CN102971272B - 粒状浮石及用于制备粒状浮石的方法 - Google Patents
粒状浮石及用于制备粒状浮石的方法 Download PDFInfo
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- CN102971272B CN102971272B CN201180025953.8A CN201180025953A CN102971272B CN 102971272 B CN102971272 B CN 102971272B CN 201180025953 A CN201180025953 A CN 201180025953A CN 102971272 B CN102971272 B CN 102971272B
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- Prior art keywords
- float stone
- emulsion
- hydrophobizing agent
- silane
- general formula
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C04B14/02—Granular materials, e.g. microballoons
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- C04B14/14—Minerals of vulcanic origin
- C04B14/16—Minerals of vulcanic origin porous, e.g. pumice
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- C04B20/004—Hollow or porous granular materials inorganic
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- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
本发明涉及粒状浮石，其中其表面被疏水性涂层涂覆。
Description
粒状浮石主要作为用于各种建筑产品和建筑化学产品的轻集料使用。可提及石膏和抹灰以及砂浆、细混凝土、外墙覆盖板和轻质板、以及防火板和防噪声板、绝缘产品等。但是，粒状浮石还作为用于塑料材料的轻集料使用。粒状浮石的优点在于其非常低的重量、高的压缩强度以及非常良好的隔热性。它还完好适于吸音，显示出高透气活性，不易燃且不含溶剂，并且气味中性，而且是100%矿物性并可回收的。
但是，作为矿物性的多孔天然产物，浮石显示出一定的吸水能力。因此，相对于不具有吸水能力或明显较低的吸水能力的轻集料，例如同样常用的硅质泡沫体，当将浮石用作轻集料时，无论是否将水用于混合，或多或少地都需加入一些水。这造成含加入浮石的混合组合物的产量或多或少地低于例如包含硅质泡沫体作为轻集料的组合物的产量。
因此，本发明致力于解决提供性质改善的浮石的问题，所述浮石特别用作轻集料以制备使用液体制成的组合物。
为了解决该问题，本发明提供了具有疏水性涂层的粒状浮石的表面。
根据本发明，作为具有一定的吸水能力的天然材料的本发明粒状浮石被疏水性表面涂层涂布，并由此疏水化。如长期测试所显示的，通过对浮石适当处理而施用的该表层使得浮石颗粒完全疏水化，并保持它们的疏水性。该疏水性表面涂层由此向本发明粒状浮石提供以前未曾确保的性质，并对于浮石的用途范围或本发明浮石所加入的产品的性质有决定性影响。首先，本发明疏水性浮石可用于各种液体体系或含流体体系，例如补充水等或溶剂的体系等。可提及瓷砖粘合剂或板材粘合剂、轻质石膏和抹灰、补强性抹刀涂抹的砂浆以及清漆、油漆和糊状体系。这些体系中的许多并非仅在现场完全混合的，而是在工厂已混合并封装，由此需确保它们能够经过长时间并保留其流体状或糊状性质不变化。与使用上述的吸水性能力虽然低的硅质泡沫体相反，这可通过使用本发明的粒状疏水性浮石有利地得到确保。此外，本发明浮石不再具有任何吸水能力，当将该浮石用作砂浆和相似组合物的轻集料时，可使得水/水泥值的设置能更精确。此外，相对于纯浮石，本发明浮石的表观颗粒密度可显著降低，从未疏水化浮石的约0.9kg/dm3降低至本发明疏水化浮石的约0.5kg/dm3。这使得产量提高，并使例如与本发明浮石掺混的砂浆或瓷砖粘合剂的干的堆密度降低。所述浮石的疏水性能还能实现其在水泥粘结体系中改善的分布，这产生改善是由于最终产品可以均匀地疏水化。这意味着成品的吸水能力比其它轻集料更低。
总之，本发明的粒状疏水化浮石提供性质范围以及由此而来的用途范围的必要拓宽。
在本发明的实施方案中，可使用疏水性的硅烷和/或硅氧烷层涂覆浮石。各种硅烷或硅氧烷、无论环状或直链硅烷或硅氧烷都可用作该硅烷或硅氧烷层。特别合适的是实际上不溶于水的直链或支化的硅烷或它们的混合物或硅氧烷。这些例如包括硅酮树脂或硅酮树脂溶液、低聚硅氧烷和聚合硅氧烷。也可使用硅酮。通常，可将任何类型的烷基聚硅氧烷和/或烷基烷氧基硅烷以及反应性有机硅氧烷和聚二甲基硅氧烷的硅氧烷混合物用作用于所述浮石表面的疏水性涂层。其中，优选使用反应性有机硅氧烷化合物和聚二甲基硅氧烷的混合物，特别优选作为乳液用于形成涂层。
另外或备选地，所述浮石还可使用至少一种有机脂肪酸或至少一种有机脂肪酸的盐的涂层进行涂布。该酸和盐例如包括硬脂酸和硬质酸的各种盐，即硬质酸盐(例如硬脂酸钠、硬脂酸钾、硬脂酸钙、硬脂酸铝、硬脂酸锌、硬脂酸锆或硬脂酸铵或硬脂酸三乙醇铵)、油酸和油酸的各种盐，即油酸盐(例如油酸钠和油酸铵)、以及妥尔油脂肪酸及其盐和树脂酸及树脂酸的盐。
另外或备选地，所述浮石表面的涂层还可由矿物油或矿物油乳液构成。矿物油主要由石蜡油、环烷油和芳族组分以及烯烃的混合物构成。
另外或备选地，所述浮石表面的涂层还可由至少一种烷烃构成。这些还包括蜡和蜡油乳液，其任选基于石蜡基。还可提及PE/HDPE蜡、细晶蜡、Fischer-Tropsch蜡、褐煤蜡、酯蜡、酰胺蜡、天然蜡、巴西棕榈蜡、PTFE蜡、蜡掺混物、聚合物-蜡掺混物或PP蜡。
另外或备选地，所述浮石表面还可具有由沥青和沥青乳化液构成的涂层。其同样具有强斥水或疏水的性质。
除了本发明浮石本身，本发明提供用于制备所述类型浮石的方法。本发明方法的特征在于使用包含至少一种疏水剂的乳液润湿所述粒状浮石，该疏水剂形成分散于外相中的内相，随后干燥浮石，所述疏水剂在浮石颗粒的表面上形成疏水性涂层。优选将所述疏水剂作为乳液使用。
尽管可通过浸渍在所述乳液中，即将浮石倒入足够大量的乳液中，在其中搅拌，并使乳液或疏水剂渗入或变得粘附于浮石，并在足够的停留时间之后，取出浮石，使其滴液并干燥来润湿浮石；本发明的一个有利的实施方案提供在浮石上喷涂疏水化乳液或其稀释液。在混合浮石的同时进行喷涂是有利的。也就是说，将浮石例如在犁头式混合器中连续混合，同时将乳液通过合适的喷涂装置连续或间歇地喷涂，使得乳液由于连续混合而混入，并由此变得细小且均匀地分散在浮石颗粒的表面上。当匹配待处理的浮石量，并包含足量的所添加疏水剂(同样匹配待处理的浮石量)的乳液已全部喷涂上并混入时，可继续混合以达到乳液分散的进一步匀化。在混合结束时，干燥浮石以除去乳液外相，即蒸发水，使得形成不含水的疏水层。
基本混合时间应在1分钟-25分钟的范围，特别是10分钟-15分钟，仅在总混合时间的一部分过程中喷涂乳液。例如，可以在20分钟的总混合时间的前5分钟进行喷涂，随后继续混合另外的15分钟，以使乳液或疏水剂分布均匀。
热处理，即浮石的干燥在0°-200°C，优选130°-180°C的温度下有利地进行，使得确保通常用作外相的水被尽可能快地除去。优选的干燥温度为约150°C。
对于疏水剂，根据本发明优选使用至少一种硅烷和/或至少一种硅氧烷，使用上述的环状和直链或支化的硅烷及它们的混合物。直链的硅烷或硅氧烷特别地显示出水不溶性。
此外，可使用一种或多种上述的基于硅烷和/或硅氧烷的材料。
根据本发明，可使用通过以下的硅烷、硅氧烷和它们的任何混合物所得到的：
A1)通式R3-Si-(OR2)3的硅烷，
其中
R2是甲基或乙基，并且
R3是具有3-12个碳原子的烷基、
或是具有1-6个碳原子的氨烷基、或
通式H2N-(CH2)xR4-(CH2)y-的基团，其中
R4是氧、硫、-NH-
或
-NH-CH2-CH2-NH-基团，并且
x≥2，并且
y≥2，或是
通式(R2O)3Si-(CH2)x-NH-(CH2)x-的基团，
R2和x如上定义，
并且n为整数1-5，
或
A2)以下通式的聚硅氧烷或硅氧烷醇(siloxanol)
其中
R5是甲基或苯基，但至少90%的基团R5是甲基，并且m=20-250，
其中混合物由A1)和A2)构成，
其中保持A1)与A2)的比值，使化合物A2)的一个SiOH基对应于化合物A1)的>1至3个OR2基团，并且R2是具有1-4个碳原子的烷基。基团R2的实例是甲基、乙基、丙基和丁基。优选甲基和乙基。组分A1)是通式R3-Si-(OR2)3的烷氧基硅烷。基团R2具有上述含义，而基团R3的特征在于它具有反应性基团，并通过碳与硅原子键接。R3可具有以下含义：
(1)R3=氨烷基，其烷基具有1-6个碳原子。该基团的实例包括乙胺基、丙胺基、丁胺基和己胺基，
优选基团-(CH2)3-NH2和
(2)R3=通式H2H-(CH2)xR4-(CH2)y-的基团，其中R4是氧、硫、-NH-或-NH-CH2-CH2-NH-基团，x≥2且y≥2。该基团的实例是H2N-(CH2-)3-和H2N-(CH2)2-NH-(CH2)3-。
(3)(R2O)3Si-(CH2)x-NH-(CH2)x-。该基团的实例是(C2H5O)3Si-(CH2)3-NH-(CH2)3-和(CH3)3Si-(CH2)2-NH-(CH2)2-。
(4)R3=通式
的基团，
并且n是整数1-5。一个特别优选的环氧化物的实例是
含义为-(CH2)3-NH2、-(CH2)2-NH-(CH2)3-NH2或(4)的基团特别优选作为基团R3。
组分A2)是以下通式的α,ω-硅氧烷醇：
其中R5是甲基或苯基。至少90%的基团R5需是甲基。特别优选的是α,ω-二甲基硅氧烷醇。m是20-250，并且优选是30-80。
设置组分A1)与A2)的比值，使化合物A2)的一个SiOH基对应于化合物A1)的>1至3个OR2基团。OH：OR2的比值优选为1：2。
硅烷A1和/或硅氧烷醇A2可单独使用或以与彼此的任何混合物使用。
所述混合物作为溶液可包含溶剂，例如醇类，特别在不含水或含水下处于乳液形式时。这些产物在水中作为乳液或在溶剂，例如醇类、烃类中作为溶液时，可具有0.1-100%的活性含量。
这些产物可具有0.1-99.9重量%的硅烷A1和/或硅氧烷醇A2，其溶于或乳化于水中或溶于溶剂，例如醇类或烃类中。
本发明制备方法的改进方案的特征在于组分A1)和A2)不单独存在，而以它们的反应产物存在，所述反应产物可通过考虑其化学计量比，通过在乳化这些组分之前将其加热至150-200°C而使组分A1)和A2)彼此完全或部分地反应而得到。已发现当使用本发明的该改进制备方法时，同样可达到斥水性作用上的良好效果。
另外或备选地，对于疏水剂，任选可使用至少一种有机脂肪酸或至少一种有机脂肪酸的盐。在此，举例来说可再次参考以上所述的有机脂肪酸或有机脂肪酸的盐。
备选或另外地，还可设想将矿物油作为疏水剂使用。
同样适用于将烷烃作为疏水剂使用。
另外或备选地，还可设想将沥青作为疏水剂使用。
根据本发明，乳液中的疏水剂含量以克计应为待润湿浮石量以克计的0.1%-2.5%，特别是0.3%-1%。其含义是为了疏水化1kg的浮石，对于例如0.5%的疏水剂的称重量，所述乳液包含例如5g量的疏水剂。所用的外相，例如水的量也有利地通过待润湿浮石的量确定。由此，外相的量，特别是水的量以克计应为同样以克计的待润湿浮石量的1/5-1/3，特别是1/4。根据1kg浮石为例，应使用例如250g的水(=250ml的水)，其中乳化有上述5g的疏水剂。
在各种研究和对比测试中，已检验本发明浮石的性质，并与各种对比性材料对比。
首先制备特定量的本发明浮石。将来自ROTECGmbH&Co.KG的商用名为“ROTOCELL”，粒径为0.09-0.3mm，堆密度为390kg/m3+/-15%的浮石用作原料。称出400g干重的该浮石。
然后量出100ml的水(=的浮石质量)以制备乳液。向水中加入2g的疏水剂，即从EvonikGoldschmidtGmbH，以商用名“Sitren595”可得的反应性有机硅氧烷/PDMS混合物(的浮石质量)。通过振摇来混合水和疏水剂，并由此使疏水剂微细地乳化。水的量可自然变化。重要的是所加入的疏水剂含量总是处于与待润湿浮石的质量的所需比值之中，并且也全部加入浮石中。基于浮石质量的硅氧烷的量被乳化的乳液产生越多，需与浮石混合的乳液也越多。
在下一步骤中，将浮石加入混合器中，其通过捏合钩混合浮石。开始混合时，使用喷涂瓶喷涂乳液，同时连续进行混合。在完成喷涂操作之后，在约5分钟之后，连续再搅拌15分钟。
当搅拌完成时，取出经润湿的浮石，并将其放置在150°C的干燥烘箱的盘中干燥。随后将经干燥的浮石取出，并在室内空气中冷却。
在长期测试中，首先测试本发明浮石的吸水能力。
为了该目的，在两个读取体积为1000ml的竖筒中放入恰好500ml量的蒸馏水。在其中一个竖筒中放入恰好100g的浮石，其以商用名“ROTOCELL”可得，粒径为0.09-0.3mm，其未根据本发明进行疏水化。在另一个竖筒中放入恰好100g上述制备的疏水化的“ROTOCELL”浮石。
在加入之后，未疏水化的浮石立即下沉。在从该浮石的孔体积中溢出空气之后，测得620ml的读取体积。
相比之下，根据本发明疏水化的浮石未下沉。测得的读取体积为720ml。
在加入浮石并测定读取体积之后，用薄膜封闭竖筒以使其气密，并在无振动下放置。
使样品放置一周，其后再次确定读取体积。发现与第一次加入浮石之后立即读取的读取体积相同，即在包含未疏水化的浮石的竖筒的情况下，体积为620ml；在包含已根据本发明疏水化的浮石的筒的情况下，体积为720ml。由此，没有出现变化。
由此可见，已根据本发明疏水化的浮石不吸收任何水，即它是完全疏水性的。
在另一试验中，制备三个不同的试样，其中一个包含已如上制备的本发明浮石，而另两个包含其它集料，测试初始制备的试样组合物的性质以及成品试样的性质。
将主要基于水泥(普通水泥)、细颗粒集料(粉碎的石灰石、硅砂)和添加剂(甲基纤维素、分散粉末、纤维素纤维、高铝酸盐水泥)的市售瓷砖粘合剂(粘合剂砂浆)用作原料。其中各称重出三份恰好600g的砂浆量。
将150g的粒径为0.1-0.3mm的市售硅质泡沫体(轻质泡沫)加入至第一份的量中。将150g的粒径为0.09-0.3mm，但未疏水化的“ROTOCELL”加入第二份砂浆量中。将150g的根据本发明的上述“ROTOCELL”浮石加入第三份砂浆量中。
随后用水混合各样品。向第一样品中加入345g的水，向第二样品中加入375g的水，向第三样品中加入345g的水。
然后首先测量各样品的产量。含硅质泡沫体的第一样品的产量为870ml。含未处理的浮石的样品显示出815ml的产量。含本发明浮石的样品表现出900ml的产量。这表示本发明浮石产生产量最高的砂浆组合物，其可归因于所述浮石的疏水性以及由此而来的其斥水性及其在组合物中的均匀分布。
随后测试制得样品的初始(fresh)总密度。在含硅质泡沫体的样品情况下其为127kg/dm3，在含未处理的浮石的第二样品的情况下其为127kg/dm3，并且在含本发明浮石的样品中其为122kg/dm3。这表明含本发明浮石的样品具有较低密度。
在按照DINEN12002，基于瓷砖粘合剂试验的下一步骤中，从各组合物制备砂浆棱柱(prism)形式的测试样品，以测试砂浆的变形行为。各棱柱长160mm，宽80mm且高80mm。将各情况下制备的棱柱体干燥数天，并随后测试。
在下表中显示各测试结果以及组合物中使用的各组分的量。
首先，测试试样的干重。在含硅质泡沫体的试样的情况下其为229g，在含未处理的浮石的试样的情况下其为227g，而在含本发明浮石的试样的情况下其为223g。这表示含本发明浮石的试样是所有试样中最轻的。
此外，测试干的总密度。在含硅质泡沫体的试样的情况下其为0.224kg/dm3，在含未处理的浮石的试样的情况下其为0.221kg/dm3，而在含本发明浮石的试样的情况下其为0.218kg/dm3。含本发明浮石的试样由此显示出最低的干总密度。
然后测试弯曲断裂载荷、弯曲拉伸强度、压缩断裂载荷和压缩强度。在该表中可找到详细的测试结果。
含硅质泡沫体的试样的断裂载荷为0.487kN。含未处理的浮石的试样的断裂载荷为0.408kN，显著低于含硅质的轻质泡沫的试样值，而含本发明浮石的试样的测试值为0.449kN，大致在含硅质的轻质泡沫试样的范围中。
硅质泡沫体试样的弯曲拉伸强度为0.143N/mm2。含未处理的浮石的试样为0.12N/mm2，在此仍然显著更低，而含本发明浮石的试样给出的值为0.132N/mm2，再次大致在硅质泡沫体试样的范围中。
在压缩断裂载荷的情况下，含本发明浮石的试样显示出最高的测试值4.52kN，而含硅质泡沫体的试样的值为4.39kN，并且含未处理的浮石的试样的值为3.56kN。在压缩强度的情况下，相对于硅质泡沫体试样情况下的0.7N/mm2和含未处理的浮石的试样情况下的0.6N/mm2，含本发明浮石的试样依然具有最高值0.71N/mm2。
对比试验显示出使用本发明浮石能够与例如瓷砖粘合剂混合，特别是相对于砂浆/含硅质泡沫体的试样，如各试样显示出的，第一其具有非常良好的产量，第二，其具有非常良好的机械性质。
Claims (17)
1.粒状浮石，其包含被疏水性涂层涂布的表面，其中所述涂层包含硅烷、硅氧烷或它们的混合物，
其中所述硅烷是：
A1)通式R3-Si-(OR2)3的硅烷：
其中
R2是甲基或乙基，并且
R3是具有3-12个碳原子的烷基、
或具有1-6个碳原子的氨烷基、或
通式H2N-(CH2)xR4-(CH2)y-的基团，其中
R4是氧、硫、-NH-
或
-NH-CH2-CH2-NH-基团，并且
x≥2，和
y≥2，或是
通式(R2O)3Si-(CH2)x-NH-(CH2)x-的基团，
其中R2和x如上定义，
或
或
其中n为整数1-5，并且
其中所述硅氧烷是：
A2)以下通式的硅氧烷醇：
其中
R5是甲基或苯基，但至少90％的基团R5是甲基，并且m＝20-250，
并且其中所述混合物包含
根据A1)的硅烷；和
根据A2)的硅氧烷，
其中保持A1)与A2)的比值，使化合物A2)的一个SiOH基对应于
化合物A1)的>1至3个OR2基团。
2.权利要求1的粒状浮石，其中所述涂层额外地包含选自有机脂肪酸和有机脂肪酸的盐的至少一种化合物。
3.权利要求1的粒状浮石，其中所述涂层额外地包含矿物油或矿物油的乳液。
4.权利要求1的粒状浮石，其中所述涂层额外地包含至少一种烷烃。
5.权利要求1的粒状浮石，其中所述涂层额外地包含沥青或沥青乳化液。
6.用于制备权利要求1的粒状浮石的方法，其包括：
使用包含至少一种疏水剂的乳液润湿粒状浮石，该疏水剂分散于乳液的外相中，并且其形成乳液的内相，和
随后干燥该粒状浮石，以使所述疏水剂在浮石颗粒的表面上形成疏水性涂层，
其中所述疏水性涂层包含至少一种硅烷、至少一种硅氧烷或它们的混合物，
其中所述硅烷是：
A1)通式R3-Si-(OR2)3的硅烷：
其中
R2是甲基或乙基，并且
R3是具有3-12个碳原子的烷基、
或具有1-6个碳原子的氨烷基、或
通式H2N-(CH2)xR4-(CH2)y-的基团，其中
R4是氧、硫、-NH-，
或
-NH-CH2-CH2-NH-基团，并且
x≥2，和
y≥2，或是
通式(R2O)3Si-(CH2)x-NH-(CH2)x-的基团，
其中R2和x如上定义，
或
或
其中n为整数1-5；
其中所述硅氧烷是：
A2)以下通式的硅氧烷醇：
其中
R5是甲基或苯基，至少90％的基团R5是甲基，并且
m＝20-250。
7.权利要求6的方法，其中将所述乳液喷涂上。
8.权利要求6的方法，其中在加入所述乳液的过程中和之后混合所述浮石。
9.权利要求8的方法，其中混合时间为1min-25min。
10.权利要求6的方法，其中在0°-200℃的温度下干燥经润湿的浮石。
11.权利要求6的方法，其中所述疏水剂额外地包括选自有机脂肪酸和有机脂肪酸的盐至少一种化合物。
12.权利要求6的方法，其中所述疏水剂额外地包含矿物油。
13.权利要求6的方法，其中所述疏水剂额外地包含烷烃。
14.权利要求6的方法，其中所述疏水剂额外地包含沥青。
15.权利要求6的方法，其中所述乳液的外相是水。
16.权利要求6的方法，其中在经润湿的粒状浮石中的疏水剂以克计的含量为以克计的经润湿的粒状浮石量的0.1％-2.5％。
17.权利要求6的方法，其中以克计的所述乳液的外相的量是以克计的经润湿的浮石量的1/5-1/3。
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| PCT/EP2011/053287 WO2011147599A1 (de) | 2010-05-26 | 2011-03-04 | Granularer bims sowie verfahren zur herstellung von granularem bims |
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| DE102010021532A1 (de) * | 2010-05-26 | 2011-12-01 | Evonik Goldschmidt Gmbh | Granularer Bims sowie Verfahren zur Herstellung von granularem Bims |
| US8915033B2 (en) | 2012-06-29 | 2014-12-23 | Intellectual Gorilla B.V. | Gypsum composites used in fire resistant building components |
| US9375899B2 (en) | 2012-06-29 | 2016-06-28 | The Intellectual Gorilla Gmbh | Gypsum composites used in fire resistant building components |
| US9243444B2 (en) | 2012-06-29 | 2016-01-26 | The Intellectual Gorilla Gmbh | Fire rated door |
| US9890083B2 (en) | 2013-03-05 | 2018-02-13 | The Intellectual Gorilla Gmbh | Extruded gypsum-based materials |
| JP6207859B2 (ja) * | 2013-03-29 | 2017-10-04 | 三商株式会社 | 表面保護剤及び表面保護工法 |
| CN111003958A (zh) | 2013-04-24 | 2020-04-14 | 知识产权古里亚有限责任公司 | 挤出的轻质热绝缘水泥基材料 |
| US9475732B2 (en) | 2013-04-24 | 2016-10-25 | The Intellectual Gorilla Gmbh | Expanded lightweight aggregate made from glass or pumice |
| US10029947B2 (en) | 2013-05-16 | 2018-07-24 | Bnz Materials, Inc. | Refractory castables with hydrophobic aggregates |
| US10125046B2 (en) * | 2013-10-15 | 2018-11-13 | S & B Industrial Minerals S.A. | Expanded, micronized surface treated aluminosilicate volcanic glass as lamellar functional filler for plastics and special coatings |
| WO2015057978A2 (en) | 2013-10-17 | 2015-04-23 | Intellectual Gorilla B.V. | High temperature lightweight thermal insulating cement and silica based materials |
| DE102013019681A1 (de) | 2013-11-22 | 2015-06-11 | Klb Klimaleichtblock Gmbh | Oberflächenbeschichter bims, verfahren zum oberflächenbeschichten von bims, verwendung einer flüssigglas-zusammensetzung zum oberflächen-beschichten von bims |
| CN106573839A (zh) | 2014-02-04 | 2017-04-19 | 知识产权古里亚有限责任公司 | 基于轻质隔热水泥的材料 |
| US11072562B2 (en) | 2014-06-05 | 2021-07-27 | The Intellectual Gorilla Gmbh | Cement-based tile |
| BR112016028409B1 (pt) | 2014-06-05 | 2022-09-20 | The Intellectual Gorilla Gmbh | Materiais à base de cimento extrusável e método para fabricar um material à base de cimento extrusável |
| DE102015102530A1 (de) * | 2015-02-23 | 2016-08-25 | Monier Roofing Gmbh | Dachstein sowie Verfahren zur Herstellung eines solchen Dachsteins |
| CN110204277A (zh) * | 2019-06-04 | 2019-09-06 | 东方雨虹民用建材有限责任公司 | 一种防结块瓷砖胶及其制备方法 |
| CN113604087B (zh) * | 2021-07-27 | 2022-07-05 | 四川纵横交安科技有限公司 | 一种环保吸音蓄能发光材料及其制备方法及应用 |
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| US20140370294A1 (en) | 2014-12-18 |
| US20130143044A1 (en) | 2013-06-06 |
| US9388075B2 (en) | 2016-07-12 |
| EP2576477A1 (de) | 2013-04-10 |
| EP2639207A1 (de) | 2013-09-18 |
| BR112012029925A2 (pt) | 2017-02-21 |
| JP2013529171A (ja) | 2013-07-18 |
| EP2576477B1 (de) | 2014-06-18 |
| CA2799983A1 (en) | 2011-12-01 |
| ES2600642T3 (es) | 2017-02-10 |
| DK2576477T6 (en) | 2015-10-12 |
| DE102010021532A1 (de) | 2011-12-01 |
| DK2639207T3 (en) | 2016-11-28 |
| US8859096B2 (en) | 2014-10-14 |
| PL2639207T3 (pl) | 2017-01-31 |
| ES2493092T3 (es) | 2014-09-11 |
| PL2576477T3 (pl) | 2014-11-28 |
| WO2011147599A1 (de) | 2011-12-01 |
| CA2799983C (en) | 2017-04-18 |
| CN102971272A (zh) | 2013-03-13 |
| ES2493092T7 (es) | 2015-10-22 |
| DK2576477T3 (da) | 2014-08-18 |
| EP2639207B1 (de) | 2016-08-03 |
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