CN111548596A - 环保抗菌芳香型热塑性弹性体发泡材料及其制备方法和应用 - Google Patents
环保抗菌芳香型热塑性弹性体发泡材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及发泡材料技术领域，具体公开一种环保抗菌芳香型热塑性弹性体发泡材料，包括如下重量份数的组分：80～100份的SEBS、8～15份的顺丁橡胶、5～8份的高抗冲击聚苯乙烯、5～10份的EVA、3～5份的发泡剂、2～4份的交联剂、0.5～1份的硬脂酸锌、2～4份的白矿油以及10～20份的改性薰衣草颗粒。本发明采用改性薰衣草颗粒，可有效控制薰衣草香气成分的挥发，达到香气效力持久，同时可增强发泡材料和制品的抗菌性能和除臭，具有除味、透气、提神醒脑、熏香兼驱虫等优点，可提高薰衣草利用率，减少废弃物的浪费和环境污染，绿色环保，适用于鞋底、鞋垫、瑜伽垫、爬行垫等生活用品和运动器材。
Description
技术领域
本发明属于发泡材料技术领域，具体涉及一种环保抗菌芳香型热塑性弹性体发泡材料及其制备方法和应用。
背景技术
热塑性弹性体材料一般是用热塑性弹性体SBS或SEBS与其它功能助剂共混改性的一种高分子材料，经过挤出、注射、模压等工艺加工后成型制成，具有防滑、弯曲性强、透气性好、粘结强度牢等优点。
薰衣草，被称为“百草之王”，香气清新优雅，性质温和，是公认为最具有镇静，舒缓，催眠作用的植物，可舒缓紧张情绪、镇定心神，平息静气，舒缓压力等功效，而制作成香包可代替樟脑丸放在橱柜内熏香兼驱虫。
中国公开专利文献(CN109401356A)公开了一种薰衣草高分子复合材料及其制备方法，薰衣草高分子复合材料，包括以下质量百分比的组份：薰衣草母料23％～27％；橡塑材料55％～65％；树脂8％～12％；交联剂4％～6％，薰衣草母料由薰衣草粉和橡塑材料在115℃～125℃的条件下存储18～20分钟作硫化处理后进入混炼机，混炼机充分混炼已硫化的原料后输送到造粒机，造粒机制出薰衣草母料。该专利技术采用了薰衣草作为薰衣草高分子复合材料的基料，充分利用了薰衣草本身的香气悠然、镇静催眠、解痉、抗菌、神经保护、降脂、治疗神经症等特性，使用时可提神醒脑，增强记忆，缓解神经，怡情养性，促进血液循环，可治疗青春痘，滋养秀发，抑制高血压、鼻敏感气喘，调节生理机能，增强免疫力，维持呼吸道机能，对鼻喉粘膜炎有很好的疗效，特别适用于生活用品、运动器材使用。
但是，薰衣草粉的香气挥发较快，存在持久效力问题。另外，热塑性弹性体发泡材料中一般还会加入AC发泡剂，AC发泡剂在发泡过程中会分解产生氨气和甲酰胺，发泡制品带有刺激的臭味，在日常使用过程中此种气味容易让人产生不舒服的感觉。
发明内容
鉴于现有技术的不足，本发明所要解决的技术问题是提供一种环保抗菌芳香型热塑性弹性体发泡材料。
为解决上述技术问题，本发明采用的技术方案是：
环保抗菌芳香型热塑性弹性体发泡材料，包括如下重量份数的组分：80～100份的SEBS、8～15份的顺丁橡胶、5～8份的高抗冲击聚苯乙烯、5～10份的EVA、3～5份的发泡剂、2～4份的交联剂、0.5～1份的硬脂酸锌、2～4份的白矿油以及10～20份的改性薰衣草颗粒。
优选地，所述发泡剂是指偶氮二甲酰胺碳酸氢铵中的一种或多种的混合物。
优选地，所述交联剂为双叔丁基过氧化异丙基苯和过氧化二异丙苯一种或两种的混合物。
优选地，所述改性薰衣草颗粒由如下重量份数的组分制成：20-30份的薰衣草粉末、5-8份的水性聚氨酯树脂、1-1.5份的碳酸氢钠、2.5-3份的抗坏血酸、1-2份的纳米氧化锌和2.5-3.0份的聚N-乙烯基乙酰胺。
所述改性薰衣草颗粒的制备方法具体如下：
a)、将破碎成100-200目的薰衣草粉末置于90℃～95℃的双氧水中处理30-45min，使薰衣草纤维素中羟基活化，过滤后清洗，得到羟基活化薰衣草粉末；
b)、将水性聚氨酯树脂溶于乙醇形成有机溶液，分别加入步骤a)的羟基活化薰衣草粉末、碳酸氢钠、抗坏血酸及聚N-乙烯基乙酰胺，低温超声分散均匀后进行喷雾干燥，得到在羟基活化薰衣草粉末表面包裹水性聚氨酯树脂、碳酸氢钠和抗坏血酸的反应颗粒；
c)、将步骤b)的反应颗粒于125℃～140℃加热发泡形成具有开孔球形泡孔结构的微孔发泡薰衣草颗粒；
d)、将步骤c)的微孔发泡薰衣草颗粒及纳米氧化锌加入乙醇溶液中，然后超声分散12-15小时得到悬浮液；
e)、将步骤d)的悬浮液上半部分取出，离心分离后置于真空干燥箱中70℃～80℃干燥，粉碎、研磨，得到表面负载有纳米氧化锌的改性薰衣草颗粒。
本发明进一步提供一种环保抗菌芳香型热塑性弹性体发泡材料制备方法，具体步骤为：
S1、制备改性薰衣草颗粒；
S2、将步骤S1的改性薰衣草与SEBS、EVA、顺丁橡胶、高抗冲击聚苯乙烯、硬脂酸锌和白矿油混合进行混炼25min～40min，待温度达到100℃时加入发泡剂和交联剂继续密炼，待温度升至110℃～115℃时排料得到混合料，将混合料加入开炼机80℃～85℃下开炼，薄通2次，薄通时出片厚度为1mm，开炼后的物料转入造粒机进行造粒，冷却，静置，得到复合粒料；
S3、向发泡机的模具上喷涂脱模剂，加入复合粒料进行模压发泡，发泡温度155℃～165℃，发泡的压力可为10～15Mpa，发泡时间为15min～20min，即得热塑性弹性体复合发泡材料。
上述环保抗菌芳香型热塑性弹性体发泡材料可以加工成鞋底、鞋垫、瑜伽垫、爬行垫等发泡制品中。
与现有技术相比，本发明具有以下有益效果：
1、本发明采用改性薰衣草颗粒，通过碳酸氢钠在薰衣草粉末表面微孔发泡形成具有开孔球形泡孔结构，这样可有效控制薰衣草香气成分的挥发，达到香气效力持久，同时利用比表面积大以及聚N-乙烯基乙酰胺，可很好地吸附纳米氧化锌，避免纳米氧化锌易团聚问题，而纳米氧化锌具有光催化抗菌效果可增强发泡材料和制品的抗菌性能，同时还起到对薰衣草粉末的热保护作用，发泡效果好。另外，负载于改性薰衣草颗粒上的纳米氧化锌还利于增强发泡材料和制品的力学性能。
2、本发明通过氧化处理使薰衣草纤维素中羟基活化，在发泡过程中能与产生的甲酰胺的羰基发生羟醛缩合反应而消耗掉甲酰胺，并且比表面积大的泡孔表面上的抗坏血酸也能够中和碱性的氨类形成铵盐，可大大减少发泡材料和制品中氨气的释放，从而达到除臭以及保证薰衣草香气的纯正。
3、本发明改性薰衣草颗粒包含聚N-乙烯基乙酰胺，其为螺旋形非离子型分散剂，可有效改善薰衣草粉末与水性聚氨酯树脂和胶料的相容性，保证发泡材料及制品良好的力学性能。
4、本发明充分利用了薰衣草本身的香气特性，发泡材料及制品具有除味、透气、提神醒脑、熏香兼驱虫等优点，特别适用于鞋底、鞋垫、瑜伽垫、爬行垫等生活用品和运动器材使用，且加工中无需添加碳酸钙或者滑石粉等填充剂就可正常发泡，可提高薰衣草利用率，减少废弃物的浪费和环境污染，绿色环保，降低了生产成本。
具体实施方式
本发明提供一种环保抗菌芳香型热塑性弹性体发泡材料，包括如下重量份数的组分：80～100份的SEBS、8～15份的顺丁橡胶、5～8份的高抗冲击聚苯乙烯、5～10份的EVA、3～5份的发泡剂、2～4份的交联剂、0.5～1份的硬脂酸锌、2～4份的白矿油以及10～20份的改性薰衣草颗粒。本发明的环保抗菌芳香型热塑性弹性体发泡材料可以加工成鞋底、鞋垫、瑜伽垫、爬行垫等发泡制品。
下面给出本发明环保抗菌芳香型热塑性弹性体发泡材料的几个具体实施例，同时也给出3个对比例，各实施例和对比例中的组分配比参见表1和表2。
其中，本发明实施例1-5中的环保抗菌芳香型热塑性弹性体发泡材料均采用如下方法制得，具体为：
S1、制备改性薰衣草颗粒；
S2、将步骤S1的改性薰衣草与SEBS、EVA、顺丁橡胶、高抗冲击聚苯乙烯、硬脂酸锌和白矿油混合进行混炼25min～40min，待温度达到100℃时加入发泡剂和交联剂继续密炼，待温度升至110℃～115℃时排料得到混合料，将混合料加入开炼机80℃～85℃下开炼，薄通2次，薄通时出片厚度为1mm，开炼后的物料转入造粒机进行造粒，冷却，静置，得到复合粒料；
S3、向发泡机的模具上喷涂脱模剂，加入复合粒料进行模压发泡，发泡温度155℃～165℃，发泡的压力可为10～15Mpa，发泡时间为15min～20min，即得热塑性弹性体发泡材料。
其中，本发明实施例1-5中的改性薰衣草颗粒均采用如下方法制得，具体为：
a)、将破碎成100-200目的薰衣草粉末置于90℃～95℃的双氧水中处理30-45min，使薰衣草纤维素中羟基活化，过滤后清洗，得到羟基活化薰衣草粉末；
b)、将水性聚氨酯树脂溶于乙醇形成有机溶液，分别加入步骤a)的羟基活化薰衣草粉末、碳酸氢钠、抗坏血酸及聚N-乙烯基乙酰胺，低温超声分散均匀后进行喷雾干燥，得到在羟基活化薰衣草粉末表面包裹水性聚氨酯树脂、碳酸氢钠和抗坏血酸的反应颗粒；
c)、将步骤b)的反应颗粒于125℃～140℃加热发泡形成具有开孔球形泡孔结构的微孔发泡薰衣草颗粒；d)、将步骤c)的微孔发泡薰衣草颗粒及纳米氧化锌加入乙醇溶液中，然后超声分散12-15小时得到悬浮液；
e)、将步骤d)的悬浮液上半部分取出，离心分离后置于真空干燥箱中70℃～80℃干燥，粉碎、研磨，得到表面负载有纳米氧化锌的改性薰衣草颗粒。
表1：本发明实施例1-5及对比例1-3的配方表
表2：本发明实施例1-5及对比例1-3中改性薰衣草颗粒组成表
| 示例1 | 示例2 | 示例3 | 示例4 | 示例5 | 对比1 | 对比2 | 对比3 | |
| 薰衣草粉末 | 25 | 20 | 25 | 30 | 30 | 25 | 25 | 25 |
| 水性聚氨酯树脂 | 5 | 8 | 5 | 6 | 6 | / | 5 | 5 |
| 碳酸氢钠 | 1.2 | 1.5 | 1 | 1 | 1.2 | / | 1.2 | 1.2 |
| 抗坏血酸 | 2.5 | 2.5 | 3 | 2.5 | 3 | 2.5 | / | 2.5 |
| 柠檬酸 | / | / | / | / | / | / | 2.5 | / |
| 纳米氧化锌 | 1.5 | 1 | 1.2 | 1.8 | 2 | 1.5 | 1.5 | 1.5 |
| 聚N乙烯基乙酰胺 | 3 | 2.5 | 2.5 | 3 | 3 | 3 | 3 | 3 |
而本发明给出的对比例1-3的复合发泡材料制备方法与上述实施例1的制备方法区别仅在于步骤S1。
其中，对比例1的步骤S1改性薰衣草颗粒由如下方法制得，具体步骤为：
1a)、将破碎成100-200目的薰衣草粉末置于90℃～95℃的双氧水中处理30-45min，使薰衣草纤维素中羟基活化，过滤后清洗，得到羟基活化薰衣草粉末；
1b)、将步骤1a)的羟基活化薰衣草粉末、抗坏血酸、纳米氧化锌及聚N-乙烯基乙酰胺加入乙醇溶液中，超声分散12-15小时得到悬浮液；
1c)、将步骤1b)的悬浮液上半部分取出，离心分离后置于真空干燥箱中70℃～80℃干燥，粉碎、研磨。
其中，对比例2的步骤S1改性薰衣草颗粒由如下方法制得，具体步骤为：
2a)、将水性聚氨酯树脂溶于乙醇形成有机溶液，分别加入破碎成100-200目的薰衣草粉末、碳酸氢钠、柠檬酸及聚N-乙烯基乙酰胺，低温超声分散均匀后进行喷雾干燥，得到在羟基活化薰衣草粉末表面包裹水性聚氨酯树脂、柠檬酸和碳酸氢钠的反应颗粒；
2b)、将步骤2a)的反应颗粒置于模具内，125℃～140℃加热发泡形成具有开孔球形泡孔结构的微孔发泡薰衣草颗粒；
2c)、将步骤2b)的微孔发泡薰衣草颗粒及纳米氧化锌加入乙醇溶液中，然后超声分散12-15小时得到悬浮液；
2d)、将步骤2c)的悬浮液上半部分取出，离心分离后置于真空干燥箱中70℃～80℃干燥，粉碎、研磨。
其中，对比例3的步骤S1改性薰衣草颗粒由如下方法制得，具体步骤为：
3a)、将破碎成100-200目的薰衣草粉末20-30份置于90℃～95℃的双氧水中处理30-45min，使薰衣草纤维素中羟基活化，过滤后清洗，得到羟基活化薰衣草粉末；
3b)、将水性聚氨酯树脂溶于乙醇形成有机溶液，分别加入步骤3a)的羟基活化薰衣草粉末、碳酸氢钠、抗坏血酸及聚N-乙烯基乙酰胺，低温超声分散均匀后进行喷雾干燥，得到在羟基活化薰衣草粉末表面包裹水性聚氨酯树脂、碳酸氢钠和抗坏血酸的反应颗粒；
3c)、将步骤3b)的反应颗粒置于模具内，125℃～140℃加热发泡形成开孔球形泡孔结构，置于真空干燥箱中70℃～80℃干燥，粉碎、研磨。
分别取上述实施例1-5及对比例1-3制得的发泡材料进行拉伸强度、回弹值、透气量、大肠杆菌、金黄色葡萄球菌和气味等测试实验，实验结果参见表3。
表3：本发明实施例1-5及对比例1-3的物性测试结果表
其中：磨损率的测定：采用万能摩擦磨损试验机测试，测试条件为：测试力为30N，转速为250r/min，测试时间30min，计算磨损率，磨损率的计算公式为：磨损率＝(磨损前质量-磨损后质量)/磨损前质量*100％。
氨味检测方法参考鞋底异味标准(GB30585-2014)，具体为：制备的发泡试片1片，重126g左右，进行水洗两分钟后，将表面的水珠除尽，进行干燥，然后将试片放置进自封袋中，于室温下密封放置24h，在进行异味判别时，将自封袋封口打开15mm左右，鼻子凑近深吸进行判别。
以上显示和描述了本发明创造的基本原理和主要特征及本发明的优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明创造精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内，本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (7)
1.环保抗菌芳香型热塑性弹性体发泡材料，其特征在于：该复合发泡材料包括如下重量份数的组分：80～100份的SEBS、8～15份的顺丁橡胶、5～8份的高抗冲击聚苯乙烯、5～10份的EVA、3～5份的发泡剂、2～4份的交联剂、0.5～1份的硬脂酸锌、2～4份的白矿油以及10～20份的改性薰衣草颗粒。
2.根据权利要求1所述的环保抗菌芳香型热塑性弹性体发泡材料，其特征在于：所述发泡剂是指偶氮二甲酰胺碳酸氢铵中的一种或多种的混合物。
3.根据权利要求1所述的环保抗菌芳香型热塑性弹性体发泡材料，其特征在于：所述交联剂为双叔丁基过氧化异丙基苯和过氧化二异丙苯一种或两种的混合物。
4.根据权利要求1至3任一项所述的环保抗菌芳香型热塑性弹性体发泡材料，其特征在于：所述改性薰衣草颗粒由如下重量份数的组分制成：20-30份的薰衣草粉末、5-8份的水性聚氨酯树脂、1-1.5份的碳酸氢钠、2.5-3份的抗坏血酸、1-2份的纳米氧化锌和2.5-3.0份的聚N-乙烯基乙酰胺。
5.根据权利要求4所述的环保抗菌芳香型热塑性弹性体发泡材料，其特征在于：所述改性薰衣草颗粒的制备方法具体如下：
a）、将破碎成100-200目的薰衣草粉末置于90℃～95℃的双氧水中处理30-45min，使薰衣草纤维素中羟基活化，过滤后清洗，得到羟基活化薰衣草粉末；
b）、将水性聚氨酯树脂溶于乙醇形成有机溶液，分别加入步骤a）的羟基活化薰衣草粉末、碳酸氢钠、抗坏血酸及聚N-乙烯基乙酰胺，低温超声分散均匀后进行喷雾干燥，得到在羟基活化薰衣草粉末表面包裹水性聚氨酯树脂、碳酸氢钠和抗坏血酸的反应颗粒；
c)、将步骤b）的反应颗粒于125℃～140℃加热发泡形成具有开孔球形泡孔结构的微孔发泡薰衣草颗粒；
d）、将步骤c）的微孔发泡薰衣草颗粒及纳米氧化锌加入乙醇溶液中，然后超声分散12-15小时得到悬浮液；
e）、将步骤d）的悬浮液上半部分取出，离心分离后置于真空干燥箱中70℃～80℃干燥，粉碎、研磨，得到表面负载有纳米氧化锌的改性薰衣草颗粒。
6.一种如权利要求1所述的环保抗菌芳香型热塑性弹性体发泡材料的制备方法，其特征在于：具体步骤为：
S1、制备改性薰衣草颗粒；
S2、将步骤S1的改性薰衣草与SEBS、EVA、顺丁橡胶、高抗冲击聚苯乙烯、硬脂酸锌和白矿油混合进行混炼25min～40min，待温度达到100℃时加入发泡剂和交联剂继续密炼，待温度升至110℃～115℃时排料得到混合料，将混合料加入开炼机80℃～85℃下开炼，薄通2次，薄通时出片厚度为1mm，开炼后的物料转入造粒机进行造粒，冷却，静置，得到复合粒料；
S3、向发泡机的模具上喷涂脱模剂，加入复合粒料进行模压发泡，发泡温度155℃～165℃，发泡的压力可为10～15Mpa，发泡时间为15min～20min，即得热塑性弹性体复合发泡材料。
7.如权利要求1所述的环保抗菌芳香型热塑性弹性体发泡材料在鞋底、鞋垫、瑜伽垫、爬行垫的应用。
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| CN113854702A (zh) * | 2021-10-08 | 2021-12-31 | 东莞疆皓塑胶制品有限公司 | 一种减震除臭袜子鞋 |
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