Preparation of Blue Crude Coper Phthalocyanine using a derivative of natural product 0.25% to give yield of 99%.

1. 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

2. 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.

3. 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.

4. Preparation of CrudeCopper Phthalocyanine
Crude CuPc Blue
In industry Crude CuPc is commonly prepared by reacting copper (i)chloride,urea, phthalic
anhydride, 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%

5. 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.

6. 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%)

7. GLASS LINED PRESSURE REACTOR
USED FOR CRUDE PREPARATION IN INDUSTRY

8. Rotary Vacuum Dryer
Used to Recollect Solvent

9. Filter Press Used to Collect the Crude Formed
Product

10. Spin Flash Dryer Used to Dry Crude CuPc

11. Problems of Manufacturing Crude CuPc
Yield
The 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.

12. Problems of Manufacturing Crude CuPc
Environmental Problem
The 90% yield and cost of waste treatment contribute to higher cost of production of crudeCuPc
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).

13. 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

14. Calculation
Material Weight used for 1
MT CuPc
Unit 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

15. 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

16. 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.

17. 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.

18. 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.

19. 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

20. 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 is
therefore replaced with other organic solvent of similar boiling
point.

21. 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 - 120C, 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.

22. 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  5C for 15 minutes
• Filter the mixture and rinse with boilng water until the filtrate is neutral.
• Heat in the oven at 80C 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

23. 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

24. 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

25. 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%.

26. 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)