CN115485254A - 包含超吸收剂的混合物 - Google Patents
包含超吸收剂的混合物 Download PDFInfo
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- CN115485254A CN115485254A CN202080100010.6A CN202080100010A CN115485254A CN 115485254 A CN115485254 A CN 115485254A CN 202080100010 A CN202080100010 A CN 202080100010A CN 115485254 A CN115485254 A CN 115485254A
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- fibers
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- mortar
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- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- AIUAMYPYEUQVEM-UHFFFAOYSA-N trimethyl(2-prop-2-enoyloxyethyl)azanium Chemical class C[N+](C)(C)CCOC(=O)C=C AIUAMYPYEUQVEM-UHFFFAOYSA-N 0.000 description 1
- USFMMZYROHDWPJ-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical class CC(=C)C(=O)OCC[N+](C)(C)C USFMMZYROHDWPJ-UHFFFAOYSA-N 0.000 description 1
- VZTGWJFIMGVKSN-UHFFFAOYSA-O trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium Chemical class CC(=C)C(=O)NCCC[N+](C)(C)C VZTGWJFIMGVKSN-UHFFFAOYSA-O 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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Abstract
本发明涉及混合物,所述混合物包含一种或多种超吸收剂聚合物以及一种或多种选自包括以下各项的组的添加剂:基于一种或多种烯键式不饱和单体的保护性胶体稳定的聚合物、增稠剂、促凝剂、缓凝剂、消泡剂和纤维,以及任选地一种或多种添加剂,条件是不包含无机粘合剂。
Description
技术领域
本发明涉及包含超吸收剂(superabsorber)和添加剂的混合物,涉及其生产方法,涉及使用该混合物生产建筑材料配制品的方法,并且涉及该混合物例如在瓷砖粘合剂、流平化合物、密封浆料或用于生产热绝缘复合材料系统中的用途。
背景技术
建筑材料配制品总体上是基于无机粘合剂(如水泥或石膏)、填料、以及添加剂,并且例如被用作涂料或粘合剂(如瓷砖粘合剂、剥落化合物(腻子膏,spackling compound)、流平化合物或接合灰浆(jointing mortar))或用于生产热绝缘复合材料系统。通过添加添加剂,建筑材料配制品是针对对应使用和对应使用地点的具体要求而定制的,并且调整所希望的产品特性。常见的添加剂是保护性胶体稳定的、水可再分散性聚合物粉末(分散体粉末)、增稠剂(尤其是纤维素醚)、促凝剂(setting accelerator)、缓凝剂(settingretarder)、纤维、泡沫稳定剂、以及许多其他添加剂。可分散的聚合物粉末用于改进硬化灰浆的特性,如粘附性、耐磨性、耐擦伤性或挠曲强度,但通常不用于调节新鲜灰浆的特性。例如,纤维提高了硬化灰浆的裂缝桥接特性或挠曲强度。分散剂被用于分散细分的添加剂,以便这些添加剂不附聚而是均匀地分布在硬化灰浆中并且该硬化的灰浆具有均匀的特性曲线(profile)。颜料用于向硬化灰浆添加颜色。同样使用增稠剂,其保水能力影响无机粘合剂的水合性并且因此最终影响硬化灰浆的强度。
除了硬化灰浆的特性之外,对于使用者而言还重要的是新鲜灰浆的特性,例如新鲜灰浆的粘附性、润湿性、可加工性或乳脂状稠度(奶油状稠度,creamy consistency),以及还有在施加过程中校正新鲜灰浆层的能力或校正铺设在灰浆层中的瓷砖的能力。这受到例如新鲜灰浆的粘度或润湿特性的显著影响。例如,具有奶油状稠度的较低粘性的瓷砖粘合剂更容易使用凹口铲施加到基底(substrate)上,并且在瓷砖已经放置在灰浆床中之后可以更容易地对其进行校正。同时,新鲜的灰浆应该是稳定的并且即使当竖直施用时也不会滑下基底。由于增强织物或隔绝板(insulation panel)可以更容易地放置在其中,所以用较低粘性的增强灰浆也更容易生产绝热复合材料系统。通过增加新鲜灰浆的润湿特性,可以改善硬化灰浆在基底上的相互作用以及因此的粘附能力以及粘结的耐久性。例如,当铺设具有低吸水率的现代瓷砖时,这些优点特别重要。
新鲜灰浆的特性通常用纤维素醚作为增稠剂来调节。然而,纤维素醚是昂贵的,因此寻求降低纤维素醚用量的方法。此外,单独的纤维素醚衍生物通常具有窄的活性谱,这意味着在每种情况下对于实现特定的特性或对于特定的灰浆配方需要特定的纤维素醚衍生物,这使得灰浆配方的产生变得复杂,并且这是为什么建筑材料配制品的混配机或制造机在其处理时需要具有大量的纤维素醚衍生物的原因。同样出于这个原因,希望在不降低新鲜灰浆的特性的情况下减少纤维素醚的使用。
发明内容
针对这种背景,一个目的是提供具有较低粘度和增加的润湿特性的新鲜灰浆。在这样做时,如果可能的话,还应当优选地有可能减少在建筑材料配制品中使用的纤维素醚的量而不会不利地影响该新鲜灰浆的上述特性。
出人意料地,用基于超吸收剂和选自包括以下各项的组的添加剂的混合物实现了该目的:烯键式不饱和单体的保护性胶体稳定的聚合物、增稠剂、促凝剂、缓凝剂、消泡剂和纤维,其中该混合物不包含无机粘合剂。确切地是将超吸收剂和添加剂以这种类型的预混合料的形式引入灰浆中,这导致实现本发明的目的。
超吸收剂在灰浆本身中的用途例如从EP1329435、DE102007027470、WO2008/151879或WO2008/151878中是已知的。为了生产干燥灰浆,将超吸收剂和其他成分以单独组分的形式引入。这些文献还旨在减少灰浆中可分散的聚合物粉末的量。除了超吸收剂之外,EP2499104的干燥灰浆还包含充当分散剂的具有聚醚侧链的支链梳状聚合物、三聚氰胺-甲醛缩合物或萘磺酸盐-甲醛缩合物,它们用作流动改进剂。流动改进剂、增塑剂以及超增塑剂通常不是交联聚合物并且不在水中形成水凝胶,而是在水性配制品中具有增塑作用。
EP2388243公开了基于(甲基)丙烯酸和烯键式不饱和聚环氧烷的水可再分散性聚合物粉末和超增塑剂(所谓的聚羧酸酯醚)的组合物,以及这种组合物在干灰浆中的用途。超吸收剂通常不具有增塑性能且已知化学上不同于增塑剂。DE19539250公开了用于水泥制剂的凝固添加剂(setting additive),其除了水溶性聚环氧烷和超吸收剂之外,还包含混凝土超增塑剂,如苯乙烯-马来酸酐。
具体实施方式
本发明提供了混合物,其包括
一种或多种超吸收剂聚合物(超吸收剂),以及
一种或多种选自包括以下各项的组的添加剂:
基于一种或多种烯键式不饱和单体的保护性胶体稳定的聚合物、增稠剂、促凝剂、缓凝剂、消泡剂、以及纤维,以及
任选地一种或多种添加剂,
条件是不存在无机粘合剂。
在混合物中,超吸收剂和添加剂优选作为单独成分,特别是作为单独颗粒组分存在。混合物可以例如以粉末形式,尤其是以水可分散或可溶性粉末形式,或以水性分散体或溶液形式存在。优选的是水可分散的粉末并且特别是水性分散体或溶液。
这些混合物包含基于这些混合物的干重优选按重量计≥30%、更优选按重量计≥70%、并且最优选按重量计≥90%的添加剂和超吸水剂。最优选地,混合物仅由超吸收剂和添加剂组成。
这些混合物包含优选按重量计≥30%、更优选按重量计≥80%、并且最优选按重量计≥90%的添加剂。这些混合物包含优选按重量计≤99.99%、更优选按重量计≤99.9%、并且最优选按重量计≤99.5%的添加剂。重量百分比是指混合物的干重。
优选的添加剂是增稠剂并且尤其是基于烯键式不饱和单体的保护性胶体稳定的聚合物。
这些混合物包含优选地按重量计≥0.01%、更优选地按重量计≥0.1%、并且最优选地按重量计≥0.5%的超吸收剂。这些混合物包含优选按重量计≤70%、更优选按重量计≤20%、并且最优选按重量计≤10%的超吸收剂。重量百分比是指混合物的干重。
超吸收剂通常是在水中或在盐水溶液中可膨胀的共聚物。与水或水性体系的接触通常导致水的溶胀和吸收,形成水凝胶。粉状超吸收剂能够吸收其重量许多倍的水。水凝胶通常理解为是指基于呈三维网络形式的亲水性但交联的水不溶性聚合物的含水凝胶。超吸收剂通常是水不溶性的。超吸收剂特别地是通过烯键式不饱和乙烯基化合物的自由基引发的聚合以及任选地随后干燥由此获得的共聚物可获得的高分子量的交联的阴离子或阳离子聚电解质。优选的是阴离子聚电解质并且特别是带有羧酸基团的聚电解质。烯键式不饱和乙烯基化合物通常包括交联单体,尤其是多重烯键式不饱和单体。
优选的超吸收剂是具有酸基如羧酸基的交联聚合物,其优选全部或部分、尤其主要以其盐(通常为碱金属盐或铵盐)形式存在。
超吸收剂优选基于
一种或多种带有离子基团的烯键式不饱和单体,
一种或多种交联的烯键式不饱和单体,
任选地一种或多种带有(甲基)丙烯酰氨基基团的单烯键式不饱和的非离子单体,以及
任选的一种或多种其他单烯键式不饱和亲水性单体。
带有离子基团的烯键式不饱和单体优选带有阴离子基团,尤其是酸基团,或阳离子基团。
超吸收剂含有具有优选9mol%至70mol%、更优选13mol%至60mol%、并且最优选18mol%至50mol%程度的离子基团的单体单元。
带有酸基团的烯键式不饱和单体可例如为单烯键式不饱和羧酸,尤其是C3-C25羧酸及其酸酐、磺酸或膦酸。
单烯键式不饱和羧酸的实例是丙烯酸、甲基丙烯酸、乙基丙烯酸、α-氯丙烯酸、巴豆酸、马来酸、马来酸酐、衣康酸、柠康酸、中康酸、戊烯二酸、乌头酸和富马酸。单烯键式不饱和磺酸的实例是乙烯基磺酸、烯丙基磺酸、丙烯酸磺基乙酯、磺基甲基丙烯酸酯、丙烯酸磺基丙酯、甲基丙烯酸磺基丙酯、烯丙基羟基丙磺酸、2-羟基-3-丙烯酰氧基丙基磺酸、2-羟基-3-甲基丙烯酰氧基丙基磺酸、苯乙烯磺酸、2-丙烯酰氨基-2-甲基丙磺酸、2-甲基丙烯酰氨基-2-甲基丙磺酸、2-丙烯酰氨基丁磺酸和2-丙烯酰氨基-2,4,4-三甲基戊磺酸。单烯键式不饱和膦酸的实例是乙烯基膦酸和烯丙基膦酸。
优选的带有酸基的烯键式不饱和单体是丙烯酸、甲基丙烯酸、乙烯基磺酸、丙烯酰氨基丙磺酸、2-甲基丙烯酰氨基-2-甲基丙磺酸、2-丙烯酰氨基丁磺酸和2-丙烯酰氨基-2,4,4-三甲基戊磺酸。特别优选丙烯酸和甲基丙烯酸。
带有阳离子基团的烯键式不饱和单体的实例是[2-(丙烯酰氧基)乙基]三甲基铵盐、[2-(甲基丙烯酰氧基)乙基]三甲基铵盐、[3-(丙烯酰基氨基)丙基]三甲基铵盐、以及[3-(甲基丙烯酰基氨基)丙基]三甲基铵盐。盐优选为卤化物或甲硫酸盐的形式。
所用的交联的烯键式不饱和单体可以是例如后交联单体或优选预交联单体。
超吸收剂含有交联单体单元至优选0.01至15mol%,更优选0.02至5mol%,并且最优选0.05至1mol%的程度。
预交联单体通常是多重烯键式不饱和单体,例如多(甲基)丙烯酸官能单体,如丁-1,4-二醇二(甲基)丙烯酸酯、1,3-丁二醇二丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、二乙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、乙氧基化双酚A二丙烯酸酯、乙氧基化双酚A二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、己-1,6-二醇二(甲基)丙烯酸酯、新戊二醇二甲基丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、三丙二醇二丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、二季戊四醇五丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇三丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、环戊二烯二丙烯酸酯、三(2-羟乙基)异氰脲酸酯三丙烯酸酯和/或三(2-羟基)异氰脲酸酯三甲基丙烯酸酯;具有多于一个乙烯基酯或烯丙基酯基团的单体,例如多元羧酸的二乙烯基酯、多元羧酸的二烯丙基酯、对苯二甲酸三烯丙基酯、马来酸二烯丙基酯、富马酸二烯丙基酯、偏苯三甲酸三乙烯基酯、己二酸二乙烯基酯和/或琥珀酸二烯丙基酯;具有多于一个(甲基)丙烯酰胺基基团的单体,如N,N’-亚甲基双丙烯酰胺和/或N,N’-亚甲基双甲基丙烯酰胺;具有多于一个马来酰亚胺基团的单体,如六亚甲基双马来酰亚胺;具有多于一个乙烯基醚或烯丙基醚基团的单体,如乙二醇二乙烯基醚、三乙二醇二乙烯基醚、季戊四醇三烯丙基醚、环己二醇二乙烯基醚、异氰脲酸三烯丙基酯、三烯丙基胺和/或四烯丙基铵盐,以及还有季戊四醇三烯丙基醚。
甲基丙烯酸官能单体优于丙烯酸官能单体。(甲基)丙烯酰氨基-、烯丙基氨基-、和烯丙基醚官能的单体是特别优选的。
后交联单体通常含有烯键式不饱和基团和至少一个另外的官能团。随后的交联可以例如通过使后交联单体的另外的官能团与酸基团反应来进行。合适的官能团是例如羟基、氨基、环氧基和氮丙啶基(aziridino group)。实例包括单烯键式不饱和羧酸的羟烷基酯,如丙烯酸2-羟基乙酯、丙烯酸羟基丙酯、丙烯酸羟基丁酯、甲基丙烯酸羟基乙酯、甲基丙烯酸羟基丙酯和甲基丙烯酸羟基丁酯,烯丙基溴化哌啶鎓,N-乙烯基咪唑类如N-乙烯基咪唑、1-乙烯基-2-甲基咪唑,N-乙烯基咪唑啉类如N-乙烯基咪唑啉、1-乙烯基-2-甲基咪唑啉、1-乙烯基-2-乙基咪唑啉或1-乙烯基-2-丙基咪唑啉,它们可以游离碱形式、季铵化形式或作为盐用于聚合中。还合适的是二烷基氨基乙基丙烯酸酯、二甲基氨基乙基甲基丙烯酸酯、二乙基氨基乙基丙烯酸酯和二乙基氨基乙基甲基丙烯酸酯、以及(甲基)丙烯酸缩水甘油酯。
带有(甲基)丙烯酰氨基基团的单烯键式不饱和的非离子单体的实例是丙烯酰胺、甲基丙烯酰胺、N-甲基(甲基)丙烯酰胺、N,N-二甲基丙烯酰胺、N-乙基丙烯酰胺、N,N-二乙基丙烯酰胺、N-环己基丙烯酰胺、N-苄基丙烯酰胺、N,N-二甲基氨基丙基丙烯酰胺、N,N-二甲基氨基乙基丙烯酰胺和/或N-叔丁基丙烯酰胺。优选甲基丙烯酰胺、N,N-二甲基丙烯酰胺和甲基丙烯酰胺,特别优选丙烯酰胺。
超吸收剂基于带有(甲基)丙烯酰胺基的单烯键式不饱和非离子单体至优选30至90mol%,更优选40至85mol%,并且最优选50至80mol%的程度。
其他单烯键式不饱和的亲水性单体优选选自包括以下各项的组:丙烯腈、甲基丙烯腈、乙烯基吡啶、乙烯基吡咯烷酮、乙烯基己内酰胺、乙酸乙烯酯、以及带有羟基的(甲基)丙烯酸酯,如羟乙基丙烯酸、羟丙基丙烯酸、以及羟丙基甲基丙烯酸。
这些超吸收剂是基于单烯键不饱和的亲水单体至优选0mol%至30mol%、更优选1mol%至20mol%的程度。
优选的超吸水剂是基于19.9mol%至49.9mol%的2-丙烯酰胺基-2-甲基丙磺酸、50mol%至80mol%的丙烯酰胺、以及还有选自包括以下各项的组的交联单体:三烯丙基胺、N,N’-亚甲基双丙烯酰胺、以及季戊四醇三烯丙基醚;19.9mol%至49.9mol%的(甲基)丙烯酸、50mol%至80mol%的丙烯酰胺、以及还有选自包括以下各项的组的交联单体:三烯丙基胺、N,N’-亚甲基双丙烯酰胺、以及季戊四醇三烯丙基醚;19.9mol%至49.9mol%的[3-(丙烯酰基氨基)丙基]三甲基氯化铵、50mol%至80mol%的丙烯酰胺、以及选自包括以下各项的组的交联单体:三烯丙基胺、N,N’-亚甲基双丙烯酰胺、以及季戊四醇三烯丙基醚。
超吸收剂优选为固体形式,尤其是粉末形式。特别优选地,超吸收剂为水性形式。固体形式的超吸收剂具有的粒度分布使得优选按重量计≥98%穿过2000μm目筛,更优选按重量计≥95%穿过500μm目筛,并且最优选按重量计≥90%穿过400μm目筛(根据依达那(edana)420.2-02标准测定)。
基于1g固体形式的超吸收剂,这些超吸收剂能够吸收优选≥5g、更优选≥15g并且最优选≥20g的水。例如,可以以与EP2499104B1的第83段所述的依达那(edana)440.2-02标准类似的方式进行该确定。
超吸收剂可以以常规方式制备,例如如EP2499104中所述。
烯键式不饱和单体的聚合物优选基于选自包括以下各项的组的一种或多种烯键式不饱和单体:具有1至15个碳原子的羧酸的乙烯基酯、羧酸与具有1至15个碳原子的无支链或支链醇的甲基丙烯酸酯或丙烯酸酯、烯烃或二烯、乙烯基芳族化合物或卤乙烯。
优选的乙烯基酯是乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、乙酸1-甲基乙烯基酯、新戊酸乙烯酯、以及具有5至13个碳原子的α-支链一元羧酸的乙烯基酯,例如VeoVa9R或VeoVa10R(Shell的商品名)。特别优选的是乙酸乙烯酯。
优选的甲基丙烯酸酯或丙烯酸酯是具有1至15个碳原子的无支链或支链醇的酯,如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己基酯、以及丙烯酸降冰片酯。特别优选的是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、以及丙烯酸2-乙基己基酯。
优选的烯烃或二烯是乙烯、丙烯、和1,3-丁二烯。优选的乙烯基芳族化合物是苯乙烯和乙烯基甲苯。优选的卤乙烯是氯乙烯。
任选地还有可能共聚辅助单体,更具体地基于该基础聚合物的总重量,按重量计0%至20%,优选按重量计0.1%至10%。辅助单体的实例是烯键式不饱和的单羧酸和二羧酸,优选丙烯酸、甲基丙烯酸、富马酸和马来酸;烯键式不饱和羧酸酰胺和羧酸腈,优选丙烯酰胺和丙烯腈;富马酸和马来酸的单酯和二酯,如二乙基酯和二异丙基酯,以及还有马来酸酐、烯键式不饱和磺酸或其盐,优选乙烯基磺酸,以及2-丙烯酰胺-2-甲基丙磺酸。另外的实例是预交联共聚单体,例如多烯键式不饱和共聚单体,例如己二酸二乙烯酯、马来酸二烯丙酯、甲基丙烯酸烯丙酯或氰尿酸三烯丙酯,或后交联共聚单体,例如丙烯酰胺乙醇酸(AGA)、甲基丙烯酰胺乙醇酸甲酯(MMAG)、N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺(NMMA)、N-羟甲基烯丙基氨基甲酸酯,烷基醚,例如N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺和N-羟甲基烯丙基氨基甲酸酯的异丁氧基醚或酯。还合适的是环氧官能化共聚单体,如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯。另外的实例是硅官能化的共聚单体,如丙烯酰氧基丙基三烷氧基硅烷和甲基丙烯酰氧基丙基三烷氧基硅烷、乙烯基三烷氧基硅烷和乙烯基甲基二烷氧基硅烷,其中烷氧基可以例如以甲氧基、乙氧基和乙氧基丙二醇醚基的形式存在。还应提及具有羟基或CO基团的单体,例如甲基丙烯酸羟烷基酯和丙烯酸羟烷基酯如丙烯酸或甲基丙烯酸的羟基乙基酯、羟基丙基酯或羟基丁基酯,以及还有化合物如二丙酮丙烯酰胺和丙烯酸或甲基丙烯酸的乙酰基乙酰氧基乙基酯。其他实例还包括乙烯基醚,如甲基乙烯基醚、乙基乙烯基醚或异丁基乙烯基醚。
适合的均聚物和共聚物的实例是乙酸乙烯酯均聚物、乙酸乙烯酯与乙烯的共聚物、乙酸乙烯酯与乙烯以及一种或多种另外的乙烯基酯的共聚物、乙酸乙烯酯与乙烯和丙烯酸酯的共聚物、乙酸乙烯酯与乙烯和氯乙烯的共聚物、苯乙烯-丙烯酸酯共聚物、以及苯乙烯-1,3-丁二烯共聚物。
优选乙酸乙烯酯均聚物;乙酸乙烯酯与按重量计1%至40%的乙烯的共聚物;乙酸乙烯酯与按重量计1%至40%的乙烯和按重量计1%至50%的来自在羧基基团中具有1至12个碳原子的乙烯基酯如丙酸乙烯酯、月桂酸乙烯酯、具有5至13个碳原子的α-支链羧酸的乙烯基酯如VeoVa9R、VeoVa10R、VeoVa11R的组的一种或多种另外的共聚单体的共聚物;乙酸乙烯酯、按重量计1%至40%的乙烯、并且优选按重量计1%至60%的具有1至15个碳原子的无支链或支链醇的丙烯酸酯(尤其是丙烯酸正丁酯或丙烯酸2-乙基己基酯)的共聚物;以及具有按重量计30%至75%的乙酸乙烯酯、按重量计1%至30%的月桂酸乙烯酯或具有5至13个碳原子的α-支链羧酸的乙烯基酯、以及按重量计1%至30%的具有1至15个碳原子的无支链或支链醇的丙烯酸酯,尤其是丙烯酸正丁酯或丙烯酸2-乙基己基酯的共聚物,其可以另外包含按重量计1%至40%的乙烯;具有乙酸乙烯酯、按重量计1%至40%的乙烯、以及按重量计1%至60%的氯乙烯的共聚物;其中聚合物可以各自另外含有所提及的量的所述辅助单体,并且在每种情况下重量百分比总计达按重量计100%。
还优选的是(甲基)丙烯酸酯聚合物,如丙烯酸正丁酯或丙烯酸2-乙基己基酯的共聚物或甲基丙烯酸甲酯与丙烯酸正丁酯和/或丙烯酸2-乙基己基酯以及任选地乙烯的共聚物;具有一种或多种来自由丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、以及丙烯酸2-乙基己基酯组成的组的单体的苯乙烯-丙烯酸酯共聚物;乙酸乙烯酯-丙烯酸酯共聚物,该共聚物具有选自由以下各项组成组的一种或多种单体:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、和丙烯酸2-乙基己基酯、以及任选地乙烯;苯乙烯-1,3-丁二烯共聚物;其中,聚合物可以另外含有所提及的量的所述辅助单体,并且在每种情况下重量百分比总计达按重量计100%。
进行单体的选择以及按重量计该共聚单体的比例的选择,以便总体上产生-50℃至+50℃、优选-30℃至+40℃的玻璃化转变温度Tg。聚合物的玻璃化转变温度Tg可以通过差示扫描量热法(DSC)以已知的方式测定。还可以通过Fox方程预先计算近似的Tg。根据FoxT.G.,Bull.Am.Physics Soc.1,3,第123页(1956):1/Tg=x1/Tg1+x2/Tg2+...+xn/Tgn,其中xn是单体n的质量分数(按重量计%/100),并且Tgn是单体n的均聚物的开尔文计玻璃化转变温度,均聚物的Tg值在Polymer Handbook 2nd Edition,J.Wiley&Sons,New York(1975)中列出。
合适的保护胶体的实例是聚乙烯醇;聚乙烯缩醛;聚乙烯吡咯烷酮;水溶性形式的多糖,如淀粉(直链淀粉和支链淀粉)、纤维素及其羧甲基、甲基、羟乙基和羟丙基衍生物、糊精和环糊精;蛋白质,如酪蛋白或酪蛋白酸盐(酪蛋白酸酯,caseinate)、大豆蛋白、明胶;木质素磺酸盐;合成聚合物如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基官能化共聚单体单元的共聚物、聚(甲基)丙烯酰胺、聚乙烯基磺酸及其水溶性共聚物;三聚氰胺-甲醛磺酸盐、萘-甲醛磺酸盐、苯乙烯-马来酸共聚物和乙烯基醚-马来酸共聚物。
优选的是具有优选80mol%至100mol%的水解度的部分或完全水解的聚乙烯醇。特别优选的是具有80mol%至95mol%的水解度、尤其是在4%的水溶液中具有1mPa·s至30mPa·s的Hoeppler粘度(在20℃下Hoeppler方法,DIN53015)的部分水解的聚乙烯醇。最优选的是具有85至94mol%的水解度,尤其是在4%的水溶液中具有3至15mPa·s的Hoeppler粘度(在20℃下Hoeppler方法,DIN53015)的聚乙烯醇。所提及的保护胶体可以通过本领域技术人员已知的方法获得。基于烯键式不饱和单体的聚合物的总重量,保护性胶体以优选按重量计1%至30%,更优选按重量计3%至20%的量存在。
基于烯键式不饱和单体的保护性胶体稳定的聚合物优选为水可再分散性粉末的形式,并且更优选为水性分散体的形式。
保护性胶体稳定的聚合物的生产是本领域的普通技术人员已知的并且例如在EP1916275中进行了描述。
基于混合物的干重,该混合物优选包含按重量计30%至99.9%、更优选按重量计80%至99.7%、并且最优选按重量计90%至99.5%的基于烯键式不饱和单体的保护性胶体稳定的聚合物。
包含基于烯键式不饱和单体的保护性胶体稳定的聚合物的混合物优选含有基于这些混合物的干重按重量计0.1%至70%、更优选按重量计0.3%至20%、并且最优选按重量计0.5%至10%的超吸收剂。
增稠剂的实例是多糖如纤维素醚和改性纤维素醚,纤维素酯,淀粉醚,瓜尔胶,黄原胶,多元羧酸如聚丙烯酸或其酯或其偏酯或其酰胺或偏酰胺或碱金属和碱土金属盐,聚丙烯酸酯,聚乙烯吡咯烷酮,酪蛋白或缔合性增稠剂(associative thickener)如聚氨酯增稠剂或聚乙烯醇。作为增稠剂的多羧酸或聚丙烯酸酯优选不含环氧烷基单元(氧化烯单元,alkylene oxide unit)。增稠剂通常不同于增塑剂。增稠剂优选不同于保护性胶体。增稠剂具有优选>4000g/mol、更优选≥10000g/mol、并且最优选≥20000g/mol的分子量。优选甲基纤维素醚、羟乙基甲基纤维素、羟丙基甲基纤维素和羟乙基纤维素。还优选无机增稠剂,尤其是片状硅酸盐,如膨润土或锂蒙脱石(hectorite)。
这些混合物包含优选基于这些混合物的干重按重量计1%至99.9%、更优选按重量计5%至99%、更优选按重量计30%至95%、并且最优选按重量计50%至90%的增稠剂。
促凝剂的实例是无机酸的碱金属盐和碱土金属盐,如碱金属或碱土金属的碳酸盐、氯化物、硫酸盐、硝酸盐或磷酸盐;铝化合物,如碱金属铝酸盐;硅酸盐,如偏硅酸盐、二硅酸盐以及水硅酸盐;碱金属氢氧化物;有机酸的碱金属或碱土金属盐,如具有1至4个碳原子的羧酸的碱金属或碱土金属盐;烷醇胺;单或双NH2封端的聚烷基二醇,例如单或双氨基封端的聚乙二醇(PEO),单或双氨基封端的聚丙二醇(PPO),和单或双氨基封端的EO-PO共聚物。
优选的促凝剂是碱金属碳酸盐、碱金属氢氧化物、硫酸铝、碱金属铝酸盐、氢氧化铝、碱金属硅酸盐、碱金属或碱土金属甲酸盐、碱金属或碱土金属乙酸盐、碱金属或碱土金属丙酸盐、碱金属或碱土金属丁酸盐、碱金属或碱土金属草酸盐、碱金属或碱土金属丙二酸盐、N,N,N’,N’-四(2-羟丙基)乙二胺、乙醇胺、二乙醇胺、三乙醇胺、N-甲基二乙醇胺、三异丙醇胺、和N,N-二甲基乙醇胺。
特别优选的是氢氧化钾、碳酸钾、碳酸钠、铝酸钾、磺基铝酸盐、磺基铝酸钙、水玻璃、甲酸钙、乙酸钙、三异丙醇胺、二乙醇胺、三乙醇胺、以及N-甲基二乙醇胺。
这些混合物包含优选基于这些混合物的干重按重量计1%至99.9%、更优选按重量计5%至99%、特别优选按重量计30%至95%、并且最优选按重量计50%至90%的凝固促进剂。
缓凝剂的实例是羟基羧酸或二羧酸或其盐、碱金属四硼酸盐如四硼酸钠、磷酸盐、糖类如蔗糖、以及季戊四醇。
优选的羟基羧酸是酒石酸、葡糖酸、柠檬酸、苹果酸、2-甲基苹果酸、以及它们的钙盐。优选的二羧酸是草酸、琥珀酸、富马酸、以及衣康酸。优选的糖类是蔗糖、葡萄糖、果糖和山梨醇。
特别优选的是酒石酸、柠檬酸、以及它们的钙盐,以及还有蔗糖、葡萄糖、以及果糖。
这些混合物包含优选地基于这些混合物的干重按重量计1%至99.9%、更优选地按重量计5%至90%、并且最优选地按重量计40%至80%的缓凝剂。
纤维可基于例如天然或合成纤维材料,例如基于有机或无机材料。纤维也称为纤条体(fibrids)。天然有机纤维的实例是棉、麻、黄麻、亚麻、木质纤维、纤维素、粘胶、皮革纤维或剑麻。合成有机纤维的实例是粘胶纤维、聚酰胺纤维、聚酯纤维、聚丙烯腈纤维、Dralon纤维、聚乙烯纤维、聚丙烯纤维、聚乙烯醇纤维或芳族聚酰胺纤维(aramid fiber)。无机纤维例如为玻璃纤维、碳纤维、矿棉纤维或金属纤维。优选棉纤维、聚丙烯腈纤维和纤维素纤维。特别优选的是纤维素纤维。纤维具有优选在0.1μm至16mm之间、优选0.5μm至1mm、更优选1μm至500μm的长度。这些纤维素纤维具有优选地<10μm的纤维直径。
该混合物优选含有基于混合物的干重,1-99.9重量%,更优选5-90重量%,最优选40-80重量%的纤维。
消泡剂的实例是矿物油、植物油、脂肪、脂肪酸、脂肪酸酯、脂肪醇、金属皂、硅酮、液态烃、以及炔二醇衍生物,尤其是gemini表面活性剂。
优选壬基酚、蓖麻油、煤油、液体石蜡、动物油、芝麻油、蓖麻油、油酸、硬脂酸、二甘醇月桂酸酯、甘油单蓖麻油酸酯、烯基琥珀酸衍生物、山梨醇单月桂酸酯、山梨醇三油酸酯、天然蜡;直链或支链的脂肪醇、乙炔醇、二醇、丙烯酸酯聚胺、硬脂酸铝、油酸钙、硅油、有机改性的聚硅氧烷、氟硅油。
还优选gemini表面活性剂。Gemini表面活性剂通常由通过间隔基连接的两个亲水头部基团组成,每个带有通常疏水性尾部基团,如EP1916275中所述。优选的gemini表面活性剂是含有两个醇基团的炔衍生物。特别优选的是炔二醇衍生物,其中这些醇基团中的一个或两个被聚乙二醇残基取代。
基于混合物的干重,这些混合物包含优选地按重量计1%至99.9%、更优选地按重量计5%至90%、并且最优选地按重量计40%至80%的消泡剂。
添加剂的实例是防腐剂、成膜助剂、分散剂、泡沫稳定剂、增塑剂、酸、碱、缓冲剂、粉末添加剂、颜料或其他染料、阻燃剂如氢氧化铝、杀生物剂和交联剂如金属或半金属氧化物,尤其是硼酸或聚硼酸盐或二醛如戊二醛。基于混合物的干重,添加剂优选以按重量计0%至30%,更优选按重量计0.1%至20%的量存在于混合物中。还特别优选不包含任何添加剂的混合物。
混合物不包含任何无机粘合剂。无机粘合剂的实例在下文给出。
混合物还可以包含一种或多种填料。填料的实例在下文给出。这些混合物包含基于这些混合物的干重优选按重量计≤70%、更优选按重量计≤60%、甚至更优选按重量计≤50%、并且特别优选按重量计≤5%的填料。最优选地,不存在填料。
混合物优选不含增塑剂、超增塑剂和/或流动改进剂。当然显而易见的是,使用这样的化合物可以降低建筑材料制剂的粘度。增塑剂的实例是聚环氧烷,尤其是水溶性聚环氧烷。超增塑剂的实例通常是(甲基)丙烯酸聚合物,尤其是聚羧酸酯醚,如(甲基)丙烯酸和烯键式不饱和聚环氧烷的共聚物、木质素磺酸盐、萘磺酸盐、三聚氰胺磺酸盐、苯乙烯-马来酸共聚物、苯乙烯-马来酸酐共聚物或蛋白质。流动改进剂的实例是具有聚醚侧链的支链或非支链聚合物,尤其是具有聚醚侧链的梳型聚合物、萘磺酸盐-甲醛缩合物、以及任选地磺化的三聚氰胺树脂和三聚氰胺磺酸盐-甲醛缩合物。
本发明进一步提供了通过混合以下各项用于生产这些混合物的方法一种或多种超吸收剂,以及
一种或多种选自包括以下各项的组的添加剂:基于一种或多种烯键式不饱和单体的保护性胶体稳定的聚合物、增稠剂、促凝剂、缓凝剂、消泡剂、以及纤维,以及
任选地一种或多种添加剂,
条件是不使用无机粘合剂。
处于干燥混合物形式的混合物可以例如通过使用一种或多种或所有处于水性形式的起始材料并且随后将它们干燥来获得。优选地,通过将处于固体形式的起始材料进行混合来生产干燥混合物。
优选地,混合物为水性形式。为了其生产,可以以含水形式使用一种或多种或所有起始材料。优选地,通过添加水将干燥混合物转化为水性混合物。
混合和任何干燥可以根据本身常规的方法在常规装置中进行。该混合还可以在处于固体形式的起始材料的任何研磨之前、之中或之后进行。
本发明进一步提供了通过混合一种或多种无机粘合剂、任选地一种或多种填料、以及任选地一种或多种添加剂,用于生产建筑材料配制品、尤其是水性建筑材料配制品的方法,其特征在于
混合一种或多种混合物,其包含
一种或多种超吸收剂,以及
一种或多种选自包括以下各项的组的添加剂:基于一种或多种烯键式不饱和单体的保护性胶体稳定的聚合物,
增稠剂、促凝剂、缓凝剂、消泡剂、以及纤维
条件是该混合物不含任何无机粘合剂。
基于建筑材料配制品的干重,建筑材料配制品优选地包含按重量计0.001%至10%、更优选地按重量计0.005%至2%、并且最优选地按重量计0.01%至0.8%的超吸收剂。
基于建筑材料配制品的干重,建筑材料配制品优选地包含按重量计0.01%至60%、更优选地按重量计0.1%至40%、并且最优选地按重量计1%至25%的添加剂。
基于建筑材料配制品的干重,建筑材料配制品优选地包含按重量计0.1%至50%、更优选地按重量计0.5%至30%、并且最优选地按重量计1%至25%的保护性胶体稳定的聚合物。
基于一种或多种烯键式不饱和单体和/或增稠剂的保护性胶体稳定的聚合物优选地仅通过混合物引入建筑材料配制品中,即,不单独地由混合物引入建筑材料配制品中。
合适的无机粘合剂的实例是水泥,尤其是波特兰水泥、铝酸盐水泥,尤其是硫铝酸钙水泥、火山灰水泥、矿渣水泥、氧化镁水泥、磷酸盐水泥、或高炉水泥,以及还有混合水泥、填充水泥、飞灰、粒状高炉矿渣、熟石灰、白色熟石灰、氧化钙(生石灰)以及石膏,如α-半水合物、β-半水合物、无水物(anhydrite)或CaSO4二水合物。优选的是波特兰水泥、铝酸盐水泥、以及矿渣水泥,并且还有混合水泥、填料水泥、熟石灰、白色熟石灰或石膏,如α-半水化物或无水物。
基于建筑材料配制品的干重,建筑材料配制品优选地包含按重量计1%至90%、更优选按重量计5%至45%、并且最优选按重量计10%至35%的无机粘合剂。
合适的填料的实例是石英砂、石英粉、石灰石粉、碳酸钙、白云石、粘土、白垩、白色熟石灰、滑石或云母、橡胶颗粒或硬填料如硅酸铝、刚玉、玄武岩、碳化物如碳化硅或碳化钛,或火山灰填料(pozzolanic fillers)如飞灰、偏高岭土、微硅粉(microsilica)和硅藻土。优选的填料是石英砂、石英粉、石灰石粉、碳酸钙、碳酸钙镁(白云石)、白垩或白色熟石灰。
填料优选与混合物分开(即作为单独组分)引入建筑材料配制品中。
基于建筑材料配制品的干重,建筑材料配制品优选地包含按重量计10%至99%,更优选按重量计30%至90%,并且最优选按重量计50%至85%的填料。
任选地,建筑材料配制品还可以包含添加剂,例如交联剂如金属氧化物或半金属氧化物,尤其是硼酸或聚硼酸盐,或二醛如戊二醛,防腐剂,成膜助剂,分散剂,泡沫稳定剂,增塑剂,流动改进剂,和阻燃剂(例如氢氧化铝),染料或杀生物剂。此外,还有可能将以上提及的添加剂中的一种或多种与本发明的混合物分开地添加到建筑材料配制品中。
基于建筑材料配制品的干重,建筑材料配制品优选地包含按重量计0.001%至30%、更优选地按重量计0.01%至8%、并且最优选地按重量计0.03%至4%的添加物。
建筑材料配制品特别适合于生产建筑粘合剂、流平化合物、灰泥、剥落化合物、拼接灰浆、密封浆料或隔热复合材料系统。在建筑粘合剂中,用于这些可分散的聚合物粉末组合物的优选的使用领域通常是瓷砖粘合剂、薄涂层或全热保护粘合剂或包埋灰浆、或灰泥。优选的应用领域是流平化合物;更优选地,流平复合物是用于地板的砂浆层找平(screed)和自流平剥落化合物(self-leveling spackling compound)。
出人意料地有可能用本发明的混合物改进新鲜灰浆的特性。例如,本发明的新鲜灰浆有利地具有低粘度以及与其相关的奶油状稠度(如用户所希望的),并且可以容易地处理。此外,本发明的混合物还能够增强新鲜灰浆的润湿作用和粘附性,在它们已经施用和固化之后,这反映在对基底的改进的粘附性中,增加建筑产品的粘附性拉伸强度和耐久性。
使用本发明的混合物,还有可能延长新鲜灰浆的开放时间和校正时间以及适用期(pot life)和时间加工窗口并且抵消过早硬化或表皮形成或甚至灰浆表面上的积垢。新鲜混合的灰浆即使在升高的温度(例如,超过30℃或35℃)下在相对长的时间段内保持其稠度并且总体上非常热稳定。例如,在已经施加新鲜的灰浆之后,甚至在相对长的时间段之后,仍然有可能将贴砖铺设在该灰浆床中并且非常容易地并且以较小的压力校正它们的位置。类似地,在绝热复合材料系统的生产中,根据本发明有可能在相对长的时间段内将增强织物铺设在包埋灰浆中。
使用本发明的混合物还可以改进硬化灰浆的早期和最终强度。这允许降低建筑材料配制品中的粘合剂的比例。因此,可以降低建筑材料配制品的成本和碳排放(碳足迹,carbon footprint)。总体上,一旦无机粘合剂凝固,根据本发明生产的硬化灰浆同样具有所希望的特性。
甚至通过使用出人意料地少量的超吸收剂也可以实现所有这些效果。
此外,通过将本发明的混合物添加到建筑材料配制品中,可以减少纤维素醚(如甲基纤维素)的其他常规使用,并且这不会降低新鲜灰浆的特性或甚至伴随灰浆特性的改进。同样,以此方式,可以降低建筑材料配制品的生产成本,并且可以减少与储存和使用专门用于特定灰浆的多种多样的纤维素醚衍生物相关联的建筑材料混合物的混配机或制造机的工作。因此,通过使用本发明的混合物,所使用的纤维素醚的量可以基于在常规建筑材料配制品中使用的纤维素醚的量(干/干),减少优选按重量计5%至100%、更优选按重量计10%至60%、并且最优选按重量计15%至50%。
在此特别令人惊奇的是,所有这些效果是通过首先本发明的混合超吸收剂和添加剂并且将它们以这种形式引入建筑材料配制品中来实现的。这些效果不能通过将超吸收剂和添加剂常规地分开引入建筑材料配制品中来实现。
以下实例用于更详细地说明本发明并且不应理解为以任何方式进行限制。
关于起始材料的信息:
–Starvis S 5514 F(BASF的商品名):超吸收剂;
–超吸收剂II:聚丙烯酸钠和丙烯酸的交联共聚物;
–VINNAPAS 5010N(Wacker Chemie的商品名):水可再分散的聚乙烯醇稳定的乙酸乙烯酯-乙烯共聚物;
–Tylose H 300 P2(SE Tylose的商品名):甲基纤维素;
–Casucol Fix 1(Avebe的商品名):淀粉醚;
–Agitan P804(Münzing Chemie的商品名):消泡剂:
–Arbocel PWC(J.Rettenmaier&Sons的商品名):纤维素纤维。
实施例1:
混合物的制备:
为了生产混合物a)至h),在室温下在Eirich混合机中混合下文指定的超吸收剂和添加剂总共10分钟。
a)30g Starvis S5514F和970g VINNAPAS 5010N;
b)30g超吸收剂II和970gVINNAPAS 5010N;
c)30g超吸收剂II和500g甲酸钙;
d)30g超吸收剂II和50g淀粉醚Casucol Fix 1;
e)30g超吸收剂II和40g消泡剂Agitan P804;
f)30g超吸收剂II和50g Arbocel PWC 500;
g)30g超吸收剂II和550g Tylose H 300P2;
h)30g超吸收剂II和50g酒石酸。
实施例2:
水性混合物的制备:
混合物a)至h)在室温下在Thinky ARE 250行星式混合器中与以下指定量的水混合5分钟。
a)将2g来自实施例1a的可分散混合物分散在44ml水中;
b)将2g来自实施例1b的可分散混合物分散于40ml水中;
c)将1.06g来自实施例1c的可分散混合物分散于40ml水中;
d)将0.16g来自实施例1d的可分散混合物分散在44ml水中;
e)将0.14g来自实施例1e的可分散混合物分散于40ml水中;
f)将0.6g的来自实施例1f的可分散的混合物分散在44ml的水中;
g)将1.16g来自实施例1g的可分散混合物溶解在40ml水中。允许溶液在室温下静置24小时以脱气;
h)将0.16g来自实施例1h的可分散混合物溶解在40ml水中。
实施例3:
干灰浆的生产:
将320.0g的Milke CEM I 42.5N水泥、331.3g的F31石英砂、331.0g的F36石英砂、以及针对对应的参考灰浆或测试灰浆指定的其他组分在Toni混合器中混合15分钟。
a)参考灰浆:
5.0g的甲酸钙,2.7g的Tylose MH 60.004 P6,
0.3gStarvisS5514F和9.7gVINNAPAS5010N;
测试灰浆:
5.0g甲酸钙和2.7gTylose MH 60.004 P6;
b)参考灰浆:
5.0g的甲酸钙,2.7g的Tylose MH 60.004 P6,
0.3g超吸收剂II和9.7gVINNAPAS 5010N;
测试灰浆:
5.0g甲酸钙和2.7gTylose MH 60.004 P6;
c)参考灰浆:
9.7g VINNAPAS 5010N,2.7g Tylose MH 60.004 P6,
5.0g甲酸钙和0.3g超吸水剂II;
测试灰浆:
9.7g VINNAPAS 5010N和2.7g Tylose MH 60.004 P6;
d)参考灰浆:
5.0g甲酸钙、9.7g VINNAPAS 5010N、2.7g Tylose MH 60.004 P6、0.3g超吸收剂II和0.5g Casucol Fix 1;
测试灰浆:
5.0g甲酸钙,9.7g VINNAPAS 5010N,和2.7g Tylose MH 60.004 P6;
e)参考灰浆:
5.0g甲酸钙,9.7g VINNAPAS 5010N,2.7g Tylose MH 60.004 P6,0.3g超吸收剂II和0.4g Agitan P 804;
测试灰浆:
5.0g甲酸钙,9.7g VINNAPAS 5010N,和2.7g Tylose MH 60.004 P6;
f)参考灰浆:
5.0g甲酸钙、9.7g VINNAPAS 5010N、2.7g Tylose MH 60.004 P6、0.5g ArbocelPWC 500和0.3g超吸收剂II;
测试灰浆:
5.0g甲酸钙,9.7g VINNAPAS 5010N,和2.7g Tylose MH 60.004 P6;
g)参考灰浆:
5.0g甲酸钙,9.7g VINNAPAS 5010 N,
0.3g超吸收剂II和5.5g Tylose H 300 P2;
测试灰浆:
5.0g的甲酸钙和9.7g的VINNAPAS 5010 N,
h)参考灰浆:
5.0g甲酸钙,9.7g VINNAPAS 5010N,2.7g Tylose MH 60.004 P6,0.5g酒石酸和0.3g超吸收剂II;
测试灰浆:
5.0g甲酸钙,9.7g VINNAPAS 5010N,和2.7g Tylose MH 60.004 P6。
实施例4:
新鲜灰浆的生产:
使用以下指定的组分,通过用手动混合器混合20秒来制备来自实施例3的对应的干灰浆。
a)参考灰浆:
200g的来自实施例3a的参考灰浆以及44ml的水;
测试灰浆:
198g的来自实施例3a的测试灰浆以及还有来自实施例2a的水性混合物;
b)参考灰浆:
200g来自实施例3b的参考灰浆和40ml水;
测试灰浆:
198g的来自实施例3b的测试灰浆以及还有来自实施例2b的水性混合物;
c)参考灰浆:
200g来自实施例3c的参考灰浆和40ml水;
测试灰浆:
198.9g的来自实施例3c的测试灰浆以及还有来自实施例2c的水性混合物;
d)参考灰浆:
200.1g来自实施例3d的参考灰浆和44ml水;
测试灰浆:
199.9g的来自实施例3d的测试灰浆以及还有来自实施例2d的水性混合物;
e)参考灰浆:
200.1g来自实施例3e的参考灰浆和40ml水;
测试灰浆:
199.9g的来自实施例3e的测试灰浆以及还有来自实施例2e的水性混合物;
f)参考灰浆:
200.1g来自实施例3f的参考灰浆和44ml水;
测试灰浆:
199.9g的来自实施例3f的测试灰浆以及还有来自实施例2f的水性混合物;
g)参考灰浆:
200.6g来自实施例3g的参考灰浆和40ml水;
测试灰浆:
199.4g的来自实施例3g的测试灰浆以及还有来自实施例2g的水性混合物;
h)参考灰浆:
200.1g来自实施例3h的参考灰浆和40ml水;
测试灰浆:
199.9g来自实施例3h的测试灰浆以及还有来自实施例2h的水性混合物。
表1:来自实施例4的新鲜灰浆的特性:
n.d.:没有进行测量。
实施例5:
测试新鲜灰浆的特性:
a)粘度的测定:
在室温下,在混合之后,使用Brookfield Helipath粘度计(5rpm,转子T96)立即确定来自实施例4的新鲜灰浆的粘度。
b)可湿性(湿润性,wettability)的测定:
使在实施例4中生产的新鲜灰浆静置10分钟,并且然后再次用手动混合器混合20秒。
这之后是根据DIN EN 1347确定润湿性。在该测试中,在10、20和30分钟后,代替玻璃板,铺设测量为5cm x5cm的未上釉型BIa瓷砖(EN12004)。
在总计40分钟之后,翻转这些瓷砖并且将这些瓷砖的背面的润湿确定为总瓷砖面积的百分比。
测试的结果总结在以上表1中。
实施例6:
具有较低比例的甲基纤维素Tylose MH 60.004 P6的灰浆。
干灰浆的生产:
i)测试灰浆:
以类似于实施例3c)的方式,但是将按重量计约20%更少的甲基纤维素(TyloseMH 60.004 P6)计量加入:
将320.2g的Milke CEM I 42.5N水泥、331.5g的F31石英砂、331.2g的F36石英砂、9.7g的VINNAPAS 5010N、以及2.16g的Tylose MH 60.004 P6在Toni混合器中混合15分钟。
ii)测试灰浆:
以类似于实施例3d)的方式,但是将按重量计约20%更少的甲基纤维素(TyloseMH 60.004 P6)计量加入:
将320.2gMilke CEM I 42.5N水泥、331.5gF31石英砂、331.2gF36石英砂、5.0g甲酸钙、9.7gVINNAPAS 5010N和2.16gTylose MH 60.004P6在Toni混合器中混合15分钟。
新鲜灰浆的混合:
i)测试灰浆:
以类似于实施例4c)的方式,在混合的同时,将198.9g的在实施例6i)中生产的干灰浆喷洒到在实施例2c)中生产的含水混合物中。用手动混合器混合该混合物。总混合时间为20秒。
ii)测试灰浆:
以类似于实施例4d)的方式,在混合的同时,将199.9g的在实施例6ii)中生产的干灰浆喷洒到在实施例2d)中生产的含水混合物中。用手动混合器混合该混合物。总混合时间为20秒。
测试新鲜灰浆的特性:
粘度和润湿性如实施例5所述进行测试。
结果总结在表2中。
表2:来自实施例6的新鲜灰浆的特性:
具有本发明的测试灰浆6i)和6ii)的实施例显示,通过与来自实施例4c)和4d)的相应参考灰浆相比较,有可能使用根据本发明的过程来减少所使用的增稠剂甲基纤维素的量并且仍然改进灰浆的润湿性或甚至进一步减少甲基纤维素的量并且仍然能够将润湿性调节到可接受的值。
此外,来自实施例6)的本发明测试灰浆有利地还具有比来自实施例4c)和4d)的相应参考灰浆更低的粘度。
比较实施例7:
比较实施例7的水性预混合物包含超吸收剂,但不含其他添加剂。
i)生产含有超吸收剂的水性预混合物:
在室温下,在Thinky ARE 250行星式混合器中,将0.3g超吸收剂II与200ml水混合并悬浮于其中,持续5min。
ii)干灰浆的生产:
c)参考灰浆与来自实施例3c)的测试灰浆的不同之处在于将甲酸钙添加至干灰浆:
将320.0g的Milke CEM I 42.5N水泥,331.3g的F31石英砂,331.0g的F36石英砂,
9.7g VINNAPAS 5010N,2.7g Tylose MH 60.004 P6,和
5.0g的甲酸钙在该Toni混合器中混合15分钟。
d)参考灰浆与来自实施例3d)的测试灰浆的不同之处在于将Casucol Fix1添加至干灰浆:
将320.0g的Milke CEM I 42.5N水泥,331.3g的F31石英砂,331.0g的F36石英砂,
9.7g VINNAPAS 5010N,2.7g Tylose MH 60.004 P6,和
0.5g的Casucol Fix1在Toni混合器中混合15分钟。
e)参考灰浆与来自实施例3e)的测试灰浆的不同之处在于将Agitan P804添加至干灰浆:
将320.0g的Milke CEM I 42.5N水泥,331.3g的F31石英砂,331.0g的F36石英砂,
9.7g VINNAPAS 5010N,2.7g Tylose MH 60.004 P6,和
0.4g Agitan P804在Toni混合器中混合15分钟。
iii)混合新鲜的灰浆:
c)参考灰浆:
在混合的同时,将199.9g的在比较实施例7-ii-c)中生产的干灰浆喷洒到40.06g的在比较实施例7-i)中生产的预混合物中。用手动混合器混合该混合物。总混合时间为20秒。
d)参考灰浆:
在混合的同时,将199.0g在比较实施例7-ii-d)中生产的干灰浆喷洒到44.06g在比较实施例7-i)中生产的预混合物中。用手动混合器混合该混合物。总混合时间为20秒。
e)参考灰浆:
在混合的同时,将199.0g在比较实施例7-ii-e)中生产的干灰浆喷洒到40.06g在比较实施例7-i)中生产的预混合物中。用手动混合器混合该混合物。总混合时间为20秒。
测试新鲜灰浆的特性:
如实施例5所述测试新鲜灰浆的粘度和润湿性。
结果总结在表3中。
表3:来自比较实施例7和实施例4c-e的新鲜灰浆的特性):
n.d.:没有进行测量。
本发明的测试灰浆4c-e)与来自比较实施例7-iii)的参考灰浆的比较表明,通过将超吸收剂和添加剂以预混物的形式引入到灰浆中改进了新鲜灰浆的粘度和润湿性。相比之下,如在比较实施例7-iii)中所做的,将超吸收剂和添加剂常规地分开引入到灰浆中没有实现所希望的效果。
Claims (13)
1.一种混合物,包括一种或多种超吸收剂聚合物和一种或多种选自包括以下各项的组的添加剂:基于一种或多种烯键式不饱和单体的保护性胶体稳定的聚合物、增稠剂、促凝剂、缓凝剂、消泡剂以及纤维,以及
任选地一种或多种添加剂,
条件是不存在无机粘合剂。
2.如权利要求1所述的混合物,其特征在于基于所述混合物的干重,所述混合物包含≥30wt%的添加剂和超吸收剂。
3.如权利要求1所述的混合物,其特征在于所述混合物仅由超吸收剂和添加剂组成。
4.如权利要求1至3所述的混合物,其特征在于基于所述混合物的干重,所述混合物包含≥30wt%的添加剂。
5.如权利要求1至4所述的混合物,其特征在于基于所述混合物的干重,所述混合物含有0.01wt%至70wt%的超吸收剂。
6.如权利要求1至5所述的混合物,其特征在于超吸收剂是基于
一种或多种带有离子基团的烯键式不饱和单体,
一种或多种交联的烯键式不饱和单体,
任选地一种或多种带有(甲基)丙烯酰氨基基团的单烯键式不饱和非离子单体,以及
任选地一种或多种其他单烯键式不饱和亲水性单体。
7.如权利要求1至6所述的混合物,其特征在于基于烯键式不饱和单体的聚合物是基于选自包括以下各项的组的一种或多种烯键式不饱和单体:具有1至15个碳原子的羧酸的乙烯基酯、羧酸与具有1至15个碳原子的非支链或支链醇的甲基丙烯酸酯或丙烯酸酯、烯烃、二烯、乙烯基芳香族化合物以及乙烯基卤化物。
8.如权利要求1至7所述的混合物,其特征在于基于所述混合物的干重,所述混合物包含30wt%至99.9wt%的基于烯键式不饱和单体的保护性胶体稳定的聚合物。
9.如权利要求1至8所述的混合物,其特征在于
所述增稠剂选自包括以下各项的组:纤维素醚和改性纤维素醚、纤维素酯、淀粉醚、瓜尔胶、黄原胶、聚丙烯酸或其酯或偏酯或其酰胺或偏酰胺或碱金属和碱土金属盐、聚丙烯酸酯、聚乙烯吡咯烷酮、酪蛋白、聚氨酯增稠剂和聚乙烯醇;并且
所述促凝剂选自包括以下各项的组:碱金属或碱土金属的碳酸盐、氯化物、硫酸盐、硝酸盐和磷酸盐;碱金属铝酸盐;偏硅酸盐、二硅酸盐和水硅酸盐;碱金属氢氧化物;具有1至4个碳原子的羧酸的碱金属盐和碱土金属盐;烷醇胺;单或双NH2封端的聚亚烷基二醇;并且
所述缓凝剂选自包括以下各项的组:羟基羧酸或二羧酸或其盐、碱金属四硼酸盐、磷酸盐、以及糖、以及季戊四醇;并且
所述纤维选自包括以下各项的组:棉纤维、麻纤维、黄麻纤维、亚麻纤维、木纤维、纤维素纤维、粘胶纤维、皮革纤维、剑麻纤维、粘胶纤维、聚酰胺纤维、聚酯纤维、聚丙烯腈纤维、Dralon纤维、聚乙烯纤维、聚丙烯纤维、聚乙烯醇纤维、芳族聚酰胺纤维、玻璃纤维、碳纤维、矿棉纤维以及金属纤维;并且
所述消泡剂选自包括以下各项的组:矿物油、植物油、脂肪、脂肪酸、脂肪酸酯、脂肪醇、金属皂、硅酮、液态烃、炔二醇衍生物以及Gemini表面活性剂。
10.如权利要求1至9所述的混合物,其特征在于,所述混合物是处于水性分散体或水溶液的形式。
11.一种通过混合一种或多种超吸收剂和一种或多种选自包括以下各项的组的添加剂来生产混合物的方法:基于一种或多种烯键式不饱和单体的保护性胶体稳定的聚合物、增稠剂、促凝剂、缓凝剂、消泡剂以及纤维,以及
任选地一种或多种添加剂,
条件是不使用无机粘合剂。
12.一种通过混合一种或多种无机粘合剂、任选地一种或多种填料以及任选地一种或多种添加物来生产建筑材料配制品的方法,其特征在于混合一种或多种在权利要求1-10中所述的混合物。
13.权利要求1至10所述的混合物在流平化合物、灰泥、腻子膏、拼接灰浆、瓷砖粘合剂、完全绝热粘合剂、密封浆料或用于生产绝热复合材料系统中的用途。
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