【作者】 王强；

【导师】 王强；

【作者基本信息】 新疆大学 ， 工程硕士（专业学位）， 2020， 硕士

【摘要】 本文以1-乙烯基-3-烷基咪唑六氟磷酸盐（[VC_nIM][PF₆]n=2,4,6,8）离子液体（ILs）作为研究对象,通过自由基聚合方法制备了线性乙烯基咪唑类聚离子液体（PILs）材料,并将其应用于氟利昂类气体示踪剂吸附领域。同时,利用反气相色谱技术（IGC）和Hansen溶解度参数模拟软件（HSPi P）对所研究ILs和PILs材料进行了表面性质和热力学性质表征。主要工作内容如下:（1）通过自由基聚合方法进行PILs制备。实验发现:（a）烷基链长度为2,4,6的ILs有聚合产物析出,烷基链长度为8时,无产物析出;（b）三种PILs数均聚合度均在6-7之间,同时具有较好的热稳定性。（2）采用IGC技术表征了四种ILs和三种PILs在303.15-343.15 K温度范围内的表面性质。结果表明:（a）四种ILs和三种PILs材料表面均呈两性偏碱特征;（b）随着阳离子上烷基链延长,四种ILs表面色散自由能和Lewis碱性均逐渐减小;（c）三种PILs表面色散自由能值均随温度升高呈现线性下降规律。（3）采用IGC测定了25种常见有机溶剂与四种ILs在303.15-343.15 K温度范围内的热力学参数。结果表明:（a）二氯甲烷、氯仿、丙酮、甲醇、乙醇、乙腈是四种ILs的共同良溶剂;（b）随着正构烷烃、芳烃化合物和醇类探针上亚甲基数量的增加,ILs与探针溶剂间的摩尔吸附焓值逐渐增大;（c）四种ILs的Hildebrand溶解度参数的值均呈单调递减。（4）以54种有机溶剂与ILs及PILs之间的溶解性实验为基础,通过HSPi P模拟了298.15 K温度下ILs及PILs材料的Hansen三维溶解度参数（δ_T、δ_D、δ_P、δ_H）。结果表明:（a）随着四种ILs上烷基侧链延长,δ_T值逐渐降低,δ_D值逐渐增大。对三种PILs而言,随着PILs骨架上烷基侧链延长,δ_T、δ_D、δ_P、δ_H值均逐渐增大;（b）二甲基甲酰胺、N-甲基吡咯烷酮、糠醛、二甲基亚砜、乙腈、丙酮对三种PILs材料均有较好的溶解效果。随着聚合物骨架上烷基侧链的延长,能互溶的溶剂越来越多。（5）评价了三种PILs吸附管对R22、R134a和R12三种氟利昂气体示踪剂的吸脱附效果。实验结果表明:（a）三种示踪剂在三种PILs表面上的吸附以物理吸附为主,同时存在化学吸附;（b）三种示踪剂与PILs间的吸附热（ΔH）和脱附活化能（E_d）随着PILs的碱性的降低而减小。对同一种PILs而言,三种氟利昂的ΔH和E_d值遵循如下规律:R134a<R22<R12;（c）三种PILs吸附管的线性和脱附率均优于活性炭吸附管。更多还原

【Abstract】 In this paper,1-vinyl-3-alkylimidazole hexafluorophosphate（[VC_nIM][PF₆]n=2,4,6,8）ionic liquids（ILs）were used as the basic research objects.Based on the polymerization,poly（ionic liquid）s（PILs）were prepared and applied to the adsorption of freon gas tracer.At the same time,the inverse gas chromatography（IGC）and Hansen Solubility Parameter in Practice（HSPi P）software were used to characterize the surface properties and thermodynamic properties of ILs and their polymers.The main work and results are divided into the following aspects:（1）All PILs were prepared by a free radical polymerization.The experiment found that:（a）The ILs with alkyl chain lengths of 2,4,6 were found to precipitate product with a yield of more than 60%,while the alkyl chain length was 8,no product was polymerized.（b）The number average polymerization degree of three obtained PILs is between 6 and 7,and has good thermal stability.（2）The surface properties of four ILs and three PILs were determined via IGC in the temperature range of 303.15-343.15 K.The experimental results showed that:（a）The surface of the four ILs and three PILs can be considered to be amphoteric with a predominantly basic character.（b）With the increase of the alkyl chain on the cation,the dispersive free energy and Lewis basicity of the four ILs were all decrease.（c）The dispersive free energy of three PILs decreases linearly with increasing temperature.（3）The thermodynamic parameters between 25 organic solvents and four ILs were measured by IGC in the temperature range of 303.15-343.15 K.The experimental results showed that:（a）Dichloromethane,chloroform,acetone,methanol,ethanol,and acetonitrile are common good solvents for the four ILs.（b）For n-alkane probes,aromatic compounds and alcohol probes,as the number of methylene groups increases,the molar adsorption enthalpy between each IL and probe solvents gradually increased.（c）The Hildebrand solubility parameters of the examined ILs are monotonic and decrease with the increase of the experimental temperature.（4）Based on the dissolution test between 54 organic solvents and ILs&PILs,the Hansen three-dimensional solubility parameters（δ_T,δ_D,δ_P,δ_H）of the four ILs and three PILs materials were predicted by HSPi P at T=298.15 K.The experimental results showed that:（a）With the extension of the alkyl side chains on the four ILs,theδ_Tvalue gradually decreases and theδ_D value gradually increases.For the three PILs,with the increase of the alkyl side chain on the PILs backbone,the values ofδ_T,δ_D,δ_Pandδ_H all increase gradually.（b）The solvents include dimethylformamide,n-methylpyrrolidone,furfural,dimethyl sulfoxide,acetonitrile and acetone have a good dissolution on the three PILs materials.With the increase of the alkyl side chain on the polymer backbone,more and more solvents can be miscible with PILs.（5）The adsorption and desorption effects of three PILs adsorption tubes on three freon gas tracers were evaluated including R22,R134a and R12.The experimental results showed that:（a）The adsorption of the three tracers on the surface of the three PILs is mainly physical adsorption,and there is chemical adsorption at the same time.（b）The heat of adsorption（ΔH）and desorption activation energy（E_d）between the three tracers and PILs decreased as the basicity of PILs decreased.For each PIL,theΔH and E_d values of the three freons follow the following rules:R134a<R22<R12.（C）The linearity and desorption rate of the three PILs adsorption tubes are better than those of activated carbon adsorption tube.更多还原