新型铁、稀土配合物染料的合成与应用研究
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摘要
金属配合物染料是一种重要的合成染料，特别适合于蛋白纤维染色。传统金属配合物染料都是Cr~3、Co~(2+)、Cu~(2+)等重金属离子与酸性媒介染料作用而成；但Cr~3、Co~(2+)等有毒重金属离子会随印染废水进入自然界，严重危害生态环境。因此，合成环境友好的新型金属配合物染料、并探讨其应用性能十分必要。
论文以相关文献为基础，合成了46支金属配合物染料，并进行了染色性能研究，同时对部分新合成的染料进行了吸附热力学研究。研究结果表明：新合成的金属配合物染料在羊毛纤维上均有较高的上染率和较好的染色牢度，可以作为传统重金属配合物染料的潜在替代品。主要工作如下：
合成了46支金属配合物染料。其中，甲簪金属配合物染料22支，12支为1：1型，10支为1：2型，中心离子为Cu~(2+)、Fe~(2+)及稀土离子RE~(3+)(RE=La、Pr、Nd、Sm、Dy)。偶氮金属配合物染料24支，均为1：2型，中心离子为Fe~(2+)、RE~(3+)(RE=La、Pr、Nd、Sm、Dy)。实验发现，金属离子分别与配体中的羟基氧原子(-OH)，偶氮键中的氮原子配位(-N=N-)。
研究了新合成的两类金属配合物染料的染色性能。讨论了染色方法、染色工艺，绘制了染色曲线，测定了这两类金属配合物在羊毛纤维上的上染率及染色牢度，得出了最佳染色工艺条件。实验发现：新合成的金属配合物染料在最佳染色工艺条件下，对羊毛纤维的上染率均在85％以上，日晒牢度能达到4-5级；皂洗牢度达到3-4级，其染色性能与传统的重金属配合物染料相当。
研究了7支酸性媒介黄GG配合物染料的吸附热力学性质。绘制了羊毛纤维在水溶液中吸附这些染料的吸附等温线，运用计量置换吸附理论，计算了出相应的吸附热力学函变及其分量。结果表明：酸性媒介黄GG配合物染料上染羊毛的结合作用为熵驱动的化学吸附过程。
此外，本文还研究了N_2气中顺丁烯二酸酐、丙二酸盐以及高分子聚氨酯的热失重过程。通过实验数据求出了热失重过程的表观活化能，判断出了机理函数，结合表观活化能和最可几机理函数，求出了指前因子。
The metal-complex dyes are important synthetic dyes used for protein fibers. Conventional metal-complex dyes have been synthesized by heavy metal ions, such as Cr~(3+), Co~(2+) and Cu~(2+), and acid mordant dye. Though widely used, those heavy metal ions produced a large amount of industrial wastewater in the exhausted dyebath, seriously polluting the ecological environment. So, it is necessary to synthesize and apply environment friendly dyes as viable alternatives.
In this thesis, 46 new metal-complex dyes have been synthesized on the basis of related studies existing. Colouristic and fastness properties of these dyes were determined and discussed. In addition, the adsorption thermodynamics of some dyes have also been carried out. Results of the study show that metal-complex dyes synthesized newly all have good dye uptake and fastness, and they can be serving as alternatives. The main contents are as follow:
46 complexed formazan dyes were synthesized. 22 of them were formazan dyes, including ten 1:1 and twelve 1:2 dyes, and the metal ions were Cu~(2+)、Fe~(2+) and RE~(3+) (RE=La、Pr、Nd、Sm、Dy). The rest were azo dyes, and they were all 1:1, the metal ions were Fe~(2+) and RE~(3+) (RE=La、Pr、Nd、Sm、Dy) . Experiments show the metal iron were coordinated by oxygen atoms from hydroxy (-OH) and one nitrogen atom from azo bond (-N=N-).
The coloristic and fastness properties of the newly synthesized dyes onto wool fiber were determined and discussed. And dyeing was optimized. All dye uptake exceed 85%, indicating that the complex synthesized were similar to those of conventional corresponding chromium complexes. The dyeings obtained have very good fastness properties, lightfastness reaching 4-5 and washingfastness reaching 3-4.
Thermodynamics property of acid chrome yellow GG complex dyes onto wool firber was investigated as well. The isotherms of dyes adsorbed from the aqueous solutions onto the wool at vary temperature were measured. And the corresponding adsorption thermodynamic function and its fraction were calculated, using stoichiometric displacement model of adsorption. The results indicate dyeing of acid chrome yellow GG complex dyes onto the wool is a chemical adsorption driven by entropy.
In addition, the thermal mass-loss behaviors of maleic anhydride, malonate and cation waterborne polyurethane were studied under non-isothermal conditions by thermogravimetry technique in N_2 atmosphere. The apparent activation energy Ea and the most probable mechanism function G(α) were obtained. And the pre-exponential factor A was obtained on the basis of Ea and G(α).
论文以相关文献为基础，合成了46支金属配合物染料，并进行了染色性能研究，同时对部分新合成的染料进行了吸附热力学研究。研究结果表明：新合成的金属配合物染料在羊毛纤维上均有较高的上染率和较好的染色牢度，可以作为传统重金属配合物染料的潜在替代品。主要工作如下：
合成了46支金属配合物染料。其中，甲簪金属配合物染料22支，12支为1：1型，10支为1：2型，中心离子为Cu~(2+)、Fe~(2+)及稀土离子RE~(3+)(RE=La、Pr、Nd、Sm、Dy)。偶氮金属配合物染料24支，均为1：2型，中心离子为Fe~(2+)、RE~(3+)(RE=La、Pr、Nd、Sm、Dy)。实验发现，金属离子分别与配体中的羟基氧原子(-OH)，偶氮键中的氮原子配位(-N=N-)。
研究了新合成的两类金属配合物染料的染色性能。讨论了染色方法、染色工艺，绘制了染色曲线，测定了这两类金属配合物在羊毛纤维上的上染率及染色牢度，得出了最佳染色工艺条件。实验发现：新合成的金属配合物染料在最佳染色工艺条件下，对羊毛纤维的上染率均在85％以上，日晒牢度能达到4-5级；皂洗牢度达到3-4级，其染色性能与传统的重金属配合物染料相当。
研究了7支酸性媒介黄GG配合物染料的吸附热力学性质。绘制了羊毛纤维在水溶液中吸附这些染料的吸附等温线，运用计量置换吸附理论，计算了出相应的吸附热力学函变及其分量。结果表明：酸性媒介黄GG配合物染料上染羊毛的结合作用为熵驱动的化学吸附过程。
此外，本文还研究了N_2气中顺丁烯二酸酐、丙二酸盐以及高分子聚氨酯的热失重过程。通过实验数据求出了热失重过程的表观活化能，判断出了机理函数，结合表观活化能和最可几机理函数，求出了指前因子。
The metal-complex dyes are important synthetic dyes used for protein fibers. Conventional metal-complex dyes have been synthesized by heavy metal ions, such as Cr~(3+), Co~(2+) and Cu~(2+), and acid mordant dye. Though widely used, those heavy metal ions produced a large amount of industrial wastewater in the exhausted dyebath, seriously polluting the ecological environment. So, it is necessary to synthesize and apply environment friendly dyes as viable alternatives.
In this thesis, 46 new metal-complex dyes have been synthesized on the basis of related studies existing. Colouristic and fastness properties of these dyes were determined and discussed. In addition, the adsorption thermodynamics of some dyes have also been carried out. Results of the study show that metal-complex dyes synthesized newly all have good dye uptake and fastness, and they can be serving as alternatives. The main contents are as follow:
46 complexed formazan dyes were synthesized. 22 of them were formazan dyes, including ten 1:1 and twelve 1:2 dyes, and the metal ions were Cu~(2+)、Fe~(2+) and RE~(3+) (RE=La、Pr、Nd、Sm、Dy). The rest were azo dyes, and they were all 1:1, the metal ions were Fe~(2+) and RE~(3+) (RE=La、Pr、Nd、Sm、Dy) . Experiments show the metal iron were coordinated by oxygen atoms from hydroxy (-OH) and one nitrogen atom from azo bond (-N=N-).
The coloristic and fastness properties of the newly synthesized dyes onto wool fiber were determined and discussed. And dyeing was optimized. All dye uptake exceed 85%, indicating that the complex synthesized were similar to those of conventional corresponding chromium complexes. The dyeings obtained have very good fastness properties, lightfastness reaching 4-5 and washingfastness reaching 3-4.
Thermodynamics property of acid chrome yellow GG complex dyes onto wool firber was investigated as well. The isotherms of dyes adsorbed from the aqueous solutions onto the wool at vary temperature were measured. And the corresponding adsorption thermodynamic function and its fraction were calculated, using stoichiometric displacement model of adsorption. The results indicate dyeing of acid chrome yellow GG complex dyes onto the wool is a chemical adsorption driven by entropy.
In addition, the thermal mass-loss behaviors of maleic anhydride, malonate and cation waterborne polyurethane were studied under non-isothermal conditions by thermogravimetry technique in N_2 atmosphere. The apparent activation energy Ea and the most probable mechanism function G(α) were obtained. And the pre-exponential factor A was obtained on the basis of Ea and G(α).
引文
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