CN116414012A - Electropositive polymer charge control agent and preparation method and application thereof - Google Patents
Electropositive polymer charge control agent and preparation method and application thereof Download PDFInfo
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- CN116414012A CN116414012A CN202111657641.0A CN202111657641A CN116414012A CN 116414012 A CN116414012 A CN 116414012A CN 202111657641 A CN202111657641 A CN 202111657641A CN 116414012 A CN116414012 A CN 116414012A
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- 229960001860 salicylate Drugs 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000005455 trithianyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0802—Preparation methods
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a electropositive polymer charge control agent P3-CCR shown in a formula I, and preparation and application thereof. The P3-CCR polymer charge control agent has the advantages of high electrification rate, high charge capacity and good electric quantity retention, the performance of the P3-CCR polymer charge control agent is no worse than that of the current commercial standard electropositive charge control agent dimethyl ditetradecyl molybdate salt, the performance requirement of high-speed printing carbon powder is completely met, and meanwhile, the P3-CCR polymer charge control agent is colorless or nearly colorless solid, and also meets the preparation requirement of color carbon powder.
Description
Technical Field
The present invention is in the field of electrophotographic technology (Electrophotography). In particular, the invention relates to charge control agent materials (Charge control agent, CCA) used in the preparation of developer carbon powders for laser printing and xerography. More particularly, the invention relates to an electropositive polymer charge control agent (Charge control resin, CCR) taking pyridine tetrafluoroborate as a structural characteristic, a preparation method and application thereof.
Background
Carbon powder (Toner, also known as Toner, toner) is a developer for laser printers/xerographic machines based on the principle of electrophotography, an important and largest consumable. The carbon powder mainly comprises Resin (Resin), pigment (Pigment), wax (Wax), charge Control Agent (CCA) and the like. The carbon powder is a fine powder composite material, which is obtained by the steps of mixing the components according to the formula proportion, then mixing, crushing, grading and the like (conventional physical method). Wherein the polymer resin is a main body and plays a role of a connecting material; pigments are the source of visibility and color; the wax is a release agent, so that the problem of adhesion to a fixing roller during fixing can be solved; the charge control agent is the most important component for imparting the charge characteristic to the carbon powder, and determines the charge polarity, the charge rate, the charge quantity, the charge distribution uniformity, the charge stability and the like.
The development process of printing/copying is based on the principle of electrostatics, and the electrical characteristics of carbon powder strongly influence the performance and print quality. Triboelectrification is a main factor of electrification of carbon powder, and the use of a charge control agent can determine charge polarity, adjust electrification rate, maintain enough and stable charge quantity and fully improve the triboelectrification characteristic of the carbon powder. So to speak, the carbon powder is carbon powder because of the CCA.
Charge control agents fall into two categories, electronegative and electropositive. Among the most widely used charge control agents at present are Azo dye metal complexes (e.g., azo-ir complex T-77), metal salicylates (e.g., zincsallite), and the like. Examples of the electropositive substance include Nigrosine (Nigrosine), azine dyes (Azine dyes), and aliphatic quaternary ammonium salts (for example, quaternary ammonium Salt TP-415).
However, these charge control agents currently in common use also present several problems that require improvement or are to be addressed. For example, nigrosine, metal complexes, and the like are poor in compatibility and dispersibility because both physical (i.e., melt pulverization) and chemical (i.e., suspension polymerization, aggregation-fusion, and the like) methods in carbon powder production require CCA to be uniformly and stably dispersed in a binder resin in the form of nano-sized particles to obtain a high-performance carbon powder product; the binding force between the salicylate of the small organic molecule, aliphatic quaternary ammonium salt and the like and the surface of the carbon powder particles is usually not strong enough, and the small organic molecule is easy to fall off in the printing (especially high-speed printing) process, so that the defects of carbon powder performance reduction and printing quality deterioration are caused; in addition, such as nigrosine, dye metal complex, etc. are themselves extremely dark colored and are not suitable for the preparation of colored carbon powder. Therefore, there is still great room for improvement and improvement in charge control materials for printing/copying toner.
Disclosure of Invention
The invention aims to provide a class of electropositive polymer charge regulators which are used for preparing developer carbon powder for laser printing and electrostatic copying.
The invention firstly provides a functional polymer compound P3-CCR containing pyridine tetrafluoroborate shown in a formula I:
in formula I, R is selected from hydrogen atom, C 1-20 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclyl, C 6-20 Aryl or 5-20 membered heteroaryl; the C is 6-10 Aryl or 5-20 membered heteroaryl optionally substituted with C 1-20 Alkyl, C 3-20 Cycloalkyl substitution;
when R is not H, m is the number of substituent R, and is an integer selected from 1-5;
n is a number of 10 to 100.
According to embodiments of the invention, R is a substituent other than a hydrogen atom, and when m is 1 or 2, R may be ortho, meta or para to the pyridine structural unit.
According to an embodiment of the invention, R is selected from the group consisting of a hydrogen atom, C 1-6 Alkyl, C 6-12 Aryl or 5-12 membered heteroaryl;
n is a number of 30 to 50.
According to a preferred embodiment of the invention, R is selected from any one of the following: H. 4-methyl, 3-phenyl or [3,2-b ] benzo; n is a number of 35 to 45.
In one embodiment, the functional polymeric compound comprising a pyridinium tetrafluoroborate salt of formula I is P3-CCR-H, wherein n is about 40:
the invention also provides a preparation method of the functional polymer compound P3-CCR containing the tetrafluoroborate pyridine salt shown in the formula I, which comprises the following steps:
wherein X in the compounds I-1 and I-3 are defined as the same and are selected from leaving group halogen; the other groups have the same definition as in formula I above;
s1, carrying out nucleophilic substitution reaction on a compound I-1 and a compound I-2 to obtain a compound I-3;
s2, carrying out anion exchange reaction on the compound I-3 and sodium fluoborate to obtain a compound I-4;
s3, carrying out free radical polymerization reaction on the compound I-4 to obtain a high molecular compound P3-CCR shown in the formula I.
According to an embodiment of the present invention, the catalyst used in the radical polymerization in step S3 is selected from Ammonium Persulfate (APS).
According to an embodiment of the invention, the free radical polymerization in step S3 is carried out in the presence of dodecyl mercaptan and cetyl trimethylammonium bromide (CTAB).
The invention also provides application of the functional polymer compound P3-CCR containing the pyridine tetrafluoroborate shown in the formula I as an electropositive polymer charge control agent (CCR).
Specifically, the functional polymer compound P3-CCR containing the pyridine tetrafluoroborate shown in the formula I is used as a positive charge control agent (P-type CCR) to be applied to the preparation of developer carbon powder for laser printing and electrostatic copying.
The invention also provides an electropositive carbon powder comprising: a binder resin, a pigment, a wax, a polymer compound P3-CCR containing a pyridinium tetrafluoroborate as shown in formula I above, as a charge control agent, and optionally, an external additive to adjust fluidity.
According to an embodiment of the present invention, the binder resin may be a styrene-acrylate copolymer resin, a polyester, or a polycarbonate;
according to an embodiment of the present invention, the pigment may be carbon black, phthalocyanine pigment, pigment red, pigment yellow, or the like.
According to an embodiment of the present invention, the wax includes natural waxes (paraffin wax, palm wax, spermatid wax, etc.) and synthetic waxes (polyethylene wax, polypropylene wax, etc.).
According to a preferred embodiment of the present invention, the charge control agent is a functional polymer compound P3-CCR-H containing a pyridine tetrafluoroborate salt represented by the above formula I.
According to an embodiment of the present invention, the external fluidity-adjusting additive is selected from silica powder, titanium pigment, and the like.
According to the embodiment of the invention, the weight part ratio of the binder resin, the pigment, the wax and the tetrafluoroborate-containing pyridine salt shown in the formula I is (80-120): (5-15): (5-15): (1 to 20), preferably (90 to 110): (8-12): (8-12): (4-12).
The invention also provides a preparation method of the electropositive carbon powder, which adopts the traditional physical method for preparation and comprises the following steps: (1) melt kneading: adding raw material binder resin, pigment, wax and a high molecular compound P3-CCR containing pyridine tetrafluoroborate shown in the formula I into a mixing mill according to a formula, and carrying out high-temperature melting, stirring, extrusion and mixing uniformly; (2) crushing: cooling and tabletting the mixed materials, and mechanically crushing the tablets to coarse particles with the particle size of 0.5-3 mm; (3) fine crushing and grading collection: feeding the coarse particles into an air flow pulverizer and a superfine pulverizing and classifying system, and collecting a raw powder sample with the particle size of 5-20 mu m (D50); optionally, (4) final mixing: adding external additive for regulating fluidity to obtain the final product.
According to an embodiment of the present invention, in the step (1), the kneading temperature is 120 to 170 ℃, the extrusion rate is 4 to 10kg/h, and the kneading time is 1 to 5 hours.
According to an embodiment of the present invention, in step (3), the jet mill has a pressure of 0.5 to 1MPa and a frequency of 20 to 50Hz.
According to an embodiment of the present invention, in the step (3), the rotation speed of the ultrafine grinding classification system is 10000-15000rpm, and the air volume is 50-100m 3 /h。
Advantageous effects
The raw powder sample can adopt a q/m method (charge-mass ratio stripping method) to measure the electrical characteristic parameters. Through the two parameters of the electrification time and the electrification amount, the electrification polarity, electrification rate, electrification amount, electrification stability and other performances of the sample can be analyzed, and further the quality of the charge control agent can be evaluated and judged.
The test result shows that the P3-CCR polymer charge control agent has the advantages of high electrification rate, high charge capacity and good electric quantity retention, the performance of the P3-CCR polymer charge control agent is no worse than that of the current commercial standard electropositive charge control agent dimethyl ditetradecyl molybdate salt, the performance requirement of high-speed printing carbon powder is completely met, and meanwhile, the polymer charge control agent P3-CCR is colorless or nearly colorless solid, and also meets the preparation requirement of color carbon powder.
In addition, the structure of the P3-CCR polymer charge control agent has good compatibility with polymer binder resin and has a certain application prospect.
Drawings
FIG. 1 is a synthetic scheme for the preparation of polymeric charge control agent P3-CCR-H in example 1.
Definition and description of terms
Unless otherwise indicated, the radical and term definitions recited in the specification and claims of this application, including as examples, exemplary definitions, preferred definitions, definitions recited in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. Such combinations and combined group definitions and structures of compounds should fall within the scope of the description herein.
Numerical ranges recited in the specification and claims herein, when the numerical range is defined as an "integer," it is understood that both endpoints of the range and each integer within the range are recited. For example, an "integer of 1 to 5" should be understood to describe each integer of 1,2, 3,4, and 5.
When a range of values is defined as a "number," it is to be understood that both endpoints of the range, each integer within the range, and each fraction within the range are delineated. For example, a "number of 10 to 100" should be understood to describe not only each integer of 10, 11, 12, 13, 14, 15 … … and 100, but also at least the sum of each integer with 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively. Other numerical ranges are defined as "30 to 50 numbers" and "35 to 45 numbers".
The term "C 1-20 Alkyl "is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having 1 to 20 carbon atoms, preferably C 1-10 An alkyl group. "C 1-10 Alkyl "is understood to mean preferably a straight-chain or branched saturated monovalent hydrocarbon radical having 1,2, 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. The alkyl is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl,1, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 2-dimethylbutyl, etc., or isomers thereof. In particular, the radicals have 1,2, 3,4, 5,6, carbon atoms ("C 1-6 Alkyl "), such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly said groups having 1,2 or 3 carbon atoms (" C 1-3 Alkyl "), such as methyl, ethyl, n-propyl or isopropyl.
The term "C 3-20 Cycloalkyl "is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably" C 3-10 Cycloalkyl groups). The term "C 3-10 Cycloalkyl "is understood to mean a saturated monovalent mono-or bicyclic hydrocarbon ring having 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. The C is 3-10 Cycloalkyl may be a monocyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as a decalin ring.
The term "3-20 membered heterocyclyl" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1 to 5 heteroatoms independently selected from N, O and S, preferably a "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1 to 5, preferably 1 to 3 heteroatoms selected from N, O and S. The heterocyclic group may be attached to the remainder of the molecule through any of the carbon atoms or a nitrogen atom, if present. In particular, the heterocyclic groups may include, but are not limited to: 4-membered rings such as azetidinyl, oxetanyl; a 5-membered ring such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6 membered ring such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or a 7-membered ring such as diazepanyl. Optionally, the heterocyclyl may be benzo-fused. The heterocyclyl may be bicyclic, such as, but not limited to, a 5,5 membered ring, such as hexahydrocyclopenta [ c ] pyrrol-2 (1H) -yl ring, or a 5,6 membered bicyclic ring, such as hexahydropyrrolo [1,2-a ] pyrazin-2 (1H) -yl ring. The nitrogen atom-containing ring may be partially unsaturated, i.e., it may contain one or more double bonds, such as, but not limited to, 2, 5-dihydro-1H-pyrrolyl, 4H- [1,3,4] thiadiazinyl, 4, 5-dihydro-oxazolyl, or 4H- [1,4] thiazinyl, or it may be benzo-fused, such as, but not limited to, dihydroisoquinolinyl. According to the invention, the heterocyclic group is non-aromatic.
The term "C 6-20 Aryl "is understood to mean a mono-, bi-or tricyclic hydrocarbon ring, preferably" C ", of monovalent aromatic or partly aromatic nature having 6 to 20 carbon atoms 6-14 Aryl group). The term "C 6-14 Aryl "is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring (" C ") having a monovalent aromatic or partially aromatic character of 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms 6-14 Aryl), in particular a ring having 6 carbon atoms ("C) 6 Aryl "), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 Aryl "), e.g. indanyl or indenyl, or a ring having 10 carbon atoms (" C 10 Aryl "), such as tetralin, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms (" C " 13 Aryl "), e.g. fluorenyl, or a ring having 14 carbon atoms (" C) 14 Aryl "), such as anthracenyl.
The term "5-20 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: it has 5,6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and it contains 1 to 5, preferably 1 to 3 heteroatoms each independently selected from N, O and S and, in addition, can be benzo-fused in each case. In particular, the heteroaryl group is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazole, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and their benzo derivatives, such as quinolinyl, quinazolinyl, isoquinolinyl, and the like; or an axcinyl group, an indolizinyl group, a purinyl group, etc., and their benzo derivatives; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
Unless otherwise indicated, heterocyclyl, heteroaryl or heteroarylene include all possible isomeric forms thereof, e.g. positional isomers thereof. Thus, for some illustrative, non-limiting examples, pyridinyl or pyridylene include pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, and pyridin-4-yl; thienyl.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
The synthetic route of the polymer charge control agent P3-CCR-H is shown in figure 1, and mainly comprises the following steps: pyridine and 4-vinylbenzyl chloride are used as starting materials, intermediate compound 1 is obtained through nucleophilic substitution reaction, intermediate compound 2 is obtained through anion exchange reaction, and the target product can be obtained through free radical polymerization reaction of intermediate compound 2.
Synthesis of 4-vinylbenzyl pyridine chloride (Compound 1): pyridine (101.4 mL,0.72 mol) and 4-vinylbenzyl chloride (57.6 mL,0.72 mol) were added separately to a 1 liter single neck round bottom flask containing 450mL acetonitrile; reactionThe mixture was stirred overnight (about 18 h) at 50 ℃. After cooling the reaction mixture, about 400mL of diethyl ether was added under stirring, and a large amount of pale yellow solid was precipitated; vacuum filtration, washing with diethyl ether until the filtrate is colorless, and vacuum drying the filter cake at room temperature to give 165g pale yellow solid powder (yield 99%). Mp 65 ℃; 1 H NMR(400MHz,D 2 o, ppm): δ8.88 (d, j=5.6 hz, 2H), 8.54 (t, j=7.6 hz, 1H), 8.05 (t, j=6.4 hz, 2H), 7.32-7.52 (m, 4H): 6.65-6.78 (m, 1H), 5.84 (d, j=17.6 hz, 1H), 5.76 (s, 2H), 5.35 (d, j=11.2 hz, 1H): elemental analysis: measurement values C-72.09, H-6.23, N-6.10, cl-14.86; theoretical value C-72.57, H-6.09, N-6.04, cl-15.30.
Synthesis of 4-vinylbenzyl pyridine tetrafluoroborate (Compound 2): compound 1 (82.2 g,0.36 mol) and sodium fluoroborate (42.0 g,0.42 mol) were each added to a 500mL single neck round bottom flask followed by 360mL acetone dried over anhydrous sodium sulfate and stirred at room temperature for 2 days. The solid was filtered under reduced pressure and washed with acetone several times. Removing most of the acetone by rotary evaporation under reduced pressure at room temperature, then flushing about 300mL of diethyl ether under stirring, and gradually solidifying the oily matter into solid powder; suction filtration under reduced pressure and washing with diethyl ether until the filtrate was colorless gave 102g of an off-white solid powder (yield 100%). The melting point of the product is 35-40 ℃. 1 H NMR(400MHz,D 2 O, ppm): δ8.88 (d, j=6.0 hz, 2H), 8.54 (t, j=8.0 hz, 1H), 8.05 (t, j=6.8 hz, 2H), 7.35-7.55 (m, 4H), 6.72-6.85 (m, 1H), 5.88 (d, j=17.6 hz, 1H), 5.78 (s, 2H), 5.37 (d, j=11.2 hz, 1H): elemental analysis: measurement values C-59.00, H-5.42, N-4.37; theoretical C-59.40, H-4.99, N-4.95.
Synthesis of Polymer P3-CCR-H: in a 500mL three-necked flask equipped with a mechanical stirrer and a thermometer, 25g of intermediate compound 2 and 300mL of toluene solvent were placed, and heated to 30℃under stirring to promote dissolution; dodecyl mercaptan (0.6 g) was added to the three-necked flask with stirring, and stirring was continued for 5 minutes; then, after Cetyl Trimethyl Ammonium Bromide (CTAB) (2 g) was added, the temperature was gradually increased until the reaction system temperature reached 95 ℃; a solution of the initiator Ammonium Persulfate (APS) (0.12 g) and sodium bicarbonate (0.1 g) in 25mL of deionized water was added dropwise to the reaction mixture; stirring and heating for 1h, and then continuously dropwise adding the rest initiator; completion of the drippingAfter that, the reaction was continued to stir at 95℃overnight. Slowly pouring the reaction mixture into 5L of methanol while the reaction mixture is hot under mechanical stirring to precipitate a polymerization product; vacuum filtering, and washing filter cake with deionized water and methanol for several times; air-dried naturally to obtain 19.5g (yield 81%) of the target product as a nearly colorless solid powder. 1 H NMR(400MHz,CDCl 3 ,ppm):δ6.82-7.20(shoulder,19H)；6.40-6.80(shoulder,10H)；1.70-2.03(br.s,5H)；1.30-1.70(br.s,10H).IR(KBr.cm -1 ) 3059,3024,2925,2850,1604,1540,1494,1447,1028,755,702.Tg 70 ℃; tf 129 ℃ (20 Kg weighted); mw=56165 da, mn=11234, dpi=5. The number of links n is calculated to be about 40.
Example 2
In the preparation of the raw powder sample of the present invention, styrene-butyl acrylate copolymer resin (Tf 150 ℃ C.; sanyo chemical Co., ltd., japan), beta-copper phthalocyanine (Japanese steam ba Co., ltd.), polypropylene wax (Tm 120 ℃ C.; sanyo chemical Co., ltd.), and the polymer charge control agent P3-CCR-H prepared in example 1 were used as the formulation components, and were prepared according to the following procedure: (1) Adding four components into a high-speed mixer according to a certain formula (specifically 100 parts by weight of styrene-butyl acrylate copolymer resin, 10 parts by weight of beta-copper phthalocyanine, 10 parts by weight of polypropylene wax and 10 parts by weight of P3-CCR-H), uniformly stirring, melting and mixing by using a mixer (the mixing temperature is 120-170 ℃, the extrusion rate is 4-10kg/H, the mixing time is 1-5H), cooling and tabletting the compound to form tablets, and mechanically crushing the tablets to coarse particles with the particle size of 1-2 mm; (2) Pulverizing the coarse granule composite in jet mill (pressure 0.5-1MPa, frequency 20-50 Hz), and transferring into superfine pulverizing classification system (rotation speed 10000-15000rpm, air volume 50-100 m) 3 And/h) carrying out classification, and collecting classified products with the D50 of 5-12 mu m.
100 parts by weight of styrene-butyl acrylate copolymer resin, 10 parts by weight of beta-copper phthalocyanine, 10 parts by weight of polypropylene wax and 10 parts by weight of P3-CCR-H are uniformly stirred in a high-speed mixer, then are melted and mixed by a mixer, cooled and pressed into tablets, the tablets are firstly mechanically crushed into coarse particles, the coarse particles are subjected to superfine crushing by a jet mill, and finally the graded carbon powder raw powder with the D50 mu m is obtained by a grading system. The electrical characteristics of the samples are shown in Table 1.
Example 3
All were the same as in example 2 except that the amount of the charge control resin P3-CCR-H was reduced to 5 parts by weight. The electrical characteristics of the samples are shown in Table 1.
Comparative example 1
Everything is the same as in example 2 except that 10 parts by weight of dimethyl ditetradecyl molybdate (commercial reference for electropositive charge control agent, commercially available from the Nippon BaoGu Co.) was used instead of P3-CCR-H. The electrical characteristics of the samples are shown in Table 1.
The triboelectric charging performance of the raw powder sample is carried out by adopting a q/m method (namely a charge-mass ratio stripping method). The specific operation is as follows: mixing 3 parts by weight of a carbon powder sample with 97 parts by weight of a coated magnetite carrier (Japanese plasma materials Co., coating of styrene-methacrylate polymer, coating/nucleosome ratio of 10:90w/w, carrier average particle size of about 90 μm), and filling the carbon powder/carrier mixture into an activation tank (insulated metal) for rolling friction electrification; the charge-to-mass ratio value was determined using a commercial charge amount analyzer (TB-200 q/m-meter, toshiba, japan). All measurements were performed at 25 ℃ and 50% rh.
Table 1.q/m method results of measurement of charged amount (. Mu.C/g) of toner sample
The data in Table 1 show that the P3-CCR-H polymer charge control agent of the invention has the advantages of high electrification rate, high charge capacity and good electric quantity retention, the performance of the P3-CCR-H polymer charge control agent is no worse than that of the current commercial standard electropositive charge control agent dimethyl ditetradecyl molybdate salt, the performance requirement of high-speed printing carbon powder is completely met, and meanwhile, the polymer charge control agent P3-CCR of the invention is colorless or nearly colorless solid and also meets the preparation requirement of color carbon powder.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Functional polymer compound P3-CCR containing tetrafluoroborate as shown in formula I:
wherein R is selected from hydrogen atom, C 1-20 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclyl, C 6-20 Aryl or 5-20 membered heteroaryl; the C is 6-10 Aryl or 5-20 membered heteroaryl optionally substituted with C 1-20 Alkyl, C 3-20 Cycloalkyl substitution;
when R is not H, m is the number of substituent R, and is an integer selected from 1-5;
n is a number of 10 to 100.
2. The functional polymer compound P3-CCR containing pyridine tetrafluoroborate as claimed in claim 1, wherein R is selected from hydrogen atom and C 1-6 Alkyl, C 6-12 Aryl or 5-12 membered heteroaryl;
n is a number of 30 to 50.
3. The functional polymer compound P3-CCR containing a pyridinium tetrafluoroborate salt according to claim 1 or 2, wherein R is selected from any one of the following: H. 4-methyl, 3-phenyl or [3,2-b ] benzo;
n is a number of 35 to 45.
4. The pyridine tetrafluoroborate salt-containing functional polymer compound P3-CCR according to claim 3, wherein the pyridine tetrafluoroborate salt-containing functional polymer compound of formula I is P3-CCR-H, wherein n is about 40:
5. the process for producing a functional polymer compound P3-CCR containing a pyridinium tetrafluoroborate represented by the formula I as claimed in any one of claims 1 to 4, comprising the steps of:
wherein X in the compounds I-1 and I-3 are defined as the same and are selected from leaving group halogen; the other groups being as defined in any one of claims 1 to 4;
s1, carrying out nucleophilic substitution reaction on a compound I-1 and a compound I-2 to obtain a compound I-3;
s2, carrying out anion exchange reaction on the compound I-3 and sodium fluoborate to obtain a compound I-4;
s3, carrying out free radical polymerization reaction on the compound I-4 to obtain a high molecular compound P3-CCR shown in the formula I.
6. The use of a functional polymer compound P3-CCR containing a pyridinium tetrafluoroborate salt of the formula I as defined in any one of claims 1 to 4 as an electropositive polymer charge control agent.
7. The application of the polymer as claimed in claim 6, wherein the functional polymer compound P3-CCR containing the tetrafluoroborate as shown in the formula I is used as an electropositive charge control agent for preparing developer carbon powder for laser printing and electrostatic copying.
8. An electropositive carbon powder comprising: a binder resin, a pigment, a wax, a tetrafluoroborate-containing polymer compound P3-CCR of formula I as set forth in any one of claims 1 to 4 as a charge control agent, and optionally, an external additive for regulating fluidity.
9. An electropositive carbon powder according to claim 8 wherein said binder resin is a styrene-acrylate copolymer resin, polyester or polycarbonate;
preferably, the pigment is carbon black, a phthalocyanine pigment, pigment red, or pigment yellow;
preferably, the wax includes natural wax and synthetic wax;
preferably, the fluidity-adjusting external additive is selected from silica powder or titanium dioxide;
preferably, the weight part ratio of the binder resin, the pigment, the wax and the high molecular compound P3-CCR containing the tetrafluoroborate pyridine salt shown in the formula I is (80-120): (5-15): (5-15): (1-20).
10. The method for preparing electropositive carbon powder of claim 8 or 9, characterized by adopting a traditional physical method for preparation, comprising the following steps: (1) melt kneading: adding raw material binder resin, pigment, wax and a high molecular compound P3-CCR containing tetrafluoroborate pyridine salt shown in formula I into a mixing mill according to a formula, and carrying out high-temperature melting, stirring, extrusion and mixing uniformly; (2) crushing: cooling and tabletting the mixed materials, and mechanically crushing the tablets to coarse particles with the particle size of 0.5-3 mm; (3) fine crushing and grading collection: feeding the coarse particles into an air flow pulverizer and a superfine pulverizing and classifying system, and collecting a raw powder sample with the particle size of 5-20 mu m (D50); optionally, (4) final mixing: adding external additive for regulating fluidity to obtain the final product.
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