超支化聚胺酯型助剂的制备及应用
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摘要
超支化聚合物是一类具有三维椭球状立体构造的高度支化聚合物。与相应的线型分子相比,超支化聚合物具有不易发生链缠结、熔体和溶液的粘度都很低、容易成膜、分子内存在空腔等特点,这些特性使超支化聚合物在诸多领域均具有潜在的应用价值。同时,由于超支化聚合物的合成相对简单,可以用“一步法”和“准一步法”合成,具有较高的工业应用价值,因而近年来超支化聚合物的制备及其性能研究受到广泛的重视。目前探讨超支化聚合物在制革工业中的应用已成为皮化领域重要的研究方向。
本文综述了超支化聚合物的研究进展;依据聚合物分子设计的原理分别制备了超支化聚(胺-酯)型助鞣剂HP-1、超支化聚(胺-酯)型甲醛捕获剂HP-2,对其结构进行了确认和表征,研究了其结构和应用性能的关系。相信本论文的研究成果对于超支化聚合物助剂的制备以及在制革生产中的应用都具有积极意义。本文的主要内容包括:
(1)以丙烯酸甲酯和二乙醇胺为主要原料,通过Michael加成反应制备了单体N,N-二羟乙基-3-胺基丙酸甲酯,以1,1,1-三羟甲基丙烷为核,经过缩合聚合反应,得到了端基为羟基的超支化聚(胺-酯),再用顺丁烯二酸酐对聚合物端基进行改性,制备了一种新型多官能团的超支化聚(胺-酯)型助鞣剂HP-1。利用在线红外光谱、红外光谱、核磁共振光谱和凝胶渗透光谱等对单体的合成过程及聚合物的结构进行了表征。
(2)将超支化聚(胺-酯)型助鞣剂HP-1应用于铬鞣及铬复鞣,探讨了聚合物的结构对坯革性能及鞣制废液中的三氧化二铬含量等方面的影响。研究结果表明:助鞣剂HP-1能很好地促进铬盐吸收,当其用量为2%时,废液中三氧化二铬的含量可以降到0.21g/L,同时还能赋予坯革良好的丰满性和柔软度。
(3)以丙烯酸甲酯和乙醇胺为主要原料,通过Michael加成反应制备了单体N-羟乙基-3-胺基-N,N-二丙酸甲酯,以丁二酸酐为核,经过缩合聚合反应,得到端酯基超支化聚(胺-酯),再用水合肼对聚合物端基进行改性,制备了肼封端的超支化聚(胺-酯)型甲醛捕获剂HP-2。将其应用于制革生产过程中,探讨其捕获坯革纤维中游离甲醛的能力。应用结果表明:HP-2可明显降低坯革中游离甲醛的含量。当HP-2的用量为2%时,第四代聚合物可将革样中的游离甲醛含量降至70mg/kg以下;并且,其对皮革中游离甲醛的捕获率可达55.6%。因此,本实验合成的肼封端的超支化聚合物对皮革纤维中游离甲醛的捕获效果较好,具有广阔的应用前景。
Hyperbranched polymers have recently been attracting attention because of their special structure and properties. Their preparation mainly relies on a repetitive and alternating siries of coupling and activation reactions. Hyperbranched polymers are three-dimensional highly branched macromolecules with numerous functional groups. Because of their unique features such as high solubility, low viscosity, and abundance of terminal groups, hyperbranched polymers are intriguing to chemists, biochemists, bilolgists and biomedical experts. Hyperbranched polymers can be synthesized through divergent or convergent approaches. Thus, hyperbranched polymers have widely application in many fields, such as chemical, material, biological medicine, environmental protection, and so on. However, the research of their application in leather and fur industry is just starting.
In this paper we summarized the research progress of hyperbranched poly (amine-ester) assistant and hyperbranched poly (amine-ester) formaldehyde capture. The main content of this paper are as follows:
(1) Hyperbranched poly (amine-ester) was prepared by 1, 1, 1-trimethylolpropane (as a core molecule) and N, N-diethylol-3-amine methylpropionate (as an AB2 monomer). The later was synthesized via Michael addition reaction of methyl acrylate and diethanolamine with one step method. Then the hyperbranched poly (amine-ester) was further reacted with maleic anhydride for obtaining a new hyperbranched polymeric assistant with various functional groups (HP-1). The synthetic procedures and the structure of this polymer were characterized by React IR spectrometer, FTIR, 1HNMR and gel permeation chromatograph. The optimum reaction conditions are described as follows: monomer was preprared in 3 hours via Michael addition; the reversal of the Michael addition was reacted during the polymeric process; hyperbranched polymer was not ideal global configuration; and the time of esterifiable reaction was controlled in 40 minutes.
(2) Hyperbranched poly (amine-ester) assistant HP-1 was applied in the leather process. The effects of polymeric characters in chrome tanning and chrome retanning were studied. According to the application results, hyperbranched polymer chrome tanning assistant could improve chrome absorption. When using 2% assistant, application properties were connected with its molecular structure; when the content of Cr2O3 in chrome waste water reduced to 0.21g/L, the fullness and softness of leather have some improved.
(3) Hyperbranched poly (amine-ester) was synthesized with N-ethoxyl-3-amino-N, N-dimethyl propionate and succinic anhydride via one-step manner. The monomer N-ethoxyl-3-amino-N, N-dimethyl propionate was synthesized by Michael addition of ethanolamine and methyl acrylate. Then the hyperbranched poly (amine-ester) was further reacted with Hydrazine Hydrate for obtaining a new hyperbranched polymeric formaldehyde capture (HP-2). Their structures were characterized by FTIR and 1HNMR. HP-2 as free-formaldehyde capture agent was used in process of leather industry, the experimental results showed that: HP-2 has well capturing free-formaldehyde in leather, when its dosage is 2%, free-formaldehyde in leather will be below 70mg/kg. So HP-2 can be a nice formaldehyde capture with terminal hydrazine.
本文综述了超支化聚合物的研究进展;依据聚合物分子设计的原理分别制备了超支化聚(胺-酯)型助鞣剂HP-1、超支化聚(胺-酯)型甲醛捕获剂HP-2,对其结构进行了确认和表征,研究了其结构和应用性能的关系。相信本论文的研究成果对于超支化聚合物助剂的制备以及在制革生产中的应用都具有积极意义。本文的主要内容包括:
(1)以丙烯酸甲酯和二乙醇胺为主要原料,通过Michael加成反应制备了单体N,N-二羟乙基-3-胺基丙酸甲酯,以1,1,1-三羟甲基丙烷为核,经过缩合聚合反应,得到了端基为羟基的超支化聚(胺-酯),再用顺丁烯二酸酐对聚合物端基进行改性,制备了一种新型多官能团的超支化聚(胺-酯)型助鞣剂HP-1。利用在线红外光谱、红外光谱、核磁共振光谱和凝胶渗透光谱等对单体的合成过程及聚合物的结构进行了表征。
(2)将超支化聚(胺-酯)型助鞣剂HP-1应用于铬鞣及铬复鞣,探讨了聚合物的结构对坯革性能及鞣制废液中的三氧化二铬含量等方面的影响。研究结果表明:助鞣剂HP-1能很好地促进铬盐吸收,当其用量为2%时,废液中三氧化二铬的含量可以降到0.21g/L,同时还能赋予坯革良好的丰满性和柔软度。
(3)以丙烯酸甲酯和乙醇胺为主要原料,通过Michael加成反应制备了单体N-羟乙基-3-胺基-N,N-二丙酸甲酯,以丁二酸酐为核,经过缩合聚合反应,得到端酯基超支化聚(胺-酯),再用水合肼对聚合物端基进行改性,制备了肼封端的超支化聚(胺-酯)型甲醛捕获剂HP-2。将其应用于制革生产过程中,探讨其捕获坯革纤维中游离甲醛的能力。应用结果表明:HP-2可明显降低坯革中游离甲醛的含量。当HP-2的用量为2%时,第四代聚合物可将革样中的游离甲醛含量降至70mg/kg以下;并且,其对皮革中游离甲醛的捕获率可达55.6%。因此,本实验合成的肼封端的超支化聚合物对皮革纤维中游离甲醛的捕获效果较好,具有广阔的应用前景。
Hyperbranched polymers have recently been attracting attention because of their special structure and properties. Their preparation mainly relies on a repetitive and alternating siries of coupling and activation reactions. Hyperbranched polymers are three-dimensional highly branched macromolecules with numerous functional groups. Because of their unique features such as high solubility, low viscosity, and abundance of terminal groups, hyperbranched polymers are intriguing to chemists, biochemists, bilolgists and biomedical experts. Hyperbranched polymers can be synthesized through divergent or convergent approaches. Thus, hyperbranched polymers have widely application in many fields, such as chemical, material, biological medicine, environmental protection, and so on. However, the research of their application in leather and fur industry is just starting.
In this paper we summarized the research progress of hyperbranched poly (amine-ester) assistant and hyperbranched poly (amine-ester) formaldehyde capture. The main content of this paper are as follows:
(1) Hyperbranched poly (amine-ester) was prepared by 1, 1, 1-trimethylolpropane (as a core molecule) and N, N-diethylol-3-amine methylpropionate (as an AB2 monomer). The later was synthesized via Michael addition reaction of methyl acrylate and diethanolamine with one step method. Then the hyperbranched poly (amine-ester) was further reacted with maleic anhydride for obtaining a new hyperbranched polymeric assistant with various functional groups (HP-1). The synthetic procedures and the structure of this polymer were characterized by React IR spectrometer, FTIR, 1HNMR and gel permeation chromatograph. The optimum reaction conditions are described as follows: monomer was preprared in 3 hours via Michael addition; the reversal of the Michael addition was reacted during the polymeric process; hyperbranched polymer was not ideal global configuration; and the time of esterifiable reaction was controlled in 40 minutes.
(2) Hyperbranched poly (amine-ester) assistant HP-1 was applied in the leather process. The effects of polymeric characters in chrome tanning and chrome retanning were studied. According to the application results, hyperbranched polymer chrome tanning assistant could improve chrome absorption. When using 2% assistant, application properties were connected with its molecular structure; when the content of Cr2O3 in chrome waste water reduced to 0.21g/L, the fullness and softness of leather have some improved.
(3) Hyperbranched poly (amine-ester) was synthesized with N-ethoxyl-3-amino-N, N-dimethyl propionate and succinic anhydride via one-step manner. The monomer N-ethoxyl-3-amino-N, N-dimethyl propionate was synthesized by Michael addition of ethanolamine and methyl acrylate. Then the hyperbranched poly (amine-ester) was further reacted with Hydrazine Hydrate for obtaining a new hyperbranched polymeric formaldehyde capture (HP-2). Their structures were characterized by FTIR and 1HNMR. HP-2 as free-formaldehyde capture agent was used in process of leather industry, the experimental results showed that: HP-2 has well capturing free-formaldehyde in leather, when its dosage is 2%, free-formaldehyde in leather will be below 70mg/kg. So HP-2 can be a nice formaldehyde capture with terminal hydrazine.
引文
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