CN102453034A - Green synthesis method of copper phthalocyanine - Google Patents
Green synthesis method of copper phthalocyanine Download PDFInfo
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- CN102453034A CN102453034A CN201110432636XA CN201110432636A CN102453034A CN 102453034 A CN102453034 A CN 102453034A CN 201110432636X A CN201110432636X A CN 201110432636XA CN 201110432636 A CN201110432636 A CN 201110432636A CN 102453034 A CN102453034 A CN 102453034A
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- copper phthalocyanine
- single crystal
- steel bomb
- starting material
- phthalocyanine
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- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 title claims abstract 5
- 238000001308 synthesis method Methods 0.000 title abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 18
- 239000010959 steel Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000007858 starting material Substances 0.000 claims abstract 4
- 150000001879 copper Chemical class 0.000 claims abstract 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims abstract 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims abstract 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- 239000004809 Teflon Substances 0.000 abstract 1
- 229920006362 Teflon® Polymers 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 abstract 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 abstract 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 9
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002475 indoles Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000005289 physical deposition Methods 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- 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
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0026—Crystal modifications; Special X-ray patterns of phthalocyanine pigments
-
- 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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/073—Preparation from isoindolenines, e.g. pyrrolenines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
本发明公开了一种酞菁铜的绿色合成法，属于有机合成技术领域，涉及酞菁铜的合同方法。包括以下步骤：（1）以0.1mmol铜盐和0.4mmol吲哚为起始原料，把起始原料放到带有聚四氟乙烯内衬的钢弹中，加入10mmLDMF溶剂；（2）把钢弹拧紧；（3）把钢弹放在烘箱里，控制温度在80℃以下，反应50-70min后，冷却至室温；（4）冷却后过滤，然后用甲醇冲洗，即得紫色针状的酞菁铜。本发明方法大大缩短了单晶生长时间，成功率非常高；用很短时间就可以生长出10.5mm左右的单晶，同时成功率100%，设备简单，成本低。
The invention discloses a green synthesis method of copper phthalocyanine, belongs to the technical field of organic synthesis, and relates to a contract method of copper phthalocyanine. Including the following steps: (1) Using 0.1mmol copper salt and 0.4mmol indole as the starting material, put the starting material into a steel bomb with a Teflon liner, and add 10mm LDMF solvent; (2) Put the steel bomb (3) Put the steel bullet in an oven, control the temperature below 80°C, react for 50-70 minutes, and cool to room temperature; (4) After cooling, filter, and then rinse with methanol to obtain purple needle-shaped phthalein Cyanine copper. The method of the invention greatly shortens the single crystal growth time, and has a very high success rate; a single crystal of about 10.5mm can be grown in a very short time, and the success rate is 100%, and the equipment is simple and the cost is low.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate to the contract method of CuPc, be specifically related to the green synthesis method of CuPc.
Background technology
Phthalocyanine is the aroma system with two dimension 18 πDian Zis of high stability, existing more than 70 kind of different metallic and the nonmetal central atom that can be used as phthalocyanine.Usually; The conjugated system of phthalocyanine refers to be made up of 18-πDian Zi fragrance cloud delocalization system; The system of forming by nine carbon nitrogen conjugated double bonds; These nine carbon nitrogen or carbon carbon conjugated double bond " surround " phthalocyanine and divide the subcenter hole, and phthalocyanine or metal phthalocyanine specific molecular structure have determined them to be replaced by different way by multiple group, and existing so far more than 5000 kind of phthalocyanine-like compound is synthesized out.
The phthalocyanines title complex has similar skeleton structure with natural porphyrin, chlorophyll, protoheme etc., is one type of compound with π-electron conjugated system, has unique physicochemical property such as light, electricity, magnetic and catalysis.According to this character, phthalocyanine is applied at many sciemtifec and technical spheres, electrochemical apparatus for example, the nonlinear optical electric material, the special material of photovoltaic, the organic effect thin film sensor, etc. the aspect application is all arranged.Find nearly 5000 kinds of phthalocyanine derivates now, had only the CuPc material in industrial production, to be able to widespread use.
The CuPc crystal is confirmed the structure of molecular crystal with XRD, is divided into eight kinds in proper order according to the crystal formation of finding crystalline structure, α-, β-, γ-, δ-, ε-. R-, p-, X-type.Since in the crystal Intermolecular Forces very a little less than, therefore loosely organized, thermal expansion percentage coupling and poor heat stability.Just be transformed into β-type so surpass 200 ℃ of other crystal formations, and except the p-type, the crystal formation of other types can directly or indirectly prepare from β-type with chemical process.
At present, the phthalocyanine-like compound monocrystalline can't directly obtain from synthetic, cultivates the phthalocyanine-like compound monocrystalline and often adopts the concentrated sulfuric acid solution recrystallization method; Gas phase physical deposition method, gas phase physical deposition method growing single-crystal is shorter, and the longest is 5mm; The solution gradient falling temperature method, the method growth cycle of liquid gradient cooling is long, about 80 hours.In a word; All there is the long shortcoming of growth cycle in this several method; Dissolve and crystalline size is little, success ratio is low owing to obtaining, be accompanied by the reasons such as loss, crystal and medium separation difficulty of solution or current-carrying gas in the crystal growing process, and make troubles to crystal growth.
Summary of the invention
The objective of the invention is for a kind of green synthesis method of CuPc is provided.
The present invention realizes through following technical scheme:
The green synthesis method of CuPc may further comprise the steps:
(1) is starting raw material with 0.1mmol mantoquita and 0.4mmol indoles, is put into starting raw material and has in the teflon-lined steel bomb, add the 10mmLDMF solvent;
(2) tighten steel bomb;
(3) be placed on steel bomb in the baking oven, controlled temperature behind the reaction 50-70min, is cooled to room temperature at 60-80 ℃;
(4) cooled and filtered is used washed with methanol then, promptly gets the acicular CuPc of purple.
Further, described mantoquita is a copper sulfate.
The present invention is a raw material with mantoquita and indoles, in water in heating, directly synthetic metal phthalocyanine compound, chemical equation is as follows:
Its molecular formula of the acicular CuPc of purple is C
32H
16CuN
8, productive rate can reach 65%, and monocrystalline is about 10.5mm.
The inventive method solves the problem that the phthalocyanine-like compound crystal growth cycle is long, success ratio is low and cost is high, so for the relevant organic functional molecular material single crystal samples of preparation how monocrystalline be that the photoelectric device of material provides new approach.
The inventive method has shortened the single crystal growing time greatly, and success ratio is very high; Just can grow the monocrystalline about 10.5mm with very short time, success ratio 100% simultaneously, equipment is simple, and cost is low.
Description of drawings
Fig. 1 is the single crystal samples picture;
Fig. 2 is the single crystal samples molecular structure;
Fig. 3 is a single crystal samples packing of molecules structure iron;
Fig. 4 is the X-ray polycrystalline diffraction spectra of single crystal samples;
Fig. 5 is the standard card of the X-ray polycrystalline diffraction spectra of single crystal samples.
Embodiment
Embodiment 1
The green synthesis method of CuPc may further comprise the steps:
(1) is starting raw material with 0.1mmol copper sulfate and 0.4mmol indoles, is put into starting raw material and has in the teflon-lined steel bomb, add the 10mmLDMF solvent;
(2) tighten steel bomb;
(3) be placed on steel bomb in the baking oven, controlled temperature behind the reaction 70min, is cooled to room temperature at 80 ℃;
(4) cooled and filtered is used washed with methanol then, promptly gets the acicular CuPc of purple.
Figure is as shown in Figure 1 for the gained single crystal samples, wherein obtains maximum crystal: 10.5 mm ', 50 mm ', 30 mm.
The single crystal samples molecular structure is as shown in Figure 2, and the CuPc molecular formula is CuN
8C
32H
16, the monocrystalline spacer is P2 (1)/n, parameter is: and a=14.668 (3), b=4.8109 (10), c=19.515 (7), α=90, β=121.04 (2), γ=90, unit volume is 1179.91 ()
3, according to above parameter, this crystal formation belongs to the β type.
Single crystal samples packing of molecules structure iron is as shown in Figure 3.
The X-ray polycrystalline diffraction spectra of single crystal samples is as shown in Figure 4, and the standard card of the X-ray polycrystalline diffraction spectra of single crystal samples is as shown in Figure 5, and wherein the position at each peak and intensity are as shown in table 1,
Table 1
Can find out that from table 1 peak position and intensity and standard shown in Figure 5 are relatively blocked identical fine.
The green synthesis method of CuPc may further comprise the steps:
(1) is starting raw material with 0.1mmol mantoquita and 0.4mmol indoles, is put into starting raw material and has in the teflon-lined steel bomb, add the 10mmLDMF solvent;
(2) tighten steel bomb;
(3) be placed on steel bomb in the baking oven, controlled temperature behind the reaction 80min, is cooled to room temperature at 70 ℃;
(4) cooled and filtered is used washed with methanol then, promptly gets the acicular CuPc of purple.
Embodiment 3
The green synthesis method of CuPc may further comprise the steps:
(1) is starting raw material with 0.1mmol mantoquita and 0.4mmol indoles, is put into starting raw material and has in the teflon-lined steel bomb, add the 10mmLDMF solvent;
(2) tighten steel bomb;
(3) be placed on steel bomb in the baking oven, controlled temperature behind the reaction 60min, is cooled to room temperature at 60 ℃;
(4) cooled and filtered is used washed with methanol then, promptly gets the acicular CuPc of purple.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110432636XA CN102453034A (en) | 2011-12-21 | 2011-12-21 | Green synthesis method of copper phthalocyanine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110432636XA CN102453034A (en) | 2011-12-21 | 2011-12-21 | Green synthesis method of copper phthalocyanine |
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| CN102453034A true CN102453034A (en) | 2012-05-16 |
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|---|---|---|---|
| CN201110432636XA Pending CN102453034A (en) | 2011-12-21 | 2011-12-21 | Green synthesis method of copper phthalocyanine |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007002981A1 (en) * | 2005-07-05 | 2007-01-11 | Silverbrook Research Pty Ltd | Red-shifted water-dispersible ir dyes |
| CN101622262A (en) * | 2007-01-11 | 2010-01-06 | 西巴控股有限公司 | Near infrared absorbing phthalocyanines and their use |
| CN101659666A (en) * | 2009-09-26 | 2010-03-03 | 运城学院 | Method for synthesizing copper phthalocyanine crystals by copper powder directly |
-
2011
- 2011-12-21 CN CN201110432636XA patent/CN102453034A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007002981A1 (en) * | 2005-07-05 | 2007-01-11 | Silverbrook Research Pty Ltd | Red-shifted water-dispersible ir dyes |
| CN101622262A (en) * | 2007-01-11 | 2010-01-06 | 西巴控股有限公司 | Near infrared absorbing phthalocyanines and their use |
| CN101659666A (en) * | 2009-09-26 | 2010-03-03 | 运城学院 | Method for synthesizing copper phthalocyanine crystals by copper powder directly |
Non-Patent Citations (1)
| Title |
|---|
| 夏道成，等: "溶剂热法直接合成酞菁铜晶体", 《高等学校化学学报》, vol. 29, no. 2, 28 February 2008 (2008-02-28), pages 244 - 246 * |
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Application publication date: 20120516 |