CN102414251B - 含氟聚醚羧酸酰胺的制造方法 - Google Patents
含氟聚醚羧酸酰胺的制造方法 Download PDFInfo
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Abstract
本发明是将通式CnF2n+1O(C3F6O)mRfCOF(其中,Rf为碳原子数1-2的碳氟基,n为1-3的整数,m为10-30的整数)所示的含氟聚醚酰氟与含氮杂环式胺化合物ArNH2(其中,Ar为含氮杂环基)反应时,使反应温度提高至80-100℃,然后使反应温度在48小时后的温度差为3-5℃的升温幅度范围内升温,进行反应,制造通式CnF2n+1O(C3F6O)mRfCONHAr(其中,Rf、Ar、n和m与上述定义相同)所示的含氟聚醚羧酸酰胺。
Description
技术领域
本发明涉及含氟聚醚羧酸酰胺的制造方法。更具体地说,涉及末端基团被具有氮原子的化合物修饰的含氟聚醚羧酸酰胺的制造方法。
背景技术
分子中具有氟原子的含氟化合物,其热稳定性和化学稳定性优异,将其一部分用其他官能基团修饰而得的物质可以作为润滑油的添加剂等使用。其中,对于末端基团被具有氮原子的化合物修饰的物质,认为其在分子结构中含有具有非共轭电子对的氮原子,因此具有适度的配位能力,在金属表面上的吸附等优异,因此作为润滑油添加剂显示优异的性能。
作为这种添加剂的例子,专利文献1中提出了一种含有由-(CF2)nO-的重复单元和末端-CH2NRR’基团构成的稳定性化合物的磁盘用润滑剂。但是,在这些化合物的制造中,需要昂贵的甲烷磺酰氯,还必须采取无水条件下的反应等特殊的反应操作等,因此不容易提高生产规模。
另外,专利文献2中提出了具有吡啶环的含氟化合物。其制造方法仅仅是在相转移催化剂的存在下将吡啶衍生物与含氟醇混合,非常简便,但是,为了获得反应中使用的含氟醇,通常如专利文献3所示,必须进行对应的酰氟的酯化和还原反应,显示需要多道工序。
并且,专利文献4中记载了使含氟聚醚酰氯与芳族胺反应、获得含氟聚醚羧酸酰胺的方法,但其中所使用的酰氯必须是将对应的酰氟水解,转变为羧酸,然后使用亚硫酰氯或五氯化磷再次转变为酰氯,反应经历多个步骤,不仅在实际制造中不利,并且反应温度保持为5℃以下,因此反应转化率低,收率为75-85%左右,较低。
专利文献1:USP6,083,600
专利文献2:日本特开2004-346318号公报
专利文献3:USP3,810,874
专利文献4:日本特开平2-49096号公报。
发明内容
本发明的目的在于提供一个分子末端为化学惰性的全氟烷基、另一分子末端被具有氮原子的杂环基修饰的含氟聚醚羧酸酰胺的制造方法。
所述本发明的目的通过以下的方法实现:
在使下述通式所示的含氟聚醚酰氟
CnF2n+1O(C3F6O)mRfCOF [II]
(其中,Rf为碳原子数1-2的碳氟基,n为1-3的整数,m为10-30的整数)
与含氮杂环式胺化合物
ArNH2
(其中,Ar为含氮杂环基)
反应时,将反应温度提高至80-100℃,然后使反应温度在48小时后的温度差为3-5℃的升温幅度的范围内升温,进行反应,制造下述通式所示的含氟聚醚羧酸酰胺,
CnF2n+1O(C3F6O)mRfCONHAr [I]
(其中,Rf、Ar、n和m与上述定义相同)。
根据本发明的方法,通过使特定的含氟聚醚酰氟与含氮杂环式胺化合物进行酰胺化反应,可以收率良好地、容易地制造一个分子末端为化学惰性的全氟烷基、另一分子末端被具有氮原子的杂环基修饰的含氟聚醚羧酸酰胺。所得含氟聚醚羧酸酰胺的着色等受到抑制,可作为润滑剂的添加剂等有效地使用。
具体实施方式
一个分子末端为化学惰性的全氟烷基、另一分子末端被具有氮原子的杂环基修饰的含氟化合物的制造中所使用的含氟聚醚酰氟由下述通式表示。
CnF2n+1O(C3F6O)mRfCOF [II]
该化合物[II]可通过公知的方法容易地获得,通常是在氟化铯催化剂和四乙二醇二甲醚溶剂的存在下,通过使六氟环氧丙烷进行低聚反应,得到通式[IV]所示的全氟聚醚酰氟。
从容易制备的观点考虑,六氟环氧丙烷的数均聚合度(m)优选10≤m≤30左右,进一步优选m=20左右。另外,聚合度可以具有一定程度的分布。通过使用该六氟环氧丙烷低聚物的制造方法,可以效率最好地获得含氟聚醚酰氟。
另外,作为不具有支链结构的全氟聚醚酰氟的其他制造方法,还有:通过金属氟化物将四氟氧杂环丁烷开环聚合,然后通过直接氟化将重复单元部分的亚甲基烃进行氟化,获得通式[V]所示的全氟聚醚酰氟的方法。不过工序变长。
如以上例子所示,碳氟基Rf是碳原子数1-2的全氟亚烷基或支链全氟亚烷基,例如可示出-CF2-、-CF2CF2-、-CF(CF3)-基等。
作为全氟聚醚酰氟[II]的改性中使用的含氮杂环式氨基化合物ArNH2[III],可举出以下的化合物,这些含氮杂环式氨基化合物可以被至少一个烷基、卤素基团等取代。
(1)吡啶衍生物
例:2-、3-或4-氨基吡啶
(2)嘧啶衍生物
例:2-氨基嘧啶
2-氨基-4,6-二甲基嘧啶
(3)苯并咪唑衍生物
例:2-氨基苯并咪唑
这些含氟聚醚酰氟和含氮杂环式胺化合物通过边加热搅拌边反应,可获得目标产物——含氟化合物。反应时,为了捕获反应产生的HF,优选使不参与主反应的叔胺(HF捕获剂)共存。从反应后容易除去的观点考虑,优选使用三烷基胺(烷基为碳原子数1-12,优选1-3),吡啶、二甲基氨基吡啶等不具有游离氨基(NH2)的吡啶类,除了反应后的容易除去程度,再从反应性、处理的容易性、价格等观点考虑,进一步优选使用三乙胺、吡啶。
对于反应,即使不特别使用溶剂也可以获得目标产物,但在由于全氟聚醚的粘度等原因而难以搅拌等的情况下,也可以使用有机溶剂来使粘度降低。考虑各反应成分的溶解性等,优选使用氢氯氟烃、氢氟烃、氢氟醚等氟系有机溶剂作为有机溶剂,实际上可以使用旭硝子制品AK-225、3M公司制品ノベックHFE等市售商品。
对于反应温度,在向含氟聚醚酰氟中滴加含氮杂环式胺化合物和HF捕获剂后,首先设定为约80-100℃,优选约90-100℃。反应时,由于胺化合物的氧化可能使反应混合物发生显著着色,为避免这种现象,可以使滴加结束后的反应温度阶段性升温,具体来说,将反应温度升温至约80-100℃后,使反应温度在48小时后的温度差为3-5℃的升温幅度的范围内升温,进行反应。使反应温度升温后,在该反应温度下持续进行反应,直至-COF的信号(IR光谱中1880-1885cm-1的吸收)消失。另外,不必要的长时间反应也是引起着色的原因,因此,升温后的反应时间设定为24-100小时,优选48-72小时左右。
反应后,通过萃取处理除去在反应中产生的胺的HF盐等,但在反应中不使用溶剂时,可以使用氟系有机溶剂作为萃取溶剂。该氟系有机溶剂可以直接使用上述市售商品。应予说明,作为使反应混合物中的水溶性物质溶解的萃取溶剂,可以使用水、盐水、低级醇等,从它们的杂质的萃取能力、层分离能力的观点考虑,优选使用甲醇。
实施例
接着,基于实施例说明本发明。
实施例1
在安装有氮封用T字形连接器、搅拌叶片、冷凝器、滴液漏斗、温度计和加热用罩式加热器的烧瓶中导入1020 g全氟聚醚酰氟CF3CF2CF2O[CF(CF3)CF2O]mCF(CF3)COF(m:12 (由F-NMR求出的六氟环氧丙烷的数均聚合度,具有一定程度的分布))并搅拌。在室温下,向其中缓慢地滴加51g (372毫摩尔) 2-氨基苯并咪唑与9 g (89毫摩尔)三乙胺的混合物,滴加结束后调节罩式加热器的温度,使内温为92±1℃,并且再次进行调节,以使48小时后的内温为96±1℃,进一步加热搅拌24小时。通过IR光谱确认1885cm-1的COF信号消失,在反应混合物中加入250 mL氟系有机溶剂(旭硝子制品AK-225),搅拌,充分溶解,然后使用膜滤器除去氨的氟酸盐等不溶性成分。
在滤液中加入100 mL上述氟系有机溶剂(AK-225)和1200 g甲醇,充分混合,将萃取底层的操作共进行3次,最后使用旋转蒸发器在减压下除去氟系有机溶剂(AK-225),得到1050 g (收率98.1%)无着色的下述含氟化合物。
实施例2
实施例1中,作为全氟聚醚酰氟,使用500 g CF3CF2CF2O(CF2CF2CF2O)mCF2CF2COF(m:20 (由F-NMR求出的六氟环氧丙烷的数均聚合度,具有一定程度的分布)),另外将2-氨基苯并咪唑量变更为18.8 g (137毫摩尔)、将三乙胺量变更为3.3 g (33毫摩尔),同样地进行加热搅拌。确认IR光谱中1880cm-1(COF)信号消失,在反应混合物中加入100 mL氟系有机溶剂(AK-225),搅拌,充分溶解,然后使用膜滤器除去胺的氟酸盐等的不溶性成分。
在滤液中加入100 mL上述氟系有机溶剂(AK-225)和600 g甲醇,充分混合,将萃取底层的操作共进行3次,最后使用旋转蒸发器在减压下除去氟系有机溶剂(AK-225),得到482 g (收率93.5%)无着色的下述含氟化合物。
实施例3
实施例1中,使用35 g (372毫摩尔)4-氨基吡啶代替2-氨基苯并咪唑,将滴加结束后的内温变为90±1℃,48小时后的内温变为95±1℃,得到998 g (收率94.8%)无着色的下述含氟化合物。
m:12 (由F-NMR求出的六氟环氧丙烷的数均聚合度,具有一定程度的分布)
实施例4
实施例1中,使用35.3 g (372毫摩尔) 2-氨基嘧啶代替2-氨基苯并咪唑,将滴加结束后的内温变为90±1℃,48小时后的内温变为95±1℃,得到1032 g (收率98.0%)无着色的下述含氟化合物。
m:12 (由F-NMR求出的六氟环氧丙烷的数均聚合度,具有一定程度的分布)
实施例5
实施例2中,使用12.9 g (137毫摩尔) 4-氨基吡啶代替2-氨基苯并咪唑,将滴加结束后的内温变为90±1℃,48小时后的内温变为95±1℃,将反应混合物的溶解中使用的氟系溶剂(AK-225)的量变为120 ml,得到502 g (收率98.4%)无着色的下述含氟化合物。
m:20 (由F-NMR求出的六氟环氧丙烷的数均聚合度,具有一定程度的分布)
实施例6
实施例2中,使用13.0 g (137毫摩尔) 2-氨基嘧啶代替2-氨基苯并咪唑,将滴加结束后的内温变为90±1℃,48小时后的内温变为95±1℃,将反应混合物的溶解中使用的氟系溶剂(AK-225)的量变为120 ml,得到498 g (收率97.5%)无着色的下述含氟化合物。
m:20 (由F-NMR求出的六氟环氧丙烷的数均聚合度,具有一定程度的分布)
比较例
向安装有氮封用T字形连接器、搅拌叶片、冷凝器、滴液漏斗、温度计和加热用罩式加热器的烧瓶中导入1000 g全氟聚醚酰氟CF3CF2CF2O[CF(CF3)CF2O]mCF(CF3)COF(m:12 (由F-NMR求出的六氟环氧丙烷的数均聚合度,具有一定程度的分布))并搅拌。在室温下,向其中缓慢滴加51 g (372毫摩尔) 2-氨基苯并咪唑与9 g (89毫摩尔)三乙胺的混合物,滴加结束后,在室温状态下进行48小时搅拌。此时可确认到IR光谱中1885cm-1的COF信号,因此,将内温升温至90℃,进行24小时加热搅拌。确认在IR中该信号消失,停止加热搅拌。向反应混合物中加入250 mL氟系有机溶剂(旭硝子制品AK-225),搅拌,充分溶解,然后使用膜滤器除去胺的氟酸盐等的不溶性成分。
向滤液中加入100 mL上述氟系有机溶剂(AK-225)和1200 g甲醇,充分混合,将萃取底层的操作共实施3次,最后使用旋转蒸发器在减压下除去氟系有机溶剂(AK-225),得到下述含氟化合物(回收量:1020 g)。所得含氟化合物的NMR与实施例1相同,但是显著着色为茶褐色。
Claims (5)
1.含氟聚醚羧酸酰胺的制造方法,所述含氟聚醚羧酸酰胺如下述通式[I]所示:
CnF2n+1O(C3F6O)mRfCONHAr [I]
式[I]中,Rf为碳原子数1-2的碳氟基,n为1-3的整数,m为10-30的整数,Ar为由下式 [IIIa]、 [IIIb]或 [IIIc]衍生的含氮杂环基,
该制造方法的特征在于,在使下述通式[II]所示的含氟聚醚酰氟与下式[IIIa]、 [IIIb]或 [IIIc]的含氮杂环式胺化合物反应时,在向含氟聚醚酰氟中滴加含氮杂环式胺化合物与叔胺HF捕获剂的混合物后,将反应温度提高至80-100℃,然后使反应温度在48小时后的温度差为3-5℃的升温幅度的范围内升温,进行反应,
CnF2n+1O(C3F6O)mRfCOF [II]
其中,Rf、n、m与上述定义相同,
或者
2.权利要求1所述的含氟聚醚羧酸酰胺的制造方法,其中,将滴加结束后的温度设定为90-100℃。
3.权利要求1所述的含氟聚醚羧酸酰胺的制造方法,其中,使反应温度升温后,在该反应温度下持续反应直至-COF的信号消失。
4.权利要求1所述的含氟聚醚羧酸酰胺的制造方法,其中,叔胺为三烷基胺或吡啶。
5.权利要求1所述的含氟聚醚羧酸酰胺的制造方法,其中,使含氟聚醚酰氟与含氮杂环式胺化合物反应时,使用氟系溶剂。
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