CN116396177A - 一种全氟烷烃类衍生物的制备方法及应用 - Google Patents
一种全氟烷烃类衍生物的制备方法及应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 74
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 15
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
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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 claims abstract description 5
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- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
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- LWHQXUODFPPQTL-UHFFFAOYSA-M sodium;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [Na+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LWHQXUODFPPQTL-UHFFFAOYSA-M 0.000 description 5
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- VVQJOPLKZYGMOY-UHFFFAOYSA-N 2-n,2-n-dibutylpropane-1,2-diamine Chemical compound CCCCN(C(C)CN)CCCC VVQJOPLKZYGMOY-UHFFFAOYSA-N 0.000 description 3
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- JNFLSJUGIONDMJ-UHFFFAOYSA-N 2-n,2-n-diethylpropane-1,2-diamine Chemical compound CCN(CC)C(C)CN JNFLSJUGIONDMJ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 description 1
- OBMOTNPABSFLBC-UHFFFAOYSA-N 2-(dibutylamino)propan-1-ol Chemical compound CCCCN(C(C)CO)CCCC OBMOTNPABSFLBC-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/63—Additives non-macromolecular organic
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/06—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having the hydroxy groups esterified by carboxylic acids having the esterifying carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms of an acyclic saturated carbon skeleton
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- C07C233/00—Carboxylic acid amides
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- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
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- C07C239/08—Hydroxylamino compounds or their ethers or esters
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Abstract
本发明提供一种全氟烷烃类衍生物的制备方法及应用,所述的全氟烷烃类衍生物的制备方法为氮气保护下将1.0mmol全氟戊基乙酸或全氟己基乙酸和1.0mmol2‑二乙氨基乙胺、2‑二乙氨基乙醇、3‑二丁氨基‑1‑丙胺或3‑二丁氨基‑1‑丙醇加入20ml溶剂中,缓慢滴加0.1mmol有机碱作为催化剂,室温反应24h,浓缩后经柱层析分离得到中间产物,然后取中间产物1.5mmol在弱氧化剂的作用下进行氧化反应,经萃取得到第二步产物全氟烷烃类衍生物。本发明的全氟烷烃类衍生物可以在在制备氟碳表面活性剂、制备自清洁材料中应用。
Description
技术领域
本发明涉及全氟烷烃类衍生物技术领域,尤其是一种全氟烷烃类衍生物的制备方法及应用。
背景技术
与传统的表面活性剂相比,氟碳表面活性剂在较低的临界胶束浓度(cmc)下具有更高的表面活性、化学稳定性和热稳定性,且具有既疏水又疏油的特点。
因此,氟碳表面活性剂在防水涂料、灭火泡沫、电镀和驱蚊剂等许多应用中发挥着重要的作用。由于长氟碳链表面活性剂,如全氟辛酸盐(PFOA)和全氟辛磺酸盐(PFOS)具有极低的表面能,目前被广泛应用于各种功能涂料中。但此类氟碳表面活性剂对生物具有较高的毒性和生物累积性以及对环境具有持续的污染等缺点,因此开发新型环境友好型氟碳表面活性剂刻不容缓。
现有证据表明,PFOA和PFOS对人类和环境产生危害源自于此类表面活性剂中含8个碳原子,且全部形成碳-氟键。此类氟碳表面活性剂极难自然分解。因此在人类和动、植物体内长期蓄积,进而对机体产生严重的危害。
目前PFOA和PFOS替代品研发思路主要集中在降低氟碳表面活性剂中碳原子的个数,从而使其能够随着人类和动、植物的新陈代谢从而排出体外,减小其在体内的蓄积情况。
发明内容
针对现有技术的不足,本发明提供一种全氟烷烃类衍生物的制备方法及应用。
本发明的技术方案为:一种全氟烷烃类衍生物,所述的全氟烷烃类衍生物为具有低表面能的新型全氟烷烃类衍生物,其结构如式1所示:
其中,n为4或5;m为0或1;R分别为乙基、丁基中的任何一种。
作为优选的,所述的具有低表面能的新型全氟烷烃类衍生物为:
1.1.N,N-二乙氨基-乙基-全氟戊基乙酰胺(2a)
1.2.N,N-二丁氨基-乙基-全氟戊基乙酰胺(2b)
1.3.N,N-二乙氨基-乙基-全氟己基乙酰胺(2c)
1.4.N,N-二丁氨基-乙基-全氟己基乙酰胺(2d)
1.5.N,N-二乙氨基-丙基-全氟戊基乙酰胺(2e)
1.6.N,N-二丁氨基-丙基-全氟戊基乙酰胺(2f)
1.7.N,N-二乙氨基-丙基-全氟己基乙酰胺(2g)
1.8.N,N-二丁氨基-丙基-全氟己基乙酰胺(2h)
1.9.全氟戊基乙酸-N,N-二乙氨基乙酯(3a)
1.10.全氟戊基乙酸-N,N-二丁氨基乙酯(3b)
1.11.全氟己基乙酸-N,N-二乙氨基乙酯(3c)
1.12.全氟己基乙酸-N,N-二丁氨基乙酯(3d)
1.13.全氟戊基乙酸-N,N-二乙氨基丙酯(3e)
1.14.全氟戊基乙酸-N,N-二丁氨基丙酯(3f)
1.15.全氟己基乙酸-N,N-二乙氨基丙酯(3g)
1.16.全氟己基乙酸-N,N-二丁氨基丙酯(3h)
1.17.N,N-二乙基-N-氧氨基-乙基-全氟戊基乙酰胺(4a)
1.18.N,N-二丁基-N-氧氨基-乙基-全氟戊基乙酰胺(4b)
1.19.N,N-二乙基-N-氧氨基-乙基-全氟己基乙酰胺(4c)
1.20.N,N-二丁基-N-氧氨基-乙基-全氟己基乙酰胺(4d)
1.21.N,N-二乙基-N-氧氨基-丙基-全氟戊基乙酰胺(4e)
1.22.N,N-二丁基-N-氧氨基-丙基-全氟戊基乙酰胺(4f)
1.23.N,N-二乙基-N-氧氨基-丙基-全氟己基乙酰胺(4g)
1.24.N,N-二丁基-N-氧氨基-丙基-全氟己基乙酰胺(4h)
1.25.全氟戊基乙酸-N,N-二乙基-N-氧氨基乙酯(5a)
1.26.全氟戊基乙酸-N,N-二丁基-N-氧氨基乙酯(5b)
1.27.全氟己基乙酸-N,N-二乙基-N-氧氨基乙酯(5c)
1.28.全氟己基乙酸-N,N-二丁基-N-氧氨基乙酯(5d)
1.29.全氟戊基乙酸-N,N-二乙基-N-氧氨基丙酯(5e)
1.30.全氟戊基乙酸-N,N-二丁基-N-氧氨基丙酯(5f)
1.31.全氟己基乙酸-N,N-二乙基-N-氧氨基丙酯(5g)
1.32.全氟己基乙酸-N,N-二丁基-N-氧氨基丙酯(5h)。
作为优选的,本发明还提供一种低表面能的全氟烷烃类衍生物的制备方法,包括以下步骤:
S1)、在氮气保护下将1.0mmol全氟戊基乙酸或全氟己基乙酸和1.0mmol 2-二乙氨基乙胺、2-二乙氨基乙醇、3-二丁氨基-1-丙胺或3-二丁氨基-1-丙醇加入20ml溶剂中,缓慢滴加0.1mmol有机碱作为催化剂,室温反应24h,浓缩后经柱层析分离得到第一步产物2a-h和3a-h;
S2)、然后取第一步产物1.5mmol在弱氧化剂的作用下进行氧化反应,经萃取得到第二步产物全氟烷烃类衍生物4a-h和5a-h;合成工艺如下:
作为优选的,所述的溶剂为甲醇、乙醇和丙醇中的一种。
作为优选的,所述的有机碱为二乙基胺(EEA)、三乙基胺(TEA)和二异丙基乙胺(DIPEA)中的一种。
作为优选的,所述的弱氧化剂为过氧化氢和次氯酸中的一种。
作为优选的,步骤1)和步骤3)中,所述的温度为0-30℃,所述的反应时间为12-48小时。
作为优选的,步骤2)和步骤4)中,所述的温度为40-80℃;所述的反应时间为12-48小时。
作为优选的,本发明的全氟烷烃类衍生物在制备氟碳表面活性剂中的应用。
作为优选的,本发明所述全氟烷烃类衍生物在制备自清洁材料中的应用。
本发明的有益效果为:
1、本发明提供全氟烷烃类衍生物可应用于氟碳表面活性剂以及功能性涂料,尤其是用于自清洁材料;
2、本发明提供的全氟烷烃类衍生物以水为研究对象,测定不同浓度所述全氟烷烃类衍生物的表面张力,结果显示所述全氟烷烃类衍生物4c的表面张力最小,效果优于全氟辛酸钠,可用于制备自清洁材料。
3、本发明的全氟烷烃类衍生物制备方法简单、制备效率高、且效果优于全氟辛酸钠。
具体实施方式
下面对本发明的具体实施方式作进一步说明:
实施例1
本实施例提供全氟烷烃类衍生物2a的制备
在氮气保护下将1.0mmol全氟戊基乙酸和1.0mmol 2-二乙氨基乙胺加入20ml乙醇中,缓慢滴加0.1mmol三乙胺作为催化剂,室温反应24h,浓缩后经柱层析分离得到白色油状物2a。
本实施例的产率为91.4%。1H NMR(500MHz,CD3OD)δ3.67(t,J=5.6Hz,2H),3.21(t,J=17.3Hz,2H),2.54(m,J=6.0Hz,6H),2.34(t,6H).13C NMR(126MHz,CD3OD)δ172.68(m),125.59,121.10,109.72,107.32,106.55,63.98,44.06,42.73,33.85,16.03.HRMS:m/z427.1123([M+H]+)。
实施例2
本实施例提供全氟烷烃类衍生物2b的制备
制备方法同实施例1,将2-二乙氨基乙胺1.0mmol改为2-二丁氨基乙胺1.0mmol,得白色油状物2b。
本实施例产率为93.7%。1H NMR(500MHz,CD3OD)δ3.71(t,J=5.4Hz,2H),3.25(t,J=16.9Hz,2H),3.14(t,J=6.1Hz,4H),3.01(t,J=6.0Hz,4H),2.54(t,J=6.3Hz,4H),2.46(4H),1.41(m,6H).13C NMR(126MHz,CD3OD)δ175.01(m),118.47,114.27,110.56,107.37,104.30,68.47,63.44,45.39,44.01,28.09,21.36.HRMS-ESI:m/z483.2547([M+H]+)。
实施例3
本实施例提供全氟烷烃类衍生物2c的制备
制备方法同实施例1,将全氟戊基乙酸1.0mmol改为全氟己基乙酸1.0mmol,得白色油状物2c。
本实施例产率为95.8%。1H NMR(500MHz,CD3OD)δ3.54(t,J=6.1Hz,2H),3.14(t,J=12.1Hz,2H),2.48(t,J=5.1Hz,2H),2.41(t,J=3.5Hz,2H),1.91(m,6H).13C NMR(126MHz,CD3OD)δ177.28(m),118.30,119.33(m),114.379,112.63,111.07,103.53,55.84,53.01,41.27,20.57.HRMS-ESI:m/z 477.2369([M+H]+)
实施例4
本实施例提供全氟烷烃类衍生物2d的制备
制备方法同实施例2,将全氟戊基乙酸1.0mmol改为全氟己基乙酸1.0mmol,得白色油状物2d。
本实施例产率为92.3%。1H NMR(500MHz,CD3OD)δ3.70(t,J=6.3Hz,2H),3.22(t,J=15.4Hz,2H),3.11(t,J=5.9Hz,4H),3.05(t,J=6.7Hz,4H),2.54(t,J=5.6Hz,4H),2.38(d,4H),1.13(s,6H).13C NMR(126MHz,CD3OD)δ173.18(m),124.06,119.54(m),112.30,106.91,103.33,101.47,65.36,64.22,48.17,41.37.,26.54,20.77.HRMS-ESI:m/z533.1794([M+H]+)。
实施例5
本实施例提供全氟烷烃类衍生物2e的制备
制备方法同实施例1,将2-二乙氨基乙胺1.0mmol改为2-二乙氨基丙胺1.0mmol,得白色油状物2e。
本实施例产率为94.3%。1H NMR(500MHz,CD3OD)δ3.68(t,J=6.0Hz,2H),3.28(t,J=4.7Hz,2H),3.05(t,J=14.3Hz,4H),2.33(t,J=2.7Hz,2H),2.07(t,J=7.8Hz,2H),1.34(s,6H).13C NMR(126MHz,CD3OD)δ172.30(m),112.17,104.27(m),101.88,100.65,100.54,100.33,52.18,50.47,48.32,29.17,21.04.HRMS-ESI:m/z441.1357([M+H]+)。
实施例6
本实施例提供全氟烷烃类衍生物2f的制备
制备方法同实施例2,将2-二丁氨基乙胺1.0mmol改为2-二丁氨基丙胺1.0mmol,得白色油状物2f。
本实施例产率为90.1%。1H NMR(500MHz,CD3OD)δ3.76(t,J=3.1Hz,2H),3.30(t,J=10.2Hz,2H),3.07(t,J=4.3Hz,4H),3.03(t,J=2.5Hz,4H),2.41(t,J=5.0Hz,4H),2.21(d,4H),1.43(s,6H).13C NMR(126MHz,CD3OD)δ172.60(m),126.36,125.47(m),121.44,114.35,102.18,99.71,60.35,52.10,44.37,39.78,33.41,25.04,22.56.HRMS-ESI:m/z497.1968([M+H]+)。
实施例7
本实施例提供全氟烷烃类衍生物2g的制备
制备方法同实施例3,将2-二乙氨基乙胺1.0mmol改为2-二乙氨基丙胺1.0mmol,得白色油状物2g。
本实施例产率为90.9%。1H NMR(500MHz,CD3OD)δ3.77(t,J=5.4Hz,2H),3.31(t,J=6.3Hz,2H),3.22(t,J=16.8Hz,4H),2.40(t,J=6.0Hz,2H),2.21(t,J=8.4Hz,2H),1.01(d,6H).13C NMR(126MHz,CD3OD)δ177.30(m),129.43(m),121.06,115.39,124.01,71.03,66.35,20.14,15.04.HRMS-ESI:m/z 491.2140([M+H]+)。
实施例8
本实施例提供全氟烷烃类衍生物2h的制备
制备方法同实施例4,将2-二丁氨基乙胺1.0mmol改为2-二丁氨基丙胺1.0mmol,得白色油状物2h。
本实施例产率为95.0%。1H NMR(500MHz,CD3OD)δ3.72(t,J=6.3Hz,2H),3.37(t,J=14.9Hz,2H),3.24(t,J=5.8Hz,4H),3.11(t,J=5.6Hz,4H),2.57(t,J=4.1Hz,4H),2.10(d,4H),1.24(t,J=7.7Hz,6H).13C NMR(126MHz,CD3OD)δ173.02(m),124.03,121.34(m),114.70,110.12.,100.38,95.34,58.14,51.66,34.18,33.87,31.04,27.89,19.03.HRMS-ESI:m/z 547.2310([M+H]+)。
实施例9
本实施例提供全氟烷烃类衍生物3a的制备
制备方法同实施例1,将2-二乙氨基乙胺1.0mmol改为2-二乙氨基乙醇1.0mmol,得白色油状物3a。
本实施例的产率为92.5%。1H NMR(500MHz,CD3OD)δ3.76(t,J=7.2Hz,2H),3.34(t,J=13.6Hz,2H),2.60(t,J=7.1Hz,6H),1.95(t,J=6.6Hz,6H).13CNMR(126MHz,CD3OD)δ171.48(m),123.87,120.01,114.57,111.38,104.37,65.60,48.31,41.35,34.17,19.60.HRMS-ESI:m/z428.1469([M+H]+)。
实施例10
本实施例提供全氟烷烃类衍生物3b的制备
制备方法同实施例1,将2-二乙氨基乙胺1.0mmol改为2-二丁氨基乙醇1.0mmol,得白色油状物3b。
本实施例产率为88.6%。1H NMR(500MHz,CD3OD)δ3.68(t,J=6.4Hz,2H),3.07(t,J=15.7Hz,2H),3.01(t,J=5.0Hz,4H),2.87(t,J=4.8Hz,4H),2.46(t,J=5.9Hz,4H),2.27(4H),1.34(t,J=4.7Hz,6H).13C NMR(126MHz,CD3OD)δ176.47(m),115.78,113.50,111.07,109.36,107.78,70.15,65.34,40.10,37.94,25.14,23.07.HRMS-ESI:m/z 484.1673([M+H]+)。
实施例11
本实施例提供全氟烷烃类衍生物3c的制备
制备方法同实施例3,将2-二乙氨基乙胺1.0mmol改为2-二乙氨基乙醇1.0mmol,得白色油状物3c。
本实施例产率为93.1%。1H NMR(500MHz,CD3OD)δ3.78(t,J=4.9Hz,2H),3.29(t,J=17.0Hz,2H),2.69(t,J=6.8Hz,2H),2.54(t,J=6.1Hz,2H),2.13(t,J=10.4Hz,6H).13CNMR(126MHz,CD3OD)δ171.88(m),120.54,114.37(m),110.21,104.17,100.10,99.14,60.38,51.77,32.10,19.48.HRMS-ESI:m/z 478.0920([M+H]+)。
实施例12
本实施例提供全氟烷烃类衍生物3d的制备
制备方法同实施例4,将2-二丁氨基乙胺1.0mmol改为2-二丁氨基乙醇1.0mmol,得白色油状物3d。
本实施例产率为94.0%。1H NMR(500MHz,CD3OD)δ3.72(t,J=5.8Hz,2H),3.27(t,J=17.8Hz,2H),3.18(t,J=6.5Hz,4H),3.01(t,J=10.0Hz,4H),2.66(t,J=5.8Hz,4H),2.48(d,4H),1.60(s,6H).13C NMR(126MHz,CD3OD)δ172.23(m),120.13,117.41(m),110.54,105.09,100.47,99.87,60.2358.14,46.13,39.54.,23.83,22.06.HRMS-ESI:m/z 534.3024([M+H]+)。
实施例13
本实施例提供全氟烷烃类衍生物3e的制备
制备方法同实施例1,将2-二乙氨基乙胺1.0mmol改为2-二乙氨基丙醇1.0mmol,得白色油状物3e。
本实施例产率为1H NMR(500MHz,CD3OD)δ3.70(t,J=5.4Hz,2H),3.37(t,J=7.8Hz,2H),3.14(t,J=16.4Hz,4H),2.56(t,J=5.9Hz,2H),2.20(t,J=6.1Hz,2H),1.64(s,6H).13C NMR(126MHz,CD3OD)δ170.11(m),118.21,106.94(m),105.78,103.10,100.88,97.87,64.20,44.87,40.69,25.41,21.07.HRMS-ESI:m/z442.2740([M+H]+)。
实施例14
本实施例提供全氟烷烃类衍生物3f的制备
制备方法同实施例1,将2-二乙氨基乙胺1.0mmol改为2-二丁氨基丙醇1.0mmol,得白色油状物3f。
本实施例产率为93.4%。1H NMR(500MHz,CD3OD)δ3.78(t,J=6.0Hz,2H),3.41(t,J=15.7Hz,2H),3.26(t,J=7.8Hz,4H),3.17(t,J=5.6Hz,4H),22.7(t,J=7.1Hz,4H),2.13(s,4H),1.71(s,6H).13C NMR(126MHz,CD3OD)δ173.12(m),119.71,114.30(m),110.48,105.82,101.17,96.53,61.01,53.06,41.19,33.12,30.10,22.13,18.05.HRMS-ESI:m/z498.4438([M+H]+)。
实施例15
本实施例提供全氟烷烃类衍生物3g的制备
制备方法同实施例3,将2-二乙氨基乙胺1.0mmol改为2-二乙氨基丙醇1.0mmol,得白色油状物3g。
本实施例产率为91.7%。1H NMR(500MHz,CD3OD)δ3.63(t,J=6.4Hz,2H),3.28(t,J=7.1Hz,2H),3.10(t,J=15.3Hz,4H),2.29(t,J=4.5Hz,2H),2.03(t,J=5.8Hz,2H),1.47(s,6H).13C NMR(126MHz,CD3OD)δ170.47(m),121.36(m),120.0,113.87,110.32,76.45,63.90,28.77,18.03.HRMS-ESI:m/z 492.0148([M+H]+)。
实施例16
本实施例提供全氟烷烃类衍生物3h的制备
制备方法同实施例4,将2-二丁氨基乙胺1.0mmol改为2-二丁氨基丙胺1.0mmol,得白色油状物3h。
本实施例产率为91.1%。1H NMR(500MHz,CD3OD)δ3.79(t,J=4.4Hz,2H),3.40(t,J=15.5Hz,2H),3.26(t,J=5.0Hz,4H),3.17(t,J=4.3Hz,4H),2.15(t,J=6.0Hz,4H),1.86(d,4H),1.33(s,6H).13C NMR(126MHz,CD3OD)δ172.53(m),126.67,125.09(m),124.80,116.37,109.78,91.57,53.01,40.48,32.20,31.39,25.58,23.45,12.53.HRMS-ESI:m/z548.7501([M+H]+)。
实施例17
本实施例提供全氟烷烃类衍生物4a的制备
所述全氟烷烃类衍生物4a的制备:氮气保护下将1.0mmol全氟烷烃类衍生物2a加入20ml乙醇中,缓慢滴加1.5mmol过氧化氢作为催化剂,60℃反应24h,浓缩后经干燥得到白色产物4a。
本实施例的产率为85.0%。1H NMR(500MHz,CD3OD)δ3.71(t,J=6.9Hz,2H),3.50(t,J=16.0Hz,2H),2.78(m,4H),2.65(m,4H),2.13(s,6H).13C NMR(126MHz,CD3OD)δ174.09(m),129.11,1120.03,105.87(m),102.17,99.07,52.43,50.36,48.07,42.13,25.03.HRMS-ESI:m/z443.1117([M+H]+)。
实施例18
本实施例提供全氟烷烃类衍生物4b的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物2b1.0mmol,得白色产物4b。
本实施例产率为81.9%。1H NMR(500MHz,CD3OD)δ3.79(t,J=3.1Hz,2H),3.30(t,J=10.2.9Hz,2H),3.07(m,4H),3.00(m,4H),2.43(m,4H),2.21(4H),1.09(m,6H).13C NMR(126MHz,CD3OD)δ170.32.01(m),123.77,121.40,115.04,110.85,106.38,77.33,70.64,56.38,50.02,31.76,28.35.HRMS-ESI:m/z 499.5471([M+H]+)。
实施例19
本实施例提供全氟烷烃类衍生物4c的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物2c1.0mmol,得白色产物4c。
本实施例产率为88.7%。1H NMR(500MHz,CD3OD)δ3.72(t,J=6.9Hz,2H),3.35(t,J=13.Hz,2H),2.63(m,2H),2.50(t,J=5.8Hz,2H),2.01(m,6H).13CNMR(126MHz,CD3OD)δ171.86(m),122.31,120.88(m),115.76,109.48,111.07,106.47,62.97,50.30,48.16,25.09.HRMS-ESI:m/z493.2014([M+H]+)。
实施例20
本实施例提供全氟烷烃类衍生物4d的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物2d1.0mmol,得白色产物4d。
本实施例产率为84.1%。1H NMR(500MHz,CD3OD)δ3.69(t,J=5.9Hz,2H),3.31(t,J=16.1Hz,2H),3.20(d,4H),3.14(m,4H),2.96(m,4H),2.42(d,4H),1.97(s,6H).13C NMR(126MHz,CD3OD)δ172.93(m),125.32,116.48(m),110.36,108.79,100.31,99.67,62.36,54.96,47.20,45.67,31.06,26.14.HRMS-ESI:m/z549.2139([M+H]+)。
实施例21
本实施例提供全氟烷烃类衍生物4e的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物2e1.0mmol,得白色产物4e。
本实施例产率为87.3%。1H NMR(500MHz,CD3OD)δ3.73(t,J=7.3Hz,2H),3.34(t,J=4.8Hz,2H),3.14(m,4H),2.50(d,2H),2.21(d,2H),1.83(s,6H).13C NMR(126MHz,CD3OD)δ172.04(m),118.71,111.34(m),108.90,104.18,102.15,98.43,58.24,56.76,50.58,31.49,20.10.HRMS-ESI:m/z 457.4801([M+H]+)。
实施例22
本实施例提供全氟烷烃类衍生物4f的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物2f1.0mmol,得白色产物4f。
本实施例产率为89.1%。1H NMR(500MHz,CD3OD)δ3.72(t,J=5.3Hz,2H),3.26(t,J=14.4Hz,2H),3.11(t,J=5.8Hz,4H),3.01(m,4H),2.66(m,4H),2.37(d,4H),1.49(s,6H).13C NMR(126MHz,CD3OD)δ172.41(m),120.48,113.01(m),110.49,106.53,103.38,100.99,57.80,50.41,46.32,38.76,35.40,23.87,20.06.HRMS-ESI:m/z 512.1096([M+H]+)。
实施例23
本实施例提供全氟烷烃类衍生物4g的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物2g1.0mmol,得白色产物4g。
本实施例产率为83.6%。1H NMR(500MHz,CD3OD)δ3.69(t,J=6.1Hz,2H),3.40(t,J=5.6Hz,2H),3.27(m,4H),3.03(m,2H),2.29(t,J=7.7Hz,2H),1.46(d,6H).13C NMR(126MHz,CD3OD)δ171.76(m),123.35(m),122.10,119.84,113.34,65.49,59.03,34.80,17.34.HRMS-ESI:m/z 507.0428([M+H]+)。
实施例24
本实施例提供全氟烷烃类衍生物4h的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物2h1.0mmol,得白色产物4h。
本实施例产率为89.1%。1H NMR(500MHz,CD3OD)δ3.68(t,J=6.9Hz,2H),3.41(t,J=16.0Hz,2H),3.13(d,4H),3.09(d,4H),2.64(d,4H),2.31(d,4H),1.39(t,J=6.4Hz,6H).13C NMR(126MHz,CD3OD)δ172.55(m),127.34,120.65(m),115.01,114.25.,109.46,100.86,60.43,58.01,37.59,35.83,32.41,26.64,20.38.HRMS-ESI:m/z 578.2007([M+H]+)。
实施例25
本实施例提供全氟烷烃类衍生物5a的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物3a1.0mmol,得白色产物5a。
本实施例的产率为90.8%。1H NMR(500MHz,CD3OD)δ3.73(t,J=7.2Hz,2H),3.20(t,J=15.7Hz,2H),2.83(t,J=5.8Hz,6H),1.53(d,6H).13C NMR(126MHz,CD3OD)δ172.83(m),126.70,125.41,120.01,117.35,109.44,62.10,53.14,49.81,36.61,15.38.HRMS-ESI:m/z444.0980([M+H]+)。
实施例26
本实施例提供全氟烷烃类衍生物5b的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物3b1.0mmol,得白色产物5b。
本实施例产率为78.5%。1H NMR(500MHz,CD3OD)δ3.73(t,J=5.7Hz,2H),3.23(J=16.0Hz,2H),3.17(d,4H),2.80(m,4H),2.54(m,4H),2.21(s,4H),1.50(m,J=5.8Hz,6H).13CNMR(126MHz,CD3OD)δ172.10(m),124.03,117.86,115.40,113.54,110.68,66.09,62.10,43.87,35.49,29.96,19.42.HRMS-ESI:m/z500.2631([M+H]+)。
实施例27
本实施例提供全氟烷烃类衍生物5c的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物3c1.0mmol,得白色产物5c。
本实施例产率为88.0%。1H NMR(500MHz,CD3OD)δ3.70(t,J=6.7Hz,2H),3.38(t,J=18.7Hz,2H),2.42(m,2H),2.20(t,J=5.5Hz,2H),2.09(m,6H).13C NMR(126MHz,CD3OD)δ172.01(m),121.07,115.26(m),113.28,110.78,107.50,98.32,61.03,58.11,30.14,15.06.HRMS-ESI:m/z494.3032([M+H]+)。
实施例28
本实施例提供全氟烷烃类衍生物5d的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物3d1.0mmol,得白色产物5d。
本实施例产率为85.4%。1H NMR(500MHz,CD3OD)δ3.70(t,J=6.0Hz,2H),3.20(t,J=15.1Hz,2H),3.07(m,4H),2.96(m),2.71(t,J=5.4Hz,4H),2.33(d,4H),1.53(s,6H).13CNMR(126MHz,CD3OD)δ171.19(m),121.54,116.32(m),112.08,109.43,105.01,101.22,58.19,55.60,43.28,34.01,27.13,20.09.HRMS-ESI:m/z 550.1804([M+H]+)。
实施例29
本实施例提供全氟烷烃类衍生物5e的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物3e1.0mmol,得白色产物5e。
本实施例产率为87.6%。1H NMR(500MHz,CD3OD)δ3.72(t,J=5.5Hz,2H),3.24(t,J=17.3Hz,2H),3.10(m,4H),2.60(m,2H),2.37(d,2H),1.99(s,6H).13C NMR(126MHz,CD3OD)δ172.54(m),121.38,115.60(m),110.29,104.37,103.69,100.21,61.06,42.11,30.69,27.80,15.53.HRMS-ESI:m/z 458.0124([M+H]+)。
实施例30
本实施例提供全氟烷烃类衍生物5f的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物3f1.0mmol,得白色产物5f。
本实施例产率为90.8%。1HNMR(500MHz,CD3OD)δ3.71(t,J=5.7Hz,2H),3.20(t,J=14.0Hz,2H),3.05(m,4H),3.01(m,4H),2.24(t,J=5.9Hz,4H),2.11(s,4H),1.59(s,6H).13C NMR(126MHz,CD3OD)δ172.18(m),121.69,113.54(m),111.33,105.06,104.37,102.13,65.08,54.50,49.46,36.12,34.47,29.30,16.54.HRMS-ESI:m/z 514.6133([M+H]+)。
实施例31
本实施例提供全氟烷烃类衍生物5g的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物3g1.0mmol,得白色产物5g。
本实施例产率为73.27%。1H NMR(500MHz,CD3OD)δ3.72(t,J=5.0Hz,2H),3.21(t,J=15.6Hz,2H),3.09(d,4H),2.57(m,2H),2.14(t,J=6.0Hz,2H),1.52(s,6H).13C NMR(126MHz,CD3OD)δ171.58(m),120.09(m),114.37,113.10,111.54.,56.2848.30,25.54,12.18.HRMS-ESI:m/z 508.1149([M+H]+)。
实施例32
本实施例提供全氟烷烃类衍生物5h的制备
制备方法同实施例17,将全氟烷烃类衍生物2a 1.0mmol改为全氟烷烃类衍生物3h1.0mmol,得白色产物5h。
本实施例产率为84.3%。1H NMR(500MHz,CD3OD)δ3.70(t,J=5.8Hz,2H),3.45(t,J=16.1Hz,2H),3.20(t,J=4.9Hz,4H),3.08(m,4H),2.21(t,J=7.5Hz,4H),2.04(d,4H),1.97(s,6H).13C NMR(126MHz,CD3OD)δ171.66(m),125.43,120.37(m),111.48,108.91,105.48,98.67,60.01,45.62,37.71,30.69,26.93,25.47,16.33MS-ESI:m/z 564.2046([M+H]+)。
实验例2
通过表面张力的测定评价全氟烷烃类衍生物作为氟碳表面活性剂的潜力。受试目标化合物均用纯水溶解,配制成不同浓度(1.25mM、2.5Mm、5mM、10mM、20mM和30mM)的水分散液,然后将溶液静置过夜,备用。然后,使用表面张力仪对目标化合物的表面性能进行表征。本项目采用铂金板法测定室温下不同浓度化合物溶液的表面张力。结果显示,所述全氟烷烃类衍生物随着浓度的增大,表面张力逐渐减小,其中化合物4c的表面张力最小,效果优于全氟辛酸钠。
实施例1所得化合物与阳性对照全氟辛酸钠的表面张力数据见表1。
表1实施例1化合物与全氟辛酸钠水溶液的表面张力
为了测试全氟烷烃类衍生物对乳液聚合的影响,本发明提供的此类化合物衍作为含氟乳化剂,与其他单体混合发生聚合反应。
乳液聚合的配方:将重量百分比为1wt%的实施例1得到全氟烷烃类衍生物与49.25wt%甲基丙烯酸十二氟庚酯、49.25wt%甲基丙烯酸丁酯、0.5wt%过硫酸钾混合后,加热搅拌反应6小时。反应结束后检测转化率和称量凝絮物的重量。
实验例3
(1)转化率和凝胶量的测定
反应结束后,用一次性滴管准确量取1ml乳液,并将其进行称重,称重完成后滴加10μl阻聚剂的水溶液,称重后放入烘箱干燥至恒重,最后计算其转化率和凝胶量。如表2显示,各个化合物都对乳液聚合的转化率和凝胶量有一定的影响,其中化合物4c的作用最明显,提示了化合物4c可有效促进乳液聚合反应。
表2全氟烷烃类衍生物对乳液转化率的影响
样品 | 转化率(wt%) | 凝胶量(wt%) |
4a | 80.4 | 2.5 |
4b | 74.7 | 4.0 |
4c | 91.3 | 1.0 |
4d | 88.2 | 2.3 |
4e | 73.3 | 3.3 |
4f | 71.0 | 2.9 |
4g | 85.4 | 1.8 |
4h | 82.0 | 3.9 |
5a | 74.5 | 2.7 |
5b | 69.9 | 3.4 |
5c | 81.6 | 1.9 |
5d | 76.4 | 4.8 |
5e | 71.9 | 3.3 |
5f | 65.4 | 5.0 |
5g | 73.7 | 5.6 |
5h | 69.5 | 4.7 |
通过上述实验分析可得,本申请提供的全氟烷烃类衍生物具有极低的表面能,尤其是化合物4c。此类化合物可以作为氟碳表面活性剂用于乳液聚合反应。
上述实施例和说明书中描述的只是说明本发明的原理和最佳实施例,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。
Claims (10)
2.根据权利要求1所述的一种全氟烷烃类衍生物,其特征在于:所述的具有低表面能的新型全氟烷烃类衍生物为:
1.1.N,N-二乙氨基-乙基-全氟戊基乙酰胺(2a);
1.2.N,N-二丁氨基-乙基-全氟戊基乙酰胺(2b);
1.3.N,N-二乙氨基-乙基-全氟己基乙酰胺(2c);
1.4.N,N-二丁氨基-乙基-全氟己基乙酰胺(2d);
1.5.N,N-二乙氨基-丙基-全氟戊基乙酰胺(2e);
1.6.N,N-二丁氨基-丙基-全氟戊基乙酰胺(2f);
1.7.N,N-二乙氨基-丙基-全氟己基乙酰胺(2g);
1.8.N,N-二丁氨基-丙基-全氟己基乙酰胺(2h);
1.9.全氟戊基乙酸-N,N-二乙氨基乙酯(3a);
1.10.全氟戊基乙酸-N,N-二丁氨基乙酯(3b);
1.11.全氟己基乙酸-N,N-二乙氨基乙酯(3c);
1.12.全氟己基乙酸-N,N-二丁氨基乙酯(3d);
1.13.全氟戊基乙酸-N,N-二乙氨基丙酯(3e);
1.14.全氟戊基乙酸-N,N-二丁氨基丙酯(3f);
1.15.全氟己基乙酸-N,N-二乙氨基丙酯(3g);
1.16.全氟己基乙酸-N,N-二丁氨基丙酯(3h);
1.17.N,N-二乙基-N-氧氨基-乙基-全氟戊基乙酰胺(4a);
1.18.N,N-二丁基-N-氧氨基-乙基-全氟戊基乙酰胺(4b);
1.19.N,N-二乙基-N-氧氨基-乙基-全氟己基乙酰胺(4c);
1.20.N,N-二丁基-N-氧氨基-乙基-全氟己基乙酰胺(4d);
1.21.N,N-二乙基-N-氧氨基-丙基-全氟戊基乙酰胺(4e);
1.22.N,N-二丁基-N-氧氨基-丙基-全氟戊基乙酰胺(4f);
1.23.N,N-二乙基-N-氧氨基-丙基-全氟己基乙酰胺(4g);
1.24.N,N-二丁基-N-氧氨基-丙基-全氟己基乙酰胺(4h);
1.25.全氟戊基乙酸-N,N-二乙基-N-氧氨基乙酯(5a);
1.26.全氟戊基乙酸-N,N-二丁基-N-氧氨基乙酯(5b);
1.27.全氟己基乙酸-N,N-二乙基-N-氧氨基乙酯(5c);
1.28.全氟己基乙酸-N,N-二丁基-N-氧氨基乙酯(5d);
1.29.全氟戊基乙酸-N,N-二乙基-N-氧氨基丙酯(5e);
1.30.全氟戊基乙酸-N,N-二丁基-N-氧氨基丙酯(5f);
1.31.全氟己基乙酸-N,N-二乙基-N-氧氨基丙酯(5g);
1.32.全氟己基乙酸-N,N-二丁基-N-氧氨基丙酯(5h)。
4.根据权利要求3所述的一种全氟烷烃类衍生物的制备方法,其特征在于:所述的溶剂为甲醇、乙醇和丙醇中的一种。
5.根据权利要求3所述的一种全氟烷烃类衍生物的制备方法,其特征在于:所述的有机碱为二乙基胺(EEA)、三乙基胺(TEA)和二异丙基乙胺(DIPEA)中的一种。
6.根据权利要求3所述的一种全氟烷烃类衍生物的制备方法,其特征在于:所述的弱氧化剂为过氧化氢和次氯酸中的一种。
7.根据权利要求3所述的一种全氟烷烃类衍生物的制备方法,其特征在于:步骤1)和步骤3)中,反应温度为0-30℃,反应时间为12-48小时。
8.根据权利要求3所述的一种全氟烷烃类衍生物的制备方法,其特征在于:步骤2)和步骤4)中,反应温度为40-80℃;所述的反应时间为12-48小时。
9.一种全氟烷烃类衍生物的应用,其特征在于:所述的权利要求1-2任一项所述的全氟烷烃类衍生物在制备氟碳表面活性剂中的应用。
10.一种全氟烷烃类衍生物的应用,其特征在于:所述的权利要求1-2任一项所述全氟烷烃类衍生物在制备自清洁材料中的应用。
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