CN100534956C - 石材防护剂及其制备方法 - Google Patents
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Abstract
本发明涉及石材防护剂技术领域，特别涉及纳米石材防护剂及其制备方法，本发明表涂剂的组份组成为：体积百分比，三烷氧基硅烷与四烷氧基硅烷的混合物溶液40～55%、1%的氟硅烷溶液30～50%、30%的纳米氧化硅溶液1.5～3.0%、10%的纳米氧化钛溶液3.0～8.5%；底涂剂为1%的氟硅烷溶液；本发明还提供了该纳米石材防护剂的制备方法；本发明可提高现有石材防护剂的耐候性，使其实现易洁不沾性，并分解由于石材的天然性特征而先天存在着的微生物的废气排放对石材造成的污物。
Description
技术领域：
本发明涉及石材防护剂技术领域，特别涉及石材防护剂及其制备方法。
背景技术：
石材的化学破坏一般是指石材中的成分因与其它化学物质反应，使石材出现成分丢失，疏松、破裂以及物理性能降低，尤其以碳酸盐为主的大理石类表现最为明显，最常见的例子是大理石类中的CaCO。与酸雨中的SO2、CO2反应，导致石材逐渐风化，并不断被水带走，形成孔洞、沟槽、裂隙；不能被水带走的则会生成尖硬的皮层，它与原石材结构不同，最终出现泡水脱落、鳞状脱落，有的出现黑层。这种化学破坏在石材文物中最为常见，也最为明显。近年来，工业发展使大气中的酸雨浓度比以往任何时候都高，SO2、SO3。最终形成的酸雨对我国及至世界石材文物造成的破坏已经逐渐显露。
除了自然对石材的化学破坏以外，人类的生活也对石材造成化学破坏，如用酸性清洗液对装饰石材清洗，厨房、卫生间的强酸、强碱都会对石材造成化学破坏。另外，石材在加工、安装、使用、维修中出现的冻损、应力、渗水、粘色等也会对石材造成破坏；具有生命的植物、微生物的新陈代谢及活动产生CO2、有机酸、磷酸等，这些也会不同程度地消耗石材中的矿物质，进一步促进石材分解、风化，从而对石材造成损伤。
石材工业发达的国家，目前在石材使用前一般都进行防护，这样才能避免日后不必要的治理。随着人们对天然石材自然美感的喜爱，我国民众已开始接受石材装修前须对石材进行防护的理念，并在一些重要工程中已身体力行，对石材的定期清洗、防护也给予了必要的重视。近年来，随着加工技术的提高，后修饰、美化石材的化工产品的普及与应用，使天然石材的品质更优越，诸如表面致密度、光泽度、几何尺寸、吸水率、耐磨、硬度、耐酸碱性等性能方面，在常人看来，几乎和玻璃质(如玻璃、微晶玻璃、铸石)、瓷(陶瓷、釉面砖)、金属(铝塑板、钛合金)一样，具备坚硬密实、不透气、耐候的特性。然而，天然石材与前述材料的本质区别恰恰就在于它是天生的多孔材料，而上面提到的则是后天工业化生产的无孔材料。由于天然石材的多孔特征，决定了它极易吸收、吸附并沉积污染物。因易吸收污染物，如水性污染、油性污染、日用化学品、药品污染、饮食污染等，而破坏其天然美感。因此，石材虽然外表坚硬，但仍免不了被侵蚀，这就须对天然石材进行必要的防护。另外，随着近年工业污染对石质文物中石质建筑、石岩画、雕刻等的破坏加重，用化学方法进行清洗后再防护，已经被文物界认可。
据了解，目前用于石材的防护剂主要有蜡、聚丙烯酸等、甲基硅酸钾(钠)、硅烷/硅氧烷类、有机氟类和一些不饱和树脂类等几大类产品共存。主要使用的溶剂有水、苯、甲苯、二甲苯、200#汽油、丙酮和一些烷烃类有机溶剂。其中蜡类及聚丙烯酸类具有成膜而不透气、时效短的缺陷。性能较好、时效较长的防护剂为溶剂型有机氟类，但又具有不环保的蔽端。
发明内容：
本发明的目的是提供一种新型的纳米石材防护剂及其制备方法，本发明要提高现有石材防护剂的耐候性，使其实现易洁不沾性，并分解由于石材的天然性特征：多孔、裂隙、多成分、吸水，因而先天存在着的生多种微生物的废气排放对石材造成的污物。
为达到上述目的，本发明采用如下技术方案：
本发明表涂剂的组份组成为(体积百分比)：
三烷氧基硅烷与四烷氧基硅烷的混合物溶液 40～55％
1％的氟硅烷【CF3(CF2)5CH2CH2Si(OC2H5)3】溶液 30～50％
30％的纳米氧化硅溶液 1.5～3.0％
10％的纳米氧化钛溶液 3.0～8.5％；
其中，底涂剂与表涂剂各组份中的溶剂为水，助溶剂为乙醇或异丙醇种；
底涂剂采用氟硅烷【CF3(CF2)5CH2CH2Si(OC2H5)3】、溶剂用水和乙醇；
由于氟硅烷【CF3(CF2)5CH2CH2Si(OC2H5)3】不能完全溶解于水，因此在配制溶液时除选用水作为溶剂的主要组分外，还加入了适量的乙醇(或丙醇)作为助溶剂；其具体操作如下：首先将氟硅烷和水按体积比为1∶49混合配称2％(体积百分比)的氟硅烷中间溶液，然后用冰乙酸调节中间液的PH值在3.0～3.8之间，调好酸度后用乙醇将中间液稀释成1％(体积百分比)的氟硅烷溶液，最后将所配制溶液在室温下充分搅拌5h左右，使其形成均匀透明液体；使用时用无油、无色、不掉毛的尼龙刷或化纤布蘸该液均匀涂刷，待充分干燥后再涂表涂剂；
其表涂层的表涂剂组份为三烷氧基硅烷、四烷氧基硅烷、氟硅烷【CF3(CF2)5CH2CH2Si(OC2H5)3】、纳米氧化硅、纳米氧化钛、溶剂，溶剂为水，助溶剂为乙醇或异丙醇种；其中三烷氧基硅烷可选用甲基三乙氧基硅烷、乙基三乙氧基硅烷、丙基三乙氧基硅烷、乙烯基三乙氧基硅烷、苯基三乙氧基硅烷，它们可单独使用，也可混合使用；四烷氧基硅烷可选用四甲氧基硅烷、四乙氧基硅烷、四丁氧基硅烷、四戊氧基硅烷、四丙氧基硅烷等，可单独使用，也可混合使用。
各组份的作用为，纳米氧化硅提高防护剂的强度、韧性和渗透性，其粒径控制在5～20nm的范围内，其紫外屏蔽率可达到70％左右。纳米氧化钛(主要是锐钛相)，可吸收阳光中的紫外线，产生光催化效应，在光的作用下，产生的自由电子-空穴对，可将石材中的有机物、有毒有害物质、NOX、SO2氧化成CO2、水和相应的酸、以达到抗菌、自洁。减少有毒有害物质对石材造成的影响，三烷氧基硅烷、四烷氧基硅烷、氟硅烷的低表面能作用，有效减少涂料分子间的库仑力，防止外界水分子的侵入对石材造成的破坏，提高石材的耐候性。
本发明还提供了纳米石材防护剂的制备方法：先将四烷氧基硅烷用水溶解，调制平均分子量在300～700之间，再按比例与三烷氧基硅烷混合，三烷氧基硅烷与四烷氧基硅烷的质量比在100∶(35～70)为最佳；如果四烷氧基硅烷的质量比小于20质量份，涂膜的耐磨、耐热性降低；大于130质量份，涂膜易出现增厚、裂纹和改变石材颜色。具体操作如下：先将四烷氧基硅烷用4倍质量份0.4％的醋酸水溶液溶解，然后加入到用1.5倍异丙醇溶解的三烷氧基硅烷溶液中，搅拌均匀后50℃下加热60分钟；25℃以下自然冷却备用；将前述1％的氟硅烷【CF3(CF2)5CH2CH2Si(OC2H5)3】溶液及30％的异丙醇基纳米氧化硅溶液、10％的异丙醇基纳米氧化钛溶液依次加入搅匀即可。
纳米材料是指尺寸介于0.1～100nm的材料。纳米材料在装饰石材上的应用如果得到开发，必将对传统的装饰石材带来突破性的技术进步。
在通常渗透型的防护剂中，除加入一些抗紫外吸收剂、活性剂外，加入纳米级二氧化硅、高分子聚合物及有关化学品，所产生渗透力更强，防护剂附着力更强的效果。一般渗透型防护剂渗入深度在5mm左右，而加入纳米级材料可在10～20mm之间，这对耐候性和持久防护十分有利。经过纳米防护剂防护的石材，若干年后再用同一种防护剂仍可涂上，也即可清洗后，其接受重涂性更为优越。
利用纳米氧化钛抗菌防护剂，通过纳米氧化钛的光催化效应，吸光后，其表面发生氧化还原反应，吸收光的能量后把石材及空气中的细菌、臭气、有毒气体等
二氧化碳和水。由于石材的天然性特征，多孔、裂隙、多成分、吸水，因而先天存在着生多种微生物，如细菌、霉菌、酵母菌、藻类、植物、虫类、微型小动物的环境，一定程度上也影响室内外已装饰装修好的石材美观，经上述纳米Tio2的光催化作用，使细菌等微生物处于无氧状态和环境，从而造成石材表面菌类和微生物死亡。
具体实施方式：
实施例1
三烷氧基硅烷与四烷氧基硅烷的混合物溶液 45％
1％的氟硅烷【CF3(CF2)5CH2CH2Si(OC2H5)3】溶液 45％
30％的纳米氧化硅溶液 3.0％
10％的纳米氧化钛溶液 7.0％
其中三烷氧基硅烷与四烷氧基硅烷的混合物溶液制备：先将40质量份四甲氧基硅烷用4倍质量份0.4％的醋酸水溶液溶解，调制平均分子量在300～700之间，再将100质量份的乙基三乙氧基硅烷加入到150质量份的异丙醇中溶解，然后将两种溶液混合，搅拌均匀后50℃下加热60分钟；25℃以下自然冷却即可。
实施例2
三烷氧基硅烷与四烷氧基硅烷的混合物溶液 40％
1％的氟硅烷【CF3(CF2)5CH2CH2Si(OC2H5)3】溶液 50％
30％的纳米氧化硅溶液 2.0％
10％的纳米氧化钛溶液 8.0％
其中三烷氧基硅烷与四烷氧基硅烷的混合物溶液制备同实施例1。
Claims (2)
1、石材防护剂，其特征在于：它包括表涂剂和底涂剂，表涂剂的组份组成为：体积百分比
三烷氧基硅烷与四烷氧基硅烷的混合液40～55％
1％的氟硅烷CF3(CF2)5CH2CH2Si(OC2H5)3溶液30～50％
30％的纳米氧化硅溶液1.5～3.0％
10％的纳米氧化钛溶液3.0～8.5％；
底涂剂为1％的氟硅烷CF3(CF2)5CH2CH2Si(OC2H5)3溶液；
其中，底涂剂与表涂剂各组份中的溶剂为水，助溶剂为乙醇或异丙醇；三烷氧基硅烷与四烷氧基硅烷的质量比为100∶(35～70)；
三烷氧基硅烷选用甲基三乙氧基硅烷、乙基三乙氧基硅烷、丙基三乙氧基硅烷、乙烯基三乙氧基硅烷、苯基三乙氧基硅烷中的一种或多种；四烷氧基硅烷选用四甲氧基硅烷、四乙氧基硅烷、四丁氧基硅烷、四戊氧基硅烷、四丙氧基硅烷中的一种或多种；
其中，制备三烷氧基硅烷与四烷氧基硅烷的混合溶液：先将四烷氧基硅烷用4倍质量份0.4％的醋酸水溶液溶解，然后加入到用1.5倍异丙醇溶解的三烷氧基硅烷溶液中，搅拌均匀后50℃下加热60分钟；25℃以下自然冷却。
2、制备如权利要求1所述的石材防护剂的方法，其特征在于：它包括以下步骤：
(1)、制备1％的氟硅烷CF3(CF2)5CH2CH2Si(OC2H5)3溶液：首先将氟硅烷和水按体积比为1∶49混合配成体积百分比为2％的氟硅烷中间溶液，然后用冰乙酸调节中间液的pH值在3.0～3.8之间，调好酸度后用乙醇将中间液稀释成体积百分比为1％的氟硅烷溶液，最后将所配制溶液在室温下充分搅拌5h之后，使其形成均匀透明液体；
(2)、制备三烷氧基硅烷与四烷氧基硅烷的混合溶液：先将四烷氧基硅烷用4倍质量份0.4％的醋酸水溶液溶解，然后加入到用1.5倍异丙醇溶解的三烷氧基硅烷溶液中，搅拌均匀后50℃下加热60分钟；25℃以下自然冷却备用；
(3)、混合：将前述1％的氟硅烷CF3(CF2)5CH2CH2Si(OC2H5)3溶液及30％的纳米氧化硅溶液、10％的纳米氧化钛溶液依次加入步骤(2)中的溶液内搅匀即可；
底涂剂为1％的氟硅烷CF3(CF2)5CH2CH2Si(OC2H5)3溶液，其中，底涂剂与表涂剂各组份中的溶剂为水，助溶剂为乙醇或异丙醇。
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| CN102731142B (zh) * | 2011-11-07 | 2014-06-18 | 罗凌利 | 一种石材浸泡式防护剂的配置方法 |
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| CN104031556A (zh) * | 2014-04-25 | 2014-09-10 | 北京中为三丰科技有限责任公司 | 一种纳米级水性保护液及其制备与应用 |
| CN104177126A (zh) * | 2014-08-08 | 2014-12-03 | 南雄鼎成化工有限公司 | 一种乳液型石材用超疏水防护剂的制备方法及应用 |
| CA2967599C (en) | 2014-11-12 | 2023-09-12 | University Of Houston System | Soil-resistant, stain-resistant fluorine-free coatings and methods of applying on materials |
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