CN113150253B - Thiopyranone-based high-molecular compound and preparation method and application thereof - Google Patents
Thiopyranone-based high-molecular compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a thiopyranone-based high-molecular compound and a preparation method and application thereof. The polymer compound provided by the inventionThe structural formula of the compound is shown as formula I: in the formula I, x is an integer of 1-16, and n is an integer of 10-20; ar is selected from any one of (a) - (c). The high molecular compound has excellent electron transmission capability, and greatly improves the compatibility and crystallization resistance of the material and film-forming resin; in addition, due to the introduction of flexible side chains in the terthiophene units, the solubility of the material in organic solvents is increased. The macromolecular compound is suitable for preparing the electropositive organic photoconductive drum of a laser printer as a macromolecular electron transmission material, effectively overcomes the defects that a micromolecular material is poor in processability and easy to precipitate from a resin film layer, and the electropositive organic photoconductive drum prepared by the macromolecular compound has excellent photoelectric property and performance retentivity.
Description
Technical Field
The invention relates to an electron transport material for an electropositive organic photoconductor drum, in particular to a Thiopyranone (TPO) -based high molecular compound and a preparation method and application thereof, belonging to the technical field of organic photoconductor drums.
Background
An Organic Photo Conductor (OPC) drum is a core component of a laser printer/xerographic printer imaging system and operates on the principle of: the OPC drum surface can be charged with a uniform charge (positive or negative) by corona charging or charging roller contact charging; when the surface of the OPC drum is irradiated by laser with proper wavelength, the charge generation material is excited to generate positive and negative charge pairs, the positive and negative charge pairs are separated under the action of an electric field, the positive charge or the negative charge is transferred to the surface of the OPC drum with the help of the charge transfer material, part of the charge is neutralized, and an electrostatic latent image is formed on the surface of the OPC drum; and finally obtaining the printed image-text through development, transfer printing and fixation. Organic photoconductor drums are classified into a positive photoconductor drum and a negative photoconductor drum according to charging properties at the time of use; according to the coating structure, the organic photoconductor drum is divided into a single-layer function composite type and a multi-layer function separation type. A multi-layer function-separated type organic photoconductor drum is generally constructed by sequentially coating a primer layer (BCL), a Charge Generation Layer (CGL), and a Charge Transport Layer (CTL) on a conductive aluminum drum base. The charge transport layer is composed of a film forming resin and a charge transport material. The charge transport material includes a hole transport material for preparing a negatively charged OPC drum and an electron transport material for preparing a positively charged OPC drum. The charge transport material and film forming resin (such as polycarbonate resin) are dissolved by a proper solvent to form a coating liquid with a certain concentration, then the coating liquid is coated on an aluminum drum base with a charge generation layer, and the coating liquid is dried to form a film, so that the charge transport layer is formed. Typically, the transport layer should form a solid solution (solid solution), i.e., the transport material is dispersed in a molecularly dispersed state in the film-forming resin matrix. However, the transport material may agglomerate, crystallize or precipitate due to factors such as solubility, compatibility with the film-forming resin, etc., resulting in a reduction or even loss of transport function, and the selection of a suitable charge transport material is critical in the preparation of a high performance OPC drum.
Thiopyranone (TPO) is the basic structure of materials with good electron transport function, and small molecule derivatives using thiopyranone as a precursor have been used in electrostatic photocopying in the last 80 th century, and the structural formula is shown in the following figures [ m.scozzafava, c.h.chen, g.a.reynolds and j.h.perlstein, u.s.4514481,1985 ]:
however, Thiopyranone (TPO) type small molecule electron transport materials have disadvantages of poor solubility, poor compatibility with matrix resins, and poor processability due to their large molecular polarity, high planar rigidity, and good symmetry. As a result, it is difficult to prepare a coating solution at a high concentration, which results in difficulty in preparing a high-performance electropositive organic photoconductor drum, and precipitation or crystallization of small TPO-like molecules of the transport layer occurs, which results in deterioration or even loss of device performance.
Disclosure of Invention
Aiming at the problems of TPO micromolecular electron transport materials in electropositive organic photoconductive drums, the invention aims to provide a thiopyranone-based high molecular compound and a preparation method and application thereof.
The invention aims to provide a high molecular compound containing TPO functional groups, which is used as an electron transport material, keeps the excellent electron transport capacity of the TPO structure, greatly improves the solubility of the material in an organic solvent and the compatibility with a film-forming resin, and has excellent electron transport performance and process handling performance; the second purpose is to provide an application of the macromolecular compound, when the macromolecular compound is used as an electron transport material to prepare an electropositive organic photoconductor drum, the macromolecular compound can effectively overcome the defects that TPO micromolecule materials are poor in processability and easy to precipitate from a resin film layer, and the electropositive organic photoconductor drum prepared by using the macromolecular compound has excellent photoelectric performance and performance retentivity.
The structural formula of the macromolecular compound provided by the invention is shown as the formula I:
in the formula I, x is an integer of 1-16, and n is an integer of 10-20; ar is selected from any one of the following (a) to (c):
in the macromolecular compounds of formula I, Ar may be
Namely, the polymer compound represented by the formula I can be specifically a polymer compound represented by the following formula I-A:
in the formula I-A, x is an integer of 1-16, and n is an integer of 10-20.
In the polymer compound represented by the formula I, x is preferably 8-14, and specifically can be 12.
The invention further provides a preparation method of the macromolecular compound shown in the formula I, which comprises the following steps: under the action of a palladium catalyst, performing Stille coupling reaction on a TPO bromo derivative shown as a formula II and a bistin reagent of a terthiophene derivative shown as a formula III in an organic solution to obtain a macromolecular compound shown as a formula I;
in the formula III, x is the same as the formula I, and Ar is the same as the formula I.
In the above preparation method, the molar ratio of the bis-tin reagent of the TPO bromo derivative represented by formula ii and the terthiophene derivative represented by formula iii may be 1: (0.5-2), specifically 1: 1.
the molar ratio of the target catalyst to the TPO brominated derivative of formula ii may be 1: (5-20), specifically 1: 10.
the palladium catalyst may be bis (acetonitrile) palladium (II) chloride, bis (triphenylphosphine) palladium dichloride or tetratriphenylphosphine palladium, preferably tetratriphenylphosphine palladium.
In the organic solution, the total molar concentration of the bistin reagent of the TPO bromo-derivative shown in the formula II and the terthiophene derivative shown in the formula III can be 0.01-0.1 mol/L, and specifically can be 0.05 mol/L; the organic solvent can be toluene, acetonitrile or dioxane;
the temperature of the Stille coupling reaction can be 85-110 ℃, and specifically can be 100 ℃; the time period may be 24 to 86 hours, specifically 72 hours.
The invention provides application of a high molecular compound shown as a formula I in preparation of an electropositive organic photoconductor drum as a high molecular electron transport material.
The invention provides an electropositive organic photoconductor drum which takes a macromolecular compound shown as a formula I as an electron transmission material.
The organic photoelectric drum comprises an anode conductive aluminum drum base, a charge generation layer coated on the anode conductive aluminum drum base and a charge transmission layer coated on the charge generation layer;
the charge generation layer may be made of a polyvinyl butyral resin and a type Y oxytitanium phthalocyanine;
the charge transport layer can be made of a high molecular compound shown in formula I and bisphenol-Z type polycarbonate resin.
In the electropositive organic photoelectric drum, the anodic conductive aluminum drum base can be an anodic alumina tube.
In the electropositive organic photoconductor drum, the mass ratio of the polyvinyl butyral resin to the Y-type oxytitanium phthalocyanine may be 1: (1-3), specifically 1: 2.
the molecular weight of the polyvinyl butyral resin can be 30000-150000, and specifically can be 40000-70000. The thickness of the charge generation layer may be 0.1 to 0.6 μm, and specifically may be 0.5 μm.
The mass ratio of the high molecular compound represented by the formula I to the bisphenol-Z type polycarbonate resin may be 1: (1-10), specifically 1: (1-2) and 1: 1 or 1: 2;
the bisphenol-Z polycarbonate resin may have a molecular weight of 20000 to 90000, and more specifically 30000.
The thickness of the charge transport layer may be 18 to 26 μm, and specifically may be 20 μm.
The invention also provides a preparation method of the electropositive organic photoelectric drum, which comprises the following steps:
(1) uniformly mixing the polyvinyl butyral resin, the Y-type oxytitanium phthalocyanine and the organic solvent I to obtain a coating liquid I; coating the coating liquid I on the anode conductive aluminum drum base, and drying to form the charge generation layer;
(2) uniformly mixing the high molecular compound shown in the formula I, the bisphenol-Z type polycarbonate resin and an organic solvent II to obtain a coating liquid II; and coating a coating liquid II on the charge generation layer, and drying to form the charge transmission layer, thereby obtaining the electropositive organic photoconductor drum.
In the above production method, the mass ratio of the sum of the mass of the polyvinyl butyral resin and the Y-type oxytitanium phthalocyanine to the coating liquid i may be (1 to 5): 100, specifically 3: 100, respectively;
the organic solvent I can be butanone or cyclohexanone;
the mass ratio of the sum of the mass of the high molecular compound represented by the formula I and the bisphenol-Z type polycarbonate resin to the coating liquid II can be (0.1-0.5): 1, specifically, it may be 0.15: 1;
the organic solvent II can be dioxane or dichloromethane.
The invention also provides a laser printer or an electrostatic copier, wherein the organic photoelectric drum is the positive-electricity organic photoelectric drum, and the protection scope of the invention is also provided.
The invention has the following beneficial effects:
(1) in the high molecular compound, a thiopyranone unit is a good electron withdrawing group (Acceptor), a trithiophene unit is a classical electron donating group (Donor), and D-A alternating curled conjugated polymer is formed by polymerization, so that an effective electron migration channel is formed, the high molecular compound has excellent electron transport capacity, and the compatibility and crystallization resistance of the material and film-forming resin are greatly improved; in addition, due to the introduction of flexible side chains in the terthiophene units, the solubility of the material in organic solvents is increased. Moreover, the macromolecular electronic compound is prepared by adopting a conventional organic synthesis method, and is simple and convenient to operate.
(2) The polymer compound is suitable for preparing an electropositive organic photoconductor drum of a laser printer as a polymer electron transmission material, effectively overcomes the defects that a small molecular material is poor in processability and easy to precipitate from a resin film layer, and the electropositive organic photoconductor drum prepared by using the polymer compound has excellent photoelectric property and property retentivity.
Drawings
FIG. 1 is a synthetic scheme of TPO-TTP12 in an example embodiment of this invention.
Detailed Description
The structural formula of the macromolecular compound provided by the invention is shown as a formula I,
in the formula I, x is an integer of 1-16, and n is an integer of 10-20; ar is selected from any one of the following (a) - (c):
in the high molecular compound shown in the formula I, a thiopyranone unit is a good electron withdrawing group (Acceptor), a trithiophene unit is a classical electron donating group (Donor), and D-A alternating curled conjugated high molecules are formed through polymerization, so that an effective electron migration channel is formed, the high molecular compound has excellent electron transmission capacity, and the compatibility and crystallization resistance of the high molecular compound and film-forming resin are greatly improved; in addition, due to the introduction of a flexible side chain into the terthiophene unit, the solubility of the material in an organic solvent is increased; the electropositive organic photoconductor drum can be used as a high molecular electron transmission material to prepare an electropositive organic photoconductor drum, the defects that a small molecular material is poor in processability and is easy to precipitate from a resin film layer are effectively overcome, and the electropositive organic photoconductor drum prepared by using the electropositive organic photoconductor drum has excellent photoelectric property and performance retentivity.
The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public perspective unless otherwise specified. The following are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
As shown in FIG. 1, the synthesis of TPO-TTP12 is used as a specific example to illustrate the preparation process of the novel polymer electron transport material of the present invention:
in this synthetic scheme, the synthesis of TPO fragments is performed with reference to the references [ N.G.rule, M.R.Detty, J.E.Kading and J.A.Sinicropi, J.Org.chem.,1995,60, 1665-containing 1673 ], including Compound 1, Compound 2, Compound 3 and Compound 4.
Synthesis of Compound 1: A1L three-necked flask containing 270 ml of ethanol was placed in an ice bath to be cooled. Subsequently, 4-bromobenzaldehyde (75 g, 0.41 mol) and acetone (9.67 g, 0.17 mol) were added. 374 ml of 10% sodium hydroxide solution was added dropwise with stirring. After the addition was complete, the ice bath was removed and stirred overnight. A large amount of yellow solid appeared in the flask, and the solid was collected by filtration, then washed with 400 ml of dichloromethane, filtered again, and collected to obtain 45.8 g of yellow crystals (yield 68.7%), which was compound 1. The melting point is 216.8-218.3 ℃; 1 H NMR(400MHz,CDCl 3 ):δ7.66(d,J＝15.88Hz,2H),7.55(AA′BB′,J＝8.16Hz,4H),7.47(AA′BB′,J＝8.12Hz,4H),7.04(d,J＝15.88Hz,2H)； 13 C NMR(100MHz,CDCl 3 ):δ186.37,140.19,131.74,130.33,127.81,123.89,122.96；HRMS(EI)C 17 H 12 Br 2 O[M] + theoretical 391.9234, measured 391.9231.
Synthesis of Compound 2: the prepared compound 1(11.76 g, 0.03 mol) was dissolved in a mixed solution of 120 ml of tetrahydrofuran and 60 ml of ethanol, and stirred; then, a solution of sodium bicarbonate (10.08 g, 0.12 mol) in 40 ml of water and a solution of sodium hydrosulfide (36 g, 0.63 mol) in 120 ml of water were added to the solution of compound 1, respectively. Stirring for two hours at normal temperature, adding 200 ml of water to dilute the reaction solution, extracting with dichloromethane, collecting an organic phase, separating by column chromatography to obtain a small amount of cis-isomer and trans-isomer of the pure compound 2, wherein the cis-isomer and the trans-isomer are white solids, and the rest is continuously used in the next step without separation. Compound 2 cis isomer: the melting point is 104.2-105.3 ℃; 1 H NMR(400MHz,CD 2 Cl 2 ):δ7.47(AA′BB′,J＝8.5Hz,4H),7.24(AA′BB′,J＝8.4Hz,4H),4.31(dd,J 1 ＝8.4Hz,J 2 ＝4.4Hz,2H),3.10(dd,J 1 ＝15.2Hz,J 2 ＝8.4Hz,2H),2.99(dd,J 1 ＝14.8Hz,J 2 ＝4.4Hz)； 13 C NMR(100MHz,CD 2 Cl 2 ):δ207.19,139.56,131.75,129.28,121.45,48.15,43.43；HRMS(EI)C 17 H 14 Br 2 OS[M] + theoretical 425.9112, measured 425.9108 compound 2 trans isomer: the melting point is 158.2-159.9 ℃; 1 H NMR(400MHz,CD 2 Cl 2 ):δ7.47(AA′BB′,J＝8.4Hz,4H),7.24(AA′BB′,J＝8.4Hz,4H),4.31(dd,J 1 ＝12.4Hz,J 2 ＝3.2Hz,2H),2.97(t,J＝13.2Hz,2H),2.88(dd,J 1 ＝13.2Hz,J 2 ＝3.2Hz)； 13 C NMR(100MHz,CD 2 Cl 2 ):δ206.37,138.61,132.00,129.00,121.85,47.76；HRMS(EI)C 17 H 14 Br 2 OS[M] + theoretical value 425.9112, measured value 425.9123.
Synthesis of Compound 3: compound 2(14 g, 0.03 mol) was dissolved in 80 ml of dichloromethane, and m-chloroperoxybenzoic acid (20.64, 0.12 mol) was added in portions over about 30 minutes, followed by reaction at room temperature for 1 hour after completion of the addition. After the reaction is finished, the mixture is quenched by dilute sodium hydroxide solution, extracted by saturated saline solution, and an organic phase is collected to obtain an isomer mixture of 18.5 g of the compound, a small amount of the isomer mixture is separated by column chromatography for structural identification, and the rest is directly used for the next reaction. Compound 3 cis isomer: the melting point is 221.7-224.9 ℃; 1 H NMR(400MHz,CDCl 3 ):δ7.56(AA′BB′,J＝8.4Hz,4H),7.26(AA′BB′,J＝8.4Hz,4H),4.45(dd,J 1 ＝8.4Hz,J 2 ＝5.1Hz,2H),3.48(dd,J 1 ＝15.6Hz,J 2 ＝8.4Hz,2H),3.36(dd,J 1 ＝15.8Hz,J 2 ＝5.0Hz)； 13 C NMR(100MHz,CDCl 3 )δ202.80,132.37,130.97,128.94,124.37,61.01,44.43；MS(EI)[M-SO 2 ] + compound 3 trans isomer: the melting point is 286.6-288.5 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.57(AA′BB′,J＝8.4Hz,4H),7.31(AA′BB′,J＝8.4Hz,4H),4.50(dd,J 1 ＝14.0Hz,J 2 ＝2.8Hz,2H),3.68(t,J＝14.4Hz,2H),2.96(dd,2H)； 13 C NMR(100MHz,CDCl 3 )δ201.05,132.37,131.05,127.18,124.55,64.13,45.56；MS(EI)[M-SO 2 ] + ＝392。
synthesis of Compound 4: compound 3(20 g, 43.7 mmol) was dissolved in 60 ml of dimethyl sulfoxide. Under magnetic stirring, 8 g of iodine and 1 ml of concentrated sulfuric acid are respectively added, heated to 100 ℃ and reacted for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, diluted with 200 ml of water, and then extracted with 100 ml of dichloromethane. The organic phase was collected and dried over anhydrous sodium sulfate. The product was isolated by column chromatography to give 18.3 g of an orange-red solid, compound 4 (92% yield). The melting point is 196.3-196.9 ℃; 1 HNMR(300MHz,CDCl 3 )δ7.58-7.78(m,8H),6.68(s,2H)； 13 C NMR(75MHz,CDCl 3 )δ178.86,152.56,132.67,130.31,127.41,127.29,127.11；HRMS(EI)C 17 H 10 Br 2 O 3 S[M] + theoretical value 453.8697, measured value 453.8690.
In the present synthesis scheme, the synthesis of TTP12 fragments is performed with reference to [ e.v. lukovskaya, a.a.kosmacheva, o.a.fedorova, a.a.bobyleva, a.v. dolganov, n.e.shepel, yu.v. fedorov, v.v. novikov and a.v. anisimov, russ.j.org.chem.,2014,50,552-558 ], including compound 5, compound 6, compound 7.
Synthesis of Compound 5: 2, 5-dibutylthiophene (13.2 g, 20.0 mmol), 2-bromo-3-dodecylthiophene (16.6 g, 50.0 mmol), palladium tetratriphenylphosphine (230 mg, 0.20 mmol), and 50 ml of anhydrous toluene were sequentially added to a 250 ml three-necked flask under nitrogen. The reaction was heated to 100 ℃ and stirred for 24 hours. After the reaction was completed, it was cooled to room temperature, filtered, and the filtrate was collected. The filtrate was spin-dried and the product was isolated by column chromatography to give compound 5(7.5 g, 64% yield). 1 HNMR(400MHz,CDCl 3 ):δ7.18(d,J＝5.20Hz,2H),7.06(s,2H),6.95(d,J＝5.2Hz,2H),2.80(t,J＝7.6Hz,4H),1.71-1.60(m,4H),1.43-1.20(m,36H),0.90(t,J＝6.8Hz,6H).
Synthesis of Compound 6: compound 5(1.60 g, 2.74 mmol) was dissolved in 30 ml of a chloroform/acetic acid (1/1 vol.) mixed solvent under exclusion of light, and N-bromosuccinimide (0.98 g, 5.48 mmol) was added slowly in portions, and after the addition, the reaction chamber was filled with the solutionThe reaction was warmed for 12 hours. The reaction was quenched with 100 ml of water, extracted with chloroform, and the organic phase was collected and the product was isolated by column chromatography to give 1.98 g of an oil, compound 6 (98% yield). 1 H NMR(400MHz,CDCl 3 ):δ6.94(s,2H),6.86(s,2H),2.68(t,J＝8.0Hz,4H),1.65-1.50(m,4H),1.38-1.19(m,4H),0.87(t,J＝7.2Hz,6H)。
Synthesis of compound 7: compound 6(1.48 g, 2.0 mmol) was dissolved in 60 ml of dry tetrahydrofuran under nitrogen and stirred. The temperature was lowered to-78 ℃, n-butyllithium (2.4 ml, 6.0 mmol) was slowly added dropwise at a concentration of 2.5 mol per liter, and tributyltin chloride (1.62 ml, 6.0 mmol) was added dropwise after stirring for 30 minutes while maintaining the temperature. After the addition was complete, the mixture was stirred at-78 ℃ for 30 minutes, then allowed to warm to room temperature and stirred for 1 hour. After the reaction is finished, 10 ml of saturated potassium fluoride solution is added for quenching, extraction is carried out by ethyl acetate, an organic phase is collected, anhydrous sodium sulfate is dried, and after rotary drying, 2.5 g of oily matter is obtained, namely the compound 7. 1 HNMR(400MHz,CDCl 3 ):δ7.04(s,2H),6.96(s,2H),2.81(t,J＝7.6Hz,4H),1.72-1.65(m,4H),1.48-1.20(m,24H),0.76(t,J＝7.6Hz,18H)。
Reference to the synthesis of TPO-TTP12 [ w. -q.qu, c. -y.gao, p. -x.zhang, x. -h.fan and l. -m.yang, RSC adv.,2021,11, 8664-: compound 7(290.8 mg, 0.25 mmol), compound 4(113.5 mg, 0.25 mmol), tetrakistriphenylphosphine palladium (28.9 mg, 0.025 mmol), and 10 ml of dry toluene were added sequentially in a 25 ml three-necked flask under nitrogen. The reaction was heated to 100 ℃ and stirred for 72 hours. After the reaction was complete, the reaction solution was cooled to room temperature and slowly poured into 100 ml of methanol, and a solid precipitated. After stirring for an additional 2 hours the solid was collected by filtration and then purified using a soxhlet extractor. The elution solvent is methanol, n-hexane and chloroform in turn. And finally, concentrating the collected chloroform solution, pouring into 100 ml of methanol again to precipitate a solid, and filtering and collecting to obtain a black red solid, namely TPO-TTP 12. Molecular weight measurement by GPC: mn 5.17kg mol -1 ,PDI:4.43； 1 H NMR(400MHz,CD 2 Cl 2 ):δ7.88(d,J＝7.2Hz,4H),7.74(d,J＝7.2Hz,4H),7.34(s,2H),7.25-6.93(m,2H),6.76(s,2H),2.95-2.56(m,4H),1.80-1.65(m,4H),1.50-0.98(m,36H),0.95-0.65(m,6H)；IR(KBr,cm -1 ):2923,2851,1600,1643,1571,1546,1308,1197,1129,829。
And (3) testing electrical properties: the electropositive organic photoconductor drums prepared in examples and comparative examples were respectively tested using a PDT-2000 LTM electrical property tester (manufactured by QEA corporation, usa); and (3) testing conditions are as follows: the temperature is 20-25 ℃, and the relative humidity RH% is 30-40; by testing the resulting charging potential (V) 0 ) Sensitivity (E) 1/2 ) Exposure potential (V) R ) And Dark Decay Rate (DDR), etc., can determine whether the electron transport material in the electropositive organic photoconductor drum can meet the requirements for photoconductor drum performance.
Method for examining whether crystallinity is precipitated in the CTL layer in the organic photoconductor drum: (1) placing the OPC drum prepared in the embodiment or the comparative example in a constant-temperature 60 ℃ oven for 6 hours, and then placing the OPC drum at room temperature for 5 days; (2) loading the OPC drum manufactured by the embodiment or the comparative example into a toner cartridge to continuously print 1000 test papers, and staying in the toner cartridge for 5 days; (3) the surface of the OPC drum manufactured in example or comparative example was lightly pressed with a finger and rubbed back and forth for 2 minutes, and then left at room temperature for 5 days. The OPC drum after the precipitation crystallinity test was taken out, the surface condition of the drum was directly observed with an optical microscope of 50 times, and then full white draft printing was performed to observe the printing defects (such as black dots, fine black lines). The absence of crystallization under all three of the above experimental conditions is defined as crystallization resistance.
The polyvinyl butyral resin in the following examples is abbreviated as PVB, is purchased from Beijing YinuoKai science and technology Limited, has a product number of A45845, and has a molecular weight of 40000-70000.
The Y-type oxytitanium phthalocyanine is abbreviated as Y-TiOPc and is purchased from Beijing YinuoKai science and technology Co., Ltd, and the product cargo number is T2272.
The bisphenol-Z type polycarbonate resin is abbreviated as PCZ and is available from Nippon Kaisha, having a product number of PCZ-300 and a molecular weight of 30000.
Example one
Adding 2 g of PVB, 4 g of Y-TiOPc, 200 ml of butanone and 200 ml of tempered glass beads (phi 2 mm-3 mm) into a 500 ml ball milling tank, and performing dispersion treatment on the mixture for 8 hours on a ball mill with the rotating speed of 180 revolutions per minute to obtain a coating liquid I; coating the coating liquid I on an anodic aluminum oxide tube (with the diameter of 24mm and the length of 240mm) in a dip-coating mode, and drying for half an hour at 80 ℃ to obtain a charge generation layer with the thickness of about 0.5 micrometer; dissolving 5 g of TPO-TTP12 and 10 g of PCZ-300 in 100 ml of dichloromethane, and uniformly mixing to obtain a coating liquid II; and coating the coating liquid II on the charge generation layer by adopting a dip coating mode, drying for 1 hour at the temperature of 80 ℃, and forming a charge transmission layer with the thickness of about 20 microns on the charge generation layer to obtain the electropositive organic photoconductor drum.
The second embodiment: everything is the same as in example one except that the amount of TPO-TTP12 was increased from 5 g to 10 g.
Comparative example one: everything is the same as in example one except that 5 g of compound 4 is used instead of 5 g of TPO-TTP 12.
Comparative example two: everything is the same as in example one except that 1 gram of compound 4 is substituted for 5 grams of TPO-TTP 12.
And (3) performance characterization: the electropositive organic photoconductor drums prepared in the first embodiment, the second embodiment, the first comparative embodiment and the second comparative embodiment are respectively subjected to electrical property test and crystallinity examination of the CTL layer in the OPC drum, and the test results are detailed in Table 1. As can be seen from the data in Table 1, compared with the TPO fragment small molecule, the compatibility or crystallization resistance of TPO-TTP12 and the film-forming resin is obviously better than that of the TPO fragment small molecule material (example one, two Vs comparative examples one and two) on the premise of ensuring the qualified photoelectric property; for TPO fragment small molecular materials, the crystallization/agglomeration resistance is poor if the qualified photoelectric properties are maintained (comparative example one), and the photoelectric properties are unqualified if the processing practicability is considered (comparative example two); the various performance and quality specifications of electropositive organic photoconductor drums prepared using TPO-TTP12 are comparable to or close to those of OEM drum (HL2240 printer original equipment drum) products (example one, two Vs OEM drums).
TABLE 1
Claims (7)
1. The application of the macromolecular compound shown in the formula I in the preparation of an electropositive organic photoconductor drum as a macromolecular electron transport material;
in the formula I, x is an integer of 1-16, and n is an integer of 10-20; ar is selected from any one of the following (a) to (c):
2. an electropositive organic photoconductor drum comprising the polymer compound described in claim 1 as an electron transport material.
3. The electropositive organic photoconductor drum of claim 2, wherein: the charge transfer coating comprises an anode conductive aluminum drum base, a charge generation layer coated on the anode conductive aluminum drum base and a charge transfer layer coated on the charge generation layer;
the charge generation layer is made of polyvinyl butyral resin and Y-type oxytitanium phthalocyanine;
the charge transport layer is made of the polymer compound and bisphenol-Z type polycarbonate resin.
4. The electropositive organic photoconductor drum of claim 3, wherein: the mass ratio of the polyvinyl butyral resin to the Y-type oxytitanium phthalocyanine is 1: (1-3);
the molecular weight of the polyvinyl butyral resin is 30000-150000;
the thickness of the charge generation layer is 0.1-0.6 μm;
the mass ratio of the high molecular compound shown as the formula I to the bisphenol-Z type polycarbonate resin is 1: (1-10);
the molecular weight of the bisphenol-Z type polycarbonate resin is 20000-90000;
the thickness of the charge transport layer is 18-26 μm.
5. The method of making the electropositive organic photoconductor drum of any of claims 3-4, comprising the steps of:
(1) uniformly mixing the polyvinyl butyral resin, the Y-type oxytitanium phthalocyanine and the organic solvent I to obtain a coating liquid I; coating the coating liquid I on the anode conductive aluminum drum base, and drying to form the charge generation layer;
(2) uniformly mixing the high molecular compound shown in the formula I, the bisphenol-Z type polycarbonate resin and an organic solvent II to obtain a coating liquid II; and coating a coating liquid II on the charge generation layer, and drying to form the charge transmission layer, thereby obtaining the electropositive organic photoconductor drum.
6. The method of claim 5, wherein: the mass ratio of the mass sum of the polyvinyl butyral resin and the Y-type oxytitanium phthalocyanine to the coating liquid I is (1-5): 100, respectively;
the organic solvent I is butanone or cyclohexanone;
the mass ratio of the sum of the mass of the high molecular compound represented by the formula I and the bisphenol-Z type polycarbonate resin to the coating liquid II is (0.1-0.5): 1;
the organic solvent II is dioxane or dichloromethane.
7. A laser printer or xerographic printer having an organic photoconductor drum according to any one of claims 2 to 4.
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