MXPA99003835A - Polyes process - Google Patents

Abstract

The present invention relates to: A process for the preparation of an unsaturated polyester comprising (i) reacting an organic dial with a cyclic alkylene carbonate in the presence of a first catalyst to thereby form a polyalkoxydiol, and (ii) adding optionally thereto an additional amount of cyclic alkylene carbonate in the presence of a second catalyst, and (iii) subsequently polycondensing the resulting mixture with a dicarboxylic acid.

Description

POLYESTER PROCESS BACKGROUND OF THE INVENTION The present invention relates in general to a process for the preparation of polyester polymers, and polyesters that can be selected for the preparation of polyester polymers that are preferably subsequently crosslinked, for use as organic pigment resins. In embodiments, the process of the present invention comprises a monomer addition process of for example, alkoxylating first a dihydroxy-containing monomer, such as a dihydroxy-alkane or a dihydroxy-aryl, with a cyclic alkylene carbonate in the presence of a catalyst such as an alkali carbonate, optionally followed by the addition of a further amount of the cyclic alkylene carbonate in the presence of a second catalyst such as an alkaline alkoxide, and followed by a subsequent addition of a diacid, such as a saturated or unsaturated aliphatic diacid, or an aromatic diacid, to allow the formation of a polyester resin, saturated or unsaturated.

REF .: 29724 PREVIOUS TECHNIQUE In general, polyester resins are generally prepared by a polycondensation process comprising the reaction of a diol monomer and a diacid or diester monomer and the production of water or an alcohol as a by-product, which is collected by distillation. Similarly, unsaturated polyester resins can be prepared by this process, with the main exception that the diacid monomer is unsaturated, ie, it is comprised of an alkene segment such as fumaric or maleic acid, or diesters thereof. The electrophotographic organic pigments are generally comprised of a resin, such as a polyester, a pigment and optionally a charge control agent. Many formulations of organic pigment are known, and more specifically, a preferred formulation of organic pigment is comprised of a polyester resin, unsaturated, crosslinked, such that low fixing temperatures, desirable and displacement properties are achieved, see, US Pat. No. 5,227,460, the disclosure of which is hereby incorporated by reference in its entirety, wherein a poly (bisphenol, propoxylated co-fumarate) is described as a preferred polyester, unsaturated resin. it is crosslinked to a gel content of up to about 40 weight percent using a peroxide to provide an organic pigment useful for electrophotographic processes. Polyester, unsaturated resins derived from bisphenol A, propoxylated, with fumaric acid are known. More specifically, the propoxylated bisphenol A used is, for example, a mixture of monomers prepared by the anionic propoxylation of bisphenol A with propylene oxide, in the presence of an alkaline hydroxide catalyst in a pressurized container, and in where the obtained mixtures are the alkaline salts of 4-. { 2-hydroxyethyl) -bisphenol A, bis 4,4 '(2-hydroxyethyl) -bisphenol A, and 4- (2'-hydroxyethyl-2-oxyethyl) -? - (2-hydroxyethyl) -bisphenol A. There is an alternative alkoxylation condensation method which can be achieved by the reaction of a diol with a cyclic alkylene carbonate, and specifically wherein the bisphenol A can be condensed with a carbonate of cyclic propylene in the presence of a catalyst and the release of carbon dioxide as the by-product at elevated temperatures, thereby producing a mixture of propoxylated bisphenol A. The latter method of condensation has numerous economic advantages in terms of monomer cost, and simplicity. In U.S. Patent No. 5,449,719, the disclosure of which is hereby fully incorporated by reference, there is illustrated a two step process for the preparation of polyester resin, unsaturated, and comprising the first reaction of a phthalate and a glycol to provide a transesterified product, and subsequently a second reaction comprising reacting the product with an unsaturated dicarboxylate monomer. This differs from the present invention in that for example, the first reaction comprises the condensation of a diol with an alkylene carbonate and generates carbon dioxide as the by-product. In U.S. Patent No. 5,407,772, the disclosure of which is hereby fully incorporated by reference, there is illustrated a linear, unsaturated polyester having repeating units of a reaction product of a first monomer, a second monomer , a third monomer and optionally a fourth monomer. Linear polymers have a glass transition temperature ranging from about 52 ° C to about 61 ° C, and the first monomer must have a weight average molecular weight of less than 200, the second monomer may be a dicarboxylic acid or a diester which It is different than the third monomer. The concentration of the second polymer residues, derived from the second monomer, ranges from about 3 weight percent to about 15 weight percent, based on the total weight of the polymer. The third monomer is an aromatic dicarboxylic acid or an ester thereof. The fourth monomer is a diol having a higher molecular weight than the first monomer. In a process for preparing the inventive polymer of the '772 patent, the first, the second, the third (and optionally a quarter) monomer and / or a catalyst are subjected to transesterification to form the linear, unsaturated polyester.

In U.S. Patent No. 4,788,122, the production of an organic pigment polyester resin obtained by the co-polycondensation of (a) a polyalkylene-bis (4-hydroxy-phenyl) propane diol component is disclosed. and (b) an acid component, enhanced by incorporating a styrene copolymer or derivative thereof and a vinyl, carboxylic monomer into the acid component. In the United States Patent No. ,466,554, there is disclosed an organic pigment composition with modified polyester resin free of acid end groups, and obtained from the condensation of a first diol monomer, a second diacid monomer, and a third such as monovalent or a monomer of diacid Similarly, in U.S. Patent No. 5,686,218, a process is described which comprises reacting an end-capped polyester resin with hydroxyl portions or groups with an organic acid anhydride, at a temperature of about 125 ° C. to about 200 ° C, thereby resulting in a polyester resin capped at the end with acidic acid-containing portions. They are illustrated in U.S. Patent Nos. 4,988,794; 4,727,011; 4,533,614 and 5,366,841 other organic pigments based on polyester and processes thereof. In the United States Patent No. 2,766,292, there is disclosed a process for preparing oxyalkylation derivatives such as oxyalkylated, substantially dilute, anhydrous derivatives of an anhydrous solid, the pentaerythritol compound susceptible with oxyalkylation, which satisfies one of the following two conditions (a) is infusible; (b) undergoes at least partial decomposition if maintained at its onset of melting temperature for a period of at least 15 minutes in the presence of an oxyalkylation catalyst, and solid which is insoluble in a solvent removable by distillation, resistant to oxyalkylation; process which consists in reacting the solid with at least one alkylene carbonate selected from the alkylene carbonate, propylene carbonate, and butylene carbonate, in the presence of an oxyalkylation catalyst at a temperature which produces carbon dioxide. In U.S. Patent No. 4,131,731, a process for preparing linear polycarbonates containing terminal hydroxyl groups with the essential exclusion of other end groups by reacting glycols having a greater carbon number > 4 and cyclic esters of carbonic acid via an ester exchange reaction of 100 ° C to 300 ° C, and 300 mm Hg. In U.S. Patent No. 5,373,030, a process for the preparation of polyurethane foams is described and similarly, in US Patent No. 5,332,860 the use of polyols for preparing polyurethane foams having an improved retention of insulating properties. United States Patent No. ,714,568, a process is described comprising the reaction of a polyfunctional organic acid or anhydride and an organic, cyclic carbonate compound in the presence of the catalyst selected from the group consisting of an alkali metal, thereby generating a polyester resin or co-polyester. Japanese Patent Publication JP 10077336 A2 describes a process for the preparation of co-polyester by the reaction of an aromatic diol with an alkylene carbonate in the presence of an alkali carbonate catalyst to form a diol, in a conversion of, for example, more than about 75 percent as measured by the emission of carbon dioxide byproduct, followed by the subsequent addition of yet another diol and a diacid and continuing polymerization at high pressure and high temperature of approximately 240 ° C, for produce the co-polyester resin, mentioned above. The isomeric mixtures in the present invention comprised, for example, of isomers I, II and II are not believed to be described in the documents of JP '336 particularly in the isomer ratios from about 0 to about 5 weight percent of the isomer I, from about 89 to about 97 percent by weight of isomer II, and from about 0 to about 15 percent by weight of isomer III, by the use of a mixture of both an alkali carbonate and an alcohol. The process of the present invention differs, for example, in that the amounts of the specific mixtures of the three isomers are controlled and obtained by the use of the specific catalyst in a multi-step process to form polyester resins which can be selected for the use as binders of organic pigment. Additionally, unsaturated polyester, poly (propoxylated bisphenol A co-fumarate) is apparently not disclosed in the above JP '336 document. The unsaturated polyesters of the present invention are of importance for crosslinking to a high gel content of for example, from about 5 to about 50 percent, gel. Additionally, in the process of the present invention, high pressures are not necessarily used in the formation of the polyester resins, and in embodiments, the highest temperature selected to generate the polyester resin is from about 200 ° C to about 215 °. C. Additionally, the '336 patent mentioned above utilizes both a diol and a diacid during the polymerization steps to form a co-polyester. This differs from the present invention, wherein in the embodiments a diacid is used to form the polyester during the polycondensation step. Japanese Patent Publication JP 10095840 A2 describes a process for the preparation of co-polyesters by the reaction of an aromatic diol with an alkylene carbonate in the presence of an alkaline carbonate catalyst to form a diol, at a conversion of for example , to more than about 75 percent as measured by the emission of the carbon dioxide byproduct, followed by the subsequent addition of yet another diol and a mixture of diacid and the continuation of polymerization at high pressure and temperature of approximately 240 ° C to produce the co-polyester resin mentioned above. The isomeric mixtures in the present invention are comprised of the isomers I, II and III which do not appear to be recognized or described in the JP '840 documents, particularly in a 3-step monomer process for producing the isomer ratios from about 0 to about 1 weight percent of the isomer I, from about 89 to about 97 weight percent of the isomer II, and from about 3 to about 15 weight percent of the isomer III, by the use of a mixture of both a alkali carbonate as an alkali derived from alcohol. Additionally, the '840 patent mentioned above utilizes both a diol and a diacid during the condensation steps to form a co-polyester. This differs from the present invention, wherein in single modalities a diacid is needed to form the polyester during the polycondensation step. Japanese Patent Publication JP 10087802 A2 describes a process for the preparation of polyester obtained by polymerizing an aromatic dicarboxylic acid and an aliphatic glycol to form a polyester oligomer terminated with carboxylic group, with an esterification degree of about 80 percent conversion , and a cyclic 5- or 6-membered alkylene carbonate fusion reaction with an aromatic diol in the presence of a catalyst such as lithium.

BRIEF DESCRIPTION OF THE INVENTION It is a feature of the present invention to provide an economical process for the preparation of polyester resins. It is another feature of this invention to provide an inexpensive, multi-step "pot" process for the preparation of polyester resins, such as a polyester resin, unsaturated, and wherein the first step is comprised of the alkoxylation of a diol, such as bisphenol A with an alkylene carbonate in the presence of an alkali carbonate such as potassium carbonate, and optionally followed by a subsequent step of adding more alkylene carbonate in the presence of a second alkaline-alkoxide catalyst such as potassium methoxide, followed by the polycondensation step of adding it to a diacid such as fumaric acid to produce the polyester resin in further heating and reducing the pressure. Additionally, it is a feature of this invention to provide a process for the preparation of an unsaturated polyester comprising (i) reacting an organic diol with a cyclic alkylene carbonate in the presence of a first catalyst to thereby form a bis-alkoxy diol, and (ii) optionally adding thereto an additional amount of cyclic alkylene carbonate in the presence of a second catalyst, and (iii) subsequently polycondensing the resulting mixture with an unsaturated diacid.

Yet, it is another feature of the invention, to provide a process for the preparation of an unsaturated polyester resin, which comprises: (i) reacting an organic diol with a cyclic alkylene carbonate in the presence of a first catalyst to form thus a bis-alkoxy diol, and wherein the bis-alkoxy diol is comprised of the isomers of Formula 1 or Formula 2 with from about 2 to about 5 weight percent of isomer I, from about 95 to about 99 weight percent of the isomer III, and from about 0 to about 3 weight percent of the isomer III, and wherein the sum of I, II, and III is about 100 percent, and wherein the isomers are from the formula as illustrated in Formula 1. In a further feature of this invention, processes are provided for the preparation of an unsaturated polyester resin comprising (i) reacting a organic diol with a cyclic alkylene carbonate in the presence of a first catalyst to thereby form a bis-alkoxy diol; and (ii) adding thereto an additional amount of cyclic alkylene carbonate in the presence of a second catalyst, and wherein the bis-alkoxy diol is comprised of the isomers with from about 0 to about 1 weight percent of the isomer I, from about 85 to about 97 weight percent of the isomer II, and from about 3 to about 15 percent by weight of isomer III, and the sum of I, II and III is approximately 100 percent and wherein the isomers are of the formula as illustrated at 1. It is also a feature of the invention to provide a crosslinked polyester, generated by the reactive extrusion of a peroxide and an unsaturated polyester. Furthermore, in yet another feature of this present invention, a polyester resin, unsaturated, poly (propoxylated bisphenol A co-fumarate), which can be crosslinked to about 50 percent gel content with a peroxide such as peroxide, is provided. of benzoyl and lauryl. In a further feature of this present invention, there is provided an organic pigment comprised of a polyester resin, unsaturated, prepared by a two- or three-step monomer addition process, a dye and optionally a charge enhancing agent. In yet a further feature, a two-step monomer addition process for the preparation of an unsaturated resin with a glass transition temperature from about 58 ° C to about 62 ° C is provided., and more preferably from about 58 ° C to about 60 ° C. In addition, in yet a further feature, a three step monomer addition process is provided for the preparation of an unsaturated resin with a vitreous transition temperature from about 52 ° C to about 57.9 ° C. In addition, in another feature, a process for the preparation of an established resin is provided, wherein the first step generates a mixture of three isomers of propoxylated bisphenol A, by using alkaline carbonate catalysts. These and other features of the present invention can be provided by first alkoxylating a dihydroxy-containing monomer, such as a dihydroxy-alkane and or dihydroxy-arylene, with an alkylene carbonate in the presence of a catalyst such as an alkali carbonate or alkoxycarbonate. alkali, to form an alkoxy, preferably in an amount of 100 percent, and preferably the isomer formulas illustrated herein, optionally followed by the second subsequent addition of the alkylene carbonate in the presence of a second catalyst alkaline alkoxide, and subsequently followed with the process of polycondensation by the addition of a diacid, such as a saturated or unsaturated aliphatic diacid or aromatic diacid, to enable the manufacture of a saturated or unsaturated polyester resin. The aspects of the present invention relate to a process for the preparation of an unsaturated polyester comprising (i) reacting an organic diol with a cyclic alkylene carbonate in the presence of a first catalyst to thereby form a polyalkoxydiol, and (ii) optionally, but preferably adding an additional amount of cyclic alkylene carbonate thereto in the presence of a second catalyst, and (iii) subsequently polycondensing the resulting mixture with a dicarboxylic acid, a process wherein the preparation of a unsaturated polyester comprises (i) reacting an organic diol in an effective amount of, for example, from about 0.95 to about 1.05 mole equivalents with a cyclic alkylene carbonate in an effective amount of for example, about 1.95 to about 2.05 mole equivalents, in the presence of a first alkaline carbonate catalyst in an amount effective, for example, about 0.001 to about 0.01 equivalent moles, to thereby form a polyalkoxydiol, and wherein the polyalkoxydiol is comprised of isomers with, for example, from about 2 to about 5 weight percent of isomer I, from about 95 up to about 99 weight percent of the isomer II, and from about 0 to about 3 weight percent of the isomer III, and the sum of I, II and III is about 100 percent and where the isomers are of the formula as illustrated in Formula 2.

II lll and followed by the subsequent polycondensation of the resulting polyalkoxydiol with a dicarboxylic acid in an amount from about 0.95 to about 1.05 mol equivalents, wherein R is an aromatic component, R 'is hydrogen or alkyl, is already zero, 1 or 2, or a mixture of zero, 1 and 2; a process wherein the preparation of an unsaturated polyester comprises (i) reacting an organic diol in an amount from about 0.95 to about 1.05 mole equivalents. with a cyclic alkylene carbonate in an amount from about 1.95 to about 2.05 mole equivalents, in the presence of a first alkaline carbonate catalyst in an amount from about 0.001 to about 0.1 mole equivalents; adding to this (ii) from about 0.05 to about 0.45 mole equivalents of cyclic alkylene carbonate in the presence of a second alkaline alkoxide catalyst in an amount from about 0.001 to about 0.1 mole equivalents, to thereby form a polyalkoxydiol comprised of the isomers with from about 0 to about 1 weight percent in isomer I, from about 85 to about 97 weight percent of isomer II and from about 3 to about 15 weight percent of isomer III and the sum of , II and III is approximately 100 percent wherein the isomers are of the formula as illustrated in Formula 1 below.

III wherein a is as illustrated herein, and followed by the subsequent polycondensation of the resulting polyalkoxydiol with a dicarboxylic acid in an amount from about 0.95 to about 1.05 mole equivalents; a process in which a crosslinked polyester is formed, generated by the reactive extrusion of a peroxide and an unsaturated polyester; a process wherein the first catalyst is an alkaline carbonate; a process wherein the second catalyst is an alkaline alkoxide; a process where the reaction is achieved in the presence of heat; a process wherein the reaction is achieved by heating a temperature from about 160 ° C to about 215 ° C; a process wherein the reaction is achieved by heating to a temperature from about 180 ° C to about 200 ° C; a process where polycondensation is achieved by heating; a process wherein the polycondensation is achieved by heating to a temperature from about 185 ° C to about 225 ° C; a process wherein the polycondensation is achieved by heating to a temperature from about 185 ° C to about 225 ° C for a duration from about 1 to about 5 hours, followed by reducing the pressure from about 760 Torr to about 1 Torr over a period of time from about 1 to about 6 hours; a process wherein subsequent to the polycondensation, the reaction mixture is cooled; a process wherein cooling is from about 25 ° C to about 40 ° C; a process where the cooling is from approximately 25 ° C; a process in which a crosslinked polyester is formed, generated by the reactive extrusion of a peroxide and an unsaturated polyester; a process wherein the crosslinking is represented by a gel content of from about 3 to about 75 percent; a process wherein the crosslinking is represented by a gel content of from about 3 to about 45 percent; a process wherein an unsaturated polyester resin of poly (bisphenol co-fumarate, propoxylated), poly (bisphenol co-fumarate, ethoxylated), poly (bisphenol co-fumarate, butyl. bisphenol fumarate, co-ethoxylated with co-propoxylated bisphenol), poly (1,2-propylene fumarate), poly (propoxylated bisphenol co-maleate), poly (bisphenol ethoxylated co-maleate), poly (co- bisphenol, butyloxylated maleate), poly (bisphenol co-maleate co-ethoxylated with co-propoxylated bisphenol), poly (1,2-propylene maleate), poly (propoxylated bisphenol co-t-taconate), poly (co- ethoxylated bisphenol itaconate), poly (butyloxylated bisphenol co-itaconate), poly (bisphenol co-i taconate, co-ethoxylated with co-propoxylated bisphenol), or poly (1,2-propylene co-itaconate); a process wherein the diol is 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, pentylene glycol, hexylene glycol, diphenol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2-bis (4-hydroxyphenyl) propane, , 2-bis- (3-hydroxy phenyl) propane, 2, 3-bis- (2-hydroxyphenyl) propane, 2, 2-bis- (3-hydroxyphenyl) propane, 2,2-bis- (5-hydroxyphenyl) propane, bisphenol A, bisphenol A ethoxyl-ado, bis- (4-hydroxyphenyl) methane, 1, 2-bis- (4-hydroxyphenyl) ethane, cis-1,4-dihydroxy-cyclohexane, trans-1,4-dihydroxycyclohexane , trans-1,3-dihydroxy-cyclohexane, cis-1,3-dihydroxy-cyclohexane, and mixtures thereof and diols which select an amount from about 0.90 mole equivalents to about 1.1 mole equivalents, based on about 1 mole equivalent of the dicarboxylic acid used; a process wherein the diol is 2,2-bis (4-hydroxyphenyl) propane or bisphenol A; a process wherein, the dicarboxylic acid is fumaric acid, malonic acid, itaconic acid, 2-methylitaconic acid, maleic acid, maleic anhydride, a) adipic, succinic acid, suberic acid, 2-ethyl-succinic acid, glutaric acid, acid dodecyl succinic acid, 2-methyladicic acid, pimelic acid, azeilic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,2-cyclohexanedioic acid, 1,3-cyclohexanedioic acid, 1,4-cyclohexanedioic acid, dialkyl esters where alkyl contains from 2 to about 22 carbon atoms and are esters of malonate, succinate, fumarate, itaconate, terephthalate, isophthalate, phthalate, cyclohexanedioate, mixtures thereof, and diacids which are optionally selected in an amount from about 0.95 mole equivalents to approximately 21.1 mol equivalents, based on 1 mol equivalent of organic diol used; a process wherein the dicarboxylic acid is fumaric acid, a process wherein the cyclic alkylene carbonate is ethylene carbonate, propylene carbonate, or butylene carbonate, and mixtures thereof, and alkylene carbonate which can be selected in an amount from about 1.90 mol equivalents to about 2.45 mol equivalents, based on approximately 1 mol equivalent of organic diol used; a process wherein the first alkaline catalyst is an alkaline carbonate; a process wherein the alkali carbonate is potassium carbonate, sodium carbonate, ruby carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, manganese carbonate, or barium carbonate, and mixtures thereof, and alkali carbonates which are selected in an amount from about 0.001 mole equivalents to about 0.01 mole, based on about 1 mole equivalent of organic diol used; a process wherein the alkali carbonate is potassium carbonate; a process wherein the second catalyst is an alkaline alkoxide; a process wherein the alkyl-alkoxide is lithium methoxide, lithium ethoxide, lithium epoxide, lithium butoxide, lithium isopropoxide, lithium isobutoxide, lithium t-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide , potassium butoxide, potassium isopropoxide, potassium isobutoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium isopropoxide, sodium isobutoxide, or sodium t-butoxide, and mixtures thereof, and alkali metal alkoxide which is selected in an amount from about 0.001 mole equivalents to about 0.05 mole equivalents, based on about 1 mole equivalent of the organic diol used; a process wherein the alkyl-alkoxide is potassium t-butoxide; a process wherein the first catalyst is selected in an amount from about 0.01 to about 0.1 mole, percent by weight of the unsaturated polyester; a process wherein the second catalyst is selected in an amount from about 0.01 to about 0.1 mole percent by weight of the unsaturated polyester; a process wherein the peroxide is an aliphatic peroxide, an aromatic peroxide, and mixtures thereof; a process wherein the peroxide is benzoyl peroxide, lauryl peroxide, t-butyl peroxide, propyl peroxide, or stearyl peroxide; a process wherein a polyester resin is formed by (i) reacting an organic diol in an amount from about 0.95 to about 1.05 mole equivalents, with a cyclic alkylene carbonate in an amount from about 1.95 to about 2.05 mole equivalents, and a catalyst in an amount from about 0.001 to about 0.1 mole equivalents at a temperature from about 175 ° C to about 205 ° C, for a duration of for example, about 1 to about 6 hours; by polycondensation with a dicarboxylic acid in an amount from about 0.95 to about 1.05 mole equivalents, for a duration of for example, about 1 to hours, and followed by reducing the pressure from about 760 Torr to about 1 Torr for a period from about 1 to about 6 hours; a process wherein a polyester resin is formed by (i) reacting an organic diol in an amount from about 0.95 to about 1.05 mole equivalents, with a cyclic alkylene carbonate in an amount from about 1.95 to about 2.05 mole equivalents, and a catalyst in an amount from about 0.001 'to about 0.1 mole equivalents, at a temperature from about 185 ° C to about 205 ° C; for a duration of about 1 to about 6 hours; (ii) adding a cyclic alkylene carbonate in an amount of from about 0.05 to about 0.35 mole equivalents, with a second alkaline alkoxide catalyst in an amount from about 0.001 to about 0.1 mole equivalents, at a temperature of about 185 ° C up to about 205 ° C; and (iii) followed by polycondensation with a dicarboxylic acid in an amount from about 0.95 to about 1.05 mole equivalents, for a duration from about 1 to about 3 hours, and followed by pressure reduction from about 760 Torr to about 1. Torr for a period from about 1 to about 6 hours; a ess wherein the polyester, unsaturated resin is obtained from the (i) condensation of from about 0.95 to about 1.05 mole equivalents of an organic diol, with from about 1.95 to about 2.05 mole equivalents of an alkylene carbonate in the presence of an first alkaline catalyst at a temperature from about 175 ° C to about 205 ° C, for a duration from about 1 to about 6 hours; and (ii) optionally adding thereto an optional amount from about 0.05 to about 0.35 moles, equivalents of a cyclic alkylene carbonate and a second catalyst at a temperature from about 185 ° C to about 205 ° C, for a duration of about 1. up to about 3 hours; and (ii) polycondensing with a dicarboxylic acid an amount from about 0.95 to about 1.05 mole equivalents, for a duration from about 1 to 3 hours, and followed by pressure reduction from about 760 Torr to about 1 Torr for a period from about 1 to about 6 hours; a ess wherein the cyclic alkylene carbonate is employed in an amount from about 1.9 equivalents to about 2.1 mole equivalents, based on about 1 mole equivalent of organic diol used; a ess wherein a cyclic alkylene carbonate is additionally added in an amount from about 0.05 mole equivalents to about 0.309 mole equivalents, based on about 1 mole equivalent of organic diol used; a ess wherein the unsaturated polyester resin is obtained from (i) condensing about 0.95 to about 1.05 mole equivalents of an organic diol, with from about 1.95 to about 2.05 mole equivalents of an alkylene carbonate in the presence of a first alkaline catalyst at a temperature from about 175 ° C to about 205 ° C, for a duration from about 1 to about 6 hours; and (ii) optionally adding thereto an additional amount from about 0.05 to about 0.35 mole equivalents of a cyclic alkylene carbonate and a second catalyst at a temperature from about 185 ° C to about 205 ° C, for a duration of about 1. up to about 3 hours; and (iii) followed by a third step comprised of adding a dicarboxylic acid, heating the mixture from about 185 ° C to about 205 ° C, followed by reducing the temperature from about 760 Torr to about 1 Torr; a ess wherein the resulting polyester is poly (oxylated bisphenol co-fumarate), poly (bisphenol ethoxylated co-fumarate), poly (butylated bisphenol co-fumarate), poly (bisphenol co-fumarate co-ethoxylated with bisphenol) co-oxylated), or poly (oxylated bisphenol co-maleate), a ess for the preparation of cross-linked polyesters obtained from the reactive extrusion of a peroxide and a polyester, unsaturated resin, and resin that is generally available (i) reacting an organic diol with a cyclic alkylene carbonate in the presence of a first catalyst to thereby form a polyalkoxydiol; (ii) optionally adding thereto an additional amount of cyclic alkylene carbonate in the presence of a second catalyst; and (iii) subsequently polycondensing the resulting mixture with a dicarboxylic acid; an organic pigment comprised of polyester and colorant; an organic pigment where the dye is a dye, or an organic pigment; wherein the organic pigment contains a wax component; an organic pigment in which the organic pigment contains a filler additive; an organic pigment wherein the organic pigment contains a wax component and a filler additive; an organic pigment in which the organic pigment contains surface additives; an organic pigment wherein the additives are comprised of silicas, metal oxides, salts of fatty acids, or mixtures thereof; a developer comprised of the organic pigment and the carrier; an organic pigment wherein the polyester is poly (propoxylated bisphenol co-fumarate); a process wherein the polyester is poly (propoxylated bisphenol), and the bis-alkoxy diol is propoxylated bisphenol A comprised of the mixture of isomers of 4- (2-hydroxyethyl) -bisphenol A, bis 4, 4 '- (2- hydroxyethyl) bisphenol A, r- (2'-hydroxyethyl-2-oxyethyl) -4'- (2-hydroxyethyl) -bisphenol A and / or bisphenol A higher order propoxylated polyols, illustrated as monomers I, II and III, respectively , of Formula 2.

II wherein R is an aromatic component, R 'is hydrogen or alkyl, and a is zero, 1 or 2 or a mixture of zero, 1 and 2; a process wherein the polyester is poly (propoxylated bisphenol), and the bis-alkoxy diol bisphenol A propoxylated comprised of mixture of isomers of 4- (2-hydroxyethyl) -bisphenol A, bis 4,4'- (2-hydroxyethyl) Bisphenol A, 4- (2'-hydroxyethyl-2-oxyethyl) -4 '- (2-hydroxyethyl) -bisphenol A and / or bisphenol A-propoxylated polyols of higher order, illustrated as monomers I, II and III, respectively , of Formula 1 III where a is as illustrated in the present; a process wherein the isomers contain from about 2 to about 5 weight percent of the isomer I, from about 90 to about 97 weight percent of the isomer II, and from about 0 to about 3 weight percent, and the sum of I, II and III is approximately 100 percent; a process wherein the preparation of an unsaturated polyester comprised of (i) reacting A or 2, 2-bis (4-hydroxy phenyl) propane with a propylene carbonate in the presence of a first catalyst to thereby form an -alkoxy diol, and (ii) adding to this an additional amount of propylene carbonate in the presence of a second catalyst, and wherein bis-alkoxy diol is comprised of the isomers of Formula 1.

III wherein a represents the number of segments and with from about 0 to about 1 weight percent of the isomer I, from about 85 to about 97 weight percent of the isomer II, and from about 3 to about 15 weight percent of the isomer III, and the sum of I, II, and III is approximately 100 percent; a process wherein the aromatic R group is a radical portion of the group selected from 2,2-bis (4-hydroxy-phenyl) propane, 2,2-bis- (3-hydroxyphenyl) propane, 2, 2-bis- ( 2-hydroxyphenyl) propane, 2,2-bis (3-hydroxyphenyl) propane, 2,2-bis- (5-hydroxyphenyl) propane, bisphenol A, ethoxylated bisphenol A, bis- (4-hydroxy-phenyl) methane, , l-bis- (4-hydroxyphenyl) ethane and hydroquinone; a process wherein the aromatic R group is a radical portion of the group selected from 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (3-hydroxyphenyl) propane, 2, 2-bis- ( 2-hydroxyphenyl) propane, 2,2-bis- (3-hydroxyphenyl) propane, 2,2-bis- (5-hydroxyphenyl) propane, bisphenol A, ethoxylated bisphenol A, bis- (4-hydroxyphenyl) methane, 1, 1-bis- (4-hydroxyphenyl) ethane and hydroquinone; and a multi-step process for the preparation of polyester polymers, especially an unsaturated polyester resin, wherein the multi-weight process can be a two-step or three-step monomer addition process, and preferably a process two-step monomer addition, comprising a first step of alkoxylating a diol such as bisphenol A or 2,2-di (4-hydroxyphenyl) propane, with a cyclic alkylene carbonate such as ethylene carbonate, propylene carbonate, and the like, in the presence of a suitable catalyst such as an alkali carbonate, such as potassium carbonate, followed by a second step comprising the addition of a suitable diacid or dicarboxylic acid, such as fumaric acid or a preferred embodiment which is a three-step monomer addition process comprised of (i) alkoxylating a diol such as bisphenol A or 2,2-di (4-hydroxyphenyl) propane, with a cyclic alkylene carbonate such as carbonate ethylene, propylene carbonate, and the like, in the presence of a suitable catalyst such as an alkali carbonate, such as potassium carbonate; (ii) adding to this an additional amount of cyclic alkylene carbonate in the presence of a second catalyst such as an alkaline alkoxide, for example, sodium methoxide or potassium t-butoxide; and followed by (iii) the addition of a suitable dioxide such as a dicarboxylic acid, and preferably fumaric acid. The polyester resin obtained is preferably an unsaturated polyester that can be subjected to crosslinking, especially to reactive extrusion processes, at a high gel content, such as from about 0.01 to about 60 percent, and preferably from about 3 to about 45 percent gel, in the presence of an initiator such as a peroxide, such as benzoyl peroxide or lauryl, and peroxide which is selected for an amount of, for example, from about 0.01 to about 5 weight percent of the resin. Organic pigments containing crosslinked polyester resins exhibit, for example, desirable low temperature fixing characteristics, such as from about 120 ° C to about 145 ° C, and high sliding properties such as from about 180 ° C to about 225 ° C. In addition, the present invention relates to an economical process for preparing an unsaturated polyester resin, such as, for example, poly (bisphenol A co-fumarate, propoxylated), from three or more propoxylated bisphenol A isomers or monomers of fumaric acid , and wherein the three or more isomers of the propoxylated bisphenol A are obtained from the condensation of bisphenol A with a cyclic alkylene carbonate in the presence of a first catalyst such as potassium carbonate, and optionally followed by the addition of a additional amount of cyclic alkylene carbonate in the presence of a second catalyst such as sodium methoxide or sodium t-butoxide. The preferred resin mentioned above, poly (propoxylated bisphenol A co-fumarate) can be prepared by a two step process comprised of (i) the alkoxylation of for example, from about 0.95 to about 1.05 mole percent of 2, 2-di (4-hydroxyphenyl) propane also known as bisphenol A, as for example, from about 1.95 to about 2.05 mole percent propylene carbonate, and for example, from about 0.0001 to about 0.2 mole percent of a catalyst such as potassium carbonate, at a suitable temperature of for example from about 160 to about 205 ° C for a suitable duration of about 1 ° to about 9 hours resulting in the formation of a propoxylated bisphenol A mixture, comprised of 4 - (2-hydroxyethyl) -bisphenol A, bis 4, 4 '- (2-hydroxyethyl) -bisphenol A, r- (2'-hydroxyethyl-2-oxyethyl) -4' - (2-hydroxyethyl) -bisphenol A and /or bisphenol A propoxylated polyols, of greater ore, illustrated as monomers I, II and III, respectively, as follows.

FORMULA 1 III where a is zero, 1, 2, or a mixture of zero, 1 and 2.

FORMULA 2 If III wherein R is an aromatic or aryl group; R 'is an alkyl or hydrogen group and a is an integer or number from about 0 to about 3; aromatic which is, for example, aryl, with, for example, from 6 to about 30 carbon atoms; and alkyl containing, for example, from 1 to 25, and preferably from about 12 carbon atoms. • The ratios of the propoxylated bisphenol A mixtures can vary, and in many cases, the ratio obtained, with reference to Formula I, is from about 1 to about 5 weight percent of monomer I, and from about 95 to about 99 weight percent of the monomer II, and from about 0 to about 3 weight percent of the monomer III, and provided that the total amounts in percent of the three monomers are about 100 percent. The second step is generally comprised of a polyesterification of the propoxylated bisphenol A, intermediate, mentioned above, with bisphenol A, with from about 0.95 to about 1.05 percent in ml of fumaric acid, at a temperature of, for example, from 180 ° C. to about 210 ° C for a duration of about 1 to about 6 hours, followed by pressure reduction for example, from about 0.1 to about 40 mm of Hg for a suitable duration of preferably, for example, about 1 to about 3 hours, to result in the formation of the 'unsaturated polyester, poly (propoxylated bisphenol A co-fumarate). In another specific embodiment of the present invention, the aforesaid mixture of the propoxylated monomers I, II and III can be varied by the addition of an excess of alkylene carbonate in the presence of a second alkaline alkoxide initiator such as t-butoxide potassium or sodium methoxide after the first step mentioned above. More specifically, in one embodiment of the present invention, the unsaturated polyester resin is prepared by a three-step monomer addition process comprised of (i) the alkoxylation of, for example, from about 0.95 to about 1.05 percent. in mol of 2,2-di (4-hydroxyphenyl) propane also known as bisphenol A, as for example, from about 1.95 to about 2.05 mole percent propylene carbonate, and for example, from about 0.0001 to about 0.2 mole. one hundred mole of a catalyst such as potassium carbonate, at a suitable temperature of for example, from about 160 to about 205 ° C for a suitable duration of for example, preferably about 1 to about 9 hours, resulting in the formation of a propoxylated bisphenol A mixture, comprised from about 2 to about 5 weight percent monomer I (F 1), and from about 95 to about 99 weight percent of monomer II, and from about 0 to about 3 weight percent of monomer III, and provided that the total amounts in percent of the three monomers are about 100 percent; followed by (ii) the further addition of from about 0.05 to about 0.25 mole percent of propylene carbonate with from about 0.001 to about 0.3 mole percent of a second alkaline alkoxide catalyst such as potassium t-butoxide at a temperature from about 180 ° C to about 205 ° C for a suitable duration of for example preferably about 1 to about 3 hours, and thereby resulting in a mixture of propoxylated bisphenol A comprised of, for example, from about 0 to about 0.5 percent by weight of monomer I, and from about 84 to about 99 weight percent of monomer II, and from about 3 to about 15 weight percent of monomer III, and with the proviso that total amounts in percent of three monomers are about 3 percent; and followed by the third step generally comprising a polystyification of the intermediate propoxylated bisphenol A, mentioned above, with from about 0.95 to about 1.05 mole percent fumaric acid, at a temperature of, for example, from 180 to about 210 °. C under reduced pressure of for example, from about 0.1 to about 40 mm Hg for a suitable duration of preferably, for example, from about 3 to about 6 hours, to result in the formation of unsaturated polyester, poly (co-fumarate) of bisphenol A, propoxylated). The unsaturated polyester, mentioned above poly (propoxylated bisphenol A co-fumarate), can be subjected to crosslinking, especially to reactive extrusion processes, at a high gel content, such as from about 0.1 to about 60 percent, and preferably from about 3 to about 45 percent gel, in the presence of an initiator such as a peroxide, such as benzoyl peroxide or lauryl and peroxide which is selected in an amount of, for example, from about 0.01 to about 5 percent by weight of the resin. The unsaturated polyester resins are preferably derived from a mixture of propoxylated bisphenol A, and wherein 4- (2-hydroxyethyl) bisphenol A (Isomer I) is minimized or prevented due to inhibition to a high degree of polymerization, and the interference with subsequent cross-linking with the peroxide initiator this last inhibition is mainly due to the portions of aryl (or phenolic) hydroxide. Thus, it is preferred that this isomer I, 4- (2-hydroxyethyl) -bisphenol A, is minimized by this process or the level control of less than about 1 weight percent of the isomeric mixture is avoided, and is preferably minimized to less than about 0.1 weight percent, or more preferably zero percent of the isomeric mixture (Formula 1).This aforementioned mixture of the propoxylated monomers I, II and III can be varied by the concentration of cyclic cycloalkene carbonate and the catalyst time. In general, alkaline carbonate catalysts such as sodium carbonate, potassium carbonate, lithium carbonate and the like, are useful in the alkoxylation of aryl diols, such as bisphenol A and the like, to produce primarily a mixture wherein the bis-4, 4 '- (2-hydroxyethyl) bisphenol A (isomer II of Formula 1), is the predominant product of about 95 to about 100 weight percent, and isomer III is minimized from about 0 to about 3 percent by weight. Also, the amount of isomer I is usually from about 2 to about 5 weight percent and this isomer may not be as effective in obtaining highly crosslinked resins due to its inhibition with peroxides. In the presence of an initiator such as alkali metal alkoxide, for example, sodium methoxide, potassium methoxide, lithium methoxide, potassium t-butoxide and the like, then the reaction of an aryl diol with a cyclic alkylene carbonate gives resulting in the formation of both bis-4, 4 '- (2-hydroxyethyl) -bisphenol A (Isomer II) in an amount from about 60 to about 85 weight percent, and 4- (2'-hydroxyethyl-2-oxyethyl) ) - '- (2-hydroxyethyl) -bisphenol A and higher order polyols (Isomer III and where a is, for example, zero, 1, 2 or mixtures of 1 and 2) in an amount of about 15 to about 40 per percent by weight, and provided that the total amounts in percent of the three monomers are approximately 100 percent, as illustrated in Comparative Example VI. Therefore, in order to continue the reaction mixture such that the three isomeric, propoxylated bisphenol A intermediate products are obtained in an amount of, for example, from about 0 to about 1 weight percent of monomer I, and about 84 to about 99 weight percent of monomer II, and about 3 to about 15 weight percent of monomer III, and with the proviso that the total amounts in percent of the three monomers are about 100 percent, is It is necessary to provide a process that is comprised of the three steps mentioned above, that is, comprised of (i) the alkoxylation of bisphenol A, propylene and a catalyst such as potassium carbonate, at a suitable temperature of for example, about 160 ° C. , up to about 205 ° C for a suitable duration of for example, preferably about 1 to about 3 hours, and will result in The formation of a propoxylated bisphenol A mixture, ranging from about 2 to about 5 weight percent of monomer I (Formula 1), and from about 95 to about 99 weight percent of monomer II, and from about 0 to about about 3 weight percent of monomer III, with the proviso that the total amounts in percent of the three monomers be about 100 percent; (ii) followed by the addition of from about 0.05 to about 0.25 mole percent of propylene carbonate and, for example, from about 0.001 to about 0.01 mole percent of a second alkaline alkoxide catalyst such as potassium t-butoxide to a temperature from about 180 to about 205 ° C for a suitable duration of for example preferably about 1 to about 3 hours, and thereby resulting in a mixture of propoxylated bisphenol A comprised of, for example, from about 0 to about 0.5 percent by weight of monomer I, and from about 84 to about 97 percent by weight of monomer II, and from about 3 to about 15 percent by weight of monomer III, and provided that the total amounts in percentage of the three monomers are approximately 100 percent. The unsaturated polyester resin poly (propoxylated bisphenol A co-fumarate), described in the two-step monomer process and using only the alkali carbonate catalyst, generally exhibits high glass transition temperatures from about 58 ° C to about 62 ° C. ° C at a molecular weight of from about 15,000 to about 20,000 grams per mole as measured by gel permeation chromatography. In many cases, it is desirable that the organic pigment resins exceed high vitreous transition temperature is from about 58 ° C to about 62 ° C, such that the block of the organic pigment is avoided and minimized, as well as the minimization of slippage copy to copy. In order to obtain a high vitreous transition temperature from about 58 ° C to about 58 ° C at a molecular weight from about 15,000 to about 20,000 grams per mole, it is necessary that the unsaturated polyester resin is derived from the mixture of propoxylated bisphenol A, wherein the predominant isomer (Formula 1) is comprised from about 95 to about 99 weight percent of isomer II, and isomer III is minimized from about 0 to about 3 percent, because the latter isomer reduces the glass transition temperature of the resin. Conversely, in many cases, an unsaturated polyester resin, for example poly (propoxylated bisphenol A co-fumarate), with the lower vitreous transition temperature such as from about 52 ° C to about 57.9 ° C if desired to a molecular weight from about 15,000 to about 20,000 grams per mole as measured by gel permeation chromatography. These unsaturated polyester resins with low vitreous transition temperatures are useful in the provision of organic pigments with low minimum melting temperatures, thereby reducing the temperature of the melting subsystem and reducing the energy consumption of the xerographic device. In order to obtain a low vitreous transition temperature from about 52 ° C to about 57.9 ° C at a molecular weight of from about 15,000 to about 20,000 grams per mole, it is necessary that the unsaturated polyester resin be derived from the bisphenol A mixture. propoxylated wherein the predominant isomer (Formula 1) is comprised of from about 84 to about 97 weight percent of isomer II, and isomer III is comprised of from about 3 to about 15 weight percent of the isomeric mixture. If isomer III is present in an amount of more than about 15 weight percent, that the corresponding unsaturated resin will be proportionately lower at the glass transition temperature. The aforementioned poly (propoxylated bisphenol A co-fumarate) of lower glass transition temperatures from about 52 ° C to about 57.9 ° C, can be obtained by the three step process, mentioned above, wherein the alkali carbonate is used in the first step, followed by the use of excess alkylene carbonate and alkaline alkoxide catalyst in the second step, followed by the poly-esterification as described in the third step; and the two-step process comprising (i) charging a condensation type vessel equipped with a distillation apparatus, and vacuum line, with from about 0.95 to about 1.05 mole percent of a diol such as 2, 2-bis ( 4-hydroxyphenyl) -propane, from about 1.95 to about 2.05 mole percent of a cyclic alkylene carbonate, with, for example, from about 1 to about 25, and preferably from about 2 to about 12, carbon atoms , a cyclic carbonate such as ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, and the like and from about 0.001 to about 0.05 weight percent in mol of a catalyst such as a metal carbonate alkali, such as potassium carbonate in sodium, followed by heating the mixture to, for example, a suitable temperature, from 160 ° C to about 205 ° for a duration of, for example, from about 3 to about 9 hours and resulting in a mixture of the propoxylated bisphenol A intermediate; (ii) adding from about 0.95 to about 1.05 mole percent of a diacid such as fumaric acid, heating the mixture with stirring at about 195 ° C to about 220 ° C for a duration of about 3 to about 6 hours, and reducing pressure from about atmospheric pressure (760 Torr) to about 2 Torr for a period, for example, from about 1 to about 3 hours, followed by pressurization of the vessel at atmospheric pressure and discharge of the resin through a bottom valve; a three step process comprising (i.) charging a condensation type vessel equipped with a distillation apparatus, and vacuum line, with from about 0.95 to about 1.05 mole percent of a diol such as 2,2-bis ( 4-hydroxyphenyl) propane, from about 1.95 to about 2.05 mole percent of a cyclic alkylene carbonate, for example, from about 1 to about 25, preferably from about 2 to about 12 carbon atoms, cyclic carbonate such such as alkylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, and the like, and from about 0.001 to about 0.05 weight percent in mol of a catalyst such as an alkali metal carbonate, such as potassium carbonate and sodium, followed by heating the mixture to, for example, at a suitable temperature, from 160 ° C to about 205 ° C for a duration of Example, about 2 to about 10 hours and resulting in a mixture of the propoxylated bisphenol A intermediate; (ii) adding thereto from about 0.05 to about 0.25 moles of alkylene carbonate such as ethylene-propylene carbonate and a second alkaline alkoxide catalyst such as potassium p-butoxide such as sodium methoxide, t-butoxy or potassium, and the like, in an amount from about 0.01 to about 0.05 weight percent in mol, and continue heating at a temperature from about 185 ° C to about 205 ° C for a duration from about 0.5 hours to about 3 hours; followed by (iii) heating from about 0.95 to about 1.05 mole percent of a diacid such as fumaric acid, and heating the mixture with stirring at about 195 ° C to about 220 ° C for a duration of about 3 to about 6 hours , and reducing the pressure from about atmospheric pressure (760 Torr) to about 2 Torr for a period of for example about 1 to about 3k hours, and followed by pressurization of the vessel at atmospheric pressure and discharging the resin through a valve of the background. Examples of polyesters obtained with the processes of the present invention are poly (propoxylated bisphenol co-fumarate), poly (propoxylated bisphenol co-fumarate), poly (butyloxylated bisphenol co-fumarate), poly (bisphenol co-fumarate co-ethoxylated with co-propoxylated bisphenol), poly (propoxylated bisphenol co-maleate), poly ( propoxylated bisphenol co-itaconate), poly (1,2-propylene fumarate), poly (propoxylated bisphenol co-maleate), poly (ethoxylated bisphenol co-maleate), poly (butyloxylated bisphenol co-maleate), and poly (bisphenol co-maleate, ethoxylated with co-propoxylated bisphenol). Specific examples of diols selected for the process of the present invention include, for example, alkylene diols such as ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, pentylene glycol, hexylene glycol, diphenol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (3-hydroxyphenyl) propane, 2,2-bis- (2-hydroxyphenyl) propane, 2,2-bis- (3- hydroxyphenyl) propane, 2, 2-bis- (5-hidoxyphenyl) propane, bisphenol A, ethoxylated bisphenol A, propoxylated bisphenol A, bis- (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, cis -1,4-hydroxy-cyclohexane, trans-1,4-dihydroxy-cyclohexane, cis-1,2-dihydroxy-cyclohexane, trans-1,2-dihodrix-cyclohexane, trans-1,3-dihydroxy-cyclohexane, cis -1, 3-dihydroxy-cyclohexane, mixtures thereof and the like inclusive of other known diols; and diols which are used, for example, in an amount of about 0.95 mole equivalents to about 1.05 mole equivalents, based on about 1 mole equivalent of dicarboxylic acid used. Examples of dicarboxylic acids, especially diacids selected for the process of the present invention, include fumaric acid, malonic acid, itaconic acid, 2-methylitaconic acid, maleic acid, maleic anhydride, adipic acid, succinic acid, suberic acid, -ethyl-succinic, glutaric acid, dodecyl succinic acid, 2-methyladipic acid, pimelic acid, azeilic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,2-cyclohexanedioic acid, 1,3-cyclohexanedioic acid, acid 1 , 4-cyclohexanedioic, dialkyl esters wherein the alkyl group is from about 1 to about 20 carbon atoms, and preferably from chains of from about 2 to about 8 carbon atoms, and are esters of malonate, succinate, fumarate, itaconate , terephthalate, isophthalate, phthalate, cyclohexanodiate, mixtures thereof, and diacids which are cooled, for example , in an amount of from about 10 to about 60 weight percent, and preferably from about 25 to about 50 weight percent in the reagents. Examples of cyclic alkylene carbonates selected for the process of the present invention contain from about 3 to about 25 carbon atoms, include ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, mixtures of the same and similar, alkylene carbonates, which are used, for example, in an amount from about 1.95 mol equivalents to about 2.40 mol equivalents, based on about 1 mol equivalent of the organic diol used. Examples of the first catalyst selected for the process of the present invention include alkali carbonates such as • sodium carbonate, lithium carbonate, potassium carbonate, sodium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, beryllium carbonate, manganese carbonate, carbonate barium and the like, which are used, for example, in an amount from about 0.001 to about 0.1 mole equivalents, based on about 1 mole equivalent of organic diol used. Examples of the second catalyst selected for the process of the present invention include alkali metal alkoxides such as lithium methoxide, lithium ethoxide, lithium propoxide, lithium butoxide, lithium isopropoxide, lithium isobutoxide, lithium t-butoxide, potassium, potassium ethoxide, potassium propoxide, potassium butoxide, potassium isopropoxide, potassium isobutoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium isopropoxide, isobutoxide sodium, sodium t-butoxide, lithium iodide, sodium iodide, potassium iodide, sodium hydroxide, potassium hydroxide, lithium hydroxide, mixtures thereof and the like, and catalysts which are used, for example, in a amount from about 0.001 mole equivalents to about 0.1 mole equivalent, based on about 1 mole equivalent of organic diol used. The various suitable, known dyes, such as dyes, pigments, and mixtures thereof and present in the organic pigment containing the polyester generated with the processes of the present invention in an effective amount, for example, from about 1 to about 25 weight percent of the organic pigment, preferably in an amount of from about 2 to about 12 weight percent, include carbon black such as REGAL 330R; magnetites, such as Mobay magnetites MO8029MR, MO8060MR, Columbian magnetites; MAPICO BLACKSMR and magnetites treated on the surface; Pfizer magnetites. CB4799MR, CB5300MR, CB5600MR 'MXC6369 R; Bayer magnetite, BAYFERROX 8600MR, 8610MR; Northern Pigment magnetites, NP-604MR. NP-608MR; magnetite Magnox TMB-100MR, or TMB-104MR; and similar. As colored pigments, cyan, magenta, yellow, red, green, brown, blue or mixtures thereof may be selected. Specific examples of pigments include HELIOGEN BLUE L6900MR, D6840MR, D7080MR, D7020MR, PYLAM OIL BLUEMR, PYLAM OIL YELLOWMR, PIGMENT BLUEMR, available from Paul Uhlich & Company, Inc., PIGMENT VIOLET 1MR, PIGMENT RED 48MR, LEMON CHROME YELLOX DCC 1026MR, E.D. TOLUIDINE REDMR, and BON RED CMR, available from Dominion Color Corporation Ltd., Toronto, Ontario, NOVAPERM YELLOW FGLMR, HOSTAPERM PINK E R from Hoechst, and CINQUASIA MAGENTAMR available from E.I. DuPont de Nermours & Company, and the like. In general, colorants such as black, cyan, magenta, or yellow, or mixtures thereof, may be selected. The examples of magenta are dye of quinacridone and anthraquinone 2, 9-dimethyl-subsides identified in the Color Index as Cl 60710, red 15 dispersed Cl, diazo dye identified in the Color Index as Cl 26050, red 19 solvent Cl , and similar. Illustrative examples of cyan include copper tetra (octadecylsulfonamido) -phthalocyanine pigment, X-copper phthalocyanine, listed in the color index as Cl 74160, Pigment Blue Cl, and Anthratren Blue, identified in the Color Index as Cl 69810, special blue X-2137, and the like; while illustrative examples of yellow are diarylido 3,3-dichlorobenzidene acetoacetanilides yellow, a monoazo pigment identified in the color index as Cl 12700, Solvent Yellow 16 Cl, a nitrophenylamine sulfonamide identified in the Color Index as Yellow Foron SE / GLN, Scattered Yellow 33, 2, 3-dimethoxy-4-sulfonaniline, phenylazo-4'-chloro-2,5-dimethoxy-acetoacetaniline, and Permanent Yellow GFL. The colored magnetites, such as mixtures of MAPICO BLACKMR, and the cyan components can also be selected as colorants. Other known dyes can be selected such as Black Levanyl A-SF (Miles, Bayer) and Black Sunsperse Coal LHD 9303 (Sun Chemicals), and colored dyes such as Blue Neopen (BASF), Blue Sudan OS (BASF), Fast Blue PV BSG01 (American Hoechst), Blue sunsperse BHD 6000 (Sun Chemicals), Blue Irgalite BCA (Ciba-Geigy), Blue Paliogen 6470 (BASF), Sudan III (Matheson, Coleman, Bell), Sudan II (Matheson, Coleman, Bell ), Suda IV (Matheson, Coleman, Bell), Orange Sudan G (Aldrich), Orange Sudan 220 (BASF), Naranga Paliogen 3040 (BASF), Orange Ortho OR 2673 (Paul Uhlich), Yellow Paliogen 152, 1560 (BASF) , Yellow Lithol Fast 0991K (BASF), Yellow Paliotol 1840 (BASF), Yellow Neopen (BASF), Yellow Novoperm FG 1 (Hoechst), Yellow Permanent YE 0305 (Paul Uhlich), Yellow Lumogen D0790 (BASF), Yellow sunsperse YHD 6001 (Sun Chemicals), Suco-Geilb L1250 (BASF), Amarillo-Suco D1355 (BASF), Rosa Hostaperm E (American Hoechst), Rosa Fanal D4830 (BASF), Magenta Cinquasia (DuPont), Escalarata Lithol D3700 (BASF), Red Toluidine (Aldrich), Scarlet for Thermoplast NSD PS PA (Ugine Kuhlmann of Canada), E.D. Red Toluidine (Aldrich), Organic Pigment Lithol Rubine (PAUL Uhlich, Scarlet Lithol 4440 (BASF), Red Bon C (Dominion Color Company), Bright Red Royal RD-8192 (Paul Uhlich), Pink Oracet RF (Ciba-Geigy), Red Paliogen 3871K (BASF), Red Paliogen 3340 (BASF), and Scarlet Fast Lithol L4300 (BASF). Various effective, known, effective, positive or negative charge enhancement additives can be selected for incorporation into the organic pigment compositions of the present invention, preferably in an amount from about 0.1 to about 10, preferably from about 1 to about 3, percent by weight. Examples of additives include quaternary ammonium compounds including alkyl pyridinium halides; alkyl pyridinium compounds, reference is made to U.S. Patent No. 4,298,672, the disclosure of which is hereby incorporated by reference in its entirety; organic sulfate and sulfonate compositions, U.S. Patent No. 4,338,390, the disclosure of which is hereby incorporated by reference in its entirety; cetyl-pyridinium tetrafluoroborates; diesteryl dimethyl ammonium methylsulfate; aluminum salts such as BONTRON EIRMR or EIIMR (Hodogaya Chemical); and similar. Other organic pigment additives, such as additive, external particles which include organic pigment additives, such as additive particles, external including flow aid additives, additives may also be mixed with the organic pigment compositions of the present invention. that are usually present on the surface of it. Examples of these additives include metal oxides such as titanium oxide, tin oxide, mixtures thereof, and the like, colloidal silicas, such as AEROSIL®, metal salts and metal salts of fatty acids including zinc stearate, oxides of aluminum, cerium oxides, and mixtures thereof, additives which are generally present in an amount from about 0.1 weight percent to about 5 weight percent, and preferably from about 0.1 weight percent to about 1 weight percent. Several of the additives mentioned above are illustrated in U.S. Patent Nos. 3,590,000 and 3,800,588; the descriptions of which are fully incorporated herein by reference. Also, coated silicas may be selected as additives from U.S. Patent Applications Serial No. (not yet assigned - D / 97370); United States Patent Serial No. (not yet assigned D / 97363); U.S. Patent Serial No. (not yet assigned D / 97365), the descriptions of which are fully incorporated herein by reference. Various known crosslinking agents or chemical initiators can be selected for the crosslinking of the polyester, unsaturated, prepared resins, and agents that are selected in an effective amount of for example, from about 0.5 to about 5 weight percent of the organic pigment, and preferably in an amount of from about 1 to about 5 weight percent, these agents preferably including peroxides such as organic peroxides or azo compounds for the generation of crosslinked organic pigment resins of the invention. Suitable organic peroxides include diacyl peroxide such as, for example, neodecanoyl peroxide, lauryl peroxide and benzoyl peroxide, ketone peroxides, such as, for example, cyclohexanone peroxide., and ethyl ethyl ketone, alkyl peroxide esters, such as, for example, t-butyl-yl-peroxy neodecanoate, 2,5-dimethyl-2,5-di (2-ethyl-hexanoyl-peroxy) hexane, T-amyl-peroxy-2-ethylhexanoate, t-butylperoxy-2-ethyl-hexanoate, t-butylperoxy acetat, t-amyl-peroxy acetate, t-butylperoxy benzoate, t-amyl-peroxy benzoate , oo-t-butyl-o-isopropyl-mono-peroxy carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, o-t-butyl-o- (2-ethylhexyl) mono-peroxy carbonate , and carb o-deo-t-amyl-o- (2-ethylhexyl) mono-peroxy, alkyl peroxides such as, for example, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butyl-cumyl peroxide, _-bis (t-butyl-peroxy) diisopropyl-benzene, di-t-butyl peroxide and 2,5-dimethyl-2,5-di- (t-butyl) -peroxy) hexine-3, alkyl hydroperoxides such as, for example, 2,5-dihydro-peroxy-2,5-dimethyl-hexane, eumenohydroperoxide, t-butyl hydroperoxide and t-amylhydroperoxide, and peroxycetals d and alkyl such as, for example, n-butyl-4, -di- (t-butyl-peroxy) -valerate, 1,1-di- (t-burtyl-peroxy) -3,3,5-trimethyl-1-cyclohexane, , 1-di- (t-but i 1-peroxy) -cycothexane, 1,1-di- (t-amyl-peroxy) cyclohexane, 2, 2, -di-t- (butyl-peroxy) -butane, ethyl-3,3-di- (t-butyl-peroxy) -butyrate and ethyl-3, 3-di- (t-amyl-peroxy) -burirate. Suitable azo compounds include azobis-isobutyronitrile, 2,2'-azobis- (methyl-butyronitrile), 1, 1-azobis (cyano-cyclohexane) and other known similar compounds. By allowing the use of low concentrations of chemical initiator and by using substantially all in the crosslinking reaction, usually in the concentration range from about 0.01 to about 10 weight percent, and preferably in the range from about 0.1 to about 4 percent by weight, residual contaminants produced in the crosslinking reaction in the preferred embodiments can be minimized. Since the crosslinking can be achieved at a high temperature such as from about 120 ° C to 180 ° C, the reaction is rapid (for example, less than 10 minutes, preferably about 2 seconds to about 5 minutes of residence time). ) and in this way little or no initiator remains in the product without reacting. Organic pigments and low-melting organic pigment resins can be prepared by a reactive melt mixing process wherein the reactive polyester resins are partially cross-linked. For example, organic pigment resins and low melting point organic pigments can be manufactured by a reactive mixing and melting process as exemplified, for example, in U.S. Patent No. ,376,494, the disclosure of which is hereby incorporated by reference in its entirety, and for example comprising the steps of (1) melting a saturated, reactive, base polyester resin obtained as illustrated herein, thereby forming a polymer melt in a fusion mixing device; (2) initiating the crosslinking of the polymer melt, preferably with a chemical crosslinking initiator and an increased reaction temperature; (3) retaining the polymer melt in the melt mixing device for a sufficient residence time such that partial crosslinking of the base resin can be achieved; (4) providing a sufficiently high shear stress during the crosslinking reaction to retain the gel particles formed during or crosslinking in a small size and well distributed in the polymer melt; (5) optionally devolatilize the polymer melt to remove any volatile effluent compound. The high temperature, reactive, melting mixing process allows rapid crosslinking that allows the production of particles of only substantially microgel particles, and the high shear stress of the process prevents the undue growth of the microgels and allows the microgel particles distribute evenly in the resin. The crosslinking of the unsaturated polyesters comprises, for example, the steps of (1) feeding the polyester, unsaturated base resin generated with a process embodiment of the present invention and an initiator to an extruder; (2) melting the base resin, thereby forming a polymer melt; (3) mixing the molten base resin and the initiator at low temperature to allow a dispersion of the initiator in the base resin before the start of crosslinking; (4) initiating the crosslinking of the base resin with the initiator by increasing the melting temperature and controlling it along the extruder channel; (5) retaining the polymer melt in the extruder for a sufficient residence time at a given temperature such that the required amount of crosslinking is achieved; (6) provide a sufficiently high shear stress during the crosslinking reaction, thereby maintaining the gel particles formed during crosslinking in small size and well distributed in the polymer melt; (7) optionally devolatilize the melt to remove any volatile effluent compound; and (8) sending the crosslinked resin melt through a nozzle to a granulator. A reagent melting mixing process can be considered a process in which chemical reactions can be terminated in the polymer in the melting phase in a melting mixing device, such as an extruder. In the preparation of organic pigment resins, these reactions can be used to modify the chemical structure and molecular weight, and thus the melting rheology and fusion properties, of the polymer. Reactive melt mixing is particularly efficient for highly viscous materials, and is advantageous mainly because it can not require solvents, and thus is easily controlled in an environmental manner. It is also advantageous because it allows a high degree of initial mixing of the resin and the initiator to take place, and provides an environment where a controlled high temperature (adjustable along the length of the extruder) is available, so that a very rapid reaction occurs, and allows a reaction to take place continuously, and in this way the reaction is not limited by the disadvantages of a batch process, where the reaction must be stopped repeatedly, so that the reaction products are can remove and the device clean and prepare for another similar reaction. Once the desired amount of joint is achieved, the reaction products can be quickly removed from the reaction chamber. The resins obtained are generally present in the organic pigment in an amount from about 40 to about 98 weight percent, and more preferably from about 30 to about 98 weight percent, although they may be present in greater or lesser amounts, suitable. For example, the polyester organic pigment resins of the present invention may be mixed subsequently recessed or otherwise mixed with a colorant, charge carrier additives, surfactants, emulsifiers, pigment dispersants, flow additives.; and similar. The resulting product can then be sprayed by known methods such as grinding to form organic pigment particles. The organic pigment particles preferably have a particle diameter by volume, on average from about 5 to about 25, more preferably about 5 to about 15 microns. The polyesters generated with the processes of the present invention can be subjected to further reactions as indicated herein and more specifically to the reactive extrusion reactions. The present invention provides an organic pigment resin, of low fixing temperature, especially an organic pigment resin of low fixing temperature based on the crosslinked resin comprised of linear and crosslinked portions, the crosslinked portion consisting essentially of microgel particles with a particle diameter in volume, average of up to 0.1 microns, preferably about 0.005 up to about 0.1 microns, the microgel particles that are distributed substantially uniformly throughout the linear portions. This resin can be prepared by a reactive melting mixing process, which includes a process described in detail in U.S. Patent No. 5,376,494, the disclosure of which is hereby fully incorporated by reference. In this resin, the crosslinked portion consists essentially of microgel particles, preferably up to about 0.1 micron in average volume particle diameter as determined by electron scanning microscopy and transmission electron microscopy. When produced by a reactive fusion mixing process where cross-linking occurs at high temperature and under high shear stress, the size of the microgel particles does not continue to grow with an increasing degree of cross-linking. Also, the microgel particles are distributed substantially uniformly throughout the linear portion. The crosslinked portions or microgel particles are prepared in such a way that there is substantially no distance between the polymer chains. In this way, the crosslinking is not preferably achieved via the monomer or polymer bridges. The polymer chains are connected directly, for example, at sites of unsaturation or other reactive sites, or in some cases by an individual intervention atom such as, for example, oxygen. Therefore, the crosslinked portions are very dense and do not swell as much as the gel produced by conventional crosslinking methods. This crosslinking structure is different from conventional crosslinking in which the crosslink distance between the chains is completely larger with several monomer units, and wherein the gels swell very well in a solvent such as tetrahydrofuran or toluene. These dense, highly crosslinked microgel particles distributed throughout the linear portion impart elasticity to the resin which improves the sliding properties of the resin, while substantially not affecting the minimum fixing temperature of the resin. The crosslinked polyester organic pigment resin contains for example, a weight portion of the microgel (gel content) in the resin mixture in the range of typically about 0.001 to about 50 weight percent, melting point about 0.1. to about 40 or 10 or 19 weight percent. The linear portion is comprised of the base resin, preferably unsaturated polyester, in the range of about 50 to about 99.999 percent by weight of the organic pigment resin, and preferably in the range of about 60 to about 99.9 or 81 or 90 percent by weight of the organic pigment resin. The linear portion of the resin preferably consists essentially of a base resin, reactive, low molecular weight that is not crosslinked during the crosslinking reaction, and preferably is an unsaturated polyester resin. The number average molecular weight (Mn) of the linear portion as measured by gel permeation chromatography (GPC) is typically in the range of from about 1,000 to about 20,000, and preferably from about 2,000 to approximately 5,000. The weight average molecular weight (Mw) of the linear portion is in the range typically from about 2,000 to about 40,000, preferably from about 4,000 to about 15,000. The molecular weight distribution (Mw / Mn) of the linear portion is in the range typically from about 1.5 to about 6, and preferably from about 2 to about 4. The vitreous transition temperature of the start (Tg) of the portion linear as measured by the differential scanning calorimeter (DSC) for preferred embodiments is in the range typically from about 50 ° C to about 70 ° C, and preferably from about 51 ° C to about 60 ° C. The melt viscosity of the linear portion of the preferred embodiments as measured with a mechanical spectrophotometer at 10 radians pro second is from about 5,000 to about 200,000 poises, and preferably from about 20,000 to about 100,000 poises, at 100 ° C, and decreases sharply with the increase in temperature from about 100 to about 5,000 poises, and preferably from about 400 to about 2,000 poises, as the temperature increases from 100 ° C to 130 ° C. The organic pigment resin may contain a mixture of crosslinked resin microgel particles of a linear portion as illustrated herein. In embodiments of the organic pigment resin of the invention, the start Tg is in the range typically from about 50 ° C to about 70 ° C, and preferably from about 51 ° C to about 60 ° C, and the viscosity The melting point as measured with a mechanical spectrometer at 10 radians per second is from about 5,000 to about 200,000 poises, more preferably from about 20,000 to about 100,000 poises, at 100 ° C and from about 10 to about 20,000 poises a 160 ° C. The low setting temperature of the organic pigment resin is a function of the molecular weight and the molecular weight distribution of the linear portion is not affected by the amount of microgel particles isolated from crosslinking. This is described by the proximity of low temperature viscosity curves, (such as, for example, 100 ° C), in which the melt viscosity is in the range of from about 20,000 to about 100,000 poises as measured with a mechanical spectrometer at 10 radians per second. The hot displacement temperature increases with the presence of microgel particles imparting elasticity to the resin. With a higher degree of crosslinking or microgel content, the hot sliding temperature is increased. This is reflected in the divergence of high temperature viscosity curves (such as, for example, at 160 ° C) in which the melt viscosity is typically in the range from about 10 to about 20 poises as measured at 10 radians per second depending on the amount of microgel particles in the resin. The organic pigment resin can provide a low melting point organic pigment with a minimum fixing temperature of about 100 ° C to about 200 ° C, preferably about 100 ° C to about 160 ° C, and more preferably approximately 110 ° C to approximately 140 ° C, to provide in the low melting organic pigment with a wide latitude of melting to minimize or prevent the displacement of the organic pigment on the fusing roll, and maintain high sputtering and organic pigment efficiencies. The low melting point organic pigment resin preferably has a melting latitude greater than 10 ° C, preferably from about 10 ° C to about 120 ° C, and more preferably more than about 20 ° C and still in more preferably more than about 30 ° C. The MFT of the organic pigment is not believed to be accessible to the crosslinking of the microgel particles of the organic pigment resin, whereas the latitude of fusion is significantly increased as a function of crosslinking or content of microgels in the pigment resin organic. In this way, it is possible to produce a series of organic pigment resins and thus organic pigments therewith. MFT, but with different fusion latitudes. The organic pigment resins and thus the organic pigments of the present invention show a minimized or substantially no vinyl displacement. As the degree of crosslinking or microgel content increases, the low temperature melt viscosity does not change appreciably, while the high temperature melt viscosity increases. In an exemplary embodiment, the hot spreading temperature may be increased to about 30 percent. This can be achieved by crosslinking in the molten state at high temperature and high shear such as, for example, by crosslinking an unsaturated polyester using a chemical initiator in an extruder resulting in the formation of microgel alone, distributed substantially evenly throughout the process. along the linear portion, and substantially without intermediate compounds or solvent portions which are crosslinked polymers with low crosslink density. When the crosslinked intermediate polymers are generated by conventional polymerization processes, the viscosity curves generally change in parallel from low to high degree of crosslinking. This is reflected in the hot, increased displacement temperature, but also in the minimum, increased fixing temperature. In a preferred embodiment, the crosslinked portion consists essentially of high molecular weight microgel particles with high density crosslinking (as measured by the gel content) and that is not soluble in substantially no solvent such as, for example, tetrahydrofuran, toluene and the like. Microgel particles are highly crosslinked polymers with a very small crosslinking distance, if any. This type of cross-linked polymer can be formed by reacting a chemical initiator with unsaturated, linear polymer and more preferably unsaturated polyester, linear, at high temperature and under high shear stress. The initiator molecule breaks into radicals and reacts with one or more double bonds or other reactive sites within the polymer chain to form a polymer radical. This polymer radical reacts with other polymer chains or polymer radicals many times, forming a highly or directly crosslinked microgel. This makes the microgel very dense and results in the microgel not swelling very well in the solvent. The dense microgel also imparts elasticity to the resin and increases its hot displacement temperature as long as it does not affect its minimum fixing temperature. The weight fraction of the microgel (gel content) in the resin can be defined as follows: Gel Content = Total Weight of the sample minus the Weight of the Soluble Polymer (Total Weight of the Sample) x 100 percent. The gel content can be calculated by measuring the relative amounts of soluble polymer, linear and non-linear cross-linked polymer using the following procedure: (1) the sample of the cross-linked resin to be analyzed, in an amount between 145 and 235 milligrams, is weighed directly in a glass centrifuge tube; (2) 45 milliliters of toluene are added and the sample is placed on a shaker for at least 3 hours, preferably overnight; (3) the sample is then centrifuged at approximately 2500 rpm for 30 minutes and then a 5 milliliter aliquot is carefully removed and placed on a pre-weighted aluminum plate; (4) toluene is allowed to evaporate in the air for about 2 hours, and then the sample is further dried in a convection oven at 60 ° C for about 6 hours or constant weight; (5) the sample that remains, nine times, gives the amount of soluble polymer. In this way, using this amount in the above equation, the gel content can be calculated in an easy manner. The unsaturated, linear polyesters selected as the base resin are condensation polymers, of low molecular weight that can be formed by the gradual reactions between diacids both saturated cpmo unsaturated (or anhydrides) and dihydric alcohols (glycols or diols) and by various processes. Steps illustrated herein, and more specifically, by a process comprising reacting an organic diol with an alkylene carbonate in the presence of an alkaline carbonate catalyst to thereby form a bis-alkoxy diol, optionally followed by it reacts by adding the bis-alkoxy diol with a cyclic alkylene carbonate in the presence of a second alkaline alkoxide catalyst, and followed by the polycondensation of the resulting mixture with an unsaturated diacid and wherein the bis-alkoxy diol is comprised of the isomers with from about 0 to about 5 weight percent of the isomer I, from aproximadame 80 to about 99 weight percent of the isomer II, and from about 0.1 to about 15 weight percent of the isomer III, and with the condition of I, II, and III being about 100 percent, and wherein the isomers are of the formula as depicted in Formula 1. The following examples are provided to further illustrate various species of the present invention, which notes that these examples are intended to illustrate and not to limit the scope of the present invention.

COMPARATIVE EXAMPLE I An unsaturated polyester resin, poly (propoxylated bisphenol co-fumarate), derived from 1 mole equivalent of fumaric acid and 1 mole equivalent of a mixture of about 4.6 weight percent of 4- (2-hydroxyethyl) -bisphenol A , 92 weight percent of bis-4, 4 '- (2-hydroxyethyl) -bisphenol A, and 3 weight percent of 4- (2'-hydroxyethyl-2-oxyethyl) -4' (2-hydroxyethyl) ) -bisphenol A, obtained from Milliken Chemical Company as Synfac 8029 was prepared as follows. A 2-liter Hoppes reactor equipped with a vacuum line, and distillation apparatus was charged with 905 grams of propoxylated bisphenol A and obtained from Milliken Chemical Company as Synfac 8029, and analyzed by LC chromatography as a mixture of 4.6 weight percent of 4- (2-hydroxyethyl) -bisphenol A, 92 weight percent of bis-4, 4 '- (2-hydroxyethyl) -bisphenol A, and 3 weight percent of 4- (2'-hydroxyethyl-2) -oxiethyl) -4 '- (2-hydroxyethyl) -bisphenol A. To this were added 306 grams of fumaric acid and 20 milligrams of hydroquinone, and the reactor was then heated to a temperature of about 208 ° C for a period of 1.5 hours, after which the mixture was kept at this temperature for an additional 3 hours during which time the pressure was reduced from atmospheric pressure, 760 to 7 Torr, and water was collected in the distillation receiver. The reactor was then pressurized to atmospheric pressure (approximately 760 Torr, and the resin was discharged through the drain valve - bottom in a vessel and allowed to cool to room temperature (approximately 25 ° C) overnight (approximately 16 hours) The resin product, poly (propoxylated bisphenol co-fumarate) exhibited a vitreous (start) transition temperature of 56.2 ° C using the DuPont differential scanning calorimeter, and obtained during the second heating cycle of the resin at a heating rate of 10 ° C per minute.The melt index of this resin was found to be 31.5 grams per 10 minutes using a weight of 2.16 kilograms at a temperature of 117 ° C. The softening point of this resin using the Mettler softening point apparatus was found to be 108.6 ° C. The weight average molecular weight was found to be 123.600 grams / mol and the number average molecular weight it was found to be 3,500 grams / mol with a polydispersity of 3.9 as measured by gel permeation chromatography and using tetrahydrofuran as the solvent and polystyrene as the alarm. The acid number of the resin was found to be 12.9 milligrams of KOH per gram of the sample. Three hundred (300) grams of the above unsaturated polyester obtained were dry blended using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water, peroxide which was obtained from Elf Atochem. The resulting mixture was extruded through a twin-screw, 15-millimeter, APV extruder, which was adjusted to 330 ° F. The strand of extruded product from the extruder nozzle was cooled in a water bath and the resulting solid strands were air dried and then ground into fine particles (95 weight percent passing through a 3.36 millimeter sieve). , less than about 3 millimeters in dimension. The gel content of the crosslinked product (A), defined as a percentage of insoluble portion in toluene that does not pass through a 0.45 micron filter in a filtration process, was found to be about as low as 7.5 percent. The above piester resin product is not effectively crosslinked using Lucidol 75, primarily due to the presence of about 4.6 percent of isomer I, in the resin which is believed to inhibit the crosslinking reaction. The disadvantages or drawbacks in this comparative example include both economic properties and the resin obtained. More specifically, the propoxylated bisphenol A obtained from Milliken Chemical Company as Synfac 8029, was commercially obtained at a higher cost of about 20 to about 50 percent more than the reagents selected for the present invention, mainly because it is obtained from the anionic reaction of bisphenol A and propylene oxide, followed by purification. Adynally, the isomers of propoxylated bisphenol A (Formula 1) contain up to 3 percent of the third isomer and result in an unsaturated polyester resin with a vitreous transition temperature of 56.2 ° C, and although this resin is useful in many applications, there is a need for a higher Tg resin, such as from about 58 to about 62 ° C, such that higher blocking temperatures as well as minimized copy movement can be obtained. a copy or reduced vinyl displacement property. Additionally, due to the presence of approximately 4.5 weight percent of isomer I, cross-linking the resin with Lucidol 75 resulted in less gel content.

EXAMPLE II It was prepared in a two-step process using potassium carbonate as the condensation catalyst in the first step, to a polyester, unsaturated resin, poly (propoxylated bisphenol co-fumarate), derivative of 1 mole equivalent of fumaric acid, 2.0 mol equivalent of propylene carbonate and 1 mol equivalent of bisphenol A. In the first step, a Hoppes reactor of 2 liters equipped with a vacuum line, and distillation apparatus was charged with 600 grams of bisphenol A obtained from Shell Chemical, 599.6 grams of propylene carbonate obtained as Jeffsol PC from Huntsman Chemicals and 1.2 grams of potassium carbonate. The mixture was heated at 190 ° C for a period of 1 hour with stirring and kept at its temperature for an additional 4 hours. A sample (approximately 1 gram) of this mixture was analyzed by LC chromatography, where it was found that 2.8 weight percent of 4- (2-hydroxyethyl) bisphenol A (Isomer I), 96.5 weight percent bis -4, 4 '- (2-hydroxyethyl) -bisphenol A (Isomer II), and 0.7 weight percent of 4- (2'-hydroxyethyl-2-oxyethyl) -4' - (2-hydroxyethyl) -bisphenol A (Isomer III), reference is made to Formula 1. In the second step, the reactor was then charged with 306 grams of fumaric acid (resin grade) from Bartek Ingredients Ink Company, 1.2 grams of butylastanoic acid obtained as FASCAT 4100 of Elf Atochem, and i220 milligrams of hydroquinone. The temperature was then increased to 190 ° C, over a period of 2 hours, and the pressure was then reduced to 6.5 Torr over a period of 3 hours, where water was collected in the distillation receiver. The poly (propoxylated bisphenol A co-fumarate resin) was then discharged through the bottom drain valve, and exhibited a glass transition temperature (start) of 60.5 ° C using the DuPont differential scanning calorimeter and was obtained during the second heating cycle of the resin at a heating rate of 10 ° C per minute. The melt index of this resin was found to be 23.4 grams per 10 minutes using a 2.16 kg weight at a temperature of 117 ° C. The softening point of this resin using the Mettler softening point apparatus was found to be 111.9 ° C. The weight average molecular weight was found to be 11,000 grams / mol and the number average molecular weight was found to be 4,700 grams / mol with a polydispersity of 2.7 as measured by gel permeation chromatography and using tetrahydrofuran as the solvent and polystyrene as the norm. The acid number of this resin was 26.3 milligrams of KOH per gram of the sample. The advantages of this process are both economic and the property of obtained resin. More specifically, propoxylated bisphenol is obtained directly from bisphenol A and propylene carbonate, and does not comprise purification. Further, for this process, less than 1 percent of the third isomer (Formula 1) was obtained and resulted in a polyester resin of a higher vitreous transition temperature (60.5 ° C), which resin was more useful as a binder of organic pigment in order to prevent block or copy displacement, compared to the resin of Comparative Example I, wherein a Tg of 56 ° C was obtained, producing an organic pigment with this resin prone to blockage and displacement. Three hundred (300) grams of the obtained unsaturated polyester were weighed and mixed dry using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water, obtained from Elf Atochem. The resulting mixture was extruded through a twin-screw, 15-millimeter, APV extruder, which was adjusted to 330 ° F. The strand of extruded product from the extruder nozzle was cooled in a water bath and the resulting solid strands were air dried and then ground into fine particles (95 weight percent passing through a 3.36 millimeter sieve)., less than about 3 millimeters in dimension. The melt index of the cross-linked product (A) was found to be 4.2 grams per 10 minutes using a weight of 16.6 kg at a temperature of 125 ° C in a Tinius-Olsen distribution plastometer. The gel content of the crosslinked product (A), defined as the percentage of the portion insoluble in toluene that does not pass through a 0.45 micron filter in a filtration process, was found to be 30.5 percent. In view of the smaller amount of isomer I present, about 2.8 weight percent, a higher gel content of about 30.5 percent was obtained in comparison to Comparative Example I, wherein only 7.5 percent gel was obtained due, believes, in the presence of a greater amount of about 4.6 weight percent isomer I, which is believed to inhibit the crosslinking of the resin with the peroxide.

EXAMPLE III A polyester resin, unsaturated, poly (propoxylated bisphenol co-fumarate), derivative of 1 mol equivalent of fumaric acid, 2.0 mol equivalents of propylene carbonate and 1 mol equivalent of bisphenol A was prepared in a two step process and using potassium carbonate as the condensation catalyst in the first step.

In the first step, a 2 Hoppes reactor equipped with a vacuum line, and distillation apparatus was charged with 600 grams of bisphenol A obtained from Shell Chemical, 614.6 grams of propylene carbonate obtained as Jeffsol PC from Huntsman chemicals and 1.2 grams of Potassium carbonate. The mixture was heated at 190 ° C for a period of 1 hour with stirring and maintained at that temperature for an additional 4 hours. A sample of this mixture was analyzed by LC chromatography, where it was found to contain 2.8 weight percent of 4- (2-hydroxyethyl) -bisphenol A (Isomer I), 97 weight percent of bis-4, 4 * - (2-hydroxyethyl) -bisphenol A (Isomer II), and 0.2 weight percent of 4- (2'-hydroxyethyl-2-oxyethyl) -4 '- (2-hydroxyethyl) -bisphenol A (Isomer III), reference is made to Formula 1. In the second step, the reactor was then charged with 306 grams of fumaric acid (resin grade) from Bartek Ingredient Ink Company, 1.2 grams of butylstanoic acid obtained as FASCAT 4100 from Elf Atochem, and 220 milligrams of hydroquinone. The temperature was then increased to 190 ° C, over a period of 2 hours, and the pressure was then reduced to 7.5 Torr over a period of 3 hours, where water was collected in the distillation receiver. The resin was then discharged through the bottom drain valve, the resin exhibited a vitreous (start) transition temperature of 58 ° C using the DuPont differential scanning calorimeter and was obtained during the second heating cycle of the resin at a heating rate of 10 ° C per minute. The melt index of this resin was found to be 38 grams per 10 minutes using a 2.16 kg weight at a temperature of 117 ° C. The softening point of this resin using the Mettler softening point apparatus was found to be 108 ° C. The weight average molecular weight was found to be 13,400 grams / mole and the number average molecular weight was found to be 3,700 grams / mole with a polydispersity of 3.6 as measured by gel permeation chromatography and using tetrahydrofuran as the solvent and polystyrene as the norm. The acid number of this resin was 12.25 milligrams of KOH per gram of sample. Three hundred (300) grams of the unsaturated polyester obtained from Example II were weighed and mixed dry using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water, of Elf Atochem. The resulting mixture was extruded through a twin-screw, 15-millimeter APV extruder, which was adjusted to 330 ° F. The strand of extruded pct from the extruder nozzle was cooled in a water bath and the resulting solid strands were air dried and then ground into fine particles (95 weight percent passing through a 3.36 millimeter sieve). , less than about 3 millimeters in dimension. The melt index of the crosslinked pct (A) was found to be 4.2 grams per 10 minutes using a weight of 16.6 kilograms at a temperature of 125 ° C in a Tinius-Olsen extrusion plastometer. The gel content of the crosslinked pct (A), defined as the percentage of the portion insoluble in toluene that does not pass through a 0.45 micron filter in a filtration procedure, was found to be 30.5 percent. The smallest amount of isomer I present, such as about 2.8 weight percent, a higher gel content of about 30.5 percent was obtained in comparison to Comparative Example I, where only 7.5 percent gel was obtained due to the presence of greater than about 4.8 percent of isomer I, which is believed to inhibit the crosslinking of the resin with the peroxide.

EXAMPLE IV A polyester resin, unsaturated, poly (propoxylated bisphenol co-fumarate), derived from 1 mole equivalent of fumaric acid, 2.10 mole equivalents of potassium carbonate and 1 mole equivalent of bisphenol A was prepared, in a three step process and using potassium carbonate and potassium t-butoxide as the catalysts in the first and second steps, respectively. In the first step, a 2 Hoppes reactor equipped with a vacuum line and distillation apparatus was charged with 600 grams of bisphenol A obtained from Shell, 599.6 grams of propylene carbonate obtained as Jeffsol PC from Huntsman chemicals and 1.2 grams of carbonate from potassium. The mixture was heated at 190 ° C for a period of 1 hour with stirring and maintained at that temperature for an additional 4 hours. A sample of this mixture was analyzed by LC chromatography, where it was found to contain 2.7 weight percent of 4- (2-hydroxyethyl) -bisphenol A (Isomer I), 97 weight percent of bis-4, 4 '- (2-hydroxyethyl) -bisphenol A (Isomer II), and 0.3 weight percent of 4- (2'-hydroxyethyl-2-oxyethyl) -4' - (2-hydroxyethyl) -bisphenol A (Isomer III) . In the second step, 30 grams of potassium carbonate and 0.5 grams of potassium t-butoxide were added and the mixture was maintained at a temperature of 195 ° C for a duration of 1 hour. • A sample of this mixture was analyzed by LC chromatography, where it was found to contain 0.5 weight percent of 4- (2-hydroxyethyl) -bisphenol A (Isomer I), 34 weight percent of bis 4, 4 '- (2-hydroxyethyl) -bisphenol A (Isomer II) and 5.5. weight percent of 4- (2'-hydroxyethyl-2-oxyethyl) - '- (2-hydroxyethyl) -bisphenol A and higher order polyol (Isomer III). In the third step, the reactor was then charged with 306 grams of fumaric acid (resin grade) from Bartek Ingredients Ink Company, 1.2 grams of butylstanoic acid obtained as FASCAT 4100 from Elf Atochem, and 220 milligrams of hydroquinone. The temperature was then increased to 190 ° C, over a period of 2 hours, and the pressure was then reduced to 7.5 Torr over a period of 3 hours, where water was collected in the distillation receiver. The resin was then discharged through the bottom drain valve, the resin exhibited a vitreous (start) transition temperature of 57.0 ° C using the DuPont differential scanning calorimeter and was obtained during the second heating cycle of the resin at a heating rate of 10 ° C per minute. The melt index of this resin was found to be 32 grams per 10 minutes using a 2.16 kilogram weight at a temperature of 117 ° C. The softening point of this resin using the Mettler softening point apparatus was found to be 107 ° C. The weight average molecular weight was found to be 13,500 grams / mol and the number average molecular weight was found to be 3,000 grams / mol with a polydispersity of 3.85 as measured by gel permeation chromatography and using tetrahydrofuran as the solvent and styrene as the norm. The acid value of this resin was 10.3 milligrams of KOH per gram of sample. Three hundred (300) grams of the unsaturated polyester were weighed and mixed dry using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water, of Elf Atochem. The resulting mixture was extruded through a twin-screw, 15-millimeter APV extruder, which was adjusted to 330 ° F. The strand of extruded product from the extruder nozzle was cooled in a water bath and the resulting solid strands were air dried and then ground into fine particles (95 weight percent passing through a 3.36 millimeter sieve), of less than about 3 millimeters in dimension. The melt index of the crosslinked product (A) was found to be 4.2 grams - for 10 minutes using a weight of 16.6 kilograms at a temperature of 125 ° C in a Tinius-Olsen extrusion plastometer. The gel content of the crosslinked product (A), defined as the percentage of the portion insoluble in toluene that does not pass through a 0.45 micron filter in a filtration procedure, was found to be 44 percent. The smallest amount of isomer I present, such as about 2.5 weight percent, a higher gel content of about 44 percent was obtained in comparison to Comparative Example I, where only 7.5 percent gel was obtained due to the presence of a greater amount of about 4.8 percent of isomer I, or Example II, where 30 of gel were obtained due mainly to the presence of approximately 2.8 percent of Isomer I.

EXAMPLE V An unsaturated polyester resin, poly (propoxylated bisphenol co-fumarate), derived from 1 mole equivalent of fumaric acid, 2.15 mole equivalents of propylene carbonate and 1 mole equivalent of bisphenol A was prepared in a two step process and using potassium carbonate and potassium t-butoxide as the condensation catalyst in the first and second steps, respectively. In the first step, a 2 Hoppes reactor equipped with a vacuum line, and distillation apparatus was charged with 600 grams of bisphenol A obtained from Shell, 599.6 grams of propylene carbonate obtained as Jeffsol PC from Huntsman Chemicals, and 1.2 grams of Potassium carbonate. The mixture was heated at 190 ° C for a period of 1 hour with stirring and maintained at that temperature for an additional 4 hours. A sample of this mixture was analyzed by LC chromatography, where it was found to contain 2.7 weight percent of 4- (2-hydroxyethyl) -bisphenol A (Isomer I), 97 weight percent of bis-4, - (2-hydroxyethyl) -bisphenol A (Isomer II), and 0.3 weight percent of 4- (2'-hydroxyethyl-2-oxyethyl) -4 '- (2-hydroxyethyl) -bisphenol A (Isomer III). In the second step, 45 grams of propylene carbonate and 0.5 grams of potassium t-butoxide were added and the mixture was maintained at a temperature of 195 ° C for a duration of 1 hour. A sample of this mixture was analyzed by LC chromatography, where it was found to contain 0.2 weight percent of 4- (2-hydroxyethyl) -bisphenol A (Isomer I), 909 weight percent of bis-4, 4 '- (2-hydroxyethyl) -bisphenol A (Isomer II), and 9.8 weight percent of 4, - (2'-hydroxyethyl-2-oxyethyl) -4' - (2-hydroxyethyl) -bisphenol A and polyol of higher order (Isomer III). In the third step, the reactor was then charged with 306 grams of fumaric acid (resin grade) from Bartek Ingredients Ink Company, 1.2 grams of butylstanoic acid such as FASCAT 4100 from Elf Atochem, and 220 milligrams of hydroquinone. The temperature was then increased to 190 ° C, over a period of 2 hours, and the pressure was then reduced to 7.0 Torr over a period of 3 hours, where water was collected in the distillation receiver. The resin was then discharged through the bottom drain valve, the resin exhibited a glass transition temperature (start) of 53 ° C using the DuPont differential scanning calorimeter and was obtained during the second resin heating cycle at a heating rate of 10 ° C per minute. The melt index of this resin was found to be 35 grams per 10 minutes using a 2.16 kilogram weight at a temperature of 117 ° C. The softening point of this resin using the Mettler softening point apparatus was found to be 106 ° C. The weight average molecular weight was found to be 15,000 grams / mol and the number average molecular weight was found to be 4,000 grams / mol with a polydispersity of 3.75 as measured by gel permeation chromatography and using tetrahydrofuran as the solvent and polystyrene as the norm. The acid number of this resin was found to be 11.3 milligrams of KOH per gram of sample.

COMPARATIVE EXAMPLE VI An unsaturated polyester resin, poly (propoxylated bisphenol co-fumarate), derived from 1 mole equivalent of fumaric acid, 2.15 mole equivalents of potassium carbonate and 1 mole equivalent of bisphenol A, was prepared in a two step process using potassium carbonate and • potassium t-butoxide as the condensation catalyst in the first step. In the first step, a 2 Hoppes reactor equipped with a vacuum line, and distillation apparatus was charged with 600 grams of bisphenol A obtained from Shell 644.6 grams of propylene carbonate obtained as Jeffsol PC from Huntsman Chemicals and 1.2 grams of carbonate of potassium and 0.5 grams of potassium t-butoxide. The mixture was heated to 195 ° C for a period of 1 hour with stirring and maintained at that temperature for an additional 1 hour. A sample of this mixture was analyzed by LC chromatography, where it was found to contain 11 weight percent of 4- (2-hydroxyethyl) -bisphenol A, 75 weight percent of bis-4, 4 '- (2-hydroxyethyl) -bisphenol A, and 14 percent by weight of 4- (2'-hydroxyethyl-2-oxyethyl) -4 '- (2-hydroxyethyl) bisphenol A. Using both alkali metal carbonate and alkali metal alkoxide, a greater amount of isomer I was obtained compared to that of the Examples II, III, IV and V. In the second step, the reactor was loaded with 306 grams of fumaric acid (resin grade) from Bartek Ingredients Ink Company, 1.2 grams of butylstanoic acid obtained as FASCAT 4100 from Elf Atochem, and 220 milligrams of hydroquinone. The temperature was then increased to 190 ° C, over a period of 2 hours, and the pressure was then reduced to 7.5 Torr over a period of 3 hours, where water was collected in the distillation receiver. The resin, then discharged through the bottom drain valve, the resin exhibited a glass transition temperature (start) of 52.0 ° C using the DuPont differential scanning calorimeter and obtained during the second resin heating cycle at a heating rate of 10 ° C per minute. The melt index of this resin was found to be 35 grams per 10 minutes using a 2.16 kilogram weight at a temperature of 117 ° C. The softening point of this resin using the Mettler softening point apparatus was found to be 107 ° C. The weight average molecular weight was found to be 15,200 grams / mole and the number average molecular weight was found to be 4,800 grams / mole with a polydispersity of 3.16 as measured by gel permeation chromatography and using tetrahydrofuran as the solvent and polystyrene as the norm. The acid number of this resin was 6.5 milligrams of KOH per gram of sample. Three hundred (300) grams of the obtained unsaturated polyester were dry blended using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water, of Elf Atochem. The resulting mixture was extruded through a twin-screw, 15-millimeter APV extruder, which was adjusted to 330 ° F. The strand of the extruded product from the extruder nozzle was cooled in a water bath and the resulting solid strands were air dried and then ground into fine particles (95 weight percent passing through a 3.36 mm sieve). ), less than about 3 millimeters in dimension. The gel content of the crosslinked product (A), defined as the percentage of the portion insoluble in toluene that does not pass through a 0.45 micron filter in a filtration process, was found to be about 0 percent. This resin is not crosslinked using Lucidol, due to the presence of approximately 11 percent isomer 1 in the resin that is believed to inhibit the crosslinking reaction.

EXAMPLE VII An organic pigment comprised of an unsaturated, cross-linked polyester resin prepared by a reactive extrusion process by mixing confusing 94 parts of the unsaturated polyester of Example IV with Lucidol 75, peroxide initiator, and 6 weight percent carbon black was prepared as follows. Three hundred (300) grams of the unsaturated polyester were weighed and mixed dry using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water, of Elf Atochem. The resulting mixture was extruded through a twin-screw, 15-millimeter APV extruder, which was adjusted to 330 ° F. The strand of extruded product from the extruder nozzle was cooled in a water bath and the resulting solid strands were air dried and then ground into fine particles (95 weight percent passing through a 3.36 millimeter sieve). , or less than approximately 3 millimeters in dimension. The melt index of the cross-linked product (A) was found to be 4.2 grams per 10 minutes using a weight of 16.6 kilograms at a temperature of 125 ° C in a Tinius-Olsen extrusion plastometer. The gel content of the crosslinked product (A), defined as the percentage of the portion insoluble in toluene that does not pass through a 0.45 micron filter in a filtration process, was found to be 44.5 percent. The crosslinked polyester resin, above (261 grams), 15 grams of carbon black (REGALR 330), 15 grams of visco 660P propylene wax by Sanyo -Chemical) and 9 grams of compatabilizer (AX-8840), a polyethylene glycidyl methacrylate, obtained from ELF Atochem) were weighed and mixed dry using a beaker for 45 minutes. The dry mix was then mixed fused together in the APV extruder, which was adjusted to 300 ° F. The strand of the extruded product was cooled in a water bath, and then dried and ground into fine particles (95 weight percent passing through the 3.36 millimeter sieve). The resulting particles of organic pigment, crushed then ground into fine organic pigments using a jet mill (0202 Jet-O-Mizer), organic client that is then classified using an AUC ACUCUT classifier. The resulting product of organic pigments was comprised of 87 weight percent crosslinked polyester, 5 weight percent carbon black (REGALR 330), 5 weight percent wax (660P) and 3 percent by weight of compatibilizer (AX-8840). The average volume diameter of the organic pigment product was 9.04 microns with 11.3 percent by fine number between 1.26 to 4 microns. The tribo of the organic pigment was found to be 5.18 microcolumb / gram as measured in a Tribo Blox-Off semi-automatic apparatus.

EXAMPLE VIII An organic pigment comprised of an unsaturated, crosslinked polyester resin prepared by a reactive extrusion process by melt blending 94 parts of the unsaturated polyester of Example V with Lucidol 75, peroxide initiator, and 6 weight percent carbon black and it was prepared as follows: Three hundred (300) grams of the unsaturated polyester obtained from Example V were weighed and mixed dry using a jar mill with 1.5 grams of Lucidol 75, a benzoyl peroxide with 25 percent water, of Elf Atochem. The resulting mixture was extruded through a 15 mm twin screw extruder of APV, which was adjusted to 330 ° F. The strand of extruded product from the extruder nozzle was cooled in a water bath and the resulting solid strands were air dried and then ground into fine particles. (95 weight percent passing through a 3.36 millimeter sieve), less than about 3 millimeters in dimension. The melt index of the cross-linked product (A) was found to be 4 grams per 10 minutes using a weight of 16.6 kilograms at a temperature of 125 ° C in a Tinius-Olsen extrusion plastometer. The gel content of the crosslinked product (A), defined as the percentage of the portion insoluble in toluene that does not pass through a 0.45 micron filter in a filtration procedure, was found to be 45 percent. Due to the presence of small amounts of isomer I in this resin, less amount of Lucidol 75 was used to crosslink the resin. The polyester resin, cross-linked, above (261 grams), 15 grams of carbon black (Regal'R330), 15 grams of polypropylene wax (Visco 660P by Sanyo Chemical) and 9 grams of (AX-8840 by ELF Atochem) were weighed and mixed dry using a baso for 45 minutes. The dry mix was then mixed fused together in the APV extruder, which was adjusted to 300 ° F. The strand of the extruded product was cooled in a water bath, and then dried and ground into fine particles (95 weight percent passing through a 3.36 millimeter sieve). The resulting particles of organic pigment, crushed then ground into fine organic pigments using a jet mill (0202 Jet-O-Mizer), organic pigment that was then classified using an AUC ACUCUT classifier. The resulting organic pigment product comprised 87 weight percent crosslinked polyester, 5 weight percent carbon black (REGALR 330), 5 weight percent wax (660P) and 3 weight percent compatibilizer (AX) -8840). The average diameter of the volume of the organic pigment product was 9.1 microns with 11 percent by number of fines between 1.2 to 4 microns. The tribo and organic pigment was found to be 5.3 microcoulome / rg as measured in a Tribo Blow Off, semi-automatic device.

COMPARATIVE EXAMPLE IX A co-polyester resin obtained from bisphenol A, propylene carbonate, ethylene glycol and acid) terephthalic with sodium carbonate was prepared as the catalyst and as described in Example I of Japanese Patent 100958440 A2. A 1-liter Parr reactor equipped with a mechanical stirrer was charged with 103.8 grams of bisphenol A, 102 grams of propylene carbonate and 0.1 grams of sodium carbonate. The reactor was purged with nitrogen and heated to an internal temperature of 180 ° C. The nitrogen purge then stopped, the reaction mixture was cooled for one hour, after which the reactor temperature was heated to 220 ° C and stirred for 1.5 hours. E analyzed a sample of this sample by LC chromatography, where it was found to contain 2.3 weight percent of 4- (2-hydroxyethyl) -bisphenol A (Isomer I), 96.9 weight percent of bis-4, 4 '- (2-hydroxyethyl) -bisphenol A (Isomer II), and 0.76 weight percent of 4- (2'-hydroxyethyl-2-oxyethyl-4' - (2-hydroxyethyl) -bisphenol A (Isomer III). To this were added 166 grams of terephthalic acid, 74 grams of ethylene glycol, and 0.38 grams of toluene sulfonic acid.The reactor was then heated to a temperature of about 240 ° C for a period of 5 hours, during which time the pressure was reduced from atmospheric pressure, 760 to about 7 Torr, and water was collected in the distillation receiver.The reactor was then pressurized to atmospheric pressure (approximately 760 Torr) and the resin was discharged through bottom drain valve in a container and allowed to cool to room temperature (approximately 25 ° C during the oche) approximately 16 hours. The co-polyester product exhibited a glass transition t (start) of 65 ° C using the DuPont differential scanning calorimeter and was obtained during the second heating cycle of the resin at a heating rate of 10 ° C per minute.

In this Comparative Example, only one kind of catalyst, alkali carbonate, was employed, resulting in an isomeric mixture wherein about 2.4 weight percent of isomer I was obtained, and lower than the isomeric mixtures obtained in the present invention, such as Examples IV and V, wherein less than about 0.5 weight percent of isomer I was obtained. Additionally, to obtain the high gel content crosslinked polyesters such as about 45 weight percent, it is necessary that less than about 1 weight percent of the isomer I used as exemplified in Examples IV and V. Additionally, the Patent '336 mentioned above uses both a diol such as ethylene glycol and a diacid such as terephthalic acid during the polymerization steps to form a co-polyester. This differs from the present invention, wherein in the embodiments only a diacid such as fumaric acid is used to form the polyester during the polycondensation step. Other embodiments and modifications of the present invention may occur to those skilled in the art subsequent to a review of the present application and the information presented therein; These embodiments, equivalent modifications, or substantial equivalents thereof, are also included within the scope of the present invention. It is noted that in relation to this date, the best method known by the applicant to carry out the present invention is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property:

Claims (57)

1. CLAIMS 1. A process for the preparation of an unsaturated polyester, characterized in that it comprises (i) reacting an organic diol with a cyclic alkylene carbon in the presence of a first catalyst to thereby form a polyalkoxydiol, and (ii) optionally adding to this an additional amount of cyclic alkylene carbonate in the presence of a second catalyst, and (iii) subsequently polycondensing the resulting mixture with a dicarboxylic acid.
2. 2. A process according to claim 1, characterized in that the preparation of the unsaturated polyester comprises (i) reacting an organic diol in an amount from about 0.95 to about 1.05 mole equivalents with a cyclic alkylene carbonate in an amount from about 1.95 to about 2.05. equivalent moles, in the presence of a first alkali carbonate catalyst in an amount from about 0.001 to about 0.1 mole equivalents, to thereby form a polyalkoxydiol, and wherein the polyalkoxydiol is comprised of isomers with from about 2 to about 5 per cent. weight percent of isomer I, from about 95 to about 99 percent isomer II, and from about 0 to about 3 percent by weight isomer III, and the sum of I, II, III is approximately 100 percent and in where the isomers are of the following formula s II III and followed by the subsequent polycondensation of the resulting polyalkoxydiol with dicarboxylic acid in an amount from about 0.95 to about 1.05 mol equivalents, wherein R is an aromatic component, R 'is hydrogen or alkyl, is already zero, 1, or 2, or a mixture of zero, 1, and 23. A process according to claim 1, characterized in that the preparation of the unsaturated polyester comprises (i) reacting an organic diol in an amount from about 0.95 to about 1.05 mole equivalents with a cyclic alkylene carbonate in an amount from about 1.95 to about 2.05 equivalent mole, in the presence of a first alkaline carbonate catalyst in an amount from about 0.001 to about 0.1 mole equivalents; add to this (ii) from about 0.05 to about 0.45 mole equivalents of the cyclic alkylene carbonate in the presence of a second alkaline alkoxide catalyst in an amount from about 0.001 to about 0.1 mole equivalents, to thereby form a polyalkoxydiol comprised of isomers with from about 0 to about 1 weight percent isomer I, from about 85 to about 97 weight percent isomer II, and from about 3 to about 15 weight percent isomer III, and the sum of , II, and III is approximately 100 percent, and where the isomers are of the formulas. III and followed by the subsequent polycondensation of the resulting polyalkoxydiol with a dicarboxylic acid in an amount from about 0.95 to about 1.05 moles equivalents, where a is zero, 1, or 2, or a mixture of zero, 1, and 2. 4. A process according to claim 1, characterized in that a crosslinked polyester generated by the reactive extrusion of a peroxide and the unsaturated polyester is formed. 5. A process according to claim 1, characterized in that the first catalyst is an alkaline carbonate. 6. A process according to claim 1, characterized in that the second catalyst is an alkaline alkoxide. 7. A process according to claim 1, characterized in that the reaction is achieved in the presence of heat. 8. A process according to claim 1, characterized in that the reaction is achieved by heating at a temperature from about 160 ° C to about 215 ° C. 9. A process according to claim 1, characterized in that the reaction is achieved by heating a temperature from about 180 ° C to about 200 ° C. 10. A process according to claim 1, characterized in that the polycondensation is achieved by heating. 11. A process according to claim 1, characterized in that the polycondensation is achieved by heating at a temperature from about 185 ° C to about 225 ° C. 12. A process according to claim 1, characterized in that the polycondensation is achieved by heating to a temperature from about 185 ° C to about 225 ° C for a duration from about 1 to about 5 hours, followed by the reduction of the pressure from about 760 Torr to about 1 Torr for a period of about 1 to about 6 hours. 13. A process according to claim 1, characterized in that subsequent to the polycondensation the reaction mixture is cooled. 14. A process according to claim 13, characterized in that the cooling is from about 25 ° C to about 40 ° C. 15. A process according to claim 13, characterized in that the cooling is at about 25 ° C. 16. A process according to claim 1, characterized in that a crosslinked polyester generated by the reactive extrusion of a peroxide and the unsaturated polyester is formed. 17. A process according to claim 16, characterized in that the crosslinking is represented by a gel content from about 3 to about 75 percent. 18. A process according to claim 16, characterized in that the crosslinking is represented by a gel content from about 3 to about 45 percent. 19. A process according to claim 1, characterized in that a polyester resin, unsaturated poly (propoxylated bisphenol co-fumarate), poly (ethoxylated bisphenol co-fumarate), poly (butylated bisphenol co-fumarate) is formed. ), poly (bisphenol co-fumarate co-ethoxylated with co-ethoxylated bisphenol), poly (1,2-propylene fumarate), poly (propoxylated bisphenol co-maleate), poly (bisphenol ethoxylated co-maleate), poly (butyloxylated bisphenol co-maleate), poly (bisphenol co-maleate co-ethoxylated with co-propoxylated bisphenol), poly (1,2-propylene maleate), poly (propoxylated bisphenol co-itaconate), poly (ethoxylated bisphenol co-itaconate), poly (butylated bisphenol co-itaconate), poly (bisphenol co-itaconate, co-ethoxylated with co-propoxylated bisphenol), or poly (1,2-propylene itaconate). 20. A process according to claim 1, characterized in that the diol is 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, pentylene glycol, hexylene glycol, diphenol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2-bis- (4-hydroxy-phenyl) -propane, 2,2-bis- (3-hydroxy-i-phenyl) -propane, 2,2-bis- (2-hydroxy-phenyl) -propane, 2,2-bis- (3-hydroxy-phenyl) -propane, 2,2-bis- (5-hydroxy-phenyl) -propane, bisphenol A, bisphenol A ethoxylate, bis- (4-hydroxy-phenyl) -methane, 1-bis - (4-hydroxy-phenyl) -ethane, cis-1,4-dihydroxy-cyclohexane, trans-1,4-dihydroxy-cyclohexane, cis-1,2-dihydroxy-cyclohexane, trans-1,2-dihydroxy-cyclohexane , trans-1, 3-dihydroxy-cyclohexane, cis-1,3-dihydroxy-cyclohexane, and mixtures thereof and diol which is optionally selected in an amount from about 0.90 mole equivalents to about 1.1 mole equivalents, based on about 1 mol equivalent of dicarboxylic acid used. 21. A process according to claim 1, characterized in that the diol is 2,2-bis- (4-hydroxy-phenyl) -propane or bisphenol A. 22. A process according to claim 1, characterized in that the dicarboxylic acid is fumaric acid, maloic acid, itaconic acid, 2-methylitaconic acid, maleic acid, maleic anhydride, adipic acid, succinic acid, suberic acid, 2-ethyl-succinic acid, glutaric acid, dodecyl succinic acid, 2-methyladic acid, pimelic acid, azelic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,2-cyclohexanedioic acid, 1,4-cyclohexanedioic acid, dialkyl esters, wherein alkyl contains from about 2 to about 22 carbon atoms, and are esters of malonate, succinate, fumarate, itaconate, terephthalate, isophthalate, phthalate, cyclohexanedioate, mixtures thereof, and diacids which are optionally selected in an amount from about 0.95 mole equivalents to about 1.1 mole equivalents, based on about 1 mole equivalent of the diol organic used 23. A process according to claim 1, characterized in that the dicarboxylic acid is fumaric acid. 24. A process according to claim 1, characterized in that the cyclic alkylene carbonate is ethylene carbonate, propylene carbonate, butylene carbonate, mixtures thereof, and alkylene carbonate which is selected in an amount of about 1.90 mol equivalents to approximately 2.45 moles equivalents, based on approximately 1 mole equivalent of the organic diol used. 25. A process according to claim 1, characterized in that the first alkaline catalyst is an alkaline carbonate. 26. A process according to claim 25, characterized in that the alkali carbonate is potassium carbonate, sodium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, manganese carbonate. , or barium carbonate, and mixtures thereof and alkali carbonate which is selected in an amount from about 0.001 mole equivalents to about 0.01 mole, based on about 1 mole equivalent of organic diol used. 27. A process according to claim 5, characterized in that the alkali carbonate is potassium carbonate. 28. A process according to claim 27, characterized in that the second catalyst is an alkaline alkoxide. 29. A process according to claim 28, characterized in that the alkyl alkoxide is lithium methoxide, lithium ethoxide, lithium propoxide, lithium butoxide, lithium isopropoxide, lithium isobutoxide, lithium t-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium butoxide, potassium isopropoxide, potassium isobutoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium isopropoxide, sodium isobutoxide, sodium t-butoxide, or mixtures thereof and alkali metal alkoxide which is selected in an amount from about 0.001 mole equivalents to about 0.05 mole equivalents, based on about 1 mole equivalent of organic diol used. 30. A process according to claim 28, characterized in that the alkyl alkoxide is potassium t-butoxide. 31. A process according to claim 1, characterized in that the first catalyst is selected in an amount from about 0.01 to about 0.1 mole percent by weight of the unsaturated polyester. 32. A process according to claim 1, characterized in that the second catalyst selects in an amount from about 0.01 to about 0.1 mole percent by weight of the unsaturated polyester. 33. A process according to claim 4, characterized in that the peroxide is an aliphatic peroxide, an aromatic peroxide or mixtures thereof. 34. A process according to claim 33, characterized in that the peroxide is benzoyl peroxide, lauryl peroxide, t-butyl peroxide, propyl peroxide, or stearyl peroxide. 35. A process according to claim 2, characterized in that a polyester resin is formed by (i) reacting an organic diol in an amount from about 0.95 to about 1.05 mol equivalents, with a cyclic alkylene carbonate in an amount from about 1.95. to about 2.05 mole equivalents, and a catalyst in an amount from about 0.001 to about 0.1 mole equivalents at a temperature from about 175 ° C to about 205 ° C for a duration of about 1 to about 6 hours; and followed by polycondensation with a dicarboxylic acid in an amount from about 0.95 to about 1.05 mole equivalents. 36. A process according to claim 1, characterized in that the polyester resin is formed by (i) reacting an organic diol in an amount from about 0.95 to about 1.05 mole equivalents, with a cyclic alkylene carbonate in an amount from about 1.95. to about 2.05 equivalent mole, and a catalyst in an amount from about 0.001 to about 0.1 mole equivalents, at a temperature from about 175 ° C to about 205 ° C; (ii) adding a cyclic alkylene carbonate in an amount of from about 0.05 to about 0.35 mole equivalents, with a second alkaline alkoxide catalyst in an amount from about 0.001 to about 0.1 mole equivalents, at a temperature of about 185 ° C up to about 205 ° C; Y (iii) followed by polycondensation with a dicarboxylic acid in an amount from about 0.95 to about 1.05 mole equivalents. 37. A process according to claim 1, characterized in that the unsaturated polyester resin is obtained from (i) condensing about 0.95 to about 1. 05 mol equivalents of an organic diol, with from about 1.95 to about 2.05 mol equivalents of an alkylene carbonate in the presence of a first alkaline catalyst at a temperature from about 175 ° C to about 205 ° C; and (ii) optionally adding thereto an amount from about 0.05 to about 0.35 mole equivalents of a cyclic alkylene carbonate and a second catalyst at a temperature from about 185 ° C to about 205 ° C, for a duration of about 1 to about 3 hours; and (iii) polycondensing with a dicarboxylic acid in an amount from about 0.95 to about 1.05 mole equivalents, for a duration of about 1 to 3 hours, and followed by the pressure reduction from about 760 Torr to about 1 Torr. 38. A process according to claim 1, characterized in that the cyclic alkylene carbonate is used in an amount from about 1.9 equivalents to about 2.1 mole equivalents, based on about 1 mole equivalent of an organic diol used. 39. A process according to claim 1, characterized in that a cyclic alkylene carbonate is additionally added in an amount from about 0.05 mole equivalents to about 0.30 mole equivalents, based on about 1 mole equivalent of the organic diol used. 40. A process according to claim 1, characterized in that the unsaturated polyester resin is obtained from (i) condensing about 0.95 to about 1.05 mole equivalents of an organic diol, with from about 1.95 to about 2.05 mole equivalents of a carbonate of alkylene in the presence of a first alkaline catalyst at a temperature from about 175 ° C to about 205 ° C, for a duration of about 1 to about 6 hours; and (ii) optionally adding thereto an additional amount from about 0.05 to about 0.35 mole equivalents of a cyclic alkylene carbonate and a second catalyst at a temperature from about 185 ° C to about 205 ° C, for a duration of about 1 to about about 3 hours; and (iii) followed by a third step comprised of adding a dicarboxylic acid, heating the mixture from about 185 ° C to about 220 ° C, followed by the pressure reduction from about 760 Torr to about 1 Torr. 41. A process according to claim 1, characterized in that the resulting polyester is poly (propoxylated bisphenol co-fumarate), poly (ethoxylated bisphenol co-fumarate), poly (butyloxylated bisphenol co-fumarate), poly (co-fumarate) of bisphenol co-ethoxylated with bisphenol co-propoxylate), or poly (propoxylated bisphenol co-maleate). 42. A process for the preparation of crosslinked polyesters, characterized in that they are obtained from the reactive extrusion of a peroxide and a polyester resin, unsaturated, and resin that is generated by (i) reacting an organic diol with a cyclic alkylene carbonate in the presence of a first catalyst to thereby form a polyalkoxydiol; (ii) optionally adding thereto an additional amount of cyclic alkylene carbonate in the presence of a second catalyst; and (iii) frequently polycondensing the resulting mixture with a dicarboxylic acid. 43. An organic pigment characterized in that it is comprised of the polyester of claim 1, and colorant. 44. An organic pigment according to claim 43, characterized in that the dye is a dye, or a pigment. 45. An organic pigment according to claim 43, characterized in that the organic pigment contains a waxy component. 46. An organic pigment according to claim 43, characterized in that the organic pigment contains a filler additive. 47. An organic pigment according to claim 43, characterized in that the organic pigment contains a wax component and a wax additive. 48. An organic pigment according to claim 47, characterized in that the organic pigment contains surface additives. 49. An organic pigment according to claim 48, characterized in that the additives are comprised of silica, metal oxides, salts of fatty acids, or mixtures thereof. 50. A developer characterized in that it is comprised of the organic pigment of claim 43 and a carrier. 51. An organic pigment according to claim 43, characterized in that the polyester is poly (propoxylated bisphenol co-fumarate). 52. A process according to claim 1 characterized in that the polyester is poly (propoxylated bisphenol), and the bis-alkoxy diol is propoxylated bisphenol A, comprised of the mixture of isomers of 4- (2-hydroxyethyl) -bisphenol A, bis 4 , 4 '- (2-hydroxyethyl) bisphenol A, 4- (2'-hydroxyethyl-2-oxyethyl) -4' - (2-hydroxyethyl) -bisphenol A and / or bisphenol A- higher order propoxylated polyols, illustrated as monomers I, II, and III, respectively, of formula 2. II III wherein R is an aromatic component, R 'is hydrogen or alkyl, and a is zero, 1 or 2, or a mixture of zero, 1 and 2. 53. A process according to claim 1, characterized in that the polyester is poly (propoxylated bisphenol), and the diol is bis-alkoxy diol of propoxylated bisphenol A comprised of the mixture of isomers of 4- (2-hydroxyethyl) -bisphenol A, bis 4, 4 '- (2-hydroxyethyl) bisphenol A, 4- (2'-hydroxyethyl-2-oxyethyl) -4' - (2-hydroxyethyl) -bisphenol A and / or higher order propoxylated bisphenol A-polyols, illustrated as monomers I, II, and III, respectively, of formula 1. III where a is zero, 1, 2 or a mixture of zero, 1 and 2. 54. A process according to claim 52, characterized in that the isomers contain from about 2 to about 5 weight percent of isomer I, from about 90 to about 97 weight percent of isomer II, and from about 0 to about 3 weight weight percent of isomer III, and the sum of I, II, and III is optionally 100 percent. 55. A process according to claim 1, characterized in that the preparation of an unsaturated polyester is comprised of (i) reacting bisphenol A or 2, 2-bis (4-hydroxy-phenyl) propane with a propylene carbonate in the the presence of a first catalyst to thereby form a bis-alkoxy diol, and (ii) adding thereto an additional amount of propylene carbonate in the presence of a second catalyst, and wherein the bis-alkoxy diol is comprised of the isomers of formula 1. III with from about 0 to about 1 weight percent of the isomer I, from about 85 to about 97 weight percent of the isomer II, and from about 3 to about 15 weight percent of the isomer III, and the sum of , II, and III is approximately '100 percent, and where a is zero, 1, 2, or 2. 56. A process according to claim 2, characterized in that the aromatic component R is a radical portion selected from the group consisting of 2,2-bis- (4-hydroxy-phenyl) -propane, 2,2-bis- (3-hydroxy-phenyl) -propane, 2,2-bis- (2-hydroxy-phenyl) -propane, 2,2-bis- (3-hydroxy-phenyl) -propane, 2, 2-bis- (5-hydroxy-phenyl) -propane, bisphenol A, bisphenol A, ethoxylated, bis- (4-hydroxy-phenyl) -methane, 1,1-bis- (4-hydroxy-phenyl) -ethane and hydroquinone. 57. A process according to claim 3, characterized in that the aromatic component R is a radical portion of 2,2-bis- (4-hydroxy-phenyl) -propane, 2,2-bis- (3-hydroxy-phenyl) - propane, 2, 2-bis- (2-hydroxy-phenyl) -propane, 2,2-bis- (3-hydroxy-phenyl) -propane, 2,2-bis- (5-hydroxy-phenyl) -propane, bisphenol A, bisphenol A, ethoxylated, bis- (4-hydroxy-phenyl) -methane, 1,1-bis- (4-hydroxy-phenyl) -ethane and hydroquinone.