CN1255929A - 赋予基材污斑脱除性的包含具有含氟低聚物和亲水性片段的聚氨基甲酸酯的含氟化合物组合物 - Google Patents
赋予基材污斑脱除性的包含具有含氟低聚物和亲水性片段的聚氨基甲酸酯的含氟化合物组合物 Download PDFInfo
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Abstract
一种制备包含聚氨基甲酸酯的含氟化合物组合物的方法,它包括使下列物质反应:(A)式(I):Mf mMn-Q1-T1的含氟化合物低聚物,其中:Mf mMn代表包含源自氟化单体的m个单元和源自无氟单体的n个单元的含氟化合物低聚物,氟化单体和无氟单体可以相同或不同;m代表2-40的值;n代表0-20的值;T1是-OH或-NH2;Q1和T1一起表示从以T1官能化的链转移剂去除一个氢原子所获得的有机残基;(B)能与异氰酸酯反应的双官能化合物;(C)能与异氰酸酯反应的单官能化合物,该化合物包含聚(氧化烯)基团;与(D)三异氰酸酯反应。用该方法制得的含氟化合物组合物处理的基材具有优良的污斑脱除性能,尤其对油性污斑和诸如葡萄酒、茶和咖啡之类的水基污斑。
Description
发明领域
本发明涉及用于处理基材,尤其是诸如织物之类的纤维基材,为基材提供污斑脱除性能的含氟化合物组合物。
发明背景
用于处理诸如皮革、织物和纸张等基材的含氟化合物组合物已为人知,这类含氟化合物组合物可用于向基材提供各种性能,如斥水和/或斥油性,防水性、污斑脱除性和防污性。例如,美国专利5,276,175揭示的包括含氟化合物低聚物的异氰酸酯衍生物。具体而言,揭示的含氟化合物组合物包含氟化物,所述氟化物包括含氟化合物低聚物部分、有机部分和在施用于纤维基材时能提供柔软手感、污斑脱除、斥水性或耐久性的基团,其中的含氟化合物低聚物部分通过源自异氰酸酯的连接基连接到有机部分。经这样的组合物处理的基材具有耐久性,耐摩擦性以及油和水的排斥性。此专利的一个实施例中,描述了基于三异氰酸酯、氟低聚物和甲氧基聚环氧乙烷二醇(methoxypolyethyleneoxide glycol)缩合物的含氟化合物组合物。证实了这种组合物在聚酯/棉掺混织物上的污斑脱除性。
美国专利5,350,795揭示的含氟化合物组合物可处理织物纤维以及织物,提供斥油性和斥水性,而无需热处理。此组合物包括一种(a)由氟化丙烯酸酯单体、聚(亚烷基)二醇丙烯酸酯或甲基丙烯酸酯、或聚(亚烷基)二醇二丙烯酸酯或二甲基丙烯酸酯组成的含氟化合物丙烯酸酯共聚物;和(b)包含由脂族或芳族的三异氰酸酯或更高级数的异氰酸酯、氟化醇、胺、或硫醇的全氟烷基侧基、以及聚(亚氧烷基)二醇或二硫醇的聚烷氧基化的聚氨基甲酸酯的基本上没有有机溶剂的水溶液或分散体。
美国专利4,788,287和4,792,354揭示的一种斥水性和斥油性化合物有至少两个末端片段和一个连接末端片段的中间片段,其分子量为800-20,000。该化合物的每个末端片段含有至少一个由-CONH-连接基连接的多氟烷基基团,中间片段是含至少两个-CONH-连接基团的氨基甲酸酯低聚物,末端片段和中间片段通过-CONH-连接基连接。美国专利4,792,354揭示的氨基甲酸酯低聚物还含有亲水性分子链。
美国专利5,491,261揭示了二、三和多-全氟烷基取代的醇和酸,以及它们的衍生物,它们可由全氟烷基碘化物和二、三或多烷基醇或酸制得。它们可以和异氰酸酯、环氧化合物、酸酐、酸或酸衍生物反应制备各种斥油和斥水组合物。
含氟化合物组合物还可以用于从诸如织物的基材脱除污渍或污垢。用各种改性添加剂,如柔软剂、硬化剂和润滑剂对织物进行常规处理,向商品织物提供所需的性能,这通常会增加织物的亲油性,其接受油污的倾向显著增加,降低其在洗涤后脱除污斑的能力。已知基于氟化化合物和非氟化的亲水性化合物的混合物、或基于含有氟化合物的疏油性片段(“F”)和非氟化的亲水性片段(“H”)的化学“杂化”化合物的含氟化合物组合物可作为污斑脱除组合物,因为在正常穿着时它们能提供斥油性,抑制油污垢通过毛细作用或扩散进入织物或纤维束,有利于洗涤期间的污斑脱除。
美国专利3,574,791揭示的由F和H片段构成的嵌段共聚物可用作污斑脱除剂。“F”片段基本上没有亲水基,而“H”片段基本上没有氟化脂族基团。此专利中指出由于这种分段,聚合物是“自动适应的(autoadaptable)”,即用这类聚合物处理的织物在大气环境中将是斥油性和斥水性的,并且在水中洗涤时,会成为亲水性,使污斑能够去除。设想有各种可能的化学键连接“F”和“H”片段,包括由醇和异氰酸酯衍生的氨基甲酸酯键。
美国专利5,509,939揭示的含氟化合物组合物能提供基材污斑脱除性能。该含氟化合物组合物包括含脲键的烷氧基聚氧化烯氟代氨基甲酸酯,可通过使(a)至少一种含至少三个异氰酸酯基团的多异氰酸酯与(b)至少一种含氟化合物试剂,该试剂含有一个有至少一个氢原子和至少两个各自有至少两个F原子的碳原子的官能团,(c)至少一种亲水性、水可溶剂化的试剂,该试剂含有一个有至少一个反应活性氢原子的官能团,和(d)至少一种含有一个反应活性氢的一种试剂反应制得,在与异氰酸酯基团反应中,产生具有对纤维基材有潜在反应活性的官能度,然后使产物与水反应,使反应物(b)、(c)和(d)与55-95%的异氰酸酯基团反应,水与其余的异氰酸酯反应。
尽管已知有许多能向基材提供污斑脱除性的含氟化合物组合物,但是仍然需要改进性能的含氟化合物组合物。要求含氟化合物组合物的性能包括天然纤维基材,如棉花以及棉花和聚酯的掺混物的易洗涤性,尤其是对油性污斑(脏的马达油、植物油)和水基污斑(茶、咖啡);低生产成本;高的储藏稳定性;即使少量使用时也具备易乳化性和具有高性能。还要求含氟化合物组合物为基材提供优良的斥污性,和斥油和/或斥水性。
发明概述
本发明涉及制备包括聚氨基甲酸酯的含氟化合物组合物的方法,该方法包括使下列物质:
(A)式(I)的含氟化合物低聚物
Mf mMn-Q1-T1 (I)
其中:
Mf mMn代表包含源自氟化单体的m个单元和源自无氟单体的n个单元的含氟化合物低聚物,氟化单体和无氟单体可以相同或不同;
m表约2-40的值;
n代表0-约20的值;
T1是-OH或-NH2;
Q1和T1一起表示从以T1官能化的链转移剂去除一个氢原子所获得的有机残基;
(B)能与异氰酸酯反应的双官能化合物;和
(C)能与异氰酸酯反应的单官能化合物,该化合物包含聚(氧化烯)基团;与
(D)三异氰酸酯反应。
本发明还提供了可通过上面方法制得的包含聚氨基甲酸酯的含氟化合物组合物,以及用该含氟化合物组合物提供基材污斑脱除性能。
还提供了用该含氟化合物组合物的一种对基材进行处理,以及用所述的一种含氟化合物组合物处理的基材。
发明详述
根据本发明,术语“单官能”化合物指仅含有一个能与异氰酸酯反应的官能团的化合物。术语“双官能”化合物指仅有两个能与异氰酸酯反应的官能团的化合物。
术语“官能化含氟化合物低聚物”指含有能与异氰酸酯反应的官能团的含氟化合物低聚物。
本发明的含氟化合物组合物可以两步法反应制得。第一步中,制得官能化含氟化合物低聚物,该低聚物在第二步中进一步反应形成聚氨基甲酸酯。
第一步中,制得式(I)的含氟化合物低聚物:
Mf mMn-Q1-T1 (I)
其中:
Mf mMn代表包含源自氟化单体的m个单元和源自无氟单体的n个单元的含化合物低聚物,氟化单体和无氟单体可以相同或不同;
m代表约2-40的值;
n代表0-约20的值;
T1是-OH或-NH2;
Q1和T1一起表示从以T1官能化的链转移剂去除一个氢原子所获得的有机残基。
含氟化合物低聚物的m值在约2-40之间,较好的在约2-20之间,更好的在约3-15之间。n值为0-约20,较好的为约3-10。根据较好的实施方案,n值小于m值。源自两种或多种不同的氟化单体和/或两种或多种不同的无氟单体的含氟化合物低聚物也属于本发明的范围。
上述式中,Q1通常表示下式的有机残基:
-S-R-
其中:
R代表有机二价连接基,宜选自直链或支链的亚烷基(较好的有约2-6个碳原子)、亚环烷基、亚芳基和亚芳烷基。
含氟化合物低聚物可通过羟基或氨基官能化链转移剂存在下自由基低聚含氟化合物单体(Rf-L1-E)或与烃单体(Rh-E’)的组合制得。本发明中术语“烃”指任何基本上无氟的含氢和碳,以及任选的一个或多个取代基的有机部分。含氟化合物低聚物的脂族骨架包括足够数量的聚合单元来使这部分呈低聚状。脂族骨架较好的包括约2-40个源自含氟化合物单体的聚合单元和0-约20个源自烃单体的聚合单元。
在含氟化合物单体中,氟代脂族基团Rf是氟化的、稳定的、惰性的、较好是饱和的、非极性的单价脂族基团。它可以是直链、支链、环或上述的组合。可以含有杂原子,如氧、二价或六价硫、或氮。较好的Rf是完全氟化的基团,但是氢或氯原子可以作为取代基存在,如果对每两个碳原子,这两种原子的任一种不超过一个原子的话。Rf基团有至少约3个至约18个碳原子,较好的约3-14,最好是约6-12个碳原子,宜含有约40-80%(重量)的氟,更好的约50-78%(重量)氟。Rf基团的末端部分是全氟化部分,较好的含有至少7个氟原子,如CF3CF2CF2-、(CF3)2CF-、F5SCF2-。较好的Rf基团是完全氟化或基本上氟化,较好遵循下式CnF2n+1,其中n约为3-18。
连接基L1将Rf基团连接到可自由基聚合的基团E。L1较好的含有1-约20个碳原子。L1可任选含有氧、氮、含硫基团或它们的组合,较好的L1没有显著干扰自由基低聚反应的官能团(如可聚合的烯烃双键、硫醇、和其它本领域技术人员已知的官能度)。合适的L1基团的例子包括直链、支链或环状的亚烷基、亚芳基。亚芳烷基、含氧基(oxy)、氧代基(oxo)、羟基、硫代、磺酰基、硫氧基(sulfoxy)、氨基、亚氨基、氨磺酰基、羧酰胺基、羰氧基(carbonyloxy)、亚氨酯基(urethanylene)、1,3-亚脲基、以及上述的组合,如氨磺酰基亚烷基。较好的连接基选自亚烷基、有约1-4个氧化烯部分的聚(氧化烯),以及根据下式的有机二价连接基:
其中:
R3代表有2-4个碳原子的直链或支链亚烷基;和
R4代表要1-4个碳原子的烷基。
Rh是无氟有机基团。
E和E’是可自由基聚合的基团,通常含有能与其本身或彼此聚合的烯键不饱和部分。合适的部分包括如源自乙烯基醚、乙烯基酯、烯丙基酯、乙烯基酮、苯乙烯、乙烯基酰胺、丙烯酰胺、马来酸酯、富马酸酯、丙烯酸酯和甲基丙烯酸酯的那些部分。其中较好的是α、β不饱和酸酯,如丙烯酸酯和甲基丙烯酸酯。
如上所述的含氟化合物单体Rf-L1-E及其制备方法已为人们所知,披露于如美国专利2,803,615。这样的化合物的例子包括含氟化合物的丙烯酸酯、甲基丙烯酸、乙烯基醚的通类、和含氟化磺酰氨基的烯丙基化合物、源自含氟化合物调聚物醇的丙烯酸酯或甲基丙烯酸酯、源自含氟化合物羧酸的丙烯酸酯或甲基丙烯酸酯、和EP-A-526 976中揭示的全氟烷基丙烯酸酯或全氟烷基甲基丙烯酸酯。
较好的含氟化合物单体的例子包括:
CF3(CF2)4CH2OCOC(CH3)=CH2
CF3(CF2)6(CH2)2OCOC(CH3)=CH2
CF3(CF2)6(CH2)2OCOCH=CH2
CF3(CF2)6CH2OCOC(CH3)=CH2
CF3(CF2)6CH2OCOCH=CH2
CF3(CF2)7(CH2)2OCOCH=CH2
R=甲基、乙基或正丁基。
合适的烃单体Rh-E’也已为人们所知,并且一般能够购得。这样的化合物的例子包括能自由基聚合的烯键化合物,例如,烯丙基酯,如乙酸烯丙基酯和庚酸烯丙基酯;烷基乙烯基醚或烷基烯丙基醚,如十六烷基乙烯基醚、十二烷基乙烯基醚、2-氯乙基乙烯基醚、乙基乙烯基醚;不饱和酸,如丙烯酸、甲基丙烯酸、α-氯丙烯酸、巴豆酸、马来酸、富马酸、衣康酸和它们的酐和酯,如乙烯基、烯丙基、甲基、丁基、异丁基、己基、庚基、2-乙基-己基、环己基、月桂基、十八烷基、异冰片基或烷氧基乙基的丙烯酸酯和甲基丙烯酸酯;α-β不饱和腈,如丙烯腈、甲基丙烯腈、2-氯丙烯腈、丙烯酸2-氰基乙酯、氰基丙烯酸烷基酯;α、β-不饱和羧酸衍生物,如烯丙基醇、甘醇酸烯丙基酯、丙烯酰胺、甲基丙烯酰胺、N-二异丙基丙烯酰胺、二乙酰丙烯酰胺(diacetoacrylamide)、甲基丙烯酸N,N-二乙基氨基乙酯、甲基丙烯酸N-叔丁基氨基乙酯;苯乙烯和其衍生物,如乙烯基甲苯、α-甲基苯乙烯、α-氰基甲基苯乙烯;含卤低级烯烃,如乙烯、丙烯、异丁烯、3-氯-1-异丁烯、异戊二烯、和烯丙基或乙烯基卤,如氯乙烯和偏二氯乙烯。能与上述含氟代脂族基团的单体共聚的共聚单体较好的包括选自甲基丙烯酸十八烷基酯、甲基丙烯酸月桂酯、丙烯酸丁酯、N-羟甲基丙烯酰胺、甲基丙烯酸异丁酯、丙烯酸乙基己酯、甲基丙烯酸乙基己酯、甲基丙烯酸缩水甘油酯、氯乙烯和偏二氯乙烯的那些单体。
可用于制备含氟化合物低聚物的羟基或氨基官能化链转移剂较好的具有下式:
HS-R-X
其中:
R按照本文定义,X是-OH和-NH2部分
链转移剂的例子包括选自2-巯基乙醇、3-巯基-2-丁醇、3-巯基-2-丙醇、3-巯基-1-丙醇或2-巯基-乙胺的那些。可以使用一种化合物或不同链转移剂的混合物。较好的链转移剂是2-巯基乙醇。
为了制备官能化的含氟化合物低聚物,通常有自由基引发剂存在。本领域皆知这类自由基引发剂,它们包括偶氮化合物,如偶氮二异丁腈(AIBN)和偶氮二(2-氰基戊酸)等,氢过氧化物,如氢过氧化枯烯、氢过氧化叔丁基、氢过氧化叔戊基;二烷基过氧化物,如过氧化二叔丁基和过氧化二枯基;过氧化酯,如过苯甲酸叔丁酯、二叔丁基过氧邻苯二甲酸酯;二酰基过氧化物,如过氧化苯甲酰和过氧化月桂酰。
第二步中,使含氟化合物低聚物(或含氟化合物低聚物的混合物)、能与异氰酸酯基反应的单官能化合物和能与异氰酸酯反应的双官能化合物与三异氰酸酯反应,可获得聚氨基甲酸酯。该反应还涉及含氟化合物低聚物和单官能和双官能化合物之外的又一种异氰酸酯反应活性化合物。本领域的技术人员应该理解根据本发明制备聚氨基甲酸酯会产生化合物的混合物。
根据本发明优选的实施方案,约6-33%的异氰酸酯基团与含氟化合物低聚物反应,约33-61%异氰酸酯基团与双官能化合物反应,约28-35%的异氰酸酯基团与单官能化合物反应,0-约10%的异氰酸酯与含氟化合物低聚物、双官能化合物和单官能化合物之外的又一种异氰酸酯反应活性化合物反应。
单官能化合物的聚(氧化烯)基团中的氧化烯基部分有约2-4个碳原子为宜。这样的部分的例子包括-OCH2-CH2-、-OCH2-CH2CH2-、-OCH(CH3)CH2-和-OCH(CH3)CH(CH3)-。聚(氧化烯)基团中的氧化烯部分可以相同(如聚(氧丙烯)),或为混合物(如混杂直链或支链或任意分布的氧化乙烯链与氧化丙烯部分的链,或嵌段氧化乙烯单元的直链或支链与氧化丙烯部分的嵌段)。聚(氧化烯)基的骨架可被一个或多个悬链键隔开,或包括这些悬链键。当悬链键为三价或更高价时,提供了用于获得氧化烯部分的支链的手段。单官能化合物所含聚(氧化烯)中的氧化烯部分的数量宜为约5-120,更好的约为17-48。
根据一个特别好的实施方案,单官能化合物具有下式:
H-W-R6-(O-R7)x-(O-R8)y-O-R9
其中:
W选自O、NH或S;
R6代表有约1-4个碳原子的亚烷基;
R7和R8各自选自有2-4个碳原子的直链或支链亚烷基;
R9代表有约1-4个碳原子的烷基;
x和y各自选自0-约60的整数,条件是x和y的总和至少约为5。
较好的R7是亚乙基,R8是直链或支链的亚丙基,x与y之比至少为1,较好的大于1。最好y是0,R7是亚乙基。
包括聚(氧化烯)基的单官能化合物的典型例子包括聚二醇的烷基醚(如聚乙二醇的甲基醚或乙基醚)、乙烯化氧和丙烯化氧的无规或嵌段共聚物的羟基端基的甲醚或乙醚,或聚乙烯化氧的氨基端基的甲醚或乙醚。
能与异氰酸酯基反应的双官能化合物较好的具有下式:
HX1-Y-X2H
其中,Y是有机二价连接基,X1和X2各自选自O或NH。Y的例子包括直链或支链亚烷基、亚芳基、亚芳烷基或亚环烷基。根据本发明特别优选的实施方案,在包括两个羟基或氨基,或一个羟基和氨基的链转移剂存在下由一种或多种上述无氟单体的低聚合反应可得到双官能化合物。这样的链转移剂的一个例子是3-巯基-1,2-丙醇。这样的低聚物更好的是通过至少一种含活化(例如加热)时能交联的官能团的单体低聚合制得。这样的官能团的典型例子包括封端的异氰酸酯基和烷氧基硅烷基。包括能在活化时交联的官能团的单体有烷氧基硅烷官能化丙烯酸酯或甲基丙烯酸酯,或含有封端的异氰酸酯的单体,如(甲基)丙烯酸2-羟基-乙酯、二异氰酸酯和异氰酸酯封端剂的反应产物。用于本发明的异氰酸酯封端剂是能与异氰酸酯基反应产生一种基团的化合物,这种产生的基团在室温下不与异氰酸酯反应活性部分反应,但在升高温度下与异氰酸酯反应活性部分反应。合适的异氰酸酯封端剂通常在约50-190℃温度下会与异氰酸酯反应活性化合物反应。可供使用的异氰酸酯封端剂的例子包括芳醇(如苯酚、甲酚、硝基苯酚、邻氯苯酚和对氯苯酚、萘酚、4-羟基联苯);C2-C8链烷酮肟(如丙酮肟、丁酮肟);二苯甲酮肟;芳基硫醇(如苯硫酚);有机阴碳离子活性氢化合物(如丙二酸二乙酯、乙酰丙酮、乙酰乙酸乙酯、氰基乙酸乙酯)和ε-己内酯。可以使用一种化合物或不同掩蔽剂或封端剂的混合物。特别优选的封端剂或掩蔽剂包括C2-C8链烷酮肟,如2-丁酮肟。较好的无氟低聚物的聚合度约为2-40,更好的约为3-20。
双官能化合物的另一些例子包括链烷二醇(如C2-C4链烷二醇,如乙二醇和1,4-丁二醇)、聚酯二醇、聚己内酰胺二醇、二胺(如C2-C4二胺,如乙二胺)、1,2-二氨基丙烷、1,3-二氨基丙烷、1,4-二氨基丁烷、1,10-氨基癸烷、1,7-二氨基庚烷、1,6-二氨基己烷、1,12-二氨基十二碳烷、1,9-二氨基壬烷、1,8-二氨基辛烷、1,5-二氨基戊烷、异佛二酮二胺、哌嗪、1,8-萘二胺、1,2/1,3/1,4苯二胺、4-甲基-1,3-苯二胺和4-甲基-1,2-苯二胺、氨基醇(如2-氨基苄醇、4-氨基-1-丁醇和乙醇胺)。
用于本发明的三异氰酸酯包括脂族和芳族异氰酸酯。例子有脂族三异氰酸酯,如1,3,6-己三异氰酸酯,芳族三异氰酸酯,如多异氰酸亚甲基多苯基酯(PAPI)、三-(4-异氰酸根苯基)-甲烷(可从Bayer以DESMODURTM R购得)和以DESMODURTM L从Bayer购得。有用的还有含源自内异氰酸酯部分的异氰酸酯,如含缩二脲的三异氰酸酯(如可以DESMODURTM N-100从Bayer购得)和含异氰脲酸酯的三异氰酸酯(如以IPDI-1890从Huls AG,Germany购得)。
包含聚氨基甲酸酯的含氟化合物组合物的制备任选包括与少量上述那些化合物之外的异氰酸酯反应活性化合物反应。这样的异氰酸酯反应活性化合物通常是只含一个异氰酸酯反应活性基团的化合物,包括单官能的无氟低聚物和异氰酸酯封端剂。这样的异氰酸酯反应活性化合物包括链烷醇,如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇。正戊醇、叔戊醇、2-乙基己醇、缩水甘油、(异)十八烷醇和伯胺或仲胺(如丁胺)。
在本领域技术人员皆知的常用条件下进行缩合反应。该反应宜在催化剂存在下进行。合适的催化剂包括锡盐(如二月桂酸二丁基锡)、辛酸亚锡、油酸亚锡、二丁基二-(2-乙基己酸)锡、氯化亚锡和其它本领域技术人员已知的那些催化剂。催化剂量取决于具体的反应,因此要列举出具体优选的浓度是不实际的。然而,合适催化剂的浓度,以反应物总重量为基础,一般约为0.001-10%(重量),较好的约为0.1-5%(重量)。
缩合反应宜在干燥条件下的极性溶剂,如乙酸乙酯、丙酮、甲基异丁基酮、甲苯等中进行。本领域的技术人员可根据具体使用的试剂、溶剂和催化剂能容易地决定合适的反应温度。列举出适合所有情况的具体温度是不切实际的,但合适温度一般在约室温至约120℃之间。
采用常规的施用方法就可以施用本发明的含氟化合物组合物,但是宜以含水乳状液使用。也可以作为溶剂中的处理组合物使用。含水乳状液一般含有水、含氟化合物组合物(其量应能对用其处理的基材提供有效的所需排斥性能)、以及表面活性剂(其量应能有效稳定该乳状液)。以本发明的含氟化合物组合物重量为100重量份计,水量宜约为70-2000重量份,表面活性剂量宜约为1-25重量份,更好是约2-10重量份。常用的阴离子型、非离子型、阳离子型和两性离子表面活性剂均合适。
含水溶剂基处理组合物施用到基材的量应足以提供基材高的污斑脱除性能。通常,处理组合物的量只要能充分提供基材重量的约0.01-5%(重量)(较好约0.05%至2%(重量))的含氟化合物组合物就已足够。充分提供要求的污斑脱除性能的处理组合物量可根据经验确定,并可按照需要或要求增加。
本发明的含氟化合物组合物中还可以加入其它的氟化产物、聚合物或辅助产品,如淀粉、糊精、酪蛋白、聚乙烯醇、纤维素和纤维素衍生物(如纤维素醚)、(甲基)丙烯酸和(甲基)丙烯酸烷基酯的共聚物、聚二醇(如聚乙二醇)、上浆剂、改善水和/或油排斥性、耐火或抗静电性能的物质、缓冲剂、抗菌剂、荧光增白剂、螯合剂、无机盐、表面活性剂或促进渗透的溶胀剂。以使用(甲基)丙烯酸烷基酯和(甲基)丙烯酸的共聚物作为含氟化合物组合物的辅助产品为宜。这类聚合物中(甲基)丙烯酸与(甲基)丙烯酸烷基酯的重量比通常在20∶80和90∶10之间,50∶50和85∶15之间更好。(甲基)丙烯酸酯单体的烷基较好是约1-6个碳原子的低级烷基。(甲基)丙烯酸烷基酯的例子包括甲基、乙基和正丁基的丙烯酸酯和甲基丙烯酸酯。(甲基)丙烯酸烷基酯和(甲基)丙烯酸的共聚物还可以含有源自烯键不饱和单体单元,但是共聚物仅由源自(甲基)丙烯酸烷基酯和(甲基)丙烯酸的单元或部分组成为宜。该共聚物还可以被诸如氢氧化钠或氢氧化铵的碱部分或完全中和。
用于含氟化合物组合物的特别合适的辅助产品包括聚乙烯醇和非离子型纤维素醚。非离子型纤维素醚衍生物包括甲基纤维素、羟丙基纤维素和甲基羟丙基纤维素。较好的醚化纤维素是高度亲水性的。因此,不选择含有大量疏水性取代基的纤维素醚,如疏水性改性纤维素醚(可以NEXTONTM从Aqualon购得)用于本发明的含氟化合物组合物。
对用本发明的含氟组合物处理的基材没有限制,基材包括塑料、金属、玻璃、纤维材料(如织物)、木材、非织造织物和纸。含氟化合物组合物对向包含天然纤维的基材,特别是由纤维素纤维组成的基材或由纤维素和聚酯纤维组成的基材提供污斑脱除性特别有用。经本发明含氟化合物组合物处理的基材对脏的马达油斑和茶渍具有特别优良的污斑脱除性能。
为对织物基材进行处理,可将基材浸在稀释的乳状液中。然后,将浸透的基材通过浸轧机(padder)/辊滚动,除去过量的乳状液,并在烘箱内干燥和固化,温度和时间应足以提供固化的处理基材。该固化过程通常在约50-190℃之间进行,取决于具体的系统或采用的施用方法。一般在约120-170℃,特别是在约150-170℃进行约20秒至10分钟,较好的进行3-5分钟为宜。
参考下面的实施例进一步说明本发明,但是本发明不受这些实施例的限制。
实施例
配制和处理方法
配制含确定量的含氟化合物处理剂的处理浴液。将处理物施用到试样基材上可通过铺垫以提供0.3%或0.6%的固体浓度(以织物重量为基准,并以SOF(织物上的固体)表示),并在150℃将样品干燥3分钟。实施例所使用的试样基材均可购得,并在下面列出:*PES/CO: 聚酯/棉67/33掺混物,可从Arlitex,Avelgem Belgium购得*100%棉: 可从UCO company,Destelbergen,Belgium购得
干燥后,试验基材的污斑脱除和排斥性能。
实施例和比较例中所示的污斑脱除、斥水性和斥油性数据是基于下面的测定方法和评价标准:
污斑脱除试验
对两种类型的污斑进行污斑脱除试验:
-脏的马达油,从General Motors Garage Houttequiet,Beveren;Belgium获得
-茶:将LiptonTM黄色茶包浸在165毫升65℃水中3分钟获得。
染污法1:滴染法
10厘米×10厘米的试样,用3滴DMO或茶染污PES/CO试样,或用4滴DMO或茶染污棉花试样。样品在室温下平衡24小时,之后使用Minolta比色计(LampD65),测定污染样品和未污染样品的反射差,来评价污染度。对每一污斑取3次测定的平均值,得到ΔLIN值。
染污法2:刷染法
对10厘米×10厘米的试验样品,在PEC/CO样品上放置0.35毫升DMO或0.5毫升茶,在棉花样品上放置0.5毫升DMO或0.6毫升茶。围绕放置在污染液体周围直径5厘米的塑料架刷3圈,将污染物刷进织物。按上面所述进行反射测定。
洗涤方法
将试验样品用别针钉在PES/CO镇重物(总重3千克)或棉花镇重物(总重4千克)上,在W832型Miele洗衣机中洗涤。加入市售的洗涤剂(20克/千克,PES/CO加入Clax100,棉花加入Clax晶体,由Diversy Lever购得)然后在70℃洗涤基材,采用主洗涤程序,随后进行四个漂洗周期和离心。样品在滚筒干燥器中干燥,并在150℃熨烫15秒。未污染的样品按照同样方式进行处理。用Minolta计测定样品,并与未污染样品进行比较,得到ΔLLD70℃值。
与ΔLIN比较所获ΔLLD70℃的负值越小,污斑脱除性能越好。根据下式可计算%ΔΔL:
%ΔΔL=(ΔLIN-ΔLLD70℃/ΔLIN)×100
所获值表示洗涤过程中污斑脱除的百分数。该值越高,污斑脱除越好。
斥水性试验(WR)
使用一系列水-异丙醇试验液体测定基材的斥水性(WR),并以术语“WR”表示处理基材的评分。WR评分对应于在基材接触15秒后还不能渗透或润湿基材表面的渗透性最强的试验液体。能被100%水(0%异丙醇)试验液体,即渗透性最小的试验液体渗透,或仅能阻止该试验液体的基材,评分为0。能阻止100%异丙醇(0%水)试验液体,即渗透性最大的试验液体的基材,评分为10。将试验液体中异丙醇的百分数除以10来计算其它中间评分,如处理基材能阻止70%/30%的异丙醇/水的掺混物,但不能阻止80%/20%的异丙醇/水的掺混物,评分为7。
斥油性(OR)
采用American Association of Textile Chemists and Colorists(AATCC)的标准试验方法No.118-1983测定基材的斥油性,该试验是基于处理基材对不同表面张力的油渗透的阻力。处理的基材仅能阻止Nujol矿物油(渗透性最小的的试验油)评分为1,而处理的基材能阻止庚烷(渗透性最大的试验液体)的评分为8。其它的中间评分可通过使用下表所示的其它纯油或油混合物来测定。
标准试验液体
AATCC斥油性评分 | 组成 |
1 | Nujol |
2 | Nujol/正十六碳烷65/35 |
3 | 正十六碳烷 |
4 | 正十四碳烷 |
5 | 正十二碳烷 |
6 | 正癸烷 |
7 | 正辛烷 |
8 | 正庚烷 |
缩写
下面为在实施例和比较例所用的缩写和商品名:EtOAc: 乙酸乙酯RSH: 2-巯基乙醇MPD: 3-巯基-1,2-丙二醇AIBN: 偶氮二异丁腈MEFOSEA: 丙烯酸N-甲基全氟辛基磺酰氨基乙酯MPEG750-2000: 聚乙二醇甲醚,上角标数字表示分子量,可从Inspecm,Belgium
获得HOEMA: 甲基丙烯酸2-羟基乙酯IPDI: 异佛尔酮二异氰酸酯BA: 丙烯酸正丁酯GMA: 甲基丙烯酸缩水甘油酯(甲基丙烯酸2,3-环氧丙酯)BO: 2-丁酮肟DBTDL: 二月桂酸二丁锡MEHQ: 甲基氢醌DESN: 脂族多异氰酸酯,可从Bayer(Germany)按DEMODURTM N获得Arquad T-50: 牛脂氯化三甲铵,可从Akzo,Littleborough,UK获得
除非特别指出,在下面实施例中的所有份、比、百分数均以重量为基准。
A.合成羟基端基的低聚物(HTO)
1.合成氨基甲酸酯丙烯酸酯HOEMA/IPDI/BO(摩尔比为1/1/1)
氨基甲酸酯丙烯酸酯HOEMA/IPDI/BO(摩尔比为1/1/1)可用于制备羟基端基的低聚物,其制备方法如下:
在配备有机械搅拌器、温度控制、加料漏斗、氮气进管和出管的圆底烧瓶中投入111克(0.5摩尔)IPDI、65克(0.5摩尔)HOEMA、200克EtOAc、0.1克吩噻嗪(phenotiazin)、0.1克MEHQ和0.2克二月桂酸二丁锡。反应混合物缓慢加热至约50℃。在1小时内加入44克(0.5摩尔)2-丁酮肟溶解在20克EtOAc中的溶液。然后反应混合物于72℃搅拌6小时。IR分析表明所有异氰酸酯基团已经反应。
2.合成羟基端基的低聚物(HTO)
采用与合成MEFOSEA/RSG4/1(表1中表示为HTO-1)相同的方法制得表1所列的羟基端基的低聚物:
在配备有两个回流冷凝器、搅拌器、温度控制、加料漏斗、氮气进管和出管的圆底烧瓶中投入2.4摩尔(1433克)MEFOSEA和987克EtOAc。于40℃加热该混合物直到所有含氟混合物单体溶解。加入0.6摩尔(46.8克)2-巯基乙醇和0.15%AIBN。该反应化合物逐渐加热至80℃。反应在氮气氛,80℃下进行16小时,反应后获得大于95%的转化率。
表1
羟基端基低聚物(HTO)的组成
低聚物 | 组成 | 摩尔比 |
HTO-1 | MEFOSEA/RSH | 4/1 |
HTO-2 | MEFOSEA/RSH | 8/1 |
HTO-3 | BA/GMA/MPD | 4/1/1 |
HTO-4 | (HOEMA/IPDI/BO)/BA/MPD | 1/3/1 |
B.合成含氟化合物(FC)
采用与下面合成DESN/HTO-1/HTO-4/MPEG750(2/2/1/2)(表2中的FC-1)相同的方法制得表2所列的含氟化合物:
在配备有冷凝器、温度计、搅拌器和氮气进管的圆底烧瓶中投入22.32克(0.025摩尔)Desmodur N100、11.65克(0.0125摩尔)HTO-4、63.05克(0.025摩尔)HTO-1和18.75克(0.025摩尔)MPEG750,随后加入257克乙酸乙酯。该反应混合物加热至50℃,之后加入催化剂(DBTDL)。该混合物温度升高至75℃,进行反应直到结束。
C.乳化
将步骤B中所获的含氟化合物(20克固体)加到含1.2克Arquad T-50(50%固体)乳化剂的去离子水中。使用超声波探头(Branson 250 sonifier)使该混合物均化,之后真空下除去有机溶剂。制得含15%的含氟化合物的乳状液。
表2
含氟化合物氨基甲酸酯(FC)的组成
FC | 含氟化合物组成 | 摩尔比 |
FC-1 | DESN/HTO-1/HTO-4/MPEG750 | 2/2/1/2 |
FC-2 | DESN/HTO-1/HTO-4/MPEG750 | 3/2/2/3 |
FC-3 | DESN/HTO-2/HTO-4/MPEG2000 | 2/2/1/2 |
FC-4 | DESN/HTO-1/HTO-3/MPEG750 | 2/2/1/2 |
实施例1和2以及比较例C-1
实施例1和2中,按照上面所述的通用方法制得本发明的含氟化合物并乳化。用该含氟化合物处理聚酯/棉花(PES/CO)掺混物,提供0.6%SOF。处理后,织物于150℃干燥3分钟。处理后的PES/CO基材采用滴染法用脏的机动车油染污。用未处理的PES/CO织物进行比较例C-1。污斑脱除以及油和水的排斥性结果列于表3。
表3
处理后PES/CO的污斑脱除(DMO-滴染)和排斥性能
实施例 | 含氟化合物 | SOF% | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLIN70℃ | %ΔΔL | |||
1 | FC-1 | 0.6 | 5 | 8 | -6.25 | -0.84 | 87 |
2 | FC-4 | 0.6 | 5 | 7 | -6.35 | -1.83 | 71 |
C-1 | -- | -- | 0 | 0 | -15.45 | -9.56 | 38 |
数据表明本发明的含氟化合物提供极优良的DMO污斑脱除。除了优良的污斑脱除性能外,还获得了优良的油和水的排斥性,作为又一个优点。
实施例3和4以及比较例C-2
实施例3和4中,重复与上面同样的试验,但是采用刷染法施用DMO。用未处理的PES/CO织物进行比较例C-2。污斑脱除以及油和水的排斥性结果列于表4。
表4
处理后PES/CO的污斑脱除(DMO-刷染)和排斥性能
实施例 | 含氟化合物 | SOF% | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLIN70℃ | %ΔΔL | |||
3 | FC-2 | 0.6 | 5 | 9 | -18.06 | -9.68 | 46 |
4 | FC-3 | 0.3 | 3 | 4 | -18.26 | -9.56 | 47 |
C-2 | -- | -- | 0 | 0 | -15.32 | -8.67 | 43 |
实施例5和6以及比较例C-3
实施例5和6中,重复与上面同样的试验,按照上述通用方法用含氟化合物处理100%棉花基材。采用刷染法在棉花基材上涂布DMO污斑。用未处理的棉花织物进行比较例C-3。污斑脱除以及油和水的排斥性结果列于表5。
表5
处理后棉花的污斑脱除(DMO-刷染)和排斥性能
实施例 | 含氟化合物 | SOF% | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLIN70℃ | %ΔΔL | |||
5 | FC-2 | 0.3 | 2 | 3 | -18.45 | -7.93 | 57 |
6 | FC-3 | 0.3 | 2 | 4 | -19.7 | -7.92 | 60 |
C-3 | -- | -- | 0 | 0 | -15.70 | -8.76 | 44 |
数据表明对棉花基材上如DMO的油性污斑可观察到优良的污斑脱除百分数(%ΔΔL)。
实施例7和8以及比较例C-4
实施例7和8中,采用滴染法,用茶染污本发明的含氟化合物处理的PES/CO掺混物。用未处理的织物进行比较例C-4。污斑脱除以及油和水的排斥性结果列于表6。
表6
处理后PES/CO的污斑脱除(茶-滴染)和排斥性能
实施例 | 含氟化合物 | SOF% | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLIN70℃ | %ΔΔL | |||
7 | FC-1 | 0.6 | 5 | 8 | -3.92 | -0.26 | 93 |
8 | FC-4 | 0.6 | 5 | 7 | -6.96 | -0.79 | 89 |
C-4 | -- | -- | 0 | 0 | -2.32 | -0.91 | 61 |
观察到对处理的样品具有高的茶污斑脱除。
实施例9和10以及比较例C-5
实施例9和10中,用茶污斑试验本发明的含氟化合物处理的PES/CO基材,但是采用刷染法。用未处理的材料进行比较例C-5。污斑脱除以及油和水的排斥性结果列于表7。
表7
处理后PES/CO的污斑脱除(茶-刷染法)和排斥性能
实施例 | 含氟化合物 | SOF% | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLIN70℃ | %ΔΔL | |||
9 | FC-2 | 0.6 | 5 | 9 | -1.32 | -0.77 | 42 |
10 | FC-3 | 0.3 | 4 | 6 | -1.42 | -0.66 | 54 |
C-5 | -- | -- | 0 | 0 | -2.62 | -1.22 | 53 |
尽管对茶污斑的脱除百分数没有或甚至比未处理样品的差,但处理后的样品的ΔLIN70℃值是比未处理样品小得多的负数值,表明用本发明的含氟化合物组合物处理的样品洗涤后,可视污斑较少。
实施例11和12以及比较例C-6
实施例11和12中,采用刷染法,用茶污斑染污本发明含氟化合物处理的棉花基材。用未处理的材料进行比较例C-6。污斑脱除以及油和水的排斥性结果列于表8。
表8
处理后棉花的污斑脱除(茶-刷染法)和排斥性能
实施例 | 含氟化合物 | SOF% | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLIN70℃ | %ΔΔL | |||
11 | FC-2 | 0.3 | 2 | 3 | -2.04 | -0.46 | 77 |
12 | FC-3 | 0.3 | 2 | 3 | -2.24 | -0.32 | 86 |
C-6 | -- | -- | 0 | 0 | -3.21 | -1.36 | 58 |
结果表明用本发明含氟化合物组合物处理的棉织物具有高的茶污斑脱除性。
Claims (17)
1.一种制备包含聚氨基甲酸酯的含氟化合物组合物的方法,该方法包括使下列物质:
(A)式(I)的含氟化合物低聚物
Mf mMn-Q1-T1 (I)其中:
Mf mMn代表包含源自氟化单体的m个单元和源自无氟单体的n个单元的含氟化合物低聚物,所述氟化单体和无氟单体可以相同或不同;
m代表2-40的值;
n代表0-20的值;
T1是-OH或-NH2;
Q1和T1一起表示从以T1官能化的链转移剂去除一个氢原子所获得的有机残基;
(B)能与异氰酸酯反应的双官能化合物;和
(C)能与异氰酸酯反应的单官能化合物,该化合物包含聚(氧化烯)基团;与
(D)三异氰酸酯反应。
2.如权利要求1所述的方法,其特征在于所述氟化单体具有下式:
Rf-L1-E其中:
Rf选自全氟化或部分氟化的脂族基团;
L1代表有机二价连接基;和
E代表可自由基聚合基团。
4.如前述权利要求中任一权利要求所述的方法,其特征在于所述Q1具有下式:
-S-R-其中:
R代表有机二价键连接基,选自直链或支链的亚烷基、亚环烷基或亚芳基。
5.如前述权利要求中任一权利要求所述的方法,其特征在于所述包含聚(氧化烯)基的单官能化合物具有下式:
H-W-R6-(O-R7)x-(O-R8)y-O-R9其中:
W选自O、NH或S;
R6代表有1-4个碳原子的亚烷基;
R7和R8各自选自有2-4个碳原子的直链或支链亚烷基;
R9代表有1-4个碳原子的烷基;
x是0-60的整数;
y是0-60的整数;和
x和y的总和至少为5。
6.如权利要求1-5中任一权利要求所述的方法,其特征在于所述用于制备所述含氟化合物组合物的双官能化合物具有下式:
HX1-Y-X2H其中:
Y是有机二价连接基,选自直链或支链的亚烷基、亚环烷基、亚芳基或亚芳烷基;
X1是O或NH;
X2是O或NH。
7.如权利要求6所述的方法,其特征在于所述双官能化合物由一种或多种无氟单体在链转移剂存在下的低聚合反应制得,所述链转移剂包含两个各自选自羟基或氨基的官能团。
8.如权利要求7所述的方法,其特征在于至少一种所述的无氟单体含有能通过加热活化交联的官能团。
9.如前述权利要求中任一权利要求所述的方法,其特征在于6-33%的异氰酸酯基团与所述含氟化合物低聚物反应,33-61%异氰酸酯基团与所述双官能化合物反应,28-35%的异氰酸酯基团与所述单官能化合物反应,0-10%的异氰酸酯与所述含氟化合物低聚物、双官能化合物和单官能化合物之外的一种异氰酸酯反应活性化合物反应。
10.一种含氟化合物组合物,可通过如权利要求1-9中任一权利要求所述的方法制得。
11.如权利要求10所述的含氟化合物组合物,其特征在于所述含氟化合物组合物还包含一种选自聚乙烯醇、(甲基)丙烯酸和(甲基)丙烯酸烷基酯的共聚物、聚乙二醇或非离子型纤维素醚的聚合物。
12.一种处理基材的方法,它包括用如权利要求10或11所述的含氟化合物组合物处理所述基材的步骤。
13.如权利要求12所述的方法,其特征在于所述基材是纤维基材。
14.如权利要求13所述的方法,其特征在于所述基材包括天然纤维。
15.如权利要求13所述的方法,其特征在于所述基材是纤维基材,所述纤维选自纤维素纤维、聚酯纤维或它们的掺混物。
16.使用如权利要求11或12所述的含氟化合物组合物,向基材提供污斑脱除性能。
17.一种基材,在其至少一个表面的至少部分表面上包括如权利要求11或12所述的含氟化合物组合物。
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AU2001273428A1 (en) * | 2000-08-14 | 2002-02-25 | 3M Innovative Properties Company | Urethane-based stain-release coatings |
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US7652117B2 (en) * | 2007-06-20 | 2010-01-26 | 3M Innovative Properties Company | Fluorochemical urethane compounds and aqueous compositions thereof |
US7897678B2 (en) | 2007-07-26 | 2011-03-01 | 3M Innovative Properties Company | Fluorochemical urethane compounds having pendent silyl groups |
US8015970B2 (en) | 2007-07-26 | 2011-09-13 | 3M Innovative Properties Company | Respirator, welding helmet, or face shield that has low surface energy hard-coat lens |
US20110091508A1 (en) | 2007-10-05 | 2011-04-21 | Interface Biologics ,Inc. | Oligofluorinated cross-linked polymers and uses thereof |
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