New Solvent Method of Preparation of Blue Crude Copper Phthalocyanine With Yield of 99%

using a standard procedure with additional of a Derivative of Natural Product 0.25%

benjaminlukas@yahoo.com

Copper Phthalocyanine Blue BLUE PIGMENT CuPc (Copper Phthalocyanine) Blue pigment CuPc is one of the most stable pigments towards light, temperature and chemicals and hence, combined with its attractive colors, this pigment is widely used in many applications such as in paints water & solvent based paints including automotive paints), in water & solvent based inks, in textiles and in plastics with temperature of operations up to 350 C.

In industry, this pigment is produced in two stages The first stage is the preparation of the Blue Crude CuPc while the 2nd is the Pigmentation of crude CuPc ie the reduction of particle size of Crude CuPc.

Preparation of Crude Copper Phthalocyanine

The preparation of crude CuPc can be classified into 2 processes:• Dry Process in which the reactants were ground together and then heated up at above 200 C

until CuPc formed. Only very few manufacturers now use dry or baking process.• Solvent Process in which the reactant are mixed together with an organic solvent and then

heated up to 200 C for several hours. This is the process used in the industry.

The solvent processes can be divided into 2 groups namely those that use phthalonitrile and those that use phthalic acid/anhydride as one of the starting materials.

Because phthalonitrile is much more expensive than phthalic anhydride and also it is highly toxic which therefore demands special care for environmental protection, the phthalonitrile process is too costly for industry compared with the phthalic acid/anhydride process.

Preparation of CrudeCopper Phthalocyanine

Crude CuPc Blue

In industry Crude CuPc is commonly prepared by reacting copper (i)chloride,urea, phthalicanhydride, and ammonium molybdate as catalyst in the presence of alkylbenzene solvent.

• CuCl + 12 H2NCONH2 + 4 C6H4 (CO)2O CuPc + NH3 + CO2 + H2O + NH4Cl

• Structure of CuPc Yield 90%

Structure of CuPc Yield 90%

Market Demand

• MARKET DEMAND for Copper Phthalocyanine World production of this product is over 110,000 tons/year while the gap between the world demand and the supply according to Business Analyst for Asahi Songwon Colors Ltd for 2011 is 19,000 tons / year.

• PRODUCTION COUNTRIES Crude CuPc was used to be produced in Japan, Europe and America but now it has been shifted to mainly China and India due to lower labor cost and also mainly as the waste regulations of these countries are not strictly followed.

Production of Crude CuPc according to Patent

Phthalic anhydride 1000 kg, urea 1350 kg, and trichlorobenzene 3000 kg are mixed in a vessel equipped with an oil bath and stirrer: 240 kg of copper(II) chloride and 5 kg of ammonium molybdate are then added.

The mixture are heated up slowly within 1 hour to 200 C . Gas evolution mostly CO2 and some NH3 with formation of phthalimide begins at 130 C. Formation of CuPc begins at 160-170 C, with simultaneous released of CO2 and NH3. After stirring at 200-205 C for 1 hour, formation of the pigment is complete.

The Phthalocyanine is filtered of ; washed with hot trichlorobenzene at 50 C, methanol and hot water; and dried.

The yield of CuPc is 870 kg( 90%)

GLASS LINED PRESSURE REACTORUSED FOR CRUDE PREPARATION IN INDUSTRY

Rotary Vacuum DryerUsed to Recollect Solvent

Filter Press Used to Collect the Crude Formed Product

Spin Flash Dryer Used to Dry Crude CuPc

Problems of Manufacturing Crude CuPc

YieldThe yield of reaction is max 90% based on copper chloride used (see List of Patents). There are therefore about 10 % of the reagents used are disposed as waste. In the reaction, none of the reagents, the intermediate product and the end product dissolve completely in the solvent. Because of this problem the yield of copper phthalocyanine is about 90% and of high impurity.

At the end of reaction, the solid is filtered, washed and dried. The effluent is treated with coagulant and then filtered as waste. The waste should be incinerated but in some countries the effluent is treated with Na2S to precipitate most of the unwanted solid and then the waste solid is dispersed in some way or burried underground.

Problems of Manufacturing Crude CuPc

Environmental Problem The 90% yield and cost of waste treatment contribute to higher cost of production of crude CuPc and

also to environmental problem. In order to solve the problem there have been numerous experiments reported as patents, for

example the reaction was carried out in two connected reactors with ammonia as additional reagents with the purpose of preventing phthalimide formed as the result of reaction of phthalic anhydride with urea , adhere to the reactor’s wall.

Others used a solvent which had a greater dissolving power instead of alkyl benzene in order to improve the stirring of the reaction.

Other works reported on addition of promoting agents to the reaction such as thioureas, guanidines, amides, imides.

All these works reported, however, have been not successful to get significant increase in yield (see list of some of the numerous patents reported).

Cost of Raw Materials Used (Jan 2011)

Phthalic anhydride

Cuprous Chloride

Urea

Ammonium molybdate

CuPc (just raw materials cost)

FOB Price of CuPc (from Baiyan China)

$ 1,500 / MT

$ 6,565 / MT

$ 350 / MT

$ 24,000 / MT

$ 3,517 / MT

$ 5,760 /MT

CalculationMaterial Weight used for 1

MT CuPcUnit Price / MT Cost

CuCl 191 kg $ 6,565 $ 1,254.00

Phthalic Anhydride 1143 kg $ 1,500 $ 1,714.50

Urea 1390 kg $ 350 $ 487.00

Catalyst 2.60 kg $ 24,000 $ 62.40

Total Cost CuPc $ 3,517.90 / MT

Profit The profit for the manufacturers of this product would increase tremendously if the yield increases to 100%. For example, a medium size manufacturer that produces 5000 MT CuPc/ year with the FOB price of the low quality CuPc is $5.76/kg, the expenses are as follow:

If the cost of raw materials ($3.52), packaging ($0.04) and energy ($0.44) to be $4.00/kg then to produce 5000 MT = $20m

And if the cost for machinery is assumed to be $1m so a 5 yrs depreciation= $0.2m/yr

And if the number of workers employed is 100 with salary assumed to be $300/month each, so salary = $0.36m/yr

Profit Then Profit would be calculated as follows:

(5000 MT x $5.76) - $20m - $0.2m - $0.36m + (9% x 5000 MT x $5.76) = $8.24m + $2.59m$10.83m/yr (before depreciation of building, Interest & Tax)

The profit should be more than this as the saving cost for the waste treatment has not been added to this amount.

Solutions to the Problems

• Adding a small amount of a derivative of a natural product 0.25% would improve the yield tremendously up to 99%

• Derv of natural product could be added at the same time as other reagents before the reaction starts or in the middle of the reaction before the temperature reaches 120 C.

Methodology

. Synthesize & analyze the purity of standard crude copper phthalocyanine using solvent method

• Synthesize & analyze the purity of crude copper phthalocyanine using solvent method in the presence of various substituted carbon chain of fatty acid ester salt in different ratio.

• Analyze the softness and color shade of the product compared with the standard sample using Muller grinder and chromameter.

New Method of Preparation of Crude CuPc

Apparatus:• Round bottom flask 1000 ml• Liebig condensor• Dean stark• Thermocouple • Homo mixer • Flask receiver• Heating mantel• Glass Beaker 250 ml• Analytical balance 0.001 g• Vacuum pump• Oven• Filter cloth• Buchner flask• Buchner funnel• Glass Beaker 5000 ml• Thermometer

New Method of Preparation of Crude CuPc

Chemicals for Preparation of CuPc: • Urea : 170.00 g• Phthalic Anhydride : 130.00 g• Cuprous Chloride : 21.60 g• Catalyst Ammonium molybdate : 0.30 g• Organic Solvent (bpt>200C) : 180.00 g• A derv of nat. product : 0.375 g Chemicals for washing crude: • Sulfuric acid 60%• NP-10• Water

Note: trichlorobenzene is no longer used in the production as it may produce toxic carcinogenic polychlorinated biphenyl (pcb), it istherefore replaced with other organic solvent of similar boilingpoint.

New Method of Preparation of Crude CuPc

Preparation of crude is divided into 2 parts :• Method of Preparation for crude• Washing of Crude

New Method of preparation of CRUDE• Set the reactor which consists of a round bottom flask, dean stark and liebig condenser with cool water running.• Pour the solvent into the reactor.• Set the homo mixer with 80 rpm speed.• Heat the solvent up to 110 - 120C, then add all other materials into the flask.• The mixture will change color several times with ammonia is evolved vigorously. During the first 1 hour the

mixture will have several color changes until it finally turns blue when the temperature reaches about 180C

The reaction proceeds very much more vigorously than the standard reaction (no co-catalyst added).

• Record the reaction temperature at every hour .• Add 100 ml solvent at the second and fourth hours.• Stop the reaction after 7 hour, filter it and then dry in the oven at 80 C until it dries.

New Method of Preparation of Crude CuPc

WASHING OF CRUDE

• Weigh 100 g of the resulting crude.• Put it into a blender and add 500 ml water, stir for 30 seconds.• Then add water 1500 ml.• Pour into a beaker and heat the mixture at 90-95C for 15 minutes. • Add NP-10 0.1 g• Stir with homo mixer at 120 – 150 rpm• Add 60% sulphuric acid 164.29 gr 165 g• Heat the mixture again to 90 5C for 15 minutes • Filter the mixture and rinse with boilng water until the filtrate is neutral.• Heat in the oven at 80C for 12 – 16 hours.• Place it in the dessicator for 30 minutes and then record the crude obtained.

After varying the concentration and length of carbon chain of co-catalyst, it can concluded that the minimum amount co-catalyst used is 0.4% per kg of CuPc which cost $0.03 extra per kg CuPc

• Yield : 127.86 g (97% Purity) or 99% (calculated with 100% Purity)• Results of analysis of new preparation of crude are comparable to the standard

Test of Purity of Crude CuPc

Test Method for the Purity of Crude CuPc• 3 g of sample was accurately weighed and dissolved in 30 g of concentrated sulphuric acid with stirring in a

beaker. • Pour the solution gently into another beaker containing 150 ml cool distilled water and stir for the next 30

minutes at 90 C.• Filter the precipitate formed and wash with cool water until the filtrate is neutral.• Dry in oven for 10 hours at 100 C.• Purity of the sample was determined by the formula:

• Purity = Weight of Precipitate (g) x100 % Weight of Sample (g)

• Crude CuPc must satisfy all the parameters specifications as listed on the next slide

Product Specification of New Crude CuPc using American Standard Test Method

Parameter

• Purity• Moisture Content• Water Soluble Matter• Alcohol Soluble Matter• pH• Conductivity• Total Grit• Iron• Sand• Fiber• Free Copper Content• PCB

Specification

• 97 % min• 1 % max• 1.5 % max• 2.0 % max• 4 - 8• 800 mho• 300 ppm max• 20 pieces max /100 g• 30 pieces max / 100 g• Trace• 3000 ppm max• 0.1 ppm max

Value of the New Method

. The economic benefit obtained from the new method is the extra yield of 9% plus the saving cost of waste treatment.

If the price of crude CuPc per kg is $7.00/Kg per Dec 2014 so for the medium size manufacturer which usually produces 5000 MT/year the added profit would roughly be

= 450000 kg x $7.00 + saving cost of waste treatment per year = about $3.5 million/year.

. Green Environment : will reduce waste from 10 % to 1%

• Besides copper phthalocyanine, this new method can be used to increase the yield enormously for other many metals phthalocyanines which are also produced in industry due to their specific uses such as Fe, Co, Ni, Zn, Al, Si and tin Pc complexes. All these metal phthalocyanines were reportedly in literature produced with yield much lower than 90%, some were even below 10%.

References

• Asahi Songwon –Annual Report 2010-11• US Patent 3188318 (1965) : 79% Yield based on CuCl used• US Patent 3985767 (1976) : 76.9% Yield based on CuCl used• US Patent 5393339 (1995) : 85% Yield based on CuCl used, • US Patent 5910585 (1999) : 89% Yield based on CuCl used• The Porphyrin Handbook, edited by KM Kadish et al, vol 19, p114, 2003. • 85-90% Yield • CN Patent 1974577 (2007) : 85% Yield based on CuCl used• US Patent 4000157 (1976)• US Patent 5393339 (1995) : 85% Yield based on CuCl used• EP 0672728 B1 (1999) • US Patent 5810585 (1999)• Japanese Patent 2001181525 (2001)• Japanese Patent 2001181529 (2001)• Japanese Patent 2002012789 (2002)• CN Patent 1428377 (2003)• CN Patent 101538415 (2009)