Process for preparation of conductive polymeric composite particles

• US 5,529,719 A
• Filed: 03/27/1995
• Issued: 06/25/1996
• Est. Priority Date: 03/27/1995
• Status: Expired due to Term

• Current Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Original Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Inventors: Mahabadi, Hadi K., Enright, Thomas E., Cunningham, Michael F.
• Primary Examiner(s): McGinty, Douglas J.
• Application Number:
  US08/411,189
• Time in Patent Office: 456 Days
• Field of Search: 252/511, 252/500, 252/502, 252/510, 252/512, 252/513, 252/518, 252/520, 252/519, 252/506, 252/507, 252/503, 252/521, 252/509, 524/779, 524/783, 524/784, 524/785, 524/847, 430/137, 430/108, 523/215, 523/200, 523/201, 523/205, 428/402, 428/922, 428/407
• US Class Current: 252/511
• CPC Class Codes: C08F 2/02 Polymerisation in bulk
• CPC Class Codes: C08F 2/44 Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• CPC Class Codes: G03G 9/0804 whereby the components are brought together in a liquid dispersing medium
• CPC Class Codes: G03G 9/0806 whereby chemical synthesis of at least one of the toner components takes place

Abstract

A process for the preparation of polymer which comprises effecting a bulk polymerization of a mixture containing at least one monomer, a chain transfer agent, a crosslinking agent, a free radical redox polymerization initiator pair, and at least one additional free radical initiator until from about 4 to about 50 weight percent of the monomer has been polymerized and one or both components in the redox initiator pair has been consumed; dispersing with a high shear mixer the aforementioned partially polymerized mixture in water containing a stabilizing component selected from the group consisting of nonionic and ionic water soluble polymeric stabilizers to obtain a suspension of particles; polymerizing the resulting suspension; and optionally subsequently insulating, washing and drying the polymer product.

Claims

1. A process for the preparation of polymer which comprises effecting a bulk polymerization of a mixture containing about 50 to about 99 percent of at least one monomer, about 0.01 to about 1 percent of a chain transfer agent, about 0.1 to about 5 percent of a crosslinking agent, about 1 to about 50 percent of a conductive additive, about 0.1 to about 3 percent of a free radical redox polymerization initiator pair, and about 0.1 to about 5 percent of at least one additional other initiator until from about 4 to about 50 weight percent of the monomer has been polymerized and one or both components in the the redox initiator pair has been consumed;

dispersing with a high shear mixer, at about 1,000 to about 20,000 rpm, 100 parts of the aforementioned partially polymerized mixture in about 200 to about 500 parts water containing about 0.01 to about 10 percent of a stabilizing component selected from the group consisting of nonionic and ionic water soluble polymeric stabilizers to obtain a suspension of particles;

polymerizing the resulting suspension by heating to between about 45°

to about 120°

C.; and

optionally subsequently isolating, washing and drying the polymer additive product, and wherein said redox polymerization initiator pair is comprised of a peroxide oxidizing agent, and a reducing agent wherein the oxidizing agent is benzoyl peroxide, lauroyl peroxide, 1-1-(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-di-(t-butylperoxy)valerate, or dicumyl peroxide, and wherein the reducing agent is the amine triethylamine, or diethylamine, is the aniline dimethylaniline, or diethylaniline, or is carbon black with a reducing agent on its surface.

6. A process in accordance with claim 1 wherein washing is accomplished with water and/or mixtures of water and alcohols by centrifugation or filtration, and drying is accomplished by freeze drying, fluidized bed drying or vacuum drying.

10. A process in accordance with claim 1 wherein from 1 to 3 additional other initiators are selected.

2. A process for the preparation of conductive polymer particles which comprises effecting at a low temperature heating of between 0°

to about 70°

C. bulk polymerization of a mixture of at least one monomer, a conductive filler, free radical redox polymerization initiator pair components, and at from about 1 to 10 weight percent other free radical initiator, or initiators until from about 4 to about 50 weight percent of the monomer has been polymerized and one or both components in the the redox initiator pair has been consumed;

optionally adding additional free radical initiator, which is the same as or different from said other free radical initiator;

dispersing with a high shear mixer the aforementioned partially polymerized mixture in water containing a stabilizing component selected from the group consisting of nonionic and ionic water soluble polymeric stabilizers to obtain a suspension of particles with an average diameter of from about 0.05 to about 5 microns;

polymerizing the resulting suspension to form polymer the conductive particles; and

subsequently optionally isolating, washing and drying the conductive polymer particles, and wherein said redox polymerization initiator pair is comprised of a peroxide oxidizing agent, and a reducing agent wherein the oxidizing agent is benzoyl peroxide, lauroyl peroxide, 1-1-(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-di-(t-butylperoxy)valerate, or dicumyl peroxide, and wherein the reducing agent is the amine triethylamine, or diethylamine, is the aniline dimethylaniline, or diethylaniline, or is carbon black with a reducing agent on its surface.

3. A process in accordance with claim 2 wherein a mixture of monomers is selected and the low temperature is from about 0°

to about 30°

C.

4. A process in accordance with claim 3 wherein the mixture contains from 2 monomers to about 20 monomers.

5. A process in accordance with claim 2 wherein polymerizing the resulting suspension is accomplished by heating.

7. A process in accordance with claim 5 wherein heating is accomplished at a temperature of from about 30°

C. to about 200°

C.

8. A process in accordance with claim 5 wherein heating is accomplished at a temperature of from about 45°

C. to about 120°

C.

9. A process in accordance with claim 2 wherein the number average molecular weight of the polymer is from between about 3,000 to about 500,000, and the weight average molecular weight of the polymer is from between about 5,000 to about 2,000,000.

11. A process in accordance with claim 2 wherein the conductive polymer particles obtained have an average particle diameter of from about 0.05 micron to about 5 microns.

12. A process in accordance with claim 2 wherein the weight percentage of conductive filler in the conductive polymer particles is from about 1 to about 50.

13. A process in accordance with claim 2 wherein the conductive filler is evenly distributed throughout the polymer matrix of the conductive polymer particles.

14. A process in accordance with claim 2 wherein the conductivity of the conductive polymer particles is from about 10^-10 to about 10^-1 (ohm-cm)^-1 as determined by measuring the electrical resistivity of a pressed pellet.

15. A process in accordance with claim 2 wherein the triboelectrical charge of the conductive polymer particles is from about +40 to about -40 microcoulombs per gram.

16. A process in accordance with claim 2 wherein the monomer is selected from the group consisting of α

-methylstyrene, p-chlorostyrene, monocarboxylic acids and the derivatives thereof;

dicarboxylic acids with a double bond and their derivatives;

vinyl ketones;

vinyl naphthalene;

unsaturated mono-olefins;

vinylidene halides;

N-vinyl compounds;

fluorinated vinyl compounds and mixtures thereof.

17. A process in accordance with claim 2 wherein the monomer is selected from the group consisting of acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methacrylic acids, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile and acrylamide;

maleic acid, monobutyl maleate, dibutyl maleate;

vinyl chloride, vinyl acetate, vinyl benzoate;

vinylidene chloride;

pentafluoro styrene allyl pentafluorobenzene and N-vinyl pyrrole.

18. A process in accordance with claim 2 wherein the conductive filler is selected from the group consisting of conductive carbon blacks, metal oxides, metals, and mixtures thereof.

19. A process in accordance with claim 2 wherein the conductive filler is selected from the group consisting of acetylene black, VULCAN BLACK®

, BLACK PEARLS L®

, CONDUCTEX SC ULTRA BLACK®

, CONDUCTEX 975 BLACK®

, KETJENBLACK®

, REGAL 330®

, RAVEN 5250®

, RAVEN 5750®

, iron oxides, titanium oxides, tin oxides, and iron powder.

20. A process in accordance with claim 2 wherein the other free radical initiator is selected from the group consisting of azo compounds and peroxides.

21. A process in accordance with claim 20 wherein the other free radical polymerization initiator is benzoyl peroxide, lauroyl peroxide, 1-1-(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-di-(t-butylperoxy)valerate, dicumyl peroxide, 2,2'"'"'-azodimethylvaleronitrile, 2,2'"'"'-azoisobutyronitrile, azobiscyclohexanenitrile, or 2-methylbutyronitrile.

22. A process in accordance with claim 2 wherein the other free radical initiator is a peroxide selected in a concentration of from about 0.01 to about 5 weight percent.

23. A process in accordance with claim 2 wherein the redox initiator pair is comprised of an oxidizing agent and a reducing agent, and wherein the amount of said pair is from about 0.1 to about 3 weight percent such that the ratio of oxidizing agent to reducing agent is from about 0.01:

1 to about 100;

1.

24. A process in accordance with claim 23 wherein the ratio selected is from about 10:

1 to about 50;

1.

25. A process in accordance with claim 2 wherein the redox initiator pair is comprised of an oxidizing agent and a reducing agent, and is present in a concentration of from about 0.1 to about 3 weight percent, and the ratio of oxidizing agent to reducing agent is from about 0.01:

1 to 100;

1.

26. A process in accordance with claim 25 wherein the oxidizing agent is a peroxide, and the reducing agent is an amine, an aniline, or a carbon black with a reducing agent on the surface thereof.

28. A process in accordance with claim 23 wherein the redox initiator pair is comprised of an oxidizing agent and a reducing agent, and wherein the amount of said pair is from about 0.1 to about 3 weight percent such that the ratio of oxidizing agent to reducing agent is from about 0.05:

1 to about 20;

1.

27. A process for the preparation of polymer which comprises effecting a bulk polymerization of a mixture containing at least one monomer, a chain transfer agent a crosslinking agent, a carbon black filler additive, a free radical redox polymerization initiator pair, and a third free radical initiator until from about 4 to about 50 weight percent of the monomer has been polymerized and one or both components in the redox initiator pair has been consumed;

optionally adding additional free radical initiator;

which is the same as or different from said third free radical initiator;

dispersing with a high shear mixer the aforementioned partially polymerized mixture in water containing a stabilizing component selected from the group consisting of nonionic and ionic water soluble polymeric stabilizers to obtain a suspension of particles;

polymerizing the resulting suspension; and

subsequently isolating, washing and drying the polymer carbon black product; and

wherein said carbon black is dispersed in said polymer, and wherein said redox polymerization initiator pair is comprised of a peroxide oxidizing agent, and a reducing agent wherein the oxidizing agent is benzoyl peroxide, lauroyl peroxide, 1-1-(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-di-(t-butylperoxy)valerate, or dicumyl peroxide, and wherein the reducing agent is the amine triethylamine, or diethylamine, is the aniline dimethylaniline, or diethylaniline, or is carbon black with a reducing agent on its surface.