CN105400315A - 一种改性纳米氟碳涂料及其制备方法 - Google Patents
一种改性纳米氟碳涂料及其制备方法 Download PDFInfo
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 44
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 24
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 15
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
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- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 20
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- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 abstract description 12
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract 2
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- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
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- UCSUOYMTZRJAIH-UHFFFAOYSA-N iron(2+) oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Fe+2] UCSUOYMTZRJAIH-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
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- -1 phenol amino alcohol Chemical class 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
本发明公开了一种改性纳米氟碳涂料，所述涂料的基料由以下原料按照重量配比制成：三氟氯乙烯40-60份、二异氰酸酯10-15份、特丁基过氧化氢0-10份、偶氮二异丁腈0-10份、三氟一氯乙烷2-5份、正十二烷基硫醇0-8份、叔十二烷基醇2-4份、乙二醇1-3份、全氟辛酸铵1-3份以及改性纳米SiO2？2-8份，其中特丁基过氧化氢和偶氮二异丁腈总量不超过10份，正十二烷基硫醇和叔十二烷基醇总量不超过8份，引入改性纳米SiO2可以使得其与氟碳树脂的交联聚合能力增加，提高其在氟碳涂料中的相容性能和分散性能，同时使改性纳米SiO2表面的有机基团和氟碳涂料中有机物共同聚合，形成具有机/无机杂化网络结构的固化膜，纳米SiO2作为刚性粒子，对氟碳涂料固化膜的机械性能起着增强作用。
Description
技术领域
本发明涉及一种改性纳米氟碳涂料及其制备方法。
背景技术
氟碳涂料是指以氟树脂为主要成膜物质的涂料，氟树脂又称氟碳树脂，由于氟原子结构上的特点，将其引入到树脂中使得含氟树脂具有不同于其他树脂的特殊性能。在各种涂料之中，氟树脂涂料由于引入的氟元素电负性大，碳氟键能强，具有特别优越的各项性能。耐候性、耐热性、耐低温性、耐化学药品性，而且具有独特的不粘性和低摩擦性。经过几十年的快速发展，氟碳涂料在建筑、化学工业、电器电子工业、机械工业、航空航天产业、家庭用品的各个领域得到广泛应用。随着氟碳涂料的应用日益广泛，对其组分进行改进以期获得更加性能优越的涂层成为研究方向。
众所周知，纳米材料与有机涂料相结合具有突出的特性，但纳米SiO2粒径小，比表面积大，亲水性能强，亲油性能差，在有机涂料中易团聚，难以均匀分散，限制了其优异性能的发挥。因此，对纳米SiO2改性以提高其和有机材料的相容性能，成为制备优异化工涂料的关键。
纳米SiO2的改性主要有物理改性和化学改性两种方法。物理改性是通过纳米SiO2对有机物的吸附，将有机物包覆在纳米SiO2表面，这种改性方法在氟碳涂料用纳米SiO2制备方面应用性能不好。而化学改性法则是利用纳米SiO2表面含Si-OH的特点，通过和有机物质的化学反应将有机化合物或聚合物以化学键的形式接枝于纳米SiO2表面，使亲水的Si-OH基团转化为亲油的Si-OR基团。该改性方法不仅可以提高纳米SiO2在有机物的相容性能，减少其在涂料中的团聚现象，还可以赋予涂料以高强度性、自洁性或交联聚合等特性。
经专利检索可发现如下现有技术，专利申请号为200610045717的专利公开了一种纳米锌铝改性环氧-氟碳涂料，包括底涂料、面涂料；底涂料是由以下组成：环氧树脂80-100份，有机硅树脂20-30份，纳米锌粉1-2份，亚微米锌粉4-6份，混合后的溶剂20-30份，酚氨基醇50-67份，混合而成；面涂料是由以下组成：树脂90-100份，二甲苯20-25份，亚微米铝粉2-5份，醋酸丁酯70-75份，纳米铝粉1-2份，二丁基二月桂酸锡0.00035份，颜料15-20份，异氰酸脂三聚体9-9.5份，混合而成。
专利申请号为201310621457公开了一种水性氟碳涂料，由以下质量百分比的原料配方组分组成：30-40％水性氟碳乳液、5-10％纤维素、2-5％淀粉、1-5％板钛矿型钛白粉、2-5％耐磨粉、1-5％纳米而氧化铝、1-5％纳米二氧化钛、1-5％纳米二氧化铁、1-5％纳米氧化碳、1-5％纳米氧化铜、1-5％纳米氧化镁、1-5％纳米氧化锌、余量为去离子水。水性氟碳涂料中不含苯、甲苯、二甲苯和乙苯和游离二异氰酸酯等有害物质，无毒、无污染，兼具涂料的装饰功能和保护功能，制得的漆膜具有优良的耐磨性、耐候性。目前对的纳米SiO2改性方法较多，但还未发现适用于氟碳树脂添加使用的改性纳米材料。
发明内容
本发明的目的在于提供一种改性纳米氟碳涂料及其制备方法，其。
本发明的技术方案为：
一种改性纳米氟碳涂料，所述涂料的基料由以下原料按照重量配比制成：三氟氯乙烯40-60份、二异氰酸酯10-15份、特丁基过氧化氢0-10份、偶氮二异丁腈0-10份、三氟一氯乙烷2-5份、正十二烷基硫醇0-8份、叔十二烷基醇2-4份、乙二醇1-3份、全氟辛酸铵1-3份，其中特丁基过氧化氢和偶氮二异丁腈总量不超过10份，正十二烷基硫醇和叔十二烷基醇总量不超过8份。
同时将由以下方法制成的改性纳米SiO22-8份加入上述制备出的氟碳树脂中得出本发明的改性纳米氟碳涂料。
该氟碳涂料的制备方法可使用单反应釜间歇聚合方式生产，具体将三氟氯乙烯40-60份、二异氰酸酯10-15份放入反应釜中，引入引发剂、溶剂和调节剂等：特丁基过氧化氢0-10份、偶氮二异丁腈0-10份、三氟一氯乙烷2-5份、正十二烷基硫醇0-8份、叔十二烷基醇2-4份、乙二醇1-3份，添加表面活性剂全氟辛酸铵1-3份，加压环境中，加热至70℃左右，搅拌保温充分反应6h以上，其中特丁基过氧化氢和偶氮二异丁腈总量不超过10份，正十二烷基硫醇和叔十二烷基醇总量不超过8份。可选择地加入分散剂、消泡剂、成膜剂、保湿剂等助剂。
与现有技术相比，本发明将三氟氯乙烯作为主反应物、引入二异氰酸酯作为非含氟单体从而降低其熔融温度，改善氟碳树脂的交联固化特性，降低氟碳树脂成本，将其与含氟单体进行共聚；引发剂选择使用特丁基过氧化氢和偶氮二异丁腈组合物，且控制其总量不超过一定量，其能够大大降低合成成本，提高单体合成率；引入正十二烷基硫醇和叔十二烷基醇组合物可以对相对分子质量进行调节，相比于单纯的粘度调剂或链转移更为有效；关键在于引入改性纳米SiO2可以使得其与氟碳树脂的交联聚合能力增加，提高其在氟碳涂料中的相容性能和分散性能，同时使改性纳米SiO2表面的有机基团和氟碳涂料中有机物共同聚合，形成具有机/无机杂化网络结构的固化膜，纳米SiO2作为刚性粒子，对氟碳涂料固化膜的机械性能起着增强作用，可以提高氟碳树脂的亲水性和自洁抗污染能力，同时还提高了涂料涂层的强度和抗腐蚀能力。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。
一种改性纳米氟碳涂料，所述涂料的基料由以下原料按照重量配比制成：三氟氯乙烯40-60份、二异氰酸酯10-15份、特丁基过氧化氢0-10份、偶氮二异丁腈0-10份、三氟一氯乙烷2-5份、正十二烷基硫醇0-8份、叔十二烷基醇2-4份、乙二醇1-3份、全氟辛酸铵1-3份以及改性纳米SiO22-8份，其中特丁基过氧化氢和偶氮二异丁腈总量不超过10份，正十二烷基硫醇和叔十二烷基醇总量不超过8份。
该氟碳涂料的制备方法可使用单反应釜间歇乳液聚合方式生产，具体将三氟氯乙烯40-60份、二异氰酸酯10-15份放入反应釜中，引入引发剂、溶剂和调节剂等：特丁基过氧化氢0-10份、偶氮二异丁腈0-10份、三氟一氯乙烷2-5份、正十二烷基硫醇0-8份、叔十二烷基醇2-4份、乙二醇1-3份，添加表面活性剂全氟辛酸铵1-3份，可选择地加入分散剂、消泡剂、成膜剂、保湿剂等助剂，加压环境中，加热至70℃左右，搅拌保温充分反应6h以上，其中特丁基过氧化氢和偶氮二异丁腈总量不超过10份，正十二烷基硫醇和叔十二烷基醇总量不超过8份。
该改性纳米SiO2的制备方法如下：在四口反应容器中将15重量份的纳米SiO2搅拌分散在200重量份的二甲苯中，缓慢依次加入30重量份的丙烯酸羟乙酯，0.5-1重量份的对甲苯磺酸和0.2重量份的对苯二酚，升温至80-90℃至回流，保温反应至无水生成后，继续反应3h，然后在真空环境中过滤，所得产物用甲苯洗涤3次以上，后用去离子水洗涤三次以上，置于50℃的鼓风干燥箱中干燥24小时得白色粉状固体。由上述方法进行对纳米SiO2的改性可以使得其与氟碳树脂的交联聚合能力增加，提高其在氟碳涂料中的相容性能和分散性能，同时使改性纳米SiO2表面的有机基团和氟碳涂料中有机物共同聚合，形成具有机/无机杂化网络结构的固化膜，纳米SiO2作为刚性粒子，对氟碳涂料固化膜的机械性能起着增强作用，从而改善了氟碳涂料的耐污性、抗老化性能以及耐腐蚀性能。
实施例1
一种改性纳米氟碳涂料，所述涂料的基料由以下原料按照重量配比制成：三氟氯乙烯40份、二异氰酸酯10份、特丁基过氧化氢2份、偶氮二异丁腈8份、三氟一氯乙烷2份、正十二烷基硫醇3份、叔十二烷基醇2份、乙二醇1份、全氟辛酸铵1份以及改性纳米SiO22份。制备方法如前所述。
实施例2
一种改性纳米氟碳涂料，所述涂料的基料由以下原料按照重量配比制成：三氟氯乙烯40份、二异氰酸酯10份、特丁基过氧化氢2份、偶氮二异丁腈8份、三氟一氯乙烷2份、正十二烷基硫醇6份、叔十二烷基醇2份、乙二醇1份、全氟辛酸铵1份以及改性纳米SiO24份。制备方法如前所述。
实施例3
一种改性纳米氟碳涂料，所述涂料的基料由以下原料按照重量配比制成：三氟氯乙烯50份、二异氰酸酯15份、特丁基过氧化氢8份、偶氮二异丁腈2份、三氟一氯乙烷3份、正十二烷基硫醇4份、叔十二烷基醇4份、乙二醇3份、全氟辛酸铵1份以及改性纳米SiO24份。制备方法如前所述。
实施例4
一种改性纳米氟碳涂料，所述涂料的基料由以下原料按照重量配比制成：三氟氯乙烯60份、二异氰酸酯15份、特丁基过氧化氢8份、偶氮二异丁腈2份、三氟一氯乙烷4份、正十二烷基硫醇6份、叔十二烷基醇2份、乙二醇3份、全氟辛酸铵2份以及改性纳米SiO26份。制备方法如前所述。
实施例5
一种改性纳米氟碳涂料，所述涂料的基料由以下原料按照重量配比制成：三氟氯乙烯60份、二异氰酸酯15份、特丁基过氧化氢8份、偶氮二异丁腈2份、三氟一氯乙烷4份、正十二烷基硫醇6份、叔十二烷基醇2份、乙二醇2份、全氟辛酸铵2份以及改性纳米SiO28份。制备方法如前所述。
对比实施例1
一种氟碳涂料，所述涂料由以下原料按照重量配比制成：三氟氯乙烯60份、二异氰酸酯15份、特丁基过氧化氢8份、偶氮二异丁腈2份、三氟一氯乙烷4份、正十二烷基硫醇6份、叔十二烷基醇2份、乙二醇2份、全氟辛酸铵2份。制备方法如前所述。
对比实施例2
一种氟碳涂料，所述涂料由以下原料按照重量配比制成：三氟氯乙烯50份、二异氰酸酯15份、特丁基过氧化氢8份、偶氮二异丁腈2份、三氟一氯乙烷3份、正十二烷基硫醇4份、叔十二烷基醇4份、乙二醇3份、全氟辛酸铵1份。制备方法如前所述。
将上述实施例1-5和对比实施例1-2得到的涂料效果参数比较如下：
实施例1-5和对比实施例1-2性能测试结果对比分析表
尽管上文对本发明的具体实施方式给予了详细描述和说明，但是应该指明的是，我们可以依据本发明的构想对上述实施方式进行各种等效改变和修改，其所产生的功能作用仍未超出说明书所涵盖的精神时，均应在本发明的保护范围之内。例如，重量份可以选择为克或其他重量单位。以上所述，仅为本发明的较佳实施例，并不用以限制本发明，凡是依据本发明的技术实质对以上实施例所作的任何细微修改、等同替换和改进，均应包含在本发明技术方案的保护范围之内。
Claims (2)
1.一种改性纳米氟碳涂料，所述涂料的基料由以下原料按照重量配比制成：三氟氯乙烯40-60份、二异氰酸酯10-15份、特丁基过氧化氢0-10份、偶氮二异丁腈0-10份、三氟一氯乙烷2-5份、正十二烷基硫醇0-8份、叔十二烷基醇2-4份、乙二醇1-3份、全氟辛酸铵1-3份以及改性纳米SiO228份，其中特丁基过氧化氢和偶氮二异丁腈总量不超过10份，正十二烷基硫醇和叔十二烷基醇总量不超过8份。
2.一种如权利要求1所述涂料的制备方法如下：可使用单反应釜间歇聚合方式生产，具体将三氟氯乙烯40-60份、二异氰酸酯10-15份放入反应釜中，引入引发剂、溶剂和调节剂：特丁基过氧化氢0-10份、偶氮二异丁腈0-10份、三氟一氯乙烷2-5份、正十二烷基硫醇0-8份、叔十二烷基醇2-4份、乙二醇1-3份，添加表面活性剂全氟辛酸铵1-3份，加压环境中，加热至70℃左右，搅拌保温充分反应6h以上，其中特丁基过氧化氢和偶氮二异丁腈总量不超过10份，正十二烷基硫醇和叔十二烷基醇总量不超过8份。
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