CN112126199B - 一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材及其制备方法 - Google Patents
一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材及其制备方法 Download PDFInfo
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Abstract
本发明公开一种具有光催化效果的PETG/TPA‑SiPc@SiO2复合线材及其制备方法。本发明以高透光树脂PETG作为载体，提供一种具有光催化效果的PETG/TPA‑SiPc@SiO2复合线材及其制备方法。本发明的技术方案如下：首先按照质量比配方为PETG（40~70），PVA（5~25），三苯胺基树枝配体取代硅酞菁负载SiO2（3~25），增塑剂4~20，稳定剂3~6，分散剂0.5~2。其具体制备方法为：干燥称料混合；熔融挤出造粒；挤出定型收卷。本发明制得的复合线材具有良好的透光性和可见光光催化性能，制备方法简单高效，可应用于污水、空气和土壤中有机污染物的光催化降解处理。
Description
技术领域
本发明属于一种具有光催化效果PETG/TPA-SiPc@SiO2复合线材及其制备方法。
背景技术
中国专利CN108948060B公开了一种三苯胺基树枝配体取代硅酞菁（TPA-SiPc）的制备方法及其应用，专利中所述的TPA-SiPc由于三苯胺的引进，赋予了酞菁较大的空间位阻，阻止聚集体形成且提高其溶解性，也改善了酞菁由于聚集而引起的猝灭效应。在此基础上，我们使三苯胺基树枝配体取代硅酞菁负载SiO2，使其具有活性氧产率高、亲水性好、不易团聚和电子转移率高等优点，可应用于工业污水处理、降解染料废水等领域。但是，固态粉状的TPA-SiPc@SiO2在实际应用中存在器件化和回收利用问题。
增材制造技术俗称3D打印技术,是近30年快速发展的先进制造技术,其优势在于三维结构的快速和自由制造,被广泛应用于新产品开发、单件小批量制造。熔融沉积成型（FDM）作为3D打印技术重要组成部分，它可将材料通过熔丝堆叠形成具有复杂结构的器件，使得材料器件化。
PETG是由对苯二甲酸二甲酯（DMT）或对苯二甲酸（PTA）、乙二醇（EG）和对苯二甲酸（CHDM）三种单体共聚而成的共聚酯。在一定的EG/CHDM比例下，由于分子链中环己烷单元的引入，降低了整个分子链的规整性，PETG为一种完全无定形的透明共聚酯。它的透明性、着色性和气密性等克服了PET在这方面的缺陷，所以在食品包装、日用品和化妆品容器、光化学及医学领域有很好的应用前景。同时，PETG具有良好的加工性能，不需要添加任何增塑剂或其他任何改性剂。目前，PETG主要应用在板材、片材、异型材和化妆品包装等领域，直接应用于3D打印领域的报道较少。
因此，将TPA-SiPc@SiO2与PETG树脂共混，同时添加水溶性聚合物聚乙烯醇（PVA）作为致孔剂制备3D打印线材，在结合FDM技术的基础上，实现TPA-SiPc@SiO2器件化并应用于污水、空气和土壤中有机污染物的光催化降解处理。
发明内容
针对上述背景和问题，本发明的目的旨在解决TPA-SiPc@SiO2存在器件化和回收利用等问题，以高透光树脂PETG作为载体，提供一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材及其制备方法。本发明制得的复合线材具有良好的透光性和可见光光催化性能，制备方法简单高效，可应用于污水、空气和土壤中有机污染物的光催化降解处理。
本发明的目的是通过如下技术方案实现的：
一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材，其特征在于，由下述的重量百分比组分制成：
PETG 40~70
PVA 5~25
TPA-SiPc@SiO2 3~25
增塑剂 4~20
稳定剂 3~6
分散剂 0.5~2
所述的增塑剂至少有一种选自甘油、乙二醇、聚乙二醇和邻苯二甲酸二酯。
所述的稳定剂至少有一种选自氢氧化钙、氧化钙、氢氧化镁。
所述的分散剂至少有一种选自硬酯酸、聚乙烯蜡、氧化聚乙烯蜡。
本发明所述的一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材的制备方法，其特征在于，包括以下步骤：
A. 将PETG和稳定剂分别真空干燥，然后将PETG、PVA、增塑剂、稳定剂、分散剂和TPA-SiPc@SiO2 按照重量百分比配方准确称量，然后将称量后的各组分置于高速混合机中混合均匀，得到混合料；
B.将混合料通过双螺杆挤出机熔融挤出造料，得到共混颗粒，料筒温度为170~230℃，螺杆转速为50-300 rpm/min；
C.将共混颗粒加入到3D线材生产线的单螺杆挤出机中进行挤出定型收卷，得到3D打印线材，料筒温度为170~230 ℃，螺杆转速为10~100 rpm/min。
本发明上述的具有光催化效果的PETG/TPA-SiPc@SiO2复合线材的应用，其特征在于：所述PETG/TPA-SiPc@SiO2复合线材应用于3D打印领域。
本发明上述的具有光催化效果的PETG/TPA-SiPc@SiO2复合线材的应用，其特征在于：所述PETG/TPA-SiPc@SiO2复合线材应用于催化降解对氯苯酚。
本发明的有益效果为：1）本发明制得的复合线材，是一种用于3D打印的高分子材料，具有能够在较低温度下成型打印，打印出来的产品质量高，性能优异，具有良好的透光性；2）本发明制得的复合线材，具有良好的透光性和可见光光催化性能，制备方法简单高效，可应用于污水、空气和土壤中有机污染物的光催化降解处理。
附图说明
图1为一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材3D打印成型产品图。
图2为一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材3D打印成型产品在可见光条件下多次催化降解对氯苯酚活性图。
具体实施方式
下面结合具体实施例子对本发明做进一步详细说明，但不应将此理解为本发明的范围仅限于以下实例。本发明实施例采用美国Eastman（伊斯曼）化学公司生产的PETG产品。
实施例1
1、一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材，其特征在于，按照重量百分比配方如下：
PETG 50
PVA 20
TPA-SiPc@SiO2 15
乙二醇 10
氢氧化镁 3.5
硬脂酸 1.5。
2、上述具有光催化效果的PETG/TPA-SiPc@SiO2复合线材的制备方法，包括如下步骤：
A.将PETG和氢氧化镁分别真空干燥，然后将PETG、PVA、乙二醇、氢氧化镁、硬脂酸和TPA-SiPc@SiO2 按照重量百分比配方准确称量，然后将称量后的各组分置于高速混合机中混合均匀，得到混合料；
B.将混合料通过双螺杆挤出机熔融加工挤出造料，再通过切粒机切粒得到共混颗粒，料筒温度依次为165、170、175、180、195、200、205、210、215、210℃，螺杆转速为165 rpm/min；
C.将共混颗粒加入到3D线材生产线的单螺杆挤出机中进行挤出定型收卷，得到3D打印线材，料筒温度依次为170、180、200、210、215℃，螺杆转速为28 rpm/min；
D.将C步骤得到的线材经过3D打印机打印，得到PETG/TPA-SiPc@SiO2复合线材3D打印成型产品，具体如图1所示；
E.以500 W卤钨灯作为光源（置于双层玻璃夹套(通冷凝水)中，滤光片保证入射光波长λ在420~800 nm之间），在200 mL对氯苯酚水溶液(1.35×10-4 mol/L)中加入D步骤产品（3.52g），进行光催化降解实验，按固定的时间间隔（0 h、0.5 h、1 h、2 h、4 h、6 h)取样，取完的样品在经过离心之后进行紫外-可见光谱分析测定样品的吸光值，根据样品溶液吸光值的变化来计算对氯苯酚水溶液浓度变化（样品最大吸光值 λ=279 nm)。在反应后回收该样品，重复上述实验两次，得到PETG/TPA-SiPc@SiO2复合线材3D打印成型产品在可见光条件下多次催化降解对氯苯酚活性图，具体如图2所示。
实施例2
1、一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材，其特征在于，按照重量百分比配方如下：
PETG 55
PVA 18
TPA-SiPc@SiO2 17
聚乙二醇 7
氢氧化钙 2
硬脂酸 1。
2、上述具有光催化效果的PETG/TPA-SiPc@SiO2复合线材的制备方法，包括如下步骤：
A.将PETG和氢氧化钙分别真空干燥，然后将PETG、PVA 、TPA-SiPc@SiO2、聚乙二醇、氢氧化钙、硬脂酸按照重量百分比配方准确称量，然后将称量后的各组分置于高速混合机中混合均匀，得到混合料；
B. 将混合料通过双螺杆挤出机熔融加工挤出造料，再通过切粒机切粒得到共混颗粒，料筒温度依次为168、175、180、190、200、205、210、218、212、210℃，螺杆转速为170rpm/min；
C.将共混颗粒加入到3D线材生产线的单螺杆挤出机中进行挤出定型收卷，得到3D打印线材，料筒温度依次为175、180、200、210、205℃，螺杆转速为30 rpm/min。
实施例3
1、一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材，其特征在于，按照重量百分比配方如下：
PETG 65
PVA 14
TPA-SiPc@SiO2 15
聚乙二醇 3
氧化钙 2
氧化聚乙烯蜡 1。
2、上述具有光催化效果的PETG/TPA-SiPc@SiO2复合线材的制备方法，包括如下步骤：
A.将PETG和氧化钙分别真空干燥，然后将PETG、PVA、聚乙二醇、氧化钙、氧化聚乙烯蜡和TPA-SiPc@SiO2按照重量百分比配方准确称量，然后将称量后的各组分置于高速混合机中混合均匀，得到混合料；
B.将混合料通过双螺杆挤出机熔融挤出造料，再通过切粒机切粒得到共混颗粒，料筒温度依次为172、178、180、190、195、200、210、218、210、206℃，螺杆转速为175 rpm/min；
C.将共混颗粒加入到3D线材生产线的单螺杆挤出机中进行挤出定型收卷，得到3D打印线材，料筒温度依次为172、180、200、210、206℃，螺杆转速为35 rpm/min。
实施例4
上述实施例1-3所用的TPA-SiPc@SiO2由下述方法制备的：
（1）将10 mL蒸馏水加入到100 mL的异丙醇中，70℃水浴条件下搅拌均匀。
（2）向步骤（1）所述混合溶液中加入浓氨水调节pH值为12，待pH稳定后再加入1 mL的三苯胺基树枝配体取代硅酞菁储备液（0.02 mol/L），继续搅拌5 min。
向溶液中加入10mL的正硅酸乙酯，继续搅拌使其充分水解，最后将溶液过滤，洗涤（每次用10mL异丙醇洗涤3次、10 mL蒸馏水洗涤5次），将固体在80~100 ℃条件下烘干，得到所需的TPA-SiPc@SiO2催化剂。
Claims (7)
1.一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材，其特征在于，由下述的重量百分比组分制成：
PETG 40~70
PVA 5~25
TPA-SiPc@SiO2 3~25
增塑剂 4~20
稳定剂 3~6
分散剂 0.5~2
所述的TPA-SiPc@SiO2的制备方法，包括如下步骤：
（1）配制母液：体积分数为60%～95%的不同配比的异丙醇水溶液或乙醇水溶液50～100mL；
（2）向步骤（1）的溶液中加入浓氨水调节pH值至7～12，混合溶液在30～80℃的水浴条件下搅拌混合均匀；
（3）向步骤（2）的溶液中加入0.2～1.5 mL的0.001～0.02 mol/L的三苯胺基树枝配体取代硅酞菁贮备液，充分搅拌后使其混合均匀；
（4）向步骤（3）的溶液中加入正硅酸乙酯，继续搅拌4～12 h使其充分水解，最后将溶液过滤，洗涤，60℃～110℃干燥即得到所需要的催化剂。
2.根据权利要求1所述的一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材，其特征在于，所述的增塑剂至少有一种选自甘油、乙二醇、聚乙二醇。
3.根据权利要求1所述的一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材，其特征在于，所述的稳定剂至少有一种选自氢氧化钙、氧化钙、氢氧化镁。
4.根据权利要求1所述的一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材，其特征在于，所述的分散剂至少有一种选自硬酯酸、聚乙烯蜡、氧化聚乙烯蜡。
5.权利要求1-4任一所述的一种具有光催化效果的PETG/TPA-SiPc@SiO2复合线材的制备方法，其特征在于，包括以下步骤：
A.将PETG和稳定剂分别真空干燥，然后将PETG、PVA、增塑剂、稳定剂、分散剂和TPA-SiPc@SiO2按照重量百分比配方准确称量，然后将称量后的各组分置于高速混合机中混合均匀，得到混合料；
B.将混合料通过双螺杆挤出机熔融挤出造料，得到共混颗粒，料筒温度为160-230 ℃，螺杆转速为50-300 rpm/min；
C.将共混颗粒加入到3D线材生产线的单螺杆挤出机中进行挤出定型收卷，得到3D打印线材，料筒温度为160-230 ℃，螺杆转速为10-100 rpm/min。
6.一种根据权利要求1-4任一所述的具有光催化效果的PETG/TPA-SiPc@SiO2复合线材或根据权利要求5所述的制备方法制得的PETG/TPA-SiPc@SiO2复合线材的应用，其特征在于：所述PETG/TPA-SiPc@SiO2复合线材应用于3D打印领域。
7.一种根据权利要求1-4任一所述的具有光催化效果的PETG/TPA-SiPc@SiO2复合线材或根据权利要求5所述的制备方法制得的PETG/TPA-SiPc@SiO2复合线材的应用，其特征在于：所述PETG/TPA-SiPc@SiO2复合线材应用于催化降解对氯苯酚。
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