CN102464730A - 含氟微乳的制备方法及应用 - Google Patents
含氟微乳的制备方法及应用 Download PDFInfo
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Abstract
本发明提供了一种微乳剂,其由水、含氟聚醚过氧化物的羧酸盐和油组成。将所述微乳剂用于含氟烯烃单体的单聚、二元共聚和多元共聚反应中,可得到微粒直径为30~200nm的乳液,其粘度低,与传统的乳液相比,它可形成稳定的单一分散微乳胶,应用于涂层中能提高涂层的抗破裂能力,同时微胶粒增加的表面积能够改进颗粒在模塑操作烧结过程中的熔融。
Description
技术领域
本发明属于高分子化学领域,具体地说,涉及一种含氟微乳、其制备方法及应用。
背景技术
微乳液是由水相(水溶液)、油相(有机溶剂)、表面活性剂至少三种成分组成的透明或半透明的,热力学上稳定分散的液体组成的宏观均匀而微观上不均匀的液体混合物,具有低粘度、各向同性等性质。微乳液将连续介质分散成为微小空间,这种微小空间粒度细小、大小均一、稳定性高,一般可以稳定存在几个月,它包括油包水型(W/O)水包油型(O/W)以及双连续相三种。
微乳液的应用十分广泛,在石油、化妆品、医药、高分子、纺织、造纸、印刷等领域都发挥着重要的作用,特别是广泛应用于农药、医学、化妆品、金属冷却液、液体洗涤剂、油田开采助剂、印染助剂等精细化工领域。
微乳液的形成主要是依靠体系中各组分的匹配。决定微乳液稳定性因素主要有表面活性剂的种类以及与油、水的比例。常用的配制微乳液的表面活性剂有多种,包括阴离子型的表面活性剂、阳离子型的表面活性剂、非离子型的表面活性剂。
常用的表面活性剂如全氟辛烷磺酰基化合物(PFOS)、全氟辛酸铵(PFOA)或含氟聚醚,由于它们的乳化能力在分散聚合和乳液聚合反应中只能达到聚合平均粒径在150~300nm的范围,强劲搅拌下,会破坏其所成型的胶束,在聚合过程提前破乳,对四氟乙烯等的聚合反应带来不安全的爆聚反应。
发明内容
本发明的目的是提供一种乳化剂为含氟聚醚过氧化物的羧酸盐的微乳剂及其制备方法和应用。
为了实现本发明目的,本发明的一种微乳剂,其含有重量比为95~105∶8~10∶2~3的水、含氟聚醚过氧化物的羧酸盐以及油相(碳原子数为5~20的氟化烷烃);所述含氟聚醚过氧化物的羧酸盐的平均分子量为300~5000,结构如式(I)所示:
A-O-(Gf-O)m(Gf-O-O)n-(CF2O)p-(CF2OO)q-(CF(CF3)O)r-B (I)
其中,Gf是-CF2CF(CF3)-或-CF(CF3)CF2-;A是-CF3、-COOM或-CF2COOM;B是-COOM或-CF2COOM;M是-H、-NH4或碱金属元素;
m、n、p、q、r满足以下条件:
(1)m、n、p、q、r是大于等于1的整数;
(2)n+q≥2;
(3)n+q≤m+p+r;
(4)m≥n+p+q+r。
优选:微乳剂所含水、含氟聚醚过氧化物的羧酸盐以及碳原子数为5~20的氟化烷烃的重量比为100∶8~10∶2.5。
制备所述含氟聚醚过氧化物的羧酸盐所使用的含氟聚醚过氧化物的羧酸的酸值为20~120mg KOH/g;过氧值为0.5%~10.0%(wt)。
本发明涉及的含氟聚醚过氧化物的羧酸参照专利GB 1,104,482制备,主要原料为全氟丙烯HFP,在低温和紫外灯照射条件下反应,然后将制得的反应物水解,取有机物层,进行负压分馏截取不同沸程的馏分(30℃-180℃之间)。用19FNMR(核磁共振)确定所得物质的组成单元及结构,用碘量法分析确定所得物质的过氧值。
本发明还提供上述微乳剂的制备方法,其是将水、含氟聚醚过氧化物的羧酸盐以及油相按照重量比混合加入反应器中,在1000~1500rpm的搅拌速率下搅拌30~100min,然后对反应器抽真空,用氮气置换3~4次,以确保混合物中氧含量低于30ppm,在室温下得到半透明的微乳剂。
本发明所述的微乳剂的油相一般包括如下的添加剂:石蜡油、氟化煤油、八氟萘、三氟氯乙烯低聚物(聚合度5~8)、全氟三丁胺、六氟苯和市售商品氟化溶剂。其中含碳原子数为5~20的氟化烷烃可以是直链或支链的有机化合物。
本发明制备的微乳剂可用于四氟乙烯分散聚合、六氟丙烯改性四氟乙烯分散聚合、可熔四氟乙烯分散聚合、四氟乙烯-六氟丙烯共聚合乳液聚合及氟橡胶的乳液聚合的聚合反应中。
本发明制备的微乳剂应用于四氟乙烯、六氟丙烯或全氟丙基乙烯基醚改性四氟乙烯分散聚合、四氟乙烯一六氟丙烯乳液聚合中,可得到微粒直径为30~150nm的乳液,应用于氟橡胶的乳液聚合中,可得到微粒直径为30~200nm的乳液。
本发明优点是用含氟聚醚过氧化物的羧酸盐的氟表面活性剂替代全氟辛酸铵盐表面活性剂制备得到高分子量氟微乳液。它区别于常规乳状液,能克服用乳化剂PFOS、PFOA和全氟聚醚等的缺点,即乳状液由混浊不透明变成半透明、透明,可用于光催化聚合反应,制高纯的聚四氟乙烯、改性聚四氟乙烯和二元共聚/多元共聚氟橡胶。本发明微乳剂制备得到的微乳液比传统乳化剂得到的聚四氟乙烯、改性聚四氟乙烯和氟橡胶乳液粘度小,平均粒径小,特别适用于制品加工的成膜材料和熔融的模压加工。本发明微乳剂能制备稳定的单一分散微胶乳,不会因微粒破裂导致涂层不均匀现象的发生,且胶粒细微,增加了它的表面积,能改进颗粒在模塑操作中的熔融烧结和成型制品加工。含氟聚醚过氧化物的羧酸盐的主链上有过氧键-O-O-和醚键。从键能和键长的角度分析,C-F键非常稳定,引入适量醚键,C-O-C链易于自由旋转、卷曲和松弛。上述结构的特点使含氟聚醚具有较好的耐高温性能和化学稳定性,非常适合用作表面活性剂。过氧键的键能小、键长长,在反应过程中不稳定、易分解,采用含氟聚醚过氧化物的羧酸盐作为生产氟单体水性分散体的表面活性剂,与引发剂等助剂协同作用,使反应诱导过程平缓进行,利于聚合控制,可降低引发剂用量或缩短反应时间。本发明制备得到的微乳液粘度低,与传统的乳液相比,它可形成稳定的单一分散微乳胶,应用于涂层中能提高涂层的抗破裂能力,同时微胶粒增加的表面积能够改进颗粒在模塑操作烧结过程中的熔融。
具体实施方式
以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例1含氟聚醚过氧化物的羧酸及其铵盐的制备
参照专利GB 1,104,482(1968)的制备方法,在容积为2L的带-70℃的回流设施的耐压钢制反应器上安置功率为125W的紫外灯(波长为250nm-400nm)照射装置,预冷反应器和原料,然后向已经预冷的反应器里加入经预冷至-45℃的全氟丙烯(HFP)2kg;向反应器底部以20L/h的速度通入氧气(O2,以标态计量)和C2F3Cl 2.5L/h(以标态计量)的混合气,保持反应温度为-45℃,反应8h;然后停止紫外灯照射,停止反应;停止冷冻,回收HFP。将釜底反应产物取出,放在有搅拌的容器内,加适量90℃的热水水解16h,停止搅拌,静置分层,取油层,得665g水解产物;将该水解产物负压分馏截取不同沸程的馏分(30℃-180℃之间),得到一定范围的酸值和/或过氧值的含氟聚醚过氧化物羧酸604g。用碘量法分析各馏分段物质的过氧值;用19FNMR确定物质的组成单元及结构。
含氟聚醚过氧化物的羧酸铵盐的制备:
称取含氟聚醚过氧化物的羧酸100g,酸值70.1mg KOH/g,加入235ml去离子水,在搅拌条件下滴加25~28ml氨水(氨水浓度28%),直至含氟聚醚过氧化物的羧酸全部溶解并测定溶液pH7~8,备用。
实施例2
按实施例1方法制备得到的含氟聚醚过氧化物羧酸[CF3O(CF2CF(CF3)O)(CF2OO)(C(CF3)FO)COOH,酸值70.1mg KOH/g],过氧值5%作为乳化剂,制备成含氟聚醚过氧化物羧酸铵盐。
在反应釜中,加入去离子水32L,含氟聚醚过氧化物的羧酸铵盐2560g、石蜡油800g、过硫酸铵5g。在1500rpm的搅拌速率进行搅拌60min。然后对反应器抽真空,用氮气置换3~4次,分析氧含量≤30ppm,在室温下得到半透明的微乳液,微乳液的pH值在7±0.5范围内。然后加热将釜内温度升至75±1℃时,通入四氟乙烯的气相单体,聚合反应开始,控制釜内温度稳步上升,聚合反应压力维持2.3±0.05MPa。当釜内温度上升至95±2℃,同时聚合反应速度开始减慢时,则终止反应,回收釜内四氟乙烯单体。得到聚四氟乙烯微乳液,聚合液固含量14%,pH5~6范围,聚合液半透明,聚合物平均粒径60nm,聚合物相对标准密度(SSG)2.17。
实施例3
按实施例1方法制备得到的含氟聚醚过氧化物羧酸[CF3O(CF2CF(CF3)O)3(CF2CF(CF3)OO)(CF2O)(C(CF3)FO)CF2COOH,酸值43mgKOH/g,过氧值2.8%]作为乳化剂,制备成含氟聚醚过氧化物羧酸铵盐。
在反应釜中,加入去离子水28L,含氟聚醚过氧化物的羧酸铵盐2240g、石蜡油700g、过硫酸铵20g。在1500rpm的搅拌速率进行搅拌60min。然后对反应器抽真空,用氮气置换3~4次,分析氧含量≤30ppm,在室温下得到半透明的微乳液,微乳液的pH值在6~7范围内。接着将釜内温度升至65±1℃,然后,向釜内投入四氟乙烯与六氟丙烯的初始单体混合物,初始混合单体的重量比为:四氟乙烯∶六氟丙烯=1∶4,聚合压力2.4±0.05Mpa,同时向釜内泵入15wt%的亚硫酸钠溶液,聚合反应开始,釜内压力下降,这时不断补加四氟乙烯/六氟丙烯的混合单体,在聚合反应全过程中,维持釜内聚合压力2.4±0.05MPa(补加混合单体的重量比为:四氟乙烯∶六氟丙烯=4∶1)。还原剂亚硫酸氢钠泵入量与聚合反应速率变化联锁控制。反应时间210min~240min。反应结束后,回收剩余混合单体,得到四氟乙烯与六氟丙烯二元共聚微乳液。共聚乳液固含量12%,聚合物熔融指数6g/10min,熔融加工性能优良。聚合物平均粒径30nm。
实施例4
按实施例1方法制备得到的含氟聚醚过氧化物羧酸[CF3O(CF2CF(CF3)O)3(CF2CF(CF3)OO)(CF2O)(C(CF3)FO)CF2COOH,酸值43mg KOH/g,过氧值2.8%]作为乳化剂,制备成含氟聚醚过氧化物羧酸铵盐。
在反应釜中,加入去离子水28L,含氟聚醚过氧化物的羧酸铵盐2240g、石蜡油700g、过硫酸铵20g。在1500rpm的搅拌速率进行搅拌60min。然后对反应器抽真空,用氮气置换3~4次,分析氧含量≤30ppm,在室温下得到半透明的微乳液,微乳液的pH值在6~7范围内。接着将釜内温度升至70±1℃,然后,向釜内投入气相偏氟乙烯与六氟丙烯的二元共聚单体,初始共聚单体混合物的重量比为:偏氟乙烯∶六氟丙烯=1∶4,聚合压力2.3±0.05Mpa,接着向釜内泵入15wt%的亚硫酸钠溶液,聚合反应开始,釜内压力下降,此时加入偏氟乙烯/六氟丙烯的混合单体,补加混合单体偏氟乙烯与六氟丙烯的重量比为1∶4,保持2.3±0.05MPa釜内聚合压力,控制聚合反应过程中的反应温度70±1℃,亚硫酸氢钠15wt%泵入量与聚合反应速率变化联锁控制。整个聚合反应时间300min。反应结束后,回收釜内混合单体,得到二元共聚体固含量14wt%,二元共聚体平均粒径50nm,聚合物门尼粘度(121℃,1+10)35,适用于氟橡胶挤出制品的加工。
实施例5
按实施例1方法制备得到的含氟聚醚过氧化物羧酸[CF3O(CF2CF(CF3)O)(CF2OO)(C(CF3)FO)COOH,酸值70.1mgKOH/g,过氧值5%]作为乳化剂,制备成含氟聚醚过氧化物羧酸铵盐。
在反应釜中,加入去离子水32L,含氟聚醚过氧化物的羧酸铵盐2560g、石蜡油800g、过硫酸铵5g、全氟丙基乙烯基醚85g,。搅拌转速1500rpm,搅拌时间60min,并抽真空,用氮气置换3~4次,釜内氧含量≤30ppm。在室温下制备半透明的微乳液,微乳液的pH值控制6.5~7之间,接着将釜内温度升至78±1℃,加入气相四氟乙烯单体至釜内压力2.4±0.05Mpa,聚合反应开始,釜内压力下降,整个聚合反应过程保持2.4±0.05MPa釜内聚合压力,控制聚合温度缓慢上升,聚合反应终止温度90±2℃,聚合中后期泵入1ml甲醇水溶液,反应结束后回收四氟乙烯单体,得到改性聚四氟乙烯微乳液固含量13wt%,微乳液平均粒度45nm,透明度比聚四氟乙烯微乳液优,聚合物相对标准密度(SSG)2.16,聚合物成膜性优。
虽然,上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
Claims (6)
1.一种微乳剂,其特征在于,其含有重量比为95~105∶8~10∶2~3的水、含氟聚醚过氧化物的羧酸盐以及碳原子数为5~20的氟化烷烃;所述含氟聚醚过氧化物的羧酸盐的平均分子量为300~5000,结构如式(I)所示:
A-O-(Gf-O)m(Gf-O-O)n-(CF2O)p-(CF2OO)q-(CF(CF3)O)r-B (I)
其中,Gf是-CF2CF(CF3)-或-CF(CF3)CF2-;A是-CF3、-COOM或-CF2COOM;B是-COOM或-CF2COOM;M是-H、-NH4或碱金属元素;
m、n、p、q、r满足以下条件:
(1)m、n、p、q、r是大于等于1的整数;
(2)n+q≥2;
(3)n+q≤m+p+r;
(4)m≥n+p+q+r。
2.根据权利要求1所述的微乳剂,其特征在于,水、含氟聚醚过氧化物的羧酸盐以及碳原子数为5~20的氟化烷烃的重量比为100∶8~10∶2.5。
3.根据权利要求1或2所述的微乳剂,其特征在于,制备所述含氟聚醚过氧化物的羧酸盐所使用的含氟聚醚过氧化物的羧酸的酸值为20~120mgKOH/g;过氧值为0.5wt%~10.0wt%。
4.根据权利要求1-3任一项所述的微乳剂,其特征在于,微乳剂的氧含量低于30ppm。
5.权利要求1-4任一项所述微乳剂的制备方法,其特征在于,将水、含氟聚醚过氧化物的羧酸盐以及碳原子数为5~20的氟化烷烃按照重量比混合加入反应器中,在1000~1500rpm的搅拌速率下搅拌30~100min,然后对反应器抽真空,用氮气置换3~4次即得。
6.权利要求1-4任一项所述的微乳剂在各种含氟烯烃单体的单聚、二元共聚和多元共聚中的应用。
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