CN100497235C - 可在水中再分散的聚合物粉末组合物用于壤土建筑材料的用途 - Google Patents
可在水中再分散的聚合物粉末组合物用于壤土建筑材料的用途 Download PDFInfo
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- CN100497235C CN100497235C CNB2005800085348A CN200580008534A CN100497235C CN 100497235 C CN100497235 C CN 100497235C CN B2005800085348 A CNB2005800085348 A CN B2005800085348A CN 200580008534 A CN200580008534 A CN 200580008534A CN 100497235 C CN100497235 C CN 100497235C
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
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- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/001—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing unburned clay
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0057—Polymers chosen for their physico-chemical characteristics added as redispersable powders
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
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- Paints Or Removers (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
本发明涉及聚合物粉末组合物在壤土建筑材料中的用途。所述的组合物可以再分散于水中，不含乳化剂，包含一种或多种成膜聚合物、一种或多种保护性胶体和可选的防粘连剂。
Description
发明领域
本发明涉及可以水再分散的聚合物粉末组合物在壤土建筑材料、特别是壤土干砂浆中的用途，所述的组合物包括一种或多种成膜聚合物，一种或多种保护性胶体和，如需要，防粘连剂(antiblocking agent)。
背景技术
壤土建筑材料数百年来用作建筑材料，特别是用于房屋建筑。壤土不是标准化的建筑材料，它的组成取决于来源而不同；它通常是粘土、粉沙(非常细的沙子)和沙子的混合物，它还可包含更粗的组分，例如卵石、砂砾或石头，其粘土含量为约10～30wt％。壤土建筑材料的优点是它们容易获得、加工简单、它们的高水分贮存作用(房屋内宜人的气氛)和它们的生态学优点(可再次使用)。
出于这些原因，壤土类建筑材料目前再次逐渐地以湿灰浆的形式、特别是以干砂浆的形式用于内部润饰，例如用于对墙壁进行抹灰(基础和装饰抹灰料)，但是也与木结构结合作为填料，或者作为壤土砖和墙壁涂料。壤土建筑材料的进一步用途是泥土的密封，例如在陆地中以及在坝建筑中。
然而，壤土建筑材料的缺点是它们承受机械负荷的能力有限(强度即内粘聚力低)、对水和潮气敏感(不耐水)、以及对各种建筑基材的粘合差(粘附力差)。
从DE-A 19800784可知，可以通过加入纤维素粘结剂来改进壤土抹灰料的耐磨性。DE-U 20008006描述了通过以蛋白质为附加粘结剂改进壤土类抹灰灰浆的耐磨性。WO-A 00/68162描述了向壤土或粘土类建筑材料加入不含多硫化物、含乳化剂的聚合物制剂。
发明内容
本发明的目的是改进壤土建筑材料、特别是壤土干砂浆的机械强度和耐水性。此外，应当仍然确保壤土建筑材料的加工性能。
本发明提供可以水再分散、不含乳化剂的聚合物粉末组合物在壤土建筑材料中的用途，该组合物包括一种或多种成膜聚合物、一种或多种保护性胶体和，如需要，防粘连剂。
合适的成膜聚合物是基于一种或多种下列单体的成膜聚合物：乙烯基酯、(甲基)丙烯酸酯、乙烯基芳族物质、烯烃、1，3-二烯烃和卤乙烯和如果需要可以与其共聚的附加单体。
合适的乙烯基酯是具有1～12个碳原子的羧酸的乙烯基酯。优选为醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、醋酸(1-甲基乙烯基)酯、特戊酸乙烯酯和具有9～11个碳原子的α-支化一元羧酸的乙烯基酯，例如VeoVa9R或VeoVa10R(Shell商品名)。特别优选为醋酸乙烯酯。
合适的选自丙烯酸酯和甲基丙烯酸酯的单体是具有1-15个碳原子的直链或支链醇的酯。优选的甲基丙烯酸酯和丙烯酸酯为丙烯酸甲酯、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、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丙烯酸(2-乙基己基)酯。特别优选为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯和丙烯酸(2-乙基己基)酯。
优选的乙烯基芳族物质是苯乙烯、甲基苯乙烯和乙烯基甲苯。优选的卤乙烯是氯乙烯。优选的烯烃是乙烯、丙烯，优选的二烯烃是1，3-丁二烯和异戊二烯。
如果需要的话，可以另外共聚有基于单体混合物总重的0.1～5wt％的辅助单体。优选地，使用0.5～2.5wt％的辅助单体。辅助单体的例子有烯属不饱和一元羧酸和二羧酸，优选为丙烯酸、甲基丙烯酸、富马酸和马来酸；烯属不饱和羧酰胺和腈，优选为丙烯酰胺和丙烯腈；富马酸和马来酸的单酯和二酯，如二乙基和二异丙基酯；还有马来酸酐、烯属不饱和磺酸或它们的盐，优选为乙烯基磺酸、2-丙烯酰胺基-2-甲基丙磺酸。其它例子有预交联共聚单体，例如烯属多不饱和共聚单体，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，或者交联后共聚单体，例如丙烯酰胺基乙醇酸(AGA)、甲基丙烯酰胺基乙醇酸甲酯(MAGME)、N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺、N-羟甲基氨基甲酸烯丙酯、烷基酯，例如下列物质的异丁氧基醚或酯：N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺和N-羟甲基氨基甲酸烯丙酯。合适的还有环氧官能化共聚单体，例如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯。其它的例子有硅官能化共聚单体，例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，其中烷氧基可以是，例如，乙氧基和乙氧基丙二醇醚基。还可以提及具有羟基或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，例如丙烯酸或甲基丙烯酸的羟乙酯、羟丙酯或羟丁酯，还有如下化合物，例如，丙烯酸或甲基丙烯酸二丙酮丙烯酰胺，以及丙烯酸或甲基丙烯酸乙酰基乙酰氧基乙酯。
单体和共聚单体的重量比例作如下选择：使得通常得到<40℃、优选为-10℃～+25℃的玻璃化转变温度Tg。可以采用已知方式通过差示扫描量热法(DSC)测定聚合物的玻璃化转变温度Tg。也可以预先通过Fox方程大致计算Tg。根据Fox T.G.，Bull.Am.Physics Soc.1，3，123页(1956)：1/Tg＝x1/Tg1+x2/Tg2+...+xn/Tgn，其中xn是单体n的质量分数(wt％/100)，Tgn是单体n的均聚物的玻璃化转变温度(以开氏温度计)。均聚物的Tg值在Polymer Handbook第2版，J.Wiley & Sons，NewYork(1975)中给出。
优选为包括一种或多种如下单体的均聚物或共聚物：醋酸乙烯酯、具有有9～11个碳原子的α-支化一元羧酸的乙烯基酯、氯乙烯、乙烯、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、苯乙烯。特别优选为包括醋酸乙烯酯和乙烯的共聚物；包括醋酸乙烯酯、乙烯和具有9～11个碳原子的α-支化一元羧酸的乙烯基酯的共聚物；包括丙烯酸正丁酯和丙烯酸(2-乙基己基)酯和/或甲基丙烯酸甲酯的共聚物；包括苯乙烯和一种或多种选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸(2-乙基己基)酯的单体的共聚物；包括醋酸乙烯酯和一种或多种选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸(2-乙基己基)酯的单体和可选的乙烯的共聚物；包括1，3-丁二烯和苯乙烯和/或甲基丙烯酸甲酯和可选的其它丙烯酸酯的共聚物；所述的这些混合物，如果适当的话，还能够包含一种或多种上文所述的辅助单体。
最优选为附加地含有基于聚合物总重的0.1～5wt％的衍生自下列一种或多种共聚单体的单体单元的上述组合物：烯属不饱和一元羧酸和二羧酸，例如丙烯酸、甲基丙烯酸、富马酸和马来酸；烯属不饱和羧酰胺和腈，例如丙烯酰胺和丙烯腈；富马酸和马来酸的单酯和二酯，以及马来酸酐；烯属不饱和磺酸；或它们的盐，优选为乙烯基磺酸、2-丙烯酰胺基-2-甲基丙磺酸。
在存在保护性胶体的条件下，通过乳液聚合法或悬浮聚合法制备成膜聚合物，优选通过乳液聚合法制备。聚合温度通常为40℃～100℃，优选为60℃～90℃，气态单体如乙烯的共聚也可以在超过大气压的压力下进行，通常在5巴～100巴下进行。通过乳液聚合或悬浮聚合中常用的水溶性或溶于单体的引发剂或氧化还原引发剂的组合来引发聚合。水溶性引发剂的例子有过硫酸钠、过氧化氢、偶氮二异丁腈。溶于单体的引发剂的例子有过氧二碳酸二鲸蜡酯、过氧二碳酸二环己酯、过氧化二苯甲酰。所述引发剂的用量通常为单体总重的0.01～0.5wt％。使用所述引发剂与还原剂结合的组合作为氧化还原引发剂。合适的还原剂为，例如，亚硫酸钠、羟基甲烷亚磺酸钠和抗坏血酸。还原剂的量优选为单体总重的0.01～0.5wt％。
为了控制分子量，可以在聚合期间使用调节物质。如果使用调节剂，它们的用量通常为待聚合单体总重的0.01～5.0wt％，其可以单独引入或者与反应组分预混合。这样物质的例子有正十二烷基硫醇、叔十二烷基硫醇、巯基丙酸、巯基丙酸甲酯、异丙醇和乙醛。优选不使用调节物质。
合适的保护性胶体是部分水解或完全水解的聚乙烯醇；聚乙烯吡咯烷酮；聚乙烯醇缩醛；水溶性形式的多糖，例如淀粉(直链淀粉和支链淀粉)、纤维素和它们的羧甲基、甲基、羟乙基、羟丙基衍生物；蛋白质，例如酪蛋白或酪蛋白酸盐、大豆蛋白、明胶；木质素磺酸酯；合成聚合物，例如聚(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、聚乙烯基磺酸和它们的水溶性共聚物；蜜胺-甲醛磺酸酯、萘-甲醛磺酸酯、苯乙烯-马来酸和乙烯基醚-马来酸共聚物。优选是部分水解或完全水解的聚乙烯醇。特别优选水解程度为80～95mol％、在强度为4％的水溶液中的
粘度为1～30mPas(在20℃下，方法，DIN53015)的部分水解的聚乙烯醇。
在聚合完成之后，可以使用已知方法进行后聚合(after-polymerization)，除去残余单体，例如通过氧化还原催化剂引发的后聚合。也可以通过蒸馏，优选减压蒸馏除去挥发性的残余单体，如果合适的话，使惰性夹带气体如空气、氮气或蒸汽通过聚合混合物或在其上方经过。可以采用此方式获得的含水分散体的固体含量为30～75wt％，优选为50～60wt％。
为了制造可以水再分散的聚合物粉末组合物，例如通过流化床干燥、冷冻干燥或喷雾干燥对分散体进行干燥，如果合适的话，在加入保护性胶体作为雾化助剂之后进行干燥。优选地，对分散体进行喷雾干燥。喷雾干燥在常规喷雾干燥装置中进行，可以通过单流体、双流化或多流体喷嘴或通过转动盘进行雾化。取决于于装置、树脂的Tg和所需的干燥程度，出口温度通常为45℃～120℃，优选为60℃～90℃。待雾化进料的粘度经由固体含量设定，以便获得<500mPas(20转和23℃下的布氏粘度)、优选为<250mPas的值。待雾化分散体的固体含量为>35％，优选为>40％。
通常，雾化助剂的总用量为分散体聚合成分的0.5～30wt％。这意味着干燥工艺之前保护性胶体的总量应当为聚合物组分的至少1～30wt％；优选使用聚合物组分的5～20wt％。
合适的雾化助剂为，例如，上述的保护性胶体。优选地，除聚乙烯醇之外，不使用其它的保护性胶体作为雾化助剂。
通常发现，含量至多为挤出聚合物的1.5wt％的消泡剂在雾化中是有利的。为通过改进粘连稳定性来改进贮存性，特别是在粉末的玻璃化转变温度低的情况下，所获粉末可以与防粘连剂(防结块剂)混合，防粘连剂的量优选为聚合组分的1～30wt％。防粘连剂的例子为碳酸钙或碳酸镁、滑石、石膏、二氧化硅、高岭土如偏高岭土、硅酸盐，其粒径优选为10nm～10μm。
为改进疏水性，可以在干燥之前向分散体中加入一种或多种选自脂肪酸、脂肪酸衍生物和有机硅化合物的疏水剂。适于此目的的化合物，例如，列于DE-A 10323205。
根据本发明改性的壤土建筑材料适于用作壤土基抹灰料、壤土装饰抹灰料和壤土装饰涂料，特别是用于内墙壁和屋顶，但也用于外墙壁和潮湿房屋；用作垒壤土砖的壤土灰浆，例如用于木制格式的填入，用作地板/墙壁/屋顶的壤土刮涂填料；和用作壤土建筑粘合剂。根据本发明改性的壤土建筑材料在壤土成形体的制造中也是有利的，以为它们提供更高的稳定性和强度，例如用于壤土/粘土轮廓、壤土/粘土砖、挤出壤土模具。
出乎意料地，通过分散体粉末对壤土灰浆进行改质导致机械强度(弯曲拉伸强度、压缩强度、粘附力)值大为增加，远远超过其它基于水泥、石膏或氢化石灰的建筑体系和灰浆中已知的程度。当使用具有疏水作用的分散体粉末时，出乎意料地，不仅可以实现水吸收大为降低，而且实现了非常良好的防水性和防潮性，使得这些产品同样适于外部用途。
具体实施方式
通过下列实施例对本发明进行说明。
使用下列再分散粉末组合物：
再分散粉末1：
Tg＝18℃的醋酸乙烯酯-乙烯共聚物
12wt％聚乙烯醇
15wt％防粘连剂
再分散粉末2：
Tg＝5℃的醋酸乙烯酯-乙烯-VeoVa10三元共聚物
12wt％聚乙烯醇
15wt％防粘连剂
在下列壤土配制剂中对再分散粉末进行测试：
350.0重量份干燥壤土粉末
70.0重量份硅砂HR(0.1-1.2mm)
250.0重量份硅砂HR(0.2-0.7mm)
300.0重量份硅砂81T(0.1-0.4mm)
0.5重量份改性膨润土(Optibent CP)
0.3重量份纤维素醚(Walocel MKX 6000 PF50L)
1.5重量份亚麻纤维F513/6
X重量份再分散粉末
粘合拉拨强度的测试：
为了测试对基材的粘合，将壤土灰浆通过模板(直径：50mm，厚度：10mm)施加于粘土砖。灰浆固化之后，27天之后通过环氧树脂粘合剂将金属拉杆胶接到待测壤土灰浆上，进行粘合拉拨强度测试。
在各种情况下，在以下贮存条件之后根据DIN CEN 1897测试粘合拉拨强度。
在标准温度和湿度条件(SC)下贮存：
在23℃、50％的大气湿度下贮存28天。
热贮存(HS)：
在标准条件下贮存14天，随后在70℃下贮存14天。
根据DIN 18156，各种情况下在进行上述贮存之后，使用Herion的拉开设备以250N/s的负荷增加速率进行粘合拉拨强度的测定。测量值以N/mm2计，并且是5次测量的平均值。在2个贮存条件之后测定粘合拉拨强度。
水吸收测试：
为测试水吸收，将4mm厚的壤土灰浆层通过抹刀应用于符合DIN52617的多孔混凝土板。壤土灰浆干燥之后，将试件在侧边缘处密封，灰浆层向下浸入水中。然后从单位面积单位时间的重量增加测定水吸收，水吸收以kg/m2h0.5计(表1)。
耐候性测试：
将各种壤土灰浆以10mm厚层应用于打底漆的混凝土板，干燥28天之后，曝露于开放空气中，风化15个月。以月为间隔，通过目测评价风化对壤土灰浆层的影响。表1指示灰浆层掉落的时间。
表1：
| 粉末1[重量份] | 0 | 5 | 20 | 40 | |||
| 粉末2[重量份] | 5 | 20 | 40 | ||||
| 粘合拉拨强度SC[N/mm<sup>2</sup>] | 0.22 | 0.66 | 2.19 | 4.54 | 1.28 | 3.68 | 6.91 |
| H<sub>2</sub>O吸收[kg/m<sup>2</sup>h<sup>0.5</sup>] | * | 1.88 | 0.05 | 0.03 | 1.81 | 1.43 | 0.41 |
| 耐候性 | 1个月 | 12个月 | ** | ** | 6个月 | ** | ** |
*＝30分钟后样品碎裂-不可能测试
**＝15个月后灰浆层仍然完全完整
Claims (9)
1.一种可水再分散和不含乳化剂的聚合物粉末组合物在壤土建筑材料中的用途，所述的组合物包括一种或多种成膜聚合物、一种或多种保护性胶体和可选的防粘连剂，其中保护性胶体是部分水解或完全水解的聚乙烯醇；聚乙烯吡咯烷酮；聚乙烯醇缩醛；淀粉、纤维素和它们的羧甲基、甲基、羟乙基、羟丙基衍生物；酪蛋白或酪蛋白酸盐、大豆蛋白、明胶；木质素磺酸酯；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、聚乙烯基磺酸和它们的水溶性共聚物；蜜胺-甲醛磺酸酯、萘-甲醛磺酸酯、苯乙烯-马来酸和乙烯基醚-马来酸共聚物。
2.根据权利要求1所述的用途，其特征在于存在有基于一种或多种下列单体的成膜聚合物：乙烯基酯、(甲基)丙烯酸酯、乙烯基芳族物质、烯烃、1，3-二烯烃和卤乙烯以及可选的能够与上述单体共聚的其它单体。
3.根据权利要求2所述的用途，其特征在于存在有选自下列物质的成膜聚合物：醋酸乙烯酯均聚物；包括醋酸乙烯酯和乙烯的共聚物；包括醋酸乙烯酯、乙烯和具有9～11个碳原子的α-支化一元羧酸的乙烯基酯的共聚物；包括丙烯酸正丁酯和丙烯酸(2-乙基己基)酯和/或甲基丙烯酸甲酯的共聚物；包括苯乙烯和一种或多种选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸(2-乙基己基)酯的单体的共聚物；包括醋酸乙烯酯和一种或多种选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸(2-乙基己基)酯的单体以及可选的乙烯的共聚物；包括1，3-丁二烯和苯乙烯和/或甲基丙烯酸甲酯以及可选的其它丙烯酸酯的共聚物。
4.根据权利要求1～3中任意一项所述的用途，其特征在于存在有0.1～30wt％的选自下列物质的保护性胶体：部分水解或完全水解的聚乙烯醇；聚乙烯吡咯烷酮；聚乙烯醇缩醛；淀粉、纤维素和它们的衍生物；蛋白质；木质素磺酸酯；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；聚乙烯基磺酸和它们的水溶性共聚物；蜜胺-甲醛磺酸酯；萘-甲醛磺酸酯；苯乙烯-马来酸和乙烯基醚-马来酸共聚物。
5.根据权利要求1～4中任意一项所述的用途，其特征在于存在有1～30wt％的防粘连剂。
6.根据权利要求1～5中任意一项所述的用途，其用于壤土基抹灰料、壤土装饰抹灰料和壤土装饰涂料。
7.根据权利要求1～5中任意一项所述的用途，其用于壤土灰浆和壤土刮涂填料。
8.根据权利要求1～5中任意一项所述的用途，其用于壤土建筑粘合剂。
9.根据权利要求1～5中任意一项所述的用途，其用于壤土成形体。
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| US7288581B2 (en) * | 2004-12-15 | 2007-10-30 | Wacker Polymer Systems Gmbh & Co. Kg | Process for the stabilization of dusting surfaces |
| CZ302139B6 (cs) * | 2008-10-23 | 2010-11-10 | Claylab S.R.O. | Nepálená hlína stabilizovaná polymery |
| DE102008044395A1 (de) | 2008-12-05 | 2010-06-10 | Wacker Chemie Ag | Dränbeton-Zusammensetzung |
| CA2741255C (en) * | 2010-06-15 | 2013-05-14 | Dow Stade Producktions Gmbh & Co. Ohg | Redispersible polymer powder compositions prepared from styrene butadiene-based latex for dry mix formulations |
| CN102070924B (zh) * | 2010-12-19 | 2012-11-07 | 陈新云 | 木质防火门多功能饰面涂层 |
| ITRE20110015A1 (it) * | 2011-03-08 | 2012-09-09 | Matteo Brioni S R L | Composizione di un impasto per rivestimento di superfici |
| KR101936113B1 (ko) * | 2011-10-28 | 2019-01-08 | 다우 글로벌 테크놀로지스 엘엘씨 | 재분산성 폴리머 분말의 내부 첨가제로서 폴리우레탄 분말의 용도 |
| AT512883B1 (de) * | 2012-04-18 | 2017-09-15 | Edmund Kern Hubert | Getrockneter, ungebrannter, diffusionsfähiger, wasserresistenter und frostresistenter, ökonomischer, ökologischer Mergel und/oder Ton und/oder Lehm und/oder Mischformen davon |
| EP2882804B1 (en) * | 2012-09-28 | 2016-08-31 | Rohm and Haas Company | Redispersible polymer powder mixtures for use in dry-mix formulations |
| CN110461888A (zh) * | 2017-02-17 | 2019-11-15 | 瓦克化学股份公司 | 聚合物水分散体在高分子多孔材料界面粘结的用途 |
| CZ307890B6 (cs) * | 2018-03-22 | 2019-07-24 | ÄŚeskĂ© vysokĂ© uÄŤenĂ technickĂ© v Praze | Nepálená hlína s regulovaným smrštěním |
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| EP1420033B1 (de) * | 2002-11-14 | 2004-08-25 | Wacker Polymer Systems GmbH & Co. KG | Schutzkolloidstabilisierte Polymerisate in Form deren wässrigen Dispersionen und in Wasser redispergierbaren Pulver |
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| EP1420033B1 (de) * | 2002-11-14 | 2004-08-25 | Wacker Polymer Systems GmbH & Co. KG | Schutzkolloidstabilisierte Polymerisate in Form deren wässrigen Dispersionen und in Wasser redispergierbaren Pulver |
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