Title of Invention

AN IMPROVED SOLID-STATE POLYMERIZATION PROCESS FOR THE PRODUCTION OF HIGH MOLECULAR WEIGHT POLYETHYLENE TEREPHTHALATE

Abstract

The invention relates to an improved process for polyester synthesis, the process comprising first reacting a dicarboxylic acid and a polyol at a temperature in the range of 250 to 290 degree celsius to obtain an ester oligomer, then reacting the oligomer in the molten state at a temperature in the range of 260 to 300 degree celsius with 0.01 to 10 percentage by weight of at least one aklyl substituted 1,3-propane diol resulting in a prepolymer having intrinsic viscosity up to 0.65 dl/g and finally reating the polymer in the solid state at a temperature of 200 to 240 degree celsius, under an inert atmosphere. The invention also relates to the polyester resin to the compositions containing the resin and to the shaped articles prepared from the composition.

Full Text

FORM 2 THE PATENT ACT 1970 (39 of 1970) & The Patents Rules, 2003 Provisional COMPLETE SPECIFICATION (See section 10 and rule 13) 1. TITLE OF THE INVENTION: An improved solid-state polymerization process for the production of high molecular weight polyethylene terephthalate. 2 APPLICANT (a) NAME : Reliance Industries Limited (b)NATIONALITY : Indian company incorporated under the Companies Act 1956 (c) ADDRESS : Reliance Technology Center, B-4 MIDC Industrial Area, Patalganga-410220, Dist- Raigad, Maharashtra, India. 3. INVENTORS (a) Name : Nadkarni Vikas Madhusudan (b) Nationality : Indian (c) Address : Al8 Garden Estate, Off D P Road Aundh, Pune -411007 Maharashtra India (a) Name : Wadekar Shreeram Ashok (b)Nationality : Indian (c) Address : 204, Mohandeep Co-Op Housing Society Ltd. Almeida Road, Chandanwadi, Panchpakhadi, Thane (West),400601 Maharashtra, India (a)Name : Ayodhya Srinivasacharya Ramacharya (b)Nationality : Indian (c) Address : Flat No. 7, Phoenix Co-operative Housing Society, Plot No. 23, Sector 9A , Vashi, Navi Mumbai 400 703 Maharashtra India (a)Name : Sudan Pushap (b)Nationality : Indian (c) Address : House no:-237, Sector-2,Baba Ajit Nagar,Upper Gadigarh,jammu ( Tawi) Jammu & Kashmir, India (a)Name : Satpathy Anil Kumar (b)Nationality : Indian (c) Address : Village/Post Banasing Dist.Dhenkanal State Orrisa-759014 India 3. PREAMBLE TO THE DESCRIPTION The following specification particularly describes the invention and the manner in which it is to be performed: TECHNICAL FIELD OF THE INVENTION: This invention relates to an improved solid-state polymerization process for the production of high molecular weight polyester resin comprising neopentyl glycol and / or 2-methyl -1,3-propanediol or such diols containing tertiary or quaternary carbon atoms with pendant groups suitable for the production of containers, films and industrial yarn applications. BACKGROUND OF THE INVENTION: PET resins are well known for making films, fibers and packaged container applications. Generally, two major and distinct process steps are involved in the production of high molecular weight polyesters. These two steps include melt polymerization and solid-state polymerization (SSP). In the polymerization process for producing polyester having high intrinsic viscosity (IV), base prepolymer of IV of about 0.4 dl/g to about 0.65 dl/g is produced by melt polymerization process. These base chips are cylindrical or spherical in shape. Base chip of prepolymer polyester is amorphous in nature. Base prepolymer is then subjected to solid-state polymerization after crystallizing it in a crystallizer so as to avoid sintering or lump formation in the SSP reactor. Using SSP process, depending on the application, different IV resin can be produced. Conventional polyester polymerization processes are disclosed in US 3,405,098; US 3,544,525; US 4,245,253; US 4,238,593; and US 5,408,035. For producing transparent polyester articles such as preforms and containers, traditionally small amount of isophthalic acid is being used. Preferably less than 10 wt% of isophthalic acid is required for producing haze free products. Apart from isophthalic acid, use of cyclohexanedimethanol, neopentyl glycol or 2-methyl-1,3 propanediol is also recorded. In the prior art, PET was modified to minimize crystallization rate during parison molding and blow molding, by adding a small quantity of isophthalic acid (IPA) together with terephthalic acid as dicarboxylic acid component of PET, or cyclohexanedimethanol (CHDM) or neopentyl glycol together with ethylene glycol as glycol component of PET, thus producing copolymeric PET having a slow crystallizing rate by conventional copolymerization (Lecture abstracts of the 11th Colloquium on Structure and Physical Properties of High Polymers, held by the Japanese High Polymer Society, Kanto Branch, on June 16, 1981, "Recent Progress in Modification of Polymers" p.3.). These co-monomers are preferably added at the stage of polymerization. A US patent 4,415,727 describes the use of 2-methyl-1, 3 propanediol for the production of PET bottles for packaging applications. A Japanese patent 2006274239 discloses the moulding components for producing dust boxes, pylons, flower vases, stools, lighting shades, umbrella stands, and powder packaging containers. Various comonomers selected from isophthalic acid, 2,6-naphthalenedicarboxylic acid, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, and/or 2-methyl-1,3-propanediol were suggested. A Japanese patent JP 2003064167 discloses the use of 2-methyl-1,3 propanediol and cyclohexanedimethanol for improving transparency, impact and heat resistance of moulded polyester products. A Japanese patent JP 2002275252 describes the di-Me 2,6-naphthalate-ethylene glycol-2-methyl-1,3-propanediol copolymer for producing bottles for packaging applications. WO 2002042354 explains the production of unsatd. terephthalate-based polyester resins (UPR) based on 2-methyl-1,3-propanediol without use of a catalyst in reasonable cycle times.. A European patent application EP 984086 assigned to M/s Dairen Chemical Corporation for the manufacture of polyester fibers containing 2-methyl-1,3-propanediol units in the molecular chain with improved dyeability and low elongation and high tensile strength. A French patent FR 2004619 discloses the use of neopentyl glycol along with 2-methyl-1,3-propanediol during polyester polymerization for producing transparent polyester articles. None of these patents discloses the solid-state polymerization process and reactivity gain in the SSP process using neopentyl glycol and 2-methyl-1, 3 propanediol. It was surprisingly found that neopentyl glycol or 2-methyl-1, 3 propanediol, increases solid-state polymerization rate. OBJECTS OF THE INVENTION: An object of the invention is to provide an improved solid-state polymerization process for the production of high molecular weight polyester prepolymer having IV of 0.5 dl/g to 1.2 dl/g produced from low molecular weight polyester prepolymer having IV of 0.4 dl/g to 0.65 dl/g comprising the co-monomer, neopentyl glycol and / or 2-methyl -1,3-propanediol along with conventional monomers. Yet another object of the present invention is to provide low molecular weight polyethylene terephthalate (PET) prepolymer having IV of 0.4 dl/g to 0.65 dl/g comprising the co-monomer, neopentyl glycol and / or 2-methyl -1,3-propanediol along with conventional monomers. Yet another object of the present invention is to provide high molecular weight polyethylene terephthalate (PET) and similar terephthalate polyesters having IV of about 0.5 dl/g to about 1.2 dl/g comprising co-monomer neopentyl glycol and / or 2-methyl -1,3-propanediol using solid-state polymerization process having faster reactivity. Yet another object of the present invention is to provide use of high molecular weight polyethylene terephthalate (PET) and similar terephthalate polyesters having IV of about 0.5 dl/g to about 1.2 dl/g comprising co-monomer neopentyl glycol and / or 2-methyl -1,3-propanediol for the production of containers, films and industrial yarns. DETAILED DESCRIPTION OF THE INVENTION: According to the invention there is provided an improved solid-state polymerization process for the production of high molecular weight polyester resin having IV of about 0.5 dl/g to about 1.2 dl/g from low molecular weight prepolymer having IV of about 0.4 dl/g to about 0.65 dl/g comprising a neopentyl glycol and / or 2-methyl-1, 3-propandiol or alike. According to the present invention, there is provided an improved solid-state polymerization process for the production of high molecular weight polyester resin from lower molecular weight polyester prepolymer comprising at least one dicarboxylic acid or mono- or di-ester of dicarboxylic acid or acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride, at least one polyol (The term "polyol" means alcohol having atleast two or more hydroxyl group) and neopentyl glycol or 2-methyl-1, 3-propanediol and alike. The IV of the prepolymer is in the range of about 0.4 dl/g to about 0.65 dl/g. The base polyester chips produced with this process are amorphous or semi crystalline in nature and have any preferred shape such as spherical, hemispherical or cylindrical. These prepolymer chips further used as a precursor for solid-state polymerization for increasing the IV. According to the invention there is provided an improved solid-state polymerization process for the production of high polyester resin suitable for the production of preforms, containers, films and technical yarns particularly beverage containers, the process comprising: a. adding among other things, at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid or 4,4'-biphenyl dicarboxylic acid or monoesters thereof or diesters thereof or anhydrides and at least one polyol selected from monoethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylenes glycol or 1,4-cyclohexane diol; b. esterifying the mixture of step (a) at temperature in the range of 250 to 290°C; c. removing excess or unreacted polyol or water produced from the step (b); d. polymerizing the esterified mixture at temperature in the range at 260°C - 300°C to obtain low molecular weight polyester prepolymer having IV of about 0.1 to about 0.45 dl/g; e. adding neopentyl glycol and / or 2-methyl-1,3-propandiol at any stage during melt polymerization steps of (a), (b), (c) or (d) but before the chips formation process; f. producing an amorphous or semi crystalline and a spherical, hemispherical or cylindrical shape prepolymer; and g. polymerizing a prepolymer by solid- state polymerization at temperature 200°C - 240°C to produce high molecular weight polyester resin suitable for the production of preforms, beverage containers, films and industrial yarns. Preferably, neopentyl glycol and / or 2-methyl-1,3-propanediol is added in the range of 0.01% to 10% by weight of polyester. More preferably, neopentyl glycol and / or 2-methyl-1,3-propanediol is added in the range of about 0.5% to about 5% by weight of polyester. Neopentyl glycol and / or 2-methyl-1,3-propanediol is added in the esterification reactor, oligomer line or UFPP particularly in the oligomer line to produce polyester prepolymer. Neopentyl glycol and / or 2-methyl-1,3-propanediol is added to the resin at any stage of melt polymerization intended for improving the rate of solid-state polymerization required for the production of preforms .containers, films and industrial yarns. Here weight % means the weight of the co-monomer with respect to the polyester. The process for the production of high molecular weight polyester resin having IV of about 0.5 dl/g to about 1.2 dl/g produced from low molecular weight prepolymer having IV of about 0.4 dl/g to about 0.65 dl/g using any known polymerization process such as disclosed in US 2465319 and 2071250 and incorporated herein as a reference in its entirety. Solid state polymerization processes for the production of high molecular weight PET from the low molecular weight prepolymer are disclosed in US 4532319; 4644049; 4755587; 4876326; 5408035; 5510454; 5,532,333; 5540868; 5714262; 5830982; and 6451966, which is incorporated herein as a reference in its entirety. However, none of these patents disclose the composition for the production of polyester resin having neopentyl glycol or 2-methyl-1,3-propanediol for increasing the rate of solid-state polymerization reaction. The term "polyester" used herein is intended to include polymer and copolymer of polyethylene terephthalate (PET) or any other polyester. Preferably, high molecular weight polyester resin comprises any suitable additives such as nucleating agents, infrared absorbers, and slip agents for the improvement of any performance of polyester article. According to the invention there is provided an improved solid-state polymerization process for the production of high molecular weight polyester prepolymer having IV of 0.5 dl/g to 1.2 dl/g produced from low molecular weight polyester prepolymer having IV of 0.4 dl/g to 0.65 dl/g According to the invention there is provided low molecular weight prepolymer comprises among other things, at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid or 4,4'-biphenyl dicarboxylic acid or monoesters thereof or diesters thereof or anhydrides thereof and at least one polyol selected from monoethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylenes glycol or 1,4-cyclohexane diol and neopentyl glycol or 2-methyl-1,3-propanediol or combinations thereof in the range of 0.01% to 10% by weight of polyester. The base prepolymer polyester chips produced with this process are amorphous or semi crystalline in nature and have any preferred shape such as spherical, hemispherical or cylindrical. These prepolymer chips further used as a precursor for solid-state polymerization for increasing the IV. According to the invention there is provided a low molecular weight polyethylene terephthalate (PET) prepolymer having IV of 0.1 dl/g to 0.4 dl/g comprising co-monomer neopentyl glycol and / or 2-methyl -1,3-propanediol and alike. According to the invention there is provided a high molecular weight polyester resin with an IV from about 0.5dl/g to about 1.2 dl/g having faster rate of solid-state polymerization prepared by the above-mentioned comonomers. According to the present invention, there is provided a polymerization process having faster reaction rate in a solid-state with the use of comonomers selected from neopentyl glycol and / or 2-methyl-1,3-propanediol as compared to comonomer isophthalic acid. According to the invention there is provided an improved solid-state polymerization process for the production of high molecular weight polyester resin having IV about 0.5 dl/g to about 1.2 dl/g produced from low molecular weight prepolymer having IV of about 0.4 dl/g to about 0.65 dl/g, comprising among other things, at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid or 4,4'-biphenyl dicarboxylic acid or monoesters thereof or diesters thereof or anhydrides thereof and at least one polyol selected from monoethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylenes glycol or 1,4-cyclohexane diol and neopentyl glycol or 2-methyl-1,3-propanediol or combinations thereof in the range of 0.01% to 10% by weight of polyester. According to the invention there is provided a high molecular weight polyethylene terephthalate (PET) having IV about 0.5 dl/g to about 1.2 dl/g produced from low molecular weight prepolymer having IV of about 0.4 dl/g to about 0.65 dl/g, comprising among other things, co-monomer neopentyl glycol and / or 2-methyl -1,3-propanediol and alike in the range of 0.01% to 10% by weight of polyester. Preferably, a high molecular weight polyester resin also comprises any suitable additives for the improvement of any performance of polyester article. According to the present invention, there is provided a high molecular weight polyester resin prepared by the above process, which is used for the production of preforms, containers and films with accepted clarity. Although the invention has been described with reference to specific examples, it will be appreciated by those skilled in the art that the invention may be embodied in many other forms. Example 1 PET prepolymer having IV of 0.6 dl/g prepared by melt-phase polymerization process. Purified terephthalic acid and monoethylene glycol (MEG) were charged in 1:2 molar ratio. To the above reaction mixture, 290 ppm of Antimony trioxide catalyst based on antimony and 25 ppm NaOH were added. The esterification reaction was carried out at 255°C. 2 wt% neopentyl glycol was added at the end of esterification reaction. The oligomer obtained was then subjected to polycondensation in the presence pf 25 ppm of cobalt as Cobalt acetate and 25 ppm of phosphorous as phosphoric acid at temperature of 285°C to obtain a prepolymer having IV up to 0.6 dl/g. After achieving the desired prepolymer IV, it was drained and cut in a granular form for further processing. The granulated prepolymer was amorphous in nature. Example 2: PET prepolymer having IV of 0.6 dl/g prepared by melt-phase polymerization process. Purified terephthalic acid and monoethylene glycol (MEG) were charged in 1:2 molar ratio. To the above reaction mixture, 290 ppm of Antimony trioxide catalyst based on antimony and 25 ppm NaOH were added. The esterification reaction was carried out at 255°C. 1.5 wt% neopentyl glycol was added at the end of esterification reaction. The oligomer obtained was then subjected to polycondensation in the presence pf 25 ppm of cobalt as Cobalt acetate and 25 ppm of phosphorous as phosphoric acid at temperature of 285°C to obtain a prepolymer having IV up to 0.6 dl/g. After achieving the desired prepolymer IV, it was drained and cut in a granular form for further processing. The granulated prepolymer was amorphous in nature. Example 3: PET prepolymer having IV of 0.6 dl/g prepared by melt-phase polymerization process. Purified terephthalic acid and monoethylene glycol (MEG) were charged in 1:2 molar ratio. To the above reaction mixture, 290 ppm of Antimony trioxide catalyst based on antimony and 25 ppm NaOH were added. The esterification reaction was carried out at 255°C. 1.3 wt% neopentyl glycol was added at the end of esterification reaction. The oligomer obtained was then subjected to polycondensation in the presence pf 25 ppm of cobalt as Cobalt acetate and 25 ppm of phosphorous as phosphoric acid at temperature of 285°C to obtain a prepolymer having IV up to 0.6 dl/g. After achieving the desired prepolymer IV, it was drained and cut in a granular form for further processing. The granulated prepolymer was amorphous in nature. Example 4: PET prepolymer having IV of 0.6 dl/g prepared by melt-phase polymerization process. Purified terephthalic acid and monoethylene glycol (MEG) were charged in 1:2 molar ratio. To the above reaction mixture, 290 ppm of Antimony trioxide catalyst based on antimony and 25 ppm NaOH were added. The esterification reaction was carried out at 255°C. 2 wt% 2-methyl-1,3 propanediol was added at the end of esterification reaction. The oligomer obtained was then subjected to polycondensation in the presence pf 25 ppm of cobalt as Cobalt acetate and 25 ppm of phosphorous as phosphoric acid at temperature of 285°C to obtain a prepolymer having IV up to 0.6 dl/g. After achieving the desired prepolymer IV, it was drained and cut in a granular form for further processing. The granulated prepolymer was amorphous in nature. Example 5: PET prepolymer having IV of 0.6 dl/g prepared by melt-phase polymerization process. Purified terephthalic acid and monoethylene glycol (MEG) were charged in 1:2 molar ratio. To the above reaction mixture, 290 ppm of Antimony trioxide catalyst based on antimony and 25 ppm NaOH were added. The esterification reaction was carried out at 255°C. 1.5 wt% 2-methyl-1,3 propanediol was added at the end of esterification reaction. The oligomer obtained was then subjected to polycondensation in the presence pf 25 ppm of cobalt as Cobalt acetate and 25 ppm of phosphorous as phosphoric acid at temperature of 285°C to obtain a prepolymer having IV up to 0.6 dl/g. After achieving the desired prepolymer IV, it was drained and cut in a granular form for further processing. The granulated prepolymer was amorphous in nature. Example 6: PET prepolymer having IV of 0.6 dl/g prepared by melt-phase polymerization process. Purified terephthalic acid and monoethylene glycol (MEG) were charged in 1:2 molar ratio. To the above reaction mixture, 290 ppm of Antimony trioxide catalyst based on antimony and 25 ppm NaOH were added. The esterification reaction was carried out at 255°C. 1.3 wt% 2-methyl-1,3 propanediol was added at the end of esterification reaction. The oligomer obtained was then subjected to polycondensation in the presence pf 25 ppm of cobalt as Cobalt acetate and 25 ppm of phosphorous as phosphoric acid at temperature of 285°C to obtain a prepolymer having IV up to 0.6 dl/g. After achieving the desired prepolymer IV, it was drained and cut in a granular form for further processing. The granulated prepolymer was amorphous in nature. Example 7: Comparative PET prepolymer of IV of 0.60 dl/g was prepared in a batch reactor by melt-phase polymerization process. Purified terephthalic acid and monoethylene glycol (MEG) were charged in 1:2 molar ratio in reactor. 2 wt % Isophthalic acid was also added along with PTA. Esterification reaction was carried out at 255°C. The oligomer obtained was then subjected to polycondensation in the presence pf 25 ppm of cobalt as Cobalt acetate and 25 ppm of phosphorous as phosphoric acid at temperature of 285°C to obtain a prepolymer having IV up to 0.6 dl/g. After achieving the desired prepolymer IV, it was drained and cut in a granular form for further processing. The granulated prepolymer was amorphous in nature. This prepolymer was considered as "Control". Example 8: Comparative PET prepolymer of IV of 0.60 dl/g was prepared a batch reactor by melt-phase polymerization process. Purified terephthalic acid and monoethylene glycol (MEG) were charged in 1:2 ratio in reactor. 1.5 wt % Isophthalic acid was also added along with PTA.. Esterification reaction was carried out at 255°C. The oligomer obtained was then subjected to polycondensation in the presence pf 25 ppm of cobalt as Cobalt acetate and 25 ppm of phosphorous as phosphoric acid at temperature of 285°C to obtain a prepolymer having IV up to 0.6 dl/g. After achieving the desired prepolymer IV, it was drained and cut in a granular form for further processing. The granulated prepolymer was amorphous in nature. This prepolymer was considered as "Control". Example 9: Comparative PET prepolymer of IV of 0.60 dl/g was prepared a batch reactor by melt-phase polymerization process. Purified terephthalic acid and monoethylene glycol (MEG) were charged in 1:2 ratio in reactor. 1.3 wt % Isophthalic acid was also added along with PTA.. Esterification reaction was carried out at 255°C. The oligomer obtained was then subjected to polycondensation in the presence pf 25 ppm of cobalt as Cobalt acetate and 25 ppm of phosphorous as phosphoric acid at temperature of 285°C to obtain a prepolymer having IV up to 0.6 dl/g. After achieving the desired prepolymer IV, it was drained and cut in a granular form for further processing. The granulated prepolymer was amorphous in nature. This prepolymer was considered as "Control". Example 10: Solid state polymerization Prepolymer having IV of 0.6 dl/g obtained in the example 1 to 9 was solid-state polymerized under an inert atmosphere to raise the IV up to 1 dl/g. Solid - state polymerization was carried out in a batch reactor. Nitrogen gas temperature for solid-state polymerization was 205°C and target SSP exit IV was 0.76± 0.02 dl/g. The solid-state polymerization reaction rates in terms of IV rise per hour are given in the table 1. TABLE 1 Example No. Prepolymer IV (dl/g) Final IV (dl/g) SSP residence time (Hrs) IV rise (dl/g) / hour 1 0.601 0.755 7 0.022 2 0.606 0.769 7 0.023 3 0.603 0.766 7 0.023 4 0.599 0.781 6 0.030 5 0.610 0.772 7 0.023 6 0.607 0.762 7 0.022 7 0.606 0.753 7 0.021 8 0.607 0.742 8 0.017 9 0.604 0.777 9 0.019 Results of Table 1 indicates the faster solid-state reaction rate with neopentyl glycol and 2-methyl-1,3 propanediol as compared to isophthalic acid. According to the present invention, haze free performs was obtained due to the addition of neopentyl glycol and 2-methyl-1,3 propanediol Bottles of 1.5 L volume were produced using SIDEL SB01 single cavity blow moulding machine. Performance of the bottles produced with neopentyl glycol and 2-methyl-1,3 propanediol was comparable to the bottles produced with isophthalic acid.

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