New Solvent Method of Preparation

of Blue Crude (Pigment) Copper

Phthalocyanine With Yield of 99%

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.

Copper Phthalocyanine Blue

CRUDE CuPc Blue

In industry Crude CuPc is commonly prepared by reacting copper (i)

chloride, urea, phthalic anhydride, catalyst in the presence of solvent.

CuCl + 12 H2NCONH2 + 4 C6H4 (CO)2O

Structure of CuPc

CuPc + NH3 + CO2 + H2O + NH4Cl

Yield 90%

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 CO 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 REACTOR

USED FOR CRUDE PREPARATION IN
INDUSTRY

ROTARY VACUUM DRYER

USED TO RECOLLECT SOLVENT USED
Filter Press Used to Collect the Crude Formed
in INDUSTRY

Filter Press Used to Collect the Crude

Formed Product Specification of Crude
CuPc in Industry

Spin Flash Dryer Used to Dry Crude CuPc

in Industry

PROBLEMS OF MANUFACTURING CRUDE CuPc

1.

2.

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.

Environmental Effect
Most of the waste of the production of crude CuPc (11,000
tons/yr) is precipitated using Na2S and then is buried
underground

 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.

COST OF RAW MATERIALS USED

(Jan 2011)

Phthalic anhydride

$ 1,500 / MT

Cuprous Chloride

$ 6,565 / MT

Urea

$ 350 / MT

Ammonium
molybdate

$ 24,000 / MT

CuPc (just raw

materials cost)

$ 3,517 / MT

FOB Price of CuPc

(from Baiyan China)

$ 5,760 /MT

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

Profit
The profit for the manufacturers of this product would increase
tremendously by 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 + (10% x 5000 MT x
$5.76) = $8.24m + $2.88m
$11.12m/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 another co catalyst would improve the yield
tremendously up to 99.9%
The co-catalyst 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.
The general chemical formula of this chemical is a complex of X-fatty
acid ester sodium salt

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.
Analyse the softness and color shade of the product compared with the
standard sample

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 gr
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 gr
Phthalic Anhydride
: 130 gr
Cuprous Chloride
: 21.60 gr
Catalyst Ammonium molybdate
: 0.30 gr
Solvent alkyl benzene
: 180 gr
Co-catalyst
: 0.50 gr
(substituted fatty acid ester sodium salt)

Chemicals for washing crude:

Sulfuric acid 60%

NP-10
Water

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.
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 100 C until it dries.

New Method of Preparation of Crude

CuPc
WASHING OF CRUDE

Weigh 100g 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 gr
Stir with homo mixer at 120 150 rpm
Add 60% sulphuric acid 164.29 gr 165 gr
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.

Yield : 127.86 gr (97% Purity) or 99% (calculated with 100% Purity)

Results of analysis of new prepn crude are comparable to the standard

Product Specification of New Crude CuPc using

American Standard Test Method
Parameter

Specification

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

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 research if successful would be 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 : reduced waste from 10 % to 1%

Besides copper phthalocyanine, there are other many metals phthalocyanines which are
also produced in industry due to their specific uses such as ZnPc, Al Pc, SiPc and SnPc which
are used for photodynamic therapy (PDT) for cancer and others. All these metal
phthalocyanines are produced with yield much lower than 90%, some are even below 10%.
If the proposed method above is successful then it would almost certain be valuable for
other metals phthalocyanines preparation.

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)