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    17 views17 pages

    US20070181416A1

    Uploaded by

    Lucas Ferreira de Paula

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    © All Rights Reserved
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    ‘US 20071 Patent Application Publication (1 Pub. No.: US 2007/0181416 Al cu») United States « Jung et al. (54) PROCESS AND APPARATUS FOR PREPARING METAL OR NONMETAL PHTHALOCYANINE (75) Inventors: Ki Suck Jung, Busan (KR); Jon Kwon, Chungcheongbuk-do (KR): Seong Soo Park, Busan (KR): Woo Ho Son, Busan (KR) Ho Comespondence Address: OBLON, SPIVAK, MCCLELLAND, MATE] NEUSTADT, PC. 1940 DUKE STREET ALENANDRIA, VA 22314 (US) (73) Assignee: DABHAN SPECIALTY CHEMICS CO. LID., Ulsan (KR) (21) Appl. Now 108586,785 PCT Filed: May 14, 2008 (86) PCTNo: — POTIKRoso1144 §371(0)0). 2), (4) Date: Mar. 20, S1416A1 (4s) Pub. Date: ‘Aug. 9, 2007 G0) Foreign Application Priority Data May 14,2003 (KR) May 14,2003 (KR) 10-2003-0030727 10-2043-0030726 Publication Classification GI) Int. BOLE 19/12 (2006.01) (2) USC 2047157.72; 204/193 6 ABSTRACT Disclosed herein is a process for preparin nonmetal phthalocyanine by using both microwave ultrasonic wave enemy in the presence of a solvent, or by using microwave energy’ in the absence of a solvent. Spe- cifically, aceording to the process, anhydrous phihalie acid phthalimide, 13-diiminolsoindoline, 1,2-dieyanobenzene, ‘an halogen derivative theeot, an alkyl_derivative thereof oF fn alkoxy derivative theroot is mixed with a metal chloride fran alkoxy metal at 130250° C. for 0.2515 hours by us microwave ata frequency of 0.1-1000 Hz and a power of 100-3,000 W and ultrasonic wave at Frequency of 1-1,000 Giiz and a power of 100-5,000 W in the presence of & solvent, of BY using microwave ata frequency of 0.1-100 Giiz ands power of 100-4,000 W in the absence of @ solvent, Further diselosed is an apparatus for preparing a ‘tal or nonmictal pihalocyanine inthe absence or presence of solvent Patent Application Publication Aug. 9, 2007 Sheet 1 of 4 US 2007/0181416 A1 Patent Application Publication Aug. 9, 2007 Sheet 2 of 4 US 2007/0181416 A1 11s ‘LI “ P* " t— 17 | te Ea 8 FIG. 3 Patent Application Publication Aug. 9, 2007 Sheet 3 of 4 US 2007/0181416 A1 Patent Application Publication Aug. 9, 2007 Sheet 4 of 4 US 2007/0181416 A1 US 2007/0181416 Al PROCESS AND APPARATUS FOR PREPARING METAL OR NONMETAL PHTHALOCYANINE, TECHNICAL FIELD. [0001] The present invention relates to @ process and aa ;pparatas for preparing « metal or nonmetal phthalocyanine using both micriwave and ultrasonic wave energy in the absence of presence of solvent. BACKGROUND ART [0002] Phihalocyanines are compounds represented by the Structural formula shown in FIG. 1, and exhibit superior stability and excellent photoelectric properties due to thei ‘unique chemical stricture, For these reasons, patalocys- nines are currently used in a wide variety of applications such as dyes, pigments, chemical sensors, electrochomic displays, photovoliagie cells, radiators, photodisks, cata Iysts, non-linear opties and the like. [0003] A phthalocyanine i commonly prepared by react Ing a starting material selected from anhydrous phthalic acid, phthalimide, 1,3-diiminoisoindoline, 1,2-dicyanoben- zene and derivatives thereof With a metal chloride or aa alkoxy metal using urea or ammonia as nitrogen source st 4 temperature of 180° C. or higher, in the presence of a ‘catalyst in an inert solvent or without any solvent. [0004] The phthalocyanine thus prepared must esseatilly "undergo pigmentation in order toe used as 2 pigment. The pPhibalocyanine pigmentation is mainly achioved by the Tollowing techniques: [0005] 1) Kneading: A phthalocyanine and finely divided salt or a metal salt are placed in a kneader, and are then kneaded for a predetermined period of time; [0006] 2) Milling and Organie solvent treatment: phtha- locyanine is subjested to dry oF wet milling, and is then treated with an onganie solvent; and [0007] 3) Milling and Kneading: A phthalocyanine is subjected to dey or wet milling, and is Wien kneaded. [0008] Japanese Patent Laid-open No. Hei 8291261 dis- loses a process for preparing phthalocyanine using a heat Source at 200-250" Cin The presence ofa solvent such as ‘hloronaphthalee. However, hi process has the following problems: i) impurities thot are diffelt to remove are Formed on a igivtemperatore portion det the difference between internal and extra temperatures of reactants, fi) Since the phiblocyanine particles are son-ubifrmly dix persed and auglomerted in a nelle shape, they must Undergo long-ta pigmentation before se pase. it) this process requis a lange quantity of energy inorder t0 recover the solvent used forthe reaction anv) this process is disadvantageous in tems of process efceney and envi roomental management [0009] Commonly. phitalocyanine may be prepared using # conventional heat source in the absence of solvent. “This preparation process aso has various problems. Fist, since reactants are not homogeneously mixed during prepa ration and are heated using electricity or thermal oil, the ‘internal temperature of the reactor is non-uniform, causing Jow yield and poor quality ofthe phihaloeyanine due to the presence of dificul-to-emove impurities formed ata high- Temperature portion 0 which relatively high heat is Aug. 9, 2007 he heat source, For these reasons, a number processes have been reported in the litera tres, However, few processes have been applicable ro mass production of phthalocyanines. Alihough some Czech and (Chinese companies have attempted and finally succeeded in ‘mass production of phihalocyanines, they sloped in the middle of produetion due to poor quality of the phthalocya- sine underoing pigmentation, [0010] I order to solve the above-mentioned problems associated with non-uniform beat transfer, electricity and thermal oil as beat sources have been replaced with micro- waves. Sueh trials can be found in many references (US. Pat. No. 6,491,796; and Fil Intemational Eletronie Con- erence on Synthetic Organie Chemistry (ECSOC-5), 1-30 September 2001, pp 4-5). Microwaves are electromagnetic ‘waves having a wavelength ranging from 0.001 m to 1 m, ‘nd have functions such as rapid eating, selective heating ‘and volume heating, ete Sinee microwaves dreetly heat an ‘object that is intended to be heated, external heating is ‘unnecessary. Accordingly te use of microwaves minimizes the fomnation of dilficull-to-remove impurities, However, since reactants are not homogenously mixed during reaction despite the use of mierowaves, the yield of phthalocyanines {snot greatly increased, the mass prodvetion of phbaloeya- nines is difficult, and the quality of phihaloeyanines is not ‘comparable fo that of phthalocyanines prepared by solvent processes. In conclusion, the preparation of a phthalocya fine using microwaves isnot suitable Tor mass production ‘and commercialization, SUMMARY OF THE INVENTION [0011] ‘Therefore, the present invention hes been made in View of the above problems of conventional solvent oF solvent-ffee processes, and the present invention provides a novel process for preparing metal or nonmetal (that is ‘metaltree) phthalocyanine wherein a conventional, heat source, such as electricity or thermal cil, is replaced with microwave energy s0 that problems resulting from non- uniform heat transfer can be avoided, and a dry or wet milling device is used for homogeneously mixing reactants so that a metal or nonmetal phibaloeyenine can be prepared in high yield and the phthalocyanine paricles ean be milled immediately after being formed, thereby preventing firm agglomeration of the phthalocyanine particles To this end, the present invention aso provides a miling-type apparatus tor preparing a metal or nonmetal phthalocyanine using rowaves inthe absence ofa solvent (hereinafter, refered to as a “solventiree milling-type microwave apparatus comprising: milling device, such as-a vertcal-type atetor for ball mil, filled with alumina or glass beads having a ameter not Iamger than 30 mm; at least one magnetron providing a fraqueney of 0.1-100 Gllz and a power of 100-4,000 W installed on an upper cover of the milling vice: a microwave-shielded infrared temperature detector {or accurately measuring and controlling the temperature of reactants; a PID temperature controller for coatrlling the power ofthe magnetron; 2 vent port for exhausting gasses, eg, ammonia, generated during reaction; an agitator motor {or rotating au agitator so as to permit homogeneous mixing nd milling inside the milling device: and a discharge valve for discharging phibalocyanine product prepared after [0012] | Purther, the present invention has been made in View ofthe above problems, ew, long US 2007/0181416 Al ‘conventional solvent processes using a eat source and microwave energy, and the present invention provides 2 process for preparing a metal or nonmetal phthalocyanine ‘wherein both microwave and ultrasonic eneray are used t0 ‘enhance the yield, purity and physical propertios of the pPhibalocyanine [0013] To this end, the present invention also provides an apparatus for preparing a metal or nonmetal phthalocyanine ‘comprising: a magneton providing a frequency of 0.1100 ‘Glizand.a power of 100-3,000 W:a mode stirrer for making the wavelength of microwaves uniform in a microwave vessel: a PID temperature controller for aeeurately measur- ing and controlling the temperature of reactants; a micro= wave-shielded Ktype thermocouple, a condenser and an agitator which are fited into thee holes formed on top ofthe microwave vessel, respectively; an ultrasonic tip fitted into athole formed at bottom of the microwave vessel; a Pyrex ‘container for secommodting reactants; and a solvent tuk, DESCRIPTION OF DRAWINGS [0014] The above and other objects, features and other ‘advaatages of the present invention will be more cleaely tunderstood from the following detailed description taken ia ‘conjunction with the accompanying drawings, in whieh [0015] FIG. 1 shows the structural formula of a metal or rhonmetal phthalocyanine, ora derivative thereof (wherein M is copper, iron, cobalt, nickel, manganese, aluminum, zallium, Vanadium, palladium, lead, i, titanium, robidium, ‘erbium, cerium, lanthanum, zinc or hydrogen: X is hydro- zen, fluor, chlor, bromo, an alk group or alkoxy group: fand'k, Lm and n dre integers of 1 to 4): [0016] FIG. 2 shows an apparatus for preparing a metal or ‘nonmetal phthalocyanine using both microwave and ultra- sonic wave energy in aovordance with the resent invention: [0017] FIG. 3 shows a solvent-five ailling-type miero= wave apparatus avcording to one embodimeat of Uke present invention; [0018] FIG. 4 shows an electron mierograph (1,500x) of a ‘copper phthalocyanine prepared using the solvent-free mill- ing-iype microwave apparatus shown in FIG. 3: [0019] FIG. § shows an electron micrograph (1,$00x) ofa ‘copper phthalocyanine prepared by using a conventional solvent process [0020] FIG. 6 shows an electron mierograph (1,500x) ofa ‘copper phihaloeyanine prepared by using’ conventional solventfiee process; and [0021] F1G.7 shows an electron mierograph (1,500x) ofa ‘copper phthalocyanine prepared by using conventional solvent-free process using microwave. DESCRIPTION OF PREFERRED EMBODIMENTS, [0022] The present invention will now be described in more detail [0023] The present invention provides a prooess for pre Paring a metal or nonmetal phthalocyanine by using both Iicrowave and ultrasonic wave energy in the presence of @ solvent of by using microwave energy as a heat source in @ Aug. 9, 2007 vertcaltype dry or wet milling devie, such a an attitor or ball mill in the absence of « solvent [0024] Anhydrous phthalic acid, phthalimide, 1.3 soisoindoline, 1,2-dicyanobenzene. a halogen derivative thereon alkyl derivative thereof, an alkoxy derivative thereof or the like is used asa starting material, and urea or ‘ammonia is used a5 4 nitrogen source. As a metal source suitable for usein the preparation of a motal phthalocyanine, a metal chloride (e, copper chloride, iron chloride, tia nium chloride, et.) or an alkoxy metal (eg. ethoxy ‘ium, propoxy titanium, butoxy titanium, ec) is used. As a reaction catalyst, ammonium molybdate, 1.8diszabicyclo [5-4.0]undec-7-ene (DBU) or 1,5-diazabieyelof4.3.0}-0n- S-ene (DBN) is used. Ava solvent, «halogenated aromatic hydrocarbon selected from alkyl benzenes, N-methyl pyrrolidone, quinoline, trichlorobeazene and I-chloronoph- ‘halene, of an aleohol selected from isoamylalcobel, a-0e- anol, 2-thylhexanol and ethyleneglyeo, 6 use. [0025] FIG. 2 shows an apparatus according 10 a first embodiment of the present invention. The apparatus com prises a magnetron 1 providing a frequeney of 0.1~100 GHz, and a power of 100-3,000 W: a mode ster 3 for making the wavelength of microwaves uniform in a microwave vessel 2; a PID temperature controller 8 made of stainless steel for securately measuring and controlling the temper lure of recetants; a microwave-shielded K-ype themno- couple 4,2 condenser § and an agitator 6 which are fitted ito three holes (diameter: about 1 em) formed on top ofthe microwave vessel, respeetively an ultrasonie tip 7 fit into ‘hole (diameter: about 1 em) formed atthe bottom of the mierowave vessel; a Pyrex container 9 for aeeommodsting reactants; and a solvent tank 10 Filled with decalin (deeaby= dronaphthalene) capable of transferring ultrasonic wave fenergy to the reuclants without any reaction with miero- [0026] a the apparatus of the present invention the reve- fants are heated ata rate of about 2-20" Cminute to 120° Cvusing microwave energy ata frequency of 01-100 GH and a passer of 100-3,000 W while heing uniformly stirred jn the presence of solvent, and are further heated at rate of about 0.2510" C minute to 130-250" C., which isthe final preparing temperature. During reaction, the temperature of the reactants can be accurately controlled using the PID temperature controller & within a deviation of 21°C, snd the microwave ata frequency of 0.1100 Giz and a power of 100-3,000 W aad uliasonie wave energy ata frequency of | 1-100 kHz. and a power of 100-5.000 W are simalta- neously used starting from the initial stage of the reaction. [0027] FIG. 3 shows another apparatus socording to @ Second embodiment of the present invention. Unlike the microwave generation apparais shown in FIG. 2, the appa- ratus shown ia FIG, 3 ses four magnetrons 11 providing @ frequency of 0.1100 Gz and a power of 100~4,000 W, and a milling device 12, such as # vericaltype atitor oF ball mil filled with slumina beads or glass bas having & ameter not lager than 30 mm as mulling media. As the microwave generation apparatus, the four magnetrons pro- viding a frequeney of 0.1~100 Griz and a power of 100~$, (000 W are installed inthe four sides of an upper cover ofthe nilling device 12 so that the miemowave wavelength can be ‘uniformly dispersed In adtion, this appara further com- prises & microwave-shielded infrared temperatre detector US 2007/0181416 Al 14 for accurately measuring and controlling the temperature ‘of reactants, a PID temperature controller 18 for controlling, the power ofthe magnetron 11,2 vent port 18 for evolving passes, eg. ammonia, generated during reaction, an agitator motor 18 for rotating an agitator 17 50 as to permit homo- ‘geneous mixing and milling inside the milling device, and @ ‘discharge valve. 19 for discharging a phthalocyanine prod tet prepared after reaction, [0028] First, reactants are introduced into the solvent-free nilling-type microwave apparatus. Thereafer, the reactants ‘are heated at a rate af about 2~20° C nine 120° C, with Stirring at a stirring spesd of 300400 rpm andl are furcher heated at arate oF abou 0.25~10" C mintte to 130-250" C., ‘which is the final preparing temperature. During reaction, the temperature of the fesctans ean be acuately controled using the PID temperature controller within deviation of 1°, and the microwave poster is controlled within the range of 100-4.000 W. While the final preparing tempera- ture is maintained, the reactants are usiformly stired for 1025-10 hours to prepare a phibalocyanine. ARer comple tion of the preparation, unreacted reactants are removed in the following procedure. The phhaloeyanine thus prepared js added wa 3% sulfuric acid solution, acid-treated at 85°C. orone hows, and washed with distilled water at 90°C. until the pH is neutral. The acid-treated phthalocyanine is rdis- pom in 1% aqueous sodium hydroxide solution, alkali teeated at 85° C- for one hour, washed with distilled water at 90°C. until the pH is neutral, and dried in a dryer at about 108° C. for 24 hours [0029] According 1 the present invention, since the com- bination of microwave and ultrasonic wave energy can prevent auglomeration of phthalocyanine particles inside the reaction slurry and promote homogeneity ofthe srry metal ‘or nonmetal phialoeyanine partiles ina small needle shape ‘ean be prepared without agglomeration under the same preparing conditions of temperature and time. Accordingly, Since the process ofthe present invention ean cans shorten the pigmentation time and enhance the quali Phihaloeyanine pigment, it is suitable for indistrial appli cations [0030] In addition, the phthalocyanine produved by the process of the present invention can markedly shorn the Time requieed for pigmentation, A phthalocyanine pigment ‘obiained after long-term pigmentation, such as kneading oF ‘dry or wet milling, of phthalocyanine prepared by 3 ‘conventional solvent-free process is inferior in quality to 3 phthalocyanine pigment prepared by 2 conventional solvent- free process, and hence it cannot be practically used. As ready reported in many references, since dry or wet milling ‘ean finely divide large panicles and loosen fimnly agglom= ‘erated particles, kneading time is shortened. In particular such dry or wet milling isan essential step inthe treatment ‘ofan orzanie solvent Accordingly already known processes further involve milling afer preparation of phthalocyanines. Incoatrast, since the phthalocyanine prepared by the process ‘of the present invention is milled immediately after prepa ration of the plitaloeyanine, the phibalocyanine ‘bas parle size by 50-60% smaller than that of phthalocyanine prepared by conventional processes, In addition, since the shape of the phthalocyanine particles prepared by the pro- ‘cess of the present invention is almost spherical, further milling is unnceessary, the time required for pigmentation ‘can be shortened by about 50% or more, and the phthalo- Aug. 9, 2007 ceyanine can be directly used as a pigment without under- f20ing additonal pigmentation according to ils intended application. Accordingly, a solvent-free process for prepar ing phthalocyanines, whieh hus been thought to be impos sible, ean be put to practical use. [0031] Pigmentation of the phthalocyanine prepared by the process of the present invention is caried out by the following techniques [0032] Pigmentation 1: Kneading [0033] A metal or nonmetal phitaloeyanine and finely vided salt are charged into a kneader equipped with @ sigma blade, and then an appropriate amount of diethylene alyeo! (DEG) js odded thoreto. The resulting mixture is kneaded at 100-110" C. for a predetermined period of time After the kneaded mixture is ken ot iti dispersed in a 5% sulfuric seid solution, washed with distilled water at 90° C. until the pH is neutral, redispersed in distilled water, filtered, washed with disiled water at 90° C. until the clecizical conductivity ofthe filiate reaches 250 CSiem oF Jess, and dried in a dryer at about 105° C. for 24 hours [0034] Pigmentation 2: Milling and Onganic Solvent Treatment [0035] A metal or nonmetal phiisloeyanine is introduced into an atitor or vibration mill, and then steel rods or balls are introduced thereinto. The phthalocyanine is dry milled {or a prodetemined period of time, Separately, a rosin solution is prepared in acconlance with the procedare described in Example | of PCT publication WO 99/54410 (Applicant Ciba Specialty Chemicals Holding Ine). That fan aqueous potassium hydroxide solution and rosin are ‘added a cern amount of water, The resulting mixture is ‘completely dissolved to prepare a rosin solution, aftr which water is added for dilution, The milled phthalocyanine is dispersed in IPS2 (Charles Tennant, UK) as a solvent, and then the rosin solution is added thereto, The resulting sixture is rfiaxed for 4 hour, Thereafter, water is added to the refluxed mixture, and distilled to collect the solvent. Hydrochloric acid is added to the solventlrce slurry to render the slury acidic. The slury is filtered, washed wt the pl is neutral, und died in a dryer. [0036] Pigmeatation 3: Milling and kneading [0037] A phthalocyanine is intretuced into an attor oF vibration mill, and thea steel rods or balls are introduced thereinto, The phihaloeyanine is dry milled for a predeter- ‘mined period of time. The milled phthalocyanine is treated in the Sime manner as in Pigmentation 1 [0038] The present invention will now be described ia ‘more detail with reference to the following examples and comparative examples. However, these examples ane not 10 be construed as limiting the seope of the invention. EXAMPLE 1 [0039] Preparation of Copper Phihalocysaine [0040]. ‘This example was done ina solvent-type apparatis according to the present invention. Specifically, 42 g of anhydrous phthalic acd, 49 gof urea, 7 xa eopper chloride, 0.1 gofammonium molybdate and 100g ofan alkylbenzene were introduced into @ Pyrex container 9, and then the reactants were uniformly sired at 180~185" C. for 3 hours US 2007/0181416 Al by using microwaves at 28 kHz and ultrasonic wave eneesy ‘at 250 W, to prepare a copper phthalocyanine. During reaction, the temperature of the reactants was aceurately ‘controlled using the PID temperature contoller 8 within 3 deviation of #1° C.. and thus the microwave power Was ‘maintained at 100-3,000 W. The microwave and ultrasonic ‘wave energy were simultaneously used staring from the inital stage of the reaction. After completion of the prep ration, the removal of the solvent was carried cut hy

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