DE2026057A1 - - Google Patents

Description

sch / Gi

Xerox Corporation, Rochester, Hew York, ίΤ.Τ, \ / \ ΐϊΰΑ

Process for the production of MetaLlphtha'-LooyanLn

Ln the XB ¹ Orat

The invention relates generally to phthalocyanine materials and 'Irin special refers to new methods: 5ur Creation of metal. LphbhaLoo.yanLnen Ln the X-Porriu

Ph'ChalooyanLn, also known as ^r I.'e drive 7,0 te Lt. ·. · Laüaporpliin and 'De traben ^ oporph.yraKLn LnI ;, can aLfJ that Kon-Ioiuia- ruppen bee; u Lehne tv / orden, Me.taLLf i'uLeö Phthal.ouyanin beiii. t:; b fol ^ endo al Lgeineinti structure:

0.0 9 8 51/2 0 7 3

- a - ■. ■

N _. G G K HN Il ι
G. \ > / Il N NH G-" ι / N G G

In addition to the metal-free phthalocyanine of the structure given above, various centrally substituted metal phthalocyanines are known in which two hydrogen atoms in the center of the molecule are replaced by metals from any group of the periodic table of the elements. It is also known that 1 ~ 16 "of the hydrogen atoms located on the outer edge in the four benzene rings of the 1'hthaLocyan.LnmoLekuls can be replaced by haloalkynes and numerous organic and inorganic groups. The following statements refer primarily to central substL tu Le ν te metal phthalocyanines, as they have been described above.

MetaL! Phthalocyanines are present in at least three known polymorphic (I) ¹ poor, namely in the a-form, in the β-form and in the 'T-form. These forms can be divided into simple forms VZoLf) O using Lhror Ilöntgens to distinguish trahleiibeiffungsmuti ter and / or their infrared spectra, It is not yet entirely clear whether the T-shape is actually a separate polymorph or whether it is only a crystal form of phthalocyanine "Lt. In addition to these well-known forms, in which both dlo metaL Lon thaL tendon and the never tall-

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free phthalocyanine are present are further polymorphs of metal-containing phthalocyanine known, namely the "R" form, which is described in U.S. Patent 3,051,721, the "Deltai" shape, which is the subject of U.S. Patent 2,160,635 and another "delta" shape disclosed in U.S. Patent 2 150 150.

In US Pat. No. 3,357,989 and in German Pat (Patent application) it is stated that a particularly sensitive form of metal-free Phthalocyanine, known as X-form metal-free phthalocyanine, can be produced in such a way that the α- or ß-form of metal-free phthalocyanine is dry milled for a longer period of time. In the British U.S. Patent 1,189,206 discloses a second method of manufacture of metal-free phthalocyanine in the X form. This process consists in creating the α-crystal form of metal-free phthalocyanine with part of the metal-free Phthalocyanine in the X form and an aliphatic organic solvent to mix and the mixture as long as it is to be left until the metal-free α-form has been converted into the metal-free X-form. Both methods are time consuming and expensive. In Belgian patent 737 814 describes a direct process for the production of metal-free phthalocyanine in the X-form, which consists in Mixing phthalonitrile into an ammonia-saturated solvent, Heat to reflux temperature and apply the mixture with a catalytic amount of phthalocyanine in the X form to inoculate.

The known methods for the production of metal phthalocyanines see the reaction of phthalonitrile with a metal or a metal salt in ghinoline or a mixture of quinoline

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2026G57

and trichlorobenzene, the conversion of phthalic anhydride, Phthalic acid or phthalamide, urea, metal salts and a catalyst, the reaction of ο-cyanοbenzamid with a Metals and the reaction of phthalocyanine or a phthalocyanine with a replaceable metal with a metal that forms a more stable phthalocyanine. Me metal phthalocyanines, which are prepared by the methods described above are generally in the polymorphic a- or ß-Porm.

Belgian patent 737 988 describes metal phthalocyanines in the polymorphic X form and a process for their Manufacturing. In particular, this method consists in rapidly forming a metal phthalocyanine polymorph under a pressure of

- 1-6

sublimate about 10 to about 10 torr. If also this method works very quickly and in a high yield of essentially pure metal phthalocyanine in the X form supplies, the use of a complicated and expensive evaporation system is still required, namely especially when metal phthalocyanine in the X form in should be manufactured on an industrial scale.

The Belgian patent 737 989 describes a process for the production of metal phthalocyanine in the X-form, which Carin, the α- or ß-polymorph to approximately Heat 600 to about 650 ° G su. Even if the metal phthalocyanine in the X-form, which is produced by this process has excellent physical properties, there are still some disadvantages associated with this synthesis. For example, you have to use a phthalocyanine polymorph as the reactant and not the starting material from which the polymorph is obtained. This is how it is designed

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this synthesis into a two step process: (1) conversion a starting material to α-phthalocyanine and (2) converting the α-form to the X-form or converting it first α-form into the ß-form and then from the ß-form to the X shape. In addition, in the production of metal-free phthalocyanine in the α-form are for further conversion many difficulties were encountered in the X shape. The use of metal-free phthalocyanine in xei'ography places considerable demands on the purity of this material. It is required that the phthalocyanine contained in a xerographic plate to be used is generally free from impurities because of such impurities can affect the xerographic system in any way, and zv / ar either when charging or at the discharge of the electrographic system. Bishex * Phfc-halocyariin has almost always been used exclusively as a pigment used.' In this case the main factors are the color, the tinting power, the lightfastness, the diapergability or similar. The purity is less important. This has the consequence that the previously known Synthesis methods (compare "Phthalocyanine Compounds" from Moser and ihoma ", Rheinhold Publishing Company, pages 104 ■ -. 109) are often carried out in such a way that complex organic materials are urgently carried out as impurities, which are difficult to remove, ■;

The aim of the invention is to create an ancestor ;;! ijuc Ht-TEi töllung / on H · - ·· ^ l L phthalocyanine in 'lev Γ form, the! tiLohl iuf: -hr die; 70rs toil:; π '! ^ ,. iüoiiildur Lon ifaohkuil.e cling, Diu'oh dhi BrCLiidUii ^ will ^ in Him :! itu'en- DLreki; ~ Ψ; ιν £ ϊχΙιννΐι; ^IUF:; .liitj-. π division of Mfit.'illphthalonvaiiin Ln. ito.t: X -ί · ';η; ηι vtJUL · Vyr.-i'lU-jung posed, this i- / ri: mi: in \ hit ί' ,, άιν uluianh ϊΐηΊ avl ^ lt-ü: i -; honest. ^j

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fast. It also works in a reliable and reproducible manner Way.

The invention provides the provision of a new system for the production of metal phthalocyanine in the X form, which consists in mixing phthalonitrile into an alkylalkanolamine solvent and ammonia, a catalytic amount of a phthalocyanine in the Σ-ΙΌπη, either containing metal or admit metals, and a metal salt and cook then reflux.

Any suitable solvent can be used in this system. Typical solvents are alkylalkanolamines such as 2-dimethylaminoethanol, 1-dimethylamino-2-propanol, 1-diethylamino-2-propanol, 2-dimethylamino-2-methyl-1-propanol, 2 -Diethylaminoethanol, 3-dimethylamino = 1-propanol, 2- (diisopropylamino) -ethanol, 2-butylaminoethanol, 2-di'butylaminoethanol, 2-dibutylaminoethanol ·, 2 [(2- (diethylamino) "ethyl) -amino] -ethanolj 2, 2 '- (butylimino) -diäthanol, 2 ~ ithylamlnoäthanol, 2 _s 2- (Ithylimino) -diäthanol, 2-methy1-aminoethanol, 2, 2' - (Methyl.imino) -diäthanol 2- (isopropyl amino. ) -äfchanol, 2,2 '- (Isopropyliinino) -diethanol, 2,2' - (tert, -tiutylimino) -diethanol and 3-I) iäthylamino-1-propanol or the like, although any suitable solvent in this system tarn can be used, it is nevertheless preferable to use such XiÜxigcJmi L "i; el which contain a primary alcohol group, since in this case a higher yield of lan fiki'.Lpt'oduktöiri 'is achieved. Although .Each suitable fiöBun niil ^ L; tel containing a primary alcohol group er-C indiu ;,. "I ^{^:::;} '" i "Ji; iänii VQV / ends are canoe, they will still noticeably 1, Loh heh '; ilLUJbeuten an MetaLllphthalooyanui in the. · X-form er-iiall; en,', / nnn 2-.Dimo bhylaminoethariol «ingese fcs b .will so that

0 0 9 β 5! / 2 over 7 3

2026Q57

• -. - 7 this solvent is particularly preferred.

Although the inventive synthesis can be carried out at any suitable temperature, so still a temperature range of about 120 to about 28O ⁰ C is particularly preferred. Even if any suitable temperature can be maintained, it is nevertheless preferable ^{to choose the temperature range between about 135 and about 150 °} C., since higher yields of the desired end product are obtained within this temperature range.

The catalytically ^ amount of X-phthalocyanine, metal-containing either / or metal-free and which is used to perform the synthesis according to the invention can be produced by any AEEI: the above-stated methods are prepared.

The Gesamtreaktionsseit the reaction it is' danger 10 to about .70 minutes and depending upon the verwendeten.'Lösungsmittel * and, depending on the temperature maintained, lasts longer than about 70 minutes, then a formation of ß-metal phthalocyanine, such that Mixtures of the X-form and the ß-form can be obtained. A preferred reaction time is about 30 to about 55 minutes when using 2-dimethylaminoethanol. In this case a high yield of pure metal phthalocyanine in the X form is obtained.

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To slurry the phthalonitrile in the solvent can any suitable mixed method can be used. A complete Conversion of the phthalonitrile is achieved when the mixture is heated and stirred during the conversion and as ammonia gas is bubbled through the mixture. That Mixing can be done by grinding with glass or steel balls or merely by stirring using a magnetic stirrer or

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a simple rotary valve. Although the phthalocyanine · nitrile can be dissolved in the solvent at any suitable temperature, it is nevertheless preferable to then dissolve these materials, when the solvent at about 90-120 ⁰ O is heated.

After the phthalonitrile has been added to the hot solvent and ammonia gas is bubbled through the mixture, a catalytic amount of X-phthalocyanine is added. A metal salt is then added to the mixture, whereupon the temperature immediately rises to the reflux temperature as a result of a rapid exothermic reaction. The mixture is then 'held over a period of about 5 to about 70 minutes under reflux ", depending on the solvent used, followed by filtered hot', washed and ^dried.

The following examples illustrate various preferred embodiments of the method according to the invention. Unless otherwise stated, the parts and percentages relate to on weight.

The crystal forms of metal phthalocyanine that are used in carrying out of each of the following examples are generated using standard X-ray and Infrafoifä'nälyse methods determined. The X-ray and infrared curves of the. materials produced according to the following examples compared with the curves for known metal-free phthalocyanine in the α-form, in the ß-form and in the .X-form, (Compare also the German patent specification. ...... (patent application) and the US patent specification 3 357 989). A comparison is made with the curves of the polymorphic α-, ß- and X-porms of metal phthalocyanines.

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example 1

Approximately 200 ml of 2-dimethylaminoethanol are added ml in a four-necked flask having a capacity of 500, equipped with a mechanical stirrer, a reflux condenser, a thermometer and a gas Inlet sr ear is provided "The solution is heated ansehliessend to about 90 ⁹ C. At this temperature approximately 65 g of phthalonitrile are added. A steady stream of ammonia gas is introduced subsequently over a period of about 15 minutes, wherein the solution is heated to about 12O ⁰ O. At this point about 0.02 g of phthalocyanine in the X form is added, followed by the addition of about 11 g of an anhydrous cupric cyanide. The reaction temperature rises immediately to reflux temperature (about 135oQ) _aru D _as heating is continued for 15 minutes over a period of about. The mixture is then filtered hot, whereupon the residue is washed thoroughly with ethanol, acetone and methanol. An aqueous solution of sodium cyanide is used to remove unreacted copper (I) cyanide. After this treatment, the blue pest is washed with water to a pH of 7, followed by washing with hydrochloric acid, then with water and then with a 1 solution of ammonium hydroxide and then again with water and finally with methanol. The product is then ^{dried in an oven at approximately 70 °} C. for a period of 2 hours. The material obtained has a brilliant royal blue color. The yield is about $ 80>. This material is subjected to an X-ray and an infrared analysis in the usual way. The analysis shows that copper phthalocyanine in the X-form has been obtained. .

B0S8 5 t / -20 7 3

Example 2

Approximately 175 ml of 2-methylaminoethanol are placed in a 500 ml flask equipped as in Example 1. The solution is slowly erhitjst to about 11O ⁰ C, where "in

"About 65 g" of phthalonitrile are added to this temperature. Then ammonia gas is passed through, the mixture during a. A period of about 25 minutes, the solution being heated to about 125 ° C. over a period of about 20 minutes. At this point, approximately 0.03 g of metal-free es phthalocyanine in the X-JOrm is added, followed by the addition of approximately 16.2 g of an anhydrous cobalt (II) chloride. The reaction temperature rises immediately to the reflux temperature (135 ^° C.). Heating continues for a period of approximately 20 MiButene. A purple precipitate is separated off from the hot reaction mixture by filtration and washed thoroughly with ethanol and acetone. The purple needle-like crystals obtained are dried in an oven at a temperature of approximately 75 ° C. for a period of approximately 1 1/2 hours. The brilliant purple material is obtained in a yield of about 85 ° . It. is sent in the usual way by means of X-rays. Radiation and infrared analysis investigated. The "analysis shows that ilbalt phthalocyanine in the X-Iorm has been produced.

^; ■ · " ^: ■ · - ^f ε. · ■■■■:"'■' ■} .'-:. ··: -. ^ Ii; ^ - v. ■ - ■ - ■■ Example 5

The experiment described in Example 1 is repeated, except that about 250 ml of 3-? dimethylamino ^ 1- / propanol can be used instead of 2-dimethylaminoethanol, where "approximately 100 g instead of the 80 g of the phthalonitrile be used. It will take about 30 minutes instead of a *

Heated about 45 minutes before filtering. The product ■ booty is about 30 #. The product is made using X-rays as well examined by means of infrared analysis. It is found that copper phthalocyanine has formed in the X shape.

Example 4 .

As a control for the conversion process according to Example 3 the experiment is repeated, whereby the. Mixture is heated for 75 minutes instead of 30 minutes before filtering. An X-ray and infrared analysis shows that the product of a mixture of copper phthalocyanines in the X-form and consists in the ß-Porm.

Example 5 '

The conversion process according to Example 1 is carried out. the mixture being heated for 90 minutes instead of 50 minutes before piltrating. X-ray and infrared analysis shows complete conversion to β-copper phthalocyanine. ,

Example 6

As a further control for the conversion process according to Example 3, the catalytic amount of is not added Phthalocyanine in the X form. The analysis shows that no conversion to the X metal form has taken place.

Example 7

The experiment of Example 1 is repeated to give 1-dimethy1-amino-2-propanol (boiling point about 126 ° C) instead of 2-dimethylaminoethanol (boiling point about 135 ⁰ C) and 0.02 g of X-Ou phthalocyanine instead of 0 .02 g of the metal-free phthalocyanine can be used. The yield of the end product,

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which is identified by X-ray and infrared analysis as copper phthalocyanine in the X-form, is lower than the yield in Example ΐ, and indeed about 25 1 ° as opposed to about 80 $>.

Examples 8-11 ·.

'- ■■ * .

Example 2 is repeated four times using _: J using 0.125 moles of anhydrous magnesium chloride, anhydrous zinc chloride, anhydrous cadmium cyanide. and j anhydrous calcium chloride in place of the 0.125 mol of cobalt (II) chloride according to Example 2 is repeated. The products obtained are subjected to X-ray and infrared analysis. The values obtained are compared with the spectra of the corresponding polymorphic α and β forms and with spectra of various X-metal phthalocyanines. The analysis reveals that magnesium phthalocyanine in the X-form, zinc phthalocyanine in the X-form, Cag.mijumphthalocyanine in the X-form and calcium phthalocyanine in the X-form were obtained. , J``JU \ -. J 3.

In addition to the substances specified in the examples, other substances are used. Further measures can also be taken, for example another purification with similar results will. ...

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Claims (1)

202 £ 057 Requested clear. ,. ; ? erJaiaren for the preparation of a metal phthalocyanine in X-form, characterized in that ■ "'".' a) Jhthalonitrile is mixed into an alkyl alkanol affine solvent,
:, b} 'ammonia to the ^; Mixture is added, '^;: c) "ine · kataiytisehe 'amount of a Hithalocyanin Χίϊ the X ~ 1? orm iZugesetat is, d) a metal is added and e) mn. Sickflsiss. Is boiled. ■■ '' '2-. " Ferfabren necliisprucli 1, characterized in that the metal salt used consists of a copper salt, a cobalt salt, a zinc salt, a gadaium salt, a metal salt or mixtures thereof. 3 »1Ter, fa.hren according to claim 1, characterized in that the The metal salt used consists of a copper salt ".. ..: $ · ... Method according to claim 1, characterized in that the used Ifeijällsalz consists of a cobalt salt. ■ ι,
"S-. Iffer & hren according to one of the claims: r & before T- 4 * characterized by the fact that the alkylalkanolamine used is a primary c
^ contains. i5. Method according to one of claims 1 - 5, characterized gekennjaeiöhnet, that the alkylalkanolamine used from; 2-JDimethy.l consists. 7. The method according to one of speaking ^ 1 ■ -; &, dadiarjß> h .gekennzeichnet that the Bithalönitril is mixed with the ösungsmittel ^ ,, when the Iiösmngsmiitel has a © lempemtur of FLHR ungeiälir 90 to 120 ⁰ G. 8, method according to -a dex -atesprueiie 1 - 7 »dadiireh 25eiclinet that the received the Ifeteicial lieiss aiach üma. Boiling on the backflow is filtered. 9. Method according to one of the principles 1 - B, according to which the ammonia is added for a period of 5 to about 30 years. ? 10 procedures ^ ^ r Aiach eijiem jMSpi iiehe 1 * - "% sseichnet because ^ s cooking at MicJcflmss been driving 30 ibis 55 minutes is durchgeflhrt long, _-: 11. The method according to any one of claims 1 - 10, dadmrch ge lcindicates that the mixture © jalaaage is being used, the formation of the ^ talli ^ thalßc ^ anine in the 3 £ ~ F ©; kbi