线性—端羟基超支化聚合物的合成、磷酸酯化及其在皮革加脂中的应用

发布时间：2018-05-04 01:34

本文选题：线性-超支化聚合物 + 磷酸酯化　；参考：《陕西科技大学》2017年硕士论文

【摘要】：三维立体球形结构的超支化聚合物是一种支化大分子,其优异性能包括具有大量末端基团、良好的溶解性和高化学活性等。近年来,超支化聚合物的合成方法已渐趋成熟,功能化改性则成为新的研究热点。超支化聚酰胺型(PAMAM)末端含有大量可用于改性的活性羟基。本论文是以PAMAM为核,利用酰氯化反应生成线性-超支化聚合物(PAMAM-n),再进行磷酸酯化反应,制备出一种线性-超支化磷酸酯聚合物。将其应用于皮革加脂工艺中,研究支化结构分子对皮革胶原纤维的作用机理以及构效关系。首先,以一代PAMAM为基体,以三乙胺为缚酸剂,在N,N-二甲基甲酰胺(DMF)溶液中,通过月桂酰氯与其端羟基进行酰氯化反应,控制摩尔比,合成了一系列线性-超支化聚合物(PAMAM-n),其中PAMAM与月桂酰氯以不同摩尔比进行反应。通过傅立叶红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)和羟值测定等分析手段表征了PAMAM-n的分子结构。同时利用表面张力仪和纳米粒度仪(DLS)等仪器研究了PAMAM-n的表面性能及其乳液粒径,结果表明,其表面张力位于21.38~27.96 mN·m-1,乳液粒径分布在120.6~457.8 nm之间,其中PAMAM-3具有最为优异的表面活性。其次,在上述反应的基础下,以PAMAM-3为中间体,对其未进行反应的羟基进行磷酸酯化反应:选择P2O5为磷酸化试剂,CCl4作分散剂,在四氢呋喃溶液(THF)中进行酯化反应,随后加入一定量的水进行水解反应,提纯后得到线性-超支化磷酸酯聚合物(PAMAM-3-P)。以磷酸化单酯与双酯含量为参考指标,优化合成条件,得到最佳反应条件:P2O5:CCl4的摩尔比1:2.5,酯化温度60℃,酯化时间6 h,水解温度65℃和水解时间3.5 h。使用FT-IR、1H-NMR、核磁共振碳谱(13C-NMR)和凝胶渗透色谱(GPC)等分析手段表征了产物的结构,使用稳态荧光法、表面张力法和DLS研究了产物的表面活性及其乳液性能,结果表明PAMAM-3-P具有优异的表面活性,其乳液具有很好的稳定性,乳液粒径约为180 nm。随后,通过PAMAM-3-P和非离子表面活性剂AEO-9进行复配,对蓖麻油进行乳化,合成一种新型的复配物。单因素试验优化其复配条件,确定了最佳复配条件:亲水亲油平衡值(HLB值)10.5、复配温度60℃、复配时间60 min、搅拌速度500 r·min-1、pH=7和复配物与油脂配比3:0.75。测定复配物的表面张力和临界胶束浓度(CMC值),同时对乳液粒径和稳定性进行表征,该复配物表面张力为30.67 mN·m-1,CMC值为0.28 g·L-1,乳液粒径为203.2 nm,并具有优异的稳定性。最后,以服装用绵羊蓝湿革为原料,将PAMAM-3、PAMAM-3-P以及复配物分别应用于皮革的加脂工序中。通过扫描电子显微镜(SEM)、X光电子能谱(XPS)、X射线衍射(XRD)、热重(TG)等现代仪器方法对比研究了PAMAM-3和PAMAM-3-P加脂前后对革样结构的微观影响。结果表明,产物以三维立体状态填充在胶原纤维之间,从而增大了纤维间距,提高了胶原纤维的无序度,但并未破坏胶原蛋白的三股螺旋结构。通过拉力机、柔软度仪和增厚仪等分析手段研究了加脂后坯革的物理机械性能、柔软度和增厚率。结果表明,加脂后皮革的柔软度和增厚率较空白试样有所提高,而复配后的柔软度和增厚率效果更为明显。与此同时,物理机械性能较空白试样也有较为明显的提升。以上结果均表明:线性-超支化聚合物以及磷酸酯化后的产物均具有良好的表面性能,有望作为新型皮革加脂剂应用于皮革领域。
[Abstract]:The hyperbranched polymer of three-dimensional spherical structure is a branched macromolecule. Its excellent properties include a large number of terminal groups, good solubility and high chemical activity. In recent years, the synthesis method of hyperbranched polymers has gradually become mature, and the functional modification has become a new research hotspot. The terminal of hyperbranched polyamide type (PAMAM) is contained. A large number of active hydroxyl groups can be used to modify the active hydroxyl group. In this paper, a linear hyperbranched polymer (PAMAM-n) was produced by the acylation reaction by PAMAM, and then a linear hyperbranched phosphate polymer was prepared. It was applied to the Leather Fatliquoring Process to study the effect of branched structural molecules on leather collagen fibers. First, a series of linear - hyperbranched polymers (PAMAM-n) were synthesized through the acyl chlorination of lauryl chloride and the end hydroxyl group in N, N- two methyl formamide (DMF) solution with a generation of PAMAM as the matrix and three ethylamine as the acid binding agent (DMF), in which PAMAM and lauryl chloride were reacted at different molar ratios. The molecular structure of PAMAM-n was characterized by Fu Liye infrared spectroscopy (FT-IR), magnetic resonance hydrogen spectrum (1H-NMR) and hydroxyl value determination. The surface properties and emulsion particle size of PAMAM-n were studied by means of surface tension instrument and nano particle size instrument (DLS). The results showed that the surface tension of PAMAM-n was located at 21.38~27.96 mN M-1 and the particle size of the emulsion. Distributed among 120.6~457.8 nm, PAMAM-3 has the most excellent surface activity. Secondly, on the basis of the reaction, PAMAM-3 is used as the intermediate to phosphorylate the hydroxyl group which is not reacted: P2O5 is the phosphorylation agent, CCl4 is used as dispersant, and the esterification reaction in tetrahydrofuran solution (THF) is carried out, then one is added. A linear - hyperbranched phosphate polymer (PAMAM-3-P) was obtained after the hydrolysis of the water. The optimum reaction conditions were obtained with the content of mono phosphorylated monoester and diester as the reference index. The optimum reaction conditions were obtained: the molar ratio of P2O5:CCl4 to 1:2.5, the esterification temperature 60 C, the esterification of 6 h, the hydrolysis temperature 65 C and the hydrolysis time 3.5 h. using FT-IR, 1H- NMR, magnetic resonance carbon spectroscopy (13C-NMR) and gel permeation chromatography (GPC) were used to characterize the structure of the products. The surface activity and emulsion properties of the products were studied by steady-state fluorescence method, surface tension method and DLS. The results show that PAMAM-3-P has excellent surface activity, the emulsion has good stability and the particle size of the emulsion is about 180 nm.. Then, the emulsification of castor oil was emulsified by PAMAM-3-P and nonionic surfactant AEO-9, and a new type of compound was synthesized. The optimum compound condition was optimized by single factor test. The optimum compound condition was determined: the equilibrium value of hydrophilic oil (HLB) 10.5, the mixing temperature 60 C, the mixing time 60 min, the stirring speed 500 R. Min-1, pH=7 and the compound. The surface tension and critical micelle concentration (CMC value) of the compound were measured by 3:0.75., and the particle size and stability of the emulsion were characterized. The surface tension of the compound was 30.67 mN. M-1, the CMC value was 0.28 g L-1, the particle size of the emulsion was 203.2 nm, and it had excellent stability. Finally, the blue wet leather of sheep was used as the raw material and PAMAM-3. PAMAM-3-P and the compound were applied to the Fatliquoring Process of leather. Through the scanning electron microscope (SEM), X photoelectron spectroscopy (XPS), X ray diffraction (XRD), and thermogravimetry (TG), the microscopic effects of PAMAM-3 and PAMAM-3-P addition on the leather structure were compared. The results showed that the products were filled with three dimensional state in the glue. Between the raw fibers, the fiber spacing is increased, the disorder degree of the collagen fiber is increased, but the three strand helical structure of collagen is not destroyed. The physical mechanical properties, softness and thickening rate of the leather after the fatliquoring are studied by the tension machine, softener and the thickening instrument. The results show that the softness and thickening of the leather after the fatliquoring have been shown. Compared with the blank sample, the softness and thickening effect of the compound are more obvious. At the same time, the physical and mechanical properties are better than that of the blank sample. All the results show that the linear hyperbranched polymers and the products after phosphorylation have good surface properties and are expected to be a new type of Leather Fatliquoring. The agent is used in the leather field.

【学位授予单位】：陕西科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ317;TS544

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