紫外吸收剂柱撑水滑石的插层组装及结构与性能研究
摘要
利用共沉淀插层组装方法,通过设计和优化反应条件,将五种有机紫外吸收剂—甲芬那酸(MFNA)、4,4'-双(2-磺酸钠苯乙烯基)联苯(CBS-X)、4,4'-(1,4-亚苯基双亚甲基)双氮烷基二苯甲酸(1,4-PMBADA)、4,4'-(1,3-亚苯基双亚甲基)双氮烷基二苯甲酸(1,3-PMBADA)和4,4'-二苯乙烯二羧酸(SDCA),以它们的阴离子形式嵌入到Zn2Al-LDHs层间,利用XRD、FT-IR、UV-Vis、TG-DTA等方法,对所得到的有机紫外吸收剂柱撑水滑石化合物Zn2Al-LDH/MFNA、Zn2Al-LDH/1,3-PMBADA、Zn2Al-LDH/1,4-PMBADA、Zn2Al-LDH/SDCA和Zn2Al-LDH/CBS-X的组成、结构及性能进行了分析表征。
研究结果表明,在共沉淀插层组装反应中,当选择原料中Zn/Al配比为2.0、控制共沉淀酸度pH 8.6-9.0左右、晶化温度80℃及晶化时间为24 h时,得到的有机紫外吸收剂柱撑水滑石结晶度高,晶相单一,化学组成明确,符合水滑石类化合物的组成通式,层间距d003(nm)分别为2.01(Zn2Al-LDH/MFNA)、1.85(Zn2Al-LDH/1,3-PMBADA)、2.14(Zn2Al-LDH/1,4-PMBADA)、2.09(Zn2Al-LDH/SDCA)和1.97(Zn2Al-LDH/CBS-X)。层间有机紫外线吸收剂仍然保持它们的原有结构,并以单层或双层交错形式在层间定向有序排布,使主客体间及客体和客体间的相互作用最大,LDHs更加稳定。
UV-Vis薄膜透过光谱表明,这五种有机紫外吸收剂柱撑水滑石对紫外线具有物理屏蔽和化学吸收的协同功能,具有很好的紫外遮蔽性能,且可见光区域透明性高。当有机紫外线吸收剂以它们的阴离子形式插入到LDHs层间后,它们的紫外吸收能力得到提高。在所制备的五种LDHs中, Zn2Al-LDH/1,3-PMBADA、Zn2Al-LDH/1,4-PMBADA及Zn2Al-LDH/SDCA主要对UV-B波段的紫外线有强吸收,对应的最大吸收峰波长分别为305 nm、306 nm及298 nm,在最大吸收波长处的的透过率均小于20%。Zn2Al-LDH/CBS-X对UV-A波段的紫外线有强吸收,对应的最大吸收峰波长为348 nm,相应的最小透过率均为12%。而Zn2Al-LDH/MFNA在UV-A及UV-B波段均有吸收峰,相对应的最大吸收峰波长分别为280 nm及355nm,相应的透过率分别为17%和28%。
蓖麻油的空气氧化反应表明,有机紫外吸收剂柱撑水滑石化合物几乎没有氧化催化活性。TG-DTA分析表明,有机紫外吸收剂柱撑水滑石化合物具有较高的热稳定性,层间有机物阴离子的分解温度达到400℃以上。
研究结果表明,共沉淀插层组装是制备有机紫外线吸收剂柱撑水滑石化合物的简便有效方法,得到的LDHs具有紫外线遮蔽效果好、可见光领域透明性高、氧化催化活性低及很好的热稳定性等特点,作为新一代紫外吸收材料,在防晒化妆品及高分子材料领域具有广泛的应用前景。
In the thesis, five organic UV absorbents, such as mefenamic acid, 4,4'-Bis [2-(2-sulfophenyl)ethenyl]biphenyl, 4,4′-[1,4-phenylenebis(methylene)] bis (azanediyl)dib- enzoic acid, 4,4′-[1,3-phenylenebis(methylene)] bis (azanediyl)dibenzoic acid, 2,4-dimeth- oxy benzoic acid, in their anionic, has been intercalated into a layered double hydroxide (LDHs) host by coprecipitation method. Five organic-inorganic composite materials, Zn2Al-LDH/MFNA, Zn2Al-LDH/1,4-PMBADA, Zn2Al-LDH/1,3-PMBADA, Zn2Al-LDH/C BS-X and Zn2Al-LDH/SDCA were obtained. Products obtained were characterized by X-ray diffraction (XRD), FT-IR, UV-Vis, TG-DTA. Thermal stability, UV shielding ability, catalytic activity for the air of castor oil and chemical stablility of the composite materials were investigated.
The results indicated that synthetic products with high crystallinity, single crystal phase, clear chemical composition in control of the experimental condition (Zn/Al=2.0, pH 8.6-9.0, Aging Temperature=80℃, Aging Time=24h). XRD patterns showed that the basal spacing of Zn2Al-LDHs were greatly expanded as 2.01 nm (Zn2Al-LDH/MFNA), 1.85nm (Zn2Al-LDH/1,3-PMBADA), 2.14 nm (Zn2Al-LDH/1,4-PMBADA), 2.09 nm (Zn2Al-LDH/SDCA) and 1.97 nm (Zn2Al-LDH/CBS-X), respectively. Organic UV absorbents still maintain original structures in the interlayer arranged orderly in the form of single-or double-staggered .
According to the UV-Vis transmittance spectra of thin films of the samples, all Zn2Al-LDHs/organic UV absorbents showed excellent UV-shielding ability and transparency in the visible light region. When intercalated into LDHs, their UV absorption were improved.
The air oxidation of castor oil showed that the organic UV absorbents pillared LDHs almost have no oxidation catalytic activity. TG-DTA analysis showed that the composite materials had well thermal stability, Organic anions between layers achieve the decomposition temperature above 400℃.
Coprecipitation method is a simple and effective method for assembly of UV absorbents pillared LDHs. All Zn2Al-LDHs/organic UV absorbents showed excellent UV-shielding ability and transparency in the visible light region; low oxidation catalytic activity; well thermal stability. As new generation of UV absorbing materials, in the area of cosmetics and polymeric materials have a wide application prospect.
研究结果表明,在共沉淀插层组装反应中,当选择原料中Zn/Al配比为2.0、控制共沉淀酸度pH 8.6-9.0左右、晶化温度80℃及晶化时间为24 h时,得到的有机紫外吸收剂柱撑水滑石结晶度高,晶相单一,化学组成明确,符合水滑石类化合物的组成通式,层间距d003(nm)分别为2.01(Zn2Al-LDH/MFNA)、1.85(Zn2Al-LDH/1,3-PMBADA)、2.14(Zn2Al-LDH/1,4-PMBADA)、2.09(Zn2Al-LDH/SDCA)和1.97(Zn2Al-LDH/CBS-X)。层间有机紫外线吸收剂仍然保持它们的原有结构,并以单层或双层交错形式在层间定向有序排布,使主客体间及客体和客体间的相互作用最大,LDHs更加稳定。
UV-Vis薄膜透过光谱表明,这五种有机紫外吸收剂柱撑水滑石对紫外线具有物理屏蔽和化学吸收的协同功能,具有很好的紫外遮蔽性能,且可见光区域透明性高。当有机紫外线吸收剂以它们的阴离子形式插入到LDHs层间后,它们的紫外吸收能力得到提高。在所制备的五种LDHs中, Zn2Al-LDH/1,3-PMBADA、Zn2Al-LDH/1,4-PMBADA及Zn2Al-LDH/SDCA主要对UV-B波段的紫外线有强吸收,对应的最大吸收峰波长分别为305 nm、306 nm及298 nm,在最大吸收波长处的的透过率均小于20%。Zn2Al-LDH/CBS-X对UV-A波段的紫外线有强吸收,对应的最大吸收峰波长为348 nm,相应的最小透过率均为12%。而Zn2Al-LDH/MFNA在UV-A及UV-B波段均有吸收峰,相对应的最大吸收峰波长分别为280 nm及355nm,相应的透过率分别为17%和28%。
蓖麻油的空气氧化反应表明,有机紫外吸收剂柱撑水滑石化合物几乎没有氧化催化活性。TG-DTA分析表明,有机紫外吸收剂柱撑水滑石化合物具有较高的热稳定性,层间有机物阴离子的分解温度达到400℃以上。
研究结果表明,共沉淀插层组装是制备有机紫外线吸收剂柱撑水滑石化合物的简便有效方法,得到的LDHs具有紫外线遮蔽效果好、可见光领域透明性高、氧化催化活性低及很好的热稳定性等特点,作为新一代紫外吸收材料,在防晒化妆品及高分子材料领域具有广泛的应用前景。
In the thesis, five organic UV absorbents, such as mefenamic acid, 4,4'-Bis [2-(2-sulfophenyl)ethenyl]biphenyl, 4,4′-[1,4-phenylenebis(methylene)] bis (azanediyl)dib- enzoic acid, 4,4′-[1,3-phenylenebis(methylene)] bis (azanediyl)dibenzoic acid, 2,4-dimeth- oxy benzoic acid, in their anionic, has been intercalated into a layered double hydroxide (LDHs) host by coprecipitation method. Five organic-inorganic composite materials, Zn2Al-LDH/MFNA, Zn2Al-LDH/1,4-PMBADA, Zn2Al-LDH/1,3-PMBADA, Zn2Al-LDH/C BS-X and Zn2Al-LDH/SDCA were obtained. Products obtained were characterized by X-ray diffraction (XRD), FT-IR, UV-Vis, TG-DTA. Thermal stability, UV shielding ability, catalytic activity for the air of castor oil and chemical stablility of the composite materials were investigated.
The results indicated that synthetic products with high crystallinity, single crystal phase, clear chemical composition in control of the experimental condition (Zn/Al=2.0, pH 8.6-9.0, Aging Temperature=80℃, Aging Time=24h). XRD patterns showed that the basal spacing of Zn2Al-LDHs were greatly expanded as 2.01 nm (Zn2Al-LDH/MFNA), 1.85nm (Zn2Al-LDH/1,3-PMBADA), 2.14 nm (Zn2Al-LDH/1,4-PMBADA), 2.09 nm (Zn2Al-LDH/SDCA) and 1.97 nm (Zn2Al-LDH/CBS-X), respectively. Organic UV absorbents still maintain original structures in the interlayer arranged orderly in the form of single-or double-staggered .
According to the UV-Vis transmittance spectra of thin films of the samples, all Zn2Al-LDHs/organic UV absorbents showed excellent UV-shielding ability and transparency in the visible light region. When intercalated into LDHs, their UV absorption were improved.
The air oxidation of castor oil showed that the organic UV absorbents pillared LDHs almost have no oxidation catalytic activity. TG-DTA analysis showed that the composite materials had well thermal stability, Organic anions between layers achieve the decomposition temperature above 400℃.
Coprecipitation method is a simple and effective method for assembly of UV absorbents pillared LDHs. All Zn2Al-LDHs/organic UV absorbents showed excellent UV-shielding ability and transparency in the visible light region; low oxidation catalytic activity; well thermal stability. As new generation of UV absorbing materials, in the area of cosmetics and polymeric materials have a wide application prospect.
引文
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