CN101506257B - 防油、防水和防污的甲基丙烯酸全氟烷基乙酯共聚物 - Google Patents

防油、防水和防污的甲基丙烯酸全氟烷基乙酯共聚物 Download PDF

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CN101506257B
CN101506257B CN200780031500XA CN200780031500A CN101506257B CN 101506257 B CN101506257 B CN 101506257B CN 200780031500X A CN200780031500X A CN 200780031500XA CN 200780031500 A CN200780031500 A CN 200780031500A CN 101506257 B CN101506257 B CN 101506257B
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H·戈茨
F·鲍尔斯
W·诺普
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Abstract

与氯乙烯和/或偏二氯乙烯、(甲基)丙烯酸C12-C22烷基酯和一种或多种可热交联的或异氰酸酯反应性的单体共聚的短链甲基丙烯酸全氟烷基乙酯可用于在特别温和的条件下纤维质基材的防水、防油和防污整理。

Description

防油、防水和防污的甲基丙烯酸全氟烷基乙酯共聚物
含氟化合物通常被用作表面活性剂或润湿剂并且被广泛用于基材的表面处理。它们频繁用于纤维质基材(fibrous substrates)例如地毯(carpets)、织物、皮革、无纺布(nonwovens)和纸以及硬基材例如木材、金属或混凝土的防油、防水和防污整理(oil-，water-，and soil-repellentfinishing)。对于如此处理的基材亲水和憎水液体的浸渗(imbibition)被降低并且已有污物的除去得以改善。
从文献中已知基于符合式I的单体的全氟烷基(甲基)丙烯酸酯共聚物
RFCH2CH2OCOC(R)＝CH2            (I)
RF为8个氟化碳原子的全氟烷基链，特别可用于制备防油、防水和防污涂层。当该RF全氟烷基链缩短至6或4个氟化碳原子时，涂层的防油、防水和防污性能变差。可以例如借助于在玻璃上均聚物涂层上水的接触角测量来证明该结构-性能关系。从甲基丙烯酸酯到丙烯酸酯所得到的临界表面张力增加，并且还随着氟化碳原子数目的增加而增加。
因此，对于使织物防油、防水和防污，必然设想尤其含有具有8个氟化碳原子的(甲基)丙烯酸全氟烷基乙酯的共聚物与具有少于8个氟化碳原子的类似化合物相比是更适合的。实际上，织物整理通常是基于包含具有6-20个氟化碳原子的全氟化碳链RF的单体的共聚物。这里，所述全氟烷基具有8-9个氟化碳原子的平均链长。
符合式I的(甲基)丙烯酸全氟烷基乙酯的代表性组合物例如是
11-17wt％的具有6个氟化碳原子的单体
48-52wt％的具有8个氟化碳原子的单体
18-22wt％的具有10个氟化碳原子的单体
1-15wt％的具有12个或多于12个氟化碳原子的单体。
然而，如上所述的通常的织物整理在所述整理的施加期间并且在每次清洗之后需要高温以实现良好的防油、防水和防污效果。
通过引入符合式I的单体，其具有含有4-20个氟化碳原子的RF全氟烷基链，所述全氟烷基基团的平均链长为6-7个氟化碳原子，相应的(甲基)丙烯酸全氟烷基乙酯共聚物即使在低整理温度也提供了好的排斥效果(repellency effects)。为此，US5344903尤其要求保护(甲基)丙烯酸全氟烷基乙酯的以下组合物：
25-70wt％的具有6个或更少的氟化碳原子的单体
20-40wt％的具有8个氟化碳原子的单体
5-25wt％的具有10个氟化碳原子的单体
0-15wt％的具有12个或多于12个氟化碳原子的单体。
该′903专利详细说明了分别具有“低分布”和“中分布”的所述相同单体的组合物。然而，所描述的所有组合物都包括具有含有8个氟化碳原子的线型全氟烷基链的单体。
然而，具有含有8个氟化碳原子的线型全氟烷基链的氟化(即含氟)化合物，包括上述的单体组合物，在某些条件下可降解形成全氟辛烷羧酸(perfluorooctanecarboxylic acid)。这些降解产物被认为是不会进一步降解并因此是持久的。此外，这些化合物被怀疑会积累在活生物体中。
本发明的目的是使用不包含具有8个氟化碳原子的线型全氟烷基链的含氟单体制备氟化共聚物，该氟化共聚物在使用有效量的氟化含水分散体的纤维质基材的表面处理中，将表面改性成高度防油、防水和防污的。
现已惊奇地发现，与氯乙烯和/或偏二氯乙烯、(甲基)丙烯酸C12-C22烷基酯和一种或多种可热交联的或异氰酸酯反应性的单体共聚的符合式II
RFCH2CH2OCOC(CH3)＝CH2                (II)
其中RF＝4和6的甲基丙烯酸全氟烷基乙酯的混合物，产生防油、防水和防污的涂层，该涂层是特别环境相容的并且在低温后处理之后还具有高效率和耐久性，而根本不需要存在具有8个氟化碳原子的线型全氟烷基链。
本发明因此提供共聚物，基于该共聚物的总重量包含：
a)40-97wt％，优选45-90wt％的甲基丙烯酸全氟烷基乙酯混合物，
b)1-50wt％，优选5-30wt％的(甲基)丙烯酸C12-C22烷基酯，和
c)0.5-10wt％，优选1-5wt％的一种或多种可热交联的或异氰酸酯反应性的单体，以及
d)1.5-50wt％，优选4-30wt％的氯乙烯和/或偏二氯乙烯。
该甲基丙烯酸全氟烷基乙酯混合物a)具有以下组成：
1-70wt％的具有4个氟化碳原子的符合式II的单体
30-99wt％的具有6个氟化碳原子的符合式II的单体。
特别优选以下的甲基丙烯酸全氟烷基乙酯混合物：
“高分布”
1-10wt％的具有4个氟化碳原子的符合式II的单体
90-99wt％的具有6个氟化碳原子的符合式II的单体
“低分布”
30-70wt％的具有4个氟化碳原子的符合式II的单体
30-70wt％的具有6个氟化碳原子的符合式II的单体。
最优选高分布的甲基丙烯酸全氟烷基乙酯混合物，因为其在纤维质材料上提供了优良的防油、防水和防污值以及良好的环境相容性。
共聚单体b)由(甲基)丙烯酸C12-C22烷基酯组成。优选以下可商购获得的丙烯酸酯和甲基丙烯酸酯以及它们的混合物：月桂基酯、肉豆蔻基酯、十六醇酯、硬脂基酯、二十二醇酯。特别优选相应的丙烯酸酯。最优选丙烯酸十六醇酯、丙烯酸硬脂酯和丙烯酸二十二醇酯。
共聚单体c)包含一个或多个可交联基团。可交联基团是能够进入与基材和/或与加入的另外的多官能化合物的反应的官能团。这类可交联的环氧基团，基团可以是：羧酸基团、烯属不饱和基团、羟基、氨基、N-羟烷基(alkylol)酰胺基团、异氰酸酯基团或被保护的异氰酸酯基团。具有一个或多个可交联基团的共聚单体的例子包括丙烯酸、甲基丙烯酸、α-氯丙烯酸、巴豆酸、马来酸、富马酸和衣康酸的不饱和羧酸和酸酐，包括羟基的单体例如(甲基)丙烯酸2-羟乙酯和(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟丁酯、甲基丙烯酸3-氯-2-羟基丙酯、聚(乙二醇)单(甲基)丙烯酸酯、聚(丙二醇)单(甲基)丙烯酸酯、聚(乙二醇)-co-聚(丙二醇)单(甲基)丙烯酸酯、聚四氢呋喃单(甲基)丙烯酸酯、N-羟基甲基(甲基)丙烯酰胺、羟丁基乙烯基醚。其它的可交联单体为例如(甲基)丙烯酸乙烯酯、(甲基)丙烯酸烯丙酯、N-甲氧基甲基丙烯酰胺、N-异丙氧基甲基丙烯酰胺、N-丁氧基甲基丙烯酰胺、N-异丁氧基甲基丙烯酰胺、(甲基)丙烯酸缩水甘油酯和α，α-二甲基-间异丙烯基苄基异氰酸酯(α，α-dimethyl-m-isopropenylbenzyl isocyanate)。其他例子是在升高的温度或者在用光照射下释放异氰酸酯的单体，例子是酚-、酮肟-和吡唑-保护的异氰酸酯封端的(甲基)丙烯酸烷基酯。
特别优选以下化合物用作共聚单体c)：甲基丙烯酸2-羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸3-氯-2-羟基丙酯、N-羟基甲基甲基丙烯酰胺、N-丁氧基甲基丙烯酰胺和甲基丙烯酸缩水甘油酯。最优选甲基丙烯酸2-羟乙酯、N-羟基甲基甲基丙烯酰胺和甲基丙烯酸缩水甘油酯。
共聚单体(d)是氯乙烯和/或偏二氯乙烯。特别优选偏二氯乙烯。
这里描述的共聚物通常通过自由基聚合技术，例如通过溶剂、乳液、微乳液或细乳液(miniemulsion)聚合技术制备。特别优选乳液聚合的变型。所述单体的乳液聚合在水、表面活性剂和任选的有机溶剂的存在下进行。所述混合物可以在聚合之前借助于高压均化器或类似的设备预先乳化。聚合通常在40℃-90℃的温度在自由基引发剂存在下进行。
可以单独或者组合使用各种阴离子、阳离子、非离子或两性表面活性剂。非离子表面活性剂的例子包括聚(乙二醇)十二烷基醚、聚(乙二醇)十三烷基醚、聚(乙二醇)十六烷基醚、聚(乙二醇)-co-聚(丙二醇)十六烷基醚、聚(乙二醇)硬脂基醚、聚(乙二醇)油基醚、聚(乙二醇)壬基苯酚醚、聚(乙二醇)辛基苯酚醚、聚(乙二醇)单月桂酸酯、聚(乙二醇)单硬脂酸酯、聚(乙二醇)单油酸酯、失水山梨糖醇单月桂酸酯、失水山梨糖醇单硬脂酸酯、失水山梨糖醇单棕榈酸酯、失水山梨糖醇单硬脂酸酯、失水山梨糖醇单油酸酯、失水山梨糖醇倍半油酸酯、失水山梨糖醇三油酸酯、聚(乙二醇)失水山梨糖醇单月桂酸酯、聚(乙二醇)失水山梨糖醇单棕榈酸酯、聚(乙二醇)失水山梨糖醇单硬脂酸酯、聚(乙二醇)失水山梨糖醇单油酸酯、聚(乙二醇)-co-聚(丙二醇)、聚甘油脂肪酸酯(polyglycerol fatty acidesters)、聚醚改性的硅油和全氟烷基-环氧乙烷加合物。相对于聚合物的重量，使用的非离子表面活性剂的量为0.1-100wt％。
根据本发明的阳离子表面活性剂的例子是基于饱和和不饱和脂肪酸胺的铵化合物，例如十八烷基乙酸铵、十二烷基三甲基氯化铵；基于氨基官能化的聚乙氧基化物和聚丙氧基化物以及它们的共聚物的铵化合物，例如聚氧乙烯月桂基单甲基氯化铵；基于芳基胺的铵化合物例如联苯基三甲基氯化铵、咪唑啉衍生物例如由牛脂(tallow)和咪唑啉形成的铵盐；硅酮-基阳离子表面活性剂和氟-基阳离子表面活性剂。相对于聚合物的重量，使用的阳离子表面活性剂的量为0.1-100wt％。
根据本发明的阴离子表面活性剂的例子包括脂肪醇硫酸盐，例如十二烷基硫酸钠和聚(乙二醇)十二烷基醚硫酸盐；烷基磺酸盐，例如十二烷基磺酸钠；烷基苯磺酸盐，例如壬基苯酚醚硫酸盐，磺基琥珀酸盐，例如己基二醚磺基琥珀酸钠(sodium hexyl diether sulphosuccinate)；脂肪醇磷酸盐例如十二烷基磷酸钠和脂肪酸盐例如硬脂酸钠盐。相对于聚合物的重量，使用的阴离子表面活性剂的量为0.1-100wt％。
自由基引发剂的例子是有机或无机过氧化物、偶氮化合物、有机和无机金属化合物和金属及它们的组合。特别优选偶氮化合物例如偶氮二异丁腈(AIBNs)、偶氮双戊腈和偶氮双(2-氰基戊酸)、2，2’-偶氮双(2-脒基丙烷)二氢氯化物；2，2’-偶氮双[2-(2-咪唑啉-2-基)丙烷二氢氯化物；氢过氧化物例如氢过氧化枯烯、叔丁基氢过氧化物和叔戊基氢过氧化物，二烷基过氧化物例如二叔丁基过氧化物和过氧化二枯基，过氧酯例如过苯甲酸叔丁酯和过邻苯二甲酸二叔丁酯，二酰基过氧化物例如过氧化苯甲酰和过氧化月桂酰；无机过氧化物例如过硫酸铵和过硫酸钾以及所述化合物与有机或无机金属化合物和金属的组合。
链转移剂可以0.01-5wt％的量用于聚合中，例子是烷基硫醇。
在溶剂和乳液聚合中的有机溶剂的例子是：酮例如丙酮、甲乙酮和甲基异丁基酮；醇例如乙醇、异丙醇和丁醇，多元醇例如1，3-丁二醇、1，6-己二醇、乙二醇、丙二醇、二丙二醇、三丙二醇和甘油；多元醇的醚和酯，例如二丙二醇单甲醚、三丙二醇单甲醚、三乙二醇二甲醚和二乙二醇单丁醚乙酸酯；酯例如乙酸乙酯、乙酸丙酯、乙酸丁酯、己二酸二丁酯和琥珀酸二丁酯；烃和卤代烃例如甲苯、二甲苯、辛烷、全氯乙烯和1，3-二氯-2，2，3，3，3-五氟丙烷。
对于制备的聚合物分散体，优选的固含量为10-50wt％。
所述氟化共聚物适用于涂覆纤维质基材例如地毯、织物、皮革、无纺布或纸，或者硬基材例如木材、金属或混凝土。它们赋予这些基材防水、防油和防污性能。
本发明因此还提供用有效量的所述氟化含水分散体表面处理纤维质基材的方法。
选择根据本发明的用于整理织物和其他片状结构体的制剂的含量以使得足够的排斥性能被转移到被处理的基材上。通过在施加之前和之后称量被整理的样品来确定吸湿量(wet pick-up)。
根据本发明的氟化织物整理剂可与其他添加剂，包括防水材料，例如蜡，硅酮，锆化合物或硬脂酸盐，以及其他防油材料，表面活性剂，杀虫剂，阻燃剂，抗静电添加剂，增塑剂，染料固色剂和防皱添加剂，以不破坏在织物上的固定和组合物的稳定性的量一起使用。
根据本发明的氟化织物整理剂可以通过加入反应性添加剂例如通过描述于US专利6437077和其中引用的参考文献中的被保护的异氰酸酯而被交联。用于该目的的其他反应性添加剂可以是蜜胺树脂或环氧化物。
将用所述氟化聚合物分散体涂覆的纤维质基材是例如地毯、织物、皮革、无纺布和纸。这些尤其由以下组成：天然纤维例如棉、亚麻和丝；合成纤维例如聚酰胺、聚酯、聚氨酯、聚烯烃、聚(甲基)丙烯酸酯、聚(氯乙烯)、聚(乙烯醇)；半合成纤维例如嫘萦(rayon)或醋酸纤维素；无机纤维例如玻璃纤维或陶瓷纤维，或所述纤维的任何所希望的组合，或者由这些材料组成的织造产品(woven products)的任何所希望的组合。
对于涂覆，通常将基材浸入由共聚物和任选的添加剂组成的稀分散体中。作为选择，可以将所述稀分散体喷到基材上。随后通过辊系统压制被饱和的基材以除去过量的分散体，在烘箱中干燥并且在足以实现所希望的排斥效果的温度和时间交联。对于根据本发明的制剂，该交联过程通常在20℃-190℃的温度进行，对于纤维质基材无需热后处理即可获得良好的排斥效果。然而，为了实现更好的排斥效果耐久性，需要约120℃-180℃，特别为约130℃-170℃的温度5秒-10分钟的时间，优选5秒-5分钟。
将所述制剂施加在基材上的另一种选择是泡沫施加，其中将制剂作为泡沫施加在基材上，其然后被干燥并且交联。对于泡沫施加，通常将所述制剂以已经与另外的发泡剂混合的浓缩泡沫形式添加。用于泡沫施加的高度浓缩的制剂通常含有数量最高为20wt％的含氟聚合物。
对于在织物上整理，这些可以在用于它们的防水、防异丙醇和防油性能的特定测试中在清洗之前和之后进行检查。
防水性通过根据AATCC标准试验方法22的喷射试验测定。将蒸馏水喷射到待测试的织物基材上并且随后使用润湿图案与该测试方法中描述的评价标准的参考图像的目测对比来生成数值。所报导的数值涉及用水喷射之后表面的外观并且具有以下含义(表1)：
表1
  防水性等级   含义
  100   没有水滴的粘附或者上表面的润湿
  90   偶尔的水滴粘附/上表面润湿
  80   在水冲击点处发生上表面润湿
  70   整个上表面部分润湿
  50   整个上表面完全润湿
  0   整个上表面和下表面完全润湿
可以采用使用一系列水-异丙醇试验溶液的第二测试来确定基材的防异丙醇性(IPA)。所报导的IPA等级是最高编号的其中织物在10秒内没有被润湿并且液滴仍然具有球形或半球形形状的试验溶液。被润湿的基材或只排斥100％水(0％异丙醇)，即最低润湿性试验溶液，的基材定级为0，而排斥100％异丙醇(0％水)的基材定级为10。同样地可以指定中间的等级。
按照AATCC标准试验方法118的防油性测试了基材排斥油性污染的能力，评价等级中越高的等级表示越好的对这类污染，特别是油性液体的排斥性。在试验中，通过小心的移液(pipetting)将由选择的一系列具有不同表面张力的烃组成的标准化试验液体的滴依次施加在待测试的样品表面上，并且在规定的接触时间之后目测评价润湿性。防油性值对应于没有造成表面润湿的最高编号的试验液体。标准试验液体具有以下组成(表2)：
表2
注释：Nujol是一种得自Plough Inc.的矿物油，其具有在38℃下360/390的Saybolt粘度和在15℃下0.880/0.900的比重。
现有技术的氟化共聚物目前给出6的防油性值；然而等级5通常已经被认为是优良的。
实施例
下面的实施例阐述了本发明的主题和优点，但实施例中列出的材料和数量应不被看作是限制性的。
材料：
FMA-6：95wt％甲基丙烯酸全氟己基乙酯和5wt％甲基丙烯酸全氟丁基乙酯的混合物
FA-6a：95wt％丙烯酸全氟己基乙酯和5wt％丙烯酸全氟丁基乙酯的混合物
FA-6b：丙烯酸全氟己基乙酯
FA-8：包含以下的混合物：
14wt％丙烯酸全氟己基乙酯
50wt％丙烯酸全氟辛基乙酯
20wt％丙烯酸全氟癸基乙酯
15wt％丙烯酸全氟十二烷基乙酯
FMA-46：33wt％甲基丙烯酸全氟己基乙酯和66wt％甲基丙烯酸全氟丁基乙酯的混合物
VC：氯乙烯
VDC：偏二氯乙烯
SA：丙烯酸硬脂酯
CA：丙烯酸十六醇酯
N-MAM：N-甲氧基甲基丙烯酰胺
HEMA：甲基丙烯酸2-羟乙酯
HEA：丙烯酸2-羟乙酯
PEPM：聚乙二醇-聚丙二醇单甲基丙烯酸酯
实施例1：用于织物整理的分散体的制备
通过在装有搅拌器、回流冷凝器和内温度计的高压釜中在惰性气体气氛下强烈搅拌以下组分制备分散体：
60.0g 甲基丙烯酸2-全氟己基乙酯
22.5g 丙烯酸硬脂酯
15.5g 偏二氯乙烯
1.0g  N-甲氧基甲基丙烯酰胺
1.0g  甲基丙烯酸羟乙酯
30.0g 二丙二醇
0.5g  十二烷硫醇
4.0g  月桂醇/16环氧乙烷加合物
3.5g  N，N-二甲基十二烷基乙酸铵
200.0g 水
将乳液加热至60℃并且加入0.6g引发剂2，2’-偶氮双-2-脒基丙烷二氢氯化物。聚合时间为在60℃下6小时。在反应后将过量的氯乙烯蒸出。所得的分散体具有约33％的固含量。为了整理织物，将该分散体酸化并且稀释至30g/l。
在得自Mathis AG(Switzerland)的HVF 59301实验室浸轧机上将分散体施加到纤维质基材上，随后在得自Mathis AG(Switzerland)的LTE实验室干燥机中在50℃和160℃/30秒干燥和热处理。使用得自NELGmbH，Neugersdorf的商购获得的织物Sahara 530306作为聚酯/棉65/35基材以比较所述施加。对于描述的所有实施例，吸湿量都为约66％。清洗/干燥工序包括在60℃下的5次清洗循环。用压载织物(ballast fabric)将相应的织物片补足至1千克的清洗负荷。所需的洗衣洗涤剂的量为7g“Coral intensive”每次清洗循环。在清洗循环之间不干燥织物片。清洗后在衣物干燥机中将衣物干燥。
还将实施例1的分散体施加在其他织物例如聚酯、棉、聚丙烯和聚酰胺上。相应的整理的织物展现出类似的效果水平。
实施例2-7和比较例A、B、C：
类似于实施例1制备织物整理分散体。单体数量报导在表3中。
比较例D：
比较例D符合US专利6716944中实施例4的配方。然而，该配方没有提供在该专利中披露的防水和防油性值。单体数量报导在表3中。
实施例1-7和比较例A、B、C & D的分散体的防异丙醇性(IPA)、防油性(oleo)和防水性(hydro)结果报导在表3中。
Figure G200780031500XD00111
Figure G200780031500XD00121
*符合US专利6716944中的实施例4的组合物

Claims (7)

1.共聚物，其由以下物质制备：基于该共聚物的总重量
a)40-97wt％的甲基丙烯酸全氟烷基乙酯混合物，
b)1-50wt％的(甲基)丙烯酸C12-C22烷基酯，和
c)0.5-10wt％的一种或多种可热交联的或异氰酸酯反应性的单体，以及
d)1.5-50wt％的氯乙烯和/或偏二氯乙烯；
其中所述甲基丙烯酸全氟烷基乙酯符合下式
RFCH2CH2OCOC(CH3)＝CH2(II)
所述甲基丙烯酸全氟烷基乙酯混合物a)具有以下组成：
1-70wt％的具有4个氟化碳原子的符合式II的单体，
30-99wt％的具有6个氟化碳原子的符合式II的单体。
2.根据权利要求1的共聚物，特征在于所述甲基丙烯酸全氟烷基乙酯混合物a)具有以下组成：
30-70wt％的具有4个氟化碳原子的符合式II的单体，
30-70wt％的具有6个氟化碳原子的符合式II的单体。
3.根据权利要求1的共聚物，特征在于所述甲基丙烯酸全氟烷基乙酯混合物a)具有以下组成：
1-10wt％的具有4个氟化碳原子的符合式II的单体，
90-99wt％的具有6个氟化碳原子的符合式II的单体。
4.根据权利要求1的共聚物，特征在于所述(甲基)丙烯酸C12-C22烷基酯包括丙烯酸十六醇酯、丙烯酸硬脂酯和/或丙烯酸二十二醇酯。
5.根据权利要求1-4的共聚物用于纤维质基材的防水、防油和防污整理的用途。
6.根据权利要求1-4的共聚物和被保护的异氰酸酯的混合物的含水混合物。
7.根据权利要求6的含水混合物用于纤维质基材的防水、防油和防污整理的用途。 
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