CN1871207A - 全氟烷基取代的丙烯酸酯单体及其聚合物 - Google Patents
全氟烷基取代的丙烯酸酯单体及其聚合物 Download PDFInfo
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- CN1871207A CN1871207A CNA200480031535XA CN200480031535A CN1871207A CN 1871207 A CN1871207 A CN 1871207A CN A200480031535X A CNA200480031535X A CN A200480031535XA CN 200480031535 A CN200480031535 A CN 200480031535A CN 1871207 A CN1871207 A CN 1871207A
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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
- 235000019394 potassium persulphate Nutrition 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—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 singly-bound oxygen atoms
- C07C233/17—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 singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
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Abstract
本发明公开了式(I)的各种氟代烷基酰氨基烷基醇及其对应的(甲基)丙烯酸酯。这些氟代烷基酰氨基烷基(甲基)丙烯酸酯单体可以与范围广泛的各种常用烯键式不饱和单体共聚合。所得的共聚物可用作纸张、纺织品和硬质表面(如圬工和木材)的防水剂、防油剂和防脂剂。
Description
背景及先有技术
全氟烷基(在下文中将其缩写为RF)取代的聚合物为各种底物(如纺织品和纸张)赋予防油和防水性能的用途世人皆知。这些聚合物的绝大多数为可用于处理纸张和纸产品以便赋予其防油和防水性能的全氟烷基取代的丙烯酸酯共聚物。美国专利3,919,183(Jager等)公开了可用作多孔底物(如各种纺织品材料和纸张)防油涂料的聚合物,这些聚合物包含全氟烷基丙烯酸乙酯。美国专利4,582,882(Lynn等)描述了全氟烷基丙烯酸酯共聚物的各种氟化纸张施胶剂。另外,Fitzgerald的美国专利5,674,961公开了用于纸张防水、防油和防脂的各种氟化物聚合物。用于合成上述全氟烷基化聚合物的单体只衍生自RF取代的醇,其中在RF与羟基之间存在亚乙基基团。
一些专利,例如美国专利5,663,273也描述了RF取代的聚氨酯。在美国专利3,769,307和3,567,500中描述了通过与全氟烷基取代的羧酸酯反应从聚乙烯亚胺中衍生的聚酰胺-氨基聚合物。这些聚合物包含RF取代的酰胺和仲氨基基团的混合物。这些聚合物为纺织品底物提供疏油性以及亲水性。
在美国专利3,754,026中指出,由1当量的二亚乙基三胺、2当量的RF酸和1当量的酸酐所制备的双RF酰胺一元羧酸可用作织物整理剂。在美国专利3,271,430中描述了可用作耐化学物质的表面活性剂的类似RF酰胺取代的聚乙烯亚胺。它们通过全氟链烷酸与超过量的乙烯亚胺进行反应获得。RF取代的酸与包含通过连接基附着于碳-碳主链上的伯氨基侧基的聚合物进行反应的产物在美国专利4,606,973中作为平滑底物的低表面能涂料提出了权利要求。
美国专利3,818,074描述了饱和与不饱和的各种氟化醇,它们可以具有将3-12个碳原子的全氟烷基基团与羟基基团分离的2-12个亚甲基。
美国专利3,498,958公开了具有1-14个将全氟烷基基团与酰氨基基团分离的亚甲基的全氟烷基酰氨基烷基醇、其(甲基)丙烯酸酯和从中衍生的各种共聚物。所述酰氨基烷基醇为下述式I的酰氨基链烷醇的饱和类似物,通过不同的合成路线获得。
发明概述
本发明的一个方面为下式I的新型RF-醇:
其中:
RF为含有4-20个碳原子的直链或支链全氟烷基基团;
R2为氢或具有1-4个碳原子的烷基基团;和
m和n彼此独立为2-11的整数。
通过以下方法合成式I的所述RF-醇:使线形末端不饱和的一元羧酸或其低级酯与氨基醇进行反应,生成酰胺-链烷醇。然后在自由基条件下使该烯键式不饱和中间产物与RF-碘化物进行反应,再用碱对产物进行脱氢卤化作用。对于制备式I的全氟烷基酰氨基烷基醇而言,此工艺可获得高的总收率。
通过使氟代烷基酰氨基醇I与醇活性化合物进行反应,式I的全氟烷基酰氨基烷基醇可用来合成各种氟化衍生物。
本发明的另一个方面提供下式II的新型丙烯酸酯或甲基丙烯酸酯单体:
其中:
RF为含有4-20个碳原子的直链或支链全氟烷基基团;
R1为氢或甲基;
R2为H或具有1-4个碳原子的烷基基团;和
m和n彼此独立为2-11的整数。
本发明的其它方面为衍生自式II丙烯酸酯或甲基丙烯酸酯单体的各种聚合物和共聚物,及其将防水、防油和防脂性能赋予所得处理后的纸张、纺织品和硬表面(如圬工和木材)的用途。残余双键可用于交联最终的聚合物。
附着于长链烃部分上的全氟烷基取代基(如十一烯基团)作为抗油剂表现出改善的表面活性和改善的效力,可能是因为这种长链烃基团通过其链与链之间的相互作用有助于相当微弱的反应RF-基团的取向所致。氢通过所述全氟烷基酰胺-烷基部分中的酰氨基基团的键合还促进了烃-碳氟化合物长链的稳定线形调整,籍此为需要良好防水和防油性能的涂料的低自由表面能作出贡献。
详尽公开
本发明的一个方面提供下式I的新型氟代烷基酰氨基烷基醇:
其中:
RF为含有4-20个碳原子的直链或支链全氟烷基基团;
R1为氢或甲基;
R2为氢或具有1-4个碳原子的烷基基团;和
m和n彼此独立为2-11的整数。
所述全氟烷基部分RF可以是单一的全氟烷基基团(如全氟己基),或这些基团的混合物(如C4F9-、C6F13-、C8F17-、C10F21-、C12F25-、C14F29-和C16F31-的混合物)。
本发明优选的化合物包括那些其中RF为饱和并且含有6-18个碳原子的化合物,是完全氟化的并含有至少一个全氟甲基的端基。最优选RF是完全氟化的平均具有约4-16个碳原子的线形碳链。
优选R2为氢或具有1-2个、优选1个碳原子的烷基。
优选n为2-11的整数、优选为8,而m为2-6的整数、特别为2或3。
本发明的另一个方面提供下式II的丙烯酸酯或甲基丙烯酸酯单体:
其中:
RF为含有4-20个碳原子的直链或支链全氟烷基基团;
R1为氢或甲基;
R2为H或具有1-4个碳原子的烷基基团;和
m和n彼此独立为2-11的整数。
对R1、R2、m、n和RF的优选与式I先前定义的相同。
本发明的另一个方面是从包含式II的氟代烷基酰氨基烷基(甲基)丙烯酸酯单体的单体混合物中制备氟化物共聚物,以及这些氟化物共聚物以内部或外部的方式应用的各种防水、防油和防脂纸张施胶剂的用途(除了防油性能之外还赋予优异的防水性能)。
在一个实施方案中,以相对于所述共聚物总重量的以下重量百分数进行共聚合,从式II的RF-酰氨基烷基(甲基)丙烯酸酯和其它烯键式不饱和单体中制备共聚物:
a)45-90%重量的下式II单体:
其中:
RF为含有4-20个碳原子的直链或支链全氟烷基基团;
R1为H或CH3;
R2为H或具有1-4个碳原子的烷基基团;和
m和n彼此独立为2-11的整数;和
b)5-30%重量的下式III的单体:
(R2)2N-(CH2)k-X1-C(=O)-C(R1)=CH2 (III)
其中:
所述氮原子被部分或全部季铵化或为盐的形式,X1为O或N(R2),其中:
R1和R2如上所定义,每一个R2为相同或不同;和
k为2-4;和
c)0-10%重量的至少一种可共聚合的非氟化乙烯基单体。
优选RF为4-16个碳原子的直链全氟烷基基团,X1为氧,R1、R2和n如上所定义。
特别优选的是其中的各种单体以相对于所述共聚物总重量的以下重量百分数进行共聚合所得的共聚物:
a)65-85%重量;b)5-30%重量;和c)0-10%重量。
最好使用RF的链长为4-16个碳原子的式II化合物的混合物来制备本发明的共聚物。在一个特别优选的实施方案中,用于制备本发明聚合物的式II的单体为RF-丙烯酸酯,其RF-链的链长分布为:13±2%C6F13、48±2%C8F17、23±2%C10F21和1.6%C12F25或更高级。
式III的优选化合物有N,N-二甲基氨基乙基(甲基)丙烯酸酯;N,N-二乙基氨基乙基(甲基)丙烯酸酯;N,N-二甲基氨基丙基甲基丙烯酰胺和N-叔丁基氨基乙基甲基丙烯酸酯,及其盐。
可用作共聚单体(c)的有大量市售的各种丙烯酸酯和甲基丙烯酸酯,以及苯乙烯;但优选甲基丙烯酸甲酯、N-羟甲基丙烯酰胺、2-羟乙基甲基丙烯酸酯、丙烯酸、甲基丙烯酸缩水甘油酯、偏二氯乙烯、乙酸乙烯酯、1-乙烯基-2-吡咯烷酮、丙烯腈、甲基丙烯腈、乙烯基氯、偏二氯乙烯和1-乙烯基-2-吡咯烷酮。
可通过以下方法合成式I的全氟烷基酰氨基烷基醇:使线形末端不饱和的C5-C14一元羧酸或其低级酯与下式III的氨基醇进行反应,
生成下式Ia的酰胺-链烷醇:
采用自由基生成机理,使该烯键式不饱和中间产物与RF-碘化物进行反应;然后用碱金属氢氧化物对该中间产物进行脱氢卤化作用,其中RF、R2、m和n如上所定义。
优选第一反应步骤在没有溶剂的条件下进行,在40-180℃的温度下加热混合物约1-5小时。优选线形末端不饱和的一元羧酸,例如4-戊烯酸和10-十一碳烯酸。在第二步骤中,采用自由基生成机理,使该烯键式不饱和中间产物与RF-碘化物进行反应。然后用碱金属氢氧化物(如氢氧化钠或氢氧化钾)对该中间产物进行脱氢卤化作用。
在自由基引发剂(如偶氮化合物或过氧化物)的存在和35-150℃的常规引发温度下,RF-碘化物加成到烯烃的反应很容易进行。然而,在少量亚硫酸根、亚硫酸氢根或连二硫酸根离子的水溶液的存在下,所述反应将进行得更快,并且得到更高的转化率。
用于将RF-碘化物加成到烯烃和随后的脱氢卤化作用以制备本发明式I化合物的通用加工条件在美国专利5,919,299中有更详尽的描述。
根据需要,在RF-碘化物加成反应期间可以存在溶剂。非限制性的例子包括各种酮,例如丙酮、甲乙酮或甲丙酮;各种酯,例如乙酸异丙酯;各种醇,例如乙醇或丁醇;各种醚,例如二烷或二(2-羟乙基)醚;各种烃,例如甲苯或辛烷;各种酰胺,例如二甲基甲酰胺和各种内酰胺,例如N-甲基吡咯烷酮。
RF-碘化物加成产物的脱氢卤化作用-般在50-100℃的水中进行,使加合物与无机强碱(如氢氧化钠或氢氧化钾)或有机强碱(如1,8-二氮杂双环(5.4.0)十一碳-7-烯(DBU))反应数小时。在非水相中得到可分离和用水洗涤的反应产物。可将溶剂汽提;或者通过在水相与有机相之间进行彻底的相分离,然后干燥有机相,从而可将产物作为溶液分离出去。分离的模式取决于具体的产物。主要形成反式烯烃,通过NMR确定顺式/反式比。
在碱(如三乙胺)的存在下(以便捕集所形成的氯化氢)通过使所述RF-酰胺-链烷醇与烯丙酰氯或甲基烯丙酰氯进行反应可制备式II的丙烯酸酯或甲基丙烯酸酯单体。可以利用其它采用锡催化剂的方法(如酯交换)和其它方法来合成式II的丙烯酸酯和甲基丙烯酸酯。
通过上述的单体混合物在水乳浊液或在溶剂中进行自由基聚合制备本发明的共聚物。对乳液聚合而言,通常采用各种水溶性的共溶剂有助于其它不溶的RF-单体经水相的迁移。可用的共溶剂包括丙酮和甲醇。适宜的自由基引发剂包括各种偶氮化合物和水溶性过氧化物,例如过硫酸钾。在含水介质中进行聚合的其它变化中,首先用表面活性剂和均化剂将所述RF-单体乳化于水中,然后再与其它单体进行共聚合。
但制备本发明聚合物的优选方法为溶液聚合。可用的溶剂为各种酮,例如丙酮、甲基异丁酮和甲乙酮;各种酯,例如乙酸异丙酯;各种醇,例如甲醇、乙醇和异丙醇;以及各种芳香烃,例如甲苯。
所述聚合一般在约50-100℃的温度下,采用自由基引发剂(通常为过氧化物或偶氮化合物)进行。可用的引发剂包括过氧化苯甲酰、1,2-偶氮-二-异丁腈(AIBN)和1,2-偶氮-二-(2-甲基丁腈)(VAZO-67)。
可以存在数量为0.01-1%摩尔的链转移剂,例如烷基硫醇。
聚合结束后,通过加入有机酸(如乙酸)的水溶液可以很容易将溶液转化为阳离子水分散体或水溶液;蒸馏出有机溶剂后得到固含量适宜为20-40%重量的分散体或溶液。
从包含本发明式II的氟代烷基酰氨基烷基(甲基)丙烯酸酯单体的单体混合物中制备的氟化物共聚物可用作多孔底物(如纸张和纺织品)上或硬质底物(如木材、金属或圬工)上的涂料。在造纸工业中,它们的主要有效性基于其将防油和防脂性能赋予用于食品包装或用于要求耐油性物质的任何其它类型应用的纸张的能力。
因此,本发明的另一个方面涉及将防油和防脂性能赋予纸张的方法,该方法包括将一定量的能够有效地赋予防油和防脂性能的本发明共聚物掺入到纸张内。
通过经胶料-压模(外部纸张施胶)到干纸张上的涂装工艺或将所述共聚物的溶液或乳化液加入到含水纸浆(内部纸张施胶)都可将所述共聚物应用于纸张上。在两种情况中,基于干纸张或纸浆重量计算,优选共聚物的施用量范围为0.02-1%重量,大致对应于将0.01-0.5%重量的氟掺入到纸张或纸浆内。
本发明的另一个方面涉及将防水、防油和防脂性能赋予纺织品材料的方法,该方法包括采用0.2-1.0%重量的能有效地将防水、防油和防脂性能赋予纺织品材料上的本发明共聚物处理织物。
适宜的纺织品材料包括各种纤维素材料(特别是棉)、聚酰胺(如尼龙)、羊毛和丝、聚酯和聚烯烃及其各种共混物,例如聚酯-棉共混物。在一个实施方案中,所述纺织品材料为地毯。
本发明还有一个方面涉及将防油和防脂性能赋予硬质底物(如木材、金属或圬工)的方法,该方法包括将一定量的能有效地赋予防油和防脂性能的本发明共聚物施用于硬质底物的表面上。这些水性氟化物共聚物组合物可以通过任何常规的方式(例如用海绵或布进行抹涂、用刷子涂覆、喷涂和其它方法)施用于其表面上。
以下的各实施例描述了本发明的一些实施方案,但本发明并非受限于这些实施例。应清楚的是:在不背离本发明精神或范畴的前提下,根据此处的公开可对所公开的各实施方案做出大量的修改。因而这些实施例并非用于限制本发明的范畴。相反,本发明的范畴仅由所附的权利要求及其等价物来决定。在这些实施例中,除非另有说明,否则所有给定的份数均以重量计。
所述非限制性的实施例举例说明如何合成本发明的各种共聚物,并且详细描述了将其施用于各种底物的方法。它们也展示了所述共聚物在各种底物上的良好性能。
实施例1
通过将例如10-十一烯酸与链烷醇胺(如乙醇胺或丙醇胺)进行缩合可合成式I的全氟烷基酰氨基烷基醇。以下给出用于合成的通用方法。
全氟烷基酰氨基烷基醇的合成
在100毫升装有机械搅拌器、温度计、蒸馏冷凝器的三颈烧瓶中装入20.2克(0.107摩尔)的10-十一烯酸。将反应烧瓶加热至50℃,然后缓慢加入9.8克(0.16摩尔)的乙醇胺。缓慢将反应温度增加至180℃,并在该温度下保持4小时。反应进程通过气相色谱进行跟踪。4小时后收集到1.8克(95%的理论值)的水。将反应混合物冷却至室温,将棕黄色产物溶解于乙醇中,然后倒入水中。过滤所得酰胺链烷醇的白色沉淀物,用水洗涤并干燥,得到24.0克(收率=97%)的白色粉末。
1H NMRδ:5.85(m,1H),5.0(m,1H),4.9(m,1H),3.6(t,2H),3.3(m,2H),2.2(2H),2.1(q,2H),1.6(b,2H),1.4(t,2H),1.35(8H)ppm。13CNMRδ:173,140,115,62,43,36,34,30,29.8,25ppm。
向100毫升装有机械搅拌器、冷凝器和氮气吹扫入口管的三颈烧瓶中加入10.0克(44毫摩尔)以上所得的酰胺链烷醇、11克正丙醇、5克水和27.0克(44毫摩尔)Tel AN(DuPont的Zonyl Tel AN,其同系物分布为:53.0%的C8F17I、30.6%的C10F21I、11.7%的C12F25I、3.6%的C14F29I和1.0%的C16F33I)。在约74℃下搅拌混合物。向反应混合物加入0.8克(4.2毫摩尔)的焦亚硫酸钠和0.25克(1.3毫摩尔)的VAZO-67。反应进程通过气相色谱进行跟踪。3小时后检测不到TelAN。在约50℃下将5.0克50%的NaOH溶液缓慢加入到烧瓶内容物,混合物在约70℃下搅拌。3小时后气相色谱显示脱氢卤化作用已完成。将反应混合物冷却至60℃;然后加入15.0克甲苯和10.0克水。停止搅拌后移出产物顶层并用20.0克水洗涤两次。在旋转蒸发仪上除去溶剂,然后产物在50℃的高真空下干燥,得到具有48%重量氟的淡黄色粘性固体的下式(101)化合物:
1H NMRδ:6.4(1H,m),5.7(1H,m),3.6(2H,m),3.3(2H,m),2.2(4H,m),1.6(2H,b),1.4(2H,b),1.3(8H)ppm。13C NMRδ:176,117(m),144(m),110-120(多重线,CF3和CF2基团),61,26,43,37,33,30.2,29.9,27ppm。
实施例2
全氟烷基酰氨基烷基丙烯酸酯的合成
向100毫升装有机械搅拌器和冷凝器的三颈烧瓶中加入8.45克(11.8毫摩尔)的全氟烷基-取代的醇(101)、30.0毫升的MIBK和2.0克(20毫摩尔)的三乙胺。在氮气气氛下向10℃的反应混合物内缓慢加入1.5克(16.6毫摩尔)的烯丙酰氯在5毫升MIBK内的溶液,然后在室温下搅拌反应混合物5小时。再加入氯化钠饱和水溶液,使混合物沉降。移出含有产物的顶层,用30.0克饱和氯化钠水溶液洗涤一次。在65℃的旋转蒸发仪上蒸发溶剂,然后在高真空下得到8.2克(收率=94%)具有43%氟的褐色式(101)固体的下式(102)化合物:
实施例3
向装有回流冷凝器、温度计和机械搅拌器的烧瓶内加入5.0克(6.37毫摩尔)实施例2的全氟烷基丙烯酸酯、2.0克(10.8毫摩尔)N,N-二乙基-氨基乙基甲基丙烯酸酯、0.2克(3毫摩尔)的甲基丙烯酸甲酯和5.0克甲基异丁酮。用氮气吹扫烧瓶,加入0.1克VAZO-67。在74-78℃的温度下搅拌混合物5小时进行聚合。然后将乙酸(在30克水中的0.1克乙酸)的水溶液加入到聚合混合物内,搅拌混合物15分钟。将混合物转移至圆底烧瓶内,在真空下除去甲基异丁酮,得到黄色共聚物水溶液。
实施例4-6
采用偶氮双异丁腈作为引发剂,以及重量比如下的共聚单体,用实施例3的方法制备实施例4-6。
共聚物的组成,%重量 | ||||
实施例 | RF-单体 | 氨基(甲基)丙烯酸酯 | 甲基丙烯酸甲酯 | 其它 |
3 | 69 | 28 | 3 | - |
4 | 83 | 17(DEEM) | - | - |
5 | 89 | 5 | 2 | 4(NVP) |
6 | 75 | 22 | 3 | - |
DEEM=二乙基氨基乙基甲基丙烯酸酯
NVP=1-乙烯基-2-吡咯烷酮
实施例6
重复实施例3的方法,采用2.4克正-十二烷基硫醇作为链转移剂。
以下实施例展示所述各种新型RF-聚合物作为内部纸张施胶剂的性能。
实施例7
如下述试验实施例3-6的化合物。
内部胶料应用和试验
在由CHINET Company提供的小型纸板制造机上做成10英寸直径的纸板。所述机器由支承三个沿径向附着的模的旋转构件组成,其中一个称为“成形模”,在步骤1中该模浸渍于纸浆内,真空下纸浆通过该模过滤到板上;旋转1/4转后纸板到达步骤2,称为“真空模”的模通过抽吸和加热模压并干燥纸板,在剩下的两个1/4旋转中到达两个十字头模,通过加热对纸板进一步干燥。纸板的最终干度受真空强度及纸浆滤水特性以及各模温度的影响。要求的最小干度至少为94%(即含有不超过6%的水分),否则所述纸板将丧失湿强度。
在以下的实验中采用了如下条件:
机器装置:10英寸板;
目标干度:95-96%;真空模:300/1.XH:385/2.XH:375。
湿部:
纸浆由CHINET Company提供,3磅/试运转,含有作为湿部化学品的以40秒间隔加入到搅拌的纸浆内的以下物质,加入次序如下:
Nalco 7607-阳离子助留剂和凝结剂(NALCO CHEM.Co.),8磅/吨;
烷基-乙烯酮二聚物(AKD)-防水剂(HERCULES Corp.),6磅/吨;
氟化物聚合物胶料-折算成加入的F的量为0.1%重量;
Nalco 625-阴离子凝结剂(NALCO CHEM.Co.),1磅/吨。
试验:进行如下两种试验:
热盐水溶液和热油试验。
步骤:
1.纸板称重;
2.将72℃的2%盐水或99℃的Mazola玉米油以足够覆盖整个表面的量倾倒至纸板上;
3.5分钟后,倒掉溶液,用纸巾擦干纸板并重新称重;
4.计算吸收重量百分数,并用肉眼将渗透程度(R)分级:
R=0=>50%;1=25-50%;2=<25%;3=无。
吸收百分数是对水/油不渗透性能更准确的度量。
对成品纸板进行“机外”试验,也即制成后不久和24小时后的试验。
“机外”纸板的干度通过重量分析进行确定。
在下表中显示了试验结果。
实施例的化合物 | 所加的F% | 热油不渗透性 | 热水不渗透性(2%盐水) | ||||
机外 | 24小时 | ||||||
R | %吸收 | R | %吸收 | R | %吸收 | ||
3 | 0.07 | 3 | 1 | 15 | 3 | 3 | |
3 | 0.15 | 3 | 1 | 15 | 3 | 3 |
结果揭示了在两种不同的氟含量下优异的油和水不渗透性能。
实施例8
以下实施例展示了所述新型共聚物作为外部纸张施胶剂的有效性。
外部胶料施用
将中和的测试溶液加入到纸张生产商淀粉(Stayco M,氧化淀粉,来自Staley Corp.)的4%水溶液内,然后通过搓涂(纸张经淀粉溶液浸渍,并穿过单压料辊)施用于未上胶的纸张上。所得纸片在环境条件下干燥15分钟,然后在200(97℃)的“Emerson Speed Drier”(具有防水布罩的加热金属板)中干燥3分钟。
防油和防脂试验
抗油脂性能试验
采用TAPPI UM 557 OIL KIT TEST确定表面的防油性能,所述试验由采用十二种在15秒内表面张力渗透递减的蓖麻油-庚烷-甲苯混合物进行确定组成,等级为最低的1至12。
Ralston-Purina(RP2)试验
采用用于宠物食品材料的Ralston-Purina试验确定防脂性能;RP-2试验,Ralston-Purina Company,包装参考手册卷06,试验方法。内容简述:将交向折皱的测试纸张置于压印有100个方格的网格片上。将5克沙置于折皱的中心。将合成油和用于显色的染料的混合物用滴管吸移到所述沙上,样品在60℃下保持24小时。使用至少两个样品,通过着色网格部分的百分数确定等级。
松节油试验
根据TAPPI T454 om-94,进行确定等级的预试验,其中可以预期油或脂穿透所述纸张。
防水和耐醇试验
Cobb施胶度试验
如TAPPI T 441 om-90中所述,采用Cobb施胶度试验可以确定防水性能。
耐IPA试验
在该试验中将异丙醇-水的混合物滴置于纸张上,3分钟后观察纸张背面的渗透情况;如果没有发生渗透,则施用下一种更高IPA含量的混合物。评价等级基于不发生渗透的最高IPA的%重量。等级基于5%IPA增量。结果示于下表中。
实施例的化合物 | %F | 抗油脂性能试验 | RP-2 | 松节油试验 | Cobb施胶度试验 | IPA不渗透性试验 |
3 | 0.09 | 8 | 4×0 | 1800+ | 21 | 10 |
4 | 0.1 | 10 | 4×0 | 1800+ | 20 | 40 |
P-5141 | 0.12 | 12 | 4×0 | 1800+ | 22 | 40 |
P-2082 | 0.10 | 10 | 4×0 | 1800 | 72 | 0 |
FC-8453 | 0.10 | 10 | 4×0 | 1800+ | 22 | 40+ |
1)Ciba LodyneP-514是可购自Ciba Specialty Chemicals Corp.的工业用聚合物氟化纸张施胶剂;
2)Ciba LodyneP-208E是可购自Ciba Specialty Chemicals Corp.的工业用磷酸酯氟化纸张施胶剂;
3)ScotchguardFC-845是可购自3M Corp.的工业用聚合物氟化纸张施胶剂。
Claims (25)
2.权利要求1的醇,其中RF是饱和的并含有6-18个碳原子,是全氟化的并含有至少一个全氟甲基端基。
3.权利要求1的醇,其中RF是全氟化的平均具有约4-16个碳原子的线形碳链,R2为氢或具有1-2个碳原子的烷基基团,n为5-10的整数,m为2-6的整数。
4.权利要求3的醇,其中RF是全氟化的平均具有约4-16个碳原子的线形碳链,R2为氢,n为8,m为2-3的整数。
6.一种下式II的丙烯酸酯或甲基丙烯酸酯:
其中:
RF为含有4-20个碳原子的直链或支链全氟烷基基团;
R1为氢或甲基;
R2为H或具有1-4个碳原子的烷基基团;和
m和n彼此独立为2-11的整数。
7.权利要求6的酯,其中RF是全氟化的平均具有约4-16个碳原子的线形碳链,R2为氢或具有1-2个碳原子的烷基基团,n为5-10的整数,m为2-6的整数。
8.一种共聚物,所述共聚物包含以相对于所述共聚物总重量的以下重量百分数进行共聚合的单体:
a)45-90%重量的下式II的单体:
其中:
RF为含有4-20个碳原子的直链或支链全氟烷基基团;
R1为H或CH3;
R2为H或具有1-4个碳原子的烷基基团;和
m和n彼此独立为2-11的整数;和
b)5-30%重量的下式III的单体:
(R2)2N-(CH2)k-X1-C(=O)-C(R1)=CH2 (III)
其中:
所述氮原子被部分或全部季铵化或为盐的形式,X1为O或N(R2),其中:
R1和R2如上所定义,每一个R2为相同或不同;和
k为2-4;和
c)0-10%重量的至少一种可共聚合的非氟化乙烯基单体。
9.权利要求8的共聚物,其中d)为0。
10.权利要求8的共聚物,其中所述单体以相对于所述共聚物总重量的以下重量百分数进行共聚合:
a)65-85%重量;b)5-30%重量;和c)0-10%重量。
11.权利要求8的共聚物,其中RF是全氟化的平均具有约4-16个碳原子的线形碳链,R2为氢或具有1-2个碳原子的烷基基团,n为5-10的整数,m为2-6的整数。
12.权利要求8的共聚物,其中式III的单体选自N,N-二甲基氨基乙基(甲基)丙烯酸酯;N,N-二乙基氨基乙基(甲基)丙烯酸酯;N,N-二甲基氨基丙基甲基丙烯酰胺和N-叔丁基氨基乙基甲基丙烯酸酯,及其盐。
13.权利要求8的共聚物,其中所述可共聚合的非氟化乙烯基单体选自苯乙烯、甲基丙烯酸甲酯、N-羟甲基丙烯酰胺、2-羟乙基甲基丙烯酸酯、丙烯酸、甲基丙烯酸缩水甘油酯、偏二氯乙烯、乙酸乙烯酯、1-乙烯基-2-吡咯烷酮、丙烯腈、甲基丙烯腈、乙烯基氯。
14.一种制备权利要求8的共聚物的方法,所述方法包括在自由基引发剂的存在下,使以下物质进行反应:
a)45-90%重量的下式II的单体:
其中:
RF为含有4-20个碳原子的直链或支链全氟烷基基团;
R1为H或CH3;
R2为H或具有1-4个碳原子的烷基基团;和
m和n彼此独立为2-11的整数;和
b)5-30%重量的下式III的单体:
(R2)2N-(CH2)k-X1-C(=O)-C(R1)=CH2 (III)
其中:
所述氮原子被部分或全部季铵化或为盐的形式,X1为O或N(R2),其中:
R1和R2如上所定义,每一个R2为相同或不同;和
k为2-4;和
c)0-10%重量的至少一种可共聚合的非氟化乙烯基单体,和
任选的链转移剂。
15.一种将防油和防脂性能赋予纸张的方法,所述方法包括将一定量能有效地赋予防油和防脂性能的权利要求8的共聚物掺入到所述纸张内。
16.权利要求15的方法,其中通过在胶料-压模的涂装工艺中或将所述共聚物加入到含水纸浆中可将所述共聚物施用于干纸张上。
17.权利要求15的方法,其中施用了基于所述纸张或纸浆的干重的0.02-1%重量的所述共聚物。
18.一种将去污和抗污特性赋予纺织品材料的方法,所述方法包括用一定量能有效地赋予去污和抗污特性的权利要求8的共聚物处理所述纺织品材料。
19.权利要求18的方法,其中用基于干纺织品材料的重量的0.02-1%重量的所述共聚物处理所述纺织品材料。
20.权利要求18的方法,其中所述纺织品材料为地毯。
21.防油和防脂的纸张或纸浆,所述纸张或纸浆包含0.02-1%重量的权利要求8的共聚物。
22.纺织品材料,所述纺织品材料包含0.02-1%重量的权利要求8的共聚物。
23.权利要求22的纺织品材料,所述纺织品材料选自各种纤维素材料、聚酰胺、聚酯和聚烯烃及其各种共混物。
24.权利要求23的纺织品材料,所述纺织品材料选自棉、尼龙、羊毛、丝和各种聚酯-棉共混物。
25.一种将防油和防脂性能赋予硬质底物的方法,所述方法包括将一定量的能有效地赋予防油和防脂性能的权利要求8的共聚物施用于所述硬质底物的表面上。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102834425A (zh) * | 2010-04-16 | 2012-12-19 | 株式会社尼欧斯 | 防污性赋予剂 |
CN105985697A (zh) * | 2015-03-18 | 2016-10-05 | 斯沃奇集团研究和开发有限公司 | 包含涂有防油扩散剂的表面的基质和该基质的防油扩散方法 |
CN106905198A (zh) * | 2017-03-08 | 2017-06-30 | 江苏理文化工有限公司 | 一种含全氟聚醚链的丙烯酸酯及其合成方法 |
CN106905201A (zh) * | 2017-03-08 | 2017-06-30 | 江苏理文化工有限公司 | 一种含多氟链的双丙烯酸酯及其合成方法 |
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US8771470B2 (en) * | 2012-01-17 | 2014-07-08 | Agc Chemicals Americas, Inc. | Method of preparing a treated article and treated article formed therefrom |
CA3069462A1 (en) | 2017-07-16 | 2019-01-24 | Neuere, Llc | Ambroxol to improve and/or extend healthspan, lifespan and/or mental acuity |
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US3271430A (en) * | 1963-02-07 | 1966-09-06 | Dow Chemical Co | Nu-perfluoroacyl polyalkylenimines |
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US3567500A (en) * | 1968-04-18 | 1971-03-02 | Us Agriculture | Fluoroamide-amino polymers and process for imparting oleophobic yet hydrophilic properties to fibrous materials |
US3498958A (en) * | 1968-06-27 | 1970-03-03 | Nat Starch Chem Corp | Water-and oil repellency agents |
US3646153A (en) * | 1969-10-17 | 1972-02-29 | Allied Chem | Synthetic fibers having improved soil and stain repellency |
CH582719A5 (zh) * | 1973-09-12 | 1976-12-15 | Ciba Geigy Ag | |
US4582882A (en) * | 1982-10-13 | 1986-04-15 | Minnesota Mining And Manufacturing Company | Fluorochemical copolymers and ovenable paperboard and textile fibers treated therewith |
US4606973A (en) * | 1984-05-11 | 1986-08-19 | The Dow Chemical Company | Substrate with perfluorocarbon polymeric coatings having low critical surface tensions |
US5491261A (en) * | 1994-07-01 | 1996-02-13 | Ciba-Geigy Corporation | Poly-perfluoroalkyl-substituted alcohols and acids, and derivatives thereof |
US5674961A (en) * | 1996-04-12 | 1997-10-07 | E. I. Du Pont De Nemours And Company | Oil water and solvent resistant paper by treatment with fluorochemical copolymers |
JP3624615B2 (ja) * | 1997-02-28 | 2005-03-02 | ユニマテック株式会社 | 新規共重合体およびそれを含有する撥水撥油剤 |
US6162369A (en) * | 1997-05-14 | 2000-12-19 | 3M Innovative Properties Company | Fluorochemical composition comprising a polyurethane having a fluorochemical oligomer and a hydrophilic segment to impart stain release properties to a substrate |
JP3876495B2 (ja) * | 1997-09-12 | 2007-01-31 | ユニマテック株式会社 | 撥水撥油剤およびその製造法 |
JP4300678B2 (ja) * | 1999-08-03 | 2009-07-22 | ユニマテック株式会社 | 防汚加工剤の製造法 |
US6451717B1 (en) * | 1999-12-14 | 2002-09-17 | E. I. Du Pont De Nemours And Company | Highly durable oil/water repellents for textiles |
US6566470B2 (en) * | 2000-04-14 | 2003-05-20 | Ciba Specialty Chemicals Corporation | Fluorinated polymeric paper sizes and soil-release agents |
WO2002024828A1 (fr) * | 2000-09-21 | 2002-03-28 | Daikin Industries, Ltd. | Dispersion aqueuse d'eau et de d'oleofuge de son procede de fabrication |
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- 2004-10-21 WO PCT/EP2004/011884 patent/WO2005049552A1/en active Application Filing
- 2004-10-21 CN CNA200480031535XA patent/CN1871207A/zh active Pending
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102834425A (zh) * | 2010-04-16 | 2012-12-19 | 株式会社尼欧斯 | 防污性赋予剂 |
CN102834425B (zh) * | 2010-04-16 | 2014-11-05 | 株式会社尼欧斯 | 防污性赋予剂 |
CN105985697A (zh) * | 2015-03-18 | 2016-10-05 | 斯沃奇集团研究和开发有限公司 | 包含涂有防油扩散剂的表面的基质和该基质的防油扩散方法 |
CN106905198A (zh) * | 2017-03-08 | 2017-06-30 | 江苏理文化工有限公司 | 一种含全氟聚醚链的丙烯酸酯及其合成方法 |
CN106905201A (zh) * | 2017-03-08 | 2017-06-30 | 江苏理文化工有限公司 | 一种含多氟链的双丙烯酸酯及其合成方法 |
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US7247691B2 (en) | 2007-07-24 |
EP1678120B1 (en) | 2010-09-22 |
US20080315147A1 (en) | 2008-12-25 |
US20050148747A1 (en) | 2005-07-07 |
DE602004029270D1 (de) | 2010-11-04 |
US20080033131A1 (en) | 2008-02-07 |
BRPI0415817A (pt) | 2006-12-26 |
ES2349712T3 (es) | 2011-01-10 |
WO2005049552A1 (en) | 2005-06-02 |
EP1678120A1 (en) | 2006-07-12 |
ATE482184T1 (de) | 2010-10-15 |
BRPI0415817B1 (pt) | 2014-06-24 |
US7754917B2 (en) | 2010-07-13 |
US7754624B2 (en) | 2010-07-13 |
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