CN1255931A - 赋予基材以污斑脱除性的包含具有氟化物低聚物和亲水链段的聚氨酯的氟化物组合物 - Google Patents
赋予基材以污斑脱除性的包含具有氟化物低聚物和亲水链段的聚氨酯的氟化物组合物 Download PDFInfo
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Abstract
本发明提供了一种制备包含聚氨酯的氟化物组合物的方法,该方法包括使下列(A)、(B)、(C)和(D)与(E)反应:(A)式(I)的氟化物低聚物:Mf mMn-Q1-T1,其中:Mf mMn表示包含由氟化单体得到的m个单元和由无氟单体得到的n个单元的氟化物低聚物,氟化单体和无氟单体可以相同或不同;m表示约2-40的值;n表示约0-20的值;T1是-OH或-NH2部分;Q1和T1共同表示用T1官能化的链转移剂除去一个氢原子所获得的有机残基;(B)能与异氰酸酯反应的单官能化合物,它包含聚(氧化烯)基团;(C)异氰酸酯封端剂或无氟低聚物;(D)除所述氟化物低聚物、所述异氰酸酯封端剂、所述无氟低聚物或所述单官能化合物以外的异氰酸酯反应性化合物;(E)二异氰酸酯或三异氰酸酯;其中33-67%数目的异氰酸基与化学式(I)的氟化物低聚物反应,33-67%数目的异氰酸基与所述单官能化合物反应;0-33%数目的异氰酸基与异氰酸酯封端剂或无氟低聚物反应,0-10%数目的异氰酸基与所述异氰酸酯反应性化合物反应。经过按上述方法制得的氟化物组合物处理的基材具有良好的污斑脱除性,尤其是对于油性污斑和水基污斑,如葡萄酒渍、茶渍和咖啡渍。
Description
发明领域
本发明涉及用于处理基材,尤其是诸如织物的纤维基材,赋予这些基材以污斑脱除性的氟化物组合物。
发明背景
用于处理诸如皮革、织物和纸张之类的基材的氟化物组合物已为人知,这类氟化物组合物可用来赋予基材以各种性能,如拒水性和/或拒油性,防水性、污斑脱除性(stain release)和防污性等。例如,美国专利No.5,276,175揭示了包含氟化物低聚物的异氰酸酯衍生物。具体而言,所揭示的氟化物组合物包含氟化物,所述氟化物包含氟化物低聚物部分、有机部分,以及能够在氟化物施用于纤维基材时提供柔软手感、污斑脱除性、拒水性或耐久性的基团,其中氟化物低聚物部分通过异氰酸酯衍生得到的连接基团与有机部分连接。如此处理的基材显示特别的耐久性、耐磨性、拒油性和拒水性。此外,在该专利的一个实施例中,表明氟化物组合物是基于三异氰酸酯、氟化物低聚物和甲氧基聚环氧乙烷二醇(methoxypolyethyleneoxide glycol)的缩合物。证实了该组合物对于聚酯/棉掺混织物的污斑脱除性。
美国专利No.5,350,795揭示了用于处理织物纤维和织品赋予它们以拒油性和拒水性而无需热处理的氟化物组合物。该组合物包含下述(a)和(b)的基本上不含有机溶剂的水溶液或水分散体:(a)氟化物丙烯酸酯共聚物,包含氟化丙烯酸酯单体、聚亚烷基二醇的丙烯酸酯或甲基丙烯酸酯、或聚亚烷基二醇的二丙烯酸酯或二甲基丙烯酸酯;(b)聚烷氧基化的聚氨酯,它具有全氟烷基侧基,包含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,以及聚氧化烯基的二醇或二硫醇。
美国专利No.4,788,287和No.4,792,354揭示了一种拒水性和拒油性的化合物,它具有至少两个末端链段和一个连接这些末端链段的中间链段,其分子量为800-20,000。该化合物的每个末端链段含有至少一个由-CONH-连接基团连接的多氟烷基基团,中间链段是每个分子至少含两个-CONH-连接基团的聚氨酯低聚物,末端链段和中间链段通过-CONH-连接基团进行连接。美国专利No.4,792,354揭示的聚氨酯低聚物还含有亲水性分子链。
美国专利No.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。它们可以与异氰酸酯、环氧化合物、酐、酸或酸衍生物反应制备多种拒油性和拒水性的组合物。
氟化物组合物还可用来帮助从诸如织物之类的基材上脱除污斑或污垢。使用改性添加剂(如柔软剂、硬化剂和润滑剂)对织物进行的常规处理能赋予市售织物以所需的性能,但通常会提高织物的亲油性,从而使织物接受油污的倾向显著增加,在洗涤后脱除污斑的能力显著下降。已知可用作污斑脱除组合物的氟化物组合物是基于氟化物和非氟化的亲水性化合物的混合物或者含有氟化物疏油链段(“F”)和非氟化的亲水链段(“H”)的化学“杂化”化合物,因为这些氟化物组合物在正常穿着期间能提供拒油性,能抑制吸油或油污扩散到织物或纤维束中,并且有助于洗涤时脱除污斑。
美国专利No.3,574,791揭示了一种由F和H链段组成的嵌段共聚物可用作污斑脱除剂。″F″链段基本上不含亲水基团,而″H″链段基本上不含氟化脂族基团。该专利中指出,由于这种分段,聚合物是“自动适应性(autoadaptable)”的,即经该聚合物处理的织物在大气环境中是拒油性和拒水性的,在水中洗涤时它会具有亲水性以使污斑能够去除。可以想到有多种可用来连接″F″和″H″链段的化学键,包括由醇和异氰酸酯反应得到的氨基甲酸酯键。
美国专利No.5,509,939揭示了一种能赋予基材以污垢脱除性能的氟化物组合物。该氟化物组合物包括含脲键的烷氧基聚氧化烯基氟代氨基甲酸酯,其制法是将以下(a)、(b)、(c)和(d)反应,(a)至少一种含至少三个异氰酸基(isocyanate group)的多异氰酸酯,(b)至少一种氟化物试剂,它含有一个具有至少一个氢原子和至少两个各自含至少两个F原子的碳原子的官能团,(c)至少一种亲水性、可水溶剂化的试剂,它含有具有至少一个活泼氢原子的单个官能团,(d)至少一种试剂,它含有一个活泼氢原子,在与异氰酸基的反应中产生的官能度对纤维基材的化学反应性暂时失效,然后使产物与水进行反应,以使反应物(b)、(c)和(d)与55-95%的异氰酸基反应,而水与其余的异氰酸基反应。
尽管已知有许多能赋予基材以污斑脱除性的氟化物组合物,但仍然需要具有改进性能的氟化物组合物。所需性能包括以天然纤维为基的基材(如棉,棉和聚酯的共混物)的可清洗性,具体是对油性污斑(脏的马达油、植物油)和水基污斑(茶、咖啡)的可清洗性;低生产成本;高贮存稳定性;即使少量使用时也易于乳化且性能良好。还要求氟化物组合物为基材提供优良的拒污性,以及拒油性和/或拒水性。
发明概述
本发明提供了一种制备包含聚氨酯的氟化物组合物的方法,该方法包括使下列(A)、(B)、(C)和(D)与(E)反应:
(A)式(I)的氟化物低聚物:
Mf mMn-Ql-Tl (I)
其中:
Mf mMn表示包含由氟化单体得到的m个单元和由无氟单体得到的n个单元的氟化物低聚物,氟化单体和无氟单体可以相同或不同;
m表示约2-40的值;
n表示约0-20的值;
Tl选自-OH和-NH2部分;和
Ql和Tl共同表示用Tl官能化的链转移剂除去一个氢原子所获得的有机残基;
(B)能与异氰酸酯反应的单官能化合物,它包含聚(氧化烯)基团;
(C)异氰酸酯封端剂或无氟低聚物;
(D)除所述氟化物低聚物、异氰酸酯封端剂、无氟低聚物或单官能化合物以外的异氰酸酯反应性化合物;
(E)二异氰酸酯或三异氰酸酯,以使得约33-67%数目的异氰酸基与化学式(I)的所述氟化物低聚物反应,约33-67%数目的异氰酸基与所述单官能化合物反应,约0-33%数目的异氰酸基与异氰酸酯封端剂或无氟低聚物反应,约0-10%数目的异氰酸基与所述异氰酸酯反应性化合物反应。
本发明还提供了可以用上述方法获得的包含聚氨酯的氟化物组合物,以及将该氟化物组合物用来向基材提供污斑脱除性能。
还提供了使用一种本文所述的氟化物组合物处理基材的方法,以及经过一种所述氟化物组合物处理的基材。
发明的详细说明
与本发明有关的术语“单官能”是指只含有一个能与异氰酸酯反应的官能团的化合物。
术语“官能化氟化物低聚物”是指含有能与异氰酸酯反应的官能团的氟化物低聚物。
本发明的氟化物组合物可以两步法反应制得。在第一步中制得官能化氟化物低聚物,它在第二步中进一步反应形成聚氨酯。
在第一步中,制得式(I)的氟化物低聚物:
Mf mMn-Ql-Tl (I)
Mf mMn表示包含由氟化单体得到的m个单元和由无氟单体得到的n个单元的氟化物低聚物,氟化单体和无氟单体可以相同或不同;
m表示约2-40的值;
n表示0-约20的值;
Tl是-OH或-NH2部分;和
Ql和Tl共同表示用Tl官能化的链转移剂除去一个氢原子所获得的有机残基;
氟化物低聚物中的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值可以是0-约20,较好的在约3-10之间。根据较佳实施方案,n值小于m值。由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得到的氟化物低聚物也属于本发明的范围。
在上式中,Ql通常表示下式的有机残基:
-S-R-
其中:
R表示有机二价连接基团,宜选自直链或支链的亚烷基(较好的是含约2-6个碳原子)、环状亚烷基、亚芳基和亚芳烷基。
氟化物低聚物可以在羟基或氨基官能化的链转移剂的存在下由氟化物单体(Rf-Ll-E)的自由基低聚合反应或者由该氟化物单体与烃类单体(Rh-E’)的自由基低聚合反应制得。与本发明有关的术语“烃(类)”是指任何基本上无氟的有机部分,它含有氢和碳,可任选的含有一个或多个取代基。氟化物低聚物的脂族主链包括足够数目的聚合单元以使这部分是低聚的。脂族主链较好的是包括约2-40个由氟化物单体得到的聚合单元和0至约20个由烃类单体得到的聚合单元。
在氟化物单体中,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、环状或上述的组合。它可以含有杂原子,如氧、二价或六价的硫、或氮。较好的Rf是完全氟化的基团,但是氢原子或氯原子可以作为取代基存在,只要对于每两个碳原子而言任一种上述原子不超过一个。Rf基团有至少约3个至约18个碳原子,较好是约3-14个,最好是约6-12个碳原子。Rf较好是含有约40-80%(重量)的氟,更好是约50-78%(重量)的氟。Rf基团的末端部分是全氟化部分,较好是含有至少7个氟原子,如CF3CF2CF2-、(CF3)2CF2-、F5SCF2-。较好的Rf基团是完全氟化或基本上氟化的,较好的是按照化学式CnF2n+1,其中n约为3-18。
连接基团Ll连接Rf基团和可自由基聚合的基团E。Ll较好的是含有1至约20个碳原子。Ll可任选地含有含氧、氮或硫的基团或者这些基团的组合,Ll较好的是不含会显著妨碍自由基低聚合反应的官能团(如可聚合的烯烃双键、硫醇和本领域技术人员已知的其它此类官能度)。合适的Ll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、硫代基、磺酰基、硫氧基、氨基、亚氨基、磺酰氨基、羧酰胺基、碳酰氧基、亚氨酯基(urethanylene)、1,3-亚脲基,以及上述这些基团的组合,如磺酰氨基亚烷基。较好的连接基团选自亚烷基、含约1-4个氧化烯部分的聚(氧化烯)基,以及下式的有机二价连接基团:
其中:
R3表示含2-4个碳原子的直链或支链亚烷基;和
R4表示含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式不饱和部分。合适的部分包括例如由乙烯基醚类、乙烯基酯类、烯丙基酯类、乙烯基甲酮类、苯乙烯类、乙烯基酰胺类、丙烯酰胺类、马来酸酯类、富马酸酯类、丙烯酸酯类和甲基丙烯酸酯类得到的那些部分。其中较好的是α,β-不饱和酸酯类,如丙烯酸酯类和甲基丙烯酸酯类。
如上所述的氟化物单体Rf-Ll-E及其制备方法已为人们所知,披露于如美国专利No.2,803,615中。这样的化合物的例子包括通用类型的氟化物丙烯酸酯类、甲基丙烯酸酯类、乙烯基醚类、和含有氟化磺酰氨基的烯丙基化合物、由氟化物调聚物醇类得到的丙烯酸酯类或甲基丙烯酸酯类、由氟化物羧酸类得到的丙烯酸酯类或甲基丙烯酸酯类,以及EP-A-526 976中揭示的全氟烷基的丙烯酸酯类或甲基丙烯酸酯类。较好的氟化物单体的例子包括:CF3(CF2)4CH2OCOC(CH3)=CH2CF3(CF2)6(CH2)2OCOC(CH3)=CH2CF3(CF2)6(CH2)2OCOCH=CH2CF3(CF2)6CH2OCOC(CH3)=CH2CF3(CF2)6CH2OCOCH=CH2CF3(CF2)7(CH2)2OCOCH=CH2 CF3CF2(CF2CF2)2-8CH2CH2OCOCH=CH2 R=甲基、乙基或正丁基。
合适的烃类单体Rh-E’也已为人们所知,通常能够购得。这类化合物的例子包括:通常类型的能自由基聚合的烯类化合物,例如烯丙基酯类,如乙酸烯丙基酯和庚酸烯丙基酯;烷基乙烯基醚类或烷基烯丙基醚类,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;不饱和酸类,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,如丙烯酸和甲基丙烯酸的乙烯基酯、烯丙基酯、甲酯、丁酯、异丁酯、己酯、庚酯、2-乙基己酯、环己酯、十二烷基酯、十八烷基酯、异冰片基酯或烷氧基乙基酯;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、正-二异丙基丙烯酰胺、二乙酰丙烯酰胺、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;苯乙烯及其衍生物,如乙烯基甲苯、α-甲基苯乙烯、α-氰基甲基苯乙烯;含卤的低级烯烃,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类,如氯乙烯和1,1-二氯乙烯。能与上述含氟代脂族基团的单体进行共聚反应的共聚单体较好的是包括选自甲基丙烯酸十八烷基酯、甲基丙烯酸十二烷基酯、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1,1-二氯乙烯的共聚单体。
用于制备氟化物低聚物的羟基或氨基官能化链转移剂较好的是具有如下化学式:
HS-R-X
其中,R按照本文定义,X是-OH或-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-巯基乙胺的链转移剂。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。
为了制备官能化的氟化物低聚物,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、过氧化苯二甲酸二叔丁酯;二酰基过氧化物,如过氧化苯甲酰和过氧化月桂酰。
在第二步中,将氟化物低聚物(或氟化物低聚物的混合物)和能与异氰酸基反应的单官能化合物与二异氰酸酯或三异氰酸酯反应。该反应还可任选地包括异氰酸酯封端剂或无氟低聚物和/或除氟化物低聚物、单官能化合物、异氰酸酯封端剂或无氟低聚物以外另外的异氰酸酯反应性化合物。本领域的技术人员应该理解根据本发明制备聚氨酯会产生化合物的混合物。
一般来说,氟化物低聚物的用量足以与约33-67%数目的异氰酸基反应,单官能化合物的用量足以与约33-67%数目的异氰酸基反应,异氰酸酯封端剂或无氟低聚物的用量能与约0-33%数目的异氰酸基反应。另外的异氰酸酯反应性化合物的用量可以与约0-10%数目的异氰酸基反应。
较好的是,单官能化合物的聚(氧化烯)基团中的氧化烯部分有约2-4个碳原子。这些氧化烯部分的例子包括-OCH2-CH2-、-OCH2-CH2-CH2-、-OCH(CH3)CH2-和-OCH(CH3)CH(CH3)-。这些氧化烯部分可以相同,如在聚(氧丙烯)中;或者可以混合物的形式存在,如直链或支链相混杂的或者无规分布的氧化乙烯与氧化丙烯部分的链,或者如直链或支链的氧化乙烯单元嵌段或氧化丙烯部分嵌段。聚(氧化烯)的链可以插入或包括一个或多个悬链键(catenary linkage)。当这些悬链键是三价或更高价时,它们提供了获得氧化烯部分的支链的手段。聚(氧化烯)基中氧化烯部分的数目较好的是在约5-120之间,更好的在17-48之间。
根据一个特别好的实施方案,单官能化合物对应于以下化学式:
H-W-R6-(O-R7)x-(O-R8)y-O-R9
其中:
W选自O、NH或S;
R6表示含约1-4个碳原子的亚烷基;
R7和R8各自选自含2-4个碳原子的直链或支链亚烷基;
R9表示含约1-4个碳原子的烷基;和
x和y各自选自0至约60的整数,条件是两者之和至少约为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,较好为大于1。最好是y是0,R7是亚乙基。
单官能化合物的典型例子包括聚氧化烯基团,包括聚二醇类的烷基醚,如聚乙二醇的甲醚或乙醚、环氧乙烷和环氧丙烷的无规共聚物或嵌段共聚物的羟基封端的甲醚或乙醚,以及聚环氧乙烷的氨基封端的甲醚或乙醚。
用于本发明的二异氰酸酯或三异氰酸酯包括脂族和芳族的异氰酸酯。它们的例子包括:芳族二异氰酸酯,如二异氰酸-4,4′-亚甲基二苯酯、4,6-二(三氟甲基)-1,3-苯二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、邻、间、对-亚二甲苯基二异氰酸酯、4,4′-二异氰酸基二苯醚、3,3′-二氯-4,4′-二异氰酸基二苯甲烷、4,5′-联苯基二异氰酸酯、4,4′-二异氰酸基联苄、3,3′-二甲氧基-4,4′-二异氰酸基联苯、3,3′-二甲基-4,4′-二异氰酸基联苯、2,2′-二氯-5,5′-二甲氧基-4,4′-二异氰酸基联苯、1,3-二异氰酸基苯、1,2-萘二异氰酸酯、4-氯-1,2-萘二异氰酸酯、1,3-萘二异氰酸酯和1,8-二硝基-2,7-萘二异氰酸酯;脂环族二异氰酸酯,如3-异氰酸基甲基-3,5,5-三甲基环己基异氰酸酯、3-异氰酸基甲基-3,5,5-三甲基环己基异氰酸酯;脂族二异氰酸酯,如1,6-己二异氰酸酯、2,2,4-三甲基-1,6-己二异氰酸酯和1,2-乙二异氰酸酯;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);环状二异氰酸酯,如异佛尔酮二异氰酸酯(IPDI)和二环己基甲烷-4,4′-二异氰酸酯。
还可以使用含有内部的由异氰酸酯得到的部分的异氰酸酯,如含缩二脲的三异氰酸酯(一些该物质可以DESMODURTM N-100购自Bayer)、含异氰脲酸酯的三异氰酸酯(一些该物质可以IPDI-1890购自Huls AG,Germany)和含有氮杂环丁烷二酮(azetedinedione)的二异氰酸酯(一些该物质可以DESMODURTM TT购自Bayer)。其它市售的二异氰酸酯或三异氰酸酯包括:以DESMODURTM L和DESMODURTM W购自Bayer的异氰酸酯,以及三(4-异氰酸基苯基)甲烷(可以DESMODURTM R购自Bayer)。
异氰酸酯封端剂可任选地使用。这些试剂包括这样的化合物,即它与异氰酸基反应时形成的化合物在室温下不与异氰酸酯反应性化合物反应,但是在室温下与异氰酸酯反应性化合物反应。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性化合物反应。可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。可以使用单一的化合物或者不同掩蔽剂或封端剂的混合物。特别好的异氰酸酯封端剂或掩蔽剂包括C2-C8链烷酮肟,如2-丁酮肟。
制备聚氨酯可任选使用的无氟低聚物可采用与制备氟化物低聚物类似的方法制备,只是使用无氟单体。合适的无氟单体包括本文上述Rh-E′类型的单体。根据一个特别优选的实施方案,无氟低聚物是通过低聚合至少一种含有能够在活化(如通过加热)时交联的官能团的单体而得到的。所述官能团的典型例子包括封端异氰酸酯和烷氧基硅烷基团。合适的无氟单体的例子包括:烷氧基硅烷官能化的丙烯酸酯类和甲基丙烯酸酯类,或者含有封端异氰酸酯的单体,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。无氟低聚物较好的聚合度约为2-40,更好约为3-20。
制备聚氨酯可任选地含有少量的除上述化合物以外的另外的异氰酸酯反应性化合物。异氰酸酯反应性化合物通常只含有一个异氰酸酯反应性基团。这些异氰酸酯反应性化合物的例子包括: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)。
在本领域技术人员熟知的常规条件下进行缩合反应。较好的是该反应在催化剂的存在下进行。合适的催化剂包括锡盐,如二月桂酸二丁锡、辛酸亚锡、油酸亚锡、二(2-乙基己酸)二丁锡(tin dibutyldi-(2-ethyl hexanoate)、氯化亚锡;以及本领域技术人员已知的其它催化剂。催化剂的存在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,合适催化剂的浓度一般约为0.001-10%(重量),较好约为0.1-5%(重量),以反应物总重量计。
缩合反应较好的是在干燥条件下于极性溶剂中进行,所述极性溶剂例如乙酸乙酯、丙酮、甲基异丁基酮、甲苯等。本领域技术人员可根据具体使用的试剂、溶剂和催化剂容易地决定合适的反应温度。虽然列举出适合所有情况的具体温度是不切实际的,但合适的温度一般约在室温至120℃之间。
采用常规的施用方法就可以施用本发明的氟化物组合物,但较好的是以水乳浊液的形式使用。或者,本发明的氟化物组合物可以以在溶剂中的处理组合物的形式使用。水乳浊液一般含有水、氟化物组合物(其含量能有效地向基材提供所需的拒斥性能)和表面活性剂(其含量能有效稳定该乳浊液)。水的存在量较好的是约70-2000重量份,以100重量份本发明氟化物组合物计。表面活性剂的存在量较好的约为1-25重量份,更好约为2-10重量份,以100重量份本发明氟化物组合物计。常用的阳离子型、非离子型、阴离子型和两性离子的表面活性剂都是适宜的。
水性或溶剂基处理组合物施用在基材上的量应足以赋予基材以高的污斑脱除性能。一般来说,足够的量是足以在待处理基材上提供基材重量的约0.01-5%(重量),较好约0.05-2%(重量)的氟化物组合物。足以赋予所需污斑脱除性能的处理组合物的用量可根据经验确定,并可根据需要增加。
本发明的氟化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、聚二醇类(如聚乙二醇)、上浆剂、改进拒水性和/或拒油性、耐火或抗静电性能的物质、缓冲剂、杀菌剂、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。较好的是将(甲基)丙烯酸烷基酯和(甲基)丙烯酸的共聚物用作氟化物组合物的辅助产品。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,更好是在50∶50和85∶15之间。较好的还有(甲基)丙烯酸酯的烷基是含约1-6个碳原子的低级烷基。(甲基)丙烯酸烷基酯的例子包括:丙烯酸和甲基丙烯酸的甲酯、乙酯和正丁酯。(甲基)丙烯酸烷基酯和(甲基)丙烯酸的共聚物还可以含有由烯键式不饱和单体得到的单元,但是较好的是该共聚物只含有由(甲基)丙烯酸烷基酯和(甲基)丙烯酸衍生得到的单元或部分。该共聚物还可以用碱(如氢氧化钠或氢氧化铵)部分或完全地中和。
用于氟化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的例子包括甲基纤维素、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的。因此,含有大量疏水性取代基的纤维素醚,如疏水性改性的纤维素醚(以NEXTONTM的商品名购自Aqualon)是不适合用于本发明的氟化物组合物的。
对用本发明的氟化物组合物处理的基材没有具体的限制,可包括塑料、金属、玻璃、纤维材料(如织物)、木材、非织造织物和纸。氟化物组合物特别有用于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)提供污斑脱除性能。经本发明氟化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。
为了对织物基材进行处理,可将基材浸在稀释的乳状液中。然后使浸透的基材经过浸轧机(padder)/滚筒,除去过量的乳状液,并在烘箱内干燥和固化,温度和时间应能足以提供经固化处理的基材。该固化过程通常在约50-190℃的温度下进行,该温度取决于具体的系统或采用的施用方法。一般来说,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分钟是适宜的。
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
配制含确定量的氟化物处理剂的处理浴。对试验基材如下进行处理:浸轧以提供浓度为0.3%或0.6%的固体(以织物重量计,表示为SOF(织物上的固体)),在150℃干燥样品3分钟。实施例所使用的试验基材均可购得,并在下面列出:*PES/CO:聚酯/棉67/33共混物,购自Arlitex,Avelgem Belgium*100%棉:购自UCO company,Destelbergen,Belgium
干燥后,试验基材的污斑脱除性能和拒斥性能。
实施例和比较例中所示的污斑脱除性、拒水性和拒油性的各自数据均基于下面的测定方法和评价标准:
污斑脱除试验
使用两种类型的污斑进行污斑脱除试验:
-脏的马达油(DMO),购自General Motors Garage Houttequiet,Beveren;Belgium
-茶:将LiptonTM黄色茶包浸在165毫升65℃水中3分钟而获得。
染污法1:滴染法
染污10厘米×10厘米的试样:对于PES/CO试样使用3滴DMO或茶,对于棉试样使用4滴DMO或茶。将这些样品在室温下平衡24小时,然后用Minolta比色计(Lamp D65)测量被污染样品与未被污染样品在反射上的差值,由此评定污染度。对每一污斑取3次测量的平均值,得到ΔLIN值。
染污法2:刷染法
在本方法中,对10厘米×10厘米的试样,在PES/CO样品上放置0.35毫升DMO或0.5毫升茶,在棉样品上放置0.5毫升DMO或0.6毫升茶。围绕着放置在污染液体附近直径为5厘米的塑料架刷整整3圈,将污染物刷进织物。如上所述进行反射测量。
洗涤方法
将试样用别针钉在PES/CO镇重物(总重3千克)或棉镇重物(总重4千克)上,在W832型Miele洗衣机中洗涤。加入市售洗涤剂(20克/千克,PES/CO加入Clax100,棉加入Clax晶体,购自Diversy Lever),在70℃洗涤基材,采用主洗涤程序,随后进行四次漂洗循环和离心。样品在转筒式干燥器中干燥,并在150℃熨烫15秒。未被污染的样品按照同样方式进行处理。用Minolta计测定样品,并与未被污染的样品进行比较,得到ΔLLD70℃值。
与ΔLIN比较所得的ΔLLD70℃的负值越小,污斑脱除性能越好。根据计算式%ΔΔL=(ΔLIN-ΔLLD70℃/ΔLIN)×100计算得到的%ΔΔL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。
拒水性试验(WR)
使用一系列水-异丙醇试验液体测定基材的拒水性(WR),其结果用经处理基材的″WR″等级表示。WR等级对应于在与基材接触15秒之后不渗透或润湿基材表面的渗透性最强的那种试验液体。能透过100%水(0%异丙醇)试验液体,即渗透性最小的试验液体或者仅能阻止该试验液体透过的基材,其等级为0。能阻止100%异丙醇(0%水)试验液体,即渗透性最强的试验液体透过的基材,其等级为10。其它中间的等级是用试验液体中异丙醇的百分数除以10来计算得到的。例如,经处理的基材能阻止70%/30%异丙醇/水的混合物,但不能阻止80%/20%的异丙醇/水的混合物,其等级为7。
拒油性(OR)
采用American Association of Textile Chemists and Colorists(AATCC)的标准试验方法No.118-1983测量基材的拒油性,该试验的基础是经处理的基材阻止不同表面张力的油透过的能力。仅能阻止Nujol矿物油(渗透性最小的的试验油)透过的经处理基材的等级为1,能阻止庚烷(渗透性最大的试验液体)透过的经处理基材的等级为8。其它中间等级可通过用下表所示的其它纯净油或油混合物测定。
标准试验液体
AATCC拒油性等级数 | 组成 |
1 | Nujol |
2 | Nujol/正十六烷65/35 |
3 | 正十六烷 |
4 | 正十四烷 |
5 | 正十二烷 |
6 | 正癸烷 |
7 | 正辛烷 |
8 | 正庚烷 |
缩写
实施例和比较例中所用的缩写和商品名如下:EtOAc: 乙酸乙酯RSH: 2-巯基乙醇AIBN: 偶氮二异丁腈HOEMA: 甲基丙烯酸2-羟乙酯BA: 丙烯酸丁酯Y11857: 三异丙氧基硅烷甲基丙烯酸酯,购自OSI company,BelgiumTMI: 1-(1-异氰酸基-1-甲基乙基)-4-(1-甲基乙烯基)苯,购自Cyanamid,
BelgiumMEFOSEA: 丙烯酸N-甲基全氟辛基磺酰氨基乙酯MPEG350-5000:聚乙二醇甲醚,上标数字表示MW,购自Inspec,BelgiumBO: 2-丁酮肟IPDI: 异佛尔酮二异氰酸酯DBTDL: 二月桂酸二丁锡MEHQ: 甲基氢醌DESN: 脂族多异氰酸酯,以DEMODURTM N购自Bayer(Germany)DESL: 芳族三异氰酸酯,以DESMODURTM L购自Bayer(Germany)PAPI: Voronate M220,多异氰酸多芳族多亚甲基酯(polyaromatic
polymethylene polyisocyanate),购自Dow Chemical(Netherlands)Arquad T-50:动物脂氯化三甲铵,购自Akzo,Littleborough,UK
除非另外说明,以下实施例中的所有份、比、百分数等都是以重量计的。
A.合成羟基封端的低聚物(HTO)
1.合成聚氨酯丙烯酸酯HOEMA/IPDI/BO(摩尔比为1/1/1)
用于制备羟基封端低聚物的聚氨酯丙烯酸酯HOEMA/IPDI/BO(摩尔比为1/1/1),其制备方法如下:
向配有机械搅拌器、温度控制器、加料漏斗和氮气进口和出口的圆底烧瓶中加入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。将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基已经反应。
2.合成羟基封端的低聚物(HTO)
按照与合成MEFOSEA/RSH 4/1(表1中表示为HTO-1)类似的方法制备表1所列的羟基封端的低聚物(HTO):
向配有两个回流冷凝器、搅拌器、温度控制器、氮气进口和真空出口的圆底烧瓶中加入2.4摩尔(1433克)MEFOSEA和987克EtOAc。于40℃加热该混合物直到所有氟化物单体溶解。加入0.6摩尔(46.8克)2-巯基乙醇和0.15%AIBN。该反应混合物逐渐加热至80℃。反应在氮气气氛中于80℃进行16小时,反应后得到大于95%的转化率。
表1羟基封端低聚物(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 | (HOEMA1/IPDI1/BO1)/BA/RSH | 1/3/1 |
HTO-4 | BA/Y11857/RSH | 4.075/0.125/1 |
HTO-5 | BA/Y11857/RSH | 4.5/0.5/1 |
HTO-6 | (TMI1/BO1)/BA/RSH | 1/3/1 |
B.合成含氟化合物(FC)
采用与合成DESL/HTO-1/MPEG750/BO 1/1/1/1(表2中的FC-7)类似的方法制备表2所列的数种含氟化合物:
向配有冷凝器、温度计、搅拌器和氮气进管的圆底烧瓶中加入7.85克(0.008摩尔)Desmodur L、20.18克HTO-1、6克(0.008摩尔)PEG750和81克甲基异丁基酮。该反应混合物加热至50℃,加入0.7克(0.008摩尔)2-丁酮肟,然后加入催化剂(DBTDL)。该混合物温度升高至85℃,进行反应直至反应完全。
C.乳化
将步骤B中得到的含氟化合物(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,然后在真空下除去有机溶剂。制得含15%含氟化合物的乳状液。
表2氟化物聚氨酯(FC)的组成
FC | 含氟化合物的组成 | 摩尔比 |
FC-1 | DESN/HTO-1/HTO-3/MPEG750 | 1/1/1/1 |
FC-2 | DESN/HTO-1/HTO-3/MPEG2000 | 1/1/1/1 |
FC-3 | DESN/HTO-2/HTO-3/MPEG2000 | 1/1/1/1 |
FC-4 | DESN/HTO-1/MPEG2000 | 1/1.5/1.5 |
FC-5 | DESN/HTO-1/MPEG5000 | 1/1.5/1.5 |
FC-6 | DESN/HTO-1/MPEG2000 | 1/1/2 |
FC-7 | DESL/HTO-1/MPEG750/BO | 1/1/1/1 |
FC-8 | DESL/HTO-2/MPEG2000/BO | 1/1/1/1 |
FC-9 | DESL/HTO-1/MPEG2000/BO | 1/1/1/1 |
FC-10 | DESL/HTO-2/MPEG750/BO | 1/1/1.5/0.5 |
FC-11 | DESN/HTO-1/HTO-4/MPEG750 | 1/1/1/1 |
FC-12 | DESN/HTO-1/HTO-5/MPEG750 | 1/1/1/1 |
FC-13 | DESN/HTO-1/HTO-6/MPEG750 | 1/1/1/1 |
FC-14 | PAPI/HTO-1/MPEG350/BO | 1/1/1/1 |
实施例1-10和比较例C-1
实施例1-10中,按照上述一般方法制得本发明的氟化物组合物并乳化。用该氟化物组合物处理聚酯/棉(PES/CO)共混物,以得到0.3%或0.6%的SOF。处理后,织物于150℃干燥3分钟。经处理的PES/CO基材采用滴染法用脏的马达油染污。用未经处理的PES/CO织物作成比较例C-1。表3中示出了污斑脱除性、拒油性和拒水性的结果。
表3经处理的PES/CO的污斑脱除性(DMO-滴染法)和拒斥性能
实施例号 | 含氟化合物 | %SOF | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLLD70℃ | %ΔΔL | |||
1 | FC-1 | 0.3 | 5 | 7 | -6.85 | -0.74 | 89 |
2 | FC-1 | 0.6 | 5 | 8 | -6.37 | -2.44 | 62 |
3 | FC-11 | 0.3 | 5 | 5 | -11.22 | -5.08 | 55 |
4 | FC-11 | 0.6 | 6 | 8 | -8.3 | -1.7 | 80 |
5 | FC-12 | 0.3 | 5 | 8 | -6.81 | -0.72 | 89 |
6 | FC-12 | 0.6 | 6 | 9 | -9.71 | -2.49 | 74 |
7 | FC-13 | 0.3 | 5 | 5 | -9.62 | -4.89 | 49 |
8 | FC-13 | 0.6 | 6 | 8 | -10.42 | -3.33 | 68 |
9 | FC-7 | 0.3 | 4 | 4 | -4.72 | -2.03 | 57 |
10 | FC-14 | 0.6 | 5 | 5 | -6.79 | -2.18 | 68 |
C-1 | -- | -- | 0 | 0 | -15.45 | -9.56 | 38 |
这些数据表明,所有的氟化物组合物都提供了良好至非常好的DMO污斑脱除性能。
实施例11-18和比较例C-2
在实施例11-18中,重复与上面同样的试验,但是这一次是采用刷染法使DMO染污织物。用未经处理的PES/CO织物作成比较例C-2。表4中示出了污斑脱除性、拒油性和拒水性的结果。
表4经处理的PES/CO的污斑脱除性(DMO-刷染法)和拒斥性能
实施例号 | 含氟化合物 | %SOF | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLLD70℃ | %ΔΔL | |||
11 | FC-2 | 0.3 | 2 | 5 | -17.88 | -7.64 | 57 |
12 | FC-3 | 0.3 | 1 | 3 | -17.67 | -8.05 | 54 |
13 | FC-4 | 0.6 | 6 | 9 | -18.09 | -6.6 | 64 |
14 | FC-5 | 0.3 | 3 | 2 | -17.97 | -9.78 | 46 |
15 | FC-6 | 0.6 | 4 | 9 | -18.73 | -7.6 | 59 |
16 | FC-8 | 0.3 | 2 | 3 | -18.01 | -7.87 | 56 |
17 | FC-9 | 0.3 | 1 | 3 | -17.77 | -7.48 | 58 |
18 | FC-10 | 0.6 | 5 | 5 | -18.17 | -9.16 | 50 |
C-2 | -- | -- | 0 | 0 | -15.32 | -8.67 | 43 |
结果表明,即使是在更严酷的刷染法中,仍观察到经氟化物组合物处理的织物显示良好的DMO污斑脱除性。氟化物组合物不仅向织物提供良好的DMO污斑脱除性,而且提供中等到高的拒油性和拒水性,这是它的又一个优点。
实施例19-26和比较例C-3
在实施例19-26中,按照上述一般方法用氟化物组合物处理100%棉基材,对它重复进行与上面相同类型的试验。采用刷染法在棉基材上进行DMO染污。用未经处理的棉织物作成比较例C-3。表5中示出了污斑脱除性、拒油性和拒水性的结果。
表5经处理的棉的污斑脱除性(DMO-刷染法)和拒斥性能
实施例号 | 含氟化合物 | %SOF | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLLD70℃ | %ΔΔL | |||
19 | FC-2 | 0.6 | 4 | 4 | -19.89 | -8.25 | 59 |
20 | FC-3 | 0.6 | 2 | 3 | -19.9 | -7.96 | 60 |
21 | FC-4 | 0.6 | 4 | 7 | -19.49 | -8.22 | 58 |
22 | FC-5 | 0.6 | 2 | 3 | -18.03 | -8.83 | 51 |
23 | FC-6 | 0.6 | 3 | 5 | -19.38 | -8.34 | 57 |
24 | FC-8 | 0.6 | 3 | 1 | -19.23 | -8.18 | 57 |
25 | FC-9 | 0.3 | 2 | 2 | -18.7 | -8.3 | 56 |
26 | FC-10 | 0.3 | 2 | 2 | -19.5 | -8.45 | 57 |
C-3 | -- | -- | 0 | 0 | -15.70 | -8.76 | 44 |
这些数据表明,用氟化物组合物处理能够向棉基材提供良好的对油性污斑(如DMO)的污斑脱除百分数(%ΔΔL)。
实施例27-35和比较例C-4
在实施例27-35中,采用滴染法将用本发明氟化物组合物处理过的PES/CO共混物用茶染污。用未经处理的织物作成比较例C-4。表6中示出了污斑脱除性、拒油性和拒水性的结果。
表6 经处理的PES/CO的污斑脱除性(茶-滴染法)和拒斥性能
观察到高的茶污斑脱除百分数。
实施例号 | 含氟化合物 | %SOF | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLLD70℃ | %ΔΔL | |||
27 | FC-1 | 0.3 | 5 | 7 | -3.73 | -0.34 | 91 |
28 | FC-1 | 0.6 | 5 | 8 | -4.14 | -0.22 | 95 |
29 | FC-11 | 0.3 | 5 | 5 | -4.01 | -0.98 | 76 |
30 | FC-11 | 0.6 | 6 | 8 | -5.82 | -0.68 | 88 |
31 | FC-12 | 0.3 | 5 | 8 | -5.44 | -0.79 | 85 |
32 | FC-12 | 0.6 | 6 | 9 | -6.79 | -0.72 | 89 |
33 | FC-13 | 0.3 | 5 | 5 | -5.73 | -0.59 | 90 |
34 | FC-7 | 0.6 | 5 | 4 | -6.68 | -0.61 | 91 |
35 | FC-14 | 0.6 | 5 | 5 | -6.31 | -0.75 | 88 |
C-4 | -- | -- | 0 | 0 | -2.32 | -0.91 | 61 |
实施例36-43和比较例C-5
在实施例36-43中,将经相同处理的PES/CO基材用茶污斑进行试验,但是采用刷染法。用未经处理的材料作成比较例C-5。表7中示出了污斑脱除性、拒油性和拒水性的结果。
表7经处理的PES/CO的污斑脱除性(茶-刷染法)和拒斥性能
实施例号 | 含氟化合物 | %SOF | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLLD70℃ | %ΔΔL | |||
36 | FC-2 | 0.3 | 2 | 5 | -1.59 | -0.75 | 53 |
37 | FC-3 | 0.3 | 1 | 3 | -1.66 | -0.65 | 61 |
38 | FC-4 | 0.6 | 6 | 9 | -2.25 | -0.72 | 68 |
39 | FC-5 | 0.3 | 3 | 2 | -2.66 | -1.13 | 58 |
40 | FC-6 | 0.6 | 4 | 9 | -2.01 | -0.55 | 73 |
41 | FC-8 | 0.6 | 3 | 4 | -2.12 | -1.05 | 50 |
42 | FC-9 | 0.6 | 3 | 4 | -2.12 | -0.9 | 58 |
43 | FC-10 | 0.6 | 5 | 5 | -1.92 | -1.24 | 35 |
C-5 | -- | -- | 0 | 0 | -2.62 | -1.22 | 53 |
尽管在一些情况下对茶污斑的脱除百分数不比未经处理的样品好多少或者甚至比之更差,但是几乎所有的经处理样品的ΔLLD70℃负值比未经处理样品小得多,这表明在经本发明氟化物组合物处理过的样品的情况下,洗涤后的可见污斑较少。
实施例44-51和比较例C-6
在实施例44-51中,将经本发明氟化物组合物处理过的棉基材用刷染法进行茶沾污。用未经处理的材料作成比较例C-6。表8中示出了污斑脱除性、拒油性和拒水性的结果。
表8经处理的棉的污斑脱除性(茶-刷染法)和拒斥性能
实施例号 | 含氟化合物 | %SOF | 最初性能 | 污斑脱除比色测定 | |||
OR | WR | ΔLIN | ΔLLD70℃ | %ΔΔL | |||
44 | FC-2 | 0.3 | 1 | 2 | -2.16 | -0.42 | 81 |
45 | FC-3 | 0.3 | 1 | 2 | -2.58 | -0.59 | 77 |
46 | FC-4 | 0.3 | 2 | 5 | -3.19 | -1.19 | 63 |
47 | FC-5 | 0.3 | 0 | 2 | -3.86 | -1.39 | 64 |
48 | FC-6 | 0.3 | 2 | 4 | -3.72 | -1.38 | 63 |
49 | FC-8 | 0.3 | 1 | 0 | -3.18 | -1.05 | 67 |
50 | FC-9 | 0.3 | 2 | 2 | -2.89 | -0.85 | 71 |
51 | FC-10 | 0.3 | 2 | 2 | -2.48 | -0.84 | 66 |
C-6 | -- | -- | 0 | 0 | -3.21 | -1.36 | 58 |
结果表明,经本发明氟化物组合物处理的棉织物显示高的茶污斑脱除性。还获得了中等拒水性。
Claims (14)
1.一种制备包含聚氨酯的氟化物组合物的方法,该方法包括使下列(A)、(B)、(C)和(D)与(E)反应:
(A)式(I)的氟化物低聚物:
Mf mMn-Ql-Tl (I)
其中:
Mf mMn表示包含由氟化单体得到的m个单元和由无氟单体得到的n个单元的氟化物低聚物,氟化单体和无氟单体可以相同或不同;
m表示2-40的值;
n表示0-20的值;
Tl是-OH或-NH2;
Ql和Tl共同表示用Tl官能化的链转移剂除去一个氢原子所获得的有机残基;
(B)能与异氰酸酯反应的单官能化合物,它包含聚(氧化烯)基团;
(C)异氰酸酯封端剂或无氟低聚物;
(D)除所述氟化物低聚物、所述异氰酸酯封端剂、所述无氟低聚物或所述单官能化合物以外的异氰酸酯反应性化合物;
(E)二异氰酸酯或三异氰酸酯;
以使得二异氰酸酯或三异氰酸酯中约33-67%数目的异氰酸基与化学式(I)的所述氟化物低聚物反应,二异氰酸酯或三异氰酸酯中约33-67%数目的异氰酸基与所述单官能化合物反应,二异氰酸酯或三异氰酸酯中约0-33%数目的异氰酸基与异氰酸酯封端剂或无氟低聚物反应,二异氰酸酯或三异氰酸酯中约0-10%数目的异氰酸基与所述异氰酸酯反应性化合物反应。
2.如权利要求1所述的方法,其中所述氟化单体对应于以下化学式:
Rf-Ll-E
其中:
Rf选自全氟化或部分氟化的脂族基团;
Ll表示有机二价连接基团;
E表示可自由基聚合的基团。
4.如以上权利要求中任一项所述的方法,其中Ql对应于下式:
-S-R-
其中:
R表示有机二价连接基团,它选自直链或支链的亚烷基、环状亚烷基和亚芳基。
5.如以上权利要求中任一项所述的方法,其中所述单官能化合物对应于以下化学式:
H-W-R6-(O-R7)x-(O-R8)y-O-R9
其中:
W选自O、NH和S;
R6表示含1-4个碳原子的亚烷基;
R7和R8各自选自含2-4个碳原子的直链或支链亚烷基;
R9表示含1-4个碳原子的烷基;和
x和y各自选自0-60的整数,条件是x和y之和至少为5。
6.一种处理基材的方法,包括使所述基材与一种包含聚氨酯的氟化物组合物接触的步骤,所述氟化物组合物是用权利要求1-5中任一项所述方法制得的。
7.如权利要求6所述的方法,其中所述基材是纤维基材。
8.如权利要求7所述的方法,其中所述基材包括天然纤维。
9.如权利要求7所述的方法,其中所述基材是纤维状的,纤维选自纤维素纤维、聚酯纤维,以及它们的组合。
10.如权利要求6-9中任一项所述的方法,其中所述氟化物组合物还包含一种聚合物,所述聚合物选自聚乙烯醇、(甲基)丙烯酸和(甲基)丙烯酸烷基酯的共聚物、聚乙二醇和非离子型纤维素醚。
11.一种包含聚氨酯的氟化物组合物,它由权利要求1-5中任一项所述的方法制得。
12.如权利要求11所述的氟化物组合物,它还包含一种聚合物,所述聚合物选自聚乙烯醇、(甲基)丙烯酸和(甲基)丙烯酸烷基酯的共聚物、聚乙二醇和非离子型纤维素醚。
13.将权利要求11或12所述的氟化物组合物用来赋予基材污斑脱除性能。
14.一种基材,在其至少一面的至少一部分上包含有权利要求11或12定义的氟化物组合物。
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---|---|---|---|---|
CN100342075C (zh) * | 2004-02-24 | 2007-10-10 | 福盈科技化学股份有限公司 | 溶剂型氟素疏水疏油剂及其制造方法 |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6391807B1 (en) | 1999-09-24 | 2002-05-21 | 3M Innovative Properties Company | Polymer composition containing a fluorochemical oligomer |
US6288157B1 (en) | 1999-05-11 | 2001-09-11 | 3M Innovative Properties Company | Alkylated fluorochemical oligomers and use thereof |
US6525127B1 (en) | 1999-05-11 | 2003-02-25 | 3M Innovative Properties Company | Alkylated fluorochemical oligomers and use thereof in the treatment of fibrous substrates |
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AU2001273428A1 (en) * | 2000-08-14 | 2002-02-25 | 3M Innovative Properties Company | Urethane-based stain-release coatings |
JPWO2004013089A1 (ja) | 2002-08-06 | 2006-09-21 | ダイキン工業株式会社 | 含フッ素ウレタン化合物およびその組成物 |
AR049208A1 (es) | 2004-06-08 | 2006-07-05 | Basf Ag | Composiciones polimericas anfifilicas y su uso |
EP1783119A4 (en) | 2004-08-03 | 2009-09-30 | Daikin Ind Ltd | FLUOROUS URETHANE |
WO2007002894A1 (en) * | 2005-06-29 | 2007-01-04 | 3M Innovative Properties Company | Polyurethanes derived from oligomeric fluoroacrylates |
US7652117B2 (en) * | 2007-06-20 | 2010-01-26 | 3M Innovative Properties Company | Fluorochemical urethane compounds and aqueous compositions thereof |
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 |
US7897678B2 (en) | 2007-07-26 | 2011-03-01 | 3M Innovative Properties Company | Fluorochemical urethane compounds having pendent silyl groups |
JP5599712B2 (ja) | 2007-10-05 | 2014-10-01 | インターフェース バイオロジクス,インコーポレーテッド | オリゴフッ素化架橋ポリマーおよびそれの使用 |
WO2010025398A1 (en) * | 2008-08-28 | 2010-03-04 | Interface Biologics Inc. | Thermally stable biuret and isocyanurate based surface modifying macromolecules and uses thereof |
JP5195373B2 (ja) * | 2008-12-08 | 2013-05-08 | 旭硝子株式会社 | ウレタン/尿素化合物、その製造方法および撥水剤組成物 |
PT2295132T (pt) | 2009-05-15 | 2016-11-15 | Interface Biologics Inc | Membranas de fibra oca antitrombogénicas, material de encapsulamento e tubulação para sangue |
US10370792B2 (en) * | 2012-04-24 | 2019-08-06 | 3M Innovative Properties Company | Surfactant-containing fluorochemical compositions, articles, and methods |
WO2013162704A1 (en) * | 2012-04-24 | 2013-10-31 | 3M Innovative Properties Company | Fluorochemical compounds, compositions, articles, and methods |
JP2014084422A (ja) * | 2012-10-25 | 2014-05-12 | Toyo Ink Sc Holdings Co Ltd | 分散剤と分散剤の製造方法、該分散剤を用いた顔料組成物および顔料分散体。 |
US9764884B2 (en) | 2014-10-06 | 2017-09-19 | Interface Biologics, Inc. | Packaging materials including a barrier film |
EP3529300A4 (en) | 2016-10-18 | 2020-03-18 | Evonik Canada Inc. | PLASTIFIED PVC ADDITIVES WITH SURFACE-MODIFYING MACROMOLECULES AND ARTICLES MADE THEREOF |
WO2019014400A1 (en) | 2017-07-14 | 2019-01-17 | Fresenius Medical Care Holdings, Inc. | PROCESS FOR OBTAINING SURFACE MODIFICATION COMPOSITION WITH ENHANCED BY-PRODUCT REMOVAL |
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US5509939A (en) * | 1989-12-29 | 1996-04-23 | E. I. Du Pont De Nemours And Company | Soil-release process |
US5276175A (en) * | 1991-04-02 | 1994-01-04 | Minnesota Mining And Manufacturing Company | Isocyanate derivatives comprising flourochemical oligomers |
US5672651A (en) * | 1995-10-20 | 1997-09-30 | Minnesota Mining And Manufacturing Company | Durable repellent fluorochemical compositions |
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1998
- 1998-05-14 DE DE69807684T patent/DE69807684T2/de not_active Expired - Fee Related
- 1998-05-14 KR KR1019997010467A patent/KR20010012512A/ko not_active Application Discontinuation
- 1998-05-14 AU AU74879/98A patent/AU7487998A/en not_active Abandoned
- 1998-05-14 AU AU74855/98A patent/AU7485598A/en not_active Abandoned
- 1998-05-14 EP EP98922268A patent/EP0981560B1/en not_active Expired - Lifetime
- 1998-05-14 JP JP54954798A patent/JP2001525874A/ja active Pending
- 1998-05-14 CN CNB988050528A patent/CN1165560C/zh not_active Expired - Fee Related
- 1998-05-14 EP EP98922296A patent/EP0981562B1/en not_active Expired - Lifetime
- 1998-05-14 JP JP54954998A patent/JP2002504938A/ja active Pending
- 1998-05-14 WO PCT/US1998/009797 patent/WO1998051723A1/en not_active Application Discontinuation
- 1998-05-14 BR BR9808774-6A patent/BR9808774A/pt not_active Application Discontinuation
- 1998-05-14 DE DE69802395T patent/DE69802395T2/de not_active Expired - Fee Related
- 1998-05-14 JP JP54951398A patent/JP2001525871A/ja active Pending
- 1998-05-14 WO PCT/US1998/009866 patent/WO1998051724A1/en not_active Application Discontinuation
- 1998-05-14 KR KR1019997010464A patent/KR20010012509A/ko not_active Application Discontinuation
- 1998-05-14 EP EP98922293A patent/EP0981561B1/en not_active Expired - Lifetime
- 1998-05-14 AU AU74876/98A patent/AU7487698A/en not_active Abandoned
- 1998-05-14 DE DE69801323T patent/DE69801323T2/de not_active Expired - Fee Related
- 1998-05-14 KR KR1019997010465A patent/KR20010012510A/ko not_active Application Discontinuation
- 1998-05-14 CN CN98805094A patent/CN1255931A/zh active Pending
- 1998-05-14 CN CN98805050A patent/CN1255929A/zh active Pending
- 1998-05-14 BR BR9808778-9A patent/BR9808778A/pt not_active Application Discontinuation
- 1998-05-14 WO PCT/US1998/009872 patent/WO1998051725A1/en not_active Application Discontinuation
- 1998-05-14 BR BR9808768-1A patent/BR9808768A/pt not_active Application Discontinuation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100342075C (zh) * | 2004-02-24 | 2007-10-10 | 福盈科技化学股份有限公司 | 溶剂型氟素疏水疏油剂及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0981561B1 (en) | 2001-08-08 |
JP2001525871A (ja) | 2001-12-11 |
WO1998051725A1 (en) | 1998-11-19 |
JP2001525874A (ja) | 2001-12-11 |
CN1255930A (zh) | 2000-06-07 |
DE69801323D1 (de) | 2001-09-13 |
DE69807684T2 (de) | 2003-06-05 |
DE69802395D1 (de) | 2001-12-13 |
EP0981560A1 (en) | 2000-03-01 |
JP2002504938A (ja) | 2002-02-12 |
KR20010012509A (ko) | 2001-02-15 |
EP0981560B1 (en) | 2001-11-07 |
WO1998051724A1 (en) | 1998-11-19 |
BR9808768A (pt) | 2000-08-01 |
DE69802395T2 (de) | 2002-07-11 |
EP0981562A1 (en) | 2000-03-01 |
EP0981561A1 (en) | 2000-03-01 |
BR9808778A (pt) | 2000-08-01 |
CN1165560C (zh) | 2004-09-08 |
BR9808774A (pt) | 2000-09-05 |
KR20010012510A (ko) | 2001-02-15 |
EP0981562B1 (en) | 2002-09-04 |
WO1998051723A1 (en) | 1998-11-19 |
AU7487998A (en) | 1998-12-08 |
AU7485598A (en) | 1998-12-08 |
DE69807684D1 (de) | 2002-10-10 |
DE69801323T2 (de) | 2002-07-25 |
AU7487698A (en) | 1998-12-08 |
KR20010012512A (ko) | 2001-02-15 |
CN1255929A (zh) | 2000-06-07 |
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