CN1342729A - Process for preparing nm-class Y-type phthalocyanine titanium oxide in batch - Google Patents
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- CN1342729A CN1342729A CN 00124736 CN00124736A CN1342729A CN 1342729 A CN1342729 A CN 1342729A CN 00124736 CN00124736 CN 00124736 CN 00124736 A CN00124736 A CN 00124736A CN 1342729 A CN1342729 A CN 1342729A
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Abstract
A process for preparing nm-class Y-type phthalocyanine titanium oxide in batches features that a crystal form regulator is added to amorphous deposition for full crystallization and oriented crystallization, and an one-step method is used. Its advantages are high specific surface area, high conversion efficiency, and nm-class granularity.
Description
The present invention relates to the preparation method of TiOPc (Y-TiOPc), be specifically related to the large-scale preparation method of nano level Y type TiOPc.
Adopt electrostatic methods, form the core component photoconductor drum that the electrostatic latent image technology successfully has been applied to make laser printer and xerographic printer on the optical conductor surface.This photosensitive drums is made up of conductive substrate and one or more layers film that contains the photoconductivity material usually.Between photoresistance and basic unit, can increase one deck carrier barrier layer, to improve the initial potential of photosensitive drums.
The light-guiding film that various ways is arranged at present.For example: the composite membrane of homogeneous unitary film (as treous selenium) and dispersion light-guide material.As an example of composite membrane, a United States Patent (USP) (U.S.Pat.No 3,121,006) has been reported by a kind of electric insulation resin tackiness agent and the ultra-fine inorganic light-guide material that is scattered in wherein and has been formed.Its inorganic light-guide material is mainly ZnO, and resin is mainly polycarbonate, polyester and polymeric amide etc.In this optical conductor film, because tackiness agent can't be long apart from the ground transmission charge, so the particle of optical conductor must keep in touch.Another kind of photosensitive drums is the function divergence type, and promptly photoresistance is made up of two portions, and one deck is that current carrier produces layer (CGL), and essential characteristic is that the light-guide material particles dispersed of organic or inorganic is in tackiness agent; Another layer is carrier blocking layers (CTL), it is characterized in that the carrier mobility dispersion of materials is in tackiness agent.The preparation method of this function divergence type photosensitive drums has been described among the United States Patent (USP) U.S.Pat.No 4,265,990.
As carrier generation materials, the sensitive volume of photocon can be expanded to visible region and near-infrared region with some phthalocyanine compound, this application to photocon is significant.In this type of phthalocyanine compound, ranadylic phthalocyanine (VOPc) and TiOPc (TiOPc) are only materials.The existing many patent reports of synthetic and aftertreatment about VOPc and TiOPc.U.S.Pat.No2 for example, 155,038; U.S.Pat.No3,825,422; U.S.Pat.No4,032,339 etc.Its synthetic method is mainly by phthalic nitrile and V
2O
5(or VOCl
3) and TiCl
4Reaction realize.Handle the approach of phthalocyanine-like compound by sedimentary method in concentrated sulfuric acid dissolution and the frozen water, have multinomial patent to relate to this mode, as U.S.Pat.No3,717,493; U.S.Pat.No2,155,038; U.S.Pat.No4,032,399; U.S.Pat.No4,076,527; Br.Pat.No502,623.Generally speaking, prepared bigger, the photosensitive efficient of phthalocyanine material granule of technology in early stage is low, the required exposure time is long, therefore is not suitable for the photoelectric device for preparing laser printer and xerographic printer.
In existing phthalocyanines crystal formation regulation technology, normally the acid paste solution of phthalocyanine-like compound is poured into and formed amorphous sediment in the frozen water, should precipitate again through repeatedly washing--the suction filtration step is until reaching neutral, and is dry then.Dried product is dispersed in two-phase solvent (as water/orthodichlorobenzene) or the single solvent (as n-butyl ether, propyl carbinol etc.) carries out crystalline form by ball milling or powerful alr mode and transform, final formation has phthalocyanine definite crystal formation, that photoconductivity is arranged.
The not only time-consuming length of said process crystal formation regulate process, and only be suitable for semimicro (＜1g) preparation.Crystal formation can not transform (transformation efficiency is no more than 70%) fully during amplification quantity preparation (more than the 10g), and the gained particle easily comprises impurity, is difficult to clean.In addition, the method for simple Ball milling can not make the particulate size arrive nano level ultra-fine degree.
Along with the development of eletrophotography technology, more and more higher to the requirement of the image taking speed of photosensitive drums and image quality.In addition, along with the continuous increase of market to the quantity of duplicating machine and laser printer, an urgent demand development is quick, easy, the technology of scale preparation high sensitivity phthalocyanine pigment.
The object of the present invention is to provide a kind of large-scale preparation method of nano level Y type TiOPc.
The large-scale preparation method of nano level Y type TiOPc of the present invention comprises following sequential steps:
A) the polymorphic phthalocyanine compound is dissolved in the vitriol oil, then this solution is poured in the mixture of ice and water.Stir, form amorphous sediment;
B) leave standstill hypsokinesis and go upper solution, add entry again, stir, leave standstill hypsokinesis and go upper solution, at least three times so repeatedly;
C) directly add the crystalline form conditioning agent at above-mentioned solution, stir and form colloidal solution, stir 8-72h, leave standstill, the supernatant liquid that inclines adds the crystalline form conditioning agent more again, stirs, and leaves standstill.
D) inclined suction filtration, washing leaching cake the upper strata stillness of night; Place low-boiling point alcohol to stir filter cake, filter,, get Y type TiOPc the filter cake oven dry.
E) polycarbonate, polyvinyl alcohol, polyamide-based, polystyrene or polyvinyl carbazole are dissolved in alkyl chloride, ketone or the ether solvent, make solution.
F) with above-mentioned TiOPc material at ball mill grinding, join in the solution of step e, form suspension, use ultrasonic dispersing, obtain high sensitivity nano level Y type TiOPc coating fluid.
In the present invention, crystal structure adjusting agent is orthodichlorobenzene or chlorobenzene, polyvalent alcohol and 4 single alcohol that carbon is above, and wherein the volume ratio of water and each solvent of crystal structure adjusting agent is: orthodichlorobenzene or chlorobenzene: polyvalent alcohol: 4 single alcohol that carbon is above: water=0.1-1: 0.5-5: 0.5-5: 1.Wherein polyvalent alcohol can be ethylene glycol or glycerol, and 4 above single alcohol of carbon can be propyl carbinol.
In the present invention, alkyl chloride, ketone or ether solvent are pimelinketone, 1, and 2-ethylene dichloride, ethylene dichloride, vinyl trichloride, trichloromethane, tetrahydrofuran (THF) or butanone partially.
In the present invention, the phthalocyanines light-guide material of granularity below 20nm comprises TiOPc, VOPc, CuPc, AlPc or InPc.
Fig. 1 is the photoelectric characteristic figure of the photoelectric device of CGM preparation for prepared TiOPc.
Fig. 2 is the prepared TiOPc particulate STM sem photograph that contains.
Fig. 3 is the X-ray crystal powder diffractogram of prepared Y-TiOPc.
Material photoelectric efficiency height, dark-decay that the present invention obtains are little, and particle size mainly is distributed in 5--20 Nm is applicable to that the laser printer OPC of the various models of preparation rouses. Contrast test shows, this material Prepared OPC drum and the original-pack drum of import (Xerox Corporation, Hewlett-Packard and CANON Deng) indices is substantially suitable. The present invention is different from existing technology, is having aspect the crystalline form conversion Distinctive feature, and be convenient to carry out the scale preparation.
Advantage of the present invention is mainly derived from the following aspects:
Adopt directly transform sour one step of paste method, make operating performance greatly easy;
The incomplete possibility that reaches to other transformation of crystals of transformation of crystal has been avoided in the employing of homogeneous phase conditioning agent The property;
The employing of one-step method has increased the specific surface of material, has improved transformation efficiency, and impurity is easy to Flush away;
Material by first ball milling after ultrasonic method, guaranteed the nano particle degree.
Luminous sensitivity E by the photoelectric device (take diethylin benzaldehyde diphenyl hydrazone as the migration material) of this material preparation1/2Be 0.47 lux..s, the wide 500-830nm of sensitization response range, light transmission is good, Photo-generated carrier efficient height, dark-decay is low, the sensitivity height, rest potential is low.
Embodiment 1:
Adjacent benzene two fine (1000g) and the TiCl of the synthetic employing of TiOPc
4Synthetic route (250ml)
With phenyl ether (4000ml) is reaction solvent, at 260 ℃ and N
2Protection is powerful the stirring down, and reaction is 8 hours, and crude product is an atropurpureus; Filtered while hot, and, use HCl solution, NaHCO then with the washing of the hot solution of phenyl ether
3Solution, DMF solution, benzene, methyl alcohol etc. wash successively, can get product 500g.Get the 200g product and be dissolved in the dense H2SO4 of 2500ml (98%), this drips of solution is added in the 10kg frozen water, the gained mixture continues to stir 1 hour, leaves standstill, and the supernatant liquid that inclines adds 5kg water again, stirs; Repeat aforesaid operations three times.After decant finishes the last time, add 1000ml ethylene glycol, the 1000ml propyl carbinol, 300ml orthodichlorobenzene and certain water gaging, making ratio is water: ethylene glycol: propyl carbinol: orthodichlorobenzene is (10: 10: 10: 3), stir after 24 hours, leave standstill the supernatant liquid that inclines, after-filtration, filter cake moves in the 2000ml methyl alcohol, thorough washing; Refilter, drying, promptly get high sensitivity Y type TiOPc pigment.Behind this pigment ball milling, be suspended in and carry out ultra-sonic dispersion in the solution that contains polycarbonate, promptly get the colloid coating fluid of nano-level pigment particle.The phthalocyanine granulates size adopts the STM transmission electron microscope to characterize in the coating fluid, and mean diameter is 10nm, and size distribution is 5-20nm; The crystalline form of this material adopts the X-RAY powder diffractometer to characterize, and is consistent with standard Y-TiOPc crystallogram.
It is that 90 ℃ of dryings were coated with 1 of last layer hydrazone compounds and polycarbonate on its surface after 1 hour on blocking layer aluminium base that this coating fluid is coated casein food grade, the 2-dichloroethane solution, 80 ℃ dry 1 hour down, finish the preparation of photocon.This photocon is characterized on static paper analyser, and charging voltage is 1400v, its sensitivity E
1/2Be 0.47lux.s.
Claims (5)
1. the large-scale preparation method of a nano level Y type TiOPc comprises following sequential steps:
A) the polymorphic phthalocyanine compound is dissolved in the vitriol oil, then this solution is poured in the mixture of ice and water.Stir, form amorphous sediment;
B) leave standstill hypsokinesis and go upper solution, add entry again, stir, leave standstill hypsokinesis and go upper solution, at least three times so repeatedly;
C) directly add the crystalline form conditioning agent at above-mentioned solution, stir and form colloidal solution, stir 8-72h, leave standstill, the supernatant liquid that inclines adds the crystalline form conditioning agent more again, stirs, and leaves standstill.
D) inclined suction filtration, washing leaching cake the upper strata stillness of night; Place low-boiling point alcohol to stir filter cake, filter,, get Y type TiOPc the filter cake oven dry.
E) polycarbonate, polyvinyl alcohol, polyamide-based, polystyrene or polyvinyl carbazole are dissolved in alkyl chloride, ketone or the ether solvent, make solution.
F) with above-mentioned TiOPc material at ball mill grinding, join in the solution of step e, form suspension, use ultrasonic dispersing, obtain high sensitivity nano level Y type TiOPc coating fluid.
2. according to the process of claim 1 wherein that described crystal structure adjusting agent is orthodichlorobenzene or chlorobenzene, polyvalent alcohol and 4 single alcohol more than the carbon.
3. according to the method for claim 2, wherein the volume ratio of water and each solvent of crystal structure adjusting agent is: orthodichlorobenzene or chlorobenzene: polyvalent alcohol: 4 single alcohol that carbon is above: water=0.1-1: 0.5-5: 0.5-5: 1.
4. according to the method for claim 2, wherein polyvalent alcohol is ethylene glycol or glycerol, and 4 above list alcohol of carbon are propyl carbinol.
5. according to the process of claim 1 wherein that described alkyl chloride, ketone or ether solvent are pimelinketone, 1,2-ethylene dichloride, ethylene dichloride partially, vinyl trichloride, trichloromethane, tetrahydrofuran (THF), or butanone.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00124736 CN1117821C (en) | 2000-09-14 | 2000-09-14 | Process for preparing nm-class Y-type phthalocyanine titanium oxide in batch |
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| CN 00124736 CN1117821C (en) | 2000-09-14 | 2000-09-14 | Process for preparing nm-class Y-type phthalocyanine titanium oxide in batch |
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| CN1117821C CN1117821C (en) | 2003-08-13 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302773C (en) * | 2002-07-09 | 2007-03-07 | 成都思摩纳米技术有限公司 | Method for preparing nanometer suspension of DHA |
| CN1308775C (en) * | 2003-01-22 | 2007-04-04 | 北京大学 | Monolayer organic light receptor positive charged as well as dedicated material and preparation method |
| CN102653679A (en) * | 2011-03-04 | 2012-09-05 | 北京大学 | Y-type titanyl phthalocyanine nano-particles and preparation method and application thereof |
| CN103613598A (en) * | 2013-11-28 | 2014-03-05 | 天津大学 | Method for preparing polymorphism photosensitivity TiOPc nano particle and application thereof in organic photoconductor |
| CN108203542A (en) * | 2016-12-16 | 2018-06-26 | 中国石油化工股份有限公司 | A kind of preparation method of selective laser sintering nylon powder |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314694C (en) * | 2004-07-12 | 2007-05-09 | 天津大学 | Method for preparing micrometer Y crystalline form oxotitanium phthalocyanine |
| CN1300154C (en) * | 2004-07-12 | 2007-02-14 | 天津大学 | Process for preparing polycrystalline oxotitanium phthalocyanine in mixed crystal regulator |
-
2000
- 2000-09-14 CN CN 00124736 patent/CN1117821C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302773C (en) * | 2002-07-09 | 2007-03-07 | 成都思摩纳米技术有限公司 | Method for preparing nanometer suspension of DHA |
| CN1308775C (en) * | 2003-01-22 | 2007-04-04 | 北京大学 | Monolayer organic light receptor positive charged as well as dedicated material and preparation method |
| CN102653679A (en) * | 2011-03-04 | 2012-09-05 | 北京大学 | Y-type titanyl phthalocyanine nano-particles and preparation method and application thereof |
| WO2012119485A1 (en) * | 2011-03-04 | 2012-09-13 | 北京大学 | Y-modification titanium oxide phthalocyanine nanoparticle, and preparation method and applications thereof |
| CN102653679B (en) * | 2011-03-04 | 2014-07-02 | 北京大学 | Y-type titanyl phthalocyanine nano-particles and preparation method and application thereof |
| US9298114B2 (en) | 2011-03-04 | 2016-03-29 | Peking University | Y-type oxotitanium phthalocyanine nanoparticles, preparation, and use thereof |
| CN103613598A (en) * | 2013-11-28 | 2014-03-05 | 天津大学 | Method for preparing polymorphism photosensitivity TiOPc nano particle and application thereof in organic photoconductor |
| CN103613598B (en) * | 2013-11-28 | 2016-09-14 | 天津大学 | The preparation method of polymorphic heliosensitivity TiOPc nanoparticle and the application in organic photoconductor thereof |
| CN108203542A (en) * | 2016-12-16 | 2018-06-26 | 中国石油化工股份有限公司 | A kind of preparation method of selective laser sintering nylon powder |
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| Publication number | Publication date |
|---|---|
| CN1117821C (en) | 2003-08-13 |
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