CN109248710A - 一种掺杂改性层状双氢氧化物的组合物及其制备方法 - Google Patents
一种掺杂改性层状双氢氧化物的组合物及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种掺杂改性层状双氢氧化物的组合物及其制备方法,含有光催化剂柱撑层状双氢氧化物或层状双氢氧化物负载光催化剂0.0025‑2wt%,高分子聚合物96‑99wt%,抗氧剂0.5‑1wt%和表面活性剂0.5‑1wt%。该发明利用LDH的阻隔作用,能够延缓聚合物材料经过光照后释放VOC的速率,同时通过添加光催化剂提高光催化效率,从源头上来控制高分子材料的VOC释放,从而有效减少车内环境污染。
Description
技术领域
本发明涉及一种掺杂改性层状双氢氧化物的组合物及其制备方法,属于功能高分子领域。
背景技术
随着汽车工业的飞速发展,全球的汽车保有量迅速增加,汽车已经迅速步入到社会的各个角落。随着私人购车量的迅速增长,人们在车内度过的时间也越来越多。而伴随汽车制造工艺的发展,“汽车轻量化”引起了人们的广泛关注。汽车的轻量化,就是在保证汽车的强度和安全性能的前提下,尽可能地降低汽车的整备质量,从而提高汽车的动力性,减少燃料消耗,降低排气污染。实验证明,若汽车整车重量降低10%,燃油效率可提高6%-8%,油耗可降低7%。目前,开发出节能、安全和环保的车型也已成为我国汽车工业可持续发展面临的突出问题。因此,采用轻质材料被广泛应用于汽车制造中。一般塑料的比重在0.9-1.5,纤维增强复合材料的比重也不会超过2.0,而金属材料的比重,A3钢为7.6,黄铜为8.4,铝为2.7。这就使得塑料材料成为汽车轻量化的首选用材。
从现代汽车使用的材料看,无论是外装饰件、内装饰件,还是功能与结构件,到处都可以看到塑料制件的影子。特别是汽车的内饰材料,基本都是由非金属材料制成,而其中高分子材料所占比例达到80%以上。目前国内外汽车内饰材料采用最多的是聚丙烯(PP)、聚氯乙烯(PVC)、聚氨酯(PU)等。高分子材料在实际应用中基本都会添加各种助剂来提高其某种性能,从而扩大其使用范围。如在高分子材料中添加增塑剂提高材料的韧性,添加相容剂以提高材料的相容性和力学性能,添加阻燃剂以提高材料的安全性能,避免材料和汽车在高温条件下发生燃烧等。然而随着高分子材料制品的使用,高分子材料自身含有的各种有机物如溶剂、未反应单体和助剂等可能会逐渐迁移到材料表面或释放出来而降低汽车内部环境质量。世界卫生组织把这些挥发性有机物统称为VOC(volatile organiccompound),并定义VOC主要包括三大类:极易挥发性有机物(VVOCs),挥发性有机物(VOCs)和半挥发性有机物(SVOCs)。如聚氨酯类可能释放的VOC主要为未反应的小分子单体、抗氧化稳定剂、挥发胺类催化剂等。聚丙烯类释放的VOC主要为长碳链的烷烃、各类添加剂,小部分为醛、酮、醇类小分子。聚氯乙烯类释放的VOC主要为增塑剂、溶剂、未反应单体及一些次级分解产物等。
近年调查结果显示:在接受调查的汽车中,有近94%的被调查车辆存在车内环境污染问题。汽车内环境污染会使人产生头痛、头晕、恶心、咳嗽等症状,影响人的心情和注意力长期暴露在较低浓度的VOC下会导致哮喘和其他一系列呼吸道疾病;而在较高浓度下,许多类的VOC会导致人体麻醉和中枢神经系统活性抑制,而且对人的眼睛,皮肤及呼吸道具有刺激作用。常用的增塑剂邻苯二甲酸酯可使儿童产生过敏症状,影响男性生殖系统的发育,降低精子质量。邻苯二甲酸二(2-乙基己基)酯是可能的人类致癌物。阻燃剂如多溴联苯(PBBs)可引起神经、免疫系统、肝、肾、甲状腺的疾患,还有可能引发人类癌症。
为了有效减少车内环境污染,最关键的方法还是从源头来控制,即减少所使用高分子材料的VOC释放。现有研究也针对车内常有材料进行了相关研究,如为了减少PU的VOC释放,可以通过在生产过程中优化其生产工艺来避免反应活性弱的小分子出现,或者通过使用挥发性小的稳定剂等VOC的浓度。而通过优化配方工艺和加工工艺来降低PP的挥发物浓度也是比较通用的方法。
随着科学技术的发展,特别是纳米技术的应用,促进了高分子材料研究领域纳米技术的高速发展。纳米复合材料因纳米效应而具有优异的力学性能、热性能以及电性能等,是近二十多年国内外纳米复合材料领域的研究热点之一。研究表明某些无机纳米化合物,不仅可以提高高分子材料的热稳定性、机械性能等,在阻止高分子材料的VOC释放检测及消除上也具有广泛应用。利用陶瓷类材料在阻隔氧气、水分及挥发性有机物等方面都具有显著效果的阻隔性能制备有机/无机复合材料包覆PVC来防止增塑剂的迁移。
层状双氢氧化物(LDH),作为一类重要的层状无机材料,具有层板化学组成、层板电荷密度、层间离子种类及定位排列、晶粒尺寸及分布的可调控性,以及热稳定性和记忆性能等特点,在气体阻隔、催化、离子交换和吸附、功能高分子材料及添加剂等方面具有广泛应用。然而类似于层状粘土,单纯的阻隔作用并不能根本消除VOC。近年来,半导体光催化剂作为一种能够从根本上消除VOC释放的纳米材料,引起了人们越来越广泛的关注。TiO2由于其光催化活性高,稳定性好,无污染且价格低廉,应用最为广泛。除了TiO2,纳米ZnO在光催化方面也有着优异的性能。把这些氧化物加入双氢氧化物(LDH)中制备氧化物柱撑层状化合物或氧化物负载层状化合物,不仅可以使这些氧化物光催化剂固定化,而且表面积的增大提高了光催化效率。
综上所述,由于目前一般使用物理方法降低VOC浓度,并没有从根本上降低或消除VOC。柱撑层状双氢氧化物或金属氧化物负载层状双氢氧化物可以克服这一难题。一方面异质原子掺杂(如N等掺杂)到氧化物光催化剂中,可以提高其对太阳能的利用率。另一方面,双氢氧化物对氧化物光催化剂的柱撑或负载,不仅可以固化氧化物光催化剂,而且也可提高其光催化效率。同时双氢氧化物本身既能够改善高分子体系阻燃和力学等方面性能,也能够对VOC起到阻隔作用。因此,柱撑层状双氢氧化物或金属氧化物负载层状双氢氧化物的加入能够有效地从根本上降低或消除其VOC的释放从而保证了环境的安全性。
发明内容
针对上述背景,本发明的目的是提供一种掺杂改性层状双氢氧化物的组合物。本发明的另一个目的是提供该组合物的制备方法和应用。
为实现上述目的,本发明采用如下技术方案:
本发明制备一种掺杂改性层状双氢氧化物的组合物,其利用LDH的阻隔作用,能够延缓聚合物材料经过光照后释放VOC的速率,同时通过对光催化剂柱撑LDH或进行LDH负载光催化剂,能够降解聚合物材料释放的VOC,从而减少VOC的释放。
一种掺杂改性层状双氢氧化物(LDH)的组合物,含有光催化剂柱撑层状双氢氧化物或层状双氢氧化物负载光催化剂0.0025-2wt%,高分子聚合物96-99wt%,抗氧剂0.5-1wt%和表面活性剂0.5-1wt%。
所述LDH为Zn/Al等层状双氢氧化物,其制备方法为:将0.2-0.4g Zn(NO3)2·6H2O和0.2-0.4g Al(NO3)3·9H2O溶于20-50mL去离子水中,得到总浓度为0.1-0.15mol/L的盐溶液,再将0.16-0.2g NaOH溶于20mL去离子水中,得到碱溶液,将两种溶液通过微反应器进行共沉淀制得Zn/Al-LDH纳米片,溶液的流速均为20-40mL/min,反应温度为20-40℃,微反应器出口处得到悬浊液,最后将悬浊液在12000-15000rmp下离心并用去离子水洗涤3-5遍,即得Zn/Al-LDH。
所述LDH还可以为Mg/Al、Ni/Fe等层状双氢氧化物。
所述光催化剂柱撑层状双氢氧化物为WO3柱撑LDH,采用焙烧还原法制备,具体步骤为:将上述制备的LDH在450-600℃焙烧1-4h,得到复合金属氧化物(LDO),称取LDO10-15g,同时加入WO31-3g和去离子水0.5-1kg,放入三口烧瓶中。在50-60℃反应12-16h,过滤,在80-100℃干燥12h,研磨,得到WO3柱撑LDH产物。
所述层状双氢氧化物负载光催化剂为LDH负载TiO2,采用共沉淀法制备,具体步骤为:将上述制备的LDH称取10-15g溶于100mL去离子水中,加入1-3gTiCl4、0.5-1gNaOH和0.1-0.2gNaCO3,控制溶液的pH达到8.0-8.5,在50-60℃在晶化16-18h,将所得产物用去离子水洗涤3次后,于100℃下干燥,研磨得到LDH负载TiO2产物。
所述的高分子聚合物包括聚丙烯、聚氨酯和聚氯乙烯等。
所述的组合物可采用熔融共混法制备,具体步骤为:
1)将WO3柱撑LDH或LDH负载TiO2、抗氧剂以及表面活性剂与高分子聚合物基体树脂高速混合0.1-3min,通过双螺杆挤出机很混合塑化并造粒,做成高浓度母粒,添加剂总重量约占母粒重量的0.5-4wt%;
2)将母粒与高分子基体树脂高速混合0.1-3分钟,母粒约占总重量的0.5-50wt%;
3)通过双螺杆挤出机混合塑化,并通过切粒机造粒。
本发明的有益效果为:提供了一种可降低VOC释放的车内饰常用高分子聚合物及其制备方法。其利用LDH的阻隔作用,能够延缓聚合物材料经过光照后释放VOC的速率,同时通过对光催化剂柱撑LDH或进行LDH负载光催化剂,能够降解聚合物材料释放的VOC,从而减少VOC的释放。
附图说明
图1是Zn/Al-LDH负载TiO2SEM照片。
具体实施方式
为让本发明的上述特征和优点更明显易懂,下文举实施例作详细说明。
实施例1
采用共沉淀法进行层状双氢氧化物的制备,以Zn/Al-LDH为例。
将0.4g Zn(NO3)2·6H2O和0.4g Al(NO3)3·9H2O溶于20mL去离子水中,Zn(NO3)2·6H2O和Al(NO3)3·9H2O购自国药试剂,得到总浓度为0.12mol/L的盐溶液,再将0.2g NaOH溶于20mL去离子水中,得到浓度为0.25mol/L的碱溶液。将两种溶液通过微反应器进行共沉淀制得Zn/Al-LDH纳米片,溶液的流速均为35mL/min,反应温度为30℃,微反应器出口处得到悬浊液,最后将悬浊液在15000rmp下离心并用去离子水洗涤5遍,即得Zn/Al-LDH,粒径为300nm。
实施例2
将WO3作为光催化剂,采用焙烧还原法制备WO3柱撑Zn/Al-LDH。
将实施例1的Zn/Al-LDH在550℃焙烧2.5h,得到Zn/Al复合金属氧化物(Zn/Al-LDO),称取Zn/Al-LDO 12g,同时加入WO3 2.5g和去离子水0.75kg,放入三口烧瓶中。在50℃下反应12-16h,过滤,在100℃干燥12h,研磨,得到WO3柱撑LDH产物。
实施例3
将TiO2作为光催化剂,采用共沉淀法制备Zn/Al-LDH负载TiO2。
将实施例1制备的Zn/Al-LDH称取12g溶于100mL去离子水中,加入1.9gTiCl4、1gNaOH和0.16gNaCO3,控制溶液的pH达到8,在60℃在晶化16h,将所得产物用去离子水洗涤3次后,于100℃下干燥,研磨得到Zn/Al-LDH负载TiO2产物,粒径为300nm,如附图1所示。
实施例4
将实施例3制备的Zn/Al-LDH负载TiO2作为添加剂,加入到PP中,制备方法为:
1)称取3g Zn/Al-LDH负载TiO2、0.5g抗氧剂168和0.5g硬脂酸加入到16g PP中,PP购自广州石化,牌号为S980,混合,高速搅拌2min;
2)放入HAAKE双螺杆挤出机中塑化挤出并使用切粒机造粒,工艺条件:
TS1/℃ | TS2/℃ | TS3/℃ | TS4/℃ | TS5/℃ | TS6/℃ | FR/% | n/r/min |
170 | 175 | 185 | 200 | 200 | 180 | 8 | 50 |
3)将母粒与80g PP放入高混机高速搅拌3min;
4)放入HAAKE双螺杆挤出机中塑化挤出并使用切粒机造粒,工艺条件:
TS1/℃ | TS2/℃ | TS3/℃ | TS4/℃ | TS5/℃ | TS6/℃ | FR/% | n/r/min |
170 | 175 | 185 | 200 | 200 | 180 | 8 | 50 |
实施例5
将实施例3制备的Zn/Al-LDH负载TiO2作为添加剂,加入到PVC中,制备方法为:
5)称取3g Zn/Al-LDH负载TiO2、0.5g抗氧剂168和0.5g硬脂酸加入到16g PVC中,PVC购自上海氯碱,牌号为1300,混合,高速搅拌2min;
6)放入HAAKE双螺杆挤出机中塑化挤出并使用切粒机造粒,工艺条件:
TS1/℃ | TS2/℃ | TS3/℃ | TS4/℃ | TS5/℃ | TS6/℃ | FR/% | n/r/min |
180 | 185 | 195 | 210 | 210 | 190 | 8 | 50 |
7)将母粒与80g PP放入高混机高速搅拌3min;
8)放入HAAKE双螺杆挤出机中塑化挤出并使用切粒机造粒,工艺条件:
表1掺杂Zn/Al-LDH负载TiO2的高分子基复合材料的测试数据
实施例4 | 实施例5 | |
拉伸强度/MPa | 29 | 21 |
弯曲强度/MPa | 45 | 83 |
TVOC/ppm | 56 | 59 |
Claims (10)
1.一种掺杂改性层状双氢氧化物(LDH)的组合物,其特征在于:光催化剂柱撑层状双氢氧化物或层状双氢氧化物负载光催化剂0.0025-2wt%,高分子聚合物96-99wt%,抗氧剂0.5-1wt%和表面活性剂0.5-1wt%。
2.如权利要求1所述的组合物,其特征在于:所述LDH为Zn/Al等层状双氢氧化物。
3.如权利要求2所述的Zn/Al层状双氢氧化物,其特征在于,制备方法为:将0.2-0.4gZn(NO3)2·6H2O和0.2-0.4g Al(NO3)3·9H2O溶于20-50mL去离子水中,得到总浓度为0.1-0.15mol/L的盐溶液,再将0.16-0.2g NaOH溶于20mL去离子水中,得到碱溶液,将两种溶液通过微反应器进行共沉淀制得Zn/Al-LDH纳米片,溶液的流速均为20-40mL/min,反应温度为20-40℃,微反应器出口处得到悬浊液,最后将悬浊液在12000-15000rmp下离心并用去离子水洗涤3-5遍,即得Zn/Al-LDH。
4.如权利要求1所述的组合物,其特征在于:所述LDH还可以为Mg/Al、Ni/Fe等层状双氢氧化物。
5.如权利要求1所述组合物中的光催化剂柱撑层状双氢氧化物,其特征在于:为WO3柱撑LDH。
6.如权利要求5所述的WO3柱撑LDH,其特征在于,采用焙烧还原法制备,具体步骤为:将上述制备的LDH在450-600℃焙烧1-4h,得到复合金属氧化物(LDO),称取LDO10-15g,同时加入WO31-3g和去离子水0.5-1kg,放入三口烧瓶中。在50-60℃反应12-16h,过滤,在80-100℃干燥12h,研磨,得到WO3柱撑LDH产物。
7.如权利要求1所述的组合物中的层状双氢氧化物负载光催化剂,其特征在于:为LDH负载TiO2。
8.如权利要求7所述的LDH负载TiO2,其特征在于,采用共沉淀法制备,具体步骤为:将上述制备的LDH称取10-15g溶于100mL去离子水中,加入1-3gTiCl4、0.5-1gNaOH和0.1-0.2gNaCO3,控制溶液的pH达到8.0-8.5,在50-60℃在晶化16-18h,将所得产物用去离子水洗涤3次后,于100℃下干燥,研磨得到LDH负载TiO2产物。
9.如权利要求1所述的组合物,其特征在于:所述的高分子聚合物包括聚丙烯、聚氨酯和聚氯乙烯等。
10.如权利要求1所述的组合物,其特征在于,采用熔融共混法制备,具体步骤为:
1)将WO3柱撑LDH或LDH负载TiO2、抗氧剂以及表面活性剂与高分子聚合物基体树脂高速混合0.1-3min,通过双螺杆挤出机很混合塑化并造粒,做成高浓度母粒,添加剂总重量约占母粒重量的0.5-4wt%;
2)将母粒与高分子基体树脂高速混合0.1-3分钟,母粒约占总重量的0.5-50wt%;
3)通过双螺杆挤出机混合塑化,并通过切粒机造粒。
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