WO2005047397A1 - Pigment bbc rouge permanent a structure supramoleculaire constituant un moyen de stabilisation de lumiere et de chaleur et son procede de preparation - Google Patents
Pigment bbc rouge permanent a structure supramoleculaire constituant un moyen de stabilisation de lumiere et de chaleur et son procede de preparation Download PDFInfo
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- WO2005047397A1 WO2005047397A1 PCT/CN2004/001116 CN2004001116W WO2005047397A1 WO 2005047397 A1 WO2005047397 A1 WO 2005047397A1 CN 2004001116 W CN2004001116 W CN 2004001116W WO 2005047397 A1 WO2005047397 A1 WO 2005047397A1
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- WIPO (PCT)
- Prior art keywords
- bbc
- light
- pigment
- hydrotalcite
- red bbc
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- 239000000049 pigment Substances 0.000 title claims abstract description 35
- 230000000087 stabilizing effect Effects 0.000 title abstract 4
- 238000002360 preparation method Methods 0.000 title description 3
- 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 37
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 37
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000001450 anions Chemical class 0.000 claims abstract description 12
- 239000011229 interlayer Substances 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 18
- 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 claims description 14
- -1 brilliant red BBC anion Chemical class 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 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 claims description 3
- MYQCVVFSYJOXKT-UHFFFAOYSA-N 2-ethoxy-1-(2-ethoxyethoxy)hexane Chemical compound C(C)OC(COCCOCC)CCCC MYQCVVFSYJOXKT-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 238000009830 intercalation Methods 0.000 abstract description 26
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 239000012860 organic pigment Substances 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- 239000000463 material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013078 crystal Substances 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
- 239000007864 aqueous solution Substances 0.000 description 2
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- 241000735284 Irena Species 0.000 description 1
- 241000204801 Muraenidae Species 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
- 239000003513 alkali Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000000744 eyelid Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 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 1
- 229940012189 methyl orange Drugs 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
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
Classifications
-
- 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
Definitions
- the invention relates to a light and heat stable type light-resistant bright red BBC pigment with a supramolecular structure and an intercalation method thereof.
- Lightfast 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, so the lightfastness of light fast red BBC is improved. 2. Heat resistance is of great significance.
- Layered Double Hydroxides (LDHs) is an anionic layered material. Because of its intercalable layer 'assembly performance, some functional species can be inserted between the hydrotalcite layers to prepare it. Supramolecular intercalation structure material with special function.
- hydrotalcite was first obtained by the urea thermal synthesis method [Zn 0. 67 Al 0. 33 (OH) 2 ] [C0 3 ]. , 165 ⁇ 0. 4H 2 0, and then reacted with NaCl and HC1 to obtain hydrotalcite Z 3 ⁇ 4 67 A1. . 33 (0H) 2 C1. 33 ⁇ 0. 4H 2 O, then Z 3 ⁇ 4 67 A1. 33 (OH) 2 C1 Q. 33 ⁇ 0.
- the purpose of the present invention is to make use of the intercalability of LDHs to insert a light-resistant bright red BBC between the hydrotalcite-like layers to prepare a light-heat stable type light-resistant bright red BBC intercalation pigment.
- naphthalene blue black 10B and methyl orange reported in the previous literature are both dyes, both of which are soluble in water, while the sun-resistant bright red BBC used in the present invention is a lake pigment, which is neither soluble in water nor soluble As most organic solvents, it is necessary to choose a suitable intercalation reaction solvent in order to intercalate the bright red BBC into LDHs.
- a hydrotalcite-like interlayer anion of which is N0 3 — is used as a precursor, and an anion exchange method is used to replace the anion of the lightfast brilliant red BBC with the N0 3 -ion between the layers of the hydrotalcite, and the interlayer anion is generated as a lightfast brilliant red BBC anion intercalated hydrotalcite (LDH-BBC).
- LDH-BBC The preparation steps of LDH-BBC are as follows:
- the light-resistant brilliant red BBC is dissolved in the same organic solvent as in step A to control the concentration to 0. 02-0. 05M;
- step C Thoroughly mix the lightfast red BBC solution prepared in step B with the hydrotalcite suspension prepared in step A, and react at a temperature of 90-150 ° C for 6-48h, filter and wash to neutrality, at 60 Dry at -100 ° C for 12-24h to obtain light-resistant bright red BBC anion intercalated hydrotalcite LDH_BBC.
- the high-boiling organic solvent used in step A may be ethylene glycol, ethylene glycol dibutyl ether, or diethylene glycol diethyl ether.
- the intercalation pigment LDH-BBC and light-resistant bright red BBC powder were placed in ovens at temperatures of 100, 150, 200, 250, and 300 ° C, respectively, and then taken out after being heated for 30 minutes. They were resistant to UV-Vis spectrophotometers.
- the thermal analysis shows that the UV-Vis curve of the bright red BBC at 200 ° C has changed greatly, and the UV-Vis curve of the intercalation pigment LDH-BBC at 300 ⁇ has just begun. Changed. This shows that the intercalation pigment has higher thermal stability than the bright red BBC.
- the intercalated hydrotalcite LDH-BBC prepared by the present invention maintains the original color of the sun-resistant bright red BBC, and can be used as a pigment, and the light and thermal stability of this new pigment is similar to that of the sun-resistant bright red BBC.
- the ratio has been greatly improved, so the use of LDH-BBC instead of light-resistant bright red BBC in composite materials can greatly reduce its degree of discoloration and speed.
- the method for preparing the precursor is simple, and the high-boiling organic solvent can be used to smoothly intercalate the bright red BBC into the hydrotalcite.
- the LDH-BBC pigment can also be used in coatings and paints instead of light-fast brilliant red BBC. detailed description
- Step A Take Mg (N0 3 ) 2 ⁇ 6 ⁇ 2 0 (15.38g, 0.06mol) and Al ( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0 (11. 25g, 0.03mol) and dissolve in 50ml to remove 0) 2 in deionized water; dissolve NaOH (7. 20g, 0.
- Step B Weigh the light-resistant brilliant red BBC (2.75 g, 0.006 mol) according to the molar ratio of the light-resistant brilliant red BBC to the hydrotalcite precursor to 1.5, and dissolve it in 100 ml of ethylene glycol. .
- Step C Suspend and swirl the bright red BBC solution and LDHs precursors in a container and mix, and then stir at 90 ° C for 48h under the protection of the filter, filter, and wash until the pH is about 7, 1G0 ° C dry At 18h, the lightfast brilliant red BBC anion intercalation LDHs material was assembled.
- Step A Mg (N0 3 ) 2 ⁇ 6 ⁇ 2 0 (17. 31g, 0.0675mol) and Al ( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0 (8. 44g, 0. 0225mol) are mixed and dissolved in 50ml to remove C0 2 in deionized water.
- Another NaOH (7.20 g, 0.18 mol) was dissolved in 75 ml of CO 2 deionized water and placed in a 250 ml three-necked bottle.
- 1M ⁇ OHOH ⁇ Slowly drip the mixed salt solution into the lye under N 2 protection, stir vigorously, and then use 0.1 M NaOHsolve The pH of the reaction system was adjusted to 10 by the liquid.
- Step B Weigh the light-resistant brilliant red BBC (4.59 g, 0.01 mol) according to the molar ratio of the light-resistant brilliant red BBC to the hydrotalcite precursor to 2.0, and dissolve it in 200 ml of ethylene glycol. .
- Step C Mix the BBC solution and LDHs precursor suspension in a container, then ⁇ Under the protection, the reaction was stirred at 100 ° C for 24h, filtered and washed to a pH of about 7, and dried at 70 ° C for 24h.
- the light-resistant bright red anion intercalation material LDH-BBC was assembled.
- the interlayer anions of the intercalation products were all BBC anions, which was a single crystal phase with a consistent structure.
- Super rammer intercalation structure material Compared with BBC, the interlaced pigment LDH-BBC has a color difference ⁇ E less than 5, which indicates that the interlaced pigment LDH-BBC and BBC are very close in color. After testing the intercalation pigment for light and thermal stability, it was found that its light and heat resistance were also significantly improved compared to the bright red BBC.
- hydrotalcite precursor whose structural formula is: Zn ⁇ 4 ⁇ 1 2 (0 ⁇ ) 12 ( ⁇ 0 3 ) 2- 4H 2 0; 2.15 g (0.003 mol) of this hydrotalcite was dispersed in 50 ml of ethylene glycol.
- Step B Weigh the light-resistant brilliant red BBC (2.06 g, 0.045 mol) according to the molar ratio of the light-resistant brilliant red BBC to the hydrotalcite precursor to 1.5, and dissolve it in 100 ml of ethylene glycol. .
- Step C Mix the lightfast red BBC solution and the LDHs precursor suspension in a container, then Then, under the protection of 95 ° C, the reaction was stirred for 36h, filtered, washed to a pH of about 7, and dried at 70 ° C for 18h.
- the light-resistant bright red BBC anion intercalation LDHs material was assembled.
- the interlaced pigment has a color difference ⁇ E less than 5 compared with the light-resistant bright red BBC, indicating that the intercalation pigment maintains the original color of the light-resistant bright red BBC.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
¾ ^结构光热稳定型耐晒艳红 BBC颜料及 层方法 技术领域
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。 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 Double Hydroxides , 简写为 LDHs)是一种阴离子型层状材料, 由于其具有可插层 '組装的性能, 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。
文献 Mohd Zobir bin Hussein , Zulkarnain Zainal , Asmah Hj. Yahaya, Azira binti Abd. Aziz, Material s Science and Engineering B88, 2002, 98-102中,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。
文献 Umberto Costantino, Natascia Colett i , and Morena Nocchett i , 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] [C03]。, 165 · 0. 4H20, 再将其与 NaCl和 HC1反应得到水 滑石 Z¾ 67A1。.33 (0H) 2C1。.33 · 0. 4H2O, 再以 Z¾ 67A1。.33 (OH) 2C1Q.33 · 0. 4H20 为前体, 以 曱基橙 (M0) 为客体, 组装得到插层水滑石 [Ζη。· 67Α1。.33 (ΟΗ) 2] [MO。.31C1。, 02〗 · 0. 85H20, 他们考察了产物的荧光性。 其 缺点是前体制备方法复杂。
发明内容
本发明的目的是利用 LDHs的可插层性, 将耐晒艳红 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。
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。
本发明以层间阴离子为 N03—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 N03-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)。
本发明制备的 LDH-BBC的化学通式为: [M2VXM3+ X (OH) 2] (BBC) 2- x/2 . mH20, 其中 0. 2<X/ (1 - X) <0. 5 , m=l - 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。
LDH-BBC的制备步骤如下:
A. 采用单滴法制备结构通式为: [M XM3+ X (OH) 2] (N03) - x · mH20的水 滑石前体, 其中 0. 2<X/ (1 - XX0. 5 , m=l - 3X/2; 将该水滑石加入高沸点 的有机溶剂中, 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;
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;
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°C的条件下反应 6-48h, 过滤、 洗涤到中性, 在 60-100°C干燥 12-24h, 得到耐晒艳红 BBC阴离子插层水滑石 LDH_BBC。
步骤 A 中所用的高沸点的有机溶剂可以是乙二醇、 乙二醇二丁基醚 或二甘醇二乙醚。
将得到的 LDH-BBC进行 XRD、 FT- IR、 UV-Vi s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。
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(ΔΕ) , 结果 ΔΕ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 (1000)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。
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°C的烘箱中受热 30分钟后取出, 用 UV-Vi s分光光度计对 其耐热性进行分析可知, 耐晒艳红 BBC在 200°C时, 其 UV- Vi s 曲线已有 较大幅度的变化, 而插层颜料 LDH- BBC在 300Ό时, 其 UV- Vi s 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。
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緩其退色程度和速度。 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。
具体实施方式
实施例 1
步驟 A:取 Mg (N03) 2 ·6Η20 (15. 38g, 0. 06mol)和 Al (Ν03) 3 · 9Η20 (11. 25g, 0. 03mol)混合,溶于 50ml脱除 0)2的去离子水中;另取 NaOH (7. 20g, 0. 18mol) 溶于 75ml脱除 C02的去离子水中, 置于 250ml三口瓶中; 在 N2保护下将 混合盐溶液緩慢滴入碱液中, 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°C的温度下陈化 39h, 最后 抽滤、 水洗得水滑石前体, 其结构式为:1^^12 (01 12 ^03) 2 ' 41120; 将该 水滑石前体 2, 20g (0. 004mol) ^L在 50ml乙二醇中待用。
步驟 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。
步骤 C: 将耐晒艳红 BBC溶液和 LDHs前体悬浮漩在容器中混合, 然 后在 ^保护下, 90°C搅拌反庶 48h, 过滤、 洗涤至 pH值约为 7, 1G0°C千 燥 18h, 组装得到耐晒艳红 BBC阴离子插层 LDHs材料。
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 ΔΕ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。
实施例 2
步骤 A:取 Mg (N03) 2 ·6Η20 (17. 31g, 0. 0675mol)和 Al (Ν03) 3 ·9Η20 (8. 44g, 0. 0225mol)混合, 溶于 50ml脱除 C02的去离子水中。 另取 NaOH (7. 20g, 0. 18mol)溶于 75ml脱除 C02的去离子水中, 置于 250ml三口瓶中。 在 N2 保护下将混合盐溶液緩慢滴入碱液中, 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 Ό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 (0H) 16 (N03) 2 · 4H20; 将该水滑石 3. 34g (0. 005mol)分散在 50ml 乙二醇中。
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. Olmol) , 使其溶于 200ml乙二醇中。
步骤 C: 将 BBC溶液和 LDHs前体悬浮液在容器中混合, 然后在!^保 护下, 100°C搅拌反应 24h, 过滤、 洗涤至 pH值约为 7, 70°C干燥 24h, 组装得到耐晒艳红阴离子插层材料 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、 结构一致的超夯子插层结构材料。 插层颜料 LDH-BBC 与 BBC 相比, 其色差 ΔΕ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。
实施例 3
步骤 A:取 Ζη (Ν03) 2 · 6Η20 (17. 85g, 0. 06mol)、 Al (N03) 3 · 9Η20 (11. 25g, 0. 03mol)和 NaN03 (4. 53g, 0. 053mol)混合, 溶于 80ml脱除 C02的去离 子水中, 置于 250ml 三口瓶中。 另取 Na0H (5. 32g, 0. 133mol)溶于 50ml 脱除(02的去离子水中。 在 ^保护下将 NaOH碱溶液緩慢滴入混合盐溶 液中, 强烈搅拌, 至 pH = 6 时停止滴加威溶液。 接着将浆状液于 70°C的 温度下陈化 24h, 最后抽滤、 水洗得水滑石前体, 其结构式为: Ζη4Α12 (0Η) 12 (Ν03) 2 - 4H20; 将该水滑石 2. 15g (0. 003mol)分散在 50ml 乙 二醇中。
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。
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 ^保护下, 95 °C搅拌反应 36h, 过滤、 洗涤至 pH值约为 7, 70°C干 燥 18h, 組装得到耐晒艳红 BBC阴离子插层 LDHs材料。
分别采用 XRD、 FT- IR、 UV-Vi s 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 ΔΕ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。
Claims
1、 一种超^^结构光热稳、定型耐晒艳红 BBC颜料, 其特征是该颜料是一 种层间阴离子为耐晒艳红 BBC阴离子的插层水滑石 LDH-BBC, 其化学通式为:
[M^3 (OH) 2] (BBC) 2-x/2 . mH20,
其中 0. 2<X/ (1 - XXO. 5, m=l - 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。
2、 根据权利要求 1所述的超分子结构光热稳定型耐晒艳红 BBC颜料, 其 特征是该颜料与耐晒艳红 BBC颜色的色差 ΔΕ小于 5, 且其光热稳定性能比耐 晒艳红 BBC有大幅度提高。
3、一种超分子结构光热稳定型耐晒艳红 BBC颜料的制备方法, 步骤如下:
A. 采用单滴法制备结构通式为: [M2VXM3+ X (OH) 2] (N03)—x■ mH20的水滑石 前体, 其中 0. 2<X/ (1 - X) <0. 5, m=l - 3X/2; 将该水滑石加入高沸点的有积容 剂中, 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;
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;
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 °C的条件下反应 -48h, 过滤、、 洗涤到中性, 在 60 - 100°C干燥 12- 24h, 得到耐晒艳红 BBC阴离子 4层水滑石 LDH-BBC。 .
4、 根据权利要求 3所述的超分子结构光热稳定型耐晒艳红 BBC颜料的制 备方法, 其特征是步骤 A 中所述的高沸点的有机溶剂可以是乙二醇、 乙二醇 二丁基 二甘醇二乙醚中的任意一种。
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CN1333005C (zh) * | 2005-12-19 | 2007-08-22 | 北京化工大学 | 超分子插层结构紫外光吸收剂及其制备方法和用途 |
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CN101982509A (zh) * | 2010-10-08 | 2011-03-02 | 北京化工大学 | 一种光、热稳定型超分子结构酸性黄17插层颜料及其制备方法 |
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CN103965654B (zh) * | 2014-04-30 | 2016-08-17 | 北京化工大学 | 一种耐光型超分子插层结构颜料及其制备方法 |
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US5414080A (en) * | 1992-11-25 | 1995-05-09 | Board Of Trustees Operating Michigan State University | Porphyrin-metallic complex intercalated layered double hydroxides |
CN1171979A (zh) * | 1996-07-29 | 1998-02-04 | 德国泰克萨科股份公司 | 制备水滑石及其金属氧化物的方法 |
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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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 (zh) * | 1996-07-29 | 1998-02-04 | 德国泰克萨科股份公司 | 制备水滑石及其金属氧化物的方法 |
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