本文選題：線性-超支化聚合物 + 磷酸酯化��； 參考：《陜西科技大學(xué)》2017年碩士論文

【摘要】：三維立體球形結(jié)構(gòu)的超支化聚合物是一種支化大分子,其優(yōu)異性能包括具有大量末端基團(tuán)、良好的溶解性和高化學(xué)活性等。近年來,超支化聚合物的合成方法已漸趨成熟,功能化改性則成為新的研究熱點(diǎn)。超支化聚酰胺型(PAMAM)末端含有大量可用于改性的活性羥基。本論文是以PAMAM為核,利用酰氯化反應(yīng)生成線性-超支化聚合物(PAMAM-n),再進(jìn)行磷酸酯化反應(yīng),制備出一種線性-超支化磷酸酯聚合物。將其應(yīng)用于皮革加脂工藝中,研究支化結(jié)構(gòu)分子對皮革膠原纖維的作用機(jī)理以及構(gòu)效關(guān)系。首先,以一代PAMAM為基體,以三乙胺為縛酸劑,在N,N-二甲基甲酰胺(DMF)溶液中,通過月桂酰氯與其端羥基進(jìn)行酰氯化反應(yīng),控制摩爾比,合成了一系列線性-超支化聚合物(PAMAM-n),其中PAMAM與月桂酰氯以不同摩爾比進(jìn)行反應(yīng)。通過傅立葉紅外光譜(FT-IR)、核磁共振氫譜(1H-NMR)和羥值測定等分析手段表征了PAMAM-n的分子結(jié)構(gòu)。同時(shí)利用表面張力儀和納米粒度儀(DLS)等儀器研究了PAMAM-n的表面性能及其乳液粒徑,結(jié)果表明,其表面張力位于21.38~27.96 mN·m-1,乳液粒徑分布在120.6~457.8 nm之間,其中PAMAM-3具有最為優(yōu)異的表面活性。其次,在上述反應(yīng)的基礎(chǔ)下,以PAMAM-3為中間體,對其未進(jìn)行反應(yīng)的羥基進(jìn)行磷酸酯化反應(yīng):選擇P2O5為磷酸化試劑,CCl4作分散劑,在四氫呋喃溶液(THF)中進(jìn)行酯化反應(yīng),隨后加入一定量的水進(jìn)行水解反應(yīng),提純后得到線性-超支化磷酸酯聚合物(PAMAM-3-P)。以磷酸化單酯與雙酯含量為參考指標(biāo),優(yōu)化合成條件,得到最佳反應(yīng)條件:P2O5:CCl4的摩爾比1:2.5,酯化溫度60℃,酯化時(shí)間6 h,水解溫度65℃和水解時(shí)間3.5 h。使用FT-IR、1H-NMR、核磁共振碳譜(13C-NMR)和凝膠滲透色譜(GPC)等分析手段表征了產(chǎn)物的結(jié)構(gòu),使用穩(wěn)態(tài)熒光法、表面張力法和DLS研究了產(chǎn)物的表面活性及其乳液性能,結(jié)果表明PAMAM-3-P具有優(yōu)異的表面活性,其乳液具有很好的穩(wěn)定性,乳液粒徑約為180 nm。隨后,通過PAMAM-3-P和非離子表面活性劑AEO-9進(jìn)行復(fù)配,對蓖麻油進(jìn)行乳化,合成一種新型的復(fù)配物。單因素試驗(yàn)優(yōu)化其復(fù)配條件,確定了最佳復(fù)配條件:親水親油平衡值(HLB值)10.5、復(fù)配溫度60℃、復(fù)配時(shí)間60 min、攪拌速度500 r·min-1、pH=7和復(fù)配物與油脂配比3:0.75。測定復(fù)配物的表面張力和臨界膠束濃度(CMC值),同時(shí)對乳液粒徑和穩(wěn)定性進(jìn)行表征,該復(fù)配物表面張力為30.67 mN·m-1,CMC值為0.28 g·L-1,乳液粒徑為203.2 nm,并具有優(yōu)異的穩(wěn)定性。最后,以服裝用綿羊藍(lán)濕革為原料,將PAMAM-3、PAMAM-3-P以及復(fù)配物分別應(yīng)用于皮革的加脂工序中。通過掃描電子顯微鏡(SEM)、X光電子能譜(XPS)、X射線衍射(XRD)、熱重(TG)等現(xiàn)代儀器方法對比研究了PAMAM-3和PAMAM-3-P加脂前后對革樣結(jié)構(gòu)的微觀影響。結(jié)果表明,產(chǎn)物以三維立體狀態(tài)填充在膠原纖維之間,從而增大了纖維間距,提高了膠原纖維的無序度,但并未破壞膠原蛋白的三股螺旋結(jié)構(gòu)。通過拉力機(jī)、柔軟度儀和增厚儀等分析手段研究了加脂后坯革的物理機(jī)械性能、柔軟度和增厚率。結(jié)果表明,加脂后皮革的柔軟度和增厚率較空白試樣有所提高,而復(fù)配后的柔軟度和增厚率效果更為明顯。與此同時(shí),物理機(jī)械性能較空白試樣也有較為明顯的提升。以上結(jié)果均表明:線性-超支化聚合物以及磷酸酯化后的產(chǎn)物均具有良好的表面性能,有望作為新型皮革加脂劑應(yīng)用于皮革領(lǐng)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.

【學(xué)位授予單位】：陜西科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ317;TS544

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