sulfuric acid in the solution is 2-4:7, and the concentration of the concentrated sulfuric acid is 72-75%; the mass volume ratio of the feldspar powder to the coupling agent ethanol solution is 1:20-30 g/ml; the mass fraction of the coupling agent ethanol solution is 5-8%, the solvent is absolute ethanol, and the coupling agent is any one of KH-550, KH-560 and KH-570.

3. The method for preparing the wear-resistant toughened rubber flooring according to claim 1, wherein in the step 2), the method for preparing the acidified carbon nanotubes comprises the following steps: mixing carbon nanotubes with 70-75% nitric acid according to the mass-to-volume ratio of 1:50-80g/ml, oscillating and dispersing for 1-2h under 250-350W ultrasonic waves, refluxing for 3-4h at 80-90 ℃, continuing ultrasonic treatment for 2-3h at normal temperature after the reflux is finished, then removing upper layer liquid, washing with deionized water, filtering until the filtrate is neutral, and then drying in an oven at 90-100 ℃ for 10-13 h.

4. The method for preparing the wear-resistant toughened rubber flooring leather as claimed in claim 1, wherein in the step 2), the mass-to-volume ratio of the hexamethylene diamine, the N, N dimethylformamide, the N, N-dicyclohexylcarbodiimide and the carbon nanotubes is 10-15 g: 80-100 ml: 1-1.5 ml: 3-6 g.

5. The method for preparing the wear-resistant toughened rubber flooring according to claim 1, wherein in the step 3), the modified feldspar powder is added in an amount of 1-4% of the weight of the bismaleimide resin; the mass volume ratio of the bismaleimide resin to the acetone is 1:10-15 g/ml; the mass ratio of the modified carbon nano tube, the diethylamine and the calcium stearate to the resin prepolymer is 1-3:5-7:2-3: 50-60.

6. The method for preparing the wear-resistant toughened rubber flooring according to claim 1, wherein in the step 4), the mass ratio of the styrene to the naphthenic oil is 1: 1; the mass ratio of the liquid coumarone resin to the toughened bismaleimide resin is 1: 2-3; the mass ratio of the liquid coumarone resin to the styrene butadiene rubber is 1: 7-9; the mass ratio of the three groups of blends is 1:4-6: 20-23; the addition amount of the dicumyl peroxide is 1-1.5% of the total amount of the blend.

7. The method for preparing the wear-resistant toughened rubber flooring according to claim 1, wherein in the step 5), the mass ratio of the toughened styrene-butadiene rubber, the natural rubber, the di-tert-butylperoxyisopropyl benzene, the anti-aging agent and the colorant is 60-70:15-25:3-5:1: 1-4.

8. The method for preparing the wear-resistant toughened rubber flooring as claimed in claim 1, wherein in the step 5), the first banburying temperature is 100-; the temperature of the head of the extruder is 90-110 ℃, and the rotating speed is 30-50 r/min; the hot-pressing setting temperature is 150-; the rotating speed of the vulcanizer is 300-400r/min, the vulcanizing temperature is 170-175 ℃, the vulcanizing pressure is 6-8MPa, and the vulcanizing time is 20-30 min.

Technical Field

The invention belongs to the technical field of floor leather, and particularly relates to a preparation method of wear-resistant toughened rubber floor leather.

Background

The plastic flooring is one of the indispensable ground materials for modern home decoration, has the advantages of light dead weight, elasticity, good mechanical strength, easy cleaning, simple construction, convenient maintenance, low price and the like, and is widely applied to large quantities of civil buildings and public places in factory buildings and laboratories with higher requirements on cleanness.

At present, the types of floor leathers on the market are various, such as linen floor leathers, rubber floor leathers, plastic floor leathers, three-dimensional floor leathers and the like. The rubber floor leather is made of natural rubber, synthetic rubber, thermoplastic elastomer and other components of high molecular materials. The styrene-butadiene, high benzene and butadiene rubber are synthetic rubber and are byproducts of petroleum, the natural rubber is rubber extracted from artificially cultured rubber trees, and the thermoplastic elastomer is a high-molecular polymer material modified on the basis of a thermoplastic material and has excellent heavy pressure rebound resistance and toughness. The rubber floor leather is bright and beautiful in appearance, soft in texture like rubber, and is a preferable floor material for places such as sports grounds, airports, libraries, high-speed rails and the like which have large traffic and have high requirements on wear resistance, foot feel and rebound performance of floors. Rubber flooring has been popular as a floor finishing material in developed countries abroad for decades and is widely used, but has just been popular in China.

However, the rubber floor leathers popular in the market at present are easy to break, deform, lose shape and the like, the surface has low general wear resistance, the phenomena of abrasion and damage are easy to occur, and the wear resistance and the toughness of the rubber floor leathers can not meet the requirements of consumers. Therefore, the wear resistance and toughness of the rubber floor leather are improved, and the rubber floor leather has positive significance in the technical field of decorative materials.

Disclosure of Invention

The invention aims to provide a preparation method of wear-resistant toughened rubber floor leather aiming at the existing problems.

The invention is realized by the following technical scheme:

a preparation method of wear-resistant toughened rubber floor leather comprises the following specific steps:

1) adding feldspar powder into an excessive solution composed of hydrogen peroxide and concentrated sulfuric acid, stirring at the normal temperature at the rotation speed of 100-150r/min for 30-40min, washing the feldspar powder to be neutral after the reaction is finished, filtering and drying, slowly adding the feldspar powder into a coupling agent ethanol solution, reacting for 2-3h at the normal temperature, washing with distilled water after the reaction is finished, filtering for 4-5 times, and drying at the temperature of 50-60 ℃ to constant weight to obtain modified feldspar powder; according to the method, the surface of the feldspar powder is etched by adopting a mixed solution of hydrogen peroxide and concentrated sulfuric acid, so that hydroxyl groups with high chemical activity are generated on the surface of the feldspar powder, then the feldspar powder is modified by adopting a coupling agent, and a siloxane structure in the coupling agent is grafted to the surface of the feldspar powder through a chemical bond through a condensation reaction to form a resin-philic coupling agent layer, so that the interface bonding strength between the feldspar powder and resin is improved, and the thermal stability and the wear resistance of the resin are improved;

2) mixing hexamethylene diamine and N, N-dimethylformamide, oscillating and dispersing for 1-2h under 300-400W ultrasonic wave, adding N, N-dicyclohexylcarbodiimide and acidified carbon nano tubes, continuing to ultrasonically disperse for 20-30min, refluxing in an oil bath under magnetic stirring at 130-140 ℃ for 25-30h, naturally cooling to room temperature after the reaction is finished, filtering and washing, and vacuum drying the filtrate at 80-90 ℃ for 10-15h to obtain modified carbon nano tubes; the carbon nano tube is chemically modified by using hexamethylene diamine, and the amido in the hexamethylene diamine and the carboxyl on the acidified carbon nano tube are subjected to an amide reaction, so that the hexamethylene diamine is grafted to the surface of the carbon nano tube, the dispersity of the carbon nano tube in a resin system is improved, the interface bonding strength between the carbon nano tube and the resin system is enhanced, and the resin strength is improved;

3) heating and melting bismaleimide resin, magnetically stirring at 175 ℃ of 160-plus materials for 30-40min, cooling to 110-plus materials, adding modified feldspar powder, continuing to stir for 20-30min, adding acetone as a solvent to obtain a resin prepolymer, adding a modified carbon nanotube into the resin prepolymer, stirring at 500r/min of 400-plus materials for 1-2h, adding diethylamine and calcium stearate, continuing to stir for 20-30min, placing in an oven, curing at 250 ℃ of 230-plus materials for 6-8h, cooling, and crushing to obtain toughened bismaleimide resin; by adding the modified feldspar powder into the molten bismaleimide resin, the added modified feldspar powder can effectively reduce the crosslinking density of the resin, so that the thermal stability of the resin can be enhanced; the added modified carbon nano tube is used as a reinforcing material of the resin prepolymer, can be successfully grafted on the surface of the resin to modify the resin, and has a reinforcing effect on the density, the mechanical property and the heat resistance of a resin system, so that the resin can be toughened;

4) uniformly mixing styrene and naphthenic oil, then preserving heat for 2-3h at 165 ℃ of 155-plus-material, blending and heating liquid coumarone resin and toughened bismaleimide resin to 170 ℃ of 160-plus-material, preserving heat for 1-2h, blending and heating liquid coumarone resin and styrene butadiene rubber to 140 ℃ of 130-plus-material, preserving heat for 1-2h, then blending the pre-mixed three groups of blends, adding a small amount of dicumyl peroxide, heating to 180 ℃ of 170-plus-material, preserving heat for 3-4h, then cooling to 110 ℃ of 100-plus-material, and continuing preserving heat for 1-2h to obtain toughened styrene butadiene rubber; the thermoplastic elastomer, the toughened bismaleimide resin and the styrene butadiene rubber are blended, added dicumyl peroxide serves as an initiator to effectively reduce the curing temperature of the toughened bismaleimide resin, so that in the curing reaction of the toughened bismaleimide resin, one end of the thermoplastic elastomer is embedded and locked in one part of the toughened bismaleimide resin cured product, the other end of the thermoplastic elastomer is embedded and locked in the other part of the toughened bismaleimide resin cured product, and the styrene butadiene rubber serves as a continuous phase to be interpenetrated with the toughened bismaleimide resin cured product, so that a system with the styrene butadiene rubber as a continuous phase and the toughened bismaleimide resin as a disperse phase is formed, and the aim of toughening the styrene butadiene rubber is fulfilled;

5) the toughened styrene-butadiene rubber, the natural rubber, the anti-heat-aging agent and the colorant are sequentially put into an internal mixer for internal mixing, the internally mixed rubber material is cooled and then put into the internal mixer with the di-tert-butylperoxyisopropyl benzene for secondary internal mixing, the internally mixed rubber material is extruded into sheets by a rubber extruder, the sheets are vulcanized by a vulcanizer after hot press forming, and the rubber floor leather can be prepared after the vulcanized rubber sheets are completely cooled.

Preferably, the preparation method of the wear-resistant toughened rubber floor leather comprises the following steps of 1), wherein the particle size of the feldspar powder is 15-30 um; the mass volume ratio of the feldspar powder to the solution is 1:80-120g/ml, the volume ratio of hydrogen peroxide to concentrated sulfuric acid in the solution is 2-4:7, and the concentration of the concentrated sulfuric acid is 72-75%; the mass volume ratio of the feldspar powder to the coupling agent ethanol solution is 1:20-30 g/ml; the mass fraction of the coupling agent ethanol solution is 5-8%, the solvent is absolute ethanol, and the coupling agent is any one of KH-550, KH-560 and KH-570.

Preferably, the preparation method of the wear-resistant toughened rubber floor leather comprises the following steps in step 2): mixing carbon nanotubes with 70-75% nitric acid according to the mass-to-volume ratio of 1:50-80g/ml, oscillating and dispersing for 1-2h under 250-350W ultrasonic waves, refluxing for 3-4h at 80-90 ℃, continuing ultrasonic treatment for 2-3h at normal temperature after the reflux is finished, then removing upper layer liquid, washing with deionized water, filtering until the filtrate is neutral, and then drying in an oven at 90-100 ℃ for 10-13 h.

Preferably, in the step 2), the mass-to-volume ratio of the hexamethylene diamine, the N, N dimethylformamide, the N, N-dicyclohexylcarbodiimide and the carbon nano tubes is 10-15 g: 80-100 ml: 1-1.5 ml: 3-6 g.

Preferably, in the step 3), the addition amount of the modified feldspar powder is 1-4% of the weight of the bismaleimide resin; the mass volume ratio of the bismaleimide resin to the acetone is 1:10-15 g/ml; the mass ratio of the modified carbon nano tube, the diethylamine and the calcium stearate to the resin prepolymer is 1-3:5-7:2-3: 50-60.

Preferably, the preparation method of the wear-resistant toughened rubber floor leather comprises the following steps of 4), wherein the mass ratio of the styrene to the naphthenic oil is 1: 1; the mass ratio of the liquid coumarone resin to the toughened bismaleimide resin is 1: 2-3; the mass ratio of the liquid coumarone resin to the styrene butadiene rubber is 1: 7-9; the mass ratio of the three groups of blends is 1:4-6: 20-23; the addition amount of the dicumyl peroxide is 1-1.5% of the total amount of the blend.

Preferably, in the step 5), the mass ratio of the toughened styrene-butadiene rubber, the natural rubber, the di-tert-butylperoxyisopropyl benzene, the anti-aging agent and the colorant is 60-70:15-25:3-5:1: 1-4.

Preferably, in the step 5), the first banburying temperature is 100-; the temperature of the head of the extruder is 90-110 ℃, and the rotating speed is 30-50 r/min; the hot-pressing setting temperature is 150-; the rotating speed of the vulcanizer is 300-400r/min, the vulcanizing temperature is 170-175 ℃, the vulcanizing pressure is 6-8MPa, and the vulcanizing time is 20-30 min.

Compared with the prior art, the invention has the following advantages:

according to the rubber floor leather prepared by the invention, the toughness and the wear resistance of the synthetic rubber in the raw materials are enhanced by modifying the synthetic rubber, so that the surface of the rubber floor leather has good wear resistance and toughness, the foot feeling of the rubber floor leather is improved, and the service life of the rubber floor leather is prolonged.

Detailed Description

The present invention will be further described with reference to specific embodiments.