CN106319110B - 皮革用聚八乙烯基笼型倍半硅氧烷‑丙烯酸纳米复合助剂及其制备方法 - Google Patents

皮革用聚八乙烯基笼型倍半硅氧烷‑丙烯酸纳米复合助剂及其制备方法 Download PDF

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CN106319110B
CN106319110B CN201610998893.2A CN201610998893A CN106319110B CN 106319110 B CN106319110 B CN 106319110B CN 201610998893 A CN201610998893 A CN 201610998893A CN 106319110 B CN106319110 B CN 106319110B
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马建中
贾潞
高党鸽
吕斌
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Shaanxi University of Science and Technology
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Abstract

本发明涉及皮革用聚八乙烯基笼型倍半硅氧烷‑丙烯酸纳米复合助剂及其制备方法。混合八乙烯基笼型倍半硅氧烷、有机溶剂、过硫酸铵、蒸馏水和表面活性剂，滴加丙烯酸恒温反应，冷却得到皮革用聚八乙烯基笼型倍半硅氧烷‑丙烯酸纳米复合助剂。本发明得到的助剂更容易渗透到胶原纤维的内部，与皮胶原纤维产生纳米级、微米级结合，能进一步提高丙烯酸聚合物与胶原的多点结合，以提高其对皮革的填充性，且不影响得革率，废液中铬含量显著降低。

Description

皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂及 其制备方法
技术领域
本发明涉及一种皮革用鞣制助剂，具体涉及一种皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂及其制备方法。
背景技术
多面体低聚倍半硅氧烷（POSS）是一种有机-无机纳米颗粒，于1946年由D.W.等首次合成。POSS的分子通式为（RSiO1.5）n（4≤n≤8），式中的R是有机取代基，可以为H、烷基、芳基等惰性基团和乙烯基、氨基等活性基团，分子具有无机骨架且分子尺寸在1-3nm之间。POSS具有一个纳米级的立方体三维结构空腔，同时在立方体结构的顶点共有8个可修饰的位点，活性基团通过化学改性可以与聚合物或者聚合物单体反应，因而具有巨大的改性前景。
丙烯酸聚合物可与铬盐形成配合物，是一种结合能力强、填充效果好的高分子鞣剂。该类鞣剂可以改善皮革的物理机械性能，对铬离子有一定的吸收固定作用。将POSS与丙烯酸聚合物相结合，在立方体的8个顶点连接聚合物，与线型聚合物相比，具有独特的多侧链结构，可大大提高侧链的活性基团数量。同时，八乙烯基笼型倍半硅氧烷与丙烯酸单体共聚形成有机-无机相间具有共价键合作用的纳米杂化材料，与皮胶原纤维产生纳米级、微米级结合，有望提高胶原材料热稳定性，并对皮胶原纤维起到良好的填充作用；多侧链的聚合物结构可以进一步增加铬与胶原的结合位点，提高了铬的吸收率，减少制革污染，实现清洁生产。
发明内容
本发明的目的是提供一种皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂及其制备方法，该助剂的使用可以提高皮革热稳定性、填充性，又可以减少鞣制过程中铬粉使用，降低鞣制废液中Cr3+含量。
本发明所采用的技术方案为：
皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂的制备方法，其特征在于：
包括以下步骤：
在装有搅拌器和冷凝装置的三口烧瓶中加入八乙烯基笼型倍半硅氧烷0.1-0.5g，有机溶剂1-15g，过硫酸铵0.4-1g，蒸馏水35-40g，表面活性剂0.05-0.4g；
将8-16g丙烯酸加入恒压滴液漏斗中，待水浴加热至60℃时向三口烧瓶中滴加丙烯酸30-60min，恒温反应6-8h，冷却，调节pH为5.0，出料，得到皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂。
所述的有机溶剂选自二氯甲烷、二甲基亚砜、二甲基甲酰胺。
所述的表面活性剂选自十二烷基硫酸钠、十二烷基苯磺酸钠。
如所述的皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂的制备方法制得的复合助剂。
本发明具有以下优点：
本发明制备的皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂是通过共价键合作用形成的纳米杂化材料，得到的材料具有独特的多侧链结构。将其配合3.5%铬粉应用于牛皮鞣制工序，与线型丙烯酸聚合物配合3.5%铬粉鞣制相比，可使蓝湿革增厚率提高21%，收缩温度提高4℃；与3.5%铬粉鞣制相比，可将蓝湿革收缩温度提高5℃，增厚率可提高96%，且不影响得革率，废液中铬含量可降低50%以上。该助剂的有利于实现皮革鞣剂的清洁化发展。
具体实施方式
下面结合具体实施方式对本发明进行详细的说明。
本发明涉及的皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂的制备方法，能进一步提高丙烯酸聚合物与胶原的多点结合，以提高其对皮革的填充性，包括以下步骤：
在装有搅拌器和冷凝装置的三口烧瓶中加入八乙烯基笼型倍半硅氧烷0.1-0.5g，有机溶剂1-15g，过硫酸铵0.4-1g，蒸馏水35-40g，表面活性剂0.05-0.4g；
将8-16g丙烯酸加入恒压滴液漏斗中，待水浴加热至60℃时向三口烧瓶中滴加丙烯酸30-60min，恒温反应6-8h，冷却，调节pH为5.0，出料，得到皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂。
所述的有机溶剂选自二氯甲烷、二甲基亚砜、二甲基甲酰胺。
所述的表面活性剂选自十二烷基硫酸钠、十二烷基苯磺酸钠。
实施例1：
在装有搅拌器和冷凝装置的三口烧瓶中加入八乙烯基笼型倍半硅氧烷0.1g，二甲基亚砜6g，过硫酸铵0.6g，蒸馏水38g，十二烷基苯磺酸钠0.05g；将10g丙烯酸加入恒压滴液漏斗中，待水浴加热至60℃时向三口烧瓶中滴加烯丙烯酸30min，恒温反应6h，冷却，调节pH为5.0，出料，得到皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂。
实施例2：
在装有搅拌器和冷凝装置的三口烧瓶中加入八乙烯基笼型倍半硅氧烷0.2g，二甲基甲酰胺12g，过硫酸铵0.7g，蒸馏水40g，十二烷基苯磺酸钠0.1g；将15g丙烯酸加入恒压滴液漏斗中，待水浴加热至60℃时向三口烧瓶中滴加烯丙烯酸40min，恒温反应7h，冷却，调节pH为5.0，出料，得到皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂。
实施例3：
在装有搅拌器和冷凝装置的三口烧瓶中加入八乙烯基笼型倍半硅氧烷0.3g，二氯甲烷10g，过硫酸铵0.5g，蒸馏水36g，十二烷基苯磺酸钠0.2g；将16g丙烯酸加入恒压滴液漏斗中，待水浴加热至60℃时向三口烧瓶中滴加烯丙烯酸50min，恒温反应8h，冷却，调节pH为5.0，出料，得到皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂。
实施例4：
在装有搅拌器和冷凝装置的三口烧瓶中加入八乙烯基笼型倍半硅氧烷0.4g，二氯甲烷4g，过硫酸铵0.9g，蒸馏水39g，十二烷基硫酸钠0.2g；将10g丙烯酸加入恒压滴液漏斗中，待水浴加热至60℃时向三口烧瓶中滴加烯丙烯酸60min，恒温反应6h，冷却，调节pH为5.0，出料，得到皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂。
实施例5：
在装有搅拌器和冷凝装置的三口烧瓶中加入八乙烯基笼型倍半硅氧烷0.1g，二甲基亚砜10g，过硫酸铵0.8g，蒸馏水35g，十二烷基硫酸钠0.3g；将8g丙烯酸加入恒压滴液漏斗中，待水浴加热至60℃时向三口烧瓶中滴加烯丙烯酸40min，恒温反应8h，冷却，调节pH为5.0，出料，得到皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂。
本发明制得的复合助剂配合3.5%铬粉应用于牛皮鞣制工序，与线型丙烯酸聚合物配合3.5%铬粉鞣制相比，可使蓝湿革增厚率提高21%，收缩温度提高4℃；与3.5%铬粉鞣制相比，可将蓝湿革收缩温度提高5℃，增厚率可提高96%，且不影响得革率，废液中铬含量可降低50%以上。
本发明的内容不限于实施例所列举，本领域普通技术人员通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换，均为本发明的权利要求所涵盖。

Claims (4)

1.皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂的制备方法，其特征在于：
包括以下步骤：
在装有搅拌器和冷凝装置的三口烧瓶中加入八乙烯基笼型倍半硅氧烷0.1-0.5g，有机溶剂1-15g，过硫酸铵0.4-1g，蒸馏水35-40g，表面活性剂0.05-0.4g；
将8-16g丙烯酸加入恒压滴液漏斗中，待水浴加热至60℃时向三口烧瓶中滴加丙烯酸30-60min，恒温反应6-8h，冷却，调节pH为5.0，出料，得到皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂。
2.根据权利要求1所述的皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂的制备方法，其特征在于：
所述的有机溶剂选自二氯甲烷、二甲基亚砜、二甲基甲酰胺。
3.根据权利要求1所述的皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂的制备方法，其特征在于：
所述的表面活性剂选自十二烷基硫酸钠、十二烷基苯磺酸钠。
4.如权利要求1所述的皮革用聚八乙烯基笼型倍半硅氧烷-丙烯酸纳米复合助剂的制备方法制得的复合助剂。
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