CN1532175A

CN1532175A - Anti-oxidation single component aromatic hydrocarbon solvent used in copper phthalocyanine synthesis

Info

Publication number: CN1532175A
Application number: CNA03111203XA
Authority: CN
Inventors: 赵维绳; 汪维凤
Original assignee: Individual
Current assignee: Individual
Priority date: 2003-03-19
Filing date: 2003-03-19
Publication date: 2004-09-29
Anticipated expiration: 2023-03-19
Also published as: CN1312093C

Abstract

The present invention relates to aromatic hydrocarbon solvent, and is especially oxidationproof single-component aromatic hydrocarbon solvent used in synthesizing copper phthalocyanine. It features the boiling point of 200-220 deg.c, density of 0.86-0.89 and refractivity of 1.5060-1.5080, and has the advantages of being environment friendly and non-toxic, high yield and high purity of copper phthalocyanine product and high oxidation resistance. The solvent may be used in preparing C.I. blue pigment with high strength and pure color.

Description

The resistance to oxidation single-component aromatic solvent of in copper phthalocyanine is synthetic, using

Technical field

The present invention relates to aromatic solvent, particularly the resistance to oxidation single-component aromatic solvent of in copper phthalocyanine is synthetic, using.

Background technology

As everyone knows, trichlorobenzene is used as the production of copper phthalocyanine reaction solvent age for a long time, use face is very wide, almost be considered to a kind of optimal solvent, but after when finding it, generating by product PCB in reaction, its application is greatly limited, and various countries all are devoted to research and develop a kind of new solvent and substitute trichlorobenzene.Describe according to Japanese Patent (spy opens clear 57-135866), the organic solvent that replaces trichlorobenzene on probation has: oil of mirbane, di-isopropyl toluene, naphthalene, anthracene, phenylformic acid alkyl ester, tetracol phenixin, naphthane, chloro alkylbenzene, kerosene, hexachlorobutadiene, C ₁～C ₄Alkylbenzene, tetraline etc.; Introduce according to Chinese patent (CN1037912 and CN1061669), the organic solvent that replaces trichlorobenzene has: bicyclohexyl, alkane (C ₁₀～C ₁₅), naphthenic hydrocarbon (C ₉～C ₁₅), alkylbenzene (R=C ₄～C ₈) etc.; Their shortcoming is that oxidation-resistance is poor during application, the products obtained therefrom poor quality.

A kind of solvent as production of copper phthalocyanine replacement trichlorobenzene should reach the requirement of following five aspects simultaneously: 1. boiling point and trichlorobenzene are approaching, convenient solvent reclaiming; 2. resistance to oxidation, thermotolerance will adapt to the requirement of production of copper phthalocyanine; 3. self toxicity little, can not generate toxic products (for example PCB) in process of production; 4. quality and the productive rate to copper phthalocyanine can not have negative impact; 5. self rate of recovery wants high, has better economic.For achieving the above object, offshore company is the breach of novel dissolvent with the alkylbenzene, large quantities of alkyl benzene solvents have appearred, as: Ortho Nitro Toluene, 2,4-toluene dichloride, dimethylated chlorobenzene, sec.-propyl-1,2,4-Three methyl Benzene, tert-butylbenzene, special hexyl benzene, tert-amylbenzene, 2-chloro-4-isopropyl toluene, diisopropyl benzene, dimethyl ethylbenzene, ditane, diethylbenzene etc.; Describe according to Japanese Patent (spy opens clear 57-65755), Solvent150 is C with the side chain ₄～C ₅Alkylbenzene be the mixture of main composition, boiling point is 150～320 ℃; But provide market the actual Nisseki Hisol P that has only Japanese petro-chemical corporation (Nipponpetrochemical Co.Ltd) exploitation that uses, this solvent is the compound of following several alkylbenzenes: tert-amylbenzene 20～25%, special hexyl benzene 55～60%, special heptyl benzene 15%, and chief constituent 5～10%; Verify through domestic production, in the process of production of copper phthalocyanine, do not generate PCB, its scale resistance is fair, but the quality of the copper phthalocyanine that is obtained and yield are very unstable, fluctuation range is very big, and copper phthalocyanine is processed into face (dying) material tinting material, the green partially phase of coloured light is very big, influences the use range of copper phthalocyanine; Its reason may be because due to the physico-chemical property difference of various alkylbenzenes, so must explore by the technological line of synthetic single component aromatic solvent.

The preparation of alkylbenzene need adopt alkylated reaction to realize: according to United States Patent (USP) (US3313860), Japanese Patent (spy opens flat 3-24021) and Chinese patent (CN1340491) are described, with the alkylbenzene is that raw material carries out alkylated reaction, the alkene that is adopted has: propylene, butylene, 4-methyl-1-pentene etc., the catalyzer of employing has: phosphoric acid, aluminum chloride, hydrogen fluoride, sulfuric acid and solid acid catalyst etc.

Summary of the invention

The object of the present invention is to provide the resistance to oxidation single-component aromatic solvent of a kind of yield height, nontoxic, result of use is good application in copper phthalocyanine is synthetic.

For achieving the above object, the technical scheme that the present invention takes is: the resistance to oxidation single-component aromatic solvent of in copper phthalocyanine is synthetic, using, and its general structure is as follows:

In the formula: R '=CH ₃Or C ₂H ₅, m=1～3, R=C ₄H ₉Its during as reaction medium boiling point be generally 200～220 ℃, density (d ₂₀) 0.86～0.89, specific refractory power (n ¹¹) 1.5060～1.5080.

Boiling point is preferably 210～216 ℃ during as reaction medium, density 0.87～0.88; The purity of aromatic solvent generally answers＞98%; Be preferably 〉=99%.

The preparation process of aromatic solvent of the present invention is as follows:

1) with the alkylbenzene be raw material, will remove the oxious component in the raw material before using, as: S based compound and double bond compound, otherwise can influence the carrying out of alkylated reaction and the scale resistance of generation aromatic solvent; The raw material alkylbenzene purity of using is best 〉=and 99%, general 〉=90%, the alkyl branches carbonatoms is C ₁～C ₄

The carbonatoms of monoolefine is C ₄, exceed viscosity and molten Jie's property that carbon atom number range can influence aromatic solvent, can make reaction undesired, the copper phthalocyanine yield is on the low side, and it is very heavy to reclaim the solvent color, and what influence solvent repeatedly applies mechanically effect; And needing before using through removing water treatment, purity is best 〉=and 99%; The catalyzer purity that adopts is greater than 97%.

2) temperature of reaction is 5～60 ℃, and the temperature low reaction time is long, and the high by product of temperature is many.

The present invention has following advantage:

1. environmental friendliness.Aromatic solvent of the present invention replaces trichlorobenzene in the production of copper phthalocyanine; thoroughly eradicated the generation of carcinogens polychlorobiphenyl (PCB); guarantee safe in utilization; and in reaction process, can not produce other toxic byproduct is arranged; for the cleaner production of copper phthalocyanine provides condition, can in Chemical Manufacture, promote environment protection.

2. effect is good.As the reaction medium of condensation reaction, prepared copper phthalocyanine all meets production requirement to aromatic solvent of the present invention on quality and yield in the production of copper phthalocyanine.

3. copper phthalocyanine yield height, purity height, coloured light are just.As reaction medium, the copper phthalocyanine yield reaches 90～94% with single-component, than the existing component of manying solvent breakthrough is arranged.

4. the solvent scale resistance is good.Its performance is constant after applying mechanically five times continuously.

5. the copper phthalocyanine that adopts the present invention to make, the C.I. pigment Blue 15 (phthalocyanine blue b) of its preparation, intensity 100%, coloured light is pure.

Embodiment

Embodiment 1

In being the glass reactor of 2 liters, volume adds 1000 parts of raw material ethylbenzenes (purity 〉=99%), 650 parts of catalyzer vitriol oils, stirring is cooled to below 20 ℃, 700 parts of iso-butylenes (purity 〉=99%) through processed, feed in the reactor by reactor bottom, during feeding, temperature of reaction remains on about 30 ℃ always, when monoolefine feeding amount during near specified amount, at any time carrying out GC (gas-chromatography) by sampling in the reactor analyzes, when finished product content reaches requirement in the reaction mixture, stopped reaction, the Separation and Recovery catalyzer is used for following batch and synthesizes, the product that is obtained by separation obtains about 1335 parts of thick product solvent, content about 90% through purifying treatment; Thick product gets 1197 parts of aromatic solvent compd As, content 98.8～99.2%, yield 89～91% by rectification and purification; Its characteristic infrared absorption peak is: 3000～2800cm ^-1, 1600～1500cm ^-1, 810～800cm ^-1Product appearance: water white is transparent, density 0.868,209～213 ℃ of boiling ranges, specific refractory power (n ¹¹) 1.507.About 130 parts of the unreacting material alkylbenzene of being retrieved by rectifying must not handle to be directly used in down batch building-up reactions again.

The control of GC method is adopted in reaction, and chromatographic instrument is HP-5890, and chromatographic column is 50m, the OV-01 capillary column of 0.2mm.

Embodiment 2

In being the glass reactor of 2 liters, volume adds 1000 parts of raw material ethylbenzenes (purity 〉=99%), 150 parts of catalyzer aluminum trichloride (anhydrous)s (purity 〉=97%), stirring is cooled to below 10 ℃, 750 parts of iso-butylenes (purity 〉=99%) through processed, feed in the reactor by reactor bottom, during feeding, temperature of reaction remains on 5～10 ℃ always, when singly-bound alkene feeding amount during near specified amount, at any time carrying out GC by sampling in the reactor analyzes, when finished product content reaches requirement in the reaction mixture, stopped reaction, Separation and Recovery catalyzer, being used for following batch synthesizes, product by separation obtains obtains about 1260 parts of thick product solvent, content about 90% through purifying treatment; Thick product gets 1130 parts of pure product solvents, content 98.2～98.5%, yield 85.3～86.4% by rectification and purification; Its characteristic infrared absorption peak, product appearance, density, boiling range, specific refractory power are all with example 1; The unreacting material alkylbenzene of being retrieved by rectifying must not handled again and can be directly used in down batch building-up reactions.

Embodiment 3

According to the identical method of embodiment 1, the synthetic aromatic solvent compd B content 98.6～99.3% that obtains, yield 89～93%, its characteristic infrared absorption peak is: 3000～2800cm ^-1, 1600～1500cm ^-1, 900～800cm ^-1Product appearance: water white is transparent, density 0.875,210～216 ℃ of boiling ranges, specific refractory power (n ¹¹) 1.5046.

Application examples 1

Stirring revolution is 80 rev/mins, volume is the stainless steel condensation still of 3 liters, add 600 parts of example 3 products obtained therefrom solvent B, 200 parts of phthalic anhydrides, 220 parts in urea, 36.5 parts of cuprous chlorides, 1 part of ammonium molybdate, under agitation be warming up to 150～160 ℃ in 1 hour, react after 3 hours, be warming up to 180～190 ℃ again, pressure remained on 2～3Mpa reaction after 5 hours, complete reaction mixture is poured out in cooling, transferring to volume is in the horizontal rake type drier of stainless steel of 3 liters, and stirring revolution is 30 rev/mins, is about 1Mpa in vacuum tightness, be heated to 160～170 ℃, steam neat solvent, the time is 6～8 hours, and reclaiming the solvent that obtains is the water white transparence, the receipts amount is about 510 parts, and yield is about 85%; The copper phthalocyanine of solvent evaporated is a dark blue look loose dry powder, and it is carried out acid-alkali treatment according to a conventional method, and drying obtains dark blue look fine powder, and must measure is 185～193 parts, yield 90～94%; The quality index of copper phthalocyanine is qualified fully: the dark blue look fine powder of outward appearance, and content＞95%, free copper≤2000ppm, moisture content≤1.0% does not contain PCB.

Annotate: each solid material specification all is same as the employed specification of enterprise.

The product solvent in the detected result of applying mechanically in the process sampling after five times continuously is: exterior water white transparence, 210～220 ℃ of boiling ranges, density (d ₂₀) 0.872, specific refractory power (n ¹¹) 1.5078.Prepared five batches of copper phthalocyanine quality are all qualified fully when applying mechanically process continuously, and outward appearance is the faint blue fine powder, content＞95%, and free copper＜2000ppm, moisture content≤1.0 do not contain PCB.

Application examples 2

Prepared five batches of copper phthalocyanines in the application examples 1, respectively carry out pigmenting and handle by the conventional acid pasting that uses of pigmenting, made five batches of C.I. pigment Blue 15s (phthalocyanine blue b), every batch detected result is identical, be: outward appearance blue powder, PCB: do not have water content≤2.0%.

Identify that by national standard " pigment intensity and chromaphotometry method " qualification result is also identical again: intensity 100%, coloured light is pure.

Describing by above application examples 1,2, prove that the product solvent has the excellent oxidation-resistance energy, is that medium institute synthetic copper phthalocyanine and phthalocyanine blue b quality meet the requirements fully with it.

Claims

1. the resistance to oxidation single-component aromatic solvent of application in copper phthalocyanine is synthetic, general structure is as follows,

In the formula: R '=CH ₃Or C ₂H ₅, m=1～3, R=C ₄H ₉It is characterized in that: boiling point is 200～220 ℃ during as reaction medium, density 0.86～0.89, specific refractory power 1.5060～1.5080.

2. according to the described resistance to oxidation single-component of claim 1 aromatic solvent, it is characterized in that: boiling point is 210～216 ℃ during as reaction medium, density 0.87～0.88, specific refractory power 1.5060～1.5080.

3. according to claim 1 or 2 described resistance to oxidation single-component aromatic solvents, it is characterized in that: the purity of aromatic solvent＞98%.

4. according to the described resistance to oxidation single-component of claim 3 aromatic solvent, it is characterized in that: the purity of aromatic solvent is 〉=99%.