CN1229107A - Preparation technology for quinacridone organic pigment - Google Patents

Abstract

A process for preparing quinacrilinone series of organic pigments including C.I.PV19 (gamma), C.I.PV19 (beta) and C.I.PR122 is a closed-loop one of 2,5-diarylamino-terephthalic acid in polyphosphoric acid (PPA), and features high output rate and stable quality.

Description

Preparation technology for quinacridone organic pigment

The invention belongs to quinacridone organic dye preparing technical field.

It is a kind of tone by orange to purple high-grade pigment dyestuff that quinacridone is shown machine pigment, and its thermotolerance, solvent resistance and resistance to migration are splendid, can be widely used in coating, plastics, printing ink, dissolve the painted of spinning etc.The synthetic method of quinacridone is more, and its main difference by starting raw material can be divided into: the succinate method; The Resorcinol method; Dibromo terephthalic acid method; The ketene dimer method; 2,5-two amido terephthalic acid methods.1. succinate method.Du pont company in 1958 adopts the succinate method to produce quinacridone, its production process be succinate under the effect of sodium ethylate, by contracting certainly, acidifying gets the succinyl diethyl succinate then in relevant solvent; Succinyl diethyl succinate and aniline condensation get 2,5-hexichol amido-3,6-dihydro diethyl terephthalate under the effect of anilinechloride; 2,5-hexichol amido-3,6-dihydro terephthalic acid diethyl fat is closed loop under the effect of the living A in road, gets 6, the 13-quinacridone; 6, the 13-quinacridone is in basic solution, and under the effect of oxygenant, the oxidation dehydrogenation gets quinacridone.2. Resorcinol method.This method is by Badische Anilin and Sodafabrik development, and process is as follows: 1. use the salicylate similar methods, obtain Resorcinol-2, the 5-dioctyl phthalate.2. with Resorcinol-2, the condensation under the effect of ammonium vanadate of 5-dioctyl phthalate and aniline gets 3,5-hexichol amido-2,5-dicarboxyl-1,4-benzoquinones.3. with 3,5-hexichol amido-2,5-dicarboxyl-1,4 benzoquinones closed loop in the vitriol oil, quinacridone quinone.4. quinacridone quinone available metal powder, zinc powder for example, in the low molten mixture of alchlor and urea, reaction in the time of 80 ℃, quinacridone quinone promptly is reduced into quinacridone.3. dibromo terephthalic acid method.This method is by Sandoz company development, and process is as follows: 1. 2, the 5-dibromoterephthalic acid under the effect of neutralized verdigris and potassiumiodide, in ethylene glycol solvent with aniline condensation, 2,5-hexichol amido terephthalic acid.2. 2,5-hexichol amido terephthalic acid closed loop in polyphosphoric acid gets quinacridone.4.2,5-two amido terephthalic acid methods.This method is by du pont company development, and process is as follows: 1. use 2,5-two amido terephthalic acids under the vitriolic effect with excessive pimelinketone condensation, make the octahydro quinacridone earlier.2. the octahydro quinacridone gets quinacridone through the pyrolysis dehydrogenation.5. ketene dimer method.This method is the development of Lonza company, and production process is as follows: 1. diketene is earlier oxidized, is become γ-chloroacetyl acetacetic ester by alcoholysis again.2. γ-chloroacetyl acetacetic ester from contract the succinyl diethyl succinate.3. succinyl diethyl succinate and aniline condensation, and then oxidation, saponification and acidifying get 2,5-hexichol amido terephthalic acid.4. 2,5-hexichol amido terephthalic acid closed loop in polyphosphoric acid, quinacridone.In the method for above-mentioned five kinds of synthetic quinacridones, in fact have only two kinds of methods in industrial-scale production, to use at present, promptly; Succinate method and diketene method.Other three kinds of methods are expensive because of raw material, cost is high, complex process, need specific installation etc. former thereby do not adopt.At present, produce the quinacridone pigment overwhelming majority in the world and all adopt the succinate method, but preparation technology is not quite similar.

The present invention adopts 2, and 5-diaryl-amine base-terephthalic acid is made raw material, the technology of closed loop system quinacridone in polyphosphoric acid, and this preparation technology's temperature of reaction is low, the yield height, and environmental pollution is few.

Feature of the present invention is that raw material directly adopts 2,5-diaryl-amine base terephthalic acid, after polyphosphoric acid (PPA) closed loop, product enters precipitating in the solvent, the pigmenting processing is carried out in press filtration again in solvent then, adds auxiliary agent, row making beating again, the time adding alkali in making beating, to make PH be 5～10, and products therefrom filter-press water-washing, drying, pulverizing, packing finally become serial pigment dyestuff C.IPV19 (γ), C.IPV19 (β), C.IPR122.

Technology of the present invention is rationally feasible.Product yield height, constant product quality.

Fig. 1 is a process flow sheet of the present invention.

The present invention prepares quinacridone and shows machine pigment C.IPV19 (γ), C.IPV19 (β), C.IPR122, illustrate respectively by following 3 embodiment: preparation method and the step of embodiment 1:C.IPV19 (γ) are as follows: in polyphosphoric acid (PPA) 100 parts of adding reactors that will prepare (part by weight, as follows), be warming up to 70 ℃, start stirring, slowly add 15 part 2,5-hexichol amido terephthalic acid (DATA), be warming up to 120～140 ℃, constant temperature 2～4 hours is poured in 300 parts of water that stirring, filter, filter cake is poured in the pigmenting reactor that is added with 120 parts of methyl alcohol, stirs, and refluxes 6～12 hours.Pressurization refluxed 2～6 hours then, and cooling adds the tensio-active agent making beating, and adding sodium hydroxide, to transfer PH be 5～10, press filtration, washing, oven dry, pulverize 12.9 parts of products C I.PV19 (γ) (in DATA, yield 95.9%).Preparation method and the step of embodiment 2:C.IPV19 (β) are as follows: in polyphosphoric acid (PPA) 90 parts of adding reactors that will prepare, be warming up to 70 ℃, start stirring, slowly add 15 part 2,5-hexichol amido terephthalic acid (DATA), be warming up to 120～140 ℃, constant temperature 2～4 hours is poured in 150 parts of methyl alcohol that stirring and is heated up, pressurization refluxed 2～6 hours, washing is filtered in cooling, and filter cake is put back in 120 parts of water and pulled an oar, add tensio-active agent, add alkali and transfer PH to 5～10, filter, washing, oven dry, pulverize 13 parts of products C .I.PV19 (β) (in DATA, yield 96.7%).Preparation method and the step of embodiment 3:C.I.PR122 are as follows: in polyphosphoric acid (PPA) 100 parts of adding reactors that will prepare, be warming up to 70 ℃, start stirring, slowly with 15 part 2,5-dimethylbenzene amido-terephthalic acid (DTTA) adds, be warming up to 110～135 ℃ then, constant temperature 2～5 hours is poured in 280 parts of water that stirring and is filtered, washing again, filter cake and 120 parts of ethanol are put into pigmenting and are handled still, temperature rising reflux 2～6 hours adds tensio-active agent, continues to reflux, cooling, transferring PH with alkali is 5～10, filters, washing, oven dry, pulverize 13.1 parts of products C .I.PR122 (in DTTA, yield 96.589%).

Claims (1)

1. a quinacridone is shown machine pigment prepared technology, it is characterized in that: raw material adopts 2, after 5-diaryl-amine base terephthalic acid is used polyphosphoric acid [PPA] closed loop, product enters precipitating in the solvent, the pigmenting processing is carried out in press filtration again in solvent then, and adds auxiliary agent, row making beating again, the time adding alkali in making beating, to make PH be 5-10, and products therefrom filter-press water-washing, drying, pulverizing, look dress be final to become serial pigment dyestuff C.I.PV19 (γ), C.I.PV19 (β), C.-I.PR122.

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