CN114525007A - 一种轻质防龟裂橡胶鞋底及其制备方法 - Google Patents
一种轻质防龟裂橡胶鞋底及其制备方法 Download PDFInfo
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Abstract
一种轻质防龟裂橡胶鞋底及其制备方法,橡胶鞋底由以下原料组成:部分氢化苯乙烯‑丁二烯嵌段共聚物、白矿油、苯乙烯‑丁二烯嵌段共聚物、部分氢化苯乙烯‑丁二烯无规共聚物、氯化聚乙烯、发泡剂、光稳定剂、硬脂酸锌、耐磨剂、生物降解剂、空心玻璃微球,本发明制备的轻质防龟裂橡胶鞋底,具有泡孔均匀、密度小、高耐磨、防滑等常规物性优势,还具有耐候性好、抗臭氧龟裂等特点,并具备可生物降解性,能缓解白色污染带来的环境问题,符合当前新材料的发展方向。
Description
技术领域
本发明属于橡胶鞋底制备领域,具体涉及一种轻质防龟裂橡胶鞋底及其制备方法。
背景技术
目前TPR热塑性橡胶鞋底存在密度大(0.9-1.1g/cm3)、耐黄变性能差、容易龟裂(尤其是鞋头翘起来的部分)等问题。
中国专利CN104356582B公开了一种微交联热塑性弹性体及其制备方法,制备的微交联热塑性弹性体,具有密度小、高耐磨、泡孔均匀等特点,并且具有良好的低温柔韧性、尺寸稳定性特点。但是其硫化温度174-175℃,加工温度高,能耗高;用作与鞋面粘合的鞋头橡胶时,存在鞋头弯曲的应力,耐候性差,容易发生龟裂现象,有待进一步改进。
发明内容
本发明的目的是克服现有技术的缺点,提供一种轻质防龟裂橡胶鞋底,另一目的是提供一种制备上述橡胶鞋底的方法。
本发明采用如下技术方案:
一种轻质防龟裂橡胶鞋底,由以下重量份的原料组成:
进一步的,所述部分氢化苯乙烯-丁二烯嵌段共聚物的丁二烯嵌段的支链末端双键被全部氢化,主链上的双键不受影响。
进一步的,所述部分氢化苯乙烯-丁二烯无规共聚物是苯乙烯-丁二烯共聚物的末端双键被全部氢化的产物。
进一步的,所述生物降解剂是聚烯烃接枝改性产物。
进一步的,所述空心玻璃微球是微米级的表面改性的中空玻璃微球。
进一步的,所述发泡剂为发泡剂AC、微胶囊发泡剂、OBSH发泡剂这些化合物中的一种或多种。
进一步的,由以下重量份的原料组成:
一种轻质防龟裂橡胶鞋底的制备方法,包括以下步骤:
步骤一,将所需重量份的苯乙烯-丁二烯嵌段共聚物和部分氢化苯乙烯-丁二烯无规共聚物在高速混合器中预混3-10分钟,然后将预混料通过双螺杆挤出机,在140-180℃范围,熔融挤出,冷却、切粒,得到弹性体颗粒;
步骤二,将步骤一制备的弹性体颗粒、部分氢化苯乙烯-丁二烯嵌段共聚物、白矿油、氯化聚乙烯、发泡剂、光稳定剂、硬脂酸锌、耐磨剂、生物降解剂、空心玻璃微球倒入密炼机混合密炼,再开炼、造粒,得到轻质防龟裂橡胶粒米;
步骤三,将轻质防龟裂橡胶粒米倒入密封鞋底模具中注塑成型,即得所述轻质防龟裂橡胶鞋底。
进一步的,所述步骤二的具体工序为:将步骤一制备的弹性体颗粒、部分氢化苯乙烯-丁二烯嵌段共聚物、白矿油、氯化聚乙烯、发泡剂、光稳定剂、硬脂酸锌、耐磨剂、生物降解剂、空心玻璃微球倒入密炼机仓,落下压锤,关闭防护门、密炼,待温度达到108℃,第一次翻料;继续密炼,待温度达到113℃,第二次翻料;继续密炼,待温度达到129℃,第三次翻料;再密炼2min,最后倒料、开炼、造粒。
进一步的,所述步骤三的具体工序为:将轻质防龟裂橡胶粒米倒入圆盘注塑机的料斗里,自动进料,经螺杆混炼熔融,挤入密封橡胶鞋底模具中注塑成型,螺杆温度135-160℃,冷却,开模,得到轻质防龟裂橡胶鞋底。
由上述对本发明的描述可知,与现有技术相比,本发明的有益效果是:
第一,本发明制备的轻质防龟裂橡胶鞋底,具有泡孔均匀、密度小、高耐磨、防滑等常规物性优势,还具有耐候性好、抗臭氧龟裂等特点,并具备可生物降解性,能缓解白色污染带来的环境问题,符合当前新材料的发展方向;
第二,通过限定发泡剂与空心玻璃微球配合,使橡胶鞋底发泡的泡孔均匀,密度控制在0.5-0.7g/cm3,且能保持较好的力学性能;苯乙烯-丁二烯嵌段共聚物、苯乙烯-丁二烯嵌段共聚物和苯乙烯-丁二烯无规共聚物都是非结晶性聚合物,添加发泡剂的话,容易发生泡孔塌陷、串孔,形成薄的位置不发泡、厚的位置中间包空的现象,导致撕裂强度、耐曲折等力学性能差;本发明申请限定发泡剂和空心玻璃微球配合使用,发泡率小,空心玻璃微球能承受一定发泡压力,提升泡孔壁的支撑力,实现发泡的泡孔均匀,且保持较好的力学性能;
第三,本申请采用支链末端双键被氢化的部分氢化苯乙烯-丁二烯嵌段共聚物和部分氢化苯乙烯-丁二烯无规共聚物,并具体限定二者的占比,以提升橡胶鞋底的抗龟裂性能,解决了橡胶鞋底鞋头龟裂的问题;支链末端双键能提升材料的抗湿滑性能和加工性能,但其反应活性高,容易被氧化,导致材料老化后,性能下降,甚至出现龟裂现象;本发明申请将支链末端双键氢化,显著提升橡胶鞋底的耐臭氧老化性能,解决了橡胶鞋底鞋头龟裂问题,同时,通过配方调控,保持较好的抗湿滑性能和加工性能。
具体实施方式
以下通过具体实施方式对本发明作进一步的描述。
一种轻质防龟裂橡胶鞋底,由以下重量份的原料组成:
其中,部分氢化苯乙烯-丁二烯嵌段共聚物是苯乙烯-丁二烯嵌段共聚物在特殊催化剂作用下的选择性氢化产物,其丁二烯嵌段的支链末端双键被全部氢化,主链上的双键不受影响;丁二烯聚合过程存在1,4加成聚合和1,2加成聚合,其中1,2加成聚合会产生支链末端双键,该双键的反应活性高,容易被氧化;其中1,4加成聚合不会产生支链末端双键。所述部分氢化苯乙烯-丁二烯嵌段共聚物的1,2加成聚合占丁二烯聚合部分的3%至30%(质量比)。所述部分氢化苯乙烯-丁二烯嵌段共聚物的苯乙烯占比15%-55%(质量比);所述部分氢化苯乙烯-丁二烯嵌段共聚物的含油0%-50%(质量比)。
部分氢化苯乙烯-丁二烯无规共聚物是苯乙烯-丁二烯共聚物的末端双键被全部氢化的产物。所述部分氢化苯乙烯-丁二烯无规共聚物是树脂,俗称K胶、K树脂。丁二烯发生1,2加成聚合时,产生末端双键,该双键的反应活性高,容易被氧化。
发泡剂至少包括发泡剂AC、微胶囊发泡剂、OBSH发泡剂中的一种或多种。
光稳定剂至少包括二苯甲酮类紫外线吸收剂、苯并***类紫外线吸收剂、受阻酚类抗氧剂、羟基苯并***类抗氧剂这些化合物中的一种。
生物降解剂是聚烯烃接枝改性产物,加速聚合物在厌氧环境下的降解速度,橡胶鞋底可实现90天厌氧填埋后,降解至少90%;具体的,生物降解剂是由聚烯烃材料注入厌氧有机助剂制成,在充满活性厌氧生物的填埋场中(垃圾填埋场和深海),生物降解剂吸引自然界微生物,并产生酶,破坏橡胶高分子结构,微生物通过消化橡胶得到所需要的能量,并加速微生物的繁殖速度,提升生物降解速率,让橡胶产品最后还原成有机腐化物(有机腐殖质)。
空心玻璃微球是微米级的表面改性的中空玻璃微球,具体的,空心玻璃微球是中空的圆球粉末状无机非金属材料,其粒径在2μm-320μm,具有比量轻、体积大、导热系数低、抗压强度高、流动性好等特点。
一种轻质防龟裂橡胶鞋底的制备方法,包括以下步骤:
步骤一,将所需重量份的苯乙烯-丁二烯嵌段共聚物和部分氢化苯乙烯-丁二烯无规共聚物在高速混合器中预混3-10分钟,然后将预混料通过双螺杆挤出机,在140-180℃范围,熔融挤出,冷却、切粒,得到弹性体颗粒;
步骤二,:将步骤一制备的弹性体颗粒、部分氢化苯乙烯-丁二烯嵌段共聚物、白矿油、氯化聚乙烯、发泡剂、光稳定剂、硬脂酸锌、耐磨剂、生物降解剂、空心玻璃微球倒入密炼机仓,落下压锤,关闭防护门、密炼,待温度达到108℃,第一次翻料;继续密炼,待温度达到113℃,第二次翻料;继续密炼,待温度达到129℃,第三次翻料;再密炼2min,最后倒料、开炼、造粒,得到轻质防龟裂橡胶粒米;
步骤三,将轻质防龟裂橡胶粒米倒入圆盘注塑机的料斗里,自动进料,经螺杆混炼熔融,挤入密封橡胶鞋底模具中注塑成型,螺杆温度135-160℃,冷却,开模,得到轻质防龟裂橡胶鞋底。
实施例1
一种轻质防龟裂橡胶鞋底,由以下重量份的原料组成:
生物降解剂是聚烯烃接枝改性产物,加速聚合物在厌氧环境下的降解速度,轻质防龟裂橡胶鞋底可实现90天厌氧填埋后,降解92%(质量比)。降解实验参考GB/T 33797,填埋90天后,计算质量损失。
一种轻质防龟裂橡胶鞋底的制备方法,包括以下步骤:
步骤一,将所需重量份的苯乙烯-丁二烯嵌段共聚物和部分氢化苯乙烯-丁二烯无规共聚物在高速混合器中预混3分钟,然后将预混料通过双螺杆挤出机,在140℃下,熔融挤出,冷却、切粒,得到弹性体颗粒;
步骤二,:将步骤一制备的弹性体颗粒、部分氢化苯乙烯-丁二烯嵌段共聚物、白矿油、氯化聚乙烯、发泡剂、光稳定剂、硬脂酸锌、耐磨剂、生物降解剂、空心玻璃微球倒入密炼机仓,落下压锤,关闭防护门、密炼,待温度达到108℃,第一次翻料;继续密炼,待温度达到113℃,第二次翻料;继续密炼,待温度达到129℃,第三次翻料;再密炼2min,最后倒料、开炼、造粒,得到轻质防龟裂橡胶粒米;
步骤三,将轻质防龟裂橡胶粒米倒入圆盘注塑机的料斗里,自动进料,经螺杆混炼熔融,挤入密封橡胶鞋底模具中注塑成型,螺杆温度135℃,冷却,开模,得到轻质防龟裂橡胶鞋底。
实施例2
一种轻质防龟裂橡胶鞋底,由以下重量份的原料组成:
生物降解剂是聚烯烃接枝改性产物,加速聚合物在厌氧环境下的降解速度,橡胶鞋底可实现90天厌氧填埋后,降解率超过90%。
一种轻质防龟裂橡胶鞋底的制备方法,包括以下步骤:
步骤一,将所需重量份的苯乙烯-丁二烯嵌段共聚物和部分氢化苯乙烯-丁二烯无规共聚物在高速混合器中预混10分钟,然后将预混料通过双螺杆挤出机,在180℃下,熔融挤出,冷却、切粒,得到弹性体颗粒;
步骤二,:将步骤一制备的弹性体颗粒、部分氢化苯乙烯-丁二烯嵌段共聚物、白矿油、氯化聚乙烯、发泡剂、光稳定剂、硬脂酸锌、耐磨剂、生物降解剂、空心玻璃微球倒入密炼机仓,落下压锤,关闭防护门、密炼,待温度达到108℃,第一次翻料;继续密炼,待温度达到113℃,第二次翻料;继续密炼,待温度达到129℃,第三次翻料;再密炼2min,最后倒料、开炼、造粒,得到轻质防龟裂橡胶粒米;
步骤三,将轻质防龟裂橡胶粒米倒入圆盘注塑机的料斗里,自动进料,经螺杆混炼熔融,挤入密封橡胶鞋底模具中注塑成型,螺杆温度160℃,冷却,开模,得到轻质防龟裂橡胶鞋底。
实施例3
一种轻质防龟裂橡胶鞋底,由以下重量份的原料组成:
生物降解剂是聚烯烃接枝改性产物,加速聚合物在厌氧环境下的降解速度,橡胶鞋底可实现90天厌氧填埋后,降解率93%。
一种轻质防龟裂橡胶鞋底的制备方法,包括以下步骤:
步骤一,将所需重量份的苯乙烯-丁二烯嵌段共聚物和部分氢化苯乙烯-丁二烯无规共聚物在高速混合器中预混7分钟,然后将预混料通过双螺杆挤出机,在160℃下,熔融挤出,冷却、切粒,得到弹性体颗粒;
步骤二,:将步骤一制备的弹性体颗粒、部分氢化苯乙烯-丁二烯嵌段共聚物、白矿油、氯化聚乙烯、发泡剂、光稳定剂、硬脂酸锌、耐磨剂、生物降解剂、空心玻璃微球倒入密炼机仓,落下压锤,关闭防护门、密炼,待温度达到108℃,第一次翻料;继续密炼,待温度达到113℃,第二次翻料;继续密炼,待温度达到129℃,第三次翻料;再密炼2min,最后倒料、开炼、造粒,得到轻质防龟裂橡胶粒米;
步骤三,将轻质防龟裂橡胶粒米倒入圆盘注塑机的料斗里,自动进料,经螺杆混炼熔融,挤入密封橡胶鞋底模具中注塑成型,螺杆温度150℃,冷却,开模,得到轻质防龟裂橡胶鞋底。
对比例1
本对比例中,一种轻质防龟裂橡胶鞋底的制备方法基本与实施例3中的制备方法相同,所不同的是:
苯乙烯-丁二烯嵌段共聚物1475替换部分氢化苯乙烯-丁二烯嵌段共聚物、苯乙烯-丁二烯无规共聚物替换部分氢化苯乙烯-丁二烯无规共聚物。
对比例2
某品牌市售产品。
将上述三个实施例制得的轻质防龟裂橡胶鞋底与现有技术中的橡胶鞋底作为对比例进行相应测试,获得如下数据:
其中,DIN耐磨按照GB/T 9867-2008测试;耐黄变测试按照HG/T 3689太阳光、50℃、24小时;耐臭氧测试采用臭氧试验机,温度50℃、湿度65%、臭氧浓度50pphm、时间24小时,样品用拉伸夹具安装,将样品长度拉伸至120%,模拟鞋头受力拉伸现象。
表1各实施例的数据性能表
综上所述,本发明制备的轻质防龟裂橡胶鞋底,具有泡孔均匀、密度小、高耐磨、防滑等常规物性优势,还具有耐候性好、抗臭氧龟裂等特点,并具备可生物降解性,能缓解白色污染带来的环境问题,符合当前新材料的发展方向;并且通过对比例1、对比例2与实施例3对比可知,本申请采用支链末端双键被氢化的部分氢化苯乙烯-丁二烯嵌段共聚物和部分氢化苯乙烯-丁二烯无规共聚物,并具体限定二者的占比,以提升橡胶鞋底的抗龟裂性能,解决了橡胶鞋底鞋头龟裂的问题。
以上所述,仅为本发明的较佳实施例而已,故不能以此限定本发明实施的范围,即依本发明申请专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明专利涵盖的范围内。
Claims (10)
2.根据权利要求1所述的一种轻质防龟裂橡胶鞋底,其特征在于:所述部分氢化苯乙烯-丁二烯嵌段共聚物的丁二烯嵌段的支链末端双键被全部氢化,主链上的双键不受影响。
3.根据权利要求1所述的一种轻质防龟裂橡胶鞋底,其特征在于:所述部分氢化苯乙烯-丁二烯无规共聚物是苯乙烯-丁二烯共聚物的末端双键被全部氢化的产物。
4.根据权利要求1所述的一种轻质防龟裂橡胶鞋底,其特征在于:所述生物降解剂是聚烯烃接枝改性产物。
5.根据权利要求1所述的一种轻质防龟裂橡胶鞋底,其特征在于:所述空心玻璃微球是微米级的表面改性的中空玻璃微球。
6.根据权利要求1所述的一种轻质放龟裂橡胶鞋底,其特征在于:所述发泡剂为发泡剂AC、微胶囊发泡剂、OBSH发泡剂这些化合物中的一种或多种。
8.一种轻质防龟裂橡胶鞋底的制备方法,其特征在于:包括以下步骤:
步骤一,将所需重量份的苯乙烯-丁二烯嵌段共聚物和部分氢化苯乙烯-丁二烯无规共聚物在高速混合器中预混3-10分钟,然后将预混料通过双螺杆挤出机,在140-180℃范围,熔融挤出,冷却、切粒,得到弹性体颗粒;
步骤二,将步骤一制备的弹性体颗粒、部分氢化苯乙烯-丁二烯嵌段共聚物、白矿油、氯化聚乙烯、发泡剂、光稳定剂、硬脂酸锌、耐磨剂、生物降解剂、空心玻璃微球倒入密炼机混合密炼,再开炼、造粒,得到轻质防龟裂橡胶粒米;
步骤三,将轻质防龟裂橡胶粒米倒入密封鞋底模具中注塑成型,即得所述轻质防龟裂橡胶鞋底。
9.根据权利要求8所述的一种轻质防龟裂橡胶鞋底的制备方法,其特征在于:所述步骤二的具体工序为:将步骤一制备的弹性体颗粒、部分氢化苯乙烯-丁二烯嵌段共聚物、白矿油、氯化聚乙烯、发泡剂、光稳定剂、硬脂酸锌、耐磨剂、生物降解剂、空心玻璃微球倒入密炼机仓,落下压锤,关闭防护门、密炼,待温度达到108℃,第一次翻料;继续密炼,待温度达到113℃,第二次翻料;继续密炼,待温度达到129℃,第三次翻料;再密炼2min,最后倒料、开炼、造粒。
10.根据权利要求8所述的一种轻质防龟裂橡胶鞋底的制备方法,其特征在于:所述步骤三的具体工序为:将轻质防龟裂橡胶粒米倒入圆盘注塑机的料斗里,自动进料,经螺杆混炼熔融,挤入密封橡胶鞋底模具中注塑成型,螺杆温度135-160℃,冷却,开模,得到轻质防龟裂橡胶鞋底。
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CN214730977U (zh) * | 2021-05-22 | 2021-11-16 | 洛阳绿之汇塑料降解科技有限公司 | 一种具备环保降解能力的快递袋 |
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CN112225946A (zh) * | 2020-10-15 | 2021-01-15 | 深圳市通产丽星股份有限公司 | 复合生物降解促进剂及其制备方法和应用 |
CN214730977U (zh) * | 2021-05-22 | 2021-11-16 | 洛阳绿之汇塑料降解科技有限公司 | 一种具备环保降解能力的快递袋 |
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