【作者】 路国超；

【导师】 杨百勤；

【作者基本信息】 陕西科技大学 ， 应用化学， 2012， 硕士

【摘要】 阳离子氟表面活性剂在氟表面活性剂的整个生产和应用中占据着十分重要的地位。目前，使用最为广泛的阳离子氟表面活性剂主要以电解氟化产物全氟烷基磺酰氟(C_nF_2n+1SO₂F)、全氟烷基酰氟(C_nF_2n+1COF)为基础原料、分别与N,N-二甲基丙二胺[NH₂（CH₂）₃N（CH₃）₂]反应，得到C_nF_2n+1SO₂NH（CH₂）N（CH₃）₂和C_nF_2n+1CONH（CH₂）₃N（CH₃）₂两种中间体，最后通过酸化或季铵化引入亲水基团，从而得到胺盐型和季铵盐型两大类阳离子氟表面活性剂。由于起始原料全氟辛基磺酰氟的成本要低廉得多，因而C₈F₇SO₂NH（CH₂）₃N（CH₃）₂衍生的胺盐型和季铵盐型就成了应用最为广泛的两类阳离子型氟表面活性剂。由于该类型阳离子氟表面活性剂工业应用性较强，报道多为专利，公开发表的研究论文不多。其结构与性能关系方面的研究相对缺乏。本文以全氟辛基磺酰氟(C₈F₁₇SO₂F)为基础，合成了四种N-[γ-（二烷基氨基）烷基]全氟辛基磺酰胺的盐酸盐[C₈F₁₇SO₂NH（CH₂）_nNHR₂Cl^-]和四种季铵盐[C₈F₁₇SO₂NH（CH₂）_nN⁺R₂（CH₃）I^-]阳离子型氟表面活性剂。通过测定溶解性、表面张力、在石蜡表面的接触角、发泡力和泡沫稳定性，研究了这些阳离子氟表面活性剂在水溶液中的溶解性、表面活性、润湿性能及泡沫性能，其中C₈F₁₇SO₂NH（CH₂）₂N（CH₃）₂HCl和C₈F₁₇SO₂NH（CH₂）₂N（CH₃）₃I的溶解性较差导致表面活性、对石蜡表面的润湿性及起泡性很差。研究结果表明，这些阳离子氟表面活性剂的cmc和γcmc都很低，说明其表面活性都很高，在一定范围内改变中间碳氢间隔基的长度和亲水头基大小主要影响表面活性剂的水溶性，但对其表面活性影响较小，它们的润湿性能和泡沫性能均呈现相似的规律。原因可能是由于全氟辛基的强疏水性，其降低表面张力的能力和效率主要决定于氟碳链的长度，掩盖了中间碳氢间隔基的长度和亲水头基大小对其表面活性的影响。因此，选择该类型的阳离子氟表面活性剂时，可以不考虑端基基团的细微变化对性能的影响，工业上应用可以优先选择溶解性好，合成工艺比较成熟，成本较低的阳离子氟表面活性剂。继续研究了六氟丙烯三聚体衍生的阴离子型氟表面活性剂全氟壬烯氧基苯磺酸钠(C₉F₁₇OC₆H₄SO₃Na,简称OBS)与反电性的碳氢表面活性剂——烷基季铵盐[C_nH_2n+1NR₃Br （C_nNR）, n=8,10,12, R=CH₃（M）, CH₂CH₃（E）]的复配性能，结果表明，通过与C_nNR复配，OBS的cmc和γ_cmc均大幅下降，达到了全面增效的结果。不同摩尔比的OBS–C₈NE混合体系中，摩尔比为1:1时表面活性最好，cmc和γ_cmc均最小；偏离等摩尔比时，OBS过量时混合体系的cmc小于C₈NE过量时混合体系的cmc，但γ_cmc相差不大。与单体系相比，OBS–C₈NE混合体系的Γt m明显增大、A_min明显变小。OBS与不同疏水链长的CnNE复配时，cmc规律为: C₈NE> C₁₀NE> C12NE，表明C_nNE疏水链长的增加能降低混合体系的cmc。通过比较CnNM和CnNE （n=8,10），发现混合体系中改变C_nNR的头基大小对混合体系的表面活性无明显影响。更多还原

【Abstract】 Cationic fluorine surfactants occupied a very important position in fluorinesurfactants’ whole productions and applications. At present, the basic rawmaterials of most widely used cationic fluorine surfactants was mainlyelectrolysis fluorination products perfluoroalkylsulfonyl fluorine (C_nF_2n+1COF),and perfluoroalkylacyl fluorine (C_nF_2n+1COF). They could respectively reactwith the N,N-dimethyl propylene amine [NH₂（CH₂）₃N（CH₃）₂] to synthesize twokinds of intermediates, CnF2n+1SO2NH（CH2）3N（CH3）2andC_nF_2n+1SO₂NH（CH₂）N（CH₃）₂. Finally two types of cationic fluorine surfactantamine salts and quaternary ammonium salts was obtained through theacidification or quaternization to introduce hydrophilic groups. Because thestarting material perfluorooctanesulfonyl fluoride costs much less, amine saltsand quaternary ammonium salts derived from C8F7SO2NH（CH2）3N（CH3）2havebecome the most widely used two kinds of cationic fluorine surfactants. Thiskind of cationic fluorine surfactants was so widely applied in industry that themajor reports were patents and publicly published research paper is not much.The research of the relationship between the structures and properties about it iswanted. In this paper cationic fluorine surfactants which wereN-[γ-（dialkylamino）alkyl]perfluorooctanesulfonamides’ derivative products (fourhydrochloride salts [C₈F₁₇SO₂NH（CH₂）_nNHR₂Cl^-] and four quaternaryammonium salts [C₈F₁₇SO₂NH（CH₂）_nN⁺R₂（CH₃）I^-]) were synthesized on thebasis of perfluoroalkylsulfonyl fluorine. These cationic fluorine surfactants’solubility in aqueous solution, surface activity, wetting abilities and foamproperties were studied through the determination of solubility, surface tension,contact angle in the paraffin’s surface, foaming force and foam stability,C₈F₁₇SO₂NH（CH₂）₂N（CH₃）₂HCl and C₈F₁₇SO₂NH（CH₂）₂N（CH₃）₃I’s poorsolubility resulting in bad surface activity, wetting ability in the paraffin’s surface and foaming ability. The results of the research showed that, these cationicfluorine surfactants’ cmc and γ_cmcwere both very low suggested its surfaceactivity were very high, in a certain range changes in the length of linker（hydrocarbon spacer） and the size of hydrophilic group, could significantlyinfluence the solubility of surfactants but insignificantly influence their surfaceactivity, their wetting ability and foaming ability appeared similar laws. Thereason may be due to perfluorineoctyl’s strong hydrophobicity, its ability andefficiency to lower the surface tension depended on the length of the fluorinecarbon chain, which overwhelming upon the influence from the length of linker（hydrocarbon spacer） and the size of hydrophilic group. Therefore, whenchoosing this kind of cationic fluorine surfactants, those which having bettersolubility, more mature synthesis technology and low cost can be preferred inindustrial application without regard to the influences of the terminal groups’subtle changes in the properties.Then anionic fluorine surfactant p-perfluorononenyloxy benzene sulfonate(C₉F₁₇OC₆H₄SO₃Na, OBS) derived from hexafluoropropene trimer was mixedwith different cationic hydrogenated surfactants C_nNR [C_nH_2n+1N（CH₃）₃Br andC_nH_2n+1N（CH₂CH₃）₃Br, n=8,10,12, abbr. C_nNM and C_nNE, respectively]. Itshowed that, after mixed with C_nNR, both the cmc and γ_cmcof OBS were greatlylowered, i.e. the efficiency was totally enhanced. Among those different molarratios between OBS and C₈NE, the molar ratio of1:1showed the best surfaceactivity, i.e. it showed the lowest cmc and γ_cmc. Meanwhile, when the molar ratiowas apart from equimolar, the cmc of OBS-excess systems were smaller thanthat of C₈NE-excess systems, however, with the γ_cmcnot significantly changed.Compared with single surfactant systems, the Γt mfor the mixtures of OBS–C₈NEwas significantly increased while the Aminwas significantly decreased. WhenOBS was mixed with C_nNE with different alkyl chain length, the sequence ofcmc for the mixtures: C₈NE> C₁₀NE> C12NE. It suggested that the increase ofhydrophobic chain length of C_nNE would induce the decrease of cmc. When theheadgroup size of C_nNR （n=8,10） was changed in the mixture, i.e., from–triethylammonium to–trimethylammonium, the surface activity for both werealmost the same. In other words, the change of the headgroup size of C_nNRshowed no significant influence on the surface activity of the mixtures.更多还原