CN1248982A - 温敏聚合物和含有该聚合物的水分散性产品 - Google Patents

温敏聚合物和含有该聚合物的水分散性产品 Download PDF

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Publication number
CN1248982A
CN1248982A CN97181985A CN97181985A CN1248982A CN 1248982 A CN1248982 A CN 1248982A CN 97181985 A CN97181985 A CN 97181985A CN 97181985 A CN97181985 A CN 97181985A CN 1248982 A CN1248982 A CN 1248982A
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Prior art keywords
polymkeric substance
water
isopropylacrylamide
structural unit
multipolymer
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CN97181985A
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English (en)
Inventor
P·S·穆米克
Y·H·常
J·H·X·王
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Kimberly Clark Worldwide Inc
Kimberly Clark Corp
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Kimberly Clark Worldwide Inc
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Publication of CN1248982A publication Critical patent/CN1248982A/zh
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/62—Compostable, hydrosoluble or hydrodegradable materials
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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    • C08F218/04—Vinyl esters
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Abstract

本发明涉及一种基于聚(丙烯酸)和N－异丙胺的反应,制备N－异丙基丙烯酸胺(NiPAm)聚合物的新型方法。本发明所公开的方法使用聚丙烯酸作为原料合成NiPAm聚合物。在一个实施方案中,本发明公开了中间体盐与丙烯酸和/或丙烯酸烷基酯在熔化状态下形成N－异丙基丙烯酸胺(NiPAm)的均聚物、共聚物和三元共聚物的缩合反应,其适合于连续反应挤出方法。也公开了含有NiPAm聚合物的粘合剂组合物、水分散性产品和可热成型制品。

Description

温敏聚合物和含有该聚合物的水分散性产品
本发明领域
本发明涉及由聚丙烯酸制备N-异丙基丙烯酰胺(NiPAm)聚合物(包括但不局限于均聚物、共聚物和三元共聚物)的新型方法。另外，本发明还涉及单独包含N-异丙基丙烯酰胺(NiPAm)聚合物或包含N-异丙基丙烯酰胺(NiPAm)聚合物和至少一种疏水性聚合物的温敏粘合剂。本发明也涉及包含N-异丙基丙烯酰胺(NiPAm)聚合物的可热成形制品。而且，本发明涉及水分散性产品，包括可冲入产品例如尿布、止血塞、妇女用垫片、内衬垫等，所述产品含有包含N-异丙基丙烯酰胺(NiPAm)聚合物的温敏粘合剂和/或可热成形制品。
本发明背景
由于它们的下部临界会溶温度或LCST，NiPAm聚合物(包括含有N-异丙基丙烯酰胺结构单元的均聚物、共聚物和三元或多元共聚物)是温敏聚合物。这里所用的术语“LCST”描述了聚合物溶液随着溶液温度升高而经历从一相(均相溶液)到两相体系(富聚合物相和富溶剂相)的相转移时的温度。这些物质在温水或合成尿(高于约28℃)中保留了相对惰性，但是在冷水(低于约25℃)中由于机械强度的即刻损失却快速分散。已经发现由于它们的逆溶解度(inverse solubility)这些温度激发物质被特别应用于水分散性产品，最优选可冲入个人护理产品例如尿布、止血塞、妇女用垫片、内衬垫等。这里使用的术语“水分散性产品”指的是一种产品，当在大约22℃的温度下暴露在流体中大约2分钟时，其溶解或碎裂成所有都能经过20目筛的碎片。
NiPAm聚合物的通用合成方法需要使用昂贵且不易获得的单体N-异丙基丙烯酰胺。温敏N-异丙基丙烯酰胺聚合物和共聚物公知是由N-异丙基丙烯酰胺的自由基聚合反应或N-异丙基丙烯酰胺与另一单体的共聚合反应而制备。例如在苯中(JP63117016)和乙酸乙酯中(JP63117017)的N-异丙基丙烯酰胺的聚合反应是公知的。如Macromolecules，26(26)，7386(1993)中所公开，交联的聚(N-异丙基丙烯酰胺)水凝胶通过N-异丙基丙烯酰胺的辐射聚合而制备。同样的水凝胶也通过N-异丙基丙烯酰胺和亚甲双丙烯酰胺在各种条件下的共聚合反应而制得。(参见Po1ym.Commun.，32(11)，322(1991)；J.Polym.Sci.，Part A：Polym.Chem.，30(10)，2121(1992))。
许多含有N-异丙基丙烯酰胺单体单元的无规、嵌段或接枝共聚物已经通过各种聚合方法被合成出来。例如，许多包括甲基丙烯酸丁酯、N-异丙基甲基丙烯酰胺和葡聚糖硫酸酯的单体已经与N-异丙基丙烯酰胺一起被聚合制备无规共聚物(J.Chem.Eng.Jpn.，26(1)，89(1993)；J.Biomater.Sci.，Polym.Ed.，5(4)，371(1994)；JP58174408；JP58215413)。Hoffman等人合成了羧基封端的聚(N-异丙基丙烯酰胺)低聚物，然后将其与生物聚合物反应形成热可逆聚合物-酶轭合物(J.Biomater.Sci.，Polym.Ed.，4(5)，545(1993))。另外，已合成出聚(N-异丙基丙烯酰胺)大单体，并接着使其与其它乙烯基单体聚合得到温敏共聚物(Makromol.Chem.，194(2)，551(1993))。
通过聚合的酰基氯的酰胺化，许多不含有N-异丙基丙烯酰胺单体单元的聚合物、特别是聚甲基丙烯酰胺的合成方法已在Makromol.Chem.，194(2)，363(1993)中有述。此文章公开了在或是含水介质或是有机介质中，聚(丙烯酸)与低分子量胺和聚合的胺反应制备聚酰胺。例如，聚(丙烯酸)与全氟烷基胺反应得到具有酰胺化度为4-100％的聚合物(JP 03243609)。DE 3700518公开了在水溶液中用长链烷基胺处理聚(丙烯酸)制得部分酰胺化了的聚合物。聚(丙烯酸)的酰胺化还在下列参考文献中公开：Yakhak Hoechi，30(5)，232(1986)；JP 60079013；Polym.Bull.，13(3)，195(1985)；DE 3009235；DE 2533443；J.Polym.Sci.，Polym.Chem.Ed.，13(12)，2859(1975)；Eur.JBiochem.，17(3)，561(1970)。
聚(N-异丙基丙烯酰胺)(PNiPAm)显示出浊点或逆溶解度特性，即聚合物在低于约34℃的水中是可溶的，而在高于此温度下不溶。聚(N-异丙基丙烯酰胺)(PNiPAm)已经在几篇专利中被引证，其中都利用了其温敏性能。N-取代的聚丙烯酰胺已被推荐作为具有良好吸收特性并容易从伤口表面去除的绷带(JP 6233809)。另外，公开了用于控制透光率的带有PNiPAm的挠性层压薄膜(JP 5177757)。美国专利U.S.5,509,913描述了通用PNiPAm在可冲入个人护理产品中的潜在用途。两个相关专利JP 58174408和JP 84042005(指定Agency of IndustrialScience and Technology)公开了N-异丙基丙烯酰胺和N-异丙基甲基丙烯酰胺的共聚物和这些共聚物作为含水粘合剂和涂料的用途。
也描述了其它温敏聚合物。例如上面提到的美国专利U.S.5,509,913涉及了宽范围的温度灵敏和离子灵敏聚合物。在J.Pharm.Pharmacol.(1978)，30(1)，1中Stafford等人描述了羟丙基纤维素(HPC)作为温敏粘合剂的用途。此外在Taft出版的美国专利U.S.4,002,171中公开了用于可冲入非织造布的盐灵敏水溶性聚氨酯粘合剂。另外，在指定LION Corp.的JP 5125123和U.S.5,312,883中公开了用于生产可冲入纸尿布、绷带和卫生毛巾的盐灵敏水溶性三元共聚物。
本领域中需要的是一种便宜和环境安全的方法，以制备用作粘合剂材料和可热成形制品的NiPAm聚合物，其容易分散于冷水中，但在温水中仍保持结构坚固。而且，也需要一种制备具有特定浊点(即在所需温度范围内的特定浊点)的NiPAm聚合物的方法。
本发明概述
本发明涉及一种N-异丙基丙烯酰胺(NiPAm)聚合物的新型制备方法，包括聚(丙烯酸)和N-异丙胺的反应。本发明公开的方法使用聚丙烯酸作为原料而不是现有技术中通常所述的昂贵单体(N-异丙基丙烯酰胺)来合成NiPAm聚合物。在一个实施方案中，本发明公开了中间体盐与丙烯酸和/或丙烯酸烷基酯在熔化状态下形成N-异丙基丙烯酰胺(NiPAm)的均聚物、共聚物和三元共聚物的缩合反应，其适合于连续反应挤出方法。
本发明还涉及用于将纤维材料粘接为整体结构的粘合剂材料，其中粘合剂材料包括上述NiPAm均聚物、共聚物或三元共聚物。另外，本发明还涉及水分散性纤维底层物，其包含至少一种纤维材料和用于将纤维材料粘接为整体结构的粘合剂材料，其中粘合剂材料包括上述NiPAm均聚物、共聚物或三元共聚物。而且，本发明还涉及包含上述N-异丙基丙烯酰胺聚合物的可热成形制品。此类制品可以是纤维、薄膜或织物的形式，并应用于各种消费品。
另外，本发明还涉及在用于防止流体如血、月经流体和尿从身体中渗出的产品中引入上述粘合剂和可热成形制品。特别地，本发明的粘合剂和可热成形制品用于各种水分散性产品、特别是吸收性产品例如卫生巾、尿布、绷带等中。当与上述体液接触时，本发明的制品显示出足够的抗张强度并保持它们的结构完整性，同时又容易地分散于水中以便用完后吸收性产品可被冲入。
织物被广泛地用作此类一次性用品如卫生巾、尿布、绷带等的组成部分。当在使用过程中，此类织物被与之接触的各种体液如血、月经流体和尿弄湿或弄潮时，如果它们要有效地起作用，就必须保持其结构完整性，并显示出满意的抗张强度。已经认识到在体液中保持其强度的同时，如果此类织物当遇到水时基本上失去其所有的抗张强度并变得容易分散于其中，那么将会基本上消除清理问题，因为织物通过与水接触能够容易和简便地被清理。本发明提供了消除涉及各种消费品的清理问题的另一机理。本发明详述
不同于制备NiPAm聚合物的通用方法，本发明公开了一种新型反应方法，使用低成本且丰富的原料聚丙烯酸的酰胺化反应来制备PNiPAm及其共聚物和三元共聚物。N-异丙基丙烯酰胺结构单元的合成实际上是在聚丙烯酸的聚合物骨架上进行的，这不再需要昂贵的原料如N-异丙基丙烯酰胺。所公开方法的另一优点是，通过使用含有活性氢的化合物如醇和胺代替单个单体，能够容易地制备各种组成的共聚物、三元共聚物或多元共聚物。另外，由所公开方法制得的PNiPAm、共聚物和三元共聚物不含有残留单体。因此，大大消除了与N-异丙基丙烯酰胺聚合物的通用制备方法相关的安全和环境上的忧虑。
通过(1)将NiPAm与一种或多种各种单体聚合以调节浊点并增加浊点之上的脱水作用，和(2)将PNiPAm或其共聚物或三元共聚物与至少一种疏水性聚合物共混以增加浊点之上的脱水作用，本发明也改进和扩展了PNiPAm及其逆溶解度特性的适用范围。已经发现所得到的共聚物、三元共聚物和共混物具有以前从未发现的用途。所公开配方的一个优选的用途是水分散性粘合剂。
本发明公开了在作为水分散性温敏粘合剂的适用范围内的各种配方，包括一种优选的粘合剂配方，该配方包含含有N-异丙基丙烯酰胺和N-叔丁基丙烯酰胺(TBAM)结构单元的共聚物，和另一优选的粘合剂配方，该配方包含N-异丙基丙烯酰胺聚合物和作为至少一种疏水性聚合物的聚乙酸乙烯酯(PVAc)，这产生了一种实际省钱的更平滑、更软的绷带。
希望的是，用作水分散性产品中的粘合剂的温敏聚合物具有下列性能：(1)在浊点之上聚合物仍然脱水，即富聚合物相仅具有少量溶剂；(2)在浊点之上聚合物具有极少量的溶液中聚合物，即富溶剂相基本上都是溶剂；和(3)聚合物的浊点是约20-40℃，更希望的是约20～30℃，最希望的是约21～25℃，这使得聚合物在实用时(即当其靠近身体时)保持不溶，而当温度低于浊点时即在冲入过程中溶解或分散于水溶液中。
本发明公开了含有N-异丙基丙烯酰胺结构单元的聚合物、共聚物和三元共聚物的制备方法，和此类聚合物在水分散性产品、特别是可冲入个人护理产品中作为粘合剂材料和可热成形制品的用途。平均分子量为约2,000-约5,000,000g/mol的聚丙烯酸或聚甲基丙烯酸树脂是优选的本发明反应方法的原料。优选的分子量范围取决于预计的所制聚(N-异丙基丙烯酰胺)(PNiPAm)的最终用途。例如，对于纤维用途，需要在约230℃时熔体流动指数是约10～1,000g/10min.或相同的挤出温度。对于薄膜用途，需要在约230℃时熔体流动指数是约0.1～20g/10min.或相同的挤出温度，以便提供成膜工艺中所需的熔体挤出性能。
有几种方法来完成本发明。本发明反应方法的第一个适合方案由两步骤法构成。在第一步中，在没有溶剂或在极性溶剂下聚丙烯酸与异丙胺反应。适合的极性溶剂包括但不局限于水、甲醇和乙醇。提供组分间的反应，制得聚丙烯酸异丙基铵盐。该盐接着被分离并提纯使其不含有溶剂和未反应的胺。
在第二步中，将该盐加入到熔融反应装置如树脂锅或双螺杆熔融混合器中，以进行缩合反应。副产物水可被排出以便提高PNiPAm的转化率。
本发明反应方法的另一适合方案是连续方法。将具有合适分子量为约2000～5,000,000和在约230℃时合适熔体流动指数为约0.1～500g/10min.的聚丙烯酸加入到挤出机中。在聚合物的熔化时，异丙胺流被注入聚丙烯酸的熔融相中，在挤出机第一反应区的最后制得中间体盐。在进一步的挤出时，聚合物盐分解成聚(N-异丙基丙烯酰胺)(PNiPAm)和水。然后将水从挤出机的最后区段排出。通过控制挤出条件，包括螺杆形状、挤出速率、螺杆速度、反应温度和温度型式，通过该工艺能够制得聚(N-异丙基丙烯酰胺)或各种组成的异丙基丙烯酰胺和丙烯酸的共聚物。
在上述连续方法的另一变例中，在连续方法过程中，脂族醇或各种醇的混合物也能够被注入挤出机中，以合成异丙基丙烯酰胺和至少一种丙烯酸烷基酯的共聚物或三元共聚物。NiPAm聚合物中丙烯酸烷基酯基团的存在提供了一种控制NiPAm聚合物的浊点或诱发温度的方法。例如，疏水性丙烯酸烷基酯基团的引入导致浊点下降。对于丙烯酸烷基酯基团，相对量的NiPAm决定了浊点下降的幅度。
与NiPAm共聚合反应所需的基团是N-叔丁基丙烯酰胺(TBAM)。在连续挤出工艺过程中，通过向反应混合物中注入N-叔丁胺，制得含有NiPAm和TBAM结构单元的聚合物。当NiPAm与至多约20mol％的N-叔丁基丙烯酰胺(TBAM)共聚合时，所得到的共聚物与N-异丙基丙烯酰胺的均聚物相比对于温水变得更加惰性。通过NiPAm与约0-20mol％的N-叔丁基丙烯酰胺(TBAM)的共聚合反应，共聚物的浊点能够下降到所需目标范围，介于约20～40℃，更优选介于约20～30℃，且最优选介于约21～25℃，由于TBAM比PNiPAm相对更具有疏水性，因此其在浊点之上具有更好的脱水作用。下面的表I说明NiPAm与TBAM共聚合反应程度和粘合剂材料的诱发温度之间的关系。当这些共聚物溶液被用作纤维底层物的粘合剂材料时，粘合剂材料在温水中保持稳定，都是在冷水中搅拌下在10秒钟内分散。表Imol％的TBAM对于粘合剂浊点和诱发温度的作用
mol％的TBAM    浊点(℃)      诱发温度(℃)
     0         34.0             33.5
     4         32.0             31.5
     8         29.0             28.5
当NiPAm聚合物与至少一种疏水性聚合物如0-60wt％聚(乙酸乙烯酯)(PVAc)共混时，与单独的NiPAm相比，所得到的共混物对于温水变得更加惰性。为了说明向聚(N-异丙基丙烯酰胺)(PNiPAm)粘合剂材料中加入至少一种疏水性聚合物的作用，将PNiPAm与普通溶剂甲醇中的聚(乙酸乙烯酯)(PVAc)共混。PVAc适合地是非表面活性剂，这使得表面活性剂不会与PNiPAm相互作用，取决于表面活性剂的类型在浊点之上将聚合物脱水或升高浊点本身。适合的PVAc是来自Air Products andChemicals，Inc.，Allentown，PA的VINACB-15。
下面的表II说明了当将20-25wt％施涂量的3～3.5wt％的PNiPAm/PVAc甲醇溶液施涂到纤维底层物中时，PVAc对于纤维底层物的分散时间的作用。所有纤维底层物在温水(＞34℃)中都保持其完整性，但在下述时间内分散于冷水(＜33.5℃)中。如表II中所示，当使用PNiPAm的均聚物与PVAc时，诱发温度保持不变，因为温度诱发由粘合剂配方中的PNiPAm部分所决定。如上所示，通过将PNiPAm与单体例如TBAM共聚合，人们能够调节诱发温度。表II共混的PVAc对于诱发温度和低于诱发温度下分散时间的作用wt％的PVAc    冷水(sec)中的诱发温度(℃)    分散时间
  0                     33.5                10
  30                    33.5                10
  50                    33.5                20
  60                    33.5                60
为了比表II中所示时间更慢地分散粘合剂，人们可以加入至多约70wt％的PVAc且仍实现分散性。由于相对于PNiPAm的Tg(～140℃)，PVAc具有更低的Tg(～29℃)，因此含有PVAc的粘合剂具有更平滑的感觉。
本发明的反应方法并不局限于上述组成。NiPAm聚合物中其它适合的单体包括但不局限于丙烯酸烷基酯和甲基丙烯酸烷基酯。对于合适单体和聚合度的选择没有限制，只要所得到的共聚物或三元共聚物在冷水中具有适合用于水分散性产品中的粘合剂性能(即冷水中的逆溶解度、分散性等)。优选地，本发明共聚物中NiPAm单体的量是基于单体结构单元总摩尔量的约50～约100mol％。最优选地，共聚物中NiPAm单体的量是基于单体结构单元总摩尔量的约70～约90mol％。
另外，本发明包括各种共混物，所述共混物包含一种或多种NiPAm聚合物与一种或多种疏水性聚合物。其它适合与一种或多种NiPAm聚合物共混的疏水性聚合物包括但不局限于聚苯乙烯、苯乙烯-丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯三元共聚物、乙烯-丙烯酸共聚物、乙烯-甲基丙烯酸共聚物、用极性官能团如丙烯酸、马来酸酐等接枝的聚烯烃、聚丙烯酸酯、聚甲基丙烯酸酯、聚乙烯醇缩丁醛、聚氨酯、聚酯、聚酰胺、聚乙烯乙酸乙烯酯和乙烯-乙烯醇共聚物。对与NiPAm聚合物共混的合适的疏水性聚合物的选择和数目没有限制，只要所得到的共混物具有适合用于水分散性产品中的粘合剂性能(即冷水中的逆溶解度、分散性等)。优选地，粘合剂共混物中NiPAm聚合物的量是基于粘合剂组合物中聚合物混合物总重量的约30～约99mol％。最优选地，共混物中NiPAm聚合物的量是基于粘合剂组合物中聚合物混合物总重量的约50～约99mol％。
除了NiPAm聚合物和至少一种疏水性聚合物外，本发明的粘合剂材料还可以含有其它组分。在一些实施方案中，可能优选的是使用一种或多种添加剂，包括但不仅限于相容剂、加工助剂、分散剂、润滑剂、增稠剂、防沫剂、和抗菌剂，根据最终产品中所需特定性能而作为生产制剂或作为改性剂。
本发明的NiPAm聚合物粘合剂组合物与各种增塑剂具有高的相容性；因此此类增塑剂可被引入其中以改进此类粘合剂组合物的性能例如挠性和抗磨耗性。当粘合剂组合物被用于与人体皮肤接触的产品例如上述的卫生巾、尿布等中时，这些性能是特别重要的。为了这些目的，能够使用水溶性增塑剂例如甘油和聚乙二醇，以及水不溶性增塑剂例如蓖麻油等。
本发明的粘合剂材料能够被施加于任何纤维底层物。纤维底层物包括但不仅限于非织造布和机织织物。对于水分散性、可冲入产品，最优选的底层物是非织造布，这是由于它们具有对流体例如血、尿和月经的渗透性。这里使用的术语“非织造布”指的是具有以垫状形式无规夹层的单个纤维或纤丝的结构的织物。非织造布可由各种方法制得，包括但不仅限于气流成网方法、湿法成网方法、水力缠结方法、短纤维梳理和粘合工艺和溶液纺丝。
形成上述织物的纤维可由各种材料(包括天然纤维、合成纤维及其混合物)制得。纤维的选择取决于例如纤维成本和所制成织物预计的最终用途。例如，适合的纤维底层物可能包括但不仅限于天然纤维例如棉布、亚麻布、黄麻、大麻、羊毛、木浆等。同样地，也可以使用再生纤维素纤维例如粘胶人造丝和铜铵人造丝、改性纤维素纤维例如醋酸纤维素或合成纤维例如由聚酯、聚酰胺、聚丙烯酸等单独或相互结合得到的那些。如果需要也可以使用一种或多种上述纤维的共混物。
纤维长度在生产本发明的织物中是重要的。纤维的最小长度取决于形成纤维底层物所选择的方法。例如，如果纤维底层物通过梳理形成，则纤维的长度通常应该是至少约20mm、且优选约25～40mm以保证均匀度。如果纤维底层物通过气流成网或湿法成网法形成，则所需纤维长度小于约15mm。具有长度大于50mm的纤维在本发明的范围内。然而，对于一些实施方案，诸如水分散性可冲入产品，已经测定当大量的长度大于约15mm的纤维被放入织物中时，虽然纤维会在水中分散并分离，但是它们的长度会形成纤维“绳”，而当在家用抽水马桶冲入时，这是不希望有的。因此，对于可冲入产品，需要纤维长度是15mm或更少，以便当纤维通过抽水马桶被冲入时不会具有形成“绳”的趋势。在大多数实施方案中，纤维具有小于约15mm的长度，使得当与水接触时纤维容易地相互分散，长度优选的范围是约6～约15mm。
已经发现由天然纤维单独或与至少一种聚烯烃、聚酯和聚酰胺纤维一起形成的非织造布特别适合于上述用途。
本发明的纤维底层物可以由单层或多层构成。在多层的实例中，各层一般以并置或面对面的关系定位，且所有或部分层可与相邻层粘合在一起。非织造纤网也可由许多单独的非织造纤网构成，其中单独的非织造纤网可由单个或多个层构成。在那些例子中，如果非织造纤网包括多个层，则非织造纤网的整个厚度都要经受粘合剂施加，或每一单个层可单独地经受粘合剂施加，然后再与并置的其它层结合以形成完整的非织造纤网。
粘合剂组合物可通过任何公知施加方法被施加到纤维底层物上。施加粘合剂材料的合适的方法包括但不仅限于印刷、喷涂、浸渍或通过其它技术。可以计量粘合剂组合物的量并将其在纤维底层物内均匀分布，或可不均匀地施加到纤维底层物上。粘合剂组合物可被分布在整个纤维底层物上或分布在许多密集的彼此隔开的区域内。优选地，粘合剂组合物被均匀分布在纤维底层物内。
为了容易地施加到纤维底层物上，含有至少一种NiPAm聚合物和任何添加剂的粘合剂可被溶解于水中，或溶解于非水溶剂中例如甲醇、乙醇等，水是一种需要的溶剂，以提供含有至多约30wt％粘合剂组合物固体、最优选约6～20wt％粘合剂组合物固体的溶液。如上面所述，增塑剂例如甘油、聚乙二醇、蓖麻油等可被加入到含有粘合剂组合物的溶液中，此类增塑剂的量根据最终织物中所需的柔软度而变化。此外，如果需要，可将香料、着色剂、防沫剂、杀菌剂、表面活性剂、增稠剂、填料和类似添加剂引入到粘合剂组分的溶液中。另外，其它水溶性或水分散性粘合剂例如诸如下面的水分散体：聚乙烯醇、聚氯乙烯、聚乙酸乙烯酯、聚丙烯酸酯、聚甲基丙烯酸酯、丙烯酸酯和甲基丙烯酸酯的共聚物、乙酸乙烯酯与乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物、丙烯酸酯和/或甲基丙烯酸酯与氯乙烯的共聚物也可被加入到粘合剂组合物溶液中以便获得具有各种所需性能的粘接的织物。
一旦粘合剂组合物被施加到底层物上，可通过任何公知方法将底层物干燥。干燥之后，当与未处理的湿法成网或干法成网的底层物的抗张强度相比时，内聚性的纤维底层物显示出改进的抗张强度，并且，当放入冷水中并搅拌时，具有快速“崩解”或解体的能力。例如，与不含有粘合剂的未处理底层物的抗张强度相比，纤维底层物的抗张强度可增加至少25％。更特别地，与不含有粘合剂的未处理底层物的抗张强度相比，纤维底层物的抗张强度可增加至少100％。甚至更特别地，与不含有粘合剂的未处理底层物的抗张强度相比，纤维底层物的抗张强度可增加至少500％。
本发明的需要的特征是，如果在最终纤维底层物中存在“施涂量”的粘合剂组合物的量相当于整个底层物的仅一小部分重量时，能够实现抗张强度的提高。“施涂量”的量根据特定用途而变化；然而，“施涂量”的最佳量能够得到在使用时具有完整性并当在水中搅拌时快速分散的底层物。例如，粘合剂组分一般是底层物总重量的至多约60wt％。更优选地，粘合剂组分可以是底层物总重量的至多约40wt％。最优选地，粘合剂组分可以是底层物总重量的至多约25wt％。
如“施涂量”一样，最终纤维底层物的密度应该使得底层物在使用时保持结构完整性，但是当在水中搅拌时能够快速分散。虽然密度根据给定的用途而变化，但是一般纤维底层物优选具有密度至多约0.4g/cm3，更优选约0.01～0.3g/cm3，且最优选约0.025～约0.2g/cm3。
在本发明的另一实施方案中，可热成形制品由通过上述挤出方法制得的至少一种NiPAm聚合物形成。可热成形产品可以呈单层或多层制品的形式，其中至少一层包含以单个纤维、薄膜或织物形式的NiPAm聚合物。可热成形制品在各种消费品、特别是水分散性产品中也是有用的。
本发明的粘合剂材料可被引入到任何水分散性产品、特别是体液吸收产品例如卫生巾、尿布、外科用绷带等中。这些产品一般包括吸收性芯层，包含一种或多种吸收性材料层。芯层也包含一层或多层流体可透部件例如纤维纸巾、纱布、塑料栅片等。这些一般被用作包装材料以将芯层组分结合在一起。另外，芯层可以包含流体不透部件或阻挡层以防止流体流经芯层和流到产品外表面上。优选地，阻挡层也是水分散性的。与上述水分散性粘合剂具有大致相同组成的NiPAm聚合物的薄膜特别适合于此目的。按照本发明，NiPAm聚合物组合物用于形成每一上述产品组分，所述组分包括吸收性芯层、流体可透部件层、包装材料层和流体不透部件层或阻挡层。
本领域熟练人员容易地明白，在用来与体液接触的各种吸收性个人护理产品的制备中，本发明的水分散性产品可被理想地使用。此类吸收性产品可能仅包含单层纤维底层物或可能包含上述部件的结合体。虽然本发明的纤维底层物特别适合于个人护理产品，但是在个人护理产品除外的各种消费品的制备中，本发明的纤维底层物可被理想地使用。
通过下面的实施例可以进一步说明本发明，但是无论如何不能解释为用来限制本发明。相反，在理解所述内容后应该清楚地明白，该方法可以有各种其它的实施方案、改进和等效手段，该方法建议本领域熟练人员不要脱离本发明的实质和/或所附权利要求的范围。实施例1
将重均分子量为450,000g/mol的500g聚丙烯酸溶解于700m1无水乙醇中。在搅拌的同时将混合物加热到60℃。在聚丙烯酸溶解后，将溶液冷却到30℃。滴加化学计量的异丙胺。形成白色沉淀物。收集沉淀物并在真空下除去乙醇。FT-IR分析显示在1540cm-1处的丙烯酸异丙基铵盐的峰。实施例2
因为聚(丙烯酸)与异丙胺成盐的程度受到溶剂极性的影响，因此在几种溶剂例如除实施例1中的乙醇外的水、水/甲醇(30/70，v/v)、甲醇、异丙醇和正丁醇中试验上述反应的产率。发现具有较高极性的溶剂例如水、甲醇和乙醇得到大约定量的产率，而异丙醇仅得到70％的盐。正丁醇不能完全溶解聚丙烯酸；8小时后仍然可见高度溶剂化的聚丙烯酸残留物。当在四氢呋喃(THF)中沉淀时，由乙醇得到的盐凝结并容易地从溶剂中分离出来。当从水中或甲醇中沉淀时，所述盐更容易分散。因此，选择乙醇作为成盐的合适溶剂。
将100g聚丙烯酸(与实施例1中相同的来源)溶解于1.5升乙醇中。在强力搅拌下立即加入125g异丙胺(1.5倍过量)。形成大量的沉淀物。在氮气下搅拌溶液24小时。起始形成的大多数沉淀物再溶解于乙醇中。所述盐接着在2升THF中沉淀并在真空下干燥。1H和13C核磁共振(NMR)光谱分析显示由该方法制得的盐是98％纯度。实施例3
该实施例涉及在Haake双螺杆混合器(使用两辊桨叶型辊压机的Rheomix 600)中聚丙烯酸异丙基铵盐的熔融相反应。将如实施例2制备的47g聚丙烯酸异丙基铵盐加入到在180℃预热的混合器中。一些泡沫形式的树脂从混合器的顶部封闭部分逸出。反应在150rpm的螺杆速度下持续11分钟。在反应过程中，起始放热导致温度升高到196℃并接着回落到163℃。
13C-NMR分析显示所得到的聚合物具有43wt％的N-异丙基丙烯酰胺衍生的结构单元和57wt％的丙烯酸单元。实施例4
该实施例涉及在Haake双螺杆混合器(使用两辊桨叶型辊压机的Rheomix 600)中聚丙烯酸异丙基铵盐的另一熔融相反应。将如实施例2制备的42g聚丙烯酸异丙基铵盐加入到在180℃预热的混合器中。将送料槽放到混合器上以阻止泡沫形成。观察到作为副产物的水以白色蒸汽的形式从混合器中逸出。将混合物在150rpm的螺杆速度下搅拌20分钟。熔体温度升高到192℃的峰值并接着回落到155℃。
13C-NMR分析显示所得到的聚合物具有45wt％的N-异丙基丙烯酰胺衍生的结构单元和55wt％的丙烯酸单元。实施例5
将50g聚丙烯酸N-异丙基铵盐放入装有机械搅拌器、温度计、氮气入口管、氮气出口管和带有冷凝器的Dean-Stark捕集器的1升反应釜中。反应温度在150～180℃保持4小时，在此期间收集5.5g水。然后用真空管路代替收集器，并使反应持续另外的2小时。对于100％转化率的理论量的水是5.2g。在反应过程中收集的过量液体被认为是副反应例如盐分解产生的。
通过红外光谱对产物的分析显示出80wt％的N-异丙基丙烯酰胺结构单元和20wt％的丙烯酸单元。实施例6
使用线绕棒(#22)将3wt％的聚(N-异丙基丙烯酰胺)(PNiPAm)水溶液施涂到底层物上以提供特定量的施涂量。底层物是由0.5″、3旦纤维制得的湿法成网的非织造布。底层物具有60wt％的聚(对苯二甲酸乙二醇酯)(PET)和40wt％的Abaca纸浆纤维。将底层物在75℃烘箱中干燥。实现介于20-25wt％的施涂量。由于PNiPAm的高Tg(～140℃)，粘合材料比底层物稍硬。将1″×1″片的该材料放入冷水中的闪烁管中，并在摇动器(来自Eberbach Corporation)上强力摇动。所述材料在10秒钟内分散。然而，通过在温水(～40℃)中强力摇动同样的试样10分钟，所述材料没有失去完整性。随着温度冷却到约33.5℃，该材料开始水合并分散。PNiPAm的浊点是34℃。实施例7
将N-异丙基丙烯酰胺(NiPAm)与N-叔丁基丙烯酰胺(TBAM)单体共聚合以制备具有96mol％NiPAm结构单元和4mol％TBAM结构单元的共聚物。将20-25wt％施涂量的3～3.5wt％的共聚物粘合剂溶液施涂到纤维底层物上。底层物是由0.5″、3旦纤维制得的湿法成网的非织造布，其中纤维包含60wt％的聚(对苯二甲酸乙二醇酯)(PET)和40wt％的Abaca纸浆纤维。
含有粘合剂的底层物在温水中保持稳定，但是在搅拌下在10秒钟内分散于冷水(31.5℃)中。粘合剂的TBAM组分将聚合物的浊点降低到32.0℃。实施例8
将N-异丙基丙烯酰胺(NiPAm)与N-叔丁基丙烯酰胺(TBAM)单体共聚合以制备具有92mol％NiPAm结构单元和8mol％TBAM结构单元的共聚物。将20-25wt％施涂量的3～3.5wt％的共聚物粘合剂溶液施涂到纤维底层物上。底层物与实施例7中的底层物相同。
含有粘合剂的底层物在温水中保持稳定，但是在搅拌下在10秒钟内分散于冷水(28.5℃)中。粘合剂的TBAM组分将聚合物的浊点降低到29.0℃。实施例9
将PNiPAm与来自普通溶剂甲醇的30wt％的聚(乙酸乙烯酯)共混。PVAc是非表面活性剂的PVAc(来自Air Products的VINACB-15)。将20-25wt％施涂量的3～3.5wt％的PNiPAm/PVAc甲醇溶液施涂到与实施例7的底层物相同的纤维底层物中。纤维底层物在温水(＞34℃)中保持其完整性，但在10秒钟内分散于冷水(＜33.5℃)中。诱发温度33.5℃不受PVAc的影响，因为温度诱发由粘合剂配方中的PNiPAm部分所决定。实施例10
重复实施例9，只是PNiPAm与60wt％的聚(乙酸乙烯酯)(PVAc)共混。纤维底层物在温水(＞34℃)中保持其完整性，但在60秒钟内分散于冷水(＜33.5℃)中。同样，诱发温度33.5℃不受PVAc的影响。
上面公开的实施例是优选的实施方案，不能用来以任何方式限制本发明的范围。很显然对于本领域普通熟练人员来说，所公开NiPAm聚合物的各种改进和其它实施方案以及用途也被认为是在本发明的范围内。

Claims (42)

1、一种制备聚合物的方法，包括：由包含聚丙烯酸和异丙胺的反应混合物制成中间体盐；和进行缩合反应，将盐转变成为聚合物和水。
2、权利要求1的方法，其中所述方法是连续挤出方法。
3、权利要求2的方法，其中在连续方法过程中，将一种或多种醇注入反应混合物中，以制备异丙基丙烯酰胺和至少一种丙烯酸烷基酯的共聚物或三元共聚物。
4、一种聚合物，含有由权利要求1的方法制得的N-异丙基丙烯酰胺结构单元。
5、权利要求4的聚合物，其中所述聚合物是共聚物或三元共聚物。
6、一种含有N-异丙基丙烯酰胺结构单元的聚合物，所述聚合物通过连续挤出方法制得，所述方法包括：由包含聚丙烯酸和异丙胺的反应混合物制成中间体盐；和进行缩合反应，将盐转变成为聚合物和水。
7、权利要求6的聚合物，其中所述聚合物是聚(N-异丙基丙烯酰胺)。
8、权利要求6的聚合物，其中所述聚合物是含有N-异丙基丙烯酰胺结构单元的共聚物或三元共聚物。
9、权利要求8的聚合物，其中所述共聚物还包含N-叔丁基丙烯酰胺结构单元。
10、权利要求9的聚合物，其中所述共聚物包含至少约80mol％的N-异丙基丙烯酰胺结构单元和小于约20mol％的N-叔丁基丙烯酰胺结构单元。
11、权利要求6的聚合物，其中所述聚合物与至少一种疏水性聚合物共混。
12、权利要求11的聚合物，其中所述至少一种疏水性聚合物包含聚乙酸乙烯酯。
13、权利要求12的聚合物，其中所述聚合物与至多约70wt％的聚乙酸乙烯酯共混。
14、一种纤维底层物，包含：
至少一种纤维材料；和
一种用于将该至少一种纤维材料粘附为整体纤网的粘合剂组合物，所述粘合剂组合物包含含有N-异丙基丙烯酰胺结构单元的聚合物，所述聚合物由连续挤出方法制得，该方法包括：
由包含聚丙烯酸和异丙胺的反应混合物制成中间体盐；和
进行缩合反应，将盐转变成为聚合物和水。
15、权利要求14的纤维底层物，其中所述聚合物是聚(N-异丙基丙烯酰胺)。
16、权利要求14的纤维底层物，其中所述聚合物是含有N-异丙基丙烯酰胺结构单元的共聚物或三元共聚物。
17、权利要求16的纤维底层物，其中所述共聚物还包含N-叔丁基丙烯酰胺结构单元。
18、权利要求17的纤维底层物，其中所述共聚物包含至少约80mol％的N-异丙基丙烯酰胺结构单元和小于约20mol％的N-叔丁基丙烯酰胺结构单元。
19、权利要求14的纤维底层物，其中所述粘合剂组合物还包含至少一种疏水性聚合物。
20、权利要求19的纤维底层物，其中所述至少一种疏水性聚合物包含聚乙酸乙烯酯。
21、权利要求20的纤维底层物，其中所述粘合剂组合物包含至少约30wt％的聚合物和小于约70wt％的聚乙酸乙烯酯。
22、权利要求14的纤维底层物，其中所述至少一种纤维材料包含天然纤维。
23、权利要求14的纤维底层物，其中所述至少一种纤维材料包含合成纤维。
24、权利要求14的纤维底层物，其中所述纤维材料包含一种非织造布。
25、一种含有至少一种纤维底层物的水分散性产品，其中所述纤维底层物包含：
至少一种纤维材料；和
一种用于将该至少一种纤维材料粘附为整体纤网的粘合剂组合物，所述粘合剂组合物包含含有N-异丙基丙烯酰胺结构单元的聚合物，所述聚合物由连续挤出方法制得，该方法包括：
由包含聚丙烯酸和异丙胺的反应混合物制成中间体盐；和
进行缩合反应，将盐转变成为聚合物和水。
26、权利要求25的水分散性产品，其中所述聚合物是聚(N-异丙基丙烯酰胺)。
27、权利要求26的水分散性产品，其中所述聚合物是含有N-异丙基丙烯酰胺结构单元的共聚物或三元共聚物。
28、权利要求29的水分散性产品，其中所述共聚物还包含N-叔丁基丙烯酰胺结构单元。
29、权利要求28的水分散性产品，其中所述共聚物包含至少约80mol％的N-异丙基丙烯酰胺结构单元和小于约20mol％的N-叔丁基丙烯酰胺结构单元。
30、权利要求25的水分散性产品，其中所述粘合剂组合物还包含至少一种疏水性聚合物。
31、权利要求30的水分散性产品，其中所述至少一种疏水性聚合物包含聚乙酸乙烯酯。
32、权利要求31的水分散性产品，其中所述粘合剂组合物包含至少约30wt％的聚合物和小于约70wt％的聚乙酸乙烯酯。
33、权利要求25的水分散性产品，其中所述至少一种纤维材料包含天然纤维。
34、权利要求25的水分散性产品，其中所述至少一种纤维材料包含合成纤维。
35、权利要求25的水分散性产品，其中所述纤维材料包含一种非织造布。
36、权利要求25的水分散性产品，还包含一种由含有N-异丙基丙烯酰胺结构单元的聚合物形成的流体不透薄膜。
37、权利要求25的水分散性产品，其中所述水分散性产品是选自于止血塞、妇女用垫片、内衬垫、尿布、绷带、湿揩布和棉纸的可冲入个人护理产品。
38、一种可热成形制品，包含一种含有至少一种N-异丙基丙烯酰胺结构单元的聚合物，所述聚合物由连续挤出方法制得，该方法包括：
由包含聚丙烯酸和异丙胺的反应混合物制成中间体盐；和
进行缩合反应，将盐转变成为聚合物和水。
39、权利要求38的可热成形制品，其中所述聚合物是共聚物或三元共聚物。
40、权利要求38的可热成形制品，其中所述制品选自于纤维、薄膜和织物。
41、权利要求40的可热成形制品，其中所述织物是熔喷法或纺粘型织物。
42、权利要求38的可热成形制品，其中所述制品包含一层或多层以薄膜或织物形式的聚合物。
CN97181985A 1996-12-31 1997-12-12 温敏聚合物和含有该聚合物的水分散性产品 Pending CN1248982A (zh)

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US6451429B2 (en) 2002-09-17
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US5969052A (en) 1999-10-19
IL130379A0 (en) 2000-06-01
KR20000069764A (ko) 2000-11-25
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