WO2002051616A2 - Methods of post-polymerisation extruder injection in condensation polymer production - Google Patents
Methods of post-polymerisation extruder injection in condensation polymer production Download PDFInfo
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- WO2002051616A2 WO2002051616A2 PCT/US2001/048440 US0148440W WO02051616A2 WO 2002051616 A2 WO2002051616 A2 WO 2002051616A2 US 0148440 W US0148440 W US 0148440W WO 02051616 A2 WO02051616 A2 WO 02051616A2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers
Definitions
- the present invention relates to the processing of condensation polymers. More particularly, the present invention relates to the late introduction of additives into condensation polymers via reactive carriers.
- polyester fibers and films are an integral component in numerous consumer products manufactured worldwide.
- Most commercial polyester used for polyester fibers and films is polyethylene terephthalate (PET) polyester.
- PET polyethylene terephthalate
- PET polyethylene terephthalate
- polyethylene terephthalate forms a lightweight and shatterproof product
- another popular use for polyethylene terephthalate is as a resin for containers, especially beverage bottles.
- DMT dimethyl terephthalate
- dimethyl terephthalate and ethylene glycol are reacted in a catalyzed ester interchange reaction to form bis (2- hydroxyethyl) terephthalate monomers and oligomers, as well as a methanol byproduct that is continuously removed.
- bis (2-hydroxyethyl) terephthalate monomers and oligomers are then polymerized via polycondensation to produce polyethylene terephthalate polymers .
- terephthalic acid Purer forms of terephthalic acid (TA) are now increasingly available. Consequently, terephthalic acid has become an acceptable, if not preferred, alternative to dimethyl terephthalate as a starting material for the production of polyethylene terephthalate.
- terephthalic acid and ethylene glycol react in a generally uncatalyzed esterification reaction to yield low molecular weight monomers and oligomers, as well as a water byproduct that is continuously removed.
- the monomers and oligomers are subsequently polymerized by polycondensation to form polyethylene terephthalate polyester.
- the resulting polyethylene terephthalate polymer is substantially identical to the polyethylene terephthalate polymer resulting from dimethyl terephthalate, albeit with some end group differences .
- Polyethylene terephthalate polyester may be produced in a batch process, where the product of the ester interchange or esterification reaction is formed in one vessel and then transferred to a second vessel for polymerization. Generally, the second vessel is agitated and the polymerization reaction is continued until the power used by the agitator reaches a level indicating that the polyester melt has achieved the desired intrinsic viscosity and, thus, the desired molecular weight. More commercially practicable, however, is to carry out the esterification or ester interchange reactions, and then the polymerization reaction as a continuous process. The continuous production of polyethylene terephthalate results in greater throughput, and so is more typical in large-scale manufacturing facilities .
- the resulting polymer melt is typically extruded and pelletized for convenient storage and transportation before being transformed into specific polyester articles
- a high activity catalyst is often employed to increase the rate of polymerization, thereby increasing the throughput of the resulting polyethylene terephthalate polyester.
- the high activity catalysts that are used in the polymerization of polyethylene terephthalate polyester can be basic, acidic, or neutral, and are often metal catalysts .
- the traditional polymerization catalysts used in the formation of polyethylene terephthalate from both terephthalic acid and dimethyl terephthalate contain antimony, most commonly antimony trioxide (Sb 2 0 3 ) .
- Sb 2 0 3 antimony trioxide
- polymerization catalysts like antimony trioxide will eventually begin to catalyze or encourage the degradation of the polyethylene terephthalate polymer.
- Such polymer degradation results in the formation of acetaldehyde, the discoloration (e.g., yellowing) of the polyethylene terephthalate polyester, and reduction of polymer molecular weight .
- thermal stability refers to a low rate of acetaldehyde generation, low discoloration, and retention of molecular weight following subsequent heat treatment or other processing.
- Late addition of the stabilizer may provide insufficient opportunity for the stabilizer to fully blend with the polymer. Consequently, the stabilizer may not prevent degradation and discoloration of the polyester. In addition, adding stabilizer during polymer processing is inconvenient and does not provide economies of scale.
- U.S. Patent No. 5,376,702 for a Process and Appara tus for the Direct and Continuous Modifica tion of Polymer Melts discloses dividing a polymer melt stream into an unmodified stream and a branch stream that receives additives.
- a side stream takes a portion of the branch stream to an extruder, where additives are introduced.
- Such techniques are not only complicated, but also costly, requiring a screw extruder and melt piping to process additives. Consequently, such arrangements are inconvenient and even impractical where total additive concentrations are low (e.g., less than one weight percent).
- U.S. Patent No. 5,898,058 discloses adding a stabilizer, which preferably contains phosphorous, at or after the end of the polymerization reaction and before polymer processing. This deactivates the polymerization catalyst and increases the throughput of the polyester without adversely affecting the thermal stability of the polyethylene terephthalate polyester. While a noteworthy improvement over conventional techniques, U.S. Patent No. 5,898,058 teaches adding the stabilizer without a carrier. Consequently, the addition of solids into the polymer necessitates the costly use of an extruder.
- U.S. parent application Ser. No. 09/738,150 for Methods of Post-Polymerization Injection in Continuous Polyethylene Terephthala te Production discloses a process for the production of high quality polyethylene terephthalate polyester that improves upon the stabilizer-addition techniques disclosed by commonly- assigned U.S. Patent No. 5,898,058.
- U.S. application Ser. No. 09/738,150 discloses a method for the late introduction of additives into a process for making polyethylene terephthalate.
- the additives are introduced during, and preferably after, the polycondensation of polyethylene terephthalate polymers.
- the method employs a reactive carrier that not only functions as a delivery vehicle for one or more additives, but also reacts with the polyethylene terephthalate, thereby binding the carrier in the polyethylene terephthalate resin.
- U.S. application Ser. No. 09/738,150 discloses that this may be achieved using a simplified additive delivery system that does not require the use of an extruder.
- U.S. application Ser. No. 09/932,150 for Methods of Post-Polymerization Extruder Inj ection in Polyethylene Terephthala te Production, which is a continuation-in-part of U.S. parent application Ser. No. 09/738,150, discloses a method for late additive introduction at an extruder during a process for making polyethylene terephthalate.
- the method employs a reactive carrier that not only functions as a delivery vehicle for one or more additives, but also reacts with the polyethylene terephthalate to bind the carrier in the polyethylene terephthalate resin. This not only prevents the emergence of the carrier from the polyethylene terephthalate during subsequent processing
- Figure 1 illustrates the theoretical loss of molecular weight (as measured by number-average degree of polymerization) for condensation polymers having an initial degree of polymerization of about 100 as a function of the concentration of the reactive carrier at various molecular weights.
- Figure 2 illustrates the theoretical loss of molecular weight (as measured by number-average degree of polymerization) for condensation polymers having an initial degree of polymerization of about 70 as a function of the concentration of the reactive carrier at various molecular weights.
- Figure 3 illustrates the theoretical loss of intrinsic viscosity of polyethylene terephthalate having an intrinsic viscosity of 0.63 dl/g as a function of the concentration of the reactive carrier at various molecular weights.
- Figure 4 illustrates the theoretical loss of intrinsic viscosity of polyethylene terephthalate having an intrinsic viscosity of 0.45 dl/g as a function of the concentration of the reactive carrier at various molecular weights.
- the invention is a novel method for late additive introduction at an extruder during the processing of condensation polymers (i.e., one or more additives are introduced into the condensation polymers by way of a reactive carrier) .
- the method employs a reactive carrier that not only functions as a delivery vehicle for one or more additives, but also reacts with the condensation polymers to bind the reactive carrier in the polymer resin. This prevents the emergence of the carrier from the condensation polymers during subsequent processing, such as solid state polymerization, drying operations, spinning operations, film extrusion, and injection molding operations. This also improves dispersion of the additive in the condensation polymers and reduces the tendency of the carrier to deposit in polymer processing equipment during solid state polymerization.
- the present invention includes combining at an extruder condensation polymers having carbonyl functionality and a reactive carrier having a molecular weight of less than about 10,000 g/mol and being the delivery vehicle for one or more additives.
- the present invention includes first polymerizing oligomeric precursors via melt phase polycondensation to form condensation polymers having carbonyl functionality. Thereafter, one or more additives are introduced into the condensation polymers at an extruder by way of a reactive carrier that has a molecular weight of less than about 10,000 g/mol.
- the concept of combining (or introducing, adding, etc.) the condensation polymers and the reactive carrier at an extruder embraces (1) introducing both the condensation polymers and the reactive carrier into the extruder; (2) introducing the reactive carrier into the condensation polymers before the extruder, and then mixing the condensation polymers and the reactive carrier within the extruder; and (3) introducing the reactive carrier into the condensation polymers after the extruder.
- Suitable polycondensation polymers according to the present invention include, without limitation, polyesters, polyurethanes, polycarbonates, polyamides, and polyimides. Polyesters, such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, are preferred.
- oligomeric precursors to condensation polymers may be formed by reacting a first polyfunctional component and a second polyfunctional component.
- oligomeric precursors to polycarbonates may be formed by reacting diols and derivatives of carbonic acid
- oligomeric precursors to polyurethanes may be formed by reacting diisocyanates and diols
- oligomeric precursors to polyamides may be formed by diacids and dianaines
- oligomeric precursors to polyimides may be formed by reacting dianhydrides and diamines. See, e . g. , Odian, Principles of Polymerization, (Second Edition 1981) . These kinds of reactions are well understood by those of ordinary skill in the polymer arts and will not be further discussed herein.
- Polyesters are the preferred polycondensation polymers, and so the present invention is herein described with particular reference to the introduction of additives into a process for making polyethylene terephthalate.
- oligomeric precursors to polyesters may be formed by reacting diacids and diols or by reacting diesters and diols.
- the diols may be either aliphatic or aromatic.
- the invention preferably includes reacting a terephthalate component and a diol component to form polyethylene terephthalate precursors, e.g., bis (2- hydroxyethyl) terephthalate .
- polyethylene terephthalate precursors e.g., bis (2- hydroxyethyl) terephthalate .
- These oligomeric precursors are then polymerized via melt phase polycondensation to form polymers of polyethylene terephthalate.
- ethylene glycol is continuously removed to create favorable reaction kinetics.
- one or more additives are introduced by way of a reactive carrier into the polyethylene terephthalate polymers (i.e., the reactive carrier functions as an additive delivery vehicle) .
- the polyethylene terephthalate polymers may be pelletized, and thereafter the polyethylene terephthalate polymers and the reactive carrier are introduced at— preferably into—an extruder.
- the reactive carrier which has a molecular weight of less than about 10,000 g/mol, not only facilitates uniform blending of the additives within the polymer melt, but also reacts with the polyethylene terephthalate polymers to ensure that the carrier does not emerge during subsequent processes.
- the reactive carrier which, as noted, has a molecular weight of less than about 10,000 g/mol, not only facilitates uniform blending of the additives within the polymer melt, but also reacts with the polyethylene terephthalate polymers to ensure that the carrier does not emerge during subsequent processes.
- Intrinsic viscosity is the ratio of the specific viscosity of a polymer solution of known concentration to the concentration of solute, extrapolated to zero concentration. Intrinsic viscosity, which is widely recognized as standard measurements of polymer characteristics, is directly proportional to average polymer molecular weight. See, e . g. , Dictionary of Fiber and Textile Technology, Hoechst Celanese Corporation (1990); Tortora & Merkel, Fairchild' s Dictionary of Textiles (7 th Edition 1996) .
- Intrinsic viscosity can be measured and determined without undue experimentation by those of ordinary skill in this art.
- OCP orthochlorophenol
- the intrinsic viscosity is determined by dissolving the copolyester in orthochlorophenol (OCP) , measuring the relative viscosity of the solution using a Schott Autoviscometer (AVS Schott and AVS 500 Viscosystem) , and then calculating the intrinsic viscosity based on the relative viscosity. See, e . g. , Dictionary of Fiber and Textile Technology (“intrinsic viscosity”) .
- a 0.6-gram sample (+/- 0.005 g) of dried polymer sample is dissolved in about 50 ml (61.0 - 63.5 grams) of orthochlorophenol at a temperature of about 105 °C. Fiber and yarn samples are typically cut into small pieces, whereas chip samples are ground. After cooling to room temperature, the solution is placed in the viscometer at a controlled, constant temperature, (e.g., between about 20°C and 25°C), and the relative viscosity is measured. As noted, intrinsic viscosity is calculated from relative viscosity.
- diol component herein refers primarily to ethylene glycol, although other diols (e.g., low molecular weight polyethylene glycol) may be used as well. It will be understood by those of ordinary skill in the art that the diol component usually forms the majority of terminal ends of the polymer chains and so is present in the composition in slightly greater fractions. For example, the molar ratio of the terephthalate component and the diol component is typically between about 1.0:1.0 and 1.0:1.6.
- terephthalate component refers to diacids and diesters that can be used to prepare polyethylene terephthalate.
- the terephthalate component mostly includes terephthalic acid and dimethyl terephthalate, but can include diacid and diester comonomers as well.
- terephthalate component mostly includes terephthalic acid and dimethyl terephthalate, but can include diacid and diester comonomers as well.
- terephthalate component mostly includes terephthalic acid and dimethyl terephthalate, but can include diacid and diester comonomers as well.
- those having ordinary skill in the art will know that there are two conventional methods for forming polyethylene terephthalate. These methods are well known to those skilled in the art.
- One method employs a direct esterification reaction using terephthalic acid and excess ethylene glycol.
- the aforementioned step of reacting a terephthalate component and a diol component includes reacting terephthalic acid and ethylene glycol in a heated esterification reaction to form monomers and oligomers of terephthalic acid and ethylene glycol, as well as a water byproduct.
- the water must be continuously removed as it is formed.
- the other method involves a two-step ester exchange reaction and polymerization using dimethyl terephthalate and excess ethylene glycol.
- the aforementioned step of reacting a terephthalate component and a diol component includes reacting dimethyl terephthalate and ethylene glycol- in a heated ester exchange reaction to form monomers and oligomers of terephthalate and ethylene glycol, as well as methanol as a byproduct.
- the ester exchange reaction To enable the ester exchange reaction to go essentially to completion, the methanol must be continuously removed as it is formed.
- the polyethylene terephthalate herein described may be a modified polyethylene terephthalate to the extent the diol ' component includes ' other glycols besides ethylene glycol, such as diethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 1,4- cyclohexane dimethanol, or the terephthalate component includes modifiers such as isophthalic acid, 2,6- naphthalene dicarboxylic acid, succinic acid, or one or more functional derivatives of terephthalic acid.
- most commercial polyethylene terephthalate polymers are modified polyethylene terephthalate polyesters.
- the direct esterification reaction is preferred over the older, two-step ester exchange reaction.
- the direct esterification technique reacts terephthalic acid and ethylene glycol to form low molecular weight monomers, oligomers, and water.
- the continuous feed enters a direct esterification vessel that is operated at a temperature of between about 240 °C and 290 °C and at a pressure of between about 5 and 85 psia for between about one and five hours.
- the reaction which is typically uncatalyzed, forms low molecular weight monomers, oligomers, and water.
- the water is removed as the esterification reaction proceeds and excess ethylene glycol is removed to provide favorable reaction kinetics.
- the low molecular weight monomers and oligomers are polymerized via polycondensation to form polyethylene terephthalate polyester.
- This polycondensation stage generally employs a series of two or more vessels and is operated at a temperature of between about 250 °C and 305 °C for between about one and four hours.
- the polycondensation reaction usually begins in a first vessel called the low polymerizer.
- the low polymerizer is operated at a pressure range of between about 0 and 70 torr.
- the monomers and oligomers polycondense to form polyethylene terephthalate and ethylene glycol.
- the ethylene glycol is removed from the polymer melt using an applied vacuum to drive the reaction to completion. In this regard, the polymer melt is typically agitated to promote the escape of the ethylene glycol from the polymer melt and to assist the highly viscous polymer melt in moving through the polymerization vessel.
- the final vessel generally called the "high polymerizer,” is operated at a pressure of between about 0 and 40 torr.
- each of the polymerization vessels is connected to a flash vessel and each is typically agitated to facilitate the removal of ethylene glycol.
- the residence time in the polymerization vessels and the feed rate of the ethylene glycol and terephthalic acid into the continuous process is determined in part based on the target molecular weight of the polyethylene terephthalate polyester.
- the intrinsic viscosity of the polymer melt is generally used to determine polymerization conditions, such as temperature, pressure, the feed rate of the reactants, and the residence time within the polymerization vessels.
- polymerization conditions such as temperature, pressure, the feed rate of the reactants, and the residence time within the polymerization vessels.
- cyclic oligomers e.g., trimer and tetramers of terephthalic acid and ethylene glycol
- cyclic oligomers may occur in minor amounts.
- the continued removal of ethylene glycol as it forms in the polycondensation reaction will generally reduce the formation of these by-products.
- the condensation polymers of the present invention are generally filtered and extruded in the melt phase to form polymer sheets, filaments, or pellets.
- the polymer melt is extruded immediately after polycondensation.
- the polymers are quenched, preferably by spraying with water or immersing in a water trough, to promote solidification.
- the solidified condensation polymers are cut into chips or pellets for storage and handling purposes.
- the term "pellets" is used generally to refer to chips, pellets, and the like.
- SSP solid state polymerization
- Solid state polymerization can be initiated either before or after introducing the reactive carrier. It should be noted that the inclusion of the reactive carrier does not adversely affect the SSP rate and often will even increase the SSP rate. Thereafter, polymer chips are then re-melted and re-extruded to form items such as containers (e.g., beverage bottles), filaments, films, or other applications.
- containers e.g., beverage bottles
- the present invention improves upon the prior art by employing a reactive carrier rather than an inert carrier or no carrier at all.
- the reactive carrier should be introduced to the condensation polymers in quantities such that bulk polymer properties are not significantly affected.
- the reactive carrier preferably is capable of combining with the condensation polymers such that it is non-extractable during subsequent processing operations.
- the invention includes introducing to an extruder condensation polymers having carbonyl functionality and a reactive carrier that is the delivery vehicle for one or more additives.
- the reactive carrier which has an average molecular weight of less than about 10,000 g/mol, is introduced to the extruder in quantities such that bulk polymer properties of the condensation polymers are not significantly affected.
- the concept of introducing to an extruder condensation polymers and a reactive carrier embraces (1) introducing both the condensation polymers and the reactive carrier into the extruder; and (2) introducing the reactive carrier into the condensation polymers before the extruder, and then mixing the condensation polymers and the reactive carrier within the extruder.
- the reactive carrier has a melting point that ensures that it is a liquid or slurry at about 100 °C, which can be achieved using low-pressure steam.
- the reactive carrier has a melting point that ensures that it is a liquid or slurry at near ambient temperatures.
- near ambient includes temperatures between about 20°C and 60 °C. Near ambient temperatures simplify the unit operations necessary to introduce additives as complicated heating systems are not needed to introduce the reactive carrier into the condensation polymers.
- condensation polymers are preferably solid
- the reactive carrier can be a solid when combined with the condensation polymers at the extruder.
- a solid reactive carrier is preferably introduced into the extruder toward the back of the extruder as this promotes melting and mixing (and reacting) of the condensation polymers and the reactive carrier.
- the reactive carrier is a liquid or slurry when combined with the condensation polymers at the extruder.
- a liquid or slurried reactive carrier can be introduced into the back or front of the . extruder.
- the reactive carrier is a liquid or slurry at near ambient temperatures.
- the reactive carrier should make up no more than about one weight percent of the polymer resin ( i . e . , 10,000 ppm) .
- the reactive carrier is introduced to the condensation polymers in quantities such that its concentration in the polymer resin is less than about 1000 ppm (i.e., 0.1 weight percent) . Reducing the reactive carrier to quantities such that its concentration in the polymer resin is less than 500 ppm (i.e., 0.05 weight percent) will further reduce potential adverse effects to bulk polymer properties.
- Figures 1 and 2 illustrate the theoretical loss of molecular weight (as measured by number-average degree of polymerization) as a function of the concentration of the reactive carrier at various molecular weights.
- Figure 1 depicts the impact of the reactive carrier upon condensation polymers that have an initial degree of polymerization of about 100.
- Figure 2 depicts the impact of the reactive carrier upon condensation polymers that have an initial degree of polymerization of about 70.
- degree of polymerization of about 100 corresponds to an intrinsic viscosity of about 0.61 dl/g and a degree of polymerization of about 70 corresponds to an intrinsic viscosity of about 0.45 dl/g.
- the reactive carriers having higher molecular weights have less adverse effect upon the polymer resin' s average degree of polymerization.
- Figures 3 and 4 illustrate the theoretical loss of intrinsic viscosity as a function of reactive carrier concentration at several molecular weights.
- Figure 3 depicts the impact of the reactive carrier upon polyethylene terephthalate having an intrinsic viscosity of 0.63 dl/g.
- Figure 4 depicts the impact of the reactive carrier upon polyethylene terephthalate having intrinsic viscosity of 0.45 dl/g.
- macromolecules having a degree of polymerization of about 70 are considered high polymers.
- polyethylene terephthalate this roughly translates to a molecular weight of at least about 13,000 g/mol. At this molecular weight, polyethylene terephthalate polymers possess sufficient molecular weight, mechanical properties, melt strength, and crystallinity to facilitate polymer processing.
- the reactive carriers according to the present invention have molecular weights that are less than about 10,000 g/mol.
- the molecular weight of the reactive carrier is typically less than 6000 g/mol, preferably less than 4000 g/mol, more preferably between about 300 and 2000 g/mol, and most preferably between about 400 and 1000 g/mol.
- molecular weight refers to number-average molecular weight, rather than weight-average molecular weight.
- Suitable reactive carriers include esters (including low polymers derived from caprolactone) , amides (including low polymers derived from caprolactam) , imides, amines, isocyanates, oxazolines, acids, and anhydrides that are capable of reacting with the condensation polymers in a way that diminishes molecular weight loss of the condensation polymers during subsequent heated processes, such as injection molding and extrusion operations.
- polyols especially polyester polyols and polyether polyols, having a molecular weight that is sufficiently high such that the polyol will not substantially reduce the average molecular weight of the condensation polymers, and a viscosity that facilitates pumping of the polyol.
- Polyethylene glycol is a preferred polyol.
- Other exemplary polyols include functional polyethers, such as polypropylene glycol that is prepared from propylene oxide, random and block copolymers of ethylene oxide and propylene oxide, and polytetramethylene glycol that is derived from the polymerization of tetrahydrofuran.
- the reactive carrier may also include dimer or trimer acids and anhydrides.
- the reactive carrier may possess, in addition to or in place of terminal functional groups, internal functional groups (e.g., esters, amides, and anhydrides) that react with the condensation polymers.
- the reactive carrier may include esters without terminal functional groups, amides without terminal functional groups, or anhydrides without terminal functional groups that are capable of reacting into the condensation polymers during solid state polymerization and that will not cause the condensation polymers to suffer loss of molecular weight during injection molding or extrusion processes.
- caprolactone and caprolactam are within the scope of the present invention.
- additives are sometimes marketed with oligomers that constitute an acceptable reactive carrier.
- TINUVIN ® 213 which is available from Ciba Specialty Chemicals, includes a hydroxyphenyl benzotriazole ultraviolet light absorber in a solution of unreacted polyethylene glycol having a molecular weight of 300 g/mol.
- polyethylene glycol is 'a preferred reactive carrier. Accordingly, the present invention embraces the use of such premixed, additive/reactive carrier products.
- An exemplary method according to the present invention includes reacting terephthalic acid and ethylene glycol in a heated esterification reaction to form monomers and oligomers of terephthalic acid and ethylene glycol, then polymerizing these monomers and oligomers via melt phase polycondensation to form polyethylene terephthalate polymers.
- the polyethylene terephthalate polymers are then formed into chips (or pellets via a polymer cutter) and solid state polymerized. Thereafter, an additive is introduced at an extruder into the polyethylene terephthalate polymers using a reactive carrier, which facilitates uniform blending within the polymer melt.
- the reactive carrier is a polyol (e.g., polyethylene glycol) having a molecular weight that permits the polyol to be pumped at near ambient temperatures (i.e., less than 60 °C) and that is introduced to the polyethylene terephthalate polymers in quantities such that bulk properties of the polyethylene terephthalate polymers are not significantly affected.
- the polyol reactive carrier combines with the polyethylene terephthalate polymer such that it is non-extractable during subsequent processing operations (e.g., forming polyester beverage containers) .
- the invention embraces the late addition of various kinds of additives via the reactive carrier. Late addition is especially desirable where the additives are volatile or subject to thermal degradation.
- Conventional additive injection prior to polycondensation such as during an esterification stage in the synthesis of polyester, or early during the polycondensation stage subjects additives to several hours of high-temperature (greater than 260°C) and reduced-pressure (less than 10 torr) conditions. Consequently, additives that have significant vapor pressure at these conditions will be lost from the process.
- the method of the present invention significantly reduces the time additives are exposed to high polycondensation temperatures.
- Additives according to the present invention can include preform heat-up rate enhancers, friction-reducing additives, stabilizers, inert particulate additives (e.g., clays or silicas), colorants, antioxidants, branching agents, oxygen barrier agents, carbon dioxide barrier agents, oxygen scavengers, flame retardants, crystallization control agents, acetaldehyde reducing agents, impact modifiers, catalyst deactivators, melt strength enhancers, anti-static agents, lubricants, chain extenders, nucleating agents, solvents, fillers, and plasticizers .
- preform heat-up rate enhancers e.g., friction-reducing additives, stabilizers, inert particulate additives (e.g., clays or silicas), colorants, antioxidants, branching agents, oxygen barrier agents, carbon dioxide barrier agents, oxygen scavengers, flame retardants, crystallization control agents, acetaldehyde reducing agents, impact modifiers, catalyst deactivators, melt strength enhancer
- the additive is an ultraviolet (UV) radiation absorber.
- UV absorbers protect the polyethylene terephthalate polymers and contents of packages from UV degradation.
- the additive is an inert particulate additive, preferably either talc (i.e., a natural hydrous magnesium silicate of representative formula 3MgO»4SiO 2 »H 2 0) or precipitated calcium carbonate.
- the inert particulate additive is introduced in low concentrations ( i . e . , about 20 and 200 ppm based on the combined weight of the condensation polymers, the reactive carrier, and the inert particulate additive) to ensure that bottles formed from the condensation polymers possess reduced frictional characteristics .
- the inert particulate additive which is preferably surface-treated to minimize haze formation in bottles, preferably has an average particle size of less than about ten microns, more preferably less than two microns.
- bottles formed from such polyethylene terephthalate condensation polymers have improved frictional characteristics that reduce, and can eliminate, the need to apply, during filling operations, external lubricants to polyester bottles.
- the additive is an exfoliated clay nanocomposite, which enhances gas barrier properties in films and containers.
- Nanocomposites preferably are in the form of platelets having a thickness of between about 6 and 15 angstroms.
- the additive carried by the reactive carrier is a catalyst stabilizer—more typically, extra catalyst stabilizer.
- any stabilizer that will deactivate the polymerization catalyst may be introduced via a reactive carrier.
- the stabilizer should be non-reactive with the polymer and possess low residual moisture.
- thermally stable polyester refers to polyester having low acetaldehyde content, low discoloration, and high retention of molecular weight despite exposure to high temperatures.
- Acetaldehyde is an objectionable byproduct of polyethylene terephthalate degradation. This is of particular concern to the food and beverage industry because acetaldehyde, even in minute amounts, adversely affects product taste. Moreover, polymer degradation will typically cause undesirable discoloration or yellowing. This is why a stabilizer, preferably containing phosphorous, is added to the polymer melt.
- the late addition of the stabilizer to the polymer melt and then again at an extruder prevents the stabilizer from inhibiting
- the stabilizer can adequately prevent discoloration and degradation of the polyethylene terephthalate polyester.
- condensation polymers are thermally stable. Accordingly, the stabilizer additive must be adequately blended with the polymer melt to deactivate polymerization catalysts.
- the reactive carrier facilitates the incorporation of the stabilizer into the polymer resin.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002246670A AU2002246670A1 (en) | 2000-12-15 | 2001-12-14 | Methods of post-polymerisation extruder injection in condensation polymer production |
DE60105197T DE60105197T2 (en) | 2000-12-15 | 2001-12-14 | POST-POLYMERIZATION-INJECTION MOLDING EXTRUSION PROCESS IN THE PRODUCTION OF CONDENSATION POLYMERS |
JP2002552739A JP2004530733A (en) | 2000-12-15 | 2001-12-14 | Method of extruder injection after polymerization in condensation polymer production. |
EP01994249A EP1349884B1 (en) | 2000-12-15 | 2001-12-14 | Methods of post-polymerisation extruder injection in condensation polymer production |
AT01994249T ATE274541T1 (en) | 2000-12-15 | 2001-12-14 | POST-POLYMERIZATION - INJECTION MOLDING EXTRUSION PROCESS IN THE PRODUCTION OF CONDENSATION POLYMERS |
CA002431823A CA2431823A1 (en) | 2000-12-15 | 2001-12-14 | Methods of post-polymerization extruder injection in condensation polymer production |
MXPA03005346A MXPA03005346A (en) | 2000-12-15 | 2001-12-14 | Methods of post-polymerisation extruder injection in condensation polymer production. |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/738,619 US6500890B2 (en) | 2000-12-15 | 2000-12-15 | Polyester bottle resins having reduced frictional properties and methods for making the same |
US09/738,619 | 2000-12-15 | ||
US09/932,150 | 2001-08-17 | ||
US09/932,150 US6569991B2 (en) | 2000-12-15 | 2001-08-17 | Methods of post-polymerization extruder injection in polyethylene terephthalate production |
US10/017,400 US6590069B2 (en) | 2000-12-15 | 2001-12-14 | Methods of post-polymerization extruder injection in condensation polymer production |
Publications (3)
Publication Number | Publication Date |
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WO2002051616A2 true WO2002051616A2 (en) | 2002-07-04 |
WO2002051616A3 WO2002051616A3 (en) | 2002-11-21 |
WO2002051616A8 WO2002051616A8 (en) | 2002-12-27 |
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PCT/US2001/048440 WO2002051616A2 (en) | 2000-12-15 | 2001-12-14 | Methods of post-polymerisation extruder injection in condensation polymer production |
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Cited By (4)
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WO2003080701A1 (en) * | 2002-03-23 | 2003-10-02 | Zimmer Ag | Polytrimethylene terephthalate resins with improved properties |
WO2005121233A1 (en) * | 2004-06-03 | 2005-12-22 | Cyclics Corporation | Intimate physical mixtures containing macrocyclic polyester oligomer and filler |
US7759449B2 (en) | 2000-12-15 | 2010-07-20 | Wellman, Inc. | Methods for introducing additives into polyethylene terephthalate |
US8022168B2 (en) | 2004-09-02 | 2011-09-20 | Grupo Petrotexmex, S.A. de C.V. | Spheroidal polyester polymer particles |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US8557950B2 (en) | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
US9267007B2 (en) | 2005-09-16 | 2016-02-23 | Grupo Petrotemex, S.A. De C.V. | Method for addition of additives into a polymer melt |
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EP0169085A1 (en) * | 1984-05-21 | 1986-01-22 | Elf Atochem S.A. | Polyamide composition with retarded combustibility |
EP0718341A2 (en) * | 1994-12-21 | 1996-06-26 | General Electric Company | High molecular weight stabilizer compounds for stabilizing polymers |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US7759449B2 (en) | 2000-12-15 | 2010-07-20 | Wellman, Inc. | Methods for introducing additives into polyethylene terephthalate |
US7858731B2 (en) | 2000-12-15 | 2010-12-28 | Wellman, Inc. | Polyester resins and polyester containers having reduced frictional properties |
WO2003080701A1 (en) * | 2002-03-23 | 2003-10-02 | Zimmer Ag | Polytrimethylene terephthalate resins with improved properties |
US7223471B2 (en) | 2002-03-23 | 2007-05-29 | Zimmer Ag | Polytrimethylene terephthalate resins with improved properties |
WO2005121233A1 (en) * | 2004-06-03 | 2005-12-22 | Cyclics Corporation | Intimate physical mixtures containing macrocyclic polyester oligomer and filler |
US8022168B2 (en) | 2004-09-02 | 2011-09-20 | Grupo Petrotexmex, S.A. de C.V. | Spheroidal polyester polymer particles |
Also Published As
Publication number | Publication date |
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WO2002051616A8 (en) | 2002-12-27 |
WO2002051616A3 (en) | 2002-11-21 |
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