MXPA00002630A - Monoesters and macrocyclic diester of phthalic acid and synthesis thereof - Google Patents

Abstract

Monoesters and macrocyclic diesters of 2,2,4-trimethyl-1,3-pentanediol and phthalic acid or a derivative thereof are described. Methods by which such monoesters and diesters may be prepared are also described. The mono- and diesters according to the invention are useful in the preparation of clear, hard thermoplastic polymers. The thermoplastic polymers are useful in coatings, inks, reinforced plastics and packaging materials.

Description

MONOESTERS AND MACROCYCLIC DIESTER OF FTALIC ACID AND SYNTHESIS OF THEM DESCRIPTION OF THE INVENTION The invention relates to monoesters and a7 macrocyclic diester of phthalic acid and derivatives thereof. Such phthalic acid esters and derivatives thereof are useful in the preparation of thermoplastic polymers. Thermoplastic polymers can be used to prepare coatings, inks, reinforced plastics and packaging. It is well known in the art the synthesis of lactones, or cyclic esters, derived from either hydroxy acids or diacids and dihydroxy compounds. (Carothers, .H., Collected Papers of Wallace Hume Carotjers on Hig Polymeric Substances, Eds. H. Mark and G.S. Whitby, Interscience Publishers, Inc., 248-259 (1940)). Examples include d-valerolactone, prepared by cyclization of 5-idroxypentanoic acid, and lactide, prepared by the dimerization of lactic acid. These simple compounds containing six-membered lactone rings are easily prepared in good yield, since they are similar lactones with five ring atoms, such as β-butyrolactone. Seven-membered ring lactones, such as, for example, e-caprolactone, can also be readily prepared. However, the synthesis of lactones with larger rings, particularly those with rings of eight to twelve atoms, has proven to be more difficult. Di and tetraester macrocyclic compounds, including cyclic esters derived from equimolar amounts of s-phthalic acid and a glyc, have been prepared (Bradshaw et al., Chem. Revs 79:37 (1979)). However, diesters, in particular those which form rings of eight to ten members, prepared from s-phthalic acid and simple glycols such as 1,2-dihydroxyethane, 1,3-dihydroxypropane and 2-methyl-1,3-dihydroxypropane , they are recovered in deficient yields of less than 5% (Ehrhart, WA, J. Org. C-jßra 33: 2930 (1986)). It is believed that the deficient yields are due to the inherent ring chain as a result of the two carbonyl groups. (Drewes et al., J.C.S. Perkin I, 2148 (1972)). The synthesis of a cyclic tetraester compound of phthalic anhydride and 1,3-dihydroxy-2,2-dimethylpropane is also achieved in very low yields of only 1.7% (Chen et al., J. Applied Appl. Poly Sci. 41: 2517 (1990)). There is still a need in the art for a synthetic route to prepare cyclic esters or lactones of a phthalic acid derivative and a simple glycol in high yield and purity. Cyclic esters provide unique intermediates in the production of thermoplastic polymers such as polyesters. These polyesters can be used in coatings, inks, reinforced plastics and packaging. The invention relates to the macrocyclic diester of the formula (III): The invention also relates to methods for preparing a diester of the formula (III) by contacting, optionally in the presence of a catalyst, a phthalic acid derivative of the formula (I): (I) with glycol 2, 2, 4 -trimethyl-1,3-pentanediol (TMPD): The invention also relates to a thermoplastic polymer resulting from the open ring polymerization of a diester of the formula (III). The invention also relates to a monoester of the formula (II): A monoester of the formula (II) is an intermediate that can be isolated in the reaction of a phthalic acid derivative of the formula (I) with TMPD to form a macroscyclic diester of the formula (III). One embodiment of the invention is a macrocyclic diester of the formula (III): In the formula (III), R1, R2, R3 and R4 are independently, hydrogen, a substituted or unsubstituted C1-C10 alkyl,? Ryl, or heteroaryl group, a nitro group, a halo group (F, Cl, Br , and I), a thio group, or an amino group. A combination of any two adjacent substituents, R1, R2, R3 and R4, together with the phenyl ring can also form a fused aromatic ring structure such as anthracene or naphthale or. Preferably, R1, R2, R3 and R4 are each hydrogen. Alternatively, at least one of R1, R2, R3 and R4 is an alkyl group of Cx-C4. The invention also includes a method for preparing a macrocyclic diester of the formula (III) via an esterification reaction. In a method of the invention, a macrocyclic diester of the formula can be prepared (III) by contacting under suitable reaction conditions, for example in a suitable solvent and, optionally, in the presence of a catalyst, a phthalic acid derivative of the formula (I): with 2, 2,4-trimethyl-l, 3-pentanediol (TMPD) In formula (I), R1, R2, R3 and R4 are as defined above while R5 and Rs are independently a hydroxyl group, a chloride group or when taken together, an oxygen to form an anhydride of phthalic acid or its derivative. The reaction can be carried out using typical esterification reaction conditions known in the art. Preferably, such a method is carried out under azeotropy distillation conditions known in the art. The azeotropic distillation conditions remove water from the reaction and carry the reaction towards completion, i.e., the formation of a macrocyclic diester of the formula (III). To prepare a macrocyclic diester of the formula (III), the molar ratio of a phthalic acid derivative of the formula (I) to TMPD is preferably about 1; 1. A slight molar excess of TMPD can be used without affecting the yield of a diester of formula (III). A large mole excess of generally more than about 50% of any reagent should be avoided since such conditions make it difficult to purify the desired macrocyclic diester of formula (III) by increasing the production of potential side products. Such side products may include a monoester resulting from the reaction between the phthalic acid derivative and the secondary alcohol position of 2,2,4-trimethyl-1,3-pentanediol (TMPD) and diester isomers. By using a large molar excess of any reagent, the total yield of the desired macrocyclic diester can be significantly reduced. The phthalic acid derivative can be any phthalic acid derivative of the formula (I) as described above capable of forming ester bonds upon reaction with TMPD. Preferably the phthalic acid derivative is phthalic anhydride, phthalic acid or phthaloyl chloride.

The esterification reaction is preferably carried out using a catalyst. The catalyst can be any esterification catalyst known in the art. The catalyst preferably increases the proportion of the reaction and the yield of the desired product. Examples of suitable catalysts include, but are not limited to, sulfonic acids, stannoic acids, titanium salts, manganese salts, and the like. Preferably the catalyst is butylstanoic aphid [(BuSn (O) OH]. Butylstanoic acid is sold as FASCAT® 4100 available from Elf Atochem of Philadelphia, PA Preferably, about 0.001 to 0.01 moles of catalyst is used per mole of acid derivative. phthalic of the formula (I) Suitable solvents for the esterification reaction are those which dissolve the reactants or facilitate esterification Preferably, the solvent facilitates the removal of water as an azeotrope, ie azeotropic distillation as discussed above. Suitable solvents include, but are not limited to, benzene, toluene and xylene Preferably, the solvent is toluene or xylene The amount of solvent used allows concentrations of combined reactants of between 10% -40% by weight of the reaction system Excess solvent increases production costs due to the added cost of the solvent in excess, cost of recovery and / or dis position of excess solvent, and cost of extra equipment required to run the reaction. Very little solvent produces high concentrations of reagents that can promote oligomer formation at the expense of diester formation. The esterification reaction can be carried out at temperatures in the range of about 50 ° -15 ° C. More preferably, the reaction temperature is in the range of about 100 ° -135 ° C. Oligomer formation can also be promoted by excessively high reaction temperatures, especially in combination with high reagent reactions. In a method of the invention, the esterification reaction of a phthalic acid derivative of the formula (I) with 2,2,4-trimethyl-1,3-pentanediol (TMPD) can be performed to first sign a monoester of the formula (II): In formula (II), R1, R2, R3 and R4 are as defined above. If desired, the monoester of the formula (II) can be isolated and purified by techniques known in the art such as, for example, recrystallization from toluene. A macrocyclic diester of the formula (III) can be prepared by heating an isolated monoester of the formula (II) under suitable reaction conditions, for example in a suitable solvent and, optionally, in the presence of a catalyst. Preferably, the conversion of an isolated monoester of the formula (II) to a macrocyclic diester of the formula (III) is carried out under azeotropic distillation conditions as described above. To promote the production of a monoester of the formula (II) without conversion of the monoester to a macrocyclic diester of the formula (III), the reaction can be carried out at temperatures in the range between 50-90 ° C. Preferably, the production of the monoester is carried out at temperatures in the range between 75-85 ° C. Performing this reaction within the above temperature range favors the production of the monoester without conversion to the diester. The termination of the esterification reactions discussed above can be determined by monitoring the reagent consumption and formation of the macrocyclic monster or diester. The consumption of the reagents and production of the macrocyclic diester can be monitored by techniques known in the art. These techniques include, for example, chromatography with vapor phase chromatography (CFV) which is a preferred technique. When cfv is used, to obtain a better analysis, the sample can be derived first, for example, with trimethylsilyl groups using bis (trimethylsilyl) trifluoroacetamide (BSTFA, commercially available from Aldrich Chemical Company of Milwaukee, Wl). When the esterification reaction is complete, the reaction solvent can be removed to produce a solid containing the desired product, for example, the macrocyclic diester of the formula (III) or the monoester of the formula (II). The reaction solvent can be removed using techniques known in the art, such as distillation, particularly distillation under reduced pressure, for example using a rotary evaporator. The macrocyclic diester product of the formula (III) or diester of the formula (II) can then be purified using known techniques such as co or recrystallization from an appropriate solvent. A macrocyclic diester of the formula (III) of solvents such as ethanol, methanol and the like can be recrystallized. A monoester of the formula (II) of solvents such as toluene, xylene and the like can be recrystallized. Preferably, a macrocyclic diester of the formula (III) of methanol can be recrystallized, and a monoester of the formula (II) of the toluene can be recrystallized. As is known in the art, the purified product can then be washed, for example with a small amount of the recrystallization solvent, to remove residual impurities. Using the reaction conditions discussed above, a macrocyclic diester of the formula (III) can be obtained in yields of about 40% or more. After purification, using techniques known in the art as described above, the macrocyclic diester of the formula (III) of > 99% purity by known techniques such as vacuum filtration. Another embodiment of the invention is a thermoplastic polymer formed of a diester of the formula (III). A thermoplastic polymer of a diester of the formula (III) can be prepared by open ring polymerization of a diester of the formula (III) in the presence of a catalyst and heat. Open ring polymerizations of cyclic diesters to form polyesters are known in the art and can be used to form the thermoplastic polymer of the invention. (Lófgren et al., J.M. S. Rev. Mocaromo, Chem. Phys., C35 (3), 379-418 (1995)). The catalyst can be any open ring polymerization known in the art, with dibutyl tin oxide being a preferred catalyst. The open ring polymerization reaction can be carried out at a temperature in the range between 15-0 ° C-250 ° C, preferably between 160 ° -180 ° C. Excessively high temperatures of >can be avoided250 ° C since polymer blackout and degradation may result. The open-ring polymerization process is also preferably carried out in an inert atmosphere and at pressures in the reduced pressure range at lightly superatmospheric pressure. Preferably, the combination of temperature and pressure is such that little to no diester of the formula (III) is volatilized and leaves the system. The thermoplastic polymer according to the invention exhibits exceptional resistance to environmental adaptability and hydrolysis due to the highly substituted nature of TMPD. In addition, the thermoplastic polymer according to the invention exhibits high molecular weight and low polydispersity.

A polyester of the invention can be used as the resin base in coatings, inks, reinforced plastics and packaging materials. The following examples are given to illustrate the present invention. It should be understood, however, that the invention is not limited to the specific conditions or details described in these examples. Example 1: Synthesis of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6,10-dioxabenzocyclonone-5,1-dione in the presence of a catalyst A solution of 14.8 g is refluxed ( 0.10 mol) of phthalic anhydride, 16.1 g (0.11 mol) of 2,2,4-trimethyl-1,3-pentanediol (TMPD), and 0.036 g of butylstanoic acid, [(BuSn (O) OH], (catalyst FASCAT ® 4100) in 125 ml of toluene under a fixed short packed column with a Dean-Stark trap for water removal as it is formed, until analysis by vapor phase chromatography (CFV) indicates that the reaction is finished. Distillation of the residue (30.0 g) at -0.9 torr, with slight heating of the distillation reactor by means of a 1200 watt heat gun, gives 11.3 g (40% yield) of the product which distills at a steam temperature between 140 ° and 155 ° C.

The distillate forms a hard paste at rest which is recrystallized from methanol (recovered, 62-67%) to give 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclononen-5, -diona, pf (differential scanning calorimetry) 101.24 ° C. Analysis: calcined molecular weight for C? 6H20O4: 276 Found (FDMS; M + 1), 277, 1 H NMR (CDC13), d 7.86 (1S); 7. 74-7.58 (m, 3H); 4.09 (d, 1H); 3.96 (d, 1H), 3.49 (d, 1H); 1. 93 (m, 1H); 1.30 (s, 3H); 1.00 (d, 3H); 0.92 (s, 3H); 0.90 (d, 3H). Ex ep-plo 2; Synthesis of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6,10-dioxabenzocyclonone-5, 11-dione in the presence of a catalyst A mixture of 74.0 g is stirred and heated ( 0.50 moles) of phthalic anhydride, 80.5 g (0.55 moles) of 2,2,4-trimethyl-1,3-pentanediol (TMPD), and 600 ml of toluene. When the solid has dissolved, 0.2 g of butylstanoic acid (FASCAT® 4100 catalyst) is added and the resulting mixture is heated to reflux. After approximately 90 hours, analysis of the mixture by vapor phase chromatography (cfv) indicates that, in a toluene-free base, egte contains 74.23% 7-isopropyl-8,8-dimethyl-8,9-dihydro -7H-6, 10-dioxabenzocyclononena-5, l-dione, 4.05% TMPD, 1.84% phthalic anhydride, 0.63% and 1.78%, respectively, of each of the two isomeric moneteresters of phthalic acid and TMPD, and 1.12% , 6.76% and 9.22%, respectively, of each of the three diesters of phthalic acid and TMPD. Phthalic acid is not present. Toluene is removed from the mixture in a rotary evaporator (20 torr, 70 ° C). The residue (151.9 g) is a thick jarabo which crystallizes slowly at rest. This residue is stirred with 150 ml of methanol, the mixture cooled to Q ° C overnight, then filtered at -10 ° C. The solid is washed with a small amount of cold methanol and dried to give 73.7 g (75% pure per cfv, 40% yield) of 7-isopropyl-8,8-dimethyl-8,9-dihydroxy-7H-6 , 10-dioxabenzocyclonone-5, 11-dione. Recrystallization of 50.0 g of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6,10-dioxabenzocyclonone-5,1-dione from 100 ml of methanol with cooling to about 0 ° C gives 42.5 g (85% recovery) of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6,10-dioxabenzocyclonone-5,1-dione as a white crystalline solid. Analysis: (vapor phase chromatography: internal standard diphenyl): 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclonone-5,1-dione, 99.97%. Example 3; Synthesis of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclonone-5, 1-dione in a more concentrated solution After the procedure of Examples 1 or 2, 2,7-isopropyl -8,8-dimethyl-8,9-dihydro-7H-6,10-dioxabenzocyclonone-5,1-dione is prepared from a solution of 14.81 g (0.1 mol) of phthalic anhydride and 16.30 g (0.11 mol) of 2, 2,4-trimethyl-1,3-pentanediol (TMPD) in 75 ml of xylene. The catalyst has 49.4 mg of FASGAT® 4100 catalyst. Xylene is removed in a rotary evaporator and the residue is distilled to give 11.09 g of distillate, b0.5 130-160 ° C which is found by vapor phase chromatography (cfv) to consist of 84% 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclonone-5,1-dione (40% yield). The residue of this distillate weighs 17.65 g. Example 4; Synthesis of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclonone-5, 1-dione in a more dilute solution, without the addition of a catalyst A solution of 114.82 g is heated ( 0.10 moles) of phthalic anhydride and 16.31 g (0.11 moles) of 2,2,4-trimethyl-1,3-pentanediol (TMPD) in 250 ml of xylene for 96 hours as described in Examples 1-3. The xylene is removed in a rotary evaporator at 20 torr, at a base temperature of 68 ° C. The residue (30.0 g) is diluted with 30 ml of methanol and the resulting suspension is cooled to 1 ° C, filtered, and washed with methanol which has been cooled to -20 ° C to give 15.9 g (58% yield) ) of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclonone-5, 11-dio, which is 99.9% pure by vapor phase chromatography (cfv). The methanol that is washed from the recovery of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7-6,10-dioxabenzocyclonone-5, 11-dione content, in a methanol-free base, 16.4% 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6,10-dioxabenzocyclonone-5,1-dione, while the residue from the xylene distillation of the original reaction mixture contained 41.2% of -isopropyl-8, 8-dimeti-8, 9-dihydro-7H-6, 10-dioxabenzocyclonone-5, 1-dione. Example 5; Synthesis of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclonone-5,1-dione in the presence of 100% molar excess of 2, 2, 4-trime-lime 1, 3-pentanediol (TMPD) The procedure of the preceding examples is followed, with a solution of 14.81 g (0.1 mol) of phthalic anhydride and 29.27 g (0.20 mol) of 2, 2, 4-trimethyl-1,3- pentanediol (TMPD) in 250 ml of xylene. Analysis of the residue, after removal of the xylene solvent, indicates that it contains 41.3% of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclonone-5, 1-dione, 3Q.9% of diesters of phthalic acid and TMPD and 24% of TMPD. The residue (28.17 g) is distilled at 2-3 torr and a reactor temperature of 200-220 ° C to give a distillate (12.60 g) containing vapor phase chromatography (cfv) 78.9% TMPD and 15.5% 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6,10-dioxabenzocyclonone-5,11-dione. The residue is diluted with cold methanol, filtered, and the crystals are washed with cold methanol to give 13.21 g (99.0% purity per cfv, 48% yield) of 7-isopropyl-8,8-dimethyl-8, 9-dihydro-7H-6, 10-dioxabenzocyclonone-5, 1-dione. The residue and sides of this separation of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclonone-5, 11-dione content, in a methanol-free base, 13.1% of 7- isopropyl-8,8-dimethyl-8,9-dihydro-7H-6,10-dioxabenzocyclonone-5,1-dione and 52.6% of diesters. of phthalic acid and TMPD. Example 6: Preparation of a linear polymer by open ring of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzosiclonone-5-yl-dione A mixture of 1,994 g of 7-isopropyl-8; 8-Dimethyl-8, 9-dihydro-7H-6, 10-dioxabenzocyclonone-5, 11-dione recrystallized and 8.0 mg of dibutyltin oxide in a tube, degassed with the cyclic diester just above the melting point (101 ° C ) and sealed under vacuum. The tube is heated in an oil bath at 170 ° C for about 96 hours. The resulting yellow, viscous product solidifies to a hard glass at room temperature. Gel phase chromatography indicates that the product contains phthalic anhydride and some residual monomer but that the polymer portion has a number average molecular weight (Mn) = 6700; weight average molecular weight (Mw) = 9600. The glass transition temperature (differential scanning calorimetry, second heating) is 39.0 ° C. Example 7: Preparation of 1- (2, 2,4-trimethyl-1,3-pentanediol) monophosphate A solution of 4.98 g (0.033 mole) of phthalic anhydride and 5.42 g (0.037 mole) of TMPD in 40 ml is stirred. of tolnene and heated to 80 ° C for about 30 hours. The solvent is evaporated and the crystalline residue is washed with cold toluene and dried to give 5.95 g of 2,2,4-trimethyl-1,3-pentanediol monophthalate. 2, 2,4-Trimethyl-1,3-pentanediol monophthalate (1.00 g) is recrystallized from 5 ml of toluene without purification and washed to give 0.95 g of 1- (2, 2, 4-trimethyl-1,3- pentanediol) unpurified monophthalate, mp (differential scanning calorimetry) 127 ° C. Analysis: calculated for C16H22O5: molecular weight 294.1467 Found (mass spectrometry) 294.1461. Example 8; Conversion of 1- (2,2-, 4-trimethyl-l, 3-pentanediol) monophthalate to 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6,10-dioxabenzocyclonone-5,11-dione A solution of 29.4 g (0.100 mol) of 2, 2, 2, 4-trimethyl-l, 3-pentanediol monophthalate in 250 ml of toluene is allowed to stand for a weekend, 32.6 mg of FASCAT 4100 ® catalyst is added, and allows to reflux the solution under a Dean-Stark trap for 102 hours, when 1.40 ml of water has been collected in the trap. Toluene is removed in the rotary evaporator. Analysis of this residue by vapor phase chromatography (cfv) indicates that it contains 72% of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclonone-5, 11-dione , as well as also minor amounts of 2, 2, 4-trimethyl-1,3-pentanediol (TMPD), phthalic anhydride, 1- (2, 2, 4-trimethyl-1,3-pentanediol) monophthalate, 3- (2 , 2, 4-trimethyl-1,3-pentanediol / monophthalate, and diesters of phthalic acid and TMPD This residual oil is diluted (28.9 g) with 30 ml of methanol, seeded with a small crystal of 7-isopropyl-8 , 8-dimethyl-3, 9-dihydro-7H-6, 10-dioxabenzocyclonone-5, 11-dione, pure and cooled to 0 ° C, and filtered.The crystals are washed with methanol.The purified solid is weighed 15.33 g) The analysis by cfv indicates that it is 99% pure 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclonone-5, 11-dionyl (55%). the filtrate from the recrystallization of methanol to remove the solvent The residual oil is analyzed (13.3 g ) per cfv.This contains 24.1% of 7-isopropyl-8,8-dimethyl-8,9-dihydro-7H-6, 10-dioxabenzocyclonone-5,1-dione, together with minor amounts of the components indicated in the oil residual of the original toluene evaporation.

Claims (21)

1. CLAIMS 1. A macrocyclic diester of the formula (III) wherein R1, R2, R3 and R4 are independently hydrogen, a substituted or unsubstituted Ci-Cio alkyl group, aryl or heteroaryl, a nitro group, a halo group, a thio group, or an amino group; and any two adjacent substituents of R1, R2, R3 and R4 when taken together with the phenyl ring form a fused aromatic ring structure.
2. 2. A macrocyclic diester according to claim 1, characterized in that R1, R2, R3 and R4 are independently hydrogen, or a group of C? -C; or any two adjacent substituents, R1, R2, R3 and R4, together with the phenyl ring form a fused aromatic ring structure selected from anthracene and naphthalene.
3. 3. A macrocyclic diester according to claim 1, characterized in that R1, R2, R3 and R4 are each hydrogen.
4. 4. A method for preparing a macrocyclic diester characterized in that it comprises the step of: contacting, optionally in the presence of a catalyst, 2, 2, 4-trimethyl-1,3-pentanediol and a phthalic acid derivative of the Formula (I): wherein R1, R2, R3 and R4 are, independently, hydrogen, a substituted or unsubstituted C?-C? alkyl group, aryl, or heteroaryl, a nitro group, a halo group, a thio group, or an amino group; any two adjacent substituents of R1, R2, R3 and R4 when taken together with the phenyl ring form a fused aromatic ring structure; and R5 and R6 are independently a hydroxyl group, a chloride group or when oxygen is taken together; under conditions sufficient to produce a diester of the formula (III): wherein R1, R2, R3 and R4 are, independently, hydrogen, a substituted or unsubstituted Ci-Cio alkyl group, or heteroaryl group, a nitro group, a halo group, a thio group, or an amino group; and any two adjacent substituents of R1, R2, R3 and R4 when taken together with the phenyl ring form a fused aromatic ring structure.
5. A method according to claim 4, characterized in that the phthalic acid derivative is selected from the group consisting of phthalic anhydride, phthalic acid, and phthaloyl chloride.
6. 6. A method according to claim 4, characterized in that R1, R2, R3 and R4 are each hydrogen.
7. 7. A method according to claim 4, characterized in that the catalyst is butylstanoic acid.
8. 8. A method according to claim 4, characterized in that the contact step is carried out under azeotropic distillation conditions.
9. 9. A method according to claim 4, characterized in that the step of contacting 2,2,4-trimethyl-1,3-pentanediol and a derivative of phyllic acid of the formula (I) first form a monoester of the formula (II) before the diester: wherein R1, R2, R3 and R4 are, independently, hydrogen, a C?-C? or substituted or unsubstituted alkyl group, aryl, or heteroaryl, a halo group, a thio group, or an amino group; and any two adjacent substituents of R1, R2, R3 and R4 when taken together with the phenyl ring form an aromatic ring structure;
10. 10. A method for preparing a macrocyclic diéter characterized in that it comprises the step of: heating, optionally in the presence of a catalyst, a monoester of the formula (II) wherein R1, R2, R3 and R4 are, independently, hydrogen, a substituted or unsubstituted C1-C10 alkyl, aryl, or heteroaryl group, a nitro group, a halo group, a thio group, or an amino group; and any two adjacent substituents of R1, R2, R3 and R4 when taken together with the phenyl ring forms a fused aromatic ring structure; under conditions sufficient to produce a macrocyclic diester of the formula (III): wherein R1, R2, R3 and R4 are, independently, hydrogen, a substituted or unsubstituted C?-C? alkyl, aryl, or heteroaryl group, a nitro group, a halo group, a thio group, or a group Not me; and any two adjacent substituents of R1, R2, R3 and R4 when taken together with the phenyl ring form a fused aromatic ring structure.
11. 11. A method according to claim 10 characterized in that R1, R2, R3 and R4 are each a hydrogen.
12. 12. A method according to claim 10, characterized in that the catalyst is butylstanoic acid.
13. 13. A method according to claim 10, characterized in that the heating step is carried out under azeotropic distillation conditions.
14. 14. A polymer characterized in that it comprises the open ring polymerization product of a diester of the formula (III): wherein R1, R2, R3 and R4 are, independently, hydrogen, a substituted or unsubstituted C?-C10 alquilo alkyl group, aryl, or heteroaryl, a nitro group, a halo group, a thio group, or an amino group; and any two adjacent substituents of R1, R2, R3 and R4 when taken together with the phenyl ring form a fused aromatic ring structure.
15. 15. A polymer according to claim 14, characterized in that R1, R2, R3 and R4 are independently a hydrogen, or an alkyl group of C? -C, or any two adjacent substituents R1, R2 *, R3 and R4, together with the phenyl ring they form a fused aromatic ring structure selected from anthracene and naphthalene.
16. 16. A polymer according to claim 14, characterized in that R1, R2, R3 and R4 are each hydrogen.
17. 17. A polymer according to claim 14, characterized in that the open ring polymerization product is a catalyzed open ring polymerization product.
18. 18. A polymer according to claim 14, characterized in that the catalyzed open ring polymerization product is prepared in the presence of a dibutyl tin oxide catalyst.
19. 19. A monoester of the formula (II) wherein R1, R2, R3 and R4 are, independently, hydrogen, a C?-C10---- substituted or unsubstituted C grupo alquilo alkyl group, aryl or heteroaryl group, a nitro group, a halo group, a thio group, or an amino group; and any two adjacent substituents of R1, R2, R3 and R4 when taken together with the phenyl ring form a fused aromatic ring structure.
20. 20. A monoester according to claim 19, characterized in that R1, R2, R3 and R4 are independently a hydrogen, or an alkyl group of C? -C4; or any two adjacent substituents R1, R2, R3 and R4, together with the phenyl ring form a fused aromatic ring structure selected from anthracene and naphthalene.
21. 21. A monoester according to claim 19, characterized in that R1, R2, R3 and R4 are each hydrogen.