阅读说明：本技术 一种高弹性耐水解合成革及其制备方法 (High-elasticity hydrolysis-resistant synthetic leather and preparation method thereof ) 是由 刘超 熊祖江 刘伟强 董斌 王有承 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种高弹性耐水解合成革及其制备方法,包括基布和位于基布上表面的改性氢化聚苯乙烯弹性体；改性氢化聚苯乙烯弹性体的制备原料,按质量份计,包括氢化度为93％-96％的氢化聚苯乙烯弹性体100份、马来酸酐8-12份。制备方法包括步骤1)称取氢化度为93％-96％的氢化聚苯乙烯弹性体100份、马来酸酐8-12份；步骤2)将称取的氢化聚苯乙烯弹性体和马来酸酐加入双螺杆挤出机中混炼10-12min,获得接枝率为2.7％-3.2％的改性氢化聚苯乙烯弹性体；其中,双螺杆挤出机的螺杆温度为145℃；步骤3)将改性氢化聚苯乙烯弹性体放置于基布上表面,并对其进行压延,压延温度为180℃。以上述配方和制备方法不仅环保、工艺简单,还提高了合成革的弹性、耐水解性。(The invention discloses a high-elasticity hydrolysis-resistant synthetic leather and a preparation method thereof, wherein the synthetic leather comprises base cloth and a modified hydrogenated polystyrene elastomer positioned on the upper surface of the base cloth; the raw materials for preparing the modified hydrogenated polystyrene elastomer comprise, by mass, 100 parts of a hydrogenated polystyrene elastomer with a hydrogenation degree of 93-96% and 8-12 parts of maleic anhydride. The preparation method comprises the steps of 1) weighing 100 parts of hydrogenated polystyrene elastomer with the hydrogenation degree of 93-96% and 8-12 parts of maleic anhydride; step 2) adding the weighed hydrogenated polystyrene elastomer and maleic anhydride into a double-screw extruder for mixing for 10-12min to obtain a modified hydrogenated polystyrene elastomer with the grafting rate of 2.7-3.2%; wherein the screw temperature of the double-screw extruder is 145 ℃; and 3) placing the modified hydrogenated polystyrene elastomer on the upper surface of the base cloth, and calendering the base cloth at the calendering temperature of 180 ℃. The formula and the preparation method are environment-friendly and simple in process, and the elasticity and hydrolysis resistance of the synthetic leather are improved.)

1. A high elasticity hydrolysis-resistant synthetic leather is characterized in that: comprises base cloth and a modified hydrogenated polystyrene elastomer positioned on the upper surface of the base cloth; the modified hydrogenated polystyrene elastomer comprises, by mass, 100 parts of a hydrogenated polystyrene elastomer with a hydrogenation degree of 93-96% and 8-12 parts of maleic anhydride.

2. The high elasticity hydrolysis resistant synthetic leather of claim 1, wherein: the base cloth is made of degradable materials.

3. A preparation method of high-elasticity hydrolysis-resistant synthetic leather is characterized by comprising the following steps: the high-elasticity hydrolysis-resistant synthetic leather is prepared by the following steps of claim 1:

step 1: weighing 100 parts of hydrogenated polystyrene elastomer with the hydrogenation degree of 93-96% and 8-12 parts of maleic anhydride;

step 2: adding the weighed hydrogenated polystyrene elastomer and maleic anhydride into a double-screw extruder to be mixed for 10-12min, and obtaining a modified hydrogenated polystyrene elastomer with the grafting rate of 2.7-3.2%; wherein the screw temperature of the double-screw extruder is 145 ℃;

and step 3: placing the modified hydrogenated polystyrene elastomer on the upper surface of base cloth, and calendering the base cloth to obtain the synthetic leather; wherein the calendering temperature is 180 ℃.

4. The method for preparing high-elasticity hydrolysis-resistant synthetic leather according to claim 3, wherein the method comprises the following steps: and 3, preparing the base cloth from the copolymer of butylene adipate and butylene terephthalate and/or the polybutylene succinate/butylene terephthalate mixed yarn by needling or spunlacing.

Technical Field

The invention relates to the technical field of synthetic leather manufacturing, in particular to high-elasticity hydrolysis-resistant synthetic leather and a preparation method thereof.

Background

Synthetic leather is increasingly used in industrial life as a substitute for genuine leather. The traditional synthetic leather mainly comprises: PVC synthetic leather, polyurethane synthetic leather and waterborne polyurethane synthetic leather.

The synthetic leathers have excellent performance, but have congenital defects. The PVC synthetic leather has good weather resistance, but has the defects of environmental-friendly production process, difficult degradation, insufficient elasticity, complicated production process and the like; with the development of polyurethane synthetic leather, although the production process becomes simpler, a large amount of DMF (dimethyl formamide) is used in the production process, so that the preparation of the synthetic leather is easy to cause environmental pollution and waste; with the birth of the waterborne polyurethane synthetic leather, although the problem of environmental pollution is solved, the strength, hydrolysis resistance and wear resistance of the synthetic leather are poor, and the synthetic leather cannot be generally applied, especially in the aspect of sports shoe materials.

Therefore, synthetic leather and the preparation method thereof in the prior art still need to be further improved.

Disclosure of Invention

The invention aims to overcome the defects in the background art and provide high-elasticity hydrolysis-resistant synthetic leather and a preparation method thereof so as to solve the problems of environmental pollution, complicated production process, poor elasticity, poor weather resistance and the like in the production process of the synthetic leather. In order to achieve the purpose, the invention adopts the following technical scheme:

a high-elasticity hydrolysis-resistant synthetic leather comprises base cloth and a modified hydrogenated polystyrene elastomer positioned on the upper surface of the base cloth; the raw materials for preparing the modified hydrogenated polystyrene elastomer comprise, by mass, 100 parts of a hydrogenated polystyrene elastomer with a hydrogenation degree of 93-96% and 8-12 parts of maleic anhydride.

Further, the base cloth is made of degradable materials.

The preparation method of the high-elasticity hydrolysis-resistant synthetic leather comprises the following steps:

step 1: weighing 100 parts of hydrogenated polystyrene elastomer with the hydrogenation degree of 93-96% and 8-12 parts of maleic anhydride;

step 2: adding the weighed hydrogenated polystyrene elastomer and maleic anhydride into a double-screw extruder to be mixed for 10-12min, and obtaining a modified hydrogenated polystyrene elastomer with the grafting rate of 2.7-3.2%; wherein the screw temperature of the double-screw extruder is 145 ℃;

and step 3: placing the modified hydrogenated polystyrene elastomer on the upper surface of base cloth, and calendering the base cloth to obtain the synthetic leather; wherein the calendering temperature is 180 ℃.

Further, the base cloth in the step 3 is prepared by copolymer of butylene adipate and butylene terephthalate and/or poly (butylene succinate)/butylene terephthalate mixed yarn through needling or spunlacing.

As can be seen from the above description of the present invention, the present invention has the following advantages over the prior art:

1. because the polystyrene elastomer is a rubber material and has good resilience, the synthetic leather prepared from the raw material has good resilience; however, because the polystyrene elastomer is polymerized by polystyrene and butadiene, the softness of the elastomer is not enough, so that double bonds in the polystyrene elastomer can be hydrogenated and added into single bonds through hydrogenation reaction to generate hydrogenated polystyrene, so as to improve the softness and the weather resistance of the elastomer; however, the hydrogenated polystyrene elastomer belongs to a nonpolar material and is inconvenient to attach in the application process of synthetic leather, so that the hydrogenated polystyrene elastomer which is not completely hydrogenated, namely has the hydrogenation degree of 93-96% is used as a preparation raw material, and the modified hydrogenated polystyrene obtained by mixing the hydrogenated polystyrene elastomer and maleic anhydride is grafted and modified, so that the modified hydrogenated polystyrene has good softness and is easy to attach; therefore, the formula of the synthetic leather is beneficial to improving the elasticity of the synthetic leather.

2. Because the base cloth is a degradable material, the synthetic leather can be recycled after aerobic composting degradation; therefore, the arrangement can reduce environmental pollution and is beneficial to environmental protection.

3. Because the modified hydrogenated polystyrene elastomer has no unsaturated bond, the modified hydrogenated polystyrene elastomer has good hydrolysis resistance compared with polyurethane synthetic leather.

4. When preparing the high-elasticity hydrolysis-resistant synthetic leather, the modified hydrogenated polystyrene elastomer is only required to be placed above the base cloth and subjected to calendering treatment; therefore, the arrangement simplifies the production process of the synthetic leather and improves the production efficiency.

5. Because the synthetic leather prepared by the modified hydrogenated polystyrene elastomer can keep excellent performance at the temperature of minus 30 ℃, the existing PVC synthetic leather or polyurethane synthetic leather is easy to harden at higher temperature or lower temperature and is inconvenient to use in winter; therefore, compared with the existing synthetic leather, the product has higher universality.

6. The modified hydrogenated polystyrene elastomer has good softness, so the modified hydrogenated polystyrene elastomer can be well bonded with base cloth in the calendering process and has excellent stripping performance.

Detailed Description

In order to make all the technical problems, technical solutions and advantageous effects of the present invention more clear and obvious, the following embodiments further describe the present invention in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Hereinafter, the copolymer of butylene adipate and butylene terephthalate is abbreviated as PBAT, and the polybutylene succinate/butylene terephthalate is abbreviated as PBST.

Example one

The invention discloses a high-elasticity hydrolysis-resistant synthetic leather and a preparation method thereof, wherein the synthetic leather comprises base cloth and a modified hydrogenated polystyrene elastomer positioned on the upper surface of the base cloth; wherein, the base cloth is made of degradable material.

In the first embodiment of the present invention, the raw material for preparing the modified hydrogenated polystyrene elastomer comprises, by mass, 10 parts of maleic anhydride and 100 parts of a hydrogenated polystyrene elastomer having a degree of hydrogenation of 93%, wherein the hydrogenated polystyrene elastomer has a tensile strength of 3.5MPA, a hardness of 55A, and a melt index of more than 15.

The preparation method of the high-elasticity hydrolysis-resistant synthetic leather comprises the following steps: step 1, 100 parts of hydrogenated polystyrene elastomer with a hydrogenation degree of 93% and 10 parts of maleic anhydride are weighed.

Step 2, adding the weighed hydrogenated polystyrene elastomer and maleic anhydride into a double-screw extruder for mixing for 12min to obtain a modified hydrogenated polystyrene elastomer with the grafting rate of 3.2%; wherein the screw temperature of the twin-screw extruder is 145 ℃.

In the step 2, the modified hydrogenated polystyrene elastomer has no unsaturated bond, so that the synthetic leather prepared from the modified hydrogenated polystyrene elastomer has good hydrolysis resistance; the hydrogenated polystyrene elastomer can still maintain excellent performance at the temperature of minus 30 ℃, so that the synthetic leather prepared from the hydrogenated polystyrene elastomer also has good weather resistance.

Step 3, placing the modified hydrogenated polystyrene elastomer on the upper surface of the base cloth, and calendering the base cloth to obtain a sample of the high-elasticity hydrolysis-resistant synthetic leather; wherein the calendering temperature is 180 ℃.

In the step 3, the base cloth is prepared by mixing yarns of PBAT and/or PBST through needling or spunlacing, and the arrangement ensures that the product can be recycled after being degraded by aerobic composting so as to reduce environmental pollution. The modified hydrogenated polystyrene elastomer has good softness because the incompletely hydrogenated polystyrene elastomer is mixed with the maleic anhydride; therefore, the modified hydrogenated polystyrene elastomer can be well combined with the base cloth in the calendering process, and has good stripping performance, the step effectively simplifies the production process of the synthetic leather, and the production efficiency is improved.

Example two

The difference between the second embodiment and the first embodiment is that: in example two of the present invention, the modified hydrogenated polystyrene elastomer obtained was different in the graft ratio depending on the parts by mass of the raw material for producing the modified hydrogenated polystyrene elastomer, the degree of hydrogenation of the hydrogenated polystyrene elastomer, and the mixing time of maleic anhydride and the hydrogenated polystyrene elastomer.

In example two of the present invention, the raw material for preparing the modified hydrogenated polystyrene elastomer comprises, in parts by mass, 8 parts of maleic anhydride and 100 parts of a hydrogenated polystyrene elastomer having a degree of hydrogenation of 95%, the elastomer having a tensile strength of 3.7MPA, a hardness of 55A and a melt index of more than 18.

In the second embodiment of the invention, the preparation method of the high-elasticity hydrolysis-resistant synthetic leather is different from the first embodiment in that: in step 2, the hydrogenated polystyrene elastomer and maleic anhydride are added into a double-screw extruder and mixed for 10min, and the modified hydrogenated polystyrene elastomer with the grafting rate of 2.7% is obtained.

EXAMPLE III

The difference between the third embodiment and the first and second embodiments is that: in example three of the present invention, the modified hydrogenated polystyrene elastomer obtained was different in the graft ratio depending on the parts by mass of the raw material for producing the modified hydrogenated polystyrene elastomer, the degree of hydrogenation of the hydrogenated polystyrene elastomer, and the mixing time of maleic anhydride and the hydrogenated polystyrene elastomer.

In the third example of the present invention, the raw material for preparing the modified hydrogenated polystyrene elastomer comprises, by mass, 12 parts of maleic anhydride and 100 parts of a hydrogenated polystyrene elastomer having a hydrogenation degree of 96%, the elastomer has a tensile strength of 2.7MPA, a hardness of 52A, and a melt index of more than 21.

The SEBS in the first comparative example, the SEBS-g-MAH prepared by the chemical method in the second comparative example, the SEBS/PP blending graft modification material prepared in the first inventive example and the SEBS/PP blending graft modification material prepared in the second inventive example are subjected to comparative experiments, and the obtained experimental data are recorded in the following first table:

the fracture strength, tear load, tensile load, breaking load, elongation at break, peel load, post hydrolysis resistance peel load, folding endurance, and Taber abrasion resistance of the high-elasticity hydrolysis-resistant synthetic leather of the first, second, and third examples were compared under different test standards, and the obtained test data are listed in the following table one:

watch 1

According to the experimental data on the upper table, the high-elasticity hydrolysis-resistant synthetic leather provided by the invention is simple in manufacturing process, environment-friendly and low in post-treatment energy consumption, and meanwhile, the synthetic leather surface layer can be recycled due to the fact that the base cloth is made of degradable materials; therefore, the synthetic leather prepared by the invention meets the national relevant physical property standard.

In conclusion, the high-elasticity hydrolysis-resistant synthetic leather and the preparation method thereof provided by the invention are environment-friendly and simple in process, and effectively improve the elasticity, softness, hydrolysis resistance and weather resistance of the synthetic leather.

The description of the above specification and examples is intended to be illustrative of the scope of the present invention and is not intended to be limiting. Modifications, equivalents and other improvements which may occur to those skilled in the art and which may be made to the embodiments of the invention or portions thereof through a reasonable analysis, inference or limited experimentation, in light of the common general knowledge, the common general knowledge in the art and/or the prior art, are intended to be within the scope of the invention.