CN103554405B - 一种水性含氟拒水拒油剂及其制备方法 - Google Patents
一种水性含氟拒水拒油剂及其制备方法 Download PDFInfo
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Abstract
<b>本发明涉及一种水性含氟拒水拒油剂及其制备方法,其为碳氟烷基一元醇、</b><b>2,2-</b><b>二羟甲基丙酸或</b><b>2,2-</b><b>二羟甲基丁酸在催化剂</b><b>1</b><b>和有机溶剂</b><b>1</b><b>的存在下发生酯化反应,生成碳氟烷基酯基二元醇,然后碳氟烷基酯基二元醇、二异氰酸酯、脂肪烃二元醇、含有水溶性基团的二元醇在催化剂</b><b>2</b><b>的存在下发生聚合反应后,生成预聚体,预聚体经中和剂、封端剂处理后即得水性含氟拒水拒油剂。本发明制备的含氟拒水拒油剂为自乳化型,具有很好的机械稳定性,有效地提高拒水拒油性能。本发明的水性含氟拒水拒油剂不仅可以用来处理各种纤维制品,还可以用于形成一些硬质表面如内外墙防污涂料、船舶涂料、陶瓷、砖石、木材等的涂层</b><b>。</b>
Description
技术领域
本发明属于高分子材料技术领域,具体涉及一种水性含氟拒水拒油剂及其制备方法。
背景技术
含氟高分子化合物具有许多优异的性能,如卓越的拒水拒油性能。氟化烷基(甲基)丙烯酸酯与烷基(甲基)丙烯酸酯的共聚物被广泛应用于制备含氟拒水拒油剂。尽管现有市场上的含氟拒水拒油剂在某些应用条件下的效果是令人满意的,但是聚合工艺较为复杂,需要选择性能优异的乳化剂,增加了合成难度。此外,在高低温、高酸碱、高剪切等环境中或者贮存时间过长,乳液会絮凝或沉淀,稳定性差,严重影响乳液的应用。而且,乳化剂的加入会降低拒水拒油剂的拒水、拒油性能。这一类型的拒水拒油剂大多为弱阳离子型,可增强与纤维的亲和力,提高初始防水性能,但加工持续性不好,而且耐洗牢度不能满足使用要求。此外,含氟丙烯酸酯类单体价格昂贵,导致相应的拒水拒油剂成本较高。因此,开发结构新颖的拒水拒油产品显得尤为迫切。
目前,有些技术工作者已经开发出一些新型的拒水拒油产品,如含氟水性聚氨酯类拒水拒油剂。含氟水性聚氨酯的制备主要有两种方法,核壳乳液聚合法和逐步聚合法。核壳乳液聚合法是最为常见的方法,是通过将含氟丙烯酸酯类单体引入聚氨酯/丙烯酸酯乳液中聚合,制备出以聚氨酯为壳,以含氟丙烯酸酯类单体和丙烯酸酯类单体的共聚物为核的核壳乳液;逐步聚合法主要是通过含氟二元醇(胺)扩链改性聚氨酯或通过氟改性软硬段单体来制备含氟聚氨酯。但是,一种具有优良的拒水拒油性能的热反应型含氟水性聚氨酯拒水拒油剂的制备方法,未见报道。
发明内容
本发明所要解决的技术问题是克服现有技术的不足,提供一种热反应型的水性含氟拒水拒油剂。
本发明所要解决的另一技术问题是提供上述水性含氟拒水拒油剂的制备方法。
为解决以上技术问题,本发明采取如下技术方案:
一种水性含氟拒水拒油剂,其为碳氟烷基一元醇、2,2-二羟甲基丙酸或2,2-二羟甲基丁酸在催化剂1和有机溶剂1的存在下发生酯化反应,生成碳氟烷基酯基二元醇,然后所述的碳氟烷基酯基二元醇、二异氰酸酯、脂肪烃二元醇、含有水溶性基团的二元醇在催化剂2的存在下发生聚合反应后,生成预聚体,所述的预聚体经中和剂、封端剂处理后即得所述的水性含氟拒水拒油剂,其中,所述的碳氟烷基一元醇与所述的2,2-二羟甲基丙酸或2,2-二羟甲基丁酸的质量比为1.5~2.5:1;所述的碳氟烷基酯基二元醇、二异氰酸酯、脂肪烃二元醇、含有水溶性基团的二元醇、中和剂、封端剂的质量比为4~9:5~13:2~10:0.8~1:0.5~0.8:1。
优选地,所述的碳氟烷基一元醇为全氟丁基乙醇、全氟己基乙醇、全氟辛基乙醇、全氟癸烷基乙醇、全氟十二烷基乙醇中的一种或多种;所述的催化剂1是为甲苯磺酸、盐酸、硫酸的一种或多种;所述的有机溶剂1为苯、甲苯、二甲苯、三氯甲烷、四氯甲烷的一种或多种。
更为优选地,碳氟烷基一元醇为全氟己基乙醇、全氟辛基乙醇,最优选地,碳氟烷基一元醇为全氟己基乙醇;最优选地,催化剂1是对甲苯磺酸;更为优选地,有机溶剂1是甲苯、二甲苯,最优选地,有机溶剂1是甲苯。
优选地,所述的二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种。
更为优选地,所述的二异氰酸酯为异佛尔酮二异氰酸酯。
优选地,所述的脂肪烃二元醇为甲烷氧基丙烷1,2-二元醇、乙烷氧基丙烷1,2-二元醇、丙烷氧基丙烷1,2-二元醇、丁烷氧基丙烷1,2-二元醇、戊烷氧基丙烷1,2-二元醇、己烷氧基丙烷1,2-二元醇、庚烷氧基丙烷1,2-二元醇、辛烷氧基丙烷1,2-二元醇、壬烷氧基丙烷1,2-二元醇、癸烷氧基丙烷1,2-二元醇、十二烷氧基丙烷1,2-二元醇、十四烷氧基丙烷1,2-二元醇、十六烷氧基丙烷1,2-二元醇、十八烷氧基丙烷1,2-二元醇的一种或多种。
更为优选地,脂肪烃二元醇为十二烷氧基丙烷1,2-二元醇、十四烷氧基丙烷1,2-二元醇、十六烷氧基丙烷1,2-二元醇、十八烷氧基丙烷1,2-二元醇中的一种或多种,特别优选地是十六烷氧基丙烷1,2-二元醇和/或十八烷氧基丙烷1,2-二元醇;
优选地,所述的含有水溶性基团的二元醇为2,2-二羟甲基丙酸和/或2,2-二羟甲基丁酸。
更为优选地,含有水溶性基团的二元醇是2,2-羟甲基丁酸
优选地,所述的催化剂2为三乙胺、三乙醇胺、三亚乙基二胺、二亚乙基三胺、二甲基十六胺吡啶、N,N-二甲基吡啶、N,N-二甲基环己胺、双甲基胺基乙基醚、二月桂酸二丁基锡、辛酸亚锡的一种或多种。
更为优选地,催化剂2是二月桂酸二丁基锡。
优选地,所述的中和剂为氢氧化钠、三乙胺、N,N-二甲基乙醇胺、二乙醇胺、三乙醇胺的一种或多种;
优选地,所述的封端剂为亚硫酸氢钠。
更为优选地,中和剂为三乙胺。
一种上述水性含氟拒水拒油剂的制备方法,包括依次进行的如下步骤:
(1)将按比例加入所述的碳氟烷基一元醇、2,2-二羟甲基丙酸或2,2-二羟甲基丁酸,然后加入催化剂1、有机溶剂1搅拌后,升温到90~150℃,在压力为0~-0.05MPa的减压状态下反应4~8小时,冷却后,经中和、水洗、减压蒸馏,得到碳氟烷基酯基二元醇;
(2)在氮气保护下,将步骤(1)得到的碳氟烷基酯基二元醇、二异氰酸酯、脂肪烃二元醇、含有水溶性基团的二元醇按比例添加至反应器中,然后加入催化剂2,在50~90℃条件下反应2~6小时,生成预聚体,降温到40~50℃,加入中和剂反应0.5~1小时,再降温到0~30℃,加入溶解有封端剂的去离子水溶液,进行封端反应1~4小时,然后加入醋酸、盐酸或硫酸调节pH值为4~6,过滤、分离,得到所述的水性含氟拒水拒油剂。
其中,步骤(1)的反应方程式为:
优选地,所述的步骤(2)中,在生成预聚体后、降温到40~50℃前,还需加入有机溶剂2,所述的有机溶剂2为丙酮、丁酮、N,N-二甲基甲酰胺、N-甲基吡咯烷酮的一种或多种。
更为优选地,有机溶剂2是丁酮。
由于以上技术方案的实施,本发明与现有技术相比具有如下优点:
本发明制备的含氟拒水拒油剂为自乳化型,具有很好的机械稳定性,并避免了外加乳化剂降低含氟拒水拒油剂的拒水性能,有效地提高拒水拒油性能。
本发明的水性含氟拒水拒油剂具有优异的拒水拒油性能,不仅可以用来处理各种纤维制品,如棉、麻、丝、毛、涤纶、锦纶、腈纶等天然纤维或合成纤维,还可以用于形成一些硬质表面如内外墙防污涂料、船舶涂料、陶瓷、砖石、木材等的涂层。此外,本发明的水性含氟拒水拒油剂可通过浸渍、喷涂或涂布、再干燥的方式施加于基体的表面,使用简便。
本发明先采用本体聚合的方法制备得到预聚体,然后在低温条件下分散于有机溶剂的水溶液中进行封端反应,得到热反应型的含氟拒水拒油剂。
具体实施方式
下面结合具体实施例对本发明做进一步详细的说明,但本发明并不限于以下实施例。实施例中采用的实施条件可以根据具体使用的不同要求做进一步调整,未注明的实施条件为本行业中的常规条件。
实施例1
(1)合成碳氟烷基酯基二元醇
将全氟己基乙醇90g、2,2-二羟甲基丙酸40g、对甲苯磺酸3.9g和130g甲苯加入装有搅拌器、温度计的反应器中,搅拌溶解后升温到140℃,使反应器呈减压状态(0~-0.05MPa),溜去水的同时反应6h,冷却后,中和、水洗,减压蒸馏,精制得到93.8g淡黄色粘稠液体全氟己基乙基酯二元醇。
2)合成水性含氟拒水拒油剂
在氮气保护下,将(1)中制备的全氟己基乙基酯二元醇40g、异佛尔酮二异氰酸酯61.55g、十八烷氧基丙烷1,2-二元醇50g、2,2-二羟甲基丙酸5g和三滴二月桂酸二丁基锡加入反应容器中,在70~75℃条件下反应6小时,生成预聚体,加入少量丁酮降低粘度,降温到40~50℃,加入三乙胺3.8g中和0.5h,降温到10℃左右,加入溶解有5g亚硫酸氢钠的去离子水溶液380g,快速搅拌进行封端反应2小时,然后加入醋酸调节pH值为5.5~6,过滤,分离,得到固含量为30%的含氟拒水拒油剂。
实施例2
(1)合成碳氟烷基酯基二元醇
将全氟己基乙醇90g、2,2-二羟甲基丙酸40g、对甲苯磺酸3.9g和130g甲苯加入装有搅拌器、温度计的反应器中,搅拌溶解后升温到140℃,使反应器呈减压状态(0~-0.05MPa),溜去水的同时反应6h,冷却后,中和、水洗,减压蒸馏,精制得到93.8g淡黄色粘稠液体全氟己基乙基酯二元醇。
(2)合成水性含氟拒水拒油剂
在氮气保护下,将(1)中制备的全氟己基乙基酯二元醇60g、甲苯二异氰酸酯61.6g、十八烷氧基丙烷1,2-二元醇30g、2,2-二羟甲基丙酸8g和三滴二月桂酸二丁基锡加入反应容器中,在60~65℃条件下反应5小时,生成预聚体,加入少量丁酮降低粘度,降温到40~50℃,加入三乙胺6g中和0.5h,降温到30℃左右,加入溶解有10g亚硫酸氢钠的去离子水溶液400g,快速搅拌进行封端反应1小时,然后加入醋酸调节pH值为5.5~6,过滤,分离,得到固含量为30%的含氟拒水拒油剂。
实施例3
(1)合成碳氟烷基酯基二元醇
将全氟己基乙醇91g、2,2-二羟甲基丁酸55.6g、对甲苯磺酸7.3g和145g甲苯加入装有搅拌器、温度计的反应器中,搅拌溶解后升温到140℃,使反应器呈减压状态(0~-0.05MPa),溜去水的同时反应5h,冷却后,中和、水洗,减压蒸馏,精制得到101.6g淡黄色粘稠液体全氟己基乙基酯二元醇。
(2)合成水性含氟拒水拒油剂
在氮气保护下,将(1)中制备的全氟己基乙基酯二元醇70g、甲苯二异氰酸酯75.9g、十六烷氧基丙烷1,2-二元醇40g、2,2-二羟甲基丁酸12.5g和三滴二月桂酸二丁基锡加入反应容器中,在60~65℃条件下反应5小时,生成预聚体,加入少量丁酮降低粘度,降温到40~50℃,加入三乙胺8.6g中和1h,降温到10℃左右,加入溶解有15g亚硫酸氢钠的去离子水溶液520g,快速搅拌进行封端反应2小时,然后加入醋酸调节pH值为5.5~6,过滤,分离,得到固含量为30%的含氟拒水拒油剂。
实施例4
(1)合成碳氟烷基酯基二元醇
将全氟己基乙醇91g、2,2-二羟甲基丁酸55.6g、对甲苯磺酸7.3g和145g甲苯加入装有搅拌器、温度计的反应器中,搅拌溶解后升温到140℃,使反应器呈减压状态(0~-0.05MPa),溜去水的同时反应5h,冷却后,中和、水洗,减压蒸馏,精制得到101.6g淡黄色粘稠液体全氟己基乙基酯二元醇。
(2)合成水性含氟拒水拒油剂
在氮气保护下,将(1)中制备的全氟己基乙基酯二元醇70g、异佛尔酮二异氰酸酯85g、十八烷氧基丙烷1,2-二元醇35g、2,2-二羟甲基丙酸10g和三滴二月桂酸二丁基锡加入反应容器中,在70~75℃条件下反应6小时,生成预聚体,加入少量丁酮降低粘度,降温到40~50℃,加入三乙胺7.6g中和0.5h,降温到5℃左右,加入溶解有12.5g亚硫酸氢钠的去离子水溶液510g,快速搅拌进行封端反应4小时,然后加入醋酸调节pH值为5.5~6,过滤,分离,得到固含量为30%的含氟拒水拒油剂。
对实施例1~4的含氟拒水拒油剂的防水防油性能和耐水性能进行测试,具体如下:
1.测试方法
(1)拒水性
a.对织物进行防水防油处理:织物一浸一轧(整理剂浓度20~50g/L,pH5.0~7.0,轧余率70%)→预烘(120℃,90s)→焙烘(150℃,3min)或(170℃,1min)。
b.拒水性能测试:使用淋水实验装置,在25~30s内,将250mL水淋洒在被测织物上,观察织物的润湿状态,按照表1评价其拒水性能。
表1
(2)拒油性
采用AATCC-118-1992的测试方法:在一块水平铺展的织物上轻柔地滴一滴表2所述的试液(约为0.05mL),静置30s后,观察试液状态,以30s内不润湿织物试液的最大等级作为拒油度。
表2
等级 | 试液 |
8 | 正庚烷 |
7 | 正辛烷 |
6 | 正癸烷 |
5 | 正十二烷 |
4 | 正十四烷 |
3 | 正十六烷 |
2 | 正十六烷35/液体石蜡65的混合液 |
1 | 液体石蜡 |
0 | 比1差 |
(3)耐久性
按照JISL-0217-103的方法,反复洗涤十次或二十次,然后评价拒水拒油性能(HL10或HL20),HL0是指未洗涤时进行的评价。
2.测试结果
实施例1~4的水性含氟拒水拒油剂的拒水拒油性能测试结果见表3。
表3
以上对本发明做了详尽的描述,其目的在于让熟悉此领域技术的人士能够了解本发明的内容并加以实施,并不能以此限制本发明的保护范围,凡根据本发明的精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围内。
Claims (7)
1.一种水性含氟拒水拒油剂,其特征在于:其为碳氟烷基一元醇、2,2-二羟甲基丙酸或2,2-二羟甲基丁酸在催化剂1和有机溶剂1的存在下发生酯化反应,生成碳氟烷基酯基二元醇,然后所述的碳氟烷基酯基二元醇、二异氰酸酯、脂肪烃二元醇、含有水溶性基团的二元醇在催化剂2的存在下发生聚合反应后,生成预聚体,所述的预聚体经中和剂、封端剂处理后即得所述的水性含氟拒水拒油剂,其中,所述的碳氟烷基一元醇与所述的2,2-二羟甲基丙酸或2,2-二羟甲基丁酸的质量比为1.5~2.5:1;所述的碳氟烷基酯基二元醇、二异氰酸酯、脂肪烃二元醇、含有水溶性基团的二元醇、中和剂、封端剂的质量比为4~9:5~13:2~10:0.8~1:0.5~0.8:1,
所述的碳氟烷基一元醇为全氟丁基乙醇、全氟己基乙醇、全氟辛基乙醇、全氟癸烷基乙醇、全氟十二烷基乙醇中的一种或多种;所述的催化剂1是为甲苯磺酸、盐酸、硫酸的一种或多种;所述的有机溶剂1为苯、甲苯、二甲苯、三氯甲烷、四氯甲烷的一种或多种;
所述的含有水溶性基团的二元醇为2,2-二羟甲基丙酸和/或2,2-二羟甲基丁酸;
所述的中和剂为氢氧化钠、三乙胺、N,N-二甲基乙醇胺、二乙醇胺、三乙醇胺的一种或多种。
2.根据权利要求1所述的水性含氟拒水拒油剂,其特征在于:所述的二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种。
3.根据权利要求1所述的水性含氟拒水拒油剂,其特征在于:所述的脂肪烃二元醇为甲烷氧基丙烷1,2-二元醇、乙烷氧基丙烷1,2-二元醇、丙烷氧基丙烷1,2-二元醇、丁烷氧基丙烷1,2-二元醇、戊烷氧基丙烷1,2-二元醇、己烷氧基丙烷1,2-二元醇、庚烷氧基丙烷1,2-二元醇、辛烷氧基丙烷1,2-二元醇、壬烷氧基丙烷1,2-二元醇、癸烷氧基丙烷1,2-二元醇、十二烷氧基丙烷1,2-二元醇、十四烷氧基丙烷1,2-二元醇、十六烷氧基丙烷1,2-二元醇、十八烷氧基丙烷1,2-二元醇的一种或多种。
4.根据权利要求1所述的水性含氟拒水拒油剂,其特征在于:所述的催化剂2为三乙胺、三乙醇胺、三亚乙基二胺、二亚乙基三胺、二甲基十六胺吡啶、N,N-二甲基吡啶、N,N-二甲基环己胺、双甲基胺基乙基醚、二月桂酸二丁基锡、辛酸亚锡的一种或多种。
5.根据权利要求1所述的水性含氟拒水拒油剂,其特征在于:所述的封端剂为亚硫酸氢钠。
6.一种如权利要求1至5中任一项所述的水性含氟拒水拒油剂的制备方法,其特征在于:包括依次进行的如下步骤:
(1)将按比例加入所述的碳氟烷基一元醇、2,2-二羟甲基丙酸或2,2-二羟甲基丁酸,然后加入催化剂1、有机溶剂1搅拌后,升温到90~150℃,在压力为0~-0.05MPa的减压状态下反应4~8小时,冷却后,经中和、水洗、减压蒸馏,得到碳氟烷基酯基二元醇;
(2)在氮气保护下,将步骤(1)得到的碳氟烷基酯基二元醇、二异氰酸酯、脂肪烃二元醇、含有水溶性基团的二元醇按比例添加至反应器中,然后加入催化剂2,在50~90℃条件下反应2~6小时,生成预聚体,降温到40~50℃,加入中和剂反应0.5~1小时,再降温到0~30℃,加入溶解有封端剂的去离子水溶液,进行封端反应1~4小时,然后加入醋酸、盐酸或硫酸调节pH值为4~6,过滤、分离,得到所述的水性含氟拒水拒油剂;
其中,所述的碳氟烷基一元醇与所述的2,2-二羟甲基丙酸或2,2-二羟甲基丁酸的质量比为1.5~2.5:1;所述的碳氟烷基酯基二元醇、二异氰酸酯、脂肪烃二元醇、含有水溶性基团的二元醇、中和剂、封端剂的质量比为4~9:5~13:2~10:0.8~1:0.5~0.8:1,
所述的碳氟烷基一元醇为全氟丁基乙醇、全氟己基乙醇、全氟辛基乙醇、全氟癸烷基乙醇、全氟十二烷基乙醇中的一种或多种;所述的催化剂1是为甲苯磺酸、盐酸、硫酸的一种或多种;所述的有机溶剂1为苯、甲苯、二甲苯、三氯甲烷、四氯甲烷的一种或多种;
所述的含有水溶性基团的二元醇为2,2-二羟甲基丙酸和/或2,2-二羟甲基丁酸;
所述的中和剂为氢氧化钠、三乙胺、N,N-二甲基乙醇胺、二乙醇胺、三乙醇胺的一种或多种。
7.根据权利要求6所述的水性含氟拒水拒油剂的制备方法,其特征在于:所述的步骤(2)中,在生成预聚体后、降温到40~50℃前,还需加入有机溶剂2,所述的有机溶剂2为丙酮、丁酮、N,N-二甲基甲酰胺、N-甲基吡咯烷酮的一种或多种。
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