Title of Invention	A PROCESS FOR THE CONTINUOUS PRODUCTION OF ATLEAST ONE OF BIS (3-HYDROXYPROPYL) TEREPHTHALATE AND LOW MOLECULAR WEIGHT OLIGOMERS OF 1,3-PROPANEDIOL AND TEREPHTHALIC ACID
Abstract	A process for the continuous production of at least one of bis(3-hydroxypropyl) terephthalate and low molecular weight oligomers of 1,3-propanediol and terephthalic acid is disclosed. According to the process, preheated 1,3-propanediol and preheated lower dialkyl esters of terephthalic acid are used in a continuous transesterification reaction. Preferably, the preheated 1,3-propanediol and the preheated terephthalic acid ester through at least one inlet to the ester exchange vessel located at or below its midpoint.

Title of Invention

A PROCESS FOR THE CONTINUOUS PRODUCTION OF ATLEAST ONE OF BIS (3-HYDROXYPROPYL) TEREPHTHALATE AND LOW MOLECULAR WEIGHT OLIGOMERS OF 1,3-PROPANEDIOL AND TEREPHTHALIC ACID

Abstract

A process for the continuous production of at least one of bis(3-hydroxypropyl) terephthalate and low molecular weight oligomers of 1,3-propanediol and terephthalic acid is disclosed. According to the process, preheated 1,3-propanediol and preheated lower dialkyl esters of terephthalic acid are used in a continuous transesterification reaction. Preferably, the preheated 1,3-propanediol and the preheated terephthalic acid ester through at least one inlet to the ester exchange vessel located at or below its midpoint.

Full Text	FORM 2 THE PATENTS ACT, 1970 [39 OF 1970] & THE PATENTS RULES, 2003 COMPLETE SPECIFICATION [See Section 10: rule 13] A PROCESS FOR THE CONTINUOUS PRODUCTION OF ATLEAST ONE OF BIS (3-HYDROXYPROPYL) TEREPHTHALATE AND LOW MOLECULAR WEIGHT OLIGOMERS OF 1,3-PROPANEDIOL AND TEREPHTHALIC ACID" E.I. DU PONT DE NEMOURS AND COMPANY, a Delaware corporation of 1007 Market Street, Wilmington, Delaware 19898, United States of America, The following specification particularly describes the nature of the invention and the manner in which it is to be performed:- FIELD OF THE INVENTION The present invention relates to a continuous process for the production of a mixture of bis(3-hydroxypropyl) terephthalate monomer and low molecular weight oligomers of 1,3-propanediol and terephthalic acid from 1,3-propanedio] and dimemylterephalate. The bis(3-hydroxypropyl) terephthalate monomer/oligomer mixture may be used as a feed material in a continuous polymerization process for the production of poly(l,3-propylene terephthalate). BACKGROUND OF THE INVENTION Batch processes for the production of bis(hydroxyalkyl) terephthalate esters are known. For example, Doerr et al., U.S. Patent No. 5,340,909 discloses a batch process for the manufacture of poly(l,3-propylene terephthalate), including a batch ester interchange reaction in which 1,3-propanediol is reacted with a lower dialkyl ester of terephthalic acid. Continuous transesterification processes are known for the production of bis(2-hydroxyethyl) terephthalate. For example, Vodonik, U.S. Patent No. 2,829,153, discloses a continuous process for the production of bis(2-hydroxyethyl) terephthalate and its low molecular weight oligomers from ethylene glycol and dimethylterephthalate. It would be highly desirable to provide a continuous ester exchange process for the production of bis(3-hydroxypropyl) terephthalate and its low molecular weight oligomers from 1,3-propanediol and dimethylterephthalate. The present invention provides such a process. SUMMARY OF THE INVENTION The invention comprises a process for the continuous production of at least one of bis(3-hydroxypropyl) terephthalate and low molecular weight oligomers of 1,3-propanediol and terephthalic acid, comprising: (a) preheating 1,3-propanediol to a temperature of about 150°C to about 200°C; (b) preheating one or more lower dialkyl esters of terephthalic acid to a temperature of about 150°C to about 220°C; (c) combining the preheated 1,3-propanediol with the preheated terephthalic acid esters to form a mixture having a mole ratio of 1,3-propanediol to terephthalic acid ester of about 1.2:1 to about 2.3:1 and maintaining the temperature of the mixture at about 150°C to about 220°C; (d) continuously feeding the preheated 1,3-propanediol/terephthalic acid ester mixture through at least one inlet to an ester exchange vessel where the mixture undergoes a continuous transesterification reaction to form a liquid reaction mixture and gaseous reaction products; (e) continuously heating and mixing the liquid reaction mixture, whereby the temperature of the mixture in a base portion of the ester exchange vessel is maintained at about 215°C to about 250°C and the pressure in a base portion of the ester exchange vessel is maintained at about 800 mm Hg to about 1,000 mm Hg (10664 to 133322 Pa), thereby continuing the transesterification reaction to form liquid reaction products and gaseous reaction products; (f) continuously separating the gaseous reaction products from the liquid reaction mixture in a separating portion of the ester exchange vessel which is above the base portion; and (g) continuously removing a stream of liquid reaction products from the base portion of the ester exchange vessel, the stream comprising at least one of bis(3-hydroxypropyl) terephthalate and low molecular weight oligomers of 1,3-propanediol and terephthalic acid. DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic representation of an apparatus useful in carrying out the process of the invention. Figure 2 is a schematic representation of a section of a bubble cap column useful in carrying out the process of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS According to the process of the invention, 1,3-propanediol and one or more lower dialkyl esters of terephthalic acid are reacted to form bis(3-hydroxypropyl) terephthalate and low molecular weight oligomers of 1,3-propanediol and terephthalic acid having an average degree of polymerization of about 1 to about 15. While lower dialkyl esters of terephthalic acid other than dimethylterephthalate may be used in the process of the invention, for simplicity, the remainder of the description refers only to dimethylterephthalate. As shown in Figure 1, a mixture of 1,3-propanediol and transesterification catalyst is fed to ester exchange column 1 from tank 2, and dimethylterephthalate is fed from tank 3, both via temperature-controlled feed lines 4. The 1,3-propanediol is mixed with a catalyst, preferably prior to mixing with dimethylterephthalate. Catalysts useful in the process of the invention include organic and inorganic compounds of titanium, lanthanum, zinc and cobalt, such as oxides, carbonates, phosphorus derivatives, and alkyl, aryl and acyl derivatives, and the like. Examples of such catalysts include tetraisopropyl titanate, tetraisobutyl titanate, lanthanum acetylacetonate and cobalt acetate. Titanium catalysts, such as tetraisopropyl titanate and tetraisobutyl titanate are preferred and are added to the 1,3-propanediol in an amount sufficient to yield 20 to 90 ppm of titanium by weight based on the weight of poly(l,3-propylene terephthalate) formed in subsequent processing. The catalyzed 1,3-propanediol is preheated to a temperature of about 150°C to about 200°C, preferably about 185°C, prior to mixing with dimethylterephthalate. The dimethylterephthalate is preheated to a temperature of about 150°C to about 220°C, preferably about 185°C, prior to mixing with catalyzed 1,3-propanediol. The preheated catalyzed 1,3-propanediol is mixed with the preheated dimethylterephthalate by means of static mixer 5 in the feed line. Optionally, preheating is continued after mixing,, such that the catalyzed 1,3-propanediol/dimethylterephthalate mixture reaches a temperature of about 150°C to about 220°C, preferably about 200°C to about 220°C, prior to being fed to the ester exchange vessel. The mole ratio of 1,3-propanediol to dimethylterephthalate is about 1.2:1 to 2.3:1, preferably about 1.3:1 to 1.7:1, and most preferably about 1.5:1 in the mixture that is fed to the ester exchange vessel. In a preferred embodiment of the invention, the ester exchange vessel has three integral sections. The base portion of the vessel is the calandria 6, above which is bubble cap column 7 and one or more condensers 8. The calandria functions as a heat exchanger to heat the liquid reactants to a temperature of about 215° to 250°C, preferably about 230° to 240°C, and most preferably about 235°C. The calandria is jacketed and heated by means of a gaseous or liquid heating medium, e.g., Dowtherm vapor. The calandria supplies all of the heat for the ester exchange column. If desired, a stream of the liquid reaction mixture can be withdrawn from the exchange vessel, passed through the external heater and heated, and then fed back to the exchange vessel to cause mixing. As shown in Figure 2, bubble cap plate section 7, also referred to as the tray section or column, has a plurality of bubble cap plates (or trays) 9, each one extending completely across the column and spaced apart vertically from one another by a distance of typically about one foot. Each bubble cap plate 9 holds a constant level of liquid on the plate during operation. Each plate 9 as a plurality of bubble caps which are evenly distributed across the plate. The bubble caps allow hot vapor to rise through the plates and up the column. Each bubble cap has a chimney 11 and a cap 12 which is notched along the lower edge and fits down onto plate 9. Vapor traveling up though a chimney 11 reverses direction when it reaches the lower surface of cap 12. The vapor then pushes the liquid under cap 12 down until it is below the notches and then bubbles up through the liquid around the outside of the bubble cap. Plates 9 also have baffles to- direct the flow of liquid 1,3-propanediol and dimethylterephthalate across the plate and around the bubble caps and a downcomer 10 to carry the liquid from one plate to the one below. Additional information regarding bubble cap columns is available, e.g., from R. H. Perry and D.W. Green, Perry's Chemical Engineers' Handbook, 7th ed., Section 14 (The McGraw-Hill Companies, 1997). Due to the structure of bubble cap column 7, there is a gradual step-wise decrease in pressure from below the first plate to above the uppermost plate in the ester exchange column. The pressure at the base of the column, i.e., above the liquid level in the calandria and below the. first plate, is maintained at a pressure of about 800 mm Hg to about 1,000 mm Hg (10,664 to 133,322 Pa), preferably about 850 to 950 mm Hg (113,305 to 126,635 Pa). The pressure at the top of the column is at or near atmospheric pressure because the top of the exchanger is vented to the atmosphere. The 1,3-propanediol/dimethylterephthalate mixture may be injected into the ester exchange column at various points at or below about the midpoint of the tray section. For example, the 1,3-propanediol/dimethylterephthalate mixture may be injected at the base of the exchanger (calandria), or onto a tray located approximately one quarter of the distance between the bottom and the top of the exchanger (hereinafter the "quarterpoint"), or onto a tray located at approximately the midpoint of the exchanger. The injection point and mole ratio are adjusted in order to minimize unconverted dimethylterephthalate and acrolein and allyl alcohol generation. The preferred process is to use a mole ratio of about 1.5:1 1,3-propanediol to dimethylterephthalate and to inject the 1,3-propanediol/dimethylterephthalate mixture into the base of the exchanger column below the first tray. Alternatively, a mole ratio of up to 2.0 moles of 1,3-propanediol per mole of dimethylterephthalate is used, and the 1,3-propanediol/dimethylterephthalate mixture is injected at the quarterpoint or midpoint of the exchanger. In this latter process, a higher mole ratio is needed to prevent higher boiling monomer from staying on the trays. This alternate process has been found to reduce the unconverted dimethylterephthalate but requires that more 1,3-propanediol be recovered in the prepolymerization step. In yet another alternative, a mixture of preheated, catalyzed 1,3-propanediol and preheated dimethylterephthalate is injected into the base of the exchanger, and additional virgin 1,3-propanediol, typically at ambient temperature, is injected at the quarterpoint of the exchange column. In this embodiment, the mixture that is injected into the base of the exchanger has a lower mole ratio of 1,3-propanediol to dimethylterephthalate and a higher catalyst concentration than the mixture used in previously described embodiments, such that the overall mole ratio and catalyst concentration remain within the above-described ranges, after taking into account the additional 1,3-propanediol that is injected at the quarterpoint. In still another alternative, preheated dimethylterephthalate and preheated catalyzed 1,3-propanediol are injected into the exchanger separately without premixing. For example, the dimethylterephthalate is injected into the base of the exchanger, and the catalyzed 1,3-propanediol is injected at the quarterpoint. At least one condenser 8 is provided for condensing the methanol vapor and other gaseous by-products produced by the transesterification reaction. A portion of the condensed methanol can be refluxed back to the bubble cap column to control the top tray temperature. Any remaining condensate is removed from the process. The methanol vapor exiting the ester exchange column typically contains other reaction by-products such as acrolein and allyl alcohol. It is desirable that the production of by-products such as acrolein and allyl alcohol be minimized because both compounds are highly toxic and cause irritation to the eyes and mucous membranes. According to the process of the invention, the amount of acrolein contained in the condensate exiting the ester exchange column is no greater than 700 ppm, preferably no greater than 350 ppm, and more preferably no greater than 30 ppm. The amount of allyl alcohol contained in the condensate exiting the ester exchange column is no greater than 1000 ppm, preferably no greater than 400 ppm, and more preferably no greater than 200 ppm. The term "ppm" is used herein to mean parts per million and is equal to micrograms per gram. The liquid reaction product containing bis(3-hydroxypropyl) terephthalate monomer and low molecular weight oligomers of 1,3-propanediol and terephthalic acid are removed from the ester exchange vessel via outlet 13 in the calandria 6. The liquid reaction product contains unreacted dimethylterephthalate in an amount not greater than 9%, preferably not greater than 4%, of the total weight of the exit stream. The monomer/oligomer mixture may be fed to a prepolymerizer, flasher or other reaction vessel where it is further reacted to produce a higher molecular weight poly(l,3-propylene terephthalate) prepolymer. The residence time in the ester exchange column is about 1 to 2 hours. EXAMPLES 1-7 Using an ester exchanger of the type indicated in the drawings, a 76.4 lb./hr (34.7 kg/hr) stream of dimethyl terephthalate (DMT) was preheated to a temperature of 185°C and continuously mixed with a stream of catalyzed 1,3-propanediol which was also preheated to a temperature of 185°C, to form a mixture. The mole ratio of 1,3-propanediol to dimethylterephthalate was varied from 1.5:1 to 1.8:1 to 2.0:1 to 2.25:1 by varying the catalyzed 1,3-propanediol stream from 44.9 lb./hr (20.4 kg/hr) to 53.9 lb./hr (24.5 kg/hr) to 59.9 lb./hr (27.2 kg/hr) to 67.3 lb./hr (30.6 kg/hr). The catalyst was tetrisoprpyl titanate (Tyzoi® TPT, available from E. I. duPont de Nemours and Company, Wilmington, DE), which was added to the glycol in an amount sufficient to yield 50 ppm or 30 ppm by weight of titanium based on the weight of poly(l,3-propylene terephthalate) formed in subsequent processing. The dimethylterephthalate/catalyzed glycol mixture was fed into the ester exchanger either at the base (calandria) or at the quarterpoint. The temperature of the liquid reactants at the base of the ester exchanger (calandria) was maintained at 237°C, and the pressure at the base of the ester exchanger was maintained at 900 to 950 mm Hg (119,970 to 126,635 Pa). The pressure at the top of the ester exchange column was atmospheric. In the ester exchanger, the 1,3-propanediol reacted with the dimethylterephthalate to form bis(3-hydroxypropyl) terephthalate monomer and low molecular weight oligomers of 1,3-propanediol and terephthalic acid, liberating methanol vapor and other by-products, which were continuously removed from the top of the ester exchanger. The monomer/oligomer mixture was continuously removed from the base of the ester exchanger to be fed to a prepolymerizer, flasher or other reaction vessel where it was further reacted to produce pol(l,3-propylene terephthalate) prepolymer. The conditions and results for the continuous ester exchange process are set forth in Table I. In Table I, the level of catalyst is given as parts per million (ppm) by weight of titanium in the finished polymer. The amount of unconverted dimethylterephthalate (DMT) is given as a weight percentage based upon the total weight of the exit stream. The acrolein and allyl alcohol levels are given in parts per million (ppm) by weight based on the total condensate that is removed from the ester exchange vessel. The dipropylene glycol (DPG) levels are given as a weight percent based on monomer/oligomer exiting the exchange vessel. TABLE I Example Catalyst Ti (ppm) Mole Ratio Glycol/ DMT Unconv. DMT (Wt.0/o) Acrolein (ppm) Allyl Alcohol (ppm) DPG (wt.%) 1 50 1.5* 5.6 76 506 0.12 2 50 1.5 5.6 22 291 0.13 3 50 1.8 5.8 37 259 0.15 .4 50 2.0* 3.4 37 202 0.25 5 50 2.0 4.5 31 222 0.19 6 50 2.25 5.3 21 146 0.19 7 30 1.5 7.1 20 246 0.13 * In Examples 1 and 4, 1,3-propanediol (glycol) and dimethylterephthalate (DMT) were premixed and fed to the ester exchanger vessel at the quarter point. In all other Examples, the 1,3-propanediol/dimethylterephthalate mixture was fed to the base of exchanger. We Claim: 1. A process for the continuous production of at least one of bis(3- hydroxypropyl) terephthalate and low molecular weight oligomers of 1,3-propanediol and terephthalic acid, comprising: (a) preheating 1,3-propanediol to a temperature of 150°C to 200°C; (b) preheating one or more lower dialkyl esters of terephthalic acid to a temperature of 150°C to 220°C; (c) continuously feeding the reheated 1,3-propanediol and the preheated terephthalic acid ester through at least one inlet to an ester exchange vessel located at or below the midpoint of the ester exchange vessel where the total, 1,3-propanediol and terephthalic acid ester added to the ester exchange vessel is in a mole ratio of 1,3- propanediol to terephthalic acid ester of 1.2:1 to 2.3:1 and the 1,3- propanediol and terephthalic acid ester undergo a ontinuous transesterification reaction to form a liquid reaction mixture and gaseous reaction products; (d) continuously heating and mixing the liquid reaction mixture, whereby the temperature of the mixture in a base portion of the ester exchange vessel is maintained at 215°C to 250°C and the pressure in a base portion of the ester exchange vessel is maintained at 800 mm Hg to 1,000 mm Hg, thereby continuing the transesterification reaction to form liquid reaction products and gaseous reaction products; (e) continuously separating the gaseous reaction products from the liquid reaction mixture in a separating portion of the ester exchange vessel which is above the base portion; and (f) continuously removing a stream of liquid reaction products from the base portion of the ester exchange vessel, the stream comprising at least one of bis(3- hydroxypropyl) terephthalate and low molecular weight oligomers of 1,3-propanediol and terephthalic acid. The process as claimed in claim 1, wherein the said preheated 1,3-propanediol is combined with the preheated terephthalic acid ester to form a mixture having a mole ratio of 1 ,3-propanediol to terephthalic acid ester of 1.2:1 to 2.3:1 and maintaining the temperature of the mixture at 150°C to 220°C and wherein the continuously feeding the preheated 1,3-propanediol and the preheated terephthalic acid ester through the at least one inlet to the ester exchange vessel located at or below the midpoint comprises continuously feeding the preheated 1,3- propanediol/terephthalic acid ester mixture through the at least one inlet to the ester exchange vessel. The process as claimed in claim 1 or 2, wherein said at least one inlet is located in a base portion of the ester exchange vessel. The process as claimed in claim 1, wherein the said preheated 1 ,3-propanediol is combined with the preheated terephthalic acid ester to form a mixture having a mole ratio of 1,3-propanediol to terephthalic acid ester of 1.2:1 to 2.3:1 and maintaining the temperature of the mixture at 150°C to 220°C; wherein the continuously feeding the preheated 1,3-propanediol and the preheated terephthalic acid ester through the at least one inlet to the ester exchange vessel located at or below about the midpoint of the ester exchange vessel comprises continuously feeding (1) the preheated 1,3 propanediol/terephthalic acid ester mixture through an inlet to an ester exchange vessel and (2) continuously feeding additional 1,3-propanediol through a separate inlet to the exchange vessel. The process as claimed in claim 4, wherein the said continuously feeding (1) the preheated 1,3-propanediol/terephthalic acid ester mixture is injected through an inlet in the base of the ester exchange vessel and (2) the additional 1,3-propanediol is injected at an inlet at about the quarter point of the ester exchange vessel. The process as claimed in claim 1, wherein the preheated 1,3-propanediol and the preheated terephthalic acid ester to an ester exchange vessel are continuously fed through separate inlets located at or below about the midpoint of the ester exchange vessel in a mole ratio of 1,3-propanediol to terephthalic acid ester of 1.2:1 to 2.3: 1 and where the 1,3-propanediol and the terephthalic acid ester undergo a continuous transesterification reaction to form a liquid reaction mixture and gaseous reaction products. The process as claimed in claim 6 wherein the said inlet where the preheated terephthalic acid ester is injected is in the base of the ester exchange vessel and the said inlet where the preheated 1,3-propanediol is injected is at about the quarter point of the ester exchange vessel. 8. The process as claimed in any of the preceding claims wherein the said terephthalic acid ester is dimethyl terephthalate. 9. The process as claimed in any of the preceding claims, wherein transesterification catalyst selected from the group consisting of organic or inorganic compounds of titanium, lanthanum, zinc and cobalt is mixed with the 1,3-propanediol prior to the preheating step. 10. The process as claimed in any of the preceding claims, wherein the separated gaseous reaction products are condensed, and the condensate contains not greater than 700 ppm of acrolein and not greater than 1000 ppm allyl alcohol, based on total condensates. 11. The process as claimed in any of the preceding claims , wherein the said separated gaseous reaction products are continuously condensed wherein the condensate contains not greater than 350 ppm of acrolein and not greater than 400 ppm allyl alcohol, based on total condensates. 12. The process as claimed in any of the preceding claims, wherein said at least one of bis(3-hydroxypropyl) terephthalate and low molecular weight oligomers have an average degree of polymerization of 1 to 15. 13. The process as claimed in any of the preceding claims, wherein the stream of liquid reaction products that is removed from the ester exchange vessel contains unreacted terephthalic acid ester in an amount not greater than 9 weight percent. 14. The process as claimed in any of the preceding claims, wherein the ester exchange vessel comprises a bubble cap column having a plurality of bubble cap plates spaced vertically apart from one another. 15. The process as claimed in any of the preceding claims, wherein a stream of the liquid reaction mixture is withdrawn from a base portion of the ester exchange vessel, the withdrawn mixture is heated by being passed through the external heater, and the withdrawn heated mixture is fed back to the base portion causing the mixing. Dated this 8th Day of July, 2002 (RANJNA MEHTA-DUTT) OF REMFRY & SAGAR ATTORNEYS FOR THE APPLICANTS

Full Text

FORM 2
THE PATENTS ACT, 1970
[39 OF 1970]
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
[See Section 10: rule 13]
A PROCESS FOR THE CONTINUOUS PRODUCTION OF ATLEAST ONE OF BIS (3-HYDROXYPROPYL) TEREPHTHALATE AND LOW MOLECULAR WEIGHT OLIGOMERS OF 1,3-PROPANEDIOL AND TEREPHTHALIC ACID"
E.I. DU PONT DE NEMOURS AND COMPANY, a Delaware corporation of 1007 Market Street, Wilmington, Delaware 19898, United States of America,
The following specification particularly describes the nature of the invention and the manner in which it is to be performed:-

FIELD OF THE INVENTION
The present invention relates to a continuous process for the production of a mixture of bis(3-hydroxypropyl) terephthalate monomer and low molecular weight oligomers of 1,3-propanediol and terephthalic acid from 1,3-propanedio] and dimemylterephalate. The bis(3-hydroxypropyl) terephthalate monomer/oligomer mixture may be used as a feed material in a continuous polymerization process for the production of poly(l,3-propylene terephthalate).
BACKGROUND OF THE INVENTION
Batch processes for the production of bis(hydroxyalkyl) terephthalate esters are known. For example, Doerr et al., U.S. Patent No. 5,340,909 discloses a batch process for the manufacture of poly(l,3-propylene terephthalate), including a batch ester interchange reaction in which 1,3-propanediol is reacted with a lower dialkyl ester of terephthalic acid.
Continuous transesterification processes are known for the production of bis(2-hydroxyethyl) terephthalate. For example, Vodonik, U.S. Patent No. 2,829,153, discloses a continuous process for the production of bis(2-hydroxyethyl) terephthalate and its low molecular weight oligomers from ethylene glycol and dimethylterephthalate.
It would be highly desirable to provide a continuous ester exchange process for the production of bis(3-hydroxypropyl) terephthalate and its low molecular weight oligomers from 1,3-propanediol and dimethylterephthalate. The present invention provides such a process.
SUMMARY OF THE INVENTION
The invention comprises a process for the continuous production of at least one of bis(3-hydroxypropyl) terephthalate and low molecular weight oligomers of 1,3-propanediol and terephthalic acid, comprising:
(a) preheating 1,3-propanediol to a temperature of about 150°C to about 200°C;
(b) preheating one or more lower dialkyl esters of terephthalic acid to a temperature of about 150°C to about 220°C;
(c) combining the preheated 1,3-propanediol with the preheated terephthalic acid esters to form a mixture having a mole ratio of 1,3-propanediol to

terephthalic acid ester of about 1.2:1 to about 2.3:1 and maintaining the temperature of the mixture at about 150°C to about 220°C;
(d) continuously feeding the preheated 1,3-propanediol/terephthalic acid ester mixture through at least one inlet to an ester exchange vessel where the mixture undergoes a continuous transesterification reaction to form a liquid reaction mixture and gaseous reaction products;
(e) continuously heating and mixing the liquid reaction mixture, whereby the temperature of the mixture in a base portion of the ester exchange vessel is maintained at about 215°C to about 250°C and the pressure in a base portion of the ester exchange vessel is maintained at about 800 mm Hg to about 1,000 mm Hg (10664 to 133322 Pa), thereby continuing the transesterification reaction to form liquid reaction products and gaseous reaction products;
(f) continuously separating the gaseous reaction products from the liquid reaction mixture in a separating portion of the ester exchange vessel which is above the base portion; and
(g) continuously removing a stream of liquid reaction products from the base portion of the ester exchange vessel, the stream comprising at least one of bis(3-hydroxypropyl) terephthalate and low molecular weight oligomers of 1,3-propanediol and terephthalic acid.
DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic representation of an apparatus useful in carrying out the process of the invention.
Figure 2 is a schematic representation of a section of a bubble cap column useful in carrying out the process of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the process of the invention, 1,3-propanediol and one or more lower dialkyl esters of terephthalic acid are reacted to form bis(3-hydroxypropyl) terephthalate and low molecular weight oligomers of 1,3-propanediol and terephthalic acid having an average degree of polymerization of about 1 to about 15. While lower dialkyl esters of terephthalic acid other than dimethylterephthalate may be used in the process of the invention, for simplicity, the remainder of the description refers only to dimethylterephthalate.
As shown in Figure 1, a mixture of 1,3-propanediol and transesterification catalyst is fed to ester exchange column 1 from tank 2, and dimethylterephthalate is fed from tank 3, both via temperature-controlled feed lines 4.

The 1,3-propanediol is mixed with a catalyst, preferably prior to mixing with dimethylterephthalate. Catalysts useful in the process of the invention include organic and inorganic compounds of titanium, lanthanum, zinc and cobalt, such as oxides, carbonates, phosphorus derivatives, and alkyl, aryl and acyl derivatives, and the like. Examples of such catalysts include tetraisopropyl titanate, tetraisobutyl titanate, lanthanum acetylacetonate and cobalt acetate. Titanium catalysts, such as tetraisopropyl titanate and tetraisobutyl titanate are preferred and are added to the 1,3-propanediol in an amount sufficient to yield 20 to 90 ppm of titanium by weight based on the weight of poly(l,3-propylene terephthalate) formed in subsequent processing.
The catalyzed 1,3-propanediol is preheated to a temperature of about 150°C to about 200°C, preferably about 185°C, prior to mixing with dimethylterephthalate. The dimethylterephthalate is preheated to a temperature of about 150°C to about 220°C, preferably about 185°C, prior to mixing with catalyzed 1,3-propanediol. The preheated catalyzed 1,3-propanediol is mixed with the preheated dimethylterephthalate by means of static mixer 5 in the feed line. Optionally, preheating is continued after mixing,, such that the catalyzed 1,3-propanediol/dimethylterephthalate mixture reaches a temperature of about 150°C to about 220°C, preferably about 200°C to about 220°C, prior to being fed to the ester exchange vessel.
The mole ratio of 1,3-propanediol to dimethylterephthalate is about 1.2:1 to 2.3:1, preferably about 1.3:1 to 1.7:1, and most preferably about 1.5:1 in the mixture that is fed to the ester exchange vessel.
In a preferred embodiment of the invention, the ester exchange vessel has three integral sections. The base portion of the vessel is the calandria 6, above which is bubble cap column 7 and one or more condensers 8. The calandria functions as a heat exchanger to heat the liquid reactants to a temperature of about 215° to 250°C, preferably about 230° to 240°C, and most preferably about 235°C.
The calandria is jacketed and heated by means of a gaseous or liquid heating medium, e.g., Dowtherm vapor. The calandria supplies all of the heat for the ester exchange column. If desired, a stream of the liquid reaction mixture can be withdrawn from the exchange vessel, passed through the external heater and heated, and then fed back to the exchange vessel to cause mixing.
As shown in Figure 2, bubble cap plate section 7, also referred to as the tray section or column, has a plurality of bubble cap plates (or trays) 9, each one extending completely across the column and spaced apart vertically from one another by a distance of typically about one foot. Each bubble cap plate 9 holds a constant level of liquid on the plate during operation. Each plate 9 as a plurality of bubble caps which

are evenly distributed across the plate. The bubble caps allow hot vapor to rise through the plates and up the column. Each bubble cap has a chimney 11 and a cap 12 which is notched along the lower edge and fits down onto plate 9. Vapor traveling up though a chimney 11 reverses direction when it reaches the lower surface of cap 12. The vapor then pushes the liquid under cap 12 down until it is below the notches and then bubbles up through the liquid around the outside of the bubble cap. Plates 9 also have baffles to- direct the flow of liquid 1,3-propanediol and dimethylterephthalate across the plate and around the bubble caps and a downcomer 10 to carry the liquid from one plate to the one below. Additional information regarding bubble cap columns is available, e.g., from R. H. Perry and D.W. Green, Perry's Chemical Engineers' Handbook, 7th ed., Section 14 (The McGraw-Hill Companies, 1997).
Due to the structure of bubble cap column 7, there is a gradual step-wise decrease in pressure from below the first plate to above the uppermost plate in the ester exchange column. The pressure at the base of the column, i.e., above the liquid level in the calandria and below the. first plate, is maintained at a pressure of about 800 mm Hg to about 1,000 mm Hg (10,664 to 133,322 Pa), preferably about 850 to 950 mm Hg (113,305 to 126,635 Pa). The pressure at the top of the column is at or near atmospheric pressure because the top of the exchanger is vented to the atmosphere.
The 1,3-propanediol/dimethylterephthalate mixture may be injected into the ester exchange column at various points at or below about the midpoint of the tray section. For example, the 1,3-propanediol/dimethylterephthalate mixture may be injected at the base of the exchanger (calandria), or onto a tray located approximately one quarter of the distance between the bottom and the top of the exchanger (hereinafter the "quarterpoint"), or onto a tray located at approximately the midpoint of the exchanger. The injection point and mole ratio are adjusted in order to minimize unconverted dimethylterephthalate and acrolein and allyl alcohol generation. The preferred process is to use a mole ratio of about 1.5:1 1,3-propanediol to dimethylterephthalate and to inject the 1,3-propanediol/dimethylterephthalate mixture into the base of the exchanger column below the first tray. Alternatively, a mole ratio of up to 2.0 moles of 1,3-propanediol per mole of dimethylterephthalate is used, and the 1,3-propanediol/dimethylterephthalate mixture is injected at the quarterpoint or midpoint of the exchanger. In this latter process, a higher mole ratio is needed to prevent higher boiling monomer from staying on the trays. This alternate process has been found to reduce the unconverted dimethylterephthalate but requires that more 1,3-propanediol be recovered in the prepolymerization step.

In yet another alternative, a mixture of preheated, catalyzed 1,3-propanediol and preheated dimethylterephthalate is injected into the base of the exchanger, and additional virgin 1,3-propanediol, typically at ambient temperature, is injected at the quarterpoint of the exchange column. In this embodiment, the mixture that is injected into the base of the exchanger has a lower mole ratio of 1,3-propanediol to dimethylterephthalate and a higher catalyst concentration than the mixture used in previously described embodiments, such that the overall mole ratio and catalyst concentration remain within the above-described ranges, after taking into account the additional 1,3-propanediol that is injected at the quarterpoint. In still another alternative, preheated dimethylterephthalate and preheated catalyzed 1,3-propanediol are injected into the exchanger separately without premixing. For example, the dimethylterephthalate is injected into the base of the exchanger, and the catalyzed 1,3-propanediol is injected at the quarterpoint.
At least one condenser 8 is provided for condensing the methanol vapor and other gaseous by-products produced by the transesterification reaction. A portion of the condensed methanol can be refluxed back to the bubble cap column to control the top tray temperature. Any remaining condensate is removed from the process.
The methanol vapor exiting the ester exchange column typically contains other reaction by-products such as acrolein and allyl alcohol. It is desirable that the production of by-products such as acrolein and allyl alcohol be minimized because both compounds are highly toxic and cause irritation to the eyes and mucous membranes. According to the process of the invention, the amount of acrolein contained in the condensate exiting the ester exchange column is no greater than 700 ppm, preferably no greater than 350 ppm, and more preferably no greater than 30 ppm. The amount of allyl alcohol contained in the condensate exiting the ester exchange column is no greater than 1000 ppm, preferably no greater than 400 ppm, and more preferably no greater than 200 ppm. The term "ppm" is used herein to mean parts per million and is equal to micrograms per gram.
The liquid reaction product containing bis(3-hydroxypropyl) terephthalate monomer and low molecular weight oligomers of 1,3-propanediol and terephthalic acid are removed from the ester exchange vessel via outlet 13 in the calandria 6. The liquid reaction product contains unreacted dimethylterephthalate in an amount not greater than 9%, preferably not greater than 4%, of the total weight of the exit stream. The monomer/oligomer mixture may be fed to a prepolymerizer, flasher or other reaction vessel where it is further reacted to produce a higher molecular weight poly(l,3-propylene terephthalate) prepolymer.
The residence time in the ester exchange column is about 1 to 2 hours.

EXAMPLES 1-7
Using an ester exchanger of the type indicated in the drawings, a 76.4 lb./hr (34.7 kg/hr) stream of dimethyl terephthalate (DMT) was preheated to a temperature of 185°C and continuously mixed with a stream of catalyzed 1,3-propanediol which was also preheated to a temperature of 185°C, to form a mixture. The mole ratio of 1,3-propanediol to dimethylterephthalate was varied from 1.5:1 to 1.8:1 to 2.0:1 to 2.25:1 by varying the catalyzed 1,3-propanediol stream from 44.9 lb./hr (20.4 kg/hr) to 53.9 lb./hr (24.5 kg/hr) to 59.9 lb./hr (27.2 kg/hr) to 67.3 lb./hr (30.6 kg/hr). The catalyst was tetrisoprpyl titanate (Tyzoi® TPT, available from E. I. duPont de Nemours and Company, Wilmington, DE), which was added to the glycol in an amount sufficient to yield 50 ppm or 30 ppm by weight of titanium based on the weight of poly(l,3-propylene terephthalate) formed in subsequent processing. The dimethylterephthalate/catalyzed glycol mixture was fed into the ester exchanger either at the base (calandria) or at the quarterpoint. The temperature of the liquid reactants at the base of the ester exchanger (calandria) was maintained at 237°C, and the pressure at the base of the ester exchanger was maintained at 900 to 950 mm Hg (119,970 to 126,635 Pa). The pressure at the top of the ester exchange column was atmospheric. In the ester exchanger, the 1,3-propanediol reacted with the dimethylterephthalate to form bis(3-hydroxypropyl) terephthalate monomer and low molecular weight oligomers of 1,3-propanediol and terephthalic acid, liberating methanol vapor and other by-products, which were continuously removed from the top of the ester exchanger. The monomer/oligomer mixture was continuously removed from the base of the ester exchanger to be fed to a prepolymerizer, flasher or other reaction vessel where it was further reacted to produce pol(l,3-propylene terephthalate) prepolymer. The conditions and results for the continuous ester exchange process are set forth in Table I.
In Table I, the level of catalyst is given as parts per million (ppm) by weight of titanium in the finished polymer. The amount of unconverted dimethylterephthalate (DMT) is given as a weight percentage based upon the total weight of the exit stream. The acrolein and allyl alcohol levels are given in parts per million (ppm) by weight based on the total condensate that is removed from the ester exchange vessel. The dipropylene glycol (DPG) levels are given as a weight percent based on monomer/oligomer exiting the exchange vessel.

TABLE I
Example Catalyst
Ti (ppm) Mole Ratio
Glycol/
DMT Unconv. DMT
(Wt.0/o) Acrolein (ppm) Allyl
Alcohol
(ppm) DPG (wt.%)
1 50 1.5* 5.6 76 506 0.12
2 50 1.5 5.6 22 291 0.13
3 50 1.8 5.8 37 259 0.15
.4 50 2.0* 3.4 37 202 0.25
5 50 2.0 4.5 31 222 0.19
6 50 2.25 5.3 21 146 0.19
7 30 1.5 7.1 20 246 0.13
* In Examples 1 and 4, 1,3-propanediol (glycol) and dimethylterephthalate (DMT) were premixed and fed to the ester exchanger vessel at the quarter point. In all other Examples, the 1,3-propanediol/dimethylterephthalate mixture was fed to the base of exchanger.

We Claim:
1. A process for the continuous production of at least one of bis(3-
hydroxypropyl) terephthalate and low molecular weight oligomers of
1,3-propanediol and terephthalic acid, comprising:
(a) preheating 1,3-propanediol to a temperature of 150°C to 200°C;
(b) preheating one or more lower dialkyl esters of terephthalic acid to
a temperature of 150°C to 220°C;
(c) continuously feeding the reheated 1,3-propanediol and the
preheated terephthalic acid ester through at least one inlet to an ester
exchange vessel located at or below the midpoint of the ester
exchange vessel where the total, 1,3-propanediol and terephthalic
acid ester added to the ester exchange vessel is in a mole ratio of 1,3-
propanediol to terephthalic acid ester of 1.2:1 to 2.3:1 and the 1,3-
propanediol and terephthalic acid ester undergo a ontinuous
transesterification reaction to form a liquid reaction mixture and
gaseous reaction products;
(d) continuously heating and mixing the liquid reaction mixture,
whereby the temperature of the mixture in a base portion of the ester
exchange vessel is maintained at 215°C to 250°C and the pressure in
a base portion of the ester exchange vessel is maintained at 800 mm
Hg to 1,000 mm Hg, thereby continuing the transesterification
reaction to form liquid reaction products and gaseous reaction
products;
(e) continuously separating the gaseous reaction products from the

liquid reaction mixture in a separating portion of the ester exchange vessel which is above the base portion; and
(f) continuously removing a stream of liquid reaction products from the base portion of the ester exchange vessel, the stream comprising at least one of bis(3- hydroxypropyl) terephthalate and low molecular weight oligomers of 1,3-propanediol and terephthalic acid. The process as claimed in claim 1, wherein the said preheated 1,3-propanediol is combined with the preheated terephthalic acid ester to form a mixture having a mole ratio of 1 ,3-propanediol to terephthalic acid ester of 1.2:1 to 2.3:1 and maintaining the temperature of the mixture at 150°C to 220°C and wherein the continuously feeding the preheated 1,3-propanediol and the preheated terephthalic acid ester through the at least one inlet to the ester exchange vessel located at or below the midpoint comprises continuously feeding the preheated 1,3- propanediol/terephthalic acid ester mixture through the at least one inlet to the ester exchange vessel.
The process as claimed in claim 1 or 2, wherein said at least one inlet is located in a base portion of the ester exchange vessel. The process as claimed in claim 1, wherein the said preheated 1 ,3-propanediol is combined with the preheated terephthalic acid ester to form a mixture having a mole ratio of 1,3-propanediol to terephthalic acid ester of 1.2:1 to 2.3:1 and maintaining the temperature of the mixture at 150°C to 220°C; wherein the continuously feeding the preheated 1,3-propanediol and the preheated terephthalic acid ester

through the at least one inlet to the ester exchange vessel located at or below about the midpoint of the ester exchange vessel comprises continuously feeding (1) the preheated 1,3 propanediol/terephthalic acid ester mixture through an inlet to an ester exchange vessel and (2) continuously feeding additional 1,3-propanediol through a separate inlet to the exchange vessel.
The process as claimed in claim 4, wherein the said continuously feeding (1) the preheated 1,3-propanediol/terephthalic acid ester mixture is injected through an inlet in the base of the ester exchange vessel and (2) the additional 1,3-propanediol is injected at an inlet at about the quarter point of the ester exchange vessel. The process as claimed in claim 1, wherein the preheated 1,3-propanediol and the preheated terephthalic acid ester to an ester exchange vessel are continuously fed through separate inlets located at or below about the midpoint of the ester exchange vessel in a mole ratio of 1,3-propanediol to terephthalic acid ester of 1.2:1 to 2.3: 1 and where the 1,3-propanediol and the terephthalic acid ester undergo a continuous transesterification reaction to form a liquid reaction mixture and gaseous reaction products.
The process as claimed in claim 6 wherein the said inlet where the preheated terephthalic acid ester is injected is in the base of the ester exchange vessel and the said inlet where the preheated 1,3-propanediol is injected is at about the quarter point of the ester exchange vessel.

8. The process as claimed in any of the preceding claims wherein the said terephthalic acid ester is dimethyl terephthalate.
9. The process as claimed in any of the preceding claims, wherein transesterification catalyst selected from the group consisting of organic or inorganic compounds of titanium, lanthanum, zinc and cobalt is mixed with the 1,3-propanediol prior to the preheating step.
10. The process as claimed in any of the preceding claims, wherein the separated gaseous reaction products are condensed, and the condensate contains not greater than 700 ppm of acrolein and not greater than 1000 ppm allyl alcohol, based on total condensates.
11. The process as claimed in any of the preceding claims , wherein the said separated gaseous reaction products are continuously condensed wherein the condensate contains not greater than 350 ppm of acrolein and not greater than 400 ppm allyl alcohol, based on total condensates.
12. The process as claimed in any of the preceding claims, wherein said at least one of bis(3-hydroxypropyl) terephthalate and low molecular weight oligomers have an average degree of polymerization of 1 to 15.

13. The process as claimed in any of the preceding claims, wherein the stream of liquid reaction products that is removed from the ester exchange vessel contains unreacted terephthalic acid ester in an amount not greater than 9 weight percent.
14. The process as claimed in any of the preceding claims, wherein the ester exchange vessel comprises a bubble cap column having a

plurality of bubble cap plates spaced vertically apart from one another. 15. The process as claimed in any of the preceding claims, wherein a stream of the liquid reaction mixture is withdrawn from a base portion of the ester exchange vessel, the withdrawn mixture is heated by being passed through the external heater, and the withdrawn heated mixture is fed back to the base portion causing the mixing.
Dated this 8th Day of July, 2002
(RANJNA MEHTA-DUTT)
OF REMFRY & SAGAR
ATTORNEYS FOR THE APPLICANTS

Documents:

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in-pct-2002-00917-mum-cancelled pages(24-01-2005).pdf

in-pct-2002-00917-mum-claims(granted)-(24-01-2005).doc

in-pct-2002-00917-mum-claims(granted)-(24-01-2005).pdf

in-pct-2002-00917-mum-correspondence(22-03-2005).pdf

in-pct-2002-00917-mum-correspondence(ipo)-(09-04-2007).pdf

in-pct-2002-00917-mum-form 1(08-07-2002).pdf

in-pct-2002-00917-mum-form 19(14-07-2004).pdf

in-pct-2002-00917-mum-form 2(granted)-(24-01-2005).doc

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in-pct-2002-00917-mum-form 3(08-07-2002).pdf

in-pct-2002-00917-mum-form 5(08-07-2002).pdf

in-pct-2002-00917-mum-form-pct-ipea-409(08-07-2002).pdf

in-pct-2002-00917-mum-form-pct-isa-210(08-07-2002).pdf

in-pct-2002-00917-mum-power of authority(08-07-2002).pdf

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Patent Number

205741

Indian Patent Application Number

IN/PCT/2002/00917/MUM

PG Journal Number

26/2007

Publication Date

29-Jun-2007

Grant Date

09-Apr-2007

Date of Filing

08-Jul-2002

Name of Patentee

E.I. DU PONT DE NEMOURS AND COMPANY

Applicant Address

1007 MARKET STREET, WILMINGTON, DELAWARE 19898, UNITED STATES OF AMERICA.

Inventors:

#	Inventor's Name	Inventor's Address
1	CARL J GIARDINO	1800 CONNIES LANE, HIXSON, TN 37343, U.S.A.
2	DAVID B. GRIFFITH	18014 SPELLBROOK DRIVE, HOUSTON, TX 77084, U.S.A.
3	CHUNG-FAH HOWARD HO	3203 HODGES ROAD, KINSTON, NC 28504, U.S.A.
4	JAMES M. HOWELL	108 SOUTH BAYWOOD LANE, GREENVILLE, NC 27834, U.S.A.
5	MICHELLE HOYT WATKINS	611 ASHBY DRIVE, WAYNESBORO, VA 22980, U.S.A.

PCT International Classification Number

C08G 63/78

PCT International Application Number

PCT/US00/21783

PCT International Filing date

2000-08-10

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	09/503,599	2000-02-11	U.S.A.