Preparation of unsaturated polyether esters

Abstract: A process for the preparation of an unsaturated polyether ester which comprises (i) reacting an organic diol like bisphenol A with a cyclic akylene carbonate in the presence of a first catalyst to thereby form a polyalkoxy diol, and (ii) optionally adding thereto a further amount of cyclic alkylene carbonate in the presence of a second catalyst, and (iii) subsequently polycondensing the resulting mixture with a dicarboxylic acid, like fumaric acid. The polyester is used for producing toners and developers in electrophotography.

Description: The present invention is generally directed to a process for the preparation of polyester polymers, and which polyesters can be selected for the preparation polyester polymers which are preferably subsequently crosslinked for utilization as toner resins. In embodiments, the process of the present invention comprises a monomer addition procedure of, for example, first alkoxylating a dihydroxy containing monomer, such as a dihydroxy alkane or dihydroxy arylene, with a cyclic akylene carbonate in the presence of a catalyst such as an alkali carbonate, optionally followed by the addition of a further amount of cyclic alkylene carbonate in the presence of a second catalyst such as an alkali alkoxide, and followed by a subsequent addition of a diacid, such as a saturated or unsaturated aliphatic diacid or aromatic diacid, to enable the formation of a saturated or unsaturated polyester resin. U.S. Patent 5,227,460 discloses as one preferred unsaturated polyester resin a poly(propoxylated bisphenol co-fumarate) which is crosslinked to a gel content of up to about 40 weight percent utilizing a peroxide to provide a toner useful for electrophotographic processes. In U.S. Patent 5,714,568, there is disclosed a process comprising the reaction of a polyfunctional organic acid or anhydride and a cyclic organic carbonate compound in the presence of a catalyst selected from the group consisting of an alkali metal, thereby generating a polyester or copolyester resin. Japanese Patent Publication JP 10077336 A2 discloses a process for the preparation of copolyesters by the reaction of an aromatic diol with an alkylene carbonate in the presence of an alkali carbonate catalyst to form a diol, at a conversion of, for example, more than about 75 percent as measured by the evolution of carbon dioxide byproduct, followed by the subsequent addition of yet another diol and a diacid and continuing the polymerization at high pressure and temperature of about 240°C to yield the aforesaid copolyester resin. The isomeric mixtures in the present invention comprised, for example, of isomers I, II and III are not believed to be disclosed in the JP '336 documents particularly in the isomer ratios of from 0 to 5 weight percent of isomer I, of from 89 to 97 weight percent of isomer II, and from 0 to 15 weight percent of isomer III, by the utitization of a mixture of both an alkali carbonate and an alcohol. The process of the present invention differs, for example, in that the specific mixtures amounts of the three isomers are controlled and obtained by the use of specific catalyst in a multistep process to form polyester resins that can be selected for use as toner binders. Furthermore, the unsaturated polyester, poly(propoxylated bisphenol A - co-fumarate) is not apparently 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 5 to 50 percent gel. Additionally, in the process of the present invention, high pressures are not necessarily utilized in forming the polyester resins, and in embodiments the highest temperature selected to generate the polyester resin is from 200°C to 215°C. Furthermore, the aforementioned '336 Patent utilizes both a diol and diacid during the polymerization steps to form a copolyester. This differs from the present invention wherein in embodiments a diacid is utilized to form the polyester during the polycondensation step. Japanese Patent publication JP 10095840 A2 discloses a process for the preparation of copolyesters by the reaction of an aromatic diol with an alkylene carbonate in the presence of an alkali carbonate catalyst to form a diol, at a conversion of for example, more than about 75 percent as measured by the evolution of carbon dioxide byproduct, followed by the subsequent addition of yet another diol and a mixture of diacid and continuing the polymerization at high pressure and temperature of about 240°C to yield the aforesaid copolyester resin. The isomeric mixtures in the present invention are comprised of isomers I, II and III which do not appear to be recognized or disclosed in the JP '840 documents, particularly in a three step monomer processes to produce the isomer ratios of from about 0 to about 1 weight percent of isomer I, of from 89 to 97 weight percent of isomer II, and from 3 to 15 weight percent of isomer III, by the utilization of a mixture of both an alkali carbonate and alcohol derived alkali. Furthermore, the aforementioned '840 patent utilizes both a diol and diacid during the polymerization steps to form a copolyester. This differs from the present invention wherein in embodiments only a diacid need be utilized to form the polyester during the polycondensation step. The present invention provides a process for the preparation of an unsaturated polyester which comprises (i) reacting an organic diol with a cyclic akylene carbonate in the presence of a first catalyst to thereby form a polyalkoxy diol, (ii) adding thereto a further amount of cyclic alkylene carbonate in the presence of a second catalyst, and (iii) subsequently polycondensing the resulting mixture with an unsaturated dicarboxylic acid, wherein the first catalyst is an alkali carbonate, and wherein the second catalyst is an alkali alkoxide. Preferred embodiments are set forth in the subclaims. It is a feature of this invention is to provide multistep "one pot" economical process for the preparation of polyester resins, such as an unsaturated polyester resin, 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 followed by a subsequent step of adding more alkylene carbonate in the presence of a second alkali alkoxide catalyst such as potassium methoxide, followed by the polycondensation step of adding thereto a diacid such as fumaric acid to produce the polyester resin upon further heating and reducing the pressure. Moreover, there is provided an unsaturated polyester resin, poly (propoxylate bisphenol A - co-fumarate), which can be crosslinked up to about 50 percent gel content with a peroxide such as benzoyl or lauryl peroxide. In a further feature there is provided a toner comprised of an unsaturated polyester resin prepared by a three step monomer addition process, a colorant and optionally a charge enhancing agent. Moreover, in yet a further feature, there is provided a three step monomer addition process for the preparation of an unsaturated resin with a glass transition temperature of from 52°C to 57.9°C. Moreover, in another feature there is provided a process for the preparation of an unsaturated resin, wherein the first step generates a mixture of three isomers of propoxylated bisphenol A, by utilizing alkali 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 or dihydroxy arylene, with an alkylene carbonate in the presence of a catalyst such a as an alkali carbonate or alkali alkoxide, to form an alkoxy diol, preferably in an amount of 100 percent, and preferably of the isomer formulas illustrated herein, followed by the second subsequent addition of alkylene carbonate in the presence of a second alkali alkoxide catalyst, and followed thereafter with the polycondensation process by the addition of a diacid, such as an unsaturated aliphatic diacid or aromatic diacid, to enable the fabrication of an unsaturated polyester resin. Aspects of the present invention relate to a process for the preparation of an unsaturated polyester which comprises (i) reacting an organic diol with a cyclic akylene carbonate in the presence of a first catalyst to thereby form a polyalkoxy diol, and (ii) adding thereto a further amount of cyclic alkylene carbonate in the presence of a second catalyst, and (iii) subsequently polycondensing the resulting mixture with an unsaturated dicarboxylic acid; wherein the first catalyst is an alkali carbonate, and wherein the second catalyst is an alkali alkoxide. The following embodiments are preferred: The preparation of the unsaturated polyester comprises (i) reacting an organic diol in an effective amount of, for example, from 0.95 to 1.05 mole equivalents with a cyclic akylene carbonate in an effective amount of, for example, from 1.95 to 2.05 mole equivalents, in the presence of a first alkali carbonate catalyst in an effective amount of, for example, from 0.001 to 0.1 mole equivalents, to thereby form a polyalkoxy diol, and wherein the polyalkoxy diol is comprised of isomers with, for example, from 2 to 5 weight percent of isomer I, from 95 to 99 weight percent of isomer II, and from 0 to 3 weight percent of isomer III, and the sum of I, II, and III is about 100 percent and wherein said isomers are of the formula as illustrated in Formula 2 and followed by subsequently polycondensing the resulting polyalkoxy diol with a dicarboxylic acid in an amount of from 0.95 to 1.05 mole equivalents, 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. The preparation of the unsaturated polyester comprises (i) reacting an organic diol in an amount of from 0.95 to 1.05 mole equivalents with a cyclic akylene carbonate in an amount of from 1.95 to 2.05 mole equivalents, in the presence of a first alkali carbonate catalyst in an amount of from 0.001 to 0.1 mole equivalents; adding thereto (ii) from 0.05 to 0.45 mole equivalents of cyclic alkylene carbonate in the presence of a second alkali alkoxide catalyst in an amount of from 0.001 to 0.1 mole equivalents, to thereby form a polyakoxy diol comprised of the isomers with from 0 to 1 weight percent of isomer I, from 85 to 97 weight percent of isomer II, and from 3 to 15 weight percent of isomer III, and the sum of I, II, and III is 100 percent and wherein said isomers are of the formula as illustrated in Formula 1 that follows wherein a is as illustrated herein, and followed by subsequently polycondensing the resulting polyalkoxy diol with a dicarboxylic add in an amount of from 0.95 to 1.05 mole equivalents. There is formed a crosslinked polyester generated by the reactive extrusion of a peroxide and an unsaturated polyester. The first catalyst is an alkali carbonate. The second catalyst is an alkali alkoxide. Said reacting is accomplished in the presence of heat; preferably at a temperature of from 160°C to 215°C; more preferably at a temperature of from 180°C to 200°C. Said polycondensing is accomplished by heating; preferably at a temperature of from 185°C to 225°C. Said polycondensing is accomplished by heating at a temperature of from 185°C to 225°C for a duration of from 1 to 5 hours, followed by reducing the pressure from 760 Torr to 1 Torr over a period of from 1 to 6 hours. Subsequent to said polycondensing the reaction mixture is cooled; preferably at a temperature of from 25°C to 40°C; more preferably, to 25°C. There is formed a crosslinked polyester generated by the reactive extrusion of a peroxide and an unsaturated polyester. Said crosslinking is preferably represented by a gel content of from 3 to 75 percent; more preferably 3 to 45 percent. There is formed an unsaturated polyester resin of poly(propoxylated bisphenol co-fumarate), poly(ethoxylated bisphenol co-fumarate), poly(butyloxylated bisphenol co-fumarate), poly(co-propoxylated bisphenol co ethoxylated bisphenol co-fumarate), poly(1,2-propylene fumarate), poly(propoxylated bisphenol co-maleate), poly(ethoxylated bisphenol co-maleate), poly(butyloxylated bisphenol co-maleate), poly(co-propoxylated bisphenol co ethoxylated bisphenol co-maleate), poly(1,2-propylene maleate), poly(propoxylated bisphenol co-itaconate), poly(ethoxylated bisphenol co-itaconate), poly(butyloxylated bisphenol co-itaconate), poly(co-propoxylated bisphenol co ethoxylated bisphenol co-itaconate), or poly(1,2-propylene itaconate). Said diol is 1,2-propanediol, 1,3-propanediol, 1,3- butane diol, pentylene glycol, hexylene glycol, diphenol, neopentyl glycol, diethylene glycol, dipropylene glycol, 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, ethoxylated bisphenol A, bis-(4-hydroxy phenyl) methane, 1,1-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 which diols are optionally selected in an amount of from 0.90 mole equivalents to 1.1 mole equivalents, based on 1 mole equivalent of dicarboxylic acid utilized. More preferably, said diol is 2,2-bis-(4-hydroxy phenyl) propane or bisphenol A. The dicarboxylic acid is fumaric acid, malonic acid, itaconic acid, 2-methylitaconic acid, maleic acid, maleic anhydride, adipic acid, succinic acid, suberic acid, 2-ethyl succinic acid, glutaric acid, dodecylsuccinic acid, 2-methyladipic 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 wherein alkyl contains from 2 to 22 carbon atoms, and are esters of malonate, succinate, fumarate, itaconate, terephthalate, isophthalate, phthalate, cyclohexanedioate, mixtures thereof, and which diacids are optionally selected in an amount of from 0.95 mole equivalent to 1.1 mole equivalents, based on 1 mole equivalent of organic diol utilized. More preferably, the dicarboxylic acid is fumaric acid. The cyclic alkylene carbonate is ethylene carbonate, propylene carbonate, or butylene carbonate, or mixtures thereof, and which alkylene carbonate can be selected in an amount of from 1.90 mole equivalents to 2.45 mole equivalents, based on 1 mole equivalent of organic diol utilized. The first alkali catalyst is an alkali carbonate. Preferably the alkali carbonate is potassium carbonate, sodium carbonate, rubedium carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, manganese carbonate, or barium carbonate and mixture thereof and which alkali carbonates are selected in an amount of from about 0.001 mole equivalent to 0.01 mole, based on 1 mole equivalent of organic diol utilized. More preferably, the alkali carbonate is potassium carbonate. The second catalyst is an alkali alkoxide. Preferably, 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, or sodium t-butoxide, and mixtures thereof, and which alkali alkoxide is selected in an amount of from 0.001 mole equivalent to 0.05 mole equivalent, based on 1 mole equivalent of organic diol utilized. More preferably, the alkyl alkoxide is potassium t-butoxide Said first catalyst is selected in an amount of from 0.01 to 0.1 mole percent by weight of the unsaturated polyester. Said second catalyst is selected in an amount of from 0.01 to 0.1 mole percent by weight of the unsaturated polyester. The peroxide is an aliphatic peroxide, an aromatic peroxide, or mixtures thereof, preferably, benzoyl peroxide, lauryl peroxide, t-butyl peroxide, propyl peroxide, or stearyl peroxide. The polyester resin is formed by (i) reacting an organic diol in an amount of from 0.95 to 1.05 mole equivalents, with a cyclic akylene carbonate in an amount of from 1.95 to 2.05 mole equivalents, and a catalyst in an amount of from 0.001 to 0.1 mole equivalents at a temperature of from 175°C to 205°C, for a duration of, for example, from 1 to 6 hours; and followed by polycondensing with a dicarboxylic acid in an amount of from 0.95 to 1.05 mole equivalents, for a duration of, for example, from 1 to 3 hours, and followed by reducing the pressure from 760 Torr to 1 Torr over a period of from 1 to 6 hours. The polyester resin is formed by (i) reacting an organic diol in an amount of from 0.95 to 1.05 mole equivalent, with a cyclic akylene carbonate in an amount of from 1.95 to 2.05 mole equivalents, and a catalyst in an amount of from 0.001 to 0.1 mole equivalent, at a temperature of from 175°C to 205°C, for a duration of from 1 to 6 hours; (ii) adding thereto a cyclic akylene carbonate in an amount of from 0.05 to 0.35 mole equivalent, with a second alkali alkoxide catalyst in an amount of from 0.001 to 0.1 mole equivalent, at a temperature of from 185°C to 205°C; and (iii) followed by polycondensing with a dicarboxylic acid in an amount of from 0.95 to 1.05 mole equivalent, for a duration of from 1 to 3 hours, and followed by reducing the pressure from 760 Torr to 1 Torr over a period of from 1 to 6 hours. The unsaturated polyester resin is obtained from (i) condensing 0.95 to 1.05 mole equivalent of an organic diol, with from 1.95 to 2.05 mole equivalent of an alkylene carbonate in the presence of a first alkali catalyst at a temperature of from 175°C to 205°C, for a duration of from 1 to 6 hours; and (ii) adding thereto a further amount of from 0.05 to 0.35 mole equivalent of a cyclic alkylene carbonate and a second catalyst a temperature of from 185°C to 205°C, for a duration of from 1 to 3 hours; and (iii) polycondensing with a dicarboxylic acid in an amount of from 0.95 to 1.05 mole equivalent, for a duration of from 1 to 3 hours, and followed by reducing the pressure from 760 Torr to 1 Torr over a period of from 1 to 6 hours. Said cyclic alkylene carbonate is employed in an amount of from 1.9 equivalents to 2.1 mole equivalents, based on 1 mole equivalent of organic diol utilized. There is further added a cyclic alkylene carbonate in an amount of from 0.05 mole equivalent to 0.30 mole equivalent, based on 1 mole equivalent of organic diol utilized. The unsaturated polyester resin is obtained from (i) condensing 0.95 to 1.05 mole equivalent of an organic diol, with from 1.95 to 2.05 mole equivalent of an alkylene carbonate in the presence of a first alkali catalyst at a temperature of from 175°C to 205°C, for a duration of from 1 to 6 hours; and (ii) adding thereto a further amount of from 0.05 to 0.35 mole equivalent of a cyclic alkylene carbonate and a second catalyst a temperature of from 185°C to 205°C, for a duration of from 1 to 3 hours; and (iii) followed by a third step comprised of adding an unsaturated dicarboxylic acid, heating the mixture of from 185°C to 220°C, followed by reducing the pressure from 760 Torr to 1 Torr. The polyester resulting is poly(propoxylated bisphenol co-fumarate), poly(ethoxylated bisphenol co-fumarate), poly(butyloxylated bisphenol co-fumarate), poly(co-propoxylated bisphenol co ethoxylated bisphenol co-fumarate), or poly(propoxylated bisphenol co-maleate). The polyester is poly(propoxylated bisphenol), and the bis-alkoxy diol is propoxylated bisphenol A 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 higher ordered propoxylated bisphenol A polyols, illustrated as monomers I, II and III, respectively, of Formula 2 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. The polyester is poly(propoxylated bisphenol), and the bis-alkoxy diol is propoxylated bisphenol A 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 higher ordered propoxylated bisphenol A polyols, illustrated as monomers I, II and III, respectively, of Formula 1 wherein a is zero, 1, 2 or a mixture of zero, 1 and 2. The isomers contain preferably from 2 to 5 weight percent of isomer I, from 90 to 97 weight percent of isomer II, and from 0 to 3 weight percent of isomer III, and the sum of I, II, and III is 100 percent. 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 presence of a first catalyst to thereby form a bis-alkoxy diol, and (ii) adding thereto a further 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 wherein a represents the number of segments and with from 0 to 1 weight percent of isomer I, from 85 to 97 weight percent of isomer II, and from 3 to 15 weight percent of isomer III, and the sum of I, II, and III is 100 percent. The aromatic R group is a radical moiety of the group selected from 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, ethoxylated bisphenol A, bis-(4-hydroxy phenyl) methane, 1,1-bis-(4-hydroxy phenyl) ethane and hydroquinone, The present invention provides also a process for the preparation of crosslinked polyesters obtained from the reactive extrusion of a peroxide and an unsaturated polyester resin, and which resin is generated by (i) reacting an organic diol with a cyclic akylene carbonate in the presence of a first catalyst to thereby form a polyalkoxy diol; (ii) adding thereto a further amount of cyclic alkylene carbonate in the presence of a second catalyst; and (iii) subsequently polycondensing the resulting mixture with an unsaturated dicarboxylic acid,wherein the first catalyst is an alkali carbonate, and wherein the second catalyst is an alkali alkoxide. The following embodiments are preferred: The colorant is a dye, or a pigment. The toner contains a wax component. The toner contains a charge additive. The toner contains a wax component and a charge additive. The toner contains surface additives. Said additives are preferably comprised of silicas, metal oxides, fatty acid salts, or mixtures thereof. The polyester is poly(propoxylated bisphenol co-fumarate). The present invention provides also a multi step process for the preparation of polyester polymers, especially an unsaturated polyester resin, wherein the multi step process is a three step monomer addition process, 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, in the presence of a suitable catalyst such as an alkali carbonate, such as potassium carbonate, followed by a second step comprising of the addition of a suitable diacid or dicarboxylic acid, such as fumaric acid, or a preferred embodiment there 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 ethylene carbonate, propylene carbonate, in the presence of a suitable catalyst such as an alkali carbonate, such as potassium carbonate; (ii) adding thereto a further amount of cyclic akylene carbonate in the presence of a second catalyst such as an alkali alkoxide, for example, sodium methoxide or potassium t-butoxide; and followed by (iii) the addition of a suitable diacid such as a dicarboxylic acid, and preferably fumaric acid. The polyester resin obtained is preferably an unsaturated polyester which can be subjected to crosslinking, especially reactive extrusion processes, to a high gel content, such as from 0.1 to 60 percent, and preferably from 3 to 45 percent gel, in the presence of an initiator such as a peroxide, like benzoyl or lauryl peroxide and which peroxide is selected in an amount of for example, from 0.01 to 5 weight percent of the resin. Toners containing crosslinked polyester resins exhibit, for example, desirable low temperature fixing characteristics such as from 120°C to 145°C, and high offset properties such as from 180°C to 225°C. Moreover, the present invention is related to an economical process for preparing an unsaturated polyesters. resin, such as for example, poly (propoxylated bisphenol A - co- fumarate), from three or more monomers or isomers of propoxylated bisphenol A and fumaric acid, and wherein the three or more isomers of propoxylated bisphenol A are obtained from the condensation of bisphenol A with a cyclic alkylene carbonate in the presence of first catalyst such as potassium carbonate, and optionally followed by the addition of a further amount of cyclic alkylene carbonate in the presence of a second catalyst such as sodium methoxide or potassium t-butoxide. The aforementioned resin, poly(propoxylated bisphenol A co-fumarate), can be prepared by a two step process comprised of (i) the alkoxylation of for example, from 0.95 to 1.05 mole percent of 2,2-di(4-hydroxyphenyl)-propane also known as bisphenol A, with for example, from 1.95 to 2.05 mole percent of propylene carbonate and for example, from 0.0001 to 0.2 mole percent of a catalyst such as potassium carbonate, at a suitable temperature of for example, from 160 to 205°C for a suitable duration of from 1 to 9 hours, resulting in the formation of a mixture of propoxylated bisphenol A, comprised 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 ordered propoxylated bisphenol A polyols, illustrated as monomers I, II and III, respectively, as follows FORMULA 1 wherein a is zero, 1, 2, or a mixture of zero, 1 and 2. FORMULA 2 wherein R is an aromatic or aryl group; R' is an alkyl group or hydrogen and a is an integer or number of from 0 to 3; aromatic being, for example, aryl with, for example, 6 to 30 carbon atoms; and alkyl containing, for example, 1 to 25, and preferably 12 carbon atoms. The ratios of the propoxylated bisphenol A mixtures can vary, and in many instances, the ratio obtained, reference Formula 1, is from 2 to 5 weight percent of monomer I, and from 95 to 99 percent by weight of monomer II, and from 0 to 3 weight percent of monomer III, and provided that the total percentage sums of the three monomers are 100 percent. The second step is generally comprised of a polyesterification of the aforementioned intermediate propoxylated bisphenol A, with from 0.95 to 1.05 mole percent of fumaric acid, at a temperature of, for example, from 180°C to 210°C for a duration of from 1 to 6 hours, followed by reducing the pressure by, for example, from 0.1 to 40 mm-Hg for a suitable duration of preferably, for example, from 1 to 3 hours, to result in the formation of the unsaturated polyester, Poly(propoxylated bisphenol A - co-fumarate). In a specific embodiment of the present invention, the aforementioned mixture of propoxylated monomers I, II and III can be varied by the addition of an excess of alkylene carbonate in the presence of a second alkali alkoxide initiator such as potassium t-butoxide or sodium methoxide after the first aforementioned step. More specifically, in an 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 0.95 to 1.05 mole percent of 2,2-di(4-hydroxyphenyl)-propane also known as bisphenol A, with for example, from 1.95 to 2.05 mole percent of propylene carbonate and for example, from 0.0001 to 0.2 mole percent of a catalyst such as potassium carbonate, at a suitable temperature of, for example, from 160 to 205°C for a suitable duration of, for example preferably from 1 to 9 hours, resulting in the formation of a mixture of propoxylated bisphenol A, comprised of 2 to 5 weight percent of monomer I (Formula 1), and from 95 to 99 percent by weight of monomer II, and from 0 to 3 weight percent of monomer III, and provided that the total percentage sums of the three monomers are 100 percent; followed by (ii) the further addition of from 0.05 to 0.25 mole percent of propylene carbonate with from 0.001 to 0.3 mole percent of a second alkali alkoxide catalyst such as potassium t-butoxide at a temperature of from 180°C to 205°C for a suitable duration of for example preferably from 1 to 3 hours, and thereby resulting in a mixture of propoxylated bisphenol A comprised of, for example, of from 0 to 0.5 weight percent of monomer I, and from 84 to 99 percent by weight of monomer 2, and from 3 to 15 weight percent of monomer 3, and provided that the total percentage sums of the three monomers are 100 percent; and followed by the third step generally comprised of a polyesterification of the aforementioned intermediate propoxylated bisphenol A, with from 0.95 to 1.05 mole percent of fumaric acid, at a temperature of for example, from 180 to 210°C under reduced pressure of, for example, from 0.1 to 40 mm-Hg for a suitable duration of preferably for example, from 3 to 6 hours, to result in the formation of the unsaturated polyester, poly(propoxylated bisphenol A - co-fumarate). The aforementioned unsaturated polyester, poly(propoxylated bisphenol A-co-fumarate), can be subjected to crosslinking, especially reactive extrusion processes, to a high gel content, such as from 0.1 to 60 percent, and preferably from 3 to 45 percent gel, in the presence of an initiator such as a peroxide, like benzoyl or lauryl peroxide and which peroxide is selected in an amount of for example, from 0.01 to 5 weight percent of the resin. The unsaturated polyester resins is preferably derived from a mixture of propoxylated bisphenol A, and wherein the 4-(2-hydroxyethyl)-bisphenol A (Isomer I) is minimized or avoided due to the inhibition to high polymerization degree, and interference with the subsequent crosslinking with the peroxide initiator. These latter inhibition is primarily due to aryl hydroxide moieties (or phenolic). Thus, it is preferred that this isomer I, the 4 (2-hydroxyethyl)-bisphenol A, is minimized by this process or avoided and controlled to a level of less than 1 weight percent of the isomeric mixture, and preferably minimized to less than 0.1 weight percent, or more preferably to zero weight percent of the isomeric mixture (Formula 1). This aforementioned mixture of propoxylated monomers I, II and III can be varied by the concentration of cyclic alkylene carbonate and type of catalyst. Generally, the alkali carbonate catalysts such as sodium carbonate, potassium carbonate, lithium carbonate are useful in the alkoxylation of aryl diols, such as bisphenol A to yield primarily a mixture of wherein the bis 4,4'(2-hydroxyethyl)-bisphenol A (isomer II of Formula 1), is the predominant product of from 95 to 100 weight percent, and isomer III is minimized of from 0 to 3 percent by weight. Also, the amount of isomer I, is usually from 2 to 5 percent by weight and this isomer may not be as effective for obtaining highly crosslinked resins due to its inhibition with peroxides. In the presence of an initiator such as an alkali alkoxide, for example, sodium methoxide, potassium methoxide, lithium methoxide, potassium t-butoxide, then the reaction of an aryl diol with a cyclic alkylene carbonates results in the formation of both the bis 4,4'-(2-hydroxyethyl)-bisphenol A (Isomer II) in an amount of from 60 to 85 weight percent, and 4-(2'-hydroxyethyl-2-oxyethyl)-4'-(2-hydroxyethyl)-bisphenol A and higher ordered polyols (Isomer III and wherein a is, for example, zero, 1, 2 or mixtures of 1 and 2) in an amount of from 15 to 40 percent by weight, and provided that the total percentage sums of the three monomers are 100 percent: as illustrated in comparative Example VI. Hence, in order to control the reaction mixture such that the three isomeric intermediate propoxylated bisphenol A products are obtained in an amount comprised, for example, of from 0 to 1 weight percent of monomer I, and from 84 to 99 percent by weight of monomer II, and from 3 to 15 weight percent of monomer III, and provided that the total percentage sums of the three monomers are 100 percent, it is necessary to provide a process which is comprised of the three aforementioned steps, that is, comprised of (i) the alkoxylation bisphenol A, propylene and a catalyst such as potassium carbonate, at a suitable temperature of, for example, from 160°C to 205°C for a suitable duration of, for example, preferably from 1 to 9 hours, resulting in the formation of a mixture of propoxylated bisphenol A, comprised of 2 to 5 weight percent of monomer I (Formula 1), and from 95 to 99 percent by weight of monomer II, and from 0 to 3 weight percent of monomer III, and provided that the total percentage sums of the three monomers are 100 percent; (ii) followed by the addition of from 0.05 to 0.25 mole percent of propylene carbonate and for example, from 0.0001 to 0.01 mole percent of a second alkali alkoxide catalyst such as potassium t-butoxide at a temperature of from 180 to 205°C for a suitable duration of for example preferably from 1 to 3 hours, and thereby resulting in a mixture of propoxylated bisphenol A comprised of, for example, of from 0 to 0.5 weight percent of monomer I, and from 84 to 97 percent by weight of monomer II, and from 3 to 15 weight percent of monomer III, and provided that the total percentage sums of the three monomers are 100 percent The unsaturated polyester resin, poly(propoxylated bisphenol A co-fumarate), described in the two step monomer process and utilizing only the alkali carbonate catalyst, generally exhibits high glass transition temperatures of from 58°C to 62°C at a molecular weight of from 15,000 to 20,000 grams per mole as measured by gel permeation chromatography. In many instances, it is desired that toner resins exhibit high glass transition temperatures of from 58°C to 62°C, such that toner blocking is avoided or minimized, as well as the minimization of copy to copy offset. In order to obtain a high glass transition temperatures of from 58°C to 62°C at a molecular weight of from 15,000 to 20,000 grams per mole, it is necessary that the unsaturated polyester resin is derived from the propoxylated bisphenol A mixture, wherein the predominant isomer (Formula 1) is comprised of from 95 to 99 weight percent of isomer II, and the isomer III is minimized of from 0 to 3 weight percent, because this latter isomer reduces the glass transition temperature of the resin. Conversely, in many instances, an unsaturated polyester resin, for example, poly(propoxylated bisphenol A - co-fumarate), with lower glass transition temperature such as from 52°C to 57.9°C is desired at a molecular weight of from 15,000 to 20,000 grams per mole as measured by gel permeation chromatography. Such unsaturated polyester resins with lower glass transition temperatures are useful in providing toners with low minimum fusing temperatures, thereby reducing the temperature of the fusing subsystem and reducing the energy consumption of the xerographic device. Examples of polyesters obtained with the processes of the present invention are poly(propoxylated bisphenol co-fumarate), poly(ethoxylated bisphenol co-fumarate), poly(butyloxylated bisphenol co-fumarate), poly(co-propoxylated bisphenol co ethoxylated bisphenol co-fumarate), 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(co-propoxylated bisphenol co ethoxylated bisphenol co-maleate). Specific examples of diols selected for the process of the present invention include for example, alkylene diols such as ethane diol, 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 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, ethoxylated bisphenol A, propoxylated bisphenol A, bis-(4-hydroxy phenyl) methane, 1,1-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, mixtures thereof inclusive of other known diols; and which diols are employed, for example, in an amount of from 0.95 mole equivalents to 1.05 mole equivalents, based on 1 mole equivalent of dicarboxylic acid utilized. Dicarboxylic acids examples, 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, 2-ethyl succinic acid, glutaric acid, dodecylsuccinic acid, 2-methyladipic 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 wherein the alkyl groups are from 1 carbon chain to 23 and preferably from 2 to 18 carbon chains, and are esters of malonate, succinate, fumarate, itaconate, terephthalate, isophthalate, phthalate, cyclohexanedioate, mixture thereof, and which diacids are employed, for example, in an amount of from 10 to 60 percent by weight, and preferably from 25 to 50 percent by weight by weight of the reactants. Examples of cyclic alkylene carbonates selected for the process of the present invention contain from 3 to 25 carbon atoms, include ethylene carbonate, 1,2-propylene carbonate, and 1,2-butylene carbonate, mixture thereof, which alkylene carbonates are employed, for example, in an amount of from 1.95 mole equivalents to 2.40 mole equivalents, based on 1 mole equivalent of organic diol utilized. First catalyst examples 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, and barium carbonate which are employed, for example, in an amount of from 0.001 to 0.1 mole equivalents, based on 1 mole equivalent of organic diol utilized. Second catalyst examples selected for the process of the present invention include alkali alkoxides such as 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, lithium iodide, sodium iodide, potassium iodide, sodium hydroxide, potassium hydroxide, lithium hydroxide, mixture thereof, and which catalysts are employed, for example, in an amount of from 0.001 mole equivalent to 0.1 mole equivalent, based on 1 mole equivalent of organic diol utilized. Various known suitable colorants, such as dyes, pigments, and mixtures thereof and present in the toner containing the polyester generated with the processes of the present invention in an effective amount of, for example, from 1 to 25 percent by weight of the toner, and preferably in an amount of from 2 to 12 weight percent, include carbon black like REGAL 330®; magnetites, such as Mobay magnetites MO8029™. MO8060™; Columbian magnetites; MAPICO BLACKS™ and surface treated magnetites; Pfizer magnetites CB4799™, CB5300™, CB5600™, MCX6369™; Bayer magnetites, BAYFERROX 8600™, 8610™; Northern Pigments magnetites, NP-604™ NP-608™; Magnox magnetites TMB-100™, or TMB-104™. As colored pigments, there can be selected cyan, magenta, yellow, red, green, brown, blue or mixtures thereof. Various known suitable effective positive or negative charge enhancing additives can be selected for incorporation into the toner compositions, preferably in an amount of 0.1 to 10, more preferably 1 to 3, percent by weight. Examples of the additives include quaternary ammonium compounds inclusive of alkyl pyridinium halides; alkyl pyridinium compounds, reference U.S. Patent 4,298,672, organic sulfate and sulfonate compositions, U.S. Patent 4,338,390, cetyl pyridinium tetrafluoroborates; distearyl dimethyl ammonium methyl sulfate; aluminum salts such as BONTRON E84™ or E88™ (Hodogaya Chemical). There can also be blended with the toner compositions toner additives, such as external additive particles including flow aid additives, which additives are usually present on the surface thereof. Examples of these additives include metal oxides like titanium oxide, tin oxide, mixtures thereof, colloidal silicas, such as AEROSIL®, metal salts and metal salts of fatty acids inclusive of zinc stearate, aluminum oxides, cerium oxides, and mixtures thereof, which additives are generally present in an amount of from 0.1 percent by weight to 5 percent by weight, and preferably in an amount of from 0.1 percent by weight to 1 percent by weight. Various known crosslinking agents or chemical initiators can be selected for the crosslinking of the prepared unsaturated polyester resins, and which agents are selected in an effective amount of, for example, from 0.5 to 5 percent by weight of the toner, and preferably in an amount of from 1 to 5 weight percent, such agents including preferably peroxides such as organic peroxides or azo-compounds for the generation of crosslinked toner resins of the invention. By permitting use of low concentrations of chemical initiator and utilizing substantially all of it in the crosslinking reaction, usually in the concentration range of from 0.01 to 10 weight percent, and preferably in the range from 0.1 to 4 weight percent, the residual contaminants produced in the crosslinking reaction in preferred embodiments can be minimal. Since the crosslinking can be accomplished at high temperature such as from 120°C to 180°C, the reaction is rapid (e.g., less than 10 minutes, preferably 2 seconds to 5 minutes residence time) and thus little or no unreacted initiator remains in the product . The low melt toners and toner resins may be prepared by a reactive melt mixing process wherein reactive polyester resins are partially crosslinked. For example, low melt toner resins and toners may be fabricated by a reactive melt mixing process as illustrated for example, in U.S. Patent 5,376,494, and for example comprising the steps of (1) melting a reactive base unsaturated polyester resin obtained as illustrated herein, thereby forming a polymer melt, in a melt mixing device; (2) initiating crosslinking of the polymer melt, preferably with a chemical crosslinking initiator and increased reaction temperature; (3) retaining the polymer melt in the melt mixing device for a sufficient residence time that a partial crosslinking of the base resin may be achieved; (4) providing sufficiently high shear during the crosslinking reaction to retain the gel particles formed during crosslinking small in size and well distributed in the polymer melt; (5) optionally de-volatilizing the polymer melt to remove any effluent volatile. The high temperature reactive melt mixing process allows for a rapid crosslinking which enables the production of substantially only microgel particles, and the high shear of the process prevents undue growth of the microgels and enables the microgel particles to be uniformly distributed in the resin. The resins obtained are generally present in the toner in an amount of from 40 to 98 percent by weight, and more preferably from 70 to 98 percent by weight, although they may be present in greater or lesser suitable amounts. For example, the polyester toner resins of the present invention can be subsequently melt blended or otherwise mixed with a colorant, charge carrier additives, surfactants, emulsifiers, pigment dispersants, flow additives. The resultant product can then be pulverized by known methods such as milling to form toner particles. The toner particles preferably have an average volume particle diameter of 5 to 25, more preferably 5 to 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 reactive extrusion reactions. The present invention provides a low fix temperature toner resin, and specifically a low fix temperature toner resin based on crosslinked resin comprised of crosslinked and linear portions, the crosslinked portion consisting essentially of microgel particles with an average volume particle diameter up to 0.1 micron, preferably 0.005 to 0.1 micron, said microgel particles being substantially uniformly distributed throughout the linear portions. This resin may be prepared by a reactive melt mixing process, including a process disclosed in detail in U.S. Patent 5,376,494. 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 scanning electron microscopy and transmission electron microscopy. When produced by a reactive melt mixing process wherein the crosslinking occurs at high temperature and under high shear, the size of the microgel particles does not continue to grow with increasing degree of crosslinking. Also, the microgel particles are distributed substantially uniformly throughout the linear portion. The crosslinked portions or microgel particles are prepared in such a manner that there is substantially no distance between the polymer chains. Thus the crosslinking is preferably not accomplished via monomer or polymer bridges. The polymer chains are directly connected, for example at unsaturation sites or other reactive sites, or in some cases by a single intervening atom such as, for example, oxygen. Therefore, the crosslinked portions are very dense and do not swell as much as gel produced by conventional crosslinking methods. This crosslink structure is different from conventional crosslinking in which the crosslink distance between chains is quite large with several monomer units, and where the gels swell very well in a solvent such as tetrahydrofuran or toluene. These highly crosslinked dense microgel particles distributed throughout the linear portion impart elasticity to the resin which improves the resin offset properties, while not substantially affecting the resin minimum fix temperature. The crosslinked polyester toner resin contains for example, a weight fraction of the microgel (gel content) in the resin mixture in the range typically from 0.001 to 50 weight percent, preferably 0.1 to 40 or 10 to 19 weight percent. The linear portion is comprised of base resin, preferably unsaturated polyester, in the range from 50 to 99.999 percent by weight of the toner resin, and preferably in the range from 60 to 99.9 or 81 to 90 percent by weight of the toner resin. The linear portion of the resin preferably consists essentially of low molecular weight reactive base resin which did not crosslink during the crosslinking reaction, and is preferably an unsaturated polyester resin. The number-average molecular weight (M n ) of the linear portion as measured by gel permeation chromatography (GPC) is in the range typically from 1,000 to 20,000, and preferably from 2,000 to 5,000. The weight average molecular weight (M w ) of the linear portion is in the range typically from 2,000 to 40,000, and preferably from 4,000 to 15,000. The molecular weight distribution (M w /M n ) of the linear portion is in the range typically from 1.5 to 6, and preferably from 2 to 4. The onset glass transition temperature (Tg) of the linear portion as measured by differential scanning calorimeter (DSC) for preferred embodiments is in the range typically from 50°C to 70°C, and preferably from 51°C to 60°C. Melt viscosity of the linear portion of preferred embodiments as measured with a mechanical spectrometer at 10 radians per second is from 5,000 to 200,000 poise, and preferably from 20,000 to 100,000 poise, at 100°C and decreases sharply with increasing temperature to from 100 to 5,000 poise, and preferably from 400 to 2,000 poise, as temperature rises from 100°C to 130°C. The toner resin can contain a mixture of crosslinked resin microgel particles and a linear portion as illustrated herein. In embodiments of the toner resin of the invention, the onset Tg is in the range typically from 50°C to 70°C, and preferably from 51°C to 60°C, and the melt viscosity as measured with a mechanical spectrometer at 10 radians per second is from 5,000 to 200,000 poise, and preferably from 20,000 to 100,000 poise, at 100°C and from 10 to 20,000 poise at 160°C. The low fix temperature of the toner resin is a function of the molecular weight and molecular weight distribution of the linear portion, and is not affected by the amount of microgel particles or degree of crosslinking. This is portrayed by the proximity of the viscosity curves at low temperature (such as, for example, at 100°C) in which the melt viscosity is in the range from 20,000 to 100,000 poise as measured with a mechanical spectrometer at 10 radians per second. The hot offset temperature is increased with the presence of microgel particles which impart elasticity to the resin. With a higher degree of crosslinking or microgel content, the hot offset temperature increases. This is reflected in divergence of the viscosity curves at high temperature (such as, for example, at 160°C) in which the melt viscosity is typically in the range from 10 to 20,000 poise as measured at 10 radians per second depending on the amount of microgel particles in the resin. The toner resin can provide a low melt toner with a minimum fix temperature of from 100°C to 200°C, preferably 100°C to 160°C, more preferably 110°C to 140°C, provide the low melt toner with a wide fusing latitude to minimize or prevent offset of the toner onto the fuser roll, and maintain high toner pulverization efficiencies. The low melt toner resin preferably has a fusing latitude greater than 10°C, preferably from 10°C to 120°C, and more preferably more than 20°C and even more preferably more than 30°C. The MFT of the toner is not believed to be sensitive to the crosslinking in the microgel particles of the toner resin, while the fusing latitude increases significantly as a function of the crosslinking or content of microgels in the toner resin. Thus, it is possible to produce a series of toner resins and thus toners with the same MFT, but with different fusing latitudes. Toner resins and thus toners of the present invention show minimized or substantially no vinyl offset. As the degree of crosslinking or microgel content increases, the low temperature melt viscosity does not change appreciably, while the high temperature melt viscosity goes up. In an exemplary embodiment, the hot offset temperature can increase approximately 30 percent. This can be achieved by crosslinking in the melt 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 uniformly throughout the linear portion, and substantially no intermediates or sol portions which are crosslinked polymers with low crosslinking density. When crosslinked intermediate polymers are generated by conventional polymerization processes, the viscosity curves generally shift in parallel from low to high degree of crosslinking. This is reflected in increased hot offset temperature, but also increased minimum fix temperature. In a preferred embodiment, the crosslinked portion consists essentially of very high molecular weight microgel particles with high density crosslinking (as measured by gel content) and which are not soluble in substantially any solvents such as, for example, tetrahydrofuran and toluene. The microgel particles are highly crosslinked polymers with a very small, if any, crosslink distance. This type of crosslinked polymer may be formed by reacting chemical initiator with linear unsaturated polymer, and more preferably linear unsaturated polyester, at high temperature and under high shear. The initiator molecule breaks into radicals and reacts with one or more double bond or other reactive site within the polymer chain forming a polymer radical. This polymer radical reacts with other polymer chains or polymer radicals many times, forming a highly and directly crosslinked microgel. This renders the microgel very dense and results in the microgel not swelling very well in solvent. The dense microgel also imparts elasticity to the resin and increases its hot offset temperature while not affecting its minimum fix temperature. The weight fraction of the microgel (gel content) in the resin may be defined as follows: Gel Content = Total Sample Weight minus the Weight of Soluble Polymer (Total Sample Weight) x 100 percent. The gel content may be calculated by measuring the relative amounts of linear, soluble polymer and the nonlinear, crosslinked polymer utilizing the following procedure: (1) the sample of the crosslinked resin to be analyzed, in an amount between 145 and 235 milligrams, is weighed directly into a glass centrifuge tube; (2) 45 milliliters toluene is added and the sample is put on a shaker for at least 3 hours, preferably overnight; (3) the sample is then centrifuged at about 2500 rpm for 30 minutes and then a 5 milliliters aliquot is carefully removed and put into a pre-weighed aluminum dish; (4) the toluene is allowed to air evaporate for about 2 hours, and then the sample is further dried in a convection oven at 60°C for about 6 hours or to constant weight; (5) the sample remaining, times nine, gives the amount of soluble polymer. Thus, utilizing this quantity in the above equation, the gel content can be easily calculated. Linear unsaturated polyesters selected as the base resin are low molecular weight condensation polymers which may be formed by the step-wise reactions between both saturated and unsaturated diacids (or anhydride) and dihydric alcohols (glycols or diols) and by the multi step processes illustrated herein, and more specifically, by a process which comprises reacting an organic diol with an akylene carbonate in the presence of an alkali carbonate catalyst to thereby form a bis- alkoxy diol, followed optionally by further reacting the bis-alkoxy diol with a cyclic akylene carbonate in the presence of a second alkali alkoxide catalyst, and followed by polycondensing the resulting mixture with an unsaturated diacid and wherein the bis-alkoxy diol is comprised of the isomers with from 0 to 5 weight percent of isomer I, from 80 to 99 weight percent of isomer II, and from 0.1 to 15 weight percent of isomer III, and provided that the sum of I, II, and III is 100 percent and wherein the isomers are of the formula as represented in Formula 1. 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 percent by weight of 4-(2-hydroxyethyl)-bisphenol A, 92 percent by weight of bis 4,4'-(2-hydroxyethyl)-bisphenol A, and 3 percent by weight 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 of 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 percent by weight of 4-(2-hydroxyethyl)-bisphenol A, 92 percent by weight of bis 4,4'-(2-hydroxyethyl)-bisphenol A, and 3 percent by weight of 4-(2'-hydroxyethyl-2-oxyethyl)-4'-(2-hydroxyethyl)-bisphenol A. To this was added 306 grams of fumaric acid and 220 milligrams of hydroquinone, and the reactor was then heated to a temperature of about 208°C over a 1.5 hour period, after which the mixture was maintained at this temperature for an additional 3 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 (about 760 Torr), and the resin was discharged through the bottom drain valve into a container and allowed to cool to ambient temperature (about 25°C) overnight (about 16 hours). The resin product poly(propoxylated bisphenol co-fumarate), exhibited a glass transition temperature (onset) 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 minute using a 2.16 kilograms weight 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 13,600 grams/mole and the number average molecular weight was found to be 3,500 grams/mole with a polydispersity of 3.9 as measured by the gel permeation chromatography and using tetrahydrofuran as the solvent and polystyrene as the standard. The acid number of this resin was found to be 12.9 milligrams of KOH per gram of sample. Three hundred (300) grams of the above unsaturated polyester obtained was dry-blended using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water, which peroxide was obtained from Elf Atochem. The resulting blended mixture was extruded through an APV 15 millimeters twin screw extruder, which were set at 330°F. The extrudate strand from the extruder die was cooled in a water bath and the solid strands resulting were air-dried and then crushed into fine particles (95 percent by weight passing through 3.36 millimeters sieve) of less than about 3 millimeters in dimension. The gel content of the crosslinked product (A), defined as the percentage of toluene insoluble portion not passing through a 0.45 micron filter in a filtration procedure, was found to be about a low 7.5 percent. The above polyester resin product was not effectively crosslinked utilizing Lucidol 75, primarily because of the presence of about 4.6 percent of isomer I, in the resin which is believed to inhibit the crosslinking reaction. Drawbacks or disadvantages in this Comparative Example include both economics and resin properties obtained. More specifically, the propoxylated bisphenol A obtained from Milliken Chemical Company as Synfac 8029, was obtained commercially at a higher cost of from about 20 to about 50 percent more than the reactants selected for the present invention, mainly because it is obtained from the anionic reaction of bisphenol A and propylene oxide, followed by purification. Furthermore, the isomers of propoxylated bisphenol A (Formula 1) contains up to 3 percent of the third isomer and resulting in an unsaturated polyester resin with a glass transition of 56.2°C, and although this resin is useful in many applications, there is a need for a resin of higher Tg, such as from 58 to 62°C, such that higher blocking temperatures can be obtained as well as minimized copy to copy offset or reduced vinyl offset properties. Additionally, due to the presence of about 4.5 percent by weight of Isomer I, the crosslinking of the resin with Lucidol 75, resulted in low gel content EXAMPLE 11 (outside the scope of the claims) An unsaturated polyester resin, poly(propoxylated bisphenol co-fumarate), derived from 1 mole equivalent of fumaric acid, 2.0 mole equivalent of propylene carbonate and 1 mole equivalent bisphenol A, was prepared in a two-step process using potassium carbonate as the condensation catalyst in the first step. In the first step, a 2 liter Hoppes Reactor 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 to 190°C over a 1 hour period with stirring and maintained at that temperature for an additional 4 hours. A sample (about 1 grams) of this mixture was analyzed by LC chromatography, wherein it was found to 2.8 percent by weight of 4-(2-hydroxyethyl)-bisphenol A (Isomer I), 96.5 percent by weight of bis 4,4'-(2-hydroxyethyl)-bisphenol A (Isomer II), and 0.7 percent by weight of 4-(2'-hydroxyethyl-2-oxyethyl)-4'-(2-hydroxyethyl)-bisphenol A (Isomer III), reference Formula 1 throughout. 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 butylstannoic acid obtained as FASCAT 4100 from Elf Atochem, and 220 milligrams of hydroquinone. The temperature was then raised to 190°C over a 2 hour period, and the pressure was then reduced to 6.5 Torr over a 3 hour period, wherein water was collected in the distillation receiver. The resin, poly(propoxylated bisphenol A co-fumarate), was then discharged through the bottom drain valve, and exhibited a glass transition temperature (onset) of 60.5°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 23.4 grams per 10 minute 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/mole and the number average molecular weight was found to be 4,700 grams/mole with a polydispersity of 2.7 as measured by the gel permeation chromatography and using tetrahydrofuran as the solvent and polystyrene as the standard. The acid number of this resin was 26.3 milligrams of KOH per gram of sample. The advantages of this process is both economics and resin property obtained. More specifically, the propoxylated bisphenol is obtained directly from bisphenol A and propylene carbonate, and does not involve a purification. Furthermore, by this process, less than 1 percent of the third Isomer (Formula 1) was obtained, and there resulted a polyester resin of a higher glass transition temperature (60.5°C), which resin was more useful as a toner binder in order to prevent blocking or copy offset, as compared to the resin of Comparative Example I, wherein a Tg of 56°C was obtained, rendering a toner with this resin prone to blocking and offset. Three hundred (300) grams of the unsaturated polyester obtained was weighed and dry-blended using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water obtained from Elf Atochem. The resulting blended mixture was extruded through an APV 15 millimeter twin screw extruder, which were set at 330°F. The extrudate strand from the extruder die was cooled in a water bath and the solid strands resulting were air-dried and then crushed into fine particles (95 percent by weight passing through 3.36 millimeters sieve) of less than about 3 millimeters in dimension. The melt index of the crosslinked product (A) was found to be 4.2 gram per 10 minutes using 16.6 kilograms weight at a temperature of 125°C on a Tinius-Olsen Extrusion Plastometer. The gel content of the crosslinked product (A), defined as the percentage of toluene insoluble portion not passing through a 0.45 micron filter in a filtration procedure, was found to be 30.5 percent. In view of the lower amount of Isomer I present, about 2.8 weight percent, a higher gel content of about 30.5 percent was obtained as compared to Comparative Example I, wherein only 7.5 percent gel was obtained due, it is believed, to the presence of a higher amount of about 4.6 percent of Isomer I, which is believed to inhibit the crosslinking of the resin with the peroxide. EXAMPLE III (outside the scope of the claims) An unsaturated polyester resin poly(propoxylated bisphenol co-fumarate), derived from 1 mole equivalent of fumaric acid, 2.05 mole equivalent of propylene carbonate and 1 mole 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 to 190°C over a 1 hour period with stirring and maintained at that temperature for an additional 4 hour. A sample of this mixture was analyzed by LC chromatography, wherein it was found to contain 2.8 percent by weight of 4-(2-hydroxyethyl)-bisphenol A (Isomer I), 97 percent by weight of bis 4,4'-(2-hydroxyethyl)-bisphenol A (Isomer II), and 0.2 percent by weight of 4-(2'-hydroxyethyl-2-oxyethyl)-4'-(2-hydroxyethyl)-bisphenol A (Isomer III), reference Formula 1 throughout. 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 butylstannoic acid obtained as FASCAT 4100 from Elf Atochem, and 220 milligrams of hydroquinone. The temperature was then raised to 190°C over a 2 hour period, and the pressure was then reduced to 7.1 Torr over a 3 hour period, wherein water was collected in the distillation receiver. The resin, was then discharged through the bottom drain valve. The resin exhibited a glass transition temperature (onset) of 58°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 38 grams per 10 minute using a 2.16 kilograms 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 the gel permeation chromatography and using tetrahydrofuran as the solvent and polystyrene as the standard. The acid number of this resin was 12.3 milligrams of KOH per gram of sample. Three hundred (300) grams of the unsaturated polyester obtained in Example II were weighed and dry-blended using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water from Elf Atochem. The resulting blended mixture was extruded through an APV 15 millimeters twin screw extruder, which were set at 330°F. The extrudate strand from the extruder die was cooled in a water bath and the solid strands resulting were air-dried and then crushed into fine particles (95 percent by weight passing through 3.36 millimeters sieve) of less than about 3 millimeters in dimension. The melt index of the crosslinked product (A) was found to be 4.2 grams per 10 minutes using 16.6 kilograms weight at a temperature of 125°C on a Tinius-Olsen Extrusion Plastometer. The gel content of the crosslinked product (A), defined as the percentage of toluene insoluble portion not passing through a 0.45 micron filter in a filtration procedure, was found to be 30.5 percent. The lower amount of Isomer I present, such as about 2.8 weight percent, a higher gel content of about 30.5 percent was obtained as compared to Comparative Example I, wherein only 7.5 percent gel was obtained due to the presence of a higher amount of about 4.8 percent of Isomer I, which is believed to inhibit the crosslinking of the resin with the peroxide. EXAMPLE IV An unsaturated polyester resin, poly(propoxylated bisphenol co-fumarate), derived from 1 mole equivalent of fumaric acid, 2.10 mole equivalent of propylene 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 step, 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 to 190°C over a 1 hour period with stirring and maintained at that temperature for an additional 4 hours. A sample of this mixture was analyzed by LC chromatography, wherein it was found to contain 2.7 percent by weight of 4-(2-hydroxyethyl)-bisphenol A (Isomer I), 97 percent by weight of bis 4,4'-(2-hydroxyethyl)-bisphenol A (Isomer II), and 0.3 percent by weight of 4-(2'-hydroxyethyl-2-oxyethyl)-4'-(2-hydroxyethyl)-bisphenol A (Isomer III). In the second step, 30 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, wherein it was found to contain 0.5 percent by weight of 4-(2-hydroxyethyl)-bisphenol A (Isomer I), 94 percent by weight of bis 4,4'-(2-hydroxyethyl)-bisphenol A (Isomer II), and 5.5 percent by weight of 4-(2'-hydroxyethyl-2-oxyethyl)-4'-(2-hydroxyethyl)-bisphenol A and higher ordered 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 butylstannoic acid obtained as FASCAT 4100 from Elf Atochem, and 220 milligrams of hydroquinone. The temperature was then raised to 190°C over a 2 hour period, and the pressure was then reduced to 7.0 Torr over a 3 hour period, wherein water was collected in the distillation receiver. The resin was then discharged through the bottom drain valve. The resin exhibited a glass transition temperature (onset) of 57.0°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 32 grams per 10 minute using a 2.16 kilograms 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/mole and the number average molecular weight was found to be 3,500 grams/mole with a polydispersity of 3.85 as measured by the gel permeation chromatography and using tetrahydrofuran as the solvent and polystyrene as the standard. The acid number of this resin was 10.3 milligrams of KOH per gram of sample. Three hundred (300) grams of the unsaturated polyester were weighed and dry-blended using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water from Elf Altochem. The resulting blended mixture was extruded through an APV 15 millimeter twin screw extruder, which were set at 330°F. The extrudate strand from the extruder die was cooled in a water bath and the solid strands resulting were air-dried and then crushed into fine particles (95 percent by weight passing through 3.36 millimeters sieve) of less than about 3 millimeters in dimension. The melt index of the crosslinked product (A) was found to be 4.2 gram per 10 minutes using 16.6 kiligrams weight at a temperature of 125°C on a Tinius-Olsen Extrusion Plastometer. The gel content of the crosslinked product (A), defined as the percentage of toluene insoluble portion not passing through a 0.45 micron filter in a filtration procedure, was found to be 44 percent. The lower amount of Isomer I present, such as about 0.5 weight percent, resulted in a higher gel content of about 44 percent was obtained as compared to Comparative Example I, wherein only 7.5 percent gel was obtained due to the presence of a higher amount of about 4.8 percent of Isomer I, or Example II wherein 30 gel was obtained due primarily to the presence of about 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 equivalent of propylene 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 condensation catalyst in the first and second step, 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 to 190°C over a 1 hour period with stirring and maintained at that temperature for an additional 4 hours. A sample of this mixture was analyzed by LC chromatography, wherein it was found to contain 2.7 percent by weight of 4-(2-hydroxyethyl)-bisphenol A (Isomer I), 97 percent by weight of bis 4,4'-(2-hydroxyethyl)-bisphenol A (Isomer II), and 0.3 percent by weight 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 maintained at a temperature of 195°C for a duration of 1 hour. A sample of this mixture was analyzed by LC chromatography, wherein it was found to contain 0.2 percent by weight of 4-(2-hydroxyethyl)-bisphenol A (Isomer I), 90 percent by weight of bis 4,4'-(2-hydroxyethyl)-bisphenol A (Isomer II), and 9.8 percent by weight of 4-(2'-hydroxyethyl-2-oxyethyl)-4'-(2-hydroxyethyl)-bisphenol A and higher ordered 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 butylstannoic acid obtained as FASCAT 4100 from Elf Atochem, and 220 milligrams of hydroquinone. The temperature was then raised to 190°C over a 2 hour period, and the pressure was then reduced to 7.0 Torr over a 3 hour period, wherein water was collected in the distillation receiver. The resin, was then discharged through the bottom drain valve. The resin exhibited a glass transition temperature (onset) of 53°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 35 grams per 10 minutes using a 2.16 kilograms 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/mole and the number average molecular weight was found to be 4,000 grams/mole with a polydispersity of 3.75 as measured by the gel permeation chromatography and using tetrahydrofuran as the solvent and polystyrene as the standard. 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 equivalent 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 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, 1.2 grams of potassium carbonate and 0.5 grams of potassium t-butoxide. The mixture was heated to 195°C over a 1 hour period with stirring and maintained at that temperature for an additional 1 hour. A sample of this mixture was analyzed by LC chromatography, wherein it was found to contain 11 percent by weight of 4-(2-hydroxyethyl)-bisphenol A, 75 percent by weight 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 carbonate and alkali alkoxide, a higher amount of Isomer I was obtained in comparison to that of Examples II, III, IV and V. 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 butylstannoic acid obtained as FASCAT 4100 from Elf Atochem, and 220 milligrams of hydroquinone. The temperature was then raised to 190°C over a 2 hour period, and the pressure was then reduced to 7.0 Torr over a 3 hour period, wherein water was collected in the distillation receiver. The resin, was then discharged through the bottom drain valve. The resin exhibited a glass transition temperature (onset) of 52.0°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 35 grams per 10 minute using a 2.16 kilograms 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 the gel permeation chromatography and using tetrahydrofuran as the solvent and polystyrene as the standard. The acid number of this resin was 6.5 milligrams of KOH per gram of sample. Three hundred (300) grams of the unsaturated polyester obtained was dry-blended using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water from Elf Atochem. The resulting blended mixture was extruded through an APV 15 millimeters twin screw extruder, which were set at 330°F. The extrudate strand from the extruder die was cooled in a water bath and the solid strands resulting were air dried and then crushed into fine particles (95 percent by weight passing through 3.36 millimeters sieve) of less than about 3 millimeters in dimension. The gel content of the crosslinked product (A), defined as the percentage of toluene insoluble portion not passing through a 0.45 micron filter in a filtration procedure, was found to be about 0 percent. This resin was not crosslinked utilizing Lucidol 75, due to the presence of about 11 percent of isomer I in the resin which is believed to inhibit the crosslinking reaction. EXAMPLE VII A toner comprised of a crosslinked unsaturated polyester resin prepared by a reactive extrusion process by melt mixing 94 parts of the unsaturated polyester of Example IV with Lucidol 75 peroxide initiator, and 6 percent by weight of carbon black was prepared as follows. Three hundred (300) grams of the unsaturated polyester were weighed and dry-blended using a jar mill with 2.0 grams of Lucidol 75, a benzoyl peroxide with 25 percent water from Elf Atochem. The resulting blended mixture was extruded through an APV 15 millimeters twin screw extruder, which were set at 330°F. The extrudate strand from the extruder die was cooled in a water bath and the solid strands resulting were air dried and then crushed into fine particles (95 percent by weight passing through 3.36 millimeters sieve) of less than about 3 millimeters in dimension. The melt index of the crosslinked product (A) was found to be 4.2 grams per 10 minutes using 16.6 kilograms weight at a temperature of 125°C on a Tinius-Olsen Extrusion Plastometer. The gel content of the crosslinked product (A), defined as the percentage of toluene insoluble portion not passing through a 0.45 micron filter in a filtration procedure was found to be 44.5 percent. The above crosslinked polyester resin (261 grams), 15 grams of carbon black (REGAL® 330), 15 grams of polypropylene wax (Visco 660P by Sanyo Chemical) and 9 grams of compatibilizer (AX-8840, a polyethylene glycidylmethacrylate, obtained from ELF Atochem) were weighted and dry-blended using a tumbler for 45 minutes. The dry blend was then melt-mixed together on the APV extruder, which was set at 300°F. The extrudate strand was cooled down in a water bath, and then dried and crushed into fine particles (95 percent by weight passing through 3.36 millimeters sieve). The resulting crushed toner particles were then ground into fine toners using a jet mill (0202 Jet-O-Mizer), which toner was then classified using an A12 ACUCUT Classifier. The resulting toner product was comprised of 87 percent by weight crosslinked polyester, 5 percent by weight carbon black (REGAL®330), 5 percent by weight wax (660P) and 3 percent by weight compatibilizer (AX-8840). The volume median diameter of the toner product was 9.04 micron with 11.3 percent by number of fines between 1.26 to 4 microns. The toner tribo was found to be 5.18 microcoulombs/gram as measured on a semi-automatic Tribo Blow-Off Apparatus. EXAMPLE VIII A toner comprised of a crosslinked unsaturated polyester resin prepared by a reactive extrusion process by melt mixing 94 parts of the unsaturated polyester of Example V with Lucidol 75 peroxide initiator, and 6 percent by weight of carbon black was prepared as follows. Three hundred (300) grams of the unsaturated polyester obtained in Example V were weighed and dry-blended using a jar mill with 1.5 grams of Lucidol 75, a benzoyl peroxide with 25 percent water from Elf Atochem. The resulting blended mixture was extruded through an APV 15 millimeters twin screw extruder, which were set at 330°F. The extrudate strand from the extruder die was cooled in a water bath and the solid strands resulting were air dried and then crushed into fine particles (95 percent by weight passing through 3.36 millimeters sieve) of less than about 3 millimeters in dimension. The melt index of the crosslinked product (A) was found to be 4 grams per 10 minutes using 16.6 kiligrams weight at a temperature of 125°C on a Tinius-Olsen Extrusion Plastometer. The gel content of the crosslinked product (A), defined as the percentage of toluene insoluble portion not passing through a 0.45 micron filter in a filtration procedure, was found to be 45 percent. Due to the presence of low amounts of Isomer I in this resin, less amount of Lucidol 75 was utilized to crosslink the resin. The above crosslinked polyester resin (261 grams), 15 grams of carbon black (Regal®330), 15 grams of polypropylene wax (Visco 660P by Sanyo Chemical) and 9 grams of (AX-8840 by ELF Atochem) were weighted and dry-blended using a tumbler for 45 minutes. The dry-blend was then melt-mixed together on the APV extruder, which was set at 300°F. The extrudate strand was cooled down in a water bath, and then dried and crushed into fine particles (95 percent by weight passing through 3.36 millimeters sieve. The resulting crushed toner particles were then ground into fine toners using a jet mill (0202 Jet-O-Mizer), which toner was then classified using an A12 ACUCUT Classifier. The resulting toner product comprised of 87 percent by weight crosslinked polyester, 5 percent by weight carbon black (REGAL®330), 5 percent by weight wax (660P) and 3 percent by weight compatibilizer (AX-8840). The volume median diameter of the toner product was 9.1 microns with 11 percent by number of fines between 1.2 to 4 microns. The toner tribo was found to be 5.3 microcoulomb/gram as measured on a semi-automatic Tribo Blow-Off Apparatus. COMPARATIVE EXAMPLE IX There was prepared a copolyester resin obtained from bisphenol A, propylene carbonate, ethylene glycol and terephthalic acid with sodium carbonate as the catalyst as disclosed by the Example I of Japanese 10095840 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 was then stopped, and the reaction mixture was stirred for 1 hour, after which the temperature of the reactor was increased to 220°C and stirred for an additional 1.5 hours. A sample of this mixture was analyzed by LC chromatography, wherein it was found to contain 2.3 percent by weight of 4-(2-hydroxyethyl)-bisphenol A (Isomer I), 96.9 percent by weight of bis 4,4'-(2-hydroxyethyl)-bisphenol A (Isomer II), and 0.76 percent by weight 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 over a 5 hour period, during which time the pressure was reduced from atmospheric pressure, 760 to about 7 Torr, and water is collected in the distillation receiver The reactor was then pressurized to atmospheric pressure (about 760 Torr), and the resin was discharged through the bottom drain valve into a container and allowed to cool to ambient temperature (about 25°C) overnight (about 16 hours). The copolyester product, exhibited a glass transition temperature (onset) of 65°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. In this Comparative Example, only one class of catalyst, alkali carbonate, was employed resulting in an isomeric mixture wherein about 2.4 percent by weight of isomer I was obtained, and inferior to the isomeric mixtures obtained in the present invention, such as Examples IV and V, wherein less than about 0.5 percent by weight of isomer I was obtained. Furthermore, to obtain crosslinked polyesters of high gel content such as about 45 percent by weight, it is necessary that less than about 1 weight percent of isomer I utilized as exemplified in Examples IV and V. Furthermore, the aforementioned '336 patent utilizes both a diol such as ethylene glycol, and a diacid such as terephthalic acid during the polymerization steps to form a copolyester. This differs from the present invention wherein in embodiments only a diacid such as fumaric acid is utilized to form the polyester during the polycondensation step.

Claims: A process for the preparation of an unsaturated polyester which comprises (i) reacting an organic diol with a cyclic alkylene carbonate in the presence of a first catalyst to thereby form a polyalkoxy diol, (ii) adding thereto a further amount of cyclic alkylene carbonate in the presence of a second catalyst, and (iii) subsequently polycondensing the resulting mixture with an unsaturated dicarboxylic acids, wherein the first catalyst is an alkali carbonate, and wherein the second catalyst is an alkali alkoxide. The process in accordance with claim 1 wherein the preparation of the unsaturated polyester comprises (i) reacting an organic diol in an amount of from 0.95 to 1.05 mole equivalents with a cyclic akylene carbonate in an amount of from 1.95 to 2.05 mole equivalents, in the presence of a first alkali carbonate catalyst in an amount of from 0.001 to 0.1 mote equivalents; adding thereto (ii) from 0.05 to 0.45 mole equivalents of cyclic alkylene carbonate in the presence of a second alkali alkoxide catalyst in an amount of from 0.001 to 0.1 mote equivalents, to thereby form a polyalkoxy diol comprised of isomers with from 0 to 1 weight percent of isomer I, from 85 to 97 weight percent of isomer II, and from 3 to 15 weight percent of isomer III, and the sum of I, II, and III is 100 percent and wherein said isomers are of the formulas and followed by subsequently polycondensing the resulting polyalkoxy diol with an unsaturated dicarboxylic acid in an amount of from 0.95 to 1.05 mole equivalent, wherein a is zero, 1, 2, or a mixture of zero, 1, and 2. The process in accordance with claims 1 or 2 wherein there is formed a crosslinked polyester generated by the reactive extrusion of a peroxide and said unsaturated polyester. The process in accordance with any of claims 1 to 3 wherein said reacting is accomplished in the presence of heat The process in accordance with any of claims 1 to 4 wherein said reaction is accomplished by heating at a temperature of from 160°C to 215°C. The process in accordance with claim 1 wherein said polyester resin is formed by (i) reacting an organic diol in an amount of from 0.95 to 1.05 mole equivalent, with a cyclic akylene carbonate in an amount of from 1.95 to 2.05 mole equivalents, and a catalyst in an amount of from 0.001 to 0.1 mole equivalent, at a temperature of from 175°C to 205°C; (ii) adding thereto a cyclic alkylene carbonate in an amount of from 0.05 to 0.35 mole equivalent, with a second alkali alkoxide catalyst in an amount of from 0.001 to 0.1 mole equivalent, at a temperature of from 185°C to 205°C; and (iii) followed by polycondensing with an unsaturated dicarboxylic acid in an amount of from 0.95 to 1.05 mole equivalent. The process in accordance with claim 1 wherein the unsaturated polyester resin is obtained from (i) condensing 0.95 to 1.05 mole equivalent of an organic diol, with from 1.95 to 2.05 mole equivalent of an alkylene carbonate in the presence of a first alkali catalyst at a temperature of from 175°C to 205°C; and (ii) adding thereto a further amount of from 0.05 to 0.35 mole equivalent of a cyclic alkylene carbonate and a second catalyst at a temperature of from 185°C to 205°C, for a duration of from 1 to 3 hours; and (iii) polycondensing with an unsaturated dicarboxylic acid in an amount of from 0.95 to 1.05 mole equivalent, for a duration of from 1 to 3 hours, and followed by reducing the pressure from 760 Torr to 1 Torr. The process in accordance with claim 1 wherein the unsaturated polyester resin is obtained from (i) condensing 0.95 to 1.05 mole equivalent of an organic diol, with from 1.95 to 2.05 mole equivalent of an alkylene carbonate in the presence of a first alkali catalyst at a temperature of from 175°C to 205°C for a duration of from 1 to 6 hours; and (ii) adding thereto a further amount of from 0.05 to 0.35 mole equivalent of a cyclic alkylene carbonate and a second catalyst at a temperature of from 185°C to 205°C, for a duration of from 1 to 3 hours; and (iii) followed by a third step comprised of adding an unsaturated dicarboxylic acid heating the mixture of from 185°C to 220°C, followed by reducing the pressure from 760 Torr to 1 Torr. The process in accordance with claim 1 wherein 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 presence of a first catalyst to thereby form a bis-alkoxy diol, and (ii) adding thereto a further 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 with from 0 to 1 weight percent of isomer I, from 85 to 97 weight percent of isomer II, and from 3 to 15 weight percent of isomer III, and the sum of I, II, and III is 100 percent, and wherein a is zero, 1, 2, or a mixture of zero, 1 and 2.

Inventors: BAYLEY ROBERT D, FOUCHER DANIEL A, KITTELBERGER STEPHEN J, LI DONGMING, SABAN MARKO D, SACRIPANTE GUERINO G, TOTH ALAN E J, BAYLEY, ROBERT D., FOUCHER, DANIEL A., KITTELBERGER, STEPHEN J., LI, DONGMING, SABAN, MARKO D., SACRIPANTE, GUERINO G., TOTH, ALAN E.J.
Applicants: XEROX CORP, XEROX CORPORATION
Application year: 1999
Main classification: C08G63
IPC codes: C08G63, G03G9