CN1213385A - 氟代硫醚封端的马来酸共聚物 - Google Patents
氟代硫醚封端的马来酸共聚物 Download PDFInfo
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Abstract
公开了一种具有式Ⅱ单元的共聚物,其中M是H、碱金属、铵阳离子或其混合物;N是OM或OM、OR和NR1R2以摩尔比(OM)∶(OR)∶(NR1R2)为[1-(e+f)]∶e∶f的混合物,其中e和f各自独立地为0—0.5,条件是(e+f)小于0.8;R、R1和R2各自独立地为H或支化或直链的C1-20烷基;Y是C2-10的烷基、C6-12的芳基或C4-12的烷氧基;X是氟代硫羟基;Z是H;和v和w各自为正数,使得v和w的摩尔比为约0.4∶1-约1.3∶1。
Description
发明背景
聚酰胺、丝和羊毛纤维易遭受沾污。几种目前尼龙地毯所用的防污剂都是基于由全氟烷基乙基醇类衍生的聚合物。通常,全氟烷基乙基醇衍生物是加入到丙烯酸类聚合物或聚氨酯聚合物中通过轧染或喷洒的方法施加到各种基体。
此外,聚酰胺、丝和羊毛纤维易遭受各种试剂,特别是通常在软饮料中见到的酸性染料如FD&C Red Dye NO.40的沾色(Stainning)。已应用了各种防沾色剂,包括聚羧酸共聚物如那些由甲基丙烯酸或马来酸和磺化酚醛缩合物衍生的共聚物。这些防沾色剂可单独使用或组合使用。端烯烃与马来酐的水解共聚物作防沾色剂是众所周知的。用磺化酚醛缩合物与端烯烃/马来酸共聚物的共混物作防沾色剂也是众所周知的。
Sato和Yamauchi在1986年3月4日公布的美国专利4,574,139中公开了几种由能够自由基聚合的和具有含氟端基,由氟代硫醇衍生的单体制备的均聚物。Sato和Yamauchi在这些单体中列举了一些制备均聚物的α-烯烃、马来酐和马来酸酯。但是,这些单体的均聚物作为防沾色剂是无效的。
通常防沾色剂是在可控的pH条件下通过水性介质施加。防沾色剂的亲和性或上染性在pH小于3时最高。在低pH时经常要用表面活性剂帮助防沾色剂的溶剂化。
含氟化合物防污剂是已知的,它可有效地防止纤维沾污,但是对酸性染料的防污作用很小。因为含氟化合物防污剂不能从水溶液中上染,它们通常通过与防沾色剂分开的操作如喷洒、轧染或发泡以及随后干燥的步骤施加的。防沾色剂和防污剂的共用是比较经济的。但是,常规防沾色剂和防污剂的共用不能得到所需要的性能。
有需要提供具有防污和防沾色两种性能又可一步施用的试剂。本发明描述了一种可提供既防污又防沾色两种性能又可一步施用的试剂。
发明概述
M是H、碱金属、铵阳离子或其混合物;
N是OM或OM、OR和NR1R2以摩尔比(OM)∶(OR)∶(NR1R2)为[1-(e+f)]∶e∶f的混合物,其中e和f各自独立地为0-0.5,条件是(e+f)小于0.8;
R、R1和R2各自独立地为H或支化或直链的C1-20烷基;
Y是C2-10的烷基、C6-12的芳基或C4-12的烷氧基;
X是氟代硫羟基;
Z是H;和
v和w各自为正数,使得v和w的摩尔比为约0.4∶1-约1.3∶1。
本发明还包括提供纤维防污性和防酸性染料沾色性的方法,该方法包括任选在其他防沾色剂存在下施用有效量的如上所述的式Ⅱ组合物。这种方法包括对地毯就地的局部施用。本发明还包括一种施用了上述式Ⅱ的组合物的纤维。
本发明还包括制备上述式Ⅱ的组合物的方法,该方法包括下面的步骤1)和2):
1)在式Ⅰ的氟代硫醇存在下使马来酐与C4-12的α-烯烃反应
Rf-(A)d-B-SH Ⅰ其中
Rf是任选被至少一个氧原子间隔的全氟代直链或支链C3-14的脂族基;
A是二价基,选自-SO2-N(R3)-、-CON(R3)-、-S-和-SO2-,其中R3是H或C1-6的烷基;
d是0或1;和
B是二价线性烃基-CnH2n-,其中n为2至约12;
得到以X和Z封端的马来酐/α-烯烃的共聚物,其中X和Z与式Ⅱ的定义相同,和
2)使所述马来酐/α-烯烃的共聚物与R4OH反应得到式Ⅱ的组合物,其中R4是C1-18的烷基、碱金属离子或铵阳离子。
发明详述
本发明包括组合物,该组合物既可提供防污又可提供防沾色两种性能,并能通过一步法由水性介质施加到聚酰胺基体,如尼龙、丝和羊毛的地毯料、家具布,以及其他的纤维中。具体地说,本发明包括将全氟烷基基团加到马来酐/端烯烃共聚物防沾色剂中,方法是每摩尔马来酐和端烯烃共聚单体加入0.5-50毫摩尔,优选为1-25毫摩尔的氟代硫醇或氟代硫醇的混合物。
氟代硫醇具有式Ⅰ的结构:
Rf-(A)d-B-S-H (式Ⅰ)其中
Rf是任选被至少一个氧原子间隔的全氟代直链或支链的脂族基;
A是二价基,选自-SO2-N(R)-、-CON(R)-、-S-或-SO2-,其中R是H或C1-6的烷基;
d是0或1;和
B是二价线性烃基-CnH2n-,其中n为2至约12和优选为2。
优选,Rf含有至少3个和不大于14个碳原子。更优选Rf含有至少5个和不大于12个碳原子,最优选至少7个和不大于10碳原子。
代表性的氟代硫醇具有的结构:
CmF(2m+1)-CON(R)-(CH2)q-S-H其中R是H或具有1-6个碳原子的烷基,m是3-14,以及q是1-12;
CmF(2m+1)-SO2N(R)-(CH2)q-S-H其中R、m和q的定义同上;
F(CF2)p(CH2)nS-H其中n的定义同上和p是3-14,优选5-12,最优选7-10;
(CF3)2CF(CF2)r(CH2)nS-H,或
(CF3)2CF-O-(CF2)r(CH2)nS-H其中n的定义同上和r是0-11,优选2-9,最优选4-7;
(CF3)2CF-O-[CF(CF3)CF2-O-]t(CH2)nS-H其中n的定义同上和t是0-5,优选1-4,最优选2-3;
(CF3)2CF-O-[CF(CF3)CF2O]uCF(CF3)CF2-CONH(CH)2S-H其中n的定义同上和u是0-4,优选1-3;和
F(CF2)nCON(R)CH2CH2S-H,或
F(CF2)nSO2N(R)CH2CH2S-H其中n和R的定义同上。
硫醇是作为链转移剂。因而得到具有氟代硫醚封端的共聚物链,增加防污性给缩多酸防沾色剂。根据共聚单体和氟代硫醇或氟代硫醇混合物的相对活性的不同,产物聚合物中加入的氟代硫醇组分为30-80%。
链转移的过程是增长的聚合物链从,在这种情况下,硫醇中抽取氢而被终止,留下氟代的硫羟基。这种活性的硫羟基然后引发新的共聚物链。产物共聚物的一端被氟代硫醚基(式Ⅱ中的X)封端,而另一端主要是氢封端(式Ⅱ中的Z)。这些结构如下面表示水解的、部分酯化或部分酰胺化的马来酐/端烯烃共聚物的式Ⅱ所示。该式仅仅描述了共聚单体在共聚物中的比例,并不表示共聚物链中的任何单体的序列。其他的端基也可能存在,例如由聚合引发剂或溶剂衍生的端基。
虽然没有氟代端基的共聚物链仅仅提供防沾色性而没有防污性,但是本发明的实践是使共聚物的氟含量最大。得到最大氟含量的方法是应用最大分子量约700的氟代硫醇或硫醇类,和采用氟代硫醇与共聚单体的适当比例。分子量大于约700的氟代硫醇类活性逐渐变小,使得加入共聚物中的氟加入量降低。
正确地制备本发明的水解的,部分酯化或部分酰胺化的共聚物的特征是在浓度约5-约50%,优选1O-30%(重量)在水中形成透明的水溶液。如果通过抽取氢而形成的氟代硫羟基的活性不足以再引发共聚合反应,它可能最终与另一个基团,例如另一个硫羟基反应,在这种具体的情况下产生相应的水不溶的二硫化物。活性不足的硫醇的特征是加入到共聚物中的氟量低,并且形成混浊的水溶液。加入率的定义是由氟分析计算的加入到共聚物中硫醇量除以加到单体混合物中的硫醇量。
另一方面,活性氟代硫醇的摩尔比太大引起过多的链转移,会使得生成的共聚物的分子量太低。过低分子量的共聚物在纤维上的带液率(take-up)差。
本发明的共聚物的数均分子量(M
n)为约500-200,000,且优选为1,500-5,000。
M是H、碱金属、铵阳离子或其混合物;
N是OM或O-M、O-R和NR1R2以摩尔比(O-M)∶(O-R)∶(NR1R2)为[1-(e+f)]∶e∶f的混合物,其中e和f各自独立地为0-0.5,条件是(e+f)小于0.8;
R、R1和R2各自独立地为H或支化或直链的具有1-20碳原子的烷基;
X是氟代硫羟基;
Y是具有2-10个碳原子的烷基、具有6-12个碳原子的芳基或具有4-12个碳原子的烷氧基;
Z是H;和
v是1至约1500的正整数或正分数,w是约2-600的正整数或正分数,条件是v和w的摩尔比为约0.4∶1-约1.3∶1。
优选e和f独立地为0-0.3,条件是(e+f)小于0.6。
X是氟代硫醇链转移剂通过氢抽取形成的氟代硫酯醚端基。X的例子是由上述式Ⅰ的氟代硫醇类除去端基氢形成的基团。Z主要是H,但是Z可能是很微量的由引发剂或溶剂形成的基团。
对于Y,合适的端烯烃单体包括1-链烯烃、乙烯基取代的芳族单体或烷基乙烯基醚,这些单体如例举,但不限于此的1-辛烯、苯乙烯和丁基乙烯基醚。v/w的比例是共聚物中马来酐与端烯烃的摩尔比。
本发明优选的单体是马来酐和C4-C12的α-烯烃。最优选的是马来酐和1-辛烯。最优选的氟代硫醇是全氟癸基乙基硫醇。
本发明式Ⅱ的含氟代硫醚端基的水解的,部分酯化或部分酰胺化的马来酐共聚物是用马来酐和一种或几种共聚单体制备的,方法是在上述式Ⅰ的氟代硫醇存在下使马来酐与C4-12的α-烯烃反应生成中间态共聚物。该中间态共聚物然后与R4OH反应得到式Ⅱ的共聚物,其中R4是C1-18的烷基、碱金属离子或铵阳离子。共聚单体与马来酐的摩尔比为0.4∶1-1.3∶1,这些反应是在所选的氟代硫醇存在下进行的,氟代硫醇的量为每摩尔总单体0.5-50毫摩尔,优选每摩尔总单体1-25毫摩尔。聚合是在惰性气氛的聚合容器中进行,任选使用溶剂如甲基异丁基酮,反应温度为40-120℃,压力为常压或高压,取决于共聚单体和引发剂的类型。使用偶氮或过氧化物基团的引发剂。合适的自由基引发剂的例子是2,2’-偶氮双(3-甲基丁腈)如杜邦公司,Wilmington,DE,的“VAZO”67,或Atochem公司,Buffalo,NY,的过辛酸叔丁酯。得到的中间态马来酐共聚物然后或者用碱性水溶液水解,或者与适量的醇或胺反应得到式Ⅱ的部分酯或部分酰胺。式Ⅱ的共聚物的数均分子量为约500-200,000,优选为1,500-5,000,通过氟代硫醇的活性和浓度控制。水解的,部分酯化或部分酰胺化的共聚物溶于水中得到含全氟烷基的透明水溶液。
本发明的水解的,部分酯化或部分酰胺化的共聚物当通过一步法由酸性水溶液施加时,可以使聚酰胺、丝或羊毛纤维具有防沾色和防污两种性能。
本发明的水解的,部分酯化或部分酰胺化的共聚物可以通过各种本领域众所周知的方法施加到织物和地毯上,诸如通过地毯的Beck染色法所实施的由酸性水浴上染法,或加到染料浴水溶液中且与染料同时上染。它们也可以在连续染色如用KUSTER或OTTING地毯染色设备施加。其他合适的方法包括,但不限于此,轧染、发泡或喷洒法。
在第二个实施方案中,本发明的水解的,部分酯化或部分酰胺化的共聚物水溶液是与其他市售的基于酚醛树脂或甲基丙烯酸或马来酸的共聚物的防沾色剂共施用的。这种共施用采用含5-95%的本发明水解的,部分酯化或部分酰胺化的共聚物的混合物。
可以与本发明的共聚物共用的磺化酚醛缩合物产物防沾色剂包括任何磺化芳族羟基化合物-甲醛缩合物产物,这些产物在现有技术中被描述用作阻染剂或固色剂,换句话说,防染剂或改进染料在聚酰胺纤维上湿牢度的试剂。
适合本发明的市售酚醛缩合物产物的例子是“BAYGARD”DT(德国Bayer公司的产品,由双(4-羟苯基)砜、甲醛和苯酚磺酸制备的缩产物,见述于美国专利3,790,344)和“ERIONAL”LY,(Ciba-Geigy公司,Greensboro NC,的产品,由萘一磺酸、双(4-羟苯基)砜和甲醛的混合物缩合制备,见述于美国专利3,71 6,39 3)。英国Allied Colloid公司的磺化芳族羟基化合物-甲醛缩合物产物“ALGARD”NS;Yorkshire化学公司,Greenville SC,的“DYAPOL”SB-40;和Sybron化学公司,Wellford SC,的“STAINFREE”也是适用的。
本发明施用到聚酰胺、羊毛或丝纤维或织物的防污/沾色剂的量是能有效地赋予防沾色和防污作用的量。本领域的技术人员应用本领域熟知的试验方法,如下文所述的那些方法,可以很容易地确定这种浓度。例如,防污/沾色剂的施用浓度为基于纤维或织物重量的0.1-5.0%(owf),优选为0.3-2.0%owf。
施用浴的pH为1.5-9。但是,为将本发明的水解的,部分酯化或部分酰胺化的共聚物上染到基体上,要求pH等于或小于4。优选2-3的较低pH值。PH低于3时需要应用表面活性剂以提供均匀、稳定的水浴溶液。表面活性剂的量可由本领域的技术人员通过观察所用的水性体系确定。通常,表面活性剂的量占防污/沾色剂的活性成分量的10-100%,优选为20-50%,可足以保持均匀的浴溶液。适合于本申请的表面活性剂包括α-烯烃磺酸酯如“WITCONATE”AOS(Witco公司,Greenwich CT)、“CALSOFT”(Pilot化学公司,Avenel NJ)、月桂基磺酸钠如“DUPONOL”(Witco公司,Greenwich CT)和烷基化二磺酸化二苯基氧化物如“DOWFAX”(Pilot化学公司,Avenel NJ)和“CALFAX”(Cytec工业公司,Stamford CT)。一价或多价的电解质如硫酸钠和硝酸镁或硫酸镁可以加入以改进防污/沾色剂的上染性,用量占浴重的0.01-1%。
1H,1H,2H,2H-全氟辛烷硫醇、1H,1H,2H,2H-全氟癸烷硫醇和1H,1H,2H,2H-全氟十二烷硫醇在转让于Ciba-Geigy公司(Ardsley NY)的加拿大专利1,242,217中描述为LODYNE Rf硫醇。本发明所用的其他氟代硫醇链转移剂可以由市售的氟代羰酰氯或氟代磺酰氯与氨基烷基硫醇或羟基烷基硫醇用常规的方法反应制备。
防污/沾色剂在浴或溶液中完成上染或固定的温度为20-100℃,时间为几秒钟至1小时,优选50-85℃,5秒钟至5分钟。经常,这样处理的纤维或织物要进行汽蒸和/或热处理以赋予最佳的性能。本文所述的防污/沾色剂也可以在纤维纺丝、加拈或热定型操作时通过给油装置直接施加。本发明的防污/沾色剂也可以在pH2-10下就地施加到已经装于居室、办公室或其他地方的聚酰胺、聚酯、聚烯烃或羊毛地毯上。它们可以简单的水性制剂或水性香波制剂的形式施加,可带有或不带有一种或几种多氟有机的拒油、拒水和/或拒污的材料。
本发明的水解的,部分酯化或部分酰胺化的共聚物可以单独和与酚醛防沾色剂的混合物的形式施加到聚酰胺纤维上,处理基材的试验方法如下所述。
施用方法
将由29盎司/平方码(0.98kg/m2)的Superba-set尼龙6/6膨化变形长丝(BCF)(杜邦公司,Wilmington DE,提供)构成的白色割绒地毯(5g)于80℃在试验室Beck型设备中处理10分钟,在pH为2,浴/织物比为20∶1,用防沾色剂溶液(防沾色剂如各实施例所述),得到按活性成分计的施加负荷量为纤维重量的1.1%(owf)。向浴中不时加入每升2.0g的“MAGNAFLO”(硝酸镁的水溶液,由Sybron化学公司,Wellford SC,提供)。在pH调节前加入表面活性剂0.02g如“DOWFAX”2A-4(Pilot化学公司,Avenel NJ)或“WITCONATE”AOS(Witco公司,Greenwich CT)。地毯然后在自来水下洗涤,通过挤压部分脱水,在121℃(250°F)的强制热风烘箱中干燥约20分钟。
沾色试验
将地毯试样(1.5X3.5英寸)(3.8X8.9 cm)绒面朝上置于平的非吸收剂表面上。将10ml红色染料水溶液(0.2g FD&C Red Dye No.40和3.2g柠檬酸配成体积1升的溶液)倒入一个直径1英寸(2.54 cm)的圆筒中,该圆筒紧密地置于试样之上。在所有的液体被吸收后移走圆筒。沾色的地毯试样静置24小时后在冷的自来水下彻底冲洗并挤干。试样的颜色用Milolta色度仪CR200(Minolta公司,Ramsey NJ)通过测定未沾色和沾色的试样之间的色差“δa”确定。这种方法提供了一种高度精确的途径测定地毯着红色的程度。“δa”越高,颜色越红。比较例和实施例的沾色试验的结果列于下面的表1和2。
加速沾污试验(滚筒试验)
用双面胶粘带将地毯试样(1.5X3.5英寸)(3.8X8.9 cm)绒面朝上贴于直径8英寸(20.3cm)的金属滚筒的内表面上,直至内表面完全被地毯覆盖。然后向滚筒内放入250ml体积脏的“SURLYN”离子键树脂丸粒,该树脂丸粒是由1升体积的“SURLYN”8528离子键树脂(杜邦公司,Wilmington DE)丸粒与20g合成油(AATCC方法123-1988)掺混而成,和250ml体积5/16英寸(0.19 cm)的球轴承。然后密封滚筒,在一个滚筒型筒式研磨机内滚动3分钟。从滚筒内取出地毯试样,用筒式真空吸尘器清洁。
沾污程度用Milolta色度仪CR200(Minolta公司,Ramsey NJ)通过测定未沾污的比较样和沾污的地毯试样之间的暗度差“δE”确定。“δE”越高,试样越暗。两个“δE”单元的差是肉眼可区别的。比较例和实施例的沾污试验的结果列于下面的表1和2。
表1示出了未处理地毯试样(对比)、比较例A和B和未共施用酚醛防沾色剂的实施例1-3的性能。表2示出了未处理地毯、比较例A和B和共施用酚醛防沾色剂的实施例1-3的性能。酚醛防沾色剂与本发明共聚物的比例为20∶80。
比较例
比较例A和B不具有如本发明的式Ⅱ中的X表示的氟代硫醇端基。
比较例A
往聚合容器内加入29.4g(0.3摩尔)马来酐、30.1g(0.3摩尔)正丁基乙烯基醚、0.6g 1-十二烷硫醇和75g甲基异丁基酮。反应混合物在氮气下搅拌并加热到95℃。在1小时内经由注射泵慢慢加入过辛酸叔丁酯引发剂(6ml)。在95℃下搅拌24小时后,通过气相色谱(GC)分析无残留的正丁基乙烯基醚测出,让反应物冷却到室温。少量产物在70-80℃和减压(10-20Pa)下干燥得到深棕色的固体,该固体在67-82℃熔融,通过凝胶渗透色谱(聚苯乙烯标准物)测定的数均分子量为11,786和Mw/Mn比为1.17。其余的产物通过用稀氢氧化钠在75℃下加热1小时进行水解,并在减压(40-80Pa)下除去溶剂得到含15.0%活性成分的带褐色的液体。
比较例B
往聚合容器内加入294g(3摩尔)马来酐、235g1-辛烯(2.09摩尔)、6.0g1-十二烷硫醇和750g甲基异丁基酮。反应混合物在氮气下搅拌并加热到95℃。在4小时内经由注射泵慢慢加入过辛酸叔丁酯引发剂(42ml)。在95℃下搅拌20小时后,通过GC分析无马来酐测出,让反应物冷却到室温。少量产物在70-80℃和减压(10-20Pa)下干燥得到琥珀色的树脂,该树脂在138-153℃熔融,通过凝胶渗透色谱(聚苯乙烯标准物)测定的数均分子量为3,320和Mw/Mn比为1.97。其余的产物通过用稀氢氧化钠在75℃下加热3小时进行水解,并在减压(40-80Pa)下除去溶剂得到含21.3%活性成分的透明的琥珀色溶液。
实施例
实施例1
往聚合容器内加入24.5g(0.25摩尔)马来酐、26.0g(0.25摩尔)苯乙烯、1.3g 1H,1H,2H,2H-全氟癸烷硫醇(2.7毫摩尔)和50g甲基异丁基酮。反应混合物在氮气下搅拌并加热到95℃。在1小时内经由注射泵慢慢加入过辛酸叔丁酯引发剂(1.5ml)。随后的放热需要进行重复冷却。从溶剂中分离出粘状物质的聚合物。95℃下搅拌3小时后,在溶剂层中无苯乙烯测出。取出少量聚合物在80℃和减压(10-20Pa)下干燥。得到的固体在189-204℃熔融,含1.49%的氟,以及通过凝胶渗透色谱(聚苯乙烯标准物)测定的数均分子量为25,300和Mw/Mn比为2.44。其余的聚合物由溶剂中分离,在稀氢氧化钠中水解,在室温静置后得到混浊粘溶液,其中含15.9%活性成分和0.075%的氟,这相应于29%的起始氟硫醇。
实施例2
往聚合容器内加入19.6g(0.2摩尔)马来酐、20.0g(0.2摩尔)正丁基乙烯基醚、0.8g 1H,lH,2H,2H-全氟癸烷硫醇(1.7毫摩尔),和50g甲基异丁基酮。反应混合物在氮气下搅拌并加热到75℃。在2小时内两次加入0.2g“VAZO”67(杜邦公司,Wilmington DE)引发剂。随后的放热通过重复冷却控制。反应物逐渐变粘,4小时后通过GC分析无残留正丁基乙烯基醚测出,让反应物冷却到室温。取出少量聚合物在80℃和减压(10-20Pa)下干燥,得到的琥珀色固体在170-160℃熔融,数均分子量为1,260和Mw/Mn比为2.4。其余的产物在减压(40-80Pa)下除去溶剂之前,通过用稀氢氧化钠在75℃下加热1小时进行水解,得到含约15.9%活性成分的黄色混浊水溶液。在室温下静置过夜后,少量固体从含0.073%氟,相应于35%的起始氟硫醇,的混浊溶液中分离。
实施例3
往聚合容器内加入20.5g(0.205摩尔)马来酐、16.5g(0.147摩尔)1-辛烯、1.0g 1H,1H,2H,2H-全氟癸烷硫醇(2.1毫摩尔),以及52g甲基异丁基酮。反应混合物在氮气下搅拌并加热到95℃。在2小时内经由注射泵慢慢加入过辛酸叔丁酯引发剂(4.5ml)。在95℃下保持19小时后,通过GC分析无马来酐测出,让反应产物冷却到室温。少量产物在70-80℃和减压(10-20Pa)下干燥得到固体树脂,该树脂在125-134℃熔融,通过凝胶渗透色谱(聚苯乙烯标准物)测定的数均分子量为2,398和Mw/Mn比为1.78。其余的产物通过用稀氢氧化钠在75℃下加热1小时进行水解,并在减压(40-80Pa)下除去溶剂得到琥珀色液体,其中含15%活性成分和含0.165%的氟,这相应于约70%的起始氟硫醇。
实施例4
往聚合容器内加入294g(2.94摩尔)马来酐、232.0g(2.07摩尔)1-辛烯、11.0g的48%1H,1H,2H,2H-全氟癸烷硫醇(11毫摩尔)和52%1H,1H,2H,2H-全氟十二烷硫醇(9.9毫摩尔)的混合物,以及500g甲基异丁基酮。反应混合物在氮气下搅拌并加热到95℃。在4小时内经由注射泵慢慢加入过辛酸叔丁酯引发剂(42ml)。反应物在95℃下搅拌21小时后,通过GC分析无马来酐测出,让反应物冷却到室温。少量产物在70-80℃和减压(10-20Pa)下干燥得到含1.15%氟的琥珀色树脂,该树脂通过凝胶渗透色谱(聚苯乙烯标准物)测定的数均分子量为3,490和Mw/Mn比为1.96。其余的产物通过用稀氢氧化钠在75℃下加热3小时进行水解,并在减压(40-80Pa)下除去溶剂得到轻微混浊的琥珀色液体,其中含23.3%活性成分和含0.169%的氟,这相应于约56%的起始氟硫醇。
实施例5
往聚合容器内加入20.5g(0.205摩尔)马来酐、16.5g(0.147摩尔)1-辛烯、0.8g 1H,1H,2H,2H-全氟辛烷硫醇(2.1毫摩尔),以及52g甲基异丁基酮。反应混合物在氮气下搅拌并加热到95℃。在1小时内经由注射泵慢慢加入过辛酸叔丁酯引发剂(4.5ml)。反应物在95℃下保持17小时后,通过GC分析无马来酐测出,让反应产物冷却到室温。少量产物在70-80℃和减压(10-20Pa)下干燥得到琥珀色树脂,该树脂在125-135℃熔融,含1.30%的氟,通过凝胶渗透色谱(聚苯乙烯标准物)测定的数均分子量为2,920和Mw/Mn比为1.85。其余的产物通过用稀氢氧化钠在75℃下加热1小时进行水解,并在减压(40-80Pa)下除去溶剂得到琥珀色液体,其中含16.0%活性成分和含0.123%的氟,这相应于约60%的起始氟硫醇。
表1防沾色性和防污性
实施例#(a) | 氟分析(ppm)(b) | 沾色性δa | 沾污性(c)δE |
对比(未处理) | … | 39 | 28 |
实施例A(d) | … | 10 | 2O |
实施例B(d) | … | 2 | 19 |
实施例1 | 80 | 5 | 15 |
实施例2 | 70 | 7 | 17 |
实施例3 | 80 | 1 | 14 |
(a)所有的施用都是在pH2.0和80℃下在白色割绒1150 Superba-set尼龙膨化变形长丝(BCF)上施加,施加量1.1%owf。
(b)氟分析是在处理的地毯上的实测值。
(c)滚筒法沾污。
(d)制备共聚物无氟代硫醇。
表2带20%酚醛防沾色剂的共混物的防沾色性和防污性
实施例#(a) | 酚醛防沾色剂的类型 | 氟分析(ppm)(b) | 沾色性δa | 沾污性(c)δE |
对比(未处理) | … | … | 40 | 37 |
实施例A(d) | “ERIONAL”LY | … | 2 | 28 |
“BAYGARD”DT | … | 1 | 25 | |
实施例B(d) | “ERIONAL”LY | … | 1 | 28 |
“BAYGARD”DT | … | 1 | 28 | |
实施例1 | “ERIONAL”LY | 110 | 4 | 15 |
“BAYGARD”DT | ND | 2 | 26 | |
实施例2 | “ERIONAL”LY | 90 | 5 | 16 |
“BAYGARD”DT | ND | 2 | 20 | |
实施例3 | “ERIONAL”LY | 110 | 1 | 15 |
“BAYGARD”DT | ND | 1 | 17 |
(a)所有的施用都是在pH2.0和80℃下在白色割绒1150 Superba-set尼龙膨化变形长丝(BCF)上施加,施加量1.1%owf。
(b)氟分析是在处理的地毯上的实测值。
(c)滚筒法沾污。
(d)制备共聚物无氟代硫醇。
ND未测出
Claims (10)
2.权利要求1的组合物,其中Y是C6的烷基。
3.权利要求1的组合物,其中X是下式的氟代硫羟基
Rf-(A)d-B-S-其中
Rf是任选被至少一个氧原子间隔的全氟代直链或支链C3-14的脂族基;
A是二价基,选自-SO2-N(R3)-、-CON(R3)-、-S-和-SO2-,其中R3是H或C1-6的烷基;
d是0或1;和
B是二价线性烃基-CnH2n-,其中n为2至约12。
5.权利要求4的方法,其中式Ⅱ的组合物有效量为占纤维重量的约0.1-约5.0%。
6.权利要求4的方法,其中式Ⅱ的组合物是与其他酚醛树脂防沾色剂或聚羧酸防沾色剂中的至少一种同时施加。
8.一种纤维,该纤维已施加了含具有式Ⅱ单元的共聚物的组合物:其中
M是H、碱金属、铵阳离子或其混合物;
N是OM或OM、OR和NR1R2以摩尔比(OM)∶(OR)∶(NR1R2)为[1-(e+f)]∶e∶f的混合物,其中e和f各自独立地为0-0.5,条件是(e+f)小于0.8;
R、R1和R2各自独立地为H或支化或直链的C1-20烷基;
Y是C2-10的烷基、C6-12的芳基或C4-12的烷氧基;
X是氟代硫羟基;
Z是H;和
v和w各自为正数,使得v和w的摩尔比为约0.4∶1-约1.3∶1。
9.权利要求8的纤维,其选自尼龙、丝或羊毛。
M是H、碱金属、铵阳离子或其混合物;
N是OM或OM、OR和NR1R2以摩尔比(OM)∶(OR)∶(NR1R2)为[1-(e+f)]∶e∶f的混合物,其中e和f各自独立地为0-0.5,条件是(e+f)小于0.8;
R、R1和R2各自独立地为H或支化或直链的C1-20烷基;
Y是C2-10的烷基、C6-12的芳基或C4-12的烷氧基;
X是氟代硫羟基;
Z是H;和
v和w各自为正数,使得v和w的摩尔比为约0.4∶1-约1.3∶1。
所述方法包括
1)在式Ⅰ的氟代硫醇存在下使马来酐与C4-12的α-烯烃反应
Rf-(A)d-B-SH Ⅰ其中
Rf是任选被至少一个氧原子间隔的全氟代直链或支链C3-14的脂族基;
A是二价基,选自-SO2-N(R3)-、-CON(R3)-、-S-和-SO2-,其中R3是H或C1-6的烷基;
d是0或1;和
B是二价线性烃基-CnH2n-,其中n为2至约12;
得到以X和Z封端的马来酐/α-烯烃的共聚物,其中X和Z与式Ⅱ的定义相同,和
2)使所述马来酐/α-烯烃的共聚物与R4OH反应得到式Ⅱ的组合物,其中R4是C1-18的烷基、碱金属离子或铵阳离子。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/617,518 | 1996-03-13 | ||
US08/617,518 US5712348A (en) | 1996-03-13 | 1996-03-13 | Maleic acid copolymers with fluorinated thioether end-cap |
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CN1213385A true CN1213385A (zh) | 1999-04-07 |
CN1105733C CN1105733C (zh) | 2003-04-16 |
Family
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Application Number | Title | Priority Date | Filing Date |
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CN97192999A Expired - Fee Related CN1105733C (zh) | 1996-03-13 | 1997-03-12 | 氟代硫醚封端的马来酸共聚物 |
Country Status (10)
Country | Link |
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US (2) | US5712348A (zh) |
EP (1) | EP0886659B1 (zh) |
JP (1) | JP3723222B2 (zh) |
KR (1) | KR19990087751A (zh) |
CN (1) | CN1105733C (zh) |
AU (1) | AU727201B2 (zh) |
CA (1) | CA2249024A1 (zh) |
DE (1) | DE69702186T2 (zh) |
TW (1) | TW377360B (zh) |
WO (1) | WO1997033926A1 (zh) |
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DE69835649T2 (de) * | 1997-10-15 | 2007-09-13 | E.I. Dupont De Nemours And Co., Wilmington | Copolymere aus Maleinsäure oder dessen Anhydrid und fluorierten Olefinen |
DE10125158A1 (de) * | 2001-05-22 | 2002-12-05 | Basf Ag | Nieder-und hochmolekulare Emulgatoren, insbesondere auf Bassis von Polyisobutylen, sowie deren Mischungen |
US7335234B2 (en) * | 2002-10-16 | 2008-02-26 | Columbia Insurance Company | Method of treating fibers, carpet yarns and carpets to enhance repellency |
US20050015886A1 (en) * | 2003-07-24 | 2005-01-27 | Shaw Industries Group, Inc. | Methods of treating and cleaning fibers, carpet yarns and carpets |
JP4726464B2 (ja) * | 2004-11-05 | 2011-07-20 | 富士フイルム株式会社 | 光学部材形成用重合性組成物、光学部材、および、光学部材の製造方法 |
US7785374B2 (en) | 2005-01-24 | 2010-08-31 | Columbia Insurance Co. | Methods and compositions for imparting stain resistance to nylon materials |
US20070050912A1 (en) * | 2005-09-02 | 2007-03-08 | Materniak Joyce M | Reduction of turmeric and iodine staining |
US20070136953A1 (en) * | 2005-12-20 | 2007-06-21 | Materniak Joyce M | Stability for coapplication |
US7901589B2 (en) | 2009-06-29 | 2011-03-08 | E.I. Du Pont De Nemours And Company | Propanediol soil resist compositions |
US8357621B2 (en) * | 2009-06-29 | 2013-01-22 | E.I. Du Pont De Nemours And Company | Soil resist method |
Family Cites Families (12)
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BE759823A (fr) * | 1969-12-03 | 1971-05-17 | Bayer Ag | Agents ameliorant la solidite au mouille |
DE1961369C3 (de) * | 1969-12-06 | 1979-03-01 | Bayer Ag, 5090 Leverkusen | Dioxydiphenylsulfon-Formaldehyd-Kondensationsprodukte und ihre Verwendung als Gerbstoffe und Naßechtheitsverbesserungsmittel |
DE3069623D1 (en) * | 1979-05-03 | 1984-12-20 | Ciba Geigy Ag | Oligomers with perfluor alkyl end groups that contain mercapto groups, process for their preparation and their use as suface-active substances and as additives in fire-extinguishing compositions |
US4574139A (en) * | 1983-06-17 | 1986-03-04 | Kuraray Co., Ltd. | Polymer having a fluorine-containing end group and production of the same |
US4592940A (en) * | 1983-12-16 | 1986-06-03 | Monsanto Company | Stain-resistant nylon carpets impregnated with condensation product of formaldehyde with mixture of diphenolsulfone and phenolsulfonic acid |
US4591591A (en) * | 1984-03-08 | 1986-05-27 | Eli Lilly And Company | Pyridazinone derivatives as inotropic agents |
FR2575165B1 (fr) * | 1984-12-26 | 1987-01-23 | Atochem | Telomeres fluores a groupements hydrophiles, leur procede de preparation et leur utilisation comme agents tensioactifs en milieu aqueux, notamment comme additifs aux emulseurs proteiniques anti-incendie |
US4948650A (en) * | 1987-12-21 | 1990-08-14 | E. I. Du Pont De Nemours And Company | Stain-resistant textile substrates |
KR920006476B1 (ko) * | 1987-12-21 | 1992-08-07 | 이 아이 듀우판 디 네모아 앤드 캄파니 | 방오성 폴리아미드 직물 지지체 및 직물 지지체에 방오성을 제공하는 방법 |
ZA889534B (en) * | 1987-12-21 | 1990-08-29 | Du Pont | Stain-resistant aromatic/meleic anhydride polymers |
US5460887A (en) * | 1990-12-13 | 1995-10-24 | E. I. Du Pont De Nemours And Company | Stain-resistant polyamide substrates |
JPH06504097A (ja) * | 1990-12-27 | 1994-05-12 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 無水マレイン酸/ビニルまたはアリルエーテルポリマー耐汚染性材料 |
-
1996
- 1996-03-13 US US08/617,518 patent/US5712348A/en not_active Expired - Fee Related
-
1997
- 1997-03-07 TW TW086102777A patent/TW377360B/zh active
- 1997-03-12 WO PCT/US1997/003914 patent/WO1997033926A1/en not_active Application Discontinuation
- 1997-03-12 JP JP53281397A patent/JP3723222B2/ja not_active Expired - Fee Related
- 1997-03-12 AU AU20776/97A patent/AU727201B2/en not_active Ceased
- 1997-03-12 CA CA002249024A patent/CA2249024A1/en not_active Abandoned
- 1997-03-12 DE DE69702186T patent/DE69702186T2/de not_active Expired - Fee Related
- 1997-03-12 CN CN97192999A patent/CN1105733C/zh not_active Expired - Fee Related
- 1997-03-12 EP EP97909022A patent/EP0886659B1/en not_active Expired - Lifetime
- 1997-03-12 KR KR1019980707223A patent/KR19990087751A/ko not_active Application Discontinuation
- 1997-09-25 US US08/937,953 patent/US5824372A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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JP3723222B2 (ja) | 2005-12-07 |
US5824372A (en) | 1998-10-20 |
CA2249024A1 (en) | 1997-09-18 |
EP0886659B1 (en) | 2000-05-31 |
EP0886659A1 (en) | 1998-12-30 |
DE69702186T2 (de) | 2001-03-01 |
AU2077697A (en) | 1997-10-01 |
CN1105733C (zh) | 2003-04-16 |
DE69702186D1 (de) | 2000-07-06 |
US5712348A (en) | 1998-01-27 |
TW377360B (en) | 1999-12-21 |
AU727201B2 (en) | 2000-12-07 |
KR19990087751A (ko) | 1999-12-27 |
WO1997033926A1 (en) | 1997-09-18 |
JP2000507282A (ja) | 2000-06-13 |
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