新型两亲性聚酰胺的合成及性质

doi:10.11944/j.issn.1000-0518.2017.03.160214

摘要/Abstract

摘要：

为了设计天然气水合物抑制剂和了解作用机理提供依据,分析两亲性聚酰胺与水相互作用的特征与本质,本文合成了新型水溶性高分子聚柠檬酰丙二胺,在此基础上合成了一种含环己基基团的两亲性聚柠檬酰丙二胺。通过核磁共振波谱、凝胶渗透色谱和示差扫描量热法对产物的结构和性能进行了表征。研究表明,改性的聚柠檬酰胺能形成不可冰冻束缚水,而且比传统的天然气水合物抑制剂聚(N-乙烯基己内酰胺)和聚维酮形成的不可冰冻束缚水多1倍。改性后聚合物中水的比热容增加约36%。聚合物和水之间产生的疏水相互作用,可将水分子更紧密地束缚在聚合物中。改性后的聚合物的疏水性强,造成了水分子彼此紧密束缚程度提高,为不可冰冻束缚水含量的增加提供了必要的环境。

关键词: 水溶性高分子, 疏水作用, 不可冰冻束缚水, 比热容

Abstract:

To provide a theoretical basis for designing natural gas hydrate inhibitors and understanding the inhibition mechanism, and to analyze the nature and characteristics of the interactions between amphiphilic polyamides and water, water soluble poly(1,3-propylene citramide) was synthesized and based upon which, a new amphiphilic polymer was prepared by the modification with cyclohexyl isocyanate. The structure and properties of the product were characterized by proton nuclear magntic resonance spectroscopy, gel permeation chromatography and differential scanning calorimetry. The results show that the modified polymer forms nonfreezable bound water(NFBW) and the amount of the NFBW is twice the level in traditional kinetic gas hydrate inhibitors such as poly(N-vinylcaprolactam) or poly(N-vinylpyrrolidone). The specific heat capacities of water in the modified polymer increases remarkably by 36%. The hydrophobic interaction force between the polymer and water is enhanced, resulting in significant hydrophobic hydration restricted in the polymer. The modified polymers show strong hydrophobicity, leading to high levels of tightly bound water molecules and providing a necessary environment for increasing amount of NFBW.

Key words: water soluble polymer, hydrophobic force, non-freezable bound water, specific heat capacity

迟咏梅, 徐松杰, 曹玉廷, 董坚. 新型两亲性聚酰胺的合成及性质[J]. 应用化学, 2017, 34(3): 269-275.

CHI Yongmei, XU Songjie, CAO Yuting, DONG Jian. Synthesis and Properties of Novel Amphiphilic Polyamides[J]. Chinese Journal of Applied Chemistry, 2017, 34(3): 269-275.

参考文献

[1]	Hammerschmidt E G. Formation of Gas Hydrates in Natural Gas Transmission Lines[J]. Ind Eng Chem,1934,26(8):851-855.
[2]	Kelkar S K,Selim M S,Sloan E D. Hydrate Dissociation Rates in Pipelines[J]. Fluid Phase Equilib, 1998,150/151(1):371-382.
[3]	ZHANG Ziyi,TONG Le,PAN Yi. Prediction of Gas Hydrate in Pipeline[J]. Contemp Chem Ind,2013,42(4):425-427(in Chinese). 张孜义,佟乐,潘一. 管道中天然气水合物的预测[J]. 当代化工,2013,42(4):425-427.
[4]	LIU Jun,MA Guiyang,PAN Zhen,et al.Experiment on Formation and Decomposition of Methane Hydrate[J]. Chem Eng,2015,43(11):35-40 (in Chinese). 刘军,马贵阳,潘振,等. 甲烷水合物生成分解的实验研究[J]. 化学工程,2015,43(11):35-40.
[5]	GONG Zhiwu,ZHANG Liang,CHENG Haiqing,et al.The Influence of Subsea Natural Gas Hydrate Dissociation on the Safety of Offshore Drilling[J]. Pet Drill Technol,2015,43(4):19-24(in Chinese). 宫智武,张亮,程海清,等. 海底天然气水合物分解对海洋钻井安全的影响[J]. 石油钻探技术,2015,43(4):19-24.
[6]	CUI Qing. The Prevention of Natural Gas Hydrates in Pipeline[J]. Appl Energy Technol,2014,(10):27-30(in Chinese). 崔青. 输气管线中天然气水合物的防治[J]. 应用能源技术,2014,(10):27-30.
[7]	BAI Yuhu,LI Qingping,ZHOU Jianliang,et al.The Potential Risk of Gas Hydrate to Deepwater Drilling and Production and the Corresponding Strategy[J]. Pet Drill Tech,2009,37(3):17-21(in Chinese). 白玉湖,李清平,周建良,等. 天然气水合物对深水钻采的潜在风险及对应性措施[J]. 石油钻探技术,2009,37(3):17-21.
[8]	ZHAO Xin,QIU Zhengsong,JIANG Lin,et al.An Experimental Analysis of Natural Gas Hydrate Formation at the Presence of Kinetic Hydrate Inhibitors[J]. Nat Gas Ind,2014,34(2):105-110(in Chinese). 赵欣,邱正松,江琳,等. 动力学抑制剂作用下天然气水合物生成过程的实验分析[J]. 天然气工业,2014,34(2):105-110.
[9]	QUAN Hongping,LI Qiang,LU Hongsheng,et al.Study on Properties of Natural Gas Hydrate Inhibitor BVP[J]. Sci Technol Eng,2013,13(6):1442-1445(in Chinese). 全红平,李强,鲁红升,等. 天然气水合物抑制剂BVP性能研究[J]. 科学技术与工程,2013,13(6):1442-1445.
[10]	FAN Shuanshi,WANG Yanhong,LANG Xuemei. Research Progress of Natural Gas Hydrate Kinetic Inhibition Technology[J]. Nat Gas Ind,2011,31(12):1-11(in Chinese). 樊栓狮,王燕鸿,郎雪梅. 天然气水合物动力学抑制技术研究进展[J]. 天然气工业,2011,31(12):1-11.
[11]	YAN Xiaoyan,HAO Hong,WANG Kai,et al.Progress in Compound Gas Hydrate Inhibitors[J]. Petrochem Technol,2013,41(11):1286-1292(in Chinese). 闫晓艳,郝红,王凯,等. 复合型天然气水合物抑制剂的研究进展[J]. 石油化工,2013,41(11):1286-1292.
[12]	LIU Jianyi,ZHANG Jing,ZHANG Guangdong,et al.Evaluation and Application of a New Hydrate Kinetic Inhibitor[J]. Nat Gas Ind,2011,31(1):65-68(in Chinese). 刘建仪,张婧,张广东,等. 新型天然气水合物动力学抑制剂评价及应用[J]. 天然气工业,2011,31(1):65-68.
[13]	HUO Hongjun,REN Shaoran,WANG Ruihe,et al.Experiment on Synergetic Effects of Kinetic and Thermodynamic Hydrate Inhibitors[J]. J China Univ Pet(Edn Nat Sci),2012,36(5):110-113(in Chinese). 霍洪俊,任韶然,王瑞和,等. 气体水合物动力学和热力学抑制剂复合作用试验[J]. 中国石油大学学报(自然科学版),2012,36(5):110-113.
[14]	TANG Cuiping,DU Jianwei,LIANG Deqing,et al.Investigation on a New Natural Gas Hydrate Kinetic Inhibitor[J]. J Xi'an Jiaotong Univ,2008,42(42):333-337(in Chinese). 唐翠萍,杜建伟,梁德青,等. 天然气水合物新型动力学抑制剂抑制性能研究[J]. 西安交通大学学报,2008,42(42):333-337.
[15]	BAI Xiaodong,HUANG Jinjun,WANG Chuan,et al.Evaluating Investigation of a New Hydrate Inhibitor HBH[J]. Pet Drill Technol,2007,35(2):36-38(in Chinese). 白小东,黄进军,王川,等. 新型水合物抑制剂HBH的评价研究[J]. 石油钻探技术,2007,35(2):36-38.
[16]	Andrea P,Musa O M,Steed J W. The Chemistry of Low Dosage Clathrate Hydrate Inhibitors[J]. Chem Soc Rev,2013,42(5):1996-2015.
[17]	ZHAO Xin,QIU Zhengsong,HUANG Weian,et al.Inhibition Mechanism and Optimized Design of Thermodynamic Gas Hydrate Inhibitors[J]. Acta Pet Sin,2015,36(6):760-766(in Chinese). 赵欣,邱正松,黄维安,等. 天然气水合物热力学抑制剂作用机制及优化设计[J]. 石油学报,2015,36(6):760-766.
[18]	LEI linglin,SHI Xiaolong. Research Progress in Natural Gas Hydrate Inhibition Technology[J]. West-China Explor Eng,2013,25(6):87-89(in Chinese). 雷玲琳,石晓栊. 天然气水合物抑制技术研究进展[J]. 西部探矿工程,2013,25(6):87-89
[19]	WANG Shumiao,WANG Guofu,LIU Hongbo,et al.Application Study on Gas Hydrate Inhibitors of Gas Transmission Pipeline[J]. Oil Gas Storage Transport,2006,25(2):43-46(in Chinese). 王书淼,王国付,刘宏波,等. 管内天然气水合物抑制剂的应用研究[J]. 油气储运,2006,25(2):43-46.
[20]	XU Jiafang,QIU Zhengsong,HE Chang. The Inhibitor Optimization of Gas Hydrates in Deepwater Drilling Fluids[J]. Acta Pet Sin,2011,32(1):149-152(in Chinese). 徐加放,邱正松,何畅. 深水钻井液中水合物抑制剂的优化[J]. 石油学报,2011,32(1):149-152.
[21]	Davenport J R,Musa O M,Paterson M J,et al.A Simple Chemical Model for Clathrate Hydrate Inhibition by Polyvinylcaprolactam[J]. Chem Commun,2011,47(35):9891-9893.
[22]	BI Man,JIA Zengqiang,WU Hongqin,et al.Update Progress in Research and Application of Natural Gas Hydrate Inhibitor[J]. Nat Gas Ind,2009,29(12):75-78(in Chinese). 毕曼,贾增强,吴红钦,等. 天然气水合物抑制剂研究与应用进展[J]. 天然气工业,2009,29(12):75-78.
[23]	Anderson B J,Tester J W,Paolo B G,et al.Properties of Inhibitors of Methane Hydrate Formation via Molecular Dynamics Simulations[J]. J Am Chem Soc,2005,127(50):17852-17862.
[24]	Yagci Y E,Antonietti M,Borner H G. Synthesis of Poly(tartar amides) as Bio-inspired Antifreeze Additives[J]. Macromol Rapid Commun,2006,19(27):1660-1664.
[25]	WANG Xuezhen,BAI Zilong,MA Hongliao,et al.Studies on Preparation and Properties of Polyglycerol Esteramide as a Gas Hydrate Kinetic Inhibitor[J]. Oilfield Chem,2010,27(2):212-215(in Chinese). 王学珍,柏子龙,马宏燎,等. 聚甘油酰胺酯高效气体水合物动力学抑制剂的研制及性能评价[J]. 油田化学,2010,27(2):212-215.
[26]	SUN Li,DONG Jian. Recent Progress in Polymers as Kinetic Hydrate Inhibitors[J]. Chinese Polym Bull,2014,(10):69-76(in Chinese). 孙力,董坚. 天然气水合物抑制剂用高分子研究进展[J]. 高分子通报,2014,(10):69-76.
[27]	Munoz F,Kelland M,Sun L,et al.Kinetic Hydrate Inhibitors: Structure-activity Relationship Studies on a Series of Branched Poly(ethylene citramide)s with Varying Lipophilic Groups[J]. Energy & Fuels,2015,29(8):4774-4782.
[28]	Varma-Nair M,Costello C A,Colle K S,et al.Thermal Analysis of Polymer-water Interactions and Their Relation to Gas Hydrate Inhibition[J]. J Appl Polym Sci,2007,103(4):2642-2653.
[29]	LU Hong,FENG Dachun,YANG Jiyou. Comparison of Differential Scanning Calorimetry and Modulated Differential Scanning Calorimetry in Measurement of Specific Heat Capacities[J]. Anal Instrum,2011,(3):70-74(in Chinese). 鲁红,冯大春,杨继佑. DSC、MDSC测定物质比热容的比较[J]. 仪器分析,2011,(3):70-74.