WO2017175101A1 - Synthesis of copper phthalocyanine using deep eutectic solvent - Google Patents
Synthesis of copper phthalocyanine using deep eutectic solvent Download PDFInfo
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- WO2017175101A1 WO2017175101A1 PCT/IB2017/051847 IB2017051847W WO2017175101A1 WO 2017175101 A1 WO2017175101 A1 WO 2017175101A1 IB 2017051847 W IB2017051847 W IB 2017051847W WO 2017175101 A1 WO2017175101 A1 WO 2017175101A1
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- chloride
- copper
- choline chloride
- glycerol
- choline
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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
- 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
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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
- 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
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
Definitions
- the present disclosure generally relates to synthesis of copper phthalocyanine.
- the present disclosure relates to a method of synthesis of copper phthalocyanine using deep eutectic solvent (DES).
- DES deep eutectic solvent
- Copper phthalocyanine is a pigment useful in coloration of inks, paints, plastics materials, textiles, leathers and coating of various substrates.
- the numbers expressing quantities of ingredients, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term "about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some embodiments of the invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
- An object of the present disclosure is to provide a method for synthesis of copper phthalocyanine that satisfies the existing needs, as well as others, and generally overcomes the deficiencies found in the existing art.
- Another object of the present disclosure is to provide a method for synthesis of copper phthalocyanine that enables the production of copper phthalocyanine without using high boiling solvents.
- Another object of the present disclosure is to provide a method for synthesis of copper phthalocyanine that enables production of copper phthalocyanine without using hazardous solvents, which are a serious ecological concern.
- Another object of the present disclosure is to provide a method for synthesis of copper phthalocyanine that allows recycling of solvents.
- Another object of the present disclosure is to provide a method for synthesis of copper phthalocyanine that is free from problems such as use of high quantity of urea, high quantity of solvent, and high quantity of unreacted starting material, and difficult separation of final product from the reaction mass.
- the present disclosure generally relates to synthesis of copper phthalocyanine.
- the present disclosure relates to a method of synthesis of copper phthalocyanine using deep eutectic solvent (DES).
- An aspect of the present disclosure relates to a method of synthesis of a copper phthalocyanine compound, said method comprising the step of reacting at least one copper source with phthalic acid or a derivative thereof in presence of a catalyst, wherein said step of reacting at least one copper source with phthalic acid or a derivative thereof in presence of a catalyst is effected in presence of at least one deep eutectic solvent (DES).
- DES deep eutectic solvent
- the at least one copper source is selected from a group consisting of copper oxide, copper sulfate, copper acetate, copper hydroxide and metallic copper.
- the phthalic acid or a derivative thereof is selected from a group consisting of phthalic anhydride, phthalimide, phthalonitrile, phthalamic acid and phthalate salt.
- the catalyst comprises any or a combination of compounds of Molybdenum, Vanadium, Phosphorous and Ammonium.
- the at least one deep eutectic solvent comprises any or a combination of choline chloride/acetamide, choline chloride/ethylene glycol, choline chloride/glycerol, choline chloride/urea, choline chloride/malonic acid, ethylammonium chloride/acetamide, ethylammonium chloride/ethylene glycol, ethylammonium chloride/glycerol, choline bromide/glycerol, terabutylammonium chloride/glycerol, triethylbenzylammonium chloride/glycerol, acetylcholine chloride/glycerol, choline chloride/formamide, choline chloride/arabinose, choline chloride/glucose, and choline chloride/xylose.
- DES deep eutectic solvent
- Another aspect of the present disclosure relates to a method of synthesis of a copper phthalocyanine compound, said method comprising the steps of:
- step (d) heating the mixture obtained from step (c) to effect synthesis of the copper
- the step of heating said reaction mass is effected at a temperature ranging from about 80°C to about 120°C and wherein the step of heating the mixture obtained from step (c) is effected at a temperature ranging from about 65°C to about 1 10°C.
- the method further comprises the steps of:
- the deep eutectic solvent comprises any or a combination of choline chloride/acetamide, choline chloride/ethylene glycol, choline chloride/glycerol, choline chloride/urea, choline chloride/malonic acid, ethylammonium chloride/acetamide, ethylammonium chloride/ethylene glycol, ethylammonium chloride/glycerol, choline bromide/glycerol, terabutylammonium chloride/glycerol, triethylbenzylammonium chloride/glycerol, acetylcholine chloride/glycerol, choline chloride/formamide, choline chloride/arabinose, choline chloride/glucose, and choline chloride/xylose.
- the phthalic acid or a derivative thereof is selected from any or a combination of phthalic anhydride, phthalimide, a phthalate salt, phthalamic acid, and phthalonitrile and wherein said copper source is selected from a group consisting of copper oxide, copper sulfate, copper acetate, copper hydroxide and metallic copper.
- the catalyst is selected from any or a combination of compounds of Molybdenum, Vanadium, Phosphorous and Ammonium. In an embodiment, the catalyst is Ammonium heptamolybdate.
- Still further aspect of the present invention provides a copper phthalocyanine compound formed in accordance with embodiments of the present disclosure.
- the numbers expressing quantities of ingredients, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term "about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable.
- the present disclosure generally relates to synthesis of copper phthalocyanine.
- the present disclosure relates to a method of synthesis of copper phthalocyaninein presence of a deep eutectic solvent (DES).
- DES deep eutectic solvent
- An aspect of the present disclosure relates to a method of synthesis of a copper phthalocyanine compound, said method comprising the step of reacting at least one copper source with phthalic acid or a derivative thereof in presence of a catalyst, wherein said step of reacting at least one copper source with phthalic acid or a derivative thereof in presence of a catalyst is effected in presence of at least one deep eutectic solvent (DES).
- the at least one copper source is selected from a group consisting of copper oxide, copper sulfate, copper acetate, copper hydroxide and metallic copper.
- the phthalic acid or a derivative thereof is selected from a group consisting of phthalic anhydride, phthalimide, phthalonitrile, phthalamic acid and phthalate salt.
- the catalyst comprises any or a combination of compounds of Molybdenum, Vanadium, Phosphorous and Ammonium.
- the at least one deep eutectic solvent comprises any or a combination of choline chloride/acetamide, choline chloride/ethylene glycol, choline chloride/glycerol, choline chloride/urea, choline chloride/malonic acid, ethylammonium chloride/acetamide, ethylammonium chloride/ethylene glycol, ethylammonium chloride/glycerol, choline bromide/glycerol, terabutylammonium chloride/glycerol, triethylbenzylammonium chloride/glycerol, acetylcholine chloride/glycerol, choline chloride/formamide, choline chloride/arabinose, choline chloride/glucose, and choline chloride/xylose.
- DES deep eutectic solvent
- Another aspect of the present disclosure relates to a method of synthesis of a copper phthalocyanine compound, said method comprising the steps of:
- step (d) heating the mixture obtained from step (c) to effect synthesis of the copper
- the step of heating said reaction mass is effected at a temperature ranging from about 80°C to about 120°C and wherein the step of heating the mixture obtained from step (c) is effected at a temperature ranging from about 65°C to about 1 10°C.
- the method further comprises the steps of:
- the deep eutectic solvent comprises any or a combination of choline chloride/acetamide, choline chloride/ethylene glycol, choline chloride/glycerol, choline chloride/urea, choline chloride/malonic acid, ethylammonium chloride/acetamide, ethylammonium chloride/ethylene glycol, ethylammonium chloride/glycerol, choline bromide/glycerol, terabutylammonium chloride/glycerol, triethylbenzylammonium chloride/glycerol, acetylcholine chloride/glycerol, choline chloride/formamide, choline chloride/arabinose, choline chloride/glucose, and choline chloride/xylose.
- the phthalic acid or a derivative thereof is selected from any or a combination of phthalic anhydride, phthalimide, a phthalate salt, phthalamic acid, and phthalonitrile and wherein said copper source is selected from a group consisting of copper oxide, copper sulfate, copper acetate, copper hydroxide and metallic copper.
- the catalyst is selected from any or a combination of compounds of Molybdenum, Vanadium, Phosphorous and Ammonium. In an embodiment, the catalyst is Ammonium heptamolybdate.
- Still further aspect of the present invention provides a copper phthalocyanine compound formed in accordance with embodiments of the present disclosure.
- a deep eutectic solvent or DES is a type of ionic solvent with special properties composed of a mixture which forms a eutectic mixture with a melting point much lower than that of either of the individual components.lt should be appreciated that any DES, asknown to or appreciated by a person skilled in the art, can be used to serve its intended purpose without departing from the spirit and scope of the present invention.
- Exemplary DES that can find utility for the present invention include any or a combination of quaternary ammonium salt with metal chloride, quaternary ammonium salt with metal chloride hydrate, quaternary ammonium salt with hydrogen bond donor, and metal chloride hydrate with hydrogen bond donor but not limited thereto.
- mixtures of choline halide with urea i.e. Choline
- phthalic acid and/or derivative(s)thereof that can be used for theinstant inventioninclude, but are not limited to, phthalic acid, phthalic anhydride, phthalimide, a salt such as sodium phthalate, phthalamic acid, phthalonitrile, or a mixture thereof.
- phthalic anhydride is used for the instant invention.
- catalysts that can be used for the instant invention include, but are not limited to, compounds of molybdenum, for example, be metal molybdenum, molybdic acid, a molybdate such as ammonium molybdate or sodium molybdate, a molybdenum compound such as ammonium phosphorus molybdate or molybdenum oxide.
- molybdenum for example, be metal molybdenum, molybdic acid, a molybdate such as ammonium molybdate or sodium molybdate, a molybdenum compound such as ammonium phosphorus molybdate or molybdenum oxide.
- ammonium molybdate can be used for the instant invention.
- any other known catalysts for the synthesis of copper phthalocyanine such as, compounds of molybdenum or vanadium and phosphoruscan be utilizedwithout departing from the scope and spirit of the instant invention.
- the copper source that can be used for the instant invention can be selected from the group comprising of copper salts such as a metal copper powder, copper oxide, copper sulfate, copper acetate and copper hydroxide.
- the copper source that can be used for the instant invention is copper sulfate.However, a person skilled in the art must appreciate that any other known copper source for the synthesis of copper phthalocyanine can be utilized without departing from the scope and spirit of the instant invention.
- the temperature range for the step b) in the synthesis of copper phthalocyanine i.e. heating of reaction mass of DES and phthalic anhydride can be from about 80°C to about 120°C.
- temperature range for the step d) in the synthesis of copper phthalocyanine i.e. heating of paste obtained after adding copper sulfate and ammonium molybdateto the reaction mass of DES and phthalic anhydride can be from about 65°C to about 110°C.
- the paste can be maintained at this temperature for 1 hour.
- the paste obtained after this step can be cooled and subsequently washed with alcohol, preferably selected from methanol or ethanol, and most preferably methanol.
- temperature range for the step e) in the synthesis of copper phthalocyanine i.e. drying of the product which is a blue colored pigment can be from about 80°C to about 120°C.In an embodiment, the drying can take from 8 to 18 hours. In another embodiment, before drying, the pigment can bewashed with alkali, acid and hot water.
- copper phthalocyanine can be synthesized by using DES, phthalic anhydride, cupric sulfate, and ammonium heptamolybdate.
- copper phthalocyanine can be synthesized by using a mixture of choline chloride and urea as DES, phthalic anhydride, cupric sulfate and ammonium heptamolybdate.
- copper phthalocyanine can be synthesized by using a mixture of choline chloride and urea as DES, phthalic anhydride, cuprous sulfate, ammonium heptamolybdate.
- copper phthalocyanine can be synthesized by using mixture of choline iodide and urea as DES, phthalic anhydride, cupric sulfate and ammonium heptamolybdate. In still further embodiment, copper phthalocyanine can be synthesized by using a mixture of choline fluoride and urea as DES, phthalic anhydride, cupric sulfate and ammonium heptamolybdate. In still further embodiment, copper phthalocyanine can be synthesized by using a mixture of choline bromide and urea as DES, phthalic anhydride, cupric sulfate and ammonium heptamolybdate. EXAMPLES
- Example 1 Synthesis of copper phthalocyanine by using choline chloride and urea in the molar ratio of 1:1 as DES.
- Example 2 Synthesis of copper phthalocyanine by using choline chloride and urea in the molar ratio of 1:2 as DES.
- Example 4 Synthesis of copper phthalocyanine by using choline chloride and urea in the molar ratio of 1:4 as DES.
- Example 5 Synthesis of copper phthalocyanine by using choline chloride and urea in the molar ratio of 1:5 as DES.
- the present disclosure provides for a method for synthesis of copper phthalocyanine that satisfies the existing needs, as well as others, and generally overcomes the deficiencies found in the prior art.
- the present disclosure provides for a method for synthesis of copper phthalocyanine which enables the production of copper phthalocyanine without using high boiling solvents.
- the present disclosure provides for a method for synthesis of copper phthalocyanine which enables the production of copper phthalocyanine without using hazardous solvents, which are a serious ecological concern.
- the present disclosure provides for a method for synthesis of copper phthalocyanine which also allows recycling of solvents.
- the present disclosure provides for a method for synthesis of copper phthalocyanine which is free from problems such as use of high quantity of urea, high quantity of solvent, and high quantity of unreacted starting material, and difficult separation of final product from the reaction mass.
Abstract
The present disclosure generally relates to synthesis of copper phthalocyanine. In particular, the present disclosure relates to a method of synthesis of copper phthalocyanine using deep eutectic solvent (DES), which can be carried out at low temperature, does not involve use of high boiling solvents, uses less urea and allows solvents used in the process to be recycled.
Description
SYNTHESIS OF COPPER PHTHALOCYANINE USING DEEP EUTECTIC SOLVENT
FIELD OF THE INVENTION
[0001] The present disclosure generally relates to synthesis of copper phthalocyanine. In particular, the present disclosure relates to a method of synthesis of copper phthalocyanine using deep eutectic solvent (DES).
BACKGROUND OF THE INVENTION
[0002] Background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
[0003] Copper phthalocyanine is a pigment useful in coloration of inks, paints, plastics materials, textiles, leathers and coating of various substrates.
[0004] Conventional methods for synthesis of copper phthalocyanine requirestringent conditions such as, high temperaturessomewhere in the range of 185-200 C andutilization of high boiling solvents such as nitrobenzene, xylene, and the like. These methods even utilizehigh quantity of urea, solvent and often result in high unreacted starting material being left at the end of the reaction (synthesis). Tedious techniques are needed insuch conventional methods to separate the final product from the reaction mass. Even more, these known methods use hazardous solvents for the synthesis of copper phthalocyanine.
[0005] In a publication by Seyyedi, Behnam, et al. titled "A new single step synthesis of copper phthalocyanine green using microwave irradiation effects in functionalisation of C— H bonds in aromatic rings", Pigment & Resin Technology 43.3 (2014): 113-117, a synthesis method for copper phthalocyanine is disclosed which uses urea, Copper (II) chloride dehydrate, and phthalic anhydride which are dissolved in saturated solution of Sodium chloride (NaCl). This method uses microwave irradiation as a chemical reaction initiator by creation of chlorine radicals. Said method also requires caution while involving use of ammonium molybdate along with microwaves in the synthesis as this may result in chlorination of other unsaturated bonds.
[0006] There is thus a need in the art for anew and improved method for synthesis of copper phthalocyanine, which does not suffer from the drawbacks of the aforementioned methods,which
are tedious, material-intensive, require loss-producing finishing treatments, and which sometimes cannot be undertaken without risks, in particular from an ecological aspect and with regard to safety.
[0007] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. Where a definition or use of a term in an incorporated reference is inconsistent or contrary to the definition of that term provided herein, the definition of that term provided herein applies and the definition of that term in the reference does not apply.
[0008] In some embodiments, the numbers expressing quantities of ingredients, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term "about." Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some embodiments of the invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
[0009] As used in the description herein and throughout the claims that follow, the meaning of "a," "an," and "the" includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein, the meaning of "in" includes "in" and "on" unless the context clearly dictates otherwise.
[0010] The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g. "such as") provided with respect to certain embodiments herein is intended merely to better illuminate the invention and does not pose a
limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.
[0011] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member can be referred to and claimed individually or in any combination with other members of the group or other elements found herein. One or more members of a group can be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified.
OBJECTS OF THE INVENTION
[0012] An object of the present disclosure is to provide a method for synthesis of copper phthalocyanine that satisfies the existing needs, as well as others, and generally overcomes the deficiencies found in the existing art.
[0013] Another object of the present disclosure is to provide a method for synthesis of copper phthalocyanine that enables the production of copper phthalocyanine without using high boiling solvents.
[0014] Another object of the present disclosure is to provide a method for synthesis of copper phthalocyanine that enables production of copper phthalocyanine without using hazardous solvents, which are a serious ecological concern.
[0015] Another object of the present disclosure is to provide a method for synthesis of copper phthalocyanine that allows recycling of solvents.
[0016] Another object of the present disclosure is to provide a method for synthesis of copper phthalocyanine that is free from problems such as use of high quantity of urea, high quantity of solvent, and high quantity of unreacted starting material, and difficult separation of final product from the reaction mass.
SUMMARY OF THE INVENTION
[0017] The present disclosure generally relates to synthesis of copper phthalocyanine. In particular, the present disclosure relates to a method of synthesis of copper phthalocyanine using deep eutectic solvent (DES).
[0018] An aspect of the present disclosure relates to a method of synthesis of a copper phthalocyanine compound, said method comprising the step of reacting at least one copper source with phthalic acid or a derivative thereof in presence of a catalyst, wherein said step of reacting at least one copper source with phthalic acid or a derivative thereof in presence of a catalyst is effected in presence of at least one deep eutectic solvent (DES). In an embodiment, the at least one copper source is selected from a group consisting of copper oxide, copper sulfate, copper acetate, copper hydroxide and metallic copper. In an embodiment, the phthalic acid or a derivative thereof is selected from a group consisting of phthalic anhydride, phthalimide, phthalonitrile, phthalamic acid and phthalate salt. In an embodiment, the catalyst comprises any or a combination of compounds of Molybdenum, Vanadium, Phosphorous and Ammonium. In an embodiment, the at least one deep eutectic solvent (DES) comprises any or a combination of choline chloride/acetamide, choline chloride/ethylene glycol, choline chloride/glycerol, choline chloride/urea, choline chloride/malonic acid, ethylammonium chloride/acetamide, ethylammonium chloride/ethylene glycol, ethylammonium chloride/glycerol, choline bromide/glycerol, terabutylammonium chloride/glycerol, triethylbenzylammonium chloride/glycerol, acetylcholine chloride/glycerol, choline chloride/formamide, choline chloride/arabinose, choline chloride/glucose, and choline chloride/xylose.
[0019] Another aspect of the present disclosure relates to a method of synthesis of a copper phthalocyanine compound, said method comprising the steps of:
(a) adding a deep eutectic solvent (DES) to phthalic acid or a derivative thereof to form a reaction mass;
(b) heating said reaction mass at an elevated temperature;
(c) adding a copper source and a catalyst to said heated reaction mass; and
(d) heating the mixture obtained from step (c) to effect synthesis of the copper
phthalocyanine compound.
[0020] In an embodiment, the step of heating said reaction mass is effected at a temperature ranging from about 80°C to about 120°C and wherein the step of heating the mixture obtained from step (c) is effected at a temperature ranging from about 65°C to about 1 10°C.
In an embodiment, the method further comprises the steps of:
(e) subjecting said copper phthalocyanine compound to washing with any or a combination of an alcohol, an acid, an alkali, and water;
(f) drying the washed copper phthalocyanine compound; and
(g) converting the dried copper phthalocyanine compound into a powder form.
[0021] In an embodiment, the deep eutectic solvent comprises any or a combination of choline chloride/acetamide, choline chloride/ethylene glycol, choline chloride/glycerol, choline chloride/urea, choline chloride/malonic acid, ethylammonium chloride/acetamide, ethylammonium chloride/ethylene
glycol, ethylammonium chloride/glycerol, choline bromide/glycerol, terabutylammonium chloride/glycerol, triethylbenzylammonium chloride/glycerol, acetylcholine chloride/glycerol, choline chloride/formamide, choline chloride/arabinose, choline chloride/glucose, and choline chloride/xylose.
[0022] In an embodiment, the phthalic acid or a derivative thereof is selected from any or a combination of phthalic anhydride, phthalimide, a phthalate salt, phthalamic acid, and phthalonitrile and wherein said copper source is selected from a group consisting of copper oxide, copper sulfate, copper acetate, copper hydroxide and metallic copper. In an embodiment, the catalyst is selected from any or a combination of compounds of Molybdenum, Vanadium, Phosphorous and Ammonium. In an embodiment, the catalyst is Ammonium heptamolybdate.
[0023] Still further aspect of the present invention provides a copper phthalocyanine compound formed in accordance with embodiments of the present disclosure.
DETAILED DESCRIPTION OF THE INVENTION
[0024] Unless the context requires otherwise, throughout the specification which follow, the word "comprise" and variations thereof, such as, "comprises" and "comprising" are to be construed in an open, inclusive sense that is as "including, but not limited to."
[0025] Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
[0026] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. It should also be noted that the term "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise.
[0027] In some embodiments, the numbers expressing quantities of ingredients, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term "about." Accordingly, in some embodiments, the numerical parameters set forth in the written description are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by
applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable.
[0028] The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g. "such as") provided with respect to certain embodiments herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.
[0029] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0030] Reference will now be made in detail to the exemplary embodiments of the present invention.
[0031] The present disclosure generally relates to synthesis of copper phthalocyanine. In particular, the present disclosure relates to a method of synthesis of copper phthalocyaninein presence of a deep eutectic solvent (DES).
[0032] An aspect of the present disclosure relates to a method of synthesis of a copper phthalocyanine compound, said method comprising the step of reacting at least one copper source with phthalic acid or a derivative thereof in presence of a catalyst, wherein said step of reacting at least one copper source with phthalic acid or a derivative thereof in presence of a catalyst is effected in presence of at least one deep eutectic solvent (DES). In an embodiment, the at least one copper source is selected from a group consisting of copper oxide, copper sulfate, copper acetate, copper hydroxide and metallic copper. In an embodiment, the phthalic acid or a derivative thereof is selected from a group consisting of phthalic anhydride, phthalimide, phthalonitrile, phthalamic acid and phthalate salt. In an embodiment, the catalyst comprises any or a combination of compounds of Molybdenum, Vanadium, Phosphorous and Ammonium. In an embodiment, the at least one deep eutectic solvent (DES) comprises any or a combination of choline chloride/acetamide, choline chloride/ethylene glycol, choline chloride/glycerol, choline chloride/urea, choline chloride/malonic acid, ethylammonium chloride/acetamide,
ethylammonium chloride/ethylene glycol, ethylammonium chloride/glycerol, choline bromide/glycerol, terabutylammonium chloride/glycerol, triethylbenzylammonium chloride/glycerol, acetylcholine chloride/glycerol, choline chloride/formamide, choline chloride/arabinose, choline chloride/glucose, and choline chloride/xylose.
[0033] Another aspect of the present disclosurerelates to a method of synthesis of a copper phthalocyanine compound, said method comprising the steps of:
(a) adding a deep eutectic solvent (DES) to phthalic acid or a derivative thereof to form a reaction mass;
(b) heating said reaction mass at an elevated temperature;
(c) adding a copper source and a catalyst to said heated reaction mass; and
(d) heating the mixture obtained from step (c) to effect synthesis of the copper
phthalocyanine compound.
[0034] In an embodiment, the step of heating said reaction mass is effected at a temperature ranging from about 80°C to about 120°C and wherein the step of heating the mixture obtained from step (c) is effected at a temperature ranging from about 65°C to about 1 10°C.
[0035] In an embodiment, the method further comprises the steps of:
(e) subjecting said copper phthalocyanine compound to washing with any or a combination of an alcohol, an acid, an alkali, and water;
(f) drying the washed copper phthalocyanine compound; and
(g) converting the dried copper phthalocyanine compound into a powder form.
[0036] In an embodiment, the deep eutectic solvent comprises any or a combination of choline chloride/acetamide, choline chloride/ethylene glycol, choline chloride/glycerol, choline chloride/urea, choline chloride/malonic acid, ethylammonium chloride/acetamide, ethylammonium chloride/ethylene glycol, ethylammonium chloride/glycerol, choline bromide/glycerol, terabutylammonium chloride/glycerol, triethylbenzylammonium chloride/glycerol, acetylcholine chloride/glycerol, choline chloride/formamide, choline chloride/arabinose, choline chloride/glucose, and choline chloride/xylose.
[0037] In an embodiment, the phthalic acid or a derivative thereof is selected from any or a combination of phthalic anhydride, phthalimide, a phthalate salt, phthalamic acid, and phthalonitrile and wherein said copper source is selected from a group consisting of copper oxide, copper sulfate, copper acetate, copper hydroxide and metallic copper.ln an embodiment, the catalyst is selected from any or a combination of compounds of Molybdenum, Vanadium, Phosphorous and Ammonium. In an embodiment, the catalyst is Ammonium heptamolybdate.
[0038] Still further aspect of the present invention provides a copper phthalocyanine compound formed in accordance with embodiments of the present disclosure.
[0039] A deep eutectic solvent or DES is a type of ionic solvent with special properties composed of a mixture which forms a eutectic mixture with a melting point much lower than that of either of the individual components.lt should be appreciated that any DES, asknown to or appreciated by a person skilled in the art, can be used to serve its intended purpose without departing from the spirit and scope of the present invention. Exemplary DES that can find utility for the present invention include any or a combination of quaternary ammonium salt with metal chloride, quaternary ammonium salt with metal chloride hydrate, quaternary ammonium salt with hydrogen bond donor, and metal chloride hydrate with hydrogen bond donor but not limited thereto.
[0040] In an embodiment, DES that can be used for the purpose of the instant invention include, but are not limited to, choline chloride/acetamide; choline chloride/ethylene glycol; choline chloride/glycerol; choline chloride/urea; choline chloride/malonic acid; ethylammonium chloride/acetamide; ethylammonium chloride/ethylene glycol; ethylammonium chloride/glycerol; choline bromide/glycerol; terabutylammonium chloride/glycerol; triethylbenzylammonium chloride/glycerol; acetylcholine chloride/glycerol; choline chloride/formamide; choline chloride/arabinose; choline chloride/glucose; or choline chloride/xylose.In a preferred embodiment, mixtures of choline halide with urea i.e. Choline bromide/urea, Choline chloride/urea, Choline iodide/urea and Choline fluoride/urea. In a preferred embodiment, a mixture of choline chloride and urea is used as DES.
[0041] In an embodiment, phthalic acid and/or derivative(s)thereof that can be used for theinstant inventioninclude, but are not limited to, phthalic acid, phthalic anhydride, phthalimide, a salt such as sodium phthalate, phthalamic acid, phthalonitrile, or a mixture thereof. In a preferred embodiment, phthalic anhydride is used for the instant invention.
[0042] In an embodiment, catalysts that can be used for the instant invention include, but are not limited to, compounds of molybdenum, for example, be metal molybdenum, molybdic acid, a molybdate such as ammonium molybdate or sodium molybdate, a molybdenum compound such as ammonium phosphorus molybdate or molybdenum oxide. In a preferred embodiment, ammonium molybdate can be used for the instant invention. However, a person skilled in the art must appreciate that any other known catalysts for the synthesis of copper phthalocyanine, such as, compounds of molybdenum or vanadium and phosphoruscan be utilizedwithout departing from the scope and spirit of the instant invention.
[0043] In an embodiment, the copper source that can be used for the instant invention can be selected from the group comprising of copper salts such as a metal copper powder, copper oxide, copper sulfate, copper acetate and copper hydroxide. In a preferred embodiment, the copper source that can be used for the instant invention is copper sulfate.However, a person skilled in the art must appreciate that any other known copper source for the synthesis of copper phthalocyanine can be utilized without departing from the scope and spirit of the instant invention.
[0044] In an embodiment, the temperature range for the step b) in the synthesis of copper phthalocyanine i.e. heating of reaction mass of DES and phthalic anhydride can be from about 80°C to about 120°C.
[0045] In an embodiment, temperature range for the step d) in the synthesis of copper phthalocyanine i.e. heating of paste obtained after adding copper sulfate and ammonium molybdateto the reaction mass of DES and phthalic anhydride can be from about 65°C to about 110°C. The paste can be maintained at this temperature for 1 hour. In an embodiment, the paste obtained after this step can be cooled and subsequently washed with alcohol, preferably selected from methanol or ethanol, and most preferably methanol.
[0046] In an embodiment, temperature range for the step e) in the synthesis of copper phthalocyanine i.e. drying of the product which is a blue colored pigmentcan be from about 80°C to about 120°C.In an embodiment, the drying can take from 8 to 18 hours. In another embodiment, before drying, the pigment can bewashed with alkali, acid and hot water.
[0047] In anembodiment, copper phthalocyanine can be synthesized by using DES, phthalic anhydride, cupric sulfate, and ammonium heptamolybdate. In another embodiment, copper phthalocyanine can be synthesized by using a mixture of choline chloride and urea as DES, phthalic anhydride, cupric sulfate and ammonium heptamolybdate. In still another embodiment, copper phthalocyanine can be synthesized by using a mixture of choline chloride and urea as DES, phthalic anhydride, cuprous sulfate, ammonium heptamolybdate. In still further embodiment, copper phthalocyanine can be synthesized by using mixture of choline iodide and urea as DES, phthalic anhydride, cupric sulfate and ammonium heptamolybdate. In still further embodiment, copper phthalocyanine can be synthesized by using a mixture of choline fluoride and urea as DES, phthalic anhydride, cupric sulfate and ammonium heptamolybdate. In still further embodiment, copper phthalocyanine can be synthesized by using a mixture of choline bromide and urea as DES, phthalic anhydride, cupric sulfate and ammonium heptamolybdate.
EXAMPLES
[0048] The present invention is further explained in the form of following examples. However it is to be understood that the foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.
Example 1: Synthesis of copper phthalocyanine by using choline chloride and urea in the molar ratio of 1:1 as DES.
[0049] Choline chloride and urea were taken in the ratio of 1 : 1 forming DES, which was viscous at room temperature.Phthalic anhydride was taken, to which DES was added. The reaction mass was stirred at room temperature and then heated to 80-120°C. Viscous white colored mass was observed to which CuS04 and ammonium heptamolybdate were added. The reaction mixture was heated at a temperature ranging from about 65°C to about 110°C and maintained for 1 hour. Dark blue colored thick paste was obtained, the reaction mass was cooled and washed with methanol to separate remaining DES from pigment. Washing was continued till colorless filtrate was obtained. The blue solid obtained was then washed with acid and alkali and then with hot water. The blue colored pigment was then dried at 80-120°C for 8-18 hr and powdered.
Example 2: Synthesis of copper phthalocyanine by using choline chloride and urea in the molar ratio of 1:2 as DES.
[0050] Choline chloride and urea were taken in the ratio of I nforming DES which was viscous at room temperature. Phthalic anhydride was taken, to which DES was added. The reaction mass was stirred at room temperature and then heated to 80-120°C. Viscous white colored mass was observed to which CuS04 and ammonium heptamolybdate were added. The reaction mixture was heated to 65-110 °C and maintained for 1 hour. Dark blue colored thick paste was obtained, the reaction mass was cooled and washed with methanol to separate remaining DES from pigment. Washing was continued till colorless filtrate was obtained. The blue solidobtained was then washed with acid and alkali and then with hot water. The blue colored pigment was then dried at 80-120°C for 8-18 hr and powdered.
Example 3: Synthesis of copper phthalocyanine by using choline chloride and urea in the molar ratio of 1:3 as DES.
[0051] Choline chloride and urea were taken in the ratio of 1 :3forming DES which was solid at room temperature and turned viscous liquid after heating to 40°C. Phthalic anhydride was taken, to which DES was added. The reaction mass was stirred at room temperature and was then heated to 80-120°C. Viscous white colored mass was observed to which CuS04 and ammonium heptamolybdate were added. The reaction mixture was heated to 65-110 °C and maintained for 1 hour. Dark blue colored thick paste was obtained, the reaction mass was cooled and washed with methanol to separate remaining DES from pigment. Washing was continued till colorless filtrate was obtained. The blue solid obtained was then washed with acid and alkali and then with hot water. The blue colored pigment was then dried at 80-120°C for 8-18 hr and powdered.
Example 4: Synthesis of copper phthalocyanine by using choline chloride and urea in the molar ratio of 1:4 as DES.
[0052] Choline chloride and urea were taken in the ratio of 1 :4 forming DES which was solid at room temperature and turned viscous liquid after heating to 40°C. Phthalic anhydride was taken, to which DES was added. The reaction mass was stirred at room temperature and was then heated to 80-120°C. Viscous white colored mass was observed to which CuS04 and ammonium heptamolybdate were added. The reaction mixture was heated to 65-110 °C and maintained for 1 hour. Dark blue colored thick paste was obtained, the reaction mass was cooled and washed with methanol to separate remaining DES from pigment. Washing was continued till colorless filtrate was obtained. The blue solid obtained was then washed with acid and alkali and then with hot water. The blue colored pigment was then dried at 80-120°C for 8-18 hr and powdered.
Example 5: Synthesis of copper phthalocyanine by using choline chloride and urea in the molar ratio of 1:5 as DES.
[0053] Choline chloride and urea were taken in the ratio of 1 :5 forming DES which was solid at room temperature and turned viscous liquid after heating to 40°C. Phthalic anhydride was taken, to which DES was added. The reaction mass was stirred at room temperature and was then heated to 80-120°C. Viscous white colored mass was observed to which CuS04 and
ammonium heptamolybdate were added. The reaction mixture was heated to 65-110 °C and maintained for 1 hour. Dark blue colored thick paste was obtained, the reaction mass was cooled and washed with methanol to separate remaining DES from pigment. Washing was continued till colorless filtrate was obtained. The blue solid obtained was then washed with acid and alkali and then with hot water. The blue colored pigment was then dried at 80-120°C for 8-18 hr and powdered.
ADVANTAGES OF THE INVENTION
[0054] The present disclosure provides for a method for synthesis of copper phthalocyanine that satisfies the existing needs, as well as others, and generally overcomes the deficiencies found in the prior art.
[0055] The present disclosure provides for a method for synthesis of copper phthalocyanine which enables the production of copper phthalocyanine without using high boiling solvents.
[0056] The present disclosure provides for a method for synthesis of copper phthalocyanine which enables the production of copper phthalocyanine without using hazardous solvents, which are a serious ecological concern.
[0057] The present disclosure provides for a method for synthesis of copper phthalocyanine which also allows recycling of solvents.
[0058] The present disclosure provides for a method for synthesis of copper phthalocyanine which is free from problems such as use of high quantity of urea, high quantity of solvent, and high quantity of unreacted starting material, and difficult separation of final product from the reaction mass.
Claims
1. A method of synthesis of a copper phthalocyanine compound, said method comprising the step of reacting at least one copper source with phthalic acid or a derivative thereof in presence of a catalyst, wherein said step of reacting at least one copper source with phthalic acid or a derivative thereof in presence of a catalyst is effected in presence of at least one deep eutectic solvent (DES).
2. The method as claimed in claim 1, wherein said at least one copper source is selected from a group consisting of copper oxide, copper sulfate, copper acetate, copper hydroxide and metallic copper.
3. The method as claimed in claim 1, wherein said phthalic acid or a derivative thereof is selected from a group consisting of phthalic anhydride, phthalimide, phthalonitrile, phthalamic acid and phthalate salt.
4. The method as claimed in claim 1, wherein said catalyst comprises any or a combination of compounds of Molybdenum, Vanadium, Phosphorous and Ammonium.
5. The method as claimed in claim 1, wherein said at least one deep eutectic solvent (DES) comprises any or a combination of choline chloride/acetamide,choline chloride/ethylene glycol,choline chloride/glycerol,choline chloride/urea,choline chloride/malonic acid,ethylammonium
chloride/acetamide,ethylammonium chloride/ethylene glycol,ethylammonium chloride/glycerol,choline bromide/glycerol,terabutylammonium chloride/glycerol,triethylbenzylammonium
chloride/glycerol, acetylcholine chloride/glycerol,choline chloride/formamide,choline
chloride/arabinose,choline chloride/glucose, and choline chloride/xylose.
6. A methodof synthesis of a copper phthalocyanine compound, said method comprising the steps of:
(a) adding a deep eutectic solvent (DES) to phthalic acid or a derivative thereof to form a reaction mass;
(b) heating said reaction mass at an elevated temperature;
(c) adding a copper source and a catalyst to said heated reaction mass; and
(d) heatingthe mixture obtained from step (c) to effect synthesis of the copper
phthalocyanine compound.
7. The method as claimed in claim 6, wherein the step of heating said reaction mass is effected at a temperature ranging from about 80°C to about 120°C and wherein the step of heating the mixture obtained from step (c) is effected at a temperature ranging from about 65°C to about 110°C.
8. The method as claimed in claim 6, wherein said method further comprises the steps of:
(e) subjecting said copper phthalocyanine compound to washing with any or a combination
of an alcohol, an acid, an alkali, and water;
(f) drying the washed copper phthalocyanine compound; and
(g) converting the dried copper phthalocyanine compound into a powder form.
9. The method as claimed in claim 6, wherein said deep eutectic solvent comprises any or a combination of choline chloride/acetamide, choline chloride/ethylene glycol, choline chloride/glycerol, choline chloride/urea, choline chloride/malonic acid,ethylammonium chloride/acetamide,ethylammonium chloride/ethylene glycol,ethylammonium chloride/glycerol, choline bromide/glycerol,terabutylammonium chloride/glycerol,triethylbenzylammonium chloride/glycerol, acetylcholine chloride/glycerol, choline chloride/formamide, choline chloride/arabinose, choline chloride/glucose, and choline chloride/xylose.
10. The method as claimed in claim 6, wherein said phthalic acid or a derivative thereof is selected from any or a combination of phthalic anhydride, phthalimide, a phthalate salt, phthalamic acid, and phthalonitrile and wherein said copper source is selected from a group consisting of copper oxide, copper sulfate, copper acetate, copper hydroxide and metallic copper.
11. The method as claimed in claim 6, wherein said catalyst is selected from any or a combination ofcompounds of Molybdenum, Vanadium, Phosphorous and Ammonium.
12. The method as claimed in claim 6, wherein said catalyst is Ammonium heptamolybdate.
13. A copper phthalocyanine compound formed according to the method as claimed in claim 6.
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| IN201621012243 | 2016-04-07 | ||
| IN201621012243 | 2016-04-07 |
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| WO2017175101A1 true WO2017175101A1 (en) | 2017-10-12 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110372711A (en) * | 2019-08-10 | 2019-10-25 | 石家庄搏澳增塑材料科技有限公司 | Urea-choline chloride catalysis phthalic nitrile synthesis metal phthalocyanine method |
| CN113463145A (en) * | 2021-07-20 | 2021-10-01 | 南京信息工程大学 | Green new method for surface anticorrosion modification of copper matrix |
| CN113578289A (en) * | 2021-08-05 | 2021-11-02 | 河北科技大学 | Eutectic solvent, carbon quantum dot-loaded porous adsorbent, and preparation method and application thereof |
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| US2302612A (en) * | 1939-10-13 | 1942-11-17 | American Cyanamid Co | Preparation of copper phthalocyanines |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110372711A (en) * | 2019-08-10 | 2019-10-25 | 石家庄搏澳增塑材料科技有限公司 | Urea-choline chloride catalysis phthalic nitrile synthesis metal phthalocyanine method |
| CN113463145A (en) * | 2021-07-20 | 2021-10-01 | 南京信息工程大学 | Green new method for surface anticorrosion modification of copper matrix |
| CN113578289A (en) * | 2021-08-05 | 2021-11-02 | 河北科技大学 | Eutectic solvent, carbon quantum dot-loaded porous adsorbent, and preparation method and application thereof |
| CN113578289B (en) * | 2021-08-05 | 2023-04-11 | 河北科技大学 | Eutectic solvent, carbon quantum dot-loaded porous adsorbent, and preparation method and application thereof |
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