Polymerization process and toner compositions therefrom

A free radical polymerization process for the preparation of a thermoplastic resin or thermoplastic resins comprising:

• heating a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin or thermoplastic resins with a high monomer to polymer conversion and with excellent polydispersities;
• cooling said mixture;
• optionally isolating said thermoplastic resin or thermoplastic resins;
• and
• optionally washing and drying said thermoplastic resin or thermoplastic resins, and wherein the heating is accomplished at a temperature of from about 100.degree. to about 160 degrees Centigrade, the monomer to polymer conversion is at least about 50 weight percent based on monomer, the resin or resins polydispersity is from about 1.1 to about 1.5.

A free radical polymerization process for the preparation of a thermoplastic resin or thermoplastic resins comprising:

• heating a mixture of a peroxide free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin or thermoplastic resins with a high monomer to polymer conversion and with excellent polydispersities;
• cooling said mixture;
• optionally isolating said thermoplastic resin or resins;
• and
• optionally washing and drying said thermoplastic resin or thermoplastic resins, and wherein the heating is accomplished at a temperature of at least about 100.degree. C., the conversion is from about 50 to about 95 weight percent, and the polydispersity is from about 1.1 to about 1.5.

A free radical polymerization process for the preparation of a thermoplastic resin comprising:

• heating a mixture of a peroxide free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin with a high monomer to polymer conversion and with excellent polydispersities;
• cooling said mixture;
• optionally isolating said thermoplastic resin;
• and
• optionally washing and drying said thermoplastic resin, and wherein the heating is accomplished at a temperature of from about 120.degree. to about 160 degrees Centigrade, the conversion is from 50 to 95 weight percent, the polydispersity is from about 1.1 to about 1.5 and wherein the heating is accomplished for a period of from about 1 to about 60 hours.

A free radical polymerization process for the preparation of a thermoplastic resin or resins comprising:

• heating a water suspension mixture of a peroxide free radical initiator, a nitroxide stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin or resins with a monomer to polymer conversion in excess of about 50 weight percent;
• cooling said mixture;
• optionally isolating said thermoplastic resin or resins;
• and
• optionally washing and drying said thermoplastic resin or resins and wherein said thermoplastic resin possesses a narrow polydispersity of from about 1.0 to about 2.0 and a modality of 1.

A free radical polymerization process for the preparation of resin comprising:

• heating a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said resin with a high monomer to polymer conversion and with excellent polydispersities;
• cooling said mixture;
• optionally isolating said resin;
• and
• optionally washing and drying said resin, and wherein the heating is accomplished at a temperature of from about 120.degree. to about 160 degrees Centigrade, the conversion is from about 50 to about 95 weight percent based on monomer, the polydispersity is from about 1.1 to about 1.4, and the free radical initiator and stable free radical agent are added into the mixture as separate components.

A free radical polymerization process for the preparation of a resin comprising:

• heating a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said resin with a high monomer to polymer conversion and with excellent polydispersities;
• cooling said mixture;
• isolating said resin, and
• optionally washing and drying said resin and wherein the heating is accomplished at a temperature of from about 120.degree. to about 160 degrees Centigrade, the conversion is from about 50 to about 95 weight percent based on monomer, and the polydispersity is from about 1.1 to about 1.4.

A polymerization process for the preparation of thermoplastic resins comprising:

• heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin;
• optionally cooling said first mixture;
• adding to said first intermediate product resin a second mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture contains the same monomer components as said polymerizable monomer compound of said first mixture, and said free radical initiator and said stable free radical agent of said second mixture are the same or different from said free radical initiator and said stable free radical agent of said first mixture, and wherein there is formed a combined mixture;
• heating said combined mixture to form a third mixture comprised of a mixture of thermoplastic resins comprised of a first product resin formed from said first intermediate product resin and added said second monomer and a second product resin formed from substantially only said second monomer;
• cooling said third mixture;
• optionally isolating said mixture of thermoplastic product resins from said third mixture;
• and
• optionally washing and drying said mixture of thermoplastic resins and wherein said first product resin and said second product resin each possess a polydispersity of about 1 to about 2.

A free radical polymerization process for the preparation of thermoplastic resin comprising:

• heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin;
• optionally cooling said first mixture;
• adding to said first intermediate product resin a second mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture contains the same components as said polymerizable monomer compound of said first mixture, and said free radical initiator and said stable free radical agent of said second mixture are the same or different from said free radical initiator and said stable free radical agent of said first mixture, and wherein there is formed a combined mixture;
• heating for a period of from about 1 to about 60 hours said combined mixture to form a third mixture comprised of a mixture of thermoplastic resins comprised of a first product resin formed from said first intermediate product resin and added said second monomer and a second product resin formed from said second monomer;
• cooling said third mixture;
• optionally isolating said mixture of thermoplastic product resins from said third mixture;
• and
• optionally washing and drying said mixture of thermoplastic resins and wherein said first product resin and said second product resin each possess a narrow polydispersity obtained in excellent conversion, which conversion is from about 50 to about 90 weight percent and which polydispersity is from about 1.1 to about 1.5;
• and wherein heating is accomplished at a temperature of from about 100.degree. to about 160 degrees Centigrade.

A polymerization process for the preparation of a block copolymer thermoplastic resin or resins comprising:

• heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin;
• optionally cooling said first mixture;
• optionally isolating said first intermediate product resin;
• adding to said first intermediate product resin a second mixture comprised of at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture is different from said polymerizable monomer compound of said first mixture, to form a combined mixture;
• heating said combined mixture to form a third mixture comprised of a block copolymer thermoplastic resin comprised of a first product resin formed from said first intermediate product resin and added said second monomer;
• cooling said third mixture containing said block copolymer thermoplastic resin;
• optionally isolating said block copolymer thermoplastic resin from said third mixture;
• and
• optionally washing and drying said block copolymer thermoplastic resin wherein said block copolymer thermoplastic resin possesses a polydispersity of about 1 to about 2.

A polymerization process for the preparation of a multiblock copolymer thermoplastic resin or resins comprising:

• heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin;
• optionally cooling said first mixture;
• optionally isolating said first intermediate product resin;
• adding to said first intermediate product resin a second mixture comprised of at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture is different from said polymerizable monomer compound of said first mixture, to form a combined mixture;
• heating said combined mixture to form a third mixture comprised of a block copolymer thermoplastic resin comprised of a first product resin formed from said first intermediate product resin and added said second monomer;
• cooling said third mixture;
• optionally isolating said third mixture;
• sequentially repeating the preceding steps of adding, heating and cooling, N times, to form a fourth mixture containing a multiblock copolymer thermoplastic resin or resins having N+2 blocks and wherein N is the number of times said sequence is repeated;
• optionally isolating said multiblock copolymer thermoplastic resin from said fourth mixture;
• and
• optionally washing and drying said multiblock copolymer thermoplastic resin and wherein said multiblock copolymer thermoplastic resin possesses a polydispersity of about 1 to about 2 and a modality of 1.

A free radical polymerization process for the preparation of a block copolymer thermoplastic resin or resins comprising:

• heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin;
• optionally cooling said first mixture;
• optionally isolating said first intermediate product resin;
• adding to said first intermediate product resin a second mixture comprised of at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture is different from said polymerizable monomer compound of said first mixture, to form a combined mixture;
• heating said combined mixture to form a third mixture comprised of a block copolymer thermoplastic resin comprised of a first product resin formed from said first intermediate product resin and added said second monomer;
• cooling said third mixture;
• optionally isolating said block copolymer thermoplastic resin from said third mixture;
• and
• optionally washing and drying said block copolymer thermoplastic resin wherein the resin possesses a narrow polydispersity and is obtained in excellent conversion, which conversion is from about 50 to about 90 weight percent based on monomer and which polydispersity is from about 1.1 to about 1.6 and which heating is at a temperature of from about 120.degree. to about 160 degrees Centigrade.