JPH08208729A - Free-radical polymerizing method and preparation of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a free-radical polymn. process for producing a thermoplastic resin having a narrow polydispersity and useful as a toner resin material by adopting a free-radical polymn. process using an ultrasonic energy and enabling the selection of a low temp.

SOLUTION: The process comprises heating a mixture comprising a free- radical initiator, a stable free-radical reagent, and at least one polymerizable monomer to about 40-100°C under exposure to an ultrasonic wave, cooling the resulting product, if necessary isolating the resulting thermoplastic resin, and washing and drying the product or resin. The stable free-radical reagent is pref. 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and is used in a molar ratio to the initiator of about 2.5-0.5. The process can be repeated many times by adding one or more kinds of monomers stepwise and can from a mixture of a resin of a single modality by changing the amts. of the initiator and the free-radical reagent.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for preparing a polymer including a homopolymer, a random copolymer, a block copolymer, a functionally activated polymer and the like, more specifically, a polymerization method and a method for forming the same. The polymer is

[0002]

BACKGROUND OF THE INVENTION The present invention is directed to narrow polydispersi.
ties), that is, where Mw is the weight average molecular weight and Mn is the number average molecular weight, the narrow molecular weight distribution shown by the ratio Mw / Mn and the easily adjustable modalities.
a stable free-radical relaxed method for producing one or more thermoplastic polymer resins having at least one Under conditions of ultrasonic radiation, heating a mixture of a free radical initiator, a stable free radical reagent and at least one polymerizable monomer compound, and cooling the mixture to effect polymerization. To stop
It relates to a method comprising isolating a thermoplastic resin product, optionally washing and drying the polymer resin product.
In the method of the present invention in one aspect, the temperature can be low, for example about 40 to about 100 ° C. The polymeric resin produced by the method of the present invention in one aspect comprises:
In one embodiment, which is essentially a monomodal and repeats the heating and sonication steps, ie, the combined initiation and polymerization steps, a single modality of polymer resin (ie narrow polydispersity and known or selectable) There is provided a means of obtaining a mixture of compositionally identical resin types) having both properties of different modalities. In some embodiments, the methods of the present invention provide a means for conducting bulk or net free radical polymerization processes on the order of kilograms or larger. Certain embodiments described above can be carried out in a single or single pot reactor environment. Further, in some embodiments, polymer chain growth proceeds by a pseudoliving mechanism,
Provide thermoplastics of various molecular weights, from very low to very high, eg from less than about 2,000 to about 300,000, while maintaining a narrow molecular weight distribution or polydispersity, eg from about 1.05 to about 1.95. The conversion of monomer to polymer is high, for example at least about 50%, and more particularly from about 50 to about 99-100%. Further, in some embodiments,
Block copolymers can be synthesized by the stable free radical-relaxed free radical polymerization method described above, and each block formed is sufficiently specified in length by the reacted monomer, for example. , Each of the formed blocks has a narrow molecular weight distribution, the block copolymer is substantially 100% block copolymer, and the formation of the homopolymer of the second monomer is not mixed. . The formation of the homopolymer of the second block monomer is carried out by the Otsu's iniferter (ini
ferter) is a possible competing reaction that occurs in other prior art, such as that of ferter).

US Pat. No. 5,322,912 exemplifies a free radical method for preparing thermoplastics.

There is a need for a method for the preparation of narrow polydisperse polymeric resins by an economical and scalable free radical polymerization technique, which polymer is a prior art methodology for free radical polymerization. While avoiding problems such as gel formation, heat generation, multi-step reaction system with limited capacity, purification, performance characteristics of polymer chain products, etc., such as hardness, low gel content, processability, transparency, It retains many or all of its desirable physical properties, such as high gloss durability. Also, with the method of the present invention, lower temperatures can be selected and the rate of polymerization can be increased, so that, for example, the reaction time required to achieve a conversion of greater than about 90% is By using sonication, it is less than 6-7 hours, preferably about 3-5 hours.

The thermoplastic resin product of the present invention can be selected for a number of applications, such as toners, developers, and more particularly as a toner resin for electrostatographic imaging processes, and is a single resin. Mixtures of single modality narrow molecular weight resins or block copolymers having a narrow molecular weight distribution within the modality or respective block component are suitable, for example, in thermoplastic film and coating technology.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to use ultrasonic energy at low temperatures, such as about 40 to about 10.
It is to provide a free radical polymerization reaction system which gives a narrow polydisperse homopolymer or copolymer thermoplastic resin product which can be selected from 0, more particularly from about 50 to about 70 ° C.

Another object of this invention is the use of ultrasonic energy to increase the rate of polymerization so as to reduce the time required to polymerize the monomers into the polymer, a narrow polydisperse single polymer. It is an object of the present invention to provide a free radical polymerization reaction system which gives a combined or copolymer thermoplastic resin product.

Another object of this invention is in the range of about 100: 1 to about 1: 1 and preferably about 20 to increase the rate of reaction by at least a factor of 3 without broadening the polydispersity of the polymer resin. It is possible to choose the addition of small amounts of organic acids with a stable free radical to organic acid molecular ratio in the range of: 1 to about 5: 1, where the acid is, for example, sulfonic acid, phosphoric acid, or benzoic acid. Such as carboxylic acid, camphor sulphonic acid, and further contains nitroxide stable radicals, which have acidic functional groups such as 2,2,
It shall contain 5,5-tetramethyl-3-carboxyl-1-pyrrolidinyloxy.

Another object of the present invention is to prepare a resin using a polymerization process in which the molecular weight of the growing homopolymer or copolymer chain is determined over the entire time period of the polymerization reaction. The% conversion or degree of polymerization of the monomer to polymer over time or number average molecular weight is approximately linear, ie the polymerization process occurs without the Trommsdorff effect.

The object of the present invention is from about 1.05 to about 1.9.
5, preferably a resin having a Mw / Mn ratio of about 1.1 to about 1.6, at a low temperature, preferably about 40 to about 100.
A method of preparing at ℃, for example, at least 50%,
Another object of the present invention is to provide a method for preparing a resin which enables a high monomer-to-polymer conversion rate of about 50 to about 100, or 50 to 95%.

Still another object of the present invention is to provide a homopolymer,
By providing a stable free radical polymerization process for obtaining, for example, styrene homopolymers, random copolymers, block copolymers, multiblock copolymers, etc., such as styrene acrylate, styrene methacrylate, styrene butadiene, among others. Yes, generally A, AA, AB, B
A, AAA, ABA, BAB, AABBAB, ABC,
It is intended that homopolymers and copolymers can be obtained by the method of the present invention in its various aspects.

[0012]

These and other objects of the present invention can be accomplished by certain embodiments of the free radical polymerization process using ultrasonic radiation at low temperatures. More specifically, the process of the present invention comprises a free radical polymerization process, wherein a free radical initiator, a stable free radical reagent, and at least one polymerizable monomer are present in the presence of low temperature and ultrasonic energy. The mixture with the compound is heated to form one or more thermoplastics having a high conversion of monomer to polymer, the mixture is cooled and, if necessary, one or more thermoplastics are added. Separating, optionally washing and drying one or more thermoplastic resins, wherein the one or more thermoplastic resins are, for example, from about 1.05 to about 1.95, preferably from about 1.1 to It has a narrow polydispersity of about 1.6.

To be precise, the present invention provides a mixture of a free radical initiator, a stable free radical reagent and at least one polymerizable monomer compound in a free radical polymerization process for the preparation of thermoplastics. Heating, said heating being carried out in the presence of ultrasonic radiation at a temperature of from about 40 to about 100 ° C., cooling said mixture, optionally isolating said thermoplastic resin, said thermoplastic resin Is a free radical polymerization method for the preparation of a thermoplastic resin, comprising:

[0014]

One aspect of the present invention is directed to a free radical polymerization process for the preparation of thermoplastics, which comprises a free radical initiator, a stable free radical reagent, and at least one A first mixture containing a polymerizable monomer compound is heated to form a first intermediate product resin, and the first mixture is cooled if necessary, and the first intermediate product resin is A second mixture comprising a free radical initiator, a stable free radical reagent, and at least one polymerizable monomer compound is added, wherein the one or more polymerizable monomers of the second mixture. Is the same as the one or more polymerizable monomers of the first mixture, and the free radical initiator and the stable free radical reagent of the second mixture are the same as the free radical initiator and the stable radical of the first mixture. Free radio The same or different than the reagent and thus forming a combined mixture, heating the combined compound at low temperature in the presence of ultrasonic energy and adding a first intermediate resin with a second one or more A third product resin formed of a first product resin formed of a second monomer and a second product resin formed of a second one or more monomers; Forming a mixture, cooling the third mixture, optionally isolating the mixture of thermoplastic product resin from the third mixture, optionally washing and drying the mixture of thermoplastic resins. Including the first product resin and the second product resin,
Each having a narrow polydispersity, the mixture of thermoplastics has a modality equal to about 1 to about 2. If desired, an effective amount of fresh or fresh mixture of one or more monomers, a free radical initiator and a stable free radical reagent is subsequently added prior to the final cooling and isolation steps. Thereby, a high modality, for example about 3 to about 20, can be conveniently achieved.

Further, in one aspect of the present invention there is provided a free radical polymerization process for the preparation of one or more block copolymer thermoplastics, which comprises from about 40 to about 10.
A first mixture comprising a free radical initiator, a stable free radical reagent, and at least one polymerizable monomer compound is heated in the presence of ultrasonic energy at a low temperature of 0 ° C. to heat the first mixture. Forming an intermediate product resin, cooling the first mixture, isolating the first intermediate product resin, and adding at least one polymerizable monomeric compound (block copolymer) to the first intermediate product resin. When preparing a coalescence, usually one monomer is added at a time and then polymerization is carried out, and then the next monomer is added, so there are many steps or the number of times that different monomers can be added. , But each time only one monomer is added) is added), wherein the polymerizable monomer compound of the second mixture is added to the mixture of the first mixture. Unlike polymerizable monomers, form a mixture thus combined And the combined mixture at low temperature by heating in the presence of ultrasonic energy, the first formed from the second monomer was added to the first intermediate product resin
Forming a third mixture containing the block copolymer thermoplastic resin containing the product resin of, cooling the third mixture, and optionally isolating the block copolymer thermoplastic resin from the third mixture. Optionally washing and drying the block copolymer thermoplastic, said block copolymer having a narrow polydispersity and a modality equal to 1. Isolation of the intermediate product resin is preferred when high purity and block integrity or homogeneity is desired.
That is, the remaining unreacted monomer (s) of the first mixture subsequently reacts with the growing polymer chains formed from the second mixture of polymerizable monomeric compounds, thereby May be incorporated. Thus, in preparing block copolymers by the method of the present invention, if high purity is desired, or if the degree of polymerization is less than about 70-90% for block or multiblock polymerization reactions,
Isolation is preferred, for example, by precipitation of an intermediate product of the polymerization reaction.

According to yet another aspect of the present invention, there is provided a free radical polymerization process for the preparation of thermoplastics, which has a power of about 200 to about 400 watts and a frequency of greater than about 20 to about 50 kHz. Sonic bath feed medium strength ultrasonic energy, or titanium horn feed medium strength ultrasonic energy of about 20 to about 50 kHz with a power output of about 200 to about 450 watts, and a useful period of about 30 minutes to about 6 hours. Between about 40 and about 100 in the presence of ultrasonic radiation during
High conversion of monomer to polymer by heating an aqueous suspension mixture of a peroxide free radical initiator, a nitroxide stable free radical reagent and at least one polymerizable monomer compound at a temperature of ° C. Rate, ie at least about 50%
Forming a thermoplastic resin having a conversion of, cooling the mixture, isolating the thermoplastic resin, optionally washing and drying the thermoplastic resin, wherein the thermoplastic resin comprises about 1.1 A narrow polydispersity of about 1.6, and in one aspect a modality of 1.

The present invention includes certain embodiments of: In a free radical polymerization process for the preparation of thermoplastics,
A mixture of a free radical initiator, a stable free radical reagent and at least one polymerizable monomer compound is heated, said heating being carried out in the presence of ultrasonic radiation at a temperature of about 40 to about 100 ° C. A free radical polymerization process comprising cooling the mixture, isolating the thermoplastic resin, washing and drying the thermoplastic resin; in a free radical polymerization process for the preparation of one or more thermoplastic resins Heating a mixture of a free radical initiator, a stable free radical reagent, and at least one polymerizable monomer compound, and having a high conversion rate of at least about 50 monomers to one or more resins The one or more thermoplastic resins form one or more thermoplastic resins having excellent polydispersity of about 1.05 to about 1.95, and the heating is ultrasonic wave emission. At a temperature of about 40 to about 100 ° C. in the presence of a free radical polymerization method comprising cooling the mixture; a free radical initiator for the preparation of a thermoplastic resin; A mixture of a free radical reagent and at least one polymerizable monomer compound to form a first intermediate product resin, optionally cooling the first mixture,
To the resulting first intermediate product resin is added a second mixture comprising a free radical initiator, a stable free radical reagent and at least one polymerizable monomer compound, wherein: And wherein the polymerizable monomer compound of the second mixture contains the same components as the polymerizable monomer compound of the first mixture, and the free radical initiator of the second mixture and the The stable free radical reagent is the same or different from the free radical initiator and the stable free radical reagent of the first mixture,
Thus forming a combined mixture, heating the combined mixture to form a first product resin formed from the first intermediate product resin and the second monomer added, and Forming a third mixture comprising a mixture of a thermoplastic resin comprising a second product resin formed from a second monomer, cooling said third mixture, said first product resin And the second product resin has a narrow polydispersity of about 1.05 to about 1.95, respectively, and the heating is performed at a temperature of about 40 to about 100 ° C. in the presence of ultrasonic radiation. A free radical polymerization process for the preparation of a bimodal thermoplastic resin, comprising a free radical initiator in the presence of ultrasonic radiation at a temperature of about 40 to about 100 ° C. And a stable free radical reagent , A first mixture containing at least one polymerizable monomeric compound to form a first intermediate product resin, optionally cooling said first mixture, said first intermediate A second mixture containing a free radical initiator, a stable free radical reagent, and at least one polymerizable monomer compound is added to the product resin, wherein the polymerization of the second mixture is performed. The polymerizable monomer compound contains the same components as the polymerizable monomer compound of the first mixture, and the free radical initiator and the stable free radical reagent of the second mixture are the same as those of the first mixture. One or more of the free radical initiator and the stable free radical reagent of one mixture, thus forming a combined mixture, about 40 to about 100 ° C.
Heating the combined mixture in the presence of ultrasonic radiation at a temperature of about 30 minutes to about 6 hours to form the first intermediate product resin and the added second monomer. Forming a third mixture containing a mixture of a thermoplastic resin containing the first product and a second product resin formed from the second monomer; Cooling the third mixture, optionally isolating the mixture of thermoplastic product resins from the third mixture, optionally washing and drying the mixture of thermoplastic resins, The first product resin and the second product resin each have a narrow polydispersity obtained with excellent conversion, and the conversion is about 50 to about 90%. Free radical polymerization method in which the property is about 1.1 to about 1.8; In the presence of ultrasonic radiation at a temperature of from about 40 to about 100 ° C., and a free radical initiator,
Heating a mixture of a stable free radical reagent and at least one monomer component, the resin comprising about 1.0
Homoacrylate and copolymer acrylate resins having a polydispersity of 5 to about 1.95, a conversion of monomer to resin of at least 50% and having narrow polydispersity properties depending on the polymerization method. The polymerization method proceeds at a high conversion rate from a monomer to a polymer, and a copolymer containing a homoacrylate and a homoacrylate moiety is produced by the acrylate polymerization method, and its number average molecular weight (M
n) is greater than about 100 and up to about 1,000 and the polydispersity ratio of weight average molecular weight (Mw) to its number average molecular weight (Mn) is about 1.0 to about 2.0, preferably about 1 1 to about 1.6, and in one embodiment as a stable free radical reagent, 4-oxo-2,2,6,6-tetramethyl-1
-Piperidinyloxy (4-oxo-TEMPO) can be selected.

The present invention provides, in one aspect, a pseudo-living polymerization process that allows the synthesis of narrow polydisperse homoacrylate and copolymer acrylate resins from acrylate and acrylate derivative monomers. It This method uses, in one embodiment, known free radical initiators in combination with oxygenated stable free radical reagents and acrylate monomers to provide narrow polydisperse homoacrylate and copolymer acrylate resins. can do.

In one embodiment of the method described above, a polymer or copolymer resin composition is obtained, wherein the one or more product resins have a weight average molecular weight (M) of from about 2,000 to about 300,000.
w) and a number average molecular weight of about 1,800 to about 153,000 (M
n) and a polydispersity of about 1.05 to about 1.95,
More specifically, Mw / Mn is from about 1.1 to about 1.6, about 1.1 to about 1.5, or slightly greater than about 1 to about 1.6.

Without wishing to be bound by theory, when the polymerization reaction process of the present invention is carried out at low bulk temperature in the presence of ultrasonic energy, mechanical or vibrational energy causes pressure to build up in the reaction mixture. Waves are considered to be generated. This action creates millions of microscopic bubbles or cavities, which expand during negative pressure excursions and contract during positive excursions. This phenomenon is called cavitation, which allows for ultrasonic probes, horn tips, such as Cole-Parmer ultrasonic homogenizer, 4710.
Horn, or ultrasonic bath with water, eg Branson Mo
A strong shear action on del 5200 occurs. Upon high-intensity ultrasonic radiation, the temperature in a given localized area rises significantly, for example from about tens of degrees to about several hundreds of degrees. Such high localized temperature breaks weak chemical bonds, such as oxygen-oxygen bonds in peroxide initiators, while maintaining a low bulk temperature for the overall system, resulting in faster polymer chains. A quick start is possible. In addition, this high localized temperature also affects weak chemical bonds in the growing polymer chain, such as the bond between the growing chain carbon atom and the nitroxide radical oxygen atom. This bond is cleaved, an additional monomer is inserted and polymerization continues.
The ultrasonic energy used depends on the initiator used,
It allows all polymer chains to be initiated at about the same time, which is the main reason for allowing the formation of polymer chain products with narrow polydispersity. Undesired chain ligation and disproportionation termination reactions, which are very predominant under some conditions of prior art free radical polymerization systems, are due to the extremely low effective concentration and availability of living free chains. This is suppressed by using the method of the present invention. Furthermore,
Since the stable free radical reagents of the present invention do not initiate polymerization, no new chains will be initiated after the initiation period, which is initiated at about the same time for all polymer chains.

The process of the present invention, in some embodiments, further comprises means for continuously repeating the monomer addition or polymerization steps, wherein the additional stable free radical and free radical initiator of the process are added to the N 2 Once added, it should give a well-specified mixture of thermoplastics, each resin in the mixture being composed of a polymer with a distinct and narrow polydispersity, N being an initiator, a stable free radical. The mixture has a modality equal to N + 1, given the number of times the reagent and monomer addition steps are repeated.

The present invention, in certain aspects, provides several particular advantages, including: Using the method of the present invention, the polydispersity of the polymer product is narrowed and the ratio of stable free radical reagent to free radical initiator molecular concentration is varied to provide a monomer / comonomer system dependent. And can vary between about 1.05 and about 1.95. If the polymerization process conditions of the present invention are attempted without the use of SFR additives, a broad molecular weight resin with a polydispersity of 2-6 is obtained.

The stable free radical reagent moderated polymerization reaction is carried out in a variety of media, such as suspension, emulsification, bulk or net or without solvent, or in aqueous or non-aqueous solutions. However, high boiling solvents such as toluene and xylene should preferably be used.

In the reaction of the monomers for forming the polymer or the mixed monomers, the reaction time is, for example, about 1 to about 6
Fluctuating between 0 hours, but preferably about 2-10 hours,
The optimum time is about 4 to 7 hours. The optimum reaction time is temperature,
It may vary depending on the volume and scale of the reaction and the amount and type of polymerization initiator and stable free radical reagent selected. The polymerization reaction temperature is kept relatively constant throughout the heating process by providing an adjustable external heat source, the temperature is about 40 ° C to about 100 ° C, preferably about 5 ° C.
Maintain at 0 ° C to about 75 ° C.

The free radical initiator selected can be any free radical polymerization initiator capable of initiating a free radical polymerization process, such as peroxide initiators such as benzoyl peroxide, and azo initiators such as Benzoyl peroxide is preferred, including azobisisobutyronitrile and the like. The concentration of the initiator used is 0.2-6% by weight of the total weight of the monomers to be polymerized and is determined by the desired molecular weight of the resin. The molecular weight of the thermoplastic resin product increases as the concentration of the initiator decreases with respect to the molar equivalent weight of the monomers used. The free radical initiator is added as a separate component to the reaction mixture and should not react with the stable free radical reagent prior to its use in the methods presented herein.

Examples of stable free radical reagents or components that can be selected include nitroxide free radicals such as proxil (2,2,5,5-tetramethyl-1-pyrrolidinyloxy), 3-carboxy-proxyl, 3- Carbamoyl-proxyl, 2,2-dimethyl-4,5-cyclohexyl-proxyl, 3-oxo-proxyl, 3-hydroxylimine-proxyl, 3-aminomethyl-proxyl, 3-methoxy-proxyl, 3-t-butyl- Proxy, 3-maleimido-proxyl, 3,4-di-t-butyl-proxyl, 3-
Carboxylic-2,2,5,5-tetramethyl-1-pyrrolidinyloxy and its derivatives, and TEMPO (2,2,6,6
-Tetramethyl-1-piperidinyloxy), 4-benzoxyloxy-TEMPO, 4-methoxy-TEMPO, 4-carboxylic
-4-amino-TEMPO, 4-chloro-TEMPO, 4-hydroxylimine-TEMPO, 4-hydroxy-TEMPO, 4-oxo-TEMPO, 4-
Oxo-TEMPO-ethylene ketal, 4-amino-TEMPO, 2,
2,6,6-Tetraethyl-1-piperidinyloxy, 2,2,6-trimethyl-6-ethyl-1-piperidinyloxy and the like, and derivatives thereof, and dialkyl nitroxide radicals such as di-t-butyl nitroxide, diphenyl nitroxide, t -Butyl-t-amyl nitroxide and its derivatives, and DOXYL (4,4-dimethyl-1-oxazolidinyloxy), 2-di-t-butyl-doxyl, 5-decane-doxyl, 2-cyclohexane- Doxyl and the like, and derivatives thereof, and 2,5-dimethyl-3,4-dicarboxylic-pyrrole, 2,5-dimethyl-3,4-diethyl ester-pyrrole, 2,3,4,5-tetraphenyl- Pyrrole, etc., and 3-cyano-pyrroline-3-carbamoyl-pyrroline, 3-carboxylic-pyrroline, etc., 1,1,3,3-tetramethylisoindoline-2-yloxyl and 1,1,3,3-tetraethyl Isoin Phosphorus-2 Irokishiru like, porphylene lexical nitroxyl radical, such as 5-cyclohexyl porphylene lexical nitroxyl and 2,2,4,5,5- pentamethyl -Δ
³ -imidazoline-3-oxide-1-oxyl, etc., and galbinoxyl, etc., 1,3,3-trimethyl-2-azabicyclo [2,2,2] octane-5-one-2-oxide and 1-azabicyclo [3 , 3,1] nonane-2-oxide and the like are included, and TEMPO is preferable. These stable free radical reagent materials are known as free radical polymerization inhibitors such as G. Moad et al., Tetrahedron Letters, 22, 1165 (1981).
Are known in the literature such as. However, under the polymerization conditions of the present invention, stable free radical reagents act primarily as palliatives to utilize the normally reactive and indiscriminate intermediate free radical species. Nitroxides include N, N-disubstituted nitroxides such as Fremy's salt.

The molecular ratio of the stable free radical (SFR) reagent to the free radical initiator (INIT) is about 2.5-
The range is 0.5, preferably about 2.0 to 0.9. Without wishing to be bound by theory, in some embodiments, about 1.3 to 1 of a stable free radical reagent, such as TEMPO, to a free radical initiator, such as benzoyl peroxide. Molecular ratio [SFR:
INIT] is considered important. In some embodiments, if [SFR: INIT] is too high, the reaction rate may decrease. If [SFR: INIT] is too low, the reaction product will have an undesirably increased polydispersity. Also, polymerizing styrene to polystyrene without the use of the stable free radical reagent of the present method results in an isolated product polymer having a polydispersity of 2.0 or greater.

In some embodiments, the molecular ratio of monomer content to stable free radical reagent to free radical initiator is from about 10: 0.5: 1 to about 10,000: 5: 1, preferably about 300 :. The range is from 1.3: 1 to about 7,000: 1.3: 1. Of importance in some embodiments is a stable free radical to initiator molecular ratio of from about 1.3 to about 1 particularly for the polymerization of styrene. For monomers other than styrene, such as acrylates, a similar ratio is chosen, namely 1.3: 1.

The method of the present invention provides, in one embodiment, a high conversion of monomer to polymer, or a degree of polymerization, for example, in one embodiment, 90% by weight or more, more specifically about 75%. ~ About 100%. Further, the method of the present invention, in some embodiments, provides a relatively high weight average molecular weight of the polymer product, wherein the weight average molecular weight is about 2,
000 to about 300,000 with a preferred range of about 2,000
~ About 250,000. In some embodiments, the method of the present invention can be used to obtain a polymer having a Mw of about 500,000.

Monomers of choice include those capable of undergoing free radical polymerization, including, but not limited to, styrene, substituted styrenes and their derivatives such as α-methylstyrene, 4- Methylstyrene, butadiene and any conjugated diene monomer that is sufficiently active and provides stable free radical reaction adducts and high molecular weight polymer products under moderated free radical relaxed polymerization reaction conditions, Examples include isoprene and myrcene, acrylates and their derivatives. Examples of the obtained polymer include styrene, acrylate, styrene acrylate, styrene butadiene and the like. The acrylate polymerization of the reaction of the present invention, in some embodiments, contributes to supplementing the solvent or co-solvent to ensure that the reaction mixture maintains a homogeneous single phase throughout the conversion of the monomers. It shall be. To select any solvent or co-solvent as long as the solvent medium is effective to allow the solvent system to avoid precipitation or phase separation of reactants or polymer products until after all polymerization reactions are complete. You can Exemplary solvents or co-solvents include polymer product compatible aliphatic alcohols, glycols, ethers,
Glycol ether, pyrrolidine, N-alkylpyrrolidinone, N-alkylpyrrolidinone, polyethylene glycol, polypropylene glycol, amides, carboxylic acids and their salts, esters, organic sulfides, sulfoxides, sulfones, alcohol derivatives, hydroxy ether derivatives, such as butyl CARBITOL (registered Trademark) or CELL
Included are OSOLVE®, amino alcohols, ketones, and their derivatives and mixtures thereof. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, glycerin, dipropylene glycol, tetrahydrofuran, etc., and mixtures thereof. When a mixture of water and a water-soluble or miscible organic liquid is selected as the reaction medium, the weight ratio of water to cosolvent is typically about 100: 0 to about 10: 9, preferably about 97 :. The range is from 3 to about 25:75.

In one embodiment, the reaction time can be increased from about 16 hours or more to about 4 to 7 hours by adding a catalytic amount of a protic acid that can accelerate the rate of monomer polymerization reaction and cannot initiate cationic polymerization. Can be reduced to This acid is an organic acid such as sulfonic acid, phosphoric acid, carboxylic acid,
And selected from the group consisting of acid functionalised nitroxides, for example 3-carboxyl-proxyl, camphor sulphonic acid is the preferred acid. The molecular ratio of stable free radical to acid can vary, but can be, for example, about 100: 1 to 1: 1 with a suitable ratio of about 20: 1 to 5: 1. Excessive addition of organic acid in excess of the above amounts broadens the polydispersity of the resin in certain embodiments.

The stable free-radical relaxed polymerization process of the present invention can be repeated many times in the same reaction vessel by delaying the addition of one or more monomers and adding further in stages. The amounts of agent and stable free radical reagent are varied to form a single modality resin mixture, where each component has a distinct molecular weight and a narrow molecular weight distribution, and N is a mono The mixture has a modality of N + 1 as an indication of the number of additional additions of the body, initiator, and stable free radical reagent.

Cooling, which can be accomplished by turning off the heating source, such as an oil bath, removing the vessel from the oil bath and allowing it to cool naturally while maintaining agitation, causes the polymerization reaction to reach ambient temperature. Effectively calm or stop the relaxed reaction with stable free radicals. Monomers, stable free radicals, while heating with ultrasonic waves,
The addition of new and subsequent initiators and new initiators gives new polymer species with a narrow molecular weight distribution, each new polymer species being independent of the other previously formed polymer species. Continue to grow.

Alternatively, a block copolymer resin can also be prepared, whereby after each desired block is formed, a fresh one or more new initiators or stable free radical reagents are added without further addition. When multiple monomers are added to form a new block, each block component becomes
It will be well defined in length, have a narrow molecular weight distribution, and will have properties depending on the monomer selected for repeated procedures and blending.

Additional optional known additives can be selected in the polymerization reaction, which can provide additional performance enhancements to the resulting product, including, for example: Colorants, lubricants, mold release or transfer agents, surfactants, stabilizers, defoamers and the like.

Separate mix of single modalities (monomodals), ie, well-specified multimodalities (multim)
Polymeric resins having a molecular weight distribution of odal) have, in certain embodiments thereof, melt rheological properties, including improved flow and elasticity, especially for electrostatographic toner compositions.
And offers several advantages such as improved performance characteristics such as tribocharging, mixing speed, and storage stability.

The method of the present invention can be selected to form a wide variety of polymers. For example, it can be used to polymerize styrene monomers to form polystyrene, butadiene to form polybutadiene, or n-
Butyl acrylate can be polymerized to form poly (n-butyl acrylate). The method of the present invention can be selected to polymerize a mixture of two or more different polymerizable monomers to form a copolymer thereof, such as polymerization of styrene and butadiene to form poly (styrene-butadiene). , Polymerization of styrene and isoprene to form poly (styrene-isoprene), polymerization of styrene and ethyl acrylate to form poly (styrene-ethyl acrylate), and combinations thereof. A polymer is included.

Suitable reaction media used to carry out the method of the present invention include bulk or net suspension, emulsification, and solution systems.

In one embodiment, the monomer is about 1,000.
Waxy components having a low molecular weight of about 20,000, such as polyethylene, alkylenes such as polypropylene wax, and mixtures thereof can be admixed. The use of this type of component is desirable for certain toner applications. Suitable low molecular weight waxes such as polyethylene and polypropylene are disclosed in US Pat. No. 4,659,641.
Toner compositions can be prepared by a number of known methods, such as resin particles obtained by the method of the present invention, such as styrene butadiene copolymer and pigment particles,
For example, magnetite, carbon black, or mixtures thereof, and cyan, yellow, magenta, green, brown, red, or mixtures thereof, and preferably about 0.5% to about 5% charge enhancing additive, The toner composition formed is removed from the device by mixing and heating in a toner extruder, such as ZSK53 available from Werner Pfleiderer. Less than about 25 microns after cooling,
For the purpose of achieving toner particles preferably having a volume median diameter of about 6 to about 12 microns, eg Sturtevant
The toner composition is subjected to pulverization by using the ultra fine pulverizer. The diameter is measured with a Coulter Counter. Then, for the purpose of removing toner particles, ie toner particles having a volume median diameter of less than about 4 microns, for example, Donald
A son Model B classifier can be used to classify the toner composition.

Examples of suitable toner resins obtainable using the method of the present invention that can be selected for toner and developer compositions include styrene acrylate, styrene butadiene, vinyl resins (homopolymers and 2 Including the copolymers of the above vinyl monomers, the vinyl monomers include styrene, p-chlorostyrene, butadiene, isoprene, and myrcene), vinyl esters such as esters of monocarboxylic acids (methyl acrylate, ethyl acrylate). , N-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, phenyl acrylate, acrylonitrile, methacrylonitrile, acrylamide and the like). Suitable toner resins include
Styrene-butadiene copolymers, mixtures thereof and the like are included. Other suitable toner resins include styrene / acrylate copolymers, PLIOLITES®, and suspension polymerized styrene butadiene. U.S. Pat.No. 4,555
Reference may be made to No. 8,108, the disclosure of which is incorporated herein in its entirety.

In the toner composition, the resin particles are present in a sufficient but effective amount, for example from about 60 to about 90% by weight. Thus, if 1 wt% charge enhancing additive is present and contains 8 wt% pigment or colorant such as carbon black, then about 91 wt% resin is selected. Further, the charge enhancing additive may be coated on the pigment particles. When used as a coating, the charge enhancing additive shall be present in an amount of from about 0.1% to about 5%, preferably from about 0.3% to about 1%.

A number of well known suitable pigments or dyes can be selected as colorants for the toner particles, for example carbon blacks such as REGAL 330®, nigrosine dyes, aniline blue, magnetite, Or a mixture of these is included. The pigment, which is preferably carbon black, should be present in an amount sufficient to render the toner composition highly colored. Generally, the pigment particles comprise from about 1% to about 20% by weight, preferably from about 2 to about 1%, based on the total weight of the toner composition.
It is assumed that it is present in an amount of 0% by weight, but higher or lower content particles can be selected.

If the pigment particles are composed of magnetite, this can optionally enable a single-component toner, the magnetite being MAPICO BLACK.
A mixture of iron oxide, including those commercially available as _{(R) (FeO · Fe 2 O 3} ), which are in the toner composition in an amount of about 10 wt% to about 70 wt%, preferably from about It should be present in an amount of 10% to about 50% by weight.
A mixture of carbon black and magnetite can be selected, from about 1 to about 15% by weight carbon black,
Preferably about 2 to about 6% by weight carbon black,
Magnetite, such as MAPICO BLACK®, is present in an amount of, for example, about 5 to about 60, preferably about 10 to about 50% by weight.

The toner composition of the present invention may be blended with external additive particles containing a flowability auxiliary additive, which additive is usually present on the surface thereof. Examples of these additives are fumed silica such as AEROSI.
L <(R)>, metal salts and metal salts of fatty acids including zinc stearate, aluminum oxide, cerium oxide, and mixtures thereof, these additives generally comprising from about 0.1% to about 5% by weight. %, Preferably about 0.1% to about 1% by weight.
Some of the aforementioned additives are set forth in US Pat. Nos. 3,590,000 and 3,800,588, the disclosures of which are incorporated herein in their entirety.

In a further aspect of the invention, about 1% by weight, based on fumed silica such as AEROSIL®.
Surface treatment with a charge additive in an amount of about 30% by weight, preferably 10% by weight, and then adding it to the toner in an amount of 0.1-10, preferably 0.1-1% by weight. You can

It is also possible to include low molecular weight waxes in the toner composition, which may be, for example, Allied C
Eastman Chemic, polypropylene and polyethylene commercially available from hemical and Petrolite Corporation
EPOLENE N-15 available from al Products, Inc.
(Registered trademark), VISCOL 550-P (registered trademark), Sanyo Kase
Low weight average molecular weight polypropylene, commercially available from iKK, and similar materials. The commercial polyethylene selected has a molecular weight of about 1,000 to about 1,500, while the commercially available polypropylene utilized for the toner composition is believed to have a molecular weight of about 4,000 to about 5,000. Many polyethylene and polypropylene compositions useful in the present invention are set forth in British Patent No. 1,442,835, the disclosure of which is incorporated herein in its entirety.

The low molecular weight wax materials will be present in the toner composition or polymer resin beads of the present invention in various amounts, but generally these waxes will be present in the toner composition at about 1%.
% To about 15% by weight, preferably about 2% to about
It should be present in an amount of about 10% by weight and, in some embodiments, can function as a release agent for fuser rolls.

Included within the scope of this invention are pigmented toner and developer compositions, which include toner resin particles, carrier particles, charge enhancing additives (shown here), and pigments or pigments. Agents include red, blue, green, brown, magenta, cyan and / or yellow particles, and mixtures thereof.

More specifically, examples of magenta materials that can be selected as pigments for the production of color images utilizing developer compositions with charge enhancing additives include, for example, 2,9-
Dimethyl-substituted quinacridone and anthraquinone dyes (Cl 60710 for color index, Cl Dispersed Red 1
5)), diazo dyes (color index Cl 26050, Cl Solvent Red 19) and the like. Examples of cyan materials that can be used as pigments include copper tetra-4- (octadecyl sulfonamide) phthalocyanine, X-copper phthalocyanine pigment (described in the color index as Cl 74160, Cl Pigment Blue), and Anthrathrene Blue. (Identified as Cl 69810, Special Blue X-2137 in the color index) and the like, while examples of yellow pigments that may be selected are Diarylide Yellow 3,3-dichlorobenzidene acetoacetanilide, Monoazo pigments (color index Cl 12700, identified as Cl Solvent Yellow 16), nitrophenylamine sulfonamide (color index Foron Yellow SE / GLN, Cl Dispers
ed Yellow 33), 2,5-dimethoxy
-4-Sulfonanilide Phenylazo-4'-chloro-2,5-dimethoxyacetoacetanilide, and Permanent Yellow
It is FGL. As long as the object of the invention is achieved, the pigments mentioned above will be incorporated into the toner composition in various suitable amounts. In one aspect, these colored pigment particles are
It should be present in the toner composition in an amount from about 2% to about 15% by weight, calculated by weight of the toner resin particles.

For the formulation of the developer composition, the toner particle carrier component, in particular the toner composition, is mixed with a triboelectrically envisaged opposite polarity. Therefore, the carrier particles are selected to have a negative polarity, which allows the positively charged toner particles to be adsorbed to surround the carrier particles. Examples of carrier particles include iron powder, steel, nickel, iron,
Ferrites including copper zinc ferrite are included. In addition, nickel berry carriers such as those shown in US Pat. No. 3,847,604 can be selected as carrier particles, the disclosure of which is incorporated herein in its entirety. The selected carrier particles can be used with or without a coating, but the coating generally contains a terpolymer of styrene, methyl methacrylate, and a silane such as triethoxysilane, Reference may be made to US Pat. No. 3,526,533, US Pat. No. 4,937,166, and US Pat. No. 4,935,326, the disclosures of all of which are incorporated herein by reference, for example, KYNAR.
A mixture of (registered trademark) and polymethylmethacrylate (40/60) is included. The coat weight may vary as indicated herein, but generally a coat weight of about 0.3 to about 2, preferably about 0.5 to about 1.5% by weight should be selected.

Further, the carrier particles, which are preferably spherical in shape, generally have a diameter of from about 50 microns to about 1,000 microns, and in one embodiment from about 70 to about 175 microns.
This allows them to have sufficient density and inertia to avoid sticking to the electrostatic image during the development process. The carrier component can be mixed with the toner composition in various suitable combinations, but from about 10 parts to about 20 parts.
About 1 to 1 toner per 0 part by weight of carrier
Best results are obtained when about 5 parts are selected.

The compositions of the present invention can be prepared by a number of known methods, such as those shown herein, which include toner resin particles obtained by the method of the present invention and pigment particles or colorants. Mechanically abrading after extrusion-melt compounding with the charge enhancing additive. Other methods include those well known in the art such as spray drying, melt dispersion, extrusion. Further, as shown here, it is also possible to add the silica surface-treated with the charge additive after preparing the toner composition without using the charge enhancing additive in the lump toner.

Toner and developer compositions can be selected for use in electrostatographic imaging devices which incorporate conventional photoreceptors therein, so long as they can be positively or negatively charged. Thus, the toner and developer compositions can be used with negatively chargeable layered photoreceptors such as those disclosed in US Pat. No. 4,265,990, the disclosure of which is incorporated herein in its entirety. Examples of inorganic photoreceptors that may be selected for the imaging and printing processes include selenium, selenium alloys such as selenium arsenic, selenium tellurium, halogen-doped selenium materials, and halogen-doped selenium alloys. Flexible layered imaging members with charge transport and photogenerating layers can be selected for the imaging and printing process.

After preparation, the toner composition is typically jetted and graded to allow toner particles of a suitable average diameter of from about 5 to about 25 microns, more preferably from about 8 to about 12 microns. The toner composition also preferably has a triboelectric charge of from about 0.1 to about 2 femto coulombs per micron, as measured by known charge spectrographs. The mixing time for the toner is about 5 seconds to 1 minute, as measured by known charge spectrograph,
More preferably, it is about 5 to about 15 seconds. These toner compositions with rapid mixing properties enable development of the image in, for example, an electrostatographic imaging device, and in some cases even at high toner dispense rates, eg, greater than 20 grams per minute, the image is Toner compositions of this type, which are substantially free of deposited background, can be selected for high speed electrophotographic machines, ie, greater than 70 copies per minute.

Toner compositions prepared from the resins of the present invention are also known when using one aspect of the charge enhancing additives of the desired narrow charge distribution, about 0.1 to about 5% by weight. Preferably 10 to about 50, more preferably about 1 per gram as measured by the Faraday Box method.
Optimal charge triboelectric charging value from 0 to about 35 microcoulombs,
And having a rapid charge time of less than 15 seconds as measured by a charge spectrograph, and more preferably in some embodiments from about 1 to about 14 seconds.

[0056]

EXAMPLES The following examples are provided to further identify certain aspects of the present invention, which are intended to illustrate, but not limit, the scope of the invention. It should be noted that there is no. Parts and percentages are by weight unless otherwise indicated. A comparative example is also shown.

In all of the method examples except Comparative Example 1,
An ultrasonic radiation source as described in Example 1 was used and the low temperature was 40-70 ° C. Comparative examples and data are also shown.

Comparative Example 1 Styrene suspension suspension without using stable free radical reagent
Alkanol (Alkano) in free radical polymerized water (100 ml)
l, 48 mg) tricalcium phosphate (3.
0 grams) and naphthalene sulfonate available from DuPont are added to the modified Parr reactor and the reactor is purged with nitrogen for 8 minutes over 8 minutes.
Heated to 0 ° C. Under 60 pounds of nitrogen per square inch, a solution of benzoyl peroxide (2.0 grams, 0.008 moles) in styrene (78 grams, 0.75 moles) was added to the reactor and heated at 80 ° C for 3 hours 20 hours. The reaction was continued for a minute.
Then, it heated at 95 degreeC and continued the reaction at that temperature for 2 hours and 20 minutes. Samples were removed from the reactor at the time intervals or reaction times (minutes) shown in Table 1 (0.5-1.0 grams in the examples unless otherwise indicated), cooled, treated with concentrated nitric acid and suspended reagent. Was dissolved, rinsed with water and dried. The molecular weight characteristics of the intermediate material and the final polystyrene product are shown in Table 1. Polydispersity (Mw / Mn) is shown in the column labeled PD.

[0059]

[Table 1]

Example 1 Ultrasonic irradiation using a stable free radical reagent (TEMPO)
50 equipped with an oil bath under the beaker to heat the bulk polymerization solution of styrene through
Styrene monomer (15 grams, 0.144 moles), benzoyl peroxide (0.052 grams, 0.215 millimoles), and a stable nitroxide radical, TEMPO (0.045 grams, per 0 milliliter metal beaker). 0.288 mmol) is added. After heating to a solution temperature of 60 ° C, 300 watt model ultrasonic horn (Cole-Parmer ultrasonic homogenizer 4710 horn)
Is placed in the monomer solution and the power adjustment setting is put in setting number 9 for 30 minutes. When ultrasonic energy is applied to the monomer solution, the metal beaker is moved in all directions in an oil bath to provide proper mixing of the solution during polymerization. At this stage, ultrasonic energy is continued for another 30 minutes after the sample of the solution is removed. This polymerization procedure is continued for a total of 4 hours. Samples (0.5 to 1.0 grams in each example unless otherwise indicated) are removed from the reaction mixture every 30 minutes and the molecular weight characteristics of the polystyrene product are measured. Mn for polystyrene is 8,826 and Mw is
38,965, and PD, polydispersity is 1.26. Mn
And Mw are refractive index detectors, HP1047, calibrated with polystyrene standards ranging from 2,000,000 to 500 Daltons.
Evaluate using a Hewlett Packard gel permeation chromatograph model HP1090 with A.

Example 1 shows that the reaction can be conveniently carried out in the absence of solvent or in bulk. The molecular ratio of TEMPO to benzoyl peroxide is 1.3: 1, which is the optimum ratio. This example also shows that overall reaction temperatures for moderated free radical polymerization of styrene can be achieved at low reaction temperatures and short times, while still producing polymers with excellent high molecular weight.

Example 2 Using a stable free radical reagent (4-oxo-TEMPO)
50 equipped with an oil bath under the beaker to heat the bulk polymerization solution of n-butyl acrylate via sonication
N-butyl acrylate monomer (15 grams, 0.117 mol), azobisisobutyronitrile (AIBN) (0.050 grams, per 0 milliliter metal beaker)
0.291 mmol), and a stable nitroxide radical, 4-oxo-TEMPO (0.085 grams, 0.500).
Mmol) is added. After heating to bring the temperature of the solution to 50 ° C., place a 300 watt model ultrasonic horn in the monomer solution and put the power adjustment setting in setting number 9 for 30 minutes. When ultrasonic energy is applied to the monomer solution, the metal beaker is moved in all directions in an oil bath to provide proper mixing of the solution during polymerization. At this stage, a sample of the solution (0.5-1 ..
After taking out 0 gram), add 3 more ultrasonic energy.
Continue for 0 minutes. This polymerization procedure is continued for a total of 4 hours. A 0.5-1.0 gram sample is removed from the reaction mixture every 30 minutes to determine the molecular weight profile of the poly (n-butyl acrylate) product. The Mn for poly (n-butyl acrylate) is 7,939, Mw is 12,247, and PD, polydispersity is 1.54. Mn and Mw are
Hewl with an HP1047A refractive index detector calibrated with polystyrene standards ranging from 2,000,000 to 500 Daltons
Evaluate using the ett Packard gel permeation chromatograph model HP1090.

Example 2 shows that the reaction can be conveniently carried out in the absence of solvent or in bulk. The molecular ratio of TEMPO to benzoyl peroxide was 1.7: 1, which is not considered to be the optimum ratio for this example, and the optimized ratio is narrower than the 1.54 obtained. Polydispersity will be possible. This example also shows that at low reaction temperatures and short times, the overall reaction temperature for moderated free radical polymerization of n-butyl acrylate can be achieved.

Example 3 Preparation and Evaluation of Magnetic Toner The polymer resin obtained by the stable free radical polymerization method of Example 2 (74% by weight of the total mixture) was 10% by weight of REGAL 330® carbon. It can be extruded with black and 16 wt% MAPICO BLACK® magnetite at 120 ° C. and the extrudate milled in a Waring blender and jetted into 8 micron number average sized particles. Positively charged magnetic toner is 0.12 grams of AEROSIL R972 in a 1: 1 weight ratio.
(Registered trademark) (Degussa Chemicals) and TP-302, naphthalenesulfonic acid and quaternary ammonium salt (Nachem / Hod
ogaya SI) can be prepared by surface treating toner (2 grams) jetted with a charge control agent.

Thereafter, 3.34 parts by weight of the above toner composition was added to an upper polymer mixture (coating weight: 70% by weight KYNAR®, polyvinylidene fluoride and 30% by weight polymethylmethacrylate). Is about 0.9%), and by mixing with 96.66 parts by weight of a carrier comprising a steel core having a diameter of 98 microns,
A developer composition can be prepared. Cascade development can be used to develop Xerox Model D photoreceptors using "negative" targets. The exposure can be set to 5-10 seconds and a negative bias can be used to dark transfer the positive toner image from the photoreceptor to the paper.

Fuse evaluation can be carried out using a Xerox 5028® soft silicone roll fusing device operating at 3 inches per second.

While a toner prepared from a resin synthesized by a free radical polymerization method without using a stable free radical reagent gives a wide polydispersity, a stable free radical polymerization having a narrow polydispersity as a toner. The minimum fixing and hot offset temperature (° F) of the polymer are expected to be improved. The actual fuser roll temperature can be measured using an Omega pyrometer and checked using a wax vapor indicator.
The extent of the developed toner image on the paper after fusing is evaluated using the Scotch tape test. Fixing levels are expected to be excellent and can be compared to fixings obtained with toner compositions prepared from other methods for preparing toners having resins with high molecular weight and narrow polydispersity. Typically 95% after stripping the tape as measured by a densitometer
Toner images that exceed 100 mm remain fixed on the copy sheet.

A supporting substrate of aluminum, a photogenerating layer of trigonal selenium, and an arylamine N, N'-diphenyl-N,
N'-bis (3-methylphenyl) 1,1'-biphenyl-4,4'-
Images can be developed in a xerographic imaging tester equipped with a negatively charged layered imaging member composed of a diamine (45% by weight dispersed in 55% by weight polycarbonate MAKROLON®). (See US Pat. No. 4,265,990), images with toner compositions prepared from the polymer products of Examples 1 and 2 have been shown to have extended times beyond about 75,000 imaging cycles. Is expected to be of excellent quality and high resolution with no background deposits over the entire imaging cycle.

Other toner compositions can be readily prepared from the polymers and copolymers of the invention by conventional means, including colored toners, single component toners, multicomponent toners, and specific performance toners. Toners containing additives and the like are included.

[0070]

Industrial Applicability The above-described stable free radical reagent-relaxed polymerization method can be applied to a wide range of organic monomers to provide a novel toner resin material having desired electrophotographic characteristics, coating and the like. . For example, the block copolymer is
It can be selected as the dispersion for the photoreceptor pigment. Multiple modality resins can be utilized as low melting toner resins, and some single modality resins can be used to modify the surface of carbon black and other pigment particles to make the pigment particles a host polymer or dispersion. It can be more miscible with the medium. Furthermore, it is narrow (PD)
Molecular weight resins such as poly (styrene-butadiene) are
It can be selected as an improved toner resin for copying applications.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Peter M. Katmaier Canada El 5 El 1 E 5 Mississauga Council, Ontario Ring Road 2421 (72) Inventor Michael Kay. Georges Canada N 1 G 3 N 8 Guelph Ironwood Road, Ontario 384 (72) Inventor Gordon Kay. Hummer Canada L5L2P4 Missouriau, South Ontario South Milway No. 1-2280 (72) Inventor Richard P.H. N. Verezin Canada El 5 El 5 Sea 3 Mississauga, State of Ontario Cherrington Crescent 3515 (72) Inventor Markody. Savan Canada M9B4N1Entobi Cork Charleston Road 65

Claims (4)

[Claims] 1. A method of free radical polymerization for the preparation of a thermoplastic resin, wherein a mixture of a free radical initiator, a stable free radical reagent and at least one polymerizable monomer compound is heated and the heating is carried out. Is performed at a temperature of about 40 to about 100 ° C. in the presence of ultrasonic radiation, the mixture is cooled, the thermoplastic resin is isolated if necessary, and the thermoplastic resin is washed and dried. A free radical polymerization method for the preparation of a thermoplastic resin, comprising: 2. One or more thermoplastic resins are obtained with a high conversion of monomer to one or more resins of at least about 50%, the one or more resins comprising about 1. The free radical polymerization process of claim 1 having an excellent polydispersity of from 05 to about 1.95. 3. A second mixture comprising a free radical initiator, a stable free radical reagent, and at least one polymerizable monomer compound is added to the resulting product resin, wherein: And wherein the polymerizable monomer compound of the second mixture contains the same components as the polymerizable monomer compound of the first mixture, and the free radical initiator of the second mixture and the The stable free radical reagent is the same as or different from the free radical initiator and the stable free radical reagent of the first mixture, thus forming a combined mixture, heating the combined mixture, and heating the combined mixture. A first product resin formed from the first intermediate product resin and the added second monomer, and a second product resin formed from the second monomer. Comprising forming a third mixture comprising a mixture of a thermoplastic resin, wherein the third mixture comprises cooling the said first product resin and said second product resin,
Each has a narrow polydispersity of about 1.05 to about 1.95, and the heating is about 40 to about 10 in the presence of ultrasonic radiation.
The free radical polymerization method according to claim 1, which is carried out at a temperature of 0 ° C. 4. A method of preparing a toner comprising: a free radical initiator, a stable free radical reagent, a pigment, and at least one monomer component at about 50 ° C. to about 100 ° C. in the presence of ultrasonic radiation. Heating the mixture with the resin, the resin having a polydispersity of about 1.05 to about 1.95 and a monomer to resin conversion of at least about 50%. Toner preparation method.