Fine clean production process of phthalocyanine green pigment

Abstract
(1) phthalonitrile preparation; (2) copper source preparation; (3) solvent selection; (4) copper
phthalocyanine obtaining; (2) copper pharmacy (5) phthalocyanine green crude product
preparation; (6) phthalocyanine green refining; (7) finished phthalocyanine green preparation; (8)
finished phthalocyanine green crystal form change. less in side reaction; the coloring power, the
brightness, the dispersibility, the transparency and the other properties are finally improved; the
production process is strong in operability, close in step combination and short in process time.
(6) translated from Chinese
1. phthalocyanine green pigment fine cleaner production processes, characterized in that it
comprises the following steps: (1) preparation of phthalonitrile: phthalimide reaction with
ammonia phthalic acid amide, and then dehydrated which obtained phthalonitrile, followed by
recrystallization from ethanol to 3-5 times, spare; (2) Preparation of copper sources: using CuCl:
CuCl2S 1: 1 ratio by crushing, grinding, filtering, and mixed to obtain copper source, prior to use
by hydrochloric acid - acetone solution for processing; (3) the choice of solvent: the choice to do
the reaction solvent nitrobenzene or glycol; (4) copper phthalocyanine obtained: Add step (I) in a
reaction vessel in The resulting phthalonitrile, step (2) obtained in the copper source,
nitrobenzene or ethylene glycol, in the course of the reaction in open gas imports were from the
upper end of the lower end of the reactor, each of the gas inlet through into Cl2, Cl2 amount of
each gas inlet through the gas flow meter controlled by the 0.6-0.8L / min, open mixing
equipment, followed by heating equipment in the reactor temperature to increase 2 V per minute
reaction kettle The temperature was gradually heated to 200 C, then add 30-40g molybdic
anhydride, the reaction vessel was reacted at 200 C ambient 5_6 hours. After completion of the
reaction, to obtain copper phthalocyanine; (5) Preparation of the crude phthalocyanine green:
Next The kettle temperature to 2 C per minute rate of cooling to 120 C, the reaction three
catalysts were added chlorosulfonic acid, liquid sulfur monochloride and iodine, while adjusting
the gas flow meter, and from the upper end of the reaction Il the amount of the lower end into the
Cl2 was adjusted to 2.4-3.2 L / min, the reaction for 5-6 hours, followed by 1 C per minute in
the reactor at a rate of temperature rise to 160-165, temperature was raised to the reaction kettle
ammonium chloride, ammonium chloride is added in an amount of crude phthalocyanine green
mass of 1/20, the reaction for 2-3 hours, and then again by the amount of Cl2 gas flow meter was
adjusted to 4-4.5 L / min, 3 hours prepared Duo phthalocyanine green crude; (6) to give
phthalocyanine green: the step (5) obtained phthalocyanine green crude was filtered, acid, caustic
washing, washing, get phthalocyanine green crude, the crude surfactant The reaction mixture
was stirred under the presence of an organic solvent with chlorobenzene for 15-20 minutes, the
adsorption of the pigment emulsified, after filtration, the filtrate was layered recovered
nitrobenzene or ethylene glycol; (7) Preparation of phthalocyanine green finished: The cake by
precipitation of inorganic salts, the precipitate cake was washed three times after the first, and
then washed three times with ethanol, and dried to obtain the finished product phthalocyanine
green; (8) finished phthalocyanine green crystal form changes: the dried finished products placed
phthalocyanine green in a kneading machine, and set within the kneading machine grinding balls
by rotating blades inside the kneader and continuous roll grinding balls for crushing large
particles pigment, thinning, surface ball, changing the crystalline state of the particle in the
kneading process to air in the stirring means.
2. According to a phthalocyanine green pigment fine clean production process according to claim
1, characterized in that: said step (4) phthalonitrile 30-50kg, copper source 10-16kg,
nitrobenzene or glycol 90-100L.
3. A phthalocyanine green pigment of claim 1, wherein the fine clean production process,
characterized in that: said step (4) in each of the gas inlet of the gas filter are provided.
4. A phthalocyanine green pigment of claim 1, wherein the fine clean production process,
characterized in that: said step (5) in chlorosulfonic acid, liquid sulfur chloride and added in an
amount of iodine were three 5 -6L, 2-3L and 2-3L.
5. A phthalocyanine green pigment fine clean production process according to claim 1, wherein:
said step (7) was added to the inorganic salt is barium chloride, calcium chloride, manganese
sulfate, three added ratio of 1: 1: 1.
6. According to a phthalocyanine green pigment fine clean production process according to claim
1, characterized in that: the grinding balls accounted for a quarter of the kneader interior space,
and about the diameter of each grinding balls where one of the outer peripheral surface
machining lap shear ring.
Description translated from Chinese
Phthalocyanine green pigment fine cleaner production processes

TECHNICAL FIELD

[0001] The present invention relates to a chemical paint production technology, and in particular
relates to a phthalocyanine green pigment fine Cleaner Production Workers

Background technique

[0002] phthalocyanine pigment for its excellent light fastness, heat, acid and alkali resistance and
bright color known as the leader in the organic pigment. Phthalocyanine green pigment is one of
the categories, is the best green pigment, it is a phthalocyanine blue (ie copper phthalocyanine)
olfactory chlorinated or chlorine mixed halogenated product. With different halogen substituents
on the phenyl ring atoms in different colors. Typically a chlorinated product of I 2 16 chlorine
atoms substituted for the bright green. Phthalocyanine green synthesis process will be divided,
mainly for direct halo and direct condensation into two categories, the raw material is concerned,
into law and phthalic anhydride method two eyes.

[0003] The so-called direct halo process is refined and copper phthalamide reaction, which in
turn was prepared copper phthalocyanine copper phthalocyanine chloride, to obtain a
phthalocyanine green that is a halogenated copper phthalocyanine, and the direct condensation
process It is the first chlorination of phthalic anhydride or tetrachlorophthalic tetrachlorophthalic
phthalic eye, and then condensation reaction with copper.

[0004] The chlorination process carried out in anhydrous A1C1 # P NaCl medium. The
advantage is that the process maturity, yield yet. Chloro, bromo or mixed halogenated apply. The
disadvantage is corrosive large, AlCl3K peace can not be recycled, serious waste and process in
a chlorinated copper phthalocyanine copper atoms are often replaced with aluminum, the product
color darkens, affecting the quality; secondly, the original process is a solid main catalyst sulfur ,
dissolved in the reaction slow, affect the catalytic effect, and phthalocyanine green ferric
chloride in the production process commonly used, antimony trichloride both inefficient and not
less soluble solid auxiliary catalyst, the subsequent processing complex, trouble; Also, according
to the general method of producing phthalocyanine green after drying is directly for sale, then the
low pigment intensity, dark color, poor application performance, coloring pigments, brightness,
dispersion, transparency and other properties are not maximized to improve, resulting in the
presence of pigment to block serious problems during use.

SUMMARY OF THE INVENTION

[0005] For the above problems, the present invention aims to provide a phthalocyanine green
pigment fine cleaner production processes, process operability, the reaction efficiency than the
existing increased by about 10%, high quality pigment obtained, to achieve cleaner production,
shorten response time, improve coloring pigments, brightness, dispersion, transparency and other
properties.

[0006] To achieve the above object, the technical scheme of the present invention is used as
follows:

Phthalocyanine green pigment fine cleaner production processes, characterized in that it

comprises the following steps:

(1) Preparation of phthalonitrile in: after phthalimide reaction with ammonia phthalic acid amide,
and then by dehydration that obtained phthalonitrile, followed by 3-5 times recrystallized from
ethanol, spare ;

(2) Preparation of copper sources: using CuCl: CuCl2S 1: 1 ratio by crushing, grinding, filtering,
and mixed to obtain a copper source, prior to use by hydrochloric acid - acetone solution for
processing;

(3) solvent selection: selection of nitrobenzene or ethylene glycol to make a reaction solvent;

(4) copper phthalocyanine obtained: Add step (I) in a reaction vessel prepared in phthalonitrile,
step (2) obtained in the copper source, nitrobenzene or ethylene glycol, in the course of the
reaction from the upper end of the lower end of the reactor gas inlet opening respectively, each
of the gas inlet pass into Cl2, Cl2 amount of each gas inlet through the gas flow through the
control 0.6-0.8L / min, open mixing equipment, followed by The heating apparatus the
temperature in the reactor to increase to 2 C per minute to a temperature of the autoclave was
gradually heated to 200 C, then add 30-40g molybdic anhydride, the reaction vessel was
reacted at 200 C ambient 5_6 hours After completion of the reaction, to obtain copper
phthalocyanine;

(5) Preparation of crude phthalocyanine green: Next, the reaction vessel temperature to 2 C per
minute rate of cooling to 120 C, the reaction three catalysts were added chlorosulfonic acid,
liquid sulfur monochloride and iodine, while adjusting the amount of gas flow, from the upper
and lower ends into the reaction Il Cl2 was adjusted to 2.4-3.2 L / min, the reaction for 5-6 hours,
followed by 1 C per minute, a rate of the temperature of the autoclave was raised to 160 165,
ammonium chloride was added to the reaction vessel after the temperature rises, the amount of
ammonium chloride was added to the crude phthalocyanine green mass of 1/20, the reaction for
2-3 hours, and then again through the gas flow meter is adjusted to the amount of Cl2 4-4.5 L /
min, the reaction for 3 hours to obtain Duo phthalocyanine green crude;

(6) to give the phthalocyanine green: the step (5) is obtained phthalocyanine green crude was
filtered, acid, caustic washing, washing, get phthalocyanine green crude, crude in the presence of
a surfactant and an organic solvent chlorobenzene After stirring the reaction for 15-20 minutes,
to emulsify the pigment adsorption, filtration, the filtrate was layered recycled nitrobenzene or
ethylene glycol;

(7) Preparation of phthalocyanine green finished products: inorganic salt precipitated by the filter
cake, the filter cake washed three times with precipitation of the first, and then washed three
times with ethanol, and dried to obtain the finished product phthalocyanine green;

(8) finished phthalocyanine green crystal changes: dry good product phthalocyanine green placed
in a kneading machine, and set the grinding balls inside the kneading machine, kneading
machine through the inside of the rotating blades and the continuous roll grinding balls of paint
The large particle breakage, thinning, surface ball, changing the crystalline state of the particle,
to air stirring means in the kneading process.

[0007] Preferably, the step (4) phthalonitrile 30_50kg, copper source 10_16kg, nitrobenzene or
ethylene glycol 90-100L.

[0008] Preferably, said step (4) in each of the gas inlet of the gas filter are provided.

[0009] Preferably, the step (5) in chlorosulfonic acid, liquid sulfur chloride and added in an
amount of iodine were three 5-6L, 2-3L and 2-3L.

[0010] Preferably, the step (7) was added to the inorganic salt is barium chloride, calcium
chloride, sulfuric acid Meng, the three joined ratio of 1: 1: 1.

[0011] Preferably, the grinding balls accounted for a quarter of the kneading machine inner space
and the outer peripheral surface of the diameter of the wound where the whole process on each
grinding balls lap shear ring.

[0012] The beneficial effects of the present invention are:

Operability, step linked closely together, the process time is shortened: The invention uses
phthalonitrile with copper source in the reaction of copper phthalocyanine in nitrobenzene or
glycol solvent, after copper phthalocyanine catalyst and chlorine Under the assistance obtained
phthalocyanine green crude, then phthalocyanine green crude through a series of processing to
obtain phthalocyanine green boutique and finished the steps of the present invention is simple,
easy to control, and the temperature of the reaction processes are adopted gradually formula
warming or cooling, avoid direct heating cooling mutation of the internal components due to raw
material, to achieve a better response than the full and complete formula by gradually heating
and cooling;

Clean, environmentally friendly, less side reaction: In liquid sulfur chloride after the main
catalyst for the reaction of sulfur replacement catalytic effect significantly improved; (2)
increasing the amount of the main catalyst addition, the abolition of ferric chloride, antimony
trichloride both difficult The solid was dissolved and inefficient auxiliary catalyst; and (3)
increasing the reaction pressure, the reaction temperature is lowered, to adjust the chlorine gas
flow rate, to improve the utilization rate of the chlorine gas; color strength, brightness,
dispersibility, transparency and ultimately improve performance: kneading machine a pair of co-
ordinated and rotating blades produce strong shearing leaving the pigment grinding and grinding
balls, grinding balls surface processing lap shear ring, with stirring paddle rotation, the material
between the stirring blade, Stirring Large particles and between the container wall, grinding balls
and pigments to produce bi-axial and radial impact, crushing, shearing, grinding, crushing the
pigment, thinning, surface ball, changing the crystalline state particles and to improve color
purity, the pigment having a bright color and high tinting strength, which has a high value.

DETAILED DESCRIPTION

[0013] In order to enable one of ordinary skill in the art to better understand the technical aspect
of the present invention, the following examples in conjunction aspect of the present invention is
further described below.

A [0014] Example: A phthalocyanine green pigment fine cleaner production processes, including
the following steps:

(1) Preparation of phthalonitrile in: after phthalimide reaction with ammonia phthalic acid amide,
and then by dehydration that obtained phthalonitrile, followed by 3-5 times recrystallized from
ethanol, spare ;

(2) Preparation of copper sources: using CuCl: CuCl2S 1: 1 ratio by crushing, grinding, filtering,
and mixed to obtain a copper source, prior to use by hydrochloric acid - acetone solution
processed using CuCl and & 1 (: 12 two kinds which contains the same chemical element copper
source, to reduce pollution in the post-production process caused by excessive element types and
handling difficult issues;

(3) solvent selection: selection of the reaction solvent nitrobenzene do;

(4) copper phthalocyanine obtained: Add step (I) is obtained phthalonitrile 30kg, step (2)
obtained in the copper source 10kg, nitrobenzene 90L in the reactor, in the course of the reaction
from the upper end of the lower end of the reactor has a gas inlet opening, respectively, each of
the gas introduced into the inlet Cl2, each of the gas inlet are provided a gas filter, the filter will
not be visible through the gas impurities contained Cl2 was filtered off, to prevent its With (: 12
into the reaction kettle affect the reaction mass, before Cl 2 pass into the needs of concentrated
sulfuric acid by washing, Cl2 amount of each gas inlet through the gas flow control via 0.61 /
minute, open mixing equipment, followed by The heating apparatus the temperature in the
reactor to increase to 2 C per minute to a temperature of the autoclave was gradually heated to
2000C, then add 30g molybdic anhydride, the reaction vessel was reacted at 200 C
environment for 5-6 hours, the reaction When finished, get copper phthalocyanine;

(5) Preparation of crude phthalocyanine green: Next, the reaction vessel temperature to 2 C per
minute rate of cooling to 120 C, the reaction kettle was added chlorosulfonic acid three
catalysts 5L, liquid sulfur monochloride and iodine 2L 2L while adjusting the gas flow, from the
reactor into the upper and lower ends of the amount of Cl2 was adjusted to 2.4 L / min, the
reaction for 5-6 hours, followed by 1 C per minute, the speed of the reaction kettle temperature
was raised to 160 -165, was added to the reaction vessel after the temperature of ammonium
chloride, ammonium chloride was added in an amount of crude phthalocyanine green mass of
1/20, ammonium chloride is a strong acid salt of a weak base, in water, to generate hydrochloric
acid hydrolysis will occur, hydrochloric acid to neutralize alkali, alkali can reduce the impact of
phthalocyanine green, alkali agent, which is mainly used as phthalocyanine green staining, the
reaction for 2-3 hours, and then again by the amount of Cl2 gas flow meter is adjusted to 4 L /
min, the reaction for 3 hours to obtain a crude phthalocyanine green;

(6) to give the phthalocyanine green: the step (5) is obtained phthalocyanine green crude was
filtered, acid, caustic washing, washing, get phthalocyanine green crude, crude in the presence of
a surfactant and an organic solvent chlorobenzene After stirring the reaction for 15-20 minutes,
to emulsify the pigment adsorption, filtration, the filtrate was layered recycled nitrobenzene or
ethylene glycol;

(7) Production of finished phthalocyanine green: The cake by precipitation of inorganic salts,
salts of barium chloride, calcium chloride, manganese sulfate, the three joined ratio of 1: 1: 1, the
use of inorganic salts first phthalocyanine After Green precipitation can be achieved more
brilliant shade, chromatographic than the whole, low production cost, cake precipitated first
washed three times, then washed three times with ethanol, and dried to obtain the finished
product phthalocyanine green;

(8) changes in the finished product green crystal phthalocyanine: dry good product
phthalocyanine green placed in a kneading machine, and kneading machine set inside grinding
balls, grinding balls representing the internal space of the kneading machine fourths First, and
where the outer peripheral surface diameter grinding balls around one working on each lap shear
ring, by rotating blades inside the kneader and continuous roll grinding balls for crushing large
particles pigment, thinning, surface ball, change crystalline state of the particles, be air agitation
means in the kneading process.

[0015] Examples of phthalocyanine finally obtained a green weight of 31.5kg.

[0016] Example II: Example of a difference is in step (4) phthalonitrile (4) copper
phthalocyanine obtained: Add step (I) in a reaction vessel prepared in phthalonitrile 40kg Step
(2) obtained in the copper source 13kg, glycol 95L, the amount of each Cl2 gas imports pass into
the control of gas flow through at 0.7L / min, was added 35g molybdic acid anhydride;
(5) Preparation of crude phthalocyanine green: Next, the reaction vessel temperature to 2 C per
minute rate of cooling to 120 C, the reaction kettle was added chlorosulfonic acid three
catalysts 5.5L, and 2.5L of liquid sulfur monochloride Iodine 2.5L, from the reaction vessel
upper and lower volume entering Cl2 was adjusted to 2.8 L / min, followed by the amount of gas
flow Cl 2 again adjusted to 4.2 L / min.

[0017] Examples The two eventually obtained phthalocyanine green weight of 43.5kg.

[0018] Example III: Example of a difference is in step (4) phthalonitrile (4) copper
phthalocyanine obtained: In an autoclave step (I) is obtained phthalonitrile 50kg Step (2)
obtained in the copper source 16kg, glycol 100L, the amount of each Cl2 gas imports pass into
the control of gas flow through at 0.8 / min, add 40g of molybdic acid anhydride;

(5) Preparation of crude phthalocyanine green: Next, the reaction vessel temperature to 2 C per
minute rate of cooling to 120 C, the reaction kettle was added chlorosulfonic acid three
catalysts 6L, liquid sulfur monochloride and iodine 3L 3L The amount from the reactor into the
upper and lower ends Cl2 was adjusted to 3.2 L / min, followed by the amount of Cl2 gas meter
again adjusted to 4.5 L / min.

[0019] Examples three resulting phthalocyanine green weight of 54.5kg.

[0020] The above are only a few preferred embodiments of the present invention, not the
technical aspect of the present invention are further defined.