CN1294211C - Super molecular structure light thermal stable light fast brilliant red BBC dye and its intercalation method - Google Patents
Super molecular structure light thermal stable light fast brilliant red BBC dye and its intercalation method Download PDFInfo
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- CN1294211C CN1294211C CNB2003101035993A CN200310103599A CN1294211C CN 1294211 C CN1294211 C CN 1294211C CN B2003101035993 A CNB2003101035993 A CN B2003101035993A CN 200310103599 A CN200310103599 A CN 200310103599A CN 1294211 C CN1294211 C CN 1294211C
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- 230000002687 intercalation Effects 0.000 title claims abstract description 20
- 238000009830 intercalation Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 9
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 title abstract description 10
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 33
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 33
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 33
- 239000000049 pigment Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 150000001450 anions Chemical class 0.000 claims abstract description 16
- 239000011229 interlayer Substances 0.000 claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- -1 BBC anion Chemical class 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- RFQLTXOJXDPLFL-UHFFFAOYSA-N C(CCC)OCC(=S)OCCO Chemical compound C(CCC)OCC(=S)OCCO RFQLTXOJXDPLFL-UHFFFAOYSA-N 0.000 claims 1
- 230000004075 alteration Effects 0.000 claims 1
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 239000012860 organic pigment Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 22
- 239000000463 material Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- 229910019427 Mg(NO3)2-6H2O Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- C09B63/00—Lakes
- C09B63/005—Metal lakes of dyes
-
- 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
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
-
- 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
- C09C1/40—Compounds of aluminium
- C09C1/42—Clays
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
本发明介绍了一种超分子结构光热稳定型耐晒艳红BBC颜料及其插层方法。为了提高有机颜料耐晒艳红BBC的耐光性和耐热性，本发明利用水滑石的可插层性，以层间阴离子为NO3 -的水滑石为前体，用离子交换法将耐晒艳红BBC的阴离子插入到水滑石层间，使耐晒艳红BBC的阴离子全部取代水滑石层间的NO3 -，得到的插层水滑石LDH-BBC颜料不但保持了耐晒艳红BBC本身的颜色，而且与耐晒艳红BBC相比，其耐光性和耐热性均有大幅度的提高。该LDH-BBC颜料可代替耐晒艳红BBC广泛用于涂料、油漆和复合材料中。The invention introduces a supramolecular structure light-heat stable sunfast brilliant red BBC pigment and its intercalation method. In order to improve the light fastness and heat resistance of the organic pigment Sunfast Brilliant Red BBC, the present invention utilizes the intercalation property of hydrotalcite, uses the hydrotalcite whose interlayer anion is NO 3 - as a precursor, and uses the ion exchange method to convert the sunfast The anions of Brilliant Red BBC are inserted into the interlayer of hydrotalcite, so that the anions of Brilliant Red BBC completely replace the NO 3 - between the layers of hydrotalcite, and the obtained intercalated hydrotalcite LDH-BBC pigment not only maintains the pigment of Brilliant Red BBC Compared with the light fast red BBC, its light fastness and heat resistance are greatly improved. The LDH-BBC pigment can replace Brilliant Red BBC and is widely used in coatings, paints and composite materials.
Description
所属领域：本发明涉及一种超分子结构光热稳定型耐晒艳红BBC颜料及其插层方法。Field: The present invention relates to a supramolecular structure light-heat stable sunfast brilliant red BBC pigment and its intercalation method.
背景技术：耐晒艳红BBC是一种含有偶氮基团的色淀颜料，由于其耐光、耐热性能差，使其应用范围和使用效果受到了极大的限制，因此提高耐晒艳红BBC的耐光、耐热性能具有十分重要的意义。类水滑石(Layered DoubleHydroxides，简写为LDHs)是一种阴离子型层状材料，由于其具有可插层组装的性能，因而利用此性能可将一些功能物种插入到水滑石层间，制备具有特殊功能的超分子插层结构材料。Background technology: Sunfast Brilliant Red BBC is a lake pigment containing azo groups. Due to its poor light resistance and heat resistance, its application range and use effect are greatly limited. Therefore, the improvement of Sunfast Brilliant Red The light resistance and heat resistance of BBC are of great significance. Hydrotalcite-like (Layered Double Hydroxides, abbreviated as LDHs) is an anionic layered material. Due to its intercalation and assembly properties, some functional species can be inserted into the interlayers of hydrotalcites by using this property, and the preparation has special functions. supramolecular intercalation materials.
文献Mohd Zobir bin Hussein，Zulkarnain Zainal，Asmah Hj.Yahaya，Azirabinti Abd.Aziz，Materials Science and Engineering B88，2002，98-102，将酸性染料萘蓝黑10B的水溶液与含有Mg2+和Al3+的水溶液混合，调整反应体系的pH＝10，得到层间为萘蓝黑10B阴离子的插层水滑石，该插层方法为共沉淀法。其研究的目的只是得到一种无机-有机纳米复合材料，并未考察产物能否作为一种新型颜料来使用。Literature Mohd Zobir bin Hussein, Zulkarnain Zainal, Asmah Hj.Yahaya, Azirabinti Abd.Aziz, Materials Science and Engineering B88, 2002, 98-102, the aqueous solution of acid dye naphthalene blue black 10B and the solution containing Mg 2+ and Al 3+ The aqueous solution is mixed, and the pH of the reaction system is adjusted to 10 to obtain an intercalated hydrotalcite with naphthalene blue black 10B anion between layers, and the intercalation method is a co-precipitation method. The purpose of the research is only to obtain an inorganic-organic nanocomposite material, and does not examine whether the product can be used as a new type of pigment.
文献Umberto Costantino，Natascia Coletti，and Morena Nocchetti，Langmuir，1999，15：4454-4460中，先采用尿素热合成法得到水滑石[Zn0.67Al0.33(OH)2][CO3]0.165·0.4H2O，再将其与NaCl和HCl反应得到水滑石Zn0.67Al0.33(OH)2Cl0.33·0.4H2O，再以Zn0.67Al0.33(OH)2Cl0.33·0.4H2O为前体，甲基橙(MO)为客体，组装得到插层水滑石[Zn0.67Al0.33(OH)2][MO0.31Cl0.02]·0.85H2O，他们考察了产物的荧光性。其缺点是前体制备方法复杂。In the literature Umberto Costantino, Natascia Coletti, and Morena Nocchetti, Langmuir, 1999, 15: 4454-4460, the hydrotalcite [Zn 0.67 Al 0.33 (OH) 2 ] [CO 3 ] 0.165 · 0.4H 2 was first obtained by urea thermal synthesis O, then react it with NaCl and HCl to get hydrotalcite Zn 0.67 Al 0.33 (OH) 2 Cl 0.33 · 0.4H 2 O, then use Zn 0.67 Al 0.33 (OH) 2 Cl 0.33 · 0.4H 2 O as the precursor, Using methyl orange (MO) as the guest, an intercalated hydrotalcite [Zn 0.67 Al 0.33 (OH) 2 ][MO 0.31 Cl 0.02 ]·0.85H 2 O was assembled. The fluorescence of the product was investigated. Its disadvantage is that the preparation method of the precursor is complicated.
发明内容：本发明的目的是利用LDHs的可插层性，将耐晒艳BBC插入到类水滑石层间，制备一种光热稳定型耐晒艳红BBC插层颜料。Summary of the invention: The purpose of the present invention is to use the intercalability of LDHs to insert Sunfast Brilliant BBC into the hydrotalcite-like layer to prepare a photothermally stable sunfast Brilliant Red BBC intercalation pigment.
前面文献中报道的萘蓝黑10B和甲基橙都是一种染料，均能溶于水，而本发明中所用的耐晒艳红BBC则是一种色淀颜料，既不溶于水也不溶于大多数有机溶剂，因此要选择合适的插层反应溶剂，才能将耐晒艳红BBC插层到LDHs中。Naphthalene blue black 10B and methyl orange reported in the previous literature are all a kind of dyestuff, all can be dissolved in water, and the sunfast brilliant red BBC used in the present invention is a kind of lake pigment, neither soluble in water nor soluble For most organic solvents, it is necessary to select a suitable intercalation reaction solvent to intercalate Brilliant Red BBC into LDHs.
本发明以层间阴离子为NO3 -的类水滑石为前体，采用离子交换法使耐晒艳红BBC的阴离子取代水滑石层间的NO3 -离子，生成层间阴离子为耐晒艳红BBC阴离子的插层水滑石(LDH-BBC)。In the present invention, the hydrotalcite-like anion in which the interlayer anion is NO 3 - is used as a precursor, and the anion of the sunfast brilliant red BBC is used to replace the NO 3 -ion in the interlayer of the hydrotalcite by an ion exchange method, and the interlayer anion is formed as the sunfast brilliant red Intercalated hydrotalcites of BBC anions (LDH-BBC).
本发明制备的LDH-BBC的化学通式为：[M2+ 1-xM3+ x(OH)2](BBC)2- x/2·mH2O，其中0.2＜X/(1-X)＜0.5，m＝1-3X/2；M2+为二价金属离子Mg2+、Zn2+、Ni2+、Fe2+或Cu2+中的任意一种，M3+为三价金属离子Al3+、Fe3+或Cr3+中的任意一种。The general chemical formula of LDH-BBC prepared in the present invention is: [M 2+ 1-x M 3+ x (OH) 2 ](BBC) 2- x/2 mH 2 O, wherein 0.2<X/(1- X)<0.5, m=1-3X/2; M 2+ is any one of divalent metal ions Mg 2+ , Zn 2+ , Ni 2+ , Fe 2+ or Cu 2+ , M 3+ is Any one of trivalent metal ions Al 3+ , Fe 3+ or Cr 3+ .
LDH-BBC的制备步骤如下：The preparation steps of LDH-BBC are as follows:
A.采用单滴法制备结构通式为：[M2+ 1-xM3+ x(OH)2](NO3)- x·mH2O的水滑石前体，其中0.2＜X/(1-X)＜0.5，m＝1-3X/2；将该水滑石加入高沸点的有机溶剂乙二醇、乙二醇二丁基醚或二甘醇二乙醚中，室温下磁力搅拌，配制成浓度为0.05-0.1M的水滑石悬浮液备用；A. Prepare the hydrotalcite precursor with the general structure formula: [M 2+ 1-x M 3+ x (OH) 2 ](NO 3 ) - x ·mH 2 O by single drop method, where 0.2<X/( 1-X)<0.5, m=1-3X/2; add the hydrotalcite into the high-boiling organic solvent ethylene glycol, ethylene glycol dibutyl ether or diethylene glycol diethyl ether, stir magnetically at room temperature, and prepare A hydrotalcite suspension with a concentration of 0.05-0.1M is used for subsequent use;
B.按照耐晒艳红BBC与水滑石前体的摩尔比为1.5-3的比例计量，将耐晒艳红BBC溶解在与步骤A相同的有机溶剂中，使其浓度控制在0.02-0.05M；B. Measure according to the molar ratio of Brilliant Red BBC and hydrotalcite precursor of 1.5-3, dissolve Brilliant Red BBC in the same organic solvent as step A, and control the concentration at 0.02-0.05M ;
C.将步骤B制备的耐晒艳红BBC溶液与步骤A制备的水滑石悬浮液充分混合，在温度为90-150℃的条件下反应6-48h，过滤、洗涤到中性，在60-100℃干燥12-24h，得到耐晒艳红BBC阴离子插层水滑石LDH-BBC。C. Fully mix the Brilliant Red BBC solution prepared in step B with the hydrotalcite suspension prepared in step A, react at a temperature of 90-150°C for 6-48h, filter, wash to neutrality, and Dry at 100°C for 12-24 hours to obtain the sunfast brilliant red BBC anion-intercalated hydrotalcite LDH-BBC.
步骤A中所用的有机溶剂较佳的是乙二醇。The organic solvent used in step A is preferably ethylene glycol.
将得到的LDH-BBC进行XRD、FT-IR、UV-Vis和TG-DTA等表征显示，耐晒艳红BBC阴离子已组装进入了层状材料LDH层间。The obtained LDH-BBC was characterized by XRD, FT-IR, UV-Vis and TG-DTA, etc., showing that the Brilliant Red BBC anion had been assembled into the interlayer of the layered material LDH.
分别按LDH-BBC、耐晒艳红BBC与PP材料的质量比为0.2％的比例，将该两种颜料复合到PP中，制成标准色板，然后用TC-P2A型全自动测色仪测定两种色板的色差(ΔE)，结果ΔE均小于5，证明插层颜料LDH-BBC保持了耐晒艳红BBC原有的颜色。把这两种复合材料同时置于功率为2000瓦的紫外灯下分别照射20、40、60和80分钟后，用测色仪测定其色差大小，结果见表1。从表1中可以看出，插层颜料LDH-BBC的耐光性明显高于耐晒艳红BBC。According to the mass ratio of LDH-BBC, Brilliant Red BBC and PP material at 0.2%, compound the two pigments into PP to make a standard color plate, and then use TC-P2A automatic color measuring instrument The color difference (ΔE) of the two swatches was measured, and the results showed that ΔE was less than 5, which proved that the intercalated pigment LDH-BBC maintained the original color of Brilliant Red BBC. The two composite materials were placed under a UV lamp with a power of 2000 watts and irradiated for 20, 40, 60 and 80 minutes respectively, and the color difference was measured with a colorimeter. The results are shown in Table 1. It can be seen from Table 1 that the light fastness of the intercalated pigment LDH-BBC is significantly higher than that of Brilliant Red BBC.
表1.LDH-BBC与耐晒艳红BBC的耐光性试验结果
将插层颜料LDH-BBC和耐晒艳红BBC粉末分别放在温度为100、150、200、250和300℃的烘箱中受热30分钟后取出，用UV-Vis分光光度计对其耐热性进行分析可知，耐晒艳红BBC在200℃时，其UV-Vis曲线已有较大幅度的变化，而插层颜料LDH-BBC在300℃时，其UV-Vis曲线刚刚开始有所变化。这就说明插层颜料比耐晒艳红BBC具有较高的热稳定性。Put the intercalation pigment LDH-BBC and the fast red BBC powder in the oven at the temperature of 100, 150, 200, 250 and 300 ℃, respectively, and take it out after heating for 30 minutes, and use the UV-Vis spectrophotometer to measure its heat resistance. It can be seen from the analysis that the UV-Vis curve of Brilliant Red BBC has changed significantly at 200°C, while the UV-Vis curve of the intercalated pigment LDH-BBC has just begun to change at 300°C. This means that the intercalated pigment has higher thermal stability than Brilliant Red BBC.
显著优点：本发明所制备的插层水滑石LDH-BBC保持了耐晒艳红BBC原有的颜色，可以作为颜料使用，并且这种新型颜料的光、热稳定性与耐晒艳红BBC相比有大幅度的提高，因此用LDH-BBC代替耐晒艳红BBC用于复合材料中可大幅度减缓其退色程度和速度。所采用的前体制备方法简便，选择高沸点的有机溶剂可使耐晒艳红BBC顺利插层到水滑石中。该LDH-BBC颜料还可代替耐晒艳红BBC用于涂料和油漆中。Significant advantages: the intercalated hydrotalcite LDH-BBC prepared by the present invention maintains the original color of the light-fast brilliant red BBC, and can be used as a pigment, and the light and thermal stability of this new type of pigment are comparable to light-fast brilliant red BBC. The ratio has been greatly improved, so using LDH-BBC instead of Brilliant Red BBC in composite materials can greatly slow down the degree and speed of fading. The preparation method of the precursor adopted is simple and convenient, and the organic solvent with a high boiling point can be used to smoothly intercalate the sunfast brilliant red BBC into the hydrotalcite. The LDH-BBC pigment can also be used in coatings and paints instead of Brilliant Red BBC.
具体实施方式：Detailed ways:
实施例1：Example 1:
步骤A：取Mg(NO3)2·6H2O(15.38g，0.06mol)和Al(NO3)3·9H2O(11.25g，0.03mol)混合，溶于50ml脱除CO2的去离子水中；另取NaOH(7.20g，0.18mol)溶于75ml脱除CO2的去离子水中，置于250ml三口瓶中；在N2保护下将混合盐溶液缓慢滴入碱液中，强烈搅拌，然后用0.1M的NaOH溶液调节反应体系的pH值为10，接着将该浆状液于65℃的温度下陈化39h，最后抽滤、水洗得水滑石前体，其结构式为：Mg4Al2(OH)12(NO3)2·4H2O；将该水滑石前体2.20g(0.004mol)分散在50ml乙二醇中待用。Step A: Mix Mg(NO 3 ) 2 ·6H 2 O (15.38g, 0.06mol) and Al(NO 3 ) 3 ·9H 2 O (11.25g, 0.03mol), dissolve in 50ml CO 2 removal In deionized water; another NaOH (7.20g, 0.18mol) was dissolved in 75ml of deionized water from which CO2 was removed, and placed in a 250ml three-necked flask; under the protection of N2 , the mixed salt solution was slowly dropped into the lye, and vigorously stirred , and then use 0.1M NaOH solution to adjust the pH value of the reaction system to 10, then age the slurry at 65°C for 39 hours, and finally filter it with suction and wash it with water to obtain the hydrotalcite precursor, whose structural formula is: Mg 4 Al 2 (OH) 12 (NO 3 ) 2 ·4H 2 O; 2.20 g (0.004 mol) of the hydrotalcite precursor was dispersed in 50 ml of ethylene glycol for use.
步骤B：按照耐晒艳红BBC与水滑石前体的摩尔比为1.5的比例来称取耐晒艳红BBC(2.75g，0.006mol)，使其溶于100ml乙二醇中。Step B: Weigh the Brilliant Red BBC (2.75 g, 0.006 mol) according to the molar ratio of the Brilliant Red BBC to the hydrotalcite precursor being 1.5, and dissolve it in 100 ml of ethylene glycol.
步骤C：将耐晒艳红BBC溶液和LDHs前体悬浮液在容器中混合，然后在N2保护下，90℃搅拌反应48h，过滤、洗涤至pH值约为7，100℃干燥18h，组装得到耐晒艳红BBC阴离子插层LDHs材料。Step C: Mix the Brilliant Red BBC solution and the LDHs precursor suspension in a container, then stir and react at 90°C for 48h under the protection of N 2 , filter and wash until the pH value is about 7, dry at 100°C for 18h, and assemble The Brilliant Red BBC anion intercalation LDHs material was obtained.
分别采用XRD、FT-IR、UV-Vis和TG-DTA等手段分析和表征得到的插层LDHs，证明该插层产物层间阴离子全部为耐晒艳红BBC阴离子，是一种晶体晶相单一、结构一致的超分子插层结构材料。插层颜料与耐晒艳红BBC相比，其色差ΔE小于3，说明插层颜料与耐晒艳红BBC的颜色基本一致。通过对该插层颜料进行光、热稳定性能的测试后可知，其耐光、耐热性能均比耐晒艳红BBC有明显提高。The obtained intercalated LDHs were analyzed and characterized by XRD, FT-IR, UV-Vis and TG-DTA, respectively, which proved that the interlayer anions of the intercalated products were all sunfast red BBC anions, which was a crystal with a single crystal phase. , Supramolecular intercalation structure material with consistent structure. Compared with Brilliant Red BBC, the intercalated pigment has a color difference ΔE of less than 3, indicating that the color of the intercalated pigment is basically the same as that of Brilliant Red BBC. After testing the light and heat stability of the intercalated pigment, it can be seen that its light resistance and heat resistance are significantly improved compared with the sunfast bright red BBC.
实施例2：Example 2:
步骤A：取Mg(NO3)2·6H2O(17.31g，0.0675mol)和Al(NO3)3·9H2O(8.44g，0.0225mol)混合，溶于50ml脱除CO2的去离子水中。另取NaOH(7.20g，0.18mol)溶于75ml脱除CO2的去离子水中，置于250ml三口瓶中。在N2保护下将混合盐溶液缓慢滴入碱液中，强烈搅拌，然后用0.1M的NaOH溶液调节反应体系的pH值为10。接着将浆状液于65℃的温度下陈化39h，最后抽滤、水洗得水滑石前体，其结构式为：Mg6Al2(OH)16(NO3)2·4H2O；将该水滑石3.34g(0.005mol)分散在50ml乙二醇中。Step A: Mix Mg(NO 3 ) 2 6H 2 O (17.31g, 0.0675mol) and Al(NO 3 ) 3 9H 2 O (8.44g, 0.0225mol) in 50ml CO 2 removal ionized water. Another NaOH (7.20 g, 0.18 mol) was dissolved in 75 ml of deionized water from which CO 2 was removed, and placed in a 250 ml three-necked flask. Under the protection of N 2 , slowly drop the mixed salt solution into the lye, stir vigorously, and then adjust the pH value of the reaction system to 10 with 0.1M NaOH solution. Then the slurry was aged at 65°C for 39 hours, and finally filtered with suction and washed with water to obtain the hydrotalcite precursor, whose structural formula was: Mg 6 Al 2 (OH) 16 (NO 3 ) 2 ·4H 2 O; 3.34g (0.005mol) of hydrotalcite was dispersed in 50ml of ethylene glycol.
步骤B：按照耐晒艳红BBC与水滑石前体的摩尔比为2.0的比例来称取耐晒艳红BBC(4.59g，0.01mol)，使其溶于200ml乙二醇中。Step B: Weigh the Brilliant Red BBC (4.59 g, 0.01 mol) according to the molar ratio of the Brilliant Red BBC to the hydrotalcite precursor being 2.0, and dissolve it in 200 ml of ethylene glycol.
步骤C：将BBC溶液和LDHs前体悬浮液在容器中混合，然后在N2保护下，100℃搅拌反应24h，过滤、洗涤至pH值约为7，70℃干燥24h，组装得到耐晒艳红阴离子插层材料LDH-BBC。Step C: Mix the BBC solution and LDHs precursor suspension in a container, then stir and react at 100°C for 24h under the protection of N 2 , filter and wash until the pH value is about 7, dry at 70°C for 24h, and assemble to obtain the sunfast color Red anion intercalation material LDH-BBC.
分别采用XRD、FT-IR、UV-Vis和TG-DTA等手段分析和表征得到的插层材料，证明该插层产物层间阴离子全部为BBC阴离子，是一种晶体晶相单一、结构一致的超分子插层结构材料。插层颜料LDH-BBC与BBC相比，其色差ΔE小于5，说明该插层颜料LDH-BBC与BBC的颜色非常接近。通过对该插层颜料进行光、热稳定性能的测试后发现，其耐光、耐热性能也均比耐晒艳红BBC有明显提高。The obtained intercalation materials were analyzed and characterized by means of XRD, FT-IR, UV-Vis and TG-DTA, respectively, and it was proved that the interlayer anions of the intercalation products were all BBC anions, which was a single crystal phase and consistent structure. Supramolecular intercalation materials. Compared with BBC, the intercalated pigment LDH-BBC has a color difference ΔE of less than 5, indicating that the intercalated pigment LDH-BBC is very close to BBC in color. After testing the light and heat stability of the intercalated pigment, it is found that its light resistance and heat resistance are also significantly improved compared with the light fast red BBC.
实施例3：Example 3:
步骤A：取Zn(NO3)2·6H2O(17.85g，0.06mol)、Al(NO3)3·9H2O(11.25g，0.03mol)和NaNO3(4.53g，0.053mol)混合，溶于80ml脱除CO2的去离子水中，置于250ml三口瓶中。另取NaOH(5.32g，0.133mol)溶于50ml脱除CO2的去离子水中。在N2保护下将NaOH碱溶液缓慢滴入混合盐溶液中，强烈搅拌，至pH＝6时停止滴加碱溶液。接着将浆状液于70℃的温度下陈化24h，最后抽滤、水洗得水滑石前体，其结构式为：Zn4Al2(OH)12(NO3)2·4H2O；将该水滑石2.15g(0.003mol)分散在50ml乙二醇中。Step A: Mix Zn(NO 3 ) 2 6H 2 O (17.85g, 0.06mol), Al(NO 3 ) 3 9H 2 O (11.25g, 0.03mol) and NaNO 3 (4.53g, 0.053mol) , dissolved in 80ml of deionized water from which CO 2 has been removed, and placed in a 250ml three-necked bottle. Another NaOH (5.32 g, 0.133 mol) was dissolved in 50 ml of deionized water with CO 2 removed. Under the protection of N 2 , slowly drop the NaOH alkali solution into the mixed salt solution, stir vigorously, and stop the dropwise addition of the alkali solution when the pH=6. Then the slurry was aged at 70°C for 24 hours, and finally filtered with suction and washed with water to obtain the hydrotalcite precursor, whose structural formula was: Zn 4 Al 2 (OH) 12 (NO 3 ) 2 ·4H 2 O; 2.15g (0.003mol) of hydrotalcite was dispersed in 50ml of ethylene glycol.
步骤B：按照耐晒艳红BBC与水滑石前体的摩尔比为1.5的比例来称取耐晒艳红BBC(2.06g，0.0045mol)，使其溶于100ml乙二醇中。Step B: Weigh the Brilliant Red BBC (2.06 g, 0.0045 mol) according to the molar ratio of the Brilliant Red BBC to the hydrotalcite precursor being 1.5, and dissolve it in 100 ml of ethylene glycol.
步骤C：将耐晒艳红BBC溶液和LDHs前体悬浮液在容器中混合，然后在N2保护下，95℃搅拌反应36h，过滤、洗涤至pH值约为7，70℃干燥18h，组装得到耐晒艳红BBC阴离子插层LDHs材料。Step C: Mix the Brilliant Red BBC solution and the LDHs precursor suspension in a container, then stir and react at 95°C for 36h under the protection of N 2 , filter and wash until the pH value is about 7, dry at 70°C for 18h, and assemble The Brilliant Red BBC anion intercalation LDHs material was obtained.
分别采用XRD、FT-IR、UV-Vis和TG-DTA等手段分析和表征得到的插层LDHs，证明该插层产物层间阴离子全部为耐晒艳红BBC阴离子，是一种晶体晶相单一、结构一致的超分子插层结构材料。插层颜料与耐晒艳红BBC相比，其色差ΔE小于5，说明插层颜料保持了耐晒艳红BBC原来的颜色。通过对该插层颜料进行光、热稳定性能的测试后可知，其耐光、耐热性能均比耐晒艳红BBC有明显提高。The obtained intercalated LDHs were analyzed and characterized by XRD, FT-IR, UV-Vis and TG-DTA, respectively, which proved that the interlayer anions of the intercalated products were all sunfast red BBC anions, which was a crystal with a single crystal phase. , Supramolecular intercalation structure material with consistent structure. Compared with Brilliant Red BBC, the intercalation pigment has a color difference ΔE of less than 5, indicating that the intercalated pigment maintains the original color of Brilliant Red BBC. After testing the light and heat stability of the intercalated pigment, it can be seen that its light resistance and heat resistance are significantly improved compared with the sunfast bright red BBC.
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| CNB2003101035993A CN1294211C (en) | 2003-11-13 | 2003-11-13 | Super molecular structure light thermal stable light fast brilliant red BBC dye and its intercalation method |
| PCT/CN2004/001116 WO2005047397A1 (en) | 2003-11-13 | 2004-09-28 | A super molecular structure permanent red bbc pigment that is light stabilizing and heat stabilizing mode and its preparation process |
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| CN1294213C (en) * | 2004-06-24 | 2007-01-10 | 北京化工大学 | Light-heat stabilizer methyl organic intercalation pigment and use thereof |
| CN1333005C (en) * | 2005-12-19 | 2007-08-22 | 北京化工大学 | Supermolecular interlayer structured ultraviolet light absorbent, its preparation method and uses |
| CN101879314B (en) * | 2009-12-08 | 2012-05-30 | 山东炳坤腾泰陶瓷科技有限公司 | Method for synthesizing bio-medicament/hydrotalcite-like composite material |
| CN101982509A (en) * | 2010-10-08 | 2011-03-02 | 北京化工大学 | Acid yellow 17 intercalation pigment with light stability, thermal stability and supramolecular structure and preparation method thereof |
| CN102732055A (en) * | 2011-04-07 | 2012-10-17 | 北京化工大学 | Multi-component chromogenic anion co-intercalation supramolecular structure pigment and preparation method thereof |
| CN103965654B (en) * | 2014-04-30 | 2016-08-17 | 北京化工大学 | A kind of supermolecular intercalation structure of resistance to light type pigment and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1056827A (en) * | 1990-05-25 | 1991-12-11 | 密歇根州州立大学托管委员会 | The multiple hydroxide of the stratiform that the polyacid root embeds |
| US5414080A (en) * | 1992-11-25 | 1995-05-09 | Board Of Trustees Operating Michigan State University | Porphyrin-metallic complex intercalated layered double hydroxides |
| CN1171979A (en) * | 1996-07-29 | 1998-02-04 | 德国泰克萨科股份公司 | Process for producing hydrotalcites and their metal oxides |
| US5730951A (en) * | 1994-04-29 | 1998-03-24 | Aluminum Company Of America | Two powder synthesis of hydrotalcite and hydrotalcite-like compounds with polyvalent inorganic anions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056827A (en) * | 1990-05-25 | 1991-12-11 | 密歇根州州立大学托管委员会 | The multiple hydroxide of the stratiform that the polyacid root embeds |
| US5414080A (en) * | 1992-11-25 | 1995-05-09 | Board Of Trustees Operating Michigan State University | Porphyrin-metallic complex intercalated layered double hydroxides |
| US5730951A (en) * | 1994-04-29 | 1998-03-24 | Aluminum Company Of America | Two powder synthesis of hydrotalcite and hydrotalcite-like compounds with polyvalent inorganic anions |
| CN1171979A (en) * | 1996-07-29 | 1998-02-04 | 德国泰克萨科股份公司 | Process for producing hydrotalcites and their metal oxides |
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