CN102675625A - Preparation method for water-solubility metal phthalocyanine derivative - Google Patents
Preparation method for water-solubility metal phthalocyanine derivative Download PDFInfo
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- CN102675625A CN102675625A CN2012101293104A CN201210129310A CN102675625A CN 102675625 A CN102675625 A CN 102675625A CN 2012101293104 A CN2012101293104 A CN 2012101293104A CN 201210129310 A CN201210129310 A CN 201210129310A CN 102675625 A CN102675625 A CN 102675625A
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Abstract
The invention relates to a preparation method for a water-solubility metal phthalocyanine derivative. The method includes (1) adopting a phthalic anhydride-urea solid phase synthesizing method to synthesize octa-carboxyl metal phthalocyanine; (2) mixing the octa-carboxyl metal phthalocyanine and polyethylene glycol, then adding an organic solvent, adding concentrated sulfuric acid as a catalyst, reacting for about 0.5-20 hours at the temperature of 100-150 DEG C, and finally washing, filtering, driving so as to obtain the metal phthalocyanine derivative indicated in a general formula 1. The preparation method is simple in reaction and operation, short in required time, fast in reaction, safe and energy-saving compared with other methods, few in raw materials and reagents required by the reaction and small in product toxicity and environment damage. The derivative is good in water solubility, easy to dissolve in organic solvents such as methanol and ethanol. The general formula 1 is as followed.
Description
Technical field
The invention belongs to the preparation field of phthalocyanine derivates, particularly a kind of preparation method of water-soluble metal phthalocyanine verivate.
Background technology
Phthalocyanine comes across 1907 the earliest, is a kind of big cyclophane aroma compounds with 18 ∏ electronics, and its center has a diameter to be about 2.7 * 10
-10The hole of m can hold many metals and transition metal, and two Wasserstoffatomss in the center cavity can be replaced by more than 70 kinds of elements, comprise nearly all metallic element and a part of non-metallic element, form metal phthalocyanine (being expressed as MPc).That phthalocyanine and phthalocyanine derivates have is bright-colored, tint permanence is excellent, good optical is stable, chemicalstability and calorifics stability, excellent light, electrical property and excellent antibiotic, smelly character disappears; Because the cavity in the phthalocyanine ring is bigger; Can hold multiple metallic element, this makes phthalocyanine be of great use increases greatly.
But the solvability of phthalocyanine has had a strong impact on the use of phthalocyanine, and therefore, the solvability that how to improve phthalocyanine has attracted the sight of a large amount of researchers.There are a lot of document patents to report both at home and abroad to improving the deliquescent method of phthalocyanine.Human DBU catalysis synthesis process such as Sergeyev have prepared a series of eight carboxyl phthalocyanine and esterified derivatives thereof, and they have improved solvability [S.Sergeyev, the E.Pouzet of phthalocyanine derivates in organic solvent; O.Debever, J.Levin, J.Gierschner; J.Cornil, R.G.Aspe, Y.H.Geerts.Liquid crystalline octaalkoxycarbonyl phthalocyanines:design; Synthesis, electronic structure, self-aggregation and mesomorphism.J.of Mater.Chem.; 2007,17:1777-1784].Chinese patent CN 1236006A has reported a kind of method for preparing water-soluble metal phthalocyanine; It is raw material that this method is selected the phthalocyanines derivates that contains sulfo group for use; And select suitable anionic dispersing agents for use, after the mixing stirring makes it homogenizing, adopt spray-dired method to prepare the water soluble metal phthalocyanine particle.Chinese patent CN 1106846A, CN 1106431A has also reported the method for preparing water-soluble dye, two kinds of methods all are first synthetic phthalocyanine SULPHURYL CHLORIDE and derivative compound thereof, obtain water soluble phthalocyanine through a series of processing.But this method relative complex for preparing water soluble metal phthalocyanine, required time is of a specified duration, and the agents useful for same material toxicity is big, and environment is had harm.
In recent years; The synthetic technology of phthalocyanines derivates is constantly ripe; Productive rate improves constantly, and human solid phase methods such as Pan Yong synthesize eight carboxyl metal phthalocyanine derivatives, and record its have certain water-soluble [Pan Yong. Chen Wenxing. Yu Zhicheng. the synthetic and catalytic oxidation performance research of eight carboxyl metal phthalocyanine derivatives. the Zhejiang Prov Engineering Academy journal; 2002,19:141-144].This method raw material and by product toxicity are little, and is little to environmental hazard, easy and simple to handle, and the reaction times is short, and productive rate is high, but solubleness is less in water.The high molecular polymer that polyoxyethylene glycol is a kind of very easily water-soluble, good biocompatibility, have no side effect.At present, also do not see with poly ethyldiol modified phthalocyanine derivates raising its water miscible report and patent.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of water-soluble metal phthalocyanine verivate (shown in general formula 1), and this method is easy and simple to handle, and required time is short, and the metal phthalocyanine derivative that obtains has polyoxyethylene glycol side chain, good water solubility.
General formula 1
Wherein M is the atoms metal that can form metal phthalocyanine, comprises Mn (II), Fe (III), Cu (II), Zn (II) and Co (II).
The preparation method of a kind of water-soluble metal phthalocyanine verivate of the present invention comprises:
(1) adopts the synthetic eight carboxyl metal phthalocyanines of phthalic anhydride-urea solid-phase synthesis, gained eight carboxyl metal phthalocyanines such as general formula 2;
General formula 2
Wherein M is the atoms metal that can form metal phthalocyanine, comprises Mn (II), Fe (III), Cu (II), Zn (II) and Co (II).
(2) above-mentioned eight carboxyl metal phthalocyanines are mixed with polyoxyethylene glycol; Add organic solvent then, add the vitriol oil again, reacted about 0.5-20 hour down at 100-150 ℃ as catalyzer; Wash at last, filter, drying, promptly getting side chain is eight carboxyl metal phthalocyanine derivatives of polyoxyethylene glycol.
Eight carboxyl metal phthalocyanines described in the step (1) comprise eight carboxyl manganese phthalocyanine, eight carboxyl FePCs, eight carboxyl CuPcs, eight carboxyl Phthalocyanine Zinc and eight carboxyl phthalocyanine cobalts.
Organic solvent described in the step (2) is a kind of among DMAc, DMSO, the DMF.
The mol ratio of eight carboxyl metal phthalocyanines described in the step (2) and polyoxyethylene glycol is 1: 8, and the equal molecular mass of the relative number of used polyoxyethylene glycol is 200-8000.
The vitriol oil described in the step (2) is the vitriol oil of mass concentration 90%-98.3%.
Beneficial effect
(1) operation of the present invention is easy, and required time is short, and speed of response is fast, reacts energy-saving safe more with additive method than this, reacts raw materials used, reagent, product toxicity is little, and is little to environmental hazard;
(2) after reaction finished, the layering in acetone soln of product and by product was repeatedly washed through acetone, obtains easily than clean product, and separating and purifying method is easy;
(3) polyoxyethylene glycol has good wetting ability, and the very big solvability of the raising phthalocyanine derivates of degree increases the range of application field of phthalocyanine derivates;
(4) except that very easily being dissolved in the water, verivate of the present invention also very easily is dissolved in organic solvents such as methyl alcohol, ethanol.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) adopt the synthetic eight carboxyl FePCs of phthalic anhydride-urea solid-phase synthesis, concrete grammar is with 23mmol pyromellitic dianhydride, 0.44mol urea, 47mmol FeCl
36H
2O and 0.16mmol Ammonium Molybdate Tetrahydrate add in the container, and microwave heating 10min, product are respectively with hot water, acetone, 6mol/L HCl washing; Oven dry back in 15%NaOH solution in 90 ℃ of reaction 6h, dilute with water, suction filtration, using the hydrochloric acid of mass concentration 36-38% to transfer to pH filtrating is 2; Leaving standstill for some time topples over the upper strata stillness of night; After water, 2mol/L hydrochloric acid, methyl alcohol repeatedly wash, centrifugal, product dried in vacuum drying oven promptly get eight carboxyl FePCs.
(2) get 0.10g step (1) gained eight carboxyl FePCs; Got the 0.52g relative molecular mass in 1: 8 in molar ratio and be 600 polyoxyethylene glycol, join among the 30mL DMAc, add 2mL 95% vitriol oil again and make catalyzer; Put into there-necked flask, 150 ℃ of following reflux 2 hours.After cooling, cross the leaching supernatant liquid, and place vacuum drying oven dry; Remove solvent DMAc,, repeatedly wash the back separatory with acetone then with remaining oily product; Take off a layer throw out and in baking oven, dry, can obtain purified water soluble metal phthalocyanine iron verivate with polyoxyethylene glycol side chain.
Embodiment 2
(1) adopt the synthetic eight carboxyl phthalocyanine cobalts of phthalic anhydride-urea solid-phase synthesis, concrete grammar is with 23mmol pyromellitic dianhydride, 0.44mol urea, 47mmol CoCl
26H
2O and 0.16mmol Ammonium Molybdate Tetrahydrate add in the container, and microwave heating 10min, product are respectively with hot water, acetone, 6mol/L HCl washing; Oven dry back in 15%NaOH solution in 90 ℃ of reaction 6h, dilute with water, suction filtration, using the hydrochloric acid of mass concentration 36-38% to transfer to pH filtrating is 2; Leaving standstill for some time topples over and supernatant liquid; After water, 2mol/L hydrochloric acid, methyl alcohol repeatedly wash, centrifugal, product dried in vacuum drying oven promptly get eight carboxyl phthalocyanine cobalts.
(2) get 0.10g step (1) gained eight carboxyl phthalocyanine cobalts; Got the 3.49g relative molecular mass in 1: 8 in molar ratio and be 4000 polyoxyethylene glycol, join among the 35mL DMSO, add 2mL 98.3% vitriol oil again and make catalyzer; Put into there-necked flask, 140 ℃ of following reflux 6 hours.After cooling, cross the leaching supernatant liquid, and place vacuum drying oven dry; Remove solvent DMSO,, repeatedly wash the back separatory with acetone then with remaining oily product; Take off a layer throw out and in baking oven, dry, can obtain purified water soluble metal phthalocyanine cobalt verivate with polyoxyethylene glycol side chain.
Embodiment 3
(1) adopt the synthetic eight carboxyl Phthalocyanine Zinc of phthalic anhydride-urea solid-phase synthesis, concrete grammar is with 23mmol pyromellitic dianhydride, 0.44mol urea, 47mmol ZnCl
2Add in the container with the 0.16mmol Ammonium Molybdate Tetrahydrate, microwave heating 10min, product are respectively with hot water, acetone, 6mol/L HCl washing; Oven dry back in 15%NaOH solution in 90 ℃ of reaction 6h, dilute with water, suction filtration, using the hydrochloric acid of mass concentration 36-38% to transfer to pH filtrating is 2; Leaving standstill for some time topples over and supernatant liquid; After water, 2mol/L hydrochloric acid, methyl alcohol repeatedly wash, centrifugal, product dried in vacuum drying oven promptly get eight carboxyl Phthalocyanine Zinc.
(2) get 0.10g step (1) gained eight carboxyl Phthalocyanine Zinc; Got the 0.17g relative molecular mass in 1: 8 in molar ratio and be 200 polyoxyethylene glycol, join among the 40mL DMF, add 2mL 90% vitriol oil again and make catalyzer; Put into there-necked flask, 130 ℃ of following reflux 10 hours.After cooling, cross the leaching supernatant liquid, and place vacuum drying oven dry; Remove solvent DMF,, repeatedly wash the back separatory with acetone then with remaining oily product; Take off a layer throw out and in baking oven, dry, can obtain purified water soluble metal phthalocyanine zinc derivative with polyoxyethylene glycol side chain.
Embodiment 4
(1) adopt the synthetic eight carboxyl CuPcs of phthalic anhydride-urea solid-phase synthesis, concrete grammar is with 23mmol pyromellitic dianhydride, 0.44mol urea, 47mmol CuCl
2Add in the container with the 0.16mmol Ammonium Molybdate Tetrahydrate, microwave heating 10min, product are respectively with hot water, acetone, 6mol/L HCl washing; Oven dry back in 15%NaOH solution in 90 ℃ of reaction 6h, dilute with water, suction filtration, using the hydrochloric acid of mass concentration 36-38% to transfer to pH filtrating is 2; Leaving standstill for some time topples over and supernatant liquid; After water, 2mol/L hydrochloric acid, methyl alcohol repeatedly wash, centrifugal, product dried in vacuum drying oven promptly get eight carboxyl CuPcs.(2) get 0.10g step (1) gained eight carboxyl CuPcs; Got the 1.75g relative molecular mass in 1: 8 in molar ratio and be 2000 polyoxyethylene glycol, join among the 45mL DMAc, add 2mL 98% vitriol oil again and make catalyzer; Put into there-necked flask, 120 ℃ of following reflux 14 hours.After cooling, cross the leaching supernatant liquid, and place vacuum drying oven dry; Remove solvent DMAc,, repeatedly wash the back separatory with acetone then with remaining oily product; Take off a layer throw out and in baking oven, dry, can obtain purified water soluble metal phthalocyanine copper verivate with polyoxyethylene glycol side chain.
Embodiment 5
(1) adopt the synthetic eight carboxyl manganese phthalocyanine of phthalic anhydride-urea solid-phase synthesis, concrete grammar is with 23mmol pyromellitic dianhydride, 0.44mol urea, 47mmol MnCl
2Add in the container with the 0.16mmol Ammonium Molybdate Tetrahydrate, microwave heating 10min, product are respectively with hot water, acetone, 6mol/L HCl washing; Oven dry back in 15%NaOH solution in 90 ℃ of reaction 6h, dilute with water, suction filtration, using the hydrochloric acid of mass concentration 36-38% to transfer to pH filtrating is 2; Leaving standstill for some time topples over and supernatant liquid; After water, 2mol/L hydrochloric acid, methyl alcohol repeatedly wash, centrifugal, product dried in vacuum drying oven promptly get eight carboxyl manganese phthalocyanine.
(2) get 0.10g step (1) gained eight carboxyl manganese phthalocyanine; Got the 0.87g relative molecular mass in 1: 8 in molar ratio and be 1000 polyoxyethylene glycol, join among the 25mL DMSO, add 2mL 98% vitriol oil again and make catalyzer; Put into there-necked flask, 100 ℃ of following reflux 16 hours.After cooling, cross the leaching supernatant liquid, and place vacuum drying oven dry; Remove solvent DMSO,, repeatedly wash the back separatory with acetone then with remaining oily product; Take off a layer throw out and in baking oven, dry, can obtain purified water soluble metal phthalocyanine manganese verivate with polyoxyethylene glycol side chain.
Claims (5)
1. the preparation method of a water-soluble metal phthalocyanine verivate comprises:
(1) adopts the synthetic eight carboxyl metal phthalocyanines of phthalic anhydride-urea solid-phase synthesis;
(2) above-mentioned eight carboxyl metal phthalocyanines are mixed with polyoxyethylene glycol, add organic solvent then, add the vitriol oil again, 100-150 ℃ of down reaction about 0.5-20 hour, wash at last, filter, drying, get final product as catalyzer.
2. the preparation method of a kind of water-soluble metal phthalocyanine verivate according to claim 1 is characterized in that: step
(1) eight carboxyl metal phthalocyanines described in are as follows:
General formula 2
Wherein M is the atoms metal that can form metal phthalocyanine, is Mn (II), Fe (III), Cu (II), Zn (II) or Co (II).
3. the preparation method of a kind of water-soluble metal phthalocyanine verivate according to claim 1 is characterized in that: the organic solvent described in the step (2) is a kind of among DMAc, DMSO, the DMF.
4. the preparation method of a kind of water-soluble metal phthalocyanine verivate according to claim 1; It is characterized in that: the mol ratio of eight carboxyl metal phthalocyanines described in the step (2) and polyoxyethylene glycol is 1: 8, and the equal molecular mass of the relative number of used polyoxyethylene glycol is 200-8000.
5. the preparation method of a kind of water-soluble metal phthalocyanine verivate according to claim 1 is characterized in that: the vitriol oil described in the step (2) is the vitriol oil of mass concentration 90%-98.3%.
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| CN103254199A (en) * | 2012-11-30 | 2013-08-21 | 苏州大学 | Preparation method of tetra-tert-butyl fluoro gallium phthalocyanine supermolecule nano-wire |
| CN105195222A (en) * | 2015-09-17 | 2015-12-30 | 中国石油大学(华东) | Occarboxyl cobalt phthalocyanine catalyst for natural gas demercaptan |
| CN105482431A (en) * | 2015-12-01 | 2016-04-13 | 东华大学 | Preparation method of antibiosis and deodorization polypropylene fibers |
| CN105583009A (en) * | 2016-01-21 | 2016-05-18 | 浙江理工大学 | FePc(COOH)8 sensitized TiO2 catalyst and synthetic method thereof |
| CN105600868A (en) * | 2016-01-21 | 2016-05-25 | 浙江理工大学 | Application of titanium dioxide catalyst sensitized by octacarboxylic iron phthalocyanine to degradation of organic dyes under visible light |
| CN105642356A (en) * | 2016-01-21 | 2016-06-08 | 浙江理工大学 | Iron tetracarboxy-phthalocyanine sensitized titanium dioxide catalyst and synthetic method thereof |
| CN105665029A (en) * | 2016-01-21 | 2016-06-15 | 浙江理工大学 | Application of tetracarboxyphthalocynine iron (III) and sensitized titanium dioxide catalyst to degrading of organic dyes in presence of visible light |
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| CN108375569A (en) * | 2018-02-09 | 2018-08-07 | 安徽工业大学 | A kind of preparation method of phthalocyanine/graphene composite sensing material for cyanide ion identification |
| CN108940365A (en) * | 2018-06-25 | 2018-12-07 | 山东大学 | A method of preparing FePC water soluble disperse nanoparticle |
| CN109983021A (en) * | 2016-10-06 | 2019-07-05 | 金科技公司 | Produce the production technology of the carboxyl metal phthalocyanine of dyestuff and pigment |
| CN110128431A (en) * | 2019-06-24 | 2019-08-16 | 哈尔滨理工大学 | A kind of solid phase synthesis process of phthalocyanine metal chemical combination object |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2172319C1 (en) * | 2000-04-26 | 2001-08-20 | Государственный научный центр Российской Федерации "НИОПИК" (ГНЦ РФ "НИОПИК") | Octa-4,5-carboxylic acid phthalocyanine cobalt esters, their inclusion complexes with beta-cyclodextrin propylene glycol ester and method of suppression of tumor growth |
| CN102268752A (en) * | 2011-06-02 | 2011-12-07 | 浙江华峰氨纶股份有限公司 | Method for manufacturing polyurethane elastic fibers containing octacarboxylic metal phthalocyanines |
-
2012
- 2012-04-27 CN CN201210129310.4A patent/CN102675625B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2172319C1 (en) * | 2000-04-26 | 2001-08-20 | Государственный научный центр Российской Федерации "НИОПИК" (ГНЦ РФ "НИОПИК") | Octa-4,5-carboxylic acid phthalocyanine cobalt esters, their inclusion complexes with beta-cyclodextrin propylene glycol ester and method of suppression of tumor growth |
| CN102268752A (en) * | 2011-06-02 | 2011-12-07 | 浙江华峰氨纶股份有限公司 | Method for manufacturing polyurethane elastic fibers containing octacarboxylic metal phthalocyanines |
Non-Patent Citations (1)
| Title |
|---|
| 潘恩霆等: "聚乙二醇固载四羧基酞菁钴的合成及其脱硫活性的研究", 《化学世界》, no. 11, 31 December 1993 (1993-12-31), pages 529 - 532 * |
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| CN105195222A (en) * | 2015-09-17 | 2015-12-30 | 中国石油大学(华东) | Occarboxyl cobalt phthalocyanine catalyst for natural gas demercaptan |
| CN105195222B (en) * | 2015-09-17 | 2017-11-10 | 中国石油大学(华东) | A kind of eight carboxyl phthalocyanine cobalt catalysts for selexol process alcohol |
| CN105482431A (en) * | 2015-12-01 | 2016-04-13 | 东华大学 | Preparation method of antibiosis and deodorization polypropylene fibers |
| CN105600868A (en) * | 2016-01-21 | 2016-05-25 | 浙江理工大学 | Application of titanium dioxide catalyst sensitized by octacarboxylic iron phthalocyanine to degradation of organic dyes under visible light |
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| CN108375569A (en) * | 2018-02-09 | 2018-08-07 | 安徽工业大学 | A kind of preparation method of phthalocyanine/graphene composite sensing material for cyanide ion identification |
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| CN108940365A (en) * | 2018-06-25 | 2018-12-07 | 山东大学 | A method of preparing FePC water soluble disperse nanoparticle |
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