CN113524836A - 一种预制型热塑性弹性体篮球场地面及其制备方法 - Google Patents

一种预制型热塑性弹性体篮球场地面及其制备方法 Download PDF

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CN113524836A
CN113524836A CN202110710463.7A CN202110710463A CN113524836A CN 113524836 A CN113524836 A CN 113524836A CN 202110710463 A CN202110710463 A CN 202110710463A CN 113524836 A CN113524836 A CN 113524836A
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parts
thermoplastic elastomer
basketball court
calcium carbonate
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CN113524836B (zh
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高文通
韩冰
赵辉
陈韶
周松乐
余辉
黄玉安
易翔
余保寅
张奕磊
张波
梁红文
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Jiangsu Regalfill Rubber And Plastic Material Co ltd
Nanjing Institute of Technology
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Nanjing Institute of Technology
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Abstract

本发明公开了一种预制型热塑性弹性体篮球场地面及其制备方法,所述篮球场地面包括弹性体组合物和覆盖于弹性体组合物表面的薄膜,弹性体组合物包括重量份20~40份SBS,30~50份碳酸钙,30~50份溶剂油,10~15份SIS,10~15份PP和0.1~1份抗氧剂;所述薄膜经过空气等离子体处理且所述薄膜的外表面经环氧树脂接枝固化改性。本发明的预制型热塑性弹性体篮球场地面是在弹性体组合物辊压成型过程中,将薄膜直接附着于弹性体组合物表面,随着辊压过程的进行同时薄膜也被加热粘接在弹性体组合物上,该方法制备的热塑性弹性体篮球场地面表面耐磨性高、防污性好,工艺环保。

Description

一种预制型热塑性弹性体篮球场地面及其制备方法
技术领域
本发明属于高分子弹性篮球场地面领域,更具体地涉及一种预制型热塑性弹性体篮球场地面及其制备方法。
背景技术
预制型热塑性弹性体篮球场作为一类新型的运动场地,以热塑性弹性体为基材,具有环保性强、全可回收等优点,且采用预制成型技术,具有不含橡胶颗粒、安装方便、卷材厚度均一、产品性能稳定等优势。热塑性弹性体用于地面类材料制备时通常会加入油等助剂以提高产品的加工成型性能,而该类助剂不可避免的会向表面迁移,另外材料整体极性也很小,极易造成表面不耐污的问题,这也困扰着该类材料在室外场地尤其室外篮球场中的应用,是行业亟需解决的问题。
专利CN 201680081526.4包括热塑性弹性体的楼面覆盖物及其制造方法,公开了包含烯烃基聚合物、接枝有酸基团/或酸酐基团的聚合物、苯乙烯基热塑性弹性体、油和填料等组份的楼面覆盖物,并提出一个塑料材料膜的覆盖层,以提高楼面覆盖物的耐磨性,但该楼面覆盖物并未解决表面极性小、不耐污的问题,且其主要应用于楼内地面,对材料的机械阻力和强度的要求较高,但由于其应用环境相对简单,其耐磨性不能满足室外地面的需要。
环氧树脂属于热固性树脂,耐磨性能优异,且属于极性材料,具有良好的表面防污性能,广泛用于室外表面防护,但其自身弹性较差,且因为自身极性缘故,较难与非极性热塑性弹性体形成紧密的粘接力。
发明内容
本发明所要解决的技术问题在于针对上述材料的不足,提供一种预制型热塑性弹性体篮球场地面及其制备方法。
本发明所提供的篮球场地面表面耐磨性高、防污性好,工艺环保。
本发明通过以下的技术方案实现上述目的:
一种预制型热塑性弹性体篮球场地面,包括弹性体组合物和覆盖于所述弹性体组合物表面的薄膜,所述弹性体组合物包括如下重量份的组分:
SBS 20~40份;
碳酸钙30~50份;
溶剂油30~50份;
SIS 10~15份;
PP 10~15份;
和抗氧剂0.1~1份;
所述薄膜经过空气等离子体处理且所述薄膜的外表面经环氧树脂接枝固化改性。
优选的,所述薄膜的材质为聚丙烯。
优选的,所述环氧树脂为丙烯酸酯封端的双酚A型环氧树脂。所述的薄膜由聚丙烯薄膜经空气等离子体双面处理后,通过热引发聚丙烯薄膜单面与丙烯酸酯封端的双酚A型环氧树脂发生共聚接枝固化反应得到。
所述双酚A型环氧丙烯酸树脂结构式如下:
Figure BDA0003132861070000021
优选的,所述的SBS为CH-4412HE、D-1112P、F675或YH-1401中的一种或多种的组合物。
优选的,所述的碳酸钙为纳米碳酸钙、600目以上超细重质碳酸钙或400目以下轻质碳酸钙中的一种或多种的组合物。
所述的溶剂油为环烷油4010、环烷油4006、白油或石蜡油中的一种或多种的组合物。
所述的SIS为D-1161、YH-1106、YH-1126或YH-1105中的一种或多种的组合物。
所述的抗氧剂为乙氧基喹啉(EQ)或2,6-二叔丁基对甲酚(BHT)中的一种或两种的组合物。
本发明还提供上述预制型热塑性弹性体篮球场地面的制备方法,包括以下步骤:
(1)混料阶段:将SBS、碳酸钙、溶剂油、SIS、PP和抗氧剂混合均匀;
(2)覆膜阶段:将步骤(1)混合均匀的物料通过挤出机挤出,挤出温度为170~200℃,随后于120~160℃条件下,在挤出的物料表面覆上所述薄膜;
所述薄膜由如下方法得到:
先将薄膜的双面经空气等离子体处理,之后将经过空气等离子体处理的薄膜的一侧表面涂覆环氧树脂,于120~160℃条件下保温5~10min即得;
(3)辊压成型阶段:将步骤(2)得到的材料辊压、冷却成型。
优选的,步骤(2)中所述的空气等离子体处理在等离子反应器内进行。
优选的,步骤(2)中所述的空气等离子体处理的条件为:空气流量为80~120mL/min,优选为100mL/min;放电功率为80~100W,优选为90W;电极间距为3.2~4.0cm,优选为3.6cm;等离子体处理的时间为3~10min。
优选的,步骤(1)所述的混合在搅拌机中进行。优选的,搅拌机的转速为1000~2000转/min,混合时间为1~2min。
优选的,步骤(2)所述的挤出机为双螺杆挤出机。
优选的,步骤(2)还包括将覆上薄膜之后保温的步骤。优选的,保温的时间为5~10min。
优选的,步骤(3)所述的辊压为采用花纹辊辊压。使得材料表面形成花纹。
本发明的有益效果在于:
(1)薄膜经过空气等离子体表面处理,其表面分子发生官能团化反应,表面分子链上产生大量含氧官能团,其中含氧官能团中存在稳定的过氧化物自由基,这些过氧化物自由基可在热引发下与丙烯酸酯封端的双酚A型环氧树脂发生共聚接枝固化反应,在表明形成极性、坚固且耐磨的环氧树脂层,可有效提高表面张力,并能够糙化表面,有效去除其表面的油污、水气和尘垢等,另外,薄膜极性的提高可有效防止内部油等助剂向表面迁移,提高材料的表面耐污性能。
(2)经等离子体处理过的薄膜,其一面与丙烯酸酯封端的双酚A型环氧树脂发生共聚接枝固化反应,另一面上稳定的过氧化物自由基可与热塑性弹性体篮球场基材中的SBS、SIS所含有的双键发生共聚接枝反应,在表面形成合金化结构,能够显著提高薄膜与篮球场基材的粘接强度。
(3)本发明的预制型热塑性弹性体篮球场地面是在弹性体组合物辊压成型过程中,将薄膜直接附着于弹性体组合物表面,随着辊压过程的进行同时薄膜也被加热粘接在弹性体组合物上,该方法制备的篮球场地面表面耐磨性高、防污性好,工艺环保。
具体实施方式
实施例1
弹性体组合物:由30份SBS(CH-4412HE),40份400目轻质碳酸钙,40份环烷油4010,15份SIS(D-1161),10份PP和1份乙氧基喹啉组成。
薄膜处理:
(1)将PP薄膜置于等离子反应器内,打开气体流量控制器,并保持空气流量为80mL/min;打开放电装置开关,控制放电功率为80W;电极间距为4.0cm;等离子体处理时间为10min,聚丙烯薄膜等离子体处理为双面处理。
(2)将等离子体处理过的PP薄膜的一侧表面均匀涂覆一层丙烯酸酯封端的双酚A型环氧树脂,控制温度为120℃,保温10min,引发PP薄膜表面过氧化物与双酚A型环氧丙烯酸树脂发生共聚接枝固化反应,反应终点为红外光谱法监测双酚A型环氧丙烯酸树脂1630cm-1处的C=C伸缩振动吸收峰和810cm-1处的=C-H弯曲振动吸收峰完全消失,得到表面接枝环氧树脂的PP薄膜。
制备方法:
(1)混料阶段:将SBS,碳酸钙,环烷油,SIS,PP和乙氧基喹啉在混合搅拌机中混合均匀,转速1000转/min,混合时间为2min。
(2)覆膜阶段:将上述混合均匀的物料通过双螺杆挤出机挤出,挤出温度为170℃,随后自然降温至120℃,在表面覆上表面接枝环氧树脂的PP薄膜,薄膜未经接枝处理的一面接触该挤出后的物料,并保温10min;
(3)辊压成型阶段:覆膜完成的弹性体组合物经花纹辊辊压形成表面花纹,冷却成型。
实施例2
弹性体组合物:由40份SBS(D-1112P),50份600目超细重质碳酸钙,50份环烷油4006,15份SIS(YH-1106),10份PP和0.5份乙氧基喹啉组成。
薄膜处理:(1)将PP薄膜置于等离子反应器内,打开气体流量控制器,并保持空气流量为120mL/min;打开放电装置开关,控制放电功率为100W;电极间距为3.2cm;等离子体处理时间为3min,聚丙烯薄膜等离子体处理为双面处理。
(2)将等离子体处理过的PP薄膜表面均匀涂覆一层丙烯酸酯封端的双酚A型环氧树脂,控制温度为160℃,保温5min,引发PP薄膜表面过氧化物与双酚A型环氧丙烯酸树脂发生共聚接枝固化反应,反应终点为红外光谱法监测双酚A型环氧丙烯酸树脂1630cm-1处的C=C伸缩振动吸收峰和810cm-1处的=C-H弯曲振动吸收峰完全消失,得到表面接枝环氧树脂的PP薄膜。
制备方法:
(1)混料阶段:将SBS,碳酸钙,环烷油,SIS,PP和乙氧基喹啉在混合搅拌机中混合均匀,转速1000转/min,混合时间为2min。
(2)覆膜阶段:将上述混合均匀的物料通过双螺杆挤出机挤出,挤出温度为200℃,随后自然降温至160℃,在表面覆上表面接枝环氧树脂的PP薄膜,薄膜未经接枝处理的一面接触该挤出后的物料,并保温5min;
(3)辊压成型阶段:覆膜完成的弹性体组合物经花纹辊辊压形成表面花纹,冷却成型。
实施例3
弹性体组合物:由30份SBS(F675),40份纳米碳酸钙,50份石蜡油,15份SIS(YH-1126),10份PP和0.5份2,6-二叔丁基对甲酚组成。
薄膜处理:
(1)将PP薄膜置于等离子反应器内,打开气体流量控制器,并保持空气流量为100mL/min;打开放电装置开关,控制放电功率为90W;电极间距为3.6cm;等离子体处理时间为8min,聚丙烯薄膜等离子体处理为双面处理。
(2)将等离子体处理过的PP薄膜表面均匀涂覆一层丙烯酸酯封端的双酚A型环氧树脂,控制温度为140℃,保温8min,引发PP薄膜表面过氧化物与双酚A型环氧丙烯酸树脂发生共聚接枝固化反应,反应终点为红外光谱法监测双酚A型环氧丙烯酸树脂1630cm-1处的C=C伸缩振动吸收峰和810cm-1处的=C-H弯曲振动吸收峰完全消失,得到表面接枝环氧树脂的PP薄膜。
制备方法:
(1)混料阶段:将SBS,碳酸钙,石蜡油,SIS,PP和2,6-二叔丁基对甲酚在混合搅拌机中混合均匀,转速2000转/min,混合时间为1min。
(2)覆膜阶段:将上述混合均匀的物料通过双螺杆挤出机挤出,挤出温度为180℃,随后自然降温至130℃,在表面覆上表面接枝环氧树脂的PP薄膜,薄膜未经接枝处理的一面接触该挤出后的物料,并保温8min;
(3)辊压成型阶段:覆膜完成的弹性体组合物经花纹辊辊压形成表面花纹,冷却成型。
实施例4
弹性体组合物:由20份SBS(YH-1401),30份800目超细重质碳酸钙,30份白油,10份SIS(YH-1105),15份PP和0.1份2,6-二叔丁基对甲酚组成。
薄膜处理:
(1)将PP薄膜置于等离子反应器内,打开气体流量控制器,并保持空气流量为100mL/min;打开放电装置开关,控制放电功率为100W;电极间距为3.4cm;等离子体处理时间为6min,聚丙烯薄膜等离子体处理为双面处理。
(2)将等离子体处理过的PP薄膜表面均匀涂覆一层丙烯酸酯封端的双酚A型环氧树脂,控制温度为150℃,保温7min,引发PP薄膜表面过氧化物与双酚A型环氧丙烯酸树脂发生共聚接枝固化反应,反应终点为红外光谱法监测双酚A型环氧丙烯酸树脂1630cm-1处的C=C伸缩振动吸收峰和810cm-1处的=C-H弯曲振动吸收峰完全消失,得到表面接枝环氧树脂的PP薄膜。
制备方法:
(1)混料阶段:将SBS,碳酸钙,石蜡油,SIS,PP和2,6-二叔丁基对甲酚在混合搅拌机中混合均匀,转速2000转/min,混合时间为1min。
(2)覆膜阶段:上述混合均匀的物料通过双螺杆挤出机挤出,挤出温度为180℃,随后自然降温至140℃,在表面覆上表面接枝环氧树脂的PP薄膜,并保温8min;
(3)辊压成型阶段:覆膜完成的弹性体组合物经花纹辊辊压形成表面花纹,冷却成型。
对比例1
弹性体组合物:由30份SBS(F675),40份纳米碳酸钙,50份石蜡油,15份SIS(YH-1126),10份PP和0.5份2,6-二叔丁基对甲酚组成。
制备方法:
(1)混料阶段:将SBS,碳酸钙,石蜡油,SIS,PP和2,6-二叔丁基对甲酚在混合搅拌机中混合均匀,转速2000转/min,混合时间为1min。
(2)覆膜阶段:将上述混合均匀的物料通过双螺杆挤出机挤出,挤出温度为180℃,随后自然降温至130℃,在表面覆上未经任何处理的PP薄膜,并保温8min;
(3)辊压成型阶段:覆膜完成的弹性体组合物经花纹辊辊压形成表面花纹,冷却成型。
对比例2
弹性体组合物:由30份SBS(F675),40份纳米碳酸钙,50份石蜡油,15份SIS(YH-1126),10份PP和0.5份2,6-二叔丁基对甲酚组成。
薄膜处理:
将PP薄膜置于等离子反应器内,打开气体流量控制器,并保持空气流量为100mL/min;打开放电装置开关,控制放电功率为90W;电极间距为3.6cm;等离子体处理时间为8min,聚丙烯薄膜等离子体处理为双面处理。
制备方法:
(1)混料阶段:将SBS,碳酸钙,石蜡油,SIS,PP和2,6-二叔丁基对甲酚在混合搅拌机中混合均匀,转速2000转/min,混合时间为1min。
(2)覆膜阶段:将上述混合均匀的物料通过双螺杆挤出机挤出,挤出温度为180℃,随后自然降温至130℃,在表面覆上仅经过等离子体处理的PP薄膜,并保温8min;
(3)辊压成型阶段:覆膜完成的弹性体组合物经花纹辊辊压形成表面花纹,冷却成型。
材料测试结果
对实施例1-4及对比例1-2得到的材料进行表面硬度和耐磨耐污性能测试,其中耐磨性能采用TABER磨耗试验仪YL-3315进行测试,每250r后计算样品的失重值,测试结果如表1所示:
表1样品性能及3个月后表面外观对比表
Figure BDA0003132861070000071

Claims (10)

1.一种预制型热塑性弹性体篮球场地面,其特征在于,包括弹性体组合物和覆盖于所述弹性体组合物表面的薄膜,所述弹性体组合物包括如下重量份的组分:
SBS 20~40份;
碳酸钙30~50份;
溶剂油30~50份;
SIS 10~15份;
PP 10~15份;
和抗氧剂0.1~1份;
所述薄膜经过空气等离子体处理且所述薄膜的外表面经环氧树脂接枝固化改性;
优选的,所述薄膜的材质为聚丙烯。
2.根据权利要求1所述的预制型热塑性弹性体篮球场地面,其特征在于,所述环氧树脂为丙烯酸酯封端的双酚A型环氧树脂。
3.根据权利要求1所述的预制型热塑性弹性体篮球场地面,其特征在于,所述的SBS为CH-4412HE、D-1112P、F675或YH-1401中的一种或多种的组合物。
4.根据权利要求1所述的预制型热塑性弹性体篮球场地面,其特征在于,所述的碳酸钙为纳米碳酸钙、600目以上超细重质碳酸钙或400目以下轻质碳酸钙中的一种或多种的组合物。
5.根据权利要求1所述的预制型热塑性弹性体篮球场地面,其特征在于,所述的溶剂油为环烷油4010、环烷油4006、白油或石蜡油中的一种或多种的组合物。
6.根据权利要求1所述的预制型热塑性弹性体篮球场地面,其特征在于,所述的SIS为D-1161、YH-1106、YH-1126或YH-1105中的一种或多种的组合物。
7.根据权利要求1所述的预制型热塑性弹性体篮球场地面,其特征在于,所述的抗氧剂为乙氧基喹啉或2,6-二叔丁基对甲酚中的一种或两种的组合物。
8.权利要求1-7任一项所述预制型热塑性弹性体篮球场地面的制备方法,其特征在于,包括以下步骤:
(1)混料阶段:将SBS、碳酸钙、溶剂油、SIS、PP和抗氧剂混合均匀;
(2)覆膜阶段:将步骤(1)混合均匀的物料通过挤出机挤出,挤出温度为170~200℃,随后于120~160℃条件下,在挤出的物料表面覆上所述薄膜;
所述薄膜由如下方法得到:
先将薄膜的双面经空气等离子体处理,之后将经过空气等离子体处理的薄膜的一侧表面涂覆环氧树脂,于120~160℃条件下保温5~10min即得;
(3)辊压成型阶段:将步骤(2)得到的材料辊压、冷却成型。
9.根据权利要求8所述的制备方法,其特征在于,步骤(2)中所述的空气等离子体处理的条件为:空气流量为80~120mL/min,优选为100mL/min;放电功率为80~100W,优选为90W;电极间距为3.2~4.0cm,优选为3.6cm;等离子体处理的时间为3~10min。
10.根据权利要求8所述的制备方法,其特征在于,步骤(2)还包括将覆上薄膜之后保温的步骤;优选的,保温的时间为5~10min。
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