CN1678696A - 二氧化硅 - Google Patents
二氧化硅 Download PDFInfo
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Abstract
硅烷化的、结构改性的、热解法制备的二氧化硅,其特征在于表面结合基团,其中所述基团为二甲基甲硅烷基和/或单甲基甲硅烷基,其由热解法制备的二氧化硅用二甲基二氯硅烷和/或单甲基三氯硅烷以已知方法处理,二甲基甲硅烷基和/或单甲基甲硅烷基结合在热解法二氧化硅的表面,然后进行结构改性和任选后研磨来制备。它们用来在漆中提高耐擦伤性。
Description
技术领域
本发明涉及硅烷化的、结构改性的、热解法制备的二氧化硅,其制备方法及其用途。
背景技术
众所周知在透明的涂料组分中使用纳米尺寸的粒子。
因此,依照美国专利第6,020,419号,热解法制备的、原位解附聚的、已经用二甲基二氯硅烷(AerosilR 972)制成疏水型的二氧化硅被用在聚氨酯漆中以改进涂层的耐擦伤性。
已知的二氧化硅的缺点在于如果没有漆的粘合剂,它就不能以粉末的形式制备。
因此存在开发没有这些缺点的二氧化硅的任务。
发明内容
本发明提供了硅烷化的、结构改性的、热解法制备的二氧化硅,其特征在于表面结合基团,所述基团是二甲基甲硅烷基和/或单甲基甲硅烷基,优选为二甲基甲硅烷基。
在本发明的一个优选实施方案中,二氧化硅可以具有下列物理-化学特性:
BET表面积m2/g 25-400
初级粒子的平均尺寸nm 5-50
pH值 3-10
碳含量% 0.1-10
DBP值% <200
依照本发明的二氧化硅可以具有100~280g/l的填充密度,优选为100~240g/l。
填充密度超过280g/l会在工业的漆沉积试验中导致更差的结果。
热解法二氧化硅可参见Winnacker-Küchler,ChemischeTechnologie,第3卷(1983),第四版,第77页以及UllmannsEncyklopdie der technischen Chemie,第四版(1982),第21卷,第462页。
特别地,热解法可以由可蒸发的硅化合物如SiCl4或有机硅化合物如三氯甲基硅烷的火焰水解制备。
本发明也提供了一种用于制备依照本发明的硅烷化的、结构改性的、热解法制备的二氧化硅的方法,其特征在于热解法制备的二氧化硅用二甲基二氯硅烷和/或单甲基三氯硅烷以公知的方法处理,二甲基甲硅烷基和/或单甲基甲硅烷基结合在热解法二氧化硅的表面上,然后进行结构改性和任选的后研磨。
在本发明的一个实施方案中,回火可以在结构改性和/或后研磨之后进行。
依照本发明的二氧化硅可以按例如如下的方法制备:
可按照DE 1 163 784中所描述的方法制备二氧化硅,然后通过机械作用进行结构改性并且可在研磨机中进行后研磨。在结构改性和/或后研磨之后可进行回火。
结构改性可以用如球磨机或连续运转的球磨机进行。后研磨可以使用如空气射流研磨机或销式研磨机进行。回火可以在如橱式干燥机中分批地或在如液化床中连续地进行。回火可以在保护气体如氮气下进行。
依照本发明的二氧化硅可以加入到漆中,结果这些漆提高了耐擦伤性。
具体实施方式
二氧化硅的制备和物理-化学特性
对比二氧化硅的制备:
对比二氧化硅1、2和3的制备按照DE 1 163 784中所描述的方法制备。
本发明的二氧化硅的制备:
按照DE 1 163 784中所描述的方法制备二氧化硅,然后通过机械作用进行结构改性并且可在研磨机中进行后研磨。在结构改性和/或后研磨之后可进行回火。
结构改性可以例如用球磨机或连续运转的球磨机进行。后研磨可以使用例如空气射流研磨机或销式研磨机进行。回火可以在例如橱式干燥机中分批地或在例如液化床中连续地进行。回火可以在保护气体如氮气下进行。
表1对比二氧化硅和本发明的二氧化硅(实施例)的制备概要
名称 | 表面结合基团 | 结构改性 | 结构改性后后研磨 | 后研磨后回火 |
对比二氧化硅1 | 二甲基甲硅烷基 | 否 | - | - |
对比二氧化硅2 | 二甲基甲硅烷基 | 否 | - | - |
对比二氧化硅3 | 二甲基甲硅烷基 | 否 | - | - |
二氧化硅1 | 二甲基甲硅烷基 | 是 | 否 | 否 |
二氧化硅2 | 二甲基甲硅烷基 | 是 | 否 | 否 |
二氧化硅3 | 二甲基甲硅烷基 | 是 | 否 | 否 |
二氧化硅4 | 二甲基甲硅烷基 | 是 | 否 | 否 |
二氧化硅5 | 二甲基甲硅烷基 | 是 | 是 | 否 |
二氧化硅6 | 二甲基甲硅烷基 | 是 | 否 | 否 |
二氧化硅7 | 二甲基甲硅烷基 | 是 | 是 | 否 |
二氧化硅8 | 二甲基甲硅烷基 | 是 | 是 | 是 |
二氧化硅9 | 二甲基甲硅烷基 | 是 | 是 | 是 |
二氧化硅10 | 二甲基甲硅烷基 | 是 | 是 | 否 |
二氧化硅11 | 二甲基甲硅烷基 | 是 | 是 | 否 |
表2依照本发明的二氧化硅(实施例)和对比二氧化硅的物理-化学数据
名称 | 填充密度[g/l] | 干燥损失[%] | 灼烧减量[%] | pH值 | C含量[%] | DBP吸附[%] | BET表面积[m2/g] |
对比二氧化硅1 | 64 | 0.1 | 0.5 | 4.0 | 0.8 | 243 | 113 |
对比二氧化硅2 | 67 | 0.5 | 0.6 | 4.8 | 1.0 | 256 | 165 |
对比二氧化硅3 | 72 | 0.7 | 1.0 | 4.0 | 1.6 | 255 | 256 |
二氧化硅1 | 236 | 0.1 | 0.6 | 4.0 | 0.8 | 127 | 115 |
二氧化硅2 | 204 | 0.1 | 0.6 | 3.9 | 0.8 | 137 | 116 |
二氧化硅3 | 223 | 0.3 | 0.7 | 4.2 | 1.0 | 160 | 169 |
二氧化硅4 | 186 | 0.3 | 0.7 | 4.2 | 1.1 | 152 | 171 |
二氧化硅5 | 109 | 0.2 | 0.7 | 4.4 | 1.1 | 159 | 167 |
二氧化硅6 | 193 | 1.2 | 0.7 | 5.2 | 1.7 | 157 | 258 |
二氧化硅7 | 125 | 0.2 | 0.7 | 4.1 | 0.8 | 130 | 110 |
二氧化硅8 | 108 | 0.7 | 1.3 | 5.0 | 1.7 | 156 | 257 |
二氧化硅9 | 123 | 0.3 | 0.5 | 4.3 | 1.1 | 157 | 165 |
二氧化硅10 | 102 | 0.7 | 1.2 | 6.2 | 1.7 | 164 | 256 |
二氧化硅11 | 160 | 0.2 | 0.7 | 4.0 | 0.8 | 132 | 115 |
实施例1:
对改进耐擦伤性的研究来说,通常使用2组分的聚氨酯漆。漆的配方及其制备,包括应用概括如下:
配方
研磨基料 | 重量份 |
丙烯酸共聚物,用合成的脂肪酸改性,60%溶液乙酸丁酯,98%二甲苯AEROSIL | 43.417.83.95.0 |
∑ | 70.7 |
漆组成 | |
二甲苯醋酸乙氧丙酯丁基乙二醇乙酸酯脂肪族聚异氰酸酯,约75%,在1-甲氧基丙基-2-乙酸酯/二甲苯1∶1中 | 11.33.41.618.6 |
∑ | 105.0 |
粘合剂浓度:40%
以研磨基料(固体)计算的AEROSIL:19.2%
以漆(总量)计算的AEROSIL:5.0%
以漆(固体)计算的AEROSIL:12.5%
漆的制备和应用
将粘合剂与溶剂混合。然后为了预分散的目的,将AEROSIL用高速混合机(圆盘45mm)合并到这种混合物中并在2000转/分钟下预分散5分钟。将混合物在实验室用的珍珠研磨机上2500转/分钟及60%的泵容量下使用玻璃珠(约1mm)预分散30分钟。研磨基料依照DIN ISO 1524使用25μm的粒度计检验。它必须小于10μm。
依照配方将研磨基料配成漆,配合剂用叶片搅拌器在2000转/分钟下混合。固化剂以同样的方式加入。
在依照DIN 53411将漆调整到适于喷淋的粘度之后,将漆通过喷雾装置涂于黑色的涂漆金属板上(涂层厚度约40-50μm),如DT36(由Q-Panel提供)。喷刷之后,金属板在室温下干燥24小时,然后在干燥箱中70℃下干燥2小时。
刮痕硬度试验:
将金属板用石英/水淤浆(100克水+1克Marlon A 350,0.25%+5克Sikron F500)利用耐磨损洗涤试验装置(Erichsen,猪鬃刷)进行磨损试验。用反射计(20°照射角)测定磨损前和磨损10分钟后的光泽。
表3在喷漆工艺方面相应的液体漆、以及涂刷和干燥的膜的性能概要
对比二氧化硅1 | 二氧化硅1 | 二氧化硅2 | 参照 | 对比二氧化硅2 | 二氧化硅3 | 二氧化硅4 | 参照 | ||
粒度计值[μm] | <10 | <10 | <10 | / | <10 | <10 | <10 | / | |
粘度(研磨基料)[mPas]6Rpm60Rpm | 47101120 | 421210 | 772264 | 571225 | 49901200 | 802279 | 772264 | 5552 | |
粘度(漆+固化剂)[mPas]6rpm60rpm | 882239 | 10575 | 21092 | 13579 | 857242 | 235100 | 10526 | 7037 | |
流动性 | 桔皮皱纹 | 好 | 好 | 好 | 桔皮皱纹 | 好 | 好 | 好 | |
耐擦伤性 | |||||||||
擦伤前20°反射计值 | 39.0 | 83.4 | 83.5 | 88.8 | 67.2 | 84.2 | 82.6 | 89.3 | |
擦伤前的纹理 | 430 | 30 | 40 | 3 | 235 | 18 | 10 | 2 | |
用Sikron F 500划40下后剩余的光泽[%] | / | 83.7 | 82.3 | 56.0 | / | 74.7 | 80.4 | 47.2 |
本发明的二氧化硅1+2和3+4可以以高浓度使用而没有削弱漆表面的外观,这是由于与对比二氧化硅1和2相比它们具有相当低的流变学效应的缘故。此外,依照本发明的二氧化硅在漆表面的耐擦伤性方面表现出相当大的改进。
实施例2
在这个实施例中,在高固含量的2组分PU清漆基础上研究了结构改性的影响。漆的配方以及它的制备,包括应用和测试概括如下:
配方
研磨基料 | 重量份 |
丙烯酸共聚物,用合成的脂肪酸改性,70%乙酸正丁基酯溶液乙酸丁酯,98%醋酸乙氧丙酯芳烃油溶剂100二甲苯Baysilon OL 17,10%二甲苯溶液(硅油)AEROSIL | 61.07.31.72.02.00.75.0 |
∑ | 79.7 |
漆组成(固化剂) | |
脂肪族聚异氰酸酯,90%乙酸正丁酯溶液乙酸丁酯,98%芳烃油溶剂100 | 22.32.01.0 |
∑ | 105.0 |
粘合剂浓度:62.8%
以研磨基料(固体)计算的AEROSIL:11.7%
以漆(总量)计算的AEROSIL:5.0%
以漆(固体)计算的AEROSIL:8.0%
漆的制备和应用
将粘合剂与溶剂混合。然后为了预分散的目的,将AEROSIL用高速混合机(圆盘45mm)合并到这种混合物中并在2000转/分钟下预分散5分钟。将混合物在实验室用的珍珠研磨机上2500转/分钟和60%的泵容量下使用玻璃珠(约1mm)预分散30分钟。研磨基料依照DIN ISO 1524使用25μm的粒度计检验。它必须小于10μm。
依照配方将研磨基料配成漆,配合剂用叶片搅拌器在2000转/分钟下混合。固化剂以同样的方式加入。
在依照DIN 53411将漆调整到适于喷淋的粘度之后,将漆通过喷雾装置涂于黑色的涂漆金属板上(涂层厚度约40-50μm),如DT36(由Q-Panel提供)。喷刷之后,金属板在室温下干燥24小时,然后在干燥箱中70℃下干燥2小时。
刮痕硬度试验:
将金属板用石英/水淤浆(100克水+1克Marlon A 350,0.25%+5克Sikron F500)利用耐磨损洗涤试验装置(Erichsen,猪鬃刷)进行磨损试验。用反射计(20°照射角)测定磨损前和磨损10分钟后的光泽。
表4在喷漆工艺方面相应的液体漆,以及涂刷和干燥的膜的性能概要
对比二氧化硅2 | 二氧化硅3 | 二氧化硅4 | 参照 | |
粒度计值[μm] | <10 | <10 | <10 | / |
粘度(研磨基料)[mPas]6rpm60rpm | 62002100 | 1500900 | 541559 | 140195 |
粘度(漆+固化剂)[mPas]6rpm60rpm | 38211320 | 1041666 | 497446 | 167195 |
流动性 | 明显的桔皮皱纹 | 好 | 好 | 好 |
擦伤前20°反射计值 | 81.0 | 83.5 | 82.8 | 88.0 |
纹理 | 25 | 5 | 6 | 2 |
用SikronF 500划40下后剩余的光泽[%] | 94.3 | 93.4 | 82.0 |
本发明的二氧化硅3+4可以以高浓度使用而没有削弱漆表面的外观,这是由于与对比二氧化硅2相比它们具有相当低的流变学效应的缘故。此外,依照本发明的二氧化硅在漆表面的耐擦伤性方面表现出相当大的改进。
实施例3:
本发明的二氧化硅与依照DE 198 11 790 A1的耐擦伤漆的直接对比,其中使用AEROSIL R 972以提高耐擦伤性。
现有技术1) | 本发明的二氧化硅2) | |
研磨基料 | ||
Desmophen A 2009/l | 190.2 | |
乙酸甲氧丙酯∶芳烃油溶剂100 1∶1 | 36.8 | |
AEROSIL | 23.0 | |
∑ | 250.0 | |
漆组成 | ||
Desmophen A YEP4-55A,包含AEROSIL R 972 | 96.0 | - |
研磨基料 | - | 48.9 |
Desmophen 2009/1 | - | 24.9 |
OL 17,10%MPA溶液 | - | - |
Modaflow 1%MPA溶液 | - | - |
MPA∶芳烃油溶剂100,1∶1 | 11.6 | 33.8 |
丁基乙二醇乙酸酯 | 10.5 | 10.5 |
Byketol OK | 7.5 | 7.5 |
Byk 141 | 0.8 | 0.8 |
固化剂的添加 | ||
Desmodur N3390 | 23.6 | 23.6 |
∑ | 150.0 | 150.0 |
漆的制备和应用
1)依照DE 198 11 790 A1使用射流分散器将对比二氧化硅1加入到粘合剂中。
2)将粘合剂与溶剂混合。然后为了预分散的目的,将AEROSIL用高速混合机(圆盘45mm)合并到这种混合物中并在2000转/分钟下预分散5分钟。将混合物在实验室用的珍珠研磨机上2500转/分钟及60%的泵容量下使用玻璃珠(约1mm)预分散30分钟。研磨基料依照DIN ISO 1524使用25μm的粒度计检验。它必须小于10μm。
依照配方将对应1)或2)的研磨基料配成漆,各组分用叶片搅拌器在2000转/分钟下混合。固化剂以同样的方式加入。
在依照DIN 53411将漆调整到适于喷淋的粘度之后,将漆通过喷雾装置涂于黑色的涂漆金属板上(涂层厚度约40-50μm),如DT36(由Q-Panel提供)。喷刷之后,金属板在室温下干燥24小时,然后在干燥箱中70℃下干燥2小时。
刮痕硬度试验:
将金属板用石英/水淤浆(100克水+1克Marlon A 350,0.25%+5克Sikron F500)利用耐磨损洗涤试验装置(Erichsen,猪鬃刷)进行磨损试验。用反射计(20°照射角)测定磨损前和磨损10分钟后的光泽。
表5在喷漆工艺方面相应的液体漆、以及涂刷和干燥的膜的性能概要
现有技术 | 二氧化硅1 | 二氧化硅4 | 参照 | |
粒度计值[μm] | <10 | <10 | <10 | / |
粘度(研磨基料)[mPas]6rpm60rpm | 5848 | 3043 | 2633 | 3040 |
波扫描长波 | 4.8 | 1.2 | 1.1 | 1.4 |
短波 | 6.5 | 3.0 | 3.1 | 4.7 |
擦伤前20°反射计值 | 89.0 | 90.2 | 89.6 | 90.8 |
擦伤前的纹理 | 4 | 4 | 3 | 4 |
用Millicarb划40下后剩余光泽[%] | 78.3 | 85.9 | 86.2 | 55.3 |
可以看出,在漆表面经过刮痕应力后的剩余光泽方面通过使用依照本发明的二氧化硅比现有技术有了相当好的改进。此外,由于它低的流变学效应,依照本发明的二氧化硅不会引起桔皮皱纹效应。
Claims (5)
1.硅烷化的、结构改性的、热解法制备的二氧化硅,其特征在于表面结合基团,其中所述基团为二甲基甲硅烷基和/或单甲基甲硅烷基。
2.权利要求1的硅烷化的、结构改性的、热解法制备的二氧化硅,其特征在于具有以下物理-化学特性:
BET表面积m2/g:25-400
初级粒子的平均尺寸nm:5-50
pH值:3-10
碳含量%:0.1-10
DBP值%:<200
3.制备权利要求1的硅烷化的、结构改性的、热解法制备的二氧化硅的方法,其特征在于将热解法制备的二氧化硅用二甲基二氯硅烷和/或单甲基三氯硅烷以已知方法处理,二甲基甲硅烷基和/或单甲基甲硅烷基结合在热解法二氧化硅的表面上,然后进行结构改性和任选后研磨。
4.权利要求3的制备硅烷化的、结构改性的、热解法制备的二氧化硅的方法,其特征在于在结构改性和/或后研磨之后进行回火。
5.硅烷化的、结构改性的、热解法制备的二氧化硅用于改进漆的耐擦伤性的用途。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101896557A (zh) * | 2007-12-11 | 2010-11-24 | 赢创德固赛有限公司 | 涂层系统 |
US8211971B2 (en) | 2005-12-23 | 2012-07-03 | Evonik Degussa Gmbh | Fumed silanized silica |
CN101100300B (zh) * | 2006-05-26 | 2012-09-05 | 赢创德固赛有限责任公司 | 具有特殊表面性能的沉淀二氧化硅 |
CN103073927A (zh) * | 2013-01-31 | 2013-05-01 | 沈阳化工股份有限公司 | 提高硅橡胶撕裂强度的表面改性气相二氧化硅及其生产方法 |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10239424A1 (de) * | 2002-08-28 | 2004-03-11 | Degussa Ag | Kieselsäuren |
DE10239425A1 (de) * | 2002-08-28 | 2004-03-11 | Degussa Ag | Lackformulierungen |
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WO2006039605A2 (en) * | 2004-09-30 | 2006-04-13 | Cabot Corporation | Metal and oxides thereof and methods to make same |
EP1700825A1 (de) * | 2004-12-23 | 2006-09-13 | Degussa AG | Oberflächenmodifizierte, strukturmodifizierte Titandioxide |
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DE102007024097A1 (de) * | 2007-05-22 | 2008-11-27 | Evonik Degussa Gmbh | Kieselsäuren |
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JP4384208B2 (ja) | 2007-07-20 | 2009-12-16 | シャープ株式会社 | 外添剤の評価方法、トナーの評価方法 |
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DE102015204896A1 (de) * | 2015-03-18 | 2016-09-22 | Evonik Degussa Gmbh | Lacksystem enthaltend ein bewuchshemmendes Metalloxid und eine pyrogene Kieselsäure |
FR3055623B1 (fr) | 2016-09-08 | 2020-04-17 | Total Marketing Services | Liant clair solide a froid |
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FR3059673B1 (fr) | 2016-12-07 | 2018-11-23 | Total Marketing Services | Liants solides |
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FR3061191B1 (fr) | 2016-12-22 | 2019-05-24 | Total Marketing Services | Composition d’asphalte coule pour la realisation de revetements |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1163784C2 (de) | 1962-03-30 | 1973-05-03 | Degussa | Verfahren zur Oberflaechenbehandlung von hochdispersen Oxyden |
DE2513608C2 (de) * | 1975-03-27 | 1982-08-05 | Degussa Ag, 6000 Frankfurt | Verfahren zur Hydrophobierung von Kieselsäuren und Silikaten mit Organosilanen |
US6193795B1 (en) * | 1993-08-02 | 2001-02-27 | Degussa Corporation | Low structure pyrogenic hydrophilic and hydrophobic metallic oxides, production and use |
DE4402370A1 (de) | 1994-01-27 | 1995-08-03 | Degussa | Silanisierte Kieselsäuren |
PT725037E (pt) * | 1995-02-04 | 2001-07-31 | Degussa | Granulados a base de dioxido de silicio preparado pirogenicamente processo para a sua preparacao e sua utilizacao |
US5959005A (en) * | 1996-04-26 | 1999-09-28 | Degussa-Huls Aktiengesellschaft | Silanized silica |
DE19616781A1 (de) * | 1996-04-26 | 1997-11-06 | Degussa | Silanisierte Kieselsäure |
US6316050B1 (en) * | 1997-12-22 | 2001-11-13 | Degussa | Method of producing hydrophobic pyrogenically produced oxides |
DE19757210A1 (de) * | 1997-12-22 | 1999-07-01 | Degussa | Hydrophobierte, pyrogen hergestellte Oxide |
DE19811790A1 (de) | 1998-03-18 | 1999-09-23 | Bayer Ag | Nanopartikel enthaltende transparente Lackbindemittel mit verbesserter Verkratzungsbeständigkeit, ein Verfahren zur Herstellung sowie deren Verwendung |
GB2357497A (en) * | 1999-12-22 | 2001-06-27 | Degussa | Hydrophobic silica |
PT1173523E (pt) * | 2000-02-29 | 2006-05-31 | Feron Aluminium | Processo para a preparacao de um material estratificado e material estratificado assim obtido |
DE10239424A1 (de) * | 2002-08-28 | 2004-03-11 | Degussa Ag | Kieselsäuren |
-
2002
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2003
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- 2003-07-29 JP JP2004531827A patent/JP2005536613A/ja active Pending
- 2003-07-29 AU AU2003255311A patent/AU2003255311A1/en not_active Abandoned
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- 2003-07-29 EP EP20030790827 patent/EP1530614A1/en not_active Withdrawn
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- 2003-07-29 KR KR1020057003442A patent/KR100755735B1/ko not_active IP Right Cessation
- 2003-07-29 US US10/524,472 patent/US7452600B2/en not_active Expired - Fee Related
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8211971B2 (en) | 2005-12-23 | 2012-07-03 | Evonik Degussa Gmbh | Fumed silanized silica |
CN101346439B (zh) * | 2005-12-23 | 2012-08-29 | 赢创德固赛有限责任公司 | 热解法硅烷化二氧化硅 |
US8552107B2 (en) | 2005-12-23 | 2013-10-08 | Evonik Degussa Gmbh | Fumed silanized silica |
CN101100300B (zh) * | 2006-05-26 | 2012-09-05 | 赢创德固赛有限责任公司 | 具有特殊表面性能的沉淀二氧化硅 |
CN101896557A (zh) * | 2007-12-11 | 2010-11-24 | 赢创德固赛有限公司 | 涂层系统 |
CN103073927A (zh) * | 2013-01-31 | 2013-05-01 | 沈阳化工股份有限公司 | 提高硅橡胶撕裂强度的表面改性气相二氧化硅及其生产方法 |
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AU2003255311A1 (en) | 2004-03-19 |
US20050244642A1 (en) | 2005-11-03 |
CA2496922A1 (en) | 2004-03-11 |
DE10239423A1 (de) | 2004-03-11 |
JP2005536613A (ja) | 2005-12-02 |
KR100755735B1 (ko) | 2007-09-06 |
CA2496922C (en) | 2012-03-13 |
US7452600B2 (en) | 2008-11-18 |
KR20050057028A (ko) | 2005-06-16 |
BR0313949A (pt) | 2005-07-12 |
EP1530614A1 (en) | 2005-05-18 |
CN102002274A (zh) | 2011-04-06 |
WO2004020532A1 (en) | 2004-03-11 |
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