CN107349870B - 油类火灾含氟灭火剂和液烃抑蒸剂及其制备方法与应用 - Google Patents
油类火灾含氟灭火剂和液烃抑蒸剂及其制备方法与应用 Download PDFInfo
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- CN107349870B CN107349870B CN201710482947.4A CN201710482947A CN107349870B CN 107349870 B CN107349870 B CN 107349870B CN 201710482947 A CN201710482947 A CN 201710482947A CN 107349870 B CN107349870 B CN 107349870B
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- benzyl
- surfactant
- azacyclo
- sulfonyloxy
- perfluoro
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- 239000007788 liquid Substances 0.000 title claims abstract description 54
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 41
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 41
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- 238000001704 evaporation Methods 0.000 title claims abstract description 40
- 230000008020 evaporation Effects 0.000 title claims abstract description 40
- 239000003112 inhibitor Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 20
- 239000011737 fluorine Substances 0.000 title abstract description 20
- 239000000126 substance Substances 0.000 title abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 239000006260 foam Substances 0.000 claims abstract description 41
- -1 per-fluoroalkyl sulfonyl oxy-benzyl azepine Chemical class 0.000 claims abstract description 38
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
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- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 8
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- KNYPRGRDEFRHRB-UHFFFAOYSA-N [4-(morpholin-4-ylmethyl)phenyl] 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonate hydrochloride Chemical compound Cl.FC(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(S(=O)(=O)OC1=CC=C(CN2CCOCC2)C=C1)F KNYPRGRDEFRHRB-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明公开了油类火灾含氟灭火剂和液烃抑蒸剂及其制备方法与应用，具体涉及一类全氟烷基磺酰氧基苄基氮杂环型表面活性剂及其油类火灾含氟灭火剂和液烃抑蒸剂的制备方法与应用。本发明以短全氟烷基磺酰氟为含氟前体材料，与对羟基苯甲醛进行磺酸酯化，与哌啶或吗啉发生还原胺化，与卤化氢、卤代烃和双氧水进行酸化、季铵化和氧化，得到全氟烷基磺酰氧基苄基氮杂环表面活性剂。本发明的表面活性剂不含全氟辛基类基团，表面活性高，临界胶束浓度低，将其复配得到的水成膜泡沫灭火剂水成膜铺展速度快，灭火、抗烧性能优异；将其复配得到的液烃抑蒸剂铺展速度快，能够形成具有一定强度的水膜，并且具有较强的吸湿性，能够长时间的抑制液烃的挥发。
Description
技术领域
本发明涉及油类火灾含氟灭火剂和抑蒸剂应用领域，具体涉及一类全氟烷基磺酰氧基苄基氮杂环型表面活性剂及其油类火灾含氟灭火剂和液烃抑蒸剂的制备方法与应用。
背景技术
油类物质多为闪点较低的易燃易爆液体，发生火灾时具有如下特点：(1)爆炸危险性大，油类物质遇热大量蒸发，蒸汽与空气混合达到一定比例时遇到明火即发生爆炸，在冲击波或高温高压作用下，继而发生设备、容器物理性爆炸。(2)火焰温度高、辐射热强，油气井喷发生火灾时，火焰中心温度可达1800～2100℃，火焰高度越大，辐射热越强；压力、产量越大，火场温度越高；油罐发生火灾，火焰中心温度可达1050～1400℃，罐壁温度可达1000℃以上。强热辐射易引起相邻油罐及其它可燃物燃烧，严重影响灭火战斗行动。(3)易形成大面积火灾，油类火灾蔓延速度快，油气四处流淌扩散，极易造成大面积火灾。(4)具有复燃性、复爆性，油类火灾在灭火后未切断可燃气体、易燃可燃液体的气源和液源的情况下，遇到火源或高温将产生复燃、复爆，对于灭火后的油罐、输油管道，由于壁温过高，如不继续冷却，会重新引起油品的燃烧。(5)产生沸溢、喷溅现象，油类火灾发生时，由于液面燃烧过程中释放大量的热辐射，上部油品温度升高，油品内自由水(或乳化水)粒开始下降，辐射对油品不断加热，热波不断向液面下传递，油品温度会迅速升温上升至250～3600℃，并形成一较薄的高温层，随着不断燃烧，该层逐渐下移增厚，一般油罐起火30分钟后，油罐上部油品会出现这样的高温层，水粒变成蒸汽泡，这种表面包含有油品的气泡，扩大为原来水体积的千倍以上，油泡浮到液面，造成沸溢，在油罐四周地面扩散，致使火灾扩大。总的来说，油类火灾一旦发生，普通灭火剂难以扑灭，危险性极大，将带来严重的经济损失以及人员伤亡。研发油类火灾灭火剂，提升灭火速度和抗烧等性能，对于防止油类火灾造成重大灾害具有重要意义。
对于油类火灾，目前主要使用氟蛋白泡沫灭火剂和水成膜泡沫灭火剂等进行扑救。氟蛋白泡沫灭火剂具有较好的灭火效果，低廉的价格，但其主要基料动物蛋白的水解产物中含硫化合物被水解生成无机硫化合物和含硫残基，导致氟蛋白型泡沫灭火剂存储一段时间后容易产生难闻的“恶臭”味。此外，氟蛋白泡沫灭火剂还普遍存在着生产工艺污染大、产品质量不稳定和存储期较短等问题，制约着蛋白型泡沫灭火剂的应用。水成膜泡沫灭火剂是以含氟表面活性剂为主要活性成分，具有形成水成膜和产生泡沫灭火的双重作用，对于油类火灾灭火性能突出，市场占比不断增加，是目前性能最好的油类火灾灭火剂。在发达国家油类灭火剂市场所占份额从上世纪七十年代的7.8％已上升到现在的71.3％。我国该灭火剂的生产还处于起步阶段，所占油类灭火剂的市场份额不足6％，发展空间巨大。
另外，油类火灾发生主要原因之一是油库区油类挥发和局部高浓度油类蒸汽的存在，抑制油类挥发对于预防油类火灾具有重要作用。油类液烃在运输、储存和使用过程中的大量挥发，不仅造成资源浪费、环境污染，而且有造成火灾的危险，使人们的生命财产收到严重的威胁。为了能够抑制液烃的蒸发，世界上许多发达国家和我国的有关单位均在研制液烃蒸发的抑制剂。到目前为止，尚未有成熟的液烃抑蒸剂在市场上销售。我国石油化工企业每年在生产过程中因液烃泄露而产生的安全事故比较多，给国家和人民生命财产造成的损失非常巨大。辜学勤等于2006年申请了液烃抑蒸剂发明专利(公开号：CN1858108)，主要以全氟辛酸铵、全氟羧酸钠、全氟烷基磺酸钾等含氟表面活性剂为主要活性成分，复配得到液烃抑蒸剂，该专利并没有抑制液烃蒸发效果的报道。因此开发一种应用范围广、抑制蒸发效果显著的液烃抑蒸剂，具有重要意义。
油类火灾水成膜泡沫灭火剂和油类液烃抑蒸剂主要活性成分是含氟表面活性剂，其与普通碳氢表面活性剂相比，突出的性能是“三高两憎”，即高表面活性、高耐热稳定性、高化学稳定性，即憎水又憎油。在现有水成膜泡沫灭火剂中，广泛采用的含氟表面活性剂是全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)类含氟表面活性剂。PFOA/PFOS化学性质稳定，极难分解，具有生物累积性、生物毒性和环境持久性，2009年4月被列入《关于持久性有机污染物的斯德哥尔摩公约》持久性有机污染物(POPs)受控名单限制使用，2020年最终实现PFOA/PFOS在各个行业全面禁止使用。PFOA/PFOS的禁用必然会对消防行业带来严重冲击。发展新型的环境友好型的含氟表面活性剂，替代PFOA/PFOS并应用于水成膜泡沫灭火剂，具有重要的经济和社会意义。
以含有短全氟烷基链的含氟表面活性剂，替代传统水成膜泡沫灭火剂中的PFOA/PFOS成分，不具有PFOA/PFOS持久有机污染物危害特性，不受国际斯德哥尔摩公约的使用限制，是解决水成膜泡沫灭火剂行业问题的关键。然而，由于短全氟烷基链表面活性剂的表面活性相对较差，需要进行分子设计，提高表面活性。将短全氟烷基链的全氟丁基、全氟己基磺酰氟以及六氟丙烯三聚体进行衍生，得到各种含全氟丁基或全氟己基的含氟表面活性剂，可以作为油类火灾水成膜泡沫灭火剂的关键成分，灭火性能优异(CN103432708A，CN103432959A，CN103464049A，CN103446943A，CN104264156A)。这些专利报道的含氟表面活性剂的合成路线比较长，或者后处理比较复杂，目标产物的总收率较低。
发明内容
本发明的首要目的在于克服现有技术存在的缺点与不足，提供一类短全氟烷基磺酰氧基苄基氮杂环型表面活性剂。
本发明的另一目的在于提供上述短全氟烷基磺酰氧基苄基氮杂环型表面活性剂的制备方法。以对羟基苯甲醛为起始原料，与两种含氮杂环(哌啶和吗啉)发生还原胺化得到中间体，再以短全氟烷基磺酰氟为含氟前体材料，与中间体进行磺酸酯化，再进一步地酸化、季铵化和氧化得到全氟烷基磺酰氧基苄基氮杂环表面活性剂。
本发明的再一目的在于提供上述短全氟烷基磺酰氧基苄基氮杂环表面活性剂在水成膜泡沫灭火剂和液烃抑蒸剂中的应用。
本发明的目的通过以下述技术方案实现：
一类短全氟烷基磺酰氧基苄基氮杂环表面活性剂，其结构通式为如下式Ⅰ～Ⅳ中的一种：
其中：Rf＝C4F9-、C6F13-；R为-H、-CH3等；X为对阴离子，包括Cl-、Br-或I-等，也可以方便地通过阴离子交换为其它阴离子。
优选的，所述的全氟烷基磺酰氧基苄基氮杂环表面活性剂包括N-(4-(全氟己基磺酰氧基)苄基)哌啶盐酸盐(T6-1)、N-(4-(全氟己基磺酰氧基)苄基)哌啶氢溴酸盐(T6-2)、N-甲基-N-(4-(全氟己基磺酰氧基)苄基)哌啶季铵盐(T6-3)、N-(4-(全氟己基磺酰氧基)苄基)氧化哌啶(T6-4)、N-(4-(全氟己基磺酰氧基)苄基)吗啉盐酸盐(T6-5)、N-(4-(全氟己基磺酰氧基)苄基)吗啉氢溴酸盐(T6-6)、N-甲基-N-(4-(全氟己基磺酰氧基)苄基)吗啉季铵盐(T6-7)、N-(4-(全氟己基磺酰氧基)苄基)氧化吗啉(T6-8)、N-(4-(全氟丁基磺酰氧基)苄基)哌啶盐酸盐(T4-1)、N-(4-(全氟丁基磺酰氧基)苄基)哌啶氢溴酸盐(T4-2)、N-甲基-N-(4-(全氟丁基磺酰氧基)苄基)哌啶季铵盐(T4-3)、N-(4-(全氟丁基磺酰氧基)苄基)氧化哌啶(T4-4)、N-(4-(全氟丁基磺酰氧基)苄基)吗啉盐酸盐(T4-5)、N-(4-(全氟丁基磺酰氧基)苄基)吗啉氢溴酸盐(T4-6)、N-甲基-N-(4-(全氟丁基磺酰氧)苄基)吗啉季铵盐(T4-7)、N-(4-(全氟丁基磺酰氧基)苄基)氧化吗啉(T4-8)，结构式分别如具体实施方式中T6-1～T6-8和T4-1～T4-8所示。
上述短全氟烷基磺酰氧基苄基阳离子表面活性剂的制备方法，包括如下步骤：
(1)对羟基苯甲醛在缚酸剂存在下，于溶剂中与全氟烷基磺酰氟发生亲核取代反应，得到全氟烷基磺酰氧基苯甲醛中间体。
(2)全氟烷基磺酰氧基苯甲醛中间体在还原剂的存在下，分别于溶剂中与哌啶或吗啉发生还原胺化反应，得到全氟烷基磺酰氧基苄基哌啶或全氟烷基磺酰氧基苄基吗啉中间体。
(3)步骤(2)得到的中间体于溶剂中与卤化氢或卤代烃或双氧水反应得到全氟烷基磺酰氧基苄基氮杂环表面活性剂。
步骤(1)中所述的缚酸剂优选为碳酸钾，所述的溶剂优选为乙腈，所述的全氟烷基磺酰氟优选为全氟己基磺酰氟或全氟丁基磺酰氟。
步骤(2)中所述的还原剂优选为硼氢化钠，所述的溶剂优选为甲醇。
步骤(3)中所述的卤化氢优选为盐酸或氢溴酸，所述的卤代烃优选为碘甲烷，所述的溶剂优选为乙腈、乙醇或丙酮。
上述短全氟烷基磺酰氧基苄基氮杂环表面活性剂，可以作为水成膜泡沫灭火剂和水成膜液烃抑蒸剂的主要活性成分，用于配制为水成膜泡沫灭火剂和水成膜液烃抑蒸剂，在扑灭油类火灾和抑制油类液烃蒸发损失以及火灾预防中有重要应用。上述短全氟烷基磺酰氧基苄基氮杂环表面活性剂通过与碳氢表面活性剂、成膜剂、起泡剂、稳泡剂、防冻剂等助剂进行复配，得到油类水成膜泡沫灭火剂和液烃抑蒸剂。其中油类水成膜泡沫灭火剂具有优异的灭火性能；液烃抑蒸剂具有优异的抑制油类液烃蒸发损失的性能。
一种水成膜泡沫灭火剂或液烃抑蒸剂，包含上述全氟烷基磺酰氧基苄基氮杂环表面活性剂。
本发明相对于现有技术具有如下优点和效果：
本发明的全氟烷基磺酰氧基苄基氮杂环表面活性剂不含有持久有机污染物特征的全氟辛基类基团，具有优异的表面活性；部分阳离子和氧化铵表面活性剂最小表面张力达到18mN/m以下，临界胶束浓度(CMC)值在1.0×10-3mol/L左右。与商品化的全氟辛基磺酸钠(最小表面张力22mN/m，CMC值为(8.5×10-3mol/L)(J.Phys.Chem.C 2008,112,16850)、十二烷基磺酸钠(最小表面张力34mN/m，CMC值为8.7×10-3mol/L)(J.ColloidInterf.Sci.2012,370,102)等相比，具有显著的优势。并且本发明地合成路线短，产率高，原料廉价易得，具有很高的工业应用价值。
将本发明的短全氟烷基磺酰氧基苄基氮杂环表面活性剂进行复配，得到水成膜泡沫灭火剂和液烃抑蒸剂，具有水成膜铺展速度快，灭火性能优异，持久抑制液烃蒸发的特点。
附图说明
图1是短全氟烷基磺酰氧基苄基氮杂环表面活性剂的结构图。
图2是中间体(M6-1～3和M4-1～3)的合成路线图。
图3是全氟烷基磺酰氧基苄基氮杂环表面活性剂(T6-1～8和T4-1～8)的合成路线图。
图4是水成膜泡沫灭火剂灭火性能测试的现场图。消防灭火实验(GB15308-2006)实验结果：灭火时间46秒，A级达标要求灭火时间1分钟。
图5是水成膜泡沫灭火剂抗烧性能测试现场图。抗烧实验(GB15308-2006)实验结果：抗烧时间11分10秒，A级达标要求抗烧时间10分钟。
图6是液烃抑蒸剂水膜形成图。
图7是液烃抑蒸剂性能测试(环己烷蒸发损失量比较)结果图，环境温度20℃，湿度40％。
具体实施方式
下面结合实施例及附图对本发明做进一步详细的描述，但本发明的实施方式不限于此。
本发明短全氟烷基磺酰氧基苄基氮杂环表面活性剂的结构图如图1所示。其中，Rf＝C4F9-、C6F13-；R为-H、-CH3等；X为对阴离子，包括Cl-、Br-或I-等，也可以方便地通过阴离子交换为其它阴离子。
实施例1～3涉及中间体(M6-1～3和M4-1～3)制备的具体实施方式，合成路线如图2所示。
实施例1中间体(M6-1或M4-1)的制备
在干燥的250mL烧瓶中加入12.2g(0.1mol)对羟基苯甲醛，用150mL乙腈溶解，搅拌下加入缚酸剂碳酸钾27.6g(0.2mol)，回流半小时，然后缓慢滴加含氟前体原料全氟己基磺酰氟48.2g(0.12mol)或者全氟丁基磺酰氟36.2g(0.12mol)，TLC监测反应终点。向反应液中加入100mL乙酸乙酯，用饱和氯化钠溶液洗3次，有机层用无水硫酸钠干燥并低温结晶，过滤得到白色固体中间体全氟己基磺酰氧基苯甲醛(M6-1)47.9g(收率为95％)或白色固体中间体全氟丁基磺酰氧基苯甲醛(M4-1)39.2g(收率为97％)。
1H NMR(400MHz,CDCl3):δ10.05(s,1H,-CHO),8.01(d,J＝8.0Hz,2H,phH),7.48(d,J＝8.0Hz,2H,phH)；
19F NMR(376MHz,CDCl3):δ-81.43(3F),-109.07(2F),-120.53(2F),-122.29(2F),-123.55(2F),-126.76(2F)；
MS(EI):504.19(M+)(计算值:504.22)。
1H NMR(600MHz,DMSO):δ10.08(s,1H,-CHO),8.13(d,J＝8.0Hz,2H,phH),7.75(d,J＝8.0Hz,2H,phH)；
19F NMR(376MHz,DMSO):δ-82.01(3F),-112.34(2F),-121.84(2F),-126.76(2F)；
MS(EI):404.09(M+)(计算值:404.20)。
实施例2中间体(M6-2或M4-2)的制备
在干燥的250mL烧瓶中加入10g(0.02mol)中间体M6-1或8g(0.02mol)中间体M4-1、100mL无水甲醇，再加入1.7g(0.02mol)哌啶，室温下搅拌2h。然后分批加入硼氢化钠0.76g(0.02mol)，继续反应10min，TLC监测反应终点。向反应液中加入100mL乙酸乙酯，用饱和氯化钠溶液洗三次，有机层用无水硫酸钠干燥并低温结晶，得到白色固体中间体全氟己基磺酰氧基苄基哌啶(M6-2)10.8g(收率为94％)或得到无色液体中间体全氟丁基磺酰氧基苄基哌啶(M4-2)8.8g(收率为93％)。
1H NMR(400MHz,CDCl3):δ7.40(d,J＝8.0Hz,2H,phH),7.21(d,J＝8.0Hz,2H,phH),3.46(s,2H,phCH2),2.36(t,4H,-CH2-),1.57(m,4H,-CH2-),1.44(m,2H,-CH2-)；
19F NMR(376MHz,CDCl3):δ-82.08(3F),-110.07(2F),-121.00(2F),-122.60(2F),-123.66(2F),-127.12(2F)；
MS(EI):573.12(M+)(计算值:573.37)。
1H NMR(400MHz,CDCl3):δ7.41(d,J＝8.0Hz,2H,phH),7.22(d,J＝8.0Hz,2H,phH),3.48(s,2H,phCH2),2.37(s,4H,-CH2-),1.58(m,4H,-CH2-),1.45(m,2H,-CH2-)；
19F NMR(376MHz,CDCl3):δ-80.62(3F),-109.07(2F),-120.84(2F),-125.76(2F)；
MS(EI):473.01(M+)(计算值:473.35)。
实施例3中间体(M6-3或M4-3)的制备
在干燥的250mL烧瓶中加入10g(0.02mol)中间体M6-1或8g(0.02mol)中间体M4-1、100mL无水甲醇，再加入1.74g(0.02mol)吗啉，室温下搅拌2h。然后分批加入硼氢化钠0.76g(0.02mol)，继续反应10min，TLC监测反应终点。向反应液中加入100mL乙酸乙酯，用饱和氯化钠溶液洗三次，有机层用无水硫酸钠干燥并低温结晶，得到白色固体中间体全氟己基磺酰氧基苄基吗啉(M6-3)11.0g(收率为96％)或白色固体中间体全氟丁基磺酰氧基苄基吗啉(M4-3)8.7g(收率为92％)。
1H NMR(400MHz,CDCl3):δ7.43(d,J＝8.0Hz,2H,phH),7.23(d,J＝8.0Hz,2H,phH),3.72(t,J＝4.0Hz,4H,-CH2-),3.51(s,2H,phCH2),2.44(t,J＝4.0Hz,4H,-CH2-)；
19F NMR(376MHz,CDCl3):δ-81.94(3F),-109.91(2F),-120.86(2F),-122.47(2F),-123.53(2F),-126.98(2F)；
MS(EI):575.15(M+)(计算值:575.35)。
1H NMR(400MHz,CDCl3):δ7.43(d,J＝8.0Hz,2H,phH),7.23(d,J＝8.0Hz,2H,phH),3.72(t,J＝4.0Hz,4H,-CH2-),3.51(s,2H,phCH2),2.44(t,J＝4.0Hz,4H,-CH2-)；
19F NMR(376MHz,CDCl3):δ-80.69(3F),-109.03(2F),-120.93(2F),-125.87(2F)；
MS(EI):475.01(M+)(计算值:475.33)。
实施例4～6涉及目标产物全氟烷基磺酰氧基苄基氮杂环表面活性剂(T6-1～8和T4-1～8)制备的具体实施方式，合成路线如图3所示。
实施例4目标产物T6-1、T6-2、T6-5、T6-6、T4-1、T4-2、T4-5、T4-6的制备
在干燥的50mL烧瓶中加入0.0035mol的中间体M6-2、M6-3、M4-2或M4-3；加入0.007mol的37％HCl溶液或40％HBr溶液；加入20mL丙酮，常温下反应过夜，抽滤。所得固体用乙醚洗涤，最后得到目标化合物：T6-1，2.2g，收率为97％；T6-2，2.24g，收率为98％；T6-5，2.01g，收率为94％；T6-6，2.09g，收率为91％；T4-1，1.7g，收率为96％；T4-2，1.88g，收率为97％；T4-5，1.7g，收率为95％；T4-6，1.77g，收率为91％。
1H NMR(400MHz,DMSO):δ11.29(s,1H,-NH),7.89(d,J＝8.0Hz,2H,phH),7.60(d,J＝8.0Hz,2H,phH),4.31(d,J＝8.0Hz,2H,phCH2),3.23(d,J＝12.0Hz,2H,-CH2-),1.80(m,5H,-CH2-),1.35(q,J＝12.0Hz,1H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.42(3F),-109.19(2F),-120.07(2F),-121.63(2F),-122.64(2F),-125.95(2F)；
HRMS:574.0746([M-Cl]+)(计算值:574.0716)。
1H NMR(400MHz,DMSO):δ9.63(s,1H,-NH),7.79(d,J＝8.0Hz,2H,phH),7.64(d,J＝8.0Hz,2H,phH),4.39(d,J＝8.0Hz,2H,phCH2),3.31(t,J＝12Hz,2H,-CH2-),2.93(t,J＝12Hz,2H,-CH2-),1.82(m,2H,-CH2-),1.70(m,2H,-CH2-),1.37(q,J＝12.0Hz,1H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.45(3F),-109.20(2F),-120.09(2F),-121.65(2F),-122.66(2F),-125.97(2F)；
HRMS:574.0744([M-Br]+)(计算值:574.0716)。
1H NMR(400MHz,DMSO):δ11.13(s,1H,-NH),7.81(d,J＝8.0Hz,2H),7.64(d,J＝8.0Hz,2H),4.39(s,2H,phCH2),3.94(d,J＝12.0Hz,2H,-CH2-),3.76(t,J＝12.0Hz,2H,-CH2-),3.22(d,J＝12.0Hz,2H,-CH2-),3.10(d,J＝12.0Hz,2H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.39(3F),-109.16(2F),-120.06(2F),-121.61(2F),-122.62(2F),-125.92(2F)；
HRMS:576.0540([M-Cl]+)(计算值:576.0509)。
1H NMR(400MHz,DMSO):δ9.95(s,1H,-NH),7.74(d,J＝8.0Hz,2H,phH),7.66(d,J＝8.0Hz,2H,phH),4.44(s,2H,phCH2),3.97(d,J＝12.0Hz,2H,-CH2-),3.65(t,J＝12.0Hz,2H,-CH2-),3.28(d,J＝12.0Hz,2H,-CH2-),3.15(d,J＝12.0Hz,2H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.41(3F),-109.16(2F),-120.07(2F),-121.62(2F),-122.63(2F),-125.93(2F)；
HRMS:576.0538([M-Br]+)(计算值:576.0514)。
1H NMR(400MHz,DMSO):δ11.28(s,1H,-NH),7.90(d,J＝8.0Hz,2H,phH),7.61(d,J＝8.0Hz,2H,phH),4.33(d,J＝4Hz,2H,phCH2),3.24(d,J＝12Hz,2H,-CH2-),2.85(q,J＝8.0Hz,2H,-CH2-),1.79(m,5H,-CH2-),1.35(q,J＝12.0Hz,1H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.22(3F),-109.27(2F),-120.89(2F),-125.55(2F).
HRMS:474.0787([M-Cl]+)(计算值:474.0780)。
1H NMR(400MHz,DMSO):δ9.64(s,1H,-NH),7.80(d,J＝8.0Hz,2H,phH),7.64(d,J＝8.0Hz,2H,phH),4.40(d,J＝4.0Hz,2H,phCH2),3.33(d,J＝12.0Hz,2H,-CH2-),2.93(q,J＝8.0Hz,2H,-CH2-),1.74(m,3H,-CH2-),1.38(q,J＝12.0Hz,1H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.13(3F),-109.18(2F),-120.81(2F),-125.49(2F).
HRMS:474.0783([M-Br]+)(计算值:474.0780)。
1H NMR(400MHz,DMSO):δ12.02(s,1H,-NH),7.91(d,J＝8.0Hz,2H),7.62(d,J＝8.0Hz,2H),4.42(d,J＝4.0Hz,2H,phCH2),3.93(d,J＝12.0Hz,2H,-CH2-),3.87(t,J＝12.0Hz,2H,-CH2-),3.20(d,J＝8.0Hz,2H,-CH2-),3.11(dd,J＝8.0Hz,8.0Hz,2H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.15(3F),-109.19(2F),-120.84(2F),-125.50(2F).
HRMS:476.0572([M-Cl]+)(计算值:476.053)。
1H NMR(400MHz,DMSO):δ10.07(s,1H,-NH),7.77(d,J＝8.0Hz,2H,phH),7.67(d,J＝8.0Hz,2H,phH),4.46(d,J＝4.0Hz,2H,phCH2),3.97(d,J＝16.0Hz,2H,-CH2-),3.68(t,J＝12.0Hz,2H,-CH2-),3.29(d,J＝12.0Hz,2H,-CH2-),3.16(dd,J＝8.0,8.0Hz,2H,,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.12(3F),-109.13(2F),-120.74(2F),-125.54(2F).
HRMS:476.0572([M-Br]+)(计算值:476.0573)。
实施例5目标产物T6-3、T6-7、T4-3、T4-7的制备
在干燥的50mL烧瓶中加入0.0035mol的中间体M6-2、M6-3、M4-2或M4-3；加入1.0g(0.007mol)CH3I和20mL乙腈，回流过夜，抽滤。所得固体用乙醚洗涤，最后得到目标化合物：T6-3，2.38g，收率为95％；T6-7，2.72g，收率为92％；T4-3，2.0g，收率为93％；T4-7，1.99g，收率为92％。
1H NMR(400MHz,DMSO):δ7.75(d,J＝8.0Hz,2H,phH),7.68(d,J＝8.0Hz,2H,phH),4.64(s,2H,phCH2),2.93(s,3H,-NCH3),2.51(t,J＝4.0Hz,4H,-CH2-),1.87(m,4H,-CH2-),1.56(m,2H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.41(3F),-109.14(2F),-120.05(2F),-121.61(2F),-122.63(2F),-125.93(2F)；
HRMS:588.0900([M-I]+)(计算值:588.0873)。
1H NMR(400MHz,DMSO):δ7.77(d,J＝8.0Hz,2H,phH),7.69(d,J＝8.0Hz,2H,phH),4.73(s,2H,phCH2),3.97(t,J＝8.0Hz,4H,-CH2-),3.54(t,J＝12.0Hz,2H,-CH2-),3.30(t,J＝12.0Hz,2H,-CH2-),3.07(s,3H,-NCH3)；
19F NMR(376MHz,DMSO):δ-80.73(3F),-109.45(2F),-120.37(2F),-121.93(2F),-122.96(2F),-126.24(2F)；
HRMS:590.0698([M-I]+)(计算值:590.0665)。
1H NMR(400MHz,DMSO):δ7.79(d,J＝8.0Hz,2H,phH),7.68(d,J＝8.0Hz,2H,phH),4.70(s,2H,phCH2),3.41(m,2H,-CH2-),3.32(m,2H,-CH2-),2.96(s,3H,-NCH3),1.88(m,4H,-CH2-),1.57(m,2H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.18(3F),-109.28(2F),-120.84(2F),-125.59(2F).
HRMS:488.0937([M-I]+)(计算值:488.0936)。
1H NMR(400MHz,DMSO):δ7.79(d,J＝8.0Hz,2H,phH),7.69(d,J＝8.0Hz,2H,phH),4.76(s,2H,phCH2),3.98(s,2H,-CH2-),3.55(s,2H,-CH2-),3.31(s,2H,-CH2-),3.08(s,2H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.15(3F),-109.21(2F),-120.82(2F),-125.57(2F).
HRMS:490.0734([M-I]+)(计算值:490.0729)。
实施例6目标产物T6-4、T6-8、T4-4、T4-8的制备
在干燥的50mL烧瓶中加入0.0035mol的中间体M6-2、M6-3、M4-2或M4-3；加入0.8g(0.007mol)30％H2O2水溶液和20mL乙醇，回流过夜，脱溶。所得固体用乙醚洗涤，最后得到目标化合物：T6-4，1.98g，收率为96％；T6-8，2.0g，收率为97％；T4-4，1.6g，收率为93％；T4-8，1.67g，收率为97％。
1H NMR(400MHz,DMSO):δ7.74(d,J＝8.0Hz,2H,phH),7.47(d,J＝8.0Hz,2H,phH),4.44(s,2H,phCH2),3.27(t,J＝12.0Hz,2H,-CH2-),2.94(t,J＝12.0Hz,2H,-CH2-),1.99(m,2H,-CH2-),1.56(m,2H,-CH2-),1.30(m,2H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.58(3F),-109.36(2F),-114.95(2F),-120.80(2F),-122.94(2F),-126.11(2F)；
HRMS:590.0693([M+H]+)(计算值:590.0671)。
1H NMR(400MHz,DMSO):δ7.77(d,J＝8.0Hz,2H,phH),7.52(d,J＝8.0Hz,2H,phH),4.45(s,2H,phCH2),4.05(t,J＝12.0Hz,2H,-CH2-),3.68(d,J＝8.0Hz,2H,-CH2-),3.49(t,J＝8.0Hz,2H,-CH2-),2.71(d,J＝12.0Hz,2H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.45(3F),-109.26(2F),-120.11(2F),-121.66(2F),-122.67(2F),-125.97(2F)；
HRMS:592.0492([M+H]+)(计算值:592.0463)。
1H NMR(400MHz,DMSO):δ7.74(d,J＝8.0Hz,2H,phH),7.47(d,J＝8.0Hz,2H,phH),4.44(s,2H,phCH2),3.27(t,J＝12.0Hz,2H,-CH2-),2.94(t,J＝12.0Hz,2H,-CH2-),1.99(m,2H,-CH2-),1.56(m,2H,-CH2-),1.30(m,2H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.33(3F),-109.16(2F),-120.82(2F),-125.55(2F).
HRMS:490.0734([M+H]+)(计算值:490.0735)。
1H NMR(400MHz,DMSO):δ7.79(d,J＝12.0Hz,2H,phH),7.52(d,J＝8.0Hz,2H,phH),4.44(s,2H,phCH2),4.06(t,J＝12.0Hz,2H,-CH2-),3.67(d,J＝12.0Hz,2H,-CH2-),3.48(t,J＝12.0Hz,2H,-CH2-),2.69(d,J＝12.0Hz,2H,-CH2-)；
19F NMR(376MHz,DMSO):δ-80.06(3F),-109.06(2F),-120.72(2F),-125.45(2F).
HRMS:492.0520([M+H]+)(计算值:492.0527)。
实施例7表面张力和临界胶束浓度(CMC)的测试
取一定量的上述全氟烷基磺酰氧基苄基氮杂环表面活性剂，用蒸馏水分别配成以下浓度梯度(单位：mmol/L)的溶液：0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.2、1.4、1.6、1.8、2.0、2.2、2.4、2.6、2.8、3.0，用OCA 20接触角测量仪进行表面张力的测定(悬滴法)，以确定其表面张力。在25℃所测得实验数据如表1所示。
表1.全氟烷基磺酰氧基苄基氮杂环表面活性剂最低表面张力和临界胶束浓度
实施例8水成膜泡沫灭火剂的配制
水成膜泡沫灭火剂的配制参照文献方法进行(Fire Sci.Techn.30(2011),825-828)，用实施例4～6制备的全氟烷基磺酰氧基氮杂环离子表面活性剂(T6-1～8和T4-1～8)配制灭火剂，添加的助剂包括：助表面活性剂CAB-35和十二烷基硫酸钠；增稠剂黄原胶；助溶剂尿素；防冻剂乙二醇、二乙二醇、丙二醇、二丙二醇或己二醇；发泡助剂乙二醇单丁醚、二乙二醇单丁醚、丙二醇单丁醚或二丙二醇单丁醚；耐腐剂苯并三氮唑；螯合剂EDTA、柠檬酸钠或酒石酸钠等。典型的含氟表面活性剂T6-2水成膜泡沫灭火剂的复配方案如表2所示。
表2.T6-2水成膜泡沫灭火剂典型的复配参数
| 6％水成膜泡沫灭火剂浓缩液 | 100g |
| 全氟烷基磺酰氧基苄基氮杂环表面活性剂 | 0.5g |
| 两性表面活性剂(CAB-35) | 1.5g |
| 十二烷基硫酸钠 | 1g |
| 黄原胶 | 1g |
| 尿素 | 30g |
| 防冻剂 | 1.5g |
| 发泡助剂 | 3g |
| 防腐添加剂 | 0.1g |
| 烷基糖苷 | 2g |
| 耐腐剂 | 0.5g |
| 螯合剂 | 0.5g |
| 水 | 58.4g |
实施例9水成膜泡沫灭火剂技术指标和性能
按照实施例8配制的泡沫灭火剂，参照文献(Chemical Research andApplication 20(2008)569-572)方法进行实验室灭火性能测试初筛。灭火试验步骤是：于500mL烧杯中加入100mL环己烷，点燃后燃烧5分钟；将表2配制的浓溶液按照质量比6:100用水稀释，振荡1分钟发泡，取10mL泡沫灭火剂加入正在燃烧环己烷的烧杯中，观察火熄灭情况。对于优选的灭火剂，参照GB15308-2006对泡沫灭火剂的技术指标进行测试。例如，由T6-2复配的泡沫灭火剂检测的性能指标如表3所示，灭火现场图片如图4所示，抗烧现场图片如图5所示。灭火试验结果表明，本发明获得的泡沫灭火剂具有优异的水成膜铺展速度和灭火、抗烧性能。
表3.T6-2复配水成膜泡沫灭火剂的性能测试结果
实施例10液烃抑蒸剂的配制
液烃抑蒸剂的配制无文献方法报道。本发明参照水成膜泡沫灭火剂的配制方案，用实施例4～6制备的全氟烷基磺酰氧基氮杂环离子表面活性剂(T6-1～8和T4-1～8)，配制液烃抑蒸剂。添加的助剂包括：助表面活性剂CAB-35，十二烷基硫酸钠，水溶性咪唑啉，烷基糖苷；成膜剂明胶；水膜稳定剂木糖醇；粘度调整剂乙二醇单丁醚、二乙二醇单丁醚、丙二醇单丁醚或二丙二醇单丁醚。典型的含氟表面活性剂T6-2液烃抑蒸剂配方案如表4所示。
表4.T6-2液烃抑蒸剂典型的复配参数
实施例11液烃抑蒸剂的性能
按照表4配制的含有任一全氟烷基磺酰氧基苄基氮杂环表面活性剂(T6-1～8和T4-1～8)的液烃抑蒸剂，参照文献(Journal of Chemical Engineering of ChineseUniversities 2004,18(3),389-393)进行抑蒸性能测试。抑蒸试验是利用减重法测量对环己烷挥发的抑制效果：在直径为9cm的表面皿上放入环己烷10g，然后缓慢从液面中央滴加一滴试验液，试验液很快在环己烷液面上铺展成膜，然后把表面皿放置在电子天平上，室温下每30min记录一次数据，其表界面张力以及铺展系数如表5所示，液烃抑蒸剂水膜形成及抑蒸性能如图6和图7所示。表界面张力数据显示此复配的试验液具有优良的表面活性，容易吸附在环己烷液面形成单分子层，铺展系数说明试验液可以快速在环己烷上铺展，且铺展之后形成一层可见的水膜，此水膜具有一定的强度，并具有一定的吸湿性，可以长时间抑制液烃的挥发。
表5.T6-2液烃抑蒸剂表界面张力及铺展系数
| 表面张力(mN/m) | 界面张力(mN/m) | 铺展系数 |
| 16.91 | 0.65 | 8 |
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一类短全氟烷基磺酰氧基苄基氮杂环表面活性剂，其特征在于：结构通式为如下式Ⅰ～Ⅳ中的一种：
其中：Rf＝C4F9-、C6F13-；R为-H、-CH3；X为Cl-、Br-或I-。
2.根据权利要求1所述的短全氟烷基磺酰氧基苄基氮杂环表面活性剂，其特征在于：包括N-(4-(全氟己基磺酰氧基)苄基)哌啶盐酸盐、N-(4-(全氟己基磺酰氧基)苄基)哌啶氢溴酸盐、N-甲基-N-(4-(全氟己基磺酰氧基)苄基)哌啶季铵盐、N-(4-(全氟己基磺酰氧基)苄基)氧化哌啶、N-(4-(全氟己基磺酰氧基)苄基)吗啉盐酸盐、N-(4-(全氟己基磺酰氧基)苄基)吗啉氢溴酸盐、N-甲基-N-(4-(全氟己基磺酰氧基)苄基)吗啉季铵盐、N-(4-(全氟己基磺酰氧基)苄基)氧化吗啉、N-(4-(全氟丁基磺酰氧基)苄基)哌啶盐酸盐、N-(4-(全氟丁基磺酰氧基)苄基)哌啶氢溴酸盐、N-甲基-N-(4-(全氟丁基磺酰氧基)苄基)哌啶季铵盐、N-(4-(全氟丁基磺酰氧基)苄基)氧化哌啶、N-(4-(全氟丁基磺酰氧基)苄基)吗啉盐酸盐、N-(4-(全氟丁基磺酰氧基)苄基)吗啉氢溴酸盐、N-甲基-N-(4-(全氟丁基磺酰氧)苄基)吗啉季铵盐、N-(4-(全氟丁基磺酰氧基)苄基)氧化吗啉。
3.权利要求1或2所述的短全氟烷基磺酰氧基苄基氮杂环表面活性剂的制备方法，其特征在于：包括如下步骤：
(1)对羟基苯甲醛在缚酸剂存在下，于溶剂中与全氟烷基磺酰氟发生亲核取代反应，得到全氟烷基磺酰氧基苯甲醛中间体；
(2)全氟烷基磺酰氧基苯甲醛中间体在还原剂的存在下，分别于溶剂中与哌啶或吗啉发生还原胺化反应，得到全氟烷基磺酰氧基苄基哌啶或全氟烷基磺酰氧基苄基吗啉中间体；
(3)步骤(2)得到的中间体于溶剂中与卤化氢或卤代烃或双氧水反应得到全氟烷基磺酰氧基苄基氮杂环表面活性剂。
4.根据权利要求3所述的短全氟烷基磺酰氧基苄基氮杂环表面活性剂的制备方法，其特征在于：步骤(1)中所述的缚酸剂为碳酸钾，所述的溶剂为乙腈，所述的全氟烷基磺酰氟为全氟己基磺酰氟或全氟丁基磺酰氟。
5.根据权利要求3所述的短全氟烷基磺酰氧基苄基氮杂环表面活性剂的制备方法，其特征在于：步骤(2)中所述的还原剂为硼氢化钠，所述的溶剂为甲醇。
6.根据权利要求3所述的短全氟烷基磺酰氧基苄基氮杂环表面活性剂的制备方法，其特征在于：步骤(3)中所述的卤化氢为盐酸或氢溴酸，所述的卤代烃为碘甲烷，所述的溶剂为乙腈、乙醇或丙酮。
7.权利要求1或2所述的短全氟烷基磺酰氧基苄基氮杂环表面活性剂在水成膜泡沫灭火剂中的应用。
8.一种水成膜泡沫灭火剂，其特征在于：包含权利要求1或2所述的短全氟烷基磺酰氧基苄基氮杂环表面活性剂。
9.权利要求1或2所述的短全氟烷基磺酰氧基苄基氮杂环表面活性剂在液烃抑蒸剂中的应用。
10.一种液烃抑蒸剂，其特征在于：包含权利要求1或2所述的短全氟烷基磺酰氧基苄基氮杂环表面活性剂。
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