CN106167630A - 一种抗菌耐水纳米二氧化硅包覆改性薄片铝粉颜料及其制备方法 - Google Patents
一种抗菌耐水纳米二氧化硅包覆改性薄片铝粉颜料及其制备方法 Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000004411 aluminium Substances 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 title claims abstract description 39
- 239000000049 pigment Substances 0.000 title claims abstract description 25
- 239000011248 coating agent Substances 0.000 title claims abstract description 14
- 238000000576 coating method Methods 0.000 title claims abstract description 14
- 230000004048 modification Effects 0.000 title claims abstract description 13
- 238000012986 modification Methods 0.000 title claims abstract description 13
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 11
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- SCCKYHTXTNPYES-UHFFFAOYSA-N [La].C(C(=C)CC(=O)O)(=O)O Chemical compound [La].C(C(=C)CC(=O)O)(=O)O SCCKYHTXTNPYES-UHFFFAOYSA-N 0.000 claims abstract description 13
- UYEKHXLXNOJAAG-UHFFFAOYSA-N azanium silver fluoride Chemical compound [Ag].[F-].[NH4+] UYEKHXLXNOJAAG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000004224 protection Effects 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims 2
- 150000002978 peroxides Chemical class 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000003115 biocidal effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000003471 anti-radiation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- ZYMPIVZAUGZPKC-UHFFFAOYSA-N carbonic acid guanidine Chemical compound C(O)(O)=O.NC(=N)N.C(O)(O)=O.NC(=N)N ZYMPIVZAUGZPKC-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
- C09C1/648—Aluminium treated with inorganic and organic, e.g. polymeric, compounds
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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Abstract
本发明公开了一种抗菌耐水纳米二氧化硅包覆改性薄片铝粉颜料,由下列重量份的原料制成:铝颜料2‑2.3、TEOS 3‑3.5、氨水4.5‑5、无水乙醇适量、蒸馏水5‑5.5、氟化氨银0.4‑0.5、衣康酸镧0.6‑0.8、碳酸胍0.2‑0.3、纳米ZnWO40.3‑0.4、丙烯酸三氟乙酯0.4‑0.5、过氧化异丙苯0.03‑0.04。本发明通过使用氟化氨银、衣康酸镧、碳酸胍进行混合改性,使得氟化氨银的表面接枝上衣康酸镧,不仅提高了氟化氨银与铝粉包膜的相容性,提高了铝粉的耐水性,减缓腐蚀;还具有良好的抗菌性,而且衣康酸镧还能提高包覆膜的耐热性。
Description
技术领域
本发明涉及铝粉颜料技术领域,尤其涉及一种抗菌耐水纳米二氧化硅包覆改性薄片铝粉颜料及其制备方法。
背景技术
薄片(0.1~1μm厚,5~50μm长或宽)金属铝颜料由于具有特殊的随角异色光学效应和金属光泽, 广泛应用于汽车涂料、工业涂料、印刷油墨及塑料加
工业中。但铝为两性活性金属, 接触酸碱溶液或者空气中的O2 极容易发生氧化而变黑, 影响其金属光泽, 还会产生大量的H2 , 影响其贮存稳定性。
提高铝粉的贮存稳定性, 防止铝粉表面被氧化,有效的方法是在铝粉微粒表面进行改性, 表面吸附一层腐蚀抑制剂或者微胶囊包覆一层惰性层, 隔绝铝与氧、水的直接接触。相比于吸附有机腐蚀抑制剂, 在铝粉表面形成一层薄而致密的钝化铬层或者SiO2 层等无机层, 具有非常好的抗氧化耐腐蚀性能 .Y .Iriyama 以正硅酸乙酯(TEOS)为前驱体, 采用等离子体聚合法在铝粉粒子表面包覆了一层SiO2 层。溶胶凝胶法因反应温度低、工艺及设备简单, 具有较广的工业应用价值。Ralf Supplit 和Ul rich Schubert 采用磷酸催化正硅酸乙酯水解对铝粉进行第一层包覆, 再用十六烷基三甲氧基硅烷或二甲基二甲氧基硅烷水解进行第二层包覆, 包覆铝粉在热水和pH =9 的碱液中具有较好的稳定性。Liu Hui 等采用甲基丙烯酰氧丙基三甲氧基硅烷对铝粉进行预处理, 再采用原位乳液聚合的方法包覆聚甲基丙烯酸甲酯。李利君等采用TEOS对薄片铝粉进行了纳米SiO2 包覆,采用TEOS和乙烯基三乙氧基硅烷同时水解对铝粉进行了杂化的纳米SiO2 包覆, 并在此基础上采用聚合物进行第二层包覆, 包覆铝粉在pH =11 的碱液中能稳定存在30 d 。Jostein Mardalen 等发现包覆硅的形态和包覆度对包覆铝粉的化学稳定性的影响比包覆硅的厚度的影响更重要。
《纳米SiO2 包覆改性薄片铝粉颜料及其耐酸性研究》一文以TEOS 为前驱体, 采用溶胶-凝胶法制备SiO2 包覆的铝粉颜料(Al/SiO2), 详细考察反应温度、反应时间、铝硅比(S =nAl/nTEOS)、水硅比(R =nH2O /nTEOS)及催化剂用量等工艺条件对包覆层形态和产品耐酸性的影响。
但是用纳米SiO2 包覆改性的薄片铝粉颜料光亮度下降,需要改进。而且铝粉颜料的耐腐蚀性、耐热性、防辐射性、耐紫外性、耐水性、耐老化性、抗菌性、耐腐蚀性、防划痕性、稳定性、散热性等性能也需要进一步的提升。
发明内容
本发明目的就是为了弥补已有技术的缺陷,提供一种抗菌耐水纳米二氧化硅包覆改性薄片铝粉颜料及其制备方法。
本发明是通过以下技术方案实现的:
一种抗菌耐水纳米二氧化硅包覆改性薄片铝粉颜料,由下列重量份的原料制成:铝颜料2-2.3、TEOS 3-3.5、氨水4.5-5、无水乙醇适量、蒸馏水5-5.5、氟化氨银0.4-0.5、衣康酸镧0.6-0.8、碳酸胍0.2-0.3、纳米ZnWO40.3-0.4、丙烯酸三氟乙酯0.4-0.5、过氧化异丙苯0.03-0.04。
所述的抗菌耐水纳米二氧化硅包覆改性薄片铝粉颜料的制备方法,包括以下步骤:
(1)将氟化氨银、衣康酸镧、碳酸胍混合,加热至60℃,研磨均匀,冷却后与纳米ZnWO4与30-35重量份的无水乙醇混合,超声分散5-10分钟,再加入丙烯酸三氟乙酯、过氧化异丙苯加热至40-45℃,搅拌反应30-40分钟,再加入TEOS,搅拌均匀,得到混合物;
(2)将铝颜料和50-55重量份的无水乙醇混合,在氮气保护下搅拌1-1.2h,然后升温至40-45℃,得到浆料;
(3)将氨水与30重量份的无水乙醇及蒸馏水混合均匀,与第(1)步得到的混合物同时滴加到第(2)得到的浆料中,控制滴加速度为1滴/秒,滴加完毕后,在40-43℃下反应6-6.5h,停止反应,真空抽滤,用无水乙醇洗涤产物3次,干燥即得。
本发明的优点是:本发明使用纳米ZnWO4、丙烯酸三氟乙酯对铝颜料进行改性,ZnWO4包覆在铝粉表面提高了铝粉的光亮性和耐腐性,丙烯酸三氟乙酯提高了铝粉的耐水性和致密性,减少空气氧化,提高了铝粉的漂浮性;通过使用氟化氨银、衣康酸镧、碳酸胍进行混合改性,使得氟化氨银的表面接枝上衣康酸镧,不仅提高了氟化氨银与铝粉包膜的相容性,提高了铝粉的耐水性,减缓腐蚀;还具有良好的抗菌性,而且衣康酸镧还能提高包覆膜的耐热性。
具体实施方式
一种抗菌耐水纳米二氧化硅包覆改性薄片铝粉颜料,由下列重量份(公斤)的原料制成:铝颜料2、TEOS 3、氨水4.5、无水乙醇适量、蒸馏水5、氟化氨银0.4、衣康酸镧0.6、碳酸胍0.2、纳米ZnWO4 0.3、丙烯酸三氟乙酯0.4、过氧化异丙苯0.03。
所述的抗菌耐水纳米二氧化硅包覆改性薄片铝粉颜料的制备方法,包括以下步骤:
(1)将氟化氨银、衣康酸镧、碳酸胍混合,加热至60℃,研磨均匀,冷却后与纳米ZnWO4与30重量份的无水乙醇混合,超声分散5分钟,再加入丙烯酸三氟乙酯、过氧化异丙苯加热至40℃,搅拌反应30分钟,再加入TEOS,搅拌均匀,得到混合物;
(2)将铝颜料和50重量份的无水乙醇混合,在氮气保护下搅拌1h,然后升温至40℃,得到浆料;
(3)将氨水与30重量份的无水乙醇及蒸馏水混合均匀,与第(1)步得到的混合物同时滴加到第(2)得到的浆料中,控制滴加速度为1滴/秒,滴加完毕后,在40℃下反应6h,停止反应,真空抽滤,用无水乙醇洗涤产物3次,干燥即得。
本实施例铝粉颜料在显微镜观察下,铝粉表面具有致密的包覆膜,而且具有荧光亮点,比表面积为10.81cm2/g.铝粉在pH =1 的酸溶液中能稳定存在30 d 而不产生H2。
Claims (2)
1.一种抗菌耐水纳米二氧化硅包覆改性薄片铝粉颜料,其特征在于由下列重量份的原料制成:铝颜料2-2.3、TEOS 3-3.5、氨水4.5-5、无水乙醇适量、蒸馏水5-5.5、氟化氨银0.4-0.5、衣康酸镧0.6-0.8、碳酸胍0.2-0.3、纳米ZnWO40.3-0.4、丙烯酸三氟乙酯0.4-0.5、过氧化异丙苯0.03-0.04。
2.根据权利要求1所述的抗菌耐水纳米二氧化硅包覆改性薄片铝粉颜料的制备方法,其特征在于包括以下步骤:
(1)将氟化氨银、衣康酸镧、碳酸胍混合,加热至60℃,研磨均匀,冷却后与纳米ZnWO4与30-35重量份的无水乙醇混合,超声分散5-10分钟,再加入丙烯酸三氟乙酯、过氧化异丙苯加热至40-45℃,搅拌反应30-40分钟,再加入TEOS,搅拌均匀,得到混合物;
(2)将铝颜料和50-55重量份的无水乙醇混合,在氮气保护下搅拌1-1.2h,然后升温至40-45℃,得到浆料;
(3)将氨水与30重量份的无水乙醇及蒸馏水混合均匀,与第(1)步得到的混合物同时滴加到第(2)得到的浆料中,控制滴加速度为1滴/秒,滴加完毕后,在40-43℃下反应6-6.5h,停止反应,真空抽滤,用无水乙醇洗涤产物3次,干燥即得。
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