CN1425030A - 共聚物及包含它们的抗油和抗水组合物 - Google Patents

共聚物及包含它们的抗油和抗水组合物 Download PDF

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Publication number
CN1425030A
CN1425030A CN00818494A CN00818494A CN1425030A CN 1425030 A CN1425030 A CN 1425030A CN 00818494 A CN00818494 A CN 00818494A CN 00818494 A CN00818494 A CN 00818494A CN 1425030 A CN1425030 A CN 1425030A
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China
Prior art keywords
composition
multipolymer
acid
ester
vinylformic acid
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CN00818494A
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D·S·索恩
D·A·奥福德
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Nano Tex Co Ltd
Nano Tex Inc
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Nano Tex Co Ltd
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Publication of CN1425030A publication Critical patent/CN1425030A/zh
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    • C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
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Abstract

本发明涉及能够形成抗水剂和抗油剂的共聚物，它能够结合到纺织品和其它材料上而不产生甲醛。根据本发明的共聚物包括a)含氟代脂族基的试剂；(b)(甲基)丙烯酸十八酯；(c)含氯化合物；和(d)单体，选自包含酸酐官能团或能够形成酸酐官能团的那些。本发明进一步提供用于纤维性和其它基材的赋予抗水性和抗油性的组合物，组合物包括以上共聚物和催化剂，如次磷酸钠，用于从共聚物中的含酸单体形成酸酐。共聚物可进一步任选地包括其它添加剂，例如聚(丙烯酸)、增量剂、软化剂、抗氧剂、表面活性剂、和/或增塑剂。

Description

共聚物及包含它们的抗油和抗水组合物
                       技术领域
本发明涉及包括如下的组合物：包含氟代脂族基团的试剂和包含酸酐官能团或能够形成酸酐官能团的单体，通过对基材的酯、酰胺、硫代酸酯、或相似键的形成，对用其处理的纤维性基材和其它材料赋予抗水性和抗油性。在另一方面，本发明涉及使用这样的组合物处理这样基材和材料的方法，和在另一方面它涉及所处理的基材和材料。在又一方面，使用耐用的软化剂/增量剂以改进组合物的抗水剂性能和改进手感。
                       发明背景
采用氟化物组合物对纤维性基材的处理以赋予抗水性和抗油性是已知的；参见，例如，Banks，Ed.，Organofluorine Chemicals and TheirIndustrial Applications(有机氟化学品和它们的工业应用)，EllisHorwood Ltd.，Chichester，England，1979，226-234页。
一般情况下，具有抗水性和抗油性的共聚物是这样的共聚物，每个包括：含有全氟烷基能够直接得到抗水性和抗油性的(甲基)丙烯酸酯单体；通过对其的亲合力，能够改进对要处理的材料，如纤维等表面的粘合性的无氟单体；能够通过自交联或与在要处理材料表面上的基团反应提供耐用性的单体，典型地它们是含有与主链结合的N-羟甲基的共聚物，如含全氟烷基(甲基)丙烯酸酯的共聚物和N-羟甲基丙烯酰胺基共聚物。然而，当采用这些共聚物处理纤维性或其它基材时，会产生甲醛，从环境和安全观点来看它是非常不需要的。
                         发明概述
本发明涉及能够形成抗水剂和抗油剂的新型共聚物，它能够结合到纤维性基材和其它材料上而不产生甲醛。
根据本发明的新型共聚物包括a)含氟代脂族基的试剂；(b)(甲基)丙烯酸十八酯；(c)含氯化合物，例如偏二氯乙烯、氯乙烯、丙烯酸2-氯乙酯、或2-氯乙基乙烯基醚；和(d)选自包含酸酐官能团或能够形成酸酐官能团的单体。
共聚物可以进一步与如下物质共聚：i)(甲基)丙烯酸羟烷基酯以增加获得共聚物的性能和持久性，ii)化合物如聚(乙二醇)(甲基)丙烯酸酯以改进共聚物在水中的溶解性，和/或iii)链终止剂，如十二烷硫醇、巯基琥珀酸、或其它相似化合物，它们用于保持聚合物的分子量较低使得它可以更容易地在水中分散和可以更好地渗透织物。
本发明进一步提供用于纤维性和其它基材的赋予抗水性和抗油性的组合物，组合物包括以上共聚物和催化剂，如次磷酸钠，用于从共聚物中的含酸单体形成酸酐。
共聚物可进一步任选地包括其它添加剂，例如聚(丙烯酸)，已经由申请人发现由于未知的机理它可增加聚合物的性能和耐用性，可能是(不受理论的限制)由于将共聚物“粘着”到织物表面上。其它任选的添加剂包括抗氧剂，如乙二胺四乙酸(EDTA)，以降低基材变黄、永久的软化剂/增量剂以改进基材的手感和增加抗水性、表面活性剂以在水中乳化聚合物、润湿剂、和/或增塑剂。
可以通过将基材与组合物接触，例如，通过将它浸入组合物浴中或通过将组合物喷涂在基材上，而将组合物涂敷，如到纤维性基材上。然后固化处理的基材以从中除去溶剂并与纺织品的反应。
本发明的组合物向采用其处理的基材赋予所需的抗水性和抗油性，而不不利地影响基材的其它所需性能，如手感(或触感)柔软。组合物允许对于棉和其它基材的非甲醛释放结合。本发明的组合物可用于向纤维性基材如纺织品、纸、非织造制品或皮革提供抗水性和抗油性。
                       发明详述
含氟代脂族基的试剂可选自用于处理织物以获得对于水和油性和含水污点排斥性的任何的那些。含氟代脂族基的试剂包括缩聚物、如聚酯、聚酰胺或聚环氧化物和乙烯基化合物，如丙烯酸酯、甲基丙烯酸酯或聚乙烯基醚。这样含氟代脂族基的赋予抗水性和抗油性试剂的另外例子包括通过全氟脂族硫代二醇与二异氰酸酯的反应以获得带有全氟代脂族基的聚氨酯形成的那些。可以使用的另一组化合物是含氟代脂族基的N-羟甲基缩合产物。另外的例子包括含氟代脂族基的聚碳二亚胺，它可以通过，例如在合适催化剂存在下全氟脂族磺酰氨基链烷醇与多异氰酸酯的反应获得。氟聚合物可包括-CF3和-CHF2端基、全氟异丙氧基(-OCF(CF3)2)、3，3，3-三氟丙基等。聚合物可包括含有全氟化或部分氟化烷基链的乙烯基醚。
氟化物组分优选选自一种或多种含氟代脂族基团的丙烯酸酯或甲基丙烯酸酯单体。这样的单体具有通式I的结构，如下：
Figure A0081849400071
在通式I的化合物中，例如：
m是0-2；
n是0或1；
o是0-2；
A是-SO2-、-N(W)-SO2-、-CONH-、-CH2-、或CF2-；
R是线型、支化、或环状氟碳，包括全部或部分氟化烃，其中R可以是，例如C1-C30氟碳；
W是氢或C1-C4低级烷基；和
X是丙烯酸酯或甲基丙烯酸酯。
含氟代脂族基的试剂是市售的或可以合成的。市售试剂包括FX-13，购自3M的氟化丙烯酸酯；FX-14，购自3M的氟化甲基丙烯酸酯；Zonyl TA-N，购自DuPont的氟化丙烯酸酯；Zonyl TM，购自DuPont的氟化甲基丙烯酸酯；和购自AlliedSignal(Morristown，NJ.)的FAVETM产品。
作为本发明共聚物组分(a)的含氟代脂族基的试剂以一定的比例共聚，以占共聚物的约30-约70wt％，优选约35-约65wt％。
作为本发明共聚物组分(b)的(甲基)丙烯酸十八酯以一定的比例共聚，以占共聚物的约25-约60wt％，优选约30-约60wt％。
作为本发明共聚物组分(c)的含氯化合物以一定的比例共聚，以占聚合物的约1-约25wt％，优选约5-约20wt％。
作为本发明共聚物组分(d)的单体选自包含酸酐官能团或能够形成酸酐官能团的那些单体。这样的单体可包括羧酸和羧酸酐和可以是，但不限于，马来酸、马来酸酐、丙烯酸、衣康酸、双丙烯酰氨基乙酸、3-丁烯-1，2，3-三羧酸、丙烯酸2-羧乙酯、甲基丙烯酸、丙烯酸酐、烯丙基琥珀酸酐、柠康酸酐、甲基丙烯酸酐、4-甲基丙烯酰氧基乙基苯三酸酐、4，4’-六氟-亚异丙基双邻苯二甲酸酐等。单体以一定的比例共聚，以占本发明共聚物的约1-约10wt％，优选约2-约5wt％。
用于本发明作为本发明共聚物任选组分的(甲基)丙烯酸羟烷基酯包括，例如，(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟丙酯、(甲基)丙烯酸3-羟丙酯、(甲基)丙烯酸2-羟丁酯、(甲基)丙烯酸4-羟丁酯等，并可以一定的比例共聚，以占共聚物的不大于约5wt％，优选约1-约3wt％，基于总共聚物。当共聚(甲基)丙烯酸羟烷基酯时，同时采用交联剂如丁烷四羧酸、聚(丙烯酸)等，可以达到耐用性的进一步改进。除非另外说明，在此使用的术语“(甲基)丙烯酸酯”表示丙烯酸酯或甲基丙烯酸酯化合物。
本发明共聚物可以根据各种已知方法，优选通过溶液聚合或通过乳液聚合制备。溶液聚合可以通过如下方式进行：将各自的单体一起溶于合适的溶剂中，随后使用自由基引发剂进行聚合反应。乳液聚合可以通过如下方式进行：使用各种表面活性剂，优选非离子表面活性剂、阴离子表面活性剂、或其混合物，将各自单体一起乳化和分散入水中，随后在自由基引发剂存在下，采用搅拌，进行聚合反应。
为形成本发明的抗油和抗水组合物，将包括如下物质：a)含氟代脂族基的试剂，(b)(甲基)丙烯酸十八酯，(c)含氯化合物，如偏二氯乙烯、氯乙烯、丙烯酸2-氯乙酯、或2-氯乙基乙烯基醚，和(d)包含酸酐官能团或能够形成酸酐官能团的单体—含有或没有任选的添加剂i)(甲基)丙烯酸羟烷基酯以增加获得共聚物的性能和持久性，ii)化合物如聚(乙二醇)(甲基)丙烯酸酯以改进共聚物在水中的溶解性，和/或iii)链终止剂—的共聚物在水中稀释并与如下物质混合在一起：形成酸酐的催化剂(需要时)，和任选地聚(丙烯酸)，抗氧剂，永久软化剂/增量剂，和/或其它添加剂。在目前优选的实施方案中，永久软化剂/增量剂是形成酸酐的单体和软质、疏水性单体(如丁二烯、乙烯、异丙烯等)的共聚物或接枝共聚物。
可在本发明制备中采用的形成酸酐催化剂包括，但不限于，碱金属次磷酸盐、碱金属亚磷酸盐、碱金属多磷酸盐、和碱金属磷酸二氢盐。这样催化剂的一些例子是NaH2PO2、H3PO2、Na3PO4、Na2HPO4、NaH2PO4、和H3PO4。
在目前优选的实施方案中，组合物包括在水中3％共聚物，4％聚丙烯酸，2％次磷酸钠水合物(催化剂)，1％EDTA(抗氧剂)，和4％软化剂/增量剂如聚(丁二烯-接枝-马来酸酐)。
在制备本发明的抗油和抗水共聚物组合物中，应当选择pH范围以与反应物相容。根据反应物的反应性，工艺温度可以广泛地变化。然而，温度应当不能高到分解反应物或低到引起反应的抑制或溶剂的凝固。除非相反地说明，在此描述的工艺在大气压下在约40℃-约250℃的温度范围进行。在此工艺要求的时间在较大程度上依赖于使用的温度和共聚物和其它材料的相对反应性。除非另外说明，希望工艺时间和条件是大约的。
本发明进一步涉及采用抗水剂和抗油剂组合物处理的纤维、纱、织物、纺织品、或制成品(在此包括在术语“纤维性基材”下)。这样的纤维性基材显示极大地改进的，“特久的抗水性和抗油性”；即，它们保持抗水剂和抗油剂，即使在多次洗涤之后，同时保留未处理基材的其它所需性能。
本发明的纤维性基材包括纤维、衍生自天然或合成纤维的织造和非织造织物和这样纤维的共混物，以及纤维素基纸、皮革等。它们可包括形式为连续或间断单丝、复丝的纤维、短纤维，和包含这样长丝和/或纤维的纱等，该纤维可具有任何所需的组成。纤维可以是天然，人造，或合成来源。也可以使用天然纤维和合成纤维的混合物。包括在纤维中的可以是非纤维性组分，如微粒填料，粘合剂，上胶剂(sizes)等。希望本发明的纤维性基材包括织物和纺织品，并且可以是由纤维或结构组分组成的片状结构[织造的(包括用于家庭装饰品织物的提花机织造的)或非织造的、编织的(包括衬纬经编)、簇绒的、或缝编的]。天然纤维的例子包括棉、羊毛、丝、黄麻、亚麻等。主要衍生自天然来源的人造纤维的例子包括再生纤维素人造丝、乙酸纤维素、三乙酸纤维素、和再生蛋白质。合成纤维的例子包括聚酯(包括聚对苯二甲酸乙二醇酯)、聚酰胺(包括尼龙，如尼龙6和6，6)、丙烯酸系、烯烃、芳族聚酰胺、人造蛋白质纤维、改良聚丙烯酸、诺沃洛伊德、奈特里尔、斯潘德克斯、乙烯基聚合物和共聚物、维纳尔、维荣等，和这样纤维和聚合物的混合物。
通过在本领域已知的方法如通过浸泡、喷涂、浸渍、流体-流动、浸轧等，以溶剂或分散体/乳液，将本发明共聚物的组合物涂敷到要处理的纤维性基材上。共聚物上的反应性基团与纤维性材料反应，通过共价键合，以连接到材料上。尽管一般优选在干燥步骤之后进行固化，可以在将处理的纺织品从溶液中取出和干燥之前或之后，进行此固化。
在涂敷本发明的共聚物组合物到要处理的纤维性基材中，应当选择pH范围以与反应物相容。根据反应物的反应性，工艺(固化)温度可以广泛地变化。然而，温度应当不能高到分解反应物或低到引起反应的抑制或溶剂的凝固。除非相反地说明，在引描述的工艺在大气压下在约110℃-约250℃的温度范围进行。在此工艺要求的时间在较大程度上依赖于使用的温度和起动网(starting web)和抗水聚合物组合物的相对反应性。除非另外说明，希望工艺时间和条件是大约的。
                      实施例
以下实施例是说明性的而不应当认为是以任何方式限制本发明。实施例1：氟化丙烯酸酯的制备
Figure A0081849400111
以等摩尔量，在合适的无水溶剂(如四氢呋喃)中，将甲基丙烯酸缩水甘油酯和氟代醇混合到20％的总重量百分比。加入1wt％路易斯酸催化剂(如三氟硼酸锌)以增加反应速率。将混合物在干燥气氛下回流3小时。实施例2：丙烯酸/氟化丙烯酸酯其聚物的制备
以1∶1单体比例，将丙烯酸和FX-13氟化丙烯酸酯单体，与AIBN和四氢呋喃(THF)混合在一起。搅拌下将混合物加热到回流6小时以得到丙烯酸-FX-13共聚物。
                      表1.1：1AA：FX-13聚合物的组成
化合物 MW(g/摩尔)   摩尔比 使用的摩尔 质量(g) 密度(g/ml) 使用的体积(ml)
丙烯酸FX-13AIBN十二烷硫醇/MSATHF     72.1625.2164.12202.472.1     1.01.00.020.222.5     0.110.110.000.022.48     7.926668.80.44.5178.5     1.11.6000.9     7.542.7200.8
总计     251.0
i.聚合物(在THF溶剂中30wt％)将丙烯酸，FX-13和链转移剂(十二烷硫醇或巯基琥珀酸)与THF混合。在所有的单体溶解之后加入AIBN。然后将混合物转移到装配有搅拌器的500ml反应烧瓶中。将烧瓶采用N2气体置换约30分钟。在含有N2气体覆盖的反应期间，将油浴的温度保持在70-95℃。将反应进行8小时或更长(通常过夜)。使用IR光谱检查完成情况。
ii.最终溶液
从以上溶液，如通过旋转蒸发，通过蒸发获得树脂。通过在碱性水(10g 1M NaOH+90g水)中稀释树脂而获得最终溶液。在树脂溶解之后，加入1-2％催化剂，3-4％PAA和3-4％lgepal。然后使用H3PO2将pH调成5.5。浸渍温度是40℃。实施例3：用丙烯酸/氟化丙烯酸酯共聚物的棉处理
为制备用于织物处理的溶液，通过在水中将它与1gepalCA-887表面活性剂(1.3％)混合在一起，溶解实施例2的共聚物(MW～1000)，它的pH已经用碱调节到pH13，以得到以4％浓度的共聚物溶液。在已经形成溶液之后，然后用酸将pH调节到pH5.5。加入次磷酸钠(催化剂；1.5％)和将溶液加热到165℃以从丙烯酸基团形成酸酐。
在40℃下，将获得的组合物浸轧于(padded onto)12-oz.白棉上达到70％纤维吸液率，并将棉在90℃下干燥20min。然后通过在165℃下加热5min将织物固化。在活化共聚物中的酸酐已经与在棉纤维上的羟基反应，以得到具有改进抗水性和抗油性的处理纺织品。
按以上所述处理已经“硫染的”棉布样品。硫的存在并不影响聚合物的性能。实施例4：马来酸/氟化丙烯酸酯共聚物的制备
除非另外说明，化学品购自Aldrich Chemical，Milwaukee，WI。
将马来酸(1g；0.32wt％)，Zonyl TA-N氟化丙烯酸酯(64g，20.41wt％；E.I.DuPont，Dhuwater，NJ)，丙烯酸十八酯(C18；18g，5.74wt％)，聚(氧化乙烯)硬脂酸酯(8g，2.55wt％；Chemax，Greenville，SC)，聚甲基丙烯酸(乙二醇)酯(2g，0.64wt％)，甲基丙烯酸2-羟乙酯(1g，0.32wt％)，十二烷硫醇(0.5g，0.16wt％)，和丙酮(50g，15.95wt％)与140g去离子水混合。将混合物均化约15分钟。在进行此操作的同时，也使用搅拌板(stirplate)将溶液加热到约45℃以增加均化速率。然后将混合物转移到装配有搅拌器的500mL反应烧瓶中。在倒入溶液之后立即开始搅拌。将烧瓶用N2气置换约30分钟。
其后加入偏二氯乙烯(18g，5.74wt％)，随后加入已经用10g稀释的自由基引发剂二盐酸化2，2’-偶氮双(2-甲基丙脒)(1g，0.32wt％)。
将油浴温度增加到60-80℃(推荐的最小温度是50℃)。将反应进行8小时或更长(通常过夜)。理论固体百分比(包括表面活性剂)是36％。实施例5：用马来酸/氟化丙烯酸酯共聚物的棉处理
为制备用于织物处理的溶液，向水中加入实施例4的共聚物(3wt％)，次磷酸钠(催化剂；2wt％)，1wt％EDTA，4wt％聚丙烯酸(MW～1800，65％水溶液；Polysciences，Inc.，Warrington，PA)，和4wt％软化剂/增量剂聚(丁二烯-接枝-马来酸酐)(Ricon 130MA13，RiconResins，Grand Junction，CO)。将该溶液加热到165℃以从马来酸基团形成酸酐。
在室温下，将获得的组合物浸轧于到12-oz.白棉上达到100％纤维吸液率，和将棉在85℃下干燥20min。然后通过在190℃下加热90秒将织物固化。在活化共聚物中的酸酐已经与在棉纤维上的羟基反应，以得到具有改进抗水性和抗油性的处理纺织品。
实施例6：比较测试喷淋等级测量
处理基材的喷淋等级(SR)是表示处理基材对撞击到处理基材上，如由衣服在暴雨中遇到的水的动态排斥性的数值。等级由在1977Technical Manual and Yearbook of the American Associationof Textile Chemists and Colorists(AATCC)公开的，标准测试号22测量，并以测试基材的“喷淋等级”表达。喷淋等级通过将水喷淋到基材上而获得和使用0-100刻度测量，其中100是最高可能的等级。抗油性测量
处理基材的抗油性(OR)由the American Association of TextileChemists and Colorists(AATCC)标准测试方法No.118-1983测量，该测试是基于处理基材耐具有变化表面张力的油渗透。仅耐Nujol.RTM.，矿物油(测试油的最小渗透)的处理基材的等级是1，而耐庚烷(测试油的最大渗透)的处理基材的等级是8。其它中间值通过使用其它纯油或油的混合物测量，如在下表中所示。
表2
标准测试液体
AATCC抗油性
等级号  组合物
1       Nujol.RTM.
2       Nujol.RTM./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       正庚烷本发明和现有技术组合物的测试
通过采用Zonyl 8300 Fabric Protector(Ciba SpecialtyChemicals Corporation，High Point，NC)的处理制备棉样品。此市售抗水性处理产品具有如下组成：
浓Zonyl 8300溶液包含70-85％水，14-20％专卖全氟烷基丙烯酸类共聚物，4％己二醇，和1-5％专卖乙氧化脂族醇。将此浓溶液稀释到6％以制备最终处理溶液。浸轧于100％纤维吸液率，在85℃下干燥20min，在165℃下固化5min。
测试Zonyl 8300-处理的织物样品和在实施例3和5中制备的样品对于家庭洗涤(“HLs”)的稳定性。具体地，将正方形织物片(大约8”x8”)放入标准家庭洗衣机中将加入制造商推荐数量的Tide洗涤剂。在“正常”洗涤和旋转循环上采用温水洗涤样品。在5，10，15，和20(在一些情况下)次HLs之后，将样品取出，采用流动自来水清洗2分钟，和在100℃下在烘箱中干燥。然后根据以上的喷淋等级和抗油性等级测试，测试洗涤的样品。结果见下表。
                         表3：油等级
                               处理样品
  #HLs          来自实施例3       来自实施例5        Zonyl 8300
  0                6               7               5.5
  5                6               7               5
  10               6               6               5
  15               6               6               4
  20               6               6               --
                        表4：喷淋等级
                               处理样品
#HLs           来自实施例3         来自实施例5        Zonyl 8300
 0                85               100              100
 5                85               90               90
 10               80               85               70
 15               80               80               70
 20               75               80               --

Claims (21)

1.一种共聚物，该共聚物包括：
(a)含氟代脂族基的试剂；
(b)(甲基)丙烯酸十八酯；
(c)含氯化合物，选自偏二氯乙烯、氯乙烯、丙烯酸2-氯乙酯、2-氯乙基乙烯基醚、和2-氯乙基乙烯基醚；和
(d)包含酸酐官能团或能够形成酸酐官能团的单体。
2.根据权利要求1的共聚物，它进一步包括(甲基)丙烯酸羟烷基酯。
3.根据权利要求1的共聚物，其中含氟代脂族基的试剂是氟化丙烯酸酯或氟化甲基丙烯酸酯。
4.根据权利要求1的共聚物，其中单体是马来酸、马来酸酐、或丙烯酸。
5.根据权利要求1的共聚物，包括：
(a)氟化丙烯酸酯；
(b)丙烯酸十八酯；
(c)含氯化合物，选自偏二氯乙烯、氯乙烯、丙烯酸2-氯乙酯、2-氯乙基乙烯基醚、和2-氯乙基乙烯基醚；
(d)马来酸；
(e)甲基丙烯酸2-羟乙酯；
(f)聚甲基丙烯酸(乙二醇)酯；
(g)十二烷硫醇；和
(h)自由基引发剂。
6.一种赋予纤维性和其它基材抗水性和抗油性的组合物，该组合物包括：
(I)一种共聚物，该共聚物包括：
(a)含氟代脂族基的试剂；
(b)(甲基)丙烯酸十八酯；
(c)含氯化合物，选自偏二氯乙烯、氯乙烯、丙烯酸2-氯乙酯、2-氯乙基乙烯基醚、和2-氯乙基乙烯基醚；和
(d)包含酸酐官能团或能够形成酸酐官能团的单体；和
(II)用于从共聚物中单体形成酸酐的催化剂。
7.根据权利要求6的组合物，其中共聚物进一步包括(甲基)丙烯酸羟烷基酯。
8.根据权利要求6的组合物，其中含氟代脂族基的试剂是氟化丙烯酸酯或氟化甲基丙烯酸酯。
9.根据权利要求6的组合物，它进一步包括聚(丙烯酸)。
10.根据权利要求7的组合物，它进一步包括聚(丙烯酸)。
11.根据权利要求8的组合物，它进一步包括聚(丙烯酸)。
12.根据权利要求6的组合物，其中催化剂是次磷酸钠。
13.根据权利要求6的组合物，它进一步包括抗氧剂。
14.根据权利要求6的组合物，它进一步包括软化剂/增量剂。
15.根据权利要求6的组合物，包括：
(I)一种共聚物，该共聚物包括：
(a)氟化丙烯酸酯；
(b)丙烯酸十八酯；
(c)含氯化合物，选自偏二氯乙烯、氯乙烯、丙烯酸2-氯乙酯、2-氯乙基乙烯基醚、和2-氯乙基乙烯基醚；和
(d)马来酸；
(e)甲基丙烯酸2-羟乙酯；
(f)聚甲基丙烯酸(乙二醇)酯；
(g)十二烷硫醇；和
(h)自由基引发剂；
(II)用于从共聚物中单体形成酸酐的催化剂；和
(III)聚(丙烯酸)。
16.根据权利要求15的组合物，其中催化剂是次磷酸钠。
17.根据权利要求15的组合物，它进一步包括抗氧剂。
18.根据权利要求17的组合物，其中抗氧剂是EDTA。
19.根据权利要求15的组合物，它进一步包括软化剂/增量剂。
20.根据权利要求19的组合物，其中软化剂/增量剂是马来化聚丁二烯。
21.一种采用权利要求6-20任意的组合物处理的纤维性基材，该纤维性基材具有持久的抗水性和抗油性。
CN00818494A 2000-01-18 2000-09-08 共聚物及包含它们的抗油和抗水组合物 Pending CN1425030A (zh)

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CN104074076A (zh) * 2014-06-11 2014-10-01 周文叶 一种用于涤纶地毯数码印花的免洗剂的配方及其应用
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US6380336B1 (en) 2002-04-30
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