含芳香基团的梳状聚合物型降凝剂与沥青质协同改善合成蜡油的流变性

doi:10.7503/cjcu20190394

摘要/Abstract

摘要：

采用流变学实验、差示扫描量热(DSC)分析、显微观察及沥青质沉淀实验研究了聚丙烯酸十八酯-马来酸酐(POM)、聚丙烯酸十八酯-马来酸酐-苯胺(POMA)及聚丙烯酸十八酯-马来酸酐-萘胺(POMN)梳状聚合物对合成蜡油的流变性能的影响规律. 实验结果表明, 这3种梳状聚合物降凝剂均能在一定程度上改善不含沥青质合成蜡油(MO-1)的低温流变性, 其中POM对MO-1蜡油的流变性改善效果最佳. 添加500 mg/kg POM后, MO-1的凝点从29 ℃降至23 ℃, 屈服值从627.20 Pa降至83.35 Pa. 而POM, POMA和POMN可以显著改善含0.3%(质量分数)沥青质的合成蜡油(MO-2)的低温流变性, 且添加500 mg/kg POMA后MO-2蜡油的流变改善效果最佳: 凝点降至3 ℃, 屈服值降至1.27 Pa. 可见, 本文制备的梳状聚合物降凝剂均能与沥青质协同改善MO-2蜡油的流变性, 并且向POM中引入芳香基团能进一步促进沥青质与降凝剂分子的相互作用, 进而增强梳状聚合物降凝剂与沥青质的协同作用.

关键词: 梳状聚合物, 沥青质, 合成蜡油, 协同效应

Abstract:

The influence of poly-octadecyl acrylate-maleic anhydride(POM), poly-octadecyl acrylate-maleic anhydride-aniline(POMA) and poly-octadecyl acrylate-maleic anhydride-naphthylamine(POMN) copolymers on the flowability of model waxy oil with/without asphaltenes was investigated through rheological tests, differential scanning calorimeter(DSC) analysis, microscopic observation and asphaltenes precipitating tests. The results showed that the above three types of comb-like polymeric pour point depressants(PPDs) could improve the flowability of the model waxy oil without asphaltenes(MO-1) to some extent and the POM showed the best flow improving efficiency on the MO-1: after adding 500 mg/kg POM, the pour point of the MO-1 decreased from 29 ℃ to 23 ℃ and yield stress reduced from 62.20 Pa to 83.35Pa. Comb-like polymers could significantly improve the flowability of model waxy oil with 0.3% asphaltenes(MO-2), and MO-2 showed the best flowability after the addition of 500 mg/kg POMA: the pour point and yield stress of MO-2 dropped to 3 ℃/1.27 Pa, respectively. Therefore, the comb-like polymeric PPDs and asphaltenes can synergistically improve the flowability of waxy oils and the introduction of aromatic pendants in the POM molecules can enhance the interaction of comb-like polymeric PPDs and asphaltenes, thus further increasing the synergistic effect of comb-like polymeric PPDs and asphaltenes.

Key words: Comb-like copolymer, Asphaltene, Model waxy oil, Synergistic effect

中图分类号:

O631.1 ⁺1

TrendMD:

杨飞,张晓平,李传宪,姚博,代抒彤,夏雪,孙广宇. 含芳香基团的梳状聚合物型降凝剂与沥青质协同改善合成蜡油的流变性. 高等学校化学学报, 2019, 40(12): 2606.

Fei YANG,Xiaoping ZHANG,Chuanxian LI,Bo YAO,Shutong DAI,Xue XIA,Guangyu SUN. Comb-like Polymeric Pour Point Depressants with Aromatic Pandents and Asphaltenes Synergistically Improve the Flow Behavior of Model Waxy Oils ^†. Chem. J. Chinese Universities, 2019, 40(12): 2606.

图/表 10

Fig.1 Carbon number distribution of the mixed paraffin wax

Scheme 1 Chemical structures of POM, POMA and POMN

Fig.2 1H NMR spectra of POM(A), POMA(B) and POMN(C)

Fig.3 Crystallization exothermic curves of POM(a), POMA(b) and POMN(c)

Table 1 Pour point and yield stress of MO-1 and MO-2 undoped/doped with 500 mg/kg POM, POMA and POMN

System	Oil sample	Undoped	POM	POMA	POMN
Pour point/℃	MO-1	29	23	23	24
	MO-2	20	9	3	5
Yield stress/Pa	MO-1	627.20	83.35	99.89	124.08
	MO-2	84.85	10.05	1.27	4.46

Fig.4 Strain-stress curves(A, B) and flow curves(C, D) of MO-1(A, C) and MO-2(B, D) undoped(a) and doped with 500 mg/kg POM(b), POMA(c) and POMN(d)

Fig.5 Structural properties of MO-1(A) and MO-2(B) undoped(a) and doped with 500 mg/kg POM(b), POMA(c) and POMN(d) under dynamic cooling process

Fig.6 DSC curves(A, C) and percentage of precipitated waxy crystals at different temperatures(B, D) of MO-1(A, B) and MO-2(C, D) undoped(a) and doped with POM(b), POMA(c) and POMN(d)

Fig.7 Microscopic characteristics of MO-1(A—D) and MO-2(E—H) undoped(A, E) and doped with 500 mg/kg POM(B, F), POMA(C, G) and POMN(D, H), respectively

Fig.8 Percentage of precipitated asphaltenes without(a) and with the addition of POM(b), POMA(c) and POMN(d)

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