CN105623643A - 一种复合荧光颜料的制备方法 - Google Patents
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- 239000000049 pigment Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
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- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 29
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
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- NOFPXGWBWIPSHI-UHFFFAOYSA-N 2,7,9-trimethylacridine-3,6-diamine;hydrochloride Chemical compound Cl.CC1=C(N)C=C2N=C(C=C(C(C)=C3)N)C3=C(C)C2=C1 NOFPXGWBWIPSHI-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005046 Chlorosilane Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- DBZJJPROPLPMSN-UHFFFAOYSA-N bromoeosin Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C(O)C(Br)=C1OC1=C(Br)C(O)=C(Br)C=C21 DBZJJPROPLPMSN-UHFFFAOYSA-N 0.000 claims description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- WENLKAKVZDPNQX-UHFFFAOYSA-N methanetetrol silicic acid Chemical compound C(O)(O)(O)O.[Si](O)(O)(O)O WENLKAKVZDPNQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 4
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- 238000001179 sorption measurement Methods 0.000 abstract 1
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- 238000000498 ball milling Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0007—Coated particulate pigments or dyes with inorganic coatings
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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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
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Abstract
一种复合荧光颜料的制备方法。将有机荧光染料溶于水或有机溶剂中，加入改性处理过的海泡石吸附，研磨、焙烧处理后，再将所得材料分散于水溶液或有机溶剂中，加入硅类化合物和催化剂进行反应，反应温度不高于100℃，反应完全后冷却过滤、洗涤、干燥得到海泡石基复合荧光颜料；其中海泡石的改性处理包括盐酸活化改性处理，或先盐酸活化后再经350℃～450℃高温改性处理，或先盐酸活化后再经十六烷基三甲基溴化铵改性处理。本发明方法制备的荧光颜料除具有其应有的荧光性能外，还具有较强的耐酸碱、耐有机溶剂、耐热、和抗紫外老化性等性能。本发明方法具有合成设备简单，无污染，成本投入少。可广泛应用于工业，广告牌、各种安全标记、服装、印刷油墨、油漆、涂料、塑料等方面。
Description
技术领域
本发明涉及一种复合荧光颜料的制备方法。
背景技术
有机荧光颜料亦称日光荧光颜料，具有特殊的性能,即在日光的照射下吸收光能，不以热量的形式散发,而以低频可见荧光将所吸收的能量发射出去。这种发射光与正常的反射光色彩相结合,形成异常鲜艳的色彩，十分引人注目。有机荧光颜料广泛用于广告牌，路标及各种安全标记、纤维制品的印花、印刷、油墨、涂料、塑料等方面。
近年来，常见荧光颜料部分是采用有机荧光染料为着色剂，并以高分子树脂为载体合成的，部分是通过在不同体系下硅溶胶凝胶法制备合成的纳米级有机/无机复合荧光染料。涂料工业PAINT&COATINGSINDUSTRY，第33卷第7期，综述了荧光颜料的研究进展。DyesandPigments80(2009)212–218，介绍了在THF/H2O体系下，通过硅溶胶凝胶法制备稳定有机/无机复合荧光染料。但这些过程存在价格昂贵、操作复杂、能耗大、耐溶剂性差、过程不易控制、污染严重等诸多问题。
发明内容
本发明的目的在于：提供一种复合荧光颜料的制备方法，所制备的复合荧光颜料具有良好的耐酸碱性，耐有机溶剂性，热稳定性，耐紫外老化性，色泽均匀，荧光强度高，拓展了该类复合颜料的应用领域。
本发明的技术解决方案是：
将有机荧光染料分子溶于水或有机溶剂中，然后加入改性处理过的海泡石吸附，研磨、焙烧处理后，再将所得材料分散于水溶液或有机溶剂中，并加入硅类化合物和催化剂在低于100℃的温度下包覆反应；反应完全后冷却过滤、洗涤、干燥得到海泡石基复合荧光颜料。其中海泡石的改性处理包括盐酸活化改性处理，或先盐酸活化后再经350℃～450℃高温改性处理，或先盐酸活化后再经十六烷基三甲基溴化铵改性处理。
本发明所用的海泡石改性处理过程中盐酸的摩尔浓度为0.5-1.5mol/l。
本发明所用的有机荧光染料分子为罗丹明B、罗丹明6G、酸性曙红、荧光黄、碱性黄HG、硫代黄素、艳绿光黄色中的一种。有机荧光染料用量为海泡石质量的0.1-10％。
本发明所用的溶剂是水、甲醇、乙醇、丙酮、甲苯、二甲基甲酰胺、二甲基亚砜中的一种。
本发明所用的硅类化合物为正硅酸乙酯、正硅酸四甲酯、正硅酸四乙酯、正硅酸四丙酯等硅酸酯，硅酸钠、硅酸钾等硅酸盐，水玻璃、甲基三乙氧基硅烷、乙基三乙氧基硅烷、苯基三乙氧基硅烷、乙烯基三乙氧基硅烷、十六烷基三乙氧基硅烷及它们的甲氧基和氯代硅烷中的一种。硅类化合物用量为海泡石质量的0.1％-10％。
本发明所用的催化剂是氨水、乙二胺、三乙胺、硫酸、硝酸、盐酸、醋酸、草酸、甲酸、苯磺酸、胺、亚硫酸氢钠、硼氢化钠或金属氧化物中的一种。催化剂用量为海泡石质量的0.1％-2％。
本发明研发过程中，考虑采用海泡石这种具有多孔结构的材料来制备复合荧光颜料，但同时，发明人也不能确定利用海泡石制成的复合颜料的耐酸碱性，耐有机溶剂性，热稳定性，耐紫外老化性等性能是否能得到提高，另外，其荧光性能是否会有影响。开始阶段，发明人研发过程中发现直接加入海泡石在制备出来的荧光颜料，并未能制备发明人所需的理想的荧光颜料。因此，发明人将海泡石先盐酸活化处理，再与染料分子吸附复合经过球磨和热处理后，最后经过二氧化硅的包覆处理。发明人通过以上处理后，惊喜的发现，发明材料的荧光强度并未降低的同时，还具有良好的耐酸、碱性能及热稳定性，且只是在有机溶剂中略有褪色而已；另外，发明人进一步研发还发现将海泡石先通过盐酸活化处理后350℃～450℃高温改性处理，或是先盐酸活化后再经十六烷基三甲基溴化铵改性处理制成复合荧光颜料，可以取得不但荧光强度并未降低而且还具有耐酸碱性，耐有机溶剂性，热稳定性好，耐紫外老化性优异等性能。
通过本发明的方法可制得廉价的复合荧光颜料。本发明的制备过程，可使得产物反应均一、充分，由于改性海泡石的引入和二氧化硅包覆的共同作用，可制得更稳定的复合荧光颜料，且不影响荧光发光效果。本发明方法具有合成设备简单，无污染，成本投入少。可广泛应用于工业，广告牌、各种安全标记、服装、印刷油墨、油漆、涂料、塑料等方面。
附图说明
附图1为本发明的复合荧光颜料罗丹明B的荧光发射光谱，激发波长为540nm。
具体实施方式
以下通过具体实施案例对本发明做进一步详细地说明，本发明技术方案不限于列举的具体实施例。
对比例1：将0.02g罗丹明B溶解于100ml水中，在搅拌条件下，加入未经任何处理的海泡石10g，室温吸附4h；球磨、焙烧处理后；取1g分散于5g水溶液中，再加入0.64g正硅酸乙酯和0.3g醋酸，室温下反应60min；过滤、洗涤、干燥得产物。
实施例1：将0.05g罗丹明B溶解于100ml水中，在搅拌条件下，加入经1mol/L盐酸活化处理12h的海泡石10g，室温吸附4h；球磨、焙烧处理后；取1g分散于15g水溶液中，再加入1.07g正硅酸乙酯和0.54g醋酸，室温下反应90min；过滤、洗涤、干燥得产物。
对比例2：将0.1g罗丹明6G溶解于100ml水中，在搅拌条件下，加入未经任何处理的海泡石10g，室温吸附5h；球磨、焙烧处理后；取1g分散于10g乙醇中，再加入0.3g硅酸钠和0.5g盐酸，升温至70℃反应5h；过滤、洗涤、干燥得产物。
实施例2：将0.1g罗丹明6G溶解于100ml水中，在搅拌条件下，加入先经0.5mol/L盐酸活化处理12h，并在400℃焙烧处理12h后的海泡石10g，室温吸附5h；球磨、焙烧处理后；取1g分散于10g乙醇中，再加入0.3g硅酸钠和0.5g盐酸，升温至70℃反应5h；过滤、洗涤、干燥得产物。
对比例3：将1g酸性曙红溶解于100ml丙酮中，在搅拌条件下，加入未经任何处理的海泡石10g，室温吸附6h；球磨、焙烧处理后；取1g分散于10g丙酮中，再加入0.3g四乙氧基硅烷和0.3g十六烷基三乙氧基硅烷和0.3g三乙胺，升温至90℃下反应12h；过滤、洗涤、干燥得产物。
实施例3：将1g酸性曙红溶解于100ml丙酮中，在搅拌条件下，加入先经0.5mol/L盐酸活化处理12h，并经十六烷基三甲基溴化铵处理后的海泡石10g，室温吸附6h；球磨、焙烧处理后；取1g分散于10g丙酮中，再加入0.3g四乙氧基硅烷和0.3g十六烷基三乙氧基硅烷和0.3g三乙胺，升温至90℃下反应12h；过滤、洗涤、干燥得产物。
表1海泡石基复合荧光颜料的稳定性
| 实施例 | 1M HCL | 1M NaOH | 有机溶剂 | 紫外线照射24h |
| 对比例1 | 有些许褪色 | 无变化 | 有些许褪色 | 无变化 |
| 实施例1 | 无变化 | 无变化 | 有些许褪色 | 无变化 |
| 对比例2 | 有些许褪色 | 有些许褪色 | 有些许褪色 | 无变化 |
| 实施例2 | 无变化 | 无变化 | 无变化 | 无变化 |
| 对比例3 | 有些许褪色 | 无变化 | 有些许褪色 | 无变化 |
| 实施例3 | 无变化 | 无变化 | 无变化 | 无变化 |
Claims (10)
1.一种复合荧光颜料的制备方法，其特征是：将有机荧光染料溶于水或有机溶剂中，加入改性处理过的海泡石吸附，研磨、焙烧处理后，再将所得材料分散于水溶液或有机溶剂中，加入硅类化合物和催化剂进行包覆反应，反应温度不高于100℃，反应完全后冷却过滤、洗涤、干燥得到海泡石基复合荧光颜料；其中海泡石的改性处理包括盐酸活化改性处理，或先盐酸活化后再经350℃～450℃高温改性处理，或先盐酸活化后再经十六烷基三甲基溴化铵改性处理。
2.根据权利要求1所述的复合荧光颜料的制备方法，其特征是：盐酸的摩尔浓度为0.5-1.5mol/l。
3.根据权利要求1所述的复合荧光颜料的制备方法，其特征是：所述的有机荧光染料分子为罗丹明B、罗丹明6G、酸性曙红、荧光黄、碱性黄HG、硫代黄素、艳绿光黄色中的一种。
4.根据权利要求1或3所述的复合荧光颜料的制备方法，其特征是：有机荧光染料用量为海泡石质量的0.1-10％。
5.根据权利要求1所述的复合荧光颜料的制备方法，其特征是：所述溶剂是水、甲醇、乙醇、丙酮、甲苯、二甲基甲酰胺、二甲基亚砜中的一种。
6.根据权利要求1所述的复合荧光颜料的制备方法，其特征是：所述的硅类化合物是硅酸酯或硅酸盐；或是水玻璃、甲基三乙氧基硅烷、乙基三乙氧基硅烷、苯基三乙氧基硅烷、乙烯基三乙氧基硅烷、十六烷基三乙氧基硅烷或它们的甲氧基或它们的氯代硅烷中的一种。
7.根据权利要求6所述的复合荧光颜料的制备方法，其特征是：所述的硅酸酯为正硅酸乙酯、正硅酸四甲酯、正硅酸四乙酯或正硅酸四丙酯；所述的硅酸盐为硅酸钠或硅酸钾。
8.根据权利要求1或6或7所述的复合荧光颜料的制备方法，其特征是：硅类化合物用量为海泡石质量的0.1％-10％。
9.根据权利要求1所述的复合荧光颜料的制备方法，其特征是：所述催化剂是氨水、乙二胺、三乙胺、硫酸、硝酸、盐酸、醋酸、草酸、甲酸、苯磺酸、亚硫酸氢钠、硼氢化钠或金属氧化物中的一种。
10.根据权利要求1或9所述的复合荧光颜料的制备方法，催化剂用量为海泡石质量的0.1％-2％。
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