CN101801889A - 用于保藏多孔物质的物质混合物和方法 - Google Patents
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Abstract
本发明涉及一种用于保藏多孔物质，特别是由石头或木材构成的物体的液态物质混合物，其中所述混合物包含选自有机改性二氧化硅，特别是有机(烷氧基)硅烷(Ormosil)的至少两种物质。本发明还涉及一种保藏多孔物质的方法。
Description
本发明涉及一种用于保藏多孔物质，特别是由石头或木材构成的物体的不含甲基丙烯酸甲酯的物质混合物。本发明还涉及一种保藏多孔物质的方法。
对侵蚀的保护和对已经受到侵蚀的天然石的保藏总是从这样的假设出发，通过导入防护材料而保护并加固岩石的表面-也就是可见的面。然而，每种防护材料的导入都在所到达的区域内引起岩石物理特性的改变。物理特性的这种改变经常带来后续损伤。因此，每种防腐措施的目标应该都是，将这种改变保持在尽可能低并且对岩石的整个横截面-也就是直至核心部分-产生保藏作用，以便避免具有不同物理特性的区域。
这种要求基本上利用1972年以来发展的丙烯酸类树脂完全浸渍方法来实现，其中在浸没浴(Vollbad)中将事先彻底干燥的岩石借助于真空和压力利用甲基丙烯酸甲酯(MMA)浸渍到核心部分，且随后将MMA聚合成丙烯酸酯玻璃。因为在这种方法中使所有浸渍溶液都固化了，使孔完全充满PMMA，从而彻底抑制了吸水性和透气性。
纪念碑养护多年以来就期望有一种开孔保护方法，在该方法中通过在孔体系内部中的保护膜-通过孔壁的内衬材料-实现保护作用和加固作用。由于在纪念碑的保护中容忍使用的四乙氧基硅烷(TEOS)-更广为人知的是术语硅酸酯(KSE)-它在反应结束后的“终产物”是由纯SiO2构成的硅胶，使得孔壁内衬的这个目的不能实现。由于完全的水解和缩聚反应，上述凝胶变得易碎且有裂缝，而且所产生的SiO2在孔隙空间中以碎块状(bruchschollenartig)存在。因此，所述保护作用和加固作用要低很多倍，此外还产生额外的微孔体系，从而不可控制地影响吸水性能和排水性能。如此改变硅胶的形成，使得产生具有足够弹性、成膜性的凝胶的尝试无法实现。为了涂布内表面，只有这样的体系是适合的，所述体系由单体构成并且因此能够到达非常小的孔。单体-聚合物体系形式的漆体系，证明适合于外部应用的纳米体系，由于缺乏对许多孔体系，特别是岩石的渗入能力而析出。
本发明的目的在于，在多孔物质特别是物体中产生在孔体系中对抗水和有害物质侵入的耐久保护层，且同时在孔体系中构成缺乏的粘合剂。
根据本发明，所述目的通过包含选自有机改性二氧化硅，特别是有机(烷氧基)硅烷(Ormosil)的至少两种物质的混合物来实现。
令人惊奇地发现，有机(烷氧基)硅烷(也称为“Ormosil”，也就是有机改性的二氧化硅＝有机改性的SiO2)适用于内表面的这类涂层。与纳米体系和由溶剂与固体组成的“漆”体系相反，由于其分子尺寸，所述物质混合物具有非常好的渗入性能并且可以到达即使是非常小的孔。
在到达内部空腔之后，这种物质混合物通过水解和缩聚作用硬化，使得保留了在4％至69％之间，特别是在8％至30％之间的固体含量作为在孔隙空间中内衬孔壁的膜。
通过水解和缩聚作用完成的硬化，特别是在大体积的物体的情况下，可通过受程序控制的温度和湿度运用得到令人惊奇地良好控制。
试验表明，在良好吸收性多孔物质中维持良好渗入性能足够时间的情况下，令人惊奇地可以添加相应的水成分以引发水解。
在孔隙空间中产生的硅胶被证实作为没有裂缝的、透明的、不溶于水的膜以良好的粘附性来覆盖所述孔壁，从而产生了预期的内衬效果。
令人惊奇的是，可以在浸渍之前很短时间添加所需的水，而不会在所需的渗入时间内对渗入性能产生较强的不利影响。
特别有利的是添加1至10％的增附剂，特别是有机硅烷。也有意义的是，得到液态的、不含丙烯酸酯的物质混合物。
本发明的有利实施方案在从属权利要求中列出。
下面详细描述本发明的实施例。
根据本发明的液态物质混合物被用来浸渍多孔物质，特别是由木材或石头构成的物体以起到保藏作用。
在注射到待保藏的物质的孔体系中之前，将由在醇溶液中的缩水甘油氧基丙基三甲氧基硅烷(GLYMO)和氨基丙基三乙氧基硅烷(APTS)组成的活性物质体系中的这两种组分按照化学计量的量合并，并且在分解出水的情况下反应生成具有六个位于边缘的(
)烷氧基团的中间产物。通过部分水解激活所述活性物质体系，并且在分解出水且分解出醇的情况下缩合成硅胶，在其结构中有机组分嵌入到Si原子之间，并且在一定程度上作为间隔基(Abstandshalter)起到构成低张力的凝胶结构的作用(图)。
所述保藏性液体可以具有不同的组成，其中所述混合物包含选自有机(烷氧基)硅烷(Ormosil)的至少一种物质。
在此特别有利的是下面的混合物：
a)所述混合物中的物质是包含至少一个环氧单元的Ormosil。
b)所述混合物中的物质是3-缩水甘油基氧丙基三甲氧基硅烷(GLYMO)。
c)所述混合物中的物质是包含至少一个胺官能团的Ormosil。
d)所述混合物中的物质是γ氨基丙基三乙氧基硅烷(APTS)。
e)所述混合物中的两种物质由前面在a)和c)中所述的Ormosil组成。
f)所述混合物中的两种物质由前面在b)和d)中所述的Ormosil组成。
作为亲水的溶剂优选添加具有一个至六个碳原子的醇，特别是乙醇或甲醇。
所述包含至少一个环氧单元的Ormosil与所述包含至少一个胺官能团的Ormosil的质量比为1∶0.2至1∶10，优选1∶0.7至1∶1.7且特别具有1∶1.07的质量比。
其它选择方案在于，除了所述具有至少一个环氧单元的Ormosil之外，且除了所述包含至少一个胺官能团的Ormosil之外，所述物质混合物还包含至少一种其它Ormosil。在此，所述其它Ormosil是
-γ甲基丙烯酰氧丙基三甲氧基硅烷，
-乙烯基三乙氧基硅烷，
-二甲基二乙氧基硅烷和/或
-二甲基二甲氧基硅烷。
有意义的是，在所述混合物中添加相应的水含量来引发水解。
其它实施例：
将多孔物质(以物体，例如一个石头或一块木材的形式)首先干燥，然后浸入到液体中，所述液体由至少两种Ormosil加上优选为乙醇的溶剂组成。在此，所述包含至少一个环氧单元的Ormosil与所述包含至少一个胺官能团的Ormosil的质量比为1∶1.07。有利的混合物由2.4g Ormosil 1，2.3g Ormosil 2和28g乙醇组成。在28g乙醇的情况下在所述物体中达到约9.5-约10％的固体沉淀。在此，乙醇的含量可以在0-50g之间选择。
通过所述方法，除了达到较高的腐蚀稳定性之外，还达到了物体较高的强度。这在E模量的显著提高中显示出来。
Claims (15)
1.用于保藏多孔物质，特别是由石头或木材构成的物体的不含甲基丙烯酸甲酯的液态物质混合物，其特征在于，所述混合物包含选自有机改性二氧化硅(Ormosil)，特别是有机(烷氧基)硅烷的至少两种物质。
2.根据权利要求1的物质混合物，其特征在于，所述混合物的物质是包含至少一个环氧单元的Ormosil。
3.根据权利要求1或2的物质混合物，其特征在于，所述混合物的物质是3-缩水甘油基氧丙基三甲氧基硅烷(GLYMO)。
4.根据前述权利要求中任一项的物质混合物，其特征在于，所述混合物的物质是包含至少一个胺官能团的Ormosil。
5.根据前述权利要求中任一项的物质混合物，其特征在于，所述混合物中的物质是γ氨基丙基三乙氧基硅烷(APTS)。
6.根据前述权利要求中任一项的物质混合物，其特征在于，添加亲水溶剂，优选具有一个至六个碳原子的醇。
7.根据权利要求6的物质混合物，其特征在于，所述醇是乙醇或甲醇。
8.根据权利要求2-7中任一项的物质混合物，其特征在于，所述包含至少一个环氧单元的Ormosil与所述包含至少一个胺官能团的Ormosil的质量比为1∶0.2至1∶10，优选1∶0.7至1∶1.7，且特别具有1∶1.07的质量比。
9.根据前述权利要求中任一项的物质混合物，其特征在于，除了所述包含至少一个环氧单元的Ormosil之外，且除了所述包含至少一个胺官能团的Ormosil之外，还包含至少一种其它Ormosil。
10.根据权利要求9的物质混合物，其特征在于，附加于所述混合物的其它Ormosil是γ甲基丙烯酰氧丙基三甲氧基硅烷。
11.根据权利要求9的物质混合物，其特征在于，附加于所述混合物的其它Ormosil是乙烯基三乙氧基硅烷。
12.根据权利要求9的物质混合物，其特征在于，附加于所述混合物的其它Ormosil是二甲基二乙氧基硅烷。
13.根据权利要求9的物质混合物，其特征在于，附加于所述混合物的其它Ormosil是二甲基二甲氧基硅烷。
14.根据前述权利要求中任一项的物质混合物，其特征在于，向所述混合物中添加相应的水成分以引发水解。
15.利用根据前述权利要求中任一项的混合物保藏所述多孔物质的方法，通过用Ormosil浸渍所述多孔物质并随后干燥。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102007030672.7 | 2007-07-02 | ||
| DE102007030672.7A DE102007030672B4 (de) | 2007-07-02 | 2007-07-02 | Verfahren zum Konservieren poröser Stoffe |
| PCT/EP2008/004968 WO2009003594A1 (de) | 2007-07-02 | 2008-06-20 | Stoffmischung und verfahren zum konservieren poröser stoffe |
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| US (1) | US20100139522A1 (zh) |
| EP (1) | EP2164821A1 (zh) |
| JP (1) | JP2010531902A (zh) |
| KR (1) | KR20100032869A (zh) |
| CN (1) | CN101801889A (zh) |
| CA (1) | CA2691909C (zh) |
| DE (1) | DE102007030672B4 (zh) |
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| WO (1) | WO2009003594A1 (zh) |
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| DE102007041487A1 (de) * | 2007-08-31 | 2009-03-05 | Ibach Steinkonservierung Gmbh & Co. Kg | Stoffmischung als Bindemittel zur Herstellung eines Mörtels |
| KR101557497B1 (ko) * | 2008-07-23 | 2015-10-06 | 삼성전자주식회사 | 물질 조성의 구배를 갖는 박막 및 그의 제조방법 |
| CN101831076B (zh) * | 2010-04-23 | 2012-07-04 | 华东理工大学 | 硅胶颗粒表面青蒿素分子印迹聚合物及其制备和应用方法 |
| US20160017501A1 (en) * | 2013-03-14 | 2016-01-21 | United Technologies Corporation | Corrosion Protection Material and Method for Protecting Aluminum Coatings |
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| US254178A (en) * | 1882-02-28 | perk van lith | ||
| DE2258901B2 (de) * | 1972-12-01 | 1980-11-06 | Dynamit Nobel Ag, 5210 Troisdorf | Imprägnieren von Mauerwerk mit neutral oder sauer reagierenden Oberflächen |
| DE3905919A1 (de) * | 1989-02-25 | 1990-08-30 | Degussa | Organosiliciumverbindungen-enthaltende gemische und deren verwendung zur hydrophobierenden und antimikrobiellen impraegnierung |
| US5051129A (en) * | 1990-06-25 | 1991-09-24 | Dow Corning Corporation | Masonry water repellent composition |
| DE4033155A1 (de) * | 1990-10-12 | 1992-04-16 | Nuenchritz Chemie Gmbh | Hydrophobier- bzw. isoliermittel auf siliconbasis |
| US5421866A (en) * | 1994-05-16 | 1995-06-06 | Dow Corning Corporation | Water repellent compositions |
| DE19816973A1 (de) * | 1998-04-17 | 1999-11-25 | Degussa | Verfahren zur Imprägnierung von mineralischen Baustoffen und dafür geeignete Organosiliciumverbindungen |
| DE19904133B4 (de) * | 1999-02-03 | 2007-02-08 | Degussa Ag | Oberflächenmodifizierter Isolator und Verfahren zur Modifizierung der Oberfläche eines Isolators |
| DE10044216A1 (de) * | 2000-09-07 | 2002-05-02 | Fraunhofer Ges Forschung | Beschichtungsmaterial für multifunktionelle, superphobe Schichten |
| DE10122626A1 (de) * | 2001-05-10 | 2002-06-06 | Wacker Chemie Gmbh | Verfahren zur hydrophobierenden Holzbehandlung |
| DE10122627A1 (de) * | 2001-05-10 | 2002-11-21 | Wacker Chemie Gmbh | Verfahren zur hydrophobierenden Holzbehandlung |
| DE10130091B4 (de) * | 2001-06-21 | 2007-10-11 | Remmers Baustofftechnik Gmbh | Verfahren zur Herstellung einer gebrauchsfertigen Injektionscreme zur Hydrophobierung von Mauerwerk und deren Verwendung |
| DE102004036073A1 (de) * | 2004-07-24 | 2006-02-16 | Degussa Ag | Verfahren zur Versiegelung von Natursteinen |
| US20060181774A1 (en) * | 2005-02-16 | 2006-08-17 | Konica Minolta Opto, Inc. | Antireflection film, production method of the same, polarizing plate and display |
| DE102005010157A1 (de) * | 2005-03-02 | 2006-09-07 | Degussa Ag | Gesteine mit erhöhter Lichttransmission, Verfahren zu ihrer Herstellung und ihre Verwendung |
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| Publication number | Publication date |
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| JP2010531902A (ja) | 2010-09-30 |
| RU2010103205A (ru) | 2011-08-10 |
| US20100139522A1 (en) | 2010-06-10 |
| EP2164821A1 (de) | 2010-03-24 |
| DE102007030672B4 (de) | 2017-05-24 |
| WO2009003594A1 (de) | 2009-01-08 |
| DE102007030672A1 (de) | 2009-01-08 |
| CA2691909C (en) | 2013-06-18 |
| CA2691909A1 (en) | 2009-01-08 |
| KR20100032869A (ko) | 2010-03-26 |
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