CN101083299A - Unsymmetrical Unsymmetrical phthalocyanine material and method for making same - Google Patents
Unsymmetrical Unsymmetrical phthalocyanine material and method for making same Download PDFInfo
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Abstract
The invention belongs to the organic semiconducting material technology area, specifically relates to an asymmetrical phthalocyanine material and its preparation method. The method used inorganic carrier method and many step response method to prepare asymmetrical phthalocyanine material, which production rate may reach above 20%, separation and purification is simple convenient, it has overcome the traditional asymmetrical phthalocyanine separation-purification difficulties and the low production rate (3%) and so on difficult problems, the invention method has simply convenient, high input-output ratio, the low cost. The asymmetrical phthalocyanine produced has the fine dissolved performance, film-forming performance and the electro-optical performance, and has the very broad application prospect, may apply in the nonlinear optics material, the molecular rectifier, the molecular conductor, the electro-optical transformation material, the gas sensor, the catalyst and light dynamics treat cancer domains and so on.
Description
Technical field
The invention belongs to the organic semiconducting materials technical field, be specifically related to a kind of unsymmetrical phthalocyanine material and preparation method thereof.
Background technology
Since the eighties in 20th century, phthalocyanine compound is as a class novel organic semi-conductor material, because of its excellent photoelectric property, to the stability of light and heat and the controllability of molecular structure, receive domestic and international researcher's very big concern, be widely used in research fields such as laser printing, liquid crystal display, optical storage, Infrared Detectors, field-effect transistor and photovoltaic cell.But traditional phthalocyanine is poorly soluble in water and organic solvent, and this gives the purifying of product, and certain difficulty has all been brought in performance characterization and film forming aspect.And traditional phthalocyanine second order non-linear optical active a little less than, also be difficult to form the LB film of high-sequential.These defectives have all limited its further research in a lot of fields and have used.In order further to open up the new function of phthalocyanine material, existing at present many research workers put into the research of the asymmetric substituted phthalocyanine material with special performance.
Compare with traditional phthalocyanine material, the unsymmetrical phthalocyanine material has than remarkable advantages and unique photoelectric properties, and for example the unsymmetrical phthalocyanine material has fine solubility in ordinary organic solvents, has the ability that forms good LB film, its LB film has strong second-order nonlinear optical property, to NO
2Very strong sensitiveness is arranged, show fast response and recovery rate.Become one of focus of present materialogy research with performance study based on the unsymmetrical phthalocyanine preparation methods.Up to now, it is several that the unsymmetrical phthalocyanine preparation methods of bibliographical information mainly contains statistic law, producing high-molecular method and inferior phthalocyanine method etc.Statistic law is modal a kind of method in the unsymmetrical phthalocyanine preparation methods, but the subject matter that this preparation method exists is very difficulty of the separation of synthetic product and purifying, often needs separate by high-efficient liquid phase chromatogram technology.The producing high-molecular method is that a kind of product separates more simple and effective method relatively, but the subject matter of the method then is to synthesize in advance a kind of adjacent benzene dicyan functional unit that links to each other with macromolecule, work difficulty is bigger, has limited the further extensive use of this method in the unsymmetrical phthalocyanine material preparation.Inferior phthalocyanine method has advantages such as high efficiency, selectivity and product are very easy to separate, yet shortcoming is also very outstanding, and the ring expansion of inferior phthalocyanine still exists uncertainty exactly, and randomized response can produce six kinds of phthalocyanine compounds, make total productive rate still less, separation and purifying are also very difficult.About the unsymmetrical phthalocyanine preparation methods report is arranged seldom also in Chinese patent database and the data of literatures.
Summary of the invention
The objective of the invention is to propose a kind ofly have good solubility property, filming performance and photoelectric properties, and productive rate is higher, preparation technology is simple and isolation and purification is easy to unsymmetrical phthalocyanine material and preparation method thereof.
The unsymmetrical phthalocyanine material that the present invention proposes, be a kind of be matrix with inorganic carriers such as porous glass, diatomite, active carbon, quartz sand or silica gel, through the organic molecule modification, and a kind of inorganic carrier bonding unsymmetrical phthalocyanine material for preparing through the multistep reaction method.Here organic molecule can dihydroxylic alcohols, diamine or amino-contained silane coupler, for example hexylene glycol, ethylenediamine and aminopropyl triethoxysilane (KH-550) etc.Remove to separate behind the inorganic carrier by alkali cleaning and obtain a kind of highly purified unsymmetrical phthalocyanine material.It separates and purification process is comparatively simple and easily, productive rate can reach more than 20%.
The unsymmetrical phthalocyanine preparation methods that the present invention proposes is as follows:
(1) earlier 5～50g inorganic carrier is joined in the 50～200ml concentrated hydrochloric acid or the concentrated sulfuric acid, under the high temperature sonicated 2-4 hour, filter, be washed to neutrality, vacuum drying again obtains the inorganic carrier of surface active;
(2) inorganic carrier behind the above-mentioned surface active of 2.5～25g is dispersed in 25～100ml anhydrous dimethyl benzene solvent, under 60～80 ℃ of conditions, drip a kind of or two or more of 10～100ml dihydroxylic alcohols, diamine and amino-contained silane coupler etc., after dropwising, be warmed up to the solvent boiling point temperature, continued back flow reaction 12～48 hours, filter out inorganic carrier, use methyl alcohol and acetone washes clean final vacuum dry more than 12 hours successively, obtain the inorganic carrier that there are amido or hydroxyl in the surface;
(3) under nitrogen protection, the inorganic carrier that the above-mentioned surface of 1～10g is had amido or hydroxyl is dispersed in the new dimethyl sulfoxide (DMSO) that steams of 50～200ml, add 1～3g nitro again and replace phthalonitrile monomer, after the stirring and dissolving, add 2～4g Anhydrous potassium carbonate powder more in three batches, reacted under the room temperature 6～12 hours, slowly be warming up to 100～120 ℃ again, reacted 24～72 hours, filter out inorganic carrier, use methyl alcohol and acetone washes clean final vacuum dry more than 12 hours successively, obtain the inorganic carrier that the surface has adjacent benzene dicyan group;
(4) under nitrogen protection; the above-mentioned surface of 0.1～1g is had the alkyl of the inorganic carrier of adjacent benzene dicyan group and other kind of 0.02～1g or alkoxyl to be replaced adjacent benzene dicyan and mixes; the urea, 0.01～0.05g anhydrous metal salt, 0.01～0.05g ammonium chloride and a small amount of ammonium molybdate that add 0.1～0.3g again; is solvent at 180～220 ℃ with 50～120ml trichloro-benzenes or nitrobenzene or quinoline, stirring reaction 6～20 hours.Organic solvents such as a large amount of chloroforms of cooling back adding dissolve not the phthalocyanine material and the unreacted raw material of keyed jointing, filter out inorganic carrier, use washes clean such as methyl alcohol and acetone and other organic solvent and vacuumize complete again, obtain a kind of novel inorganic carrier bonding unsymmetrical phthalocyanine material;
(5) alkaline solutions such as the NaOH of the above-mentioned inorganic carrier bonding of 0.1～0.5g unsymmetrical phthalocyanine material and 10～100ml4～10mol/L or sodium carbonate are mixed, the N that adds 30～300ml again, organic solvent such as dinethylformamide or dioxane, 90～100 ℃ of following stirring and refluxing 6～24 hours, the filtrate that filtration obtains is poured in a large amount of deionized waters again, regulate the pH value to 6.0-7.0, have blue flocculent deposit to separate out.Filter out precipitation, vacuumize with chloroform redissolve and purification, obtains a kind of unsymmetrical phthalocyanine material.
Among the present invention, used inorganic carrier can be inorganic carriers such as porous glass, diatomite, active carbon, quartz sand or silica gel.
Among the present invention, used dihydroxylic alcohols, can be ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, methyl propanediol, DPG, 3-chloro-1,2-propylene glycol, 2-butyl-2-ethyl-1, ammediol, butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, isoamyl glycol, 2-methyl-2,4-pentanediol, neopentyl glycol, 1,6-hexylene glycol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol or different Buddhist glycol etc.Used diamine, can be ethylenediamine, tetramethylethylenediamine, N-ethyl-ethylenediamine, diphenyl ethylene diamine, N, N-dibenzyl-ethylenediamin, 1,2-propane diamine, 1,3-propane diamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, positive pentanediamine, secondary pentanediamine, isoamyl diamines, methyl ring pentanediamine, hexamethylene diamine, nonamethylene diamine, decamethylene diamine, 1,2-diaminopropanes, N, N-diethyl-1,3-diaminopropanes, N, N-two-tertiary butyl-ethylenediamine, TCD-diamines or IPD etc.Used amino-contained silane coupler can be γ-amido triethoxysilane (KH-550), N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan (KH-792), γ-hexamethylene aminopropyl silane coupler, diethyl amino methyl triethoxysilane, anilinomethyl triethoxysilane or N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan etc.
Among the present invention, used nitro replaces phthalonitrile monomer, can be that the 3-nitro replaces adjacent benzene dicyan, the 4-nitro replaces phthalonitrile monomer or 3, and the 4-dinitro replaces adjacent benzene dicyan.
Among the present invention, used organic solvent, can be benzene, toluene, ortho-xylene, meta-xylene, paraxylene, chlorobenzene, o-dichlorohenzene, m-dichlorobenzene, paracide, trichloro-benzenes, dichloroethanes, tetrachloroethanes, dimethyl sulfoxide (DMSO), N, dinethylformamide, N, N-dimethylacetylamide, 1,4-dioxane, carrene, chloroform, nitrobenzene or quinoline etc.
Advantage of the present invention is: 1. the present invention utilizes inorganic carrier method and multistep reaction method can prepare a kind of unsymmetrical phthalocyanine material, its productive rate can reach more than 20%, separation and purifying are simple and convenient, and it has overcome traditional a unsymmetrical phthalocyanine separation and purification difficulty and the lower difficult problems such as (3%) of productive rate; Advantage such as that preparation method 2. of the present invention has is simple and convenient, input-output ratio is high, with low cost and application prospect is extensive; 3. this unsymmetrical phthalocyanine material has good solubility property, filming performance and photoelectric properties, have boundless application prospect, can be applicable to fields such as nonlinear optical material, molecular rectifier, molecular conductor, photoelectric conversion material, gas sensing property transducer, catalyst and photodynamic therapy cancer.
Description of drawings
Fig. 1 is the uv-visible absorption spectroscopy figure of unsymmetrical phthalocyanine material.Wherein, a is the weak solution of no substituted phthalocyanine in the concentrated sulfuric acid; B is the weak solution of unsymmetrical phthalocyanine in chloroform.
Fig. 2 is the X-ray diffractogram of unsymmetrical phthalocyanine material.
Embodiment
Adopt the 20g Bio-sil as inorganic carrier, place the 150mL single necked round bottom flask, add the 100mL concentrated hydrochloric acid, sonicated 30min subsequently at 100 ℃ of following backflow 6h, filters and obtains filter cake, washes to neutral with deionized water, and 60 ℃ of following vacuumizes are complete.The Bio-sil of getting after 10g activates places the 150mL single necked round bottom flask, adds 12mL silane resin acceptor kh-550 and 50mL toluene, at 130 ℃ of following backflow 10h.Filter out silica gel, wash back 150 ℃ of following vacuumizes with toluene and ethanol successively, obtain surface-treated Bio-sil.
In the 150mL single necked round bottom flask, add the new N that steams of 30mL, the Bio-sil of the adjacent benzene dicyan of N '-dimethyl formamide, 1.73g (10mmol) 3-nitro, 3.0g Anhydrous potassium carbonate and the above-mentioned processing of 5g, stirring at room reaction 24～72h under condition of nitrogen gas, and repeatedly add Anhydrous potassium carbonate 3g.Filter out silica gel, with toluene, oxolane and distilled water washing, 60 ℃ of following vacuumizes obtain the Bio-sil of surface with adjacent benzene dicyan group fully successively.
Get the dry above-mentioned surface of crossing of 2g with the Bio-sil of adjacent benzene dicyan group, replace adjacent benzene dicyan, 1.5g urea, 0.105g stannous chloride, 0.112g ammonium chloride and a small amount of ammonium molybdate with 0.72g (3.6mmol) dodecyloxy and mix, at 180 ℃ of following nitrobenzene is solvent, stirring reaction 6h.Add the unreacted reactants of dissolving such as a large amount of chloroforms and ethanol after the cooling, filter out silica gel,,, after the vacuumize, get a kind of green phthalocyanine bonding Bio-sil again through washing with the most dotetracontane oxygen of oxolane flush away base CuPc.
With the Bio-sil of the above-mentioned surface of 1g band phthalocyanine, with 20mL dioxane, 30mL N, N '-dimethyl formamide and 50mL concentration are that the KOH solution of 6mol/L mixes, and at 100 ℃ of following stirring and refluxing 12h, filter and obtain filtrate.Filtrate is poured in the 500mL ionized water again, drip the hydrochloric acid of 6mol/L, adjust pH has blue flocculent deposit to separate out to the 6.0-7.0.After filtration and the vacuumize, with chloroform dissolving and purification, obtain green unsymmetrical phthalocyanine material at last, its productive rate is approximately 20.6%.Its solubility property such as table 1, Fig. 1 and Fig. 2 are respectively its uv-visible absorption spectroscopy figure and X-ray diffractogram.
Identical with embodiment 1, but Bio-sil changes diatomite into.
Embodiment 3
Identical with embodiment 1, but Bio-sil changes quartz sand into.
Embodiment 4
Identical with embodiment 1, but silane resin acceptor kh-550 changes hexylene glycol into.
Embodiment 5
Identical with embodiment 1, but silane resin acceptor kh-550 changes hexamethylene diamine into.
Embodiment 6
Identical with embodiment 1, change the isoamyl alkoxyl into and replace adjacent benzene dicyan but dodecyloxy replaces adjacent benzene dicyan.
Embodiment 7
Identical with embodiment 1, but the consumption of silane resin acceptor kh-550 changes 15ml into by 12ml.
Embodiment 8
Identical with embodiment 1, but the consumption of silane resin acceptor kh-550 changes 25ml into by 12ml.
Embodiment 9
Identical with embodiment 1, but reaction temperature changes 200 ℃ into for 180 ℃, nitrobenzene changes quinoline into, and the reaction time, 6h changed 12h into.
Identical with embodiment 1, but the concentration of KOH solution changes 4.5mol/L into by 6mol/L.
Embodiment 11
Identical with embodiment 1, but the concentration of KOH solution changes 9mol/L into by 6mol/L.
Unsymmetrical phthalocyanine material that obtains among the embodiment 2-11 and the material of embodiment 1 have similar performance.
Table 1
| Methyl alcohol | Acetone | Toluene | Chloroform | DMF | Oxolane | DMSO | |
| No substituted phthalocyanine | Insoluble | Insoluble | Insoluble | Insoluble | Insoluble | Insoluble | Insoluble |
| Asymmetric substituted phthalocyanine | Slightly soluble | Molten entirely | Molten entirely | Molten entirely | Molten entirely | Molten entirely | Molten entirely |
Claims (8)
1, a kind of unsymmetrical phthalocyanine material, it is characterized in that with the inorganic carrier being carrier, modify through organic molecule, a kind of inorganic carrier unsymmetrical phthalocyanine material for preparing through the multistep reaction method again, wherein, described inorganic carrier is porous glass, diatomite, active carbon or silica gel, and described organic molecule is dihydroxylic alcohols, diamine or amino-contained silane coupler.
2, a kind of unsymmetrical phthalocyanine preparation methods as claimed in claim 1 is characterized in that concrete steps are:
(1) earlier 5～50g inorganic carrier is joined in the 50～200ml concentrated hydrochloric acid or the concentrated sulfuric acid, under the high temperature sonicated 2-4 hour, filter, be washed to neutrality, vacuum drying again obtains the inorganic carrier of surface active;
(2) inorganic carrier behind the above-mentioned surface active of 2.5～25g is dispersed in 25～100ml anhydrous dimethyl benzene solvent, under 60～80 ℃ of conditions, drip a kind of or two or more of 10～100ml dihydroxylic alcohols, diamine and amino-contained silane coupler, after dropwising, be warmed up to the solvent boiling point temperature, continued back flow reaction 12～48 hours, filter out inorganic carrier, use methyl alcohol and acetone washes clean final vacuum dry more than 12 hours successively, obtain the inorganic carrier that the surface has amido or hydroxyl;
(3) under nitrogen protection, the inorganic carrier that the above-mentioned surface of 1～10g is had amido or hydroxyl is dispersed in the new dimethyl sulfoxide (DMSO) that steams of 50～200ml, add 1～3g nitro again and replace phthalonitrile monomer, after the stirring and dissolving, add 2～4g Anhydrous potassium carbonate powder more in three batches, reacted under the room temperature 6～12 hours, slowly be warming up to 100～120 ℃ of reactions 24～72 hours again, filter out inorganic carrier, use methyl alcohol and acetone washes clean final vacuum dry more than 12 hours successively, obtain the inorganic carrier that the surface has adjacent benzene dicyan group;
(4) under nitrogen protection, the above-mentioned surface of 0.1～1g is had the alkyl of the inorganic carrier of adjacent benzene dicyan group and other kind of 0.02～1g or alkoxyl to be replaced adjacent benzene dicyan and mixes, the urea, 0.01～0.05g anhydrous metal salt, 0.01～0.05g ammonium chloride and a small amount of ammonium molybdate that add 0.1～0.3g again, is solvent at 180～220 ℃ with 50～120ml trichloro-benzenes or nitrobenzene or quinoline, stirring reaction 6～20 hours; Cooling back adds a large amount of organic solvents and dissolves not the phthalocyanine material and the unreacted raw material of keyed jointing, filters out inorganic carrier, and is clean and vacuumize is complete with organic solvent washing again, obtains a kind of novel inorganic carrier bonding unsymmetrical phthalocyanine material;
(5) NaOH or the sodium carbonate alkaline solution with the above-mentioned inorganic carrier bonding of 0.1～0.5g unsymmetrical phthalocyanine material and 10～100ml, 4～10mol/L mixes, the N that adds 30～300ml again, dinethylformamide or dioxane organic solvent, 90～100 ℃ of following stirring and refluxing 6～24 hours, the filtrate that filtration obtains is poured in a large amount of deionized waters again, regulate the pH value to the 6.0-7.0, have blue flocculent deposit to separate out; Filter out precipitation, vacuumize with chloroform redissolve and purification, promptly obtains a kind of unsymmetrical phthalocyanine material.
3, preparation method according to claim 2 is characterized in that described used inorganic carrier is porous glass, diatomite, active carbon, quartz sand or silica gel.
4, preparation method according to claim 2 is characterized in that used dihydroxylic alcohols is ethylene glycol, propylene glycol, butanediol, isoamyl glycol, 1,6-hexylene glycol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol or different Buddhist glycol.
5, preparation method according to claim 2 is characterized in that used diamine is ethylenediamine, propane diamine, butanediamine, pentanediamine, diamines, nonamethylene diamine or decamethylene diamine.
6, preparation method according to claim 2, it is characterized in that said amino-contained silane coupler, is γ-amido triethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-hexamethylene aminopropyl silane coupler, diethyl amino methyl triethoxysilane, anilinomethyl triethoxysilane or N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan.
7, preparation method according to claim 2 is characterized in that it is that the 3-nitro replaces adjacent benzene dicyan, the 4-nitro replaces phthalonitrile monomer or 3 that said nitro replaces phthalonitrile monomer, and the 4-dinitro replaces adjacent benzene dicyan.
8, preparation method according to claim 2, it is characterized in that used organic solvent is for being benzene, toluene, ortho-xylene, meta-xylene, paraxylene, chlorobenzene, o-dichlorohenzene, m-dichlorobenzene, paracide, trichloro-benzenes, dichloroethanes, tetrachloroethanes, dimethyl sulfoxide (DMSO), N, dinethylformamide, N, N-dimethylacetylamide, 1,4-dioxane, carrene, chloroform, nitrobenzene or quinoline.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101969101A (en) * | 2010-09-30 | 2011-02-09 | 昆明物理研究所 | Phthalocyanine rare earth organic infrared semiconductor light guide detector |
| CN101648696B (en) * | 2009-08-13 | 2012-07-04 | 同济大学 | Method for preparing graphene-phthalocyanin nano composite material by mercaptan-alkene clicking chemical method |
| CN108164539A (en) * | 2017-12-29 | 2018-06-15 | 先尼科化工（上海）有限公司 | A kind of novel green phthalocyanine compound and preparation method thereof |
| CN111334065A (en) * | 2020-03-30 | 2020-06-26 | Tcl华星光电技术有限公司 | Phthalocyanine dye, optical filter and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1356329A (en) * | 2001-08-16 | 2002-07-03 | 天津青迈信息材料有限公司 | Unsymmetric phthalocyanine derivative and its application in optical record medium |
| CN1299377C (en) * | 2003-12-31 | 2007-02-07 | 山东理工大学 | Application of products with active carbon surface chemically decorated by porphyrin and phthalocyanine in fuel cells |
| EP1920436A2 (en) * | 2005-07-28 | 2008-05-14 | Ciba Specialty Chemicals Holding, Inc. | Optical data storage |
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2007
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648696B (en) * | 2009-08-13 | 2012-07-04 | 同济大学 | Method for preparing graphene-phthalocyanin nano composite material by mercaptan-alkene clicking chemical method |
| CN101969101A (en) * | 2010-09-30 | 2011-02-09 | 昆明物理研究所 | Phthalocyanine rare earth organic infrared semiconductor light guide detector |
| CN101969101B (en) * | 2010-09-30 | 2012-07-25 | 昆明物理研究所 | Phthalocyanine rare earth organic infrared semiconductor light guide detector |
| CN108164539A (en) * | 2017-12-29 | 2018-06-15 | 先尼科化工（上海）有限公司 | A kind of novel green phthalocyanine compound and preparation method thereof |
| CN108164539B (en) * | 2017-12-29 | 2020-09-18 | 先尼科化工（上海）有限公司 | Green phthalocyanine compound and preparation method thereof |
| CN111334065A (en) * | 2020-03-30 | 2020-06-26 | Tcl华星光电技术有限公司 | Phthalocyanine dye, optical filter and preparation method thereof |
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