CN109173922B - 一种磺酸盐型氟硅阴离子表面活性剂及其制备方法 - Google Patents
一种磺酸盐型氟硅阴离子表面活性剂及其制备方法 Download PDFInfo
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- 239000003945 anionic surfactant Substances 0.000 title claims abstract description 42
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title claims abstract description 36
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims abstract description 31
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- 238000000034 method Methods 0.000 claims abstract description 12
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- 239000000126 substance Substances 0.000 claims description 41
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- 239000001110 calcium chloride Substances 0.000 claims description 4
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052990 silicon hydride Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 241001465754 Metazoa Species 0.000 description 2
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
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- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种磺酸盐型氟硅阴离子表面活性剂及其制备方法,该制备方法以易降解、低毒含氟化合物C6F13SO2F为起点,首先与N‑甲基烯丙胺进行双分子亲核取代(SN2)反应制备NSF6,然后NSF6依次与含氢硅油(PMHS)和烯丙基缩水甘油醚(AGE)进行硅氢化反应,最后再与NaHSO3进行磺化反应合成磺酸盐型氟硅阴离子表面活性剂PSF6AS,并测定了其表面张力和临界胶束浓度。该表面活性剂与传统氟碳表面活性剂相比,具有较好的水溶性及生物降解性;并且为我国磺酸盐型氟硅阴离子表面活性剂的开发和应用提供一个新的研究方法和思路。
Description
技术领域
本发明涉及一种磺酸盐型氟硅阴离子表面活性剂及其制备方法。
背景技术
氟硅阴离子表面活性剂是以Si-O-Si为主链,在侧链或两端接枝含氟疏水基团和磺酸基或羧基等亲水基团的一种新型表面活性剂,根据亲水基团结构的不同,可分为磺酸型、羧酸型、硫酸酯型和磷酸酯型等四种类型,具有较好的去污、发泡、润湿、乳化和分散等特性。氟硅阴离子表面活性剂兼有氟碳表面活性剂和有机硅表面活性剂的优点,与传统表面活性剂相比具有其独特的性能,已成为材料领域的研究热点,并广泛应用于纺织、油田、建材、橡胶及航天航空等领域。
Salvatore率先提出由环氧化法来制备脂肪醇醚磺酸盐类表面活性剂的方法,即将脂肪醇醚与环氧氯丙烷反应生成末端连有环氧烷基的化合物,然后再与亚硫酸钠和亚硫酸氢钠进行磺化反应,从而制得醇醚羟丙基磺酸盐型阴离子表面活性剂。张乐以八甲基环四硅氧烷、1,3,5-三甲基-1,3,5-三(3,3,3-三氟丙基)环三硅氧烷、四甲基二硅氧烷、烯丙基环氧基聚醚、KHSO3为原料,经开环聚合、硅氢加成和磺化反应制得一种磺酸盐型阴离子氟硅表面活性剂FPESS,结果表明,FPESS的临界胶束质量浓度(cmc)为2.0g/L,表面张力(γcmc)为21.01mN/m,且具有较强的耐酸碱盐化学稳定性。
全氟辛烷磺酸和全氟辛酸因成本低廉、工艺成熟,故被通常作为合成含氟表面活性剂的起始原料,但全氟辛酸和全氟辛烷磺酸具有良好的热稳定性和化学稳定性,因而在环境中很难水解、光解或微生物降解,并通过食物链进入人和动物的组织而累计在生物体内,对环境和人类健康造成很大的危害,是一类新型持久性有机污染物,各国纷纷采取各种措施禁止或者限制该类产品的使用;鉴于氟硅表面活性剂优异的物理化学性能,故而寻找低毒高效的氟硅表面活性剂来代替PFOA/PFOS类氟碳表面活性剂,业已成为国内外共同研究的热点课题之一。
相关文献报道已表明,可以通过改变氟碳链结构的方法,即通过缩短氟碳链的“有效长度”或者在氟碳链中插入N、O等杂原子的方法,使含氟表面活性剂不仅仍具有较高的表面活性,而且对环境的危害也大大降低。
发明内容
本发明其目的就在于提供一种磺酸盐型氟硅阴离子表面活性剂及其制备方法,解决了现有全氟辛烷磺酸和全氟辛酸存在在环境中很难水解、光解或微生物降解,并通过食物链进入人和动物的组织而累计在生物体内,对环境和人类健康造成很大危害的问题。
为实现上述目的而采取的技术方案是,一种磺酸盐型氟硅阴离子表面活性剂,该化合物的化学结构式为:
其中Rf为:C6F13SO2;Me为CH3;x和y均为正整数。
所述的磺酸盐型氟硅阴离子表面活性剂在水溶液中的临界胶束浓度为0.10~0.18g/L,在水溶液中的最低表面张力为32.8~37.5mN/m。
一种磺酸盐型氟硅阴离子表面活性剂的制备方法,该制备方法包括以下步骤:
(1)在装有搅拌器、温度计、滴液漏斗和回流冷凝管的50mL四口烧瓶中加入20mL乙酸乙酯和1.78gN-甲基烯丙胺,所述回流冷凝管上装有无水CaCl2干燥管,所述1.78g N-甲基烯丙胺的浓度为0.025mol,室温下逐渐滴加4.02g全氟己基磺酰氟,所述4.02g全氟己基磺酰氟的浓度为0.01mol,控制30min滴加完毕,在40℃下继续搅拌反应2h;停止反应后,将反应液倒入100mL水中,分层后取下层淡黄色液体,依次用50mL 5%HCl水溶液、30mL饱和NaCO3水溶液和2×30mL水进行洗涤,无水硫酸钠干燥,得淡黄色透明液体,黄色透明液体为C6F13SO2N(CH3)CH2CH=CH2;
(2)将2.5g高含氢硅油、0.54g C6F13SO2N(CH3)CH2CH=CH2和甲苯20mL加入100mL的三口圆底烧瓶中,然后加入浓度为16.123g/L的Karstedt催化剂,接上冷凝装置和温度计,磁力搅拌,油浴升温加热至90℃;当硅氢化转化率达到3%时,加入4.54g烯丙基缩水甘油醚,继续反应至硅氢化反应转化率基本恒定为止,
反应体系中高含氢硅油中硅氢物质的量为40.85mmol,C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量分别为1.23mmol和39.62mmol,三者物质的量比例为高含氢硅油中硅氢:C6F13SO2N(CH3)CH2CH=CH2中碳碳双键:烯丙基缩水甘油醚中碳碳双键=10:0.3:9.7;
(3)反应结束后将反应物在35℃真空旋转蒸发以除去甲苯和易挥发组分,然后在真空干燥箱中,50℃真空干燥4h,以进一步除去残留的甲苯和和易挥发组分,得到高含氢硅油中硅氢、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量比例为10:0.3:9.7的硅氢化产物,为淡黄色粘稠液体;
(4)取硅氢化产物2.0g、乙醇15mL、水5mL加入100mL单口圆底烧瓶中,然后加入NaHSO3 0.6g,接上冷凝回流装置,磁力搅拌,油浴升温加热至80℃,回流反应24h,有白色不溶物生成;减压抽滤除去不溶物,在35℃真空旋转蒸发以除去乙醇和水,得到淡黄色粘稠液体,即为氟硅阴离子表面活性剂。
在保持高含氢硅油2.5g不变的条件下,使高含氢硅油中硅氢、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量三者的比例还可以分别为10:0.6:9.4、10:0.9:9.1和10:1.2:8.8。
有益效果
与现有技术相比本发明具有以下优点。
本发明的优点是,作为一种新的氟硅表面活性剂丰富了氟硅表面活性剂的种类,与传统氟碳表面活性剂相比,具有较好的水溶性及生物降解性,其应用范围得以拓展;以易降解、低毒含氟C6类化合物C6F13SO2F为起点,通过亲核取代反应、硅氢化反应和磺化反应合成磺酸盐型氟硅阴离子表面活性剂,为我国氟硅阴离子表面活性剂的开发和应用提供一个新的研究方法和思路。
附图说明
以下结合附图对本发明作进一步详述。
图1为本发明中C6F13SO2N(CH3)CH2CH=CH2的傅里叶红外FT-IR谱图;
图2为本发明中C6F13SO2N(CH3)CH2CH=CH2的1HNMR图;
图3为本发明中磺酸盐型氟硅阴离子表面活性剂的傅里叶红外FT-IR谱图;
图4为本发明中磺酸盐型氟硅阴离子表面活性剂的γ-lgc曲线。
具体实施方式
一种磺酸盐型氟硅阴离子表面活性剂,该化合物的化学结构式为:
其中Rf为:C6F13SO2;Me为CH3;x和y均为正整数。
所述的磺酸盐型氟硅阴离子表面活性剂在水溶液中的临界胶束浓度为0.10~0.18g/L,在水溶液中的最低表面张力为32.8~37.5mN/m。
一种磺酸盐型氟硅阴离子表面活性剂的制备方法,如图1-4所示,该制备方法包括以下步骤:
(1)在装有搅拌器、温度计、滴液漏斗和回流冷凝管的50mL四口烧瓶中加入20mL乙酸乙酯和1.78gN-甲基烯丙胺,所述回流冷凝管上装有无水CaCl2干燥管,所述1.78g N-甲基烯丙胺的浓度为0.025mol,室温下逐渐滴加4.02g全氟己基磺酰氟,所述4.02g全氟己基磺酰氟的浓度为0.01mol,控制30min滴加完毕,在40℃下继续搅拌反应2h;停止反应后,将反应液倒入100mL水中,分层后取下层淡黄色液体,依次用50mL 5%HCl水溶液、30mL饱和NaCO3水溶液和2×30mL水进行洗涤,无水硫酸钠干燥,得淡黄色透明液体,黄色透明液体为C6F13SO2N(CH3)CH2CH=CH2;
(2)将2.5g高含氢硅油、0.54g C6F13SO2N(CH3)CH2CH=CH2和甲苯20mL加入100mL的三口圆底烧瓶中,然后加入浓度为16.123g/L的Karstedt催化剂,接上冷凝装置和温度计,磁力搅拌,油浴升温加热至90℃;当硅氢化转化率达到3%时,加入4.54g烯丙基缩水甘油醚,继续反应至硅氢化反应转化率基本恒定为止,
反应体系中高含氢硅油中硅氢物质的量为40.85mmol,C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量分别为1.23mmol和39.62mmol,三者物质的量比例为高含氢硅油中硅氢:C6F13SO2N(CH3)CH2CH=CH2中碳碳双键:烯丙基缩水甘油醚中碳碳双键=10:0.3:9.7;
(3)反应结束后将反应物在35℃真空旋转蒸发以除去甲苯和易挥发组分,然后在真空干燥箱中,50℃真空干燥4h,以进一步除去残留的甲苯和和易挥发组分,得到高含氢硅油中硅氢、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量比例为10:0.3:9.7的硅氢化产物,为淡黄色粘稠液体;
(4)取硅氢化产物2.0g、乙醇15mL、水5mL加入100mL单口圆底烧瓶中,然后加入NaHSO3 0.6g,接上冷凝回流装置,磁力搅拌,油浴升温加热至80℃,回流反应24h,有白色不溶物生成;减压抽滤除去不溶物,在35℃真空旋转蒸发以除去乙醇和水,得到淡黄色粘稠液体,即为氟硅阴离子表面活性剂。
在保持高含氢硅油2.5g不变的条件下,使高含氢硅油中硅氢、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量比例还可以分别为10:0.6:9.4、10:0.9:9.1和10:1.2:8.8。
实施例1
本实施例的一种基于磺酸盐型氟硅阴离子表面活性剂的制备方法,包括如下步骤:
(1)C6F13SO2N(CH3)CH2CH=CH2的合成
在装有搅拌器、温度计、滴液漏斗和回流冷凝管(上装一无水CaCl2干燥管)的50mL四口烧瓶中加入20mL乙酸乙酯和1.78g(0.025mol)N-甲基烯丙胺,室温下逐渐滴加4.02g(0.01mol)全氟己基磺酰氟,控制约30min滴加完毕,在40℃下继续搅拌反应2h。停止反应后,将反应液倒入100mL水中,分层后取下层淡黄色液体,依次用50mL5%HCl水溶液、30mL饱和NaCO3水溶液和2×30mL水进行洗涤,无水硫酸钠干燥,得淡黄色透明液体,收率91.8%(以全氟己基磺酰氟计)。
(2)硅氢化产物的合成
将2.5g高含氢硅油、0.54g C6F13SO2N(CH3)CH2CH=CH2和甲苯20mL加入100mL的三口圆底烧瓶中,然后加入浓度为16.123g/L的Karstedt催化剂,接上冷凝装置和温度计,磁力搅拌,油浴升温加热至90℃;当硅氢化转化率达到3%时,加入4.54g烯丙基缩水甘油醚,继续反应至硅氢化反应转化率基本恒定为止,
反应体系中高含氢硅油中硅氢物质的量为40.85mmol,C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量分别为1.23mmol和39.62mmol,三者物质的量比例为高含氢硅油中硅氢:C6F13SO2N(CH3)CH2CH=CH2中碳碳双键:烯丙基缩水甘油醚中碳碳双键=10:0.3:9.7。反应结束后将反应物料在35℃真空旋转蒸发以除去甲苯和易挥发组分,然后在真空干燥箱中,50℃真空干燥4h,以进一步除去残留的甲苯和易挥发组分,得到高含氢硅油中硅氢、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量比例为10:0.3:9.7的硅氢化产物,为淡黄色粘稠液体。
(3)磺酸盐型氟硅阴离子表面活性剂的合成
取硅氢化产物2.0g、乙醇15mL和水5mL加入100mL单口圆底烧瓶中,然后加入NaHSO30.6g,接上冷凝回流装置,磁力搅拌,油浴升温加热至80℃,回流反应24h,有白色不溶物生成。减压抽滤除去不溶物,在35℃真空旋转蒸发以除去乙醇和水,得到淡黄色粘稠液体,即为高含氢硅油中硅氢、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量比例为10:0.3:9.7的氟硅阴离子表面活性剂。
本实例的上述方法中的三步合成工艺,反应原理如下:
(1)C6F13SO2N(CH3)CH2CH=CH2的制备
(2)硅氢化产物的制备
(3)磺酸盐型氟硅阴离子表面活性剂的制备
对上述所制备的C6F13SO2N(CH3)CH2CH=CH2进行FT-IR和1HNMR表征,数据如下所示。
FTIR(cm-1):在1351.0cm-1处为磺酰胺非对称振动吸收峰;1140.6cm-1处为磺酰胺对称振动吸收峰,
1HNMR(CDCl3,ppm):δa=5.33(dd,1H),δb=5.35(dd,1H),δc=5.80(m,1H),δd=4.19(s,1H),δe=3.81(s,1H),δf=3.04(s,3H)。
通过C6F13SO2N(CH3)CH2CH=CH2的FT-IR和1HNMR的谱图可知,所合成的产物与目标产物结构相符合。
对上述所制备的磺酸盐型氟硅阴离子表面活性剂进行FT-IR表征,数据如下所示。
FTIR(cm-1):3439cm-1为-OH伸缩振动吸收峰;2934和2874cm-1为-CH2、-CH3的不对称伸缩振动吸收峰;1260cm-1为Si-CH3的-CH3对称变形振形振动吸收峰;1195cm-1为C-F伸缩振动吸;1099和1044cm-1为Si-O-Si伸缩振动吸收峰;800cm-1为Si-C伸缩振动吸收峰。
通过磺酸盐型氟硅阴离子表面活性剂的FT-IR的谱图可知,所合成的产物与目标产物结构相符合。
本实施例将制备的磺酸盐型氟硅阴离子表面活性剂配制成一系列不同浓度的待测样品溶液,室温下平衡48h,使用表面张力仪(QBZY型)采用铂金板法测其浓临界胶束浓度(cmc)和临界胶束浓度浓度下的表面张力γcmc。
磺酸盐型氟硅阴离子表面活性剂的表面张力随浓度变化趋势如图4所示;其浓临界胶束浓度(cmc)和临界胶束浓度浓度下的表面张力γcmc如表1所示。由表1可知,当高含氢硅油中硅氢、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量比例为10:0.3:9.7时,磺酸盐型氟硅阴离子表面活性剂的cmc和γcmc分别为0.13g/L和35.5mN/m。
实施例2
本实施例与实施例1相同,不同点在于:
(2)硅氢化产物的合成
将2.5g高含氢硅油、1.08g C6F13SO2N(CH3)CH2CH=CH2和甲苯20mL加入100mL的三口圆底烧瓶中,然后加入浓度为16.123g/L的Karstedt催化剂,接上冷凝装置和温度计,磁力搅拌,油浴升温加热至90℃;当硅氢化转化率达到6%时,加入4.40g烯丙基缩水甘油醚,继续反应至硅氢化反应转化率基本恒定为止。
反应体系中高含氢硅油中硅氢物质的量为40.85mmol,C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量分别为2.45mmol和38.40mmol,三者物质的量的比例为10:0.6:9.4。由表1可知,当高含氢硅油中硅氢、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量比例为10:0.6:9.4时,磺酸盐型氟硅阴离子表面活性剂的cmc和γcmc分别为0.12g/L和32.8mN/m。
实施例3
本实施例与实施例1相同,不同点在于:
(2)硅氢化产物的合成
将2.5g高含氢硅油、1.62g C6F13SO2N(CH3)CH2CH=CH2和甲苯20mL加入100mL的三口圆底烧瓶中,然后加入浓度为16.123g/L的Karstedt催化剂,接上冷凝装置和温度计,磁力搅拌,油浴升温加热至90℃;当硅氢化转化率达到9%时,加入4.26g烯丙基缩水甘油醚,继续反应至硅氢化反应转化率基本恒定为止。
反应体系中高含氢硅油中硅氢物质的量为40.85mmol,C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量分别为3.69mmol和37.17mmol,三者物质的量比例为10:0.9:9.1。由表1可知,当高含氢硅油中硅氢、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量比例为10:0.9:9.1时,磺酸盐型氟硅阴离子表面活性剂的cmc和γcmc分别为0.10g/L和36.1mN/m。
实施例4
本实施例与实施例1相同,不同点在于:
(2)硅氢化产物的合成
将2.5g高含氢硅油、2.16g C6F13SO2N(CH3)CH2CH=CH2和甲苯20mL加入100mL的三口圆底烧瓶中,然后加入浓度为16.123g/L的Karstedt催化剂,接上冷凝装置和温度计,磁力搅拌,油浴升温加热至90℃;当硅氢化转化率达到12%时,加入4.12g烯丙基缩水甘油醚,继续反应至硅氢化反应转化率基本恒定为止。
反应体系中高含氢硅油中硅氢物质的量为40.85mmol,C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量分别为4.92mmol和35.94mmol,三者物质的量比例为10:1.2:8.8。由表1可知,当高含氢硅油中硅氢、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量比例为10:1.2:8.8时,磺酸盐型氟硅阴离子表面活性剂的cmc和γcmc分别为0.18g/L和37.5mN/m。
表1磺酸盐型氟硅阴离子表面活性剂的cmc与γcmc
Claims (4)
2.根据权利要求1所述的一种磺酸盐型氟硅阴离子表面活性剂,其特征在于,所述的磺酸盐型氟硅阴离子表面活性剂在水溶液中的临界胶束浓度为0.10~0.18g/L,在水溶液中的最低表面张力为32.8~37.5mN/m。
3.根据权利要求1所述的一种磺酸盐型氟硅阴离子表面活性剂的制备方法,其特征在于,该制备方法包括以下步骤:
(1)在装有搅拌器、温度计、滴液漏斗和回流冷凝管的50mL四口烧瓶中加入20mL乙酸乙酯和1.78gN-甲基烯丙胺,所述回流冷凝管上装有无水CaCl2干燥管,所述1.78g N-甲基烯丙胺的浓度为0.025mol,室温下逐渐滴加4.02g全氟己基磺酰氟,所述4.02g全氟己基磺酰氟的浓度为0.01mol,控制30min滴加完毕,在40℃下继续搅拌反应2h;停止反应后,将反应液倒入100mL水中,分层后取下层淡黄色液体,依次用50mL 5%HCl水溶液、30mL饱和NaCO3水溶液和2×30mL水进行洗涤,无水硫酸钠干燥,得淡黄色透明液体,黄色透明液体为C6F13SO2N(CH3)CH2CH=CH2;
(2)将2.5g高含氢硅油、0.54g C6F13SO2N(CH3)CH2CH=CH2和甲苯20mL加入100mL的三口圆底烧瓶中,然后加入浓度为16.123g/L的Karstedt催化剂,接上冷凝装置和温度计,磁力搅拌,油浴升温加热至90℃;当硅氢化转化率达到3%时,加入4.54g烯丙基缩水甘油醚,继续反应至硅氢化反应转化率基本恒定为止。
反应体系中高含氢硅油中硅氢物质的量为40.85mmol,C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量分别为1.23mmol和39.62mmol,三者物质的量比例为高含氢硅油中硅氢:C6F13SO2N(CH3)CH2CH=CH2中碳碳双键:烯丙基缩水甘油醚中碳碳双键=10:0.3:9.7。
(3)反应结束后将反应物在35℃真空旋转蒸发以除去甲苯和易挥发组分,然后在真空干燥箱中,50℃真空干燥4h,以进一步除去残留的甲苯和和易挥发组分,得到高含氢硅油中硅氢、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量比例为10:0.3:9.7的硅氢化产物,为淡黄色粘稠液体;
(4)取硅氢化产物2.0g、乙醇15mL、水5mL加入100mL单口圆底烧瓶中,然后加入NaHSO30.6g,接上冷凝回流装置,磁力搅拌,油浴升温加热至80℃,回流反应24h,有白色不溶物生成;减压抽滤除去不溶物,在35℃真空旋转蒸发以除去乙醇和水,得到淡黄色粘稠液体,即为氟硅阴离子表面活性剂。
4.根据权利要求3所述的一种磺酸盐型氟硅阴离子表面活性剂的制备方法,其特征在于,所述步骤(2)中,高含氢硅油中硅氢物质的量、C6F13SO2N(CH3)CH2CH=CH2和烯丙基缩水甘油醚中碳碳双键的物质的量比例还可以分别为10:0.6:9.4、10:0.9:9.1和10:1.2:8.8。
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