CN110643251B - 基于氟硅丙烯酸树脂的饰面型石材防护剂及其制备方法 - Google Patents
基于氟硅丙烯酸树脂的饰面型石材防护剂及其制备方法 Download PDFInfo
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- CN110643251B CN110643251B CN201910910411.7A CN201910910411A CN110643251B CN 110643251 B CN110643251 B CN 110643251B CN 201910910411 A CN201910910411 A CN 201910910411A CN 110643251 B CN110643251 B CN 110643251B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
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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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
- C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了基于氟硅丙烯酸树脂的饰面型石材防护剂及其制备方法;按照重量份数计,其由以下的原料组分构成:氟硅丙烯酸树脂溶液5~20份;硅烷偶联剂10~50份;低分子量端羟基硅油1~10份;稀释剂20~85份,催化剂0.5~2份。制备时,将氟硅共聚树脂溶液、硅烷偶联剂、羟端基硅油、稀释剂和催化剂均匀混合后,喷涂在石材表面。本发明氟硅丙烯酸树脂分子结构中存在全氟己基侧基、相对较长的硅氧烷侧基、甲基丙烯酸酯与含可交联官能团的侧基。本发明成本合理,工艺简单,有利于大规模生产,制得的石材防护剂具有良好的防水拒油效果,不会改变石材的自然外观与透气性,且不含有8个碳及以上的全氟链段,满足环保需求。
Description
技术领域
本发明涉及一种石材防护剂,特别是涉及一种基于氟硅丙烯酸树脂的饰面型石材防护剂及其制备方法,属于防护剂技术领域。
技术背景
装饰石材是近现代建筑的重要装饰装修材料。我国是石材荒料进口大国,同时是石材加工制成品出口大国,是名副其实的石材加工厂。据中国石材协会统计,2016年,全球石材产量有32%来自中国,全国规模以上企业共3158家,实现主营业收入4468亿元,同比增长11.6%。随着国内城镇化程度不断提高,商品化住宅房的普及,内需也在不断上升,对装饰石材清洗、防护、翻新、日常维护的需求量不断提升。石材防护剂的使用可以有效地减少石材清洗或翻新的频率,降低维护成本,其需求量也在不断上升。
中国发明专利申请CN 104017488 A公开了一种有机硅石材防护剂,工艺简单,成本低,具有良好的防水效果,但其对油污的防护能力差;中国发明专利申请CN 109233478 A公开了一种含氟有机硅石材防护剂,将含氟化合物引入有机硅防护剂,提高了对油污的防护效果,但其使用的含氟化合物为含有氟碳链长的全氟烷基聚合物。
长全氟烷基(CnF2n+1-,n≥8)的最终氧化降解产物多为全氟辛酸类化合物(PFOA)。PFOA在关于《物质和混合物分类、标签和包装法规》(EC)1272/2008法规中和持久性、生物累积性和毒性(PBT)中已被归为生殖毒性(对生殖系统有害)1B类和致癌2类,从2013年6月以来,PFOA就已经出现在高关注物质(SHVCs)候选列表中。由于PFOA造成的生物危害性,欧盟已经在REACH法规附件XVII新增第68项中禁止或限制带全氟庚基(C7F15-)或全氟辛基(C8F17-)等长全氟烷基结构作为其中一种结构要素的PFOA-相关物质的使用,该条款将分阶段执行,并于2020年7月4日开始执行。
发明内容
本发明的目的是提供一种基于氟硅共聚树脂的饰面型型石材防护剂,在不改变石材天然外观的基础上,解决有机硅石材防护剂对油污防护能力的不足,同时避免含长全氟烷基链的氟硅防护剂存在的环保问题。
本发明的另一目的是提供一种基于氟硅丙烯酸树脂的饰面型石材防护剂的制备方法。
本发明采用全氟己基乙基(甲基)丙烯酸酯合成用于石材防护剂的丙烯酸树脂,满足了欧盟的环保要求,同时在树脂分子上引入相对较长的硅氧烷侧基,弥补了因为氟碳链过短造成的防护效果的下降,再将该树脂与硅烷偶联剂、端羟基硅油、有机溶剂稀释混合后喷涂至干净的石材表面,固化后便可以达到良好的防水防油效果。加入适量的催化剂可以缩短防水剂固化的时间。全氟己基(C6F13-)不属于PFOA-相关物质,尚未发现其具有生物危害性,也没有任何机构限制其使用,满足环保需求。
本发明提供一种基于氟硅共聚树脂的饰面型石材防护剂及其制备方法。
为了解决上述问题,本发明采用的技术方案如下:
一种基于氟硅丙烯酸树脂的饰面型石材防护剂,按照重量份数计,其由以下的原料组分构成:
氟硅丙烯酸树脂溶液5~20份;
硅烷偶联剂10~50份;
端羟基硅油1~10份;
稀释剂20~85份
催化剂0.5~2份
所述的氟硅丙烯酸树脂溶液的合成方法:将占溶剂总量60~80wt%的有机溶剂加热到65~90℃,加入占引发剂总量50~85wt%的引发剂,得含有引发剂的溶液;将含氟丙烯酸酯单体、单端丙烯酸改性的有机硅单体、丙烯酸酯单体、丙烯酸酯交联单体与占有机溶剂总量10~20wt%的有机溶剂均匀混合后,得混合溶液;
向含有引发剂的溶液中滴加所述的混合溶液,滴加时间为2~4小时,滴加完后保温0.5~2小时;将剩余的有机溶剂与剩余的引发剂均匀混合,得含引发剂的有机溶剂;向保温结束的溶液中滴加所述的含引发剂的有机溶剂,滴加时间为0.5~1小时;最后升温至95~100℃,恒温1~2小时,冷却至室温后得到氟硅共聚丙烯酸树脂溶液;
单端丙烯酸改性的有机硅单体的结构式为:
其中R1为-CH3或-H;R2为-CH2-或-COO-;R3为-Si(CH3)3或-Si(CH3)2OCH3;m=0~3,n=10~25,单端丙烯酸改性的有机硅单体的数均分子量为500~2000。
为进一步实现本发明目的,优选地,所述的氟硅丙烯酸树脂溶液的合成方法中,各反应单体按占总单体重量百分比计,其单体组份为:含氟丙烯酸酯单体45~65%、单端丙烯酸改性的有机硅单体体15~25%、丙烯酸酯单体18~28%、丙烯酸酯交联单体2~5%;总单体占总反应体系的重量百分数为25~35%。
优选地,所述的含氟丙烯酸酯单体为全氟己基乙基甲基丙烯酸酯或全氟己基乙基丙烯酸酯;
所述的丙烯酸酯单体为甲基丙烯酸甲酯、甲基丙烯酸异冰片酯、甲基丙烯酸辛酯、甲基丙烯酸月桂酯、甲基丙烯酸十八酯、甲基丙烯酸苯氧乙酯、甲基丙烯酸苄基酯和甲基丙烯酸环己酯中的一种或多种;
所述的羟基丙烯酸酯单体为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯和甲基丙烯酸羟丁酯中的一种或多种。
优选地,所述的硅烷偶联剂为甲基三乙氧基硅烷、甲基三甲氧基硅烷、乙基三乙氧基硅烷、乙基三甲氧基硅烷、丙基三乙氧基硅烷、丙基三甲氧基硅烷、甲基三异丙氧基硅烷、辛基三乙氧基硅烷、辛基三甲氧基硅烷、十二烷基三甲氧基硅烷、十二烷基三乙氧基硅烷十六烷基三甲氧基硅烷和十六烷基三乙氧基硅烷中的一种或多种。
优选地,所述的催化剂为异辛酸锡、月桂酸二丁基锡、二醋酸二丁基锡、新癸酸铋、月桂酸铋、异辛酸铋、环烷酸铋、正硅酸乙酯、钛酸正丁酯和钛酸异丙酯中的一种或多种。
优选地,所述的引发剂为偶氮二异丁腈、偶氮二异庚腈、过氧化二苯甲酰中的一种或多种;
所述的有机溶剂为乙酸丁酯、甲基异丁基甲酮中、乙二醇二乙醚和乙二醇甲醚醋酸酯的一种或多种。
优选地,所述的端羟基硅油为粘度介于25~30CP之间的低分子量端羟基聚二甲基硅氧烷。
优选地,所述的稀释剂为乙酸乙酯、乙酸丁酯、甲基异丁基酮或溶剂油。
优选地,所述的溶剂油为D30、D40、D60、6#、120#、S100和S150中的一种或多种。
所述的基于氟硅丙烯酸树脂的饰面型石材防护剂的制备方法:将氟硅共聚树脂溶液、硅烷偶联剂、羟端基硅油、稀释剂和催化剂均匀混合后,喷涂在石材表面。
相对于现有技术,本发明具有以下优点:
1)本发明所用的氟硅丙烯酸树脂用全氟己基代替全氟辛基等长全氟烷基链,本发明中全氟碳链为全氟己基,不会氧化降解为全氟辛酸类化合物或全氟辛基磺酰基类化合物,满足环保要求,规避了全氟辛基的生物危害性。
2)本发明将相对较长的硅氧烷侧基引入含全氟己基的丙烯酸树脂分子中,改善全氟己基的防水耐油污效果,再将该树脂与含氟聚硅氧烷、硅烷偶联剂等配制成石材防护剂,用于石材防护。该防护剂既能保持石材的自然色泽,又能保证良好的防水性、耐油性与透气性。
3)本发明防护剂中的各组分在溶剂的带动下渗透至石材表面的微孔之中,在催化剂的作用下,硅烷偶联剂中的烷氧基基团与石材表面、氟硅丙烯酸树脂以及端羟基氟硅油中的羟基反应,形成稳定的硅氧键,提高了氟硅丙烯酸树脂对基材的耐久性和附着力,以此达到长久的防护效果。
4)本发明防护剂喷涂至石材表面后,全氟己基侧基与相对较长的硅氧烷侧基会自发向上富集至石材表面,降低石材表面的表面能,赋予石材表面优异的防水耐油污性能,使大理石表面的水接触角由0°上升至135°以上,十六烷接触角由0°上升至80°以上。
5)本发明树脂的合成与防护剂的配制使用方法简单,有利于大规模生产,降低综合成本,市场推广性强。
6)本发明石材防护剂不改变石材本身的颜色、不影响石材的透气性,还具有优异的抗紫外线、耐酸性、耐碱性。
附图说明
图1为实施例1与4中树脂分子的红外吸收光谱测试图。
图2为实施例2与5中树脂分子的红外吸收光谱测试图。
图3为实施例3与6中树脂分子的红外吸收光谱测试图。
具体实施方式
本发明结合以下实施对基于氟硅丙烯酸树脂的石材防护剂及其制备方法做进一步描述。可以理解的是,此处所描述的具体实施例仅仅用于解释相关发明,而非对该发明的限定。
实施例1
制备氟硅丙烯酸树脂溶液:将44.7g乙酸丁酯加入反应釜内加热至75℃后,一次加入0.2g偶氮二异丁腈。再将14.5g全氟己基乙基丙烯酸酯、5.5g DCA-2208(广州锐聚化工有限公司,分子量≈1900)有机硅单体、1.0g甲基丙烯酸月桂酯、1.0g甲基丙烯酸环己酯、2.5g甲基丙烯酸甲酯、0.5g甲基丙烯酸羟丙酯与15.0g乙酸丁酯均匀混合后得混合物,向反应釜中滴加所述的混合物。2.5小时滴完后保温0.5小时。随后将0.1g偶氮二异丁腈溶于10.0g乙酸丁酯中滴加到反应釜中,0.5小时滴完。最后升温至95℃,恒温1.5小时,冷却至室温后得到氟硅丙烯酸树脂溶液。
配制石材防护剂:以质量份数计,将5份氟硅丙烯酸树脂溶液、15份甲基三乙氧基硅烷、10份十二烷基三乙氧基硅烷、5份端羟基硅油、64份D40溶剂、1份异辛酸锡均匀混合。
实施例2
制备树脂溶液:将42g甲基异丁基酮加热至75℃后,一次加入0.24g偶氮二异丁腈,再将17.3g全氟己基乙基甲基丙烯酸酯、6.6g硅烷改性的乙烯基单体SMV(广州双键贸易有限公司,分子量≈1500)、1.2g甲基丙烯酸月桂酯、4.2g甲基丙烯酸甲酯、0.6g甲基丙烯酸羟乙酯与14g甲基异丁基酮均匀混合后,向含有偶氮二异丁腈的甲基异丁基酮中滴加上述混合溶液,2.5小时滴完,滴加完成后保温0.5小时,随后将0.06g偶氮二异丁腈溶于14g甲基异丁基酮中,向保温结束的溶液中滴加上述含引发剂的甲基异丁基酮,0.5小时滴完。最后升温至95℃,恒温1.5小时,冷却至室温后结束反应得到目标聚合物溶液。
硅烷改性的乙烯基单体SMV的结构式为:
配制石材防护剂:以质量份数计,将10份氟硅丙烯酸树脂溶液、10份乙基三乙氧基硅烷、10份十六烷基三乙氧基硅烷、10份端羟基硅油均、59份120#溶剂油、1份月桂酸二丁基锡均匀混合。
实施例3
制备树脂溶液:将24.5g乙酸丁酯与24.5g甲基异丁基酮均匀混合后加热至85℃后,一次加入0.28g过氧化二苯甲酰,再将21.6g全氟己基乙基丙烯酸酯、7.5g DCA-2206(广州锐聚化工有限公司,分子量≈1200)、4.9g甲基丙烯酸异冰片酯、1.0g甲基丙烯酸羟乙酯与16.3g甲基异丁基酮均匀混合后,向含有过氧化二苯甲酰的的乙酸丁酯中滴加上述混合溶液,3.5小时滴完,滴加完成后保温1.5小时,随后将0.07g过氧化二苯甲酰溶于16.3g乙酸丁酯中,向保温结束的溶液中滴加上述含引发剂的乙酸丁酯,0.5小时滴完。最后升温至99℃,恒温2小时,冷却至室温后结束反应得到目标聚合物溶液。
配制石材防护剂:以质量份数计,将将5份氟硅丙烯酸树脂溶液、10份乙基三乙氧基硅烷、15份辛基三乙氧基硅烷、5份羟基硅油、63份60#溶剂油、2份正硅酸乙酯均匀混合。
实施例4
制备树脂溶液:制备方法同实施例1
配制石材防护剂:以质量份数计,将12份氟硅丙烯酸树脂溶液、20份乙基三乙氧基硅烷、20份十二烷基三乙氧基硅烷、3份端羟基硅油、44份乙酸乙酯溶剂、1份新癸酸铋均匀混合。
图1为实施例1与4中树脂分子的红外吸收光谱测试图。如图1所示,3050cm-1附近未出现吸收峰,说明溶液中不存在C=C结构,所有单体均参与聚合,所得溶液为聚合物溶液;3529cm-1为-OH的特征吸收峰,结合合成过程,证明有甲基丙烯酸羟丙酯参与聚合;802cm-1为Si-CH3的特征吸收峰,结合合成过程,证明有DCA2208参与聚合;1024cm-1~1260cm-1为Si-O、C-F、C-C等多种结构的特征吸收峰重叠后形成的谱带,结合合成过程与接触角测试结果,可以说明有全氟己基乙基甲基丙烯酸酯参与聚合;1732cm-1为C=O的特征吸收峰,证明了酯基的存在;2963cm-1与1455cm-1为-CH2-与-CH3的特征吸收峰,是聚合后形成的碳链、甲基丙烯酸辛酯聚合后侧基上的辛基与甲基丙烯酸乙酯聚合后侧基上的乙基的吸收峰。综上所述,在实施例1和4中,成功制备了含氟硅共聚丙烯酸树脂的溶液。
实施例5
制备树脂溶液:制备方法同实施例2
配制石材防护剂:以质量份数计,将15份氟硅丙烯酸树脂溶液、15份甲基三乙氧基硅烷、30份辛基三乙氧基硅烷、38份6#溶剂油、2份异辛酸铋均匀混合。
图2为实施例2与5中树脂分子的红外吸收光谱测试图。如2所示,3050cm-1附近未出现吸收峰,说明溶液中不存在C=C结构,所有单体均参与聚合,所得溶液为聚合物溶液;3532cm-1为-OH的特征吸收峰,结合合成过程,证明有甲基丙烯酸羟乙酯参与聚合;800cm-1为Si-CH3的特征吸收峰,结合合成过程,证明有反应型爽滑改性单体SPS参与聚合;1025cm-1~1248cm-1为Si-O、C-F、C-C等多种结构的特征吸收峰重叠后形成的谱带,结合合成过程与接触角测试结果,可以说明有全氟己基乙基甲基丙烯酸酯参与聚合;1733cm-1为C=O的特征吸收峰,证明了酯基的存在;2963cm-1与1470cm-1为-CH2-与-CH3的特征吸收峰,是聚合后形成的碳链、甲基丙烯酸甲酯聚合后侧基上的甲基与甲基丙烯酸月桂酯聚合后侧基上的十二烷基的吸收峰。综上所述,在实施例2和5中,成功制备了含氟硅共聚丙烯酸树脂的溶液。
实施例6
制备树脂溶液:制备方法同实施例3
配制石材防护剂:以质量份数计,将20份氟硅丙烯酸树脂溶液、15份甲基三乙氧基硅烷、25份辛基三乙氧基硅烷、5份羟基硅油、34份乙酸乙酯溶剂、1份环烷酸铋均匀混合。
图3为实施例3与6中树脂分子的红外吸收光谱测试图。如图3所示,3050cm-1附近未出现吸收峰,说明溶液中不存在C=C结构,所有单体均参与聚合,所得溶液为聚合物溶液;3546cm-1为-OH的特征吸收峰,结合合成过程,证明有甲基丙烯酸羟乙酯参与聚合;801cm-1为Si-CH3的特征吸收峰,结合合成过程,证明有DCA2206参与聚合;1024cm-1~1258cm-1为Si-O、C-F、C-C等多种结构的特征吸收峰重叠后形成的谱带,结合合成过程与接触角测试结果,可以说明有全氟己基乙基甲基丙烯酸酯参与聚合;1734cm-1为C=O的特征吸收峰,证明了酯基的存在;2963cm-1与1455cm-1为-CH2-与-CH3的特征吸收峰,是聚合后形成的碳链与甲基丙烯酸异冰片酯聚合后侧基上的异冰片基的吸收峰。综上所述,在实施例3和6中,成功制备了含氟硅共聚丙烯酸树脂的溶液。
防水防油性能实验
将各实施例配制的石材防护剂用乙酸乙酯稀释15倍后分别喷涂至干净的大理石与花岗岩表面,室温放置24小时后根据标准GB/T 24368-2009进行接触角测试,接触角越大则防水防油效果越好。测试结果如表1、表2所示:
表1.大理石表面的接触角测试结果
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | |
水接触角 | 139 | 144 | 149 | 145 | 150 | 153 |
十六烷接触角 | 81 | 84 | 89 | 84 | 90 | 91 |
表2.花岗岩表面的接触角测试结果
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | |
水接触角 | 143 | 150 | 152 | 151 | 155 | 157 |
十六烷接触角 | 86 | 90 | 91 | 90 | 92 | 94 |
根据中华人民共和国国家标准GB/T32837-2016《天然石材防护剂》对上述各实施例进行石材防护测试,测试所用石材为G3503天然花岗岩;测试结果如表3所示:
表3.根据GB/T32837-2016进行石材防护测试所得的测试结果
从接触角实验结果可以看出,处理后,大理石表面的水接触角为139~153°,高于中国发明专利CN 104017488 A中的100~120°;花岗岩的水接触角为143~157°,高于中国发明专利CN 104017488 A中的121~126°。
SSL1~SSL6分别代表实施例1~实施例6中配制的石材防护剂;按照GB/T32837-2016的测试的表3结果可以看出,本发明的饰面型石材防护剂满足标准中规定的饰面型防护剂的技术要求:使用防护剂后,石材颜色基本不变;pH在5~11之间;无分层、漂油和沉淀;防水性>80%;毛细吸水下降率>85%;耐污实验中石材表面无污染;耐酸性、耐碱性与耐紫外老化性均>55%;属于较好的A级防护剂。
本发明中的氟硅共聚树脂属于丙烯酸树脂,透光性好,其他组份也不会改变石材的颜色,因此使用该防护剂后,石材颜色基本不变。氟碳链的存在让该树脂的拒油能力好于有机硅石材防护剂,长硅氧烷侧链的存在又使得该树脂拥有媲美全氟辛基的疏水拒油效果。
本发明通过在树脂分子链上引入相对较长的硅氧烷链,规避了全氟烷基(CnF2n+1-,n≥8)的生物危害性,并使得改性后的树脂拥有了媲美含全氟辛基的树脂的疏水拒油效果;将该树脂按本发明的方法配置成饰面型石材防护剂后,测试结果表明,对于大理石与花岗岩,本发明的石材防护剂均有较好的防水拒油效果,根据GB/T32837-2016本发明的防护剂属于A级防护剂,能较好地用于饰面石材的防护。
需要说明的是,对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下做出若干替代或明显变型的实施例,这些都应当视为属于本发明的保护范围内。
Claims (10)
1.一种基于氟硅丙烯酸树脂的饰面型石材防护剂,其特征在于,按照重量份数计,其由以下的原料组分构成:
氟硅丙烯酸树脂溶液5~20份;
硅烷偶联剂10~50份;
端羟基硅油1~10份;
稀释剂20~85份
催化剂0.5~2份
所述的氟硅丙烯酸树脂溶液的合成方法:将占溶剂总量60~80wt%的有机溶剂加热到65~90℃,加入占引发剂总量50~85wt%的引发剂,得含有引发剂的溶液;将含氟丙烯酸酯单体、单端丙烯酸改性的有机硅单体、丙烯酸酯单体、丙烯酸酯交联单体与占有机溶剂总量10~20wt%的有机溶剂均匀混合后,得混合溶液;所述的含氟丙烯酸酯单体为全氟己基乙基甲基丙烯酸酯或全氟己基乙基丙烯酸酯;
向含有引发剂的溶液中滴加所述的混合溶液,滴加时间为2~4小时,滴加完后保温0.5~2小时;将剩余的有机溶剂与剩余的引发剂均匀混合,得含引发剂的有机溶剂;向保温结束的溶液中滴加所述的含引发剂的有机溶剂,滴加时间为0.5~1小时;最后升温至95~100℃,恒温1~2小时,冷却至室温后得到氟硅共聚丙烯酸树脂溶液;
单端丙烯酸改性的有机硅单体的结构式为:
其中R1为-CH3或-H;R2为-CH2-或-COO-;R3为-Si(CH3)3或-Si(CH3)2OCH3;m=0~3,n=10~25,单端丙烯酸改性的有机硅单体的数均分子量为500~2000。
2.根据权利要求1所述的基于氟硅丙烯酸树脂的饰面型石材防护剂,其特征在于,所述的氟硅丙烯酸树脂溶液的合成方法中,各反应单体按占总单体重量百分比计,其单体组份为:含氟丙烯酸酯单体45~65%、单端丙烯酸改性的有机硅单体体15~25%、丙烯酸酯单体18~28%、丙烯酸酯交联单体2~5%;总单体占总反应体系的重量百分数为25~35%。
3.根据权利要求1所述的基于氟硅丙烯酸树脂的饰面型石材防护剂,其特征在于,所述的丙烯酸酯单体为甲基丙烯酸甲酯、甲基丙烯酸异冰片酯、甲基丙烯酸辛酯、甲基丙烯酸月桂酯、甲基丙烯酸十八酯、甲基丙烯酸苯氧乙酯、甲基丙烯酸苄基酯和甲基丙烯酸环己酯中的一种或多种;
所述的丙烯酸酯交联单体为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯和甲基丙烯酸羟丁酯中的一种或多种。
4.根据权利要求1所述的基于氟硅丙烯酸树脂的饰面型石材防护剂,其特征在于,所述的硅烷偶联剂为甲基三乙氧基硅烷、甲基三甲氧基硅烷、乙基三乙氧基硅烷、乙基三甲氧基硅烷、丙基三乙氧基硅烷、丙基三甲氧基硅烷、甲基三异丙氧基硅烷、辛基三乙氧基硅烷、辛基三甲氧基硅烷、十二烷基三甲氧基硅烷、十二烷基三乙氧基硅烷十六烷基三甲氧基硅烷和十六烷基三乙氧基硅烷中的一种或多种。
5.根据权利要求1所述的基于氟硅丙烯酸树脂的饰面型石材防护剂,其特征在于,所述的催化剂为异辛酸锡、月桂酸二丁基锡、二醋酸二丁基锡、新癸酸铋、月桂酸铋、异辛酸铋、环烷酸铋、正硅酸乙酯、钛酸正丁酯和钛酸异丙酯中的一种或多种。
6.根据权利要求1所述的基于氟硅丙烯酸树脂的饰面型石材防护剂,其特征在于,所述的引发剂为偶氮二异丁腈、偶氮二异庚腈、过氧化二苯甲酰中的一种或多种;
所述的有机溶剂为乙酸丁酯、甲基异丁基甲酮中、乙二醇二乙醚和乙二醇甲醚醋酸酯的一种或多种。
7.根据权利要求1所述的基于氟硅丙烯酸树脂的饰面型石材防护剂,其特征在于,所述的端羟基硅油为粘度介于25~30CP之间的低分子量端羟基聚二甲基硅氧烷。
8.根据权利要求1所述的基于氟硅丙烯酸树脂的饰面型石材防护剂,其特征在于,所述的稀释剂为乙酸乙酯、乙酸丁酯、甲基异丁基酮或溶剂油。
9.根据权利要求8所述的基于氟硅丙烯酸树脂的饰面型石材防护剂,其特征在于,所述的溶剂油为D30、D40、D60、6#、120#、S100和S150中的一种或多种。
10.权利要求1-9任一项所述的基于氟硅丙烯酸树脂的饰面型石材防护剂的制备方法,其特征在于,将氟硅共聚树脂溶液、硅烷偶联剂、羟端基硅油、稀释剂和催化剂均匀混合后,喷涂在石材表面。
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